JPH03179446A - Production of damping waterless planographic printing plate material - Google Patents
Production of damping waterless planographic printing plate materialInfo
- Publication number
- JPH03179446A JPH03179446A JP31985889A JP31985889A JPH03179446A JP H03179446 A JPH03179446 A JP H03179446A JP 31985889 A JP31985889 A JP 31985889A JP 31985889 A JP31985889 A JP 31985889A JP H03179446 A JPH03179446 A JP H03179446A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- silicone rubber
- light
- weight
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000007639 printing Methods 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 238000013016 damping Methods 0.000 title 1
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 54
- 239000004945 silicone rubber Substances 0.000 claims abstract description 52
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 43
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 abstract description 6
- 238000013007 heat curing Methods 0.000 abstract description 3
- 230000002411 adverse Effects 0.000 abstract description 2
- 230000008961 swelling Effects 0.000 abstract description 2
- 239000003595 mist Substances 0.000 abstract 3
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 230000006866 deterioration Effects 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 119
- 239000010408 film Substances 0.000 description 64
- -1 etc. Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 13
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- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 229920000642 polymer Polymers 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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
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- 229920006026 co-polymeric resin Polymers 0.000 description 4
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- 150000002148 esters Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 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
- 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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229920005601 base polymer Polymers 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013039 cover film Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000009503 electrostatic coating Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- NFVPEIKDMMISQO-UHFFFAOYSA-N 4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C=C1 NFVPEIKDMMISQO-UHFFFAOYSA-N 0.000 description 2
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
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- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- XZSZONUJSGDIFI-UHFFFAOYSA-N n-(4-hydroxyphenyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC1=CC=C(O)C=C1 XZSZONUJSGDIFI-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
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- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
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- 239000001055 blue pigment Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- VQXINLNPICQTLR-UHFFFAOYSA-N carbonyl diazide Chemical compound [N-]=[N+]=NC(=O)N=[N+]=[N-] VQXINLNPICQTLR-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
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- 239000010941 cobalt Substances 0.000 description 1
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- 238000001723 curing Methods 0.000 description 1
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- 229910001873 dinitrogen Inorganic materials 0.000 description 1
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- 239000011133 lead Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 239000000025 natural resin Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
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- 229920002866 paraformaldehyde Polymers 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
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- 229920002647 polyamide Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
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- 229920005992 thermoplastic resin Polymers 0.000 description 1
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- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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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、湿し水不要平版印刷版材料の製造方法に関し
、詳しくは耐刷性を雑持した上で真空密着性を改良する
ことができる湿し水不要平版印刷版材料の製造方法に関
する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a lithographic printing plate material that does not require dampening water, and more specifically, a method for producing a lithographic printing plate material that does not require dampening water, and more specifically, a method that improves vacuum adhesion while maintaining printing durability. The present invention relates to a method for producing a lithographic printing plate material that does not require dampening water.
湿し水不要平版印刷版材料に画像を形成するためには、
通常原画を通して活性光線による露光が行われるが、原
画を忠実に再現するためには、該版材上面に原画を完全
に密着させることが必要であった。このため、一般的に
はゴムシートと圧着ガラスの間に、該版材と原画とを重
ねて配置し、ゴムシートと圧着ガラスの間を真空にして
密着させる真空密着法が用いられてきた。To form an image on a lithographic printing plate material that does not require dampening water,
Normally, the original image is exposed to actinic light, but in order to faithfully reproduce the original image, it is necessary to bring the original image into complete contact with the upper surface of the printing plate. For this reason, a vacuum adhesion method has generally been used in which the printing plate and the original are placed one on top of the other between a rubber sheet and a pressure-bonding glass, and the space between the rubber sheet and the pressure-bonding glass is evacuated to bring them into close contact.
しかし、真空密着性を十分にすることは困難であり、こ
れらを改良するために種々の技術が提案されている。However, it is difficult to achieve sufficient vacuum adhesion, and various techniques have been proposed to improve this.
特開昭８２−２４７８８８号には、フィルム上にグラビ
アロールによって樹脂液を塗布することにより。In JP-A No. 82-247888, a resin liquid is applied onto a film using a gravure roll.
グラビアロールの彫刻に応じた凹凸のパターンを設けた
フィルムを作った後、このフィルムの平滑面（凹凸を宥
しない表面）がシリコーンゴム層と接するようにラミネ
ートすることによって、カバーフィルム上にマット層を
設ける方法が開示されている。After making a film with an uneven pattern corresponding to the engraving of the gravure roll, the film is laminated so that the smooth surface (the surface that does not tolerate unevenness) is in contact with the silicone rubber layer, thereby creating a matte layer on the cover film. Disclosed is a method for providing.
また特開昭５５−５５３４３号には、最上層のシリコー
ンゴム層上に凹凸の透明フィルムを被覆する技術が開示
され、凹凸をつける方法として、実質的に平滑な保護フ
ィルム上に無機粒子を含む溶液を塗布する方法も有効で
あると記載されている。Furthermore, JP-A No. 55-55343 discloses a technique for coating an uneven transparent film on the uppermost silicone rubber layer, and as a method for providing unevenness, inorganic particles are coated on a substantially smooth protective film. A method of applying a solution is also described as being effective.
しかし、従来方法は、いずれも塗布する樹脂の溶媒でカ
バーフィルムが膨潤して、シリコーン層から剥離してし
まったり、また膨潤しないまでも浸透した溶媒がシリコ
ーン層の硬化やシリコーン層と感光層の間の接着性に悪
影響を与え現像の時にシリコーン層が剥がれ、耐刷性が
劣るという問題がある。However, in all conventional methods, the cover film swells with the solvent of the resin being applied and peels off from the silicone layer.Also, even if the cover film does not swell, the solvent that penetrates may cause the silicone layer to harden or the silicone layer and photosensitive layer to separate. There is a problem that this adversely affects the adhesion between the silicone layer and the silicone layer peels off during development, resulting in poor printing durability.
そこで本発明の目的は、真空密着性を改良しつつ耐刷性
を向上できる湿し水不要平版印刷版材料の製造方法を提
供することにある。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method for producing a lithographic printing plate material that does not require dampening water and can improve vacuum adhesion and printing durability.
本発明者は、上記目的を遠戚すべく鋭意検討の結果、本
発明に至った。The inventors of the present invention have conducted intensive studies to achieve the above-mentioned object, and as a result, have arrived at the present invention.
即ち、本発明に係る湿し水不要平版印刷版材料の製造方
法は、支持体上に、感光層及びシリコーンゴム層又は感
光性シリコーンゴム層、及び光透過性フィルム層を有す
る湿し水不要平版印刷版材料の製造方法において、前記
シリコーンゴム層上に光透過性フィルム層を形威し、次
いで樹脂を溶解又は分散させた塗布液の微細な液滴を前
記光透過性フィルム層上に付着後乾燥又は熱硬化して該
光透過性フィルム層上に固体粒子が固着された不連続マ
ット層を形成することを特徴とする。That is, the method for producing a dampening water-free planographic printing plate material according to the present invention provides a dampening water-free planographic plate having a photosensitive layer, a silicone rubber layer or a photosensitive silicone rubber layer, and a light-transmitting film layer on a support. In the method for producing a printing plate material, a light-transparent film layer is formed on the silicone rubber layer, and then fine droplets of a coating liquid in which a resin is dissolved or dispersed are deposited on the light-transparent film layer. It is characterized in that it is dried or thermally cured to form a discontinuous matte layer on which solid particles are fixed on the light-transmitting film layer.
本発明の好ましい態様としては、前記塗布液の微細な液
滴を静電的に噴霧して前記光透過性フィルム層上に付着
させることであり、また塗布液の溶媒が、水又は沸点１
３０℃未満の有機溶剤であることである。In a preferred embodiment of the present invention, fine droplets of the coating liquid are electrostatically sprayed and deposited on the light-transmitting film layer, and the solvent of the coating liquid is water or boiling point 1
It is an organic solvent with a temperature of less than 30°C.
本発明の湿し水不要平版印刷版材料の製造方法は、塗布
液が微ｍＷｌ状の液滴になって光透過性フィルム層上に
付着するため、その付着するまでの間に液滴中の溶媒が
蒸発しやすく溶剤による膨潤等の問題をなくすことがで
きる。また光透過性フィルム層上に付着させるのに最低
限必要な溶剤量（若干粘着が残る程度）に減らした後に
付着させることができるので、シリコーンゴム層と感光
層との接着性やシリコーンゴム層と光透過性フィルム層
との接着性に悪影響がなく、従って耐刷性の低下を招く
こともない、即ち本発明の製造方法によって得られた不
連続マット層によれば、真空密着性を改良し耐刷性を向
上でき、本発明の目的が遠戚される。In the method for producing a lithographic printing plate material that does not require dampening water according to the present invention, since the coating liquid forms droplets in the form of micromWl and adheres to the light-transmitting film layer, the amount of water in the droplets is The solvent evaporates easily and problems such as swelling caused by the solvent can be eliminated. In addition, since the amount of solvent can be reduced to the minimum required for adhesion onto the light-transmitting film layer (slight adhesion remains), the adhesion between the silicone rubber layer and the photosensitive layer can be improved. The discontinuous matte layer obtained by the production method of the present invention has no adverse effect on the adhesion between the light-transmitting film layer and the light-transmitting film layer, and therefore does not cause a decrease in printing durability. Therefore, the printing durability can be improved, which is a distant relative of the object of the present invention.
以下１本発明について詳説する。 The present invention will be explained in detail below.
（支持体）
支持体としては１通常の平版印刷機にセットできるたわ
み性と印刷時に加わる荷重に耐えうるちのであることが
好ましく、例えばアルミニウム、亜鉛、銅、鋼等の金属
板、及びクロム、亜鉛、銅、ニッケル、アルミニウム及
び鉄等がメツキ又は蒸着された金属板、紙、プラスチッ
クフィルム及びガラス板、樹脂コート紙、アルミニウム
等の金属箔が張られた紙、親木化処理したプラスチック
フィルム等が挙げられる。これらのうち好ましいのはア
ルミニウム板である。アルミニウム板を使用する場合、
砂目立て処理、陽極酸化処理等の粗面化処理等が施され
ていてもよい。(Support) The support is preferably one that is flexible enough to be set in a normal lithographic printing machine and that can withstand the load applied during printing, such as metal plates such as aluminum, zinc, copper, and steel; Metal plates plated or vapor-deposited with zinc, copper, nickel, aluminum, iron, etc., paper, plastic films and glass plates, resin-coated paper, paper covered with metal foil such as aluminum, plastic films treated with wood-filtering, etc. can be mentioned. Among these, aluminum plates are preferred. When using aluminum plate,
Surface roughening treatments such as graining treatment and anodizing treatment may be performed.
