JPH04369653A - Coloring photosensitive resin composition - Google Patents
Coloring photosensitive resin compositionInfo
- Publication number
- JPH04369653A JPH04369653A JP3242897A JP24289791A JPH04369653A JP H04369653 A JPH04369653 A JP H04369653A JP 3242897 A JP3242897 A JP 3242897A JP 24289791 A JP24289791 A JP 24289791A JP H04369653 A JPH04369653 A JP H04369653A
- Authority
- JP
- Japan
- Prior art keywords
- photosensitive
- composition
- photosensitive resin
- pattern
- coating film
- 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 27
- 238000004040 coloring Methods 0.000 title abstract 4
- 239000000203 mixture Substances 0.000 claims abstract description 72
- -1 carboxylic acid compound Chemical class 0.000 claims abstract description 37
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 28
- 239000004760 aramid Substances 0.000 claims abstract description 27
- 239000012860 organic pigment Substances 0.000 claims abstract description 27
- 230000002378 acidificating effect Effects 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 13
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 9
- 239000002798 polar solvent Substances 0.000 claims description 9
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 7
- 238000000576 coating method Methods 0.000 abstract description 46
- 239000011248 coating agent Substances 0.000 abstract description 45
- 239000000758 substrate Substances 0.000 abstract description 39
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 150000002894 organic compounds Chemical class 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 230000008961 swelling Effects 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 48
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 22
- 239000004952 Polyamide Substances 0.000 description 12
- 229920002647 polyamide Polymers 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 11
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 10
- 150000004984 aromatic diamines Chemical class 0.000 description 10
- 239000000049 pigment Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000001056 green pigment Substances 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- ILBBNQMSDGAAPF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-1-one Chemical compound CCC(=O)C1C=CC=CC1(C)O ILBBNQMSDGAAPF-UHFFFAOYSA-N 0.000 description 5
- 206010034972 Photosensitivity reaction Diseases 0.000 description 5
- 238000005562 fading Methods 0.000 description 5
- 230000036211 photosensitivity Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LDQMZKBIBRAZEA-UHFFFAOYSA-N 2,4-diaminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C(N)=C1 LDQMZKBIBRAZEA-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 3
- LKFKFNXPGMGBIS-XCVCLJGOSA-N (e)-1,3-bis(4-aminophenyl)prop-2-en-1-one Chemical compound C1=CC(N)=CC=C1\C=C\C(=O)C1=CC=C(N)C=C1 LKFKFNXPGMGBIS-XCVCLJGOSA-N 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 2
- QLVKECUOHNDWOI-UHFFFAOYSA-N 2-oxo-1,3,2$l^{5}-diazaphosphonan-2-amine Chemical compound NP1(=O)NCCCCCCN1 QLVKECUOHNDWOI-UHFFFAOYSA-N 0.000 description 2
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 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
- 230000001476 alcoholic effect Effects 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 229930016911 cinnamic acid Natural products 0.000 description 2
- 235000013985 cinnamic acid Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 230000001678 irradiating effect Effects 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
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- ZZSIDSMUTXFKNS-UHFFFAOYSA-N perylene red Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N(C(=O)C=1C2=C3C4=C(OC=5C=CC=CC=5)C=1)C(=O)C2=CC(OC=1C=CC=CC=1)=C3C(C(OC=1C=CC=CC=1)=CC1=C2C(C(N(C=3C(=CC=CC=3C(C)C)C(C)C)C1=O)=O)=C1)=C2C4=C1OC1=CC=CC=C1 ZZSIDSMUTXFKNS-UHFFFAOYSA-N 0.000 description 2
- 238000000016 photochemical curing Methods 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
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 2
- DPNWQJXXLMZUPO-UHFFFAOYSA-N (2,4-diaminophenyl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=C(N)C=C1N DPNWQJXXLMZUPO-UHFFFAOYSA-N 0.000 description 1
- ICBFXMFMUMSALX-UHFFFAOYSA-N (3,5-diaminophenyl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC(N)=CC(N)=C1 ICBFXMFMUMSALX-UHFFFAOYSA-N 0.000 description 1
- WOGITNXCNOTRLK-VOTSOKGWSA-N (e)-3-phenylprop-2-enoyl chloride Chemical compound ClC(=O)\C=C\C1=CC=CC=C1 WOGITNXCNOTRLK-VOTSOKGWSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- AOKSIVVSCQOMRN-UHFFFAOYSA-N 1,3-bis(3-aminophenyl)prop-2-en-1-one Chemical compound NC1=CC=CC(C=CC(=O)C=2C=C(N)C=CC=2)=C1 AOKSIVVSCQOMRN-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- FBMQNRKSAWNXBT-UHFFFAOYSA-N 1,4-diaminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=CC=C2N FBMQNRKSAWNXBT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- VWBVCOPVKXNMMZ-UHFFFAOYSA-N 1,5-diaminoanthracene-9,10-dione Chemical compound O=C1C2=C(N)C=CC=C2C(=O)C2=C1C=CC=C2N VWBVCOPVKXNMMZ-UHFFFAOYSA-N 0.000 description 1
- CXCJRDOERHOGMC-UHFFFAOYSA-N 1-(3-amino-4-methoxyphenyl)-3-(4-aminophenyl)prop-2-en-1-one Chemical compound C1=C(N)C(OC)=CC=C1C(=O)C=CC1=CC=C(N)C=C1 CXCJRDOERHOGMC-UHFFFAOYSA-N 0.000 description 1
- MDAHMOQFFILZCJ-UHFFFAOYSA-N 1-(3-amino-4-methylphenyl)-3-(4-aminophenyl)prop-2-en-1-one Chemical compound C1=C(N)C(C)=CC=C1C(=O)C=CC1=CC=C(N)C=C1 MDAHMOQFFILZCJ-UHFFFAOYSA-N 0.000 description 1
- XTZGKMKTRMDYGP-UHFFFAOYSA-N 1-(3-aminophenyl)-3-(4-aminophenyl)prop-2-en-1-one Chemical compound C1=CC(N)=CC=C1C=CC(=O)C1=CC=CC(N)=C1 XTZGKMKTRMDYGP-UHFFFAOYSA-N 0.000 description 1
- HWEONUWVYWIJPF-OWOJBTEDSA-N 1-azido-4-[(e)-2-(4-azidophenyl)ethenyl]benzene Chemical compound C1=CC(N=[N+]=[N-])=CC=C1\C=C\C1=CC=C(N=[N+]=[N-])C=C1 HWEONUWVYWIJPF-OWOJBTEDSA-N 0.000 description 1
- HABJWTMJQUIKSY-UHFFFAOYSA-N 10,10-bis(4-aminophenyl)anthracen-9-one Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C(=O)C2=CC=CC=C21 HABJWTMJQUIKSY-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- YJGUVTBNQCVSQB-UHFFFAOYSA-N 2,2-diphenylpropanedioic acid Chemical compound C=1C=CC=CC=1C(C(O)=O)(C(=O)O)C1=CC=CC=C1 YJGUVTBNQCVSQB-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- UZNOMHUYXSAUPB-UHFFFAOYSA-N 2,6-bis[(4-azidophenyl)methylidene]cyclohexan-1-one Chemical compound C1=CC(N=[N+]=[N-])=CC=C1C=C(CCC1)C(=O)C1=CC1=CC=C(N=[N+]=[N-])C=C1 UZNOMHUYXSAUPB-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- CPELGENCLYYBLN-UHFFFAOYSA-N 2-aminobenzoic acid;2-(dimethylamino)benzoic acid Chemical compound NC1=CC=CC=C1C(O)=O.CN(C)C1=CC=CC=C1C(O)=O CPELGENCLYYBLN-UHFFFAOYSA-N 0.000 description 1
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- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- ZSLJCCBJHCWFIR-UHFFFAOYSA-N 3-(3,5-diaminophenyl)-1-phenylprop-2-en-1-one Chemical compound NC1=CC(N)=CC(C=CC(=O)C=2C=CC=CC=2)=C1 ZSLJCCBJHCWFIR-UHFFFAOYSA-N 0.000 description 1
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- AJYDKROUZBIMLE-UHFFFAOYSA-N 4-[2-[2-[2-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=CC=C(OC=2C=CC(N)=CC=2)C=1C(C)(C)C1=CC=CC=C1OC1=CC=C(N)C=C1 AJYDKROUZBIMLE-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
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- 241000526960 Amaranthus acanthochiton Species 0.000 description 1
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- GXCSNALCLRPEAS-CFYXSCKTSA-N azane (Z)-hydroxyimino-oxido-phenylazanium Chemical compound N.O\N=[N+](/[O-])c1ccccc1 GXCSNALCLRPEAS-CFYXSCKTSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- KGQLBLGDIQNGSB-UHFFFAOYSA-N benzene-1,4-diol;methoxymethane Chemical compound COC.OC1=CC=C(O)C=C1 KGQLBLGDIQNGSB-UHFFFAOYSA-N 0.000 description 1
- LHMRXAIRPKSGDE-UHFFFAOYSA-N benzo[a]anthracene-7,12-dione Chemical compound C1=CC2=CC=CC=C2C2=C1C(=O)C1=CC=CC=C1C2=O LHMRXAIRPKSGDE-UHFFFAOYSA-N 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 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
- 150000001789 chalcones Chemical class 0.000 description 1
- 235000005513 chalcones Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 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
- 238000005259 measurement Methods 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- RNVCVTLRINQCPJ-UHFFFAOYSA-N ortho-methyl aniline Natural products CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 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
- 238000002834 transmittance Methods 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Optical Filters (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】この発明は、概略、感光性芳香族
ポリアミドなどの感光性樹脂と光重合開始剤とカルボン
酸化合物と酸性有機顔料とを含有する着色感光性樹脂組
成物に係わるものである。この発明の着色感光性樹脂組
成物は、その組成物の塗膜(皮膜)を基材上に形成し、
その塗膜上に光照射してパターン状に光硬化させ、最後
に、現像液で該塗膜の未露光部分(未硬化部分)を除去
する現像操作を行うことによって、カラー撮像素子や、
カラーセンサー、カラーディスプレー等の微細色分解用
のカラーフィルターなどの着色パターン部材の製造方法
において使用することができる。[Field of Industrial Application] This invention generally relates to a colored photosensitive resin composition containing a photosensitive resin such as a photosensitive aromatic polyamide, a photopolymerization initiator, a carboxylic acid compound, and an acidic organic pigment. be. The colored photosensitive resin composition of the present invention is obtained by forming a coating film (film) of the composition on a base material,
By irradiating the coating film with light to photocure it in a pattern, and finally performing a development operation in which the unexposed portion (uncured portion) of the coating film is removed using a developer, color imaging elements,
It can be used in a method for manufacturing colored pattern members such as color filters for fine color separation of color sensors, color displays, etc.
