JPWO2014091818A1 - Copolymer, photosensitive resin composition and resin film containing the same - Google Patents
Copolymer, photosensitive resin composition and resin film containing the same Download PDFInfo
- Publication number
- JPWO2014091818A1 JPWO2014091818A1 JP2014551921A JP2014551921A JPWO2014091818A1 JP WO2014091818 A1 JPWO2014091818 A1 JP WO2014091818A1 JP 2014551921 A JP2014551921 A JP 2014551921A JP 2014551921 A JP2014551921 A JP 2014551921A JP WO2014091818 A1 JPWO2014091818 A1 JP WO2014091818A1
- Authority
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- Japan
- Prior art keywords
- acrylate
- meth
- copolymer
- 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.)
- Granted
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 52
- 239000011342 resin composition Substances 0.000 title claims abstract description 50
- 229920005989 resin Polymers 0.000 title claims description 41
- 239000011347 resin Substances 0.000 title claims description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 60
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 59
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims abstract description 15
- -1 2-isocyanatoethyl Chemical group 0.000 claims description 34
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical group [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 claims description 3
- 238000002845 discoloration Methods 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 8
- 239000010408 film Substances 0.000 description 51
- 239000000243 solution Substances 0.000 description 26
- 238000000034 method Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 10
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- PJMXUSNWBKGQEZ-UHFFFAOYSA-N (4-hydroxyphenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=C(O)C=C1 PJMXUSNWBKGQEZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 150000003217 pyrazoles Chemical class 0.000 description 3
- 125000006850 spacer group Chemical group 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
- ZVEMLYIXBCTVOF-UHFFFAOYSA-N 1-(2-isocyanatopropan-2-yl)-3-prop-1-en-2-ylbenzene Chemical group CC(=C)C1=CC=CC(C(C)(C)N=C=O)=C1 ZVEMLYIXBCTVOF-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
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- CPEXFJVZFNYXGU-UHFFFAOYSA-N 2,4,6-trihydroxybenzophenone Chemical compound OC1=CC(O)=CC(O)=C1C(=O)C1=CC=CC=C1 CPEXFJVZFNYXGU-UHFFFAOYSA-N 0.000 description 2
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 2
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- WXYSZTISEJBRHW-UHFFFAOYSA-N 4-[2-[4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl]propan-2-yl]phenol Chemical compound C=1C=C(C(C)(C=2C=CC(O)=CC=2)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WXYSZTISEJBRHW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 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
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- IPTNXMGXEGQYSY-UHFFFAOYSA-N acetic acid;1-methoxybutan-1-ol Chemical compound CC(O)=O.CCCC(O)OC IPTNXMGXEGQYSY-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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 1
- QWRVAXMLZCMVSL-UHFFFAOYSA-N (2,4,6-trihydroxyphenyl)-(3,4,5-trihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC(O)=C1C(=O)C1=CC(O)=C(O)C(O)=C1 QWRVAXMLZCMVSL-UHFFFAOYSA-N 0.000 description 1
- ZDROXNKXVHPNBJ-UHFFFAOYSA-N (2,6-dihydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=C(O)C=CC=C1O ZDROXNKXVHPNBJ-UHFFFAOYSA-N 0.000 description 1
- DIBYQTLCOMYUAP-UHFFFAOYSA-N (2-hydroxy-4-methylphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound OC1=CC(C)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O DIBYQTLCOMYUAP-UHFFFAOYSA-N 0.000 description 1
- HZBSQYSUONRRMW-UHFFFAOYSA-N (2-hydroxyphenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1O HZBSQYSUONRRMW-UHFFFAOYSA-N 0.000 description 1
- IUSXXDHQFMPZQX-UHFFFAOYSA-N (2-hydroxyphenyl) prop-2-enoate Chemical compound OC1=CC=CC=C1OC(=O)C=C IUSXXDHQFMPZQX-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- NTHRHRINERQNSR-UHFFFAOYSA-N (3-hydroxyphenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC(O)=C1 NTHRHRINERQNSR-UHFFFAOYSA-N 0.000 description 1
- DRZPXZMMDBMTHL-UHFFFAOYSA-N (3-hydroxyphenyl) prop-2-enoate Chemical compound OC1=CC=CC(OC(=O)C=C)=C1 DRZPXZMMDBMTHL-UHFFFAOYSA-N 0.000 description 1
- HWZREQONUGCFIT-UHFFFAOYSA-N (3-hydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound OC1=CC=CC(C(=O)C=2C(=C(O)C(O)=CC=2)O)=C1 HWZREQONUGCFIT-UHFFFAOYSA-N 0.000 description 1
- FVHMFMMVURPZFE-UHFFFAOYSA-N (4-hydroxy-3-methoxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound C1=C(O)C(OC)=CC(C(=O)C=2C(=C(O)C(O)=CC=2)O)=C1 FVHMFMMVURPZFE-UHFFFAOYSA-N 0.000 description 1
- NIUHGYUFFPSEOW-UHFFFAOYSA-N (4-hydroxyphenyl) prop-2-enoate Chemical compound OC1=CC=C(OC(=O)C=C)C=C1 NIUHGYUFFPSEOW-UHFFFAOYSA-N 0.000 description 1
- ZRDYULMDEGRWRC-UHFFFAOYSA-N (4-hydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O ZRDYULMDEGRWRC-UHFFFAOYSA-N 0.000 description 1
- WNHHRXSVKWWRJY-UHFFFAOYSA-N (5-methyl-5-bicyclo[2.2.1]hept-2-enyl)methanol Chemical compound C1C2C(C)(CO)CC1C=C2 WNHHRXSVKWWRJY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- PECUPOXPPBBFLU-UHFFFAOYSA-N 1-ethenyl-3-methoxybenzene Chemical compound COC1=CC=CC(C=C)=C1 PECUPOXPPBBFLU-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
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- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SFBTTWXNCQVIEC-UHFFFAOYSA-N o-Vinylanisole Chemical compound COC1=CC=CC=C1C=C SFBTTWXNCQVIEC-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- WLVPQQDEYVVXJF-UHFFFAOYSA-N phenyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C(C=C2)CC2C1C(=O)OC1=CC=CC=C1 WLVPQQDEYVVXJF-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity 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
- 230000035945 sensitivity Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 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
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
-
- 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
- C08K5/07—Aldehydes; Ketones
- C08K5/08—Quinones
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本発明の共重合体は、ヒドロキシフェニル（メタ）アクリレート由来の繰り返し単位と、ブロックされたイソシアネート基含有不飽和化合物由来の繰り返し単位とを含む。ヒドロキシフェニル（メタ）アクリレート由来の繰り返し単位は、３０ｍｏｌ％〜９０ｍｏｌ％、ブロックされたイソシアネート基含有不飽和化合物由来の繰り返し単位は、１０ｍｏｌ％〜７０ｍｏｌ％含まれることが好ましい。本発明の共重合体を含有する感光性樹脂組成物は、透明性、耐熱変色性及び電気特性に優れ、塗布性、現像性、硬化性及び保存安定性が良好である。The copolymer of the present invention includes a repeating unit derived from hydroxyphenyl (meth) acrylate and a repeating unit derived from a blocked isocyanate group-containing unsaturated compound. The repeating unit derived from hydroxyphenyl (meth) acrylate is preferably contained in an amount of 30 mol% to 90 mol%, and the repeating unit derived from a blocked isocyanate group-containing unsaturated compound is preferably contained in an amount of 10 mol% to 70 mol%. The photosensitive resin composition containing the copolymer of the present invention is excellent in transparency, heat discoloration, and electrical characteristics, and has good coatability, developability, curability and storage stability.
Description
本発明は、感光性樹脂組成物、詳しくは液晶表示素子、集積回路素子、固体撮像素子などの電子部品の保護膜、平坦化膜もしくは層間絶縁膜の形成、マイクロレンズもしくはマイクロレンズアレイの形成、液晶表示素子の光拡散反射膜、配向制御用突起もしくはスペーサーの形成、カラーフィルターの形成、又は光導波路の形成に好適な感光性樹脂組成物に関する。 The present invention relates to a photosensitive resin composition, specifically a protective film for electronic parts such as a liquid crystal display element, an integrated circuit element, a solid-state imaging element, a planarization film or an interlayer insulating film, a microlens or a microlens array, The present invention relates to a photosensitive resin composition suitable for formation of a light diffusive reflection film, alignment control protrusions or spacers of a liquid crystal display element, formation of a color filter, or formation of an optical waveguide.
従来、ＴＦＴ型液晶表示素子、磁気ヘッド素子、集積回路素子、固体撮像素子などの電子部品の劣化や損傷を防止するための保護膜、又は層状に配置される配線の間を絶縁するための層間絶縁膜の形成には感光性樹脂組成物が用いられてきた。中でも液晶表示素子の場合には、層間絶縁膜の上にＩＴＯ等の透明導電回路層を形成し、更にその上に液晶配向膜を形成する工程を経て製造されるため、層間絶縁膜は、透明電極膜の形成工程において高温条件に曝されたり、電極のパターン形成に使用されるレジストの剥離液に曝されることとなるため、これらに対する十分な耐性が必要となる。従って、層間絶縁膜を形成する感光性樹脂組成物には、現像性に優れ、透明性、耐熱性、平坦性、密着性、耐薬品性及び電気特性に優れた樹脂膜を形成できることが求められる。 Conventionally, a protective film for preventing deterioration or damage of electronic parts such as TFT liquid crystal display elements, magnetic head elements, integrated circuit elements, solid-state imaging elements, or interlayers for insulating between wirings arranged in layers. A photosensitive resin composition has been used to form an insulating film. In particular, in the case of a liquid crystal display element, since a transparent conductive circuit layer such as ITO is formed on an interlayer insulating film and further a liquid crystal alignment film is formed thereon, the interlayer insulating film is transparent. In the electrode film forming process, the film is exposed to a high temperature condition or exposed to a resist stripping solution used for forming an electrode pattern. Therefore, a photosensitive resin composition for forming an interlayer insulating film is required to be able to form a resin film having excellent developability and excellent transparency, heat resistance, flatness, adhesion, chemical resistance and electrical properties. .
