CN106662815B - Negative photosensitive resin composition, resin cured film, partition wall, and optical element - Google Patents
Negative photosensitive resin composition, resin cured film, partition wall, and optical element Download PDFInfo
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- CN106662815B CN106662815B CN201580038938.5A CN201580038938A CN106662815B CN 106662815 B CN106662815 B CN 106662815B CN 201580038938 A CN201580038938 A CN 201580038938A CN 106662815 B CN106662815 B CN 106662815B
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- China
- Prior art keywords
- resin composition
- ink
- photosensitive resin
- negative photosensitive
- alkali
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 134
- 238000005192 partition Methods 0.000 title claims abstract description 116
- 229920005989 resin Polymers 0.000 title claims abstract description 105
- 239000011347 resin Substances 0.000 title claims abstract description 105
- 230000003287 optical effect Effects 0.000 title claims abstract description 57
- 239000005871 repellent Substances 0.000 claims abstract description 150
- 239000002253 acid Substances 0.000 claims abstract description 134
- 239000010408 film Substances 0.000 claims abstract description 133
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 87
- 230000002940 repellent Effects 0.000 claims abstract description 83
- 239000000758 substrate Substances 0.000 claims abstract description 47
- 239000010409 thin film Substances 0.000 claims abstract description 37
- 239000002096 quantum dot Substances 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims description 91
- 238000000034 method Methods 0.000 claims description 51
- 125000001153 fluoro group Chemical group F* 0.000 claims description 35
- 229910052731 fluorine Inorganic materials 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 20
- 239000003505 polymerization initiator Substances 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 11
- 239000007870 radical polymerization initiator Substances 0.000 claims description 11
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 35
- 239000003999 initiator Substances 0.000 abstract description 16
- 238000003491 array Methods 0.000 abstract description 13
- 230000002829 reductive effect Effects 0.000 abstract description 7
- 239000000976 ink Substances 0.000 description 141
- -1 silane compound Chemical class 0.000 description 98
- 239000010410 layer Substances 0.000 description 61
- 238000001723 curing Methods 0.000 description 46
- 239000000203 mixture Substances 0.000 description 41
- 239000000243 solution Substances 0.000 description 40
- 238000005401 electroluminescence Methods 0.000 description 39
- 239000003822 epoxy resin Substances 0.000 description 28
- 229920000647 polyepoxide Polymers 0.000 description 28
- 230000015572 biosynthetic process Effects 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 24
- 238000011161 development Methods 0.000 description 23
- 229910000077 silane Inorganic materials 0.000 description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- 239000011521 glass Substances 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 230000002378 acidificating effect Effects 0.000 description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 14
- 150000001450 anions Chemical class 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000003431 cross linking reagent Substances 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 150000004756 silanes Chemical class 0.000 description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 12
- 239000004033 plastic Substances 0.000 description 11
- 229920003023 plastic Polymers 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 239000003513 alkali Substances 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000010526 radical polymerization reaction Methods 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 125000004849 alkoxymethyl group Chemical group 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 125000003396 thiol group Chemical group [H]S* 0.000 description 8
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 125000001309 chloro group Chemical group Cl* 0.000 description 7
- 239000003086 colorant Substances 0.000 description 7
- 230000000873 masking effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000001226 reprecipitation Methods 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 125000005409 triarylsulfonium group Chemical group 0.000 description 6
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical group C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- IAXXETNIOYFMLW-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-methylprop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C(=C)C)CC1C2(C)C IAXXETNIOYFMLW-UHFFFAOYSA-N 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 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 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000000206 photolithography Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 3
- MCNPOZMLKGDJGP-UHFFFAOYSA-N 2-[2-(4-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 MCNPOZMLKGDJGP-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- NCCTVAJNFXYWTM-UHFFFAOYSA-N 2-tert-butylcyclohexa-2,5-diene-1,4-dione Chemical compound CC(C)(C)C1=CC(=O)C=CC1=O NCCTVAJNFXYWTM-UHFFFAOYSA-N 0.000 description 3
- RQPNXPWEGVCPCX-UHFFFAOYSA-N 3-sulfanylbutanoic acid Chemical compound CC(S)CC(O)=O RQPNXPWEGVCPCX-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 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 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 229920003180 amino resin Polymers 0.000 description 3
- 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 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000007974 melamines Chemical class 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- LQNUZADURLCDLV-IDEBNGHGSA-N nitrobenzene Chemical group [O-][N+](=O)[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 LQNUZADURLCDLV-IDEBNGHGSA-N 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- QYGBYAQGBVHMDD-XQRVVYSFSA-N (z)-2-cyano-3-thiophen-2-ylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C/C1=CC=CS1 QYGBYAQGBVHMDD-XQRVVYSFSA-N 0.000 description 2
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical group C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical class NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 2
- GYQQFWWMZYBCIB-UHFFFAOYSA-N 1-[diazo-(4-methylphenyl)sulfonylmethyl]sulfonyl-4-methylbenzene Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(=[N+]=[N-])S(=O)(=O)C1=CC=C(C)C=C1 GYQQFWWMZYBCIB-UHFFFAOYSA-N 0.000 description 2
- WQVIVQDHNKQWTM-UHFFFAOYSA-N 1-tert-butyl-4-iodobenzene Chemical compound CC(C)(C)C1=CC=C(I)C=C1 WQVIVQDHNKQWTM-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 2
- ZJRNXDIVAGHETA-UHFFFAOYSA-N 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=C(OC)C(OC)=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 ZJRNXDIVAGHETA-UHFFFAOYSA-N 0.000 description 2
- XOPKKHCDIAYUSK-UHFFFAOYSA-N 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound O1C(C)=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 XOPKKHCDIAYUSK-UHFFFAOYSA-N 0.000 description 2
- PNDRGJCVJPHPOZ-UHFFFAOYSA-N 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C=CC=2OC=CC=2)=N1 PNDRGJCVJPHPOZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- DRYBUHKBBRHEAE-UHFFFAOYSA-N 2-[diazo(propan-2-ylsulfonyl)methyl]sulfonylpropane Chemical compound CC(C)S(=O)(=O)C(=[N+]=[N-])S(=O)(=O)C(C)C DRYBUHKBBRHEAE-UHFFFAOYSA-N 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical class [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical group C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
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- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
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- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
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- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
Abstract
The invention provides a negative photosensitive resin composition for manufacturing optical elements (organic EL elements, quantum dot displays, TFT arrays, thin film solar cells) and the like, wherein the upper surface of a partition wall has good ink-repellency and residues of an opening part can be reduced, a resin cured film for the optical elements, the upper surface of which has good ink-repellency, a partition wall for the optical elements, and the optical elements with the partition wall, wherein fine and high-precision patterns can be formed. A negative photosensitive resin composition comprising a photocurable alkali-soluble resin or alkali-soluble monomer, a photopolymerization initiator, an acid generator, an acid curing agent and an ink repellent, and an optical element having a plurality of dots on a substrate surface and the partition wall between adjacent dots, a cured film and a partition wall formed using the negative photosensitive resin composition, and the optical element are provided.
Description
Technical Field
The present invention relates to a negative photosensitive resin composition, a resin cured film, a partition wall, and an optical element used for manufacturing an optical element such as an organic EL element, a quantum dot display, a TFT array, and a thin film solar cell, and more particularly, to an organic EL element, a quantum dot display, a TFT array, a thin film solar cell, and the like.
Background
In the production of optical elements such as organic EL (Electro-Luminescence) elements, quantum dot displays, tft (thin film transistor) arrays, and thin film solar cells, a method of pattern-printing an organic layer such as a light-emitting layer or an inorganic layer into dots by an Inkjet (IJ) method is sometimes used. In this method, a partition wall is provided along the outline of a dot to be formed, and ink containing a material of an organic layer or an inorganic layer is injected into a partition (hereinafter, also referred to as an "opening") surrounded by the partition wall, and dried and/or heated, thereby forming a dot of a desired pattern.
When pattern printing is performed by the Inkjet (IJ) method, the upper surface of the partition wall needs to have ink repellency in order to prevent mixing of ink between adjacent dots and to uniformly apply ink at the time of dot formation. On the other hand, the dot-forming openings surrounded by the partition walls including the side surfaces of the partition walls need to have ink affinity. Therefore, in order to obtain a partition wall having an ink-repellent property on the upper surface, a method of forming a partition wall corresponding to a pattern of dots by photolithography using a photosensitive resin composition containing an ink-repellent agent is known.
In recent years, in order to obtain a product with higher precision in such an optical element such as an organic EL element, for example, patent document 1 proposes a photosensitive resin composition capable of forming a coating film having excellent ink repellency and ink rolling property and further capable of forming a fine pattern. In patent document 1, the above-described effects are obtained by using a photosensitive resin composition of the following (1) or (2) as a photosensitive resin composition for forming partition walls, and containing a special fluororesin as an ink repellent, the photosensitive resin composition of the following (1) containing an acid generator and an acid curing agent, the acid curing agent being a compound having 2 or more reactive groups capable of crosslinking with an acid group, and the photosensitive resin composition of the following (2) containing a photo radical polymerization initiator and a radical crosslinking agent, the radical crosslinking agent being a compound having 2 or more ethylenic double bonds and having no acid group.
However, in the production of organic EL devices, quantum dot displays, TFT arrays, and thin-film solar cells, from the viewpoint of improving production efficiency, a photosensitive resin composition containing an ink-repellent agent, particularly a photosensitive resin composition classified as (2) in patent document 1, is required to have higher sensitivity. Therefore, in such a photosensitive resin composition, a high sensitivity can be achieved by increasing the amount of the radical initiator, and a partition wall having an ink-repellent property on the upper surface can be formed even with a low exposure amount, but there is a problem that the line width is easily increased and the pattern formability is deteriorated.
In addition, for example, patent document 2 proposes a photosensitive composition for an organic EL element, which contains a hydrophilic epoxy resin (a), a polyfunctional monomer (B), a cationically polymerizable compound (C), a hydrolyzable silane compound (D), a photo-radical polymerization initiator (E), and an acid generator (F), as a negative photosensitive resin composition having high sensitivity, high resolution, excellent adhesion between a cured product thereof and a substrate, and excellent elastic recovery properties, and capable of alkali development. However, the composition in patent document 2 is difficult to achieve high sensitivity, and is insufficient in liquid repellency.
Documents of the prior art
Patent document
Patent document 2 Japanese patent laid-open No. 2012-014931
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a negative photosensitive resin composition for manufacturing optical elements such as organic EL elements, quantum dot displays, TFT arrays, and thin-film solar cells, which has excellent ink repellency on the upper surface of a partition wall, can reduce residues at an opening portion, and can be applied to flexible applications (flexible application) using a plastic substrate, in order to form a fine and precise pattern using the obtained partition wall while maintaining good production efficiency.
The purpose of the present invention is to provide a resin cured film having good ink repellency on the upper surface, and a partition wall for an optical element, such as an organic EL element, a quantum dot display, a TFT array, or a thin-film solar cell, which can form a fine and highly precise pattern by virtue of having good ink repellency on the upper surface, and which can be applied to flexible applications using a plastic substrate.
It is another object of the present invention to provide optical elements such as organic EL elements, quantum dot displays, TFT arrays, and thin film solar cells, which have dots formed accurately by uniformly applying ink to openings defined by partition walls, and particularly optical elements for flexible applications including plastic substrates.
The invention provides a negative photosensitive resin composition, a resin cured film, a partition wall and an optical element having the following configurations [1] to [9 ].
[1] A negative photosensitive resin composition comprising a photocurable alkali-soluble resin or alkali-soluble monomer (A), a photoradical polymerization initiator (B), a photoacid generator (C), an acid curing agent (D), and an ink repellent (E) having a fluorine atom.
[2] The negative photosensitive resin composition according to [1], further comprising a compound (F) having 2 or more unsaturated double bonds in a molecule and having no acid group or fluorine atom.
[3] The negative photosensitive resin composition according to [1] or [2], wherein the acid curing agent (D) is at least 1 selected from a melamine-based compound, a urea-based compound, and an epoxy-based compound.
[4] The negative photosensitive resin composition according to any one of [1] to [3], which is used for producing an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell.
[5] A resin cured film formed using the negative photosensitive resin composition according to any one of the above [1] to [4 ].
[6] A partition wall formed in a shape dividing a substrate surface into a plurality of partitions for forming dots, characterized by being composed of a cured resin film of [5 ].
[7] An optical element having a plurality of dots and partitions between adjacent dots on a surface of a substrate, wherein the partitions are formed by the partitions of [6 ].
[8] The optical element according to [7], wherein the optical element is an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell.
[9] The optical element according to [7] or [8], wherein the dots are formed by an inkjet method.
According to the present invention, it is possible to provide a negative photosensitive resin composition for manufacturing optical elements such as organic EL elements, quantum dot displays, TFT arrays, thin film solar cells, and the like, which can form fine and highly precise patterns by the partition walls by reducing the residue of the openings while maintaining good production efficiency.
The resin cured film of the present invention has good ink repellency on the upper surface, and the partition walls have good ink repellency on the upper surface, and can form a fine and precise pattern, and thus can be suitably used for organic EL elements, quantum dot displays, TFT arrays, thin film solar cells, and the like, particularly optical elements including flexible applications using plastic substrates.
The optical element of the present invention is an optical element having dots formed with high precision by uniformly applying ink to openings defined by partition walls, and specifically, an organic EL element, a quantum dot display, a TFT array, a thin film solar cell, and the like. According to the present invention, the above-described effects can be achieved even in an optical element including a flexible application using a plastic substrate.
Drawings
Fig. 1A is a process diagram schematically showing a method for manufacturing a partition wall according to an embodiment of the present invention.
Fig. 1B is a process diagram schematically showing a method for manufacturing a partition wall according to an embodiment of the present invention.
Fig. 1C is a process diagram schematically showing a method for manufacturing a partition wall according to an embodiment of the present invention.
Fig. 1D is a process diagram schematically showing a method for manufacturing a partition wall according to an embodiment of the present invention.
Fig. 2A is a process diagram schematically showing a method for manufacturing an optical element according to an embodiment of the present invention.
Fig. 2B is a process diagram schematically showing a method for manufacturing an optical element according to an embodiment of the present invention.
