CN117795420A - Photosensitive resin composition, cured product, and image display device - Google Patents
Photosensitive resin composition, cured product, and image display device Download PDFInfo
- Publication number
- CN117795420A CN117795420A CN202280053681.0A CN202280053681A CN117795420A CN 117795420 A CN117795420 A CN 117795420A CN 202280053681 A CN202280053681 A CN 202280053681A CN 117795420 A CN117795420 A CN 117795420A
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- China
- Prior art keywords
- meth
- crosslinkable
- monomer
- photosensitive resin
- resin composition
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 67
- 239000000178 monomer Substances 0.000 claims abstract description 204
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- 125000000524 functional group Chemical group 0.000 claims abstract description 104
- 229920005989 resin Polymers 0.000 claims abstract description 50
- 239000011347 resin Substances 0.000 claims abstract description 50
- 125000006850 spacer group Chemical group 0.000 claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 23
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 24
- 230000001681 protective effect Effects 0.000 claims description 5
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- 230000003287 optical effect Effects 0.000 claims description 3
- 238000005192 partition Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 28
- 239000001257 hydrogen Substances 0.000 description 48
- 229910052739 hydrogen Inorganic materials 0.000 description 48
- 239000000047 product Substances 0.000 description 40
- 239000010408 film Substances 0.000 description 30
- 239000000203 mixture Substances 0.000 description 27
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- 239000000758 substrate Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 15
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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 6
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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 5
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- 238000003825 pressing Methods 0.000 description 5
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
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- 238000003756 stirring Methods 0.000 description 4
- 229940014800 succinic anhydride Drugs 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
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- 125000003700 epoxy group Chemical group 0.000 description 3
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229940042596 viscoat Drugs 0.000 description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-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
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
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- 239000004593 Epoxy Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
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- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 2
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical class SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 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
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- VTLHIRNKQSFSJS-UHFFFAOYSA-N [3-(3-sulfanylbutanoyloxy)-2,2-bis(3-sulfanylbutanoyloxymethyl)propyl] 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCC(COC(=O)CC(C)S)(COC(=O)CC(C)S)COC(=O)CC(C)S VTLHIRNKQSFSJS-UHFFFAOYSA-N 0.000 description 1
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000007822 coupling agent Substances 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
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 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
- 125000004386 diacrylate group Chemical group 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 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
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 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
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 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
- 230000017525 heat dissipation Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002346 layers by function 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
- 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 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
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
-
- G—PHYSICS
- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials For Photolithography (AREA)
- Liquid Crystal (AREA)
Abstract
The invention provides a photosensitive resin composition capable of forming a cured product such as a photoresist spacer having both high elastic recovery rate and excellent flexibility, a cured product obtained from the photosensitive resin composition, and an image display device comprising the cured product. The photosensitive resin composition comprises: an alkali-soluble resin (A) having a double bond equivalent of 200g/mol or less; a monomer group (B) comprising a first crosslinkable (meth) acrylate monomer (B1) and a second crosslinkable (meth) acrylate monomer (B2) and having an acid value of 1mgKOH/g to 20mgKOH/g, wherein the first crosslinkable (meth) acrylate monomer (B1) has 6 or more crosslinkable functional groups and at least one of the crosslinkable functional groups is a hydrogen-bonding type crosslinkable functional group, and the second crosslinkable (meth) acrylate monomer (B2) has 6 or more crosslinkable functional groups and the number of the hydrogen-bonding type crosslinkable functional groups in the crosslinkable functional groups is smaller than the number of the hydrogen-bonding type crosslinkable functional groups in the first crosslinkable (meth) acrylate monomer (B1); a photopolymerization initiator (C).
Description
Technical Field
The present invention relates to a photosensitive resin composition, a cured product obtained from the photosensitive resin composition, and an image display device including the cured product.
Background
In a liquid crystal display device, a thickness of a liquid crystal layer sandwiched between a color filter (color filter) side substrate and a Thin Film Transistor (TFT) side substrate is maintained by using a photo spacer (gap control material).
In order to suppress the variation in cell gap due to stress when using a liquid crystal display device, the resist spacers are required to have a high elastic recovery rate.
For example, patent document 1 proposes an active energy ray-curable resin composition which provides a cured product exhibiting an excellent elastic recovery rate against deformation due to an external load, and patent document 1 proposes a photosensitive resin composition comprising a polymerizable (meth) acrylic polymer (a), a polyfunctional (meth) acrylate monomer component (B) and a photopolymerization initiator (C), wherein the polymerizable (meth) acrylic polymer (a) comprises the following monomer unit (1), monomer unit (2) and monomer unit (3) as constituent elements: a monomer unit (1) having branched side chains each having 2 to 3 terminals ending with a radically polymerizable substituent; a monomer unit (2) having a side chain having a terminal end ending in a carboxyl group and a terminal end ending in a radical polymerizable substituent, which form two branches; and a monomer unit (3) having a side chain having a terminal end terminating in a radically polymerizable substituent.
In addition, since the liquid crystal display element is easily deformed when pressure or impact is applied from the outside, the following problems may occur: the deformed photoresist spacers fracture, and the deformed photoresist spacers damage (shave) the alignment film of the TFT-side substrate. Therefore, there is a need for a resist spacer which is less likely to be broken and less likely to damage an alignment film and has excellent flexibility.
For example, an object of patent document 2 is to provide a photosensitive resin composition which can suppress a high recovery rate of plastic deformation of a resist spacer when used as a spacer and at the same time greatly suppress scraping of a liquid crystal alignment film provided on an opposite substrate. For this purpose, patent document 2 proposes a photosensitive resin composition containing an alkali-soluble resin, a photopolymerization initiator, and a polymerizable compound, wherein the urethane equivalent weight obtained in the solid content of the resin composition is 1000 to 50000g/mol and the ethylenically unsaturated group equivalent weight is 100 to 155g/mol.
Further, an object of patent document 3 is to provide a negative photosensitive resin composition capable of forming a resist spacer having a high elastic recovery rate and excellent flexibility. For this purpose, patent document 3 proposes a negative photosensitive resin composition containing (a) an alkali-soluble resin, (B) a photo-radical polymerization initiator, and (C) a photo-polymerizable monomer, wherein the content of the alkali-soluble resin is 3 to 45 parts by weight based on 100 parts by weight of the total of the alkali-soluble resin and the photo-polymerizable monomer, and the photo-polymerizable monomer contains a di (meth) acrylate having a poly (oxyalkylene) group.
Prior art literature
Patent literature
Patent document 1 International publication No. 2018/169036
Patent document 2 International publication No. 2019/216107
Patent document 3 Japanese patent laid-open No. 2020-71483
Disclosure of Invention
Problems to be solved by the invention
Although patent documents 2 and 3 describe photosensitive resin compositions capable of forming a resist spacer having a high elastic recovery rate and excellent flexibility, the two characteristics are insufficient, and development of a photosensitive resin composition capable of forming a resist spacer having more excellent two characteristics is currently demanded.
The present invention aims to provide a photosensitive resin composition which can form a cured product (for example, a photoresist spacer) having both a high elastic recovery rate and excellent flexibility, and also aims to provide a cured product obtained from the photosensitive resin composition and an image display device comprising the cured product.
Means for solving the problems
The inventors of the present application have conducted intensive studies to solve the above problems, and as a result, have found that the above object can be achieved by using the following photosensitive resin composition, and have completed the present invention.
