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WO2017002860A1 - Composition de résine photosensible négative, film durci, procédé de production de film durci et dispositif à semi-conducteurs - Google Patents

Composition de résine photosensible négative, film durci, procédé de production de film durci et dispositif à semi-conducteurs Download PDF

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Publication number
WO2017002860A1
WO2017002860A1 PCT/JP2016/069276 JP2016069276W WO2017002860A1 WO 2017002860 A1 WO2017002860 A1 WO 2017002860A1 JP 2016069276 W JP2016069276 W JP 2016069276W WO 2017002860 A1 WO2017002860 A1 WO 2017002860A1
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group
resin composition
photosensitive resin
general formula
negative photosensitive
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PCT/JP2016/069276
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English (en)
Japanese (ja)
Inventor
悠 岩井
渋谷　明規
一郎 小山
健志 川端
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富士フイルム株式会社
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Priority to JP2017526401A priority Critical patent/JP6522756B2/ja
Priority to KR1020177035558A priority patent/KR102041204B1/ko
Publication of WO2017002860A1 publication Critical patent/WO2017002860A1/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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • 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
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • 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
    • G03F7/075—Silicon-containing compounds
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

Definitions

  • the present invention relates to a negative photosensitive resin composition, a cured film, a method for producing a cured film, and a semiconductor device.
  • the present invention relates to a negative photosensitive resin composition suitable for an interlayer insulating film for a rewiring layer.
  • Thermosetting resins that are cured by cyclization are used for insulating layers of semiconductor devices because they are excellent in heat resistance and insulation.
  • polyimide since polyimide has low solubility in a solvent, it is used in the state of a precursor (heterocycle-containing polymer precursor) before cyclization reaction, applied to a substrate, etc., and then heated to produce a heterocycle-containing polymer precursor. The body is cyclized to form a cured film.
  • Patent Document 1 describes: (A) The following general formula (1): (In Formula (1), X 1 is a tetravalent organic group, Y 1 is a divalent organic group, n is an integer of 2 to 150, and R 1 and R 2 are respectively Independently, a hydrogen atom, the following general formula (2): (Wherein R 3 , R 4 and R 5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m is an integer of 2 to 10). A valent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, R 1 and R 2 are not simultaneously hydrogen atoms.
  • Polyimide precursor having a structure represented by: 100 parts by mass, (B) Photopolymerization initiator: 1 to 20 parts by mass, and (C) a monocarboxylic acid compound having 2 to 30 carbon atoms having at least one functional group selected from the group consisting of a hydroxyl group, an ether group and an ester group: 0.01 to 10 parts by mass, A negative-type photosensitive resin composition containing the above is disclosed.
  • Patent Document 2 includes (a) a polyimide resin having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), and (b) a positive type containing a quinonediazide compound. It is a photosensitive resin composition, and the imidation ratio of the polyimide resin having the structural unit represented by (a) the following general formula (1) and the structural unit represented by the following general formula (2) is 85%. The ratio of the structural unit represented by the following general formula (1) to the structural unit represented by the following general formula (2) is in the range of 30:70 to 90:10. A type photosensitive resin composition is disclosed.
  • X 1 represents a tetracarboxylic acid residue having 1 to 4 aromatic rings
  • Y 1 represents an aromatic diamine residue having 1 to 4 aromatic rings.
  • X 2 represents a tetracarboxylic acid residue having 1 to 4 aromatic rings
  • Y 2 represents a diamine residue having at least two alkylene glycol units in the main chain.
  • the exposure latitude of the negative photosensitive resin composition can be broadened by adopting a polyimide precursor having a predetermined structure in the negative photosensitive resin composition. It has been found that it is possible to solve this problem. Specifically, the above problem has been solved by the following ⁇ 1>, preferably ⁇ 2> to ⁇ 15>.
  • a negative photosensitive resin composition comprising a polyimide precursor having a repeating unit represented by the following general formula (1) and a radical photopolymerization initiator;
  • General formula (1) A 1 and A 2 each independently represents an oxygen atom or —NH—, R 11 is a divalent linking group having a group represented by — (L—O—) n1 — in the main chain, L is an alkylene group or —Si (R) 2 —, and R is hydrogen An atom or a monovalent organic group, n1 is an integer of 2 or more, R 12 represents a tetravalent organic group, R 13 and R 14 each independently represents a hydrogen atom or a monovalent organic group.
  • R 11 is a structure represented by the following general formula (2), a structure represented by the following general formula (3), and a structure represented by the following general formula (4).
  • R 21 and R 22 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and a plurality of R 21 may be the same or different; n2 Is an integer greater than or equal to 2; * represents the position linked to —NH— in the general formula (1);
  • General formula (3) In General Formula (3), R 31 and R 32 each independently represent a hydrogen atom or a monovalent organic group, L 31 represents a single bond or a divalent organic group, and L 32 and L 33 represent Each independently represents a divalent organic group, n3 is an integer of 2 or more; * represents a position linked to —NH— in the general formula (1);
  • General formula (4) In the general formula (4), R 41 and R 42 each independently represent
  • ⁇ 3> The negative photosensitive resin composition according to ⁇ 1> or ⁇ 2>, wherein at least one of R 13 and R 14 in the general formula (1) includes a radical polymerizable group.
  • ⁇ 4> The negative photosensitive resin composition according to any one of ⁇ 1> to ⁇ 3>, further comprising a radical polymerizable compound.
  • ⁇ 5> The negative photosensitive resin composition according to ⁇ 4>, wherein the radical polymerizable compound is a bifunctional or higher functional compound.
  • ⁇ 6> The negative photosensitive resin composition according to ⁇ 4>, wherein the radical polymerizable compound is a bifunctional compound.
  • ⁇ 7> The negative photosensitive resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein R 12 in the general formula (1) is a tetravalent organic group containing an aromatic ring.
  • R 12 in the general formula (1) is a tetravalent organic group containing an aromatic ring.
  • n1 in the general formula (1) is an integer of 2 to 200.
  • ⁇ 11> The cured film according to ⁇ 10>, which is an interlayer insulating film for a rewiring layer.
  • ⁇ 12> A method for producing a cured film, comprising using the negative photosensitive resin composition according to any one of ⁇ 1> to ⁇ 9>.
  • ⁇ 13> a step of applying the negative photosensitive resin composition to a substrate; A step of exposing the negative photosensitive resin composition applied to the substrate by irradiation with actinic rays or radiation, and The manufacturing method of the cured film as described in ⁇ 12> which has the process of developing with respect to the said exposed negative photosensitive resin composition.
  • ⁇ 14> The method for producing a cured film according to ⁇ 13>, further comprising a step of heating the developed negative photosensitive resin composition at a temperature of 50 to 500 ° C. after the step of performing the development treatment.
  • ⁇ 15> A semiconductor device having the cured film according to ⁇ 10> or ⁇ 11> or the cured film produced by the method according to any one of ⁇ 12> to ⁇ 14>.
  • the present invention makes it possible to provide a negative photosensitive resin composition having a wide exposure latitude, a cured film, a method for producing a cured film, and a semiconductor device.
  • the description of the components in the present invention described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
  • the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • active light means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.
  • light means actinic rays or radiation.
  • exposure means not only exposure using far ultraviolet rays, X-rays, EUV light typified by mercury lamps and excimer lasers, but also particle beams such as electron beams and ion beams, unless otherwise specified. Include drawing in the exposure.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • (meth) acrylate represents both and / or “acrylate” and “methacrylate”
  • (meth) allyl means both “allyl” and “methallyl”
  • (Meth) acryl” represents either “acryl” and “methacryl” or any one
  • “(meth) acryloyl” represents both “acryloyl” and “methacryloyl”, or Represents either.
  • the term “process” not only means an independent process, but also if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes, include.
  • solid content concentration is the mass percentage of the mass of the other component except a solvent with respect to the gross mass of a composition.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-converted values in gel permeation chromatography (GPC) measurement unless otherwise specified.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel.
  • Negative photosensitive resin composition contains the polyimide precursor which has a repeating unit represented by following General formula (1), and radical photopolymerization initiator.
  • General formula (1) In the general formula (1), A 1 and A 2 each independently represent an oxygen atom or —NH—, and R 11 has a group represented by — (L—O—) n1 — in the main chain.
  • a valent linking group L is an alkylene group or —Si (R) 2 —, R is a hydrogen atom or a monovalent organic group, n1 is an integer of 2 or more, and R 12 is a tetravalent group.
  • R 13 and R 14 each independently represents a hydrogen atom or a monovalent organic group.
  • the exposure latitude can be widened by incorporating a flexible structure in the portion of R 11 .
  • the solubility could be improved by incorporating a flexible structure.
  • the adhesion to the substrate can be improved while widening the exposure latitude. Furthermore, it is possible to maintain heat resistance while achieving these effects. Details of the present invention will be described below.
  • the negative photosensitive resin composition of the present invention includes a polyimide precursor having a repeating unit represented by the above general formula (1) (hereinafter sometimes referred to as “specific polyimide precursor”).
  • the specific polyimide precursor may have only one type of repeating unit represented by the general formula (1), or may have two or more types.
  • the negative photosensitive resin composition of this invention may contain only 1 type of specific polyimide precursors, and may contain 2 or more types.
  • the negative photosensitive resin composition of the present invention may contain other repeating units that are imide precursors other than the repeating unit represented by the general formula (1).
  • a 1 and A 2 each independently represents an oxygen atom or —NH—, preferably an oxygen atom.
  • R 11 is a divalent linking group having a group represented by — (L—O—) n1 — in the main chain, L is an alkylene group or —Si (R) 2 —, and R is hydrogen It is an atom or a monovalent organic group, and n1 is an integer of 2 or more.
  • L is an alkylene group
  • the alkylene group may be a linear, branched or cyclic alkylene group, but a linear or branched alkylene group is preferred.
  • the alkylene group preferably has 1 to 22 carbon atoms, more preferably 2 to 16, more preferably 2 to 8, and particularly preferably 2 to 4.
