JPS62279327A - Photosensitive lithographic printing plate - Google Patents
Photosensitive lithographic printing plateInfo
- Publication number
- JPS62279327A JPS62279327A JP12289986A JP12289986A JPS62279327A JP S62279327 A JPS62279327 A JP S62279327A JP 12289986 A JP12289986 A JP 12289986A JP 12289986 A JP12289986 A JP 12289986A JP S62279327 A JPS62279327 A JP S62279327A
- Authority
- JP
- Japan
- Prior art keywords
- group
- printing plate
- lithographic printing
- positive
- photosensitive lithographic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000007639 printing Methods 0.000 title claims abstract description 78
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 43
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 25
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 22
- 125000005843 halogen group Chemical group 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
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- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 11
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 10
- 125000001424 substituent group Chemical group 0.000 claims abstract description 10
- 150000002576 ketones Chemical class 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 7
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 24
- 150000003459 sulfonic acid esters Chemical class 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 5
- 125000004957 naphthylene group Chemical group 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims 1
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- 239000000243 solution Substances 0.000 description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 22
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000011230 binding agent Substances 0.000 description 16
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- 235000011121 sodium hydroxide Nutrition 0.000 description 5
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
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- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 3
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
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- 229930192627 Naphthoquinone Natural products 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 102100031296 Tsukushi Human genes 0.000 description 1
- 101710086958 Tsukushi Proteins 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229940051881 anilide analgesics and antipyretics Drugs 0.000 description 1
- 150000003931 anilides Chemical class 0.000 description 1
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical compound C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- HRBFQSUTUDRTSV-UHFFFAOYSA-N benzene-1,2,3-triol;propan-2-one Chemical compound CC(C)=O.OC1=CC=CC(O)=C1O HRBFQSUTUDRTSV-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229940118056 cresol / formaldehyde Drugs 0.000 description 1
- OBRMNDMBJQTZHV-UHFFFAOYSA-N cresol red Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(C)C(O)=CC=2)=C1 OBRMNDMBJQTZHV-UHFFFAOYSA-N 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical class OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- MYTMXVHNEWBFAL-UHFFFAOYSA-L dipotassium;carbonate;hydrate Chemical compound O.[K+].[K+].[O-]C([O-])=O MYTMXVHNEWBFAL-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- OUGJKAQEYOUGKG-UHFFFAOYSA-N ethyl 2-methylidenebutanoate Chemical compound CCOC(=O)C(=C)CC OUGJKAQEYOUGKG-UHFFFAOYSA-N 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
- JVICFMRAVNKDOE-UHFFFAOYSA-M ethyl violet Chemical compound [Cl-].C1=CC(N(CC)CC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 JVICFMRAVNKDOE-UHFFFAOYSA-M 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 235000004611 garlic Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229960004337 hydroquinone Drugs 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 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
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- AWJZTPWDQYFQPQ-UHFFFAOYSA-N methyl 2-chloroprop-2-enoate Chemical compound COC(=O)C(Cl)=C AWJZTPWDQYFQPQ-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 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
- 150000007522 mineralic acids Chemical class 0.000 description 1
- YDKJSAXEBRKYLM-UHFFFAOYSA-N n-(3-methoxyphenyl)prop-2-enamide Chemical compound COC1=CC=CC(NC(=O)C=C)=C1 YDKJSAXEBRKYLM-UHFFFAOYSA-N 0.000 description 1
- PJASPDPXLKIZHB-UHFFFAOYSA-N n-(3-nitrophenyl)prop-2-enamide Chemical compound [O-][N+](=O)C1=CC=CC(NC(=O)C=C)=C1 PJASPDPXLKIZHB-UHFFFAOYSA-N 0.000 description 1
- JEPAGMKWFWQECH-UHFFFAOYSA-N n-(4-chlorophenyl)prop-2-enamide Chemical compound ClC1=CC=C(NC(=O)C=C)C=C1 JEPAGMKWFWQECH-UHFFFAOYSA-N 0.000 description 1
- NYJIXHQKWMNVNP-UHFFFAOYSA-N n-(5-hydroxynaphthalen-1-yl)-2-methylprop-2-enamide Chemical compound C1=CC=C2C(NC(=O)C(=C)C)=CC=CC2=C1O NYJIXHQKWMNVNP-UHFFFAOYSA-N 0.000 description 1
- BPCNEKWROYSOLT-UHFFFAOYSA-N n-phenylprop-2-enamide Chemical compound C=CC(=O)NC1=CC=CC=C1 BPCNEKWROYSOLT-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 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
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 125000004385 trihaloalkyl group Chemical group 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000006886 vinylation reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野］
本発明はポジ型感光性平版印刷版に関し、更に詳しくは
、０−ナフトキノンジアジドスルホン酸エステルと特定
の構造単位を有する樹脂とを組合せた感光層を有するポ
ジ型感光性平版印刷版に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a positive-working photosensitive lithographic printing plate, and more specifically to a photosensitive lithographic printing plate made of a combination of 0-naphthoquinonediazide sulfonic acid ester and a resin having a specific structural unit. The present invention relates to a positive-working photosensitive lithographic printing plate having layers.
ポジ型感光性平版印刷版とは一般に親水性支持体上に露
光により可溶化するインキ受容性悪光層を形成したもの
である。この感光層に画像露光を行い現像すると、画線
部を残して非画線部は除去されるので、画像が形成され
る。印刷においては、画像部が親油性で非画像部が親水
性であるという性質上の差が利用される。A positive-working photosensitive lithographic printing plate generally has an ink-receptive anti-glare layer formed on a hydrophilic support, which becomes solubilized by exposure to light. When this photosensitive layer is subjected to imagewise exposure and development, the non-image areas are removed while leaving the image areas, thereby forming an image. In printing, the difference in properties of image areas being lipophilic and non-image areas being hydrophilic is utilized.
一般に平版印刷版には、耐剛力、耐薬品性、現像ラチチ
ュード、インキ受容性、感度等が必要であるが、特にポ
ジ型の場合には、良好な耐薬品性、耐剛力、現像ラチチ
ュードが望まれている。ここで耐薬品性とは、印刷時に
使われる種々の薬品、例えばイソプロピルアルコール、
インキ、整面液、プレートクリーナー等に対する適性で
ある。In general, lithographic printing plates require good stiffness, chemical resistance, development latitude, ink receptivity, sensitivity, etc., but especially for positive type plates, good chemical resistance, stiffness resistance, and development latitude are desirable. It is rare. Chemical resistance here refers to various chemicals used during printing, such as isopropyl alcohol,
Suitable for ink, surface preparation liquid, plate cleaner, etc.
感光層としては０−ナフトキノンジアジド化合物が広く
使用されているが、それ自体は高分子化合物ではないの
で、ノボラック樹脂等と混合したり、あるいは縮合反応
させたりして、機械的強度の向上が図られている。樹脂
が結合した０−ナフトキノンジアジド化合物の例として
、特公昭４３−２８４０３号はピロガロールとアセトン
との重縮合樹脂の０−ナフトキノンジアジドスルホン酸
エステルを開示している。しかしこれは比較的良好な性
能を示すものの、バインダーとして通常のノボラック樹
脂、例えばｍ−タレゾールノボラック樹脂を使用した場
合は、特にＵＶインキを使用すると耐刷力が不足すると
いう欠点を有する。O-naphthoquinonediazide compounds are widely used as photosensitive layers, but since they are not polymeric compounds themselves, they can be mixed with novolac resins or subjected to condensation reactions to improve mechanical strength. It is being As an example of a resin-bound O-naphthoquinonediazide compound, Japanese Patent Publication No. 43-28403 discloses an O-naphthoquinonediazide sulfonic acid ester of a polycondensation resin of pyrogallol and acetone. However, although this exhibits relatively good performance, it has the disadvantage that printing durability is insufficient, especially when UV ink is used, when a normal novolac resin, such as m-talesol novolak resin, is used as the binder.
そのため、耐剛力、耐薬品性等の上記緒特性を一層向上
するために、種々の感光体及びバインダーを含有する感
光性組成物が提案された。Therefore, in order to further improve the above-mentioned properties such as stiffness resistance and chemical resistance, photosensitive compositions containing various photoreceptors and binders have been proposed.
特開昭５５−７６３４６号に開示された感光性組成物は
、レゾルシノール又はその誘導体とピロガロールとアセ
トンとの共縮合重合により得られたポリヒドロキシフェ
ニル化合物と、ハロゲノスルホニル基を有する０−キノ
ンジアジド化合物とを縮合させて得られる怒光性樹脂と
、バインダーとしてフェノール・ホルムアルデヒド樹脂
等のアルカリ可溶性樹脂とを含有する。また特公昭５６
−５４６２１号に開示された感光性組成物は、０−キノ
ンジアジド化合物感光体と、フェノールとｍ−、ｐ−混
合クレゾールとアルデヒドとを共縮合させてなる樹脂の
バインダーとを含有する。しかし、これらの感光性組成
物においては、バインダーとしていわゆるノボラック樹
脂が使用されているために、画像部の感光層の皮膜強度
が低く、耐剛力が劣るという欠点があった。The photosensitive composition disclosed in JP-A-55-76346 comprises a polyhydroxyphenyl compound obtained by cocondensation polymerization of resorcinol or its derivative, pyrogallol, and acetone, and an 0-quinonediazide compound having a halogenosulfonyl group. and an alkali-soluble resin such as phenol/formaldehyde resin as a binder. Also, special public service in 1984
The photosensitive composition disclosed in No. 54621 contains an 0-quinonediazide compound photoreceptor and a resin binder formed by co-condensing phenol, m- and p-mixed cresol, and aldehyde. However, in these photosensitive compositions, since a so-called novolak resin is used as a binder, the film strength of the photosensitive layer in the image area is low and the stiffness resistance is poor.
そこで、耐刷力を向上させる方法として露光、現像後、
高温で加熱処理する方法（バーニング処理と呼ばれる）
が一般に用いられている。ところがバーニング処理を行
なうと、加熱時に画像部の感光層より樹脂のモノマー成
分が非画像部等に付着したりして、印刷時に地汚れを発
生しやすくなるという問題がある。Therefore, as a method to improve printing durability, after exposure and development,
Method of heat treatment at high temperatures (called burning treatment)
is commonly used. However, when the burning process is performed, there is a problem in that the monomer component of the resin adheres to non-image areas etc. from the photosensitive layer of the image area during heating, and background smear is likely to occur during printing.
一方、特公昭５２−２８４０１号に開示の感光性組成物
は、０−ナフトキノンジアジドスルホン酸誘専体からな
る感光性付与剤と、下記一般式（式中、Ｒ１およびＲ２
は水素原子、アルキル基またはカルボン酸基であり、Ｒ
３は水素原子、ハロゲン原子またはアルキル基、Ｒ４は
水素原子、アルキル基、フェニル基またはアラルキル基
であり、Ｘは窒素原子と芳香族環炭素原子とを連結する
２価の有機基、ｎはＯまたは１、Ｙは置換基を有しても
よいフェニレン基または置換基を有してもいナフチレン
基をあられす。）
により表される構造単位を有する高分子化合物からなる
バインダーとを含有する。この感光性組成物はバインダ
ーとしてノボラック樹脂の代りに上記構造単位を有する
高分子化合物を使用しているので、良好な感光層皮膜強
度及び耐剛性を有する。On the other hand, the photosensitive composition disclosed in Japanese Patent Publication No. 52-28401 contains a photosensitizing agent consisting of an 0-naphthoquinonediazide sulfonic acid derivative and the following general formula (in which R1 and R2
is a hydrogen atom, an alkyl group or a carboxylic acid group, and R
3 is a hydrogen atom, a halogen atom, or an alkyl group, R4 is a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group, X is a divalent organic group connecting a nitrogen atom and an aromatic ring carbon atom, n is O Alternatively, 1, Y represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent. ) A binder made of a polymer compound having a structural unit represented by: Since this photosensitive composition uses a polymer compound having the above-mentioned structural unit as a binder instead of a novolac resin, it has good photosensitive layer film strength and rigidity.