Detailed Description
In the present specification, the following terms are used in the following meanings, respectively.
"(meth) acryloyl" is a generic term for "methacryloyl" and "acryloyl". (meth) acryloyloxy, (meth) acrylic acid, (meth) acrylate, (meth) acrylamide and (meth) acrylic resin are also used herein.
The group represented by the formula (x) is sometimes abbreviated as group (x). The compound represented by the formula (y) may be abbreviated as compound (y). Here, the formulae (x) and (y) represent arbitrary formulae.
"a resin mainly composed of a certain component" or "a resin mainly composed of a certain component" means that the proportion of the component is 50% by mass or more relative to the total amount of the resin.
The "side chain" is a group other than a hydrogen atom or a halogen atom bonded to a carbon atom constituting the main chain in a polymer in which the main chain is constituted by a repeating unit formed of carbon atoms.
The "total solid content of the photosensitive resin composition" refers to a component forming a cured film described later among components contained in the photosensitive resin composition, and can be determined from a residue obtained by heating the photosensitive resin composition at 140 ℃ for 24 hours to remove a solvent. The total solid content may be calculated from the charged amount.
A film formed of a cured product of a composition containing a resin as a main component is referred to as a "resin cured film". The film coated with the photosensitive resin composition is referred to as a "coating film", and the film obtained by drying the coating film is referred to as a "dried film". The film obtained by curing the "dried film" is a "resin cured film". The "resin cured film" may be simply referred to as a "cured film".
The resin cured film may be in the form of partition walls formed in a shape that divides a predetermined region into a plurality of sections. For example, the following "ink" is injected into the partition defined by the partition, that is, the opening surrounded by the partition, to form a "dot".
"ink" is a term that collectively refers to liquids that have optical and/or electrical functionality after being dried, cured, etc. In optical devices such as organic EL devices, quantum dot displays, TFT arrays, thin-film solar cells, and color filters, dots as various constituent elements are sometimes pattern-printed by an Inkjet (IJ) method using the dot forming ink. "ink" includes inks used in such applications.
The "ink repellency" is a property of repelling the above ink, and has both water repellency and oil repellency. The ink repellency can be evaluated by, for example, the contact angle when the ink is dropped. The "ink affinity" is a property opposite to the ink repellency, and can be evaluated by the contact angle at the time of dropping the ink, similarly to the ink repellency. Alternatively, the oleophilic property can be evaluated by evaluating the degree of wetting spread of the ink (wetting spread of the ink) when the ink is dropped, with a predetermined standard.
"dot" means the smallest area of the optical element that can be modulated by light. In optical elements such as organic EL elements, quantum dot displays, TFT arrays, thin-film solar cells, and color filters, 1 dot is 1 pixel in black-and-white display, and 3 dots (R (red), G (green), B (blue), and the like) are 1 pixel in color display, for example. "optical element" is used as a term to encompass electronic devices. "percentage (%)" represents mass% without specific description.
Hereinafter, embodiments of the present invention will be described.
[ negative photosensitive resin composition ]
The negative photosensitive resin composition of the present invention is characterized by containing a photocurable alkali-soluble resin or alkali-soluble monomer (a), a photo radical polymerization initiator (B), a photoacid generator (C), an acid curing agent (D), and an ink repellent (E) having a fluorine atom. In the present specification, the acid curing agent (D) is a curing agent which reacts with an acidic group such as a carboxylic acid or a phenolic hydroxyl group in the presence of an acid. The negative photosensitive resin composition of the present invention can be suitably used for producing optical devices such as organic EL devices, quantum dot displays, TFT arrays, thin film solar cells, and color filters, and particularly, significant effects can be expected in organic EL devices, quantum dot displays, TFT arrays, and thin film solar cells.
In general, a negative photosensitive resin composition is cured by exposure to light to form a cured film. In this case, when the exposed portion and the unexposed portion having a predetermined shape are formed by masking or the like, the unexposed portion is not cured and can be selectively removed by an alkali developer. As a result, the cured film can be formed into a partition wall having a shape dividing the predetermined region into a plurality of sections.
The negative photosensitive resin composition of the present invention is a negative photosensitive resin composition in which an alkali-soluble resin or an alkali-soluble monomer (a) is polymerized and cured in the exposed portion by radicals generated from a photo radical polymerization initiator (B) to form a cured film. Here, the alkali-soluble resin or the alkali-soluble monomer (a) does not contain a fluorine atom. The ink-repellent agent (E) has a property of migrating to the upper surface during the formation of the cured film by having a fluorine atom (upper surface migration property), and the ink-repellent agent (E) migrating to the upper surface is fixed to the upper surface of the cured film.
Here, in the radical polymerization reaction using light, the surface of the cured film in contact with the atmosphere is more likely to be inhibited by the reaction due to oxygen. In the negative photosensitive resin composition of the present invention, the photoacid generator (C) generates an acid upon exposure, and the acid curing agent (D) reacts with an acid group of an alkali-soluble resin or a carboxylic acid of an alkali-soluble monomer (a) in the presence of the acid to cure. In addition, it is also considered that the acid curing agents (D) react with each other at this time to contribute to curing. Unlike radical polymerization, this curing reaction is not affected by oxygen. Therefore, the negative photosensitive resin composition of the present invention can provide a cured film, particularly a cured film having improved curability of the alkali-soluble resin or the alkali-soluble monomer (a) and fixation of the ink repellent (E) on the upper surface of the cured film. Further, a cured film having curability equivalent to that of a conventional cured film, particularly curability of the upper surface, even with a low exposure amount was obtained.
As described above, in the negative photosensitive resin composition of the present invention, curing inside the cured film can be sufficiently performed by combining the radical polymerization reaction using light and the curing reaction in the presence of acid generated by light. Therefore, the cured portion as an exposed portion is resistant to corrosion and peeling by an alkali developing solution during development. Therefore, the exposed portion is less susceptible to long-term development, and therefore, is advantageous for removal of residues in the opening portion and the like.
The negative photosensitive resin composition of the present invention further contains, as necessary, a compound (F) (hereinafter also referred to as "crosslinking agent (F)"), a thiol compound (G) (hereinafter also referred to as "thiol compound (G)"), a phosphoric acid compound (H), a polymerization inhibitor (I), a solvent (J), a colorant (K), and other optional components, wherein the compound (F) has 2 or more unsaturated double bonds in a molecule and does not have any one of an acidic group and a fluorine atom, and the thiol compound (G) has 3 or more mercapto groups in 1 molecule.
(alkali-soluble resin or alkali-soluble monomer (A))
The alkali-soluble resin symbol (AP) and the alkali-soluble monomer symbol (AM) will be described separately. In the following description, these may be collectively referred to as "alkali-soluble resin (a)".
The alkali-soluble resin (a) has photocurability. The alkali-soluble resin (a) does not have a fluorine atom. In the negative photosensitive resin composition, the radical polymerization initiator (B) generates radicals and the photoacid generator (C) generates an acid by exposure. At this time, the alkali-soluble resin (a) undergoes a polymerization reaction by itself by the radical, and is reacted with the acid curing agent (D) in the presence of the acid to crosslink, thereby being sufficiently cured. The alkali-soluble resins (a) do not react with each other due to an acid.
The exposed portion of the negative photosensitive resin composition is sufficiently cured as described above. The exposed portion thus sufficiently cured is not easily removed by the alkali developer. In addition, since the alkali-soluble resin (a) is alkali-soluble, the non-exposed portions of the uncured negative photosensitive resin composition can be selectively removed by an alkali developer. As a result, the cured film can be formed into a partition wall having a shape dividing the predetermined region into a plurality of sections.
As the alkali-soluble resin (AP), a photosensitive resin having an acidic group and an ethylenic double bond in 1 molecule is preferable. The alkali-soluble resin (AP) has an ethylenic double bond in the molecule, and is polymerized by the radicals generated by the photo-radical polymerization initiator (B). The alkali-soluble resin (AP) has an acidic group in the molecule, and reacts with the acid curing agent (D) in the presence of an acid generated by the photoacid generator (C). Further, having an acidic group makes the polymer alkali-soluble.
Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group and the like, and 1 kind of these groups may be used alone or 2 or more kinds may be used in combination.
Examples of the ethylenic double bond include double bonds having addition polymerizability such as (meth) acryloyl group, allyl group, vinyl group, vinyloxy group, and vinyloxyalkyl group. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds. Some or all of the hydrogen atoms in the ethylenic double bond may be substituted with an alkyl group such as a methyl group.
Examples of the alkali-soluble resin (AP) having an ethylenic double bond include a resin (A-1) having a side chain having an acidic group and a side chain having an ethylenic double bond, and a resin (A-2) having an acidic group and an ethylenic double bond introduced into an epoxy resin. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
As such an alkali-soluble resin (AP), those described in, for example, paragraphs [0108] and [0126] of International publication No. 2014/046209 (hereinafter, referred to as WO2014/046209) and paragraphs [0067] [0085] of International publication No. 2014/069478 (hereinafter, referred to as WO2014/069478) can be used.
The alkali-soluble resin (AP) is preferably the resin (a-2) in view of being able to obtain a pattern of dots with high resolution by suppressing peeling of the cured film during development, in view of being good in linearity of the pattern when the dots are linear, and in view of easily obtaining a smooth cured film surface. The good linearity of the pattern means that the obtained partition wall has no notch or the like at the edge and is linear.
As the resin (a-2), particularly preferred are resins in which an acidic group and an ethylenic double bond are introduced into epoxy resins such as bisphenol a type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol methane type epoxy resin, epoxy resin having a naphthalene skeleton, epoxy resin having a biphenyl skeleton, and fluorenyl-substituted bisphenol a type epoxy resin, respectively.
The number of ethylenic double bonds in 1 molecule of the alkali-soluble resin (AP) is preferably 3 or more on average, and particularly preferably 6 or more. When the number of ethylenic double bonds is not less than the lower limit of the above range, a difference in alkali solubility between the exposed portion and the unexposed portion is easily imparted, and a fine pattern can be formed with a smaller amount of exposure.
The mass-average molecular weight (Mw) of the alkali-soluble resin (AP) is preferably 1.5X 103～30×103Particularly preferably 2X 103～15×103. In addition, the number average molecular weight (Mn) is preferably 500 to 20X 103Particularly preferably 1.0X 103～10×103. When the mass average molecular weight (Mw) and the number average molecular weight (Mn) are not less than the lower limit of the above range, curing at the time of exposure is sufficient, and when they are not more than the upper limit of the above range, developability is good.
In the present specification, the number average molecular weight (Mn) and the mass average molecular weight (Mw) are values measured by gel permeation chromatography using polystyrene as a standard substance unless otherwise specified.
The acid value of the alkali-soluble resin (AP) is preferably 10 to 300mgKOH/g, and particularly preferably 30 to 150 mgKOH/g. When the acid value is within the above range, the negative photosensitive composition can be developed satisfactorily.
As the alkali-soluble monomer (AM), for example, a monomer (A-3) having an acidic group and an ethylenic double bond is preferably used. The acidic group and ethylenic double bond are the same as those of the alkali-soluble resin (AP). The acid value of the alkali-soluble monomer (AM) is also preferably in the same range as that of the alkali-soluble resin (AP).
Examples of the monomer (A-3) include 2,2, 2-triacryloxymethylethylphthalic acid and the like.
The alkali-soluble resin or the alkali-soluble monomer (a) contained in the negative photosensitive resin composition may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The content of the alkali-soluble resin or the alkali-soluble monomer (a) in the total solid content of the negative photosensitive resin composition is preferably 5 to 80% by mass, and particularly preferably 10 to 60% by mass. When the content ratio is within the above range, the negative photosensitive resin composition is excellent in photocurability and developability.
(photo radical polymerization initiator (B))
The photo radical polymerization initiator (B) of the present invention is not particularly limited as long as it is a compound having a function of a photo radical polymerization initiator generating radicals by active light. Hereinafter, the photo radical polymerization initiator (B) is also simply referred to as "photopolymerization initiator (B)".
Examples of the photopolymerization initiator (B) include the photopolymerization initiators described in, for example, paragraphs [0130] and [0131] of WO2014/046209 and paragraphs [0089] [0090] of WO 2014/069478.
Of the photopolymerization initiators (B), benzophenones, aminobenzoic acids, and aliphatic amines are preferably used together with other radical initiators in some cases because they exhibit a sensitizing effect. The photopolymerization initiator (B) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The content of the photopolymerization initiator (B) in the total solid content of the negative photosensitive resin composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 1 to 15% by mass. When the content ratio is within the above range, the negative photosensitive resin composition is excellent in photocurability and developability.
(acid Generator (C))
The photoacid generator (C) is not particularly limited as long as it is a compound that decomposes to generate an acid upon irradiation with active light. In general, any compound can be selected from compounds used as photoacid generators in photosensitive resin compositions using cation-polymerizable alkali-soluble resins. Hereinafter, the photoacid generator (C) is also simply referred to as "acid generator (C)".
As described above, in the negative photosensitive resin composition of the present invention, the acid generated from the acid generator (C) participates in the binding of the alkali-soluble resin (a) and the acid curing agent (D) described below.
The acid generator (C) is decomposed by irradiation with active light to generate an acid. Specific examples of the active rays include high-energy rays such as ultraviolet light, X-rays, and electron beams. When the negative photosensitive resin composition is used for producing the partition wall for an optical element, i-ray (365nm), h-ray (405nm) and g-ray (436nm) are preferably used for exposure. As the acid generator (C), it is preferable to select an acid generator (C) having a large absorbance at the wavelength of light used for exposure. An acid generator having absorption at 350 to 450nm is preferable, and particularly an acid generator having absorption for at least 1 of i-ray (365nm), h-ray (405nm) and g-ray (436nm) is preferable because of high curability.
Specific examples of the acid generator (C) include:
a salt-based acid generator and a nonionic acid generator. As
Examples of the salt-based acid generator include compounds having a mono-to triphenylsulfonium skeleton represented by the following formula (C0)
Salt and iodine
Salt-based compounds, and the like.
