JP6458236B2 - Alkali-soluble resin, photosensitive resin composition and use thereof - Google Patents
Alkali-soluble resin, photosensitive resin composition and use thereof Download PDFInfo
- Publication number
- JP6458236B2 JP6458236B2 JP2014196958A JP2014196958A JP6458236B2 JP 6458236 B2 JP6458236 B2 JP 6458236B2 JP 2014196958 A JP2014196958 A JP 2014196958A JP 2014196958 A JP2014196958 A JP 2014196958A JP 6458236 B2 JP6458236 B2 JP 6458236B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- alkali
- meth
- resin composition
- photosensitive resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920005989 resin Polymers 0.000 title claims description 63
- 239000011347 resin Substances 0.000 title claims description 63
- 239000011342 resin composition Substances 0.000 title claims description 54
- 239000000178 monomer Substances 0.000 claims description 46
- 229920000642 polymer Polymers 0.000 claims description 43
- 229920001577 copolymer Polymers 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 125000005370 alkoxysilyl group Chemical group 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 20
- 239000003431 cross linking reagent Substances 0.000 claims description 19
- 150000003138 primary alcohols Chemical class 0.000 claims description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 10
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 150000003333 secondary alcohols Chemical class 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 125000005504 styryl group Chemical group 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 95
- -1 oxyoxybutyl Chemical group 0.000 description 36
- 239000000049 pigment Substances 0.000 description 19
- 239000004593 Epoxy Substances 0.000 description 18
- 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 12
- 238000004132 cross linking Methods 0.000 description 11
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000003086 colorant Substances 0.000 description 10
- 239000011229 interlayer Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 229910000077 silane Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 238000010292 electrical insulation Methods 0.000 description 5
- 239000003504 photosensitizing agent Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920006243 acrylic copolymer Polymers 0.000 description 4
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 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
- 238000000059 patterning Methods 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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 3
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- URLYGBGJPQYXBN-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methyl prop-2-enoate Chemical compound OCC1CCC(COC(=O)C=C)CC1 URLYGBGJPQYXBN-UHFFFAOYSA-N 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N alpha-Methyl-n-butyl acrylate Natural products CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 2
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- NQMUGNMMFTYOHK-UHFFFAOYSA-N 1-methoxynaphthalene Chemical compound C1=CC=C2C(OC)=CC=CC2=C1 NQMUGNMMFTYOHK-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 239000004386 Erythritol Substances 0.000 description 2
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
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- 229920000877 Melamine resin Polymers 0.000 description 2
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- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 2
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- 125000001743 benzylic group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- 125000002091 cationic group Chemical group 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
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- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
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- ONJJGUNDDUSPKW-UHFFFAOYSA-N 1,4-diethoxychrysene Chemical compound C1=CC2=C3C=CC=CC3=CC=C2C2=C1C(OCC)=CC=C2OCC ONJJGUNDDUSPKW-UHFFFAOYSA-N 0.000 description 1
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- 230000003606 oligomerizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 150000002987 phenanthrenes Chemical class 0.000 description 1
- 229940067265 pigment yellow 138 Drugs 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- WPPDXAHGCGPUPK-UHFFFAOYSA-N red 2 Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=2C=3C4=CC=C5C6=CC=C7C8=C(C=9C=CC=CC=9)C9=CC=CC=C9C(C=9C=CC=CC=9)=C8C8=CC=C(C6=C87)C(C=35)=CC=2)C4=C1C1=CC=CC=C1 WPPDXAHGCGPUPK-UHFFFAOYSA-N 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、電気絶縁性、耐熱性、耐水性、耐薬品性、機械的強度等の特性に優れ、半導体素子の表面保護膜や層間絶縁膜等の材料として好適に利用することができるアルカリ可溶性樹脂、感光性樹脂組成物及びその用途に関する。 The present invention is excellent in properties such as electrical insulation, heat resistance, water resistance, chemical resistance and mechanical strength, and is alkali-soluble that can be suitably used as a material such as a surface protective film or an interlayer insulation film of a semiconductor element. The present invention relates to a resin, a photosensitive resin composition, and uses thereof.
近年、電子材料分野におけるパソコン、スマートフォン、タブレット等の電子回路素子では、高精細化が急速に進んでおり、画素の開口率を維持するために配線の細線化が進行している。それに伴って、配線を保護する電気絶縁膜も一層の細線化が求められている。例えば、ＴＦＴ液晶表示素子、有機ＥＬ表示素子、集積回路表示素子等では、層間に配置される配線の間を電気的に絶縁するために層間絶縁膜が形成されている。 In recent years, electronic circuit elements such as personal computers, smartphones, and tablets in the field of electronic materials have been rapidly increasing in definition, and wiring has been made thinner in order to maintain the aperture ratio of pixels. Along with this, further thinning of the electrical insulating film for protecting the wiring is required. For example, in a TFT liquid crystal display element, an organic EL display element, an integrated circuit display element, and the like, an interlayer insulating film is formed to electrically insulate between wirings arranged between layers.
この種の層間絶縁膜として用いられる感光性樹脂組成物が特許文献１に開示されている。当該感光性樹脂組成物は、不飽和カルボン酸、エポキシ基含有不飽和化合物及びシラン系単量体を共重合させて得られるアクリル系共重合体と、１，２−キノンアジド化合物と、溶媒とを含むものであり、アルカリ可溶性を有している。 A photosensitive resin composition used as an interlayer insulating film of this type is disclosed in Patent Document 1. The photosensitive resin composition comprises an acrylic copolymer obtained by copolymerizing an unsaturated carboxylic acid, an epoxy group-containing unsaturated compound, and a silane monomer, a 1,2-quinone azide compound, and a solvent. It is included and has alkali solubility.
前記特許文献１に記載されている従来の感光性樹脂組成物を構成するアクリル系共重合体にはカルボン酸が含まれるとともに、シラン系単量体中には加水分解性のシリル基が含まれている。このシラン系単量体の加水分解性シリル基には、メトキシ基やエトキシ基が含まれている。従って、シラン系単量体は経時的にシリル基の加水分解を起こしやすく、その結果架橋反応が生じてアクリル系共重合体の分子量が増大する。このような分子量が増大したアクリル系共重合体を感光性樹脂として使用すると、感光の際に現像性が極端に悪くなり、適切なパターン形成が困難になるという問題がある。 The acrylic copolymer constituting the conventional photosensitive resin composition described in Patent Document 1 contains carboxylic acid, and the silane monomer contains a hydrolyzable silyl group. ing. The hydrolyzable silyl group of this silane monomer contains a methoxy group or an ethoxy group. Accordingly, the silane monomer easily causes hydrolysis of the silyl group over time, and as a result, a crosslinking reaction occurs and the molecular weight of the acrylic copolymer increases. When such an acrylic copolymer having an increased molecular weight is used as a photosensitive resin, there is a problem that developability becomes extremely poor during exposure and it becomes difficult to form an appropriate pattern.
そこで本発明の目的とするところは、加水分解性シリル基の架橋反応を抑制して経時的安定性を得ることができるアルカリ可溶性樹脂、感光性樹脂組成物及びその用途を提供することにある。 Accordingly, an object of the present invention is to provide an alkali-soluble resin, a photosensitive resin composition and its use capable of suppressing the crosslinking reaction of hydrolyzable silyl groups and obtaining stability over time.
上記の目的を達成するために、請求項１に記載の発明のアルカリ可溶性樹脂は、カルボキシル基を含む重合単位と、アルコキシシリル基を含む重合単位とを有効成分として含有する共重合体が溶媒に溶解されたアルカリ可溶性樹脂であって、前記溶媒は、アルキル基の炭素数が４又は５の直鎖又は分岐鎖を有するアルコールを含むことを特徴とする。 In order to achieve the above object, the alkali-soluble resin of the invention according to claim 1 is characterized in that a copolymer containing, as active ingredients, a polymer unit containing a carboxyl group and a polymer unit containing an alkoxysilyl group is used as a solvent. A dissolved alkali-soluble resin, wherein the solvent includes an alcohol having a linear or branched chain in which the alkyl group has 4 or 5 carbon atoms.
請求項２に記載の発明のアルカリ可溶性樹脂は、請求項１に係る発明において、前記カルボキシル基を含む重合単位は不飽和カルボン酸、不飽和カルボン酸無水物又はこれらの混合物から誘導される重合単位であり、アルコキシシリル基を含む重合単位は下記の式（１）で表される単量体から誘導される重合単位であり、さらに共重合体が前記以外の共重合性単量体から誘導される重合単位を含有することを特徴とする。 The alkali-soluble resin of the invention according to claim 2 is the invention according to claim 1, wherein the polymer unit containing the carboxyl group is a polymer unit derived from an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof. The polymerized unit containing an alkoxysilyl group is a polymerized unit derived from a monomer represented by the following formula (1), and the copolymer is derived from a copolymerizable monomer other than those described above. It is characterized by containing a polymerization unit.
Ｘ−（ＣＨ２）ａ−Ｓｉ（ＯＲ）ｂ（ＣＨ３）３−ｂ ・・・（１）
但し、式（１）中のＸはビニル基、スチリル基又は（メタ）アクリロイル基、Ｒはメチル基又はエチル基、ａは０〜３の整数、ｂは１〜３の整数である。
X- (CH 2) a -Si ( OR) b (CH 3) 3-b ··· (1)
However, X in Formula (1) is a vinyl group, a styryl group, or a (meth) acryloyl group, R is a methyl group or an ethyl group, a is an integer of 0-3, b is an integer of 1-3.
請求項３に記載の発明のアルカリ可溶性樹脂は、請求項２に係る発明において、前記共重合体が水酸基含有不飽和単量体から誘導される水酸基を含む重合単位を含有する。
請求項４に記載の発明のアルカリ可溶性樹脂は、請求項１から請求項３のいずれか１項に係る発明において、前記アルコールは、アルキル基の炭素数が４又は５の第一級アルコール又は第二級アルコールである。
The alkali-soluble resin according to a third aspect of the present invention is the invention according to the second aspect, wherein the copolymer contains a polymer unit containing a hydroxyl group derived from a hydroxyl group-containing unsaturated monomer.
The alkali-soluble resin according to a fourth aspect of the present invention is the invention according to any one of the first to third aspects, wherein the alcohol is a primary alcohol having 4 or 5 alkyl groups or a primary alcohol. Secondary alcohol.
請求項５に記載の発明のアルカリ可溶性樹脂は、請求項４に係る発明において、前記アルコールは、アルキル基の炭素数が４又は５の第一級アルコールである。
請求項６に記載の発明のアルカリ可溶性樹脂は、請求項５に係る発明において、前記アルキル基の炭素数が４の第一級アルコールは、１−ブタノールである。
The alkali-soluble resin of the invention according to claim 5 is the invention according to claim 4, wherein the alcohol is a primary alcohol having an alkyl group with 4 or 5 carbon atoms.
In the alkali-soluble resin of the invention according to claim 6, in the invention according to claim 5, the primary alcohol having 4 carbon atoms in the alkyl group is 1-butanol.
請求項７に記載の発明の感光性樹脂組成物は、請求項１から請求項６のいずれか一項に記載のアルカリ可溶性樹脂と、架橋剤と、感光剤とを含有するものである。
請求項８に記載の発明の感光性樹脂組成物の硬化物は、請求項７に記載の感光性樹脂組成物を活性エネルギー線により硬化させてなるものである。
A photosensitive resin composition according to a seventh aspect of the invention contains the alkali-soluble resin according to any one of the first to sixth aspects, a crosslinking agent, and a photosensitive agent.
A cured product of the photosensitive resin composition of the invention according to claim 8 is obtained by curing the photosensitive resin composition according to claim 7 with active energy rays.
