JPH0456863A - Plate making method for planographic printing plate - Google Patents
Plate making method for planographic printing plateInfo
- Publication number
- JPH0456863A JPH0456863A JP16526790A JP16526790A JPH0456863A JP H0456863 A JPH0456863 A JP H0456863A JP 16526790 A JP16526790 A JP 16526790A JP 16526790 A JP16526790 A JP 16526790A JP H0456863 A JPH0456863 A JP H0456863A
- Authority
- JP
- Japan
- Prior art keywords
- printing plate
- photosensitive
- photosensitive layer
- acid
- reduced pressure
- 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
- 238000000034 method Methods 0.000 title claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- 239000010410 layer Substances 0.000 claims abstract description 18
- 230000002829 reductive effect Effects 0.000 claims abstract description 12
- 239000011241 protective layer Substances 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000035699 permeability Effects 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229920000620 organic polymer Polymers 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 230000035945 sensitivity Effects 0.000 abstract description 12
- 229920000642 polymer Polymers 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract 2
- 238000006467 substitution reaction Methods 0.000 abstract 2
- -1 polyethylene terephthalate Polymers 0.000 description 21
- 239000000203 mixture Substances 0.000 description 18
- 238000011282 treatment Methods 0.000 description 12
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 10
- 239000000975 dye Substances 0.000 description 10
- 239000000600 sorbitol Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000178 monomer Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000012719 thermal polymerization Methods 0.000 description 5
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 3
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OAKFFVBGTSPYEG-UHFFFAOYSA-N (4-prop-2-enoyloxycyclohexyl) prop-2-enoate Chemical compound C=CC(=O)OC1CCC(OC(=O)C=C)CC1 OAKFFVBGTSPYEG-UHFFFAOYSA-N 0.000 description 1
- ABFQGXBZQWZNKI-UHFFFAOYSA-N 1,1-dimethoxyethanol Chemical compound COC(C)(O)OC ABFQGXBZQWZNKI-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- OGBWMWKMTUSNKE-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CCCCCC(OC(=O)C(C)=C)OC(=O)C(C)=C OGBWMWKMTUSNKE-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- APJRQJNSYFWQJD-GGWOSOGESA-N 2-[(e)-but-2-enoyl]oxyethyl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OCCOC(=O)\C=C\C APJRQJNSYFWQJD-GGWOSOGESA-N 0.000 description 1
- APJRQJNSYFWQJD-GLIMQPGKSA-N 2-[(z)-but-2-enoyl]oxyethyl (z)-but-2-enoate Chemical compound C\C=C/C(=O)OCCOC(=O)\C=C/C APJRQJNSYFWQJD-GLIMQPGKSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
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- YBKWKURHPIBUEM-UHFFFAOYSA-N 2-methyl-n-[6-(2-methylprop-2-enoylamino)hexyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCCCCCCNC(=O)C(C)=C YBKWKURHPIBUEM-UHFFFAOYSA-N 0.000 description 1
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- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
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- FQMIAEWUVYWVNB-UHFFFAOYSA-N 3-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OC(C)CCOC(=O)C=C FQMIAEWUVYWVNB-UHFFFAOYSA-N 0.000 description 1
- OBYOFMNDYOOIPV-UHFFFAOYSA-N 3-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C=C1C(C)(C)C OBYOFMNDYOOIPV-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- KTZOPXAHXBBDBX-FCXRPNKRSA-N 4-[(e)-but-2-enoyl]oxybutyl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OCCCCOC(=O)\C=C\C KTZOPXAHXBBDBX-FCXRPNKRSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 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
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は平版印刷版の製版方法に関するものである。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for making a lithographic printing plate.
付加重合性不飽和結合を有する重合可能な化合物と光重
合開始剤と更に必要に応じて適当な皮膜形成能を有する
結合剤、熱重合禁止剤を混和させた感光性組成物を用い
て、写真的手法により画像の複製を行なう方法は、現在
知られるところである。すなわち、米国特許第2.92
7.022号、同2、902.356号あるいは同3.
870.524号に記載されているように、この種の感
光性組成物は光照射により光重合を起こし、硬化し不溶
化することから、該感光性組成物を適当な皮膜となし、
所望の陰画像を通して光照射を行ない、適当な溶媒によ
り未露光部のみを除去する(以下、単に現像と呼ぶ)こ
とにより所望の光重合性組成物の硬化画像を形成するこ
とができる。このタイプの感光性組成物は印刷版等を作
成するために使用されるものとして極めて有用であるこ
とは論をまたない。A photosensitive composition is prepared by mixing a polymerizable compound having an addition-polymerizable unsaturated bond, a photopolymerization initiator, and, if necessary, a binder having an appropriate film-forming ability and a thermal polymerization inhibitor. Methods for duplicating images using manual techniques are currently known. That is, U.S. Patent No. 2.92
No. 7.022, No. 2, No. 902.356 or No. 3.
As described in No. 870.524, this type of photosensitive composition undergoes photopolymerization, hardens, and becomes insolubilized by irradiation with light.
A desired cured image of the photopolymerizable composition can be formed by irradiating light through the desired negative image and removing only the unexposed areas using a suitable solvent (hereinafter simply referred to as development). It goes without saying that this type of photosensitive composition is extremely useful for making printing plates and the like.
また、近年、紫外線に対する高感度化や、レーザーを用
いて画像を形成する方法が検討され、印刷版作成におけ
るUVプロジェクション露光法、レーザー直接製版、レ
ーザーファクシミリ、ホログラフィ−等が既に実用の段
階にあり、これらに使用できる高感度な感光材料が開発
されている。In addition, in recent years, increased sensitivity to ultraviolet rays and methods of forming images using lasers have been studied, and methods such as UV projection exposure for printing plate creation, laser direct plate making, laser facsimile, and holography are already in practical use. , high-sensitivity photosensitive materials that can be used in these applications have been developed.
これらの光重合性感光層はラジカル重合によって反応が
進行するが、その際酸素によって重合は阻害される。そ
の為に特開昭50−59101号公報には、光重合性感
光層上にポリエチレンテレフタレート、セロファン、ポ
リ塩化ビニリデン、ポリ塩化ビニル、ポリビニルアルコ
ール、ポリプロピレンやポリエチレン等の酸素透過防止
性の被覆層を設けることが記載されている。In these photopolymerizable photosensitive layers, the reaction proceeds by radical polymerization, but the polymerization is inhibited by oxygen. For this purpose, JP-A-50-59101 discloses that an oxygen permeation-preventing coating layer such as polyethylene terephthalate, cellophane, polyvinylidene chloride, polyvinyl chloride, polyvinyl alcohol, polypropylene, or polyethylene is provided on the photopolymerizable photosensitive layer. It is stated that it should be provided.
