JP2007206369A - Colored alkali developable photosensitive resin composition and color filter obtained by using the same - Google Patents
Colored alkali developable photosensitive resin composition and color filter obtained by using the same Download PDFInfo
- Publication number
- JP2007206369A JP2007206369A JP2006025026A JP2006025026A JP2007206369A JP 2007206369 A JP2007206369 A JP 2007206369A JP 2006025026 A JP2006025026 A JP 2006025026A JP 2006025026 A JP2006025026 A JP 2006025026A JP 2007206369 A JP2007206369 A JP 2007206369A
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- JP
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- Prior art keywords
- compound
- resin composition
- photosensitive resin
- group
- epoxy
- 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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- 239000011342 resin composition Substances 0.000 title claims abstract description 123
- 239000003513 alkali Substances 0.000 title claims abstract description 58
- 150000001875 compounds Chemical class 0.000 claims abstract description 267
- 239000004593 Epoxy Substances 0.000 claims abstract description 94
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 46
- 239000002253 acid Substances 0.000 claims abstract description 23
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 21
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000011161 development Methods 0.000 claims description 39
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 238000004040 coloring Methods 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000003086 colorant Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 9
- 230000032050 esterification Effects 0.000 abstract description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 47
- -1 methylcyclohexyl Chemical group 0.000 description 37
- 230000018109 developmental process Effects 0.000 description 36
- 238000004519 manufacturing process Methods 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 29
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 27
- 238000001816 cooling Methods 0.000 description 20
- 229910003460 diamond Inorganic materials 0.000 description 19
- 239000010432 diamond Substances 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 19
- 239000004305 biphenyl Substances 0.000 description 18
- 229940014800 succinic anhydride Drugs 0.000 description 18
- 125000003700 epoxy group Chemical group 0.000 description 17
- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 description 17
- 239000000049 pigment Substances 0.000 description 16
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 15
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 15
- 239000000975 dye Substances 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 11
- 239000011572 manganese Substances 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000007796 conventional method Methods 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 235000019241 carbon black Nutrition 0.000 description 5
- 229940049920 malate Drugs 0.000 description 5
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 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
- 238000007259 addition reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000007261 regionalization Effects 0.000 description 3
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 3
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N Vilsmeier-Haack reagent Natural products CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- FFSAXUULYPJSKH-UHFFFAOYSA-N butyrophenone Chemical compound CCCC(=O)C1=CC=CC=C1 FFSAXUULYPJSKH-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 2
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- 238000001035 drying Methods 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-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
- 238000002156 mixing Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 125000005591 trimellitate group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- JIAFOCJABIEPNM-BYPYZUCNSA-N (2s)-2-(3-sulfanylpropanoylamino)propanoic acid Chemical compound OC(=O)[C@H](C)NC(=O)CCS JIAFOCJABIEPNM-BYPYZUCNSA-N 0.000 description 1
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- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ADXGNEYLLLSOAR-UHFFFAOYSA-N tasosartan Chemical compound C12=NC(C)=NC(C)=C2CCC(=O)N1CC(C=C1)=CC=C1C1=CC=CC=C1C=1N=NNN=1 ADXGNEYLLLSOAR-UHFFFAOYSA-N 0.000 description 1
- 235000007586 terpenes Nutrition 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
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000001017 thiazole dye Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 229940103494 thiosalicylic acid Drugs 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000001003 triarylmethane dye Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 1
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- Optical Filters (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
本発明は、液晶ディスプレイ、プラズマディスプレイ、エレクトロルミネッセンスパネル、ビデオカメラ等に用いられるカラーフィルタの作成に好適に使用される着色アルカリ現像型感光性樹脂組成物、及び該着色アルカリ現像型感光性樹脂組成物を用いたカラーフィルタに関する。 The present invention relates to a colored alkali-developable photosensitive resin composition suitably used for producing a color filter used in a liquid crystal display, a plasma display, an electroluminescence panel, a video camera and the like, and the colored alkali-developable photosensitive resin composition The present invention relates to a color filter using an object.
着色アルカリ現像型感光性樹脂組成物は、エチレン性不飽和結合を有する特定の化合物を含有するアルカリ現像性樹脂組成物に、顔料又は染料等の色材、及び光重合開始剤を含有させたものである。この着色アルカリ現像型感光性樹脂組成物は、紫外線もしくは電子線を照射することによって重合硬化させることができるので、光硬化性インキ、感光性印刷版、プリント配線版、各種フォトレジスト等に用いられている。最近、電子機器の軽薄短小化や高機能化の進展に伴い、微細パターンを精度良く形成することが望まれている。 The colored alkali-developable photosensitive resin composition comprises an alkali-developable resin composition containing a specific compound having an ethylenically unsaturated bond, a coloring material such as a pigment or a dye, and a photopolymerization initiator. It is. This colored alkali-developable photosensitive resin composition can be polymerized and cured by irradiation with ultraviolet rays or an electron beam, so it is used for photo-curable inks, photosensitive printing plates, printed wiring plates, various photoresists, and the like. ing. Recently, with the progress of miniaturization and high functionality of electronic devices, it is desired to form fine patterns with high accuracy.
アルカリ現像性樹脂組成物及びアルカリ現像型感光性樹脂組成物に関し、下記特許文献１には、エチレン性不飽和結合を持つプレポリマーを含有する感光性樹脂組成物が提案されている。また、下記特許文献２には、不飽和基含有ポリカルボン酸樹脂を含有する感光性樹脂組成物が提案されている。しかし、これらの公知のアルカリ現像型感光性樹脂組成物は、解像度や現像性が充分でなく、これらのアルカリ現像型感光性樹脂組成物を用いた着色アルカリ現像型感光性樹脂組成物では適切なパターン形状や微細パターンを得ることが困難であった。そのため、解像度、現像性に優れ、微細パターンを精度良く形成できる着色アルカリ現像型感光性樹脂組成物が望まれていた。 Regarding the alkali-developable resin composition and the alkali-developable photosensitive resin composition, the following Patent Document 1 proposes a photosensitive resin composition containing a prepolymer having an ethylenically unsaturated bond. Patent Document 2 below proposes a photosensitive resin composition containing an unsaturated group-containing polycarboxylic acid resin. However, these known alkali-developable photosensitive resin compositions have insufficient resolution and developability, and are suitable for colored alkali-developable photosensitive resin compositions using these alkali-developable photosensitive resin compositions. It was difficult to obtain pattern shapes and fine patterns. Therefore, a colored alkali development type photosensitive resin composition that is excellent in resolution and developability and can form a fine pattern with high accuracy has been desired.
解決しようとする問題点は、上述したように、高解像度で現像性に優れ、適切なパターン形状や微細パターンを得ることのできる着色アルカリ現像型感光性樹脂組成物がこれまでなかったということである。 As described above, the problem to be solved is that, as described above, there has been no colored alkali development type photosensitive resin composition capable of obtaining an appropriate pattern shape and fine pattern with high resolution and excellent developability. is there.
従って、本発明の目的は、感度、解像度、現像性等に優れ、微細パターンを精度良く形成できる着色アルカリ現像型感光性樹脂組成物、及び該着色アルカリ現像型感光性樹脂組成物を用いたカラーフィルタを提供することにある。 Accordingly, an object of the present invention is to provide a colored alkali-developable photosensitive resin composition that is excellent in sensitivity, resolution, developability, etc., and can form a fine pattern with high accuracy, and a color using the colored alkali-developable photosensitive resin composition. To provide a filter.
本発明は、下記一般式（I）で表されるエポキシ化合物（Ａ）に不飽和一塩基酸（Ｂ）を付加させた構造を有するエポキシ付加物に、多塩基酸無水物（Ｃ）をエステル化させて得られる反応生成物に、エポキシ化合物（Ｄ）を付加させ、さらに多塩基酸無水物（Ｅ）をエステル化させて得られる構造を有する光重合性不飽和化合物（Ｘ）を含有するアルカリ現像性樹脂組成物に、さらに光重合開始剤（Ｆ）及び色材（Ｇ）を含有させることを特徴とする着色アルカリ現像型感光性樹脂組成物を提供することにより、上記目的を達成したものである。 In the present invention, polybasic acid anhydride (C) is esterified to an epoxy adduct having a structure in which unsaturated monobasic acid (B) is added to epoxy compound (A) represented by the following general formula (I). Containing the photopolymerizable unsaturated compound (X) having a structure obtained by adding the epoxy compound (D) to the reaction product obtained by the polymerization and further esterifying the polybasic acid anhydride (E) The object was achieved by providing a colored alkali-developable photosensitive resin composition characterized by further containing a photopolymerization initiator (F) and a colorant (G) in the alkali-developable resin composition. Is.
また、本発明は、上記光重合性不飽和化合物（Ｘ）に、さらにエポキシ化合物（Ｄ）を付加させ、続いて多塩基酸無水物（Ｅ）をエステル化させることを１回以上繰り返して得られる構造を有する光重合性不飽和化合物（Ｙ）を含有するアルカリ現像性樹脂組成物に、さらに光重合開始剤（Ｆ）及び色材（Ｇ）を含有させることを特徴とする着色アルカリ現像型感光性樹脂組成物を提供することにより、上記目的を達成したものである。
また、本発明は、上記着色アルカリ現像型感光性樹脂組成物を用いたカラーフィルタを提供することにより、上記目的を達成したものである。
Further, the present invention is obtained by repeatedly adding the epoxy compound (D) to the photopolymerizable unsaturated compound (X) and then esterifying the polybasic acid anhydride (E) one or more times. A colored alkali development type characterized by further containing a photopolymerization initiator (F) and a colorant (G) in an alkali developable resin composition containing a photopolymerizable unsaturated compound (Y) having a structure as described above The above object is achieved by providing a photosensitive resin composition.
Moreover, this invention achieves the said objective by providing the color filter using the said colored alkali development type photosensitive resin composition.
本発明の着色アルカリ現像型感光性樹脂組成物は、感度、解像度、現像性に優れ、微細パターンを精度良く形成でき、カラーフィルタとして好適である。 The colored alkali development type photosensitive resin composition of the present invention is excellent in sensitivity, resolution, and developability, can form a fine pattern with high accuracy, and is suitable as a color filter.
以下、本発明の着色アルカリ現像型感光性樹脂組成物について、好ましい実施形態に基づき詳細に説明する。 Hereinafter, the colored alkali development type photosensitive resin composition of the present invention will be described in detail based on preferred embodiments.
本発明の着色アルカリ現像型感光性樹脂組成物は、光重合性不飽和化合物（Ｘ）又は（Ｙ）を含有するアルカリ現像性樹脂組成物に、光重合開始剤（Ｆ）及び顔料又は染料等の色材（Ｇ）を含有させてなるものであり、具体的には光重合性不飽和化合物（Ｘ）又は該光重合性不飽和化合物（Ｘ）に、さらにエポキシ化合物（Ｄ）を付加させ、続いて多塩基酸無水物（Ｅ）をエステル化させることを１回以上繰り返して得られる構造を有する光重合性不飽和化合物（Ｙ）の含有量が、上記着色アルカリ現像型感光性樹脂組成物中、1〜７０質量％であり、上記光重合開始剤（Ｆ）の含有量が、上記着色アルカリ現像型感光性樹脂組成物中、０．１〜３０質量％であり、上記色材（Ｇ）の含有量が、該着色アルカリ現像型感光性樹脂組成物から溶媒を除く全固形成分中０．５〜７０質量％であるものである。 The colored alkali-developable photosensitive resin composition of the present invention includes a photopolymerization initiator (F), a pigment, a dye, and the like in an alkali-developable resin composition containing the photopolymerizable unsaturated compound (X) or (Y). In particular, the epoxy compound (D) is further added to the photopolymerizable unsaturated compound (X) or the photopolymerizable unsaturated compound (X). Subsequently, the content of the photopolymerizable unsaturated compound (Y) having a structure obtained by repeating the esterification of the polybasic acid anhydride (E) at least once is determined by the above-described colored alkali development type photosensitive resin composition. 1 to 70% by mass in the product, and the content of the photopolymerization initiator (F) is 0.1 to 30% by mass in the colored alkali development type photosensitive resin composition. The content of G) is a solvent from the colored alkali development type photosensitive resin composition It is 0.5 to 70% by mass in the total solid components excluding.
本発明の着色アルカリ現像型感光性樹脂組成物は、上記一般式（Ｉ）で表されるエポキシ化合物（Ａ）に、不飽和一塩基酸（Ｂ）を、上記エポキシ化合物（Ａ）のエポキシ基1個に対し、上記不飽和一塩基酸（Ｂ）のカルボキシル基が０．１〜１．０個となる比率で付加させた構造を有するエポキシ付加物に対し、多塩基酸無水物（Ｃ）を、上記エポキシ付加物の水酸基1個に対し酸無水物構造が０．１〜１．０個となる比率で、続いて上記エポキシ化合物（Ｄ）を、上記エポキシ付加物の水酸基1個に対しエポキシ基が０．１〜１．０個となる比率で付加し、続いて上記多塩基酸無水物（Ｅ）を、上記エポキシ化合物の水酸基１個に対し酸無水物構造が０．１〜１．０個となる比率でエステル化させた構造を有する光重合性不飽和化合物を含有する。
上記エポキシ化合物（Ａ）のエポキシ基１個に対する上記不飽和一塩基酸（Ｂ）のカルボキシル基の比率は、好ましくは０．４〜１．０個である。また、上記エポキシ化合物の水酸基１個に対し、多塩基酸無水物（Ｃ）の酸無水物構造の比率は好ましくは０．３〜０．９５個であり、上記エポキシ化合物（Ｄ）のエポキシ基の比率は好ましくは０．３〜０．９個であり、上記多塩基酸無水物（Ｅ）の酸無水物構造の比率は好ましくは０．３〜０．７個である。
The colored alkali-developable photosensitive resin composition of the present invention comprises an unsaturated monobasic acid (B) and an epoxy group of the epoxy compound (A) represented by the epoxy compound (A) represented by the general formula (I). Polybasic acid anhydride (C) with respect to an epoxy adduct having a structure in which a carboxyl group of the unsaturated monobasic acid (B) is added at a ratio of 0.1 to 1.0 with respect to one At a ratio of 0.1 to 1.0 acid anhydride structure with respect to one hydroxyl group of the epoxy adduct, and then the epoxy compound (D) to one hydroxyl group of the epoxy adduct. An epoxy group is added at a ratio of 0.1 to 1.0, and then the polybasic acid anhydride (E) is added in an acid anhydride structure of 0.1 to 1 with respect to one hydroxyl group of the epoxy compound. Contains a photopolymerizable unsaturated compound having a structure esterified at a ratio of 0.0 That.