請求項９に記載の発明の層間絶縁膜は、請求項８に記載の硬化物により形成され、層間に配置される配線間を電気的に絶縁するものである。 An interlayer insulating film according to a ninth aspect of the present invention is formed of the cured product according to the eighth aspect, and electrically insulates between wirings arranged between the layers.
本発明のアルカリ可溶性樹脂によれば、加水分解性シリル基の架橋反応を抑制して経時的安定性を得ることができるという効果を奏する。 According to the alkali-soluble resin of the present invention, there is an effect that the cross-linking reaction of the hydrolyzable silyl group can be suppressed and the stability over time can be obtained.
以下、本発明を具体化した実施形態について詳細に説明する。
まず、アルカリ可溶性樹脂について説明する。本実施形態のアルカリ可溶性樹脂は、カルボキシル基（−ＣＯＯＨ）を含む重合単位と、アルコキシシリル基〔後述する式（１）の−Ｓｉ（ＯＲ）ｂ（ＣＨ３）３−ｂ〕を含む重合単位とを有効成分として含有する共重合体が溶媒に溶解されたものである。前記溶媒は、アルキル基の炭素数が４又は５の直鎖又は分岐鎖を有する特定のアルコールを含んでいる。このアルカリ可溶性樹脂は、カルボキシル基を有する単量体及びアルコキシシリル基を有する単量体等の単量体が溶媒中で重合開始剤により常法に従って重合されて形成され、通常ランダム共重合体が溶媒に溶解された状態で形成される。
DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments embodying the present invention will be described in detail.
First, the alkali-soluble resin will be described. The alkali-soluble resin of the present embodiment includes a polymer unit containing a carboxyl group (—COOH) and an alkoxysilyl group [-Si (OR) b (CH 3 ) 3 -b of formula (1) described later]. Are dissolved in a solvent. The solvent contains a specific alcohol having a linear or branched chain in which the alkyl group has 4 or 5 carbon atoms. This alkali-soluble resin is formed by polymerizing monomers such as a monomer having a carboxyl group and a monomer having an alkoxysilyl group in a solvent by a polymerization initiator according to a conventional method. It is formed in a state dissolved in a solvent.
前記カルボキシル基を含む重合単位は、側鎖にカルボキシル基を含む重合単位であればよいが、不飽和カルボン酸、不飽和カルボン酸無水物又はこれらの混合物から誘導される重合単位が好ましい。 The polymer unit containing a carboxyl group may be a polymer unit containing a carboxyl group in the side chain, but a polymer unit derived from an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof is preferred.
前記アルコキシシリル基を含む重合単位は、側鎖にアルコキシシリル基を含む重合単位であればよいが、下記の式（１）で表される単量体から誘導される重合単位が好ましい。
Ｘ−（ＣＨ２）ａ−Ｓｉ（ＯＲ）ｂ（ＣＨ３）３−ｂ ・・・（１）
但し、式（１）中のＸはビニル基、スチリル基又は（メタ）アクリロイル基、Ｒはメチル基又はエチル基、ａは０〜３の整数、ｂは１〜３の整数である。
The polymer unit containing an alkoxysilyl group may be a polymer unit containing an alkoxysilyl group in the side chain, but a polymer unit derived from a monomer represented by the following formula (1) is preferred.
X- (CH 2) a -Si ( OR) b (CH 3) 3-b ··· (1)
However, X in Formula (1) is a vinyl group, a styryl group, or a (meth) acryloyl group, R is a methyl group or an ethyl group, a is an integer of 0-3, b is an integer of 1-3.
また、前記共重合体には、水酸基含有不飽和単量体から誘導される水酸基を含む重合単位を含有することが好ましい。
さらに、共重合体には、前記単量体以外のその他の共重合性単量体から誘導されるその他の重合単位を含有することが好ましい。
Moreover, it is preferable that the said copolymer contains the polymer unit containing the hydroxyl group induced | guided | derived from a hydroxyl-containing unsaturated monomer.
Furthermore, it is preferable that the copolymer contains other polymerization units derived from other copolymerizable monomers other than the monomer.
次に、アルカリ可溶性樹脂の各構成要素について順に説明する。
〔共重合体〕
（カルボキシル基を含む重合単位）
このカルボキシル基を含む重合単位は、共重合体をアルカリ性現像液により溶解させる機能を発現する。カルボキシル基を含む重合単位を形成するための不飽和カルボン酸としては、例えば(メタ)アクリル酸、マレイン酸、フマル酸、クロトン酸、イタコン酸、シトラコン酸、メサコン酸及びケイ皮酸等が挙げられる。不飽和カルボン酸無水物としては、例えば無水マレイン酸、無水イタコン酸、無水シトラコン酸、無水フタル酸、無水テトラヒト゛ロフタル酸、無水トリメリット酸及び無水ヒ゜ロメリット酸等が挙げられる。また、これらの不飽和カルボン酸と不飽和カルボン酸無水物との混合物を用いてもよい。
Next, each component of alkali-soluble resin is demonstrated in order.
[Copolymer]
(Polymerized unit containing carboxyl group)
This polymerized unit containing a carboxyl group expresses a function of dissolving the copolymer with an alkaline developer. Examples of the unsaturated carboxylic acid for forming a polymer unit containing a carboxyl group include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, mesaconic acid, and cinnamic acid. . Examples of the unsaturated carboxylic acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, tetrahuman hydrophthalic anhydride, trimellitic anhydride, and pyromellitic anhydride. Moreover, you may use the mixture of these unsaturated carboxylic acid and unsaturated carboxylic anhydride.
これらの中でも、（メタ）アクリル酸は、層間絶縁膜を形成するとき綺麗なパターン形状が得られることから好ましい。共重合体中におけるカルボキシル基を含む重合単位の含有量は、アルカリ可溶性樹脂中のアルカリ性現像液により溶解させたい部分を綺麗に溶解させるために３質量％以上が好ましく、一方溶解させない部分をしっかり残すために５０質量％以下が好ましい。このカルボキシル基を含む重合単位の含有量は、５〜３０質量％が特に好ましい。 Among these, (meth) acrylic acid is preferable because a beautiful pattern shape can be obtained when an interlayer insulating film is formed. The content of the polymerization unit containing a carboxyl group in the copolymer is preferably 3% by mass or more in order to cleanly dissolve the portion to be dissolved by the alkaline developer in the alkali-soluble resin, while leaving the portion not to be dissolved firmly. Therefore, 50 mass% or less is preferable. The content of the polymerization unit containing a carboxyl group is particularly preferably 5 to 30% by mass.
（アルコキシシリル基を含む重合単位）
このアルコキシシリル基を含む重合単位は、共重合体の耐熱性、耐薬品性等の特性を発現させる機能を有する。アルコキシシリル基を含む重合単位を形成する前記式（１）で表される単量体としては、式（１）の条件を満たす単量体であれば特に制限されないが、ｂが２又は３であることが好ましい。ｂが１の場合、共重合体の架橋密度が低くなり、充分な耐熱性や耐薬品性が得られない傾向を示す。
(Polymerized unit containing alkoxysilyl group)
This polymerized unit containing an alkoxysilyl group has a function of developing characteristics such as heat resistance and chemical resistance of the copolymer. The monomer represented by the formula (1) forming a polymer unit containing an alkoxysilyl group is not particularly limited as long as it satisfies the condition of the formula (1), but b is 2 or 3. Preferably there is. When b is 1, the crosslinking density of the copolymer is low, and sufficient heat resistance and chemical resistance tend not to be obtained.
このような単量体としては、例えば3-(メタ)アクリロキシフ゜ロヒ゜ルメチルシ゛メトキシシラン、3-(メタ)アクリロキシフ゜ロヒ゜ルトリメトキシシラン、3-(メタ)アクリロキシフ゜ロヒ゜ルメチルシ゛エトキシシラン、3-(メタ)アクリロキシフ゜ロヒ゜ルトリエトキシシラン、p-スチリルトリメトキシシラン、ヒ゛ニルトリメトキシシラン、ヒ゛ニルトリエトキシシラン、ヒ゛ニルトリアセトキシシラン、アクリルトリメトキシシラン等又はこれらの単量体をオリゴマー化又はポリマー化した化合物が挙げられる。 Examples of such a monomer include 3- (meth) acryloxyfluoromethyldimethoxysilane, 3- (meth) acryloxyfluorotrimethoxysilane, 3- (meth) acryloxyfluoromethyldiethoxysilane, 3- (meth) (Meth) acryloxyfluorotriethoxysilane, p-styryltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, acryltrimethoxysilane, etc., or compounds obtained by oligomerizing or polymerizing these monomers Is mentioned.
共重合体中におけるアルコキシシリル基を含む重合単位の含有量は、共重合体の耐熱性及び耐薬品性を得る上で１質量％以上が好ましく、貯蔵安定性を損なわないために５０質量％以下が好ましい。このアルコキシシリル基を含む重合単位の含有量は、５〜３０質量％が特に好ましい。 The content of the polymer unit containing an alkoxysilyl group in the copolymer is preferably 1% by mass or more in order to obtain the heat resistance and chemical resistance of the copolymer, and 50% by mass or less in order not to impair the storage stability. Is preferred. The content of the polymerization unit containing the alkoxysilyl group is particularly preferably 5 to 30% by mass.
（水酸基を含む重合単位）
この水酸基を含む重合単位は、共重合体に架橋構造を形成し、機械的強度等の特性を付与する機能を発現する。水酸基を含む重合単位を形成する水酸基含有不飽和単量体としては、水酸基を含有する単量体であれば特に制限されない。この水酸基含有不飽和単量体としては、例えば2-ヒト゛ロキシエチル(メタ)アクリレート、4-ヒト゛ロキシフ゛チル(メタ)アクリレート、5-ヒト゛ロキシヘ゜ンチル(メタ)アクリレート、6-ヒト゛ロキシヘキシル(メタ)アクリレート、8-ヒト゛ロキシオクチル(メタ)アクリレート等のアルキル基の炭素数が１〜１６の(メタ)アクリル酸ヒト゛ロキシアルキルエステル、カフ゜ロラクトン変性2-ヒト゛ロキシエチル(メタ)アクリレート等のカフ゜ロラクトン変性単量体、シ゛エチレンク゛リコール(メタ)アクリレート、ホ゜リエチレンク゛リコール(メタ)アクリレート等のオキシアルキレン変性単量体、その他2-アクリロイロキシエチル-2-ヒト゛ロキシエチルフタル酸、N-メチロール(メタ)アクリルアミト゛、N-ヒト゛ロキシエチル(メタ)アクリルアミト゛、1,4-シクロヘキサンシ゛メタノールモノアクリレート等の第１級水酸基含有単量体;2-ヒト゛ロキシフ゜ロヒ゜ル(メタ)アクリレート、2-ヒト゛ロキシフ゛チル(メタ)アクリレート、2-ヒト゛ロキシ-3-フェノキシフ゜ロヒ゜ル(メタ)アクリレート、3-クロロ2-ヒト゛ロキシフ゜ロヒ゜ル(メタ)アクリレート等の第２級水酸基含有単量体;2,2-シ゛メチル2-ヒト゛ロキシエチル(メタ)アクリレート等の第３級水酸基含有単量体が挙げられる。
(Polymerized unit containing hydroxyl group)
This polymerized unit containing a hydroxyl group expresses a function of forming a crosslinked structure in the copolymer and imparting properties such as mechanical strength. The hydroxyl group-containing unsaturated monomer that forms a polymer unit containing a hydroxyl group is not particularly limited as long as it is a monomer containing a hydroxyl group. Examples of the hydroxyl group-containing unsaturated monomer include 2-human oxyethyl (meth) acrylate, 4-human oxyoxybutyl (meth) acrylate, 5-human oxyhexyl (meth) acrylate, 6-human oxyhexyl (meth) acrylate, 8- (Meth) acrylic acid human alkyloxyalkyl ester having 1 to 16 carbon atoms, such as human oxyoctyl (meth) acrylate, caprolactone-modified 2-human oxyethyl (meth) acrylate, etc., chlorolactone-modified monomer, diethylene glycol (meth) acrylate Oxyalkylene-modified monomers such as polyethylene glycol (meth) acrylate, 2-acryloyloxyethyl-2-humanoxyethylphthalic acid, N-methylol (meth) acrylamido, N-humanoxyethyl (meth) acrylamido, Primary hydroxyl group-containing monomer such as 1,4-cyclohexanedimethanol monoacrylate; 2-human oxypropyl (meth) acrylate, 2-human oxyoxybutyl (meth) acrylate, 2-human oxy-3-phenoxy chloropropyl (meth) acrylate And secondary hydroxyl group-containing monomers such as 3-chloro-2-humanoxypropyl (meth) acrylate; and tertiary hydroxyl group-containing monomers such as 2,2-dimethyl-2-humanhydroxyethyl (meth) acrylate.