また、特開昭63−262645号には、染料存在下予
備露光により感光層中の溶存酸素を1重項状態に変換し
、重合を阻害しないようにする試みがなされている。Further, in JP-A-63-262645, an attempt has been made to convert dissolved oxygen in the photosensitive layer into a singlet state by preliminary exposure in the presence of a dye so as not to inhibit polymerization.
しかし、この系では、感度が不十分であり、また、予備
露光に大きな光量を必要とした。However, this system had insufficient sensitivity and required a large amount of light for preliminary exposure.
本発明の目的は高感度かつ調子再現性にすぐれた平版印
刷版の製版方法を提供することである。An object of the present invention is to provide a method for making a lithographic printing plate with high sensitivity and excellent tone reproducibility.
本発明者は上記目的を達成すべく、鋭意研究を重ねた結
果
1)支持体上に、
ll)活性光線により光重合が可能な少なくとも1個の
エチレン性不飽和結合を有する重合可能な化合物と光重
合開始剤と線状有機高分子重合体とを含む光重合性感光
層と、
111)酸素透過度が30〜300cc/m’・day
−atm(25℃/湿度35%)である透明な保護層を
設けてなる感光性平版印刷版を、減圧下に置き、感光層
中の溶存酵素を除去したのち、窒素ガスで置換後、画像
露光、現像することにより、高感度かつ調子再現性にす
ぐれた平版印刷版が得られることを見比し、本発明に到
達したものである。In order to achieve the above object, the present inventor has conducted extensive research and as a result 1) on a support, ll) a polymerizable compound having at least one ethylenically unsaturated bond that can be photopolymerized by actinic rays; a photopolymerizable photosensitive layer containing a photopolymerization initiator and a linear organic polymer; 111) an oxygen permeability of 30 to 300 cc/m'day;
-atm (25°C/35% humidity), a photosensitive lithographic printing plate provided with a transparent protective layer is placed under reduced pressure to remove dissolved enzymes in the photosensitive layer, and after replacing with nitrogen gas, images are formed. The present invention was developed based on the fact that a lithographic printing plate with high sensitivity and excellent tone reproducibility can be obtained by exposure and development.
本発明においては、感光性・平版印刷版を減圧下に置く
ことによって、感光層中に含まれる溶存酸素を除き、酸
素による重合禁止効果をなくすことにより、高感度化お
よび調子再現性の良化が可能となる。また減圧による溶
存酸素除去後、空気中の酸素が再び感光層中に流入する
のを防ぐため、該感光層の上に、減圧により酸素を除く
ことは可能であるが、常圧下では酸素遮断性を有する透
明保護層を設ける。この保護層は、酸素透過度が30〜
300CC/ml−day−atm(25℃/湿度35
%)のものである。酸素透過度がこの範囲外のものでは
、減圧下における酸素除去、常圧下における酸素遮断を
適切に行うことができない。In the present invention, by placing the photosensitive lithographic printing plate under reduced pressure, dissolved oxygen contained in the photosensitive layer is removed and the polymerization inhibiting effect caused by oxygen is eliminated, thereby increasing sensitivity and improving tone reproducibility. becomes possible. In addition, in order to prevent oxygen in the air from flowing into the photosensitive layer again after removing dissolved oxygen by reducing the pressure, it is possible to remove oxygen by reducing the pressure on the photosensitive layer, but under normal pressure the oxygen barrier property A transparent protective layer is provided. This protective layer has an oxygen permeability of 30~
300CC/ml-day-atm (25℃/humidity 35
%)belongs to. If the oxygen permeability is outside this range, oxygen removal under reduced pressure and oxygen blocking under normal pressure cannot be performed appropriately.
減圧条件は、保護層の酸素透過度により任意に設定する
ことができるが、より好ましくは、5 mmHg以下で
1分以上静置することである。減圧状態から窒素ガスで
常圧にもどしたのち、窒素雰囲気下で1分以上静置する
ことが好ましい。The reduced pressure conditions can be arbitrarily set depending on the oxygen permeability of the protective layer, but it is more preferable to leave it standing at 5 mmHg or less for 1 minute or more. It is preferable to return the pressure from the reduced pressure state to normal pressure using nitrogen gas, and then leave it standing in a nitrogen atmosphere for 1 minute or more.
本発明では、真空容器から感光性平版印刷版を取り出し
てから10分以内に画像露光を行なうことが好ましく、
より好ましくは、5分以内に行なうことである。In the present invention, image exposure is preferably carried out within 10 minutes after taking out the photosensitive lithographic printing plate from the vacuum container,
More preferably, it is carried out within 5 minutes.
本発明では必要に応じ、画像露光中又は画像露光後、加
熱することにより、調子再現性を損うことなく、高感度
化することができる。加熱温度は200℃以下が好まし
く、より好ましくは、40〜150℃である。In the present invention, if necessary, by heating during or after image exposure, sensitivity can be increased without impairing tone reproducibility. The heating temperature is preferably 200°C or less, more preferably 40 to 150°C.
本発明に使用する支持体としては、寸度的に安定な板状
物が用いられる。該寸度的に安定な板状物としては、紙
、プラスチック(例えばポリエチレン、ポリプロピレン
、ポリスチレンなど)がラミネートされた紙、また、例
えばアルミニウム(アルミニウム合金も含む。)、亜鉛
、銅などのような金属の板、さらに、例えば二酢酸セル
ロース、三酢酸セルロース、プロピオン酸セルロース、
酪酸セルロース、酢酸酪酸セルロース、硝酸セルロース
、ポリエチレンテレフタレート、ポリエチレン、ポリス
チレン、ポリプロピレン、ポリカーボネート、ポリビニ
ルアセタールなどのようなプラスチックのフィルム、上
記の如き金属がラミネートもしくは蒸着された紙もしく
はプラスチックフィルムなどがあげられる。これらの支
持体のうち、アルミニウム板は寸度的に著しく安定であ
り、しかも安価であるので特に好ましい。更に、特公昭
48−18327号に記載されているようなポリエチレ
ンテレフタレートフィルム上にアルミニウムシートが結
合された複合体シートも好ましい。As the support used in the present invention, a dimensionally stable plate-like material is used. Examples of the dimensionally stable plate-like material include paper, paper laminated with plastic (for example, polyethylene, polypropylene, polystyrene, etc.), and materials such as aluminum (including aluminum alloys), zinc, copper, etc. Metal plates, furthermore, for example cellulose diacetate, cellulose triacetate, cellulose propionate,
Examples include plastic films such as cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., and paper or plastic films laminated or vapor-deposited with metals such as those mentioned above. Among these supports, aluminum plates are particularly preferred because they are extremely dimensionally stable and inexpensive. Furthermore, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 is also preferred.
