JPH107981A - Resin composition for cured coating film, and color filter protection film and color filter produced from the same - Google Patents
Resin composition for cured coating film, and color filter protection film and color filter produced from the sameInfo
- Publication number
- JPH107981A JPH107981A JP16019296A JP16019296A JPH107981A JP H107981 A JPH107981 A JP H107981A JP 16019296 A JP16019296 A JP 16019296A JP 16019296 A JP16019296 A JP 16019296A JP H107981 A JPH107981 A JP H107981A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- color filter
- coating film
- copolymer resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 54
- 239000011248 coating agent Substances 0.000 title claims abstract description 51
- 239000011342 resin composition Substances 0.000 title claims description 13
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 49
- -1 acrylic ester Chemical class 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 9
- 150000007513 acids Chemical class 0.000 claims abstract description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 5
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000001681 protective effect Effects 0.000 claims description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 9
- 125000002723 alicyclic group Chemical group 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 150000003923 2,5-pyrrolediones Chemical class 0.000 claims description 7
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 claims description 3
- DABFKTHTXOELJF-UHFFFAOYSA-N 1-propylpyrrole-2,5-dione Chemical compound CCCN1C(=O)C=CC1=O DABFKTHTXOELJF-UHFFFAOYSA-N 0.000 claims description 3
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 claims description 3
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 claims description 3
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 14
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 72
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 39
- 239000000203 mixture Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 23
- 239000002904 solvent Substances 0.000 description 21
- 239000000758 substrate Substances 0.000 description 17
- 239000011521 glass Substances 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 10
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000004793 Polystyrene Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 5
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 5
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000037303 wrinkles Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-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
- 229920000178 Acrylic resin Polymers 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-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
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 239000003759 ester based solvent Substances 0.000 description 3
- 239000005453 ketone based solvent Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- IAXXETNIOYFMLW-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-methylprop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C(=C)C)CC1C2(C)C IAXXETNIOYFMLW-UHFFFAOYSA-N 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 2
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 2
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 2
- SKKHNUKNMQLBTJ-QIIDTADFSA-N [(1s,4r)-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@H]2C(OC(=O)C(=C)C)C[C@@H]1C2 SKKHNUKNMQLBTJ-QIIDTADFSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 150000008360 acrylonitriles Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LBHPSYROQDMVBS-UHFFFAOYSA-N (1-methylcyclohexyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1(C)CCCCC1 LBHPSYROQDMVBS-UHFFFAOYSA-N 0.000 description 1
- CJCGDEYGAIPAEN-UHFFFAOYSA-N (1-methylcyclohexyl) prop-2-enoate Chemical compound C=CC(=O)OC1(C)CCCCC1 CJCGDEYGAIPAEN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MZVABYGYVXBZDP-UHFFFAOYSA-N 1-adamantyl 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC2CC1(OC(=O)C(=C)C)C3 MZVABYGYVXBZDP-UHFFFAOYSA-N 0.000 description 1
- PHPRWKJDGHSJMI-UHFFFAOYSA-N 1-adamantyl prop-2-enoate Chemical compound C1C(C2)CC3CC2CC1(OC(=O)C=C)C3 PHPRWKJDGHSJMI-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- BJINVQNEBGOMCR-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl acetate Chemical compound COCCOCCOC(C)=O BJINVQNEBGOMCR-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- ODGCZQFTJDEYNI-UHFFFAOYSA-N 2-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)C=CCCC1C(O)=O ODGCZQFTJDEYNI-UHFFFAOYSA-N 0.000 description 1
- UCNCZASVJWGNBZ-UHFFFAOYSA-N 3-(2-ethyl-5-methyl-1h-imidazol-4-yl)propanenitrile Chemical compound CCC1=NC(CCC#N)=C(C)N1 UCNCZASVJWGNBZ-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- IQYMRQZTDOLQHC-ZQTLJVIJSA-N [(1R,4S)-2-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@H]2C(OC(=O)C=C)C[C@@H]1C2 IQYMRQZTDOLQHC-ZQTLJVIJSA-N 0.000 description 1
- PSGCQDPCAWOCSH-OPQQBVKSSA-N [(1s,3r,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@]2(C)[C@H](OC(=O)C=C)C[C@H]1C2(C)C PSGCQDPCAWOCSH-OPQQBVKSSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- KVXNKFYSHAUJIA-UHFFFAOYSA-N acetic acid;ethoxyethane Chemical compound CC(O)=O.CCOCC KVXNKFYSHAUJIA-UHFFFAOYSA-N 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- LJZJMIZQMNDARW-UHFFFAOYSA-N decan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCCCC(CC)OC(=O)C(C)=C LJZJMIZQMNDARW-UHFFFAOYSA-N 0.000 description 1
- OKQAAFJXUODTHO-UHFFFAOYSA-N decane;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCCCCCCCCC OKQAAFJXUODTHO-UHFFFAOYSA-N 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000010971 suitability test Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000007740 vapor deposition Methods 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
- 239000008096 xylene Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Optical Filters (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する利用分野】本発明は、硬化塗膜用樹脂組
成物、これを用いたカラーフィルタ保護膜およびカラー
フィルタに関する。The present invention relates to a resin composition for a cured coating film, a color filter protective film and a color filter using the same.
【０００２】[0002]
【従来の技術】各種物品の表面の劣化や損傷を防止する
目的でコーティング膜を形成することがしばしば行われ
ている。このような、コーティング膜においては、平滑
な塗膜が得られること、基体との密着性が高いこと、強
靱であること、耐水性及び耐薬品性、耐溶剤性が優れて
いること、耐熱性及び耐光性が高くて長期間変質をおこ
さないこと等の性能が要求される。また、近年では液晶
表示素子、太陽電池、光ディスク等に用いられるコーテ
ィング膜として前述の性能に加えて透明性等の要求され
る用途が増加している。例えば、近年、カラーフィルタ
を内蔵したカラー液晶表示素子が種々発表されている。
このカラー液晶表示素子の作製にあたっては、ガラス等
の透明基板上にカラーフィルタを設け、この上にインジ
ウムチンオキシド（ＩＴＯ）等からなる無機薄膜を蒸着
し、ホトリソグラフィー法によって、パターニングして
透明電極を形成した後、さらにこの上に液晶を配置する
方法が主流になっている。この場合、カラーフィルタに
はこの上にＩＴＯを蒸着して、ホトリソグラフィー法で
透明電極を形成するプロセスに耐え得るだけの耐熱性、
耐薬品性が備わっていないため、ＩＴＯを蒸着する前に
カラーフィルタ上に保護膜を形成しておく必要がある。2. Description of the Related Art A coating film is often formed for the purpose of preventing deterioration or damage of the surface of various articles. In such a coating film, a smooth coating film can be obtained, high adhesion to a substrate, toughness, excellent water resistance and chemical resistance, excellent solvent resistance, heat resistance In addition, performance such as high light resistance and no deterioration for a long time is required. In recent years, applications requiring transparency and the like in addition to the above-mentioned performance have been increasing as coating films used for liquid crystal display elements, solar cells, optical disks, and the like. For example, in recent years, various color liquid crystal display elements incorporating a color filter have been announced.
In manufacturing this color liquid crystal display device, a color filter is provided on a transparent substrate such as glass, and an inorganic thin film made of indium tin oxide (ITO) is deposited thereon, and patterned by photolithography to form a transparent electrode. After forming a liquid crystal, a method of further disposing a liquid crystal thereon has become mainstream. In this case, the color filter is formed by depositing ITO thereon and has heat resistance enough to withstand a process of forming a transparent electrode by photolithography.
Since it does not have chemical resistance, it is necessary to form a protective film on a color filter before depositing ITO.
【０００３】このカラーフィルタ保護膜に要求される特
性としては、耐熱性、耐薬品性の他にガラス基板やカラ
ーフィルタとの密着性、コーティング性、透明性、耐傷
性等があげられる。このうち、耐熱性は保護膜上にＩＴ
Ｏ等の透明電極を蒸着により形成する際に、保護膜表面
が、通常２００℃以上に加熱されるため、この条件下で
安定であることが必要である。また、耐薬品性として
は、液晶材料や通常配向膜ワニスの溶剤に用いられるＮ
−メチルピロリドン（ＮＭＰ）に侵されないことが必要
である。The properties required for the color filter protective film include heat resistance, chemical resistance, adhesion to glass substrates and color filters, coating properties, transparency, scratch resistance, and the like. Among them, heat resistance is IT
When a transparent electrode of O or the like is formed by vapor deposition, the surface of the protective film is usually heated to 200 ° C. or higher, so that it is necessary to be stable under this condition. In addition, as for chemical resistance, N.sub.2 which is used for a liquid crystal material or a solvent of a varnish for an alignment film is usually used.
-It must be free from methylpyrrolidone (NMP).
【０００４】また、従来、洗浄処理に適用されていたフ
ロン洗浄剤に代えて、近年ではイソプロピルアルコール
（ＩＰＡ）が用いられている。すなわちこのＩＰＡを用
いた洗浄はカラーフィルタ、保護膜、ＩＴＯ等を形成す
る際にまず水洗浄し、常温条件でＩＰＡ溶液による洗浄
を行った後、乾燥ムラを防ぐため高温(70〜90℃)条件で
ＩＰＡベーパーによる洗浄処理を行う方法である。とこ
ろが、従来の保護膜ではフロン洗浄剤に対しては耐性を
有するものの、ＩＰＡベーパーに対しては、耐性が低い
ため、保護膜上に形成されたＩＴＯ膜をパターニング後
にＩＰＡベーパーによる洗浄を行うと、保護膜面が膨潤
してＩＴＯ／保護膜界面が盛り上がり、パネルの表示品
質に影響を及ぼしてしまうことが分かった。[0004] In recent years, isopropyl alcohol (IPA) has been used in place of the chlorofluorocarbon cleaning agent used in the cleaning process. That is, the cleaning using IPA is carried out by first washing with water when forming a color filter, a protective film, ITO, etc., and then washing with an IPA solution at room temperature, and then a high temperature (70 to 90 ° C.) to prevent drying unevenness. This is a method of performing a cleaning process using IPA vapor under conditions. However, although the conventional protective film has resistance to the chlorofluorocarbon cleaning agent, it has low resistance to IPA vapor. Therefore, when the ITO film formed on the protective film is cleaned by IPA vapor after patterning. It was also found that the surface of the protective film swelled and the interface between the ITO and the protective film was raised, which affected the display quality of the panel.
【０００５】[0005]
【発明が解決しようとする課題】このような耐熱性、耐
薬品性等に優れたコーティング用材料としては、特開昭
５８−１９６５０６号公報や特開昭６２−１１９５０１
号公報記載のアクリル系樹脂、特開昭６０−２１６３０
７号公報、および特開平４−２０２４１８号公報記載の
ポリグリシジル（メタ）アクリレート系樹脂、特開昭６
３−１３１１０３号公報記載のメラミン樹脂、エポキシ
樹脂、その他ポリイミド樹脂等が提案されている。しか
しながら、従来提案されている材料では、それぞれ欠点
があり、すべての要求特性を満足するバランスのとれた
材料は無い。As coating materials having such excellent heat resistance and chemical resistance, there are JP-A-58-196506 and JP-A-62-119501.