【0002】0002
【従来技術の説明】従来、カラーフィルター等の着色パ
ターン部材の製造方法としては、(a)ガラス等の透明
基板上にゼラチン等を用いて染色型有機色素フィルター
を生成し、該フィルターを接着剤により固体撮像素子上
に貼り合わせる方法、(b)カラーフィルターの如き多
色表面着色体を製造するための最も簡便な手段としては
、印刷による方法、(c)特開昭60−237403号
公報には、感光性を有する耐熱性フィルム形成材料とし
て知られているポリイミド樹脂を用いてカラーフィルタ
ーを製造する方法、(d)特開昭62−212603号
公報には、透明な感光性ポリアミドを用いる方法などが
示されている。[Description of the Prior Art] Conventionally, as a method for producing colored pattern members such as color filters, (a) a dyed organic dye filter is produced using gelatin or the like on a transparent substrate such as glass, and the filter is attached with an adhesive. (b) The simplest method for manufacturing a multicolored surface-colored object such as a color filter is a printing method. (c) Japanese Patent Application Laid-Open No. 60-237403 (d) JP-A No. 62-212603 discloses a method of manufacturing a color filter using polyimide resin, which is known as a heat-resistant film-forming material with photosensitivity, and (d) a method of using transparent photosensitive polyamide. etc. are shown.
【0003】前述のゼラチンを用いた従来公知のカラー
フィルターは、耐熱性に乏しく加工工程において褪色し
たりする問題があった。また、前記の印刷による方法は
、多色刷りの際の位置決めが難しく、位置精度及び寸法
精度に制限があり、高精度且つ高細度なカラーフィルタ
ーを製造することができなかった。[0003] Conventionally known color filters using gelatin described above have a problem of poor heat resistance and fading during processing steps. Further, in the printing method described above, positioning during multicolor printing is difficult, and positional accuracy and dimensional accuracy are limited, making it impossible to manufacture highly accurate and fine color filters.
【0004】また、特開昭60−237403号公報に
記載された方法では、感光性ポリイミド樹脂がポリイミ
ド前駆体として供されるため、良好な皮膜特性を有する
ポリイミドに転換するためには、200〜300℃又は
それ以上の高温処理が必要であり、そのために熱により
有機顔料が劣化するなどの問題がある。さらに、特開昭
62−212603号公報に記載の方法は、感光性ポリ
アミド樹脂組成物の耐熱性が良好ではあるが、感度が充
分ではなかった。Furthermore, in the method described in JP-A No. 60-237403, since the photosensitive polyimide resin is used as a polyimide precursor, in order to convert it into a polyimide having good film properties, it is necessary to A high temperature treatment of 300° C. or higher is required, which poses problems such as deterioration of organic pigments due to heat. Furthermore, in the method described in JP-A-62-212603, although the heat resistance of the photosensitive polyamide resin composition was good, the sensitivity was not sufficient.
【0005】特開平2−12317号公報には、前述の
公知の技術における問題を解決することができる着色感
光性組成物として、感光性基を有する耐熱性ポリアミド
と、ビスアジド化合物との組成物に、有機顔料が分散さ
れている着色感光性ポリアミド組成物について開示され
ている。[0005] JP-A-2-12317 discloses a composition of a heat-resistant polyamide having a photosensitive group and a bisazide compound as a colored photosensitive composition that can solve the problems in the above-mentioned known techniques. , discloses a colored photosensitive polyamide composition in which an organic pigment is dispersed.
【0006】しかし、前記の公知の着色感光性ポリアミ
ド組成物は、選択的に可視光を透過させ、遮蔽すること
を目的とするために顔料などをかなりな量含有しており
、その結果、基材上の皮膜(塗膜)の光硬化に必要な『
感光性を起こさせるに必要な近紫外の光』が、着色感光
性組成物で形成された皮膜の底部(基材の表面)まで充
分に到達せず、現像液による現像操作の際に、光照射さ
れた着色パターン部の剥がれ、膨れ、変形等がしばしば
生じるという問題があり、着色感光性組成物の光硬化層
からなる着色パターン(カラーフィルターなど)の色の
濃度等を満足させようとして顔料の配合量を増加させよ
うとしても、そのような顔料が高配合された着色感光性
組成物ではその皮膜の感光性が不満足なものとなってい
た。However, the above-mentioned known colored photosensitive polyamide compositions contain a considerable amount of pigment etc. for the purpose of selectively transmitting and blocking visible light. The "
The near-ultraviolet light necessary to cause photosensitivity does not reach the bottom of the film formed from the colored photosensitive composition (the surface of the substrate), and light There is a problem that peeling, blistering, deformation, etc. of the irradiated colored pattern part often occurs, and when trying to satisfy the color density etc. of a colored pattern (such as a color filter) consisting of a photocured layer of a colored photosensitive composition, pigment Even if attempts were made to increase the amount of such pigments, colored photosensitive compositions containing a high amount of such pigments had unsatisfactory photosensitivity of the film.
【0007】また、前記の公知の着色感光性ポリアミド
組成物は、顔料を単にポリマー溶液中に分散して得られ
た溶液組成物を基材に塗布して形成された皮膜として使
用されるためにその皮膜中の顔料の分散が充分でなく、
顔料の分散性の悪い溶液から得られる塗膜(皮膜)は平
坦性、平滑性に劣り、着色パターン(カラーフィルター
等)の色度の均一性を悪化させるだけではなく、その皮
膜の感度、解像度などが不充分となるのである。[0007] Furthermore, the above-mentioned known colored photosensitive polyamide compositions are used as a film formed by simply dispersing a pigment in a polymer solution and applying the resulting solution composition to a substrate. The pigment in the film is not sufficiently dispersed,
Paint films obtained from solutions with poor pigment dispersibility have poor flatness and smoothness, which not only deteriorates the uniformity of chromaticity of colored patterns (color filters, etc.), but also reduces the sensitivity and resolution of the film. etc. will be insufficient.
【0008】さらに、前記の公知の着色感光性ポリアミ
ド組成物からなる皮膜は、パターンマスクを通して露光
してパターン光硬化し、現像液で充分に現像すると、現
像液が皮膜内に膨潤してパターンが変形したり、あるい
は、皮膜中の顔料が流出したりするという問題があった
。Furthermore, the film made of the above-mentioned known colored photosensitive polyamide composition is exposed through a pattern mask to photocure the pattern, and when sufficiently developed with a developer, the developer swells within the film and the pattern is formed. There was a problem that the film was deformed or the pigment in the film leaked out.
【0009】[0009]
【本発明が解決しようとする問題点】この発明の目的は
、着色パターン(特にカラーフィルター等)の形成など
に使用される公知の着色感光性組成物が有していた、顔
料の分散性が悪く平滑な皮膜を形成することが困難であ
ること、あるいは、皮膜の感度、解像度が充分ではない
こと、さらに、現像時に光硬化したパターンが現像液の
膨潤により変形すること、および、パターンから顔料が
流出すること等の種々の欠点を一挙に改良することを目
的とする。[Problems to be Solved by the Present Invention] The purpose of the present invention is to improve the dispersibility of pigments, which is present in known colored photosensitive compositions used for forming colored patterns (particularly color filters, etc.). It is difficult to form a smooth film, or the sensitivity and resolution of the film are not sufficient.Furthermore, the photocured pattern is deformed by the swelling of the developer during development, and pigments are removed from the pattern. The purpose is to improve all at once various drawbacks such as the outflow of water.
【0010】0010
【問題点を解決するための手段】この発明は、炭素−炭
素不飽和結合を有する感光性樹脂、光重合開始剤、カル
ボン酸化合物、および、酸性有機顔料を含有することを
特徴とする着色感光性樹脂組成物に関する。[Means for Solving the Problems] The present invention provides a colored photosensitive resin characterized by containing a photosensitive resin having a carbon-carbon unsaturated bond, a photopolymerization initiator, a carboxylic acid compound, and an acidic organic pigment. The present invention relates to a synthetic resin composition.