The ratio of the carboxyl group of the unsaturated monobasic acid (B) to one epoxy group of the epoxy compound (A) is preferably 0.4 to 1.0. The ratio of the acid anhydride structure of the polybasic acid anhydride (C) to one hydroxyl group of the epoxy compound is preferably 0.3 to 0.95, and the epoxy group of the epoxy compound (D) The ratio of is preferably 0.3 to 0.9, and the ratio of the acid anhydride structure of the polybasic acid anhydride (E) is preferably 0.3 to 0.7.
上記一般式（Ｉ）中、Ｃｙで示される炭素原子数３〜１０のシクロアルキル基としては、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、メチルシクロヘキシル、シクロヘプチル、シクロオクチル、シクロノニル、シクロデシル等が挙げられる。
Ｘで表される炭素原子数３〜１０のシクロアルキル基としては、例えば、Ｃｙで示される炭素原子数３〜１０のシクロアルキル基として例示したものが挙げられる。Ｘで示されるフェニル基又は炭素原子数３〜１０のシクロアルキル基を置換してもよい炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基及びハロゲン原子としては、それぞれ、Ｙ及びＺで示されるものとして後に例示するものが挙げられる。
Ｙ及びＺで示される炭素原子数１〜１０のアルキル基としては、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、第二ブチル、第三ブチル、アミル、イソアミル、第三アミル、ヘキシル、へプチル、オクチル、イソオクチル、第三オクチル、２−エチルヘキシル、ノニル、イソノニル、デシル、イソデシル等が挙げられる。Ｙ及びＺで示される炭素原子数１〜１０のアルコキシ基としてはメトキシ、エトキシ、プロピルオキシ、ブチルオキシ、メトキシエチル、エトキシエチル、プロピロキシエチル、メトキシエトキシエチル、エトキシエトキシエチル、プロピロキシエトキシエチル、メトキシプロピル等が挙げられる。Ｙ及びＺで示される炭素原子数２〜１０のアルケニル基としては、ビニル、アリル、ブテニル、プロペニル等が挙げられる、Ｙ及びＺで示されるハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられる。
また、Ｘで示されるフェニル基及び炭素原子数３〜１０のシクロアルキル基を置換してもよい上記のアルキル基及びアルコキシ基、並びにＹ及びＺで示される上記のアルキル基、アルコキシ基及びアルケニル基は、ハロゲン原子で置換されていてもよく、該ハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられる。例えば、フッ素原子で置換された炭素原子数１〜１０のアルキル基としては、モノフルオロメチル、ジフルオロメチル、トリフルオロメチル、トリフルオロエチル、パーフルオロエチル等が挙げられる。
In the general formula (I), examples of the cycloalkyl group having 3 to 10 carbon atoms represented by Cy include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like. .
Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by X include those exemplified as the cycloalkyl group having 3 to 10 carbon atoms represented by Cy. As the phenyl group represented by X or the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms and the halogen atom which may be substituted with the cycloalkyl group having 3 to 10 carbon atoms, What is illustrated later as what is shown by Y and Z is mentioned.
Examples of the alkyl group having 1 to 10 carbon atoms represented by Y and Z include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl Octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl and the like. Examples of the alkoxy group having 1 to 10 carbon atoms represented by Y and Z include methoxy, ethoxy, propyloxy, butyloxy, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, methoxy And propyl. Examples of the alkenyl group having 2 to 10 carbon atoms represented by Y and Z include vinyl, allyl, butenyl, propenyl, etc. Examples of the halogen atom represented by Y and Z include fluorine, chlorine, bromine and iodine. It is done.
In addition, the above-mentioned alkyl group and alkoxy group which may be substituted for the phenyl group represented by X and the cycloalkyl group having 3 to 10 carbon atoms, and the above-described alkyl group, alkoxy group and alkenyl group represented by Y and Z May be substituted with a halogen atom, and examples of the halogen atom include fluorine, chlorine, bromine and iodine. For example, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl etc. are mentioned as a C1-C10 alkyl group substituted by the fluorine atom.
本発明の着色アルカリ現像型感光性樹脂組成物は、その調製に用いられるエポキシ化合物（Ａ）がトリアリールモノシクロアルキルメタン骨格を有することにより、硬化物の基材への密着性、耐アルカリ性、加工性、強度等が優れるため、非硬化部を現像除去する際に、微細パターンであっても鮮明な画像を精度良く形成できるものと考えられる。エポキシ化合物（Ａ）としては、上記一般式（Ｉ）において、Ｃｙがシクロヘキシルであるもの；Ｘがフェニル基であるもの；ｐ及びｒが０であるもの；ｎが０〜５であるものが好ましい。 The colored alkali-developable photosensitive resin composition of the present invention has an epoxy compound (A) used for its preparation having a triarylmonocycloalkylmethane skeleton, whereby the adhesion of the cured product to the substrate, alkali resistance, Since processability, strength, and the like are excellent, it is considered that a clear image can be formed with high accuracy even if the pattern is a fine pattern when the uncured portion is developed and removed. As the epoxy compound (A), in general formula (I), those in which Cy is cyclohexyl; those in which X is a phenyl group; those in which p and r are 0; those in which n is 0 to 5 are preferable. .
上記一般式（Ｉ）で表されるエポキシ化合物（Ａ）の具体例としては、以下の化合物Ｎｏ．１〜Ｎｏ．９の化合物が挙げられる。ただし、本発明は以下の化合物により何ら制限を受けるものではない。 Specific examples of the epoxy compound (A) represented by the general formula (I) include the following compound Nos. 1-No. 9 compounds are mentioned. However, the present invention is not limited by the following compounds.
上記アルカリ現像性樹脂組成物に含有される、（Ａ）成分に（Ｂ）成分を付加させた構造を有するエポキシ付加物に対し、（Ｃ）成分をエステル化させた構造を有する反応生成物に、さらに（Ｄ）成分を付加し、続いて（Ｅ）成分をエステル化した構造を有する光重合性不飽和化合物（Ｘ）は、例えば、下記[化１１]の反応式で示される方法によって製造することができる。
まず、（Ａ）成分であるエポキシ化合物（１）に、（Ｂ）成分である不飽和一塩基酸（２）を付加させて、エポキシ付加物である化合物（３）を含む樹脂組成物を得る。（Ａ）成分への（Ｂ）成分の付加反応は、常法に従って行なうことができるが、好ましくは、９０〜１５０℃で５〜３０時間反応させる。
続いて、エポキシ付加物である化合物（３）に、（Ｃ）成分である多塩基酸無水物（４）を反応させてエステル化反応を行い、エステル化合物である化合物（５）を含む樹脂組成物を得る。エポキシ付加物と（Ｃ）成分とのエステル化反応は、常法に従って行なうことができるが、好ましくは、３０〜１５０℃で５〜３０時間反応させる。
続いて、エステル化合物である化合物（５）に、更に（Ｄ）成分のエポキシ化合物である化合物（６）を付加反応させて、化合物（７）を得る。エステル化合物と（Ｄ）成分との付加反応は、常法に従って行なうことができるが、好ましくは、５０〜１５０℃で２〜３０時間反応を行なう。
続いて、化合物（７）に、更に（Ｅ）成分の多塩基酸無水物である化合物（８）を反応させてエステル化を行ない、目的の反応生成物である化合物（９）〔光重合性不飽和化合物（Ｘ）〕を含む樹脂組成物を得ることができる。上記化合物（７）と（Ｅ）成分とのエステル化反応は、常法に従って行なうことができるが、好ましくは、３０〜１５０℃で２〜１０時間反応を行なう。
また、上記光重合性不飽和化合物（Ｘ）に、さらにエポキシ化合物（Ｄ）を付加させ、続いて多塩基酸無水物（Ｅ）をエステル化させることを１回以上繰り返して得られる構造を有する光重合性不飽和化合物（Ｙ）も同様にして製造することができる。
A reaction product having a structure in which (C) component is esterified with respect to an epoxy adduct having a structure in which (B) component is added to (A) component contained in the alkali-developable resin composition. Further, the photopolymerizable unsaturated compound (X) having a structure obtained by further adding the component (D) and then esterifying the component (E) is produced, for example, by the method represented by the following reaction formula [Chemical Formula 11] can do.
First, the unsaturated monobasic acid (2) as the component (B) is added to the epoxy compound (1) as the component (A) to obtain a resin composition containing the compound (3) as an epoxy adduct. . The addition reaction of the component (B) to the component (A) can be carried out according to a conventional method, but is preferably performed at 90 to 150 ° C. for 5 to 30 hours.
Subsequently, the compound (3) which is an epoxy adduct is reacted with the polybasic acid anhydride (4) which is the component (C) to carry out an esterification reaction, and a resin composition containing the compound (5) which is an ester compound Get things. The esterification reaction between the epoxy adduct and the component (C) can be carried out according to a conventional method, but is preferably performed at 30 to 150 ° C. for 5 to 30 hours.
Subsequently, the compound (5) which is an ester compound is further subjected to an addition reaction with the compound (6) which is an epoxy compound of the component (D) to obtain a compound (7). The addition reaction between the ester compound and the component (D) can be carried out according to a conventional method, but the reaction is preferably carried out at 50 to 150 ° C. for 2 to 30 hours.
Subsequently, the compound (7) is further reacted with the compound (8) which is a polybasic acid anhydride of the component (E) for esterification, and the target reaction product compound (9) [photopolymerizable property] A resin composition containing the unsaturated compound (X)] can be obtained. The esterification reaction between the compound (7) and the component (E) can be performed according to a conventional method, but the reaction is preferably performed at 30 to 150 ° C. for 2 to 10 hours.
In addition, the photopolymerizable unsaturated compound (X) has a structure obtained by further adding an epoxy compound (D) and then esterifying the polybasic acid anhydride (E) one or more times. The photopolymerizable unsaturated compound (Y) can be produced in the same manner.
また、（Ａ）成分に（Ｂ）成分を付加させた構造を有するエポキシ付加物である化合物（３）を得る方法は、上記[化１１]中に示した上記の方法に限定されるわけではなく、例えば、化合物（３）におけるｎが０の場合、下記[化１２]の反応式に示すように、ビスフェノール（１０）とグリシジルメタクリレート（１１）を含むモノエポキシ化合物を反応させる方法によって化合物（３）を得ることもできる。 Moreover, the method of obtaining the compound (3) which is an epoxy adduct having a structure in which the component (B) is added to the component (A) is not limited to the method described above in [Chemical Formula 11]. For example, when n in compound (3) is 0, as shown in the following reaction formula [Chemical Formula 12], compound (10) is reacted with a monoepoxy compound containing bisphenol (10) and glycidyl methacrylate (11). 3) can also be obtained.
本発明の着色アルカリ現像型感光性樹脂組成物の調製に使用される不飽和一塩基酸（Ｂ）としては、例えば、アクリル酸、メタクリル酸、クロトン酸、桂皮酸、ソルビン酸、ヒドロキシエチルメタクリレート・マレート、ヒドロキシエチルアクリレート・マレート、ヒドロキシプロピルメタクリレート・マレート、ヒドロキシプロピルアクリレート・マレート、ジシクロペンタジエン・マレートあるいは１個のカルボキシル基と２個以上の（メタ）アクリロイル基とを有する多官能（メタ）アクリレート等が挙げられる。 Examples of the unsaturated monobasic acid (B) used for the preparation of the colored alkali development type photosensitive resin composition of the present invention include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate, Malate, hydroxyethyl acrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl acrylate / malate, dicyclopentadiene / malate or polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups Etc.
上記１個のカルボキシル基と２個以上の（メタ）アクリロイル基とを有する多官能（メタ）アクリレートは、例えば１分子中に１個のヒドロキシル基と２個以上の（メタ）アクリロイル基とを有する多官能（メタ）アクリレートと二塩基酸無水物又はカルボン酸とを反応させることによって得ることができる。 The polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups has, for example, one hydroxyl group and two or more (meth) acryloyl groups in one molecule. It can be obtained by reacting a polyfunctional (meth) acrylate with a dibasic acid anhydride or carboxylic acid.
上記１個のカルボキシル基と２個以上の（メタ）アクリロイル基とを有する多官能（メタ）アクリレートとしては、下記化合物Ｎｏ．１０〜１４を挙げることができる。 Examples of the polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups include the following compound Nos. 10-14 can be mentioned.
本発明の着色アルカリ現像型感光性樹脂組成物の調製に使用される多塩基酸無水物（Ｃ）としては、コハク酸無水物、マレイン酸無水物、トリメリット酸無水物、ピロメリット酸無水物、２，２’−３，３’−ベンゾフェノンテトラカルボン酸無水物、３，３’−４，４’−ベンゾフェノンテトラカルボン酸無水物、エチレングリコールビスアンヒドロトリメリテート、グリセロールトリスアンヒドロトリメリテート、無水フタル酸、ヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、テトラヒドロ無水フタル酸、ナジック酸無水物、メチルナジック酸無水物、トリアルキルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、５−（２，５−ジオキソテトラヒドロフリル）−３−メチル−３−シクロヘキセン−１，２−ジカルボン酸無水物、トリアルキルテトラヒドロ無水フタル酸−無水マレイン酸付加物、ドデセニル無水コハク酸、無水メチルハイミック酸等が挙げられる。これらの中でも、コハク酸無水物、トリメリット酸無水物、ヘキサヒドロ無水フタル酸が好ましい。 Examples of the polybasic acid anhydride (C) used for the preparation of the colored alkali development type photosensitive resin composition of the present invention include succinic acid anhydride, maleic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride. 2,2′-3,3′-benzophenone tetracarboxylic acid anhydride, 3,3′-4,4′-benzophenone tetracarboxylic acid anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimelli Tate, phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2, 5-Dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-di Carboxylic acid anhydride, trialkyl tetrahydrophthalic anhydride - maleic acid adduct, dodecenyl succinic anhydride, and anhydride and methyl high Mick acid. Among these, succinic anhydride, trimellitic anhydride, and hexahydrophthalic anhydride are preferable.