The present invention relates to a photosensitive resin composition comprising: an alkali-soluble resin (A) having a double bond equivalent of 200g/mol or less; a monomer group (B) comprising a first crosslinkable (meth) acrylate monomer (B1) having 6 or more crosslinkable functional groups at least one of which is a hydrogen-bond-type crosslinkable functional group, and a second crosslinkable (meth) acrylate monomer (B2) having 6 or more crosslinkable functional groups at least one of which is a hydrogen-bond-type crosslinkable functional group, the number of hydrogen-bond-type crosslinkable functional groups being smaller than the number of the first crosslinkable (meth) acrylate monomer (B1), the acid value of the first crosslinkable (meth) acrylate monomer (B2) being 1mgKOH/g to 20 mgKOH/g; and a photopolymerization initiator (C).
The hydroxyl value of the monomer group (B) is preferably 15mgKOH/g to 70mgKOH/g.
The second crosslinkable (meth) acrylate monomer (B2) preferably does not have a hydrogen bond-type crosslinkable functional group.
The photosensitive resin composition of the present invention preferably contains 80 to 200 parts by mass of the monomer group (B) per 100 parts by mass of the alkali-soluble resin (a).
The mass ratio (B1: B2) of the first crosslinkable (meth) acrylate monomer (B1) to the second crosslinkable (meth) acrylate monomer (B2) is preferably 1:10 to 10:1.
The cured product of the present invention is obtained from the photosensitive resin composition. The cured product is preferably a photoresist spacer, a partition wall material, a lens material, an interlayer insulating film material, a protective film material, an optical waveguide material, or a planarizing film material.
The present invention also relates to an image display device including the cured product.
Effects of the invention
The photosensitive resin composition of the present invention is characterized by comprising an alkali-soluble resin (A) having a double bond equivalent of 200g/mol or less and comprising two crosslinkable monomers, namely a first crosslinkable (meth) acrylate monomer (B1) and a second crosslinkable (meth) acrylate monomer (B2), as monomer groups (B), and by using these three components, a cured product having both a high elastic recovery rate and excellent flexibility can be formed. For example, when the cured product of the present invention is a photoresist spacer, the photoresist spacer of the present invention has a high elastic recovery rate, and thus can effectively suppress variation in cell gap due to stress when a liquid crystal display device is used. In addition, the resist spacer of the present invention has excellent flexibility, and is therefore less likely to be broken, and is less likely to damage the alignment film (the alignment film is less likely to be scratched) of the TFT side substrate. Further, the photosensitive resin composition of the present invention can produce a cured product (for example, a resist spacer) which is excellent in solubility in a developer (hereinafter simply referred to as "solubility in a developer") and has a small degree of variation in height (uneven scanning, uneven lens) when used as a resist material.
Detailed Description
In the present invention, "(meth) acrylic" means acrylic acid and/or methacrylic acid. The meaning of "(meth) acrylate" and the like also means the same meaning. In the present invention, the "crosslinkable functional group" means a functional group that forms a crosslinked structure by reacting with other functional groups or by interacting with other atoms. The "hydrogen bond-type crosslinkable functional group" refers to one of crosslinkable functional groups, which is a functional group as described below: the functional group forming a crosslinked structure by interaction with other monomers (not only the same monomer but also the same monomer) in the vicinity of the alkali-soluble resin (a) and the structure capable of forming a hydrogen bond. The structure capable of forming hydrogen bonds is not particularly limited as long as it is a structure capable of forming hydrogen bonds in the structure of the other monomer or the alkali-soluble resin (a), and may be a crosslinkable functional group itself.
The double bond equivalent in the present invention means: the gram number of the object relative to 1mol of the group having a double bond can be obtained by double bond equivalent= (amount of object (g)/number of groups having a double bond (mol) contained in the object). The group having a double bond is not particularly limited, and an ethylenically unsaturated group is typically exemplified, and examples of the ethylenically unsaturated group include an acryl group and a methacryl group.
The acid value in the present invention means the mass (mg) of potassium hydroxide required for neutralizing 1g of an acidic component contained in an object, and is a theoretical value calculated from the molecular weight obtained based on the structure of the object and the number of functional groups per molecule (the number of acid groups). Specifically, the acid value of the object is a value obtained by [ the number of moles of acid groups (mmol) of the object) ]× [ 56.11/amount of the object (g) ]. The hydroxyl value in the present invention means the mass (mg) of potassium hydroxide required for neutralizing the hydroxyl-bonded acetic acid after acetylation of 1g of the object, and is a theoretical value calculated from the molecular weight obtained based on the structure of the object and the number of functional groups per molecule (the number of hydroxyl groups). Specifically, the hydroxyl value of the object is a value obtained by [ the number of moles of hydroxyl groups of the object (mmol) ]× [ 56.11/amount of the object (g) ]. Examples of the object of the acid value and the hydroxyl value include an alkali-soluble resin (a) and a monomer group (B).
Examples of the target substances among the double bond equivalent, acid value and hydroxyl value include the alkali-soluble resin (a) and the monomer group (B), and the structures of these target substances and the content in the photosensitive resin composition can be measured by analyzing the photosensitive resin composition by a known method, and can also be measured from the structures and ratios of raw materials (target substances) used in producing the photosensitive resin composition.
The photosensitive resin composition of the present invention comprises an alkali-soluble resin (A), a monomer group (B) and a photopolymerization initiator (C). The double bond equivalent of the alkali-soluble resin (A) is 200g/mol or less. The monomer group (B) contains a first crosslinkable (meth) acrylate monomer (B1) and a second crosslinkable (meth) acrylate monomer (B2) and has an acid value of 1mgKOH/g to 20mgKOH/g. The first crosslinkable (meth) acrylate monomer (B1) has 6 or more crosslinkable functional groups, and at least one of the crosslinkable functional groups is a hydrogen-bond-type crosslinkable functional group. The second crosslinkable (meth) acrylate monomer (B2) has 6 or more crosslinkable functional groups, and the number of hydrogen bond type crosslinkable functional groups in the crosslinkable functional groups is smaller than the number of hydrogen bond type crosslinkable functional groups of the first crosslinkable (meth) acrylate monomer (B1).
While not being limited by theory, the reason why a cured product having both high elastic recovery and excellent flexibility can be obtained by using the photosensitive resin composition of the present invention is presumed to be as follows. When a monomer having a large number of polymerizable functional groups is used in the photosensitive resin composition, a crosslinked structure in which one monomer unit is bonded to a large number of other monomers is formed without forming a main chain structure by serial bonding (polymerization) of the monomers. In this case, the inventors of the present application found that the crosslinkable functional groups in the monomer units become easily bonded to each other, and as a result, the elastic recovery rate and flexibility of the resulting cured film are adversely affected. Accordingly, the inventors of the present application have found that, using two (meth) acrylate monomers, at least one of which has a hydrogen bond type crosslinking functional group and the other of which has a smaller number than the hydrogen bond type crosslinking functional group of the former (meth) acrylate monomer, it is possible to prevent the crosslinking functional groups in the monomer units from becoming easier to bond with each other, promote the formation of bonds between different monomer units (not only means that bonds between different monomers but also include the same kind of monomer) or promote the bonding of the monomer with the alkali-soluble resin (a). Further, at least one (meth) acrylate monomer contains a hydrogen bond type crosslinkable functional group, whereby all of the crosslinkable functional groups do not form a covalent bond having a strong bonding force, and at least a part of the hydrogen bond type crosslinkable functional groups are crosslinked with a hydrogen bond having a weak bonding force to a structure capable of forming a hydrogen bond possessed by another monomer in the vicinity. In addition, when the side chain of the alkali-soluble resin (a) has a structure capable of forming a hydrogen bond with the hydrogen bond-type crosslinkable functional group, the structure and the hydrogen bond-type crosslinkable functional group of the monomer are crosslinked by a hydrogen bond having a weak bonding force generated by the hydrogen bond. As described above, in the present invention, it is considered that the rigidity and elasticity of the cured product are precisely controlled by combining a hydrogen bond having a weak bonding force and a covalent bond having a strong bonding force in the cured product. Thus, it is presumed that a network structure having both a high elastic recovery rate and excellent flexibility is formed when the photosensitive resin composition is cured.