〔発明が解決しようとする問題点〕
しかしながら、特公昭５２−２８４０１号の感光性組成
物からなる感光層を有するポジ型感光性平版印刷版は、
通常の印刷では比較的良好な耐剛力と耐薬品性を示すに
もかかわらず、ＵＶ印刷においては不十分であることが
わかった。また現像ラチチュードが狭いという欠点も認
められた。ここでＵＶ印刷とは紫外線吸収剤を含むイン
キ（ＵＶインキ）を用いて行う印刷をいう。ＵＶ印刷に
適さない理由は、ＵＶ印刷に使用されるインキや薬剤に
対して感光層の耐薬品性が低いことにあることがわかっ
た。[Problems to be Solved by the Invention] However, the positive-working photosensitive lithographic printing plate having a photosensitive layer made of the photosensitive composition of Japanese Patent Publication No. 52-28401,
Despite exhibiting relatively good rigidity and chemical resistance in conventional printing, it was found to be insufficient in UV printing. In addition, the drawback was that the development latitude was narrow. Here, UV printing refers to printing performed using ink (UV ink) containing an ultraviolet absorber. It has been found that the reason why it is not suitable for UV printing is that the photosensitive layer has low chemical resistance to the inks and chemicals used for UV printing.
従って、本発明の目的は、耐薬品性が極めて良好で、バ
ーニング処理を行なうことなくＵＶインキ印刷も可能な
、耐剛力に優れたポジ型感光性平版印刷版を提供するこ
とである。Therefore, an object of the present invention is to provide a positive-working photosensitive lithographic printing plate which has extremely good chemical resistance, allows UV ink printing without burning treatment, and has excellent rigidity resistance.
更に別の目的は、地汚れが発生せず現像ラチチュードが
広いポジ型感光性平版印刷版を提供することにある。Still another object is to provide a positive-working photosensitive lithographic printing plate that does not cause scumming and has a wide development latitude.
本発明者等は上記感光性組成物の欠点につき鋭意検討を
行った結果、感光性付与剤として０−ナフトキノンジア
ジドスルホン酸のｍ４体が、低分子エステル類、アミド
類、アジド類か、フェノール、クレゾール及びキシレノ
ールのような１価のフェノール類のノボラック樹脂から
生成されているために、ＵＶ印刷における耐薬品性及び
耐剛力が劣ることを発見した。さらに、０−ナフトキノ
ンジアジドスルホン酸の誘導体を生成すべき化合物につ
いて種々検討した結果、特定の構造単位ををする高分子
化合物バインダーと組合さるべき〇−ナフトキノンジア
ジドスルホン酸エステルに、多価フェノールとアルデヒ
ド又はケトンとの重縮合樹脂が結合したものを使用する
と、ＵＶ印刷における耐薬品性及び耐刷力に優れたポジ
型感光性平版印刷版が得られることを発見し、本発明に
想到した。The present inventors have conducted intensive studies on the drawbacks of the above-mentioned photosensitive compositions, and have found that the m4 form of 0-naphthoquinonediazide sulfonic acid as a photosensitizing agent is selected from low-molecular esters, amides, azides, phenols, It has been discovered that the chemical resistance and rigidity resistance in UV printing are poor because it is produced from novolac resins of monohydric phenols such as cresol and xylenol. Furthermore, as a result of various studies on compounds that should produce derivatives of 0-naphthoquinonediazide sulfonic acid, we found that 0-naphthoquinonediazide sulfonic acid ester, which should be combined with a polymer compound binder having a specific structural unit, was combined with polyhydric phenol and aldehyde. The present inventors discovered that a positive-working photosensitive lithographic printing plate having excellent chemical resistance and printing durability in UV printing can be obtained by using a polycondensation resin combined with a ketone.
すなわち、本発明のポジ型感光性平版印刷版は（八）多
価フェノールとアルデヒド又はケトンとの重縮合樹脂の
０−ナフトキノンジアジドスルホン酸エステルと、
（Ｂ）下記一般式（Ｉｌ
ＣＯＮＲ４→Ｘ升、Ｙ−ＯＨ
（式中、Ｒ３およびＲ２は水素原子、ハロゲン原子、ア
ルキル基、アリール基またはカルボン酸基であり、Ｒ３
は水素原子、ハロゲン原子、アルキル基または了り−ル
基であり、Ｒ４は水素原子、アルキル基、アリール基ま
たはアラルキル基であり、Ｙは置換基を有してもよい芳
香族基であり、Ｘは窒素原子と前記芳香族基の炭素原子
とを連結する２価の打機基であり、ｎは０〜５の整数で
ある。）により表わされる構造単位を有する高分子化合
物とを含有する感光層を支持体上に有することを特徴と
する。That is, the positive-working photosensitive lithographic printing plate of the present invention comprises (8) 0-naphthoquinonediazide sulfonic acid ester of a polycondensation resin of polyhydric phenol and aldehyde or ketone, and (B) the following general formula (Il CONR4→X square) , Y-OH (wherein R3 and R2 are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a carboxylic acid group, and R3
is a hydrogen atom, a halogen atom, an alkyl group or an aralkyl group, R4 is a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and Y is an aromatic group which may have a substituent, X is a divalent group that connects the nitrogen atom and the carbon atom of the aromatic group, and n is an integer of 0 to 5. ) on a support.
本発明の０−ナフトキノンジアジドスルホン酸エステル
に使用する多価フェノールとしては、カテコール、（メ
チル）レゾルシン、ヒドロキノン、ピロガロール、フロ
ログルシン等が好ましく、より好ましくはピロガロール
である。ケトン又はアルデヒドとしては、アセトン、ホ
ルムアルデヒド、アセトアルデヒド、ヘンズアルデヒド
、クロトンアルデヒド等が好ましく、より好ましくはア
セトンである。多価フェノールは２種以上を組合せて使
用することも可能である。As the polyhydric phenol used in the 0-naphthoquinonediazide sulfonic acid ester of the present invention, catechol, (methyl)resorcinol, hydroquinone, pyrogallol, phloroglucin, etc. are preferable, and pyrogallol is more preferable. As the ketone or aldehyde, acetone, formaldehyde, acetaldehyde, henzaldehyde, crotonaldehyde, etc. are preferred, and acetone is more preferred. It is also possible to use a combination of two or more types of polyhydric phenols.
多価フェノール類とケトン又はアルデヒドとの重縮合樹
脂は公知の方法により合成することができる。まず多価
フェノール類をケトン又アルデヒド頻に、必要に応じて
適当な溶媒を加えて溶解させ、塩酸、オキシ塩化リン、
シュウ酸等の適当な酸の存在下で重縮合反応を起こさせ
、重縮合体を得る。適当な溶媒としては、例えばジオキ
サン、メタノール、エタノール、テトラヒドロフラン、
水またはこれらの混合物等がある。Polycondensation resins of polyhydric phenols and ketones or aldehydes can be synthesized by known methods. First, polyhydric phenols are dissolved in ketones or aldehydes, often by adding an appropriate solvent if necessary, hydrochloric acid, phosphorus oxychloride,
A polycondensation reaction is caused in the presence of a suitable acid such as oxalic acid to obtain a polycondensate. Suitable solvents include, for example, dioxane, methanol, ethanol, tetrahydrofuran,
water or a mixture of these.
重縮合条件としては、公知の方法より重合初期から高い
温度で重縮合反応を行うのが好ましい。As for the polycondensation conditions, it is preferable to carry out the polycondensation reaction at a higher temperature from the initial stage of polymerization than in known methods.
例えば、塩酸、硫酸、シュウ酸、オキシ塩化リン等の酸
触媒を多価フェノール類とケトン又はアルデヒド（必要
に応じて適当な溶媒を含有）の混合物中に滴下すると同
時に、還流の定常状態にもっていくようにするのが好ま
しい。For example, an acid catalyst such as hydrochloric acid, sulfuric acid, oxalic acid, phosphorus oxychloride, etc. is added dropwise into a mixture of polyhydric phenols and ketones or aldehydes (containing a suitable solvent if necessary), and at the same time the mixture is brought to a steady state of reflux. It is preferable to do so.
これらの方法で得る多価フェノール系高分子化金物の分
子量は、ゲルパーミェーションクロマトグラフィー（以
下ＧＰＣと略記する）法によりポリスチレンを標準とし
て求める。多価フェノール系高分子化合物の数平均分子
量Ｍ７は好ましくは３００〜２０００であり、重量平均
分子量Ｍ８は好ましくは５００〜４０００である。より
好ましくはＭｆｉが４００〜１５００、Ｍｗが７００〜
３５００である。The molecular weight of the polyhydric phenol-based polymerized metal obtained by these methods is determined by gel permeation chromatography (hereinafter abbreviated as GPC) using polystyrene as a standard. The number average molecular weight M7 of the polyhydric phenol-based polymer compound is preferably 300 to 2,000, and the weight average molecular weight M8 is preferably 500 to 4,000. More preferably Mfi is 400-1500 and Mw is 700-1500.
It is 3500.
現像性及び耐処理薬品性の両方を満足するこれらの多価
フェノール類の重縮合体の好ましい例は、上記分子量範
囲のレゾルシンベンズアルデヒド樹脂、メチルレゾルシ
ンベンズアルデヒド樹脂、ビロガール・アセトン樹脂等
であり、より好ましくはビロガール・アセトン樹脂であ
る。Preferred examples of polycondensates of these polyhydric phenols that satisfy both developability and processing chemical resistance include resorcin benzaldehyde resin, methylresorcin benzaldehyde resin, bilogal acetone resin, etc. having the above molecular weight range, and more preferably is Bilogal acetone resin.
これら多価フェノール類の重縮合体の０−ナフトキノン
ジアジドスルホン酸エステルは次に示す合成法により得
られる。まず多価フェノール類の重縮合体を適当な溶媒
、例えばジオキサン等に溶解させて、これに０−ナフト
キノンジアジドスルホニルクロライドを投入し、次に炭
酸アルカリを当量点まで滴下することによりエステル化
する。O-naphthoquinonediazide sulfonic acid esters of polycondensates of these polyhydric phenols can be obtained by the following synthesis method. First, a polycondensate of polyhydric phenols is dissolved in a suitable solvent such as dioxane, 0-naphthoquinonediazide sulfonyl chloride is added thereto, and then alkali carbonate is added dropwise to the equivalence point for esterification.
このエステル化体の実質縮合率（多価フェノールのＯＨ
基１個に対する０−ナフトキノンジアジドスルホニルク
ロライドの割合）は１０〜５０モル％が好ましく、より
好ましくは１０〜４０モル％であり、更に好ましくは１
５〜３５モル％である。The actual condensation rate of this esterified product (OH of polyhydric phenol
The ratio of 0-naphthoquinonediazide sulfonyl chloride to one group is preferably 10 to 50 mol%, more preferably 10 to 40 mol%, even more preferably 1
It is 5 to 35 mol%.
５０モル％を超えると分子量に関係なく、現像液による
消去性が不良となり、１０モル％未満であるとオーバー
現像性が不良となり、画線部の損失を招きやすい。If it exceeds 50 mol %, the erasability with a developer will be poor regardless of the molecular weight, and if it is less than 10 mol %, the over-developability will be poor, which tends to cause loss of image areas.