また金属、特にアルミニウムの表面を有する支持体の場
合には、砂目立て処理、珪酸ソーダ、弗化ジルコニウム
酸カリウム、燐酸塩等の水溶液への浸漬処理、あるいは
陽極酸化処理などの表面処理がなされていることが好ま
しい。In addition, in the case of a support having a metal surface, especially aluminum, surface treatments such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment are performed. Preferably.
さらに、砂目立てしたのちに珪酸ナトリウム水溶液に浸
漬処理されたアルミニウム板が好ましく使用できる。特
公昭47−5125号に記載されているようにアルミニ
ウム板を陽極酸化処理したのちに、アルカリ金属珪酸塩
の水溶液に浸漬処理したものが好適に使用される。上記
陽極酸化処理は、例えば、燐酸、クロム酸、硫酸、硼酸
等の無機酸、若しくは蓚酸、スルファミン酸等の有機酸
またはこれらの塩の水溶液又は非水溶液の単独又は二種
以上を組み合わせた電解液中でアルミニウム板を陽極と
して電流を流すことにより実施される。Furthermore, an aluminum plate that has been grained and then immersed in an aqueous sodium silicate solution can be preferably used. As described in Japanese Patent Publication No. 47-5125, an aluminum plate which is anodized and then immersed in an aqueous solution of an alkali metal silicate is preferably used. The above anodizing treatment can be carried out using an electrolytic solution, for example, of an aqueous or non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, or a combination of two or more thereof. This is carried out by passing an electric current through the aluminum plate as an anode.
また、米国特許第3.658.662号に記載されてい
るようなシリケート電着も有効である。Also effective is silicate electrodeposition as described in US Pat. No. 3,658,662.
更に、特公昭46−27481号、特開昭525860
2号、特開昭52−30503号に開示されているよう
な電解ダレインを施した支持体と、上記陽極酸化処理お
よび珪酸ソーダ処理を組合せた表面処理も有用である。Furthermore, Japanese Patent Publication No. 46-27481, Japanese Patent Publication No. 525860
Also useful is a surface treatment that combines a support subjected to electrolytic duplexing as disclosed in No. 2, JP-A-52-30503, and the above-mentioned anodic oxidation treatment and sodium silicate treatment.
また、特開昭56−28893号に開示されているよう
な機械的粗面化、化学的エツチング、電解ダレイン、陽
極酸化処理さらに珪酸ソーダ処理を順に行ったものも好
適である。Also suitable are those which have been sequentially subjected to mechanical roughening, chemical etching, electrolytic etching, anodic oxidation, and sodium silicate treatment as disclosed in JP-A No. 56-28893.
更に、これらの処理を行った後に、水溶性の樹脂、たと
えばポリビニルホスホン酸、スルホン酸基を側鎖に有す
る重合体および共重合体、ポリアクリル酸、水溶性金属
塩(例えば硼酸亜鉛)もしくは、黄色染料、アミン塩等
を下塗りしたものも好適である。Furthermore, after these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having sulfonic acid groups in their side chains, polyacrylic acid, water-soluble metal salts (e.g. zinc borate), or Undercoating with yellow dye, amine salt, etc. is also suitable.
これらの親水化処理は、支持体の表面を親水性とするた
めに施される以外に、その上に設けられる光重合性組成
物の有害な反応を防ぐため、かつ感光層の密着性の向上
環のために施されるものである。These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions of the photopolymerizable composition provided thereon, and to improve the adhesion of the photosensitive layer. It is done for the ring.
本発明に使用される活性光線により光重合が可能な少な
くとも1個のエチレン性不飽和結合を有する重合可能な
化合物は、末端エチレン性不飽和結合を少なくとも1個
、好ましくは2個以上有する化合物から選ばれる。The polymerizable compound having at least one ethylenically unsaturated bond that can be photopolymerized by actinic rays used in the present invention is a compound having at least one terminal ethylenically unsaturated bond, preferably two or more terminal ethylenically unsaturated bonds. To be elected.
例えばモノマー、プレポリマー、すなわち2量体、3量
体およびオリゴマー、又はそれらの混合物ならびにそれ
らの共重合体などの化学的形態をもつものである。モノ
マーおよびその共重合体の例としては、不飽和カルボン
酸(例えば、アクリル酸、メタクリル酸、イタコン酸、
クロトン酸、イソクロトン酸、マレイン酸など)と脂肪
族多価アルコール化合物とのエステル、不飽和カルボン
酸と脂肪族多価アミン化合物とのアミド等があげられる
。For example, it has chemical forms such as monomers, prepolymers, ie, dimers, trimers, and oligomers, or mixtures thereof, and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid,
Examples include esters of crotonic acid, isocrotonic acid, maleic acid, etc.) and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds.
脂肪族多価アルコール化合物と不飽和カルボン酸とのエ
ステルの千ツマ−の具体例としては、アクリル酸エステ
ルとして、エチレングリコールジアクリレート、トリエ
チレングリコールジアクリレート、1.3−ブタンジオ
ールジアクリレート、テトラメチレングリコールジアク
リレート、プロピレングリコールジアクリレート、ネオ
ペンチルグリコールジアクリレート、トリメチロールプ
ロパントリアクリレート、トリメチロールプロパントリ
(アクリロイルオキシプロピル)エーテル、トリメチ
ロールエタントリアクリレート、ヘキサンジオールジア
クリレート、1.4−シクロヘキサンジオールジアクリ
レート、テトラエチレングリコールジアクリレート、ペ
ンタエリスリトールジアクリレート、ペンタエリスリト
ールトリアクリレート、ペンタエリスリトールテトラア
クリレート、ジペンタエリスリトールジアクリレート、
ジペンタエリスリトールへキサアクリレート、ソルビト
ールトリアクリレート、ソルビトールテトラアクリレー
ト、ソルビトールペンタアクリレート、ソルビトールへ
キサアクリレート、トリ (アクリロイルオキシエチル
)イソシアヌレート、ポリエステルアクリレートオリコ
マ−等がある。Specific examples of esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetraethylene glycol diacrylate. Methylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri(acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate,
Examples include dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri(acryloyloxyethyl)isocyanurate, polyester acrylate oligomer, and the like.