Acrylic resin described in JP-A-60-21630
7, polyglycidyl (meth) acrylate resins described in JP-A-4-202418,
A melamine resin, an epoxy resin, and other polyimide resins described in JP-A-3-131103 have been proposed. However, the conventionally proposed materials each have disadvantages, and there is no well-balanced material that satisfies all the required characteristics.
【０００６】例えば、アクリル系樹脂では耐熱性が不十
分であり、ＩＴＯ等の蒸着時に膜の表面にシワやクラッ
クを生じるという問題点がある。メラミン樹脂は、比較
的耐熱性は高いものの、ガラス基板やカラーフィルタと
の密着性が極端に悪く、基板やフィルタ上でハジキを生
じやすい。またポリイミド樹脂は、透明性が不十分な上
に、ワニスの保存安定性に欠ける点や、カラーフィルタ
を侵すような溶剤しか使用できないというような問題点
がある。エポキシ樹脂は密着性の良いものは、耐熱性が
不十分であり、耐熱性の高いものは密着性やコーティン
グ性が劣るため要求特性のバランスをとることができな
い。これらに対して、ポリグリシジル（メタ）アクリレ
ート系樹脂は、耐熱性、透明性は良好であるが、密着
性、耐アルカリ性に問題がある。For example, an acrylic resin has insufficient heat resistance, and has a problem that wrinkles and cracks are formed on the surface of the film during the deposition of ITO or the like. Although melamine resin has relatively high heat resistance, adhesion to a glass substrate or a color filter is extremely poor, and cissing easily occurs on the substrate or the filter. In addition, the polyimide resin has problems such as insufficient transparency, lack of storage stability of the varnish, and the use of only a solvent that damages the color filter. Epoxy resins having good adhesiveness have insufficient heat resistance, and those having high heat resistance have poor adhesion and coating properties, so that the required properties cannot be balanced. On the other hand, polyglycidyl (meth) acrylate resins have good heat resistance and transparency, but have problems in adhesion and alkali resistance.
【０００７】このため、高温高湿下における密着性を向
上させる保護膜材料として、特開平６−１４５５９４号
公報では、グリシジル（メタ）アクリレート及び脂環式
炭化水素基を有する（メタ）アクリレートを成分として
含む共重合体並びにＮ−置換マレイミド及び（メタ）ア
クリル酸を成分として含む共重合体を含有してなる硬化
性組成物が提案されている。しかし、上記公報に具体的
に開示される材料を用いて形成される塗膜であっても、
ＩＰＡベーパーに対する耐性が不十分であることが分か
った。本発明は前記した従来の材料の欠点を解決し、耐
熱性、耐薬品性、密着性、塗布性、透明性、耐傷性等の
要求特性を満足し、かつ耐ＩＰＡベーパー性を格段に向
上させた新規な硬化塗膜用樹脂組成物、これを用いたカ
ラーフィルタ保護膜およびカラーフィルタを提供するも
のである。For this reason, as a protective film material for improving the adhesion under high temperature and high humidity, JP-A-6-145594 discloses glycidyl (meth) acrylate and (meth) acrylate having an alicyclic hydrocarbon group as components. And a curable composition comprising a copolymer containing N-substituted maleimide and (meth) acrylic acid as components. However, even a coating film formed using the materials specifically disclosed in the above publication,
It was found that the resistance to IPA vapor was insufficient. The present invention solves the above-mentioned drawbacks of the conventional materials, satisfies the required properties such as heat resistance, chemical resistance, adhesion, applicability, transparency, and scratch resistance, and significantly improves IPA vapor resistance. And a novel resin composition for a cured coating film, a color filter protective film and a color filter using the same.
【０００８】[0008]
【課題を解決するための手段】本発明になる硬化塗膜用
樹脂組成物は、 Ａ．（１）メタクリル酸グリシジルエステルおよび／ま
たはアクリル酸グリシジルエステル６０〜９０重量部お
よび （２）環内に３級炭素を含む炭素数７〜２０の脂環式メ
タクリル酸エステルおよび／またはアクリル酸エステル
１０〜４０重量部および必要により、共重合可能な不飽
和単量体０〜３０重量部を総量が１００重量部となる量
で重合して得られる共重合樹脂１００重量部 Ｂ．（３）Ｎ−置換マレイミド （４）アクリル酸および／またはメタクリル酸および （５）必要により他の不飽和単量体を重合して得られる
共重合樹脂２０〜２００重量部 Ｃ．多価カルボン酸無水物および多価カルボン酸からな
る群より選ばれる少なくとも１種の化合物５〜５０重量
部ならびに Ｄ．官能性シランカップリング剤３０〜１００重量部を
含有してなるものである。また本発明はこの硬化塗膜用
樹脂組成物を用いたカラーフィルタ保護膜及びこれを用
いたカラーフィルタに関する。Means for Solving the Problems The resin composition for a cured coating film according to the present invention comprises: (1) 60 to 90 parts by weight of glycidyl methacrylate and / or glycidyl acrylate and (2) alicyclic methacrylate and / or acrylate 10 having 7 to 20 carbon atoms containing a tertiary carbon in the ring. A. 100 parts by weight of a copolymer resin obtained by polymerizing 0 to 30 parts by weight and, if necessary, 0 to 30 parts by weight of a copolymerizable unsaturated monomer in a total amount of 100 parts by weight. (3) N-substituted maleimide (4) Acrylic acid and / or methacrylic acid and (5) 20 to 200 parts by weight of a copolymer resin obtained by polymerizing another unsaturated monomer as required. C. 5 to 50 parts by weight of at least one compound selected from the group consisting of polycarboxylic anhydrides and polycarboxylic acids; It contains 30 to 100 parts by weight of a functional silane coupling agent. The present invention also relates to a color filter protective film using the resin composition for a cured coating film and a color filter using the same.
【０００９】[0009]
【発明の実施の形態】本発明における上記のＡ成分であ
る共重合樹脂を構成するモノマー成分としての上記の
（１）メタクリル酸グリシジルエステルまたはアクリル
酸グリシジルエステルは２種以上を併用しても良い。BEST MODE FOR CARRYING OUT THE INVENTION Two or more of the above-mentioned (1) glycidyl methacrylate or glycidyl acrylate as a monomer component constituting a copolymer resin as the above-mentioned component A in the present invention may be used in combination. .
【００１０】本発明におけるＡ成分である共重合樹脂を
構成するモノマー成分としての上記の（２）環内に３級
炭素を含む炭素数７〜２０の脂環式構造を有する脂環式
メタクリル酸エステルおよび／またはアクリル酸エステ
ルとしては、メタクリル酸ノルボルニル、メタクリル酸
ノルボルニルメチル、メタクリル酸アダマンチル、メタ
クリル酸トリシクロ［５．２．１．０２，６］デカン−
８−イル、メタクリル酸トリシクロ［５．２．１．０
２，６］デカン−３（または４）−イルメチル、メタク
リル酸ボルニル、メタクリル酸イソボルニル、メタクリ
ル酸メチルシクロヘキシル等のメタクリル酸エステル
と、アクリル酸ノルボルニル、アクリル酸ノルボルニル
メチル、アクリル酸アダマンチル、アクリル酸トリシク
ロ［５．２．１．０２，６］デカン−８−イル、アクリ
ル酸トリシクロ［５．２．１．０２，６］デカン−３
（または４）−イルメチル、アクリル酸ボルニル、アク
リル酸イソボルニル、アクリル酸メチルシクロヘキシル
等のアクリル酸エステルがあげられる。耐熱性の点から
はメタクリル酸エステルが好ましい。The above-mentioned (2) alicyclic methacrylic acid having an alicyclic structure of 7 to 20 carbon atoms containing a tertiary carbon in the ring as a monomer component constituting the copolymer resin as the component A in the present invention. Examples of the ester and / or acrylate include norbornyl methacrylate, norbornylmethyl methacrylate, adamantyl methacrylate, tricyclo [5.2.1.02,6] decane-methacrylate.
8-yl, tricyclomethacrylate [5.2.1.0
2,6] decane-3 (or 4) -ylmethyl, bornyl methacrylate, isobornyl methacrylate, methylcyclohexyl methacrylate, and other methacrylates, norbornyl acrylate, norbornylmethyl acrylate, adamantyl acrylate, and acrylic acid Tricyclo [5.2.1.02,6] decane-8-yl, tricyclo [5.2.1.02,6] decane-3 acrylate
(Or 4) acrylates such as -ylmethyl, bornyl acrylate, isobornyl acrylate, methylcyclohexyl acrylate, and the like. Methacrylic acid esters are preferred from the viewpoint of heat resistance.
【００１１】本発明におけるＡ成分である共重合樹脂
は、それを構成するモノマーとして上記（１）及び
（２）の成分以外に、他の共重合可能な不飽和単量体を
含んでいても良い。このようなものとしては、不飽和脂
肪酸エステル、芳香族ビニル化合物、Ｎ−置換マレイミ
ド、シアン化ビニル化合物等がある。The copolymer resin which is the component A in the present invention may contain other copolymerizable unsaturated monomers in addition to the above-mentioned components (1) and (2). good. These include unsaturated fatty acid esters, aromatic vinyl compounds, N-substituted maleimides, vinyl cyanide compounds and the like.
【００１２】上記の不飽和脂肪酸エステルとしては、例
えば、アクリル酸メチル、アクリル酸エチル、アクリル
酸ブチル、アクリル酸２−エチルヘキシル等のアクリル
酸アルキルエステル、アクリル酸シクロヘキシル等の上
記の（１）成分以外のアクリル酸シクロアルキルエステ
ル、アクリル酸フェニル、アクリル酸ベンジル等のアク
リル酸芳香族エステル、アクリル酸２−ヒドロキシエチ
ル等のアクリル酸エステル、またはメタクリル酸メチ
ル、メタクリル酸エチル、メタクリル酸ブチル、メタク
リル酸２−エチルヘキシル等のメタクリル酸アルキルエ
ステル、メタクリル酸シクロヘキシル等の上記の（１）
成分以外のメタクリル酸シクロアルキルエステル、メタ
クリル酸フェニル、メタクリル酸ベンジル等のメタクリ
ル酸芳香族エステル、メタクリル酸２−ヒドロキシエチ
ル等のメタクリル酸エステルなどがある。The above unsaturated fatty acid esters include, for example, alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate, and components other than the above-mentioned component (1) such as cyclohexyl acrylate. Aromatic esters such as cycloalkyl acrylate, phenyl acrylate and benzyl acrylate, acrylates such as 2-hydroxyethyl acrylate, or methyl methacrylate, ethyl methacrylate, butyl methacrylate, and methacrylic acid 2 The above-mentioned (1) such as alkyl methacrylates such as -ethylhexyl and cyclohexyl methacrylate;
Other than the components, there are cycloalkyl methacrylate, aromatic methacrylate such as phenyl methacrylate and benzyl methacrylate, and methacrylate such as 2-hydroxyethyl methacrylate.
