JP3787435B2 - Aluminum support for lithographic printing plate and method for producing photosensitive lithographic printing plate - Google Patents
Aluminum support for lithographic printing plate and method for producing photosensitive lithographic printing plate Download PDFInfo
- Publication number
- JP3787435B2 JP3787435B2 JP19799298A JP19799298A JP3787435B2 JP 3787435 B2 JP3787435 B2 JP 3787435B2 JP 19799298 A JP19799298 A JP 19799298A JP 19799298 A JP19799298 A JP 19799298A JP 3787435 B2 JP3787435 B2 JP 3787435B2
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- JP
- Japan
- Prior art keywords
- printing plate
- fluoride
- lithographic printing
- water
- aluminum
- 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.)
- Expired - Fee Related
Links
- 238000007639 printing Methods 0.000 title claims description 79
- 229910052782 aluminium Inorganic materials 0.000 title claims description 54
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 238000011282 treatment Methods 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 14
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical group [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 14
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 12
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 239000011775 sodium fluoride Substances 0.000 claims description 7
- 235000013024 sodium fluoride Nutrition 0.000 claims description 7
- 239000011698 potassium fluoride Substances 0.000 claims description 5
- 235000003270 potassium fluoride Nutrition 0.000 claims description 5
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- 229910021569 Manganese fluoride Inorganic materials 0.000 claims description 2
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 2
- 229910021563 chromium fluoride Inorganic materials 0.000 claims description 2
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 claims description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 claims description 2
- 238000000034 method Methods 0.000 description 55
- 229920005989 resin Polymers 0.000 description 30
- 239000011347 resin Substances 0.000 description 30
- 239000000203 mixture Substances 0.000 description 26
- 239000000243 solution Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 238000005530 etching Methods 0.000 description 13
- -1 fluoride compound Chemical class 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 238000011161 development Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
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- 238000004381 surface treatment Methods 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
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- 239000007864 aqueous solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
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- 239000010407 anodic oxide Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
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- 239000008187 granular material Substances 0.000 description 4
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
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- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
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- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- LRBQNJMCXXYXIU-QWKBTXIPSA-N gallotannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@H]2[C@@H]([C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-QWKBTXIPSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 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
- 239000006224 matting agent Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- ZZSKMNCIAKKVRB-UHFFFAOYSA-N morpholin-4-yl-(2-nitrophenyl)methanone Chemical compound [O-][N+](=O)C1=CC=CC=C1C(=O)N1CCOCC1 ZZSKMNCIAKKVRB-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
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- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
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- 229940093932 potassium hydroxide Drugs 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
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- 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
- QPGHONURGOTMCR-UHFFFAOYSA-N potassium;propan-2-yl naphthalene-1-sulfonate Chemical compound [K].C1=CC=C2C(S(=O)(=O)OC(C)C)=CC=CC2=C1 QPGHONURGOTMCR-UHFFFAOYSA-N 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
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- 229940005574 sodium gluconate Drugs 0.000 description 1
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- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- BYKRNSHANADUFY-UHFFFAOYSA-M sodium octanoate Chemical compound [Na+].CCCCCCCC([O-])=O BYKRNSHANADUFY-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000626 sulfinic acid group Chemical group 0.000 description 1
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- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229940062627 tribasic potassium phosphate Drugs 0.000 description 1
- 229940001496 tribasic sodium phosphate Drugs 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- ROVRRJSRRSGUOL-UHFFFAOYSA-N victoria blue bo Chemical compound [Cl-].C12=CC=CC=C2C(NCC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 ROVRRJSRRSGUOL-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N3/00—Preparing for use and conserving printing surfaces