【0011】この発明の着色感光性樹脂組成物は、例え
ば、■炭素−炭素二重結合(感光性基)を有する感光性
(芳香族)ポリアミド、感光性(芳香族)ポリイミドな
どの『感光性樹脂』、■ビスアジド化合物、ベンジル類
、ベンゾインエーテル類、チオキサントン類等の『光重
合開始剤』、■シュウ酸、グリコール酸、マレイン酸、
コハク酸、フタル酸、乳酸等の『カルボン酸化合物』及
び■『酸性有機顔料』が、均一に配合、混合又は分散さ
れている着色感光性樹脂組成物、或いはその溶液組成物
が好適である。[0011] The colored photosensitive resin composition of the present invention can be applied to photosensitive resin compositions such as photosensitive (aromatic) polyamides and photosensitive (aromatic) polyimides having carbon-carbon double bonds (photosensitive groups). ■Photopolymerization initiators such as bisazide compounds, benzyl, benzoin ethers, and thioxanthone, ■Oxalic acid, glycolic acid, maleic acid,
A colored photosensitive resin composition or a solution composition thereof in which a "carboxylic acid compound" such as succinic acid, phthalic acid, lactic acid, etc. and (1) "acidic organic pigment" are uniformly blended, mixed or dispersed is suitable.
【0012】前記の炭素−炭素不飽和結合を有する感光
性樹脂としては、(メタ)アクリレート化されたエポキ
シ樹脂、(メタ)アクリレート化されたウレタン樹脂、
(メタ)アクリレート化されたポリエステル樹脂などの
多官能性アクリレート系樹脂、あるいは、感光性ポリア
ミド、感光性ポリイミド、感光性ポリシロキサン、感光
性ポリアルキル(メタ)アクリレート、感光性ポリビニ
ルアルコール、又は、それらの誘導体などの炭素−炭素
不飽和結合を有する感光性重合体を挙げることができる
。[0012] Examples of the photosensitive resin having a carbon-carbon unsaturated bond include (meth)acrylated epoxy resin, (meth)acrylated urethane resin,
Multifunctional acrylate resin such as (meth)acrylated polyester resin, photosensitive polyamide, photosensitive polyimide, photosensitive polysiloxane, photosensitive polyalkyl (meth)acrylate, photosensitive polyvinyl alcohol, or the like. Examples include photosensitive polymers having carbon-carbon unsaturated bonds such as derivatives of.
【0013】前記の感光性樹脂としては、特開平2−1
2317号公報などの記載されている炭素−炭素不飽和
結合を有する可溶性の感光性芳香族ポリアミドが、感光
性、耐熱性などの点において、好適である。[0013] As the photosensitive resin, JP-A-2-1
A soluble photosensitive aromatic polyamide having a carbon-carbon unsaturated bond described in Japanese Patent No. 2317 and the like is suitable in terms of photosensitivity, heat resistance, and the like.
【0014】前記の感光性芳香族ポリアミドとしては、
例えば、下記一般式(I)[0014] As the photosensitive aromatic polyamide,
For example, the following general formula (I)
【化1】
(但し、Ar1及びAr2はそれぞれ芳香族残基を示し
、Ar2は感光性基を有する芳香族残基を示す。)で示
される構成単位を40〜100モル%、および、40 to 100 mol% of the structural unit represented by the formula (wherein, Ar1 and Ar2 each represent an aromatic residue, and Ar2 represents an aromatic residue having a photosensitive group), and
【00
15】下記一般式(II)00
15] The following general formula (II)
【化2】
(但し、Ar3及びAr4はそれぞれAr1およびAr
2以外の芳香族残基を示す。)で示される構成単位を0
〜60モル%の割合で有する耐熱性芳香族ポリアミドが
好ましい。[Chemical formula 2] (However, Ar3 and Ar4 are Ar1 and Ar, respectively.
Indicates an aromatic residue other than 2. ) is shown as 0
Preferably, the heat-resistant aromatic polyamide has a proportion of ~60 mol%.
【0016】前記の感光性芳香族ポリアミドとしては、
一般式(I)で示される構成単位のみからなる感光性の
芳香族ポリアミドを20重量%以上と、一般式(II)
で示される構成単位のみからなる芳香族ポリアミドを8
0重量%未満の割合で混合された芳香族ポリアミドの混
合物であってもよい。[0016] As the photosensitive aromatic polyamide,
20% by weight or more of a photosensitive aromatic polyamide consisting only of structural units represented by general formula (I), and general formula (II)
An aromatic polyamide consisting only of the structural units shown in 8
It may also be a mixture of aromatic polyamides mixed in a proportion of less than 0% by weight.
【0017】前記一般式(I)及び(II)において、
Ar1及びAr3で示される芳香族残基は、芳香族ジカ
ルボン酸類の芳香族残基が最適であり、前記芳香族ジカ
ルボン酸類としては、例えば、テレフタル酸、イソフタ
ル酸、4,4’−ジカルボキシビフェニル、4,4’−
ジカルボキシジフェニルメタン、4,4’−ジカルボキ
シジフェニルエーテルなどの芳香族ジカルボン酸、また
はそれらの酸ハロゲン化物を挙げることができる。これ
らの芳香族ジカルボン酸成分のうちでも、上記芳香族ジ
カルボン酸の酸ハロゲン化物、特に芳香族ジカルボン酸
塩化物が好ましい。In the general formulas (I) and (II),
The aromatic residues represented by Ar1 and Ar3 are optimally aromatic residues of aromatic dicarboxylic acids, and examples of the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, and 4,4'-dicarboxybiphenyl. , 4,4'-
Aromatic dicarboxylic acids such as dicarboxydiphenylmethane and 4,4'-dicarboxydiphenyl ether, or acid halides thereof can be mentioned. Among these aromatic dicarboxylic acid components, acid halides of the above-mentioned aromatic dicarboxylic acids, particularly aromatic dicarboxylic acid chlorides, are preferred.
【0018】また、前記一般式(I)において、Ar2
で示される感光性基を有する芳香族残基は、「感光性の
炭素−炭素不飽和結合を有する有機基(エチレン基、ア
セチレン基、メタアクリロイル基等)などの感光性基を
有する芳香族ジアミン」に基づく芳香族残基が最適であ
る。Furthermore, in the general formula (I), Ar2
The aromatic residue having a photosensitive group represented by "aromatic diamine having a photosensitive group such as an organic group having a photosensitive carbon-carbon unsaturated bond (ethylene group, acetylene group, methacryloyl group, etc.)" ” aromatic residues are optimal.
【0019】そのような芳香族ジアミンとしては、例え
ば、3,5−ジアミノ安息香酸エチルメタクリル酸エス
テル、2,4−ジアミノ安息香酸エチルメタクリル酸エ
ステル、3,5−ジアミノ安息香酸ジグリシジルメタク
リレートエステル、2,4−ジアミノ安息香酸ジグリシ
ジルメタクリレートエステル、3,5−ジアミノ安息香
酸ケイ皮酸エステル、2,4−ジアミノ安息香酸ケイ皮
酸エステル等の安息香酸エステル類、3,5−ジアミノ
ベンジルメタクリレート、2,4−ジアミノベンジルメ
タクリレート等のベンジルメタクリレート類、4−メタ
クリルアミド−3,4’−ジアミノジフェニルエーテル
、2−メタクリルアミド−3,4’−ジアミノジフェニ
ルエーテル、4−シンナムアミド−3,4’−ジアミノ
ジフェニルエーテル、3,4’−ジメタクリルアミド−
3’,4−ジアミノジフェニルエーテル、3,4’−ジ
シンナムアミド−3’,4−ジアミノジフェニルエーテ
ル、4−メチル−2’−(2−メタクリロイルオキシエ
トキシカルボニル)−3,4’−ジアミノジフェニルエ
ーテル等のジフェニルエーテル類、及び、4,4’−ジ
アミノカルコン、3,3’−ジアミノカルコン、3,4
’−ジアミノカルコン、3’,4−ジアミノカルコン、
4’−メチル−3’,4−ジアミノカルコン、4’−メ
トキシ−3’,4−ジアミノカルコン、3’−メチル−
3,5−ジアミノカルコン等のカルコン類などを挙げる
ことができる。Examples of such aromatic diamines include 3,5-diaminobenzoic acid ethyl methacrylate, 2,4-diaminobenzoic acid ethyl methacrylate, 3,5-diaminobenzoic acid diglycidyl methacrylate, Benzoic acid esters such as 2,4-diaminobenzoic acid diglycidyl methacrylate ester, 3,5-diaminobenzoic acid cinnamic acid ester, 2,4-diaminobenzoic acid cinnamic acid ester, 3,5-diaminobenzyl methacrylate, Benzyl methacrylates such as 2,4-diaminobenzyl methacrylate, 4-methacrylamido-3,4'-diaminodiphenyl ether, 2-methacrylamido-3,4'-diaminodiphenyl ether, 4-cinnamamide-3,4'-diaminodiphenyl ether , 3,4'-dimethacrylamide-
Diphenyl ethers such as 3',4-diaminodiphenyl ether, 3,4'-dicinnamamide-3',4-diaminodiphenyl ether, 4-methyl-2'-(2-methacryloyloxyethoxycarbonyl)-3,4'-diaminodiphenyl ether , and 4,4'-diaminochalcone, 3,3'-diaminochalcone, 3,4
'-diaminochalcone, 3',4-diaminochalcone,
4'-Methyl-3',4-diaminochalcone, 4'-methoxy-3',4-diaminochalcone, 3'-methyl-
Examples include chalcones such as 3,5-diaminochalcone.
