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WO2008105552A1 - Composition de résine sensible à un rayonnement, élément d'espacement pour un élément d'affichage à cristaux liquides, film de protection et procédé pour produire un élément d'espacement pour un élément d'affichage à cristaux liquides ou un film de - Google Patents

Composition de résine sensible à un rayonnement, élément d'espacement pour un élément d'affichage à cristaux liquides, film de protection et procédé pour produire un élément d'espacement pour un élément d'affichage à cristaux liquides ou un film de Download PDF

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Publication number
WO2008105552A1
WO2008105552A1 PCT/JP2008/053723 JP2008053723W WO2008105552A1 WO 2008105552 A1 WO2008105552 A1 WO 2008105552A1 JP 2008053723 W JP2008053723 W JP 2008053723W WO 2008105552 A1 WO2008105552 A1 WO 2008105552A1
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Prior art keywords
compound
radiation
resin composition
weight
group
Prior art date
Application number
PCT/JP2008/053723
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English (en)
Japanese (ja)
Inventor
Katsuya Nagaya
Takahiro Sakai
Daigo Ichinohe
Hitoshi Hamaguchi
Original Assignee
Jsr Corporation
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Publication date
Application filed by Jsr Corporation filed Critical Jsr Corporation
Priority to KR1020097017775A priority Critical patent/KR101421764B1/ko
Priority to JP2009501329A priority patent/JP4844774B2/ja
Publication of WO2008105552A1 publication Critical patent/WO2008105552A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G02F1/13392—Gaskets; Spacers; Sealing of cells spacers dispersed on the cell substrate, e.g. spherical particles, microfibres
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G02F1/13394—Gaskets; Spacers; Sealing of cells spacers regularly patterned on the cell subtrate, e.g. walls, pillars
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/50—Protective arrangements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/02—Materials and properties organic material
    • G02F2202/022—Materials and properties organic material polymeric

Definitions

  • the present invention particularly relates to a radiation sensitive resin composition extremely suitable for forming a spacer and a protective film in a liquid crystal display device, a spacer and a protective film, methods of forming them, and a liquid crystal display device.
  • Fine 1
  • spacers such as glass beads and plastic beads having a predetermined particle diameter have been used in order to keep the distance (cell gap) between two substrates constant. Since these spacers are scattered at random on a transparent substrate such as a glass substrate, if the spacer is present in the pixel formation region, the phenomenon of reflection of the spacer or incidence of light will occur. There is a problem that light is scattered and the contrast as a liquid crystal display element is lowered.
  • a method of forming a spacer by photolithography has come to be adopted.
  • a radiation-sensitive resin composition is applied onto a substrate, exposed to, for example, ultraviolet light through a predetermined mask, and then developed to form a dot-like or stripe-like spacer. Since the spacer can be formed only at a predetermined place other than the pixel formation region, the problems as described above can be basically solved (Japanese Patent Application Laid-Open No. 200 1-3 0 2 7 1 2) See the official gazette).
  • the radiation sensitive resin composition used to form the protective film covering only the formation region it is also required to be able to form a finer pattern than in the prior art.
  • Problems in forming fine patterns include diffraction of exposed light at the mask opening, and diffusion and scattering of exposed light by the radiation sensitive resin composition itself. It is. That is, in the case of forming a spacer or a protective film using a so-called negative radiation-sensitive resin composition, diffraction, diffusion, and scattering of exposed light cause the original exposed area to Since a wider range than the opening of a mask is exposed, the size of the pattern to be formed becomes significantly larger than the size of the opening of the mask, and a desired fine pattern can be formed. It was difficult.
  • An object of the present invention is to provide a radiation-sensitive resin composition excellent in resolution performance capable of forming a fine pattern.
  • Another object of the present invention is to provide a liquid crystal display spacer or protective film formed from the above-mentioned radiation sensitive resin composition, and a liquid crystal display device comprising the same.
  • Still another object of the present invention is to provide a method of forming the spacer or protective film for liquid crystal display.
  • the problem is firstly:
  • [A] (a 1) from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (A 2) a copolymer of an unsaturated compound other than (a 1), (B) a polymerizable unsaturated compound, (C) a radiation sensitive polymerization initiator, and (D) a nitroxyl
  • A (a 1) from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides
  • a 2 a copolymer of an unsaturated compound other than (a 1), (B) a polymerizable unsaturated compound, (C) a radiation sensitive polymerization initiator, and (D) a nitroxyl
  • the present invention provides a radiation-sensitive resin composition characterized by containing a compound.
  • said task is secondly:
  • the third problem is:
  • the solution is achieved by a method of forming a spacer or a protective film for a liquid crystal display element, comprising at least the following steps in the order described below.
  • the fourth problem is:
  • the copolymer [A] contained in the radiation sensitive resin composition of the present invention is at least one selected from the group consisting of (al) unsaturated carboxylic acid and unsaturated carboxylic acid anhydride ( Hereinafter, it is referred to as “compound l)”. And (a 2) (a 1) and other unsaturated compounds (hereinafter referred to as “compound (a 2)”).
  • compound (a 2-l) an [A1] compound (al) and an unsaturated compound having at least one hydroxyl group in one molecule
  • Acrylic acid methacrylic acid, crotonic acid, 2-acryloyloxy-succinic acid, 2-methacryloyloxy-sethyl-succinic acid, 2-acryloyloxy-t-hexyl hexahydrophthalic acid, 2- Monocarboxylic acids such as methacryloyloxethyl hexahydrophthalic acid;
  • the acid anhydride of the said dicarboxylic acid etc. can be mentioned.
  • acrylic acid methacrylic acid
  • 2-acrylic acid in view of copolymerization reactivity, solubility of the obtained polymer and copolymer in an alkaline developer and availability thereof.
  • royloxetylsuccinic acid 2-methacryloyloxysethylsuccinic acid
  • the compounds (al) can be used alone or in combination of two or more.
  • the content of repeating units derived from the compound (al) is preferably 5 to 60% by weight, more preferably 10 to 50% by weight, Particularly preferably, it is 15 to 40% by weight. If the content of the repeating unit derived from the compound (al) is less than 5% by weight, the resulting polymer tends to lower the solubility in an aqueous developer, while 60% by weight If it exceeds, the solubility of the polymer in an alkaline developer may be too high.
  • (meth) acrylic acid 4-hydroxy-cyclohexyl ester (meth) acrylic acid 4-hydroxymethyl-cyclohexyl methyl ester, (meth) acrylic acid 4-hydroxy-cyclohexyl-hexylethyl ester , (Meth) acrylic acid 3-hydroxybicyclo [2.2.1] hept-1-en-2-yl ester, (meth) acrylic acid 3-hydroxymethylbicyclo [2.2.1] hepto-5-ene H. 2-Iymethyl ester, (meth) acrylic acid 3-hydroxy-butyl-bicyclo [2.2.1] Hepto-5-en-2-yl-ethyl ester, (meth) acrylic acid 8-hydroxy-bicyclo [2.2.
  • other compounds 2-1) are particularly preferable from the viewpoints of the improvement of the developability and the compression performance of the obtained spacer.
  • acrylic acid 2- (6-hydroxyhexanoyl) hydroxyethyl ester methacrylic acid 2- (6-hydroxyhexanoyl) Preferred is ethyl ester.
