WO2022168974A1 - Alkali-soluble resin, photosensitive resin composition, cured product, and image display device - Google Patents
Alkali-soluble resin, photosensitive resin composition, cured product, and image display device Download PDFInfo
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- WO2022168974A1 WO2022168974A1 PCT/JP2022/004685 JP2022004685W WO2022168974A1 WO 2022168974 A1 WO2022168974 A1 WO 2022168974A1 JP 2022004685 W JP2022004685 W JP 2022004685W WO 2022168974 A1 WO2022168974 A1 WO 2022168974A1
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- WIPO (PCT)
- Prior art keywords
- group
- carbon atoms
- alkali
- soluble resin
- base
- Prior art date
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- 229920005989 resin Polymers 0.000 title claims abstract description 105
- 239000011347 resin Substances 0.000 title claims abstract description 105
- 239000011342 resin composition Substances 0.000 title claims abstract description 44
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 86
- 125000000962 organic group Chemical group 0.000 claims abstract description 84
- 125000005647 linker group Chemical group 0.000 claims abstract description 45
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 30
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- -1 acryloyloxy, methacryloyloxy Chemical group 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 239000011229 interlayer Substances 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 238000005192 partition Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 9
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- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 6
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- 125000005843 halogen group Chemical group 0.000 description 6
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
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- 239000007787 solid Substances 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 2
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
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- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
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- 125000004429 atom Chemical group 0.000 description 2
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- 125000004185 ester group Chemical group 0.000 description 2
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- VYGUBTIWNBFFMQ-UHFFFAOYSA-N [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O Chemical group [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O VYGUBTIWNBFFMQ-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- JMVIPXWCEHBYAH-UHFFFAOYSA-N cyclohexanone;ethyl acetate Chemical compound CCOC(C)=O.O=C1CCCCC1 JMVIPXWCEHBYAH-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- HOXINJBQVZWYGZ-UHFFFAOYSA-N fenbutatin oxide Chemical compound C=1C=CC=CC=1C(C)(C)C[Sn](O[Sn](CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C1=CC=CC=C1 HOXINJBQVZWYGZ-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F120/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- 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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
- C08F290/126—Polymers of unsaturated carboxylic acids or derivatives thereof
-
- 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
- C08F8/00—Chemical modification by after-treatment
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Definitions
- the present invention relates to alkali-soluble resins, photosensitive resin compositions, cured products, and image display devices.
- photospacers are used to maintain the thickness of the liquid crystal layer sandwiched between the substrate on the color filter side and the substrate on the thin film transistor (TFT) side.
- TFT thin film transistor
- a photospacer is generally formed by applying a photosensitive resin composition to a substrate, drying it, exposing it to light through a photomask having a predetermined fine pattern, and developing it.
- Patent Literature 1 provides a negative photosensitive resin composition that is excellent in development adhesion and resolution even when processed to a thick film of 10 ⁇ m or more and is capable of forming a fine photospacer with a good shape. with the aim of (A) an alkali-soluble resin, (B) a radical photopolymerization initiator and (C) a photopolymerizable monomer, wherein the (C) photopolymerizable monomer contains (C-1) an isocyanuric acid skeleton.
- a negative photosensitive resin composition containing a monomer and (C-2) a photopolymerizable monomer having a fluorene skeleton has been proposed.
- Patent Document 2 aims to provide a photosensitive resin composition that can form a gap of 10 ⁇ m or more, has good adhesion to a substrate, and can ensure transparency after exposure.
- component binder polymer
- component photopolymerizable compound
- C component: photopolymerization initiator
- D component: mercapto group-containing hydrogen donor
- the (B) photopolymerizable A photosensitive resin composition has been proposed in which a compound is used as a spacer-forming material containing a photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric ring structure.
- the present inventors have made intensive studies to solve the above problems, and found that the above objects can be achieved by using the following alkali-soluble resin and a photosensitive resin composition containing the alkali-soluble resin.
- the present invention has been completed.
- alkali-soluble resin A containing one or more repeating structural units X represented by the following general formula (1).
- R 1 is hydrogen or a methyl group
- R 2 is a linking group having 1 or more carbon atoms
- R 3 is represented by the following general formula (2) bonded to a carbon atom of the linking group.
- R 4 is an organic group
- R 4 is a hydroxy group or an organic group bonded to the carbon atom of the linking group.
- R 5 is an organic group having a base of 3 to 8 carbon atoms and containing a hetero atom, or an organic group having a base of 2 to 7 carbon atoms and a carboxy group.
- the present invention includes one or more repeating structural units X' represented by the following general formula (1'), provided that each branched side having 2 to 3 terminals ending in a radically polymerizable substituent
- the present invention relates to an alkali-soluble resin (hereinafter also referred to as "alkali-soluble resin B") that does not contain a repeating structural unit with a chain.
- R 1 is hydrogen or a methyl group
- R 2 is a linking group having 1 or more carbon atoms
- R 3′ is a carbon atom of the linking group represented by the following general formula (2′) and R 4 is a hydroxy group or an organic group bonded to the carbon atom of the linking group.
- R 5′ is a hydrocarbon group having a base having 2 to 7 carbon atoms, an organic group having a base having 3 to 8 carbon atoms and containing a hetero atom, or a base having 2 to 7 carbon atoms. and is an organic group having a carboxy group.
- the linking group of R 2 is a hydrocarbon group having 1 to 10 carbon atoms in the base, or an organic group having 1 to 10 carbon atoms in the base and containing a hetero atom.
- the linking group of R 2 is a hydrocarbon group having 1 to 10 carbon atoms in the base, or an organic group having 1 to 10 carbon atoms in the base and containing a hetero atom.
- the organic group for R4 is selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, an acyloxy group, an amidooxy group, an alkoxy group, an aryloxy group, an amino group, and a nitrogen-containing heterocyclic ring. It is preferably an organic group containing one or more selected functional groups.
- the linking group of R 2 is a hydrocarbon group having a base having 1 to 7 carbon atoms, or an organic group having a base having 1 to 7 carbon atoms and containing a hetero atom.
- R 4 is preferably a hydroxy group, an acryloyloxy group, or a methacryloyloxy group bonded to the carbon atom of the linking group of R 2 .
- the linking group of R 2 is a hydrocarbon group having a base having 1 to 7 carbon atoms, or an organic group having a base having 1 to 7 carbon atoms and containing a hetero atom.
- the R 5 or the R 5' is an organic group represented by the following general formula (3)
- R 4 is preferably a hydroxy group, an acryloyloxy group, a methacryloyloxy group, or an organic group represented by the following general formula (4), which is bonded to the carbon atom of the linking group of R 2 .
- each of R 6 and R 7 is independently a hydrocarbon group having 1 to 6 carbon atoms in the base, and the total number of carbon atoms in the base of R 6 and R 7 is 3 to 8.
- R 8 is hydrogen or a methyl group
- R 9 is a hydrocarbon group having 1 to 5 carbon atoms as a base, or an organic group having 1 to 5 carbon atoms as a base and containing a hetero atom. be.
- the content of the repeating structural unit X or X' is preferably 5 to 50 mol% in all repeating structural units.
- the alkali-soluble resin A or B preferably has an acid value of 20 to 120 mgKOH/g.
- the alkali-soluble resin A or B preferably has a weight average molecular weight of 5,000 to 40,000.
- the photosensitive resin composition of the present invention contains at least the alkali-soluble resins A and/or B, a polymerizable monomer, and a photopolymerization initiator.
- the cured product of the present invention is obtained from the photosensitive resin composition.
- the cured product is preferably a photospacer, partition wall material, lens material, interlayer insulating film material, protective film material, optical waveguide material, or flattening film material.
- the present invention also relates to an image display device containing the cured product.
- the alkali-soluble resin A or B of the present invention contains one or more repeating structural units X or X' represented by the general formula (1) or (1'), and in the repeating structural unit X or X'
- the main feature is that the length of the side chain is longer than a certain length, and it has a structure having a carboxyl group at the end of the side chain. Due to its characteristic structure, the alkali-soluble resin A or B of the present invention can provide a cured film excellent in development adhesion and resolution even when the film is thickened.
- the alkali-soluble resin A or B of the present invention since the alkali-soluble resin A or B of the present invention has a hydroxy group or an organic group bonded to the carbon atom of the linking group R2 , it can further have properties derived from these groups.
- the photosensitive resin composition containing the alkali-soluble resin A and / or B of the present invention can be developed in a short time even when using a weakly alkaline developer, the productivity of cured products such as photospacers is improved. be able to.
- R 4 is an organic group
- the alkali-soluble resin A or B of the present invention has a branched structure in the side chain, so that even when the film is thickened, a cured film having even better development adhesion and resolution can be obtained. be able to.
- the reason for this, although not necessarily bound by theory, is that when R 3 or R 3′ is somewhat long (has a large number of atoms), the terminal carboxy group tends to face the main chain.
- the number of carboxyl groups that can participate in adhesion to the substrate increases. Furthermore, when the R 4 is an organic group, the side chain of the alkali-soluble resin A or B has a branched structure, so that the terminal carboxy group of the R 3 or R 3′ This is probably because the orientation becomes easier, and the number of carboxyl groups that can participate in adhesion to the substrate increases.
- the alkali-soluble resin A of the present invention contains one or more repeating structural units X represented by the following general formula (1).
- R 1 is hydrogen or a methyl group
- R 2 is a linking group having 1 or more carbon atoms
- R 3 is represented by the following general formula (2) bonded to a carbon atom of the linking group.
- R 4 is a hydroxy group or an organic group bonded to the carbon atom of the linking group.
- R 5 is an organic group having a base of 3 to 8 carbon atoms and containing a hetero atom, or an organic group having a base of 2 to 7 carbon atoms and a carboxy group.
- the alkali-soluble resin B of the present invention contains one or more repeating structural units X' represented by the following general formula (1'), provided that each has 2 to 3 terminals ending in radically polymerizable substituents. does not contain repeating structural units with branched side chains having (Wherein, R 1 is hydrogen or a methyl group, R 2 is a linking group having 1 or more carbon atoms, and R 3′ is a carbon atom of the linking group represented by the following general formula (2′) and R 4 is a hydroxy group or an organic group bonded to the carbon atom of the linking group.) (Wherein, R 5′ is a hydrocarbon group having a base having 2 to 7 carbon atoms, an organic group having a base having 3 to 8 carbon atoms and containing a hetero atom, or a base having 2 to 7 carbon atoms. and is an organic group having a carboxy group.)
- (meth)acryl means acrylic or methacrylic
- (meth)acryloyl means acryloyl or methacryloyl
- (meth)acrylic acid means acrylic acid or methacrylic acid
- (meth)acrylate means acrylate or methacrylate, respectively.
- the number of carbon atoms in the base means the number of carbon atoms in the main skeleton group excluding substituents.
- R 2 is a linking group having 1 or more carbon atoms
- R 3 and R 4 , or R 3′ and R 4 are oxygen atoms of an ester bond.
- the linking group include linear or branched aliphatic saturated or unsaturated hydrocarbon groups, alicyclic saturated or unsaturated hydrocarbon groups (including bridged rings and condensed rings), and aromatic hydrocarbon groups.
- a hydrogen group an organic group in which some of the carbon atoms constituting the hydrocarbon group are substituted with a hetero atom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom, etc.), and an organic group in which two or more of these are bonded etc.
- the hydrocarbon group or the organic group includes various substituents (e.g., halogen group, hydroxy group, carboxyl group, amino group, alkyl group, alkenyl group, alkoxy group, aryl group, etc.) and functional groups (e.g., , ester bond, amide bond, ether bond, thioether bond, urethane bond, etc.).
- the linking group is a hydrocarbon group having 1 to 10 carbon atoms in the base, or an organic is preferably a group.
- the linking group is a hydrocarbon group having a parent body having 1 to 7 carbon atoms, or a parent body having a carbon number of 1 to 7 and a hetero atom (eg, an oxygen atom, a nitrogen atom, a sulfur atom, etc.). more preferably an organic group containing
- the hetero atom possessed by the linking group is the portion other than the bonding portion with R 3 or R 3′ in the general formula (1) or (1′), the It is present in the portion other than the bonding portion with R 4 and in the portion other than the bonding portion with the oxygen atom of the ester bond.
- the linking group may be a linear or branched aliphatic saturated or unsaturated hydrocarbon group having 2 to 7 carbon atoms in the base, or a saturated or unsaturated alicyclic group having 3 to 7 carbon atoms in the base.
- R 3 is an organic group represented by general formula (2) that bonds to the carbon atom of the linking group of R 2 .
- R 5 is an organic group having 3 to 8 carbon atoms in the base and containing a hetero atom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom, etc.), or a carbon in the base It is an organic group having a number of 2 to 7 and having a carboxy group.
- R 5 is preferably an organic group having a matrix of 2 to 7 carbon atoms and a carboxy group.
- the number of carboxy groups is not particularly limited, but preferably 1-2.
- the organic groups include various substituents (e.g., halogen groups, hydroxy groups, carboxyl groups, amino groups, alkyl groups, alkenyl groups, alkoxy groups, and aryl groups) and functional groups (e.g., ester bonds, amide bonds, ether bond, thioether bond, urethane bond, etc.).
- substituents e.g., halogen groups, hydroxy groups, carboxyl groups, amino groups, alkyl groups, alkenyl groups, alkoxy groups, and aryl groups
- functional groups e.g., ester bonds, amide bonds, ether bond, thioether bond, urethane bond, etc.
- the organic group represented by the general formula (2) is preferably any one of the following organic groups.
- R 3′ is an organic group represented by general formula (2′) that bonds to the carbon atom of the linking group of R 2 .
- R 5′ is a hydrocarbon group having 2 to 7 carbon atoms in the base, a 3 to 8 carbon base in the base, and a hetero atom (e.g., oxygen atom, nitrogen atom, , and a sulfur atom), or an organic group having a base having 2 to 7 carbon atoms and a carboxy group.
- R 5′ is preferably a hydrocarbon group having a base of 2 to 7 carbon atoms or an organic group having a base of 2 to 7 carbon atoms and a carboxy group.
- R 5′ has a carboxy group
- the number of carboxy groups is not particularly limited, but preferably 1-2.
- the hydrocarbon group include linear or branched aliphatic saturated or unsaturated hydrocarbon groups, alicyclic saturated or unsaturated hydrocarbon groups (including bridged rings and condensed rings), and aromatic hydrocarbons. groups, and hydrocarbon groups in which two or more of these groups are bonded.
- the hydrocarbon group or the organic group may contain various substituents (e.g., halogen groups, hydroxy groups, carboxyl groups, amino groups, alkyl groups, alkenyl groups, alkoxy groups, and aryl groups) or functional groups (e.g., ester groups). bond, amide bond, ether bond, thioether bond, urethane bond, etc.).
- the organic group represented by the general formula (2') is preferably any one of the following organic groups.
- R 5 or R 5' is preferably an organic group represented by the following general formula (3).
- each of R 6 and R 7 is independently a hydrocarbon group having 1 to 6 carbon atoms in the base, and the total number of carbon atoms in the base of R 6 and R 7 is 3 to 8.
- hydrocarbon group examples include linear or branched aliphatic saturated or unsaturated hydrocarbon groups, aromatic hydrocarbon groups, and alicyclic saturated or unsaturated hydrocarbon groups.
- the hydrocarbon group may have various substituents (eg, halogen group, hydroxy group, carboxy group, amino group, alkyl group, alkenyl group, alkoxy group, aryl group, etc.).
- Examples of the organic group represented by the general formula (3) include the following.
- R 6 and R 7 are each independently a hydrocarbon group having 1 to 5 carbon atoms as a base, and the total number of carbon atoms in the base of R 6 and R 7 is preferably 3 to 7.
- the organic group represented by the general formula (2) or (2') is preferably any one of the following organic groups.
- R 4 is a hydroxy group or an organic group bonded to the carbon atom of the linking group of R 2 .
- R4 is a hydroxy group
- the developability can be further improved.
- R 4 is an organic group
- properties derived from the organic group eg developability, adhesiveness, solubility, etc.
- the organic group is not particularly limited, and examples include linear or branched aliphatic saturated or unsaturated hydrocarbon groups, alicyclic saturated or unsaturated hydrocarbon groups (including bridged rings and condensed rings), an aromatic hydrocarbon group, an organic group in which some of the carbon atoms constituting the hydrocarbon group are substituted with heteroatoms (e.g., oxygen atoms, nitrogen atoms, sulfur atoms, etc.), and two or more of these bonded together and the like.
- heteroatoms e.g., oxygen atoms, nitrogen atoms, sulfur atoms, etc.
- hydrocarbon group or the organic group includes various substituents (e.g., halogen group, hydroxy group, carboxyl group, amino group, alkyl group, alkenyl group, alkoxy group, aryl group, etc.) and functional groups (e.g., , ester bond, amide bond, ether bond, thioether bond, urethane bond, etc.).
- substituents e.g., halogen group, hydroxy group, carboxyl group, amino group, alkyl group, alkenyl group, alkoxy group, aryl group, etc.
- functional groups e.g., ester bond, amide bond, ether bond, thioether bond, urethane bond, etc.
- the organic group for R4 is one or more functional groups selected from the group consisting of acryloyloxy, methacryloyloxy, acyloxy, amidooxy, alkoxy, aryloxy, amino, and nitrogen-containing heterocycles. and more preferably an acryloyloxy group, a methacryloyloxy group, or an organic group represented by any of the following formulas. (Wherein, R 10 and R 11 are each independently an organic group described in paragraph [0039].)
- R 4 is preferably a hydroxy group, an acryloyloxy group, a methacryloyloxy group, or an organic group represented by the following general formula (4), which is bonded to the carbon atom of the linking group of R 2 .
- R 8 is hydrogen or a methyl group
- R 9 is a hydrocarbon group having 1 to 5 carbon atoms as a base, or an organic group having 1 to 5 carbon atoms as a base and containing a hetero atom. be.
- R 9 is a hydrocarbon group having 1 to 5 carbon atoms in the base, or a heteroatom (for example, an oxygen atom, a nitrogen atom, and sulfur atoms).
- a heteroatom for example, an oxygen atom, a nitrogen atom, and sulfur atoms.