  • R is a hydrogen atom or a monovalent organic group, preferably a monovalent organic group, and examples of the monovalent organic group include an alkyl group, an aryl group, an alkoxy group Group and an alkenyl group are preferable, and an alkyl group and an aryl group are more preferable.
  • the alkyl group a linear alkyl group is preferable.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, more preferably 1 to 5 and particularly preferably 1 to 3.
  • aryl group a phenyl group is preferable.
  • n1 is an integer of 2 or more, preferably an integer of 2 to 200, more preferably an integer of 4 to 200, and still more preferably an integer of 4 to 60.
  • L may be included in one R 11 , or may be included in two or more.
  • R 11 is, - (L-O-) n1 - with or made of group only represented, - (L-O-) n1 - is preferably made of a group and the alkylene group represented by. Examples of the alkylene group herein include linear or branched alkylene groups having 1 to 10 carbon atoms.
  • R 11 is preferably selected from a structure represented by general formula (2), a structure represented by general formula (3), and a structure represented by general formula (4). More preferably, the structure is represented by the general formula (2).
  • General formula (2) In the general formula (2), R 21 and R 22 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and a plurality of R 21 may be the same or different; n2 Is an integer greater than or equal to 2; * represents a position linked to —NH— in the general formula (1).
  • R 31 and R 32 each independently represent a hydrogen atom or a monovalent organic group, L 31 represents a single bond or a divalent organic group, and L 32 and L 33 represent Each independently represents a divalent organic group, n3 is an integer of 2 or more; * represents a position connected to —NH— in formula (1).
  • R 41 and R 42 each independently represent a hydrogen atom or a monovalent organic group, L 41 represents a single bond or a divalent organic group, and L 42 and L 43 represent Each independently represents a divalent organic group, n4 is an integer of 2 or more; * represents a position linked to —NH— in formula (1).
  • R 21 and R 22 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or a linear alkyl group having 1 to 10 carbon atoms, Alternatively, a linear alkyl group having 1 to 5 carbon atoms is more preferable, and a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms is more preferable.
  • n2 is an integer of 2 or more, preferably an integer of 2 to 200, more preferably an integer of 4 to 200, and still more preferably an integer of 4 to 60.
  • R 31 and R 32 each independently represent a hydrogen atom or a monovalent organic group, preferably a monovalent organic group, more preferably an alkyl group, an aryl group, an alkoxy group, or an alkenyl group. Of these, an alkyl group and an aryl group are particularly preferable.
  • the alkyl group a linear alkyl group is preferable.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, more preferably 1 to 5 and particularly preferably 1 to 3.
  • aryl group a phenyl group is preferable.
  • L 31 represents a single bond or a divalent organic group, preferably a single bond or an alkylene group, and more preferably a single bond.
  • alkylene group examples include linear or branched alkylene groups having 1 to 10 carbon atoms.
  • L 32 and L 33 each independently represent a divalent organic group, preferably an alkylene group, and more preferably a linear or branched alkylene group having 1 to 10 carbon atoms.
  • n3 is an integer of 2 or more, preferably an integer of 2 to 200, more preferably an integer of 4 to 200, and still more preferably an integer of 4 to 60.
  • R 41 and R 42 each independently represent a hydrogen atom or a monovalent organic group, preferably a monovalent organic group, more preferably an alkyl group, an aryl group, an alkoxy group or an alkenyl group. Of these, an alkyl group and an aryl group are particularly preferable.
  • a linear alkyl group is preferable.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, more preferably 1 to 5 and particularly preferably 1 to 3.
  • a phenyl group is preferable.
  • a plurality of R 41 and R 42 contained in one molecule may be the same or different.
  • L 41 represents a single bond or a divalent organic group, preferably a single bond or an alkylene group, and more preferably a single bond.
  • the alkylene group include linear or branched alkylene groups having 1 to 10 carbon atoms.
  • L 42 and L 43 each independently represent a divalent organic group, preferably an alkylene group, and more preferably a linear or branched alkylene group having 1 to 10 carbon atoms.
  • n4 is an integer of 2 or more, preferably an integer of 2 to 200, more preferably an integer of 4 to 200, and still more preferably an integer of 4 to 60.
  • x, y, z, n and m are arbitrary numbers, and indicate the molar ratio of each repeating unit.
  • x is an integer from 2 to 200
  • y is an integer from 2 to 200
  • z is an integer from 2 to 200
  • n is an integer from 2 to 200
  • m is an integer from 2 to 200. It is.
  • R 11 is also preferably a diamine residue remaining after removal of the amino group of a diamine containing two or more ethylene glycol chains or propylene glycol chains in one molecule, and more preferably an aromatic ring. Also included are diamine residues that do not contain.
  • Examples include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 ( Trade names, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propane Examples include, but are not limited to, -2-yl) oxy) propan-2-amine and the like.
  • x, y, and z are average values.
  • R 11 is also preferably a diamine residue containing three or more divalent linking chains having silicon.
  • the diamine residue containing three or more divalent linking chains having silicon include diamine residues of diamines represented by the following general formula (5).
  • R 51 and R 52 each independently represent a hydrogen atom or a monovalent organic group
  • L 51 represents a single bond or a divalent organic group
  • L 52 and L 53 represent Each independently represents a divalent organic group
  • n4 is an integer of 2 or more
  • * represents a position linked to —NH— in formula (1).
  • L 51 and R 52 a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group and the like can be mentioned independently.
  • L 51 is preferably a single bond from the viewpoint of raw material availability.
  • Examples of L 52 and L 53 include a methylene group, an ethylene group, a butylene group, and a phenylene group, which may have a substituent.
  • N4 is preferably an integer of 2 to 200, more preferably an integer of 4 to 100, and still more preferably an integer of 4 to 60.
  • Examples include both-end amine-modified methyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008; Chisso Corporation: Cypralane FM-3311 , FM-3321, FM-3325), and both-end amine-modified phenyl silicone oils (manufactured by Shin-Etsu Chemical Co., Ltd .: X22-1660B-3, X-22-9409).
  • R 12 represents a tetravalent organic group, preferably a tetravalent group containing an aromatic ring, represented by the following general formula (1-1) or general formula (1-2). More preferred are the groups
  • R 112 represents a single bond or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—, —
  • a group selected from SO 2 — and —NHCO—, and combinations thereof, is preferably a single bond or an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, —O More preferably, it is a divalent group selected from —, —CO—, —S— and —SO 2 —, and —CH 2 —, —C (CF 3 ) 2 —, —C (CH 3 ) 2 More preferred is a divalent group selected from the group consisting of —, —O—, —CO—, —S— and —SO 2 —.
  • R 12 is Examples thereof include a tetracarboxylic acid residue remaining after removal of an anhydride group from tetracarboxylic dianhydride. Specific examples include tetracarboxylic acid residues remaining after the removal of anhydride groups from the following tetracarboxylic dianhydrides.
  • examples of R 12 include tetracarboxylic acid residues remaining after removal of anhydride groups from tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below.
  • R 12 preferably has an OH group. More specifically, preferred examples of R 12 include tetracarboxylic acid residues remaining after removal of anhydride groups from (DAA-1) to (DAA-5).
  • R 13 and R 14 each independently represent a hydrogen atom or a monovalent organic group.
  • a substituent that improves the solubility in a developer is preferably used.
  • R 13 and R 14 are preferably a hydrogen atom or a monovalent organic group.
  • the monovalent organic group include an aryl group and an aralkyl group having one, two or three, preferably one acidic group, bonded to the carbon atom of the aryl group.
  • Specific examples include an aryl group having 6 to 20 carbon atoms having an acidic group and an aralkyl group having 7 to 25 carbon atoms having an acidic group. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned.
  • the acidic group is preferably an OH group.
  • R 13 and R 14 are preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.
  • R 13 and R 14 are preferably monovalent organic groups.
  • the monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, and an aryl group, and more preferably an alkyl group substituted with an aryl group.
  • the alkyl group preferably has 1 to 30 carbon atoms.
  • the alkyl group may be linear, branched or cyclic.
  • linear or branched alkyl group examples 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 nonyl group, a decyl group, a dodecyl group, a tetradecyl group, and an octadecyl group.
  • the cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group.
  • Examples of the monocyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • Examples of the polycyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group, and a pinenyl group. Is mentioned. Among these, a cyclohexyl group is most preferable from the viewpoint of achieving high sensitivity. Moreover, as an alkyl group substituted by the aryl group, the linear alkyl group substituted by the aryl group mentioned later is preferable.
  • aryl group examples include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, anthracene.
  • Examples of the polymerizable group possessed by R 13 and R 14 include an epoxy group, an oxetanyl group, a group having an ethylenically unsaturated bond, a blocked isocyanate group, an alkoxymethyl group, a methylol group, and an amino group.
  • an embodiment including a radical polymerizable group is exemplified, and a group having an ethylenically unsaturated bond is more preferable.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III), and the like.
  • R 200 represents hydrogen or methyl, and methyl is more preferable.
  • R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH (OH) CH 2 — or a polyoxyalkylene group having 4 to 30 carbon atoms.
  • suitable R 201 are ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, —CH 2 CH (OH) CH 2 —, And ethylene, propylene, trimethylene, and —CH 2 CH (OH) CH 2 — are more preferable.
  • R 200 is methyl and R 201 is ethylene.
  • R 13 and R 14 in the general formula (1) contain a polymerizable group (preferably a radical polymerizable group)
  • the molar ratio of polymerizable group: non-polymerizable group is preferably 100: 0 to 5 : 95, more preferably 100: 0 to 20:80, and still more preferably 100: 0 to 50:50.
  • the counter amine salt may be formed with the tertiary amine compound.
  • the tertiary amine compound having such a tyrenic unsaturated bond include N, N-dimethylaminopropyl methacrylate.
  • the specific polyimide precursor preferably has a fluorine atom in the structural unit from the viewpoint of improving resolution.
  • the fluorine atom imparts water repellency to the surface of the film during alkali development, and soaking in from the surface can be suppressed.