メタクリル酸エステルとしては、テトラメチレングリコ
ールジメタクリレート、トリエチレングリコールジメタ
クリレート、ネオペンチルグリコールジメタクリレート
、トリメチロールプロパントリメタクリレート、トリメ
チロールエタントリメタクリレート、エチレングリコー
ルジメタクリレート、1.3−ブタンジオールジメタク
リレート、ヘキサンジオールジメタクリレート、ペンタ
エリスリトールジメタクリレート、ペンタエリスリトー
ルトリメタクリレート、ペンタエリスリトールテトラメ
タクリレート、ジペンタエリスリトールジメタクリレー
ト、ジペンタエリスリトールへキサメタクリレート、ソ
ルビトールトリメタクリレート、ソルビトールテトラメ
タクリレート、ビス[p−(3−メタクリルオキシ−2
−ヒドロキシプロポキシ)フェニル〕ジメチルメタン、
ビス−[p−(アクリルオキシエトキシ)フェニルフジ
メチルメタン等がある。Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis[p-(3-methacryloxy) -2
-hydroxypropoxy)phenyl]dimethylmethane,
Examples include bis-[p-(acryloxyethoxy)phenylfudimethylmethane.
イタコン酸エステルとしては、エチレングリコールシイ
タコネート、プロピレングリコールシイタコネート、1
.3−ブタンジオールシイタコネート、1,4−ブタン
ジオールシイタコネート、テトラメチレングリコールシ
イタコネート、ペンタエリスリトールシイタコネート、
ソルビトールテトライタコネート等がある。As the itaconic acid ester, ethylene glycol shitaconate, propylene glycol shitaconate, 1
.. 3-butanediol shiitaconate, 1,4-butanediol shiitaconate, tetramethylene glycol shiitaconate, pentaerythritol shiitaconate,
Examples include sorbitol tetrataconate.
クロトン酸エステルとしては、エチレングリコールジク
ロトネート、テトラメチレングリコールジクロトネート
、ペンタエリスリトールジクロトネート、ソルビトール
テトラマレートネート等がある。Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetramaleate.
イソクロトン酸エステルとしては、エチレングリコール
ジイソクロトネート、ペンタエリスリトールジインクロ
トネート、ソルビトールテトライソクロトネート等があ
る。Isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diincrotonate, sorbitol tetraisocrotonate, and the like.
マレイン酸エステルとしては、エチレングリコールシマ
レート、トリエチレングリコールシマレート、ペンタエ
リスリトールシマレート、ソルビトールテトラマレート
等がある。Examples of maleic esters include ethylene glycol simarate, triethylene glycol simarate, pentaerythritol simarate, and sorbitol tetramaleate.
さらに、前述のエステルモノマーの混合物もあげること
ができる。Furthermore, mixtures of the aforementioned ester monomers may also be mentioned.
また、脂肪族多価アミン化合物と不飽和カルボン酸との
アミドの千ツマ−の具体例としては、メチレンビス−ア
クリルアミド、メチレンビス−メタクリルアミド、1.
6−へキサメチレンビスアクリルアミド、1.6−へキ
サメチレンビスメタクリルアミド、ジエチレントリアミ
ントリスアクリルアミド、キシリレンビスアクリルアミ
ド、キシリレンビスメタクリルアミド等がある。Specific examples of amides of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1.
Examples include 6-hexamethylenebisacrylamide, 1,6-hexamethylenebismethacrylamide, diethylenetriamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like.
その他の例としては、特公昭48−41708号公報中
に記載されている1分子に2個以上のイソシアネート基
を有するポリイソシアネート化合物に、下記の一般式(
A)で示される水酸基を含有するビニルモノマーを付加
せしめた1分子中に2個以上の重合性ビニル基を含有す
るビニルウレタン化合物等があげられる。As another example, the following general formula (
Examples include vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule to which a vinyl monomer containing a hydroxyl group shown in A) is added.
[1:H,=C(R)COOCH,口H(R’ )叶
(A)(ただし、RおよびR′
はHあるいはCH3を示す。)
また、特開昭51−37193号に記載されているよう
なウレタンアクリレート類、特開昭4864183号、
特公昭49−43191号、特公昭52−30490号
各公報明細載されているようなポリエステルアクリレー
ト類、エポキシ樹脂と(メタ)アクリル酸を反応させた
エポキシアクリレート類等の多官能のアクリレートやメ
タクリレートをあげることができる。さらに日本接着協
会誌vol、20、No、 7.300〜308ページ
(1984年)に光硬化性モノマーおよびオリコマ−と
して紹介されているものも使用することができる。なお
、これらの使用量は、全成分に対して5〜90重量%(
以下%と略称する。)、好ましくは10〜70%である
。[1: H, = C (R) COOCH, mouth H (R') Kano (A) (However, R and R'
indicates H or CH3. ) In addition, urethane acrylates as described in JP-A-51-37193, JP-A-4864183,
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates made by reacting epoxy resin and (meth)acrylic acid as described in Japanese Patent Publication No. 49-43191 and Japanese Patent Publication No. 52-30490. I can give it to you. Furthermore, those introduced as photocurable monomers and olicomers in Japan Adhesive Association Journal Vol. 20, No. 7.300-308 (1984) can also be used. The amount used is 5 to 90% by weight (based on the total ingredients).
Hereinafter, it will be abbreviated as %. ), preferably 10 to 70%.