- the heteroatom of the organic group is, in the general formula (4), the portion other than the bonding portion with the nitrogen atom of the urethane bond, and the (meth)acryloyloxy group. It is present in the portion other than the bonding portion with the oxygen atom.
- the hydrocarbon group includes a linear or branched aliphatic saturated or unsaturated hydrocarbon group.
- the hydrocarbon group or the organic group may contain various substituents (e.g., halogen groups, hydroxy groups, carboxyl groups, amino groups, alkyl groups, alkenyl groups, alkoxy groups, and aryl groups) or functional groups (e.g., ester groups). bond, amide bond, ether bond, thioether bond, urethane bond, etc.).
- R 9 is preferably a hydrocarbon group having 1 to 5 carbon atoms as a base, more preferably an ethylene group or a propylene group.
- Examples of the monomer that is the source of the repeating structural unit other than the repeating structural unit X or X′ constituting the alkali-soluble resin A or B include (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, Carboxyl group-containing monomers such as maleic acid and itaconic acid; carboxylic anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl Alkyl (meth)acrylates such as (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ethoxyethyl (meth)acrylate, and glycidyl (meth)acrylate Acrylates; cyclohex
- styrene, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, n-butylmaleimide, laurylmaleimide, silicone-containing monomers, and the like may be used as copolymerizable monomers. These monomers may be used alone or in combination of two or more.
- the alkali-soluble resin B contains a repeating structural unit (hereinafter also referred to as "repeating structural unit Y") having a branched side chain having 2 to 3 terminals each ending in a radically polymerizable substituent.
- the repeating structural unit Y is a monomer unit (1) described in WO 2018/169036.
- each of the radically polymerizable substituents is, for example, on the hydrocarbon chain (L)
- Each substituted, the hydrocarbon chain (L) is attached to the main chain of the polymer via, for example, a --COO-- group.
- the number of carbon atoms constituting the hydrocarbon chain (L) is, for example, 3 to 5, 3 or 4, or 3.
- the radically polymerizable substituent is, for example, a (meth)acryloyloxy group.
- the alkali-soluble resin A or B of the present invention is prepared by, for example, reacting a polymer having an epoxy group in a side chain obtained by polymerizing a monomer composition containing an epoxy group-containing (meth)acrylate with a carboxy group-containing compound.
- a polymer having an ethylenically unsaturated group and a carboxy group is reacted with a compound having an ethylenically unsaturated group and a carboxyl group to convert a side chain having a hydroxy group and an ethylenically unsaturated group, and a hydroxy group such as an isocyanate group is added to the hydroxy group.
- a compound having a functional group that reacts with the group is reacted, and a compound having a functional group that reacts with an ethylenically unsaturated group such as a hydroxyl group, a thiol group, and an amino group and a carboxy group is added to the ethylenically unsaturated group. It can be synthesized by reaction method (2) or the like.
- the alkali-soluble resin A or B may be a homopolymer composed of the repeating structural unit X or X', or a random polymer composed of the repeating structural unit X or X' and another repeating structural unit. It may be a copolymer, block copolymer, alternating copolymer, or periodic copolymer.
- the content of the repeating structural unit X or X' is not particularly limited. From the viewpoint of enabling development in a short time even when a liquid is used, it is preferably 5 to 50 mol %, more preferably 5 to 25 mol % in all repeating structural units.
- the weight average molecular weight of the alkali-soluble resin A or B is not particularly limited, it is preferably 5,000 to 40,000, more preferably 5,000 to 20,000 from the viewpoint of sensitivity and developability.
- the weight-average molecular weight is a polystyrene-equivalent value measured using gel permeation chromatography (GPC) and is a value measured according to JIS 7252-4.
- GPC gel permeation chromatography
- the acid value of the alkali-soluble resin A or B is not particularly limited, it is preferably 20 to 120 mgKOH/g, more preferably 20, from the viewpoint of enabling development in a short time even when a weakly alkaline developer is used. ⁇ 80 mg KOH/g.
- the photosensitive resin composition of the present invention contains at least the alkali-soluble resins A and/or B, a polymerizable monomer, and a photopolymerization initiator.
- the content ratio of the alkali-soluble resin A and / or B to the total solid content in the photosensitive resin composition is not particularly limited, but even when the film is thickened, development From the viewpoint of forming a cured film with excellent adhesion and resolution, and from the viewpoint of enabling development in a short time even when using a weakly alkaline developer, it is usually about 40 to 90% by mass, preferably 40 to 80% by mass. and more preferably 50 to 70% by mass.
- the polymerizable monomer is not particularly limited, and examples include nonylphenyl carbitol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxyethyl (meth) ) Monofunctional monomers such as acrylates and N-vinylpyrrolidone, and polyfunctional aromatic vinyl monomers such as divinylbenzene, diallyl phthalate, and diallylbenzene phosphonate; (di) ethylene glycol di (meth) acrylate, propylene glycol di ( meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dip
- the content of the polymerizable monomer is not particularly limited, but from the viewpoint of sufficiently obtaining the effects of the present invention, the alkali-soluble resin A and / or B 100 parts by mass (when used in combination, the total.) 30 ⁇ It is preferably 100 parts by mass, more preferably 40 to 80 parts by mass, even more preferably 50 to 70 parts by mass.
- the photopolymerization initiator is not particularly limited, and examples thereof include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenones such as; 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and other anthraquinones; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.
- benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether
- acetophenones such as; 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone
- thioxanthones ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one and 2-benzyl -2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; acylphosphine oxides and xanthones.
- photopolymerization initiators may be used alone or in combination of two or more.
- the content of the photopolymerization initiator is not particularly limited, but it is 0.1 to 5 parts by mass with respect to 100 parts by mass of the alkali-soluble resin A and / or B (the total when used in combination). It is preferably 0.2 to 4 parts by mass, and still more preferably 0.5 to 3 parts by mass.
- a photopolymerization initiation aid may be added to the photosensitive resin composition.
- photopolymerization initiation aids include 1,3,5-tris(3-mercaptopropionyloxyethyl)-isocyanurate, 1,3,5-tris(3-mercaptobutyloxyethyl)-isocyanurate (Showa Denko manufactured by Karenz MT (registered trademark) NR1), trifunctional thiol compounds such as trimethylolpropane tris (3-mercaptopropionate); butyrate) (manufactured by Showa Denko Co., Ltd., Karenz MT (registered trademark) PEI) and other tetrafunctional thiol compounds; dipentaerythritol hexakis (3-propionate) and other hexafunctional thiol compounds.
- These photopolymerization initiation aids may be used alone or in combination of two or more.
- thermal polymerization initiators include, for example, cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-butylperoxy-2 -organic peroxides such as ethylhexanoate and t-amylperoxy-2-ethylhexanoate; 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), azo compounds such as 2,2'-azobis(2,4-dimethylvaleronitrile) and dimethyl 2,2'-azobis(2-methylpropionate); These thermal polymerization initiators may be used alone or in combination of two or more.
- Radically polymerizable oligomers such as unsaturated polyesters, epoxy acrylates, urethane acrylates and polyester acrylates; curable resins such as epoxy resins may be added to the photosensitive resin composition.
- the photosensitive resin composition may contain a solvent.
- solvents include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy esters such as butyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; mentioned. These solvents may be used alone or in combination of two or more. In addition, the content of the solvent may be appropriately set according to the optimum viscosity when using the composition.
- the photosensitive resin composition contains fillers such as aluminum hydroxide, talc, clay, barium sulfate, etc., dyes, pigments, antifoaming agents, coupling agents, leveling agents, and sensitizers, as long as the effects of the present invention are not impaired.
- known additives such as agents, release agents, lubricants, plasticizers, antioxidants, UV absorbers, flame retardants, polymerization inhibitors, thickeners and dispersants.
- the cured product of the present invention is obtained by curing the photosensitive resin composition.
- the photosensitive resin composition is injected into a mold (resin mold), or the photosensitive resin composition is placed on a substrate (substrate) or various functional layers.
- a method of curing the photosensitive resin composition by irradiating it with light (for example, ultraviolet rays) after forming it into a desired shape by coating may be mentioned. Curing conditions are appropriately adjusted according to the photosensitive resin composition to be used.
- the cured product is suitably used as a photospacer, partition wall material, lens material, interlayer insulating film material, protective film material, optical waveguide material, or flattening film material, and is particularly suitably used as a photospacer.
- the method for forming the photospacer is not particularly limited, and for example, the photosensitive resin composition may be applied to a substrate such as glass or a transparent plastic film, dried to form a coating film, and then formed by photolithography. can.
- photolithography for example, a photomask is placed on the coating film, the coating film is photocured by irradiating with ultraviolet rays, and an alkaline aqueous solution is sprayed on the coating film after the ultraviolet irradiation to dissolve and remove the unexposed areas. The remaining exposed portions are washed with water and developed to form photospacers. A post-bake may then be performed.
- a photospacer having a film thickness of 10 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, or even 50 ⁇ m or more can be produced with high development adhesion and high resolution.
- a photospacer having an aspect ratio of 4.0 or more can be produced.
- the photosensitive resin composition of the present invention can be developed in a short time even when a weakly alkaline developer is used, the photospacer can be produced with high productivity.
- Alkali-soluble resin 1 containing the following repeating structural units A and X1 was synthesized by the following production method. 100 g of glycidyl methacrylate and 212 g of propylene glycol monomethyl ether acetate were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. After the gas phase in the system was replaced with nitrogen, 17 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated at 80°C, and reacted at the same temperature for 8 hours.
- the molecular weight was measured by gel permeation chromatography (manufactured by Tosoh Corporation, product number: HLC-8120, column: two connections of G-5000HXL and G-3000HXL, detector: RI, mobile phase: tetrahydrofuran). .
- the weight average molecular weight was measured by the same method below.
- the acid value of the alkali-soluble resin 1 was 21 mgKOH/g.
- Alkali-soluble resin 4 containing the following repeating structural units A and X1 was synthesized by the following production method. 100 g of glycidyl methacrylate and 150 g of propylene glycol monomethyl ether acetate were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. After the gas phase in the system was replaced with nitrogen, 5.2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated at 80°C, and reacted at the same temperature for 8 hours.
- Alkali-Soluble Resin 5 containing the following repeating structural units A, B and X2 was synthesized by the following production method. 100 g of glycidyl methacrylate and 160 g of propylene glycol monomethyl ether acetate were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. After the gas phase in the system was replaced with nitrogen, 7.5 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated at 80°C, and reacted at the same temperature for 8 hours.
- Alkali-soluble resin 6 containing the following repeating structural units A and X3 was synthesized by the following production method. 100 g of glycidyl methacrylate and 212 g of propylene glycol monomethyl ether acetate were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. After the gas phase in the system was replaced with nitrogen, 17 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated at 80°C, and reacted at the same temperature for 8 hours.
- Examples 1-7 and Comparative Examples 1-3 [Preparation of photosensitive resin composition] 100 parts by mass of the solution containing 45% by mass of the alkali-soluble resin 1, 60 parts by mass of dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.), 1.6 parts by mass of a photopolymerization initiator (SPEEDCURE TPO manufactured by LAMBSON) part, a photopolymerization initiator (BASF Japan Ltd., Irgacure OXE01) 1.0 parts by mass, and a surfactant (manufactured by BYK, BYK-307) 0.2 parts by mass, and the solid content in the composition is A photosensitive resin composition of 50% was prepared (Example 1).
- each photosensitive resin composition prepared in Examples 1 to 7 and Comparative Examples 1 to 3 using a spin coater After adjusting the rotation speed of the spin coater.
- Each coating film was formed by coating so that the height of the photospacer was 30 ⁇ m, and each coating film was heated on a hot plate at 100° C. for 2 minutes to completely remove the solvent.
- each of the obtained coating films was irradiated with 100 mJ/cm 2 of light from an ultra-high pressure mercury lamp through a photospacer forming mask having 100 openings per 1 cm 2 with a diameter of 4 to 30 ⁇ m in increments of 1 ⁇ m ( i-line conversion illuminance 21 mW/cm 2 ).
- the distance (exposure gap) between the mask and the substrate was set to 100 ⁇ m for exposure.
- alkali development was performed using a 0.3% Na 2 CO 3 aqueous solution.
- the development time was set to 1.5 times the shortest development time measured by the method described above.
- post-baking was performed at 230° C. for 30 minutes to form a photospacer.
- the photosensitive resin compositions of Examples 1 to 7 have the same photosensitive properties as those of Comparative Examples 1 to 3. It can be seen that development can be completed in a shorter time than with the resin composition, and a cured film having excellent development adhesion can be formed.
- the alkali-soluble resin of the present invention and the photosensitive resin composition containing the alkali-soluble resin can be used as a photospacer, a partition wall material, a lens material, an interlayer insulating film material, a protective film material, an optical waveguide material, or a flattening film material. It is suitably used as a raw material.
Abstract
A purpose of the present invention is to provide: an alkali-soluble resin able to form a cured film having excellent development adhesiveness and resolution even if the film is thick; and a photosensitive resin composition that contains the alkali-soluble resin. Another purpose of the present invention is to provide a photosensitive resin composition which, in addition to the characteristics mentioned above, can be developed in a short time even if a weakly alkaline developing solution is used. This alkali-soluble resin contains one or more types of repeating unit X represented by general formula (1). (In the formula, R1 is hydrogen or a methyl group, R2 is a linking group having one or more carbon atoms, R3 is an organic group which is represented by general formula (2) and bonds to a carbon atom in the linking group, and R4 is a hydroxyl group or organic group which bonds to a carbon atom in the linking group.) (In the formula, R5 is an organic group which includes a heteroatom and which has 3-8 carbon atoms in the main structure, or an organic group which includes a carboxyl group and which has 2-7 carbon atoms in the main structure.)
Description
本発明は、アルカリ可溶性樹脂、感光性樹脂組成物、硬化物、及び画像表示装置に関する。
The present invention relates to alkali-soluble resins, photosensitive resin compositions, cured products, and image display devices.
液晶表示素子においては、カラーフィルタ側基板と薄膜トランジスタ（ＴＦＴ）側基板の間に挟持される液晶層の厚みを保持するために、フォトスペーサーが用いられている。
In liquid crystal display elements, photospacers are used to maintain the thickness of the liquid crystal layer sandwiched between the substrate on the color filter side and the substrate on the thin film transistor (TFT) side.
フォトスペーサーは、一般に感光性樹脂組成物を基板に塗布し、乾燥した後に所定の微細パターンを有するフォトマスクを通した光で露光し、現像することにより形成される。
A photospacer is generally formed by applying a photosensitive resin composition to a substrate, drying it, exposing it to light through a photomask having a predetermined fine pattern, and developing it.
近年、液晶表示装置などの画像表示装置の高機能化（例えば、３Ｄ立体視化、視野角拡大化など）に伴い、フォトスペーサーの厚膜化（１０μｍ以上）が求められている。
In recent years, along with the sophistication of image display devices such as liquid crystal display devices (for example, 3D stereoscopic vision, widening of viewing angle, etc.), there is a demand for thicker photospacers (10 μm or more).
例えば、特許文献１には、膜厚１０μｍ以上の厚膜加工を行っても現像密着性および解像度に優れ、形状が良好な微細フォトスペーサーを形成することができるネガ型感光性樹脂組成物を提供することを目的として、
（Ａ）アルカリ可溶性樹脂、（Ｂ）光ラジカル重合開始剤および（Ｃ）光重合性モノマーを含有し、前記（Ｃ）光重合性モノマーが、（Ｃ－１）イソシアヌル酸骨格を有する光重合性モノマーおよび（Ｃ－２）フルオレン骨格を有する光重合性モノマーを含有するネガ型感光性樹脂組成物が提案されている。 For example, Patent Literature 1 provides a negative photosensitive resin composition that is excellent in development adhesion and resolution even when processed to a thick film of 10 μm or more and is capable of forming a fine photospacer with a good shape. with the aim of
(A) an alkali-soluble resin, (B) a radical photopolymerization initiator and (C) a photopolymerizable monomer, wherein the (C) photopolymerizable monomer contains (C-1) an isocyanuric acid skeleton. A negative photosensitive resin composition containing a monomer and (C-2) a photopolymerizable monomer having a fluorene skeleton has been proposed.
（Ａ）アルカリ可溶性樹脂、（Ｂ）光ラジカル重合開始剤および（Ｃ）光重合性モノマーを含有し、前記（Ｃ）光重合性モノマーが、（Ｃ－１）イソシアヌル酸骨格を有する光重合性モノマーおよび（Ｃ－２）フルオレン骨格を有する光重合性モノマーを含有するネガ型感光性樹脂組成物が提案されている。 For example, Patent Literature 1 provides a negative photosensitive resin composition that is excellent in development adhesion and resolution even when processed to a thick film of 10 μm or more and is capable of forming a fine photospacer with a good shape. with the aim of
(A) an alkali-soluble resin, (B) a radical photopolymerization initiator and (C) a photopolymerizable monomer, wherein the (C) photopolymerizable monomer contains (C-1) an isocyanuric acid skeleton. A negative photosensitive resin composition containing a monomer and (C-2) a photopolymerizable monomer having a fluorene skeleton has been proposed.
また、特許文献２には、１０μｍ以上のギャップが形成可能であり、基板との密着性が良好で、かつ露光後の透明性を確保可能な感光性樹脂組成物を提供することを目的として、
（Ａ）成分：バインダーポリマー、（Ｂ）成分：光重合性化合物、（Ｃ）成分：光重合開始剤、及び（Ｄ）成分：メルカプト基含有水素供与体を含み、前記（Ｂ）光重合性化合物が、エチレン性不飽和基及びイソシアヌル環構造を有する光重合性化合物を含むスペーサー形成材料として用いられる感光性樹脂組成物が提案されている。 In addition, Patent Document 2 aims to provide a photosensitive resin composition that can form a gap of 10 μm or more, has good adhesion to a substrate, and can ensure transparency after exposure.
(A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: photopolymerization initiator, and (D) component: mercapto group-containing hydrogen donor, the (B) photopolymerizable A photosensitive resin composition has been proposed in which a compound is used as a spacer-forming material containing a photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric ring structure.