[ alkali-soluble resin (A) ]
The alkali-soluble resin (A) is not particularly limited as long as it has a double bond equivalent of 200g/mol or less. In the present invention, the elastic recovery rate can be improved by using an alkali-soluble resin having a double bond equivalent of 200g/mol or less, that is, a lower double bond equivalent value. The double bond equivalent of the alkali-soluble resin (A) is preferably 160g/mol or less.
The monomer for forming the alkali-soluble resin (a) is not particularly limited, and examples thereof include: carboxyl group-containing monomers such as (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, maleic acid and itaconic acid; carboxylic anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, dodecyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethoxyethyl (meth) acrylate, and glycidyl (meth) acrylate; alicyclic (meth) acrylates such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentenyl (meth) acrylate. In addition, styrene, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, n-butylmaleimide, laurylmaleimide, polysiloxane (silicone) -containing monomers and the like may also be used as comonomers. These monomers may be used singly or in combination of two or more.
The alkali-soluble resin (a) may have an acid group in a side chain in order to impart alkali developability to the photosensitive resin composition. The method of introducing the acid group into the side chain of the alkali-soluble resin (a) is not particularly limited, and known methods can be employed, and examples thereof include the following methods: a method of copolymerizing a carboxyl group-containing monomer and a carboxylic acid anhydride group-containing monomer; a method in which a polymer obtained by copolymerizing a carboxyl group-containing monomer such as (meth) acrylic acid is added to an epoxy group-containing compound such as glycidyl (meth) acrylate, and the resulting hydroxyl group is added to an acid anhydride; and a method in which a polymer obtained by copolymerizing an epoxy group-containing monomer such as glycidyl (meth) acrylate is added to a carboxyl group-containing compound such as (meth) acrylic acid, and an acid anhydride is added to the hydroxyl group thus formed.
In addition, an ethylenically unsaturated group may be introduced into the side chain of the alkali-soluble resin (A). Examples of the method for introducing an ethylenically unsaturated group into the side chain of the alkali-soluble resin (a) include: a method in which a polymer obtained by copolymerizing an epoxy group-containing monomer such as glycidyl (meth) acrylate is added to a compound having an ethylenically unsaturated group and a carboxyl group such as (meth) acrylic acid; a method in which a polymer obtained by copolymerizing a carboxyl group-containing monomer such as (meth) acrylic acid is added to a compound having an ethylenically unsaturated group such as glycidyl (meth) acrylate; and a method in which a polymer obtained by copolymerizing a hydroxyl group-containing monomer such as hydroxyethyl (meth) acrylate is added to a compound having an ethylenically unsaturated group and an isocyanate group such as (meth) acryloyloxyethyl isocyanate.
At least one of the main chain and the side chain of the alkali-soluble resin (a) may also contain a structure capable of forming hydrogen bonds with the hydrogen-bonding crosslinkable functional group of the (meth) acrylate monomer (B1) or (B2). As described above, this is because the rigidity and elasticity of the cured product can be precisely adjusted by combining a hydrogen bond having a weak bonding force and a covalent bond having a strong bonding force in the cured product. The structure of the alkali-soluble resin (A) that can form a hydrogen bond with the hydrogen-bonding-type crosslinkable functional group in the main chain and side chain thereof includes, for example, -COOH, -OH, and-NH-, and is preferably, -COOH, -OH from the viewpoint of easily retaining a hydrogen bond. In addition, from the viewpoint of easy formation of hydrogen bonds, the side chain of the alkali-soluble resin (a) preferably contains a structure capable of forming hydrogen bonds.
The weight average molecular weight (Mw) of the alkali-soluble resin (a) is not particularly limited, but when the photosensitive resin composition is used as a resist material such as a resist spacer, it is preferably 5000 to 100000, more preferably 10000 to 30000, from the viewpoint of obtaining good exposure sensitivity and good developability (hereinafter simply referred to as "the viewpoint of improving exposure sensitivity and heat resistance"). The weight average molecular weight can be obtained by Gel Permeation Chromatography (GPC) according to JIS K7252-1:2016, which is a value obtained in terms of standard polystyrene.
The double bond equivalent of the alkali-soluble resin (A) is 200g/mol or less, preferably 180g/mol, more preferably 170g/mol or less, and still more preferably 160g/mol or less, from the viewpoint of improving the heat resistance of the photosensitive resin composition with good exposure sensitivity.
The acid value of the alkali-soluble resin (a) is not particularly limited, but is preferably 10 to 200mgKOH/g, more preferably 15 to 150mgKOH/g, still more preferably 20 to 100mgKOH/g, particularly preferably 25 to 75mgKOH/g, and most preferably 30 to 50mgKOH/g, from the viewpoint of imparting good developability to the photosensitive resin composition.
As the alkali-soluble resin (A), a polymerizable (meth) acrylic polymer (A) described in International publication No. 2018/169036 may be used.
Monomer group (B)
The monomer group (B) is a monomer group containing at least both the first crosslinkable (meth) acrylate monomer (B1) and the second crosslinkable (meth) acrylate monomer (B2). When the monomer group (B) contains three or more crosslinkable (meth) acrylate monomers and all of them contain hydrogen bond type crosslinkable functional groups, the second crosslinkable (meth) acrylate monomer (B2) is the one having the smallest number of hydrogen bond type crosslinkable functional groups. When the monomer group (B) contains three or more crosslinkable (meth) acrylate monomers, and one or more of them is a crosslinkable (meth) acrylate monomer having no hydrogen bond type crosslinkable functional group, the crosslinkable (meth) acrylate monomer having no hydrogen bond type crosslinkable functional group is used as the second crosslinkable (meth) acrylate monomer (B2).
The photosensitive resin composition of the present invention includes, for example, the following embodiments (1) to (5).
(1) A solution comprising a plurality of first crosslinkable (meth) acrylate monomers (B1) and a plurality of second crosslinkable (meth) acrylate monomers (B2).
(2) Comprises a plurality of first crosslinkable (meth) acrylate monomers (B1) and a single second crosslinkable (meth) acrylate monomer (B2).
(3) Comprises a single first crosslinkable (meth) acrylate monomer (B1) and a plurality of second crosslinkable (meth) acrylate monomers (B2).
(4) Comprises a single first crosslinkable (meth) acrylate monomer (B1) and a single second crosslinkable (meth) acrylate monomer (B2).
(5) The composition of any one of (1) to (4) above further comprises other monomers.
In the embodiments (1) and (2), the number of crosslinkable functional groups may be the same or different for a plurality of monomers corresponding to the first crosslinkable (meth) acrylate monomer (B1), and the number of hydrogen bond type crosslinkable functional groups may be the same or different. The number of hydrogen bond type crosslinkable functional groups in the second crosslinkable (meth) acrylate monomer (B2) is smaller than the number of hydrogen bond type crosslinkable functional groups in the plurality of monomers corresponding to the first crosslinkable (meth) acrylate monomer (B1) which have the smallest number of hydrogen bond type crosslinkable functional groups. In the embodiment (1) above, the number of crosslinkable functional groups may be the same or different for a plurality of monomers corresponding to the second crosslinkable (meth) acrylate monomer (B2), but the number of hydrogen bond type crosslinkable functional groups is the same for all monomers corresponding to the second crosslinkable (meth) acrylate monomer (B2). In the case of the above (3), the number of hydrogen bond type crosslinkable functional groups is the same for all the monomers corresponding to the second crosslinkable (meth) acrylate monomer (B2).