本発明に使用する光重合開始剤としては、ベンジル、ベ
ンゾイン、ベンゾインエーテル、ミヒラーケトン、アン
トラキノン、アクリジン、フェナジン、ベンゾフェノン
、2−エチルアントラキノン、トリハロメチルトリアジ
ン化合物など、また、米国特許第2850445号に記
載のある種の光還元性染料、例えばローズベンガル、エ
オシン、エリスロシンなど、あるいは、染料と開始剤と
の組合せによる系例えば、染料とアミンの複合開始系(
特公昭44−20189号など)、ヘキサアリールビイ
ミダゾールとラジカル発生剤および染料の系(特公昭4
5−37377号など)、ヘキサアリールビイミダゾー
ルとP−ジアルキルアミノベンジリデンケトンの系(特
公昭47−2528号、特開昭54−155292号な
ど)、染料と有機過酸化物の系(特公昭62−1641
号、特開昭59−1504号、特開昭59−14020
3号、特開昭59−189340号、米国特許第476
6055号、特開昭61−174203号など)、染料
と活性ハロゲン化合物の系(特開昭54
15102号、特開昭58−15503号、特開昭63
−178105号、特開昭63
258903号、特開平2−63054号など)、染料
とボレート化合物の系(特開昭62−143044号、
特開昭62−150242号、特開昭61−13140
号、特開昭64−13141号、特開昭64−1314
2号、特開昭64−13143号、特開昭64−131
44号、特開昭64 17048号、特開昭64721
50号、特開平1−229003号、特開平1−29’
8348号、特開平1−138204号など)などが挙
げられる。Examples of the photopolymerization initiator used in the present invention include benzyl, benzoin, benzoin ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone, 2-ethylanthraquinone, and trihalomethyltriazine compounds; Certain photoreducible dyes, such as rose bengal, eosin, erythrosin, etc., or systems based on combinations of dyes and initiators, such as complex initiation systems of dyes and amines (
(Special Publication No. 44-20189, etc.), system of hexaarylbiimidazole, radical generator and dye (Special Publication No. 44-20189, etc.);
5-37377, etc.), systems of hexaarylbiimidazole and P-dialkylaminobenzylidene ketone (Japanese Patent Publication No. 47-2528, JP-A-54-155292, etc.), systems of dyes and organic peroxides (Japanese Patent Publication No. 1983-155292, etc.) -1641
No., JP-A-59-1504, JP-A-59-14020
No. 3, JP-A-59-189340, U.S. Patent No. 476
6055, JP-A-61-174203, etc.), systems of dyes and active halogen compounds (JP-A-54-15102, JP-A-58-15503, JP-A-63)
-178105, JP-A-63-258903, JP-A-2-63054, etc.), dye and borate compound systems (JP-A-62-143044, JP-A-62-143044, etc.);
JP-A-62-150242, JP-A-61-13140
No., JP-A-64-13141, JP-A-64-1314
No. 2, JP-A-64-13143, JP-A-64-131
No. 44, JP-A-64 No. 17048, JP-A-64721
No. 50, JP-A-1-229003, JP-A-1-29'
No. 8348, JP-A No. 1-138204, etc.).
本発明に使用される線状有機高分子重合体としては、光
重合可能なエチレン性不飽和化合物と相溶性を有してい
る線状有機高分子重合体である限り、どれを使用しても
よい。好ましくは水現像或は弱アルカリ水現像を可能と
する水あるいは弱アルカリ水可溶性又は膨潤性である線
状有機高分子重合体が選択される。線状有機高分子重合
体は、該組成物の皮膜形成剤としてだけでなく、水、弱
アルカリ水或は有機溶剤現像剤としての用途に応じて選
択使用される。例えば、水可溶性有機高分子重合体を用
いると水現像が可能になる。この様な線状有機高分子重
合体としては、側鎖にカルボン酸を有する付加重合体、
例えば特開昭59−44615号、特公昭54−343
27号、特公昭58−12577号、特公昭54−25
957号、特開昭54−92723号、特開昭5953
836号、特開昭59−71048号に記載されている
もの、すなわち、メタクリル酸共重合体、アクリル酸共
重合体、イタコン酸共重合体、クロトン酸共重合体、マ
レイン酸共重合体、部分エステル化マレイン酸共重合体
等がある。また同様に側鎖にカルボン酸を有する酸性セ
ルロース誘導体がある。その他、水酸基を有する付加重
合体に溝状酸無水物を付加させたものなどが有用である
。特にこれらの中で〔ベンジル(メタ)アクリレート/
(メタ)アクリル酸/必要に応じてその他の付加重合性
ビニルモノマー]共重合体及び〔アリル(メタ)アクリ
レート/(メタ)アクリル酸/必要に応じてその他の付
加重合性ビニルモノマー)共重合体が好適である。この
他に水溶性線状有機高分子として、ポリビニルピロリド
ンやポリエチレンオキサイド等が有用である。また硬化
皮膜の強度をあげるためにアルコール可溶性ナイロンや
2. 2−ビス−(4−ヒドロキンフェニル)−プロパ
ンとエビクロロヒドリンノホリエーテル等も有用である
。これらの線状有機高分子重合体は全組成物中に任意な
量を混和させることができる。しかし90%を越える場
合には形成させる画像強度等の点で好ましい結果を与え
ない。好ましくは30〜85%である。また光重合可能
なエチレン性不飽和化合物と線状有機高分子重合体は、
重量比で1/9〜7/3の範囲とするのが好ましい。よ
り好ましい範囲は3/7〜515である。Any linear organic polymer can be used as long as it is compatible with the photopolymerizable ethylenically unsaturated compound. good. Preferably, a linear organic polymer is selected which is soluble or swellable in water or weakly alkaline water and is capable of being developed in water or weakly alkaline water. The linear organic polymer is used not only as a film-forming agent of the composition, but also as a water, weak alkaline water, or organic solvent developer depending on the use. For example, water development becomes possible when a water-soluble organic high molecular weight polymer is used. Examples of such linear organic polymers include addition polymers having carboxylic acid in the side chain,
For example, Japanese Patent Publication No. 59-44615, Japanese Patent Publication No. 54-343
No. 27, Special Publication No. 58-12577, Special Publication No. 54-25
No. 957, JP-A-54-92723, JP-A-5953
836, JP-A No. 59-71048, namely methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partial Examples include esterified maleic acid copolymers. Similarly, there are acidic cellulose derivatives having carboxylic acid in their side chains. In addition, an addition polymer having a hydroxyl group to which a grooved acid anhydride is added is useful. Especially among these [benzyl (meth)acrylate/
(meth)acrylic acid/other addition-polymerizable vinyl monomers as necessary] copolymers and [allyl (meth)acrylate/(meth)acrylic acid/other addition-polymerizable vinyl monomers as necessary) copolymers is suitable. Other useful water-soluble linear organic polymers include polyvinylpyrrolidone and polyethylene oxide. In addition, to increase the strength of the cured film, alcohol-soluble nylon or 2. Also useful are 2-bis-(4-hydroquinphenyl)-propane and shrimp chlorohydrinopholiether. Any amount of these linear organic high molecular weight polymers can be mixed into the entire composition. However, if it exceeds 90%, it will not give favorable results in terms of image strength, etc. to be formed. Preferably it is 30-85%. In addition, photopolymerizable ethylenically unsaturated compounds and linear organic polymers are
The weight ratio is preferably in the range of 1/9 to 7/3. A more preferable range is 3/7 to 515.