【００１３】上記の芳香族ビニル化合物としては、例え
ば、スチレンまたはα−メチルスチレン、α−エチルス
チレン等のα−置換スチレン、クロロスチレン、ビニル
トルエン、ｔ−ブチルスチレン等の核置換スチレン等が
ある。上記のＮ−置換マレイミドとしては、公知のもの
が使用できるが、Ｎ−メチルマレイミド、Ｎ−エチルマ
レイミド、Ｎ−プロピルマレイミド、Ｎ−ブチルマレイ
ミド等のＮ−アルキル基置換マレイミド、Ｎ−シクロヘ
キシルマレイミド等のＮ−シクロアルキル基置換マレイ
ミド、Ｎ−フェニルマレイミド等のＮ−アリール基置換
マレイミドからなる群より選ばれる少なくとも１種の化
合物を使用することができる。上記のシアン化ビニル化
合物としては、例えば、アクリロニトリル、メタクリロ
ニトリル等がある。Examples of the above aromatic vinyl compounds include styrene or α-substituted styrene such as α-methylstyrene and α-ethylstyrene, and nucleus-substituted styrene such as chlorostyrene, vinyltoluene and t-butylstyrene. . As the above N-substituted maleimide, known ones can be used, but N-alkyl group-substituted maleimides such as N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, etc. And at least one compound selected from the group consisting of N-aryl-substituted maleimides such as N-cycloalkyl-substituted maleimide and N-phenylmaleimide. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.
【００１４】前記した各単量体は、これらＡ成分の総量
を１００重量部として（１）成分を６０〜９０重量部、
（２）成分を１０〜４０重量部および他の共重合可能な
不飽和単量体を０〜３０重量部として重合させる。
（１）成分が上記の範囲より少ないと、十分な架橋密度
の膜が得られないために耐湿性が低下し、また逆に多い
と得られる塗膜と基板との密着性が不十分となる傾向が
ある。（２）成分が上記の範囲より少ないと、得られる
塗膜の密着性が不十分となり、また逆に多いと耐熱性が
低下する傾向がある。他の共重合可能な不飽和単量体が
上記の範囲より多いと本発明の効果が不十分となる傾向
がある。Each of the above-mentioned monomers contains 60 to 90 parts by weight of the component (1) based on 100 parts by weight of the total amount of the component A,
(2) 10 to 40 parts by weight of the component and 0 to 30 parts by weight of another copolymerizable unsaturated monomer.
If the amount of the component (1) is less than the above range, a film having a sufficient cross-linking density cannot be obtained, resulting in a decrease in moisture resistance. Tend. If the amount of the component (2) is less than the above range, the adhesion of the resulting coating film becomes insufficient, and if it is too large, the heat resistance tends to decrease. If the amount of the other copolymerizable unsaturated monomer is larger than the above range, the effect of the present invention tends to be insufficient.
【００１５】Ａ成分である共重合樹脂は前記（１）成
分，（２）成分および必要により他の共重合可能な不飽
和単量体の各単量体を配合し、共重合させることにより
製造することができる。共重合するにあたっては、ラジ
カル重合やイオン重合等の公知の方法を使用できる。例
えば、重合開始剤の存在下で塊状重合法、溶液重合法、
懸濁重合法、乳化重合法等の方法で製造できる。The copolymer resin as the component A is produced by blending the above-mentioned components (1) and (2) and, if necessary, other copolymerizable unsaturated monomers, and copolymerizing them. can do. For copolymerization, known methods such as radical polymerization and ionic polymerization can be used. For example, bulk polymerization in the presence of a polymerization initiator, solution polymerization,
It can be produced by a method such as a suspension polymerization method or an emulsion polymerization method.
【００１６】重合開始剤としては、例えば、過酸化ベン
ゾイル、過酸化ラウロイル、ジ−ｔ−ブチルペルオキシ
ヘキサヒドロフタレート、ｔ−ブチルペルオキシ−２−
エチルヘキサノエート、１，１−ジ−ｔ−ブチルペルオ
キシ−３，３，５−トリメチルシクロヘキサノン等の有
機過酸化物、アゾビスイソブチロニトリル、アゾビス−
４−メトキシ−２，４−ジメチルバレロニトリル、アゾ
ビスシクロヘキサノン−１−カルボニトリル、アゾジベ
ンゾイル等のアゾ化合物、過硫酸カリウム、過硫酸アン
モニウムに代表される水溶性触媒および過酸化物あるい
は過硫酸塩と還元剤の組み合わせによるレドックス触媒
等、通常のラジカル重合に使用できるものはいずれも使
用することができる。重合触媒は（１），（２）および
他の共重合可能な不飽和単量体の総量に対して０．０１
〜１０重量部の範囲で使用するのが好ましい。また、重
合調節剤としてメルカプタン系化合物、チオグリコー
ル、四臭化炭素、α−メチルスチレンダイマー等を分子
量調節のために必要に応じて添加することができる。重
合温度は０〜２００℃の範囲で適宜選択するのが好まし
く、５０〜１２０℃であるのがより好ましい。Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, di-t-butylperoxyhexahydrophthalate, and t-butylperoxy-2-.
Organic peroxides such as ethylhexanoate, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexanone, azobisisobutyronitrile, azobis-
Azo compounds such as 4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile and azodibenzoyl; water-soluble catalysts represented by potassium persulfate and ammonium persulfate; and peroxides or persulfates Any of those that can be used for ordinary radical polymerization, such as a redox catalyst using a combination of a catalyst and a reducing agent, can be used. The polymerization catalyst is 0.01% based on the total amount of (1), (2) and other copolymerizable unsaturated monomers.
It is preferably used in the range of 10 to 10 parts by weight. Further, as a polymerization regulator, a mercaptan compound, thioglycol, carbon tetrabromide, α-methylstyrene dimer, or the like can be added as needed for controlling the molecular weight. The polymerization temperature is preferably appropriately selected within the range of 0 to 200 ° C, and more preferably 50 to 120 ° C.
【００１７】溶液重合における溶媒としては、通常のラ
ジカル重合に使用される溶媒が使用できる。具体例とし
ては、ベンゼン、トルエン、キシレン等の芳香族系溶
剤；アセトン、メチルエチルケトン、メチルイソブチル
ケトン、シクロヘキサノン等のケトン系溶剤；ジエチル
エーテル、イソプロピルエーテル、テトラヒドロフラ
ン、ジオキサン、エチレングリコールジメチルエーテ
ル、エチレングリコールジエチルエーテル、ジエチレン
グリコールジメチルエーテル、ジエチレングリコールジ
エチルエーテル等のエーテル系溶剤；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、エチレングリコールモノメチルエーテルアセター
ト、エチレングリコールモノエチルエーテルアセター
ト、エチレングリコールモノブチルエーテルアセター
ト、ジエチレングリコールモノメチルエーテルアセター
ト、ジエチレングリコールモノエチルエーテルアセター
ト、プロピレングリコールモノメチルエーテルアセター
ト、プロピレングリコールモノエチルエーテルアセター
ト、プロピレングリコールジアセタート、γ−ブチロラ
クトン等のエステル系溶剤；ジメチルホルムアミド、ジ
メチルアセトアミド、Ｎ−メチルピロリドン等のアミド
系溶剤等が挙げられる。これらの溶剤のうち、エステル
系溶剤およびケトン系溶剤が好ましく、単独または２種
類以上を混合して使用することができる。なお、硬化塗
膜用樹脂組成物として用いる場合は溶剤を含有している
ので、同じ溶剤を用いて溶液重合法によって重合するの
が好ましいが、重合体製造後メタノール再沈法等の方法
によりポリマを単離し、他の溶剤に溶解して使用に供す
ることも可能である。As the solvent in the solution polymerization, a solvent used in ordinary radical polymerization can be used. Specific examples include aromatic solvents such as benzene, toluene, and xylene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether. , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether and other ether solvents; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether Acetate, diethylene glycol monomethyl ether acetate, diethylene glycol Ester-based solvents such as monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol diacetate, and γ-butyrolactone; amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone Solvents and the like. Of these solvents, ester solvents and ketone solvents are preferred, and they can be used alone or as a mixture of two or more. When used as a resin composition for a cured coating film, since it contains a solvent, it is preferable to polymerize by a solution polymerization method using the same solvent.However, after producing the polymer, the polymer is produced by a method such as methanol reprecipitation method. Can be isolated and used after being dissolved in another solvent.
【００１８】本発明におけるＡ成分の共重合樹脂の分子
量は、本発明の組成物を基体に均一な膜として塗布する
ことができる限り特に限定されないが、通常５，０００
〜３００，０００（ポリスチレン換算重量平均分子量）
であり、形成する硬化塗膜の膜厚、塗布方法等の塗膜形
成の目的や条件に応じて適宜選択することができる。The molecular weight of the copolymer resin of the component A in the present invention is not particularly limited as long as the composition of the present invention can be applied to a substrate as a uniform film.
~ 300,000 (weight average molecular weight in terms of polystyrene)
The thickness can be appropriately selected according to the purpose and conditions of the coating film formation, such as the thickness of the cured coating film to be formed and the coating method.
【００１９】本発明におけるＢ成分である共重合樹脂を
構成するモノマー成分としてのＮ−置換マレイミドとし
ては、公知のものが使用できるが、Ｎ−メチルマレイミ
ド、Ｎ−エチルマレイミド、Ｎ−プロピルマレイミド、
Ｎ−ブチルマレイミド等のＮ−アルキル基置換マレイミ
ド、Ｎ−シクロヘキシルマレイミド等のＮ−シクロアル
キル置換マレイミド、Ｎ−フェニルマレイミドおよびＮ
−アルキル基置換マレイミドからなる群より選ばれる少
なくとも１種の化合物を使用することが、耐熱性および
基材との密着性の観点から好ましい。これらのうちでも
Ｎ−シクロヘキシルマレイミドおよびＮ−フェニルマレ
イミドが特に好ましい。本発明におけるＢ成分である共
重合樹脂におけるアクリル酸またはメタクリル酸を使用
する際はこれらを併用してもよい。本発明におけるＢ成
分の共重合樹脂のモノマー成分として（３）Ｎ−置換マ
レイミドまたは（４）アクリル酸またはメタクリル酸以
外の他の共重合可能な不飽和単量体を使用してもよい。
このような不飽和単量体としては、不飽和脂肪酸エステ
ル、芳香族ビニル化合物、シアン化ビニル化合物等があ
り、これらの具体例としては、Ａ成分の共重合樹脂のモ
ノマー成分としての他の共重合可能な不飽和単量体とし
て例示したものを挙げることができる。As the N-substituted maleimide as a monomer component constituting the copolymer resin as the component B in the present invention, known ones can be used, and N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide,
N-alkyl group-substituted maleimides such as N-butylmaleimide; N-cycloalkyl-substituted maleimides such as N-cyclohexylmaleimide; N-phenylmaleimide;
It is preferable to use at least one compound selected from the group consisting of -alkyl-substituted maleimide from the viewpoint of heat resistance and adhesion to a substrate. Among these, N-cyclohexylmaleimide and N-phenylmaleimide are particularly preferred. When acrylic acid or methacrylic acid in the copolymer resin as the component B in the present invention is used, these may be used in combination. As the monomer component of the copolymer resin of the component B in the present invention, another copolymerizable unsaturated monomer other than (3) N-substituted maleimide or (4) acrylic acid or methacrylic acid may be used.
Examples of such unsaturated monomers include unsaturated fatty acid esters, aromatic vinyl compounds, vinyl cyanide compounds, and the like. Specific examples thereof include other copolymers as the monomer component of the copolymer resin of the component A. Examples of the polymerizable unsaturated monomer include those exemplified above.