In the formula (C0), Ra1And Ra2Represents an alkyl group or phenyl group having 1 to 20 carbon atoms which may have a substituent, Ra3Represents an organic group having a valence of 1. w is an integer of 0 to 5. X－Represents an anion, and specifically includes SbF6 －Phosphorus based anions such as PF6 －、(Rf1)nPF6－n －(Rf1Is fluoroalkyl, n is 1 to 3), sulfonate anion such as RaSO3 －(RaAn alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 18 carbon atoms, part or all of which may be substituted with fluorine atoms). As RaSO3 －R of (A) to (B)aFor example, there may be mentioned-CF3、－C4F9、－C8F17Iso-perfluoroalkyl group, -C6F5Isoperfluoroaryl, -Ph-CH3(wherein Ph represents a phenyl group), an aryl group, etc.
As the compound (C0), R is preferreda1And Ra2All are phenyl (which may be substituted). Specifically, those having a triphenylsulfonium skeleton represented by the following formula (C1) or the following formula (C2) are preferable
And (3) salt. In the compound (C1) and the compound (C2), a compound in which a hydrogen atom of a phenyl group having a triphenylsulfonium skeleton is substituted may be used as the acid generator (C).
In the formulae (C1) and (C2), Xa－And Xb－Represents an anion, and specifically includes an anion similar to X in the above formula (C0)-The same anion. As Xa-And Xb-Phosphorus-based anions and sulfonate-based anions are preferable.
Note that these should be mentioned
In the salt, the cation portion absorbs the irradiated light, and the anion portion serves as a generation source of the acid.
As the compound (C0), there may be mentioned the compound represented by the following formula (C0-1)
Salts as compounds having a monophenylsulfonium skeleton
And (3) salt.
In addition, as a compound having a triphenylsulfonium skeleton
Of the salt compounds (C1) and (C2), examples of the compounds used for exposure to i-ray radiation (365nm) include triphenylsulfonium nonafluorobutane sulfonate represented by the following formula (C1-1), and triarylsulfonium PF represented by the following formulae (C2-1) and (C2-2), respectively6Salts and triarylsulfonium special phosphorus salts. These compounds are preferable in terms of large absorbance at a wavelength of 365nm and easy availability.
In the formula (C2-2), Rf1Is fluoroalkyl, and n is 1 to 3.
As iodine
The salt compound includes diarylsRadical iodine
Salts, triarylsulfonium salts.
As diaryl iodides
Specific examples of the cation moiety of the salt include diphenyliodine
4-methoxyphenyl phenyl iodide
Bis (4-tert-butylphenyl) iodide
And the like. As diaryl iodides
Specific examples of the anion portion of the salt include trifluoromethanesulfonate, nonafluorobutanesulfonate, p-toluenesulfonate, pentafluorobenzenesulfonate, hexafluorophosphate, tetrafluoroborate, hexafluoroantimonate and the like.
Diaryl iodides
The salt is composed of the cation portion and the anion portion, and is composed of a combination of 1 kind of the specific example of the cation portion and 1 kind of the specific example of the anion portion. For example, bis (4-tert-butylphenyl) iodide
Trifluoromethanesulfonate is an example.
Specific examples of the cationic moiety of the triarylsulfonium salt include triphenylsulfonium, diphenyl-4-methylphenylsulfonium, and diphenyl-2, 4, 6-trimethylphenylsulfonium. Specific examples of the anion moiety of the triarylsulfonium salt include the diaryliodonium salts
Specific examples of the anionic portion of the salt.
The triarylsulfonium salt is composed of the cation moiety and anion moiety, and is composed of a combination of 1 kind of specific example of the cation moiety and 1 kind of specific example of the anion moiety. For example, triphenylsulfonium trifluoromethanesulfonate is an example.
Examples of the nonionic acid generator include compounds having a naphthalimide skeleton, a nitrobenzene skeleton, a diazomethane skeleton, a phenylacetophenone skeleton, a 9-thioxanthone skeleton, a triazine skeleton, to which a chlorine atom is bonded, alkanesulfonic acids, arylsulfonic acids, and the like.
Specific examples of such compounds include compounds having a structure represented by the following formula (C3), the following formula (C4), the following formula (C5), the following formula (C6), and the following formula (C7) each having a naphthalimide skeleton, a nitrobenzene skeleton (wherein the position is 2 or 4 when 1 nitro group is present and the position is 2 or 5 when 2 nitro groups are present), a diazomethane skeleton, a phenylacetophenone skeleton, and a thioxanthone skeleton to which an alkanesulfonic acid or an arylsulfonic acid is bonded. Further, there may be mentioned compounds having a triazine skeleton and a chlorine atom, represented by the following formula (C8). Further, a sulfonyl compound of dialkylglyoxime represented by the following formula (C9), a sulfonyloxyiminoacetonitrile compound represented by the formula (C10), a (sulfonyloxyimino) thiophen-3 (2H) -ylidene-2- (2-methylphenyl) acetonitrile compound represented by the formula (C11), and the like can be given.
In the compounds (C3), (C4), (C6), (C7) and (C11), compounds in which the hydrogen atom of the benzene ring forming the skeleton of each compound is substituted may also function as an acid generator.
R in formulas (C3) to (C7), (C9), (C10) and (C11)b1～Rb5、Rb7、Rb9And Rb11Each independently is a part or allA linear, branched or cyclic (including those having a cyclic structure in part) alkyl group having 1 to 12 carbon atoms or aryl group having 6 to 18 carbon atoms, which may be substituted with a fluorine atom. R in the formulae (C8), (C9), (C10)b6、Rb8And Rb10Each independently is an organic group having 1 to 18 carbon atoms which may have a substituent, an unsaturated bond, or a heterocyclic ring.
Specific examples of the compound having a nitrobenzene skeleton represented by the above formula (C4) (wherein the position is 2-or 4-position when the number of nitro groups is 1 and the positions are 2 and 5 when the number of nitro groups is 2) include 2-nitrobenzyl-p-toluenesulfonate.
Specific examples of the bis-sulfonyl diazomethane compound represented by the above formula (C5) include bis (p-toluenesulfonyl) diazomethane, bis (2, 4-dimethylphenylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (isopropylsulfonyl) diazomethane.
Specific examples of the compound having a triazine skeleton and a chlorine atom represented by the formula (C8) include 2-methyl-4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1, 3, 5-triazine represented by the following formula (C8-1), 2- (2-furyl) vinyl-bis (trichloromethyl) -1, 3, 5-triazine, 2- (5-methyl-2-furyl) vinyl-4, 6-bis (trichloromethyl) -1, 3, 5-triazine represented by the following formula (C8-2), 2- (4-methoxyphenyl) vinyl-4, 6-bis (trichloromethyl) -1, 3, 5-triazine represented by the following formula (C8-3), 2- (3, 4-dimethoxyphenyl) vinyl-4, 6-bis (trichloromethyl) -1, 3, 5-triazine, and the like.
Specific examples of the sulfonyloxyiminoacetonitrile compound represented by the formula (C10) include α - (methylsulfonoxyimino) -phenylacetonitrile, α - (methylsulfonoxyimino) -4-methoxyphenylacetonitrile, α - (trifluoromethylsulfonyloxyimino) -phenylacetonitrile, α - (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α - (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α - (propylsulfonyloxyimino) -4-methylphenylacetonitrile, and α - (methylsulfonoxyimino) -4-bromophenylacetonitrile.
Specific examples of the (sulfonyloxyimino) thiophen-3 (2H) -ylidene-2- (2-methylphenyl) acetonitrile compound represented by the formula (C11) includeb112- [ 2- (n-propylsulfonyloxyimino) thiophen-3 (2H) -ylidene as n-propyl]-2- (2-methylphenyl) acetonitrile), Rb112- [ 2- (n-octylsulfonyloxyimino) thiophen-3 (2H) -ylidene as n-octyl]-2- (2-methylphenyl) acetonitrile, Rb112- [ 2- (4-Methylphenylsulfonyloxyimino) thiophen-3 (2H) -ylidene for 4-methylphenyl]-2- (2-methylphenyl) acetonitrile and the like.
In these nonionic acid generators, a portion to which a chlorine atom, an alkanesulfonic acid, an arylsulfonic acid, or the like is bonded serves as an acid generation source.
As the nonionic acid generator, for example, as a compound used for exposure to i-ray (365nm), N-trifluoromethanesulfonic acid-1, 8-naphthalimide represented by the following formula (C3-1), 2-phenyl-2- (p-toluenesulfonyloxy) acetophenone represented by the following formula (C6-1), 2- (4-methoxyphenyl) vinyl-4, 6-bis (trichloromethyl) -1, 3, 5-triazine represented by the above formula (C8-3) and the like are preferable in terms of large absorbance at a wavelength of 365nm and easy availability.
As the nonionic acid generator, for example, a nonionic acid generator containing at least 1 kind of i-ray (365nm), h-ray (405nm) and g-ray (436nm)Examples of the compound to be exposed to light include a compound having a triazine skeleton represented by the above formula (C8) and a chlorine atom, a (sulfonyloxyimino) thiophen-3 (2H) -ylidene-2- (2-methylphenyl) acetonitrile compound represented by the above formula (C-11), and the like. Particularly, from the viewpoint of a large absorbance at a wavelength of 405nm and/or 436nm and easy availability, 2- (2-furyl) vinyl-bis (trichloromethyl) -1, 3, 5-triazine, 2- (5-methyl-2-furyl) vinyl-4, 6-bis (trichloromethyl) -1, 3, 5-triazine represented by the formula (C8-2), 2- (4-methoxyphenyl) vinyl-4, 6-bis (trichloromethyl) -1, 3, 5-triazine represented by the formula (C8-3), 2- (3, 4-dimethoxyphenyl) vinyl-4, 6-bis (trichloromethyl) -1, 3, 5-triazine, R in the formula (C-11) are preferableb11A compound which is n-propyl, n-octyl or 4-methylphenyl, etc.
In addition, under the action of light, the light from these
The acid generated by the salt-based acid generator and the nonionic acid generator is hydrochloric acid, alkanesulfonic acid, arylsulfonic acid partially or completely fluorinated, alkanesulfonic acid, or the like.
The acid generator (C) may be composed of 1 or 2 or more of the above compounds. The content of the acid generator (C) in the total solid content of the negative photosensitive resin composition is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 0.3 to 3% by mass. When the content of the acid generator (C) is in the above range, a partition wall having a sufficient ink repellency on the upper surface and capable of forming a fine and highly precise pattern can be obtained.
In addition, the use of a sensitizer described below in combination is preferable because the sensitivity is high. Examples of the sensitizer for the acid generator include 9, 10-diethoxyanthracene, 9, 10-dipropoxyanthracene, 9, 10-dibutoxyanthracene, 9, 10-bis (2-ethylhexyloxy) anthracene, 9, 10-bis (octyloxy) anthracene and the like.
(acid curing agent (D))
The acid curing agent (D) is not particularly limited as long as it is a compound that reacts with an acidic group such as a carboxylic acid or a phenolic hydroxyl group in the presence of an acid.
The acid curing agent (D) is preferably selected from amino resins, epoxy compounds, epoxy resins,
at least 1 of the oxazoline compounds. These compounds may be used alone, or 2 or more of them may be used in combination.
Examples of the amino resin include melamine compounds such as melamine compounds, guanamine compounds, urea compounds, and the like, in which a part or all of the amino groups are hydroxymethylated, melamine compounds represented by the following formula (D1) in which a part or all of the hydroxyl groups of the hydroxymethylated compounds are etherified with methanol, ethanol, n-butanol, 2-methyl-1-propanol, and the like, guanamine compounds represented by the following formula (D2), urea compounds represented by the following formula (D3), (D4), or (D5), and resins thereof.
R in the formulae (D1) to (D5)11～R32Each independently a hydrogen atom, a hydroxymethyl group or an alkoxymethyl group. R11～R16At least 1 of which is an alkoxymethyl group, R17～R20At least 1 of which is an alkoxymethyl group, R21～R24At least 1 of which is an alkoxymethyl group, R27～R30At least 1 of which is an alkoxymethyl group, R31And R32At least 1 of which is an alkoxymethyl group. R33～R36Each independently is a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group, and Xc is a single bond, a methylene group or an oxygen atom.
R11～R32The number of carbon atoms of the alkoxy group in the case of an alkoxymethyl group is preferably 1 to 6, more preferably 1 to 3. R33～R36When the alkoxy group is used, the number of carbon atoms is preferably 1 to 6, more preferably 1 to 3. Examples of the alcohol to be an alkoxy group include methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, and 2-methyl-1-propanol.
In the compounds (D1) to (D4), it is preferable that all substituents each have the same alkoxymethyl group in view of ease of production.
Examples of the urea compound represented by the formula (D5) include the following compounds.
When the acid curing agent (D) is an amino resin, 2,4, 6-tris [ bis (methoxymethyl) amino ] -1, 3, 5-triazine represented by the following formula (D1-1) or a resin thereof, 1,3,4, 6-tetrakis (methoxymethyl) glycoluril represented by the following formula (D3-1) or a resin thereof, and the like are preferable.
Examples of the epoxy compound include glycidyl ethers such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, triphenol methane type epoxy resin, and brominated epoxy resin, alicyclic epoxy resins such as 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate and bis (2, 3-epoxycyclopentyl) ether, glycidyl esters such as hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, and phthalic acid diglycidyl ester, glycidyl amines such as tetraglycidyl diaminodiphenylmethane and triglycidyl p-aminophenol, and heterocyclic epoxy resins such as triglycidyl isocyanurate.
As the epoxy compound, for example, a dicyclopentadiene type epoxy resin represented by the following formula (De1) and a naphthalene type epoxy resin represented by the following formula (De2) are preferable.
(in the formula (De1), n is an integer of 0 to 30.)
As
As the oxazoline compound, 2-vinyl-2-substituted oxazoline compounds are mentioned
Oxazoline, 2-vinyl-4-methyl-2-
Oxazoline, 2-vinyl-5-methyl-2-
Oxazoline, 2-isopropenyl-2-
Oxazoline, 2-isopropenyl-4-methyl-2-
Copolymers of polymerizable monomers such as oxazoline.