支持体の厚みは、５０〜４００ ＪＬ■が好ましく、よ
り好ましくは１００〜３００ ＩＬ■である。The thickness of the support is preferably 50 to 400 JL, more preferably 100 to 300 IL.
（プライマー層）
支持体上にはプライマー層を有していてもよく、該プラ
イマー層には樹脂やシランカップリング剤、シリコーン
プライマーなどを用いることができ、また有機チタネー
ト等が好ましく用いられる。(Primer layer) A primer layer may be provided on the support, and a resin, a silane coupling agent, a silicone primer, etc. can be used for the primer layer, and organic titanates and the like are preferably used.
樹脂としては１例えばポリエステル樹脂、塩化ビニル−
酢酸ビニル共重合体、アクリル樹脂、塩化ビニル樹脂、
ポリアミド樹脂、ポリビニルブチラール樹脂、エポキシ
樹脂、アクリレート系共重合体、酢酸ビニル系共重合体
、フェノキシ樹脂。Examples of resins include polyester resin, vinyl chloride, etc.
Vinyl acetate copolymer, acrylic resin, vinyl chloride resin,
Polyamide resin, polyvinyl butyral resin, epoxy resin, acrylate copolymer, vinyl acetate copolymer, phenoxy resin.
ポリウレタン樹脂、ポリカーボネート樹脂、ポリアクリ
ロニトリルブタジェン、ポリ酢酸ビニル等が挙げられる
。Examples include polyurethane resin, polycarbonate resin, polyacrylonitrile butadiene, polyvinyl acetate, and the like.
中でもアルコール性ＯＨ基を有する（メタ）アクリル酸
エステル、例えば２−ヒドロキシエチルメタクリレート
の共重合体樹脂を光架橋あるいは熱架橋した樹脂が好ま
しい。Among these, resins obtained by photocrosslinking or thermally crosslinking copolymer resins of (meth)acrylic esters having alcoholic OH groups, such as 2-hydroxyethyl methacrylate, are preferred.
本発明に用いられるプライマー層では、感光層の塗布溶
媒や現像液の有機溶剤に対する耐溶剤性を向上させるた
め架橋させることが好ましい。The primer layer used in the present invention is preferably crosslinked in order to improve solvent resistance to the coating solvent of the photosensitive layer and the organic solvent of the developer.
この架橋させる成分としては、多価インシアネー・ト化
合物、ジアゾ樹脂、多価エポキシ化合物、２個以上の重
合可能なエチレン性不飽和二重結合を有する化合物等が
用いられる。As the component to be crosslinked, a polyvalent incyanate compound, a diazo resin, a polyvalent epoxy compound, a compound having two or more polymerizable ethylenically unsaturated double bonds, etc. are used.
多価イソシアネート化合物としては、例えばジフェニル
メタン−４，４′−ジイソシアネート、へキサメチレン
ジイソシアネート、コロネートＥ。Examples of the polyvalent isocyanate compound include diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, and Coronate E.
ＨＬ、ＥＨ（日本ポリウレタン工業社製、多価インシア
ネート化合物）等が挙げられる。Examples include HL and EH (manufactured by Nippon Polyurethane Industries, Ltd., polyvalent incyanate compounds).
ジアゾ樹脂としては、４−ジアゾジフェニルアミン、六
フッ化リン酸塩−ホルムアルデヒド樹脂、３−メトキシ
−ジフェニルアミン−４−ジアゾニウム塩と４．４′−
ビス−メトキシメチル−ジフェニルエーテルの縮合物の
メシチレンスルホネート塩等が挙げられる。The diazo resins include 4-diazodiphenylamine, hexafluorophosphate-formaldehyde resin, 3-methoxy-diphenylamine-4-diazonium salt and 4.4'-
Examples include mesitylene sulfonate salt of a condensate of bis-methoxymethyl-diphenyl ether.
多価エポキシ化合物としては、ビスフェノール系エポキ
シ樹脂、ビスフェノールＦジグリシジルエーテル、ノボ
ラックグリシジルエーテル、ヘキサヒドロフタル酸グリ
シジルエーテル、トリグリシジルイソシアヌレート等が
挙げられる。Examples of the polyvalent epoxy compound include bisphenol epoxy resin, bisphenol F diglycidyl ether, novolac glycidyl ether, hexahydrophthalic acid glycidyl ether, triglycidyl isocyanurate, and the like.
２個以上の重合可能なエチレン性不飽和二重結合を有す
る化合物としては、トリメチロールプロパントリアクリ
レート、テトラメチロールメタントリアクリレート、ア
リルアクリレート、１．４−ブタンジオールジメタクリ
レート等が挙げられる。なおエチレン性不飽和二重結合
を有する化合物を使用する場合には重合開始剤あるいは
光重合開始剤を併用する。Examples of the compound having two or more polymerizable ethylenically unsaturated double bonds include trimethylolpropane triacrylate, tetramethylolmethane triacrylate, allyl acrylate, and 1,4-butanediol dimethacrylate. In addition, when using a compound having an ethylenically unsaturated double bond, a polymerization initiator or a photopolymerization initiator is used together.
以上の架橋剤のうち好ましいのはジアゾ樹脂である。Among the above crosslinking agents, diazo resins are preferred.
（感光層）
感光層は支持体又は必要に応じて設けられるプライマー
層上に、リバースロールコータ、エアーナイフコータ、
メーヤバーコータなどの通常のコータあるいはホエラー
のような回転塗布装置を用いて、感光性組成物溶液を塗
布・乾燥して形成される。なお必要に応じて熱キユアさ
れる。(Photosensitive layer) The photosensitive layer is coated on the support or a primer layer provided as necessary using a reverse roll coater, an air knife coater,
It is formed by applying and drying a photosensitive composition solution using an ordinary coater such as a Meyer bar coater or a spin coating device such as a Whaler. Note that heat curing is performed as necessary.
感光層の構成は特に限定されず、各種の感光性物質が用
いられる。以下その代表的なものについて説明する。The structure of the photosensitive layer is not particularly limited, and various photosensitive substances can be used. Typical examples will be explained below.
先ず、従来公知の０−ナフトキノンジアジド化合物の如
きキノンジアジド型のポジ型感光性物質が挙げられる。First, quinonediazide-type positive photosensitive materials such as conventionally known 0-naphthoquinonediazide compounds are mentioned.
好適な０−ナフトキノンジアジド化合物としては、米国
特許３，０４８，１２０号明細書中に記載されているナ
フトキノン−（１，２）−ジアジド−（２）−スルホン
酸クロライドとフェノールまたはクレゾール−ホルムア
ルデヒド樹脂とのエステルがある。その他有用な０−ナ
フトキノンジアジド化合物としては１例えば米国特許３
，８３５．７０１３号に記載されているピロガロール−
アセトン樹脂と０−ナフトキノンジアジドスルホン酸ク
ロライドのエステル、特開昭５５−７８３４８号、同５
Ｂ−１０４４号及び同５１１ｉ−１０４５号に記載され
ているポリヒドロキシフェニル樹脂とＯ−ナフトキノン
ジアジドスルホン酸クロライドのエステル、特開昭５０
−１１３３０５号に記載されているようなｐ−ヒドロキ
シスチレンのホモポリマーまたはこれと他の共重合し得
るモノマーとの共重合体に０−ナフトキノンジアジドス
ルホン酸クロライドをエステル反応させたもの、特公昭
４Ｅｌ−１７４８１号記載のスチレンモノマニとフェノ
ール誘導体との重合体生成物と０−キノンジアジドスル
ホン酸との反応生成物、またポリヒドロキシベンゾフェ
ノンと０−ナフトキノンジアジドスルホン酸クロライド
のエステル等が挙げられる。Suitable 0-naphthoquinone diazide compounds include naphthoquinone-(1,2)-diazide-(2)-sulfonic acid chloride and phenol or cresol-formaldehyde resins described in U.S. Pat. No. 3,048,120. There is an ester with. Other useful 0-naphthoquinone diazide compounds include 1, for example, U.S. Pat.
, 835.7013.
Ester of acetone resin and 0-naphthoquinonediazide sulfonic acid chloride, JP-A-55-78348, JP-A-55-78348, JP-A-55-78348;
Ester of polyhydroxyphenyl resin and O-naphthoquinonediazide sulfonic acid chloride described in No. B-1044 and No. 511i-1045, JP-A-1989-1989
A homopolymer of p-hydroxystyrene or a copolymer of this with other copolymerizable monomers as described in Japanese Patent Publication No. 113305 and ester-reacted with 0-naphthoquinonediazide sulfonic acid chloride. -17481, a reaction product of a polymer product of styrene monomer and a phenol derivative and 0-quinonediazide sulfonic acid, and an ester of polyhydroxybenzophenone and 0-naphthoquinonediazide sulfonic acid chloride.
かかるキノンジアジド型の感光性物質を含有する感光性
組成物は必要に応じて結合剤を添加することができる０
例えば好適なものとしてアルカリ水溶液可溶性のノボラ
ック樹脂が挙げられる。このようなノボラック樹脂の例
としては、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、ｐ−ｔｅｒｔ−ブチルフ
ェノール−ホルムアルデヒド樹脂、フェノール変性キシ
レン樹脂などを代表例として挙げることができる。A binder may be added to a photosensitive composition containing such a quinonediazide type photosensitive substance, if necessary.
For example, suitable examples include novolac resins soluble in aqueous alkaline solutions. Typical examples of such novolac resins include phenol-formaldehyde resin, cresol-formaldehyde resin, p-tert-butylphenol-formaldehyde resin, and phenol-modified xylene resin.
感光性組成物中のキノンジアジド化合物の量は１０〜５
０重量％であり、より好ましくは２０〜４０重量％であ
る。また上記結合剤の配合量は感光性組成物中の４５〜
８０ｉ量％であり、好ましくは５０〜７０重量％である
。The amount of quinonediazide compound in the photosensitive composition is 10-5
It is 0% by weight, more preferably 20 to 40% by weight. In addition, the amount of the above-mentioned binder is 45 to 45% in the photosensitive composition.