  • the fluorine atom content in the specific polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less from the viewpoint of solubility in an alkaline aqueous solution.
  • the specific polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
  • the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.
  • the specific polyimide precursor is end-capped with a main chain terminal such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound and the like. It is preferable to seal with a stopper. Of these, it is more preferable to use a monoamine.
  • a monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene and 1-hydroxy-6-aminonaphthalene.
  • the specific polyimide precursor may contain a repeating unit other than the repeating unit represented by the general formula (1) (hereinafter sometimes referred to as “other repeating unit”).
  • other repeating units a divalent organic group other than a divalent linking group having R 11 in the main chain having a group represented by — (L—O—) n1 — in the general formula (1). (hereinafter, sometimes referred to R 111) repeating units is preferably. That is, in the general formula (1), a group in which R 11 is replaced with R 111 described below is preferable.
  • Examples of the divalent organic group represented by R 111 include linear or branched aliphatic groups, cyclic aliphatic groups, and groups containing aryl groups, and linear or branched aliphatic groups having 2 to 20 carbon atoms. And a group consisting of a cyclic aliphatic group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a combination thereof, more preferably an aryl group having 6 to 20 carbon atoms. The following are mentioned as an example of an aryl group.
  • specific polyimide precursor, the general formula R 11 (1) may contain a structure and another repeating unit, such as listed below.
  • Examples of the divalent organic group that may be partially used at the position of R 11 include a diamine residue remaining after removal of the amino group of the diamine.
  • Examples of the diamine include aliphatic, cycloaliphatic or aromatic diamines. Specific examples include diamine residues remaining after removal of the amino groups of the following diamines.
  • 1,2-diaminoethane 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1, 2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3 -Aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- and p-phenylenediamine, diaminotoluene, 4,4'- and 3,3'-diaminobiphenyl, 4,4'- and 3,3'-diaminodiphenyl ether
  • R 111 also include diamine residues remaining after removal of the amino groups of diamines (DA-1) to (DA-18) shown below.
  • R 111 is preferably a diamine residue remaining after removal of the amino group of the following diamine.
  • R 111 is more preferably a diamine residue remaining after removal of the amino group of the following diamine.
  • p-phenylenediamine, 4,4′-diaminobiphenyl, 4,4′-diaminodiphenyl ether 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-) Hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-aminopropyl) tetramethyldisiloxane, 4,4′-diamino-2,2′-bis (trifluoromethyl) Biphenyl; the above (DA-7), (DA-8), (DA-12), (DA-13); Jeffamine (registered trademark) KH-511, ED-600, ED-900, EDR-148, EDR-176, D-200, D-400, D-2000 (trade names, manufactured by HUNTSMAN Co., Ltd
  • the other repeating units other than the repeating unit represented by the general formula (1) are A 1 and A 2 in the general formula (1) in the general formula (1) except for R 11 being R 111. , R 12 , R 13 and R 14 , and the preferred range is also the same. Note that in particular polyimide precursor, in the repeating unit represented by the general formula (1), A 1, A 2, R 12, R 13 and R 14 and A 1, A 2 in the other repeating units, R 12, R 13 and R 14 may be the same or different.
  • the content of the other repeating units is preferably 1 to 60 mol%, and more preferably 5 to 50 mol%.
  • the weight average molecular weight (Mw) of the specific polyimide precursor is preferably 20000 to 28000, more preferably 22000 to 27000, and further preferably 23000 to 25000.
  • the dispersity (Mw / Mn) of the specific polyimide precursor is not particularly defined, but is preferably 1.0 or more, more preferably 2.5 or more, and 2.8 or more. Further preferred.
  • the upper limit of the degree of dispersion of the specific polyimide precursor is not particularly defined, but is preferably 4.5 or less, for example, or 3.4 or less.
  • the content of the specific polyimide precursor in the negative photosensitive resin composition of the present invention is preferably 20 to 100% by mass, more preferably 50 to 99% by mass with respect to the total solid content of the negative photosensitive resin composition. 70 to 99% by mass is more preferable, and 80 to 99% by mass is particularly preferable.
  • the negative photosensitive resin composition of the present invention may contain a polyimide precursor other than the specific polyimide precursor.
  • a polyimide precursor which does not contain the repeating unit represented by General formula (1), such as a polyimide precursor which consists only of said other repeating unit, is illustrated.
  • it can also be set as the structure which does not contain another polyimide precursor substantially. “Substantially free” means, for example, that the content of the other polyimide precursor contained in the negative photosensitive resin composition of the present invention is 3% by mass or less of the content of the specific polyimide precursor. .
  • the negative photosensitive resin composition of the present invention may contain other resin components without departing from the spirit of the present invention.
  • other resin components include polybenzoxazole precursors and polyimide resins.
  • it can also be set as the structure which does not contain resin other than a polyimide precursor substantially. “Substantially free” means, for example, that the content of the resin other than the polyimide precursor contained in the negative photosensitive resin composition of the present invention is 3% by mass or less of the content of the polyimide precursor. .
  • the negative photosensitive resin composition of the present invention contains a radical photopolymerization initiator.
  • the photo-radical polymerization initiator can perform negative development by initiating polymerization of a radical polymerizable group that the repeating unit represented by the general formula (1) may have or a radical polymerizable compound described later. it can. More specifically, after applying a negative photosensitive resin composition to a semiconductor wafer or the like to form a layered composition layer, irradiation with light causes curing by radicals, and solubility in the light irradiation part. Can be reduced. For this reason, there exists an advantage that the area
  • the radical photopolymerization initiator is not particularly limited as long as it has the ability to initiate a polymerization reaction (crosslinking reaction) of a radically polymerizable compound or the like, and can be appropriately selected from known radical photopolymerization initiators. For example, those having photosensitivity to light in the ultraviolet region to the visible region are preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.
  • the radical photopolymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (preferably 330 to 500 nm). The molecular extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.
  • radical photopolymerization initiator known compounds can be used without limitation.
  • halogenated hydrocarbon derivatives for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group
  • Acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo Compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, and the like.
  • halogenated hydrocarbon derivatives having a triazine skeleton examples include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F . C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, Examples thereof include compounds described in Japanese Patent No. 4221976.
  • Examples of the compounds described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloro Methyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 (2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl)- 1,3,4-oxadiazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) 1,3,4-oxadiazole, 2-trichloromethyl-5-
  • radical photopolymerization initiators other than the above, compounds described in paragraph No. 0086 of JP-A-2015-087611, JP-A-53-133428, JP-B-57-1819, JP-A-57-1 Examples thereof include compounds described in Japanese Patent No. 6096 and US Pat. No. 3,615,455, the contents of which are incorporated herein.
  • Examples of the ketone compound include compounds described in paragraph No. 0087 of JP-A-2015-087611, the contents of which are incorporated herein.
  • Kaya Cure DETX manufactured by Nippon Kayaku Co., Ltd.
  • Nippon Kayaku Co., Ltd. is also preferably used.
  • hydroxyacetophenone compounds As the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
  • hydroxyacetophenone-based initiator IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone initiator commercially available IRGACURE-907, IRGACURE-369, IRGACURE-784, and IRGACURE-379 (all trade names: manufactured by BASF) can be used. IRGACURE is a registered trademark.
  • aminoacetophenone-based initiator compounds described in JP-A-2009-191179 whose absorption wavelength is matched with a light source of 365 nm or 405 nm can also be used.
  • acylphosphine initiator commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.
  • an oxime compound is more preferable.
  • the oxime compound compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166 can be used.
  • Preferred oxime compounds include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxy And imino-1-phenylpropan-1-one.
  • Examples of oxime compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660, J.A. C. S. Perkin II (1979) pp. 156-162, and Journal of Photopolymer Science and Technology (1995) pp. And the compounds described in JP-A 2000-66385, JP-A 2000-80068, JP-T 2004-534797, and JP-A 2006-342166.
  • IRGACURE-OXE01 manufactured by BASF
  • IRGACURE-OXE02 manufactured by BASF
  • N-1919 manufactured by ADEKA
  • JP-A-2007-231000 and JP-A-2007-322744 can also be suitably used.
  • the cyclic oxime compounds fused to carbazole dyes described in JP 2010-32985 A and JP 2010-185072 A in particular have high light absorption and high sensitivity.
  • a compound described in JP-A-2009-242469, which is a compound having an unsaturated bond at a specific site of the oxime compound can also be suitably used.
  • an oxime compound having a fluorine atom It is also possible to use an oxime compound having a fluorine atom.
  • an initiator include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph No. 0345 of JP 2014-500852 A, JP Examples thereof include compound (C-3) described in paragraph No. 0101 of 2013-164471.
  • Specific examples include the following compounds.
  • As the most preferred oxime compounds there are oxime compounds having a specific substituent, as disclosed in JP 2007-267979 A, and oxime compounds having a thioaryl group, as disclosed in JP 2009-191061 A.
  • the photo radical polymerization initiator is a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, Selected from the group consisting of allylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivatives thereof, cyclopentadiene-benzene-iron complex and salt thereof, halomethyloxadiazole compound, 3-aryl substituted coumarin compound Are preferred.
  • trihalomethyltriazine compounds More preferred are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzophenone compounds, and acetophenone compounds, and more preferred are trihalomethyltriazine compounds. , ⁇ -aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds, and most preferably oxime compounds.
  • the content of the photo radical polymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0 to the total solid content of the negative photosensitive resin composition. 1 to 10% by mass.
  • the radically polymerizable compound is preferably contained in an amount of 1 to 20 parts by mass, more preferably 3 to 10 parts by mass with respect to 100 parts by mass of the radically polymerizable compound.
  • One type of radical photopolymerization initiator may be sufficient, and 2 or more types may be sufficient as it. When there are two or more radical photopolymerization initiators, the total is preferably in the above range.
  • the negative photosensitive resin composition of the present invention may contain a radical polymerizable compound other than the polyimide precursor.
