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TW201817722A - Compound, resin, composition, and pattern forming method - Google Patents

Compound, resin, composition, and pattern forming method Download PDF

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TW201817722A
TW201817722A TW106124617A TW106124617A TW201817722A TW 201817722 A TW201817722 A TW 201817722A TW 106124617 A TW106124617 A TW 106124617A TW 106124617 A TW106124617 A TW 106124617A TW 201817722 A TW201817722 A TW 201817722A
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compound
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carbon atoms
acid
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越後雅敏
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日商三菱瓦斯化學股份有限公司
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    • C07C43/00Ethers; Compounds having groups, groups or groups
    • C07C43/02Ethers
    • C07C43/20Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
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    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00Ethers; Compounds having groups, groups or groups
    • C07C43/02Ethers
    • C07C43/20Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
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    • C08F216/02Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
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    • C08F224/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031Organic compounds not covered by group G03F7/029
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    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
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    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105After-treatment
    • H01L21/311Etching the insulating layers by chemical or physical means
    • H01L21/31144Etching the insulating layers by chemical or physical means using masks

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Abstract

A compound represented by the following formula (o).

Description

化合物、樹脂、組成物及圖型形成方法  Compound, resin, composition and pattern forming method  

本發明係關於具有特定結構的化合物、樹脂及含有此等的組成物。又關於使用該組成物的圖型形成方法。 The present invention relates to a compound having a specific structure, a resin, and a composition containing the same. Further, there is a pattern forming method using the composition.

對於半導體裝置的製造,雖有藉由使用光阻材料的光刻之微細加工的進行,但近年來隨著LSI的高集成度與高速度化,藉由圖型規定之進一步微型化被期待著。又,使用於抗蝕圖型形成時的光刻用光源為自KrF準分子激光(248nm)至ArF準分子激光(193nm)被短波長化,極端紫外光(EUV、13.5nm)的導入亦被預測著。 In the manufacture of a semiconductor device, the microfabrication by photolithography is carried out. However, in recent years, with the high integration and high speed of LSI, further miniaturization by pattern specifications is expected. . Further, the light source for lithography used in the formation of the resist pattern is short-wavelength from the KrF excimer laser (248 nm) to the ArF excimer laser (193 nm), and the introduction of extreme ultraviolet light (EUV, 13.5 nm) is also Forecasting.

然而,在使用過去的高分子系抗蝕材料的光刻中,該分子量為較大的1萬~10萬程度,分子量分布亦廣,故於圖型表面上產生粗糙度的圖型尺寸之控制變的困難,微型化有極限。於此,至今欲賦予更高解像性的抗蝕圖型,已有種種低分子量抗蝕材料被提案。因低分子量抗 蝕材料的分子尺寸為小,故期待賦予解像性高,且粗糙度小的抗蝕圖型。 However, in the photolithography using the conventional polymer-based resist material, the molecular weight is as large as 10,000 to 100,000, and the molecular weight distribution is also wide, so that the control of the pattern size on the surface of the pattern is generated. Difficult to change, miniaturization has limits. Heretofore, various types of low molecular weight resist materials have been proposed to provide a resist pattern having higher resolution. Since the molecular size of the low molecular weight corrosion resistant material is small, it is expected to provide a resist pattern having high resolution and low roughness.

現在作為如此低分子系抗蝕材料,已知有種種。例如已提出將低分子量多核多酚化合物作為主成分使用的鹼顯像型負型感放射線性組成物(例如參考專利文獻1及專利文獻2),作為具有高耐熱性之低分子量抗蝕材料的候補者,亦有提出將低分子量環狀多酚化合物作為主成分使用的鹼顯像型負型感放射線性組成物(例如參考專利文獻3及非專利文獻1)。又作為抗蝕材料的基礎化合物,多酚化合物雖低分子量但可賦予高耐熱性,故已知可作為抗蝕圖型解像性或粗糙度的改善上使用(例如參照非專利文獻2)。 As such a low molecular resistance resist material, various kinds are known. For example, an alkali-developing negative-type radiation-sensitive linear composition using a low-molecular-weight polynuclear polyphenol compound as a main component (for example, refer to Patent Document 1 and Patent Document 2) has been proposed as a low-molecular-weight resist material having high heat resistance. As a candidate, an alkali-developing negative-type radiation-sensitive linear composition using a low molecular weight cyclic polyphenol compound as a main component has been proposed (for example, refer to Patent Document 3 and Non-Patent Document 1). Further, as a base compound of a resist material, the polyphenol compound has a low molecular weight and can impart high heat resistance. Therefore, it is known to be used as an improvement in resist pattern resolution or roughness (see, for example, Non-Patent Document 2).

本發明者們,至今作為具有優良蝕刻耐性的同時,亦在溶劑中為可溶而可適用於濕式製程的材料,有提出含有特定結構的化合物及有機溶劑之抗蝕組成物(參照專利文獻4)。 The inventors of the present invention have been proposed to have a coating composition containing a specific structure and an organic solvent as a material which has excellent etching resistance and is soluble in a solvent and can be applied to a wet process (refer to the patent literature). 4).

又,若繼續進行抗蝕圖型微型化,因會產生解像度的問題或者於顯像後傾倒抗蝕圖型之問題,故變的期待抗蝕之薄膜化。然而,若僅進行抗蝕薄膜化時,於基板加工上得到充分抗蝕圖型膜厚變的困難。因此,製作出不僅為抗蝕圖型,且抗蝕與進行加工的半導體基板之間製作出抗蝕下層膜,對於該抗蝕下層膜亦使其具有作為基板加工時的遮罩之功能的製程成為必須。 Further, if the resist pattern miniaturization is continued, there is a problem of resolution or a problem of dumping the resist pattern after development, and thus the film of the resist is expected to be thinned. However, when only the resist thin film formation is performed, it becomes difficult to obtain a sufficient resist pattern thickness on the substrate processing. Therefore, a resist underlayer film is formed not only for the resist pattern but also between the resist and the processed semiconductor substrate, and the underlayer film is also provided with a function as a mask for processing the substrate. Become a must.

現在作為如此製程用抗蝕下層膜,已知有種 種。例如作為實現與過去蝕刻速度快的抗蝕下層膜相異,且具有接近抗蝕的乾蝕刻速度之選擇比的光刻用抗蝕下層膜者,已有提出含有至少具有藉由輸入所定能量,末端基經脫離後產生磺酸殘基之取代基的樹脂成分與溶劑之多層抗蝕製程用下層膜形成材料(參考專利文獻5)。又,作為實現具有與抗蝕相比為小的乾蝕刻速度之選擇比的光刻用抗蝕下層膜者,已有提出含有具有特定重複單位之聚合物的抗蝕下層膜材料(參考專利文獻6)。且,作為實現與半導體基板相比具有較小乾蝕刻速度之選擇比的光刻用抗蝕下層膜者,已有提出含有共聚合苊烯類的重複單位與具有取代或非取代的羥基之重複單位所成的聚合物之抗蝕下層膜材料(參考專利文獻7)。 Various types of underlayer films for such processes are known. For example, as a resist underlayer film for lithography which is different from the resist underlayer film which has a fast etching speed in the past and has a selection ratio close to the dry etching speed of the resist, it has been proposed to contain at least a predetermined energy by input. The underlayer film forming material for a multilayer resist process for forming a resin component having a substituent of a sulfonic acid residue after leaving the terminal group and a solvent (refer to Patent Document 5). Further, as a resist underlayer film for lithography which has a selection ratio of a dry etching rate which is smaller than that of a resist, a resist underlayer film material containing a polymer having a specific repeating unit has been proposed (refer to the patent literature). 6). Further, as a resist underlayer film for lithography which has a smaller selection ratio of dry etching speed than a semiconductor substrate, it has been proposed to repeat a repeating unit containing a copolymerized terpene and a substituted or unsubstituted hydroxyl group. A resist underlayer film material of a polymer formed by a unit (refer to Patent Document 7).

另一方面,對於該抗蝕下層膜,作為具有高蝕刻耐性之材料,已知有將甲烷氣、乙烷氣、乙炔氣等作為原料使用而藉由CVD所形成的非晶質碳下層膜。然而,由製程上之觀點來看,在旋轉塗佈法與絲網印刷等濕式製程可形成抗蝕下層膜之抗蝕下層膜材料被期待著。 On the other hand, as the material having high etching resistance, an amorphous carbon underlayer film formed by CVD using methane gas, ethane gas, acetylene gas or the like as a raw material is known. However, from the viewpoint of the process, a resist underlayer film material which can form a resist underlayer film by a wet process such as a spin coating method or screen printing is expected.

又,本發明者們對於作為具有優良蝕刻耐性之同時,其耐熱性高且於溶劑為可溶之可適用於濕式製程的材料,已提出含有特定結構的化合物及有機溶劑之光刻用下層膜形成組成物(參照專利文獻8)。 Further, the inventors of the present invention have proposed a lower layer for lithography containing a compound having a specific structure and an organic solvent, which is excellent in heat resistance and soluble in a solvent, and which is suitable for a wet process. A film formation composition (refer to Patent Document 8).

且,有關在3層製程中對於抗蝕下層膜之形成所使用的中間層的形成方法,例如已知有矽氮化膜的形成方法(參照專利文獻9)或矽氮化膜的CVD形成方法(參照專 利文獻10)。又,作為3層製程用之中間層材料,已知有含有倍半矽氧烷基為基之矽化合物的材料(參考專利文獻11及12)。 Further, regarding a method of forming an intermediate layer used for forming a resist underlayer film in a three-layer process, for example, a method of forming a tantalum nitride film (refer to Patent Document 9) or a method of forming a tantalum nitride film by CVD is known. (Refer to Patent Document 10). Further, as the intermediate layer material for the three-layer process, a material containing a sesquiterpoxyalkyl group-based ruthenium compound is known (refer to Patent Documents 11 and 12).

作為光學零件形成組成物已有種種者被提出,例如有丙烯酸系樹脂(參考專利文獻13~14)或以烯丙基衍生的具有特定結構的多酚(專利文獻15參照)。 There are various types of optical component forming compositions, and examples thereof include acrylic resins (see Patent Documents 13 to 14) or polyphenols having a specific structure derived from allyl groups (see Patent Document 15).

[先前技術文獻]  [Previous Technical Literature]   [專利文獻]  [Patent Literature]  

[專利文獻1]特開2005-326838號公報 [Patent Document 1] JP-A-2005-326838

[專利文獻2]特開2008-145539號公報 [Patent Document 2] JP-A-2008-145539

[專利文獻3]特開2009-173623號公報 [Patent Document 3] JP-A-2009-173623

[專利文獻4]國際公開第2013/024778號 [Patent Document 4] International Publication No. 2013/024778

[專利文獻5]特開2004-177668號公報 [Patent Document 5] JP-A-2004-177668

[專利文獻6]特開2004-271838號公報 [Patent Document 6] JP-A-2004-271838

[專利文獻7]特開2005-250434號公報 [Patent Document 7] JP-A-2005-250434

[專利文獻8]國際公開第2013/024779號 [Patent Document 8] International Publication No. 2013/024779

[專利文獻9]特開2002-334869號公報 [Patent Document 9] JP-A-2002-334869

[專利文獻10]國際公開第2004/066377號 [Patent Document 10] International Publication No. 2004/066377

[專利文獻11]特開2007-226170號公報 [Patent Document 11] JP-A-2007-226170

[專利文獻12]特開2007-226204號公報 [Patent Document 12] JP-A-2007-226204

[專利文獻13]特開2010-138393號公報 [Patent Document 13] JP-A-2010-138393

[專利文獻14]特開2015-174877號公報 [Patent Document 14] JP-A-2015-174877

[專利文獻15]國際公開第2014/123005號 [Patent Document 15] International Publication No. 2014/123005

[非專利文獻]  [Non-patent literature]  

[非專利文獻1]T.Nakayama,M.Nomura,K.Haga,M.Ueda : Bull.Chem.Soc.Jpn.,71,2979(1998) [Non-Patent Document 1] T. Nakayama, M. Nomura, K. Haga, M. Ueda: Bull. Chem. Soc. Jpn., 71, 2979 (1998)

[非專利文獻2]岡崎信次等22名「光阻材料開發之新展開」CMC股份有限公司出版,2009年9月,p.211-259 [Non-Patent Document 2] 22 "New Development of Photoresist Materials Development" by Megaki Shinji, published by CMC Corporation, September 2009, p.211-259

如上述,過去雖已提出多數使用抗蝕用途的光刻用膜形成組成物及使用下層膜用途的光刻用膜形成組成物,但對於不僅具有可適用於旋轉塗佈法或絲網印刷等濕式製程的高溶劑溶解性,且並非有在高次元下兼具耐熱性及蝕刻耐性者,故正期待著新材料之開發。 As described above, in the past, many lithographic film forming compositions for resist use and lithographic film forming compositions for use in underlayer films have been proposed, but they are not only applicable to spin coating or screen printing. We are looking forward to the development of new materials because of the high solvent solubility of the wet process and the fact that it does not have heat resistance and etching resistance at high temperatures.

又,可得到優良鹼顯像性、光感度及解像度的抗蝕永久膜之較佳的新穎材料的開發亦期待著。 Further, development of a novel novel material capable of obtaining a resist permanent film excellent in alkali developability, light sensitivity, and resolution is also expected.

且,在過去雖有多數的使用於光學構件之組成物被提出,但並未有在高次元下兼具耐熱性、透明性及折射率,故期待新穎的材料之開發。 Further, although many compositions for optical members have been proposed in the past, heat resistance, transparency, and refractive index have not been obtained in a high degree, and development of novel materials is expected.

本發明為有鑑於上述課題者,其目的為提供一種可適用於濕式製程,且在形成具有優良耐熱性、溶解性及蝕刻耐性的光阻及光阻用下層膜上為有用的化合物、樹脂、光刻用膜形成組成物者。又,提供使用該組成物的抗蝕膜、抗蝕下層膜、抗蝕永久膜、圖型形成方法。且提 供使用於光學構件之組成物。 The present invention has been made in view of the above problems, and an object thereof is to provide a compound and a resin which are useful for a wet process and which are useful for forming an underlayer film for photoresist and photoresist having excellent heat resistance, solubility, and etching resistance. A film for lithography forms a composition. Further, a resist film, a resist underlayer film, a resist permanent film, and a pattern forming method using the composition are provided. And a composition for use in an optical member is provided.

本發明者們欲解決上述課題而進行重複詳細檢討結果,發現藉由具有特定結構之化合物或樹脂可解決上述課題而完成本發明。 The present inventors have made it possible to solve the above problems and repeat the detailed review results, and have found that the present invention can be solved by solving the above problems by a compound or a resin having a specific structure.

即,本發明如以下所示。 That is, the present invention is as follows.

[1]下述式(0)所示的化合物。 [1] A compound represented by the following formula (0).

(式(0)中,RY為氫原子、碳數1~30的烷基或碳數6~30的芳基,RZ為碳數1~60的N價基或單鍵,RT各獨立為可具有取代基之碳數1~30的烷基、可具有取代基之碳數6~30的芳基、可具有取代基之碳數2~30的烯基、可具有取代基之碳數1~30的烷氧基、鹵素原子、硝基、胺基、羧酸基、硫醇基、羥基或羥基的氫原子 可由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基、前述烷基、前述芳基、前述烯基、前述烷氧基可含有醚鍵、酮鍵或酯鍵,其中,RT的至少一個為,含有羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基,X表示氧原子、硫原子或無交聯者,m各獨立為0~9的整數,其中,m的至少一個為1~9的整數,N為1~4的整數,其中,N為2以上的整數時,N個[ ]內之結構式可為相同或相異,r各獨立為0~2的整數。) (In the formula (0), R Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R Z is an N-valent group or a single bond having 1 to 60 carbon atoms, and each of R T An alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and a carbon which may have a substituent The hydrogen atom of an alkoxy group, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group of 1 to 30 may be selected from an allyloxyalkyl group, a propyleneoxyalkyl group or an A group. a group substituted with one group of a acryloxyalkyl group, the aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group, and the above alkoxy group may have an ether bond, a keto bond or an ester bond, wherein at least one of R T Is a hydrogen atom containing a hydroxyl group substituted by one group selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacryloxyalkyl, and X represents an oxygen atom, a sulfur atom or none. For the crosslinker, m is independently an integer of 0 to 9, wherein at least one of m is an integer of 1 to 9, and N is an integer of 1 to 4, wherein when N is an integer of 2 or more, N [ ] The structural formulas may be the same or different, and each of r is independently 0~2. number.)

[2]前述式(0)所示化合物為下述式(1)所示化合物之上述[1]所記載的化合物。 [2] The compound represented by the above formula (0) is a compound described in the above [1], which is a compound represented by the following formula (1).

(式(1)中,R0與前述RY同義,R1為碳數1~60的N價基或單鍵,R2~R5各獨立為可具有取代基之碳數1~30的烷基、可具有取代基之碳數6~30的芳基、可具有取代基之碳數2~30的烯基、可具有取代基之碳數1~30的烷氧基、鹵素原子、硝基、胺基、羧酸基、硫醇基、羥基或羥基的氫原子可由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基、前述烷基、前述芳基、前述烯基、前述烷氧基可含有醚鍵、酮鍵或酯鍵,其中,R2~R5的至少一個為,含有羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基,m2及m3各獨立為0~8的整數,m4及m5各獨立為0~9的整數,但,m2、m3、m4及m5不會同時成為0,n為與前述N同義,其中,n為2以上的整數時,N個[ ]內之結構式可為相同或相異,p2~p5與前述r同義。) (In the formula (1), R 0 is synonymous with the above R Y , R 1 is an N-valent group or a single bond having 1 to 60 carbon atoms, and each of R 2 to R 5 is independently a carbon number of 1 to 30 which may have a substituent. An alkyl group, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, and a nitrate The hydrogen atom of the group, the amine group, the carboxylic acid group, the thiol group, the hydroxyl group or the hydroxyl group may be substituted by one group selected from the group consisting of an allyloxyalkyl group, a propyleneoxyalkyl group or a methacryloxyalkyl group. The group, the alkyl group, the aryl group, the aforementioned alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond or an ester bond, wherein at least one of R 2 to R 5 is a hydrogen atom containing a hydroxyl group selected from a group substituted with one group of allyloxyalkyl, acryloxyalkyl or methacryloxyalkyl, m 2 and m 3 are each independently an integer of 0-8, m 4 and m 5 Each of the independent integers is 0 to 9, but m 2 , m 3 , m 4 , and m 5 do not simultaneously become 0, and n is synonymous with the above N. When n is an integer of 2 or more, N [ ] The structural formulas may be the same or different, and p 2 ~p 5 are synonymous with the aforementioned r.)

[3]前述式(0)所示化合物為下述式(2)所示化合物之上述[1]所記載的化合物。 [3] The compound of the above formula (0) is a compound of the above formula (2), which is the compound of the above formula (2).

(式(2)中,R0A與前述RY同義,R1A為碳數1~60的NA價基或單鍵,R2A各獨立為可具有取代基之碳數1~30的烷基、可具有取代基之碳數6~30的芳基、可具有取代基之碳數2~30的烯基、可具有取代基之碳數1~30的烷氧基、鹵素原子、硝基、胺基、羧酸基、硫醇基、羥基或羥基的氫原子可由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基、前述烷基、前述芳基、前述烯基、前述烷氧基可含有醚鍵、酮鍵或酯鍵,其中,R2A的至少一個為,含有羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基,nA為前述N同義,其中,nA為2以上的整數時,nA個[ ]內之結構式可為相同或相異,XA表示氧原子、硫原子或無交聯者,m2A各獨立為0~7的整數,但,至少一個的m2A為1~7的整數, qA各獨立為0或1。) (In the formula (2), R 0A is synonymous with the above R Y , R 1A is a N A valent group or a single bond having 1 to 60 carbon atoms, and R 2A is each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent. An aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, The hydrogen atom of an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group may be substituted with a group selected from an allyloxyalkyl group, a propyleneoxyalkyl group or a methacryloxyalkyl group. The alkyl group, the aforementioned aryl group, the aforementioned alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond or an ester bond, wherein at least one of R 2A is a hydrogen atom containing a hydroxyl group selected from an allyloxy group. an alkyl group, an alkyl group, a propylene group or a methyl group, Bing Xixi substituted alkyl group, n a is the same meaning as N, where, n a is an integer of 2 or more, n a number in [] The structural formula may be the same or different, X A represents an oxygen atom, a sulfur atom or a non-crosslinker, and m 2A is independently an integer of 0-7, but at least one m 2A is an integer of 1-7, q A is independent of 0 or 1.)

[4]前述式(1)所示化合物為下述式(1-1)所示化合物的上述[2]所記載的化合物。 [4] The compound of the above formula (1) is a compound described in the above [2], which is a compound represented by the following formula (1-1).

(式(1-1)中,R0、R1、R4、R5、n、p2~p5、m4及m5為與前述同義,R6~R7各獨立為可具有取代基之碳數1~30的烷基、可具有取代基之碳數6~30的芳基、可具有取代基之碳數2~30的烯基、鹵素原子、硝基、胺基、羧酸基、硫醇基,R10~R11各獨立為氫原子或選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基,其中,R10~R11的至少一個為選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基,m6及m7各獨立為0~7的整數,但,m4、m5、m6及m7不會同時為0。) (In the formula (1-1), R 0 , R 1 , R 4 , R 5 , n, p 2 to p 5 , m 4 and m 5 are synonymous with the above, and R 6 to R 7 are each independently substituted. An alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, and a carboxylic acid a thiol group, each of R 10 to R 11 independently being a hydrogen atom or a group selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacryloxyalkyl, wherein R 10 At least one of ~R 11 is a group selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacryloxyalkyl, and m 6 and m 7 are each independently an integer of 0-7. However, m 4 , m 5 , m 6 and m 7 will not be 0 at the same time.)

[5]前述式(1-1)所示化合物為下述式(1-2)所示化合物之上述[4]所記載的化合物。 [5] The compound of the above formula (1-1) is a compound described in the above [4], which is a compound represented by the following formula (1-2).

(式(1-2)中,R0、R1、R6、R7、R10、R11、n、p2~p5、m6及m7為與前述同義,R8~R9與前述R6~R7同義,R12~R13與前述R10~R11同義,m8及m9各獨立為0~8的整數,但,m6、m7、m8及m9不會同時為0。) (In the formula (1-2), R 0 , R 1 , R 6 , R 7 , R 10 , R 11 , n, p 2 to p 5 , m 6 and m 7 are synonymous with the above, R 8 to R 9 Synonymous with R 6 to R 7 described above, R 12 to R 13 are synonymous with R 10 to R 11 described above, and m 8 and m 9 are each independently an integer of 0 to 8, but m 6 , m 7 , m 8 and m 9 Will not be 0 at the same time.)

[6]前述式(2)所示化合物為下述式(2-1)所示化合物之上述[3]所記載的化合物。 [6] The compound represented by the above formula (2) is a compound described in the above [3], which is a compound represented by the following formula (2-1).

(式(2-1)中,R0A、R1A、nA、qA及XA與前述式(2)中者同義,R3A各獨立為可具有取代基之碳數1~30的烷基、可具有取代基之碳數6~30的芳基、可具有取代基之碳數2~30的烯基、鹵素原子、硝基、胺基、羧酸基、硫醇基,R4A各獨立為氫原子或羥基的氫原子可由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基,其中,R4A的至少一個為選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基,m6A各獨立為0~5的整數。) (In the formula (2-1), R 0A , R 1A , n A , q A and X A are synonymous with those in the above formula (2), and each of R 3A is independently an alkane having 1 to 30 carbon atoms which may have a substituent. An aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group, and each of R 4A A hydrogen atom independently a hydrogen atom or a hydroxyl group may be substituted by one group selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacryloxyalkyl, wherein at least one of R 4A It is a group selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacryloxyalkyl, and m 6A is independently an integer of 0 to 5.)

[7]將上述[1]所記載的化合物作為單體所得之樹脂。 [7] A resin obtained by using the compound described in the above [1] as a monomer.

[8]具有下述式(3)所示結構之上述[7]所記載的樹脂。 [8] The resin described in the above [7] having the structure represented by the following formula (3).

(式(3)中,L為可具有取代基之碳數1~30的伸烷基、可具有取代基之碳數6~30的伸芳基、可具有取代基之碳數1~30的伸烷氧基或單鍵,前述伸烷基、前述伸芳基、前述伸烷氧基可含有醚鍵、酮鍵或酯鍵,R0與前述RY同義,R1為碳數1~60的N價基或單鍵,R2~R5各獨立為可具有取代基之碳數1~30的烷基、可具有取代基之碳數6~30的芳基、可具有取代基之碳數2~30的烯基、可具有取代基之碳數1~30的烷氧基、鹵素原子、硝基、胺基、羧酸基、硫醇基、羥基或羥基的氫原子可由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基、前述烷基、前述芳基、前述烯基、前述烷氧基可含有醚鍵、酮鍵或酯鍵,其中,R2~R5的至少一個為含有羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代 的基,m2及m3各獨立為0~8的整數,m4及m5各獨立為0~9的整數,但,m2、m3、m4及m5不會同時成為0,R2~R5的至少一個為羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基) (In the formula (3), L is an alkylene group having 1 to 30 carbon atoms which may have a substituent, an extended aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number of 1 to 30 which may have a substituent An alkoxy group or a single bond, the alkylene group, the aforementioned aryl group, the alkoxy group may have an ether bond, a ketone bond or an ester bond, R 0 is synonymous with the aforementioned R Y , and R 1 is a carbon number of 1 to 60. N valent or single bond, R 2 to R 5 are each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon which may have a substituent The number of 2 to 30 alkenyl groups, the alkoxy group having a carbon number of 1 to 30 which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group may be selected from alkene. a group substituted with one group of a propyloxyalkyl group, a acryloxyalkyl group or a methacryloxyalkyl group; the aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group, and the aforementioned alkoxy group may contain an ether bond a ketone bond or an ester bond, wherein at least one of R 2 to R 5 is a hydroxyl group-containing hydrogen atom selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacryloxyalkylene a group substituted group, m 2 and m 3 each independently 0 to 8 Integer, m 4 and m 5 each independently an integer of 0 to 9, but, m 2, m 3, m 4 and m 5 at the same time does not become 0, R 2 ~ R 5 is at least one hydroxyl group selected from a hydrogen atom by a a group substituted with one group of allyloxyalkyl, acryloxyalkyl or methacryloxyalkyl)

[9]具有下述式(4)所示結構的上述[7]所記載的樹脂。 [9] The resin according to the above [7] having the structure represented by the following formula (4).

(式(4)中,L為可具有取代基之碳數1~30的伸烷基、可具有取代基之碳數6~30的伸芳基、可具有取代基之碳數1~30的伸烷氧基或單鍵,前述伸烷基、前述伸芳基、前述伸烷氧基可含有醚鍵、酮鍵或酯鍵,R0A與前述RY同義,R1A為碳數1~30的NA價基或單鍵,R2A各獨立為可具有取代基之碳數1~30的烷基、可具有取代基之碳數6~30的芳基、可具有取代基之碳數2~30 的烯基、可具有取代基之碳數1~30的烷氧基、鹵素原子、硝基、胺基、羧酸基、硫醇基、羥基或羥基的氫原子可由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基、前述烷基、前述芳基、前述烯基、前述烷氧基可含有醚鍵、酮鍵或酯鍵,其中,R2A的至少一個為含有羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基,nA為前述N同義,其中,nA為2以上的整數時,nA個[ ]內之結構式可為相同或相異,XA表示氧原子、硫原子或無交聯者,m2A各獨立為0~7的整數,但,至少一個m2A為1~7的整數,qA各獨立為0或1。) (In the formula (4), L is an alkylene group having 1 to 30 carbon atoms which may have a substituent, an extended aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number of 1 to 30 which may have a substituent An alkoxy group or a single bond, the alkylene group, the aforementioned aryl group, the alkoxy group may have an ether bond, a ketone bond or an ester bond, R 0A is synonymous with the aforementioned R Y , and R 1A is a carbon number of 1 to 30. N A valent or single bond, R 2A each independently is an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number which may have a substituent 2 The alkenyl group of ~30, the alkoxy group having a carbon number of 1 to 30 which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group may be selected from allyl groups. a group substituted with one group of an oxyalkyl group, a acryloxyalkyl group or a methacryloxyalkyl group; the alkyl group, the aryl group, the aforementioned alkenyl group, and the alkoxy group may contain an ether bond or a ketone a bond or an ester bond, wherein at least one of R 2A is a hydrogen atom having a hydroxyl group substituted by one group selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacryloxyalkyl; group, n A is synonymous with the N, wherein when n A is an integer of 2 or more, n A structural formula [] may be within the same or different, X A represents an oxygen atom, a sulfur atom or noncrosslinked persons, m 2A are each independently an integer of 0 to 7, However, at least one m 2A is an integer from 1 to 7, and q A is independently 0 or 1.

[10]含有選自由上述[1]~[6]中任一所記載的化合物及上述[7]~[9]中任一所記載的樹脂所成群的1種以上之組成物。 [10] The one or more components selected from the group consisting of the compound according to any one of the above [1] to [6], and the resin according to any one of the above [7] to [9].

[11]進一步含有溶劑之上述[10]所記載的組成物。 [11] A composition according to the above [10], which further contains a solvent.

[12]進一步含有酸產生劑之上述[10]或[11]所記載的組成物。 [12] The composition according to the above [10] or [11], further comprising an acid generator.

[13] 進一步含有交聯劑之上述[10]~[12]中任一所記載的組成物。 [13] The composition according to any one of the above [10] to [12], further comprising a crosslinking agent.

[14]前述交聯劑為選自由酚化合物、環氧化合物、氰酸酯化合物、胺基化合物、苯並噁嗪化合物、三聚氰胺化合物、胍胺化合物、乙二醇脲化合物、脲化合物、異氰酸酯化合物及疊氮化合物所成群的至少1種之前述[13]所記載的組成物。 [14] The foregoing crosslinking agent is selected from the group consisting of a phenol compound, an epoxy compound, a cyanate compound, an amine compound, a benzoxazine compound, a melamine compound, a guanamine compound, an ethylene glycol urea compound, a urea compound, and an isocyanate compound. And at least one of the compositions described in the above [13] in which the azide compound is grouped.

[15]前述交聯劑為至少具有1個烯丙基之前述[13]或[14]所記載的組成物。 [15] The crosslinking agent is the composition according to the above [13] or [14] which has at least one allyl group.

[16]前述交聯劑的含有比例對於將含有選自由前述[1]~[6]中任一所記載的化合物及前述[7]~[9]中任一一項所記載的樹脂所成群的1種以上之組成物的合計質量作為100質量份時為0.1~100質量份之前述[13]~[15]中任一所記載的組成物。 [16] The content of the above-mentioned crosslinking agent is a resin which is a resin according to any one of the above [1] to [6], and the resin according to any one of the above [7] to [9]. The composition according to any one of the above [13] to [15], wherein the total mass of the one or more components of the group is 0.1 to 100 parts by mass.

[17]進一步含有交聯促進劑之前述[13]~[16]中任一所記載的組成物。 [17] The composition according to any one of the above [13] to [16], which further comprises a crosslinking accelerator.

[18]前述交聯促進劑為選自由胺類、咪唑類、有機膦類、及路易氏酸所成群的至少1種之前述[17]所記載的組成物。 [18] The crosslinking accelerator is a composition described in the above [17], which is at least one selected from the group consisting of amines, imidazoles, organic phosphines, and Lewis acids.

[19]前述交聯促進劑的含有比例對於將含有選自由前述[1]~[6]中任一所記載的化合物及前述[7]~[9]中任一所記載的樹脂所成群的1種以上之組成物的合計質量作為100質量份時為0.1~5質量份之前述[17]或[18]所記載的組成物。 [19] The content of the crosslinking accelerator is a group of the resin according to any one of the above [1] to [6], and the resin according to any one of the above [7] to [9]. The composition described in the above [17] or [18] is 0.1 to 5 parts by mass based on 100 parts by mass of the total mass of the one or more components.

[20]進一步含有自由基聚合起始劑的前述[10]~[19]中任一所記載的組成物。 [20] The composition according to any one of [10] to [19] further comprising a radical polymerization initiator.

[21]前述自由基聚合起始劑為選自由酮系光聚合起始劑、有機過氧化物系聚合起始劑及偶氮系聚合起始劑所成群的至少1種之前述[10]~[20]中任一所記載的組成物。 [21] The radical polymerization initiator is at least one selected from the group consisting of a ketone photopolymerization initiator, an organic peroxide polymerization initiator, and an azo polymerization initiator. [10] The composition according to any one of [20].

[22]前述自由基聚合起始劑的含有比例對於將含有選自由前述[1]~[6]中任一所記載的化合物及前述[7]~[9]中任一項所記載的樹脂所成群的1種以上之組成物的合計質量作為100質量份時為0.05~25質量份之前述[10]~[21]中任一所記載的組成物。 [22] The content of the above-mentioned radical polymerization initiator is a resin according to any one of the above [1] to [6], and the resin according to any one of the above [7] to [9] The composition described in any one of the above [10] to [21], which is 0.05 to 25 parts by mass, in a total mass of one or more of the components.

[23]使用於光刻用膜形成的前述[10]~[22]中任一所記載的組成物。 [23] The composition according to any one of the above [10] to [22], which is used for forming a film for lithography.

[24]使用於抗蝕永久膜形成的前述[10]~[22]中任一所記載的組成物。 [24] The composition according to any one of the above [10] to [22], which is used for the formation of a resistive permanent film.

[25]使用於光學零件形成的前述[10]~[22]中任一所記載的組成物。 [25] The composition according to any one of the above [10] to [22], which is used for forming an optical component.

[26]含有於基板上使用前述[23]所記載的組成物形成光阻層後,於前述光阻層的所定區域照射放射線並進行顯 像的步驟之抗蝕圖型形成方法。 [26] A resist pattern forming method comprising the step of forming a photoresist layer on the substrate by using the composition described in the above [23], irradiating radiation in a predetermined region of the photoresist layer, and performing development.

[27]含有於基板上使用前述[23]所記載的組成物形成下層膜,於前述下層膜上形成至少1層光阻層後,於前述光阻層所定區域照射放射線並進行顯像之步驟的抗蝕圖型形成方法。 [27] A step of forming a lower layer film on the substrate by using the composition described in the above [23], forming at least one photoresist layer on the underlayer film, and irradiating radiation in a predetermined region of the photoresist layer to perform development A method of forming a resist pattern.

[28]含有於基板上使用前述[23]所記載的組成物形成下層膜,於前述下層膜上使用抗蝕中間層膜材料形成中間層膜,於前述中間層膜上形成至少1層光阻層後,於前述光阻層的所定區域照射放射線並顯像後形成抗蝕圖型,其後將前述抗蝕圖型作為遮罩對前述中間層膜進行蝕刻,將所得之中間層膜圖型作為蝕刻遮罩對前述下層膜進行蝕刻,將所得之下層膜圖型作為蝕刻遮罩對基板進行蝕刻後於基板上形成圖型之步驟的電路圖型形成方法。 [28] forming a lower layer film on the substrate using the composition according to [23], forming an intermediate layer film on the underlayer film using a resist interlayer film material, and forming at least one layer of photoresist on the intermediate layer film. After the layer is irradiated with radiation in a predetermined area of the photoresist layer to form a resist pattern, and then the resist pattern is used as a mask to etch the intermediate layer film, and the obtained intermediate layer film pattern is obtained. The circuit pattern forming method of etching the underlayer film as an etching mask, and forming the underlying film pattern as an etching mask to etch the substrate and forming a pattern on the substrate.

本發明中之化合物及樹脂為對安全溶劑之溶解性高,具有良好耐熱性及蝕刻耐性者。又,含有本發明中之化合物及/或樹脂的抗蝕組成物可賦予良好抗蝕圖型形狀。 The compound and the resin in the present invention have high solubility in a safe solvent and have good heat resistance and etching resistance. Further, the resist composition containing the compound and/or resin of the present invention can impart a good resist pattern shape.

[實施發明的形態]  [Formation of the Invention]  

以下對於欲實施本發明的形態(以下亦稱為「本實施形態」)進行說明。且,以下實施形態為欲說明 本發明的例示,本發明並未僅限定於該實施形態。 Hereinafter, the form in which the present invention is to be carried out (hereinafter also referred to as "this embodiment") will be described. Further, the following embodiments are illustrative of the present invention, and the present invention is not limited to the embodiments.

本實施形態中之化合物、樹脂及含有此的組成物可適用於濕式製程,對於欲形成具有優良耐熱性及蝕刻耐性之光阻下層膜為有用。又,於本實施形態中之組成物因使用耐熱性及高溶劑溶解性且具有特定結構之化合物或樹脂,故可形成可抑制高溫燒烤時之膜劣化,對於氧電漿蝕刻等亦具有優良蝕刻耐性之抗蝕及下層膜。另外,形成下層膜時,因與抗蝕層之密著性亦優良,故可形成優良的抗蝕圖型。 The compound, the resin, and the composition containing the same in the present embodiment are applicable to a wet process, and are useful for forming a photoresist underlayer film having excellent heat resistance and etching resistance. Further, since the composition of the present embodiment is a compound or a resin having a specific structure by using heat resistance and high solvent solubility, it is possible to form a film which can suppress deterioration of the film during high-temperature baking, and also has excellent etching for oxygen plasma etching or the like. Resistant anti-corrosion and underlayer film. Further, when the underlayer film is formed, it is excellent in adhesion to the resist layer, so that an excellent resist pattern can be formed.

又,於本實施形態中之化合物及樹脂為使用於感光性材料時的感度或解像度亦優良者,可維持高耐熱性下,進一步在形成與汎用有機溶劑或其他化合物、樹脂成分及添加劑之相溶性優良的抗蝕永久膜上為有用。 Further, in the case where the compound and the resin in the present embodiment are excellent in sensitivity or resolution when used in a photosensitive material, it is possible to maintain a high heat resistance and further form a phase with a general-purpose organic solvent or other compound, a resin component, and an additive. It is useful on a permanent film of excellent corrosion resistance.

且,由折射率高,由自低溫至高溫的廣範圍之熱處理所造成的著色亦可被抑制,故作為各種光學形成組成物亦有用。 Further, since the coloring is high because of the high refractive index and the heat treatment from a wide range of temperatures from low temperature to high temperature is suppressed, it is also useful as various optical forming compositions.

[式(0)所示化合物]  [Compound represented by formula (0)]  

本實施形態中之化合物為下述式(0)所示。 The compound in the present embodiment is represented by the following formula (0).

(式(0)中,RY為氫原子、碳數1~30的烷基或碳數6~30的芳基,RZ為碳數1~60的N價基或單鍵,RT各獨立為可具有取代基之碳數1~30的烷基、可具有取代基之碳數6~30的芳基、可具有取代基之碳數2~30的烯基、可具有取代基之碳數1~30的烷氧基、鹵素原子、硝基、胺基、羧酸基、硫醇基、羥基或羥基的氫原子可由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基、前述烷基、前述芳基、前述烯基、前述烷氧基可含有醚鍵、酮鍵或酯鍵,其中,RT的至少一個為,含有羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基,X表示氧原子、硫原子或無交聯者,m各獨立為0~9的整數,其中,m的至少一個為1~9的整數,N為1~4的整數,其中,N為2以上的整數時,N個[ ]內之結構式可為相同或相異, r各獨立為0~2的整數。) (In the formula (0), R Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R Z is an N-valent group or a single bond having 1 to 60 carbon atoms, and each of R T An alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and a carbon which may have a substituent The hydrogen atom of an alkoxy group, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group of 1 to 30 may be selected from an allyloxyalkyl group, a propyleneoxyalkyl group or an A group. a group substituted with one group of a acryloxyalkyl group, the aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group, and the above alkoxy group may have an ether bond, a keto bond or an ester bond, wherein at least one of R T Is a hydrogen atom containing a hydroxyl group substituted by one group selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacryloxyalkyl, and X represents an oxygen atom, a sulfur atom or none. For the crosslinker, m is independently an integer of 0 to 9, wherein at least one of m is an integer of 1 to 9, and N is an integer of 1 to 4, wherein when N is an integer of 2 or more, N [ ] The structural formulas may be the same or different, and each of r is independently 0~2. Number.)

RY為氫原子、碳數1~30的烷基或碳數6~30的芳基。烷基可使用直鏈狀、支鏈狀或者環狀的烷基。RY為氫原子、碳數1~30的直鏈狀、支鏈狀或者環狀的烷基或碳數6~30的芳基,故可賦予優良的耐熱性及溶劑溶解性。 R Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. As the alkyl group, a linear, branched or cyclic alkyl group can be used. R Y is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, so that excellent heat resistance and solvent solubility can be imparted.

Rz為碳數1~60的N價基或單鍵,介著該Rz鍵結各芳香環。N為1~4的整數,N為2以上的整數時,N個[ ]內之結構式可為相同或相異。且,所謂前述N價基為,N=1時為碳數1~60的烷基,N=2時為碳數1~30的伸烷基,N=3時為碳數2~60的烷烴丙基,N=4時為碳數3~60的烷烴四基。作為前述N價基,例如可舉出具有直鏈狀烴基、支鏈狀烴基或脂環式烴基者等。其中,對於前述脂環式烴基,亦含有有橋脂環式烴基。又,前述N價烴基可具有脂環式烴基、雙鍵、雜原子或者碳數6~60的芳香族基。 R z is an N-valent group or a single bond having 1 to 60 carbon atoms, and each of the aromatic rings is bonded via the R z . N is an integer of 1 to 4, and when N is an integer of 2 or more, the structural formulae of N [ ] may be the same or different. Further, the N-valent group is an alkyl group having 1 to 60 carbon atoms when N=1, an alkylene group having 1 to 30 carbon atoms when N=2, and an alkane having 2 to 60 carbon atoms when N=3. The propyl group, when N=4, is an alkane tetra group having a carbon number of 3 to 60. Examples of the N-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group or an alicyclic hydrocarbon group. Among them, the alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group. Further, the N-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 60 carbon atoms.

RT各獨立為可具有取代基之碳數1~30的烷基、可具有取代基之碳數6~30的芳基、可具有取代基之碳數2~30的烯基、可具有取代基之碳數1~30的烷氧基、鹵素原子、硝基、胺基、羧酸基、硫醇基、羥基或羥基的氫原子可由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基、前述烷基、前述芳基、前述烯基、前述烷氧基可含有醚鍵、酮鍵或酯鍵,其中,RT的至少一個為含有羥基的氫原子由選自烯丙基氧基 烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基。且前述烷基、烯基及烷氧基可為直鏈狀、支鏈狀或者環狀的基。 R T is each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and may have a substitution. The hydrogen atom having an alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group may be selected from the group consisting of allyloxyalkyl groups and acryloxyalkylene groups. a group substituted with one group of a methacryloxyalkyl group, the above alkyl group, the above aryl group, the aforementioned alkenyl group, and the aforementioned alkoxy group may have an ether bond, a keto bond or an ester bond, wherein R T At least one of the hydroxyl group-containing hydrogen atoms is substituted by one group selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacryloxyalkyl. Further, the alkyl group, the alkenyl group and the alkoxy group may be a linear, branched or cyclic group.

其中,所謂羥基的氫原子可由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基,其為具有選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基之基,例如可舉出烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基等。 Wherein the hydrogen atom of the hydroxyl group may be substituted by a group selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacryloxyalkyl, which has a hydroxy group selected from the group consisting of allyloxy groups The one group of the alkyl group, the acryloxyalkyl group or the methacryloxyalkyl group may, for example, be an allyloxyalkyl group, a propyleneoxyalkyl group or a methacryloxyalkylene oxide. Base.

X表示氧原子、硫原子或無交聯者,X為氧原子或硫原子時,因有表現高耐熱性之傾向故佳,以氧原子者為較佳。X由溶解性之觀點來看,以無交聯者為佳。又,m各獨立為0~9的整數,m的至少一個為1~9的整數。 X represents an oxygen atom, a sulfur atom or a non-crosslinker. When X is an oxygen atom or a sulfur atom, it tends to exhibit high heat resistance, and an oxygen atom is preferred. From the viewpoint of solubility, X is preferably a non-crosslinker. Further, m is independently an integer of 0 to 9, and at least one of m is an integer of 1 to 9.

式(0)中,萘結構所示部位在r=0時為單環結構,在r=1時為二環結構,在r=2時為三環結構。r各獨立為0~2的整數。上述m為配合以r所決定的環結構而決定其數值範圍。 In the formula (0), the moiety represented by the naphthalene structure has a monocyclic structure at r=0, a bicyclic structure when r=1, and a tricyclic structure when r=2. r is independently an integer of 0~2. The above m is determined by the ring structure determined by r.

[式(1)所示化合物]  [Compound represented by formula (1)]  

於本實施形態中之化合物(0)由耐熱性及溶劑溶解性的觀點來看,以下述式(1)所示化合物為佳。 The compound (0) in the present embodiment is preferably a compound represented by the following formula (1) from the viewpoint of heat resistance and solvent solubility.

上述(1)式中,R0為氫原子、碳數1~30的烷基或碳數6~30的芳基。R0為氫原子、碳數1~30的直鏈狀、支鏈狀或者環狀的烷基或碳數6~30的芳基時,耐熱性變的比較高,有提高溶劑溶解性之傾向。又,R0由抑制氧化分解且抑制化合物之著色,並提高耐熱性及溶劑溶解性的觀點來看,以碳數1~30的直鏈狀、支鏈狀或者環狀的烷基或碳數6~30的芳基者為佳。 In the above formula (1), R 0 is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. When R 0 is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, heat resistance is relatively high, and there is a tendency to improve solvent solubility. . Further, R 0 is a linear, branched or cyclic alkyl group or carbon number having 1 to 30 carbon atoms from the viewpoint of suppressing oxidative decomposition, suppressing coloration of a compound, and improving heat resistance and solvent solubility. 6 to 30 aryl is preferred.

R1為碳數1~60的N價基或單鍵,介著R1鍵結各芳香環。 R 1 is an N-valent group or a single bond having 1 to 60 carbon atoms, and each aromatic ring is bonded via R 1 .

R2~R5各獨立為可具有取代基之碳數1~30的烷基、可具有取代基之碳數6~30的芳基、可具有取代基之碳數2~30的烯基、可具有取代基之碳數1~30的烷氧基、鹵素原子、硝基、胺基、羧酸基、硫醇基、羥基或羥基的氫原子可由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基、前述烷基、前述芳基、前述烯基、前述烷氧基可含有醚鍵、酮鍵或酯鍵,其中,R2 ~R5的至少一個為含有羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代之基。 R 2 to R 5 are each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, The hydrogen atom having an alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group which may have a substituent may be selected from an allyloxyalkyl group and a propylene group. a group substituted with one group of an oxyalkyl group or a methacryloxyalkyl group, the aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group, and the aforementioned alkoxy group may have an ether bond, a keto bond or an ester bond, wherein At least one of R 2 to R 5 is a group in which a hydrogen atom having a hydroxyl group is substituted with one group selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacryloxyalkyl.

m2及m3各獨立為0~8的整數,m4及m5各獨立為0~9的整數。但,m2、m3、m4及m5不會同時為0。 m 2 and m 3 are each independently an integer of 0 to 8, and m 4 and m 5 are each independently an integer of 0 to 9. However, m 2 , m 3 , m 4 and m 5 are not simultaneously zero.

n為1~4的整數。其中,n為2以上的整數時,n個[ ]內的結構式可為相同或相異。 n is an integer from 1 to 4. However, when n is an integer of 2 or more, the structural formulae in n [ ] may be the same or different.

p2~p5各獨立為0~2的整數。 Each of p 2 to p 5 is an integer of 0 to 2.

其中,前述烷基、烯基及烷氧基亦可為直鏈狀、支鏈狀或者環狀的基。 The alkyl group, the alkenyl group and the alkoxy group may be a linear, branched or cyclic group.

且,所謂前述n價基為,n=1時表示碳數1~60的烷基,n=2時表示碳數1~30的伸烷基,n=3時表示碳數2~60的烷烴丙基,n=4時表示碳數3~60的烷烴四基。作為前述n價基,例如可舉出具有直鏈狀烴基、支鏈狀烴基或脂環式烴基者等。其中,對於前述脂環式烴基亦包含有橋脂環式烴基。又,前述n價基可具有碳數6~60的芳香族基。 Further, the n-valent group is an alkyl group having 1 to 60 carbon atoms when n=1, an alkylene group having 1 to 30 carbon atoms when n=2, and an alkane having 2 to 60 carbon atoms when n=3. The propyl group, when n=4, represents an alkane tetra group having a carbon number of 3 to 60. Examples of the n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group or an alicyclic hydrocarbon group. Among them, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group. Further, the n-valent group may have an aromatic group having 6 to 60 carbon atoms.

又,前述n價烴基可具有脂環式烴基、雙鍵、雜原子或者碳數6~60的芳香族基。其中,對於前述脂環式烴基亦含有有橋脂環式烴基。 Further, the n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 60 carbon atoms. Among them, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group.

上述式(1)所示化合物即使為比較低分子量,因該結構的剛直度而具有較高耐熱性,故亦可在高溫燒烤條件下使用。又,於分子中具有3級碳或4級碳,結晶性受到抑制,可作為可使用於光刻用膜製造的光刻用膜形成組 成物適用。 The compound represented by the above formula (1) can be used under high-temperature barbecue conditions even if it has a relatively low molecular weight and has high heat resistance due to the rigidity of the structure. Further, it has three grades of carbon or four grades of carbon in the molecule, and the crystallinity is suppressed, and it can be applied as a film forming composition for lithography which can be used for the production of a film for lithography.

又,對於安全溶劑之溶解性為高,因耐熱性及蝕刻耐性為良好,故含有上述式(1)所示化合物之光刻用抗蝕形成組成物可賦予良好抗蝕圖型形狀。 In addition, since the solubility in a safe solvent is high and the heat resistance and the etching resistance are good, the resist formation composition for lithography containing the compound represented by the above formula (1) can be provided with a good resist pattern shape.

且,在比較性低分子量為低黏度,故即使為具有段差之基板(特別為微細空間或孔圖型等),可均勻地填充至該段差的角落下,亦可容易提高膜之平坦性,其結果使用此的光刻用下層膜形成組成物具有良好的埋入及平坦化特性。又,因具有比較性碳濃度之化合物,亦可賦予高蝕刻耐性。 Moreover, since the comparative low molecular weight is low in viscosity, even if it is a substrate having a step (especially in a fine space or a hole pattern), it can be uniformly filled under the corner of the step, and the flatness of the film can be easily improved. As a result, the underlayer film forming composition for lithography using this has good embedding and planarization characteristics. Further, high etching resistance can be imparted by a compound having a comparative carbon concentration.

且因芳香族密度高故折射率高,又因即使藉由自低溫至高溫的廣範圍熱處理亦可抑制著色,故作為各種光學零件形成組成物時亦為有用。其中亦以抑制化合物的氧化分解並抑制著色,使耐熱性及溶劑溶解性提高的觀點,以具有4級碳的化合物為佳。作為光學零件,除薄膜狀、薄片狀的零件以外,作為塑質透鏡(棱鏡透鏡、柱狀透鏡、微透鏡、菲涅爾透鏡、視野角控制透鏡、對比提高透鏡等)、相位差薄膜、電磁波屏蔽用薄膜、棱鏡、光纖、可撓性印刷配線用焊接抗蝕、電鍍抗蝕、多層印刷電路板用層間絶緣膜、感光性光波導路為有用。 Further, since the aromatic density is high, the refractive index is high, and even if the coloring is suppressed by a wide range of heat treatment from a low temperature to a high temperature, it is also useful as a composition for forming various optical components. Among them, a compound having a carbon of 4 grade is preferable from the viewpoint of suppressing oxidative decomposition of the compound and suppressing coloration, and improving heat resistance and solvent solubility. As an optical component, it is a plastic lens (a prism lens, a lenticular lens, a microlens, a Fresnel lens, a viewing angle control lens, a contrast improving lens, etc.), a retardation film, and an electromagnetic wave, in addition to a film-like or sheet-like component. A film for shielding, a prism, an optical fiber, a solder resist for a flexible printed wiring, a plating resist, an interlayer insulating film for a multilayer printed wiring board, and a photosensitive optical waveguide are useful.

上述式(1)所示化合物由交聯的容易度與對有機溶劑之溶解性的觀點來看,以下述式(1-1)所示化合物者為佳。 The compound represented by the above formula (1) is preferably a compound represented by the following formula (1-1) from the viewpoints of easiness of crosslinking and solubility in an organic solvent.

式(1-1)中,R0、R1、R4、R5、n、p2~p5、m4及m5為與前述同義,R6~R7各獨立為可具有取代基之碳數1~30的烷基、可具有取代基之碳數6~30的芳基、可具有取代基之碳數2~30的烯基、鹵素原子、硝基、胺基、羧酸基、硫醇基,R10~R11各獨立為氫原子或選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基,其中,R10~R11的至少一個為選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基,m6及m7各獨立為0~7的整數,但,m4、m5、m6及m7不會同時為0。 In the formula (1-1), R 0 , R 1 , R 4 , R 5 , n, p 2 to p 5 , m 4 and m 5 are synonymous with the above, and each of R 6 to R 7 may independently have a substituent. An alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, and a carboxylic acid group And a thiol group, each of R 10 to R 11 is independently a hydrogen atom or a group selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacryloxyalkyl, wherein R 10 ~ At least one of R 11 is a group selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacryloxyalkyl, and m 6 and m 7 are each independently an integer of 0 to 7, but , m 4 , m 5 , m 6 and m 7 will not be 0 at the same time.

又,上述式(1-1)所示化合物,進一步由交聯的容易度與對有機溶劑的溶解性之觀點來看,以下述式(1-2)所示化合物者為佳。 Further, the compound represented by the above formula (1-1) is preferably a compound represented by the following formula (1-2) from the viewpoints of easiness of crosslinking and solubility in an organic solvent.

式(1-2)中,R0、R1、R6、R7、R10、R11、n、p2~p5、m6及m7為與前述同義,R8~R9與前述R6~R7為同義,R12~R13與前述R10~R11為同義,m8及m9各獨立為0~8的整數。 In the formula (1-2), R 0 , R 1 , R 6 , R 7 , R 10 , R 11 , n, p 2 to p 5 , m 6 and m 7 are synonymous with the above, and R 8 to R 9 are R 6 to R 7 are synonymous, R 12 to R 13 are synonymous with R 10 to R 11 , and m 8 and m 9 are each independently an integer of 0 to 8.

但,m6、m7、m8及m9不會同時為0。 However, m 6 , m 7 , m 8 and m 9 will not be 0 at the same time.

又,上述式(1-1)所示化合物由原料之供給性觀點來看,以下述式(1a)所示化合物者為佳。 Further, the compound represented by the above formula (1-1) is preferably a compound represented by the following formula (1a) from the viewpoint of availability of a raw material.

上述式(1a)中,R0~R5、m2~m5及n與上述式(1)所說明者同義。 In the above formula (1a), R 0 to R 5 , m 2 to m 5 and n are synonymous with those described in the above formula (1).

上述式(1a)所示化合物由對有機溶劑之溶解性的觀點來看,以下述式(1b)所示化合物為較佳。 The compound represented by the above formula (1a) is preferably a compound represented by the following formula (1b) from the viewpoint of solubility in an organic solvent.

上述式(1b)中,R0、R1、R4、R5、m4、m5、n與上述式(1)所說明者同義,R6、R7、R10、R11、m6、m7與上述式(1-1)所說明者同義。 In the above formula (1b), R 0 , R 1 , R 4 , R 5 , m 4 , m 5 and n have the same meanings as those described in the above formula (1), and R 6 , R 7 , R 10 , R 11 and m 6 and m 7 are synonymous with those described in the above formula (1-1).