このエステル化体の分子量はＯＨ基の実質縮合率により
若干変動するが、概して０１１基の実質縮合率１０モル
％乃至５０モル％のエステル化体については、Ｍ、ｌが
５００〜３６００でＭ。が７００〜５８００であるのが
好ましく、より好ましくはＭｆｉが６００〜２４００で
Ｍ８が９００〜４０００である。更に好ましくはＭ。が
７００〜２１００でＭ、が１０００〜３６００である。The molecular weight of this esterified product varies slightly depending on the actual condensation rate of the OH group, but in general, for an esterified product with an actual condensation rate of 011 groups of 10 mol % to 50 mol %, M and l are 500 to 3,600. is preferably 700 to 5,800, more preferably Mfi is 600 to 2,400 and M8 is 900 to 4,000. More preferably M. is 700-2100 and M is 1000-3600.
Ｍｎが３６００より大きくかっＭＨが５８００より大き
い多価フェノ、−ル類の重縮合体の。−ナフトキノンジ
アジドスルホン酸エステルを使用した場合には、アンダ
ー現像性が不良となり、地汚れが発生しやすくなる上に
消去性が不良となる。A polycondensate of polyhydric phenols having Mn greater than 3,600 and MH greater than 5,800. - When naphthoquinonediazide sulfonic acid ester is used, under-developability becomes poor, background smearing tends to occur, and erasability becomes poor.
一方、Ｍ、、が５００より小さくかつＭ８が７００より
小さい多価フェノール類の重縮合体の０−ナフトキノン
ジアジドスルホン酸エステルを使用した場合には、オー
バー現像性が不良となり画像部の損失を招き、また画像
部の耐処理薬品性が悪くなる傾向にあり、好ましくはな
い。On the other hand, when using 0-naphthoquinonediazide sulfonic acid ester, which is a polycondensate of polyhydric phenols with M of less than 500 and M8 of less than 700, over-developability is poor, resulting in loss of image areas. Also, the processing chemical resistance of the image area tends to deteriorate, which is not preferable.
このエステル化体の怒光層中における含有量は、その種
類によっても異なるが、概して５〜４０重量％が好まし
く、より好ましくは１０〜３０重世％である。The content of this esterified product in the phosphorus layer varies depending on its type, but is generally preferably 5 to 40% by weight, more preferably 10 to 30% by weight.
また下記の一般式〔１〕
Ｃ０ＮＲ，、−（Ｘ）ｉ−Ｙ −０１１（式中、Ｒ１お
よびＲ２は水素原子、ハロゲン原子、アルキル基、了り
−ル基またはカルボン酸基であり、Ｒ３は水素原子、ハ
ロゲン原子、アルキル基またはアリール基であり、Ｒ４
は水素原子、アルキル基、了り−ル基またはアラルキル
基であり、Ｙは置換基を有してもよい芳香族基であり、
Ｘは窒素原子と前記芳香族基の炭素原子とを連結する２
価の有機基であり、ｎはＯ〜５の整数である。）により
表わされる構造単位を有する高分子化合物は、上記構造
単位のみの繰り返し構造を有する単独重合体でもよいが
、上記構造単位の他に１種又は２種以上の単量体単位を
存する共重合体でもよい。In addition, the following general formula [1] C0NR,, -(X)i-Y -011 (wherein R1 and R2 are a hydrogen atom, a halogen atom, an alkyl group, an aryol group or a carboxylic acid group, and R3 is a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and R4
is a hydrogen atom, an alkyl group, an aralkyl group, or an aralkyl group, and Y is an aromatic group that may have a substituent,
X connects the nitrogen atom and the carbon atom of the aromatic group 2
It is a valent organic group, and n is an integer of O to 5. ) may be a homopolymer having a repeating structure of only the above structural units, but it may also be a copolymer having one or more monomer units in addition to the above structural units. May be combined.
上記構造単位において、Ｒ＋およびＲ２は水素原子、メ
チル基やエチル基等のアルキル基、またはカルボン酸基
が好ましく、より好ましくは水素原子である。Ｒ３は水
素原子、臭素や塩素等のハロゲン原子、またはメチル基
やエチル基等のアルキル基が好ましく、より好ましくは
水素原子またはメチル基である。Ｙは好ましくは置換基
を有してもよいフェニレン基またはナフチレン基であり
、置換基としてはメチル基やエチル基等のアルキル等、
臭素や塩素等のハロゲン原子、カルボン酸基、メトキシ
基やエトキシ基等のアルコキシ基、水５５５、スルホン
酸基、シアノ基、ニトロ基、アシル基等がある。より好
ましくはＹは無置換かまたはメチル基を有するフェニレ
ン基またはナフチレン基である。Ｘは窒素原子と芳香族
炭素とを連結する２価の有機基であるが、アルキレン基
が好ましく、またｎはＯ〜５であり、好ましくは０〜３
、より好ましくは０である。In the above structural unit, R+ and R2 are preferably a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, or a carboxylic acid group, and more preferably a hydrogen atom. R3 is preferably a hydrogen atom, a halogen atom such as bromine or chlorine, or an alkyl group such as a methyl group or an ethyl group, and more preferably a hydrogen atom or a methyl group. Y is preferably a phenylene group or a naphthylene group which may have a substituent, and examples of the substituent include alkyl such as a methyl group and an ethyl group,
Examples include halogen atoms such as bromine and chlorine, carboxylic acid groups, alkoxy groups such as methoxy and ethoxy groups, water 555, sulfonic acid groups, cyano groups, nitro groups, and acyl groups. More preferably, Y is an unsubstituted phenylene group or a naphthylene group having a methyl group. X is a divalent organic group connecting a nitrogen atom and an aromatic carbon, preferably an alkylene group, and n is O-5, preferably 0-3
, more preferably 0.
共重合体型の構造を存する本発明の高分子化合物におい
て、前記式で示される構造単位と組み合わせて用いるこ
とができる単量体単位としては、例えばエチレン、プロ
ピレン、イソブチレン、ブタジェン、イソプレン等のエ
チレン系不飽和オレフィン類、例えばスチレン、α−メ
チルスチレン、ｐ−メチルスチレン、ｐ−クロロスチレ
ン等のスチレン類、例えばアクリル酸、メタクリル酸等
のアクリル酸類、例えばイタコン酸、マレイン酸、無水
マレイン酸等の不飽和脂肪族ジカルボン酸類、例えばア
クリル酸メチル、アクリル酸エチル、アクリル酸ｎ−ブ
チル、アクリル酸イソブチル、アクリル酸ドデシル、ア
クリル酸２−クロロエチル、アクリル酸フェニル、α−
クロロアクリル酸メチル、メタクリル酸メチル、メタク
リル酸エチル、エタクリル酸エチル等のα−メチレン脂
肪族モノカルボン酸のエステル類、例えばアクリロニト
リル、メタアクリロニトリル等のニトリル類、例えばア
クリルアミド等のアミド類、例えばアクリルアニリド、
ｐ−クロロアクリルアニリド、ｍ−ニトロアクリルアニ
リド、ｍ−メトキシアクリルアニリド等のアニリド類、
例えば酢酸ビニル、プロピオン酸ビニル、ベンジェ酸ビ
ニル、酪酸ビニル等のど、ニルエステル類、例えばメチ
ルビニルエーテル、エチルビニルエーテル、イソブチル
ビニルエーテル、β−クロロエチルビニルエーテル等の
ビニルエーテル類、塩化ビニル、ビニリデンクロライド
、ビニリデンシアナイド、例えば１−メチル−１′−メ
トキシエチレン、１．１′−ジメトキシエチレン、１．
２−ジメトキシエチレン、１．１’−ジメトキシカルボ
ニルエチレン、ニーメチル−１′−二トロエチレン等の
エチレン誘導体類、例えばＮ−ビニルビロール、Ｎ−ビ
ニルカルバゾール、Ｎ−ビニルインドール、Ｎ−ビニル
ピロリドン、Ｎ−ビニルピロリドン等のＮ−ビニル化１
、等のビニル系単量体がある。これらのビニル系単量体
は不飽和二重結合が開裂した構造で高分子化合物中に存
在する。In the polymer compound of the present invention having a copolymer-type structure, examples of monomer units that can be used in combination with the structural unit represented by the above formula include ethylene-based monomer units such as ethylene, propylene, isobutylene, butadiene, and isoprene. Unsaturated olefins, such as styrenes such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, acrylic acids such as acrylic acid and methacrylic acid, such as itaconic acid, maleic acid, maleic anhydride, etc. Unsaturated aliphatic dicarboxylic acids, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-
Esters of α-methylene aliphatic monocarboxylic acids such as methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, and ethyl ethacrylate; nitriles such as acrylonitrile and methacrylonitrile; amides such as acrylamide; e.g. acrylanilide; ,
Anilides such as p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide,
For example, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, For example, 1-methyl-1'-methoxyethylene, 1.1'-dimethoxyethylene, 1.
Ethylene derivatives such as 2-dimethoxyethylene, 1,1'-dimethoxycarbonylethylene, dimethyl-1'-ditroethylene, such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone, N- N-vinylation of vinylpyrrolidone etc. 1
There are vinyl monomers such as . These vinyl monomers exist in polymer compounds with a structure in which unsaturated double bonds are cleaved.
上記の単量体のうち、構造単位（’Ｉ）と組み合わせて
用いるものとして、（メタ）アクリル酸類、脂肪族モノ
カルボン酸のエステル類、ニトリル類が総合的にみて優
れた性能を示し、好ましい。より好ましくは、メタクリ
ル酸、メタクリル酸メチル、アクリロニトリル、アクリ
ル酸エチル等である。Among the above monomers, (meth)acrylic acids, esters of aliphatic monocarboxylic acids, and nitrites are preferred as they exhibit excellent overall performance and are used in combination with the structural unit ('I). . More preferred are methacrylic acid, methyl methacrylate, acrylonitrile, ethyl acrylate, and the like.
これらの単量体は高分子化合物中にブロック又はランダ
ムのいずれの状態で結合していてもよい。These monomers may be bound in a block or random manner in the polymer compound.
本発明の高分子化合物（Ｂ）の代表的な例をあげる。な
お下記に例示の化合物において、Ｍ、は重量平均分子量
、Ｍ、は数平均分子量、ｓ、に、ｌ。Representative examples of the polymer compound (B) of the present invention are given below. In the compounds exemplified below, M is weight average molecular weight, M is number average molecular weight, s, and l.
ｍおよびｎは、それぞれ構造単位のモル％を表わす。m and n each represent mol% of the structural unit.
ａ）＋弐（Ｔ）−）−ｉｆ→ＣＨ２−ＣＲ，＋０ＯＲｚ
（Ｒ＋、Ｒｚは水素原子、アルキル基、ハロゲン基）ｂ
）千式（１）ｈＨＣＨｚ −ＣＲ山→Ｃ）１２ Ｃ１
ｈｈ−］ Ｉ
Ｃ０ＯＲ２ＣＮ
（Ｒ１”’Ｒ３は水素原子、アルキル基、ハロゲン原子
）ｅ）千載（Ｉ ）−）−＝（ＣＨ２−ＣＲ＋ｈ→ＣＨ
，−ＣＲ３）７−ＣＯＯＲｚ Ｃ００ｔｌ
（Ｒ，〜Ｒ３は水素原子、アルキル基、ハロゲン原子）
ｆ）千成（ｒ）ｈ→Ｃ１１ｚ ＣＲ＋）ｉ→ＣＨｚ
ＣＲｉｈ−ＣＯＯＲｚ Ｃ００Ｈ
−−イＣＨ，−ＣＲ，，）−ｒ−
Ｎ
（Ｒ，〜Ｒ４は水素原子、アルキル基、ハロゲン原子）
ｇ）千成（Ｉ ）＋ｒ−（−Ｃ）１２− ＣＲｌ ）Ｔ
→ＣＨｚ ＣＲｚ＋ＣＯＯＣＪ４０ＨＣ００Ｒ１
ＣＮ Ｃ００Ｈ
（Ｒ＋”Ｒｓは水素原子、アルキル基、ハロゲン原子）
ｈ）千成（Ｉ ）−）−ｉ←ＣＨ，−ＣＲ，ｉ→ＣＨ２
ＣＲｚｈ−ＣＯＯＣＪｔＯＨＣ０ＯＲ＊
−ＨＣＨｚ −ＣＲ４）Ｔ
Ｎ
（Ｒ，〜Ｒ６は水素原子、アルキル基、ハロゲン原子）
更に、具体的には、
ＣＨ２Ｃｌ。a)+2(T)-)-if→CH2-CR,+0ORz (R+, Rz are hydrogen atoms, alkyl groups, halogen groups)b
) Senshiki (1) hHCHz - CR mountain → C) 12 C1
hh-] I C0OR2CN (R1'''R3 is a hydrogen atom, an alkyl group, a halogen atom) e) 1,000 (I)-)-=(CH2-CR+h→CH
, -CR3)7-COORz C00tl (R, ~R3 are hydrogen atoms, alkyl groups, halogen atoms)
f) Sennari (r) h → C11z CR+) i → CHz
CRih-COORz C00H --iCH, -CR,,)-r- N (R, ~R4 are hydrogen atoms, alkyl groups, halogen atoms)
g) Sennari (I)+r-(-C)12-CRl)T
→CHz CRz+COOCJ40HC00R1 CN C00H (R+"Rs is hydrogen atom, alkyl group, halogen atom)
h) Sennari (I)-)-i←CH,-CR,i→CH2
CRzh-COOCJtOHC0OR* -HCHz -CR4)T N (R, ~R6 are hydrogen atoms, alkyl groups, and halogen atoms)
Furthermore, specifically, CH2Cl.