  • a radical polymerizable compound By containing a radically polymerizable compound, a cured film having better heat resistance can be formed. Furthermore, pattern formation can also be performed by photolithography.
  • the radical polymerizable compound a compound having an ethylenically unsaturated bond is preferable, and a compound containing two or more ethylenically unsaturated groups is more preferable.
  • the radically polymerizable compound may be in any of chemical forms such as monomers, prepolymers, oligomers and mixtures thereof, and multimers thereof.
  • a monomer type radical polymerizable compound (hereinafter also referred to as a radical polymerizable monomer) is a compound different from a polymer compound.
  • the radical polymerizable monomer is typically a low molecular compound, preferably a low molecular compound having a molecular weight of 2000 or less, more preferably a low molecular compound having a molecular weight of 1500 or less, and a low molecular compound having a molecular weight of 900 or less. More preferably, it is a compound.
  • the molecular weight of the radical polymerizable monomer is usually 100 or more.
  • the oligomer type radical polymerizable compound is typically a polymer having a relatively low molecular weight, and is preferably a polymer in which 10 to 100 radical polymerizable monomers are bonded.
  • the molecular weight is preferably 2000 to 20000, more preferably 2000 to 15000, and still more preferably 2000 to 10000 in terms of polystyrene in gel permeation chromatography (GPC).
  • the number of functional groups of the radical polymerizable compound means the number of radical polymerizable groups in one molecule.
  • the radical polymerizable compound preferably contains at least one bifunctional or higher functional radical polymerizable compound containing two or more radical polymerizable groups, and preferably contains at least one bifunctional radical polymerizable compound. More preferably.
  • ⁇ Compound having an ethylenically unsaturated bond As a group having an ethylenically unsaturated bond, a styryl group, a vinyl group, a (meth) acryloyl group and a (meth) allyl group are preferable, and a (meth) acryloyl group is more preferable.
  • the compound having an ethylenically unsaturated bond include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters thereof, amides, and these Preferred are an ester of an unsaturated carboxylic acid and a polyhydric alcohol compound, an amide of an unsaturated carboxylic acid and a polyvalent amine compound, and a multimer thereof.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters thereof esters thereof, amides
  • these Preferred are an ester of an unsaturated carboxylic acid and a polyhydric alcohol compound, an amide of an unsaturated carboxylic acid and a polyvalent amine compound, and a multimer thereof.
  • a dehydration condensation product with a polyfunctional carboxylic acid is preferably used.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
  • esters of polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate.
  • Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxyp Epoxy) phenyl] dimethyl methane, bis - (methacryloxy
  • Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
  • crotonic acid esters examples include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.
  • isocrotonic acid esters examples include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
  • maleic acid esters examples include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.
  • esters examples include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59-5240.
  • the compounds having an aromatic skeleton described in JP-A No. 59-5241, JP-A-2-226149, compounds containing an amino group described in JP-A 1-165613, and the like are also preferably used. It is done.
  • amide monomers of polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylic.
  • examples include amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.
  • Examples of other preferable amide monomers include monomers having a cyclohexylene structure described in JP-B No. 54-21726.
  • urethane-based addition-polymerizable monomers produced using an addition reaction of isocyanate and hydroxyl group are also suitable.
  • Specific examples thereof include, for example, one molecule described in JP-B-48-41708.
  • Examples thereof include a vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group to a polyisocyanate compound having two or more isocyanate groups.
  • urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in Japanese Patent No. 17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable.
  • the compounds described in paragraph numbers 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.
  • the compound which has an ethylenically unsaturated bond the compound which has a boiling point of 100 degreeC or more under a normal pressure is also preferable.
  • monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol ( (Meth) acrylate, trimethylolpropane
  • n is an integer of 0 to 14, and m is an integer of 1 to 8.
  • a plurality of R and T present in one molecule may be the same or different.
  • Specific examples of the compound having an ethylenically unsaturated bond represented by the general formulas (MO-1) to (MO-5) are described in paragraph numbers 0248 to 0251 of JP-A-2007-267979. The compound can be suitably used in the present invention.
  • JP-A-10-62986 compounds represented by general formulas (1) and (2) together with specific examples thereof, which are (meth) acrylated after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol are also included. Can be used as a polymerizable compound.
  • Examples of the compound having an ethylenically unsaturated bond include dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320).
  • the compound having an ethylenically unsaturated bond may be a polyfunctional monomer having an acid group such as a carboxy group, a sulfonic acid group, or a phosphoric acid group.
  • the polyfunctional monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. More preferably, the ester is a polyfunctional monomer in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.
  • Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • the polyfunctional monomer having an acid group one kind may be used alone, or two or more kinds may be mixed and used. Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as needed.
  • a preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the polyfunctional monomer is in the above range, the production and handling properties are excellent, and further, the developability is excellent. Moreover, radical polymerizability is favorable.
  • a compound having a caprolactone structure can also be used.
  • the compound having a caprolactone structure and an ethylenically unsaturated bond is not particularly limited as long as it has a caprolactone structure in the molecule.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents a number of 1 or 2
  • “*” represents a bond.
  • R 1 represents a hydrogen atom or a methyl group, and “*” represents a bond.
  • the compounds having a caprolactone structure and an ethylenically unsaturated bond can be used alone or in admixture of two or more.
  • the compound having an ethylenically unsaturated bond is also preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).
  • each E independently represents — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) —
  • Each y independently represents an integer of 0 to 10
  • each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxy group.
  • the total number of (meth) acryloyl groups is 3 or 4
  • each m independently represents an integer of 0 to 10
  • the total of each m is an integer of 0 to 40.
  • any one of X is a carboxy group.
  • the total number of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. However, when the total of each n is 0, any one of X is a carboxy group.
  • m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
  • n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.
  • the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
  • bonds with is preferable.
  • a form in which all six Xs are acryloyl groups is preferable.
  • the compound represented by the general formula (i) or (ii) is a conventionally known process in which a ring-opening skeleton is bonded by a ring-opening addition reaction of ethylene oxide or propylene oxide with pentaerythritol or dipentaerythritol. And a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or (ii).
  • pentaerythritol derivatives and dipentaerythritol derivatives are more preferable.
  • Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”).
  • exemplary compounds (a), (f) b), (e) and (f) are preferred.
  • Examples of commercially available polymerizable compounds represented by general formulas (i) and (ii) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.
  • Examples of the compound having an ethylenically unsaturated bond include those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765.
  • Urethane acrylates and urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. It is.
  • polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are described as polymerizable compounds. Monomers can also be used.
  • urethane oligomer UAS-10 UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A -9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Bremer PME400 (manufactured by NOF Corporation) and the like can be mentioned.
  • the compound having an ethylenically unsaturated bond preferably has a partial structure represented by the following formula from the viewpoint of heat resistance. However, * in the formula is a connecting hand.
  • Specific examples of the compound having an ethylenically unsaturated bond having the above partial structure include, for example, trimethylolpropane tri (meth) acrylate, isocyanuric acid ethylene oxide-modified di (meth) acrylate, and isocyanuric acid ethylene oxide-modified tri (meth).
  • the content of the radical polymerizable compound is 1 to 50% by mass with respect to the total solid content of the negative photosensitive resin composition from the viewpoint of good radical polymerizability and heat resistance. Is preferred.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 30% by mass or less, and further preferably 25% by mass or less.
  • a radically polymerizable compound may be used alone or in combination of two or more.
  • the mass ratio of the polyimide precursor to the compound having a radical polymerizable compound is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, 90/10 to 50/50 is more preferable, and 90/10 to 70/30 is more preferable. If the mass ratio of a polyimide precursor and a radically polymerizable compound is the said range, the cured film excellent in sclerosis
  • the negative photosensitive resin composition of the present invention may contain a photobase generator.
  • a photobase generator generates a base upon exposure and does not exhibit activity under normal conditions of normal temperature and pressure. However, when an electromagnetic wave is irradiated and heated as an external stimulus, the base (basic substance) is generated. ) Is not particularly limited as long as it generates. Since the base generated by the exposure works as a catalyst for curing the polyimide precursor by heating, it can be suitably used in the negative type.
  • the content of the photobase generator is not particularly limited as long as it can form a desired pattern, and can be a general content.
  • the content of the photobase generator is preferably in the range of 0.05 to 30 parts by mass with respect to 100 parts by mass of the negative photosensitive resin composition, and 0.1 to 25 parts by mass. More preferably, it is in the range of 0.2 parts by mass to 20 parts by mass.
  • photobase generators can be used.
  • M.M. Shirai, and M.M. Tsunooka Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kadooka, polymer processing, 46, 2 (1997); Kutal, Coord. Chem. Rev. , 211, 353 (2001); Kaneko, A .; Sarker, and D.C. Neckers, Chem. Mater. 11, 170 (1999); Tachi, M .; Shirai, and M.M. Tsunooka, J. et al. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K.K. Graziano, J. et al. Photopolym.
  • An ionic compound neutralized by forming a salt with a base component, or a nonionic compound in which the base component is made latent by a urethane bond or an oxime bond such as a carbamate derivative, an oxime ester derivative, or an acyl compound can be mentioned.
  • the photobase generator that can be used in the present invention is not particularly limited and known ones can be used.
  • the basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines.
  • the generated basic substance is preferably a compound having an amino group having a higher basicity. This is because the catalytic action for the dehydration condensation reaction or the like in the imidization of the polyimide precursor is strong, and the catalytic effect in the dehydration condensation reaction or the like at a lower temperature can be expressed with a smaller amount of addition. That is, since the catalytic effect of the generated basic substance is large, the apparent sensitivity as a negative photosensitive resin composition is improved. From the viewpoint of the catalytic effect, an amidine and an aliphatic amine are preferable.
  • the photobase generator is preferably a photobase generator that does not contain salt in the structure. Moreover, it is preferable that there is no electric charge on the nitrogen atom of the base part generated in the photobase generator.
