EP0105170A2 - Procédé de posttraitement de couches d'oxyde d'aluminium avec des solutions aqueuses contenant du silicate alcalin et son application dans la fabrication des supports pour plaques d'impression - Google Patents
Procédé de posttraitement de couches d'oxyde d'aluminium avec des solutions aqueuses contenant du silicate alcalin et son application dans la fabrication des supports pour plaques d'impression Download PDFInfo
- Publication number
- EP0105170A2 EP0105170A2 EP83108259A EP83108259A EP0105170A2 EP 0105170 A2 EP0105170 A2 EP 0105170A2 EP 83108259 A EP83108259 A EP 83108259A EP 83108259 A EP83108259 A EP 83108259A EP 0105170 A2 EP0105170 A2 EP 0105170A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- treatment
- aqueous
- alkali silicate
- aluminum
- der
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000011282 treatment Methods 0.000 title claims abstract description 37
- 229910052910 alkali metal silicate Inorganic materials 0.000 title claims abstract description 19
- 238000007645 offset printing Methods 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 title claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 44
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 25
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000956 alloy Substances 0.000 claims abstract description 4
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 32
- -1 alkaline earth metal salts Chemical class 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 159000000008 strontium salts Chemical class 0.000 claims description 2
- 238000007654 immersion Methods 0.000 abstract description 6
- 239000011888 foil Substances 0.000 abstract description 3
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 53
- 238000007639 printing Methods 0.000 description 34
- 239000004793 Polystyrene Substances 0.000 description 29
- 239000012876 carrier material Substances 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 14
- 239000003513 alkali Substances 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000012954 diazonium Substances 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007788 roughening Methods 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000001680 brushing effect Effects 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- 239000011975 tartaric acid Substances 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
- LXFQSRIDYRFTJW-UHFFFAOYSA-N 2,4,6-trimethylbenzenesulfonic acid Chemical compound CC1=CC(C)=C(S(O)(=O)=O)C(C)=C1 LXFQSRIDYRFTJW-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 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
- 239000000654 additive Substances 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- LRMHFDNWKCSEQU-UHFFFAOYSA-N ethoxyethane;phenol Chemical compound CCOCC.OC1=CC=CC=C1 LRMHFDNWKCSEQU-UHFFFAOYSA-N 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 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 2
- RIBSIXLJGIEVSH-UHFFFAOYSA-N n-phenyl-n-phenyldiazenylaniline Chemical compound C1=CC=CC=C1N=NN(C=1C=CC=CC=1)C1=CC=CC=C1 RIBSIXLJGIEVSH-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- ZRYCRPNCXLQHPN-UHFFFAOYSA-N 3-hydroxy-2-methylbenzaldehyde Chemical compound CC1=C(O)C=CC=C1C=O ZRYCRPNCXLQHPN-UHFFFAOYSA-N 0.000 description 1
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 241001295925 Gegenes Species 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N N-phenyl aniline Natural products C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005137 alkenylsulfonyl group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003096 carboxylic acid amide acetal group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QVEIBLDXZNGPHR-UHFFFAOYSA-N naphthalene-1,4-dione;diazide Chemical class [N-]=[N+]=[N-].[N-]=[N+]=[N-].C1=CC=C2C(=O)C=CC(=O)C2=C1 QVEIBLDXZNGPHR-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium 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
- 238000005406 washing Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S205/00—Electrolysis: processes, compositions used therein, and methods of preparing the compositions
- Y10S205/921—Electrolytic coating of printing member, other than selected area coating
Definitions
- the invention relates to an aftertreatment process for roughened and anodically oxidized aluminum, in particular of support materials for offset printing plates with aqueous solutions containing alkali silicate.
- Carrier materials for offset printing plates are provided either by the consumer directly or by the manufacturer of precoated printing plates on one or both sides with a radiation-sensitive layer (reproduction layer), with the help of which a printing image of a template is generated in a photomechanical way. After production of these printing form from the printing plate of the substrate bearing the ink-carrying in the subsequent printing image areas and forms in the image-free during subsequent printing points (non-image areas) the hydrophilic image background for the lithographic D ruckvor- gear.
