JPH0563318B2 - - Google Patents
Info
- Publication number
- JPH0563318B2 JPH0563318B2 JP10572382A JP10572382A JPH0563318B2 JP H0563318 B2 JPH0563318 B2 JP H0563318B2 JP 10572382 A JP10572382 A JP 10572382A JP 10572382 A JP10572382 A JP 10572382A JP H0563318 B2 JPH0563318 B2 JP H0563318B2
- Authority
- JP
- Japan
- Prior art keywords
- chromium
- support
- printing plate
- plate
- lithographic printing
- 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 - Lifetime
Links
- 238000007639 printing Methods 0.000 claims description 74
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 64
- 239000000463 material Substances 0.000 claims description 49
- 229910052742 iron Inorganic materials 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 17
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 150000002222 fluorine compounds Chemical class 0.000 claims description 10
- 150000001553 barium compounds Chemical class 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 62
- 239000011651 chromium Substances 0.000 description 54
- 229910052804 chromium Inorganic materials 0.000 description 53
- 239000010410 layer Substances 0.000 description 46
- 238000011282 treatment Methods 0.000 description 37
- 238000000034 method Methods 0.000 description 33
- 239000000203 mixture Substances 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 239000000126 substance Substances 0.000 description 25
- 239000013078 crystal Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 16
- 229910000831 Steel Inorganic materials 0.000 description 15
- -1 nitrate ions Chemical class 0.000 description 15
- 238000012545 processing Methods 0.000 description 15
- 239000010959 steel Substances 0.000 description 15
- 238000004070 electrodeposition Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 12
- 125000004429 atom Chemical group 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 10
- 239000008151 electrolyte solution Substances 0.000 description 10
- 238000005530 etching Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000005238 degreasing Methods 0.000 description 9
- 238000011161 development Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910000975 Carbon steel Inorganic materials 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000002178 crystalline material Substances 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 239000010962 carbon steel Substances 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 4
- 229910001632 barium fluoride Inorganic materials 0.000 description 4
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 238000010884 ion-beam technique Methods 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 229910000669 Chrome steel Inorganic materials 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 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 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- VZQBDGHUOBRFAA-UHFFFAOYSA-N 2-(2,6-dihydroxyphenyl)benzaldehyde Chemical compound C1(O)=C(C(O)=CC=C1)C1=CC=CC=C1C=O VZQBDGHUOBRFAA-UHFFFAOYSA-N 0.000 description 1
- ZRUOTKQBVMWMDK-UHFFFAOYSA-N 2-hydroxy-6-methylbenzaldehyde Chemical compound CC1=CC=CC(O)=C1C=O ZRUOTKQBVMWMDK-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- DQYSALLXMHVJAV-UHFFFAOYSA-M 3-heptyl-2-[(3-heptyl-4-methyl-1,3-thiazol-3-ium-2-yl)methylidene]-4-methyl-1,3-thiazole;iodide Chemical compound [I-].CCCCCCCN1C(C)=CS\C1=C\C1=[N+](CCCCCCC)C(C)=CS1 DQYSALLXMHVJAV-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000000864 Auger spectrum Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910000617 Mangalloy Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- XZSZONUJSGDIFI-UHFFFAOYSA-N n-(4-hydroxyphenyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC1=CC=C(O)C=C1 XZSZONUJSGDIFI-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- SQTLECAKIMBJGK-UHFFFAOYSA-I potassium;titanium(4+);pentafluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[K+].[Ti+4] SQTLECAKIMBJGK-UHFFFAOYSA-I 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 229910003438 thallium oxide Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 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
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
Landscapes
- Printing Plates And Materials Therefor (AREA)
Description
【発明の詳細な説明】
本発明は平版印刷版用支持体の製造方法に関
し、更に詳しくは、クロム系被覆層を有する鉄材
からなる平版印刷版用支持体の製造方法の改良に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a support for a lithographic printing plate, and more particularly, to an improvement in the method for producing a support for a lithographic printing plate made of an iron material having a chromium-based coating layer.
従来、平版印刷版用支持体の基材としてはアル
ミニウム板が使用されていた。支持体は、通常、
アルミニウム板を脱脂し、物理的あるいは電気化
学的に砂目立て処理し、次いで陽極酸化処理など
の表面処理をした後、必要に応じて熱水等による
封孔処理を施すことにより製造される。 Conventionally, an aluminum plate has been used as a base material for a support for a lithographic printing plate. The support is usually
It is manufactured by degreasing an aluminum plate, subjecting it to physical or electrochemical graining treatment, then subjecting it to surface treatment such as anodizing treatment, and then subjecting it to sealing treatment with hot water or the like as necessary.
このように従来技術にあつては、第１に基材と
して高価格のアルミニウム板を採用しなければな
らない。第２にアルミニウム板の物理的強度が弱
いためオフセツト印刷機に取り付けて高速度で印
刷する場合、その鋭角に曲げた取り付け部が切断
する故障（所謂くわえ切れ。）が発生し易い。第
３にアルミニウム板は軟質であるため、製版時や
印刷の際の取り扱いでへこみ等の変化が起こり易
い。第４に砂目立て処理、陽極酸化処理等の表面
処理を必要とし、多大な時間を費し生産効率が悪
かつた。 As described above, in the prior art, firstly, an expensive aluminum plate must be used as the base material. Second, since the physical strength of the aluminum plate is weak, when it is attached to an offset printing machine and printed at high speed, the sharply bent attachment part is likely to break (so-called grip breakage). Thirdly, since the aluminum plate is soft, it is susceptible to changes such as dents when handled during plate making or printing. Fourth, surface treatments such as graining and anodizing were required, which took a lot of time and resulted in poor production efficiency.
一方、比較的安価な鉄材を基材とする平版印刷
版用支持体については、特開昭55−145193号にほ
ぼ平担な外面及び比較的鋭い突起面が実際上ない
電着クロム層を有する平版印刷版用支持体が開示
されている。しかし、この支持体は画像部との接
着性が十分でなく、平版印刷版に使用した場合
に、長期印刷中に画像部が一部剥離したり、非画
像部に汚れを生じため、網点のからみが発生した
りして耐刷性が劣つていた。又現像性の寛容度が
狭いため、自動現像機を用いずスポンジに現像液
を含ませて版を擦つて現像するいわゆる“手現
像”などの摩擦現像液処理すると、画現部の損傷
故障が起きやすいという問題があつた。更に、電
着クロム層を形成する処理工程とは別に、ビフル
オライド粒子化槽で処理する工程を必要とし、鉄
材の場合、の処理工程に時間を多く費し、また電
着クロム層形成に際し、使用する総電気量が大き
く生産コストが高くつき、更に電着クロム層形成
浴の許容温度範囲が狭く、温度制御に注意を払わ
なくてはならず生産能率が悪かつた。 On the other hand, regarding a support for a lithographic printing plate based on a relatively inexpensive iron material, JP-A-55-145193 has an electrodeposited chromium layer with an almost flat outer surface and virtually no relatively sharp protruding surfaces. A support for a lithographic printing plate is disclosed. However, this support does not have sufficient adhesion to the image area, and when used in lithographic printing plates, part of the image area peels off during long-term printing, and stains occur in the non-image area, resulting in halftone dots. The printing durability was poor due to the occurrence of tangles. In addition, because the latitude in developing performance is narrow, if a friction developer process is used, such as so-called "hand development" in which a sponge is soaked with developer and developed by rubbing the plate without using an automatic processor, damage to the image area may occur. I had a problem with it being easy to wake up. Furthermore, in addition to the treatment process for forming the electrodeposited chromium layer, a treatment process in a bifluoride atomization tank is required, which requires a lot of time in the case of iron materials, and also The total amount of electricity required was large, resulting in high production costs.Furthermore, the permissible temperature range of the electrodeposited chromium layer forming bath was narrow, requiring careful temperature control, resulting in poor production efficiency.
従つて本発明の目的は機械的強度が高く、感光
層との接着性、耐刷性、及び現像性の寛容度にお
いて十分な性能を有する平版印刷版用支持体の製
造方法を提供することにある。 Therefore, an object of the present invention is to provide a method for producing a support for a lithographic printing plate that has high mechanical strength and has sufficient performance in terms of adhesion with a photosensitive layer, printing durability, and developability latitude. be.
本発明の別の目的は、安価な鉄材を基材として
用い簡単な処理工程でかつ生産効率良く平版印刷
版用支持体を製造する方法を提供することにあ
る。本発明のその他の目的は以下の記載から明ら
かとなろう。 Another object of the present invention is to provide a method for manufacturing a lithographic printing plate support using an inexpensive iron material as a base material through simple processing steps and with high production efficiency. Other objects of the invention will become apparent from the description below.
本発明者等は、種々研究を重ねた結果、無水ク
ロム酸（CrO3）及バリウム化合物を含有する25
℃を超える温度のめつき液中で鉄材上に電着被覆
をすることにより前記目的を達成し得ることを見
出した
本発明に係る製造方法の特徴は、無水クロム酸
を含有する電解液中に、バリウム化合物を少量含
有せしめて25℃を超える温度で電解処理する点に
あり、このような条件の組合せによる電解処理は
平版印刷版用支持体の分野においては全く新規な
ものである。 As a result of various studies, the present inventors discovered that 25
It has been discovered that the above object can be achieved by electrodeposition coating on iron material in a plating solution at a temperature exceeding , a barium compound is contained in a small amount and the electrolytic treatment is performed at a temperature exceeding 25° C., and the electrolytic treatment using such a combination of conditions is completely new in the field of lithographic printing plate supports.