ＣＩｌ＋ ＣＨ：＋ １ ］ ＣＨ３ （ｍ：ｎ：Ａ＝４０ ： ２０ ： ４０Ｃ１（３ ＣＨ。CIl+ CH:+ 1 ] CH3 (m:n:A=40:20:40C1(3 CH.
ＣＨ。CH.
墓
’ｍ：ｎ：Ｊ＝３０：３５：３５
ＣＨ，Ｃ１１゜
Ｃ１ｈ ＣＬ
ＣＩ ＣＨ３ＣＨ３−±ＣＩ□−Ｃ
ト÷ｒ
ＣＮ
Ｃｔｊ３Ｂｒ ＣＨｌ
ｌ １ １Ｈ３
一←ＣＨ２−Ｃ−＋ｒ−
ＣＮ
’ｍ：ｎ：Ａ：に＝２０：３５：５：４０−←ＣＨ，−
Ｃト÷「
ＣＮ
一←ＣＨ２ＣＨ→τ−−（ＣＨ２−Ｃ±「ＣＮ
Ｃ０ＯＨ
本発明の高分子化合物（Ｂ）はつぎのようにして合成す
ることができる。まず、α・β−不飽和酸クロライド類
、またはα・β−不飽和酸無水物類とフェノール性水酸
基を有する第１級または第２級アミン類とを必要に応じ
て塩基性触媒を用いて反応せしめ、前記一般式（１）で
示される構造単位を有する単量体を合成する。次にその
単量体を常法に従って単独重合させるか、あるいはその
単量体と少くとも１種の他のビニル系単量体とを共重合
させ、本発明の高分子化合物を得ることができる。この
際各車量体の仕込みモル比および重合条件を種々変える
ことにより、高分子化合物（Ｂ）の分子量ならびに各構
造単位のモル比を広範囲に設定することができる。しか
し、本発明の目的とする用途に有効に供するためには、
分子量は５，０００乃至１００，０００ 、前記一般式
（１）で示される構造単位のモル含有率は少くとも１０
モル％であるものが望ましい。Tomb'm:n:J=30:35:35 CH, C11゜C1h CL CI CH3CH3-±CI□-C
T÷r CN Ctj3Br CHl l 1 1H3 1←CH2−C−+r− CN 'm:n:A:=20:35:5:40−←CH,−
C ÷ "CN 1←CH2CH→τ--(CH2-C±"CN
C0OH The polymer compound (B) of the present invention can be synthesized as follows. First, α/β-unsaturated acid chlorides or α/β-unsaturated acid anhydrides and primary or secondary amines having a phenolic hydroxyl group are mixed using a basic catalyst as necessary. A monomer having the structural unit represented by the general formula (1) is synthesized by reaction. Next, the monomer is homopolymerized according to a conventional method, or the monomer and at least one other vinyl monomer are copolymerized to obtain the polymer compound of the present invention. . At this time, the molecular weight of the polymer compound (B) and the molar ratio of each structural unit can be set over a wide range by varying the charging molar ratio of each carmer and the polymerization conditions. However, in order to effectively serve the purpose of the present invention,
The molecular weight is 5,000 to 100,000, and the molar content of the structural unit represented by the general formula (1) is at least 10
It is desirable that the amount is mol%.
本発明の感光層を形成する組成物中には、公知のアルカ
リ可溶性の高分子化合物を含有させることができる。ア
ルカリ可溶性の高分子化合物としてノボラック樹脂、例
えばフェノール・ホルムアルデヒド樹脂、クレゾール・
ホルムアルデヒド樹脂やフェノール変性キシレン樹脂、
ポリヒドロキシスチレン等があげられるが、このような
アルカリ可溶性の高分子化合物は全組成物の４０重量％
以下の添加量で用いられる。The composition for forming the photosensitive layer of the present invention may contain a known alkali-soluble polymer compound. Novolac resins such as phenol/formaldehyde resins, cresol/
formaldehyde resin, phenol-modified xylene resin,
Examples include polyhydroxystyrene, but such alkali-soluble polymer compounds account for 40% by weight of the total composition.
It is used in the following amounts.
ポジ型感光性平版印刷版は一般にそのほかに露光可視画
付与剤及び色素を含有する。露光可視画付与剤としては
、露光により酸を発生する物質、色素としてはこの酸と
塩を形成する化合物を用いるのが一般的である。Positive-working photosensitive lithographic printing plates generally also contain an exposure visible image-imparting agent and a dye. As the exposure visible image imparting agent, a substance that generates an acid upon exposure to light is generally used, and as the dye, a compound that forms a salt with this acid is generally used.
露光により酸を発生する化合物としては、下記一般式■
または■で表されるトリハロアルキル化合物またはジア
ゾニウム塩化合物が好ましい。As a compound that generates acid upon exposure to light, the following general formula ■
A trihaloalkyl compound or a diazonium salt compound represented by or (■) is preferred.
（ただし、Ｘａは炭素原子数１〜３のトリハロアルキル
基であり、ＷはＮまたはＰであり、Ｚは０゜ＳまたはＳ
ｅであり、ＹはＷとＺを環化させるとともに発色団を有
する基である。）
Ａｒ−ＮＺ” Ｘ−＝・ｍ
（Ａｒはアリール基であり、Ｘは無機化合物の対イオン
である。）
具体的には、式■のトリハロアルキル化合物としては、
例えば下記の一般式ｔｌａ、Ｉｌｂ、［Ｉｃで表される
化合物がある。(However, Xa is a trihaloalkyl group having 1 to 3 carbon atoms, W is N or P, and Z is 0°S or S
e, and Y is a group that cyclizes W and Z and has a chromophore. ) Ar-NZ''
For example, there are compounds represented by the following general formulas tla, Ilb, and [Ic.
Ｎ −Ｎ
ＩＩ ＩＩ
Ｘａ ＯＢ
Ｃ＝Ｎ Ｂ
Ｘａ
Ｘａ
（ただし、Ａは置換若しくは非置換子り−ル基又は複素
環式基であり、Ｂは水素又はメチル基であり、ｎはＯ〜
２の整数である。）
露光可視画付与剤の添加量は、感光層の全組成物の０．
０１〜２０重四％であるのが好ましく、より好ましくは
０．１〜１０重世％である。N -N II II Xa OB C=N B
It is an integer of 2. ) The added amount of the exposed visible image imparting agent is 0.000000000000000000000000000000,000,000,000,000.
It is preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight.
一方、色素としては一般に酸により塩を形成する化合物
であればいずれも使用可能であり、例えばトリフェニル
メタン系染料、シアニン染料、ジアゾ染料、スチリル染
料等が挙げられる。On the other hand, as the dye, any compound that generally forms a salt with an acid can be used, such as triphenylmethane dyes, cyanine dyes, diazo dyes, styryl dyes, and the like.
具体的にはビクトリアピュアブルーＢ○、エチルバイオ
レット、クリスタルバイオレット、ブリリアントグリー
ン、ヘイシックツクシン、エオシン、フェノールフタレ
イン、キシレノールブルー、コンゴーレッド、マラカイ
トグリーン、オイルブルー＃６０３、オイルピンク＃３
１２、クレゾールレッド、オーラミン、４− ｐ−ジエ
チルアミノフェニルイミノナフトキノン、ロイコマラカ
イトグリーン、ロイコクリスタルバイオレット等が挙げ
られる。色素の添加量は感光層の全組成物の約０．０１
〜１０重量％が好ましく、より好ましくは０．０５〜８
重量％である。Specifically, Victoria Pure Blue B○, Ethyl Violet, Crystal Violet, Brilliant Green, Heisik Tsukushin, Eosin, Phenolphthalein, Xylenol Blue, Congo Red, Malachite Green, Oil Blue #603, Oil Pink #3
12, cresol red, auramine, 4-p-diethylaminophenylimino naphthoquinone, leucomalachite green, leuco crystal violet and the like. The amount of the dye added is approximately 0.01 of the total composition of the photosensitive layer.
~10% by weight is preferred, more preferably 0.05~8%
Weight%.
本発明のポジ型感光性平版印刷版の感光層組成物中には
、その他に目的に応じて各種の添加剤を加えることがで
きる。例えば塗布性を向上させるために界面活性剤、感
度向上のために各種増感剤、塗膜の物性改良のために可
塑剤等、また、画像の印刷インキ着肉性を高めるために
、疎水性基を有する各種添加剤、例えばｐ−オクチルフ
ェノール−ホルマリンノボラック樹脂、ｐ−ｔ−ブチル
フェノール−ホルマリンノボラック樹脂、ｐ−ｔ−ブチ
ルフェノール・ベンズアルデヒド樹脂、ロジン変性ノボ
ラック樹脂等の変性ノボラック樹脂、これらの変性ノボ
ラック樹脂の０−ナフトキノンジアジドスルホン酸エス
テル（０１１基のエステル化率２０〜７０モル％）等を
添加することができる。Various other additives may be added to the photosensitive layer composition of the positive-working photosensitive lithographic printing plate of the present invention depending on the purpose. For example, surfactants are used to improve coating properties, various sensitizers are used to improve sensitivity, plasticizers are used to improve the physical properties of coating films, and hydrophobic agents are used to improve printing ink receptivity for images. Various additives having groups such as modified novolac resins such as p-octylphenol-formalin novolak resin, p-t-butylphenol-formalin novolak resin, p-t-butylphenol benzaldehyde resin, rosin-modified novolak resin, and these modified novolak resins. 0-naphthoquinonediazide sulfonic acid ester (esterification rate of 011 group: 20 to 70 mol%), etc. can be added.
これらの添加剤の含有量はその種類と目的によって異な
るが、概して感光層の全組成物に対して０．０１〜２０
重量％、好ましくは０．０５〜１０重量％である。The content of these additives varies depending on their type and purpose, but is generally 0.01 to 20% of the total composition of the photosensitive layer.
% by weight, preferably from 0.05 to 10% by weight.
上記感光層組成物は、各種溶媒、例えばメチル（エチル
）セロソルブ、メチル（エチル）セロソルブアセテート
等のセロソルブ類、ジメチルホルムアミド、ジメチルス
ルホキシド、ジオキサン、アセトン、シクロヘキサノン
、トリクロロエチレン等の塗布溶媒に溶解して支持体上
に塗布し、乾燥することにより形成される。The photosensitive layer composition can be supported by being dissolved in various solvents, such as cellosolves such as methyl (ethyl) cellosolve and methyl (ethyl) cellosolve acetate, coating solvents such as dimethyl formamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone, and trichloroethylene. It is formed by applying it on the body and drying it.
