WO2022009676A1 - Photosensitive resin composition and cured resin film obtained therefrom - Google Patents

Photosensitive resin composition and cured resin film obtained therefrom Download PDF

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Publication number
WO2022009676A1
WO2022009676A1 PCT/JP2021/023720 JP2021023720W WO2022009676A1 WO 2022009676 A1 WO2022009676 A1 WO 2022009676A1 JP 2021023720 W JP2021023720 W JP 2021023720W WO 2022009676 A1 WO2022009676 A1 WO 2022009676A1
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WIPO (PCT)
Prior art keywords
resin composition
photosensitive resin
copolymer
meth
group
Prior art date
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PCT/JP2021/023720
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French (fr)
Japanese (ja)
Inventor
正偉 周
健宏 木下
Original Assignee
昭和電工株式会社
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Publication date
Application filed by 昭和電工株式会社 filed Critical 昭和電工株式会社
Priority to CN202180047283.3A priority Critical patent/CN115867867A/en
Priority to KR1020227044047A priority patent/KR20230013063A/en
Priority to JP2022535006A priority patent/JPWO2022009676A1/ja
Publication of WO2022009676A1 publication Critical patent/WO2022009676A1/en

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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • 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
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains

Definitions

  • the present invention relates to a photosensitive resin composition that can be developed with an alkali, an overcoat obtained by curing the photosensitive resin composition, an interlayer insulating film, a surface protective film, and other cured resin films.
  • These members can be suitably used as members constituting an image display device such as a touch panel, a liquid crystal display device, and an organic EL device.
  • Patent Document 1 discloses a radiation-sensitive resin composition containing a polymer having a specific structural unit, an epoxy compound, and a radiation-sensitive compound. It is described that the radiation-sensitive resin composition can form a cured film through steps such as coating on a substrate, prebaking, exposure, development, and post-baking.
  • the present invention has been made to solve the above-mentioned problems, and is a photosensitive resin composition capable of obtaining a resin cured film having excellent developability, low-temperature curability, hardness, transparency, and adhesion. The purpose is to provide things.
  • a photosensitive resin composition containing (A) a copolymer, (B) a photoacid generator, and (C) a solvent.
  • the (A) copolymer is derived from the structural unit (a-1) derived from the polymerizable unsaturated compound having (A-1) alkoxysilyl group and (A-2) derived from the polymerizable unsaturated compound having an acid group. It is a copolymer containing the constituent unit (a-2) of A photosensitive resin composition, wherein the content of the structural unit (a-1) in the total structural units of the (A) copolymer is 45 to 99 mol%.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 to R 4 are independent hydrogen atoms, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
  • n is an integer of 1 to 10.
  • at least one of R 2 to R 4 is an alkoxy group having 1 to 6 carbon atoms.
  • the content of the (B) photoacid generator is 0.1 to 10 parts by mass with respect to 100 parts by mass of the (A) copolymer, according to any one of [1] to [9].
  • the mass ratio of the (A) copolymer to the (D) reactive diluent is 40:60 to 99: 1, and the content of the (E) photopolymerization initiator is the above (D).
  • the photosensitive resin composition according to [9] which is 0.1 to 30 parts by mass with respect to 100 parts by mass of the reactive diluent.
  • a resin cured film obtained by curing the photosensitive resin composition according to any one of [1] to [11].
  • the present invention it is possible to provide a photosensitive resin composition having good developability and excellent low temperature curability. Further, it is possible to provide a resin cured film having excellent hardness, transparency and adhesion obtained by curing the photosensitive resin composition, and an image display element provided with the resin cured film.
  • (meth) acrylic acid means at least one selected from methacrylic acid and acrylic acid.
  • (meth) acrylate means at least one selected from methacrylic acid and acrylic acid.
  • the photosensitive resin composition of the present embodiment contains (A) a copolymer, (B) a photoacid generator, and (C) a solvent.
  • the photosensitive resin composition further contains (D) a reactive diluent and (E) a photopolymerization initiator, if necessary.
  • the photosensitive resin composition of the present embodiment is polymerized and cured by being irradiated with light to form a resin cured film.
  • the (A) copolymer of the present embodiment is a structural unit (a-1) derived from a polymerizable unsaturated compound having an (A-1) alkoxysilyl group (hereinafter, also simply referred to as “constituent unit (a-1)”).
  • (A-2) a structural unit (a-2) derived from a polymerizable unsaturated compound having an acid group (hereinafter, also simply referred to as “constituent unit (a-2)”).
  • the (A) copolymer of the present embodiment is, if necessary, a structural unit (a-3) derived from (A-3) another polymerizable unsaturated compound (hereinafter, simply “constituent unit (a-3)”. Also referred to as.).
  • the structural unit (a-1) derived from the polymerizable unsaturated compound having the (A-1) alkoxysilyl group contained in the (A) copolymer of the present embodiment has the (A-1) alkoxysilyl group.
  • the polymerizable unsaturated compound is not particularly limited as long as it is a monomer having an alkoxysilyl group and an ethylenically unsaturated group.
  • the alkoxy group of the alkoxysilyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 1 to 2 carbon atoms.
  • the number of alkoxy groups in the alkoxysilyl group may be 1 or more, but the trialkoxysilyl group having 3 groups is more preferable in that it has many cross-linking points and has better curability.
  • the structural unit (a-1) is a structural unit derived from (A-1a) an alkoxysilyl group-containing (meth) acrylate from the viewpoint of the ease of reaction when synthesizing the (A) copolymer and the availability of raw materials.
  • (A-1a) is preferable, and it is more preferable that the structural unit is represented by the following formula (1).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 to R 4 are independent hydrogen atoms, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
  • n is an integer of 1 to 10.
  • at least one of R 2 to R 4 is an alkoxy group having 1 to 6 carbon atoms.
  • R 1 represents a hydrogen atom or a methyl group, and a methyl group is preferable.
  • the alkyl group of R 2 ⁇ R 4 is C 1 -C 6 shown preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms.
  • Alkoxy group R 2 ⁇ R 4 is C 1 -C 6 shown preferably has 1 to 4 carbon atoms, and more preferably 1 to 2 carbon atoms. It is preferable that R 2 to R 4 are independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and two of R 2 to R 4 have 1 to 6 carbon atoms.
  • R 2 to R 4 are each independently preferably a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and at least one of R 2 to R 4 is a methoxy group or an ethoxy group. More preferred.
  • n is an integer of 1 to 10, and most preferably 1 to 4.
  • 3- (meth) acryloyloxypropyltrimethoxysilane and 3- (meth) acryloyloxypropyltriethoxy are considered from the viewpoint of easy availability of materials and reactivity in synthesizing (A) copolymer.
  • a silane-derived structural unit is preferred.
  • the content of the structural unit (a-1) in all the structural units constituting the (A) copolymer of the present embodiment is 45 mol% or more, preferably 50 mol% or more, preferably 60 mol%. The above is more preferable, and 73 mol% or more is further preferable. If the content of the structural unit (a-1) is less than 45 mol%, there is a concern that the storage stability and development performance of the photosensitive resin composition will be insufficient, or the hardness of the cured resin film will be insufficient. To.
  • the content of the structural unit (a-1) is 99 mol% or less, preferably 90 mol% or less, and more preferably 85 mol% or less. If the content of the structural unit (a-1) is larger than 99 mol%, there is a concern that the developability of the photosensitive resin composition and the flatness of the coating film are inferior.
  • the unsaturated compound has an acid group and an ethylenically unsaturated group, and is not particularly limited as long as it is a compound that does not contain silicon.
  • a carboxy group is more preferable from the viewpoint of developability as a photosensitive resin composition.
  • the structural unit (a-2) include (meth) acrylic acid, crotonic acid, cinnamic acid, vinyl sulfonic acid, 2- (meth) acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, and the like.
  • examples thereof include constituent units derived from 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl acid phosphate and the like.
  • a structural unit derived from (meth) acrylic acid is preferable from the viewpoint of easy availability and (A) reactivity when synthesizing a copolymer.
  • the content of the structural unit (a-2) in all the structural units constituting the (A) copolymer of the present embodiment is preferably 1 to 55 mol%, preferably 15 to 40 mol%. More preferably, it is more preferably 15 to 30 mol%.
  • the content of the structural unit (a-2) is 1 mol% or more, the developability of the photosensitive resin composition is good.
  • the content of the structural unit (a-2) is 55 mol% or less, the content of the structural unit (a-1) is sufficiently large, and good hardness can be obtained as a resin cured film.
  • the (A-3) other polymerizable unsaturated compounds include acid groups and alkoxys other than the (A-1) polymerizable unsaturated compound having an alkoxysilyl group and the (A-2) polymerizable unsaturated compound having an acid group. It is a polymerizable unsaturated compound having no silyl group.
  • Examples of the compound (A-3) include dienes such as butadiene, (meth) acrylic acid esters, (meth) acrylic acid amides, vinyl compounds, styrenes, unsaturated dicarboxylic acid diesters, and unsaturated polybasic acids. Contains anhydride.
  • Specific examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylic rate, and sec-butyl.
  • N N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N-tert-butylaminoethyl.
  • a blocking agent N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N-tert-butylaminoethyl.
  • Examples of the ethylenically unsaturated compound having an isocyanato group include 2-isocyanatoethyl (meth) acrylate, 2-isocyanatopropyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, and 2-isocyanato-. Examples thereof include 1-methylethyl (meth) acrylate, 2-isocyanato-1,1-dimethylethyl (meth) acrylate, and 4-isocyanatocyclohexyl (meth) acrylate.
  • (meth) acrylic acid amides include (meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, and (meth) acrylic acid N, N. -Dipropylamide, (meth) acrylic acid N, N-di-isopropylamide, (meth) acrylic acid anthracenylamide, N-isopropyl (meth) acrylamide, (meth) acrylic morpholine, diacetone (meth) acrylamide Etc. are included.
  • vinyl compound examples include norbornene (bicyclo [2.2.1] hept-2-ene), 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2. 1] Hept-2-ene, tetracyclo [4.4.0.1 2,5 . 17 and 10 ] Dodeca-3-ene, 8-methyltetracyclo [4.4.0.1 2,5 . 17 and 10 ] Dodeca-3-ene, 8-ethyltetracyclo [4.4.0.1 2,5 .
  • unsaturated dicarboxylic acid diesters include diethyl citraconic acid, diethyl maleate, diethyl fumaric acid, diethyl itaconic acid and the like.
  • unsaturated polybasic acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride and the like.
  • Methyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, glycidyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, styrene and vinyltoluene are more preferred. ..
  • alkyl (meth) acrylate is preferable, and methyl (meth) acrylate, benzyl (meth) acrylate, and dicyclopentanyl (meth) acrylate are more preferable from the viewpoint of heat-resistant decomposition and heat-resistant yellowing.
  • a polymerizable compound having a functional group that reacts with an acid group is preferable, and specific examples thereof include a polymerizable compound having a glycidyl group, an oxetanyl group, an isocyanato group, or a blocked isocyanato group. Be done. More preferably, from the viewpoint of availability and reactivity, glycidyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl methacrylate and the like can be mentioned.
  • oxidases such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, ⁇ -propiolactam; methanol, ethanol, propanol, butanol, ethylene glycol, methylcellosolve, butylcellosolve, methylcarbitol.
  • Oximes such as benzyl alcohol, phenylcellosolve, flufuryl alcohol, cyclohexanol; butylphenols such as phenol, cresol, xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, p-tert-octylphenol, nonylphenol, di Phenols such as nonylphenol, styrenated phenol, oxybenzoic acid ester, timol, p-naphthol, p-nitrophenol, p-chlorophenol; dimethyl malonate, diethyl malonate, methyl acetate acetate, ethyl acetate, acetylacetone, etc.
  • butylphenols such as phenol, cresol, xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol,
  • Active oxime system mercaptan system such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan; amine system such as diphenylamine, phenylnaphthylamine, aniline, carbazole; acid amide system such as acetoanilide, acetoaniside, acetate amide, benzamide; succinic acidimide, Oxime-based such as maleic acidimide; imidazole-based such as imidazole, 2-methylimidazole, 2-ethylimidazole; urea-based such as urea, thiourea and ethyleneurea; carbamide such as phenyl N-phenylcarbamate and 2-oxazolidone.
  • mercaptan system such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan
  • amine system such as diphenylamine, phenyl
  • Acid salt-based Oxime-based such as ethyleneimine and polyethyleneimin; Oxime-based such as formaldehyde, acetaldoxime, acetoxime, methylethylketooxime, methylisobutylketooxime, cyclohexanoneoxime; Includes sulfites, etc.
  • the content of the structural unit (a-3) in all the structural units may be 0.1 to 40 mol%. It is preferably 1 to 30 mol%, more preferably 5 to 20 mol%.
  • the content of the structural unit (a-3) is 0.1 mol% or more, the function derived from the structural unit (a-3) can be sufficiently imparted to the photosensitive resin composition.
  • the content of the structural unit (a-3) is 40 mol% or less, the contents of the structural unit (a-1) and the structural unit (a-2) are sufficiently large, so that the photosensitive resin composition can be used as a photosensitive resin composition.
  • a resin cured film having good developability and excellent hardness and adhesion can be obtained.
  • the weight average molecular weight (Mw) of the (A) copolymer of the present embodiment is preferably 2000 to 30,000, more preferably 3000 to 10000, and further preferably 3000 to 6000 in terms of polystyrene. preferable.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) of the copolymer is 2000 or more, the developability is good.
  • Mw weight average molecular weight (Mw) of the copolymer is 30,000 or less, the development time can be adjusted within an appropriate range.
  • the value of the weight average molecular weight (Mw) of the (A) copolymer of the present embodiment is measured by gel permeation chromatography (GPC) under the following conditions and calculated in terms of polystyrene.
  • GPC gel permeation chromatography
  • the molecular weight distribution (Mw / Mn) of the (A) copolymer of the present embodiment is preferably 1.3 to 3.0, more preferably 1.5 to 2.5, and 1.5. It is more preferably ⁇ 2.0.
  • the target numerical range such as the weight average molecular weight and the acid value is optimized, and (A) the reaction when producing the copolymer. Conditions and the like can be set with a certain width, which is efficient.
  • the molecular weight distribution (Mw / Mn) of the copolymer is less than 3.0, the performance of the photosensitive resin composition such as developability does not vary. The molecular weight distribution is measured from the above GPC measurement chromatogram.
  • the acid value of the (A) copolymer of the present embodiment is not particularly limited, but is preferably 15 KOH mg / g to 150 KOH mg / g, more preferably 25 KOH mg / g to 100 KOH mg / g, and further preferably 30 KOH mg / g to 70 KOH mg / g. g.
  • (A) When the acid value of the copolymer is 15 KOHmg / g or more, better developability can be obtained.
  • the acid value of the (A) copolymer is 150 KOHmg / g or less, good developability can be obtained without dissolving the exposed portion (photocured portion) in the alkaline developer.
  • the acid value of the (A) copolymer is a value measured using a mixed indicator of bromothymol blue and phenol red according to JIS K6901 5.3, and is contained in 1 g of the (A) copolymer. It means the number of mg of potassium hydroxide required to neutralize the acidic component.
  • the silyl group equivalent of the copolymer (A) of the present embodiment is not particularly limited, but is preferably 290 g / mol to 450 g / mol, more preferably 300 g / mol to 420 g / mol, and most preferably 300 g / mol to 400 g. / Mol.
  • the silyl group equivalent of the (A) copolymer is 290 g / mol or more, it is effective in further increasing the hardness and developability.
  • the silyl group equivalent of the (A) copolymer is 450 g / mol or less, sufficient hardness can be secured as a resin cured film.
  • the silyl group equivalent of the (A) copolymer is a value obtained by dividing the molecular weight of the (A) copolymer by the average number of silyl groups per molecule, and (A) when synthesizing the copolymer.
  • (A-1) The calculated value is calculated based on the amount of the polymerizable unsaturated compound having an alkoxysilyl group charged.
  • the (B) photoacid generator of the present embodiment is not particularly limited as long as it decomposes by light irradiation and generates an acid, but an agent that generates an acid by irradiating light having a wavelength of 190 to 500 nm is used. preferable.
  • a sulfonium salt compound or an iodonium salt compound is preferable, an aromatic sulfonium salt compound or an aromatic iodonium salt compound is more preferable, and an aromatic iodonium salt compound is preferable because it is easily available and has good storage stability as a photosensitive resin composition.
  • Sulfonium salt compounds are more preferred, and triarylsulfonium salt compounds are particularly preferred.
  • the anion species contained in the (B) photoacid generator of the present embodiment is not particularly limited, but borate anions and phosphorus-based anions are preferable, and borate anions are particularly preferable from the viewpoint of low-temperature curability as a photosensitive resin composition. preferable.
  • the borate anion, BF 4 -, (C 6 F 5) 4 B -, (C 6 H 5) (C 6 F 5) 3 B -, ((CF 3) 2 C 6 H 3) 4 B - like Can be mentioned. Of these, a fluoroalkyl group-containing borate anion is preferable.
  • Examples of the phosphorus-based anion PF 6 -, (CF 3 CF 2) 3 PF 3 -, (CF 3 CF 2 CF 2 CF 2) 3 PF 3 - , and the like. Of these, fluoroalkyl group-containing phosphorus anions are preferable.
  • the (B) photoacid generator examples include the photoacid generators disclosed in JP-A-2012-27290, JP-A-2011-201803, JP-A-2011-195499, and the like; San-Apro Co., Ltd. Examples thereof include sulfonium salt compounds such as CPI-200K, CPI-210S, CPI-310B, and CPI-410S manufactured by Chemical Industries; and iodonium salt compounds such as IK-1. Among them, CPI-210S and CPI-310B are preferable because they have good low-temperature curability as a photosensitive resin composition and are excellent in hardness and transmittance as a resin cured film. These (B) photoacid generators may be used alone or in combination of two or more.
  • the content of the (B) photoacid generator needs to be adjusted according to the amount and rate of acid generated.
  • (A) is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and 0.3 to 3 parts by mass with respect to 100 parts by mass of the copolymer. Is even more preferable.
  • (B) When the content of the photoacid generator is 0.1 part by mass or more, the amount of generated acid is sufficient and sufficient hardness can be obtained as a cured film. When the content is 10 parts by mass or less, the appearance of the cured resin film is good, and (B) coloring due to the addition of the photoacid generator does not occur.
  • the solvent (C) of the present embodiment is not particularly limited as long as it is a solvent that is inert to each component of the photosensitive resin composition and can dissolve each component.
  • (A) When synthesizing the copolymer it may be synthesized using the same solvent as the solvent (C), and the solvent may be used as it is as the solvent (C) of the photosensitive resin composition without separation and removal. Alternatively, it may be newly added when mixing each component of the photosensitive resin composition. It may be a solvent that coexists with each component of the photosensitive resin composition when it is mixed.
  • a primary alcohol or a secondary alcohol having 3 to 10 carbon atoms it is preferable to contain at least one of a primary alcohol or a secondary alcohol having 3 to 10 carbon atoms, and the third to 10 carbon atoms. It is more preferable to contain primary alcohol.
  • the primary alcohol or the secondary alcohol solvent having 3 to 10 carbon atoms include monoalcohols, (poly) alkylene glycol monoalkyl ethers and the like.
  • monoalcohols include propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, dodecyl alcohol, benzyl alcohol and the like.
  • (poly) alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, and tri.
  • Ethylene glycol monomethyl ether triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono Includes -n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, 3-methoxy-1-butanol and the like.
  • (poly) alkylene glycol monoalkyl ethers are preferable from the viewpoint of easy availability and storage stability as a photosensitive resin composition. These solvents may be used alone or in combination of two or more.
  • the solvent (C) of the present embodiment may contain other solvents in addition to the above-mentioned solvent.
  • other solvents include tertiary alcohols such as tert-butyl alcohol and diacetone alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like.