- B41N3/03—Chemical or electrical pretreatment
Description
【０００１】
【発明の属する技術分野】
本発明は、平版印刷版用アルミニウム支持体及び感光性平版印刷版に関するものであり、特にアルミニウム表面を改質し、耐刷性及び不感脂性と保水性に優れ、地汚れや消去跡汚れや印刷再開時汚れが発生せず、階調コントラストにも優れた平版印刷版用アルミニウム支持体及び感光性平版印刷版に関するものである。
【０００２】
【従来の技術】
アルミニウム板上に感光性組成物を塗設した感光性平版印刷版（以下、「ＰＳ版」と略す。）は、アルミニウム板をブラシ研磨やボール研磨のような機械的な方法や、電解エッチングのような電気化学的な方法やこれら両者を組み合せた方法等の粗面化処理を行って、表面を凹凸状の起伏状態を作り、その後、所望により酸又はアルカリの水溶液によりエッチングし、さらに必要に応じて陽極酸化処理及び／又は親水化処理を施し、その上に感光層を設けることにより製造される。
このＰＳ版は、通常、像露光、現像、（修正）、ガム引き工程を経て平版印刷版とされ、これを印刷機に取り付けて印刷する。
【０００３】
上記の粗面化処理や陽極酸化処理は、耐刷性や保水性の向上の目的として行われ、従来は、表面をより以上にエッチングなどして深くあるいは粗くして砂目を作っていた。
【０００４】
しかし、このままでは現像後の非画像部（砂目中）に感光層の一部が残渣として残り、これが地汚れの原因になったり、あるいは陽極酸化の孔の中に染料などの着色剤がしみこみ、非画像部の色残りにもなっていた。また、不要部分を消去液等で削除した時に、消去液からにじみ出た溶剤等で上記残渣が浮き上がり、そこにインキが付着して、汚れ（消去跡汚れ）になる場合が多かった。
【０００５】
これらを改善するため、従来は、陽極酸化処理したアルミニウム支持体を米国特許第３１８１４６１号明細書に記載されているようなアルカリ金属ケイ酸塩中に浸漬する方法、米国特許第３２７６８６８号及び第４１５３４６１号明細書に記載されているような親水性のポリビニルホスホン酸を下塗りする方法、特開昭４９−１２９０３号明細書に開示されているリン酸根で被覆する方法、特開昭４９−９６８０３号明細書に開示されている水溶性金属塩を含む親水性セルロースを下塗りする方法、あるいは特開昭６２−１９４９４号明細書に開示されているリン酸塩を含む親水層を設ける方法などが提案されている。
【０００６】
しかしながらこれらの方法では、非画像部の残渣を完全に取り除くことはできず、地汚れの原因になったり、上述の消去跡汚れを無くすことはできない。
また、上述のような親水層を設けたり、親水性のものを下塗りする方法では、感光性組成物の密着性が悪くなり、耐刷性が極端に低下するなどの問題があり、満足できるものではなかった。
【０００７】
特開平５−５０７７９号明細書には、陽極酸化皮膜の孔中に１０００オングストローム（０．１μｍ）以下の水酸基を持つ無機粒子を含有させ、孔外（表面）の無機粒子から形成される膜を溶解・除去する方法が開示されている。
しかし、この方法は、陽極酸化皮膜の孔中だけに無機粒子が含有され、孔外（表面）の無機粒子から形成される膜を溶解・除去するので、陽極酸化皮膜表面に吸着した僅かな感光層を完全に取り除くことができず、このために消去跡汚れや非画像部の色残りを完全になくすことができない。
【０００８】
さらに、特開平４−４３３５９号明細書には、有機官能基と、加水分解につづいて重縮合する基とを有する有機金属化合物を液中で加水分解及び重縮合させて得られる無機高分子を含む液状組成物を、金属表面に塗布した後、その上に感光性樹脂層を設けた感光性平版印刷版が開示されている。
この方法は、前記無機高分子を含む液状組成物を、金属表面に塗布し、前記無機高分子がゲル化すると同時に金属表面と密着させる方法であるが、塗布量をコントロールするのが難しく、表面滑り性や保水性等は改善されない。
【０００９】
そして、特開平２−１３９５６号明細書には、アルミニウム板上に水性コロイダルシリカ層を塗布する方法が開示されている。
しかし、この方法は、水性コロイダルシリカの粒子が５〜３０μｍであり、粒子径が大きすぎて保水性の改善にならず、逆にこの粒子間に、印刷中、インキが染み込んで汚れの原因にもなる。
【００１０】
【発明が解決しようとする課題】
従って、本発明の目的は、画像露光し、現像処理したとき、階調コントラストの良い画像を得ることと同時に、非画像部での画像残査が全く無く、印刷時の地汚れの問題や非画像部の色残りを解消し、消去液によるリング状の消去跡汚れも発生しない平版印刷版用アルミニウム支持体及び感光性平版印刷版を提供することである。さらに他の目的は、印刷時において、耐刷性及び不感脂性と保水性に優れ、酸化汚れ（印刷再開時の汚れ）も発生しない平版印刷版用アルミニウム支持体及び感光性平版印刷版を提供するものである。
【００１１】
【課題を解決するための手段】
本発明者らは、上記目的を達成すべく、鋭意検討した結果、本発明をなすに至ったものである。本発明は、粗面化処理及び陽極酸化処理されたアルミニウム支持体の表面に、平均粒径５μｍ以下の粒状の生成物を設けた後、熱湯及び／又は熱風で処理することを特徴とする平版印刷版用アルミニウム支持体を提供するものであり、前記粒状の生成物を設けるための処理液が金属フッ化物を含有した処理液を用い、さらに、これら処理されたアルミニウム支持体に感光層を塗設した感光性平版印刷版を提供するものである。
【００１２】
アルミニウム支持体を熱湯等の手段で処理する方法としては、特開昭５１−３４００７号に陽極酸化処理されたアルミニウムをエッチングしたのち、熱水又は水蒸気で処理する方法あるいは特開平２−８９１９号に陽極酸化処理されたアルミニウムを温度５０〜３００℃かつ水蒸気圧９０Torr以上の雰囲気中に曝す方法などが開示されているが、いずれも本発明のような表面に粒状の生成物を設けた表面を熱湯処理する方法とは異質のものである。
【００１３】
また、本発明の表面処理は、従来より公知の陽極酸化皮膜のエッチングや封孔処理あるいは化学薬品や水溶性樹脂等の下塗り方法とは全く異質のものであり、ある特定の処理薬品により表面処理を行い、生成過程は不明ではあるが、支持体表面のアルミニウムと処理薬品との反応生成物を該アルミニウム表面に付着させる方法である。この生成物の形状は、高倍率の光学顕微鏡あるいは走査電子顕微鏡により観察することができ、５０００倍以下のような低倍率で観察すると、円形状及び／又はウロコ状の粒子に見えるが、一万倍以上のような高倍率で観察すると、円形状に見えるものもあるが、角張った粒状に見えるものもあり、またその表面にひびが入っているものもある。
これらの粒子が砂目の凹凸の起伏状に、あるいは電気化学的な研磨により生成した凹凸の小さなピットの底から表面までランダム状にあるいは全面的に均一に突起状に付着する。
【００１４】
この上に感光層を塗布すると、この粒子が感光層中に食い込み、耐刷性を向上させ、現像時には、この粒子間に現像液がよく浸透するためか、現像がスムースに行われ、感光層がきれいに現像されるので、画像の階調コントラストが良くなり、非画像部においては、現像残りによる地汚れもなく、消去液で非画像部をこすっても、残渣が浮き上がらず、汚れるようなことはない。また、この粒子状物が陽極酸化皮膜及び陽極酸化の孔の上を覆うために、陽極酸化皮膜に染料や感光層が吸着されることなく、また、孔の中にも染料などが染み込むのを防ぐので、非画像部の色残りが無い。
印刷時における、この粒子物の効果は、粒子間に湿し水が浸透して、保水性が良くなり、少量の湿し水で印刷できるので、高品質の印刷物が得られる。
【００１５】
さらに別の効果として、粒子状物で表面が覆われているので、滑りやすく、校正刷り等で行われる水を含んだスポンジで表面をこすった場合にスポンジカスが付きずらく、また粒子があるために、表面の反射率が下がり、ハレーション防止効果があるので、点減りすることなく、網点再現性に優れたものになる。
【００１６】
アルミニウム支持体をフッ化物系化合物で処理する方法として、特開昭４７−３０４０５号明細書には、金属の粗面化表面をフッ化物を主成分として含有する水溶液を用いて処理する方法が開示されている。
しかし、この方法は、陽極酸化されていない金属の粗面化表面を処理する方法であり、本発明のような陽極酸化皮膜上に粒子物を生成付着させる方法とは異質のものであり、前記明細書に記載の方法では、粒子は生成されず、本発明のような効果は期待できない。
【００１７】
次に、アルミニウム支持体上に粒子を付着させる方法として、特開昭５５−１４５１９３号明細書には、フッ化水素アンモニウム及びフッ化水素ナトリウムからなる群で金属べース支持体を処理し、粒子を作り、その上にクロム層をメッキする方法が開示されているが、この方法は、クロムメッキをより密接に金属べースに付着させるためのものであり、本発明のような粒子状の表面を直接、印刷版の支持体表面に利用するものではない。
【００１８】
従来は、印刷時の保水性や耐刷性を向上させるために、砂目をより以上に削ったり、エッチング等して、深くあるいは粗くし、エッチング途中に出るカスなどはきれいに除いていたのが通例であった。これらの方法によれば、ある程度の効果は期待できるが、砂目のエッヂが鋭利になり、このためにインキ粒子がひっかかり、薄汚れになったり、感光層の現像時の抜け性が悪く、現像残りによる汚れとなる場合が多かった。しかし、本発明は、今まで全く見られなかった方法であり、ある特定の表面処理により生成された生成物をそのまま砂目上に残し、さらにその上から熱湯及び／又は熱風をかける方法である。その結果、この粒子生成物により、感光層との密着性が上がり、現像時には、感光層の抜けが良くなり、印刷時には、粒子により表面積が増加し、粒子間に湿し水が良く浸透して保水性が良くなる等の効果があることを見い出し、本発明に結び付いたものである。
従って、この生成物の被覆付着量を、表面の３０％以下になるように減らした場合には、本発明の効果は薄くなり、良好なる平版印刷版用アルミニウム支持体を得ることは難しい。
【００１９】
【発明の実施の形態】
以下、本発明の実施形態について順を追って詳しく説明する。
本発明において用いられるアルミニウム板は、アルミニウム主成分とする純アルミニウムや微量の異原子を含むアルミニウム合金等の板状体である。このような異原子には、珪素、鉄、銅、マンガン、マグネシウム、ニッケル、亜鉛、チタンなどがある。本発明に適用されるアルミニウム板は、その組成が特定されるものでなく、従来公知、公用の素材のものを適宜利用することができる。本発明に用いられるアルミニウム板の厚さは、およそ０．１ｍｍ〜０．４ｍｍ程度が好適である。
【００２０】
アルミニウム板を粗面化処理するに先立ち、圧延時に表面に付着した油分を除去するため、例えば、界面活性剤又はアルカリ水溶液により脱脂処理が行われる。
【００２１】
本発明における粗面化には、機械的に表面を粗面化する方法、電気化学的に表面を粗面化する方法及びこの両者を組み合わせた方法がある。機械的に表面を粗面化する方法としては、ブラシ研磨法、ボール研磨法、ブラスト研磨法、バフ研磨法等と称される公知の方法を用いることができる。また、電気化学的に表面を粗面化する方法としては、塩酸又は硝酸電解液中で交流又は直流により行う方法がある。
【００２２】
このように粗面化されたアルミニウム板は、陽極酸化処理する前に、必要に応じてアルカリエッチングされることが望ましい。
アルカリエッチングに使用するアルカリ剤は、水酸化ナトリウム、水酸化カリウム、第三燐酸ナトリウム、第三燐酸カリウム、アルミン酸ナトリウム、炭酸ナトリウム、メタケイ酸ナトリウム、オルトケイ酸ナトリウム、グルコン酸ナトリウムなどが挙げられ、これらの単独液あるいは二種以上の混合液を用いることができる。
アルカリエッチング液の濃度は、１〜６０重量％が好ましく、３０〜１００℃の液温において、２〜６０秒間処理し、０．１〜１３ｇ／ｍ2 エッチングする。エッチングを行う方法としては、アルミニウム板をエッチング液浴に浸漬する方法、スプレーやノズルでエッチング液をかける方法などがある。
【００２３】
上記アルカリエッチングを施したのち、必要に応じて、硝酸、燐酸、硫酸又はこれらの二種以上の酸を含む混酸でデスマットするか、あるいは単なる水洗、場合によっては高圧力水洗を行ってスマット除去を行う。
【００２４】
次いで、アルミニウム板は陽極酸化処理されるが、使用される電解質としては、一般に硫酸、燐酸、シュウ酸、クロム酸あるいはそれらの混酸が用いられる。陽極酸化の処理条件は用いる電解質により種々かわるので一概に特定し得ないが、一般的には電解質の濃度が１〜５０重量％、液温は５〜４５℃、電流密度が１〜４０Ａ／ｄｍ2 、電圧５〜５０Ｖ及び処理時間５秒〜１０分の範囲ならば好適である。
陽極酸化皮膜の量は０．５ｇ／ｍ2 以上が好適であるが、より好ましくは１．０〜４．０ｇ／ｍ2 の範囲である。陽極酸化皮膜が０．５ｇ／ｍ2 以下の場合には表面に傷がつき易くなり、印刷時に、傷の部分にインキが付着して、汚れになり易くなる。また逆に陽極酸化皮膜が４．０ｇ／ｍ2 以上の場合には、現像速度が遅くなり、感度の低下が生じるので好ましくない。
【００２５】
引き続き、水洗した後、本発明に適う表面処理が行われる。本発明は、主として１．０重量％以上の金属フッ化物を含有する処理液で、陽極酸化皮膜をエッチング（腐食）させない程度の濃度液で成し遂げることができる。さらに、陽極酸化皮膜をエッチング（腐食）させない程度の酸性物質を加えると、金属フッ化物の濃度を下限として０．５重量％程度まで下げることができる。この処理は、陽極酸化処理し、水洗の後、陽極酸化皮膜を軽度のエッチングや種々の方法により封孔処理を行った後、あるいは、リン酸又はリン酸塩処理やケイ酸塩処理等の後処理を行った後、実施することも可能である。
【００２６】
本発明では、陽極酸化処理されたアルミニウム表面に、まず始めに、金属フッ化物あるいは金属フッ化物と酸性物質を含む水溶液で処理し、陽極酸化皮膜はほとんどエッチングせず、また、陽極酸化皮膜のセルの形状も変えずに、アルミニウム表面の砂目の凹凸の起伏状あるいは電解研磨により生成された孔の底から表面まで、平均粒径５μｍ以下の粒状物、たとえば、円形状及び／又はウロコ状と表現できる反応生成物を、ランダム状にあるいは全面的に突起状で生成させる。次いで、熱湯及び／又は熱風の組み合せによる処理を行う。
【００２７】
このときの生成物は、大部分が円形状及び／又はウロコ状を呈しているが、中には、円形がくずれて角張った結晶状に見える場合もある。
生成物は、処理条件によっても異なるが、陽極酸化表面上を少なくとも３０％以上被覆状に設けられるのが好ましく、より好ましい範囲としては、４０〜１００％の範囲である。生成物の被覆率が３０％以下の場合には、保水性、耐刷性などの効果が得られないので好ましくない。
また、粒子径は５μｍ以下が好ましく、より好ましくは０．０１〜２μｍである。０．０１μｍ未満であると、保水性、耐刷性及び表面のスベリ性が悪くなり、逆に５μｍをこえると、保水性が悪くなり、印刷中、インキがこの粒子間に染み込んで汚れになるので好ましくない。
【００２８】
生成物の付着量を重量的に見ると、およそ０．００５〜２．０ｇ／ｍ2 の範囲で設けられるのが好適であり、より好ましくは、０．０１〜１．５ｇ／ｍ2 である。生成物が０．００５ｇ／ｍ2 未満の場合には、やはり耐刷性や地汚れや消去跡の汚れの改善にならず、また逆に２．０ｇ／ｍ2 をこえると、現像性が悪くなり、疲労した現像液では現像しずらくなるので好ましくない。この重量変化はアルミ板を処理する前と後でアルミ板の重量を計り、その差から求めることができる。
【００２９】
上記のような粒状の生成物を設けた表面の反射率は、粒状の生成物を設ける前の表面の反射率より、最大で、反射率にして約２５％下がる。その結果、表面のハレーションが少なくなり、感光性印刷版での露光時の光散乱が抑えられ、点減りが少なく、網点再現性が良くなる。
【００３０】
これら表面の様相は高倍率の光学顕微鏡あるいは走査電子顕微鏡により観察することができる。
図１は、本発明の表面処理を施す前の陽極酸化皮膜を有するアルミニウム支持体の表面であり、図２は本発明の表面処理を施した後のアルミニウム支持体の表面である。
【００３１】
本発明の表面処理に好ましく使用され、ある濃度範囲では、陽極酸化皮膜をエッチングさせない金属フッ化物の具体例としては、フッ化ナトリウム、フッ化マグネシウム、フッ化バリウム、フッ化カリウム、フッ化クロム、フッ化リチウム、フッ化マンガンなどが挙げられ、これらの単独あるいは二種以上を混合して用いる。これらの中でフッ化ナトリウム、フッ化カリウムが特に好ましい。
陽極酸化皮膜をエッチングさせない金属フッ化物濃度は、０．５〜４０重量％の範囲が適当であり、好ましくは１．０〜３０重量％である。０．５重量％未満では、粒子が生成しずらくなり、本発明の目的効果が得られず、４０重量％をこえると、粒子径が小さくなりすぎたり、陽極酸化皮膜をエッチングし易くなったり、金属フッ化物が溶解しずらくなるので好ましくない。
【００３２】
上記金属フッ化物を含有する処理液に、粒子の生成を妨げず、陽極酸化皮膜をエッチングさせない他の化合物を含ますこともできる。例えば、硫酸、硝酸、塩酸、リン酸、酢酸及びこれらのアルミニウム塩、アンモニウム塩、ナトリウム塩、カリウム塩、カルシウム塩、亜鉛塩、マグネシウム塩、リチウム塩などが挙げられる。さらに、シュウ酸、タンニン酸、ミョウバン、クロムミョウバン、ホウ酸、無水クロム酸あるいはクロム酸塩類等が挙げられる。これらの単独に、あるいは二種以上を加えても良い。また、従来より平版印刷版用のエッチ液あるいはカウンターエッチ液として知られている組成物を用いても良い。
【００３３】
上記物質の添加される濃度としては、硫酸、硝酸、塩酸、リン酸、酢酸のような強酸の場合には、０．１〜１．０重量％の範囲が適当であり、好ましくは０．２〜０．６重量％である。０．１重量％未満では、保水性の向上が見込めず、１．０重量％をこえると、陽極酸化皮膜をエッチングするので好ましくない。それ以外の上記化合物の場合には、０．２〜５０重量％の範囲が適当であり、好ましくは０．５〜４０重量％である。０．２重量％未満では、やはり保水性の向上が見込めず、５０重量％以上では、現像速度が遅くなるので好ましくない。
これらの成分を主とし、さらに、表面に付着した生成物を溶解（エッチング）あるいは除去させない程度のケイ酸金属塩、スケール防止剤、界面活性剤、有機溶剤、水溶性樹脂、水不溶性物質でエマルジョン化された物質、ハレーション防止用の染料又は顔料等を処理液の中に含ませることもできる。
【００３４】
処理方法としては、浸漬方法、噴霧方法、スプレー方法、塗布方法などが利用できる。
処理温度は１０〜８０℃、処理時間は１〜６０秒間の範囲が適当であり、ｐＨは１．０〜６．５であることが望ましい。このような処理している時に、直流あるいは交流の電流を流し、陽極酸化と同様な方法でアルミニウム板を処理することもでき、この場合には処理時間を短縮させることができる。
また、処理液濃度を濃くしたり、処理時間を長くすると、円形状あるいはウロコ状の生成物が、びっしり平面状に変化していく場合もあるが、ある程度、円形状あるいはウロコ状で生成物が付着していた方が、本発明の効果をより一層発揮できる。
【００３５】
本発明においては、上記金属フッ化物を含有する処理液で処理した後、陽極酸化皮膜表面上に生成された粒状物をより強固に陽極酸化皮膜表面上に密着させ、保水性や耐刷性のさらなる向上目的のために、水洗の後あるいは水洗なしで熱湯処理して乾燥するか、熱風のみで乾燥するか、あるいは熱湯処理後熱風にて乾燥する処理を行う。
【００３６】
熱湯の温度は少なくとも５０℃以上必要であり、熱風は５０〜１８０℃の範囲がより効果的である。
熱湯あるいは熱風の温度が５０℃未満の場合には、印刷部数が大量な場合、陽極酸化皮膜表面上の粒状物が、印刷途中で取れ易くなり、その結果、不感脂性や保水性が悪くなるおそれがある。また、画像部の下にある粒状物も衝撃に対して弱くなり、剥がれやすくなって画像の剥離につながり、耐刷性の欠如になるおそれがあるので好ましくない。
一方、熱風の温度が１８０℃をこえる場合には、アルミニウム支持体にゆがみや延びが生じ、全体的な平面性が悪くなるので好ましくない。
【００３７】
熱湯処理の方法としては、浸漬方法、かけ流し、ノズル滴下方法、スプレー方法などが適当であり、熱風処理は、温めたエアーをブロアーから板面に吹き付けるなどして行う。
【００３８】
このように処理されたアルミニウム支持体は、このまま平版印刷版用支持体として使用することができるが、必要によりさらに、熱湯及び／又は熱風処理の前後に表面処理を施すことができる。
【００３９】
好適な表面処理として、硫酸、燐酸、硝酸、ホウ酸、クロム酸、ケイ酸及びこれらのアンモニウム塩あるいはアルカリ金属塩の水溶液による処理、界面活性剤や水滴防止剤による処理、さらに、例えばポリアクリル酸、ポリビニルアルコール、ポリビニルホスホン酸、ポリビニルピロリドン、カルボキシメチルセルロース、デキストリン等の水溶性化合物からなる下塗り層を設ける処理、ハレーション防止用の染料又は顔料を下塗りする処理などが挙げられるが、やはりこの場合にも表面に付着した生成物を溶解あるいは除去させるような処理方法、処理条件は適当ではない。
また、上記の各薬品あるいは化合物類を熱湯中に加えることも可能である。
【００４０】
以上のように処理されたアルミニウム支持体は、常法に従って感光層を設けて感光性平版印刷版（ＰＳ版）を得ることができる。ここで適用される感光層の感光性組成物は特に限定されるものでなく、一般的に周知のものが適用でき、例えば、ｏ−キノンジアジド化合物を主成分とするポジ型のもの、ジアゾ樹脂を主成分とするネガ型のもの、不飽和二重結合含有モノマーを主成分とする光重合性化合物、桂皮酸やジメチルマレイミド基を含む光架橋性化合物よりなるネガ型のもの、あるいはヒートモード書き込み型化合物などを感光物とするネガ又はポジ型のものが用いられる。また、特開昭５５−１６１２５０号、特開平４−１０００５２号明細書等に記載の電子写真感光層や物理現像核層とハロゲン化銀乳剤層を設けた銀錯塩拡散転写法を利用した感光層も使用することができる。
さらに、上記ＰＳ版用以外の用途として、インキジェットや紫外線硬化インキで直接アルミニウム板上に画像を設けるための支持体としても使用できる。
【００４１】
上記感光物のうち不飽和二重結合含有モノマーを主成分とする光重合性化合物としては、例えば米国特許第２，７６０，８６３号明細書及び特開平５−２６２８１１号公報に記載の末端エチレン基を有する付加重合性不飽和化合物と光重合開始剤よりなる組成物が使用できる。また、ジメチルマレイミド基を含む光架橋性化合物を含むネガ型感光物としては、例えば特開昭５２−９８８号及び特開昭６２−７８５４４号公報に記載の感光性組成物を挙げることができる。
【００４２】
ポジ型の感光性組成物として用いられるｏ−キノンジアジド化合物としては、米国特許第３，０４６，１２０号に記載されているナフトキノン−１，２−ジアジド−５（又は４）−スルホニルクロライドとフェノール・ホルムアルデヒド樹脂とのエステル化合物、特開昭４３−２８４０３号に記載されているナフトキノン−１，２−ジアジド−５（又は４）−スルホニルクロライドとピロガロール・アセトン樹脂とのエステル化合物、あるいは２，３，４−トリヒドロキシベンゾフェノン又は分子量１０００以下のポリヒドロキシ化合物とナフトキノン−１，２−ジアジド−５（又は４）−スルホニルクロライドとのエステル化合物等が挙げられる。
【００４３】
該ｏ−キノンジアジド化合物は、単独でも感光層を構成することができるが、アルカリ可溶性樹脂をバインダー樹脂として併用することが好ましい。このようなバインダー樹脂としては、ノボラック型の樹脂があり、例えばフェノール・ホルムアルデヒド樹脂、ｏ−、ｍ−及びｐ−クレゾール・ホルムアルデヒド樹脂、ｍ／ｐ−混合クレゾール・ホルムアルデヒド樹脂、フェノール／クレゾール（ｍ−、ｐ−、又はｍ−／ｐ−混合のいずれでもよい）混合・ホルムアルデヒド樹脂、ｔ−ブチルフェノール・ホルムアルデヒド樹脂などが挙げられる。また、ポリビニルフェノール樹脂、ｔ−ブチル置換ポリビニルフェノール樹脂、ｐ−イソプロペニルフェノールの単独重合体あるいは他のモノマーとの共重合体、水酸基又はカルボキシル基を有するフェニルマレイミドの単独重合体あるいは他のモノマーとの共重合体、アルカリ可溶性ポリウレタン樹脂、ポリアミド樹脂、スチレン−無水マレイン酸樹脂等も用いることができる。
【００４４】
ポジ型の感光性組成物には、上記のｏ−キノンジアジド化合物とバインダー樹脂の他に、必要に応じて更に、染料、光酸発生剤、可塑剤、界面活性剤、環状酸無水物、有機酸類、感脂化剤等の添加剤を加えることができる。
【００４５】
次に、ネガ型のＰＳ版の感光性組成物としては、ジアゾ樹脂を含む感光性組成物、光重合性組成物、あるいは光架橋性感光性組成物等があるが、このうちジアゾ樹脂を含む感光性組成物について例を挙げて詳しく説明する。
該ジアゾ樹脂としては、例えばｐ−ジアゾジフェニルアミンとホルムアルデヒドもしくはアセトアルデヒドとの縮合物と、ヘキサフルオロリン酸塩、テトラフルオロホウ酸塩との反応生成物である有機溶媒可溶性ジアゾ樹脂無機塩、又は前記縮合物とスルホン酸類、例えば、パラトルエンスルホン酸、ドデシルベンゼンスルホン酸又はその塩、ヒドロキシル基含有化合物、例えば、２，４−ジヒドロキシベンゾフェノン、２−メトキシ−４−ヒドロキシ−５−ベンゾイルベンゼンスルホン酸又はその塩の反応生成物である有機溶媒可溶性ジアゾ樹脂有機塩等が挙げられる。
その他のジアゾ樹脂としては、カルボキシル基、スルホン酸基、スルフィン酸基及びヒドロキシル基のうち少なくとも一つの有機基を有する芳香族化合物と芳香族ジアゾニウム化合物とを構造単位として含む共縮合物と、上記無機あるいは有機化合物との塩類が挙げられる。
【００４６】
これらのジアゾ樹脂塩は、アルカリ可溶性樹脂をバインダー樹脂として併用することが好ましい。このようなバインダー樹脂として、例えば、特開昭５０−１１８８０２号あるいは特開昭５４−８８４０３号に記載されているような脂肪族性水酸基を有する単量体と他の単量体との共重合体、特開昭５４−９８６１４号に記載されているような芳香族水酸基を有する単量体と他の単量体との共重合体、ｐ−イソプロペニルフェノールと他の単量体との共重合体、Ｎ−（ｐ−ヒドロキシフェニル）マレイミド共重合体、あるいはカルボキシル基及び／又はヒドロキシル基を有するポリウレタン樹脂等を挙げることができる。
【００４７】
また、ジアゾ樹脂塩を含む感光性組成物には、上記の素材の他、必要に応じて更に染料、光酸発生剤、可塑剤、界面活性剤、環状酸無水物、有機酸類、感脂化剤、保存安定剤、マット剤等の添加剤を加えることができる。
【００４８】
かくして得られたＰＳ版は、透明原画を通して、カーボンアーク灯、水銀灯、メタルハライドランプ、キセノンランプ、ケミカルランプ、アルゴンレーザー、ヘリウム・カドミウムレーザー、赤外レーザー、半導体レーザーなどを光源とする活性光線により露光された後、現像処理される。かかるＰＳ版の現像液及び補充液としては、従来より知られているアルカリ水溶液が使用できる。例えば、水酸化ナトリウム、水酸化カリウム、アルカリ金属ケイ酸塩、オクタン酸ナトリウム、アルキルアミン類及びテトラメチルアンモニウムハイドロオキサイドなどが使用できる。これらのアルカリ剤は単独もしくは２種以上を組み合わせて用いられる。
【００４９】
現像液及び補充液には、現像性の促進や抑制、現像カスの分散の目的で、必要に応じて種々の界面活性剤や有機溶剤、さらに還元剤等を添加することができる。このように現像処理されたＰＳ版は、水洗水、界面活性剤、酸類などを含むリンス液、アラビアガムや澱粉誘導体あるいはデキストリンを含む不感脂化液等で後処理される。
【００５０】
【実施例】
以下、本発明を実施例により更に詳細に説明するが、本発明はこれに限定するものではない。
実施例１〜３、比較例１〜３
厚さ０．２４ｍｍのアルミニウム板の両面をよく脱脂したのち、ナイロンブラシとパーミストンの水懸濁液を用いてその表面を砂目立てした後、よく水で洗浄した。１５重量％水酸化ナトリウムに８０℃で１０秒間浸漬してエッチングした後、流水で水洗後、１Ｎ塩酸浴中で２００クーロン／ｄｍ2 で電解粗面化処理を行った。ひきつづいて水洗した後、１５重量％水酸化ナトリウム水溶液で表面を再度エッチングし、水洗を行った後、２０重量％の硫酸水溶液に浸漬して、デスマットした。次いで、１５％硫酸水溶液中で表面に２．０ｇ／ｍ2 の陽極酸化皮膜を設ける処理を行い、水洗の後、以下の各処理を行った。
実施例１：５０℃の２重量％フッ化ナトリウム溶液中に１５秒間浸漬し、次いで９０℃の熱湯中１０秒間浸漬した後、４０℃の温風で乾燥した。
実施例２：５０℃の２重量％フッ化ナトリウム溶液中に１５秒間浸漬し、次いで水洗した後、１００℃の熱風を１０秒間かけて乾燥した。
実施例３：５０℃の２重量％フッ化ナトリウム溶液中に１５秒間浸漬し、次いで９０℃の熱湯中１０秒間浸漬した後、１００℃の熱風を１０秒間かけて乾燥した。
比較例１：５０℃の２重量％フッ化ナトリウム溶液中に１５秒間浸漬し、次いで水洗した後、４０℃の温風で乾燥した。
比較例２：水洗後、１００℃の熱風で乾燥した。
比較例３：水洗後、４０℃の温風で乾燥した。
なお、実施例１〜３におけるアルミ表面上の粒状物の形状は、平均粒径０．１２μｍで、生成量は０．１８ｇ／ｍ2 であった。
【００５１】
このように処理した各例のアルミニウム板に下記組成の感光液（１）を乾燥後の塗布重量が２．０ｇ／ｍ2 となるように塗布して感光層を設けた。
感光液（１）
ナフトキノン−１，２−ジアジド−５−スルホニルクロライトと２，３，４−トリヒドロキシベンゾフェノンとのエステル化物 ２．５ｇ
ｍ−クレゾール・ホルムアルデヒドノボラック樹脂 ６．０ｇ
ナフトキノン−１，２−ジアジド−４−スルホニルクロライド ０．１ｇ
オイルブルー６１３ ０．２ｇ
メチルセロソルブ ５０ｇ
プロピレングリコールモノメチルエーテル ５０ｇ
このようにして得られた各６種の感光性平版印刷版（ＰＳ版）に、原稿フイルム及びステップタブレットを真空密着した後、３ＫＷのメタルハライドランプを用いて距離１ｍより５０秒露光した。
【００５２】
次に、下記組成を有する２５℃の現像液に２０秒間浸漬して画像を形成した。
組成
ＪＩＳ３号ケイ酸ナトリウム ２５ｇ
水酸化カリウム １５ｇ
両性界面活性剤 １ｇ
水 １ｋｇ
【００５３】
このように現像した後、ステップタブレットのクリヤー段数及びベタ段数より階調コントラストを評価し、水洗の後、ガム引きして不感脂化処理を行い、次いで、常法の手段で印刷した。このときの印刷中の非画像部の地汚れや印刷再開時汚れ（一時停止した印刷を再開させた時に発生する微点状の汚れ。酸化汚れとも言う。）及び印刷版としての耐刷力の評価を行った。さらに各基板の感光性平版印刷版を上記現像液にて５ｍ2 ／リットル現像した疲労現像液にて現像した版での消去跡汚れを評価した。それらの結果を表１に示す。
【００５４】
【表１】
上記評価の基準は、以下の方法により評価した。
階調コントラストの評価
各印刷版での現像されたステップタブレットのクリヤー段数及びベタ段数を読み取る。このベタ段数値とクリヤー段数値の差（階調差）が狭いほど階調コントラストが良いことを示す。
【００５６】
地汚れの評価
各印刷版を使用して、約２万部刷った後、ブランケット上の非画像部に当たる部分の汚れ具合及び印刷紙面上の汚れについて目視で観察する。
Ｏ：ブランケット及び印刷紙面上に汚れが全く見られない。
△：ブランケット面はうす黒く汚れるが、印刷紙面上には汚れが目立たない。
×：ブランケット面が黒く汚れ、印刷紙面上にも微点状の汚れが見られる。
【００５７】
酸化汚れ（印刷再開時の汚れ）
各印刷版を使用して、約１５，０００部刷った後、いったん印刷機を停止し、１時間放置した後、印刷を再開した時に、印刷物に生じた微点状の汚れを観察し、その汚れの個数で酸化汚れを評価する。
【００５８】
消去跡汚れ
疲労現像液にて現像された各基板よりなる印刷版の画像部及び非画像部に市販のＰＳ消去液（ＲＰ−１Ｓ：富士写真フイルム社製）を筆で塗り付け、水洗後、インキングして消去によるフリンジ汚れや消去部の汚れを確認した。
○：消去跡も見えず、汚れもない。
△：消去跡は確認できるが、インキは着肉しない。
×：消去跡が確認でき、インキが着肉して汚れになる。
【００５９】
耐刷力の評価
画像ベタ部がかすれてきて、インキ着肉が悪くなり、印刷物上の濃度に異常が現れるまでの刷り枚数を調べた。
【００６０】
実施例４、比較例４〜５
実施例１と同様にアルミニウム板を粗面化処理した後、陽極酸化処理を行い、水洗の後、以下の処理をおこなった。
実施例４：６０℃の２重量％フッ化カリウムと１５重量％燐酸二水素ナトリウムの混合溶液中に１０秒間浸漬し、次いで８０℃の熱湯中５秒間浸漬した後、水洗し、次いで、１０重量％ケイ酸ナトリウム溶液を用いて、７０℃、２０秒間浸漬処理を行い、水洗した後、４０℃の温風で乾燥した。
比較例４：６０℃の２重量％フッ化カリウムと１５重量％燐酸二水素ナトリウムの混合溶液中に１０秒間浸漬し、水洗の後、１０重量％ケイ酸ナトリウム溶液を用いて、７０℃、２０秒間浸漬処理を行い、水洗した後、４０℃の温風で乾燥した。
比較例５：１０重量％ケイ酸ナトリウム溶液を用いて、７０℃、２０秒間浸漬処理を行い、水洗した後、４０℃の温風で乾燥した。
なお、実施例４におけるアルミニウム表面上の粒状物の形状は、平均粒径０．２０μｍで、生成量は０．２８ｇ／ｍ2 であった。
【００６１】
このように処理したアルミニウム板に下記組成の感光液（２）を乾燥後の塗布重量が１．８ｇ／ｍ2 となるように塗布して感光層を設けた。
感光液（２）
２−ヒドロキシ−３−フェノキシプロピルメタクリレート ／２−ヒドロキシエチルメタクリレート／メタクリル酸／メチルメタクリレート／アクリロニトリル＝３０／２０／ ５／２０／２５重量比の共重合体： ３０ｇ
４−ジアゾジフェニルアミンとホルムアルデヒドの縮合物の２−メトキシ−４−ヒドロキシ−５−ベンゾイルベンゼンスルホン酸塩： ３ｇ
ビクトリアピュアーブルーＢＯＨ（保土ヶ谷化学工業社製） １ｇ
シュウ酸 ０．３ｇ
メチルセロソルブ １００ｇ
Ｎ，Ｎ’−ジメチルホルムアミド １０ｇ
【００６２】
このようにして作られた感光性平版印刷版を、ネガフィルム及びステップタブレットの下で３ＫＷのメタルハライドランプを用いて距離１ｍより５０秒露光した。
【００６３】
次に、下記組成を有する２５℃の現像液に２０秒間浸漬して画像を形成した。
組成
ケイ酸カリウム １０ｇ
フェニルグリコール ４０ｇ
イソプロピルナフタレンスルホン酸カリウム ５ｇ
亜硫酸カリウム ２ｇ
水 ９００ｇ
【００６４】
このように現像した後、ステップタブレットのベタ段数及びクリヤー段数より階調コントラストを評価し、水洗の後、ガム引きして不感脂化処理を行い、次いで、常法の手段で印刷した。このときの非画像部の地汚れや酸化汚れ及び耐刷力の評価を行った。その結果を表２に示す。
なお、評価基準は表１と同じである。
【００６５】
【表２】
【発明の効果】
本発明の平版印刷版用アルミニウム支持体を用いた感光性印刷版は、印刷部数が増加した場合においても、画像の階調コントラストが良く、印刷中においては非画像部の地汚れや印刷再開時汚れ（酸化汚れ）もなく、耐刷力に優れ、また消去跡も認められず、その周辺部も汚れない等の優れた版となる。
【図面の簡単な説明】
【図１】本発明の表面処理を施す前の陽極酸化皮膜を有するアルミニウム支持体の表面を示す電子顕微鏡写真である。
【図２】本発明の表面処理を施した後のアルミニウム支持体の表面を示す電子顕微鏡写真である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an aluminum support for a lithographic printing plate and a photosensitive lithographic printing plate, and in particular, the surface of the aluminum is modified to have excellent printing durability, non-sensitivity and water retention, and dirt and erasure stains and printing. The present invention relates to an aluminum support for a lithographic printing plate and a photosensitive lithographic printing plate which are free from smearing at the time of restart and excellent in gradation contrast.
[0002]
[Prior art]
A photosensitive lithographic printing plate (hereinafter abbreviated as “PS plate”) in which a photosensitive composition is coated on an aluminum plate is used for mechanical methods such as brush polishing and ball polishing, and for electrolytic etching. The surface is roughened by an electrochemical method such as the above or a combination of these two methods to create an uneven surface, and then etched with an acid or alkali aqueous solution if desired. Accordingly, anodization treatment and / or hydrophilization treatment is performed, and a photosensitive layer is provided thereon.
This PS plate is usually converted into a lithographic printing plate through image exposure, development, (correction), and gumming processes, which are attached to a printing press for printing.
[0003]
The above roughening treatment and anodizing treatment are performed for the purpose of improving printing durability and water retention, and conventionally, the surface is deepened or roughened by etching or the like to make a grain.
[0004]
However, in this state, a part of the photosensitive layer remains as a residue in the non-image area after development (in the grain), which may cause a background stain or a colorant such as a dye soaks into the anodic oxidation hole. It was also a color residue in the non-image area. In addition, when the unnecessary portion was deleted with an erasing solution, the residue was lifted by a solvent that oozed out from the erasing solution, and ink adhered to the residue, often resulting in contamination (erasure traces).
[0005]
In order to remedy these problems, the conventional method is to immerse an anodized aluminum support in an alkali metal silicate as described in US Pat. No. 3,181,461, US Pat. Nos. 3,276,868 and 4,153,461. A method of undercoating hydrophilic polyvinylphosphonic acid as described in the specification of JP-A-49-96803, a method of coating with phosphate groups disclosed in JP-A-49-12903, and JP-A-49-96803 Proposed is a method of undercoating hydrophilic cellulose containing a water-soluble metal salt disclosed in a book, or a method of providing a hydrophilic layer containing a phosphate disclosed in Japanese Patent Application Laid-Open No. 62-19494. Yes.
[0006]
However, these methods cannot completely remove the residue in the non-image area, and cannot cause background contamination or the above-mentioned erasure mark contamination.
In addition, the method of providing a hydrophilic layer as described above or undercoating with a hydrophilic layer has problems such as poor adhesion of the photosensitive composition and extremely low printing durability. It wasn't.
[0007]
Japanese Patent Application Laid-Open No. 5-50779 discloses a film formed from inorganic particles outside the surface (surface) by containing inorganic particles having a hydroxyl group of 1000 angstroms (0.1 μm) or less in the pores of the anodized film. A method of dissolving and removing is disclosed.
However, this method contains inorganic particles only in the pores of the anodized film, and dissolves / removes the film formed from the inorganic particles outside the surface (surface). The layer cannot be completely removed, so that it is impossible to completely eliminate erasure stains and color residue in the non-image area.
[0008]
Further, JP-A-4-43359 discloses an inorganic polymer obtained by hydrolyzing and polycondensing an organometallic compound having an organic functional group and a group that undergoes polycondensation following hydrolysis in a liquid. A photosensitive lithographic printing plate in which a liquid composition containing the composition is applied to a metal surface and a photosensitive resin layer is provided thereon is disclosed.
This method is a method in which a liquid composition containing the inorganic polymer is applied to a metal surface, and the inorganic polymer is gelled and at the same time is in close contact with the metal surface. The slipperiness and water retention are not improved.
[0009]
Japanese Patent Application Laid-Open No. 2-13956 discloses a method of applying an aqueous colloidal silica layer on an aluminum plate.
However, in this method, the particles of the aqueous colloidal silica are 5 to 30 μm, and the particle diameter is too large to improve the water retention. On the contrary, the ink soaks between the particles during printing and causes stains. Also become.
[0010]
[Problems to be solved by the invention]
Therefore, an object of the present invention is to obtain an image with good gradation contrast when image exposure and development are performed, and at the same time, there is no image residue in the non-image area, and there is no problem of background smudges during printing. An object of the present invention is to provide an aluminum support for a lithographic printing plate and a photosensitive lithographic printing plate which eliminates the color residue in the image area and does not cause ring-shaped erasure marks due to the erasing liquid. Still another object is to provide an aluminum support for a lithographic printing plate and a photosensitive lithographic printing plate that are excellent in printing durability, insensitivity and water retention during printing, and do not cause oxidation stains (stains upon resumption of printing). Is.
[0011]
[Means for Solving the Problems]
The inventors of the present invention have made the present invention as a result of intensive studies to achieve the above object. The present invention provides a lithographic plate characterized by providing a granular product having an average particle size of 5 μm or less on the surface of a roughened and anodized aluminum support and then treating with hot water and / or hot air. An aluminum support for a printing plate is provided, and a processing solution for providing the granular product is a processing solution containing a metal fluoride, and a photosensitive layer is coated on the processed aluminum support. The photosensitive lithographic printing plate provided is provided.
[0012]
As a method of treating the aluminum support by means of hot water or the like, Japanese Patent Application Laid-Open No. 51-34007 discloses a method of etching anodized aluminum and then treating it with hot water or steam, or Japanese Patent Application Laid-Open No. 2-8919. A method of exposing anodized aluminum to an atmosphere having a temperature of 50 to 300 ° C. and a water vapor pressure of 90 Torr or more has been disclosed. In any case, the surface provided with a granular product on the surface as in the present invention is heated with hot water. The processing method is different.
[0013]
Further, the surface treatment of the present invention is completely different from the conventionally known anodic oxide film etching and sealing treatment or undercoating methods such as chemicals and water-soluble resins. Although the production process is unknown, the reaction product of aluminum on the surface of the support and the treatment chemical is adhered to the aluminum surface. The shape of this product can be observed with a high-magnification optical microscope or scanning electron microscope. When observed at a low magnification of 5000 times or less, it looks like circular and / or scale-like particles. When observed at a high magnification such as twice or more, some of them look circular, but some of them look like angular grains, and others have cracks on their surfaces.
These particles adhere in a rugged relief pattern, or from the bottom to the surface of a small pit having irregularities generated by electrochemical polishing, randomly or evenly on the entire surface.
[0014]
When a photosensitive layer is coated on the photosensitive layer, the particles bite into the photosensitive layer to improve the printing durability. During development, the developer is smoothly penetrated between the particles, or the photosensitive layer is developed. Is developed neatly, and the gradation contrast of the image is improved. In the non-image area, there is no background smudge due to the development residue, and even if the non-image area is rubbed with an erasing liquid, the residue does not float up and becomes dirty. There is no. In addition, since the particulate matter covers the anodized film and the anodized hole, the dye or the photosensitive layer is not adsorbed to the anodized film, and the dye or the like penetrates into the hole. This prevents color residue in the non-image area.
The effect of the particulate matter at the time of printing is that dampening water penetrates between the particles, water retention is improved, and printing can be performed with a small amount of dampening water, so that a high-quality printed matter can be obtained.
[0015]
As another effect, since the surface is covered with particulate matter, it is easy to slip, and when the surface is rubbed with a sponge containing water used in proof printing etc., the sponge residue does not stick easily and there are particles. For this reason, the reflectance of the surface is lowered and the anti-halation effect is obtained, so that the dot reproducibility is excellent without reducing the dot.
[0016]
As a method for treating an aluminum support with a fluoride compound, JP-A-47-30405 discloses a method for treating a roughened metal surface with an aqueous solution containing fluoride as a main component. Has been.
However, this method is a method of treating a roughened surface of a metal that has not been anodized, and is different from the method of generating and adhering particles on the anodized film as in the present invention, In the method described in the specification, particles are not generated, and the effect of the present invention cannot be expected.
[0017]
Next, as a method for depositing particles on an aluminum support, Japanese Patent Application Laid-Open No. 55-145193 describes that a metal base support is treated with a group consisting of ammonium hydrogen fluoride and sodium hydrogen fluoride, A method of making particles and plating a chrome layer thereon is disclosed, but this method is intended to adhere the chrome plating more closely to the metal base, as in the present invention. This surface is not directly used as the support surface of the printing plate.
[0018]
In the past, in order to improve the water retention and printing durability during printing, the grain was made to be deeper or rougher by grinding or etching more than the grain, and the debris that emerged during the etching was removed cleanly. It was customary. According to these methods, a certain degree of effect can be expected, but the edge of the grain becomes sharp, which causes the ink particles to get caught and become lightly soiled, or the photosensitive layer is not easily removed during development. In many cases, it was soiled by the rest. However, the present invention is a method that has never been seen so far, and is a method in which a product produced by a specific surface treatment is left on the grain, and hot water and / or hot air is further applied thereon. . As a result, the particle product improves the adhesion with the photosensitive layer, and during the development, the photosensitive layer is easily removed, and during printing, the surface area is increased by the particles, and the dampening water penetrates well between the particles. It has been found that there is an effect such as improved water retention, and has been linked to the present invention.
Therefore, when the coating adhesion amount of this product is reduced to 30% or less of the surface, the effect of the present invention is diminished and it is difficult to obtain a good lithographic printing plate aluminum support.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail in order.
The aluminum plate used in the present invention is a plate-like body such as pure aluminum containing aluminum as a main component or an aluminum alloy containing a small amount of foreign atoms. Such heteroatoms include silicon, iron, copper, manganese, magnesium, nickel, zinc, titanium, and the like. The composition of the aluminum plate applied to the present invention is not specified, and conventionally known and publicly available materials can be used as appropriate. The thickness of the aluminum plate used in the present invention is preferably about 0.1 mm to 0.4 mm.
[0020]
Prior to roughening the aluminum plate, for example, a degreasing treatment is performed with a surfactant or an aqueous alkali solution in order to remove oil adhering to the surface during rolling.
[0021]
The roughening in the present invention includes a method of mechanically roughening the surface, a method of electrochemically roughening the surface, and a method combining both. As a method for mechanically roughening the surface, a known method called a brush polishing method, a ball polishing method, a blast polishing method, a buff polishing method, or the like can be used. Further, as a method of electrochemically roughening the surface, there is a method of performing alternating current or direct current in hydrochloric acid or nitric acid electrolyte.
[0022]
The roughened aluminum plate is preferably alkali-etched as necessary before anodizing.
Examples of the alkali agent used for alkali etching include sodium hydroxide, potassium hydroxide, tribasic sodium phosphate, tribasic potassium phosphate, sodium aluminate, sodium carbonate, sodium metasilicate, sodium orthosilicate, and sodium gluconate. These single solutions or a mixture of two or more of them can be used.
The concentration of the alkali etching solution is preferably 1 to 60% by weight, and is treated at a solution temperature of 30 to 100 ° C. for 2 to 60 seconds, and 0.1 to 13 g / m.2Etch. As a method for etching, there are a method of immersing an aluminum plate in an etching solution bath, a method of applying an etching solution with a spray or a nozzle, and the like.
[0023]
After performing the alkali etching, if necessary, desmutting with nitric acid, phosphoric acid, sulfuric acid, or a mixed acid containing two or more of these acids, or simply rinsing with water, and in some cases with high pressure water to remove the smut. Do.
[0024]
Next, the aluminum plate is anodized, and as the electrolyte to be used, sulfuric acid, phosphoric acid, oxalic acid, chromic acid or a mixed acid thereof is generally used. The treatment conditions for anodization vary depending on the electrolyte used, and thus cannot be specified in general. In general, the concentration of the electrolyte is 1 to 50% by weight, the liquid temperature is 5 to 45 ° C., and the current density is 1 to 40 A / dm.2A voltage of 5 to 50 V and a processing time of 5 seconds to 10 minutes are preferable.
The amount of anodized film is 0.5g / m2The above is preferable, but more preferably 1.0 to 4.0 g / m.2Range. Anodized film 0.5g / m2In the following cases, the surface is likely to be scratched, and during printing, the ink adheres to the scratched part and becomes easily stained. Conversely, the anodized film is 4.0 g / m.2In the above case, the development speed is slow and the sensitivity is lowered, which is not preferable.
[0025]
Subsequently, after washing with water, a surface treatment suitable for the present invention is performed. The present invention can be achieved with a treatment liquid mainly containing 1.0% by weight or more of a metal fluoride and a concentration liquid that does not etch (corrode) the anodic oxide film. Furthermore, when an acidic substance is added to such an extent that the anodized film is not etched (corroded), the concentration of the metal fluoride can be lowered to about 0.5% by weight as the lower limit. This treatment is performed after anodizing, washing with water, sealing the anodic oxide film by light etching or various methods, or after phosphoric acid or phosphate treatment or silicate treatment. It is also possible to carry out after the processing.
[0026]
In the present invention, the anodized aluminum surface is first treated with a metal fluoride or an aqueous solution containing a metal fluoride and an acidic substance, and the anodized film is hardly etched. The shape of the grain of the aluminum surface is not changed, and the granular surface having an average particle size of 5 μm or less from the bottom to the surface of the hole generated by electrolytic polishing, for example, circular shape and / or scale shape A reaction product that can be expressed is generated randomly or entirely in the form of protrusions. Subsequently, the process by the combination of hot water and / or hot air is performed.
[0027]
Most of the product at this time has a circular shape and / or a scale shape, but in some cases, the circular shape may be broken and look like an angular crystal.
Although the product varies depending on the treatment conditions, it is preferable that at least 30% or more of the anodized surface is provided in a covering state, and a more preferable range is 40 to 100%. When the coverage of the product is 30% or less, effects such as water retention and printing durability cannot be obtained, which is not preferable.
The particle size is preferably 5 μm or less, more preferably 0.01 to 2 μm. If it is less than 0.01 μm, the water retention, printing durability and surface slipping will be poor, and conversely if it exceeds 5 μm, the water retention will be poor and the ink will soak into the particles and become dirty during printing. Therefore, it is not preferable.
[0028]
When the amount of product deposited is viewed by weight, it is approximately 0.005 to 2.0 g / m.2Is preferably provided in the range of 0.01 to 1.5 g / m.2It is. Product is 0.005 g / m2If it is less than the range, the printing durability, the background stains and the erasure marks will not be improved.2Exceeding the above range is not preferable because the developability deteriorates and it becomes difficult to develop with a fatigued developer. This change in weight can be obtained from the difference between the weight of the aluminum plate before and after the treatment.
[0029]
The reflectance of the surface provided with the granular product as described above is about 25% lower than the reflectance of the surface before providing the granular product. As a result, halation on the surface is reduced, light scattering during exposure on the photosensitive printing plate is suppressed, dot loss is reduced, and dot reproducibility is improved.
[0030]
The appearance of these surfaces can be observed with a high magnification optical microscope or scanning electron microscope.
FIG. 1 shows the surface of an aluminum support having an anodized film before the surface treatment of the present invention, and FIG. 2 shows the surface of the aluminum support after the surface treatment of the present invention.
[0031]
Specific examples of metal fluorides that are preferably used for the surface treatment of the present invention and do not etch the anodized film in a certain concentration range include sodium fluoride, magnesium fluoride, barium fluoride, potassium fluoride, chromium fluoride, Lithium fluoride, manganese fluoride, etc. are mentioned, These are used individually or in mixture of 2 or more types. Of these, sodium fluoride and potassium fluoride are particularly preferred.
The metal fluoride concentration that does not etch the anodized film is suitably in the range of 0.5 to 40% by weight, preferably 1.0 to 30% by weight. If the amount is less than 0.5% by weight, it is difficult to produce particles, and the intended effect of the present invention cannot be obtained. If the amount exceeds 40% by weight, the particle diameter becomes too small, or the anodized film can be easily etched. This is not preferable because the metal fluoride is difficult to dissolve.
[0032]
The treatment liquid containing the metal fluoride may contain other compounds that do not interfere with the generation of particles and do not etch the anodized film. For example, sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, acetic acid and aluminum salts, ammonium salts, sodium salts, potassium salts, calcium salts, zinc salts, magnesium salts, lithium salts and the like thereof can be mentioned. Furthermore, oxalic acid, tannic acid, alum, chrome alum, boric acid, chromic anhydride, chromates, etc. are mentioned. You may add these individually or in combination of 2 or more types. In addition, a composition conventionally known as an etchant or counter etchant for planographic printing plates may be used.
[0033]
As the concentration of the above substances, in the case of strong acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid and acetic acid, a range of 0.1 to 1.0% by weight is appropriate, preferably 0.2. ~ 0.6% by weight. If it is less than 0.1% by weight, water retention cannot be improved, and if it exceeds 1.0% by weight, the anodized film is etched, which is not preferable. In the case of the above-mentioned other compounds, the range of 0.2 to 50% by weight is appropriate, preferably 0.5 to 40% by weight. If it is less than 0.2% by weight, improvement in water retention cannot be expected, and if it is 50% by weight or more, the development speed becomes slow, which is not preferable.
Mainly composed of these components, and further emulsified with metal silicate salts, scale inhibitors, surfactants, organic solvents, water-soluble resins, and water-insoluble substances that do not dissolve (etch) or remove the products attached to the surface. The treated liquid, a dye or pigment for preventing halation can be included in the processing liquid.
[0034]
As a treatment method, an immersion method, a spray method, a spray method, a coating method, or the like can be used.
The treatment temperature is suitably 10 to 80 ° C., the treatment time is suitably 1 to 60 seconds, and the pH is preferably 1.0 to 6.5. During such treatment, a direct current or alternating current can be passed to treat the aluminum plate in the same manner as anodization, and in this case, the treatment time can be shortened.
In addition, when the treatment liquid concentration is increased or the treatment time is lengthened, the circular or scale-like product may change into a tight flat shape, but to some extent, the product is circular or scale-like. The effect of the present invention can be further exerted if it is attached.
[0035]
In the present invention, after the treatment with the treatment liquid containing the metal fluoride, the granular material produced on the surface of the anodized film is more firmly adhered to the surface of the anodized film, and water retention and printing durability are improved. For the purpose of further improvement, a hot water treatment is performed after water washing or without water washing and drying is performed, or only hot air is dried, or hot water treatment is performed and then drying with hot air is performed.
[0036]
The temperature of the hot water is required to be at least 50 ° C., and the hot air is more effective in the range of 50 to 180 ° C.
When the temperature of hot water or hot air is less than 50 ° C., if the number of printed parts is large, particulate matter on the surface of the anodized film can be easily removed during printing, and as a result, the oil insensitivity and water retention may be deteriorated. There is. In addition, the granular material under the image area is also unfavorable because it becomes weak against impact, easily peels off, leads to peeling of the image, and lack of printing durability.
On the other hand, when the temperature of the hot air exceeds 180 ° C., the aluminum support is distorted and stretched, and the overall flatness is deteriorated.
[0037]
As a hot water treatment method, a dipping method, pouring, a nozzle dropping method, a spray method, and the like are appropriate, and hot air treatment is performed by blowing warm air from a blower onto a plate surface.
[0038]
The aluminum support thus treated can be used as it is as a support for a lithographic printing plate, but if necessary, it can be subjected to surface treatment before and after hot water and / or hot air treatment.
[0039]
Suitable surface treatments include treatment with sulfuric acid, phosphoric acid, nitric acid, boric acid, chromic acid, silicic acid and aqueous solutions of these ammonium salts or alkali metal salts, treatment with surfactants or water-drop inhibitors, and for example, polyacrylic acid. , Treatment for providing an undercoat layer made of a water-soluble compound such as polyvinyl alcohol, polyvinyl phosphonic acid, polyvinyl pyrrolidone, carboxymethyl cellulose, dextrin, treatment for undercoating a dye or pigment for preventing halation, and the like. Treatment methods and treatment conditions that dissolve or remove the product adhering to the surface are not appropriate.
It is also possible to add the above chemicals or compounds to hot water.
[0040]
The aluminum support treated as described above can be provided with a photosensitive layer according to a conventional method to obtain a photosensitive lithographic printing plate (PS plate). The photosensitive composition of the photosensitive layer applied here is not particularly limited, and generally known ones can be applied. For example, a positive type mainly composed of an o-quinonediazide compound, a diazo resin Negative type with main component, photopolymerizable compound with main component of unsaturated double bond-containing monomer, negative type with photocrosslinkable compound containing cinnamic acid or dimethylmaleimide group, or heat mode writing type A negative or positive type using a compound or the like as a photosensitive material is used. In addition, a photosensitive layer using an electrophotographic photosensitive layer described in JP-A Nos. 55-161250 and 4-100052, or a silver complex diffusion transfer method provided with a physical development nucleus layer and a silver halide emulsion layer. Can also be used.
Furthermore, it can be used as a support for providing an image directly on an aluminum plate with an ink jet or ultraviolet curable ink as a use other than the above-mentioned PS plate.
[0041]
Examples of the photopolymerizable compound containing an unsaturated double bond-containing monomer as a main component in the photosensitive material include, for example, terminal ethylene groups described in U.S. Pat. No. 2,760,863 and JP-A-5-262811. A composition comprising an addition-polymerizable unsaturated compound having a photopolymerization initiator and a photopolymerization initiator can be used. Examples of the negative photosensitive material containing a photocrosslinkable compound containing a dimethylmaleimide group include photosensitive compositions described in JP-A Nos. 52-988 and 62-78544.
[0042]
Examples of the o-quinonediazide compound used as the positive photosensitive composition include naphthoquinone-1,2-diazide-5 (or 4) -sulfonyl chloride described in US Pat. No. 3,046,120 and phenol. Ester compound with formaldehyde resin, ester compound of naphthoquinone-1,2-diazide-5 (or 4) -sulfonyl chloride and pyrogallol / acetone resin described in JP-A-43-28403, or 2,3 Examples include 4-trihydroxybenzophenone or an ester compound of a polyhydroxy compound having a molecular weight of 1000 or less and naphthoquinone-1,2-diazide-5 (or 4) -sulfonyl chloride.
[0043]
The o-quinonediazide compound alone can constitute a photosensitive layer, but it is preferable to use an alkali-soluble resin as a binder resin. Examples of such binder resins include novolak type resins, such as phenol / formaldehyde resins, o-, m- and p-cresol / formaldehyde resins, m / p-mixed cresol / formaldehyde resins, phenol / cresol (m- , P-, or m- / p-mixed)) mixed / formaldehyde resin, t-butylphenol / formaldehyde resin, and the like. Also, polyvinylphenol resin, t-butyl substituted polyvinylphenol resin, p-isopropenylphenol homopolymer or copolymer with other monomers, phenylmaleimide homopolymer or other monomers having a hydroxyl group or a carboxyl group Copolymers, alkali-soluble polyurethane resins, polyamide resins, styrene-maleic anhydride resins, and the like can also be used.
[0044]
In addition to the o-quinonediazide compound and the binder resin, the positive photosensitive composition may further include a dye, a photoacid generator, a plasticizer, a surfactant, a cyclic acid anhydride, and an organic acid, if necessary. Additives such as a sensitizer can be added.
[0045]
Next, as the photosensitive composition of the negative PS plate, there are a photosensitive composition containing a diazo resin, a photopolymerizable composition, a photocrosslinkable photosensitive composition, etc., of which a diazo resin is included. The photosensitive composition will be described in detail with examples.
Examples of the diazo resin include an organic solvent-soluble diazo resin inorganic salt which is a reaction product of a condensate of p-diazodiphenylamine and formaldehyde or acetaldehyde and hexafluorophosphate or tetrafluoroborate, or the above-mentioned condensation. And sulfonic acids such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid or salts thereof, hydroxyl group-containing compounds such as 2,4-dihydroxybenzophenone, 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid or the like Organic solvent-soluble diazo resin organic salts, which are reaction products of salts, and the like.
Other diazo resins include a cocondensate containing an aromatic compound having at least one organic group of a carboxyl group, a sulfonic acid group, a sulfinic acid group and a hydroxyl group and an aromatic diazonium compound as a structural unit, and the above inorganic Or the salt with an organic compound is mentioned.
[0046]
These diazo resin salts are preferably used in combination with an alkali-soluble resin as a binder resin. As such a binder resin, for example, copolymerization of a monomer having an aliphatic hydroxyl group described in JP-A-50-118802 or JP-A-54-88403 with another monomer Copolymers, copolymers of monomers having an aromatic hydroxyl group and other monomers as described in JP-A-54-98614, copolymers of p-isopropenylphenol and other monomers Examples thereof include a polymer, an N- (p-hydroxyphenyl) maleimide copolymer, and a polyurethane resin having a carboxyl group and / or a hydroxyl group.
[0047]
In addition to the above-mentioned materials, the photosensitive composition containing a diazo resin salt may further include a dye, a photoacid generator, a plasticizer, a surfactant, a cyclic acid anhydride, an organic acid, and a sensitized oil as necessary. Additives such as additives, storage stabilizers, matting agents can be added.
[0048]
The PS plate thus obtained is exposed to actinic rays through a transparent original, using a carbon arc lamp, mercury lamp, metal halide lamp, xenon lamp, chemical lamp, argon laser, helium / cadmium laser, infrared laser, semiconductor laser, etc. as a light source. Then, it is developed. A conventionally known alkaline aqueous solution can be used as the developer and replenisher for the PS plate. For example, sodium hydroxide, potassium hydroxide, alkali metal silicate, sodium octoate, alkylamines and tetramethylammonium hydroxide can be used. These alkali agents are used alone or in combination of two or more.
[0049]
Various surfactants, organic solvents, and reducing agents can be added to the developer and replenisher as necessary for the purpose of promoting and suppressing developability and dispersing development residue. The PS plate thus developed is post-treated with a rinsing solution containing washing water, a surfactant, acids and the like, a desensitizing solution containing gum arabic, a starch derivative or dextrin, and the like.
[0050]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this.
Examples 1-3, Comparative Examples 1-3
After thoroughly degreasing both sides of an aluminum plate having a thickness of 0.24 mm, the surface was grained with a nylon brush and a water suspension of Permiston, and then thoroughly washed with water. After etching by dipping in 15 wt% sodium hydroxide at 80 ° C. for 10 seconds, washing with running water, 200 coulomb / dm in 1N hydrochloric acid bath2Then, an electrolytic surface roughening treatment was performed. Subsequently, after washing with water, the surface was etched again with a 15% by weight aqueous sodium hydroxide solution, washed with water, then immersed in a 20% by weight sulfuric acid aqueous solution and desmutted. Next, 2.0 g / m on the surface in a 15% sulfuric acid aqueous solution.2The treatment for providing the anodic oxide film was performed, and after washing with water, the following treatments were performed.
Example 1 It was immersed in a 2 wt% sodium fluoride solution at 50 ° C. for 15 seconds, then immersed in hot water at 90 ° C. for 10 seconds, and then dried with hot air at 40 ° C.
Example 2: It was immersed in a 2 wt% sodium fluoride solution at 50 ° C for 15 seconds, washed with water, and then dried with hot air at 100 ° C for 10 seconds.
Example 3: After dipping in a 2 wt% sodium fluoride solution at 50 ° C. for 15 seconds and then in hot water at 90 ° C. for 10 seconds, hot air at 100 ° C. was dried for 10 seconds.
Comparative Example 1: The film was immersed in a 2 wt% sodium fluoride solution at 50 ° C. for 15 seconds, washed with water, and then dried with hot air at 40 ° C.
Comparative Example 2: After washing with water, it was dried with hot air at 100 ° C.
Comparative Example 3: After washing with water, it was dried with warm air of 40 ° C.
In addition, the shape of the granular material on the aluminum surface in Examples 1 to 3 has an average particle size of 0.12 μm, and the generated amount is 0.18 g / m.2Met.