本発明のポジ型感光性平版印刷版の感光層は、用途によ
っても異なるが、一般的に固形分として０．５〜３．０
ｇ／ｒ＋（となるように形成するのが好ましい。The photosensitive layer of the positive photosensitive lithographic printing plate of the present invention generally has a solid content of 0.5 to 3.0, although it varies depending on the use.
It is preferable to form it so that g/r+(.
本発明のポジ型感光性平版印刷版に用いる支持体として
は、アルミニウム板が好ましい。アルミニウム板に対し
ては、砂目立て処理、陽極酸化処理及び必要に応じて封
孔処理等の表面処理を施すのが好ましい。これらの処理
は公知の方法により行うことができる。As the support used in the positive photosensitive lithographic printing plate of the present invention, an aluminum plate is preferable. The aluminum plate is preferably subjected to surface treatments such as graining, anodizing, and if necessary, sealing. These treatments can be performed by known methods.
砂目立て処理の方法としては、機械的方法および電解に
より工・ノチングする方法が挙げられる。Examples of methods for graining include mechanical methods and electrolytic notching methods.
機械的方法としては、例えば、ボール研磨法、ブラシ研
磨法、液体ホーニングによる研磨法、ハフ研磨法等が挙
げられる。アルミニウム材の組成等に応じて、上記の方
法を単独または組合せて用いることができる。好ましい
のは電解エツチング法である。Examples of the mechanical method include a ball polishing method, a brush polishing method, a polishing method using liquid honing, and a Hough polishing method. Depending on the composition of the aluminum material, the above methods can be used alone or in combination. Preferred is electrolytic etching.
電解エツチングは、リン酸、硫酸、塩酸、硝酸等の無機
酸を１種または２種以上含有する浴中にアルミニウム板
を浸漬することにより行う。砂目立て処理の後、必要に
応じてアルカリあるいは酸の水溶液９によってデスマッ
ト処理を行って中和し、水洗する。Electrolytic etching is performed by immersing the aluminum plate in a bath containing one or more inorganic acids such as phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid. After the graining treatment, if necessary, a desmut treatment is performed with an aqueous alkali or acid solution 9 to neutralize it, followed by washing with water.
陽極酸化処理は、電解液として硫酸、クロム酸、シュウ
酸、リン酸、マロン酸等を１種または２種以上含む溶液
を用い、アルミニウム板を陽極にして電解することによ
り行う。形成された陽極酸化皮膜量は１〜５０■／ｄｍ
２が適当であり、好ましくは１０〜４０ ｍｇ／ｄｍ２
である。ここで陽極酸化皮膜量は、例えばアルミニウム
液をリン酸クロム酸溶液（８５％リン酸水溶液３５ｍｎ
と、酸化クロム（Ｖ［）２０ｇとを１１の水に溶解して
生成）に浸漬して酸化皮膜を溶解し、板の皮膜溶解前後
の重量変化を測定することにより求めることができる。The anodizing treatment is performed by electrolyzing using an aluminum plate as an anode using a solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid, etc. as an electrolytic solution. The amount of anodic oxide film formed is 1 to 50 μ/dm
2 is suitable, preferably 10 to 40 mg/dm2
It is. Here, the amount of anodized film is, for example, aluminum solution mixed with phosphoric acid chromic acid solution (35 mL of 85% phosphoric acid aqueous solution).
and chromium oxide (V[) 20g dissolved in 11 water) to dissolve the oxide film, and measure the change in weight of the plate before and after the film is dissolved.
封孔処理としては、沸腋水処理、水蒸気処理、ケイ酸ソ
ーダ処理、重クロム酸塩水溶液処理等がある。この他に
アルミニウム支持体に対して、水溶性裔分子化合物や、
フッ化ジルコン酸等の金属塩の水溶液により下引処理を
施すこともできる。Pore sealing treatments include boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, and the like. In addition, water-soluble progeny molecular compounds,
Subbing treatment can also be performed using an aqueous solution of a metal salt such as fluorinated zirconate.
このようにして得られたポジ型感光性平版印刷版は公知
の方法により使用することができる。典型的には、感光
性印刷版にポジ型フィルムを密着させ、超高圧水銀灯、
メタルハライドランプ等で露光し、メタケイ酸ソーダ、
メタケイ酸カリ、リン酸ソーダ、カセイソーダ等のアル
カリ水溶液により現像し、印刷版とする。The positive-working photosensitive planographic printing plate thus obtained can be used by a known method. Typically, a positive film is attached to a photosensitive printing plate, and an ultra-high pressure mercury lamp,
After exposure with a metal halide lamp, etc., sodium metasilicate,
It is developed with an alkaline aqueous solution of potassium metasilicate, sodium phosphate, caustic soda, etc. to form a printing plate.
このようにして作製された平版印刷版は枚葉、オフ輸用
印刷機において使用することができる。The lithographic printing plates thus produced can be used in sheet-fed, off-line printing presses.
（実施例〕 本発明を以下の実施例によりさらに詳細に説明する。(Example〕 The present invention will be explained in further detail by the following examples.
まず、本発明に使用する感光体およびバインダーの合成
例を以下に示す。First, synthetic examples of the photoreceptor and binder used in the present invention are shown below.
金底開１
ピロガロール１００ｇおよびアセトン７００ｇをウォー
ターハス中にセットした３頭コルベン中に投入し、窒素
ガスを吹込んで、窒素置換を行った後、オキシ塩化リン
１０ｇを投入して重縮合反応を行った。反応温度は２０
°Ｃに保ち一昼夜反応を継続した。反応終了後、水３０
！中に強力にかくはんしながら生成物を徐々に投入し、
重縮合物を沈殿させた。Opening the gold bottom 1 100 g of pyrogallol and 700 g of acetone were placed in a three-headed Kolben set in a water lotus, nitrogen gas was blown in to perform nitrogen substitution, and then 10 g of phosphorus oxychloride was added to perform a polycondensation reaction. Ta. The reaction temperature is 20
The reaction was continued overnight while keeping the temperature at °C. After the reaction is complete, 30 liters of water
! Gradually add the product while stirring vigorously,
The polycondensate was precipitated.
析出した樹脂をｒ別し、水でほぼ中性になるまで洗浄し
た。沈殿物は４０°Ｃ以下で乾燥した。このようにして
淡褐色状の樹脂１００ｇを得た。The precipitated resin was separated and washed with water until it became almost neutral. The precipitate was dried below 40°C. In this way, 100 g of light brown resin was obtained.
この樹脂の分子量を、ＧＰＣＣ日立、６３５型、カラム
ショデソクス（Ｓｈｏｄｅｘ）Ａ ８０４．Ａ ８０３
゜Ａ３０２の直列〕によりポリスチレンを標準として測
定した。ＭＢ、Ｍｙの算出は拓殖等、日本化学会誌、１
９７２年（４月号）第８００真に記載の方法により、オ
リゴマー領域のピークをならす（ピークの山と谷の中心
を結ぶ）方法により行った。The molecular weight of this resin was determined by GPCC Hitachi, Model 635, Column Shodex A 804. A 803
゜A302 in series] using polystyrene as a standard. Calculation of MB and My is by Takushoku et al., Journal of the Chemical Society of Japan, 1
The measurement was carried out according to the method described in No. 800 of the April issue of 1997, in which the peaks of the oligomer region were leveled (the centers of the peaks and valleys were connected).
その結果、Ｍ、、は２０００．Ｍ、は３４００であった
。As a result, M, is 2000. M was 3400.
次にこの樹脂６０ｇをジオキサン７２０ｍｆｆに溶解し
、１，２−ナフトキノンジアジド−５−スルホニルクロ
ライド７０ｇを投入し、溶解後１３重世％の炭酸カリ水
溶液６０ｇを滴下し、４０〜５０゛Ｃで約１時量線合反
応を行わせた。得られた反応液を大量の希塩酸水（濃塩
酸１．３ｍｆ、水３１）中に投入し、沈殿した樹脂をが
刑し、乾燥した。Next, 60 g of this resin was dissolved in 720 mff of dioxane, 70 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride was added, and after dissolving, 60 g of a 13% potassium carbonate aqueous solution was added dropwise, and the mixture was heated at 40 to 50°C to approx. A 1-hour linear combination reaction was performed. The obtained reaction solution was poured into a large amount of diluted hydrochloric acid water (concentrated hydrochloric acid 1.3 mf, water 31 ml), and the precipitated resin was boiled and dried.
このようにして、ピロガロール−アセトン（ｂ１脂の１
．２−ナフトキノンジアジド−５−スルホン酸エステル
の黄色粉末樹脂５６ｇが得られた。分析の結果、ＯＨ基
の縮合率は２０％であることが判明した。このエステル
体の分子量を上記ＧＰＣにより測定したところ、Ｍ、は
２３００、Ｍ 、は３０３０であった。In this way, pyrogallol-acetone (1 of b1 fat)
．． 56 g of a yellow powder resin of 2-naphthoquinonediazide-5-sulfonic acid ester was obtained. As a result of analysis, it was found that the condensation rate of OH groups was 20%. When the molecular weight of this ester was measured by the above GPC, M was 2,300 and M was 3,030.
合成例２
レゾルシン８７．２ ｇおよびメタノール２６０ｇを、
ウォーターバス中にセットした３頭コルヘン中に投入し
、レゾルシンが溶解した後、ヘンズアルデヒド７８ｇを
加え、更に濃塩酸０．５ｍＡを加え、約１０分後にメタ
ノールが還流するように加温コントロールを行った。還
流が始まって約２時間後、反応液を約４１の水中に滴下
し、決別し、水洗を行って室温で乾燥した。このように
して淡褐色粉末状樹脂１１２ｇが得られた。合成例１と
同様にＧＰＣによる分子量測定を行った結果、Ｍｌは７
８０、Ｍ、は１３２０であった。Synthesis Example 2 87.2 g of resorcinol and 260 g of methanol,
Three animals were placed in a colchen set in a water bath, and after the resorcinol had dissolved, 78 g of henzaldehyde was added, followed by 0.5 mA of concentrated hydrochloric acid, and the heating was controlled so that the methanol refluxed after about 10 minutes. Ta. Approximately 2 hours after the start of reflux, the reaction solution was dropped into approximately 41 g of water, separated, washed with water, and dried at room temperature. In this way, 112 g of light brown powdered resin was obtained. As a result of measuring the molecular weight by GPC in the same manner as in Synthesis Example 1, Ml was 7.
80,M, was 1320.
次にこの樹脂６６ｇをジオキサン７２０ｍ＃に熔解し、
０−ナフトキノンジアジド−５−スルホニルクロライド
９０ｇを投入し、溶解後、１３重量％の炭酸カリ水溶液
２１３ｇを滴下し、４０〜５０℃で約１時量線合反応を
行った。その後反応液を合成例１と同様に大量の希塩酸
中に投入し、炉別し、１３２ｇのレゾルシン・ベンズア
ルデヒド樹脂の０−ナフトキノンジアジドスルホン酸エ
ステル樹脂を得た。分析の結果、０］１基の縮合率は２
３％であった。ＧＰＣによる分子量測定の結果、Ｍｌｌ
は１５５０、Ｍ、は１７８０であった。Next, 66 g of this resin was dissolved in 720 m# of dioxane,
90 g of 0-naphthoquinonediazide-5-sulfonyl chloride was charged, and after dissolving, 213 g of a 13% by weight aqueous potassium carbonate solution was added dropwise, and a linear combination reaction was carried out at 40 to 50° C. for about 1 hour. Thereafter, the reaction solution was poured into a large amount of dilute hydrochloric acid in the same manner as in Synthesis Example 1, and separated in a furnace to obtain 132 g of 0-naphthoquinonediazide sulfonic acid ester resin of resorcinol benzaldehyde resin. As a result of analysis, the condensation rate of 0]1 group is 2
It was 3%. As a result of molecular weight measurement by GPC, Mll
was 1550, and M was 1780.