【0020】また、一般式(II)において、Ar4で
示される芳香族残基は、「感光性基を有していない芳香
族ジアミン」に基づく芳香族残基である。前記の感光性
基を有していない芳香族ジアミンとしては、例えば、(
i)3,5−ジアミノ安息香酸、パラフェニレンジアミ
ン、メタフェニレンジアミン、2,4−ジアミノトルエ
ンなどの1個のベンゼン環を有する芳香族ジアミン、(
ii)4,4’−ジアミノジフェニルエーテル、4,4
’−ジアミノジフェニルメタン、o−トリジン、o−ト
ルイジンスルホン、4,4’−ジアミノベンゾフェノン
、4’−N,N−ジメチルアミノ−3,5−ジアミノベ
ンゾフェノン等の2個のベンゼン環を有する芳香族ジア
ミン、(iii)1,4−ビス(4−アミノフェノキシ
)ベンゼン、2,2−ビス(4−アミノフェノキシフェ
ニル)プロパン、及び、9,9−ビス(4−アミノフェ
ニル)−10−アンスロン、1,5−ジアミノアントラ
キノン、1,4−ジアミノアントラキノン、1−ジメチ
ルアミノ−4−(3,5−ジアミノベンゾフェノン)−
ナフタレン等の3個以上のベンゼン環を有する芳香族ジ
アミンなどを挙げることができる。Further, in the general formula (II), the aromatic residue represented by Ar4 is an aromatic residue based on "aromatic diamine having no photosensitive group." Examples of the above-mentioned aromatic diamines having no photosensitive group include (
i) Aromatic diamines having one benzene ring such as 3,5-diaminobenzoic acid, paraphenylenediamine, metaphenylenediamine, 2,4-diaminotoluene, (
ii) 4,4'-diaminodiphenyl ether, 4,4
Aromatic diamines having two benzene rings such as '-diaminodiphenylmethane, o-tolidine, o-toluidine sulfone, 4,4'-diaminobenzophenone, 4'-N,N-dimethylamino-3,5-diaminobenzophenone , (iii) 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenoxyphenyl)propane, and 9,9-bis(4-aminophenyl)-10-anthrone, 1 , 5-diaminoanthraquinone, 1,4-diaminoanthraquinone, 1-dimethylamino-4-(3,5-diaminobenzophenone)-
Examples include aromatic diamines having three or more benzene rings such as naphthalene.
【0021】前記の感光性芳香族ポリアミドは、例えば
、前述の芳香族ジカルボン酸類の酸成分と、前述の感光
性基を有する芳香族ジアミン及び前述の感光性基を有し
ていない芳香族ジアミンからなる芳香族ジアミン成分と
を、大略等モル使用して、有機極性溶媒中、80℃以下
の反応温度下に、1〜20時間重合反応を行うことによ
り製造される。The photosensitive aromatic polyamide is made of, for example, the acid component of the aromatic dicarboxylic acids described above, the aromatic diamine having the aforementioned photosensitive group, and the aromatic diamine not having the aforementioned photosensitive group. It is produced by carrying out a polymerization reaction in an organic polar solvent at a reaction temperature of 80° C. or less for 1 to 20 hours using approximately equimolar amounts of the aromatic diamine component.
【0022】前記の感光性芳香族ポリアミドにおいて、
一般式(II)で示される構成単位の存在はポリアミド
の熱的性質を向上させる効果があるが、多過ぎると、ポ
リマー鎖中での感光性基の濃度が低くなり光感度が低下
するので、前記の割合の範囲内となるように適宜調整す
ることが好ましい。[0022] In the photosensitive aromatic polyamide,
The presence of the structural unit represented by general formula (II) has the effect of improving the thermal properties of polyamide, but if it is too large, the concentration of photosensitive groups in the polymer chain becomes low and the photosensitivity decreases. It is preferable to adjust the ratio appropriately so that it falls within the above range.
【0023】また、前記の感光性芳香族ポリアミドは、
該芳香族ポリアミドの濃度が0.5g/100ml;N
−メチル−2−ピロリドンである溶液を調製して、30
℃の温度で測定した対数粘度が0.1〜3.5、特に0
.2〜2.5程度であることが好ましい。[0023] Furthermore, the photosensitive aromatic polyamide is
The concentration of the aromatic polyamide is 0.5 g/100 ml; N
-Methyl-2-pyrrolidone and 30
The logarithmic viscosity measured at a temperature of 0.1 to 3.5, especially 0
.. It is preferably about 2 to 2.5.
【0024】前記の感光性芳香族ポリアミドは、例えば
、N,N−ジメチルホルムアミド、N,N−ジメチルア
セトアミド、N−メチル−2−ピロリドン、ジメチルス
ルホキシド、ヘキサメチレンホスホルアミド、ジグライ
ム、トリグライム、テトラグライム、γ−ブチロラクト
ンなどの有機極性溶媒に可溶性であり、該有機溶媒に約
1〜40重量%の濃度で均一に溶解させて用いることが
好ましい。Examples of the photosensitive aromatic polyamides include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, hexamethylenephosphoramide, diglyme, triglyme, and tetraglyme. It is soluble in organic polar solvents such as glyme and γ-butyrolactone, and is preferably used after being uniformly dissolved in the organic solvent at a concentration of about 1 to 40% by weight.
【0025】前記の感光性芳香族ポリアミドは、ポリア
ミドを含有する前述の反応液中に、メタクリル酸クロラ
イド、ケイ皮酸クロライド、酢酸クロライド、塩化ベン
ジル、パラアジド塩化ベンゾイル等の反応性有機化合物
を添加し、−5〜100℃の温度で0.1〜50時間、
反応させて、前記ポリアミドのアミド結合の水素原子を
アセチル基、メタクロイル基、シンナモイル基、パラア
ジドベンゾイル基等の有機基へ置換反応をさせて得られ
た変性ポリアミドであってもよい。The above-mentioned photosensitive aromatic polyamide is produced by adding a reactive organic compound such as methacrylic acid chloride, cinnamic acid chloride, acetic acid chloride, benzyl chloride, para-azide benzoyl chloride, etc. to the above-mentioned reaction solution containing the polyamide. , 0.1 to 50 hours at a temperature of -5 to 100°C,
It may also be a modified polyamide obtained by reacting and substituting the hydrogen atoms of the amide bonds of the polyamide with organic groups such as acetyl groups, methacroyl groups, cinnamoyl groups, and para-azidobenzoyl groups.
【0026】また、この発明の着色感光性組成物で使用
される酸性有機顔料は、透明性が良く、且つ、耐熱性、
耐光性及び耐溶剤性に優れた酸性有機顔料が好ましく、
その例としては、フタロシニングリーン等のフタロシア
ニン系有機顔料、イソインドリノンイエロー等のイソイ
ンドリノン系有機顔料、ペリレンレッド等のペリレン系
有機顔料を挙げることができる。上記有機顔料は、光透
過性、膜表面の均一性等の観点から、その粒径が1μm
以下のものを用いることが好ましい。[0026] Furthermore, the acidic organic pigment used in the colored photosensitive composition of the present invention has good transparency, heat resistance,
Acidic organic pigments with excellent light resistance and solvent resistance are preferred;
Examples include phthalocyanine organic pigments such as phthalocyanine green, isoindolinone organic pigments such as isoindolinone yellow, and perylene organic pigments such as perylene red. The above organic pigment has a particle size of 1 μm from the viewpoint of light transmittance, uniformity of the film surface, etc.
It is preferable to use the following.
【0027】この発明の着色感光性組成物に配合される
光重合開始剤としては、例えば、ビスアジド化合物、ミ
ヒラーズケトン、ベンゾイン、ベンゾインメチルエーテ
ル、ベンゾインエチルエーテル、ベンゾインイソプロピ
ルエーテル、2−t−ブチルアントラキノン、1,2−
ベンゾ−9,10−アントラキノン、ベンジル、アニシ
ル、4,4−ビス(ジエチルアミノ)ベンゾフェノン、
アセトフェノン、ベンゾフェノン、1,5−アセナフテ
ン、チオキサントン又はその誘導体、アントラニル酸ジ
メチルアミノベンゾエート等の光重合開始剤を挙げるこ
とができる。Examples of the photopolymerization initiator to be incorporated into the colored photosensitive composition of the present invention include bisazide compounds, Michler's ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 1,2-
benzo-9,10-anthraquinone, benzyl, anisyl, 4,4-bis(diethylamino)benzophenone,
Examples include photopolymerization initiators such as acetophenone, benzophenone, 1,5-acenaphthene, thioxanthone or its derivatives, and anthranilic acid dimethylaminobenzoate.
【0028】前記の着色感光性組成物において光重合開
始剤として使用されるビスアジド化合物としては、4,
4’−ジアジドカルコン、4,4’−ジアジドベンザル
アセトン、2,6−ジ−(4’−アジドベンザル)シク
ロヘキサノン、4,4’−ジアジドスチルベン等を好適
に挙げることができる。また、光重合開始剤として使用
される前記のチオキサントン類としては、2,4−ジエ
チルチオキサントン、2−クロルチオキサントン等を挙
げることができる。The bisazide compounds used as photopolymerization initiators in the colored photosensitive composition include 4,
Preferred examples include 4'-diazidochalcone, 4,4'-diazidobenzalacetone, 2,6-di-(4'-azidobenzal)cyclohexanone, and 4,4'-diazidostilbene. Further, examples of the thioxanthone used as a photopolymerization initiator include 2,4-diethylthioxanthone and 2-chlorothioxanthone.
【0029】上記光重合開始剤の配合量は、前記感光性
ポリアミドなどの感光性樹脂100重量部に対して、0
.2〜40重量部、特に0.5〜30重量部の割合とな
る量とすることが好ましい。前記の配合量が少な過ぎる
と、得られる組成物の感度が低くなり、また、多くなり
過ぎると得られる組成物により形成される膜の耐熱性が
低下するので好ましくない。The amount of the photopolymerization initiator to be blended is 0 to 100 parts by weight of the photosensitive resin such as the photosensitive polyamide.