（Ａ）成分：バインダーポリマー、（Ｂ）成分：光重合性化合物、（Ｃ）成分：光重合開始剤、及び（Ｄ）成分：メルカプト基含有水素供与体を含み、前記（Ｂ）光重合性化合物が、エチレン性不飽和基及びイソシアヌル環構造を有する光重合性化合物を含むスペーサー形成材料として用いられる感光性樹脂組成物が提案されている。 In addition, Patent Document 2 aims to provide a photosensitive resin composition that can form a gap of 10 μm or more, has good adhesion to a substrate, and can ensure transparency after exposure.
(A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: photopolymerization initiator, and (D) component: mercapto group-containing hydrogen donor, the (B) photopolymerizable A photosensitive resin composition has been proposed in which a compound is used as a spacer-forming material containing a photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric ring structure.
しかし、特許文献１又は２に記載の感光性樹脂組成物は、フォトスペーサーの厚膜化に際して、現像密着性及び解像度について改善の余地があった。また、環境面から希薄な弱アルカリ性水溶液で現像可能な感光性樹脂組成物が求められるが、特許文献１又は２に記載の感光性樹脂組成物は、弱アルカリ性水溶液で現像すると現像時間が長くなり、生産性が低下するという問題が懸念される。
However, the photosensitive resin compositions described in Patent Documents 1 and 2 have room for improvement in development adhesion and resolution when thickening the photospacer. In addition, from an environmental point of view, there is a demand for a photosensitive resin composition that can be developed with a dilute weakly alkaline aqueous solution. , there is concern about the problem of reduced productivity.
本発明は、厚膜化した場合でも現像密着性及び解像度に優れる硬化膜を形成可能なアルカリ可溶性樹脂、及び前記アルカリ可溶性樹脂を含有する感光性樹脂組成物を提供することを目的とする。また本発明は、前記特性に加え、弱アルカリ性現像液を用いた場合でも短時間で現像可能な感光性樹脂組成物を提供することを目的とする。さらに本発明は、前記感光性樹脂組成物から得られる硬化物、及び前記硬化物を含む画像表示装置を提供することを目的とする。
An object of the present invention is to provide an alkali-soluble resin capable of forming a cured film with excellent development adhesion and resolution even when the film is thickened, and a photosensitive resin composition containing the alkali-soluble resin. Another object of the present invention is to provide a photosensitive resin composition which, in addition to the above properties, can be developed in a short period of time even when a weakly alkaline developer is used. Another object of the present invention is to provide a cured product obtained from the photosensitive resin composition and an image display device containing the cured product.
本発明者らは、前記課題を解決すべく鋭意検討を重ねた結果、下記のアルカリ可溶性樹脂、及び当該アルカリ可溶性樹脂を含有する感光性樹脂組成物を用いることにより上記目的を達成できることを見出し、本発明を完成するに至った。
The present inventors have made intensive studies to solve the above problems, and found that the above objects can be achieved by using the following alkali-soluble resin and a photosensitive resin composition containing the alkali-soluble resin. The present invention has been completed.
本発明は、下記一般式（１）で表される繰り返し構造単位Ｘを１種以上含むアルカリ可溶性樹脂（以下、「アルカリ可溶性樹脂Ａ」ともいう。）に関する。
（式中、Ｒ１は水素又はメチル基であり、Ｒ２は炭素数が１以上の連結基であり、Ｒ３は前記連結基の炭素原子に結合する下記一般式（２）で表される有機基であり、Ｒ４は前記連結基の炭素原子に結合するヒドロキシ基又は有機基である。）
（式中、Ｒ５は母体の炭素数が３～８であり、かつヘテロ原子を含む有機基、又は母体の炭素数が２～７であり、かつカルボキシ基を有する有機基である。）
The present invention relates to an alkali-soluble resin (hereinafter also referred to as "alkali-soluble resin A") containing one or more repeating structural units X represented by the following general formula (1).
(In the formula, R 1 is hydrogen or a methyl group, R 2 is a linking group having 1 or more carbon atoms, and R 3 is represented by the following general formula (2) bonded to a carbon atom of the linking group. is an organic group, and R 4 is a hydroxy group or an organic group bonded to the carbon atom of the linking group.)
(In the formula, R 5 is an organic group having a base of 3 to 8 carbon atoms and containing a hetero atom, or an organic group having a base of 2 to 7 carbon atoms and a carboxy group.)
また、本発明は、下記一般式（１’）で表される繰り返し構造単位Ｘ’を１種以上含む、ただし、各々がラジカル重合性置換基に終わる２～３個の末端を有する分岐した側鎖を備えた繰り返し構造単位を含まない、アルカリ可溶性樹脂（以下、「アルカリ可溶性樹脂Ｂ」ともいう。）に関する。
（式中、Ｒ１は水素又はメチル基であり、Ｒ２は炭素数が１以上の連結基であり、Ｒ３’は前記連結基の炭素原子に結合する下記一般式（２’）で表される有機基であり、Ｒ４は前記連結基の炭素原子に結合するヒドロキシ基又は有機基である。）
（式中、Ｒ５’は母体の炭素数が２～７の炭化水素基、母体の炭素数が３～８であり、かつヘテロ原子を含む有機基、又は母体の炭素数が２～７であり、かつカルボキシ基を有する有機基である。）
In addition, the present invention includes one or more repeating structural units X' represented by the following general formula (1'), provided that each branched side having 2 to 3 terminals ending in a radically polymerizable substituent The present invention relates to an alkali-soluble resin (hereinafter also referred to as "alkali-soluble resin B") that does not contain a repeating structural unit with a chain.
(Wherein, R 1 is hydrogen or a methyl group, R 2 is a linking group having 1 or more carbon atoms, and R 3′ is a carbon atom of the linking group represented by the following general formula (2′) and R 4 is a hydroxy group or an organic group bonded to the carbon atom of the linking group.)
(Wherein, R 5′ is a hydrocarbon group having a base having 2 to 7 carbon atoms, an organic group having a base having 3 to 8 carbon atoms and containing a hetero atom, or a base having 2 to 7 carbon atoms. and is an organic group having a carboxy group.)
前記アルカリ可溶性樹脂Ａ又はＢにおいて、前記Ｒ２の連結基は、母体の炭素数が１～１０の炭化水素基、又は母体の炭素数が１～１０であり、かつヘテロ原子を含む有機基であることが好ましい。
In the alkali-soluble resin A or B, the linking group of R 2 is a hydrocarbon group having 1 to 10 carbon atoms in the base, or an organic group having 1 to 10 carbon atoms in the base and containing a hetero atom. Preferably.
前記アルカリ可溶性樹脂Ａ又はＢにおいて、前記Ｒ４の有機基は、アクリロイルオキシ基、メタクリロイルオキシ基、アシルオキシ基、アミドオキシ基、アルコキシ基、アリールオキシ基、アミノ基、及び含窒素複素環からなる群より選択される１種以上の官能基を含む有機基であることが好ましい。
In the alkali-soluble resin A or B, the organic group for R4 is selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, an acyloxy group, an amidooxy group, an alkoxy group, an aryloxy group, an amino group, and a nitrogen-containing heterocyclic ring. It is preferably an organic group containing one or more selected functional groups.
また、前記アルカリ可溶性樹脂Ａ又はＢにおいて、前記Ｒ２の連結基は、母体の炭素数が１～７の炭化水素基、又は母体の炭素数が１～７であり、かつヘテロ原子を含む有機基であり、
前記Ｒ４は、前記Ｒ２の連結基の炭素原子に結合するヒドロキシ基、アクリロイルオキシ基、又はメタクリロイルオキシ基であることが好ましい。 In addition, in the alkali-soluble resin A or B, the linking group of R 2 is a hydrocarbon group having a base having 1 to 7 carbon atoms, or an organic group having a base having 1 to 7 carbon atoms and containing a hetero atom. is the basis,
R 4 is preferably a hydroxy group, an acryloyloxy group, or a methacryloyloxy group bonded to the carbon atom of the linking group of R 2 .
前記Ｒ４は、前記Ｒ２の連結基の炭素原子に結合するヒドロキシ基、アクリロイルオキシ基、又はメタクリロイルオキシ基であることが好ましい。 In addition, in the alkali-soluble resin A or B, the linking group of R 2 is a hydrocarbon group having a base having 1 to 7 carbon atoms, or an organic group having a base having 1 to 7 carbon atoms and containing a hetero atom. is the basis,
R 4 is preferably a hydroxy group, an acryloyloxy group, or a methacryloyloxy group bonded to the carbon atom of the linking group of R 2 .
また、前記アルカリ可溶性樹脂Ａ又はＢにおいて、前記Ｒ２の連結基は、母体の炭素数が１～７の炭化水素基、又は母体の炭素数が１～７であり、かつヘテロ原子を含む有機基であり、
前記Ｒ５又は前記Ｒ５’は、下記一般式（３）で表される有機基であり、
前記Ｒ４は、前記Ｒ２の連結基の炭素原子に結合するヒドロキシ基、アクリロイルオキシ基、メタクリロイルオキシ基、又は下記一般式（４）で表される有機基であることが好ましい。
（式中、Ｒ６及びＲ７はそれぞれ独立に母体の炭素数が１～６の炭化水素基であり、Ｒ６及びＲ７の母体の合計炭素数が３～８である。）
（式中、Ｒ８は水素又はメチル基であり、Ｒ９は母体の炭素数が１～５の炭化水素基、又は母体の炭素数が１～５であり、かつヘテロ原子を含む有機基である。）
In addition, in the alkali-soluble resin A or B, the linking group of R 2 is a hydrocarbon group having a base having 1 to 7 carbon atoms, or an organic group having a base having 1 to 7 carbon atoms and containing a hetero atom. is the basis,
The R 5 or the R 5' is an organic group represented by the following general formula (3),
R 4 is preferably a hydroxy group, an acryloyloxy group, a methacryloyloxy group, or an organic group represented by the following general formula (4), which is bonded to the carbon atom of the linking group of R 2 .
(In the formula, each of R 6 and R 7 is independently a hydrocarbon group having 1 to 6 carbon atoms in the base, and the total number of carbon atoms in the base of R 6 and R 7 is 3 to 8.)
(In the formula, R 8 is hydrogen or a methyl group, and R 9 is a hydrocarbon group having 1 to 5 carbon atoms as a base, or an organic group having 1 to 5 carbon atoms as a base and containing a hetero atom. be.)
前記Ｒ５又は前記Ｒ５’は、下記一般式（３）で表される有機基であり、
前記Ｒ４は、前記Ｒ２の連結基の炭素原子に結合するヒドロキシ基、アクリロイルオキシ基、メタクリロイルオキシ基、又は下記一般式（４）で表される有機基であることが好ましい。
The R 5 or the R 5' is an organic group represented by the following general formula (3),
R 4 is preferably a hydroxy group, an acryloyloxy group, a methacryloyloxy group, or an organic group represented by the following general formula (4), which is bonded to the carbon atom of the linking group of R 2 .
前記アルカリ可溶性樹脂Ａ又はＢにおいて、前記繰り返し構造単位Ｘ又はＸ’の含有量は、全繰り返し構造単位中に５～５０ｍｏｌ％であることが好ましい。
In the alkali-soluble resin A or B, the content of the repeating structural unit X or X' is preferably 5 to 50 mol% in all repeating structural units.
前記アルカリ可溶性樹脂Ａ又はＢは、酸価が２０～１２０ｍｇＫＯＨ／ｇであることが好ましい。
The alkali-soluble resin A or B preferably has an acid value of 20 to 120 mgKOH/g.
前記アルカリ可溶性樹脂Ａ又はＢは、重量平均分子量が５０００～４００００であることが好ましい。
The alkali-soluble resin A or B preferably has a weight average molecular weight of 5,000 to 40,000.
本発明の感光性樹脂組成物は、少なくとも前記アルカリ可溶性樹脂Ａ及び／又はＢ、重合性モノマー、及び光重合開始剤を含有する。
The photosensitive resin composition of the present invention contains at least the alkali-soluble resins A and/or B, a polymerizable monomer, and a photopolymerization initiator.
本発明の硬化物は、前記感光性樹脂組成物から得られるものである。
The cured product of the present invention is obtained from the photosensitive resin composition.
前記硬化物は、フォトスペーサー、隔壁材、レンズ材、層間絶縁膜材、保護膜材、光導波路材、又は平坦化膜材であることが好ましい。
The cured product is preferably a photospacer, partition wall material, lens material, interlayer insulating film material, protective film material, optical waveguide material, or flattening film material.
また、本発明は、前記硬化物を含む画像表示装置に関する。
The present invention also relates to an image display device containing the cured product.
本発明のアルカリ可溶性樹脂Ａ又はＢは、前記一般式（１）又は（１’）で表される繰り返し構造単位Ｘ又はＸ’を１種以上含んでおり、前記繰り返し構造単位Ｘ又はＸ’において側鎖の長さが一定以上の長さであり、その側鎖の末端にカルボキシ基を有する構造を持っている点を主たる特徴とする。本発明のアルカリ可溶性樹脂Ａ又はＢは、その特徴ある構造によって、厚膜化した場合でも現像密着性及び解像度に優れる硬化膜を得ることができる。また、本発明のアルカリ可溶性樹脂Ａ又はＢは、連結基Ｒ２の炭素原子に結合するヒドロキシ基又は有機基を有するため、これらの基に由来する特性をさらに有することができる。また、本発明のアルカリ可溶性樹脂Ａ及び／又はＢを含む感光性樹脂組成物は、弱アルカリ性現像液を用いた場合でも短時間で現像できるため、フォトスペーサー等の硬化物の生産性を向上させることができる。特に、前記Ｒ４が有機基である場合、本発明のアルカリ可溶性樹脂Ａ又はＢは側鎖が分岐した構造を有するため、厚膜化した場合でも現像密着性及び解像度にさらに優れる硬化膜を得ることができる。この理由としては、必ずしも理論に拘束されるものではないが、前記Ｒ３又はＲ３’がある程度長い（原子数が多い）ことで、末端のカルボキシ基が主鎖と対向する方向に向きやすいため、基材との密着に関与できるカルボキシ基の数が多くなるためと考えられる。さらに、前記Ｒ４が有機基である場合、アルカリ可溶性樹脂Ａ又はＢの側鎖は分岐した構造となるため、前記Ｒ３又はＲ３’の末端のカルボキシ基が主鎖と対向する方向にさらに向きやすくなり、基材との密着に関与できるカルボキシ基の数がさらに多くなるためと考えられる。
The alkali-soluble resin A or B of the present invention contains one or more repeating structural units X or X' represented by the general formula (1) or (1'), and in the repeating structural unit X or X' The main feature is that the length of the side chain is longer than a certain length, and it has a structure having a carboxyl group at the end of the side chain. Due to its characteristic structure, the alkali-soluble resin A or B of the present invention can provide a cured film excellent in development adhesion and resolution even when the film is thickened. In addition, since the alkali-soluble resin A or B of the present invention has a hydroxy group or an organic group bonded to the carbon atom of the linking group R2 , it can further have properties derived from these groups. In addition, since the photosensitive resin composition containing the alkali-soluble resin A and / or B of the present invention can be developed in a short time even when using a weakly alkaline developer, the productivity of cured products such as photospacers is improved. be able to. In particular, when R 4 is an organic group, the alkali-soluble resin A or B of the present invention has a branched structure in the side chain, so that even when the film is thickened, a cured film having even better development adhesion and resolution can be obtained. be able to. The reason for this, although not necessarily bound by theory, is that when R 3 or R 3′ is somewhat long (has a large number of atoms), the terminal carboxy group tends to face the main chain. , the number of carboxyl groups that can participate in adhesion to the substrate increases. Furthermore, when the R 4 is an organic group, the side chain of the alkali-soluble resin A or B has a branched structure, so that the terminal carboxy group of the R 3 or R 3′ This is probably because the orientation becomes easier, and the number of carboxyl groups that can participate in adhesion to the substrate increases.
本発明のアルカリ可溶性樹脂Ａは、下記一般式（１）で表される繰り返し構造単位Ｘを１種以上含む。
（式中、Ｒ１は水素又はメチル基であり、Ｒ２は炭素数が１以上の連結基であり、Ｒ３は前記連結基の炭素原子に結合する下記一般式（２）で表される有機基であり、Ｒ４は前記連結基の炭素原子に結合するヒドロキシ基又は有機基である。）
（式中、Ｒ５は母体の炭素数が３～８であり、かつヘテロ原子を含む有機基、又は母体の炭素数が２～７であり、かつカルボキシ基を有する有機基である。）
The alkali-soluble resin A of the present invention contains one or more repeating structural units X represented by the following general formula (1).
(In the formula, R 1 is hydrogen or a methyl group, R 2 is a linking group having 1 or more carbon atoms, and R 3 is represented by the following general formula (2) bonded to a carbon atom of the linking group. is an organic group, and R 4 is a hydroxy group or an organic group bonded to the carbon atom of the linking group.)
(In the formula, R 5 is an organic group having a base of 3 to 8 carbon atoms and containing a hetero atom, or an organic group having a base of 2 to 7 carbon atoms and a carboxy group.)
また、本発明のアルカリ可溶性樹脂Ｂは、下記一般式（１’）で表される繰り返し構造単位Ｘ’を１種以上含み、ただし、各々がラジカル重合性置換基に終わる２～３個の末端を有する分岐した側鎖を備えた繰り返し構造単位を含まない。
（式中、Ｒ１は水素又はメチル基であり、Ｒ２は炭素数が１以上の連結基であり、Ｒ３’は前記連結基の炭素原子に結合する下記一般式（２’）で表される有機基であり、Ｒ４は前記連結基の炭素原子に結合するヒドロキシ基又は有機基である。）
（式中、Ｒ５’は母体の炭素数が２～７の炭化水素基、母体の炭素数が３～８であり、かつヘテロ原子を含む有機基、又は母体の炭素数が２～７であり、かつカルボキシ基を有する有機基である。）
Further, the alkali-soluble resin B of the present invention contains one or more repeating structural units X' represented by the following general formula (1'), provided that each has 2 to 3 terminals ending in radically polymerizable substituents. does not contain repeating structural units with branched side chains having
(Wherein, R 1 is hydrogen or a methyl group, R 2 is a linking group having 1 or more carbon atoms, and R 3′ is a carbon atom of the linking group represented by the following general formula (2′) and R 4 is a hydroxy group or an organic group bonded to the carbon atom of the linking group.)