また、本発明においては以上の基本成分の他に感光性組
成物の製造中あるいは保存中において重合可能なエチレ
ン性不飽和化合物の不要な熱重合を阻止するた約に少量
の熱重合防止剤を添加することが望ましい。適当な熱重
合防止剤としてはノ\イドロキノン、p−メトキシフェ
ノール、ジ−t−フチルーp−クレゾール、ピロガロー
ル、tブチルカテコール、ベンゾキノン、4,4′−チ
オビス(3−メチル−6−t−ブチルフェノール)、2
.2′−メチレンビス(4−メチル−5−tブチルフェ
ノール)、N−ニトロソフェニルヒドロキシアミン第一
セリウム塩等が挙げられる。熱重合防止剤の添加量は、
全組成物の重量に対して約0.G1%〜1%〜約5まし
い。また必要に応じて、酸素による重合阻害を防止する
ためにベヘン酸やベヘン酸アミドのような高級脂肪酸誘
導体等を添加して、塗布後の乾燥の過程で感光層の表面
に偏在させてもよい。高級脂肪酸誘導体の添加量は、全
組成物の約0.5〜約10%が好ましい。さらに、感光
層の着色を目的として染料もしくは顔料を添加してもよ
い。染料および顔料の添加量は全組成物の約0.5%〜
約5%が好ましい。加えて、硬化皮膜の物性を改良する
ために無機充填剤や、その他の公知の添加剤を加えても
よい。In addition to the above-mentioned basic ingredients, in the present invention, a small amount of a thermal polymerization inhibitor is added to prevent unnecessary thermal polymerization of polymerizable ethylenically unsaturated compounds during the production or storage of the photosensitive composition. It is desirable to add. Suitable thermal polymerization inhibitors include nohydroquinone, p-methoxyphenol, di-t-phthyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-t-butylphenol). ), 2
.. Examples thereof include 2'-methylenebis(4-methyl-5-t-butylphenol) and N-nitrosophenylhydroxyamine cerous salt. The amount of thermal polymerization inhibitor added is
Approximately 0.0% based on the weight of the total composition. G1% to 1% to about 5%. If necessary, higher fatty acid derivatives such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition caused by oxygen, and may be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. . The amount of the higher fatty acid derivative added is preferably about 0.5 to about 10% of the total composition. Furthermore, dyes or pigments may be added for the purpose of coloring the photosensitive layer. The amount of dyes and pigments added is approximately 0.5% to the total composition.
About 5% is preferred. In addition, inorganic fillers and other known additives may be added to improve the physical properties of the cured film.
本発明の光重合性組成物を支持体上に塗布する際には種
々の有機溶剤に溶かして使用に供される。When applying the photopolymerizable composition of the present invention onto a support, it can be used after being dissolved in various organic solvents.
ここで使用する溶媒としては、アセトン、メチルエチル
ケトン、シクロヘキサン、酢酸エチル、エチレンジクロ
ライド、テトラヒドロフラン、トルエン、エチレングリ
コールモノメチルエーテル、エチレングリコールモノエ
チルエーテル、エチレングリコールジメチルエーテル、
プロピレングリコールモノメチルエーテル、プロピレン
グリコールモノエチルエーテル、アセチルアセトン、シ
クロヘキサノン、ジアセトンアルコーノベエチレングリ
コールモノメチルエーテルアセテート、エチレングリコ
ールエチルエーテルアセテート、エチレングリコールモ
ノイソプロピルエーテル、エチレングリコールモノブチ
ルエーテルアセテート、3−メトキシプロパツール、メ
トキシメトキシエタノール、ジエチレングリコールモノ
メチルエーテル、ジエチレングリコールモノエチルエー
テル、ジエチレングリコールジメチルエーテル、ジエチ
レングリコールジエチルエーテル、プロピレングリコー
ルモノメチルエーテルアセテート、プロピレングリコー
ルモノエチルエーテルアセテート、3−メトキシプロピ
ルアセテート、N、N−ジメチルホルムアミド、ジメチ
ルスルホキシド、T−ブチロラクトン、乳酸メチル、乳
酸エチルなどがある。これらの溶媒は、単独あるいは混
合して使用することができる。そして、塗布溶液中の固
形分の濃度は、2〜50重量%が適当である。The solvents used here include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether,
Propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxy Methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,N-dimethylformamide, dimethyl sulfoxide, T- These include butyrolactone, methyl lactate, and ethyl lactate. These solvents can be used alone or in combination. The appropriate concentration of solids in the coating solution is 2 to 50% by weight.
その被覆量は乾燥後の重量で約0.1g/m’〜約10
g/m″の範囲が適当である。より好ましくは0.5〜
5 g / m’である。The coating amount is about 0.1 g/m' to about 10 g/m' after drying.
g/m'' range is appropriate. More preferably 0.5~
5 g/m'.
本発明に用いられる「酸素透過度が30〜300cc/
m”day −atm (25℃/湿度35%)より
小さい透明な保護層」の形成材料としては、ポリビニル
アルコール特にケン化度95モル%以上のポリビニルア
ルコール、ポリ塩化ビニ’J fン、ポリアクリロニト
リルなどが挙げられる。保護層の被覆量は乾燥後の重量
で0.01g/m’〜50g/m’、より好ましくは0
.1〜10g/m’が適当である。この様な保護層の塗
布方法については、例えば米国特許第3.458.31
1号、特公昭5549729号に詳しく記載されている
。The oxygen permeability used in the present invention is 30 to 300 cc/
Materials for forming the "transparent protective layer smaller than m"day-atm (25°C/35% humidity) include polyvinyl alcohol, especially polyvinyl alcohol with a degree of saponification of 95 mol% or more, polyvinyl chloride, polyacrylonitrile. Examples include. The coating amount of the protective layer is 0.01 g/m' to 50 g/m', more preferably 0.01 g/m' to 50 g/m' in weight after drying.
.. 1 to 10 g/m' is suitable. A method of applying such a protective layer is described, for example, in U.S. Pat. No. 3.458.31.
It is described in detail in No. 1 and Special Publication No. 5549729.