前述式(1a)所示化合物由反應性的觀點來看,以下述式(1b’)所示化合物者為更佳。 The compound represented by the above formula (1a) is more preferably a compound represented by the following formula (1b') from the viewpoint of reactivity.

上述式(1b’)中,R0、R1、R4、R5、m4、m5、n與上述式(1)所說明者同義,R6、R7、R10、R11、m6、m7與上述式(1-1)所說明者同義。 In the above formula (1b'), R 0 , R 1 , R 4 , R 5 , m 4 , m 5 and n have the same meanings as those described in the above formula (1), and R 6 , R 7 , R 10 and R 11 , m 6 and m 7 have the same meanings as those described in the above formula (1-1).

上述式(1b)所示化合物由對有機溶劑之溶解性的觀點來看,以下述式(1c)所示化合物者為更佳。 The compound represented by the above formula (1b) is more preferably a compound represented by the following formula (1c) from the viewpoint of solubility in an organic solvent.

上述式(1c)中,R0、R1、R6~R13、m6~m9、n與上述式(1-2)所說明者同義。 In the above formula (1c), R 0 , R 1 , R 6 to R 13 , m 6 to m 9 and n are synonymous with those described in the above formula (1-2).

前述式(1b’)所示化合物由反應性的觀點來看 以下述式(1c’)所示化合物者為更佳。 The compound represented by the above formula (1b') is more preferably a compound represented by the following formula (1c') from the viewpoint of reactivity.

前述式(1c’)中,R0、R1、R6~R13、m6~m9、n與前述式(1-2)所說明者同義。 In the above formula (1c'), R 0 , R 1 , R 6 to R 13 , m 6 to m 9 and n are synonymous with those described in the above formula (1-2).

上述式(0)所示化合物的具體例子雖於以下例示,但式(0)所示化合物並未限定於於此所列舉的具體例子。 Specific examples of the compound represented by the above formula (0) are exemplified below, but the compound represented by the formula (0) is not limited to the specific examples listed herein.

上述式中,X與上述式(0)所說明者同義,RT’與上述式(0)所說明的RT為同義,m各獨立為1~6的整數。 In the above formulas, X in the formula (0) as described by synonymous, R T 'and R T as described in the above-described formula (0) are synonymous, m are each independently an integer of 1 to 6.

雖可進一步將上述式(0)所示化合物的具體例子如以下例示,但式(0)所示化合物並未限定於此所列舉的具體例子。 Although a specific example of the compound represented by the above formula (0) can be further exemplified below, the compound represented by the formula (0) is not limited to the specific examples listed herein.

上述式中,X與上述式(0)所說明者同義,RY’、RZ’與上述式(0)所說明的RY、RZ同義。且OR4A的至少一個為含有羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基。 In the above formulas, X in the formula (0) as described by synonymous, R Y ', R Z' and R Y as explained in the above formula (0), R Z synonymous. And at least one of OR 4A is a group in which a hydrogen atom containing a hydroxyl group is substituted with one group selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacryloxyalkyl.

以下雖例示上述式(1)所示化合物之具體例子,式(1)所示化合物並未限定於此所列舉的化合物。 Specific examples of the compound represented by the above formula (1) are exemplified below, and the compound represented by the formula (1) is not limited to the compounds exemplified above.

前述式中,R2、R3、R4、R5與上述式(1)所說明者同義。m2及m3為0~6的整數,m4及m5為0~7的整數。但,選自R2、R3、R4、R5的至少1個為含有羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基,m2、m3、m4、m5不會同時成為0。 In the above formula, R 2 , R 3 , R 4 and R 5 have the same meanings as those described in the above formula (1). m 2 and m 3 are integers of 0 to 6, and m 4 and m 5 are integers of 0 to 7. However, at least one selected from the group consisting of R 2 , R 3 , R 4 and R 5 is a hydrogen atom containing a hydroxyl group selected from an allyloxyalkyl group, a propyleneoxyalkyl group or a methacryloxyalkyl group. The groups substituted by one group, m 2 , m 3 , m 4 , and m 5 do not simultaneously become zero.

於以下進一步例示出上述式(1)所示化合物的具體例子,但式(1)所示化合物並未限定於此列舉的化合物。 Specific examples of the compound represented by the above formula (1) are further exemplified below, but the compound represented by the formula (1) is not limited to the compounds listed herein.

前述式中,R10、R11、R12、R13與上述式(1-2)所說明者同義,R10~R13的至少一個為選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基。 In the above formula, R 10 , R 11 , R 12 and R 13 are the same as those described in the above formula (1-2), and at least one of R 10 to R 13 is selected from allyloxyalkyl group and propyleneoxy group. One group of an alkyl group or a methacryloxyalkyl group.

前述式(1)所示化合物進一步由對有機溶劑之溶解性的觀點來看,以下述式(BiF-1)~(BiF-10)所示化合物者特佳。 The compound represented by the above formula (1) is particularly preferably a compound represented by the following formula (BiF-1) to (BiF-10) from the viewpoint of solubility in an organic solvent.

前述式中,R10~R13各獨立為氫原子或選自由烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的 1個基,其中R10~R13的至少一個為選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基。 In the above formula, R 10 to R 13 are each independently a hydrogen atom or a group selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacryloxyalkyl, wherein R 10 to R 13 At least one of them is one group selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacryloxyalkyl.

以下進一步例示出上述式(0)所示化合物的具體例子,但式(0)所示化合物並未限定於於此所列舉的具體例子。 Specific examples of the compound represented by the above formula (0) are further exemplified below, but the compound represented by the formula (0) is not limited to the specific examples listed herein.

前述式中,R0、R1、n與上述式(1-1)所說明者同義,R10’及R11’與上述式(1-1)所說明的R10及R11為同義,R4’及R5’各獨立為可具有取代基之碳數1~30的烷基、可具有取代基之碳數6~30的芳基、可具有取代基之碳數2~30的烯基、可具有取代基之碳數1~30的烷氧基、鹵素原子、硝基、胺基、羧酸基、硫醇基、羥基或羥基的氫原子可由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基,前述烷基、前述芳基、前述烯基、前述烷氧基可含有醚鍵、酮鍵或酯鍵,R10’及R11’的至少一個為選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基。m4’及m5’為0~8的整數,m10’及m11’為1 ~9的整數,m4’+m10’及m4’+m11’各獨立為1~9的整數。 In the formula, R 0, R 1, n and the above-described formula (1-1) are synonymous, R 10 'and R 11' and R 10 and R explained in the above formulas (1-1) 11 are synonymous, R 4 ' and R 5 ' are each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an alkenyl group having 2 to 30 carbon atoms which may have a substituent. The hydrogen atom of the alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group which may have a substituent may be selected from an allyloxyalkyl group. a group substituted with one group of a acryloxyalkyl group or a methacryloxyalkyl group, the alkyl group, the aryl group, the aforementioned alkenyl group, and the alkoxy group may have an ether bond, a ketone bond or an ester bond At least one of R 10 ' and R 11 ' is a group selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacryloxyalkyl. m 4 ' and m 5 ' are integers from 0 to 8, m 10 ' and m 11 ' are integers from 1 to 9, m 4 ' + m 10 ' and m 4 ' + m 11 ' are each independently from 1 to 9. Integer.

作為R0,例如可舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、三十烷基、苯基、萘基、蒽基、芘基、聯苯基、七苯基。 Examples of R 0 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group, and a triacontane. Base, phenyl, naphthyl, anthracenyl, fluorenyl, biphenyl, heptaphenyl.

作為R4’及R5’,例如可舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、三十烷基、環丙基、環丁基、環戊基、環己基、環庚基、環辛基、環壬基、環癸基、環十一烷基、環十二烷基、環三十烷基、降冰片基、金剛烷基、苯基、萘基、蒽基、芘基、聯苯基、七苯基、乙烯基、烯丙基、三十碳烯基、甲氧基、乙氧基、三十碳烯氧基、氟原子、氯原子、溴原子、碘原子、硫醇基。 Examples of R 4 ' and R 5 ' include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, and a dodecane group. Base, triacontanyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, Cyclotridecyl, norbornyl, adamantyl, phenyl, naphthyl, anthracenyl, fluorenyl, biphenyl, heptaphenyl, vinyl, allyl, tridecenyl, methoxy An ethoxy group, a tridecenyloxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or a thiol group.

前述R0、R4’、R5’的各例示含有異構物。例如丁基為含有n-丁基、異丁基、sec-丁基、tert-丁基。 Each of R 0 , R 4 ' and R 5 ' is exemplified to contain an isomer. For example, butyl contains n-butyl, isobutyl, sec-butyl, tert-butyl.

前述式中,R10~R13與前述式(1-2)所說明者同義,R16為碳數1~30的直鏈狀、支鏈狀或者環狀的伸烷基、碳數6~30的2價芳基或碳數2~30的2價烯基。 In the above formula, R 10 to R 13 have the same meanings as those described in the above formula (1-2), and R 16 is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms and a carbon number of 6~. a divalent aryl group of 30 or a divalent alkenyl group having 2 to 30 carbon atoms.

作為R16,例如可舉出伸甲基、伸乙基、丙烯 基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、十一碳烯基、十二碳烯基、三十碳烯基、環丙烯基、環丁烯基、環戊烯基、環己烯基、環庚烯基、環辛烯基、環壬烯基、環癸烯基、環十一碳烯基、環十二碳烯基、環三十碳烯基、2價降冰片基、2價金剛烷基、2價苯基、2價萘基、2價蒽基、2價芘基、2價聯苯基、2價七苯基、2價乙烯基、2價的烯丙基、2價三十碳烯基。 Examples of R 16 include a methyl group, an ethyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a nonenyl group, and an undecene group. Alkenyl, dodecenyl, tridecenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, ring Decenyl, cycloundecenyl, cyclododecenyl, cyclodecenyl, divalent norbornyl, divalent adamantyl, divalent phenyl, divalent naphthyl, divalent quinone a base, a divalent fluorenyl group, a divalent biphenyl group, a divalent heptaphenyl group, a divalent vinyl group, a divalent allyl group, and a divalent tridecenyl group.

前述R16的各例示含有異構物。例如丁基含有n-丁基、異丁基、sec-丁基、tert-丁基。 Each of the above R 16 examples contains an isomer. For example, butyl contains n-butyl, isobutyl, sec-butyl, tert-butyl.

前述式中,R10~R13與前述式(1-2)所說明者同義,R14各獨立為碳數1~30的直鏈狀、支鏈狀或者環狀的烷基、碳數6~30的芳基,或碳數2~30的烯基、碳數1~30的烷氧基、鹵素原子、硫醇基,m14為0~5的整數,m14’為0~4的整數。 In the above formula, R 10 to R 13 have the same meanings as those described in the above formula (1-2), and each of R 14 is independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms and a carbon number of 6 An aryl group of ~30, or an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom or a thiol group, m 14 is an integer of 0 to 5, and m 14' is 0 to 4 Integer.

作為R14,例如可舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、三十烷基、環丙基、環丁基、環戊基、環己基、環庚基、環辛基、環壬基、環癸基、環十一烷基、環十二烷基、環三十烷基、降冰片基、金剛烷基、苯基、萘基、蒽基、芘基、聯苯基、七苯基、乙烯基、烯丙基、三十碳烯基、甲氧基、乙氧基、三十碳烯氧基、氟原子、氯原子、溴原子、碘原子、硫醇基。 Examples of R 14 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group, and a triacontane. , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl , norbornyl, adamantyl, phenyl, naphthyl, anthracenyl, fluorenyl, biphenyl, heptaphenyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, a trideceneoxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a thiol group.

前述R14的各例示含有異構物。例如丁基含有n-丁基、異丁基、sec-丁基、tert-丁基。 Each of the above R 14 is illustrative of an isomer. For example, butyl contains n-butyl, isobutyl, sec-butyl, tert-butyl.

前述式中,R0、R4’、R5’、m4’、m5’、m10’、m11’與前述為同義,R1’為碳數1~60的基。 In the above formula, R 0 , R 4′ , R 5′ , m 4′ , m 5′ , m 10′ and m 11′ are synonymous with the above, and R 1′ is a group having 1 to 60 carbon atoms.

前述式中,R10~R13與前述式(1-2)所說明者同義,R14各獨立為碳數1~30的直鏈狀、支鏈狀或者環狀的烷基、碳數6~30的芳基或碳數2~30的烯基、碳數1~30的烷氧基、鹵素原子、硫醇基,m14為0~5的整數,m14’為0~4的整數,m14’’為0~3的整數。 In the above formula, R 10 to R 13 have the same meanings as those described in the above formula (1-2), and each of R 14 is independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms and a carbon number of 6 An aryl group of ~30 or an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom or a thiol group, m 14 is an integer of 0 to 5, and m 14' is an integer of 0 to 4 , m 14'' is an integer from 0 to 3.

作為R14,例如可舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、三十烷基、環丙基、環丁基、環戊基、環己基、環庚基、環辛基、環壬基、環癸基、環十一烷基、環十二烷基、環三十烷基、降冰片基、金剛烷基、苯基、萘基、蒽基、芘基、聯苯基、七苯基、乙烯基、烯丙基、三十碳烯基、甲氧基、乙氧基、三十碳烯氧基、氟原子、氯原子、溴原子、碘原子、硫醇基。 Examples of R 14 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group, and a triacontane. , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl , norbornyl, adamantyl, phenyl, naphthyl, anthracenyl, fluorenyl, biphenyl, heptaphenyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, a trideceneoxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a thiol group.

前述R14的各例示含有異構物。例如丁基含有n-丁基、異丁基、sec-丁基、tert-丁基。 Each of the above R 14 is illustrative of an isomer. For example, butyl contains n-butyl, isobutyl, sec-butyl, tert-butyl.

前述式中,R10~R13與前述式(1-2)所說明者同 義,R15為碳數1~30的直鏈狀、支鏈狀或者環狀的烷基、碳數6~30的芳基或碳數2~30的烯基、碳數1~30的烷氧基、鹵素原子、硫醇基。 In the above formula, R 10 to R 13 have the same meanings as those described in the above formula (1-2), and R 15 is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms and a carbon number of 6 to 30. An aryl group or an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom or a thiol group.

作為R15,例如可舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、三十烷基、環丙基、環丁基、環戊基、環己基、環庚基、環辛基、環壬基、環癸基、環十一烷基、環十二烷基、環三十烷基、降冰片基、金剛烷基、苯基、萘基、蒽基、芘基、聯苯基、七苯基、乙烯基、烯丙基、三十碳烯基、甲氧基、乙氧基、三十碳烯氧基、氟原子、氯原子、溴原子、碘原子、硫醇基。 Examples of R 15 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group, and a triacontane. , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl , norbornyl, adamantyl, phenyl, naphthyl, anthracenyl, fluorenyl, biphenyl, heptaphenyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, a trideceneoxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a thiol group.

前述R15的各例示含有異構物。例如丁基含有n-丁基、異丁基、sec-丁基、tert-丁基。 Each of the above R 15 is illustrative of an isomer. For example, butyl contains n-butyl, isobutyl, sec-butyl, tert-butyl.

前述式中,R10~R13與前述式(1-2)所說明者同義。 In the above formula, R 10 to R 13 have the same meanings as those described in the above formula (1-2).

前述式(0)所示化合物由原料的獲得性之觀點來看,更佳為以下列舉的化合物。 The compound represented by the above formula (0) is more preferably a compound listed below from the viewpoint of availability of a raw material.

前述式中,R10~R13與前述式(1-2)所說明者同義。 In the above formula, R 10 to R 13 have the same meanings as those described in the above formula (1-2).

且前述式(0)所示化合物由蝕刻耐性的觀點來看,以具有以下結構的化合物者為佳。 Further, the compound represented by the above formula (0) is preferably a compound having the following structure from the viewpoint of etching resistance.

前述式中,R0A與前述式(0)中之RY為同義,R1A’與前述式(0)中的RZ為同義,R10~R13與前述式(1-2)所說明者同義。 In the above formula, R 0A is synonymous with R Y in the above formula (0), R 1A′ is synonymous with R Z in the above formula (0), and R 10 to R 13 are as described in the above formula (1-2). Synonymous.

前述式中,R10~R13與前述式(1-2)所說明者同義。R14各獨立為碳數1~30的直鏈狀、支鏈狀或者環狀的烷基、碳數6~30的芳基或碳數2~30的烯基、碳數1~30的烷氧基、鹵素原子、硫醇基,m14為0~4的整數。 In the above formula, R 10 to R 13 have the same meanings as those described in the above formula (1-2). R 14 is independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkyl group having 1 to 30 carbon atoms. An oxy group, a halogen atom or a thiol group, and m 14 is an integer of 0 to 4.

作為R14,例如可舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、三十烷基、環丙基、環丁基、環戊基、環己基、環庚基、環辛基、環壬基、環癸基、環十一烷基、環十二烷基、環三十烷基、降冰片基、金剛烷基、苯基、萘基、蒽基、七苯基、乙烯基、烯丙基、三十碳烯基、甲氧基、乙氧基、三十碳烯氧基、氟原子、氯原子、溴原子、碘原子、硫醇基。 Examples of R 14 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group, and a triacontane. , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl , norbornyl, adamantyl, phenyl, naphthyl, anthryl, heptaphenyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, tridecenyloxy, A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a thiol group.

前述R14的各例示含有異構物。例如丁基含有n-丁基、異丁基、sec-丁基、tert-丁基。 Each of the above R 14 is illustrative of an isomer. For example, butyl contains n-butyl, isobutyl, sec-butyl, tert-butyl.

前述式中,R10~R13與前述式(1-2)所說明者同義,R15為碳數1~30的直鏈狀、支鏈狀或者環狀的烷基、碳數6~30的芳基或碳數2~30的烯基、碳數1~30的烷氧基、鹵素原子、硫醇基。 In the above formula, R 10 to R 13 have the same meanings as those described in the above formula (1-2), and R 15 is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms and a carbon number of 6 to 30. An aryl group or an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom or a thiol group.

作為R15,例如可舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、三十烷基、環丙基、環丁基、環戊基、環己基、環庚基、環辛基、環壬基、環癸基、環十一烷基、環十二烷基、環三十烷基、降冰片基、金剛烷基、苯基、萘基、蒽基、七苯基、乙烯基、烯丙基、三十碳烯基、甲氧基、乙氧基、三十碳烯氧基、氟原子、氯原子、溴原子、碘原子、硫醇基。 Examples of R 15 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group, and a triacontane. , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl , norbornyl, adamantyl, phenyl, naphthyl, anthryl, heptaphenyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, tridecenyloxy, A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a thiol group.

前述R15的各例示含有異構物。例如丁基含有n-丁基、異丁基、sec-丁基、tert-丁基。 Each of the above R 15 is illustrative of an isomer. For example, butyl contains n-butyl, isobutyl, sec-butyl, tert-butyl.

前述式中,R10~R13與前述式(1-2)所說明者同義,R16為碳數1~30的直鏈狀、支鏈狀或者環狀的伸烷基、碳數6~30的2價芳基或碳數2~30的2價烯基。 In the above formula, R 10 to R 13 have the same meanings as those described in the above formula (1-2), and R 16 is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms and a carbon number of 6~. a divalent aryl group of 30 or a divalent alkenyl group having 2 to 30 carbon atoms.

作為R16,例如可舉出伸甲基、伸乙基、丙烯基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、十一碳烯基、十二碳烯基、三十碳烯基、環丙烯基、環丁烯基、環戊烯基、環己烯基、環庚烯基、環辛烯基、環壬烯基、環癸烯基、環十一碳烯基、環十二碳烯基、環三十碳烯基、2價降冰片基、2價金剛烷基、2價苯基、2價萘基、2價蒽基、2價七苯基、2價乙烯基、2價烯丙基、2價三十碳烯基。 Examples of R 16 include a methyl group, an ethyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a nonenyl group, and an undecene group. Alkenyl, dodecenyl, tridecenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, ring Decenyl, cycloundecenyl, cyclododecenyl, cyclodecenyl, divalent norbornyl, divalent adamantyl, divalent phenyl, divalent naphthyl, divalent quinone Base, divalent heptaphenyl, divalent vinyl, divalent allyl, divalent tridecenyl.

前述R16的各例示含有異構物。例如丁基含有n-丁基、異丁基、sec-丁基、tert-丁基。 Each of the above R 16 examples contains an isomer. For example, butyl contains n-butyl, isobutyl, sec-butyl, tert-butyl.

前述式中,R10~R13與前述式(1-2)所說明者同義,R14各獨立為碳數1~30的直鏈狀、支鏈狀或者環狀的烷基、碳數6~30的芳基或碳數2~30的烯基、碳數1~30的烷氧基、鹵素原子、硫醇基,m14’為0~4的整數。 In the above formula, R 10 to R 13 have the same meanings as those described in the above formula (1-2), and each of R 14 is independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms and a carbon number of 6 An aryl group of ~30 or an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom or a thiol group, and m 14' is an integer of 0 to 4.

作為R14,例如可舉出甲基、乙基、丙基、丁 基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、三十烷基、環丙基、環丁基、環戊基、環己基、環庚基、環辛基、環壬基、環癸基、環十一烷基、環十二烷基、環三十烷基、降冰片基、金剛烷基、苯基、萘基、蒽基、七苯基、乙烯基、烯丙基、三十碳烯基、甲氧基、乙氧基、三十碳烯氧基、氟原子、氯原子、溴原子、碘原子、硫醇基。 Examples of R 14 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group, and a triacontane. , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl , norbornyl, adamantyl, phenyl, naphthyl, anthryl, heptaphenyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, tridecenyloxy, A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a thiol group.

前述R14的各例示含有異構物。例如丁基含有n-丁基、異丁基、sec-丁基、tert-丁基。 Each of the above R 14 is illustrative of an isomer. For example, butyl contains n-butyl, isobutyl, sec-butyl, tert-butyl.

前述式中,R10~R13與前述式(1-2)所說明者同義,R14各獨立為碳數1~30的直鏈狀、支鏈狀或者環狀的烷基、碳數6~30的芳基或碳數2~30的烯基、碳數1~30的烷氧基、鹵素原子、硫醇基,m14為0~5的整數。 In the above formula, R 10 to R 13 have the same meanings as those described in the above formula (1-2), and each of R 14 is independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms and a carbon number of 6 An aryl group of ~30 or an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom or a thiol group, and m 14 is an integer of 0 to 5.

作為R14,例如可舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、三十烷基、環丙基、環丁基、環戊基、環己基、環庚基、環辛基、環壬基、環癸基、環十一烷基、環十二烷基、環三十烷基、降冰片基、金剛烷基、苯基、萘基、蒽基、七苯基、乙烯基、烯丙基、三十碳烯基、甲氧基、乙氧基、三十碳烯氧基、氟原子、氯原子、溴原子、碘原子、硫醇基。 Examples of R 14 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group, and a triacontane. , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl , norbornyl, adamantyl, phenyl, naphthyl, anthryl, heptaphenyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, tridecenyloxy, A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a thiol group.

前述R14的各例示含有異構物。例如丁基含有n-丁基、異丁基、sec-丁基、tert-丁基。 Each of the above R 14 is illustrative of an isomer. For example, butyl contains n-butyl, isobutyl, sec-butyl, tert-butyl.

前述式中,R10~R13與前述式(1-2)所說明者同義。 In the above formula, R 10 to R 13 have the same meanings as those described in the above formula (1-2).

於上述所列舉的化合物之中,亦以耐熱性的觀點來看,以具有二苯並呫噸骨架的化合物者為較佳。 Among the above-exemplified compounds, those having a dibenzoxanthene skeleton are also preferred from the viewpoint of heat resistance.

式(0)所示化合物由原料的獲得性之觀點來看,更佳為於以下所列舉的化合物。 The compound represented by the formula (0) is more preferably a compound exemplified below from the viewpoint of availability of a raw material.

前述式中,R10~R13與前述式(1-2)所說明者同義。 In the above formula, R 10 to R 13 have the same meanings as those described in the above formula (1-2).

在上述所列舉的化合物之中,由耐熱性的觀點來看,以具有二苯並呫噸骨架的化合物為佳。 Among the above-exemplified compounds, a compound having a dibenzoxanthene skeleton is preferred from the viewpoint of heat resistance.

作為上述式(0)所示化合物,可進一步舉出以下式所示化合物。 Further, as the compound represented by the above formula (0), a compound represented by the following formula may be mentioned.

前述式中,R0A與前述式(0)中之RY為同義,R1A’與前述式(0)中之RZ為同義,R10~R13與前述式(1-2)所說明者同義。 In the above formula, R 0A is synonymous with R Y in the above formula (0), R 1A′ is synonymous with R Z in the above formula (0), and R 10 to R 13 are as described in the above formula (1-2). Synonymous.

在前述所列舉的化合物由耐熱性的觀點來看,以具有呫噸骨架的化合物者為較佳。 Among the above-exemplified compounds, those having a xanthene skeleton are preferred from the viewpoint of heat resistance.

作為上述式(0)所示化合物,可進一步舉出以下式所示化合物 Further, as the compound represented by the above formula (0), a compound represented by the following formula may be further mentioned.

前述式中,R10~R13與前述式(1-2)所說明者同義,R14、R15、R16、m14、m14’與前述式所說明者同義。 In the above formula, R 10 to R 13 have the same meanings as those described in the above formula (1-2), and R 14 , R 15 , R 16 , m 14 and m 14' have the same meanings as those described in the above formula.

作為以下式(0)所示化合物的製造方法之一例子,對於式(1)所示化合物及式(2)所示化合物之製造方法做說明。 The production method of the compound represented by the formula (1) and the compound represented by the formula (2) will be described as an example of the production method of the compound represented by the following formula (0).

[式(1)所示化合物之製造方法]  [Method for Producing Compound of Formula (1)]  

於本實施形態中之式(1)所示化合物可應用公知手法進行適宜合成,該合成手法並無特別限定。 The compound represented by the formula (1) in the present embodiment can be suitably synthesized by a known method, and the synthesis method is not particularly limited.

例如在常壓下將雙酚類、雙萘酚類或雙蒽酚與對應的醛類或酮類在酸觸媒下進行聚縮合反應後得到多酚化合 物,繼續於多酚化合物的至少一個酚性羥基上導入羥基烷基,於該羥基上導入選自烯丙基、丙烯酸基或甲基丙烯酸基的1個基後而可得。又,視必要可在加壓下進行。 For example, a polyphenol compound is obtained by polycondensation of a bisphenol, a bis-naphthol or a bisphenol with a corresponding aldehyde or a ketone under an acid catalyst under normal pressure to continue at least one phenol of the polyphenol compound. A hydroxyalkyl group is introduced into the hydroxyl group, and a group selected from the group consisting of an allyl group, an acryl group, and a methacryl group is introduced into the hydroxyl group. Further, it can be carried out under pressure as necessary.

且,導入羥基烷基的時間點不僅為雙萘酚類與醛類或酮類之縮合反應後,亦可在縮合反應之前段階。又,可於進行後述樹脂的製造後導入。 Further, the time point at which the hydroxyalkyl group is introduced is not only the condensation reaction of the bis-naphthol with the aldehyde or the ketone, but also the stage before the condensation reaction. Further, it can be introduced after the production of the resin described later.

倒入選自烯丙基、丙烯酸基或甲基丙烯酸基的1個基的時間點為導入羥基烷基後即可,亦可在縮合反應的前段階、後段階或進行後述樹脂之製造後導入。 The time point at which one group selected from the group consisting of allyl group, acryl group or methacryl group is poured may be introduced after the introduction of the hydroxyalkyl group, or may be introduced after the production of the resin described later in the first stage or the latter stage of the condensation reaction. .

作為前述雙酚類,例如可舉出雙酚、甲基雙酚、甲氧基雙萘酚等,但並未限定於此等。這些可單獨使用1種或組合2種以上使用。此等中亦由原料的安定供給性之觀點來看,使用雙酚為較佳。 Examples of the bisphenols include bisphenol, methyl bisphenol, and methoxybis naphthol, but are not limited thereto. These may be used alone or in combination of two or more. In the above, from the viewpoint of the stability of the raw material supply, it is preferred to use bisphenol.

作為前述雙萘酚類,例如可舉出雙萘酚、甲基雙萘酚、甲氧基雙萘酚等,但並未限定於此等。這些可單獨使用1種或組合2種以上使用。這些中亦由提高碳原子濃度及提高耐熱性之觀點來看,使用雙萘酚為較佳。 Examples of the bis-naphthols include bisnaphthol, methyl bis naphthol, and methoxy bis naphthol, but are not limited thereto. These may be used alone or in combination of two or more. Among these, from the viewpoint of increasing the concentration of carbon atoms and improving heat resistance, it is preferred to use bisnaphthol.

作為前述醛類,例如可舉出甲醛、三噁烷、三聚乙醛、苯甲醛、乙醛、丙基醛、苯基乙醛、苯基丙基醛、羥基苯甲醛、氯苯甲醛、硝基苯甲醛、甲基苯甲醛、乙基苯甲醛、丁基苯甲醛、聯苯基醛、萘醛、蒽甲醛、菲甲醛、芘甲醛、糠醛等,但並未限定於此等。這些可單獨使用1種或組合2種以上使用。這些中亦由賦予較高耐熱性之觀點來看,使用苯甲醛、苯基乙醛、苯基丙基醛、羥基 苯甲醛、氯苯甲醛、硝基苯甲醛、甲基苯甲醛、乙基苯甲醛、丁基苯甲醛、環己基苯甲醛、聯苯基醛、萘醛、蒽甲醛、菲甲醛、芘甲醛、糠醛者為佳,由提高蝕刻耐性之觀點來看,使用苯甲醛、羥基苯甲醛、氯苯甲醛、硝基苯甲醛、甲基苯甲醛、乙基苯甲醛、丁基苯甲醛、環己基苯甲醛、聯苯基醛、萘醛、蒽甲醛、菲甲醛、芘甲醛、糠醛為較佳。 Examples of the aldehydes include formaldehyde, trioxane, paraldehyde, benzaldehyde, acetaldehyde, propyl aldehyde, phenylacetaldehyde, phenylpropyl aldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, and nitrate. Butbenzaldehyde, methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, biphenyl aldehyde, naphthaldehyde, hydrazine formaldehyde, phenanthrene aldehyde, hydrazine formaldehyde, furfural, etc., but are not limited thereto. These may be used alone or in combination of two or more. Among these, benzaldehyde, phenylacetaldehyde, phenylpropyl aldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzene are also used from the viewpoint of imparting higher heat resistance. Formaldehyde, butyl benzaldehyde, cyclohexylbenzaldehyde, biphenyl aldehyde, naphthaldehyde, hydrazine formaldehyde, phenanthrene aldehyde, hydrazine formaldehyde, furfural are preferred. From the viewpoint of improving etching resistance, benzaldehyde and hydroxybenzaldehyde are used. , chlorobenzaldehyde, nitrobenzaldehyde, methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, cyclohexylbenzaldehyde, biphenyl aldehyde, naphthaldehyde, hydrazine formaldehyde, phenanthrene formaldehyde, hydrazine formaldehyde, furfural good.

作為前述酮類,例如可舉出丙酮、甲基乙基酮、環丁酮、環戊酮、環己酮、降冰片酮、三環己酮、三環癸酮、金剛烷酮、芴酮、苯並芴酮、苊醌、苊酮、蒽醌、苯乙酮、二乙醯苯、三乙醯苯、乙醯萘酸、二苯基羰基萘、苯基羰基聯苯基、二苯基羰基聯苯基、二苯甲酮、二苯基羰基苯、三苯基羰基苯、苯並萘酸、二苯基羰基萘、苯基羰基聯苯基、二苯基羰基聯苯基等,但並未限定於此等。這些可單獨使用或組合2種以上使用。此等中由賦予高耐熱性之觀點來看,使用環戊酮、環己酮、降冰片酮、三環己酮、三環癸酮、金剛烷酮、芴酮、苯並芴酮、苊醌、苊酮、蒽醌、苯乙酮、二乙醯苯、三乙醯苯、乙醯萘酸、二苯基羰基萘、苯基羰基聯苯基、二苯基羰基聯苯基、二苯甲酮、二苯基羰基苯、三苯基羰基苯、苯並萘酸、二苯基羰基萘、苯基羰基聯苯基、二苯基羰基聯苯基為佳,由提高蝕刻耐性之觀點來看,以使用苯乙酮、二乙醯苯、三乙醯苯、乙醯萘酸、二苯基羰基萘、苯基羰基聯苯基、二苯基羰基聯苯基、二苯甲酮、二苯基羰基苯、三 苯基羰基苯、苯並萘酸、二苯基羰基萘、苯基羰基聯苯基、二苯基羰基聯苯基為較佳。 Examples of the ketones include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornene, tricyclohexanone, tricyclic fluorenone, adamantanone, anthrone, and Benzofluorenone, anthracene, anthrone, anthracene, acetophenone, diethyl benzene, triethyl benzene, ethyl phthalic acid, diphenyl carbonyl naphthalene, phenyl carbonyl biphenyl, diphenyl carbonyl Biphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthoic acid, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, etc. Not limited to this. These can be used individually or in combination of 2 or more types. Among these, from the viewpoint of imparting high heat resistance, cyclopentanone, cyclohexanone, norbornene, tricyclohexanone, tricyclic fluorenone, adamantanone, anthrone, benzoxanone, anthracene are used. , anthrone, anthracene, acetophenone, diethyl benzene, triethyl benzene, ethyl phthalic acid, diphenyl carbonyl naphthalene, phenyl carbonyl biphenyl, diphenyl carbonyl biphenyl, diphenyl Ketone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthoic acid, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl are preferred, from the viewpoint of improving etching resistance To use acetophenone, diethyl benzene, triethyl benzene, ethyl phthalic acid, diphenyl carbonyl naphthalene, phenyl carbonyl biphenyl, diphenyl carbonyl biphenyl, benzophenone, diphenyl Alkylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthoic acid, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl are preferred.

作為醛類或酮類,由兼具高耐熱性及高蝕刻耐性的觀點來看,使用具有芳香環之醛或具有芳香族之酮者為佳。 As the aldehyde or ketone, it is preferred to use an aromatic aldehyde or an aromatic ketone from the viewpoint of having both high heat resistance and high etching resistance.

對於使用於上述反應之酸觸媒,可適宜地選自公知者,並無特別限定。作為如此酸觸媒,無機酸或有機酸廣被得知,例如可舉出鹽酸、硫酸、磷酸、氫溴酸、氫氟酸等無機酸;草酸、丙二酸、琥珀酸、己二酸、癸二酸、檸檬酸、富馬酸、馬來酸、甲酸、p-甲苯磺酸、甲磺酸、三氟乙酸、二氯乙酸、三氯乙酸、三氟甲磺酸、苯磺酸、萘磺酸、萘二磺酸等有機酸;氯化鋅、氯化鋁、氯化鐵、三氟化硼等路易氏酸,或矽鎢酸、磷鎢酸、矽鉬酸或磷鉬酸等固體酸等,並未特別限定於此等。此等中亦由製造上的觀點來看,以有機酸及固體酸為佳,由獲得知容易性或處理容易性等製造上的觀點來看,以使用鹽酸或硫酸者為較佳。且對於酸觸媒,可單獨使用1種或組合2種以上使用。又,酸觸媒之使用量可配合所使用的原料及觸媒種類,進一步配合反應條件等可適宜設定,但並無特別限定,對於反應原料100質量份以0.01~100質量份者為佳。 The acid catalyst used in the above reaction can be suitably selected from known ones, and is not particularly limited. As such an acid catalyst, an inorganic acid or an organic acid is widely known, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; oxalic acid, malonic acid, succinic acid, and adipic acid. Azelaic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalene Organic acids such as sulfonic acid and naphthalene disulfonic acid; Lewis acid such as zinc chloride, aluminum chloride, iron chloride or boron trifluoride; or solid such as tungstic acid, phosphotungstic acid, lanthanum molybdate or phosphomolybdic acid The acid or the like is not particularly limited to these. In the above, from the viewpoint of production, it is preferable to use an organic acid or a solid acid, and it is preferable to use hydrochloric acid or sulfuric acid from the viewpoint of obtaining ease of production or ease of handling. Further, the acid catalyst may be used singly or in combination of two or more. In addition, the amount of the acid catalyst to be used may be appropriately set in accordance with the type of the raw material and the catalyst to be used, and the reaction conditions may be appropriately adjusted, and it is not particularly limited, and it is preferably 0.01 to 100 parts by mass based on 100 parts by mass of the reaction raw material.

在上述反應時,可使用反應溶劑。作為反應溶劑,僅可進行使用的醛類或酮類與雙酚類、雙萘酚類或雙蒽二醇之反應者即可,並無特別限定,可適宜地選自公知者而使用。作為反應溶劑,例如可舉出水、甲醇、乙醇、丙醇、丁醇、四氫呋喃、二噁烷、乙二醇二甲基醚、 乙二醇二乙基醚或這些混合溶劑等。且溶劑可單獨使用1種或組合2種以上使用。 In the above reaction, a reaction solvent can be used. The reaction solvent is not particularly limited as long as it can be used as a reaction between an aldehyde or a ketone and a bisphenol, a bis-naphthol or a diterpene glycol, and can be suitably selected from known ones. The reaction solvent may, for example, be water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or a mixed solvent thereof. Further, the solvent may be used alone or in combination of two or more.

又,這些反應溶劑之使用量可配合所使用的原料及觸媒種類,進一步配合反應條件等做適宜設定,並無特別限定,對於反應原料100質量份以0~2000質量份的範圍者為佳。且上述反應中之反應溫度可配合反應原料之反應性做適宜選擇,並無特別限定,通常為10~200℃之範圍。 In addition, the amount of the reaction solvent to be used may be appropriately set in accordance with the type of the raw material and the catalyst to be used, and the reaction conditions are not particularly limited, and it is preferably in the range of 0 to 2000 parts by mass based on 100 parts by mass of the reaction raw material. . Further, the reaction temperature in the above reaction can be appropriately selected in accordance with the reactivity of the reaction raw material, and is not particularly limited, and is usually in the range of 10 to 200 °C.

欲得到多酚化合物,以反應溫度較高者為佳,具體以60~200℃的範圍為佳。且,反應方法可適宜地選擇公知手法使用,並無特別限定,可舉出將雙酚類、雙萘酚類或雙蒽二醇、醛類或酮類、觸媒一並裝入的方法或將雙酚類、雙萘酚類或雙蒽二醇或醛類或酮類在觸媒存在下滴入的方法。聚縮合反應終了後,所得之化合物的分離可依據常法進行,並無特別限定。例如欲除去存在於系統內之未反應原料或觸媒等,藉由採用將反應釜的溫度上升至130~230℃,在1~50mmHg程度下除去揮發部分等一般手法,可分離目的物之化合物。 In order to obtain a polyphenol compound, it is preferred to have a higher reaction temperature, and it is preferably in the range of 60 to 200 °C. Further, the reaction method can be appropriately selected from known methods, and is not particularly limited, and examples thereof include a method of incorporating bisphenols, bis-naphthols or diterpenediols, aldehydes or ketones, and a catalyst together. A method of dropping a bisphenol, a bis-naphthol or a diterpene glycol or an aldehyde or a ketone in the presence of a catalyst. After the completion of the polycondensation reaction, the separation of the obtained compound can be carried out according to a usual method, and is not particularly limited. For example, in order to remove unreacted raw materials or catalysts present in the system, the compound of the target substance can be isolated by using a general method such as increasing the temperature of the reaction vessel to 130 to 230 ° C and removing the volatile portion at a level of 1 to 50 mmHg. .

作為較佳反應條件,對於醛類或酮類1莫耳,將雙酚類、雙萘酚類或雙蒽二醇使用1莫耳~過剩量,及將酸觸媒使用0.001~1莫耳,在常壓於50~150℃下進行20分鐘~100小時程度反應者可舉出。 As preferred reaction conditions, for aldehydes or ketones 1 mole, bisphenols, bis-naphthols or diterpenediols are used in an amount of 1 mole to excess, and acid catalysts are used in an amount of 0.001 to 1 mole. The reaction can be carried out at a pressure of 50 to 150 ° C for 20 minutes to 100 hours.

反應終了後藉由公知方法可分離目的物。例如濃縮反應液,加入純水並析出反應生成物,冷卻至室溫 後,進行過濾使其分離,將所得之固體物經過濾、乾燥後,藉由管柱色譜儀與副生成物進行分離純化,將溶劑餾去、過濾、乾燥後可得到目的物之前述式(1)所示化合物。 After the end of the reaction, the object can be isolated by a known method. For example, the reaction solution is concentrated, pure water is added thereto, and the reaction product is precipitated. After cooling to room temperature, the mixture is filtered and separated, and the obtained solid is filtered and dried, and then separated and purified by column chromatography and by-products. The solvent is distilled off, filtered, and dried to obtain a compound represented by the above formula (1).

又,於多酚化合物之至少一個的酚性羥基中導入羥基烷基,於該羥基導入烯丙基、丙烯酸或甲基丙烯酸基之方法亦為公知。 Further, a method of introducing a hydroxyalkyl group into a phenolic hydroxyl group of at least one of the polyphenol compounds and introducing an allyl group, an acrylic acid group or a methacrylic acid group into the hydroxyl group is also known.

例如如以下,於前述化合物的至少一個的酚性羥基可導入羥基烷基。 For example, as follows, a phenolic hydroxyl group of at least one of the above compounds may be introduced into a hydroxyalkyl group.

羥基烷基可介著氧基烷基導入於酚性羥基,例如導入羥基烷氧基烷基或羥基烷氧基烷氧基烷基。 The hydroxyalkyl group may be introduced into the phenolic hydroxyl group via an oxyalkyl group, for example, a hydroxyalkoxyalkyl group or a hydroxyalkoxy alkoxyalkyl group.

使用於導入羥基烷基之化合物可藉由公知方法進行合成或者容易獲得者,例如可舉出氯乙醇、溴乙醇、乙酸-2-氯乙酯、乙酸-2-溴乙酯、乙酸-2-碘乙酯、環氧乙烷、環氧丙烷、環氧丁烷、伸乙基碳酸酯、伸丙基碳酸酯、丁伸基碳酸酯,但並未限定於此等。 The compound used for introducing a hydroxyalkyl group can be synthesized or easily obtained by a known method, and examples thereof include chlorohydrin, bromoethanol, 2-chloroethyl acetate, 2-bromoethyl acetate, and acetic acid-2- Iodine ethyl ester, ethylene oxide, propylene oxide, butylene oxide, ethyl acrylate, propyl carbonate, and butyl carbonate, but are not limited thereto.

例如於丙酮、四氫呋喃(THF)、丙二醇單甲基醚乙酸酯等非質子性溶劑將前述化合物溶解或懸浮。繼續在金屬烷氧化物(甲氧化鈉、乙氧化鈉、甲氧化鉀、乙氧化鉀等鹼金屬或鹼土類金屬烷氧化物等)、金屬氫氧化物(氫氧化鈉、氫氧化鉀等鹼金屬或鹼土類金屬碳酸鹽等)、碳酸氫鈉、碳酸氫鉀等鹼金屬或鹼土類碳酸氫鹽、胺類(例如第3級胺類(三乙基胺等三烷基胺、N,N-二甲基苯胺等的芳香族第3級胺、1-甲基咪唑等雜環式第3級胺)等、 羧酸金屬鹽(乙酸鈉、乙酸鈣等乙酸鹼金屬或鹼土類金屬鹽等)的有機鹼等鹼觸媒之存在下,在常壓下於20~150℃進行0.5~100小時反應。將反應液以酸中和後,加入於蒸餾水並析出白色固體後,將經分離的固體以蒸餾水洗淨,或將溶劑進行蒸發乾固後,視必要以蒸餾水洗淨並乾燥後,可得到羥基之氫原子由羥基伸烷基所取代的化合物。 For example, the aforementioned compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF) or propylene glycol monomethyl ether acetate. Continued with metal alkoxides (alkali metals such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, etc.) or metal hydroxides (alkali metals such as sodium hydroxide or potassium hydroxide) Or alkaline earth metal carbonates, etc., alkali metal or alkaline earth hydrogencarbonates such as sodium hydrogencarbonate or potassium hydrogencarbonate, and amines (for example, tertiary amines (trialkylamines such as triethylamine, N, N-) An aromatic third-order amine such as dimethylaniline or a heterocyclic third-order amine such as 1-methylimidazole, or a metal carboxylate such as an alkali metal acetate or an alkaline earth metal salt such as sodium acetate or calcium acetate. In the presence of an alkali catalyst such as an organic base, the reaction is carried out at a pressure of from 20 to 150 ° C for 0.5 to 100 hours under normal pressure. After the reaction solution is neutralized with an acid, it is added to distilled water to precipitate a white solid, and then separated. The solid is washed with distilled water, or the solvent is evaporated to dryness, and after washing with distilled water as necessary, and drying, a compound in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group can be obtained.

使用乙酸-2-氯乙酯、乙酸-2-溴乙酯、乙酸-2-碘乙酯時,導入乙醯氧基乙基後,產生脫醯基反應後導入羥基乙基。 When 2-chloroethyl acetate, 2-bromoethyl acetate, and 2-iodoethyl acetate were used, an ethyl ethoxyethyl group was introduced, and after deamination reaction, a hydroxyethyl group was introduced.

使用伸乙基碳酸酯、伸丙基碳酸酯、丁伸基碳酸酯,使伸烷基碳酸酯加成,藉由產生脫碳酸反應而導入羥基烷基。 The ethyl hydroxyalkyl ester, the propyl carbonate, and the butyl carbonate are used to form an alkyl carbonate, and a hydroxyalkyl group is introduced by a decarboxylation reaction.

繼續,例如如以下,可於前述化合物的至少一個羥基導入烯丙基、丙烯酸或甲基丙烯酸基。於羥基導入烯丙基、丙烯酸或甲基丙烯酸基的方法亦為公知。 Continuing, for example, as described below, an allyl group, an acrylic group or a methacryl group may be introduced into at least one hydroxyl group of the above compound. Processes for introducing an allyl, acrylic or methacrylic group into a hydroxy group are also known.

使用於導入烯丙基、丙烯酸或甲基丙烯酸基的化合物可藉由公知方法進行合成或者容易獲得者,例如可舉出氯化烯丙基、溴化烯丙基、碘化烯丙基、丙烯酸、丙烯酸氯化物、甲基丙烯酸、甲基丙烯酸氯化物,但並未限定於此等。 The compound used for introducing the allyl group, the acrylic acid group or the methacryl group group can be synthesized or easily obtained by a known method, and examples thereof include allyl chloride, allyl bromide, allyl group iodide, and acrylic acid. , acrylic acid chloride, methacrylic acid, methacrylic acid chloride, but is not limited thereto.

首先,於丙酮、四氫呋喃(THF)、丙二醇單甲基醚乙酸酯等非質子性溶劑使前述化合物溶解或懸浮。繼續在氫氧化鈉、氫氧化鉀、甲氧化鈉、乙氧化鈉等鹼觸媒存在下,在常壓於20~150℃反應6~72小時。將反應液以 酸中和,析出於蒸餾水所加入的白色固體後,將分離的固體以蒸餾水洗淨,或使溶劑進行蒸發乾固,視必要藉由蒸餾水洗淨並乾燥後,可得到羥基之氫原子為烯丙基、丙烯酸或以甲基丙烯酸基所取代的化合物。 First, the above compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF) or propylene glycol monomethyl ether acetate. Continue to react in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide at normal pressure at 20 to 150 ° C for 6 to 72 hours. The reaction solution is neutralized with an acid, and the white solid added by the distilled water is precipitated, and the separated solid is washed with distilled water, or the solvent is evaporated and dried, and if necessary, washed with distilled water and dried to obtain a hydroxyl group. The hydrogen atom is an allyl group, an acrylic acid or a compound substituted with a methacrylic group.

對於本實施形態,由烯丙基、丙烯酸或甲基丙烯酸基所取代的基在自由基或酸/鹼之存在下進行反應,對於塗佈溶劑或使用於顯像液的酸、鹼或有機溶劑的溶解性產生變化。由前述烯丙基、丙烯酸或甲基丙烯酸基所取代的基,以具有欲使更高感度.高解像度之圖型形成成為可能,在自由基或酸/鹼之存在下引起連鎖反應的性質者為佳。 In the present embodiment, a group substituted with an allyl group, an acrylic group or a methacryl group is reacted in the presence of a radical or an acid/base, and is a coating solvent or an acid, a base or an organic solvent used in a developing solution. The solubility changes. The group substituted by the aforementioned allyl group, acrylic acid or methacrylic group is capable of forming a pattern with higher sensitivity and high resolution, and is capable of causing a chain reaction in the presence of a radical or an acid/base. It is better.

[將式(1)所示化合物作為單體所得之樹脂]  [Resin obtained by using the compound represented by the formula (1) as a monomer]  

前述式(1)所示化合物,作為使用於光刻用膜形成或光學零件形成的組成物(以下亦簡稱為「組成物」),可直接使用。又,可將前述式(1)所示化合物作為單體所得之樹脂作為組成物使用。樹脂,例如反應前述式(1)所示化合物與具有交聯反應性之化合物而得。 The compound represented by the above formula (1) can be used as it is as a composition for film formation for photolithography or formation of an optical component (hereinafter also simply referred to as "composition"). Further, a resin obtained by using the compound represented by the above formula (1) as a monomer can be used as a composition. The resin is obtained, for example, by reacting a compound represented by the above formula (1) with a compound having cross-linking reactivity.

作為將前述式(1)所示化合物作為單體所得之樹脂,例如可舉出具有以下式(3)所示結構者。即,於本實施形態中之組成物亦可為含有具有下述式(3)所示結構之樹脂者。 The resin obtained by using the compound represented by the above formula (1) as a monomer may, for example, be a structure having the following formula (3). In other words, the composition in the present embodiment may be a resin containing a structure having the structure represented by the following formula (3).

式(3)中,L為可具有取代基之碳數1~30的伸烷基、可具有取代基之碳數6~30的伸芳基、可具有取代基之碳數1~30的伸烷氧基或單鍵,前述伸烷基、前述伸芳基、前述伸烷氧基亦可含有醚鍵、酮鍵或酯鍵。又,前述伸烷基、伸烷氧基亦可為直鏈狀、支鏈狀或者環狀之基。 In the formula (3), L is an alkylene group having 1 to 30 carbon atoms which may have a substituent, an extended aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number of 1 to 30 which may have a substituent. The alkoxy group or a single bond, the alkylene group, the above-mentioned extended aryl group, and the aforementioned alkoxy group may further contain an ether bond, a ketone bond or an ester bond. Further, the alkylene group and the alkylene group may be a linear, branched or cyclic group.

R0、R1、R2~R5、m2及m3、m4及m5、p2~p5、n與前述式(1)中者同義。 R 0 , R 1 , R 2 to R 5 , m 2 and m 3 , m 4 and m 5 , p 2 to p 5 and n are synonymous with those in the above formula (1).

但,m2、m3、m4及m5不會同時成為0,R2~R5的至少一個為羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代之基。 However, m 2 , m 3 , m 4 and m 5 do not simultaneously become 0, and at least one of R 2 to R 5 is a hydroxyl group having a hydrogen atom selected from the group consisting of allyloxyalkyl, acryloxyalkyl or A A group substituted with one group of a acryloxyalkyl group.

[將式(1)所示化合物作為單體所得之樹脂的製造方法]  [Method for Producing Resin Obtained by Using Compound of Formula (1) as Monomer]  

於本實施形態中之樹脂係藉由將上述式(1)所示化合物與具有交聯反應性之化合物進行反應而得。作為具有交聯反應性之化合物,若將前述式(1)所示化合物進行寡聚 物化或聚合物化所得者即可,並未特別限定於公知者而可使用。作為該具體例子,例如可舉出醛、酮、羧酸、羧酸鹵化物、鹵素含有化合物、胺基化合物、亞胺化合物、異氰酸酯、不飽和烴基含有化合物等,並未特別限定於此等。 The resin in the present embodiment is obtained by reacting a compound represented by the above formula (1) with a compound having crosslinking reactivity. The compound having the crosslinking reactivity may be obtained by oligomerizing or polymerizing the compound represented by the above formula (1), and is not particularly limited to those known to be used. Specific examples of the aldehyde, ketone, carboxylic acid, carboxylic acid halide, halogen-containing compound, amine compound, imine compound, isocyanate, and unsaturated hydrocarbon group-containing compound are not particularly limited.

作為具有前述式(3)所示結構的樹脂之具體例子,例如可舉出藉由將上述式(1)所示化合物與具有交聯反應性之化合物的醛及/或酮進行縮合反應等使其酚醛清漆化的樹脂。 Specific examples of the resin having the structure represented by the above formula (3) include a condensation reaction of an aldehyde and/or a ketone having a compound having the crosslinking reactivity with a compound represented by the above formula (1). Its phenolic varnished resin.

其中,作為使用於將前述式(1)所示化合物進行酚醛清漆化時的醛,例如可舉出甲醛、三噁烷、三聚乙醛、苯甲醛、乙醛、丙基醛、苯基乙醛、苯基丙基醛、羥基苯甲醛、氯苯甲醛、硝基苯甲醛、甲基苯甲醛、乙基苯甲醛、丁基苯甲醛、聯苯基醛、萘醛、蒽甲醛、菲甲醛、芘甲醛、糠醛等,並未特別限定於此等。作為酮可舉出前述酮類。彼等中,以甲醛為較佳。且這些醛及/或酮類可單獨使用1種或組合2種以上使用。又,上述醛及/或酮類的使用量雖無特別限定,對於上述式(1)所示化合物1莫耳,以0.2~5莫耳者為佳,較佳為0.5~2莫耳。 In addition, examples of the aldehyde used when the compound represented by the above formula (1) is subjected to novolak-forming include formaldehyde, trioxane, paraldehyde, benzaldehyde, acetaldehyde, propyl aldehyde, and phenyl b. Aldehyde, phenylpropyl aldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, biphenyl aldehyde, naphthaldehyde, hydrazine formaldehyde, phenanthrene aldehyde, The formaldehyde, furfural, and the like are not particularly limited thereto. The ketones are exemplified as the ketone. Among them, formaldehyde is preferred. Further, these aldehydes and/or ketones may be used alone or in combination of two or more. Further, the amount of the aldehyde and/or ketone used is not particularly limited, and the compound 1 represented by the above formula (1) is preferably 0.2 to 5 moles, more preferably 0.5 to 2 moles.

對於前述式(1)所示化合物與醛及/或酮之縮合反應,亦可使用酸觸媒。對於其中所使用的酸觸媒,可使用適宜選自公知者,並無特別限定。作為如此酸觸媒,無機酸或有機酸已廣泛被知,例如可舉出鹽酸、硫酸、磷酸、氫溴酸、氫氟酸等無機酸;草酸、丙二酸、琥珀酸、 己二酸、癸二酸、檸檬酸、富馬酸、馬來酸、甲酸、p-甲苯磺酸、甲磺酸、三氟乙酸、二氯乙酸、三氯乙酸、三氟甲磺酸、苯磺酸、萘磺酸、萘二磺酸等有機酸;氯化鋅、氯化鋁、氯化鐵、三氟化硼等路易氏酸或者矽鎢酸、磷鎢酸、矽鉬酸或磷鉬酸等固體酸等,但並未特別限定於此等。這些中亦由製造上的觀點來看,以有機酸及固體酸為佳,由獲得容易性或處理容易性等製造上的觀點來看,以鹽酸或硫酸為佳。且,對於酸觸媒可單獨使用1種或組合2種以上使用。 An acid catalyst can also be used for the condensation reaction of the compound represented by the above formula (1) with an aldehyde and/or a ketone. The acid catalyst to be used therein may be appropriately selected from those known in the art, and is not particularly limited. As such an acid catalyst, inorganic acids or organic acids are widely known, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; oxalic acid, malonic acid, succinic acid, and adipic acid; Azelaic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalene Organic acids such as sulfonic acid and naphthalene disulfonic acid; Lewis acid such as zinc chloride, aluminum chloride, iron chloride or boron trifluoride or solid acid such as tungstic acid, phosphotungstic acid, lanthanum molybdate or phosphomolybdic acid Etc., but it is not particularly limited to this. Among these, from the viewpoint of production, organic acid and solid acid are preferred, and hydrochloric acid or sulfuric acid is preferred from the viewpoint of availability, ease of handling, and the like. Further, the acid catalyst may be used singly or in combination of two or more.