本発明の電解液中の無水クロム酸量は、100〜
500ｇ／が好ましい範囲であり、バリウム化合
物については、１〜10ｇ／が好ましい範囲であ
る。又、本発明において特に望ましい他の共存化
合物としては、フツ素化合物及び酢酸が挙げられ
る。電解液中に含まれるフツ素化合物量は20ｇ／
以下が好ましく、又酢酸については10ｇ／以
下が好ましい。更に本発明において望ましい共存
イオンとしては、硝酸イオンおよアンモニウムイ
オンが挙げられる。電解液中における硝酸イオン
濃度は１モル／以下が好ましく、アンモニウム
イオン濃度も１モル／以下が好ましい。 The amount of chromic anhydride in the electrolyte of the present invention is 100 to
The preferred range is 500g/, and for barium compounds, the preferred range is 1-10g/. Further, particularly desirable coexisting compounds in the present invention include fluorine compounds and acetic acid. The amount of fluorine compounds contained in the electrolyte is 20g/
The following is preferable, and for acetic acid, 10 g/or less is preferable. Furthermore, desirable coexisting ions in the present invention include nitrate ions and ammonium ions. The nitrate ion concentration in the electrolytic solution is preferably 1 mol/or less, and the ammonium ion concentration is also preferably 1 mol/or less.
めつき液に含有せしめるバリウム化合物として
は例えば硝酸バリウム、酢酸バリウム、フツ化バ
リウム等が挙げられ、フツ素化合物としてはフツ
化水素、フツ化アンモニウム、酸性フツ化アンモ
ニウム等が挙げられる。硝酸イオンを供給する化
合物としては、硝酸、硝酸塩（例えば硝酸バリウ
ム等）等が有利に用いられ、更にアンモニウムイ
オンを供給する化合物としては、アンモニア水、
フツ化アンモニウム、酸性フツ化アンモニウム等
が有利に用いられる。 Examples of barium compounds to be included in the plating solution include barium nitrate, barium acetate, barium fluoride, etc., and examples of fluorine compounds include hydrogen fluoride, ammonium fluoride, acidic ammonium fluoride, and the like. As compounds that supply nitrate ions, nitric acid, nitrates (for example, barium nitrate, etc.) are advantageously used, and as compounds that supply ammonium ions, aqueous ammonia,
Ammonium fluoride, acidic ammonium fluoride, and the like are advantageously used.
又、K+，Na+，Fe2+，Fe3+，CO2- 3，BO3- 3，
Cl-，O2-等は本発明を実施するための電解液に
含有させても本発明の作用効果を損うことがない
ので、これらとバリウムイオン、フツ素イオン、
硝酸イオン及びアンモニウムイオンとが結合した
化合物は該イオンの供給源、バリウム化合物及び
フツ素化合物として有効に用いることができる。 Also, K + , Na + , Fe 2+ , Fe 3+ , CO 2- 3 , BO 3- 3 ,
Even if Cl - , O 2-, etc. are included in the electrolytic solution for carrying out the present invention, the effects of the present invention will not be impaired.
A compound in which nitrate ions and ammonium ions are combined can be effectively used as a source of the ions, a barium compound, and a fluorine compound.
本発明の電解液中の上記イオン及び各化合物の
量は公知の方法で測定できるので所望の量に調節
することは容易である。例えば、フツ素化合物及
び硝酸イオンの分析は、日本工業規格K0102に記
載の方法で行なうことができ、バリウム化合物の
分析は硫酸バリウムによる検出とその重量測定で
行なえる。 The amounts of the above-mentioned ions and each compound in the electrolytic solution of the present invention can be measured by known methods, so it is easy to adjust them to desired amounts. For example, fluorine compounds and nitrate ions can be analyzed by the method described in Japanese Industrial Standard K0102, and barium compounds can be analyzed by detection using barium sulfate and weight measurement.
本発明の電解液において上記成分は広汎な濃度
範囲において用いることができ、且つそれらの成
分濃度を種々組合せた条件において本発明の効果
を奏することができる。 In the electrolytic solution of the present invention, the above-mentioned components can be used in a wide range of concentrations, and the effects of the present invention can be achieved under various combinations of these component concentrations.
なお、フツ素化合物及びアンモニウムイオンの
供給源としては適度な還元力を維持するために、
フツ化水素アンモニウム（NH4HF2）として電
解液へ添加するのが好ましい。 In addition, in order to maintain appropriate reducing power as a source of fluorine compounds and ammonium ions,
It is preferably added to the electrolyte as ammonium hydrogen fluoride (NH 4 HF 2 ).
本発明における鉄材は純鉄の他、鉄と他の元素
との合金を包含する。鉄と合金をつくる他の元素
としては、炭素、マンガン、ニツケル等が挙げら
れる。 The iron material in the present invention includes not only pure iron but also alloys of iron and other elements. Other elements that form alloys with iron include carbon, manganese, and nickel.
合金としては、具体的には炭素鋼（炭素（0.04
〜1.7％）と鉄の合金）、炭素鋼より炭素含有率の
高い鋳鉄、更に他の元素（例えばマンガン、ニツ
ケル、クロム、コバルト、タングステン、モリブ
デン）を加えた特殊鋼（例えばマンガン鋼、ニツ
ケル鋼、クロム鋼、ニツケル−クロム鋼）等が挙
げられる。上記炭素鋼としては、炭素の含有量に
応じて、極軟鋼（炭素0.25％以下）、軟鋼（炭素
0.25〜0.5％）、硬鋼（炭素0.5〜1.0％）、極硬鋼
（炭素1.0％以上）が含まれる。 Specifically, the alloy is carbon steel (carbon (0.04
~1.7%) and iron alloys), cast iron with a higher carbon content than carbon steel, and special steels containing other elements (e.g. manganese, nickel, chromium, cobalt, tungsten, molybdenum) (e.g. manganese steel, nickel steel) , chrome steel, nickel-chrome steel), etc. Depending on the carbon content, the above carbon steels include extremely mild steel (0.25% carbon or less), mild steel (carbon
0.25-0.5%), hard steel (0.5-1.0% carbon), and extremely hard steel (1.0% or more carbon).
本発明の方法を適用して製造された平版印刷版
用支持体の好ましい態様を述べると、鉄材上にク
ロム電着層を有する平版印刷版用支持体であつ
て、該電着層の表面は角のある結晶状物が露出し
た形状を有し、該電着層の表面側部の元素組成は
クロム及び酸素から実質的になり、該部のクロム
及び酸素の各元素組成比が該表面から同一深さに
おいて、かつ該表面の各部分において実質的に均
一である構成を有している。そして該電着層表面
から基材側へ向つての酸素、クロム及び鉄等の基
材を構成する原子の構成比変化はおおむね酸素原
子については、表面から増加することなく、又は
若干増加した後じきに減少しはじめ、クロム原子
については表面から基材側に向つて増加した後、
基材に近づくにつれて減少していき、鉄等の基材
を構成する原子については、ある程度の深さのと
ころから存在し、深くなるにつれて増加していく
態様を有する。ここで基材とは支持体から電着層
を除いた部分である。 A preferred embodiment of the lithographic printing plate support produced by applying the method of the present invention is a lithographic printing plate support having a chromium electrodeposited layer on an iron material, wherein the surface of the electrodeposited layer is The electrodeposition layer has a shape in which angular crystals are exposed, and the elemental composition of the surface side portion of the electrodeposited layer is substantially composed of chromium and oxygen, and the elemental composition ratio of chromium and oxygen in this portion is lower than that from the surface. It has a configuration that is substantially uniform at the same depth and on each portion of the surface. The change in the composition ratio of atoms constituting the base material such as oxygen, chromium, and iron from the surface of the electrodeposited layer toward the base material is generally such that oxygen atoms do not increase from the surface or after a slight increase. It soon begins to decrease, and chromium atoms increase from the surface toward the base material, and then
The atoms decrease as the distance approaches the base material, and atoms constituting the base material such as iron exist from a certain depth and increase as the depth increases. Here, the base material is the part of the support excluding the electrodeposited layer.
クロム電着層は基材側においては実質的に基材
を構成する原子及びクロム原子から構成され、か
つ該基材に近づくにつれて基材を構成する原子の
構成比は大に、クロム原子の構成比は小に連続的
に変化している。クロム電着層とは、支持体表面
から基材を構成する原子の構成原子数とクロム原
子の構成原子数が一致するところまでをいい、そ
の厚さは0.01〜10μmが好ましく、特に0.01〜4μm
が好ましい。この膜厚はケイ光Ｘ線分析により、
基準の膜厚既知のクロムメツキ層により、予め作
成しておいた検量線より定量して平均値として求
めることができる。 On the base material side, the chromium electrodeposition layer is substantially composed of atoms constituting the base material and chromium atoms, and as it approaches the base material, the composition ratio of the atoms constituting the base material increases, and the composition of chromium atoms increases. The ratio changes continuously. The chromium electrodeposition layer refers to the area from the surface of the support to the point where the number of atoms constituting the base material and the number of atoms constituting the chromium atoms match, and its thickness is preferably 0.01 to 10 μm, particularly 0.01 to 4 μm.
is preferred. This film thickness was determined by fluorescent X-ray analysis.
Using a chrome plating layer with a known standard film thickness, it is possible to determine the average value by quantifying from a calibration curve prepared in advance.
上記の「クロム電着層が基材側においては実質
的に基材を構成する原子及びクロム原子から構成
される」とは、基材を構成する原子及びクロム原
子の各原子数比率の合計が60％以上であることを
意味し、また、「クロム電着層の表面側部」とは
該電着層表面から基材を構成する原子の原子数比
率が20％をこえるところまでをいい、「表面側部
の元素組成はクロム及び酸素から実質的になる。」
とは、クロム原子及び酸素原子の各原子数比率の
合計が50％以上であることを意味し、クロム原子
及び酸素原子以外に本発明の効果を阻害しない範
囲でこれら以外の成分例えば、炭素原子、塩素原
子、硫黄原子、カルシウム、窒素原子、フツ素原
子等を含んでいても差し支えないことを意味す
る。 The above statement that "the chromium electrodeposited layer is substantially composed of atoms constituting the base material and chromium atoms" means that the total atomic ratio of the atoms constituting the base material and chromium atoms is 60% or more, and the "surface side part of the chromium electrodeposited layer" refers to the area from the surface of the electrodeposited layer to the point where the atomic ratio of atoms constituting the base material exceeds 20%, "The elemental composition of the side surfaces consists essentially of chromium and oxygen."
means that the total ratio of each atomic number of chromium atoms and oxygen atoms is 50% or more, and in addition to chromium atoms and oxygen atoms, components other than these, such as carbon atoms, may not be contained within the range that does not impede the effects of the present invention. , chlorine atom, sulfur atom, calcium, nitrogen atom, fluorine atom, etc.