The acid value of the monomer group (B) is 1mgKOH/g to 20mgKOH/g, preferably 3mgKOH/g to 15mgKOH/g, more preferably 6mgKOH/g to 12mgKOH/g, from the viewpoint of forming the crosslinked structure between the above-mentioned different monomer units and promoting the formation of the crosslinked structure of the monomer and the alkali-soluble resin (A). The monomer group (B) contains at least a first crosslinkable (meth) acrylate monomer (B1) and a second crosslinkable (meth) acrylate monomer (B2), and further contains other monomers as needed. Accordingly, the setting of the acid value for the monomer group (B) is as follows: the acid value of each monomer is calculated, the acid value of each monomer is calculated and the value obtained by multiplying the mass ratio of the monomer in the monomer group (B) is calculated, and these values are summed up. The same setting is also made for the respective acid values when the plurality of first crosslinkable (meth) acrylate monomers (B1) are contained and when the plurality of second crosslinkable (meth) acrylate monomers (B2) are contained. These aspects are also set for the hydroxyl value described later.
The hydroxyl value of the monomer group (B) is preferably 15 to 70mgKOH/g, more preferably 20 to 60mgKOH/g, and even when the cured product is repeatedly pressed, the hydroxyl value is preferably 25 to 55mgKOH/g, from the viewpoints of formation of a crosslinked structure with the above-mentioned different monomer, promotion of formation of a crosslinked structure between the monomer and the alkali-soluble resin (a), maintenance of a high elastic recovery rate and excellent flexibility (hereinafter referred to as "having high durability") even when the cured product is repeatedly pressed, and good adhesion to a coating object when the photosensitive resin composition is applied to a substrate or the like, and excellent solubility to a developer.
< first crosslinkable (meth) acrylate monomer (B1) >)
The first crosslinkable (meth) acrylate monomer (B1) has 6 or more crosslinkable functional groups, and at least one of the crosslinkable functional groups is a hydrogen-bond-type crosslinkable functional group. In addition, at least one crosslinkable functional group is an acryl or methacryl group.
The crosslinkable functional group is not particularly limited, and examples thereof include: acryl, methacryl, vinyl, carboxyl, hydroxyl, thio, amino, epoxy, isocyanate, and the like. These crosslinkable functional groups may be contained in two or more kinds. The acryl and methacryl groups are considered to be different from the vinyl groups, although they contain a vinyl structure in their structures. Similarly, a carboxyl group is considered to be different from a hydroxyl group, although it also contains-OH. The first crosslinkable (meth) acrylate monomer (B1) may have a functional group other than the crosslinkable functional group. These aspects are also similar to those of the crosslinkable functional group of the second crosslinkable (meth) acrylate monomer (B2) described later.
The hydrogen bond-type crosslinkable functional group is not particularly limited as long as it is a functional group capable of forming a hydrogen bond with other monomer units or the like, and examples thereof include a carboxyl group, a hydroxyl group, an amino group, and the like. These hydrogen bond-type crosslinkable functional groups may be contained in one kind or two or more kinds. From the viewpoint of easy maintenance of hydrogen bonds, it is preferable that the hydrogen bond type crosslinkable functional group has at least one of a carboxyl group and a hydroxyl group, and it is more preferable that one of a carboxyl group and a hydroxyl group is present and the other is absent.
The first crosslinkable (meth) acrylate monomer (B1) has 6 or more crosslinkable functional groups from the viewpoint of obtaining a cured product having both a high elastic recovery rate and excellent flexibility. The first crosslinkable (meth) acrylate monomer (B1) may have 7 or more, 8 or more, or 9 or more crosslinkable functional groups. The upper limit of the number of crosslinkable functional groups is not particularly limited, but is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less from the viewpoint of suppressing the decrease in flexibility of the cured product. The number of the hydrogen bond type crosslinkable functional groups in the first crosslinkable (meth) acrylate monomer (B1) is not particularly limited if it is 1 or more, but is preferably 3 or less, more preferably 2 or less, and particularly preferably 1 from the viewpoint of preventing the strength of the resulting cured product from being lowered.
Examples of the monomer that can be used as the first crosslinkable (meth) acrylate monomer (B1) include: dipentaerythritol penta (meth) acrylate [ number of crosslinkable functional groups ] is 6, wherein the number of (meth) acrylic acid groups (also referred to as "(meth) acryl number", hereinafter the same) is 5, hydroxyl number is 1, dipentaerythritol tetra (meth) acrylate [ number of crosslinkable functional groups ] is 6, wherein the number of (meth) acrylic acid groups is 4, hydroxyl number is 2, tripentaerythritol hexa (meth) acrylate [ number of crosslinkable functional groups ] is 8, wherein the number of (meth) acrylic acid groups is 6, hydroxyl number is 2, tripentaerythritol penta (meth) acrylate [ number of crosslinkable functional groups ] is 8, wherein the number of (meth) acrylic acid groups is 5, hydroxyl number is 3, succinic anhydride addition-modified dipentaerythritol penta (meth) acrylate [ number of crosslinkable functional groups ] is 6, wherein the number of (meth) acrylic acid groups is 5, carboxyl number is 1, sorbitol penta (meth) acrylate [ number of crosslinkable functional groups ] is 6, wherein the number of (meth) acrylic acid groups is 5, hydroxyl number is 1, adipic acid penta (meth) acrylate [ number of crosslinkable functional groups ] is 6, wherein the number of (meth) acrylic acid groups is 5, carboxyl number of adipic acid groups is 5, pentaerythritol (meth) acrylate [ number of crosslinkable functional groups ] is 6, wherein the number of (meth) propenes is 5, the number of hydroxyl groups is 1, etc. These monomers may be used singly or in combination of two or more.
< second crosslinkable (meth) acrylate monomer (B2) >)
The second crosslinkable (meth) acrylate monomer (B2) has 6 or more crosslinkable functional groups, and the number of hydrogen bond type crosslinkable functional groups in the crosslinkable functional groups is smaller than the number of hydrogen bond type crosslinkable functional groups in the first crosslinkable (meth) acrylate monomer (B1). In addition, at least one crosslinkable functional group of the second crosslinkable (meth) acrylate monomer (B2) is an acryl or methacryl group.
From the viewpoint of obtaining a cured product having both a high elastic recovery rate and excellent flexibility, the second crosslinkable (meth) acrylate monomer (B2) has 6 or more crosslinkable functional groups. The second crosslinkable (meth) acrylate monomer (B2) may have 7 or more, 8 or more, or 9 or more crosslinkable functional groups. The upper limit of the number of crosslinkable functional groups is not particularly limited, but is preferably 30 or less, more preferably 25 or less, and further preferably 20 or less from the viewpoint of solubility in a developer. The number of the hydrogen bond type crosslinkable functional groups of the second crosslinkable (meth) acrylate monomer (B2) is not particularly limited as long as the number is smaller than the number of the hydrogen bond type crosslinkability of the first crosslinkable (meth) acrylate monomer (B1), and the number of the hydrogen bond type crosslinkable functional groups of the first crosslinkable (meth) acrylate monomer (B1) may be 1, 2, or 3. In addition, from the viewpoint of suppressing the excessive decrease in elasticity and hardness of the cured product, the number of hydrogen bond-type crosslinkable functional groups of the second crosslinkable (meth) acrylate monomer (B2) is preferably 1 or less, more preferably 0.