(Wherein, R 5′ is a hydrocarbon group having a base having 2 to 7 carbon atoms, an organic group having a base having 3 to 8 carbon atoms and containing a hetero atom, or a base having 2 to 7 carbon atoms. and is an organic group having a carboxy group.)
本発明において（メタ）アクリルとはアクリル又はメタクリルを、（メタ）アクリロイルとはアクリロイル又はメタクリロイルを、（メタ）アクリル酸とはアクリル酸又はメタクリル酸を、（メタ）アクリレートとはアクリレート又はメタクリレートをそれぞれ意味する。また、本発明において母体の炭素数とは、置換基を除いた主骨格となる基の炭素数を意味する。
In the present invention, (meth)acryl means acrylic or methacrylic, (meth)acryloyl means acryloyl or methacryloyl, (meth)acrylic acid means acrylic acid or methacrylic acid, and (meth)acrylate means acrylate or methacrylate, respectively. means. In the present invention, the number of carbon atoms in the base means the number of carbon atoms in the main skeleton group excluding substituents.
前記一般式（１）又は（１’）において、前記Ｒ２は炭素数が１以上の連結基であり、前記Ｒ３及び前記Ｒ４、又は前記Ｒ３’及び前記Ｒ４をエステル結合の酸素原子に連結させることができる炭素数が１以上の基であれば特に制限されない。前記連結基としては、例えば、直鎖状又は分岐鎖状の脂肪族飽和又は不飽和炭化水素基、脂環式飽和又は不飽和炭化水素基（橋かけ環、縮合環を含む）、芳香族炭化水素基、前記炭化水素基を構成する炭素原子の一部がヘテロ原子（例えば、酸素原子、窒素原子、及び硫黄原子など）で置換された有機基、及びこれらの２種以上が結合した有機基などが挙げられる。また、前記炭化水素基又は前記有機基は、種々の置換基（例えば、ハロゲン基、ヒドロキシ基、カルボキシ基、アミノ基、アルキル基、アルケニル基、アルコキシ基、及びアリール基など）や官能基（例えば、エステル結合、アミド結合、エーテル結合、チオエーテル結合、及びウレタン結合など）を有していてもよい。
In the general formula (1) or (1′), R 2 is a linking group having 1 or more carbon atoms, and R 3 and R 4 , or R 3′ and R 4 are oxygen atoms of an ester bond. There is no particular limitation as long as it is a group having 1 or more carbon atoms that can be linked to an atom. Examples of the linking group include linear or branched aliphatic saturated or unsaturated hydrocarbon groups, alicyclic saturated or unsaturated hydrocarbon groups (including bridged rings and condensed rings), and aromatic hydrocarbon groups. A hydrogen group, an organic group in which some of the carbon atoms constituting the hydrocarbon group are substituted with a hetero atom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom, etc.), and an organic group in which two or more of these are bonded etc. In addition, the hydrocarbon group or the organic group includes various substituents (e.g., halogen group, hydroxy group, carboxyl group, amino group, alkyl group, alkenyl group, alkoxy group, aryl group, etc.) and functional groups (e.g., , ester bond, amide bond, ether bond, thioether bond, urethane bond, etc.).
前記連結基は、母体の炭素数が１～１０の炭化水素基、又は母体の炭素数が１～１０であり、かつヘテロ原子（例えば、酸素原子、窒素原子、及び硫黄原子など）を含む有機基であることが好ましい。また、前記連結基は、母体の炭素数が１～７の炭化水素基、又は母体の炭素数が１～７であり、かつヘテロ原子（例えば、酸素原子、窒素原子、及び硫黄原子など）を含む有機基であることがより好ましい。なお、前記連結基がヘテロ原子を含む場合、前記連結基が有するヘテロ原子は、前記一般式（１）又は（１’）において、前記Ｒ３又はＲ３’との結合部以外の部分、前記Ｒ４との結合部以外の部分、及びエステル結合の酸素原子との結合部以外の部分に有する。また、前記連結基は、母体の炭素数が２～７である直鎖状又は分岐鎖状の脂肪族飽和又は不飽和炭化水素基、母体の炭素数が３～７の脂環式飽和又は不飽和炭化水素基、母体の炭素数が４～７であり、かつメチレン基と脂環式飽和又は不飽和炭化水素基が結合した炭化水素基、母体の炭素数が５～７であり、かつ直鎖状又は分岐鎖状の脂肪族飽和又は不飽和炭化水素基と脂環式飽和又は不飽和炭化水素基が結合した炭化水素基、又は母体の炭素数が２～７であり、かつエーテル結合を含む有機基であることが更に好ましい。
The linking group is a hydrocarbon group having 1 to 10 carbon atoms in the base, or an organic is preferably a group. In addition, the linking group is a hydrocarbon group having a parent body having 1 to 7 carbon atoms, or a parent body having a carbon number of 1 to 7 and a hetero atom (eg, an oxygen atom, a nitrogen atom, a sulfur atom, etc.). more preferably an organic group containing When the linking group contains a hetero atom, the hetero atom possessed by the linking group is the portion other than the bonding portion with R 3 or R 3′ in the general formula (1) or (1′), the It is present in the portion other than the bonding portion with R 4 and in the portion other than the bonding portion with the oxygen atom of the ester bond. The linking group may be a linear or branched aliphatic saturated or unsaturated hydrocarbon group having 2 to 7 carbon atoms in the base, or a saturated or unsaturated alicyclic group having 3 to 7 carbon atoms in the base. a saturated hydrocarbon group, a hydrocarbon group in which a methylene group and an alicyclic saturated or unsaturated hydrocarbon group are bonded, a parent body having 5 to 7 carbon atoms, and a straight A hydrocarbon group in which a chain or branched aliphatic saturated or unsaturated hydrocarbon group and an alicyclic saturated or unsaturated hydrocarbon group are bonded, or a base having 2 to 7 carbon atoms and an ether bond more preferably an organic group containing
前記一般式（１）において、前記Ｒ３は、前記Ｒ２の連結基が有する炭素原子に結合する前記一般式（２）で表される有機基である。前記一般式（２）において、前記Ｒ５は、母体の炭素数が３～８であり、かつヘテロ原子（例えば、酸素原子、窒素原子、及び硫黄原子など）を含む有機基、又は母体の炭素数が２～７であり、かつカルボキシ基を有する有機基である。前記Ｒ５は、母体の炭素数が２～７であり、かつカルボキシ基を有する有機基であることが好ましい。前記Ｒ５がカルボキシ基を有する場合、カルボキシ基の数は特に制限されないが、１～２であることが好ましい。前記有機基は、種々の置換基（例えば、ハロゲン基、ヒドロキシ基、カルボキシ基、アミノ基、アルキル基、アルケニル基、アルコキシ基、及びアリール基など）や官能基（例えば、エステル結合、アミド結合、エーテル結合、チオエーテル結合、及びウレタン結合など）を有していてもよい。
In general formula (1), R 3 is an organic group represented by general formula (2) that bonds to the carbon atom of the linking group of R 2 . In the general formula (2), R 5 is an organic group having 3 to 8 carbon atoms in the base and containing a hetero atom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom, etc.), or a carbon in the base It is an organic group having a number of 2 to 7 and having a carboxy group. R 5 is preferably an organic group having a matrix of 2 to 7 carbon atoms and a carboxy group. When R 5 has a carboxy group, the number of carboxy groups is not particularly limited, but preferably 1-2. The organic groups include various substituents (e.g., halogen groups, hydroxy groups, carboxyl groups, amino groups, alkyl groups, alkenyl groups, alkoxy groups, and aryl groups) and functional groups (e.g., ester bonds, amide bonds, ether bond, thioether bond, urethane bond, etc.).
前記一般式（２）で表される有機基は、下記のいずれかの有機基であることが好ましい。
The organic group represented by the general formula (2) is preferably any one of the following organic groups.
前記一般式（１’）において、前記Ｒ３’は、前記Ｒ２の連結基が有する炭素原子に結合する前記一般式（２’）で表される有機基である。前記一般式（２’）において、前記Ｒ５’は、母体の炭素数が２～７の炭化水素基、母体の炭素数が３～８であり、かつヘテロ原子（例えば、酸素原子、窒素原子、及び硫黄原子など）を含む有機基、又は母体の炭素数が２～７であり、かつカルボキシ基を有する有機基である。前記Ｒ５’は、母体の炭素数が２～７の炭化水素基、又は母体の炭素数が２～７であり、かつカルボキシ基を有する有機基であることが好ましい。前記Ｒ５’がカルボキシ基を有する場合、カルボキシ基の数は特に制限されないが、１～２であることが好ましい。前記炭化水素基としては、直鎖状又は分岐鎖状の脂肪族飽和又は不飽和炭化水素基、脂環式飽和又は不飽和炭化水素基（橋かけ環、縮合環を含む）、芳香族炭化水素基、及びこれらの２種以上が結合した炭化水素基などが挙げられる。前記炭化水素基又は前記有機基は、種々の置換基（例えば、ハロゲン基、ヒドロキシ基、カルボキシ基、アミノ基、アルキル基、アルケニル基、アルコキシ基、及びアリール基など）や官能基（例えば、エステル結合、アミド結合、エーテル結合、チオエーテル結合、及びウレタン結合など）を有していてもよい。
In general formula (1′), R 3′ is an organic group represented by general formula (2′) that bonds to the carbon atom of the linking group of R 2 . In the general formula (2′), R 5′ is a hydrocarbon group having 2 to 7 carbon atoms in the base, a 3 to 8 carbon base in the base, and a hetero atom (e.g., oxygen atom, nitrogen atom, , and a sulfur atom), or an organic group having a base having 2 to 7 carbon atoms and a carboxy group. R 5′ is preferably a hydrocarbon group having a base of 2 to 7 carbon atoms or an organic group having a base of 2 to 7 carbon atoms and a carboxy group. When R 5′ has a carboxy group, the number of carboxy groups is not particularly limited, but preferably 1-2. Examples of the hydrocarbon group include linear or branched aliphatic saturated or unsaturated hydrocarbon groups, alicyclic saturated or unsaturated hydrocarbon groups (including bridged rings and condensed rings), and aromatic hydrocarbons. groups, and hydrocarbon groups in which two or more of these groups are bonded. The hydrocarbon group or the organic group may contain various substituents (e.g., halogen groups, hydroxy groups, carboxyl groups, amino groups, alkyl groups, alkenyl groups, alkoxy groups, and aryl groups) or functional groups (e.g., ester groups). bond, amide bond, ether bond, thioether bond, urethane bond, etc.).
前記一般式（２’）で表される有機基は、下記のいずれかの有機基であることが好ましい。
The organic group represented by the general formula (2') is preferably any one of the following organic groups.
また、前記一般式（２）又は（２’）において、前記Ｒ５又はＲ５’は、下記一般式（３）で表される有機基であることが好ましい。
（式中、Ｒ６及びＲ７はそれぞれ独立に母体の炭素数が１～６の炭化水素基であり、Ｒ６及びＲ７の母体の合計炭素数が３～８である。）
Moreover, in the general formula (2) or (2'), the R 5 or R 5' is preferably an organic group represented by the following general formula (3).
(In the formula, each of R 6 and R 7 is independently a hydrocarbon group having 1 to 6 carbon atoms in the base, and the total number of carbon atoms in the base of R 6 and R 7 is 3 to 8.)
前記炭化水素基としては、直鎖状又は分岐鎖状の脂肪族飽和又は不飽和炭化水素基、芳香族炭化水素基、脂環式飽和又は不飽和炭化水素基などが挙げられる。前記炭化水素基は、種々の置換基（例えば、ハロゲン基、ヒドロキシ基、カルボキシ基、アミノ基、アルキル基、アルケニル基、アルコキシ基、及びアリール基など）を有していてもよい。
Examples of the hydrocarbon group include linear or branched aliphatic saturated or unsaturated hydrocarbon groups, aromatic hydrocarbon groups, and alicyclic saturated or unsaturated hydrocarbon groups. The hydrocarbon group may have various substituents (eg, halogen group, hydroxy group, carboxy group, amino group, alkyl group, alkenyl group, alkoxy group, aryl group, etc.).
上記一般式（３）で表される有機基の一例としては、下記のものが挙げられる。
Examples of the organic group represented by the general formula (3) include the following.
前記Ｒ６及びＲ７はそれぞれ独立に母体の炭素数が１～５の炭化水素基であり、Ｒ６及びＲ７の母体の合計炭素数が３～７であることが好ましい。
R 6 and R 7 are each independently a hydrocarbon group having 1 to 5 carbon atoms as a base, and the total number of carbon atoms in the base of R 6 and R 7 is preferably 3 to 7.
前記一般式（２）又は（２’）で表される有機基は、下記のいずれかの有機基であることが好ましい。
The organic group represented by the general formula (2) or (2') is preferably any one of the following organic groups.
前記一般式（１）又は（１’）において、前記Ｒ４は、前記Ｒ２の連結基が有する炭素原子に結合するヒドロキシ基又は有機基である。前記Ｒ４がヒドロキシ基である場合、さらに現像性を向上させることができる。また、前記Ｒ４が有機基である場合、その有機基に由来する特性（例えば、現像性、密着性、及び溶解性など）をさらに付与することができる。前記有機基は特に制限されず、例えば、直鎖状又は分岐鎖状の脂肪族飽和又は不飽和炭化水素基、脂環式飽和又は不飽和炭化水素基（橋かけ環、縮合環を含む）、芳香族炭化水素基、前記炭化水素基を構成する炭素原子の一部がヘテロ原子（例えば、酸素原子、窒素原子、及び硫黄原子など）で置換された有機基、及びこれらの２種以上が結合した有機基などが挙げられる。また、前記炭化水素基又は前記有機基は、種々の置換基（例えば、ハロゲン基、ヒドロキシ基、カルボキシ基、アミノ基、アルキル基、アルケニル基、アルコキシ基、及びアリール基など）や官能基（例えば、エステル結合、アミド結合、エーテル結合、チオエーテル結合、及びウレタン結合など）を有していてもよい。
In the general formula (1) or (1′), R 4 is a hydroxy group or an organic group bonded to the carbon atom of the linking group of R 2 . When R4 is a hydroxy group, the developability can be further improved. In addition, when R 4 is an organic group, properties derived from the organic group (eg developability, adhesiveness, solubility, etc.) can be further imparted. The organic group is not particularly limited, and examples include linear or branched aliphatic saturated or unsaturated hydrocarbon groups, alicyclic saturated or unsaturated hydrocarbon groups (including bridged rings and condensed rings), an aromatic hydrocarbon group, an organic group in which some of the carbon atoms constituting the hydrocarbon group are substituted with heteroatoms (e.g., oxygen atoms, nitrogen atoms, sulfur atoms, etc.), and two or more of these bonded together and the like. In addition, the hydrocarbon group or the organic group includes various substituents (e.g., halogen group, hydroxy group, carboxyl group, amino group, alkyl group, alkenyl group, alkoxy group, aryl group, etc.) and functional groups (e.g., , ester bond, amide bond, ether bond, thioether bond, urethane bond, etc.).
前記Ｒ４の有機基は、アクリロイルオキシ基、メタクリロイルオキシ基、アシルオキシ基、アミドオキシ基、アルコキシ基、アリールオキシ基、アミノ基、及び含窒素複素環からなる群より選択される１種以上の官能基を含む有機基であることが好ましく、アクリロイルオキシ基、メタクリロイルオキシ基、又は下記式のいずれかで表される有機基であることがより好ましい。
（式中、Ｒ１０及びＲ１１はそれぞれ独立に段落[００３９]に記載の有機基である。）
The organic group for R4 is one or more functional groups selected from the group consisting of acryloyloxy, methacryloyloxy, acyloxy, amidooxy, alkoxy, aryloxy, amino, and nitrogen-containing heterocycles. and more preferably an acryloyloxy group, a methacryloyloxy group, or an organic group represented by any of the following formulas.
(Wherein, R 10 and R 11 are each independently an organic group described in paragraph [0039].)
また、前記Ｒ４は、前記Ｒ２の連結基の炭素原子に結合するヒドロキシ基、アクリロイルオキシ基、メタクリロイルオキシ基、又は下記一般式（４）で表される有機基であることが好ましい。
（式中、Ｒ８は水素又はメチル基であり、Ｒ９は母体の炭素数が１～５の炭化水素基、又は母体の炭素数が１～５であり、かつヘテロ原子を含む有機基である。）
R 4 is preferably a hydroxy group, an acryloyloxy group, a methacryloyloxy group, or an organic group represented by the following general formula (4), which is bonded to the carbon atom of the linking group of R 2 .
(In the formula, R 8 is hydrogen or a methyl group, and R 9 is a hydrocarbon group having 1 to 5 carbon atoms as a base, or an organic group having 1 to 5 carbon atoms as a base and containing a hetero atom. be.)
前記一般式（４）において、前記Ｒ９は、母体の炭素数が１～５の炭化水素基、又は母体の炭素数が１～５であり、かつヘテロ原子（例えば、酸素原子、窒素原子、及び硫黄原子など）を含む有機基である。なお、前記有機基がヘテロ原子を含む場合、前記有機基が有するヘテロ原子は、前記一般式（４）において、ウレタン結合の窒素原子との結合部以外の部分、及び（メタ）アクリロイルオキシ基の酸素原子との結合部以外の部分に有する。前記炭化水素基としては、直鎖状又は分岐鎖状の脂肪族飽和又は不飽和炭化水素基が挙げられる。前記炭化水素基又は前記有機基は、種々の置換基（例えば、ハロゲン基、ヒドロキシ基、カルボキシ基、アミノ基、アルキル基、アルケニル基、アルコキシ基、及びアリール基など）や官能基（例えば、エステル結合、アミド結合、エーテル結合、チオエーテル結合、及びウレタン結合など）を有していてもよい。前記Ｒ９は、好ましくは母体の炭素数が１～５の炭化水素基であり、より好ましくはエチレン基、又はプロピレン基である。
In the general formula (4), R 9 is a hydrocarbon group having 1 to 5 carbon atoms in the base, or a heteroatom (for example, an oxygen atom, a nitrogen atom, and sulfur atoms). When the organic group contains a heteroatom, the heteroatom of the organic group is, in the general formula (4), the portion other than the bonding portion with the nitrogen atom of the urethane bond, and the (meth)acryloyloxy group. It is present in the portion other than the bonding portion with the oxygen atom. The hydrocarbon group includes a linear or branched aliphatic saturated or unsaturated hydrocarbon group. The hydrocarbon group or the organic group may contain various substituents (e.g., halogen groups, hydroxy groups, carboxyl groups, amino groups, alkyl groups, alkenyl groups, alkoxy groups, and aryl groups) or functional groups (e.g., ester groups). bond, amide bond, ether bond, thioether bond, urethane bond, etc.). R 9 is preferably a hydrocarbon group having 1 to 5 carbon atoms as a base, more preferably an ethylene group or a propylene group.