.. The amount is preferably 2 to 40 parts by weight, particularly 0.5 to 30 parts by weight. If the amount is too small, the sensitivity of the composition obtained will be low, and if it is too large, the heat resistance of the film formed from the composition will be reduced, which is not preferable.
【0030】前記の感光性芳香族ポリアミドなどの感光
性樹脂と酸性有機顔料との混合割合は、該感光性樹脂1
00重量部に対して、該酸性有機顔料が5〜200重量
部、特に10〜100重量部の割合であることが好まし
い。The mixing ratio of the photosensitive resin such as the photosensitive aromatic polyamide and the acidic organic pigment is as follows:
It is preferable that the acidic organic pigment is present in a proportion of 5 to 200 parts by weight, particularly 10 to 100 parts by weight, based on 00 parts by weight.
【0031】この発明の着色感光性組成物では、カルボ
ン酸化合物の配合割合が、感光性樹脂100重量部に対
して、0.1〜15重量部、特に0.2〜10重量部で
あることが好ましい。なお、この発明では、前記のカル
ボン酸化合物は、高い酸性度(pKa>5)であり、分
子量が300以下であって、しかも、有機極性溶媒に対
して2重量%以上の可溶性を有することが、カルボン酸
化合物の添加量を少なくできたり、加熱処理後のパター
ン内から昇華、蒸発、分解などで実質的に除去されやす
いので好ましい。In the colored photosensitive composition of the present invention, the blending ratio of the carboxylic acid compound is 0.1 to 15 parts by weight, particularly 0.2 to 10 parts by weight, based on 100 parts by weight of the photosensitive resin. is preferred. In addition, in this invention, the carboxylic acid compound has a high acidity (pKa>5), a molecular weight of 300 or less, and a solubility of 2% by weight or more in an organic polar solvent. This is preferable because the amount of carboxylic acid compound added can be reduced, and it can be substantially removed from the pattern after heat treatment by sublimation, evaporation, decomposition, etc.
【0032】この発明では、前記のカルボン酸化合物と
酸性有機顔料とが併用されていることが、特に特徴的な
要件である。カルボン酸化合物と酸性有機顔料とが併用
された着色感光性樹脂組成物の塗膜に対して少ない露光
量の光照射であっても〔或いは、その塗膜の底部(基材
側)まで到達する光の量がすなくても〕、微細な着色パ
ターンを効果的に形成することができるのである。[0032] In this invention, a particularly characteristic requirement is that the above-mentioned carboxylic acid compound and acidic organic pigment are used together. Even if the coating film of a colored photosensitive resin composition in which a carboxylic acid compound and an acidic organic pigment are used together is irradiated with a small amount of light [or the light reaches the bottom of the coating film (substrate side)] Even if the amount of light is low, fine colored patterns can be effectively formed.
【0033】この発明の着色感光性樹脂組成物では、カ
ルボン酸化合物の配合量が少なくなり過ぎると、該組成
物の光硬化に係わる感度の向上がなくなるので好ましく
なく、また、カルボン酸化合物の配合量が多くなり過ぎ
ると、該組成物中の分散安定性が低下し、未露光部分に
残査が残りやすくなり、現像性が低下することがあるの
で好ましくない。In the colored photosensitive resin composition of the present invention, if the amount of the carboxylic acid compound is too small, the sensitivity of the composition regarding photocuring will not improve, which is undesirable. If the amount is too large, the dispersion stability in the composition decreases, residues tend to remain in unexposed areas, and developability may deteriorate, which is not preferable.
【0034】また、この発明の着色感光性樹脂組成物の
溶液は、種々の配合手順で調製することができ、その溶
液の調製法が特に限定されることはないが、例えば、感
光性樹脂を前記の有機極性溶媒に均一に溶解した溶液を
調製し、その溶液に酸性有機顔料及びカルボン酸化合物
を添加して、最後に、光重合開始剤を添加することによ
って調製することが好ましい。Further, the solution of the colored photosensitive resin composition of the present invention can be prepared by various compounding procedures, and the method for preparing the solution is not particularly limited. It is preferable to prepare a solution uniformly dissolved in the organic polar solvent, add an acidic organic pigment and a carboxylic acid compound to the solution, and finally add a photopolymerization initiator.
【0035】前記の感光性樹脂組成物の溶液に酸性有機
顔料を添加して分散せる方法としては、ボールミル法、
ロール法、超音波法などを採用することができ、これら
の方法を併用することができる。なお、カルボン酸化合
物の添加は、前述の酸性有機顔料の添加の前であっても
、後であってもよい。Methods for adding and dispersing the acidic organic pigment into the solution of the photosensitive resin composition include ball milling,
A roll method, an ultrasonic method, etc. can be employed, and these methods can be used in combination. Note that the carboxylic acid compound may be added before or after the above-mentioned addition of the acidic organic pigment.
【0036】この発明の着色感光性樹脂組成物の溶液は
、該組成物の濃度が3〜40重量%、特に5〜30重量
%程度であり、そして、その容液の回転粘度(25℃)
が、0.1〜1000ポイズ、特に0.2〜500ポイ
ズ程度であることが好ましい。The solution of the colored photosensitive resin composition of the present invention has a concentration of about 3 to 40% by weight, particularly about 5 to 30% by weight, and has a rotational viscosity (at 25° C.) of the solution.
is preferably about 0.1 to 1000 poise, particularly about 0.2 to 500 poise.
【0037】この発明の着色感光性樹脂組成物の溶液に
は、必要に応じて、酸性有機顔料などの分散性を高める
ために界面活性剤などの分散剤を加えてもよく、また、
前記の着色感光性樹脂組成物の支持体(基材)との密着
性を高めるためにシランカップリング剤などの結合促進
剤を加えてもよい。[0037] If necessary, a dispersant such as a surfactant may be added to the solution of the colored photosensitive resin composition of the present invention in order to improve the dispersibility of the acidic organic pigment.
A bonding promoter such as a silane coupling agent may be added to enhance the adhesion of the colored photosensitive resin composition to the support (substrate).
【0038】また、この発明の着色感光性樹脂組成物(
の溶液)には、ハイドロキノン、2,6−t−ブチル−
4−メチルフェノール(BHT)、メチルエーテルハイ
ドロキノン、フェノチアジン、N−ニトロソフェニルヒ
ドロキシルアミンアンモニウム塩等の熱重合防止剤が配
合されていてもよい。[0038] Furthermore, the colored photosensitive resin composition of the present invention (
solution) contains hydroquinone, 2,6-t-butyl-
A thermal polymerization inhibitor such as 4-methylphenol (BHT), methyl ether hydroquinone, phenothiazine, and N-nitrosophenylhydroxylamine ammonium salt may be blended.
【0039】この発明の着色感光性樹脂組成物は、例え
ば、そのの溶液を基材上に0〜60℃の温度で塗布し乾
燥して該組成物の塗膜(乾燥塗膜)を形成し、次いで、
その塗膜上にパターンマスクを介して超高圧水銀灯の平
行光線を光照射して、その塗膜を各パターン状に光硬化
し、その後、現像溶液に浸漬させて、該塗膜の未露光部
分(未硬化部分)を溶出させ除去する現像を行って、着
色パターンを基材上に形成させることができる。[0039] The colored photosensitive resin composition of the present invention can be obtained by, for example, applying a solution thereof onto a substrate at a temperature of 0 to 60°C and drying it to form a coating film (dry coating film) of the composition. , then
The coating film is irradiated with parallel light from an ultra-high pressure mercury lamp through a pattern mask to photocure the coating film in each pattern, and then immersed in a developer solution to remove the unexposed parts of the coating film. A colored pattern can be formed on the substrate by performing development to elute and remove the (uncured portion).
【0040】その着色感光性樹脂組成物の溶液を基材の
表面へ塗布するには、回転塗布法、ロールコート法、浸
漬法、スプレー法等の方法により行うことができる。前
記の塗布膜の乾燥は、熱風乾燥器、ホットプレートなど
により、150℃以下、特に100℃以下で1〜60分
間、特に2〜30分間程度行うことが好ましい。この乾
燥の際に減圧してもよい。The solution of the colored photosensitive resin composition can be applied to the surface of the substrate by a spin coating method, a roll coating method, a dipping method, a spraying method, or the like. The coating film is preferably dried using a hot air dryer, a hot plate, or the like at 150° C. or lower, particularly 100° C. or lower, for about 1 to 60 minutes, especially about 2 to 30 minutes. The pressure may be reduced during this drying.
【0041】また、上記着色感光性樹脂組成物からなる
塗膜(乾燥後の皮膜)の厚さは、通常、約0.1〜3.
0μm程度であることが好ましい。前述のように現像液
に光硬化された塗膜を有する基材を浸漬させる際には、
超音波を作用させてもよい。[0041] The thickness of the coating film (film after drying) made of the above-mentioned colored photosensitive resin composition is usually about 0.1 to 3.
The thickness is preferably about 0 μm. As mentioned above, when immersing a substrate with a photocured coating in a developer,
Ultrasonic waves may also be applied.