Examples of the monomer that can be used as the second crosslinkable (meth) acrylate monomer (B2) include: dipentaerythritol hexa (meth) acrylate having a crosslinking functional group number of 6, wherein the number of (meth) propylene groups is 6, sorbitol hexa (meth) acrylate having a crosslinking functional group number of 6, wherein the number of (meth) propylene groups is 6, tripentaerythritol octa (meth) acrylate having a crosslinking functional group number of 8, wherein the number of (meth) propylene groups is 8, and the like. The monomer exemplified as the first crosslinkable (meth) acrylate monomer (B1) may be used as the second crosslinkable (meth) acrylate monomer (B2) on the premise that the relationship with the number of hydrogen bond type crosslinkable functional groups of the first crosslinkable (meth) acrylate monomer (B1) is satisfied. These monomers may be used singly or in combination of two or more.
The first crosslinkable (meth) acrylate monomer (B1) and the second crosslinkable (meth) acrylate monomer (B2) are often obtained as a mixture containing two monomers, and are sometimes sold as a product containing two monomers. The mixing ratio of the two monomers can be controlled, for example, by adjusting the conditions under which the mixture containing the two monomers is produced by esterifying the alcohol with (meth) acrylic acid. Examples of the method for adjusting the conditions during production include known methods such as adjusting the mass ratio of alcohol to (meth) acrylic acid during esterification, the reaction time and reaction temperature, and the purification (purification) method and purification time of the product obtained by esterification. The same applies when the first crosslinkable (meth) acrylate monomer is a modified product. The mixture may be used alone or after further mixing. In addition, they may be used in cases where the individual monomers can be obtained and manufactured not as a mixture but as a single product. These may be used alone or in combination.
< other monomer >
The monomer group (B) may contain a known monomer other than the first crosslinkable (meth) acrylate monomer (B1) and the second crosslinkable (meth) acrylate monomer (B2) within a range that does not impair the effect of the present invention.
[ photopolymerization initiator (C) ]
The photopolymerization initiator (C) is not particularly limited, and examples thereof include: benzoin such as benzoin, benzoin methyl ether and benzoin ethyl ether and alkyl ethers thereof; acetophenones such as acetophenone, 2-dimethoxy-2-phenylacetophenone, and 1, 1-dichloroacetophenone; anthraquinones such as 2-methylanthraquinone, 2-pentylalnthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; thioxanthones (thioxanthones) such as 2, 4-dimethylthioxanthone, 2, 4-diisopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; diphenyl ketone such as diphenyl ketone; 2-methyl-1- [4- (methylsulfanyl) phenyl ] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; acyl phosphine oxides, xanthones, and the like. These photopolymerization initiators may be used alone or in combination of two or more.
[ photosensitive resin composition ]
The photosensitive resin composition of the present invention preferably contains 80 to 200 parts by mass, more preferably 100 to 170 parts by mass, and still more preferably 120 to 150 parts by mass of the monomer group (B) per 100 parts by mass of the alkali-soluble resin (a) from the viewpoints of obtaining a cured product having both a high elastic recovery rate and excellent flexibility, improving solubility in a developer, suppressing a variation in the height of the cured product, and the like. In this case, the monomer group (B) preferably contains 80 parts by mass or more of the first crosslinkable (meth) acrylate monomer (B1) and the second crosslinkable (meth) acrylate monomer (B2) in total. In particular, from the viewpoint of improving the elastic recovery rate, the alkali-soluble resin (a) preferably contains 100 parts by mass or more in total, more preferably 120 parts by mass or more in total of the first crosslinkable (meth) acrylate monomer (B1) and the second crosslinkable (meth) acrylate monomer (B2) in total. Further, from the viewpoint of suppressing the variation in the height of the cured product and ensuring good solubility in the solvent when the solvent is used, the first crosslinkable (meth) acrylate monomer (B1) and the second crosslinkable (meth) acrylate monomer (B2) are preferably contained in an amount of 200 parts by mass or less, more preferably 170 parts by mass or less, still more preferably 150 parts by mass or less in total, with respect to 100 parts by mass of the alkali-soluble resin (a).
The photosensitive resin composition of the present invention is preferably 1:10 to 10:1, more preferably 1:5 to 5:1, still more preferably 1:3 to 3:1, and particularly preferably 1:2 to 2:1, from the viewpoints of obtaining a cured product having both a high elastic recovery rate and excellent flexibility, improving solubility in a developer, suppressing a variation in the height of the cured product, and the like.
The content of the photopolymerization initiator (C) is not particularly limited, but is preferably 1 to 60 parts by weight, more preferably 3 to 40 parts by weight, further preferably 4 to 35 parts by weight, and particularly preferably 6 to 25 parts by weight, relative to 100 parts by weight of the alkali-soluble resin (a) from the viewpoints of solubility and curability of the photosensitive resin composition.
The photosensitive resin composition of the present invention may contain a photopolymerization initiator aid. Examples of photopolymerization initiator auxiliary agents include: trifunctional thiol compounds such as 1,3, 5-tris (3-mercaptopropionyloxyethyl) -isocyanurate, 1,3, 5-tris (3-mercaptobutoxyethyl) -isocyanurate (Karenz MT (registered trademark) NR1, manufactured by Showa Denko Co., ltd.), and trimethylolpropane tris (3-mercaptopropionate); tetrafunctional thiol compounds such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz MT (registered trademark) PEI, manufactured by Showa Denko Co., ltd.); and multifunctional mercaptans such as hexafunctional mercaptan compounds such as dipentaerythritol hexa (3-propionate). These photopolymerization initiator may be used alone or in combination of two or more.
The photosensitive resin composition of the present invention may also contain a thermal polymerization initiator. Examples of the thermal polymerization initiator include: organic peroxides such as cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butyl isopropyl carbonate peroxide, t-butyl-2-ethyl hexanoate peroxide, and t-amyl-2-ethyl hexanoate peroxide; azo compounds such as 2,2 '-azobis (isobutyronitrile), 1' -azobis (cyclohexanecarbonitrile), 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.
The photosensitive resin composition of the present invention may also comprise: radical polymerizable oligomers such as unsaturated polyesters, epoxy acrylates, urethane acrylates, and polyester acrylates, and curable resins such as epoxy resins.
The photosensitive resin composition of the present invention may also contain a solvent. Examples of the solvent include: ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and the like; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and the like; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, etc.; chloroform, dimethylsulfoxide, etc. These solvents may be used singly or in combination of two or more. In addition, the solvent content may be appropriately set according to the viscosity most suitable when the composition is used.
The photosensitive resin composition of the present invention may also contain, within a range that does not impair the effects of the present invention: filling materials such as aluminum hydroxide, talc, clay, barium sulfate and the like; dyes, pigments, defoamers, coupling agents, leveling agents, sensitizers, mold release agents, lubricants, plasticizers, antioxidants, ultraviolet absorbers, flame retardants, polymerization inhibitors, thickeners, dispersants, and other known additives.
[ cured product ]
The cured product of the present invention is obtained by curing the photosensitive resin composition. Examples of the method for producing the cured product of the present invention include the following methods: the photosensitive resin composition is injected into a molding die (resin die), cured by heating (prebaking) or the like as needed to a degree that the shape can be maintained, and then taken out from the die, or the photosensitive resin composition is coated on a base material (substrate) and various functional layers to be formed into a desired shape, and then the photosensitive resin composition is cured by irradiation with light (for example, ultraviolet rays). The curing conditions can be appropriately adjusted according to the photosensitive resin composition used.