−較金底貫工
ｍ−クレゾール２１６ｇ、３７％ホルムアルデヒド水溶
液６０ｇおよびシュウ酸２．５ｇをオイルバスにセット
した３頭コルベン中に投入し、かくはんしながら昇温し
た。９０ ’Ｃ付近で激しく発泡し、一時的に冷却した
後再び昇温し、コルベン内の温度を１０５℃にした。- 216 g of cresol, 60 g of a 37% formaldehyde aqueous solution, and 2.5 g of oxalic acid were placed in a three-headed colben set in an oil bath, and the temperature was raised while stirring. It foamed violently at around 90'C, and after being temporarily cooled, the temperature was raised again to bring the temperature inside the Colben to 105C.
約３時間反応させた後、更に１７５“Ｃまで昇温しで水
を留去した。２時間後２００℃に昇温するとともに１０
０ ＋ｕｌ１ｇに減圧し、残留モノマーを留去した。１
時間後反応を止め、反応物をテフロン・パット上に流し
出し、固化させた。この樹脂の分子量を、ＧＰＣで測定
した結果、Ｍ、、は５００、Ｍ８は１５００であった。After reacting for about 3 hours, the temperature was further raised to 175"C and water was distilled off. After 2 hours, the temperature was raised to 200"C and 10
The pressure was reduced to 0 + ul1 g, and the residual monomer was distilled off. 1
After a period of time, the reaction was stopped and the reaction product was poured onto a Teflon pad and allowed to solidify. The molecular weight of this resin was measured by GPC, and as a result, M was 500 and M8 was 1500.
次にこの樹脂６０ｇをジオキサン７２０ｍ１ｌ！にン容
解し、０−ナフトキノンジアジド−５−スルホニルクロ
ライド１００ｇを投入し、溶解後、１３重量％の炭酸カ
リ水を容ン夜１１５ｇを７商下し、４０〜５０°Ｃで約
１時量線合反応を行った。その後反応液を大量の希塩酸
（濃塩酸１３ｍ１、水１２１）中に投入し、沈殿した樹
脂をが別し、乾燥した。Next, add 60 g of this resin to 720 ml of dioxane! Dissolve the garlic, add 100 g of 0-naphthoquinonediazide-5-sulfonyl chloride, and after dissolving, add 13% by weight potassium carbonate water, drop 115 g for 7 hours, and heat at 40 to 50°C for about 1 hour. A dose-matching reaction was performed. Thereafter, the reaction solution was poured into a large amount of dilute hydrochloric acid (13 ml of concentrated hydrochloric acid, 121 ml of water), and the precipitated resin was separated and dried.
このようにして１０５ｇのｍ−クレゾール・ホルムアル
デヒド樹脂の０−ナフトキノンジアジドスルホン酸エス
テル樹脂が得られた。分析の結果０１１基の縮合率は３
０％であった。In this way, 105 g of 0-naphthoquinonediazide sulfonic acid ester resin of m-cresol formaldehyde resin was obtained. As a result of analysis, the condensation rate of 011 group is 3
It was 0%.
前述の方法でＭ、、、Ｍ８の算出を行った結果、Ｍ。As a result of calculating M, . . . M8 using the method described above, M.
は８５０、Ｍ８は１７５０であった。was 850, and M8 was 1750.
金威遣ロー
前記（ｂ−１）の高＼子ヒ合物の合成
ｐ−ヒドロキシアニリン４００ ｇ、ハイドロキノンモ
ノメチルエーテル４ｇ、アセトン４１およびピリジン３
６０ｇを混合し、寒剤を用いて外部より冷却し、内温か
一１０°Ｃまで下った時点でメタクリル酸クロライド４
２０ｇを攪拌下に滴下した。反応温度が０°Ｃ以下にな
るよう滴下速度を調節し、滴下終了後０〜３°Ｃで約２
時間攪拌した。Synthesis of the high-carbon compound of (b-1) above: p-hydroxyaniline 400 g, hydroquinone monomethyl ether 4 g, acetone 41 and pyridine 3
Mix 60g of methacrylic acid chloride, cool it from the outside using a cryogen, and when the internal temperature drops to -10°C,
20g was added dropwise while stirring. Adjust the dropping rate so that the reaction temperature is below 0°C, and after the dropwise addition is completed, the reaction temperature is about 2°C at 0-3°C.
Stir for hours.
次いで２５°Ｃで２時間攪拌後反応液を１／３位になる
まで濃縮し、これを希塩酸（ｐＨ約１．０）１０１中に
注入し、生じた沈殿を吸引が過して白色の固体を得た。After stirring at 25°C for 2 hours, the reaction solution was concentrated to 1/3, poured into 101ml of diluted hydrochloric acid (pH approx. 1.0), and the resulting precipitate was filtered off with suction to form a white solid. I got it.
この白色の固体を加温したメタノ−で暗赤色のこの溶液
を５％塩酸水溶液８２中に注入して多量の沈殿を生成さ
せ、これを吸引１濾過し、乾燥して淡桃色の固体を得た
。これをエタノールと水との混合溶媒より再結晶して、
融点１５５〜１５６°Ｃのｐ−ヒドロキシメタクリル７
ニリドの無色針状晶４５０ｇを得た。This white solid was heated with methanol and the dark red solution was injected into a 5% aqueous hydrochloric acid solution 82 to form a large amount of precipitate, which was filtered with suction and dried to obtain a pale pink solid. Ta. This was recrystallized from a mixed solvent of ethanol and water,
p-hydroxymethacrylate 7 with melting point 155-156°C
450 g of colorless needle crystals of nilide were obtained.
このようにして得たｐ−ヒドロキシメタクリルアニリド
（ｌｌｙＰＭ八）５３．２ｇ、アクリロニトリル（ＡＮ
）１５．９ｇ、メタクリル酸メチル（ＭＭＡ）４０、０
ｇおよびα・α′−アヅビスイソブチロニトリル０．
８２ ｇをアセトン：エタノール（Ｌ ： ２）のイ昆
合）各課１９０ｍβ中に溶解し、窒素ガス置換した後、
６５°Ｃで４時間加熱し、重合体溶液を得た。この重合
体溶液を３βの５％１ｌｃｊ２水溶液中に注ぎ、生じた
白色の沈殿物を濾過し、乾燥して、白色重合体７０ｇを
得た。得られた重合体の分子量をＧＰＣで測定したら、
Ｍｏが３２００．Ｍｗが２２０００であった。53.2 g of p-hydroxymethacrylanilide (llyPM8) thus obtained, acrylonitrile (AN
) 15.9g, methyl methacrylate (MMA) 40.0
g and α・α′-azubisisobutyronitrile 0.
82 g was dissolved in 190 mβ of each section of acetone:ethanol (L: 2), and after replacing with nitrogen gas,
The mixture was heated at 65°C for 4 hours to obtain a polymer solution. This polymer solution was poured into a 5% 1lcj2 aqueous solution of 3β, and the resulting white precipitate was filtered and dried to obtain 70 g of a white polymer. After measuring the molecular weight of the obtained polymer by GPC,
Mo is 3200. Mw was 22,000.
令Ｊむ１ん
合成例１で得たｐ−ヒドロキシメタクリルアニリド（）
１ｙＰＭＡ） ５０．０ ｇ、アクリロニトリル（Ａ、
Ｎ ）１５、０ ｇ、アクリル酸エチル（ＥＡ）４２
．０ｇおよびα・α′−アゾビスイソブチロニトリル０
．３０ｇをアセトン：エタノール（１： ２）の混合？
ｇ 媒１９０ ｍβ中に溶解し、窒素ガス置換した後、
６５℃で４時間加熱し、重合体溶液を得た。この重合体
溶液を３１の５％１Ｉｃｊ２水溶液中に注ぎ、生じた白
色の沈殿物を濾過し、乾燥して、白色重合体６５ｇを得
た。Ｃ，ＰＣで分子量を測定したら、Ｍ、が２８００、
Ｍ、が６００００であった。p-Hydroxy methacrylanilide () obtained in Synthesis Example 1
1yPMA) 50.0 g, acrylonitrile (A,
N) 15.0 g, ethyl acrylate (EA) 42
．． 0g and α・α′-azobisisobutyronitrile 0
．． Mix 30g of acetone:ethanol (1:2)?
After dissolving in g medium 190 mβ and replacing with nitrogen gas,
The mixture was heated at 65° C. for 4 hours to obtain a polymer solution. This polymer solution was poured into a 5% 1Icj2 aqueous solution of 31, and the resulting white precipitate was filtered and dried to obtain 65 g of a white polymer. When I measured the molecular weight with C, PC, M was 2800.
M, was 60,000.
合成例３
旦附劇ユし少意分ヱ囮皇皇少令戒
ｍ−ヒドロキシ−ｐ−シアノアニリン４００ｇ、ハイド
ロキノンモノメチルエーテル４ｇ１アセトン４１および
ピリジン３６０ｇを混合し、寒剤を用いて外部より冷却
し、内温か一１０℃まで下った時点でメタクリル酸クロ
ライド４２０ｇを撹拌下に滴下した。以下、合成例１と
同様にして、ｍ−ヒドロキシ−ｐ−シアノメタクリルア
ニリド３５０ｇを得た。Synthesis Example 3 400g of m-hydroxy-p-cyanoaniline, 4g of hydroquinone monomethyl ether, 41g of acetone, and 360g of pyridine were mixed, cooled from the outside using a cryogen, and cooled internally using a cryogen. When the temperature had dropped to -10°C, 420 g of methacrylic acid chloride was added dropwise with stirring. Thereafter, in the same manner as in Synthesis Example 1, 350 g of m-hydroxy-p-cyanomethacrylanilide was obtained.
このようにして得たｍ−ヒドロキシ−ｐ−シアノメタク
リルアニリド７６．８ｇ（０，３８モル）を、エチルメ
ククリレーｈ ６８．４ ｇ （０，６０モル）、アク
リル酸１．４４ｇ（０，０２モル）およびα・α′−ア
ゾビスイソブチロニトリル０．７ｇとともに、アセトン
：エタノール（１： ２）の混合溶媒３００ｍ１中に溶
解し、窒素ガス置換した後、６５°Ｃで４時間加熱し、
重合体溶液を得た。この重合体溶液を３ｐの５％Ｈ（Ｊ
水溶液中に注ぎ、生じた白色の沈殿物をｔ濾過し、乾燥
して、白色重合体７５ｇを得た。ＧＰＣで分子量を測定
したら、Ｍ７が４７００、Ｍ、、が３３０００であった
。76.8 g (0.38 mol) of m-hydroxy-p-cyanomethacrylanilide thus obtained were mixed with 68.4 g (0.60 mol) of ethyl meccryl and 1.44 g (0.6 mol) of acrylic acid. 02 mol) and 0.7 g of α・α′-azobisisobutyronitrile in 300 ml of acetone:ethanol (1:2) mixed solvent, purged with nitrogen gas, and heated at 65°C for 4 hours. death,
A polymer solution was obtained. This polymer solution was mixed with 3p of 5% H (J
The resulting white precipitate was filtered and dried to obtain 75 g of a white polymer. When the molecular weight was measured by GPC, M7 was 4,700 and M, 33,000.