上記原子数比率は、光電子分光法（例えばＸ線
光電子分光法等）、及びオージエ電子分光法等の
表面分析手段により求めることができる。 The atomic ratio can be determined by surface analysis means such as photoelectron spectroscopy (for example, X-ray photoelectron spectroscopy) and Auger electron spectroscopy.
クロム電着層の深さ方向元素分布は、オージエ
電子分光法によつて求められ、例えばPerkin
Elmer社製、走査型オージエ電子顕微鏡
（Scanning Auger Microprobe）PHI.Model
595又は600による局所分析により、クロム電着層
の表面側の各部分における各種の深さでの原子数
比率が求められる。 The elemental distribution in the depth direction of the chromium electrodeposited layer is determined by Auger electron spectroscopy, for example Perkin
Elmer, Scanning Auger Microprobe PHI.Model
By local analysis using 595 or 600, the atomic ratio at various depths in each part on the surface side of the chromium electrodeposited layer can be determined.
クロム電着層の表面側部の元素組成としては表
面の法線上の深さ方向におけるクロム及び酸素の
原子数比率変化において表面からXnmの深さに
おけるクロムの原子数比率Ya％が式（）Ya≦
−0.464X2＋7.82X＋70（０≦Ｘ≦６）及び式
（）Ya≧−0.0398X2＋1.99X＋15（０≦Ｘ≦25）
の条件式をみたす範囲内にあり、酸素の原子数比
率Yb％が式（）Yb≦0.0884X2−4.46X＋80（０
≦Ｘ≦25）及び式（）Yb≧0.5X2−8.1X＋20
（０≦Ｘ≦３）の条件式をみたす範囲内にあり、
更にYa及びYbの和が式（）Ya＋Yb≧−
0.0187X2＋1.23X＋50（但し０≦Ｘ≦25）をみた
す範囲内にあることが好ましい。又、Xnm＜
1.0nmにおいてYb＞Yaであり、Ya＝Ybになる
深さXonmが1.0≦Xo≦14.0である場合が更に好
ましく、特に好ましいのは1.5≦Xo≦８の場合で
ある。 As for the elemental composition of the surface side of the chromium electrodeposited layer, the atomic ratio Ya% of chromium at a depth of X nm from the surface is expressed by the formula () Ya ≦
−0.464X 2 +7.82X+70 (0≦X≦6) and formula ()Ya≧−0.0398X 2 +1.99X+15 (0≦X≦25)
It is within the range that satisfies the conditional formula, and the oxygen atomic number ratio Yb% is within the range that satisfies the formula ()Yb≦0.0884X 2 −4.46X+80(0
≦X≦25) and formula () Yb≧0.5X 2 −8.1X+20
It is within the range that satisfies the conditional expression (0≦X≦3),
Furthermore, the sum of Ya and Yb is expressed as ()Ya+Yb≧−
It is preferable to fall within a range satisfying 0.0187X 2 +1.23X+50 (0≦X≦25). Also, Xnm<
It is more preferable that Yb>Ya at 1.0 nm, and the depth Xonm at which Ya=Yb is 1.0≦Xo≦14.0, and particularly preferable is the case that 1.5≦Xo≦8.
なお、上記の表面からの深さは下記の深さ方向
分析に基づき変換により求めたものである。 Note that the above depth from the surface was determined by conversion based on the depth direction analysis described below.
前記PHI Model 595による深さ方向分析の測
定条件は、イオン銃としてはアルゴンイオンを使
用し、エツチング速度は酸化タリウム（Ta2O5）
を基準として20Å／分以下（膜厚既知のTa2O5を
エツチングする時間より求めた。）で行ない、更
に元素組成比の計算に際しては、使用したオージ
エスペクトル（微分形）のピーク強度は、クロム
については529eVのピーク、酸素については
503eVのピークに関してのもので、クロムと酸素
の相対感度は、L.E.Davis，P.W.Palmberg，G.
E.Riach，R.E.Weber，N.C.MacDonald著
“Handbook of Muger Electron Spectroscopy
sec.ed.”（Physical Electronics Division
Perkin−Elmer Corp.発行1976年）に記載されて
いる値を用いる。又、一次電子線の直径は500Å
〜1μmに絞つて結晶状部分と非結晶状部分を区別
し微少領域分析を行なう。結晶状部分の測定に際
して、一次電子線は結晶状部分の中心部に正確に
照射させ、結晶状部分の縁が該ビーム照射領域に
含まれないようにして行なう。例えば、板状結晶
部については、該平面部中心に照射させる。また
エツチングのイオンビームは結晶状部面及び非結
晶状部面に対し45゜〜90゜の入射角度で照射する。
この際、分析個所にない周囲の他の結晶状物等に
より該イオンビームの分析個所への入射が妨害さ
れてはならない。更に一次電子銃と電子エネルギ
ー分析器とは、同方向軸に設置されている（コア
キシヤルタイプ）ものが本測定に望ましい。 The measurement conditions for the depth direction analysis using the PHI Model 595 were as follows: argon ions were used as the ion gun, and thallium oxide (Ta 2 O 5 ) was used as the etching rate.
The peak intensity of the Auger spectrum ( differential form) used was , a peak of 529eV for chromium, and for oxygen
The relative sensitivities of chromium and oxygen, with respect to the 503 eV peak, are given by LEDavis, PWPalmberg, G.
“Handbook of Muger Electron Spectroscopy” by E. Riach, REWeber, NC MacDonald
sec.ed.” (Physical Electronics Division
Perkin-Elmer Corp., 1976). Also, the diameter of the primary electron beam is 500Å
Microregion analysis is performed by narrowing down to ~1 μm and distinguishing between crystalline and non-crystalline parts. When measuring a crystalline part, the primary electron beam is irradiated accurately to the center of the crystalline part, and the measurement is carried out in such a way that the edges of the crystalline part are not included in the beam irradiation area. For example, in the case of a plate-shaped crystal part, the beam is irradiated to the center of the flat part. The etching ion beam is irradiated onto the crystalline and non-crystalline surfaces at an incident angle of 45° to 90°.
At this time, the incidence of the ion beam onto the analysis site must not be obstructed by other surrounding crystalline substances that are not present at the analysis site. Furthermore, it is preferable for this measurement that the primary electron gun and the electron energy analyzer are installed on the same axis (coaxial type).
上記の表面からの深さXnmは前記エツチング
速度からエツチング時間を深さに変換したもの
で、すべての組成物を酸化クロム（Cr2O3）とし
て計算したものである。更に前記元素組成比は単
位面積当りの原子数の比を示す。 The depth Xnm from the surface is calculated by converting the etching time from the etching rate into depth, and assumes that all compositions are chromium oxide (Cr 2 O 3 ). Furthermore, the elemental composition ratio indicates the ratio of the number of atoms per unit area.
クロム電着層表面側部のクロム及び酸素の各元
素組成比が該表面から同一深さにおいて、かつ該
表面の各部において実質的に均一であるとは、表
面の結晶状物が露出した形状の部分、その他の部
分を問わず、クロム及び酸素の各元素組成比が実
質的に同一であることを意味し、実質的に同一と
は各部分における深さ方向の元素分布において
Xoの値が±80％以上に誤差範囲内であることを
意味する。上記誤差とは、２つの値の差を両者の
うち大きい方の値で割り、100を乗じたものであ
る。 The fact that the elemental composition ratios of chromium and oxygen on the sides of the surface of the chromium electrodeposited layer are substantially uniform at the same depth from the surface and in each part of the surface means that the shape of exposed crystals on the surface This means that the elemental composition ratios of chromium and oxygen are substantially the same, regardless of whether they are in the same part or in other parts, and "substantially the same" means that the elemental distribution in the depth direction in each part is
This means that the value of Xo is within the error range of ±80% or more. The above error is the difference between two values divided by the larger of the two, multiplied by 100.
本発明の方法により製造されるクロム電着層の
表面側部は深さの方向の元素分析から、クロム酸
化物（この酸化物には水和物も包含される。）及
び金属クロムから実質的に構成され、深くなるに
つれて金属クロムの比率が多くなつていると判断
される。クロム酸化物としては２価、３価又は６
価のクロム酸化物が挙げられるが主として３価ク
ロムの酸化物である。 Elemental analysis in the depth direction reveals that the surface side of the chromium electrodeposited layer produced by the method of the present invention is substantially composed of chromium oxide (this oxide also includes hydrates) and metallic chromium. It is judged that the ratio of metallic chromium increases as the depth increases. Divalent, trivalent or hexavalent chromium oxide
Examples include valent chromium oxides, but mainly trivalent chromium oxides.
クロム電着層の表面の角のある結晶状物が露出
した表面形状としては、板状もしくは６面体状、
例えば立方体状の結晶状物、これらの結晶状物の
凝集体又は該結晶状物及／又は該凝集体の混合物
が露出した形状が好ましい。板状結晶状物として
は、多角形、主として６角形の板状のものが好ま
しく、多角形状の面の径は0.5〜5μmのものが好
ましく、厚さは0.01〜0.8μmのものが好ましい。
６面体結晶状物としては立方体状、特に辺長が
0.1〜2μmのものが好ましい。 The surface shape of the exposed angular crystals on the surface of the chromium electrodeposited layer is plate-like, hexahedral-like,
For example, a shape in which a cubic crystalline substance, an aggregate of these crystalline substances, or a mixture of the crystalline substance and/or the aggregate is exposed is preferable. The plate-like crystalline material is preferably polygonal, mainly hexagonal, with a diameter of 0.5 to 5 .mu.m and a thickness of 0.01 to 0.8 .mu.m.
As a hexahedral crystal, it has a cubic shape, especially the side length.
A thickness of 0.1 to 2 μm is preferable.