- a radiation-sensitive layer production layer
- Aluminum, steel, copper, brass or zinc, but also plastic films or paper can be used as the base material for such layers. These raw materials are modified by suitable modifications such.
- Aluminum, which is probably the most frequently used base material for offset printing plates today, is roughened on the surface by known methods by dry brushing, wet brushing, sandblasting, chemical and / or electrochemical treatment. In order to increase the abrasion resistance, the roughened substrate can also be subjected to an anodizing step to build up a thin oxide layer.
- a cellulose ether such as sodium carboxymethyl cellulose or hydroxyethyl cellulose
- a water-soluble Zn, Ca Contains Mg, Ba, Sr, Co or Mn salt.
- Such adhesive layers are intended to give the plate a longer service life and to prevent the non-image areas of a printing form produced therefrom from "toning" during printing, but this layer does not achieve any appreciable increase in alkali resistance.
- the object of the present invention is to propose a method for the aftertreatment of flat aluminum, which can be carried out in addition to anodic oxidation of the aluminum and leads to a surface on the aluminum oxide produced in this way, which in particular meets the practical requirements of a high-performance printing plate described at the outset.
- the invention is based on the known process for the production of plate, sheet or strip-shaped materials based on chemically, mechanically and / or electrochemically roughened and anodically oxidized aluminum or one of its alloys, the aluminum oxide layers of which are post-treated with an aqueous alkali silicate solution.
- the process according to the invention is then characterized in that after carrying out treatment a) with an aqueous alkali silicate solution, a treatment b) is additionally carried out with a solution containing aqueous alkaline earth metal salts.
- water-soluble calcium or strontium salts in particular nitrates, are used as the alkaline earth metal salts.
- the solution contains in particular 0.1 to 10% by weight of the alkaline earth metal salts, preferably 0.5 to 3% by weight.
- stage a) can also be carried out electrochemically, the latter procedure often already having a certain increase in alkali resistance of the material not yet treated with b).
- the electrochemical process variant is carried out in particular with direct or alternating current, trapezoidal, rectangular or triangular current or overlapping forms of these types of current; the current density is generally 0.1 to 10 A / dm 2 and / or the voltage is 1 to 100 V , the rest of the parameters depend on z. B. from the electrode spacing or the electrolyte composition.
- the treatment of the materials can be carried out discontinuously or continuously in the modern belt systems, the treatment times - for the respective treatment stage - expediently in the range from 0.5 to 120 seconds and the treatment temperatures at 15 to 80 ° C, in particular 20 to 75 ° C.
- the aqueous alkali silicate solution in stage a) generally contains 0.5 to 15% by weight, in particular 0.8 to 12% by weight, of an alkali silicate (such as Na metasilicate or the Na contained in the "water glass”) tri and tetrasilicates). It is assumed that a firmly adhering cover layer forms in the pores of the aluminum oxide layer, which protects the oxide from attacks.
- the procedure used changes the previously generated surface topography (such as roughness and oxide pores) practically not or only insignificantly, so that the method according to the invention is particularly suitable for the treatment of materials in which the retention of this topography plays a major role, for example for printing plate support materials.
- suitable base materials for use in the process according to the invention include those made of aluminum or one of its alloys, which have, for example, a content of more than 98.5% by weight of Al and proportions of Si, Fe, Ti, Cu and Zn.
- the aluminum support materials for printing plates found in practice are mechanically (e.g. by brushing and / or with abrasive treatments), chemically (e.g. by etching agents) or electrochemically (e.g. by alternating current treatment) before the photosensitive layer is applied in aqueous acid or salt solutions, which may also contain additives such as corrosion inhibitors).
- Aluminum printing plates with electrochemical roughening in aqueous HC1 and / or HN0 3 solutions are used in particular for the present invention.
- the process parameters in the roughening stage are in the following ranges: the temperature of the electrolyte between 20 and 60 ° C., the active substance (acid, salt) concentration between 5 and 100 g / 1 (in the case of salts also higher), the current density between 15 and 130 A / dm 2 , the residence time between 10 and 100 sec and the electrolyte flow rate in continuous processes on the surface of the workpiece to be treated between 5 and 100 cm / sec; AC is usually used as the type of current, but modified types of current such as AC with different amplitudes of the current strength for the anode and cathode current are also possible.