  • Aromatic hydrocarbons include carboxylic acid amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like.
  • carboxylic acid amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like.
  • (poly) such as propylene glycol monomethyl ether acetate from the viewpoint of compatibility with primary alcohols having 3 to 10 carbon atoms or secondary alcohols and solubility of each component of the photosensitive resin composition.
  • An alkylene glycol monoalkyl ether acetate solvent is preferred.
  • the content of the solvent (C) is preferably from 30 parts by mass to 1000 parts by mass, more preferably from 50 parts by mass when the total of the components of the photosensitive resin composition excluding the solvent (C) is 100 parts by mass. It is 800 parts by mass, most preferably 100 parts by mass to 500 parts by mass. (C) When the blending amount of the solvent is within the above range, the viscosity of the photosensitive resin composition can be adjusted to an appropriate range.
  • the photosensitive resin composition of the present embodiment may contain (D) a reactive diluent, if necessary.
  • the reactive diluent (D) is not particularly limited as long as it is a low molecular weight compound having an ethylenically unsaturated group such as a vinyl group, an allyl group and a (meth) acryloyloxy group.
  • Specific examples of the (D) reactive diluent include aromatic vinyl-based monomers; polycarboxylic acid monomers such as vinyl acetate and vinyl adipic acid; (meth) acrylates; polyfunctional (meth) acrylates; and triallylsia. Including monomers and the like.
  • aromatic vinyl-based monomers include styrene, ⁇ -methylstyrene, ⁇ -chloromethylstyrene, vinyltoluene, divinylbenzene, diallylphthalate, diallylbenzenephosphonate and the like.
  • (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, ⁇ -hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and the like. including.
  • polyfunctional (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, and trimethyl propandi (meth). Includes acrylate, trimethylol propantri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate and the like. Among these, polyfunctional (meth) acrylates are particularly preferable. These (D) reactive diluents may be used alone or in combination of two or more.
  • the amount of the (D) reactive diluent is preferably blended so that the mass ratio of the (A) copolymer to the (D) reactive diluent is 40:60 to 99: 1, preferably 50. : 50 to 95: 5 is more preferable, and 60:40 to 90:10 is even more preferable.
  • the blending amount of the reactive diluent is within the above range, the viscosity and photocurability of the photosensitive resin composition can be appropriately adjusted.
  • (E) Photopolymerization Initiator When the photosensitive resin composition of the present embodiment contains (D) a reactive diluent, (E) a photopolymerization initiator is also used.
  • the (E) photopolymerization initiator is not particularly limited as long as it is a compound that generates a radical by irradiation with light, but for example, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether and its alkyl ethers; acetophenone, 2, Acetphenones such as 2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4- (1-t-butyldioxy-1-methylethyl) acetophenone; 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl Alkylphenones such as -1-phenylpropan-1-one; anthracinones such as 2-methylanthraquinone, 2-
  • the content of the (E) photopolymerization initiator is preferably 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the (D) reactive diluent. It is more preferably 1 to 15 parts by mass, further preferably 1 to 15 parts by mass.
  • the content of the photopolymerization initiator is 0.1 parts by mass or more, the photosensitive resin composition has sufficient photocurability.
  • the content is 30 parts by mass or less, the storage stability of the photosensitive resin composition and the performance of the cured resin film are not adversely affected.
  • the photosensitive resin composition of the present embodiment may contain known additives such as known leveling agents and thermal polymerization inhibitors in order to impart predetermined properties.
  • the blending amount of these additives in the photosensitive resin composition is not particularly limited as long as it does not impair the effects of the present invention.
  • the viscosity of the photosensitive resin composition of the present embodiment can be appropriately adjusted according to the thickness of the target resin cured film.
  • the viscosity of the photosensitive resin composition is preferably 4 to 25 mP ⁇ s, more preferably 6 to 20 mP ⁇ s, and further preferably 8 to 15 mP ⁇ s. preferable.
  • the total content of silicon contained in the photosensitive resin composition of the present embodiment is 4.0 to 20% by mass with respect to the total mass of all the components excluding the solvent (C) from the photosensitive resin composition. It is preferably 4.5 to 10% by mass, more preferably 5.0 to 9.5% by mass. When the total content of silicon is 4.0% by mass or more, the cured resin film has sufficient hardness. When the total content of silicon is 20% by mass or less, the developability of the photosensitive resin composition and the flatness of the cured resin film are good.
  • the total silicon content is a calculated value calculated from the amount of raw materials charged.
  • the (A) copolymer of the present embodiment is a polymerizable unsaturated compound having (A-1) an alkoxysilyl group and (A-2) polymerizable having an acid group in the presence of (C-1) solvent. It can be prepared by copolymerizing an unsaturated compound and a monomer mixture consisting of (A-3) and other polymerizable unsaturated compounds used as necessary according to a radical polymerization method known in the art. For example, the compound (A-1), the compound (A-2) and the compound (A-3) are dissolved in the solvent (C-1) to prepare a solution, and then a polymerization initiator is added to the solution. The reaction may be carried out at 50 ° C.
  • the number of repetitions of each compound and the order in which each compound is bonded are not particularly limited. Further, after preparing a copolymer containing no of the constituent units (a-1), the constituent units (a-2) and the constituent units (a-3), the insufficient constituent units are subjected to a modification reaction in the copolymer. By introducing into the above, a copolymer containing a structural unit (a-1), a structural unit (a-2) and a structural unit (a-3) may be prepared.
  • the (A-1) compound and the (A-2) compound for the same reason as defining the content ratios of the structural units (a-1) to (a-3) constituting the (A) copolymer described above.
  • the compounding amount of the compound can be specified. That is, when the total of the compounds (A-1) to (A-3) is 100 mol%, the blending amount of the compound (A-1) is 45 to 99 mol%, and 50 to 90 mol%. It is preferably 60 to 85 mol%, more preferably 70 to 85 mol%, and even more preferably 70 to 85 mol%.
  • the blending amount of the compound (A-2) is preferably 1 to 55 mol%, more preferably 15 to 40 mol%, still more preferably 15 to 30 mol%. When the compound (A-3) is used, the blending amount is preferably 0.1 to 40 mol%, more preferably 1 to 30 mol%, still more preferably 5 to 20 mol%. ..
  • the solvent (C-1) is not particularly limited as long as it is a solvent that is inert to the polymerization reaction. It is preferable to use a solvent similar to the solvent (C) used as the above-mentioned photosensitive resin composition because it is not necessary to separate and remove the solvent for the polymerization reaction. Further, from the viewpoint of (A) controlling the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the copolymer within a predetermined range and obtaining a photosensitive resin composition having desired storage stability, carbon is used. It is preferable to use a solvent containing at least either a primary alcohol or a secondary alcohol having a molecular weight of 3 to 10.
  • the content ratio of the primary alcohol or the secondary alcohol solvent having 3 to 10 carbon atoms is the solvent. It is preferably 10 to 100% by mass, and more preferably 20 to 100 parts by mass with respect to the total amount of.
  • the content ratio is within the above range, the weight molecular weight and molecular weight distribution (Mw / Mn) of the (A) copolymer can be easily controlled within a predetermined range, and the solvent can be used as the (C) solvent of the photosensitive resin composition. If used as it is, the storage stability of the photosensitive resin composition can be further improved.
  • the amount of the solvent used for producing the (A) copolymer is not particularly limited, but is preferably 30 when the total amount of the compounds (A-1) to (A-3) charged is 100 parts by mass. It is a mass part to 1000 parts by mass, more preferably 50 parts by mass to 800 parts by mass. When the amount used is 30 parts by mass or more, the polymerization reaction can be stably carried out, and (A) coloring and gelation of the copolymer can be prevented. When the amount used is 1000 parts by mass or less, the decrease in the molecular weight of the (A) copolymer due to the chain transfer action can be suppressed, and the viscosity of the reaction solution can be controlled within an appropriate range.
  • the polymerization initiator that can be used in this copolymerization reaction is not particularly limited, and is, for example, 2,2'-azobis (isobutyronitrile) and 2,2'-azobis (2,4-dimethylvaleronitrile). ), 2,2'-azobis (isobutyric acid) dimethyl, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate and the like. These polymerization initiators may be used alone or in combination of two or more.
  • the amount of the polymerization initiator used is not particularly limited, but is preferably 0 when the total amount of the compound (A-1), (A-2) and (A-3) charged is 100 parts by mass. .1 part by mass to 20 parts by mass, more preferably 0.5 part by mass to 16 parts by mass.
  • the photosensitive resin composition of the present embodiment may be prepared by mixing the above-mentioned components using a known mixing device.
  • a composition containing (A) a copolymer and (C-1) a solvent is prepared, and then (B) a photoacid generator and an optional component. It may be prepared by adding (D) a reactive diluent and (E) a photopolymerization initiator and mixing them.
  • "After preparing the composition containing (A) copolymer and (C-1) solvent” means "(A-1) compound, (A-2) compound and (A-3) compound".
  • the (C-2) solvent may be additionally added after the copolymerization.
  • the (C) solvent contained in the photosensitive resin composition includes the (C-1) solvent and the (C-2) solvent.
  • the (C-2) solvent may be the same as or different from the (C-1) solvent, and is preferably the same as the (C-1) solvent. That is, the solvent (C) contained in the photosensitive resin composition is preferably the same as the solvent for producing the photopolymer.
  • the photosensitive resin composition of the present embodiment Since the photosensitive resin composition of the present embodiment has alkaline developability, it can be developed by using an alkaline aqueous solution. In particular, the photosensitive resin composition of the present embodiment can give a pattern having excellent developability. Therefore, the photosensitive resin composition of the present embodiment is suitably used as a resist used for producing an overcoat, a protective film, and an insulating film incorporated in an organic EL display device, a liquid crystal display device, and a solid-state image sensor.
  • the cured resin film of the present embodiment is formed by applying the photosensitive resin composition to a substrate, prebaking, exposing, and post-baking.
  • a pattern is formed by a photolithography method
  • the photosensitive resin composition is applied to a substrate, prebaked, and then the formed coating film is exposed through a photomask of a predetermined pattern to illuminate the exposed portion. Let it cure. Then, if necessary, after exposure and heat treatment, the unexposed portion is dissolved in an alkaline aqueous solution, developed, and then post-baked to form a predetermined pattern.
  • the coating method of the photosensitive resin composition is not particularly limited, but a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, a slit coating method and the like are used.
  • Pre-bake step After forming a coating film by a coating step, it is preferable to pre-bake (preheat treatment) in order to dry the coating film and reduce the residual amount of solvent in the coating film.
  • the prebaking step can be carried out at a temperature of generally 70 to 120 ° C., preferably 90 to 110 ° C., for 10 to 600 seconds, preferably 120 to 180 seconds when using a hot plate.
  • Exposure step The formed coating film surface is exposed by light irradiation.
  • the surface of the coating film is exposed through a photomask of a predetermined pattern.
  • the light source used for light irradiation is not particularly limited, and for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is used. Further, the exposure amount is not particularly limited, and is appropriately set according to the composition of the photosensitive resin composition.
  • Post-exposure heating process When a pattern is formed, post-exposure heat treatment (Post Exposure Backing) can be performed as necessary after the exposure process. By this step, the dissolution contrast between the exposed portion and the unexposed portion of the coating film can be made more remarkable. Unlike the step (6) post-baking described later, this step is not performed to completely cure the coating film, but only the pattern of the exposed portion is left on the substrate after the developing step, and the unexposed portion is coated. This is done so that the film can be reliably removed by development. Therefore, it is not an indispensable step in forming the resin cured film of the present embodiment. When heat treatment is performed after exposure, a hot plate, an oven, furnace, or the like can be used. The heating temperature range is preferably 40 ° C.
  • the heating temperature is 40 ° C. or higher, the dissolution contrast between the exposed portion and the unexposed portion of the coating film can be improved, and the effect of the post-exposure heat treatment can be fully exhibited.
  • the heating temperature is 70 ° C. or lower, the acid generated in the exposed portion does not diffuse to the unexposed portion, and good dissolution contrast can be obtained.
  • the heating time is preferably 20 seconds to 600 seconds. If it is 20 seconds or more, the temperature history of the entire coating film can be made uniform. If it is 600 seconds or less, the acid generated in the exposed portion does not diffuse to the unexposed portion, and a good dissolution contrast can be obtained.
  • the alkaline aqueous solution used for development is not particularly limited, but is, for example, an aqueous solution of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide and the like; an aqueous solution of an amine compound such as ethylamine, diethylamine and dimethylethanolamine.
  • An aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide; 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline , 3-Methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline and their sulfates, hydrochlorides
  • an aqueous solution of a p-phenylenediamine compound such as p-toluenesulfonate is used.
  • aqueous solution of a p-phenylenediamine-based compound it is preferable to use an aqueous solution of a p-phenylenediamine-based compound. If necessary, a defoaming agent or a surfactant may be added to these alkaline aqueous solutions. Further, it is preferable to wash with water and dry after developing with the above alkaline aqueous solution.
  • Post-baking is performed after the developing step to obtain a resin cured film.
  • the post-baking conditions are not particularly limited, and the heat treatment may be performed according to the composition of the photosensitive resin composition. For example, it may be heated at a temperature of 80 ° C. to 250 ° C. for 10 minutes to 60 minutes.
  • the temperature range of the post-baking process is preferably 80 ° C. to 130 ° C., preferably 80 ° C. to 100 ° C. from the viewpoint of reducing damage due to heat of the base material and the circuit. It is more preferable to do so.
  • the resin cured film of this embodiment has high light transmittance and excellent transparency. Further, since the hardness of the cured resin film is good, it can be suitably used for an overcoat on the upper part of a color filter, various protective films, and the like. Further, it can be suitably used as various insulating materials such as an insulating film between electrodes such as ITO of a touch panel and an interlayer insulating film of a TFT.
  • the image display device of the present embodiment has an image display element provided with the above-mentioned resin cured film.
  • the image display element is not particularly limited as long as it includes the above-mentioned resin cured film, and examples thereof include a liquid crystal display element and an organic EL display element.
  • the photosensitive resin composition of the present embodiment can produce a resin cured film without having a heating step in a high temperature range, it is suitable for an image display device that does not use a glass substrate, such as a folding smartphone or a flexible display. Is also effective.
  • 2,2'-azobis (isobutyric acid) dimethyl (2,2'-azobis (isobutyric acid) dimethyl (isobutyric acid) dimethyl (2,2'-azobis (isobutyric acid) dimethyl) was added to a monomer mixture consisting of 7.1 g (0.1 mol) of acrylic acid and 258.4 g (0.9 mol) of 3-methacryloxypropyltriethoxysilane.
  • a product to which 34.5 g of a polymerization initiator) was added was added dropwise to the flask from the dropping funnel. After completion of the dropping, the copolymerization reaction was carried out by stirring at 105 ° C. for 2 hours.
  • Rate of increase in molecular weight (([Molecular weight after test]-[Molecular weight before test]) / [Molecular weight before test]) x 100% (I)
  • the criteria for this evaluation are as follows. ⁇ : Increase rate less than 30% ⁇ : Increase rate 30% or more Table 1 shows the above evaluation results of storage stability.
  • a photosensitive resin composition was prepared according to the compounding components and compounding ratios shown in Tables 2 and 3.
  • the blending amount of the (A) copolymer in Tables 2 and 3 does not include the amount of the solvent used when synthesizing the (A) copolymer.
  • Example 1 Using the obtained sample 1 (solid content concentration 30% by mass), (A) 100 g of solid content as a copolymer, 0.5 g of CPI-310B as a photoacid generator, and 3-methoxy-1- as a solvent.
  • the photosensitive resin composition was prepared by blending 300 g of butanol. The 300 g of solvent contains the solvent contained in sample 1.
  • the prepared photosensitive resin composition was evaluated for hardness, transmittance, adhesion, and developability by the following methods. The results are shown in Table 2.
  • Examples 2 to 16, Comparative Examples 1 to 4 The photosensitive resin composition was prepared in the same manner as in Example 1 except that the raw materials shown in Tables 2 and 3 were used, and the hardness, transmittance, adhesion, and development were evaluated. The results are shown in Tables 2 and 3.
  • Pencil hardness The prepared photosensitive resin composition is applied onto a 5 cm square glass substrate (non-alkali glass substrate) by a spin coater method, and heated at 100 ° C. for 3 minutes to volatilize the solvent. A coating film was formed on the glass substrate. Next, the coating film was irradiated with light having a wavelength of 365 nm at an exposure amount of 200 mJ / cm 2 , and the coating film was photocured. Then, it was allowed to stand in a dryer at 130 ° C. for 30 minutes or 80 ° C. for 60 minutes for heat treatment (post-baking) to obtain a resin cured film having a film thickness of 1.5 ⁇ m.
  • the pencil hardness of the resin cured film produced as described above was measured according to JIS K5600-5-4 using a pencil hardness tester (No. 553-M, manufactured by Yasuda Seiki Seisakusho). The results are shown in Tables 2-4.
  • Example 17 to 18 The photosensitive resin composition was prepared in the same manner as in Example 1 except that the compositions shown in Table 5 were used. A resin cured film was prepared and the pencil hardness was measured in the same manner as in (1) Pencil hardness evaluation method described above, except that the post-baking conditions shown in Table 5 were used. The results are shown in Table 5.
  • the photosensitive resin compositions of Examples 1 to 16 were excellent in developability, and a cured resin film having excellent hardness, transparency, and adhesion could be obtained.
  • Comparative Example 1 in which the photoacid generator was not used, a resin cured film having poor developability and sufficient hardness and adhesion could not be obtained. It is considered that this is because the heating process such as the post-baking process requires higher temperature conditions, resulting in insufficient curing.
  • Comparative Example 2 in which acrylic acid was not used the result was that developability could not be obtained.
  • Comparative Examples 3 and 4 in which the content of the structural unit (a-1) derived from the polymerizable unsaturated compound having the (A-1) alkoxysilyl group in the (A) copolymer is small is inferior in developability. rice field. Since the degree of cross-linking derived from the alkoxysilyl group is low, the exposed and unexposed parts of the coating film are also dissolved in the pattern, resulting in poor developability.
  • a photosensitive resin composition that provides a cured resin film having excellent hardness, transparency and adhesion, has good developability, and is also excellent in storage stability. Further, a resin cured film having excellent hardness, transparency and adhesion, and an image display element provided with the resin cured film are provided.
  • the photosensitive resin composition can be preferably used as a transparent film, a protective film, an insulating film, an overcoat, a photo spacer, a black matrix, a black column spacer, and a resist for a color filter.

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Abstract

Provided are a photosensitive resin composition having satisfactory developability and excellent low-temperature curability, a cured resin film obtained by curing the photosensitive resin composition, and an image display element including the cured resin film. This photosensitive resin composition comprises (A) a copolymer, (B) a photoacid generator, and (C) a solvent. The copolymer (A) is a copolymer comprising a constituent unit (a-1) derived from (A-1) a polymerizable unsaturated compound having an alkoxysilyl group and a constituent unit (a-2) derived from (A-2) a polymerizable unsaturated compound having an acid group. The content of the constituent unit (a-1) in all the constituent units of the copolymer (A) is 45-99 mol%.

Description

感光性樹脂組成物及びその樹脂硬化膜Photosensitive resin composition and its resin cured film
　本発明は、アルカリ現像可能な感光性樹脂組成物、該感光性樹脂組成物を硬化させてなるオーバーコート、層間絶縁膜、表面保護膜などの樹脂硬化膜に関する。これらの部材は、特にタッチパネル、液晶表示装置、有機ＥＬ装置などの画像表示装置を構成する部材として、好適に用いることができる。
　本願は、２０２０年７月６日に、日本に出願された特願２０２０－１１６５１８号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a photosensitive resin composition that can be developed with an alkali, an overcoat obtained by curing the photosensitive resin composition, an interlayer insulating film, a surface protective film, and other cured resin films. These members can be suitably used as members constituting an image display device such as a touch panel, a liquid crystal display device, and an organic EL device.
