CN1010897B - Hydrophilic base material of offset plate, manufacture process and use - Google Patents
Hydrophilic base material of offset plate, manufacture process and useInfo
- Publication number
- CN1010897B CN1010897B CN86101022A CN86101022A CN1010897B CN 1010897 B CN1010897 B CN 1010897B CN 86101022 A CN86101022 A CN 86101022A CN 86101022 A CN86101022 A CN 86101022A CN 1010897 B CN1010897 B CN 1010897B
- Authority
- CN
- China
- Prior art keywords
- supporting body
- body material
- aluminium
- coating
- acrylamide
- 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
Links
- 239000000463 material Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims description 34
- 230000008569 process Effects 0.000 title description 14
- 238000004519 manufacturing process Methods 0.000 title description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 45
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000576 coating method Methods 0.000 claims abstract description 41
- 239000011248 coating agent Substances 0.000 claims abstract description 39
- 238000007645 offset printing Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- -1 phosphonic acid compound Chemical class 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001768 cations Chemical class 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 239000004411 aluminium Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 11
- 229910000838 Al alloy Inorganic materials 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- CRIRYPVZQBDACX-UHFFFAOYSA-N P(O)(O)(O)=O.CC(C)=C.C(C=C)(=O)N Chemical compound P(O)(O)(O)=O.CC(C)=C.C(C=C)(=O)N CRIRYPVZQBDACX-UHFFFAOYSA-N 0.000 claims description 5
- 239000007859 condensation product Substances 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000012267 brine Substances 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012954 diazonium Substances 0.000 claims description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 2
- 238000006317 isomerization reaction Methods 0.000 claims description 2
- 230000008707 rearrangement Effects 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims 1
- 150000002433 hydrophilic molecules Chemical class 0.000 claims 1
- 239000006166 lysate Substances 0.000 claims 1
- 238000005554 pickling Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 22
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000002585 base Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000007639 printing Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229920002401 polyacrylamide Polymers 0.000 description 6
- 230000000007 visual effect Effects 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000007767 bonding agent Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical class COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 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 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 229920003086 cellulose ether Polymers 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- 230000003313 weakening effect Effects 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 241001597008 Nomeidae Species 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-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
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 2
- 238000003287 bathing Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000002872 contrast media Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- XYZXOFUXTBSQQI-UHFFFAOYSA-N iron(3+);tricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-] XYZXOFUXTBSQQI-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- ACNUVXZPCIABEX-UHFFFAOYSA-N 3',6'-diaminospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(N)C=C1OC1=CC(N)=CC=C21 ACNUVXZPCIABEX-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241000920033 Eugenes Species 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
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- 235000015511 Liquidambar orientalis Nutrition 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004870 Styrax Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 150000001218 Thorium Chemical class 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000641 acridinyl group Chemical class C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 229940027998 antiseptic and disinfectant acridine derivative Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000003096 carboxylic acid amide acetal group Chemical group 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium 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
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- KKTHRZMKMWBNQQ-UHFFFAOYSA-N ethene;phosphoric acid Chemical compound C=C.OP(O)(O)=O KKTHRZMKMWBNQQ-UHFFFAOYSA-N 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000003979 granulating agent Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- DAONPBQTUWQEQJ-UHFFFAOYSA-N n-(oxomethylidene)prop-1-ene-1-sulfonamide Chemical compound CC=CS(=O)(=O)N=C=O DAONPBQTUWQEQJ-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QFVGCVZHAQQIMT-UHFFFAOYSA-L nickel(2+);prop-2-enoate Chemical compound [Ni+2].[O-]C(=O)C=C.[O-]C(=O)C=C QFVGCVZHAQQIMT-UHFFFAOYSA-L 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical class [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-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
- B41N3/038—Treatment with a chromium compound, a silicon compound, a phophorus compound or a compound of a metal of group IVB; Hydrophilic coatings obtained by hydrolysis of organometallic compounds
-
- 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
- B41N3/036—Chemical or electrical pretreatment characterised by the presence of a polymeric hydrophilic coating
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Printing Plates And Materials Therefor (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
A support material in the form of plates, sheets or webs for offset printing plates, composed of aluminum, which may have been pretreated, or its alloys, carrying on at least one side a hydrophilic coating of a phosphonic acid compound, wherein the hydrophilic coating comprises a polymer of acrylamidoisobutylenephosphonic acid or a copolymer of acrylamide and acrylamidoisobutylenephosphonic acid or a salt with an at least divalent metal cation.
Description
The present invention relates to the supporting body material of offset printing aluminium plate hydrophilic layer, its form has sheet material, light sheet or roll of material ， And to relate to these preparation methods and the use in offset printing forme is produced.
The offset printing forme supporting body material both can directly be provided by the user, can be provided by the producer that makes precoating galley again, and promptly one side or two faces in version all have photosensitive layer (examining the shellfish layer), can make printed image by this photosensitive Ceng And by the photomechanical production method.After printed image makes, just have the printed image part on the support, make lithographic image have hydrophilic background in no image area (non-area of image) simultaneously.
Preparation scribbles the lithographic plate of photochromics, and its support must satisfy following requirement:
1. photosensitive layer is after exposure, and bigger that part of of solubility when developing, must be easy to remove from support, and not leave a trace, so that obtain hydrophilic non-image area comparatively speaking.
2. the exposed support of non-image area must have very high affinity to water, just very high water wettability must be arranged, and just can adsorb moisture content soon, enduringly like this in the flat stamping process, and And has enough elimination abilities to oleaginous printing-ink.
3. all enough stickabilitys must be arranged with the photosensitive layer and the photosensitive layer of back that expose before the exposure with the printing position.
Sheet metal aluminium, steel, copper, brass or zinc also have plastic base or paper, all can be used as the version sill of this support.These starting material can be by suitable operation.For example, granulation does not have damp chromium spraying plate-making, surface oxidation and/or uses middle fixation layer, and it is become the support of offset printing forme.Now, the chances are uses the version sill of the widest offset printing forme for aluminium sheet.It is to pass through to do brush, wet brush, husky mill or chemistry and/or electrochemical treatment with the method for knowing, and alligatoring is carried out on the surface.In order to improve wearing quality, coarse substrate also can carry out anodization, to form the skim oxide film.