The cured product is suitable as a resist spacer, a partition wall material, a lens material, an interlayer insulating film material, a protective film material, an optical waveguide material, or a planarizing film material, and is particularly suitable as a resist spacer.
[ Photoresist spacer ]
The method for forming the resist spacer is not particularly limited, and the resist spacer may be formed by, for example, coating a substrate such as glass or a transparent plastic film with the photosensitive resin composition, drying the substrate to form a coating film, and then, performing photolithography. In the photolithography method, for example, a photomask is placed on a coating film, the coating film is photo-cured by irradiation with ultraviolet rays, an alkali aqueous solution is spread on the coating film after irradiation with ultraviolet rays to dissolve unexposed portions, and the exposed portions remaining after removal are washed with water and developed, thereby forming a resist spacer. Thereafter, post baking may also be performed.
The shape of the resist spacer is not particularly limited, but examples thereof include a columnar shape, a prismatic shape, a truncated cone shape, a truncated pyramid shape, and the like.
The photoresist spacer of the present invention has the following features: since the liquid crystal display device has a high elastic recovery rate, variation in cell gap due to stress when the liquid crystal display device is used can be effectively suppressed, and the liquid crystal display device has excellent flexibility, and is not easily broken, so that an alignment film of a TFT side substrate is not easily damaged (it is difficult to scratch the alignment film).
Examples
The present invention is illustrated by way of examples and is not limited in any way by the examples below.
Production example 1
[ Synthesis of alkali-soluble resin (A-1) ]
100 parts by mass of Glycidyl Methacrylate (GMA) and 150 parts by mass of propylene glycol monomethyl ether acetate (PGMAc) were placed in a glass flask equipped with a heating, cooling and stirring apparatus, a reflux condenser, and a nitrogen inlet tube. After substituting the gas phase portion in the system with nitrogen, 8.7 parts by mass of 2,2' -azobis (2, 4-dimethylvaleronitrile) was added and heated to 80℃and reacted at the same temperature for 8 hours. To the resulting solution were further added 80 parts by mass of acrylic anhydride, 15 parts by mass of Acrylic Acid (AA), 2.0 parts by mass of tetrabutylammonium chloride, 0.3 part by mass of hydroquinone, 173 parts by mass of propylene glycol monomethyl ether acetate, and reacted at 70℃for 12 hours. Thereafter, 14 parts by mass of succinic anhydride was added to the reacted solution, and the reaction was carried out at 70℃for 6 hours to obtain a 40% by mass solution of the alkali-soluble resin (A-1). The acid value of the alkali-soluble resin (A-1) was 37.4mgKOH/g, the weight average molecular weight (Mw) as measured by GPC was 24000, and the double bond equivalent was 154g/mol.
Production example 2
[ Synthesis of alkali-soluble resin (A-2) ]
686 parts by mass of PGMAc, 332 parts by mass of GMA, and 6.6 parts by mass of Azobisisobutyronitrile (AIBN) were charged into a glass flask equipped with a heating, cooling and stirring apparatus, a reflux condenser, and a nitrogen introducing tube. A solution of a polymer (GMA polymer) obtained by polymerizing GMA was obtained by heating at 80℃for 6 hours while nitrogen was blown into the system. To the polymer solution of the resulting GMA, 168 parts by mass of Acrylic Acid (AA), 0.05 parts by mass of hydroquinone monomethyl ether (MQ), and 0.5 parts by mass of Triphenylphosphine (TPP) were added, and the mixture was heated at 100 ℃ for 24 hours while blowing air, to obtain a solution of an acrylic acid adduct of the GMA polymer. To a solution of the acrylic acid adduct of the GMA polymer, 186 parts by mass of tetrahydrophthalic anhydride was added and heated at 70℃for 10 hours to obtain a 50.2% by mass solution of the alkali-soluble resin (A-2). The acid value of the alkali-soluble resin (A-2) was 99mgKOH/g, and the double bond equivalent was 294g/mol.
Production example 3
[ Synthesis of monomer mixture alpha ]
1557.5 parts by mass of dipentaerythritol, 3442.5 parts by mass of 98% acrylic acid, 7.5 parts by mass of p-methoxyphenol, 250 parts by mass of p-toluenesulfonic acid, and 750 parts by mass of cyclohexane were charged into a reaction apparatus equipped with a condenser pipe with a water separator, a stirrer, a thermometer, and an air-blowing pipe. Then, while air was blown into the reaction solution at a flow rate of 300 mL/min, the temperature in the reaction system was raised to 85℃over 1 hour, and cyclohexane was refluxed. The reflux was continued while maintaining the temperature at 85 to 92℃and the water produced was removed from the system. The reaction liquid a was obtained by analyzing the reaction liquid at any time by High Performance Liquid Chromatography (HPLC) under the following conditions, and ending the reaction with about 30 mass% of dipentaerythritol pentaacrylate (DPEPA) and about 70 mass% of dipentaerythritol hexaacrylate (DPEHA) in the reaction liquid.
(analysis of composition in reaction solution A)
Device Waters HPLC (Millipore Co., ltd., japan)
Column YMC PACK ODS (mountain village chemical institute)
Detector Rl
Mobile phase methanol/water=7/3
Flow rate 1mL/min
(neutralization and washing step)
515.6 parts by mass of reaction solution A, 103.1 parts by mass of cyclohexane and 412.5 parts by mass of toluene were added to the beaker, followed by slowly adding 240.8 parts by mass of a 20% aqueous solution of sodium hydroxide with stirring, and stirring for about 30 minutes, whereby unreacted acrylic acid was neutralized. Then, the neutralized solution was transferred to a separating funnel and allowed to stand for 1 hour, and the water layer was removed to finish the neutralization step. Further, 257.8 parts by mass of deionized water was added to the separating funnel, and after shaking vigorously, the mixture was left standing for 1 hour to remove the aqueous layer. This washing operation was repeated 2 times (i.e., a total of 3 times of washing operations were performed), and the washing process was completed. Thus, 831.8 parts by mass of a pale yellow organic layer was obtained. To the total amount of the organic layers, 0.07 parts by mass of p-methoxyphenol was added, and the organic solvent was distilled off by vacuum operation while blowing a small amount of air, thereby obtaining 328.7 parts by mass of a purified product. Next, the content of p-methoxyphenol in the purified product was adjusted to 500ppm.
(modification step)
250 parts by mass of the purified product having the p-methoxyphenol content of 500ppm, 16 parts by mass of succinic anhydride, and 0.13 part by mass of MQ were charged into a 500mL reaction vessel flask equipped with a stirrer, a condenser, and a thermometer, and the temperature was raised to 85 ℃. After 1.3 parts by mass of Triethylamine (TEA) was charged therein, the reaction was carried out at 80℃for an hour under an oxygen/nitrogen mixed gas atmosphere (oxygen: nitrogen=5:95 capacity ratio) to obtain a monomer mixture α. The monomer mixture α contained succinic anhydride addition-modified dipentaerythritol penta (meth) acrylate [ AM-DPEPA, having a crosslinkable functional group number of 6, wherein the propylene number was 5, the carboxyl number was 1] at about 30 parts by mass and DPEHA at about 70 parts by mass.
Production example 4
[ Synthesis of monomer mixture beta ]
A monomer mixture β was obtained in the same manner as in production example 3 above, except that the modification step was not performed. The monomer mixture beta is a mixture of DPEPA and DPEHA, and the mass ratio of the monomer mixture beta is DPEPA: dpeha=about 30 parts by mass, about 70 parts by mass.