This application claims priority based on Japanese Patent Application No. 2020-116518 filed in Japan on July 6, 2020, the contents of which are incorporated herein by reference.
　従来より、画像表示装置の部材として用いるオーバーコート、層間絶縁膜、保護膜などを形成するため、光硬化性樹脂組成物が広く使用されている。例えば特許文献１には、特定の構成単位を有する重合体、エポキシ化合物、感放射線性化合物を含有する感放射線性樹脂組成物が開示されている。該感放射線性樹脂組成物は、基板への塗布、プレベーク、露光、現像、ポストベークなどの工程を経て、硬化膜を形成できることが記載されている。 Conventionally, a photocurable resin composition has been widely used for forming an overcoat, an interlayer insulating film, a protective film, etc. used as a member of an image display device. For example, Patent Document 1 discloses a radiation-sensitive resin composition containing a polymer having a specific structural unit, an epoxy compound, and a radiation-sensitive compound. It is described that the radiation-sensitive resin composition can form a cured film through steps such as coating on a substrate, prebaking, exposure, development, and post-baking.
特開２０１７－１０７０２４号公報Japanese Unexamined Patent Publication No. 2017-107024
　一方、近年では折りたたみスマホやフレキシブルディスプレイの普及に伴い、基板の材質がガラスから樹脂に置き換わってきている。この変化に伴い、特許文献１のように高温でのポストベークを必要とする、従来の感光性樹脂組成物が使用できない問題がある。これは、基板や回路へのダメージを低減し、省エネルギー化する等の観点から、高温域での加熱工程を必要としない感光性樹脂組成物が求められるためである。
　従って、本発明は上記のような課題を解決するためになされた物であり、現像性、低温硬化性に優れ、硬度、透明性、密着性に優れた樹脂硬化膜が得られる感光性樹脂組成物を提供することを目的とする。 On the other hand, in recent years, with the spread of folding smartphones and flexible displays, the material of the substrate has been replaced from glass to resin. Along with this change, there is a problem that the conventional photosensitive resin composition, which requires post-baking at a high temperature as in Patent Document 1, cannot be used. This is because a photosensitive resin composition that does not require a heating step in a high temperature range is required from the viewpoint of reducing damage to the substrate and the circuit and saving energy.
Therefore, the present invention has been made to solve the above-mentioned problems, and is a photosensitive resin composition capable of obtaining a resin cured film having excellent developability, low-temperature curability, hardness, transparency, and adhesion. The purpose is to provide things.
　本発明は以下の態様を含む。
［１］　（Ａ）共重合体と、（Ｂ）光酸発生剤と、（Ｃ）溶剤とを含有する感光性樹脂組成物であって、
　前記（Ａ）共重合体が、（Ａ－１）アルコキシシリル基を有する重合性不飽和化合物由来の構成単位（ａ－１）と、（Ａ－２）酸基を有する重合性不飽和化合物由来の構成単位（ａ－２）とを含む共重合体であり、
　前記（Ａ）共重合体における全構成単位中の前記構成単位（ａ－１）の含有量が、４５～９９モル％であることを特徴とする感光性樹脂組成物。
［２］　前記（Ａ）共重合体の酸価が１５～１５０ＫＯＨｍｇ／ｇである［１］に記載の感光性樹脂組成物。
［３］　前記構成単位（ａ－１）が（Ａ－１ａ）アルコキシシリル基含有（メタ）アクリレート由来の構成単位（ａ－１ａ）である［１］又は［２］に記載の感光性樹脂組成物。［４］　前記構成単位（ａ－１ａ）が、下記式（１）で表される［３］に記載の感光性樹脂組成物。
Figure JPOXMLDOC01-appb-C000002
 ［式（１）中、Ｒ１は水素原子又はメチル基を表し、Ｒ２～Ｒ４は各々独立に、水素原子、炭素原子数１～６のアルキル基又は炭素原子数１～６のアルコキシ基を表し、ｎは１～１０の整数である。ただし、Ｒ２～Ｒ４のうち少なくとも１つは炭素原子数１～６のアルコキシ基である。］
［５］　前記構成単位（ａ－２）が有する酸基がカルボキシ基である請求項［１］～［４］のいずれかに記載の感光性樹脂組成物。
［６］　前記（Ｃ）溶剤が、炭素原子数３～１０の第一級アルコール又は第二級アルコールのいずれかを少なくとも含む溶剤である［１］～［５］のいずれかに記載の感光性樹脂組成物。
［７］　前記（Ｂ）光酸発生剤が、スルホニウム塩化合物である［１］～［６］のいずれかに記載の感光性樹脂組成物。
［８］　前記（Ａ）共重合体の重量平均分子量が、２０００～３００００である［１］～［７］のいずれかに記載の感光性樹脂組成物。
［９］　（Ｄ）反応性希釈剤、および（Ｅ）光重合開始剤をさらに含む［１］～［８］のいずれかに記載の感光性樹脂組成物。
［１０］　前記（Ｂ）光酸発生剤の含有量が、前記（Ａ）共重合体１００質量部に対して、０．１～１０質量部である［１］～［９］のいずれかに記載の感光性樹脂組成物。
［１１］　前記（Ａ）共重合体と前記（Ｄ）反応性希釈剤との質量比が、４０：６０～９９：１であり、前記（Ｅ）光重合開始剤の含有量が前記（Ｄ）反応性希釈剤１００質量部に対して０．１～３０質量部である［９］に記載の感光性樹脂組成物。
［１２］　［１］～［１１］のいずれかに記載の感光性樹脂組成物を硬化させてなる樹脂硬化膜。
［１３］　前記樹脂硬化膜が、オーバーコート、保護膜、及び絶縁膜からなる群から選択される一種である［１２］に記載の樹脂硬化膜。
［１４］［１２］に記載の樹脂硬化膜を具備する画像表示装置。 The present invention includes the following aspects.
[1] A photosensitive resin composition containing (A) a copolymer, (B) a photoacid generator, and (C) a solvent.
The (A) copolymer is derived from the structural unit (a-1) derived from the polymerizable unsaturated compound having (A-1) alkoxysilyl group and (A-2) derived from the polymerizable unsaturated compound having an acid group. It is a copolymer containing the constituent unit (a-2) of
A photosensitive resin composition, wherein the content of the structural unit (a-1) in the total structural units of the (A) copolymer is 45 to 99 mol%.
[2] The photosensitive resin composition according to [1], wherein the acid value of the (A) copolymer is 15 to 150 KOHmg / g.
[3] The photosensitive resin composition according to [1] or [2], wherein the structural unit (a-1) is the structural unit (a-1a) derived from the (A-1a) alkoxysilyl group-containing (meth) acrylate. thing. [4] The photosensitive resin composition according to [3], wherein the structural unit (a-1a) is represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000002
 [In the formula (1), R 1 represents a hydrogen atom or a methyl group, and R 2 to R 4 are independent hydrogen atoms, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Represents, and n is an integer of 1 to 10. However, at least one of R 2 to R 4 is an alkoxy group having 1 to 6 carbon atoms. ]
[5] The photosensitive resin composition according to any one of claims [1] to [4], wherein the acid group of the structural unit (a-2) is a carboxy group.
[6] The photosensitive according to any one of [1] to [5], wherein the solvent (C) is a solvent containing at least one of a primary alcohol or a secondary alcohol having 3 to 10 carbon atoms. Resin composition.
[7] The photosensitive resin composition according to any one of [1] to [6], wherein the (B) photoacid generator is a sulfonium salt compound.
[8] The photosensitive resin composition according to any one of [1] to [7], wherein the (A) copolymer has a weight average molecular weight of 2000 to 30,000.
[9] The photosensitive resin composition according to any one of [1] to [8], further comprising (D) a reactive diluent and (E) a photopolymerization initiator.
[10] The content of the (B) photoacid generator is 0.1 to 10 parts by mass with respect to 100 parts by mass of the (A) copolymer, according to any one of [1] to [9]. The photosensitive resin composition according to the above.
[11] The mass ratio of the (A) copolymer to the (D) reactive diluent is 40:60 to 99: 1, and the content of the (E) photopolymerization initiator is the above (D). ) The photosensitive resin composition according to [9], which is 0.1 to 30 parts by mass with respect to 100 parts by mass of the reactive diluent.
[12] A resin cured film obtained by curing the photosensitive resin composition according to any one of [1] to [11].
[13] The resin cured film according to [12], wherein the resin cured film is one selected from the group consisting of an overcoat, a protective film, and an insulating film.
[14] An image display device provided with the resin cured film according to [12].
　本発明によれば、現像性が良好であるとともに、低温硬化性に優れた感光性樹脂組成物を提供することができる。また、上記感光性樹脂組成物を硬化させてなる硬度、透明性、密着性に優れた樹脂硬化膜、これを具備する画像表示素子を提供することができる。 According to the present invention, it is possible to provide a photosensitive resin composition having good developability and excellent low temperature curability. Further, it is possible to provide a resin cured film having excellent hardness, transparency and adhesion obtained by curing the photosensitive resin composition, and an image display element provided with the resin cured film.
　以下、本発明の実施形態について詳細に説明する。ただし、本発明は、以下に示す実施形態に限定されるものではない。なお、本発明において、「（メタ）アクリル酸」は、メタクリル酸及びアクリル酸から選択される少なくとも１種を意味する。「（メタ）アクリレート」についても同様である。 Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments shown below. In the present invention, "(meth) acrylic acid" means at least one selected from methacrylic acid and acrylic acid. The same applies to "(meth) acrylate".
＜感光性樹脂組成物＞
　本実施形態の感光性樹脂組成物は、（Ａ）共重合体と、（Ｂ）光酸発生剤と、（Ｃ）溶剤とを含有するものである。前記感光性樹脂組成物は、必要に応じて、（Ｄ）反応性希釈剤と、（Ｅ）光重合開始剤とをさらに含有する。本実施形態の感光性樹脂組成物は、光照射されることにより重合硬化し、樹脂硬化膜を形成する。 <Photosensitive resin composition>
The photosensitive resin composition of the present embodiment contains (A) a copolymer, (B) a photoacid generator, and (C) a solvent. The photosensitive resin composition further contains (D) a reactive diluent and (E) a photopolymerization initiator, if necessary. The photosensitive resin composition of the present embodiment is polymerized and cured by being irradiated with light to form a resin cured film.
［（Ａ）共重合体］
　本実施形態の（Ａ）共重合体は、（Ａ－１）アルコキシシリル基を有する重合性不飽和化合物由来の構成単位（ａ－１）（以下、単に「構成単位（ａ－１）」とも言う。）と、（Ａ－２）酸基を有する重合性不飽和化合物由来の構成単位（ａ－２）（以下、単に「構成単位（ａ－２）」とも言う。）とを含む。本実施形態の（Ａ）共重合体は、必要に応じて（Ａ－３）その他の重合性不飽和化合物由来の構成単位（ａ－３）（以下、単に「構成単位（ａ－３）」とも言う。）を含んでもよい。 [(A) Copolymer]
The (A) copolymer of the present embodiment is a structural unit (a-1) derived from a polymerizable unsaturated compound having an (A-1) alkoxysilyl group (hereinafter, also simply referred to as “constituent unit (a-1)”). ) And (A-2) a structural unit (a-2) derived from a polymerizable unsaturated compound having an acid group (hereinafter, also simply referred to as “constituent unit (a-2)”). The (A) copolymer of the present embodiment is, if necessary, a structural unit (a-3) derived from (A-3) another polymerizable unsaturated compound (hereinafter, simply “constituent unit (a-3)”. Also referred to as.).
［（Ａ－１）アルコキシシリル基を有する重合性不飽和化合物由来の構成単位（ａ－１）］
　本実施形態の（Ａ）共重合体に含まれる、（Ａ－１）アルコキシシリル基を有する重合性不飽和化合物由来の構成単位（ａ－１）について、（Ａ－１）アルコキシシリル基を有する重合性不飽和化合物は、アルコキシシリル基とエチレン性不飽和基を有するモノマーであれば特に限定されない。アルコキシシリル基のアルコキシ基は、炭素数１～６であることが好ましく、炭素数１～４であることがより好ましく、炭素数１～２であることがさらに好ましい。アルコキシシリル基におけるアルコキシ基の数が１以上であればよいが、３つであるトリアルコキシシリル基は架橋点が多くて硬化性がより良い面でより好ましい。 [(A-1) Structural unit derived from a polymerizable unsaturated compound having an alkoxysilyl group (a-1)]
The structural unit (a-1) derived from the polymerizable unsaturated compound having the (A-1) alkoxysilyl group contained in the (A) copolymer of the present embodiment has the (A-1) alkoxysilyl group. The polymerizable unsaturated compound is not particularly limited as long as it is a monomer having an alkoxysilyl group and an ethylenically unsaturated group. The alkoxy group of the alkoxysilyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 1 to 2 carbon atoms. The number of alkoxy groups in the alkoxysilyl group may be 1 or more, but the trialkoxysilyl group having 3 groups is more preferable in that it has many cross-linking points and has better curability.
　構成単位（ａ－１）は、（Ａ）共重合体を合成する際の反応容易性や原料の入手容易性の観点から、（Ａ－１a）アルコキシシリル基含有（メタ）アクリレート由来の構成単位（ａ－１a）であることが好ましく、下記式（１）で表される構成単位であることがより好ましい。 The structural unit (a-1) is a structural unit derived from (A-1a) an alkoxysilyl group-containing (meth) acrylate from the viewpoint of the ease of reaction when synthesizing the (A) copolymer and the availability of raw materials. (A-1a) is preferable, and it is more preferable that the structural unit is represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000003
 ［式（１）中、Ｒ１は水素原子又はメチル基を表し、Ｒ２～Ｒ４は各々独立に、水素原子、炭素原子数１～６のアルキル基又は炭素原子数１～６のアルコキシ基を表し、ｎは１～１０の整数である。ただし、Ｒ２～Ｒ４のうち少なくとも１つは炭素原子数１～６のアルコキシ基である。］
Figure JPOXMLDOC01-appb-C000003
 [In the formula (1), R 1 represents a hydrogen atom or a methyl group, and R 2 to R 4 are independent hydrogen atoms, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Represents, and n is an integer of 1 to 10. However, at least one of R 2 to R 4 is an alkoxy group having 1 to 6 carbon atoms. ]
　式（１）中、Ｒ１は水素原子またはメチル基を表し、メチル基が好ましい。
　式（１）中、Ｒ２～Ｒ４が示す炭素原子数１～６のアルキル基は、炭素原子数１～４が好ましく、炭素原子数１～２がより好ましい。Ｒ２～Ｒ４が示す炭素原子数１～６のアルコキシ基は、炭素数１～４であることが好ましく、炭素数１～２であることがより好ましい。Ｒ２～Ｒ４は各々独立に、炭素原子数１～６のアルキル基又は炭素原子数１～６のアルコキシ基であることが好ましく、Ｒ２～Ｒ４のうち２つが炭素原子数１～６のアルコキシ基であることがより好ましく、Ｒ２～Ｒ４のうち３つ全てが炭素原子数１～６のアルコキシ基であることがさらに好ましい。具体例としては、Ｒ２～Ｒ４は各々独立に、メチル基、エチル基、メトキシ基、又はエトキシ基が好ましく、Ｒ２～Ｒ４のうち少なくとも１つはメトキシ基又はエトキシ基であることがより好ましい。ｎは１～１０の整数であり、１～４であることが最も好ましい。
In the formula (1), R 1 represents a hydrogen atom or a methyl group, and a methyl group is preferable.
In the formula (1), the alkyl group of R 2 ~ R 4 is C 1 -C 6 shown preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms. Alkoxy group R 2 ~ R 4 is C 1 -C 6 shown preferably has 1 to 4 carbon atoms, and more preferably 1 to 2 carbon atoms. It is preferable that R 2 to R 4 are independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and two of R 2 to R 4 have 1 to 6 carbon atoms. more preferably an alkoxy group, more preferably all three of R 2 ~ R 4 is an alkoxy group having 1 to 6 carbon atoms. As a specific example, R 2 to R 4 are each independently preferably a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and at least one of R 2 to R 4 is a methoxy group or an ethoxy group. More preferred. n is an integer of 1 to 10, and most preferably 1 to 4.
　上記式（１）で表される構成単位の具体例としては、例えば、
３－（メタ）アクリロイルオキシプロピルメチルジメトキシシラン（式（１）中、Ｒ１：水素原子又はメチル基；Ｒ２：メチル基；Ｒ３、Ｒ４：メトキシ基；ｎ：３）、
３－（メタ）アクリロイルオキシプロピルエチルジメトキシシラン（式（１）中、Ｒ１：水素原子又はメチル基；Ｒ２：エチル基；Ｒ３、Ｒ４：メトキシ基；ｎ：３）、
３－（メタ）アクリロイルオキシプロピルメチルジエトキシシラン（式（１）中、Ｒ１：水素原子又はメチル基；Ｒ２：メチル基；Ｒ３、Ｒ４：エトキシ基；ｎ：３）、
３－（メタ）アクリロイルオキシプロピルエチルジエトキシシラン（式（１）中、Ｒ１：水素原子又はメチル基；Ｒ２：エチル基；Ｒ３、Ｒ４：エトキシ基；ｎ：３）、
３－（メタ）アクリロイルオキシプロピルトリメトキシシラン（式（１）中、Ｒ１：水素原子又はメチル基；Ｒ２～Ｒ４：メトキシ基；ｎ：３）、
３－（メタ）アクリロイルオキシプロピルトリエトキシシラン（式（１）中、Ｒ１：水素原子又はメチル基；Ｒ２～Ｒ４：エトキシ基；ｎ：３）
等の化合物由来の構成単位が挙げられる。これらの中でも、材料入手のし易さ及び（Ａ）共重合体を合成する際の反応性の観点から、３－（メタ）アクリロイルオキシプロピルトリメトキシシラン及び３－（メタ）アクリロイルオキシプロピルトリエトキシシラン由来の構成単位が好ましい。 As a specific example of the structural unit represented by the above formula (1), for example,
3- (Meta) acryloyloxypropylmethyldimethoxysilane (in formula (1), R 1 : hydrogen atom or methyl group; R 2 : methyl group; R 3 , R 4 : methoxy group; n: 3),
3- (Meta) acryloyloxypropyl ethyldimethoxysilane (in formula (1), R 1 : hydrogen atom or methyl group; R 2 : ethyl group; R 3 , R 4 : methoxy group; n: 3),
3- (Meta) acryloyloxypropylmethyldiethoxysilane (in formula (1), R 1 : hydrogen atom or methyl group; R 2 : methyl group; R 3 , R 4 : ethoxy group; n: 3),
3- (Meta) acryloyloxypropyl ethyldiethoxysilane (in formula (1), R 1 : hydrogen atom or methyl group; R 2 : ethyl group; R 3 , R 4 : ethoxy group; n: 3),
3- (meth) acryloyloxy propyl trimethoxy silane (formula (1), R 1: a hydrogen atom or a methyl group; R 2 ~ R 4: a methoxy group; n: 3),
3- (meth) acryloyloxy propyl triethoxysilane (formula (1), R 1: a hydrogen atom or a methyl group; R 2 ~ R 4: ethoxy group; n: 3)
Examples thereof include structural units derived from compounds such as. Among these, 3- (meth) acryloyloxypropyltrimethoxysilane and 3- (meth) acryloyloxypropyltriethoxy are considered from the viewpoint of easy availability of materials and reactivity in synthesizing (A) copolymer. A silane-derived structural unit is preferred.