前記アルカリ可溶性樹脂Ａ又はＢを構成する前記繰り返し構造単位Ｘ又はＸ’以外の繰り返し構造単位の元となるモノマーとしては、例えば、（メタ）アクリル酸、２－（メタ）アクリロイルオキシエチルコハク酸、マレイン酸、及びイタコン酸等のカルボキシル基含有モノマー；無水マレイン酸、及び無水イタコン酸等のカルボン酸無水物基含有モノマー；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、ベンジル（メタ）アクリレート、ラウリル（メタ）アクリレート、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、エトキシエチル（メタ）アクリレート、及びグリシジル（メタ）アクリレート等のアルキル（メタ）アクリレート；シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、及びジシクロペンテニル（メタ）アクリレート等の脂環式（メタ）アクリレート等が挙げられる。また、スチレン、シクロヘキシルマレイミド、フェニルマレイミド、メチルマレイミド、エチルマレイミド、ｎ－ブチルマレイミド、ラウリルマイレミド、及びシリコーン含有モノマー等を共重合モノマーとして用いてもよい。これらモノマーは、単独で用いてもよく、２種以上を併用してもよい。
Examples of the monomer that is the source of the repeating structural unit other than the repeating structural unit X or X′ constituting the alkali-soluble resin A or B include (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, Carboxyl group-containing monomers such as maleic acid and itaconic acid; carboxylic anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl Alkyl (meth)acrylates such as (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ethoxyethyl (meth)acrylate, and glycidyl (meth)acrylate Acrylates; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate and other cycloaliphatic (meth)acrylates, and the like. Also, styrene, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, n-butylmaleimide, laurylmaleimide, silicone-containing monomers, and the like may be used as copolymerizable monomers. These monomers may be used alone or in combination of two or more.
ただし、前記アルカリ可溶性樹脂Ｂは、各々がラジカル重合性置換基に終わる２～３個の末端を有する分岐した側鎖を備えた繰り返し構造単位（以下、「繰り返し構造単位Ｙ」ともいう。）を含まない。前記繰り返し構造単位Ｙは、国際公開第２０１８／１６９０３６号に記載されているモノマー単位（１）であり、詳しくは、前記各々のラジカル重合性置換基は、例えば、炭化水素鎖（Ｌ）上にそれぞれ置換しており、当該炭化水素鎖（Ｌ）は、例えば、－ＣＯＯ－基を介して、ポリマーの主鎖に結合している。当該炭化水素鎖（Ｌ）を構成する炭素数は、例えば、３～５個、３又は４個、あるいは３個である。前記ラジカル重合性置換基は、例えば、（メタ）アクリロイルオキシ基である。
However, the alkali-soluble resin B contains a repeating structural unit (hereinafter also referred to as "repeating structural unit Y") having a branched side chain having 2 to 3 terminals each ending in a radically polymerizable substituent. Not included. The repeating structural unit Y is a monomer unit (1) described in WO 2018/169036. Specifically, each of the radically polymerizable substituents is, for example, on the hydrocarbon chain (L) Each substituted, the hydrocarbon chain (L) is attached to the main chain of the polymer via, for example, a --COO-- group. The number of carbon atoms constituting the hydrocarbon chain (L) is, for example, 3 to 5, 3 or 4, or 3. The radically polymerizable substituent is, for example, a (meth)acryloyloxy group.
本発明のアルカリ可溶性樹脂Ａ又はＢは、例えば、エポキシ基含有（メタ）アクリレートを含むモノマー組成物を重合して得られる側鎖にエポキシ基を有する重合体に、カルボキシ基含有化合物を反応させてヒドロキシ基を有する側鎖に変換し、そして前記ヒドロキシ基にカルボン酸無水物を反応させる方法（１）、あるいはエポキシ基含有（メタ）アクリレートを含むモノマー組成物を重合して得られる側鎖にエポキシ基を有する重合体に、エチレン性不飽和基とカルボキシ基とを有する化合物を反応させてヒドロキシ基とエチレン性不飽和基を有する側鎖に変換し、そして前記ヒドロキシ基に、イソシアネート基等のヒドロキシ基と反応する官能基を有する化合物を反応させ、さらに前記エチレン性不飽和基に、水酸基、チオール基、及びアミノ基等のエチレン性不飽和基と反応する官能基とカルボキシ基とを有する化合物を反応させる方法（２）などにより合成することができる。
The alkali-soluble resin A or B of the present invention is prepared by, for example, reacting a polymer having an epoxy group in a side chain obtained by polymerizing a monomer composition containing an epoxy group-containing (meth)acrylate with a carboxy group-containing compound. Method (1) of converting a side chain having a hydroxy group and reacting the hydroxy group with a carboxylic acid anhydride, or adding an epoxy to the side chain obtained by polymerizing a monomer composition containing an epoxy group-containing (meth)acrylate A polymer having an ethylenically unsaturated group and a carboxy group is reacted with a compound having an ethylenically unsaturated group and a carboxyl group to convert a side chain having a hydroxy group and an ethylenically unsaturated group, and a hydroxy group such as an isocyanate group is added to the hydroxy group. A compound having a functional group that reacts with the group is reacted, and a compound having a functional group that reacts with an ethylenically unsaturated group such as a hydroxyl group, a thiol group, and an amino group and a carboxy group is added to the ethylenically unsaturated group. It can be synthesized by reaction method (2) or the like.
前記アルカリ可溶性樹脂Ａ又はＢは、前記繰り返し構造単位Ｘ又はＸ’から構成されるホモポリマーであってもよく、また、前記繰り返し構造単位Ｘ又はＸ’と他の繰り返し構造単位から構成されるランダム共重合体、ブロック共重合体、交互共重合体、又は周期的共重合体であってもよい。
The alkali-soluble resin A or B may be a homopolymer composed of the repeating structural unit X or X', or a random polymer composed of the repeating structural unit X or X' and another repeating structural unit. It may be a copolymer, block copolymer, alternating copolymer, or periodic copolymer.
前記アルカリ可溶性樹脂Ａ又はＢにおいて、前記繰り返し構造単位Ｘ又はＸ’の含有量は特に制限されないが、厚膜化した場合でも現像密着性及び解像度に優れる硬化膜を形成する観点、及び弱アルカリ性現像液を用いた場合でも短時間で現像可能にする観点から、全繰り返し構造単位中に５～５０ｍｏｌ％であることが好ましく、より好ましくは５～２５ｍｏｌ％である。
In the alkali-soluble resin A or B, the content of the repeating structural unit X or X' is not particularly limited. From the viewpoint of enabling development in a short time even when a liquid is used, it is preferably 5 to 50 mol %, more preferably 5 to 25 mol % in all repeating structural units.
前記アルカリ可溶性樹脂Ａ又はＢの重量平均分子量は特に制限されないが、感度及び現像性の観点から、５０００～４００００であることが好ましく、より好ましくは５０００～２００００である。前記重量平均分子量は、ゲル浸透クロマトグラフィー（ＧＰＣ）を用いて測定したポリスチレン換算による値であり、ＪＩＳ ７２５２－４に準拠して測定した値である。後述の実施例において記載された重量平均分子量も、本項の記載に従って求めた値である。
Although the weight average molecular weight of the alkali-soluble resin A or B is not particularly limited, it is preferably 5,000 to 40,000, more preferably 5,000 to 20,000 from the viewpoint of sensitivity and developability. The weight-average molecular weight is a polystyrene-equivalent value measured using gel permeation chromatography (GPC) and is a value measured according to JIS 7252-4. The weight-average molecular weights described in Examples below are also values obtained according to the description in this section.
前記アルカリ可溶性樹脂Ａ又はＢの酸価は特に制限されないが、弱アルカリ性現像液を用いた場合でも短時間で現像可能にする観点から、２０～１２０ｍｇＫＯＨ／ｇであることが好ましく、より好ましくは２０～８０ｍｇＫＯＨ／ｇである。
Although the acid value of the alkali-soluble resin A or B is not particularly limited, it is preferably 20 to 120 mgKOH/g, more preferably 20, from the viewpoint of enabling development in a short time even when a weakly alkaline developer is used. ~80 mg KOH/g.
本発明の感光性樹脂組成物は、少なくとも前記アルカリ可溶性樹脂Ａ及び／又はＢ、重合性モノマー、及び光重合開始剤を含有する。
The photosensitive resin composition of the present invention contains at least the alkali-soluble resins A and/or B, a polymerizable monomer, and a photopolymerization initiator.
前記感光性樹脂組成物中の全固形分の含有量に対する前記アルカリ可溶性樹脂Ａ及び／又はＢの含有割合（併用する場合は合計である。）は特に制限されないが、厚膜化した場合でも現像密着性及び解像度に優れる硬化膜を形成する観点、及び弱アルカリ性現像液を用いた場合でも短時間で現像可能にする観点から、通常４０～９０質量％程度であり、好ましくは４０～８０質量％であり、より好ましくは５０～７０質量％である。
The content ratio of the alkali-soluble resin A and / or B to the total solid content in the photosensitive resin composition (when used in combination, it is the total) is not particularly limited, but even when the film is thickened, development From the viewpoint of forming a cured film with excellent adhesion and resolution, and from the viewpoint of enabling development in a short time even when using a weakly alkaline developer, it is usually about 40 to 90% by mass, preferably 40 to 80% by mass. and more preferably 50 to 70% by mass.
前記重合性モノマーは特に制限されず、例えば、ノニルフェニルカルビトール（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、２－エチルヘキシルカルビトール（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、及びＮ－ビニルピロリドン等の単官能モノマーや、ジビニルベンゼン、ジアリルフタレート、及びジアリルベンゼンホスホネート等の多官能芳香族ビニル系モノマー；（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、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ジ（メタ）アクリレート、ペンタエリスリトールトリ（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ジ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジ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ペンタ（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、及びトリス（ヒドロキシエチル）イソシアヌレートのトリ（メタ）アクリレート等の多官能（メタ）アクリレート等の多官能モノマーが挙げられる。これら重合性モノマーは、単独で用いてもよく、２種以上を併用してもよい。
The polymerizable monomer is not particularly limited, and examples include nonylphenyl carbitol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxyethyl (meth) ) Monofunctional monomers such as acrylates and N-vinylpyrrolidone, and polyfunctional aromatic vinyl monomers such as divinylbenzene, diallyl phthalate, and diallylbenzene phosphonate; (di) ethylene glycol di (meth) acrylate, propylene glycol di ( meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate (meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris(hydroxyethyl)isocyanurate Polyfunctional monomers such as polyfunctional (meth)acrylates such as tri(meth)acrylate can be used. These polymerizable monomers may be used alone or in combination of two or more.
前記重合性モノマーの含有量は特に制限されないが、本発明の効果を十分に得る観点から、前記アルカリ可溶性樹脂Ａ及び／又はＢ１００質量部（併用する場合は合計である。）に対して３０～１００質量部であることが好ましく、より好ましくは４０～８０質量部であり、更に好ましくは５０～７０質量部である。
The content of the polymerizable monomer is not particularly limited, but from the viewpoint of sufficiently obtaining the effects of the present invention, the alkali-soluble resin A and / or B 100 parts by mass (when used in combination, the total.) 30 ~ It is preferably 100 parts by mass, more preferably 40 to 80 parts by mass, even more preferably 50 to 70 parts by mass.
前記光重合開始剤は特に制限されず、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等のアセトフェノン類；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；ベンゾフェノン等のベンゾフェノン類；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－オンや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；アシルホスフィンオキサイド類およびキサントン類等が挙げられる。これら光重合開始剤は、単独で用いてもよく、２種以上を併用してもよい。
The photopolymerization initiator is not particularly limited, and examples thereof include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenones such as; 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and other anthraquinones; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc. thioxanthones; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one and 2-benzyl -2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; acylphosphine oxides and xanthones. These photopolymerization initiators may be used alone or in combination of two or more.
前記光重合開始剤の含有量は特に制限されないが、前記アルカリ可溶性樹脂Ａ及び／又はＢ１００質量部（併用する場合は合計である。）に対して、０．１～５質量部であることが好ましく、より好ましくは０．２～４質量部であり、更に好ましくは０．５～３質量部である。
The content of the photopolymerization initiator is not particularly limited, but it is 0.1 to 5 parts by mass with respect to 100 parts by mass of the alkali-soluble resin A and / or B (the total when used in combination). It is preferably 0.2 to 4 parts by mass, and still more preferably 0.5 to 3 parts by mass.
前記感光性樹脂組成物には、光重合開始助剤を添加してもよい。光重合開始助剤としては、例えば、１，３，５－トリス（３－メルカプトプロピオニルオキシエチル）－イソシアヌレート、１，３，５－トリス（３－メルカプトブチルオキシエチル）－イソシアヌレート（昭和電工社製、カレンズＭＴ（登録商標）ＮＲ１）、トリメチロールプロパントリス（３－メルカプトプロピオネート）等の３官能チオール化合物；ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）（昭和電工社製、カレンズＭＴ（登録商標）ＰＥＩ）等の４官能チオール化合物；ジペンタエリスリトールヘキサキス（３－プロピオネート）等の６官能チオール化合物等の多官能チオールが挙げられる。これら光重合開始助剤は、単独で用いてもよく、２種以上を併用してもよい。
A photopolymerization initiation aid may be added to the photosensitive resin composition. Examples of photopolymerization initiation aids include 1,3,5-tris(3-mercaptopropionyloxyethyl)-isocyanurate, 1,3,5-tris(3-mercaptobutyloxyethyl)-isocyanurate (Showa Denko manufactured by Karenz MT (registered trademark) NR1), trifunctional thiol compounds such as trimethylolpropane tris (3-mercaptopropionate); butyrate) (manufactured by Showa Denko Co., Ltd., Karenz MT (registered trademark) PEI) and other tetrafunctional thiol compounds; dipentaerythritol hexakis (3-propionate) and other hexafunctional thiol compounds. These photopolymerization initiation aids may be used alone or in combination of two or more.
前記感光性樹脂組成物には、熱重合開始剤を添加してもよい。熱重合開始剤としては、例えば、クメンハイドロパーオキサイド、ジイソプロピルベンゼンパーオキサイド、ジ－ｔ－ブチルパーオキサイド、ラウリルパーオキサイド、ベンゾイルパーオキサイド、ｔ－ブチルパーオキシイソプロピルカーボネート、ｔ－ブチルパーオキシ－２－エチルヘキサノエート、ｔ－アミルパーオキシ－２－エチルヘキサノエート等の有機過酸化物；２，２’－アゾビス（イソブチロニトリル）、１，１’－アゾビス（シクロヘキサンカルボニトリル）、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、ジメチル２，２’－アゾビス（２－メチルプロピオネート）等のアゾ化合物等が挙げられる。これら熱重合開始剤は、単独で用いてもよく、２種以上を併用してもよい。
A thermal polymerization initiator may be added to the photosensitive resin composition. Thermal polymerization initiators include, for example, cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-butylperoxy-2 -organic peroxides such as ethylhexanoate and t-amylperoxy-2-ethylhexanoate; 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), azo compounds such as 2,2'-azobis(2,4-dimethylvaleronitrile) and dimethyl 2,2'-azobis(2-methylpropionate); These thermal polymerization initiators may be used alone or in combination of two or more.
前記感光性樹脂組成物には、不飽和ポリエステル、エポキシアクリレート、ウレタンアクリレート、ポリエステルアクリレート等のラジカル重合性オリゴマー；エポキシ樹脂等の硬化性樹脂を添加してもよい。
Radically polymerizable oligomers such as unsaturated polyesters, epoxy acrylates, urethane acrylates and polyester acrylates; curable resins such as epoxy resins may be added to the photosensitive resin composition.
前記感光性樹脂組成物は、溶媒を含有してもよい。溶媒としては、例えば、テトラヒドロフラン、ジオキサン、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ジメチルエーテル等のエーテル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類；酢酸エチル、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート、３－メトキシブチルアセテート等のエステル類；メタノール、エタノール、イソプロパノール、ｎ－ブタノール、エチ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メチルエーテル等のアルコール類；トルエン、キシレン、エチルベンゼン等の芳香族炭化水素類；クロロホルム、ジメチルスルホキシド等が挙げられる。これら溶媒は、単独で用いてもよく、２種以上を併用してもよい。なお、溶媒の含有量は、当該組成物を使用する際の最適粘度に応じて適宜設定すればよい。
The photosensitive resin composition may contain a solvent. Examples of solvents include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy esters such as butyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; mentioned. These solvents may be used alone or in combination of two or more. In addition, the content of the solvent may be appropriately set according to the optimum viscosity when using the composition.
前記感光性樹脂組成物は、本発明の効果を損なわない範囲で、水酸化アルミニウム、タルク、クレー、硫酸バリウム等の充填材、染料、顔料、消泡剤、カップリング剤、レベリング剤、増感剤、離型剤、滑剤、可塑剤、酸化防止剤、紫外線吸収剤、難燃剤、重合抑制剤、増粘剤、及び分散剤等の公知の添加剤を含有していてもよい。
The photosensitive resin composition contains fillers such as aluminum hydroxide, talc, clay, barium sulfate, etc., dyes, pigments, antifoaming agents, coupling agents, leveling agents, and sensitizers, as long as the effects of the present invention are not impaired. known additives such as agents, release agents, lubricants, plasticizers, antioxidants, UV absorbers, flame retardants, polymerization inhibitors, thickeners and dispersants.