また、水酸基含有不飽和単量体としてシ゛エチレンク゛リコール(メタ)アクリレート、ホ゜リエチレンク゛リコールモノ(メタ)アクリレート等のホ゜リエチレンク゛リコール誘導体、ホ゜リフ゜ロヒ゜レンク゛リコールモノ(メタ)アクリレート等のホ゜リフ゜ロヒ゜レンク゛リコール誘導体、ホ゜リ(エチレンク゛リコール-フ゜ロヒ゜レンク゛リコール)モノ(メタ)アクリレート、ホ゜リ(エチレンク゛リコール-テトラメチレンク゛リコール)モノ(メタ)アクリレート、ホ゜リ(フ゜ロヒ゜レンク゛リコール-テトラメチレンク゛リコール)モノ(メタ)アクリレート等のオキシアルキレン変性単量体、ク゛リセロール(メタ)アクリレートを用いてもよい。 Polyhydroxyethylene derivatives such as polyethylene glycol (meth) acrylate and polyethylene glycol mono (meth) acrylate, polyfluoroethylene glycol mono (meth) acrylate, etc. Oxyalkylene-modified monomers such as mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (fluoroethylene glycol-tetramethylene glycol) mono (meth) acrylate, and glycerol (meth) acrylate It may be used.
共重合体中における水酸基を含む重合単位の含有量は、共重合体の機械的強度等の特性を得る上で３質量％以上が好ましく、貯蔵安定性を損なわないために４０質量％以下が好ましい。この水酸基を含む重合単位の含有量は、５〜３５質量％が特に好ましい。 The content of the polymer unit containing a hydroxyl group in the copolymer is preferably 3% by mass or more for obtaining characteristics such as mechanical strength of the copolymer, and is preferably 40% by mass or less in order not to impair the storage stability. . The content of the polymerization unit containing a hydroxyl group is particularly preferably 5 to 35% by mass.
（その他の重合単位）
その他の重合単位は、共重合体の主な骨格を形成し、共重合体の機械的強度等の特性を得るためのものである。その他の重合単位を形成するその他の共重合性単量体は、特に制限されない。その他の共重合性単量体として具体的には、スチレン、α-メチルスチレン、tert-フ゛チルスチレン、o-ヒ゛ニルトルエン、m-ヒ゛ニルトルエン、p-ヒ゛ニルトルエン、p-クロロスチレン、o-メトキシスチレン、m-メトキシスチレン、p-メトキシスチレン、o-ヒ゛ニルヘ゛ンシ゛ルメチルエーテル、m-ヒ゛ニルヘ゛ンシ゛ルメチルエーテル、p-ヒ゛ニルヘ゛ンシ゛ルメチルエーテル、o-ヒ゛ニルヘ゛ンシ゛ルク゛リシシ゛ルエーテル、m-ヒ゛ニルヘ゛ンシ゛ルク゛リシシ゛ルエーテル、及びp-ヒ゛ニルヘ゛ンシ゛ルク゛リシシ゛ルエーテル等の芳香族ヒ゛ニル化合物、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-フ゜ロヒ゜ル(メタ)アクリレート、i-フ゜ロヒ゜ル(メタ)アクリレート、n-フ゛チル(メタ)アクリレート、i-フ゛チル(メタ)アクリレート、sec-フ゛チル(メタ)アクリレート、t-フ゛チル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート、n-ノニル(メタ)アクリレート、i-ノニル(メタ)アクリレート、n-テ゛シル(メタ)アクリレート、i-テ゛シル(メタ)アクリレート、ラウリル(メタ)アクリレート、トリテ゛シル(メタ)アクリレート、セチル(メタ)アクリレート、n-ステアリル(メタ)アクリレート、i-ステアリル(メタ)アクリレート、ヘ゛ヘニル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、フェニル(メタ)アクリレート、テトラヒト゛ロフリフリル(メタ)アクリレート、イソホ゛ルニル(メタ)アクリレート、2-メチル-2-アタ゛マンチル(メタ)アクリレート、2-エチル-2-アタ゛マンチル(メタ)アクリレート及び2-イソフ゜ロヒ゜ル-2-アタ゛マンチル(メタ)アクリレート、2-メトキシエチル(メタ)アクリレート、2-フェノキシエチル(メタ)アクリレート、シ゛エチレンク゛リコールモノメチルエーテル(メタ)アクリレート、トリエチレンク゛リコールモノメチルエーテル(メタ)アクリレート、フ゜ロヒ゜レンク゛リコールモノメチルエーテル(メタ)アクリレート、シ゛フ゜ロヒ゜レンク゛リコールモノメチルエーテル(メタ)アクリレート、イソホ゛ルニル(メタ)アクリレート、2-ヒト゛ロキシ-3-フェノキシフ゜ロヒ゜ル(メタ)アクリレート、2-アミノエチル(メタ)アクリレート、2-シ゛メチルアミノエチル(メタ)アクリレート、2-アミノフ゜ロヒ゜ル(メタ)アクリレート、2-シ゛メチルアミノフ゜ロヒ゜ルアクリレート、3-アミノフ゜ロヒ゜ル(メタ)アクリレート、3-シ゛メチ ルアミノフ゜ロヒ゜ル(メタ)アクリレート、ク゛リシシ゛ル(メタ)アクリレート、2,2,2-トリフロロエチル(メタ)アクリレート、2,2,3,3-テトラフロロフ゜ロヒ゜ル(メタ)アクリレート、2,2,3,3,3-ヘ゜ンタフロロフ゜ロヒ゜ル(メタ)アクリレート、2,2,3,4,4,4-ヘキサフロロフ゛チル(メタ)アクリレート、2-(ハ゜ーフロロフ゛チル)エチル(メタ)アクリレート、3-ハ゜ーフロロフ゛チル-2-ヒト゛ロキシフ゜ロヒ゜ル(メタ)アクリレート、2-(ハ゜ーフロロヘキシル)エチル(メタ)アクリレート、3-ハ゜ーフロロヘキシル-2-ヒト゛ロキシフ゜ロヒ゜ル(メタ)アクリレート、1H,1H,3H-テトラフロロフ゜ロヒ゜ル(メタ)アクリレート、1H,1H,5H-オクタフロロヘ゜ンチル(メタ)アクリレート、1H,1H,7H-ト゛テ゛カフロロヘフ゜チル(メタ)アクリレート、ハ゜ーフロロオクチルエチル(メタ)アクリレート等の不飽和カルボン酸エステル等が挙げられる。
(Other polymer units)
The other polymerized units are for forming the main skeleton of the copolymer and obtaining properties such as mechanical strength of the copolymer. Other copolymerizable monomers that form other polymerized units are not particularly limited. Specific examples of other copolymerizable monomers include styrene, α-methylstyrene, tert-butylstyrene, o-phenyltoluene, m-vinyltoluene, p-phenyltoluene, p-chlorostyrene, and o-methoxystyrene. , M-methoxy styrene, p-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzylic ether, m-vinyl benzylic ether, and p-benzyl ether Aromatic vinyl compounds such as benzyl ether, methyl (meth) acrylate, ethyl (meth) acrylate, n-fluoro (meth) acrylate, i-fluoro (meth) acrylate, n-butyl (meth) acrylate, i-phenyl ( (Meta) acryle , Sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, n-nonyl (meth) acrylate, i-nonyl (meth) acrylate, n- Decyl (meth) acrylate, i-decyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, n-stearyl (meth) acrylate, i-stearyl (meth) acrylate, hehenyl ( (Meth) acrylates, cyclohexyl (meth) acrylates, phenyl (meth) acrylates, tetrahedrofurfuryl (meth) acrylates, isobornyl (meth) acrylates, 2-methyl-2-adamantyl (meth) acrylates, 2-ethyl-2-adamantyl ( (Meth) acrylate and 2-isofluoro-2-adaman (Meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, fluoropolyethylene monomethyl ether (meth) acrylate , Difluoroethylene glycol monomethyl ether (meth) acrylate, isobornyl (meth) acrylate, 2-humanoxy-3-phenoxypropyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2 -Aminopropyl (meth) acrylate, 2-dimethylaminophenyl acrylate, 3-aminopropyl (meth) acrylate, 3-dimethylaminopropyl (medium) ) Acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3,3-genta Fluorofluoropropyl (meth) acrylate, 2,2,3,4,4,4-Hexafluorobutyl (meth) acrylate, 2- (fluorofluoroethyl) ethyl (meth) acrylate, 3-fluorofluoro-2-butyloxypropyl (Meth) acrylate, 2- (fluorofluorohexyl) ethyl (meth) acrylate, 3-fluorofluoro-2-hydroxypropyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H , 5H-octafluorohexyl (meth) acrylate, 1H, 1H, 7H-decafluoroheptyl (meth) acrylate, unsaturated fluorooctylethyl (meth) acrylate, etc. Examples thereof include carboxylic acid esters.
共重合体中におけるその他の重合単位の含有量は、共重合体の機械的強度等の特性を得る上で４０質量％以上が好ましく、共重合体中における前記有効成分を確保するために９０質量％以下が好ましい。その他の重合単位の含有量は、６０〜８０質量％が特に好ましい。 The content of the other polymer units in the copolymer is preferably 40% by mass or more in order to obtain characteristics such as mechanical strength of the copolymer, and 90% by mass in order to ensure the active ingredient in the copolymer. % Or less is preferable. The content of other polymerized units is particularly preferably 60 to 80% by mass.
〔溶媒〕
（特定のアルコール）
溶媒のアルコールは、加水分解性シリル基の加水分解を抑え、架橋反応を抑制する観点から、アルキル基の炭素数が４又は５の直鎖又は分岐鎖を有する特定のアルコールが用いられる。この特定のアルコールとしては、例えば1-フ゛タノール、2-フ゛タノール、イソフ゛タノール、1-ヘ゜ンタノール、2-ヘ゜ンタノール、2-メチル-1-フ゛タノール、3-メチル-1フ゛タノール、3-メチル-2-フ゛タノール、2,2-シ゛メチル-1-フ゜ロハ゜ノール等が挙げられる。
〔solvent〕
(Specific alcohol)
As the solvent alcohol, a specific alcohol having a linear or branched chain in which the alkyl group has 4 or 5 carbon atoms is used from the viewpoint of suppressing hydrolysis of the hydrolyzable silyl group and suppressing a crosslinking reaction. Examples of this specific alcohol include 1-butanol, 2-butanol, isobutanol, 1-hexane, 2-hexane, 2-methyl-1-butanol, 3-methyl-1 butanol, and 3-methyl-2- Examples include butanol and 2,2-dimethyl-1-fluorophenol.
