JP5528652B2 - Photosensitive resin and photosensitive resin composition - Google Patents
Photosensitive resin and photosensitive resin composition Download PDFInfo
- Publication number
- JP5528652B2 JP5528652B2 JP2006203084A JP2006203084A JP5528652B2 JP 5528652 B2 JP5528652 B2 JP 5528652B2 JP 2006203084 A JP2006203084 A JP 2006203084A JP 2006203084 A JP2006203084 A JP 2006203084A JP 5528652 B2 JP5528652 B2 JP 5528652B2
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- JP
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- Prior art keywords
- meth
- acrylate
- photosensitive resin
- mass
- parts
- 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 50
- 239000011347 resin Substances 0.000 title claims description 50
- 239000011342 resin composition Substances 0.000 title claims description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 91
- 239000010408 film Substances 0.000 claims description 53
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 19
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000000059 patterning Methods 0.000 claims description 3
- -1 alicyclic acrylate compounds Chemical class 0.000 description 35
- 229920000642 polymer Polymers 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 150000003254 radicals Chemical class 0.000 description 14
- 239000000243 solution Substances 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 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 8
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 8
- XYXBMCIMPXOBLB-UHFFFAOYSA-N 3,4,5-tris(dimethylamino)-2-methylphenol Chemical compound CN(C)C1=CC(O)=C(C)C(N(C)C)=C1N(C)C XYXBMCIMPXOBLB-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000003384 imaging method Methods 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000004973 liquid crystal related substance Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000007787 solid 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
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000002845 discoloration Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000758 substrate Substances 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
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000010538 cationic polymerization reaction Methods 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-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
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 239000000126 substance 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-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
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 2
- JFWFAUHHNYTWOO-UHFFFAOYSA-N 2-[(2-ethenylphenyl)methoxymethyl]oxirane Chemical compound C=CC1=CC=CC=C1COCC1OC1 JFWFAUHHNYTWOO-UHFFFAOYSA-N 0.000 description 2
- OCKQMFDZQUFKRD-UHFFFAOYSA-N 2-[(3-ethenylphenyl)methoxymethyl]oxirane Chemical compound C=CC1=CC=CC(COCC2OC2)=C1 OCKQMFDZQUFKRD-UHFFFAOYSA-N 0.000 description 2
- ZADXFVHUPXKZBJ-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methoxymethyl]oxirane Chemical compound C1=CC(C=C)=CC=C1COCC1OC1 ZADXFVHUPXKZBJ-UHFFFAOYSA-N 0.000 description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-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
- XAYDWGMOPRHLEP-UHFFFAOYSA-N 6-ethenyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCCC2OC21C=C XAYDWGMOPRHLEP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-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
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 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
- 229930006000 Sucrose Natural products 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000012965 benzophenone Substances 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
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
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- 229940011051 isopropyl acetate Drugs 0.000 description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 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
- 229920002223 polystyrene Polymers 0.000 description 2
- 229940090181 propyl acetate Drugs 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003303 reheating Methods 0.000 description 2
- 230000035945 sensitivity Effects 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
- 229910000679 solder Inorganic materials 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
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- 239000004094 surface-active agent Substances 0.000 description 2
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
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- 239000008096 xylene Substances 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-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
- 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
- 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
- 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
- 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 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-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
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- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
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- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- OQQTZLSEKBDXRS-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyl carbonate Chemical compound CC(C)OC(=O)OC(=O)OC(C)C OQQTZLSEKBDXRS-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
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- ROEHNQZQCCPZCH-UHFFFAOYSA-N tert-butyl 2-tert-butylperoxycarbonylbenzoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)OC(C)(C)C ROEHNQZQCCPZCH-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- BZBMBZJUNPMEBD-UHFFFAOYSA-N tert-butyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC(C)(C)C)CC1C=C2 BZBMBZJUNPMEBD-UHFFFAOYSA-N 0.000 description 1
- JZFHXRUVMKEOFG-UHFFFAOYSA-N tert-butyl dodecaneperoxoate Chemical compound CCCCCCCCCCCC(=O)OOC(C)(C)C JZFHXRUVMKEOFG-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
- 239000002562 thickening agent Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 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
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
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Landscapes
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Materials For Photolithography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Optical Filters (AREA)
Description
本発明は感光性樹脂及びそれを含む感光性樹脂組成物に関するものであり、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や層間絶縁膜、カラーフィルタを形成する三原色（赤、緑、青）の画素、ブラックマトリッス、平坦化膜、柱状スペーサーを形成する材料、有機ＥＬ素子の絶縁膜、マイクロレンズ材料、更には光導波路材料として有用である。 The present invention relates to a photosensitive resin and a photosensitive resin composition containing the same, and more specifically, forms a protective film, an interlayer insulating film, and a color filter for electronic components such as liquid crystal display elements, integrated circuit elements, and solid-state imaging elements. It is useful as a pixel for three primary colors (red, green, blue), black matrix, flattening film, columnar spacer, organic EL element insulating film, microlens material, and optical waveguide material.
従来よりＴＦＴ型液晶表示素子や磁気ヘッド素子、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や、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。 Conventionally, a protective film for preventing deterioration and damage of electronic components such as TFT liquid crystal display elements, magnetic head elements, integrated circuit elements, solid-state imaging elements, and 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.
従って、層間絶縁膜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、耐熱性、平坦性、密着性、耐薬品性、電気特性に優れた被膜を形成できることが求められる。
同様に液晶表示素子や固体撮像素子などに使用されるカラーフィルタを製作するために用いられる材料としては、様々なネガ型の感光性樹脂組成物が使用されているが、パターン特性や現像性には、まだまだ改良の余地がある。
Therefore, the photosensitive resin composition for forming the interlayer insulating film is required to be excellent in developability and to be able to form a film excellent in transparency, heat resistance, flatness, adhesion, chemical resistance, and electrical characteristics.
Similarly, various negative photosensitive resin compositions are used as materials used to manufacture color filters used in liquid crystal display elements and solid-state imaging elements. There is still room for improvement.
また、ファクシミリ、電子複写機、固体撮像素子等に用いられる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、また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、メルトフロー性かつ耐熱性が求められ、集光度の観点から高い屈折率が求められる。 Moreover, as an optical system material for an imaging optical system of an on-chip color filter or an optical fiber connector used for a facsimile, an electronic copying machine, a solid-state imaging device, or the like, a microlens having a lens diameter of about 3 to 100 μm, or a microlens thereof. A microlens array in which lenses are regularly arranged 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.
また、近年、動作周波数及び伝送速度の増加に伴い光電気混載基板用の光導波路材料として、透明性、耐熱性に優れるフッ素化ポリイミド等が検討されているが、経済的に問題があり、また、アクリル系光硬化樹脂、ポリカーボネート、脂環式ポリマー等は、耐熱性が不十分であり実用化を妨げている。 In recent years, fluorinated polyimide having excellent transparency and heat resistance has been studied as an optical waveguide material for an opto-electric hybrid board with an increase in operating frequency and transmission speed. However, there are economical problems. In addition, acrylic photo-curing resins, polycarbonates, alicyclic polymers, and the like are insufficient in heat resistance and hinder practical application.
これらの透明性や耐熱性に優れる光硬化性樹脂としては、例えば特許文献１に示される脂環式アクリレート化合物から得られるアルカリ現像可能な硬化性樹脂、特許文献２に示されるカルボキシル基及び（メタ）アクリロイル基を有する重合体を含む感光性樹脂組成物等が検討されている。しかし、パターン形成における感度及び解像度、硬化物の透明性、耐熱性及び耐熱変色性等においては充分満足できるものではない。 Examples of these photocurable resins having excellent transparency and heat resistance include alkali-developable curable resins obtained from alicyclic acrylate compounds disclosed in Patent Document 1, carboxyl groups and (Metal) described in Patent Document 2. ) A photosensitive resin composition containing a polymer having an acryloyl group has been studied. However, the sensitivity and resolution in pattern formation, transparency of the cured product, heat resistance and heat discoloration are not fully satisfactory.
また、一般的に光硬化性樹脂としてアクリレート化合物が使用されているが、耐熱性が必要な点で、プリント基板のソルダーレジスト等にはノボラック樹脂をベースとしたエポキシアクリレートが使用されている。また、半導体の実装材料として、半田バンプ形成用の厚膜レジスト等にはポリヒドロキシスチレンをベースとしたネガ型樹脂組成物が使用されている。例えば、特許文献３にはアルケニルフェノールに不飽和基を導入した単位を含む重合体からなる光硬化性組成物が記載されている。
本発明は感光性樹脂及びそれを含む感光性樹脂組成物に関するものであり、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や層間絶縁膜、カラーフィルタを形成する三原色（赤、緑、青）の画素、ブラックマトリックス、平坦化膜、柱状スペーサーを形成する材料、有機ＥＬ素子の絶縁膜、マイクロレンズ材料、更には光導波路材料として好適な物であり、本発明の目的は、光硬化性、硬化物の透明性、耐熱性及び耐熱変色性に優れる感光性樹脂及びそれを含む感光性樹脂組成物を提供することにある。 The present invention relates to a photosensitive resin and a photosensitive resin composition containing the same, and more specifically, forms a protective film, an interlayer insulating film, and a color filter for electronic components such as liquid crystal display elements, integrated circuit elements, and solid-state imaging elements. The present invention is suitable as a pixel for three primary colors (red, green, blue), a black matrix, a planarizing film, a material for forming a columnar spacer, an insulating film for an organic EL element, a microlens material, and an optical waveguide material. The objective of this is to provide the photosensitive resin excellent in photocurability, transparency of hardened | cured material, heat resistance, and heat discoloration, and the photosensitive resin composition containing the same.
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）アクリレートを含む重合体または共重合体に不飽和二重結合を導入した感光性樹脂、及び該感光性樹脂と光ラジカル開始剤、ラジカル重合性モノマー及び／又は有機溶剤を含有する感光性樹脂組成物により上記目的を達成できることを見出した。
即ち、本発明は以下の通りである。
As a result of earnest studies to achieve the above object, a photosensitive resin in which an unsaturated double bond is introduced into a polymer or copolymer containing hydroxyphenyl (meth) acrylate, the photosensitive resin, a photo radical initiator, and a radical It has been found that the above object can be achieved by a photosensitive resin composition containing a polymerizable monomer and / or an organic solvent.
That is, the present invention is as follows.
（１）グリシジル（メタ）アクリレートと２０モル％以上のヒドロキシフェニル（メタ）アクリレートを構成成分として含有する共重合体のグリシジル基に対して、不飽和二重結合を有する化合物を付加反応させて得られる感光性樹脂。 (1) A compound having an unsaturated double bond is added to a glycidyl group of a copolymer containing glycidyl (meth) acrylate and 20 mol% or more of hydroxyphenyl (meth) acrylate as constituent components. The obtained photosensitive resin.
（２）不飽和二重結合を有する化合物が、不飽和一塩基酸である上記（１）に記載の感光性樹脂。
（３）平均分子量（Ｍｗ）が１，５００〜５０，０００である上記（１）または（２）に記載の感光性樹脂。
（４）上記（１）〜（３）のいずれかに記載の感光性樹脂、光ラジカル開始剤、ラジカル重合性モノマー及び／又は有機溶剤を含有する感光性樹脂組成物。
（５）上記（４）に記載の感光性樹脂組成物を塗布、乾燥して得られる塗膜。
（６）上記（５）に記載の塗膜をパターニングして得られる薄膜。
(2) The photosensitive resin as described in said (1) whose compound which has an unsaturated double bond is unsaturated monobasic acid.
(3) The photosensitive resin as described in said (1) or (2) whose average molecular weight (Mw) is 1,500-50,000.
(4) The photosensitive resin composition containing the photosensitive resin in any one of said (1)- (3) , a photoradical initiator, a radically polymerizable monomer, and / or an organic solvent.
(5) The coating film obtained by apply | coating and drying the photosensitive resin composition as described in said (4) .
(6) A thin film obtained by patterning the coating film according to (5) .
本発明の感光性樹脂及び感光性樹脂組成物を使用する事で光硬化性、硬化物の透明性、耐熱性及び耐熱変色性に優れる皮膜を形成することができ、電子部品の保護膜や層間絶縁膜、カラーフィルタを形成する材料、有機ＥＬ素子の絶縁膜、マイクロレンズ材料、更には光導波路材料として好適に使用できる。 By using the photosensitive resin and the photosensitive resin composition of the present invention, a film excellent in photocurability, transparency of the cured product, heat resistance, and heat discoloration can be formed. It can be suitably used as an insulating film, a material for forming a color filter, an insulating film for an organic EL element, a microlens material, and an optical waveguide material.
以下、本発明の感光性樹脂及び感光性樹脂組成物について詳述する。
本発明の感光性樹脂はヒドロキシフェニル（メタ）アクリレートを含む重合体または共重合体に不飽和二重結合を導入した樹脂である。
先ず、ヒドロキシフェニル（メタ）アクリレートを含む重合体または共重合体について説明する。
ヒドロキシフェニル（メタ）アクリレートを含む重合体は、ヒドロキシフェニル（メタ）アクリレートからなる構成単位を必須成分として含み、具体的には、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の重合体が挙げられ、これらの単独又は２種以上を組み合わせて使用できる。
Hereinafter, the photosensitive resin and photosensitive resin composition of the present invention will be described in detail.
The photosensitive resin of the present invention is a resin in which an unsaturated double bond is introduced into a polymer or copolymer containing hydroxyphenyl (meth) acrylate.
First, a polymer or copolymer containing hydroxyphenyl (meth) acrylate will be described.
The polymer containing hydroxyphenyl (meth) acrylate contains a constituent unit composed of hydroxyphenyl (meth) acrylate as an essential component, specifically, o-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate. , Polymers of o-hydroxyphenyl methacrylate, m-hydroxyphenyl methacrylate, and p-hydroxyphenyl methacrylate can be used, and these can be used alone or in combination of two or more.
ヒドロキシフェニル（メタ）アクリレートを含む共重合体はヒドロキシフェニル（メタ）アクリレートと不飽和基含有重合性化合物との共重合体である。この場合、ヒドロキシフェニル（メタ）アクリレートの共重合割合として、全成分の２０モル％以上、好ましくは４０モル％以上の範囲が良い。共重合割合が２０モル％未満の場合、アルカリ溶解性が不十分になり良好なパターンを形成できない。 The copolymer containing hydroxyphenyl (meth) acrylate is a copolymer of hydroxyphenyl (meth) acrylate and an unsaturated group-containing polymerizable compound. In this case, the copolymerization ratio of hydroxyphenyl (meth) acrylate is in the range of 20 mol% or more, preferably 40 mol% or more of all components. When the copolymerization ratio is less than 20 mol%, the alkali solubility becomes insufficient and a good pattern cannot be formed.