上述の「角のある結晶状物」とは、球状ないし
はだ円体状の結晶状物及びこれらが融合したもの
とは異なり、角ばつた結晶状物を意味し、3000倍
ないし30000倍程度の電子顕微鏡写真において、
クロム電着層の表面形状における結晶状に見える
突出部分の有する角が第１図ないし第７図に示す
結晶状物の角、即ち面角及び稜の曲率半径と同程
度またはそれより小であると認められるものを包
含する。 The above-mentioned "angular crystalline material" refers to a crystalline material with an angular shape, which is different from a spherical or ellipsoidal crystalline material or a fusion of these. In electron micrographs,
The angles of the crystal-like protrusions in the surface shape of the chromium electrodeposited layer are the same or smaller than the angles of the crystalline objects shown in Figures 1 to 7, that is, the face angles and curvature radius of the edges. Includes those recognized as such.
これらの結晶状物が露出した形状の部分の投影
面積率としては20％以上が好ましい。ここに投影
面積率は本発明の電着層を有する支持体面に垂直
な方向の投影、即ち正投影におけるものであつて
該面積率は顕微鏡写真等により測定できる。 The projected area ratio of the portion in which these crystalline substances are exposed is preferably 20% or more. The projected area ratio here refers to projection in a direction perpendicular to the surface of the support having the electrodeposited layer of the present invention, that is, orthogonal projection, and the area ratio can be measured using a micrograph or the like.
第１図〜第７図は、本発明の方法により製造さ
れる代表的な平版印刷版用支持体のクロム電着層
表面を走査式電子顕微鏡を用いて撮影した写真で
あり、第１図〜第５図は各種の板状結晶状物が、
第６図及び第７図は立方体結晶状物及立方体状結
晶状物の凝集体が露出した形状を有するものであ
る。 1 to 7 are photographs taken using a scanning electron microscope of the surface of the chromium electrodeposited layer of a typical lithographic printing plate support manufactured by the method of the present invention. Figure 5 shows various plate-like crystals.
FIGS. 6 and 7 show shapes in which cubic crystals and aggregates of cubic crystals are exposed.
本発明の方法の実施において、鉄材に本発明の
電着クロム層を形成する電解処理を施す前に必要
に応じて、脱脂あるいはサビ取り等の前処理を行
ない表面を清浄にすることが望ましい。 In carrying out the method of the present invention, it is desirable to perform pretreatment such as degreasing or rust removal as necessary to clean the surface before subjecting the iron material to the electrolytic treatment for forming the electrodeposited chromium layer of the present invention.
脱脂処理としては、溶剤脱脂、アルカリ脱脂、
電解脱脂、エマルジヨン脱脂、機械的脱脂などの
方法が挙げられる。本発明では特に電解脱脂によ
る陽極処理が好ましく、無水クロム酸水溶液に硝
酸を加えたものを電解液としたものが、次の本処
理に際し液中に持ち込みがあつても悪影響を及ぼ
さないので有効に用いられる。前処理としての陽
極処理用電解液および電解条件の代表例を下記に
示す。 Degreasing treatments include solvent degreasing, alkaline degreasing,
Methods include electrolytic degreasing, emulsion degreasing, mechanical degreasing, and the like. In the present invention, anodic treatment by electrolytic degreasing is particularly preferred, and an electrolyte prepared by adding nitric acid to an aqueous chromic acid anhydride solution is effective because it will not have an adverse effect even if it is brought into the solution during the next main treatment. used. Representative examples of the electrolytic solution and electrolytic conditions for anodization as pretreatment are shown below.
電解液
無水クロム酸 80〜200ｇ
硝 酸（６％） 0.5〜１ml／
水 1000ml
電解条件
電流密度 ２〜10A／ｄm2
液 温 10〜40℃
陰 極 鉄電極
陽 極 鉄 材
陰極と陽極の面積比 １：１
処理時間 30秒〜５分
このように前処理した鉄材にシヤワー等により
水を吹きかけて水洗した後、本処理、即ち本発明
の電着クロム層形成処理に移る。 Electrolyte Chromic anhydride 80~200g Nitric acid (6%) 0.5~1ml/Water 1000ml Electrolytic conditions Current density 2~10A/dm Two liquids Temperature 10~40℃ Cathode Iron electrode Anode Iron material Area ratio of cathode and anode 1:1 Treatment time: 30 seconds to 5 minutes After washing the thus pretreated iron material by spraying it with water using a shower or the like, the process proceeds to the main treatment, that is, the electrodeposition chromium layer forming treatment of the present invention.
この電着クロム層形成工程において、その電解
条件について述べると、温度は25℃を超えること
が必要であり、電流密度は１〜150A／ｄm2の範
囲が好ましく、より好ましくは5A／ｄm2を超え
て60A／ｄm2以下であり、特に７〜60A／ｄm2が
好ましい。陰極を電着クロム層を形成させる鉄材
とし、陽極としては主として鉛電極を用いること
が好ましい。又、陰極と陽極との面積比は１：１
〜１：1.5が好ましい。更に処理時間は少なくと
も10秒間は必要とし、10分程度で充分といえる。
温度は100℃以下であることが望ましい。温度が
高い程、できあがつた支持体表面の色調が白色化
し、クロム電着層表面に露出した角のある結晶状
物が大きくなる。又、処理時間が長い程該結晶状
物の表面に占める密度が大となる。 Regarding the electrolytic conditions in this electrodeposited chromium layer forming step, the temperature needs to exceed 25°C, and the current density is preferably in the range of 1 to 150 A/ dm2 , more preferably 5 A/ dm2 . more than 60 A/dm 2 , particularly preferably 7 to 60 A/dm 2 . It is preferable to use an iron material for forming an electrodeposited chromium layer as the cathode, and to use mainly a lead electrode as the anode. Also, the area ratio of the cathode and anode is 1:1.
~1:1.5 is preferred. Furthermore, a processing time of at least 10 seconds is required, and about 10 minutes is sufficient.
It is desirable that the temperature is below 100°C. The higher the temperature, the whiter the color tone of the surface of the formed support becomes, and the larger the angular crystals exposed on the surface of the chromium electrodeposition layer become. Furthermore, the longer the treatment time, the greater the density occupied on the surface of the crystalline material.
なお電解液は液調整後予備電解してから電解を
行なう。 Note that the electrolytic solution is prepared and subjected to preliminary electrolysis before electrolysis.
電解液中のフツ素化合物の添加量は、クロム電
着層のつき廻りの点から10ｇ／以下が特に好ま
しく、又、クロム電着層表面に結晶状物が形成し
やすいという点から0.01ｇ／以上が特に好まし
い。 The amount of the fluorine compound added to the electrolytic solution is particularly preferably 10 g/or less from the viewpoint of coverage of the chromium electrodeposition layer, and 0.01 g/or less from the viewpoint of easy formation of crystalline substances on the surface of the chromium electrodeposition layer. The above is particularly preferable.
本発明のクロム電着層を施した鉄材は水洗し乾
燥して使用に供することができるが、下記のよう
な後処理を施すことが好ましい。 Although the iron material coated with the chromium electrodeposition layer of the present invention can be used after being washed with water and dried, it is preferable to perform the following post-treatment.
例えば、カルボキシメチルセルロースナトリウ
ム塩水溶液、ポリビニルアルコール水溶液、ポリ
メタアクリル酸溶液、ポリアクリル酸溶液、アル
ギン酸ナトリウム水溶液、等の親水性樹脂の水溶
液、又、リン酸、硫酸アルミニウム等の酸類、カ
セイソーダ等のアルカリ類、及びフツ化ジルコン
酸カリウム、フツ化チタンカリウム等のフツ化
物、更にモリブデン酸アンモン、リンタングステ
ン酸、リンタングステン酸ナトリウム、リンモリ
ブデン酸ナトリウム、ケイタングステン酸等の第
５，６族金属を含む塩の水溶液等で適当な温度で
版材を洗浄あるいは浸漬させ処理することができ
る。 For example, aqueous solutions of hydrophilic resins such as carboxymethylcellulose sodium salt aqueous solution, polyvinyl alcohol aqueous solution, polymethacrylic acid solution, polyacrylic acid solution, sodium alginate aqueous solution, acids such as phosphoric acid and aluminum sulfate, and alkalis such as caustic soda. and fluorides such as potassium zirconate fluoride and potassium titanium fluoride, and group 5 and 6 metals such as ammonium molybdate, phosphotungstic acid, sodium phosphotungstate, sodium phosphomolybdate, and tungstosilicic acid. The plate material can be treated by washing or immersing it in an aqueous salt solution or the like at an appropriate temperature.
本発明の製造方法によつて製造された支持体は
その電着クロム層の持つ表面形状のため、感光性
平版印刷板として用いられた際、その上に設けら
れる感光層等親油性表面を有する多くの高分子化
合物を有する層との接着性に優れており、耐刷性
が良好である。又、現像性の寛容度が広いため、
必要以上の摩耗を伴なう現像処理である“手現
像”でも画像部が損失することが極めて少ない。 Because of the surface shape of the electrodeposited chromium layer, the support produced by the production method of the present invention has a lipophilic surface such as a photosensitive layer provided thereon when used as a photosensitive lithographic printing plate. It has excellent adhesion to layers containing many polymer compounds and has good printing durability. In addition, because of the wide latitude in developability,
Even in "manual development," which is a development process that involves more wear than necessary, there is extremely little loss of image areas.
更にその表面形状のため印刷時において保水性
が良く水の管理が容易である。 Furthermore, due to its surface shape, it has good water retention properties and easy water management during printing.
又、従来の支持体であるアルミニウム板やクロ
ムめつき鉄材に対して、製造工程が単純であり、
生産性が高く生産コストが低い。 In addition, the manufacturing process is simple compared to conventional supports such as aluminum plates and chrome-plated iron materials.
High productivity and low production costs.
なお、本発明の方法は、電解液と被電着物との
間の比較的速り相対的運動（例えば電解液の撹拌
等）を伴う電着方法にも有利であり、高速電着あ
るいは連続高速電着による平版印刷版用支持体の
製造方法に特に有用である。 The method of the present invention is also advantageous for electrodeposition methods that involve relatively fast relative motion between the electrolyte and the electrodeposited material (for example, stirring of the electrolyte), and is suitable for high-speed electrodeposition or continuous high-speed electrodeposition. It is particularly useful in methods for producing supports for lithographic printing plates by electrodeposition.