　本実施形態の（Ａ）共重合体を構成する全構成単位中の構成単位（ａ－１）の含有量は、４５モル％以上であり、５０モル%以上であることが好ましく、６０モル％以上であることがより好ましく、７３モル％以上であることがさらに好ましい。構成単位（ａ－１）の含有量が４５モル％未満であると、感光性樹脂組成物の保存安定性や現像性能が不十分であったり、樹脂硬化膜の硬度が不足することが懸念される。また構成単位（ａ－１）の含有量は、９９モル%以下であり、９０モル％以下であることが好ましく、８５モル％以下であることがより好ましい。構成単位（ａ－１）の含有量が９９モル％より大きいと、感光性樹脂組成物の現像性や塗膜の平坦性が劣ることが懸念される。 The content of the structural unit (a-1) in all the structural units constituting the (A) copolymer of the present embodiment is 45 mol% or more, preferably 50 mol% or more, preferably 60 mol%. The above is more preferable, and 73 mol% or more is further preferable. If the content of the structural unit (a-1) is less than 45 mol%, there is a concern that the storage stability and development performance of the photosensitive resin composition will be insufficient, or the hardness of the cured resin film will be insufficient. To. The content of the structural unit (a-1) is 99 mol% or less, preferably 90 mol% or less, and more preferably 85 mol% or less. If the content of the structural unit (a-1) is larger than 99 mol%, there is a concern that the developability of the photosensitive resin composition and the flatness of the coating film are inferior.
［（Ａ－２）酸基を有する重合性不飽和化合物由来の構成単位（ａ－２）］
　本実施形態の（Ａ）共重合体に含まれる、（Ａ－２）酸基を有する重合性不飽和化合物由来の構成単位（ａ－２）について、（Ａ－２）酸基を有する重合性不飽和化合物は、酸基とエチレン性不飽和基を有し、ケイ素を含まない化合物であれば特に限定されない。構成単位（ａ－２）が有する酸基は、特に限定されないが、通常、カルボキシ基、リン酸基（－Ｏ－Ｐ(＝Ｏ)(ＯＨ)２）、スルホン酸基（－Ｓ（＝Ｏ）２ＯＨ）等が好ましい。これらの中でも、感光性樹脂組成物としての現像性の観点から、カルボキシ基がより好ましい。 [(A-2) Structural unit derived from a polymerizable unsaturated compound having an acid group (a-2)]
Regarding the structural unit (a-2) derived from the polymerizable unsaturated compound having (A-2) acid group contained in the (A) copolymer of the present embodiment, the polymerizable property having (A-2) acid group The unsaturated compound has an acid group and an ethylenically unsaturated group, and is not particularly limited as long as it is a compound that does not contain silicon. The acid group of the structural unit (a-2) is not particularly limited, but is usually a carboxy group, a phosphoric acid group (-OP (= O) (OH) 2 ), a sulfonic acid group (-S (= O)). ) 2 OH) and the like are preferable. Among these, a carboxy group is more preferable from the viewpoint of developability as a photosensitive resin composition.
　構成単位（ａ－２）の具体例としては、例えば、（メタ）アクリル酸、クロトン酸、桂皮酸、ビニルスルホン酸、２－（メタ）アクリロイルオキシエチルコハク酸、２－アクリロイルオキシエチルフタル酸、２－（メタ）アクリロイルオキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイルオキシエチルアシッドホスフェート等に由来する構成単位が挙げられる。これらの中でも、入手のし易さ及び（Ａ）共重合体を合成する際の反応性の観点から、（メタ）アクリル酸由来の構成単位が好ましい。 Specific examples of the structural unit (a-2) include (meth) acrylic acid, crotonic acid, cinnamic acid, vinyl sulfonic acid, 2- (meth) acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, and the like. Examples thereof include constituent units derived from 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl acid phosphate and the like. Among these, a structural unit derived from (meth) acrylic acid is preferable from the viewpoint of easy availability and (A) reactivity when synthesizing a copolymer.
　本実施形態の（Ａ）共重合体を構成する全構成単位中の構成単位（ａ－２）の含有量は、１～５５モル％であることが好ましく、１５～４０モル％であることがより好ましく、１５～３０モル％であることがさらに好ましい。構成単位（ａ－２）の含有量が１モル％以上であると、感光性樹脂組成物としての現像性が良好である。構成単位（ａ－２）の含有量が５５モル％以下であると、構成単位（ａ－１）の含有量が十分に多くなり、樹脂硬化膜として良好な硬度が得られる。 The content of the structural unit (a-2) in all the structural units constituting the (A) copolymer of the present embodiment is preferably 1 to 55 mol%, preferably 15 to 40 mol%. More preferably, it is more preferably 15 to 30 mol%. When the content of the structural unit (a-2) is 1 mol% or more, the developability of the photosensitive resin composition is good. When the content of the structural unit (a-2) is 55 mol% or less, the content of the structural unit (a-1) is sufficiently large, and good hardness can be obtained as a resin cured film.
［（Ａ－３）その他の重合性不飽和化合物由来の構成単位（ａ－３）］
　本実施形態の（Ａ）共重合体は、構成単位（ａ－１）および構成単位（ａ－２）に加えて、（Ａ－３）その他の重合性不飽和化合物由来の構成単位（ａ－３）を有していてもよい。（Ａ－３）その他の重合性不飽和化合物は、（Ａ－１）アルコキシシリル基を有する重合性不飽和化合物や（Ａ－２）酸基を有する重合性不飽和化合物以外の酸基やアルコキシシリル基を有さない重合性不飽和化合物である。（Ａ－３）化合物の例は、ブタジエン等のジエン類、（メタ）アクリル酸エステル類、（メタ）アクリル酸アミド類、ビニル化合物類、スチレン類、不飽和ジカルボン酸ジエステル、不飽和多塩基酸無水物を含む。
　（メタ）アクリル酸エステル類の具体例は、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリルレート、ｓｅｃ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリルレート、ペンチル（メタ）アクリレート、ネオペンチル（メタ）アクリレート、ベンジル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、ラウリル（メタ）アクリレート、ドデシル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、メチルシクロヘキシル（メタ）アクリレート、エチルシクロヘキシル（メタ）アクリレート、１，４－シクロヘキサンジメタノールモノ（メタ）アクリレート、ロジン（メタ）アクリレート、ノルボルニル（メタ）アクリレート、５－メチルノルボルニル（メタ）アクリレート、５－エチルノルボルニル（メタ）アクリレート、アリル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、１，１，１－トリフルオロエチル（メタ）アクリレート、パーフルオロエチル（メタ）アクリレート、パーフルオロ－ｎ－プロピル（メタ）アクリレート、パーフルオロ－イソプロピル（メタ）アクリレート、トリフェニルメチル（メタ）アクリレート、クミル（メタ）アクリレート、３－（Ｎ，Ｎ－ジメチルアミノ）プロピル（メタ）アクリレート、グリセリロールモノ（メタ）アクリレート、ブタントリオールモノ（メタ）アクリレート、ペンタントリオールモノ（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、ナフタレン（メタ）アクリレート、アントラセン（メタ）アクリレート、２－（２－ビニロキシエトキシ）エチル（メタ）アクリレート、グリシジル（メタ）アクリレート、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート、（３－エチルオキセタン－３－イル）メチル（メタ）アクリレート、イソシアナト基を有するエチレン性不飽和化合物、前記のイソシアナト基を有するエチレン性不飽和化合物のイソシアナト基を、ブロック剤を用いてブロック化したブロックイソシアナト基を有する化合物、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレート、Ｎ－ｔｅｒｔ－ブチルアミノエチル（メタ）アクリレート、テトラメチルピペリジル（メタ）アクリレート、ヘキサメチルピペリジル（メタ）アクリレート等を含む。前記のイソシアナト基を有するエチレン性不飽和化合物としては、例えば、２－イソシアナトエチル（メタ）アクリレート、２－イソシアナトプロピル（メタ）アクリレート、３－イソシアナトプロピル（メタ）アクリレート、２－イソシアナト－１－メチルエチル（メタ）アクリレート、２－イソシアナト－１，１－ジメチルエチル（メタ）アクリレート、４－イソシアナトシクロヘキシル（メタ）アクリレートが挙げられる。
　（メタ）アクリル酸アミド類の具体例は、（メタ）アクリル酸アミド、（メタ）アクリル酸Ｎ，Ｎ－ジメチルアミド、（メタ）アクリル酸Ｎ，Ｎ－ジエチルアミド、（メタ）アクリル酸Ｎ，Ｎ－ジプロピルアミド、（メタ）アクリル酸Ｎ，Ｎ－ジ－イソプロピルアミド、（メタ）アクリル酸アントラセニルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、（メタ）アクリルモルフォリン、ダイアセトン（メタ）アクリルアミド等を含む。　ビニル化合物の具体例は、ノルボルネン（ビシクロ［２．２．１］ヘプト－２－エン）、５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－エチルビシクロ［２．２．１］ヘプト－２－エン、テトラシクロ［４．４．０．１２，５．１７，１０］ドデカ－３－エン、８－メチルテトラシクロ［４．４．０．１２，５．１７，１０］ドデカ－３－エン、８－エチルテトラシクロ［４．４．０．１２，５．１７，１０］ドデカ－３－エン、ジシクロペンタジエン、トリシクロ［５．２．１．０２，６］デカ－８－エン、トリシクロ［５．２．１．０２，６］デカ－３－エン、トリシクロ［４．４．０．１２，５］ウンデカ－３－エン、トリシクロ［６．２．１．０１，８］ウンデカ－９－エン、トリシクロ［６．２．１．０１，８］ウンデカ－４－エン、テトラシクロ［４．４．０．１２，５．１７，１０．０１，６］ドデカ－３－エン、８－メチルテトラシクロ［４．４．０．１２，５．１７，１０．０１，６］ドデカ－３－エン、８－エチリデンテトラシクロ［４．４．０．１２，５．１７，１２］ドデカ－３－エン、８－エチリデンテトラシクロ［４．４．０．１２，５．１７，１０．０１，６］ドデカ－３－エン、ペンタシクロ［６．５．１．１３，６．０２，７．０９，１３］ペンタデカ－４－エン、ペンタシクロ［７．４．０．１２，５．１９，１２．０８，１３］ペンタデカ－３－エン、５－ノルボルネン－２，３－ジカルボン酸無水物、（メタ）アクリル酸アニリド、（メタ）アクリロイルニトリル、アクロレイン、塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、ビニルピリジン、酢酸ビニル、ビニルトルエン等を含む。
　スチレン頼の具体例は、スチレン、スチレンのα－、ｏ－、ｍ－、ｐ－アルキル、ニトロ、シアノ、アミド誘導体を含む。
　不飽和ジカルボン酸ジエステルの具体例は、シトラコン酸ジエチル、マレイン酸ジエチル、フマル酸ジエチル、イタコン酸ジエチル等を含む。
　不飽和多塩基酸無水物の具体例は、無水マレイン酸、無水イタコン酸、無水シトラコン酸等を含む。
　これらの（Ａ－３）化合物は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　これらの中でも、入手のし易さ及び反応性の観点から、メチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、グリシジル（メタ）アクリレート、（３－エチルオキセタン－３－イル）メチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレート、（メタ）アクリル酸Ｎ，Ｎ－ジメチルアミド、（メタ）アクリルモルフォリン、スチレン、ビニルトルエン及びノルボルネンが好ましい。メチル（メタ）アクリレート、ベンジル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、グリシジル（メタ）アクリレート、（３－エチルオキセタン－３－イル）メチル（メタ）アクリレート、スチレン及びビニルトルエンがより好ましい。
　これらの中でも耐熱分解性及び耐熱黄変性の観点から、アルキル（メタ）アクリレートが好ましく、メチル（メタ）アクリレート、ベンジル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレートがより好ましい。また、耐溶剤性向上の観点から、酸基と反応する官能基を有する重合性化合物が好ましく、具体的にはグリシジル基、オキセタニル基、イソシアナト基、又はブロックイソシアナト基を有する重合性化合物が挙げられる。より好ましくは、入手のし易さ及び反応性の観点から、グリシジル（メタ）アクリレート、（３－エチルオキセタン－３－イル）メチルメタクリレートなどが挙げられる。 [(A-3) Structural unit derived from other polymerizable unsaturated compounds (a-3)]
In the copolymer (A) of the present embodiment, in addition to the structural unit (a-1) and the structural unit (a-2), the structural unit (a-) derived from (A-3) and other polymerizable unsaturated compounds is used. 3) may be possessed. The (A-3) other polymerizable unsaturated compounds include acid groups and alkoxys other than the (A-1) polymerizable unsaturated compound having an alkoxysilyl group and the (A-2) polymerizable unsaturated compound having an acid group. It is a polymerizable unsaturated compound having no silyl group. Examples of the compound (A-3) include dienes such as butadiene, (meth) acrylic acid esters, (meth) acrylic acid amides, vinyl compounds, styrenes, unsaturated dicarboxylic acid diesters, and unsaturated polybasic acids. Contains anhydride.
Specific examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylic rate, and sec-butyl. (Meta) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylic rate, pentyl (meth) acrylate, neopentyl (meth) acrylate, benzyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-Ethylhexyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) Acrylate, 1,4-Cyclohexanedimethanol mono (meth) acrylate, rosin (meth) acrylate, norbornyl (meth) acrylate, 5-methylnorbornyl (meth) acrylate, 5-ethylnorbornyl (meth) acrylate, allyl (Meta) acrylate, tetrahydrofurfuryl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-isopropyl (Meta) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, glycerilol mono (meth) acrylate, butanetriol mono (meth) acrylate , Pentantriol mono (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, naphthalene (meth) acrylate, anthracene (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, isocyanato The ethylenically unsaturated compound having a group and the above-mentioned isoshianato group having an ethylenically unsaturated compound. Compounds having a blocked isocyanato group obtained by blocking anato groups with a blocking agent, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N-tert-butylaminoethyl. Includes (meth) acrylate, tetramethylpiperidyl (meth) acrylate, hexamethylpiperidyl (meth) acrylate and the like. Examples of the ethylenically unsaturated compound having an isocyanato group include 2-isocyanatoethyl (meth) acrylate, 2-isocyanatopropyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, and 2-isocyanato-. Examples thereof include 1-methylethyl (meth) acrylate, 2-isocyanato-1,1-dimethylethyl (meth) acrylate, and 4-isocyanatocyclohexyl (meth) acrylate.
Specific examples of (meth) acrylic acid amides include (meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, and (meth) acrylic acid N, N. -Dipropylamide, (meth) acrylic acid N, N-di-isopropylamide, (meth) acrylic acid anthracenylamide, N-isopropyl (meth) acrylamide, (meth) acrylic morpholine, diacetone (meth) acrylamide Etc. are included. Specific examples of the vinyl compound include norbornene (bicyclo [2.2.1] hept-2-ene), 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2. 1] Hept-2-ene, tetracyclo [4.4.0.1 2,5 . 17 and 10 ] Dodeca-3-ene, 8-methyltetracyclo [4.4.0.1 2,5 . 17 and 10 ] Dodeca-3-ene, 8-ethyltetracyclo [4.4.0.1 2,5 . 1 7, 10 ] Dodeca-3-en, Dicyclopentadiene, Tricyclo [5.2.1.0 2,6 ] Deca-8-en, Tricyclo [5.2.1.0 2,6 ] Deca-3 -En, Tricyclo [4.4.0.1 2,5 ] Undec-3-en, Tricyclo [6.2.1.0 1,8 ] Undec-9-En, Tricyclo [6.2.1.0] 1,8 ] Undeca-4-en, tetracyclo [4.4.0.1 2,5 . 17 and 10 . 0 1,6 ] Dodeca-3-ene, 8-methyltetracyclo [4.4.0.1 2,5 . 17 and 10 . 0 1,6 ] Dodeca-3-en, 8-ethylidenetetracyclo [4.4.0.1 2,5 . 17 and 12 ] Dodeca-3-en, 8-ethylidenetetracyclo [4.4.0.1 2,5 . 17 and 10 . 0 1,6 ] Dodeca-3-ene, pentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13] pentadeca-4-ene, pentacyclo [7.4.0.1 2,5. 19 and 12 . 0 8,13] pentadeca-3-ene, 5-norbornene-2,3-dicarboxylic acid anhydride, (meth) anilide acrylic acid, (meth) acryloyl nitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, Includes vinylidene chloride, vinylpyridine, vinyl acetate, vinyltoluene and the like.
Specific examples of styrene reliance include styrene, α-, o-, m-, p-alkyl, nitro, cyano, and amide derivatives of styrene.
Specific examples of unsaturated dicarboxylic acid diesters include diethyl citraconic acid, diethyl maleate, diethyl fumaric acid, diethyl itaconic acid and the like.
Specific examples of the unsaturated polybasic acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride and the like.
These (A-3) compounds may be used alone or in combination of two or more.
Among these, from the viewpoint of availability and reactivity, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, glycidyl (meth) acrylate , (3-Ethyloxetane-3-yl) methyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic morpholine, styrene, vinyl Toluene and norbornen are preferred. Methyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, glycidyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, styrene and vinyltoluene are more preferred. ..
Among these, alkyl (meth) acrylate is preferable, and methyl (meth) acrylate, benzyl (meth) acrylate, and dicyclopentanyl (meth) acrylate are more preferable from the viewpoint of heat-resistant decomposition and heat-resistant yellowing. Further, from the viewpoint of improving solvent resistance, a polymerizable compound having a functional group that reacts with an acid group is preferable, and specific examples thereof include a polymerizable compound having a glycidyl group, an oxetanyl group, an isocyanato group, or a blocked isocyanato group. Be done. More preferably, from the viewpoint of availability and reactivity, glycidyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl methacrylate and the like can be mentioned.
　上記したブロック剤の例は、ε－カプロラクタム、δ－バレロラクタム、γ－ブチロラクタム、β－プロピオラクタム等のラクタム系；メタノール、エタノール、プロパノール、ブタノール、エチレングリコール、メチルセロソルブ、ブチルセロソルブ、メチルカルビトール、ベンジルアルコール、フェニルセロソルブ、フルフリルアルコール、シクロヘキサノール等のアルコール系；フェノール、クレゾール、キシレノール、エチルフェノール、ｏ－イソプロピルフェノール、ｐ－ｔｅｒｔ－ブチルフェノール等のブチルフェノール、ｐ－ｔｅｒｔ－オクチルフェノール、ノニルフェノール、ジノニルフェノール、スチレン化フェノール、オキシ安息香酸エステル、チモール、ｐ－ナフトール、ｐ－ニトロフェノール、ｐ－クロロフェノール等のフェノール系；マロン酸ジメチル、マロン酸ジエチル、アセト酢酸メチル、アセト酢酸エチル、アセチルアセトン等の活性メチレン系；ブチルメルカプタン、チオフェノール、ｔｅｒｔ－ドデシルメルカプタン等のメルカプタン系；ジフェニルアミン、フェニルナフチルアミン、アニリン、カルバゾール等のアミン系；アセトアニリド、アセトアニシジド、酢酸アミド、ベンズアミド等の酸アミド系；コハク酸イミド、マレイン酸イミド等の酸イミド系；イミダゾール、２－メチルイミダゾール、２－エチルイミダゾール等のイミダゾール系；尿素、チオ尿素、エチレン尿素等の尿素系；Ｎ－フェニルカルバミン酸フェニル、２－オキサゾリドン等のカルバミド酸塩系；エチレンイミン、ポリエチレンイミン等のイミン系；ホルムアルドオキシム、アセトアルドオキシム、アセトオキシム、メチルエチルケトオキシム、メチルイソブチルケトオキシム、シクロヘキサノンオキシム等のオキシム系；重亜硫酸ソーダ、重亜硫酸カリウム等の重亜硫酸塩系等を含む。 Examples of the above-mentioned blocking agents are oxidases such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam; methanol, ethanol, propanol, butanol, ethylene glycol, methylcellosolve, butylcellosolve, methylcarbitol. , Oximes such as benzyl alcohol, phenylcellosolve, flufuryl alcohol, cyclohexanol; butylphenols such as phenol, cresol, xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, p-tert-octylphenol, nonylphenol, di Phenols such as nonylphenol, styrenated phenol, oxybenzoic acid ester, timol, p-naphthol, p-nitrophenol, p-chlorophenol; dimethyl malonate, diethyl malonate, methyl acetate acetate, ethyl acetate, acetylacetone, etc. Active oxime system; mercaptan system such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan; amine system such as diphenylamine, phenylnaphthylamine, aniline, carbazole; acid amide system such as acetoanilide, acetoaniside, acetate amide, benzamide; succinic acidimide, Oxime-based such as maleic acidimide; imidazole-based such as imidazole, 2-methylimidazole, 2-ethylimidazole; urea-based such as urea, thiourea and ethyleneurea; carbamide such as phenyl N-phenylcarbamate and 2-oxazolidone. Acid salt-based: Oxime-based such as ethyleneimine and polyethyleneimin; Oxime-based such as formaldehyde, acetaldoxime, acetoxime, methylethylketooxime, methylisobutylketooxime, cyclohexanoneoxime; Includes sulfites, etc.