- the average roughness depth R z of the roughened surface is in the range of about 1 to 15 pm, in particular in the range from 2 to 8 ⁇ m.
- the roughness depth is determined in accordance with DIN 4768 in the version from October 1970, the roughness depth R z is then the arithmetic mean of the individual roughness depths of five adjacent individual measuring sections.
- Direct current is preferably used for the anodic oxidation, but alternating current or a combination of these types of current (eg direct current with superimposed alternating current) can also be used; the electrolyte is in particular a water containing H 2 S0 4 and / or H 3 P0 4 solution.
- the layer weights of aluminum oxide range from 1 to 10 g / m 2 , corresponding to a layer thickness of approximately 0.3 to 3.0 ⁇ m.
- a radiation-sensitive coating is applied to the carrier material either by the manufacturer of presensitized printing plates or directly by the consumer.
- all layers are suitable as radiation (light) sensitive layers which, after irradiation (exposure), optionally with subsequent development and / or fixation, provide an image-like area from which printing can take place.
- offset printing plates obtained from the carrier materials according to the invention are converted into the desired printing form in a known manner by imagewise exposure or irradiation and washing out of the non-image areas with a developer, preferably an aqueous developer solution.
- a developer preferably an aqueous developer solution.
- offset printing plates, the base support materials of which were post-treated by the two-stage process according to the invention, are distinguished from those in which the same base material was post-treated in one stage with aqueous solutions containing only silicates, by improved hydrophilicity of the non-image areas, a lower tendency to form color fog, and improved resistance to alkali and achieving a steeper gradation (measured with a halftone step part).
- An aluminum foil is electrochemically roughened in a dilute aqueous solution containing HN0 3 using alternating current and anodically oxidized in a dilute aqueous solution containing H 2 SO 4 using direct current.
- a) specimens are immersed for 2 SiO 3 ⁇ 5 H 2 0 containing solution in an aqueous Na (duration, temperature and concentration, see Table I), then with distilled water.
- H 2 0 rinsed this intermediate cleaning can also be omitted, see Table I
- the silication in immersed in the aqueous solution of an alkaline earth metal nitrate at room temperature duration, type of cation and concentration see Table I.
- the contact angle and / or the light-sensitive coating again with dist.
- H 2 0 rinsed and dried or dried directly (see Table I).
- the contact angles in the comparative examples VI and V5 are 74.0 ° and 19.0 ° and in examples 9 and 21 7.0 ° and 11.3 °.
- stage b) is generally omitted, and stages a) and b) are also omitted.
- Table I and the contact angle measurements show the clear difference in the better hydrophilicity and the better alkali resistance of the products treated according to the invention compared to the prior art.
- the use of the intermediate rinses also shows a certain influence in the alkali resistance, it is generally better in the case of samples which have not been rinsed after the silicatization stage than in the case of samples which have been rinsed, but also in this case still significantly better than in the prior art.
- Example Groups 1 to 23 The procedure described in Example Groups 1 to 23 is followed, but the silicatization step is carried out electrochemically at room temperature (see Table II).
- a print run of over 100,000 prints can be created from the printing form created after exposure and development.
- a print run of more than 150,000 prints can be created from the printing form created after exposure and development.
- Example 35 The procedure of Example 35 is followed, but the two-stage treatment with silicates and alkaline earth metal salts is not used, but is instead post-treated with an aqueous polyvinylphosphonic acid solution.
- the gradation of the image areas in V19 is one to two wedge steps softer (i.e. less steep) than in Example 35, and the circulation is 130,000 prints.