又,酸觸媒的使用量可依據所使用的原料及觸媒種類,進一步配合反應條件等做適宜設定,並無特別限定,對於反應原料100質量份,以0.01~100質量份者為佳。但,與具有茚、羥基茚、苯並呋喃、羥基蒽、苊烯、聯苯基、雙酚、三酚、二環戊二烯、四氫茚、4-乙烯基環己烯、冰片二烯、5-乙烯基降冰片-2-烯、α-蒎烯、β-蒎烯、檸檬烯等非共軛雙鍵的化合物之共聚合反應時,醛類並非必要。 In addition, the amount of the acid catalyst to be used may be appropriately set depending on the type of the raw material and the catalyst to be used, and the reaction conditions are not particularly limited, and it is preferably 0.01 to 100 parts by mass based on 100 parts by mass of the reaction raw material. However, with hydrazine, hydroxy hydrazine, benzofuran, hydroxy hydrazine, decene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroanthracene, 4-vinylcyclohexene, borneadiene When a copolymerization reaction of a compound of a non-conjugated double bond such as 5-vinylnorborn-2-ene, α-pinene, β-pinene or limonene is carried out, an aldehyde is not essential.

對於前述式(1)所示化合物與醛及/或酮之縮合反應,可使用反應溶劑。作為該聚縮合中之反應溶劑,可使用適宜地選自公知者,並無特別限定,例如可舉出水、甲醇、乙醇、丙醇、丁醇、四氫呋喃、二噁烷或這些混合溶劑等。且,溶劑可單獨使用1種或組合2種以上後使用。 A reaction solvent can be used for the condensation reaction of the compound represented by the above formula (1) with an aldehyde and/or a ketone. The reaction solvent in the polycondensation is suitably selected from known ones, and is not particularly limited, and examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane or a mixed solvent thereof. Further, the solvent may be used singly or in combination of two or more.

又,這些溶劑之使用量可依據所使用的原料及觸媒之種類,進一步依據反應條件等做適宜設定,並無 特別限定,但對於反應原料100質量份以0~2000質量份的範圍者為佳。且反應溫度可依據反應原料之反應性而做適宜選擇,並無特別限定,通常為10~200℃之範圍。且,反應方法可適宜地選擇公知手法使用,並無特別限定,但可舉出一併投入上述式(1)所示化合物、醛及/或酮類、觸媒之方法或將上述式(1)所示化合物或醛及/或酮類在觸媒存在下滴入的方法。 In addition, the amount of the solvent to be used may be appropriately set depending on the reaction conditions and the like, and is not particularly limited, but it is in the range of 0 to 2000 parts by mass based on 100 parts by mass of the reaction raw material. good. Further, the reaction temperature is appropriately selected depending on the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 °C. Further, the reaction method can be appropriately selected from known methods, and is not particularly limited. However, a method of adding the compound represented by the above formula (1), an aldehyde and/or a ketone, a catalyst, or the above formula (1) may be mentioned. A method in which a compound or an aldehyde and/or a ketone is added dropwise in the presence of a catalyst.

聚縮合反應終了後,所得之化合物的分離可依據常法進行,並無特別限定。例如欲除去存在於系統內之未反應原料或觸媒等,藉由採用將反應釜的溫度上升至130~230℃,在1~50mmHg程度下除去揮發部分等一般的手法,可分離目的物之經酚醛清漆化的樹脂。 After the completion of the polycondensation reaction, the separation of the obtained compound can be carried out according to a usual method, and is not particularly limited. For example, in order to remove unreacted raw materials or catalysts present in the system, the object can be separated by a general method such as increasing the temperature of the reaction vessel to 130 to 230 ° C and removing the volatile portion at a level of 1 to 50 mmHg. A phenolic varnished resin.

其中,具有前述式(3)所示結構之樹脂亦可為前述式(1)所示化合物的單獨聚合物,亦可為與其他酚類之共聚物。其中,作為可共聚合之酚類,例如可舉出酚、甲酚、二甲基酚、三甲基酚、丁基酚、苯基酚、二苯基酚、萘酚、間苯二酚、甲基間苯二酚、鄰苯二酚、丁基鄰苯二酚、甲氧基酚、甲氧基酚、丙基酚、鄰苯三酚、麝香草酚等,並未特別限定於此等。 Among them, the resin having the structure represented by the above formula (3) may be a single polymer of the compound represented by the above formula (1), or may be a copolymer with other phenols. Among them, examples of the phenol which can be copolymerized include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthol, and resorcin. Methyl resorcinol, catechol, butyl catechol, methoxy phenol, methoxy phenol, propyl phenol, pyrogallol, thymol, etc., are not particularly limited thereto. .

又,具有前述式(3)所示結構之樹脂除上述其他酚類以外,亦可為與可聚合之單體進行共聚合者。作為該共聚合單體,例如可舉出萘酚、甲基萘酚、甲氧基萘酚、二羥基萘、茚、羥基茚、苯並呋喃、羥基蒽、苊烯、聯苯基、雙酚、三酚、二環戊二烯、四氫茚、4-乙烯基環 己烯、冰片二烯、乙烯基降冰片烯、蒎烯、檸檬烯等,並未特別限定於此等。且,具有前述式(3)所示結構之樹脂即使為前述式(1)所示化合物與上述酚類的2元以上(例如2~4元系)共聚物,即使為前述式(1)所示化合物與上述共聚合單體之2元以上(例如2~4元系)共聚物,即使為前述式(1)所示化合物與上述酚類與上述共聚合單體之3元以上(例如3~4元系)共聚物亦可。 Further, the resin having the structure represented by the above formula (3) may be copolymerized with a polymerizable monomer in addition to the above other phenols. Examples of the copolymerizable monomer include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, anthracene, hydroxyanthracene, benzofuran, hydroxyanthracene, decene, biphenylyl, and bisphenol. Further, triol, dicyclopentadiene, tetrahydroanthracene, 4-vinylcyclohexene, norbornadiene, vinyl norbornene, decene, limonene or the like is not particularly limited. Further, even if the resin having the structure represented by the above formula (3) is a copolymer of two or more (for example, two to four elements) of the compound represented by the above formula (1) and the above phenol, even if it is a compound of the above formula (1) The copolymer of the compound and the above-mentioned copolymerized monomer of 2 or more (for example, 2 to 4 member) is a compound of the above formula (1) and the above phenol and the above-mentioned copolymerized monomer are 3 or more (for example, 3) ~4 element system) copolymer can also be.

具有前述式(3)所示結構之樹脂的分子量並無特別限定,以聚苯乙烯換算之重量平均分子量(Mw)為500~30,000者為佳,較佳為750~20,000。又,由提高交聯效率之同時抑制燒烤中之揮發成分的觀點來看,具有前述式(3)所示結構之樹脂以分散度(重量平均分子量Mw/數平均分子量Mn)為1.2~7之範圍內者為佳。且,上述Mw及Mn可藉由後述實施例所記載的方法求得。 The molecular weight of the resin having the structure represented by the above formula (3) is not particularly limited, and the weight average molecular weight (Mw) in terms of polystyrene is preferably from 500 to 30,000, preferably from 750 to 20,000. Moreover, the resin having the structure represented by the above formula (3) has a degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of 1.2 to 7 from the viewpoint of improving the crosslinking efficiency and suppressing the volatile component in the roasting. Those within the range are preferred. Further, the above Mw and Mn can be obtained by the method described in the examples below.

具有前述式(3)所示結構之樹脂由可更容易適用於濕式製程等觀點來看,對於溶劑具有較高溶解性者佳。更具體為,將1-甲氧基-2-丙醇(PGME)及/或丙二醇單甲基醚乙酸酯(PGMEA)作為溶劑時,對於該溶劑之溶解度以10質量%以上者為佳。其中,對於PGME及/或PGMEA的溶解度定義為「樹脂質量÷(樹脂質量+溶劑質量)×100(質量%)」。例如前述樹脂10g對於PGMEA90g進行溶解時,前述樹脂對於PGMEA之溶解度成為「10質量%以上」,不溶解時為「未達10質量%」。 The resin having the structure represented by the above formula (3) is preferred because it can be more easily applied to a wet process, and has a high solubility in a solvent. More specifically, when 1-methoxy-2-propanol (PGME) and/or propylene glycol monomethyl ether acetate (PGMEA) is used as the solvent, the solubility of the solvent is preferably 10% by mass or more. The solubility of PGME and/or PGMEA is defined as "resin mass ÷ (resin mass + solvent mass) × 100 (% by mass)". For example, when 10 g of the resin is dissolved in PGMEA 90 g, the solubility of the resin to PGMEA is "10% by mass or more", and when it is not dissolved, it is "less than 10% by mass".

[式(2)所示化合物]  [Compound represented by formula (2)]  

本實施形態中之化合物(0)由耐熱性及溶劑溶解性的觀點來看,以下述式(2)所示化合物者為佳。 The compound (0) in the present embodiment is preferably a compound represented by the following formula (2) from the viewpoint of heat resistance and solvent solubility.

式(2)中,R0A為氫原子、碳數1~30的烷基或碳數6~30的芳基。 In the formula (2), R 0A is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms.

R1A為碳數1~60的NA價基或單鍵,R2A各獨立為可具有取代基之碳數1~30的直鏈狀、支鏈狀或者環狀的烷基、可具有取代基之碳數6~30的芳基、可具有取代基之碳數2~30的烯基、可具有取代基之碳數1~30的烷氧基、鹵素原子、硝基、胺基、羧酸基、硫醇基、羥基或羥基的氫原子可由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代的基、前述烷基、前述芳基、前述烯基、前述烷氧基可含有醚鍵、酮鍵或酯鍵,其中,R2A的至少一個為含有羥基的 氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代之基。 R 1A is a N A valent group or a single bond having 1 to 60 carbon atoms, and each of R 2A is independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, and may have a substitution. An aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, and a carboxyl group The hydrogen atom of the acid group, the thiol group, the hydroxyl group or the hydroxyl group may be a group substituted with one group selected from the group consisting of an allyloxyalkyl group, a acryloxyalkyl group or a methacryloxyalkyl group, and the aforementioned alkyl group The aryl group, the aforementioned alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond or an ester bond, wherein at least one of R 2A is a hydroxyl group-containing hydrogen atom selected from the group consisting of allyloxyalkyl groups and propylene oxide. A group substituted with one group of a base alkyl group or a methacryloxyalkyl group.

nA為1~4的整數,其中,式(2)中,nA為2以上的整數時,nA個[ ]內之結構式可為相同或相異。 n A is an integer of 1 to 4, and in the formula (2), when n A is an integer of 2 or more, the structural formulas in n A [ ] may be the same or different.

XA各獨立表示氧原子、硫原子或無交聯。其中,XA因具有表現優良耐熱性之傾向,以氧原子或硫原子者為佳,以氧原子為較佳。XA由溶解性之觀點來看以無交聯者為佳。 X A each independently represents an oxygen atom, a sulfur atom or no crosslinking. Among them, X A has a tendency to exhibit excellent heat resistance, and an oxygen atom or a sulfur atom is preferred, and an oxygen atom is preferred. X A is preferably a non-crosslinker from the viewpoint of solubility.

m2A各獨立為0~6的整數。但,至少一個的m2A為1~6的整數。 m 2A are each independently an integer of 0-6. However, at least one of m 2A is an integer of 1 to 6.

qA各獨立為0或1。 q A is independently 0 or 1.

且,所謂前述n價基,n=1時,表示碳數1~60的烷基,n=2時,表示碳數1~30的伸烷基,n=3時,表示碳數2~60的烷烴丙基,n=4時,表示碳數3~60的烷烴四基。作為前述n價基,例如可舉出具有直鏈狀烴基、支鏈狀烴基或脂環式烴基者等。其中,對於前述脂環式烴基,亦含有有橋脂環式烴基。又,前述n價基可具有碳數6~60的芳香族基。 Further, the n-valent group, when n=1, represents an alkyl group having 1 to 60 carbon atoms, and when n=2, it represents an alkylene group having 1 to 30 carbon atoms, and when n=3, it represents a carbon number of 2 to 60. The alkane propyl group, when n = 4, represents an alkane tetra group having a carbon number of 3 to 60. Examples of the n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group or an alicyclic hydrocarbon group. Among them, the alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group. Further, the n-valent group may have an aromatic group having 6 to 60 carbon atoms.

又,前述n價烴基可具有脂環式烴基、雙鍵、雜原子或者碳數6~60的芳香族基。其中,對於前述脂環式烴基亦含有有橋脂環式烴基。 Further, the n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 60 carbon atoms. Among them, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group.

又,前述n價烴基可具有脂環式烴基、雙鍵、雜原子或者碳數6~30的芳香族基。其中,對於前述脂環 式烴基亦含有有橋脂環式烴基。 Further, the n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 30 carbon atoms. Among them, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group.

上述式(2)所示化合物即使為比較低分子量,因該結構之剛直性而具有高耐熱性,故亦可在高溫燒烤條件使用。又,於分子中具有3級碳或4級碳,結晶性受到抑制,可作為可使用於光刻用膜製造之光刻用膜形成組成物。 The compound represented by the above formula (2) can be used in a high-temperature barbecue condition even if it has a relatively low molecular weight and has high heat resistance due to the rigidity of the structure. Further, it has three grades of carbon or four grades of carbon in the molecule, and the crystallinity is suppressed, and it can be used as a composition for forming a film for lithography for use in film production for lithography.

又,因對於安全溶劑之溶解性高,耐熱性及蝕刻耐性為良好,含有上述式(2)所示化合物之光刻用抗蝕形成組成物可賦予良好抗蝕圖型形狀。 Moreover, since the solubility in a safe solvent is high, heat resistance and etching resistance are good, and the resist formation composition for lithography containing the compound represented by the above formula (2) can provide a favorable resist pattern shape.

且,比較低分子量具有低黏度,故即使為具有段差之基板(特別為微細空間或孔圖型等),可均勻地填充至該段差的角落下,亦可容易提高膜之平坦性,其結果使用此的光刻用下層膜形成組成物具有良好的埋入及平坦化特性。又,因具有比較性碳濃度之化合物,亦可賦予高蝕刻耐性。 Moreover, since the relatively low molecular weight has a low viscosity, even if it is a substrate having a step (especially in a fine space or a hole pattern), it can be uniformly filled under the corner of the step, and the flatness of the film can be easily improved. The underlayer film forming composition for lithography using this has good embedding and planarization characteristics. Further, high etching resistance can be imparted by a compound having a comparative carbon concentration.

進一步又因芳香族密度高故折射率為高,又因藉由自低溫至高溫的廣範圍熱處理下亦可抑制著色,故作為各種光學零件形成組成物亦有用。其中亦由抑制化合物的氧化分解而抑制著色,並提高耐熱性及溶劑溶解性之觀點來看,以具有4級碳之化合物為佳。作為光學零件,除薄膜狀、薄片狀零件以外,作為塑質透鏡(棱鏡透鏡、柱狀透鏡、微透鏡、菲涅爾透鏡、視野角控制透鏡、對比提高透鏡等)、相位差薄膜、電磁波屏蔽用薄膜、棱鏡、光纖、可撓性印刷配線用焊接抗蝕、電鍍抗蝕、多層印刷 電路板用層間絶緣膜、感光性光波導路為有用。 Further, since the aromatic density is high, the refractive index is high, and since coloring can be suppressed by a wide range of heat treatment from low temperature to high temperature, it is also useful as a composition for forming various optical components. Among them, a compound having a carbon of 4 grade is preferable from the viewpoint of suppressing oxidative decomposition of the compound to suppress coloration and improving heat resistance and solvent solubility. As an optical component, it is a plastic lens (a prism lens, a lenticular lens, a microlens, a Fresnel lens, a viewing angle control lens, a contrast-enhancing lens, etc.), a retardation film, and an electromagnetic wave shield in addition to a film-like or sheet-like component. It is useful for a film, a prism, an optical fiber, a solder resist for a flexible printed wiring, an electroplating resist, an interlayer insulating film for a multilayer printed wiring board, and a photosensitive optical waveguide.

上述式(2)所示化合物由交聯的容易性與對有機溶劑之溶解性的觀點來看,以下述式(2-1)所示化合物者為佳。 The compound represented by the above formula (2) is preferably a compound represented by the following formula (2-1) from the viewpoints of easiness of crosslinking and solubility in an organic solvent.

式(2-1)中,R0A、R1A、nA及qA及XA與上述式(2)所說明者同義。 In the formula (2-1), R 0A , R 1A , n A and q A and X A have the same meanings as those described in the above formula (2).

R3A為可具有取代基之碳數1~30的直鏈狀、支鏈狀或者環狀的烷基、可具有取代基之碳數6~30的芳基、可具有取代基之碳數2~30的烯基、鹵素原子、硝基、胺基、羧酸基、硫醇基,對於相同萘環或苯環可為相同或相異。 R 3A is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number which may have a substituent 2 The alkenyl group, the halogen atom, the nitro group, the amine group, the carboxylic acid group, and the thiol group of ~30 may be the same or different for the same naphthalene ring or benzene ring.

R4A各獨立為氫原子或選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基,其中,R4A的至少一個為選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基,m6A各獨立為0~5的整數。 R 4A is each independently a hydrogen atom or a group selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacryloxyalkyl, wherein at least one of R 4A is selected from allyl groups. One group of an oxyalkyl group, a propyleneoxyalkyl group or a methacryloxyalkyl group, and m 6A are each independently an integer of 0 to 5.

將上述式(2-1)所示化合物作為鹼顯像正型抗 蝕用或有機顯像負型抗蝕用光刻用膜形成組成物使用時,R4A的至少一個為酸解離性基。另一方面,將式(2-1)所示化合物作為鹼顯像負型抗蝕用光刻用膜形成組成物、下層膜用光刻用膜形成組成物或光學零件形成組成物使用時,R4A的至少一個為氫原子。 When the compound represented by the above formula (2-1) is used as a composition for forming a film for lithography for alkali development positive resist or organic development negative resist, at least one of R 4A is an acid dissociable group. On the other hand, when the compound represented by the formula (2-1) is used as a composition for forming a film for lithography for alkali-developing negative resist, or a composition for forming a film for lithography for a lower film, or an optical component-forming composition, At least one of R 4A is a hydrogen atom.

又,上述式(2-1)所示化合物由原料之供給性的觀點來看,以下述式(2a)所示化合物者為佳。 Further, the compound represented by the above formula (2-1) is preferably a compound represented by the following formula (2a) from the viewpoint of the supply property of the raw material.

上述式(2a)中,XA、R0A~R2A、m2A及nA與上述式(2)所說明者同義。 In the above formula (2a), X A , R 0A to R 2A , m 2A and n A have the same meanings as those described in the above formula (2).

又,上述式(2-1)所示化合物由對於有機溶劑之溶解性的觀點來看,以下述式(2b)所示化合物為較佳。 Further, the compound represented by the above formula (2-1) is preferably a compound represented by the following formula (2b) from the viewpoint of solubility in an organic solvent.

上述式(2b)中,XA、R0A、R1A、R3A、R4A、m6A及nA與上述式(2-1)所說明者同義。 In the above formula (2b), X A , R 0A , R 1A , R 3A , R 4A , m 6A and n A have the same meanings as those described in the above formula (2-1).

又,上述式(2-1)所示化合物由對於有機溶劑之溶解性的觀點來看,以下述式(2c)所示化合物為更佳。 Further, the compound represented by the above formula (2-1) is more preferably a compound represented by the following formula (2c) from the viewpoint of solubility in an organic solvent.

上述式(2c)中,XA、R0A、R1A、R3A、R4A、m6A及nA與上述式(2-1)所說明者同義。 In the above formula (2c), X A , R 0A , R 1A , R 3A , R 4A , m 6A and n A have the same meanings as those described in the above formula (2-1).

上述式(2)所示化合物進一步由對於有機溶劑 之溶解性的觀點來看,以下述式(BisN-1)~(BisN-4)、(XBisN-1)~(XBisN-3)、(BiN-1)~(BiN-4)或(XBiN-1)~(XBiN-3)所示化合物為特佳。 The compound represented by the above formula (2) is further represented by the following formula (BisN-1) to (BisN-4), (XBisN-1) to (XBisN-3), (BiN) from the viewpoint of solubility in an organic solvent. The compound represented by -1) to (BiN-4) or (XBiN-1) to (XBiN-3) is particularly preferred.

[式(2)所示化合物之製造方法]  [Method for Producing Compound of Formula (2)]  

於本實施形態中之式(2)所示化合物可應用公知手法而適宜合成,該合成手法並無特別限定。 The compound represented by the formula (2) in the present embodiment can be suitably synthesized by a known method, and the synthesis method is not particularly limited.

例如在常壓下藉由將酚類、萘酚類與對應的醛類或酮類在酸觸媒下進行聚縮合反應而得到多酚化合物,接著於多酚化合物的至少一個酚性羥基上導入羥基烷基,可藉由於該羥基導入選自烯丙基、丙烯酸基或甲基丙烯酸基的1個基而得。又,視必要可在加壓下進行。 For example, a polyphenol compound is obtained by a polycondensation reaction of a phenol or a naphthol with a corresponding aldehyde or a ketone under an acid catalyst under normal pressure, followed by introduction onto at least one phenolic hydroxyl group of the polyphenol compound. The hydroxyalkyl group can be obtained by introducing the hydroxyl group into one group selected from the group consisting of an allyl group, an acryl group or a methacryl group. Further, it can be carried out under pressure as necessary.

且,導入羥基烷基的時間點不僅為酚類、萘 酚類與醛類或酮類的縮合反應後,亦可在縮合反應之前段階。又,亦可在進行後述樹脂的製造後導入。 Further, the time point at which the hydroxyalkyl group is introduced is not only a condensation reaction of a phenol or a naphthol with an aldehyde or a ketone, but also a stage before the condensation reaction. Further, it may be introduced after the production of the resin described later.

導入選自烯丙基、丙烯酸基或甲基丙烯酸基的1個基之時間點僅在導入羥基烷基後即可,亦可在縮合反應之前段階、後段階或進行後述樹脂之製造後導入。 The introduction of the hydroxyalkyl group may be carried out only after the introduction of the hydroxyalkyl group at a time selected from the group consisting of allyl groups, acrylic groups or methacryl groups, or may be introduced after the production of the resin described later before or after the condensation reaction.

作為前述萘酚類,並無特別限定,例如可舉出萘酚、甲基萘酚、甲氧基萘酚、萘二醇等,其中由可容易製作呫噸結構的觀點來看,使用萘二醇者為佳。 The naphthol is not particularly limited, and examples thereof include naphthol, methylnaphthol, methoxynaphthol, and naphthalenediol. Among them, naphthalene is used from the viewpoint of easily producing a xanthene structure. Alcohol is better.

作為前述酚類,並無特別限定,例如可舉出酚、甲基酚、甲氧基苯、鄰苯二酚、間苯二酚、氫醌、三甲基氫醌等。 The phenol is not particularly limited, and examples thereof include phenol, methylphenol, methoxybenzene, catechol, resorcin, hydroquinone, and trimethylhydroquinone.

作為前述醛類,例如可舉出甲醛、三噁烷、三聚乙醛、苯甲醛、乙醛、丙基醛、苯基乙醛、苯基丙基醛、羥基苯甲醛、氯苯甲醛、硝基苯甲醛、甲基苯甲醛、乙基苯甲醛、丁基苯甲醛、聯苯基醛、萘醛、蒽甲醛、菲甲醛、芘甲醛、糠醛等,並未特別限定於此等。這些可單獨使用或組合2種以上使用。彼等中亦由賦予高耐熱性之觀點來看,使用苯甲醛、苯基乙醛、苯基丙基醛、羥基苯甲醛、氯苯甲醛、硝基苯甲醛、甲基苯甲醛、乙基苯甲醛、丁基苯甲醛、環己基苯甲醛、聯苯基醛、萘醛、蒽甲醛、菲甲醛、芘甲醛、糠醛為佳,由提高蝕刻耐性之觀點來看,使用苯甲醛、羥基苯甲醛、氯苯甲醛、硝基苯甲醛、甲基苯甲醛、乙基苯甲醛、丁基苯甲醛、環己基苯甲醛、聯苯基醛、萘醛、蒽甲醛、菲甲醛、芘甲醛、糠醛為 較佳。 Examples of the aldehydes include formaldehyde, trioxane, paraldehyde, benzaldehyde, acetaldehyde, propyl aldehyde, phenylacetaldehyde, phenylpropyl aldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, and nitrate. The benzaldehyde, methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, biphenyl aldehyde, naphthaldehyde, hydrazine formaldehyde, phenanthrene aldehyde, hydrazine formaldehyde, furfural, and the like are not particularly limited thereto. These can be used individually or in combination of 2 or more types. They also use benzaldehyde, phenylacetaldehyde, phenylpropyl aldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methyl benzaldehyde, ethylbenzene from the viewpoint of imparting high heat resistance. Formaldehyde, butyl benzaldehyde, cyclohexylbenzaldehyde, biphenyl aldehyde, naphthaldehyde, hydrazine formaldehyde, phenanthrene aldehyde, hydrazine formaldehyde, furfural are preferred. From the viewpoint of improving etching resistance, benzaldehyde, hydroxybenzaldehyde, Chlorobenzaldehyde, nitrobenzaldehyde, methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, cyclohexylbenzaldehyde, biphenyl aldehyde, naphthaldehyde, hydrazine formaldehyde, phenanthrene aldehyde, hydrazine formaldehyde, furfural are preferred .

作為前述酮類,例如可舉出丙酮、甲基乙基酮、環丁酮、環戊酮、環己酮、降冰片酮、三環己酮、三環癸酮、金剛烷酮、芴酮、苯並芴酮、苊醌、苊酮、蒽醌、苯乙酮、二乙醯苯、三乙醯苯、乙醯萘酸、二苯基羰基萘、苯基羰基聯苯基、二苯基羰基聯苯基、二苯甲酮、二苯基羰基苯、三苯基羰基苯、苯並萘酸、二苯基羰基萘、苯基羰基聯苯基、二苯基羰基聯苯基等,但並未特別限定於此等。這些可單獨使用或組合2種以上使用。彼等中由賦予高耐熱性的觀點來看,使用環戊酮、環己酮、降冰片酮、三環己酮、三環癸酮、金剛烷酮、芴酮、苯並芴酮、苊醌、苊酮、蒽醌、苯乙酮、二乙醯苯、三乙醯苯、乙醯萘酸、二苯基羰基萘、苯基羰基聯苯基、二苯基羰基聯苯基、二苯甲酮、二苯基羰基苯、三苯基羰基苯、苯並萘酸、二苯基羰基萘、苯基羰基聯苯基、二苯基羰基聯苯基為佳,由提高蝕刻耐性之觀點來看,使用苯乙酮、二乙醯苯、三乙醯苯、乙醯萘酸、二苯基羰基萘、苯基羰基聯苯基、二苯基羰基聯苯基、二苯甲酮、二苯基羰基苯、三苯基羰基苯、苯並萘酸、二苯基羰基萘、苯基羰基聯苯基、二苯基羰基聯苯基為較佳。 Examples of the ketones include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornene, tricyclohexanone, tricyclic fluorenone, adamantanone, anthrone, and Benzofluorenone, anthracene, anthrone, anthracene, acetophenone, diethyl benzene, triethyl benzene, ethyl phthalic acid, diphenyl carbonyl naphthalene, phenyl carbonyl biphenyl, diphenyl carbonyl Biphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthoic acid, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, etc. It is not particularly limited to this. These can be used individually or in combination of 2 or more types. Among them, from the viewpoint of imparting high heat resistance, cyclopentanone, cyclohexanone, norbornene, tricyclohexanone, tricyclic fluorenone, adamantanone, anthrone, benzoxanone, anthracene are used. , anthrone, anthracene, acetophenone, diethyl benzene, triethyl benzene, ethyl phthalic acid, diphenyl carbonyl naphthalene, phenyl carbonyl biphenyl, diphenyl carbonyl biphenyl, diphenyl Ketone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthoic acid, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl are preferred, from the viewpoint of improving etching resistance , using acetophenone, diethyl benzene, triethyl benzene, acetamidine, diphenyl carbonyl naphthalene, phenyl carbonyl biphenyl, diphenyl carbonyl biphenyl, benzophenone, diphenyl Carbonylbenzene, triphenylcarbonylbenzene, benzonaphthoic acid, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl are preferred.

作為酮類,由兼具高耐熱性及高蝕刻耐性的觀點來看,使用具有芳香環之酮為佳。 As the ketone, a ketone having an aromatic ring is preferably used from the viewpoint of having both high heat resistance and high etching resistance.

對於使用於上述反應之酸觸媒,可使用適宜地選自公知者,並無特別限定。作為酸觸媒,可適宜地選 自周知無機酸、有機酸,例如可舉出鹽酸、硫酸、磷酸、氫溴酸、氫氟酸等無機酸;草酸、甲酸、p-甲苯磺酸、甲磺酸、三氟乙酸、三氟甲磺酸、苯磺酸、萘磺酸、萘二磺酸等有機酸;氯化鋅、氯化鋁、氯化鐵、三氟化硼等路易氏酸;或者矽鎢酸、磷鎢酸、矽鉬酸或磷鉬酸等固體酸。彼等中由獲得容易性或處理容易性等製造上的觀點來看,使用鹽酸或硫酸為佳。對於酸觸可單獨使用1種或組合2種以上使用。 The acid catalyst used in the above reaction can be suitably selected from those known in the art, and is not particularly limited. The acid catalyst may be suitably selected from known inorganic acids and organic acids, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; oxalic acid, formic acid, p-toluenesulfonic acid, and methanesulfonic acid; An organic acid such as acid, trifluoroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid or naphthalene disulfonic acid; Lewis acid such as zinc chloride, aluminum chloride, iron chloride or boron trifluoride; A solid acid such as tungstic acid, phosphotungstic acid, lanthanum molybdate or phosphomolybdic acid. Among them, hydrochloric acid or sulfuric acid is preferred from the viewpoint of ease of production, ease of handling, and the like. The acid contact may be used alone or in combination of two or more.

於上述反應時可使用反應溶劑。作為反應溶劑,若可進行所使用的醛類或酮類與萘酚類等反應者即可,並無特別限定,例如可使用水、甲醇、乙醇、丙醇、丁醇、四氫呋喃、二噁烷或這些混合溶劑。反應溶劑的量並無特別限定,例如對於反應原料100質量份而言為0~2000質量份範圍。 A reaction solvent can be used in the above reaction. The reaction solvent is not particularly limited as long as it can be reacted with an aldehyde or a ketone or a naphthol, and for example, water, methanol, ethanol, propanol, butanol, tetrahydrofuran or dioxane can be used. Or these mixed solvents. The amount of the reaction solvent is not particularly limited, and is, for example, in the range of 0 to 2000 parts by mass based on 100 parts by mass of the reaction raw material.

反應溫度並無特別限定,可配合反應原料之反應性做適宜選擇,但以10~200℃的範圍者為佳。於本實施形態中由可選擇性良好地合成式(2)所示化合物的觀點來看,以溫度較低者為佳,以10~60℃的範圍者為較佳。 The reaction temperature is not particularly limited, and may be appropriately selected in accordance with the reactivity of the reaction raw material, but it is preferably in the range of 10 to 200 °C. In the present embodiment, from the viewpoint of selectively synthesizing the compound represented by the formula (2), those having a lower temperature are preferred, and those having a temperature of from 10 to 60 ° C are preferred.

反應方法並無特別限定,例如可舉出一併裝入萘酚類等、醛類或酮類、觸媒的方法,或在觸媒存在下滴入萘酚類或醛類或酮類的方法。聚縮合反應終了後,欲除去存在於系統內的未反應原料、觸媒等,可將反應釜溫度上升至130~230℃,在1~50mmHg程度下除去揮發成 分。 The reaction method is not particularly limited, and examples thereof include a method in which a naphthol or the like, an aldehyde or a ketone, a catalyst, or a method of dropping a naphthol or an aldehyde or a ketone in the presence of a catalyst. . After the end of the polycondensation reaction, the unreacted raw material, the catalyst, and the like which are present in the system are removed, and the temperature of the reactor can be raised to 130 to 230 ° C to remove the volatile component at a level of 1 to 50 mmHg.

原料的量並無特別限定,例如對於醛類或酮類1莫耳,使用萘酚類等2莫耳~過剩量及酸觸媒0.001~1莫耳,在常壓下,在20~60℃進行20分鐘~100小時程度的反應者為佳。 The amount of the raw material is not particularly limited. For example, for aldehydes or ketones, 1 mole of naphthol, etc., 2 moles to excess amount and acid catalyst 0.001 to 1 mole, and under normal pressure, at 20 to 60 ° C. It is better to carry out a reaction of about 20 minutes to 100 hours.

反應終了後,藉由公知方法分離目的物。目的物之分離方法並無特別限定,例如可舉出濃縮反應液,加入純水並析出反應生成物,冷卻至室溫後,進行過濾並分離,過濾所得之固體物,經乾燥後,藉由管柱色譜儀與副生成物分離並純化,進行溶劑餾去、過濾、乾燥後分離目的化合物之方法。 After the reaction is completed, the object is separated by a known method. The method for separating the target product is not particularly limited. For example, a concentrated reaction liquid is added, pure water is added thereto, and the reaction product is precipitated. After cooling to room temperature, the mixture is filtered and separated, and the obtained solid is filtered, and dried. The column chromatography and the by-product are separated and purified, and the solvent is distilled off, filtered, and dried to separate the objective compound.

又,於多酚化合物的至少一個酚性羥基上導入羥基烷基,於該羥基導入烯丙基、丙烯酸或甲基丙烯酸基的方法亦為公知。 Further, a method of introducing a hydroxyalkyl group into at least one phenolic hydroxyl group of the polyphenol compound and introducing an allyl group, an acrylic acid group or a methacryl group group into the hydroxyl group is also known.

例如如以下所示,於前述化合物之至少一個的酚性羥基上可導入羥基烷基。 For example, as shown below, a hydroxyalkyl group can be introduced into the phenolic hydroxyl group of at least one of the above compounds.

羥基烷基可介著氧基烷基導入於酚性羥基。例如導入羥基烷氧基烷基或羥基烷氧基烷氧基烷基。 The hydroxyalkyl group may be introduced into the phenolic hydroxyl group via an oxyalkyl group. For example, a hydroxyalkoxyalkyl group or a hydroxyalkoxy alkoxyalkyl group is introduced.

欲導入羥基烷基的化合物可藉由公知方法進行合成或者容易獲得者,例如可舉出氯乙醇、溴乙醇、乙酸-2-氯乙酯、乙酸-2-溴乙酯、乙酸-2-碘乙酯、環氧乙烷、環氧丙烷、環氧丁烷、伸乙基碳酸酯、伸丙基碳酸酯、丁伸基碳酸酯,但並未特別限定於此等。 The compound to be introduced with a hydroxyalkyl group can be synthesized or easily obtained by a known method, and examples thereof include chlorohydrin, bromoethanol, 2-chloroethyl acetate, 2-bromoethyl acetate, and 2-iodine acetate. Ethyl ester, ethylene oxide, propylene oxide, butylene oxide, ethyl acrylate, propyl carbonate, and butyl carbonate, but it is not particularly limited thereto.

例如於丙酮、四氫呋喃(THF)、丙二醇單甲基 醚乙酸酯等非質子性溶劑使前述化合物溶解或懸浮。接著在金屬烷氧化物(甲氧化鈉、乙氧化鈉、甲氧化鉀、乙氧化鉀等鹼金屬或鹼土類金屬烷氧化物等)、金屬氫氧化物(氫氧化鈉、氫氧化鉀等鹼金屬或鹼土類金屬碳酸鹽等)、碳酸氫鈉、碳酸氫鉀等鹼金屬或鹼土類碳酸氫鹽、胺類(例如第3級胺類(三乙基胺等三烷基胺、N,N-二甲基苯胺等的芳香族第3級胺、1-甲基咪唑等雜環式第3級胺)等羧酸金屬鹽(乙酸鈉、乙酸鈣等乙酸鹼金屬或鹼土類金屬鹽等)的有機鹼等鹼觸媒存在下,在常壓於20~150℃進行0.5~100小時反應。將反應液以酸中和,析出於蒸餾水所加入的白色固體後,將分離的固體以蒸餾水洗淨,或使溶劑進行蒸發乾固,視必要藉由蒸餾水洗淨並乾燥後,得到羥基的氫原子由羥基伸烷基所取代的化合物。 For example, the aforesaid compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF) or propylene glycol monomethyl ether acetate. Next, in the metal alkoxide (sodium hydroxide, sodium ethoxide, potassium oxychloride, potassium oxychloride, etc., alkali metal or alkaline earth metal alkoxide, etc.), metal hydroxide (alkali metal such as sodium hydroxide or potassium hydroxide) Or alkaline earth metal carbonates, etc., alkali metal or alkaline earth hydrogencarbonates such as sodium hydrogencarbonate or potassium hydrogencarbonate, and amines (for example, tertiary amines (trialkylamines such as triethylamine, N, N-) a metal carboxylate such as an aromatic third-order amine such as dimethylaniline or a heterocyclic third-order amine such as 1-methylimidazole; an alkali metal acetate or an alkaline earth metal salt such as sodium acetate or calcium acetate; In the presence of an alkali catalyst such as an organic base, the reaction is carried out at a normal pressure at 20 to 150 ° C for 0.5 to 100 hours. The reaction solution is neutralized with an acid, and the white solid added by the distilled water is precipitated, and the separated solid is washed with distilled water. The solvent is evaporated or dried, and if necessary, washed with distilled water and dried to obtain a compound in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group.

使用乙酸-2-氯乙酯、乙酸-2-溴乙酯、乙酸-2-碘乙酯時,導入乙醯氧基乙基後,藉由產生脫醯基反應而導入羥基乙基。 When 2-ethyl chloroacetate, 2-bromoethyl acetate, and 2-iodoethyl acetate were used, after introducing an ethoxyethyl group, a hydroxyethyl group was introduced by a deoximation reaction.

使用伸乙基碳酸酯、伸丙基碳酸酯、丁伸基碳酸酯時,加成伸烷基碳酸酯,產生脫碳酸反應後導入羥基烷基。 When an ethyl carbonate, a propyl carbonate, or a butyl carbonate is used, an alkyl carbonate is added to cause a decarboxylation reaction to introduce a hydroxyalkyl group.

繼續,例如如以下所示,於前述化合物之至少一個的羥基上可導入烯丙基、丙烯酸或甲基丙烯酸基。於該羥基上導入烯丙基、丙烯酸或甲基丙烯酸基之方法亦為公知。 Continuing, for example, as shown below, an allyl group, an acrylic group or a methacryl group may be introduced into the hydroxyl group of at least one of the aforementioned compounds. Methods for introducing an allyl, acrylic or methacrylic group onto the hydroxyl group are also known.

使用於導入烯丙基、丙烯酸或甲基丙烯酸基 的化合物為,藉由公知方法所合成或者為容易獲得者,例如可舉出氯化烯丙基、溴化烯丙基、碘化烯丙基、丙烯酸、丙烯酸氯化物、甲基丙烯酸、甲基丙烯酸氯化物,但並未特別限定於此等。 The compound used for introducing an allyl group, an acrylic acid group or a methacrylic acid group is synthesized by a known method or is easily obtained, and examples thereof include allyl chloride, allyl bromide, and allyl iodide. Acrylic acid, acrylic acid chloride, methacrylic acid, or methacrylic acid chloride, but is not particularly limited thereto.

首先,於丙酮、四氫呋喃(THF)、丙二醇單甲基醚乙酸酯等非質子性溶劑將前述化合物溶解或懸浮。繼續在氫氧化鈉、氫氧化鉀、甲氧化鈉、乙氧化鈉等鹼觸媒存在下,在常壓於20~150℃進行6~72小時反應。將反應液以酸中和,析出於蒸餾水所加入的白色固體後,將分離的固體以蒸餾水洗淨,或使溶劑進行蒸發乾固,視必要藉由蒸餾水洗淨並乾燥後,可得到羥基之氫原子為烯丙基、丙烯酸或以甲基丙烯酸基所取代的化合物。 First, the above compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF) or propylene glycol monomethyl ether acetate. The reaction is continued for 6 to 72 hours under normal pressure at 20 to 150 ° C in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide. The reaction solution is neutralized with an acid, and the white solid added by the distilled water is precipitated, and the separated solid is washed with distilled water, or the solvent is evaporated and dried, and if necessary, washed with distilled water and dried to obtain a hydroxyl group. The hydrogen atom is an allyl group, an acrylic acid or a compound substituted with a methacrylic group.

對於本實施形態,由烯丙基、丙烯酸或甲基丙烯酸基所取代的基為在自由基或酸/鹼之存在下進行反應,對於塗佈溶劑或使用於顯像液的酸、鹼或有機溶劑的溶解性產生變化。前述由烯丙基、丙烯酸或甲基丙烯酸基所取代的基為,進一步欲使高感度.高解像度之圖型形成成為可能,具有在自由基或酸/鹼的存在下可引起連鎖反應之性質者為佳。 In the present embodiment, the group substituted with an allyl group, an acrylic group or a methacryl group is a reaction in the presence of a radical or an acid/base, and is an acid, a base or an organic solvent for a coating solvent or a developing solution. The solubility of the solvent changes. The above-mentioned group substituted by an allyl group, an acrylic group or a methacrylic group is further capable of forming a pattern of high sensitivity and high resolution, and has a property of causing a chain reaction in the presence of a radical or an acid/base. It is better.

[將式(2)所示化合物作為單體所得之樹脂]  [Resin obtained by using the compound represented by the formula (2) as a monomer]  

前述式(2)所示化合物在作為光刻用膜形成組成物或使用於光學零件形成的組成物時,可直接使用。又,將前述式(2)所示化合物作為單體所得之樹脂可作為組成物使 用。樹脂為例如係由反應前述式(2)所示化合物與具有交聯反應性之化合物而得。 When the compound represented by the above formula (2) is used as a composition for forming a film for lithography or a composition for use in an optical component, it can be used as it is. Further, a resin obtained by using the compound represented by the above formula (2) as a monomer can be used as a composition. The resin is obtained, for example, by reacting a compound represented by the above formula (2) with a compound having crosslinking reactivity.

將前述式(2)所示化合物作為單體所得之樹脂,例如可舉出具有以下式(4)所示結構者。即,於本實施形態中之組成物亦可為含有具有下述式(4)所示結構之樹脂者。 The resin obtained by using the compound represented by the above formula (2) as a monomer may, for example, be a structure having the following formula (4). In other words, the composition in the present embodiment may be a resin containing a structure having the structure represented by the following formula (4).

式(4)中,L為可具有取代基之碳數1~30的伸烷基、可具有取代基之碳數6~30的伸芳基、可具有取代基之碳數1~30的伸烷氧基或單鍵,前述伸烷基、前述伸芳基、前述伸烷氧基為可含有醚鍵、酮鍵或酯鍵。又,前述伸烷基、伸烷氧基亦可為直鏈狀、支鏈狀或者環狀之基。 In the formula (4), L is an alkylene group having 1 to 30 carbon atoms which may have a substituent, an extended aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number of 1 to 30 which may have a substituent. An alkoxy group or a single bond, the above alkylene group, the above-mentioned extended aryl group, and the aforementioned alkoxy group may contain an ether bond, a ketone bond or an ester bond. Further, the alkylene group and the alkylene group may be a linear, branched or cyclic group.

R0A、R1A、R2A、m2A、nA、qA及XA與前述式(2)中者為同義,但,nA為2以上的整數時,nA個[ ]內之結構式可為相同或相異,至少一個的m2A為1~6的整數,R2A的至少一個 為含有羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯醯氧基烷基的1個基所取代之基。 R 0A , R 1A , R 2A , m 2A , n A , q A and X A are synonymous with those in the above formula (2), but when n A is an integer of 2 or more, n A structures in [ ] The formula may be the same or different, at least one of m 2A is an integer of 1 to 6, and at least one of R 2A is a hydrogen atom containing a hydroxyl group selected from an allyloxyalkyl group, a propyleneoxyalkyl group or a methyl group. A group substituted with one group of a propylene methoxyalkyl group.

[將式(2)所示化合物作為單體所得之樹脂的製造方法]  [Method for Producing Resin Obtained by Using Compound of Formula (2) as Monomer]  

於本實施形態中之樹脂可藉由將上述式(2)所示化合物與具有交聯反應性的化合物進行反應而得。作為具有交聯反應性之化合物,僅為將前述式(2)所示化合物進行寡聚物化或聚合物化所得者即可,對於公知者並無特別限制下使用。作為該具體例子,例如可舉出醛、酮、羧酸、羧酸鹵化物、鹵素含有化合物、胺基化合物、亞胺化合物、異氰酸酯、不飽和烴基含有化合物等,但並未特別限定於此等。 The resin in the present embodiment can be obtained by reacting a compound represented by the above formula (2) with a compound having crosslinking reactivity. The compound having cross-linking reactivity may be obtained by merely oligomerizing or polymerizing the compound represented by the above formula (2), and is not particularly limited as long as it is known to the public. Examples of the specific examples include an aldehyde, a ketone, a carboxylic acid, a carboxylic acid halide, a halogen-containing compound, an amine compound, an imine compound, an isocyanate, and an unsaturated hydrocarbon group-containing compound. However, the compound is not particularly limited thereto. .

作為具有前述式(4)所示結構之樹脂的具體例子,例如可舉出藉由將上述式(2)所示化合物與具有交聯反應性的化合物之醛及/或酮進行縮合反應等經酚醛清漆化的樹脂。 Specific examples of the resin having the structure represented by the above formula (4) include, for example, a condensation reaction between a compound represented by the above formula (2) and an aldehyde and/or a ketone having a compound having crosslinking reactivity. A novolak-refined resin.

其中,作為將前述式(2)所示化合物使用於酚醛清漆化時的醛,例如可舉出甲醛、三噁烷、三聚乙醛、苯甲醛、乙醛、丙基醛、苯基乙醛、苯基丙基醛、羥基苯甲醛、氯苯甲醛、硝基苯甲醛、甲基苯甲醛、乙基苯甲醛、丁基苯甲醛、聯苯基醛、萘醛、蒽甲醛、菲甲醛、芘甲醛、糠醛等,但並未特別限定於此等。作為酮,可舉出前述酮類。此等中亦以甲醛為較佳。且,這些醛及/或酮類可單獨使用1種或組合2種以上使用。又,上述醛及/或 酮類之使用量並無特別限定,但對於上述式(2)所示化合物1莫耳,以0.2~5莫耳為佳,較佳為0.5~2莫耳。 In addition, examples of the aldehyde used when the compound represented by the above formula (2) is used for novolak formation include formaldehyde, trioxane, paraldehyde, benzaldehyde, acetaldehyde, propyl aldehyde, and phenyl acetaldehyde. , phenylpropyl aldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, biphenyl aldehyde, naphthaldehyde, hydrazine formaldehyde, phenanthrene, hydrazine Formaldehyde, furfural, etc., but it is not specifically limited to these. The ketones include the above ketones. Formaldehyde is also preferred in these. Further, these aldehydes and/or ketones may be used alone or in combination of two or more. Further, the amount of the aldehyde and/or ketone used is not particularly limited, but the compound 1 of the above formula (2) is preferably 0.2 to 5 moles, more preferably 0.5 to 2 moles.

對於前述式(2)所示化合物與醛及/或酮的縮合反應,可使用酸觸媒。對於其中所使用的酸觸媒,可使用適宜地選自公知者,但並無特別限定。作為如此酸觸媒,無機酸或有機酸已廣為人知,例如可舉出鹽酸、硫酸、磷酸、氫溴酸、氫氟酸等無機酸;草酸、丙二酸、琥珀酸、己二酸、癸二酸、檸檬酸、富馬酸、馬來酸、甲酸、p-甲苯磺酸、甲磺酸、三氟乙酸、二氯乙酸、三氯乙酸、三氟甲磺酸、苯磺酸、萘磺酸、萘二磺酸等有機酸;氯化鋅、氯化鋁、氯化鐵、三氟化硼等路易氏酸或矽鎢酸、磷鎢酸、矽鉬酸或磷鉬酸等固體酸等,但並未特別限定於此等。彼等中由製造上的觀點來看,以有機酸或固體酸為佳,由獲得容易性或處理容易性等製造上的觀點來看,以鹽酸或硫酸為佳。又,對於酸觸媒可單獨使用1種或組合2種以上使用。 An acid catalyst can be used for the condensation reaction of the compound represented by the above formula (2) with an aldehyde and/or a ketone. The acid catalyst used therein may be appropriately selected from those known from the public, but is not particularly limited. As such an acid catalyst, an inorganic acid or an organic acid is widely known, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; oxalic acid, malonic acid, succinic acid, adipic acid, and hydrazine. Acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid An organic acid such as naphthalene disulfonic acid; a solid acid such as zinc chloride, aluminum chloride, iron chloride or boron trifluoride; or a solid acid such as tungstic acid, phosphotungstic acid, lanthanum molybdate or phosphomolybdic acid; However, it is not particularly limited to this. Among them, from the viewpoint of production, an organic acid or a solid acid is preferred, and hydrochloric acid or sulfuric acid is preferred from the viewpoint of availability, ease of handling, and the like. Further, the acid catalyst may be used singly or in combination of two or more.

又,酸觸媒的使用量可配合所使用的原料及觸媒種類,進一步可配合反應條件等做適宜設定,並無特別限定,但對於反應原料100質量份而言,以0.01~100質量份者為佳。但在與茚、羥基茚、苯並呋喃、羥基蒽、苊烯、聯苯基、雙酚、三酚、二環戊二烯、四氫茚、4-乙烯基環己烯、冰片二烯、5-乙烯基降冰片-2-烯、α-蒎烯、β-蒎烯、檸檬烯等具有非共軛雙鍵的化合物之共聚合反應時,醛類並非必要。 In addition, the amount of the acid catalyst to be used may be appropriately set in accordance with the reaction conditions and the like, and is not particularly limited. However, the amount of the reaction raw material is 0.01 to 100 parts by mass based on 100 parts by mass of the reaction raw material. It is better. But in combination with hydrazine, hydroxy hydrazine, benzofuran, hydroxy hydrazine, decene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroanthracene, 4-vinylcyclohexene, borneol, When a copolymerization reaction of a compound having a non-conjugated double bond such as 5-vinylnorborn-2-ene, α-pinene, β-pinene or limonene is carried out, an aldehyde is not essential.

對於前述式(2)所示化合物與醛及/或酮的縮合反應,可使用反應溶劑。作為該聚縮合中之反應溶劑,可使用適宜地選自公知者,並無特別限定,例如可舉出水、甲醇、乙醇、丙醇、丁醇、四氫呋喃、二噁烷或這些混合溶劑等。且溶劑可單獨使用1種或組合2種以上後使用。 A reaction solvent can be used for the condensation reaction of the compound represented by the above formula (2) with an aldehyde and/or a ketone. The reaction solvent in the polycondensation is suitably selected from known ones, and is not particularly limited, and examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane or a mixed solvent thereof. Further, the solvent may be used singly or in combination of two or more.

又,這些溶劑之使用量可配合所使用的原料及觸媒種類,進一步可配合反應條件等而適宜設定,並無特別限定,對於反應原料100質量份而言以0~2000質量份的範圍者為佳。且反應溫度可配合反應原料之反應性而做適宜選擇,並無特別限定,通常為10~200℃之範圍。且,反應方法可適宜地選擇公知手法使用,並無特別限定,可舉出一併裝入上述式(2)所示化合物、醛及/或酮類、觸媒的方法,或將上述式(2)所示化合物或醛及/或酮類在觸媒存在下滴入的方法。 In addition, the amount of the solvent to be used may be appropriately set in accordance with the reaction materials and the like, and is not particularly limited, and is in the range of 0 to 2000 parts by mass based on 100 parts by mass of the reaction raw material. It is better. Further, the reaction temperature is appropriately selected in accordance with the reactivity of the reaction raw material, and is not particularly limited, and is usually in the range of 10 to 200 °C. Further, the reaction method can be appropriately selected from known methods, and is not particularly limited, and a method of incorporating the compound represented by the above formula (2), an aldehyde and/or a ketone, a catalyst, or the above formula ( 2) A method of dropping the compound or aldehyde and/or ketone shown in the presence of a catalyst.

聚縮合反應終了後,所得之化合物的分離可依據常法進行,但並無特別限定。例如欲除去存在於系統內的未反應原料或觸媒等,可藉由將反應釜溫度上升至130~230℃,在1~50mmHg程度下除去揮發成分等一般手法,分離目的物之經酚醛清漆化的樹脂。 After the completion of the polycondensation reaction, the separation of the obtained compound can be carried out according to a usual method, but is not particularly limited. For example, in order to remove unreacted raw materials or catalysts present in the system, a general method such as removing volatile components at a temperature of from 1 to 50 mmHg can be carried out by raising the temperature of the reaction vessel to 130 to 230 ° C to separate the target phenol varnish. Resin.

其中,具有前述式(4)所示結構之樹脂可為前述式(2)所示化合物的單獨聚合物,但亦可為與其他酚類的共聚物。其中,作為可共聚合的酚類,例如可舉出酚、甲酚、二甲基酚、三甲基酚、丁基酚、苯基酚、二苯基酚、萘酚、間苯二酚、甲基間苯二酚、鄰苯二酚、丁基鄰 苯二酚、甲氧基酚、甲氧基酚、丙基酚、鄰苯三酚、麝香草酚等,但並未特別限定於此等。 Among them, the resin having the structure represented by the above formula (4) may be a single polymer of the compound represented by the above formula (2), but may be a copolymer with other phenols. In addition, examples of the phenol which can be copolymerized include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthol, and resorcinol. Methyl resorcinol, catechol, butyl catechol, methoxy phenol, methoxy phenol, propyl phenol, pyrogallol, thymol, etc., but is not particularly limited thereto Wait.

又,具有前述式(4)所示結構的樹脂除上述其他酚類以外,亦可為與可聚合的單體進行共聚合者。作為該共聚合單體,例如可舉出萘酚、甲基萘酚、甲氧基萘酚、二羥基萘、茚、羥基茚、苯並呋喃、羥基蒽、苊烯、聯苯基、雙酚、三酚、二環戊二烯、四氫茚、4-乙烯基環己烯、冰片二烯、乙烯基降冰片烯、蒎烯、檸檬烯等,但並未特別限定於此等。且,具有前述式(4)所示結構之樹脂即使為前述式(2)所示化合物與上述酚類的2元以上之(例如2~4元系)共聚物,即使為前述式(2)所示化合物與上述共聚合單體的2元以上(例如2~4元系)共聚物,即使為前述式(2)所示化合物與上述酚類與上述共聚合單體的3元以上之(例如3~4元系)共聚物亦可。 Further, the resin having the structure represented by the above formula (4) may be copolymerized with a polymerizable monomer in addition to the above other phenols. Examples of the copolymerizable monomer include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, anthracene, hydroxyanthracene, benzofuran, hydroxyanthracene, decene, biphenylyl, and bisphenol. And tris, dicyclopentadiene, tetrahydroanthracene, 4-vinylcyclohexene, borneol, vinyl norbornene, decene, limonene, etc., but are not particularly limited thereto. Further, even if the resin having the structure represented by the above formula (4) is a copolymer of two or more (for example, two to four elements) of the compound represented by the above formula (2) and the above phenol, even if it is the above formula (2) The copolymer of the above-mentioned compound and the above-mentioned copolymerized monomer of two or more (for example, two to four-membered) copolymer is not more than three or more of the compound represented by the above formula (2) and the above phenol and the above-mentioned copolymerized monomer ( For example, a 3 to 4 member copolymer) may also be used.