  • a commercial product of a mixture of methacrylic acid 2- (6-hydroxyhex) ethyl ester and methacrylic acid 2-hydroxyl ester is a trade name: PLACCEL FM 1 D, FM 2 D (Daicel Chemical Industries, Ltd.) It can be obtained as
  • the compound (a2-1) in the copolymer [], can be used alone or in combination of two or more.
  • the content of the repeating unit derived from the compound (a 2-1) is preferably 1 to 50% by weight, more preferably 3 to 40% by weight, particularly preferably 5 to 3 It is 0% by weight.
  • the content of the repeating unit derived from the compound (a 2-1) is less than 1% by weight, the rate of introduction of the unsaturated isocyanate compound into the polymer tends to decrease, and the sensitivity tends to decrease.
  • it exceeds 50% by weight the storage stability of the polymer obtained by the reaction with the unsaturated isocyanate compound tends to decrease.
  • the compound (a 2-2) in the copolymer [ ⁇ ] for example, (meth) glycidyl acrylate, (meth) acrylic acid 2-methyl dalysidyl, 4-hydroxybutyl (meth) acrylate Glycidyl ether, (meth) acrylic acid 3, 4-epoxypeptyl, (meth) acrylic acid 6, 7-epoxyheptyl, (meth) acrylic acid 3, 4- epoxycyclohexyl, (meth) acrylic acid 3, 4— (meth) acrylic acid epoxy (cyclo) alkyl esters such as epoxycyclohexylmethyl;
  • glycidyl methacrylate, 2-methyl methyl methacrylate, methacrylic acid 3, 4 -epoxyhexyl hexyl, methacrylic acid 3, 4-epoxyhexyl hexylmethyl, 3-methyl-3-methacryloyloxy Preferred are methyloxetane, 3-ethyl 3-methacryloyloxymethyl oxetane and the like from the viewpoint of the polymerizability.
  • the compounds (a 2-2) can be used alone or in combination of two or more.
  • the content of the repeating unit derived from the compound (a 2 -2) is preferably 0.5 to 70% by weight, more preferably 1 to 60% by weight, particularly preferably 3 to 50 It is weight%. If the content of the repeating unit derived from the compound (a 2-2) is less than 0.5% by weight, the heat resistance of the resulting copolymer tends to decrease, while if it exceeds 70% by weight, the copolymer Storage stability tends to decrease.
  • another compound (a 2) different from the compound (a 2-l) and the compound (a 2-2) is referred to as “compound (a 2-i)” 3) ”.
  • alkyl acrylates of acrylic acid such as methyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate and the like;
  • Methacrylate such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, etc.
  • Acid alkyl ester such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, etc.
  • Acid alkyl ester such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, etc.
  • Acrylic acid cyclohexyl acrylic acid 2-methylcyclohexyl, acrylic acid tricyclo [5. 2. 2. 0 2 6 ] decane 8-yl, acrylic acid 2-(tricyclo [5. 2. 1. 0] 2 '6] decane one 8-Iruokishi) Echiru, Akuriru San'abura cyclic esters such as acrylic Sani Soporoniru; Cyclohexyl methacrylate cyclo hexyl, the methacrylic acid 2-methylcyclohexyl, main Yuku acrylic acid tricyclo [5.2.2 1.0 2 '6] decane one 8-I le, 2- methacrylate (Bok Rishikuro [5.2 . 1.0 2 '6] decane one 8-Iruokishi) Echiru, methacrylic San'abura cyclic esters such Metaku Isoporoniru acrylic acid;
  • Aryl ester or alkyl ester of acrylic acid such as phenyl acrylate or benzyl acrylate;
  • Aryl esters or methacrylates of methacrylic acid such as phenyl methacrylate and benzyl methacrylate;
  • Unsaturated dicarboxylic acid dialkyl esters such as jetyl maleate, jetyl fumarate, jetyl itaconate;
  • It has an oxygen-containing five-membered ring or an oxygen-containing six-membered ring such as tetrahydrofuran, 2-yl methacrylate, tetrahydropyran methacrylate, 2-methyl tetrahydropyran methacrylate, etc.
  • Methacrylic acid ester tetrahydrofuran, 2-yl methacrylate, tetrahydropyran methacrylate, 2-methyl tetrahydropyran methacrylate, etc.
  • Vinyl aromatic compounds such as styrene, methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene and the like;
  • conjugated gen compounds such as 1, 3-butadiene, isoprene and 2, 3-dimethyl-1, 3-butadiene,
  • n-butyl methacrylate, 2-methyl dalysyl methacrylate, benzyl methacrylate, tricyclo methacrylate [5.
  • the compound 2-3 is independently used. Or two or more can be mixed and used.
  • the content of repeating units derived from the compound (a 2-3) is preferably 10 to 70% by weight, more preferably 20 to 50 % By weight, particularly preferably 30 to 50% by weight. If the content of the repeating unit of the compound (a 2-3) is less than 10% by weight, the molecular weight of the copolymer tends to decrease, while if it exceeds 70% by weight, the compound (al), the compound (a) The effects exerted by the components 2-l) and the compound (a 2-2) decrease.
  • S] can be produced by polymerization in a suitable solvent in the presence of a radical polymerization initiator.
  • Alcohols such as methanol, ethanol, n-propanol and i-propanol;
  • Tetrahydrofuran ethers such as dioxane
  • Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether; ethylene glycol mono-methyl ether acetate Ethylene glycol monoetheric acid terehydrate, ethylenediaryl mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, etc. ethylene glycol monoalkyl ether tereacetate;
  • Dipropylene diaryl alkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyletyl ether, dipropylene diallyl methyl ethyl ether;
  • Propylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether tere acetate, propylene diallyl mono-n-butyl ether acetate, etc. ⁇ ;
  • Propylene glycol monoalkyl ether such as propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene dicaryl mono n-propyl ether propionate, propylene glycol mono-n-butyl ether propionate, etc. Monoterpropionate; aromatic hydrocarbons such as toluene and xylene;
  • Ketones such as methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone etc;
  • diethylene glycol alkyl ether diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, acetic acid ester and the like are preferable.
  • the said solvent can be used individually or in mixture of 2 or more types.
  • the radical polymerization initiator is not particularly limited, and, for example, 2, 2, 2-azobisisobutyronitrile, 2, 2, 2-azobis (2, 4-dimethylvaleronitrile), 2,2,2-azobisone (4-methoxy-2, 4-dimethylvaleronitrile), 4,4'-azobis (4-1cyanovaleric acid), dimethyl 2 2, 2-azobis (2-methylpropionate), 2, 2 Azo compounds such as 4-azobis (4-methoxy-2, 4-dimethylvaleronitrile); benzyl peroxide, lauroyl beroxide, t-butyl peroxypivalate, 1, 1-bis (t-butyl peroxy) cyclo Organic peroxides such as xanthan; hydrogen peroxide etc. can be mentioned.
  • a peroxide When used as a radical polymerization initiator, it may be used in combination with a reducing agent as a redox type initiator.
  • radical polymerization initiators can be used alone or in combination of two or more.