本発明の着色アルカリ現像型感光性樹脂組成物の調製に使用されるエポキシ化合物（Ｄ）としては、単官能又は多官能エポキシ化合物が挙げられる。
上記単官能エポキシ化合物としては、グリシジルメタクリレート、メチルグリシジルエーテル、エチルグリシジルエーテル、プロピルグリシジルエーテル、イソプロピルグリシジルエーテル、ブチルグリシジルエーテル、イソブチルグリシジルエーテル、ｔ−ブチルグリシジルエーテル、ペンチルグリシジルエーテル、ヘキシルグリシジルエーテル、ヘプチルグリシジルエーテル、オクチルグリシジルエーテル、ノニルグリシジルエーテル、デシルグリシジルエーテル、ウンデシルグリシジルエーテル、ドデシルグリシジルエーテル、トリデシルグリシジルエーテル、テトラデシルグリシジルエーテル、ペンタデシルグリシジルエーテル、ヘキサデシルグリシジルエーテル、２−エチルヘキシルグリシジルエーテル、アリルグリシジルエーテル、プロパルギルグリシジルエーテル、p−メトキシエチルグリシジルエーテル、フェニルグリシジルエーテル、ｐ−メトキシグリシジルエーテル、ｐ−ブチルフェノールグリシジルエーテル、クレジルグリシジルエーテル、２−メチルクレジルグリシジルエーテル、４−ノニルフェニルグリシジルエーテル、ベンジルグリシジルエーテル、ｐ−クミルフェニルグリシジルエーテル、トリチルグリシジルエーテル、２，３−エポキシプロピルメタクリレート、エポキシ化大豆油、エポキシ化アマニ油、グリシジルブチレート、ビニルシクロヘキサンモノオキシド、１，２−エポキシ−４−ビニルシクロヘキサン、スチレンオキシド、ピネンオキシド、メチルスチレンオキシド、シクロヘキセンオキシド、プロピレンオキシド、下記化合物No.15〜No.18等が挙げられる。
As an epoxy compound (D) used for preparation of the colored alkali development type photosensitive resin composition of this invention, a monofunctional or polyfunctional epoxy compound is mentioned.
Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl. Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidylate , Propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether Ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4-vinyl Cyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, cyclohexene oxide, propylene oxide, the following compounds No. 15 to No .18 etc.
上記多官能エポキシ化合物としては、ビスフェノール型エポキシ化合物及びグリシジルエーテル類を用いることができる。
上記ビスフェノール型エポキシ化合物としては、上記一般式(I)で表されるアルキリデンビスフェノールポリグリシジルエーテル型エポキシ樹脂を用いることができる他、例えば、水添ビスフェノール型エポキシ化合物等のビスフェノール型エポキシ化合物も用いることができる。
上記グリシジルエーテル類としては、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、１，４−ブタンジオールジグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、１，８−オクタンジオールジグリシジルエーテル、１，１０−デカンジオールジグリシジルエーテル、２，２−ジメチル−１，３−プロパンジオールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、トリエチレングリコールジグリシジルエーテル、テトラエチレングリコールジグリシジルエーテル、ヘキサエチレングリコールジグリシジルエーテル、１，４−シクロヘキサンジメタノールジグリシジルエーテル、１，１，１−トリ（グリシジルオキシメチル）プロパン、１，１，１−トリ（グリシジルオキシメチル）エタン、１，１，１−トリ（グリシジルオキシメチル）メタン、１，１，１，１−テトラ（グリシジルオキシメチル）メタンが挙げられる。
As the polyfunctional epoxy compound, bisphenol type epoxy compounds and glycidyl ethers can be used.
As the bisphenol type epoxy compound, an alkylidene bisphenol polyglycidyl ether type epoxy resin represented by the above general formula (I) can be used, for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used. Can do.
Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1 , 10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-tri ( Glycidyl oxy methyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- tetra (glycidyloxymethyl) include methane.
上記多官能エポキシ化合物としては、その他、フェノールノボラック型エポキシ化合物、ビフェニルノボラック型エポキシ化合物、クレゾールノボラック型エポキシ化合物、ビスフェノールＡノボラック型エポキシ化合物、ジシクロペンタジエンノボラック型エポキシ化合物等のノボラック型エポキシ化合物；３，４−エポキシ−６−メチルシクロヘキシルメチル−３’，４’−エポキシ−６’−メチルシクロヘキサンカルボキシレート、３，４−エポキシシクロヘキシルメチル−３’，４’−エポキシシクロヘキサンカルボキシレート、１−エポキシエチル−３，４−エポキシシクロヘキサン等の脂環式エポキシ化合物；フタル酸ジグリシジルエステル、テトラヒドロフタル酸ジグリシジルエステル、ダイマー酸グリシジルエステルなどのグリシジルエステル類；テトラグリシジルジアミノジフェニルメタン、トリグリシジルＰ−アミノフェノール、Ｎ，Ｎ−ジグリシジルアニリンなどのグリシジルアミン類；１，３−ジグリシジル−５，５−ジメチルヒダントイン、トリグリシジルイソシアヌレート等の複素環式エポキシ化合物；ジシクロペンタジエンジオキシド等のジオキシド化合物；ナフタレン型エポキシ化合物、トリフェニルメタン型エポキシ化合物、ジシクロペンタジエン型エポキシ化合物等を用いることができる。 Other polyfunctional epoxy compounds include other novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds; 3 , 4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1-epoxyethyl -Alicyclic epoxy compounds such as 3,4-epoxycyclohexane; phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, dimer acid glycidyl ester, etc. Glycidyl esters; glycidyl amines such as tetraglycidyl diaminodiphenylmethane, triglycidyl P-aminophenol, N, N-diglycidyl aniline; complex such as 1,3-diglycidyl-5,5-dimethylhydantoin, triglycidyl isocyanurate Cyclic epoxy compounds; Dioxide compounds such as dicyclopentadiene dioxide; naphthalene type epoxy compounds, triphenylmethane type epoxy compounds, dicyclopentadiene type epoxy compounds, and the like can be used.
本発明の着色アルカリ現像型感光性樹脂組成物の調製に使用される多塩基酸無水物（Ｅ）としては、上記多塩基酸無水物（Ｃ）として挙げたものを用いることができる。
（Ａ）〜（Ｅ）の各成分を反応させた構造を有する光重合性不飽和化合物に、さらにエポキシ化合物（Ｄ）を付加させ、続いて多塩基酸無水物（Ｅ）をエステル化させることを繰り返してもよく、また、（Ａ）〜（Ｅ）の各成分を反応させた構造を有する光重合性不飽和化合物に、さらにエポキシ化合物（Ｄ）を付加させた後、多塩基酸無水物（Ｅ）に代えてラクトン化合物をエステル化させてもよい。
As the polybasic acid anhydride (E) used for the preparation of the colored alkali development type photosensitive resin composition of the present invention, those mentioned as the polybasic acid anhydride (C) can be used.
An epoxy compound (D) is further added to a photopolymerizable unsaturated compound having a structure obtained by reacting each component of (A) to (E), and then a polybasic acid anhydride (E) is esterified. Or a polybasic acid anhydride after adding an epoxy compound (D) to a photopolymerizable unsaturated compound having a structure obtained by reacting the components (A) to (E). Instead of (E), a lactone compound may be esterified.
（Ａ）〜（Ｅ）の各成分を反応させて得られる光重合性不飽和化合物（Ｘ）及び、該光重合性不飽和化合物（Ｘ）さらにエポキシ化合物（Ｄ）を付加させ、続いて多塩基酸無水物（Ｅ）をエステル化させることを１回以上繰り返して得られる構造を有する光重合性不飽和化合物（Ｙ）は、それらの含有量が、上記アルカリ現像性樹脂組成物中、１〜７０質量％、特に３〜３０質量％であるのが好ましく、固形分の酸価が３５〜１２０ｍｇ／ＫＯＨ、特に４０〜１００ｍｇ／ＫＯＨの範囲であるのが好ましい。 The photopolymerizable unsaturated compound (X) obtained by reacting the components (A) to (E), the photopolymerizable unsaturated compound (X), and the epoxy compound (D) are added, The photopolymerizable unsaturated compound (Y) having a structure obtained by esterifying the basic acid anhydride (E) one or more times has a content of 1 in the alkali-developable resin composition. It is preferable that it is -70 mass%, especially 3-30 mass%, and it is preferable that the acid value of solid content is 35-120 mg / KOH, Especially it is the range of 40-100 mg / KOH.
上記アルカリ現像性樹脂組成物には、上記光重合性不飽和化合物（Ｘ）又は（Ｙ）の他に、溶媒を含有させてもよく、例えば、光重合性不飽和化合物の含有量を上記の好ましい範囲とする場合、光重合性不飽和化合物以外の残部には溶媒を用いることができる。該溶媒の具体例としては、後述の着色アルカリ現像型感光性樹脂組成物に用いられる溶媒として例示するものが挙げられる。また、上記光重合性不飽和化合物（Ｘ）又は（Ｙ）を合成する際に用いた溶媒を除去せず、そのまま本発明のアルカリ現像性樹脂組成物に含有させてもよい。 In addition to the photopolymerizable unsaturated compound (X) or (Y), the alkali-developable resin composition may contain a solvent. For example, the content of the photopolymerizable unsaturated compound may be set as described above. In the case of a preferred range, a solvent can be used for the remainder other than the photopolymerizable unsaturated compound. Specific examples of the solvent include those exemplified as the solvent used in the colored alkali development type photosensitive resin composition described later. Moreover, you may make it contain in the alkali developable resin composition of this invention as it is, without removing the solvent used when synthesize | combining the said photopolymerizable unsaturated compound (X) or (Y).
上記光重合性不飽和化合物（Ｘ）又は（Ｙ）の含有量は、上記アルカリ現像性樹脂組成物に、光重合開始剤（Ｆ）及び顔料又は染料等の色材（Ｇ）を含有させて得られる着色アルカリ現像型感光性樹脂組成物中、１〜７０質量％、特に３〜３０質量％であるのが好ましく、固形分の酸価が３５〜１２０ｍｇ／ＫＯＨ、特に４０〜１００ｍｇ／ＫＯＨの範囲であるのが好ましい。 Content of the said photopolymerizable unsaturated compound (X) or (Y) makes the said alkali developable resin composition contain color materials (G), such as a photoinitiator (F) and a pigment or dye. It is preferable that it is 1-70 mass% in the colored alkali development type photosensitive resin composition obtained, especially 3-30 mass%, and the acid value of solid content is 35-120 mg / KOH, especially 40-100 mg / KOH. A range is preferred.
本発明の着色アルカリ現像型感光性樹脂組成物に用いられる光重合開始剤（Ｆ）としては、従来既知の化合物を用いることが可能であり、例えば、ベンゾフェノン、フェニルビフェニルケトン、１−ヒドロキシ−１−ベンゾイルシクロヘキサン、ベンジル、ベンジルジメチルケタール、１−ベンジル−１−ジメチルアミノ−１−（４'−モルホリノベンゾイル）プロパン、２−モルホリル−２−（４'−メチルメルカプト）ベンゾイルプロパン、チオキサントン、１−クロル−４−プロポキシチオキサントン、イソプロピルチオキサントン、ジエチルチオキサントン、エチルアントラキノン、４−ベンゾイル−４'−メチルジフェニルスルフィド、ベンゾインブチルエーテル、２−ヒドロキシ−２−ベンゾイルプロパン、２−ヒドロキシ−２−（４'−イソプロピル）ベンゾイルプロパン、４−ブチルベンゾイルトリクロロメタン、４−フェノキシベンゾイルジクロロメタン、ベンゾイル蟻酸メチル、１，７−ビス（９'−アクリジニル）ヘプタン、９−ｎ−ブチル−３，６−ビス（２'−モルホリノイソブチロイル）カルバゾール、２−メチル−１−[４−（メチルチオ）フェニル]−２−モルホリノプロパン−１−オン、２−メチル−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−フェニル−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−ナフチル−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、下記化合物No.19、No.20等が挙げられる。これらの中でも、ベンゾフェノン、２−メチル−１−[４−（メチルチオ）フェニル]−２−モルホリノプロパン−１−オンが好ましい。 As the photopolymerization initiator (F) used in the colored alkali development type photosensitive resin composition of the present invention, conventionally known compounds can be used. For example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1 -Benzoylcyclohexane, benzyl, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4'-morpholinobenzoyl) propane, 2-morpholy-2- (4'-methylmercapto) benzoylpropane, thioxanthone, 1- Chlor-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone, 4-benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- ( '-Isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9'-acridinyl) heptane, 9-n-butyl-3,6-bis (2 '-Morpholinoisobutyroyl) carbazole, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-methyl-4,6-bis (trichloromethyl) -s-triazine 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine, the following compounds No. 19, No. 20 and the like. . Among these, benzophenone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one are preferable.
本発明の着色アルカリ現像型感光性樹脂組成物において、上記光重合開始剤（Ｆ）の含有量は、着色アルカリ現像型感光性樹脂組成物中、０．１〜３０質量％、特に０．５〜５質量％が好ましい。 In the colored alkali-developable photosensitive resin composition of the present invention, the content of the photopolymerization initiator (F) is 0.1 to 30% by mass, particularly 0.5 in the colored alkali-developable photosensitive resin composition. -5 mass% is preferable.
本発明で用いられる溶媒としては、通常、前記の各成分を溶解または分散しえる溶媒であれば特に制限はないが、例えば、メチルエチルケトン、メチルアミルケトン、ジエチルケトン、アセトン、メチルイソプロピルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類；エチルエーテル、ジオキサン、テトラヒドロフラン、１，２−ジメトキシエタン、１，２−ジエトキシエタン、ジプロピレングリコールジメチルエーテル等のエーテル系溶媒；酢酸メチル、酢酸エチル、酢酸−ｎ−プロピル、酢酸イソプロピル、酢酸ｎ−ブチル等のエステル系溶媒；エチ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、プロピレングリコールモノメチルエーテルアセテート等のセルソルブ系溶媒；メタノール、エタノール、イソ−又はｎ−プロパノール、イソ−又はｎ−ブタノール、アミルアルコール等のアルコール系溶媒；ベンゼン、トルエン、キシレン等のＢＴＸ系溶媒；ヘキサン、ヘプタン、オクタン、シクロヘキサン等の脂肪族炭化水素系溶媒；テレピン油、Ｄ−リモネン、ピネン等のテルペン系炭化水素油；ミネラルスピリット、スワゾール＃３１０（コスモ松山石油（株））、ソルベッソ＃１００（エクソン化学（株））等のパラフィン系溶媒；四塩化炭素、クロロホルム、トリクロロエチレン、塩化メチレン等のハロゲン化脂肪族炭化水素系溶媒；クロロベンゼン等のハロゲン化芳香族炭化水素系溶媒；カルビトール系溶媒、アニリン、トリエチルアミン、ピリジン、酢酸、アセトニトリル、二硫化炭素、テトラヒドロフラン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルピロリドン等が挙げられ、中でも、ケトン類あるいはセロソルブ系溶媒が好ましい。これらの溶媒は１種又は２種以上の混合溶媒として使用することができる。 The solvent used in the present invention is not particularly limited as long as it is a solvent that can dissolve or disperse the above-mentioned components. For example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl Ketones such as ketone and cyclohexanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, acetic acid-n- Ester solvents such as propyl, isopropyl acetate, n-butyl acetate; Cellsolv solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate; methanol Alcohol solvents such as ethanol, iso- or n-propanol, iso- or n-butanol and amyl alcohol; BTX solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane Terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; paraffinic solvents such as mineral spirits, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.) Halogenated aliphatic hydrocarbon solvents such as carbon, chloroform, trichloroethylene and methylene chloride; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, Tetrahydrofuran, N, - dimethylformamide, N- methylpyrrolidone, and among these, ketones or cellosolve solvent. These solvents can be used as one or a mixture of two or more.