- example groups 1 to 23 The procedure of example groups 1 to 23 is followed, but the two-stage treatment with silicates and alkaline earth metal salts is not used, but the roughened and oxidized aluminum samples are for 30 seconds in aqueous solutions with a content of 2 g / 1 of sodium carboxymethyl cellulose (in V20 with a viscosity of 300 mPa ⁇ s, in V20 with a viscosity of 30,000 mPa ⁇ s, each with a degree of substitution of about 0.7) and 2 g / 1 of Sr (N0 3 ) 2 immersed at 25 ° C (in Based on DE-AS 23 64 177). In both comparisons, the zincate test times are 31 seconds for samples not rinsed after this treatment and for those with dist. H 2 0 sec nachge (2004)ten samples at 25, not that these N achANsart affects virtually or only slightly on the alkali resistance of the oxide layer.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Printing Plates And Materials Therefor (AREA)
- Electrochemical Coating By Surface Reaction (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19823232485 DE3232485A1 (de) | 1982-09-01 | 1982-09-01 | Verfahren zur nachbehandlung von aluminiumoxidschichten mit alkalisilikat enthaltenden waessrigen loesungen und dessen verwendung bei der herstellung von offsetdruckplattentraegern |
DE3232485 | 1982-09-01 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0105170A2 true EP0105170A2 (fr) | 1984-04-11 |
EP0105170A3 EP0105170A3 (en) | 1986-08-06 |
EP0105170B1 EP0105170B1 (fr) | 1988-01-13 |
Family
ID=6172219
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP83108259A Expired EP0105170B1 (fr) | 1982-09-01 | 1983-08-22 | Procédé de posttraitement de couches d'oxyde d'aluminium avec des solutions aqueuses contenant du silicate alcalin et son application dans la fabrication des supports pour plaques d'impression |
Country Status (8)
Country | Link |
---|---|
US (1) | US4492616A (fr) |
EP (1) | EP0105170B1 (fr) |
JP (1) | JPS5959897A (fr) |
AU (1) | AU553196B2 (fr) |
BR (1) | BR8304765A (fr) |
CA (1) | CA1225961A (fr) |
DE (2) | DE3232485A1 (fr) |
ZA (1) | ZA836092B (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0683248A1 (fr) * | 1994-05-21 | 1995-11-22 | Hoechst Aktiengesellschaft | Procédé de post-traitement de plaques, feuilles ou bandes et son application comme support pour plaques d'impression |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6019593A (ja) * | 1983-07-14 | 1985-01-31 | Fuji Photo Film Co Ltd | 平版印刷版用支持体の製造方法 |
JPH0694234B2 (ja) * | 1984-01-17 | 1994-11-24 | 富士写真フイルム株式会社 | 感光性平版印刷版 |
DE3406102A1 (de) * | 1984-02-21 | 1985-08-22 | Hoechst Ag, 6230 Frankfurt | Verfahren zur nachbehandlung von aluminiumoxidschichten mit alkalimetallsilikat enthaltenden waessrigen loesungen und deren verwendung bei der herstellung von offsetdruckplattentraegern |
DE3406101A1 (de) * | 1984-02-21 | 1985-08-22 | Hoechst Ag, 6230 Frankfurt | Verfahren zur zweistufigen hydrophilierenden nachbehandlung von aluminiumoxidschichten mit waessrigen loesungen und deren verwendung bei der herstellung von offsetdruckplattentraegern |
JPS6282089A (ja) * | 1985-10-04 | 1987-04-15 | Fuji Photo Film Co Ltd | 平版印刷版用支持体の製造方法 |
US4983497A (en) * | 1985-10-10 | 1991-01-08 | Eastman Kodak Company | Treated anodized aluminum support and lithographic printing plate containing same |
JPH0790669B2 (ja) * | 1986-03-19 | 1995-10-04 | 大日本インキ化学工業株式会社 | 平版印刷版用支持体の製造方法 |