Among them, melamine-based compounds, urea-based compounds, and epoxy-based compounds are preferable as the acid curing agent (D). The acid curing agent (D) may be composed of 1 or more of the above compounds. The content of the acid curing agent (D) in the negative photosensitive resin composition is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, and particularly preferably 5 to 20 parts by mass, based on 100 parts by mass of the alkali-soluble resin (a). When the content of the acid curing agent (D) is in the above range, a partition wall having a sufficient ink repellency on the upper surface and capable of forming a fine and highly precise pattern can be obtained. In particular, if the content of the acid curing agent (D) is in the range of 5 to 20 parts by mass, the negative photosensitive resin composition has good storage stability, and a partition wall having excellent linearity of a pattern can be obtained from the composition.
(ink-repellent agent (E))
The ink repellent (E) of the present invention has a fluorine atom in the molecule. Thus, the ink repellent (E) has a property of migrating to the upper surface (upper surface migration property) and an ink repellency in the process of forming a cured film using the negative photosensitive resin composition containing the same. By using the ink repellent (E), the upper layer portion including the upper surface of the obtained cured film becomes a layer in which the ink repellent (E) is densely present (hereinafter, also referred to as "ink repellent layer"), and the ink repellency is imparted to the upper surface of the cured film.
The fluorine atom content in the ink repellent (E) is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, and particularly preferably 10 to 32% by mass. When the fluorine atom content of the ink repellent (E) is not less than the lower limit of the above range, good ink repellency can be imparted to the upper surface of the cured film, and when it is not more than the upper limit, compatibility with other components in the negative photosensitive resin composition becomes good.
In the ink-repellent layer, the ink-repellent agent (E) is present in a form of being embedded in a cured resin obtained by polymerization or crosslinking reaction of a photocurable component such as the alkali-soluble resin (a) or the acid curing agent (D) in the negative photosensitive resin composition, when the ink-repellent agent (E) itself is non-reactive. In general, when radical polymerization of ethylenic double bonds is performed, the surface of the cured film or partition wall in contact with the atmosphere is more likely to be inhibited by reaction due to oxygen. Since the ink-repellent layer is in contact with the atmosphere, radical polymerization during photocuring of the alkali-soluble resin (a) is likely to be inhibited in the ink-repellent layer portion. However, the reaction between the alkali-soluble resin (a) and the acid curing agent (D) in the negative photosensitive resin composition of the present invention is hardly inhibited by the reaction due to oxygen, and proceeds sufficiently even in the ink-repellent layer portion. This ensures sufficient fixing of the ink repellent (E) in the ink repellent layer.
That is, in order to improve the fixing property of the ink repellent (E) in the ink repellent layer, it is important to sufficiently progress the curing reaction of the alkali-soluble resin (a) and the acid curing agent (D). For this reason, it is particularly advantageous to use, as the acid generator (C), an acid generator (C) having high curability which generates an acid by an active light having a relatively long wavelength (350 to 450nm) during curing at a low exposure.
In addition, from the viewpoint of improving the fixing property of the ink repellent (E) to the ink repellent layer, the ink repellent (E) is preferably a compound having an ethylenic double bond. Since the ink-repellent agent (E) has an ethylenic double bond, radicals act on the ethylenic double bond of the ink-repellent agent (E) transferred to the upper surface, and the ink-repellent agents (E) or the ink-repellent agent (E) and other components having an ethylenic double bond contained in the negative photosensitive resin composition can be crosslinked by (co) polymerization. The reaction can be promoted by the thiol compound (G) (described later) optionally contained.
Thus, in the production of a cured film obtained by curing the negative photosensitive resin composition, the fixing property of the ink repellent (E) to the upper layer portion of the cured film, that is, the ink repellent layer can be improved. In particular, when the thiol compound (G) is contained in the negative photosensitive resin composition of the present invention, the ink-repellent agent (E) can be sufficiently fixed to the ink-repellent layer even when the exposure amount at the time of exposure is low.
As described above, in general, the surface of the cured film or partition wall in contact with the atmosphere is more easily inhibited by oxygen when the ethylenic double bond is radically polymerized, but the radical reaction by the thiol compound (G) is hardly inhibited by oxygen, and therefore, it is particularly advantageous for fixing the ink repellent (E) with a low exposure amount. Further, in the production of the partition wall, the ink-repellent agent (E) can be sufficiently prevented from coming off the ink-repellent layer or peeling off the upper surface of the ink-repellent layer during development.
Examples of the ink repellent (E) include a partial hydrolysis condensate of a hydrolyzable silane compound. The hydrolyzable silane compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds. Specific examples of the ink-repellent agent (E) containing a fluorine atom and composed of a partially hydrolyzed condensate of a hydrolyzable silane compound include the following ink-repellent agents (E1). As the ink repellent (E) having a fluorine atom, an ink repellent (E2) comprising a compound having a hydrocarbon chain as a main chain and a fluorine atom as a side chain can be used.
The ink-repellent agent (E1) and the ink-repellent agent (E2) may be used alone or in combination. In the negative photosensitive resin composition of the present invention, the ink repellent (E1) is particularly preferably used in view of excellent ultraviolet/ozone resistance.
< ink-repellent agent (E1) >
The ink repellent (E1) is a partial hydrolysis condensate of a mixture of hydrolyzable silane compounds (hereinafter, also referred to as "mixture (M)"). The mixture (M) contains, as an essential component, a hydrolyzable silane compound (hereinafter, also referred to as "hydrolyzable silane compound (s 1)") having a fluoroalkylene group and/or a fluoroalkyl group and a group in which a hydrolyzable group is bonded to a silicon atom, and optionally contains a hydrolyzable silane compound other than the hydrolyzable silane compound (s 1). Examples of the hydrolyzable silane compound optionally contained in the mixture (M) include the following hydrolyzable silane compounds (s2) and (s 3). As the hydrolyzable silane compound optionally contained in the mixture (M), the hydrolyzable silane compound (s2) is particularly preferable.
Hydrolyzable silane Compound (s2) A hydrolyzable silane compound in which 4 hydrolyzable groups are bonded to a silicon atom.
And a hydrolyzable silane compound (s3) which contains a group having an ethylenic double bond and a group having a hydrolyzable group bonded to a silicon atom and does not contain a fluorine atom.
The mixture (M) may optionally contain 1 or 2 or more hydrolyzable silane compounds other than the hydrolyzable silane compounds (s1) to (s 3).
Examples of the other hydrolyzable silane compound include a hydrolyzable silane compound having only a hydrocarbon group and a hydrolyzable group as a group bonded to a silicon atom (s4), a hydrolyzable silane compound having a mercapto group and a hydrolyzable group and containing no fluorine atom (s5), a hydrolyzable silane compound having an epoxy group and a hydrolyzable group and containing no fluorine atom (s6), and a hydrolyzable silane compound having an oxyalkylene group and a hydrolyzable silyl group and containing no fluorine atom (s 7).
Examples of the hydrolyzable silane compounds (s1) to (s3) and other hydrolyzable silane compounds include those described in paragraphs [0034] to [0072] of WO2014/046209 and paragraphs [0096] to [0136] of WO 2014/069478.
Examples of the ink repellent (E1) include a partial hydrolysis condensate of a mixture (M) of a compound containing n1 (s1), a compound containing n2 (s2), and a compound containing n3 (s 3).
Here, n1 to n3 represent the mole fractions of the respective constituent units with respect to the total mole amount of the constituent units. n1>0, n2 ≥ 0, n3 ≥ 0 and n1+ n2+ n3 ═ 1.
n1: n2: n3 corresponds to the charge composition of compounds (s1), (s2), (s3) of mixture (M).
The molar ratio of each component can be designed in accordance with the balance of the effects of each component.
n1 is preferably 0.02 to 0.4 in the amount that the fluorine atom content of the ink repellent (E1) falls within the above preferred range.
n2 is preferably 0 to 0.98, particularly preferably 0.05 to 0.6.
n3 is preferably 0 to 0.8, particularly preferably 0.2 to 0.5.
The mass average molecular weight (Mw) of the ink repellent (E1) is preferably 500 or more, preferably less than 1000000, and particularly preferably 5000 or less.
When the mass average molecular weight (Mw) is not less than the lower limit, the ink repellent (E1) is likely to migrate to the upper surface when a cured film is formed using the negative photosensitive resin composition. If the content is less than the upper limit, the opening residue is preferably reduced.
The mass average molecular weight (Mw) of the ink repellent (E1) can be adjusted according to the production conditions.
The ink repellent (E1) can be produced by subjecting the above mixture (M) to hydrolysis and condensation reaction by a known method.
In this reaction, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, or organic acids such as acetic acid, oxalic acid and maleic acid, which are generally used, are preferably used as a catalyst. Further, an alkali catalyst such as sodium hydroxide or tetramethylammonium hydroxide (TMAH) may be used as necessary.
The reaction can be carried out using a known solvent.
The ink repellent (E1) obtained by the above reaction can be blended in the negative photosensitive resin composition together with a solvent in the form of a solution.
< ink-repellent agent (E2) >
The ink repellent (E2) is a compound having a hydrocarbon chain as a main chain and containing a side chain having a fluorine atom. The mass-average molecular weight (Mw) of the ink repellent (E2) is preferably 100 to 1000000, and particularly preferably 5000 to 100000. When the mass average molecular weight (Mw) is not less than the lower limit, the ink repellent (E2) is likely to migrate to the upper surface when a cured film is formed using the negative photosensitive resin composition. If the amount is less than the upper limit, the opening residue is preferably reduced.
Specific examples of the ink-repellent agent (E2) include those described in [0079] to [0102] of WO2014/046209 and those described in [0144] to [0171] of WO 2014/069478.
The content of the ink repellent (E) in the total solid content of the negative photosensitive resin composition is preferably 0.01 to 15% by mass, more preferably 0.01 to 5% by mass, and particularly preferably 0.03 to 1.5% by mass. When the content ratio is not less than the lower limit of the above range, the upper surface of the cured film formed from the negative photosensitive resin composition has excellent ink repellency. When the upper limit value of the above range is less than or equal to the upper limit value, the adhesion between the cured film and the substrate is good.
(crosslinking agent (F))
The crosslinking agent (F) optionally contained in the negative photosensitive resin composition of the present invention is a compound having 2 or more unsaturated double bonds, that is, ethylenic double bonds in 1 molecule and having neither an acid group nor a fluorine atom. When the negative photosensitive resin composition contains the crosslinking agent (F), the curability of the negative photosensitive resin composition at the time of exposure is improved, and a cured film can be formed even with a low exposure amount.
Specific examples of the crosslinking agent (F) include crosslinking agents described in, for example, [0137], [0138] of WO2014/046209 and crosslinking agents described in, for example, [0194], [0195] of WO 2014/069478.
The crosslinking agent (F) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The content of the crosslinking agent (F) in the total solid content of the negative photosensitive resin composition is preferably 10 to 60% by mass, and particularly preferably 20 to 55% by mass.
(thiol Compound (G))
The thiol compound (G) optionally contained in the negative photosensitive resin composition of the present invention is a compound having 2 or more mercapto groups in 1 molecule. When the negative photosensitive resin composition of the present invention contains the thiol compound (G), a so-called ene-thiol reaction occurs in which radicals generated from the photopolymerization initiator (B) at the time of exposure generate radicals of the thiol compound (G) and act on ethylenic double bonds of the alkali-soluble resin (a). Unlike the radical polymerization of general ethylenic double bonds, this ene-thiol reaction is not inhibited by reaction due to oxygen, and therefore has advantages such as high chain transferability, and further, crosslinking proceeds simultaneously with polymerization, and therefore, the shrinkage rate when a cured product is obtained is also low, and a uniform network structure is easily obtained.
When the negative photosensitive resin composition of the present invention contains the thiol compound (G), it can be sufficiently cured even with a low exposure amount as described above, and particularly, it can be sufficiently photocured in the upper layer portion including the upper surface of the partition wall which is easily inhibited from reaction by oxygen, and therefore, it is possible to impart good ink repellency to the upper surface of the partition wall.
The thiol compound (G) preferably contains 2 to 10 mercapto groups, more preferably 3 to 8 mercapto groups, and still more preferably 3 to 5 mercapto groups in 1 molecule.
The molecular weight of the thiol compound (G) is not particularly limited. From the viewpoint of curability at low exposure, the thiol equivalent (hereinafter, also referred to as "SH equivalent") represented by [ molecular weight/number of thiol groups ] of the thiol compound (G) is preferably 40 to 1000, more preferably 40 to 500, and particularly preferably 40 to 250.
Specific examples of the thiol compound (G) include tris (2-mercaptopropionyloxyethyl) isocyanurate, pentaerythritol tetrakis (3-mercaptobutyrate), trimethylolpropane trimercaptoacetate, pentaerythritol tetramercaptoacetate, dipentaerythritol hexamercaptoacetate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tris- [ (3-mercaptopropionyloxy) -ethyl ] -isocyanurate, dipentaerythritol hexa (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexa (3-mercaptobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), 1,3, 5-tris (3-mercaptobutyryloxyethyl) -1, 3, 5-triazine-2, 4,6(1H,3H,5H) -trione, trisphenolmethanetris (3-mercaptopropionate), trisphenolmethanetris (3-mercaptobutyrate), trimethylolethanetris (3-mercaptobutyrate), 2,4, 6-trimercapto-s-triazine, 1, 4-bis (3-mercaptobutyryloxy) butane, and the like.
The thiol compound (G) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
When the negative photosensitive resin composition contains the thiol compound (G), the content thereof is preferably 0.0001 to 1 mol, more preferably 0.0005 to 0.5 mol, and particularly preferably 0.001 to 0.5 mol, based on 1 mol of the mercapto group of the ethylenic double bond in the total solid content in the negative photosensitive resin composition. When the content ratio is within the above range, the negative photosensitive resin composition has good photocurability and developability even with a low exposure amount.
The thiol compound (G) is very effective for fixing the ink repellent (E) at a low exposure amount in the ink repellent layer, but the carboxylic acid derived from (a) tends to be less likely to be consumed by the reaction and less effective for improving the pattern formability than the acid generator (C) and the acid curing agent (D) which have the same fixing effect of the ink repellent (E) at a low exposure amount. Therefore, even when the negative photosensitive resin composition contains the thiol compound (G), the acid generator (C) and the acid curing agent (D) are preferably contained in the above-mentioned predetermined amounts.
(phosphoric acid Compound (H))
The negative photosensitive resin composition of the present invention may optionally contain a phosphoric acid compound (H) in order to improve the adhesion of the obtained cured film to a substrate, a transparent electrode material such as ITO, or the like.