Production example 5
[ Synthesis of monomer mixture gamma ]
A monomer mixture gamma was obtained in the same manner as in production example 3 above, except that the modification step was not performed. The monomer mixture γ was a mixture of DPEPA and DPEHA, and the mass ratio thereof was DPEPA: dpeha=about 37.5 parts by mass and about 62.5 parts by mass.
Example 1
[ preparation of photosensitive resin composition ]
250 parts by mass of a 40% by mass solution of an alkali-soluble resin (A-1) [ 100 parts by mass of the content of the alkali-soluble resin (A-1) ], 40 parts by mass of a monomer mixture α as a monomer component (B), 80 parts by mass of a monomer mixture β, 6 parts by mass of Irgacure OXE01 (manufactured by BASF Japanese Co., ltd.) as a photopolymerization initiator (C), and 2.5 parts by mass of Tinuvin 479 (manufactured by BASF Japanese Co., ltd.) as an ultraviolet absorber were mixed to prepare a photosensitive resin composition having a solid content of 2.6% by mass in the composition. The AM-DPEPA and the DPEPA correspond to the first crosslinkable (meth) acrylate monomer (B1) in the monomer group (B), and the total content thereof is 68 parts by mass. The DPEHA corresponds to the second crosslinkable (meth) acrylate monomer (B2) and the content thereof is 52 parts by mass. The acid value of the monomer unit (B) was 8mgKOH/g, and the hydroxyl value was 53mgKOH/g.
Examples 2 to 4 and comparative examples 1 to 8
A photosensitive resin composition was produced in the same manner as in example 1, except that the composition was changed to the composition shown in table 1. The values in table 1 are expressed in terms of parts by mass, and the values obtained from the maximum value and the minimum value of the range are described as the ranges in terms of the characteristics of the product in the monomer group (B) as the content ratio and the values calculated from the content. In table 1, the contents of the monomer group (B) not mentioned above, the trade names of the photopolymerization initiator (C) and the ultraviolet absorber, and the manufacturers are as follows.
Monomer set (B)
Viscoat #295 (trimethylolpropane triacrylate, manufactured by Osaka organic chemical Co., ltd., crosslinking functional group number 3, wherein propylene number is 3, hydroxyl number is 0)
Viscoat #700 (EO 3.8 mol adduct diacrylate of bisphenol A, manufactured by Osaka organic chemical Co., ltd., wherein the number of the crosslinkable functional groups is 2, and the number of the hydroxyl groups is 0)
Viscoat #802 (mixture of 55 to 85 parts by mass of tripentaerythritol acrylate, 10 to 20 parts by mass of dipentaerythritol acrylate, 5 to 15 parts by mass of dipentaerythritol acrylate manufactured by Osaka organic chemical Co., ltd.)
DPEA-12 (ethylene oxide modified dipentaerythritol hexaacrylate, available from Nippon Kagaku Co., ltd., wherein the number of the crosslinkable functional groups is 6, and the number of the hydroxyl groups is 0)
Photopolymerization initiator (C)
TR-PBG-304: trade name TR-PBG-304 (manufactured by Changzhou Strong front end electronic materials Co., ltd.)
OXE-01: trade name Irgacure OXE01 (manufactured by BASF Japanese Co., ltd.)
Irg-819: trade name Irgacure 819
EMK: SPEEDCURE EMK (manufactured by LAMBSON)
NCI-100: trade name ADEKA ARKLS NCI-100 (manufactured by ADEKA of Co., ltd.)
Ultraviolet absorber
SEESORB106: trade name SEESORB106 (SHIPRO chemical Co., ltd.)
Tinuvin479: trade name Tinuvin479 (manufactured by BASF Japanese Co., ltd.)
[ method of measurement and evaluation ]
(elastic recovery rate)
The photosensitive resin compositions prepared in examples 1 to 4 and comparative examples 1 to 8 were each applied to a 10cm×10cm square glass substrate by using a spin coater to form a coating film. Next, the resulting coating film was heated on a heating plate at 90 ℃ for 2 minutes, and the solvent in the coating film was completely removed. Thereafter, the light of the extra-high pressure mercury lamp was passed through a band-pass filter (band-pass filter) to take out only the i-line every 1cm 2 Mask for forming a plurality of resist spacers having 100 openings with different diameters of 6 μm, 8 μm, 9 μm, 10 μm or 11 μm, at 90mJ/cm 2 The obtained coating film was irradiated (the illuminance in terms of i-line was 33mW/cm 2 ). The exposure was performed so that the distance between the mask and the substrate (exposure gap) was 50 μm. Thereafter, 0.3% Na was used 2 CO 3 The aqueous solution was developed, and after washing with water, the photoresist spacers of different sizes were formed by heating at 230℃for 30 minutes. From the obtained resist spacers, a resist spacer having an upper bottom diameter of 7 μm, a lower bottom diameter of 10 μm and a height of 3 μm was selected, and the elastic recovery was measured by the following method. Here, the upper and lower bottoms are defined as follows.
And (3) upper bottom: a diameter of 90% of the film thickness was set to 100%;
and (3) bottom: the diameter of the 10% portion was set to 100% film thickness.
The measurement was performed by using a micro hardness tester (manufactured by Fischer Instruments Co., ltd., product name: FISCHERCOPE HM-2000), setting the applied load speed and the removed load speed to 2.0 mN/sec by a planar indenter having a diameter of 50 μm, applying a load to 40mN to the obtained resist spacer (height of 3 μm), holding for 5 seconds, and then removing the load to 0mN, holding for 5 seconds, thereby preparing a load-deflection curve when the load was applied and a load-deflection curve when the load was removed. Next, the deformation amount under 40mN under load when the load was applied was L1, the deformation amount under 0mN under load when the load was removed was L2, and the elastic recovery rate was calculated according to the following equation and evaluated based on the following criteria.
Elastic recovery (%) = { (L1-L2) ×100}/L1
< evaluation criterion >
A: the elastic recovery rate is more than 85 percent;
b: the elastic recovery rate is more than 80% and less than 85%;
c: the elastic recovery rate is more than 70% and less than 80%;
f: the elastic recovery rate is less than 70%.
(repeated pressing resistance at high temperature)
Using the photosensitive resin compositions prepared in examples 1 to 4 and comparative examples 1 to 3 and 5, a resist spacer having a height of 2.5 μm, a width of 10 μm on the upper surface and a width of 14 μm on the lower surface was prepared in the same manner as described above on a glass substrate, and a repeated pressing test was performed for 250 cycles by the above-described microhardness tester with "maximum load of 30mN, applied load speed of 3.33mN/sec, held maximum load time of 5 seconds, minimum load of 0.2mN, and removed load speed of 3.33mN/s" as 1 cycle. The heights of each resist spacer before and after the pressing test were measured by a white light interferometer under the conditions of 23 to 25℃near room temperature and 80℃at a high temperature, and the difference in height between before and after the test was evaluated. The height change before and after the repeated pressing test at room temperature was designated Δh1, and the height change before and after the repeated pressing test at 80 ℃ was designated Δh2. Although the measurement was not performed for comparative examples 4 and 6 to 8, it was assumed that the results of evaluation for any of the comparative examples were F from the point that the acid value of the monomer group (B) was 0. In table 1, the estimated values are shown by letters with brackets, and other evaluations are similar.
< evaluation criterion >
A: height change Δh1:0 μm +.DELTA.H2 +.0.1 μm, +.DELTA.H2-. DELTA.H2 +.0.02 μm;
b: height change Δh1:0.1 μm < ΔH2+.0.15 μm, ΔH2- ΔH2+.0.04 μm;
f: height change Δh1:0.15 μm < ΔH2, or ΔH2- ΔH2 >0.40 μm.
