EP0161608B1 - Verfahren zur Nachbehandlung von Aluminiumoxidschichten mit Phosphoroxo-Anionen enthaltenden wässrigen Lösungen und deren Verwendung bei der Herstellung von Offsetdruckplattenträgern - Google Patents
Verfahren zur Nachbehandlung von Aluminiumoxidschichten mit Phosphoroxo-Anionen enthaltenden wässrigen Lösungen und deren Verwendung bei der Herstellung von Offsetdruckplattenträgern Download PDFInfo
- Publication number
- EP0161608B1 EP0161608B1 EP85105492A EP85105492A EP0161608B1 EP 0161608 B1 EP0161608 B1 EP 0161608B1 EP 85105492 A EP85105492 A EP 85105492A EP 85105492 A EP85105492 A EP 85105492A EP 0161608 B1 EP0161608 B1 EP 0161608B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- layers
- aqueous solution
- anions
- aluminum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 41
- 239000007864 aqueous solution Substances 0.000 title claims description 22
- 150000001450 anions Chemical class 0.000 title claims description 10
- 238000007645 offset printing Methods 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title 3
- 239000000463 material Substances 0.000 claims description 23
- 238000011282 treatment Methods 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 230000005855 radiation Effects 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 7
- 229940005740 hexametaphosphate Drugs 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229940005739 hexasodium hexametaphosphate Drugs 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 1
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 238000007639 printing Methods 0.000 description 22
- -1 phosphorus oxo anions Chemical class 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- 239000011734 sodium Substances 0.000 description 13
- 239000012876 carrier material Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 238000007788 roughening Methods 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000012954 diazonium Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 230000001680 brushing effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- LRMHFDNWKCSEQU-UHFFFAOYSA-N ethoxyethane;phenol Chemical compound CCOCC.OC1=CC=CC=C1 LRMHFDNWKCSEQU-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- LXFQSRIDYRFTJW-UHFFFAOYSA-M 2,4,6-trimethylbenzenesulfonate Chemical compound CC1=CC(C)=C(S([O-])(=O)=O)C(C)=C1 LXFQSRIDYRFTJW-UHFFFAOYSA-M 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
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 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 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000005137 alkenylsulfonyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 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
- 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
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 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
- 238000005237 degreasing agent Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- IIRVGTWONXBBAW-UHFFFAOYSA-M disodium;dioxido(oxo)phosphanium Chemical compound [Na+].[Na+].[O-][P+]([O-])=O IIRVGTWONXBBAW-UHFFFAOYSA-M 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
- 238000002474 experimental method Methods 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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
- 230000014759 maintenance of location Effects 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
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 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
- 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 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
- 229920003986 novolac Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 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
- 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
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- BFDWBSRJQZPEEB-UHFFFAOYSA-L sodium fluorophosphate Chemical compound [Na+].[Na+].[O-]P([O-])(F)=O BFDWBSRJQZPEEB-UHFFFAOYSA-L 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 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
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 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
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 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
-
- 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
-
- 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 phosphorus oxo anions.
- 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 (light) sensitive layer (reproduction layer), with the help of which a printing image of a template is generated photomechanically.
- the layer support carries the image points which will guide the color during later printing and at the same time forms the hydrophilic background for the lithographic printing process at the non-image points (non-image points) during later printing.
- Aluminum is used in particular as the base material for such substrates. It is roughened according to 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 anodization step to build up a thin oxide layer.
- the carrier materials in particular anodically oxidized carrier materials based on aluminum, are subjected to a further treatment step to improve the layer adhesion, to increase the hydrophilicity and / or to facilitate the developability of the radiation-sensitive layers before the application of a radiation-sensitive layer for example the following methods.
- the US-A 3 808 000 describes similarly.
- stage b) phosphoric acid (H 3 P0 4 ), sodium dihydrogen phosphate (NaH 2 P0 4 ), disodium hydrogen phosphate (Na 2 HP0 4 ), trisodium phosphate (Na 3 P0 4 ), phosphorous acid (H 3 P0 3 ), disodium phosphite (Na 2 HPO 3 ), diphosphoric acid (H 4 P 2 0 7 ), sodium pyrophosphate (Na 4 P 2 0 7 ), triphosphoric acid (H5P 3 0 10 ), sodium triphosphate (Na 5 P 3 O 10 ), Polyphosphoric acid (H n + 2 P n 0 3n + 1 ), hexasodium tetrapolyphosphate (Na 6 P 4 0 13 ), hexasodium metaphosphate [Na 6 (P0 3 ) 61 , disodium monofluorophosphate (Na 2 PO 2 F) and potassium
- DE-A 2 609 577 describes a process for producing sealed anodic oxide thin layers on aluminum and aluminum alloys prior to their coating, the oxide layer being treated in an aqueous solution which contains phosphorus compounds at at least 80.degree.