  • the generated base is preferably latentized using a covalent bond, and the base generation mechanism is such that the covalent bond between the nitrogen atom of the generated base moiety and the adjacent atom is cleaved. More preferably, the compound generates a base.
  • the base generator does not contain a salt in the structure, the base generator can be neutralized, so that the solvent solubility is good and the pot life is improved.
  • the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.
  • the photobase generator preferably has a latent base generated using a covalent bond as described above, and the generated base uses an amide bond, carbamate bond, or oxime bond. It is more preferable that it is latent.
  • the base generator according to the present invention include a base generator having a cinnamic acid amide structure as disclosed in Japanese Patent Application Laid-Open No. 2009-80452 and International Publication No. WO 2009/123122, and Japanese Patent Application Laid-Open No. 2006-189591.
  • a base generator having a carbamate structure as disclosed in JP-A-2008-247747, an oxime structure and a carbamoyloxime structure as disclosed in JP-A-2007-249013 and 2008-003581 examples thereof include, but are not limited to, a base generator having a known structure.
  • the photobase generator that can be used in the present invention will be described with specific examples.
  • the ionic compound include those having the following structural formula.
  • acyl compound examples include compounds represented by the following formula.
  • examples of the photobase generator include compounds represented by the following general formula (PB-1).
  • R 41 and R 42 each independently represent a hydrogen atom or an organic group, and may be the same or different, provided that at least one of R 41 and R 42 is present.
  • R 41 and R 42 may be bonded to each other to form a ring structure and may contain a heteroatom bond, and R 43 and R 44 are each an organic group.
  • R 45, R 46, R 47 and R 48 are each independently a hydrogen atom, halogen atom , Hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, or an organic group, may be different even in the same .
  • R 45, R 46, R 47 and R 48 are each independently a hydrogen atom, halogen atom , Hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammoni
  • examples of the photobase generator include compounds described in paragraph numbers 0185 to 0188, 0199 to 0200 and 0202 of JP2012-93746A, compounds described in paragraph numbers 0022 to 0069 of JP2013-194205A. Examples thereof include compounds described in JP-A-2013-204019, paragraphs 0026 to 0074, and compounds described in paragraph No. 0052 of WO2010 / 064631.
  • the negative photosensitive resin composition of the present invention may contain a thermal base generator.
  • the type of the thermal base generator is not particularly defined, but is selected from an acidic compound that generates a base when heated to 40 ° C. or higher, and an ammonium salt having an anion having an pKa1 of 0 to 4 and an ammonium cation. It is preferable to include a thermal base generator containing at least one kind.
  • pKa1 represents a logarithmic representation ( ⁇ Log 10 Ka) of the dissociation constant (Ka) of the first proton of the polyvalent acid.
  • the cyclization reaction of a polyimide precursor can be performed at low temperature, and it can be set as the negative photosensitive resin composition excellent in stability more. Moreover, since the base is not generated unless heated, the thermal base generator can suppress cyclization of the polyimide precursor during storage even if it coexists with the polyimide precursor, and is excellent in storage stability.
  • the thermal base generator in the present invention is at least one selected from an acidic compound (A1) that generates a base when heated to 40 ° C. or higher, and an ammonium salt (A2) having an anion having a pKa1 of 0 to 4 and an ammonium cation. including. Since the acidic compound (A1) and the ammonium salt (A2) generate a base when heated, the base generated from these compounds can accelerate the cyclization reaction of the polyimide precursor, thereby cyclizing the polyimide precursor. Can be performed at low temperatures.
  • the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C. or higher, more preferably 120 to 200 ° C.
  • the upper limit of the base generation temperature is more preferably 190 ° C or lower, further preferably 180 ° C or lower, and further preferably 165 ° C or lower.
  • the lower limit of the base generation temperature is more preferably 130 ° C or higher, and still more preferably 135 ° C or higher. If the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C. or higher, it is difficult to generate a base during storage. Therefore, it is possible to prepare a negative photosensitive resin composition having excellent stability. it can.
  • the cyclization temperature of the polyimide precursor can be lowered.
  • the base generation temperature is measured, for example, by using differential scanning calorimetry, heating the compound to 250 ° C. at 5 ° C./min in a pressure capsule, reading the peak temperature of the lowest exothermic peak, and measuring the peak temperature as the base generation temperature. can do.
  • the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since tertiary amine has high basicity, the cyclization temperature of a polyimide precursor can be made lower. Further, the boiling point of the base generated by the thermal base generator is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and most preferably 140 ° C. or higher. The molecular weight of the generated base is preferably 80 to 2000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. The molecular weight value is a theoretical value obtained from the structural formula.
  • the acidic compound (A1) preferably contains one or more selected from an ammonium salt and a compound represented by the following general formula (1).
  • the ammonium salt (A2) is preferably an acidic compound.
  • the ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C. or higher (preferably 120 to 200 ° C.), or 40 ° C. or higher (preferably 120 to 200 ° C.). ) May be a compound other than an acidic compound that generates a base when heated.
  • the ammonium salt means a salt of an ammonium cation represented by the following general formula (1) or general formula (2) and an anion.
  • the anion may be bonded to any part of the ammonium cation via a covalent bond, and may be outside the molecule of the ammonium cation, but is preferably outside the molecule of the ammonium cation.
  • numerator of an ammonium cation means the case where an ammonium cation and an anion are not couple
  • the anion outside the molecule of the cation moiety is also referred to as a counter anion.
  • R 1 to R 6 each independently represents a hydrogen atom or a hydrocarbon group
  • R 7 represents a hydrocarbon group
  • R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 5 and R 7 may be bonded to form a ring.
  • the ammonium salt preferably has an anion having an pKa1 of 0 to 4 and an ammonium cation.
  • the upper limit of the anion pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less.
  • the lower limit is more preferably 0.5 or more, and further preferably 1.0 or more. If the pKa1 of the anion is in the above range, the polyimide precursor can be cyclized at a low temperature, and further, the stability of the negative photosensitive resin composition can be improved. If pKa1 is 4 or less, the stability of the thermal base generator is good, the generation of a base without heating can be suppressed, and the stability of the negative photosensitive resin composition is good.
  • the kind of anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is more preferable because both the stability of the salt and the thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
  • the carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxy groups, and more preferably a divalent carboxylic acid anion.
  • the stability, curability and developability of the negative photosensitive resin composition can be further improved by using an anion of a divalent carboxylic acid.
  • the carboxylic acid anion is preferably a carboxylic acid anion having a pKa1 of 4 or less.
  • pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less.
  • the stability of the negative photosensitive resin composition can be further improved.
  • pKa1 represents the logarithm of the reciprocal of the first dissociation constant of the acid.
  • the carboxylate anion is preferably represented by the following general formula (X1).
  • EWG represents an electron-withdrawing group.
  • the electron-withdrawing group means a group having a positive Hammett's substituent constant ⁇ m.
  • ⁇ m is a review by Yugo Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) P.I. 631-642.
  • the electron-withdrawing group of the present invention is not limited to the substituents described in the above documents.
  • Me represents a methyl group
  • Ac represents an acetyl group
  • Ph represents a phenyl group.
  • EWG preferably represents a group represented by the following general formulas (EWG-1) to (EWG-6).
  • R x1 to R x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, or a carboxy group
  • Ar represents an aryl group.
  • the carboxylate anion is also preferably represented by the following general formula (X).
  • L 10 represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an arylene group, —NR X —, and a combination thereof
  • R X represents a hydrogen atom Represents an alkyl group, an alkenyl group or an aryl group.
  • carboxylate anion examples include a maleate anion, a phthalate anion, an N-phenyliminodiacetic acid anion, and an oxalate anion. These can be preferably used.
  • ammonium cation is preferably represented by any one of the following general formulas (Y1-1) to (Y1-6).
  • R 101 represents an n-valent organic group
  • R 102 to R 111 each independently represents a hydrogen atom or a hydrocarbon group
  • R 150 and R 151 each independently represent a hydrocarbon group
  • R 104 and R 105 , R 104 and R 150 , R 107 and R 108 , and R 109 and R 110 may be bonded to each other to form a ring
  • Ar 101 and Ar 102 each independently represent an aryl group
  • n represents an integer of 1 or more
  • m represents an integer of 0 to 5.
  • the acidic compound is also preferably a compound represented by the following general formula (A1). Although this compound is acidic at room temperature, the carboxy group is lost by decarboxylation or dehydration cyclization by heating, so that the amine site that has been neutralized and inactivated becomes active, and thus the base is activated. It becomes sex.
  • general formula (A1) is demonstrated.
  • a 1 represents a p-valent organic group
  • R 1 represents a monovalent organic group
  • L 1 represents a (m + 1) -valent organic group
  • m represents an integer of 1 or more
  • P represents an integer of 1 or more.
  • a 1 represents a p-valent organic group.
  • the organic group include an aliphatic group and an aryl group, and an aryl group is preferable.
  • the compound represented by the general formula (A1) is preferably a compound represented by the following general formula (1a).
  • a 1 , L 1 , L 2 , m, n, and p in the general formula (1a) have the same meaning as the range described in the general formula (1), and the preferable range is also the same.
  • the compound represented by the general formula (A1) is preferably N-aryliminodiacetic acid.
  • a 1 in the general formula (A1) is an aryl group
  • L 1 and L 2 are methylene groups
  • m is 1
  • n is 1
  • p is 1.
  • N-aryliminodiacetic acid tends to generate a tertiary amine having a high boiling point at 120 to 200 ° C.
  • thermal base generator in the present invention is not limited to these. These can be used alone or in admixture of two or more. Me in the following formulas represents a methyl group.
  • thermal base generator used in the present invention, compounds described in paragraph Nos. 0015 to 0055 of Japanese Patent Application No. 2015-034388 are also preferably used, the contents of which are incorporated herein.
  • the content of the thermal base generator in the negative photosensitive resin composition is preferably 0.1 to 50% by mass with respect to the total solid content of the negative photosensitive resin composition.
  • the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
  • the upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
  • 1 type (s) or 2 or more types can be used for a thermal base generator. When using 2 or more types, it is preferable that a total amount is the said range.