In fact, this supporting body material is particularly used anodised aluminium plate supporting body material, before being coated with photosensitive layer, usually also will further process, and improving the stickability of this one deck, strengthens water wettability and/or is convenient to the development of photosensitive layer.For example, following method has comprised these steps:
At DE-C907,147(=US-A2,714,066), DE-B1,471,707(=US-A3,181,461 and US-A3,280,734) or DE-A2,532,769(-US-A3,902,976) in, narrated the galley hydrophilization methods of making supporting body material with the aluminium plate of anodic oxidation processing.And these materials are to handle under the situation that passes to electric current or obstructed electric current with the aqueous solution of sodium silicate to make.
From DE-A1,134,093(=US-A3,276,868) and DE-Cl, 621,478(=US-A4,153,461) recognize in, use tygon phosphoric acid or ethene phosphoric acid, be based copolymers, as can be with the hydrophilic supporting body material of anodised printing aluminium plate as olefin(e) acid and vinyl acetate (or salt).Also mentioned the salt that uses these compounds, but be not described in more detail.
According to DE-B1,300,415(US-A3,440,050) use the fluorinated complex of titanium, zirconium or hafnium, cause the alumina layer hydrophiling on the galley support material to increase equally.
Except the hydrophilization methods that these are known, also once narrated available following polymers in this area, for example:
At DE-B1, narrated the water-soluble linear copolymers that in the photosensitive layer of galley, has used based on alkyl vinyl ether and maleic anhydride in 056,931.In these multipolymers, maleic anhydride component and ammonia, alkali metal hydroxide or alcohol or not reaction or reaction to some extent in those hydrophilic especially multipolymers.
DE-B1,091,433 discloses the hydrophilic supporting body material of operplate printing version, is the organic polymer with film forming, and for example, polymethylacrylic acid or sodium carboxymethyl cellulose or sodium hydroxyethlcellulose are applied on the aluminium sheet.Or be applied on the magnesium plate with the multipolymer of a kind of ethylene methacrylic ether and maleic anhydride.
According to DE-B1,173,917(=GB-A907,718) the hydrophilic supporting body material of operplate printing version be with a kind of be the synthetic resin of water miscible multifunctional amino/urea/aldehyde or the synthetic resin of sulfonation urea/aldehyde originally, it is applied on the sheet metal, is water-fast state after the curing.
According to DE-B1,200,847(=US-A3,232,783) hydrophilic coating on the supporting body material of preparation galley, a) on support, be coated with earlier the aqueous dispersion of the urea/formaldehyde resin of one deck modification, a kind of alkylating methylol melamine resin or melamine/formaldehyde/poly-inferior hydrocarbon polyamines resin, b then) aqueous dispersions of coating one deck polyhydroxy or multi-carboxy compound, for example, sodium carboxymethyl cellulose, c) base material that will coat is so at last handled with the aqueous solution of zirconium, hafnium, titanium or thorium salt.
At DE-B1,257,170(=US-A2,991,204) narrated in the multipolymer except that containing acrylic acid, acrylate, acrylamide or Methacrylamide, also included the trisubstituted vinyl silane of silicon unit, its hydrophilizing agent as the galley supporting body material.
From DE-A1,471,706(=US-A3,298,852) in recognize with the hydrophilizing agent of polyacrylic acid as aluminium, copper or zinc galley supporting body material.
According to DE-C2,107,901(=US-A3,733,200), the hydrophilic layer on the galley supporting body material, be that homopolymer or multipolymer by water-fast hydrophilic acrylic acid ester or methacrylate forms, its suction is at least 20%(by weight).
At DE-B2,305,231(=GB-A1,414,575) in, narrated the hydrophiling of galley supporting body material, be that dispersion liquid or a kind of solution with the potpourri of a kind of aldehyde and a kind of synthetic polyacrylamide is applied on the support.
DE-A2,308,196(=US-A3,861,917) disclosing the hydrophilic of alligatoring and anodised aluminium galley support, is to have used ethene or ethylene methacrylic ether/copolymer-maleic anhydride, polyacrylic acid, carboxymethyl cellulose, poly--(vinyl benzene-2,4 disulfonic acid) sodium or polyacrylamide.
At DE-B2,364,177(=US-A3,860,426) in, the hydrophilic adhesive coating of aluminium glue offset plate narrated.It is to anchor between anodised surface of galley support and the photosensitive layer.Except the plain ether of fibre-bearing, also contain water miscible zinc, calcium, magnesium, barium, strontium, cobalt or manganese salt in the layer.In hydrophilic adhesive coating, the weight of fiber ether layer is 0.2 to 1.1 milligram/decimeter
2, layer heavy phase together concerning water soluble salt.Use the cellulose ether of aqueous solution and the potpourri of salt, can suitably add a little organic solvents and/or surfactant, be applied on the support again.
According to US-A3,672,966, the aqueous solution of the multipolymer of use acrylic acid, polyacrylic acid, polymethylacrylic acid, poly or maleic acid and methylene or vinyl alcohol compresses the anodised aluminium surface behind the sealing of hole, to avoid the sealing of hole deposition.
According to US-A4,049,746, the hydrophilizing agent of galley supporting body material contains the salt shape reaction product of the water-soluble polypropylene acid resin and the poly-inferior hydrocarbon imines/urea/urea formaldehyde of carboxyl.
At GB-A1, in 246,696, narrated hydrophilic colloid, for example, hydroxyethyl cellulose, polyacrylamide, oxidic polyethylene, polyvinylpyrrolidone, starch or gum arabic can both be as the hydrophilizing agents of anodised printing aluminium plate support.
JP-A64/29982 has delivered with the tygon benzene sulfonic acid and has made the hydrophiling of operplate printing plate support.
With regard to the state of the art, those disclosed metal complexs include low-molecular-weight ligand as hydrophilic galley supporting body material, comprise following example:
1. according to DE-A2,807,396(=US-A4,208,212) complex ion of divalence or multivalent metal cation and ligand such as ammonia, water, ethylenediamine, nitrogen oxide, urea or ethylenediamine tetraacetic aldehydic acid ester.
2. according to US-A3,769,043 or/and US-A4, iron cyanide complex such as K in 420,549
4(Fe(CN)
6) or Na
3(Fe(CN
6)), heteropoly acid is wherein arranged, for example, phosphomolybdic acid or phosphomolybdate and phosphate exist.
3. according to NL-A6809,658(=US-A3,672,885) in the iron cyanide complex, the complex compound of phosphate and front is wherein arranged, for example ethylene dinitrilotetra-acetic acid exists, it can be used to have the electricity of the zinc oxide surface galley of taking pictures.
EP-A0,069,320(=US-A4,427,765) narrated a kind of method, the salt of tygon phosphoric acid, polyvinyl sulfonic acid, tygon methyl hypophosphorous acid wherein also has other polyvinyl, all can be used as post-treatment agent:
At US-A4, in 214,531, used the method for handling the offset plate of band image with polyacrylamide or polyacrylamide and polyacrylic potpourri.