これら特定のアルコールのうち、加水分解性シリル基の架橋反応を一層抑制できる点から、アルキル基の炭素数が４又は５の第一級アルコール又は第二級アルコールが好ましく、さらにアルキル基の炭素数が４又は５の第一級アルコールが好ましい。これらのうち、アルキル基の炭素数が４の第一級アルコールとしては、１−ブタノール（ｎ−ブタノール）及びイソブタノールが挙げられる。前記アルキル基の炭素数が４の第一級アルコールのうち、加水分解性シリル基の架橋反応を抑制する機能が最も高い点から、１−ブタノールが好ましい。 Of these specific alcohols, a primary alcohol or secondary alcohol having 4 or 5 alkyl groups is preferred, and the number of carbon atoms in the alkyl group is more preferable because the crosslinking reaction of the hydrolyzable silyl group can be further suppressed. Of 4 or 5 are preferred. Among these, 1-butanol (n-butanol) and isobutanol are mentioned as a primary alcohol whose carbon number of an alkyl group is 4. Of the primary alcohols having 4 carbon atoms in the alkyl group, 1-butanol is preferred because it has the highest function of suppressing the crosslinking reaction of hydrolyzable silyl groups.
前記溶媒としては、上記特定のアルコール以外のアルコール等のその他の溶媒が含まれていてもよい。
溶媒中における特定のアルコールの含有量は、アルカリ可溶性樹脂の貯蔵安定性の観点から２０〜１００質量％が好ましく、４０〜１００質量％がさらに好ましく、６０〜１００質量％が特に好ましい。
As said solvent, other solvents, such as alcohol other than the said specific alcohol, may be contained.
The content of the specific alcohol in the solvent is preferably 20 to 100% by mass, more preferably 40 to 100% by mass, and particularly preferably 60 to 100% by mass from the viewpoint of the storage stability of the alkali-soluble resin.
前記共重合体に対する溶媒の含有量は、共重合性単量体の共重合の円滑な進行及び感光性樹脂組成物の調製や利用の容易性等の観点から、共重合体１００質量部に対して５０〜３００質量部が好ましく、１００〜２００質量部がさらに好ましい。 The content of the solvent with respect to the copolymer is based on 100 parts by mass of the copolymer from the viewpoint of smooth progress of copolymerization of the copolymerizable monomer and ease of preparation and use of the photosensitive resin composition. 50 to 300 parts by mass is preferable, and 100 to 200 parts by mass is more preferable.
（その他の溶媒）
その他の溶媒として例えば、メタノール、エタノール、フ゜ロハ゜ノール、ヘキサノ-ル等の特定のアルコール以外のアルコール、エチレンク゛リコールモノメチルエーテルアセテート、エチレンク゛リコールモノエチルエーテルアセテート等のエチレンク゛リコールモノアルキルエーテルアセテート類、フ゜ロヒ゜レンク゛リコールモノメチルエーテル、フ゜ロヒ゜レンク゛リコールモノエチルエーテル等のフ゜ロヒ゜レンク゛リコールモノアルキルエーテル類、フ゜ロヒ゜レンク゛リコールシ゛メチルエーテル、フ゜ロヒ゜レンク゛リコールシ゛エチルエーテル等のフ゜ロヒ゜レンク゛リコールシ゛アルキルエーテル類、フ゜ロヒ゜レンク゛リコールモノメチルエーテルアセテート、フ゜ロヒ゜レンク゛リコールモノエチルエーテルアセテート等のフ゜ロヒ゜レンク゛リコールモノアルキルエーテルアセテート類、エチルセロソルフ゛、フ゛チルセロソルフ゛等のセロソルフ゛類、フ゛チルカルヒ゛トール等のカルヒ゛トール類、乳酸メチル、乳酸エチル、乳酸n-フ゜ロヒ゜ル、乳酸イソフ゜ロヒ゜ル等の乳酸エステル類、酢酸エチル、酢酸n-フ゜ロヒ゜ル、酢酸イソフ゜ロヒ゜ル、酢酸n-フ゛チル、酢酸イソフ゛チル、酢酸n-アミル、酢酸イソアミル、フ゜ロヒ゜オン酸イソフ゜ロヒ゜ル、フ゜ロヒ゜オン酸n-フ゛チル、フ゜ロヒ゜オン酸イソフ゛チル等の脂肪族カルホ゛ン酸エステル類、3-メトキシフ゜ロヒ゜オン酸メチル、3-メトキシフ゜ロヒ゜オン酸エチル、3-エトキシフ゜ロヒ゜オン酸メチル、3-エトキシフ゜ロヒ゜オン酸エチル、ヒ゜ルヒ゛ン酸メチル、ヒ゜ルヒ゛ン酸エチル等の他のエステル類、トルエン、キシレン等の芳香族炭化水素類、2-ヘフ゜タノン、3-ヘフ゜タノン、4-ヘフ゜タノン、シクロヘキサノン等のケトン類、N-シ゛メチルホルムアミト゛、N-メチルアセトアミト゛、N,N-シ゛メチルアセトアミト゛、N-メチルヒ゜ロリト゛ン等のアミト゛類、γ-フ゛チロラクトン等のラクトン類等が挙げられる。
(Other solvents)
Other solvents include, for example, alcohols other than specific alcohols such as methanol, ethanol, chloroform and hexanole, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, and fluoropolyethylene monomethyl ether. Fluorene glycol monoalkyl ethers such as fluorene glycol monoethyl ether, fluorene glycol dimethyl ether, fluorene glycol dimethyl ether, fluorene glycol monoalkyl ether ethyl acetate, Cellulose such as chloroethylene glycol monoalkyl ether acetates, ethyl cellosolve, butyl cellosolve, carbitols such as butylcarbitol, lactate esters such as methyl lactate, ethyl lactate, lactate n-fluoropropyl, lactoisopropyl lactate, acetic acid Aliphatic carboxylic acid esters such as ethyl, n-fluoroacetate, isofluoroacetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isofluoropropyl fluorophosphate, n-butyl hydrofluorate, isobutyl hydrofluorate, Methyl methoxyfluorophosphate, ethyl 3-methoxyfluoroformate, methyl 3-ethoxyfluoroformate, ethyl 3-ethoxyfluoroformate, methyl benzoate, ethyl benzoate Other esters such as toluene, aromatic hydrocarbons such as toluene and xylene, ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N-dimethylformamido, N-methylacetamido, N, N -Amidides such as dimethylacetamide and N-methylpyrrolidone, and lactones such as γ-butyrolactone.
次に、感光性樹脂組成物について説明する。
本実施形態の感光性樹脂組成物は、前述したアルカリ可溶性樹脂と、架橋剤と、感光剤とを含有するものであるが、さらに増感剤、着色剤等が含まれていてもよい。以下に、アルカリ可溶性樹脂以外の成分について説明する。
Next, the photosensitive resin composition will be described.
The photosensitive resin composition of the present embodiment contains the alkali-soluble resin, the cross-linking agent, and the photosensitizer described above, but may further contain a sensitizer, a colorant, and the like. Below, components other than alkali-soluble resin are demonstrated.
〔架橋剤〕
架橋剤は、光反応性を有する多官能単量体又はオリゴマーを意味し、活性エネルギー線の照射により架橋、硬化する。前記光反応性は、ラジカル硬化型とカチオン硬化型とに分類される。
[Crosslinking agent]
A crosslinking agent means the polyfunctional monomer or oligomer which has photoreactivity, and bridge | crosslinks and hardens | cures by irradiation of an active energy ray. The photoreactivity is classified into a radical curable type and a cationic curable type.
ラジカル硬化型の架橋剤としては、エチレンク゛リコールシ゛(メタ)アクリレート、シ゛シクロヘ゜ンテニルシ゛(メタ)アクリレート、トリエチレンク゛リコールシ゛アクリレート、テトラエチレンク゛リコールシ゛(メタ)アクリレート、トリシクロテ゛カンシ゛イルシ゛メチレンシ゛(メタ)アクリレート、トリス (2-ヒト゛ロキシエチル)イソシアヌレートシ゛(メタ)アクリレート、トリス(2-ヒト゛ロキシエチル)イソシアヌレートトリ(メタ)アクリレート、カフ゜ロラクトン変性トリス(2-ヒト゛ロキシエチル)イソシアヌレートトリ(メタ)アクリレート、トリメチロールフ゜ロハ゜ントリ(メタ)アクリレート、エチレンオキシト゛（以下、EOという）変性トリメチロールフ゜ロハ゜ントリ(メタ)アクリレート、フ゜ロヒ゜レンオキシト゛（以下、POという）変性トリメチロールフ゜ロハ゜ントリ(メタ)アクリレート、トリフ゜ロヒ゜レンク゛リコールシ゛(メタ)アクリレート、ネオヘ゜ンチルク゛リコールシ゛(メタ)アクリレート、ヒ゛スフェノールAシ゛ク゛リ シシ゛ルエーテルの両末端(メタ)アクリル酸付加物、1,4-フ゛タンシ゛オールシ゛(メタ)アクリレート、1,6-ヘキサンシ゛オールシ゛(メタ)アクリレート、ヘ゜ンタエリスリトールトリ(メタ)アクリレート、ヘ゜ンタエリスリトールテトラ(メタ)アクリレート、ホ゜リエステルシ゛(メタ)アクリレート、ホ゜リエチレンク゛リコールシ゛(メタ)アクリレート、シ゛ヘ゜ンタエリスリトールヘキサ(メタ)アクリレート、シ゛ヘ゜ンタエリスリトールヘ゜ンタ(メタ)アクリレート、シ゛ヘ゜ンタエリス リトールテトラ(メタ)アクリレート、カフ゜ロラクトン変性シ゛ヘ゜ンタエリスリトールヘキサ(メタ)アクリレート、カフ゜ロラクトン変性シ゛ヘ゜ンタエリスリトール ヘ゜ンタ(メタ)アクリレート、シ゛トリメチロールフ゜ロハ゜ンテトラ(メタ)アクリレート、EO変性ヒ゛スフェノールAシ゛(メタ)アクリレート、PO変性ヒ゛スフェ ノールAシ゛(メタ)アクリレート、EO変性水添ヒ゛スフェノールAシ゛(メタ)アクリレート、PO変性水添ヒ゛スフェノールAシ゛(メタ)アクリレート、EO変性 ヒ゛スフェノールFシ゛(メタ)アクリレート、フェノールノホ゛ラックホ゜リク゛リシシ゛ルエーテルの(メタ)アクリレート、(メタ)アクリロイル基を持つシルセスキオキサン誘導体等が挙げられる。 Examples of radical curing type crosslinking agents include ethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, triethylene glycol acrylate, tetraethylene glycol (meth) acrylate, and tricyclodecane dimethyl dimethylene (meth). Acrylate, Tris (2-Hydroxyethyl) isocyanurate di (meth) acrylate, Tris (2-Hydroxyethyl) isocyanurate tri (meth) acrylate, Caprolactone-modified tris (2-humanoxyxyethyl) isocyanurate tri (meth) acrylate, Tri Methylol fluorotri (meth) acrylate, ethylene oxide (hereinafter referred to as EO) modified trimethylol fluorotri (meth) acrylate, fluoroethylene oxide (hereinafter referred to as PO) C) Modified trimethylol chlorotritri (meth) acrylate, trifluoroethylene glycol (meth) acrylate, neopentyl glycol acrylate (meth) acrylate, bisphenol A benzyl ether ether end (meth) acrylic acid adduct, 1,4- Butanediol (meth) acrylate, 1,6-hexanediol (meth) acrylate, Hentaerythritol tri (meth) acrylate, Hentaerythritol tetra (meth) acrylate, Polyester (meth) acrylate, Polyethylene glycol (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, cuff Lactone modified diamine erythritol hexa (meth) acrylate, caprolactone modified diamine erythritol menta (meth) acrylate, dimethylol chloroform tetra (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) Acrylate, EO-modified hydrogenated bisphenol A di (meth) acrylate, PO-modified hydrogenated bisphenol A di (meth) acrylate, EO-modified biphenol F di (meth) acrylate, (meth) acrylate of phenol novolac polycyclic ether, (meth) Examples thereof include silsesquioxane derivatives having an acryloyl group.