【００２０】上記の不飽和脂肪酸エステルとしては、前
記したＡ成分である共重合樹脂の成分とすることができ
る不飽和脂肪酸エステルがあり、前記（２）成分である
環内に３級炭素を含む炭素数７〜２０の脂環式メタクリ
ル酸エステルおよび／またはアクリル酸エステルを使用
しても良い。上記の芳香族ビニル化合物としては、例え
ばスチレンまたはα−メチルスチレン、α−エチルスチ
レン等のα−置換スチレン、クロロスチレン、ビニルト
ルエン、ｔ−ブチルスチレン等の核置換スチレンなどが
ある。上記のシアン化ビニル化合物としては、例えばア
クリロニトリル、メタクリロニトリル等がある。Examples of the unsaturated fatty acid ester include unsaturated fatty acid esters which can be used as a component of the copolymer resin as the above-mentioned component A, and include a tertiary carbon in the ring which is the above-mentioned component (2). An alicyclic methacrylate and / or acrylate having 7 to 20 carbon atoms may be used. Examples of the aromatic vinyl compound include styrene or α-substituted styrene such as α-methylstyrene and α-ethylstyrene, and nucleus-substituted styrene such as chlorostyrene, vinyltoluene and t-butylstyrene. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.
【００２１】前記した各単量体は、これらの総量を１０
０重量部として、（３）成分を２０〜７０重量部、
（４）成分を５〜３０重量部および他の不飽和単量体を
０〜５０重量部の範囲内の割合で使用することが好まし
い。（３）Ｎ−置換マレイミドが上記の範囲より少ない
と、得られる硬化塗膜の耐熱性が不十分となり、逆に多
いと密着性やコーティング性に不都合を生じる傾向があ
る。（４）アクリル酸および／またはメタクリル酸が上
記の範囲より少ないと、得られる塗膜の耐熱性、耐傷性
が不十分となる傾向があり、逆に多いと塗布性や塗膜の
耐薬品性が低下する傾向がある。他の不飽和単量体が上
記の範囲を越えると本発明の効果が不十分となりやす
い。またＢ成分である共重合樹脂は、前記（３）成分、
（４）成分および他の不飽和単量体成分の各単量体を配
合し、共重合させることにより製造することができる。
この場合における重合法、使用しうる重合開始剤、重合
調節剤、重合温度、溶液重合における溶媒については、
Ａ成分である共重合樹脂の場合と同様である。Each of the above-mentioned monomers has a total amount of 10
0 parts by weight, 20 to 70 parts by weight of the component (3),
It is preferable to use 5 to 30 parts by weight of the component (4) and 0 to 50 parts by weight of the other unsaturated monomer. (3) When the amount of N-substituted maleimide is less than the above range, the heat resistance of the obtained cured coating film becomes insufficient, and when it is too large, there is a tendency to cause problems in adhesion and coating properties. (4) If the amount of acrylic acid and / or methacrylic acid is less than the above range, the heat resistance and scratch resistance of the resulting coating film tend to be insufficient, and if the amount is too large, the coating property and the chemical resistance of the coating film tend to be insufficient. Tends to decrease. If the other unsaturated monomer exceeds the above range, the effect of the present invention tends to be insufficient. Further, the copolymer resin as the component B is the component (3),
It can be produced by blending and copolymerizing each monomer of the component (4) and other unsaturated monomer components.
In this case, a polymerization method, a polymerization initiator that can be used, a polymerization regulator, a polymerization temperature, and a solvent in solution polymerization,
This is the same as the case of the copolymer resin as the component A.
【００２２】また本発明においては、Ｃ成分として多価
カルボン酸無水物および多価カルボン酸からなる群より
選ばれる少なくとも１種の化合物を使用する。上記の多
価カルボン酸無水物としては、無水イタコン酸、無水マ
レイン酸、無水コハク酸、無水シトラコン酸、無水ドデ
セニルコハク酸、無水テトラヒドロフタル酸、無水ヘキ
サヒドロフタル酸、無水メチルテトラヒドロフタル酸、
無水メチルヘキサヒドロフタル酸、無水エンドメチレン
テトラヒドロフタル酸、無水メチルエンドメチレンテト
ラヒドロフタル酸等の脂肪族ジカルボン酸無水物； シ
クロペンタンテトラカルボン酸二無水物、１，２，３，
４−ブタンテトラカルボン酸二無水物等の脂肪族多価カ
ルボン酸二無水物； 無水フタル酸、無水トリメリット
酸、無水ピロメリット酸、無水ベンゾフェノンテトラカ
ルボン酸、３，３´，４，４´−ジフェニルスルホンテ
トラカルボン酸二無水物等の芳香族多価カルボン酸無水
物；エチレングリコールビストリメリテート、グリセリ
ントリストリメリテート等のエステル基含有酸無水物を
挙げることができる。また、上記の多価カルボン酸とし
てはイタコン酸、マレイン酸、コハク酸、シトラコン
酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、メ
チルテトラヒドロフタル酸、シクロペンタンテトラカル
ボン酸等の脂肪族多価カルボン酸； フタル酸、テレフ
タル酸、イソフタル酸、トリメリット酸、ピロメリット
酸、ベンゾフェノンテトラカルボン酸等の芳香族多価カ
ルボン酸を挙げることができる。In the present invention, at least one compound selected from the group consisting of polycarboxylic anhydrides and polycarboxylic acids is used as the component C. Examples of the polycarboxylic anhydride include itaconic anhydride, maleic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride,
Aliphatic dicarboxylic anhydrides such as methylhexahydrophthalic anhydride, endmethylenetetrahydrophthalic anhydride, and methylendmethylenetetrahydrophthalic anhydride; cyclopentanetetracarboxylic dianhydride, 1,2,3
Aliphatic polycarboxylic dianhydrides such as 4-butanetetracarboxylic dianhydride; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, 3,3 ′, 4,4 ′ Aromatic polycarboxylic anhydrides such as diphenylsulfonetetracarboxylic dianhydride; ester group-containing anhydrides such as ethylene glycol bistrimellitate and glycerin tristrimellitate. Examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as itaconic acid, maleic acid, succinic acid, citraconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, and cyclopentanetetracarboxylic acid; Examples thereof include aromatic polycarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, and benzophenonetetracarboxylic acid.
【００２３】多価カルボン酸無水物および多価カルボン
酸は１種類のみで用いても、２種類以上を組み合わせて
用いてもよい。耐熱性の点から芳香族多価カルボン酸無
水物および芳香族多価カルボン酸が好ましく、また耐熱
性と溶剤に対する溶解性のバランスの点から無水トリメ
リット酸が特に好ましい。The polycarboxylic anhydride and the polycarboxylic acid may be used alone or in combination of two or more. Aromatic polycarboxylic anhydrides and aromatic polycarboxylic acids are preferred from the viewpoint of heat resistance, and trimellitic anhydride is particularly preferred from the viewpoint of the balance between heat resistance and solubility in solvents.
【００２４】また本発明においては、密着性及び耐ＩＰ
Ａベーパー性の向上のためにＤ成分として官能性シラン
カップリング剤を使用する。官能性シランカップリング
剤としては、ビニル基、メタクリロイル基、水酸基、カ
ルボキシル基、アミノ基、イソシアネート基、エポキシ
基等の反応性置換基を有するシランカップリング剤、具
体的にはビニルトリメトキシシラン、ビニルトリエトキ
シシラン、γ−メタクリロキシプロピルトリメトキシシ
ラン、γ−イソシアナートプロピルトリエトキシシラ
ン、γ−グリシドキシプロピルトリメトキシシラン等を
挙げることができる。特にエポキシ基を有するシランカ
ップリング剤が密着性、耐薬品性等に優れているため好
ましい。これらの官能性シランカップリング剤は１種類
のみで用いても２種類以上を組み合わせて用いてもよ
い。In the present invention, adhesion and IP resistance
A functional silane coupling agent is used as the D component for improving the vapor property. As the functional silane coupling agent, a silane coupling agent having a reactive substituent such as a vinyl group, a methacryloyl group, a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, and an epoxy group, specifically, vinyltrimethoxysilane, Vinyl triethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane and the like can be mentioned. Particularly, a silane coupling agent having an epoxy group is preferable because of excellent adhesion, chemical resistance and the like. These functional silane coupling agents may be used alone or in combination of two or more.
【００２５】本発明の組成物において、Ａ成分の共重合
樹脂１００重量部に対するＢ成分の共重合樹脂の配合量
は２０〜２００重量部であり、特に好ましくは４０〜１
００重量部である。Ｂ成分の共重合樹脂が２０重量部よ
り少ないと密着性が低下する傾向があり、２００重量部
より多いと耐薬品性が不十分となる傾向がある。前記Ｃ
成分の多価カルボン酸無水物または多価カルボン酸から
なる群より選ばれる少なくとも１種の化合物の配合量
は、Ａ成分である共重合樹脂１００重量部に対して５〜
５０重量部であり、特に好ましくは１０〜４０重量部で
ある。多価カルボン酸無水物または多価カルボン酸が５
重量部より少ないと耐熱性が不十分となる傾向があり、
５０重量部より多いと塗布性、耐薬品性等が低下する傾
向がある。さらに前記Ｄ成分の官能性シランカップリン
グ剤の配合量は、Ａ成分の共重合樹脂１００重量部に対
して、３０〜１００重量部とされ、好ましくは３０〜６
０重量部である。３０重量部より少ないと密着性や耐Ｉ
ＰＡベーパー性が不十分となる傾向があり、１００重量
部より多いと塗布性や耐熱性が低下する傾向がある。In the composition of the present invention, the blending amount of the component B copolymer resin is 20 to 200 parts by weight, particularly preferably 40 to 1 part by weight, per 100 parts by weight of the component A copolymer resin.
00 parts by weight. If the amount of the component B copolymer resin is less than 20 parts by weight, the adhesiveness tends to decrease, and if it exceeds 200 parts by weight, the chemical resistance tends to be insufficient. Said C
The compounding amount of at least one compound selected from the group consisting of polycarboxylic anhydrides and polycarboxylic acids is 5 to 100 parts by weight of the copolymer resin as the component A.
The amount is 50 parts by weight, particularly preferably 10 to 40 parts by weight. 5 polycarboxylic anhydrides or polycarboxylic acids
If the amount is less than the weight part, the heat resistance tends to be insufficient,
If the amount is more than 50 parts by weight, applicability, chemical resistance and the like tend to decrease. The compounding amount of the functional silane coupling agent of the component D is 30 to 100 parts by weight, preferably 30 to 6 parts by weight, per 100 parts by weight of the copolymer resin of the component A.
0 parts by weight. If it is less than 30 parts by weight, adhesion and I resistance
PA vapor properties tend to be insufficient, and if it is more than 100 parts by weight, coating properties and heat resistance tend to decrease.