　本実施形態の（Ａ）共重合体が構成単位（ａ－３）を有する場合、全構成単位中の構成単位（ａ－３）の含有量は、０．１～４０モル％であることが好ましく、１～３０モル％であることがより好ましく、５～２０モル％であることがさらに好ましい。構成単位（ａ－３）の含有量が０．１モル％以上であると、感光性樹脂組成物に対して、構成単位（ａ－３）に起因する機能を十分に付与することができる。構成単位（ａ－３）の含有量が４０モル％以下であると、構成単位（ａ－１）および構成単位（ａ－２）の含有量が十分に多くなるため、感光性樹脂組成物として良好な現像性を有し、硬度や密着性に優れた樹脂硬化膜が得られる。 When the (A) copolymer of the present embodiment has a structural unit (a-3), the content of the structural unit (a-3) in all the structural units may be 0.1 to 40 mol%. It is preferably 1 to 30 mol%, more preferably 5 to 20 mol%. When the content of the structural unit (a-3) is 0.1 mol% or more, the function derived from the structural unit (a-3) can be sufficiently imparted to the photosensitive resin composition. When the content of the structural unit (a-3) is 40 mol% or less, the contents of the structural unit (a-1) and the structural unit (a-2) are sufficiently large, so that the photosensitive resin composition can be used as a photosensitive resin composition. A resin cured film having good developability and excellent hardness and adhesion can be obtained.
　本実施形態の（Ａ）共重合体の重量平均分子量（Ｍｗ）は、ポリスチレン換算で、２０００～３００００であることが好ましく、３０００～１００００であることがより好ましく、３０００～６０００であることがさらに好ましい。（Ａ）共重合体の重量平均分子量（Ｍｗ）が２０００以上であると、現像性が良好である。（Ａ）共重合体の重量平均分子量（Ｍｗ）が３００００以下であると、現像時間を適切な範囲に調整できる。 The weight average molecular weight (Mw) of the (A) copolymer of the present embodiment is preferably 2000 to 30,000, more preferably 3000 to 10000, and further preferably 3000 to 6000 in terms of polystyrene. preferable. (A) When the weight average molecular weight (Mw) of the copolymer is 2000 or more, the developability is good. (A) When the weight average molecular weight (Mw) of the copolymer is 30,000 or less, the development time can be adjusted within an appropriate range.
　本実施形態の（Ａ）共重合体の重量平均分子量（Ｍｗ）の値は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）を用いて、下記条件にて測定し、ポリスチレン換算にて算出されるものである。
　カラム：ショウデックス（登録商標）ＬＦ－８０４＋ＬＦ－８０４（昭和電工株式会社製）
　カラム温度：４０℃
　試料：（Ａ）共重合体の含有量が０．２質量％のテトラヒドロフラン溶液
　展開溶媒：テトラヒドロフラン
　検出器：示差屈折計（商品名：ショウデックス（登録商標）ＲＩ－７１Ｓ、昭和電工株式会社製）
　流速：１ｍＬ／ｍｉｎ The value of the weight average molecular weight (Mw) of the (A) copolymer of the present embodiment is measured by gel permeation chromatography (GPC) under the following conditions and calculated in terms of polystyrene. Is.
Column: Showdex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko KK)
Column temperature: 40 ° C
Sample: (A) Tetrahydrofuran solution with a copolymer content of 0.2% by mass Developing solvent: Tetrahydrofuran Detector: Differential refractometer (trade name: Shodex (registered trademark) RI-71S, manufactured by Showa Denko KK)
Flow rate: 1 mL / min
　本実施形態の（Ａ）共重合体の分子量分布（Ｍｗ／Ｍｎ）は、１．３～３．０であることが好ましく、１．５～２．５であることがより好ましく、１．５～２．０であることがさらに好ましい。（Ａ）共重合体の分子量分布（Ｍｗ／Ｍｎ）が１．３以上であると、重量平均分子量や酸価など、目標数値範囲の最適化や（Ａ）共重合体を製造する際の反応条件等を一定の幅をもって設定することができ、効率的である。（Ａ）共重合体の分子量分布（Ｍｗ／Ｍｎ）が３．０未満であると、現像性など感光性樹脂組成物としての性能にばらつきが生じることもない。分子量分布は、上記ＧＰＣ測定のクロマトグラムから測定する。 The molecular weight distribution (Mw / Mn) of the (A) copolymer of the present embodiment is preferably 1.3 to 3.0, more preferably 1.5 to 2.5, and 1.5. It is more preferably ~ 2.0. When the molecular weight distribution (Mw / Mn) of the (A) copolymer is 1.3 or more, the target numerical range such as the weight average molecular weight and the acid value is optimized, and (A) the reaction when producing the copolymer. Conditions and the like can be set with a certain width, which is efficient. (A) When the molecular weight distribution (Mw / Mn) of the copolymer is less than 3.0, the performance of the photosensitive resin composition such as developability does not vary. The molecular weight distribution is measured from the above GPC measurement chromatogram.
　本実施形態の（Ａ）共重合体の酸価は、特に限定されないが、好ましくは１５ＫＯＨｍｇ／ｇ～１５０ＫＯＨｍｇ／ｇ、より好ましくは２５ＫＯＨｍｇ／ｇ～１００ＫＯＨｍｇ／ｇ、さらに好ましくは３０ＫＯＨｍｇ／ｇ～７０ＫＯＨｍｇ／ｇである。（Ａ）共重合体の酸価が１５ＫＯＨｍｇ／ｇ以上であれば、より良好な現像性が得られる。一方、（Ａ）共重合体の酸価が１５０ＫＯＨｍｇ／ｇ以下であれば、アルカリ現像液に対して露光部分（光硬化部分）が溶解することなく良好な現像性が得られる。
　なお、（Ａ）共重合体の酸価とは、ＪＩＳ　Ｋ６９０１　５．３に従ってブロモチモールブルーとフェノールレッドの混合指示薬を用いて測定された値であって、（Ａ）共重合体１ｇ中に含まれる酸性成分を中和するのに要する水酸化カリウムのｍｇ数を意味する。 The acid value of the (A) copolymer of the present embodiment is not particularly limited, but is preferably 15 KOH mg / g to 150 KOH mg / g, more preferably 25 KOH mg / g to 100 KOH mg / g, and further preferably 30 KOH mg / g to 70 KOH mg / g. g. (A) When the acid value of the copolymer is 15 KOHmg / g or more, better developability can be obtained. On the other hand, when the acid value of the (A) copolymer is 150 KOHmg / g or less, good developability can be obtained without dissolving the exposed portion (photocured portion) in the alkaline developer.
The acid value of the (A) copolymer is a value measured using a mixed indicator of bromothymol blue and phenol red according to JIS K6901 5.3, and is contained in 1 g of the (A) copolymer. It means the number of mg of potassium hydroxide required to neutralize the acidic component.
　本実施形態の（Ａ）共重合体のシリル基当量は、特に限定されないが、好ましくは２９０ｇ／ｍｏｌ～４５０ｇ／ｍｏｌ、より好ましくは３００ｇ／ｍｏｌ～４２０ｇ／ｍｏｌ、最も好ましくは３００ｇ／ｍｏｌ～４００ｇ／ｍｏｌである。（Ａ）共重合体のシリル基当量が２９０ｇ／ｍｏｌ以上であれば、硬度及び現像性をより高めるのに効果的である。一方、（Ａ）共重合体のシリル基当量が４５０ｇ／ｍｏｌ以下であれば、樹脂硬化膜として十分な硬度を確保できる。
　なお、（Ａ）共重合体のシリル基当量は、（Ａ）共重合体の分子量を１分子当たりのシリル基の平均個数で割った値であり、（Ａ）共重合体を合成する際の（Ａ－１）アルコキシシリル基を有する重合性不飽和化合物の仕込み量に基づいて算出される計算値とする。 The silyl group equivalent of the copolymer (A) of the present embodiment is not particularly limited, but is preferably 290 g / mol to 450 g / mol, more preferably 300 g / mol to 420 g / mol, and most preferably 300 g / mol to 400 g. / Mol. When the silyl group equivalent of the (A) copolymer is 290 g / mol or more, it is effective in further increasing the hardness and developability. On the other hand, when the silyl group equivalent of the (A) copolymer is 450 g / mol or less, sufficient hardness can be secured as a resin cured film.
The silyl group equivalent of the (A) copolymer is a value obtained by dividing the molecular weight of the (A) copolymer by the average number of silyl groups per molecule, and (A) when synthesizing the copolymer. (A-1) The calculated value is calculated based on the amount of the polymerizable unsaturated compound having an alkoxysilyl group charged.
［（Ｂ）光酸発生剤］
　本実施形態の（Ｂ）光酸発生剤としては、光照射によって分解し、酸を発生するものであれば特に限定されないが、波長１９０～５００ｎｍの光を照射することによって酸を発生するものが好ましい。中でも入手が容易で、感光性樹脂組成物としての保存安定性が良好である点から、スルホニウム塩化合物またはヨードニウム塩化合物が好ましく、芳香族スルホニウム塩化合物または芳香族ヨードニウム塩化合物がより好ましく、芳香族スルホニウム塩化合物がさらに好ましく、トリアリールスルホニウム塩化合物が特に好ましい。　本実施形態の（Ｂ）光酸発生剤が有するアニオン種としては、特に限定されないが、ボレートアニオンやリン系アニオンが好ましく、感光性樹脂組成物としての低温硬化性の観点から、ボレートアニオンが特に好ましい。ボレートアニオンとしては、ＢＦ４ －、（Ｃ６Ｆ５）４Ｂ－、（Ｃ６Ｈ５）（Ｃ６Ｆ５）３Ｂ－、（（ＣＦ３）２Ｃ６Ｈ３）４Ｂ－等が挙げられる。中でもフルオロアルキル基含有ボレートアニオンが好ましい。リン系アニオンとしては、ＰＦ６ －、（ＣＦ３ＣＦ２）３ＰＦ３ －、（ＣＦ３ＣＦ２ＣＦ２ＣＦ２）３ＰＦ３ －等が挙げられる。中でもフルオロアルキル基含有リン系アニオンが好ましい。 [(B) Photoacid generator]
The (B) photoacid generator of the present embodiment is not particularly limited as long as it decomposes by light irradiation and generates an acid, but an agent that generates an acid by irradiating light having a wavelength of 190 to 500 nm is used. preferable. Among them, a sulfonium salt compound or an iodonium salt compound is preferable, an aromatic sulfonium salt compound or an aromatic iodonium salt compound is more preferable, and an aromatic iodonium salt compound is preferable because it is easily available and has good storage stability as a photosensitive resin composition. Sulfonium salt compounds are more preferred, and triarylsulfonium salt compounds are particularly preferred. The anion species contained in the (B) photoacid generator of the present embodiment is not particularly limited, but borate anions and phosphorus-based anions are preferable, and borate anions are particularly preferable from the viewpoint of low-temperature curability as a photosensitive resin composition. preferable. The borate anion, BF 4 -, (C 6 F 5) 4 B -, (C 6 H 5) (C 6 F 5) 3 B -, ((CF 3) 2 C 6 H 3) 4 B - like Can be mentioned. Of these, a fluoroalkyl group-containing borate anion is preferable. Examples of the phosphorus-based anion, PF 6 -, (CF 3 CF 2) 3 PF 3 -, (CF 3 CF 2 CF 2 CF 2) 3 PF 3 - , and the like. Of these, fluoroalkyl group-containing phosphorus anions are preferable.
　前記（Ｂ）光酸発生剤の具体例としては、特開２０１２－２７２９０号公報、特開２０１１－２０１８０３号公報、特開２０１１－１９５４９９号公報等に開示の光酸発生剤；サンアプロ（株）化学社製の商品名ＣＰＩ－２００Ｋ、ＣＰＩ－２１０Ｓ、ＣＰＩ－３１０Ｂ、ＣＰＩ－４１０Ｓ等のスルホニウム塩化合物；ＩＫ－１等のヨードニウム塩化合物等が挙げられる。中でも、感光性樹脂組成物としての低温硬化性が良好であり、樹脂硬化膜としての硬度や透過率が優れる点からＣＰＩ－２１０Ｓ、ＣＰＩ－３１０Ｂが好ましい。これらの（Ｂ）光酸発生剤は、単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Specific examples of the (B) photoacid generator include the photoacid generators disclosed in JP-A-2012-27290, JP-A-2011-201803, JP-A-2011-195499, and the like; San-Apro Co., Ltd. Examples thereof include sulfonium salt compounds such as CPI-200K, CPI-210S, CPI-310B, and CPI-410S manufactured by Chemical Industries; and iodonium salt compounds such as IK-1. Among them, CPI-210S and CPI-310B are preferable because they have good low-temperature curability as a photosensitive resin composition and are excellent in hardness and transmittance as a resin cured film. These (B) photoacid generators may be used alone or in combination of two or more.
　前記（Ｂ）光酸発生剤の含有量は、生成する酸の発生量、発生速度に応じて調整が必要である。例えば（Ａ）共重合体１００質量部に対して、０．１～１０質量部であることが好ましく、０．１～５質量部であることがより好ましく、０．３～３質量部であることがさらに好ましい。（Ｂ）光酸発生剤の含有量が、０．１質量部以上であると、発生する酸の量が十分であり、硬化膜として十分な硬度が得られる。含有量が１０質量部以下であると、樹脂硬化膜の外観が良好であり、（Ｂ）光酸発生剤の添加に起因する着色も発生しない。 The content of the (B) photoacid generator needs to be adjusted according to the amount and rate of acid generated. For example, (A) is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and 0.3 to 3 parts by mass with respect to 100 parts by mass of the copolymer. Is even more preferable. (B) When the content of the photoacid generator is 0.1 part by mass or more, the amount of generated acid is sufficient and sufficient hardness can be obtained as a cured film. When the content is 10 parts by mass or less, the appearance of the cured resin film is good, and (B) coloring due to the addition of the photoacid generator does not occur.
［（Ｃ）溶剤］
　本実施形態の（Ｃ）溶剤は、感光性樹脂組成物の各成分に対し不活性で、各成分を溶解可能な溶剤であれば特に限定されない。（Ａ）共重合体の合成の際に、（Ｃ）溶剤と同様の溶剤を用いて合成し、この溶媒を分離、除去することなくそのまま感光性樹脂組成物の（Ｃ）溶剤として用いてもよいし、感光性樹脂組成物の各成分を混合する際に新たに追加してもよい。感光性樹脂組成物の各成分を混合する際にそれらの成分と共存する溶剤であってもよい。中でも、感光性樹脂組成物としての保存安定性の観点から、炭素原子数３～１０の第一級アルコール又は第二級アルコールのいずれかを少なくとも含むことが好ましく、炭素原子数３～１０の第一級アルコールを含むことがより好ましい。炭素原子数３～１０の第一級アルコール又は第二級アルコール溶剤の具体例としては、例えば、モノアルコール類、（ポリ）アルキレングリコールモノアルキルエーテル類等が挙げられる。
　モノアルコール類の具体例は、プロピルアルコール、ブチルアルコール、ペンチルアルコール、ヘキシルアルコール、オクチルアルコール、ノニルアルコール、デシルアルコール、ドデシルアルコール、ベンジルアルコール等を含む。
　（ポリ）アルキレングリコールモノアルキルエーテル類の具体例は、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ－ｎ－プロピルエーテル、ジエチレングリコールモノ－ｎ－ブチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノ－ｎ－プロピルエーテル、ジプロピレングリコールモノ－ｎ－ブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノエチルエーテル、３－メトキシ－１－ブタノール等を含む。
　これらの中でも、入手のし易さおよび感光性樹脂組成物としての保存安定性の観点から、（ポリ）アルキレングリコールモノアルキルエーテル類が好ましい。これらの溶剤は、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 [(C) Solvent]
The solvent (C) of the present embodiment is not particularly limited as long as it is a solvent that is inert to each component of the photosensitive resin composition and can dissolve each component. (A) When synthesizing the copolymer, it may be synthesized using the same solvent as the solvent (C), and the solvent may be used as it is as the solvent (C) of the photosensitive resin composition without separation and removal. Alternatively, it may be newly added when mixing each component of the photosensitive resin composition. It may be a solvent that coexists with each component of the photosensitive resin composition when it is mixed. Above all, from the viewpoint of storage stability as a photosensitive resin composition, it is preferable to contain at least one of a primary alcohol or a secondary alcohol having 3 to 10 carbon atoms, and the third to 10 carbon atoms. It is more preferable to contain primary alcohol. Specific examples of the primary alcohol or the secondary alcohol solvent having 3 to 10 carbon atoms include monoalcohols, (poly) alkylene glycol monoalkyl ethers and the like.
Specific examples of monoalcohols include propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, dodecyl alcohol, benzyl alcohol and the like.
Specific examples of (poly) alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, and tri. Ethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono Includes -n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, 3-methoxy-1-butanol and the like.
Among these, (poly) alkylene glycol monoalkyl ethers are preferable from the viewpoint of easy availability and storage stability as a photosensitive resin composition. These solvents may be used alone or in combination of two or more.
　本実施形態の（Ｃ）溶剤は、上記記載の溶剤の以外に、その他の溶剤を含んでもよい。その他の溶剤の具体例は、ｔｅｒｔ－ブチルアルコール、ダイアセトンアルコール等の第三級アルコール類；エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等の（ポリ）アルキレングリコールモノアルキルエーテルアセテート類；ジエチレングリコールジメチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジエチルエーテル、テトラヒドロフラン等の他のエーテル類；メチルエチルケトン、シクロヘキサノン、２－ヘプタノン、３－ヘプタノン等のケトン類；２－ヒドロキシプロピオン酸メチル、２－ヒドロキシプロピオン酸エチル、２－ヒドロキシ－２－メチルプロピオン酸メチル、２－ヒドロキシ－２－メチルプロピオン酸エチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２－ヒドロキシ－３－メチル酪酸メチル、３－メチル－３－メトキシブチルアセテート、３－メチル－３－メトキシブチルプロピオネート、酢酸エチル、酢酸ｎ－ブチル、酢酸ｎ－プロピル、酢酸ｉ－プロピル、酢酸ｎ－ブチル、酢酸ｉ－ブチル、酢酸ｎ－アミル、酢酸ｉ－アミル、プロピオン酸ｎ－ブチル、酪酸エチル、酪酸ｎ－プロピル、酪酸ｉ－プロピル、酪酸ｎ－ブチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸ｎ－プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソ酪酸エチル等のエステル類；トルエン、キシレン等の芳香族炭化水素類；Ｎ－メチルピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等のカルボン酸アミド類等を含む。これらの中でも、炭素原子数３～１０の第一級アルコール又は第二級アルコールとの相溶性や感光性樹脂組成物の各成分の溶解性の観点から、プロピレングリコールモノメチルエーテルアセテート等の（ポリ）アルキレングリコールモノアルキルエーテルアセテート系溶剤が好ましい。 The solvent (C) of the present embodiment may contain other solvents in addition to the above-mentioned solvent. Specific examples of other solvents include tertiary alcohols such as tert-butyl alcohol and diacetone alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like. (Poly) alkylene glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; 2- Methyl hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propio Nate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, butyric acid Esters such as n-propyl, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate; toluene, xylene, etc. Aromatic hydrocarbons; include carboxylic acid amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like. Among these, (poly) such as propylene glycol monomethyl ether acetate from the viewpoint of compatibility with primary alcohols having 3 to 10 carbon atoms or secondary alcohols and solubility of each component of the photosensitive resin composition. An alkylene glycol monoalkyl ether acetate solvent is preferred.