[0051]
The coating weight after drying the photosensitive solution (1) having the following composition on the aluminum plate of each example thus treated was 2.0 g / m.2A photosensitive layer was provided by coating.
Photosensitive solution (1)
2.5 g of esterified product of naphthoquinone-1,2-diazido-5-sulfonyl chlorite and 2,3,4-trihydroxybenzophenone
6.0 g of m-cresol formaldehyde novolac resin
Naphthoquinone-1,2-diazide-4-sulfonyl chloride 0.1 g
Oil blue 613 0.2g
Methyl cellosolve 50g
50g propylene glycol monomethyl ether
Each of the six types of photosensitive lithographic printing plates (PS plates) thus obtained was vacuum-contacted with the original film and the step tablet, and then exposed for 50 seconds from a distance of 1 m using a 3 KW metal halide lamp.
[0052]
Next, it was immersed in a 25 ° C. developer having the following composition for 20 seconds to form an image.
composition
JIS3 sodium silicate 25g
Potassium hydroxide 15g
Amphoteric surfactant 1g
1kg of water
[0053]
After developing in this manner, the gradation contrast was evaluated from the number of clear steps and solid steps of the step tablet, washed with water, degummed by gumming, and then printed by conventional means. At this time, the non-image area during printing, stains at the time of resuming printing (spot-like stains generated when resuming temporarily stopped printing, also referred to as oxidation stains), and printing durability as a printing plate Evaluation was performed. Further, the photosensitive lithographic printing plate of each substrate is 5 m with the above developer.2The erasure mark stain was evaluated on a plate developed with a fatigue developer that was developed per liter. The results are shown in Table 1.
[0054]
[Table 1]
The above evaluation criteria were evaluated by the following methods.
Tone contrast evaluation
Read the clear step number and solid step number of the developed step tablet on each printing plate. The narrower the difference (gradation difference) between the solid stage value and the clear stage value, the better the gradation contrast.
[0056]
Evaluation of dirt
After printing about 20,000 copies using each printing plate, the degree of soiling on the non-image area on the blanket and the stain on the printing paper surface are visually observed.
O: No dirt is seen on the blanket and the printed paper surface.
Δ: The blanket surface is slightly black and dirty, but the stain is not noticeable on the printing paper surface.
X: The blanket surface is black and dirty, and fine dot-like stains are also seen on the printing paper surface.
[0057]
Oxidized stain (dirt when printing resumes)
After printing about 15,000 copies using each printing plate, once the printing press was stopped and left for 1 hour, when printing was resumed, the smudges on the printed material were observed. Evaluate oxidized dirt by the number of dirt.
[0058]
Erase trace dirt
A commercially available PS erasing solution (RP-1S: manufactured by Fuji Photo Film Co., Ltd.) is applied with a brush to the image and non-image areas of the printing plate made of each substrate developed with the fatigue developer, washed with water, and then inked. The fringe stain due to erasure and the erasure area were confirmed.
○: There is no erasure mark and no dirt.
Δ: An erasure mark can be confirmed, but ink does not deposit.
X: An erasure mark can be confirmed, and ink is deposited and becomes dirty.
[0059]
Evaluation of printing durability
The number of printed sheets was examined until the solid image portion became faint, ink deposition deteriorated, and the density on the printed matter appeared abnormal.
[0060]
Example 4, Comparative Examples 4-5
The aluminum plate was roughened in the same manner as in Example 1, then anodized, washed with water, and then subjected to the following treatment.
Example 4: It was immersed in a mixed solution of 2% by weight potassium fluoride at 60 ° C. and 15% by weight sodium dihydrogen phosphate for 10 seconds, then immersed in hot water at 80 ° C. for 5 seconds, washed with water, and then 10% by weight. A 20% sodium silicate solution was used for immersion treatment at 70 ° C. for 20 seconds, washed with water, and then dried with warm air at 40 ° C.
Comparative Example 4: It was immersed in a mixed solution of 2% by weight potassium fluoride and 15% by weight sodium dihydrogen phosphate at 60 ° C. for 10 seconds, washed with water, and then at 70 ° C., 20% using 10% by weight sodium silicate solution After immersing for 2 seconds and washing with water, it was dried with warm air of 40 ° C.
Comparative Example 5: A 10 wt% sodium silicate solution was used for immersion treatment at 70 ° C for 20 seconds, washed with water, and then dried with hot air at 40 ° C.
In addition, the shape of the granular material on the aluminum surface in Example 4 is an average particle diameter of 0.20 μm, and the generation amount is 0.28 g / m.2Met.
[0061]
The coating weight after drying the photosensitive solution (2) having the following composition on the aluminum plate thus treated was 1.8 g / m.2A photosensitive layer was provided by coating.
Photosensitive solution (2)
2-hydroxy-3-phenoxypropyl methacrylate / 2-hydroxyethyl methacrylate / methacrylic acid / methyl methacrylate / acrylonitrile = 30/20/5/20/25 weight ratio copolymer: 30 g
2-Methoxy-4-hydroxy-5-benzoylbenzenesulfonate salt of condensate of 4-diazodiphenylamine and formaldehyde: 3 g
Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 1g
Oxalic acid 0.3g
Methyl cellosolve 100g
N, N'-dimethylformamide 10g
[0062]
The photosensitive lithographic printing plate thus prepared was exposed for 50 seconds from a distance of 1 m using a 3 KW metal halide lamp under a negative film and a step tablet.
[0063]
Next, it was immersed in a 25 ° C. developer having the following composition for 20 seconds to form an image.
composition
Potassium silicate 10g
Phenyl glycol 40g
Isopropyl naphthalene sulfonate potassium 5g
Potassium sulfite 2g
900g of water
[0064]
After developing in this manner, the gradation contrast was evaluated from the number of solid steps and the number of clear steps of the step tablet, washed with water, degummed by gumming, and then printed by conventional means. At this time, the background stain, oxidation stain and printing durability of the non-image area were evaluated. The results are shown in Table 2.
The evaluation criteria are the same as in Table 1.
[0065]
[Table 2]
【The invention's effect】
The photosensitive printing plate using the aluminum support for a lithographic printing plate of the present invention has good gradation contrast of the image even when the number of printed copies is increased, and during printing, when the non-image portion is stained or when printing is resumed. There are no stains (oxidation stains), excellent printing durability, no erasure marks, and no stains on the periphery.
[Brief description of the drawings]
FIG. 1 is an electron micrograph showing the surface of an aluminum support having an anodized film before the surface treatment of the present invention.
FIG. 2 is an electron micrograph showing the surface of an aluminum support after the surface treatment of the present invention is performed.
Claims (3)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19799298A JP3787435B2 (en) | 1998-06-29 | 1998-06-29 | Aluminum support for lithographic printing plate and method for producing photosensitive lithographic printing plate |
| IT1999RM000401A IT1306158B1 (en) | 1998-06-29 | 1999-06-22 | PROCEDURE FOR THE FORMATION OF AN ALUMINUM SUBSTRATE FOR A LASTRALITHOGRAPHIC, AND A PRESENSITIZED LITHOGRAPHIC SHEET. |
| DE19929716A DE19929716B4 (en) | 1998-06-29 | 1999-06-24 | Process for preparing an aluminum substrate for a lithographic printing plate and for producing a presensitized lithographic printing plate |
| FR9908520A FR2780337B1 (en) | 1998-06-29 | 1999-06-29 | PROCESS FOR FORMING AN ALUMINUM SUBSTRATE FOR A LITHOGRAPHIC PLATE AND FOR A PRESENSITIZED LITHOGRAPHIC PLATE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19799298A JP3787435B2 (en) | 1998-06-29 | 1998-06-29 | Aluminum support for lithographic printing plate and method for producing photosensitive lithographic printing plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000015948A JP2000015948A (en) | 2000-01-18 |
| JP3787435B2 true JP3787435B2 (en) | 2006-06-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19799298A Expired - Fee Related JP3787435B2 (en) | 1998-06-29 | 1998-06-29 | Aluminum support for lithographic printing plate and method for producing photosensitive lithographic printing plate |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP3787435B2 (en) |
| DE (1) | DE19929716B4 (en) |
| FR (1) | FR2780337B1 (en) |
| IT (1) | IT1306158B1 (en) |
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|---|---|---|---|---|
| JP4527509B2 (en) | 2003-12-26 | 2010-08-18 | 岡本化学工業株式会社 | Aluminum support for lithographic printing plate and lithographic printing plate precursor |
| EP1557283B1 (en) * | 2004-01-20 | 2007-01-03 | Konica Minolta Medical & Graphic, Inc. | Printing plate material and its developing process |
| JP6004181B2 (en) * | 2013-01-18 | 2016-10-05 | スズキ株式会社 | Anodized film and method for producing the same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3160506A (en) * | 1962-10-19 | 1964-12-08 | Polychrome Corp | Planographic printing plate and method for preparing same |
| US3440050A (en) * | 1965-02-05 | 1969-04-22 | Polychrome Corp | Lithographic plate |
| JPS5146003B1 (en) * | 1970-08-03 | 1976-12-07 | ||
| US4148649A (en) * | 1977-02-09 | 1979-04-10 | Polychrome Corporation | Method for producing lithographic printing plates |
| JP2775534B2 (en) * | 1991-08-27 | 1998-07-16 | 富士写真フイルム株式会社 | Method for producing a lithographic printing plate support |
-
1998
- 1998-06-29 JP JP19799298A patent/JP3787435B2/en not_active Expired - Fee Related
-
1999
- 1999-06-22 IT IT1999RM000401A patent/IT1306158B1/en active
- 1999-06-24 DE DE19929716A patent/DE19929716B4/en not_active Expired - Fee Related
- 1999-06-29 FR FR9908520A patent/FR2780337B1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| FR2780337A1 (en) | 1999-12-31 |
| ITRM990401A0 (en) | 1999-06-22 |
| DE19929716A1 (en) | 2000-02-10 |
| ITRM990401A1 (en) | 2000-12-22 |
| DE19929716B4 (en) | 2006-07-06 |
| FR2780337B1 (en) | 2001-08-17 |
| IT1306158B1 (en) | 2001-05-30 |
| JP2000015948A (en) | 2000-01-18 |
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