  • copolymer [] and the copolymer [jS] thus obtained can be used as a solution [A] even if it is used for the production of a polymer, or once separated from the solution to produce a [A] polymer You may use it for
  • the polystyrene equivalent weight average molecular weight (hereinafter referred to as “Mw”) of the copolymer [] and the copolymer [iS] by gel permeation chromatography (GPC) is preferably 2,000 to 100, 0 0 0, more preferably 5, 0 0 0 to 5 0, 0 0 0. If 1 ⁇ is less than 2,000, the resulting film may have reduced alkali developability, residual film ratio, etc., and pattern shape, heat resistance, etc. may be impaired. If it exceeds 0, 0, the resolution may be reduced or the pattern shape may be lost.
  • the polymer [A] in the present invention is obtained by reacting an unsaturated isocyanate compound with the copolymer [0!].
  • Acrylic acid 2- [2- (2-isocyanatoethoxy) ethoxy] ethyl, acrylic acid 2- ⁇ 2- [2- [2- (2-isocyanatoethoxy) ethoxy] ethoxy] ethyl, acrylic acid 2-— (2-— (Isosocyanate propoxy)
  • Acrylic acid derivatives of acrylic acid such as 2- [2- (2-isocyanatoprovoxy) provoxy] ethyl;
  • methacrylic acid derivatives such as methacrylic acid 2- [2- (2-isosocyanato provoxy) provoxy] ethyl and the like.
  • 2-acryloyl oxetyl isocyanate As a commercial product of 2-acryloyl oxetyl isocyanate, it is a brand name, and it is a commercial name under a brand name. It is a commercial lens of Force lens AO I (made by Showa Denko KK), and 2-s-methyl methacrylate isocyanato. Products are trade names by force lenses MO I (manufactured by Showa Denko KK), and commercially available products of methyacrylic acid 2- (2-isocyanato ethoxy) cetyl are trade names by force lens MO I — EG (manufactured by Showa Denko KK) can be mentioned.
  • unsaturated isocyanate compounds may be used alone or in combination of two or more.
  • the reaction of the copolymer [0!] With the unsaturated isocyanate compound can be carried out, for example, by using a catalyst such as di-n-butyltin (IV) dilaurate and a polymerization inhibitor such as p-methoxyphenol. It can be carried out by charging the unsaturated isocyanate compound into the polymer solution while stirring at room temperature or under heating.
  • a catalyst such as di-n-butyltin (IV) dilaurate
  • a polymerization inhibitor such as p-methoxyphenol
  • the amount of the unsaturated isocyanate compound used in producing the polymer is preferably 0.1 to 95 moles relative to 1 equivalent of the hydroxyl group of the compound (a 2-1) in the copolymer []. %, More preferably 1 to 80 mol%, particularly preferably 5 to 75 mol%.
  • the amount of the unsaturated isocyanato compound used is less than 0.1 mol%, the effect on the sensitivity, heat resistance and elastic property is small, while when it exceeds 95 mol%, the unsaturated unsaturated isocyanate compound is unreacted. Remaining, the polymer solution obtained and the storage stability of the radiation sensitive resin composition tend to be lowered.
  • each of the polymer and the copolymer [jS] can be used alone, but the storage stability of the resulting radiation-sensitive resin composition and the strength and heat resistance of the spacer are further increased. From the viewpoint of improvement, it is more preferable to use the [A] polymer and the copolymer [/ 3] in combination.
  • the amount of the copolymer [) 6] used is preferably 0 parts by weight to 100 parts by weight of the [A] polymer. 5 to 50 parts by weight, more preferably 1 to 40 parts by weight, particularly preferably 3 to 30 parts by weight.
  • the amount of the copolymer [/ 3] used is less than 0.5 part by weight, the effect of improving the strength and heat resistance of the spacer is small, while when it exceeds 50 parts by weight, the radiation sensitive resin composition It tends to lower the storage stability of the material.
  • the polymerizable unsaturated compound is composed of an unsaturated compound which is polymerized by exposure to radiation in the presence of a radiation sensitive polymerization initiator.
  • Such a [B] polymerizable unsaturated compound is not particularly limited.
  • a compound having four or more polymerizable unsaturated bonds in one molecule hereinafter, referred to as “polymerizable unsaturated compound [B 1 And at least one compound each having one to three polymerizable unsaturated bonds in one molecule (hereinafter referred to as “polymerizable unsaturated compound [B2]”) Is preferred.
  • a polymerizable unsaturated compound [B 1] for example, pendolyl erythritol tetra (meth) acrylate, dipentaerythritol! ⁇ ⁇ ⁇ ⁇ ⁇ (Meta) Special, ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ !
  • the urethane (meth) acrylate compound etc. which are obtained by making it react with the compound which has an one or more hydroxyl group and has a 3-5 (meth) acrylo xylo group inside can be mentioned.
  • Examples of the above-mentioned polymerizable unsaturated compound [B2] include ⁇ -propoxypolycabrolactone mono (meth) acrylate, ethylene glycol (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9 nannonio Rudi (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bis phenoxy ethanol fluo orange (meth) acrylate, dimethyl di methacrylate Cyclodecandi (meth) acrylate, 2 -hydroxy 3- (meth) acryloyloxypropyl methacrylate, 2-(2'- vinyloxyethoxy) hydroxyethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate
  • salmon pentaerythritol tri (meth)
  • the [B] polymerizable unsaturated compound can be used alone or in combination of two or more.
  • the proportion of the [B] polymerizable unsaturated compound in the radiation sensitive resin composition of the present invention is preferably 40 to 250 parts by weight, more preferably 100 parts by weight of the [A] copolymer. 60 to L 80 parts by weight.
  • the ratio of the polymerizable unsaturated compound [B 1] to the total of them is preferably 40 to 9 It is 9% by weight, more preferably 60 to 95% by weight.
  • the radiation-sensitive resin composition of the present invention can form a fine pattern close to the size of the mask opening, and a low exposure dose can be obtained. It is easy to obtain sufficient curability at
  • the radiation-sensitive polymerization initiator generates an active species capable of initiating polymerization of the polymerizable unsaturated compound [B] by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, charged particle beam, and X-ray.
  • radiation such as visible light, ultraviolet light, far ultraviolet light, charged particle beam, and X-ray.
  • Such [C] radiation-sensitive polymerization initiators include, for example, an alpha-hydroxy compound, an acetyl-phenone compound, a biimidazoyl compound, a benzoin compound, a benzophenone compound, an ⁇ -diketone compound, and a polynuclear quinone. There can be mentioned, for example, based compounds, xanthone compounds, phosphine compounds and triazine compounds.
  • the radiation-sensitive resin composition of the present invention preferably contains, as a radiation-sensitive polymerization initiator (C), an ⁇ -Shaloxime compound.
  • the amount of the [C] radiation-sensitive polymerization initiator used is preferably 0.01 to 1 parts by weight of the [B] polymerizable unsaturated compound 100. 20 parts by weight, more preferably 1 to 100 parts by weight. If the amount of the radiation-sensitive polymerization initiator used is less than 0.01 parts by weight, the residual film ratio at the time of development tends to decrease, and if it exceeds 120 parts by weight, alkali in the unexposed area at the time of development The solubility in the developer tends to decrease.