The phosphoric acid compound (H) is not particularly limited as long as it can improve the adhesion of the cured film to a substrate, a transparent electrode material, or the like, and is preferably a phosphoric acid compound having an ethylenically unsaturated double bond in the molecule.
As the phosphoric acid compound having an ethylenically unsaturated double bond in the molecule, a phosphoric acid (meth) acrylate compound, that is, a compound having at least an O ═ P structure derived from phosphoric acid and a (meth) acryloyl group as an ethylenically unsaturated double bond derived from a (meth) acrylic compound in the molecule, and a phosphoric acid vinyl compound are preferable.
Examples of the phosphoric acid (meth) acrylate compound used in the present invention include mono (2- (meth) acryloyloxyethyl) acid phosphate, di (2-acryloyloxyethyl) acid phosphate, tri ((meth) acryloyloxyethyl) acid phosphate, mono (2-methacryloyloxyethyl) hexanoate acid phosphate, and the like.
The negative photosensitive resin composition of the present invention may contain 1 or 2 or more of the compounds classified as the phosphoric acid compound (H) alone.
When the negative photosensitive resin composition contains the phosphoric acid compound (H), the content thereof is preferably 0.01 to 10% by mass, and particularly preferably 0.1 to 5% by mass, based on the total solid content in the negative photosensitive resin composition. When the content ratio is within the above range, the obtained cured film has good adhesion to a substrate or the like.
(polymerization inhibitor (I))
The polymerization inhibitor (I) of the present invention is not particularly limited as long as it has a function as a polymerization inhibitor, and a compound which generates a radical inhibiting the reaction of the alkali-soluble resin (a) is preferable. In the negative photosensitive resin composition of the present invention, polymerization is controlled by adjusting the amount of light irradiated during exposure using the polymerization inhibitor (I), and curing of the composition can be smoothly performed. This suppresses the progress of curing in the unexposed area, and contributes to the reduction of development residue in the opening. Further, a high-resolution dot pattern can be obtained, and the improvement of the linearity of the pattern is facilitated.
Specific examples of the polymerization inhibitor (I) include common polymerization inhibitors such as diphenylpicrylhydrazide, tris-p-nitrophenylmethyl group, p-benzoquinone, p-tert-butylcatechol, picric acid, copper chloride, methylhydroquinone, 4-methoxyphenol, tert-butylhydroquinone, 2-tert-butyl-1, 4-benzoquinone, and 2, 6-di-tert-butyl-p-cresol. Among them, 2-methylhydroquinone, 2, 6-di-tert-butyl-p-cresol, 4-methoxyphenol and the like are preferable. Further, hydroquinone-based and quinone-based polymerization inhibitors are preferable from the viewpoint of storage stability, and 2-methylhydroquinone and 2-tert-butyl-1, 4-benzoquinone are particularly preferably used.
The content of the polymerization inhibitor (I) in the total solid content of the negative photosensitive resin composition is preferably 0.001 to 20% by mass, more preferably 0.005 to 10% by mass, and particularly preferably 0.01 to 5% by mass. When the content ratio is within the above range, the development residue of the negative photosensitive resin composition is reduced, and the linearity of the pattern is good.
(solvent (J))
The negative photosensitive resin composition of the present invention contains the solvent (J), and therefore, the viscosity is reduced, and the negative photosensitive resin composition can be easily applied to the surface of a substrate. As a result, a coating film of the negative photosensitive resin composition having a uniform film thickness can be formed.
As the solvent (J), a known solvent is used. The solvent (J) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Examples of the solvent (J) include alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, alcohols, solvent naphtha and the like. Among them, at least 1 solvent selected from alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, and alcohols is preferable, and at least 1 solvent selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, and 2-propanol is more preferable.
The content of the solvent (J) in the negative photosensitive resin composition is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and particularly preferably 65 to 90% by mass, based on the total amount of the composition.
(colorant (K))
The negative photosensitive resin composition of the present invention contains a colorant (K) when it is necessary to impart light-shielding properties to a cured film, particularly a partition wall, according to the application. Examples of the colorant (K) of the present invention include carbon black, aniline black, anthraquinone black pigments, and perylene black pigments, and specifically include c.i. pigment black 1, 6, 7, 12, 20, and 31. Mixtures of organic and/or inorganic pigments such as red, blue and green pigments may also be used.
The colorant (K) may be used alone in 1 kind, or may be used in combination of 2 or more kinds. When the negative photosensitive resin composition of the present invention contains the colorant (K), the content of the colorant (K) in the total solid content is preferably 5 to 65% by mass, and particularly preferably 10 to 50% by mass. When the amount is within the above range, the obtained negative photosensitive resin composition has good sensitivity, and the barrier rib formed has excellent light-shielding properties.
(other Components)
The negative photosensitive resin composition of the present invention may further contain 1 or 2 or more kinds of other additives such as a thermal crosslinking agent, a polymer dispersant, a dispersion aid, a silane coupling agent, fine particles, a curing accelerator, a thickener, a plasticizer, an antifoaming agent, a leveling agent, and a shrinkage preventing agent, as required.
The negative photosensitive resin composition of the present invention can be obtained by mixing predetermined amounts of the above components. The negative photosensitive resin composition of the present invention can be used for manufacturing optical devices such as organic EL devices, quantum dot displays, TFT arrays, thin film solar cells, and color filters. Specifically, the cured film and the partition wall are used for optical elements such as organic EL elements, quantum dot displays, TFT arrays, and thin film solar cells, and can exhibit particularly advantageous effects. By using the negative photosensitive resin composition of the present invention, a cured film, particularly a partition wall, having a good ink repellency on the upper surface can be produced. The ink-repellent agent (E) is substantially sufficiently fixed to the ink-repellent layer, and the ink-repellent agent (E) present at a low concentration on the partition walls in the lower portion of the ink-repellent layer is also sufficiently photo-cured on the partition walls, so that the ink-repellent agent (E) is less likely to migrate into the openings surrounded by the partition walls during development, and therefore, openings in which ink can be uniformly applied are obtained.
[ cured resin film and partition wall ]
The resin cured film according to the embodiment of the present invention is formed using the negative photosensitive resin composition according to the present invention. The resin cured film according to the embodiment of the present invention can be obtained, for example, by applying the negative photosensitive resin composition of the present invention to the surface of a substrate such as a substrate, drying the composition as needed to remove a solvent or the like, and then exposing the composition to light. The resin cured film according to the embodiment of the present invention exhibits a particularly significant effect when used in an optical device, particularly an organic EL device, a quantum dot display, a TFT array, and a thin film solar cell.
The partition wall of the present invention is a partition wall formed of the cured film of the present invention described above, which is formed in a shape dividing a substrate surface into a plurality of sections for forming dots. The partition wall can be obtained, for example, by masking a portion to be a partition for dot formation before exposure and developing the portion after exposure in the production of the resin cured film. By the development, the portions not exposed to light due to masking are removed, and openings corresponding to the dot forming partitions are formed together with the partition walls. The partition wall according to the embodiment of the present invention exhibits a particularly significant effect when used in an optical element, particularly an organic EL element, a quantum dot display, a TFT array, and a thin film solar cell.
The partition wall according to the embodiment of the present invention does not necessarily require high-temperature treatment in the manufacturing process, and therefore can be applied to flexible applications using plastic substrates such as polyethylene terephthalate (PET) and polycarbonate, for example, as described below.
An example of a method for manufacturing a partition wall according to an embodiment of the present invention will be described below with reference to fig. 1A to 1D, but the method for manufacturing a partition wall is not limited to the following. The following production method is described with respect to the case where the negative photosensitive resin composition contains the solvent (J).
As shown in fig. 1A, a negative photosensitive resin composition is applied to the entire main surface of one side of a substrate 1 to form a coating film 21. At this time, the ink repellent (E) is dissolved and uniformly dispersed in the entire coating film 21. Note that, in fig. 1A, the ink repellent (E) is schematically shown, and is not actually present in such a particle shape.
Next, as shown in fig. 1B, the coating film 21 is dried to form a dried film 22. Examples of the drying method include heat drying, drying under reduced pressure, and heat drying under reduced pressure. Although it depends on the kind of the solvent (J), the heating temperature is preferably 50 to 120 ℃ in the case of heat drying.
During this drying process, the ink repellent (E) migrates to the upper layer portion of the dried film. Note that, even when the negative photosensitive resin composition does not contain the solvent (J), the migration of the ink repellent (E) to the upper surface in the coating film is similarly achieved.
Next, as shown in fig. 1C, the dry film 22 is exposed by irradiating light through a photomask 30, the photomask 30 having a mask portion 31 having a shape corresponding to the opening surrounded by the partition walls. The film obtained by exposing the dried film 22 is referred to as an exposed film 23. In the exposed film 23, the exposed portion 23A is photocured, and the unexposed portion 23B is in the same state as the dried film 22.
Examples of the light to be irradiated include visible light; ultraviolet rays; extreme ultraviolet light; KrF excimer laser, ArF excimer laser, F2Excimer laser, Kr2Excimer laser, KrAr excimer laser and Ar2Excimer laser such as excimer laser; x-rays; electron beams, and the like.
The light to be irradiated is preferably light having a wavelength of 100 to 600nm, more preferably light having a wavelength of 300 to 500nm, and particularly preferably light containing i-ray (365nm), h-ray (405nm) or g-ray (436 nm). Further, light having a wavelength of 330nm or less may be cut off as necessary.
As the light to be irradiated during exposure, it is necessary to select light rays having wavelengths for activating the photopolymerization initiator (B) and the acid generator (C) contained in the negative photosensitive resin composition.
Examples of the exposure method include one-time exposure over the entire surface, scanning exposure, and the like. The exposure may be performed on the same position in a fraction of times. In this case, the exposure conditions may be the same or different for a plurality of times.
The exposure amount is preferably, for example, 5 to 1000mJ/cm in any of the above exposure modes2More preferably 5 to 500mJ/cm2More preferably 5 to 300mJ/cm2Particularly preferably 5 to 200mJ/cm2Most preferably 5 to 50mJ/cm2. The exposure amount can be appropriately optimized by the wavelength of the light to be irradiated, the composition of the negative photosensitive resin composition, the thickness of the coating film, and the like.
The exposure time per unit area is not particularly limited, and may be designed according to the exposure power of the exposure apparatus used, the required exposure amount, and the like. In the case of scanning exposure, the exposure time may be determined from the scanning speed of light.
The exposure time per unit area is usually about 1 to 60 seconds.
In the negative photosensitive resin composition of the present invention, radical polymerization of the alkali-soluble resin (a) is carried out in the exposure portion during exposure, and the acid generator (C) generates an acid by exposure, and in the presence of the acid, the acid curing agent (D) reacts with an acid group of the alkali-soluble resin (a) such as a carboxylic acid. Thus, the negative photosensitive resin composition of the present invention can provide a cured film, particularly a cured film having improved curability of the alkali-soluble resin (a) and fixation of the ink repellent (E) on the upper surface of the cured film. Further, a cured film having curability equivalent to that of a conventional cured film, particularly curability of the upper surface, even with a low exposure amount, was obtained.
Next, as shown in fig. 1D, development using an alkali developer is performed to form the partition walls 4 only including the portions corresponding to the exposure portions 23A of the exposure film 23. The opening 5 surrounded by the partition wall 4 is a portion of the exposed film 23 where the non-exposed portion 23B exists, and fig. 1D shows a state where the non-exposed portion 23B is removed by development. As described above, the unexposed portions 23B are dissolved and removed by the alkali developing solution in a state where the ink-repellent agent (E) migrates to the upper layer and the layer below the upper layer is almost free of the ink-repellent agent (E), and therefore the ink-repellent agent (E) hardly remains in the openings 5.
In the partition wall 4 shown in fig. 1D, the uppermost layer including the upper surface thereof is an ink-repellent layer 4A. When the ink-repellent agent (E) does not contain a side chain having an ethylenic double bond, the ink-repellent agent (E) is present in the uppermost layer at a high concentration as it is during exposure, and becomes an ink-repellent layer. In the exposure, the alkali-soluble resin (a) present around the ink-repellent agent (E) is strongly photocured with the acid curing agent (D), particularly in the presence of an acid generated from the acid generator (C), and the ink-repellent agent (E) is fixed to the ink-repellent layer. Further, when the negative photosensitive resin composition optionally contains the thiol compound (G), the reaction based on the ethylenic double bond is promoted, and the ink-repellent layer is more firmly cured.
Even in the case where the ink repellent (E) includes a side chain having an ethylenic double bond, the alkali-soluble resin (a) is strongly photocured with the acid curing agent (D) in the presence of an acid generated from the acid generator (C), and the ink repellent (E) is simultaneously photocured together with each other and/or the alkali-soluble resin (a), and optionally the thiol compound (G) and other photocuring components, to form the ink repellent layer 4A in which the ink repellent (E) is strongly bonded.
In any of the above cases, a layer 4B containing mainly the alkali-soluble resin (a), the acid curing agent (D), and optionally the thiol compound (G) and other photocurable components, which is photocured by radical polymerization using radicals generated by the photopolymerization initiator (B) and cationic polymerization in the presence of an acid generated by the acid generator (C), and which contains almost no ink-repellent agent (E), is formed below the ink-repellent layer 4A.
By the above operation, the ink-repellent agent (E) is sufficiently fixed to the partition wall including the ink-repellent layer 4A and the lower layer 4B thereof, and therefore hardly migrates to the opening portion at the time of development.
As described above, in the negative photosensitive resin composition of the present invention, the surface and the inside of the cured film are sufficiently cured by combining the radical polymerization reaction by light and the curing reaction in the presence of the acid generated by light. Therefore, the cured portion as the exposed portion is resistant to corrosion and peeling by an alkali developing solution during development. Therefore, the exposed portion is less susceptible to long-term development, and therefore, is advantageous in removing residues in the opening portion.
After development, the partition walls 4 may be further heated. The heating temperature is preferably 80-250 ℃. By heating, the partition wall 4 is more firmly cured. In addition, the ink-repellent agent (E) is more firmly fixed within the ink-repellent layer 4A. The composition of the present invention can exhibit high liquid repellency even when cured at low temperatures, and can further exhibit high liquid repellency when immersed in a chemical agent such as an acid or an organic solvent. Particularly, when a plastic substrate such as a PET film or polycarbonate is used, the heating temperature needs to be set to a low level. In this case, the heating temperature is preferably 150 ℃ or lower, and more preferably 120 ℃ or lower. The composition of the present invention maintains liquid repellency even when heated at low temperatures as described above, and has excellent chemical resistance.