一方、ファクシミリ、電子複写機、固体撮像素子等のオンチップカラーフィルターの結像光学系あるいは光ファイバコネクタの光学系材料として、３〜１００μｍ程度のレンズ径を有するマイクロレンズ、又はそれらのマイクロレンズを規則的に配列したマイクロレンズアレイが使用されている。中でもデジタルカメラ等に使用されるＣＣＤ素子は、近年、画素数の向上とともに微細化が進み、ＣＣＤ素子１つ当たりの受光エリアが減少してきている。そのため受光量を高める手段として、ＣＣＤ素子の上に凸レンズ状のマイクロレンズを形成する事が試みられている。ＣＣＤ素子に用いるマイクロレンズとしては、フォトレジスト膜を露光、現像して凹凸パターンを形成し、この凹凸パターンをガラス転移点以上の温度で加熱することで流動させ、表面張力により半球状のマイクロレンズを形成する方法が知られている。従って、マイクロレンズを形成する感光性樹脂組成物としては現像性に優れ、透明性、メルトフロー性及び耐熱性が求められ、集光度の観点から高い屈折率が求められる。 On the other hand, as an optical system material for an imaging optical system of an on-chip color filter such as a facsimile, an electronic copying machine, a solid-state image sensor, or an optical fiber connector, a microlens having a lens diameter of about 3 to 100 μm, or a microlens thereof. A regularly arranged microlens array is used. In particular, CCD elements used in digital cameras and the like have recently been miniaturized as the number of pixels has increased, and the light receiving area per CCD element has decreased. Therefore, as a means for increasing the amount of received light, it has been attempted to form a convex lens-shaped microlens on the CCD element. As a microlens used for a CCD element, a photoresist film is exposed and developed to form a concavo-convex pattern, and the concavo-convex pattern is flowed by heating at a temperature equal to or higher than the glass transition point. A method of forming is known. Accordingly, the photosensitive resin composition for forming the microlens is required to have excellent developability, transparency, melt flow property, and heat resistance, and a high refractive index from the viewpoint of light collection.
上記感光性樹脂組成物としては、例えば、特許文献１には、（ａ）不飽和カルボン酸とエポキシ基含有重合性不飽和化合物との共重合体、（ｂ）不飽和カルボン酸とそれ以外のモノオレフィン系不飽和化合物との共重合体、（ｃ）キノンジアジド基含有化合物、及び（ｄ）有機溶媒を含む感光性樹脂組成物が記載されている。また、特許文献２には、（ａ）不飽和カルボン酸とエポキシ基含有重合性不飽和化合物との共重合体、（ｂ）スチレン類と不飽和カルボン酸との共重合体、（ｃ）キノンジアジド基含有化合物、及び（ｄ）有機溶媒を含む感光性樹脂組成物が記載されている。
特許文献３には、［Ａ］不飽和カルボン酸とエポキシ基含有不飽和化合物とそれら以外のオレフィン系不飽和化合物との共重合体、及び［Ｂ］特定のフェノール化合物と１，２−ナフトキノンジアジドスルホン酸ハライドとの縮合物を含む感放射線性樹脂組成物が記載されている。
また、特許文献４及び５には、不飽カルボン酸と脂環式エポキシ基含有不飽和化合物との共重合体、及び１，２−ナフトキノンジアジドスルホン酸エステルを含む感光性樹脂組成物が記載されている。Examples of the photosensitive resin composition include, for example, Patent Document 1, (a) a copolymer of an unsaturated carboxylic acid and an epoxy group-containing polymerizable unsaturated compound, and (b) an unsaturated carboxylic acid and other compounds. A photosensitive resin composition containing a copolymer with a monoolefin unsaturated compound, (c) a quinonediazide group-containing compound, and (d) an organic solvent is described. Patent Document 2 discloses (a) a copolymer of an unsaturated carboxylic acid and an epoxy group-containing polymerizable unsaturated compound, (b) a copolymer of styrenes and an unsaturated carboxylic acid, (c) a quinonediazide. A photosensitive resin composition containing a group-containing compound and (d) an organic solvent is described.
Patent Document 3 includes [A] a copolymer of an unsaturated carboxylic acid, an epoxy group-containing unsaturated compound, and another olefinic unsaturated compound, and [B] a specific phenol compound and 1,2-naphthoquinonediazide. A radiation sensitive resin composition containing a condensate with a sulfonic acid halide is described.
Patent Documents 4 and 5 describe a photosensitive resin composition containing a copolymer of an unsaturated carboxylic acid and an alicyclic epoxy group-containing unsaturated compound, and 1,2-naphthoquinonediazide sulfonic acid ester. ing.
上記した従来の感光性樹脂は、アルカリ溶解性を発現する成分として、何れもメタクリル酸等の不飽和カルボン酸を使用しているところが共通している。しかし、これらの感光性樹脂は、フェノール性水酸基を有するものと比べて酸性度が高いため、現像性の管理が困難である上に、エポキシ基との反応性に優れる反面、現像マージン及び保存安定性が不十分であるという問題がある。この問題は、モノオレフィン系不飽和化合物を共重合成分の一部として用いることで改善されるものの、スカムの原因となり得るため、解決手段として充分とは言えない。 The above-described conventional photosensitive resins are common in that unsaturated carboxylic acids such as methacrylic acid are used as components that exhibit alkali solubility. However, these photosensitive resins have higher acidity than those having a phenolic hydroxyl group, so that it is difficult to manage developability and have excellent reactivity with epoxy groups, but development margin and storage stability. There is a problem that the property is insufficient. Although this problem can be improved by using a monoolefin unsaturated compound as a part of the copolymerization component, it can cause scum, so it cannot be said to be sufficient as a solution.
また、特許文献６には、（Ａ）ヒドロキシスチレンとメタクリル酸メチルとの共重合体、（Ｂ）キノンジアジド基含有化合物、及び（Ｃ）熱硬化性樹脂を含む感光性樹脂組成物が記載されている。この樹脂組成物は、アルカリ溶解性を発現する成分として、ヒドロキシスチレンを使用しているところに特徴を有する。しかし、この感光性樹脂組成物は、フェノール性水酸基を有するため、上記問題点の解決手段としては有効であるものの、加熱により着色するという欠点を有している。 Patent Document 6 describes a photosensitive resin composition containing (A) a copolymer of hydroxystyrene and methyl methacrylate, (B) a quinonediazide group-containing compound, and (C) a thermosetting resin. Yes. This resin composition is characterized in that hydroxystyrene is used as a component that exhibits alkali solubility. However, since this photosensitive resin composition has a phenolic hydroxyl group, it is effective as a means for solving the above-mentioned problems, but has a drawback of being colored by heating.
また、特許文献７には、ヒドロキシフェニル（メタ）アクリレートとエポキシ基含有不飽和化合物とを重合成分として含む共重合体、及びキノンジアジド基含有化合物を含む感光性樹脂組成物が記載されている。この感光性樹脂組成物は、上記した感光性樹脂組成物が有する技術課題を克服すべく開発されたものであるが、電気特性及び耐熱変色性が十分とは言えなかった。 Patent Document 7 discloses a photosensitive resin composition containing a copolymer containing hydroxyphenyl (meth) acrylate and an epoxy group-containing unsaturated compound as polymerization components, and a quinonediazide group-containing compound. This photosensitive resin composition was developed to overcome the technical problems of the photosensitive resin composition described above, but it could not be said that the electrical characteristics and the heat discoloration were sufficient.
本発明は、このような状況に鑑み、透明性、耐熱変色性及び電気特性に優れ、塗布性、現像性、硬化性及び保存安定性の良好な感光性樹脂組成物、及びこれらの特性を発現するための共重合体を提供することを目的とする。 In view of such circumstances, the present invention expresses a photosensitive resin composition that is excellent in transparency, heat discoloration, and electrical characteristics, and has good coatability, developability, curability, and storage stability, and these characteristics. An object of the present invention is to provide a copolymer.
本発明者らは、上記目的を達成するため鋭意検討した結果、ヒドロキシフェニル（メタ）アクリレート由来の繰り返し単位と、ブロックされたイソシアネート基含有不飽和化合物由来の繰り返し単位とを含む共重合体が、上記目的を達成し得ることを見出し、本発明を完成するに至った。
即ち、本発明は、以下の［１］〜［９］で示される。
［１］ヒドロキシフェニル（メタ）アクリレート由来の繰り返し単位と、ブロックされたイソシアネート基含有不飽和化合物由来の繰り返し単位とを含むことを特徴とする共重合体。
［２］前記ヒドロキシフェニル（メタ）アクリレート由来の繰り返し単位３０ｍｏｌ％〜９０ｍｏｌ％と、前記ブロックされたイソシアネート基含有不飽和化合物由来の繰り返し単位１０ｍｏｌ％〜７０ｍｏｌ％とを含むことを特徴とする［１］に記載の共重合体。
［３］前記ブロックされたイソシアネート基含有不飽和化合物が、ブロックされた２−イソシアナトエチル（メタ）アクリレートであることを特徴とする［１］又は［２］に記載の共重合体。
［４］前記ブロックが、メチルエチルケトンオキシムによるものであることを特徴とする［１］〜［３］の何れかに記載の共重合体。
［５］前記ブロックされたイソシアネート基含有不飽和化合物が、２−（０−［１’−メチルプロピリデンアミノ］カルボキシアミノ）エチル（メタ）アクリレートであることを特徴とする［１］〜［４］の何れかに記載の共重合体。
［６］［１］〜［５］の何れかに記載の共重合体及びキノンジアジド基含有化合物を含有することを特徴とする感光性樹脂組成物。
［７］前記共重合体１００質量部に対して、前記キノンジアジド基含有化合物を５〜６０質量部含むことを特徴とする［６］に記載の感光性樹脂組成物。
［８］溶媒以外の成分の合計量１００質量部に対して、溶媒を３０〜４０００質量部含むことを特徴とする［６］又は［７］に記載の感光性樹脂組成物。
［９］［６］〜［８］の何れかに記載の感光性樹脂組成物を基板上に塗布し、乾燥して得られることを特徴とする樹脂膜。As a result of intensive studies to achieve the above object, the present inventors have found that a copolymer comprising a repeating unit derived from hydroxyphenyl (meth) acrylate and a repeating unit derived from a blocked isocyanate group-containing unsaturated compound is obtained. The inventors have found that the above object can be achieved and have completed the present invention.