且,具有前述式(4)所示結構之樹脂的分子量並無特別限定,但聚苯乙烯換算的重量平均分子量(Mw)以500~30,000者為佳,較佳為750~20,000。又,由提高交聯效率之同時可抑制燒烤中之揮發成分的觀點來看,具有前述式(4)所示結構之樹脂的分散度(重量平均分子量Mw/數平均分子量Mn)以1.2~7的範圍內者為佳。且,上述Mw及Mn可藉由後述實施例所記載的方法求得。 Further, the molecular weight of the resin having the structure represented by the above formula (4) is not particularly limited, but the weight average molecular weight (Mw) in terms of polystyrene is preferably from 500 to 30,000, preferably from 750 to 20,000. Moreover, the degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of the resin having the structure represented by the above formula (4) is 1.2 to 7 from the viewpoint of suppressing the crosslinking component while improving the crosslinking efficiency. The range is better. Further, the above Mw and Mn can be obtained by the method described in the examples below.

具有前述式(4)所示結構的樹脂,由濕式製程的適用變的更容易等觀點來看,以對溶劑之溶解性高者為佳。更具體為將1-甲氧基-2-丙醇(PGME)及/或丙二醇單甲 基醚乙酸酯(PGMEA)作為溶劑時,對於該溶劑之溶解度以10質量%以上者為佳。其中,對於PGME及/或PGMEA之溶解度被定義為「樹脂質量÷(樹脂質量+溶劑質量)×100(質量%)」。例如前述樹脂10g對於PGMEA90g為溶解時,前述樹脂對於PGMEA之溶解度成為「10質量%以上」,未溶解時成為「未達10質量%」。 The resin having the structure represented by the above formula (4) is preferably one having a high solubility in a solvent from the viewpoint of easiness of application to a wet process. More specifically, when 1-methoxy-2-propanol (PGME) and/or propylene glycol monomethyl ether acetate (PGMEA) is used as the solvent, the solubility of the solvent is preferably 10% by mass or more. The solubility of PGME and/or PGMEA is defined as "resin mass ÷ (resin mass + solvent mass) × 100 (% by mass)". For example, when 10 g of the resin is dissolved in PGMEA 90 g, the solubility of the resin to PGMEA is "10% by mass or more", and when it is not dissolved, it is "less than 10% by mass".

[化合物及/或樹脂之純化方法]  [Purification method of compound and / or resin]  

於本實施形態中之化合物及/或樹脂的純化方法為含有將選自前述式(1)所示化合物、前述式(1)所示化合物作為單體而得之樹脂、前述式(2)所示化合物、及將前述式(2)所示化合物作為單體而得之樹脂的1種以上溶解於溶劑中得到溶液(S)之步驟、將所得之溶液(S)與酸性水溶液接觸後,萃取前述化合物及/或前述樹脂中之雜質的步驟(第一萃取步驟),在得到前述溶液(S)之步驟所使用的溶劑含有與水不會任意混合的溶劑。 The method for purifying the compound and/or the resin in the present embodiment is a resin obtained by using a compound selected from the above formula (1) and a compound represented by the above formula (1) as a monomer, and the above formula (2) One or more kinds of the compound obtained by using the compound represented by the above formula (2) as a monomer are dissolved in a solvent to obtain a solution (S), and the obtained solution (S) is contacted with an acidic aqueous solution, followed by extraction. The step (first extraction step) of the compound and/or the impurities in the resin described above, the solvent used in the step of obtaining the solution (S) contains a solvent which is not arbitrarily mixed with water.

對於第一萃取步驟,上述樹脂係以藉由上述式(1)所示化合物及/或式(2)所示化合物與具有交聯反應性的化合物之反應而得之樹脂者為佳。所謂本實施形態的純化方法,可減低具有上述特定結構的化合物或樹脂中作為雜質所含的種種金屬之含有量。 In the first extraction step, the resin is preferably a resin obtained by reacting a compound represented by the above formula (1) and/or a compound represented by the formula (2) with a compound having crosslinking reactivity. In the purification method of the present embodiment, the content of various metals contained as impurities in the compound or resin having the above specific structure can be reduced.

更詳細為,對於本實施形態之純化方法,將前述化合物及/或前述樹脂溶解於與水不會任意混合的有機溶劑後得到溶液(S),可進一步將該溶液(S)與酸性水溶液接觸後 進行萃取處理。藉此,將含於前述溶液(S)之金屬部分移至水相後,分離有機相與水相得到金屬含有量經減低之化合物及/或樹脂。 More specifically, in the purification method of the present embodiment, the compound (and the resin) is dissolved in an organic solvent which is not arbitrarily mixed with water to obtain a solution (S), and the solution (S) can be further contacted with an acidic aqueous solution. After the extraction treatment. Thereby, after the metal portion contained in the solution (S) is transferred to the aqueous phase, the organic phase and the aqueous phase are separated to obtain a compound and/or a resin having a reduced metal content.

在本實施形態的純化方法所使用的化合物及/或樹脂可單獨使用,亦可混合2種以上後使用。又,前述化合物或樹脂可含有各種界面活性劑、各種交聯劑、各種酸產生劑、各種安定劑等。 The compound and/or the resin used in the purification method of the present embodiment may be used singly or in combination of two or more kinds. Further, the above compound or resin may contain various surfactants, various crosslinking agents, various acid generators, various stabilizers, and the like.

作為於本實施形態的純化方法中所使用的與水不會任意混合的溶劑,並無特別限定,以可在半導體製造製程中安全適用的有機溶劑為佳,具體而言在室溫下對於水之溶解度未達30%,較佳為未達20%,更佳為未達10%的有機溶劑。該有機溶劑之使用量對於所使用的化合物與樹脂的合計量而言以1~100質量倍者為佳。 The solvent which is used in the purification method of the present embodiment and which is not arbitrarily mixed with water is not particularly limited, and is preferably an organic solvent which can be safely applied in a semiconductor manufacturing process, specifically, water at room temperature. The solubility is less than 30%, preferably less than 20%, more preferably less than 10% organic solvent. The amount of the organic solvent used is preferably from 1 to 100 times by mass based on the total amount of the compound to be used and the resin.

作為與水不會任意混合的溶劑之具體例子,並未限定於以下,例如可舉出二乙基醚、二異丙基醚等醚類;乙酸乙酯、乙酸n-丁酯、乙酸異戊酯等酯類、甲基乙基酮、甲基異丁基酮、乙基異丁基酮、環己酮、環戊酮、2-庚酮、2-戊酮等酮類;乙二醇單乙基醚乙酸酯、乙二醇單丁基醚乙酸酯、丙二醇單甲基醚乙酸酯(PGMEA)、丙二醇單乙基醚乙酸酯等甘醇醚乙酸酯類;n-己烷、n-庚烷等脂肪族烴類;甲苯、二甲苯等的芳香族烴類;二氯甲烷、氯仿等鹵素化烴類等。彼等中,亦以甲苯、2-庚酮、環己酮、環戊酮、甲基異丁基酮、丙二醇單甲基醚乙酸酯、乙酸乙酯為佳,以甲基異丁基酮、乙酸乙酯、環己酮、丙二 醇單甲基醚乙酸酯為較佳,以甲基異丁基酮、乙酸乙酯為更佳。甲基異丁基酮、乙酸乙酯等因上述化合物及將該化合物作為構成成分含有的樹脂之飽和溶解度比較高且沸點比較低,故可減低餾去工業上溶劑時或藉由乾燥除去的步驟之負荷。這些溶劑可各單獨使用,亦可混合2種以上使用。 Specific examples of the solvent which is not arbitrarily mixed with water are not limited to the following, and examples thereof include ethers such as diethyl ether and diisopropyl ether; ethyl acetate, n-butyl acetate, and isoamyl acetate; Ketones such as esters, esters such as methyl ethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 2-pentanone; Glycol ether acetate such as ethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate; n-hexane An aliphatic hydrocarbon such as n-heptane; an aromatic hydrocarbon such as toluene or xylene; or a halogenated hydrocarbon such as dichloromethane or chloroform. Among them, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate are preferred, and methyl isobutyl ketone is preferred. Ethyl acetate, cyclohexanone, and propylene glycol monomethyl ether acetate are preferred, and methyl isobutyl ketone or ethyl acetate is more preferred. Methyl isobutyl ketone, ethyl acetate, etc., because the above compound and the resin containing the compound as a constituent component have a relatively high saturated solubility and a relatively low boiling point, the step of distilling off the industrial solvent or removing it by drying can be reduced. The load. These solvents may be used alone or in combination of two or more.

作為本實施形態之純化方法中所使用的酸性水溶液,可適宜地選自將一般已知的有機系化合物或者無機系化合物溶解於水之水溶液中者。作為酸性水溶液,雖未限定於以下所示者,例如可舉出將鹽酸、硫酸、硝酸、磷酸等無機酸溶解於水之無機酸水溶液;將乙酸、丙酸、草酸、丙二酸、琥珀酸、富馬酸、馬來酸、酒石酸、檸檬酸、甲磺酸、酚磺酸、p-甲苯磺酸、三氟乙酸等有機酸溶解於水的有機酸水溶液。這些酸性水溶液可各單獨使用,或組合2種以上後使用。這些酸性水溶液之中,亦以選自由鹽酸、硫酸、硝酸及磷酸所成群的1種以上無機酸水溶液或選自由乙酸、丙酸、草酸、丙二酸、琥珀酸、富馬酸、馬來酸、酒石酸、檸檬酸、甲磺酸、酚磺酸、p-甲苯磺酸及三氟乙酸所成群的1種以上有機酸水溶液者為佳,以硫酸、硝酸、及乙酸、草酸、酒石酸、檸檬酸等羧酸的水溶液為較佳,以硫酸、草酸、酒石酸、檸檬酸的水溶液為更佳,以草酸的水溶液為更較佳。草酸、酒石酸、檸檬酸等多元羧酸因配位於金屬離子上,產生螯合效果,故亦被認為可更有效果地除去金屬之傾向者。又,於此所使用 的水為依據本實施形態之純化方法的目的,使用金屬含有量較少的水,例如使用離子交換水等者為佳。 The acidic aqueous solution used in the purification method of the present embodiment can be suitably selected from those in which an organic compound or an inorganic compound which is generally known is dissolved in an aqueous solution of water. The acidic aqueous solution is not limited to the ones described below, and examples thereof include an aqueous solution of an inorganic acid in which a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid is dissolved in water; acetic acid, propionic acid, oxalic acid, malonic acid, and succinic acid are used. An organic acid aqueous solution in which an organic acid such as fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid or trifluoroacetic acid is dissolved in water. These acidic aqueous solutions may be used singly or in combination of two or more. Among these acidic aqueous solutions, one or more inorganic acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid are also selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, and Malay. It is preferred to use one or more kinds of organic acid aqueous solutions in the group of acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid, and sulfuric acid, nitric acid, and acetic acid, oxalic acid, tartaric acid, An aqueous solution of a carboxylic acid such as citric acid is preferred, and an aqueous solution of sulfuric acid, oxalic acid, tartaric acid or citric acid is more preferred, and an aqueous solution of oxalic acid is more preferred. Polycarboxylic acids such as oxalic acid, tartaric acid, and citric acid are also known to be more effective in removing metals because they are coordinated to metal ions to produce a chelate effect. Further, the water used herein is preferably a water having a small metal content, for example, ion-exchanged water or the like, for the purpose of the purification method according to the present embodiment.

對於本實施形態的純化方法中所使用的酸性水溶液之pH並無特別限定,但若考慮到對上述化合物或樹脂的影響,調整水溶液之酸性度為佳。酸性水溶液之pH通常為0~5程度,較佳為pH0~3程度。 The pH of the acidic aqueous solution used in the purification method of the present embodiment is not particularly limited, but the acidity of the aqueous solution is preferably adjusted in consideration of the influence on the above compound or resin. The pH of the acidic aqueous solution is usually from 0 to 5, preferably from 0 to 3.

對於本實施形態的純化方法中所使用的酸性水溶液之使用量並無特別限定,由減低欲進行金屬除去之萃取次數的觀點及考慮到全體液量而確保操作性之觀點來看,調整使用量為佳。由上述觀點得知,酸性水溶液的使用量對於前述溶液(S)100質量%而言,以10~200質量%為佳,較佳為20~100質量%。 The amount of the acidic aqueous solution to be used in the purification method of the present embodiment is not particularly limited, and the amount of use is adjusted from the viewpoint of reducing the number of extractions for which metal removal is required, and from the viewpoint of ensuring operability in consideration of the total amount of liquid. It is better. From the above viewpoints, the amount of the acidic aqueous solution used is preferably from 10 to 200% by mass, preferably from 20 to 100% by mass, based on 100% by mass of the solution (S).

對於本實施形態的純化方法為藉由將前述酸性水溶液與前述溶液(S)接觸,可由溶液(S)中之前述化合物或前述樹脂萃取出金屬部分。 In the purification method of the present embodiment, the metal portion can be extracted from the compound or the resin in the solution (S) by bringing the acidic aqueous solution into contact with the solution (S).

對於本實施形態之純化方法,以前述溶液(S)進一步含有與水任意混合的有機溶劑者為佳。溶液(S)含有與水任意混合的有機溶劑時,可增加前述化合物及/或樹脂的裝入量,又有著分液性提高,在高釜效率下可進行純化之傾向。加入與水任意混合的有機溶劑之方法並無特別限定,例如可為預先加入於含有有機溶劑的溶液之方法、預先加入於水或酸性水溶液的方法、於含有有機溶劑的溶液與水或酸性水溶液進行接觸後加入的方法中任一者皆可。這些中亦由操作的作業性或裝入量之管理容易性的 觀點來看,以預先加入於含有有機溶劑之溶液的方法為佳。 In the purification method of the present embodiment, it is preferred that the solution (S) further contains an organic solvent which is optionally mixed with water. When the solution (S) contains an organic solvent which is optionally mixed with water, the amount of the compound and/or the resin to be added can be increased, and the liquid separation property can be improved, and the purification can be carried out under high autoclave efficiency. The method of adding an organic solvent arbitrarily mixed with water is not particularly limited, and examples thereof include a method of previously adding a solution containing an organic solvent, a method of previously adding to water or an acidic aqueous solution, a solution containing an organic solvent, and water or an acidic aqueous solution. Any of the methods of adding after contact may be used. Among these, a method of previously adding a solution containing an organic solvent is preferred from the viewpoint of ease of management of handling workability and loading amount.

作為對於本實施形態之純化方法所使用的與水任意混合的有機溶劑,並無特別限定,於半導體製造製程上可安全適用之有機溶劑為佳。與水任意混合的有機溶劑之使用量若溶液相與水相為分離範圍下即可,並無特別限定,但對於使用的化合物與樹脂之合計量而言,以0.1~100質量倍者為佳,以0.1~50質量倍者為較佳,以0.1~20質量倍者為更佳。 The organic solvent to be arbitrarily mixed with water used in the purification method of the present embodiment is not particularly limited, and an organic solvent which can be safely applied to a semiconductor manufacturing process is preferred. The amount of the organic solvent to be arbitrarily mixed with water is not particularly limited as long as the solution phase and the aqueous phase are separated, but it is preferably 0.1 to 100 times the total amount of the compound to be used and the resin. It is preferably 0.1 to 50 mass times, and more preferably 0.1 to 20 mass times.

作為對於本實施形態之純化方法所使用的與水任意混合的有機溶劑之具體例子,雖未限定於以下者,但可舉出四氫呋喃、1,3-二呋喃等醚類;甲醇、乙醇、異丙醇等醇類;丙酮、N-甲基吡咯啶酮等酮類;乙二醇單乙基醚、乙二醇單丁基醚、丙二醇單甲基醚(PGME)、丙二醇單乙基醚等甘醇醚類等脂肪族烴類。這些中亦以N-甲基吡咯啶酮、丙二醇單甲基醚等為佳,以N-甲基吡咯啶酮、丙二醇單甲基醚為較佳。這些溶劑各可單獨使用,亦可混合2種以上後使用。 Specific examples of the organic solvent to be arbitrarily mixed with water used in the purification method of the present embodiment are not limited to the following, and examples thereof include ethers such as tetrahydrofuran and 1,3-difuran; and methanol, ethanol, and the like. Alcohols such as propanol; ketones such as acetone and N-methylpyrrolidone; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, etc. An aliphatic hydrocarbon such as a glycol ether. Among them, N-methylpyrrolidone, propylene glycol monomethyl ether and the like are preferred, and N-methylpyrrolidone and propylene glycol monomethyl ether are preferred. These solvents may be used singly or in combination of two or more.

進行萃取處理時的溫度通常為20~90℃,較佳為30~80℃的範圍。萃取操作例如藉由攪拌等使其充分混合後,藉由靜置而進行。藉此含於溶液(S)中之金屬部分移至水相。又,藉由本操作,溶液之酸性度降低,可抑制化合物及/或樹脂之變質。 The temperature at which the extraction treatment is carried out is usually 20 to 90 ° C, preferably 30 to 80 ° C. The extraction operation is carried out by standing still, for example, by stirring or the like. Thereby, the metal portion contained in the solution (S) is moved to the aqueous phase. Moreover, by this operation, the acidity of the solution is lowered, and deterioration of the compound and/or the resin can be suppressed.

前述混合溶液為藉由靜置,分離為含有化合 物及/或樹脂與溶劑之溶液相與水相,故藉由傾析等可回收溶液相。靜置時間並無特別限定,由可更良好地分離含有溶劑之溶液相與水相的觀點來看,調整該靜置時間為佳。通常靜置時間為1分鐘以上,以10分鐘以上為佳,較佳為30分鐘以上。又,萃取處理可僅為1次,但可重複進行多次的混合、靜置、分離之操作亦為有效。 The mixed solution is separated into a liquid phase containing a compound and/or a resin and a solvent by standing, so that the solution phase can be recovered by decantation or the like. The standing time is not particularly limited, and it is preferable to adjust the standing time from the viewpoint of more preferably separating the solvent phase and the aqueous phase. The standing time is usually 1 minute or longer, preferably 10 minutes or longer, preferably 30 minutes or longer. Further, the extraction treatment may be performed only once, but it is also effective to repeat the mixing, standing, and separation operations.

對於本實施形態之純化方法為含有於前述第一萃取步驟後,將含有前述化合物或前述樹脂之溶液相進一步與水接觸,萃取前述化合物或前述樹脂中之雜質的步驟(第二萃取步驟)者為佳。具體為,例如使用酸性水溶液進行上述萃取處理後,將含有由該水溶液所萃取並回收的化合物及/或樹脂與溶劑之溶液相,進一步藉由水進行萃取處理者為佳。藉由該水的萃取處理並無特別限定,例如將前述溶液相與水藉由攪拌等充分混合後,藉由靜置所得之混合溶液而進行。該靜置後之混合溶液因分離為含有化合物及/或樹脂與溶劑之溶液相與水相,故可藉由傾析等回收溶液相。 The purification method of the present embodiment is a step (second extraction step) in which the solution containing the compound or the resin is further contacted with water after the first extraction step, and the impurities in the compound or the resin are extracted. It is better. Specifically, for example, after the above-described extraction treatment using an acidic aqueous solution, it is preferred to further include a solution containing a compound and/or a resin extracted and recovered from the aqueous solution and a solvent, and further extracting the solution by water. The extraction treatment of the water is not particularly limited. For example, the solution phase and the water are sufficiently mixed by stirring or the like, and then the resulting mixed solution is allowed to stand. Since the mixed solution after the standing is separated into a solution phase containing a compound and/or a resin and a solvent, the solution phase can be recovered by decantation or the like.

又,其中所使用的水為依據本實施的形態之目的,以金屬含有量較少的水,例如以離子交換水等者為佳。萃取處理可僅進行1次,但混合、靜置、分離之操作可重複進行數次亦為有效。又,對於萃取處理中之兩者的使用比例或溫度、時間等條件並無特別限定與前述的與酸性水溶液的接觸處理情況相同。 Further, the water to be used therein is preferably a water having a small metal content, for example, ion-exchanged water or the like, for the purpose of the embodiment according to the present embodiment. The extraction treatment can be carried out only once, but it is also effective to repeat the operation of mixing, standing and separating several times. Moreover, the conditions of use, temperature, time, and the like of the two in the extraction treatment are not particularly limited as in the case of the above-described contact treatment with an acidic aqueous solution.

對於混入於含有所得之化合物及/或樹脂與溶 劑的溶液之水分,藉由施予減壓蒸餾等操作可容易除去。又,視必要於前述溶液加入溶劑,可調整化合物及/或樹脂之濃度至任意濃度。 The water mixed in the solution containing the obtained compound and/or the resin and the solvent can be easily removed by an operation such as vacuum distillation. Further, the concentration of the compound and/or the resin may be adjusted to any concentration as necessary to add the solvent to the solution.

由含有所得之化合物及/或樹脂與溶劑的溶液,分離化合物及/或樹脂的方法並無特別限定,可進行減壓除去、藉由再沈澱之分離及此等組合等公知方法。視必要可進行濃縮操作、過濾操作、離心分離操作、乾燥操作等公知處理。 The method for separating the compound and/or the resin from the solution containing the obtained compound and/or the resin and the solvent is not particularly limited, and a known method such as removal under reduced pressure, separation by reprecipitation, and combinations thereof may be employed. A known treatment such as a concentration operation, a filtration operation, a centrifugal separation operation, and a drying operation may be performed as necessary.

[光刻用膜形成組成物]  [Film forming composition for lithography]  

於本實施形態中之光刻用膜形成組成物含有選自由前述式(1)所示化合物、將前述式(1)所示化合物作為單體所得之樹脂、前述式(2)所示化合物及將前述式(2)所示化合物作為單體所得之樹脂所成群的1種以上。 The film forming composition for lithography according to the present embodiment contains a resin selected from the compound represented by the above formula (1), a compound obtained by using the compound represented by the above formula (1) as a monomer, and a compound represented by the above formula (2). One or more types of the resin obtained by using the compound represented by the above formula (2) as a monomer.

[使用於化學增幅型抗蝕用途之光刻用膜形成組成物]  [Film forming composition for lithography used for chemical amplification type resist]  

於本實施形態中之使用於化學增幅型抗蝕用途的光刻用膜形成組成物(以下亦稱為「抗蝕組成物」)為含有選自由前述式(1)所示化合物、將前述式(1)所示化合物作為單體所得之樹脂、前述式(2)所示化合物及將前述式(2)所示化合物作為單體所得之樹脂所成群的1種以上作為抗蝕基材。 The film forming composition for lithography (hereinafter also referred to as "resist composition") used for the chemical amplification type resist is contained in the present embodiment, and contains the compound represented by the above formula (1). (1) One or more types of the resin obtained as a monomer, the compound represented by the above formula (2), and the resin obtained by using the compound represented by the above formula (2) as a monomer are used as a resist substrate.

又,於本實施形態中之抗蝕組成物以具有溶劑者為佳。作為溶劑,並無特別限定,例如可舉出乙二醇 單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單-n-丙基醚乙酸酯、乙二醇單-n-丁基醚乙酸酯等乙二醇單烷基醚乙酸酯類;乙二醇單甲基醚、乙二醇單乙基醚等乙二醇單烷基醚類;丙二醇單甲基醚乙酸酯(PGMEA)、丙二醇單乙基醚乙酸酯、丙二醇單-n-丙基醚乙酸酯、丙二醇單-n-丁基醚乙酸酯等丙二醇單烷基醚乙酸酯類;丙二醇單甲基醚(PGME)、丙二醇單乙基醚等丙二醇單烷基醚類;乳酸甲酯、乳酸乙酯、乳酸n-丙酯、乳酸n-丁酯、乳酸n-戊酯等乳酸酯類;乙酸甲酯、乙酸乙酯、乙酸n-丙酯、乙酸n-丁酯、乙酸n-戊酯、乙酸n-己酯、丙酸甲酯、丙酸乙酯等脂肪族羧酸酯類;3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-甲氧基-2-甲基丙酸甲酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲氧基-3-甲基丙酸丁酯、3-甲氧基-3-甲基丁酸丁基、乙醯乙酸甲酯、丙酮酸甲基、丙酮酸乙基等其他酯類;甲苯、二甲苯等芳香族烴類;2-庚酮、3-庚酮、4-庚酮、環戊酮(CPN)、環己酮(CHN)等酮類;N,N-二甲基甲醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮等醯胺類;γ-內酯等內酯類等,但並未特別限定於此等。這些溶劑可單獨使用,亦可併用2種以上。 Further, the resist composition in the present embodiment is preferably a solvent. The solvent is not particularly limited, and examples thereof include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol. Ethylene glycol monoalkyl ether acetate such as alcohol mono-n-butyl ether acetate; ethylene glycol monoalkyl ether such as ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; propylene glycol single Propylene glycol monoalkyl ether acetate such as methyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, n-amyl lactate, etc. Lactic acid esters; aliphatic carboxylic acids such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-pentyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate Esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxy-2 -methyl methacrylate, 3-methoxybutyl acetate, 3-methyl-3-methoxy Acetate, butyl 3-methoxy-3-methylpropanoate, butyl 3-methoxy-3-methylbutyrate, methyl ethyl acetate, methyl pyruvate, ethyl pyruvate Other esters; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), cyclohexanone (CHN); N, N - lactones such as dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, and lactones such as γ-lactone, but It is not particularly limited to this. These solvents may be used singly or in combination of two or more.

在本實施形態所使用的溶劑以安全溶劑者為佳,較佳為選自PGMEA、PGME、CHN、CPN、2-庚酮、苯甲醚、乙酸丁酯、丙酸乙酯及乳酸乙酯的至少1種,更佳為選自PGMEA、PGME及CHN的至少一種。 The solvent used in the present embodiment is preferably a safe solvent, and is preferably selected from the group consisting of PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, ethyl propionate, and ethyl lactate. At least one, more preferably at least one selected from the group consisting of PGMEA, PGME, and CHN.

對於本實施形態,固體成分量與溶劑量並無特別限定,對於固體成分量與溶劑之合計質量100質量%而言,以固體成分1~80質量%及溶劑20~99質量%者為佳,較佳為固體成分1~50質量%及溶劑50~99質量%,更佳為固體成分2~40質量%及溶劑60~98質量%,特佳為固體成分2~10質量%及溶劑90~98質量%。 In the present embodiment, the solid content and the amount of the solvent are not particularly limited, and the solid content is preferably from 1 to 80% by mass and the solvent is from 20 to 99% by mass based on 100% by mass of the total mass of the solvent. It is preferably 1 to 50% by mass of the solid component and 50 to 99% by mass of the solvent, more preferably 2 to 40% by mass of the solid component and 60 to 98% by mass of the solvent, and particularly preferably 2 to 10% by mass of the solid component and 90% of the solvent. 98% by mass.

本實施形態的抗蝕組成物為,作為其他固體成分,可含有選自由酸產生劑(C)、交聯劑(G)、酸擴散控制劑(E)及其他成分(F)所成群的至少一種。且,本說明書中之「固體成分」表示溶劑以外的成分。 The resist composition of the present embodiment may contain, as other solid components, a group selected from the group consisting of an acid generator (C), a crosslinking agent (G), an acid diffusion controlling agent (E), and other components (F). At least one. Further, the "solid content" in the present specification means a component other than the solvent.

其中,對於酸產生劑(C)、交聯劑(G)、酸擴散控制劑(E)及其他成分(F)可使用公知者,並無特別限定,例如以國際公開第2013/024778號所記載者為佳。 In addition, the acid generator (C), the crosslinking agent (G), the acid diffusion controlling agent (E), and other components (F) can be used, and it is not specifically limited, for example, International Publication No. 2013/024778 The record is better.

[各成分之配合比例]  [mixing ratio of each component]  

對於本實施形態之抗蝕組成物,作為抗蝕基材所使用的化合物及/或樹脂之含有量並無特別限定,以固體成分的全質量(含有抗蝕基材、酸產生劑(C)、交聯劑(G)、酸擴散控制劑(E)及其他成分(F)等任意使用的成分之固體成分的總合,以下同樣。)之50~99.4質量%者為佳,較佳為55~90質量%,更佳為60~80質量%,特佳為60~70質量%。作為抗蝕基材所使用的化合物及/或樹脂之含有量若在上述範圍時,有著解像度可進一步提高,線邊緣粗糙度(LER進一步變小的傾向。 In the anticorrosive composition of the present embodiment, the content of the compound and/or the resin used as the resist substrate is not particularly limited, and the total mass of the solid component (including the resist substrate and the acid generator (C)) The total of the solid components of the arbitrarily used component such as the crosslinking agent (G), the acid diffusion controlling agent (E), and the other component (F) is preferably the same as the following: 50 to 99.4% by mass, preferably 55 to 90% by mass, more preferably 60 to 80% by mass, particularly preferably 60 to 70% by mass. When the content of the compound and/or the resin used as the resist base material is in the above range, the resolution can be further improved, and the line edge roughness (LER tends to be further small).

且,作為抗蝕基材含有化合物與樹脂雙方時,前述含有量為兩成分之合計量。 Further, when both the compound and the resin are contained as the resist substrate, the content is the total amount of the two components.

[其他成分(F)]  [Other ingredients (F)]  

於本實施形態中之抗蝕組成物中,不阻礙本發明之目的的範圍下,視必要作為抗蝕基材、酸產生劑(C)、交聯劑(G)及酸擴散控制劑(E)以外成分,可添加1種或2種以上的溶解促進劑、溶解控制劑、增感劑、界面活性劑、有機羧酸或磷之含氧酸或者其衍生物、熱及/或光硬化觸媒、聚合禁止劑、難燃劑、填充劑、偶合劑、熱硬化性樹脂、光硬化性樹脂、染料、顏料、增黏劑、滑劑、消泡劑、塗平劑、紫外線吸收劑、界面活性劑、著色劑、非離子系界面活性劑等各種添加劑。且,對於本說明書可將其他成分(F)稱為任意成分(F)。 In the anticorrosive composition of the present embodiment, as a resist substrate, an acid generator (C), a crosslinking agent (G), and an acid diffusion controlling agent (E), if it does not inhibit the object of the present invention. The other components may be added with one or more kinds of dissolution promoters, dissolution control agents, sensitizers, surfactants, organic carboxylic acids or phosphorus oxyacids or derivatives thereof, heat and/or photohardenable touches. Medium, polymerization inhibiting agent, flame retardant, filler, coupling agent, thermosetting resin, photocurable resin, dye, pigment, tackifier, slip agent, antifoaming agent, coating agent, ultraviolet absorber, interface Various additives such as an active agent, a colorant, and a nonionic surfactant. Further, for the present specification, the other component (F) may be referred to as an optional component (F).

對於本實施形態的抗蝕組成物,抗蝕基材(以下亦稱為「成分(A)」)、酸產生劑(C)、交聯劑(G)、酸擴散控制劑(E)、任意成分(F)的含有量(成分(A)/酸產生劑(C)/交聯劑(G)/酸擴散控制劑(E)/任意成分(F))為在固體物基準之質量%下,以50~99.4/0.001~49/0.5~49/0.001~49/0~49為佳,較佳為55~90/1~40/0.5~40/0.01~10/0~5,更佳為60~80/3~30/1~30/0.01~5/0~1,特佳為60~70/10~25/2~20/0.01~3/0。 In the resist composition of the present embodiment, a resist substrate (hereinafter also referred to as "component (A)"), an acid generator (C), a crosslinking agent (G), an acid diffusion controlling agent (E), or any The content of the component (F) (component (A) / acid generator (C) / crosslinking agent (G) / acid diffusion controlling agent (E) / optional component (F)) is based on the mass% of the solid matter Preferably, it is 50~99.4/0.001~49/0.5~49/0.001~49/0~49, preferably 55~90/1~40/0.5~40/0.01~10/0~5, more preferably 60~80/3~30/1~30/0.01~5/0~1, especially good 60~70/10~25/2~20/0.01~3/0.

各成分的配合比例為欲使該總合成為100質量%,而自各範圍選擇。各成分之配合比例若在上述範圍時,其具有感度、解像度、顯像性等性能優良的傾向。 The mixing ratio of each component is such that the total synthesis is 100% by mass, and is selected from the respective ranges. When the blending ratio of each component is in the above range, it tends to have excellent properties such as sensitivity, resolution, and development.

本實施形態之抗蝕組成物通常在使用時,將各成分溶解於溶劑中使其成為均勻溶液,其後視必要,例如以孔徑0.2μm程度的濾器等進行過濾而調製。 In the case of using the resist composition of the present embodiment, the components are dissolved in a solvent to form a homogeneous solution, and then, for example, a filter having a pore diameter of about 0.2 μm is used for filtration.

本實施形態的抗蝕組成物在不阻礙本發明之目的的範圍下,可含有本實施形態的樹脂以外之其他樹脂。作為其他樹脂,雖無特別限定,例如可舉出酚醛清漆樹脂、聚乙烯酚類、聚丙烯酸、聚乙烯醇、苯乙烯-馬來酸酐樹脂及將丙烯酸、乙烯基醇或乙烯基酚作為單體單位含有之聚合物或者這些衍生物等。其他樹脂的含有量並無特別限定,可配合所使用的成分(A)之種類做適宜調節,但對於成分(A)100質量份以30質量份以下者為佳,較佳為10質量份以下,更佳為5質量份以下,特佳為0質量份。 The resist composition of the present embodiment may contain a resin other than the resin of the present embodiment, within a range not inhibiting the object of the present invention. The other resin is not particularly limited, and examples thereof include novolac resin, polyvinyl phenol, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and acrylic acid, vinyl alcohol or vinyl phenol as monomers. The polymer contained in the unit or these derivatives. The content of the other resin is not particularly limited, and may be appropriately adjusted depending on the type of the component (A) to be used. However, it is preferably 30 parts by mass or less, and preferably 10 parts by mass or less, based on 100 parts by mass of the component (A). More preferably, it is 5 parts by mass or less, and particularly preferably 0 parts by mass.

[抗蝕組成物之物性等]  [Physical properties of the resist composition, etc.]  

使用本實施形態的抗蝕組成物,藉由旋塗可形成非晶質膜。又,本實施形態的抗蝕組成物可適用於一般半導體製造製程。依據上述式(1)及/或式(2)所示化合物、將這些作為單體所得之樹脂的種類及/或使用的顯像液之種類,可分為正型抗蝕圖型及負型抗蝕圖型中任一。 Using the resist composition of the present embodiment, an amorphous film can be formed by spin coating. Further, the resist composition of the present embodiment can be applied to a general semiconductor manufacturing process. According to the compound represented by the above formula (1) and/or formula (2), the type of the resin obtained as a monomer and/or the type of the developing liquid used, it can be classified into a positive resist pattern and a negative type. Any of the resist patterns.

正型抗蝕圖型之情況為將本實施形態的抗蝕組成物經旋塗所形成的非晶質膜在23℃中對於顯像液的溶 解速度以5Å/sec以下者為佳,以0.05~5Å/sec者為較佳,以0.0005~5Å/sec者為更佳。溶解速度若在5Å/Sec以下時,於顯像液為不溶,有著容易作為抗蝕之傾向。又,溶解速度若為0.0005Å/sec以上時,有提高解像性之情況。此推測藉由將上述式(1)及(2)所示化合物及/或該化合物作為構成成分含有樹脂曝光前後的溶解性變化,溶解於顯像液之曝光部與為溶解於顯像液之未曝光部的界面對比較大所引起。又,亦見到LER的減低、瑕疵之減低效果。 In the case of the positive resist pattern, the amorphous film formed by spin coating the resist composition of the present embodiment preferably has a dissolution rate of 5 Å/sec or less for the developing solution at 23 ° C, and is 0.05. It is better to use ~5Å/sec, and it is better to use 0.0005~5Å/sec. When the dissolution rate is 5 Å/sec or less, it is insoluble in the developing solution, and tends to be easily resisted. Further, when the dissolution rate is 0.0005 Å/sec or more, the resolution is improved. This is estimated by dissolving the solubility change before and after exposure of the compound represented by the above formulas (1) and (2) and/or the compound as a constituent component in the exposure portion of the developing solution and dissolving it in the developing solution. The interface of the unexposed part is relatively large. Also, see the reduction of LER and the effect of reducing it.

負型抗蝕圖型的情況為,將本實施形態的抗蝕組成物進行旋塗所形成的非晶質膜在23℃中對顯像液的溶解速度以10Å/sec以上者為佳。溶解速度為10Å/sec以上時,於顯像液為易溶,對於抗蝕為適合。又,溶解速度為10Å/sec以上時,有時會有解像性提高的情況。此推測為將上述式(1)及(2)所示化合物及/或該化合物作為構成成分含有的樹脂之微表面部位被溶解,使LER減低所引起。亦見到瑕疵之減低效果。 In the case of the negative resist pattern, it is preferable that the amorphous film formed by spin coating the resist composition of the present embodiment has a dissolution rate of the developing solution at 23 ° C of 10 Å/sec or more. When the dissolution rate is 10 Å/sec or more, it is easily soluble in the developing solution, and is suitable for the resist. Moreover, when the dissolution rate is 10 Å/sec or more, the resolution may be improved. This is presumed to be caused by the dissolution of the micro surface portion of the resin contained in the compound represented by the above formulas (1) and (2) and/or the compound as a constituent component to reduce the LER. I also saw the effect of reducing the 瑕疵.

前述溶解速度係由在23℃將非晶質膜浸漬於所定時間顯像液,將該浸漬前後的膜厚藉由目視、橢偏儀或QCM法等公知方法進行測定而決定。 The dissolution rate is determined by immersing the amorphous film in a predetermined time developing solution at 23 ° C, and measuring the film thickness before and after the immersion by a known method such as a visual, ellipsometer or QCM method.

在正型抗蝕圖型之情況時,將本實施形態的抗蝕組成物進行旋塗所形成的非晶質膜藉由KrF準分子激光、極端紫外線、電子線或X線等放射線進行曝光之部分在23℃對於顯像液之溶解速度以10Å/sec以上者為佳。溶解速度為10Å/sec以上時,於顯像液為易溶,對於抗蝕為 適合。又,溶解速度為10Å/sec以上時,有時會有解像性提高的情況。此推測為將上述式(1)及(2)所示化合物及/或該化合物作為構成成分含有的樹脂之微表面部位被溶解,使LER減低所引起。亦見到瑕疵之減低效果。 In the case of a positive resist pattern, the amorphous film formed by spin coating the resist composition of the present embodiment is exposed by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. It is preferred that the dissolution rate of the developing solution is 10 Å/sec or more at 23 ° C. When the dissolution rate is 10 Å/sec or more, it is easily soluble in the developing solution, and is suitable for the resist. Moreover, when the dissolution rate is 10 Å/sec or more, the resolution may be improved. This is presumed to be caused by the dissolution of the micro surface portion of the resin contained in the compound represented by the above formulas (1) and (2) and/or the compound as a constituent component to reduce the LER. I also saw the effect of reducing the 瑕疵.

在負型抗蝕圖型之情況時,將本實施形態的抗蝕組成物進行旋塗所形成的非晶質膜之藉由KrF準分子激光、極端紫外線、電子線或X線等放射線進行曝光的部分在23℃中對於顯像液之溶解速度以5Å/sec以下者為佳,0.05~5Å/sec者為較佳,0.0005~5Å/sec者為更佳。溶解速度為5Å/sec以下時,於顯像液為不溶,有著容易作為抗蝕之傾向。又,溶解速度為0.0005Å/sec以上時,有時亦可提高解像性。此被推測為將上述式(1)及(2)所示化合物及/或該化合物作為構成成分含有的樹脂之曝光前後的溶解性之變化,溶解於顯像液之未曝光部與未溶解於顯像液的曝光部之界面的對比變大所造成。又,亦見到LER之減低、瑕疵之減低效果。 In the case of a negative resist pattern, the amorphous film formed by spin coating of the resist composition of the present embodiment is exposed by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. The portion is preferably 5 Å/sec or less for the dissolution rate of the developing solution at 23 ° C, preferably 0.05 to 5 Å / sec, and more preferably 0.0005 to 5 Å / sec. When the dissolution rate is 5 Å/sec or less, the developing solution is insoluble, and it tends to be easily used as a resist. Further, when the dissolution rate is 0.0005 Å/sec or more, the resolution may be improved. It is presumed that the change in solubility before and after exposure of the resin containing the compound represented by the above formulas (1) and (2) and/or the compound as a constituent component is dissolved in the unexposed portion of the developing solution and is not dissolved in The contrast of the interface of the exposure portion of the developing liquid is increased. In addition, we also saw the reduction of LER and the effect of reducing it.

[使用於非化學增幅型抗蝕用途的光刻用膜形成組成物]  [Film forming composition for lithography for non-chemical amplification type resist use]  

含於使用於本實施形態的非化學增幅型抗蝕用途之光刻用膜形成組成物(以下亦稱為「感放射線性組成物」)的成分(A)與後述二偶氮萘醌光活性化合物(B)併用,藉由照射g線、h線、i線、KrF準分子激光、ArF準分子激光、極端紫外線、電子線或X線,作為成為容易溶解於顯像液之化合物的正型抗蝕用基材為有用。藉由g線、h線、i線、 KrF準分子激光、ArF準分子激光、極端紫外線、電子線或X線,雖成分(A)的性質並無太大的變化,因於顯像液為難溶的二偶氮萘醌光活性化合物(B)會變成容易溶解的化合物,可藉由顯像步驟製作抗蝕圖型。 The component (A) of the composition for forming a film for lithography (hereinafter also referred to as "radiation-sensitive composition") used in the non-chemically amplified resist for use in the present embodiment, and the photoactivity of diazonaphthylquinone described later The compound (B) is used in combination as a positive type which is a compound which is easily dissolved in a developing solution by irradiating a g-line, an h-line, an i-line, a KrF excimer laser, an ArF excimer laser, an extreme ultraviolet ray, an electron beam or an X-ray. A substrate for resist is useful. By g-line, h-line, i-line, KrF excimer laser, ArF excimer laser, extreme ultraviolet light, electron beam or X-ray, although the properties of component (A) do not change much, it is difficult for imaging liquid. The dissolved diazonaphthoquinone photoactive compound (B) becomes a compound which is easily dissolved, and a resist pattern can be produced by a developing step.

含於本實施形態之感放射線性組成物的成分(A)因為比較低分子量的化合物,故所得之抗蝕圖型的粗糙度非常小。又,前述式(1)中,含有選自由R0~R5所成群的至少1個碘原子之基者為佳,又,前述式(2)中,選自由R0A、R1A及R2A所成群的至少1個為含有碘原子之基者為佳。本實施形態的感放射線性組成物為適用於具有含有碘原子的基之成分(A)時,增加對於電子線、極端紫外線(EUV)、X線等放射線的吸收能,其結果因可提高感度而較佳。 Since the component (A) contained in the radiation sensitive composition of the present embodiment has a relatively low molecular weight compound, the roughness of the obtained resist pattern is extremely small. Further, in the above formula (1), it is preferable to contain a group of at least one iodine atom selected from the group consisting of R 0 to R 5 , and in the above formula (2), it is selected from R 0A , R 1A and R It is preferred that at least one of the groups of 2A is a group containing an iodine atom. When the radiation sensitive composition of the present embodiment is applied to the component (A) having a group containing an iodine atom, the absorption energy for radiation such as electron beams, extreme ultraviolet rays (EUV), and X-rays is increased, and as a result, the sensitivity can be improved. Better.

含於本實施形態的感放射線性組成物之成分(A)的玻璃轉移溫度以100℃以上為佳,較佳為120℃以上,更佳為140℃以上,特佳為150℃以上。成分(A)的玻璃轉移溫度之上限值並無特別限定,例如為400℃。藉由成分(A)的玻璃轉移溫度在上述範圍內,對於半導體光刻加工,有著具有維持圖型形狀的耐熱性,且提高高解像度等性能之傾向。 The glass transition temperature of the component (A) of the radiation sensitive composition of the present embodiment is preferably 100 ° C or higher, preferably 120 ° C or higher, more preferably 140 ° C or higher, and particularly preferably 150 ° C or higher. The upper limit of the glass transition temperature of the component (A) is not particularly limited and is, for example, 400 °C. When the glass transition temperature of the component (A) is within the above range, the semiconductor photolithography process has a tendency to maintain heat resistance in a pattern shape and to improve performance such as high resolution.

藉由含於本實施形態的感放射線性組成物之成分(A)的玻璃轉移溫度的差示掃描熱量分析所求得之結晶化發熱量以未達20J/g為佳。又,結晶化溫度)-(玻璃轉移溫度)以70℃以上為佳,較佳為80℃以上,更佳為100℃ 以上,特佳為130℃以上。結晶化發熱量未達20J/g,或(結晶化溫度)-(玻璃轉移溫度)為上述範圍內時,藉由旋塗感放射線性組成物容易形成非晶質膜,且長期保持在抗蝕上所必要的成膜性,並具有可提高解像性之傾向。 The crystallization heat amount obtained by differential scanning calorimetry of the glass transition temperature of the component (A) of the radiation sensitive composition of the present embodiment is preferably less than 20 J/g. Further, the crystallization temperature)-(glass transition temperature) is preferably 70 ° C or higher, preferably 80 ° C or higher, more preferably 100 ° C or higher, and particularly preferably 130 ° C or higher. When the crystallization heat generation amount is less than 20 J/g, or (crystallization temperature) - (glass transition temperature) is within the above range, the amorphous film is easily formed by spin-coating the radiation-sensitive composition, and is kept on the resist for a long period of time. The film forming property necessary for the above has a tendency to improve the resolution.

對於本實施形態,前述結晶化發熱量、結晶化溫度及玻璃轉移溫度可藉由使用島津製作所製DSC/TA-50WS的差示掃描熱量分析而求得。將試料約10mg放入鋁製非密封容器,在氮氣気流中(50mL/分)昇溫速度20℃/分下升溫至熔點以上。急冷後,再次於氮氣流中(30mL/分)以昇溫速度20℃/分升溫至熔點以上。且急冷後,再次於氮氣流中(30mL/分)中以昇溫速度20℃/分升溫至400℃。將變化為階梯狀的底線之段差中點(一半變化為比熱時)的溫度作為玻璃轉移溫度(Tg),其後出現的發熱吸收峰之溫度作為結晶化溫度。由包圍發熱吸收峰與底線的區域面積求得發熱量,作為結晶化發熱量。 In the present embodiment, the crystallization heat generation amount, the crystallization temperature, and the glass transition temperature can be determined by differential scanning calorimetry using DSC/TA-50WS manufactured by Shimadzu Corporation. About 10 mg of the sample was placed in an unsealed container made of aluminum, and the temperature was raised to a melting point or higher under a nitrogen gas flow (50 mL/min) at a temperature increase rate of 20 ° C / min. After quenching, the temperature was raised to a temperature above the melting point again at a temperature increase rate of 20 ° C / min in a nitrogen stream (30 mL / min). After quenching, the temperature was raised again to 400 ° C at a temperature increase rate of 20 ° C / min in a nitrogen stream (30 mL / min). The temperature at which the midpoint of the step line of the stepped line is changed (half the change to the specific heat) is taken as the glass transition temperature (Tg), and the temperature of the heat absorption peak appearing thereafter is taken as the crystallization temperature. The calorific value is obtained from the area of the region surrounding the heat absorption peak and the bottom line as the crystallization heat.

含於本實施形態的感放射線性組成物之成分(A)在常壓下為100以下,以120℃以下為佳,較佳為130℃以下,更佳為140℃以下,特佳為150℃以下,因昇華性較低故佳。所謂昇華性低,表示對於熱重量分析中,在所定溫度保持10分忠實的重量減少為10%以下,以5%以下為佳,較佳為3%以下,更佳為1%以下,特佳為0.1%以下。藉由昇華性為低,可防止藉由曝光時的漏氣所引起的曝光裝置之污染。又,可得到低粗糙度良好之圖型形狀。 The component (A) contained in the radiation sensitive composition of the present embodiment is preferably 100 or less at normal pressure, preferably 120 ° C or lower, preferably 130 ° C or lower, more preferably 140 ° C or lower, and particularly preferably 150 ° C. Below, it is better because of lower sublimation. The low sublimation property means that in the thermogravimetric analysis, a weight loss of 10 minutes at a predetermined temperature is 10% or less, preferably 5% or less, preferably 3% or less, and more preferably 1% or less. It is 0.1% or less. By sublimation is low, contamination of the exposure device caused by air leakage during exposure can be prevented. Further, a pattern shape with a low roughness can be obtained.

含於本實施形態的感放射線性組成物之成分 (A)為選自由丙二醇單甲基醚乙酸酯(PGMEA)、丙二醇單甲基醚(PGME)、環己酮(CHN)、環戊酮(CPN)、2-庚酮、苯甲醚、乙酸丁酯、丙酸乙酯及乳酸乙酯所成群,且對於成分(A)亦顯示最高溶解能的溶劑中,在23℃以1質量%以上為佳,較佳為5質量%以上,更佳為10質量%以上溶解。特佳為選自由PGMEA、PGME、CHN所成群,且於對於(A)抗蝕基材顯示最高溶解能的溶劑中,在23℃為20質量%以上,特佳為對於PGMEA,在23℃溶解20質量%以上。藉由滿足上述條件,在實際生產上的半導體製造步驟的使用會變的容易。 The component (A) contained in the radiation sensitive composition of the present embodiment is selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), and cyclopentanone. (CPN), 2-heptanone, anisole, butyl acetate, ethyl propionate and ethyl lactate, and the highest solubility energy in the component (A), at 1 °C at 23 ° C More preferably, it is more than 5% by mass, more preferably 5% by mass or more, more preferably 10% by mass or more. It is particularly preferably selected from the group consisting of PGMEA, PGME, and CHN, and the solvent exhibiting the highest solubility in the (A) resist substrate is 20% by mass or more at 23° C., particularly preferably, for PGMEA at 23° C. Dissolved in an amount of 20% by mass or more. By satisfying the above conditions, the use of semiconductor manufacturing steps in actual production becomes easy.

[二偶氮萘醌光活性化合物(B)]  [Diazonaphthoquinone photoactive compound (B)]  

含於本實施形態的感放射線性組成物的二偶氮萘醌光活性化合物(B)為含有聚合物性及非聚合物性二偶氮萘醌光活性化合物之二偶氮萘醌物質,一般對於正型抗蝕組成物,可作為感光性成分(感光劑)使用者即可,並無特別限制,可任意選擇1種或2種以上使用。 The diazo naphthoquinone photoactive compound (B) contained in the radiation sensitive composition of the present embodiment is a diazonaphthylquinone substance containing a polymerizable and non-polymeric diazonaphthoquinone photoactive compound, generally for positive The type of the anti-corrosive composition can be used as a photosensitive component (photosensitive agent), and it is not particularly limited, and one type or two or more types can be used arbitrarily.

作為成分(B),以藉由將萘醌二疊氮化物磺酸氯化物或苯醌二疊氮化物磺酸氯化物等與可與具有這些酸氯化物可進行縮合反應的官能基之低分子化合物或高分子化合物進行反應所得之化合物為佳。其中,作為可與酸氯化物進行縮合的官能基,並無特別限定,例如可舉出羥基、胺基等,特別以羥基為佳。作為可與含有羥基的酸氯化物進行縮合之化合物,並無特別限定,例如可舉出氫 醌、間苯二酚、2、4-二羥基二苯甲酮、2、3、4-三羥基二苯甲酮、2、4、6-三羥基二苯甲酮、2、4、4’-三羥基二苯甲酮、2、3、4、4’-四羥基二苯甲酮、2、2’、4、4’-四羥基二苯甲酮、2、2’、3、4、6’-五羥基二苯甲酮等羥基二苯甲酮類;雙(2、4-二羥基苯基)甲烷、雙(2、3、4-三羥基苯基)甲烷、雙(2、4-二羥基苯基)丙烷等羥基苯基烷烴類;4、4’、3”、4”-四羥基-3、5、3’、5’-四甲基三苯基甲烷、4、4’、2”、3”、4”-五羥基-3、5、3’、5’-四甲基三苯基甲烷等羥基三苯基甲烷類等。 As the component (B), a naphthoquinonediazide sulfonate chloride or a benzoquinonediazide sulfonate chloride or the like and a low molecule which can be subjected to a condensation reaction with these acid chlorides A compound obtained by reacting a compound or a polymer compound is preferred. In particular, the functional group which can be condensed with the acid chloride is not particularly limited, and examples thereof include a hydroxyl group and an amine group, and particularly preferably a hydroxyl group. The compound which can be condensed with the acid chloride containing a hydroxyl group is not particularly limited, and examples thereof include hydroquinone, resorcin, 2, 4-dihydroxybenzophenone, and 2,3,4-trihydroxyl group. Benzophenone, 2,4,6-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2 2', 4, 4'-tetrahydroxybenzophenone, 2, 2', 3, 4, 6'-pentahydroxybenzophenone and other hydroxybenzophenones; bis (2, 4-dihydroxybenzene) Hydroxyphenyl alkane such as methane, bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)propane; 4,4',3",4"-four Hydroxy-3,5,3',5'-tetramethyltriphenylmethane, 4,4',2",3",4"-pentahydroxy-3,5,3',5'-tetramethyl Hydroxytriphenylmethane such as triphenylmethane.

又,作為萘醌二疊氮化物磺酸氯化物或苯醌二疊氮化物磺酸氯化物等酸氯化物,例如可舉出較佳者之1、2-萘醌二疊氮化物-5-磺醯基氯化物、1、2-萘醌二疊氮化物-4-磺醯基氯化物等。 Further, examples of the acid chloride such as naphthoquinonediazide sulfonate chloride or benzoquinonediazide sulfonate chloride include 1,2-naphthoquinonediazide-5-. Sulfonyl chloride, 1, 2-naphthoquinonediazide-4-sulfonyl chloride, and the like.

本實施形態的感放射線性組成物,例如於使用時將各成分溶解於溶劑作為均勻溶液,其後視必要例如藉由以孔徑0.2μm程度之濾器等過濾後調製出者為佳。 In the radiation sensitive composition of the present embodiment, for example, each component is dissolved in a solvent as a homogeneous solution, and it is preferably prepared by filtering it with a filter having a pore size of about 0.2 μm, for example.

[感放射線性組成物之特性]  [Characteristics of Radiation-Linear Compositions]  

使用本實施形態的感放射線性組成物,藉由旋塗可形成非晶質膜。又,本實施形態的感放射線性組成物可適用於一般半導體製造製程。藉由所使用的顯像液之種類,可分為正型抗蝕圖型及負型抗蝕圖型中任一。 Using the radiation sensitive composition of the present embodiment, an amorphous film can be formed by spin coating. Further, the radiation sensitive composition of the present embodiment can be applied to a general semiconductor manufacturing process. The type of the developing liquid to be used can be classified into any one of a positive resist pattern and a negative resist pattern.