- the main phosphorus compounds used are orthophosphoric acid, phosphorous acid and salts of the acids mentioned, and phosphorus compounds of tungsten or molybdic acid.
- the purpose of the treatment is to prevent hairline cracks in these oxide layers, for example to improve the application of paint.
- 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 thus produced, which in particular meets the practical requirements of a high-performance printing plate described at the outset and already known dipping methods improved in effect.
- the invention is based on the known process for the production of sheet, film or strip materials based on chemically, mechanically and / or electrochemically roughened and anodically oxidized aluminum or one of its alloys, the aluminum oxide layers of which contain an aqueous solution containing phosphorus oxo anions be treated.
- the process according to the invention is then characterized in that the aftertreatment of the aluminum oxide layer is not carried out electrolytically by immersion treatment in an aqueous solution containing hexametaphosphate anions.
- the aqueous solution generally contains 1 to 300 g / l of hexametaphosphate anions, preferably 3 to 150 g / l and in particular 5 to 100 g / l.
- the aftertreatment is carried out discontinuously or preferably continuously in the modern belt systems.
- the treatment times are expediently in the range from 0.5 to 120 seconds and the treatment temperatures are from 15 to 80 ° C., in particular from 20 to 75 ° C.
- 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 the material to be treated 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 flat aluminum is first mechanically, if necessary after pre-cleaning, (for example by brushing and / or with an abrasive treatment); roughened chemically (e.g. by etching agents) and / or electrochemically (e.g. by alternating current treatment in aqueous acid or salt solutions).
- the electrochemical roughening is preferably carried out in the process according to the invention, but these aluminum carrier materials can also be roughened mechanically (for example by brushing with wire or nylon brushes and / or with an abrasive treatment) even before the electrochemical stage. All process steps can be carried out discontinuously with plates or foils, but they are preferably carried out continuously with tapes.
- the process parameters in particular in the case of a continuous process, in the electrochemical roughening stage lie in the following ranges: the temperature of the aqueous electrolyte generally containing 0.3 to 5.0% by weight of acid (s) (also higher in the case of salts) 20 and 60 ° C, the current density between 3 and 200 A / dm 2 , the residence time of a material point to be roughened in the electrolyte between 3 and 100 seconds and the electrolyte flow rate on the surface of the material to be roughened between 5 and 100 cm / sec; in the batchwise process, the required current densities tend to be in the lower part and the dwell times are in the upper part of the ranges specified, and the flow of the electrolyte can also be dispensed with.
- alternating current of a frequency of 50 to 60 Hz is usually used as the type of current, but modified types of current such as alternating current with different amplitudes of the current strength for the anode and cathode current, lower frequencies, current interruptions or superimposition of two currents of different frequency and waveform are also possible.
- the average roughness depth R 2 of the roughened surface is in the range from 1 to 15 ⁇ m, in particular from 1.5 to 8.0 ⁇ m.
- the aqueous electrolyte contains acid (s), in particular HCl and / or HN0 3 , aluminum ions in the form of aluminum salts, in particular Al (N0 3 ) 3 and / or AICI 3 can also be added to it; the addition of certain other acids and salts such as boric acid or borates or of corrosion inhibitors such as amines is also known.
- the pre-cleaning includes, for example, treatment with aqueous NaOH solution with or without Degreasing agents and / or complexing agents, trichlorethylene, acetone, methanol or other commercially available aluminum stains.
- the roughening or, in the case of several roughening stages, also between the individual stages, an abrasive treatment can additionally be carried out, in particular a maximum of 2 g / m 2 being removed (up to 5 g / m 2 between the stages);
- aqueous solutions of alkali metal hydroxide or aqueous solutions of alkaline salts or aqueous acid solutions based on HN0 3 , H 2 SO 4 or H 3 PO 4 are used as abrasive solutions.
- non-electrochemical treatments are also known which essentially only have a rinsing and / or cleaning effect and, for example, for removing deposits formed during roughening ("Schmant") or simply for Serve removal of electrolyte residues; For example, dilute aqueous alkali hydroxide solutions or water are used for these purposes.
- anodic oxidation of the aluminum follows in a further process step, for example to improve the abrasion and adhesion properties of the surface of the carrier material.
- the usual electrolytes such as H 2 S0 4 , H 3 P0 4 , H 2 C 2 0 4 , amidosulfonic acid, sulfosuccinic acid, sulfosalicylic acid or mixtures thereof can be used for anodic oxidation; in particular, H 2 S0 4 and H 3 P0 4 are used alone, in a mixture and / or in a multi-stage anodizing process; an aqueous solution containing H 2 S0 4 and A1 3 + ions is particularly preferably used.
- the oxide layer weights are generally in particular between 1 and 8 g / m 2 (corresponding to about 0.3 to 2.5 ⁇ m layer thickness).
- the materials produced according to the invention are preferably used as supports for offset printing plates, i. H. a radiation-sensitive coating is applied to one or both sides of the carrier material either by the manufacturer of presensitized printing plates or directly by the consumer.
- a radiation-sensitive coating is applied to one or both sides of 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 imagewise surface from which printing can take place.
- photoconductive layers such as z. B. in DE-C 1 117 391, 1 522 497, 1 572 312, 2 322 046 and 2 322 047 are described, applied to the carrier materials produced according to the invention, whereby highly light-sensitive, electrophotographic printing plates are formed.
- coated offset printing plates obtained from the carrier materials produced 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.
- offset printing plates whose base support materials have been post-treated by the two-stage process according to the invention, are distinguished in particular by a lower tendency to form color fog compared to those plates in which the same base material has been post-treated with other aqueous solutions containing phosphorus oxo anions (see the following comparative experiments).
- This special effect of the hexametaphosphate anions in a pure immersion treatment was not predictable, since the whole group of anions shows a similar effect in the electrochemical treatment.
- An aluminum strip is electrochemically roughened in an aqueous solution containing 1.4% of HN0 3 and 6% of Al (N0 3 ) 3 using alternating current (115 A / dm 2 at 35 ° C.) and in an aqueous H 2 S0 4 and Al 3 + - ion containing solution anodized with direct current.
- the oxide layer which has a layer weight of approximately 2.5 g / m 2 , is immersed for 15 seconds at a temperature of 45 to 50 ° C. in an aqueous solution of pH 7 containing hexasodium hexametaphosphate (Na 6 P 6 0 18 ).
- the changes in the dye adsorption obtained with increasing proportions of this salt are shown in the table.
- the comparative example is carried out without an aftertreatment.
- Example 1 The procedure of Example 1 is followed, but roughened in an aqueous solution containing 0.9% of HCl.
- Example 2 The procedure is as in Example 1, but the Na 6 P 6 O 18 solution additionally contains 10 g / 1 of citric acid and thus a pH of 2.5.
- Example 2 The procedure is as in Example 2, but the Na 6 P 6 O 18 solution additionally contains 10 g / l of citric acid and thus a pH of 2.5.
- Example 1 V5 to V12
- Example 2 V13 to V20
- the effect is affected by a change in pH, e.g. B. with the addition of citric acid, significantly increased again; it also occurs with the addition of other, not too strong acids, in the pH range from 1 to 5 in a similar order of magnitude.
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)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19843418111 DE3418111A1 (de) | 1984-05-16 | 1984-05-16 | Verfahren zur nachbehandlung von aluminiumoxidschichten mit phosphoroxo-anionen enthaltenden waessrigen loesungen und deren verwendung bei der herstellung von offsetdruckplattentraegern |
DE3418111 | 1984-05-16 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0161608A1 EP0161608A1 (de) | 1985-11-21 |
EP0161608B1 true EP0161608B1 (de) | 1987-08-12 |
Family
ID=6235962
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP85105492A Expired EP0161608B1 (de) | 1984-05-16 | 1985-05-06 | Verfahren zur Nachbehandlung von Aluminiumoxidschichten mit Phosphoroxo-Anionen enthaltenden wässrigen Lösungen und deren Verwendung bei der Herstellung von Offsetdruckplattenträgern |
Country Status (7)
Country | Link |
---|---|
US (1) | US4650739A (enrdf_load_stackoverflow) |
EP (1) | EP0161608B1 (enrdf_load_stackoverflow) |
JP (1) | JPS60253597A (enrdf_load_stackoverflow) |
BR (1) | BR8502292A (enrdf_load_stackoverflow) |
CA (1) | CA1271958A (enrdf_load_stackoverflow) |
DE (2) | DE3418111A1 (enrdf_load_stackoverflow) |
ZA (1) | ZA853680B (enrdf_load_stackoverflow) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07119151B2 (ja) * | 1987-12-07 | 1995-12-20 | 富士写真フイルム株式会社 | 平版印刷版用支持体 |
US5230988A (en) * | 1991-03-12 | 1993-07-27 | Fuji Photo Film Co., Ltd. | Method of making lithographic printing plate |
ATE336390T1 (de) * | 1998-12-22 | 2006-09-15 | Fuji Photo Film Co Ltd | Verfahren zur herstellung einer lichtempfindlichen flachdruckplatte |
JP4868020B2 (ja) * | 2008-12-26 | 2012-02-01 | 株式会社デンソー | アルミニウムの陽極酸化方法、および陽極酸化アルミニウム |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL273557A (enrdf_load_stackoverflow) * | 1961-01-25 | |||
BE630566A (enrdf_load_stackoverflow) * | 1962-04-03 | |||
US3373021A (en) * | 1964-01-29 | 1968-03-12 | Harris Intertype Corp | Presensitized positive working lithographic plate |
US3511661A (en) * | 1966-07-01 | 1970-05-12 | Eastman Kodak Co | Lithographic printing plate |
ZA6807938B (enrdf_load_stackoverflow) * | 1967-12-04 | |||
CH526399A (de) * | 1968-12-06 | 1972-08-15 | Hasek Josef | Verfahren zur Herstellung einer Offsetdruckplatte |
US3679419A (en) * | 1969-05-20 | 1972-07-25 | Azoplate Corp | Light-sensitive diazo condensate containing reproduction material |
GB1410768A (en) * | 1971-10-22 | 1975-10-22 | Vickers Ltd | Lithographic printing plates comprising anodised aluminium |
BE792852A (fr) * | 1971-12-17 | 1973-06-15 | Henkel & Cie Gmbh | Procede de traitement de surfaces d'aluminium par oxydation suivie d'une densification |
US3808000A (en) * | 1972-03-28 | 1974-04-30 | Grace W R & Co | Printing plate and method of preparation |
CA1011279A (en) * | 1972-07-27 | 1977-05-31 | Yoshiaki Miyosawa | Method of after-treatment for lithographic printing plates |
US4116695A (en) * | 1974-09-12 | 1978-09-26 | Fuji Photo Film Co., Ltd. | Method of producing a support for a printing plate |
JPS51101741A (ja) * | 1975-03-06 | 1976-09-08 | Yoshida Kogyo Kk | Taishokuseiyokyokusankahimakunotosoho |
JPS52150104A (en) * | 1976-06-07 | 1977-12-13 | Fuji Photo Film Co Ltd | Photoosensitive lithographic press plate material |
DE3006094A1 (de) * | 1980-02-19 | 1981-08-20 | Hoechst Ag, 6000 Frankfurt | Verfahren zum konservieren von flachdruckformen |
DE3126636A1 (de) * | 1981-07-06 | 1983-01-27 | Hoechst Ag, 6000 Frankfurt | Hydrophilierte traegermaterialien fuer offsetdruckplatten, ein verfahren zu ihrer herstellung und ihre verwendung |
DE3206470A1 (de) * | 1982-02-23 | 1983-09-01 | Hoechst Ag, 6230 Frankfurt | Verfahren zur herstellung von traegermaterialien fuer offsetdruckplatten |
US4414311A (en) * | 1982-03-18 | 1983-11-08 | American Hoechst Corporation | Cathodic deposition of light sensitive components |
JPS58193194A (ja) * | 1982-05-06 | 1983-11-10 | Fuji Photo Film Co Ltd | 平版印刷版用版画保護剤 |
JPS59214651A (ja) * | 1983-05-20 | 1984-12-04 | Fuji Photo Film Co Ltd | 感光性平版印刷版を用いた製版方法 |
-
1984
- 1984-05-16 DE DE19843418111 patent/DE3418111A1/de not_active Withdrawn
-
1985
- 1985-05-06 DE DE8585105492T patent/DE3560465D1/de not_active Expired
- 1985-05-06 EP EP85105492A patent/EP0161608B1/de not_active Expired
- 1985-05-14 CA CA000481442A patent/CA1271958A/en not_active Expired - Fee Related
- 1985-05-15 BR BR8502292A patent/BR8502292A/pt not_active IP Right Cessation
- 1985-05-15 ZA ZA853680A patent/ZA853680B/xx unknown
- 1985-05-15 US US06/734,147 patent/US4650739A/en not_active Expired - Fee Related
- 1985-05-16 JP JP60102825A patent/JPS60253597A/ja active Granted
Also Published As
Publication number | Publication date |
---|---|
BR8502292A (pt) | 1986-01-21 |
US4650739A (en) | 1987-03-17 |
ZA853680B (en) | 1985-12-24 |
DE3560465D1 (en) | 1987-09-17 |
EP0161608A1 (de) | 1985-11-21 |
CA1271958A (en) | 1990-07-24 |
DE3418111A1 (de) | 1985-11-21 |
JPS60253597A (ja) | 1985-12-14 |
JPH0545437B2 (enrdf_load_stackoverflow) | 1993-07-09 |
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