本発明の着色アルカリ現像型感光性樹脂組成物において、上記溶媒の含有量は、着色アルカリ現像型感光性樹脂組成物に占める全固形分濃度が５〜４０質量％、特に１５〜３０質量％となるように調整するとよい。 In the colored alkali-developable photosensitive resin composition of the present invention, the content of the solvent is such that the total solid concentration in the colored alkali-developable photosensitive resin composition is 5 to 40% by mass, particularly 15 to 30% by mass. It is good to adjust so that it becomes.
本発明の着色アルカリ現像型感光性樹脂組成物に用いられる色材（Ｇ）としては、顔料及び染料を挙げることができる。どちらを添加するかについては特に制限されず、顔料及び染料のいずれか一方を用いても、あるいは両方を併用してもよい。 Examples of the color material (G) used in the colored alkali development type photosensitive resin composition of the present invention include pigments and dyes. Which is added is not particularly limited, and either one of a pigment and a dye may be used, or both may be used in combination.
本発明の着色アルカリ現像型感光性樹脂組成物に色材として使用される顔料としては、従来のカラーフィルタの製造に使用されている公知の顔料をいずれも用いることができる。以下に、有機顔料の具体例をカレーインデックス（Ｃ．Ｉ．）ナンバーで示す。尚、下記一覧中、「ｘ」で表されるのはＣ．Ｉ．ナンバーから任意で選択できる整数である。
・Ｐｉｇｍｅｎｔ Ｂｌｕｅ：
＜Ｃ．Ｉ＞１，１：２，１：ｘ，９：ｘ，１５，１５：１，１５：２，１５：３，１５：４，１５：５，１５：６，１６，２４，２４：ｘ，５６，６０，６１，６２
・Ｐｉｇｍｅｎｔ Ｇｒｅｅｎ：
＜Ｃ．Ｉ＞１，１：ｘ，２，２：ｘ，４，７，１０，３６
・Ｐｉｇｍｅｎｔ Ｏｒａｎｇｅ
＜Ｃ．Ｉ＞２，５，１３，１６，１７：１，３１，３４，３６，３８，４３，４６，４８，４９，５１，５２，５９，６０，６１，６２，６４
・Ｐｉｇｍｅｎｔ Ｒｅｄ
＜Ｃ．Ｉ＞１，２，３，４，５，６，７，９，１０，１４，１７，２２，２３，３１，３８，４１，４８：１，４８：２，４８：３，４８：４，４９，４９：１，４９：２，５２：１，５２：２，５３：１，５７：１，６０：１，６３：１，６６，６７，８１：１，８１：３，８１：ｘ，８３，８８，９０，１１２，１１９，１２２，１２３，１４４，１４６，１４９，１６６，１６８，１６９，１７０，１７１，１７２，１７５，１７６，１７７，１７８，１７９，１８４，１８５，１８７，１８８，１９０，２００，２０２，２０６，２０７，２０８，２０９，２１０，２１６，２２４、２２６
・Ｐｉｇｍｅｎｔ Ｖｉｏｌｅｔ：
＜Ｃ．Ｉ＞１，１：ｘ，３，３：３，３：ｘ，５：１，１９，２３，２７，３２，４２
・Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ
＜Ｃ．Ｉ＞１，３，１２，１３，１４，１６，１７，２４，５５，６０，６５，７３，７４，８１，８３，９３，９５，９７，９８，１００，１０１，１０４，１０６，１０８，１０９，１１０，１１３，１１４，１１６，１１７，１１９，１２０，１２６，１２７，１２８，１２９，１３８，１３９，１５０，１５１，１５２，１５３，１５４，１５６，１７５
As the pigment used as the coloring material in the colored alkali development type photosensitive resin composition of the present invention, any of the known pigments used in the production of conventional color filters can be used. Below, the specific example of an organic pigment is shown with a curry index (CI) number. In the list below, “x” represents C.I. I. It is an integer that can be arbitrarily selected from the numbers.
・ Pigment Blue:
<C. I> 1, 1: 2, 1: x, 9: x, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 24, 24: x, 56, 60, 61, 62
・ Pigment Green:
<C. I> 1,1: x, 2,2: x, 4,7,10,36
・ Pigment Orange
<C. I> 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 59, 60, 61, 62, 64
・ Pigment Red
<C. I> 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 3, 81: x, 83, 88, 90, 112, 119, 122, 123, 144, 146, 149, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 224, 226
・ Pigment Violet:
<C. I> 1, 1: x, 3, 3: 3, 3: x, 5: 1, 19, 23, 27, 32, 42
・ Pigment Yellow
<C. I> 1, 3, 12, 13, 14, 16, 17, 24, 55, 60, 65, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109,110,113,114,116,117,119,120,126,127,128,129,138,139,150,151,152,153,154,156,175
また、黒色顔料としては、三菱化学社製のカーボンブラック＃２４００、＃２３５０、＃２３００、＃２２００、＃１０００、＃９８０、＃９７０、＃９６０、＃９５０、＃９００、＃８５０、ＭＣＦ８８、＃６５０、ＭＡ６００、ＭＡ７、ＭＡ８、ＭＡ１１、ＭＡ１００、ＭＡ２２０、ＩＬ３０Ｂ、ＩＬ３１Ｂ、ＩＬ７Ｂ、ＩＬ１１Ｂ、ＩＬ５２Ｂ、＃４０００、＃４０１０、＃５５、＃５２、＃５０、＃４７、＃４５、＃４４、＃４０、＃３３、＃３２、＃３０、＃２０、＃１０、＃５、ＣＦ９、＃３０５０、＃３１５０、＃３２５０、＃３７５０、＃３９５０、ダイヤブラックＡ、ダイヤブラックＮ２２０Ｍ、ダイヤブラックＮ２３４、ダイヤブラックＩ、ダイヤブラックＬＩ、ダイヤブラックＬＨ、ダイヤブラックＮ３３９、ダイヤブラックＳＨ、ダイヤブラックＳＨＡ、ダイヤブラックＬＨ、ダイヤブラックＨ、ダイヤブラックＨＡ、ダイヤブラックＳＦ，ダイヤブラックＮ５５０Ｍ、ダイヤブラックＥ、ダイヤブラックＧ、ダイヤブラックＲ、ダイヤブラックＮ７６０Ｍ、ダイヤブラックＬＲ、キャンカーブ社製のカーボンブラックサーマックスＮ９９０、Ｎ９９１、Ｎ９０７、Ｎ９０８、Ｎ９９０、Ｎ９９１、Ｎ９０８、旭カーボン社製のカーボンブラック旭＃８０、旭＃７０、旭＃７０Ｌ、旭Ｆ−２００、旭＃６６、旭＃６６Ｕ、旭＃５０、旭＃３５、旭＃１５、アサヒサーマル、デグザ社製のカーボンブラックＣｏｌｏｒＢｌａｃｋ Ｆｗ２００、ＣｏｌｏｒＢｌａｃｋ Ｆｗ２、ＣｏｌｏｒＢｌａｃｋ Ｆｗ２Ｖ、ＣｏｌｏｒＢｌａｃｋ Ｆｗ１、ＣｏｌｏｒＢｌａｃｋ Ｆｗ１８、ＣｏｌｏｒＢｌａｃｋ Ｓ１７０、ＣｏｌｏｒＢｌａｃｋ Ｓ１６０、ＳｐｅｃｉａｌＢｌａｃｋ６、ＳｐｅｃｉａｌＢｌａｃｋ５、ＳｐｅｃｉａｌＢｌａｃｋ４、ＳｐｅｃｉａｌＢｌａｃｋ４Ａ、ＳｐｅｃｉａｌＢｌａｃｋ２５０、ＳｐｅｃｉａｌＢｌａｃｋ３５０、ＰｒｉｎｔｅｘＵ、ＰｒｉｎｔｅｘＶ、Ｐｒｉｎｔｅｘ１４０Ｕ、Ｐｒｉｎｔｅｘ１４０Ｖ（いずれも商品名）等が挙げられる。 Further, as black pigments, carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, # manufactured by Mitsubishi Chemical Corporation 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40 , # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, diamond black LI, diamond black LH, diamond black N339, diamond Rack SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LR, Can Curve Inc. Carbon Black Thermax N990, N991, N907, N908, N990, N991, N908 manufactured by Asahi Carbon Co., Ltd. Carbon Black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal, Degussa's carbon black ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2V, ColorBlack Fw1, ColorBl ack Fw18, ColorBlack S170, ColorBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, SpecialBlack250, Pr, 140, etc.
その他顔料としては、ミロリブルー、酸化鉄、酸化チタン、炭酸カルシウム、炭酸マグネシウム、シリカ、アルミナ、コバルト系、マンガン系、タルク、クロム酸塩、フェロシアン化物、各種金属硫酸塩、硫化物、セレン化物、リン酸塩群青、紺青、コバルトブルー、セルリアンブルー、ピリジアン、エメラルドグリーン、コバルトグリーン等の無機顔料も使用することができる。これらの顔料は単独で、あるいは複数を混合して用いることができる。 Other pigments include miloli blue, iron oxide, titanium oxide, calcium carbonate, magnesium carbonate, silica, alumina, cobalt, manganese, talc, chromate, ferrocyanide, various metal sulfates, sulfides, selenides, Inorganic pigments such as phosphate ultramarine blue, bitumen, cobalt blue, cerulean blue, pyridiane, emerald green, and cobalt green can also be used. These pigments can be used alone or in combination.
上記色材として用いることのできる染料としては、アゾ染料、アントラキノン染料、インジゴイド染料、トリアリールメタン染料、キサンテン染料、アリザリン染料、アクリジン染料スチルベン染料、チアゾール染料、ナフトール染料、キノリン染料、ニトロ染料、インダミン染料、オキサジン染料、フタロシアニン染料、シアニン染料等の染料等が挙げられ、これらは単独で用いても、複数を混合して用いてもよい。 The dyes that can be used as the colorant include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine Examples thereof include dyes such as dyes, oxazine dyes, phthalocyanine dyes, and cyanine dyes. These may be used alone or in combination.
本発明の着色アルカリ現像型感光性樹脂組成物において、上記色材（Ｇ）の含有量は、着色アルカリ現像型感光性樹脂組成物から溶媒を除く全固形分の合計質量に占める割合で０．５〜７０％、特に５〜６０質量％が好ましい。 In the colored alkali-developable photosensitive resin composition of the present invention, the content of the color material (G) is 0. 0% in the total mass of the total solid content excluding the solvent from the colored alkali-developable photosensitive resin composition. 5 to 70%, particularly 5 to 60% by mass is preferable.
本発明の着色アルカリ現像型感光性樹脂組成物には、さらに不飽和結合を有するモノマー、連鎖移動剤、界面活性剤等を併用することができる。 The colored alkali development type photosensitive resin composition of the present invention may further contain a monomer having an unsaturated bond, a chain transfer agent, a surfactant and the like.
上記不飽和結合を有するモノマーとしては、アクリル酸−２−ヒドロキシエチル、アクリル酸−２−ヒドロキシプロピル、アクリル酸イソブチル、アクリル酸N−オクチル、アクリル酸イソオクチル、アクリル酸イソノニル、アクリル酸ステアリル、アクリル酸メトキシエチル、アクリル酸ジメチルアミノエチル、アクリル酸亜鉛、１,６−ヘキサンジオールジアクリレート、トリメチロールプロパントリアクリレート、メタクリル酸−２−ヒドロキシエチル、メタクリル酸−２−ヒドロキシプロピル、メタクリル酸ブチル、メタクリル酸ターシャリーブチル、メタクリル酸シクロヘキシル、トリメチロールプロパントリメタクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールトリアクリレート、トリシクロデカンジメチロールジアクリレート等が挙げられる。 Examples of the monomer having an unsaturated bond include: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, N-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, acrylic acid Methoxyethyl, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, methacrylic acid Tertiary butyl, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol Lithol tetraacrylate, pentaerythritol triacrylate, tricyclodecane dimethylol diacrylate and the like.
本発明の着色アルカリ現像型感光性樹脂組成物において、上記不飽和結合を有するモノマーの含有量は、着色アルカリ現像型感光性樹脂組成物から溶媒を除く全固形分の合計質量に占める割合で０．０１〜２０質量％、特に０．１〜１０質量％が好ましい。 In the colored alkali-developable photosensitive resin composition of the present invention, the content of the monomer having an unsaturated bond is 0% of the total mass of the total solid content excluding the solvent from the colored alkali-developable photosensitive resin composition. 0.01 to 20% by mass, particularly 0.1 to 10% by mass is preferable.
上記連鎖移動剤としては、チオグリコール酸、チオリンゴ酸、チオサリチル酸、２−メルカプトプロピオン酸、３−メルカプトプロピオン酸、３−メルカプト酪酸、Ｎ−（２−メルカプトプロピオニル）グリシン、２−メルカプトニコチン酸、３−〔Ｎ−（２−メルカプトエチル）カルバモイル〕プロピオン酸、３−〔Ｎ−（２−メルカプトエチル）アミノ〕プロピオン酸、Ｎ−（３−メルカプトプロピオニル）アラニン、２−メルカプトエタンスルホン酸、３−メルカプトプロパンスルホン酸、４−メルカプトブタンスルホン酸、ドデシル（４-メチルチオ）フェニルエーテル、２−メルカプトエタノール、３−メルカプト−１，２−プロパンジオール、１−メルカプト−２−プロパノール、３−メルカプト−２−ブタノール、メルカプトフェノール、２−メルカプトエチルアミン、２−メルカプトイミダゾール、２−メルカプト−３−ピリジノール、２−メルカプトベンゾチアゾール、メルカプト酢酸、トリメチロールプロパントリス（3-メルカプトプロピオネート）、ペンタエリスリトールテトラキス（3-メルカプトプロピオネート）等のメルカプト化合物、該メルカプト化合物を酸化して得られるジスルフィド化合物、ヨード酢酸、ヨードプロピオン酸、２−ヨードエタノール、２−ヨードエタンスルホン酸、３−ヨードプロパンスルホン酸等のヨード化アルキル化合物が挙げられる。 Examples of the chain transfer agent include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3 -Mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto- 2-butanol, mercaptov Enol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopro Mercapto compounds such as pionate), disulfide compounds obtained by oxidizing the mercapto compound, iodinated alkyls such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Compounds.
上記界面活性剤としては、パーフルオロアルキルリン酸エステル、パーフルオロアルキルカルボン酸塩等のフッ素界面活性剤、高級脂肪酸アルカリ塩、アルキルスルホン酸塩、アルキル硫酸塩等のアニオン系界面活性剤、高級アミンハロゲン酸塩、第四級アンモニウム塩等のカチオン系界面活性剤、ポリエチレングリコールアルキルエーテル、ポリエチレングリコール脂肪酸エステル、ソルビタン脂肪酸エステル、脂肪酸モノグリセリド等の非イオン界面活性剤、両性界面活性剤、シリコーン系界面活性剤等の界面活性剤を用いることができ、これらは組み合わせて用いてもよい。 Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.