It is 80i% by weight, preferably 50 to 70% by weight.
また感光性物質としては、芳香族ジアゾニウム塩とホル
ムアルデヒドとの縮合物で代表されるジアゾ樹脂も用い
られる。Further, as the photosensitive substance, a diazo resin typified by a condensate of an aromatic diazonium salt and formaldehyde is also used.
特に好ましくは、Ｐ−ジアゾジフェニルアミンとホルム
アルデヒドまたはアセトアルデヒドとの縮合物の塩、例
えばヘキサフルオロ燐酸塩、テトラフルオロホウ酸塩、
過塩素酸塩または過ヨウ素酸塩と前記縮合物との反応生
成物であるジアゾ樹脂無機塩や、米国特許３，３００，
３０９号に記載されているような、前記縮合物とスルホ
ン酸類の反応生成物であるジアゾ樹脂有機塩等が挙げら
れる。ざらにジアゾ樹脂は、好ましくは結合剤と共に使
用される。かかる結合剤としては種々の高分子化合物が
使用され得るが、好ましくは特開昭５←９８ｆｔ１３号
に記載されているような芳香族性水酸基を有する単量体
、例えばＮ−（４−ヒドロキシフェニル）アクリルアミ
ド、 Ｎ−（４−ヒドロキシフェニル）メタクリルアミ
ド、ｏ−、ｍ−１またはｐ−ヒドロキシスチレン、ｏ−
１１、またはｐ−ヒドロキシフェニルメタクリレート等
と他の単量体との共重合体、米国特許４．１２３，２７
８号に記載されているようなヒドロキシエチルアクリレ
ート単位またはヒドロキシエチルメタクリレート単位を
主なる繰り返し単位として含むポリマー、シェラツク、
ロジン等の天然樹脂、ポリビニルアルコール、米国特許
３，７５１，２５７号に記載されているポリアミド樹脂
、米国特許３．８８０，０１３７号に記載されている線
状ポリウレタン樹脂、ポリビニルアルコールのフタレー
ト化樹脂、ビスフェノールＡとエピクロルヒドリンから
縮合されたエポキシ樹脂、酢酸セルロース、セルロース
アセテートフタレート等のセルロース類が包含される。Particularly preferred are salts of condensates of P-diazodiphenylamine and formaldehyde or acetaldehyde, such as hexafluorophosphates, tetrafluoroborates,
A diazo resin inorganic salt which is a reaction product of a perchlorate or a periodate and the above-mentioned condensate, and U.S. Pat.
Examples include diazo resin organic salts, which are reaction products of the above condensate and sulfonic acids, as described in No. 309. The diazo resin is preferably used together with a binder. Various polymeric compounds can be used as such a binder, but monomers having an aromatic hydroxyl group such as those described in JP-A-5-98FT13, such as N-(4-hydroxyphenyl), are preferable. ) acrylamide, N-(4-hydroxyphenyl)methacrylamide, o-, m-1 or p-hydroxystyrene, o-
11, or a copolymer of p-hydroxyphenyl methacrylate, etc. and other monomers, U.S. Pat. No. 4,123,27
Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as a main repeating unit as described in No. 8, shellac,
Natural resins such as rosin, polyvinyl alcohol, polyamide resins described in U.S. Pat. No. 3,751,257, linear polyurethane resins described in U.S. Pat. No. 3,880,0137, phthalated resins of polyvinyl alcohol, Epoxy resins condensed from bisphenol A and epichlorohydrin, celluloses such as cellulose acetate and cellulose acetate phthalate are included.
また重合体主鎖または側鎖に感光基として−ＣＨ＝ Ｃ
Ｈ−Ｃ−を含むポリエステル類、ポリアミド１
類、ポリカーボネート類のような感光性重合体を主成分
とするものも挙げられる０例えば、特開昭５５−４０４
１５号に記載されているような、フェニレンジエチルア
クリレートと水素添加したビスフェノールＡおよびトリ
エチレングリコールとの縮合で得られる感光性ポリエス
テル、米国特許２，９５６．８７８号に記載されている
ような、シンナミリデン−Ｆ ａ ７酸等（７） （２
−プロベリデン）マロ′ン酸化合物及び二官能性グリコ
ール類から誘導される感光性ポリエステル類等が挙げら
れる。Also, -CH=C as a photosensitive group in the main chain or side chain of the polymer.
Examples include those whose main component is a photosensitive polymer such as polyesters containing H-C-, polyamides 1, and polycarbonates. For example, JP-A-55-404
15, photosensitive polyesters obtained by condensation of phenylene diethyl acrylate with hydrogenated bisphenol A and triethylene glycol; cinnamylidene, as described in U.S. Pat. No. 2,956,878; -F a 7 acids etc. (7) (2
Photosensitive polyesters derived from -probeliden) malonic acid compounds and difunctional glycols, and the like.
さらにアジド基が直接またはカルボニル基又はスルホニ
ル基を介して芳香環に結合している芳香族アジド化合物
も挙げられる０例えば、米国特許３．０９８，３１１号
に記載されているようなポリアジドスチレン、ポリビニ
ル−ｐ−アジドベンゾアート、ポリビニル−ｐ−アジド
ベンザール、特公昭４５−８６１３号に記載の７ジドア
リールスルフアニルクロリドと不飽和炭化水素系ポリマ
ーとの反応生成物、また特公昭４３−２１０１１７号、
同４←２２８号、同４４−２２９５４号及び同４５−２
４９１５号に記載されているような、スルホニルアジド
やカルボニルアジドを持つポリマー等が挙げられる。Further examples include aromatic azide compounds in which the azide group is bonded directly or via a carbonyl or sulfonyl group to an aromatic ring. For example, polyazidostyrene as described in U.S. Pat. No. 3,098,311; Polyvinyl-p-azidobenzoate, polyvinyl-p-azidobenzal, the reaction product of 7didoarylsulfanyl chloride and an unsaturated hydrocarbon polymer described in Japanese Patent Publication No. 1986-8613, and No. 210117,
4←No. 228, No. 44-22954 and No. 45-2
Examples include polymers having sulfonyl azide and carbonyl azide, as described in No. 4915.
さらにまた、付加重合性不飽和化合物からなる光重合性
組成物も挙げられる。Furthermore, a photopolymerizable composition comprising an addition polymerizable unsaturated compound may also be mentioned.
感光層の膜厚は０．０５〜１０ＪＬｍが好ましく、より
好ましくは０．１〜２ＪＬ鵬である。The thickness of the photosensitive layer is preferably 0.05 to 10 JLm, more preferably 0.1 to 2 JLm.
本発明において、感光性物質にはさらに、充填剤１色素
、染料、顔料、塗布性改良のための界面活性剤及び他の
常用の添加剤及び助剤を含有することができる。In the present invention, the photosensitive material may further contain filler 1 dyes, dyes, pigments, surfactants for improving coating properties and other conventional additives and auxiliaries.
なお、必要に応じて該感光層のうえに同様な方法で塗布
、乾燥することにより接着層を設けてもよい。Note that, if necessary, an adhesive layer may be provided on the photosensitive layer by coating and drying in a similar manner.
（シリコーンゴム層）
感光層又は必要に応じて設けられる接着層の上にシリコ
ーンゴム溶液を前記と同様の方法で塗布し、通常１００
〜１２０℃の温度で数分間加熱処理して十分に硬化せし
めてシリコーンゴム層を形成する。(Silicone rubber layer) A silicone rubber solution is coated on the photosensitive layer or an adhesive layer provided as necessary in the same manner as above, and usually 100%
Heat treatment at a temperature of ~120° C. for several minutes to fully cure and form a silicone rubber layer.
シリコーンゴム層に用いられるシリコーンゴムとしては
、次のようなくり返し単位を有する分子量数千〜数十万
の主鎖中又は主鎖の末端にＯＨ基を有する線状有機ポリ
シロキサンを主成分とするものが好ましい。The silicone rubber used in the silicone rubber layer is mainly composed of a linear organic polysiloxane having the following repeating units, a molecular weight of several thousand to several hundred thousand, and an OH group in the main chain or at the end of the main chain. Preferably.
（−Ｓｉ −０＋ｎ
ここでｎは２以上の整数、Ｒは炭゛素数１〜１０のアル
キル基、ハロゲン化アルキル基、ビニル基、アリール基
、シラノール基（０）１基）であり、Ｈの６０％以上が
メチル基であるものが好ましい。(-Si -0+n where n is an integer of 2 or more, R is an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, a vinyl group, an aryl group, one silanol group (0)), and Preferably, 60% or more of the methyl groups are methyl groups.
なお上記シラノール基（ＯＨ基）は主鎖中又は主鎖の末
端のどちらにあってもよいが、末端にあることが好まし
い。The silanol group (OH group) may be located either in the main chain or at the end of the main chain, but is preferably located at the end.
本発明において有用なシリコーンゴムは、このようなシ
リコーン・ベースポリマーと、次にあげるようなシリコ
ーン架橋剤との縮合反応によって得られるものである。The silicone rubber useful in the present invention is obtained by a condensation reaction between such a silicone base polymer and a silicone crosslinking agent as listed below.
（１） Ｒ−５ｉ＋ＯＲ”）
（２） Ｒ−Ｓｉ＋０Ａｃ）
（３） Ｒ−９ｉ＋０？ＣＲ”２）ｚ
ここでＲは先に説明したＲと同じ意味であり、Ｒ′はメ
チル基、エチル基などのアルキル基であり、ＡＣはアセ
チル基である。(1) R-5i+OR") (2) R-Si+0Ac) (3) R-9i+0?CR"2)z Here, R has the same meaning as R explained earlier, and R' is a methyl group or an ethyl group. and AC is an acetyl group.
これらのシリコーンゴムは市販品としても入手でき、例
えば東芝シリコーン社製ＹＥ−３０８５等がある。These silicone rubbers are also available as commercial products, such as YE-3085 manufactured by Toshiba Silicone Corporation.
また、その他の有用なシリコーンゴムは、上に挙げたよ
うなベースポリマーと、次のような繰り返し単位を有す
るシリコーンオイルとの反応、或いはＲの３％程度がビ
ニル基であるシリコーンベースポリマーとの付加反応、
或いは該シリコーンオイル同志の反応によっても得るこ
とかできる。Other useful silicone rubbers can be produced by reacting the base polymers listed above with silicone oils having the following repeating units, or by reacting silicone base polymers in which about 3% of R is vinyl groups. addition reaction,
Alternatively, it can also be obtained by a reaction between the silicone oils.