  • O-acisoxime compounds examples include: 1- [9-ethyl 6-benzyl-9. H. one-force rubazole- 3-yl] nononan-1, 2-nonan- 1 2- oxymu O-benzoate; 9 9 ⁇ ⁇ 6 ⁇ 6 6-Benzyl-9. H. ⁇ ⁇ 3 1 ⁇ ⁇ 1 ⁇ ⁇ 2 ⁇ ⁇ O 1 2 ⁇ ⁇ O O O ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ 1 1 ⁇ ⁇ ⁇ ⁇ 6 6 —Carbazole-3—yl ”—Pentane-1 1 2-Pentyl 1 2-Oxim O O-case 1 1 [9-Ethyl 6-Benzoyl 9 1 H. One-hand rubazole 3-yl] 1 Option 1 1 1 On Oxim 1 O-Acetate, 1 1 ⁇ 9 6 6-(2-Methyl 08053723
  • H.-Power rubazole-3 _ Yl one, one one (O one-year-old cetiloxime), 1, 2-ox dione one 1-[4 one (phenylthio) phenyl] -2- (O- benzoyloxy), 1, 1 2-butanedione 1 1- (4-(phenylthio) phenyl) 1-2 (0-benzoxim 1, 2, butandione-1 1 [41 (phenylthio) phenyl] -2- ( ⁇ 1 acetyloxy sim), 1, 2, 1 grade 1 dione 1 1 [41 (methylthio) phenyl] 1 2— (01 benzoyloxy), 1,2 year-old creadione 1 1 1 4 (phenyl) phenyl) 1 2 (O) (4 methyl benzyloxy) 1, 2, 2 And the like, such as 1 1 [4 1 (phenylthio) —, 2 — (01 1 hydroxyoxyl)].
  • a highly sensitive radiation sensitive resin composition can be obtained by using an O-acisoxime compound, and it is possible to obtain a spacer or a protective film having good adhesion. .
  • the radiation-sensitive resin composition of the present invention it is more preferable to use one or more other radiation-sensitive polymerization initiators together with an o-cyanoxime-type polymerization initiator as a [c] radiation-sensitive polymerization initiator. .
  • acetophenone-based compounds examples include ⁇ -hydroxy ketone-based compounds and ⁇ -amino ketone-based compounds.
  • Examples of the above-mentioned ⁇ -hydroxy ketone compounds include: 1-phenyl-2-hydroxy-1-methylpropane-1-one, 1- (4-i-propylphenyl) -12-hydroxy-2-methyl Examples thereof include propane-1-one, 4- (2-hydroxyethoxy) phenyl-1- (2-hydroxy-2-propyl) ketone and 1-hydroxycyclophenyl phenyl ketone.
  • —amino ketone compounds examples include 2-methyl-1- (4-methylthiophenyl) -1-monomorpholinopropane-1-one, 2-methyl-1- (41-hydroxy-thiol) phenyl 2-morpholino propane 1 1 one, 2-benzine 2 2 dimethyl amino 1 (4 1 morpholino phenyl) 1 butane 1 1 one, 2-(4 methyl benzyl) 1 2-(dimethylamino) 1 1 ( 4-morpholinophenyl) One butane, one one one, etc. can be mentioned.
  • examples of other than acetophenone compounds may include, for example, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, and 2,2-dimethoxy-2-phenacetophenone.
  • acetophenone compounds can be used alone or in combination of two or more.
  • examples of the above biimidazo-based compounds include: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2,2-biimidazo One, two, two, bis (2-bromophenyl)-one, four, four ', five, five'-tetrakis (4-ethoxycarboxylphenyl)-1,2'- biimidazole, two, two Bis (2-chlorophenyl) mono, 4, 5, 5'-tetraphenyl-1,2, 2-biimidazoyl, 2,2 'mono-bis (2, 4-dichlorophenyl) mono, 4, 4 ,, 5,5-Tetraphenyl-1,2,2-biimidazole-2,2 bis (2,4,6-trichlorophenyl) mono 4,4,5,5-tetraphenyl 1,2, -Biimidazole, 2,2'-bis (2-
  • 2,2'-bis (2-chlorophenyl) di-, 4-, 4, 5, 5-tetraphenyl-1,2-biimidazole, 2, 2, monobisbis (2, 4-dichloro-phenyl) mono-, 4-, 5'- tetraphenyl 1, 2, 2-biimidazoyl, 2, 2 'mono-bis (2, 4, 6- trichlorophenyl)- 4,4,5,5-tetraphenyl-1,2-biimidazolyl and the like are preferable, and in particular, 2,2,1-bis (2,4-dichlorophenyl) mono- 4,4 ', 5,5'-tetraphenyl Preferred is 1,2,2-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4,5,5,1-tetraphenyl-1,2-biimidazole.
  • the above biimidazole compounds may be used alone or in combination of two or more. It is possible. In the present invention, it is possible to further improve the sensitivity, resolution and adhesion by using a biimidazoline-based compound in combination.
  • amino sensitizer an aliphatic or aromatic compound having a dialkyamino group
  • amino sensitizers examples include N-methylesteramineramine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-monobis (getilamino) benzophenone, p-dimethylaminobenzoic acid ethyl, p-dimethylaminoresorpant. Acid i-amyl etc. can be mentioned.
  • amino sensitizers in particular, 4,4′-monobis (getilamino) benzophenone is preferred.
  • the above amino sensitizers can be used alone or in combination of two or more.
  • a thiol compound can be added as a hydrogen donor compound.
  • the biimidazoline compound is sensitized by the above-mentioned amino type sensitizer and is cleaved to generate an imidazole radical, but high polymerization initiation ability is not expressed as it is, and the resulting spacer is a reverse tete. It often results in an undesirable shape such as a one-piece shape.
  • Examples of the above-mentioned thiol compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazoyl, 2-mercaptobenzimidazolyl, 2-mercapto-5-methoxybenzothiazole, 2-mercaptobenzone.
  • Aromatic compounds such as 5-methoxybenzimidazole; 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, 3-mercaper Aliphatic monothiols such as octoyl propionate; Bifunctionals such as 3,6-dioxalic acid 1,8-octanedithiol, pentaerythritol tetra (mercapto acetate) and pentaerythritol tetra (3-mercapto propionate)
  • the above aliphatic thiols can be mentioned.
  • 2-mercaptobenzothiazole is particularly preferable.
  • the above-mentioned thiol compounds can be used alone or in combination of two or more.
  • the ratio of the other radiation-sensitive polymerization initiator in the case of using the O-acisoxime compound and the other radiation-sensitive polymerization initiator in combination is the total radiation-sensitive polymerization initiator
  • the content is preferably 30 to 8% by weight, more preferably 40 to 95% by weight. If the proportion of other radiation-sensitive polymerization initiators used is less than 30% by weight, a fine pattern may not be formed, while if it exceeds 98% by weight, the sensitivity may be reduced. .
  • the addition amount of the amino sensitizer is preferably 0.1 to 10 parts by weight with respect to 10 parts by weight of the biimidazole compound. Part, more preferably 1 to 120 parts by weight. If the addition amount of the amino sensitizer is less than 0.1 part by weight, the improvement effect on sensitivity, resolution and adhesion tends to be reduced, while if it exceeds 150 parts by weight, the obtained spacer 1 is obtained The shape tends to be lost.
  • the amount of thiol compound added is preferably 1 to 80 parts by weight, relative to 100 parts by weight of biimidazole compound, More preferably, it is 5 to 60 parts by weight. If the amount of the thiol compound added is less than 1 part by weight, the effect of improving the shape of the obtained spacer tends to decrease or the residual film ratio tends to decrease. On the other hand, the amount exceeds 80 parts by weight And, the shape of the obtained spacer tends to be lost.