以下、実施例によつて本発明を更に詳細に説明
する。ただし本発明の実施態様はこれらに限定さ
れるものではない。 Hereinafter, the present invention will be explained in more detail with reference to Examples. However, the embodiments of the present invention are not limited to these.
実施例 １
厚さ0.15mmの炭素鋼板に前処理工程として表１
に示す電解液に対向電極板として鉄板を用い、
第２表に示す電解条件で電解処理を施した。Example 1 Table 1 was performed as a pretreatment process on a carbon steel plate with a thickness of 0.15 mm.
Using an iron plate as a counter electrode plate for the electrolyte shown in
Electrolytic treatment was performed under the electrolytic conditions shown in Table 2.
表１ 電解液
無水クロム酸 100Kg
硝 酸（64Kg） 0.8
水 1000
表２ 電解条件
電流密度 4A／ｄm2
液 温 25℃
陰 極 鉄板（1.2m2）
陽 極 支持体用鉄板（1.2m2）
処理時間 １分
このようにして前処理工程を終了した炭素鋼板
は、続いてシヤワー水洗を行ない、本発明の電着
被覆を施すために次の本処理工程を施した。本処
理工程の電解液の組成および電解条件を表
３、表４に示す。 Table 1 Electrolyte Chromic acid anhydride 100Kg Nitric acid (64Kg) 0.8 Water 1000 Table 2 Electrolysis conditions Current density 4A/dm 2 liquids Temperature 25℃ Cathode Iron plate (1.2m 2 ) Anode Iron plate for support (1.2m 2 ) Treatment Time: 1 minute The carbon steel plate that had undergone the pretreatment step in this manner was then washed with shower water, and subjected to the next main treatment step in order to apply the electrodeposition coating of the present invention. The composition of the electrolytic solution and electrolysis conditions in this treatment step are shown in Tables 3 and 4.
表３ 電解液
無水クロム酸 430Kg
硝酸バリウム 3.8Kg
硝 酸（64％） 1.2
弗化水素アンモニウム ５Kg
酢 酸 0.2Kg
弗化バリウム 0.1Kg
水 1000
表４ 電解条件
電流密度 20A／ｄm2
液温度 30℃
陰 極 支持体用鉄板（1.2m2）
陽 極 鉛板（1.6m2）
処理時間 ３分
このようにして本処理工程を終了した炭素鋼板
は、続いてシヤワー水洗を行ない、次の後処理工
程に移した。後処理工程では、先ずはじめに５％
カセイソーダ水溶液に40℃にて１分間浸漬し、続
いてシヤワー水洗を行ない、次にカルボキシメチ
ルセルロースナトリウム塩水溶液（0.07重量％）
に室温にて約１分間浸漬し続いてシヤワー水洗を
行つた。後処理工程を終了した後、冷風にて乾燥
を行つた。 Table 3 Electrolyte Chromic acid anhydride 430Kg Barium nitrate 3.8Kg Nitric acid (64%) 1.2 Ammonium hydrogen fluoride 5Kg Acetic acid 0.2Kg Barium fluoride 0.1Kg Water 1000 Table 4 Electrolysis conditions Current density 20A/dm 2 liquid temperature 30℃ Negative Electrode Steel plate for support (1.2m 2 ) Anode Lead plate (1.6m 2 ) Processing time 3 minutes After the main treatment process has been completed in this way, the carbon steel plate is then showered and washed with water, and is ready for the next post-treatment process. Moved. In the post-processing process, first 5%
Immerse in caustic soda aqueous solution at 40℃ for 1 minute, then shower and rinse, then carboxymethylcellulose sodium salt aqueous solution (0.07% by weight)
The sample was immersed in water for about 1 minute at room temperature, and then washed with shower water. After completing the post-treatment process, drying was performed with cold air.
前記の方法で製造した電着クロム層を有する支
持体の表面には、微粒子集合状の地はだの上に板
状結晶状物が突出して散在する表面が形成されて
いることが電子顕微鏡写真（第１，２図）で確認
された。また形成された電着クロム層表面につい
て、オージエ電子分析装置（Perkin Elmer社製
走査型オージエ電子顕微鏡PHI Model 595）を
用いてその組成を分析し、第８図及び第９図の深
さ方向の元素分析結果を得た。第８図は結晶状物
が露出した部分についてのものであり、第９図は
非露出部分についてのものである。 Electron micrographs show that the surface of the support having the electrodeposited chromium layer manufactured by the above method has a surface in which plate-shaped crystals protrude and are scattered on a base of fine particle aggregates. This was confirmed in (Figures 1 and 2). In addition, the composition of the surface of the formed electrodeposited chromium layer was analyzed using an Auger electron analyzer (Perkin Elmer scanning Auger electron microscope PHI Model 595), and the depth direction in Figures 8 and 9 was analyzed. Elemental analysis results were obtained. FIG. 8 shows the part where the crystalline substance is exposed, and FIG. 9 shows the part where the crystalline substance is not exposed.
測定条件は、イオン銃：4KeV、25mA、
raster5mm×５mm、アルゴンイオン使用、エツチ
ング速度：Ta2O5を基準として20Å／分、一次電
子銃：10KeV、電子線の直径は約500Åに絞り、
結晶状物の分析の際は、第１，２図におけるよう
な板状結晶部の平面部中心に電子線を照射させ、
照射領域内に結晶部の縁が含まれないようにし
て、イオンビームは板状結晶状部の平面部に対し
てほぼ90゜近い入射角度で照射させ、分析個所の
板状結晶でないその周囲の他の板状結晶物により
イオンビームの分析個所への入射が防害されない
ように測定対象の結晶状物を選択した。又測定の
前後で分析個所の板状結晶状部が正しくエツチン
グされているかを上記PHI Model 595の走査型
電子顕微鏡で確認した。 Measurement conditions are ion gun: 4KeV, 25mA,
raster 5 mm x 5 mm, using argon ions, etching rate: 20 Å/min based on Ta 2 O 5 , primary electron gun: 10 KeV, electron beam diameter narrowed to approximately 500 Å,
When analyzing a crystalline substance, an electron beam is irradiated onto the center of the flat part of the plate-like crystal part as shown in Figures 1 and 2.
The ion beam is irradiated at an angle of incidence of approximately 90° to the flat surface of the plate-like crystal part, making sure that the edge of the crystal part is not included in the irradiation area. The crystalline material to be measured was selected so that other plate-like crystalline materials would not prevent the ion beam from entering the analysis site. In addition, before and after the measurement, it was confirmed using the PHI Model 595 scanning electron microscope that the plate-like crystal part at the analysis location was etched correctly.
又元素組成比の計算に関して、使用したオージ
エスペクトル（微分形）のピーク強度は、クロム
は529eVのピーク、酸素は503eVのピークのもの
であり、クロムの相対感度を0.28、酸素の相対感
度を0.35として行なつた。第８図及び第９図の横
軸の表面からの深さは、前記エツチング速度から
エツチング時間を深さに変換したもので、すべて
の組成物をCr2O3とみなして計算したものであ
る。 In addition, regarding the calculation of the elemental composition ratio, the peak intensities of the Augier spectra (differential form) used are 529 eV peak for chromium and 503 eV peak for oxygen.The relative sensitivity of chromium is 0.28, and the relative sensitivity of oxygen is 0.28. I did it as 0.35. The depth from the surface on the horizontal axis in FIGS. 8 and 9 is the etching time converted from the etching rate to the depth, and is calculated assuming that all the compositions are Cr 2 O 3 . .
更に、第１０図は結晶状物が露出していない部
分について基材に到るまでエツチングして得た深
さ方向の分析結果である。測定条件は、エツチン
グ速度を85Å／分（Ta2O5を基準として）とした
以外は上記と同である。第１０図の横軸は上記と
同様にエツチング時間を深さに変換したもので、
すべて組成物を酸化クロム（Cr2O3）とみなして
計算したものである。又、結晶部についても同様
に基材の鉄に到るまでエツチングして第１０図と
同様の深さ方向の元素分布が得られた。これらの
結果から、基材側において、実質的に鉄原子及び
クロム原子から構成され、かつ該基材に近づくに
つれて鉄の構成比は大に、クロム原子の構成比は
小に連続的に変化していることがわかる。 Further, FIG. 10 shows the analysis results in the depth direction obtained by etching the portion where the crystalline material is not exposed down to the base material. The measurement conditions were the same as above except that the etching rate was 85 Å/min (based on Ta 2 O 5 ). The horizontal axis in Figure 10 is the etching time converted to depth in the same way as above.
All calculations were made assuming that the composition was chromium oxide (Cr 2 O 3 ). Further, the crystalline portions were similarly etched down to the iron base material, and an elemental distribution in the depth direction similar to that shown in FIG. 10 was obtained. These results show that the base material side is substantially composed of iron atoms and chromium atoms, and as it approaches the base material, the composition ratio of iron increases and the composition ratio of chromium atoms changes continuously. You can see that
次いで、この支持体上に下記組成の感光性塗布
液を回転塗布機を用いて塗布し、100℃で４分間
乾燥し、平版印刷版材料を得た。 Next, a photosensitive coating solution having the following composition was coated onto this support using a rotary coater and dried at 100°C for 4 minutes to obtain a lithographic printing plate material.
（感光性塗布液組成）
Γナフトキノン−（１，２）−ジアジド−(2)−５−
スルホン酸クロライドとｍ−クレゾール・ホル
ムアルデヒドノボラツク樹脂とのエステル化物
（縮合率25モル％） 3.5ｇ
Γｍ−クレゾール・ホルムアルデヒドノボラツク
樹脂 8.0ｇ
Γナフトキノン−（１，２）−ジアジド−(2)−４−
スルホン酸クロライド 0.15ｇ
Γｐ−オクチルフエノールノボラツク樹脂とナフ
トキノン−（１，２）−ジアジド−(2)−５−スル
ホン酸クロライドとのエステル化物（縮合率50
モル％） 0.12ｇ
Γオイルブルー＃603（オリエント化学工業(株)社
製） 0.2ｇ
Γエチルセロソルブ 100ｇ
乾燥後の塗布重量は約2.7ｇ／m2であつた。(Photosensitive coating liquid composition) Γnaphthoquinone-(1,2)-diazide-(2)-5-
Esterified product of sulfonic acid chloride and m-cresol formaldehyde novolak resin (condensation rate 25 mol%) 3.5g Γm-cresol formaldehyde novolak resin 8.0g Γnaphthoquinone-(1,2)-diazide-(2)- 4-
Sulfonic acid chloride 0.15g Esterified product of Γp-octylphenol novolac resin and naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid chloride (condensation rate 50
(mol%) 0.12 g Γ Oil Blue #603 (manufactured by Orient Chemical Industry Co., Ltd.) 0.2 g Γ Ethyl Cellosolve 100 g The coating weight after drying was approximately 2.7 g/m 2 .