The resin cured film of the present invention and the partition wall 4 obtained by the above operation have good ink repellency on the upper surface even when exposure is performed at a low exposure amount. In addition, the partition walls 4 are almost free of the ink repellent (E) in the openings 5 after development, and uniform coating properties of the ink in the openings 5 can be sufficiently ensured.
For the purpose of more reliably obtaining the ink affinity of the opening 5, the substrate 1 with the partition wall 4 may be subjected to ultraviolet/ozone treatment after the heating to remove development residue and the like of the negative photosensitive resin composition that may be present in the opening 5.
The partition wall formed of the negative photosensitive resin composition of the present invention has a width of preferably 100 μm or less, and particularly preferably 20 μm or less. The distance between adjacent partition walls (width of pattern) is preferably 300 μm or less, and particularly preferably 100 μm or less. The height of the partition walls is preferably 0.05 to 50 μm, and particularly preferably 0.2 to 10 μm.
When the partition wall formed of the negative photosensitive resin composition of the present invention is formed to have the above-described width, the unevenness at the edge portion is small and the linearity is excellent. The high linearity of the partition wall is particularly remarkable when a resin (a-2) in which an acidic group and an ethylenic double bond are introduced into an epoxy resin is used as the alkali-soluble resin. This enables formation of a pattern with high pattern accuracy even when the pattern is fine. If such high-precision patterning can be performed, the organic EL element is particularly useful as a partition wall for an organic EL element, a quantum dot display, a TFT array, and a thin film solar cell.
When pattern printing is performed by the IJ method, the partition wall of the present invention can be used as a partition wall having an opening portion as an ink injection region. When the partition wall of the present invention is formed and used so that the opening portions thereof coincide with the desired ink injection regions in pattern printing by the IJ method, the upper surface of the partition wall has good ink repellency, and therefore, injection of ink beyond the partition wall into the ink injection regions, which are undesired opening portions, can be suppressed. Further, since the opening surrounded by the partition walls has good ink wettability expansibility, the ink can be uniformly printed in a desired region without causing white spots or the like.
By using the partition wall of the present invention, as described above, pattern printing by the IJ method can be performed precisely. Therefore, the partition wall of the present invention is useful as a partition wall of an optical element having a plurality of dots formed by the IJ method on a substrate surface and a partition wall located between adjacent dots, particularly an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell.
[ optical element ]
The optical element of the present invention, particularly an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell, is an optical element having a plurality of dots and the above-described partition wall of the present invention located between the adjacent dots on the surface of a substrate. In the optical element of the present invention, particularly an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell, it is preferable to form dots by the IJ method.
The organic EL element has a structure in which a light emitting layer of an organic thin film is sandwiched between an anode and a cathode, and the partition wall of the present invention can be used for a partition wall for partitioning an organic light emitting layer, a partition wall for partitioning an organic TFT layer, a partition wall for partitioning a coating-type oxide semiconductor, and the like.
The organic TFT array element is an element in which a plurality of dots are arranged in a matrix shape in a plan view, pixel electrodes and TFTs serving as switching elements for driving the pixel electrodes are provided at each dot, and an organic semiconductor layer is used as a semiconductor layer including a channel layer of the TFTs. The organic TFT array element may be provided as a TFT array substrate on an organic EL element, a liquid crystal element, or the like, for example.
An example in which dots are formed in the opening by the IJ method using the partition wall obtained above will be described below with respect to an optical element according to an embodiment of the present invention, for example, an organic EL element. The method of forming dots in an optical element such as an organic EL element according to the present invention is not limited to the following.
Fig. 2A and 2B are views schematically showing a method for manufacturing an organic EL element using the partition wall 4 formed on the substrate 1 shown in fig. 1D. Here, the partition walls 4 on the substrate 1 are formed so that the openings 5 match the dot pattern of the organic EL element to be manufactured.
As shown in fig. 2A, ink 10 is dropped from the inkjet head 9 to the opening 5 surrounded by the partition wall 4, and a predetermined amount of the ink 10 is injected into the opening 5. As the ink, a known ink for an organic EL element can be appropriately selected and used in accordance with the function of the dot.
Next, depending on the type of the ink 10 used, for example, for the purpose of solvent removal and curing, a treatment such as drying and/or heating is performed, and as shown in fig. 2B, an organic EL element 12 in which desired dots 11 are formed in a shape adjacent to the partition walls 4 is obtained.
The optical element, particularly the organic EL element, the quantum dot display, the TFT array or the thin-film solar cell according to the embodiment of the present invention is an optical element, particularly an organic EL element, a quantum dot display, a TFT array or a thin-film solar cell, in which dots can be formed with high accuracy by uniformly wetting and spreading ink in openings defined by the barrier ribs without unevenness in the manufacturing process by using the barrier ribs of the present invention.
The organic EL element can be produced, for example, as follows, but is not limited thereto.
A light-transmissive electrode such as tin-doped indium oxide (ITO) is formed on a light-transmissive substrate made of plastic such as glass or PET by a sputtering method or the like. The light-transmissive electrode is patterned as necessary.
Next, using the negative photosensitive resin composition of the present invention, partition walls are formed in a lattice shape in a plan view along the outline of each point by a photolithography method including coating, exposure, and development.
Next, materials for the hole injection layer, the hole transport layer, the light-emitting layer, the hole blocking layer, and the electron injection layer were applied to the dots by the IJ method, and dried, and these layers were stacked in this order. The kind and number of organic layers formed in the dots may be appropriately designed.
Finally, a reflective electrode made of aluminum or the like is formed by vapor deposition or the like.
The quantum dot display can be manufactured as follows, for example, but is not limited thereto.
A light-transmissive electrode such as tin-doped indium oxide (ITO) is formed on a light-transmissive substrate made of plastic such as glass or PET by a sputtering method or the like. The light-transmissive electrode may be patterned as necessary.
Next, using the negative photosensitive resin composition of the present invention, partition walls are formed in a lattice shape in a plan view along the outline of each point by a photolithography method including coating, exposure, and development.
Next, materials for the hole injection layer, the hole transport layer, the quantum dot layer, the hole blocking layer, and the electron injection layer were applied to the inside of the dot by the IJ method, and dried, and these layers were sequentially stacked. The kind and number of organic layers formed in the dots can be appropriately designed.
Finally, a reflective electrode such as aluminum or a translucent electrode such as ITO is formed by vapor deposition or the like.
Furthermore, the optical element according to the embodiment of the present invention can be applied to, for example, a blue light conversion type quantum dot display manufactured as follows.
The negative photosensitive resin composition of the present invention is used to form barrier ribs in a grid shape in a plan view along the outline of each dot on a light-transmitting substrate made of plastic such as glass or PET.
Next, a nanoparticle solution for converting blue light into green light, a nanoparticle solution for converting blue light into red light, and a color ink of blue color as needed are applied to the dots by an IJ method and dried to produce a module. A liquid crystal display excellent in color reproducibility was obtained by using a light source that develops blue as a backlight and the above-described module as a substitute for a color filter.
The TFT array can be manufactured as follows, for example, but is not limited thereto.
A gate electrode of aluminum, an alloy thereof, or the like is formed on a light-transmitting substrate of plastic such as glass, PET, or the like by a sputtering method or the like. The gate electrode may be patterned as desired.
Next, a gate insulating film such as silicon nitride is formed by a plasma CVD method or the like. A source electrode and a drain electrode may be formed on the gate insulating film. The source electrode and the drain electrode can be formed by forming a metal thin film of aluminum, gold, silver, copper, an alloy thereof, or the like by vacuum evaporation or sputtering, for example. As a method for patterning the source electrode and the drain electrode, there is a method in which after a metal thin film is formed, a resist is applied, exposure and development are performed, the resist is left in a portion where an electrode is to be formed, then the exposed metal is removed with phosphoric acid, aqua regia, or the like, and finally the resist is removed. In the case of forming a metal thin film of gold or the like, there is a method of applying a resist in advance, exposing and developing the resist to leave a portion where no electrode is to be formed, and then removing the resist together with the metal thin film after forming the metal thin film. The source electrode and the drain electrode may be formed by an ink jet method or the like using a metal nano-colloid such as silver or copper.
Next, using the negative photosensitive resin composition of the present invention, partition walls are formed in a lattice shape in a plan view along the outline of each point by a photolithography method including coating, exposure, and development.
Next, a semiconductor solution was applied to the spot by an IJ method and the solution was dried, thereby forming a semiconductor layer. As the semiconductor solution, an organic semiconductor solution or an inorganic coating type oxide semiconductor solution can be used. The source electrode and the drain electrode can be formed by an ink jet method or the like after the semiconductor layer is formed.
Finally, a transparent electrode such as ITO is formed by sputtering or the like, and a protective film such as silicon nitride is formed.
Examples
The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Examples 1 to 10 are examples, and examples 11 to 13 are comparative examples.
Each measurement was performed by the following method.
[ number average molecular weight (Mn), Mass average molecular weight (Mw) ]
The number average molecular weight (Mn) and the mass average molecular weight (Mw) were measured by gel permeation chromatography using polystyrene as a standard substance. HPLC-8220 GPC (manufactured by Tosoh corporation) was used as the gel permeation chromatograph. As the column, a column to which 3 shodex LF-604 was attached was used. As the detector, an RI detector is used. EasiCal PS1 (product of Polymer Laboratories) was used as a standard substance. Further, in the measurement of the number average molecular weight and the mass average molecular weight, the column was maintained at 37 ℃ and tetrahydrofuran was used as an eluent at a flow rate of 0.2 mL/min, and 40. mu.L of a 0.5% tetrahydrofuran solution of the measurement sample was injected.
[ fluorine atom content ]
The fluorine atom content of 1, 4-bis (trifluoromethyl) benzene as a standard substance19F NMR was measured and calculated.
[ acid value ]
The acid value is theoretically calculated from the blending ratio of the raw materials.
The compounds used in the following examples are shown below for short.
(alkali-soluble resin (A))
Alkali-soluble resin (A1) composition A resin (alkali-soluble resin (A1), acid value 60mgKOH/g) which was obtained by reacting a cresol novolak-type epoxy resin with acrylic acid, then reacting the resulting resin with 1,2,3, 6-tetrahydrophthalic anhydride to introduce an acryloyl group and a carboxyl group, and purifying the obtained resin with hexane (solid content 70% by mass, PGMEA 30% by mass)
Alkali-soluble resin (A2) composition A composition of a resin having carboxyl groups and ethylenic double bonds introduced into a bisphenol A-type epoxy resin (alkali-soluble resin (A2), acid value 100mgKOH/g) (solid content 70 mass%, PGMEA30 mass%).
Alkali-soluble resin (A3) composition A composition (solid content 70 mass%, PGMEA30 mass%) of a resin having an ethylenic double bond and an acidic group introduced into an epoxy resin having a biphenyl skeleton represented by the following formula (A-2 a) (alkali-soluble resin (A3), acid value 70 mgKOH/g).
(in the formula (A-2 a), v is an integer of 1 to 50, preferably an integer of 2 to 10. furthermore, the hydrogen atoms of the benzene ring may be independently substituted by an alkyl group having 1 to 12 carbon atoms, a halogen atom or a phenyl group, and a part of the hydrogen atoms of the phenyl group may be substituted by a substituent.)
Alkali-soluble resin (A-R-1) A1L reaction tank equipped with a stirrer and having an internal volume was charged with acetone (555g), AA (acrylic acid) (36.0g), 2-HEMA (108.0g), IBMA (72.0g), a chain transfer agent DSH (9.7g), and a polymerization initiator V-70 (5.1g), and the mixture was polymerized at 40 ℃ for 18 hours under nitrogen with stirring to obtain a solution of the alkali-soluble resin (A-R-1). The obtained acetone solution of the alkali-soluble resin (A-R-1) was reprecipitated and purified with water, followed by reprecipitation and purification with petroleum ether and vacuum drying to obtain 235g of the alkali-soluble resin (A-R-1). The number average molecular weight (Mn) of the alkali-soluble resin (A-R-1) was 5000, and the acid value of the alkali-soluble resin (A-R-1) was 119 mgKOH/g.
(photopolymerization initiator (B))
IR907 2-methyl-1- [ 4- (methylthio) phenyl ] -2-morpholinopropan-1-one (product name IRGACURE907, manufactured by BASF corporation).
OXE02 ethanone 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyl oxime) (product name: OXE02, manufactured by BASF corporation).
(acid Generator (C))
PAG-A2- (5-methyl-2-furyl) vinyl-4, 6-bis (trichloromethyl) -1, 3, 5-triazine (Compound represented by the formula (C8-2) above)
PAG-B2- [ 2- (n-propylsulfonyloxyimino) thiophen-3 (2H) -ylidene]-2- (2-methylphenyl) acetonitrile (R in the compound represented by the formula (C11)b11Compounds being n-propyl groups)
WPAG199 bis (p-toluenesulfonyl) diazomethane
SI-150L aromatic sulfonium SbF represented by the formula (C0-1)6 －Salt (trade name: San-aid SI-150L, manufactured by Sanxin chemical industries Co., Ltd.)
(acid curing agent (D))
Epoxy A an epoxy compound containing a dicyclopentane ring represented by the formula (De1)
Epoxy B a naphthalene ring-containing epoxy compound represented by the formula (De2)
Melamine A2, 4, 6-tris [ bis (methoxymethyl) amino ] -1, 3, 5-triazine (compound represented by the above formula (D1-1))
Melamine B1, 3,4, 6-tetrakis (methoxymethyl) glycoluril (compound represented by the above formula (D3-1))
(raw Material for ink-repellent agent (E1))
Compound (s 1-1) corresponding to Compound (s1) F (CF)2)6CH2CH2Si(OCH3)3(manufactured by a known method).
Compound (s 2-1) corresponding to compound (s2) Si (OC)2H5)4(manufactured by colcoat Co., Ltd.).
Compound (s 3-1) corresponding to Compound (s3) CH2＝CHCOO(CH2)3Si(OCH3)3(manufactured by Tokyo chemical industry Co., Ltd.).