That is, this invention is shown by the following [1]-[9].
[1] A copolymer comprising a repeating unit derived from hydroxyphenyl (meth) acrylate and a repeating unit derived from a blocked isocyanate group-containing unsaturated compound.
[2] It contains 30 mol% to 90 mol% of repeating units derived from the hydroxyphenyl (meth) acrylate and 10 mol% to 70 mol% of repeating units derived from the blocked isocyanate group-containing unsaturated compound [1] ] The copolymer as described in.
[3] The copolymer according to [1] or [2], wherein the blocked isocyanate group-containing unsaturated compound is blocked 2-isocyanatoethyl (meth) acrylate.
[4] The copolymer according to any one of [1] to [3], wherein the block is made of methyl ethyl ketone oxime.
[5] The blocked isocyanate group-containing unsaturated compound is 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl (meth) acrylate, [1] to [4] ] The copolymer in any one of.
[6] A photosensitive resin composition comprising the copolymer according to any one of [1] to [5] and a quinonediazide group-containing compound.
[7] The photosensitive resin composition as described in [6], comprising 5 to 60 parts by mass of the quinonediazide group-containing compound with respect to 100 parts by mass of the copolymer.
[8] The photosensitive resin composition as described in [6] or [7], wherein the solvent is contained in an amount of 30 to 4000 parts by mass with respect to 100 parts by mass of the total amount of components other than the solvent.
[9] A resin film obtained by applying the photosensitive resin composition according to any one of [6] to [8] on a substrate and drying it.
本発明によれば、透明性、耐熱変色性及び電気特性に優れ、塗布性、現像性、硬化性及び保存安定性の良好な感光性樹脂組成物、及びこれらの特性を発現するための共重合体を提供することができる。 According to the present invention, a photosensitive resin composition having excellent transparency, heat discoloration, and electrical characteristics, and good coating properties, developability, curability, and storage stability, and a co-polymer for exhibiting these characteristics. Coalescence can be provided.
以下、本発明の感光性樹脂組成物について詳述する。
なお、明細書及び特許請求の範囲において、（メタ）アクリレートとは、メタクリレート又はアクリレートを意味する。
本発明の感光性樹脂組成物において必須成分として含まれる共重合体［Ａ］は、（ａ１）ヒドロキシフェニル（メタ）アクリレート由来の繰り返し単位と、（ａ２）ブロックされたイソシアネート基含有不飽和化合物由来の繰り返し単位とを含むものである。
（ａ１）ヒドロキシフェニル（メタ）アクリレートの具体例としては、ｏ−ヒドロキシフェニルアクリレート、ｍ−ヒドロキシフェニルアクリレート、ｐ−ヒドロキシフェニルアクリレート、ｏ−ヒドロキシフェニルメタクリレート、ｍ−ヒドロキシフェニルメタクリレート、ｐ−ヒドロキシフェニルメタクリレートなどが挙げられる。これらは単独で使用してもよいし、２種以上を組み合わせて使用してもよい。また、これらの中でも、ｐ−ヒドロキシフェニルメタクリレートが好ましい。Hereinafter, the photosensitive resin composition of the present invention will be described in detail.
In the specification and claims, (meth) acrylate means methacrylate or acrylate.
The copolymer [A] contained as an essential component in the photosensitive resin composition of the present invention is derived from (a1) a repeating unit derived from hydroxyphenyl (meth) acrylate and (a2) a blocked isocyanate group-containing unsaturated compound. The repeating unit is included.
(A1) Specific examples of hydroxyphenyl (meth) acrylate include o-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, o-hydroxyphenyl methacrylate, m-hydroxyphenyl methacrylate, and p-hydroxyphenyl methacrylate. Etc. These may be used alone or in combination of two or more. Of these, p-hydroxyphenyl methacrylate is preferred.
共重合体［Ａ］において、（ａ１）ヒドロキシフェニル（メタ）アクリレート由来の繰り返し単位は、３０ｍｏｌ％〜９０ｍｏｌ％含まれることが好ましく、４０ｍｏｌ％〜８０ｍｏｌ％含まれることが更に好ましい。（ａ１）ヒドロキシフェニル（メタ）アクリレート由来の繰り返し単位が３０ｍｏｌ％未満であると、アルカリ溶解性が不十分になる場合があり、一方、９０ｍｏｌ％を超えると、良好なパターンを形成できない場合がある。 In the copolymer [A], the repeating unit derived from (a1) hydroxyphenyl (meth) acrylate is preferably contained in an amount of 30 mol% to 90 mol%, more preferably 40 mol% to 80 mol%. (A1) When the repeating unit derived from hydroxyphenyl (meth) acrylate is less than 30 mol%, the alkali solubility may be insufficient. On the other hand, when it exceeds 90 mol%, a good pattern may not be formed. .
（ａ２）ブロックされたイソシアネート基含有不飽和化合物は、イソシアネート基含有不飽和化合物を公知又は周知のブロック化剤と反応させることにより、イソシアネート基をブロックして容易に得られる。イソシアネート基含有不飽和化合物としては、２−イソシアナトエチル（メタ）アクリレート、イソプロペニル−α，α−ジメチルベンジルイソシアネートなどのイソシアネート基含有エチレン性不飽和化合物が挙げられる。ブロック化剤としては、アルキルケトキシム類、フェノール類、アルコール類、ピラゾール類、β−ジケトン類及びラクタム類が好ましく、アルキルケトキシム類、フェノール類、アルコール類及びピラゾール類がより好ましく、アルキルケトキシム類及びピラゾール類が最も好ましい。ブロックされたイソシアネート基含有不飽和化合物の具体例としては、２−（０−[１'−メチルプロピリデンアミノ］カルボキシアミノ）エチルアクリレート、２−（０−[１'−メチルプロピリデンアミノ］カルボキシアミノ）エチルメタクリレート、２−[（３，５−ジメチルピラゾリル）カルボニルアミノ］エチルアクリレート、２−[（３，５−ジメチルピラゾリル）カルボニルアミノ］エチルメタクリレート、２−[（フタルイミド）カルボニルアミノ］エチルアクリレート、２−[（フタルイミド）カルボニルアミノ］エチルメタクリレート、２−[（スクシンイミド）カルボニルアミノ］エチルアクリレート、２−[（スクシンイミド）カルボニルアミノ］エチルメタクリレートなどのイソシアネート基がブロックされた２−イソシアナトエチル（メタ）アクリレート、２−（０−[１'−メチルプロピリデンアミノ］カルボキシアミノ）３−イソプロペニル−α，α−ジメチルベンジル、２−（０−[１'−メチルプロピリデンアミノ］カルボキシアミノ）４−イソプロペニル−α，α−ジメチルベンジル、２−[（３，５−ジメチルピラゾリル）カルボニルアミノ］３−イソプロペニル−α，α−ジメチルベンジル、２−[（３，５−ジメチルピラゾリル）カルボニルアミノ］４−イソプロペニル−α，α−ジメチルベンジルなどのイソシアネート基がブロックされたイソプロペニル−α，α−ジメチルベンジルイソシアネートが挙げられる。これらは単独で使用してもよいし、２種以上を組み合わせて使用してもよい。これらの中でも、共重合性という観点から、イソシアネート基がブロックされた２−イソシアナトエチル（メタ）アクリレートが好ましい。 (A2) The blocked isocyanate group-containing unsaturated compound can be easily obtained by blocking the isocyanate group by reacting the isocyanate group-containing unsaturated compound with a known or well-known blocking agent. Examples of the isocyanate group-containing unsaturated compound include isocyanate group-containing ethylenically unsaturated compounds such as 2-isocyanatoethyl (meth) acrylate and isopropenyl-α, α-dimethylbenzyl isocyanate. As the blocking agent, alkyl ketoximes, phenols, alcohols, pyrazoles, β-diketones and lactams are preferable, alkyl ketoximes, phenols, alcohols and pyrazoles are more preferable, alkyl ketoximes. And pyrazoles are most preferred. Specific examples of the blocked isocyanate group-containing unsaturated compound include 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl acrylate and 2- (0- [1′-methylpropylideneamino] carboxyl. Amino) ethyl methacrylate, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl acrylate, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate, 2-[(phthalimido) carbonylamino] ethyl acrylate 2-isocyanato with blocked isocyanate groups such as 2-[(phthalimido) carbonylamino] ethyl methacrylate, 2-[(succinimide) carbonylamino] ethyl acrylate, 2-[(succinimide) carbonylamino] ethyl methacrylate Ethyl (meth) acrylate, 2- (0- [1′-methylpropylideneamino] carboxyamino) 3-isopropenyl-α, α-dimethylbenzyl, 2- (0- [1′-methylpropylideneamino] carboxy Amino) 4-isopropenyl-α, α-dimethylbenzyl, 2-[(3,5-dimethylpyrazolyl) carbonylamino] 3-isopropenyl-α, α-dimethylbenzyl, 2-[(3,5-dimethylpyrazolyl) ) Carbonylamino] 4-isopropenyl-α, α-dimethylbenzyl and the like, such as isopropenyl-α, α-dimethylbenzyl isocyanate blocked with an isocyanate group. These may be used alone or in combination of two or more. Among these, 2-isocyanatoethyl (meth) acrylate in which an isocyanate group is blocked is preferable from the viewpoint of copolymerization.