本発明の硬化物は、前記感光性樹脂組成物を硬化することにより得られる。前記硬化物の製造方法としては、例えば、前記感光性樹脂組成物を成型金型（樹脂金型）へ注入したり、あるいは前記感光性樹脂組成物を基材（基板）や各種機能層上へコーティングして所望の形状にした後に、光（例えば、紫外線）を照射して前記感光性樹脂組成物を硬化する方法が挙げられる。硬化の条件は、使用する前記感光性樹脂組成物に応じて適宜調整する。
The cured product of the present invention is obtained by curing the photosensitive resin composition. As a method for producing the cured product, for example, the photosensitive resin composition is injected into a mold (resin mold), or the photosensitive resin composition is placed on a substrate (substrate) or various functional layers. A method of curing the photosensitive resin composition by irradiating it with light (for example, ultraviolet rays) after forming it into a desired shape by coating may be mentioned. Curing conditions are appropriately adjusted according to the photosensitive resin composition to be used.
前記硬化物は、フォトスペーサー、隔壁材、レンズ材、層間絶縁膜材、保護膜材、光導波路材、又は平坦化膜材として好適に用いられ、特にフォトスペーサーとして好適に用いられる。
The cured product is suitably used as a photospacer, partition wall material, lens material, interlayer insulating film material, protective film material, optical waveguide material, or flattening film material, and is particularly suitably used as a photospacer.
フォトスペーサーの形成方法は特に制限されず、例えば、前記感光性樹脂組成物をガラス又は透明プラスチックフィルム等の基板に塗布し、乾燥して塗膜を形成し、次いで、フォトリソグラフィーにより形成することができる。フォトリソグラフィーにおいては、例えば、塗膜上にフォトマスクを配置し、紫外線を照射することにより塗膜を光硬化させ、紫外線照射後の塗膜にアルカリ水溶液を散布し、未露光部を溶解、除去して残った露光部を水洗して現像することにより、フォトスペーサーを形成する。その後、ポストベークを行ってもよい。
The method for forming the photospacer is not particularly limited, and for example, the photosensitive resin composition may be applied to a substrate such as glass or a transparent plastic film, dried to form a coating film, and then formed by photolithography. can. In photolithography, for example, a photomask is placed on the coating film, the coating film is photocured by irradiating with ultraviolet rays, and an alkaline aqueous solution is sprayed on the coating film after the ultraviolet irradiation to dissolve and remove the unexposed areas. The remaining exposed portions are washed with water and developed to form photospacers. A post-bake may then be performed.
本発明の感光性樹脂組成物を用いることにより、膜厚が１０μｍ以上、２０μｍ以上、３０μｍ以上、さらには５０μｍ以上のフォトスペーサーを、高い現像密着性かつ高解像度で製造することができる。また、本発明の感光性樹脂組成物を用いることにより、アスペクト比が４．０以上のフォトスペーサーを製造することができる。また、本発明の感光性樹脂組成物は、弱アルカリ性現像液を用いた場合でも短時間で現像できるため、フォトスペーサーを生産性よく製造することができる。
By using the photosensitive resin composition of the present invention, a photospacer having a film thickness of 10 µm or more, 20 µm or more, 30 µm or more, or even 50 µm or more can be produced with high development adhesion and high resolution. Moreover, by using the photosensitive resin composition of the present invention, a photospacer having an aspect ratio of 4.0 or more can be produced. Moreover, since the photosensitive resin composition of the present invention can be developed in a short time even when a weakly alkaline developer is used, the photospacer can be produced with high productivity.
以下に実施例をあげて本発明を説明するが、本発明はこれら実施例によりなんら限定されるものではない。
Although the present invention will be described with reference to examples below, the present invention is not limited by these examples.
［合成例１］アルカリ可溶性樹脂１の合成
下記の製造方法により、下記の繰り返し構造単位Ａ及びＸ１を含むアルカリ可溶性樹脂１を合成した。
加熱冷却・撹拌装置、還流冷却管、及び窒素導入管を備えたガラス製フラスコに、グリシジルメタクリレート１００ｇ、及びプロピレングリコールモノメチルエーテルアセテート２１２ｇを仕込んだ。系内の気相部分を窒素で置換したのち、２，２’－アゾビス（２，４－ジメチルバレロニトリル）１７ｇを添加し、８０℃で加熱し、同温度で８時間反応させた。得られた溶液に、更にアクリル酸５３．２ｇ、トリフェニルホスフィン１．０ｇ、ハイドロキノン０．０２ｇ、及びプロピレングリコールモノメチルエーテルアセテート６．０ｇを添加し、１００℃で１６時間反応させた。反応後、反応溶液に更に無水コハク酸３．７ｇ、及びプロピレングリコールモノメチルエーテルアセテート１３．０ｇを添加し、６５℃で６時間反応させて、アルカリ可溶性樹脂１を４５質量％含む溶液を得た。ＧＰＣにて分子量測定した結果、アルカリ可溶性樹脂１の重量平均分子量（Ｍｗ）は７，０００であった。なお、分子量測定は、ゲルパーミエイションクロマトグラフィー（東ソー社製、品番:HLC-8120、カラム：G-5000HXLおよびG-3000HXLの２連結、検出器：RI、移動相：テトラヒドロフラン）にて行った。以下でも同様の方法で重量平均分子量を測定した。また、アルカリ可溶性樹脂１の酸価は２１ｍｇＫＯＨ／ｇであった。
[Synthesis Example 1] Synthesis of alkali-soluble resin 1 Alkali-soluble resin 1 containing the following repeating structural units A and X1 was synthesized by the following production method.
100 g of glycidyl methacrylate and 212 g of propylene glycol monomethyl ether acetate were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. After the gas phase in the system was replaced with nitrogen, 17 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated at 80°C, and reacted at the same temperature for 8 hours. Further, 53.2 g of acrylic acid, 1.0 g of triphenylphosphine, 0.02 g of hydroquinone, and 6.0 g of propylene glycol monomethyl ether acetate were added to the obtained solution and reacted at 100° C. for 16 hours. After the reaction, 3.7 g of succinic anhydride and 13.0 g of propylene glycol monomethyl ether acetate were further added to the reaction solution and reacted at 65° C. for 6 hours to obtain a solution containing 45% by mass of alkali-soluble resin 1. As a result of molecular weight measurement by GPC, the weight average molecular weight (Mw) of alkali-soluble resin 1 was 7,000. The molecular weight was measured by gel permeation chromatography (manufactured by Tosoh Corporation, product number: HLC-8120, column: two connections of G-5000HXL and G-3000HXL, detector: RI, mobile phase: tetrahydrofuran). . The weight average molecular weight was measured by the same method below. Moreover, the acid value of the alkali-soluble resin 1 was 21 mgKOH/g.
下記の製造方法により、下記の繰り返し構造単位Ａ及びＸ１を含むアルカリ可溶性樹脂１を合成した。
［合成例２］アルカリ可溶性樹脂２の合成
反応溶液への無水コハク酸の添加量を１１．０ｇ、及びプロピレングリコールモノメチルエーテルアセテートの添加量を２２．０ｇに変更した以外は、合成例１と同様の製造方法でアルカリ可溶性樹脂２を４５質量％含む溶液を得た。ＧＰＣにて分子量測定した結果、アルカリ可溶性樹脂２の重量平均分子量（Ｍｗ）は７，０００であった。また、アルカリ可溶性樹脂２の酸価は５４ｍｇＫＯＨ／ｇであった。 [Synthesis Example 2] Synthesis of alkali-soluble resin 2 Same as Synthesis Example 1, except that the amount of succinic anhydride added to the reaction solution was changed to 11.0 g, and the amount of propylene glycol monomethyl ether acetate added to the reaction solution was changed to 22.0 g. A solution containing 45% by mass of alkali-soluble resin 2 was obtained by the production method of . As a result of molecular weight measurement by GPC, the weight average molecular weight (Mw) of alkali-soluble resin 2 was 7,000. Moreover, the acid value of the alkali-soluble resin 2 was 54 mgKOH/g.
反応溶液への無水コハク酸の添加量を１１．０ｇ、及びプロピレングリコールモノメチルエーテルアセテートの添加量を２２．０ｇに変更した以外は、合成例１と同様の製造方法でアルカリ可溶性樹脂２を４５質量％含む溶液を得た。ＧＰＣにて分子量測定した結果、アルカリ可溶性樹脂２の重量平均分子量（Ｍｗ）は７，０００であった。また、アルカリ可溶性樹脂２の酸価は５４ｍｇＫＯＨ／ｇであった。 [Synthesis Example 2] Synthesis of alkali-soluble resin 2 Same as Synthesis Example 1, except that the amount of succinic anhydride added to the reaction solution was changed to 11.0 g, and the amount of propylene glycol monomethyl ether acetate added to the reaction solution was changed to 22.0 g. A solution containing 45% by mass of alkali-soluble resin 2 was obtained by the production method of . As a result of molecular weight measurement by GPC, the weight average molecular weight (Mw) of alkali-soluble resin 2 was 7,000. Moreover, the acid value of the alkali-soluble resin 2 was 54 mgKOH/g.
［合成例３］アルカリ可溶性樹脂３の合成
反応溶液への無水コハク酸の添加量を１８．５ｇ、及びプロピレングリコールモノメチルエーテルアセテートの添加量を３１．０ｇに変更した以外は、合成例１と同様の製造方法でアルカリ可溶性樹脂３を４５質量％含む溶液を得た。ＧＰＣにて分子量測定した結果、アルカリ可溶性樹脂３の重量平均分子量（Ｍｗ）は７，０００であった。また、アルカリ可溶性樹脂３の酸価は６６ｍｇＫＯＨ／ｇであった。 [Synthesis Example 3] Synthesis of alkali-soluble resin 3 Same as Synthesis Example 1, except that the amount of succinic anhydride added to the reaction solution was changed to 18.5 g, and the amount of propylene glycol monomethyl ether acetate added to the reaction solution was changed to 31.0 g. A solution containing 45% by mass of alkali-soluble resin 3 was obtained by the production method of . As a result of molecular weight measurement by GPC, the weight average molecular weight (Mw) of alkali-soluble resin 3 was 7,000. Moreover, the acid value of the alkali-soluble resin 3 was 66 mgKOH/g.
反応溶液への無水コハク酸の添加量を１８．５ｇ、及びプロピレングリコールモノメチルエーテルアセテートの添加量を３１．０ｇに変更した以外は、合成例１と同様の製造方法でアルカリ可溶性樹脂３を４５質量％含む溶液を得た。ＧＰＣにて分子量測定した結果、アルカリ可溶性樹脂３の重量平均分子量（Ｍｗ）は７，０００であった。また、アルカリ可溶性樹脂３の酸価は６６ｍｇＫＯＨ／ｇであった。 [Synthesis Example 3] Synthesis of alkali-soluble resin 3 Same as Synthesis Example 1, except that the amount of succinic anhydride added to the reaction solution was changed to 18.5 g, and the amount of propylene glycol monomethyl ether acetate added to the reaction solution was changed to 31.0 g. A solution containing 45% by mass of alkali-soluble resin 3 was obtained by the production method of . As a result of molecular weight measurement by GPC, the weight average molecular weight (Mw) of alkali-soluble resin 3 was 7,000. Moreover, the acid value of the alkali-soluble resin 3 was 66 mgKOH/g.
［合成例４］アルカリ可溶性樹脂４の合成
下記の製造方法により、下記の繰り返し構造単位Ａ及びＸ１を含むアルカリ可溶性樹脂４を合成した。
加熱冷却・撹拌装置、還流冷却管、及び窒素導入管を備えたガラス製フラスコに、グリシジルメタクリレート１００ｇ、及びプロピレングリコールモノメチルエーテルアセテート１５０ｇを仕込んだ。系内の気相部分を窒素で置換したのち、２，２’－アゾビス（２，４－ジメチルバレロニトリル）５．２ｇを添加し、８０℃で加熱し、同温度で８時間反応させた。得られた溶液に、更にアクリル酸５３．２ｇ、トリフェニルホスフィン２．０ｇ、ハイドロキノン０．０２ｇ、及びプロピレングリコールモノメチルエーテルアセテート１．０ｇを添加し、１００℃で７時間反応させた。反応後、反応溶液に更に無水コハク酸１１ｇ、及びプロピレングリコールモノメチルエーテルアセテート９．３ｇを添加し、６５℃で６時間反応させて、アルカリ可溶性樹脂４を５２質量％含む溶液を得た。ＧＰＣにて分子量測定した結果、アルカリ可溶性樹脂４の重量平均分子量（Ｍｗ）は１３，０００であった。また、アルカリ可溶性樹脂４の酸価は５１ｍｇＫＯＨ／ｇであった。
[Synthesis Example 4] Synthesis of Alkali-Soluble Resin 4 Alkali-soluble resin 4 containing the following repeating structural units A and X1 was synthesized by the following production method.
100 g of glycidyl methacrylate and 150 g of propylene glycol monomethyl ether acetate were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. After the gas phase in the system was replaced with nitrogen, 5.2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated at 80°C, and reacted at the same temperature for 8 hours. Further, 53.2 g of acrylic acid, 2.0 g of triphenylphosphine, 0.02 g of hydroquinone, and 1.0 g of propylene glycol monomethyl ether acetate were added to the obtained solution and reacted at 100° C. for 7 hours. After the reaction, 11 g of succinic anhydride and 9.3 g of propylene glycol monomethyl ether acetate were further added to the reaction solution and reacted at 65° C. for 6 hours to obtain a solution containing 52% by mass of alkali-soluble resin 4 . As a result of molecular weight measurement by GPC, the weight average molecular weight (Mw) of alkali-soluble resin 4 was 13,000. Moreover, the acid value of the alkali-soluble resin 4 was 51 mgKOH/g.
下記の製造方法により、下記の繰り返し構造単位Ａ及びＸ１を含むアルカリ可溶性樹脂４を合成した。
［合成例５］アルカリ可溶性樹脂５の合成
下記の製造方法により、下記の繰り返し構造単位Ａ、Ｂ及びＸ２を含むアルカリ可溶性樹脂５を合成した。
加熱冷却・撹拌装置、還流冷却管、及び窒素導入管を備えたガラス製フラスコに、グリシジルメタクリレート１００ｇ、及びプロピレングリコールモノメチルエーテルアセテート１６０ｇを仕込んだ。系内の気相部分を窒素で置換したのち、２，２’－アゾビス（２，４－ジメチルバレロニトリル）７．５ｇを添加し、８０℃で加熱し、同温度で８時間反応させた。得られた溶液に、更にアクリル酸５３．２ｇ、トリフェニルホスフィン０．３ｇ、及びハイドロキノン０．０２ｇを添加し、１００℃で１５時間反応させた。反応後、反応溶液に更に２－イソシアネートエチルメタクリレート（昭和電工社製、カレンズＭＯＩ）８７ｇ、ハイドロキノン０．０１ｇ、及びＮ，Ｎ’－ジメチルベンジルアミン０．１ｇを添加し、６５℃で１５時間反応させてた。反応後、反応溶液に更にチオグリコール酸２６．０ｇ、プロピレングリコールモノメチルエーテルアセテート５０ｇ、ハイドロキノン０．００３ｇ、メトキノン０．５ｇ、及びＮ，Ｎ’－ジメチルベンジルアミン０．５ｇを添加し、７０℃で２０時間反応させて、アルカリ可溶性樹脂５を５０質量％含む溶液を得た。ＧＰＣにて分子量測定した結果、アルカリ可溶性樹脂５の重量平均分子量（Ｍｗ）は２８，０００であった。また、アルカリ可溶性樹脂５の酸価は５９ｍｇＫＯＨ／ｇであった。
[Synthesis Example 5] Synthesis of Alkali-Soluble Resin 5 Alkali-soluble resin 5 containing the following repeating structural units A, B and X2 was synthesized by the following production method.
100 g of glycidyl methacrylate and 160 g of propylene glycol monomethyl ether acetate were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. After the gas phase in the system was replaced with nitrogen, 7.5 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated at 80°C, and reacted at the same temperature for 8 hours. Further, 53.2 g of acrylic acid, 0.3 g of triphenylphosphine, and 0.02 g of hydroquinone were added to the resulting solution and reacted at 100° C. for 15 hours. After the reaction, 87 g of 2-isocyanatoethyl methacrylate (manufactured by Showa Denko, Karenz MOI), 0.01 g of hydroquinone, and 0.1 g of N,N'-dimethylbenzylamine were further added to the reaction solution, and reacted at 65°C for 15 hours. I let you After the reaction, 26.0 g of thioglycolic acid, 50 g of propylene glycol monomethyl ether acetate, 0.003 g of hydroquinone, 0.5 g of methoquinone, and 0.5 g of N,N'-dimethylbenzylamine were further added to the reaction solution, and the mixture was stirred at 70°C. After reacting for 20 hours, a solution containing 50% by mass of alkali-soluble resin 5 was obtained. As a result of molecular weight measurement by GPC, the weight average molecular weight (Mw) of alkali-soluble resin 5 was 28,000. Moreover, the acid value of the alkali-soluble resin 5 was 59 mgKOH/g.
下記の製造方法により、下記の繰り返し構造単位Ａ、Ｂ及びＸ２を含むアルカリ可溶性樹脂５を合成した。
［合成例６］アルカリ可溶性樹脂６の合成
下記の製造方法により、下記の繰り返し構造単位Ａ及びＸ３を含むアルカリ可溶性樹脂６を合成した。
加熱冷却・撹拌装置、還流冷却管、及び窒素導入管を備えたガラス製フラスコに、グリシジルメタクリレート１００ｇ、及びプロピレングリコールモノメチルエーテルアセテート２１２ｇを仕込んだ。系内の気相部分を窒素で置換したのち、２，２’－アゾビス（２，４－ジメチルバレロニトリル）１７ｇを添加し、８０℃で加熱し、同温度で８時間反応させた。得られた溶液に、更にアクリル酸５３．２ｇ、トリフェニルホスフィン１．０ｇ、ハイドロキノン０．０２ｇ、及びプロピレングリコールモノメチルエーテルアセテート６．０ｇを添加し、１００℃で１６時間反応させた。反応後、反応溶液に更に５－ノルボルネン－２，３－ジカルボン酸無水物を１８．２ｇ、及びプロピレングリコールモノメチルエーテルアセテート３１．０ｇを添加し、６５℃で１９時間反応させて、アクリル可溶性樹脂６を４５質量％含む溶液を得た。ＧＰＣにて分子量測定した結果、アルカリ可溶性樹脂６の重量平均分子量（Ｍｗ）は８，０００であった。また、アルカリ可溶性樹脂６の酸価は５８ｍｇＫＯＨ／ｇであった。
[Synthesis Example 6] Synthesis of Alkali-Soluble Resin 6 Alkali-soluble resin 6 containing the following repeating structural units A and X3 was synthesized by the following production method.