At US-A647, in 142, the multipolymer of acrylamide and vinyl monomer is used for hydrophilic offset printing forme.
At DE-C2,615,075(=GB-A1,495,895) in, for same purpose, used polyacrylamide.
DE-C1,091,433 has narrated a kind of method of using the polymkeric substance aftertreatment offset printing forme support of methacrylic acid, methyl vinyl ether and maleic anhydride.
At DE-A2, also narrate in 540,561 with acrylamide and handle the galley support.
Because same purpose is particularly in order to improve the bin stability of galley.DE-A2,947,708 have narrated except acrylamide and acrylic acid nickel salt solution, also have the nickel salt solution of acrylamide and vinylpyrrolidone.
Yet all above-mentioned methods are having critical defect in varying degrees, and the supporting body material that makes it to produce in this way usually no longer can satisfy the requirement of current offset printing.
1. for example, after the alkali silicate processing, can cause good developing performance and water-wet behavior, but should admit, with its coating, the bin stability of photosensitive layer has certain reduction.
2. though transition metal complex can improve the water-wet behavior on anodised aluminium surface in principle, they have the shortcoming that very easily is dissolved in water, so, when photosensitive layer develops with aqueous developer, very easy being removed.Especially containing in the nearest developing system has the very surfactant and/or the chelating of high affinity to these metals
Form thing.Therefore, the concentration of transition metal complex significantly or less degree ground when descending can cause weakening of hydrophilic effects on this surface.
3. when handling support with water-soluble polymers, the latter has molten preferably Jie's degree, particularly uses the liquid alkali developing agent, for example, mainly is the development that is used for the positive type photosensitive layer, and this also can cause obviously weakening of hydrophilic effects.
3. when handling support with water-soluble polymers, the latter has molten preferably Jie's degree, particularly uses the liquid alkali developing agent, for example, mainly is the development that is used for the positive type photosensitive layer, and this also can cause obviously weakening of hydrophilic effects.
4. in containing the polymkeric substance of acidic-group, produced opposite effect, because the diazonium kation in acid group of free kation and the negativity type photosensitive layer interacts.Owing to after developing, preserved residual diazo-compounds, produced tangible colored photographic fog at non-visual position.
4. the result of the potpourri chemical combination of water-soluble polymers such as cellulose ether and water-soluble metal salt, because photosensitive layer increases the weight of, and selected bed thickness relatively uprises (DE-B2364177) thereby the cohesiveness that can cause coating itself to be showed reduces.For example, during developing, there is the visual position of developer liquids can lose cohesiveness.
Therefore, preparation has the supporting body material of the offset printing forme of fine hydrophilicity, purpose of the present invention that Here it is.These materials are fit to do the support of positive type, negativity type or electric photographic photosensitive layer equally, can not reduce bin stability, can not make between hydrophilizing agent and the photosensitive layer cohesiveness that reacts, also can not reduce coating.
The present invention is begun by supporting body material, as the form of offset printing forme sheet material, light sheet or roll of material is arranged, and it is a kind of through pretreated aluminium or a kind of aluminium alloy.And have at least one side to scribble the hydrophilic layer of phosphate cpd.
Distinguished characteristics are to include a) acrylamide isobutylene phosphoric acid polymerization thing or b in the hydrophilic layer) multipolymer of acrylamide and acrylamide isobutylene phosphoric acid, or c) have divalent metal at least a) or b) salt.
In copolymer salt, it is 1 to 3 that metal cation is aggregated the complexing position that the functional group of thing occupies, preferably 2.
In order to prepare c) reaction product, the form of the general metal cation that uses is the salt that has inorganic anion, or acetate; Here, be good with divalence, trivalent or quadrivalent cation, bivalent cation preferably.These kations are respectively V
5+, Bi
3+, AL
3+, Fe
3+, Zr
4+, Sn
4+, Ca
4+, Ba
2+, Sr
2+, Ti
3+, Co
2+, Fe
2+, Me
2+, Ni
2+, Cu
2+, Zn
2+Or Mg
2+Ion.
Can prepare these reaction product with simple mode, promptly in aqueous solution, temperature is 20 to 100 ℃.Preferably 25 to 40 ℃.Slaine is dissolved in the water, or if necessary, is dissolvable in water in rare mineral acid, then this solution slowly is added dropwise in the aqueous solution of polymkeric substance, then the component of reaction just begins to be transformed into above-mentioned product at once.After the reaction beginning, along with the self speed of having accelerated of reaction, because the variation that the effect of employed metal cation has produced solution colour immediately, or the generation of precipitation.
In order to purify, reaction product can make it to generate precipitation with the alkali metal hydroxide or the ammonia solution neutralization reaction solution of dilution, and unconverted initial product is then stayed in the solution.This reaction yield surpasses 90%.Also possible, different described polymeric acid forms, and with the cationic salt form of its monovalence, for example sodium or ammonia salt.
According to the present invention, the chemical constitution of polymer/metal complex compound can be represented with following formula:
Mainly be:
If central ion of M=is divalent metal, then A=B=H
2O, if during trivalent metal cation, A=H
2O
B=NO
- 3, Cl
-, HSO
- 2, H
2PO
- 4, CH
3COO
-, DH
-Or similar negative ion.
Particularly when polymer solution slowly is added drop-wise in the excessive slaine, just generated such complex compound.
The aluminium surface of offset printing forme supporting body material prepared in accordance with the present invention utilizes concentration to be 0.02 to 5%, preferably concentration is that 0.1 to 1% aqueous copolymers solution is handled.
The base version of prepared offset printing forme support material is handled with the salt of multipolymer according to the present invention, separates and the dry reaction product, and is preferably that it is molten in 0.1 to 10% mineral acid, especially 0.5 to 3% mineral acid.Wherein phosphoric acid is best, and concentration is 0.05 to 5%, is good with 0.1 to 1% especially.
Handling these base materials with these solution is very easily, as long as these base materials are immersed in the formic ether, or with the body lotion of drum base material by these solution.Bathing temperature is 20 to 95 ℃, and preferably 25 to 60 ℃, the residence time is 2 seconds to 10 minutes, and preferably 10 seconds to 3 minutes, these conditions proved suitable in practice.Bathing temperature increases, and then the chemisorption of the metal complex of multipolymer on the base material and polymkeric substance is quickened.This just makes the residence time obviously shorten, and particularly the water that immersion treatment helps subsequently under the situation of handling roll of material continuously washes.To carry out drying through the base material of such processing then, temperature is good with 110 to 130 ℃.