本発明の光重合性組成物を用いた感光材料は、画像露光
したのち、現像液で感光層の未露光部を除去し、画像を
得る。これらの光重合性組成物を平版印刷版の作成に使
用する際の好ましい現像液としては、特公昭57−74
27号に記載されているような現像液があげられ、ケイ
酸ナトリウム、ケイ酸カリウム、水酸化ナトリウム、水
酸化カリウム、水酸化リチウム、第三リン酸ナトリウム
、第ニリン酸ナトリウム、第三リン酸アンモニウム、第
ニリン酸アンモニウム、メタケイ酸ナトリウム、重炭酸
ナトリウム、アンモニア水などのような無機アルカリ剤
やモノエタノールアミン又(λジェタノールアミンなど
のような有機アルカリ剤の水溶液が適当である。該アル
カリ溶液の濃度が0.1〜10重量%、好ましくは0.
5〜5重量%になるように添加される。After imagewise exposure of a photosensitive material using the photopolymerizable composition of the present invention, unexposed areas of the photosensitive layer are removed with a developer to obtain an image. Preferred developing solutions for using these photopolymerizable compositions in preparing lithographic printing plates include those disclosed in Japanese Patent Publication No. 57-74
Examples include developers such as those described in No. 27, including sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, and triphosphoric acid. Suitable are aqueous solutions of inorganic alkaline agents such as ammonium, ammonium diphosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc., and organic alkaline agents such as monoethanolamine or (λjetanolamine). The concentration of the solution is 0.1 to 10% by weight, preferably 0.
It is added in an amount of 5 to 5% by weight.
また、該アルカリ性水溶液には、必要に応じ界面活性剤
やベンジルアルコール、2−フェノキシエタノール、2
−ブトキシェタノールのような有機溶媒を少量含むこと
ができる。例えば、米国特許第3.375.171号お
よび同第3.615.480号に記載されているものを
挙げることができる。In addition, the alkaline aqueous solution may contain surfactants, benzyl alcohol, 2-phenoxyethanol, 2
- Small amounts of organic solvents such as butoxetanol may be included. For example, those described in US Pat. No. 3,375,171 and US Pat. No. 3,615,480 can be mentioned.
更に、特開昭50−26601号、同58−54341
号、特公昭56−39464号、同56−42860号
の各公報に記載されている現像液も優れている。Furthermore, JP-A-50-26601 and JP-A-58-54341
The developing solutions described in Japanese Patent Publication No. 56-39464 and Japanese Patent Publication No. 56-42860 are also excellent.
本発明の平版印刷版の製版方法は、特にレーザー光源に
よる画像露光を行なう際に良好な結果が得られる。The plate-making method for a lithographic printing plate of the present invention provides good results, particularly when performing image exposure using a laser light source.
光源としては、超高圧・高圧・中圧・低圧の各水銀灯、
ケミカルランプ、カーボンアーク灯、キャノン灯、タン
グステン灯、メタルハライド灯、ケイ光灯、太陽光、お
よび各種レーザー光源、例えばHe−Neレーザー、A
r+レーザー、半導体レーザー、YAGレーザーなどが
使用できる。Light sources include ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps,
Chemical lamps, carbon arc lamps, cannon lamps, tungsten lamps, metal halide lamps, fluorescent lamps, sunlight, and various laser light sources such as He-Ne laser, A
An r+ laser, a semiconductor laser, a YAG laser, etc. can be used.
本発明により、高感度かつ調子再現性にすぐれた平版印
刷版の製版が可能となった。The present invention has made it possible to make a lithographic printing plate with high sensitivity and excellent tone reproducibility.
以下実施例をもって本発明を説明するが、本発明はこれ
らの実施例に限定されるものではない。The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.
(感光材料の作製)
厚さ0.30 mmのアルミニウム板をナイロンブラシ
と400メツシユのパミストンの水懸濁液とを用いその
表面を砂目立てした後、よく水で洗浄した。10%水酸
化す) IJウムに70℃で60秒間浸漬してエツチン
グした後、流水で水洗後20%硝酸で中和洗浄し、次い
で水洗した。これをVA= 12.7 Vの条件下で正
弦波の交番波形電流を用いて1%硝酸水溶液中で160
ク一ロン/dm2の陽極特電気量で電解粗面化処理を行
った。その表面粗さを測定したところ、0.6μ(R,
表示)であった。引き続いて30%の硫酸水溶液中に浸
漬し55℃で2分間デスマットした後、20%硫酸水溶
液中、電流密度2A/dm2において陽極酸化皮膜の厚
さが2.7g/m’になるように2分間陽極酸化処理し
た。(Preparation of photosensitive material) The surface of an aluminum plate having a thickness of 0.30 mm was grained using a nylon brush and a 400 mesh water suspension of pumice stone, and then thoroughly washed with water. After etching by immersing in IJum (10% hydroxide) at 70° C. for 60 seconds, washing with running water, neutralizing with 20% nitric acid, and then washing with water. This was heated to 160°C in a 1% nitric acid aqueous solution using a sinusoidal alternating current waveform under the condition of VA = 12.7 V.
Electrolytic surface roughening treatment was carried out using a special anode electricity amount of Coulomb/dm2. When the surface roughness was measured, it was found to be 0.6μ (R,
display). Subsequently, it was immersed in a 30% sulfuric acid aqueous solution and desmutted at 55°C for 2 minutes, and then desmutted in a 20% sulfuric acid aqueous solution at a current density of 2 A/dm2 so that the thickness of the anodic oxide film was 2.7 g/m'. Anodized for minutes.
このように処理されたアルミニウム板上に、下記組成の
感光性組成物を乾燥塗布重量が14g/m’となるよう
に塗布し、80℃で2分間乾燥させ感光層を形成させた
。On the thus treated aluminum plate, a photosensitive composition having the following composition was coated so that the dry coating weight was 14 g/m' and dried at 80° C. for 2 minutes to form a photosensitive layer.
チル
2、tlg
光重合開始剤 x3フッ素系
ノニオン界面活性剤 0.03gメチルエチル
ケトン 20gこの感光層上に、ポ
リビニルアルコール(ケン化度86.5〜89モル%、
重合度1000)の3重量%の水溶液を乾燥塗布量が2
g/m″となるように塗布し、100℃/2分間乾燥さ
せ保護層を作成した。この保護層の酸素透過度は、37
cc/m’ ・day −atm(25℃/湿度35
%)であった(日本分光工業社製Gasperm−10
0で測定)。Chill 2, tlg Photopolymerization initiator x3 Fluorinated nonionic surfactant 0.03 g Methyl ethyl ketone 20 g
A 3% by weight aqueous solution with a degree of polymerization of 1000) was applied in a dry coating amount of 2.
g/m'' and dried at 100°C for 2 minutes to create a protective layer.The oxygen permeability of this protective layer was 37.
cc/m' ・day -atm (25℃/humidity 35
%) (Gasperm-10 manufactured by JASCO Corporation)
(measured at 0).