カチオン硬化型の架橋剤としては、多官能エホ゜キシ化合物、ヒ゛スフェノールA型エホ゜キシ、ヒ゛スフェノールF型エホ゜キシ、水添ヒ゛スフェノールA型エホ゜キシ、水添ヒ゛スフェノールF型エホ゜キシ、ヒ゛スフェノールS型エホ゜キシ、臭素化ヒ゛スフェノールA型エホ゜キシ、ヒ゛フェニル型エホ゜キシ、ナフタレン型エホ゜キシ、フルオレン型エホ゜キシ、スヒ゜ロ環型エホ゜キシ、ヒ゛スフェノールアルカン類エホ゜キシ、フェノールノホ゛ラック型エホ゜キシ、オルソクレソ゛ールノホ゛ラック型エホ゜キシ、臭素化クレソ゛ールノホ゛ラック型エホ゜キシ、トリスヒト゛ロキシメタン型エホ゜キシ、テトラフェニロールエタン型エホ゜キシ、アルコール型エホ゜キシ、脂環型エホ゜キシ、オキセタン樹脂等が挙げられる。 Examples of the cationic curing type crosslinking agent include polyfunctional epoxy compounds, bisphenol A type epoxy, bisphenol F type epoxy, hydrogenated bisphenol A epoxy, hydrogenated bisphenol F type epoxy, bisphenol S type epoxy, brominated bisphenol A type epoxy, Biphenyl-type epoxy, Naphthalene-type epoxy, Fluorene-type epoxy, Cyclo-ring-type epoxy, Bisphenol alkane epoxy, Phenol novolac-type epoxy, Ortho-cresol novolak-type epoxy, Brominated cresol no-voloxy-type Ethoxy-trioxy-epoxy Type epoxy, alcohol type epoxy, alicyclic epoxy, oxetane resin and the like.
さらに、架橋剤としてビスフェノールＡ型エポキシ樹脂にシリカ成分が含まれるハイブリット樹脂が挙げられ、具体的には荒川化学工業（株）製のコンホ゜セランE102B、E202Cが挙げられる。加えて、メチロールメラミン樹脂、アルコキシメチル化メラミン樹脂、アルコキシメチル化ヘ゛ンソ゛ク゛アナミン樹脂及びアルコキシメチル化尿素樹脂等が挙げられ、具体的には（株）三和ケミカル製のニカラックMW-30HM、MW-750LM、MW-270、MW-280、MW-290等が挙げられる。 Furthermore, as a crosslinking agent, a hybrid resin in which a silica component is contained in a bisphenol A type epoxy resin can be mentioned, and specifically, constellants E102B and E202C manufactured by Arakawa Chemical Industries, Ltd. can be mentioned. In addition, methylol melamine resin, alkoxymethylated melamine resin, alkoxymethylated benzguanamine resin, alkoxymethylated urea resin, and the like can be mentioned. Specifically, Nikalac MW-30HM, MW-750LM manufactured by Sanwa Chemical Co., Ltd. MW-270, MW-280, MW-290 etc. are mentioned.
また、架橋剤としてビニル基及びエポキシ基含有シルセスキオキサン誘導体が挙げられ、具体的には荒川化学工業（株）製のコンホ゜セランSQ506が挙げられる。
この架橋剤の含有量は、アルカリ可溶性樹脂を１００質量部とした場合、感光性樹脂組成物の硬化物に充分な強度を持たせるために１０質量部以上が好ましく、感光性樹脂組成物による充分なパターニング性を得るために１００質量部以下が好ましい。架橋剤の含有量は、アルカリ可溶性樹脂１００質量部に対して２０〜５０質量部が特に好ましい。
Examples of the cross-linking agent include vinyl group and epoxy group-containing silsesquioxane derivatives, and specific examples thereof include Amorpha Chemical Co., Ltd. Sequen SQ506.
The content of the cross-linking agent is preferably 10 parts by mass or more in order to give the cured product of the photosensitive resin composition sufficient strength when the alkali-soluble resin is 100 parts by mass. In order to obtain good patterning properties, 100 parts by mass or less is preferable. As for content of a crosslinking agent, 20-50 mass parts is especially preferable with respect to 100 mass parts of alkali-soluble resin.
〔感光剤〕
（光カチオン重合開始剤）
光カチオン重合開始剤としての光酸発生剤は、光照射により酸が発生し、カチオン重合を開始させることが可能な化合物であれば特に制限されない。
[Photosensitive agent]
(Photocationic polymerization initiator)
The photoacid generator as the photocationic polymerization initiator is not particularly limited as long as it is a compound capable of generating an acid upon irradiation with light and initiating cationic polymerization.
代表的な光酸発生剤として、ヨート゛ニウム,4-メチルフェニル[4-(2-メチルフ゜ロヒ゜ル)フェニル]-ヘキサフルオロフォスフェート(1-)、トリフェニルスルホニウム,トリフルオロメタンスルホネート、シ゛フェニル-4-メチルフェニルスルホニウム,トリフルオロメタンスルホネート、シ゛フェニル-2,4,6-トリメチルフェニルスルホニウム,p-トルエンスルホネート、4-(4-ヘ゛ンソ゛イル-フェニルチオ)フェニル-シ゛-(4-フルオロフェニル)スルホニウムヘキサフルオロホスフェート、4-(4-ヘ゛ンソ゛イルフェニルチオ)フェニル-シ゛-(4-(β-ヒト゛ロキシエトキシ)フェニル)スルホニウ ムヘキサフルオロアンチモネート、(トリルクミル)ヨート゛ニウムテトラキス(ヘ゜ンタフルオロフェニル)等が挙げられる。 Typical photoacid generators include iodonium, 4-methylphenyl [4- (2-methylfluorophenyl) phenyl] -hexafluorophosphate (1-), triphenylsulfonium, trifluoromethanesulfonate, diphenyl-4-methylphenyl Sulfonium, trifluoromethanesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium, p-toluenesulfonate, 4- (4-benzoyl-phenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate, 4- ( 4-Benzoylphenylthio) phenyl-di- (4- (β-human ethoxyethoxy) phenyl) sulfonium hexafluoroantimonate, (tolylcumyl) iodonium tetrakis (hentafluorophenyl) and the like.
光酸発生剤の含有量は、アルカリ可溶性樹脂を１００質量部とした場合、充分な反応性を得るために１質量部以上が好ましく、感光性樹脂組成物の貯蔵安定性を損なわないために１０質量部以下が好ましい。 The content of the photoacid generator is preferably 1 part by mass or more in order to obtain sufficient reactivity when the alkali-soluble resin is 100 parts by mass, and 10% in order not to impair the storage stability of the photosensitive resin composition. The mass part or less is preferable.
（光ラジカル重合開始剤）
光ラジカル重合開始剤は、光照射によりラジカルを発生し、ラジカル重合を開始させることが可能な化合物であれば特に制限されない。光ラジカル重合開始剤の代表的な化合物として、ヒ゛ス(2,4,6-トリメチルヘ゛ンソ゛イル)-フェニルフォスフィンオキサイト゛、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノフ゜ロハ゜ン-1-オン、2-シ゛メチルアミノ-2-(4-メチルヘ゛ンシ゛ル)-1-(4-モルフォリン-4-イル-フェニル)-フ゛タン-1-オン、2-ヘ゛ンシ゛ル-2-シ゛メチルアミノ-1-(4-モルフォリノフェニル)-フ゛タノン-1、ヒ゛ス(2,4,6-トリメチルヘ゛ンソ゛イル)-フェニルフォスフィンオキサイト゛、2,4,6-トリメチルヘ゛ンソ゛イルフェニルホスフィンオキサイト゛、1,2-オクタンシ゛オン,1-[4-(フェニルチオ)-,2-(O-ヘ゛ンソ゛イルオキシム)]、エタノン,1-[9-エチル-6-(2-メチルヘ゛ンソ゛イル)-9H-カルハ゛ソ゛ール-3-イル]-,1-(0-アセチルオキシム)、ヒ゛ス(η5-2,4-シクロヘ゜ンタシ゛エン-1-イル)-ヒ゛ス(2,6-シ゛フルオロ-3-(1H-ヒ゜ロール-1-イル)-フェニル)チタニウム等が挙げられる。
(Photo radical polymerization initiator)
The radical photopolymerization initiator is not particularly limited as long as it is a compound capable of generating radicals by light irradiation and initiating radical polymerization. As representative compounds of radical photopolymerization initiators, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinofluoro- 1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine oxide, 1,2-octanethione, 1- [4- (Phenylthio)-, 2- (O-benzoyloxime)], Ethanone, 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0 -Acetyl oxime), bis (η5-2,4-cyclopentadien-1-yl)-゛Su (2,6-di-fluoro-3-(1H-pin roll-1-yl) - phenyl) titanium, and the like.
光ラジカル重合開始剤の含有量は、アルカリ可溶性樹脂１００質量部に対して、充分な反応性を得るために１質量部以上が好ましく、感光性樹脂組成物の貯蔵安定性を損なわないために２０質量部以下が好ましい。 The content of the photo radical polymerization initiator is preferably 1 part by mass or more in order to obtain sufficient reactivity with respect to 100 parts by mass of the alkali-soluble resin, and 20% in order not to impair the storage stability of the photosensitive resin composition. The mass part or less is preferable.
〔増感剤〕
増感剤としては、2,4-シ゛エチルチオキサンテン-9-オン、1-メトキシナフタレン、1,4-ヒ゛ス(2-ヒト゛ロキシフ゛トキシ)ナフタレン等のナフタレン誘導体、9,10-シ゛メトキシアントラセン、2-エチル-9,10-シ゛メトキシアントラセン等のアントラセン誘導体、1,4-シ゛メトキシクリセン、1,4-シ゛エトキシクリセン等のクリセン誘導体、9-ヒト゛ロキシフェナントレン、9-メトキシフェナントレン等のフェナントレン誘導体、キサントン、チオキサントン、2,4-シ゛エチルチオキサンテン-9-オン等の(チオ)キサントン誘導体、カルハ゛ソ゛ール、N-ヒ゛ニルカルハ゛ソ゛ール等のカルハ゛ソ゛ール誘導体等が挙げられる。
[Sensitizer]
Sensitizers include 2,4-diethylthioxanthen-9-one, 1-methoxynaphthalene, naphthalene derivatives such as 1,4-bis (2-humanoxybutoxy) naphthalene, 9,10-dimethoxyanthracene, 2-ethyl Anthracene derivatives such as -9,10-dimethoxyanthracene, chrysene derivatives such as 1,4-dimethoxychrysene and 1,4-diethoxychrysene, phenanthrene derivatives such as 9-human doxyphenanthrene and 9-methoxyphenanthrene, xanthone, thioxanthone, 2 (Thio) xanthone derivatives such as 1,4-diethylthioxanthen-9-one, and carbazole derivatives such as carbazole and N-vinylcarbazole.
この増感剤の含有量は、アルカリ可溶性樹脂１００質量部とした場合、充分な反応性を得るために１質量部以上が好ましく、感光性樹脂組成物の貯蔵安定性を損なわないために２０質量部以下が好ましい。 The content of the sensitizer is preferably 1 part by mass or more in order to obtain sufficient reactivity when the alkali-soluble resin is 100 parts by mass, and 20 parts by mass in order not to impair the storage stability of the photosensitive resin composition. Part or less is preferred.
〔着色剤〕
着色剤としては、顔料、染料等が用いられる。この着色剤としては、有機系着色剤と無機系着色剤がある。有機系着色剤としては、例えば染料、有機顔料、天然色素等が挙げられる。また、無機系着色剤としては、例えば無機顔料、体質顔料等が挙げられる。
[Colorant]
As the colorant, pigments, dyes and the like are used. Examples of the colorant include an organic colorant and an inorganic colorant. Examples of the organic colorant include dyes, organic pigments, natural pigments, and the like. Examples of the inorganic colorant include inorganic pigments and extender pigments.