かくして得られた平版印刷版材料上にポジ原稿
フイルム及感度測定用ステツプタブレツト（イー
ストマン・コダツク社製No.２、濃度差0.15づつで
21段階のもの）を密着して2KWメタルハライド
ランプ（岩崎電気(株)社製アイドルフイン2000）を
光源として1mの距離から80秒間露光を行ない、
４％メタケイ酸ナトリウム水溶液で25℃にて45秒
間現像し、平版印刷版を得た。 A positive original film and step tablets for sensitivity measurement (No. 2 manufactured by Eastman Kodak Co., Ltd., each with a density difference of 0.15) were placed on the lithographic printing plate material thus obtained.
21 steps) and exposed for 80 seconds from a distance of 1 m using a 2KW metal halide lamp (Idol Fin 2000 manufactured by Iwasaki Electric Co., Ltd.) as the light source.
It was developed with a 4% aqueous sodium metasilicate solution at 25° C. for 45 seconds to obtain a lithographic printing plate.
支持体と画線部との接着性及び印刷版の耐刷性
を検討するために、耐処理薬品性試験及び印刷試
験を行なつた。耐処理薬品性試験としては、ダー
ルグレン湿し水装置で用いられているイソプロピ
ルアルコール水溶液に対する耐久性を調べた。 In order to examine the adhesion between the support and the image area and the printing durability of the printing plate, a treatment chemical resistance test and a printing test were conducted. As a treatment chemical resistance test, durability against an aqueous isopropyl alcohol solution used in a Dahlgren dampening device was investigated.
上記グレースケールの階段上に濃度差を持つ画
像ができた印刷版を35％イソプロピルアルコール
水溶液に室温で20分間浸漬の後、水洗し水を含ま
せた脱脂綿で画像部をこすり、その画像部をイソ
プロピルアルコールに浸漬前の画像部と比較する
ことにより、画像部の薬品に対する侵食性を判断
した。その結果、前記印刷版は画像部の侵食がな
く良好な耐処理薬品性を示した。耐刷性試験は、
オフセツト印刷機（ハマダスター900CDX）に印
刷機をかけて印刷を行ない、画像部に損傷が生じ
印刷不可能となるまでに得られた印刷物の枚数で
評価した。その結果、前記印刷版では20万枚まで
良好な印刷物が得られた。 The printing plate, which has an image with density differences on the gray scale steps, is immersed in a 35% isopropyl alcohol aqueous solution for 20 minutes at room temperature, washed with water, and rubbed with absorbent cotton soaked in water to remove the image area. The erodibility of the image area to chemicals was determined by comparing it with the image area before immersion in isopropyl alcohol. As a result, the printing plate had no erosion in the image area and exhibited good resistance to processing chemicals. The printing durability test is
Printing was performed using an offset printing machine (Hamadustar 900CDX), and evaluation was made based on the number of prints obtained until the image area was damaged and printing became impossible. As a result, up to 200,000 copies of good printed matter were obtained using the printing plate.
比較例 １
炭素鋼板上に電着クロム層を設けた平版印刷版
用支持体を特開昭55−145193号公報に記載の方法
に従つて製造した。すなわち、実施例１と同種の
炭素鋼板を、40℃の予備洗浄槽（希塩酸）に30秒
間浸漬し、水洗した後、フツ化水素アンモニウム
を水１あたり60ｇ含む40℃の粒状化槽に５分間
浸漬し、水洗し、水１当り無水クロム酸250ｇ、
硫酸２ｇを含むメツキ浴中に浸漬し、陰極に結合
して浴温35℃、電流密度110A／ｄm2で60秒間の
メツキ処理を行なつた。このようにして得られた
表面に電着クロム層を有する鋼板支持体上に実施
例１と同じ処方で同様に塗布して平版印刷版材料
を得た。Comparative Example 1 A lithographic printing plate support having an electrodeposited chromium layer provided on a carbon steel plate was manufactured according to the method described in JP-A-55-145193. That is, a carbon steel plate of the same type as in Example 1 was immersed in a pre-cleaning tank (diluted hydrochloric acid) at 40°C for 30 seconds, washed with water, and then immersed in a granulation tank at 40°C containing 60 g of ammonium hydrogen fluoride per water 1 for 5 minutes. Soak, rinse with water, chromic anhydride 250g per 1 water,
It was immersed in a plating bath containing 2 g of sulfuric acid, connected to the cathode, and plated at a bath temperature of 35° C. and a current density of 110 A/dm 2 for 60 seconds. A lithographic printing plate material was obtained by coating the thus obtained steel plate support having an electrodeposited chromium layer on its surface using the same formulation as in Example 1.
かかる平版印刷版材料に実施例１と同様に露
光、現像を行ない平版印刷版を得て、これについ
て、上記実施例１と同様の耐処理薬品性試験及び
印刷試験を行なつた。その結果、この印刷版は画
像部の侵食が著しく認められ耐処理薬品性が不良
であり、また５万枚程印刷したところで非画像部
の汚れ、画像部の網点のからみが発生し回復せず
印刷不可能となつた。 The lithographic printing plate material was exposed and developed in the same manner as in Example 1 to obtain a lithographic printing plate, which was subjected to the same processing chemical resistance test and printing test as in Example 1 above. As a result, this printing plate showed significant erosion in the image area and poor processing chemical resistance, and after about 50,000 sheets were printed, stains in the non-image area and entanglement of halftone dots in the image area occurred, and it was difficult to recover. It became impossible to print.
実施例 ２
厚さ0.1mmの鋼板を実施例１と同様にして前処
理工程の電解処理を行なつた。Example 2 A steel plate having a thickness of 0.1 mm was subjected to electrolytic treatment as a pretreatment process in the same manner as in Example 1.
このようにして前処理工程を終了した鋼板をシ
ヤワー水洗し、次の本処理工程を施した。本処理
工程の電解液の組成および電解条件を表５お
よび表６に示す。 The steel plate that had undergone the pretreatment step in this manner was washed with water under a shower, and then subjected to the next main treatment step. The composition of the electrolytic solution and the electrolytic conditions in this treatment step are shown in Tables 5 and 6.
表５ 電解液
無水クロム酸 400Kg
硝酸バリウム 3.8Kg
硝 酸（64％） 1.2
弗化水素アンモニウム ５Kg
酢 酸 0.1Kg
弗化バリウム 0.1Kg
水 1000
表６ 電解条件
電流密度 10A／ｄm2
液温度 30℃
陰 極 支持体としての鋼板（1.2m2）
陽 極 鉛板（1.2m2）
処理時間 ５分
このようにして本処理工程を終了した鋼板をシ
ヤワー水洗したのち室温で風乾した。 Table 5 Electrolyte Chromic acid anhydride 400Kg Barium nitrate 3.8Kg Nitric acid (64%) 1.2 Ammonium hydrogen fluoride 5Kg Acetic acid 0.1Kg Barium fluoride 0.1Kg Water 1000 Table 6 Electrolysis conditions Current density 10A/dm 2 liquid temperature 30℃ Negative Pole: Steel plate as support (1.2 m 2 ) Anode: Lead plate (1.2 m 2 ) Treatment time: 5 minutes The steel plate that had undergone the main treatment step in this manner was washed with water under a shower, and then air-dried at room temperature.
前記の方法で製造した電着クロム層被覆鋼板の
表面には立方体状結晶状物及びその凝集体が散在
することが電子顕微鏡写真によつて確認された。
該写真の１例を第６図に示す。又この形成された
電着クロム層表面について、実施例１と同様にオ
ージエ電子分析装置により解析したところ、第８
図と類似した深さ方向の元素分布が得られ、表面
近傍が実施例１で製造した支持体と同じようなク
ロム及び酸素の構成を有することが確認された。 It was confirmed by electron micrographs that cubic crystals and aggregates thereof were scattered on the surface of the steel sheet coated with the electrodeposited chromium layer produced by the above method.
An example of the photograph is shown in FIG. Furthermore, the surface of the formed electrodeposited chromium layer was analyzed using an Auger electron analyzer in the same manner as in Example 1, and it was found that
An element distribution in the depth direction similar to that shown in the figure was obtained, and it was confirmed that the vicinity of the surface had the same chromium and oxygen composition as the support produced in Example 1.
次いでこの支持体に下記の組成を有する感光性
塗布液を回転塗布機を用いて塗布し、85℃で３分
間乾燥し平版印刷版材料を得た。 Next, a photosensitive coating solution having the following composition was coated on this support using a rotary coater and dried at 85° C. for 3 minutes to obtain a lithographic printing plate material.
（感光性塗布液組成）
Γ共重合体Ａ 5.0ｇ
Γジアゾ樹脂Ｂ 0.5ｇ
ΓジユリマーAC−10L（日本純薬(株)社製） 0.05ｇ
ΓビクトリアピユアーブルーBOH（保土ケ谷化学
(株)社製） 0.1ｇ
Γメチルセロソルブ 100ml
但し、上記共重合体Ａは、モル比でｐ−ヒドロ
キシフエニルメタクリルアミド／アクリロニトリ
ル／エチルアクリレート／メタクリル酸／アゾビ
スイソブチロニトリル＝10／30／60／６／１の組
成をメチルセロソルブに溶解し、窒素置換した封
管中で65℃で10時間加熱し、反応終了後、反応液
を水中に撹拌下注ぎ生じた白色沈澱を取乾燥し
て得たものである。ジアゾ樹脂Ｂは室温で５％の
ジアゾ樹脂（商品名、E.H.C(株)製Ｄ−012）水溶
液と、10％ヘキサフルオロリン酸アンモニウム水
溶液を混合し、生じた沈澱物を吸収過し、30〜
40℃で減圧乾燥して得たヘキサフルオロリン酸塩
である。上記共重合体の重量平均分子量は80000
であり、更に上記ジアゾ樹脂の分子量分布をゲル
パーミネーシヨンクロマトグラフイー（GPC）
によつて測定したところ、３量体以下が全体の93
モル％であつた。(Photosensitive coating liquid composition) Γ copolymer A 5.0 g Γ diazo resin B 0.5 g Γ Diyurimer AC-10L (manufactured by Nippon Pure Chemical Industries, Ltd.) 0.05 g Γ Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.)