(製版・評価)
次に、これらの感材材料を用い、減圧下に置いた(必要
に応じて画像露光後の加熱)場合と、そうでない場合と
の感度および調子再現性を比較した。減圧処理は、真空
デシケータ−中に置いた試料を真空ポンプ(日立社製4
VP−C5)により、1、0 mmHgに30分間保っ
たのち、窒素ガスで常圧にもどし、5分間静置したのち
、真空デシケータ−から取り出し、5分以内に画像露光
を行なった。(Plate Making/Evaluation) Next, using these light-sensitive materials, the sensitivity and tone reproducibility were compared between cases where they were placed under reduced pressure (heating after image exposure, if necessary) and cases where they were not placed under reduced pressure. For depressurization treatment, the sample placed in a vacuum desiccator was placed in a vacuum pump (Hitachi 4).
After maintaining the pressure at 1.0 mmHg for 30 minutes using VP-C5), the pressure was returned to normal pressure using nitrogen gas, and after being allowed to stand for 5 minutes, it was taken out from the vacuum dessicator and image exposure was performed within 5 minutes.
画像露光は、平坦な運搬台上を1.7 ++nn/ s
ecの速度で移動する版に対して垂直方向に54m/s
ecの速度で移動するAr”レーザービーム(スポット
径35μ)によって65線/インチの網点を書かせるこ
とにより行なった。評価は50%網点を5C%として再
現するときを適正露光とし、その時の30%及び70%
網点の面積を測定することにより行なった。Image exposure is 1.7 ++nn/s on a flat carrier
54 m/s perpendicular to the plate moving at a speed of ec
This was done by writing halftone dots at 65 lines/inch using an Ar'' laser beam (spot diameter 35μ) moving at a speed of 30% and 70% of
This was done by measuring the area of halftone dots.
加熱を行なう場合は、画像露光後、60℃のオーブン中
で5分間加熱を行なったのち現像した。When heating was performed, after image exposure, the film was heated in an oven at 60° C. for 5 minutes and then developed.
(加熱を行なわない場合は画像露光後1分で現像した。(When heating was not performed, the image was developed 1 minute after exposure.
) 現像は、 て行った。) The development is I went.
Kケイ酸カリウム [全酸化カリウム 下記の現像液に25℃、 1分間浸漬し 結果を表1に示す。Potassium K silicate [Total potassium oxide 25℃ in the following developer solution. Soak for 1 minute The results are shown in Table 1.
この結果、感光材料A、Bとも、減圧処理を行なうこと
により、高感度となり、調子再現性も良化しており、露
光後加熱することにより、更に、高感度化できた。As a result, both photosensitive materials A and B had high sensitivity and improved tone reproducibility by performing the reduced pressure treatment, and the sensitivity could be further increased by heating after exposure.
Claims (2)
エチレン性不飽和結合を有する重合可能な化合物と光重
合開始剤と線状有機高分子重合体とを含む光重合性感光
層と、 iii)酸素透過度が30〜300cc/m^2・da
y・atm(25℃/湿度35%)である透明な保護層 を設けてなる感光性平版印刷版を減圧下に置き、感光層
中の溶存酸素を除去したのち、窒素ガスで置換後、画像
露光、現像することを特徴とする平版印刷版の製版方法
。(1) i) on a support, ii) a polymerizable compound having at least one ethylenically unsaturated bond that can be photopolymerized by actinic rays, a photopolymerization initiator, and a linear organic polymer; iii) an oxygen permeability of 30 to 300 cc/m^2・da;
A photosensitive lithographic printing plate provided with a transparent protective layer of Y.ATM (25°C/humidity 35%) is placed under reduced pressure to remove dissolved oxygen in the photosensitive layer, and then replaced with nitrogen gas. A method for making a lithographic printing plate characterized by exposure and development.
像することを特徴とする請求項(1)記載の方法。(2) The method according to claim (1), characterized in that development is carried out after heat treatment during or after image exposure.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16526790A JPH0456863A (en) | 1990-06-22 | 1990-06-22 | Plate making method for planographic printing plate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16526790A JPH0456863A (en) | 1990-06-22 | 1990-06-22 | Plate making method for planographic printing plate |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0456863A true JPH0456863A (en) | 1992-02-24 |
Family
ID=15809084
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP16526790A Pending JPH0456863A (en) | 1990-06-22 | 1990-06-22 | Plate making method for planographic printing plate |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0456863A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006301565A (en) * | 2005-03-23 | 2006-11-02 | Fuji Photo Film Co Ltd | Planographic printing plate precursor and platemaking method thereof |
JP2007093662A (en) * | 2005-09-27 | 2007-04-12 | Fujifilm Corp | Lithographic printing original plate and its plate-making method |
JP2010079265A (en) * | 2008-08-29 | 2010-04-08 | Fujifilm Corp | Photomask blanks and photomask |
WO2012029583A1 (en) * | 2010-08-31 | 2012-03-08 | 富士フイルム株式会社 | Method for producing lithographic printing plate |
-
1990
- 1990-06-22 JP JP16526790A patent/JPH0456863A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006301565A (en) * | 2005-03-23 | 2006-11-02 | Fuji Photo Film Co Ltd | Planographic printing plate precursor and platemaking method thereof |
JP4574506B2 (en) * | 2005-03-23 | 2010-11-04 | 富士フイルム株式会社 | Planographic printing plate precursor and its plate making method |
JP2007093662A (en) * | 2005-09-27 | 2007-04-12 | Fujifilm Corp | Lithographic printing original plate and its plate-making method |
JP4619912B2 (en) * | 2005-09-27 | 2011-01-26 | 富士フイルム株式会社 | Planographic printing plate precursor and its plate making method |
JP2010079265A (en) * | 2008-08-29 | 2010-04-08 | Fujifilm Corp | Photomask blanks and photomask |
WO2012029583A1 (en) * | 2010-08-31 | 2012-03-08 | 富士フイルム株式会社 | Method for producing lithographic printing plate |
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