【００２６】また、本発明の組成物には硬化促進剤を配
合することが望ましい。硬化促進剤としては、通常エポ
キシ樹脂の硬化に際して用いられるものをそのまま使用
できる。具体的には、塩酸等の無機酸、酢酸、シュウ酸
等の有機酸、トリエチルアミン、ベンジルジメチルアミ
ン等の第三級アミン類、１−ベンジル−２−メチルイミ
ダゾール、２−エチル−４−メチルイミダゾール、１−
シアノエチル−２−エチル−４−メチルイミダゾール等
のイミダゾール類、トリフェニルホスフィン等のホスフ
ィン類、ＢＦ３等のルイス酸またはルイス酸塩等を挙げ
ることができ、好ましくは第三級アミン類、またはイミ
ダゾール類が用いられる。硬化促進剤の配合量は、Ａ成
分の共重合樹脂１００重量部に対して好ましくは０．１
〜１０重量部であり、より好ましくは０．５〜５重量部
である。硬化促進剤が０．１重量部より少ないと耐熱性
が不十分となる傾向があり、１０重量部より多いと耐湿
性、耐薬品性等が低下する傾向がある。It is desirable that the composition of the present invention contains a curing accelerator. As the curing accelerator, those usually used for curing an epoxy resin can be used as they are. Specifically, inorganic acids such as hydrochloric acid, organic acids such as acetic acid and oxalic acid, tertiary amines such as triethylamine and benzyldimethylamine, 1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole , 1-
Imidazoles such as cyanoethyl-2-ethyl-4-methylimidazole, phosphines such as triphenylphosphine, Lewis acids or Lewis acid salts such as BF3, and the like, preferably tertiary amines or imidazoles Is used. The amount of the curing accelerator is preferably 0.1 to 100 parts by weight of the copolymer resin of the component A.
10 to 10 parts by weight, more preferably 0.5 to 5 parts by weight. If the amount of the curing accelerator is less than 0.1 part by weight, heat resistance tends to be insufficient, and if it is more than 10 parts by weight, moisture resistance, chemical resistance, and the like tend to decrease.
【００２７】本発明の組成物は、通常、溶剤に溶解して
基材に塗布し、加熱硬化させることによって塗膜を形成
させることができる。溶剤としては、本発明の組成物を
溶解し、かつこれらの成分と反応しないものであれば、
特に制限はない。具体的には、本発明のＡ成分またはＢ
成分の共重合樹脂を溶液重合させる際の溶媒として例示
した溶剤が挙げられる。これらの溶剤のうちエステル系
溶剤およびケトン系溶剤が好ましく、単独または２種類
以上を混合して使用することができる。The composition of the present invention can be usually dissolved in a solvent, applied to a substrate, and cured by heating to form a coating film. As a solvent, as long as it dissolves the composition of the present invention and does not react with these components,
There is no particular limitation. Specifically, the component A or B of the present invention
Solvents exemplified as the solvent when the copolymer resin of the component is subjected to solution polymerization are exemplified. Among these solvents, ester solvents and ketone solvents are preferable, and they can be used alone or in combination of two or more.
【００２８】本発明の組成物を溶剤に溶解して、組成物
溶液を調製する方法には特に制限はなく、全成分を同時
に溶剤に溶解して組成物溶液を調製してもよく、必要に
応じて各成分を適宜２つ以上の溶液としておいて、使用
時にこれらの溶液を混合して組成物溶液としてもよい。
このようにして組成物溶液を調製する場合の溶剤の使用
量は、塗布に供せられる最終的な組成物溶液全量のうち
５０〜９５重量部とすることが好ましい。５０重量部未
満では固形分濃度が高すぎて塗膜のレベリング性が低下
したり、塗膜の透明性が低下する傾向があり、一方９５
重量部を越える場合は固形分濃度が低すぎて、塗膜の耐
薬品性等が不十分となる傾向がある。また、本発明の組
成物には必要に応じて、エピビス型やノボラック型等の
エポキシ樹脂、界面活性剤、酸化防止剤、紫外線吸収剤
等の安定剤などを添加することもできる。The method for preparing the composition solution by dissolving the composition of the present invention in a solvent is not particularly limited, and the composition solution may be prepared by simultaneously dissolving all the components in the solvent. Accordingly, each component may be appropriately prepared as two or more solutions, and these solutions may be mixed at the time of use to form a composition solution.
The amount of the solvent used in preparing the composition solution in this manner is preferably 50 to 95 parts by weight based on the total amount of the final composition solution to be applied. If the amount is less than 50 parts by weight, the solid content concentration is too high, and the leveling property of the coating film tends to decrease, and the transparency of the coating film tends to decrease.
If the amount exceeds the weight part, the solid content concentration is too low, and the chemical resistance of the coating film tends to be insufficient. The composition of the present invention may contain, if necessary, an epoxy resin such as an epibis-type or a novolak-type, a surfactant, an antioxidant, and a stabilizer such as an ultraviolet absorber.
【００２９】本発明の組成物溶液を塗布する方法は特に
限定されず、浸漬法、スプレー法、ロールコート法、回
転塗布法、スクリーン印刷、オフセット印刷等の印刷に
よる塗布方法などにより基材に塗布することができる。
本発明の組成物の加熱硬化条件は組成物の各成分の具体
的種類、配合割合等によって適宜選択されるが、通常、
５０〜３００℃で０．１〜１０時間、好ましくは１００
〜２５０℃で１〜５時間程度である。The method of applying the composition solution of the present invention is not particularly limited, and the composition solution is applied to a substrate by a dipping method, a spray method, a roll coating method, a spin coating method, a screen coating method, a printing method such as offset printing, or the like. can do.
The heat-curing conditions of the composition of the present invention are appropriately selected depending on the specific types of each component of the composition, the mixing ratio, and the like.
0.1 to 10 hours at 50 to 300 ° C., preferably 100
It is about 1 to 5 hours at ~ 250 ° C.
【００３０】本発明の組成物により形成される硬化塗膜
はガラス、金属、プラスチック等の種々の材料に対して
優れた密着性を示し、平滑、強靱で耐光性、耐熱性、耐
水性、耐溶剤性及び透明性に優れているため、各種物品
のコーティング膜として有用である。特にカラーフィル
タ保護膜として、ゼラチン、グリュー、ポリビニルアル
コール、アクリル系樹脂等の種々のバインダー樹脂を染
料による染色や、顔料分散によって着色して得られる種
々のカラーフィルタの表面保護層、平坦化層として有用
である。カラーフィルタ保護膜として用いる場合は加熱
硬化後の膜厚が０．００５〜３０μｍ、好ましくは０．
１〜１０μｍ程度となるように、適宜、塗布して用いる
ことができる。透明ガラス基板の上に、ストライプ状の
赤、緑、青の染色式カラーフィルターを形成してカラー
フィルター基材を得、この上に本発明になる硬化塗膜用
組成物を塗布、乾燥して保護膜付きカラーフィルターが
製造される。The cured coating film formed by the composition of the present invention exhibits excellent adhesion to various materials such as glass, metal, plastic and the like, and is smooth, tough, light-resistant, heat-resistant, water-resistant and water-resistant. Since it has excellent solvent properties and transparency, it is useful as a coating film for various articles. In particular, as a color filter protective film, as a surface protective layer, a flattening layer of various color filters obtained by dyeing various binder resins such as gelatin, glue, polyvinyl alcohol, and acrylic resin with a dye or dispersing a pigment. Useful. When used as a color filter protective film, the film thickness after heat curing is 0.005 to 30 μm, preferably 0.1 to 30 μm.
It can be appropriately coated and used so as to have a thickness of about 1 to 10 μm. On a transparent glass substrate, a striped red, green, blue dyeing type color filter is formed to obtain a color filter base material, and the composition for a cured coating film according to the present invention is applied thereon and dried. A color filter with a protective film is manufactured.
【００３１】本発明者らの研究によれば、従来のポリグ
リシジル（メタ）アクリレート樹脂を用いる技術は、こ
の樹脂を低分子量の多価カルボン酸無水物または多価カ
ルボン酸と反応させるものであるが、得られる塗膜は脆
弱すぎて密着性が悪いこと、また架橋にあずかるエステ
ル結合の数が多すぎるため、耐アルカリ性が悪いことが
判明した。また、従来技術では塗布性、密着性、耐熱性
等のすべての要求特性を満足させるものはなかったが、
本発明になる組成物は特定の構造の化合物を組み合わせ
ることにより、これらの各要求特性をバランス良く満足
させることができる。According to the study of the present inventors, the conventional technique using a polyglycidyl (meth) acrylate resin is to react this resin with a low molecular weight polycarboxylic anhydride or polycarboxylic acid. However, it was found that the obtained coating film was too brittle and had poor adhesion, and that the number of ester bonds participating in crosslinking was too large, resulting in poor alkali resistance. Further, in the prior art, none of the required properties such as applicability, adhesion, and heat resistance were satisfied.
The composition according to the present invention can satisfy each of these required characteristics in a well-balanced manner by combining a compound having a specific structure.
【００３２】[0032]
【実施例】以下、実施例により本発明を具体的に説明す
るが、本発明はこれらの実施例によって制限されるもの
ではない。 製造例１ 共重合樹脂溶液Ａ−１の合成 攪拌機、温度計、窒素導入管、還流冷却管、および滴下
ロートの備わった１リットルフラスコに、エチルセロソ
ルブアセテート（アセトキシエトキシエタン）２６０重
量部を仕込み、フラスコ内を窒素置換した。メタクリル
酸トリシクロ［５．２．１．０２，６］デカン−８−イ
ル（日立化成工業（株）製、ＦＡ−５１３Ｍ）６０重量
部、メタクリル酸グリシジル１４０重量部、アゾビスイ
ソブチロニトリル１．０重量部をエチルセロソルブアセ
テート１００重量部に溶解し、前述の１リットルフラス
コに窒素気流中９０℃で３時間かけて滴下した。さらに
９０℃で１時間攪拌した後、アゾビスイソブチロニトリ
ル０．２重量部をエチルセロソルブアセテート４０重量
部に溶解した溶液を添加し、その後１２０℃に昇温して
２時間保った。得られた共重合樹脂溶液は粘度が３２０
センチポアズ（２５℃）であり、この共重合樹脂をＨＬ
Ｃ分析（ＧＰＣモード；カラム：日立化成工業（株）製
ゲルパックＡ−１２０＋ゲルパックＡ−１４０＋ゲル
パックＡ−１５０、溶離液；テトラヒドロフラン、検出
器：示差屈折計）したところ、ポリスチレン換算の重量
平均分子量は約５０，０００であった。EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. Production Example 1 Synthesis of Copolymer Resin Solution A-1 260 parts by weight of ethyl cellosolve acetate (acetoxyethoxyethane) was charged into a 1-liter flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a reflux condenser, and a dropping funnel. The atmosphere in the flask was replaced with nitrogen. 60 parts by weight of tricyclo [5.2.1.02,6] decane-8-yl methacrylate (manufactured by Hitachi Chemical Co., Ltd., FA-513M), 140 parts by weight of glycidyl methacrylate, azobisisobutyronitrile 1 0.0 parts by weight were dissolved in 100 parts by weight of ethyl cellosolve acetate, and added dropwise to the above-mentioned one-liter flask at 90 ° C. for 3 hours in a nitrogen stream. After stirring at 90 ° C. for 1 hour, a solution of 0.2 parts by weight of azobisisobutyronitrile dissolved in 40 parts by weight of ethyl cellosolve acetate was added, and then the temperature was raised to 120 ° C. and maintained for 2 hours. The obtained copolymer resin solution has a viscosity of 320.