Handling the also available two step method of aluminium base with the salt of multipolymer carries out, in this case, for example, the first step immerses 0.01 to 10% with base material, preferably in the aqueous solution of 0.1 to 5% initial polymer, does not wash in advance and drying, base material is transferred in second body lotion subsequently, the brine solution that above-mentioned polyvalent metal ion is arranged in the bath of liquid, its concentration are 0.1% to saturated, preferably 0.5 to 10%.As single stage method, wash and drying.And two step method is handled, and then above-mentioned reaction product just forms on base material during handling.Utilize this distinct methods, in addition in dense acetic aid medium sl. sol. trivalent metal ion reaction product, can use this base material.
The weight measurement of used hydrophilic coating has become problem, because with quite a spot of product, and the effect ， And that can show and all fixing quite doughtily on the supporting body material surface He in the face just.Yet, can think, use 0.1 milligram/decimeter
2Following amount just effectively, especially is lower than 0.08 milligram/decimeter
2For best.
Like this, apply supporting body material prepared in accordance with the present invention with various photosensitive layers and can produce many offset printing versions.
Supporting body material prepared in accordance with the present invention, its suitable substrates are to comprise aluminium or a kind of aluminium alloy.For example, these base materials are:
" fine aluminium " (Deutsche industry norm (DIN) (DIN) material NO 3,0255) just consists of 〉=99.5% aluminium and following allow impurity (total amount is 0.5% to the maximum); 0.3% silicon, 0.4% iron, 0.03% titanium, 0.02% copper, 0.07% zinc and other impurity of 0.03%.
Or " aluminium alloy 3003 " is (with DIN material № 3,0515 is similar) promptly consist of 〉=98.5% aluminium, 0 to 0.3% magnesium and 0.8 to 1.5% manganese is as the composition of alloy, the impurity of allowing below also having is 0.5% silicon, 0.5% iron, 0.2% titanium, 0.2% zinc, 0.1 copper and other impurity of 00.15%.
Yet the method according to this invention also can change other aluminium alloy into.
In fact; the galley that usually can run into the aluminium support material is before the coating photosensitive layer; generally will be (for example with mechanical means; brushing and/or abrasion are handled), with chemical method (for example; etching) or come the surface of alligatoring aluminium with electrochemical method (for example, passing to alternating current in hydrochloric acid or aqueous solution of nitric acid handles).The present invention mainly is an electricity consumption chemical roughen aluminium galley.
Usually, the technological parameter in this step of alligatoring is generally within the following scope: dielectric temperature between 20 and 60 ℃, the concentration of agent (acid, salt) between 5 and 100 grams per liters, current density is at 15 and 130 amperes/decimeter
2Between, the residence time is between 10 and 100 seconds, and dielectric is between 5 and 100 cels at the lip-deep flow velocity of processed workpiece, used current type, most applications is to use alternating current, but also available different current type, for example, also can be with negative electrode that has various amplitude strength of current and anode exchange current.
Average height R between the peak-paddy of coarse surface
2, its scope is greatly about 1 to 15 micron, and the scope between 4 to 8 microns is better.
According to DIN4768(1970 version in October) the mensuration peak-to-valley height.Peak-to-valley height R
2It is the arithmetical mean of the single peak-to-valley height of continuous 5 measuring points.Single peak-to-valley height is the distance between the regulation two wires parallel with center line, and it correspondingly approaches highs and lows on the coarse vertical section of single measuring point.Single measuring point is to be used for directly estimating 1/5th of that part length on the coarse vertical section, and this part length is perpendicular to that part that center line protrudes.Center line is a general direction that is parallel to the coarse vertical section of drawing by geometric standard section, and it coarse vertical section separately makes the top total area that is full of material equal not have the bottom total area of material like this.
After finishing the galvanochemistry coarsening process, can further process anodizing of aluminium, for example, for the grinding and the cohesiveness on the surface of improving supporting body material, general dielectric such as H
2SO
4, H
3PO
4, H
2C
2O
4, amide group sulfonic acid, sulfo-succinic acid, the acid of sulfo-water, or their potpourri can be used for anodic oxidation.Below standard method as one with reference to example, when alumilite process, use H
2SO
4For water-soluble dielectric (relevant this respect, referring to example B, M Schenk " aluminium and its anodic oxidation " Francke Verlag-Berne 1948, the 760th page; The 395th page of " plating is put into practice " Eugen GLeuze Verlag-Saulgau 1970 and following and the 518/519th page; WHubner and CT SPeisen " alumilite process is put into practice " Verlag-Dusseldorf, 1977 the 3rd versions, the 137th page and following):
1. direct current sulfuric acid process, wherein anodic oxidation was carried out 10 to 60 minutes, used moisture dielectric, each rises usually 230 gram H in the solution
2SO
4, temperature is 0.5 to 2.5 ampere/decimeter at 10 to 22 ℃, current density
2, the concentration of sulfuric acid in electricity Jie aqueous solution also can reduce to 8 to the 10%(weight in sulfuric acid here) and (sulfuric acid that 100 grams are arranged during approximately each rises), also can be increased to 30%(by weight) (sulfur acid 365 grams in every liter) and higher.
2. this " strong anodization " carried out in vitriolated aqueous medium, and the concentration of sulfuric acid is every liter 166 gram (or sulfuric acid of about every liter 230 gram), and operating temperature is 0 to 5 ℃, and current density is 2 to 3 amperes/decimeter
2When handling beginning, voltage rises to about 25 to 30 volts, and processing is approximately more than 40 to 100 volts when finishing, and operates and lasts 30 to 200 minutes.
Except that this job operation of the anodic oxidation of above-mentioned galley supporting body material, can also be in the following method, for example, aluminium is containing H
2SO
4And AL
3+Carry out anodic oxidation, AL in the aqueous solution dielectric of ion component
3+The content of ion is adjusted to greater than the value of 12 gram/liters (according to DE-A2,811,396=US-A4,211,619) can contain H
2SO
4And H
3PO
4The water power medium in carry out (according to DE-A, 2,707,810=US-A4,049,504).Also H can contained
2SO
4, H
3PO
4And AL
3+Carry out in the water power medium of ion (according to DE-A2,836,803=US-A4,229,226).
Direct current is preferably used in anodic oxidation, but the combination of alternating current or these type electric currents also can be used (direct current that the alternating current stack for example, is arranged).The weight of alumina layer is at 1 to 10 gram/rice
2Scope within, its corresponding coating thickness is approximately 0.3 to 3 micron.