  • the nitroxyl compound is a diffraction phenomenon of the exposed light at the mask opening, P2008 / 053723
  • a component that suppresses the photopolymerization reaction of the radiation sensitive resin composition outside the original exposed area due to diffusion and scattering of the exposed light by the radiation sensitive resin composition itself By including such a component, it is possible to form a fine pattern close to the size of the mask opening without impairing the sensitivity and the shape of the obtained spacer.
  • Examples of such [D] nitroxyl compounds include compounds represented by the following formulas (1-1), (1-2) and (1-3).
  • each R independently represents an alkyl group having 1 to 12 carbon atoms
  • Z and T each represent a group required to complete a 5- or 6-membered ring
  • E is 2 or 3
  • n represents an integer of 2 or 3.
  • R in the formula (1-1) for example, a methyl group, an ethyl group and the like can be mentioned.
  • preferred ones are also P2008 / 053723
  • X represents a hydrogen atom, a hydroxyl group, an alkoxy group, an amido group or an imide group
  • preferred ones include, for example, compounds represented by the following formulas (1-3-1) and (1-3-2) be able to.
  • Y represents a methylene group, an alkylene group having 2 to 12 carbon atoms or an alkenylene group, a cyclohexane group, a cyclohexyl group or an aryl group having 6 to 12 carbon atoms.
  • R 1 represents an alkyl group having 1 to 12 carbon atoms
  • nitroxyl compounds in particular, bis (1oxyl2,2,6,6-tetramethylpiperidine-1-yl) sebacate, 2,4,6-tris- [N-peptyl N— (Ioxyl 2, 2, 6, 6-Tetramethylpiperidine 4-yl) Mono-s-triazine, or 4, 4 'Ethylenebis (1-oxoyl 2, 2, 6, 6-tetramethylpiperazine (3- on) is preferred.
  • the amount of the [D] nitroxyl compound used is preferably 0.01 to 2 parts by weight, more preferably 0. 01 to 100 parts by weight of the [A] copolymer. 1 part by weight. [D] If the amount of the nitroxyl compound used is less than 0.001 part by weight, the desired effect may not be obtained, while if it exceeds 2 parts by weight, the sensitivity may be reduced and the pattern shape may be lost. There is.
  • [E] Chain Transfer Agent-In the radiation sensitive resin composition of the present invention it is preferable to further contain the [E] chain transfer agent.
  • [E] By using a chain transfer agent in combination with the [D] nitroxyl compound, it becomes possible to form a finer pattern closer to the size of the mask opening.
  • the compound is not particularly limited as long as it is a compound that can be used, but examples include compounds represented by the following formula (2) and thiols.
  • each R 2 independently represents hydrogen or an alkyl group having 3 or less carbon atoms.
  • R in the formula (2) for example, methyl, acetyl, n-propyl and i-propyl groups can be mentioned. '
  • chain transfer agent examples include, for example, a compound represented by the above formula (2) such as 2, 4-diphenyldimethyl 4-methyl- 1-pentene; 1-butanethiol, ptyl 3-mercaptopropionate, 3 -Aliphatic monothiols such as mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, 3-mercaptopropyl propionate, isobutyl ester, iso-butyl 3-mercaptopropionate, etc .; 3, 6-dioxor 1, 8 Examples thereof include aliphatic thiols having two or more functional groups such as octane dithiol, pentyl alcohol erythyl) ⁇ monotetra (mercapto acetate), and pennular erythei ⁇ mono tetra (3-mer capto propionate).
  • a compound represented by the above formula (2) such as 2, 4-diphenyldimethyl 4-methyl
  • chain transfer agents compounds represented by the above-mentioned formula (2) are preferable, and in particular, 2,4-diphenyldi-4-methyl-1-pentene is preferable.
  • the amount of the [E] chain transfer agent used is preferably 3 parts by weight or less, more preferably 0 parts by weight with respect to 100 parts by weight of the [A] copolymer. 5 to 2 parts by weight. [E] If the amount of chain transfer agent used exceeds 3 parts by weight, the sensitivity may be reduced and the pattern shape may be impaired.
  • a surfactant such as heat improvers can also be blended.
  • the surfactant is a component having an effect of improving the coating property, and a fluorine-based surfactant and a silicone-based surfactant are preferable.
  • the fluorine-based surfactant is preferably a compound having a fluoroalkyl group or a fluoroalkylene group at at least one of an end, a main chain and a side chain.
  • 1,1,2,2-tetrafluoro (octyl) (1,1,2,2-tetrafluoro-n-propyl) ether
  • 1,1,2,2-tetrafluoro-n-octyl ( n-Hexyl) ether 1,1,2,2-tetrafluoro-n-octyl ( n-Hexyl) ether
  • fluorosurfactants are trade names, for example, BM-1000, Identical 1 100 (above, manufactured by BM CHEMIE), Megafuck F 142 D, F 172, F 173 , F 183, F 178, F 1 91, F 47 1, F476 (above, Dainippon Ink and Chemicals, Inc.), Florard FC 1 70 C, 1st FC-171, 1st FC-430, 1st FC-431 (above, Sumitomo Siemm Co., Ltd.) , C.-S, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104 SC-105, SC-106 (above, Asahi Glass Co., Ltd.
  • F-top EF 301, EF 303, EF 352 above, Shin-Akita Kasei Co., Ltd.
  • Ftergent FT-100 Same FT-110, Same FT-14 OA, Same FT-150, Same FT-250, Same FT-251, Same FTX-251, Same FTX-218, Same FT-300, Same FT-310, FT — 400 S (above, manufactured by Neos Co., Ltd.) and the like.
  • silicone surfactant as a commercial product, for example,
  • polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene ethylene stearyl ether, polyoxyethylene allyl ether, etc .
  • polyoxyethylene n-octylphenyl. Ether Polyoxyethylene diaryl ether such as poloxetylene n-nonyl phenyl ether
  • Polyoxyethylene dialkyl ester such as polyoxyethylene dilaurate or polyoxyethylene distearate Etc.
  • KP 3 41 Shin-Etsu Chemical Co., Ltd.
  • Polyflow No. 57 No. 95 (Kyoeisha Chemical Co., Ltd.), etc.
  • the surfactants may be used alone or in combination of two or more.
  • the blending amount of the surfactant is preferably 5 times with respect to 100 parts by weight of the polymer [A].
  • the film tends to be rough during coating.
  • the adhesion aiding agent is a component having the function of further improving the adhesion between the spacer and the substrate, and is preferably functional silane coupling agent power S.
  • Examples of the functional silane coupling agent include a compound having a reactive functional group such as an epoxy group, a vinyl group, a vinyl group, an isocyanate group, or an epoxy group. More specifically, there may be mentioned trimethoxysilylbenzoic acid, silane, vinyltrimethoxysilane, isocyanatopropyltriethoxysilane (hydroxyl) detritrimethoxysilane and the like.
  • adhesion promoters can be used alone or in combination of two or more.
  • the compounding amount of the adhesion promoter is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the polymer [A]. If the blending amount of the adhesion promoter exceeds 20 parts by weight, the development residue tends to easily occur.
  • Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitroso compounds, and the like. More specifically, 4-methoxyphenol, N-nitroso N-fu Enyl hydroxyl amine etc. can be mentioned.
  • These storage stabilizers can be used alone or in combination of two or more.
