WO2022009676A1 - 感光性樹脂組成物及びその樹脂硬化膜 - Google Patents

感光性樹脂組成物及びその樹脂硬化膜 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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Prior art keywords
resin composition
photosensitive resin
copolymer
meth
group
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PCT/JP2021/023720
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English (en)
French (fr)
Japanese (ja)
Inventor
正偉 周
健宏 木下
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昭和電工株式会社
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Priority to JP2022535006A priority Critical patent/JPWO2022009676A1/ja
Priority to KR1020227044047A priority patent/KR20230013063A/ko
Priority to CN202180047283.3A priority patent/CN115867867A/zh
Publication of WO2022009676A1 publication Critical patent/WO2022009676A1/ja

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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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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007304545A (ja) * 2005-09-13 2007-11-22 Fujifilm Corp ポジ型レジスト組成物及びそれを用いたパターン形成方法
JP2008076889A (ja) * 2006-09-22 2008-04-03 Jsr Corp レジスト下層膜用組成物及びその製造方法
WO2008090827A1 (ja) * 2007-01-22 2008-07-31 Nissan Chemical Industries, Ltd. ポジ型感光性樹脂組成物
WO2011096400A1 (ja) * 2010-02-02 2011-08-11 日産化学工業株式会社 ポジ型感光性樹脂組成物及び撥液性被膜
JP2019159330A (ja) * 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 感光性シロキサン組成物

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Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007304545A (ja) * 2005-09-13 2007-11-22 Fujifilm Corp ポジ型レジスト組成物及びそれを用いたパターン形成方法
JP2008076889A (ja) * 2006-09-22 2008-04-03 Jsr Corp レジスト下層膜用組成物及びその製造方法
WO2008090827A1 (ja) * 2007-01-22 2008-07-31 Nissan Chemical Industries, Ltd. ポジ型感光性樹脂組成物
WO2011096400A1 (ja) * 2010-02-02 2011-08-11 日産化学工業株式会社 ポジ型感光性樹脂組成物及び撥液性被膜
JP2019159330A (ja) * 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 感光性シロキサン組成物

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