共重合体［Ａ］において、（ａ２）ブロックされたイソシアネート基含有不飽和化合物由来の繰り返し単位は、１０ｍｏｌ％〜７０ｍｏｌ％含まれることが好ましく、２０ｍｏｌ％〜６０ｍｏｌ％含まれることが更に好ましい。（ａ２）ブロックされたイソシアネート基含有不飽和化合物由来の繰り返し単位が１０ｍｏｌ％未満であると、耐熱性、耐薬品性及び電気特性が低下する場合があり、一方、７０ｍｏｌ％を超えると、アルカリ溶解性が不十分になる場合がある。 In the copolymer [A], the repeating unit derived from the (a2) blocked isocyanate group-containing unsaturated compound is preferably contained in an amount of 10 mol% to 70 mol%, more preferably 20 mol% to 60 mol%. (A2) If the repeating unit derived from the blocked isocyanate group-containing unsaturated compound is less than 10 mol%, the heat resistance, chemical resistance and electrical properties may be deteriorated. May be insufficient.
共重合体［Ａ］は、（ａ１）ヒドロキシフェニル（メタ）アクリレート及び（ａ２）ブロックされたイソシアネート基含有不飽和化合物のみからなる共重合体であってもよいし、（ａ１）ヒドロキシフェニル（メタ）アクリレート及び（ａ２）ブロックされたイソシアネート基含有不飽和化合物と共重合し得る、別のエチレン性不飽和化合物を共重合成分として含む共重合体であってもよい。別の不飽和化合物としては、例えば、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、フマル酸、シトラコン酸、メサコン酸、イタコン酸、無水マレイン酸、無水フマル酸、無水シトラコン酸、無水メサコン酸、無水イタコン酸、ビニル安息香酸、ｏ−カルボキシフェニル（メタ）アクリレート、ｍ−カルボキシフェニル（メタ）アクリレート、ｐ−カルボキシフェニル（メタ）アクリレート、ｏ−カルボキシフェニル（メタ）アクリルアミド、ｍ−カルボキシフェニル（メタ）アクリルアミド、ｐ−カルボキシフェニル（メタ）アクリルアミド、コハク酸モノ〔２−（メタ）アクリロイルオキシエチル〕、フタル酸モノ〔２−（メタ）アクリロイルオキシエチル〕、ω−カルボキシポリカプロラクトンモノ（メタ）アクリレート、５−カルボキシビシクロ［２．２．１］ヘプト−２−エン、５，６−ジカルボキシビシクロ［２．２．１］ヘプト−２−エン、５−カルボキシ−５−メチルビシクロ［２．２．１］ヘプト−２−エン、５−カルボキシ−５−エチルビシクロ［２．２．１］ヘプト−２−エン、５−カルボキシ−６−メチルビシクロ［２．２．１］ヘプト−２−エン、５−カルボキシ−６−エチルビシクロ［２．２．１］ヘプト−２−エン、５，６−ジカルボキシビシクロ［２．２．１］ヘプト−２−エン無水物、トリシクロ［５．２．１．０2,6］デカン−８−イル（メタ）アクリレート、トリシクロ［５．２．１．０2,6］デカン−８−イルオキシエチル（メタ）アクリレート、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｓｅｃ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ｎ−ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、ｎ−ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−メチルシクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ヒドロキシメチル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、ジエチレングリコールモノ（メタ）アクリレート、２，３−ジヒドロキシプロピル（メタ）アクリレート、２−（メタ）アクリロイルオキシエチルグリコサイド、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、ｏ−メトキシフェニル（メタ）アクリレート、ｍ−メトキシフェニル（メタ）アクリレート、ｐ−メトキシフェニル（メタ）アクリレート、３−メチル−４−ヒドロキシフェニル（メタ）アクリレート、２−メチル−４−ヒドロキシフェニル（メタ）アクリレート、ジメチルヒドロキシフェニル（メタ）アクリレート、マレイン酸ジエチル、フマル酸ジエチル、イタコン酸ジエチル、ビシクロ［２．２．１］ヘプト−２−エン、５−メチルビシクロ［２．２．１］ヘプト−２−エン、５−エチルビシクロ［２．２．１］ヘプト−２−エン、５−メトキシビシクロ［２．２．１］ヘプト−２−エン、５−エトキシビシクロ［２．２．１］ヘプト−２−エン、５，６−ジメトキシビシクロ［２．２．１］ヘプト−２−エン、５，６−ジエトキシビシクロ［２．２．１］ヘプト−２−エン、５−ｔ−ブトキシカルボニルビシクロ［２．２．１］ヘプト−２−エン、５−シクロヘキシルオキシカルボニルビシクロ［２．２．１］ヘプト−２−エン、５−フェノキシカルボニルビシクロ［２．２．１］ヘプト−２−エン、５，６−ジ（ｔ−ブトキシカルボニル）ビシクロ［２．２．１］ヘプト−２−エン、５，６−ジ（シクロヘキシルオキシカルボニル）ビシクロ［２．２．１］ヘプト−２−エン、５−（２’−ヒドロキシエチル）ビシクロ［２．２．１］ヘプト−２−エン、５，６−ジヒドロキシビシクロ［２．２．１］ヘプト−２−エン、５，６−ジ（ヒドロキシメチル）ビシクロ［２．２．１］ヘプト−２−エン、５，６−ジ（２’−ヒドロキシエチル）ビシクロ［２．２．１］ヘプト−２−エン、５−ヒドロキシ−５−メチルビシクロ［２．２．１］ヘプト−２−エン、５−ヒドロキシ−５−エチルビシクロ［２．２．１］ヘプト−２−エン、５−ヒドロキシメチル−５−メチルビシクロ［２．２．１］ヘプト−２−エン、スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、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、１，３−ブタジエン、イソプレン、２，３−ジメチル−１，３−ブタジエン、アクリロニトリル、メタクリロニトリル、塩化ビニル、塩化ビニリデン、アクリルアミド、メタクリルアミド、酢酸ビニル、ｏ−ヒドロキシフェニル（メタ）アクリルアミド、ｍ−ヒドロキシフェニル（メタ）アクリルアミド、ｐ−ヒドロキシフェニル（メタ）アクリルアミド、３，５−ジメチル−４−ヒドロキシベンジル（メタ）アクリルアミド、フェニルマレイミド、ヒドロキシフェニルマレイミド、シクロヘキシルマレイミド、ベンジルマレイミド、トリフルオロメチル（メタ）アクリレートなどが挙げられる。これらは単独で使用してもよいし、２種以上を組み合わせて使用してもよい。これらの不飽和化合物は、透明性、耐熱性、密着性、耐薬品性、電気特性、屈折率、塗布性、現像性、保存安定性、機械的強度等の調整のため、各特性に悪影響を与えない範囲内で任意の割合で使用することができる。The copolymer [A] may be a copolymer composed only of (a1) hydroxyphenyl (meth) acrylate and (a2) blocked isocyanate group-containing unsaturated compound, or (a1) hydroxyphenyl (meta It may be a copolymer containing, as a copolymerization component, another ethylenically unsaturated compound that can be copolymerized with acrylate) and (a2) a blocked isocyanate group-containing unsaturated compound. Examples of other unsaturated compounds include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, maleic anhydride, fumaric anhydride, citraconic anhydride, mesaconic anhydride, Itaconic anhydride, vinyl benzoic acid, o-carboxyphenyl (meth) acrylate, m-carboxyphenyl (meth) acrylate, p-carboxyphenyl (meth) acrylate, o-carboxyphenyl (meth) acrylamide, m-carboxyphenyl (meta ) Acrylamide, p-carboxyphenyl (meth) acrylamide, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate 5 Carboxycyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] Hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5- Carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, tricyclo [5.2.1.0 2,6 ] decan-8-yl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yloxyethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate , N-butyl (meth) Acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate, n-stearyl ( (Meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl Luglycoside, phenyl (meth) acrylate, benzyl (meth) acrylate, o-methoxyphenyl (meth) acrylate, m-methoxyphenyl (meth) acrylate, p-methoxyphenyl (meth) acrylate, 3-methyl-4-hydroxy Phenyl (meth) acrylate, 2-methyl-4-hydroxyphenyl (meth) acrylate, dimethylhydroxyphenyl (meth) acrylate, diethyl maleate, diethyl fumarate, diethyl itaconate, bicyclo [2.2.1] hept-2 -Ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept- 2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5 6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] ] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di ( t-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxy) Ethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2. 1] Hept- -Ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, Acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, o-hydroxyphenyl (meth) acrylic M-hydroxyphenyl (meth) acrylamide, p-hydroxyphenyl (meth) acrylamide, 3,5-dimethyl-4-hydroxybenzyl (meth) acrylamide, phenylmaleimide, hydroxyphenylmaleimide, cyclohexylmaleimide, benzylmaleimide, trifluoro And methyl (meth) acrylate. These may be used alone or in combination of two or more. These unsaturated compounds adversely affect each property for adjustment of transparency, heat resistance, adhesion, chemical resistance, electrical properties, refractive index, coatability, developability, storage stability, mechanical strength, etc. It can be used at any ratio within the range not given.