A compound (s 5-1) corresponding to the compound (s 5):
a compound (s 6-1) corresponding to the compound (s 6):
(raw Material for ink-repellent agent (E2))
C6FMA:CH2＝C(CH3)COOCH2CH2(CF2)6F
X-174 DX methyl acrylate containing dimethyl Silicone chain (trade name X-22-174 DX, manufactured by shin-Etsu chemical Co., Ltd.)
X-8201 methyl acrylate containing a dimethylsilone chain (trade name X-24-8201, product of shin-Etsu chemical Co., Ltd.)
C4 α -Cl acrylate CH2＝C(Cl)COOCH2CH2(CF2)4F
C8FA:CH2＝CHCOOCH2CH2(CF2)8F
CHMA cyclohexyl methacrylate
MAA methacrylic acid
2-HEMA 2-hydroxyethyl methacrylate
MMA methyl methacrylate
GMA glycidyl methacrylate
IBMA isobornyl methacrylate
V-65 (2, 2' -azobis (2, 4-dimethylvaleronitrile))
V-70: 2, 2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile)
DSH n-dodecyl mercaptan
AOI 2-acryloyloxyethyl isocyanate)
DBTDL dibutyltin dilaurate
TBQ tert-butyl p-benzoquinone
MEK 2-butanone
(crosslinking agent (F))
DPHA dipentaerythritol hexaacrylate
(others)
KBM403: 3-glycidoxypropyltrimethoxysilane
Mercaptan compound pentaerythritol tetrakis (3-mercaptobutyrate)
MHQ 2-methylhydroquinone
(solvent (J))
PGME propylene glycol monomethyl ether
EDM diethylene glycol ethyl methyl ether
IPA 2-propanol
DEGDM diethylene glycol dimethyl Ether
PGMEA propylene glycol monomethyl ether acetate
[ Synthesis of ink-repellent agent (E) ]
The ink repellent (E) was synthesized or prepared as follows.
(Synthesis example 1 Synthesis of ink repellent (E-1))
An internal volume of 1000cm in a vessel equipped with a stirrer3The autoclave was charged with 420.0g of MEK, 99.0g of C6FMA99.0g, 9.0g of MAA9, 2-HEMA 18.0g, 45.0g of MMA45, 9.0g of IBMA9, 5.0g of a polymerization initiator V-653.0 g and 5.0g of DSH, and the mixture was polymerized at 50 ℃ for 24 hours while stirring in a nitrogen atmosphere, and further heated at 70 ℃ for 5 hours to deactivate the polymerization initiator to obtain a solution (solid content concentration; 30 mass%) of a copolymer (ink-repellent agent (E-1)). This solution was used for the production of a negative photosensitive resin composition described later. In the following synthesis of the ink repellent, when the ink repellent is obtained in the state of a solution containing the ink repellent, the concentration of the solid content is measured or adjusted, and then the solution is used for producing the negative photosensitive resin composition.
The ink-repellent agent (E-1) had a number average molecular weight of 14200, a mass average molecular weight of 21500, a fluorine atom content of 31.4 mass%, and an acid value of 32.6 (mgKOH/g).
(Synthesis example 2 Synthesis of ink repellent (E-2))
An internal volume of 1000cm in a vessel equipped with a stirrer3The autoclave was charged with 415.1g of MEK, 81.0g of C6FMA81.0g of MAA18.0g, 81.0g of 2-HEMA, 4.7g of polymerization initiators V-655.0 g and DSH, and the mixture was polymerized at 50 ℃ for 24 hours while stirring under nitrogen atmosphere, and further heated at 70 ℃ for 5 hours to induce polymerizationThe hair agent is deactivated to obtain a solution of the copolymer. The number average molecular weight of the copolymer was 5540, and the mass average molecular weight was 13200.
Next, the inner volume of the container was 300cm3The autoclave was charged with 130.0g of the above copolymer solution, 33.5g of BEI, 0.13g of DBTDL and 1.5g of TBQ, and reacted at 40 ℃ for 24 hours with stirring to synthesize a crude polymer. Hexane was added to the obtained crude polymer solution to purify the polymer by reprecipitation, followed by vacuum drying to obtain an ink repellent (E-2). The ink repellent (E-2) had a number average molecular weight of 7540, a mass average molecular weight of 16200, a fluorine atom content of 14.8 mass%, and an acid value of 35.1 (mgKOH/g).
(Synthesis example 3 Synthesis of ink repellent (E-3))
An internal volume of 1000cm in a vessel equipped with a stirrer3The autoclave was charged with MEK 420.0g, C6FMA99.0g, MAA9.0g, 2-HEMA 18.0g, GMA 18.0g, MMA 36.0g, polymerization initiators V-653.0 g and DSH 5.0g, and the mixture was polymerized at 50 ℃ for 24 hours under stirring in a nitrogen atmosphere, and further heated at 70 ℃ for 5 hours to deactivate the polymerization initiators, thereby obtaining a solution (solid content concentration; 30 mass%) of a copolymer (ink-repellent agent (E-3)).
The ink-repellent agent (E-3) had a number average molecular weight of 14850, a mass average molecular weight of 22700, a fluorine atom content of 31.4 mass%, and an acid value of 32.6 (mgKOH/g).
(preparation of ink repellent (E-4))
As the ink repellent (E-4), Megafac RS102 (trade name, manufactured by DIC) having a repeating unit represented by the following formula (E2F) with n/m of 3 to 4 was prepared. The ink repellent (E-4) had a number average molecular weight of 5700, a mass average molecular weight of 8800, and a fluorine atom content of 19.0 mass%.
(Synthesis example 5 Synthesis of ink repellent (E-5))
An internal volume of 2000cm equipped with a stirrer3317.5g of C4 α -Cl acrylate, 79.4g of MAA79 and IBMA 47 were placed in the autoclave7g, 52.9g of 2-HEMA, 4.6g of DSH, 4.6g of polymerization initiator V-702.0 g, and 1160g of MEK were polymerized at 50 ℃ for 24 hours under stirring in a nitrogen atmosphere, and then heated at 70 ℃ for 5 hours to deactivate the polymerization initiator and obtain a copolymer solution. The number average molecular weight of the copolymer was 5060 and the mass average molecular weight was 8720. The solid content concentration was measured and found to be 30% by mass.
Next, the inner volume of the container was 300cm3The autoclave was charged with 130.0g of the above copolymer solution, 3.6g of AOI (equivalent amount to 0.8 of hydroxyl group of the copolymer), 0.014g of DBTDL0, and 0.18g of TBQ, and reacted at 40 ℃ for 24 hours with stirring to synthesize a crude polymer. Hexane was added to the obtained crude polymer solution to purify the polymer by reprecipitation, followed by vacuum drying to obtain an ink repellent (E-5). The ink repellent (E-5) had a number average molecular weight of 8000, a mass average molecular weight of 10600, a fluorine atom content of 28.0 mass%, and an acid value of 93.3 (mgKOH/g).
(Synthesis example 6 Synthesis of ink repellent (E-6))
A1L autoclave having an internal volume equipped with a stirrer was charged with 555.0g of acetone, 60.0g of C6FMA60, 120.0g of X-174 DX, 24.0g of MAA24, 36.0g of CHMAH, 5.4g of chain transfer agent DSH, and V-702.0 g of polymerization initiator, and polymerized at 40 ℃ for 18 hours under nitrogen with stirring to obtain an ink repellent (E-6) solution.
Water was added to the acetone solution of the ink repellent (E-6) thus obtained to purify it by reprecipitation, followed by reprecipitation purification with petroleum ether and vacuum drying to obtain the ink repellent (E-6). The ink repellent (E-6) had a number average molecular weight of 9000, a mass average molecular weight of 11700, a fluorine atom content of 14.7% by mass, and an acid value of 65 mgKOH/g.
(Synthesis example 7 Synthesis of ink repellent (E-7))
A1L autoclave having an internal volume equipped with a stirrer was charged with 555.0g of acetone, C8FA48.0g, X-8201120.0 g, MAA12.0g, IBMA 60.0g, 10.8g of chain transfer agent DSH, and V-703.0 g of polymerization initiator, and the mixture was polymerized at 40 ℃ for 18 hours under stirring in a nitrogen atmosphere to obtain an ink repellent (E-7) solution.
Water was added to the acetone solution of the ink repellent (E-7) thus obtained to purify it by reprecipitation, followed by reprecipitation purification with petroleum ether and vacuum drying to obtain the ink repellent (E-7). The ink-repellent agent (E-7) had a number average molecular weight of 4500, a mass average molecular weight of 5590, a fluorine atom content of 12.5 mass%, and an acid value of 33 mgKOH/g.
The raw material compositions and properties of the ink-repellent agents (E-1) to (E-7) obtained or prepared as described above are summarized in Table 1.
[ Table 1]
(Synthesis example 8 Synthesis of ink repellent (E-8))
In a 1000cm frame equipped with a stirrer315.0g of the compound (s 1-1), 20.0g of the compound (s 2-1) and 27.0g of the compound (s 3-1) were placed in a three-necked flask to obtain a mixture of hydrolyzable silane compounds. Subsequently, 284.3g of IPA was added to the mixture to prepare a raw material solution.
30.0g of a 1% aqueous hydrochloric acid solution was added dropwise to the obtained raw material solution. After completion of the dropwise addition, the mixture was stirred at 40 ℃ for 5 hours to obtain an IPA solution of the ink-repellent agent (E-8) (concentration of the ink-repellent agent (E-8): 10 mass%).
After the reaction was completed, the components of the reaction solution were measured by a gas chromatograph, and it was confirmed that each compound as a raw material was not more than the detection limit.
(Synthesis examples 9 and 10: Synthesis of ink-repellent Agents (E-9) and (E-10))
An IPA solution of an ink repellent (E-9) (concentration of the ink repellent (E-9): 10 mass%) and an IPA solution of an ink repellent (E-10) (concentration of the ink repellent (E-10): 10 mass%) were obtained in the same manner as in Synthesis example 8, except that the hydrolyzable silane compound of the monomer component and the amount thereof in Synthesis example 8 were changed as shown in Table 2.
Table 2 shows the amounts of hydrolyzable silane compounds as raw materials used for producing the ink-repellent agents ((E-8) to (E-10)). In table 2, the silane compound represents a hydrolyzable silane compound. The measurement results of the number average molecular weight (Mn), the mass average molecular weight (Mw) and the fluorine atom content (% by mass) of the obtained ink-repellent agents ((E-8) to (E-10)) are shown in Table 2.
[ Table 2]
Example 1 production of negative photosensitive resin composition and production of cured film and partition wall (Pattern film)
(production of negative photosensitive resin composition)
An alkali-soluble resin (A1) composition in an amount of 10.0g of solid content (resin (A1)), IR9070.30g, OXE020.10g, EAB 0.20g, PAG-A0.30 g, epoxy A1.60g, ink-repellent agent (E-3) 0.05g, DPHA5.0g, and EDM 30.0g were placed in a container of 200cm3The stirring vessel of (3) was charged with PGME in a total amount of 100g, and stirred for 3 hours to prepare a negative photosensitive resin composition 1.
(production of cured film)
A10 cm square glass substrate was ultrasonically cleaned with ethanol for 30 seconds, followed by 5 minutes of UV/O3And (6) processing. UV/O3PL 2001N-58 (manufactured by Sen Engineering) was used as UV/O3Generating the device. The optical power (light output) at 254nm was 10mW/cm2。
The negative photosensitive resin composition 1 obtained above was applied to the surface of the cleaned glass substrate using a spinner, and then dried on a hot plate at 100 ℃ for 2 minutes to form a dried film having a thickness of 2.4 μm (1.2 μm in example 3 only). The obtained dried film was irradiated once with an exposure power (exposure output) of 300mW/cm in terms of 365nm on the entire surface2UV light of the ultra-high pressure mercury lamp. By this method, the exposure dose is 30mJ/cm2Or 50mJ/cm22 kinds of cured films were produced by adjusting the irradiation time. In either case, light of 330nm or less is cut off at the time of exposure.
Next, the glass substrate after the exposure treatment was immersed in a 2.38% aqueous tetramethylammonium hydroxide solution for 10 seconds, rinsed with water, and dried. Then, the resultant was heated at 230 ℃ for 60 minutes on a hot plate to obtain a cured film having no opening.
(production of Pattern film 1)
A10 cm square glass substrate was ultrasonically cleaned with ethanol for 30 seconds, and then subjected to UV/O for 5 minutes3And (6) processing. UV/O3PL 2001N-58 (manufactured by Sen Engineering) was used as UV/O3Generating the device. The optical power (light output) at 254nm was 10mW/cm2。
The negative photosensitive resin composition 1 obtained above was applied to the surface of the cleaned glass substrate using a spinner, and then dried on a hot plate at 100 ℃ for 2 minutes to form a dried film having a thickness of 2.4 μm (1.2 μm in example 3 only). The obtained dried film was once irradiated with an exposure power (exposure output) of 300mW/cm in terms of 365nm through a photomask having a masking portion (non-exposed portion) of 2.5cm × 5cm2UV light (exposure amount of 30 mJ/cm) of the extra-high pressure mercury lamp2Or 50mJ/cm2). Upon exposure, light of 330nm or less was cut off. The distance between the dry film and the photomask was 50 μm. The photomask used was designed to have a line/pitch of 20 μm/50 μm, 10 μm/50 μm, 8 μm/50 μm, 6 μm/50 μm, or 4 μm/50 μm.
Next, the glass substrate after the exposure treatment was immersed in a 2.38% aqueous tetramethylammonium hydroxide solution for 40 seconds to be developed, and the unexposed portion was washed with water and dried. Then, the resultant was heated on a hot plate at 230 ℃ for 60 minutes to obtain a pattern film 1 as a cured film having an opening corresponding to the masking portion of the photomask.