  • the negative photosensitive resin composition of the present invention may contain a thermal radical polymerization initiator.
  • a thermal radical polymerization initiator a known thermal radical polymerization initiator can be used.
  • the thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound can be advanced when the cyclization reaction of the polyimide precursor is advanced.
  • Thermal radical polymerization initiators include aromatic ketones, onium salt compounds, peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogens. Examples thereof include a compound having a bond and an azo compound. Among these, a peroxide or an azo compound is more preferable, and a peroxide is particularly preferable.
  • the thermal radical polymerization initiator used in the present invention preferably has a 10-hour half-life temperature of 90 to 130 ° C, more preferably 100 to 120 ° C.
  • Specific examples include compounds described in paragraph numbers 0074 to 0118 of JP-A-2008-63554.
  • perbutyl Z and park mill D made by NOF Corporation can be used conveniently.
  • the content of the thermal radical polymerization initiator is preferably 0.1 to 50% by mass with respect to the total solid content of the negative photosensitive resin composition. 0.1 to 30% by mass is more preferable, and 0.1 to 20% by mass is particularly preferable. Further, the thermal radical polymerization initiator is preferably contained in an amount of 0.1 to 50 parts by mass, and more preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the polymerizable compound. According to this aspect, it is easy to form a cured film having more excellent heat resistance. Only one type of thermal radical polymerization initiator may be used, or two or more types may be used. When there are two or more thermal radical polymerization initiators, the total is preferably in the above range.
  • a corrosion inhibitor to the negative photosensitive resin composition of the present invention.
  • the corrosion inhibitor is added for the purpose of preventing the outflow of ions from the metal wiring.
  • Examples of the compound include a rust inhibitor described in paragraph No. 0094 of JP2013-15701A, and JP2009-283711A.
  • the compounds described in Paragraph Nos. 0073 to 0076, the compound described in Paragraph No. 0052 of JP 2011-59656 A, the compounds described in Paragraph Nos. 0114, 0116, and 0118 of JP 2012-194520 A are used. be able to.
  • a compound having a triazole ring or a compound having a tetrazole ring can be preferably used.
  • 1,2,4-triazole, 1,2,3-benzotriazole, 5-methyl-1H-benzotriazole, 1H-tetrazole 5-methyl-1H-tetrazole is more preferred, and 1H-tetrazole is most preferred.
  • the corrosion inhibitor is added, the amount of the corrosion inhibitor is preferably in the range of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the polyimide precursor. It is a range. Only one type of corrosion inhibitor may be used, or two or more types may be used. When there are two or more corrosion inhibitors, the total is preferably in the above range.
  • the negative photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to a metal material used for electrodes, wirings and the like.
  • metal adhesion improvers include sulfide compounds described in paragraph numbers 0046 to 0049 of JP-A-2014-186186 and paragraph numbers 0032 to 0043 of JP-A-2013-072935.
  • the compounding amount of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts per 100 parts by mass of the polyimide precursor. It is the range of mass parts.
  • membrane and metal after thermosetting becomes favorable, and the heat resistance of the film
  • Only one type of metal adhesion improver may be used, or two or more types may be used.
  • the negative photosensitive resin composition of the present invention preferably contains a silane coupling agent in terms of improving the adhesion to the substrate.
  • the silane coupling agent include compounds described in paragraphs 0062 to 0073 of JP2014-191002, compounds described in paragraphs 0063 to 0071 of WO2011 / 080992A1, and JP2014-191252A. And the compounds described in paragraph Nos. 0060 to 0061 of JP-A No. 2014-41264, the compounds described in paragraph Nos. 0045 to 0052 of JP 2014-41264 A, and the compounds described in paragraph No. 0055 of WO 2014/097594.
  • the amount of the silane coupling agent is preferably in the range of 0.1 to 20 parts by mass, more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the polyimide precursor. It is. When it is 0.1 part by mass or more, sufficient adhesion to the substrate can be imparted, and when it is 20 parts by mass or less, problems such as an increase in viscosity during storage at room temperature can be further suppressed. Only one type of silane coupling agent may be used, or two or more types may be used. When using 2 or more types of silane coupling agents, it is preferable that the sum total is the said range.
  • the negative photosensitive resin composition of the present invention may contain a sensitizing dye.
  • a sensitizing dye absorbs specific actinic radiation and enters an electronically excited state.
  • the sensitizing dye in an electronically excited state is brought into contact with a thermal base generator, a thermal radical polymerization initiator, a photo radical polymerization initiator or the like, and causes actions such as electron transfer, energy transfer, and heat generation.
  • a thermal base generator, a thermal radical polymerization initiator, and a photo radical polymerization initiator cause a chemical change and are decomposed to generate radicals, acids, or bases.
  • preferable sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in the range of 300 nm to 450 nm.
  • polynuclear aromatics for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9.10-dialkoxyanthracene
  • xanthenes for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
  • thioxanthones for example, 2,4-diethylthioxanthone
  • cyanines for example thiacarbocyanine, oxacarbocyanine
  • merocyanines for example merocyanine, carbomerocyanine
  • thiazines for example thionine, methylene blue, toluidine blue
  • acridines Eg, acridine orange, chloroflavin, acriflavine
  • anthrdines
  • polynuclear aromatics for example, phenanthrene, anthracene, pyrene, perylene, triphenylene
  • thioxanthones for example, phenanthrene, anthracene, pyrene, perylene, triphenylene
  • thioxanthones for example, thioxanthones
  • distyrylbenzenes for example, thioxanthones
  • distyrylbenzenes for example, phenanthrene, anthracene, pyrene, perylene, triphenylene
  • thioxanthones for example, phenanthrene, anthracene, pyrene, perylene, triphenylene
  • thioxanthones for example, thioxanthones
  • distyrylbenzenes for example, thioxanthones
  • distyrylbenzenes for example, thioxanthones
  • the content of the sensitizing dye is preferably 0.01 to 20% by mass, based on the total solid content of the negative photosensitive resin composition, 0.1 Is more preferably 15 to 15% by mass, and further preferably 0.5 to 10% by mass.
  • a sensitizing dye may be used individually by 1 type, and may use 2 or more types together.
  • the negative photosensitive resin composition of the present invention may contain a chain transfer agent.
  • the chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (edited by the Polymer Society, 2005) pages 683-684.
  • As the chain transfer agent for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These can donate hydrogen to low-activity radical species to generate radicals, or can be oxidized and then deprotonated to generate radicals.
  • thiol compounds for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.
  • 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc. can be preferably used.
  • the content of the chain transfer agent is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the negative photosensitive resin composition. More preferably, it is 1 to 10 parts by mass, and still more preferably 1 to 5 parts by mass. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more chain transfer agents, the total is preferably in the above range.
  • the negative photosensitive resin composition of the present invention preferably contains a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polyimide precursor and the radical polymerizable compound during production or storage.
  • a polymerization inhibitor examples include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert).
  • the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the negative photosensitive resin composition. Only one polymerization inhibitor may be used, or two or more polymerization inhibitors may be used. When using 2 or more types of polymerization inhibitors, it is preferable that the sum total is the said range.
  • Various surfactants may be added to the negative photosensitive resin composition of the present invention from the viewpoint of further improving coatability.
  • the surfactant various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • a fluorosurfactant liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the uniformity of coating thickness and liquid-saving properties can be further improved.
  • the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid, and the coated surface The coating property of is improved. For this reason, even when a thin film of about several ⁇ m is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
  • the fluorine content of the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility.
  • fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.
  • a block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
  • the following compounds are also exemplified as the fluorosurfactant used in the present invention.
  • the weight average molecular weight of the above compound is, for example, 14,000.
  • nonionic surfactant examples include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1) Solsperse 20000 (Lubrizol Japan Co., Ltd.), and the like.
  • cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
  • phthalocyanine derivatives trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.
  • organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
  • (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 manufactured by Kyoeisha Chemical Co., Ltd.
  • W001 manufactured by Yusho Co., Ltd.
  • anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
  • silicone surfactant examples include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd.
  • the content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the negative photosensitive resin composition. More preferably, the content is 0.005 to 1.0% by mass. Only one surfactant may be used, or two or more surfactants may be used. When two or more surfactants are contained, the total is preferably in the above range.
  • a negative fatty acid derivative such as behenic acid or behenamide is added to the negative photosensitive resin composition of the present invention, and the negative photosensitive resin composition in the drying process after coating. It may be unevenly distributed on the surface of the photosensitive resin composition.
  • the content of the higher fatty acid derivative or the like is preferably 0.1 to 10% by mass with respect to the total solid content of the negative photosensitive resin composition. . Only one type of higher fatty acid derivative or the like may be used. When two or more higher fatty acid derivatives are contained, the total is preferably within the above range.
  • ⁇ Solvent> When the negative photosensitive resin composition of the present invention is layered by coating, it is preferable to blend a solvent. If a negative photosensitive resin composition can be formed in a layer form, a well-known thing can be used for a solvent without a restriction
  • the solvent used in the negative photosensitive resin composition of the present invention include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate.
  • alkyl oxyacetate eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, Butyl methoxyacetate, methyl ethoxyacetate, ethyl e
  • the solvent is preferably in the form of a mixture of two or more types from the viewpoint of improving the coated surface.
  • a mixed solution composed of two or more selected from dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable.
  • the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
  • the content of the solvent should be such that the total solid content concentration of the negative photosensitive resin composition is 5 to 80% by mass from the viewpoint of applicability. It is preferably 5 to 70% by mass, more preferably 10 to 60% by mass. One type of solvent may be sufficient and 2 or more types may be sufficient as it. When two or more solvents are contained, the total is preferably in the above range.
  • the content of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide is such that the negative photosensitive resin composition can be used from the viewpoint of film strength. It is preferably less than 5% by mass, more preferably less than 1% by mass, further preferably less than 0.5% by mass, and particularly preferably less than 0.1% by mass with respect to the total mass.