In principle, suitable photosensitive layer is, can be suitable for after the exposure subsequently development and/photographic fixing, obtain the surface of image, this just can be used for galley.They are applicable to common supporting body material.The manufacturer that both can be pre-coating light sensitive plate uses, and also can directly use for the user.
Except the coating that contains silver halide every field is used, the various coatings of other types know that also for example, Jaromir Kosar narrated in " photosensitive system ", by John Wiley; Sons, New york, nineteen sixty-five publishes: the colloid layer (Kosa the 2nd chapter) that contains chromate and dichromate; The coating that contains unsaturated compound, and these compounds in the coating, during exposure by isomerization, rearrangement, cyclisation or crosslinked (Kosar, the 4th chapter); Contain the coating ， And of can light poly-compound and monomer or the prepolymer in the coating, when exposure, can suitably add a kind of initiating agent, polymerization reaction take place (Kosar the 5th chapter); The coating that contains adjacent one diazonium-quinone, for example naphthoquinones-two triazo-compound, to the condensation product (Kesar the 7th chapter) of one diazonium-quinone or diazo salt.Suitable coating compounds also comprises electric photographic coating, that is to say to contain a kind of inorganic or organic optical conductor in the coating.Except this photoactive substance, in these coatings, also should contain more component, for example, resin, dyestuff or plastifier.
Especially, following photosensitive composition or compound can be used for applying the supporting body material by technology preparation of the present invention.
Positive type o-quinone-two triazo-compound, neighbour-naphthoquinones-two triazo-compound preferably, at DE-C854,890,865,109,879,203,894,959,938,233,1,109,521,1,144,705,1, describe to some extent in 118,606,1,120,273 and 1,124,817.
The condensation product of negativity type aromatic series diazo salt and the compound with pendant carboxylic group, the preferably condensation product of diphenyl amino diazo salt and formaldehyde.They are described in DE-C596, in 731,1,138,399,1,138,400,1,138,401,1,142,871 and 1,154,123, US-A2,679,498 and 3,050,502 and GB-A712,606.
The mixing condensation product of negativity type aromatic diazo compound (for example, according to DE-A 2,024,244).At least contain a kind of in the potpourri by general type A(-D) unit of n and B, divalence bridging knot with the carboxyl compound that derives from the energy condensation, the symbolic representation here is as follows: A is a kind of group of compound, this compound contain at least two aromatic carbon rings and/or heteronucleus ， And in acid medium can with active carbonyl compound condensation on 1 position at least.D is the diazo salt group that is connected on the aromatic series carbon atom of A; N is from 1 to 10 integer, and B is a kind of group of compound, and this compound does not contain diazonium groups, but can be in acid medium and active carbonyl compound condensation on a position of molecule at least.
According to DE-A2,610,842 positive type, coating (for example includes a kind of compound of eliminating acid when irradiation, a kind of compound that has the C-O-C group that an energy eliminated by acid at least, o-carboxylic acid ester group or carboxylic acid amide-acetal group), if suitable, also can contain a kind of bonding agent.
Phtotpolymerizable and the suitable monomer that more closes, light trigger, bonding agent, adjuvant are arranged in the negativity type coating.Here used monomer, for example, acrylate and methacrylate, the perhaps reaction product of the part ester of diisocyanate and polyhydroxy-alcohol.For example, be described in US-A2, in 760,863 and 3,060,023 and DE-A2,064,079 and 2,361,041.The light trigger that is fit to especially styrax, benzoin ether, encircle quinone, acridine derivatives, azophenlyene derivant, quinoxaline derivatices, quinazoline derivant, or the Synergistic blend of multiple ketone more.A large amount of different solubility organic polymers all can be used as bonding agent.For example, polyamide, polyester, alkyd resin, polyvinyl alcohol (PVA), polyvinylpyrrolidone, oxidic polyethylene, gelatin or cellulose ether.
In (according to DE-A3,036,077) negativity type coating, as the polycondensation product that diazo salt is arranged of light-sensitive compound, perhaps organic azide.And alkylene sulfonyl-or the high molecular polymer of cycloalkenyl group sulfonyl-urethanes side group arranged as bonding agent.
Photoelectricity-coated semiconductor for example, is described in DE-C1, in 117,391,1,522,497,1,572,312,2,322,046 and 2,322,047, also goes for supporting body material, can produce high electrification photographic coating thus.
According to the present invention, from the offset printing forme that supporting body material obtains applying, with the mode of knowing, by imaging exposure or irradiation, And washes out non-visual position with developer, preferably uses the aqueous solution developer, and it is become desired galley.Beyond thoughtly be, the basic plate material of the offset printing forme of handling according to the present invention, with polyvinyl phosphoric acid or only handle with hot water, the forme of Chu Liing is had any different with those versions of handling with the acrylamide of homopolymerization as a comparison like this, and the former has obviously low Se Ban And and has changed water-wet behavior.To get well than comparative sample aspect the cohesiveness on photosensitive layer and support surface by many samples that the present invention handles.
The preparation of embodiment A-alligatoring and anodic oxidation galley support
Embodiment A 1
0.3 the press polish aluminium strip of millimeters thick (DIN material № 30255) with the Acidwash solution of 2% buck, cleans greasy under about 50 to 70 ℃ high temperature.Carry out on aluminium surface effectively galvanochemistry alligatoring indirect current in containing the nitric acid dielectric; Gained surface coarsening degree R
2Value is 6 microns.According to DE-A2,811,396 methods of being narrated are carried out anodic oxidation in vitriolated dielectric subsequently, and oxide weight approximately is 3.0 gram/rice
2
The support that makes in this way is designated by numeral 1 in table 2 and table 3.
The aluminium strip that makes in this way contains a kind of polymkeric substance or a kind of contrast material (NI is to NV13) by the warm bath (60 ℃) that 0.5% solution is arranged according to this solution of the present invention.The constituent of these solution is listed in table 1.The time that stops in bath is 30 seconds.At rinse stage, excessive solution rinses out with tap water.Aluminium strip is dry in the hot-air between 100 and 130 ℃ in temperature.
Embodiment A 2
0.3 the press polish aluminium strip of millimeters thick (DIN material № 30515), with the Acidwash solution of 2% buck, be approximately clean under 50 to 70 ℃ the high temperature greasy.Aluminium surface effectively galvanochemistry alligatoring is that indirect current carries out in hydrochloric dielectric, gained surface coarsening degree R
2Value is 6 microns, and subsequently according to DE-A2,811,396 described methods are carried out anodic oxidation in the dielectric of sulfuric acid is arranged, and oxide weight approximately is 3.0 gram/rice
2
The support that makes in this way is designated by numeral 2 in table 2 and table 3.