５−アミノ−α−ナフビール２２７ｇ、ハイドロキノン
モノメチルエーテル１ｇおよびピリジン２１を混合し、
寒剤を用いて一１０℃に冷却して、メタクリル酸クロラ
イド１１０ｇを撹拌下に滴下した。滴下終了後０〜３℃
で２時間攪拌した。次いで２５℃で２時間攪拌後、反応
液を２０２の氷水中に注入して沈殿を生成させ、これを
ｉ濾過し、水洗して乾燥した。得られた固体をメタノー
ルと５％炭酸ナトリウム水溶液の混合液（１：１）２１
中に加えて４０°Ｃで３０分間攪拌した後、５％塩酸４
１中に注入して多量の沈殿を生成させた。Mix 227 g of 5-amino-α-naf beer, 1 g of hydroquinone monomethyl ether and 21 g of pyridine,
The mixture was cooled to -10° C. using a cryogen, and 110 g of methacrylic acid chloride was added dropwise with stirring. 0~3℃ after completion of dripping
The mixture was stirred for 2 hours. After stirring at 25° C. for 2 hours, the reaction solution was poured into 202 ice water to generate a precipitate, which was filtered, washed with water, and dried. The obtained solid was mixed with a mixture of methanol and 5% sodium carbonate aqueous solution (1:1)21
After stirring at 40°C for 30 minutes, 5% hydrochloric acid 4
1 to produce a large amount of precipitate.
これを吸引濾過後、エタノールで再結晶して、融点２２
３〜２２４℃のＮ−（５−ヒドロキシ−α−ナフチル）
メタクリルアミド２１０ｇを得た。After suction filtration, this was recrystallized with ethanol, and the melting point was 22.
N-(5-hydroxy-α-naphthyl) at 3-224°C
210 g of methacrylamide was obtained.
このようにして得たＮ−（５−ヒドロキシ−α−ナフチ
ル）メタクリルアミド６８ｇ（０，３モル）を、２−ヒ
ドロキシエチルメタクリレート１０ｇ（０，１モル）、
メチルメククリレート３０ ｇ （０，３モル）、アク
リロニトリル１５．９ｇ（０，３モル）およびα・α′
−アヅビスイソブチロニトリル０、５０ ｇとともに、
アセトン：エタノール（１： ２）のｌ捏合Ｙ各課２０
０ｍ＋２に′）容解した。１昇られた）容ン夜を窒素ガ
ス置換した封管中で、６５°Ｃで８時間加熱し、共重合
体溶液を得た。この共重合体溶液をメタノール１００ｍ
Ａで希釈した後、水中に注入し、生じた沈殿物を？濾過
し、乾燥して、白色重合体７０ｇを得た。ＧＰＣで分子
量を測定したら、Ｍｌが９１００．Ｍ、が４８０００で
あった。68 g (0.3 mol) of N-(5-hydroxy-α-naphthyl)methacrylamide thus obtained was mixed with 10 g (0.1 mol) of 2-hydroxyethyl methacrylate,
30 g (0.3 mol) of methyl meccrylate, 15.9 g (0.3 mol) of acrylonitrile and α・α′
- with 0.50 g of azubisisobutyronitrile,
Mixture of acetone:ethanol (1:2) Y 20 for each section
It was dissolved at 0m+2. The mixture was heated at 65°C for 8 hours in a sealed tube purged with nitrogen gas to obtain a copolymer solution. Add this copolymer solution to 100ml of methanol.
After diluting with A, inject into water and remove the resulting precipitate. After filtering and drying, 70 g of a white polymer was obtained. When the molecular weight was measured by GPC, Ml was 9100. M, was 48,000.
比較金戊炎上
合成例１においてｐ−ヒドロキシメタクリルアニリドの
代りに２−ヒドロキシエチルメタクリレートを使用した
以外は、同一の条件で反応を行った。得られた重合体の
分子量をＧＰＣで測定したら、Ｍ、が２３００、Ｍ８が
１５０００であった。The reaction was carried out under the same conditions as Comparative Synthesis Example 1 except that 2-hydroxyethyl methacrylate was used instead of p-hydroxymethacrylanilide. When the molecular weight of the obtained polymer was measured by GPC, M was 2,300 and M8 was 15,000.
比較金炭炎又
ｍ−クレゾール９０ｇ、、ｐ−クレゾール５６ｇ５フエ
ノール５４ｇ、３７％ホルムアルデヒド水ｌ容液１０５
ｇおよびシュウ酸２．５ｇをオイルハスにセントした３
頭コルヘン中に投入し、かくはんしなから昇温した。９
０℃付近で激しく発泡し一時的に冷却した後再び昇温し
、内温を１０５°Ｃにした。約３時間反応後、再び１７
５°Ｃまで昇温し、水を留去した。２時間後２００ ”
Ｃに昇温するとともに１００龍１ｇまで減圧し、残留モ
ノマーを留去した。１０分後反応を止め、反応物をテフ
ロン・バットへ流し出し、固化させた。この樹脂の分子
量をＧＰＣでポリスチレンを標準として測定した。Comparison: 90 g of m-cresol, 56 g of p-cresol, 54 g of phenol, 1 volume of 37% formaldehyde water 105 g
g and 2.5 g of oxalic acid in oil lotus 3
The head was poured into colchen, and the temperature was raised without stirring. 9
It foamed violently at around 0°C, was temporarily cooled, and then raised again to bring the internal temperature to 105°C. After about 3 hours of reaction, 17
The temperature was raised to 5°C and water was distilled off. 200 after 2 hours”
The temperature was raised to C. and the pressure was reduced to 1 g to 100 g to distill off the residual monomer. After 10 minutes, the reaction was stopped, and the reaction product was poured into a Teflon vat and solidified. The molecular weight of this resin was measured by GPC using polystyrene as a standard.
Ｍ、 、Ｍ、の算出は前述と同様にして行った。その結
果、Ｍ７は１３５０、Ｍ、は６７５０であった。The calculations of M, , M, were performed in the same manner as described above. As a result, M7 was 1350 and M was 6750.
ス１貧１１
厚さ０．２４ ｍｍのアルミニウム板を５％水酸化ナト
リウム水溶液中で脱脂処理した後、０．３モル硝酸水溶
液中で、温度３０℃、電流密度５０Ａ／ｄｍ”、処理時
間３０秒間の条件で、電解エツチング処理を行った。次
いで、５％水酸化ナトリウム水溶液でデスマット処理を
施し、しかる後硫酸溶液中で陽極酸化処理を行った。陽
極酸化皮膜量を前述の方法で測定したところ、２０■／
ｄｍｚであった。After degreasing an aluminum plate with a thickness of 0.24 mm in a 5% aqueous sodium hydroxide solution, it was degreased in a 0.3 molar nitric acid aqueous solution at a temperature of 30°C, a current density of 50 A/dm, and a treatment time of 30 Electrolytic etching treatment was carried out under conditions of 2 seconds.Next, desmutting treatment was carried out with a 5% aqueous sodium hydroxide solution, and then anodization treatment was carried out in a sulfuric acid solution.The amount of anodic oxide film was measured using the method described above. Tokoro, 20■/
It was dmz.
次に９０℃の熱水溶液に浸漬し封孔処理を行った。Next, it was immersed in a hot aqueous solution at 90°C for pore sealing treatment.
このようにして得られたアルミニウム支持体に下記の組
成の感光性塗布液を回転塗布機を用いて塗布し、１００
℃で４分間乾燥し、膜厚２４■／ｄｍ”の感光性平版印
刷版を得た。A photosensitive coating solution having the following composition was coated on the aluminum support obtained in this way using a rotary coater, and
It was dried at .degree. C. for 4 minutes to obtain a photosensitive lithographic printing plate having a film thickness of 24 .mu./dm".
得られた感光性平版印刷版を３ｋＨの超高圧水銀灯で６
０ｃｍの距離から３０秒間露光し、次にｐｓ版版木ポジ
型現像液５ＤＰ−１” 〔小西六写真工業■製〕の７倍
希釈液を用いて、２５°Ｃで４５秒間現像処理を行った
。得られた平版印刷版の感度および耐薬品性を測定した
。The obtained photosensitive planographic printing plate was heated with a 3kHz ultra-high pressure mercury lamp for 6 hours.
It was exposed for 30 seconds from a distance of 0 cm, and then developed for 45 seconds at 25°C using a 7-fold dilution of PS printing block positive developer 5DP-1" [manufactured by Konishiroku Photo Industry ■]. The sensitivity and chemical resistance of the obtained lithographic printing plate were measured.
実施例２
合成例１のバインダーの代りに合成例２のバインダーを
使用した以外実施例１と同一の方法により感光性塗布液
（感光液２）を調製し、これを用いて実施例１と同一の
方法で平版印刷版を作製し、同一の測定を行った。Example 2 A photosensitive coating liquid (photosensitive liquid 2) was prepared in the same manner as in Example 1 except that the binder of Synthesis Example 2 was used instead of the binder of Synthesis Example 1, and the same method as in Example 1 was prepared using this. A lithographic printing plate was prepared using the method described above, and the same measurements were performed.
比較班上
合成例１のバインダーの代りに比較合成例２のバインダ
ーを使用した以外実施例１と同一の方法により感光性塗
布液（比較感光液１）を調製し、これを用いて実施例１
と同一の方法で平版印刷版を作製し、同一の測定を行っ
た。Comparative Group A photosensitive coating liquid (comparative photosensitive liquid 1) was prepared in the same manner as in Example 1 except that the binder of Comparative Synthesis Example 2 was used instead of the binder of Synthesis Example 1.
A lithographic printing plate was prepared in the same manner as described above, and the same measurements were performed.
実施例１、実施例２および比較例１の測定結果を表１に
示す。Table 1 shows the measurement results of Example 1, Example 2, and Comparative Example 1.
表１から本発明の印刷版は耐薬品性（含ＵＶインキ適性
）が極めて良好であることがわかる。Table 1 shows that the printing plate of the present invention has extremely good chemical resistance (suitability for UV inks).
叉施斑ユ
実施例１の平版印刷版の印刷適性、現像性および耐剛力
について試験をした。The lithographic printing plate of Example 1 was tested for printability, developability, and stiffness resistance.
印刷適性については、平版印刷版を枚葉オフセット印刷
機にかけ、上質紙に印刷を行って地汚れの有無を調べる
ことにより評価した。印刷の結果、地汚れは全く発生せ
ず、良好な印刷物を得ることができた。これにより印刷
適性が優れていることがわかる。Printability was evaluated by applying the lithographic printing plate to a sheet-fed offset printing machine, printing on high-quality paper, and examining the presence or absence of scumming. As a result of printing, there was no background smudge at all, and a good printed matter could be obtained. This shows that the printability is excellent.
現像性を評価するために、４０ ’Ｃの温度、８０％の
湿度で７日間感光性平版印刷版の強制劣化を行い、その
後で露光し、４ｍ′／βの５ＤＰ−１疲労現像液（７倍
希釈）で現像し、印刷を行った。To evaluate the developability, forced aging of photosensitive lithographic printing plates was carried out for 7 days at a temperature of 40'C and a humidity of 80%, after which they were exposed to light and treated with 4 m'/β of 5DP-1 fatigue developer (7 The film was developed with a double dilution) and printed.
その結果地汚れは発生せず、良好な印刷物が得られた。As a result, no scumming occurred and good printed matter was obtained.
これにより現像性に優れていることがわかる。This shows that the developability is excellent.
さらに耐剛力を評価するために、下記の条件でＵＶイン
キによる印刷を行った。Furthermore, in order to evaluate the stiffness resistance, printing with UV ink was performed under the following conditions.