正型抗蝕圖型的情況為,對於旋塗本實施形態的感放射線性組成物所形成的非晶質膜在23℃中對於顯 像液之溶解速度以5Å/sec以下者為佳,0.05~5Å/sec者為較佳,0.0005~5Å/sec者為更佳。溶解速度為5Å/sec以下時,於顯像液為不溶,有著容易作為抗蝕之傾向。又,溶解速度為0.0005Å/sec以上時,有解像性提高的情況。此被推測為將上述式(1)及(2)所示化合物及/或該化合物作為構成成分含有的樹脂之曝光前後的溶解性之變化,溶解於顯像液的曝光部與未溶解於顯像液的未曝光部之界面的對比變大所造成。又,亦見到LER之減低、瑕疵之減低效果。 In the case of the positive resist pattern, it is preferable that the amorphous film formed by spin coating the radiation sensitive composition of the present embodiment has a dissolution rate of 5 Å/sec or less for the developing solution at 23 ° C, 0.05. It is better for ~5Å/sec, and it is better for 0.0005~5Å/sec. When the dissolution rate is 5 Å/sec or less, the developing solution is insoluble, and it tends to be easily used as a resist. Moreover, when the dissolution rate is 0.0005 Å/sec or more, the resolution is improved. This is presumed to be a change in the solubility of the resin contained in the compound represented by the above formulas (1) and (2) and/or the compound as a constituent component before and after exposure, and is dissolved in the exposed portion of the developing solution and is not dissolved in the display. The contrast of the interface of the unexposed portion like the liquid becomes large. In addition, we also saw the reduction of LER and the effect of reducing it.

負型抗蝕圖型的情況為,塗布本實施形態的感放射線性組成物所形成的非晶質膜在23℃中對於顯像液之溶解速度以10Å/sec以上者為佳。該溶解速度為10Å/sec以上時,於顯像液為易溶,對於抗蝕為適合。又,溶解速度為10Å/sec以上時,有時會有解像性提高的情況。此推測為將上述式(1)及(2)所示化合物及/或該化合物作為構成成分含有的樹脂之微表面部位被溶解,使LER減低所引起。亦見到瑕疵之減低效果。 In the case of the negative resist pattern, it is preferable that the amorphous film formed by applying the radiation sensitive composition of the present embodiment has a dissolution rate of 10 Å/sec or more for the developing solution at 23 °C. When the dissolution rate is 10 Å/sec or more, it is easily soluble in the developing solution, and is suitable for the resist. Moreover, when the dissolution rate is 10 Å/sec or more, the resolution may be improved. This is presumed to be caused by the dissolution of the micro surface portion of the resin contained in the compound represented by the above formulas (1) and (2) and/or the compound as a constituent component to reduce the LER. I also saw the effect of reducing the 瑕疵.

前述溶解速度為在23℃將非晶質膜浸漬於所定時間顯像液,將該浸漬前後之膜厚藉由目視、橢偏儀或QCM法等公知方法進行測定而決定。 The dissolution rate is such that the amorphous film is immersed in a predetermined time developing solution at 23 ° C, and the film thickness before and after the immersion is determined by a known method such as a visual, ellipsometer or QCM method.

正型抗蝕圖型之情況時,將本實施形態的感放射線性組成物進行旋塗所形成的非晶質膜藉由KrF準分子激光、極端紫外線、電子線或X線等放射線進行照射後,或在20~500℃進行加熱後的經曝光部分的在23℃中對於顯像液之溶解速度以10Å/sec以上為佳,10~ 10000Å/sec為較佳100~1000Å/sec為更佳。溶解速度為10Å/sec以上時,於顯像液為易溶,對於抗蝕為適合。又,在溶解速度為10000Å/sec以下時,亦有解像性提高的情況。此推測為將上述式(1)及(2)所示化合物及/或該化合物作為構成成分含有的樹脂之微表面部位被溶解,使LER減低所引起。亦見到瑕疵之減低效果。 In the case of a positive resist pattern, the amorphous film formed by spin coating the radiation sensitive composition of the present embodiment is irradiated with radiation such as KrF excimer laser light, extreme ultraviolet light, electron beam or X-ray. Or, in the exposed portion after heating at 20 to 500 ° C, the dissolution rate of the developing solution at 23 ° C is preferably 10 Å / sec or more, and preferably 10 to 10000 Å / sec is preferably 100 to 1000 Å / sec. . When the dissolution rate is 10 Å/sec or more, it is easily soluble in the developing solution, and is suitable for the resist. Moreover, when the dissolution rate is 10000 Å/sec or less, the resolution is also improved. This is presumed to be caused by the dissolution of the micro surface portion of the resin contained in the compound represented by the above formulas (1) and (2) and/or the compound as a constituent component to reduce the LER. I also saw the effect of reducing the 瑕疵.

負型抗蝕圖型的情況為,將本實施形態的感放射線性組成物進行旋塗所形成的非晶質膜藉由KrF準分子激光、極端紫外線、電子線或X線等放射線進行照射後,或在20~500℃進行加熱後的經曝光部分的在23℃中對於顯像液之溶解速度以5Å/sec以下者為佳,以0.05~5Å/sec者為較佳,以0.0005~5Å/sec者為更佳。溶解速度為5Å/sec以下時,於顯像液為不溶,有著容易作為抗蝕之傾向。又,溶解速度為0.0005Å/sec以上時,有時亦可提高解像性。此被推測為將上述式(1)及(2)所示化合物及/或該化合物作為構成成分含有的樹脂之曝光前後的溶解性之變化,溶解於顯像液之未曝光部與未溶解於顯像液的曝光部之界面的對比變大所造成。又,亦見到LER之減低、瑕疵之減低效果。 In the case of the negative resist pattern, the amorphous film formed by spin coating the radiation sensitive composition of the present embodiment is irradiated with radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. Or, in the exposed portion after heating at 20 to 500 ° C, the dissolution rate of the developing solution at 23 ° C is preferably 5 Å / sec or less, preferably 0.05 to 5 Å / sec, preferably 0.0005 to 5 Å. /sec is better. When the dissolution rate is 5 Å/sec or less, the developing solution is insoluble, and it tends to be easily used as a resist. Further, when the dissolution rate is 0.0005 Å/sec or more, the resolution may be improved. It is presumed that the change in solubility before and after exposure of the resin containing the compound represented by the above formulas (1) and (2) and/or the compound as a constituent component is dissolved in the unexposed portion of the developing solution and is not dissolved in The contrast of the interface of the exposure portion of the developing liquid is increased. In addition, we also saw the reduction of LER and the effect of reducing it.

[各成分之配合比例]  [mixing ratio of each component]  

對於本實施形態之感放射線性組成物,成分(A)的含有量對於固體成分全重量(成分(A)、二偶氮萘醌光活性化合物(B)及其他成分(D)等任意中所使用的固體成分之總 合,以下相同)為1~99質量%,較佳為5~95質量%,更佳為10~90質量%,特佳為25~75質量%。本實施形態的感放射線性組成物若成分(A)的含有量若在上述範圍內時,有可在高感度下得到粗糙度小的圖型之傾向。 In the radiation sensitive composition of the present embodiment, the content of the component (A) is any one of the total weight of the solid component (component (A), diazo naphthoquinone photoactive compound (B), and other components (D). The total solid content used is the same as 1 to 99% by mass, preferably 5 to 95% by mass, more preferably 10 to 90% by mass, particularly preferably 25 to 75% by mass. When the content of the component (A) in the radiation sensitive composition of the present embodiment is within the above range, there is a tendency that a pattern having a small roughness can be obtained with high sensitivity.

對於本實施形態之感放射線性組成物,二偶氮萘醌光活性化合物(B)的含有量對於固體成分全重量(成分(A)、二偶氮萘醌光活性化合物(B)及其他成分(D)等任意中所使用的固體成分之總合,以下相同)以1~99質量%為佳,較佳為5~95質量%,更佳為10~90質量%,特佳為25~75質量%。本實施形態之感放射線性組成物的二偶氮萘醌光活性化合物(B)之含有量若在上述範圍內時,有可在高感度下得到粗糙度小的圖型之傾向。 In the radiation sensitive composition of the present embodiment, the content of the diazo naphthoquinone photoactive compound (B) is the total weight of the solid component (component (A), diazo naphthoquinone photoactive compound (B), and other components. The total of the solid components used in any of (D) and the like, the same applies hereinafter, preferably 1 to 99% by mass, preferably 5 to 95% by mass, more preferably 10 to 90% by mass, particularly preferably 25 to 5% by mass. 75 mass%. When the content of the diazonaphthoquinone photoactive compound (B) of the radiation sensitive composition of the present embodiment is within the above range, there is a tendency that a pattern having a small roughness can be obtained with high sensitivity.

[其他成分(D)]  [Other ingredients (D)]  

對於本實施形態之感放射線性組成物,在不損害本發明之目的的範圍下,視必要作為成分(A)及二偶氮萘醌光活性化合物(B)以外的成分,可添加酸產生劑、交聯劑、酸擴散控制劑、溶解促進劑、溶解控制劑、增感劑、界面活性劑、有機羧酸或磷的含氧酸或者其衍生物、熱及/或光硬化觸媒、聚合禁止劑、難燃劑、填充劑、偶合劑、熱硬化性樹脂、光硬化性樹脂、染料、顏料、增黏劑、滑劑、消泡劑、塗平劑、紫外線吸收劑、界面活性劑、著色劑、非離子系界面活性劑等各種添加劑之1種或2種以上。且,對於本說明書,將其他成分(D)有時稱為任意成分 (D)。 In the radiation sensitive composition of the present embodiment, an acid generator may be added as a component other than the component (A) and the diazo naphthoquinone photoactive compound (B), as long as the object of the present invention is not impaired. , cross-linking agent, acid diffusion control agent, dissolution promoter, dissolution control agent, sensitizer, surfactant, oxo acid or derivative of organic carboxylic acid or phosphorus, heat and/or photo-curing catalyst, polymerization Prohibition agent, flame retardant, filler, coupling agent, thermosetting resin, photocurable resin, dye, pigment, tackifier, slip agent, antifoaming agent, coating agent, ultraviolet absorber, surfactant, One or two or more kinds of various additives such as a coloring agent and a nonionic surfactant. Further, in the present specification, the other component (D) is sometimes referred to as an arbitrary component (D).

對於本實施形態的感放射線性組成物,各成分之配合比例(成分(A)/二偶氮萘醌光活性化合物(B)/任意成分(D))在固體成分基準之質量%下,以1~99/99~1/0~98為佳,較佳為5~95/95~5/0~49,更佳為10~90/90~10/0~10,更較佳為20~80/80~20/0~5,特佳為25~75/75~25/0。 In the radiation sensitive composition of the present embodiment, the blending ratio of each component (component (A) / diazonaphthoquinone photoactive compound (B) / optional component (D)) is based on the mass % of the solid content standard. 1~99/99~1/0~98 is preferred, preferably 5~95/95~5/0~49, more preferably 10~90/90~10/0~10, more preferably 20~ 80/80~20/0~5, especially good 25~75/75~25/0.

各成分之配合比例可選自可使該總合成為100質量%之各範圍。本實施形態的感放射線性組成物之各成分的配合比例在上述範圍時,除粗糙度優良外,亦有感度、解像度等性能優良的傾向。 The mixing ratio of each component may be selected from various ranges in which the total synthesis can be made 100% by mass. When the blending ratio of each component of the radiation sensitive composition of the present embodiment is in the above range, in addition to the excellent roughness, the properties such as sensitivity and resolution tend to be excellent.

本實施形態的感放射線性組成物在不阻礙本發明之目的的範圍下,可含有其他樹脂。作為如此其他樹脂,可舉出將酚醛清漆樹脂、聚乙烯酚類、聚丙烯酸、聚乙烯醇、苯乙烯-馬來酸酐樹脂、及丙烯酸、乙烯基醇或乙烯基酚作為單體單位含有的聚合物或者這些衍生物等。這些樹脂的配合量可配合所使用的成分(A)之種類而做適宜調節,對於成分(A)100質量份以30質量份以下者為佳,較佳為10質量份以下,更佳為5質量份以下,特佳為0質量份。 The radiation sensitive composition of the present embodiment may contain other resins in a range that does not inhibit the object of the present invention. Examples of such other resins include polymerization of a novolak resin, a polyvinyl phenol, a polyacrylic acid, a polyvinyl alcohol, a styrene-maleic anhydride resin, and acrylic acid, vinyl alcohol or vinyl phenol as a monomer unit. Things or these derivatives. The amount of the resin to be added may be appropriately adjusted in accordance with the type of the component (A) to be used, and it is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass per 100 parts by mass of the component (A). The amount is preferably 0 parts by mass or less.

[抗蝕圖型之形成方法]  [Formation method of resist pattern]  

於本實施形態中之抗蝕圖型的形成方法為含有使用上述本實施形態的抗蝕組成物或感放射線性組成物,在基板上形成光阻層後,於前述光阻層的所定區域照射放射線並進行顯像之步驟。 In the method for forming a resist pattern according to the present embodiment, the resist composition or the radiation sensitive composition of the present embodiment is used, and after forming a photoresist layer on the substrate, the resist layer is irradiated on a predetermined region of the photoresist layer. The step of radiation and imaging.

更詳細為,具備使用上述本實施形態的抗蝕組成物或感放射線性組成物於基板上形成抗蝕膜之步驟、曝光所形成的抗蝕膜之步驟與顯像前述抗蝕膜並形成抗蝕圖型之步驟。於本實施形態中之抗蝕圖型亦可作為多層製程中之上層抗蝕而形成。 More specifically, the step of forming a resist film on the substrate by using the resist composition or the radiation sensitive composition of the present embodiment, the step of exposing the resist film, and developing the resist film to form an anti-etching film The steps of the etch pattern. The resist pattern in the present embodiment can also be formed as an upper layer resist in a multilayer process.

作為形成抗蝕圖型的方法,雖並無特別限定,例如可舉出以下方法。首先於過去公知基板上將抗蝕組成物或感放射線性組成物藉由轉動塗佈、流延塗佈、輥塗佈等塗佈手段進行塗佈後形成抗蝕膜。所謂過去公知基板並無特別限定,例如可舉出電子零件用基板或於此形成所定配線圖型者等。更具體可舉出矽晶圓、銅、鉻、鐵、鋁等金屬製基板或玻璃基板等。作為配線圖型之材料,例如可舉出銅、鋁、鎳、金等。又,亦可為視必要於前述基板上設置無機系及/或有機系膜者。作為無機系的膜,可舉出無機反射防止膜(無機BARC)。作為有機系的膜,可舉出有機反射防止膜(有機BARC)。於基板上亦可藉由六伸甲基二矽氮烷等進行表面處理。 The method for forming the resist pattern is not particularly limited, and examples thereof include the following methods. First, a resist film or a radiation sensitive composition is applied onto a conventionally known substrate by a coating means such as spin coating, cast coating, or roll coating to form a resist film. The conventionally known substrate is not particularly limited, and examples thereof include a substrate for an electronic component or a predetermined wiring pattern. More specifically, a metal substrate such as a germanium wafer, copper, chromium, iron, or aluminum, or a glass substrate can be given. Examples of the material of the wiring pattern include copper, aluminum, nickel, gold, and the like. Further, an inorganic or/or organic film may be provided on the substrate as necessary. An inorganic antireflection film (inorganic BARC) is mentioned as an inorganic film. An organic antireflection film (organic BARC) is mentioned as an organic film. The substrate may also be surface-treated by hexamethylenediazine or the like on the substrate.

其次,視必要加熱塗布抗蝕組成物或感放射線性組成物之基板。加熱條件雖依據抗蝕組成物或感放射線組成物之配合組成等而改變,但以20~250℃者為佳, 較佳為20~150℃。藉由加熱,因有對於抗蝕基板的密著性會提高的傾向故較佳。其次,藉由選自由可見光線、紫外線、準分子激光、電子線、極端紫外線(EUV)、X線、及離子束所成群的任一放射線,將抗蝕膜曝光成所望圖型。曝光條件等可配合抗蝕組成物或感放射線性組成物之配合組成等做適宜選定。對於本實施形態,因可穩定地形成曝光中之高精度微細圖型,故於放射線照射後進行加熱者為佳。加熱條件可藉由抗蝕組成物或感放射線性組成物之配合組成等而改變,以20~250℃者為佳,較佳為20~150℃。 Next, the substrate on which the resist composition or the radiation-sensitive composition is applied is heated as necessary. The heating condition varies depending on the composition of the resist composition or the radiation sensitive composition, and is preferably 20 to 250 ° C, preferably 20 to 150 ° C. It is preferable that the adhesion to the resist substrate is improved by heating. Next, the resist film is exposed to a desired pattern by any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam. The exposure conditions and the like can be appropriately selected in accordance with the composition of the resist composition or the radiation-sensitive linear composition. In the present embodiment, since it is possible to stably form a high-precision fine pattern during exposure, it is preferable to perform heating after radiation irradiation. The heating condition may be changed by a composition of the resist composition or the radiation-sensitive linear composition, etc., preferably 20 to 250 ° C, preferably 20 to 150 ° C.

其次,藉由將經曝光的抗蝕膜以顯像液進行顯像,形成所定抗蝕圖型。作為顯像液,選擇接近對於將使用的式(1)或者式(2)所示化合物或式(1)或者式(2)所示化合物作為單體所得之樹脂的溶解度參數(SP值)之溶劑者為佳,可使用酮系溶劑、酯系溶劑、醇系溶劑、醯胺系溶劑、醚系溶劑等極性溶劑、烴系溶劑或鹼水溶液。 Next, a predetermined resist pattern is formed by developing the exposed resist film as a developing liquid. As the developing solution, a solubility parameter (SP value) close to the resin obtained by using the compound represented by the formula (1) or the formula (2) or the compound represented by the formula (1) or the formula (2) as a monomer is selected. The solvent is preferably used, and a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent or an ether solvent, a hydrocarbon solvent or an aqueous alkali solution can be used.

作為酮系溶劑,例如可舉出1-辛酮、2-辛酮、1-壬酮、2-壬酮、丙酮、4-庚酮、1-己酮、2-己酮、二異丁基酮、環己酮、甲基環己酮、苯基丙酮、甲基乙基酮、甲基異丁基酮、乙醯丙酮、丙酮基丙酮、紫羅蘭酮、二丙酮醇、乙醯甲醇、苯乙酮、甲基萘酮、異佛爾酮、伸丙基碳酸酯等。 Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, and diisobutyl group. Ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetamidine acetone, acetone acetone, ionone, diacetone alcohol, acetamethanol, phenylethyl Ketone, methylnaphthone, isophorone, propyl carbonate, and the like.

作為酯系溶劑,例如可舉出乙酸甲酯、乙酸丁酯、乙酸乙酯、乙酸異丙酯、乙酸戊酯、丙二醇單甲基 醚乙酸酯、乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯、二乙二醇單乙基醚乙酸酯、乙基-3-乙氧基丙酸酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、甲酸甲酯、甲酸乙酯、甲酸丁酯、甲酸丙酯、乳酸乙酯、乳酸丁酯、乳酸丙酯等。 Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate. Diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxy propionate, 3-methoxybutyl acetate, 3-methyl 3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, and the like.

作為醇系溶劑,例如可舉出甲基醇、乙基醇、n-丙基醇、異丙醇(2-丙醇)、n-丁基醇、sec-丁基醇、tert-丁基醇、異丁基醇、n-己基醇、4-甲基-2-戊醇、n-庚基醇、n-辛基醇、n-癸醇等醇或乙二醇、二乙二醇、三乙二醇等甘醇系溶劑或乙二醇單甲基醚、丙二醇單甲基醚、乙二醇單乙基醚、丙二醇單乙基醚、二乙二醇單甲基醚、三乙二醇單乙基醚、甲氧基甲基丁醇等甘醇醚系溶劑等。 Examples of the alcohol-based solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropanol (2-propanol), n-butyl alcohol, sec-butyl alcohol, and tert-butyl alcohol. , isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-nonanol, etc., or ethylene glycol, diethylene glycol, three Glycol-based solvent such as ethylene glycol or ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol A glycol ether solvent such as monoethyl ether or methoxymethylbutanol.

作為醚系溶劑,例如可舉出上述甘醇醚系溶劑以外,亦舉出二噁烷、四氫呋喃等。 Examples of the ether solvent include diethylene glycol, tetrahydrofuran, and the like, in addition to the above glycol ether solvent.

作為醯胺系溶劑,例如可舉出N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、六甲基磷醯三胺、1,3-二甲基-2-咪唑啉酮等。 Examples of the guanamine-based solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and hexamethylphosphonium triamine. , 1,3-dimethyl-2-imidazolidinone, and the like.

作為烴系溶劑,例如可舉出甲苯、二甲苯等的芳香族烴系溶劑、戊烷、己烷、辛烷、癸烷等脂肪族烴系溶劑。 Examples of the hydrocarbon-based solvent include an aromatic hydrocarbon solvent such as toluene or xylene, and an aliphatic hydrocarbon solvent such as pentane, hexane, octane or decane.

上述溶劑可混合複數種,亦可在具有性能之範圍內使用與上述以外的溶劑或水之混合。但,由可充分達到本發明之效果的觀點來看,作為顯像液全體的含水率以未達70質量%者為佳,以未達50質量%者為較佳,以未 達30質量%者為更佳,以未達10質量%者更較佳,實質上未含有水分者為特佳。即,對於顯像液之有機溶劑的含有量對於顯像液之全量而言,以30質量%以上100質量%以下者為佳,以50質量%以上100質量%以下者為較佳,以70質量%以上100質量%以下者為更佳,以90質量%以上100質量%以下者為更較佳,以95質量%以上100質量%以下者為特佳。 The above solvent may be mixed in plural kinds, and a mixture with a solvent other than the above or water may be used within a range of properties. However, from the viewpoint of sufficiently achieving the effects of the present invention, the water content of the entire development liquid is preferably less than 70% by mass, preferably less than 50% by mass, and less than 30% by mass. It is more preferably, it is more preferably less than 10% by mass, and it is particularly preferable that it does not contain water substantially. In other words, the content of the organic solvent in the developing solution is preferably 30% by mass or more and 100% by mass or less based on the total amount of the developing liquid, and preferably 50% by mass or more and 100% by mass or less, and 70% or more. It is more preferably 90% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less.

作為鹼水溶液,例如可舉出單-、二-或者三烷基胺類、單-、二-或者三鏈烷醇胺類、雜環式胺類、四甲基銨氫氧化物(TMAH)、科林等鹼性化合物。 Examples of the aqueous alkali solution include mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, and tetramethylammonium hydroxide (TMAH). Basic compounds such as Colin.

特別作為顯像液,由改善抗蝕圖型之解像性或粗糙度等抗蝕性能的觀點來看,有選自酮系溶劑、酯系溶劑、醇系溶劑、醯胺系溶劑及醚系溶劑的至少1種溶劑的顯像液為佳。 In particular, the developing solution is selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether system from the viewpoint of improving the resist performance such as the resolution of the resist pattern or the roughness. A developing solution of at least one solvent of the solvent is preferred.

顯像液的蒸汽壓在20℃下以5kPa以下者為佳,以3kPa以下者為較佳,以2kPa以下者為更佳。顯像液的蒸汽壓為5kPa以下時,顯像液的基板上或者顯像杯內的蒸發受到抑制,而提高晶圓面內之溫度均勻性,作為結果具有晶圓面內之尺寸均勻性良化的傾向。 The vapor pressure of the developing solution is preferably 5 kPa or less at 20 ° C, preferably 3 kPa or less, and more preferably 2 kPa or less. When the vapor pressure of the developing liquid is 5 kPa or less, evaporation of the liquid on the substrate of the developing liquid or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved, and as a result, the dimensional uniformity in the wafer surface is good. The tendency to change.

作為於20℃中具有5kPa以下的蒸汽壓之具體顯像液的例子,可舉出1-辛酮、2-辛酮、1-壬酮、2-壬酮、4-庚酮、2-己酮、二異丁基酮、環己酮、甲基環己酮、苯基丙酮、甲基異丁基酮等酮系溶劑;乙酸丁酯、乙酸戊酯、丙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸 酯、二乙二醇單丁基醚乙酸酯、二乙二醇單乙基醚乙酸酯、乙基-3-乙氧基丙酸酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、甲酸丁酯、甲酸丙酯、乳酸乙酯、乳酸丁酯、乳酸丙酯等酯系溶劑;n-丙基醇、異丙醇、n-丁基醇、sec-丁基醇、tert-丁基醇、異丁基醇、n-己基醇、4-甲基-2-戊醇、n-庚基醇、n-辛基醇、n-癸醇等醇系溶劑;乙二醇、二乙二醇、三乙二醇等甘醇系溶劑;乙二醇單甲基醚、丙二醇單甲基醚、乙二醇單乙基醚、丙二醇單乙基醚、二乙二醇單甲基醚、三乙二醇單乙基醚、甲氧基甲基丁醇等甘醇醚系溶劑;四氫呋喃等醚系溶劑;N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺的醯胺系溶劑;甲苯、二甲苯等的芳香族烴系溶劑;辛烷、癸烷等脂肪族烴系溶劑。 Examples of the specific developing liquid having a vapor pressure of 5 kPa or less at 20 ° C include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, and 2-hexyl a ketone solvent such as ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone or methyl isobutyl ketone; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxy propionate, 3-methyl An ester solvent such as oxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate or propyl lactate; n- Propyl alcohol, isopropanol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl An alcohol solvent such as an alcohol, n-octyl alcohol or n-nonanol; a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol; ethylene glycol monomethyl ether or propylene glycol monomethyl ether; Ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxy a glycol ether solvent such as methyl butanol; an ether solvent such as tetrahydrofuran; N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide A phthalamide solvent; an aromatic hydrocarbon solvent such as toluene or xylene; or an aliphatic hydrocarbon solvent such as octane or decane.

作為在20℃下具有2kPa以下之蒸汽壓的具體顯像液之例子,可舉出1-辛酮、2-辛酮、1-壬酮、2-壬酮、4-庚酮、2-己酮、二異丁基酮、環己酮、甲基環己酮、苯基丙酮等酮系溶劑;乙酸丁酯、乙酸戊酯、丙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯、二乙二醇單乙基醚乙酸酯、乙基-3-乙氧基丙酸酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、乳酸乙酯、乳酸丁酯、乳酸丙酯等酯系溶劑;n-丁基醇、sec-丁基醇、tert-丁基醇、異丁基醇、n-己基醇、4-甲基-2-戊醇、n-庚基醇、n-辛基醇、n-癸醇等醇系溶劑;乙二醇、二乙二醇、三乙二醇等甘醇系溶劑;乙二醇單甲 基醚、丙二醇單甲基醚、乙二醇單乙基醚、丙二醇單乙基醚、二乙二醇單甲基醚、三乙二醇單乙基醚、甲氧基甲基丁醇等甘醇醚系溶劑;N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺的醯胺系溶劑、二甲苯等的芳香族烴系溶劑;辛烷、癸烷等脂肪族烴系溶劑。 Examples of the specific developing liquid having a vapor pressure of 2 kPa or less at 20 ° C include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, and 2-hexyl a ketone solvent such as ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone or phenylacetone; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxy propionate, 3-methoxybutyl acetate , an ester solvent such as 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate or propyl lactate; n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol Alcohol solvent such as isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-nonanol; ethylene glycol, diethylene glycol Glycol solvent such as triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethyl Glycol ether solvent such as diol monoethyl ether or methoxymethylbutanol; N-methyl-2-pyrrolidone, N,N-dimethyl Aromatic hydrocarbon solvents Amides, N, N- acyl amine-based solvent is dimethylformamide, xylene and the like; octane, decane and other aliphatic hydrocarbon solvents.

於顯像液中,視必要可添加適量的界面活性劑。作為界面活性劑,並無特別限定,例如可使用離子性或非離子性氟系及/或矽系界面活性劑等。作為這些氟及/或矽系界面活性劑,例如可舉出特開昭62-36663號公報、特開昭61-226746號公報、特開昭61-226745號公報、特開昭62-170950號公報、特開昭63-34540號公報、特開平7-230165號公報、特開平8-62834號公報、特開平9-54432號公報、特開平9-5988號公報、美國專利第5405720號說明書、同5360692號說明書、同5529881號說明書、同5296330號說明書、同5436098號說明書、同5576143號說明書、同5294511號說明書、同5824451號說明書所記載的界面活性劑,較佳為非離子性界面活性劑。作為非離子性界面活性劑並無特別限定,較佳為氟系界面活性劑或矽系界面活性劑。 In the developing solution, an appropriate amount of a surfactant may be added as necessary. The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and/or a lanthanoid surfactant can be used. For example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, and JP-A-62-170950 Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The non-ionic surfactant is preferably the same as the surfactant described in the specification of No. 5,360,692, the specification of No. 5,529,881, the specification of No. 5,296,330, the specification of No. 5,546,098, the specification of No. 5,576,143, the specification of No. 5,294,411, and the specification of No. 5,842,451. . The nonionic surfactant is not particularly limited, and is preferably a fluorine-based surfactant or a lanthanoid surfactant.

界面活性劑的使用量對於顯像液之全量而言,通常為0.001~5質量%,以0.005~2質量%為佳,更佳為0.01~0.5質量%。 The amount of the surfactant to be used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass, based on the total amount of the developing solution.

作為顯像方法,例如可適用於裝滿顯像液之槽中將基板浸漬一定時間的方法(浸漬法)、於基板表面將 顯像液藉由表面張力使其展開後靜置一定時間而顯像之方法(攪拌法)、於基板表面使顯像液噴霧的方法(噴霧法)、在以一定速度進行轉動的基板上以一定速度將顯像液塗出噴嘴一邊掃描一邊繼續塗布顯像液之方法(動態分配方法)等。作為進行圖型顯像之時間,雖無特別限制,較佳為10秒~90秒。 As a developing method, for example, it can be applied to a method of immersing a substrate in a bath filled with a developing solution for a certain period of time (dipping method), and the developing liquid is allowed to stand on the surface of the substrate by surface tension and then left to stand for a certain period of time. In the method (stirring method), a method of spraying a developing solution on the surface of a substrate (spray method), and applying a developing solution to a nozzle at a constant speed at a constant speed while scanning, the coating liquid is continuously applied. Method (dynamic allocation method), etc. The time for performing the pattern development is not particularly limited, but is preferably 10 seconds to 90 seconds.

又,於進行顯像之步驟後,可實施一邊取代為其他溶劑,一邊停止顯像的步驟。 Further, after the step of developing the image, the step of stopping the development while replacing the solvent with another solvent can be carried out.

以含有於顯像後使用含有有機溶劑之輕洗液進行洗淨的步驟者為佳。 It is preferred to use a step of washing with a light lotion containing an organic solvent after development.

作為使用於顯像後之輕洗步驟的輕洗液,僅不會溶解藉由交聯使其硬化的抗蝕圖型者即可,並無特別限制,可使用一般含有有機溶劑之溶液或水。作為前述輕洗液,使用含有選自烴系溶劑、酮系溶劑、酯系溶劑、醇系溶劑、醯胺系溶劑及醚系溶劑的至少1種類有機溶劑的輕洗液者為佳。較佳為於顯像後,進行使用含有選自由酮系溶劑、酯系溶劑、醇系溶劑、醯胺系溶劑所成群的至少1種類有機溶劑之輕洗液進行洗淨的步驟。更佳為於顯像後,使用含有醇系溶劑或酯系溶劑之輕洗液進行洗淨的步驟。更較佳為於顯像後,進行使用含有單元醇之輕洗液之洗淨的步驟。特佳為於顯像後,進行使用含有碳數5以上的單元醇的輕洗液進行洗淨的步驟。作為進行圖型輕洗之時間,並無特別限制,較佳為10秒~90秒。 The light lotion used as the light-washing step after development is not limited to a resist pattern which is hardened by crosslinking, and is not particularly limited, and a solution or water generally containing an organic solvent can be used. . As the light washing liquid, a light lotion containing at least one type of organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent is preferably used. After the development, it is preferred to carry out a step of washing with a light washing liquid containing at least one type of organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine solvent. More preferably, it is a step of washing with a light washing liquid containing an alcohol solvent or an ester solvent after development. More preferably, after the development, the step of washing with a light lotion containing a unit alcohol is carried out. It is particularly preferable to carry out a step of washing with a light washing liquid containing a unit alcohol having 5 or more carbon atoms after development. The time for performing the pattern light washing is not particularly limited, and is preferably from 10 seconds to 90 seconds.

其中,作為在顯像後輕洗步驟所使用的單元 醇,可舉出直鏈狀、支鏈狀、環狀單元醇,具體可使用1-丁醇、2-丁醇、3-甲基-1-丁醇、tert-丁基醇、1-戊醇、2-戊醇、1-己醇、4-甲基-2-戊醇、1-庚醇、1-辛醇、2-己醇、環戊醇、2-庚醇、2-辛醇、3-己醇、3-庚醇、3-辛醇、4-辛醇等,作為特佳碳數5以上的單元醇,可舉出1-己醇、2-己醇、4-甲基-2-戊醇、1-戊醇、3-甲基-1-丁醇等。 Here, as the unit alcohol used in the light washing step after development, a linear, branched, or cyclic unit alcohol may be mentioned, and specifically, 1-butanol, 2-butanol, or 3-methyl- may be used. 1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol , cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, etc., and particularly preferred as a unit alcohol having 5 or more carbon atoms. 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and the like.

前述各成分可為複數混合,亦使用與上述以外有機溶劑進行混合者。 Each of the above components may be mixed in plural, and may be mixed with an organic solvent other than the above.

輕洗液中之含水率以10質量%以下者為佳,較佳為5質量%以下,更佳為3質量%以下。將輕洗液中之含水率設定在10質量%以下時,有著可得到更良好顯像特性之傾向。 The water content in the light lotion is preferably 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less. When the water content in the light lotion is set to 10% by mass or less, there is a tendency that better development characteristics can be obtained.

使用於顯像後之輕洗液的蒸汽壓在20℃時為0.05kPa以上、以5kPa以下者為佳,以0.1kPa以上、5kPa以下者為較佳,以0.12kPa以上、3kPa以下者為更佳。輕洗液之蒸汽壓為0.05kPa以上、5kPa以下時,可進一步提高晶圓面內之溫度均勻性,且可進一步抑制因輕洗液的浸透所引起的膨潤,具有晶圓面內之尺寸均勻性更良化之傾向。 The vapor pressure of the light washing liquid used for development is 0.05 kPa or more at 20 ° C, preferably 5 kPa or less, preferably 0.1 kPa or more and 5 kPa or less, and more preferably 0.12 kPa or more and 3 kPa or less. good. When the vapor pressure of the light lotion is 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface can be further improved, and the swelling due to the penetration of the light washing liquid can be further suppressed, and the size in the wafer surface is uniform. The tendency to be more benign.

於輕洗液亦可使用適當量的界面活性劑。 An appropriate amount of surfactant can also be used in the light lotion.

對於輕洗步驟為,將進行顯像的晶圓使用含有前述有機溶劑之輕洗液進行洗淨處理。洗淨處理之方法並無特別限定,例如可適用以一定速度下轉動的基板上繼 續塗布輕洗液之方法(轉動塗佈法)、於裝滿輕洗液的槽中將基板浸漬一定時間之方法(浸漬法)、於基板表面噴霧輕洗液的方法(噴霧法)等,其中亦藉由轉動塗佈方法進行洗淨處理,於洗淨後將基板以2000rpm~4000rpm的轉動數進行轉動,將輕洗液字基板上除去者為佳。 In the light washing step, the wafer to be developed is subjected to a washing treatment using a light washing liquid containing the organic solvent. The method of the washing treatment is not particularly limited. For example, a method of continuously applying a light washing liquid on a substrate rotating at a constant speed (rotary coating method) can be applied, and the substrate is immersed in a tank filled with a light washing liquid for a certain period of time. a method (dipping method), a method of spraying a light washing liquid on a surface of a substrate (spraying method), etc., wherein the substrate is also subjected to a washing treatment by a spin coating method, and after the washing, the substrate is rotated at a number of revolutions of 2000 rpm to 4000 rpm. It is preferred to remove the light wash liquid substrate.

形成抗蝕圖型後,藉由進行蝕刻可得到圖型配線基板。蝕刻的方法為可藉由使用電漿氣的乾蝕刻及鹼溶液、氯化第二銅溶液、氯化第二鐵溶液等濕蝕刻等公知方法進行。 After the resist pattern is formed, the pattern wiring substrate can be obtained by etching. The etching method can be carried out by a known method such as dry etching using a plasma gas, wet etching such as an alkali solution, a second copper chloride solution, or a second iron chloride solution.

形成抗蝕圖型後,可進行鍍敷。作為鍍敷法,例如可舉出銅鍍敷、焊錫鍍敷、鎳鍍敷、金鍍敷等。 After the resist pattern is formed, plating can be performed. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.

蝕刻後之殘存抗蝕圖型可藉由有機溶劑進行剝離。作為有機溶劑,可舉出PGMEA(丙二醇單甲基醚乙酸酯)、PGME(丙二醇單甲基醚)、EL(乳酸乙酯)等。作為剝離方法,例如可舉出浸漬方法、噴霧方式等。又,形成抗蝕圖型之配線基板亦可為多層配線基板,亦可具有小徑通孔。 The residual resist pattern after etching can be peeled off by an organic solvent. Examples of the organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), and EL (ethyl lactate). Examples of the peeling method include a dipping method, a spraying method, and the like. Further, the wiring substrate on which the resist pattern is formed may be a multilayer wiring substrate or may have a small-diameter through hole.

於本實施形態中之配線基板可藉由抗蝕圖型形成後將金屬在真空中進行蒸鍍,其後將抗蝕圖型溶解於溶液的方法,即可藉由提離法形成。 In the wiring substrate of the present embodiment, the metal can be vapor-deposited in a vacuum after forming a resist pattern, and then the resist pattern can be dissolved in a solution, which can be formed by lift-off.

[使用於下層膜用途之光刻用膜形成組成物]  [Film forming composition for lithography used for underlayer film]  

於本實施形態中之使用於下層膜用途的光刻用膜形成組成物(以下亦稱為「下層膜形成材料」)為含有選自由上 述式(1)所示化合物、將上述式(1)所示化合物作為單體而得之樹脂、式(2)所示化合物及將式(2)所示化合物作為單體而得之樹脂所成群的至少1種物質。於本實施形態中之前述物質由塗佈性及品質安定性的觀點來看,下層膜形成材料中,以1~100質量%者為佳,以10~100質量%者為較佳,以50~100質量%者更佳為,以100質量%者為特佳。 The film forming composition for lithography (hereinafter also referred to as "underlayer film forming material") used in the underlayer film in the present embodiment contains the compound represented by the above formula (1) and the above formula (1) The compound obtained as a monomer, at least one of a resin obtained as a monomer, a compound represented by the formula (2), and a resin obtained by using the compound represented by the formula (2) as a monomer. The above-mentioned substance in the present embodiment is preferably from 1 to 100% by mass, more preferably from 10 to 100% by mass, and preferably from 50% to 100% by mass of the underlayer film forming material. It is more preferable to use 100% by mass, and 100% by mass.

本實施形態的下層膜形成材料可是用於濕式製程中,具有優良的耐熱性及蝕刻耐性。且,本實施形態之下層膜形成材料因使用上述物質,高溫燒烤時之膜的劣化受到抑制,可形成對於氧電漿蝕刻等之蝕刻耐性亦優良的下層膜。且本實施形態之下層膜形成材料因具有與抗蝕層之密著性優良,故可得到優良的抗蝕圖型。且,本實施形態的下層膜形成材料於不損害本發明之效果的範圍下,可含有已知的光刻用下層膜形成材料等。 The underlayer film forming material of the present embodiment may be used in a wet process and has excellent heat resistance and etching resistance. In addition, in the layer film forming material of the present embodiment, deterioration of the film at the time of high-temperature grilling is suppressed by using the above-mentioned substance, and an underlayer film excellent in etching resistance such as oxygen plasma etching can be formed. Further, since the film forming material of the present embodiment has excellent adhesion to the resist layer, an excellent resist pattern can be obtained. In addition, the underlayer film forming material of the present embodiment may contain a known underlayer film forming material for lithography, etc., within a range that does not impair the effects of the present invention.

[溶劑]  [solvent]  

於本實施形態中之下層膜形成材料可含有溶劑。作為使用於下層膜形成材料之溶劑,若為至少可溶解上述物質者即可,可適用公知者。 In the present embodiment, the underlayer film forming material may contain a solvent. As a solvent used for the underlayer film forming material, those which are at least soluble in the above-mentioned materials can be used.

作為溶劑之具體例子,並無特別限定,例如可舉出丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮系溶劑;丙二醇單甲基醚、丙二醇單甲基醚乙酸酯等溶纖劑系溶劑;乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸丁酯、乙酸異戊酯、乳酸乙酯、甲氧基丙酸甲酯、羥基異丁酸甲酯 等酯系溶劑;甲醇、乙醇、異丙醇、1-乙氧基-2-丙醇等醇系溶劑;甲苯、二甲苯、苯甲醚等的芳香族系烴等。這些溶劑可單獨使用1種或組合2種以上後使用。 Specific examples of the solvent are not particularly limited, and examples thereof include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; propylene glycol monomethyl ether and propylene glycol monomethyl ether B; Solvents such as acid esters; esters of ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc. A solvent; an alcohol solvent such as methanol, ethanol, isopropanol or 1-ethoxy-2-propanol; or an aromatic hydrocarbon such as toluene, xylene or anisole. These solvents may be used alone or in combination of two or more.

上述溶劑之中由安全性的觀點來看,亦以環己酮、丙二醇單甲基醚、丙二醇單甲基醚乙酸酯、乳酸乙酯、羥基異丁酸甲酯、苯甲醚特佳。 Among the above solvents, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl hydroxyisobutyrate, and anisole are particularly preferred from the viewpoint of safety.

溶劑之含有量並無特別限定,由溶解性及製膜上的觀點來看,對於前述下層膜形成材料100質量份,以100~10,000質量份者為佳,以200~5,000質量份者為較佳,以200~1,000質量份者為更佳。 The content of the solvent is not particularly limited. From the viewpoint of solubility and film formation, 100 parts by mass of the underlayer film forming material is preferably 100 to 10,000 parts by mass, and 200 to 5,000 parts by mass. Good, preferably 200 to 1,000 parts by mass.

[交聯劑]  [crosslinking agent]  

於本實施形態中之下層膜形成材料由抑制互混等觀點來看,視必要可含有交聯劑。作為交聯劑並無特別限定,例如可舉出於國際公開第2013/024779號所記載者。 In the present embodiment, the underlayer film forming material may contain a crosslinking agent as necessary from the viewpoint of suppressing mutual mixing and the like. The crosslinking agent is not particularly limited, and examples thereof include those described in International Publication No. 2013/024779.

作為對於本實施形態中可使用的交聯劑之具體例子,例如可舉出酚化合物、環氧化合物、氰酸酯化合物、胺基化合物、苯並噁嗪化合物、丙烯酸酯化合物、三聚氰胺化合物、胍胺化合物、乙二醇脲化合物、脲化合物、異氰酸酯化合物、疊氮化合物等,並未特別限定於此等。這些交聯劑可單獨使用1種或組合2種以上後使用。彼等中亦以苯並噁嗪化合物、環氧化合物或氰酸酯化合物為佳,由提高蝕刻耐性的觀點來看,以苯並噁嗪化合物為較佳。 Specific examples of the crosslinking agent which can be used in the present embodiment include a phenol compound, an epoxy compound, a cyanate compound, an amine compound, a benzoxazine compound, an acrylate compound, a melamine compound, and a hydrazine. The amine compound, the ethylene glycol urea compound, the urea compound, the isocyanate compound, the azide compound, and the like are not particularly limited thereto. These crosslinking agents may be used alone or in combination of two or more. Among them, a benzoxazine compound, an epoxy compound or a cyanate compound is preferred, and a benzoxazine compound is preferred from the viewpoint of improving etching resistance.

作為前述酚化合物,可使用公知者。例如作為酚類,除酚以外,可舉出甲酚類、二甲酚類等的烷基酚類、氫醌等多價酚類、萘酚類、萘二醇類等多環酚類、雙酚A、雙酚F等雙酚類或者酚酚醛清漆、酚芳烷基樹脂等多官能性酚化合物等。其中由耐熱性及溶解性的觀點來看,以芳烷基型酚樹脂為佳。 As the phenol compound, a known one can be used. Examples of the phenols include, in addition to phenol, alkylphenols such as cresols and xylenols, polyvalent phenols such as hydroquinone, polycyclic phenols such as naphthols and naphthalenediols, and A bisphenol such as phenol A or bisphenol F, or a polyfunctional phenol compound such as a phenol novolak or a phenol aralkyl resin. Among them, an aralkyl type phenol resin is preferred from the viewpoint of heat resistance and solubility.

作為前述環氧化合物,可使用公知者,選自於1分子中具有2個以上環氧基者。例如可舉出雙酚A、雙酚F、3,3’,5,5’-四甲基-雙酚F、雙酚S、芴雙酚、2,2’-雙酚、3,3’,5,5’-四甲基-4,4’-二羥基雙酚、間苯二酚、萘二醇類等2價酚類之環氧化物、參-(4-羥基苯基)甲烷、1,1,2,2-肆(4-羥基苯基)乙烷、參(2,3-環氧丙基)異氰脲酸酯、三羥甲基甲烷三縮水甘油基醚、三羥甲基丙烷三縮水甘油基醚、三羥乙基乙烷三縮水甘油基醚、酚酚醛清漆、o-甲酚酚醛清漆等3價以上之酚類的環氧化物、二環戊二烯與酚類之共縮合樹脂的環氧化物、由酚類與對亞二甲苯二氯化物等所合成的酚芳烷基樹脂類之環氧化物、由酚類與雙氯甲基聯苯基等所合成的聯苯基芳烷基型酚樹脂之環氧化物、由萘酚類與對亞二甲苯二氯化物等所合成的萘酚芳烷基樹脂類之環氧化物等。這些環氧樹脂可單獨使用亦可併用2種以上。其中亦由耐熱性與溶解性的觀點來看,以由酚芳烷基樹脂類、聯苯基芳烷基樹脂類所得之環氧樹脂等在常溫為固體狀環氧樹脂者為佳。 As the epoxy compound, a known one can be used, and it is selected from those having two or more epoxy groups in one molecule. Examples thereof include bisphenol A, bisphenol F, 3,3', 5,5'-tetramethyl-bisphenol F, bisphenol S, bisphenol, 2,2'-bisphenol, 3,3' , 5,5'-tetramethyl-4,4'-dihydroxybisphenol, resorcinol, naphthalenediol, etc., epoxides of divalent phenols, ginseng-(4-hydroxyphenyl)methane, 1,1,2,2-indole (4-hydroxyphenyl)ethane, ginseng (2,3-epoxypropyl)isocyanurate, trishydroxymethylmethane triglycidyl ether, trishydroxyl Ethylene oxides, dicyclopentadienes and phenols of trivalent or higher phenols such as propane triglycidyl ether, trishydroxyethyl ethane triglycidyl ether, phenol novolac, o-cresol novolac An epoxide of a co-condensation resin, an epoxide of a phenol aralkyl resin synthesized from a phenol and a p-xylene dichloride, or the like, and a phenol and a bischloromethylbiphenyl group. An epoxide of a biphenyl aralkyl type phenol resin, an epoxide of a naphthol aralkyl resin synthesized from a naphthol and a p-xylene dichloride, or the like. These epoxy resins may be used alone or in combination of two or more. Among them, from the viewpoint of heat resistance and solubility, an epoxy resin obtained from a phenol aralkyl resin or a biphenyl aralkyl resin is preferably a solid epoxy resin at normal temperature.

作為前述氰酸酯化合物,若為於1分子中具有 2個以上氰酸酯基的化合物者即可並無特別限制,亦可使用公知者。對於本實施形態,作為較佳氰酸酯化合物,可舉出於1分子中具有2個以上羥基之化合物的羥基取代為氰酸酯基的結構者。又,氰酸酯化合物係以具有芳香族基者為佳,使用氰酸酯基直接鍵結於芳香族基的結構者為佳。作為如此氰酸酯化合物,例如可舉出雙酚A、雙酚F、雙酚M、雙酚P、雙酚E、酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、二環戊二烯酚醛清漆樹脂、四甲基雙酚F、雙酚A酚醛清漆樹脂、溴化雙酚A、溴化酚酚醛清漆樹脂、3官能酚、4官能酚、萘型酚、聯苯基型酚、酚芳烷基樹脂、聯苯基芳烷基樹脂、萘酚芳烷基樹脂、二環戊二烯芳烷基樹脂、脂環式酚、含有磷之酚等將羥基由氰酸酯基所取代的結構者。這些氰酸酯化合物可單獨使用或適宜地組合2種以上後使用。又,上述氰酸酯化合物可為單體、寡聚物及樹脂中任一形態。 The cyanate ester compound is not particularly limited as long as it has a compound having two or more cyanate groups in one molecule, and a known one can also be used. In the present embodiment, a preferred cyanate ester compound is a structure in which a hydroxyl group of a compound having two or more hydroxyl groups in one molecule is substituted with a cyanate group. Further, the cyanate ester compound is preferably one having an aromatic group and a structure in which a cyanate group is directly bonded to an aromatic group. Examples of such a cyanate ester compound include bisphenol A, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolac resin, cresol novolak resin, and dicyclopentadiene novolac resin. , tetramethyl bisphenol F, bisphenol A novolak resin, brominated bisphenol A, brominated phenol novolac resin, trifunctional phenol, tetrafunctional phenol, naphthalene phenol, biphenyl phenol, phenol aralkyl A resin, a biphenyl aralkyl resin, a naphthol aralkyl resin, a dicyclopentadiene aralkyl resin, an alicyclic phenol, a phosphorus-containing phenol, or the like, which has a hydroxyl group substituted by a cyanate group. These cyanate ester compounds can be used singly or in combination of two or more kinds as appropriate. Further, the cyanate compound may be in any form of a monomer, an oligomer, and a resin.

作為前述胺基化合物,例示出m-亞苯二胺、p-亞苯二胺、4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基丙烷、4,4’-二胺基二苯基醚、3,4’-二胺基二苯基醚、3,3’-二胺基二苯基醚、4,4’-二胺基二苯基碸、3,4’-二胺基二苯基碸、3,3’-二胺基二苯基碸、4,4’-二胺基二苯基硫化物、3,4’-二胺基二苯基硫化物、3,3’-二胺基二苯基硫化物、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(3-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、雙[4-(4-胺基苯氧基)苯基]碸、2,2-雙[4-(4-胺基苯氧基)苯基]丙 烷、2,2-雙[4-(3-胺基苯氧基)苯基]丙烷、4,4’-雙(4-胺基苯氧基)聯苯基、4,4’-雙(3-胺基苯氧基)聯苯基、雙[4-(4-胺基苯氧基)苯基]醚、雙[4-(3-胺基苯氧基)苯基]醚、9,9-雙(4-胺基苯基)芴、9,9-雙(4-胺基-3-氯苯基)芴、9,9-雙(4-胺基-3-氟苯基)芴、O-三嗪、m-三嗪、4,4’-二胺基苯甲醯苯胺、2,2’-雙(三氟甲基)-4,4’-二胺基聯苯基、4-胺基苯基-4-胺基苯甲酸酯、2-(4-胺基苯基)-6-胺基苯並噁唑等。且亦可舉出4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基丙烷、4,4’-二胺基二苯基醚、3,4’-二胺基二苯基醚、3,3’-二胺基二苯基醚、4,4’-二胺基二苯基碸、3,3’-二胺基二苯基碸、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(3-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、雙[4-(4-胺基苯氧基)苯基]碸、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(3-胺基苯氧基)苯基]丙烷、4,4’-雙(4-胺基苯氧基)聯苯基、4,4’-雙(3-胺基苯氧基)聯苯基、雙[4-(4-胺基苯氧基)苯基]醚、雙[4-(3-胺基苯氧基)苯基]醚等的芳香族胺類、二胺基環己烷、二胺基二環己基甲烷、二甲基-二胺基二環己基甲烷、四甲基-二胺基二環己基甲烷、二胺基二環己基丙烷、二胺基聯環[2.2.1]庚烷、雙(胺基甲基)-聯環[2.2.1]庚烷、3(4),8(9)-雙(胺基甲基)三環[5.2.1.02,6]癸烷、1,3-聯胺基甲基環己烷、異佛爾酮二胺等脂環式胺類、乙二胺、六伸甲基二胺、八伸甲基二胺、十伸甲基二胺、二伸乙基三胺、三伸乙基四胺等脂肪族胺類等。 As the above-mentioned amine compound, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4, are exemplified. 4'-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl hydrazine, 3,4'-Diaminodiphenylphosphonium, 3,3'-diaminodiphenylphosphonium, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl Base sulfide, 3,3'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]fluorene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 4,4'-double (4-Aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, Bis[4-(3-aminophenoxy)phenyl]ether, 9,9-bis(4-aminophenyl)anthracene, 9,9-bis(4-amino-3-chlorophenyl) Ruthenium, 9,9-bis(4-amino-3-fluorophenyl)anthracene, O-triazine, m-triazine, 4,4'-diaminobenzimidazole Amine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4-aminophenyl-4-aminobenzoate, 2-(4-amino group Phenyl)-6-aminobenzoxazole and the like. Also, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,4'-di Aminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 1,4- Bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-double ( 3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3- Aromatic phenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, aromatic amine such as bis[4-(3-aminophenoxy)phenyl]ether , diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, tetramethyl-diaminodicyclohexylmethane, diaminodicyclohexylpropane, two Aminobicyclo[2.2.1]heptane, bis(aminomethyl)-bicyclo[2.2.1]heptane, 3(4),8(9)-bis(aminomethyl)tricyclo[ 5.2.1.02,6]decane, 1,3-diaminomethylcyclohexane, isophor An aliphatic such as an alicyclic amine such as a diamine, an ethylenediamine, a hexamethylenediamine, an octamethylamine, a decylmethyldiamine, a diethylidenetriamine or a trisoleethyltetramine Amines, etc.

作為前述苯並噁嗪化合物,可舉出由二官能性二胺類與單官能酚類所得之P-d型苯並噁嗪、由單官能性二胺類與二官能性酚類所得之F-a型苯並噁嗪等。 Examples of the benzoxazine compound include a Pd-type benzoxazine obtained from a difunctional diamine and a monofunctional phenol, and a Fa-type benzene derived from a monofunctional diamine and a difunctional phenol. And oxazine and so on.

作為前述三聚氰胺化合物之具體例子,例如可舉出六羥甲基三聚氰胺、六甲氧基甲基三聚氰胺、六羥甲基三聚氰胺的1~6個羥甲基經甲氧基甲基化的化合物或其混合物、六甲氧基乙基三聚氰胺、六醯氧基甲基三聚氰胺、六羥甲基三聚氰胺的羥甲基之1~6個經醯氧基甲基化的化合物或其混合物等。 Specific examples of the melamine compound include, for example, hexamethylol melamine, hexamethoxymethyl melamine, hexamethylol melamine, a methoxymethylated compound of 1 to 6 methylol groups, or a mixture thereof. And hexamethoxyethyl melamine, hexamethoxymethyl melamine, hydroxymethyl group of hexamethylol melamine, 1 to 6 methoxymethylated compounds or a mixture thereof.

作為前述胍胺化合物之具體例子,例如可舉出四羥甲基胍胺、四甲氧基甲基胍胺、四羥甲基胍胺的1~4個羥甲基經甲氧基甲基化的化合物或其混合物、四甲氧基乙基胍胺、四醯氧基胍胺、四羥甲基胍胺的1~4個羥甲基經醯氧基甲基化的化合物或其混合物等。 Specific examples of the guanamine compound include methoxymethylation of 1 to 4 methylol groups of tetramethylol decylamine, tetramethoxymethyl decylamine, and tetrahydroxymethyl decylamine. The compound or a mixture thereof, tetramethoxyethyl decylamine, tetradecyl decylamine, tetrahydroxymethyl decylamine, a 1,4-hydroxymethylmethylated compound or a mixture thereof, or the like.