  • the compounding amount of the storage stabilizer is preferably 3 parts by weight or less, more preferably 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the polymer [A]. If the amount of the storage stabilizer exceeds 3 parts by weight, the sensitivity S may be reduced to impair the pattern shape.
  • Examples of the heat resistance improver include N- (alkoxymethyl) glycoluril compounds, N- (alkoxymethyl) melamine compounds and the like.
  • Examples of the N- (alkoxymethyl) glycoluril compound include Three
  • N- (alkoxymethyl) glycoluril compounds in particular, ⁇ ', ⁇ ", ⁇ '", ⁇ ""-tetra (methoxymethyl) glycoluril are preferred, and ⁇ - (alkoxymethyl) is preferred.
  • melamine compound for example,
  • the heat resistance improver may be used alone or in combination of two or more.
  • the compounding amount of the heat resistance improver is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the polymer. If the amount of the heat resistance improver is more than 0 parts by weight, the storage stability of the radiation sensitive resin composition tends to decrease.
  • the radiation sensitive resin composition of the present invention is preferably used as a composition solution dissolved in a suitable solvent.
  • a suitable solvent one which dissolves each component constituting the radiation sensitive resin composition uniformly, does not react with each component, and has appropriate volatility, but the dissolution ability of each component, each component and Alcohols, ethylene glycol monoalkyl ether acetate, dimethylene glycol monoalkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, from the viewpoint of the reactivity and ease of film formation.
  • Dipropylene daryl alcohol, alkyl alkoxy propionate, acetic acid ester and the like are preferable, and in particular, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol mono-n-butyl ether acetate, Diethylene glycol Monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol dimethyl ether Ether, acetic acid 3-methoxybutyl, acetic acid 2-methoxyethyl etc. are preferred.
  • the solvents may be used alone or in combination of two or more.
  • a high boiling point solvent may be used in combination with the solvent.
  • high-boiling point solvents examples include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetoamide, N, N-dimethylacetoamide, N-methylpyrrolidone , Dimethyl sulfoxide, benzeneyl ether, di-n-hexyl ether, asetonylacetone, isophorone, cabronic acid, purilic acid, one-year-old ctanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoate ethyl acetate, shiyu Examples thereof include jetyl acid, diethyl ethyl maleate, apeptilolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate and the like.
  • These high boiling point solvents can be used alone or in combination of two or more.
  • composition solution prepared as described above is a Millipore having a pore diameter of about 0.5 m. It can also be filtered using filter paper etc. and used for use.
  • the radiation sensitive resin composition of the present invention can be very suitably used particularly for the formation of a spacer or protective film for a liquid crystal display element.
  • the formation of the spacer or protective film of the present invention includes at least the following steps in the order described below.
  • a pixel consisting of a red, green and blue colored layer is formed on a transparent substrate, and a radiation sensitive resin composition is preferably formed on the colored layer, preferably as a composition solution. After coating, the coated surface is heated (prebaked) to form a film. Further, in forming the spacer, a transparent conductive film is formed on the transparent substrate on which the pixels are formed or on a transparent substrate on which a protective film is further formed, and the transparent conductive film is formed. A radiation-sensitive resin composition is preferably applied as a composition solution, and then a coated surface is formed to form a film. Examples of the transparent substrate used herein include glass substrates and resin substrates.
  • glass substrates such as soda lime glass, non-alkali glass, etc .; polyethylene terephthalate, polybutylene terephthalate, etc.
  • resin substrates made of plastics such as rate, polyester tersulphone, polybasic propionate, and polyimide.
  • a transparent conductive film provided on one surface of a transparent substrate for example, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO 2 ), indium oxide-tin oxide An ITO film or the like made of (In 2 0 3 -S n 0 2 ) can be used.
  • a NESA film registered trademark of PPG, USA
  • tin oxide SnO 2
  • ITO film or the like made of (In 2 0 3 -S n 0 2 ) can be used.
  • composition solution As a method of applying the composition solution, as a method of forming a film of the radiation sensitive resin composition of the present invention, for example, (1) application method, (2) dry film method can be used.
  • an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a ball coating method, an inkjet coating method is adopted.
  • spin coating method spin coating method
  • slit die coating method a slit die coating method
  • ball coating method a ball coating method
  • inkjet coating method an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a ball coating method, an inkjet coating method.
  • spin coating and slit dye coating are preferred.
  • the dry film when forming a film of the radiation sensitive resin composition of the present invention, when (2) dry film method is adopted, the dry film is preferably a base film, preferably a flexible base film, It is one formed by laminating a radiation sensitive layer comprising the radiation sensitive resin composition of the present invention (hereinafter referred to as “photosensitive dry film”).
  • the photosensitive dry film can be formed by laminating a radiation-sensitive layer on a base film by preferably applying the radiation-sensitive resin composition of the present invention as a liquid composition and then drying.
  • a base film of the photosensitive dry film for example, a film of synthetic resin such as polyethylene terephthalate (PET), polyethylene, polypropylene, polycarbonate, polyvinyl chloride and the like can be used.
  • PET polyethylene terephthalate
  • the thickness of the base film is suitably in the range of 15 to 125 m.
  • the thickness of the radiation-sensitive layer to be obtained is preferably in the order of 1 to 30 x m.
  • the photosensitive dry film can also be stored by laminating a force film on the radiation sensitive layer when not used.
  • This cover film needs to have a suitable releasability so that it can not be peeled off when not in use and can be easily peeled off in use.
  • a cover film which satisfies such conditions for example, a film obtained by applying or baking a silicone-based release agent on the surface of a synthetic resin film such as a PET film, a polypropylene film, a polyethylene film, a polyvinyl chloride film or the like is used. can do.
  • the thickness of the cover film is usually about 25 zm.
  • the conditions of pre-baking also differ depending on the type of each component and the mixing ratio, etc. Usually, it is about 1 to 15 minutes at 70 to 120 ° C.
  • the formed coating is exposed.
  • it is usually exposed through a photomask having a predetermined pattern.
  • radiation used for exposure for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like can be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable, and particularly ultraviolet light of 365 nm. Radiation containing is preferred.
  • the exposure dose is usually 100 to 10, 000 JZm as a value obtained by measuring the intensity at a wavelength of 365 nm of the radiation to be exposed using a luminometer (manufactured by AI mod el 356, OA I Optical Associates I nc.) 2 , preferably 500 to 3,000 J / m 2 .
  • an alkaline developing solution is preferable, and examples thereof include sodium hydroxide, potassium salt of 7jC acid, sodium carbonate, sodium caycate, sodium metasilicate, inorganic alkali such as ammonia; Aliphatic primary amine such as n-propylamine; Aliphatic secondary amine such as getilamine and di n-propylamine; Aliphatic tertiary amine such as trimethylamine, methylgetilamine, dimethylethamine, toretilamine; pyrrole , Piperidine, N-methylbiperidine, N-methyl pyrrolidine, 1,8-diazabicyclo [5. 4.
  • Aromatic tertiary amine such as pyridine, collidine, lutidine, quinoline, etc .; ethanol dime Ruamin, Mechiruje evening Noruamin, Torietano Ruamin etc. alkanol ⁇ Min; can be exemplified an aqueous solution of tetramethylammonium Niu arm hydroxide, Te tiger Edji Ruan monitor ⁇ beam hydroxide quaternary Anmoniumu alkalinizing compounds such as salts and the like.
  • a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous solution of the alkaline compound.