JPH062434B2 (ja) * | 1986-11-20 | 1994-01-12 | 富士写真フイルム株式会社 | 平版印刷版用支持体 |
JP2595635B2 (ja) * | 1988-03-24 | 1997-04-02 | 富士電機株式会社 | 電子写真用感光体 |
EP0373510A3 (fr) * | 1988-12-13 | 1990-07-11 | Konica Corporation | Procédé de fabrication d' une plaque d'impression lithographique photosensible |
US5672390A (en) * | 1990-11-13 | 1997-09-30 | Dancor, Inc. | Process for protecting a surface using silicate compounds |
US5258263A (en) * | 1991-09-10 | 1993-11-02 | Polaroid Corporation | Printing plate and methods of making and use same |
DE69512321T2 (de) | 1994-06-16 | 2000-05-11 | Kodak Polychrome Graphics Llc | Lithographische Druckplatten mit einer oleophilen bilderzeugenden Schicht |
EP0799717B1 (fr) * | 1996-04-03 | 1999-11-17 | Agfa-Gevaert N.V. | Procédé de fabrication d'une surface hydrophile d'une plaque d'impression lithographique |
US6664019B2 (en) | 1996-06-19 | 2003-12-16 | Printing Developments Inc. | Aluminum printing plates and method of making |
GB9624224D0 (en) † | 1996-11-21 | 1997-01-08 | Horsell Graphic Ind Ltd | Planographic printing |
JP3830114B2 (ja) * | 1997-09-29 | 2006-10-04 | 富士写真フイルム株式会社 | ポジ型感光性平版印刷版 |
US6358616B1 (en) | 2000-02-18 | 2002-03-19 | Dancor, Inc. | Protective coating for metals |
US6405651B1 (en) * | 2000-03-03 | 2002-06-18 | Alcoa Inc. | Electrocoating process for making lithographic sheet material |
US6374737B1 (en) * | 2000-03-03 | 2002-04-23 | Alcoa Inc. | Printing plate material with electrocoated layer |
US6376377B1 (en) * | 2000-04-03 | 2002-04-23 | Taiwan Semiconductor Manufacturing Company | Post chemical mechanical polish (CMP) planarizing substrate cleaning method employing enhanced substrate hydrophilicity |
JP4268345B2 (ja) * | 2001-04-20 | 2009-05-27 | 富士フイルム株式会社 | 平版印刷版用支持体 |
ES2195765B1 (es) * | 2002-01-29 | 2005-02-01 | Planchas Y Productos Para Offset Lithoplate, S.A. | Plancha para la impresion offset y procedimiento para su fabricacion. |
US20040188262A1 (en) * | 2002-02-05 | 2004-09-30 | Heimann Robert L. | Method for treating metallic surfaces and products formed thereby |
JP2004106200A (ja) | 2002-09-13 | 2004-04-08 | Fuji Photo Film Co Ltd | 平版印刷版用支持体、その製造方法および平版印刷版原版 |
EP1873278A1 (fr) * | 2006-06-30 | 2008-01-02 | Henkel Kommanditgesellschaft Auf Aktien | Traitement par du silicate de pieces d 'aluminium anodisees et colmatées |
US8173221B2 (en) * | 2008-03-18 | 2012-05-08 | MCT Research & Development | Protective coatings for metals |
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US2882154A (en) * | 1954-02-04 | 1959-04-14 | Polychrome Corp | Planographic printing plate |
GB965837A (en) * | 1962-06-19 | 1964-08-06 | Charles Calvin Cohn | Treatment of aluminum oxide coatings |
US3749596A (en) * | 1970-05-13 | 1973-07-31 | Okuno Chem Ind Co | Method for sealing anodized aluminum |
FR2385819A1 (fr) * | 1977-03-30 | 1978-10-27 | Yoshida Kogyo Kk | Procede pour la fabrication d'une pellicule de revetement sur une pellicule superficielle anodisee et resistant a la corrosion d'articles en aluminium |
JPS565999A (en) * | 1979-06-28 | 1981-01-22 | Daidou Kofunyuugenkoushi | Forming of antiicorrosion aluminum oxide film |
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BE507657A (fr) * | 1950-12-06 | |||
BE551658A (fr) * | 1955-10-10 | |||
US2922715A (en) * | 1956-03-26 | 1960-01-26 | Polychrome Corp | Presensitized printing plate and method for preparing same |