（ＵＶインキによる印刷条件）
印 刷 機 ：ハフダスターＣＤＸ−９００印刷インキ
：東洋フラッシュドライ−ＯＬ −［ＡＩ）（東洋イ
ンキ社製）
レジューサｍ：東洋フラッシュドライレジューサ−ｏｐ
（東洋インキ社製）
祇 ：上質紙
印刷スピード：’ｙｏｏｏ枚／時
その結果、５万枚を刷了し、印刷物は地汚れもなく良好
であった。(Printing conditions using UV ink) Printing machine: Huff Duster CDX-900 Printing ink: Toyo Flash Dry-OL-[AI] (manufactured by Toyo Ink Co., Ltd.) Reducer m: Toyo Flash Dry Reducer-OP
(manufactured by Toyo Ink Co., Ltd.) G: High-quality paper Printing speed: 'yooo sheets/hour As a result, 50,000 sheets were printed, and the printed matter was in good condition without background stains.
これに対し、比較例１の平版印刷版を用いて、同一条件
でＵＶ印刷を行ったところ、印刷開始後まもなく印刷版
の画像が消失した。On the other hand, when UV printing was performed using the lithographic printing plate of Comparative Example 1 under the same conditions, the image on the printing plate disappeared shortly after printing started.
比較例２
実施例１のバインダーを合成例１のものから比較合成例
１のものに変更しくｐ−ヒドロキシメタクリルアニリド
（ｌＩｙＰＭＡ） 単位を２−ヒドロキシエチルメタク
リレ−１・に変更し）、その他は実施例１と同じ組成に
して、感光性平版印刷版を得た。Comparative Example 2 The binder of Example 1 was changed from that of Synthesis Example 1 to that of Comparative Synthesis Example 1, and the p-hydroxymethacrylanilide (lIyPMA) unit was changed to 2-hydroxyethylmethacryle-1. A photosensitive lithographic printing plate was obtained using the same composition as in Example 1.
実施例１と同様に露光・現像を行なったが、現像できな
かった。これによりフェノール性水酸基が必須であるこ
とがわかる。Exposure and development were carried out in the same manner as in Example 1, but development was not possible. This shows that the phenolic hydroxyl group is essential.
几孤炎ユ
実施例１の怒光体を合成例１のものから比較合成例１の
ものに変更した以外は、同じ組成の感光性平版印刷版を
１７た。A photosensitive lithographic printing plate having the same composition was prepared except that the photoreceptor of Example 1 was changed from that of Synthesis Example 1 to that of Comparative Synthesis Example 1.
この印刷版の現像性を評価するために、露光前に強制劣
化（４０°Ｃ１８０％、７日）させ、実施例１と同様に
露光し、４ｄ／！の５ＤＰ−１疲労現像液（７倍希釈）
で現像し、現像インキ（ＳＰＯ−１）盛をした。その結
果汚れが認められた。In order to evaluate the developability of this printing plate, it was forcibly aged (40°C, 180%, 7 days) before exposure, exposed in the same manner as in Example 1, and 4d/! 5DP-1 fatigue developer (7 times diluted)
The film was developed and coated with developing ink (SPO-1). As a result, stains were observed.
犬旌±工２５． ６
厚さ０．３ ｘｖｈのアルミニウム板を５％水酸化ナト
リウム水溶液中で脱脂処理を行った後、０．５モル塩酸
水溶液中において、温度２５℃、電流密度６０ Ａ／ｄ
ｍ２−処理時間３０秒間の条件で電解エツチング処理を
行った。次いで５％水酸化ナトリウム水溶液でデスマッ
ト処理を施した後、硫酸溶液中で陽極酸化処理を行った
。陽極酸化皮膜量を前述の方法で測定したところ、２７
ｍｇ／ｄｍ”であった。次に９０°Ｃの熱水溶液に浸漬
し、封孔処理を行った。続いて、得られたアルミニウム
支持体に下記の組成の感光性塗布液を回転塗布機を用い
て塗布し、１００″Ｃで４分間乾燥し、膜厚２４■／ｄ
ｍ２の感光性平版印刷版を得た。Inujo ± engineering 25. 6 After degreasing an aluminum plate with a thickness of 0.3 x vh in a 5% aqueous sodium hydroxide solution, it was heated at a temperature of 25°C and a current density of 60 A/d in a 0.5 molar aqueous hydrochloric acid solution.
Electrolytic etching treatment was performed under conditions of m2-treatment time of 30 seconds. Next, a desmut treatment was performed with a 5% aqueous sodium hydroxide solution, and then an anodization treatment was performed in a sulfuric acid solution. When the amount of anodic oxide film was measured using the method described above, it was found to be 27
mg/dm". Next, it was immersed in a hot aqueous solution at 90°C for pore sealing. Subsequently, a photosensitive coating solution having the following composition was applied to the obtained aluminum support using a spin coating machine. The film was coated using
A photosensitive lithographic printing plate of m2 was obtained.
屋友淡主−土一】
合成例２のＳ光体 ３０部合成例１
．３．４のバインダー ７０部ビクトリアブ
ルーＢ ＯＨ１部
メチルセロソルブ ７００部実施例１
と同様に露光・現像し、平版印刷版を得た。現像した印
刷版を用い、下記の印刷条件で、ＵＶインキによる印刷
を行なった。[Yatomo Tanji - Tsuchiichi] S light material of Synthesis Example 2 30 parts Synthesis Example 1
．． 3.4 Binder 70 parts Victoria Blue B 1 part OH Methyl Cellosolve 700 parts Example 1
Exposure and development were carried out in the same manner as above to obtain a lithographic printing plate. Using the developed printing plate, printing with UV ink was performed under the following printing conditions.
（ＩＪＶインキによる印刷条件）
印 刷 機 −へマダスターＣＤＸ−９００印刷インキ
二ニューダイキュア・Ｚプロセス紅（大日本インキ化
学社製）
レジューサー：ダイキュアＡＫレジューサ−（大日本イ
ンキ化学社製）
紙 ：上質紙
印刷スピードニア０００枚／時
全て３万枚を刷了し、良好なＵＶインキ適性であること
がわかった。(Printing conditions using IJV ink) Printing machine - Hema Duster CDX-900 printing ink Ninew Daicure Z Process Red (manufactured by Dainippon Ink Chemicals) Reducer: Daicure AK Reducer (manufactured by Dainippon Ink Chemicals) Paper :High-quality paper printing speed Near 000 sheets/hour 30,000 sheets were printed in all cases, and it was found to have good suitability for UV ink.
性平版印刷版は著しく向上した耐薬品性を有し、バーニ
ングなしでもＵ■インキ印印加可能で、しかも現像ラチ
チュードが良好で、地汚れが発生しないという優れた効
果を奏するものである。The lithographic printing plate has significantly improved chemical resistance, can be applied with U⋯ ink without burning, has good development latitude, and exhibits excellent effects in that scumming does not occur.
Claims (4)
の重縮合樹脂のｏ−ナフトキノンジアジドスルホン酸エ
ステルと、 （Ｂ）下記一般式〔 I 〕により表わされる構造単位を
有する高分子化合物、 ▲数式、化学式、表等があります▼・・・〔 I 〕 （式中、Ｒ＿１およびＲ＿２は水素原子、ハロゲン原子
、アルキル基、アリール基またはカルボン酸基であり、
Ｒ＿３は水素原子、ハロゲン原子、アルキル基またはア
リール基であり、Ｒ＿４は水素原子、アルキル基、アリ
ール基またはアラルキル基であり、Ｙは置換基を有して
もよい芳香族基であり、Ｘは窒素原子と前記芳香族基の
炭素原子とを連結する２価の有機基であり、ｎは０〜５
の整数である。）とを含有する感光層を支持体上に有す
ることを特徴とするポジ型感光性平版印刷版。(1) (A) o-naphthoquinonediazide sulfonic acid ester of polycondensation resin of polyhydric phenol and aldehyde or ketone, (B) polymer compound having a structural unit represented by the following general formula [I], ▲Math. , chemical formulas, tables, etc.▼...[I] (In the formula, R_1 and R_2 are hydrogen atoms, halogen atoms, alkyl groups, aryl groups, or carboxylic acid groups,
R_3 is a hydrogen atom, a halogen atom, an alkyl group, or an aryl group; R_4 is a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group; Y is an aromatic group that may have a substituent; It is a divalent organic group that connects the nitrogen atom and the carbon atom of the aromatic group, and n is 0 to 5.
is an integer. ) A positive-working photosensitive lithographic printing plate, characterized in that it has a photosensitive layer on a support.
印刷版において、前記一般式〔 I 〕中のＹは置換基を
有してもよいフェニレン基または置換基を有してもよい
ナフチレン基であることを特徴とするポジ型感光性平版
印刷版。(2) In the positive-working photosensitive lithographic printing plate according to claim 1, Y in the general formula [I] is a phenylene group that may have a substituent or a phenylene group that may have a substituent. A positive-working photosensitive lithographic printing plate characterized by a good naphthylene group.
感光性平版印刷版において、前記ｏ−ナフトキノンジア
ジドスルホン酸エステルは前記感光層の５〜４０重量％
であることを特徴とするポジ型感光性平版印刷版。(3) In the positive-working photosensitive lithographic printing plate according to claim 1 or 2, the o-naphthoquinonediazide sulfonic acid ester is 5 to 40% by weight of the photosensitive layer.
A positive photosensitive lithographic printing plate characterized by:
載のポジ型感光性平版印刷版において、前記支持体は陽
極酸化処理されたアルミニウム基板であることを特徴と
するポジ型感光性平版印刷版。(4) In the positive-working photosensitive lithographic printing plate according to any one of claims 1 to 3, the support is an anodized aluminum substrate. Lithographic printing plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12289986A JPH0658531B2 (en) | 1986-05-28 | 1986-05-28 | Photosensitive lithographic printing plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12289986A JPH0658531B2 (en) | 1986-05-28 | 1986-05-28 | Photosensitive lithographic printing plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62279327A true JPS62279327A (en) | 1987-12-04 |
| JPH0658531B2 JPH0658531B2 (en) | 1994-08-03 |
Family
ID=14847373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12289986A Expired - Lifetime JPH0658531B2 (en) | 1986-05-28 | 1986-05-28 | Photosensitive lithographic printing plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0658531B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63226641A (en) * | 1986-12-15 | 1988-09-21 | Fuji Photo Film Co Ltd | Photosensitive composition |
| JPS6421440A (en) * | 1987-07-17 | 1989-01-24 | Mitsubishi Chem Ind | Photosensitive planographic printing plate |
| JPH0224662A (en) * | 1988-07-13 | 1990-01-26 | Konica Corp | Method of processing planographic printing plate |
| US5182183A (en) * | 1987-03-12 | 1993-01-26 | Mitsubishi Kasei Corporation | Positive photosensitive planographic printing plates containing specific high-molecular weight compound and photosensitive ester of O-napthoquinonediazidosulfonic acid with polyhydroxybenzophenone |
| EP1577330A1 (en) * | 2003-08-22 | 2005-09-21 | Okamoto Chemical Industry Co., Ltd | Copolymer, image-froming composition and plate for lithography |
-
1986
- 1986-05-28 JP JP12289986A patent/JPH0658531B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63226641A (en) * | 1986-12-15 | 1988-09-21 | Fuji Photo Film Co Ltd | Photosensitive composition |
| US5182183A (en) * | 1987-03-12 | 1993-01-26 | Mitsubishi Kasei Corporation | Positive photosensitive planographic printing plates containing specific high-molecular weight compound and photosensitive ester of O-napthoquinonediazidosulfonic acid with polyhydroxybenzophenone |
| JPS6421440A (en) * | 1987-07-17 | 1989-01-24 | Mitsubishi Chem Ind | Photosensitive planographic printing plate |
| JPH0224662A (en) * | 1988-07-13 | 1990-01-26 | Konica Corp | Method of processing planographic printing plate |
| EP1577330A1 (en) * | 2003-08-22 | 2005-09-21 | Okamoto Chemical Industry Co., Ltd | Copolymer, image-froming composition and plate for lithography |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0658531B2 (en) | 1994-08-03 |
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| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |