JPH03160453A - Planographic printing plate material requiring no damping water and production thereof - Google Patents
Planographic printing plate material requiring no damping water and production thereofInfo
- Publication number
- JPH03160453A JPH03160453A JP30025389A JP30025389A JPH03160453A JP H03160453 A JPH03160453 A JP H03160453A JP 30025389 A JP30025389 A JP 30025389A JP 30025389 A JP30025389 A JP 30025389A JP H03160453 A JPH03160453 A JP H03160453A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- light
- silicone rubber
- plate material
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims description 39
- 238000007639 printing Methods 0.000 title claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 29
- 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 53
- 239000004945 silicone rubber Substances 0.000 claims abstract description 52
- 239000002245 particle Substances 0.000 claims abstract description 37
- 239000007787 solid Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims description 51
- 239000011347 resin Substances 0.000 claims description 51
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000004927 fusion Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 121
- 239000010408 film Substances 0.000 description 71
- 238000000034 method Methods 0.000 description 25
- -1 polyethylene terephthalate Polymers 0.000 description 25
- 229920001296 polysiloxane Polymers 0.000 description 15
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000013039 cover film Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004698 Polyethylene Substances 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
- 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 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000010954 inorganic particle Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
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- 239000000843 powder Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 239000004793 Polystyrene 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229920005601 base polymer Polymers 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 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 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-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
- 239000004925 Acrylic resin Substances 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000002253 acid Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 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
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920000306 polymethylpentene Polymers 0.000 description 2
- 239000011116 polymethylpentene Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000012192 staining solution Substances 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- PJMXUSNWBKGQEZ-UHFFFAOYSA-N (4-hydroxyphenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=C(O)C=C1 PJMXUSNWBKGQEZ-UHFFFAOYSA-N 0.000 description 1
- KNNFDCWYZOSALE-UHFFFAOYSA-N 1-diethoxysilyl-3-phenylprop-2-en-1-one Chemical compound C(C=CC1=CC=CC=C1)(=O)[SiH](OCC)OCC KNNFDCWYZOSALE-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- BLPUXJIIRIWMSQ-QPJJXVBHSA-N 2-[(e)-3-phenylprop-2-enylidene]propanedioic acid Chemical compound OC(=O)C(C(O)=O)=C\C=C\C1=CC=CC=C1 BLPUXJIIRIWMSQ-QPJJXVBHSA-N 0.000 description 1
- MWGATWIBSKHFMR-UHFFFAOYSA-N 2-anilinoethanol Chemical compound OCCNC1=CC=CC=C1 MWGATWIBSKHFMR-UHFFFAOYSA-N 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical compound [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 235000015178 Asplenium bulbiferum subsp bulbiferum Nutrition 0.000 description 1
- 244000178908 Asplenium bulbiferum subsp bulbiferum Species 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 101100096319 Drosophila melanogaster Spc25 gene Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical class OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 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
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Landscapes
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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及びその製造方法
に関し、詳しくは酎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及びその
製造方法に関する．（従来の技術）
湿し水不要平版印刷版材料に画像を形戒するためには，
通常Ｍ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、該版村上面に原画を完全
に密着させることが必要であった．このため、一般的に
はゴムシ一トと圧着ガラスの間に、該版材と原画とを重
ねて配置し，ゴムシ一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．
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．
特開昭６２−２４７８６８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、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（凹凸を有しない
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暦を設ける
方法が開示されている．
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イ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．（発明が解決しようとするＷ１
題）
しかし、特開１１ｉ ６２−２４７８６８号に記載の方
法では． ＰＥＴ（ポリエチレンテレフタレート）のよ
うに比較的フィルムの機械的強度か強く，塗布乾燥時の
加熱の＃も安定したフィルムの材質を有しているものを
用いる場合にはそれほど問題とならないが，ボリプロビ
レンやポリエチレンのように機械的強度が低く、加熱し
た時や張力をかけた時の寸法安定性の小さなフィルムを
用いた場合には凹凸を有するフィルムを製造する際にし
わが入ったり伸びてしまったりする問題かある．また例
え製造することができたとしても、あまり張力をかけた
り，熱を加えたりできないため，塗春スピードをあげら
れず，製版性能が劣るという問題がある．従って、上記
方法ではフィルムの厚さを厚くして、フィルムの機械的
強度、加熱時の安定性を確保する必要がある．しかしこ
の場合原稿と感光層間の間隙が大きくなり、網点再現性
が悪くなる問題がある．
上記問題を解決するする方法としては，平滑なカバーフ
ィルムをラミネートした後、グラビアロールによって凹
凸のパターンを塗設する方法が考えられる．この方法は
カバーフィルムがシリコーン層と接着しているため，フ
ィルム自体の熱的安定性，機械的強度は前記方法ほど問
題とならない．しかし、この方法では塗布する樹脂の溶
媒でカバーフィルムが１１１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わ
ずかな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、酎刷性が劣るという問題がある．このよう
な問題はカバーフィルムがＰＵＴの場合にも同様に生じ
ることが判った．また特開昭５５−５５３４３号に記載
のような、実質的に平滑な保護フィルム上に無機粒子を
含む溶液を塗血する方法においても，やはり塗布溶媒を
用いているため，カバーフィルムが膨潤する等の問題が
ある．更に無機粒子を用いているため以下のような問題
がある．即ち，無機粒子はそれ単独あるいはわずかな溶
媒だけでは、例え加熱してもカバーフィルムに固着する
ことはできず、バインダーとなる塗血液樹脂が必要とな
る．従ってこのバインダーが乾燥固化されることによっ
て連続マット歴が形成され、カバーフィルムの上部に更
にもう１層の樹脂層が形成されることになる．このため
カバーフィルムが結果として厚くなり，画像再現性が悪
くなるという問題がある．
そこで本発明の第１の目的は、真空密着性を改良しつつ
画像再現性が向上した湿し水不要平版印刷版材料を提供
することにある．
また本発明の第２の目的は，製版性能が高く、真空密着
性を改良しっつ耐刷性を向上す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．
（課題を解決するための手段）
本発明者は，上記目的を達成すべく鋭意検討の結果、未
発明に至った．
即ち，本発明に係る湿し水不要平版印刷版材料は、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
要平版印刷版材料において、前記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有することを
特徴とする．
また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成し、次い
で該光透過性フィルム層上に固体粒子を加熱手段を介し
て固着することにより不Ｊ！［続マット層を形成するこ
とを特徴とする．
木発明の好ましい態様としては，光透過性フィルム層が
比較的機械的強度及び寸法安定性が低い樹脂によって形
成されていることであり，また本発明の好ましい他の態
様としては，熱可塑性を有する樹脂粒子を光透過性フィ
ルム層上にａ１ｒＩｔ，．熱融着して紘光透過性フィル
ム層上に固着して不連続マット層を形成することである
．
（作用）
本発明の湿し水不要平版印刷版材料は，光透過性フィル
ム層上に固体粒子が固着された不ｍ続マット層としたた
め、特開昭５５−５５３４３号に記載のように連続マッ
ト層を形成するのと異なって，光透過性フィルムを薄く
できる．このように光透過性フィルムを薄くできるため
に，網点再現性若しくは画像再現性が向上する．従って
第１の目的が達威される．
また本発明の湿し水不要平版印刷版材料の製造方法は，
光透過性フィルム層上に固体粒子を加熱手段を介して固
着することにより不連続マット層を形成する方法を裸用
するため，溶剤をほとんど使わないか、または悪影響を
与えない程度に低減できるため，例えシリコーンゴム層
上にボリブロピレンやポリエチレンのように比較的機械
的強度及び寸法安定性が低い樹脂によって光透過性フィ
ルム層を形成しても、しわ等のｒＲ１題や製版性能低下
という問題を解消でき，更に溶剤による膨ｆｉｌｌ等に
起因する酎刷性の低下を招くこともない．即ち木発明の
製造方法によれば、製版性能が高いたけでなく，真空密
着性を改良し耐刷性を向上できる．従って本発明の第２
の目的が達成される．（発明の構成）
以下，本発明について詳説する．
本発明の湿し水不要平版印刷版材料（以下−，湿し水不
要版材または単に版材ともいう．）は，その一例を挙げ
ると、第１図に示すような支持体ｌの上に，感光層２、
シリコーンゴム暦３及び光透過性フィルム層４を有し、
該光透過性フィルム層４上に固体粒子が固着された不連
続マット層５を有するものである．
また感光層２及びシリコーンゴム層３は，１層の感光性
シリコーンゴム層であってもよい．支持体としては、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
る荷重に耐えうるものであることが好ましく、例えばア
ルくニウム，亜鉛、銅、鋼等の金属板，及びクロム，亜
鉛、銅，ニッケル，アルくニウム及び鉄等がメッキ又は
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．Ｓ水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
．アルく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．
支持体の厚みは、５０〜４００μ匹が好ましく、より好
ましくは１００〜３００ル１である．支持体上にはプラ
イマー層を肴レていてもよく，該プライマー層には樹脂
やシランヵップリング剤が好ましく，樹脂としては，例
えばポリエステル樹脂，１１Ｋ化ビニルー酢酸ビニル共
重合体、アクリル樹脂、塩化ビニル樹脂、ボリアくド樹
脂，ポリビニルブチラール樹脂，エボキシ樹脂，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
捌脂，ポリウレタン樹脂、ボリカーボネート樹脂，ポリ
アクリロニトリルブタジエン、ポリ酢酸ビニル等が挙げ
られる．
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−ヒト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．
また上記プライマー層を構成するアンカー剤としては，
例えば前記のシリコーンゴム層に用いられるシランカッ
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なども有効である．
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．
先ず，従来公知のＯ−ナフトキノンジアジト化合物の如
きキノンジアジト型のボジ型感光性物質か挙げられる．
好適な０−ナフトキノンジアジト化合物としては、米国
特許３，０４６，１２０号明細書中に記載されているナ
フトキノンー（１．２）一ジアジド−（２）ースルホン
酸クロライトとフェノールまたはタレゾールーホルムア
ルデヒド樹脂とのエステルがある．その他有用な０−ナ
フトキノンジアジト化合物としては，例えば米国特許３
，６３５，７０９号に記載されているビロガロールーア
セトン樹脂と０−ナフトキノンジアジトスルホン酸クロ
ライドのエステル，特開昭５５−７６３４６号、同５６
−１０４４号及び同５６−１０４５号に記載されている
ポリヒト口キシフェニル樹脂と０−ナフトキノンジアジ
トスルホン酸クロライドのエステル、特開昭５０−１１
３３０５号に記載されているようなｐ−ヒトロキシスチ
レンのホモボリマーまたはこれと他の共重合し得る七ノ
マーとの共重合体に０−ナフトキノンジアジトスルホン
酸クロライドをエステル反応させたもの、特公昭４９−
１７４８１号記載のスチレンモノマーとフェノール誘導
体との重合体生ｔＣ物と０−キノンジアジトスルホン酸
との反応生ｒ＆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トスルホン酸クロライドのエ
ステル等が挙げられる．
かかるキノンジアジト型の感光性物質を含塙する感光性
組威物は必要に応じて結合剤を添加することができる．
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
ック樹脂か挙げられる．このようなノボラック樹脂の例
としては，フェノールーホルムアルデヒド樹脂，クレゾ
ールーホルムアルデヒド樹脂． ｐ｛ｅｒｔ−ブチルフ
ェノールー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．感光
性組成物中のキノンジアジト化合物の量は１０〜５０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ｍ成物中の４５〜８０
重量％であり、好ましくは５０〜７０ｉ量％である．
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金物で代表されるジアゾ樹脂も用い
られる．
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４ｌ１ａ！や、米ｒＢ＃許３，
３００，３０９号ニ記１１．サレ”Ｃイるような，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５４
−９８６１：ｌ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−ヒトロキシフェニ
ル）アクリルアｔ ｝’． ． Ｎ−（４−ヒトロキシ
フェニル）メタクリノレアくド， ０−，鳳−、または
ｐ−ヒトロキシスチレン、ｏ−， ｍ−、またはｐ−ヒ
トロキシフェニルメタクリレート等と他のＩＪｉ量体と
の共重合体、米国特許４，１２３．２７６号に記載され
ているようなヒト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
単位として含むボリマー，シエラック，ロジン等の天然
樹脂、ポリビニルアルコール、米国特許３，７５１，２
５７号に記載されているボリアミド捌脂、米国特許３，
５５１），０９７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とエビクロルヒトリンから縮合されたエボ
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．
また重合体主鎖または側鎖に感光基として類，ボリカー
ボネート類のような感光性重合体を主戒分とするものも
挙げられる．例えば，特開昭５５−４０４１５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２，９ＳＩｉ．８７８号に記載されているような、
シンナミリデンマロン酸等の（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．
さらにアジト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ト化合物
も挙げられる．例えば，米国特許３，０９６，３１１号
に記載されているようなポリアジトスチレン，ポリビニ
ルーｐ−アジトベンゾアート，ポリビニルーｐ−アジト
ベンザール、特公昭４５一９６１３号に記載のアジトア
リールスルファニルクロリドと不飽和炭化水素系ボリマ
ーとの反応生成物，また特公昭４３−２１０６７号、同
４４−２２９号、同４４−２２９５４号及び同４５−２
４９１５号に記載されているような、スルホニルアジト
やカルボニルアジトを持つボリマー等が挙げられる．
さらにまた，付加重合性不飽和化合物からなる光重合性
組或物も挙げられる．
感光層の膜厚は０．０５〜１０ト箇か好ましく，より好
ましくは０．１〜２μ鵬である．
本発明において，感光性物質にはさらに、充填剤、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膚することができる．
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ボリ
シロキサンを主成分とするものが好ましい．
Ｒ
％Ｓｉ −０九
Ｒ
ここでｎは２以上の整数、Ｒは炭素数ｌ〜ｌＯ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（ＯＨ基）であり、凡の６０％以上がメ
チル基であるものが好ましい．なお上記シラノール基（
ＯＨ基）は主鎖中又は主釦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．
本発明において宥用なシリコーンゴムは、このようなシ
リコーン・ベースボリマーと、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．
（１） Ｒ−Ｓｉ＋Ｏｎ’）
（２） Ｒ−Ｓｉ＋ＯＡｃ）
（３） Ｒ−Ｓｉ−｛−ＯＮ−ＣＲ’ａ）＊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．
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．
また、その他の有用なシリコーンゴムは，上に挙げたよ
うなベースボリマーと，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ボ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
とができる．
（式中，Ｒは先のＲと同じ意味であり，Ｓは２以上の整
数，ｎは０又は１以上の整数である．）このような架橋
反応によって、シリコーンゴムな得るためには、上記の
威分の他に、錫、亜鉛，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（ ＩＩ ）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．
また、シリコーンゴムの強度を向上し、印刷作東中に生
じる摩擦力に耐え得るシリコーンゴムな得るためには，
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ョンとして
市販されており，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ａンが好
んで用いられる．このような例とレては，トーレシリコ
ーン社製Ｓ３１１ ０ｆｆ ２３、ＳＲＸ−２５７、Ｓ
Ｈ２３７などのペーパーコーティング用シリコーンゴム
デイスバージョンがある．
本発明においては，縮合架橘タイプのシリコーンゴムを
用いることが好ましい．
本発明においては、上記の威分の他に，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．
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看していることが
好ましい．
シランカップリンク剤と．しては、例えば次のようなも
のかある．
（ａ） ｌｌＪＣＨａＣＩＩｚＮ１１ＣＣＨ２ＣＩｌ，
ＣＨｘＳｉ（ＯＣｌｌｔ）＋（ｂ）黒ｊジｌｌｃＨ＊ｏ
（Ｃｌｌｔ）ｉｓｉ（ＯＣＩＩ＋）ｚ０
（ｅ） ＩＩｓ（（：ＩＩｓ）３ｓｆ（ＯＣＩＩｚ）ｚ
（ｄ） Ｃａｌ２〜ＣｌｌＳｉ（ＯＣＯＣＨ：＋）ｚ（
ｆ） ＣＩＩ＊−ＣＩＩＳｉ（ＯＣｌｌｔＣＨ３）ｚ（
ｇ） ＨＪＣＨ＊ＣＨＪＨ（Ｃｕｔ）ｚｓｉ（ＯＣＩｌ
ｉ）ｔ（ＣＨ３）（ｈ）クロルシラン
シリコーンゴム暦の膜厚は、 ロ．１〜１０μ鵬が好ま
しく、より好ましくは０．５〜２ルーである．
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
チルボリシロキサンの末端ＯＨ基にγ−メタクリルオキ
シブロビルトリメトキシシラン，あるいはモノシンナモ
イルジエトキシシランを脱アルコール縮合させた化合物
，またはポリジ才ルガノシロキサンにビスアジト化合物
を添加，あるいはアクリロイルクロリドやｐ−アジトベ
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．
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，例えば活
性光線（波長３００ｎ一〜５００ｎｍ）に対して光線透
過率が５０％以上のものをいう．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，エチレンーブテン共重合体等
のポリオレフィン，ボリスチレン、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ト化合物，ジアゾ樹脂を用いた場
合に墳効である．即ちこれらの感光層は露光によってｈ
ガスが発生するが，これらの樹脂は良好なＮ，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．
本発明においては，感光層としてキノンジアジト化合物
、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、ボリカーボネート、ポリメチルメタクリレ
ート、ボリイミト，ポリアクリロニトリル等を用いるこ
とができる．
光透過性フィルム層の厚みは、ロ，５〜２０目が好まし
く，より好ましくは３〜８ＪＬａである．木発明におい
て，マット層は固体粒子が光透過性フィルム層に固着さ
れて形成された不連続層である．
固体粒子は露光用活性光線を実質的に透過可能なものが
用いられるが、固体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、黄色染ネＬ黄色顔料等
を含墳させることもできる．
光透過性フィルム層の固体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
のように不連続マッ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．
固体粒子の具体例としては、
■ 例えば、ポリエチレン、ポリメチルメタクリレート
、ボリスチレン、フェノール樹脂，アイオノマー樹脂，
ＡＢＳ樹脂，エチレンー酢酸ビニル共重合体、塩化
ビニル樹脂，ボリアミト樹脂．フッ素樹脂，ポリエステ
ル樹脂、エボキシ樹脂（硬化前）、スチレンー（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、エボキシ樹脂、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■ 二酸化珪素
，酸化亜鉛、酸化チタン．Ｓ化ジルコニウム，ガラス粒
子，アルミナ、澱粉を上記■及び■の樹脂によって被覆
したものこれら■〜■の固体粒子は２種以上を併用して
もよい．なお、米国特許２，７０１，２４５号、同２，
９９２，１０１号に記載されているマット剤を使用する
ことができる．
固体粒子として上記■又は■の樹脂を用いる場合には，
その融点（ａ．ｐ．）は，光透過性フィルム層への熱融
着の容易性を考慮して６０〜１５０℃が好ましい。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a lithographic printing plate material that does not require dampening water and a method for producing the same, and more specifically, to improve vacuum adhesion while having good printability. This paper relates to a lithographic printing plate material that does not require dampening water and a method for manufacturing the same. (Prior art) In order to imprint an image on a lithographic printing plate material that does not require dampening water,
Normally, exposure to active light is carried out through the M image, but in order to faithfully reproduce the original image, it was necessary to bring the original image into complete contact with the upper surface of the printing plate. For this reason, a vacuum adhesion method is generally 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 a vacuum is created between the rubber sheet and the pressure-bonding glass to bring them into close contact. Ta. However, it is difficult to achieve sufficient vacuum adhesion, and various techniques have been proposed to improve this. JP-A No. 62-247868 discloses that after applying a resin liquid onto a film using a gravure roll, a film with an uneven pattern corresponding to the engraving of the gravure roll is made, and then the smooth surface (unevenness) of this film is A method is disclosed for providing a matte calendar on a cover film by laminating the cover film so that the surface (not having a silicone rubber layer) is in contact with a silicone rubber layer. Furthermore, JP-A No. 55-55343 discloses a technique of coating an uneven transparent film on the uppermost silicone rubber layer, and as a method of providing unevenness, inorganic particles are coated on a substantially smooth protective film. The method of applying a solution is also described as effective. (W1 that the invention attempts to solve
However, the method described in JP-A No. 11i 62-247868. This is not so much of a problem when using a film material such as PET (polyethylene terephthalate), which has relatively strong mechanical strength and stable heating during coating and drying. When using a film such as polyethylene, which has low mechanical strength and low dimensional stability when heated or under tension, there is a problem that it wrinkles or stretches when producing a film with unevenness. There is. Furthermore, even if it were possible to manufacture it, it would not be possible to apply much tension or heat, so the coating speed could not be increased, resulting in poor plate-making performance. Therefore, in the above method, it is necessary to increase the thickness of the film to ensure its mechanical strength and stability during heating. However, in this case, there is a problem that the gap between the original and the photosensitive layer becomes large, resulting in poor halftone dot reproducibility. One possible method to solve the above problem is to laminate a smooth cover film and then apply a pattern of unevenness using a gravure roll. In this method, the cover film is bonded to the silicone layer, so the thermal stability and mechanical strength of the film itself are not as important as in the previous method. However, with this method, the cover film becomes wet with the solvent of the applied resin and peels off from the silicone layer, and even if it does not swell, the small amount of solvent that penetrates may cause hardening of the silicone layer or the gap between the silicone layer and the photosensitive layer. This has a negative effect on the adhesion of the film, causing the silicone layer to peel off during development, resulting in poor printability. It was found that similar problems also occur when the cover film is PUT. Furthermore, in the method described in JP-A No. 55-55343, in which a solution containing inorganic particles is applied onto a substantially smooth protective film, a coating solvent is also used, which causes the cover film to swell. There are problems such as. Furthermore, since inorganic particles are used, there are the following problems. That is, the inorganic particles cannot be fixed to the cover film alone or with only a small amount of solvent, even if heated, and a coating resin is required as a binder. Therefore, when this binder is dried and solidified, a continuous matte history is formed, and another resin layer is formed on top of the cover film. As a result, the cover film becomes thicker, resulting in a problem of poor image reproducibility. Therefore, the first object of the present invention is to provide a lithographic printing plate material that does not require dampening water and has improved vacuum adhesion and improved image reproducibility. A second object of the present invention is to provide a method for producing a lithographic printing plate material that does not require dampening water and has high plate-making performance, improved vacuum adhesion, and improved printing durability. (Means for Solving the Problems) As a result of intensive studies to achieve the above object, the inventors have come up with an uninvented invention. That is, the dampening water-free planographic printing plate material according to the present invention is a dampening water-free planographic printing plate material having a photosensitive layer, a silicone rubber layer or a photosensitive silicone rubber layer, and a light-transmitting film layer on a support. The method is characterized in that it has a discontinuous matte layer on which solid particles are fixed on the light-transmitting film layer. Further, the method for producing a dampening water-free lithographic printing plate material according to the present invention includes a dampening water-free planographic printing method comprising, on a support, a photosensitive layer, a silicone rubber layer or a photosensitive silicone rubber layer, and a light-transmitting film layer. In the method for producing a plate material, a light-transmitting film layer is formed on the silicone rubber layer, and solid particles are then fixed on the light-transmitting film layer using a heating means, so that non-J! [It is characterized by forming a continuous matte layer.] A preferred embodiment of the wood invention is that the light-transmissive film layer is formed of a resin having relatively low mechanical strength and dimensional stability, and another preferred embodiment of the present invention is that the light-transmitting film layer is formed of a resin having relatively low mechanical strength and dimensional stability. The resin particles are placed on the light-transmissive film layer a1rIt, . It is heat-sealed and fixed onto a transparent film layer to form a discontinuous matte layer. (Function) The lithographic printing plate material that does not require dampening water of the present invention has a discontinuous matte layer in which solid particles are fixed on the light-transmitting film layer, so that it is not continuous as described in JP-A-55-55343. Unlike forming a matte layer, the light-transmitting film can be made thinner. Since the light-transmissive film can be made thinner in this way, halftone dot reproducibility or image reproducibility improves. Therefore, the first objective is achieved. Furthermore, the method for producing the lithographic printing plate material that does not require dampening water of the present invention is as follows:
Since a method of forming a discontinuous matte layer by fixing solid particles on a light-transmitting film layer using heating means is used, almost no solvent is used or the amount of solvent can be reduced to a level that does not have any adverse effects. , Even if a light-transmitting film layer is formed on a silicone rubber layer using a resin with relatively low mechanical strength and dimensional stability, such as polypropylene or polyethylene, the problem of rR1 problems such as wrinkles and deterioration of plate-making performance can be solved. Furthermore, it does not cause a decrease in printing properties due to swelling and filling caused by solvents. In other words, according to the manufacturing method of the Moki Invention, not only high plate-making performance but also vacuum adhesion and printing durability can be improved. Therefore, the second aspect of the present invention
The purpose of is achieved. (Structure of the Invention) The present invention will be explained in detail below. The lithographic printing plate material that does not require dampening water of the present invention (hereinafter also referred to as dampening water-free printing plate material or simply plate material) can be used, for example, on a support l as shown in FIG. , photosensitive layer 2,
It has a silicone rubber calendar 3 and a light-transparent film layer 4,
It has a discontinuous matte layer 5 on which solid particles are fixed on the light-transmitting film layer 4. Further, the photosensitive layer 2 and the silicone rubber layer 3 may be a single layer of photosensitive silicone rubber. 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 aluminium, zinc, copper, and steel, and metal plates such as chromium, zinc, Metal plates plated or vapor-deposited with copper, nickel, aluminium, iron, etc., paper, plastic films, glass plates, resin coated paper, paper covered with metal foils such as aluminum. Examples include plastic films treated with S hydration, and among these, aluminum plates are preferred. When using an aluminum plate, it may be subjected to surface roughening treatments such as graining or anodizing. The thickness of the support is preferably 50 to 400 microns, more preferably 100 to 300 microns. A primer layer may be provided on the support, and the primer layer is preferably a resin or a silane coupling agent. Examples of the resin include polyester resin, 11K vinyl-vinyl acetate copolymer, acrylic resin, chloride resin, etc. Examples include vinyl resin, polyacrylate resin, polyvinyl butyral resin, epoxy resin, acrylate copolymer, vinyl acetate copolymer, phenoxy resin, polyurethane resin, polycarbonate resin, polyacrylonitrile butadiene, polyvinyl acetate, etc. ．． 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. In addition, the anchoring agent constituting the primer layer is as follows:
For example, the silane coupling agents and silicone primers used in the silicone rubber layer described above can be used, and organic titanates and the like are also effective. The structure of the photosensitive layer is not particularly limited, and various photosensitive substances can be used. Below we will explain some of the typical ones. First, mention may be made of quinonediazide-type positive type photosensitive materials such as conventionally known O-naphthoquinonediazide compounds.
Suitable 0-naphthoquinone diazito compounds include naphthoquinone-(1.2) monodiazide-(2)-sulfonic acid chlorite and phenol or talesol-formaldehyde as described in U.S. Pat. No. 3,046,120. There are esters with resins. Other useful 0-naphthoquinonediazide compounds include, for example, U.S. Pat.
Ester of birogallol-acetone resin and 0-naphthoquinone diazitosulfonic acid chloride described in JP-A-55-76346, JP-A-55-76346, JP-A-55-76346;
Ester of polyhuman xyphenyl resin and 0-naphthoquinone diazitosulfonic acid chloride described in No. 1044 and No. 56-1045, JP-A No. 50-11
A homopolymer of p-hydroxystyrene as described in No. 3305 or a copolymer of this and other copolymerizable heptanomers with 0-naphthoquinone diazitosulfonic acid chloride, produced by Tokko Sho 49-
17481, a reaction product of a polymer raw tC product of a styrene monomer and a phenol derivative and 0-quinone diazitosulfonic acid, and an ester of polyhydroxybenzophenone and 0-naphthoquinone diazitosulfonic acid chloride. ．． A binder may be added to the photosensitive composition containing such a quinonediazide type photosensitive substance, if necessary.
For example, suitable examples include novolac resins soluble in aqueous alkaline solutions. Examples of such novolac resins are phenol-formaldehyde resin and cresol-formaldehyde resin. Representative examples include p{ert-butylphenol-formaldehyde resin and phenol-modified xylene resin. The amount of the quinonediazide compound in the photosensitive composition is 10 to 50% by weight, more preferably 20 to 40% by weight.
In addition, the amount of the above-mentioned binder is 45 to 80% in the photosensitive composition.
% by weight, preferably 50 to 70% by weight. Diazo resins, typified by metal condensates of aromatic diazonium salts and formaldehyde, are also used as photosensitive substances. Particularly preferred are salts of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde, such as hexafluorophosphates, tetrafluoroborates,
No 4l1a diazo resin which is the reaction product of perchlorate or periodate and the above condensate! Ya, U.S.rB #H3,
300, 309 No. D 11. Examples include organic salts of diazo resins, which are reaction products of the above condensates and sulfonic acids, such as "C".The diazo resins are preferably used together with a binder.There are a variety of such binders. may be used, preferably the polymer compound disclosed in JP-A-54
-9861: A monomer having an aromatic hydroxyl group as described in No. 1, such as N-(4-hydroxyphenyl)acrylate t }'. ．． Copolymerization of N-(4-hydroxyphenyl)methacrynolead, 0-, o-, or p-hydroxystyrene, o-, m-, or p-hydroxyphenyl methacrylate, etc. with other IJi polymers Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as the main repeating unit as described in U.S. Pat. No. 4,123.276, natural resins such as Sierrac, rosin, polyvinyl alcohol, U.S. Pat. ,751,2
57, U.S. Patent No. 3,
551), 097, phthalated polyvinyl alcohol resins, epoxy resins condensed from bisphenol A and ebichlorohythrin, celluloses such as cellulose acetate and cellulose acetate phthalate. ．． In addition, there are also those that have photosensitive polymers such as polycarbonates as photosensitive groups in the main chain or side chain of the polymer. For example, it is described in Japanese Patent Application Laid-Open No. 55-40415. A photosensitive polyester obtained by condensation of phenylene diethyl acrylate with hydrogenated bisphenol A and triethylene glycol, as in US Pat. No. 2,9 SIi. As stated in No. 878,
Examples include photosensitive polyesters derived from (2-probeliden)malonic acid compounds such as cinnamylidenemalonic acid and difunctional glycols. Further examples include aromatic azide compounds in which the azide group is bonded to an aromatic ring directly or via a carbonyl group or a sulfonyl group. For example, polyazitostyrene as described in U.S. Pat. Reaction products with saturated hydrocarbon polymers, as well as Japanese Patent Publications No. 43-21067, No. 44-229, No. 44-22954, and No. 45-2
Examples include polymers having sulfonylazide or carbonyl azide, as described in No. 4915. Furthermore, photopolymerizable compositions comprising addition-polymerizable unsaturated compounds may also be mentioned. The thickness of the photosensitive layer is preferably 0.05 to 10 μm, more preferably 0.1 to 2 μm. In the present invention, the photosensitive material may further contain fillers, pigments, dyes, pigments, surfactants for improving coating properties and other conventional additives and auxiliaries. 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 something. R %Si -09R where n is an integer of 2 or more, R is an alkyl group having 1 to 10 carbon atoms, halogen. These include alkyl groups, vinyl groups, aryl groups, and silanol groups (OH groups), and those in which 60% or more are methyl groups are preferred. Note that the above silanol group (
The OH group) may be located either in the main chain or at the end of the main button, but is preferably located at the end. The silicone rubber suitable for 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-Si+On') (2) R-Si+OAc) (3) R-Si-{-ON-CR'a) *Here, R has the same meaning as R explained earlier, and R' is methyl. group, an alkyl group such as an ethyl group, and Ac is an acetyl group. These silicone rubbers are also available as commercial products, such as YE-3085 manufactured by Toshiba Silicone Co., Ltd. In addition, other useful silicone rubbers can be produced by reacting the above-mentioned base polymers with silicone oils having the following repeating units, or by adding silicone base polymers in which about 3% of R is vinyl groups. reaction,
Alternatively, it can also be obtained by a reaction between the silicone oils. (In the formula, R has the same meaning as R above, S is an integer of 2 or more, and n is an integer of 0 or 1 or more.) In order to obtain silicone rubber by such a crosslinking reaction, the above-mentioned In addition to organic carboxylates of metals such as tin, zinc, cobalt, lead, calcium, and manganese, such as dibutyltin laurate, tin (II) octoate, cobalt naphthenate, etc., or chloroplatinic acid, etc. Catalyst is added. In addition, in order to improve the strength of silicone rubber and obtain a silicone rubber that can withstand the frictional forces generated during printing,
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
V or LTV silicone rubber Disvergian a is preferably used. Examples of this include S311 0ff 23, SRX-257, and SRX-257 made by Toray Silicone.
There are silicone rubber disc versions for paper coating such as H237. In the present invention, it is preferable to use a condensed orange type silicone rubber. In the present invention, in addition to the above ingredients, a small amount of photosensitizer can be included in the silicone rubber layer. Preferably, the silicone rubber layer further contains a silane coupling agent to improve adhesion to the photosensitive layer. Silane coupling agent. For example, something like this: (a) llJCHaCIIzN11CCH2CIl,
CHxSi (OCllt) + (b) black jjillcH*o
(Cllt)isi(OCII+)z0 (e) IIs((:IIs)3sf(OCIIz)z
(d) Cal2~CllSi(OCOCH:+)z(
f) CII*-CIISi(OClltCH3)z(
g) HJCH*CHJH(Cut)zsi(OCIl
i) t(CH3)(h) The film thickness of the chlorosilane silicone rubber is as follows: b. It is preferably 1-10μ, more preferably 0.5-2. Note that a photosensitive silicone rubber layer does not require a photosensitive layer, and such a photosensitive silicone rubber may include γ-methacryloxybrobyltrimethoxysilane or monocinnamoyldiethoxysilane at the terminal OH group of dimethylborisiloxane. Examples include compounds obtained by dealcoholization condensation of silane, compounds obtained by adding a bisazito compound to polydiluganosiloxane, or compounds obtained by reacting acryloyl chloride or p-azitobenzoate. A light transmitting film layer is a layer composed of a film having light transmittance, and here, light transmittance means, for example, a layer having a light transmittance of 50% or more for active light (wavelength 300 nm to 500 nm). It means. Preferred examples of the resin used in the light-transmissive film layer include polyolefins such as polypropylene, polyethylene, polymethylpentene, and ethylene-butene copolymers, polystyrene, and fluororesins. Using these resins,
This is effective when a quinonediazide compound or diazo resin is used in the photosensitive layer. That is, these photosensitive layers are exposed to h
Although gas is generated, these resins exhibit good N and gas permeability. Note that these resins have low mechanical strength and dimensional stability. In the present invention, when a substance other than a quinonediazide compound or diazo resin is used for 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, polyvinyl alcohol, etc. Carbonate, polymethyl methacrylate, polyimide, polyacrylonitrile, etc. can be used. The thickness of the light-transmitting film layer is preferably 5 to 20 JLa, and more preferably 3 to 8 JLa. In the wood invention, the matte layer is a discontinuous layer formed by solid particles fixed to a light-transmissive film layer.The solid particles used are those that can substantially transmit the actinic rays for exposure, but the ill effects of the scattered light caused by the solid particles can be avoided. In order to prevent this, the solid particles may contain an ultraviolet absorber, a yellow pigment, etc. The coverage rate of the solid particles of the light-transmitting film layer is 0.5 to 0.5.
It is preferably 30%, more preferably 1 to 5%. In this way, the discontinuous matte layer does not cover the entire light-transmitting film layer, so the gas permeability of the light-transmitting film is good. Specific examples of solid particles include: ■ For example, polyethylene, polymethyl methacrylate, polystyrene, phenolic resin, ionomer resin,
ABS resin, ethylene-vinyl acetate copolymer, vinyl chloride resin, polyamide resin. Fluororesin, polyester resin, epoxy resin (before curing), styrene (meta)
Thermoplastic resins such as acrylic acid or methacrylic acid ester copolymer resins ■Resins made by adding a curing agent to epoxy resins, phenol resins, unsaturated polyester resins, etc.■ Silicon dioxide, zinc oxide, titanium oxide. Zirconium sulfide, glass particles, alumina, and starch are coated with the resins (1) and (2) above.Two or more of these solid particles (1) to (2) may be used in combination. In addition, U.S. Patent No. 2,701,245, U.S. Patent No. 2,
The matting agents described in No. 992,101 can be used. When using the resin of ■ or ■ above as solid particles,
Its melting point (a.p.) is preferably 60 to 150° C. in consideration of ease of thermal fusion to the light-transmitting film layer.
固体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固
体粒子は、その高さが１〜５０ＪＬＩ．大きさ（幅）１
０〜２００ ｇ ｔｓの半球形，半楕円体形、円柱形が
好ましい．
本発明においては，固体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．押圧手段手
段としては、版材を加熱ロール間に通す等の手段が挙げ
られる．
次に本発明の湿し水不要版材の製造方法を説明する．
支持体上に、リバースロールコー夕、エアーナイフコー
タ、メーヤバーコー夕などの通常のコータあるいはホエ
ラーのような回転ａ７ｔＹ装置を用い、感光層を構戒す
べきＡ［１成物溶液を塗布乾燥および必要に応じて熱キ
ュア後、必要ならば該感光層のうえに同様な方法で接着
層を＊＊、乾燥後，シリコーンゴム溶液を接着層上に同
様の方法で塗布し、通常１００〜１２０℃の温度で数分
間熱処理して，十分に硬化せしめてシリコーンゴム暦を
形成する．
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
ートする．光透過性フィルムとしては，比較的機械的強
度及び寸法安定性が低い樹脂を用いることができる．比
較的機械的及び寸法安定性が低い樹脂としては，前述の
ボリブロピレン、ポリエチレン、ポリメチルベンテン、
エチレンーブテン共重合体等のポリオレフィン，ボリス
チレン，フッ素樹脂が好ましい例として挙げられる．次
いで光透過性フィルム上に固体粒子を加熱手段を介して
同着することにより不連続マット層を形或する．
本発明において、不連続マット層を形處する方法として
好ましい一例としては，熱可塑性を有する樹脂粒子を光
透過性フィルム層上に略々均一に散布し，熱融着して該
光透過性フィルム層上に固着して不連続マット層を形或
する方法が挙げられる．この方法で用いられる熱可塑性
を有する樹脂粒子としては、前記■の樹脂の粒子又は■
の粒子あるいは硬化前でまだ熱可塑性を有している固体
状の熱硬化性樹脂（例えばエボキシ樹脂で分子量９００
以上のもの）が挙げられる，
硬化前でまだ熱可塑性を有している固体状の熱硬化性樹
脂を用いる場合には，かかる樹脂を粉砕して、粉体にし
た後、分級し，一定の範囲の粒径の粒子のみを分取し，
光透過性フィルム層上に散布した後、加熱により粒子を
熱融着させるのと同時に樹脂を硬化させる方法を採用で
きる．また他の例としては，液状の熱硬化性樹脂を光透
過性フィルム層上に噴霧して液体粒子を形成し，その後
の加熱により樹脂を硬化して該光透過性フィルム層上に
固体粒子を固着して不連続マット層を形或する方法も挙
げられる．この方法で用いられる熱硬化性樹脂としては
，前記■の捌脂が挙げられる．
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．
原稿であるボ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．
このとき不連続マット層の存在によって，真空密着性が
向上する．
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．
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．
（発明の効果）
請求項ｌ記載の発明によれば、真空密着性を改良しつつ
画像再現性が向上した湿し水不要平版印刷版材料を提供
することができる．
また請求項２〜４記載の発明によれば、製版性能が高く
，真空＠着性を改良しつつ酎刷性を向上する湿し木不要
平版印刷版材料の製造方法を提供することかできる．
〔実施例〕
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．
実施例１
（ジアゾ樹脂−１の合成）
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４０．９ｇの濃硫酸に溶解した．
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．
この反応混合物を水冷下、 ５０１）ｓｌのエタノール
に滴下し、生じた沈澱を濾過した．エタノールで洗浄後
，この沈澱物をｌ００■！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
じた沈澱を濾過した後、エタノールで洗浄し、これを１
５０ｍｌ純水に溶解した．この液に８８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．（アルミニウム板ａの製造）；
厚さ０．２４層■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／ｄｒｒｒ’の条件
でｌＯ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゜０で３７秒間浸漬し，更
に温度９０℃の水（ｐ｝１８．５）に２５秒間浸漬し，
水洗，乾燥して、アルミニウム板ａを得た．（版材の作
戊）
アルミニウム板ａに下記組威のプライマー層組威物を塗
布し、８５℃で３分間乾燥した後．３ＫＷ超高圧水銀灯
を用いて１０００ｍＪ ／ｃｍ″の全面露光を行なった
．更に １００゜Ｃで４分間乾燥して厚さ０．８ル■の
プライマー層を形成した．［プライマー暦紹或物］
（１） ジアゾ樹脂−１ ８ｆｉｌ
１部（２）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３４／８８の共重合樹脂−１８
２重量部
（３） メチルセロンルブ ｓｏｏｉｉ部
次に上記プライマー層上に下記のＡｌｌ戊の感光性！ｔ
ｉ戊物を塗布し１００℃で２分間乾燥して厚さ０．３μ
厘の感光層を形成した．
［感光性組成物Ｊ
（１） ジアゾ樹脂−１ ５０重量部
（２）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２
０／８０の共重合樹脂−１ ５０１量部（３） ビ
クトリアビュアブルーＢＯＨ （保土ケ谷化学■製染料
） １重量部（５） メチルセ
ロソルブ ９００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／ｔｎ
’になるように塗布し、９０℃で４分間乾燥した．
［シリコーンゴム層組或物］
両末端に水＃基を有する
ジメチルボリシロ午サン １００ｉ量部（分子量８
２，０００）
トリアセトキシメチルシラン １０！ｉ量部ジブチ
ル錫ラウレート０．８ｆｉ量部
アイソパーＥ（エッソ化学製） ９００１ｉ量部次
に，上記シリコーンゴム層上に厚さ５ＪＬｍの片側がコ
ロナ処理されたボリプロビレンフィルム（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
になるようにラくネートした。The shape and size of the solid particles are not particularly limited when they are powder before being fixed, but the solid particles fixed on the light-transmitting film layer have a height of 1 to 50 JLI. Size (width) 1
Hemispherical, semiellipsoidal, and cylindrical shapes of 0 to 200 g ts are preferred. In the present invention, the height of the convex portions can be made uniform by pressing the surface of the solid particles. Examples of the pressing means include means such as passing the plate material between heated rolls. Next, the method for producing the dampening water-free plate material of the present invention will be explained. On the support, use a conventional coater such as a reverse roll coater, an air knife coater, a Meyer bar coater, or a rotary a7tY apparatus such as a Whaler to apply a solution of A[1] to form a photosensitive layer, dry and coat as necessary. After heat curing depending on the conditions, if necessary, apply an adhesive layer on the photosensitive layer in the same manner**. After drying, apply a silicone rubber solution on the adhesive layer in the same manner, and heat the adhesive layer at a temperature of usually 100 to 120°C. Heat-treat at high temperature for several minutes to fully cure and form silicone rubber. Next, a light-transmitting film is laminated onto the silicone rubber layer. As the light-transmitting film, resins with relatively low mechanical strength and dimensional stability can be used. Resins with relatively low mechanical and dimensional stability include the aforementioned polypropylene, polyethylene, polymethylbentene,
Preferred examples include polyolefins such as ethylene-butene copolymers, polystyrene, and fluororesins. Next, a discontinuous matte layer is formed by depositing solid particles onto the light-transmitting film using heating means. In the present invention, one preferred method for shaping the discontinuous matte layer is to disperse thermoplastic resin particles almost uniformly onto the light-transmitting film layer and heat-sealing the light-transmitting film layer. One method is to form a discontinuous mat layer by adhering to the layer. The thermoplastic resin particles used in this method include particles of the resin described in (1) above or
particles or solid thermosetting resins that still have thermoplasticity before curing (for example, epoxy resins with a molecular weight of 900
When using a solid thermosetting resin that still has thermoplastic properties before curing, the resin is crushed into powder, which is then classified and processed into a certain amount. Only particles with a particle size within a range are separated,
It is possible to adopt a method in which the resin is cured at the same time as the particles are thermally fused by heating after being dispersed onto the light-transparent film layer. Another example is to spray a liquid thermosetting resin onto a light-transparent film layer to form liquid particles, and then harden the resin by heating to form solid particles on the light-transparent film layer. Another method is to fix the material to form a discontinuous mat layer. Examples of the thermosetting resin used in this method include the above-mentioned resin. Next, a method for manufacturing a printing plate that does not require dampening water using the dampening water-free printing plate material of the present invention will be explained. The original body film is vacuum-adhered to the plate surface and exposed. The light sources used for this exposure include mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, and fluorescent lamps that emit abundant ultraviolet light. At this time, the presence of a discontinuous matte layer improves vacuum adhesion. After exposure, the light-transmissive film is peeled off and developed with a developer to remove only the unexposed silicone rubber layer and photosensitive layer or silicone rubber layer. As described above, a printing plate with a concave image area formed thereon can be obtained. (Effects of the Invention) According to the invention described in claim 1, it is possible to provide a lithographic printing plate material that does not require dampening water and has improved vacuum adhesion and improved image reproducibility. Further, according to the invention as set forth in claims 2 to 4, it is possible to provide a method for producing a lithographic printing plate material that does not require dampening wood and has high plate-making performance, improves vacuum adhesion and improves printing properties. [Example] Below. The present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 (Synthesis of diazo resin-1) p-diazodiphenylamine sulfate 14.5g (50
mmol) was dissolved in 40.9 g of concentrated sulfuric acid under water cooling.
1.35 g (45 mmol) of paraformaldehyde was slowly added to this reaction solution so that the reaction temperature did not exceed 10°C. This reaction mixture was added dropwise to 501 sl of ethanol under water cooling, and the resulting precipitate was filtered. After washing with ethanol, remove this precipitate by 100■! Dissolve in pure water and add 8% to this solution.
．． A cold concentrated aqueous solution containing 8 g of zinc chloride was added. After filtering the resulting precipitate, it was washed with ethanol and
Dissolved in 50ml pure water. A cold concentrated aqueous solution containing 88 ammonium hexafluorophosphate was added to this solution. The resulting precipitate was filtered, washed with water, and then dried to obtain diazo resin-1. (Production of aluminum plate a): An aluminum plate with a thickness of 0.24 layers 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 at 5 A/drrr'. Anodic oxidation was performed for 10 seconds under the following conditions, washed with water, immersed in a 2% sodium metasilicate aqueous solution at a temperature of 85°C for 37 seconds, and further immersed in water (p} 18.5) at a temperature of 90°C for 25 seconds.
After washing with water and drying, an aluminum plate a was obtained. (Preparation of plate material) A primer layer composition of 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 light at 1000 mJ/cm'' using a 3KW ultra-high pressure mercury lamp. Further, it was dried at 100°C for 4 minutes to form a primer layer with a thickness of 0.8 l. 1) Diazo resin-1 8fil
1 part (2) Copolymer resin-18 of 2-hydroxyethyl methacrylate and methyl methacrylate in a molar ratio of 34/88
2 parts by weight (3) Methylceronlube sooii part Next, apply the following photosensitive layer on the primer layer! t
Apply i-bomono and dry at 100℃ for 2 minutes to a thickness of 0.3μ.
A photosensitive layer was formed. [Photosensitive composition J (1) Diazo resin-1 50 parts by weight (2) 2-hydroxyethyl methacrylate, N- (
Molar ratio of 4-hydroxyphenyl)methacrylamide 2
0/80 copolymer resin-1 501 parts by weight (3) Victoria Blue BOH (dye manufactured by Hodogaya Chemical ■) 1 part by weight (5) Methyl cellosolve 900 parts by weight Next, the following silicone rubber composition was dried on the photosensitive layer. Weight: 1.8g/tn
' and dried at 90°C for 4 minutes. [Silicone rubber layer composition] 100 parts of dimethyl borosiloxane having water groups at both ends (molecular weight 8
2,000) Triacetoxymethylsilane 10! i part dibutyltin laurate 0.8 fi parts Isopar E (manufactured by Esso Chemical Co., Ltd.) 9001 i parts Alphan EM201) was laminated with the corona-treated side facing upward.
次にスチレン：メチルメタアクリレート；アクリル酸：
ブチルアクリレート＝３０： ３０： ３０： ｉｏモ
ル比，融点９５℃の共重合樹脂を粉砕した後、分級し、
粒径ｌＯ〜６０目の粒子を分取した粉体を光透過性フィ
ルム層上にパウダリングし，１２０℃で３０秒間加熱し
て、熱融着させた．
粒子の高さが平均１５μ●，大きさ（幅）が２０〜１０
０ＩＬｓ ．光透過性フィルム層の被ｒＩＩ率が９％の
不連続マット層が得られた．
上記の版材の上面にボ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トランプを用いて露光し，光透
過性フィルムを剥離した．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バットで擦ることにより、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．
更に、上記印刷版の画線部は下記組或の染色液を布につ
け版上を軽くこすった後，水洗することにより鮮やかに
染色することができた．（現像液−ｌ）
β−アニリノエタノール ０．５重Ｊｉｍ
プロピレングリコール １．０重量部ｐ
− ｔａｒｔ−ブチル安怠香酸 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＠量部亜硫酸
カリウム ２．０重量部メタケイ
酸カリウム ３．（ｌ重Ｉｊｋ部水
８１重量部（現像
液−２）
ベンジルアルコール ８ｔ量ｍペレ
ックスＮＢＬ （花王アトラス社製 ７ニオン界面活性
剤３５％水溶液） ５重量部ジエタノール
アミン ２重量部水
８５重ｉ部（染色液
）
ンルフィット（クラレイソブレン化学■製溶剤）２０ｌ
ｉｌ部
レオドールＴＶ−０１２０（花王■界面活性剤）０．５
重量部
ベンジルアルコール ５．０重量部ビク
トリアビュアブルーＢ Ｏ Ｈ １．Ｏｆｉｉ
部水 １００重量部実
施例２
ブラシ研磨加工したアルミ板上に次の組戊を有する厚さ
５ル１の光重合性感光層を設けた．ａ．大日本インキ化
学社製不！１！和ポリエステル「ボリライ｝ ＴＯＲ
一目３１ＲＪの固形物（ビスフェノールＡ，プロピレン
オキサイＦ． 無水マレイン酸の重縮合物）４ｏｆｆｉ
量％
ｂ．グリシジルメタクリレート４モルとキシリレンジア
ミン１モルの付加反応物 ５５重量％Ｃ．ベンゾイン
メチルエーテル ５重量％この感光層の上に東芝シ
リコーン社製ＲＴＶシリコーンゴムディスパージ竺ンｒ
ＹＥ− ３０８５Ｊをｎ−ヘプタンで希釈して塗布し
乾燥して、厚さ２ｕＬ閣のシリコーンゴム層を設けた．
次にシリコーンゴム層の上に厚さＩＱＩＬｍのポリメチ
ルペンテンフィルムをラミネートして光透過性フィルム
層を形成した．
次に光透過性フィルム層上に実施例ｌと同様にバウダリ
ングし、 １２０℃で３０秒間加熱した．粒子の高さが
平均ＩＳＪＬｓ ．大きさ（幅）が２０〜１００ｇｍ
．光透過性フィルム層の被覆率が９％の不連続マット層
が得られた．
この版村上にボジフィルムをあてがい、真空密着時間を
３０秒にて、３κ賃の超高圧水銀灯の光をｌｍの距離か
ら３分間照射し，光透過性フィルムを剥離した後，直ち
にｎ−へブタンで現像したところ、未露光部のシリコー
ンゴム層が除去され，ボジフィルムを忠実に再現した平
版印刷版が得られた．
比較例ｌ
実施例に１においてマット層を設けなかった以外は同様
にして版材を得た．この版材を用いた場合には５分間真
空密着しても焼ぼけが起こり，網点の再現が不十分であ
った．
比較例２
特開昭８２−２４７８８８号の実施例１と同様の方法で
上記実施例ｌで用いた厚さ５井一のポリプロピレンフィ
ルムに凹凸の樹脂層をグラビア塗布し、片面に凹凸を有
するポリプロピレンフィルムを得た．
このポリゾロビレンフィルムを実施例ｌ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
ラミネートシ，版材を得た．この版材に実施例ｌと同様
に露光したところ，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．
実施例ｌ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．
比較例２
実施例ｌと同様に光透過性（カバー）フィルムをラミネ
ートした版材を作成した．
次いで，直ちに特開昭８２−２４７８８８号の実施例一
ｌで用いられているグラビアロールと塗布液を用いて、
光透過性（カバー）フィルムに凹凸を塗布した．このと
き光透過性（カバー）フィルムはシリコーン層から剥れ
てしまい、光透過性（カバー）フィルム上にマット層を
有する水なし版材は得られなかった．Next, styrene: methyl methacrylate; acrylic acid:
Butyl acrylate = 30: 30: 30: io molar ratio, after pulverizing the copolymer resin with a melting point of 95 ° C., it was classified,
A powder containing particles having a particle size of 10 to 60 was powdered onto a light-transmissive film layer and heated at 120° C. for 30 seconds to thermally fuse the powder. The average height of the particles is 15 μ●, and the size (width) is 20 to 10
0ILs. A discontinuous matte layer with a light-transmitting film layer having an rII coverage of 9% was obtained. After vacuum-adhering the film to the top of the above plate material,
A metal halide lamp was used as the light source for exposure, and the light-transparent film was peeled off. Next, after immersing it in developer-1 or developer-2 below for 1 minute, the surface of the plate material is rubbed with a vat impregnated with the developer to separate the silicone rubber layer and photosensitive layer in the unexposed areas. A printing plate with well-reproduced halftone dots was obtained. Furthermore, the image area of the above printing plate could be vividly dyed by applying the following staining solution to a cloth, lightly rubbing the plate, and then washing with water. (Developer-l) β-anilinoethanol 0.5 weight Jim
Propylene glycol 1.0 parts by weight p
- tart-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. (L heavy Ijk part water
81 parts by weight (Developer-2) Benzyl alcohol 8 tons Perex NBL (Kao Atlas 7-ion surfactant 35% aqueous solution) 5 parts by weight Diethanolamine 2 parts by weight Water
85 parts I (staining solution) Nlufit (solvent manufactured by Kuraray Sobren Chemical ■) 20l
IL part Rheodol TV-0120 (Kao ■surfactant) 0.5
Parts by weight Benzyl alcohol 5.0 parts by weight Victoria Viewer Blue B O H 1. Ofii
Part water: 100 parts by weight Example 2 A photopolymerizable photosensitive layer having the following structure and having a thickness of 5 1 was provided on a brush-polished aluminum plate. a. Not manufactured by Dainippon Ink Chemical Co., Ltd.! 1! Japanese polyester "Borirai" TOR
Hitome 31RJ solid (bisphenol A, propylene oxy-F. polycondensate of maleic anhydride) 4offi
Amount% b. Addition reaction product of 4 moles of glycidyl methacrylate and 1 mole of xylylene diamine 55% by weight C.I. 5% by weight of benzoin methyl ether RTV silicone rubber disperge made by Toshiba Silicone Co., Ltd.
YE-3085J was diluted with n-heptane, applied, and dried to form a silicone rubber layer with a thickness of 2 μL. Next, a polymethylpentene film having a thickness of IQILm was laminated on the silicone rubber layer to form a light-transmitting film layer. Next, bordering was performed on the light-transmissive film layer in the same manner as in Example 1, and heated at 120°C for 30 seconds. The height of the particles is the average ISJLs. Size (width) is 20~100gm
．． A discontinuous matte layer with a coverage of the light-transmitting film layer of 9% was obtained. A body film was applied to this Murakami plate, the vacuum contact time was 30 seconds, and the light from a 3κ ultra-high pressure mercury lamp was irradiated for 3 minutes from a distance of 1 m. After peeling off the light-transparent film, immediately exposed to n-heptane. When developed, the silicone rubber layer in the unexposed areas was removed, and a lithographic printing plate that faithfully reproduced the positive film was obtained. Comparative Example 1 A plate material was obtained in the same manner as in Example 1 except that the matte layer was not provided. When this plate material was used, blurring occurred even after 5 minutes of vacuum contact, and halftone dot reproduction was insufficient. Comparative Example 2 An uneven resin layer was gravure coated on the 5-well thick polypropylene film used in Example 1 above using the same method as Example 1 of JP-A No. 82-247888, and polypropylene having unevenness on one side was coated. I got the film. This polyzoropylene film was laminated onto 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 printing plate. When this plate material was exposed to light in the same manner as in Example 1, nitrogen gas generated during exposure was trapped between the light-transmissive (cover) film and the silicone layer, and air bubbles were generated. When developed in the same manner as in Example 1, printing blurring occurred and halftone dot reproducibility was poor. Comparative Example 2 A plate material laminated with a light transmitting (cover) film was prepared in the same manner as in Example 1. Next, immediately using the gravure roll and coating liquid used in Example 11 of JP-A No. 82-247888,
Irregularities were applied to the light-transmissive (cover) film. At this time, the light-transmitting (cover) film peeled off from the silicone layer, and a waterless plate material having a matte layer on the light-transmitting (cover) film could not be obtained.
第１図は本発明の湿し水不要版材の一例を示す要部拡大
断面図である．
１：支持体
２：感光層
３：シリコーンゴム層
４：光透過性フィルム層
５：不連続マット層Figure 1 is an enlarged cross-sectional view of the main parts of an example of the dampening water-free plate material of the present invention. 1: Support 2: Photosensitive layer 3: Silicone rubber layer 4: Light-transparent film layer 5: Discontinuous matte layer
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において、前記光透過性フィ
ルム層上に固体粒子が固着された不連続マット層を有す
ることを特徴とする湿し水不要平版印刷版材料。 ２、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成し、次い
で該光透過性フィルム層上に固体粒子を加熱手段を介し
て固着することにより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。 ３、光透過性フィルム層が、比較的機械的強度及び寸法
安定性が低い樹脂によって形成されていることを特徴と
する請求項２記載の湿し水不要平版印刷版材料の製造方
法。 ４、熱可塑性を有する樹脂粒子を光透過性フィルム層上
に散布し、熱融着して該光透過性フィルム層上に固着し
て不連続マット層を形成することを特徴とする請求項２
又は３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 fountain solution-free lithographic printing plate material having a photosensitive layer and a silicone rubber layer or a photosensitive silicone rubber layer and a light-transparent film layer on a support, wherein the light-transparent film layer A lithographic printing plate material that does not require dampening water and has a discontinuous matte layer on which solid particles are fixed. 2. In the 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-transparent film layer on a support, a light-transparent layer is provided on the silicone rubber layer. A method for producing a lithographic printing plate material that does not require dampening water, comprising forming a film layer and then fixing solid particles on the light-transmissive film layer using a heating means to form a discontinuous matte layer. . 3. The method for producing a lithographic printing plate material that does not require dampening water according to claim 2, wherein the light-transmitting film layer is formed of a resin having relatively low mechanical strength and dimensional stability. 4. Claim 2, characterized in that resin particles having thermoplasticity are dispersed on the light-transmitting film layer and are fixed on the light-transmitting film layer by heat fusion to form a discontinuous matte layer.
Or the method for producing a lithographic printing plate material that does not require dampening water according to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30025389A JPH03160453A (en) | 1989-11-17 | 1989-11-17 | Planographic printing plate material requiring no damping water and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30025389A JPH03160453A (en) | 1989-11-17 | 1989-11-17 | Planographic printing plate material requiring no damping water and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03160453A true JPH03160453A (en) | 1991-07-10 |
Family
ID=17882559
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30025389A Pending JPH03160453A (en) | 1989-11-17 | 1989-11-17 | Planographic printing plate material requiring no damping water and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03160453A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58186746A (en) * | 1982-04-26 | 1983-10-31 | Toray Ind Inc | Manufacture of lithographic plate material requiring no dampening water |
| JPS60191262A (en) * | 1984-03-12 | 1985-09-28 | Fuji Photo Film Co Ltd | Production of photosensitive lithographic printing plate without requiring damping 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
- 1989-11-17 JP JP30025389A patent/JPH03160453A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58186746A (en) * | 1982-04-26 | 1983-10-31 | Toray Ind Inc | Manufacture of lithographic plate material requiring no dampening water |
| JPS60191262A (en) * | 1984-03-12 | 1985-09-28 | Fuji Photo Film Co Ltd | Production of photosensitive lithographic printing plate without requiring damping 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 |
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