本発明の着色アルカリ現像型感光性樹脂組成物には、さらに熱可塑性有機重合体を用いることによって、硬化物の特性を改善することもできる。該熱可塑性有機重合体としては、例えば、ポリスチレン、ポリメチルメタクリレート、メチルメタクリレート−エチルアクリレート共重合体、ポリ（メタ）アクリル酸、スチレン−（メタ）アクリル酸共重合体、（メタ）アクリル酸−メチルメタクリレート共重合体、ポリビニルブチラール、セルロースエステル、ポリアクリルアミド、飽和ポリエステル等が挙げられる。 In the colored alkali development type photosensitive resin composition of the present invention, the properties of the cured product can be improved by further using a thermoplastic organic polymer. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- Examples include methyl methacrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester.
また、本発明の着色アルカリ現像型感光性樹脂組成物には、必要に応じて、アニソール、ハイドロキノン、ピロカテコール、第三ブチルカテコール、フェノチアジン等の熱重合抑制剤；可塑剤；接着促進剤；充填剤；消泡剤；分散剤；レベリング剤；シランカップリング剤等の慣用の添加物を加えることができる。 In addition, the colored alkali development type photosensitive resin composition of the present invention, if necessary, a thermal polymerization inhibitor such as anisole, hydroquinone, pyrocatechol, tert-butylcatechol, phenothiazine; plasticizer; adhesion promoter; filling Conventional additives such as an agent, an antifoaming agent, a dispersant, a leveling agent, and a silane coupling agent can be added.
本発明の着色アルカリ現像型感光性樹脂組成物は、ロールコーター、カーテンコーター、各種の印刷、浸漬等の公知の手段で、金属、紙、プラスチック等の支持基体上に適用される。また、一旦フィルム等の支持基体上に施した後、他の支持基体上に転写することもでき、その適用方法に制限はない。 The colored alkali-developable photosensitive resin composition of the present invention is applied onto a support substrate such as metal, paper, or plastic by a known means such as a roll coater, curtain coater, various printing, or immersion. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.
本発明の着色アルカリ現像型感光性樹脂組成物は、その用途に特に制限はなく、光硬化性塗料、光硬化性接着剤、印刷版、印刷配線板用フォトレジスト等の各種の用途に使用することができるが、特に、液晶ディスプレイ、プラズマディスプレイ、エレクトロルミネッセンスパネル、ビデオカメラ等に使用されるカラーフィルタの画素部の形成に用いるのに好適である。 The use of the colored alkali development type photosensitive resin composition of the present invention is not particularly limited, and is used for various applications such as a photocurable coating, a photocurable adhesive, a printing plate, and a photoresist for a printed wiring board. However, it is particularly suitable for use in forming a pixel portion of a color filter used in a liquid crystal display, a plasma display, an electroluminescence panel, a video camera or the like.
本発明の着色アルカリ現像型感光性樹脂組成物を用いたカラーフィルタは、常法により製造することができる。 A color filter using the colored alkali development type photosensitive resin composition of the present invention can be produced by a conventional method.
また、本発明の着色アルカリ現像型感光性樹脂組成物を硬化させる際に用いられる活性光の光源としては、波長３００〜４５０ｎｍの光を発光するものを用いることができ、例えば、超高圧水銀、水銀蒸気アーク、カーボンアーク、キセノンアーク等を用いることができる。 Moreover, as the light source of the active light used when curing the colored alkali development type photosensitive resin composition of the present invention, one that emits light having a wavelength of 300 to 450 nm can be used. Mercury vapor arc, carbon arc, xenon arc, etc. can be used.
以下、実施例等を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。尚、下記実施例等において、「％」は、質量％を意味する。
製造例１〜８は、光重合性不飽和化合物の製造及び該光重合性不飽和化合物を含有するアルカリ現像性樹脂組成物Ｎｏ．１〜Ｎｏ．８の調製を示し、比較製造例１及び２は、比較光重合性不飽和化合物の製造及び該比較光重合性不飽和化合物を含有する比較アルカリ現像性樹脂組成物Ｎｏ．９及びＮｏ．１０の調製を示す。実施例１〜８は、製造例１〜８で得られたアルカリ現像性樹脂組成物Ｎｏ．１〜Ｎｏ．８に、光重合開始剤、色材及び溶媒を混合して得られた着色アルカリ現像型感光性樹脂組成物Ｎｏ．１〜Ｎｏ．８の調製を示し、比較例１及び２は、比較製造例１及び２で得られた比較アルカリ現像性樹脂組成物Ｎｏ．９又はＮｏ．１０に、それぞれ光重合開始剤、色材及び溶媒を混合して得られた比較着色アルカリ現像型感光性樹脂組成物Ｎｏ．９及びＮｏ．１０の調製を示す。
EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples. In the following examples and the like, “%” means mass%.
Production Examples 1 to 8 show the production of a photopolymerizable unsaturated compound and an alkali developable resin composition No. 1 containing the photopolymerizable unsaturated compound. 1-No. Comparative Production Examples 1 and 2 show the production of a comparative photopolymerizable unsaturated compound and comparative alkaline developable resin composition No. 1 containing the comparative photopolymerizable unsaturated compound. 9 and no. 10 preparations are shown. Examples 1-8 are the alkali-developable resin composition Nos. Obtained in Production Examples 1-8. 1-No. 8 is obtained by mixing a photopolymerization initiator, a coloring material and a solvent with a colored alkali development type photosensitive resin composition No. 1-No. 8 and Comparative Examples 1 and 2 are comparative alkali-developable resin composition Nos. Obtained in Comparative Production Examples 1 and 2. 9 or No. No. 10, a comparative colored alkali development type photosensitive resin composition No. obtained by mixing a photopolymerization initiator, a coloring material and a solvent, respectively. 9 and no. 10 preparations are shown.
[製造例１] 光重合性不飽和化合物の製造及び該光重合性不飽和化合物を含有するアルカリ現像性樹脂組成物Ｎｏ．１の調製
１，１−ビス（４’―エポキシプロピルオキシフェニル）−１−（１’’−ビフェニル）−１−シクロヘキシルメタン（エポキシ当量２７７、以下、化合物ａ−１ともいう）３７７ｇ、アクリル酸（以下、化合物ｂともいう）９８．１ｇ、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．６ｇ、テトラブチルアンモニウムアセテート２．５ｇ及びプロピレングリコール−１−モノメチルエーテル−２−アセテート３１８ｇを仕込み、１２０℃で１５時間撹拌した。室温まで冷却し、プロピレングリコール−１−モノメチルエーテル−２−アセテート１７７ｇ及び無水コハク酸（以下化合物ｃともいう）１２８ｇ及びテトラブチルアンモニウムアセテート５.７ｇを加えて１００℃で６時間撹拌した。更に１，１−ビス（４’―エポキシプロピルオキシフェニル）−１−（１’’−ビフェニル）−１−シクロヘキシルメタン（以下、化合物ｄ−１ともいう）２２６ｇ及び２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．６ｇ、プロピレングリコール−１−モノメチルエーテル−２−アセテート１００ｇを加えて９０℃で１時間、１２０℃で８時間撹拌した。室温まで冷却し、無水コハク酸（以下、化合物ｅ−１ともいう）４０ｇを加えて１００℃で５時間攪拌した。室温まで冷却し、プロピレングリコール−１−モノメチルエーテル−２−アセテート４７２ｇを加えて、プロピレングリコール−１−モノメチルエーテル−２−アセテート溶液として目的物であるアルカリ現像性樹脂組成物Ｎｏ．１を得た（Ｍｗ＝１２０００、Ｍｎ＝３６００、酸価（固形分）５６ｍｇＫＯＨ／ｇ）。
尚、アルカリ現像性樹脂組成物Ｎｏ．１が含有する光重合性不飽和化合物は、（Ａ）成分である化合物ａ−１に（Ｂ）成分である化合物ｂを付加させた構造を有するエポキシ付加物の水酸基１個に対し、（Ｃ）成分である化合物ｃの酸無水物構造が０．９４個の比率で、（Ｄ）成分である化合物ｄ−１のエポキシ基が０．６個の比率で、（Ｅ）成分である化合物ｅ−１の酸無水物構造が０．２９個の比率で、エポキシ付加物と化合物ｃ及び化合物ｄ−１、続いて化合物ｅ−１とを反応させて得られたものである。また、上記エポキシ付加物は、化合物ａ−１のエポキシ基１個に対し、化合物ｂのカルボキシル基が１．０個の比率で付加させた構造を有するものである。
[Production Example 1] Production of a photopolymerizable unsaturated compound and alkaline developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 1 377 g of 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, hereinafter also referred to as compound a-1), acrylic acid (Hereinafter also referred to as compound b) 98.1 g, 2,6-di-tert-butyl-p-cresol 1.6 g, tetrabutylammonium acetate 2.5 g and propylene glycol-1-monomethyl ether-2-acetate 318 g The mixture was charged and stirred at 120 ° C. for 15 hours. After cooling to room temperature, 177 g of propylene glycol-1-monomethyl ether-2-acetate, 128 g of succinic anhydride (hereinafter also referred to as compound c) and 5.7 g of tetrabutylammonium acetate were added and stirred at 100 ° C. for 6 hours. Furthermore, 226 g of 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (hereinafter also referred to as compound d-1) and 2,6-di-tert- 1.6 g of butyl-p-cresol and 100 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 90 ° C. for 1 hour and at 120 ° C. for 8 hours. After cooling to room temperature, 40 g of succinic anhydride (hereinafter also referred to as compound e-1) was added and stirred at 100 ° C. for 5 hours. The mixture was cooled to room temperature, and 472 g of propylene glycol-1-monomethyl ether-2-acetate was added to obtain the target alkali-developing resin composition No. 1 as a propylene glycol-1-monomethyl ether-2-acetate solution. 1 was obtained (Mw = 12000, Mn = 3600, acid value (solid content) 56 mgKOH / g).
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound contained in 1 represents (C) for one hydroxyl group of an epoxy adduct having a structure in which compound (b) as component (B) is added to compound (a-1) as component (A). Compound c, which is the component (c), has a ratio of 0.94 acid anhydride structures, and (D) the compound d-1, which is the component (D), has a ratio of 0.6, -1 acid anhydride structure was obtained by reacting an epoxy adduct with compound c and compound d-1, followed by compound e-1 at a ratio of 0.29. The epoxy adduct has a structure in which the carboxyl group of compound b is added at a ratio of 1.0 to one epoxy group of compound a-1.
[製造例２] 光重合性不飽和化合物の製造及び該光重合性不飽和化合物を含有するアルカリ現像性樹脂組成物Ｎｏ．２の調製
１，１−ビス（４’―エポキシプロピルオキシフェニル）−１−（１’’−ビフェニル）−１−シクロヘキシルメタン（エポキシ当量２７７、化合物ａ−１）３７７ｇ、アクリル酸９８．１ｇ（化合物ｂ）、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．６ｇ、テトラブチルアンモニウムアセテート２．５ｇ及びプロピレングリコール−１−モノメチルエーテル−２−アセテート３１８ｇを仕込み、１２０℃で１５時間撹拌した。室温まで冷却し、プロピレングリコール−１−モノメチルエーテル−２−アセテート１７７ｇ及び無水コハク酸（化合物ｃ）１２８ｇ及びテトラブチルアンモニウムアセテート５.７ｇを加えて１００℃で６時間撹拌した。更に１，１−ビス（４’―エポキシプロピルオキシフェニル）−１−（１’’−ビフェニル）−１−シクロヘキシルメタン（化合物ｄ−１）２２６ｇ及び２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．６ｇ、プロピレングリコール−１−モノメチルエーテル−２−アセテート１００ｇを加えて９０℃で１時間、１２０℃で８時間撹拌した。室温まで冷却し、無水コハク酸６４ｇ（化合物ｅ−１）を加えて１００℃で５時間撹拌した。室温まで冷却し、プロピレングリコール−１−モノメチルエーテル−２−アセテート５０２ｇを加えて、プロピレングリコール−１−モノメチルエーテル−２−アセテート溶液として目的物であるアルカリ現像性樹脂組成物Ｎｏ．２を得た（Ｍｗ＝１２０００、Ｍｎ＝３８００、酸価（固形分）７１ｍｇＫＯＨ／ｇ）。
尚、アルカリ現像性樹脂組成物Ｎｏ．２が含有する光重合性不飽和化合物は、（Ａ）成分である化合物ａ−１に（Ｂ）成分である化合物ｂを付加させた構造を有するエポキシ付加物の水酸基１個に対し、（Ｃ）成分である化合物ｃの酸無水物構造が０．９４個の比率で、（Ｄ）成分である化合物ｄ−１のエポキシ基が０．６個の比率で、（Ｅ）成分である化合物ｅ−１の酸無水物構造が０．４７個の比率で、エポキシ付加物と化合物ｃ及び化合物ｄ−１、続いて化合物ｅ−１とを反応させて得られたものである。また、上記エポキシ付加物は、化合物ａのエポキシ基１個に対し、化合物ｂのカルボキシル基が１．０個の比率で付加させた構造を有するものである。
[Production Example 2] Production of photopolymerizable unsaturated compound and alkali-developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 2 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, compound a-1) 377 g, acrylic acid 98.1 g ( Compound b), 1.6 g of 2,6-di-tert-butyl-p-cresol, 2.5 g of tetrabutylammonium acetate and 318 g of propylene glycol-1-monomethyl ether-2-acetate were charged and stirred at 120 ° C. for 15 hours. did. After cooling to room temperature, 177 g of propylene glycol-1-monomethyl ether-2-acetate, 128 g of succinic anhydride (compound c) and 5.7 g of tetrabutylammonium acetate were added and stirred at 100 ° C. for 6 hours. Further, 226 g of 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (compound d-1) and 2,6-di-tert-butyl-p- 1.6 g of cresol and 100 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 90 ° C. for 1 hour and at 120 ° C. for 8 hours. The mixture was cooled to room temperature, 64 g of succinic anhydride (Compound e-1) was added, and the mixture was stirred at 100 ° C. for 5 hours. After cooling to room temperature, 502 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the alkali-developing resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution was added. 2 was obtained (Mw = 12000, Mn = 3800, acid value (solid content) 71 mgKOH / g).
In addition, alkali developable resin composition No. 2 includes a photopolymerizable unsaturated compound (C) with respect to one hydroxyl group of an epoxy adduct having a structure in which compound (b) as component (B) is added to compound a-1 as component (A). Compound c, which is the component (c), has a ratio of 0.94 acid anhydride structures, and (D) the compound d-1, which is the component (D), has a ratio of 0.6, -1 acid anhydride structure was obtained by reacting an epoxy adduct with compound c and compound d-1, followed by compound e-1 at a ratio of 0.47. The epoxy adduct has a structure in which the carboxyl group of compound b is added at a ratio of 1.0 to one epoxy group of compound a.