有機顔料の具体例としては、カラーインデックス（C.I.；THE SOCIETY OF DYERS AND COLOURISTS 社発行）においてピグメント（PIGMENT）に分類されている化合物、例えば、C.I.ピグメントイエロー１、C.I.ピグメントイエロー３、C.I.ピグメントイエロー１２、C.I.ピグメントイエロー１３、C.I. ピグメントイエロー１３８、C.I.ピグメントイエロー１５０、C.I.ピグメントイエロー１８０、C.I.ピグメントイエロー１８５等のイエロー系ピグ メント；C.I.ピグメントレッド１、C.I.ピグメントレッド２、C.I.ピグメントレッド３、C.I.ピグメントレッド２５４、C.I.ピグメント レッド１７７等のレッド系ピグメント；及び、C.I.ピグメントブルー１５、C.I.ピグメントブルー１５：３、C.I.ピグメントブルー１５：４、 C.I.ピグメントブルー１５：６等のブルー系ピグメント；C.I.ピグメントバイオレット２３：１９；C.I.ピグメントグリーン３６が挙げられる。 Specific examples of organic pigments include compounds classified as PIGMENT in the color index (CI; issued by THE SOCIETY OF DYERS AND COLORISTS), such as CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12 CI Pigment Yellow 13, CI Pigment Yellow 138, CI Pigment Yellow 150, CI Pigment Yellow 180, CI Pigment Yellow 185 and the like; CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 254, red pigments such as CI Pigment Red 177; and blue pigments such as CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6 C.I. Pigment Violet 23:. 19; C.I Pigment Green 36, and the like.
また、前記無機顔料又は体質顔料の具体例としては、酸化チタン、アルミナ白、硫酸バリウム、炭酸カルシウム、亜鉛華、硫酸鉛、黄色鉛、亜鉛黄、べんがら（赤色酸化鉄(III)）、カドミウム赤、群青、紺青、酸化クロム緑、コバルト緑、アンバー、カーボンブラック（ＣＢ）、チタンブラック、酸化クロム、酸化鉄、アニリンブラック、ペリレン系顔料、及びＣ．Ｉ．ソルベントブラック１２３等カーボンブラック等が挙げられる。着色剤は、単独又は２種以上を混合して使用することができる。 Specific examples of the inorganic pigment or extender pigment include titanium oxide, alumina white, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron oxide (III)), and cadmium red. , Ultramarine, bitumen, chromium oxide green, cobalt green, amber, carbon black (CB), titanium black, chromium oxide, iron oxide, aniline black, perylene pigment, and C.I. I. Carbon black etc., such as solvent black 123, are mentioned. A coloring agent can be used individually or in mixture of 2 or more types.
着色剤の含有量は、アルカリ可溶性樹脂１００質量部に対して、着色力を得るために１０質量部以上が好ましく、感光性樹脂組成物のパターニング性に悪影響を及ぼさないために７０質量部以下が好ましい。 The content of the colorant is preferably 10 parts by mass or more in order to obtain coloring power with respect to 100 parts by mass of the alkali-soluble resin, and 70 parts by mass or less in order not to adversely affect the patterning property of the photosensitive resin composition. preferable.
次に、感光性樹脂組成物の硬化物について説明する。
感光性樹脂組成物の硬化物（硬化膜）は、例えば以下のようにして形成することができる。
Next, the cured product of the photosensitive resin composition will be described.
The cured product (cured film) of the photosensitive resin composition can be formed, for example, as follows.
上述した感光性樹脂組成物を、例えば電極付きガラス基板やシリコンウエハ等の支持体に塗工し、乾燥により溶媒等を揮発させる。その後、所望のマスクパターンを介して露光し、アルカリ性現像液により現像して、未露光部を溶解、除去することによって所望のパターンを得ることができる。さらに、高温で加熱処理を行うことにより、強固な硬化物を形成できる。 The above-described photosensitive resin composition is applied to a support such as a glass substrate with an electrode or a silicon wafer, and the solvent is volatilized by drying. Then, it exposes through a desired mask pattern, It develops with an alkaline developing solution, A desired pattern can be obtained by melt | dissolving and removing an unexposed part. Furthermore, a hardened | cured material can be formed by heat-processing at high temperature.
感光性樹脂組成物を支持体に塗布する方法としては、例えばディッピング法、スプレー法、バーコート法、ロールコート法、スピンコート法等が採用される。また、塗布の厚さは、塗布手段、感光性樹脂組成物の固形分濃度や粘度を調節することにより、適宜制御することができる。塗布後の加熱処理条件は特に制限されないが、感光性樹脂組成物に含まれる溶媒の沸点前後が好ましい。加熱設備としては、ホットプレート、オーブン、赤外線炉等が用いられる。 As a method for applying the photosensitive resin composition to the support, for example, a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, or the like is employed. Moreover, the thickness of application | coating can be suitably controlled by adjusting the solid content density | concentration and viscosity of an application | coating means and the photosensitive resin composition. The heat treatment conditions after coating are not particularly limited, but are preferably around the boiling point of the solvent contained in the photosensitive resin composition. As the heating equipment, a hot plate, an oven, an infrared furnace or the like is used.
露光に用いられる活性エネルギー線としては、例えば低圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、メタルハライドランプ、ｇ線ステッパ、ｉ線ステッパ等の紫外線や電子線、レーザ光線等が挙げられる。露光量は、使用する光源や塗布膜厚等によって適宜設定されるが、例えば超高圧水銀ランプからの紫外線照射の場合、塗布膜厚が１〜１０μmであれば、１０〜５００ｍＪ／ｃｍ２程度である。 Examples of active energy rays used for exposure include ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, g-line steppers, and i-line steppers, electron beams, and laser beams. The exposure amount is appropriately set depending on the light source used, the coating film thickness, and the like. For example, in the case of ultraviolet irradiation from an ultra-high pressure mercury lamp, if the coating film thickness is 1 to 10 μm, it is about 10 to 500 mJ / cm 2 . is there.
アルカリ性現像液による現像方法としては、シャワー現像法、スプレー現像法、浸漬現像法、パドル現像法等が挙げられ、現像条件は、通常２０〜４０℃で１〜１０分程度である。上記アルカリ性現像液としては、例えば水酸化ナトリウム、水酸化カリウム、アンモニア水、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）等のアルカリ性化合物を水に溶解して濃度が０．１〜１０質量％程度になるように調製したアルカリ性水溶液が用いられる。前記アルカリ性水溶液には、例えばメタノール、エタノール等の水溶性の有機溶剤や界面活性剤等を適量添加することもできる。なお、アルカリ性現像液で現像した後、パターニングした塗布膜を水で洗浄し、乾燥させる。 Examples of the developing method using an alkaline developer include a shower developing method, a spray developing method, an immersion developing method, and a paddle developing method, and the developing conditions are usually 20 to 40 ° C. for about 1 to 10 minutes. As the alkaline developer, for example, an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide (TMAH) is dissolved in water so that the concentration becomes about 0.1 to 10% by mass. The alkaline aqueous solution prepared in (1) is used. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution. In addition, after developing with an alkaline developer, the patterned coating film is washed with water and dried.
露光後の加熱処理条件は特に制限されず、感光性樹脂組成物の配合量や塗布膜厚等によって異なるが、通常１５０〜３００℃、好ましくは２００〜２５０℃で１〜１２０分程度である。加熱設備としては、ホットプレート、オーブン、赤外線炉等を使用できる。 The heat treatment conditions after the exposure are not particularly limited and vary depending on the blending amount of the photosensitive resin composition, the coating film thickness, and the like, but are usually 150 to 300 ° C., preferably 200 to 250 ° C. for about 1 to 120 minutes. As a heating facility, a hot plate, an oven, an infrared furnace, or the like can be used.
得られる感光性樹脂組成物の硬化物は、電気絶縁性、耐熱性、耐水性、耐薬品性、機械的強度等の特性に優れている。従って、感光性樹脂組成物は、特に半導体素子の表面保護膜や層間絶縁膜等の材料として好適に使用することができる。これらの表面保護膜や層間絶縁膜等には、ホールパターン、レリーフパターン等のパターンが形成される。 The resulting cured product of the photosensitive resin composition is excellent in properties such as electrical insulation, heat resistance, water resistance, chemical resistance, and mechanical strength. Therefore, the photosensitive resin composition can be suitably used as a material for a surface protective film or an interlayer insulating film of a semiconductor element. A pattern such as a hole pattern or a relief pattern is formed on the surface protective film or the interlayer insulating film.
次に、本実施形態のアルカリ可溶性樹脂及び感光性樹脂組成物について作用を説明する。
さて、アルカリ可溶性樹脂を調製する場合には、カルボキシル基を有する単量体、アルコキシシリル基を有するシラン系単量体等を前記特定のアルコールの存在下に共重合することにより得られる。このとき、シラン系単量体には加水分解性シリル基、すなわち加水分解しやすいアルコキシ基（−ＯＲ）が含まれており、そのアルコキシ基の加水分解が生じて架橋反応が進行する。この加水分解による架橋反応は、シラン系単量体のアルコキシ基がメトキシ基やエトキシ基の場合に生じやすい。
Next, an effect | action is demonstrated about the alkali-soluble resin and photosensitive resin composition of this embodiment.
Now, when preparing an alkali-soluble resin, it is obtained by copolymerizing a monomer having a carboxyl group, a silane monomer having an alkoxysilyl group, etc. in the presence of the specific alcohol. At this time, the silane monomer contains a hydrolyzable silyl group, that is, an easily hydrolyzed alkoxy group (—OR), and the alkoxy group is hydrolyzed to cause a crosslinking reaction. This crosslinking reaction by hydrolysis tends to occur when the alkoxy group of the silane monomer is a methoxy group or an ethoxy group.
しかしながら、本実施形態で用いる溶媒には、アルキル基の炭素数が４又は５の特定のアルコールが含まれている。このため、特定のアルコールの炭素数４又は５のアルキル基がシラン系単量体のアルコキシ基に何らかの反応をし、アルコキシ基が置き換えられ難くなって加水分解が抑えられるものと推測される。その結果、加水分解性シリル基の加水分解が抑えられ、アルカリ可溶性樹脂の分子量の増大が抑制される。 However, the solvent used in the present embodiment contains a specific alcohol having an alkyl group with 4 or 5 carbon atoms. For this reason, it is presumed that the alkyl group having 4 or 5 carbon atoms of the specific alcohol reacts with the alkoxy group of the silane monomer in some way, making it difficult to replace the alkoxy group and suppressing hydrolysis. As a result, hydrolysis of the hydrolyzable silyl group is suppressed, and an increase in the molecular weight of the alkali-soluble resin is suppressed.
このようにして得られたアルカリ可溶性樹脂に架橋剤、感光剤等が添加されて感光性樹脂組成物が調製される。この感光性樹脂組成物に例えば紫外線を照射することにより、感光性樹脂組成物が光重合して硬化物が形成され、層間絶縁膜等として用いられる。その後、アルカリ性現像液に浸漬させることにより、ホールパターン等のパターンが形成される。 A crosslinking agent, a photosensitizer, and the like are added to the alkali-soluble resin thus obtained to prepare a photosensitive resin composition. By irradiating the photosensitive resin composition with, for example, ultraviolet rays, the photosensitive resin composition is photopolymerized to form a cured product, which is used as an interlayer insulating film or the like. Then, a pattern such as a hole pattern is formed by immersing in an alkaline developer.