（式中、Ｒは先のＲと同じ意味であり、鵬は２以上の整
数、ｎはＯ又は１以上の整数である。）このような架橋
反応によって、シリコーンゴムを得るためには、上記の
成分の他に、錫、亜鉛。(In the formula, R has the same meaning as R above, Peng is an integer of 2 or more, and n is O or an integer of 1 or more.) In order to obtain silicone rubber by such a crosslinking reaction, the above-mentioned In addition to the ingredients, tin and zinc.
コバルト、鉛、カルシウム、マンガンなどの金属の有機
カルボン酸塩、例えばラウリン酸ジブチルスズ、スズ（
ｎ）オクトエート、ナフテン酸コバルトなど、或いは塩
化白金酸のような触媒が添加される。Organic carboxylates of metals such as cobalt, lead, calcium, manganese, etc., such as dibutyltin laurate, tin (
n) Catalysts such as octoate, cobalt naphthenate, etc. or chloroplatinic acid are added.
また、シリコーンゴムの強度を向上し、印刷作業中に生
じる摩擦力に耐え得るシリコーンゴムを得るためには、
充填材（フィラー）を混合することもできる。予めフィ
ラーの混合されたシリコーンゴムは、シリコーンゴムス
トック、或いはシリコーンゴムディスバージ、ンとして
市販されており１本発明のようにコーティングにより、
シリコーンゴム膜を得ることが好ましい場合には、ＲＴ
Ｖ或いはＬＴＶシリコーンゴムのディスバージョンが好
んで用いられる。このような例としては、トーレシリコ
ーン社製Ｓｙｌ （：Ｈｆ ２３．５ＲＸ−２５７゜５
Ｈ２３７などのペーパーコーチインク用シリコーンゴム
ディスバージョンがある。In addition, in order to improve the strength of silicone rubber and obtain silicone rubber that can withstand the frictional forces generated during printing operations,
Fillers can also be mixed. Silicone rubber pre-mixed with filler is commercially available as silicone rubber stock or silicone rubber dispersion, and as in the present invention, it can be coated with
If it is preferred to obtain a silicone rubber film, RT
Disversions of V or LTV silicone rubber are preferably used. An example of this is Syl (:Hf 23.5RX-257゜5) manufactured by Toray Silicone Co., Ltd.
There are silicone rubber dispersions for paper coach inks such as H237.
本発明においては、縮合架橋タイプのシリコーンゴムを
用いることが好ましい。In the present invention, it is preferable to use condensation and crosslinking type silicone rubber.
本発明においては、上記の成分の他に、シリコーンゴム
層中に光増感剤を少量含有せしめることができる。In the present invention, in addition to the above-mentioned components, a small amount of photosensitizer can be included in the silicone rubber layer.
シリコーンゴム層には、更に感光層との接着性を向上さ
せるためにシランカップリング剤を含有していることが
好ましい。Preferably, the silicone rubber layer further contains a silane coupling agent to improve adhesion to the photosensitive layer.
シランカップリング剤としては１例えば次のようなもの
がある。Examples of silane coupling agents include the following.
（ａ） Ｈ２ＮＣＨ２ＣＨ２ＨＨＣＣＩｈＣＨ２Ｃ１ｈ
ＳｉＣＯＣＨ３）ｓ（ｂ） ＣＴｏＣ）ＩＣＨ２０（Ｃ
）１２）３ｓｉ（ＯＣＨ：＋）ｘ＼／
（ｃ） ＨＳ（ＣＨ２ｈＳｉ（ＱＣ）Ｉ３）ｘ（ｄ）
ＧＨｚ−ＣＨＳｉ（ＯＣＯＣＨ３）ｚ（ｆ） ＧＨｚ−
ＣＨＳｉ（ＯＣＲ２ＣＨｘｈ（ｇ） ）１２ＮＧＨｚＧ
８２？１Ｈ（ＣＨ２ｈＳｉ（ＯＣＨ３）ｚ（ＯＨ３）（
ｈ）クロルシラン
シリコーンゴム層の膜厚は、０．１〜ｌ０ｇｍが好まし
く、より好ましくは０．５〜２μ璽である。(a) H2NCH2CH2HHCCIhCH2C1h
SiCOCH3)s(b) CToC)ICH20(C
)12)3si(OCH:+)x\/ (c) HS(CH2hSi(QC)I3)x(d)
GHz-CHSi(OCOCH3)z(f) GHz-
CHSi(OCR2CHxh(g))12NGHzG
82?1H(CH2hSi(OCH3)z(OH3)(
h) The thickness of the chlorosilane silicone rubber layer is preferably 0.1 to 10 gm, more preferably 0.5 to 2 gm.
なお感光性シリコーンゴム層とする場合には感光層は不
要であり、かかる感光性シリコーンゴムとしては、ジメ
チルポリシロキサンの末端ＯＨ基にγ−メタクリルオキ
シプロピルトリメトキシシラン、あるいはモノシンナモ
イルジェトキシシランを脱アルコール縮合させた化合物
、またはポリジオルガノシロキサンにビスアジド化合物
を添加、あるいはアクリロイルクロリドやｐ−アジドベ
ンゾエートを反応させた化合物などを挙げることができ
る。Note that in the case of forming a photosensitive silicone rubber layer, a photosensitive layer is not necessary, and as such a photosensitive silicone rubber, γ-methacryloxypropyltrimethoxysilane or monocinnamoyljetoxysilane is added to the terminal OH group of dimethylpolysiloxane. Examples include compounds obtained by dealcoholization condensation of polydiorganosiloxane, compounds obtained by adding a bisazide compound to polydiorganosiloxane, or compounds obtained by reacting acryloyl chloride or p-azidobenzoate.
（光透過性フィルム層）
次いでシリコーンゴム層上に光透過性フィルムをラミネ
ートして光透過性フィルム層を形成する。(Light-transparent film layer) Next, a light-transparent film is laminated on the silicone rubber layer to form a light-transparent film layer.
光透過性フィルム層は光透過性を有するフィルムによっ
て構成される層であり、ここに光透過性とは１例えば活
性光線（波長３０Ｇ＋１＋〜５００！Ｉ■）に対して光
線透過率が５０％以上のものをいう。A light transmitting film layer is a layer composed of a film having light transmittance, and here, light transmittance is defined as having a light transmittance of 50% or more for active light (wavelength 30G+1+ to 500!I■). It refers to something.
光透過性フィルム層に用いられる樹脂としては、ポリプ
ロピレン、ポリエチレン、ポリメチルペンテン、エチレ
ン−ブテン共重合体等のポリオレフィン、ポリスチレン
、フッ素樹脂が好ましい例として挙げられる。これらの
樹脂を用いることは、感光層にキノンジアジド化合物、
ジアゾ樹脂を用いた場合に有効である。即ちこれらの感
光層は露光によってＮ２ガスが発生するが、これらの樹
脂は良好なＮ２ガス透過性を示すからである。なおこれ
らの樹脂は機械的強度及び寸法安定性が低いものである
。Preferred examples of the resin used in the light-transmitting film layer include polyolefins such as polypropylene, polyethylene, polymethylpentene, and ethylene-butene copolymers, polystyrene, and fluororesins. Using these resins means that the photosensitive layer contains a quinonediazide compound,
This is effective when using diazo resin. That is, these photosensitive layers generate N2 gas when exposed to light, but these resins exhibit good N2 gas permeability. Note that these resins have low mechanical strength and dimensional stability.
本発明においては、感光層としてキノンジアジド化合物
、ジアゾ樹脂以外の物質を用いた場合には、光透過性フ
ィルム層に用いられる樹脂は上記に限定されず、例えば
ポリエチレンテレフタレート、ナイロン、ポリビニルア
ルコール、ポリカーボネート、ポリメチルメタクリレー
ト、ポリイミド、ポリアクリロニトリル等を用いること
ができる。In the present invention, when a substance other than a quinone diazide compound or diazo resin is used as the photosensitive layer, the resin used for the light-transmitting film layer is not limited to the above, and includes, for example, polyethylene terephthalate, nylon, polyvinyl alcohol, polycarbonate, Polymethyl methacrylate, polyimide, polyacrylonitrile, etc. can be used.
光透過性フィルム層の厚みは、 ０．５〜２０＃Ｌｍが
好ましく、より好ましくは３ｍ８川厘である。The thickness of the light-transmitting film layer is preferably 0.5 to 20 #Lm, more preferably 3 m8 thick.
（不連続マット層）
樹脂を溶解又は分散させた塗布液の微細な液滴を前記光
透過性フィルム層上に付着後乾燥又は熱硬化して該光透
過性フィルム層上に固体粒子が固着された不連続マー２
１層を形成する。(Discontinuous matte layer) Fine droplets of a coating liquid in which a resin is dissolved or dispersed are deposited on the light-transparent film layer, and then dried or thermally cured to fix solid particles on the light-transparent film layer. Discontinuous mark 2
Form one layer.
塗布液は樹脂を溶解または分散させた有機溶媒の溶液ま
たは分散液、水性の溶液１分散液またはエマルジョン溶
液等である。The coating liquid is a solution or dispersion of an organic solvent in which a resin is dissolved or dispersed, an aqueous solution, a dispersion, an emulsion solution, or the like.
本発明に用いられる塗布液の溶媒は、水又は沸点１３０
℃未満の有機溶剤であることが好ましい。The solvent of the coating liquid used in the present invention is water or boiling point 130
Preferably, the organic solvent has a temperature of less than .degree.
ただし沸点が１３０℃以上の宥機溶媒を５〜４０％含有
してもよい。However, it may contain 5 to 40% of a softener solvent with a boiling point of 130° C. or higher.