100 g of glycidyl methacrylate and 212 g of propylene glycol monomethyl ether acetate were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. After the gas phase in the system was replaced with nitrogen, 17 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated at 80°C, and reacted at the same temperature for 8 hours. Further, 53.2 g of acrylic acid, 1.0 g of triphenylphosphine, 0.02 g of hydroquinone, and 6.0 g of propylene glycol monomethyl ether acetate were added to the obtained solution and reacted at 100° C. for 16 hours. After the reaction, 18.2 g of 5-norbornene-2,3-dicarboxylic anhydride and 31.0 g of propylene glycol monomethyl ether acetate were further added to the reaction solution and reacted at 65° C. for 19 hours to obtain acrylic soluble resin 6. A solution containing 45% by mass of was obtained. As a result of molecular weight measurement by GPC, the weight average molecular weight (Mw) of alkali-soluble resin 6 was 8,000. Moreover, the acid value of the alkali-soluble resin 6 was 58 mgKOH/g.
下記の製造方法により、下記の繰り返し構造単位Ａ及びＸ３を含むアルカリ可溶性樹脂６を合成した。
［合成例７］アルカリ可溶性樹脂７の合成
加熱冷却・撹拌装置、還流冷却管、及び窒素導入管を備えたガラス製フラスコに、メタクリル酸２５．０ｇ、メタクリル酸メチル１２．８ｇ、ジシクロペンタニルメタクリレート２０．２ｇ、及びプロピレングリコールモノメチルエーテルアセテート９４．６ｇを入れたのち、２，２’－アゾビス（２，４－ジメチルバレロニトリル）６．４ｇを添加し、窒素雰囲気下、８０℃で８時間反応させた。得られた溶液に、更にグリシジルメタクリレート１２．３ｇ、ハイドロキノン０．２ｇ、及びプロピレングリコールモノメチルエーテルアセテート２．５ｇを添加し、１００℃で１９時間反応させて、アルカリ可溶性樹脂７を４５質量％含む溶液を得た。ＧＰＣにて分子量測定した結果、アルカリ可溶性樹脂７の重量平均分子量（Ｍｗ）は１１，８００であった。また、アルカリ可溶性樹脂７の酸価は１０７ｍｇＫＯＨ／ｇであった。 [Synthesis Example 7] Synthesis of alkali-soluble resin 7 In a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube, 25.0 g of methacrylic acid, 12.8 g of methyl methacrylate, and dicyclopentanyl were added. After adding 20.2 g of methacrylate and 94.6 g of propylene glycol monomethyl ether acetate, 6.4 g of 2,2′-azobis(2,4-dimethylvaleronitrile) was added, and the mixture was stirred at 80° C. for 8 hours under a nitrogen atmosphere. reacted. 12.3 g of glycidyl methacrylate, 0.2 g of hydroquinone, and 2.5 g of propylene glycol monomethyl ether acetate were further added to the obtained solution, and reacted at 100° C. for 19 hours to obtain a solution containing 45% by mass of alkali-soluble resin 7. got As a result of molecular weight measurement by GPC, the weight average molecular weight (Mw) of alkali-soluble resin 7 was 11,800. Moreover, the acid value of the alkali-soluble resin 7 was 107 mgKOH/g.
加熱冷却・撹拌装置、還流冷却管、及び窒素導入管を備えたガラス製フラスコに、メタクリル酸２５．０ｇ、メタクリル酸メチル１２．８ｇ、ジシクロペンタニルメタクリレート２０．２ｇ、及びプロピレングリコールモノメチルエーテルアセテート９４．６ｇを入れたのち、２，２’－アゾビス（２，４－ジメチルバレロニトリル）６．４ｇを添加し、窒素雰囲気下、８０℃で８時間反応させた。得られた溶液に、更にグリシジルメタクリレート１２．３ｇ、ハイドロキノン０．２ｇ、及びプロピレングリコールモノメチルエーテルアセテート２．５ｇを添加し、１００℃で１９時間反応させて、アルカリ可溶性樹脂７を４５質量％含む溶液を得た。ＧＰＣにて分子量測定した結果、アルカリ可溶性樹脂７の重量平均分子量（Ｍｗ）は１１，８００であった。また、アルカリ可溶性樹脂７の酸価は１０７ｍｇＫＯＨ／ｇであった。 [Synthesis Example 7] Synthesis of alkali-soluble resin 7 In a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube, 25.0 g of methacrylic acid, 12.8 g of methyl methacrylate, and dicyclopentanyl were added. After adding 20.2 g of methacrylate and 94.6 g of propylene glycol monomethyl ether acetate, 6.4 g of 2,2′-azobis(2,4-dimethylvaleronitrile) was added, and the mixture was stirred at 80° C. for 8 hours under a nitrogen atmosphere. reacted. 12.3 g of glycidyl methacrylate, 0.2 g of hydroquinone, and 2.5 g of propylene glycol monomethyl ether acetate were further added to the obtained solution, and reacted at 100° C. for 19 hours to obtain a solution containing 45% by mass of alkali-soluble resin 7. got As a result of molecular weight measurement by GPC, the weight average molecular weight (Mw) of alkali-soluble resin 7 was 11,800. Moreover, the acid value of the alkali-soluble resin 7 was 107 mgKOH/g.
［合成例８］アルカリ可溶性樹脂８の合成
加熱冷却・撹拌装置、還流冷却管、及び窒素導入管を備えたガラス製フラスコに、メタクリル酸２５．０ｇ、メタクリル酸メチル２２．６ｇ、メタクリル酸ブチル１８．４ｇ、及びプロピレングリコールモノメチルエーテルアセテート９９．０ｇを入れたのち、２，２’－アゾビス（２，４－ジメチルバレロニトリル）５．６ｇを添加し、窒素雰囲気下、８０℃で８時間反応させた。得られた溶液に、更にグリシジルメタクリレート１８．４ｇ、ハイドロキノン０．２ｇ、及びプロピレングリコールモノメチルエーテルアセテート４．３ｇを添加し、１００℃で１９時間反応させて、アルカリ可溶性樹脂８を４５質量％含む溶液を得た。ＧＰＣにて分子量測定した結果、アルカリ可溶性樹脂８の重量平均分子量（Ｍｗ）は１０，８００であった。また、アルカリ可溶性樹脂８の酸価は１０６ｍｇＫＯＨ／ｇであった。 [Synthesis Example 8] Synthesis of alkali-soluble resin 8 In a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube, 25.0 g of methacrylic acid, 22.6 g of methyl methacrylate, and 18 g of butyl methacrylate were added. .4 g and 99.0 g of propylene glycol monomethyl ether acetate were added, then 5.6 g of 2,2′-azobis(2,4-dimethylvaleronitrile) was added and reacted at 80° C. for 8 hours under a nitrogen atmosphere. rice field. Further, 18.4 g of glycidyl methacrylate, 0.2 g of hydroquinone, and 4.3 g of propylene glycol monomethyl ether acetate were added to the obtained solution and reacted at 100° C. for 19 hours to obtain a solution containing 45% by mass of alkali-soluble resin 8. got As a result of molecular weight measurement by GPC, the weight average molecular weight (Mw) of alkali-soluble resin 8 was 10,800. Moreover, the acid value of the alkali-soluble resin 8 was 106 mgKOH/g.
加熱冷却・撹拌装置、還流冷却管、及び窒素導入管を備えたガラス製フラスコに、メタクリル酸２５．０ｇ、メタクリル酸メチル２２．６ｇ、メタクリル酸ブチル１８．４ｇ、及びプロピレングリコールモノメチルエーテルアセテート９９．０ｇを入れたのち、２，２’－アゾビス（２，４－ジメチルバレロニトリル）５．６ｇを添加し、窒素雰囲気下、８０℃で８時間反応させた。得られた溶液に、更にグリシジルメタクリレート１８．４ｇ、ハイドロキノン０．２ｇ、及びプロピレングリコールモノメチルエーテルアセテート４．３ｇを添加し、１００℃で１９時間反応させて、アルカリ可溶性樹脂８を４５質量％含む溶液を得た。ＧＰＣにて分子量測定した結果、アルカリ可溶性樹脂８の重量平均分子量（Ｍｗ）は１０，８００であった。また、アルカリ可溶性樹脂８の酸価は１０６ｍｇＫＯＨ／ｇであった。 [Synthesis Example 8] Synthesis of alkali-soluble resin 8 In a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube, 25.0 g of methacrylic acid, 22.6 g of methyl methacrylate, and 18 g of butyl methacrylate were added. .4 g and 99.0 g of propylene glycol monomethyl ether acetate were added, then 5.6 g of 2,2′-azobis(2,4-dimethylvaleronitrile) was added and reacted at 80° C. for 8 hours under a nitrogen atmosphere. rice field. Further, 18.4 g of glycidyl methacrylate, 0.2 g of hydroquinone, and 4.3 g of propylene glycol monomethyl ether acetate were added to the obtained solution and reacted at 100° C. for 19 hours to obtain a solution containing 45% by mass of alkali-soluble resin 8. got As a result of molecular weight measurement by GPC, the weight average molecular weight (Mw) of alkali-soluble resin 8 was 10,800. Moreover, the acid value of the alkali-soluble resin 8 was 106 mgKOH/g.
［合成例９］アルカリ可溶性樹脂９の合成
加熱冷却・撹拌装置、還流冷却管、及び窒素導入管を備えたガラス製フラスコに、グリシジルメタクリレート１００ｇ、及びプロピレングリコールモノメチルエーテルアセテート２１２ｇを仕込んだ。系内の気相部分を窒素で置換したのち、２，２’－アゾビス（２，４－ジメチルバレロニトリル）１７ｇを添加し、８０℃で加熱し、同温度で８時間反応させた。得られた溶液に、更にアクリル酸５３．２ｇ、トリフェニルホスフィン１．０ｇ、ハイドロキノン０．０２ｇ、及びプロピレングリコールモノメチルエーテルアセテート６．０ｇを添加し、１００℃で１２時間反応させて、アルカリ可溶性樹脂９を４４質量％含む溶液を得た。ＧＰＣにて分子量測定した結果、アルカリ可溶性樹脂９の重量平均分子量（Ｍｗ）は９，０００であった。また、アルカリ可溶性樹脂９の酸価は１２ｍｇＫＯＨ／ｇであった。 [Synthesis Example 9] Synthesis of Alkali-Soluble Resin 9 100 g of glycidyl methacrylate and 212 g of propylene glycol monomethyl ether acetate were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. After the gas phase in the system was replaced with nitrogen, 17 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated at 80°C, and reacted at the same temperature for 8 hours. Further, 53.2 g of acrylic acid, 1.0 g of triphenylphosphine, 0.02 g of hydroquinone, and 6.0 g of propylene glycol monomethyl ether acetate were added to the obtained solution and reacted at 100° C. for 12 hours to obtain an alkali-soluble resin. A solution containing 44% by mass of 9 was obtained. As a result of molecular weight measurement by GPC, the weight average molecular weight (Mw) of alkali-soluble resin 9 was 9,000. Moreover, the acid value of the alkali-soluble resin 9 was 12 mgKOH/g.
加熱冷却・撹拌装置、還流冷却管、及び窒素導入管を備えたガラス製フラスコに、グリシジルメタクリレート１００ｇ、及びプロピレングリコールモノメチルエーテルアセテート２１２ｇを仕込んだ。系内の気相部分を窒素で置換したのち、２，２’－アゾビス（２，４－ジメチルバレロニトリル）１７ｇを添加し、８０℃で加熱し、同温度で８時間反応させた。得られた溶液に、更にアクリル酸５３．２ｇ、トリフェニルホスフィン１．０ｇ、ハイドロキノン０．０２ｇ、及びプロピレングリコールモノメチルエーテルアセテート６．０ｇを添加し、１００℃で１２時間反応させて、アルカリ可溶性樹脂９を４４質量％含む溶液を得た。ＧＰＣにて分子量測定した結果、アルカリ可溶性樹脂９の重量平均分子量（Ｍｗ）は９，０００であった。また、アルカリ可溶性樹脂９の酸価は１２ｍｇＫＯＨ／ｇであった。 [Synthesis Example 9] Synthesis of Alkali-Soluble Resin 9 100 g of glycidyl methacrylate and 212 g of propylene glycol monomethyl ether acetate were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. After the gas phase in the system was replaced with nitrogen, 17 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated at 80°C, and reacted at the same temperature for 8 hours. Further, 53.2 g of acrylic acid, 1.0 g of triphenylphosphine, 0.02 g of hydroquinone, and 6.0 g of propylene glycol monomethyl ether acetate were added to the obtained solution and reacted at 100° C. for 12 hours to obtain an alkali-soluble resin. A solution containing 44% by mass of 9 was obtained. As a result of molecular weight measurement by GPC, the weight average molecular weight (Mw) of alkali-soluble resin 9 was 9,000. Moreover, the acid value of the alkali-soluble resin 9 was 12 mgKOH/g.
［合成例１０］アルカリ可溶性樹脂１０の合成
５－ノルボルネン－２，３－ジカルボン酸無水物１８．２ｇの代わりにトリメリット酸無水物１４．２ｇを添加し、プロピレングリコールモノメチルエーテルアセテートの添加量を３１．０ｇから２６．２ｇに変更した以外は、合成例６と同様の製造方法でアルカリ可溶性樹脂１０を４５質量％含む溶液を得た。ＧＰＣにて分子量測定した結果、アルカリ可溶性樹脂１０の重量平均分子量（Ｍｗ）は１６，０００であった。また、アルカリ可溶性樹脂１０の酸価は６２ｍｇＫＯＨ／ｇであった。 [Synthesis Example 10] Synthesis of alkali-soluble resin 10 Instead of 18.2 g of 5-norbornene-2,3-dicarboxylic anhydride, 14.2 g of trimellitic anhydride was added, and the amount of propylene glycol monomethyl ether acetate added was A solution containing 45% by mass of alkali-soluble resin 10 was obtained in the same production method as in Synthesis Example 6, except that the amount was changed from 31.0 g to 26.2 g. As a result of molecular weight measurement by GPC, the weight average molecular weight (Mw) of the alkali-soluble resin 10 was 16,000. Moreover, the acid value of the alkali-soluble resin 10 was 62 mgKOH/g.
５－ノルボルネン－２，３－ジカルボン酸無水物１８．２ｇの代わりにトリメリット酸無水物１４．２ｇを添加し、プロピレングリコールモノメチルエーテルアセテートの添加量を３１．０ｇから２６．２ｇに変更した以外は、合成例６と同様の製造方法でアルカリ可溶性樹脂１０を４５質量％含む溶液を得た。ＧＰＣにて分子量測定した結果、アルカリ可溶性樹脂１０の重量平均分子量（Ｍｗ）は１６，０００であった。また、アルカリ可溶性樹脂１０の酸価は６２ｍｇＫＯＨ／ｇであった。 [Synthesis Example 10] Synthesis of alkali-soluble resin 10 Instead of 18.2 g of 5-norbornene-2,3-dicarboxylic anhydride, 14.2 g of trimellitic anhydride was added, and the amount of propylene glycol monomethyl ether acetate added was A solution containing 45% by mass of alkali-soluble resin 10 was obtained in the same production method as in Synthesis Example 6, except that the amount was changed from 31.0 g to 26.2 g. As a result of molecular weight measurement by GPC, the weight average molecular weight (Mw) of the alkali-soluble resin 10 was 16,000. Moreover, the acid value of the alkali-soluble resin 10 was 62 mgKOH/g.
実施例１～７、及び比較例１～３
[感光性樹脂組成物の調製]
アルカリ可溶性樹脂１を４５質量％含む前記溶液１００質量部、ジペンタエリスリトールヘキサアクリレート（日本化薬社製、ＫＡＹＡＲＡＤ ＤＰＨＡ）６０質量部、光重合開始剤（ＬＡＭＢＳＯＮ社製、ＳＰＥＥＤＣＵＲＥ ＴＰＯ）１．６質量部、光重合開始剤（ＢＡＳＦジャパン株式会社、Ｉｒｇａｃｕｒｅ ＯＸＥ０１）１．０質量部、及び界面活性剤（ＢＹＫ製、ＢＹＫ－３０７）０．２質量部を混合して、組成物中の固形分が５０％である感光性樹脂組成物を調製した（実施例１）。アルカリ可溶性樹脂１を４５質量％含む前記溶液１００質量部の代わりに、アルカリ可溶性樹脂２～１０を前記各質量％含む前記各溶液１００質量部を用いた以外は、上記と同様の方法で、組成物中の固形分が５０％である感光性樹脂組成物を調製した（実施例２～７及び比較例１～３）。 Examples 1-7 and Comparative Examples 1-3
[Preparation of photosensitive resin composition]
100 parts by mass of the solution containing 45% by mass of the alkali-soluble resin 1, 60 parts by mass of dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.), 1.6 parts by mass of a photopolymerization initiator (SPEEDCURE TPO manufactured by LAMBSON) part, a photopolymerization initiator (BASF Japan Ltd., Irgacure OXE01) 1.0 parts by mass, and a surfactant (manufactured by BYK, BYK-307) 0.2 parts by mass, and the solid content in the composition is A photosensitive resin composition of 50% was prepared (Example 1). Instead of 100 parts by mass of the solution containing 45% by mass of alkali-soluble resin 1, 100 parts by mass of each of the solutions containing 2 to 10 of each of the alkali-soluble resins 2 to 10 were used. A photosensitive resin composition having a solid content of 50% was prepared (Examples 2 to 7 and Comparative Examples 1 to 3).