本発明の共重合体の重量平均分子量（Ｍｗ）は、ポリスチレン換算で好ましくは１，５００〜５０，０００であり、より好ましくは２，０００〜２０，０００である。重量平均分子量が１，５００未満であると、平坦な樹脂膜が得られなかったり、現像後の残膜率が低下したり、あるいは得られる樹脂膜のパターン形状及び耐熱性の悪化を招く場合があり、一方、５０，０００を超えると、感度が低下したり、パターン形状が悪化する場合がある。 The weight average molecular weight (Mw) of the copolymer of the present invention is preferably 1,500 to 50,000, more preferably 2,000 to 20,000 in terms of polystyrene. If the weight average molecular weight is less than 1,500, a flat resin film may not be obtained, the remaining film ratio after development may be reduced, or the pattern shape and heat resistance of the resulting resin film may be deteriorated. On the other hand, if it exceeds 50,000, the sensitivity may decrease or the pattern shape may deteriorate.
なお、本発明における共重合体の分子量の値は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）を用いて、下記条件にて測定し、ポリスチレン換算にて算出されるものである。ＧＰＣの立ち上がり時間から２１分までを計算範囲として、重量平均分子量及び分子量分布を計算する。
カラム：ショウデックス（登録商標） ＫＦ−８０１＋ＫＦ−８０２＋ＫＦ−８０２＋ＫＦ−８０３
カラム温度：４０℃
展開溶媒：テトラヒドロフラン
検出器：示差屈折計（ショウデックス（登録商標） ＲＩ−１０１）
流速：１ｍＬ／ｍｉｎIn addition, the value of the molecular weight of the copolymer in this invention is measured on the following conditions using gel permeation chromatography (GPC), and is calculated in polystyrene conversion. The weight average molecular weight and molecular weight distribution are calculated with the calculation range from the rise time of GPC to 21 minutes.
Column: Shodex (registered trademark) KF-801 + KF-802 + KF-802 + KF-803
Column temperature: 40 ° C
Developing solvent: Tetrahydrofuran Detector: Differential refractometer (Showex (registered trademark) RI-101)
Flow rate: 1 mL / min
本発明の共重合体を得るための重合反応は、特に制限されず、ラジカル重合、カチオン重合、アニオン重合、配位アニオン重合などが挙げられる。具体的には、（ａ１）ヒドロキシフェニル（メタ）アクリレート及び（ａ２）イソシアネート基含有不飽和化合物を必須成分とし、必要により別の不飽和化合物を合計で好ましくは１０質量％〜６０質量％の範囲で含有する反応溶媒中で、重合開始剤を用いて重合することができる。分子量の調整は、反応溶媒の使用量、開始剤の使用量、及び重合温度を調整することで可能である。また、分子量の調整は、メルカプタン類に代表される連鎖移動剤を使用することでも可能である。 The polymerization reaction for obtaining the copolymer of the present invention is not particularly limited, and examples thereof include radical polymerization, cationic polymerization, anionic polymerization, and coordinated anionic polymerization. Specifically, (a1) hydroxyphenyl (meth) acrylate and (a2) an isocyanate group-containing unsaturated compound are essential components, and if necessary, another unsaturated compound is preferably added in a range of preferably 10% by mass to 60% by mass. It can superpose | polymerize in a reaction solvent contained by using a polymerization initiator. The molecular weight can be adjusted by adjusting the amount of reaction solvent used, the amount of initiator used, and the polymerization temperature. The molecular weight can also be adjusted by using a chain transfer agent typified by mercaptans.
反応溶媒の具体例としては、メタノール、エタノール、１−プロパノール、イソプロピルアルコール、ブタノール、エチレングリコール、アセトン、メチルエチルケトン、メチルイソブチルケトン、テトラヒドロフラン、ジオキサン、トルエン、キシレン、エチルアセテート、イソプロピルアセテート、ノルマルプロピルアセテート、ブチルアセテート、エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、酢酸３−メトキシブチル等のメトキシブチルアセテート、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、３−メトキシブタノール、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミド、乳酸エチル、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールジメチルエーテル、メトキシプロピオン酸メチル、エトキシプロピオン酸エチルなどが挙げられる。
重合開始剤としては、例えば、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２−ブチロニトリル）、２，２’−アゾビスイソブチロニトリル、ジメチル−２，２’−アゾビスイソブチレート、１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）等のアゾ系開始剤やベンゾイルパーオキサイド、ラウリルパーオキサイド、オクタノイルパーオキサイド、アセチルパーオキサイド、ジ−ｔ−ブチルパーオキサイド、ｔ−ブチルクミルパーオキサイド、ジクミルパーオキサイド、ｔ−ブチルパーオキシアセテート、ｔ−ブチルパーオキシベンゾエート等の有機過酸化物が挙げられる。Specific examples of the reaction solvent include methanol, ethanol, 1-propanol, isopropyl alcohol, butanol, ethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, toluene, xylene, ethyl acetate, isopropyl acetate, normal propyl acetate, Butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, methoxybutyl acetate such as 3-methoxybutyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, The Pyrene glycol monomethyl ether, ethylene glycol monoethyl ether, 3-methoxybutanol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, ethyl lactate, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, methyl methoxypropionate, Examples include ethyl ethoxypropionate.
Examples of the polymerization initiator include 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-butyronitrile), 2,2′-azobisisobutyronitrile, dimethyl- Azo initiators such as 2,2′-azobisisobutyrate, 1,1′-azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di Examples thereof include organic peroxides such as -t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, t-butyl peroxyacetate, and t-butyl peroxybenzoate.
本発明の感光性樹脂組成物において必須成分として含まれるキノンジアジド基含有化合物［Ｂ］は、感光剤であり、キノンジアジド基を有する化合物であれば特に限定されない。例えば、フェノール性化合物又はアルコール性化合物と、１，２−ナフトキノンジアジドスルホン酸ハライドとの縮合により得ることのできるエステルが好ましいものとして挙げられる。中でも、感光性及び樹脂膜の透明性という観点から、フェノール性化合物又はアルコール性化合物中の水酸基に対して、３０〜８５ｍｏｌ％に相当する１，２−ナフトキノンジアジドスルホン酸ハライドを縮合させたものが更に好ましく、５０〜７０ｍｏｌ％に相当する１，２−ナフトキノンジアジドスルホン酸ハライドを縮合させたものが最も好ましい。当該フェノール性化合物又はアルコール性化合物の具体例としては、２，３，４−トリヒドロキシベンゾフェノン、２，４，６−トリヒドロキシベンゾフェノン、２，２’，４，４’−テトラヒドロキシベンゾフェノン、２，３，４，３’−テトラヒドロキシベンゾフェノン、２，３，４，４’−テトラヒドロキシベンゾフェノン、２，３，４，２’−テトラヒドロキシ−４’−メチルベンゾフェノン、２，３，４，４’−テトラヒドロキシ−３’−メトキシベンゾフェノン、２，３，４，２’，６’−ペンタヒドロキシベンゾフェノン、２，４，６，３’，４’，５’−ヘキサヒドロキシベンゾフェノン、３，４，５，３’，４’，５’−ヘキサヒドロキシベンゾフェノン、２−メチル−２−（２，４−ジヒドロキシフェニル）−４−（４−ヒドロキシフェニル）−７−ヒドロキシクロマン、２−［ビス｛（５−イソプロピル−４−ヒドロキシ−２−メチル）フェニル｝メチル］フェノール、１−［１−（３−｛１−（４−ヒドロキシフェニル）−１−メチルエチル｝−４，６−ジヒドロキシフェニル）−１−メチルエチル］−３−（１−（３−｛１−（４−ヒドロキシフェニル）−１−メチルエチル｝−４，６−ジヒドロキシフェニル）−１−メチルエチル）ベンゼン、４，６−ビス｛１−（４−ヒドロキシフェニル）−１−メチルエチル｝−１，３−ジヒドロキシベンゼンビス（２，４−ジヒドロキシフェニル）メタン、ビス（ｐ−ヒドロキシフェニル）メタン、トリ（ｐ−ヒドロキシフェニル）メタン、１，１，１−トリ（ｐ−ヒドロキシフェニル）エタン、ビス（２，３，４−トリヒドロキシフェニル）メタン、２，２−ビス（２，３，４−トリヒドロキシフェニル）プロパン、１，１，３−トリス（２，５−ジメチル−４−ヒドロキシフェニル）−３−フェニルプロパン、１−［１−（４−ヒドロキシフェニル）イソプロピル］−４−［１，１−ビス（４−ヒドロキシフェニル）エチル］ベンゼン、ビス（２，５−ジメチル−４−ヒドロキシフェニル）−２−ヒドロキシフェニルメタン、３，３，３’，３’−テトラメチル−１，１’−スピロビインデン−５，６，７，５’，６’，７’−ヘキサノール、２，２，４−トリメチル−７，２’，４’−トリヒドロキシフラバンなどが挙げられる。これらは単独で使用してもよいし、２種以上を組み合わせて使用してもよい。キノンジアジド基を有する化合物［Ｂ］としては、１−［１−（４−ヒドロキシフェニル）イソプロピル］−４−［１，１−ビス（４−ヒドロキシフェニル）エチル］ベンゼンの１，２−ナフトキノンジアジドスルホン酸エステルが好ましい。 The quinonediazide group-containing compound [B] contained as an essential component in the photosensitive resin composition of the present invention is a photosensitizer and is not particularly limited as long as it is a compound having a quinonediazide group. For example, an ester that can be obtained by condensation of a phenolic compound or an alcoholic compound with 1,2-naphthoquinonediazidesulfonic acid halide is preferred. Among these, from the viewpoint of photosensitivity and transparency of the resin film, a product obtained by condensing 1,2-naphthoquinonediazide sulfonic acid halide corresponding to 30 to 85 mol% with respect to the hydroxyl group in the phenolic compound or alcoholic compound. More preferred is a product obtained by condensing 1,2-naphthoquinonediazide sulfonic acid halide corresponding to 50 to 70 mol%. Specific examples of the phenolic compound or alcoholic compound include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2, 3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3,4,2′-tetrahydroxy-4′-methylbenzophenone, 2,3,4,4 ′ -Tetrahydroxy-3'-methoxybenzophenone, 2,3,4,2 ', 6'-pentahydroxybenzophenone, 2,4,6,3', 4 ', 5'-hexahydroxybenzophenone, 3,4,5 , 3 ′, 4 ′, 5′-hexahydroxybenzophenone, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4 Hydroxyphenyl) -7-hydroxychroman, 2- [bis {(5-isopropyl-4-hydroxy-2-methyl) phenyl} methyl] phenol, 1- [1- (3- {1- (4-hydroxyphenyl)] -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxy Phenyl) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzenebis (2,4-dihydroxyphenyl) methane, bis ( p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 1,1,1-tri (p-hydroxyphenyl) ethane, bis (2,3 4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane , 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxy Phenylmethane, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol, 2,2,4-trimethyl- Examples include 7,2 ′, 4′-trihydroxyflavan. These may be used alone or in combination of two or more. As the compound [B] having a quinonediazide group, 1,2-naphthoquinonediazidesulfone of 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene Acid esters are preferred.