この不飽和基含有重合性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）アクリロイロキシエチル〕、フタル酸モノ〔２−（メタ）アクリロイロキシエチル〕、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、 Examples of the unsaturated group-containing polymerizable compound include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, maleic anhydride, fumaric anhydride, citraconic anhydride, and mesaconic anhydride. Acid, itaconic anhydride, vinyl benzoic acid, o-carboxyphenyl (meth) acrylate, m-carboxyphenyl (meth) acrylate, p-carboxyphenyl (meth) acrylate, o-carboxyphenyl (meth) acrylamide, m-carboxyphenyl (Meth) acrylamide, p-carboxyphenyl (meth) acrylamide, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (Meta) Acrelay 5-carboxybicyclo [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,
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）アクリロイロキシエチルグリコサイド、 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) ac Relate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2- (meth) acryloyloxyethylglycoside,
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、 Phenyl (meth) acrylate, benzyl (meth) acrylate, o-methoxyphenyl (meth) acrylate, m-methoxyphenyl (meth) acrylate, p-methoxyphenyl (meth) acrylate, 3-methyl-4-hydroxyphenyl (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. .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′-hydroxyethyl) 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-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [ 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,
グリシジル（メタ）アクリレート、α−エチル（メタ）アクリル酸グリシジル、（メタ）アクリル酸−３，４−エポキシブチル、α−エチル（メタ）アクリル酸−３，４−エポキシブチル、（メタ）アクリル酸−６，７−エポキシヘプチル、α−エチル（メタ）アクリル酸−６，７−エポキシヘプチル、ビニルグリシジルエーテル、アリルグリシジルエーテル、イソプロペニルグリシジルエーテル、ｏ−ビニルベンジルグリシジルエーテル、ｍ−ビニルベンジルグリシジルエーテル、ｐ−ビニルベンジルグリシジルエーテル、ビニルシクロヘキセンモノオキサイド、３，４−エポキシシクロヘキシルメチル（メタ）アクリレート、２−（メタ）アクリロイルオキシエチルイソシアネート Glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, (meth) acrylic acid-3,4-epoxybutyl, α-ethyl (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid -6,7-epoxyheptyl, α-ethyl (meth) acrylic acid-6,7-epoxyheptyl, vinyl glycidyl ether, allyl glycidyl ether, isopropenyl glycidyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether , P-vinylbenzyl glycidyl ether, vinylcyclohexene monooxide, 3,4-epoxycyclohexylmethyl (meth) acrylate, 2- (meth) acryloyloxyethyl isocyanate
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）アクリレート等が挙げられ、これらの単独又は２種以上を組み合わせて使用できる。これらは透明性、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。上記の中では（メタ）アクリル酸、グリシジル（メタ）アクリレートが好ましい。 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) acrylamide, m-hydroxyphenyl (meth) acrylamide, p-hydroxyphenyl ( (Meth) acrylamide, 3,5-dimethyl-4-hydroxybenzyl (meth) acrylamide, phenylmaleimide, hydroxyphenylmaleimide, cyclohexylmaleimide, benzylmaleimide, trifluoromethyl (meth) acyl Rate and the like, can be used in combination of at least these alone or in combination. In order to adjust transparency, heat resistance, adhesion, chemical resistance, electrical properties, refractive index, coatability, developability, storage stability, mechanical strength, etc., within the range that does not adversely affect each property. Any ratio can be used. Among the above, (meth) acrylic acid and glycidyl (meth) acrylate are preferable.
ヒドロキシフェニル（メタ）アクリレートを必須成分とする重合体またはヒドロキシフェニル（メタ）アクリレートと上記の不飽和化合物との共重合体を得る方法としてはラジカル重合、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、ヒドロキシフェニル（メタ）アクリレート、必要により別の不飽和化合物の合計量を好ましくは１０〜５０質量％の範囲で含有する重合溶媒中で、重合開始剤を用いて重合することができる。分子量の調整は溶媒量、開始剤量、重合温度を調整することで可能であり、ポリスチレン換算重量平均分子量はＭｗ：１，５００〜４５，０００、好ましくは２，０００〜２０，０００の範囲内が良い。分子量が１，５００未満では平坦な塗膜が得られなかったり、現像後の残膜率の低下、あるいは得られるパターンの形状、耐熱性の悪化などを招き、４０，０００を越えると現像性が低下したり、パターン形状が悪化することがあり好ましくない。これらの分子量範囲の重合体又は共重合体を使用することで、Ｍｗ：１，５００〜５０，０００の感光性樹脂が得られる。
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も出来る。
As a method for obtaining a polymer comprising hydroxyphenyl (meth) acrylate as an essential component or a copolymer of hydroxyphenyl (meth) acrylate and the above unsaturated compound, radical polymerization, cationic polymerization, anionic polymerization, coordination anionic polymerization, etc. Is mentioned. Specifically, polymerization may be carried out using a polymerization initiator in a polymerization solvent containing hydroxyphenyl (meth) acrylate and, if necessary, the total amount of another unsaturated compound, preferably in the range of 10 to 50% by mass. it can. The molecular weight can be adjusted by adjusting the amount of the solvent, the amount of the initiator, and the polymerization temperature. The weight average molecular weight in terms of polystyrene is Mw: 1,500 to 45,000, preferably 2,000 to 20,000. Is good. If the molecular weight is less than 1,500, a flat coating film cannot be obtained, or the remaining film ratio after development is reduced, or the shape of the resulting pattern and the heat resistance are deteriorated. It is not preferable because it may decrease or the pattern shape may deteriorate. By using a polymer or copolymer in the molecular weight range, a photosensitive resin having Mw of 1,500 to 50,000 can be obtained.
The molecular weight can be adjusted by using a chain transfer agent typified by mercaptans.
反応溶媒としては、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、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、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などが使用できる。 As reaction solvents, 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, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dimethyl sulfoxide, dimethylformamide, dimethylacetamide and the like can be used.
重合開始剤は、ラジカル重合開始剤、カチオン重合開始剤、アニオン重合開始剤等を使用できるが、ラジカル重合開始剤としては例えば、アゾビスイソブチロニトリル、アゾビス−２，４−ジメチルバレロニトリル、アゾビスシクロヘキサンカルボニトリル、アゾビス−２−アミジノプロパン塩酸塩、アゾビスイソ酪酸ジメチル、アゾビスイソブチルアミジン塩酸塩または４，４‘−アゾビス−４−シアノ吉草酸等のアゾ系開始剤、過酸化ベンゾイル、２，４−ジクロル過酸化ベンゾイル、過酸化ジ−ｔｅｒｔ−ブチル、過酸化ラウロイル、過酸化アセチル、過酸化ジイソプロピルジカーボネート、クメンヒドロパーオキシド、ｔｅｒｔ−ブチルヒドロパーオキシド、ジクミルパーオキシド、ｐ−メタンヒドロパーオキシド、ピナンヒドロパーオキシド、メチルエチルケトンパーオキシド、シクロヘキサノンパーオキシド、ジイソプロピルパーオキシジカルボナート、ｔｅｒｔ−ブチルパーオキシラウレート、ｔｅｒｔ−ブチルパーオキシベンゾエート、ジ−ｔｅｒｔ−ブチルパーオキシフタレート、ジベンジルオキシドまたは２，５−ジメチルヘキサン−２，５−ジヒドロパーオキシド等の過酸化物系開始剤、または過酸化ベンゾイル−Ｎ，Ｎ−ジメチルアニリンまたはペーオキソ二硫酸−亜硫酸水素ナトリウム等のレドック系開始剤が挙げられる。これらのラジカル重合開始剤は、単独でもまたは２種以上を同時にまたは順次使用する事ができる。 As the polymerization initiator, a radical polymerization initiator, a cationic polymerization initiator, an anionic polymerization initiator and the like can be used. Examples of the radical polymerization initiator include azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, Azo initiators such as azobiscyclohexanecarbonitrile, azobis-2-amidinopropane hydrochloride, dimethyl azobisisobutyrate, azobisisobutylamidine hydrochloride or 4,4′-azobis-4-cyanovaleric acid, benzoyl peroxide, 2 , 4-Dichlorobenzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, acetyl peroxide, diisopropyl dicarbonate, cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, p-methane Hydroperoxide, Pinan hydropa Oxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, di-tert-butyl peroxyphthalate, dibenzyl oxide or 2,5-dimethyl Examples thereof include peroxide initiators such as hexane-2,5-dihydroperoxide, and redox initiators such as benzoyl peroxide-N, N-dimethylaniline or peroxodisulfuric acid-sodium hydrogen sulfite. These radical polymerization initiators can be used alone or in combination of two or more simultaneously or sequentially.