作為前述乙二醇脲化合物之具體例子,例如可舉出四羥甲基乙二醇脲、四甲氧基乙二醇脲、四甲氧基甲基乙二醇脲、四羥甲基乙二醇脲的羥甲基之1~4個經甲氧基甲基化的化合物或其混合物、四羥甲基乙二醇脲的羥甲基之1~4個經醯氧基甲基化的化合物或其混合物等。 Specific examples of the ethylene glycol urea compound include tetramethylol glycol urea, tetramethoxyethylene glycol urea, tetramethoxymethyl glycol urea, and tetrahydroxymethyl ethylene glycol. 1 to 4 methoxymethylated compounds of a hydroxymethyl group of a glycol urea or a mixture thereof, 1 to 4 methoxymethylated compounds of a hydroxymethyl group of tetramethylol glycol urea Or a mixture thereof, and the like.

作為前述脲化合物之具體例子,例如可舉出四羥甲基脲、四甲氧基甲基脲、四羥甲基脲的1~4個羥甲基經甲氧基甲基化的化合物或其混合物、四甲氧基乙基脲等。 Specific examples of the urea compound include, for example, a methoxymethylated compound of 1,4-hydroxymethyl urea, tetramethoxymethyl urea, and tetramethylol urea of 1 to 4 methylol groups or Mixture, tetramethoxyethyl urea, and the like.

又,對於本實施形態,由交聯性向上的觀點 來看,亦可使用具有至少1個烯丙基之交聯劑。作為具有至少1個烯丙基之交聯劑的具體例子,可舉出2,2-雙(3-烯丙基-4-羥基苯基)丙烷、1,1,1,3,3,3-六氟-2,2-雙(3-烯丙基-4-羥基苯基)丙烷、雙(3-烯丙基-4-羥基苯基)碸、雙(3-烯丙基-4-羥基苯基)硫化物、雙(3-烯丙基-4-羥基苯基)醚等的烯丙基酚類、2,2-雙(3-烯丙基-4-氰酸苯基)丙烷、1,1,1,3,3,3-六氟-2,2-雙(3-烯丙基-4-氰酸苯基)丙烷、雙(3-烯丙基-4-氰酸苯基)碸、雙(3-烯丙基-4-氰酸苯基)硫化物、雙(3-烯丙基-4-氰酸苯基)醚等的烯丙基氰酸酯類、二烯丙基鄰苯二甲酸酯、二烯丙基間苯二甲酸酯、二烯丙基對苯二甲酸乙二醇酯、三烯丙基異氰脲酸酯、三羥甲基丙烷二烯丙基醚、季戊四醇烯丙基醚等,並未限定於此等例示者。這些可單獨,亦可為2種類以上之混合物。此等中亦以2,2-雙(3-烯丙基-4-羥基苯基)丙烷、1,1,1,3,3,3-六氟-2,2-雙(3-烯丙基-4-羥基苯基)丙烷、雙(3-烯丙基-4-羥基苯基)碸、雙(3-烯丙基-4-羥基苯基)硫化物、雙(3-烯丙基-4-羥基苯基)醚等的烯丙基酚類為佳。 Further, in the present embodiment, a crosslinking agent having at least one allyl group may be used from the viewpoint of crosslinkability. Specific examples of the crosslinking agent having at least one allyl group include 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 1,1,1,3,3,3. -hexafluoro-2,2-bis(3-allyl-4-hydroxyphenyl)propane, bis(3-allyl-4-hydroxyphenyl)anthracene, bis(3-allyl-4- Allyl phenol such as hydroxyphenyl) sulfide, bis(3-allyl-4-hydroxyphenyl)ether, 2,2-bis(3-allyl-4-c-phenylphenyl)propane 1,1,1,3,3,3-hexafluoro-2,2-bis(3-allyl-4-c-phenylphenyl)propane, bis(3-allyl-4-cyanate benzene Allyl cyanate, diene (3-allyl-4-c-phenylphenyl) sulfide, bis(3-allyl-4-c-phenylphenyl) ether, etc. Propyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl isocyanurate, trimethylolpropane diene The propyl ether, pentaerythritol allyl ether, and the like are not limited to these examples. These may be used alone or in a mixture of two or more types. These are also 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3-allyl 4-hydroxyphenyl)propane, bis(3-allyl-4-hydroxyphenyl)fluorene, bis(3-allyl-4-hydroxyphenyl) sulfide, bis(3-allyl) Allyl phenols such as 4-hydroxyphenyl)ether are preferred.

下層膜形成材料中之交聯劑的含有量並無特別限定,但對於下層膜形成材料100質量份,以0.1~100質量份者為佳,以5~50質量份為較佳,更佳為10~40質量份。交聯劑之含有量若在上述範圍時,有著與抗蝕層之混雜現象的產生受到抑制之傾向,又有的反射防止效果提高,交聯後之膜形成性提高的傾向。 The content of the crosslinking agent in the underlayer film forming material is not particularly limited, but it is preferably 0.1 to 100 parts by mass, more preferably 5 to 50 parts by mass, more preferably 100 parts by mass of the underlayer film forming material. 10 to 40 parts by mass. When the content of the crosslinking agent is in the above range, the occurrence of a phenomenon of mixing with the resist layer tends to be suppressed, and the effect of preventing reflection is improved, and the film formability after crosslinking tends to be improved.

[交聯促進劑]  [Crosslinking accelerator]  

於本實施形態的下層膜形成材料中,視必要可使用可促進交聯、硬化反應的交聯促進劑。 In the underlayer film forming material of the present embodiment, a crosslinking accelerator which can promote crosslinking and curing reaction can be used as necessary.

作為前述交聯促進劑,若為促進交聯、硬化反應者即可,並無特別限定,例如可舉出胺類、咪唑類、有機膦類、路易氏酸等。這些交聯促進劑可單獨使用1種或組合2種以上後使用。此等中亦以咪唑類或有機膦類為佳,由交聯溫度之低溫化的觀點來看,以咪唑類為較佳。 The cross-linking accelerator is not particularly limited as long as it promotes cross-linking or hardening reaction, and examples thereof include amines, imidazoles, organic phosphines, and Lewis acid. These crosslinking accelerators may be used alone or in combination of two or more. Among these, imidazoles or organic phosphines are preferred, and imidazoles are preferred from the viewpoint of lowering the crosslinking temperature.

作為前述交聯促進劑,雖未限定為以下,但例如可舉出1,8-二氮雜雙環(5,4,0)十一碳烯-7、三乙二胺、苯甲基二甲基胺、三乙醇胺、二甲基胺基乙醇、參(二甲基胺基甲基)酚等三級胺、2-甲基咪唑、2-苯基咪唑、2-乙基-4-甲基咪唑、2-苯基-4-甲基咪唑、2-十七基咪唑、2,4,5-三苯基咪唑等咪唑類、三丁基膦、甲基二苯基膦、三苯基膦、二苯基膦、苯基膦等有機膦類、四苯基鏻.四苯基硼酸鹽、四苯基鏻.乙基三苯基硼酸鹽、四丁基鏻.四丁基硼酸鹽等四取代鏻.四取代硼酸鹽、2-乙基-4-甲基咪唑.四苯基硼酸鹽、N-甲基嗎啉.四苯基硼酸鹽等四苯基硼鹽等。 The crosslinking accelerator is not limited to the following, and examples thereof include 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, and benzyldimethyl Tertiary amines such as cisamine, triethanolamine, dimethylaminoethanol, ginseng (dimethylaminomethyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methyl Imidazoles such as imidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, 2,4,5-triphenylimidazole, tributylphosphine, methyldiphenylphosphine, triphenylphosphine , organic phosphines such as diphenylphosphine and phenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium, ethyltriphenylborate, tetrabutylphosphonium, tetrabutylborate, etc. Instead of a tetraphenylborate such as a tetrasubstituted borate, 2-ethyl-4-methylimidazole, tetraphenylborate, N-methylmorpholine or tetraphenylborate.

作為交聯促進劑之配合量,通常將下層膜形成材料全體作為100質量份時,以0.1~10質量份為佳,較佳為由控制的容易性及經濟性的觀點來看為0.1~5質量份,更佳為0.1~3質量份。 When the total amount of the underlayer film forming material is 100 parts by mass, the amount of the crosslinking agent is preferably 0.1 to 10 parts by mass, preferably 0.1 to 5 from the viewpoint of easiness of control and economy. The mass fraction is more preferably 0.1 to 3 parts by mass.

[自由基聚合起始劑]  [Free radical polymerization initiator]  

於本實施形態的下層膜形成材料中,視必要可添加自由基聚合起始劑。作為自由基聚合起始劑,可為藉由光而開始進行自由基聚合的光聚合起始劑,亦可為藉由熱而開始進行自由基聚合的熱聚合起始劑。 In the underlayer film forming material of the present embodiment, a radical polymerization initiator may be added as necessary. The radical polymerization initiator may be a photopolymerization initiator which starts radical polymerization by light, or a thermal polymerization initiator which starts radical polymerization by heat.

作為如此自由基聚合起始劑,並無特別限制,可適宜地採用過去使用者。例如可舉出1-羥基環己基苯基酮、苯甲基二甲基縮酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷-1-酮、2-羥基-1-{4-[4-(2-羥基-2-甲基-丙醯基)-苯甲基]苯基}-2-甲基丙烷-1-酮、2,4,6-三甲基苯甲醯基-二苯基-氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦等酮系光聚合起始劑、甲基乙基酮過氧化物、環己酮過氧化物、甲基環己酮過氧化物、甲基乙醯乙酸酯過氧化物、乙醯乙酸酯過氧化物、1,1-雙(t-己基過氧)-3,3,5-三甲基環己烷、1,1-雙(t-己基過氧)-環己烷、1,1-雙(t-丁基過氧)-3,3,5-三甲基環己烷、1,1-雙(t-丁基過氧)-2-甲基環己烷、1,1-雙(t-丁基過氧)-環己烷、1,1-雙(t-丁基過氧)環十二烷、1,1-雙(t-丁基過氧)丁烷、2,2-雙(4,4-二-t-丁基過氧環己基)丙烷、p-蓋萜烷過氧化氫、二異丙基苯過氧化氫、1,1,3,3-四甲基丁基過氧化氫、異丙苯過氧化氫、t-己基過氧化氫、t-丁基過氧化氫、α,α’-雙(t-丁基過氧)二異丙基苯、二異丙苯過氧化物、2,5-二甲基-2,5-雙(t-丁基過氧)己烷、t-丁基異丙苯過氧化物、二-t-丁基過氧化物、2,5-二甲基-2,5-雙(t-丁 基過氧)己炔-3、異丁醯基過氧化物、3,5,5-三甲基己醯基過氧化物、辛醯基過氧化物、月桂醯基過氧化物、硬脂醯基過氧化物、琥珀酸酸過氧化物、m-甲苯醯苯甲醯基過氧化物、苯甲醯基過氧化物、二-n-丙基過氧二碳酸酯、二異丙基過氧二碳酸酯、雙(4-t-丁基環己基)過氧二碳酸酯、二-2-乙氧基乙基過氧二碳酸酯、二-2-乙氧基己基過氧二碳酸酯、二-3-甲氧基丁基過氧二碳酸酯、二-s-丁基過氧二碳酸酯、二(3-甲基-3-甲氧基丁基)過氧二碳酸酯、α,α’-雙(新癸醯基過氧)二異丙基苯、異丙苯過氧新癸酸酯、1,1,3,3-四甲基丁基過氧新癸酸酯、1-環己基-1-甲基乙基過氧新癸酸酯、t-己基過氧新癸酸酯、t-丁基過氧新癸酸酯、t-己基過氧新戊酸酯、t-丁基過氧新戊酸酯、1,1,3,3-四甲基丁基過氧-2-乙基己酸酯、2,5-二甲基-2,5-雙(2-乙基己醯基過氧)己酸酯、1-環己基-1-甲基乙基過氧-2-乙基己酸酯、t-己基過氧-2-乙基己酸酯、t-丁基過氧-2-乙基己酸酯、t-己基過氧異丙基單碳酸酯、t-丁基過氧異丁酸酯、t-丁基過氧蘋果酸酯、t-丁基過氧-3,5,5-三甲胺酚(metol)己酸酯、t-丁基過氧月桂酸酯、t-丁基過氧異丙基單碳酸酯、t-丁基過氧-2-乙基己基單碳酸酯、t-丁基過氧乙酸酯、t-丁基過氧-m-甲苯甲醯基苯甲酸酯、t-丁基過氧苯甲酸酯、雙(t-丁基過氧)間苯二甲酸酯、2,5-二甲基-2,5-雙(m-甲苯甲醯基過氧)己烷、t-己基過氧苯甲酸酯、2,5-二甲基-2,5-雙(苯甲醯基過氧)己烷、t-丁基過氧烯丙基單碳酸酯、t-丁基三甲基矽基過氧化物、3,3’,4,4’-四(t-丁 基過氧羰基)二苯甲酮、2,3-二甲基-2,3-二苯基丁烷等有機過氧化物系聚合起始劑。 The radical polymerization initiator is not particularly limited, and may be suitably used in the past. Examples thereof include 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-[4-(2-hydroxyl). Ethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionate) -Phenylmethyl]phenyl}-2-methylpropan-1-one, 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, bis(2,4,6- Ketone photopolymerization initiators such as trimethylbenzhydryl)-phenylphosphine oxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl ethyl Indole acetate peroxide, acetamidine acetate peroxide, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-double (t -hexylperoxy)-cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy) -2-methylcyclohexane, 1,1-bis(t-butylperoxy)-cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 1,1-double (t-butylperoxy)butane, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, p-calendane hydrogen peroxide, diisopropylbenzene peroxidation Hydrogen, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide T-hexyl hydroperoxide, t-butyl hydroperoxide, α,α'-bis(t-butylperoxy)diisopropylbenzene, diisopropylbenzene peroxide, 2,5-dimethyl -2,5-bis(t-butylperoxy)hexane, t-butyl cumene peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5- Bis(t-butylperoxy)hexyne-3, isobutylguanidino peroxide, 3,5,5-trimethylhexyl peroxide, octyl peroxide, lauryl peroxide, stearic acid Mercapto peroxide, succinic acid peroxide, m-tolylbenzyl peroxide, benzhydryl peroxide, di-n-propyl peroxydicarbonate, diisopropyl Oxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate , bis-3-methoxybutylperoxydicarbonate, di-s-butylperoxydicarbonate, bis(3-methyl-3-methoxybutyl)peroxydicarbonate, α , α'-bis(new fluorenylperoxy)diisopropylbenzene, cumene peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, 1 -cyclohexyl-1-methylethyl peroxy neodecanoate , t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 1,1,3,3 -tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexanoate, 1-cyclohexyl- 1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexyl Oxypropyl isopropyl carbonate, t-butyl peroxy isobutyrate, t-butyl peroxy malate, t-butyl peroxy-3,5,5-trimethylol (metol) hexanoic acid Ester, t-butylperoxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butyl peroxyacetate , t-butyl peroxy-m-tolylmethyl benzoate, t-butyl peroxybenzoate, bis(t-butyl peroxy) isophthalate, 2,5- Dimethyl-2,5-bis(m-tolylmethyl peroxy)hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzylidene) Peroxy)hexane, t-butylperoxyallyl monocarbonate, t-butyltrimethylsulfonyl peroxide, 3,3',4,4'-tetra(t-butylperoxy) Carbonyl An organic peroxide-based polymerization initiator such as benzophenone or 2,3-dimethyl-2,3-diphenylbutane.

又,可舉出2-苯基偶氮-4-甲氧基-2,4-二甲基戊腈、1-[(1-氰基-1-甲基乙基)偶氮]甲醯胺、1,1’-偶氮雙(環己烷-1-甲腈)、2,2’-偶氮雙(2-甲基丁腈)、2,2’-偶氮二異丁腈、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2’-偶氮雙(2-甲基丙酸脒)二氫氯化物、2,2’-偶氮雙(2-甲基-N-苯基丙酸脒)二氫氯化物、2,2’-偶氮雙[N-(4-氯苯基)-2-甲基丙酸脒]二氫化物氯化物、2,2’-偶氮雙[N-(4-氫苯基)-2-甲基丙酸脒]二氫氯化物、2,2’-偶氮雙[2-甲基-N-(苯基甲基)丙酸脒]二氫氯化物、2,2’-偶氮雙[2-甲基-N-(2-丙烯基)丙酸脒]二氫氯化物、2,2’-偶氮雙[N-(2-羥基乙基)-2-甲基丙酸脒]二氫氯化物、2,2’-偶氮雙[2-(5-甲基-2-咪唑啉-2-基)丙烷]二氫氯化物、2,2’-偶氮雙[2-(2-咪唑啉-2-基)丙烷]二氫氯化物、2,2’-偶氮雙[2-(4,5,6,7-四氫-1H-1,3-二吖庚因-2-基)丙烷]二氫氯化物、2,2’-偶氮雙[2-(3,4,5,6-四氫嘧啶-2-基)丙烷]二氫氯化物、2,2’-偶氮雙[2-(5-羥基-3,4,5,6-四氫嘧啶-2-基)丙烷]二氫氯化物、2,2’-偶氮雙[2-[1-(2-羥基乙基)-2-咪唑啉-2-基]丙烷]二氫氯化物、2,2’-偶氮雙[2-(2-咪唑啉-2-基)丙烷]、2,2’-偶氮雙[2-甲基-N-[1,1-雙(羥基甲基)-2-羥基乙基]丙醯胺]、2,2’-偶氮雙[2-甲基-N-[1,1-雙(羥基甲基)乙基]丙醯胺]、2,2’-偶氮雙[2-甲基-N-(2-羥基乙基)丙醯胺]、2,2’-偶氮雙(2-甲基丙醯胺)、2,2’-偶氮雙(2,4,4-三甲基戊烷)、2,2’-偶氮雙(2-甲基丙烷)、二甲基-2,2-偶氮雙 (2-甲基丙酸酯)、4,4’-偶氮雙(4-氰基戊烷酸)、2,2’-偶氮雙[2-(羥基甲基)丙腈]等偶氮系聚合起始劑。作為於本實施形態中之自由基聚合起始劑,可單獨使用這些中的1種,亦可組合2種以上使用,更可組合其他公知聚合起始劑而使用。 Further, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile and 1-[(1-cyano-1-methylethyl)azo]carbamamine are mentioned. 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2 , 2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionate) dihydrochloride, 2,2'-azobis ( 2-methyl-N-phenylpropionate hydrazine) dihydrochloride, 2,2'-azobis[N-(4-chlorophenyl)-2-methylpropionate]dihydride chloride , 2,2'-azobis[N-(4-hydrophenyl)-2-methylpropionate]dihydrochloride, 2,2'-azobis[2-methyl-N-( Phenylmethyl)phosphonium propionate]dihydrochloride, 2,2'-azobis[2-methyl-N-(2-propenyl)propionate]dihydrochloride, 2,2'- Azobis[N-(2-hydroxyethyl)-2-methylpropionate]dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2 -yl)propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-( 4,5,6,7-tetrahydro-1H-1,3-dioxan-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(3,4,5 ,6-tetrahydropyrimidin-2-yl)propane] Hydrochloride, 2,2'-azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane]dihydrochloride, 2,2'-azo Bis[2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2- Propyl], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propanamide], 2,2'-even Nitrogen bis[2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propanamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl) Acetylamine], 2,2'-azobis(2-methylpropionamide), 2,2'-azobis(2,4,4-trimethylpentane), 2,2 '-Azobis(2-methylpropane), dimethyl-2,2-azobis(2-methylpropionate), 4,4'-azobis(4-cyanopentanoic acid) An azo polymerization initiator such as 2,2'-azobis[2-(hydroxymethyl)propanenitrile]. As the radical polymerization initiator in the present embodiment, one type of these may be used alone or two or more types may be used in combination, and other known polymerization initiators may be used in combination.

作為前述自由基聚合起始劑之含有量,若為化學量理論上的必要量即可,但將前述下層膜形成材料作為100質量份時,以0.05~25質量份者為佳,以0.1~10質量份者為較佳。自由基聚合起始劑的含有量若為0.05質量份以上時,有著可防止硬化分充分的情況之傾向,另一方面,自由基聚合起始劑的含有量為25質量份以下時,有著可防止在下層膜形成材料之室溫的長期保存安定性損害的傾向。 The content of the radical polymerization initiator is a theoretically necessary amount of the chemical amount. However, when the underlayer film forming material is used as 100 parts by mass, it is preferably 0.05 to 25 parts by mass, and 0.1 to 0.1. 10 parts by mass is preferred. When the content of the radical polymerization initiator is 0.05 parts by mass or more, the curing fraction may be prevented from being sufficient. On the other hand, when the content of the radical polymerization initiator is 25 parts by mass or less, The tendency of long-term storage stability damage at room temperature of the underlayer film forming material is prevented.

[酸產生劑]  [acid generator]  

於本實施形態中之下層膜形成材料由藉由進一步促進藉由熱之交聯反應的等觀點來看,視必要可含有酸產生劑。作為酸產生劑,已知有藉由熱分解產生酸者、藉由光照射產生酸者等,皆可使用。作為酸產生劑,例如可使用記載於國際公開第2013/024779號者。 In the present embodiment, the underlayer film forming material may contain an acid generator as necessary, from the viewpoint of further promoting the crosslinking reaction by heat. As the acid generator, those which generate an acid by thermal decomposition, generate an acid by light irradiation, or the like can be used. As the acid generator, for example, those described in International Publication No. 2013/024779 can be used.

下層膜形成材料中之酸產生劑的含有量並無特別限定,對於下層膜形成材料100質量份而言以0.1~50質量份者為佳,較佳為0.5~40質量份。若將酸產生劑的含有量設定在上述範圍時,有著酸產生量變多而使交聯反 應提高的傾向,又有著與抗蝕層之混雜現象的產生受到抑制的傾向。 The content of the acid generator in the underlayer film forming material is not particularly limited, and is preferably 0.1 to 50 parts by mass, and preferably 0.5 to 40 parts by mass, per 100 parts by mass of the underlayer film forming material. When the content of the acid generator is set to the above range, the amount of acid generated tends to increase, and the crosslinking reaction tends to increase, and the occurrence of a phenomenon of mixing with the resist layer tends to be suppressed.

[鹼性化合物]  [alkaline compound]  

於本實施形態中之下層膜形成材料由可提高保存安定性等觀點來看,亦可含有鹼性化合物。 In the present embodiment, the underlayer film forming material may contain a basic compound from the viewpoint of improving storage stability and the like.

鹼性化合物為欲防止自酸產生劑所產生的微量酸進行交聯反應而扮演的對於酸的淬滅劑之角色。作為如此鹼性化合物,並無特別限定,例如可舉出國際公開第2013/024779號所記載者。 The basic compound is a role as a quencher for an acid which is intended to prevent a trace amount of acid generated from an acid generator from undergoing a crosslinking reaction. The basic compound is not particularly limited, and examples thereof include those described in International Publication No. 2013/024779.

下層膜形成材料中之鹼性化合物的含有量並無特別限定,對於下層膜形成材料100質量份而言,以0.001~2質量份者為佳,較佳為0.01~1質量份。將鹼性化合物的含有量設定在上述範圍時,有著交聯反應不會過度損失下提高保存安定性之傾向。 The content of the basic compound in the underlayer film forming material is not particularly limited, and is preferably 0.001 to 2 parts by mass, and preferably 0.01 to 1 part by mass, based on 100 parts by mass of the underlayer film forming material. When the content of the basic compound is set to the above range, there is a tendency that the crosslinking stability is improved without excessive loss of the crosslinking reaction.

[其他添加劑]  [Other additives]  

又,於本實施形態中之下層膜形成材料在控制藉由熱或光之硬化性的賦予或吸光度的目的下,可含有其他樹脂及/或化合物。作為如此其他樹脂及/或化合物,可舉出萘酚樹脂、二甲苯樹脂萘酚變性樹脂、萘樹脂之酚變性樹脂;聚羥基苯乙烯、二環戊二烯樹脂、(甲基)丙烯酸酯、二甲基丙烯酸酯、三甲基丙烯酸酯、四甲基丙烯酸酯、乙烯基萘、聚苊烯等萘環、菲醌、芴等聯苯基環、噻吩、茚 等含有具有雜原子的雜環之樹脂或未含有芳香族環之樹脂;松香系樹脂、環糊精、金剛烷(聚)醇、三環癸烷(聚)醇及這些衍生物等含有脂環結構之樹脂或化合物等,但並未特別限定於此等。且於本實施形態中之下層膜形成材料為亦可含有公知添加劑。作為公知添加劑,雖未限定於以下,例如可舉出熱及/或光硬化觸媒、聚合禁止劑、難燃劑、填充劑、偶合劑、熱硬化性樹脂、光硬化性樹脂、染料、顏料、增黏劑、滑劑、消泡劑、塗平劑、紫外線吸收劑、界面活性劑、著色劑、非離子系界面活性劑等。 Further, in the present embodiment, the underlayer film forming material may contain other resins and/or compounds for the purpose of controlling the imparting or absorbance by heat or light. Examples of such other resins and/or compounds include naphthol resins, xylene resin naphthol denatured resins, and phenol-modified resins of naphthalene resins; polyhydroxystyrene, dicyclopentadiene resins, and (meth)acrylates; a naphthalene ring such as dimethacrylate, trimethacrylate, tetramethacrylate, vinyl naphthalene or polydecene, biphenyl ring such as phenanthrenequinone or anthracene, thiophene or anthracene containing a heterocyclic ring having a hetero atom a resin or a resin not containing an aromatic ring; a rosin-based resin, a cyclodextrin, an adamantane (poly) alcohol, a tricyclodecane (poly)ol, and a resin or a compound containing an alicyclic structure, etc., but It is not particularly limited to this. Further, in the present embodiment, the underlayer film forming material may contain a known additive. The known additive is not limited to the following, and examples thereof include heat and/or photo-curing catalyst, polymerization inhibitor, flame retardant, filler, coupling agent, thermosetting resin, photocurable resin, dye, and pigment. , tackifiers, slip agents, defoamers, leveling agents, UV absorbers, surfactants, colorants, nonionic surfactants, etc.

[光刻用下層膜及多層抗蝕圖型之形成方法]  [Formation method of underlayer film for lithography and multilayer resist pattern]  

於本實施形態中之光刻用下層膜係由上述下層膜形成材料所形成。 The underlayer film for lithography in the present embodiment is formed of the underlayer film forming material.

又,本實施形態之抗蝕圖型形成方法係含有使用上述組成物於基板上形成下層膜,於前述下層膜上形成至少1層光阻層後,於前述光阻層所定區域照射放射線,進行顯像之步驟。更詳細為含有於基板上使用本實施形態之下層膜形成材料形成下層膜之步驟(A-1)、於前述下層膜上形成至少1層光阻層的步驟(A-2)與在前述(A-2)步驟後,於前述光阻層的所定區域照射放射線,進行顯像之步驟(A-3)。 Further, in the resist pattern forming method of the present embodiment, the underlayer film is formed on the substrate by using the composition, and at least one photoresist layer is formed on the underlayer film, and then radiation is irradiated on a predetermined region of the photoresist layer. The steps of visualization. More specifically, the step (A-1) of forming the underlayer film using the underlayer film forming material of the present embodiment on the substrate, and the step (A-2) of forming at least one photoresist layer on the underlayer film are as described above. After the step A-2), the radiation is irradiated to a predetermined region of the photoresist layer to perform a development step (A-3).

且,本實施形態之電路圖型形成方法為含有使用上述組成物於基板上形成下層膜,於前述下層膜上使用抗蝕中間層膜材料形成中間層膜,於前述中間層膜上形 成至少1層光阻層的步驟、於前述光阻層的所定區域照射放射線,經顯像形成抗蝕圖型的步驟、將前述抗蝕圖型作為遮罩蝕刻前述中間層膜,將所得之中間層膜圖型作為蝕刻遮罩蝕刻前述下層膜,將所得之下層膜圖型作為蝕刻遮罩,藉由將基板進行蝕刻而於基板形成圖型的步驟。 Further, in the circuit pattern forming method of the present embodiment, the underlayer film is formed on the substrate by using the composition, and the interlayer film is formed on the underlayer film using a resist interlayer film material, and at least one layer is formed on the interlayer film. a step of forming a photoresist layer, irradiating radiation on a predetermined region of the photoresist layer, forming a resist pattern by developing, and etching the intermediate layer film by using the resist pattern as a mask, and obtaining the obtained intermediate layer film The step of etching the underlayer film as an etch mask and using the obtained underlayer film pattern as an etch mask to form a pattern on the substrate by etching the substrate.

更詳細為,具有於基板上使用本實施形態之下層膜形成材料形成下層膜的步驟(B-1)、於前述下層膜上使用含有矽原子之抗蝕中間層膜材料而形成中間層膜的步驟(B-2)、於前述中間層膜上形成至少1層光阻層的步驟(B-3)、於前述步驟(B-3)之後於前述光阻層的所定區域照射放射線,經顯像形成抗蝕圖型的步驟(B-4)與前述步驟(B-4)之後,將前述抗蝕圖型作為遮罩蝕刻前述中間層膜,將所得之中間層膜圖型作為蝕刻遮罩蝕刻前述下層膜,將所得之下層膜圖型作為蝕刻遮罩蝕刻基板後於基板形成圖型之步驟(B-5)。 More specifically, the step (B-1) of forming a lower layer film using the underlayer film forming material of the present embodiment on the substrate, and the use of a resist interlayer film material containing germanium atoms on the underlayer film to form an interlayer film are provided. Step (B-2), a step (B-3) of forming at least one photoresist layer on the intermediate layer film, and irradiating radiation in a predetermined region of the photoresist layer after the step (B-3), After the step (B-4) of forming a resist pattern and the step (B-4), the resist pattern is used as a mask to etch the interlayer film, and the obtained interlayer film pattern is used as an etching mask. The underlayer film is etched, and the obtained underlayer film pattern is used as an etching mask to etch the substrate, and then a step (B-5) is formed on the substrate.

於本實施形態中之光刻用下層膜若為由本實施形態之下層膜形成材料所形成者即可,該形成方法並無特別限定,可適用公知手法。例如將本實施形態的下層膜材料以旋塗或絲網印刷等公知塗佈法或印刷法等賦予基板上後,揮發有機溶劑等而除去,再藉由公知方法使其交聯、硬化,可形成本實施形態之光刻用下層膜。作為交聯方法,可舉出熱硬化、光硬化等手法。 The underlayer film for lithography in the present embodiment is not particularly limited as long as it is formed of the underlayer film forming material of the present embodiment, and a known method can be applied. For example, the underlayer film material of the present embodiment is applied to a substrate by a known coating method such as spin coating or screen printing, or a printing method, and then the organic solvent or the like is removed and removed, and then crosslinked and cured by a known method. The underlayer film for lithography of this embodiment is formed. Examples of the crosslinking method include heat curing and light curing.

於下層膜之形成時,欲抑制與上層抗蝕的混雜現象之產生的同時,亦促進交聯反應時,施予燒烤為佳。此時,燒烤溫度並無特別限定,以80~450℃的範圍內者為佳,較佳為200~400℃。又,燒烤時間並無特別限定,以10~300秒的範圍內者為佳。且,下層膜的厚度可配合要求性能而適宜選定,並無特別限定,通常以30~20,000nm程度者為佳,較佳為50~15,000nm。 In the formation of the underlayer film, it is preferable to apply a barbecue when suppressing the occurrence of a phenomenon of mixing with the upper layer of the resist and also promoting the crosslinking reaction. In this case, the grilling temperature is not particularly limited, and is preferably in the range of 80 to 450 ° C, preferably 200 to 400 ° C. Further, the grilling time is not particularly limited, and it is preferably in the range of 10 to 300 seconds. Further, the thickness of the underlayer film can be appropriately selected in accordance with the required properties, and is not particularly limited, and is usually preferably from 30 to 20,000 nm, preferably from 50 to 15,000 nm.

製作下層膜後,2層製程時,於該上面可製作出含矽的抗蝕層或由一般烴所成的單層抗蝕,3層製程時於該上面製造出含矽的中間層、進一步於該上面製作出未含有矽的單層抗蝕層者為佳。此時,作為使用於形成該抗蝕層時的光阻材料,可使用公知者。 After the underlayer film is formed, in the two-layer process, a resist layer containing ruthenium or a single-layer resist formed of a general hydrocarbon can be formed thereon, and a ruthenium-containing intermediate layer is further formed on the top layer during the three-layer process, and further It is preferred to produce a single-layer resist layer containing no antimony on the upper surface. At this time, as a photoresist used when forming the resist layer, a known one can be used.

於基板上製作下層膜後,2層製程之情況為,於該下層膜上可製作出含有矽之抗蝕層或者由一般烴所成的單層抗蝕。3層製程之情況為,該下層膜上製作出含有矽之中間層,進一步於該含有矽的中間層上製作出未含有矽的單層抗蝕層。對於此等情況,使用於形成抗蝕層之光阻材料可適宜地選自公知者而使用,並無特別限定。 After the underlayer film is formed on the substrate, in the case of the two-layer process, a resist layer containing ruthenium or a single-layer resist formed of a general hydrocarbon can be formed on the underlayer film. In the case of the three-layer process, an intermediate layer containing germanium was formed on the underlayer film, and a single-layer resist layer containing no germanium was further formed on the intermediate layer containing germanium. In such a case, the photoresist material used for forming the resist layer can be suitably selected from known ones, and is not particularly limited.

作為2層製程用之含有矽的抗蝕材料,由氧氣蝕刻耐性的觀點來看,作為基礎聚合物使用聚倍半矽氧烷衍生物或乙烯基矽烷衍生物等含有矽原子之聚合物,進一步使用含有有機溶劑、酸產生劑、視必要含有鹼性化合物等正型光阻材料為佳。其中作為含有矽原子之聚合物,可使用在該種抗蝕材料所使用的公知聚合物。 From the viewpoint of oxygen etching resistance, a resist material containing ruthenium for a two-layer process is a polymer containing a ruthenium atom such as a polysilsesquioxane derivative or a vinyl decane derivative, and further used as a base polymer. It is preferred to use a positive photoresist material containing an organic solvent, an acid generator, and, if necessary, a basic compound. Among them, as the polymer containing a ruthenium atom, a known polymer used for such a resist material can be used.

作為3層製程用之含有矽的中間層,使用聚倍半矽氧烷基底之中間層為佳。藉由於中間層具有作為反射防止膜的效果,有著可有效地抑制反射之傾向。例如對於193nm曝光用製程,使用作為下層膜含有多數芳香族基的基板蝕刻耐性較高材料時,有著k值變高,基板反射變高的傾向,但藉由在中間層抑制反射,可使基板反射在0.5%以下。作為具有如此反射防止效果的中間層,並未限定於以下,但作為193nm曝光用,可使用具有苯基或導入矽-矽鍵的吸光基之在酸或熱下進行交聯的聚倍半矽氧烷者為。 As the intermediate layer containing ruthenium for the three-layer process, it is preferred to use an intermediate layer of a polysilsesquioxane bottom. Since the intermediate layer has an effect as an antireflection film, there is a tendency that reflection can be effectively suppressed. For example, in the case of a 193 nm exposure process, when a substrate having a high degree of etching resistance is used as a substrate containing a large number of aromatic groups, the k value tends to be high and the substrate reflection tends to be high. However, by suppressing reflection in the intermediate layer, the substrate can be made. The reflection is below 0.5%. The intermediate layer having such an antireflection effect is not limited to the following. However, as the 193 nm exposure, a polybenzazole having a phenyl group or a light-absorbing group introduced with a ruthenium-iridium bond may be used to crosslink under acid or heat. Oxygen is for.

又,亦可使用以Chemical Vapour Deposition(CVD)法所形成的中間層。作為在CVD法製作的作為反射防止膜的效果為高之中間層,並無以下之限定,例如已知有SiON膜。一般為藉由CVD法進行旋轉塗佈法或藉由絲網印刷等濕式製程形成中間層時,其為更簡便且有的成本的優點。且,於3層製程中之上層抗蝕可為正型或負型中任一種,又可使用與一般使用的單層抗蝕相同者。 Further, an intermediate layer formed by a Chemical Vapour Deposition (CVD) method can also be used. The intermediate layer having a high effect as an antireflection film produced by the CVD method is not limited to the following. For example, an SiON film is known. Generally, when the intermediate layer is formed by a spin coating method by a CVD method or a wet process such as screen printing, it is an advantage of being simpler and more costly. Moreover, the upper layer resist in the 3-layer process may be either a positive type or a negative type, and the same as the single-layer resist which is generally used.

且於本實施形態中之下層膜可作為一般單層抗蝕用之反射防止膜或抑制圖型傾倒的基底材使用。下層膜因使用於基底加工的蝕刻耐性優良,故亦可期待作為使用於基底加工的硬光罩之功能。 Further, in the present embodiment, the underlayer film can be used as a general antireflection film for single-layer resist or a substrate for suppressing pattern dumping. Since the underlayer film is excellent in etching resistance for use in substrate processing, it is also expected to function as a hard mask for substrate processing.

對於藉由上述光阻材料形成抗蝕層之情況,與形成上述下層膜的情況同樣地,可使用旋轉塗佈法或絲網印刷等濕式製程為佳。又,將抗蝕材料藉由旋轉塗佈法 等進行塗佈後,通常雖進行預烘烤,但該預烘烤係在80~180℃的10~300秒之範圍下進行為佳。其後依據常法進行曝光,藉由進行曝光後燒烤(PEB)、顯像,可得到抗蝕圖型。且,抗蝕膜的厚度並無特別限制,一般以30~500nm為佳,較佳為50~400nm。 In the case where the resist layer is formed of the above-mentioned photoresist material, a wet process such as a spin coating method or a screen printing method can be preferably used as in the case of forming the underlayer film. Further, after the resist material is applied by a spin coating method or the like, it is usually pre-baked, but the prebaking is preferably carried out in the range of 10 to 300 seconds at 80 to 180 °C. Thereafter, exposure is carried out according to a conventional method, and a resist pattern can be obtained by performing post-exposure bake (PEB) and development. Further, the thickness of the resist film is not particularly limited, and is preferably 30 to 500 nm, more preferably 50 to 400 nm.

又,曝光的光可配合所使用的光阻材料而適宜選擇後使用即可。一般為波長300nm以下的高能量線,具體可舉出248nm、193nm、157nm的準分子激光、3~20nm的軟X線、電子束、X線等。 Further, the exposed light can be appropriately selected and used in combination with the photoresist material to be used. Generally, a high-energy line having a wavelength of 300 nm or less is specifically an excimer laser of 248 nm, 193 nm, and 157 nm, a soft X-ray of 3 to 20 nm, an electron beam, an X-ray, or the like.

藉由上述方法所形成的抗蝕圖型成為因下層膜所引起的圖型傾倒受到抑制者。因此,藉由使用於本實施形態中之下層膜,可得到更微細圖型,又欲得到該抗蝕圖型時必須降低必要曝光量。 The resist pattern formed by the above method is suppressed by the pattern dump caused by the underlayer film. Therefore, by using the underlayer film in the present embodiment, a finer pattern can be obtained, and the necessary exposure amount must be reduced in order to obtain the resist pattern.

其此,將所得之抗蝕圖型作為遮罩進行蝕刻。作為2層製程中之下層膜的蝕刻,使用氣蝕刻為佳。作為氣蝕刻,使用氧氣的蝕刻為佳。除氧氣以外,亦可入He、Ar等惰性氣體或CO、CO2、NH3、SO2、N2、NO2、H2氣。又,可未使用氧氣下,僅使用CO、CO2、NH3、N2、NO2、H2氣進行氣蝕刻。特別後者的氣體可使用於欲使圖型側壁之底切(Bottom Off)防止的側壁保護上為佳。 Here, the obtained resist pattern is etched as a mask. As the etching of the underlayer film in the two-layer process, it is preferable to use gas etching. As the gas etching, etching using oxygen is preferred. In addition to oxygen, an inert gas such as He or Ar or CO, CO 2 , NH 3 , SO 2 , N 2 , NO 2 , H 2 gas may be introduced. Further, it is possible to perform gas etching using only CO, CO 2 , NH 3 , N 2 , NO 2 , H 2 gas without using oxygen. In particular, the latter gas may be used for sidewall protection to prevent Bottom Off of the sidewalls of the pattern.

另一方面,對於3層製程中之中間層的蝕刻,使用氣蝕刻為佳。作為氣蝕刻,可適用與上述2層製程中所說明的相同者。換言之,對於3層製程中之中間層的加工以使用氟利昂系氣體使抗蝕圖型遮罩者為佳。其後如上 述將中間層圖型進行遮罩,例如進行氧氣蝕刻,可進行下層膜之加工。 On the other hand, for etching of the intermediate layer in the 3-layer process, it is preferred to use gas etching. As the gas etching, the same as those described in the above two-layer process can be applied. In other words, it is preferable to process the intermediate layer in the three-layer process to use a Freon-based gas to make the resist pattern mask. Thereafter, the intermediate layer pattern is masked as described above, for example, by oxygen etching, and the underlayer film can be processed.

其中,作為中間層形成無機硬光罩中間層膜時,藉由CVD法或ALD法等形成矽氧化膜、矽氮化膜、矽氧化氮化膜(SiON膜)。作為氮化膜的形成方法,雖未限定於以下,例如可使用特開2002-334869號公報(專利文獻6)、WO2004/066377(專利文獻7)所記載的方法。於如此中間層膜的上面可直接形成光阻膜,但於中間層膜的上面將有機反射防止膜(BARC)進行旋塗而形成,於該上面形成光阻膜。 When the inorganic hard mask intermediate layer film is formed as the intermediate layer, a tantalum oxide film, a tantalum nitride film, or a tantalum oxide nitride film (SiON film) is formed by a CVD method, an ALD method, or the like. The method of forming the nitride film is not limited to the following. For example, the method described in JP-A-2002-334869 (Patent Document 6) and WO2004/066377 (Patent Document 7) can be used. A photoresist film can be directly formed on the upper surface of the interlayer film, but an organic anti-reflection film (BARC) is spin-coated on the upper surface of the interlayer film to form a photoresist film thereon.

作為中間層,亦可使用聚倍半矽氧烷基底之中間層。藉由使其具有於抗蝕中間層膜作為反射防止膜的效果,有著可有效地抑制反射的傾向。對於聚倍半矽氧烷基底之中間層的具體材料雖未限定於以下,例如可使用特開2007-226170號(專利文獻8)、特開2007-226204號(專利文獻9)所記載者。 As the intermediate layer, an intermediate layer of a polysilsesquioxane bottom can also be used. By having the effect of using the resist interlayer film as an antireflection film, there is a tendency that reflection can be effectively suppressed. The specific material of the intermediate layer of the poly-sesquiterpoxyalkylene group is not limited to the following, and those described in JP-A-2007-226170 (Patent Document 8) and JP-A-2007-226204 (Patent Document 9) can be used.

又,其次基板蝕刻亦可依據常法進行,例如若基板為SiO2、SiN,可進行將氟利昂系氣作為主體的蝕刻、若為p-Si或Al、W,可進行將氯系、溴系氣作為主體的蝕刻。將基板以氟利昂系氣進行蝕刻時,2層抗蝕製程之含有矽的抗蝕與3層製程的含有矽的中間層與基板加工同時被剝離。另一方面,以氯系或溴系氣蝕刻基板時,含有矽之抗蝕層或含有矽的中間層的剝離另外進行,一般於基板加工後進行藉由氟利昂系氣之乾蝕刻剝離。 Further, the second substrate etching can be carried out according to a conventional method. For example, if the substrate is SiO 2 or SiN, etching with a Freon-based gas as a main component, and if p-Si, Al or W, a chlorine-based or bromine-based system can be used. Gas is etched as the main body. When the substrate is etched with a Freon-based gas, the ruthenium-containing resist of the two-layer resist process and the ruthenium-containing intermediate layer of the three-layer process are simultaneously peeled off from the substrate processing. On the other hand, when the substrate is etched with a chlorine-based or bromine-based gas, the peeling of the resist layer containing ruthenium or the intermediate layer containing ruthenium is performed separately, and generally, after the substrate processing, dry etching by Freon-based gas is performed.

於本實施形態中之下層膜具有優良的基板之蝕刻耐性為特徵者。且作為基板,可適宜地選擇使用公知者,並無特別限定,可舉出Si、α-Si、p-Si、SiO2、SiN、SiON、W、TiN、Al等。又,基板亦可為於基材(支持體)上具有被加工膜(被加工基板)的層合體。作為如此被加工膜,可舉出Si、SiO2、SiON、SiN、p-Si、α-Si、W、W-Si、Al、Cu、Al-Si等種種Low-k膜及其阻擋膜等,通常使用與基材(支持體)相異的材質者。且,成為加工對象之基板或被加工膜厚度並無特別限定,通常以50~10,000nm程度者為佳,較佳為75~5,000nm。 In the present embodiment, the underlayer film is characterized by excellent etching resistance of the substrate. Further, the substrate can be appropriately selected and used, and is not particularly limited, and examples thereof include Si, α-Si, p-Si, SiO 2 , SiN, SiON, W, TiN, and Al. Further, the substrate may be a laminate having a film to be processed (substrate to be processed) on a substrate (support). Examples of such a film to be processed include various Low-k films such as Si, SiO 2 , SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si, and barrier films thereof. Usually, a material different from the substrate (support) is used. Further, the thickness of the substrate to be processed or the film to be processed is not particularly limited, and is usually preferably from 50 to 10,000 nm, preferably from 75 to 5,000 nm.

塗布於本實施形態中之組成物而成的抗蝕永久膜,視必要形成抗蝕圖型後,作為於最終製品亦殘存的永久膜為佳。作為永久膜之具體例子,在半導體裝置關連中,於焊接抗蝕、封裝材、底層填料材、電路元件等封裝接著層或集成電路元件與電路基板之接著層、薄型顯示器關連中可舉出薄膜電晶體保護膜、液晶彩色過濾器保護膜、黑色矩陣、間隔物等。特別由於本實施形態中之組成物所成的永久膜因具有優良的耐熱性或耐濕性故有著藉由昇華成分的污染性較少的非常優良的利點。特別對於顯示材料,成為藉由嚴重污染的畫質劣化較少之兼具高感度、高耐熱、吸濕信頼性的材料。 The resist permanent film to be applied to the composition of the present embodiment is preferably a permanent film remaining in the final product after forming a resist pattern as necessary. As a specific example of the permanent film, in the connection of the semiconductor device, a film may be affixed in the connection of the solder resist, the package material, the underfill material, the circuit component, or the like, or the connection layer of the integrated circuit device and the circuit substrate, and the thin display. A transistor protective film, a liquid crystal color filter protective film, a black matrix, a spacer, and the like. In particular, since the permanent film formed by the composition in the present embodiment has excellent heat resistance or moisture resistance, it has a very excellent advantage in that the contamination of the sublimation component is small. In particular, the display material is a material having high sensitivity, high heat resistance, moisture absorption and reliability, which is less deteriorated by severely contaminated image quality.

將於本實施形態中之組成物使用於抗蝕永久膜用途時,藉由加入硬化劑的其他進一步視必要的其他樹脂、界面活性劑或染料、填充劑、交聯劑、溶解促進劑等 各種添加劑,溶解於有機溶劑,可成為抗蝕永久膜用組成物。 When the composition of the present embodiment is used for a resist permanent film application, other resins, surfactants or dyes, fillers, crosslinking agents, dissolution promoters, etc., which are further necessary depending on the addition of the curing agent, may be used. The additive is dissolved in an organic solvent and can be used as a composition for a resist permanent film.

於本實施形態中之光刻用膜形成組成物或抗蝕永久膜用組成物為,添加上述各成分,藉由使用攪拌機等進行混合而調製。又,於本實施形態中之抗蝕下層膜用組成物或抗蝕永久膜用組成物為含有填充劑或顏料時,使用溶解裝置、均質機、3根輥混合等分散裝置進行分散或者混合而可調製。 In the composition for forming a film for lithography or the composition for a resistive permanent film in the present embodiment, the above components are added and mixed by using a stirrer or the like. In addition, when the composition for a resist underlayer film or the composition for a resist permanent film of the present embodiment contains a filler or a pigment, it is dispersed or mixed by using a dispersing device such as a dissolving device, a homogenizer, or three rolls. Can be modulated.

[實施例]  [Examples]  

以下將本實施形態藉由合成例及實施例做更詳細說明,但本實施形態並未藉由這些例子做任何限定者。 Hereinafter, the present embodiment will be described in more detail by way of Synthesis Examples and Examples, but the present embodiment is not limited by these examples.

(碳濃度及氧濃度)  (carbon concentration and oxygen concentration)  

藉由有機元素分析測定碳濃度及氧濃度(質量%)。 The carbon concentration and the oxygen concentration (% by mass) were determined by organic element analysis.

裝置:CHN塗布器MT-6(Yanako分析工業(股)製) Device: CHN coater MT-6 (Yanako Analytical Industry Co., Ltd.)

(分子量)  (molecular weight)  

化合物的分子量使用Water公司製Acquity UPLC/MALDI-Synapt HDMS,藉由LC-MS分析測定。 The molecular weight of the compound was determined by LC-MS analysis using Acquity UPLC/MALDI-Synapt HDMS manufactured by Water Corporation.

又,以以下條件進行凝膠滲透層析法(GPC)分析,求得聚苯乙烯換算之重量平均分子量(Mw)、數平均分子量(Mn)及分散度(Mw/Mn)。 Further, gel permeation chromatography (GPC) analysis was carried out under the following conditions to obtain a weight average molecular weight (Mw), a number average molecular weight (Mn), and a dispersity (Mw/Mn) in terms of polystyrene.

裝置:Shodex GPC-101型(昭和電工(股)製) Device: Shodex GPC-101 (Showa Denko (share) system)

管柱:KF-80M×3 Column: KF-80M×3

溶離液:THF 1mL/min Dissolved solution: THF 1mL/min

溫度:40℃ Temperature: 40 ° C

(溶解性)  (solubility)  

在23℃,將化合物攪拌溶解至對於丙二醇單甲基醚(PGME)、環己酮(CHN)、乳酸乙酯(EL)、甲基戊基酮(MAK)或四甲基脲(TMU)成為3質量%溶液,將1星期後的結果依據以下基準進行評估。 The compound was stirred and dissolved at 23 ° C to become propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), methyl amyl ketone (MAK) or tetramethyl urea (TMU). The results of 1 week after the 1% by mass solution were evaluated based on the following criteria.

評估A:藉由目視確認在所有溶劑無析出物 Evaluation A: By visual confirmation, no precipitates in all solvents

評估C:藉由目視確認在所有溶劑有析出物 Evaluation C: Confirmation of precipitates in all solvents by visual inspection

(化合物之結構)  (structure of the compound)  

化合物的結構為使用Bruker公司製「Advance600II spectrometer」,在以下條件下進行1H-NMR測定並確認。 The structure of the compound was measured by 1 H-NMR measurement under the following conditions using an "Advance 600 II spectrometer" manufactured by Bruker.

頻率數:400MHz Frequency: 400MHz

溶劑:d6-DMSO Solvent: d6-DMSO

內部標準:TMS Internal standard: TMS

測定溫度:23℃ Measuring temperature: 23 ° C

<合成例1>XBisN-1之合成  <Synthesis Example 1> Synthesis of XBisN-1  

於具備攪拌機、冷卻管及滴定管的內容積100ml之容器中,將2,6-萘二醇(Sigma-Aldrich公司製試藥)3.20g(20mmol)與4-聯苯基羧基醛(三菱瓦斯化學公司 製)1.82g(10mmol)投入30ml甲基異丁基酮,加入95%的硫酸5ml,將反應液在100℃進行6小時攪拌並進行反應。其次濃縮反應液,加入純水50g並析出反應生成物,冷卻至室溫後,進行過濾並分離。將所得之固體物經過濾,使其乾燥後,藉由管柱色譜儀進行分離純化,得到下述式所示目的化合物3.05g。藉由400MHz-1H-NMR確認具有下述式之化學結構。 2,6-naphthalenediol (a reagent manufactured by Sigma-Aldrich Co., Ltd.) 3.20 g (20 mmol) and 4-biphenylcarboxyaldehyde (Mitsubishi Gas Chemistry) in a 100 ml container equipped with a stirrer, a cooling tube and a burette The company made 1.82 g (10 mmol), and added 30 ml of methyl isobutyl ketone, and added 5 ml of 95% sulfuric acid, and the reaction liquid was stirred at 100 ° C for 6 hours to carry out a reaction. Next, the reaction liquid was concentrated, 50 g of pure water was added thereto, and the reaction product was precipitated, and after cooling to room temperature, it was filtered and separated. The obtained solid was filtered, dried, and then purified by column chromatography to give 3.05 g of the desired compound. The chemical structure having the following formula was confirmed by 400 MHz - 1 H-NMR.

1H-NMR:(d-DMSO、內部標準TMS) 1 H-NMR: (d-DMSO, internal standard TMS)

δ(ppm)9.7(2H,O-H)、7.2~8.5(19H,Ph-H)、6.6(1H,C-H) δ (ppm) 9.7 (2H, O-H), 7.2~8.5 (19H, Ph-H), 6.6 (1H, C-H)

且,2,6-萘二醇的取代位置為第1位係由第3位與第4位的質子信號為雙重而得到確認。 Further, the substitution position of 2,6-naphthalenediol was confirmed to be the first position by the proton signal of the third and fourth positions.

<合成例1A>E-XBisN-1之合成  <Synthesis Example 1A> Synthesis of E-XBisN-1  

於具備攪拌機、冷卻管及滴定管的內容積100ml之容器中,將上述式所示化合物(XBisN-1)10g(21mmol)與碳酸 鉀14.8g(107mmol)投入於50ml二甲基甲醯胺,加入乙酸-2-氯乙酯6.56g(54mmol),將反應液在90℃進行12小時攪拌並進行反應。其次,將反應液在冰浴冷卻後析出結晶,進行過濾並分離。繼續於具備攪拌機、冷卻管及滴定管的內容積100ml之容器中,裝入前述結晶40g、甲醇40g、THF100g及24%氫氧化鈉水溶液,將反應液在迴流下進行4小時攪拌並進行反應。其後,在冰浴冷卻,將反應液濃縮並將析出固體物進行過濾,使其乾燥後,藉由管柱色譜儀進行分離純化,得到下述式所示目的化合物5.9g。藉由400MHz-1H-NMR確認具有下述式之化學結構。 10 g (21 mmol) of the compound (XBisN-1) and 14.8 g (107 mmol) of potassium carbonate were added to 50 ml of dimethylformamide in a vessel having a volume of 100 ml of a stirrer, a cooling tube and a burette. 6.56 g (54 mmol) of 2-chloroethyl acetate was added, and the reaction solution was stirred at 90 ° C for 12 hours to carry out a reaction. Next, the reaction liquid was cooled in an ice bath, and crystals were precipitated, filtered, and separated. The container was placed in a container having a volume of 100 ml of a stirrer, a cooling tube, and a burette, and 40 g of the crystal, 40 g of methanol, 100 g of THF, and a 24% aqueous sodium hydroxide solution were placed, and the reaction liquid was stirred under reflux for 4 hours to carry out a reaction. Then, it was cooled in an ice bath, and the reaction liquid was concentrated, and the solid matter was precipitated, filtered, dried, and then separated and purified by column chromatography to obtain 5.9 g of the objective compound of the following formula. The chemical structure having the following formula was confirmed by 400 MHz - 1 H-NMR.