　（Ｃ）溶剤の含有量は、感光性樹脂組成物の（Ｃ）溶剤を除く成分の総和を１００質量部としたときに、好ましくは３０質量部～１０００質量部、より好ましくは５０質量部～８００質量部、最も好ましくは１００質量部～５００質量部である。（Ｃ）溶剤の配合量が、上記範囲内であると、感光性樹脂組成物の粘度を適切な範囲に調整することができる。 The content of the solvent (C) is preferably from 30 parts by mass to 1000 parts by mass, more preferably from 50 parts by mass when the total of the components of the photosensitive resin composition excluding the solvent (C) is 100 parts by mass. It is 800 parts by mass, most preferably 100 parts by mass to 500 parts by mass. (C) When the blending amount of the solvent is within the above range, the viscosity of the photosensitive resin composition can be adjusted to an appropriate range.
［（Ｄ）反応性希釈剤］
　本実施形態の感光性樹脂組成物は必要に応じて（Ｄ）反応性希釈剤を配合してもよい。（Ｄ）反応性希釈剤としては、ビニル基、アリル基、（メタ）アクリロイルオキシ基等のエチレン性不飽和基を有する低分子量化合物であれば特に限定されない。（Ｄ）反応性希釈剤の具体例は、芳香族ビニル系モノマー類；酢酸ビニル、アジピン酸ビニル等のポリカルボン酸モノマー類；（メタ）アクリレート類；多官能（メタ）アクリレート類；トリアリルシアヌレート等を含む。
　芳香族ビニル系モノマー類の具体例は、スチレン、α－メチルスチレン、α－クロロメチルスチレン、ビニルトルエン、ジビニルベンゼン、ジアリルフタレート、ジアリルベンゼンホスホネート等を含む。
　（メタ）アクリレート類の具体例は、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、β－ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート等を含む。　多官能（メタ）アクリレート類の具体例は、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリス（ヒドロキシエチル）イソシアヌレートのトリ（メタ）アクリレート等を含む。これらの中でも、多官能（メタ）アクリレート類が特に好ましい。これらの（Ｄ）反応性希釈剤は、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 [(D) Reactive Diluent]
The photosensitive resin composition of the present embodiment may contain (D) a reactive diluent, if necessary. The reactive diluent (D) is not particularly limited as long as it is a low molecular weight compound having an ethylenically unsaturated group such as a vinyl group, an allyl group and a (meth) acryloyloxy group. Specific examples of the (D) reactive diluent include aromatic vinyl-based monomers; polycarboxylic acid monomers such as vinyl acetate and vinyl adipic acid; (meth) acrylates; polyfunctional (meth) acrylates; and triallylsia. Including monomers and the like.
Specific examples of aromatic vinyl-based monomers include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallylphthalate, diallylbenzenephosphonate and the like.
Specific examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, β-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and the like. including. Specific examples of polyfunctional (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, and trimethyl propandi (meth). Includes acrylate, trimethylol propantri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate and the like. Among these, polyfunctional (meth) acrylates are particularly preferable. These (D) reactive diluents may be used alone or in combination of two or more.
　（Ｄ）反応性希釈剤の配合量は、（Ａ）共重合体と（Ｄ）反応性希釈剤との質量比が、４０：６０～９９：１となるように配合することが好ましく、５０：５０～９５：５がより好ましく、６０：４０～９０：１０がさらに好ましい。（Ｄ）反応性希釈剤の配合量が上記範囲内であると、感光性樹脂組成物としての粘度および光硬化性を適切に調整することができる。 The amount of the (D) reactive diluent is preferably blended so that the mass ratio of the (A) copolymer to the (D) reactive diluent is 40:60 to 99: 1, preferably 50. : 50 to 95: 5 is more preferable, and 60:40 to 90:10 is even more preferable. (D) When the blending amount of the reactive diluent is within the above range, the viscosity and photocurability of the photosensitive resin composition can be appropriately adjusted.
［（Ｅ）光重合開始剤］
　本実施形態の感光性樹脂組成物が（Ｄ）反応性希釈剤を含有する場合には、併せて（Ｅ）光重合開始剤を用いる。（Ｅ）光重合開始剤としては、光照射によりラジカルを発生する化合物であれば特に限定されないが、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル等のベンゾインとそのアルキルエーテル類；アセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、１，１－ジクロロアセトフェノン、４－（１－ｔ－ブチルジオキシ－１－メチルエチル）アセトフェノン等のアセトフェノン類；１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン等のアルキルフェノン類；２－メチルアントラキノン、２－アミルアントラキノン、２－ｔ－ブチルアントラキノン、１－クロロアントラキノン等のアントラキノン類；２，４－ジメチルチオキサントン、２，４－ジイソプロピルチオキサントン、２－クロロチオキサントン等のチオキサントン類；アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類；ベンゾフェノン、４－（１－ｔ－ブチルジオキシ－１－メチルエチル）ベンゾフェノン、３，３’，４，４’－テトラキス（ｔ－ブチルジオキシカルボニル）ベンゾフェノン等のベンゾフェノン類；１，２－オクタンジオン，１－［４－（フェニルチオ）－２－（ｏ－ベンゾイルオキシム）］、エタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］，１－（ｏ－アセチルオキシム）等のオキシムエステル類；２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノ－プロパン－１－オン；２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）ブタノン－１；２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）フェニルホスフィンオキサイド等のアシルホスフィンオキサイド類；キサントン類等が挙げられる。これらの（Ｅ）光重合開始剤は、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 [(E) Photopolymerization Initiator]
When the photosensitive resin composition of the present embodiment contains (D) a reactive diluent, (E) a photopolymerization initiator is also used. The (E) photopolymerization initiator is not particularly limited as long as it is a compound that generates a radical by irradiation with light, but for example, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether and its alkyl ethers; acetophenone, 2, Acetphenones such as 2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4- (1-t-butyldioxy-1-methylethyl) acetophenone; 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl Alkylphenones such as -1-phenylpropan-1-one; anthracinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2, Thioxanthons such as 4-diisopropylthioxanthone and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, 3,3', 4 , 4'-Tetrakiss (t-butyldioxycarbonyl) benzophenone and other benzophenones; 1,2-octanedione, 1- [4- (phenylthio) -2- (o-benzoyloxime)], etanone, 1-[ Oxym esters such as 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl], 1- (o-acetyloxime); 2-methyl-1- [4- (methylthio) phenyl] -2-Molholino-Propane-1-one; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Butanone-1; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4) 6-trimethylbenzoyl) Acylphosphine oxides such as phenylphosphine oxide; xanthons and the like can be mentioned. These (E) photopolymerization initiators may be used alone or in combination of two or more.
　（Ｅ）光重合開始剤の含有量は、（Ｄ）反応性希釈剤１００質量部に対して、０．１～３０質量部であることが好ましく、０．５～２０質量部であることがより好ましく、１～１５質量部であることがさらに好ましい。（Ｅ）光重合開始剤の含有量が０．１質量部以上であると、感光性樹脂組成物が十分な光硬化性を有する。含有量が３０質量部以下であると、感光性樹脂組成物の保存安定性や樹脂硬化膜の性能に悪影響を及ぼすことがない。 The content of the (E) photopolymerization initiator is preferably 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the (D) reactive diluent. It is more preferably 1 to 15 parts by mass, further preferably 1 to 15 parts by mass. (E) When the content of the photopolymerization initiator is 0.1 parts by mass or more, the photosensitive resin composition has sufficient photocurability. When the content is 30 parts by mass or less, the storage stability of the photosensitive resin composition and the performance of the cured resin film are not adversely affected.
　本実施形態の感光性樹脂組成物には、上記の成分に加えて、所定の特性を付与するために、公知のレベリング剤、熱重合禁止剤等の公知の添加剤を配合してもよい。感光性樹脂組成物におけるこれらの添加剤の配合量は、本発明の効果を阻害しない範囲であれば特に限定されない。 In addition to the above components, the photosensitive resin composition of the present embodiment may contain known additives such as known leveling agents and thermal polymerization inhibitors in order to impart predetermined properties. The blending amount of these additives in the photosensitive resin composition is not particularly limited as long as it does not impair the effects of the present invention.
　本実施形態の感光性樹脂組成物の粘度は、目的とする樹脂硬化膜の厚さに応じて適宜調整することができる。例えば、樹脂硬化膜の厚さを１～４μmに調整する場合、感光性樹脂組成物の粘度は、４～２５ｍＰ・ｓが好ましく、６～２０ｍＰ・ｓがより好ましく、８～１５ｍＰ・ｓがさらに好ましい。 The viscosity of the photosensitive resin composition of the present embodiment can be appropriately adjusted according to the thickness of the target resin cured film. For example, when the thickness of the cured resin film is adjusted to 1 to 4 μm, the viscosity of the photosensitive resin composition is preferably 4 to 25 mP · s, more preferably 6 to 20 mP · s, and further preferably 8 to 15 mP · s. preferable.
　本実施形態の感光性樹脂組成物に含まれるケイ素の総含有量は、感光性樹脂組成物から（Ｃ）溶剤を除いた全成分の合計質量に対し、４．０～２０質量％であり、４．５～１０質量％であることが好ましく、５．０～９．５質量％であることがより好ましい。ケイ素の総含有量が４．０質量％以上であると、樹脂硬化膜が十分な硬度を有する。ケイ素の総含有量が２０質量％以下であると、感光性樹脂組成物の現像性や樹脂硬化膜の平坦性が良好である。ケイ素の総含有量は、原料の仕込み量から算出した計算値である。 The total content of silicon contained in the photosensitive resin composition of the present embodiment is 4.0 to 20% by mass with respect to the total mass of all the components excluding the solvent (C) from the photosensitive resin composition. It is preferably 4.5 to 10% by mass, more preferably 5.0 to 9.5% by mass. When the total content of silicon is 4.0% by mass or more, the cured resin film has sufficient hardness. When the total content of silicon is 20% by mass or less, the developability of the photosensitive resin composition and the flatness of the cured resin film are good. The total silicon content is a calculated value calculated from the amount of raw materials charged.
＜（Ａ）共重合体の製造方法＞
　本実施形態の（Ａ）共重合体は、（Ｃ－１）溶剤の存在下で、（Ａ－１）アルコキシシリル基を有する重合性不飽和化合物、（Ａ－２）酸基を有する重合性不飽和化合物、および必要に応じて用いる（Ａ－３）その他の重合性不飽和化合物からなるモノマー混合物を、当該技術分野において公知のラジカル重合方法に従って共重合させることにより調製することができる。例えば、（Ａ－１）化合物、（Ａ－２）化合物及び（Ａ－３）化合物を（Ｃ－１）溶剤に溶解して、溶液を調製した後、その溶液に重合開始剤を添加し、５０℃～１３０℃にて１時間～２０時間反応させればよい。（Ａ）共重合体における、それぞれの化合物の繰り返し数や、それぞれの化合物が結合する順番は特に限定されない。また、構成単位（ａ－１）、構成単位（ａ－２）及び構成単位（ａ－３）のいずれかを含まない共重合体を調製した後に、不足する構成単位を変性反応により共重合体内に導入することで、構成単位（ａ－１）、構成単位（ａ－２）及び構成単位（ａ－３）を含む共重合体を調製してもよい。 <(A) Method for producing copolymer>
The (A) copolymer of the present embodiment is a polymerizable unsaturated compound having (A-1) an alkoxysilyl group and (A-2) polymerizable having an acid group in the presence of (C-1) solvent. It can be prepared by copolymerizing an unsaturated compound and a monomer mixture consisting of (A-3) and other polymerizable unsaturated compounds used as necessary according to a radical polymerization method known in the art. For example, the compound (A-1), the compound (A-2) and the compound (A-3) are dissolved in the solvent (C-1) to prepare a solution, and then a polymerization initiator is added to the solution. The reaction may be carried out at 50 ° C. to 130 ° C. for 1 hour to 20 hours. (A) In the copolymer, the number of repetitions of each compound and the order in which each compound is bonded are not particularly limited. Further, after preparing a copolymer containing no of the constituent units (a-1), the constituent units (a-2) and the constituent units (a-3), the insufficient constituent units are subjected to a modification reaction in the copolymer. By introducing into the above, a copolymer containing a structural unit (a-1), a structural unit (a-2) and a structural unit (a-3) may be prepared.
　前記（Ａ－１）～（Ａ－３）化合物については、上述の各構成単位（ａ－１）～（ａ－３）を構成する化合物として挙げたものを用いることができる。 As for the compounds (A-1) to (A-3), those listed as the compounds constituting the above-mentioned structural units (a-1) to (a-3) can be used.
　上記した（Ａ）共重合体を構成する構成単位（ａ－１）～（ａ－３）の含有比率を規定したのと同様の理由で、（Ａ－１）化合物、（Ａ－２）化合物及び（Ａ－３）化合物の配合量を規定することができる。すなわち、（Ａ－１）～（Ａ－３）化合物の合計を１００モル％としたときに、（Ａ－１）化合物の配合量は、４５～９９モル％であり、５０～９０モル％であることが好ましく、６０～８５モル％であることがより好ましく、７０～８５モル％であることがさらに好ましい。（Ａ－２）化合物の配合量は、１～５５モル％であることが好ましく、１５～４０モル％であることがより好ましく、１５～３０モル％であることがさらに好ましい。（Ａ－３）化合物を用いる場合の配合量は、０．１～４０モル％であることが好ましく、１～３０モル％であることがより好ましく、５～２０モル％であることがさらに好ましい。 The (A-1) compound and the (A-2) compound for the same reason as defining the content ratios of the structural units (a-1) to (a-3) constituting the (A) copolymer described above. And (A-3) the compounding amount of the compound can be specified. That is, when the total of the compounds (A-1) to (A-3) is 100 mol%, the blending amount of the compound (A-1) is 45 to 99 mol%, and 50 to 90 mol%. It is preferably 60 to 85 mol%, more preferably 70 to 85 mol%, and even more preferably 70 to 85 mol%. The blending amount of the compound (A-2) is preferably 1 to 55 mol%, more preferably 15 to 40 mol%, still more preferably 15 to 30 mol%. When the compound (A-3) is used, the blending amount is preferably 0.1 to 40 mol%, more preferably 1 to 30 mol%, still more preferably 5 to 20 mol%. ..
　前記（Ｃ－１）溶剤については、重合反応に不活性の溶剤であれば特に限定されない。前述の感光性樹脂組成物として用いる（Ｃ）溶剤と同様の溶剤を使用すれば、重合反応用溶媒を分離、除去する必要が無いので好ましい。また、（Ａ）共重合体の重量平均分子量（Ｍｗ）及び分子量分布（Ｍｗ／Ｍｎ）を所定の範囲に制御すると共に、所望の保存安定性を有する感光性樹脂組成物を得る観点から、炭素原子数３～１０の第一級アルコール又は第二級アルコールのいずれかを少なくとも含む溶剤を使用することが好ましい。 The solvent (C-1) is not particularly limited as long as it is a solvent that is inert to the polymerization reaction. It is preferable to use a solvent similar to the solvent (C) used as the above-mentioned photosensitive resin composition because it is not necessary to separate and remove the solvent for the polymerization reaction. Further, from the viewpoint of (A) controlling the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the copolymer within a predetermined range and obtaining a photosensitive resin composition having desired storage stability, carbon is used. It is preferable to use a solvent containing at least either a primary alcohol or a secondary alcohol having a molecular weight of 3 to 10.
　溶剤が炭素原子数３～１０の第一級アルコール又は第二級アルコールのいずれかの溶剤を含む場合、炭素原子数３～１０の第一級アルコール又は第二級アルコール溶剤の含有比率は、溶剤の合計量に対して、１０～１００質量％であることが好ましく、２０～１００質量部であることがより好ましい。含有比率が上記範囲内であると、（Ａ）共重合体の重量分子量及び分子量分布（Ｍｗ／Ｍｎ）を所定の範囲により制御し易く、該溶剤を感光性樹脂組成物の（Ｃ）溶剤としてそのまま使用すれば、感光性樹脂組成物の保存安定性をより向上させることができる。 When the solvent contains either a primary alcohol or a secondary alcohol having 3 to 10 carbon atoms, the content ratio of the primary alcohol or the secondary alcohol solvent having 3 to 10 carbon atoms is the solvent. It is preferably 10 to 100% by mass, and more preferably 20 to 100 parts by mass with respect to the total amount of. When the content ratio is within the above range, the weight molecular weight and molecular weight distribution (Mw / Mn) of the (A) copolymer can be easily controlled within a predetermined range, and the solvent can be used as the (C) solvent of the photosensitive resin composition. If used as it is, the storage stability of the photosensitive resin composition can be further improved.
　（Ａ）共重合体の製造に用いる溶剤の使用量は、特に限定されないが、（Ａ－１）～（Ａ－３）化合物の仕込み量の合計を１００質量部としたときに、好ましくは３０質量部～１０００質量部、より好ましくは５０質量部～８００質量部である。使用量が３０質量部以上であると、重合反応を安定して行うことができ、（Ａ）共重合体の着色やゲル化を防止できる。使用量が１０００質量部以下であると、連鎖移動作用による（Ａ）共重合体の分子量の低下を抑制し、反応溶液の粘度を適切な範囲に制御することができる。 The amount of the solvent used for producing the (A) copolymer is not particularly limited, but is preferably 30 when the total amount of the compounds (A-1) to (A-3) charged is 100 parts by mass. It is a mass part to 1000 parts by mass, more preferably 50 parts by mass to 800 parts by mass. When the amount used is 30 parts by mass or more, the polymerization reaction can be stably carried out, and (A) coloring and gelation of the copolymer can be prevented. When the amount used is 1000 parts by mass or less, the decrease in the molecular weight of the (A) copolymer due to the chain transfer action can be suppressed, and the viscosity of the reaction solution can be controlled within an appropriate range.
　この共重合反応に用いることが可能な重合開始剤としては、特に限定されないが、例えば、２，２’－アゾビス（イソブチロニトリル）、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、２，２’－アゾビス（イソ酪酸）ジメチル、過酸化ベンゾイル、ｔ－ブチルパーオキシ－２－エチルヘキサノエート等が挙げられる。これらの重合開始剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　重合開始剤の使用量は、特に限定されないが、（Ａ－１）化合物、（Ａ－２）化合物及び（Ａ－３）化合物の仕込み量の合計を１００質量部としたときに、好ましくは０．１質量部～２０質量部、より好ましくは０．５質量部～１６質量部である。 The polymerization initiator that can be used in this copolymerization reaction is not particularly limited, and is, for example, 2,2'-azobis (isobutyronitrile) and 2,2'-azobis (2,4-dimethylvaleronitrile). ), 2,2'-azobis (isobutyric acid) dimethyl, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate and the like. These polymerization initiators may be used alone or in combination of two or more.
The amount of the polymerization initiator used is not particularly limited, but is preferably 0 when the total amount of the compound (A-1), (A-2) and (A-3) charged is 100 parts by mass. .1 part by mass to 20 parts by mass, more preferably 0.5 part by mass to 16 parts by mass.