カチオン重合開始剤としては、通常のカチオン重合において用いられる開始剤は何れも使用する事ができ、例えば、三フッ化ホウ素、三塩化アルミニウム、四塩化錫、四塩化チタン、五塩化アンチモン等のフリーデル・クラフツ型触媒、硫酸、塩酸、リン酸等の水素酸、ヨード、その他広義の酸を挙げることができる。 As the cationic polymerization initiator, any initiator used in ordinary cationic polymerization can be used, for example, free of boron trifluoride, aluminum trichloride, tin tetrachloride, titanium tetrachloride, antimony pentachloride, etc. Examples include Dell-Crafts-type catalysts, hydrogen acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, iodine, and other broadly defined acids.
アニオン重合開始剤としては、リチウム、ナトリウム等のアルカリ金属およびアルカリアミド、アルカリアルコラート、或いは有機アルカリ金属化合物、グリニヤール試薬、有機アルカリ土類金属化合物、その他広義の塩基を挙げることができる。 Examples of the anionic polymerization initiator include alkali metals such as lithium and sodium, alkali amides, alkali alcoholates, organic alkali metal compounds, Grignard reagents, organic alkaline earth metal compounds, and other broad bases.
次に、ヒドロキシフェニル（メタ）アクリレートを含む重合体または共重合体に不飽和二重結合を導入する方法について説明する。
導入方法は特に制限なく、一般的にはビニル基、アリル基、（メタ）アクリロイル基、などの不飽和二重結合を有する化合物をヒドロキシフェニル（メタ）アクリレートを含む重合体または共重合体に付加反応させることが挙げられる。
この好ましい態様としては例えば、ヒドロキシフェニル（メタ）アクリレートを少なくとも構成成分として含有する重合体にグリシジル（メタ）アクリレートを付加させる方法、ヒドロキシフェニル（メタ）アクリレート及び（メタ）アクリル酸を少なくとも構成成分として含有する重合体にグリシジル（メタ）アクリレートを付加させる方法、ヒドロキシフェニル（メタ）アクリレート及びグリシジル（メタ）アクリレートを少なくとも構成成分として含有する重合体に不飽和一塩基酸を付加させる方法等が挙げられる。
Next, a method for introducing an unsaturated double bond into a polymer or copolymer containing hydroxyphenyl (meth) acrylate will be described.
The introduction method is not particularly limited, and generally a compound having an unsaturated double bond such as a vinyl group, an allyl group or a (meth) acryloyl group is added to a polymer or copolymer containing hydroxyphenyl (meth) acrylate. The reaction can be mentioned.
As this preferable embodiment, for example, a method of adding glycidyl (meth) acrylate to a polymer containing at least hydroxyphenyl (meth) acrylate as a constituent component, hydroxyphenyl (meth) acrylate and (meth) acrylic acid as at least constituent components Examples thereof include a method of adding glycidyl (meth) acrylate to the polymer to be contained, a method of adding unsaturated monobasic acid to a polymer containing at least hydroxyphenyl (meth) acrylate and glycidyl (meth) acrylate as constituent components, and the like. .
その他付加反応に使用できる化合物としてはエポキシ基含有不飽和重合性化合物、イソシアネート基含有重合性化合物などが挙げられる。例えば脂肪族エポキシ基含有不飽和化合物としては具体的には、グリシジル（メタ）アクリレート、α−エチル（メタ）アクリル酸グリシジル、（メタ）アクリル酸−３，４−エポキシブチル、α−エチル（メタ）アクリル酸−３，４−エポキシブチル、（メタ）アクリル酸−６，７−エポキシヘプチル、α−エチル（メタ）アクリル酸−６，７−エポキシヘプチル、ビニルグリシジルエーテル、アリルグリシジルエーテル、イソプロペニルグリシジルエーテル、ｏ−ビニルベンジルグリシジルエーテル、ｍ−ビニルベンジルグリシジルエーテル、ｐ−ビニルベンジルグリシジルエーテルなどが挙げられ、脂環式エポキシ基含有不飽和化合物としては、ビニルシクロヘキセンモノオキサイド、３，４−エポキシシクロヘキシルメチル（メタ）アクリレート、２−（メタ）アクリロイルオキシエチルイソシアネートなどが挙げられ、これらの単独又は２種以上を組み合わせて使用できる。 Other compounds that can be used in the addition reaction include an epoxy group-containing unsaturated polymerizable compound and an isocyanate group-containing polymerizable compound. For example, specific examples of the aliphatic epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, α-ethyl (meth) ) Acrylic acid 3,4-epoxybutyl, (meth) acrylic acid-6,7-epoxyheptyl, α-ethyl (meth) acrylic acid-6,7-epoxyheptyl, vinyl glycidyl ether, allyl glycidyl ether, isopropenyl Examples include glycidyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and alicyclic epoxy group-containing unsaturated compounds include vinyl cyclohexene monooxide and 3,4-epoxy. Cyclohexylmethyl (meth) a Relate, 2- (meth) acrylate such as acryloyloxyethyl isocyanate and the like, it can be used in combination of at least these alone or in combination.
カルボキシル基及びフェノール性水酸基と反応し得る上記不飽和重合性化合物をヒドロキシフェニル（メタ）アクリレートを含む重合体または共重合体に付加反応させるには、無触媒でも良いが、アミン系触媒、リン系触媒、金属触媒等を用いて、６０℃から１３０℃、好ましくは７０℃から１２０℃で１時間から１２時間程度で反応できる。反応中のゲル化防止の目的でエアーバブリングやヒドロキノン等の重合禁止剤を併用することが好ましい。付加モル数は特に規定はしないが、現像性、光硬化性、塗膜物性等を考慮して決めることができる。例えば、上記不飽和重合性化合物がグリシジル（メタ）アクリレートの場合は以下の割合で反応させるのが良い。 For the addition reaction of the unsaturated polymerizable compound capable of reacting with a carboxyl group and a phenolic hydroxyl group to a polymer or copolymer containing hydroxyphenyl (meth) acrylate, no catalyst may be used. Using a catalyst, a metal catalyst or the like, the reaction can be carried out at 60 to 130 ° C., preferably 70 to 120 ° C. for about 1 to 12 hours. For the purpose of preventing gelation during the reaction, it is preferable to use a polymerization inhibitor such as air bubbling or hydroquinone together. The number of added moles is not particularly specified, but can be determined in consideration of developability, photocurability, coating film properties, and the like. For example, when the unsaturated polymerizable compound is glycidyl (meth) acrylate, the reaction is preferably carried out at the following ratio.