Centipoise (25 ° C.).
C analysis (GPC mode; column: Gelpack A-120 + Gelpack A-140 + Gelpack A-150, manufactured by Hitachi Chemical Co., Ltd., eluent: tetrahydrofuran, detector: differential refractometer) showed a weight average molecular weight in terms of polystyrene. It was about 50,000.
【００３３】製造例２ 共重合樹脂溶液Ａ−２の合成 製造例１において、メタクリル酸トリシクロ［５．２．
１．０２，６］デカン−８−イルの代わりにメタクリル
酸ボルニルを用いた以外は製造例１と全く同様に行った
ところ、得られた共重合樹脂溶液は粘度が２４０センチ
ポアズ（２５℃）であり、この共重合樹脂をＨＬＣ分析
したところ、ポリスチレン換算の重量平均分子量は約４
５，０００であった。Production Example 2 Synthesis of Copolymer Resin Solution A-2 The same procedure as in Production Example 1 was carried out except for the preparation of tricyclomethacrylate [5.2.
1.02,6] Performed in exactly the same manner as in Production Example 1 except that bornyl methacrylate was used in place of decane-8-yl, the resulting copolymer resin solution had a viscosity of 240 centipoise (25 ° C.). According to HLC analysis of this copolymer resin, the weight average molecular weight in terms of polystyrene was about 4
It was 5,000.
【００３４】製造例３ 共重合樹脂溶液Ａ−３の合成 製造例１において、メタクリル酸トリシクロ［５．２．
１．０２，６］デカン−８−イルの代わりにメタクリル
酸イソボルニルを用いた以外は製造例１と全く同様に行
ったところ、得られた共重合樹脂溶液は粘度が２２０セ
ンチポアズ（２５℃）であり、この共重合樹脂をＨＬＣ
分析したところ、ポリスチレン換算の重量平均分子量は
約４２，０００であった。Production Example 3 Synthesis of Copolymer Resin Solution A-3 The same procedure as in Production Example 1 was carried out except for using tricyclomethacrylate [5.2.
1.02,6] The procedure of Production Example 1 was repeated, except that isobornyl methacrylate was used instead of decane-8-yl. The resulting copolymer resin solution had a viscosity of 220 centipoise (25 ° C.). Yes, this copolymer resin is HLC
As a result of analysis, the weight average molecular weight in terms of polystyrene was about 42,000.
【００３５】製造例４ 共重合樹脂溶液Ａ−４の合成 製造例１において、メタクリル酸トリシクロ［５．２．
１．０２，６］デカン−８−イルの代わりにメタクリル
酸ノルボルニルを用いた以外は製造例１と全く同様に行
ったところ、得られた共重合樹脂溶液は粘度が２７０セ
ンチポアズ（２５℃）であり、この共重合樹脂をＨＬＣ
分析したところ、ポリスチレン換算の重量平均分子量は
約４０，０００であった。Production Example 4 Synthesis of Copolymer Resin Solution A-4 In Production Example 1, tricyclomethacrylate [5.2.
1.02,6] The same procedure as in Preparation Example 1 was repeated, except that norbornyl methacrylate was used instead of decane-8-yl. The resulting copolymer resin solution had a viscosity of 270 centipoise (25 ° C.). Yes, this copolymer resin is HLC
As a result of analysis, the weight average molecular weight in terms of polystyrene was about 40,000.
【００３６】製造例５ 共重合樹脂溶液Ｂ−１の合成 攪拌機、温度計、窒素導入管、還流冷却管、および滴下
ロートの備わった１リットルフラスコに、エチルセロソ
ルブアセテート１５０重量部を仕込み、フラスコ内を窒
素置換した。Ｎ−フェニルマレイミド１４０重量部、メ
タクリル酸４０重量部、アクリル酸エチル２０重量部、
アゾビスイソブチロニトリル３．０重量部をエチルセロ
ソルブアセテート３００重量部に溶解し、前述の１リッ
トルフラスコに窒素気流中９０℃で３時間かけて滴下し
た。さらに９０℃で１時間攪拌した後、アゾビスイソブ
チロニトリル０．２重量部をエチルセロソルブアセテー
ト１６．７重量部に溶解した溶液を添加し、その後１２
０℃に昇温して２時間保った。得られた共重合樹脂溶液
は粘度が５６０センチポアズ（２５℃）であり、この共
重合樹脂をＨＬＣ分析したところ、ポリスチレン換算の
重量平均分子量は約２２，０００であった。Production Example 5 Synthesis of Copolymer Resin Solution B-1 150 parts by weight of ethyl cellosolve acetate was charged into a 1-liter flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a reflux condenser, and a dropping funnel. Was replaced with nitrogen. 140 parts by weight of N-phenylmaleimide, 40 parts by weight of methacrylic acid, 20 parts by weight of ethyl acrylate,
Azobisisobutyronitrile (3.0 parts by weight) was dissolved in ethyl cellosolve acetate (300 parts by weight) and added dropwise to the above-mentioned one-liter flask at 90 ° C. for 3 hours in a nitrogen stream. After further stirring at 90 ° C. for 1 hour, a solution of 0.2 parts by weight of azobisisobutyronitrile dissolved in 16.7 parts by weight of ethyl cellosolve acetate was added.
The temperature was raised to 0 ° C. and kept for 2 hours. The viscosity of the obtained copolymer resin solution was 560 centipoise (25 ° C.). The HLC analysis of this copolymer resin revealed that the weight average molecular weight in terms of polystyrene was about 22,000.
【００３７】製造例６ 共重合樹脂溶液Ｂ−２の合成 製造例５において、モノマー成分をＮ−シクロヘキシル
マレイミド１２０重量部、メタクリル酸４０重量部、メ
タクリル酸メチル４０重量部に代えた以外は製造例５と
全く同様に行ったところ、得られた共重合樹脂溶液は粘
度が４８０センチポアズ（２５℃）であり、この共重合
樹脂をＨＬＣ分析したところ、ポリスチレン換算の重量
平均分子量は約２０，０００であった。Preparation Example 6 Synthesis of Copolymer Resin Solution B-2 Preparation Example 5 was repeated except that the monomer components were changed to 120 parts by weight of N-cyclohexylmaleimide, 40 parts by weight of methacrylic acid, and 40 parts by weight of methyl methacrylate. The same procedure as in Example 5 was carried out, and the resulting copolymer resin solution had a viscosity of 480 centipoise (25 ° C.). The copolymer was subjected to HLC analysis to find that the weight average molecular weight in terms of polystyrene was about 20,000. there were.
【００３８】製造例７ 共重合樹脂溶液Ｂ−３の合成 製造例５において、モノマー成分をＮ−フェニルマレイ
ミド１００重量部、メタクリル酸４０重量部、メタクリ
ル酸トリシクロ［５．２．１．０２，６］デカン−８−
イル６０重量部に代えた以外は製造例５と全く同様に行
ったところ、得られた共重合樹脂溶液は粘度が３５０セ
ンチポアズ（２５℃）であり、この共重合樹脂をＨＬＣ
分析したところ、ポリスチレン換算の重量平均分子量は
約１２，０００であった。Production Example 7 Synthesis of Copolymer Resin Solution B-3 In Production Example 5, the monomer components were changed to 100 parts by weight of N-phenylmaleimide, 40 parts by weight of methacrylic acid, and tricyclo [5.2.1.02,6, methacrylate]. ] Decane-8-
Except that the amount was changed to 60 parts by weight, the same procedure as in Preparation Example 5 was carried out. The resulting copolymer resin solution had a viscosity of 350 centipoise (25 ° C.).
As a result of analysis, the weight average molecular weight in terms of polystyrene was about 12,000.
【００３９】実施例１〜１２ 共重合樹脂溶液Ａ−１〜４のいずれか３００重量部に対
し、共重合樹脂溶液Ｂ−１〜３のいずれか３００重量
部、無水トリメリット酸３０重量部、γ−グリシドキシ
プロピルトリメトキシシラン（ＳＨ−６０４０；東レ・
ダウコーニング・シリコーン（株）商品名）４０重量
部、１−シアノエチル−２−エチル−４−メチルイミダ
ゾール２重量部、エチルセロソルブアセテート１００重
量部、及びブチルセロソルブアセテート３５０重量部を
加えて室温で均一に混合、溶解させた。共重合樹脂溶液
ＡおよびＢの組み合わせを表１に示す。この溶液を、孔
径０．２μｍのメンブランフィルタで濾過した後、スピ
ンコーターを用いてガラス板（ダウコーニング社 ７０
５９材、無アルカリガラス）上に回転数７００ｒｐｍで
回転塗布した。塗布後、ガラス板を１８０℃のクリーン
オーブン中で１時間処理し、塗膜を硬化させた。得られ
た塗膜の表面は極めて平滑であり、ピンホール等は全く
見られなかった。触針式膜厚計（Ｄｅｋｔａｋ３；日本
真空技術（株）商品名）によって測定した膜厚は１．５
〜２．０μｍであった。Examples 1 to 12 300 parts by weight of any of copolymer resin solutions B-1 to B-3, 30 parts by weight of trimellitic anhydride, and 300 parts by weight of any one of copolymer resin solutions A-1 to A-4 γ-glycidoxypropyltrimethoxysilane (SH-6040; Toray Industries, Inc.)
40 parts by weight of Dow Corning Silicone Co., Ltd.), 2 parts by weight of 1-cyanoethyl-2-ethyl-4-methylimidazole, 100 parts by weight of ethyl cellosolve acetate, and 350 parts by weight of butyl cellosolve acetate were added, and the mixture was uniformly mixed at room temperature. Mix and dissolve. Table 1 shows the combinations of the copolymer resin solutions A and B. The solution was filtered through a membrane filter having a pore size of 0.2 μm, and then a glass plate (Dow Corning 70
(59 materials, non-alkali glass) at 700 rpm. After the application, the glass plate was treated in a clean oven at 180 ° C. for 1 hour to cure the coating. The surface of the obtained coating film was extremely smooth, and no pinholes or the like were observed. The film thickness measured by a stylus type film thickness meter (Dektak3; trade name of Japan Vacuum Engineering Co., Ltd.) is 1.5
２．０2.0 μm.
【００４０】このようにして作製した塗膜について以下
の試験を行った。塗膜のガラス板との密着性を調べるた
めにテープ剥離によるゴバン目試験（ＪＩＳ−Ｋ−５４
００）を行った。その結果、残存数１００／１００であ
り、剥離は全く見られなかった。次に塗膜の４００ｎｍ
〜８００ｎｍにおける吸収スペクトルを塗布したものと
同じガラス板をリファレンスとして測定したところ、光
線透過率は全領域で９５％以上であった。また、この塗
膜をつけたガラス板をプレッシャークッカーテスト（１
２０℃、２気圧）３０時間（以下、ＰＣＴ処理とい
う）、Ｎ−メチルピロリドン中に室温で３０分浸漬（以
下、ＮＭＰ処理という）、５重量％水酸化ナトリウム水
溶液に室温で１時間浸漬（以下、ＮａＯＨ処理とい
う）、および２８０℃のギヤオーブン中に１時間放置
（以下、２８０℃処理という）の処理を別々に行い、各
処理後で上記のゴバン目試験および光線透過率の測定を
行った。これらの結果を塗膜製造直後（硬化直後）の試
験結果と比較したところ、いずれの場合も接着性や光線
透過率は良好であった。ゴバン目試験結果を表２に、光
線透過率試験結果を表３にそれぞれ示す。The following tests were performed on the coating films thus prepared. Goban eye test (JIS-K-54) by tape peeling to examine the adhesion of the coating film to the glass plate
00). As a result, the remaining number was 100/100, and no peeling was observed. Next, 400nm of coating film
The light transmittance was 95% or more in the whole region when the same glass plate as that on which the absorption spectrum at -800 nm was applied was measured as a reference. In addition, the glass plate with the coating film was subjected to a pressure cooker test (1.