(extent of the uncomfortableness)
The photosensitive resin compositions prepared in examples 1 to 4 and comparative examples 1 to 8 were applied to a glass substrate, and exposed to light of 100mJ/cm using an ultra-high pressure mercury lamp 2 The dried pre-baked film was exposed to light and developed (in terms of i-line), and heated in an oven at 230℃for 40 minutes, thereby forming a cured film having a thickness of 3. Mu.m. The pencil hardness test was carried out on each cured film in accordance with JIS K5600-5-4:1999, and evaluated on the basis of the following criteria.
< evaluation criterion >
A: the pencil hardness is less than 5H;
f: the pencil hardness is above 5H.
(developer solubility)
The photosensitive resin compositions prepared in examples 1 to 4 and comparative examples 1 to 6 and 8 were applied onto a glass substrate by a spin coater, dried under reduced pressure, and then left to stand on a heating plate heated to 90℃for 2 minutes. After the heat dissipation of the glass substrate, the glass substrate was placed in a petri dish having a diameter of 12cm phi so that the coated surface became the upper surface, 50mg of a developing solution (20-fold pure water dilution of CD-379, manufactured by ADEKA) was added, and the petri dish was horizontally shaken for 2 minutes, after which a solution was collected. The turbidity of the collected solution was measured by using a turbidimeter 2100Q manufactured by HACH corporation, and evaluated on the basis of the following criteria. In addition, although comparative example 7 was not measured, the acid value of the monomer group (B) was 0 and the first crosslinkable (meth) acrylate monomer (B1) and the second crosslinkable (meth) acrylate monomer (B2) were not contained, and the result after evaluation was assumed to be F.
< evaluation criterion >
A: transparent (haze less than 10);
b: cloudiness (turbidity 10 or more and less than 100);
c: white turbidity (turbidity 100 or more);
f: many precipitates
[ height deviation (scanning unevenness, lens unevenness) ]
The photosensitive resin compositions prepared in examples 1 to 4 and comparative examples 1 to 8 were applied to a substrate with a protective film by a spin coater by performing a cleaning treatment on the substrate with a protective film with a predetermined exposure amount using a UV/ozone apparatus. The article was dried (prebaked) in an oxidation-free oven at 105℃for 10 minutes to form a coating film having a thickness of 3.50. Mu.m. Next, the substrate was cooled to room temperature, and exposure was performed by a negative photomask [ -circular ] pattern design, Φ being 10 μm, using a multiple lens scanning system (Multi-lens scanning system).
Then, the development was performed by spraying with an automatic developing device, further washing with water and air-drying. Finally, the resist spacers were dried (post-baked) in a non-oxidizing oven at 230℃for 30 minutes to form O (round) pattern.
In the formed resist spacers, the height deviation (maximum height-minimum height) of 20 resist spacers was measured at a constant interval by a height difference measuring instrument in a direction perpendicular to the direction in which a plurality of lenses were arranged in two rows in the substrate surface, in a range of 20mm square in the substrate surface corresponding to the joint portion between the lenses, and the scanning unevenness of the resist spacers was evaluated on the basis of the following criteria.
< evaluation criterion >
A: the height deviation of the photoresist spacers is less than 0.03 mu m;
f: the height deviation of the photoresist spacers is more than 0.03 mu m.
TABLE 1
Industrial applicability
The photosensitive resin composition of the present invention is suitable for use as a material for forming a resist spacer.
Claims (8)
1. A photosensitive resin composition comprising:
an alkali-soluble resin (A) having a double bond equivalent of 200g/mol or less;
a monomer group (B) comprising a first crosslinkable (meth) acrylate monomer (B1) having 6 or more crosslinkable functional groups at least one of which is a hydrogen-bond-type crosslinkable functional group, and a second crosslinkable (meth) acrylate monomer (B2) having 6 or more crosslinkable functional groups at least one of which is a hydrogen-bond-type crosslinkable functional group, the number of hydrogen-bond-type crosslinkable functional groups being smaller than the number of the first crosslinkable (meth) acrylate monomer (B1), the acid value of the first crosslinkable (meth) acrylate monomer (B2) being 1mgKOH/g to 20 mgKOH/g; and
a photopolymerization initiator (C).
2. The photosensitive resin composition according to claim 1, wherein the hydroxyl value of the monomer group (B) is 15mgKOH/g to 70mgKOH/g.
3. The photosensitive resin composition according to claim 1 or 2, wherein the second crosslinkable (meth) acrylate monomer (B2) does not have a hydrogen-bonding crosslinkable functional group.
4. The photosensitive resin composition according to any one of claims 1 to 3, wherein 80 to 200 parts by mass of the monomer group (B) is contained with respect to 100 parts by mass of the alkali-soluble resin (a).
5. The photosensitive resin composition according to any one of claims 1 to 4, wherein a mass ratio (B1: B2) of the first crosslinkable (meth) acrylate monomer (B1) to the second crosslinkable (meth) acrylate monomer (B2) is 1:10 to 10:1.
6. A cured product obtained from the photosensitive resin composition according to any one of claims 1 to 5.
7. The cured product according to claim 6, which is a photoresist spacer, a partition wall material, a lens material, an interlayer insulating film material, a protective film material, an optical waveguide material, or a planarizing film material.
8. An image display device comprising the cured product according to claim 6 or 7.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2021135644 | 2021-08-23 | ||
| JP2021-135644 | 2021-08-23 | ||
| PCT/JP2022/031524 WO2023027010A1 (en) | 2021-08-23 | 2022-08-22 | Photosensitive resin composition, cured product, and image display device |
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| CN117795420A true CN117795420A (en) | 2024-03-29 |
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| Country | Link |
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| JP (1) | JPWO2023027010A1 (en) |
| KR (1) | KR20240032114A (en) |
| CN (1) | CN117795420A (en) |
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| JP4821206B2 (en) * | 2005-07-29 | 2011-11-24 | 東レ株式会社 | Photosensitive coloring composition for color filter and color filter |
| JP6082248B2 (en) | 2009-05-26 | 2017-02-15 | オプトドット コーポレイション | Batteries utilizing an anode coated directly on a nanoporous separator |
| JP2014041310A (en) * | 2012-07-27 | 2014-03-06 | Fujifilm Corp | Colored curable composition, color filter, and display device |
| JP6385853B2 (en) * | 2015-02-20 | 2018-09-05 | 富士フイルム株式会社 | Photosensitive composition, method for producing cured film, cured film, touch panel, touch panel display device, liquid crystal display device, and organic EL display device |
| JP6996078B2 (en) * | 2016-10-04 | 2022-01-17 | 三菱ケミカル株式会社 | Colored resin composition, color filter and image display device |
| JP6461222B2 (en) | 2017-03-30 | 2019-01-30 | 本田技研工業株式会社 | Oil strainer and power transmission device |
| CN111149058B (en) * | 2017-09-22 | 2024-03-08 | 东丽株式会社 | Transparent photosensitive resin composition and application thereof, photoetching spacer, liquid crystal display device and manufacturing method thereof |
| JP2020071483A (en) | 2018-10-29 | 2020-05-07 | 東レ株式会社 | Negative photosensitive resin composition, and photospacer and image display device using the same |
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- 2022-08-22 JP JP2023543891A patent/JPWO2023027010A1/ja active Pending
- 2022-08-22 CN CN202280053681.0A patent/CN117795420A/en active Pending
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| KR20240032114A (en) | 2024-03-08 |
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