  • any of a liquid deposition method, a dipping method, a shower method and the like may be used, and a developing time is usually about 10 to 100 seconds.
  • a desired pattern is formed, for example, by washing with running water for 30 to 90 seconds and then air drying with, for example, compressed air or compressed nitrogen.
  • the obtained pattern is heated at a predetermined temperature, for example, 100 ° C. to 230 ° C., for a predetermined time, for example, 5 minutes to 30 minutes on the hot plate.
  • a predetermined temperature for example, 100 ° C. to 230 ° C.
  • a predetermined time for example, 5 minutes to 30 minutes on the hot plate.
  • the liquid crystal display element of the present invention can be produced, for example, by the following method (a) or (b).
  • a pair (two sheets) of transparent substrates having a transparent conductive film (electrode) on one side is prepared, and the radiation sensitive resin composition of the present invention is used on the transparent conductive film of one of the substrates.
  • a spacer or a protective film or both are formed according to the method described above.
  • an alignment film having liquid crystal alignment ability is formed on the transparent conductive film and spacer or protective film of these substrates.
  • These substrates are disposed facing each other with a certain gap (cell gap) such that the liquid crystal alignment direction of each alignment film is orthogonal or antiparallel with the surface on which the alignment film is formed inward.
  • the liquid crystal is filled in the cell gap defined by the surface (alignment film) of the substrate and the spacer, and the filling holes are sealed to constitute a liquid crystal cell. Then, polarizing plates are attached to both outer surfaces of the liquid crystal cell such that the polarization direction thereof is aligned with or orthogonal to the liquid crystal alignment direction of the alignment film formed on one surface of the substrate, the liquid crystal display device of the present invention. You can get
  • liquid crystal used in each of the above methods examples include nematic liquid crystal and smectic liquid crystal.
  • nematic type liquid crystals are preferable.
  • a system liquid crystal, a bicyclo alcohol type liquid crystal, a cubane type liquid crystal, etc. are used.
  • liquid crystals are also sold as cholesteric liquid crystals such as, for example, colestil chloride, cholesteryl nonaate, cholesteryl mono-ponate, and as “C-15”, “CB-15” (all manufactured by Merck). It is also possible to add and use such chiral agents.
  • ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate can also be used.
  • a polarizing plate used outside the liquid crystal cell it is possible to use a polarizing plate called a H film which absorbs iodine while stretching and orienting polyvinyl alcohol, or a polarizing plate obtained by sandwiching a cellulose acetate protective film or the H film itself. And the like.
  • the radiation sensitive resin composition of the present invention has high resolution and can form a fine pattern in a high definition night crystal display device.
  • GPC-KF-801 Column: GPC-KF-801, GPC-KF-802, GPC-KF-8
  • the solid content concentration of this solution was 33.0% by weight, and the Mw of the copolymer [A-1] was 11,000.
  • the Mw of the obtained copolymer [A-2] was measured to be 12,000. Met.
  • the Mw of the obtained copolymer [1] was measured to be 13, 000.
  • Example 14 A-1 / A-2 50/50 B-1 / B-3 / B-4 120/10/10 C-2 / C-5 / C-7 / C-8 5/5/20 / 0.5
  • Example 15 A-3 100 B-1 / B-3 / B-4 120/15/10 C-2 / C-5 / C-6 5/5/20
  • Example 16 A-3 100 B-1 / B-3 / B-4 120/10/15 C-2 / C-5 / C-7 5/5/15
  • Example 17 A-3 100 B-1 / B-3 / B-4 120/10 / 15 C-2 / C-5 / C-7 5/5/15
  • Example 18 A-3 100 B-1 / B-3 / B-4 130/10/15 C-2 / C-5 / C -7 / G-8 3/5/15 / 0.5
  • Example 19 A-1 / A-4 100 B-1 / B-3 / B-4 120/10/15 C-2 / C-5 / C- 7 5/5/20
  • Example 20 A-1 / A-4 100 B-1 / B-3 / B-4 120/15/15 G-2 /
  • B-2 A polymerizable unsaturated monomer containing a polyfunctional urethane acrylate compound (trade name: KAYARAD DPHA-40H, manufactured by Nippon Kayaku Co., Ltd.)
  • B-3 1, 9-nonane acrylate (trade name: Light acrylate 1, 9- NDA, manufactured by Kyoeisha Co., Ltd.)
  • the film thickness is 4.0. A coating of m was formed.
  • the obtained film was exposed to ultraviolet light with an intensity of 25 OWZm 2 at 365 nm as the exposure time with a variable exposure time through a photomask having a circular pattern with a diameter of 14 m as an opening.
  • the plate After development with a 0.05% aqueous solution of potassium hydroxide at 25 ° C. for 60 seconds, the plate is washed with pure water for 1 minute and then postbaked in an oven at 230 ° C. for 20 minutes. Formed a spacer.
  • the sensitivity is defined as the minimum exposure amount at which the residual film ratio after the post bake (film thickness after the post bake X film thickness after exposure to 100Z) becomes 90% or more. When the sensitivity is less than 1,000 J / m 2, it can be said that the sensitivity is good.
  • a spacer was formed on the substrate in the same manner as in (1) Evaluation of sensitivity, except that the exposure dose was 1,000 J / m 2 and the development time was 40 seconds. At this time, the case where the pattern was formed without the occurrence of the residue was evaluated as ⁇ , and the case where the residue was generated was evaluated as X.
  • a spacer was formed on a substrate in the same manner as in (1) Evaluation of sensitivity, except that the amount of exposure was (1) an exposure corresponding to the sensitivity determined in the evaluation of sensitivity.
  • the obtained pattern is observed using a scanning electron microscope, and it is good if the surface of the feather is smooth.
  • a cured film was formed on the substrate in the same manner as in (1) Evaluation of sensitivity, except that the photomask was not used and the amount of exposure was the exposure equivalent to the sensitivity determined in (1) Evaluation of sensitivity. . After that, of the adhesion tests of J I S K-5400 (1900) 8.5, it was evaluated by the 8.5 ⁇ 2 grid tape method. At this time, Table 2 shows the number of remaining grids out of 100 grids.
  • a solution of the radiation-sensitive resin composition prepared above was used to form a S i 0 2 film on the surface to prevent dissolution of sodium ions, and further a soda having an ITO (indium tin oxide alloy) electrode deposited in a predetermined shape After spin-coating on a glass substrate, it was pre-baked for 10 minutes in a clean oven at 90 ° C to form a coating of 2. O ⁇ m thickness.
  • ITO indium tin oxide alloy
  • the coating film was exposed to radiation containing each wavelength of 365 nm, 405 nm and 436 nm at an exposure amount of 1,000 J / m 2 .
  • the substrate is immersed in a developing solution consisting of a 0.44% by weight aqueous solution of potassium hydroxide at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further dried at 230 ° C.
  • the film was post-baked for a minute and cured to form a permanent cured film.
  • liquid crystal M LC 6608 manufactured by Merck The liquid crystal cell was fabricated by injecting
  • the liquid crystal cell is put in a temperature-controlled layer at 60, and the voltage holding ratio of the liquid crystal cell is It was measured using a liquid crystal voltage holding ratio measurement system VHR-1 type A (trade name) manufactured by TEC.
  • the applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz.