【0042】上記の現像液としては、N,N−ジメチル
ホルムアミド、N,N−ジメチルアセトアミド、ジメチ
ルスルホキシド、N−メチル−2−ピロリドン、ヘキサ
メチレンホスホルアミド、ジグライム、トリグライム、
シクロヘキサノン、γ−ブチルラクトン等の「感光性樹
脂を溶解させることができる有機極性溶媒(a)」から
なる現像液、或いは、これらの有機極性溶媒とメタノー
ル、エタノール、エチルセロソルブ、ブチルセロソルブ
、エチルカルビトール、ブチルカルビトールなどの「ア
ルコール性水酸基を有する有機溶媒(b)」との混合系
の現像液を用いることが好ましい。Examples of the above developer include N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, hexamethylenephosphoramide, diglyme, triglyme,
A developer consisting of "organic polar solvent (a) capable of dissolving photosensitive resin" such as cyclohexanone and γ-butyllactone, or these organic polar solvents and methanol, ethanol, ethyl cellosolve, butyl cellosolve, and ethyl carbitol. It is preferable to use a developer mixed with "an organic solvent (b) having an alcoholic hydroxyl group" such as butyl carbitol.
【0043】前記の混合系現像液においては、有機極性
溶媒(a)を10〜50重量%の配合割合、及び、アル
コール性水酸基を有する有機溶媒(b)を50〜90重
量%の配合割合で含有していることが好ましい。前記混
合系現像液は、有機極性溶媒(a)の配合割合が余りに
少なくなり過ぎると着色感光性樹脂組成物の塗膜の未露
光部分が充分に溶解せずに着色パターンを確実に形成で
きない場合があり、好ましくない。In the above mixed developer, the organic polar solvent (a) is blended in a proportion of 10 to 50% by weight, and the organic solvent (b) having an alcoholic hydroxyl group is blended in a proportion of 50 to 90% by weight. It is preferable that it contains. In the mixed developer, if the blending ratio of the organic polar solvent (a) is too low, the unexposed parts of the coating film of the colored photosensitive resin composition will not be sufficiently dissolved and a colored pattern cannot be reliably formed. This is not desirable.
【0044】前述の現像後、形成された着色パターン(
画像)を、1,1,1−トリクロルエタン、エタノール
、イソプロピルアルコール、エチルカルビトール、水な
ど水酸基を有する溶媒によりリンスし、次いで、熱風乾
燥器、ホットプレート等により、約150℃以下、特に
100℃以下の温度で、1〜60分間、特に2〜30分
間、熱処理(ポストベーク)することが好ましい。After the above-mentioned development, the formed colored pattern (
(image) is rinsed with a solvent having a hydroxyl group such as 1,1,1-trichloroethane, ethanol, isopropyl alcohol, ethyl carbitol, water, etc., and then heated to about 150° C. or lower, especially at 100° C., using a hot air dryer, hot plate, etc. It is preferable to perform a heat treatment (post-baking) at a temperature of 1 to 60 minutes, particularly 2 to 30 minutes, at a temperature of 0.degree. C. or lower.
【0045】前記の着色パターンの形成法の具体的な例
としては、例えば、洗剤等で充分に脱脂し乾燥した方形
のガラスなどの基板(一辺の長さ:約10〜15cm)
上に、その塗布膜を乾燥した後の塗膜の厚さが0.1〜
100μm、特に0.5〜50μmとなるように、溶液
組成物のをスピンコートで塗布して(コートして)塗布
膜を形成し、約50〜150℃、特に60〜100℃の
温度で、0.1〜50分間、特に1〜20分間、乾燥さ
せて、溶媒を実質的に除去して、乾燥された塗膜を形成
する。As a specific example of the method for forming the colored pattern, for example, a rectangular glass substrate (length of one side: about 10 to 15 cm) that has been thoroughly degreased with detergent and dried is used.
The thickness of the coating film after drying is 0.1~
The solution composition is applied (coated) by spin coating to form a coating film to a thickness of 100 μm, particularly 0.5 to 50 μm, and at a temperature of about 50 to 150°C, particularly 60 to 100°C, Drying is performed for 0.1 to 50 minutes, particularly 1 to 20 minutes, to substantially remove the solvent and form a dried coating.
【0046】次いで、前述のようにして形成された塗膜
に、4〜100μmまでのストライプパターンを有する
パターンを介して、高圧水銀灯(5mW/cm2)で露
光して、パターン状に光硬化された塗膜を形成し、最後
に、そのパターン硬化された塗膜を有する基板を、前述
のように、現像溶液に浸漬すると共に、高い周波数の超
音波を作用させる現像操作を行って、未露光部分を実質
的に除去して、光硬化による着色パターンが形成されて
いる基板を得ることができる。Next, the coating film formed as described above was exposed to light using a high-pressure mercury lamp (5 mW/cm2) through a pattern having a stripe pattern of 4 to 100 μm to photocure it in a pattern. A coating film is formed, and finally, as described above, the substrate with the pattern-cured coating film is immersed in a developing solution and subjected to a development operation in which high-frequency ultrasonic waves are applied to remove the unexposed areas. can be substantially removed to obtain a substrate on which a colored pattern is formed by photocuring.
【0047】[0047]
【実施例】以下、炭素−炭素不飽和結合を有する感光性
樹脂(感光性芳香族ポリアミド)の製造例およびこの発
明の着色感光性樹脂組成物の溶液の調製例、ならびに、
着色パターンの形成法の実施例を例示して、この発明を
さらに詳しく説明する。[Examples] Below are examples of producing a photosensitive resin (photosensitive aromatic polyamide) having a carbon-carbon unsaturated bond, and examples of preparing a solution of the colored photosensitive resin composition of the present invention, and
The present invention will be explained in more detail by illustrating an example of a method for forming a colored pattern.
【0048】各実施例などにおいて、基材上に着色パタ
ーンを形成する際に、基材上に形成された『着色感光性
樹脂組成物の塗膜』の平坦性は、その溶液組成物を回転
塗布機で基材上にスピンコートし、その塗布膜を乾燥し
て、着色感光性樹脂組成物からなる乾燥塗膜を形成した
後に、その塗膜(皮膜)の回転中心及びその中心から5
mm間隔毎に塗膜の膜厚を測定し、その膜厚の平均値と
標準偏差で、平坦性を示した。In each example, when forming a colored pattern on a substrate, the flatness of the "coating film of the colored photosensitive resin composition" formed on the substrate is determined by rotating the solution composition. After spin-coating onto a substrate with a coating machine and drying the coating film to form a dry coating film made of a colored photosensitive resin composition, the center of rotation of the coating film (film) and 5 points from the center are
The film thickness of the coating film was measured at every mm interval, and the flatness was indicated by the average value and standard deviation of the film thickness.
【0049】また、各実施例などにおいて、前記の着色
感光性樹脂組成物からなる塗膜(皮膜)の平滑性は、そ
の塗膜の表面状態をJIS B0601−1982に
記載された表面粗さ規格に基づき測定して、そのRma
x値で、平滑性を示した。[0049] In each example, the smoothness of the coating film (film) made of the colored photosensitive resin composition was determined by measuring the surface condition of the coating film according to the surface roughness standard described in JIS B0601-1982. Measured based on the Rma
The smoothness was indicated by the x value.
【0050】参考例1
〔感光性の芳香族ポリアミドの製造〕三ッ口フラスコに
乾燥した空気を通してフラスコ内のガスを置換した後、
3,5−ジアミノ安息香酸エチルメタクリル酸エステル
119.98gを入れ、これにN−メチル−2−ピロリ
ドン(NMP)720ミリリットルを加えて溶解させた
。この溶液を冷却後、0℃に冷却し攪拌しながら、テレ
フタル酸ジクロライド91.16gを少しづつ加えた。
この際に発熱があり、溶液の温度が上昇するが、約10
℃以下に維持した。この溶液を、さらに、氷水中で、2
時間攪拌し、重合反応を行った。Reference Example 1 [Production of photosensitive aromatic polyamide] After replacing the gas in the flask by passing dry air into a three-necked flask,
119.98 g of 3,5-diaminobenzoic acid ethyl methacrylate was added, and 720 ml of N-methyl-2-pyrrolidone (NMP) was added and dissolved therein. After cooling this solution, 91.16 g of terephthalic acid dichloride was added little by little while cooling to 0° C. and stirring. At this time, heat is generated and the temperature of the solution rises, but about 10
The temperature was maintained below ℃. This solution was further added to ice water for 2 hours.
The mixture was stirred for hours to carry out a polymerization reaction.
【0051】次いで、反応液にNMP500ミリリット
ルを加えて希釈した後、この溶液をNMP1リットルと
水10リットルとの混合液に加えて芳香族ポリアミドを
析出させ、その析出物を濾過・回収し乾燥して芳香族ポ
リアミド白色粉末167.8gを得た。この感光性の芳
香族ポリアミドの粉末の対数粘度(濃度;0.5g/1
00ml溶媒、溶媒;NMP、測定温度;30℃)は0
.88であった。Next, after diluting the reaction solution by adding 500 ml of NMP, this solution was added to a mixture of 1 liter of NMP and 10 liters of water to precipitate aromatic polyamide, and the precipitate was filtered, collected, and dried. 167.8 g of aromatic polyamide white powder was obtained. Logarithmic viscosity (concentration; 0.5 g/1
00ml solvent, solvent; NMP, measurement temperature; 30°C) is 0
.. It was 88.