1H-NMR:(d-DMSO、內部標準TMS) 1 H-NMR: (d-DMSO, internal standard TMS)

δ(ppm)8.6(2H,O-H)、7.2~7.8(19H,Ph-H)、6.7(1H,C-H)、4.0(4H,-O-CH2-)、3.8(4H,-CH2-OH) δ (ppm) 8.6 (2H, OH), 7.2 to 7.8 (19H, Ph-H), 6.7 (1H, CH), 4.0 (4H, -O-CH 2 -), 3.8 (4H, -CH 2 -OH )

<合成實施例1-1>AlE-XBisN-1之合成  <Synthesis Example 1-1> Synthesis of AlE-XBisN-1  

於具備攪拌機、冷卻管及滴定管的內容積100ml之容器中,投入將上述式(E-XBisN-1)所示化合物10.3g(21mmol)與碳酸鉀6.2g(45mmol)加入於100ml丙酮的溶液,進一步加入溴化烯丙基5.4(45mmol)g及2.0g的10-冠-6,將所得之反應液在迴流下進行9小時攪拌並進行反應。其次由反應液過濾並除去固體成分,在冰浴冷卻並濃縮反應液而析出固體物。過濾析出之固體物,使其乾燥後,藉由管柱色譜儀進行分離純化,得到下述式(AlE-XBisN-1)所示目的化合物3.2g。 A solution of 10.3 g (21 mmol) of the compound represented by the above formula (E-XBisN-1) and 6.2 g (45 mmol) of potassium carbonate in 100 ml of acetone was placed in a container having a volume of 100 ml of a stirrer, a cooling tube and a burette. Further, bromoallyl 5.4 (45 mmol) g and 2.0 g of 10-crown-6 were added, and the resulting reaction solution was stirred under reflux for 9 hours to carry out a reaction. Next, the reaction mixture was filtered and the solid component was removed, and the reaction mixture was cooled in an ice bath to precipitate a solid. The precipitated solid was filtered, dried, and then separated and purified by column chromatography to obtain 3.2 g of the objective compound of the formula (AlE-XBisN-1).

藉由400MHz-1H-NMR,確認具有下述式(AlE-XBisN-1)之化學結構。 The chemical structure of the following formula (AlE-XBisN-1) was confirmed by 400 MHz- 1 H-NMR.

1H-NMR:(d-DMSO、內部標準TMS) 1 H-NMR: (d-DMSO, internal standard TMS)

δ(ppm)7.2~7.8(19H,Ph-H)、6.7(1H,C-H)、6.1(2H,-CH-CH2)、5.4~5.5(4H,-CH-CH2)、4.7(4H,-O-CH2-)、4.0(4H,-O-CH2-)、3.8(4H,-CH2-OH) δ (ppm) 7.2 to 7.8 (19H, Ph-H), 6.7 (1H, CH), 6.1 (2H, -CH-CH 2 ), 5.4 to 5.5 (4H, -CH-CH 2 ), 4.7 (4H, -O-CH 2 -), 4.0 (4H, -O-CH 2 -), 3.8 (4H, -CH 2 -OH)

對於所得之化合物,藉由前述方法測定分子量的結果為634。 The molecular weight of the obtained compound was determined by the method described above to be 634.

熱分解溫度為390℃,玻璃轉移點為105℃,熔點為205℃,具有高耐熱性被確認。 The thermal decomposition temperature was 390 ° C, the glass transition point was 105 ° C, and the melting point was 205 ° C, and high heat resistance was confirmed.

<合成實施例1-2>AcE-XBisN-1之合成  <Synthesis Example 1-2> Synthesis of AcE-XBisN-1  

取代上述溴化烯丙基,使用丙烯酸以外,進行與合成實施例1-1之同樣反應,得到下述式(AcE-XBisN-1)所示目的化合物4.0g。 In the same manner as in the synthesis of Example 1-1, except for the above-mentioned brominated allyl group, 4.0 g of the objective compound of the following formula (AcE-XBisN-1) was obtained.

藉由400MHz-1H-NMR,確認具有下述式(AcE-XBisN-1)之化學結構。 The chemical structure of the following formula (AcE-XBisN-1) was confirmed by 400 MHz- 1 H-NMR.

1H-NMR:(d-DMSO、內部標準TMS) 1 H-NMR: (d-DMSO, internal standard TMS)

δ(ppm)7.2~7.8(19H,Ph-H)、6.7(1H,C-H)、5.8~6.4(6H,-CH-CH2)、4.0(4H,-O-CH2-)、3.8(4H,-CH2-OH) δ (ppm) 7.2~7.8 (19H, Ph-H), 6.7 (1H, CH), 5.8~6.4 (6H, -CH-CH 2 ), 4.0 (4H, -O-CH 2 -), 3.8 (4H , -CH 2 -OH)

<合成例2>BisF-1之合成  <Synthesis Example 2> Synthesis of BisF-1  

準備具備攪拌機、冷卻管及滴定管之內容積200ml的容器。於該容器中投入4,4-雙酚(東京化成公司製試藥)30g(161mmol)、4-聯苯基醛(三菱瓦斯化學公司製)15g(82mmol)與乙酸丁酯100ml,加入p-甲苯磺酸(關東化學公司製試藥)3.9g(21mmol),調製出反應液。將該反應液在90℃進行3小時攪拌並進行反應。其次,濃縮反應液,加入庚烷50g析出反應生成物,冷卻至室溫後,進行過濾並分離。乾燥藉由過濾所得之固體物後,藉由管柱色譜儀進行分離純化,得到下述式所示目的化合物(BisF-1)5.8g。 A container having a 200 ml internal volume of a stirrer, a cooling tube, and a burette was prepared. Into this container, 30 g (161 mmol) of 4,4-bisphenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 15 g (82 mmol) of 4-biphenylaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and 100 ml of butyl acetate were placed, and p- was added thereto. Toluenesulfonic acid (manufactured by Kanto Chemical Co., Ltd.) was 3.9 g (21 mmol) to prepare a reaction liquid. The reaction solution was stirred at 90 ° C for 3 hours to carry out a reaction. Next, the reaction liquid was concentrated, and 50 g of heptane was added to precipitate a reaction product, which was cooled to room temperature, and then filtered and separated. The solid obtained by filtration was separated and purified by column chromatography to obtain 5.8 g of the objective compound (BisF-1).

且藉由400MHz-1H-NMR發現以下吸收峰,確認具有下述式化學結構。 Further, the following absorption peak was found by 400 MHz - 1 H-NMR, and it was confirmed to have a chemical structure of the following formula.

1H-NMR:(d-DMSO、內部標準TMS) 1 H-NMR: (d-DMSO, internal standard TMS)

δ(ppm)9.4(4H,O-H)、6.8~7.8(22H,Ph-H)、6.2(1H,C-H) δ (ppm) 9.4 (4H, O-H), 6.8~7.8 (22H, Ph-H), 6.2 (1H, C-H)

對於所得之化合物,藉由前述方法測定分子量的結果為536。 The molecular weight of the obtained compound was determined by the above method to be 536.

<合成例2A>  <Synthesis Example 2A>  

於具備攪拌機、冷卻管及滴定管的內容積100ml之容器中,將上述式(BisF-1)所示化合物11.2g(21mmol)、碳酸鉀14.8g(107mmol)投入於50ml二甲基甲醯胺,加入乙酸-2-氯乙酯6.56g(54mmol),將反應液在90℃進行12小時攪拌並進行反應。其次,將反應液在冰浴冷卻後析出結晶,進行過濾並分離。繼續於具備攪拌機、冷卻管及滴定管的內容積100ml之容器中,投入前述結晶40g、甲醇40g、THF100g及24%氫氧化鈉水溶液,將反應液在迴流下進行4小時攪拌並進行反應。其後,在冰浴冷卻,將反應液濃縮並將析出固體物進行過濾,使其乾燥後,藉由管柱色譜儀進行分離純化,得到下述式(E-BisF-1)所示目的化合物5.9g。 11.2 g (21 mmol) of the compound represented by the above formula (BisF-1) and potassium carbonate 14.8 g (107 mmol) were placed in 50 ml of dimethylformamide in a container having a volume of 100 ml of a stirrer, a cooling tube and a burette. 6.56 g (54 mmol) of 2-chloroethyl acetate was added, and the reaction liquid was stirred at 90 ° C for 12 hours to carry out a reaction. Next, the reaction liquid was cooled in an ice bath, and crystals were precipitated, filtered, and separated. Into a vessel having a volume of 100 ml equipped with a stirrer, a cooling tube and a burette, 40 g of the crystal, 40 g of methanol, 100 g of THF and a 24% aqueous sodium hydroxide solution were charged, and the reaction liquid was stirred under reflux for 4 hours to carry out a reaction. Thereafter, the mixture was cooled in an ice bath, and the reaction liquid was concentrated, and the solid matter was precipitated, filtered, dried, and then purified by column chromatography to obtain the objective compound of the formula (E-BisF-1). 5.9g.

藉由400MHz-1H-NMR,確認具有下述式(E-BisF-1)的化學結構。 The chemical structure having the following formula (E-BisF-1) was confirmed by 400 MHz - 1 H-NMR.

1H-NMR:(d-DMSO、內部標準TMS) 1 H-NMR: (d-DMSO, internal standard TMS)

δ(ppm)8.6(4H,O-H)、6.8~7.8(22H,Ph-H)、6.2(1H,C-H)、4.0(8H,-O-CH2-)、3.8(8H,-CH2-OH) δ (ppm) 8.6 (4H, OH), 6.8 to 7.8 (22H, Ph-H), 6.2 (1H, CH), 4.0 (8H, -O-CH 2 -), 3.8 (8H, -CH 2 -OH )

對於所得之化合物,藉由前述方法測定分子量的結果為712。 The molecular weight of the obtained compound was determined by the above method to be 712.

<合成實施例2-1>AlE-BisF-1之合成  <Synthesis Example 2-1> Synthesis of AlE-BisF-1  

取代上述式(E-XBisN-1)所示化合物使用上述式(E-BisF-1)所示化合物以外,進行與合成實施例1-1之同樣反應,得到下述式(AlE-BisF-1)所示目的化合物3.0g。 The compound of the above formula (E-XBisN-1) was used in the same manner as in the synthesis of Example 1-1 except for the compound of the above formula (E-BBisN-1), and the following formula (AlE-BisF-1) was obtained. ) The indicated compound was 3.0 g.

藉由400MHz-1H-NMR,確認具有下述式(AlE-BisF-1)之化學結構。 The chemical structure of the following formula (AlE-BisF-1) was confirmed by 400 MHz- 1 H-NMR.

1H-NMR:(d-DMSO、內部標準TMS) 1 H-NMR: (d-DMSO, internal standard TMS)

δ(ppm)6.8~7.8(22H,Ph-H)、6.2(1H,C-H)、6.1(4H,-CH-CH2)、5.4~5.5(8H,-CH-CH2)、4.7(8H,-O-CH2-)、4.0(8H,-O-CH2-)、3.8(8H,-CH2-OH) δ (ppm) 6.8~7.8 (22H, Ph-H), 6.2 (1H, CH), 6.1 (4H, -CH-CH 2 ), 5.4~5.5 (8H, -CH-CH 2 ), 4.7 (8H, -O-CH 2 -), 4.0 (8H, -O-CH 2 -), 3.8 (8H, -CH 2 -OH)

熱分解溫度為380℃,玻璃轉移點為70℃,熔點為200℃,具有高耐熱性被確認。 The thermal decomposition temperature was 380 ° C, the glass transition point was 70 ° C, and the melting point was 200 ° C, and high heat resistance was confirmed.

對於所得之化合物,藉由前述方法測定分子量的結果為872。 The molecular weight of the obtained compound was determined by the above method to be 872.

<合成實施例2-2>AcE-BisF-1之合成  <Synthesis Example 2-2> Synthesis of AcE-BisF-1  

取代上述式(E-XBisN-1)所示化合物,使用上述式(E-BisF-1)所示化合物,取代溴化烯丙基使用丙烯酸以外,進行與合成實施例1-1之同樣反應,得到下述式(AcE-BisF-1)所示目的化合物3.3g。 The same reaction as in Synthesis Example 1-1 was carried out, except that the compound represented by the above formula (E-XBisN-1) was used, and the compound represented by the above formula (E-BisF-1) was used, and the bromoallyl group was replaced with acrylic acid. 3.3 g of the objective compound represented by the following formula (AcE-BisF-1) was obtained.

藉由400MHz-1H-NMR,確認具有下述式(AcE-BisF-1)的化學結構。 The chemical structure having the following formula (AcE-BisF-1) was confirmed by 400 MHz - 1 H-NMR.

1H-NMR:(d-DMSO、內部標準TMS) 1 H-NMR: (d-DMSO, internal standard TMS)

δ(ppm)6.8~7.8(22H,Ph-H)、6.2(1H,C-H)、5.8~6.4(6H,-CH-CH2)、4.0(8H,-O-CH2-)、3.8(8H,-CH2-OH) δ (ppm) 6.8~7.8 (22H, Ph-H), 6.2 (1H, CH), 5.8~6.4 (6H, -CH-CH 2 ), 4.0 (8H, -O-CH 2 -), 3.8 (8H , -CH 2 -OH)

對於所得之化合物,藉由前述方法測定分子量的結果為928。 The molecular weight of the obtained compound was determined by the method described above to be 928.

熱分解溫度為375℃,玻璃轉移點為65℃,熔點為190℃,具有高耐熱性被確認。 The thermal decomposition temperature was 375 ° C, the glass transition point was 65 ° C, the melting point was 190 ° C, and high heat resistance was confirmed.

<合成例3>BiN-1之合成  <Synthesis Example 3> Synthesis of BiN-1  

對於具備攪拌機、冷卻管及滴定管的內容積300mL的容器,將2-萘酚(Sigma-Aldrich公司製試藥)10g(69.0mmol)在120℃進行熔融後,投入硫酸0.27g,加入4-乙醯聯苯基(Sigma-Aldrich公司製試藥)2.7g(13.8mmol),將內容物在120℃進行6小時攪拌並進行反應,得到反應液。其次於反應液加入N-甲基-2-吡咯啶酮(關東化學股份有限公司製)100mL、純水50mL後,藉由乙酸乙酯進行萃取。其次加入純水使其成為中性為止後進行分液後,進行濃縮後得到溶液。 10 g (69.0 mmol) of 2-naphthol (a reagent manufactured by Sigma-Aldrich Co., Ltd.) was melted at 120 ° C in a container having a volume of 300 mL equipped with a stirrer, a cooling tube, and a burette, and then 0.27 g of sulfuric acid was added thereto, and 4-B was added. 2.7 g (13.8 mmol) of a biphenyl group (manufactured by Sigma-Aldrich Co., Ltd.) was stirred, and the content was stirred at 120 ° C for 6 hours to carry out a reaction to obtain a reaction liquid. Next, 100 mL of N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Ltd.) and 50 mL of pure water were added to the reaction mixture, followed by extraction with ethyl acetate. Next, pure water was added to make it neutral, and liquid separation was carried out, followed by concentration to obtain a solution.

將所得之溶液藉由管柱層析進行分離後,得到下述式(BiN-1)所示目的化合物(BiN-1)1.0g。 The obtained solution was separated by column chromatography to obtain 1.0 g of the objective compound (BiN-1) represented by the following formula (BiN-1).

對於所得之化合物(BiN-1),藉由上述方法測定分子量之結果為466。 The molecular weight of the obtained compound (BiN-1) was determined by the above method to be 466.

對於所得之化合物(BiN-1),以上述測定條件下,進行NMR測定後,發現以下吸收峰,確認具有下述式(BiN-1)之化學結構。 The obtained compound (BiN-1) was subjected to NMR measurement under the above-mentioned measurement conditions, and the following absorption peak was observed, and the chemical structure of the following formula (BiN-1) was confirmed.

δ(ppm)9.69(2H,O-H)、7.01~7.67(21H,Ph-H)、2.28(3H,C-H) δ (ppm) 9.69 (2H, O-H), 7.01~7.67 (21H, Ph-H), 2.28 (3H, C-H)

<合成例3A>E-BiN-1之合成  <Synthesis Example 3A> Synthesis of E-BiN-1  

於具備攪拌機、冷卻管及滴定管的內容積100ml之容器中,將上述式所示化合物(BiN-1)10.5g(21mmol)與碳酸鉀14.8g(107mmol)投入50ml二甲基甲醯胺,加入乙酸-2-氯乙酯6.56g(54mmol),將反應液在90℃進行12小時攪拌並進行反應。其次,將反應液在冰浴冷卻後析出結晶,進行過濾並分離。繼續於具備攪拌機、冷卻管及滴定管的內容 積100ml之容器中,投入前述結晶40g、甲醇40g、THF100g及24%氫氧化鈉水溶液,將反應液在迴流下進行5小時攪拌並進行反應。其後,在冰浴冷卻,將反應液濃縮並將析出固體物進行過濾,使其乾燥後,藉由管柱色譜儀進行分離純化,得到下述式所示目的化合物4.6g。藉由400MHz-1H-NMR確認具有下述式之化學結構。 10.5 g (21 mmol) of the compound (BiN-1) of the above formula and 14.8 g (107 mmol) of potassium carbonate were added to 50 ml of dimethylformamide in a container having a volume of 100 ml of a stirrer, a cooling tube and a burette. 6.56 g (54 mmol) of 2-chloroethyl acetate was added, and the reaction solution was stirred at 90 ° C for 12 hours to carry out a reaction. Next, the reaction liquid was cooled in an ice bath, and crystals were precipitated, filtered, and separated. The container was charged with 40 g of the above-mentioned crystals, 40 g of methanol, 100 g of THF, and 24% aqueous sodium hydroxide solution, and the reaction liquid was stirred under reflux for 5 hours to carry out a reaction. Then, the reaction mixture was cooled in an ice bath, and the reaction mixture was concentrated, and the solid was precipitated, filtered, dried, and then purified by column chromatography to obtain 4.6 g of the objective compound of the formula. The chemical structure having the following formula was confirmed by 400 MHz - 1 H-NMR.

1H-NMR:(d-DMSO、內部標準TMS) 1 H-NMR: (d-DMSO, internal standard TMS)

δ(ppm)8.6(2H,O-H)、7.2~7.8(19H,Ph-H)、6.7(1H,C-H)、4.0(4H,-O-CH2-)、3.8(4H,-CH2-OH) δ (ppm) 8.6 (2H, OH), 7.2 to 7.8 (19H, Ph-H), 6.7 (1H, CH), 4.0 (4H, -O-CH 2 -), 3.8 (4H, -CH 2 -OH )

<合成實施例3-1>AlE-BiN-1之合成  <Synthesis Example 3-1> Synthesis of AlE-BiN-1  

於具備攪拌機、冷卻管及滴定管的內容積100ml之容器中,投入將上述式(E-BiN-1)所示化合物12.3g(21mmol)與碳酸鉀6.2g(45mmol)加入於100ml丙酮的溶液溶液,再加入溴化烯丙基5.4g(45mmol)及10-冠-6之2.0g,將所得之 反應液在迴流下進行7小時攪拌並進行反應。其次由反應液過濾並除去固體成分,在冰浴冷卻並濃縮反應液而析出固體物。過濾析出之固體物,使其乾燥後,藉由管柱色譜儀進行分離純化,得到下述式(AlE-BiN-1)所示目的化合物4.0g。 A solution of 12.3 g (21 mmol) of the compound of the above formula (E-BiN-1) and 6.2 g (45 mmol) of potassium carbonate in 100 ml of acetone was placed in a container having a volume of 100 ml of a stirrer, a cooling tube and a burette. Further, 5.4 g (45 mmol) of allylic bromopropyl group and 2.0 g of 10-crown-6 were further added, and the obtained reaction liquid was stirred under reflux for 7 hours to carry out a reaction. Next, the reaction mixture was filtered and the solid component was removed, and the reaction mixture was cooled in an ice bath to precipitate a solid. The precipitated solid was filtered, dried, and then separated and purified by column chromatography to obtain 4.0 g of the objective compound of the formula (AlE-BiN-1).

藉由400MHz-1H-NMR,確認具有下述式(AlE-BiN-1)之化學結構。 The chemical structure of the following formula (AlE-BiN-1) was confirmed by 400 MHz- 1 H-NMR.

1H-NMR:(d-DMSO、內部標準TMS) 1 H-NMR: (d-DMSO, internal standard TMS)

δ(ppm)7.2~7.8(19H,Ph-H)、6.7(1H,C-H)、6.1(2H,-CH-CH2)、5.4~5.5(4H,-CH-CH2)、4.7(4H,-O-CH2-)、4.0(4H,-O-CH2-)、3.8(4H,-CH2-OH) δ (ppm) 7.2 to 7.8 (19H, Ph-H), 6.7 (1H, CH), 6.1 (2H, -CH-CH 2 ), 5.4 to 5.5 (4H, -CH-CH 2 ), 4.7 (4H, -O-CH 2 -), 4.0 (4H, -O-CH 2 -), 3.8 (4H, -CH 2 -OH)

對於所得之化合物,藉由前述方法測定分子量的結果為634。 The molecular weight of the obtained compound was determined by the method described above to be 634.

熱分解溫度為380℃,玻璃轉移點為115℃,熔點為215℃,具有高耐熱性被確認。 The thermal decomposition temperature was 380 ° C, the glass transition point was 115 ° C, and the melting point was 215 ° C, and high heat resistance was confirmed.

<合成實施例3-2>AcE-BiN-1之合成  <Synthesis Example 3-2> Synthesis of AcE-BiN-1  

取代上述溴化烯丙基,使用丙烯酸以外,進行與合成實施例3-1相同反應,得到下述式(AcE-BiN-1)所示目的化合物3.3g。 The same reaction as in Synthesis Example 3-1 was carried out, except that the above-mentioned brominated allyl group was used, and 3.3 g of the objective compound represented by the following formula (AcE-BiN-1) was obtained.

藉由400MHz-1H-NMR,確認具有下述式(AcE-BiN-1)之化學結構。 The chemical structure of the following formula (AcE-BiN-1) was confirmed by 400 MHz- 1 H-NMR.

1H-NMR:(d-DMSO、內部標準TMS) 1 H-NMR: (d-DMSO, internal standard TMS)

δ(ppm)7.2~7.8(19H,Ph-H)、6.7(1H,C-H)、5.8~6.4(6H,-CH-CH2)、4.0(4H,-O-CH2-)、3.8(4H,-CH2-OH) δ (ppm) 7.2~7.8 (19H, Ph-H), 6.7 (1H, CH), 5.8~6.4 (6H, -CH-CH 2 ), 4.0 (4H, -O-CH 2 -), 3.8 (4H , -CH 2 -OH)

對於所得之化合物,藉由前述方法測定分子量的結果為662。 The molecular weight of the obtained compound was determined by the above method to be 662.

熱分解溫度為371℃,玻璃轉移點為102℃,熔點為221℃,具有高耐熱性被確認。 The thermal decomposition temperature was 371 ° C, the glass transition point was 102 ° C, and the melting point was 221 ° C, and high heat resistance was confirmed.

<合成例4>BiP-1之合成  <Synthesis Example 4> Synthesis of BiP-1  

取代2-萘酚使用o-苯基酚以外進行與合成例3同樣反應,得到下述式(BiP-1)所示目的化合物1.0g。 The 2-naphthol was reacted in the same manner as in Synthesis Example 3 except that the o-phenylphenol was used, and 1.0 g of the objective compound represented by the following formula (BiP-1) was obtained.

對於所得之化合物(BiP-1),藉由上述方法測定分子量之結果為466。 The molecular weight of the obtained compound (BiP-1) was determined by the above method to be 466.

對於所得之化合物(BiP-1),在上述測定條件下進行NMR測定後,發現以下吸收峰,確認具有下述式(BiP-1)之化學結構。 The obtained compound (BiP-1) was subjected to NMR measurement under the above-mentioned measurement conditions, and the following absorption peak was observed, and the chemical structure of the following formula (BiP-1) was confirmed.

δ(ppm)9.67(2H,O-H)、6.98~7.60(25H,Ph-H)、2.25(3H,C-H) δ (ppm) 9.67 (2H, O-H), 6.98~7.60 (25H, Ph-H), 2.25 (3H, C-H)

<合成例4A>E-BiP-1之合成  <Synthesis Example 4A> Synthesis of E-BiP-1  

於具備攪拌機、冷卻管及滴定管的內容積100ml之容器中,將上述式(BiP-1)所示化合物11.2g(21mmol)與碳酸鉀14.8g(107mmol)投入50ml二甲基甲醯胺,加入乙酸-2-氯乙酯6.56g(54mmol),將反應液在90℃進行12小時攪拌並 進行反應。其次,將反應液在冰浴冷卻後析出結晶,進行過濾並分離。繼續於具備攪拌機、冷卻管及滴定管的內容積100ml之容器中,投入前述結晶40g、甲醇40g、THF100g及24%氫氧化鈉水溶液,將反應液在迴流下進行4小時攪拌並進行反應。其後,在冰浴冷卻,將反應液濃縮並將析出固體物進行過濾,使其乾燥後,藉由管柱色譜儀進行分離純化,得到下述式(E-BiP-1)所示目的化合物5.9g。 11.2g (21mmol) of the compound of the above formula (BiP-1) and 14.8g (107mmol) of potassium carbonate were added to 50ml of dimethylformamide in a container having a volume of 100 ml of a stirrer, a cooling tube and a burette. 6.56 g (54 mmol) of 2-chloroethyl acetate was added, and the reaction solution was stirred at 90 ° C for 12 hours to carry out a reaction. Next, the reaction liquid was cooled in an ice bath, and crystals were precipitated, filtered, and separated. Into a vessel having a volume of 100 ml equipped with a stirrer, a cooling tube and a burette, 40 g of the crystal, 40 g of methanol, 100 g of THF and a 24% aqueous sodium hydroxide solution were charged, and the reaction liquid was stirred under reflux for 4 hours to carry out a reaction. After that, it was cooled in an ice bath, and the reaction liquid was concentrated, and the solid matter was precipitated, filtered, dried, and then separated and purified by a column chromatography to obtain the objective compound represented by the following formula (E-BiP-1). 5.9g.

藉由400MHz-1H-NMR,確認具有下述式(E-BiP-1)之化學結構。 The chemical structure of the following formula (E-BiP-1) was confirmed by 400 MHz - 1 H-NMR.

1H-NMR:(d-DMSO、內部標準TMS) 1 H-NMR: (d-DMSO, internal standard TMS)

δ(ppm)8.6(4H,O-H)、6.8~7.6(25H,Ph-H)、4.0(4H,-O-CH2-)、3.8(4H,-CH2-OH)、2.2(3H,C-H) δ (ppm) 8.6 (4H, OH), 6.8 to 7.6 (25H, Ph-H), 4.0 (4H, -O-CH 2 -), 3.8 (4H, -CH 2 -OH), 2.2 (3H, CH )

對於所得之化合物,藉由前述方法測定分子量的結果為606。 The molecular weight of the obtained compound was determined by the above method to be 606.

<合成實施例4-1>AlE-BiP-1之合成  <Synthesis Example 4-1> Synthesis of AlE-BiP-1  

取代上述式(E-BiN-1)所示化合物使用上述式(E-BiP-1)所示化合物以外進行與合成實施例3-1的同樣反應,得到下述式(AlE-BiP-1)所示目的化合物3.0g。 The compound of the above formula (E-BiN-1) was used in the same manner as in the synthesis of Example 3-1 except for the compound of the above formula (E-BiP-1), and the following formula (AlE-BiP-1) was obtained. The indicated compound was 3.0 g.

藉由400MHz-1H-NMR,確認具有下述式(AlE-BiP-1)之化學結構。 The chemical structure of the following formula (AlE-BiP-1) was confirmed by 400 MHz- 1 H-NMR.

1H-NMR:(d-DMSO、內部標準TMS) 1 H-NMR: (d-DMSO, internal standard TMS)

δ(ppm)6.8~7.8(25H,Ph-H)、6.1(4H,-CH-CH2)、5.4~5.5(4H,-CH-CH2)、4.7(4H,-O-CH2-)、4.0(4H,-O-CH2-)、3.8(4H,-CH2-OH)、2.2(3H,C-H) δ (ppm) 6.8~7.8 (25H, Ph-H), 6.1 (4H, -CH-CH 2 ), 5.4~5.5 (4H, -CH-CH 2 ), 4.7 (4H, -O-CH 2 -) , 4.0(4H,-O-CH 2 -), 3.8(4H,-CH 2 -OH), 2.2(3H,CH)

熱分解溫度為390℃,玻璃轉移點為74℃,熔點為202℃,具有高耐熱性被確認。 The thermal decomposition temperature was 390 ° C, the glass transition point was 74 ° C, the melting point was 202 ° C, and high heat resistance was confirmed.

對於所得之化合物,藉由前述方法測定分子量的結果為686。 The molecular weight of the obtained compound was determined by the above method to be 686.

<合成實施例4-2>AcE-BiP-1之合成  <Synthesis Example 4-2> Synthesis of AcE-BiP-1  

取代上述式(E-XBisN-1)所示化合物使用上述式(E-BiP-1)所示化合物,取代溴化烯丙基使用丙烯酸以外,進行與合成實施例1-1之同樣反應,得到下述式(AcE-BiP-1)所示目的化合物3.8g。 The compound represented by the above formula (E-XBisN-1) is used in the same manner as in the synthesis example 1-1 except that the compound represented by the above formula (E-BiP-1) is used, and the substituted bromoallyl group is made of acrylic acid. The target compound represented by the following formula (AcE-BiP-1) was 3.8 g.

藉由400MHz-1H-NMR,確認具有下述式(AcE-BiP-1)之化學結構。 The chemical structure of the following formula (AcE-BiP-1) was confirmed by 400 MHz - 1 H-NMR.

1H-NMR:(d-DMSO、內部標準TMS) 1 H-NMR: (d-DMSO, internal standard TMS)

δ(ppm)6.8~7.8(25H,Ph-H)、5.8~6.4(3H,-CH-CH2)、4.0(4H,-O-CH2-)、3.8(4H,-CH2-OH)、2.2(3H,C-H)、 δ (ppm) 6.8~7.8 (25H, Ph-H), 5.8~6.4 (3H, -CH-CH 2 ), 4.0 (4H, -O-CH 2 -), 3.8 (4H, -CH 2 -OH) , 2.2 (3H, CH),

對於所得之化合物,藉由前述方法測定分子量的結果為700。 With respect to the obtained compound, the molecular weight was measured by the aforementioned method to be 700.

熱分解溫度為365℃,玻璃轉移點為85℃,熔點為220℃,具有高耐熱性被確認。 The thermal decomposition temperature was 365 ° C, the glass transition point was 85 ° C, and the melting point was 220 ° C, and high heat resistance was confirmed.

(合成例5~17)  (Synthesis Examples 5 to 17)  

將合成例3的原料之2-萘酚(原料1)及4-乙醯聯苯基(原 料2)變更為如表1以外,其他進行與合成例3之同樣反應,得到各目的化合物。 The 2-naphthol (raw material 1) and the 4-ethylbiphenyl (raw material 2) of the raw material of Synthesis Example 3 were changed to the same conditions as in the above-mentioned Example 1, and the same reaction product as in Synthesis Example 3 was carried out to obtain each objective compound.

各目的化合物以1H-NMR鑑定。 Each compound of interest was identified by 1H-NMR.

(合成例18~20)  (Synthesis Examples 18 to 20)  

將合成例3的原料之2-萘酚(原料1)及4-聯苯基醛(原料2)變更如表3所示以外,其他進行與合成例3之同樣反應,得到各目的化合物。 The 2-naphthol (raw material 1) and the 4-biphenylaldehyde (raw material 2) of the raw material of the synthesis example 3 were changed as shown in Table 3, and the same reaction as in the synthesis example 3 was carried out to obtain each objective compound.

各目的化合物以1H-NMR進行鑑定。 Each compound of interest was identified by 1 H-NMR.

(合成例21~22)  (Synthesis Examples 21 to 22)  

將合成例3的原料之2-萘酚(原料1)及4-乙醯聯苯基(原料2)變更如表5所示,除水1.5mL、十二烷基硫醇73mg(0.35mmol)、37%鹽酸2.3g(22mmol)以外將反應溫度變更為55℃,其他與合成例3進行同樣反應,得到各目的化合物。 2-naphthol (raw material 1) and 4-ethylbiphenyl (raw material 2) of the raw material of Synthesis Example 3 were changed as shown in Table 5, and 1.5 mL of water and 73 mg (0.35 mmol) of dodecyl mercaptan were removed. The reaction temperature was changed to 55 ° C except for 2.3 g (23 mmol) of 37% hydrochloric acid, and the same reaction was carried out in the same manner as in Synthesis Example 3 to obtain the objective compound.

各目的化合物藉由1H-NMR進行鑑定。 Each compound of interest was identified by 1 H-NMR.

(合成例5A~22A)  (Synthesis Example 5A to 22A)  

將合成例3A的原料之前述式(BiN-1)所示化合物變更為如表7所示,其他在與合成例3A的同樣條件下進行合成,得到目的化合物。各目的化合物之結構為藉由400MHz-1H-NMR(d-DMSO、內部標準TMS)及LC-MS確認分子量而進行鑑定。 The compound represented by the above formula (BiN-1) of the starting material of Synthesis Example 3A was changed to the same as shown in Table 7, and the other compound was synthesized under the same conditions as in Synthesis Example 3A to give the objective compound. The structure of each compound of interest was identified by confirming the molecular weight by 400 MHz - 1 H-NMR (d-DMSO, internal standard TMS) and LC-MS.

(合成實施例5-1~22-1)  (Synthesis Examples 5-1 to 22-1)  

將合成實施例3-1的原料之前述式(E-BiN-1)所示化合物變更為表7所示,其他在與合成實施例3-1之同樣條件下進行合成,得到各目的物。各化合物之結構以400MHz-1H-NMR(d-DMSO、內部標準TMS)及LC-MS確認分子量並進行鑑定。 The compound of the above formula (E-BiN-1) of the starting material of Synthesis Example 3-1 was changed to the one shown in Table 7, and the other was synthesized under the same conditions as in Synthesis Example 3-1 to obtain each object. The structure of each compound was confirmed by 400 MHz- 1 H-NMR (d-DMSO, internal standard TMS) and LC-MS.

(合成實施例5-2~22-2)  (Synthesis Example 5-2 to 22-2)  

將合成實施例3-2的原料之前述式(E-BiN-1)所示化合物變更為表7所示,其他在與合成實施例3-2之同樣條件下進行合成,得到各目的物。各化合物的結構藉由400MHz-1H-NMR(d-DMSO、內部標準TMS)及LC-MS確認分子量並進行鑑定。 The compound of the above formula (E-BiN-1) of the starting material of Synthesis Example 3-2 was changed to the one shown in Table 7, and the other was synthesized under the same conditions as in Synthesis Example 3-2 to obtain each object. The structure of each compound was confirmed by 400 MHz- 1 H-NMR (d-DMSO, internal standard TMS) and LC-MS.

(合成例23)樹脂(R1-XBisN-1)之合成  (Synthesis Example 23) Synthesis of Resin (R1-XBisN-1)  

準備具備迪姆羅回流冷卻管、溫度計及攪拌翼之可去除底的內容積1L之四口燒瓶。於該四口燒瓶,氮氣流中投入在合成例1所得之化合物(XBisN-1)32.6g(70mmol、三菱瓦斯化學(股)製)、40質量%甲醛水溶液21.0g(作為甲醛280mmol、三菱瓦斯化學(股)製)及98質量%硫酸(關東化學(股)製)0.97mL,在常壓下以100℃使其迴流下進行7小時反應。其後,作為稀釋溶劑將鄰二甲苯(和光純藥工業(股)製試藥特級)180.0g加入於反應液,靜置後,除去下相之水相。且進行中和及水洗,藉由將鄰二甲苯在減壓下餾去,得到褐色固體之樹脂(R1-XBisN-1)34.1g。 A four-necked flask containing an internal volume of 1 D with a Dimro reflux cooling tube, a thermometer and a stirring blade was prepared. Into the four-necked flask, 32.6 g (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 21.0 g of a 40% by mass aqueous formaldehyde solution (manufactured as 280 mmol of formaldehyde, Mitsubishi Gas) were added to the compound (XBisN-1) obtained in Synthesis Example 1 in a nitrogen gas stream. Chemical (manufactured by the company) and 0.97 mL of 98% by mass sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) were reacted under reflux at 100 ° C for 7 hours under normal pressure. Thereafter, 180.0 g of o-xylene (Special grade of Wako Pure Chemical Industries, Ltd.) was added to the reaction liquid as a diluent solvent, and after standing, the aqueous phase of the lower phase was removed. Further, neutralization and water washing were carried out, and o-xylene was distilled off under reduced pressure to give 34.1 g of a brown solid resin (R1-XBisN-1).

所得之樹脂(R1-XBisN-1)為,Mn:1975、Mw:3650、Mw/Mn:1.84。 The obtained resin (R1-XBisN-1) was Mn: 1975, Mw: 3650, and Mw/Mn: 1.84.

(合成例24)樹脂(R2-XBisN-1)之合成  (Synthesis Example 24) Synthesis of Resin (R2-XBisN-1)  

準備具備迪姆羅回流冷卻管、溫度計及攪拌翼之可去除底的內容積1L之四口燒瓶。於該四口燒瓶,氮氣流中投 入在合成例1所得之化合物(XBisN-1)32.6g(70mmol、三菱瓦斯化學(股)製)、4-聯苯基醛50.9g(280mmol、三菱瓦斯化學(股)製)、苯甲醚(關東化學(股)製)100mL及草酸二水合物(關東化學(股)製)10mL,在常壓下以100℃使其迴流下進行7小時反應。其後,作為稀釋溶劑將鄰二甲苯(和光純藥工業(股)製試藥特級)180.0g加入於反應液,靜置後除去下相之水相。且進行中和及水洗,將有機相的溶劑及未反應之4-聯苯基醛在減壓下餾去後得到褐色固體之樹脂(R2-XBisN-2)34.7g。 A four-necked flask containing an internal volume of 1 D with a Dimro reflux cooling tube, a thermometer and a stirring blade was prepared. Into the four-necked flask, 32.6 g (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 4-diphenylaldehyde 50.9 g (280 mmol, Mitsubishi Gas Chemicals) of the compound (XBisN-1) obtained in Synthesis Example 1 was placed in a nitrogen gas stream. 100 mL of anisole (manufactured by Kanto Chemical Co., Ltd.) and 10 mL of oxalic acid dihydrate (manufactured by Kanto Chemical Co., Ltd.) were reacted under reflux at 100 ° C for 7 hours under normal pressure. Thereafter, 180.0 g of o-xylene (Special grade of the reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added to the reaction liquid as a diluent solvent, and after standing, the aqueous phase of the lower phase was removed. After neutralizing and washing with water, the solvent of the organic phase and the unreacted 4-biphenylaldehyde were distilled off under reduced pressure to give a brown solid resin (R2-XBisN-2) 34.7 g.

所得之樹脂(R2-XBisN-1)為Mn:1610、Mw:2567、Mw/Mn:1.59。 The obtained resin (R2-XBisN-1) was Mn: 1610, Mw: 2567, and Mw/Mn: 1.59.

<合成例23A>E-R1-XBisN-1之合成  <Synthesis Example 23A> Synthesis of E-R1-XBisN-1  

於具備攪拌機、冷卻管及滴定管之內容積500ml的容器中,將上述的樹脂(R1-XBisN-1)30g與碳酸鉀29.6g(214mmol)投入於100ml二甲基甲醯胺,加入乙酸-2-氯乙酯13.12g(108mmol),將反應液在90℃進行12小時攪拌並進行反應。其次,將反應液在冰浴冷卻後析出結晶,進行過濾並分離。繼續於具備攪拌機、冷卻管及滴定管的內容積100ml之容器中,投入前述結晶40g、甲醇80g、THF100g及24%氫氧化鈉水溶液,將反應液在迴流下進行4小時攪拌並進行反應。其後,在冰浴冷卻,將反應液濃縮並將析出固體物進行過濾,乾燥後得到褐色固體之樹脂(E-R1-XBisN-1)26.5g。 30 g of the above resin (R1-XBisN-1) and 29.6 g (214 mmol) of potassium carbonate were placed in 100 ml of dimethylformamide and acetic acid-2 was added to a vessel having a volume of 500 ml of a stirrer, a cooling tube and a burette. 13.12 g (108 mmol) of chloroethyl ester, and the reaction liquid was stirred at 90 ° C for 12 hours to carry out a reaction. Next, the reaction liquid was cooled in an ice bath, and crystals were precipitated, filtered, and separated. 40 g of the above-mentioned crystals, 80 g of methanol, 100 g of THF, and a 24% aqueous sodium hydroxide solution were placed in a container having a volume of 100 ml of a stirrer, a cooling tube, and a burette, and the reaction liquid was stirred under reflux for 4 hours to carry out a reaction. Thereafter, the mixture was cooled in an ice-bath, and the reaction mixture was concentrated, and the solid matter was precipitated and filtered, and dried to give 26.5 g of a brown solid resin (E-R1-XBisN-1).

所得之樹脂(E-R1-XBisN-1)為Mn:2176、Mw:3540、Mw/Mn:1.62。 The obtained resin (E-R1-XBisN-1) was Mn: 2176, Mw: 3540, and Mw/Mn: 1.62.

<合成實施例23-1>AlE-R1-XBisN-1之合成  <Synthesis Example 23-1> Synthesis of AlE-R1-XBisN-1  

於具備攪拌機、冷卻管及滴定管之內容積500ml的容器中頭入將上述式(E-R1-XBisN-1)所示化合物30.6g與碳酸鉀12.4g(90mmol)加入於200ml丙酮的溶液,進一步加入溴化烯丙基10.8(90mmol)g及10-冠-6之4.0g,將所得之反應液在迴流下進行9小時攪拌並進行反應。其次由反應液過濾並除去固體成分,在冰浴冷卻並濃縮反應液而析出固體物。過濾析出之固體物,使其乾燥後得到灰色固體之(AlE-R1-XBisN-1)所示樹脂46.2g。 A solution containing 30.6 g of the compound of the above formula (E-R1-XBisN-1) and 12.4 g of potassium carbonate (90 mmol) in 200 ml of acetone was placed in a vessel having a volume of 500 ml of a stirrer, a cooling tube and a burette, and further added. Allyl bromide 10.8 (90 mmol) g and 4.0 g of 10-crown-6 were added, and the obtained reaction liquid was stirred under reflux for 9 hours to carry out a reaction. Next, the reaction mixture was filtered and the solid component was removed, and the reaction mixture was cooled in an ice bath to precipitate a solid. The precipitated solid was filtered and dried to give 46.2 g of a resin (yield of (E.sup.).

所得之樹脂(AlE-R1-XBisN-1)為Mn:2021、Mw:3040、Mw/Mn:1.50。 The obtained resin (AlE-R1-XBisN-1) was Mn: 2021, Mw: 3040, and Mw/Mn: 1.50.

<合成實施例23-2>AcE-R1-XBisN-1之合成  <Synthesis Example 23-2> Synthesis of AcE-R1-XBisN-1  

取代上述溴化烯丙基,使用丙烯酸以外,進行與合成實施例23-1之同樣反應,得到褐色固體之(AcE-R1-XBisN-1)所示樹脂5.0g。 The same procedure as in the synthesis of Example 23-1 was carried out, except that the bromoallyl group was used, to obtain a resin (5.0 g) of a resin (AcE-R1-XBisN-1) as a brown solid.

所得之樹脂(AcE-R1-XBisN-1)為Mn:2476、Mw:3930、Mw/Mn:1.61。 The obtained resin (AcE-R1-XBisN-1) was Mn: 2476, Mw: 3930, and Mw/Mn: 1.61.

<合成例24A>E-R2-XBisN-1之合成  <Synthesis Example 24A> Synthesis of E-R2-XBisN-1  

於具備攪拌機、冷卻管及滴定管的內容積500ml之容 器中,將上述樹脂(R2-XBisN-1)30g與碳酸鉀29.6g(214mmol)投入於100ml二甲基甲醯胺,加入乙酸-2-氯乙酯13.12g(108mmol),將反應液在90℃進行12小時攪拌並進行反應。其次,將反應液在冰浴冷卻後析出結晶,進行過濾並分離。繼續於具備攪拌機、冷卻管及滴定管的內容積100ml之容器中,投入前述結晶40g、甲醇80g、THF100g及24%氫氧化鈉水溶液,將反應液在迴流下進行4小時攪拌並進行反應。其後,在冰浴冷卻,將反應液濃縮並將析出固體物進行過濾,使其乾燥後得到褐色固體之樹脂(E-R2-XBisN-1)22.3g。 30 g of the above resin (R2-XBisN-1) and 29.6 g (214 mmol) of potassium carbonate were placed in 100 ml of dimethylformamide in a vessel having a volume of 500 ml equipped with a stirrer, a cooling tube and a burette, and acetic acid-2- was added thereto. 13.12 g (108 mmol) of chloroethyl ester, and the reaction liquid was stirred at 90 ° C for 12 hours to carry out a reaction. Next, the reaction liquid was cooled in an ice bath, and crystals were precipitated, filtered, and separated. 40 g of the above-mentioned crystals, 80 g of methanol, 100 g of THF, and a 24% aqueous sodium hydroxide solution were placed in a container having a volume of 100 ml of a stirrer, a cooling tube, and a burette, and the reaction liquid was stirred under reflux for 4 hours to carry out a reaction. Thereafter, the mixture was cooled in an ice-bath, and the reaction mixture was concentrated, and the solid matter was precipitated and filtered, and dried to give 22.3 g of a brown solid resin (E-R2-XBisN-1).

所得之樹脂(E-R2-XBisN-1)為Mn:2516、Mw:3960、Mw/Mn:1.62。 The obtained resin (E-R2-XBisN-1) was Mn: 2516, Mw: 3960, and Mw/Mn: 1.62.

<合成實施例24-1>AlE-R2-XBisN-1之合成  <Synthesis Example 24-1> Synthesis of AlE-R2-XBisN-1  

取代上述式(E-R1-XBisN-1)使用上述式(E-R2-XBisN-1)所示化合物30.6g以外,進行與合成實施例23-1之同樣反應,得到灰色固體之(AlE-R2-XBisN-1)所示樹脂36.5g。 In the same manner as in the synthesis example 23-1 except that 30.6 g of the compound of the above formula (E-R2-XBisN-1) was used instead of the above formula (E-R1-XBisN-1), a gray solid (AlE-) was obtained. The resin represented by R2-XBisN-1) was 36.5 g.

所得之樹脂(AlE-R2-XBisN-1)為Mn:2411、Mw:3845、Mw/Mn:1.59。 The obtained resin (AlE-R2-XBisN-1) was Mn: 2411, Mw: 3845, and Mw/Mn: 1.59.

<合成實施例24-2>AcE-R1-XBisN-1之合成  <Synthesis Example 24-2> Synthesis of AcE-R1-XBisN-1  

取代上述溴化烯丙基,使用丙烯酸以外,進行與合成實施例24-1之同樣反應,得到褐色固體之(AcE-R2-XBisN-1)所示樹脂5.0g。 In the same manner as in the synthesis of Example 24-1, except for the above-mentioned bromoallyl propyl group, 5.0 g of a resin (AcE-R2-XBisN-1) was obtained as a brown solid.

所得之樹脂(AcE-R2-XBisN-1)為Mn:2676、Mw:4630、Mw/Mn:1.73。 The obtained resin (AcE-R2-XBisN-1) was Mn: 2676, Mw: 4630, and Mw/Mn: 1.73.

(合成比較例1)  (Synthesis Comparative Example 1)  

準備具有迪姆羅回流冷卻管、溫度計及攪拌翼之可除去底的內容積10L之四口燒瓶。於該四口燒瓶,在氮氣流中,投入1,5-二甲基萘1.09kg(7mol、三菱瓦斯化學(股)製)、40質量%甲醛水溶液2.1kg(作為甲醛28mol、三菱瓦斯化學(股)製)及98質量%硫酸(關東化學(股)製)0.97ml,在常壓下以100℃使其迴流下進行7小時反應。其後作為稀釋溶劑將乙基苯(和光純藥工業(股)製試藥特級)1.8kg加入於反應液,靜置後除去下相之水相。且進行中和及水洗,將乙基苯及未反應的1,5-二甲基萘在減壓下餾去後得到淡褐色固體之二甲基萘甲醛樹脂1.25kg。 A four-necked flask of 10 L in internal volume with a Dymro reflux cooling tube, a thermometer and a stirring blade was prepared. In the four-necked flask, 1.09 kg of 1,5-dimethylnaphthalene (7 mol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 2.1 kg of a 40% by mass aqueous formaldehyde solution were placed in a nitrogen gas stream (as formaldehyde 28 mol, Mitsubishi Gas Chemical ( (manufactured by the company) and 0.97 ml of 98% by mass sulfuric acid (manufactured by Kanto Chemical Co., Ltd.), and reacted under reflux at 100 ° C for 7 hours under normal pressure. Then, 1.8 kg of ethylbenzene (Special grade of the reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added to the reaction liquid as a diluent solvent, and after standing, the aqueous phase of the lower phase was removed. After neutralizing and washing with water, ethylbenzene and unreacted 1,5-dimethylnaphthalene were distilled off under reduced pressure to give 1.25 kg of dimethylnaphthalene formaldehyde resin as a pale brown solid.

所得之二甲基萘甲醛的分子量為Mn:562。 The molecular weight of the obtained dimethylnaphthalene formaldehyde was Mn: 562.

繼續準備具備迪姆羅回流冷卻管、溫度計及攪拌翼之內容積0.5L的四口燒瓶。於該四口燒瓶,在氮氣流下,投入如上述所得之二甲基萘甲醛樹脂100g(0.51mol)與對甲苯磺酸0.05g,升溫至190℃並加熱2小時後並攪拌。其後進一步加入1-萘酚52.0g(0.36mol),升溫至220℃並進行2小時反應。溶劑稀釋後進行中和及水洗,將溶劑在減壓除去後,得到黑褐色固體之變性樹脂(CR-1)126.1g。 Continue to prepare a four-necked flask with a volume of 0.5 L of the Dimro reflux cooling tube, thermometer and stirring wing. Into the four-necked flask, 100 g (0.51 mol) of dimethylnaphthalene formaldehyde resin and 0.05 g of p-toluenesulfonic acid obtained as described above were placed under a nitrogen stream, and the mixture was heated to 190 ° C for 2 hours, and then stirred. Thereafter, 52.0 g (0.36 mol) of 1-naphthol was further added, and the mixture was heated to 220 ° C and reacted for 2 hours. After the solvent is diluted, it is neutralized and washed with water, and the solvent is decompressed. After removal, 126.1 g of a dendritic resin (CR-1) of a dark brown solid was obtained.

所得之樹脂(CR-1)為Mn:885、Mw:2220、 Mw/Mn:4.17。 The obtained resin (CR-1) was Mn: 885, Mw: 2220, and Mw/Mn: 4.17.

(實施例1-1~24-2、比較例1)  (Examples 1-1 to 24-2, Comparative Example 1)  

使用上述合成實施例1-1~24-2所記載的化合物或者樹脂、合成比較例1之CR-1進行溶解度試驗。結果如表8所示。 The solubility test was carried out by using the compound or resin described in the above Synthesis Examples 1-1 to 24-2 and synthesizing CR-1 of Comparative Example 1. The results are shown in Table 8.

又,各調製出如表8所示的組成之光刻用下層膜形成材料。其次將這些光刻用下層膜形成材料在矽基板上進行轉動塗佈後,在240℃進行60秒燒烤,進一步在400℃進行120秒燒烤,製作出各膜厚200nm之下層膜。對於酸產生劑、交聯劑及有機溶劑使用如以下者。 Further, each of the underlayer film forming materials for lithography having the composition shown in Table 8 was prepared. Next, these underlayer film forming materials for lithography were spin-coated on a ruthenium substrate, and then baked at 240 ° C for 60 seconds, and further baked at 400 ° C for 120 seconds to prepare a film having a thickness of 200 nm. The following are used for the acid generator, the crosslinking agent, and the organic solvent.

酸產生劑:綠化學公司製 二第三丁基二苯基碘鎓九氟甲烷磺酸酯(DTDPI) Acid generator: manufactured by Green Chemical Co., Ltd. Di-tert-butyldiphenyliodonium nonafluoromethanesulfonate (DTDPI)

交聯劑:三和化學公司製NicaracMX270(Nicarac) Crosslinking agent: NicaracMX270 (Nicarac) manufactured by Sanwa Chemical Co., Ltd.

有機溶劑:丙二醇單甲基醚乙酸酯乙酸酯(PGMEA) Organic solvent: propylene glycol monomethyl ether acetate acetate (PGMEA)

(實施例25~44)  (Examples 25 to 44)  

又,調製出下述表9所示的各組成之光刻用下層膜形成材料。其次將這些光刻用下層膜形成材料於矽基板上進行轉動塗佈,其後在110℃進行60秒燒烤並除去塗膜之溶劑後,藉由高壓水銀燈,在積分曝光量600mJ/cm2、照射時間20秒下使其硬化,製造出各膜厚200nm之下層膜。對於光自由基聚合起始劑、交聯劑及有機溶劑使用以下者。 Moreover, the underlayer film forming material for lithography of each composition shown in the following Table 9 was prepared. Next, these lithographic underlayer film forming materials are spin-coated on a ruthenium substrate, and then subjected to a microwave grilling at 110 ° C for 60 seconds to remove the solvent of the coating film, and then an integrated exposure amount of 600 mJ/cm 2 by a high pressure mercury lamp. The irradiation time was hardened for 20 seconds, and a film having a thickness of 200 nm or less was produced. The following are used for the photoradical polymerization initiator, the crosslinking agent, and the organic solvent.

自由基聚合起始劑:BASF公司製 IRGACURE184 Free radical polymerization initiator: IRGACURE184 manufactured by BASF

交聯劑: Crosslinker:

(1)三和化學公司製NicaracMX270(Nicarac) (1) NicaracMX270 (Nicarac) manufactured by Sanwa Chemical Co., Ltd.

(2)三菱瓦斯化學製 二烯丙基雙酚A型氰酸酯(DABPA-CN) (2) Mitsubishi Gas Chemicals Diallyl bisphenol A type cyanate (DABPA-CN)

(3)小西化學工業製 二烯丙基雙酚A(BPA-CA) (3) Dixypropyl bisphenol A (BPA-CA) manufactured by Xiaoxi Chemical Industry Co., Ltd.

(4)小西化學工業製 苯並噁嗪(BF-BXZ) (4) Sigma-based chemical industry benzoxazine (BF-BXZ)

(5)日本化藥製 聯苯基芳烷基型環氧樹脂(NC-3000-L) (5) Nippon Chemical Co., Ltd. Biphenyl aralkyl type epoxy resin (NC-3000-L)

有機溶劑:丙二醇單甲基醚乙酸酯乙酸酯(PGMEA) Organic solvent: propylene glycol monomethyl ether acetate acetate (PGMEA)

上述交聯劑的結構如下述式所示。 The structure of the above crosslinking agent is as shown in the following formula.

而在下述所示條件下進行蝕刻試驗,評估蝕刻耐性。評估結果如表8及表9所示。 An etching test was performed under the conditions shown below to evaluate the etching resistance. The evaluation results are shown in Tables 8 and 9.

[蝕刻試驗]  [etching test]  

蝕刻裝置:Samco International公司製RIE-10NR Etching device: RIE-10NR manufactured by Samco International

出力:50W Output: 50W

壓力:20Pa Pressure: 20Pa

時間:2min Time: 2min

蝕刻氣 Etching gas

Ar氣流量:CF4氣流量:O2氣流量=50:5:5(sccm) Ar gas flow: CF 4 gas flow: O 2 gas flow = 50: 5: 5 (sccm)

[蝕刻耐性之評估]  [Evaluation of Etch Resistance]  

蝕刻耐性之評估如以下程序進行。 The evaluation of the etching resistance was carried out as follows.