  • the voltage holding ratio is the value of (the voltage applied in 0 milliseconds after the liquid crystal cell potential difference Z 10.7 milliseconds). If the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell can not hold the applied voltage at a predetermined level for 16.7 milliseconds, which means that the liquid crystal can not be aligned sufficiently. There is a high risk of causing burn-in.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition de résine sensible à un rayonnement contenant un copolymère [A] d'un acide carboxylique insaturé et/ou d'un anhydride d'acide carboxylique insaturé et un composé insaturé différent de ceux-ci, un composé insaturé polymérisable [B], un initiateur de polymérisation sensible à un rayonnement [C] et un composé nitroxyle [D] tel que du bis(1-oxyl-2,2,6,6-tétraméthylpipéridin-4-yl)sébacate. Cette composition de résine sensible à un rayonnement présente une excellente efficacité de résolution et permet de former une structure fine.
PCT/JP2008/053723 2007-02-27 2008-02-26 Composition de résine sensible à un rayonnement, élément d'espacement pour un élément d'affichage à cristaux liquides, film de protection et procédé pour produire un élément d'espacement pour un élément d'affichage à cristaux liquides ou un film de WO2008105552A1 (fr)

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JP2009501329A JP4844774B2 (ja) 2007-02-27 2008-02-26 感放射線性樹脂組成物、液晶表示素子用スペーサーおよび保護膜ならびにそれらの形成方法

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JP2009001653A (ja) * 2007-06-21 2009-01-08 Jsr Corp 側鎖不飽和重合体、感放射線性樹脂組成物および液晶表示素子用スペーサー
JP2010152302A (ja) * 2008-11-28 2010-07-08 Toray Ind Inc ネガ型感光性樹脂組成物およびそれを用いたタッチパネル用材料
CN101794075A (zh) * 2009-01-28 2010-08-04 Jsr株式会社 感射线性树脂组合物和液晶显示元件的分隔物及其形成方法
JP2010224067A (ja) * 2009-03-19 2010-10-07 Jsr Corp 感放射線性樹脂組成物、液晶表示素子の層間絶縁膜、保護膜及びスペーサーとその形成方法
CN101872123A (zh) * 2009-04-27 2010-10-27 Jsr株式会社 放射线敏感性树脂组合物、液晶显示用隔片或保护膜及其形成方法
JP2011145668A (ja) * 2009-12-14 2011-07-28 Fujifilm Corp 着色感光性組成物、カラーフィルタの製造方法、カラーフィルタ、及び液晶表示装置
JP2011221508A (ja) * 2010-03-26 2011-11-04 Sumitomo Chemical Co Ltd 感光性樹脂組成物
JP2012198507A (ja) * 2011-03-08 2012-10-18 Sumitomo Chemical Co Ltd 着色感光性樹脂組成物
US8999460B2 (en) 2011-04-21 2015-04-07 Merck Patent Gmbh Compounds and liquid-crystalline medium
JP2015069161A (ja) * 2013-09-30 2015-04-13 東京応化工業株式会社 感光性樹脂組成物、樹脂パターンの製造方法、及び表示装置
WO2016080375A1 (fr) * 2014-11-17 2016-05-26 日立化成株式会社 Composition de résine photosensible, élément photosensible, procédé pour la formation de motif de réserve, et procédé pour la fabrication de carte de câblage imprimé
JP2017223954A (ja) * 2017-06-15 2017-12-21 東京応化工業株式会社 感光性組成物、パターン形成方法、硬化膜、絶縁膜、及び表示装置
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EP3327103B1 (fr) * 2012-10-18 2020-10-14 Merck Patent GmbH Fluide à base de cristaux liquides, son procédé de stabilisation et affichage à base de cristaux liquides
JP6499568B2 (ja) * 2015-11-30 2019-04-10 富士フイルム株式会社 感光性組成物、硬化膜の製造方法、硬化膜、タッチパネル、及び、表示装置
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JP2006163339A (ja) * 2004-05-12 2006-06-22 Fuji Photo Film Co Ltd パターン形成材料、並びにパターン形成装置及びパターン形成方法
JP2006011397A (ja) * 2004-05-21 2006-01-12 Nippon Kayaku Co Ltd ネガ型着色感光性組成物
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JP2009001653A (ja) * 2007-06-21 2009-01-08 Jsr Corp 側鎖不飽和重合体、感放射線性樹脂組成物および液晶表示素子用スペーサー
JP2010152302A (ja) * 2008-11-28 2010-07-08 Toray Ind Inc ネガ型感光性樹脂組成物およびそれを用いたタッチパネル用材料
CN101794075A (zh) * 2009-01-28 2010-08-04 Jsr株式会社 感射线性树脂组合物和液晶显示元件的分隔物及其形成方法
JP2010224067A (ja) * 2009-03-19 2010-10-07 Jsr Corp 感放射線性樹脂組成物、液晶表示素子の層間絶縁膜、保護膜及びスペーサーとその形成方法
CN101872123A (zh) * 2009-04-27 2010-10-27 Jsr株式会社 放射线敏感性树脂组合物、液晶显示用隔片或保护膜及其形成方法
JP2011145668A (ja) * 2009-12-14 2011-07-28 Fujifilm Corp 着色感光性組成物、カラーフィルタの製造方法、カラーフィルタ、及び液晶表示装置
JP2011221508A (ja) * 2010-03-26 2011-11-04 Sumitomo Chemical Co Ltd 感光性樹脂組成物
JP2012198507A (ja) * 2011-03-08 2012-10-18 Sumitomo Chemical Co Ltd 着色感光性樹脂組成物
US8999460B2 (en) 2011-04-21 2015-04-07 Merck Patent Gmbh Compounds and liquid-crystalline medium
US9920248B2 (en) 2011-04-21 2018-03-20 Merck Patent Gmbh Compounds and liquid-crystalline medium
US10465117B2 (en) 2012-10-18 2019-11-05 Merck Patent Gmbh Liquid-crystalline medium, method for the stabilization thereof, and liquid-crystal display
JP2015069161A (ja) * 2013-09-30 2015-04-13 東京応化工業株式会社 感光性樹脂組成物、樹脂パターンの製造方法、及び表示装置
WO2016080375A1 (fr) * 2014-11-17 2016-05-26 日立化成株式会社 Composition de résine photosensible, élément photosensible, procédé pour la formation de motif de réserve, et procédé pour la fabrication de carte de câblage imprimé
KR20170085038A (ko) * 2014-11-17 2017-07-21 히타치가세이가부시끼가이샤 감광성 수지 조성물, 감광성 엘리먼트, 레지스터 패턴의 형성 방법 및 프린트 배선판의 제조 방법
JPWO2016080375A1 (ja) * 2014-11-17 2017-08-24 日立化成株式会社 感光性樹脂組成物、感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法
TWI695225B (zh) * 2014-11-17 2020-06-01 日商日立化成股份有限公司 感光性樹脂組成物、感光性元件、抗蝕劑圖案的形成方法及印刷配線板的製造方法
KR102595962B1 (ko) 2014-11-17 2023-11-01 가부시끼가이샤 레조낙 감광성 수지 조성물, 감광성 엘리먼트, 레지스터 패턴의 형성 방법 및 프린트 배선판의 제조 방법
JP2017223954A (ja) * 2017-06-15 2017-12-21 東京応化工業株式会社 感光性組成物、パターン形成方法、硬化膜、絶縁膜、及び表示装置

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