本発明の感光性樹脂組成物において、キノンジアジド基含有化合物［Ｂ］の配合量は、共重合体［Ａ］（固形分）１００質量部に対して、５質量部〜６０質量部であることが好ましく、１０質量部〜５０質量部であることが更に好ましい。キノンジアジド基含有化合物［Ｂ］の配合量が５質量部未満であると、現像不良を起こす場合があり、一方、６０質量部を超えると、現像不良を起こしたり、樹脂膜の透明性、絶縁性及び平坦性が悪くなる場合がある。 In the photosensitive resin composition of the present invention, the compounding amount of the quinonediazide group-containing compound [B] is 5 to 60 parts by mass with respect to 100 parts by mass of the copolymer [A] (solid content). Preferably, it is 10 mass parts-50 mass parts. When the compounding amount of the quinonediazide group-containing compound [B] is less than 5 parts by mass, poor development may occur. On the other hand, when it exceeds 60 parts by mass, poor development may occur or the transparency and insulation of the resin film may occur. In addition, the flatness may be deteriorated.
本発明の感光性樹脂組成物は、共重合体［Ａ］及びキノンジアジド基含有化合物［Ｂ］を必須成分として含有するが、本発明の効果を損なわない範囲で必要に応じて、紫外線吸収剤、増感剤、増感助剤、可塑剤、増粘剤、有機溶媒、分散剤、消泡剤、界面活性剤、密着助剤、感熱性酸生成化合物、共重合体［Ａ］及びキノンジアジド基含有化合物［Ｂ］と架橋反応し得る化合物を含有することができる。 The photosensitive resin composition of the present invention contains a copolymer [A] and a quinonediazide group-containing compound [B] as essential components, and an ultraviolet absorber, if necessary, as long as the effects of the present invention are not impaired. Sensitizer, sensitization aid, plasticizer, thickener, organic solvent, dispersant, antifoaming agent, surfactant, adhesion aid, thermosensitive acid generating compound, copolymer [A] and quinonediazide group A compound capable of undergoing a crosslinking reaction with the compound [B] can be contained.
また、本発明の感光性樹脂組成物は、共重合体［Ａ］及びキノンジアジド基含有化合物［Ｂ］並びに上記の如き任意に添加される他の成分を均一に混合することによって調製され、適当な溶媒に溶解されて溶液状態で用いることができる。 The photosensitive resin composition of the present invention is prepared by uniformly mixing the copolymer [A] and the quinonediazide group-containing compound [B] and other components optionally added as described above. It can be used in a solution state after being dissolved in a solvent.
溶媒としては、共重合体［Ａ］及びキノンジアジド基含有化合物［Ｂ］、並びに任意的に配合されるその他の成分を均一に溶解し、各成分と反応しないものが用いられ、上述した共重合体［Ａ］を製造するために使用できる溶媒として例示したものと同様のものが挙げられる。中でも、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、メトキシブチルアセテート、メトキシプロピオン酸メチル、及びエトキシプロピオン酸エチルは、各成分の溶解性、各成分との反応性、塗膜形成のしやすさ等の点で好ましく使用できる。更に、これらの溶媒とともに膜厚の面内均一性を高めるため、Ｎ−メチルピロリドン、γ−ブチロラクトン、Ｎ，Ｎ−ジメチルアセトアミドなどの高沸点溶媒を併用することもできる。 As the solvent, a copolymer [A], a quinonediazide group-containing compound [B], and other components that are optionally blended are uniformly dissolved, and those that do not react with each component are used. The thing similar to what was illustrated as a solvent which can be used in order to manufacture [A] is mentioned. Among them, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methoxybutyl acetate, methyl methoxypropionate, and ethyl ethoxypropionate are soluble in each component, reactive with each component, It can be preferably used in terms of ease of forming a coating film. Furthermore, in order to improve the in-plane uniformity of the film thickness together with these solvents, a high boiling point solvent such as N-methylpyrrolidone, γ-butyrolactone, N, N-dimethylacetamide may be used in combination.
本発明の感光性樹脂組成物を溶液状態で調製する際、共重合体［Ａ］（固形分）及びキノンジアジド基含有化合物［Ｂ］並びに任意的に添加されるその他の成分の合計量１００質量部に対して、上記溶媒（単独で使用してもよいし、２種以上を組み合わせて使用してもよい）を、３０質量部〜４，０００質量部、好ましくは５０質量部〜３，０００質量部で配合できる。 When preparing the photosensitive resin composition of the present invention in a solution state, the total amount of the copolymer [A] (solid content), the quinonediazide group-containing compound [B] and other components optionally added is 100 parts by mass. On the other hand, the above-mentioned solvent (which may be used alone or in combination of two or more) is 30 to 4,000 parts by mass, preferably 50 to 3,000 parts by mass. Can be blended in parts.
本発明の感光性樹脂組成物は、塗布性、現像性、硬化性及び保存安定性が良好で、これを使用することで透明性、耐熱変色性及び電気特性に優れる樹脂膜を形成することができる。この樹脂膜は、電子部品の保護膜、平坦化膜もしくは層間絶縁膜の形成、マイクロレンズもしくはマイクロレンズアレイの形成、液晶表示素子の光拡散反射膜、配向制御用突起もしくはスペーサーの形成、カラーフィルターの形成、又は光導波路の形成に好適に使用できる。 The photosensitive resin composition of the present invention has good coatability, developability, curability and storage stability, and by using this, a resin film excellent in transparency, heat discoloration and electrical characteristics can be formed. it can. This resin film is a protective film for electronic parts, planarization film or interlayer insulation film formation, microlens or microlens array formation, light diffusive reflection film for liquid crystal display element, formation of alignment control projection or spacer, color filter Or the formation of an optical waveguide.
次に、本発明の感光性樹脂組成物を用いた樹脂膜の形成方法について説明する。先ず、ガラス基板、シリコンウエハー及びこれらの表面に各種金属が形成された基板上に、本発明の感光性樹脂組成物を塗布し、乾燥して感放射線性樹脂膜を形成する。感光性樹脂組成物の塗布方法としては、特に限定されず、例えば、スプレー法、ロールコート法、回転塗布法、バー塗布法、スリット塗布法などの適宜の方法が挙げられる。乾燥条件は、各成分の種類、使用割合などによっても異なるが、例えば６０℃〜１１０℃で３０秒間〜３０分間程度とすることができる。 Next, a method for forming a resin film using the photosensitive resin composition of the present invention will be described. First, the photosensitive resin composition of the present invention is applied on a glass substrate, a silicon wafer, and a substrate on which various metals are formed, and dried to form a radiation-sensitive resin film. The method for applying the photosensitive resin composition is not particularly limited, and examples thereof include appropriate methods such as a spray method, a roll coating method, a spin coating method, a bar coating method, and a slit coating method. The drying conditions vary depending on the type of each component, the use ratio, and the like, but can be, for example, 60 ° C. to 110 ° C. for about 30 seconds to 30 minutes.