首先取代化合物(AlE-XBisN-1)使用酚醛清漆(群栄化學公司製PSM4357)以外,與實施例1之同樣條件下,製作出酚醛清漆之下層膜。而將該酚醛清漆之下層膜作為對象,進行上述蝕刻試驗,測定此時的蝕刻速率。 A novolac underlayer film was produced under the same conditions as in Example 1 except that a novolac (PSM 4357 manufactured by Gunchem Chemical Co., Ltd.) was used as the substitution compound (AlE-XBisN-1). On the other hand, the undercoat film of the novolac was subjected to the above etching test, and the etching rate at this time was measured.

其次,將各實施例及比較例1的下層膜作為對象,進行與上述相同蝕刻試驗,測定此時的蝕刻速率。 Next, the underlayer films of the respective Examples and Comparative Example 1 were subjected to the same etching test as described above, and the etching rate at this time was measured.

而將酚醛清漆的下層膜之蝕刻速率作為基準,以以下評估基準評估蝕刻耐性。 On the basis of the etching rate of the underlayer film of the novolac, the etching resistance was evaluated on the following evaluation criteria.

[評估基準]  [Evaluation Benchmark]  

A:與酚醛清漆之下層膜相比,蝕刻速率為未達-10% A: The etching rate is less than -10% compared with the film under the novolac

B:與酚醛清漆之下層膜相比,蝕刻速率為-10%~+5% B: The etching rate is -10% to +5% compared to the film under the novolac

C:與酚醛清漆之下層膜相比,蝕刻速率為超過+5% C: The etching rate is more than +5% compared to the film under the novolac

(實施例45~48)  (Examples 45 to 48)  

其次將含有AlE-XBisN-1、AcE-XBisN-1、AlE-BisF-1或AcE-BisF-1的光刻用下層膜形成材料之各溶液塗布於膜厚300nm之SiO2基板上,在240℃進行60秒燒烤,進一步在400℃進行120秒燒烤後,形成膜厚70nm之下層膜。於該下層膜上塗布ArF用抗蝕溶液,藉由在130℃進行60秒燒烤後,形成膜厚140nm之光阻層。且,作為ArF抗蝕溶液,使用添加下述式(11)之化合物:5質量份、三苯基硫鎓九 氟甲烷磺酸酯:1質量份、三丁基胺:2質量份及PGMEA:92質量份所調製者。 Next, each solution of the underlayer film forming material for lithography containing AlE-XBisN-1, AcE-XBisN-1, AlE-BisF-1 or AcE-BisF-1 was applied onto a SiO 2 substrate having a thickness of 300 nm, at 240 The mixture was baked for 60 seconds at ° C, and further baked at 400 ° C for 120 seconds to form a film having a film thickness of 70 nm. A resist solution for ArF was applied onto the underlayer film, and after baking at 130 ° C for 60 seconds, a photoresist layer having a film thickness of 140 nm was formed. Further, as the ArF resist solution, a compound to which the following formula (11) is added: 5 parts by mass, triphenylsulfonium nonafluoromethanesulfonate: 1 part by mass, tributylamine: 2 parts by mass, and PGMEA: 92 parts by mass of the modulator.

式(11)的化合物係將2-甲基-2-甲基丙烯醯氧金剛烷4.15g、甲基丙烯醯氧基-γ-丁內酯3.00g、3-羥基-1-金剛烷基甲基丙烯酸酯2.08g、偶氮二異丁腈0.38g溶解於四氫呋喃80mL中作為反應溶液。將該反應溶液在氮環境下將反應溫度保持在63℃,進行22小時聚合後,將反應溶液滴入400ml的N-己烷中。將如此所得之生成樹脂進行凝固純化,將生成的白色粉末經過濾並在減壓下於40℃進行一晚乾燥而得。 The compound of the formula (11) is 4-methyl-2-methylpropenyl adamantane 4.15 g, methacryloxy-γ-butyrolactone 3.00 g, 3-hydroxy-1-adamantyl group 2.08 g of acrylate and 0.38 g of azobisisobutyronitrile were dissolved in 80 mL of tetrahydrofuran as a reaction solution. The reaction solution was kept at 63 ° C under a nitrogen atmosphere, and after polymerization for 22 hours, the reaction solution was dropped into 400 ml of N-hexane. The resulting resin thus obtained was subjected to solidification purification, and the resulting white powder was filtered and dried under reduced pressure at 40 ° C overnight.

上述式(11)中,40、40、20係表示各構成單位之比率者,非表示嵌段共聚物。 In the above formula (11), 40, 40, and 20 represent the ratio of each constituent unit, and do not represent a block copolymer.

其次,使用電子線繪畫裝置(Ellionics公司製;ELS-7500,50keV),使光阻層曝光,在115℃進行90秒燒烤(PEB),藉由以2.38質量%四甲基銨氫氧化物(TMAH)水溶液進行60秒顯像後得到正型抗蝕圖型。 Next, an electron beam painting apparatus (ELS-7500, 50 keV) was used to expose the photoresist layer, and a 90 second barbecue (PEB) was performed at 115 ° C by using 2.38 mass % tetramethylammonium hydroxide ( The TMAH aqueous solution was subjected to 60 second development to obtain a positive resist pattern.

觀察所得之55nmL/S(1:1)及80nmL/S(1:1)的 抗蝕圖型之形狀及缺陷。 The shape and defects of the obtained resist pattern of 55 nmL/S (1:1) and 80nmL/S (1:1) were observed.

對於顯像後之抗蝕圖型的形狀,若為非圖型傾倒,具有良好矩形性者評估為「良好」,此以外者評估為「不良」。又,前述觀察結果將無圖型傾倒,矩形性為良好的最小線寬作為「解像性」,作為評估指標。且,將良好圖型形狀可繪畫之最小電子線能量做「感度」,作為評估之指標。評估結果如表10所示。 For the shape of the resist pattern after development, if it is a non-pattern, the person with good rectangularity is evaluated as "good", and the others are evaluated as "poor". Further, the observation result is that the pattern is not dumped, and the squareness is a good minimum line width as "resolution" and is used as an evaluation index. Moreover, the minimum electron beam energy that can be drawn by a good figure shape is used as a "sensitivity" as an indicator of evaluation. The evaluation results are shown in Table 10.

(比較例2)  (Comparative Example 2)  

除不進行下層膜之形成以外,與實施例45同樣地,將光阻層於SiO2基板上直接形成,得到正型抗蝕圖型。結果如表10所示。 A photoresist layer was directly formed on the SiO 2 substrate in the same manner as in Example 45 except that the underlayer film was not formed, and a positive resist pattern was obtained. The results are shown in Table 10.

如表8所示,確認在使用於本實施形態中之化合物或者樹脂的實施例1-1~24-2中,耐熱性、溶解度及 蝕刻耐性中任一點皆為良好。一方面,使用CR-1(酚變性二甲基萘甲醛樹脂)的比較例1中,蝕刻耐性為不良。 As shown in Table 8, it was confirmed that in Examples 1-1 to 24-2 used in the compound or resin of the present embodiment, any of heat resistance, solubility, and etching resistance was good. On the other hand, in Comparative Example 1 using CR-1 (phenol-denatured dimethylnaphthalene formaldehyde resin), the etching resistance was poor.

又,對於實施例45~48,確認顯像後之抗蝕圖型形狀為良好,亦未見到缺陷。與省略下層膜之形成的比較例2相比,確認解像性及感度皆顯著優良。 Further, in Examples 45 to 48, it was confirmed that the shape of the resist pattern after development was good, and no defects were observed. Compared with Comparative Example 2 in which the formation of the underlayer film was omitted, it was confirmed that the resolution and the sensitivity were remarkably excellent.

由顯像後之抗蝕圖型形狀的相異性來看,對於實施例45~48中所使用的光刻用下層膜形成材料顯示與抗蝕材料之密著性良好。 From the viewpoint of the dissimilarity of the resist pattern shape after development, the underlayer film forming materials for lithography used in Examples 45 to 48 showed good adhesion to the resist material.

<實施例49~52>  <Examples 49 to 52>  

將實施例1-1~2-2的光刻用下層膜形成材料之溶液塗布於膜厚300nm之SiO2基板上,在240℃進行60秒燒烤,進一步在400℃進行120秒燒烤後,形成膜厚80nm之下層膜。於該下層膜上塗布含有矽的中間層材料,在200℃進行60秒燒烤後,形成膜厚35nm之中間層膜。進一步在該中間層膜上塗布前述ArF用抗蝕溶液,在130℃進行60秒燒烤後,形成膜厚150nm之光阻層。且,作為含有矽的中間層材料,使用特開2007-226170號公報<合成例1>所記載的含有矽原子之聚合物。 The solutions of the underlayer film forming materials for lithography of Examples 1-1 to 2-2 were applied onto a SiO 2 substrate having a thickness of 300 nm, baked at 240 ° C for 60 seconds, and further baked at 400 ° C for 120 seconds to form a solution. The film is under a film thickness of 80 nm. An intermediate layer material containing ruthenium was applied onto the underlayer film, and after baking at 200 ° C for 60 seconds, an interlayer film having a film thickness of 35 nm was formed. Further, the ArF resist solution was applied onto the interlayer film, and after baking at 130 ° C for 60 seconds, a photoresist layer having a film thickness of 150 nm was formed. Further, as the intermediate layer material containing ruthenium, a polymer containing a ruthenium atom described in <Synthesis Example 1> of JP-A-2007-226170 is used.

其次使用電子線繪畫裝置(Ellionics公司製;ELS-7500,50keV),將光阻層進行遮罩曝光,在115℃進行90秒燒烤(PEB),以2.38質量%四甲基銨氫氧化物(TMAH)水溶液進行60秒顯像後得到55nmL/S(1:1)之正型抗蝕圖型。 Next, using an electron beam drawing apparatus (ELS-7500, 50 keV manufactured by Ellionics Co., Ltd.), the photoresist layer was subjected to mask exposure, and a 90 second barbecue (PEB) was performed at 115 ° C to obtain 2.38 mass % tetramethylammonium hydroxide ( The TMAH) aqueous solution was subjected to 60 second development to obtain a positive resist pattern of 55 nmL/s (1:1).

其後,使用Samco International公司製RIE-10NR, 將所得之抗蝕圖型作為遮罩進行含有矽的中間層膜(SOG)之乾蝕刻加工,繼續將所得之含有矽的中間層膜圖型作為遮罩的下層膜之乾蝕刻加工與將所得之下層膜圖型作為遮罩之SiO2膜的乾蝕刻加工依序進行。 Thereafter, RIE-10NR manufactured by Samco International Co., Ltd. was used, and the obtained resist pattern was used as a mask to perform dry etching of an interlayer film (SOG) containing ruthenium, and the obtained interlayer film pattern containing ruthenium was continuously used. The dry etching process of the underlying film of the mask and the dry etching process of the SiO 2 film using the obtained underlying film pattern as a mask are sequentially performed.

各蝕刻條件如下述所示。 Each etching condition is as follows.

對抗蝕圖型之抗蝕中間層膜的蝕刻條件 Etching conditions for a resist pattern intermediate resist film

出力:50W Output: 50W

壓力:20Pa Pressure: 20Pa

時間:1min Time: 1min

蝕刻氣 Etching gas

Ar氣流量:CF4氣流量:O2氣流量=50:8:2(sccm) Ar gas flow: CF 4 gas flow: O 2 gas flow = 50: 8: 2 (sccm)

對抗蝕中間膜圖型之抗蝕下層膜的蝕刻條件 Etching conditions of the resist underlayer film of the resist interlayer film pattern

出力:50W Output: 50W

壓力:20Pa Pressure: 20Pa

時間:2min Time: 2min

蝕刻氣 Etching gas

Ar氣流量:CF4氣流量:O2氣流量=50:5:5(sccm) Ar gas flow: CF 4 gas flow: O 2 gas flow = 50: 5: 5 (sccm)

對抗蝕下層膜圖型之SiO2膜的蝕刻條件 Etching conditions for SiO 2 film of resist underlayer film pattern

出力:50W Output: 50W

壓力:20Pa Pressure: 20Pa

時間:2min Time: 2min

蝕刻氣 Etching gas

Ar氣流量:C5F12氣流量:C2F6氣流量:O2氣流量=50:4:3:1(sccm) Ar gas flow: C 5 F 12 gas flow: C 2 F 6 gas flow: O 2 gas flow = 50: 4: 3: 1 (sccm)

[評估]  [assessment]  

將如上述所得之圖型截面(蝕刻後之SiO2膜的形狀)使用(股)日立製作所製電子顯微鏡(S-4800)進行觀察後,確認使用本實施形態之下層膜的實施例在多層抗蝕加工中之蝕刻後的SiO2膜之形狀為矩形,亦未確認到缺陷的良好者。 The cross-section of the pattern (the shape of the SiO 2 film after the etching) obtained as described above was observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd., and it was confirmed that the layer film was used in the multilayer film of the embodiment. The shape of the SiO 2 film after etching in the etching process was a rectangle, and no defect was confirmed.

[實施例53~56]  [Examples 53 to 56]  

使用在前述合成例、及合成實施例所合成的各化合物,以下述表11所示配合調製出光學零件形成組成物。且,表4中之光學零件形成組成物的各成分中,對於酸產生劑、交聯劑、酸擴散抑制劑及溶劑為使用以下者。 Using the respective compounds synthesized in the above Synthesis Examples and Synthesis Examples, the optical component forming compositions were blended as shown in Table 11 below. Further, among the components of the optical component forming composition in Table 4, the following were used for the acid generator, the crosslinking agent, the acid diffusion inhibitor, and the solvent.

酸產生劑:綠化學公司製 二第三丁基二苯基碘鎓九氟甲烷磺酸酯(DTDPI) Acid generator: manufactured by Green Chemical Co., Ltd. Di-tert-butyldiphenyliodonium nonafluoromethanesulfonate (DTDPI)

交聯劑:三和化學公司製NicaracMX270(Nicarac) Crosslinking agent: NicaracMX270 (Nicarac) manufactured by Sanwa Chemical Co., Ltd.

有機溶劑:丙二醇單甲基醚乙酸酯乙酸酯(PGMEA) Organic solvent: propylene glycol monomethyl ether acetate acetate (PGMEA)

[膜形成之評估]  [Evaluation of Membrane Formation]  

將均勻狀態之光學零件形成組成物於清淨矽晶圓上進行轉動塗佈後,在110℃之烤箱中進行預燒烤(prebake:PB),形成厚度1μm之光學零件形成膜。對於調製之光學零件形成組成物,當膜形成為良好時評估為「A」,於所形成的膜有缺陷時評估為「C」。 The optical component forming composition in a uniform state was spin-coated on a clean wafer, and then prebaked (prebake: PB) in an oven at 110 ° C to form an optical component forming film having a thickness of 1 μm. The composition for forming the optical component to be prepared was evaluated as "A" when the film was formed well, and was evaluated as "C" when the film formed was defective.

[折射率及透過率之評估]  [Evaluation of refractive index and transmittance]  

將均勻光學零件形成組成物轉動塗布於清淨矽晶圓上後,在110℃的烤箱中進行PB,形成厚度1μm之膜。對於該膜,以JA Woollam製多入射角分光橢偏儀VASE,測定在25℃中之折射率(λ=589.3nm)。對於所調製的膜,若折射率為1.65以上時評估為「A」,若為1.6以上,未達1.65時評估為「B」,未達1.6時評估為「C」。又,透過率(λ=632.8nm)為90%以上時評估為「A」,未達90%時評估為「C」。 After the uniform optical component forming composition was spin-coated on the cleaned wafer, PB was performed in an oven at 110 ° C to form a film having a thickness of 1 μm. For this film, a refractive index (λ = 589.3 nm) at 25 ° C was measured using a multi-incidence angle spectroscopic ellipsometer VASE manufactured by JA Woollam. The film to be prepared was evaluated as "A" when the refractive index was 1.65 or more, "B" when it was 1.6 or more, and "C" when it was less than 1.6. Further, when the transmittance (λ = 632.8 nm) was 90% or more, it was evaluated as "A", and when it was less than 90%, it was evaluated as "C".

[實施例57~60]  [Examples 57 to 60]  

使用在前述合成實施例所合成的各化合物,以下述表12所示配合調製出抗蝕組成物。且,於表12中之抗蝕組成物的各成分中,對於自由基發生劑、自由基擴散抑制劑及溶劑使用如以下者。 Using the respective compounds synthesized in the above Synthesis Examples, a resist composition was prepared in accordance with the following Table 12. Further, among the components of the resist composition in Table 12, the following are used for the radical generator, the radical diffusion inhibitor, and the solvent.

自由基發生劑:BASF公司製IRGACURE184 Free radical generator: IRGACURE 184 manufactured by BASF

自由基擴散控制劑:BASF公司製IRGACURE1010 Free radical diffusion control agent: IRGACURE1010 manufactured by BASF

有機溶劑:丙二醇單甲基醚乙酸酯乙酸酯(PGMEA) Organic solvent: propylene glycol monomethyl ether acetate acetate (PGMEA)

[評估方法]  [evaluation method]   (1)抗蝕組成物之保存安定性及薄膜形成  (1) Preservation stability and film formation of the resist composition  

抗蝕組成物之保存安定性為做成抗蝕組成物後,在23℃且50%RH下靜置3天,以目視觀察析出的有無而進行評估。對於3天靜置後的抗蝕組成物,均勻溶液而無析出時評估為A,有析出時評估為C。又,將均勻狀態之抗蝕組成物轉動塗布於清淨矽晶圓上後,在110℃之烤箱中進行曝光前燒烤(PB),形成厚度40nm之抗蝕膜。對於作成之抗蝕組成物,薄膜形成為良好時評估為A,所形成的膜上有缺陷者評估為C。 The storage stability of the anticorrosive composition was set to a resist composition, and then allowed to stand at 23 ° C and 50% RH for 3 days, and the presence or absence of precipitation was visually observed. The resist composition after standing for 3 days was evaluated as A when it was a homogeneous solution without precipitation, and as C when it was precipitated. Further, after the resist composition in a uniform state was spin-coated on the cleaned wafer, the pre-exposure bake (PB) was performed in an oven at 110 ° C to form a resist film having a thickness of 40 nm. For the prepared resist composition, when the film was formed to be good, it was evaluated as A, and the formed film was evaluated as C.

(2)抗蝕圖型之圖型評估  (2) Pattern evaluation of resist pattern  

將均勻抗蝕組成物轉動塗布於清淨矽晶圓上後,在110℃的烤箱中進行曝光前燒烤(PB),形成厚度60nm之抗蝕膜。對於所得之抗蝕膜,使用電子線繪畫裝置(ELS-7500、(股)Ellionics公司製),照射50nm、40nm及30nm間隔之1:1的線和空間設定之電子線。於該照射後,將抗蝕膜在個所定溫度下進行90秒加熱,於PGME浸漬60秒進行顯像。其後將抗蝕膜在超純水進行30秒洗淨並乾燥,形成負型抗蝕圖型。對於所形成之抗蝕圖型,將線和空間藉由掃描型電子顯微鏡((股)日立High technology製S-4800)觀 察,藉由抗蝕組成物之電子線照射評估反應性。 After the uniform resist composition was spin-coated on the cleaned wafer, the pre-exposure bake (PB) was performed in an oven at 110 ° C to form a resist film having a thickness of 60 nm. For the obtained resist film, an electron beam drawing device (ELS-7500, manufactured by Ellionics Co., Ltd.) was used to irradiate a line of 1:1 line and space set at intervals of 50 nm, 40 nm, and 30 nm. After the irradiation, the resist film was heated at a predetermined temperature for 90 seconds, and immersed in PGME for 60 seconds for development. Thereafter, the resist film was washed in ultrapure water for 30 seconds and dried to form a negative resist pattern. With respect to the formed resist pattern, the line and the space were observed by a scanning electron microscope (S-4800, manufactured by Hitachi High Technology Co., Ltd.), and the reactivity was evaluated by electron beam irradiation of the resist composition.

感度表示得到圖型時必要之每單位面積的最小能量,依據以下進行評估。 Sensitivity indicates the minimum energy per unit area necessary to obtain a pattern, and is evaluated based on the following.

A:在未達50μC/cm2下得到圖型之情況 A: The case where the pattern is obtained at less than 50 μC/cm 2

C:在50μC/cm2以上得到圖型之情況 C: A case where a pattern is obtained at 50 μC/cm 2 or more

圖型形成為係將所得之圖型形狀以SEM(掃描型電子顯微鏡:Scanning Electron Microscope)進行觀察,並依據以下進行評估。 The pattern was formed by observing the obtained pattern shape by SEM (Scanning Electron Microscope) and evaluating it according to the following.

A:得到矩形圖型之情況 A: The case of getting a rectangular pattern

B:得到幾乎為矩形圖型之情況 B: When you get an almost rectangular pattern

C:得到非矩形圖型之情況 C: The case of obtaining a non-rectangular pattern

如上述,本發明並非僅限定於上述實施形態及實施例者,不脫離該要旨的範圍內,可進一步適宜地變更。 As described above, the present invention is not limited to the above-described embodiments and examples, and may be modified as appropriate without departing from the scope of the invention.

本實施形態的化合物及樹脂為對於安全溶劑的溶解性高,耐熱性及蝕刻耐性為良好,且本實施形態之抗蝕組成物可賦予良好抗蝕圖型形狀。 The compound and the resin of the present embodiment have high solubility in a safe solvent, and are excellent in heat resistance and etching resistance, and the resist composition of the present embodiment can impart a good resist pattern shape.

又,可實現可適用於濕式製程,使用形成耐熱性及蝕 刻耐性優良的光阻下層膜之有用化合物、樹脂及光刻用膜形成組成物。而該光刻用膜形成組成物因使用耐熱性高,溶劑溶解性亦高,具有特定結構之化合物或樹脂,高溫燒烤時之膜的劣化受到抑制,可形成對於氧電漿蝕刻等蝕刻耐性亦優良的抗蝕及下層膜。且,形成下層膜時,因與抗蝕層之密著性亦為優良,故可形成優良的抗蝕圖型。 Further, it is possible to form a composition which can be applied to a wet process and which uses a useful compound for forming a photoresist underlayer film which is excellent in heat resistance and etching resistance, a resin, and a film for lithography. On the other hand, the film forming composition for lithography has a high heat resistance and a high solvent solubility, and has a compound or a resin having a specific structure. The deterioration of the film during high-temperature baking is suppressed, and etching resistance such as oxygen plasma etching can be formed. Excellent corrosion and underlayer film. Further, when the underlayer film is formed, the adhesion to the resist layer is also excellent, so that an excellent resist pattern can be formed.

且由折射率高,又藉由低溫~高溫處理可抑制著色來看,作為各種光學零件形成組成物時亦為有用。 Moreover, it is also useful as a composition for forming various optical components because of its high refractive index and suppression of coloration by low-temperature to high-temperature treatment.

因此,本發明例如可在電氣用絶緣材料、抗蝕用樹脂、半導體用封止樹脂、印刷電路板用接著劑、電氣機器.電子機器.產業機器等搭載的電氣用層合板、電氣機器.電子機器.產業機器等搭載的預浸料之基體樹脂、累積層合板材料、纖維強化塑質用樹脂、液晶顯示板之封止用樹脂、塗料、各種塗布劑、接著劑、半導體用塗布劑、半導體用抗蝕用樹脂、下層膜形成用樹脂、薄膜狀、薄片狀使用以外,對於塑質透鏡(棱鏡透鏡、柱狀透鏡、微透鏡、菲涅爾透鏡、視野角控制透鏡、對比提高透鏡等)、相位差薄膜、電磁波屏蔽用薄膜、棱鏡、光纖、可撓性印刷配線用焊接抗蝕、電鍍抗蝕、多層印刷電路板用層間絶緣膜、感光性光波導路等光學零件等,可廣泛且有效地利用。 Therefore, the present invention can be used, for example, in electrical insulating materials, resist resins, semiconductor sealing resins, adhesives for printed circuit boards, and electrical equipment. Electronic machine. Electrical laminates and electrical equipment installed in industrial equipment. Electronic machine. Base resin, cumulative laminate material, fiber reinforced plastic resin, liquid crystal display panel sealing resin, coating material, various coating agents, adhesives, semiconductor coating agents, and semiconductor anti-resistance For the etching resin, the resin for forming the underlayer film, the film or the sheet, the plastic lens (prism lens, lenticular lens, microlens, Fresnel lens, viewing angle control lens, contrast enhancing lens, etc.), phase Widely and efficiently, such as a poor film, a film for electromagnetic wave shielding, a prism, an optical fiber, a solder resist for a flexible printed wiring, an electroplating resist, an interlayer insulating film for a multilayer printed wiring board, and an optical component such as a photosensitive optical waveguide. use.

本申請案係以2016年7月21日在日本國特許廳所申請的日本專利申請案(日本特願2016-143659號)為基礎者,該內容皆作為參考資料而記載於此。 The present application is based on Japanese Patent Application No. Hei. No. Hei. No. 2016-143659, filed on Jan.

[產業上可利用性]  [Industrial availability]  

本發明係關於於光刻用抗蝕、光刻用下層膜及多層抗蝕用下層膜及光學零件的領域中具有產業上可利用性者。 The present invention relates to an industrially usable person in the field of resist for lithography, underlayer film for lithography, and underlayer film for multilayer resist and optical parts.

Claims (28)

一種下述式(0)所示之化合物,其為 (式(0)中,R Y為氫原子、碳數1~30的烷基或碳數6~30的芳基,R Z為碳數1~60的N價基或單鍵,R T各獨立為可具有取代基之碳數1~30的烷基、可具有取代基之碳數6~30的芳基、可具有取代基之碳數2~30的烯基、可具有取代基之碳數1~30的烷氧基、鹵素原子、硝基、胺基、羧酸基、硫醇基、羥基或羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯酸氧基烷基的1個基所取代的基,前述烷基、前述芳基、前述烯基、前述烷氧基可含有醚鍵、酮鍵或酯鍵,其中R T的至少1個含有羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯酸氧基烷基的1個基所取代的基,X表示氧原子、硫原子或無交聯, m各獨立為0~9的整數,其中m的至少1個為1~9的整數,N為1~4的整數,其中N為2以上的整數時,N個[ ]內的結構式可為相同或相異,r各獨立為0~2的整數)。 a compound represented by the following formula (0), which is (In the formula (0), R Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R Z is an N-valent group or a single bond having 1 to 60 carbon atoms, and each of R T An alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and a carbon which may have a substituent The hydrogen atom of 1 to 30 alkoxy groups, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group is selected from an allyloxyalkyl group, a propyleneoxyalkyl group or a group a group substituted with one group of a hydroxyalkyl group; the alkyl group, the aryl group, the above alkenyl group, and the alkoxy group may have an ether bond, a ketone bond or an ester bond, wherein at least one of R T is contained The hydrogen atom of the hydroxy group is substituted by a group selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacrylic oxyalkyl, and X represents an oxygen atom, a sulfur atom or no crosslinking, m Each of the independent integers is 0 to 9, wherein at least one of m is an integer from 1 to 9, and N is an integer from 1 to 4, wherein when N is an integer of 2 or more, the structural formulas in N [ ] may be the same Or different, r is independently an integer from 0 to 2). 如請求項1之化合物,其中前述式(0)所示化合物為下述式(1)所示化合物; (式(1)中,R 0與前述R Y同義,R 1為碳數1~60的n價基或單鍵,R 2~R 5各獨立為可具有取代基之碳數1~30的烷基、可具有取代基之碳數6~30的芳基、可具有取代基之碳數2~30的烯基、可具有取代基之碳數1~30的烷氧基、鹵素原子、硝基、胺基、羧酸基、硫醇基、羥基或羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯酸氧基烷基的1個基所取代的基,前述烷基、前述芳基、前述 烯基、前述烷氧基可含有醚鍵、酮鍵或酯鍵,其中R 2~R 5的至少1個含有羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯酸氧基烷基的1個基所取代的基,m 2及m 3各獨立為0~8的整數,m 4及m 5各獨立為0~9的整數,但m 2、m 3、m 4及m 5不會同時為0,n為與前述N同義,其中,n為2以上的整數時,N個[ ]內之結構式可為相同或相異,p 2~p 5與前述r同義)。 The compound of claim 1, wherein the compound represented by the above formula (0) is a compound represented by the following formula (1); (In the formula (1), R 0 is synonymous with the above R Y , R 1 is an n-valent group or a single bond having 1 to 60 carbon atoms, and each of R 2 to R 5 is independently a carbon number of 1 to 30 which may have a substituent. An alkyl group, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, and a nitrate a hydrogen atom of a group, an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group is substituted by a group selected from an allyloxyalkyl group, a propyleneoxyalkyl group or an oxyalkyl group of methacrylic acid. The alkyl group, the aforementioned aryl group, the aforementioned alkenyl group, and the alkoxy group may have an ether bond, a ketone bond or an ester bond, wherein at least one hydrogen atom containing a hydroxyl group of R 2 to R 5 is selected from an allyl group. a group substituted with one group of an oxyalkyl group, a propyleneoxyalkyl group or an oxyalkyl group of methacrylic acid, m 2 and m 3 are each independently an integer of 0 to 8, and m 4 and m 5 are each independently 0. An integer of ~9, but m 2 , m 3 , m 4 , and m 5 are not simultaneously 0, and n is synonymous with the above N. When n is an integer of 2 or more, the structural formula of N [ ] may be The same or different, p 2 ~ p 5 is synonymous with the aforementioned r). 如請求項1之化合物,其中前述式(0)所示化合物為下述式(2)所示化合物, (式(2)中,R 0A與前述R Y同義,R 1A為碳數1~60的n A價基或單鍵,R 2A各獨立為可具有取代基的碳數1~30的烷基、可具有取代基的碳數6~30的芳基、可具有取代基的碳數2~30 的烯基、可具有取代基的碳數1~30的烷氧基、鹵素原子、硝基、胺基、羧酸基、硫醇基、羥基或羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯酸氧基烷基的1個基所取代的基,前述烷基、前述芳基、前述烯基、前述烷氧基可含有醚鍵、酮鍵或酯鍵,其中R 2A的至少1個含有羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯酸氧基烷基的1個基所取代的基,n A與前述N同義,其中,n A為2以上的整數時,n A個[ ]內的結構式可為相同或相異,X A表示氧原子、硫原子或無交聯,m 2A各獨立為0~7的整數,但至少1個m 2A為1~7的整數,q A各獨立為0或1)。 The compound of claim 1, wherein the compound represented by the above formula (0) is a compound represented by the following formula (2), (In the formula (2), R 0A is synonymous with the above R Y , R 1A is an n A valent group or a single bond having 1 to 60 carbon atoms, and R 2A is each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent. An aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, and a nitro group. a hydrogen atom of an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group is substituted by one group selected from the group consisting of an allyloxyalkyl group, a propyleneoxyalkyl group or an oxyalkyl group of methacrylic acid group, The alkyl group, the aryl group, the aforementioned alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond or an ester bond, wherein at least one hydrogen atom containing a hydroxyl group of R 2A is selected from an allyloxyalkyl group. a group substituted with one group of a acryloxyalkyl group or an oxyalkyl group of methacrylic acid, and n A is synonymous with the above N. When n A is an integer of 2 or more, the structural formula in n A [ ] may be Is the same or different, X A represents an oxygen atom, a sulfur atom or no cross-linking, m 2A are each independently an integer of 0-7, but at least one m 2A is an integer of 1-7, and q A is independently 0 or 1). 如請求項2之化合物,其中前述式(1)所示化合物為下述式(1-1)所示化合物, (式(1-1)中,R 0、R 1、R 4、R 5、n、p 2~p 5、m 4及m 5與前述同義,R 6~R 7各獨立為可具有取代基的碳數1~30的烷基、可具有取代基的碳數6~30的芳基、可具有取代基的碳數2~30的烯基、鹵素原子、硝基、胺基、羧酸基、硫醇基,R 10~R 11各獨立為選自氫原子或烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯酸氧基烷基的1個基,其中,R 10~R 11的至少1個為選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯酸氧基烷基的1個基,m 6及m 7各獨立為0~7的整數,但,m 4、m 5、m 6及m 7不會同時為0)。 The compound of the above formula (1), which is a compound represented by the following formula (1-1), (In the formula (1-1), R 0 , R 1 , R 4 , R 5 , n, p 2 to p 5 , m 4 and m 5 have the same meanings as defined above, and R 6 to R 7 each independently may have a substituent. An alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, and a carboxylic acid group And a thiol group, each of R 10 to R 11 independently being a group selected from a hydrogen atom or an allyloxyalkyl group, a propyleneoxyalkyl group or an oxyalkyl group of methacrylic acid, wherein R 10 to R At least one of 11 is a group selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacryloxyalkyl, and m 6 and m 7 are each independently an integer of 0 to 7, but m 4 , m 5 , m 6 and m 7 are not simultaneously 0). 如請求項4之化合物,其中前述式(1-1)所示化合物為下述式(1-2)所示化合物, (式(1-2)中,R 0、R 1、R 6、R 7、R 10、R 11、n、p 2~p 5、m 6 及m 7與前述同義,R 8~R 9與前述R 6~R 7同義,R 12~R 13與前述R 10~R 11同義,m 8及m 9各獨立為0~8的整數,但,m 6、m 7、m 8及m 9不會同時為0)。 The compound of claim 4, wherein the compound represented by the above formula (1-1) is a compound represented by the following formula (1-2). (In the formula (1-2), R 0 , R 1 , R 6 , R 7 , R 10 , R 11 , n, p 2 to p 5 , m 6 and m 7 are synonymous with the above, and R 8 to R 9 are R 6 to R 7 are synonymous, R 12 to R 13 are synonymous with R 10 to R 11 , and m 8 and m 9 are each independently an integer of 0 to 8, but m 6 , m 7 , m 8 and m 9 are not Will be 0) at the same time. 如請求項3之化合物,其中前述式(2)所示化合物為下述式(2-1)所示化合物, (式(2-1)中,R 0A、R 1A、n A、q A及X A與前述式(2)中者同義,R 3A各獨立為可具有取代基的碳數1~30的烷基、可具有取代基的碳數6~30的芳基、可具有取代基的碳數2~30的烯基、鹵素原子、硝基、胺基、羧酸基、硫醇基,R 4A各獨立為氫原子或羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯酸氧基烷基的1個基所取代的基,其中R 4A的至少1個為選自烯丙基氧基烷基、丙 烯氧基烷基或甲基丙烯酸氧基烷基的1個基,m 6A各獨立為0~5的整數)。 The compound of claim 3, wherein the compound represented by the above formula (2) is a compound represented by the following formula (2-1). (In the formula (2-1), R 0A , R 1A , n A , q A and X A are synonymous with those in the above formula (2), and each of R 3A is independently an alkyl group having 1 to 30 carbon atoms which may have a substituent. a group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group, and each of R 4A a hydrogen atom independently a hydrogen atom or a hydroxyl group is substituted by one group selected from the group consisting of an allyloxyalkyl group, a propyleneoxyalkyl group or an oxyalkyl methacrylate group, wherein at least one of R 4A is One group selected from the group consisting of allyloxyalkyl groups, acryloxyalkyl groups, and oxyalkyl methacrylates, and m 6A are each independently an integer of 0 to 5). 一種樹脂,其特徵為將如請求項1之化合物作為單體而得者。  A resin characterized by using the compound of claim 1 as a monomer.   如請求項7之樹脂,其為具有下述式(3)所示結構, (式(3)中,L為可具有取代基的碳數1~30的伸烷基、可具有取代基的碳數6~30的伸芳基、可具有取代基的碳數1~30的伸烷氧基或單鍵,前述伸烷基、前述伸芳基、前述伸烷氧基可含有醚鍵、酮鍵或酯鍵,R 0與前述R Y同義,R 1為碳數1~60的n價基或單鍵,R 2~R 5各獨立為可具有取代基的碳數1~30的烷基、 可具有取代基的碳數6~30的芳基、可具有取代基的碳數2~30的烯基、可具有取代基的碳數1~30的烷氧基、鹵素原子、硝基、胺基、羧酸基、硫醇基、羥基或羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯酸氧基烷基的1個基所取代的基,前述烷基、前述芳基、前述烯基、前述烷氧基可含有醚鍵、酮鍵或酯鍵,其中,R 2~R 5的至少1個含有羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯酸氧基烷基的1個基所取代的基,m 2及m 3各獨立為0~8的整數,m 4及m 5各獨立為0~9的整數,但,m 2、m 3、m 4及m 5不會同時為0,R 2~R 5的至少1個為羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯酸氧基烷基的1個基所取代的基)。 The resin of claim 7, which has a structure represented by the following formula (3), (In the formula (3), L is an alkylene group having 1 to 30 carbon atoms which may have a substituent, an extended aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number of 1 to 30 which may have a substituent An alkoxy group or a single bond, the alkylene group, the aforementioned aryl group, the alkoxy group may have an ether bond, a ketone bond or an ester bond, R 0 is synonymous with the aforementioned R Y , and R 1 is a carbon number of 1 to 60. The n valent group or the single bond, and each of R 2 to R 5 is independently a C 1-3 alkyl group which may have a substituent, a C 6 to 30 aryl group which may have a substituent, and a carbon which may have a substituent The number of 2 to 30 alkenyl groups, a substituent having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group may be selected from alkene. a group substituted with one group of a propyloxyalkyl group, a acryloxyalkyl group or an oxyalkyl group of methacrylic acid; the alkyl group, the aryl group, the above alkenyl group, and the alkoxy group may contain an ether bond; a ketone bond or an ester bond, wherein at least one hydrogen atom containing a hydroxyl group of R 2 to R 5 is one base selected from the group consisting of allyloxyalkyl, acryloxyalkyl or methacrylic oxyalkyl The substituted group, m 2 and m 3 are each independently an integer of 0-8 m 4 and m 5 are each independently an integer of 0 to 9, but m 2 , m 3 , m 4 and m 5 are not simultaneously 0, and at least one hydrogen atom of R 2 to R 5 is selected from a hydroxyl group. a group substituted with one group of an allyloxyalkyl group, a acryloxyalkyl group or an oxyalkyl group of methacrylic acid). 如請求項7之樹脂,其為具有下述式(4)所示結構, (式(4)中,L為可具有取代基的碳數1~30的伸烷基、可具有取代基的碳數6~30的伸芳基、可具有取代基的碳數1~30的伸烷氧基或單鍵,前述伸烷基、前述伸芳基、前述伸烷氧基可含有醚鍵、酮鍵或酯鍵,R 0A與前述R Y同義,R 1A為碳數1~30的n A價基或單鍵,R 2A各獨立為可具有取代基的碳數1~30的烷基、可具有取代基的碳數6~30的芳基、可具有取代基的碳數2~30的烯基、可具有取代基的碳數1~30的烷氧基、鹵素原子、硝基、胺基、羧酸基、硫醇基、羥基或羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯酸氧基烷基的1個基所取代的基,前述烷基、前述芳基、前述烯基、前述烷氧基可含有醚鍵、酮鍵或酯鍵,其中,R 2A的至少1個含有羥基的氫原子由選自烯丙基氧基烷基、丙烯氧基烷基或甲基丙烯酸氧基烷基的1個基所取代的基,n A與前述N同義,其中,n A為2以上的整數時,n A個[ ]內的結構式可為相同或相異,X A表示氧原子、硫原子或無交聯,m 2A各獨立為0~7的整數,但至少1個m 2A為1~7的整數,q A各獨立為0或1)。 The resin of claim 7, which has a structure represented by the following formula (4), (In the formula (4), L is an alkylene group having 1 to 30 carbon atoms which may have a substituent, an extended aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number of 1 to 30 which may have a substituent An alkoxy group or a single bond, the alkylene group, the aforementioned aryl group, the alkoxy group may have an ether bond, a ketone bond or an ester bond, R 0A is synonymous with the aforementioned R Y , and R 1A is a carbon number of 1 to 30. n A valent group or single bond, R 2A are each independently a C 1~30 alkyl group which may have a substituent, a 6 to 30 carbon atom which may have a substituent, and a carbon number which may have a substituent 2 The alkenyl group of ~30, the alkoxy group having a carbon number of 1 to 30 which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group is selected from an allyl group. a group substituted with one group of an oxyalkyl group, a propyleneoxyalkyl group or an oxyalkyl group of methacrylic acid, wherein the alkyl group, the aryl group, the aforementioned alkenyl group, and the alkoxy group may have an ether bond or a ketone bond. Or an ester bond, wherein at least one hydrogen atom containing a hydroxyl group of R 2A is substituted by a group selected from the group consisting of an allyloxyalkyl group, a acryloxyalkyl group or an oxyalkyl methacrylate group; n A is synonymous with the aforementioned N, where n A is 2 In the above integer, the structural formulas in n A [ ] may be the same or different, X A represents an oxygen atom, a sulfur atom or no cross-linking, and m 2A are each independently an integer of 0-7, but at least 1 m 2A is an integer from 1 to 7, and q A is independently 0 or 1). 一種組成物,其特徵為含有選自由如請求項1~6中任一項的化合物及如請求項7~9中任一項的樹脂所成群的1 種以上者。  A composition comprising one or more selected from the group consisting of a compound according to any one of claims 1 to 6 and a resin according to any one of claims 7 to 9.   如請求項10之組成物,其中進一步含有溶劑。  The composition of claim 10, further comprising a solvent.   如請求項10或11之組成物,其中進一步含有酸產生劑。  The composition of claim 10 or 11, further comprising an acid generator.   如請求項10或11之組成物,其中進一步含有交聯劑。  The composition of claim 10 or 11, which further comprises a crosslinking agent.   如請求項13之組成物,其中前述交聯劑為選自由酚化合物、環氧化合物、氰酸酯化合物、胺基化合物、苯並噁嗪化合物、三聚氰胺化合物、胍胺化合物、乙二醇脲化合物、脲化合物、異氰酸酯化合物及疊氮化合物所成群的至少1種。  The composition of claim 13, wherein the crosslinking agent is selected from the group consisting of a phenol compound, an epoxy compound, a cyanate compound, an amine compound, a benzoxazine compound, a melamine compound, a guanamine compound, and an ethylene glycol urea compound. At least one of a group of urea compounds, isocyanate compounds, and azide compounds.   如請求項13之組成物,其中前述交聯劑具有至少1個烯丙基。  The composition of claim 13, wherein the aforementioned crosslinking agent has at least one allyl group.   如請求項13之組成物,其中前述交聯劑的含有比例,對於將含有選自由如請求項1~6中任一項之化合物及如請求項7~9中任一項之樹脂所成群的1種以上之組成物的合計質量作為100質量份時,其為0.1~100質量份。  The composition of claim 13, wherein the content ratio of the foregoing crosslinking agent is grouped for a resin which is selected from the group consisting of a compound according to any one of claims 1 to 6 and a resin according to any one of claims 7 to 9 When the total mass of the one or more components is 100 parts by mass, it is 0.1 to 100 parts by mass.   如請求項13之組成物,其中進一步含有交聯促進劑。  The composition of claim 13, which further comprises a crosslinking accelerator.   如請求項17之組成物,其中前述交聯促進劑為選自由胺類、咪唑類、有機膦類、及路易氏酸所成群的至少1種。  The composition of claim 17, wherein the crosslinking accelerator is at least one selected from the group consisting of amines, imidazoles, organic phosphines, and Lewis acids.   如請求項17之組成物,其中前述交聯促進劑的含有比例,對於將含有選自由如請求項1~6中任一項之化合物及如請求項7~9中任一項之樹脂所成群的1種以上之組成物的合計質量為100質量份時,其為0.1~5質量份。  The composition of claim 17, wherein the content ratio of the crosslinking accelerator is a resin which is selected from the group consisting of the compound according to any one of claims 1 to 6 and the resin according to any one of claims 7 to 9 When the total mass of one or more components of the group is 100 parts by mass, it is 0.1 to 5 parts by mass.   如請求項10或11之組成物,其中進一步含有自由基聚合起始劑。  The composition of claim 10 or 11, further comprising a radical polymerization initiator.   如請求項20之組成物,其中前述自由基聚合起始劑為選自由酮系光聚合起始劑、有機過氧化物系聚合起始劑及偶氮系聚合起始劑所成群的至少1種。  The composition of claim 20, wherein the radical polymerization initiator is at least 1 selected from the group consisting of a ketone photopolymerization initiator, an organic peroxide polymerization initiator, and an azo polymerization initiator. Kind.   如請求項20之組成物,其中前述自由基聚合起始劑的含有比例,對於將含有選自由如請求項1~6中任一項之化合物及如請求項7~9中任一項之樹脂所成群的1種以上之組成物的合計質量為100質量份時,其為0.05~25質量份。  The composition of claim 20, wherein the content of the radical polymerization initiator is a resin selected from the group consisting of the compound of any one of claims 1 to 6 and the resin according to any one of claims 7 to 9 When the total mass of the one or more components in the group is 100 parts by mass, it is 0.05 to 25 parts by mass.   如請求項10或11之組成物,其為使用於光刻用膜形成 上。  The composition of claim 10 or 11, which is used for film formation for lithography.   如請求項10或11之組成物,其為使用於抗蝕永久膜形成上。  The composition of claim 10 or 11, which is used for the formation of a permanent film of resist.   如請求項10或11之組成物,其為使用於光學零件形成上。  The composition of claim 10 or 11 is for use in the formation of optical parts.   一種抗蝕圖型形成方法,其特徵為含有使用如請求項23之組成物,於基板上形成光阻層後,於前述光阻層的所定區域照射放射線,進行顯像的步驟。  A method for forming a resist pattern, comprising the step of forming a photoresist layer on a substrate by using the composition of claim 23, irradiating radiation in a predetermined region of the photoresist layer, and performing development.   一種抗蝕圖型形成方法,其特徵為含有使用如請求項23之組成物,於基板上形成下層膜,於前述下層膜上,形成至少1層光阻層後,於前述光阻層的所定區域照射放射線,進行顯像的步驟。  A method for forming a resist pattern, comprising: forming a lower film on a substrate using the composition of claim 23, forming at least one photoresist layer on the underlying film, and determining the photoresist layer The area is irradiated with radiation to perform a development process.   一種電路圖型形成方法,其特徵為含有使用如請求項23之組成物,於基板上形成下層膜,於前述下層膜上使用抗蝕中間層膜材料,形成中間層膜,於前述中間層膜上,形成至少1層光阻層的步驟、於前述光阻層的所定區域照射放射線,經顯像形成抗蝕圖型之步驟、藉由將前述抗蝕圖型作為遮罩,蝕刻前述中間層膜, 將所得之中間層膜圖型作為蝕刻遮罩,蝕刻前述下層膜,將所得之下層膜圖型作為蝕刻遮罩,蝕刻基板後,於基板形成圖型之步驟。  A circuit pattern forming method comprising the steps of: forming a lower film on a substrate using the composition of claim 23, and using a resist intermediate film material on the underlying film to form an intermediate film on the intermediate film a step of forming at least one photoresist layer, irradiating radiation in a predetermined region of the photoresist layer, forming a resist pattern by developing, and etching the interlayer film by using the resist pattern as a mask The obtained interlayer film pattern is used as an etching mask, and the underlayer film is etched, and the obtained underlayer film pattern is used as an etching mask to etch the substrate, and then a pattern is formed on the substrate.  
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI716141B (en) * 2018-10-08 2021-01-11 台灣積體電路製造股份有限公司 Photoresist composition and method of forming pattern in photoresist
CN112513737A (en) * 2018-07-31 2021-03-16 三菱瓦斯化学株式会社 Underlayer film-forming composition
US11215928B2 (en) 2016-09-16 2022-01-04 Jsr Corporation Composition for resist underlayer film formation, resist underlayer film and method for forming the same, and production method of a patterned substrate

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7194356B2 (en) * 2016-07-21 2022-12-22 三菱瓦斯化学株式会社 Compound, resin and composition, resist pattern forming method and circuit pattern forming method
WO2018016614A1 (en) * 2016-07-21 2018-01-25 三菱瓦斯化学株式会社 Compound, resin, composition, and pattern forming method
JP7128582B2 (en) * 2017-10-25 2022-08-31 田岡化学工業株式会社 Bisaryl alcohols having a naphthalene skeleton and method for producing the same
TWI797246B (en) 2018-01-31 2023-04-01 日商三菱瓦斯化學股份有限公司 Compound, resin, composition, method for forming resist pattern, method for forming circuit pattern, and method for purifying resin
JP7139622B2 (en) * 2018-02-28 2022-09-21 三菱瓦斯化学株式会社 Compound, resin, composition and pattern forming method
CN112218844B (en) 2018-05-28 2024-04-26 三菱瓦斯化学株式会社 Compound, resin, composition, resist pattern forming method, circuit pattern forming method, and resin purifying method
CN112400138A (en) * 2018-06-26 2021-02-23 三菱瓦斯化学株式会社 Material for forming film for lithography, composition for forming film for lithography, underlayer film for lithography, and pattern formation method
TW202019864A (en) * 2018-07-31 2020-06-01 日商三菱瓦斯化學股份有限公司 Composition for forming optical component and optical component, and compound and resin
KR20210045357A (en) 2018-08-20 2021-04-26 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 Film-forming material for lithography, film-forming composition for lithography, underlayer film for lithography, and method for forming patterns
JP7523871B2 (en) * 2021-08-02 2024-07-29 信越化学工業株式会社 Thermosetting resin composition

Family Cites Families (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3223104A1 (en) * 1982-06-21 1983-12-22 Hoechst Ag, 6230 Frankfurt PHOTOPOLYMERIZABLE MIXTURE AND PHOTOPOLYMERIZABLE COPY MATERIAL MADE THEREOF
JPH04253716A (en) * 1991-02-05 1992-09-09 Dainippon Ink & Chem Inc Novel energy ray curable resin composition
JP4365494B2 (en) * 1999-10-27 2009-11-18 日本ペイント株式会社 Photosensitive composition for volume hologram recording and hologram obtained therefrom
AU2002222558B2 (en) * 2000-12-13 2006-07-06 Tokuyama Corporation Photochromic curable composition and cured articles thereof
JP3774668B2 (en) 2001-02-07 2006-05-17 東京エレクトロン株式会社 Cleaning pretreatment method for silicon nitride film forming apparatus
JP2003012660A (en) * 2001-06-28 2003-01-15 Sumitomo Bakelite Co Ltd Epoxyacrylate compound and method for producing the same
EP1455200A4 (en) * 2001-11-30 2005-09-28 Nikon Corp Precursor composition for optical resin, resin for optical use, optical element, and optical article
JP3914493B2 (en) 2002-11-27 2007-05-16 東京応化工業株式会社 Underlayer film forming material for multilayer resist process and wiring forming method using the same
EP1592051A4 (en) 2003-01-24 2012-02-22 Tokyo Electron Ltd CVD method for forming a silicon nitride film on a target substrate
JP3981030B2 (en) 2003-03-07 2007-09-26 信越化学工業株式会社 Resist underlayer film material and pattern forming method
JP4388429B2 (en) 2004-02-04 2009-12-24 信越化学工業株式会社 Resist underlayer film material and pattern forming method
KR101145088B1 (en) 2004-04-15 2012-05-11 미츠비시 가스 가가쿠 가부시키가이샤 Resist composition
JP4630806B2 (en) * 2005-12-09 2011-02-09 キヤノン株式会社 Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus
JP4781280B2 (en) 2006-01-25 2011-09-28 信越化学工業株式会社 Antireflection film material, substrate, and pattern forming method
JP4638380B2 (en) 2006-01-27 2011-02-23 信越化学工業株式会社 Antireflection film material, substrate having antireflection film, and pattern forming method
JP4858136B2 (en) 2006-12-06 2012-01-18 三菱瓦斯化学株式会社 Radiation-sensitive resist composition
US8586154B2 (en) * 2007-03-09 2013-11-19 3M Innovative Properties Company Triphenyl monomers suitable for microstructured optical films
JP5446118B2 (en) 2007-04-23 2014-03-19 三菱瓦斯化学株式会社 Radiation sensitive composition
TW200906873A (en) * 2007-05-30 2009-02-16 Toagosei Co Ltd Active energy ray curable composition, coating composition, coating member, and optical material
TW200906869A (en) * 2007-05-30 2009-02-16 Toagosei Co Ltd Active energy ray curable composition and optical material
JP5251523B2 (en) * 2008-07-08 2013-07-31 日立化成株式会社 Photosensitive resin composition, photosensitive element using the same, resist pattern forming method, and printed wiring board manufacturing method
JP2010138393A (en) 2008-11-13 2010-06-24 Nippon Kayaku Co Ltd Energy ray-curable resin composition for optical lens sheet, and cured product thereof
JP5423004B2 (en) * 2009-01-08 2014-02-19 東レ株式会社 Negative photosensitive resin composition and touch panel material using the same
KR101842728B1 (en) * 2010-05-07 2018-03-27 쓰리엠 이노베이티브 프로퍼티즈 컴파니 Antireflective films comprising microstructured surface
JP5778462B2 (en) * 2011-04-18 2015-09-16 旭有機材工業株式会社 Anthracene derivative and method for producing the same, curable composition, and cured product
TWI611255B (en) 2011-08-12 2018-01-11 三菱瓦斯化學股份有限公司 Resist composition, method for forming resist pattern, polyphenol compounds used in the method, and phenolic compounds derived therefrom
KR101907481B1 (en) 2011-08-12 2018-10-12 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 Underlayer film-forming material for lithography, underlayer film for lithography, and pattern formation method
CN102778814B (en) * 2012-07-05 2014-04-23 常州强力先端电子材料有限公司 Photo-sensitive composition containing ketoximes ester type photoinitiator and application thereof
EP2955169B1 (en) 2013-02-08 2017-03-15 Mitsubishi Gas Chemical Company, Inc. Novel allyl compound and method for producing the same
SG11201607444VA (en) * 2014-03-13 2016-10-28 Mitsubishi Gas Chemical Co Compound, resin, material for forming underlayer film for lithography, underlayer film for lithography, pattern forming method, and method for purifying the compound or resin
JP2015174877A (en) 2014-03-13 2015-10-05 日産化学工業株式会社 Resin composition containing specified hardening acceleration catalyst
WO2016104214A1 (en) * 2014-12-25 2016-06-30 三菱瓦斯化学株式会社 Compound, resin, underlayer film forming material for lithography, underlayer film for lithography, pattern forming method and purification method
JP6853957B2 (en) * 2015-07-23 2021-04-07 三菱瓦斯化学株式会社 New (meth) acryloyl compound and its production method
WO2017014284A1 (en) * 2015-07-23 2017-01-26 三菱瓦斯化学株式会社 Novel compound and method for producing same
JP6919838B2 (en) * 2015-08-31 2021-08-18 三菱瓦斯化学株式会社 Underlayer film forming material for lithography, composition for forming an underlayer film for lithography, underlayer film for lithography and its manufacturing method, pattern forming method, resin, and purification method.
KR20180048799A (en) * 2015-08-31 2018-05-10 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 A lower layer film forming material for lithography, a composition for forming a lower layer film for lithography, a lower layer film for lithography, a manufacturing method thereof, and a resist pattern forming method
TW201722893A (en) * 2015-09-03 2017-07-01 三菱瓦斯化學股份有限公司 Compound and method for preparing the same and composition comprising the same, composition for forming optical component, composition for forming lithographic film, resist composition, method for forming resist pattern, radiation sensitive composition
CN108137478B (en) * 2015-09-10 2021-09-28 三菱瓦斯化学株式会社 Compound, composition thereof, purification method, resist pattern formation method, and amorphous film production method
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WO2018016615A1 (en) * 2016-07-21 2018-01-25 三菱瓦斯化学株式会社 Compound, resin, composition, resist pattern formation method, and circuit pattern formation method
CN109476580A (en) * 2016-07-21 2019-03-15 三菱瓦斯化学株式会社 Compound, resin, composition and pattern forming method
WO2018016614A1 (en) * 2016-07-21 2018-01-25 三菱瓦斯化学株式会社 Compound, resin, composition, and pattern forming method
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