  • the negative photosensitive resin composition of the present invention is various additives, for example, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet rays, as necessary, as long as the effects of the present invention are not impaired.
  • Absorbers, anti-aggregation agents and the like can be blended. When mix
  • the water content of the negative photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass from the viewpoint of the coated surface.
  • the metal content of the negative photosensitive resin composition of the present invention is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and particularly preferably less than 0.5 ppm by mass.
  • the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are included, the total of these metals is preferably in the above range.
  • a negative photosensitive resin composition in which a raw material having a low metal content is selected as a raw material constituting the negative photosensitive resin composition. Filter the raw material constituting the conductive resin composition, and line the inside of the apparatus with polytetrafluoroethylene or the like, and perform distillation under the conditions that suppress contamination as much as possible. .
  • the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass from the viewpoint of wiring corrosion.
  • a halogen ion is less than 5 mass ppm, more preferably less than 1 mass ppm, and especially less than 0.5 mass ppm.
  • the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms, or chloride ions and bromide ions is preferably in the above range.
  • the negative photosensitive resin composition of the present invention can be prepared by mixing the above components.
  • the mixing method is not particularly limited, and can be performed by a conventionally known method.
  • the pore size of the filter is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
  • the filter material is preferably a polytetrafluoroethylene, polyethylene, or nylon filter. A filter that has been washed in advance with an organic solvent may be used.
  • a plurality of types of filters may be connected in series or in parallel.
  • filters having different pore diameters and / or materials may be used in combination.
  • various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.
  • you may pressurize and filter and the pressure to pressurize is 0.05 MPa or more and 0.3 MPa or less.
  • impurities may be removed using an adsorbent.
  • the adsorbent a known adsorbent can be used.
  • inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
  • the negative photosensitive resin composition of the present invention can be cured and used as a cured film. Since the negative photosensitive resin composition of the present invention can form a cured film having excellent heat resistance and insulation, it can be preferably used for an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, and the like. In particular, it can be preferably used for an interlayer insulating film for a rewiring layer in a three-dimensional mounting device. It can also be used as a photoresist for electronics (galvanic resist, galvanic resist, etching resist, solder top resist). It can also be used for the production of printing plates such as offset printing plates or screen printing plates, the etching of molded parts, the production of protective lacquers and dielectric layers in electronics, in particular microelectronics.
  • the method for producing a cured film is not particularly defined as long as it is formed using the negative photosensitive resin composition of the present invention.
  • the method for producing a cured film of the present invention preferably includes a step of applying the negative photosensitive resin composition of the present invention to a substrate and a step of curing the negative photosensitive resin composition applied to the substrate. .
  • Step of applying negative photosensitive resin composition to substrate Examples of the method for applying the negative photosensitive resin composition to the substrate include spinning, dipping, doctor blade coating, suspension casting, coating, spraying, electrostatic spraying, reverse roll coating, and the like. Electrostatic spraying and reverse roll coating are preferred because they can be applied uniformly on the substrate.
  • Examples of the substrate include inorganic substrates, resins, and resin composite materials.
  • Examples of the inorganic substrate include a glass substrate, a quartz substrate, a silicon substrate, a silicon nitride substrate, and a composite substrate obtained by depositing molybdenum, titanium, aluminum, copper, or the like on such a substrate.
  • polystyrene polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, Fluorine resin such as polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, Groups consisting of synthetic resins such as aromatic ethers, maleimide-olefins, cellulose, episulfide compounds And the like.
  • TFT thin film transistor
  • the amount (layer thickness) and type of substrate (layer carrier) to which the negative photosensitive resin composition is applied depends on the field of application desired. It is particularly advantageous that the photosensitive resin composition can be used in layer thicknesses that can be varied over a wide range.
  • the range of the layer thickness is preferably 0.5 to 100 ⁇ m.
  • the cyclization reaction of the polyimide precursor proceeds and a cured film having excellent heat resistance can be formed.
  • the heating temperature is preferably 50 to 300 ° C, more preferably 100 to 250 ° C. According to the present invention, since many isomers with a faster cyclization rate are contained, the cyclization reaction of the polyimide precursor can be performed at a lower temperature.
  • the rate of temperature rise is preferably 3 to 5 ° C./min, with 20 to 150 ° C. being the heating start temperature.
  • the heating temperature is 200 to 240 ° C.
  • the heating time is preferably 180 minutes or more.
  • the upper limit is preferably 240 minutes or less.
  • the heating time is preferably 90 minutes or more.
  • the upper limit is preferably 180 minutes or less.
  • the heating temperature is 300 to 380, the heating time is preferably 60 minutes or more.
  • the upper limit is preferably 120 minutes or less.
  • the cooling rate is preferably 1 to 5 ° C./min. Heating may be performed in stages. For example, the temperature is raised from 20 ° C. to 150 ° C. at 5 ° C./minute, placed at 150 ° C. for 30 minutes, heated from 150 ° C. to 230 ° C. at 5 ° C./minute, and placed at 230 ° C. for 180 minutes A process is mentioned.
  • the heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of a polyimide precursor such as polyimide.
  • the oxygen concentration is preferably 50 ppm by volume or less, more preferably 20 ppm by volume or less.
  • the pattern forming step can be performed by, for example, a photolithography method.
  • a photolithography method For example, the method of performing through the process of exposing and the process of developing is mentioned.
  • the pattern formation by the photolithography method is preferably performed using a photosensitive resin composition containing a polyimide precursor and a radical photopolymerization initiator.
  • a photosensitive resin composition containing a polyimide precursor and a radical photopolymerization initiator.
  • the negative photosensitive resin composition applied to the substrate is irradiated with a predetermined pattern of actinic rays or radiation.
  • the wavelength of the actinic ray or radiation varies depending on the composition of the negative photosensitive resin composition, but is preferably 200 to 600 nm, and more preferably 300 to 450 nm.
  • a light source a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, or the like can be used.
  • Actinic rays having a wavelength of 300 nm to 450 nm can be preferably used.
  • irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
  • the exposure dose is preferably 1 to 1000 mJ / cm 2 , more preferably 200 to 800 mJ / cm 2 .
  • the value of the present invention is high in that it can be developed with high developability in such a wide range.
  • various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, and a laser exposure can be used.
  • the unexposed portion of the negative photosensitive resin composition is developed using a developer.
  • a developer an aqueous alkaline developer, an organic solvent, or the like can be used.
  • the alkali compound used in the aqueous alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, and metasilicic acid. Examples include potassium, ammonia, and amine.
  • amines examples include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, tetramethylammonium hydroxide. (TMAH) or tetraethylammonium hydroxide.
  • TMAH tetramethylammonium hydroxide
  • alkali compounds containing no metal are preferred.
  • Suitable aqueous alkaline developers are generally up to 0.5 N with respect to alkali, but may be diluted appropriately prior to use.
  • an aqueous alkaline developer having a concentration of about 0.15 to 0.4 N, preferably 0.20 to 0.35 N is also suitable. Only one alkali compound may be used, or two or more alkali compounds may be used. When using 2 or more types of alkali compounds, it is preferable that the sum total is the said range.
  • an organic solvent the thing similar to the solvent which can be used for the negative photosensitive resin composition mentioned above can be used. For example, preferred are n-butyl acetate, ⁇ -butyrolactone, cyclopentanone, and a mixture thereof. Further, it is preferable to include a step of heating the developed negative photosensitive resin composition at a temperature of 50 to 500 ° C. after the step of performing the development treatment. By passing through such a process, there exists a merit that heat resistance and adhesiveness with a board
  • the method for producing a cured film of the present invention can be preferably used for an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, and the like. Particularly, since the resolution is good, it can be preferably used for an interlayer insulating film for a rewiring layer in a three-dimensional mounting device. It can also be used as a photoresist for electronics (galvanic resist, galvanic resist, etching resist, solder top resist). Also. It can also be used for the production of printing plates such as offset printing plates or screen printing plates, etching of molded parts, the production of protective lacquers and dielectric layers in electronics, in particular microelectronics.
  • a semiconductor device 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a stacked body 101 in which a plurality of semiconductor elements (semiconductor chips) 101 a to 101 d are stacked is arranged on a wiring board 120.
  • the case where the number of stacked semiconductor elements (semiconductor chips) is four will be mainly described.
  • the number of stacked semiconductor elements (semiconductor chips) is not particularly limited. It may be a layer, 8 layers, 16 layers, 32 layers, or the like. Moreover, one layer may be sufficient.
  • Each of the plurality of semiconductor elements 101a to 101d is made of a semiconductor wafer such as a silicon substrate.
  • the uppermost semiconductor element 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof.
  • the semiconductor elements 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) provided integrally with the through electrodes are provided on both surfaces of each semiconductor element.
  • the stacked body 101 has a structure in which a semiconductor element 101a having no through electrode and semiconductor elements 101b to 101d having through electrodes 102b to 102d are flip-chip connected. That is, the electrode pad of the semiconductor element 101a having no through electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b having the adjacent through electrode 102b are connected by the metal bump 103a such as a solder bump, The connection pad on the other side of the semiconductor element 101b having the electrode 102b is connected to the connection pad on the semiconductor element 101b side of the semiconductor element 101c having the penetrating electrode 102c adjacent thereto by a metal bump 103b such as a solder bump.
  • connection pad on the other side of the semiconductor element 101c having the through electrode 102c is connected to the connection pad on the semiconductor element 101c side of the semiconductor element 101d having the adjacent through electrode 102d by the metal bump 103c such as a solder bump. ing.
  • An underfill layer 110 is formed in the gaps between the semiconductor elements 101a to 101d, and the semiconductor elements 101a to 101d are stacked via the underfill layer 110.
  • the stacked body 101 is stacked on the wiring board 120.
  • the wiring substrate 120 for example, a multilayer wiring substrate using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a base material is used.
  • the wiring board 120 to which the resin board is applied include a multilayer copper-clad laminate (multilayer printed wiring board).