次に、形成された樹脂膜に、所定のパターンを有するマスクを介して、放射線を照射した後、現像液を用いて現像処理することでパターニングを行うことができる。このとき用いられる放射線としては、例えばｇ線（波長４３６ｎｍ）、ｉ線（波長３６５ｎｍ）、ＫｒＦエキシマレーザー、ＡｒＦエキシマレーザー、Ｘ線、電子線などが挙げられ、その光源としては、低圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、エキシマレーザー発生装置などが挙げられる。現像処理に用いられる現像液としては、例えば、水酸化ナトリウム、水酸化カリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニア、エチルアミン、ｎ−プロピルアミン、ジエチルアミン、ジエチルアミノエタノール、ジ−ｎ−プロピルアミン、トリエチルアミン、メチルジエチルアミン、ジメチルエタノールアミン、トリエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、ピロール、ピペリジン、１，８−ジアザビシクロ〔５，４，０〕−ウンデセ−７−エン、１，５−ジアザビシクロ〔４，３，０〕−ノネ−５−エンなどのアルカリ（塩基性化合物）の水溶液を用いることができる。また、上記のアルカリの水溶液にメタノール、エタノール等の水溶性有機溶媒や界面活性剤を適当量添加した水溶液、又は本発明の感光性樹脂組成物を溶解する各種有機溶媒を現像液として使用することができる。更に、現像方法としては、液盛り法、ディッピング法、揺動浸漬法、シャワー法などの適宜の方法を利用することができる。このときの現像時間は、感光性樹脂組成物の組成によって異なるが、例えば、３０秒間〜１２０秒間とすることができる。 Next, patterning can be performed by irradiating the formed resin film with radiation through a mask having a predetermined pattern and then developing with a developer. Examples of the radiation used at this time include g-line (wavelength 436 nm), i-line (wavelength 365 nm), KrF excimer laser, ArF excimer laser, X-ray, electron beam, and the like. Examples include mercury lamps, ultra-high pressure mercury lamps, chemical lamps, and excimer laser generators. Examples of the developer used in the development processing include sodium hydroxide, potassium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, and triethylamine. , Methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -undec-7-ene, 1,5- An aqueous solution of an alkali (basic compound) such as diazabicyclo [4,3,0] -none-5-ene can be used. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent or surfactant such as methanol or ethanol to the aqueous alkali solution described above, or various organic solvents that dissolve the photosensitive resin composition of the present invention may be used as a developing solution. Can do. Further, as a developing method, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time at this time varies depending on the composition of the photosensitive resin composition, but can be, for example, 30 seconds to 120 seconds.
次に、パターニングされた樹脂膜に対して、好ましくは例えば流水洗浄によるリンス処理を行い、更に、好ましくは放射線を全面に照射することにより、当該樹脂膜中に残存するキノンジアジド基含有化合物［Ｂ］の分解処理を行う。キノンジアジド基含有化合物［Ｂ］は光を吸収する原因となるため、この後露光により樹脂膜の透明性が向上する。 Next, the patterned resin film is preferably rinsed, for example, by washing with running water, and more preferably by irradiating the entire surface with a quinonediazide group-containing compound [B] remaining in the resin film. Disassembling process. Since the quinonediazide group-containing compound [B] causes light absorption, the post-exposure improves the transparency of the resin film.
次に、ホットプレート、オーブンなどにより加熱処理（ポストベーク処理）することにより、硬化処理を行うことができる。この硬化処理における焼成温度は、例えば、１２０℃〜２５０℃である。加熱時間は、加熱機器の種類により異なるが、例えば、ホットプレート上で加熱処理を行う場合には５分間〜３０分間、オーブン中で加熱処理を行う場合には３０分間〜９０分間とすることができる。特に、マイクロレンズ及び配向制御用突起を形成する際には、２回以上の加熱工程を行うステップベーク法を用いることもでき、具体的にはパターン化された樹脂膜のガラス転移温度以上の温度での初期加熱により、パターンを流動させ、表面張力により半球状にし、次いで、より高温での加熱で架橋を進行させて所定の形状とする。 Next, a curing process can be performed by heat treatment (post-bake process) using a hot plate, an oven, or the like. The baking temperature in this hardening process is 120 to 250 degreeC, for example. The heating time varies depending on the type of the heating device. For example, when heat treatment is performed on a hot plate, it may be 5 minutes to 30 minutes, and when heat treatment is performed in an oven, it may be 30 minutes to 90 minutes. it can. In particular, when forming the microlens and the alignment control protrusion, a step baking method in which the heating process is performed twice or more can be used. Specifically, the temperature is higher than the glass transition temperature of the patterned resin film. The pattern is made to flow by initial heating at, and made hemispherical by surface tension, and then the crosslinking is advanced by heating at a higher temperature to obtain a predetermined shape.
このようにして、目的とする保護膜、平坦化膜、層間絶縁膜、マイクロレンズ又はマイクロレンズアレイ、光拡散反射膜、配向制御用突起、スペーサー、カラーフィルター、光導波路等の各用途に対応する、パターン状薄膜を基板の表面上に形成することができる。このように形成された樹脂膜は、透明性、耐熱変色性及び電気特性に優れたものとなる。 In this way, it corresponds to each application such as a target protective film, planarization film, interlayer insulating film, microlens or microlens array, light diffusion reflection film, alignment control protrusion, spacer, color filter, optical waveguide, etc. A patterned thin film can be formed on the surface of the substrate. The resin film thus formed is excellent in transparency, heat discoloration, and electrical characteristics.
以下、実施例及び比較例を示して、本発明を具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to a following example.
＜共重合体の合成＞
〔実施例１〕
還流冷却器及び攪拌機を備えたフラスコに、ｐ−ヒドロキシフェニルメタクリレート４２質量部、２−（０−［１’−メチルプロピリデンアミノ］カルボキシアミノ）エチルメタクリレート５８質量部、プロピレングリコールモノメチルエーテルアセテート４００質量部及び２，２’−アゾビスイソブチロニトリル６質量部を仕込み、窒素置換した後、攪拌しながら液温を８０℃に上昇させ、８０℃で６時間反応させた。ゲル・パーミエーション・クロマトグラフィーによりモノマーの消失を確認し、１００℃に昇温して３０分間エージングを行った。８０℃、減圧下でプロピレングリコールモノメチルエーテルアセテートを蒸留により取り除き、固形分濃度を３０質量％に調整して、共重合体［Ａ−１］を含む樹脂溶液（Ｓ−１）を得た。
樹脂溶液中に含まれる共重合体［Ａ−１］のポリスチレン換算重量平均分子量（Ｍｗ）は８，７００であり、分子量分布（Ｍｗ／Ｍｎ）は３．５であった。<Synthesis of copolymer>
[Example 1]
In a flask equipped with a reflux condenser and a stirrer, 42 parts by mass of p-hydroxyphenyl methacrylate, 58 parts by mass of 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate, 400 parts by mass of propylene glycol monomethyl ether acetate And 6 parts by mass of 2,2′-azobisisobutyronitrile were charged, and the atmosphere was purged with nitrogen. Then, the liquid temperature was raised to 80 ° C. while stirring, and the mixture was reacted at 80 ° C. for 6 hours. The disappearance of the monomer was confirmed by gel permeation chromatography, and the temperature was raised to 100 ° C. and aging was performed for 30 minutes. Propylene glycol monomethyl ether acetate was removed by distillation under reduced pressure at 80 ° C., and the solid content concentration was adjusted to 30% by mass to obtain a resin solution (S-1) containing the copolymer [A-1].
The copolymer [A-1] contained in the resin solution had a polystyrene-reduced weight average molecular weight (Mw) of 8,700 and a molecular weight distribution (Mw / Mn) of 3.5.
〔実施例２〕
還流冷却器及び攪拌機を備えたフラスコに、ｐ−ヒドロキシフェニルメタクリレート４１質量部、２−[（３，５−ジメチルピラゾリル）カルボニルアミノ］エチルメタクリレート５９質量部、プロピレングリコールモノメチルエーテルアセテート４００質量部及び２，２'−アゾビスイソブチロニトリル６質量部を仕込み、実施例１と同様に反応を行って、共重合体［Ａ−２］を含む樹脂溶液（Ｓ−２）を得た。
樹脂溶液中に含まれる共重合体［Ａ−２］のポリスチレン換算重量平均分子量（Ｍｗ）は８，８００であり、分子量分布（Ｍｗ／Ｍｎ）は３．５であった。[Example 2]
In a flask equipped with a reflux condenser and a stirrer, 41 parts by mass of p-hydroxyphenyl methacrylate, 59 parts by mass of 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate, 400 parts by mass of propylene glycol monomethyl ether acetate and 2 , 2′-azobisisobutyronitrile was charged in an amount of 6 parts by mass and reacted in the same manner as in Example 1 to obtain a resin solution (S-2) containing the copolymer [A-2].
The copolymer [A-2] contained in the resin solution had a polystyrene-reduced weight average molecular weight (Mw) of 8,800 and a molecular weight distribution (Mw / Mn) of 3.5.
〔実施例３〕
還流冷却器及び攪拌機を備えたフラスコに、ｐ−ヒドロキシフェニルメタクリレート３６質量部、２−（０−[１'−メチルプロピリデンアミノ］カルボキシアミノ）エチルメタクリレート５１質量部、ｎ−ブチルアクリレート１３質量部、プロピレングリコールモノメチルエーテルアセテート４００質量部及び２，２'−アゾビスイソブチロニトリル６質量部を仕込み、実施例１と同様に反応を行って、共重合体［Ａ−３］を含む樹脂溶液（Ｓ−３）を得た。
樹脂溶液中に含まれる共重合体［Ａ−３］のポリスチレン換算重量平均分子量（Ｍｗ）は８，３００であり、分子量分布（Ｍｗ／Ｍｎ）は３．３であった。Example 3
In a flask equipped with a reflux condenser and a stirrer, 36 parts by mass of p-hydroxyphenyl methacrylate, 51 parts by mass of 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate, 13 parts by mass of n-butyl acrylate , 400 parts by mass of propylene glycol monomethyl ether acetate and 6 parts by mass of 2,2′-azobisisobutyronitrile were prepared and reacted in the same manner as in Example 1 to obtain a resin solution containing the copolymer [A-3] (S-3) was obtained.
The copolymer [A-3] contained in the resin solution had a polystyrene-reduced weight average molecular weight (Mw) of 8,300 and a molecular weight distribution (Mw / Mn) of 3.3.