[製造例３] 光重合性不飽和化合物の製造及び該光重合性不飽和化合物を含有するアルカリ現像性樹脂組成物Ｎｏ．３の調製
エポキシ化合物である化合物Ｎｏ．１（エポキシ当量６１０、ｎ＝１．５、以下、化合物ａ−２ともいう）３６４ｇ、アクリル酸（化合物ｂ）４３．０ｇ、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．３ｇ、テトラブチルアンモニウムアセテート３．３ｇ及びプロピレングリコール−１−モノメチルエーテル−２−アセテート２６６ｇを仕込み、１２０℃で１０時間撹拌した。室温まで冷却し、プロピレングリコール−１−モノメチルエーテル−２−アセテート１２６ｇ及び無水コハク酸（化合物ｃ）７９ｇを加えて１００℃で５時間撹拌した。更にグリシジルメタクリレート（以下、化合物ｄ−２ともいう）１０６ｇ及び２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．３ｇを加えて９０℃で１時間、１２０℃で１０時間撹拌した。室温まで冷却し、無水テトラヒドロフタル酸９８ｇ（以下、化合物ｅ−２ともいう）を加えて１００℃で５時間撹拌した。室温まで冷却し、プロピレングリコール−１−モノメチルエーテル−２−アセテート３５７ｇを加えて、プロピレングリコール−１−モノメチルエーテル−２−アセテート溶液として目的物であるアルカリ現像性樹脂組成物Ｎｏ．３を得た（Ｍｗ＝５３００、Ｍｎ＝３２００、酸価（固形分）６２ｍｇＫＯＨ／ｇ）。
尚、アルカリ現像性樹脂組成物Ｎｏ．３が含有する光重合性不飽和化合物は、（Ａ）成分である化合物ａ−２に（Ｂ）成分である化合物ｂを付加させた構造を有するエポキシ付加物の水酸基１個に対し、（Ｃ）成分である化合物ｃの酸無水物構造が０．７５個の比率で、（Ｄ）成分である化合物ｄ−２のエポキシ基が０．７個の比率で、（Ｅ）成分である化合物ｅ−２の酸無水物構造が０．６個の比率でエポキシ付加物と化合物ｃ及び化合物ｄ−２、続いて化合物ｅ−２とをエステル化反応させて得られたものである。また、上記エポキシ付加物は、化合物ａ−２のエポキシ基１個に対し、化合物ｂのカルボキシル基が１．０個の比率で付加させた構造を有するものである。
[Production Example 3] Production of a photopolymerizable unsaturated compound and alkaline developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of Compound No. 3 which is an epoxy compound 1 (epoxy equivalent 610, n = 1.5, hereinafter also referred to as compound a-2) 364 g, acrylic acid (compound b) 43.0 g, 2,6-di-tert-butyl-p-cresol 1.3 g, Tetrabutylammonium acetate 3.3 g and propylene glycol-1-monomethyl ether-2-acetate 266 g were charged and stirred at 120 ° C. for 10 hours. After cooling to room temperature, 126 g of propylene glycol-1-monomethyl ether-2-acetate and 79 g of succinic anhydride (compound c) were added and stirred at 100 ° C. for 5 hours. Further, 106 g of glycidyl methacrylate (hereinafter also referred to as compound d-2) and 1.3 g of 2,6-di-tert-butyl-p-cresol were added, and the mixture was stirred at 90 ° C. for 1 hour and at 120 ° C. for 10 hours. After cooling to room temperature, 98 g of tetrahydrophthalic anhydride (hereinafter also referred to as compound e-2) was added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 357 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the alkali-developable resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution was added. 3 was obtained (Mw = 5300, Mn = 3200, acid value (solid content) 62 mgKOH / g).
In addition, alkali developable resin composition No. 3 contains a photopolymerizable unsaturated compound (C) with respect to one hydroxyl group of an epoxy adduct having a structure in which compound (b) as component (B) is added to compound a-2 as component (A). Compound c, which is the component (c), has a ratio of 0.75 acid anhydride structures, and the compound (d), which is the component d-2, has a ratio of 0.7, and the compound e, which is the component (E). -2 acid anhydride structure is obtained by esterifying the epoxy adduct, compound c and compound d-2, and then compound e-2 at a ratio of 0.6. The epoxy adduct has a structure in which the carboxyl group of compound b is added at a ratio of 1.0 to one epoxy group of compound a-2.
[製造例４] 光重合性不飽和化合物の製造及び該光重合性不飽和化合物を含有するアルカリ現像性樹脂組成物Ｎｏ．４の調製
１，１−ビス（４’―エポキシプロピルオキシフェニル）−１−（１’’−ビフェニル）−１−シクロヘキシルメタン（エポキシ当量２７７、化合物ａ−１）３６８ｇ、アクリル酸（化合物ｂ）９５．７ｇ、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．７ｇ、テトラブチルアンモニウムアセテート２．４ｇ及びプロピレングリコール−１−モノメチルエーテル−２−アセテート３１０ｇを仕込み、１２０℃で１５時間撹拌した。室温まで冷却し、プロピレングリコール−１−モノメチルエーテル−２−アセテート１５８ｇ及び無水コハク酸（化合物ｃ）１０６ｇ及びテトラブチルアンモニウムアセテート５．６ｇを加えて１００℃で５時間撹拌した。更に１，１−ビス（４’―エポキシプロピルオキシフェニル）−１−（１’’−ビフェニル）−１−シクロヘキシルメタン１４７ｇ（エポキシ当量２７７、ｎ＝０、化合物ｄ−１）及び２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．７ｇ、プロピレングリコール−１−モノメチルエーテル−２−アセテート６８ｇを加えて１００℃で３時間撹拌した。室温まで冷却し、グリシジルメタクリレート（化合物ｄ−２）７６ｇを加えて、１２０℃で７時間撹拌した。更に無水コハク酸８６ｇ（化合物ｅ−１）を加えて１００℃で３時間撹拌した。室温まで冷却し、プロピレングリコール−１−モノメチルエーテル−２−アセテート５４６ｇを加えて、プロピレングリコール−１−モノメチルエーテル−２−アセテート溶液として目的物であるアルカリ現像性樹脂組成物Ｎｏ．４を得た（Ｍｗ＝５６００、Ｍｎ＝２９００、酸価（固形分）５９ｍｇＫＯＨ／ｇ）。
尚、アルカリ現像性樹脂組成物Ｎｏ．４が含有する光重合性不飽和化合物は、（Ａ）成分である化合物ａ−１に（Ｂ）成分である化合物ｂを付加させた構造を有するエポキシ付加物の水酸基１個に対し、（Ｃ）成分である化合物ｃの酸無水物構造が０．８個の比率で、（Ｄ）成分である化合物ｄ−１及び化合物ｄ−２のエポキシ基が０．８個の比率で、（Ｅ）成分である化合物ｅ−１の酸無水物構造が０．６５個の比率でエポキシ付加物と化合物ｃ及び化合物ｄ−１並びに化合物ｄ−２、続いて化合物ｅ−１とをエステル化反応させて得られたものである。また、上記エポキシ付加物は、化合物ａ−１のエポキシ基１個に対し、化合物ｂのカルボキシル基が１．０個の比率で付加させた構造を有するものである。
[Production Example 4] Production of a photopolymerizable unsaturated compound and alkaline developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 4 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, compound a-1) 368 g, acrylic acid (compound b) 95.7 g, 2,6-di-tert-butyl-p-cresol 1.7 g, tetrabutylammonium acetate 2.4 g and propylene glycol-1-monomethyl ether-2-acetate 310 g were charged and stirred at 120 ° C. for 15 hours. did. After cooling to room temperature, 158 g of propylene glycol-1-monomethyl ether-2-acetate, 106 g of succinic anhydride (compound c) and 5.6 g of tetrabutylammonium acetate were added and stirred at 100 ° C. for 5 hours. Further, 147 g of 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, n = 0, compound d-1) and 2,6- Di-tert-butyl-p-cresol (1.7 g) and propylene glycol-1-monomethyl ether-2-acetate (68 g) were added, and the mixture was stirred at 100 ° C. for 3 hours. After cooling to room temperature, 76 g of glycidyl methacrylate (Compound d-2) was added and stirred at 120 ° C. for 7 hours. Further, 86 g of succinic anhydride (Compound e-1) was added and stirred at 100 ° C. for 3 hours. After cooling to room temperature, 546 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the alkali-developable resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution was added. 4 was obtained (Mw = 5600, Mn = 2900, acid value (solid content) 59 mgKOH / g).
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound contained in 4 is a compound (C) with respect to one hydroxyl group of an epoxy adduct having a structure in which the compound b (component (B)) is added to the compound a-1 (component (A)). The component (c) is an acid anhydride structure in a ratio of 0.8, the component (D) is a compound d-1 and the compound d-2 has a ratio of 0.8 epoxy groups, and (E) Compound e-1, which is a component, has an acid anhydride structure in a ratio of 0.65, and an esterification reaction is performed between epoxy adduct, compound c, compound d-1, compound d-2, and then compound e-1. It is obtained. The epoxy adduct has a structure in which the carboxyl group of compound b is added at a ratio of 1.0 to one epoxy group of compound a-1.
[製造例５] 光重合性不飽和化合物の製造及び該光重合性不飽和化合物を含有するアルカリ現像性樹脂組成物Ｎｏ．５の調製
１，１−ビス（４’―エポキシプロピルオキシフェニル）−１−（１’’−ビフェニル）−１−シクロヘキシルメタン（エポキシ当量２７７、化合物ａ−１）７８２ｇ、アクリル酸２０３ｇ（化合物ｂ）、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール３．１ｇ、テトラブチルアンモニウムアセテート５．１ｇ及びプロピレングリコール−１−モノメチルエーテル−２−アセテート６６０ｇを仕込み、１２０℃で１３時間撹拌した。室温まで冷却し、プロピレングリコール−１−モノメチルエーテル−２−アセテート３３５ｇ及び無水コハク酸（化合物ｃ）２２６ｇ及びテトラブチルアンモニウムアセテート１１．９ｇを加えて１００℃で５時間撹拌した。更に１，１−ビス（４’―エポキシプロピルオキシフェニル）−１−（１’’−ビフェニル）−１−シクロヘキシルメタン２３５ｇ（化合物ｄ−１）及び２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール３．１ｇを加えて１００℃で３時間撹拌した。更にグリシジルメタクリレート（化合物ｄ−２）１００ｇを加えて、１２０℃で７時間撹拌した。室温まで冷却し、トリメリット酸無水物（以下、化合物ｅ−３ともいう）８１ｇを加えて１００℃で３時間撹拌した。室温まで冷却し、プロピレングリコール−１−モノメチルエーテル−２−アセテート８９９ｇを加えて、プロピレングリコール−１−モノメチルエーテル−２−アセテート溶液として目的物であるアルカリ現像性樹脂組成物Ｎｏ．５を得た（Ｍｗ＝４２００、Ｍｎ＝２３００、酸価（固形分）５７ｍｇＫＯＨ／ｇ）。
尚、アルカリ現像性樹脂組成物Ｎｏ．５が含有する光重合性不飽和化合物は、（Ａ）成分である化合物ａ−１に（Ｂ）成分である化合物ｂを付加させた構造を有するエポキシ付加物の水酸基１個に対し、（Ｃ）成分である化合物ｃの酸無水物構造が０．８個の比率で、（Ｄ）成分である化合物ｄ−１及び化合物ｄ−２のエポキシ基が０．５５個の比率で、（Ｅ）成分である化合物ｅ−３の酸無水物構造が０．１５個の比率でエポキシ付加物と化合物ｃ及び化合物ｄ−１並びに化合物ｄ−２、続いて化合物ｅ−３とをエステル化反応させて得られたものである。また、上記エポキシ付加物は、化合物ａ−１のエポキシ基１個に対し、化合物ｂのカルボキシル基が１．０個の比率で付加させた構造を有するものである。
[Production Example 5] Production of a photopolymerizable unsaturated compound and alkali-developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 5 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, compound a-1) 782 g, acrylic acid 203 g (compound b ), 2,6-di-tert-butyl-p-cresol (3.1 g), tetrabutylammonium acetate (5.1 g) and propylene glycol-1-monomethyl ether-2-acetate (660 g), and the mixture was stirred at 120 ° C. for 13 hours. After cooling to room temperature, 335 g of propylene glycol-1-monomethyl ether-2-acetate, 226 g of succinic anhydride (compound c) and 11.9 g of tetrabutylammonium acetate were added and stirred at 100 ° C. for 5 hours. Further, 235 g of 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (compound d-1) and 2,6-di-tert-butyl-p- Cresol 3.1g was added and it stirred at 100 degreeC for 3 hours. Further, 100 g of glycidyl methacrylate (Compound d-2) was added and stirred at 120 ° C. for 7 hours. After cooling to room temperature, 81 g of trimellitic anhydride (hereinafter also referred to as compound e-3) was added and stirred at 100 ° C. for 3 hours. After cooling to room temperature, 899 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the alkali-developable resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution was added. 5 was obtained (Mw = 4200, Mn = 2300, acid value (solid content) 57 mgKOH / g).
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound contained in 5 is a compound (C) for one hydroxyl group of an epoxy adduct having a structure in which a compound b (B) is added to a compound a-1 (A). The component (c) is an acid anhydride structure having a ratio of 0.8, and the component (D) is a compound d-1 and the compound d-2 has an epoxy group of 0.55. Compound e-3, which is a component, has an acid anhydride structure at a ratio of 0.15, and an esterification reaction is carried out between epoxy adduct, compound c, compound d-1, compound d-2, and then compound e-3. It is obtained. The epoxy adduct has a structure in which the carboxyl group of compound b is added at a ratio of 1.0 to one epoxy group of compound a-1.