【0052】実施例1
〔緑色感光性組成物Aの溶液の調製〕 N−メチル−
2−ピロリドン(NMP)64gに、緑色顔料としてフ
タロシアニングリーン(大日本インキ(株)製、Fas
tgen green S0)2.8g、参考例1
で得られた感光性芳香族ポリアミドの粉末7gおよび熱
重合防止剤としてハイドロキノンモノメチルエーテル(
MEHQ)0.07gを、50Wの超音波(27Hz)
で約1時間作用さながら溶解及び分散させ、次いでこの
溶液を1μmのフッ素樹脂製フィルター(テフロンフィ
ルター)を用いて加圧濾過し、緑色顔料が均一に分散し
ているNMP溶液を得た。Example 1 [Preparation of solution of green photosensitive composition A] N-methyl-
Phthalocyanine Green (manufactured by Dainippon Ink Co., Ltd., Fas) was added to 64 g of 2-pyrrolidone (NMP) as a green pigment.
tgen green S0) 2.8g, Reference Example 1
7 g of the photosensitive aromatic polyamide powder obtained above and hydroquinone monomethyl ether (
MEHQ) 0.07g, 50W ultrasonic wave (27Hz)
This solution was then filtered under pressure using a 1 μm fluororesin filter (Teflon filter) to obtain an NMP solution in which the green pigment was uniformly dispersed.
【0053】次いで、前記の緑色顔料分散NMP溶液に
、カルボン酸化合物としてグリコール酸0.42g、光
重合開始剤として4,4’−ジアミノカルコン0.28
g、および、密着促進剤としてγ−グリシドキシプロピ
ルトリメトキシシラン0.24gを加えて攪拌して、充
分に攪拌し均一な粘稠液とした後、水槽中で30Wの超
音波(10Hz)を約30分間作用させて、さらに、1
μmのフッ素樹脂製のフィルター(テフロンフィルター
)を用いて加圧濾過し緑色顔料が均一に分散している緑
色感光性芳香族ポリアミド組成物の溶液(緑色感光性組
成物Aの溶液組成物)を調製した。Next, 0.42 g of glycolic acid as a carboxylic acid compound and 0.28 g of 4,4'-diaminochalcone as a photopolymerization initiator were added to the green pigment-dispersed NMP solution.
g, and 0.24 g of γ-glycidoxypropyltrimethoxysilane as an adhesion promoter, stirred thoroughly to make a uniform viscous liquid, and then heated with 30 W ultrasonic waves (10 Hz) in a water tank. Let it act for about 30 minutes, and then add 1
A solution of a green photosensitive aromatic polyamide composition (solution composition of green photosensitive composition A) in which a green pigment is uniformly dispersed is filtered under pressure using a μm fluororesin filter (Teflon filter). Prepared.
【0054】〔緑色パターンの形成〕前記の緑色顔料が
均一に分散している緑色感光性組成物Aの溶液を、ガラ
ス基板上での乾燥塗膜の膜厚が1.5μmになるように
、該基板上に回転塗布(スピンコート)して塗布膜を形
成し、そして、80℃で10分間乾燥して溶媒を実質的
に除去し、ガラス基板上に緑色感光性組成物Aからなる
皮膜(塗膜)を形成した。[Formation of a green pattern] A solution of the green photosensitive composition A in which the green pigment is uniformly dispersed is coated on a glass substrate so that the thickness of the dried coating film is 1.5 μm. A coating film is formed by spin coating on the substrate, and is dried at 80° C. for 10 minutes to substantially remove the solvent, thereby forming a film of green photosensitive composition A on the glass substrate ( A coating film) was formed.
【0055】次いで、該皮膜に対して、10μmの間隔
を有するストライブ状のパターンマスクを介して、超高
圧水銀灯の光源で40秒間で200mjの露光をして、
該塗膜をパターン状に光硬化した。Next, the film was exposed to 200 mj of light for 40 seconds using a light source of an ultra-high pressure mercury lamp through a striped pattern mask having an interval of 10 μm.
The coating film was photocured in a pattern.
【0056】次いで、パターン露光された緑色感光性組
成物Aの皮膜が形成されている基板を、ジグライム及び
エチルセロソルブの混合液(ジグライムとエチルセロソ
ルブとの容量比が30:70である)からなる現像液に
常温で浸漬すると同時に15Wの超音波(27KHzの
周波数)を作用させながら、4分間、現像操作を行って
青色パターン付基板を作成した。Next, the substrate on which the pattern-exposed film of the green photosensitive composition A is formed is treated with a mixed solution of diglyme and ethyl cellosolve (the volume ratio of diglyme and ethyl cellosolve is 30:70). A blue patterned substrate was prepared by immersing it in a developer at room temperature and simultaneously applying a 15 W ultrasonic wave (27 KHz frequency) for 4 minutes to develop the substrate.
【0057】その基板について、最後に、エチルセロソ
ルブでリンスし、その後、その基板を200℃で30分
間熱処理して、10μmの緑色ストライブパターンから
なる鮮明な緑色パターンが形成された基板(緑色パター
ン付基板)を製造した。Finally, the substrate was rinsed with ethyl cellosolve, and then heat treated at 200° C. for 30 minutes to form a substrate with a clear green pattern consisting of a 10 μm green stripe pattern (green pattern). (with attached substrate) was manufactured.
【0058】前述のようにして形成された緑色感光性組
成物Aの塗膜(皮膜)は、平坦性が1.52±0.06
μmであり、また、平滑性がRmax:0.05μmで
あった。また、前記のパターン露光された緑色感光性組
成物Aの皮膜が形成されている基板の現像操作において
、60秒間の現像でパターンが現れ、4分間現像を行っ
てもパターントビ、膨れ、変形などは認められなかった
。
〔緑色パターンの性状〕前述のようにして得られた緑色
パターン付基板は250℃で1時間、加熱したが、変色
や、褪色はいずれも認められなかった。The coating film (film) of green photosensitive composition A formed as described above had a flatness of 1.52±0.06.
.mu.m, and the smoothness was Rmax: 0.05 .mu.m. Further, in the development operation of the substrate on which the pattern-exposed film of the green photosensitive composition A is formed, a pattern appears after 60 seconds of development, and even after 4 minutes of development, pattern distortion, blistering, and deformation occur. was not recognized. [Properties of green pattern] The green patterned substrate obtained as described above was heated at 250° C. for 1 hour, but no discoloration or fading was observed.
【0059】比較例1
〔緑色感光性組成物Bの溶液の調製〕グリコール酸をま
ったく使用しないほかは、実施例1と同様にしてグリコ
ール酸がまったく配合されていない緑色感光性組成物B
の溶液を調製した。
〔緑色パターンの形成〕その緑色感光性組成物Bを使用
したほかは、実施例1と同様にして、緑色パターン付基
板を形成した。Comparative Example 1 [Preparation of solution of green photosensitive composition B] Green photosensitive composition B containing no glycolic acid was prepared in the same manner as in Example 1 except that no glycolic acid was used.
A solution was prepared. [Formation of green pattern] A substrate with a green pattern was formed in the same manner as in Example 1, except that the green photosensitive composition B was used.
【0060】前述のようにして形成された緑色感光性組
成物Bの塗膜(皮膜)は、平坦性が1.50±0.05
μmであり、また、平滑性がRmax:0.05μmで
あった。また、前記のパターン露光された緑色感光性組
成物Bの皮膜が形成されている基板の現像操作において
は、40秒間の現像でパターンが現れ、1.5分間の現
像で緑色パターンにハクリが認められた。The coating film (film) of green photosensitive composition B formed as described above has a flatness of 1.50±0.05.
.mu.m, and the smoothness was Rmax: 0.05 .mu.m. In addition, in the development operation of the substrate on which the pattern-exposed film of green photosensitive composition B was formed, the pattern appeared after 40 seconds of development, and peeling was observed in the green pattern after 1.5 minutes of development. It was done.
【0061】実施例2〜3
〔緑色感光性組成物CおよびDの溶液の調製〕カルボン
酸化合物として、シュウ酸・2水和物0.14g(実施
例2)または0.28g(実施例4)を使用したほかは
、実施例1と同様にして、緑色顔料が均一に分散してい
る緑色感光性芳香族ポリアミド組成物の溶液(緑色感光
性組成物C及びDの溶液組成物)をそれぞれ調製した。
〔緑色パターンの形成〕 緑色感光性組成物C又はD
の各溶液を使用したほかは、実施例1と同様にして、各
緑色パターン付基板をそれぞれ形成した。Examples 2 to 3 [Preparation of solutions of green photosensitive compositions C and D] As the carboxylic acid compound, 0.14 g (Example 2) or 0.28 g (Example 4) of oxalic acid dihydrate was used. ), except that a solution of a green photosensitive aromatic polyamide composition in which a green pigment was uniformly dispersed (solution compositions of green photosensitive compositions C and D) was prepared in the same manner as in Example 1. Prepared. [Formation of green pattern] Green photosensitive composition C or D
Green patterned substrates were formed in the same manner as in Example 1, except that each solution was used.
【0062】前述のようにして形成された緑色感光性組
成物Cの塗膜(皮膜)は、平坦性が1.51±0.04
μmであり、また、平滑性がRmax:0.04μmで
あり、そして、緑色感光性組成物Dの塗膜は、平坦性が
1.48±0.04μmであり、また、平滑性がRma
x:0.05μmであった。The coating film (film) of the green photosensitive composition C formed as described above had a flatness of 1.51±0.04.
The coating film of green photosensitive composition D has a flatness of 1.48±0.04 μm and a smoothness of Rmax: 0.04 μm.
x: 0.05 μm.
【0063】また、前記のパターン露光された緑色感光
性組成物C又はDの各皮膜が形成されている基板の各現
像操作においては、いずれも、1分間の現像でパターン
が現れ、4分間の現像を行ってもパターントビ、剥がれ
、変形などがまったく認められなかった。
〔緑色パターンの性状〕前述のようにして実施例2及び
3で得られた各緑色パターン付基板はいずれも250℃
で1時間加熱したが、変色、褪色はいずれも認められな
かった。In addition, in each development operation of the substrate on which each film of green photosensitive composition C or D was formed after pattern exposure, the pattern appeared after 1 minute of development, and the pattern appeared after 4 minutes of development. Even after development, no pattern distortion, peeling, or deformation was observed. [Properties of green pattern] Each green patterned substrate obtained in Examples 2 and 3 as described above was heated at 250°C.