ヒドロキシフェニル（メタ）アクリレートからなる重合体のフェノール性水酸基にグリシジル（メタ）アクリレートを付加させる場合には、重合体中のフェノール性水酸基１．０当量に対して、グリシジル（メタ）アクリレートを０．２〜０．８当量の割合で反応させるのが良い。 When glycidyl (meth) acrylate is added to the phenolic hydroxyl group of a polymer composed of hydroxyphenyl (meth) acrylate, glycidyl (meth) acrylate is added to 1.0 equivalent of 1.0 equivalent of phenolic hydroxyl group in the polymer. It is good to make it react in the ratio of 2-0.8 equivalent.
また、ヒドロキシフェニル（メタ）アクリレート及び（メタ）アクリル酸からなる重合体のカルボキシル基にグリシジル（メタ）アクリレートを付加させる場合には、先ずヒドロキシフェニル（メタ）アクリレート及び（メタ）アクリル酸を４０〜８０モル％：６０〜２０モル％で共重合し、共重合体中のカルボキシル基１．０当量に対して、グリシジル（メタ）アクリレートを０．８〜１．５当量の割合で反応させるのが良い。 Moreover, when adding glycidyl (meth) acrylate to the carboxyl group of the polymer which consists of hydroxyphenyl (meth) acrylate and (meth) acrylic acid, first, hydroxyphenyl (meth) acrylate and (meth) acrylic acid are 40- 80 mol%: copolymerization is performed at 60 to 20 mol%, and glycidyl (meth) acrylate is reacted at a ratio of 0.8 to 1.5 equivalents with respect to 1.0 equivalent of carboxyl groups in the copolymer. good.
また、ヒドロキシフェニル（メタ）アクリレート及びグリシジル（メタ）アクリレートからなる重合体のグリシジル基に不飽和一塩基酸を付加させる場合には、先ずヒドロキシフェニル（メタ）アクリレートとグリシジル（メタ）アクリレートを２０〜８０モル％：８０〜２０モル％で共重合し、共重合体中のグリシジル基１．０当量に対して、不飽和一塩基酸を０．５〜１．０当量の割合で反応させるのが良い。 When an unsaturated monobasic acid is added to the glycidyl group of a polymer comprising hydroxyphenyl (meth) acrylate and glycidyl (meth) acrylate, first, hydroxyphenyl (meth) acrylate and glycidyl (meth) acrylate are added in an amount of 20 to 80 mol%: copolymerization is performed at 80 to 20 mol%, and an unsaturated monobasic acid is reacted at a ratio of 0.5 to 1.0 equivalent with respect to 1.0 equivalent of glycidyl group in the copolymer. good.
これらの範囲から逸脱すると、現像性の低下、感度の低下、塗膜物性の低下を招く恐れがある。 If deviating from these ranges, the developability, sensitivity, and film properties may be degraded.
本発明の感光性樹脂の使用方法について記載する。本発明の感光性樹脂は好ましくは次に記載する感光性樹脂組成物として使用することが好ましいが、本感光性樹脂にラジカル重合性モノマー及び／又は有機溶剤を添加して、塗膜形成後、加熱のみで硬化させる事もできる。 It describes about the usage method of the photosensitive resin of this invention. The photosensitive resin of the present invention is preferably used as the photosensitive resin composition described below, but after adding a radical polymerizable monomer and / or an organic solvent to the photosensitive resin and forming a coating film, It can be cured only by heating.
次に、本発明の感光性樹脂組成物について記載する。本発明の感光性樹脂組成物は、上述した感光性樹脂の他、光ラジカル開始剤、ラジカル重合性モノマー及び／又は有機溶剤を含有する感光性樹脂組成物である。 Next, the photosensitive resin composition of the present invention will be described. The photosensitive resin composition of the present invention is a photosensitive resin composition containing a photo radical initiator, a radical polymerizable monomer and / or an organic solvent in addition to the above-described photosensitive resin.
光ラジカル開始剤としては、ベンゾイン類、アセトフェノン類、ベンゾフェノン類、アントラキノン類、キサントン類、チオキサントン類、ケタール類、ホスフィンオキサイド類などが挙げられ、具体的には例えば２，２‘−ジメトキシ−１，２−ジフェニルエタン−１−オン、１−ヒドロキシ−シクロヘキシル−フェニル−ケトン、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン、ベンゾフェノン、１−[４−（２−ヒドロキシエトキシ）−フェニル]−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、２−メチル−１−[４−（メチルチオ）フェニル]−２−モルフォリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１、ビス（２，６−ジメトキシベンゾイル）２，４，４−トリメチル−ペンチルフォスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド等を挙げることができ、これらの１種若しくは２種以上を組み合わせても良い。又、必要に応じて増感剤アミン類、例えばジメチルアミノエチルメタクリレート、ｎ−ブチルアミン、トリエチルアミン、４−ジメチルアミノ安息香酸イソアミル等を適量併用することができる。光ラジカル開始剤は、活性エネルギー線の光源として、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、キセノンランプ、レーザー光線、エックス線などの照射によりラジカルを発生する。 Examples of the photo radical initiator include benzoins, acetophenones, benzophenones, anthraquinones, xanthones, thioxanthones, ketals, and phosphine oxides. Specifically, for example, 2,2′-dimethoxy-1, 2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzophenone, 1- [4- (2-hydroxyethoxy) -Phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,6-dimethoxybe Nzoyl) 2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like, and one or more of these may be combined good. If necessary, sensitizer amines such as dimethylaminoethyl methacrylate, n-butylamine, triethylamine, isoamyl 4-dimethylaminobenzoate and the like can be used in appropriate amounts. The radical photoinitiator generates radicals by irradiation of a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a xenon lamp, a laser beam, an X-ray or the like as a light source of active energy rays.
ラジカル重合性モノマーとしてはフェノールエチレンオキサイド変性（メタ）アクリレート、パラクミルフェノールエチレンオキサイド変性（メタ）アクリレート、ノニルフェノールエチレンオキサイド変性（メタ）アクリレート、ノニルフェノールプロピレンオキサイド変性（メタ）アクリレート、２−エチルヘキシルカルビトール（メタ）アクリレート、Ｎ−ビニル−２−ピロリドン、イソボルニル（メタ）アクリレート、ビスフェノールＦエチレンオキサイド変性ジ（メタ）アクリレート、イソシアヌル酸エチレンオキサイド変性（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレートモノステアレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンエチレンオキサイド変性トリ（メタ）アクリレート、トリメチロールプロパンプロピレンオキサイド変性トリ（メタ）アクリレート、イソシアヌル酸エチレンオキサイド変性トリ（メタ）アクリレート等が挙げられ、これらの単独又は２種以上を組み合わせて使用できる。 Examples of the radical polymerizable monomer include phenol ethylene oxide modified (meth) acrylate, paracumyl phenol ethylene oxide modified (meth) acrylate, nonylphenol ethylene oxide modified (meth) acrylate, nonylphenol propylene oxide modified (meth) acrylate, 2-ethylhexyl carbitol ( (Meth) acrylate, N-vinyl-2-pyrrolidone, isobornyl (meth) acrylate, bisphenol F ethylene oxide modified di (meth) acrylate, isocyanuric acid ethylene oxide modified (meth) acrylate, tripropylene glycol di (meth) acrylate, pentaerythritol Di (meth) acrylate monostearate, polyethylene glycol di (meth) acrylate, polypro Lenglycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, isocyanuric Examples include acid ethylene oxide-modified tri (meth) acrylate, and these can be used alone or in combination of two or more.