[製造例６] 光重合性不飽和化合物の製造及び該光重合性不飽和化合物を含有するアルカリ現像性樹脂組成物Ｎｏ．６の調製
１，１−ビス（４’―エポキシプロピルオキシフェニル）−１−（１’’−ビフェニル）−１−シクロヘキシルメタン（エポキシ当量２７７、化合物ａ−１）５６６ｇ、アクリル酸１４７ｇ（化合物ｂ）、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール２．３ｇ、テトラブチルアンモニウムアセテート３．７ｇ及びプロピレングリコール−１−モノメチルエーテル−２−アセテート４７７ｇを仕込み、１２０℃で１６時間撹拌した。室温まで冷却し、プロピレングリコール−１−モノメチルエーテル−２−アセテート２４２ｇ及び無水コハク酸（化合物ｃ）１６４ｇ及びテトラブチルアンモニウムアセテート８．６ｇを加えて１００℃で５時間撹拌した。更にネオペンチルグリコールジグリシジルエーテル１５１ｇ（エポキシ当量１４８、以下、化合物ｄ−３ともいう）及び２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール２．３ｇを加えて９０℃で１時間、１２０℃で３時間撹拌した。更に３，４−エポキシシクロヘキシルメチルアクリレート（エポキシ当量１８９、以下、化合物ｄ−４ともいう）５７．９ｇを加えて、１２０℃で８時間撹拌した。室温まで冷却し、無水テトラヒドロフタル酸１４０ｇ（化合物ｅ−２）を加えて１００℃で３時間撹拌した。室温まで冷却し、プロピレングリコール−１−モノメチルエーテル−２−アセテート７８２ｇを加えて、プロピレングリコール−１−モノメチルエーテル−２−アセテート溶液として目的物であるアルカリ現像性樹脂組成物Ｎｏ．６を得た（Ｍｗ＝４９００、Ｍｎ＝２４００、酸価（固形分）５９ｍｇＫＯＨ／ｇ）。
尚、アルカリ現像性樹脂組成物Ｎｏ．６が含有する光重合性不飽和化合物は、（Ａ）成分である化合物ａ−１に（Ｂ）成分である化合物ｂを付加させた構造を有するエポキシ付加物の水酸基１個に対し、（Ｃ）成分である化合物ｃの酸無水物構造が０．８個の比率で、（Ｄ）成分である化合物ｄ−３及び化合物ｄ−４のエポキシ基が０．６５個の比率で、（Ｅ）成分である化合物ｅ−２の酸無水物構造が０．４５個の比率でエポキシ付加物と化合物ｃ及び化合物ｄ−３並びに化合物ｄ−４、続いて化合物ｅ−２とをエステル化反応させて得られたものである。また、上記エポキシ付加物は、化合物ａ−１のエポキシ基１個に対し、化合物ｂのカルボキシル基が１．０個の比率で付加させた構造を有するものである。
[Production Example 6] Production of a photopolymerizable unsaturated compound and alkaline developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 6 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, compound a-1) 566 g, acrylic acid 147 g (compound b) ), 2.3 g of 2,6-di-tert-butyl-p-cresol, 3.7 g of tetrabutylammonium acetate and 477 g of propylene glycol-1-monomethyl ether-2-acetate, and stirred at 120 ° C. for 16 hours. After cooling to room temperature, 242 g of propylene glycol-1-monomethyl ether-2-acetate, 164 g of succinic anhydride (compound c) and 8.6 g of tetrabutylammonium acetate were added and stirred at 100 ° C. for 5 hours. Further, 151 g of neopentyl glycol diglycidyl ether (epoxy equivalent 148, hereinafter also referred to as compound d-3) and 2.3 g of 2,6-di-tert-butyl-p-cresol were added, and 90 ° C. for 1 hour, 120 ° C. For 3 hours. Further, 57.9 g of 3,4-epoxycyclohexylmethyl acrylate (epoxy equivalent 189, hereinafter also referred to as compound d-4) was added and stirred at 120 ° C. for 8 hours. After cooling to room temperature, 140 g (compound e-2) of tetrahydrophthalic anhydride was added and stirred at 100 ° C. for 3 hours. After cooling to room temperature, 782 g of propylene glycol-1-monomethyl ether-2-acetate was added, and the alkali developing resin composition No. 1 as the target product as a propylene glycol-1-monomethyl ether-2-acetate solution was added. 6 was obtained (Mw = 4900, Mn = 2400, acid value (solid content) 59 mgKOH / g).
In addition, alkali developable resin composition No. 6 includes a photopolymerizable unsaturated compound (C) with respect to one hydroxyl group of an epoxy adduct having a structure in which the compound (b) as the component (B) is added to the compound a-1 as the component (A). The component (c) is an acid anhydride structure in a ratio of 0.8, and the component (D) is a compound d-3 and the compound d-4 has an epoxy group in a ratio of 0.65. Compound e-2, which is a component, has an acid anhydride structure at a ratio of 0.45, and an esterification reaction is performed between epoxy adduct, compound c, compound d-3, compound d-4, and then compound e-2. It is obtained. The epoxy adduct has a structure in which the carboxyl group of compound b is added at a ratio of 1.0 to one epoxy group of compound a-1.
[製造例７] 光重合性不飽和化合物の製造及び該光重合性不飽和化合物を含有するアルカリ現像性樹脂組成物Ｎｏ．７の調製
１，１−ビス（４’―エポキシプロピルオキシフェニル）−１−（１’’−ビフェニル）−１−シクロヘキシルメタン（エポキシ当量２７７、化合物ａ−１）３７７ｇ、アクリル酸（化合物ｂ）９８．１ｇ、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．６ｇ、テトラブチルアンモニウムアセテート２．５ｇ及びプロピレングリコール−１−モノメチルエーテル−２−アセテート３１８ｇを仕込み、１２０℃で１５時間撹拌した。室温まで冷却し、プロピレングリコール−１−モノメチルエーテル−２−アセテート１７７ｇ及び無水コハク酸（化合物ｃ）１２８ｇ及びテトラブチルアンモニウムアセテート５.７ｇを加えて１００℃で６時間撹拌した。更に１，１−ビス（４’―エポキシプロピルオキシフェニル）−１−（１’’−ビフェニル）−１−シクロヘキシルメタン（化合物ｄ−１）２２６ｇ及び２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．６ｇ、プロピレングリコール−１−モノメチルエーテル−２−アセテート１００ｇを加えて９０℃で１時間、１２０℃で８時間撹拌した。室温まで冷却し、無水コハク酸（化合物ｅ−１）４０ｇを加えて１００℃で５時間攪拌した。続いて、１，１−ビス（４’―エポキシプロピルオキシフェニル）−１−（１’’−ビフェニル）−１−シクロヘキシルメタン（化合物ｄ−１）２２６ｇ及び２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．６ｇ、プロピレングリコール−１−モノメチルエーテル−２−アセテート１００ｇを加えて９０℃で１時間、１２０℃で８時間撹拌した。室温まで冷却し、無水コハク酸（化合物ｅ−１）４０ｇを加えて１００℃で５時間攪拌した。室温まで冷却し、プロピレングリコール−１−モノメチルエーテル−２−アセテート４７２ｇを加えて、プロピレングリコール−１−モノメチルエーテル−２−アセテート溶液として目的物であるアルカリ現像性樹脂組成物Ｎｏ．７を得た（Ｍｗ＝１８０００、Ｍｎ＝４２００、酸価（固形分）５１ｍｇＫＯＨ／ｇ）。
尚、アルカリ現像性樹脂組成物Ｎｏ．７が含有する光重合性不飽和化合物は、（Ａ）成分である化合物ａ−１に（Ｂ）成分である化合物ｂを付加させた構造を有するエポキシ付加物の水酸基１個に対し、（Ｃ）成分である化合物ｃの酸無水物構造が０．９４個の比率で、（Ｄ）成分である化合物ｄ−１のエポキシ基が０．６個の比率で、（Ｅ）成分である化合物ｅ−１の酸無水物構造が０．２９個の比率で、続いて（Ｄ）成分である化合物ｄ−１のエポキシ基が０．６個の比率で、（Ｅ）成分である化合物ｅ−１の酸無水物構造が０．２９個の比率で、エポキシ付加物と化合物ｃ及び化合物ｄ−１、続いて化合物ｅ−１、さらに化合物ｄ−１、続いて化合物ｅ−１とを反応させて得られたものである。また、上記エポキシ付加物は、化合物ａ−１のエポキシ基１個に対し、化合物ｂのカルボキシル基が１．０個の比率で付加させた構造を有するものである。
[Production Example 7] Production of a photopolymerizable unsaturated compound and alkaline developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 7 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, compound a-1) 377 g, acrylic acid (compound b) 98.1 g, 1.6 g of 2,6-di-tert-butyl-p-cresol, 2.5 g of tetrabutylammonium acetate and 318 g of propylene glycol-1-monomethyl ether-2-acetate were charged and stirred at 120 ° C. for 15 hours. did. After cooling to room temperature, 177 g of propylene glycol-1-monomethyl ether-2-acetate, 128 g of succinic anhydride (compound c) and 5.7 g of tetrabutylammonium acetate were added and stirred at 100 ° C. for 6 hours. Further, 226 g of 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (compound d-1) and 2,6-di-tert-butyl-p- 1.6 g of cresol and 100 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 90 ° C. for 1 hour and at 120 ° C. for 8 hours. The mixture was cooled to room temperature, 40 g of succinic anhydride (Compound e-1) was added, and the mixture was stirred at 100 ° C. for 5 hours. Subsequently, 226 g of 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (compound d-1) and 2,6-di-tert-butyl- 1.6 g of p-cresol and 100 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 90 ° C. for 1 hour and at 120 ° C. for 8 hours. The mixture was cooled to room temperature, 40 g of succinic anhydride (Compound e-1) was added, and the mixture was stirred at 100 ° C. for 5 hours. The mixture was cooled to room temperature, and 472 g of propylene glycol-1-monomethyl ether-2-acetate was added to obtain the target alkali-developing resin composition No. 1 as a propylene glycol-1-monomethyl ether-2-acetate solution. 7 was obtained (Mw = 18000, Mn = 4200, acid value (solid content) 51 mgKOH / g).
In addition, alkali developable resin composition No. 7 contains a photopolymerizable unsaturated compound having one structure (C) for one hydroxyl group of an epoxy adduct having a structure in which compound (b) as component (B) is added to compound a-1 as component (A). Compound c, which is the component (c), has a ratio of 0.94 acid anhydride structures, and (D) the compound d-1, which is the component (D), has a ratio of 0.6, -1 acid anhydride structure at a ratio of 0.29, followed by a ratio of 0.6 epoxy group of the compound d-1 as the component (D), and compound e-1 as the component (E) In the ratio of 0.29 acid anhydride structures, the epoxy adduct was reacted with compound c and compound d-1, followed by compound e-1, further compound d-1, and then compound e-1. It is obtained. The epoxy adduct has a structure in which the carboxyl group of compound b is added at a ratio of 1.0 to one epoxy group of compound a-1.
[製造例８] 光重合性不飽和化合物の製造及び該光重合性不飽和化合物を含有するアルカリ現像性樹脂組成物Ｎｏ．８の調製
１，１−ビス（４’―エポキシプロピルオキシフェニル）−１−（１’’−ビフェニル）−１−シクロヘキシルメタン（エポキシ当量２７７、化合物ａ−１）３７７ｇ、アクリル酸（化合物ｂ）９８．１ｇ、無水コハク酸（化合物ｃ）１２８ｇ、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．６ｇ、テトラブチルアンモニウムアセテート８．２ｇ及びプロピレングリコール−１−モノメチルエーテル−２−アセテート４９５ｇを仕込み、１１０℃で２０時間撹拌した。続いて、１，１−ビス（４’―エポキシプロピルオキシフェニル）−１−（１’’−ビフェニル）−１−シクロヘキシルメタン（化合物ｄ−１）２２６ｇ及び２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．６ｇ、プロピレングリコール−１−モノメチルエーテル−２−アセテート１００ｇを加えて９０℃で１時間、１２０℃で８時間撹拌した。室温まで冷却し、無水コハク酸（化合物ｅ−１）４０ｇを加えて１００℃で５時間攪拌した。続いて、１，１−ビス（４’―エポキシプロピルオキシフェニル）−１−（１’’−ビフェニル）−１−シクロヘキシルメタン（化合物ｄ−１）２２６ｇ及び２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．６ｇ、プロピレングリコール−１−モノメチルエーテル−２−アセテート１００ｇを加えて９０℃で１時間、１２０℃で８時間撹拌した。室温まで冷却し、無水コハク酸（化合物ｅ−１）４０ｇを加えて１００℃で５時間攪拌した。室温まで冷却し、プロピレングリコール−１−モノメチルエーテル−２−アセテート４７２ｇを加えて、プロピレングリコール−１−モノメチルエーテル−２−アセテート溶液として目的物であるアルカリ現像性樹脂組成物Ｎｏ．８を得た（Ｍｗ＝１１０００、Ｍｎ＝３５００、酸価（固形分）５７ｍｇＫＯＨ／ｇ）。
尚、アルカリ現像性樹脂組成物Ｎｏ．８が含有する光重合性不飽和化合物は、（Ａ）成分である化合物ａ−１に（Ｂ）成分である化合物ｂを付加させた構造を有するエポキシ付加物の水酸基１個に対し、（Ｃ）成分である化合物ｃの酸無水物構造が０．９４個の比率で、（Ｄ）成分である化合物ｄ−１のエポキシ基が０．６個の比率で、（Ｅ）成分である化合物ｅ−１の酸無水物構造が０．２９個の比率で、続いて（Ｄ）成分である化合物ｄ−１のエポキシ基が０．６個の比率で、（Ｅ）成分である化合物ｅ−１の酸無水物構造が０．２９個の比率で、エポキシ付加物と化合物ｃ及び化合物ｄ−１、続いて化合物ｅ−１、さらに化合物ｄ−１、続いて化合物ｅ−１とを反応させて得られたものである。また、上記エポキシ付加物は、化合物ａ−１のエポキシ基１個に対し、化合物ｂのカルボキシル基が１．０個の比率で付加させた構造を有するものである。
[Production Example 8] Production of a photopolymerizable unsaturated compound and alkali-developable resin composition No. 1 containing the photopolymerizable unsaturated compound. Preparation of 8 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277, compound a-1) 377 g, acrylic acid (compound b) 98.1 g, 128 g of succinic anhydride (compound c), 1.6 g of 2,6-di-tert-butyl-p-cresol, 8.2 g of tetrabutylammonium acetate and 495 g of propylene glycol-1-monomethyl ether-2-acetate And stirred at 110 ° C. for 20 hours. Subsequently, 226 g of 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (compound d-1) and 2,6-di-tert-butyl- 1.6 g of p-cresol and 100 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 90 ° C. for 1 hour and at 120 ° C. for 8 hours. The mixture was cooled to room temperature, 40 g of succinic anhydride (Compound e-1) was added, and the mixture was stirred at 100 ° C. for 5 hours. Subsequently, 226 g of 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (compound d-1) and 2,6-di-tert-butyl- 1.6 g of p-cresol and 100 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 90 ° C. for 1 hour and at 120 ° C. for 8 hours. The mixture was cooled to room temperature, 40 g of succinic anhydride (Compound e-1) was added, and the mixture was stirred at 100 ° C. for 5 hours. The mixture was cooled to room temperature, and 472 g of propylene glycol-1-monomethyl ether-2-acetate was added to obtain the target alkali-developing resin composition No. 1 as a propylene glycol-1-monomethyl ether-2-acetate solution. 8 was obtained (Mw = 11000, Mn = 3500, acid value (solid content) 57 mgKOH / g).