以上の実施形態によって発揮される効果について、以下にまとめて記載する。
（１）本実施形態のアルカリ可溶性樹脂は、カルボキシル基を含む重合単位と、アルコキシシリル基を含む重合単位とを有効成分として含有する共重合体が溶媒に溶解されたものであり、その溶媒はアルキル基の炭素数が４又は５の直鎖又は分岐鎖を有する特定のアルコールを含んでいる。このため、特に共重合体を形成する際に特定のアルコールがアルコキシシリル基に作用してアルコキシシリル基の加水分解が抑えられる。従って、アルコキシシリル基の加水分解による架橋反応が規制され、アルカリ可溶性樹脂の分子量増大が防止される。
The effects exhibited by the above embodiment will be described collectively below.
(1) The alkali-soluble resin of the present embodiment is obtained by dissolving a copolymer containing a polymer unit containing a carboxyl group and a polymer unit containing an alkoxysilyl group as active ingredients in a solvent. Specific alcohols having a linear or branched chain in which the alkyl group has 4 or 5 carbon atoms are included. For this reason, especially when forming a copolymer, a specific alcohol acts on an alkoxysilyl group and hydrolysis of the alkoxysilyl group is suppressed. Accordingly, the crosslinking reaction due to hydrolysis of the alkoxysilyl group is regulated, and an increase in the molecular weight of the alkali-soluble resin is prevented.
よって、本実施形態のアルカリ可溶性樹脂によれば、加水分解性シリル基の架橋反応を抑制して経時的安定性を得ることができるという効果を奏する。
（２）前記カルボキシル基を含む重合単位は不飽和カルボン酸、不飽和カルボン酸無水物又はこれらの混合物から誘導される重合単位であり、アルコキシシリル基を含む重合単位は前記の式（１）で表される単量体から誘導される重合単位であり、さらに共重合体が前記以外の共重合性単量体から誘導される重合単位を含有している。
Therefore, according to the alkali-soluble resin of the present embodiment, there is an effect that the cross-linking reaction of the hydrolyzable silyl group can be suppressed and the temporal stability can be obtained.
(2) The polymer unit containing a carboxyl group is a polymer unit derived from an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride or a mixture thereof, and the polymer unit containing an alkoxysilyl group is represented by the formula (1). It is a polymerization unit derived from the monomer represented, and the copolymer further contains a polymerization unit derived from a copolymerizable monomer other than those described above.
そのため、共重合体は、側鎖にカルボキシル基をもつ重合単位、側鎖にアルコキシシリル基をもつ重合単位及び側鎖にアルキル基等をもつ重合単位を含むように構成される。従って、アルカリ可溶性樹脂は、アルカリ可溶性を示し、耐熱性、耐薬品性等の優れた特性を発揮することができる。 Therefore, the copolymer is configured to include a polymer unit having a carboxyl group in the side chain, a polymer unit having an alkoxysilyl group in the side chain, and a polymer unit having an alkyl group in the side chain. Therefore, the alkali-soluble resin is alkali-soluble and can exhibit excellent properties such as heat resistance and chemical resistance.
（３）前記共重合体は、水酸基含有不飽和単量体から誘導される水酸基を含む重合単位を含有する。従って、共重合体に架橋構造を形成でき、共重合体の機械的強度等の特性を向上させることができる。 (3) The copolymer contains a polymer unit containing a hydroxyl group derived from a hydroxyl group-containing unsaturated monomer. Therefore, a crosslinked structure can be formed in the copolymer, and properties such as mechanical strength of the copolymer can be improved.
（４）前記アルコールは、アルキル基の炭素数が４又は５の第一級アルコール又は第二級アルコールであることが好ましく、さらにアルキル基の炭素数が４又は５の第一級アルコールであることが好ましく、そのアルキル基の炭素数が４の第一級アルコールとしては１−ブタノールが好ましい。この場合、前記共重合体中のアルコキシシリル基の加水分解を有効に抑制することができる。 (4) The alcohol is preferably a primary alcohol or secondary alcohol having 4 or 5 carbon atoms in the alkyl group, and is a primary alcohol having 4 or 5 carbon atoms in the alkyl group. 1-butanol is preferable as the primary alcohol whose alkyl group has 4 carbon atoms. In this case, hydrolysis of the alkoxysilyl group in the copolymer can be effectively suppressed.
（５）感光性樹脂組成物は、前記アルカリ可溶性樹脂と、架橋剤と、感光剤とを含有し、活性エネルギー線により硬化して硬化物が形成される。このため、感光性樹脂組成物は、活性エネルギー線によって速やかに硬化して硬化物を形成することができ、半導体素子のパターン形成を容易に行うことができる。 (5) The photosensitive resin composition contains the alkali-soluble resin, a crosslinking agent, and a photosensitive agent, and is cured by active energy rays to form a cured product. For this reason, the photosensitive resin composition can be quickly cured by an active energy ray to form a cured product, and a pattern of a semiconductor element can be easily formed.
（６）層間絶縁膜は、前記硬化物により形成され、層間に配置される配線間を電気的に絶縁するものである。従って、感光性樹脂組成物の硬化物により簡単に層間絶縁膜を形成でき、ＴＦＴ液晶表示素子、有機ＥＬ表示素子、集積回路表示素子等の層間に配置される配線相互間の絶縁を確保できる。 (6) The interlayer insulating film is formed of the cured product and electrically insulates between the wirings arranged between the layers. Therefore, an interlayer insulating film can be easily formed with a cured product of the photosensitive resin composition, and insulation between wirings arranged between layers of a TFT liquid crystal display element, an organic EL display element, an integrated circuit display element, etc. can be secured.
以下に、実施例及び比較例を挙げて前記実施形態をさらに具体的に説明する。
（実施例１〜１５及び比較例１〜３、アルカリ可溶性樹脂の調製）
撹拌機、温度計、コンデンサー及び窒素ガス導入管を備えたフラスコ内に表１に示す溶媒を仕込み、窒素ガス雰囲気下に適正温度まで昇温した。それとは別に、表１に示す単量体及び重合開始剤を混合して混合液を調製し、その混合液を前記溶媒中に４時間かけて滴下した。その後、３時間反応させてアルカリ可溶性樹脂を調製した。なお、表１中の配合量は質量部を表す。
Hereinafter, the embodiment will be described more specifically with reference to examples and comparative examples.
(Examples 1-15 and Comparative Examples 1-3, preparation of alkali-soluble resin)
The solvent shown in Table 1 was charged into a flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introduction tube, and the temperature was raised to an appropriate temperature in a nitrogen gas atmosphere. Separately, a monomer and a polymerization initiator shown in Table 1 were mixed to prepare a mixed solution, and the mixed solution was dropped into the solvent over 4 hours. Then, it was made to react for 3 hours and alkali-soluble resin was prepared. In addition, the compounding quantity in Table 1 represents a mass part.
AA：アクリル酸
MAA：メタクリル酸
KBM503：γ-メタクリロキシフ゜ロヒ゜ルトリメトキシシラン
KBM502：γ-メタクリロキシフ゜ロヒ゜ルメチルシ゛メトキシシラン
KBE503：γ-メタクリロキシフ゜ロヒ゜ルトリエトキシシラン
KBM1403：p-スチリルトリメトキシシラン
KBE502：γ-メタクリロキシフ゜ロヒ゜ルメチルシ゛エトキシシラン
KBM1003：ヒ゛ニルトリメトキシシラン
HEMA：2-ヒト゛ロキシエチルメタクリレート
HPMA：2-ヒト゛ロキシフ゜ロヒ゜ルメタクリレート
CHDMMA：1,4-シクロヘキサンシ゛メタノールモノアクリレート
Sty：スチレン
MMA：メチルメタクリレート
BMA：フ゛チルメタクリレート
CHMA：シクロヘキシルメタクリレート
IBX-A：イソホ゛ルニアクリレート
PBO：t-フ゛チルハ゜ーオキシ-2-エチルヘキサノエイト
〔アルカリ可溶性樹脂の経時安定性評価〕
（初期サンプルの作製）
実施例１〜１５及び比較例１〜３のアルカリ可溶性樹脂を、固形分が２質量％になるようにテトラヒドロフラン（ＴＨＦ）に溶解させ、ゲル浸透クロマトグラフィー（ＧＰＣ）により質量平均分子量（ＭＷ）を測定した。その結果を初期分子量として表２に示した。
AA: Acrylic acid
MAA: Methacrylic acid
KBM503: γ-Methacryloxyfluorotrimethoxysilane
KBM502: γ-Methacryloxyfluoromethyldimethoxysilane
KBE503: γ-Methacryloxyfluorotriethoxysilane
KBM1403: p-styryltrimethoxysilane
KBE502: γ-methacryloxyfluoromethyldiethoxysilane
KBM1003: Vinyltrimethoxysilane
HEMA: 2-Hydroxyethyl methacrylate
HPMA: 2-Hydroxypropyl methacrylate
CHDMMA: 1,4-cyclohexanedimethanol monoacrylate
Sty: Styrene
MMA: Methyl methacrylate
BMA: Butyl methacrylate
CHMA: cyclohexyl methacrylate
IBX-A: Isobornyl acrylate
PBO: t-butyl hydrogenoxy-2-ethylhexanoate [Evaluation of stability over time of alkali-soluble resin]
(Preparation of initial sample)
The alkali-soluble resins of Examples 1 to 15 and Comparative Examples 1 to 3 were dissolved in tetrahydrofuran (THF) so that the solid content was 2% by mass, and the mass average molecular weight (MW) was determined by gel permeation chromatography (GPC). It was measured. The results are shown in Table 2 as the initial molecular weight.
（経時安定性評価用サンプルの作製）
実施例１〜１５及び比較例１〜３のアルカリ可溶性樹脂を、４０℃のオーブンに入れて２週間静置した後、固形分が２質量％になるようにＴＨＦに溶解させ、ＧＰＣにより質量平均分子量（ＭＷ）を測定した。その結果を経時分子量として表２に示した。
(Preparation of samples for stability evaluation over time)
The alkali-soluble resins of Examples 1 to 15 and Comparative Examples 1 to 3 were placed in an oven at 40 ° C. and allowed to stand for 2 weeks, then dissolved in THF so that the solid content was 2% by mass, and mass averaged by GPC. Molecular weight (MW) was measured. The results are shown in Table 2 as molecular weight with time.
また、初期分子量に対する経時分子量の分子量増加率（％）を表２に示した。 Table 2 shows the molecular weight increase rate (%) of the molecular weight with time relative to the initial molecular weight.
（実施例１６〜３３及び比較例４〜６、感光性樹脂組成物の調製及び評価）
実施例１〜１５及び比較例１〜３のアルカリ可溶性樹脂（調製初期のアルカリ可溶性樹脂と、４０℃、２週間静置したアルカリ可溶性樹脂とを使用）、表３に示す架橋剤及び感光剤を混合して感光性樹脂組成物を調製した。なお、表３中の配合量は質量部を表す。
(Examples 16 to 33 and Comparative Examples 4 to 6, preparation and evaluation of photosensitive resin composition)
The alkali-soluble resins of Examples 1 to 15 and Comparative Examples 1 to 3 (using the alkali-soluble resin at the initial stage of preparation and the alkali-soluble resin that was allowed to stand for 2 weeks at 40 ° C.), the crosslinking agents and the photosensitizers shown in Table 3 were used. A photosensitive resin composition was prepared by mixing. In addition, the compounding quantity in Table 3 represents a mass part.