＜感光性樹脂組成物の製造方法＞
　本実施形態の感光性樹脂組成物は、公知の混合装置を用い、上記の成分を混合することによって調製してもよい。あるいは、本実施形態の感光性樹脂組成物は、先に、（Ａ）共重合体及び（Ｃ－１）溶剤を含む組成物を調製した後、（Ｂ）光酸発生剤、および任意成分の（Ｄ）反応性希釈剤、（Ｅ）光重合開始剤を添加し、混合することによって調製してもよい。「（Ａ）共重合体及び（Ｃ－１）溶剤を含む組成物を調製した後」ということは、即ち、「（Ａ－１）化合物、（Ａ－２）化合物及び（Ａ－３）化合物からなるモノマー混合物を、（Ｃ－１）溶剤の存在下で共重合させた後」のことである。後者の調製方法では、必要に応じて、共重合後に（Ｃ－２）溶剤を追加で添加してもよい。共重合後に（Ｃ－２）溶剤を追加で添加する場合、感光性樹脂組成物に含まれている（Ｃ）溶剤は、（Ｃ－１）溶剤と（Ｃ－２）溶剤を含む。（Ｃ－２）溶剤は、（Ｃ－１）溶剤と同じでも、異なってもよく、（Ｃ－１）溶剤と同じであることが好ましい。すなわち、感光性樹脂組成物に含まれている（Ｃ）溶剤は、光重合体の製造用溶剤と同じであることが好ましい。 <Manufacturing method of photosensitive resin composition>
The photosensitive resin composition of the present embodiment may be prepared by mixing the above-mentioned components using a known mixing device. Alternatively, in the photosensitive resin composition of the present embodiment, first, a composition containing (A) a copolymer and (C-1) a solvent is prepared, and then (B) a photoacid generator and an optional component. It may be prepared by adding (D) a reactive diluent and (E) a photopolymerization initiator and mixing them. "After preparing the composition containing (A) copolymer and (C-1) solvent" means "(A-1) compound, (A-2) compound and (A-3) compound". After copolymerizing a monomer mixture composed of (C-1) in the presence of a solvent (C-1). " In the latter preparation method, if necessary, the (C-2) solvent may be additionally added after the copolymerization. When the (C-2) solvent is additionally added after the copolymerization, the (C) solvent contained in the photosensitive resin composition includes the (C-1) solvent and the (C-2) solvent. The (C-2) solvent may be the same as or different from the (C-1) solvent, and is preferably the same as the (C-1) solvent. That is, the solvent (C) contained in the photosensitive resin composition is preferably the same as the solvent for producing the photopolymer.
　本実施形態の感光性樹脂組成物は、アルカリ現像性を有しているので、アルカリ水溶液を用いることによって現像を行うことができる。特に、本実施形態の感光性樹脂組成物は、現像性に優れたパターンを与えることができる。そのため、本実施形態の感光性樹脂組成物は、有機ＥＬ表示装置、液晶表示装置、固体撮像素子に組み込まれるオーバーコート、保護膜、絶縁膜を製造するために用いられるレジストとして好適に用いられる。 Since the photosensitive resin composition of the present embodiment has alkaline developability, it can be developed by using an alkaline aqueous solution. In particular, the photosensitive resin composition of the present embodiment can give a pattern having excellent developability. Therefore, the photosensitive resin composition of the present embodiment is suitably used as a resist used for producing an overcoat, a protective film, and an insulating film incorporated in an organic EL display device, a liquid crystal display device, and a solid-state image sensor.
＜樹脂硬化膜＞
　本実施形態の樹脂硬化膜は、前記感光性樹脂組成物を基材に塗布、プリベーク、露光、ポストベークすることにより形成される。フォトリソグラフィ法によりパターンを形成する場合には、前記感光性樹脂組成物を基材に塗布、プリベークした後、形成した塗布膜を所定のパターンのフォトマスクを介して露光することにより露光部分を光硬化させる。そして、必要に応じて露光後加熱処理をした後、未露光部分をアルカリ水溶液で溶解して現像した後、ポストベークすることにより所定のパターンを形成することができる。 <Resin cured film>
The cured resin film of the present embodiment is formed by applying the photosensitive resin composition to a substrate, prebaking, exposing, and post-baking. When a pattern is formed by a photolithography method, the photosensitive resin composition is applied to a substrate, prebaked, and then the formed coating film is exposed through a photomask of a predetermined pattern to illuminate the exposed portion. Let it cure. Then, if necessary, after exposure and heat treatment, the unexposed portion is dissolved in an alkaline aqueous solution, developed, and then post-baked to form a predetermined pattern.
（１）塗布工程
　感光性樹脂組成物の塗布方法としては、特に限定されないが、スクリーン印刷法、ロールコート法、カーテンコート法、スプレーコート法、スピンコート法、スリットコート法等が用いられる。 (1) Coating Step The coating method of the photosensitive resin composition is not particularly limited, but a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, a slit coating method and the like are used.
（２）プリベーク工程
　塗布工程により塗膜を形成させたのち、その塗膜を乾燥させて塗膜中の溶剤残存量を減少させるため、プリベーク（前加熱処理）することが好ましい。プリベーク工程は、一般に７０～１２０℃、好ましくは９０～１１０℃の温度で、ホットプレートによる場合には１０～６００秒間、好ましくは１２０～１８０秒間実施することができる。 (2) Pre-bake step After forming a coating film by a coating step, it is preferable to pre-bake (preheat treatment) in order to dry the coating film and reduce the residual amount of solvent in the coating film. The prebaking step can be carried out at a temperature of generally 70 to 120 ° C., preferably 90 to 110 ° C., for 10 to 600 seconds, preferably 120 to 180 seconds when using a hot plate.
（３）露光工程
　形成した塗膜表面を、光照射により露光する。パターンを形成する場合には、塗膜表面を所定のパターンのフォトマスクを介して露光する。光照射に用いられる光源としては、特に限定されないが、例えば、低圧水銀ランプ、中圧水銀ランプ、高圧水銀ランプ、キセノンランプ、メタルハライドランプ等が用いられる。また、露光量も、特に限定されず、感光性樹脂組成物の組成に応じて適宜設定される。 (3) Exposure step The formed coating film surface is exposed by light irradiation. When forming a pattern, the surface of the coating film is exposed through a photomask of a predetermined pattern. The light source used for light irradiation is not particularly limited, and for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is used. Further, the exposure amount is not particularly limited, and is appropriately set according to the composition of the photosensitive resin composition.
（４）露光後加熱工程
　パターンを形成する場合には、露光工程後に必要に応じて露光後加熱処理（Ｐｏｓｔ Ｅｘｐｏｓｕｒｅ Ｂａｋｉｎｇ）を行うことができる。この工程により、塗膜の露光部と未露光部の溶解コントラストをより顕著に出すことができる。この工程は、後述する（６）ポストベークの工程とは異なり、塗膜を完全に硬化させるために行うものではなく、現像工程後に露光部のパターンだけを基板上に残し、未露光部の塗膜を現像により確実に除去することが可能となるように行う。従って、本実施形態の樹脂硬化膜の形成において、必須の工程ではない。露光後加熱処理を行う場合、ホットプレート、オーブン、またはファーネス等を使用することができる。加熱温度の範囲としては、４０℃～７０℃が好ましく、５０℃～６０℃が更に好ましい。加熱温度が４０℃以上であれば、塗膜の露光部と未露光部の溶解コントラストを向上させて、露光後加熱処理の効果を十分に発揮することができる。加熱温度が７０℃以下であれば、露光部に発生した酸が未露光部まで拡散することもなく良好な溶解コントラストを得られる。加熱時間の範囲としては、２０秒～６００秒が好ましい。２０秒以上であれば塗膜全体の温度履歴を均一にすることができる。６００秒以下であれば、露光部に発生した酸が未露光部まで拡散することもなく良好な溶解コントラストを得られる。 (4) Post-exposure heating process When a pattern is formed, post-exposure heat treatment (Post Exposure Backing) can be performed as necessary after the exposure process. By this step, the dissolution contrast between the exposed portion and the unexposed portion of the coating film can be made more remarkable. Unlike the step (6) post-baking described later, this step is not performed to completely cure the coating film, but only the pattern of the exposed portion is left on the substrate after the developing step, and the unexposed portion is coated. This is done so that the film can be reliably removed by development. Therefore, it is not an indispensable step in forming the resin cured film of the present embodiment. When heat treatment is performed after exposure, a hot plate, an oven, furnace, or the like can be used. The heating temperature range is preferably 40 ° C. to 70 ° C., more preferably 50 ° C. to 60 ° C. When the heating temperature is 40 ° C. or higher, the dissolution contrast between the exposed portion and the unexposed portion of the coating film can be improved, and the effect of the post-exposure heat treatment can be fully exhibited. When the heating temperature is 70 ° C. or lower, the acid generated in the exposed portion does not diffuse to the unexposed portion, and good dissolution contrast can be obtained. The heating time is preferably 20 seconds to 600 seconds. If it is 20 seconds or more, the temperature history of the entire coating film can be made uniform. If it is 600 seconds or less, the acid generated in the exposed portion does not diffuse to the unexposed portion, and a good dissolution contrast can be obtained.
（５）現像工程
　　露光後、必要に応じて露光後加熱を行ったあと、塗膜を現像処理する。現像の際に用いられる現像液としては、従来、感光性組成物の現像に用いられている任意の現像液を用いることができる。現像に用いられるアルカリ水溶液としては、特に限定されないが、例えば、炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、水酸化ナトリウム、水酸化カリウム等の水溶液；エチルアミン、ジエチルアミン、ジメチルエタノールアミン等のアミン系化合物の水溶液；水酸化テトラメチルアンモニウム等の第４級アンモニウム塩の水溶液；３－メチル－４－アミノ－Ｎ，Ｎ－ジエチルアニリン、３－メチル－４－アミノ－Ｎ－エチル－Ｎ－β－ヒドロキシエチルアニリン、３－メチル－４－アミノ－Ｎ－エチル－Ｎ－β－メタンスルホンアミドエチルアニリン、３－メチル－４－アミノ－Ｎ－エチル－Ｎ－β－メトキシエチルアニリン及びこれらの硫酸塩、塩酸塩又はｐ－トルエンスルホン酸塩等のｐ－フェニレンジアミン系化合物の水溶液等が用いられる。これらの中でも、ｐ－フェニレンジアミン系化合物の水溶液を用いることが好ましい。なお、これらのアルカリ水溶液には、必要に応じて、消泡剤や界面活性剤を添加してもよい。また、上記のアルカリ水溶液による現像の後、水洗して乾燥させることが好ましい。 (5) Development step After exposure, if necessary, heat is applied after exposure, and then the coating film is developed. As the developer used for development, any developer conventionally used for developing a photosensitive composition can be used. The alkaline aqueous solution used for development is not particularly limited, but is, for example, an aqueous solution of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide and the like; an aqueous solution of an amine compound such as ethylamine, diethylamine and dimethylethanolamine. An aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide; 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline , 3-Methyl-4-amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides Alternatively, an aqueous solution of a p-phenylenediamine compound such as p-toluenesulfonate is used. Among these, it is preferable to use an aqueous solution of a p-phenylenediamine-based compound. If necessary, a defoaming agent or a surfactant may be added to these alkaline aqueous solutions. Further, it is preferable to wash with water and dry after developing with the above alkaline aqueous solution.
（６）ポストベーク工程
　現像工程後にポストベークを行い、樹脂硬化膜を得る。ポストベークの条件は、特に限定されず、感光性樹脂組成物の組成に応じて加熱処理を行えばよい。例えば、８０℃～２５０℃の温度にて、１０分～６０分間加熱すればよい。基材に各種樹脂フィルムなどを用いる場合には、基材や回路の熱によるダメージ低減の観点からポストベーク工程の温度範囲を、８０℃～１３０℃とすることが好ましく、８０℃～１００℃とすることがより好ましい。 (6) Post-baking step Post-baking is performed after the developing step to obtain a resin cured film. The post-baking conditions are not particularly limited, and the heat treatment may be performed according to the composition of the photosensitive resin composition. For example, it may be heated at a temperature of 80 ° C. to 250 ° C. for 10 minutes to 60 minutes. When various resin films are used as the base material, the temperature range of the post-baking process is preferably 80 ° C. to 130 ° C., preferably 80 ° C. to 100 ° C. from the viewpoint of reducing damage due to heat of the base material and the circuit. It is more preferable to do so.
　本実施形態の樹脂硬化膜は、光透過率が高く透明性に優れる。また、樹脂硬化膜の硬度が良好であるため、カラーフィルター上部のオーバーコート、各種保護膜などに好適に用いることができる。また、タッチパネルのＩＴＯなど電極間の絶縁膜やＴＦＴの層間絶縁膜など、各種絶縁材料としても好適に用いることができる。 The resin cured film of this embodiment has high light transmittance and excellent transparency. Further, since the hardness of the cured resin film is good, it can be suitably used for an overcoat on the upper part of a color filter, various protective films, and the like. Further, it can be suitably used as various insulating materials such as an insulating film between electrodes such as ITO of a touch panel and an interlayer insulating film of a TFT.
＜画像表示装置＞
　本実施形態の画像表示装置は、上述した樹脂硬化膜を具備した画像表示素子を有する。前記画像表示素子としては、上述した樹脂硬化膜を具備していれば特に限定されないが、例えば、液晶表示素子、有機ＥＬ表示素子等が挙げられる。特に、本実施形態の感光性樹脂組成物は、高温域の加熱工程を有することなく樹脂硬化膜を作製することができるため、折りたたみスマホやフレキシブルディスプレイなど、ガラス基板を用いない画像表示装置に対しても有効である。 <Image display device>
The image display device of the present embodiment has an image display element provided with the above-mentioned resin cured film. The image display element is not particularly limited as long as it includes the above-mentioned resin cured film, and examples thereof include a liquid crystal display element and an organic EL display element. In particular, since the photosensitive resin composition of the present embodiment can produce a resin cured film without having a heating step in a high temperature range, it is suitable for an image display device that does not use a glass substrate, such as a folding smartphone or a flexible display. Is also effective.
　以下、実施例及び比較例により本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
　（Ａ）共重合体の合成例を以下に示す。 (A) An example of synthesizing the copolymer is shown below.
［合成例１］
　攪拌装置、滴下ロート、コンデンサー、温度計及びガス導入管を備えたフラスコに、３－メトキシ－１－ブタノール７００ｇを入れ、窒素置換しながら攪拌し、１０５℃に昇温した。
　次に、アクリル酸７．１ｇ（０．１モル）、３－メタクリロイルオキシプロピルトリエトキシシラン２５８．４ｇ（０．９モル）からなるモノマー混合物に、２，２’－アゾビス（イソ酪酸）ジメチル（重合開始剤）３４．５ｇを添加したものを、滴下ロートから前記フラスコ中に滴下した。
　滴下終了後、１０５℃にて２時間攪拌して共重合反応を行い、（Ａ）共重合体と溶剤を含む試料１（重量平均分子量（Ｍｗ）：３８００、数平均分子量（Ｍｎ）：２５００、分子量分布（Ｍｗ／Ｍｎ）：１．５、酸価：５．６ＫＯＨｍｇ／ｇ、シリル基当量：３３７ｇ／ｍｏｌ）を得た。試料１の固形分濃度３０質量％とした。なお、固形分とは、試料を１３０℃で２時間加熱したときの加熱残分を意味し、試料１の固形分は（Ａ）共重合体が主成分となる。 [Synthesis Example 1]
700 g of 3-methoxy-1-butanol was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube, and the mixture was stirred while being replaced with nitrogen, and the temperature was raised to 105 ° C.
Next, 2,2'-azobis (isobutyric acid) dimethyl (2,2'-azobis (isobutyric acid) dimethyl (isobutyric acid) dimethyl (2,2'-azobis (isobutyric acid) dimethyl) was added to a monomer mixture consisting of 7.1 g (0.1 mol) of acrylic acid and 258.4 g (0.9 mol) of 3-methacryloxypropyltriethoxysilane. A product to which 34.5 g of a polymerization initiator) was added was added dropwise to the flask from the dropping funnel.
After completion of the dropping, the copolymerization reaction was carried out by stirring at 105 ° C. for 2 hours. (A) Sample 1 containing the copolymer and the solvent (weight average molecular weight (Mw): 3800, number average molecular weight (Mn): 2500, The molecular weight distribution (Mw / Mn): 1.5, acid value: 5.6 KOHmg / g, silyl group equivalent: 337 g / mol) was obtained. The solid content concentration of Sample 1 was set to 30% by mass. The solid content means the heating residue when the sample is heated at 130 ° C. for 2 hours, and the solid content of the sample 1 is mainly composed of the (A) copolymer.
［合成例２～１０、比較合成例１～３］
　表１に記載の原料を用い、また、得られた試料の固形分濃度が３０質量％になるようにそれぞれの３－メトキシ－１－ブタノールの添加量を調整した。また表１に示す各分子量（重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ））になるように重合開始剤の添加量を調整した以外は合成例１と同様にして、共重合反応を行い、（Ａ）共重合体と溶剤を含む試料２～１３を得た。得られた試料の重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）、分子量分布（Ｍｗ／Ｍｎ）、酸価及びシリル基当量を、表１に示す。 [Synthesis Examples 2 to 10, Comparative Synthesis Examples 1 to 3]
The raw materials shown in Table 1 were used, and the amount of each 3-methoxy-1-butanol added was adjusted so that the solid content concentration of the obtained sample was 30% by mass. Further, the copolymerization reaction was carried out in the same manner as in Synthesis Example 1 except that the addition amount of the polymerization initiator was adjusted so as to have each molecular weight (weight average molecular weight (Mw), number average molecular weight (Mn)) shown in Table 1. , (A) Samples 2 to 13 containing the copolymer and the solvent were obtained. Table 1 shows the weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn), acid value and silyl group equivalent of the obtained sample.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
＜（Ａ）共重合体の評価＞
（１）保存安定性
　得られた試料１～１３を用いて、以下の方法に従い、保存安定性の評価を行った。
　試料を２０ｍｌのガラス容器に１０ｇずつ計り取ってサンプルとし、ＧＰＣ（ＧＰＣ－１０１、Ｓｈｏｄｅｘ製）を使用して重量平均分子量を測定した。続いて、これらのサンプルをそれぞれ１２℃に保った恒温器の中に３ヶ月間静置して保存した後、再び重量平均分子量を測定した。保存安定性試験前後の重量平均分子量を用いて、下記式（Ｉ）より分子量の増加率を求めた。
　分子量の増加率＝（（［試験後の分子量］－［試験前の分子量］）／［試験前の分子量］）×１００％　　　　（Ｉ）
　この評価の基準は以下の通りである。
　○：増加率３０％未満
　×：増加率３０％以上
　上記の保存安定性の評価結果を表１に示す。 <(A) Evaluation of copolymer>
(1) Storage stability Using the obtained samples 1 to 13, the storage stability was evaluated according to the following method.
The sample was weighed in a 20 ml glass container in an amount of 10 g each to prepare a sample, and the weight average molecular weight was measured using GPC (GPC-101, manufactured by Shodex). Subsequently, each of these samples was allowed to stand in an incubator kept at 12 ° C. for 3 months and stored, and then the weight average molecular weight was measured again. Using the weight average molecular weight before and after the storage stability test, the rate of increase in molecular weight was determined from the following formula (I).
Rate of increase in molecular weight = (([Molecular weight after test]-[Molecular weight before test]) / [Molecular weight before test]) x 100% (I)
The criteria for this evaluation are as follows.
◯: Increase rate less than 30% ×: Increase rate 30% or more Table 1 shows the above evaluation results of storage stability.
＜感光性樹脂組成物の調製＞
　得られた試料１～１３を用いて、表２および表３に示す配合成分及び配合割合に従って、感光性樹脂組成物を調製した。
　なお、表２および表３における（Ａ）共重合体の配合量は、（Ａ）共重合体を合成する際に用いた溶剤の量を含まない。 <Preparation of photosensitive resin composition>
Using the obtained samples 1 to 13, a photosensitive resin composition was prepared according to the compounding components and compounding ratios shown in Tables 2 and 3.