In addition, alkali developable resin composition No. The photopolymerizable unsaturated compound contained in 8 is a compound (C) for one hydroxyl group of an epoxy adduct having a structure obtained by adding the compound (b) as the component (B) to the compound a-1 as the component (A). Compound c, which is the component (c), has a ratio of 0.94 acid anhydride structures, and (D) the compound d-1, which is the component (D), has a ratio of 0.6, -1 acid anhydride structure at a ratio of 0.29, followed by a ratio of 0.6 epoxy group of the compound d-1 as the component (D), and compound e-1 as the component (E) In the ratio of 0.29 acid anhydride structures, the epoxy adduct was reacted with compound c and compound d-1, followed by compound e-1, further compound d-1, and then compound e-1. It is obtained. The epoxy adduct has a structure in which the carboxyl group of compound b is added at a ratio of 1.0 to one epoxy group of compound a-1.
[比較製造例１] 比較光重合性不飽和化合物の製造及び該比較光重合性不飽和化合物を含有する比較アルカリ現像性樹脂組成物Ｎｏ．９の調製
１，１−ビス（４’―エポキシプロピルオキシフェニル）−１−（１’’−ビフェニル）−１−シクロヘキシルメタン（エポキシ当量２７７）３７７ｇ、アクリル酸９８．１ｇ、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．５ｇ、テトラブチルアンモニウムアセテート２．５ｇ及びプロピレングリコール−１−モノメチルエーテル−２−アセテート３１８ｇを仕込み、１２０℃で１５時間撹拌した。室温まで冷却し、プロピレングリコール−１−モノメチルエーテル−２−アセテート１６１ｇ及び無水コハク酸１０９ｇ及びテトラブチルアンモニウムアセテート５．７ｇを加えて１００℃で６時間撹拌した。更に１，１−ビス（４’―エポキシプロピルオキシフェニル）−１−（１’’−ビフェニル）−１−シクロヘキシルメタン２００ｇ及び２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．５ｇ、プロピレングリコール−１−モノメチルエーテル−２−アセテート８６ｇを加えて９０℃で１時間、１２０℃で８時間撹拌した。室温まで冷却し、プロピレングリコール−１−モノメチルエーテル−２−アセテート３９５ｇを加えて、プロピレングリコール−１−モノメチルエーテル−２−アセテート溶液として比較アルカリ現像性樹脂組成物Ｎｏ．９を得た（Ｍｗ＝７２００、Ｍｎ＝２９００、酸価（固形分）３０ｍｇＫＯＨ／ｇ）。
[Comparative Production Example 1] Production of a comparative photopolymerizable unsaturated compound and comparative alkali-developable resin composition No. 1 containing the comparative photopolymerizable unsaturated compound. Preparation of 9 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (epoxy equivalent 277) 377 g, acrylic acid 98.1 g, 2,6-di -1.5 g of tert-butyl-p-cresol, 2.5 g of tetrabutylammonium acetate and 318 g of propylene glycol-1-monomethyl ether-2-acetate were charged and stirred at 120 ° C. for 15 hours. After cooling to room temperature, 161 g of propylene glycol-1-monomethyl ether-2-acetate, 109 g of succinic anhydride and 5.7 g of tetrabutylammonium acetate were added and stirred at 100 ° C. for 6 hours. Furthermore, 1,1-bis (4′-epoxypropyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane 200 g and 2,6-di-tert-butyl-p-cresol 1.5 g, propylene 86 g of glycol-1-monomethyl ether-2-acetate was added and stirred at 90 ° C. for 1 hour and at 120 ° C. for 8 hours. After cooling to room temperature, 395 g of propylene glycol-1-monomethyl ether-2-acetate was added to give a comparative alkali developable resin composition No. 1 as a propylene glycol-1-monomethyl ether-2-acetate solution. 9 was obtained (Mw = 7200, Mn = 2900, acid value (solid content) 30 mgKOH / g).
[比較製造例２] 比較光重合性不飽和化合物の製造及び該比較光重合性不飽和化合物を含有する比較アルカリ現像性樹脂組成物Ｎｏ．１０の調製
エポキシ化合物である化合物Ｎｏ．１（エポキシ当量６２０、ｎ＝１．６）３６４ｇ、アクリル酸４２．３ｇ、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．３ｇ、テトラブチルアンモニウムアセテート３．３ｇ及びプロピレングリコール−１−モノメチルエーテル−２−アセテート２６６ｇを仕込み、１２０℃で１０時間撹拌した。室温まで冷却し、プロピレングリコール−１−モノメチルエーテル−２−アセテート１２６ｇ及び無水コハク酸７９ｇを加えて１００℃で５時間撹拌した。更にグリシジルメタクリレート１０６ｇ及び２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１ｇを加えて９０℃で１時間、１２０℃で１０時間撹拌した。室温まで冷却し、プロピレングリコール−１−モノメチルエーテル−２−アセテート３３３ｇを加えて、プロピレングリコール−１−モノメチルエーテル−２−アセテート溶液として比較アルカリ現像性樹脂組成物Ｎｏ．１０を得た（Ｍｗ＝７８００、Ｍｎ＝３０００、酸価（固形分）１５ｍｇＫＯＨ／ｇ）。
[Comparative Production Example 2] Production of a comparative photopolymerizable unsaturated compound and comparative alkali-developable resin composition No. 1 containing the comparative photopolymerizable unsaturated compound. Preparation of Compound No. 10 which is an epoxy compound 1 (epoxy equivalent 620, n = 1.6) 364 g, acrylic acid 42.3 g, 2,6-di-tert-butyl-p-cresol 1.3 g, tetrabutylammonium acetate 3.3 g and propylene glycol-1- 266 g of monomethyl ether-2-acetate was charged and stirred at 120 ° C. for 10 hours. The mixture was cooled to room temperature, 126 g of propylene glycol-1-monomethyl ether-2-acetate and 79 g of succinic anhydride were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, 106 g of glycidyl methacrylate and 1 g of 2,6-di-tert-butyl-p-cresol were added and stirred at 90 ° C. for 1 hour and at 120 ° C. for 10 hours. After cooling to room temperature, 333 g of propylene glycol-1-monomethyl ether-2-acetate was added to give a comparative alkali developable resin composition No. 1 as a propylene glycol-1-monomethyl ether-2-acetate solution. 10 was obtained (Mw = 7800, Mn = 3000, acid value (solid content) 15 mgKOH / g).
[実施例１〜８（製造例１〜８で得られたアルカリ現像性樹脂組成物Ｎｏ．１〜Ｎｏ．８をそれぞれ含有する着色アルカリ現像型感光性樹脂組成物Ｎｏ．１〜Ｎｏ．８の調製）及び比較例１及び２（比較製造例１及び２で得られた比較アルカリ現像性樹脂組成物Ｎｏ．９又は１０を含有する比較着色アルカリ現像型感光性樹脂組成物Ｎｏ．９及びＮｏ．１０の調製）]
製造例１〜８で得られたアルカリ現像性樹脂組成物Ｎｏ．１〜８並びに比較製造例１及び２で得られた比較アルカリ現像性樹脂組成物Ｎｏ．９又はＮｏ．１０の１２ｇに対し、トリメチロールプロパントリアクリレート８．０ｇ、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキシド１．８ｇ、カーボンブラック(三菱化学社製「ＭＡ１００」)３．２ｇ及びプロピレングリコール−１−モノメチルエーテル−２−アセテート７５ｇを加えてよく撹拌し、着色アルカリ現像型感光性樹脂組成物Ｎｏ．１〜８及び比較着色アルカリ現像型感光性樹脂組成物Ｎｏ．９及びＮｏ．１０を得た。
[Examples 1 to 8 (colored alkali-developable photosensitive resin compositions No. 1 to No. 8 respectively containing alkali-developable resin compositions No. 1 to No. 8 obtained in Production Examples 1 to 8) Preparation) and Comparative Examples 1 and 2 (comparative colored alkali-developable photosensitive resin compositions No. 9 and No. 10 containing comparative alkali-developable resin composition No. 9 or 10 obtained in Comparative Production Examples 1 and 2). 10 preparation)]
Alkali-developable resin composition Nos. Obtained in Production Examples 1-8. 1 to 8 and Comparative Alkali Developable Resin Composition Nos. 1 and 2 obtained in Comparative Production Examples 1 and 2. 9 or No. 10, 12 g of trimethylolpropane triacrylate, 1.8 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 3.2 g of carbon black (“MA100” manufactured by Mitsubishi Chemical Corporation) and propylene glycol-1- Monomethyl ether-2-acetate (75 g) was added and stirred well, and the colored alkali development type photosensitive resin composition No. 1-8 and comparative coloring alkali development type photosensitive resin composition No.1. 9 and no. 10 was obtained.
上記実施例例１〜８で調整した着色アルカリ現像型感光性樹脂組成物Ｎｏ．１〜Ｎｏ．８並びに比較例１及び２で調製した比較着色アルカリ現像型感光性樹脂組成物Ｎｏ．９及びＮｏ．１０の評価を以下のようにして行った。
すなわち、基板上にγ−グリシドキシプロピルメチルエトキシシランをスピンコートして良くスピン乾燥させた後、上記着色アルカリ現像型感光性樹脂組成物をスピンコート（１３００ｒ．ｐ．ｍ、５０秒間）し乾燥させた。７０℃で２０分間プリベークを行った後、ポリビニルアルコール５質量％溶液をコートして酸素遮断膜とした。７０℃２０分間の乾燥後、所定のマスクを用い、光源として超高圧水銀ランプを用いて露光後、２．５質量％炭酸ナトリウム溶液に２５℃で３０秒間浸漬して現像し、良く水洗した。水洗乾燥後、２３０℃で１時間ベークしてパターンを定着させた。得られたパターンについて、以下の評価を行った。結果を表１に示す。
The colored alkali development type photosensitive resin composition No. adjusted in Examples 1 to 8 above. 1-No. 8 and comparative colored alkali-developable photosensitive resin composition No. 1 prepared in Comparative Examples 1 and 2. 9 and no. Ten evaluations were performed as follows.
Specifically, γ-glycidoxypropylmethylethoxysilane was spin-coated on a substrate and spin-dried well, and then the above-mentioned colored alkali development type photosensitive resin composition was spin-coated (1300 rpm) for 50 seconds. Dried. After pre-baking at 70 ° C. for 20 minutes, a 5% by mass polyvinyl alcohol solution was coated to form an oxygen barrier film. After drying at 70 ° C. for 20 minutes, the film was exposed using an ultrahigh pressure mercury lamp as a light source using a predetermined mask, then developed by immersing in a 2.5% by weight sodium carbonate solution at 25 ° C. for 30 seconds, and thoroughly washed with water. After washing with water and drying, the pattern was fixed by baking at 230 ° C. for 1 hour. The following evaluation was performed about the obtained pattern. The results are shown in Table 1.
＜感度＞
露光時に、露光量が１００ｍＪ／ｃｍ2で十分だったものをａ、１００ｍＪ／ｃｍ2では不十分で、１５０ｍＪ／ｃｍ2で露光したものをｂ、１５０ｍＪ／ｃｍ2では不十分で、２００ｍＪ／ｃｍ2で露光したものをｃとした。
＜解像度＞
露光現像時に、線幅１０μｍ以下でも良好にパターン形成できたものをＡ、線幅１０〜１５μｍであれば良好にパターン形成できたものをＢ、線幅１５μｍ以上のものでないと良好なパターン形成ができなかったものをＣと評価した。
＜現像性＞
現像して得られた１５μｍラインアンドスペースの線間に残存する現像残渣の有無で判断した。残渣が認められなかったものを○、残渣が認められたものを×とした。
<Sensitivity>
At the time of exposure, the exposure amount of 100 mJ / cm 2 is sufficient for a, 100 mJ / cm 2 is insufficient, b is 150 mJ / cm 2 for exposure, 150 mJ / cm 2 is insufficient, and 200 mJ / cm 2 The one exposed in 2 was designated as c.
<Resolution>
At the time of exposure and development, A is good pattern formation even if the line width is 10 μm or less, B is good pattern formation if the line width is 10 to 15 μm, and good pattern formation is required unless the line width is 15 μm or more. What was not made was evaluated as C.
<Developability>
Judgment was made based on the presence or absence of a development residue remaining between 15 μm line and space lines obtained by development. A sample in which no residue was observed was marked with ◯, and a sample in which a residue was identified was marked with ×.
また、実施例１〜８で得られた着色アルカリ現像型感光性樹脂組成物Ｎｏ．１〜Ｎｏ．８を用い、常法に従ってカラーフィルターを製造したところ、良好なカラーフィルタが得られた。 In addition, the colored alkali development type photosensitive resin composition Nos. Obtained in Examples 1 to 8 were used. 1-No. When a color filter was produced according to a conventional method using 8, a good color filter was obtained.
実施例１〜８の着色アルカリ現像型感光性樹脂組成物は、高感度で解像度及び現像性に優れるものであった。
それに対して、比較例１〜２の比較着色アルカリ現像型感光性樹脂組成物Ｎｏ．９及びＮｏ．１０は、感度が低いため露光量を多くせざるを得ず、解像度が低下し、線幅１５μｍ以上でないと形成できず、また、現像性も思わしくなかった。
また、本発明の着色アルカリ現像型感光性樹脂組成物を用いたカラーフィルタは、実用に耐える良好なものであった。
The colored alkali-developable photosensitive resin compositions of Examples 1 to 8 had high sensitivity and excellent resolution and developability.
On the other hand, comparative coloring alkali development type photosensitive resin composition No. 1 of Comparative Examples 1-2 was used. 9 and no. No. 10 could not be formed unless the exposure amount was increased due to the low sensitivity, the resolution was lowered, the line width was not more than 15 μm, and the developability was not satisfactory.
In addition, the color filter using the colored alkali development type photosensitive resin composition of the present invention was satisfactory for practical use.
Claims (5)
A color filter comprising the colored alkali development type photosensitive resin composition according to claim 1.
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| JP2000053746A (en) * | 1998-08-06 | 2000-02-22 | Nippon Shokubai Co Ltd | Production of photosensitive resin and photosensitive resin composition containing resin produced by the method |
| WO2006137257A1 (en) * | 2005-06-20 | 2006-12-28 | Toppan Printing Co., Ltd. | Colored alkali-developable photosensitive resin composition and color filters made by using the same |
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| JP2000053746A (en) * | 1998-08-06 | 2000-02-22 | Nippon Shokubai Co Ltd | Production of photosensitive resin and photosensitive resin composition containing resin produced by the method |
| WO2006137257A1 (en) * | 2005-06-20 | 2006-12-28 | Toppan Printing Co., Ltd. | Colored alkali-developable photosensitive resin composition and color filters made by using the same |
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