Co., Ltd.) 0.1g Γ Methyl Cellosolve 100ml However, the above copolymer A has a molar ratio of p-hydroxyphenyl methacrylamide/acrylonitrile/ethyl acrylate/methacrylic acid/azobisisobutyronitrile = 10/30 /60/6/1 was dissolved in methyl cellosolve and heated at 65°C for 10 hours in a sealed tube purged with nitrogen. After the reaction was complete, the reaction solution was poured into water with stirring and the white precipitate formed was removed and dried. This is what I got. Diazo resin B is obtained by mixing a 5% aqueous solution of diazo resin (trade name, D-012 manufactured by EHC Co., Ltd.) and a 10% aqueous ammonium hexafluorophosphate solution at room temperature, absorbing and filtering the resulting precipitate.
Hexafluorophosphate obtained by drying under reduced pressure at 40°C. The weight average molecular weight of the above copolymer is 80000
Furthermore, the molecular weight distribution of the above diazo resin was determined by gel permeation chromatography (GPC).
As measured by
It was in mol%.
乾燥後の塗布重量は約2.0ｇ／m2であつた。 The coating weight after drying was approximately 2.0 g/m 2 .
かくして得られた平版印刷版材料上にネガ原稿
フイルムを密着して2KWメタルハライドランプ
（岩崎電気(株)社製アイドルフイン2000）を光源と
して1mの距離から84秒間露光を行ない、下記の
組成の現像液で現像し、平版印刷版を得た。 A negative original film was closely adhered to the lithographic printing plate material obtained in this way, and it was exposed for 84 seconds from a distance of 1 m using a 2KW metal halide lamp (Idolfin 2000, manufactured by Iwasaki Electric Co., Ltd.) as a light source, and the following composition was developed. A lithographic printing plate was obtained by developing with liquid.
（現像液組成） Γフエニルセロソルブ 160ｇ Γジエタノールアミン 70ｇ ΓパイオニンＡ−44B（竹本油脂(株)社製） 50ｇ Γ水 780ｇ 現像条件は25℃、45秒間である。(Developer composition) Γ phenyl cellosolve 160g Γ diethanolamine 70g Γ Pionin A-44B (manufactured by Takemoto Yushi Co., Ltd.) 50g Γ water 780g The development conditions were 25°C and 45 seconds.
支持体と画像部との接着性、現像性の寛容度及
び印刷版の耐刷性を検討するために、現像につい
て自動現像機により処理の他に“手現像”処理試
験を行ない、又印刷試験を行なつた。 In order to examine the adhesion between the support and the image area, the latitude of developability, and the printing durability of the printing plate, we conducted a "hand development" processing test in addition to processing with an automatic developing machine, and a printing test. I did this.
手現像は、スポンジに上記現像液を充分含ま
せ、皿の中に置いた上記露光済みの平版印刷版材
料表面をそのスポンジで２分間均一にかるく擦
り、その後水洗いすることによつて行なつた。そ
の結果、上記平版印刷版材料は手現像によつても
画像部が損なわれることはまつたくなかつた。印
刷試験は実施例１と同様にして行なつた。その結
果、本発明の方法により製造された支持体を用い
た平版印刷版は20万枚まで良好な印刷物が得られ
た。 Manual development was carried out by thoroughly soaking a sponge with the developer, rubbing the surface of the exposed lithographic printing plate material placed in a dish lightly and uniformly for 2 minutes, and then washing with water. . As a result, the image area of the lithographic printing plate material was not damaged even by manual development. The printing test was conducted in the same manner as in Example 1. As a result, good printed matter was obtained up to 200,000 sheets using the lithographic printing plate using the support produced by the method of the present invention.
比較例 ２
別にコントロールとして下記の試料を作成し比
較した。即ち実施例２と同種の鋼板に比較例１と
同様にして電着クロム層を設けた版材を製造し、
この鋼板支持体上に実施例２に記載された感光性
塗布液を同様に塗布、乾燥し、平版印刷版材料を
得た。次にこれを実施例２と同様にして平版印刷
版を作成し、耐刷性試験を行なつた。その結果、
手現像処理において、画線部が著しく損なわれ、
ほとんど剥離してしまつた。更に、印刷において
は、８万枚印刷して画線部の一部が剥離してしま
い印刷不可能となつた。Comparative Example 2 The following sample was separately prepared as a control and compared. That is, a plate material was manufactured by providing the same type of steel plate as in Example 2 with an electrodeposited chromium layer in the same manner as in Comparative Example 1,
The photosensitive coating solution described in Example 2 was applied onto this steel plate support in the same manner and dried to obtain a lithographic printing plate material. Next, a lithographic printing plate was prepared in the same manner as in Example 2, and a printing durability test was conducted. the result,
During hand development processing, the image area is significantly damaged,
It almost peeled off. Furthermore, after printing 80,000 sheets, part of the image area peeled off, making printing impossible.
実施例 ３
厚さ0.15mmの鉄板に前処理工程として実施例１
と同様にして前処理工程の電解処理を行なつた。Example 3 Example 1 was applied as a pretreatment process to a 0.15 mm thick iron plate.
Electrolytic treatment as a pretreatment step was carried out in the same manner as above.
このようにして前処理工程を終了した鉄板をシ
ヤワー水洗し、次の本処理工程を施した。本処理
工程の電解液の組成、および電解条件を表７
及び表８に示す。 The iron plate that had undergone the pretreatment step in this manner was washed with water under a shower, and then subjected to the next main treatment step. Table 7 shows the composition of the electrolytic solution and electrolytic conditions in this treatment step.
and shown in Table 8.
表７ 電解液
無水クロム酸 430Kg
硝酸バリウム 3.8Kg
硝 酸（64％） 1.2
弗化水素アンモニウム ５Kg
酢 酸 0.2Kg
弗化バリウム 0.1Kg
水 1000
表８ 電解条件
電流密度 20A／ｄm2
液温度 40℃
陰 極 支持体用鉄板（1.2m2）
陽 極 鉛板（1.6m2）
処理時間 ５分
このようにして本処理工程を終了した鉄板は続
いてシヤワー水洗を行い、次の後処理工程に移し
た。後処理工程では、先ずはじめに５％カセイソ
ーダ水溶液に40℃にて１分間浸漬し、続いてシヤ
ワー水洗を行い、次にフツ化ジルコン酸カリウム
の水溶液（１重量％）に室温にて約１分間浸漬
し、続いてシヤワー水洗を行つた。後処理工程を
終了した鉄板は冷風にて乾燥を行つた。 Table 7 Electrolyte Chromic acid anhydride 430Kg Barium nitrate 3.8Kg Nitric acid (64%) 1.2 Ammonium hydrogen fluoride 5Kg Acetic acid 0.2Kg Barium fluoride 0.1Kg Water 1000 Table 8 Electrolysis conditions Current density 20A/dm 2 liquid temperature 40℃ Negative Pole: Steel plate for support (1.2 m 2 ) Anode: Lead plate (1.6 m 2 ) Processing time: 5 minutes After the main treatment process was completed, the steel plate was then washed with shower water and moved to the next post-treatment process. . In the post-treatment process, first, it was immersed in a 5% caustic soda aqueous solution at 40°C for 1 minute, followed by shower washing, and then immersed in a potassium fluoride zirconate aqueous solution (1% by weight) at room temperature for about 1 minute. Then, I showered and washed. After completing the post-treatment process, the iron plate was dried with cold air.
前記の方法で製造した電着クロム層被覆鉄板の
表面には立方体状結晶が構成要素となつている凝
集体状結晶が形成されている。又この形成された
電着クロム層表面について実施例１と同様にオー
ジエ電子分析装置により解析したところ、第８図
と類似した深さ方向の元素分布が得られ、表面近
傍が実施例１で製造した支持体と同じようなクロ
ム及び酸素の構成を有することが確認された。 On the surface of the iron plate coated with the electrodeposited chromium layer produced by the method described above, aggregate-like crystals consisting of cubic crystals are formed. Furthermore, when the surface of the formed electrodeposited chromium layer was analyzed using an Auger electron analyzer in the same manner as in Example 1, an elemental distribution in the depth direction similar to that shown in FIG. It was confirmed that the chromium and oxygen composition was similar to that of the support that was prepared.
次いでこの鉄板に、下記の組成を有する感光性
塗布機を回転塗布機を用いて塗布し、100℃で４
分間乾燥し、平版印刷版材料を得た。 Next, a photosensitive coater having the following composition was applied to this iron plate using a rotary coater, and the coating was applied at 100°C for 4 hours.
After drying for a minute, a lithographic printing plate material was obtained.