有機溶剤としては、本発明の感光性樹脂、光ラジカル開始剤、必要により添加するラジカル重合性モノマー及びその他の添加剤を溶解する物であれば特に限定はしないが、例えば、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、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、プロピレングリコールモノメチルエーテル、プルピレングリコールモノメチルエーテルアセテート、メトキシプロピオン酸メチル、エトキシプロピオン酸エチル等が挙げられ、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。 The organic solvent is not particularly limited as long as it is a substance that dissolves the photosensitive resin of the present invention, a radical photoinitiator, a radically polymerizable monomer to be added if necessary, and other additives. For example, 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, ethylene glycol monobutyl ether acetate , Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene 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, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxypropionate, ethyl ethoxypropionate, etc., and together with these solvents to increase the in-plane uniformity of film thickness , N-Me Rupiroridon can γ- butyrolactone, N, also be used in combination with high boiling point solvent such as N- dimethylacetamide.
本発明の感光性樹脂組成物は、本発明の感光性樹脂、光ラジカル開始剤、ラジカル重合性モノマー及び／又は有機溶剤を必須成分として含有するが、その他必要に応じて、重合禁止剤、無機充填剤、レベリング剤、顔料や染料、紫外線吸収剤、増感剤、増感助剤、可塑剤、増粘剤、分散剤、消泡剤、界面活性剤、密着助材、難燃剤などを含有することができる。 The photosensitive resin composition of the present invention contains the photosensitive resin of the present invention, a photo radical initiator, a radical polymerizable monomer and / or an organic solvent as essential components. Contains fillers, leveling agents, pigments and dyes, UV absorbers, sensitizers, sensitizers, plasticizers, thickeners, dispersants, antifoaming agents, surfactants, adhesion aids, flame retardants, etc. can do.
次に本発明の感光性樹脂の使用方法であるが、先ず、ガラス基板、シリコンウエハーおよ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、乾燥して塗膜を形成する。組成物溶液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、バー塗布法等の適宜の方法が挙げられる。乾燥条件は、各成分の種類、使用割合等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, the method of using the photosensitive resin of the present invention is as follows. First, the photosensitive resin composition of the present invention is applied and dried on a glass substrate, a silicon wafer, and a substrate on which various metals are formed. To form a coating film. The method for applying the composition solution is not particularly limited, and examples thereof include an appropriate method such as a spray method, a roll coating method, a spin coating method, and a bar coating method. The drying conditions vary depending on the type of each component, the use ratio, and the like, but can be, for example, about 60 to 110 ° C. for 30 seconds to 30 minutes.
次に、形成された塗膜に所定のパターンを有するマスクを介して、露光した後、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。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−エン等のアルカリ（塩基性化合物）の水溶液を用いることができ、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、または本発明の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。さらに、現像方法としては、液盛り法、ディッピング法、揺動浸漬法、シャワー法等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、組成物の組成によって異なるが、例えば３０〜１２０秒間とすることができる。 Next, after the exposed coating film is exposed through a mask having a predetermined pattern, patterning is performed by developing using a developer. 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, triethylamine, Methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -undec-7-ene, 1,5-diazabicyclo An aqueous solution of an alkali (basic compound) such as [4,3,0] -none-5-ene can be used. In addition, a water-soluble organic solvent such as methanol or ethanol, or a surfactant is added to the aqueous alkali solution. Suitable Aqueous solution was added in an amount or various organic solvents capable of dissolving the composition of the present invention can be used as a developer. Furthermore, 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 composition, but can be, for example, 30 to 120 seconds.
次に、パターニングされた薄膜に対して、好ましくは例えば流水洗浄によるリンス処理を行い、必要により全面露光、ホットプレート、オーブン等により加熱処理（ポストベーク処理）することにより、硬化度を上げることが出来る。 Next, the patterned thin film is preferably rinsed, for example, by washing with running water, and if necessary, the entire film can be exposed to heat, heated by a hot plate, oven, etc. (post-baking) to increase the degree of curing. I can do it.
このようにして、目的と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、形成された膜は透明性、耐熱性、耐熱変色性に優れる被膜となる。 In this way, the target patterned thin film can be formed on the surface of the substrate, and the formed film becomes a film excellent in transparency, heat resistance, and heat discoloration.
以下に実施例を示して、本発明をさらに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。
なお、実施例１〜５は参考例として示す。
感光性樹脂の平均分子量の測定は以下の方法により行った。
（平均分子量の測定）
得られた感光性樹脂の重量平均分子量（Ｍｗ）、及び分子量分布（Ｍｗ／Ｍｎ）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した。
カラム：ショウデックス 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 ＲＩ−１０１）
流速：１ｍｌ／ｍｉｎ
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
In addition, Examples 1-5 are shown as reference examples.
The average molecular weight of the photosensitive resin was measured by the following method.
(Measurement of average molecular weight)
The weight average molecular weight of the obtained photosensitive resin (Mw), the values of and molecular weight distribution (Mw / Mn) by gel-Pami instantiation chromatography (GPC), was measured under the following conditions, in terms of polystyrene Calculated.
Column: sucrose c Dex KF-801 + KF-802 + KF-802 + KF-803
Column temperature: 40 ° C
Developing solvent: tetrahydrofuran Detector: differential refractometer (sucrose c index RI-101)
Flow rate: 1 ml / min
感光性樹脂の合成
各実施例及び比較例にて得られた感光性樹脂の重量平均分子量、及び分子量分布を表１に示す。
Synthesis of Photosensitive Resins Table 1 shows the weight average molecular weight and molecular weight distribution of the photosensitive resins obtained in each Example and Comparative Example.
実施例１
還流冷却器、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１００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５００質量部、２，２’−アゾビスイソブチロニトリル８質量部を仕込み、窒素雰囲気下、攪拌しながら液温を８０℃まで上昇させ、８０℃で８時間反応し、１００℃で１時間エージングを行って重合体を得た。次に、フラスコ内を空気雰囲気下に替え、ハイドロキノン０．０５質量部、トリスジメチルアミノメチルフェノール０．１質量部、グリシジルメタクリレート３１．９質量部を添加し、８０℃で６時間反応した。固形分濃度を４０質量％（以下の例も質量％）に調整し、感光性樹脂［Ａ−１］を含む樹脂溶液を得た。この樹脂の構造式を下記に示す。式中の４０、６０は配合割合から求めた各組成比（モル％）を意味する。以下同じ。
A flask equipped with a reflux condenser and a stirrer was charged with 100 parts by mass of p-hydroxyphenyl methacrylate, 500 parts by mass of propylene glycol monomethyl ether acetate, and 8 parts by mass of 2,2′-azobisisobutyronitrile. While stirring, the liquid temperature was raised to 80 ° C., reacted at 80 ° C. for 8 hours, and aged at 100 ° C. for 1 hour to obtain a polymer. Next, the inside of the flask was changed to an air atmosphere, 0.05 parts by mass of hydroquinone, 0.1 parts by mass of trisdimethylaminomethylphenol and 31.9 parts by mass of glycidyl methacrylate were added and reacted at 80 ° C. for 6 hours. The solid content concentration was adjusted to 40% by mass (the following example was also mass%) to obtain a resin solution containing the photosensitive resin [A-1]. The structural formula of this resin is shown below. 40 and 60 in a formula mean each composition ratio (mol%) calculated | required from the mixture ratio. same as below.
実施例２
実施例１のグリシジルメタクリレート３１．９質量部を４７．９質量部に変更した以外は同様に行い、感光性樹脂［Ａ−２］を含む樹脂溶液を得た。
It carried out similarly except having changed 31.9 mass parts of glycidyl methacrylate of Example 1 into 47.9 mass parts, and obtained the resin solution containing photosensitive resin [A-2].