The blending amount of the (A) copolymer in Tables 2 and 3 does not include the amount of the solvent used when synthesizing the (A) copolymer.
［実施例１］
　得られた試料１（固形分濃度３０質量％）を用いて、（Ａ）共重合体として固形分を１００ｇ、光酸発生剤としてＣＰＩ－３１０Ｂを０．５ｇ、溶剤として３－メトキシ－１－ブタノールを３００ｇの配合で感光性樹脂組成物を調整した。３００ｇの溶剤には、試料１に含まれている溶剤を含む。調整した感光性樹脂組成物について、以下の方法で硬度、透過率、密着性、現像性の評価を行った。結果を表２に示す。 [Example 1]
Using the obtained sample 1 (solid content concentration 30% by mass), (A) 100 g of solid content as a copolymer, 0.5 g of CPI-310B as a photoacid generator, and 3-methoxy-1- as a solvent. The photosensitive resin composition was prepared by blending 300 g of butanol. The 300 g of solvent contains the solvent contained in sample 1. The prepared photosensitive resin composition was evaluated for hardness, transmittance, adhesion, and developability by the following methods. The results are shown in Table 2.
［実施例２～１６、比較例１～４］
　表２および表３に記載の原料を用いる以外は実施例１と同様にして感光性樹脂組成物を調整し、硬度、透過率、密着性、現像の評価を行った。結果を表２および表３に示す。 [Examples 2 to 16, Comparative Examples 1 to 4]
The photosensitive resin composition was prepared in the same manner as in Example 1 except that the raw materials shown in Tables 2 and 3 were used, and the hardness, transmittance, adhesion, and development were evaluated. The results are shown in Tables 2 and 3.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表２および表３に記載の材料は以下のものを用いた。
・光酸発生剤：ＣＰＩ－３１０Ｂ（トリアリールスルホニウムボレート塩、サンアプロ（株）化学社製）
・光酸発生剤：ＣＰＩ－２１０Ｓ（トリアリールスルホニウム・特殊リン系アニオン塩、サンアプロ（株）化学社製）
・反応性希釈剤：ＤＰＨＡ（ジペンタエリスリトールヘキサアクリレート、東亞合成（株）社製）
・光重合開始剤：ＯＸＥ－０１（商品名、ＢＡＳＦジャパン社製） The following materials were used as the materials shown in Tables 2 and 3.
-Photoacid generator: CPI-310B (triarylsulfonium borate salt, manufactured by San-Apro Co., Ltd.)
-Photoacid generator: CPI-210S (triarylsulfonium, special phosphorus anion salt, manufactured by San-Apro Co., Ltd.)
-Reactive diluent: DPHA (dipentaerythritol hexaacrylate, manufactured by Toagosei Co., Ltd.)
-Photopolymerization initiator: OXE-01 (trade name, manufactured by BASF Japan Ltd.)
＜感光性樹脂組成物の評価＞
（１）現像性
　調製された感光性樹脂組成物を、スピンコーター法により５ｃｍ角のガラス基板（無アルカリガラス基板）上に塗布し、１００℃にて３分間加熱（プリベーク）することで溶剤を揮発させ、ガラス基板上に塗布膜を形成した。次に、幅３～１００μｍのライン＆スペースのパターンを有するフォトマスクを、塗布膜から１００μｍの距離に配置し、このフォトマスクを介して超高圧水銀灯の光を２００ｍＪ／ｃｍ２照射した。次いで、６０℃の露光後加熱処理を、表２および表３に記載の処理時間で行った。その後、セミクリーンＤＬ－Ａ１０現像液（５倍希釈）を使用し、温度２３℃、圧力０．１ＭＰａ、現像時間６０秒の条件で未露光部を除去し、膜厚１．７μｍの塗膜を得た。上記のようにして作製したパターンを有する塗膜の顕微鏡観察を行い、解像された最小ライン幅（最小現像寸法）および未露光部の残渣の有無を評価した。最小現像寸法については、良好に現像できずパターンが判別できなかったものについては「×」で示した。
　残渣の有無については、以下の基準で示す。
　　残渣○：未露光部に残渣無し
　　残渣×：未露光部に残渣あり
　上記の現像性の評価結果を表２および表３に示す。 <Evaluation of photosensitive resin composition>
(1) Developability The prepared photosensitive resin composition is applied onto a 5 cm square glass substrate (non-alkali glass substrate) by the spin coater method, and heated (prebaked) at 100 ° C. for 3 minutes to remove a solvent. It was volatilized to form a coating film on a glass substrate. Next, a photomask having a line & space pattern with a width of 3 to 100 μm was placed at a distance of 100 μm from the coating film, and the light of an ultrahigh pressure mercury lamp was irradiated at 200 mJ / cm 2 through the photomask. Then, the post-exposure heat treatment at 60 ° C. was performed at the treatment times shown in Tables 2 and 3. Then, using a semi-clean DL-A10 developer (diluted 5 times), the unexposed portion was removed under the conditions of a temperature of 23 ° C., a pressure of 0.1 MPa, and a development time of 60 seconds to form a coating film having a thickness of 1.7 μm. Obtained. The coating film having the pattern produced as described above was observed under a microscope, and the resolved minimum line width (minimum development dimension) and the presence or absence of residue in the unexposed portion were evaluated. The minimum development dimensions were indicated by "x" for those that could not be developed well and the pattern could not be discriminated.
The presence or absence of a residue is indicated by the following criteria.
Residual ◯: No residue in the unexposed area Residue ×: Residue in the unexposed area The above evaluation results of developability are shown in Tables 2 and 3.
＜樹脂硬化膜の評価＞
（１）鉛筆硬度
　調製された感光性樹脂組成物を、スピンコーター法により５ｃｍ角のガラス基板（無アルカリガラス基板）上に塗布し、１００℃にて３分間加熱することで溶剤を揮発させ、ガラス基板上に塗布膜を形成した。次に、塗布膜に波長３６５ｎｍの光を２００ｍＪ／ｃｍ２の露光量で照射し、塗布膜を光硬化させた。次いで、乾燥機中に１３０℃３０分又は８０℃６０分の条件で静置して加熱処理（ポストベーク）を行い、膜厚１．５μｍの樹脂硬化膜を得た。
　上記のようにして作製した樹脂硬化膜の鉛筆硬度を、鉛筆硬度計（Ｎｏ．５５３－Ｍ、安田精機製作所製）を用いて、ＪＩＳ　Ｋ５６００－５－４に従い測定した。結果を表２～４に示す。 <Evaluation of cured resin film>
(1) Pencil hardness The prepared photosensitive resin composition is applied onto a 5 cm square glass substrate (non-alkali glass substrate) by a spin coater method, and heated at 100 ° C. for 3 minutes to volatilize the solvent. A coating film was formed on the glass substrate. Next, the coating film was irradiated with light having a wavelength of 365 nm at an exposure amount of 200 mJ / cm 2 , and the coating film was photocured. Then, it was allowed to stand in a dryer at 130 ° C. for 30 minutes or 80 ° C. for 60 minutes for heat treatment (post-baking) to obtain a resin cured film having a film thickness of 1.5 μm.
The pencil hardness of the resin cured film produced as described above was measured according to JIS K5600-5-4 using a pencil hardness tester (No. 553-M, manufactured by Yasuda Seiki Seisakusho). The results are shown in Tables 2-4.
（２）透過率
　上記（１）鉛筆硬度の評価と同様にして作製した樹脂硬化膜を有する基板について、分光光度計（ＵＶ－１６５０ＰＣ、島津製作所製）を用いて４００～８００ｎｍの分光透過率を測定した。４００ｎｍにおける透過率を表２に示す。 (2) Transmittance For a substrate having a resin cured film prepared in the same manner as in the above (1) Evaluation of pencil hardness, a spectrophotometer (UV-1650PC, manufactured by Shimadzu Corporation) was used to determine the spectral transmittance at 400 to 800 nm. It was measured. Table 2 shows the transmittance at 400 nm.
（３）密着性
　上記（１）鉛筆硬度の評価と同様にして作製した樹脂硬化膜を有する基板について、ＪＩＳ　Ｋ５６００－５－６のクロスカット法により樹脂硬化膜の密着性を評価した。碁盤目１００個中、残った塗膜の面積の割合を算出した。以下の基準に従って判定し、結果を表２および表３に示す。
　判定の基準は以下の通りである。
　　判定○：密着性１００
　　判定×：密着性１００未満 (3) Adhesion The adhesion of the resin cured film was evaluated by the cross-cut method of JIS K5600-5-6 for the substrate having the resin cured film prepared in the same manner as in the above (1) Evaluation of pencil hardness. The ratio of the area of the remaining coating film to 100 grids was calculated. Judgment was made according to the following criteria, and the results are shown in Tables 2 and 3.
The criteria for judgment are as follows.
Judgment ○: Adhesion 100
Judgment ×: Adhesion less than 100
　総合判定の基準は以下の通りである。結果を表２および表３に示す。
Figure JPOXMLDOC01-appb-T000007
 The criteria for comprehensive judgment are as follows. The results are shown in Tables 2 and 3.
Figure JPOXMLDOC01-appb-T000007
［実施例１７～１８］
　表５に記載の組成を用いる以外は実施例１と同様にして感光性樹脂組成物を調整した。表５に記載のポストベーク条件を用いる以外は、上記（１）鉛筆硬度の評価方法と同様にして、樹脂硬化膜を作製し、鉛筆硬度の測定を行った。結果を表５に示す。 [Examples 17 to 18]
The photosensitive resin composition was prepared in the same manner as in Example 1 except that the compositions shown in Table 5 were used. A resin cured film was prepared and the pencil hardness was measured in the same manner as in (1) Pencil hardness evaluation method described above, except that the post-baking conditions shown in Table 5 were used. The results are shown in Table 5.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　表２及び表３に示される通り、実施例１～１６の感光性樹脂組成物は現像性に優れ、硬度、透明性、密着性に優れた樹脂硬化膜を得ることができた。一方、光酸発生剤を使用しなかった比較例１は、現像性に劣り、硬度や密着性が十分な樹脂硬化膜が得られなかった。これは、ポストベーク工程等の加熱工程において、より高い温度条件が必要であるために、硬化不足が生じているためと考えられる。アクリル酸を使用しなかった比較例２は、現像性が得られない結果となった。（Ａ）共重合体における、（Ａ－１）アルコキシシリル基を有する重合性不飽和化合物由来の構成単位（ａ－１）の含有量が少ない比較例３および４は現像性が劣る結果となった。アルコキシシリル基に由来する架橋度が低いので、パターンで塗膜の露光部と未露光部も溶解して現像性に劣った。 As shown in Tables 2 and 3, the photosensitive resin compositions of Examples 1 to 16 were excellent in developability, and a cured resin film having excellent hardness, transparency, and adhesion could be obtained. On the other hand, in Comparative Example 1 in which the photoacid generator was not used, a resin cured film having poor developability and sufficient hardness and adhesion could not be obtained. It is considered that this is because the heating process such as the post-baking process requires higher temperature conditions, resulting in insufficient curing. In Comparative Example 2 in which acrylic acid was not used, the result was that developability could not be obtained. Comparative Examples 3 and 4 in which the content of the structural unit (a-1) derived from the polymerizable unsaturated compound having the (A-1) alkoxysilyl group in the (A) copolymer is small is inferior in developability. rice field. Since the degree of cross-linking derived from the alkoxysilyl group is low, the exposed and unexposed parts of the coating film are also dissolved in the pattern, resulting in poor developability.
　表５に示される通り、実施例１７～１８の感光性樹脂組成物は、ポストベークの温度条件を８０℃に下げても十分な硬度の樹脂硬化膜が得られることが分かった。 As shown in Table 5, it was found that the photosensitive resin compositions of Examples 17 to 18 could obtain a cured resin film having sufficient hardness even when the temperature condition of post-baking was lowered to 80 ° C.
　本発明によれば、優れた硬度、透明性および密着性を有する樹脂硬化膜を与え、現像性が良好であると共に、保存安定性にも優れる感光性樹脂組成物が提供される。また、硬度、透明性および密着性に優れた樹脂硬化膜、これを具備する画像表示素子が提供される。該感光性樹脂組成物は、透明膜、保護膜、絶縁膜、オーバーコート、フォトスペーサー、ブラックマトリックス、ブラックカラムスペーサー、カラーフィルター用のレジストとして好ましく用いることができる。 According to the present invention, there is provided a photosensitive resin composition that provides a cured resin film having excellent hardness, transparency and adhesion, has good developability, and is also excellent in storage stability. Further, a resin cured film having excellent hardness, transparency and adhesion, and an image display element provided with the resin cured film are provided. The photosensitive resin composition can be preferably used as a transparent film, a protective film, an insulating film, an overcoat, a photo spacer, a black matrix, a black column spacer, and a resist for a color filter.

Claims (14)

  1. 　（Ａ）共重合体と、（Ｂ）光酸発生剤と、（Ｃ）溶剤とを含有する感光性樹脂組成物であって、
    　前記（Ａ）共重合体が、（Ａ－１）アルコキシシリル基を有する重合性不飽和化合物由来の構成単位（ａ－１）と、（Ａ－２）酸基を有する重合性不飽和化合物由来の構成単位（ａ－２）とを含む共重合体であり、
    　前記（Ａ）共重合体における全構成単位中の前記構成単位（ａ－１）の含有量が、４５～９９モル％であることを特徴とする感光性樹脂組成物。     A photosensitive resin composition containing (A) a copolymer, (B) a photoacid generator, and (C) a solvent.
    The (A) copolymer is derived from the structural unit (a-1) derived from the polymerizable unsaturated compound having (A-1) alkoxysilyl group and (A-2) derived from the polymerizable unsaturated compound having an acid group. It is a copolymer containing the constituent unit (a-2) of
    A photosensitive resin composition, wherein the content of the structural unit (a-1) in the total structural units of the (A) copolymer is 45 to 99 mol%.
  2. 　前記（Ａ）共重合体の酸価が１５～１５０ＫＯＨｍｇ／ｇである請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the acid value of the (A) copolymer is 15 to 150 KOH mg / g.
  3. 　前記構成単位（ａ－１）が（Ａ－１ａ）アルコキシシリル基含有（メタ）アクリレート由来の構成単位（ａ－１ａ）である請求項１又は２に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1 or 2, wherein the structural unit (a-1) is a structural unit (a-1a) derived from (A-1a) an alkoxysilyl group-containing (meth) acrylate.
  4. 　前記構成単位（ａ－１ａ）が、下記式（１）で表される請求項３に記載の感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     ［式（１）中、Ｒ１は水素原子又はメチル基を表し、Ｒ２～Ｒ４は各々独立に、水素原子、炭素原子数１～６のアルキル基又は炭素原子数１～６のアルコキシ基を表し、ｎは１～１０の整数である。ただし、Ｒ２～Ｒ４のうち少なくとも１つは炭素原子数１～６のアルコキシ基である。］     The photosensitive resin composition according to claim 3, wherein the structural unit (a-1a) is represented by the following formula (1).
    Figure JPOXMLDOC01-appb-C000001
     [In the formula (1), R 1 represents a hydrogen atom or a methyl group, and R 2 to R 4 are independent hydrogen atoms, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Represents, and n is an integer of 1 to 10. However, at least one of R 2 to R 4 is an alkoxy group having 1 to 6 carbon atoms. ]
  5. 　前記構成単位（ａ－２）が有する酸基がカルボキシ基である請求項１～４のいずれか一項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 4, wherein the acid group of the structural unit (a-2) is a carboxy group.
  6. 　前記（Ｃ）溶剤が、炭素原子数３～１０の第一級アルコール又は第二級アルコールのいずれかを少なくとも含む溶剤である請求項１～５のいずれか一項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 5, wherein the solvent (C) is a solvent containing at least one of a primary alcohol or a secondary alcohol having 3 to 10 carbon atoms. ..
  7. 　前記（Ｂ）光酸発生剤が、スルホニウム塩化合物である請求項１～６のいずれか一項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 6, wherein the (B) photoacid generator is a sulfonium salt compound.
  8. 　前記（Ａ）共重合体の重量平均分子量が、２０００～３００００である請求項１～７のいずれか一項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 7, wherein the (A) copolymer has a weight average molecular weight of 2000 to 30,000.
  9. 　（Ｄ）反応性希釈剤、および（Ｅ）光重合開始剤をさらに含む請求項１～８のいずれか一項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 8, further comprising (D) a reactive diluent and (E) a photopolymerization initiator.
  10. 　前記（Ｂ）光酸発生剤の含有量が、前記（Ａ）共重合体１００質量部に対して、０．１～１０質量部である請求項１～９のいずれか一項に記載の感光性樹脂組成物。 The photosensitive according to any one of claims 1 to 9, wherein the content of the (B) photoacid generator is 0.1 to 10 parts by mass with respect to 100 parts by mass of the (A) copolymer. Sex resin composition.
  11. 　前記（Ａ）共重合体と前記（Ｄ）反応性希釈剤との質量比が、４０：６０～９９：１であり、前記（Ｅ）光重合開始剤の含有量が前記（Ｄ）反応性希釈剤１００質量部に対して０．１～３０質量部である請求項９に記載の感光性樹脂組成物。 The mass ratio of the (A) copolymer to the (D) reactive diluent is 40:60 to 99: 1, and the content of the (E) photopolymerization initiator is the (D) reactive. The photosensitive resin composition according to claim 9, which is 0.1 to 30 parts by mass with respect to 100 parts by mass of the diluent.
  12. 　請求項１～１１のいずれか一項に記載の感光性樹脂組成物を硬化させてなる樹脂硬化膜。 A resin cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 11.
  13. 　オーバーコート、保護膜、及び絶縁膜からなる群から選択される一種である請求項１２に記載の樹脂硬化膜。 The resin cured film according to claim 12, which is a kind selected from the group consisting of an overcoat, a protective film, and an insulating film.
  14. 　請求項１２に記載の樹脂硬化膜を具備する画像表示装置。 An image display device provided with the resin cured film according to claim 12.
PCT/JP2021/023720 2020-07-06 2021-06-23 Photosensitive resin composition and cured resin film obtained therefrom WO2022009676A1 (en)

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JP2007304545A (en) * 2005-09-13 2007-11-22 Fujifilm Corp Positive resist composition and pattern-forming method using same
JP2008076889A (en) * 2006-09-22 2008-04-03 Jsr Corp Composition for resist underlayer film and method for preparing the same
WO2008090827A1 (en) * 2007-01-22 2008-07-31 Nissan Chemical Industries, Ltd. Positive photosensitive resin composition
WO2011096400A1 (en) * 2010-02-02 2011-08-11 日産化学工業株式会社 Positive photosensitive resin composition and liquid-repellent film
JP2019159330A (en) * 2016-03-25 2019-09-19 アーゼッド・エレクトロニック・マテリアルズ（ルクセンブルグ）ソシエテ・ア・レスポンサビリテ・リミテ Photosensitive siloxane composition

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JP2007304545A (en) * 2005-09-13 2007-11-22 Fujifilm Corp Positive resist composition and pattern-forming method using same
JP2008076889A (en) * 2006-09-22 2008-04-03 Jsr Corp Composition for resist underlayer film and method for preparing the same
WO2008090827A1 (en) * 2007-01-22 2008-07-31 Nissan Chemical Industries, Ltd. Positive photosensitive resin composition
WO2011096400A1 (en) * 2010-02-02 2011-08-11 日産化学工業株式会社 Positive photosensitive resin composition and liquid-repellent film
JP2019159330A (en) * 2016-03-25 2019-09-19 アーゼッド・エレクトロニック・マテリアルズ（ルクセンブルグ）ソシエテ・ア・レスポンサビリテ・リミテ Photosensitive siloxane composition

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