The aluminium strip that makes like this is by the warm bath (50 ℃) that 0.5% solution is arranged, according to containing a kind of polymkeric substance or a kind of contrast material (NI is to NV13) in this solution of the present invention.The constituent of these solution is listed in table 1.
Embodiment A 3
0.2 the press polish aluminium strip of millimeters thick (DIN material № 30255) with the Acidwash solution of 2% buck, cleans greasyly being approximately under 50 to 70 ℃ the high temperature, use grinding granulating agent polish-brush support then.The surfaceness R that obtains like this
2Value is 4 microns, subsequently according to DE-C1, and 671,614(=US-A3,511,661) in the phosphoric acid dielectric, carry out anodic oxidation, oxide weight is 0.9 gram/rice
2
The aluminium strip of Chu Liing is cut into the thin plate of 50 * 45 centimetres of sizes like this.
The support that makes in this way is designated by numeral 3 in table 2 and 3.
The support that makes like this is immersed in the warm bath (60 ℃) of 0.4% aqueous solution, contains in the aqueous solution and lists in a kind of polymkeric substance of NI to NV13 in the table 1.The time that stops in bath is 60 seconds.Excess solution is washed off with deionized water in rinse stage subsequently, and support is at air drying.
The preparation of Embodiment B-reaction product (polymer/metal complex compound):
Get 0.2 mole in this polymkeric substance (with respect to the phosphoric acid of a unit quantity) of listing in N3 in the table 1, be dissolved in 600 milliliters the water and form solution, again with 0.2 mole Co(NO
3)
2Be dissolved in 200 ml waters, be added dropwise at leisure then in this solution; Behind reinforced the end, potpourri was stirred more than 1 hour, slowly adds the neutralization of diluted alkaline NaoH solution in the reactant liquor, have simultaneously thickness, elastomeric, purplish cobalt complex precipitation separates out.Filter out precipitation, first water is washed with methyl alcohol then.And is dry in 60 ℃ drying box.Excessive Co
2+Ion is then stayed in the filtrate.Polymkeric substance also can use the same method with other ions and react, but is divalent metal at least.
Table 1
1 2 3
Numbering constituent monomer ratio
N1 p-AMIP＊/AM＊＊ 1∶99
N2 ″ 3∶97
N3 ″ 10∶90
N4 ″ 50∶50
N5 ″ 70∶30
N6 p-AMIP＊ 100∶0
N7 p-AMIP/AM-Ca＊＊＊ 3∶97
N8 p-AMIP/AM-Sr＊＊＊ 10∶90
N9 p-AMIP/AM-Co＊＊＊ 10∶90
N10 p-AMIP/AM-Mg＊＊＊ 1∶99
NV11 water
NV12 p-VPS
NV13 AM
The implication of abbreviation is:
* acrylamide isobutylene phosphoric acid
The * acrylamide
* * is according to the slaine (Ca, Sr, Mg or Co) of the co-polymeric acids of Embodiment B preparation
The P multipolymer
At many supporting body materials that A1 narrates in the A3, all use 13 kinds of broad processing of difference for every kind, obtain ading up to 39 kinds of supports after the processing, they with measurement result list in table 2 Zhong ， And be situated between release as follows:
Except A1 to the immersion treatment that A3 narrated, some support will carry out galvanochemistry aftertreatment ， And and be described below:
Embodiment C-electrochemical treatment
Support in the embodiment A 2 is immersed in 40 ℃ 0.2% the solution, this solution is by (table 1) of NI to the preparation of product of NV12, connects support and makes anode, with the Direct current treatment of 10V 20 seconds.In processing procedure, electric current is from original 3 amperes/decimeter
2Reduce to 0.2 ampere/decimeter
2Then, excess solution is washed off with deionized water at wash phase.Support is at air drying.Support that obtains like this and measurement result are listed in table 3 ， And and are narrated below.
To according to resulting each supporting body material of embodiment, all measure one by one.
The surface alkali resistance test (according to US-A3,940,321 the 3rd and the 4th sections, the 29th to 68 row and the 1st to 8 row):
The alkaline-resisting degree of alumina layer is to measure this layer molten Jie speed in the zincate aqueous slkali in the several seconds, and this one deck is more alkaline-resisting, then molten its required time of Jie is longer, this layer thickness should be roughly similar, because actually, they also represent a parameter of molten Jie's speed.With the potassium hydroxide of 500 ml distilled waters, 480 grams and the zinc paste wiring solution-forming of 80 grams, get this drips of solution on the surface of determinand, And measures the time of occurrence of metallic zinc, and itself is shown by research position blackout.This " zincate test ", narration to some extent in the stringer 4 of table 2.
Water-wet behavior test according to the supporting body material of the present invention preparation
This test is to measure the contact angle that drops in the water droplet on the support.In this test, the mensuration support is surperficial and by the angle between the tangent line of drop contact, in general, angle is between 0 ° and 90 °, and is better wetting, and then angle is littler, about the data of these contact angle determination, lists in file 5 at table 2.
Embodiment D-applies support with photochromics
Embodiment D1
Each support of narrating in embodiment A 1 to A3 is respectively got one, applies with following solution:
6.6 part (by weight) metacresol/formaldehyde novolac (softening point range of measuring according to DIN53181 is 105 °-120 ℃).
1.1 part (by weight) 4-(2-phenyl-propenyl)-phenylnaphthalene-1.2 quinones-2-two nitrine-4-sulfonate.
0.6 part (by weight) 2.2-pair-(naphthalene-1.2-quinone-2-two nitrine-5-sulfonylamino acid)-1.1 '-dinaphthyl methane.
0.24 part (by weight) naphthalene-1.2-quinone-two nitrine-4-sulfonylamino acid chlorine.
0.08 part (by weight) crystal violet and
91.36 part (by weight) mixed solvent, 4 parts of (by volume) ethylene glycol-methyl ethers wherein, 5 parts of (by volume) tetrahydrofurans and 1 part of (by volume) butyl acetate.
The support of coating is dried in the dry flue up to 120 ℃, and the galley that makes is like this used the developer development of the former figure printing down ， And of positivity with following constituent:
5.3 part (by weight) sodium silicate * 9H
2O
3.4 part (by weight) tertiary sodium phosphate * 12H
2O
0.3 part (by weight) sodium dihydrogen phosphate (anhydrous) and
91.0 part (by weight) water.