(production of Pattern film 2)
A10 cm square glass substrate was ultrasonically cleaned with ethanol for 30 seconds, and then subjected to UV/O for 5 minutes3And (6) processing. UV/O3PL 2001N-58 (manufactured by Sen Engineering) was used as UV/O3Generating the device. The optical power (light output) at 254nm was 10mW/cm2。
The surface of the cleaned glass substrate was coated with the negative photosensitive resin composition 1 using a spinner, and then the resultant was heated at 100 ℃This was dried on a hot plate for 2 minutes to form a dried film having a thickness of 2.4 μm (1.2 μm in example 3 only). The obtained dried film was once irradiated with an exposure power (exposure output) of 300mW/cm in terms of 365nm through a photomask having a masking portion (non-exposed portion) of 2.5cm × 5cm2UV light (exposure amount of 30 mJ/cm) of the extra-high pressure mercury lamp2Or 50mJ/cm2). Upon exposure, light of 330nm or less was cut off. The distance between the dry film and the photomask was 50 μm. The photomask used was designed to have a line/pitch of 20 μm/50 μm, 10 μm/50 μm, 8 μm/50 μm, 6 μm/50 μm, or 4 μm/50 μm.
Next, the glass substrate after the exposure treatment was immersed in a 2.38% aqueous tetramethylammonium hydroxide solution for 200 seconds to be developed, and the unexposed portion was washed with high-pressure water of 1.5MPa for 10 seconds and then dried. Then, the resultant was heated at 230 ℃ for 60 minutes on a hot plate to obtain a pattern film 2 as a cured film having an opening corresponding to the masking portion of the photomask.
(production of Pattern film 3)
An ITO substrate having an ITO layer on a glass substrate was used, and the negative photosensitive resin composition 1 was applied on the ITO layer using a spinner, and then dried on a hot plate at 100 ℃ for 2 minutes to form a dried film having a film thickness of 2.4 μm (1.2 μm in example 3 only). The obtained dried film was irradiated once with 365 nm-converted exposure power (exposure output) of 300mW/cm through a photomask having an opening pattern (a lattice pattern having a light-shielding portion of 100. mu. m × 200. mu.m and a light-transmitting portion of 20 μm)2UV light of the ultra-high pressure mercury lamp. Upon exposure, light of 330nm or less was cut off. The distance between the dry film and the photomask was 50 μm. In each example, the exposure time was 4 seconds and the exposure amount was 100mJ/cm2。
Next, the glass substrate after the exposure treatment was immersed in a 2.38 mass% aqueous tetramethylammonium hydroxide solution for 40 seconds to be developed, and the unexposed portion was washed with water and dried. Subsequently, the resultant was heated on a hot plate at 230 ℃ for 60 minutes to obtain a patterned film 3 as a cured film having a pattern corresponding to the opening pattern of the photomask.
The negative photosensitive resin composition 1, the cured film, and the pattern films 1 to 3 were evaluated as follows. The evaluation results are shown in table 3 together with the composition of the negative photosensitive resin composition 1.
(evaluation)
< thickness of cured film >
The measurement was carried out using a laser microscope (product of Keyence, device name: VK-8500).
< ink repellency >
The contact angle of PGMEA on the upper surface of the cured film obtained above was measured by the following method to evaluate the ink repellency.
PGMEA droplets were placed on the cured film upper surface 3 according to JIS R3257 "wettability test method for substrate glass surface" by the static drop method, and each PGMEA droplet was measured. The drop size was 2. mu.L/drop, and the measurement was carried out at 20 ℃. The contact angle was determined from the average of the values measured at 3.
The PGMEA contact angle of the upper surface of the cured film obtained above was measured by the above method.
◎ contact angle is more than 45 DEG
○ contact angle is 40-45 deg
△ contact angle is more than 35 degrees and less than 40 degrees
Contact angle less than 35 °
< Pattern Forming Property >
The pattern film 1 was evaluated for pattern formability by the following criteria. The line width of the line portion having a line/pitch of 20 μm/50 μm was measured.
◎ line width within 3 μm with respect to the mask size.
○ line width greater than + -3 μm and within 5 μm relative to the mask size.
X the line width is larger than ± 5 μm or peeling occurs with respect to the mask size.
< development time (200 seconds) residual resolution >
The pattern film 2 was evaluated for peel resistance to long-term development according to the following criteria.
◎ lines with a line width of at least 10 μm remain.
○ lines with a line width of at least 20 μm remain.
Part of the wire was peeled off in all wire/space samples.
< opening residue >
A surface analysis was performed on the central portion of the opening of the ITO substrate with the patterned film 3 by X-ray photoelectron spectroscopy (XPS) under the following conditions, and the F/In value (F1s/In3d 5; ratio of indium atom concentration to carbon atom concentration) of the opening surface measured by XPS was "◎", 1.0 to 2.0 was "○", and 2.0 or more was "X".
[ conditions of XPS ]
Device Quantera-SXM manufactured by ULVAC-PHI
X-ray source Al K α
Beam size of X-ray about 20 μm phi
Measurement region of about 20 μm phi
Angle of detection of 45 DEG from sample surface
Measurement Peak F1s
The measurement Time (measured as Acquired Time) is within 5 minutes
Analytic software MultiPak
[ examples 2 to 13]
A negative photosensitive resin composition, partition walls, and a cured film were produced in the same manner as in example 1 except that the negative photosensitive resin composition in example 1 was changed to the composition shown in table 3, table 4, or table 5, and the same evaluation as in example 1 was performed. The evaluation results of the examples are shown in tables 3,4 and 5 together with the composition of the negative photosensitive resin composition.
[ Table 3]
[ Table 4]
[ Table 5]
Examples 1 to 10 corresponding to examples of the negative photosensitive resin composition of the present invention contain an alkali-soluble resin or alkali-soluble monomer (A) having an unsaturated double bond, a photopolymerization initiator (B), an acid generator (C) and an acid curing agent (D), and thus the amount of exposure is, for example, 30mJ/cm2In that case, high liquid repellency was also obtained at a low exposure amount. In addition, even if the exposure amount is 50mJ/cm2The line width is not easily thickened, and the pattern formability is good.
On the other hand, in examples 11 and 12 corresponding to comparative examples, since they did not contain either of the photopolymerization initiator (B) and the acid generator (C), the exposure amount was, for example, 30mJ/cm2In the case of a low exposure amount as described above, the liquid repellency is insufficient. Therefore, the ink repellency of the upper surface of the cured film is insufficient. Example 13 corresponding to comparative example was sufficient in liquid repellency because the amount of the photopolymerization initiator (B) was increased, but was free from the acid generator (C), even at an exposure amount of, for example, 30mJ/cm2In the case of a low exposure amount, the line width is also easily increased, and the pattern formability is insufficient.
Description of the symbols
1 … substrate, 21 … coating film, 22 … drying film, 23 … exposed film, 23a … exposed portion, 23B … unexposed portion, 4 … partition wall, 4a … ink-repellent layer, 5 … opening portion, 31 … mask portion, 30 … photomask, 9 inkjet head, 10 … ink, 11 … dots, 12 … optical element.
Claims (10)
1. A negative photosensitive resin composition comprising a photocurable fluorine-atom-free alkali-soluble resin or alkali-soluble monomer (A), a photoradical polymerization initiator (B), a photoacid generator (C), an acid curing agent (D), and an ink repellent (E) having a fluorine atom,
the negative photosensitive resin composition contains 5 to 80 mass% of an alkali-soluble resin or alkali-soluble monomer (A), 0.1 to 50 mass% of a photo radical polymerization initiator (B), 0.01 to 10 mass% of a photoacid generator (C), 0.01 to 15 mass% of an ink repellent (E) in the total solid content,
the content of the acid curing agent (D) is 0.1 to 100 parts by mass per 100 parts by mass of the alkali-soluble resin or the alkali-soluble monomer (A),
the ink repellent (E) has a fluorine atom content of 1 to 40 mass%, and has an ethylenic double bond.
2. The negative photosensitive resin composition according to claim 1, further comprising a compound (F) having 2 or more unsaturated double bonds in a molecule and having no acid group or fluorine atom.
3. The negative photosensitive resin composition according to claim 1 or 2, wherein the acid curing agent (D) is at least 1 selected from a melamine-based compound, a urea-based compound, and an epoxy-based compound.
4. The negative photosensitive resin composition according to claim 1 or 2, which is used for producing an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell.
5. The negative photosensitive resin composition according to claim 3, which is used for producing an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell.
6. A resin cured film formed by using the negative photosensitive resin composition according to any one of claims 1 to 5.
7. A partition wall formed in a shape dividing a surface of a substrate into a plurality of partitions for forming dots, the partition wall being formed of the resin cured film according to claim 6.
8. An optical element having a plurality of dots and partitions between adjacent dots on a surface of a substrate, the partitions being formed by the partitions claimed in claim 7.
9. The optical element according to claim 8, wherein the optical element is an organic EL element, a quantum dot display, a TFT array, or a thin film solar cell.
10. The optical element according to claim 8 or 9, wherein the dots are formed by an inkjet method.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2014-148345 | 2014-07-18 | ||
| JP2014148345 | 2014-07-18 | ||
| PCT/JP2015/070289 WO2016010077A1 (en) | 2014-07-18 | 2015-07-15 | Negative-type photosensitive resin composition, and resin cured film, partition and optical element |
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| CN106662815A CN106662815A (en) | 2017-05-10 |
| CN106662815B true CN106662815B (en) | 2020-06-16 |
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| KR102622857B1 (en) * | 2017-02-09 | 2024-01-10 | 동우 화인켐 주식회사 | Black photo sensitive resin composition for a forming pixel defined layer of oled and qled |
| KR20190116307A (en) * | 2017-02-21 | 2019-10-14 | 니폰 제온 가부시키가이샤 | Negative photosensitive resin composition |
| KR102469945B1 (en) | 2017-07-14 | 2022-11-23 | 삼성디스플레이 주식회사 | Display device and manufacturing method thereof |
| KR102146095B1 (en) | 2017-09-15 | 2020-08-19 | 주식회사 엘지화학 | Photoacid generator and photoresist composition for thick layer comprising the same |
| CN110412829A (en) * | 2018-04-26 | 2019-11-05 | 东友精细化工有限公司 | Negative light-sensitive resin combination, photocuring pattern and image display device |
| KR102311491B1 (en) * | 2019-02-13 | 2021-10-08 | 삼성에스디아이 주식회사 | Composition for double layer partition wall, double layer partition wall using the same and display device including the double layer partition wall |
| CN111752097A (en) * | 2019-03-29 | 2020-10-09 | 常州强力电子新材料股份有限公司 | Self-luminous photosensitive resin composition, color filter and image display device |
| KR20200135682A (en) | 2019-05-24 | 2020-12-03 | 삼성디스플레이 주식회사 | Display apparatus and manufacturing the same |
| KR20220149673A (en) * | 2020-03-04 | 2022-11-08 | 에이지씨 가부시키가이샤 | Positive photosensitive resin composition |
| KR20210121917A (en) * | 2020-03-31 | 2021-10-08 | 동우 화인켐 주식회사 | Light Conversion Ink Composition, Color Filter and Display Device |
| CN116438218A (en) | 2020-10-28 | 2023-07-14 | 中央硝子株式会社 | Fluorine-containing resin, liquid repellent, photosensitive resin composition, cured product, and display |
| JPWO2022210797A1 (en) * | 2021-03-29 | 2022-10-06 | ||
| CN114203748A (en) * | 2021-12-10 | 2022-03-18 | Tcl华星光电技术有限公司 | Display panel and method for manufacturing the same |
| KR20240002709A (en) | 2022-06-29 | 2024-01-05 | 샌트랄 글래스 컴퍼니 리미티드 | Photosensitive resin composition, resin film, cured product, dividing wall, organic electroluminescent element, wavelength conversion layer, display, method for producing cured product and method for producing dividing wall |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE60318884T2 (en) * | 2002-11-06 | 2009-01-22 | Asahi Glass Co., Ltd. | Barrier rib and process for its production |
| JP2004277494A (en) | 2003-03-13 | 2004-10-07 | Asahi Glass Co Ltd | Fluororesin and photosensitive resin composition |
| JP4474991B2 (en) * | 2004-04-27 | 2010-06-09 | 旭硝子株式会社 | Resist composition and coating film thereof |
| JP4671338B2 (en) * | 2005-06-27 | 2011-04-13 | 日本化薬株式会社 | Fluorine-containing polysiloxane, photosensitive resin composition using the same, and cured product thereof |
| JP4809006B2 (en) * | 2005-07-05 | 2011-11-02 | 太陽ホールディングス株式会社 | Colored photosensitive resin composition and cured product thereof |
| JP2009003442A (en) * | 2007-05-23 | 2009-01-08 | Mitsubishi Chemicals Corp | Photosensitive resin composition, liquid crystal alignment control rib, spacer, color filter and image display device |
| JP2009251392A (en) * | 2008-04-08 | 2009-10-29 | Fujifilm Corp | Negative resist composition and pattern forming method |
| KR20110050409A (en) * | 2008-07-30 | 2011-05-13 | 아사히 가라스 가부시키가이샤 | Method for manufacturing substrate with partition walls and pixels formed therein |
| JP2011048064A (en) * | 2009-08-26 | 2011-03-10 | Asahi Kasei E-Materials Corp | Photosensitive resin composition and laminate, and electromagnetic wave shield and transparent conductive substrate using the same |
| JP5562739B2 (en) * | 2010-06-30 | 2014-07-30 | 三洋化成工業株式会社 | Photosensitive resin composition |
| JP2012014931A (en) | 2010-06-30 | 2012-01-19 | Sanyo Chem Ind Ltd | Photosensitive resin composition |
| WO2012086610A1 (en) * | 2010-12-20 | 2012-06-28 | 旭硝子株式会社 | Photosensitive resin composition, partition wall, color filter, and organic el element |
| JP2012185430A (en) * | 2011-03-08 | 2012-09-27 | Sumitomo Chemical Co Ltd | Colored curable resin composition |
| JP2013167687A (en) * | 2012-02-14 | 2013-08-29 | Mitsubishi Chemicals Corp | Photosensitive coloring resin composition, color filter, and liquid-crystal display |
| KR102107962B1 (en) * | 2012-11-28 | 2020-05-07 | 에이지씨 가부시키가이샤 | Negative photosensitive resin composition, cured resin film, partition wall and optical element |
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| KR102411740B1 (en) | 2022-06-21 |
| JP6536578B2 (en) | 2019-07-03 |
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| TWI660239B (en) | 2019-05-21 |
| WO2016010077A1 (en) | 2016-01-21 |
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