[感光性樹脂組成物の調製]
アルカリ可溶性樹脂１を４５質量％含む前記溶液１００質量部、ジペンタエリスリトールヘキサアクリレート（日本化薬社製、ＫＡＹＡＲＡＤ ＤＰＨＡ）６０質量部、光重合開始剤（ＬＡＭＢＳＯＮ社製、ＳＰＥＥＤＣＵＲＥ ＴＰＯ）１．６質量部、光重合開始剤（ＢＡＳＦジャパン株式会社、Ｉｒｇａｃｕｒｅ ＯＸＥ０１）１．０質量部、及び界面活性剤（ＢＹＫ製、ＢＹＫ－３０７）０．２質量部を混合して、組成物中の固形分が５０％である感光性樹脂組成物を調製した（実施例１）。アルカリ可溶性樹脂１を４５質量％含む前記溶液１００質量部の代わりに、アルカリ可溶性樹脂２～１０を前記各質量％含む前記各溶液１００質量部を用いた以外は、上記と同様の方法で、組成物中の固形分が５０％である感光性樹脂組成物を調製した（実施例２～７及び比較例１～３）。 Examples 1-7 and Comparative Examples 1-3
[Preparation of photosensitive resin composition]
100 parts by mass of the solution containing 45% by mass of the alkali-soluble resin 1, 60 parts by mass of dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.), 1.6 parts by mass of a photopolymerization initiator (SPEEDCURE TPO manufactured by LAMBSON) part, a photopolymerization initiator (BASF Japan Ltd., Irgacure OXE01) 1.0 parts by mass, and a surfactant (manufactured by BYK, BYK-307) 0.2 parts by mass, and the solid content in the composition is A photosensitive resin composition of 50% was prepared (Example 1). Instead of 100 parts by mass of the solution containing 45% by mass of alkali-soluble resin 1, 100 parts by mass of each of the solutions containing 2 to 10 of each of the alkali-soluble resins 2 to 10 were used. A photosensitive resin composition having a solid content of 50% was prepared (Examples 2 to 7 and Comparative Examples 1 to 3).
［現像性の評価］
１０ｃｍ×１０ｃｍ四方の各ガラス基板上に、スピンコーターを用いて実施例１～７及び比較例１～３で調製した感光性樹脂組成物をそれぞれ塗布して膜厚３０μｍの塗膜を形成し、当該塗膜を９０℃のホットプレート上で２分間加熱して溶剤を完全に除去した。その後、得られた塗膜に対して、０．３％Ｎａ２ＣＯ３水溶液を用いてアルカリ現像を行い、塗膜が溶解除去される時間を最短現像時間として現像性の評価を行った。この値が小さいほど現像性に優れているといえる。以下の基準によりランク分けした。
Ａ：最短現像時間が６０秒以内
Ｂ：最短現像時間が６０秒超８０秒以内
Ｃ：最短現像時間が８０秒超１００秒以内
Ｆ：最短現像時間が１００秒超 [Evaluation of developability]
The photosensitive resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 3 were each applied onto each glass substrate of 10 cm×10 cm square using a spin coater to form a coating film having a thickness of 30 μm, The coating film was heated on a hot plate at 90° C. for 2 minutes to completely remove the solvent. After that, the obtained coating film was subjected to alkali development using a 0.3% Na 2 CO 3 aqueous solution, and developability was evaluated with the shortest development time being the time required for the coating film to be dissolved and removed. It can be said that the smaller this value, the better the developability. They were ranked according to the following criteria.
A: Shortest development time within 60 seconds B: Shortest development time over 60 seconds and within 80 seconds C: Shortest development time over 80 seconds and within 100 seconds F: Shortest development time over 100 seconds
１０ｃｍ×１０ｃｍ四方の各ガラス基板上に、スピンコーターを用いて実施例１～７及び比較例１～３で調製した感光性樹脂組成物をそれぞれ塗布して膜厚３０μｍの塗膜を形成し、当該塗膜を９０℃のホットプレート上で２分間加熱して溶剤を完全に除去した。その後、得られた塗膜に対して、０．３％Ｎａ２ＣＯ３水溶液を用いてアルカリ現像を行い、塗膜が溶解除去される時間を最短現像時間として現像性の評価を行った。この値が小さいほど現像性に優れているといえる。以下の基準によりランク分けした。
Ａ：最短現像時間が６０秒以内
Ｂ：最短現像時間が６０秒超８０秒以内
Ｃ：最短現像時間が８０秒超１００秒以内
Ｆ：最短現像時間が１００秒超 [Evaluation of developability]
The photosensitive resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 3 were each applied onto each glass substrate of 10 cm×10 cm square using a spin coater to form a coating film having a thickness of 30 μm, The coating film was heated on a hot plate at 90° C. for 2 minutes to completely remove the solvent. After that, the obtained coating film was subjected to alkali development using a 0.3% Na 2 CO 3 aqueous solution, and developability was evaluated with the shortest development time being the time required for the coating film to be dissolved and removed. It can be said that the smaller this value, the better the developability. They were ranked according to the following criteria.
A: Shortest development time within 60 seconds B: Shortest development time over 60 seconds and within 80 seconds C: Shortest development time over 80 seconds and within 100 seconds F: Shortest development time over 100 seconds
［フォトスペーサーの作製］
１０ｃｍ×１０ｃｍ四方の各ガラス基板上に、スピンコーターを用いて実施例１～７及び比較例１～３で調製した各感光性樹脂組成物を、スピンコーターの回転数を調整して形成後のフォトスペーサーの高さが３０μｍになるように塗布して塗膜をそれぞれ形成し、各塗膜を１００℃のホットプレート上で２分間加熱して溶剤を完全に除去した。その後、得られた各塗膜に対して、１ｃｍ２あたり１００個、直径４～３０μｍまで１μｍ刻みで開口部を有するフォトスペーサー形成用マスクを通して、超高圧水銀灯の光を１００ｍＪ／ｃｍ２照射した（ｉ線換算で照度２１ｍＷ／ｃｍ２）。なお、マスクと基板との間隔（露光ギャップ）は１００μｍにて露光を行った。その後、０．３％Ｎａ２ＣＯ３水溶液を用いてアルカリ現像を行った。現像時間は前述の方法で測定した最短現像時間の１．５倍とした。水洗したのち、２３０℃で３０分間ポストベークを行い、フォトスペーサーを形成した。 [Production of photospacer]
On each glass substrate of 10 cm × 10 cm square, each photosensitive resin composition prepared in Examples 1 to 7 and Comparative Examples 1 to 3 using a spin coater, after adjusting the rotation speed of the spin coater. Each coating film was formed by coating so that the height of the photospacer was 30 μm, and each coating film was heated on a hot plate at 100° C. for 2 minutes to completely remove the solvent. After that, each of the obtained coating films was irradiated with 100 mJ/cm 2 of light from an ultra-high pressure mercury lamp through a photospacer forming mask having 100 openings per 1 cm 2 with a diameter of 4 to 30 μm in increments of 1 μm ( i-line conversion illuminance 21 mW/cm 2 ). The distance (exposure gap) between the mask and the substrate was set to 100 μm for exposure. After that, alkali development was performed using a 0.3% Na 2 CO 3 aqueous solution. The development time was set to 1.5 times the shortest development time measured by the method described above. After washing with water, post-baking was performed at 230° C. for 30 minutes to form a photospacer.
１０ｃｍ×１０ｃｍ四方の各ガラス基板上に、スピンコーターを用いて実施例１～７及び比較例１～３で調製した各感光性樹脂組成物を、スピンコーターの回転数を調整して形成後のフォトスペーサーの高さが３０μｍになるように塗布して塗膜をそれぞれ形成し、各塗膜を１００℃のホットプレート上で２分間加熱して溶剤を完全に除去した。その後、得られた各塗膜に対して、１ｃｍ２あたり１００個、直径４～３０μｍまで１μｍ刻みで開口部を有するフォトスペーサー形成用マスクを通して、超高圧水銀灯の光を１００ｍＪ／ｃｍ２照射した（ｉ線換算で照度２１ｍＷ／ｃｍ２）。なお、マスクと基板との間隔（露光ギャップ）は１００μｍにて露光を行った。その後、０．３％Ｎａ２ＣＯ３水溶液を用いてアルカリ現像を行った。現像時間は前述の方法で測定した最短現像時間の１．５倍とした。水洗したのち、２３０℃で３０分間ポストベークを行い、フォトスペーサーを形成した。 [Production of photospacer]
On each glass substrate of 10 cm × 10 cm square, each photosensitive resin composition prepared in Examples 1 to 7 and Comparative Examples 1 to 3 using a spin coater, after adjusting the rotation speed of the spin coater. Each coating film was formed by coating so that the height of the photospacer was 30 μm, and each coating film was heated on a hot plate at 100° C. for 2 minutes to completely remove the solvent. After that, each of the obtained coating films was irradiated with 100 mJ/cm 2 of light from an ultra-high pressure mercury lamp through a photospacer forming mask having 100 openings per 1 cm 2 with a diameter of 4 to 30 μm in increments of 1 μm ( i-line conversion illuminance 21 mW/cm 2 ). The distance (exposure gap) between the mask and the substrate was set to 100 μm for exposure. After that, alkali development was performed using a 0.3% Na 2 CO 3 aqueous solution. The development time was set to 1.5 times the shortest development time measured by the method described above. After washing with water, post-baking was performed at 230° C. for 30 minutes to form a photospacer.
［現像密着性の評価］
前述の方法で形成したフォトスペーサーのうち、現像で除去されることなく形成されている最小のパターンの線幅を現像密着性として評価を行った。この値が小さいほど現像密着性に優れているといえる。以下の基準によりランク分けした。
Ａ：最小パターンが１５μｍ未満
Ｂ：最小パターンが１５μｍ以上２０μｍ未満
Ｃ：最小パターンが２０μｍ以上
Ｆ：現像不可 [Evaluation of development adhesion]
Among the photospacers formed by the above-described method, the line width of the smallest pattern formed without being removed by development was evaluated as development adhesion. It can be said that the smaller this value, the better the development adhesion. They were ranked according to the following criteria.
A: The minimum pattern is less than 15 μm B: The minimum pattern is 15 μm or more and less than 20 μm C: The minimum pattern is 20 μm or more F: Undevelopable
前述の方法で形成したフォトスペーサーのうち、現像で除去されることなく形成されている最小のパターンの線幅を現像密着性として評価を行った。この値が小さいほど現像密着性に優れているといえる。以下の基準によりランク分けした。
Ａ：最小パターンが１５μｍ未満
Ｂ：最小パターンが１５μｍ以上２０μｍ未満
Ｃ：最小パターンが２０μｍ以上
Ｆ：現像不可 [Evaluation of development adhesion]
Among the photospacers formed by the above-described method, the line width of the smallest pattern formed without being removed by development was evaluated as development adhesion. It can be said that the smaller this value, the better the development adhesion. They were ranked according to the following criteria.
A: The minimum pattern is less than 15 μm B: The minimum pattern is 15 μm or more and less than 20 μm C: The minimum pattern is 20 μm or more F: Undevelopable
表１の結果から、パターン高さが３０μｍ程度である厚膜パターンの形成において弱アルカリ現像液を使用した場合、実施例１～７の感光性樹脂組成物は、比較例１～３の感光性樹脂組成物に比べて短時間で現像できており、かつ現像密着性に優れる硬化膜を形成できていることがわかる。
From the results of Table 1, when a weak alkaline developer is used in forming a thick film pattern having a pattern height of about 30 μm, the photosensitive resin compositions of Examples 1 to 7 have the same photosensitive properties as those of Comparative Examples 1 to 3. It can be seen that development can be completed in a shorter time than with the resin composition, and a cured film having excellent development adhesion can be formed.
本発明のアルカリ可溶性樹脂、及び当該アルカリ可溶性樹脂を含有する感光性樹脂組成物は、フォトスペーサー、隔壁材、レンズ材、層間絶縁膜材、保護膜材、光導波路材、又は平坦化膜材の原料として好適に用いられる。
The alkali-soluble resin of the present invention and the photosensitive resin composition containing the alkali-soluble resin can be used as a photospacer, a partition wall material, a lens material, an interlayer insulating film material, a protective film material, an optical waveguide material, or a flattening film material. It is suitably used as a raw material.
Claims (14)
- 下記一般式（１）で表される繰り返し構造単位Ｘを１種以上含むアルカリ可溶性樹脂。
- 下記一般式（１’）で表される繰り返し構造単位Ｘ’を１種以上含む、ただし、各々がラジカル重合性置換基に終わる２～３個の末端を有する分岐した側鎖を備えた繰り返し構造単位を含まない、アルカリ可溶性樹脂。
- 前記Ｒ２の連結基は、母体の炭素数が１～１０の炭化水素基、又は母体の炭素数が１～１０であり、かつヘテロ原子を含む有機基である、請求項１又は２に記載のアルカリ可溶性樹脂。 3. The linking group of R 2 according to claim 1 or 2, wherein the base is a hydrocarbon group having 1 to 10 carbon atoms or an organic group having 1 to 10 carbon atoms and containing a hetero atom. alkali-soluble resin.
- 前記Ｒ４の有機基は、アクリロイルオキシ基、メタクリロイルオキシ基、アシルオキシ基、アミドオキシ基、アルコキシ基、アリールオキシ基、アミノ基、及び含窒素複素環からなる群より選択される１種以上の官能基を含む有機基である、請求項１～３のいずれかに記載のアルカリ可溶性樹脂。 The organic group for R4 is one or more functional groups selected from the group consisting of acryloyloxy, methacryloyloxy, acyloxy, amidooxy, alkoxy, aryloxy, amino, and nitrogen-containing heterocycles. The alkali-soluble resin according to any one of claims 1 to 3, which is an organic group containing.
- 前記Ｒ２の連結基は、母体の炭素数が１～７の炭化水素基、又は母体の炭素数が１～７であり、かつヘテロ原子を含む有機基であり、
前記Ｒ４は、前記Ｒ２の連結基の炭素原子に結合するヒドロキシ基、アクリロイルオキシ基、又はメタクリロイルオキシ基である、請求項１又は２に記載のアルカリ可溶性樹脂。 The linking group of R 2 is a hydrocarbon group having 1 to 7 carbon atoms in the base, or an organic group having 1 to 7 carbon atoms in the base and containing a hetero atom,
The alkali-soluble resin according to claim 1 or 2 , wherein said R4 is a hydroxy group, an acryloyloxy group, or a methacryloyloxy group bonded to the carbon atom of the linking group of said R2. - 前記Ｒ２の連結基は、母体の炭素数が１～７の炭化水素基、又は母体の炭素数が１～７であり、かつヘテロ原子を含む有機基であり、
前記Ｒ５は、下記一般式（３）で表される有機基であり、
前記Ｒ４は、前記Ｒ２の連結基の炭素原子に結合するヒドロキシ基、アクリロイルオキシ基、メタクリロイルオキシ基、又は下記一般式（４）で表される有機基である、請求項１に記載のアルカリ可溶性樹脂。
R 5 is an organic group represented by the following general formula (3),
2. The R 4 according to claim 1, wherein R 2 is a hydroxy group, an acryloyloxy group, a methacryloyloxy group, or an organic group represented by the following general formula (4), which is bonded to the carbon atom of the linking group of R 2 . Alkali-soluble resin.
- 前記Ｒ２の連結基は、母体の炭素数が１～７の炭化水素基、又は母体の炭素数が１～７であり、かつヘテロ原子を含む有機基であり、
前記Ｒ５’は、下記一般式（３）で表される有機基であり、
前記Ｒ４は、前記Ｒ２の連結基の炭素原子に結合するヒドロキシ基、アクリロイルオキシ基、メタクリロイルオキシ基、又は下記一般式（４）で表される有機基である、請求項２に記載のアルカリ可溶性樹脂。
The R 5' is an organic group represented by the following general formula (3),
3. The R 4 according to claim 2, wherein R 2 is a hydroxy group, an acryloyloxy group, a methacryloyloxy group, or an organic group represented by the following general formula (4), which is bonded to the carbon atom of the linking group of R 2 . Alkali-soluble resin.
- 前記繰り返し構造単位Ｘ又はＸ’の含有量は、全繰り返し構造単位中に５～５０ｍｏｌ％である請求項１～７のいずれかに記載のアルカリ可溶性樹脂。 The alkali-soluble resin according to any one of claims 1 to 7, wherein the content of the repeating structural unit X or X' is 5 to 50 mol% in all repeating structural units.
- 前記アルカリ可溶性樹脂は、酸価が２０～１２０ｍｇＫＯＨ／ｇである請求項１～８のいずれかに記載のアルカリ可溶性樹脂。 The alkali-soluble resin according to any one of claims 1 to 8, wherein the alkali-soluble resin has an acid value of 20 to 120 mgKOH/g.
- 前記アルカリ可溶性樹脂は、重量平均分子量が５０００～４００００である請求項１～９のいずれかに記載のアルカリ可溶性樹脂。 The alkali-soluble resin according to any one of claims 1 to 9, wherein the alkali-soluble resin has a weight average molecular weight of 5,000 to 40,000.
- 少なくとも請求項１～１０のいずれかに記載のアルカリ可溶性樹脂、重合性モノマー、及び光重合開始剤を含有する感光性樹脂組成物。 A photosensitive resin composition containing at least the alkali-soluble resin according to any one of claims 1 to 10, a polymerizable monomer, and a photopolymerization initiator.
- 請求項１１に記載の感光性樹脂組成物から得られる硬化物。 A cured product obtained from the photosensitive resin composition according to claim 11.
- 前記硬化物は、フォトスペーサー、隔壁材、レンズ材、層間絶縁膜材、保護膜材、光導波路材、又は平坦化膜材である請求項１２に記載の硬化物。 The cured product according to claim 12, wherein the cured product is a photospacer, partition wall material, lens material, interlayer insulating film material, protective film material, optical waveguide material, or flattening film material.
- 請求項１２又は１３に記載の硬化物を含む画像表示装置。 An image display device comprising the cured product according to claim 12 or 13.
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| KR1020237026699A KR20230128119A (en) | 2021-02-08 | 2022-02-07 | Alkali-soluble resin, photosensitive resin composition, cured product, and image display device |
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| JP2019124929A (en) | 2018-01-18 | 2019-07-25 | 東レ株式会社 | Negative photosensitive resin composition, and photospacer and image display device including the same |
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| JP2009138156A (en) * | 2007-12-10 | 2009-06-25 | Showa Highpolymer Co Ltd | Photosensitive resin and photosensitive resin composition |
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