The many galleys that obtain are evaluated with visual, the dyestuff residue that non-image area still exists (blue spot), and this results are shown in the file 6 of table 2.
Embodiment D2
Each support of narrating in embodiment A 1 to A3 is respectively got one, scribbles following negativity type photosensitive layer:
16.75 the polyvinyl butyral of part (by weight) %, its molecular weight is 70000 to 80000, consist of 71%(by weight) ethene butyral, 2% vinyl acetate and 27%(by weight) vinyl alcohol, with the reaction product solution of propenyl sulfonyl isocyanate.
2.14 2 of part (by weight), 6-pair-(4-azido-benzal)-4-methyl ring ethyl ketone.
0.23 (R) Rhodamin 6GDN of part (by weight) adds
0.21 the 2-benzoyl methylene-1-methyl-β-aphthothiazoles of part (by weight) is dissolved in during the tetrahydrochysene of the ethylene glycol-methyl ether of 100 parts (by volumes) and 50 parts (by volumes) mutters.
The dry following narration of this support.
Dry coating weighs 0.75 gram/rice
2The surreptitious edition coating was exposed 35 seconds under egative film with the metal halide lamp of 5 kw of power.Being exposed layer developer solution degree of depth corrosion liquid layer with following constituent develops:
5 parts of (by weight) NaLSs
1 part of (by weight) sodium silicate * 5H
2O and
94 parts of (by volume) water
Whether the non-visual position of gained galley comes still to have on the inspection layer residue to exist with visual.Compare with (NV12) existing technological level (NV12), evaluation result is shown in the file 7 of table 2.
The meaning of symbol is in the table 2:
One, poor than the process condition of comparative example's solution NV12
Zero, the process condition with comparative example's solution NV12 is the same good
Ten, to get well than the process condition of comparative example's solution NV12
Embodiment D3:
In order to prepare the electric offset plate of composing and laying out of taking a picture, be coated with following solution on the anodic oxidation support by 15 preparations of embodiment in the table 2:
10 parts (by weight) 2.5-pair-(4 '-the diethylamino phenyl)-1,3, the 4-oxadiazoles,
The multipolymer of 10 parts of (by weight) styrene and maleic anhydride, its softening point is 210 ℃,
0.02 part (by weight) be rhodamine FB(C.I.45170 (R)) and
300 parts of (by weight) ethylene glycol monomethyl ethers.
The drying of these supports is described in below 3.
Make coating in the dark with going up about 400 volts negative charge with corona.Charged version exposes to image in process camera, then the suspension developing liquid developing of electricity consumption photograph; Suspending liquid is to be suspended in 7.5 parts of (by weight) pentaerythrite esterification resins and 1200 parts of (by volume) boiling spreads in 185 to 210 ℃ isoparaffins mixture by 3.0 parts of (by weight) magnesium sulphate.After excessive developer solution was removed, photographic fixing then was soaked in 60 seconds in the following solution to galley.
35 parts of (by weight) sodium silicate * 9H
2O
140 parts of (by volume) glycerine
550 parts of (by volume) ethylene glycol and
140 parts of (by volume) ethanol
With strong current galley is washed then, those places that do not covered by toner on the photoconductive layer are washed out, this galley just can be prepared printing, the non-image area of this galley, present extremely good water wettability, both made effect, also do not show the sign of corrosion through aqueous slkali.Use this galley, can obtain number with the measured printed matter of multifarious matter.
Table 2 has proved according to product of the present invention, will get well under the existing process condition of many performances, and also all these product neither ones are relatively poor.
Table 3
1) * positive type coating 2) * negativity type coating
Compared with the table 2 that is obtained by galvanochemistry aftertreatment support, table 3 has provided goodish numerical value, particularly the further improvement of zincate trial value.
Except all supports of above-mentioned usefulness had carried out test, according to 1 to the 3 prepared support of embodiment in the table 2, the positive type photosensitive layer coating with being described in D1 by exposure and development, had made galley.Print test with these galleys, then obtain more than 210,000 parts, the measured printed matter of matter.And by to this ratio NV12(table 2) the similar galley that makes of support, provided and rolled performance on relatively poor, after 170,000 parts of printed matters, reproduce not correctly very thin shadow tone site.
Claims (14)
1, the supporting body material of offset printing version has sheet material, light sheet or roll of material, by forming by pretreated aluminum or aluminum alloy, it is characterized in that simultaneously having at it at least the hydrophilic coating of phosphate cpd, and its hydrophilic coating comprises:
A) acrylamide isobutylene phosphoric acid polymerization thing or
B) multipolymer of acrylamide and acrylamide isobutylene phosphoric acid or
C) a) or b) have a kind of salt of divalent metal at least.
2, the supporting body material of narrating according to claim 1, acrylamide/acrylamide isobutylene phosphonic acids monomer wherein is at b) or c) ratio in the multipolymer be 0≤by 99: 1.
3, the supporting body material of narrating according to claim 1, wherein the ratio of monomer is 97: 3 to 90: 10
4, according in the claim 1 to 3 narration any supporting body material, its floating coat c) in metal cation be V
5+, Bi
3+, Al
3+, Fe
3+, Zr
4+, Sn
4+, Ca
2+, Ba
2+, Sr
2+, Ti
3+, Co
2+, Fe
2+, Mn
2+, Ni
2+, Cu
2+, Zn
2+Or Mg
2+Ion.
5, according to any supporting body material of narration in the claim 1 to 4, its floating coat include product a) and/or b) and/or potpourri c).
6, according to any supporting body material of narration in the claim 1 to 5, wherein aluminium is by pickling.
7, according to any supporting body material of narration in the claim 1 to 6, wherein aluminium is by alligatoring.
8, according to any supporting body material of narration in the claim 1 to 7, wherein aluminium is by anodic oxidation.
9, according to any supporting body material of narrating in the claim 6 to 8, wherein the peak-to-valley height R of aluminium
2It is 3 to 10 microns.
10, according to Claim 8 or 9 supporting body materials of being narrated, wherein the oxidated layer thickness of aluminium is 0.3 to 3.0 micron.
11,, use a) to c according to the preparation method of any offset printing forme supporting body material of narration in the claim 1 to 10) lysate or their potpourri apply aluminum or aluminum alloy; Concentration be 0.02 to 5.0%(by weight) aqueous solution.Supporting body material can acidifying, with soak or electrochemical treatment ， And with the coating drying.