Although it was heated for 1 hour, no discoloration or fading was observed.
【0064】実施例4
〔緑色感光性組成物Eの溶液の調製〕カルボン酸化合物
として乳酸0.28gを使用したほかは、実施例2と同
様にして、緑色顔料が均一に分散している緑色感光性芳
香族ポリアミド組成物の溶液(緑色感光性組成物Eの溶
液組成物)を調製した。
〔緑色パターンの形成〕その緑色感光性組成物Eの溶液
を使用したほかは、実施例1と同様にして、緑色パター
ン付基板を形成した。Example 4 [Preparation of solution of green photosensitive composition E] A green color in which the green pigment is uniformly dispersed was prepared in the same manner as in Example 2, except that 0.28 g of lactic acid was used as the carboxylic acid compound. A solution of a photosensitive aromatic polyamide composition (solution composition of green photosensitive composition E) was prepared. [Formation of green pattern] A substrate with a green pattern was formed in the same manner as in Example 1, except that the solution of green photosensitive composition E was used.
【0065】前述のようにして形成された緑色感光性組
成物Eの塗膜(皮膜)は、平坦性が1.53±0.05
μmであり、また、平滑性がRmax:0.04μmで
あった。また、前記のパターン露光された緑色感光性組
成物Eの皮膜が形成されている基板の現像操作において
、1分間の現像でパターンが現れ、4分間の現像でも緑
色パターンにパターントビ、剥がれ、変形等がまったく
認められなかった。
〔緑色パターンの性状〕前述のようにして実施例4で得
られた緑色パターン付基板は、250℃で1時間、加熱
したが、変色や、褪色が認められなかった。The coating film (film) of green photosensitive composition E formed as described above had a flatness of 1.53±0.05.
μm, and the smoothness was Rmax: 0.04 μm. In addition, in the development operation of the substrate on which the pattern-exposed film of the green photosensitive composition E is formed, a pattern appears after 1 minute of development, and even after 4 minutes of development, the green pattern shows pattern skipping, peeling, and deformation. were not recognized at all. [Properties of green pattern] The green patterned substrate obtained in Example 4 as described above was heated at 250° C. for 1 hour, but no discoloration or fading was observed.
【0066】実施例5
〔赤色感光性組成物Fの溶液の調製〕有機顔料としてペ
リレンレッド2.8gを使用し、カルボン酸化合物とし
てグルコール酸0.28gを使用したほかは、実施例1
と同様にして、赤色顔料が均一に分散している赤色感光
性芳香族ポリアミド組成物の溶液(赤色感光性組成物F
の溶液組成物)を調製した。
〔緑色パターンの形成〕その赤色感光性組成物Fの溶液
を使用したほかは、実施例1と同様にして、赤色パター
ン付基板を形成した。Example 5 [Preparation of solution of red photosensitive composition F] Example 1 except that 2.8 g of perylene red was used as the organic pigment and 0.28 g of glycolic acid was used as the carboxylic acid compound.
In the same manner as above, a solution of a red photosensitive aromatic polyamide composition in which a red pigment was uniformly dispersed (red photosensitive composition F) was prepared.
solution composition) was prepared. [Formation of green pattern] A red patterned substrate was formed in the same manner as in Example 1, except that the solution of red photosensitive composition F was used.
【0067】前述のようにして形成された赤色感光性組
成物Fの塗膜(皮膜)は、平坦性が1.54±0.06
μmであり、また、平滑性がRmax:0.12μmで
あった。また、前記のパターン露光された赤色感光性組
成物Fの皮膜が形成されている基板の現像操作において
、1分間の現像でパターンが現れ、4分間の現像でも赤
色パターンにパターントビ、剥がれ、変形等がまったく
認められなかった。
〔赤色パターンの性状〕前述のようにして実施例5で得
られた赤色パターン付基板は、250℃で1時間、加熱
したが、変色や、褪色が認められなかった。The coating film (film) of the red photosensitive composition F formed as described above had a flatness of 1.54±0.06.
μm, and the smoothness was Rmax: 0.12 μm. In addition, in the development operation of the substrate on which the pattern-exposed film of the red photosensitive composition F is formed, a pattern appears after 1 minute of development, and even after 4 minutes of development, the red pattern shows pattern skipping, peeling, and deformation. were not recognized at all. [Properties of red pattern] The red patterned substrate obtained in Example 5 as described above was heated at 250° C. for 1 hour, but no discoloration or fading was observed.
【0068】[0068]
【発明の作用効果】この発明は、概略、感光性芳香族ポ
リアミドなどの感光性樹脂と光重合開始剤とカルボン酸
化合物と酸性有機顔料とを含有する着色感光性組成物に
係わるものであり、前記のカルボン酸化合物が酸性有機
化合物の二次構造の形成を促進するために、この発明の
着色感光性組成物の塗膜(皮膜)が露光され、現像され
る際に、光硬化されたパターン部分に現像液が膨潤した
り、変形したりすることがなく、しかも前記パターン部
分から有機顔料が流出することもないのである。[Operations and Effects of the Invention] The present invention generally relates to a colored photosensitive composition containing a photosensitive resin such as a photosensitive aromatic polyamide, a photopolymerization initiator, a carboxylic acid compound, and an acidic organic pigment. In order to promote the formation of a secondary structure of an acidic organic compound, the carboxylic acid compound forms a photocured pattern when the coating film (film) of the colored photosensitive composition of the present invention is exposed and developed. The developing solution does not swell or deform in the patterned areas, and the organic pigment does not flow out from the patterned areas.
【0069】この発明の着色感光性組成物は、その組成
物の塗膜(皮膜)を基材上に形成し、その塗膜上に光照
射してパターン状に光硬化させ、最後に、現像液で該塗
膜の未露光部分(未硬化部分)を除去する現像操作を行
うことによって、カラー撮像素子や、カラーセンサー、
カラーディスプレー等の微細色分解用のカラーフィルタ
ーなどの着色パターン部材を製造する方法において使用
することができる。The colored photosensitive composition of the present invention is obtained by forming a coating film (film) of the composition on a substrate, irradiating the coating film with light to photocure it in a pattern, and finally developing it. By performing a development operation that removes the unexposed parts (uncured parts) of the coating film with a liquid, color imaging elements, color sensors,
It can be used in a method for manufacturing colored pattern members such as color filters for fine color separation in color displays and the like.
Claims (3)
、光重合開始剤、カルボン酸化合物、および、酸性有機
顔料を含有することを特徴とする着色感光性組成物。1. A colored photosensitive composition comprising a photosensitive resin having a carbon-carbon unsaturated bond, a photopolymerization initiator, a carboxylic acid compound, and an acidic organic pigment.
に、感光性樹脂、光重合開始剤及びカルボン酸化合物が
溶解されていると共に、酸性有機顔料が分散されている
請求項1に記載の着色感光性樹脂組成物。2. The method according to claim 1, wherein the photosensitive resin, a photopolymerization initiator, and a carboxylic acid compound are dissolved in an organic polar solvent capable of dissolving the photosensitive resin, and an acidic organic pigment is dispersed therein. colored photosensitive resin composition.
する感光性基を多数有する感光性芳香族ポリアミドであ
る請求項1に記載の着色感光性樹脂組成物。3. The colored photosensitive resin composition according to claim 1, wherein the photosensitive resin is a photosensitive aromatic polyamide having a large number of photosensitive groups containing carbon-carbon double bonds.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3242897A JPH04369653A (en) | 1991-06-18 | 1991-06-18 | Coloring photosensitive resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3242897A JPH04369653A (en) | 1991-06-18 | 1991-06-18 | Coloring photosensitive resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04369653A true JPH04369653A (en) | 1992-12-22 |
Family
ID=17095847
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3242897A Pending JPH04369653A (en) | 1991-06-18 | 1991-06-18 | Coloring photosensitive resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04369653A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0780731A2 (en) | 1995-12-22 | 1997-06-25 | Mitsubishi Chemical Corporation | Photopolymerizable composition for a color filter, color filter and liquid crystal display device |
US5677096A (en) * | 1995-09-19 | 1997-10-14 | Ricoh Company, Ltd. | Electrophotographic photoconductor |
JP2010083997A (en) * | 2008-09-30 | 2010-04-15 | Fujifilm Corp | Curable coloring composition, method for producing the same, color filter, and solid-state image pick-up device |
JP2012137531A (en) * | 2010-12-24 | 2012-07-19 | Jsr Corp | Coloring composition, color filter, and display element |
-
1991
- 1991-06-18 JP JP3242897A patent/JPH04369653A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5677096A (en) * | 1995-09-19 | 1997-10-14 | Ricoh Company, Ltd. | Electrophotographic photoconductor |
EP0780731A2 (en) | 1995-12-22 | 1997-06-25 | Mitsubishi Chemical Corporation | Photopolymerizable composition for a color filter, color filter and liquid crystal display device |
JP2010083997A (en) * | 2008-09-30 | 2010-04-15 | Fujifilm Corp | Curable coloring composition, method for producing the same, color filter, and solid-state image pick-up device |
JP2012137531A (en) * | 2010-12-24 | 2012-07-19 | Jsr Corp | Coloring composition, color filter, and display element |
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