実施例３
還流冷却器、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８７．７質量部、メタクリル酸メチル１２．３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５００質量部、２，２’−アゾビスイソブチロニトリル８質量部を仕込み、窒素雰囲気下、攪拌しながら液温を８０℃まで上昇させ、８０℃で８時間反応し、１００℃で１時間エージングを行って共重合体を得た。次に、フラスコ内を空気雰囲気下に替え、ハイドロキノン０．０５質量部、トリスジメチルアミノメチルフェノール０．１質量部、グリシジルメタクリレート３５．０質量部を添加し、８０℃で６時間反応した。固形分濃度を４０％に調整し、感光性樹脂［Ａ−３］を含む溶液を得た。
In a flask equipped with a reflux condenser and a stirrer, 87.7 parts by mass of p-hydroxyphenyl methacrylate, 12.3 parts by mass of methyl methacrylate, 500 parts by mass of propylene glycol monomethyl ether acetate, 2,2′-azobisisobutyro Nitrile (8 parts by mass) was charged, and the liquid temperature was raised to 80 ° C. with stirring in a nitrogen atmosphere, reacted at 80 ° C. for 8 hours, and aged at 100 ° C. for 1 hour to obtain a copolymer. Next, the inside of the flask was changed to an air atmosphere, 0.05 parts by mass of hydroquinone, 0.1 parts by mass of trisdimethylaminomethylphenol, and 35.0 parts by mass of glycidyl methacrylate were added and reacted at 80 ° C. for 6 hours. The solid content concentration was adjusted to 40% to obtain a solution containing the photosensitive resin [A-3].
実施例４
還流冷却器、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７６．４質量部、ジシクロペンタニルメタクリレート２３．６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５００質量部、２，２’−アゾビスイソブチロニトリル８質量部を仕込み、窒素雰囲気下、攪拌しながら液温を８０℃まで上昇させ、８０℃で８時間反応し、１００℃で１時間エージングを行って共重合体を得た。次に、フラスコ内を空気雰囲気下に替え、ハイドロキノン０．０５質量部、トリスジメチルアミノメチルフェノール０．１質量部、グリシジルメタクリレート３０．５質量部を添加し、８０℃で６時間反応した。固形分濃度を４０％に調整し、感光性樹脂［Ａ−４］を含む溶液を得た。
In a flask equipped with a reflux condenser and a stirrer, 76.4 parts by mass of p-hydroxyphenyl methacrylate, 23.6 parts by mass of dicyclopentanyl methacrylate, 500 parts by mass of propylene glycol monomethyl ether acetate, 2,2′-azobisiso 8 parts by mass of butyronitrile was charged, the liquid temperature was raised to 80 ° C. with stirring in a nitrogen atmosphere, the reaction was performed at 80 ° C. for 8 hours, and aging was performed at 100 ° C. for 1 hour to obtain a copolymer. Next, the inside of the flask was changed to an air atmosphere, 0.05 parts by mass of hydroquinone, 0.1 parts by mass of trisdimethylaminomethylphenol, and 30.5 parts by mass of glycidyl methacrylate were added and reacted at 80 ° C. for 6 hours. The solid content concentration was adjusted to 40% to obtain a solution containing the photosensitive resin [A-4].
実施例５
還流冷却器、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８２．８質量部、メタクリル酸１７．２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５００質量部、２，２’−アゾビスイソブチロニトリル８質量部を仕込み、窒素雰囲気下、攪拌しながら液温を８０℃まで上昇させ、８０℃で８時間反応し、１００℃で１時間エージングを行って共重合体を得た。次に、フラスコ内を空気雰囲気下に替え、ハイドロキノン０．０５質量部、トリスジメチルアミノメチルフェノール０．１質量部、グリシジルメタクリレート３７．８質量部を添加し、８０℃で６時間反応した。固形分濃度を４０％に調整し、感光性樹脂［Ｂ−１］を含む溶液を得た。
In a flask equipped with a reflux condenser and a stirrer, 82.8 parts by mass of p-hydroxyphenyl methacrylate, 17.2 parts by mass of methacrylic acid, 500 parts by mass of propylene glycol monomethyl ether acetate, 2,2′-azobisisobutyronitrile. 8 parts by mass was added, the liquid temperature was raised to 80 ° C. while stirring in a nitrogen atmosphere, the reaction was performed at 80 ° C. for 8 hours, and aging was performed at 100 ° C. for 1 hour to obtain a copolymer. Next, the inside of the flask was changed to an air atmosphere, 0.05 parts by mass of hydroquinone, 0.1 parts by mass of trisdimethylaminomethylphenol, and 37.8 parts by mass of glycidyl methacrylate were added and reacted at 80 ° C. for 6 hours. The solid content concentration was adjusted to 40% to obtain a solution containing the photosensitive resin [B-1].
実施例６
還流冷却器、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６５．３質量部、グリシジルメタクリレート３４．７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５００質量部、２，２’−アゾビスイソブチロニトリル８質量部を仕込み、窒素雰囲気下、攪拌しながら液温を８０℃まで上昇させ、８０℃で８時間反応し、１００℃で１時間エージングを行って共重合体を得た。次に、フラスコ内を空気雰囲気下に替え、ハイドロキノン０．０５質量部、トリスジメチルアミノメチルフェノール０．１質量部、アクリル酸１７．６質量部を添加し、８０℃で６時間反応した。固形分濃度を４０％に調整し、感光性樹脂［Ｃ−１］を含む溶液を得た。
In a flask equipped with a reflux condenser and a stirrer, 65.3 parts by mass of p-hydroxyphenyl methacrylate, 34.7 parts by mass of glycidyl methacrylate, 500 parts by mass of propylene glycol monomethyl ether acetate, 2,2′-azobisisobutyronitrile. 8 parts by mass was added, the liquid temperature was raised to 80 ° C. while stirring in a nitrogen atmosphere, the reaction was performed at 80 ° C. for 8 hours, and aging was performed at 100 ° C. for 1 hour to obtain a copolymer. Next, the inside of the flask was changed to an air atmosphere, 0.05 part by mass of hydroquinone, 0.1 part by mass of trisdimethylaminomethylphenol and 17.6 parts by mass of acrylic acid were added, and the reaction was carried out at 80 ° C. for 6 hours. The solid content concentration was adjusted to 40% to obtain a solution containing the photosensitive resin [C-1].
比較例１
還流冷却器、攪拌機を備えたフラスコに、メタクリル酸メチル４３．７質量部、メタクリル酸５６．３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５００質量部、２，２’−アゾビスイソブチロニトリル８質量部を仕込み、窒素雰囲気下、攪拌しながら液温を８０℃まで上昇させ、８０℃で８時間反応し、１００℃で１時間エージングを行って共重合体を得た。次に、フラスコ内を空気雰囲気下に替え、ハイドロキノン０．０５質量部、トリスジメチルアミノメチルフェノール０．１質量部、グリシジルメタクリレート６２．０質量部を添加し、８０℃で６時間反応した。固形分濃度を４０％に調整し、感光性樹脂［Ｄ−１］を含む溶液を得た。
In a flask equipped with a reflux condenser and a stirrer, 43.7 parts by mass of methyl methacrylate, 56.3 parts by mass of methacrylic acid, 500 parts by mass of propylene glycol monomethyl ether acetate, 8 parts by mass of 2,2′-azobisisobutyronitrile. The liquid temperature was raised to 80 ° C. while stirring under a nitrogen atmosphere, the reaction was carried out at 80 ° C. for 8 hours, and aging was carried out at 100 ° C. for 1 hour to obtain a copolymer. Next, the inside of the flask was changed to an air atmosphere, 0.05 parts by mass of hydroquinone, 0.1 parts by mass of trisdimethylaminomethylphenol, and 62.0 parts by mass of glycidyl methacrylate were added and reacted at 80 ° C. for 6 hours. The solid content concentration was adjusted to 40% to obtain a solution containing the photosensitive resin [D-1].