沸点１３０℃未満の有機溶剤としては、メチルセロソル
ブ、アセトン、メタノール、エタノール、プロパツール
、ブタノール、酢酸エチル、メチルエチルケトン、トル
エン、キシレン、メチルブチルケトン、メチルイソブチ
ルケトン、酢酸ブチル、酢酸プロピル、ジオキサン、プ
ロピレングリコールモノメチルエーテル、テトラヒドロ
フラン等があり、これらのうちから１ｍ又は２種以上を
選択使用できる。Organic solvents with a boiling point of less than 130°C include methyl cellosolve, acetone, methanol, ethanol, propatool, butanol, ethyl acetate, methyl ethyl ketone, toluene, xylene, methyl butyl ketone, methyl isobutyl ketone, butyl acetate, propyl acetate, dioxane, propylene. There are glycol monomethyl ether, tetrahydrofuran, etc., and 1 m or 2 or more types can be selected and used from these.
沸点１３０℃以上の有機溶剤としては、エチレングリコ
ール、ジエチレングリコール七ツメチルエーテル、乳酸
メチル、ジプロピレングリコール、シクロヘキサノン等
がある。Examples of organic solvents with a boiling point of 130° C. or higher include ethylene glycol, diethylene glycol 7-methyl ether, methyl lactate, dipropylene glycol, and cyclohexanone.
塗布液に用いられる樹脂は。What resin is used in the coating solution?
■ 例えば、ポリエチレン、ポリメチルメタクリレート
、ポリスチレン、フェノール樹脂、アイオノマー樹脂、
＾ＢＳ［脂、エチレン−酢酸ビニル共重合体、塩化ビニ
ル樹脂、ポリアミド樹脂。■ For example, polyethylene, polymethyl methacrylate, polystyrene, phenolic resin, ionomer resin,
^BS [fat, ethylene-vinyl acetate copolymer, vinyl chloride resin, polyamide resin.
フッ素樹脂、ポリエステル樹脂、エポキシ樹脂（硬化＃
） 、 スチレン−（メタ）アクリル酸或いはメタアク
リル酸エステル共重合樹脂等の熱可塑性樹脂
■ 例えば、エポキシ樹脂、フェノール樹脂、不飽和ポ
リエステル樹脂等に硬化剤を加えた樹脂等が挙げられる
。Fluororesin, polyester resin, epoxy resin (cured #
), Thermoplastic resins such as styrene-(meth)acrylic acid or methacrylic acid ester copolymer resins (2) Examples include resins obtained by adding a curing agent to epoxy resins, phenol resins, unsaturated polyester resins, etc.
前記塗布液の微細な液滴を光透過性フィルム層上に付着
させる方法は特に限定される訳ではないが、例えば静電
的に付着させる方法等がある。The method for depositing the fine droplets of the coating liquid on the light-transmissive film layer is not particularly limited, but includes, for example, a method for depositing them electrostatically.
静電的に付着される方法としては、公知の静電ｘ７−ス
プレー法、 ＋ｅｔｔｔエアーレススプレー法。Examples of electrostatic attachment methods include the well-known electrostatic x7-spray method and the +ettt airless spray method.
回転霧化式静電塗布法、特公昭５５−２８７４０号に記
載の静電塗布法等がある６本発明においては、静電的に
噴ｎ（スプレー）する方法が好ましい。Examples include a rotary atomization electrostatic coating method and an electrostatic coating method described in Japanese Patent Publication No. 55-28740.6 In the present invention, an electrostatic spraying method is preferred.
本発明の方法を用いる場合には、液滴状に噴霧した段階
、即ち液滴が空気中に分散している状態の間にできるだ
け有機溶剤を蒸発させ、液滴粒子の溶剤含有量をできる
だけ少なくしてから（光透過性フィルムに対して粘着性
を有する程度）、光透過性フィルムに付着させる。付着
の時点での溶剤の含有量を出来るだけ少なくして溶剤の
影響をなくすためである。When using the method of the present invention, the organic solvent is evaporated as much as possible during the stage of spraying into droplets, that is, while the droplets are dispersed in the air, to reduce the solvent content of the droplet particles as much as possible. After that (to the extent that it has adhesiveness to the light-transmitting film), it is attached to the light-transmitting film. This is to eliminate the influence of the solvent by reducing the solvent content as much as possible at the time of adhesion.
光透過性フィルムに対して粘着性を失う程度まで蒸発さ
せる場合には樹脂に融点が８０〜１５０℃のもの（例え
ばスチレン：メチルメタクリレート：アクリル酸ニブチ
ルアクリレート共重合体等）を用い、加熱融着させる方
法を採用することが好ましい。If the resin is to be evaporated to the extent that it loses its adhesion to the light-transmitting film, use a resin with a melting point of 80 to 150°C (for example, styrene: methyl methacrylate: nibutyl acrylate copolymer, etc.) and heat-melt it. It is preferable to adopt a method of wearing the cloth.
上記の方法によって形成された不連続マット層を構成す
る粒子は、露光用活性光線を実質的に透過可能であり、
粒子による散乱光の悪影響を防ぐために該固体粒子に紫
外線吸収剤、黄色染料、黄色顔料等を含有させることも
できる。The particles constituting the discontinuous matte layer formed by the above method can substantially transmit the exposing actinic rays,
The solid particles can also contain an ultraviolet absorber, a yellow dye, a yellow pigment, etc. in order to prevent the harmful effects of light scattered by the particles.
光透過性フィルム層の粒子による被覆率は０．５〜３０
％が好ましく、より好ましくは１〜５％である。このよ
うに不連続マー２ト層は光透過性フィルム層全体を被覆
していないので、光透過性フィルムのガス透過性が良い
。The coverage ratio of the particles of the light-transmitting film layer is 0.5 to 30
%, more preferably 1 to 5%. In this way, since the discontinuous mer2 layer does not cover the entire light-transmitting film layer, the light-transmitting film has good gas permeability.
粒子の形及び大きさは、固着前の粉体のときは特に限定
されないが、光透過性フィルム層上に固着された粒子は
、その高さが１〜５０ｐｍ 、さらに好ましくは３〜１
５ＩＬｍ、大きさ（幅）５〜２００ＩＬ１１、さらに好
ましくはＩＯ〜１（１（ｌ ｇ ｍの半球形、半楕円体
形１円柱形か好ましい。The shape and size of the particles are not particularly limited when they are powder before fixation, but the height of the particles fixed on the light-transmitting film layer is 1 to 50 pm, more preferably 3 to 1 pm.
5 ILm, size (width) 5 to 200 IL11, more preferably IO to 1 (1 (l g m) hemispherical, semi-ellipsoidal, 1 cylindrical or preferred.
本発明においては、粒子の表面を押圧することにより、
凸部の高さを均一にすることができる。In the present invention, by pressing the surface of the particles,
The height of the convex portion can be made uniform.
抑圧手段としては１版材を加熱ロール間に通す等の手段
か挙げられる。Examples of the suppressing means include passing one plate material between heating rolls.
以上の製造方法によって得られた湿し水不要平版印刷版
材料は４支持体の上に、感光層、シリコーンゴム層及び
光透過性フィルム層を膚し、該光透過性フィルム層上に
固体粒子が固着された不連続マット層を肴するものであ
る。The dampening water-free lithographic printing plate material obtained by the above production method has a photosensitive layer, a silicone rubber layer and a light-transparent film layer on the four supports, and solid particles are formed on the light-transparent film layer. This is a discontinuous mat layer to which is adhered.
また感光層及びシリコーンゴム層は、１層の感光性シリ
コーンゴム層であってもよい。Further, the photosensitive layer and the silicone rubber layer may be a single photosensitive silicone rubber layer.
次に本発明の湿し水不要版材を用いて湿し水不要印刷版
を製造する方法を説明する。Next, a method for manufacturing a printing plate that does not require dampening water using the plate material that does not require dampening water of the present invention will be explained.
原稿であるポジフィルムを版材表面に真空密着させ、露
光する。この露光用の光源は、紫外線を豊富に発生する
水銀灯、カーボンアーク灯、キセノンランプ、メタルハ
ライドランプ、蛍光灯などが用いられる。A positive film, which is the manuscript, is vacuum-adhered to the surface of the plate and exposed. As a light source for this exposure, a mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, etc., which generate abundant ultraviolet light, are used.
このとき不連続マー、ト暦の存在によって、真空密着性
が向上する。At this time, the vacuum adhesion is improved due to the presence of discontinuous particles.
露光後、光透過性フィルムを剥離し、現像液で現像する
と、未露光部のシリコーンゴム層及び感光層あるいはシ
リコーンゴム層のみが除去される。After exposure, the light-transmissive film is peeled off and developed with a developer to remove only the silicone rubber layer and photosensitive layer or silicone rubber layer in the unexposed areas.
上記のようにして凹部画線部が形成された刷版を得るこ
とができる。A printing plate in which the recessed image portion is formed can be obtained as described above.
本発明によれば、真空密着性を改良しっつ耐刷性を向上
できる湿し水不要平版印刷版材料の製造方法を提供する
ことができる。According to the present invention, it is possible to provide a method for producing a lithographic printing plate material that does not require dampening water and can improve vacuum adhesion and improve printing durability.
以下、本発明の実施例を挙げて本発明を更に詳説するが
、本発明はこれらの実施例によって限定されるものでは
ない。Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
実施例１
（ジアゾ樹脂−１の合Ｉ＆）
ｐ−ジアゾジフェニルアミン硫酸塩１４．５ｇ （５０
ミリモル）を水冷下で４０．９．の濃硫酸に溶解した。Example 1 (Synthesis I of diazo resin-1) p-diazodiphenylamine sulfate 14.5 g (50
40.9 mmol) under water cooling. of concentrated sulfuric acid.
この反応液に１．３５ｇ （４５ミリモル）のパラホル
ムアルデヒドをゆっくり反応温度が１０℃を超えないよ
うに添加した。1.35 g (45 mmol) of paraformaldehyde was slowly added to this reaction solution so that the reaction temperature did not exceed 10°C.
この反応混合物を水冷下、 ５００ｍ１のエタノールに
滴下し、生じた沈澱を濾過した。エタノールで洗冷後、
この沈澱物を１００ｍ１の純水に溶解し、この液に８．
８ｇの塩化亜鉛を溶解した冷濃厚水溶液を加えた。生じ
た沈澱を纏過した後、エタノールで洗浄し、これを １
５０ｍ１純水に溶解した。この液に８ｇのへキサフルオ
ロリン酸アンモニウムを溶解した冷濃厚水溶液を加えた
。生じた沈澱を濾過し、水洗した後、乾燥してジアゾ樹
脂−１を得た。This reaction mixture was added dropwise to 500 ml of ethanol under water cooling, and the resulting precipitate was filtered. After washing and cooling with ethanol,
This precipitate was dissolved in 100 ml of pure water, and 8.