30 hours (hereinafter referred to as PCT treatment) at 30 ° C. in N-methylpyrrolidone (hereinafter referred to as NMP treatment) for 30 hours (hereinafter referred to as NMP treatment). , NaOH treatment) and left for 1 hour in a 280 ° C. gear oven (hereinafter referred to as 280 ° C. treatment), and after each treatment, the above-mentioned Gobang test and measurement of light transmittance were performed. . When these results were compared with the test results immediately after the production of the coating film (immediately after curing), the adhesiveness and light transmittance were good in all cases. Table 2 shows the results of the Goban test, and Table 3 shows the results of the light transmittance test.
【００４１】[0041]
【表１】 ──────────────────────────────────── 表１ 実施例１〜１２の配合 ──────────────────────────────────── 共重合樹脂溶液Ａ 共重合樹脂溶液Ｂ ──────────────────────────────────── 実施例１ Ａ−１ Ｂ−１ 〃 ２ Ａ−１ Ｂ−２ 〃 ３ Ａ−１ Ｂ−３ 〃 ４ Ａ−２ Ｂ−１ 〃 ５ Ａ−２ Ｂ−２ 〃 ６ Ａ−２ Ｂ−３ 〃 ７ Ａ−３ Ｂ−１ 〃 ８ Ａ−３ Ｂ−２ 〃 ９ Ａ−３ Ｂ−３ 〃 10 Ａ−４ Ｂ−１ 〃 11 Ａ−４ Ｂ−２ 〃 12 Ａ−４ Ｂ−３ ────────────────────────────────────Table 1 Table 1 Formulations of Examples 1 to 12 ─────────────────────────────────── Copolymer resin solution A Copolymer resin solution B ───── << Example 1 A-1 B-1 << 2 A-1 B-2 >> 3 A-1 B-3 ４4 A-2 B-1 ５5 A-2 B-2 〃6 A-2 B-3 ７7 A-3 B-1 ８8 A-3 B-2 ９9 A- 3 B-3 〃 10 A-4 B-1 〃 11 A-4 B-2 〃 12 A-4 B-3 ────────────────────── ──────────────
【００４２】比較例１ ポリメタクリル酸グリシジル（ポリスチレン換算分子量
約８０，０００）１００重量部、無水トリメリット酸１
０重量部、γ−グリシドキシプロピルトリメトキシシラ
ン（ＳＨ−６０４０；東レ・ダウコーニング・シリコー
ン（株）商品名）１．０重量部、エチルセロソルブアセ
テート５８０重量部を室温で均一に混合溶解し、得られ
た溶液を実施例と同様にしてガラス板上に塗布、加熱硬
化させて、塗膜の各種特性試験を行った。ゴバン目試験
結果を表２に、光線透過率試験結果を表３にそれぞれ示
す。Comparative Example 1 100 parts by weight of polyglycidyl methacrylate (polystyrene equivalent molecular weight: about 80,000), trimellitic anhydride 1
0 parts by weight, 1.0 part by weight of γ-glycidoxypropyltrimethoxysilane (SH-6040; trade name of Dow Corning Toray Silicone Co., Ltd.) and 580 parts by weight of ethyl cellosolve acetate are uniformly mixed and dissolved at room temperature. The obtained solution was applied to a glass plate and cured by heating in the same manner as in the example, and various characteristics tests of the coating film were performed. Table 2 shows the results of the Goban test, and Table 3 shows the results of the light transmittance test.
【００４３】比較例２ 製造例１で得られた共重合樹脂溶液Ａ−１ ３００重量
部に対し、無水トリメリット酸３０重量部、γ−グリシ
ドキシプロピルトリメトキシシラン（ＳＨ−６０４０；
東レ・ダウコーニング・シリコーン（株）商品名）４０
重量部、１−シアノエチル−２−エチル−４−メチルイ
ミダゾール２重量部、エチルセロソルブアセテート１２
０重量部、ブチルセロソルブアセテート２３０重量部を
加えて室温で均一に混合溶解し、得られた溶液を実施例
と同様にしてガラス板上に塗布、加熱硬化させて、塗膜
の各種特性試験を行った。ゴバン目試験結果を表２に、
光線透過率試験結果を表３にそれぞれ示す。Comparative Example 2 30 parts by weight of trimellitic anhydride and γ-glycidoxypropyltrimethoxysilane (SH-6040; 300 parts by weight of copolymer resin solution A-1 obtained in Production Example 1)
Toray Dow Corning Silicone Co., Ltd.) 40
1 part by weight, 2 parts by weight of 1-cyanoethyl-2-ethyl-4-methylimidazole, ethyl cellosolve acetate 12
0 parts by weight and 230 parts by weight of butyl cellosolve acetate were added and uniformly mixed and dissolved at room temperature, and the obtained solution was applied on a glass plate and cured by heating in the same manner as in the example, and various properties tests of the coating film were performed. Was. Table 2 shows the results of the Goban test.
Table 3 shows the results of the light transmittance test.
【００４４】比較例３ 実施例３のγ−グリシドキシプロピルトリメトキシシラ
ン（ＳＨ−６０４０；東レ・ダウコーニング・シリコー
ン（株）商品名）を４０重量部から５重量部に変更した
以外は、実施例３と同様にしてガラス板上に塗布、加熱
硬化させて、塗膜の各種特性試験を行った。ゴバン目試
験結果を表２に、光線透過率試験結果を表３にそれぞれ
示す。Comparative Example 3 γ-glycidoxypropyltrimethoxysilane (SH-6040; trade name of Dow Corning Toray Silicone Co., Ltd.) of Example 3 was changed from 40 parts by weight to 5 parts by weight. The coating was performed on a glass plate and cured by heating in the same manner as in Example 3, and various properties of the coating film were tested. Table 2 shows the results of the Goban test, and Table 3 shows the results of the light transmittance test.
【００４５】 表２ ゴバン目試験結果（残存数／１００） ──────────────────────────────────── 硬化直後 ＰＣＴ ＮＭＰ ＮａＯＨ ２８０℃ 処理後 処理後 処理後 処理後 ──────────────────────────────────── 実施例１ 100/100 100/100 100/100 100/100 100/100 〃 ２ 100/100 100/100 100/100 100/100 100/100 〃 ３ 100/100 100/100 100/100 100/100 100/100 〃 ４ 100/100 100/100 100/100 100/100 100/100 〃 ５ 100/100 100/100 100/100 100/100 100/100 〃 ６ 100/100 100/100 100/100 100/100 100/100 〃 ７ 100/100 100/100 100/100 100/100 100/100 〃 ８ 100/100 100/100 100/100 100/100 100/100 〃 ９ 100/100 100/100 100/100 100/100 100/100 〃 10 100/100 100/100 100/100 100/100 100/100 〃 11 100/100 100/100 100/100 100/100 100/100 〃 12 100/100 100/100 100/100 100/100 100/100 比較例１ 100/100 0/100 100/100 0/100 100/100 〃 ２ 100/100 10/100 100/100 100/100 100/100 〃 ３ 100/100 50/100 100/100 100/100 100/100 ────────────────────────────────────Table 2 Result of Goban Order Test (Remaining Number / 100)直 後 Immediately after curing PCT NMP NaOH 280 ℃ After treatment After treatment After treatment After treatment ────────────────────────────────── ── Example 1 100/100 100/100 100/100 100/100 100/100 〃 2 100/100 100/100 100/100 100/100 100/100 〃 3 100/100 100/100 100/100 100 / 100 100/100 ４ 4 100/100 100/100 100/100 100/100 100/100 〃 5 100/100 100/100 100/100 100/100 100/100 ６ 6 100/100 100/100 100/100 100 / 100 100/100 〃 7 100/100 100/100 100/100 100/100 100/100 〃 8 100/100 100/100 100/100 100/100 100/100 ９ 9 100/100 100/100 100/100 100/100 100/100 〃 10 100/100 100/100 100/100 100/100 100/100 〃 11 100/100 100/100 100/100 100/100 100/100 〃 12 100/100 100/100 100 / 100 100/100 100/100 Comparative Example 1 100/100 0/100 100/100 0/100 100/100 〃 2 100/100 10/100 100/100 100/100 100/100 〃 3 100/100 50/100 100/100 100/100 100/100 ─────── ─────────────────────────────
【００４６】 表３ 光線透過率試験結果（400〜800nm） ──────────────────────────────────── 硬化直後 ＰＣＴ ＮＭＰ ＮａＯＨ ２８０℃ 処理後 処理後 処理後 処理後 ──────────────────────────────────── 実施例１ 95%以上 95%以上 95%以上 95%以上 90% 〃 ２ 95%以上 95%以上 95%以上 95%以上 90% 〃 ３ 95%以上 95%以上 95%以上 95%以上 90% 〃 ４ 95%以上 95%以上 95%以上 95%以上 95%以上 〃 ５ 95%以上 95%以上 95%以上 95%以上 95%以上 〃 ６ 95%以上 95%以上 95%以上 95%以上 95%以上 〃 ７ 95%以上 95%以上 95%以上 95%以上 90% 〃 ８ 95%以上 95%以上 95%以上 95%以上 90% 〃 ９ 95%以上 95%以上 95%以上 95%以上 90% 〃 10 95%以上 95%以上 95%以上 95%以上 95%以上 〃 11 95%以上 95%以上 95%以上 95%以上 95%以上 〃 12 95%以上 95%以上 95%以上 95%以上 95%以上 比較例１ 95%以上 50%以下 80% 50%以下 95%以上 〃 ２ 95%以上 80% 95%以上 80% 90% 〃 ３ 95%以上 90% 95%以上 95%以上 90% ────────────────────────────────────Table 3 Light transmittance test results (400-800 nm)直 後 Immediately after curing PCT NMP NaOH 280 ℃ After treatment After treatment After treatment After treatment ────────────────────────────────── ── Example 1 95% or more 95% or more 95% or more 90% 〃 2 95% or more 95% or more 95% or more 95% or more 90% 〃 3 95% or more 95% or more 95% or more 95% or more 90 % ４ 4 95% or more 95% or more 95% or more 95% or more 95% or more ５ 5 95% or more 95% or more 95% or more 95% or more 95% or more ６ 6 95% or more 95% or more 95% or more 95% or more 95 % Or more ７ 7 95% or more 95% or more 95% or more 95% or more 90% ８ 8 95% or more 95% or more 95% or more 95% or more 90% ９ 9 95% or more 95% or more 95% or more 95% or more 90% 〃 10 95% or more 95% or more 95% or more 95% or more 95% or more 〃 11 95% or more 95% or more 95% or more 95% or more 95% or more 〃 12 95% or more 95% or more 95% or more 95% or more 95% or more Comparative Example 1 95% or more 50% or less 80% 50% or less 95% or more 〃 2 95% or more 80% 95% or more 80% 90% ３ 3 95% 90% 95% or more 95% or more 90% 以上
【００４７】実施例１３ 実施例１〜１２で調製した組成物溶液を一般的に知られ
ている方法で作製したカラーフィルター基材上に塗布し
た後、加熱硬化して保護膜を形成し、保護膜付きカラー
フィルターの特性を調べた。Example 13 The composition solutions prepared in Examples 1 to 12 were applied on a color filter substrate prepared by a generally known method, and then heated and cured to form a protective film, The characteristics of the color filter with a film were examined.