〔比較例１〕
還流冷却器及び攪拌機を備えたフラスコに、ｐ−ヒドロキシフェニルメタクリレート５６質量部、グリシジルメタクリレート４４質量部、プロピレングリコールモノメチルエーテルアセテー６００質量部及び２，２’−アゾビスイソブチロニトリル６質量部を仕込み、窒素置換した後、攪拌しながら液温を８０℃に上昇させ、８０℃で６時間反応した。ゲル・パーミエーション・クロマトグラフィーによりモノマーの消失を確認し、１００℃に昇温して３０分間エージングを行った。１００℃、減圧下でプロピレングリコールモノメチルエーテルアセテートを蒸留により取り除き、固形分濃度を３０質量％に調整して、共重合体［Ａ’−４］を含む樹脂溶液（Ｓ−４）を得た。
樹脂溶液中に含まれる共重合体［Ａ’−４］のポリスチレン換算重量平均分子量（Ｍｗ）は８，４００であり、分子量分布（Ｍｗ／Ｍｎ）は３．１であった。[Comparative Example 1]
In a flask equipped with a reflux condenser and a stirrer, 56 parts by mass of p-hydroxyphenyl methacrylate, 44 parts by mass of glycidyl methacrylate, 600 parts by mass of propylene glycol monomethyl ether acetate and 6 parts by mass of 2,2′-azobisisobutyronitrile. Then, the temperature of the solution was raised to 80 ° C. with stirring, and the reaction was carried out at 80 ° C. for 6 hours. The disappearance of the monomer was confirmed by gel permeation chromatography, and the temperature was raised to 100 ° C. and aging was performed for 30 minutes. Propylene glycol monomethyl ether acetate was removed by distillation at 100 ° C. under reduced pressure, and the solid content concentration was adjusted to 30% by mass to obtain a resin solution (S-4) containing the copolymer [A′-4].
The copolymer [A′-4] contained in the resin solution had a polystyrene-reduced weight average molecular weight (Mw) of 8,400 and a molecular weight distribution (Mw / Mn) of 3.1.
＜評価＞
（１）透明性
樹脂溶液（Ｓ−１）〜（Ｓ−４）を、ガラス基板上に膜厚３μｍとなるように塗布し、オーブンにて８０℃で３０分間乾燥した。得られた樹脂膜付きのガラス基板について、分光光度計を使用して、波長４００〜８００ｎｍでの最低透過率をガラス基板をブランクとして測定した。透過率が大きいほど透明性が高い。結果を表１に示す。<Evaluation>
(1) Transparency Resin solutions (S-1) to (S-4) were applied on a glass substrate so as to have a film thickness of 3 μm and dried in an oven at 80 ° C. for 30 minutes. About the obtained glass substrate with a resin film, the minimum transmittance | permeability in wavelength 400-800 nm was measured using the glass substrate as the blank using the spectrophotometer. The greater the transmittance, the higher the transparency. The results are shown in Table 1.
（２）硬化性
樹脂溶液（Ｓ−１）〜（Ｓ−４）を、１５０℃のホットプレート上に膜厚約０．５ｍｍとなるように塗布し、ゲル化するまでの時間を測定した。時間が短いほど硬化性が良好である。結果を表１に示す。(2) Curability The resin solutions (S-1) to (S-4) were applied on a hot plate at 150 ° C. so as to have a film thickness of about 0.5 mm, and the time until gelation was measured. The shorter the time, the better the curability. The results are shown in Table 1.
（３）電気特性
樹脂溶液（Ｓ−１）〜（Ｓ−４）を、金属基板上に膜厚３μｍとなるように塗付し、オーブンにて８０℃で３０分間乾燥した。乾燥した塗膜を２００℃のオーブンで３０分間加熱硬化させた。得られた硬化塗膜の１ＭＨｚでの誘電率を測定した。誘電率が小さいほど電気特性が良好である。結果を表１に示す。(3) Electrical characteristics Resin solutions (S-1) to (S-4) were applied on a metal substrate to a film thickness of 3 μm and dried in an oven at 80 ° C. for 30 minutes. The dried coating film was cured by heating in an oven at 200 ° C. for 30 minutes. The dielectric constant at 1 MHz of the obtained cured coating film was measured. The smaller the dielectric constant, the better the electrical characteristics. The results are shown in Table 1.
＜感光性樹脂組成物の調製＞
〔実施例４〕
実施例１で得られた樹脂溶液（Ｓ−１）１００質量部、１−［１−（４−ヒドロキシフェニル）イソプロピル］−４−［１，１−ビス（４−ヒドロキシフェニル）エチル］ベンゼン−１，２−ナフトキノンジアジド−５−スルホン酸エステル６．２５質量部及びプロピレングリコールモノメチルエーテルアセテート７５質量部を混合溶解し、０．２μｍのメンブランフィルターで濾過を行い、溶液状態の感光性樹脂組成物（Ｓ−５）を調製した。<Preparation of photosensitive resin composition>
Example 4
100 parts by mass of the resin solution (S-1) obtained in Example 1, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene- 6.25 parts by mass of 1,2-naphthoquinonediazide-5-sulfonic acid ester and 75 parts by mass of propylene glycol monomethyl ether acetate are mixed and dissolved, filtered through a 0.2 μm membrane filter, and a photosensitive resin composition in a solution state (S-5) was prepared.
〔実施例５〕
実施例２で得られた樹脂溶液（Ｓ−２）を用い、実施例４と同様に溶液状態の感光性樹脂組成物（Ｓ−６）を調製した。Example 5
Using the resin solution (S-2) obtained in Example 2, a photosensitive resin composition (S-6) in a solution state was prepared in the same manner as in Example 4.
〔実施例６〕
実施例３で得られた樹脂溶液（Ｓ−３）を用い、実施例４と同様に溶液状態の感光性樹脂組成物（Ｓ−７）を調製した。Example 6
Using the resin solution (S-3) obtained in Example 3, a photosensitive resin composition (S-7) in a solution state was prepared in the same manner as in Example 4.
〔比較例２〕
比較例１で得られた樹脂溶液（Ｓ−４）を用い、実施例４と同様に溶液状態の感光性樹脂組成物（Ｓ−８）を調製した。[Comparative Example 2]
Using the resin solution (S-4) obtained in Comparative Example 1, a photosensitive resin composition (S-8) in a solution state was prepared in the same manner as in Example 4.
＜評価＞
（１）保存安定性
感光性樹脂組成物（Ｓ−５）〜（Ｓ−８）を室温で１ヶ月間保存した後の粘度を測定した。なお、粘度は、Ｅ型粘度計を用いて２５℃で測定を行った。調製直後の粘度に対し、室温１ヶ月間保存後の粘度上昇率が１０％未満の場合を○、１０％以上の場合を×とした。結果を表２に示す。<Evaluation>
(1) Storage stability The viscosity after storing the photosensitive resin compositions (S-5) to (S-8) at room temperature for 1 month was measured. The viscosity was measured at 25 ° C. using an E-type viscometer. The case where the rate of increase in viscosity after storage for 1 month at room temperature is less than 10% with respect to the viscosity immediately after the preparation is indicated as ◯, and the case where it is 10% or more is indicated as x. The results are shown in Table 2.
（２）塗布性
感光性樹脂組成物（Ｓ−５）〜（Ｓ−８）を、ガラス基板上に膜厚３μｍとなるように塗布し、オーブンにて８０℃で３０分間乾燥した。何れの感光性樹脂組成物でも厚さが均一な透明な樹脂膜が得られ、塗布性は良好（○）であった。(2) Coating property The photosensitive resin compositions (S-5) to (S-8) were coated on a glass substrate so as to have a film thickness of 3 µm, and dried in an oven at 80 ° C for 30 minutes. In any photosensitive resin composition, a transparent resin film having a uniform thickness was obtained, and the coating property was good (◯).
（３）現像性
乾燥した樹脂膜にポジパターンマスクを介して超高圧水銀灯で露光し、２．３８重量％テトラメチルアンモニウムヒドロキシドの水溶液にて１分間浸漬して現像し、純水でリンスを行った。何れの感光性樹脂組成物でもポジパターンが転写され、現像性は良好（○）であった。(3) Developability The dried resin film is exposed with an ultra-high pressure mercury lamp through a positive pattern mask, immersed in an aqueous solution of 2.38 wt% tetramethylammonium hydroxide for 1 minute, and rinsed with pure water. went. In any photosensitive resin composition, the positive pattern was transferred and the developability was good (◯).
（４）透明性
乾燥した樹脂膜にポジパターンマスクを介さずに全面露光し、オーブンにて２００℃で３０分間加熱硬化させた。得られた硬化樹脂膜付きのガラス基板について、分光光度計を使用して、波長４００〜８００ｎｍでの最低透過率をガラス基板をブランクとして測定した。透過率が大きいほど透明性が高い。結果を表２に示す。(4) Transparency The entire surface of the dried resin film was exposed without using a positive pattern mask, and was cured by heating at 200 ° C. for 30 minutes in an oven. About the obtained glass substrate with a cured resin film, the minimum transmittance | permeability in wavelength 400-800 nm was measured using the glass substrate as the blank using the spectrophotometer. The greater the transmittance, the higher the transparency. The results are shown in Table 2.
（５）耐熱変色性
２００℃で３０分間加熱硬化させた後、再び２３０℃で１０時間加熱処理し、波長４００ｎｍでの透過率をガラス基板をブランクとして測定した。透過率が大きいほど耐熱変色性が高い。結果を表２に示す。(5) Heat-resistant discoloration property After heat-curing at 200 ° C. for 30 minutes, heat treatment was again performed at 230 ° C. for 10 hours, and the transmittance at a wavelength of 400 nm was measured using a glass substrate as a blank. The greater the transmittance, the higher the heat discoloration. The results are shown in Table 2.
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| JP2012118279A (en) * | 2010-11-30 | 2012-06-21 | Jsr Corp | Radiation-sensitive resin composition, cured film for display element, formation method of cured film for display element, and display element |
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