A cold concentrated aqueous solution of 8 g of zinc chloride was added. After filtering off the resulting precipitate, it was washed with ethanol, and this was washed with 1
It was dissolved in 50ml of pure water. To this liquid was added a cold concentrated aqueous solution in which 8 g of ammonium hexafluorophosphate was dissolved. The resulting precipitate was filtered, washed with water, and then dried to obtain diazo resin-1.
（アルミニウム板ａの製造）
厚さ０．２４ｍｍのアルミニウム板を３％水酸化ナトリ
ウム水溶液に浸漬して脱脂し、水洗した後、３２％硫酸
水溶液中において温度３０℃で５Ａ／ｄｍ″の条件で１
０秒間、陽極酸化を行い、水洗し、２％メタケイ酸ナト
リウム水溶液に温度８５℃で３７秒間浸漬し、更に温度
８０℃の水（ｐＨ８，５）に２５秒間浸漬し、水洗、乾
燥して、アルミニウム板ａを得た。(Manufacture of aluminum plate a) An aluminum plate with a thickness of 0.24 mm is immersed in a 3% aqueous sodium hydroxide solution to degrease it, washed with water, and then immersed in a 32% aqueous sulfuric acid solution at a temperature of 30°C and a condition of 5 A/dm''. 1
Anodized for 0 seconds, washed with water, immersed in a 2% sodium metasilicate aqueous solution at a temperature of 85°C for 37 seconds, further immersed in water (pH 8.5) at a temperature of 80°C for 25 seconds, washed with water, dried, An aluminum plate a was obtained.
（版材の作成）
アルミニウム板ａに下記組成のプライマー層組成物を塗
布し、８５℃で３分間乾燥した後、３ＫＷ超高圧水銀灯
を用いて＋０００ｍＪ ／ｃｍ″の全面露光を行なった
。更に １００℃で４分間乾燥して厚さ０．８井口のプ
ライマー層を形成した。(Preparation of plate material) A primer layer composition having the following composition was applied to an aluminum plate a, and after drying at 85° C. for 3 minutes, the entire surface was exposed to +000 mJ/cm'' using a 3 KW ultra-high pressure mercury lamp. It was dried at ℃ for 4 minutes to form a primer layer with a thickness of 0.8 in.
［プライマー層組成物］
ジアゾ樹脂−１８重量部
２−ヒドロキシエチルメタクリレート、メタクリル酸メ
チルのモル比３４／ＩＬＬＳの共重合樹脂−１９２重量
部
メチルセロソルブ ８００重量部次に上記プ
ライマー層上に下記の組成の感光性組成物を塗布し１０
０℃で２分間乾燥して厚さ０．３ｐｍの感光層を形成し
た。[Primer layer composition] Diazo resin - 18 parts by weight 2-hydroxyethyl methacrylate, methyl methacrylate, copolymer resin with a molar ratio of 34/ILLS - 192 parts by weight Methyl cellosolve 800 parts by weight Next, the following composition was applied on the primer layer: Apply a photosensitive composition of 10
It was dried at 0° C. for 2 minutes to form a photosensitive layer with a thickness of 0.3 pm.
［感光性組成物］
ジアゾ樹脂−１５０重量部
２−ヒドロキシエチルメタクリレート、Ｎ−（４−ヒド
ロキシフェニル）メタクリルアミドのモル比２０７８０
の共重合樹脂−１５０重量部
ビクトリアピュアブルーＢＯ，Ｈ（保土ケ谷化学■製染
料） １重量部メチルセロソルブ
８００重量部次いで上記感光層上に下記
シリコーンゴム組成物を乾燥重量で１．８ｇ／ｍ’にな
るように塗布し、８０℃で４分間乾燥した。[Photosensitive composition] Diazo resin - 150 parts by weight Molar ratio of 2-hydroxyethyl methacrylate to N-(4-hydroxyphenyl)methacrylamide 20780
Copolymer resin - 150 parts by weight Victoria Pure Blue BO, H (dye manufactured by Hodogaya Chemical ■) 1 part by weight Methyl cellosolve 800 parts by weight Next, the following silicone rubber composition was applied to the photosensitive layer at a dry weight of 1.8 g/m' It was applied and dried at 80°C for 4 minutes.
［シリコーンゴム層組成物］
両末端に水酸基を右する
ジメチルポリシロキサン ＩＱＯｆｉ量部（分子量
８２，０００）
トリアセトキシメチルシラン １０ｆｉ量部ジブチ
ル錫ラウレート０．８重量部
アイソパーＥ（エッソ化学製）ＳＯＯ重量部次いで、シ
リコーンゴム層上に厚さ５ＩＬｍの片側がコロナ処理さ
れたポリプロピレンフィルム（本州製紙社製、アルファ
ンＥＭ２０１）をコロナ処理された面が上面になるよう
にラミネートした。[Silicone rubber layer composition] Dimethylpolysiloxane having hydroxyl groups at both ends IQOfi parts (molecular weight 82,000) Triacetoxymethylsilane 10 parts dibutyltin laurate 0.8 parts Isopar E (manufactured by Esso Chemical) SOO weight Next, a polypropylene film (Alphan EM201, manufactured by Honshu Paper Industries Co., Ltd.) having a thickness of 5 ILm and which had been corona-treated on one side was laminated on the silicone rubber layer so that the corona-treated side was the top surface.
上記のようにして得られた光透過性フィルム層の表面に
、下記塗布液を静電エアータイプのスプレーで塗布し、
１２０℃で３分間加熱硬化させた。The following coating solution was applied to the surface of the light-transmissive film layer obtained as above using an electrostatic air type spray.
It was heated and cured at 120°C for 3 minutes.
（塗布液）
エピコート１００１ １００重量部
メチルテトラヒドロ無水フタル酸 ３６重量部２．４
．８−）リス（ジメチルアミノ
メチル）フェノール １０重量部メチルセ
ロソルブ １０００ｉ量部粒子の高さが
平均８７Ｌｍ、大きさが１５〜１５０μｍ、光透過性フ
ィルム層の被覆率が１０％のマット層を有する湿し水不
要平版印刷版材料を得た。(Coating liquid) Epikote 1001 100 parts by weight Methyltetrahydrophthalic anhydride 36 parts by weight 2.4
．． 8-) Lis(dimethylaminomethyl)phenol 10 parts by weight Methyl cellosolve 1000i parts A moisturizer having a matte layer with particles having an average height of 87 Lm, a size of 15 to 150 μm, and a coverage of the light-transmitting film layer of 10%. A water-free lithographic printing plate material was obtained.
上記の版材の上面にポジフィルムを真空密着させた後、
光源としてメタルハライドランプを用いて露光し、光透
過性フィルムを剥離した。After vacuum-adhering the positive film to the top surface of the above plate material,
Exposure was performed using a metal halide lamp as a light source, and the light-transmitting film was peeled off.
次に、下記の現像液−１あるいは現像液−２に１分間浸
漬した後、版材の表面を、現像液を染み込ませたパッド
で擦ることにより、未露光部分のシリコーンゴム層と感
光層が除去され、網点が良好に再現された印刷版が得ら
れた。Next, after immersing it in developer-1 or developer-2 below for 1 minute, the surface of the plate material is rubbed with a pad impregnated with the developer to separate the unexposed portions of the silicone rubber layer and the photosensitive layer. A printing plate with good halftone dot reproduction was obtained.
これを湿し水供給装置をはずしたハイデルベルグＧＴＯ
印刷機に取り付け、東洋インキ社製ＴＯＹＯＫＩＮＧ
ｔｌＬＴＲＡ−丁ＫＵアクワレスＧ紅インキにより印刷
したところ、汚れのない印刷物が２，０万枚得られ、ハ
イライト部の再現性も良好であった。This is a Heidelberg GTO with the dampening water supply system removed.
Installed on the printing machine, TOYOKING manufactured by Toyo Ink Co., Ltd.
When printed with tlLTRA-Ding KU Aquares G red ink, 2,000,000 prints without stains were obtained, and the reproducibility of highlighted areas was also good.
（現像液−１）
β−アニリノエタノール ０．５重量部プ
ロピレングリコール ｔ、ｏ重Ｈ部ｐ −
ｔｅｒｔ−ブチル安息香酸 １．０重量部水酸
化カリウム １．０重量部ポリオ
キシエチレンラウリルエーテル０．２重量部亜硫酸カリ
ウム ２．０重量部メタケイ酸カ
リウム ３．０重量部水
９１重量部（現像液−２）
ベンジルアルコール ８重量部ペレッ
クスＮＢＬ（花王アトラス社製 アニオン界面活性剤３
５％水溶液） ５重量部ジェタノールアミ
ン ２重量部水
８５重量部実施例２
実施例１で得られた光透過性フィルム層の表面に、下記
塗布液をカップ状回転霧化頭を有する静電塗布装置によ
り微細液滴を付着乾燥させた。(Developer-1) β-anilinoethanol 0.5 parts by weight Propylene glycol t, o heavy H parts p −
Tert-butylbenzoic acid 1.0 parts by weight Potassium hydroxide 1.0 parts by weight Polyoxyethylene lauryl ether 0.2 parts by weight Potassium sulfite 2.0 parts by weight Potassium metasilicate 3.0 parts by weight Water
91 parts by weight (Developer-2) Benzyl alcohol 8 parts by weight Perex NBL (manufactured by Kao Atlas Co., Ltd. Anionic surfactant 3
5% aqueous solution) 5 parts by weight jetanolamine 2 parts by weight water
85 parts by weight Example 2 On the surface of the light-transmitting film layer obtained in Example 1, fine droplets of the following coating solution were applied and dried using an electrostatic coating device having a cup-shaped rotary atomizing head.
（塗布液）
メチルメタクリレート：エチルアクリレート：アクリル
酸ンーダ共重合体
（仕込重量比６８：２０：１２） １０重量部水
７０重量部エチレング
リコール ２ｏｉＨ［粒子の高さが平均８
川重、大きさが１５〜１５０川鵬、光透過性フィルム層
の被覆率が１０％のマット層を有する湿し水不要平版印
刷版材料を得た。(Coating liquid) Methyl methacrylate: Ethyl acrylate: Acrylic acid-undercopolymer (Preparation weight ratio 68:20:12) 10 parts by weight Water 70 parts by weight Ethylene glycol 2oiH [average particle height 8
A lithographic printing plate material which does not require dampening water and has a matte layer having a size of 15 to 150 Kawaho and a light-transmitting film layer coverage of 10% was obtained.