  • a surface electrode 120 a is provided on one surface of the wiring board 120.
  • An insulating layer 115 in which a rewiring layer 105 is formed is disposed between the wiring substrate 120 and the stacked body 101, and the wiring substrate 120 and the stacked body 101 are electrically connected via the rewiring layer 105. It is connected.
  • the insulating layer 115 is formed by using the negative photosensitive resin composition of the present invention. That is, one end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d on the rewiring layer 105 side through a metal bump 103d such as a solder bump.
  • the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump.
  • An underfill layer 110 a is formed between the insulating layer 115 and the stacked body 101.
  • an underfill layer 110 b is formed between the insulating layer 115 and the wiring substrate 120.
  • reaction mixture was then cooled to ⁇ 10 ° C. and 16.12 g (135.5 mmol) of SOCl 2 was added over 10 minutes while maintaining the temperature at ⁇ 10 ⁇ 4 ° C. During the addition of SOCl 2 the viscosity increased. After dilution with 50 ml N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours.
  • the reaction mixture was then stirred overnight at room temperature. Then, it was poured into 5 liters of water to precipitate the polyimide precursor, and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was collected by filtration, poured into 4 liters of water again, stirred for another 30 minutes, and filtered again. Next, the obtained polyimide precursor was dried at 45 ° C. under reduced pressure for 3 days to obtain a polyimide precursor (A-3).
  • Synthesis Example 4 Polyimide precursor (A-4) composed of pyromellitic dianhydride, poly (propylene glycol) bis (2-aminopropyl ether), 4,4′-oxydianiline, and 2-hydroxyethyl methacrylate )> 14.06 g (64.5 mmol) pyromellitic dianhydride (dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g hydroquinone, 10.7 g Of pyridine and 140 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate.
  • reaction mixture was then cooled to ⁇ 10 ° C. and 16.12 g (135.5 mmol) of SOCl 2 was added over 10 minutes while maintaining the temperature at ⁇ 10 ⁇ 4 ° C. During the addition of SOCl 2 the viscosity increased. After dilution with 50 ml N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours.
  • polyimide precursor was collected by filtration, poured into 4 liters of water again, stirred for another 30 minutes, and filtered again. Next, the obtained polyimide precursor was dried at 45 ° C. under reduced pressure for 3 days to obtain a polyimide precursor (A-4) having a repeating unit represented by the following formula.
  • n (average) is 6.
  • the molar ratio of the left repeating unit to the right repeating unit is 50:50.
  • Polyimide precursor (A) composed of 3,3′4,4′-diphenyl ether tetracarboxylic dianhydride, poly (propylene glycol) bis (2-aminopropyl ether), and 2-hydroxyethyl methacrylate -5)> Except changing 14.06 g (64.5 mmol) of pyromellitic dianhydride of Synthesis Example 1 to 20.00 g (64.5 mmol) of 3,3′4,4′-diphenyl ether tetracarboxylic dianhydride was synthesized by the same method as in Synthesis Example 1 to obtain a polyimide precursor (A-5) having a repeating unit represented by the following formula. In the above, n (average) is 6.
  • reaction mixture was then cooled to ⁇ 10 ° C. and 16.12 g (135.5 mmol) of SOCl 2 was added over 10 minutes while maintaining the temperature at ⁇ 10 ⁇ 4 ° C. During the addition of SOCl 2 the viscosity increased. After dilution with 50 ml N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 11.8 g (58.7 mmol) of 4,4′-oxydianiline dissolved in 100 ml of N-methylpyrrolidone was dropped into the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred overnight at room temperature.
  • ⁇ Synthesis Example 7 Polyimide precursor comprising pyromellitic dianhydride, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, and 2-hydroxyethyl methacrylate (RA-2 for comparative example) 11.8 g (58.7 mmol) of 4,4′-oxydianiline of Synthesis Example 6 was converted to 14.6 g (58.7 mmol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane.
  • a polyimide precursor (RA-2) having a repeating unit represented by the following formula was obtained by synthesis in the same manner as in Synthesis Example 6 except for changing.
  • Each negative photosensitive resin composition was subjected to pressure filtration through a filter having a pore width of 0.8 ⁇ m and then applied to a silicon wafer by spinning (3500 rpm, 30 seconds).
  • the silicon wafer to which the negative photosensitive resin composition was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform photosensitive resin composition layer having a thickness of 16 ⁇ m on the silicon wafer.
  • the photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR2005 i9C). The exposure is performed with i-line, and at a wavelength of 365 nm, using a line and space photomask in increments of 1 ⁇ m from 5 ⁇ m to 25 ⁇ m with each exposure energy of 200, 300, 400, 500, 600, 700, 800 mJ / cm 2. , Exposure was performed.
  • the exposed photosensitive resin composition layer was developed with cyclopentanone for 60 seconds.
  • the line width that was able to have good edge sharpness was evaluated according to the following criteria. The smaller the line width of the photosensitive resin composition layer, the greater the difference in solubility in the developer between the light-irradiated part and the light non-irradiated part, which is a preferable result. Further, if the change in the line width is small with respect to the change in exposure energy, it indicates that the exposure latitude is wide, which is a preferable result. The measurement limit is 5 ⁇ m. The results are shown in Table 5. A: 5 ⁇ m to 8 ⁇ m B: Over 8 ⁇ m to 10 ⁇ m or less C: Over 10 ⁇ m to 15 ⁇ m or less D: Over 15 ⁇ m to 20 ⁇ m or less E: Over 20 ⁇ m.
  • Each negative photosensitive resin composition was subjected to pressure filtration through a filter having a pore width of 0.8 ⁇ m, and then applied to a silicon wafer by spinning (3500 rpm, 30 seconds). After a silicon wafer to which the negative photosensitive resin composition is applied is dried on a hot plate at 100 ° C. for 5 minutes, a uniform photosensitive resin composition layer having a thickness of 16 ⁇ m is formed on the 4-inch wafer on the silicon wafer. The entire surface was exposed with an exposure energy of 500 mJ / cm 2 using i-line, and further heated at 300 ° C. for 3 hours to prepare a sample for warpage measurement.
  • the bow value was measured using a FLX-2320 manufactured by KLA-Tencor as a sample for warpage measurement. One inch is 2.54 cm.
  • Each negative photosensitive resin composition was subjected to pressure filtration through a filter having a pore width of 0.8 ⁇ m, and then applied to a copper substrate by spinning (3500 rpm, 30 seconds).
  • the copper substrate to which the negative photosensitive resin composition was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform photosensitive resin composition layer having a thickness of 16 ⁇ m on the 4-inch wafer on the copper substrate. Thereafter, the entire surface was exposed with an exposure energy of 500 mJ / cm 2 using i-line, and further heated at 300 ° C. for 3 hours.
  • the adhesive properties with the copper substrate were evaluated based on the following criteria.
  • Photosensitive resin composition layer adhered to the substrate is less than 50
  • A Polyimide precursor Polyimide precursor used in the above synthesis example
  • B Photoradical polymerization initiator
  • B-1 Irgacure OXE-01 (manufactured by BASF)
  • B-2 Irgacure 369 (BASF)
  • B-3 Irgacure 784 (BASF)
  • C-1 NK ester M-40G (manufactured by Shin-Nakamura Chemical Co., Ltd .; monofunctional methacrylate; structure shown below)
  • C-2 NK ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd .; bifunctional metallate; structure shown below)
  • C-3 NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd .; trifunctional acrylate; structure shown below)
  • C-4 NK ester A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd .; bifunctional acrylate; the following structure)
  • C-5 NK ester A-HD-N (manufactured by Shin-Nakamura Chemical Co., Ltd .; bifunctional acrylate; the following structure)
  • Example 100 The negative photosensitive resin composition of Example 1 was subjected to pressure filtration through a filter having a pore width of 0.8 ⁇ m and then applied to a resin substrate on which a thin copper layer was formed by spinning (3500 rpm, 30 seconds). did.
  • the negative photosensitive resin composition applied to the resin substrate was dried at 100 ° C. for 5 minutes and then exposed using an aligner (Karl-Suss MA150). Exposure was performed with a high-pressure mercury lamp, and exposure energy at a wavelength of 365 nm was measured. After exposure, the image was developed with cyclopentanone for 75 seconds. Subsequently, it heated at 180 degreeC for 20 minutes.

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Abstract

La présente invention concerne une composition de résine photosensible négative présentant une latitude de pose élevée, un film durci, un procédé de production de film durci et un dispositif à semi-conducteurs. Cette composition de résine photosensible négative comprend un précurseur polyimide ayant un motif à répétition représenté par la formule générale (1), et un photo-initiateur de polymérisation radicalaire ; dans la formule générale (1), A1 et A2 représentent chacun indépendamment un atome d'oxygène ou -NH-, R11 est un groupe de liaison divalent ayant un groupe représenté par -(L-O-)n1- dans la chaîne principale, L est un groupe alkylène ou -Si(R)2-, R est un groupe organique monovalent, n1 est un nombre entier supérieur ou égal à 2, R12 représente un groupe organique tétravalent, et R13 et R14 représentent chacun indépendamment un atome d'hydrogène ou un groupe organique monovalent.
PCT/JP2016/069276 2015-06-30 2016-06-29 Composition de résine photosensible négative, film durci, procédé de production de film durci et dispositif à semi-conducteurs WO2017002860A1 (fr)

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KR1020177035558A KR102041204B1 (ko) 2015-06-30 2016-06-29 네거티브형 감광성 수지 조성물, 경화막, 경화막의 제조 방법 및 반도체 디바이스

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JPWO2020255859A1 (fr) * 2019-06-17 2020-12-24
US20220145009A1 (en) * 2019-07-30 2022-05-12 Fujifilm Corporation Coloring resin composition, film, color filter, solid-state imaging element, and image display device
WO2023228613A1 (fr) * 2022-05-24 2023-11-30 パナソニックＩｐマネジメント株式会社 Polyimide, procédé de production d'un composé imide, et procédé de production de polyimide recyclé

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