比較例２
還流冷却器、攪拌機を備えたフラスコに、ポリヒドロキシスチレン１００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５００質量部、ハイドロキノン０．０５質量部、トリスジメチルアミノメチルフェノール０．１質量部、グリシジルメタクリレート４７．３質量部を添加し、８０℃で６時間反応した。固形分濃度を４０％に調整し、感光性樹脂［Ｄ−２］を含む溶液を得た。
In a flask equipped with a reflux condenser and a stirrer, 100 parts by mass of polyhydroxystyrene, 500 parts by mass of propylene glycol monomethyl ether acetate, 0.05 parts by mass of hydroquinone, 0.1 parts by mass of trisdimethylaminomethylphenol, 47.3 glycidyl methacrylate. A part by mass was added and reacted at 80 ° C. for 6 hours. The solid content concentration was adjusted to 40% to obtain a solution containing the photosensitive resin [D-2].
感光性樹脂組成物の調製、及び塗膜の作成
感光性樹脂組成物の各特性を表２及び表３に示す。
Preparation of photosensitive resin composition and creation of coating film Table 2 and Table 3 show the characteristics of the photosensitive resin composition.
（実施例７〜１２及び比較例３〜４）
実施例１〜６及び比較例１〜２で得られた感光性樹脂溶液１００質量部、光ラジカル開始剤として２，２−ジメトキシ−２−フェニルアセトフェノン３質量部を添加して感光性樹脂組成物を得た。得られた感光性樹脂組成物をアセトンで脱脂したガラス板に厚さ５０μｍで塗布し、８０℃オーブンで２０分間乾燥させて、感光性樹脂の塗膜を得た。
(Examples 7-12 and Comparative Examples 3-4)
A photosensitive resin composition obtained by adding 100 parts by mass of the photosensitive resin solutions obtained in Examples 1 to 6 and Comparative Examples 1 and 2, and 3 parts by mass of 2,2-dimethoxy-2-phenylacetophenone as a photo radical initiator. Got. The obtained photosensitive resin composition was applied to a glass plate degreased with acetone at a thickness of 50 μm and dried in an oven at 80 ° C. for 20 minutes to obtain a photosensitive resin coating film.
（実施例１３〜１８及び比較例５〜６）
実施例１〜６及び比較例１〜２で得られた感光性樹脂溶液１００質量部、光ラジカル開始剤として２，２−ジメトキシ−２−フェニルアセトフェノン４質量部、ペンタエリスリトールテトラアクリレート４質量部を添加して感光性樹脂組成物を得た。得られた感光性樹脂組成物をアセトンで脱脂したガラス板に厚さ５０μｍで塗布し、８０℃オーブンで２０分間乾燥させて、感光性樹脂の塗膜を得た。
(Examples 13 to 18 and Comparative Examples 5 to 6)
100 parts by mass of the photosensitive resin solutions obtained in Examples 1 to 6 and Comparative Examples 1 to 2, 4 parts by mass of 2,2-dimethoxy-2-phenylacetophenone and 4 parts by mass of pentaerythritol tetraacrylate as a photo radical initiator It added and obtained the photosensitive resin composition. The obtained photosensitive resin composition was applied to a glass plate degreased with acetone at a thickness of 50 μm and dried in an oven at 80 ° C. for 20 minutes to obtain a photosensitive resin coating film.
現像性の評価
［現像性］
乾燥した塗膜にパターンマスクを介して超高圧水銀灯を用いて５００ｍＪ／ｃｍ2露光し、２．３８％テトラメチルアンモニウムヒドロキシドの水溶液にて２分間浸漬して現像し、純水でリンスを行った。格子状の凹凸パターンが転写された物を○、パターンが転写されなかった物を×とした。
Evaluation of developability [Developability]
The dried coating film is exposed to 500 mJ / cm 2 using a super high pressure mercury lamp through a pattern mask, developed by immersing in an aqueous solution of 2.38% tetramethylammonium hydroxide for 2 minutes, and rinsed with pure water. It was. The thing with which the grid | lattice-like uneven | corrugated pattern was transcribe | transferred was set as (circle), and the thing in which the pattern was not transferred was set as x.
［透明性］
乾燥した塗膜に超高圧水銀灯を用いて５００ｍＪ／ｃｍ2全面露光し、２００℃、３０分間オーブンで加熱処理して硬化塗膜を得た。得られた硬化塗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の最低透過率をガラス基板をブランクとして測定した。９０％以上を○、８０〜９０％を△、８０％未満を×とした。
[transparency]
The dried coating film was exposed to an entire surface of 500 mJ / cm 2 using an ultra-high pressure mercury lamp and heat-treated in an oven at 200 ° C. for 30 minutes to obtain a cured coating film. About the obtained glass substrate with a cured coating film, the minimum transmittance | permeability of wavelength 400-800 nm was measured using the glass substrate as the blank using the spectrophotometer. 90% or more was evaluated as ◯, 80 to 90% as Δ, and less than 80% as ×.
［耐熱性］
２００℃、３０分間加熱処理させた後、再び２３０℃で２時間、更に２５０℃で１時間加熱処理し、膜厚測定を行った。２００℃、３０分間加熱処理後膜厚に対して、再加熱後の膜厚変化を膜厚減少率で算出した。再加熱後の膜厚減少率が２０％未満の場合を○、２０〜３０％を△、３０％以上の場合を×とした。
[Heat-resistant]
After heat treatment at 200 ° C. for 30 minutes, the film thickness was measured again at 230 ° C. for 2 hours and further at 250 ° C. for 1 hour. With respect to the film thickness after heat treatment at 200 ° C. for 30 minutes, the change in film thickness after reheating was calculated as the film thickness reduction rate. The film thickness reduction rate after reheating was less than 20%, and 20 to 30% was Δ, and the case of 30% or more was x.
［耐熱変色性］
２００℃、３０分間加熱処理させた後、再び２３０℃で２時間、更に２５０℃で１時間加熱処理し、波長４００〜８００ｎｍの最低透過率をガラス基板をブランクとして測定した。８０％以上を○、７０〜８０％を△、７０％未満を×とした。
[Heat-resistant discoloration]
After heat treatment at 200 ° C. for 30 minutes, heat treatment was again performed at 230 ° C. for 2 hours and further at 250 ° C. for 1 hour, and the minimum transmittance at a wavelength of 400 to 800 nm was measured using a glass substrate as a blank. 80% or more was evaluated as ◯, 70-80% as Δ, and less than 70% as X.
本発明の感光性樹脂及び感光性樹脂組成物は光硬化性、硬化物の透明性、耐熱性及び耐熱変色性に優れる皮膜を形成することができ、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や層間絶縁膜、カラーフィルタを形成する材料、有機ＥＬ素子の絶縁膜、マイクロレンズ材料、更には光導波路材料として好適に使用できる。 The photosensitive resin and photosensitive resin composition of the present invention can form a film excellent in photocurability, transparency of a cured product, heat resistance, and heat discoloration, and can be used for liquid crystal display elements, integrated circuit elements, solid-state imaging elements. It can be suitably used as a protective film for an electronic component such as an interlayer insulating film, a material for forming a color filter, an insulating film for an organic EL element, a microlens material, and an optical waveguide material.
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