BE606888A (fr) * | 1960-08-05 | 1900-01-01 | ||
US3181461A (en) * | 1963-05-23 | 1965-05-04 | Howard A Fromson | Photographic plate |
ZA6807938B (fr) * | 1967-12-04 | |||
AT309942B (de) * | 1971-05-18 | 1973-09-10 | Isovolta | Verfahren zum anodischen Oxydieren von Gegenständen aus Aluminium oder seinen Legierungen |
US3860426A (en) * | 1972-12-22 | 1975-01-14 | Eastman Kodak Co | Subbed lithographic printing plate |
US3902976A (en) * | 1974-10-01 | 1975-09-02 | S O Litho Corp | Corrosion and abrasion resistant aluminum and aluminum alloy plates particularly useful as support members for photolithographic plates and the like |
CA1112600A (fr) * | 1975-11-13 | 1981-11-17 | Shyoichi Anada | Traitement superficiel de l'aluminium par voie electrolytique dans un bain d'hydroxyde ou de sel additionne d'acide |
JPS5926480B2 (ja) * | 1978-03-27 | 1984-06-27 | 富士写真フイルム株式会社 | 平版印刷版用支持体 |
JPS5582695A (en) * | 1978-12-18 | 1980-06-21 | Osaka Insatsu Ink Chubu Hanbai Kk | Surface treatment of aluminum material |
EP0016298B1 (fr) * | 1979-01-22 | 1983-08-17 | Ball Corporation | Solution pour conférer une resistance au ternissage à des surfaces d'aluminium et procédé d'application |
JPS55109693A (en) * | 1979-02-19 | 1980-08-23 | Osaka Insatsu Ink Chubu Hanbai Kk | Surface treatment of aluminum printing material |
-
1982
- 1982-09-01 DE DE19823232485 patent/DE3232485A1/de not_active Withdrawn
-
1983
- 1983-08-17 CA CA000434745A patent/CA1225961A/fr not_active Expired
- 1983-08-18 JP JP58149729A patent/JPS5959897A/ja active Granted
- 1983-08-18 ZA ZA836092A patent/ZA836092B/xx unknown
- 1983-08-19 US US06/524,591 patent/US4492616A/en not_active Expired - Lifetime
- 1983-08-19 AU AU18147/83A patent/AU553196B2/en not_active Ceased
- 1983-08-22 EP EP83108259A patent/EP0105170B1/fr not_active Expired
- 1983-08-22 DE DE8383108259T patent/DE3375307D1/de not_active Expired
- 1983-08-31 BR BR8304765A patent/BR8304765A/pt not_active IP Right Cessation
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US2882154A (en) * | 1954-02-04 | 1959-04-14 | Polychrome Corp | Planographic printing plate |
GB965837A (en) * | 1962-06-19 | 1964-08-06 | Charles Calvin Cohn | Treatment of aluminum oxide coatings |
US3749596A (en) * | 1970-05-13 | 1973-07-31 | Okuno Chem Ind Co | Method for sealing anodized aluminum |
FR2385819A1 (fr) * | 1977-03-30 | 1978-10-27 | Yoshida Kogyo Kk | Procede pour la fabrication d'une pellicule de revetement sur une pellicule superficielle anodisee et resistant a la corrosion d'articles en aluminium |
JPS565999A (en) * | 1979-06-28 | 1981-01-22 | Daidou Kofunyuugenkoushi | Forming of antiicorrosion aluminum oxide film |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0683248A1 (fr) * | 1994-05-21 | 1995-11-22 | Hoechst Aktiengesellschaft | Procédé de post-traitement de plaques, feuilles ou bandes et son application comme support pour plaques d'impression |
Also Published As
Publication number | Publication date |
---|---|
JPS5959897A (ja) | 1984-04-05 |
CA1225961A (fr) | 1987-08-25 |
JPH0314916B2 (fr) | 1991-02-27 |
EP0105170A3 (en) | 1986-08-06 |
BR8304765A (pt) | 1984-04-10 |
DE3375307D1 (en) | 1988-02-18 |
AU1814783A (en) | 1984-03-08 |
DE3232485A1 (de) | 1984-03-01 |
ZA836092B (en) | 1984-04-25 |
AU553196B2 (en) | 1986-07-03 |
EP0105170B1 (fr) | 1988-01-13 |
US4492616A (en) | 1985-01-08 |
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