架橋剤Ａ：3’,4’-エホ゜キシシクロヘキシルメチル 3,4-エホ゜キシシクロヘキサンカルホ゛キシレート
架橋剤Ｂ：エーテル化メチロールメラミン〔（株）三和ケミカル製のニカラックMW30M〕
架橋剤Ｃ：エホ゜キシシリカハイフ゛リット樹脂〔荒川化学工業（株）製のコンホ゜セランE102B〕
架橋剤Ｄ：トリメチロールフ゜ロハ゜ントリメタクリレート
感光剤Ｅ：ヨート゛ニウム,4-メチルフェニル[4-(2-メチルフ゜ロヒ゜ル)フェニル]-ヘキサフルオロフォスフェート
感光剤Ｆ：（2,4,6-トリメチルヘ゛ンソ゛イル）-フェニルフォスフィンオキサイト゛
次に、スピンコート法により約３μｍの膜厚になるように感光性樹脂組成物をガラス基板上に塗布し、１０５℃のホットプレート上で１３０秒プリベークした。続いて、線幅２０μｍのホールラインパターンの描写されたマスクを介して紫外線露光装置〔（株）三永電気製作所製のUVE-251S〕により紫外線を照射した。このとき、紫外線の積算照射量を２００ｍＪ／ｃｍ２とした。
Crosslinking agent A: 3 ', 4'-Epoxycyclohexylmethyl 3,4-Epoxycyclohexanecarboxylate Crosslinking agent B: Etherified methylol melamine [Nikalac MW30M manufactured by Sanwa Chemical Co., Ltd.]
Crosslinking agent C: Epoxysilica hybrid resin [Akogawa Selan E102B manufactured by Arakawa Chemical Industries, Ltd.]
Crosslinking agent D: Trimethylol fluorotrimethacrylate Photosensitizer E: Iodonium, 4-methylphenyl [4- (2-methylfluorophenyl) phenyl] -hexafluorophosphate Photosensitizer F: (2,4,6-trimethylbenzodiyl)- Phenylphosphine oxide Next, a photosensitive resin composition was applied on a glass substrate so as to have a film thickness of about 3 μm by spin coating, and prebaked on a hot plate at 105 ° C. for 130 seconds. Subsequently, ultraviolet rays were irradiated by an ultraviolet exposure apparatus (UVE-251S manufactured by Mitsunaga Electric Co., Ltd.) through a mask on which a hole line pattern with a line width of 20 μm was drawn. At this time, the integrated dose of ultraviolet rays was set to 200 mJ / cm 2 .
次に、アルカリ性現像液として０．４質量％ＴＭＡＨ水溶液（温度：２５℃）を用い、３０秒間浸漬させた後水洗を行うことにより、所定のパターンを形成した。そして、下記の判定基準に基づいて感光性樹脂組成物のパターン形成の良否を判定した。これらの試験結果を表４に示した。 Next, a 0.4% by mass TMAH aqueous solution (temperature: 25 ° C.) was used as an alkaline developer, and after immersion for 30 seconds, washing was performed to form a predetermined pattern. And the quality of pattern formation of the photosensitive resin composition was determined based on the following criteria. The test results are shown in Table 4.
判定基準：
○：線幅２０μｍのホールラインパターンが描写された。
×：線幅２０μｍのホールラインパターンが描写されなかった。
Judgment criteria:
○: A hole line pattern having a line width of 20 μm was drawn.
X: A hole line pattern having a line width of 20 μm was not drawn.
前記調製初期のアルカリ可溶性樹脂についてのパターンを初期パターン、２週間静置したアルカリ可溶性樹脂についてのパターンを経時パターンとして表４に示した。 The pattern for the alkali-soluble resin at the initial stage of preparation was shown in Table 4 as the initial pattern, and the pattern for the alkali-soluble resin that was allowed to stand for 2 weeks as a time-dependent pattern.
また、実施例１６〜２６及び３０〜３３の感光性樹脂組成物について、触針式表面形状測定装置〔（株）アルバック製のDekTak〕を用い、現像前後の膜厚（μｍ）を測定し、その差から残膜率を下記式により算出した。 Moreover, about the photosensitive resin composition of Examples 16-26 and 30-33, the film thickness (micrometer) before and behind image development was measured using the stylus type surface shape measuring apparatus [DekTak made from ULVAC, Inc.] From the difference, the remaining film ratio was calculated by the following formula.
残膜率（％）＝（現像後の膜厚／初期の膜厚）×１００
この試験結果を表５に示した。
Residual film ratio (%) = (film thickness after development / initial film thickness) × 100
The test results are shown in Table 5.
次に、実施例１６〜３３の感光性樹脂組成物について、下記に示す方法で電気絶縁性を評価し、その結果を表６に示した。
（電気絶縁性の評価方法）
スピンコート法により約３μｍの厚さになるようにＩＴＯが蒸着されたガラス基板上に感光性樹脂組成物を塗布し、１０５℃のホットプレート上で１３０秒プリベークした。次に、前記と同じ紫外線露光装置により紫外線を照射した。このとき、紫外線の積算照射量を２００ｍＪ／ｃｍ２とした。次に、２３０℃に加熱したオーブンに投入し、１時間加熱した。そして、下記の判定基準に基づいて電気絶縁性を判定した。
Next, the electrical insulating properties of the photosensitive resin compositions of Examples 16 to 33 were evaluated by the method shown below, and the results are shown in Table 6.
(Evaluation method for electrical insulation)
The photosensitive resin composition was applied on a glass substrate on which ITO was deposited to a thickness of about 3 μm by spin coating, and prebaked on a hot plate at 105 ° C. for 130 seconds. Next, ultraviolet rays were irradiated by the same ultraviolet exposure apparatus as described above. At this time, the integrated dose of ultraviolet rays was set to 200 mJ / cm 2 . Next, it was put into an oven heated to 230 ° C. and heated for 1 hour. And electrical insulation was determined based on the following criteria.
（判定基準）
テスターを用いて、導通性のチェックを行った。
〇：導通性無し、×：導通性有り
(Criteria)
Conductivity was checked using a tester.
○: No conductivity, ×: Conductivity
なお、前記実施形態を、次のように変更して実施することも可能である。
・ 前記溶媒として、アルキル基の炭素数が４又は５の直鎖又は分岐鎖を有する特定のアルコールを複数選択して使用してもよい。
It should be noted that the above-described embodiment can be modified as follows.
-As the solvent, a plurality of specific alcohols having a straight chain or branched chain in which the alkyl group has 4 or 5 carbon atoms may be used.
・ 前記共重合体のカルボキシル基を含む重合単位を、２種以上の不飽和カルボン酸又は２種以上の不飽和カルボン酸無水物で形成してもよい。
・ 前記共重合体のアルコキシシリル基を含む重合単位を、前記式（１）で表される複数の単量体により形成してもよい。
-You may form the polymer unit containing the carboxyl group of the said copolymer with 2 or more types of unsaturated carboxylic acid or 2 or more types of unsaturated carboxylic acid anhydride.
-You may form the polymer unit containing the alkoxy silyl group of the said copolymer by the several monomer represented by the said Formula (1).
Claims (15)
前記溶媒は、アルキル基の炭素数が４又は５の直鎖又は分岐鎖を有するアルコールを含むことを特徴とする絶縁膜形成用アルカリ可溶性樹脂溶液。 An alkali-soluble resin solution for forming an insulating film in which a copolymer containing a polymer unit containing a carboxyl group and a polymer unit containing an alkoxysilyl group as an active ingredient is dissolved in a solvent,
An alkali-soluble resin solution for forming an insulating film , wherein the solvent contains a linear or branched alcohol having 4 or 5 carbon atoms in an alkyl group.
Ｘ−（ＣＨ２）ａ−Ｓｉ（ＯＲ）ｂ（ＣＨ３）３−ｂ ・・・（１）
但し、式（１）中のＸはビニル基、スチリル基又は（メタ）アクリロイル基、Ｒはメチル基又はエチル基、ａは０〜３の整数、ｂは１〜３の整数である。 The polymer unit containing a carboxyl group is a polymer unit derived from an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride or a mixture thereof, and the polymer unit containing an alkoxysilyl group is represented by the following formula (1). 2. The insulating film forming device according to claim 1, wherein the copolymer is a polymerized unit derived from a monomer, and the copolymer further comprises a polymerized unit derived from a copolymerizable monomer other than the above . Alkali-soluble resin solution .
X- (CH 2) a -Si ( OR) b (CH 3) 3-b ··· (1)
However, X in Formula (1) is a vinyl group, a styryl group, or a (meth) acryloyl group, R is a methyl group or an ethyl group, a is an integer of 0-3, b is an integer of 1-3.
前記アルカリ可溶性樹脂溶液は、カルボキシル基を含む重合単位と、アルコキシシリル基を含む重合単位とを有効成分として含有する共重合体が溶媒に溶解されたアルカリ可溶性樹脂溶液であって、The alkali-soluble resin solution is an alkali-soluble resin solution in which a copolymer containing a polymer unit containing a carboxyl group and a polymer unit containing an alkoxysilyl group as an active ingredient is dissolved in a solvent,
前記溶媒は、アルキル基の炭素数が４又は５の直鎖又は分岐鎖を有するアルコールを含むことを特徴とする、感光性樹脂組成物。The said solvent contains the alcohol which has the linear or branched chain whose carbon number of an alkyl group is 4 or 5, The photosensitive resin composition characterized by the above-mentioned.
Ｘ−（ＣＨX- (CH ２2 ）) ａa −Ｓｉ（ＯＲ）-Si (OR) ｂb （ＣＨ(CH ３3 ）) ３−ｂ3-b ・・・（１） ... (1)
但し、式（１）中のＸはビニル基、スチリル基又は（メタ）アクリロイル基、Ｒはメチル基又はエチル基、ａは０〜３の整数、ｂは１〜３の整数である。However, X in Formula (1) is a vinyl group, a styryl group, or a (meth) acryloyl group, R is a methyl group or an ethyl group, a is an integer of 0-3, b is an integer of 1-3.
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| CN201580051227.1A CN106715598B (en) | 2014-09-26 | 2015-09-24 | Alkali soluble resins, photosensitive polymer combination and application thereof |
| PCT/JP2015/076970 WO2016047703A1 (en) | 2014-09-26 | 2015-09-24 | Alkali-soluble resin, photosensitive resin composition, and use thereof |
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| JP7035889B2 (en) * | 2017-09-28 | 2022-03-15 | Jsr株式会社 | Radiation-sensitive resin compositions and their uses |
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| JP7047652B2 (en) * | 2017-09-28 | 2022-04-05 | Jsr株式会社 | Radiation-sensitive resin compositions and their uses |
| CN113966489A (en) | 2019-06-25 | 2022-01-21 | 昭和电工株式会社 | Photosensitive resin composition, cured resin film and image display element |
| TW202204475A (en) * | 2020-06-03 | 2022-02-01 | 日商富士軟片股份有限公司 | Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device |
| WO2024042106A1 (en) | 2022-08-26 | 2024-02-29 | Merck Patent Gmbh | Composition |
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| JPS60206802A (en) * | 1984-03-30 | 1985-10-18 | Dainippon Ink & Chem Inc | Production of vinyl polymer having silyl group of improved hydrolyzability |
| JPS60206812A (en) * | 1984-03-31 | 1985-10-18 | Dainippon Ink & Chem Inc | Room temperature-setting resin composition containing vinyl polymer having silyl group of improved hydrolyzability |
| JPH02233709A (en) * | 1989-03-08 | 1990-09-17 | Kansai Paint Co Ltd | Resin, organic liquid, non-aqueous dispersion, aqueous liquid, curable composition and coating composition |
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| JP2006337567A (en) * | 2005-05-31 | 2006-12-14 | Sekisui Chem Co Ltd | Photocuring resin composition for photoresist, column spacer, and liquid crystal display element |
| JP5135820B2 (en) * | 2007-02-20 | 2013-02-06 | Ｊｓｒ株式会社 | Alkali-soluble polymer, radiation-sensitive composition for forming colored layer, color filter, and liquid crystal display device |
| JP5108480B2 (en) * | 2007-11-28 | 2012-12-26 | 東京応化工業株式会社 | Photosensitive resin composition for interlayer insulation film |
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