この版材を用いて、実施例１と同様に湿し水不要平版印
刷版を得、実施例１と同様に印刷を行ったところ、汚れ
のない印刷物が２．０万枚得られ、ハイライト部の再現
性も良好であった。Using this plate material, a lithographic printing plate requiring no dampening water was obtained in the same manner as in Example 1, and printing was performed in the same manner as in Example 1. 20,000 sheets of clean prints were obtained, with highlights The reproducibility of the parts was also good.
実施例３
実施例１で得られた光透過性フィルム層の表面に、下記
塗布液をカップ状回転霧化頭を有する静電塗布装置によ
り微細液滴を付着乾燥させた。Example 3 Fine droplets of the following coating solution were applied and dried on the surface of the light-transmissive film layer obtained in Example 1 using an electrostatic coating device having a cup-shaped rotating atomizing head.
（塗布液）
メチルメタクリレート＝２−ヒドロキシエチルメタクリ
レート：エチルアクリレート共重合体（仕込重量比８０
：２０：２０） ｔｏ重量部メチルセロソルブ
７０重量部ジエチレングリコール七ツメ
チルエーテル２０重量部
粒子の高さが平均８ル■、大きさが１５〜１５０ル量、
光透過性フィルム層の被覆率が１０％のマット層を有す
る湿し水不要平版印刷版材料を得た。(Coating liquid) Methyl methacrylate = 2-hydroxyethyl methacrylate: ethyl acrylate copolymer (charged weight ratio 80
:20:20) to parts by weight methyl cellosolve
70 parts by weight diethylene glycol 70 parts methyl ether 20 parts by weight Particles have an average height of 8 l and a size of 15 to 150 l,
A dampening water-free lithographic printing plate material having a matte layer with a light-transmitting film layer coverage of 10% was obtained.
この版材を用いて、実施例１と同様に湿し水不要平版印
刷版を得、実施例１と同様に印刷を行つたところ、汚れ
のない印刷物が２，０万枚得られ、ハイライト部の再現
性も良好であった。Using this plate material, a lithographic printing plate requiring no dampening water was obtained in the same manner as in Example 1, and printing was performed in the same manner as in Example 1. 2,000,000 sheets of clean prints were obtained, with highlights The reproducibility of the parts was also good.
実施例４
実施例１で得られた光透過性フィルム層の表面に、下記
塗布液をカップ状回転霧化頭を有する静電塗布装置によ
り微細液滴を付着した。付着後１００℃で１分間加熱し
て融着させた。Example 4 Fine droplets of the following coating solution were applied to the surface of the light-transmissive film layer obtained in Example 1 using an electrostatic coating device having a cup-shaped rotating atomizing head. After attachment, it was heated at 100° C. for 1 minute to fuse it.
（塗布液）
スチレン：メチルメタクリレート：アクリル酸ニブチル
アクリレート共重合体
（仕込重量比３０：３０：３０：１０ ） １０
重量部メチルセロソルブ ９０重量部２
０重量部
粒子の高さが平均８川重、大きさが２０〜１７０ドｌ、
光透過性フィルム層の被覆率が１０％のマット層を有す
る湿し水不要平版印刷版材料を得た。(Coating liquid) Styrene: Methyl methacrylate: Nibutyl acrylate copolymer (charged weight ratio 30:30:30:10) 10
Parts by weight Methyl cellosolve 90 parts by weight 2
The average height of the particles is 8 parts by weight, the size is 20 to 170 dollars,
A dampening water-free lithographic printing plate material having a matte layer with a light-transmitting film layer coverage of 10% was obtained.
この版材を用いて、実施例１と同様に湿し水不要平版印
刷版を得、実施例１と同様に印刷を行ったところ、汚れ
のない印刷物が２．０万枚得られ、ハイライト部の再現
性も良好であった。Using this plate material, a lithographic printing plate requiring no dampening water was obtained in the same manner as in Example 1, and printing was performed in the same manner as in Example 1. 20,000 sheets of clean prints were obtained, with highlights The reproducibility of the parts was also good.
実施例５
実施例１で得られた光透過性フィルム層の表面に、実施
例２で用いた塗布液をノズル径ｌａｍの２流体ノズル、
ルミナＮｏ、４０５５Ｔ−５（いけうち社製）空気圧３
Ｋｇ／ｃｍ２にて噴霧することにより微細液滴を付着乾
燥させた。Example 5 The coating liquid used in Example 2 was applied to the surface of the light-transmissive film layer obtained in Example 1 using a two-fluid nozzle with a nozzle diameter of lam.
Lumina No. 4055T-5 (manufactured by Ikeuchi) Air pressure 3
The fine droplets were attached and dried by spraying at Kg/cm2.
粒子の高さが平均８ド■、大きさが２０〜２００１Ｌ鵬
、光透過性フィルム層の被覆率が１０％のマット層を有
する湿し水不要平版印刷版材料を得た。A lithographic printing plate material which does not require dampening water and has a matte layer having a particle height of 8 mm on average, a size of 20 to 2001 L, and a coverage of the light-transmitting film layer of 10% was obtained.
この版材を用いて、実施例１と同様に湿し水不要平版印
刷版を得、実施例１と同様に印刷を行ったところ、汚れ
のない印刷物が２，０万枚得られ、ハイライト部の再現
性も良好であった。Using this plate material, a lithographic printing plate requiring no dampening water was obtained in the same manner as in Example 1, and printing was performed in the same manner as in Example 1. 2,000,000 sheets of clean prints were obtained, with highlights The reproducibility of the parts was also good.
実施例６
通常の方法で脱脂したスムースアルミニウム板上に乾燥
膜厚で２ＪＬ■になるように下記のプライマー層用組成
物を塗布し、１２０℃で５分間加熱硬化させた。Example 6 The following composition for a primer layer was applied to a smooth aluminum plate degreased in a conventional manner to a dry film thickness of 2 JL, and cured by heating at 120° C. for 5 minutes.
【プライマー層用組成物１
エピコー） １００１ （シェル化学社製のビスフェノ
ールＡ系エポキシ樹脂、
エポキシ当量は４５０〜５００） ｔｏｏ重量重量
デメチルテトラヒドロ無水フタル酸３６重量部２．４．
８−）リス（ジメチルアミノメチル）フェノール
ＩＯ重量都メチルセロンルブアセテー
ト６００重量部トルエン ＳＯ
Ｏ！ｉ量部メチ北部メチルエチルケトン ８００重
量部上記プライマー層を塗設したアルミニウム板上に、
シランカップリング剤及び有機スズ化合物を含有する下
記の感光性組成物を乾燥膜厚で０．２５ｇｍになるよう
塗布し、乾燥した。[Composition 1 for Primer Layer (Epicor) 1001 (Bisphenol A epoxy resin manufactured by Shell Chemical Co., Ltd., epoxy equivalent: 450-500) too weight: 36 parts by weight of demethyltetrahydrophthalic anhydride 2.4.
8-) Lis(dimethylaminomethyl)phenol
IO weight city Methylseronlube acetate 600 parts by weight toluene SO
O! i part Methi Northern Methyl Ethyl Ketone 800 parts by weight On an aluminum plate coated with the above primer layer,
The following photosensitive composition containing a silane coupling agent and an organic tin compound was applied to a dry film thickness of 0.25 gm and dried.
［感光性組成物］
ｐ−フェニレンジアクリル酸エステル
と１．４−ジヒドロキシエチルオキシ
シクロヘキサンとの１＝１（モル比）
重縮合による感光性不飽和
ポリエステル １０重量部ｌ−メチル−２
−ベンゾイルメチレン
−βナフトチアゾリン ０．６重量部Ｎ−（β
アミノエチル）アミノメチル
フェネチルトリメトキシシラン
０．４重量部
ジブチル錫ジオクタノエー） ０．８．を蓋部
スミトーンシアニンブルーＶＨ５１４
（住友化学社製フタロシアニン
ブルー顔料）２！ｉ量部
メチルセロソルブアセテート６００重量部トルエン
３００重量部次に、上記感光層
上に下記のシリコーンゴム組成物を乾燥膜厚で２．０ｐ
ｍになるよう塗布し、乾燥し、シリコーンゴム硬化層を
得た。[Photosensitive composition] 1=1 (molar ratio) of p-phenylene diacrylic acid ester and 1,4-dihydroxyethyloxycyclohexane Photosensitive unsaturated polyester obtained by polycondensation 10 parts by weight l-methyl-2
-benzoylmethylene-βnaphthothiazoline 0.6 parts by weight N-(β
(aminoethyl)aminomethylphenethyltrimethoxysilane 0.4 parts by weight dibutyltindioctanoate) 0.8. The lid part Sumitone Cyanine Blue VH514 (phthalocyanine blue pigment manufactured by Sumitomo Chemical Co., Ltd.) 2! i part methyl cellosolve acetate 600 parts by weight toluene
300 parts by weight Next, the following silicone rubber composition was applied on the photosensitive layer to a dry film thickness of 2.0 parts.
The silicone rubber cured layer was obtained by applying the coating to a thickness of m and drying.
［シリコーンゴムＪ＃Ｉ威物１
両末端に水酸基を有するジメチルポリ
シロキサン（分子量約１０００００） １００重量部
両末端にトリメチルシリル基を肴する
メチルハイドロジエンポリシロキサン
〔分子量約２５００） ６．０重量部
ｌ−メトキシシリルプロピル−３，５−ジアリルインシ
アヌレート３．３重量部ジブチル錫ジオクタノエート３
．３重量部アインパーＧ（エッソ化学社製） ２００
０重量部次いで、シリコーンゴム層上に厚さ５ＪＬｍの
片側がコロナ処理されたポリプロピレンフィルム（本州
製紙社製、フルファンＥＮ２０１）をコロナ処理された
面が上面になるようにラミネートした。[Silicone Rubber J#I Product 1 100 parts by weight of dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight: approx. 100,000) 6.0 parts by weight of methylhydrodienepolysiloxane having trimethylsilyl groups at both ends (molecular weight: approx. 2500) -Methoxysilylpropyl-3,5-diallyl in cyanurate 3.3 parts dibutyltin dioctanoate 3
．． 3 parts by weight Einpar G (manufactured by Esso Chemical Co., Ltd.) 200
0 parts by weight Next, a 5 JLm thick polypropylene film (manufactured by Honshu Paper Industries, Furufan EN201) which had been corona treated on one side was laminated on the silicone rubber layer so that the corona treated side was the top side.