（感光性塗布液組成）
Γナフトキノン−（１，２）−ジアジド−(2)−５−
スルホン酸クロライドとレゾルシン−ベンズア
ルデヒド樹脂との縮合物（特開昭56−1044号公
報実施例１に記載された方法で合成されたも
の） 3.5ｇ
Γフエノールとｍ−ｐ−混合クレゾールとホルム
アルデヒドとの共重縮合樹脂（フエノールとク
レゾールのモル比が３：７重量平均分子量
1500） ８ｇ
Γナフトキノン−（１，２）−ジアジド−(2)−４−
スルホン酸クロライド 0.15ｇ
Γオイルブルー＃603（オリエント化学工業(株)社
製） 0.2ｇ
Γｐ−ｔ−ブチルフエノール・ホルムアルデヒド
ノボラツク樹脂 0.15ｇ
Γメチルセロソルブ 100ｇ
乾燥後の塗布重量は約2.5ｇ／m2であつた。(Photosensitive coating liquid composition) Γnaphthoquinone-(1,2)-diazide-(2)-5-
Condensate of sulfonic acid chloride and resorcinol-benzaldehyde resin (synthesized by the method described in Example 1 of JP-A-56-1044) 3.5 g Condensate of Γ phenol, m-p-mixed cresol and formaldehyde Copolycondensation resin (molar ratio of phenol and cresol is 3:7 weight average molecular weight)
1500) 8g Γnaphthoquinone-(1,2)-diazide-(2)-4-
Sulfonic acid chloride 0.15g Γ Oil Blue #603 (manufactured by Orient Chemical Industry Co., Ltd.) 0.2g Γp-t-butylphenol formaldehyde novolac resin 0.15g Γmethyl cellosolve 100g Coating weight after drying is approximately 2.5g/m It was 2 .
かくして得られた平版印刷版材料上に感度測定
用ステツプタブレツト（イーストマン・コダツク
社製No.２）及びポジ原稿フイルムを密着して
2KWメタルハライドランプ（岩崎電気(株)社製ア
イドルフイン2000）を光源として1mの距離から
80秒間露光を行ない、４％メタケイ酸ナトリウム
水溶液で25℃にて45秒間現像し、平版印刷版を得
た。 A step tablet for sensitivity measurement (No. 2 manufactured by Eastman Kodak Co.) and a positive manuscript film were tightly attached onto the lithographic printing plate material thus obtained.
From a distance of 1m using a 2KW metal halide lamp (Idolfin 2000 manufactured by Iwasaki Electric Co., Ltd.) as a light source.
Exposure was carried out for 80 seconds, and development was carried out with a 4% aqueous sodium metasilicate solution at 25° C. for 45 seconds to obtain a lithographic printing plate.
支持体と画線部との接着性及び印刷版の耐刷性
を検討するために、耐処理薬品性試験及印刷試験
を行なつた。耐処理薬品性試験として、印刷中非
画像部に発生する地汚れを除去する洗浄液として
用いられるウルトラプレートクリーナー（A.B.
C.ケミカル(株)社製）に対する耐久性を調べた。 In order to examine the adhesion between the support and the image area and the printing durability of the printing plate, a processing chemical resistance test and a printing test were conducted. As part of the processing chemical resistance test, Ultra Plate Cleaner (AB
(manufactured by C. Chemical Co., Ltd.) was investigated.
上記グレースケールの階段上に濃度差を持つ画
像ができた印刷版をウルトラプレートクリーナー
原液に室温で20分間浸漬の後水洗し、浸漬前の画
像部と比較することにより、画像部の処理薬品に
対する侵食度を判定した。その結果、前記印刷板
は画像部の侵食がなく又網点についても面積率２
％の網点まで保存され良好な耐処理薬品性を示し
た。耐刷性試験は、実施例１と同様に行ない、そ
の結果、前記印刷板では25万枚まで良好な印刷物
が得られた。また保水性が良く印刷管理が容易で
あつた。 A printing plate with an image with density differences on the gray scale steps above was immersed in Ultra Plate Cleaner stock solution for 20 minutes at room temperature, then washed with water, and compared with the image area before immersion. The degree of erosion was determined. As a result, the printing plate has no erosion in the image area, and the area ratio of halftone dots is 2.
% halftone dots were preserved and showed good processing chemical resistance. The printing durability test was carried out in the same manner as in Example 1, and as a result, good prints were obtained up to 250,000 sheets using the printing plate. It also had good water retention and was easy to manage printing.
比較例 ３
別にコントロールとして下記の試料を作成し比
較した。即ち実施例３と同種の鉄板に比較例１と
同様にして電着クロム層を設けた支持体を製造
し、この鉄板支持体上に実施例３に記載された感
光性塗布液を同様に塗布、乾燥し、次に同様に露
光、現像し平版印刷版を得た。これについて実施
例３と同じ耐処理薬品性試験及耐刷性試験を行な
つた。その結果、画像部はウルトラプレートクリ
ーナーによつてほとんど損失し、網点もすべて面
積率５％のものまでも失なわれ著しく耐処理薬品
性が悪かつた。一方印刷では、６万枚印刷して画
像部の一部が剥離して印刷不可能となつた。Comparative Example 3 The following sample was separately prepared as a control and compared. That is, a support was prepared by providing an electrodeposited chromium layer on the same type of iron plate as in Example 3 in the same manner as in Comparative Example 1, and the photosensitive coating liquid described in Example 3 was similarly applied onto this iron plate support. , dried, and then exposed and developed in the same manner to obtain a lithographic printing plate. Regarding this, the same processing chemical resistance test and printing durability test as in Example 3 were conducted. As a result, most of the image area was lost by the ultra plate cleaner, and all halftone dots with an area ratio of 5% were also lost, resulting in extremely poor processing chemical resistance. On the other hand, after printing 60,000 sheets, part of the image area peeled off and printing became impossible.
第１図（写真）板状結晶状物が露出した形状を
有する支持体表面の走査式電子顕微鏡写真（3000
倍、傾斜角30度）、第２図（写真）第１図と同じ
試料の10000倍の走査式電子顕微鏡写真（傾斜角
30度）、第３図（写真）板状結晶状物が露出した
形状を有する支持体表面の走査式電子顕微鏡写真
（10000倍、正投影）、第４図（写真）第３図と同
じ試料の傾斜角30度の走査式電子顕微鏡写真
（10000倍）、第５図（写真）板状結晶状物が露出
した形状を有する支持体表面の走査式電子顕微鏡
写真（3000倍、傾斜角30度）、第６図（写真）及
び第７図（写真）立方体状結晶状物及びその凝集
体が露出した形状を有する支持体表面の走査式電
子顕微鏡写真（第６図10000倍、正投影、第７図
30000倍、傾斜角30度）、第８図オージエ
（Auger）局所分析（結晶状物露出部）結果を示
すグラフ、第９図オージエ（Auger）局所分析
（結晶状物非露出部）結果を示すグラフ、第１０
図オージエ（Auger）局所分析結果を示すグラ
フ。
Figure 1 (Photo) Scanning electron micrograph of the surface of a support with exposed plate-like crystals (3000
Fig. 2 (photo) Scanning electron micrograph of the same sample as in Fig. 1, magnified 10,000 times (tilt angle: 30 degrees);
30 degrees), Figure 3 (Photo) Scanning electron micrograph of the surface of a support with exposed plate-like crystals (10,000x, orthographic projection), Figure 4 (Photo) Same sample as Figure 3 Scanning electron micrograph (10000x) with a tilt angle of 30 degrees, Figure 5 (photo) Scanning electron micrograph (3000x, tilt angle 30 degrees) of the surface of a support with a shape in which plate-like crystals are exposed ), Fig. 6 (photo) and Fig. 7 (photo) Scanning electron micrographs of the surface of a support having a shape in which cubic crystals and their aggregates are exposed (Fig. 6 10000x, orthographic projection, Figure 7
30,000 times, tilt angle 30 degrees), Figure 8 is a graph showing the results of Auger local analysis (crystalline substance exposed area), Figure 9 is a graph showing the results of Auger local analysis (crystalline substance non-exposed area) graph, 10th
Figure Graph showing Auger local analysis results.
Claims (1)
する25℃を超える温度のめつき液中で鉄材上に電
着被覆をすることを特徴とする平版印刷版用支持
体の製造方法。 ２ 上記無水クロム酸の添加量が100〜500ｇ／
であり、上記バリウム化合物の添加量が１〜10
ｇ／であることを特徴とする特許請求の範囲第
１項に記載の平版印刷版用支持体の製造方法。 ３ 上記めつき液がフツ素化合物を含有すること
を特徴とする特許請求範囲第１項または第２項記
載の平版印刷版用支持体の製造方法。 ４ 上記フツ素化合物の添加量が20ｇ／以下で
あることを特徴とする特許請求の範囲第３項に記
載の平版印刷板用支持体の製造方法。 ５ 上記めつき液が酢酸を含有することを特徴と
する特許請求範囲第１項ないし第４項記載の平版
印刷版用支持体の製造方法。 ６ 上記酢酸の添加量が10ｇ／以下であること
を特徴とする特許請求の範囲第５項に記載の平版
印刷版用支持体の製造方法。[Claims] 1. A method for producing a support for a lithographic printing plate, which comprises electrodepositing a coating on an iron material in a plating solution containing chromic anhydride and a barium compound at a temperature of over 25°C. . 2 The amount of chromic anhydride added is 100 to 500g/
and the amount of the barium compound added is 1 to 10
The method for producing a support for a lithographic printing plate according to claim 1, wherein the support is 3. The method for producing a support for a lithographic printing plate according to claim 1 or 2, wherein the plating solution contains a fluorine compound. 4. The method for producing a support for a lithographic printing plate according to claim 3, wherein the amount of the fluorine compound added is 20 g/or less. 5. The method for producing a support for a lithographic printing plate according to claims 1 to 4, wherein the plating solution contains acetic acid. 6. The method for producing a support for a lithographic printing plate according to claim 5, wherein the amount of acetic acid added is 10 g/or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10572382A JPS58220796A (en) | 1982-06-18 | 1982-06-18 | Production of base for lithographic printing plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10572382A JPS58220796A (en) | 1982-06-18 | 1982-06-18 | Production of base for lithographic printing plate |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15286489A Division JPH02131992A (en) | 1989-06-14 | 1989-06-14 | Support for lithographic printing plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58220796A JPS58220796A (en) | 1983-12-22 |
| JPH0563318B2 true JPH0563318B2 (en) | 1993-09-10 |
Family
ID=14415237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10572382A Granted JPS58220796A (en) | 1982-06-18 | 1982-06-18 | Production of base for lithographic printing plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58220796A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012172572A2 (en) * | 2011-06-15 | 2012-12-20 | Titan Industries Ltd | Non-cyanide based electro chemical polishing |
-
1982
- 1982-06-18 JP JP10572382A patent/JPS58220796A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58220796A (en) | 1983-12-22 |
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