【００４８】カラーフィルター基材は透明ガラス基板上
にゼラチンと重クロム酸カリウム溶液を用いて、常法に
よりストライプ状の赤、緑、青の３色の染色式カラーフ
ィルターがついた基材を作製した（ストライプ幅１００
μｍ）。この基材の表面凹凸を触針式膜厚計（Ｓｕｒｆ
ｃｏｍ；東京精密（株）商品名）によって測定したとこ
ろ、１．０μｍであった。次に、このカラーフィルター
基材上に前記組成物溶液を７００ｒｐｍで回転塗布し、
１８０℃で１時間乾燥することにより保護層付きカラー
フィルタを作製した。このようにして作製された保護膜
付きカラーフィルター上に、インジウムチンオキシド
（ＩＴＯ）を常法に従い蒸着した後、ホトリソグラフィ
ーによりパターニングした。このＩＴＯのパターンを有
するカラーフィルターを、光学顕微鏡で詳細に観察した
が、カラーフィルターや保護膜にシワやクラック等は全
く認められず、カラーフィルターと保護膜、ＩＴＯと保
護膜との密着性も表４に示すように良好であった。さら
に、このＩＴＯのパターンを有するカラーフィルターを
イソプロピルアルコール（ＩＰＡ）のベーパー槽に３０
分間放置後、光学顕微鏡で詳細に観察したが、ＩＴＯ面
及び保護膜面に異常は見られなかった。A color filter substrate is prepared by using a gelatin and potassium dichromate solution on a transparent glass substrate and using a dyeing type color filter of three colors of red, green and blue in a striped manner by a conventional method. (Stripe width 100
μm). The surface unevenness of this substrate is measured by a stylus type film thickness meter (Surf
com; Tokyo Seimitsu Co., Ltd.) was 1.0 μm. Next, the composition solution was spin-coated on the color filter substrate at 700 rpm,
By drying at 180 ° C. for 1 hour, a color filter with a protective layer was produced. Indium tin oxide (ITO) was vapor-deposited on the thus-prepared color filter with a protective film according to a conventional method, and then patterned by photolithography. The color filter having the ITO pattern was observed in detail with an optical microscope, but no wrinkles or cracks were observed in the color filter or the protective film, and the adhesion between the color filter and the protective film, and the adhesion between the ITO and the protective film were also observed. It was good as shown in Table 4. Further, the color filter having the pattern of ITO is placed in a vapor tank of isopropyl alcohol (IPA) for 30 minutes.
After standing for a minute, it was observed in detail with an optical microscope, but no abnormality was found on the ITO surface and the protective film surface.
【００４９】比較例５ 比較例１〜４で調製した組成物溶液を用いた以外は実施
例１３と全く同様にしてカラーフィルタ基材への適性を
調べた。結果を表４に示す。 表４ カラーフィルター基材適性試験結果 ───────────────────────────────── ITO蒸着後の 1) カラーフィルター、ITO 2) IPAヘ゛ーハ゜ー槽に放置 3) シワ、クラックの発生 との密着性 後の外観変化 ───────────────────────────────── 実施例１ ○ △ ○ 〃 ２ ○ ○ ○ 〃 ３ ○ ○ ○ 〃 ４ ○ ○ ○ 〃 ５ ○ ○ ○ 〃 ６ ○ ○ ○ 〃 ７ ○ △ ○ 〃 ８ ○ ○ ○ 〃 ９ ○ ○ ○ 〃 10 ○ ○ ○ 〃 11 ○ ○ ○ 〃 12 ○ ○ ○ 比較例１ × × × 〃 ２ ○ × ○ 〃 ３ ○ ○ × ────────────────────────────────── 1)異常のないものを○、シワ、クラックが発生したものを×とした。 2)ゴバン目試験により、剥がれのないものを○、部分的に剥がれのある ものを△、完全に剥がれたものを×とした。 3)ＩＰＡベーパー槽に放置後、外観変化のないものを○、保護膜やＩＴ Ｏ面、またはその界面に膨れが発生したものを×とした。Comparative Example 5 The suitability for a color filter substrate was examined in exactly the same manner as in Example 13 except that the composition solutions prepared in Comparative Examples 1 to 4 were used. Table 4 shows the results. Table 4 Color filter substrate suitability test results ───────────────────────────────── 1) Color filter after ITO deposition , ITO 2) Leave in IPA overhaul tank 3) Change in appearance after adhesion with wrinkles and cracks ────────────────────────── ─────── Example 1 ○ △ ○ 〃 2 ○ ○ ○ 〃 3 ○ ○ ○ ○ 4 ○ ○ ○ ○ 5 ○ ○ ○ 〃 6 ○ ○ ○ ○ 7 ○ △ ○ 〃 8 ○ ○ ○ 〃 9 ○ ○ ○ 〃 10 ○ ○ ○ 〃 11 ○ ○ ○ 〃 12 ○ ○ ○ Comparative Example 1 × × × 〃 2 ○ × ○ 〃 3 ○ ○ × ──────────────── ────────────────── 1) No abnormality was indicated by ○, wrinkles and cracks were indicated by X. 2) In the Goban test, those with no peeling were rated as ○, those with partial peeling were rated as Δ, and those with complete peeling were rated as x. 3) A sample having no change in appearance after standing in an IPA vapor tank was rated as “O”, and a sample having blisters generated on the protective film, the ITO surface, or its interface was rated as “X”.
【００５０】[0050]
【発明の効果】請求項１〜３のいずれかにおける硬化塗
膜用樹脂組成物から形成される塗膜は、平滑であり、透
明性、接着性、耐湿性、耐薬品性、耐熱性、耐傷性等に
極めて優れている。また請求項４におけるカラーフィル
タ保護膜は、請求項１〜３のいずれかにおける硬化塗膜
用樹脂組成物を用いて形成され、前記樹脂組成物から形
成される塗膜と同様に優れた特性を示す。さらに請求項
５におけるカラーフィルタは、請求項４のカラーフィル
タ保護膜を用いて形成され、前記のカラーフィルタ保護
膜と同様に優れた特性を示す。According to the present invention, the coating film formed from the resin composition for a cured coating film according to any one of claims 1 to 3 is smooth and has transparency, adhesion, moisture resistance, chemical resistance, heat resistance, and scratch resistance. Excellent in properties and the like. The color filter protective film according to claim 4 is formed using the resin composition for a cured coating film according to any one of claims 1 to 3, and has excellent characteristics similarly to a coating film formed from the resin composition. Show. Further, the color filter of claim 5 is formed using the color filter protective film of claim 4, and exhibits excellent characteristics similarly to the color filter protective film.
Claims (5)
テルおよび／またはアクリル酸グリシジルエステル６０
〜９０重量部および （２）環内に３級炭素を含む炭素数７〜２０の脂環式メ
タクリル酸エステルおよび／またはアクリル酸エステル
１０〜４０重量部および必要により、他の共重合可能な
不飽和単量体０〜３０重量部を総量が１００重量部とな
る量で重合して得られる共重合樹脂１００重量部 Ｂ．（３）Ｎ−置換マレイミド （４）アクリル酸および／またはメタクリル酸および （５）必要により他の不飽和単量体を重合して得られる
共重合樹脂２０〜２００重量部 Ｃ．多価カルボン酸無水物および多価カルボン酸からな
る群より選ばれる少なくとも１種の化合物５〜５０重量
部ならびに Ｄ．官能性シランカップリング剤３０〜１００重量部を
含有してなる硬化塗膜用樹脂組成物。1. A. First Embodiment (1) Glycidyl methacrylate and / or glycidyl acrylate 60
To 90 parts by weight and (2) 10 to 40 parts by weight of an alicyclic methacrylate and / or acrylate having 7 to 20 carbon atoms containing a tertiary carbon in the ring, and if necessary, other copolymerizable copolymers. A. 100 parts by weight of a copolymer resin obtained by polymerizing 0 to 30 parts by weight of a saturated monomer so that the total amount becomes 100 parts by weight. (3) N-substituted maleimide (4) Acrylic acid and / or methacrylic acid and (5) 20 to 200 parts by weight of a copolymer resin obtained by polymerizing another unsaturated monomer as required. C. 5 to 50 parts by weight of at least one compound selected from the group consisting of polycarboxylic anhydrides and polycarboxylic acids; A resin composition for a cured coating film containing 30 to 100 parts by weight of a functional silane coupling agent.
イミド、Ｎ−エチルマレイミド、Ｎ−プロピルマレイミ
ド、Ｎ−ブチルマレイミド、Ｎ−シクロヘキシルマレイ
ミド、Ｎ−フェニルマレイミドおよびＮ−アルキル基置
換マレイミドからなる群より選ばれる少なくとも１種の
化合物である請求項１記載の硬化塗膜用樹脂組成物。2. The group consisting of N-substituted maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and N-alkyl-substituted maleimide. The resin composition for a cured coating film according to claim 1, which is at least one compound selected from the group consisting of:
脂環式メタクリル酸エステルおよび／またはアクリル酸
エステルが、ノルボルニル基またはボルニル基を有する
脂環式メタクリル酸エステルおよび／またはアクリル酸
エステルである請求項１または２記載の硬化塗膜用樹脂
組成物。3. The alicyclic methacrylate and / or acrylate having 7 to 20 carbon atoms containing a tertiary carbon in the ring is an alicyclic methacrylate and / or acryl having a norbornyl group or a bornyl group. The resin composition for a cured coating film according to claim 1, which is an acid ester.
樹脂組成物を用いたカラーフィルタ保護膜。4. A color filter protective film using the resin composition for a cured coating film according to claim 1, 2, or 3.
用いたカラーフィルタ。5. A color filter using the color filter protective film according to claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16019296A JPH107981A (en) | 1996-06-20 | 1996-06-20 | Resin composition for cured coating film, and color filter protection film and color filter produced from the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16019296A JPH107981A (en) | 1996-06-20 | 1996-06-20 | Resin composition for cured coating film, and color filter protection film and color filter produced from the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH107981A true JPH107981A (en) | 1998-01-13 |
Family
ID=15709812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16019296A Pending JPH107981A (en) | 1996-06-20 | 1996-06-20 | Resin composition for cured coating film, and color filter protection film and color filter produced from the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH107981A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000103937A (en) * | 1998-09-29 | 2000-04-11 | Jsr Corp | Thermosetting resin composition |
-
1996
- 1996-06-20 JP JP16019296A patent/JPH107981A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000103937A (en) * | 1998-09-29 | 2000-04-11 | Jsr Corp | Thermosetting resin composition |
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