上記のようにして得られた光透過性フィルム層の表面に
、下記塗布液を静電エアータイプのスプレーで塗布し、
１２０℃で３分間加熱硬化させた。The following coating solution was applied to the surface of the light-transmissive film layer obtained as above using an electrostatic air type spray.
It was heated and cured at 120°C for 3 minutes.
（塗布Ｗ１）
エピコート１００１ １００重量部
メチルテトラヒドロ無水フタル酸 ３Ｂ重量部２．４
，１１−トリス（ジメチルアミノメチル）フェノール
１０重量部メチルセロソルブ
１０００重量部粒子の高さが平均８ＩＬｍ、大きさ
が１５〜１５０ＪＬＩＩ、光透過性フィルム層の被覆率
が１０％のマット層を有する湿し水不要平版印刷版材料
を得た。(Coating W1) Epicoat 1001 100 parts by weight Methyltetrahydrophthalic anhydride 3B parts by weight 2.4
,11-tris(dimethylaminomethyl)phenol
10 parts by weight methyl cellosolve
A dampening water-free lithographic printing plate material having 1000 parts by weight particles having an average height of 8 ILm, a size of 15 to 150 JLII, and a matte layer with a coverage of the light-transmitting film layer of 10% was obtained.
、この版材にポジフィルムを重ね、真空密着させヌアー
ク社製ＥＴ２８Ｖ Ｕ［ｌＮＳ ＵＬＴＲＡ−ＰＬＵＳ
ＦＬＩＰ−ＴＯＰ ＰＬＡＴＥ ＭＡＫＥＲにより３
０カウント露光した後、光透過性フィルムを剥離し、ア
イソパーＨ（エッソ化学社製）８０重量部、ジエチレン
グリコールモノブチルエーテル７重量部、ジエチレング
リコールモノエチルエーテル３重量部及びコハク酸ジエ
チル５重量部よりなる現像液に１分間浸漬し、現像パッ
ドで１〜２分こすったところ、未露光部分の感光層及び
シリコーンゴム層が除去された。このようにして、印刷
版全面にわたって、ポジフィルムの画像を忠実に再現し
た湿し水不要平版印刷版が得られた。A positive film was layered on this plate material, and the film was vacuum-adhered using Nuark's ET28V U
3 by FLIP-TOP PLATE MAKER
After 0 count exposure, the light-transmissive film was peeled off and developed with 80 parts by weight of Isopar H (manufactured by Esso Chemical Co., Ltd.), 7 parts by weight of diethylene glycol monobutyl ether, 3 parts by weight of diethylene glycol monoethyl ether, and 5 parts by weight of diethyl succinate. When it was immersed in the liquid for 1 minute and rubbed with a developing pad for 1 to 2 minutes, the photosensitive layer and silicone rubber layer in the unexposed areas were removed. In this way, a lithographic printing plate that did not require dampening water was obtained, which faithfully reproduced the image of the positive film over the entire surface of the printing plate.
この版材を用いて、実施例１と同様に湿し水不要平版印
刷版を得、実施例１と同様に印刷を行ったところ、汚れ
のない印刷物が２，０万枚得られ、ハイライト部の再現
性も良好であった。Using this plate material, a lithographic printing plate requiring no dampening water was obtained in the same manner as in Example 1, and printing was performed in the same manner as in Example 1. 2,000,000 sheets of clean prints were obtained, with highlights The reproducibility of the parts was also good.
比較例１
特開昭８２−２４７８６８号の実施例１と同様の方法で
上記実施例１で用いた厚さ５ＩＬｍのポリプロピレンフ
ィルムに凹凸の樹脂層をグラビア検相し、片面に凹凸を
右するポリプロピレンフィルムをｍた。Comparative Example 1 An uneven resin layer was subjected to gravure phase inspection on the 5ILm thick polypropylene film used in Example 1 using the same method as in Example 1 of JP-A No. 82-247868. I got the film.
このポリプロピレンフィルムを実施例１のシリコーンゴ
ム層の表面に平滑面がシリコーンゴム層と接するように
ラミネートし、版材を得た。This polypropylene film was laminated on the surface of the silicone rubber layer of Example 1 so that the smooth surface was in contact with the silicone rubber layer to obtain a plate material.
この版材に実施例１と同様に露光したところ。This plate material was exposed in the same manner as in Example 1.
光透過性（カバー）フィルムとシリコーン層の間に露光
で発生した窒素ガスがたまり、気泡が発生していた。Nitrogen gas generated during exposure was trapped between the light-transmissive (cover) film and the silicone layer, causing bubbles.
実施例１と同様に現像したところ、焼ボケが生じ、網点
再現性が不良であった。When developed in the same manner as in Example 1, printing blur occurred and halftone dot reproducibility was poor.
Claims (1)
性シリコーンゴム層、及び光透過性フィルム層を有する
湿し水不要平版印刷版材料の製造方法において、前記シ
リコーンゴム層上に光透過性フィルム層を形成し、次い
で樹脂を溶解又は分散させた塗布液の微細な液滴を前記
光透過性フィルム層上に付着後乾燥又は熱硬化して該光
透過性フィルム層上に固体粒子が固着された不連続マッ
ト層を形成することを特徴とする湿し水不要平版印刷版
材料の製造方法。 ２、前記塗布液の微細な液滴を静電的に噴霧して前記光
透過性フィルム層上に付着させることを特徴とする請求
項１記載の湿し水不要平版印刷版材料の製造方法。 ３、塗布液の溶媒が、水又は沸点１３０℃未満の有機溶
剤であることを特徴とする請求項１又は２記載の湿し水
不要平版印刷版材料の製造方法。[Scope of Claims] 1. A method for producing a dampening water-free lithographic printing plate material having a photosensitive layer and a silicone rubber layer or a photosensitive silicone rubber layer and a light-transmitting film layer on a support, wherein the silicone rubber A light-transparent film layer is formed on the layer, and then fine droplets of a coating liquid in which a resin is dissolved or dispersed are deposited on the light-transparent film layer and then dried or thermally cured to form the light-transparent film layer. A method for producing a lithographic printing plate material that does not require dampening water, comprising forming a discontinuous matte layer on which solid particles are fixed. 2. The method for producing a lithographic printing plate material that does not require dampening water according to claim 1, characterized in that fine droplets of the coating liquid are electrostatically sprayed and deposited on the light-transmitting film layer. 3. The method for producing a lithographic printing plate material that does not require dampening water according to claim 1 or 2, wherein the solvent of the coating liquid is water or an organic solvent with a boiling point of less than 130°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31985889A JPH03179446A (en) | 1989-12-08 | 1989-12-08 | Production of damping waterless planographic printing plate material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31985889A JPH03179446A (en) | 1989-12-08 | 1989-12-08 | Production of damping waterless planographic printing plate material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03179446A true JPH03179446A (en) | 1991-08-05 |
Family
ID=18115022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31985889A Pending JPH03179446A (en) | 1989-12-08 | 1989-12-08 | Production of damping waterless planographic printing plate material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03179446A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009080422A (en) * | 2007-09-27 | 2009-04-16 | Toray Ind Inc | Waterless planographic printing plate precursor |
| JP2011034114A (en) * | 2010-11-08 | 2011-02-17 | Toray Ind Inc | Method for manufacturing waterless lithographic printing precursor, and waterless lithographic printing precursor |
| JP2011039558A (en) * | 2010-11-08 | 2011-02-24 | Toray Ind Inc | Waterless lithographic printing plate precursor |
| US8029915B2 (en) | 2002-10-28 | 2011-10-04 | Nippon Steel Corporation | Highly corrosion-resistant hot-dip galvanized steel product excellent in surface smoothness and formability and process for producing same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58163944A (en) * | 1982-03-25 | 1983-09-28 | Toray Ind Inc | Manufacture of lithographic original plate requiring no dampening water |
| JPS58186746A (en) * | 1982-04-26 | 1983-10-31 | Toray Ind Inc | Manufacture of lithographic plate material requiring no dampening water |
| JPS6127545A (en) * | 1984-07-17 | 1986-02-07 | Fuji Photo Film Co Ltd | Manufacture of photosensitive lithographic plate requiring no dampening water |
| JPH01159653A (en) * | 1987-12-16 | 1989-06-22 | Fuji Photo Film Co Ltd | Damping waterless photosensitive planographic printing master plate |
| JPH01257949A (en) * | 1988-04-08 | 1989-10-16 | Konica Corp | Damping-waterless planographic printing plate material |
-
1989
- 1989-12-08 JP JP31985889A patent/JPH03179446A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58163944A (en) * | 1982-03-25 | 1983-09-28 | Toray Ind Inc | Manufacture of lithographic original plate requiring no dampening water |
| JPS58186746A (en) * | 1982-04-26 | 1983-10-31 | Toray Ind Inc | Manufacture of lithographic plate material requiring no dampening water |
| JPS6127545A (en) * | 1984-07-17 | 1986-02-07 | Fuji Photo Film Co Ltd | Manufacture of photosensitive lithographic plate requiring no dampening water |
| JPH01159653A (en) * | 1987-12-16 | 1989-06-22 | Fuji Photo Film Co Ltd | Damping waterless photosensitive planographic printing master plate |
| JPH01257949A (en) * | 1988-04-08 | 1989-10-16 | Konica Corp | Damping-waterless planographic printing plate material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8029915B2 (en) | 2002-10-28 | 2011-10-04 | Nippon Steel Corporation | Highly corrosion-resistant hot-dip galvanized steel product excellent in surface smoothness and formability and process for producing same |
| JP2009080422A (en) * | 2007-09-27 | 2009-04-16 | Toray Ind Inc | Waterless planographic printing plate precursor |
| JP2011034114A (en) * | 2010-11-08 | 2011-02-17 | Toray Ind Inc | Method for manufacturing waterless lithographic printing precursor, and waterless lithographic printing precursor |
| JP2011039558A (en) * | 2010-11-08 | 2011-02-24 | Toray Ind Inc | Waterless lithographic printing plate precursor |
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