12, according to the preparation method of any supporting body material of narrating in the claim 1 to 10, it has comprised coating c) the preparation method.The disposal route of aluminum or aluminum alloy be earlier with 0.01 to 10.0% a) and/or b) polymer solution, arrive saturatedly then with 0.1%, cationic brine solution V is preferably arranged
5+, Bi
3+, Al
3+, Fe
3+, Zr
4+, Sn
4+, Ca
2+, Ba
2+, Sr
2+, Ti
2+, Co
2+, Fe
2+, Mn
2+, Ni
2+, Cu
2+, Zn
2+, or Mg
2+Ion is handled, and the dry coating that makes from reaction product.
13, the method for preparing claim 11 or 12 described supporting body materials is comprising before with the hydrophilic compounds coating aluminum or aluminum alloy being carried out acidleach and/or anodic oxidation.
14, any purposes that scribbles the supporting body material of photosensitive layer described in the claim 1 to 13, after exposure, develop and/or photographic fixing, obtain the image surface, wherein photosensitive layer contains silver halide, chromate and dichromate, the unsaturated compound of isomerization, rearrangement, cyclisation or cross-linking reaction takes place through exposure, can be repeated quinone, right-the diazonium quinone, diazo salt condensation product or inorganic and organic photoconductor by the compound of photopolymerization, adjacent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3504331.8 | 1985-02-08 | ||
| DE19853504331 DE3504331A1 (en) | 1985-02-08 | 1985-02-08 | HYDROPHILIZED CARRIER MATERIALS FOR OFFSET PRINTING PLATES, A METHOD FOR THEIR PRODUCTION AND THEIR USE |
| DEP3504331.8 | 1985-02-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86101022A CN86101022A (en) | 1986-08-06 |
| CN1010897B true CN1010897B (en) | 1990-12-19 |
Family
ID=6262020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86101022A Expired CN1010897B (en) | 1985-02-08 | 1986-02-03 | Hydrophilic base material of offset plate, manufacture process and use |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0190643B1 (en) |
| JP (1) | JPS61182988A (en) |
| CN (1) | CN1010897B (en) |
| AU (1) | AU5328086A (en) |
| BR (1) | BR8600541A (en) |
| CA (1) | CA1299007C (en) |
| DE (2) | DE3504331A1 (en) |
| ES (1) | ES8705981A1 (en) |
| ZA (1) | ZA86876B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0790669B2 (en) * | 1986-03-19 | 1995-10-04 | 大日本インキ化学工業株式会社 | Method for producing support for lithographic printing plate |
| DE4039920A1 (en) * | 1990-12-14 | 1992-06-17 | Basf Ag | NEW POLYETHYLENIMINE AND POLYVINYLAMINE DERIVATIVES, CARRIER MATERIALS COATED WITH THESE DERIVATIVES ON THE BASIS OF ALUMINUM AND THE USE THEREOF FOR THE PRODUCTION OF OFFSET PRINTING PLATES |
| US5368974A (en) * | 1993-05-25 | 1994-11-29 | Eastman Kodak Company | Lithographic printing plates having a hydrophilic barrier layer comprised of a copolymer of vinylphosphonic acid and acrylamide overlying an aluminum support |
| EP0689096B1 (en) | 1994-06-16 | 1999-09-22 | Kodak Polychrome Graphics LLC | Lithographic printing plates utilizing an oleophilic imaging layer |
| DE4423140A1 (en) | 1994-07-01 | 1996-01-04 | Hoechst Ag | Hydrophilized carrier material and recording material produced therewith |
| DE19543934A1 (en) | 1995-11-25 | 1997-05-28 | Hoechst Ag | Carrier material made of aluminum or its alloys, with a hydrophilizing layer, and method for producing the carrier material |
| WO1997020698A1 (en) * | 1995-12-01 | 1997-06-12 | Toyo Boseki Kabushiki Kaisha | Laminated substrate, and original plate using the substrate for photosensitive and direct drawing lithographic printing |
| GB9726994D0 (en) * | 1997-12-23 | 1998-02-18 | Ici Plc | Polymeric film |
| TR200101883T2 (en) * | 1998-10-15 | 2002-05-21 | Henkel Corporation | Hydrophilizing agent for metallic material, hydrophilization liquid, hydrophilization method, metallic material and heat exchanger |
| KR101344792B1 (en) * | 2010-12-17 | 2013-12-24 | 제일모직주식회사 | Hardmask composition and method of forming patterns and semiconductor integrated circuit device including the patterns |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3126626A1 (en) * | 1981-07-06 | 1983-01-20 | Hoechst Ag, 6000 Frankfurt | HYDROPHILIZED CARRIER MATERIALS FOR OFFSET PRINTING PLATES, A METHOD FOR THEIR PRODUCTION AND THEIR USE |
| DE3126636A1 (en) * | 1981-07-06 | 1983-01-27 | Hoechst Ag, 6000 Frankfurt | HYDROPHILIZED CARRIER MATERIALS FOR OFFSET PRINTING PLATES, A METHOD FOR THEIR PRODUCTION AND THEIR USE |
-
1985
- 1985-02-08 DE DE19853504331 patent/DE3504331A1/en not_active Withdrawn
-
1986
- 1986-01-28 EP EP86101090A patent/EP0190643B1/en not_active Expired - Lifetime
- 1986-01-28 DE DE8686101090T patent/DE3670804D1/en not_active Expired - Fee Related
- 1986-02-03 CN CN86101022A patent/CN1010897B/en not_active Expired
- 1986-02-05 CA CA000501187A patent/CA1299007C/en not_active Expired - Fee Related
- 1986-02-06 ES ES551694A patent/ES8705981A1/en not_active Expired
- 1986-02-06 ZA ZA86876A patent/ZA86876B/en unknown
- 1986-02-06 AU AU53280/86A patent/AU5328086A/en not_active Abandoned
- 1986-02-07 BR BR8600541A patent/BR8600541A/en unknown
- 1986-02-07 JP JP61024266A patent/JPS61182988A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61182988A (en) | 1986-08-15 |
| EP0190643A3 (en) | 1987-10-21 |
| ES8705981A1 (en) | 1987-05-16 |
| DE3504331A1 (en) | 1986-08-14 |
| ZA86876B (en) | 1986-09-24 |
| DE3670804D1 (en) | 1990-06-07 |
| BR8600541A (en) | 1986-10-21 |
| ES551694A0 (en) | 1987-05-16 |
| EP0190643B1 (en) | 1990-05-02 |
| AU5328086A (en) | 1986-08-14 |
| CA1299007C (en) | 1992-04-21 |
| CN86101022A (en) | 1986-08-06 |
| EP0190643A2 (en) | 1986-08-13 |
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