EP1243413B1 - Procédé pour la fabrication d'un précurseur de type négatif d'une plaque d'impression lithographique thermosensible - Google Patents
Procédé pour la fabrication d'un précurseur de type négatif d'une plaque d'impression lithographique thermosensible Download PDFInfo
- Publication number
- EP1243413B1 EP1243413B1 EP20020100128 EP02100128A EP1243413B1 EP 1243413 B1 EP1243413 B1 EP 1243413B1 EP 20020100128 EP20020100128 EP 20020100128 EP 02100128 A EP02100128 A EP 02100128A EP 1243413 B1 EP1243413 B1 EP 1243413B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- image
- temperature
- particles
- printing plate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002243 precursor Substances 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229920000642 polymer Polymers 0.000 claims description 57
- 239000002245 particle Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 21
- 229920001169 thermoplastic Polymers 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 18
- 230000002209 hydrophobic effect Effects 0.000 claims description 17
- 230000005660 hydrophilic surface Effects 0.000 claims description 9
- 230000009477 glass transition Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims description 2
- 125000002560 nitrile group Chemical group 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 125000000565 sulfonamide group Chemical group 0.000 claims description 2
- 150000008360 acrylonitriles Chemical group 0.000 claims 1
- 239000012670 alkaline solution Substances 0.000 claims 1
- 230000001939 inductive effect Effects 0.000 claims 1
- 238000003384 imaging method Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 239000002585 base Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- -1 polyethylene Polymers 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000008119 colloidal silica Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 5
- 230000015271 coagulation Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000004581 coalescence Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
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- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229920001600 hydrophobic polymer Polymers 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 241001479434 Agfa Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910003439 heavy metal oxide Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229920001480 hydrophilic copolymer Polymers 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006290 polyethylene naphthalate film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
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- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
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- 239000000080 wetting agent Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
- B41C1/1025—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials using materials comprising a polymeric matrix containing a polymeric particulate material, e.g. hydrophobic heat coalescing particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/04—Negative working, i.e. the non-exposed (non-imaged) areas are removed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/06—Developable by an alkaline solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
- B41C2210/262—Phenolic condensation polymers, e.g. novolacs, resols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
- B41M5/366—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties using materials comprising a polymeric matrix containing a polymeric particulate material, e.g. hydrophobic heat coalescing particles
Definitions
- the present invention relates to a method of preparing a negative-working printing plate precursor having a hydrophilic substrate and a heat-sensitive image-recording layer provided thereon as well as a method of making a printing plate using such a material.
- Lithographic printing presses use a so-called printing master such as a printing plate which is mounted on a cylinder of the printing press.
- the master carries a lithographic image on its surface and a print is obtained by applying ink to said image and then transferring the ink from the master onto a receiver material, which is typically paper.
- ink as well as an aqueous fountain solution also called dampening liquid
- the lithographic image which consists of oleophilic (or hydrophobic, i.e. ink-accepting, water-repelling) areas as well as hydrophilic (or oleophobic, i.e. water-accepting, ink-repelling) areas.
- so-called driographic printing the lithographic image consists of ink-accepting and ink-abhesive (ink-repelling) areas and during driographic printing, only ink is supplied to the master.
- Printing masters are generally obtained by the so-called computer-to-film method wherein various pre-press steps such as typeface selection, scanning, color separation, screening, trapping, layout and imposition are accomplished digitally and each color selection is transferred to graphic arts film using an image-setter.
- the film can be used as a mask for the exposure of an imaging material called plate precursor and after plate processing, a printing plate is obtained which can be used as a master.
- a typical printing plate precursor for computer-to-film methods comprise a hydrophilic support and an image-recording layer of a photosensitive polymer layers which include UV-sensitive diazo compounds, dichromate-sensitized hydrophilic colloids and a large variety of synthetic photopolymers. Particularly diazo-sensitized systems are widely used.
- Upon image-wise exposure typically by means of a film mask in a UV contact frame, the exposed image areas become insoluble and the unexposed areas remain soluble in an aqueous alkaline developer.
- the plate is then processed with the developer to remove the diazonium salt or diazo resin in the unexposed areas. So the exposed areas define the image areas (printing areas) of the printing master, and such printing plate precursors are therefore called 'negative-working'.
- heat-sensitive printing plate precursors are known. Such materials offer the advantage of daylight stability and are especially used in the so-called computer-to-plate method wherein the plate precursor is directly exposed, i.e. without the use of a film mask.
- the material is exposed to heat or to infrared light and the generated heat triggers a (physico-)chemical process, such as ablation, polymerization, insolubilization by cross-linking of a polymer, decomposition, or particle coagulation of a thermoplastic polymer latex.
- a (physico-)chemical process such as ablation, polymerization, insolubilization by cross-linking of a polymer, decomposition, or particle coagulation of a thermoplastic polymer latex.
- a daylight-stable material with high lithographic performance and typical prior art examples of such heat-sensitive materials will now be discussed.
- thermoplastic polymer particles By image-wise exposure to an infrared laser, the thermoplastic polymer particles are image-wise coagulated thereby rendering the exposed areas ink-receptive without any further development.
- EP-A-514145 discloses a heat-sensitive imaging element including a coating comprising core-shell particles having a water insoluble heat softenable core component and a shell component which is soluble or swellable in aqueous alkaline medium. Red or infrared laser light directed image-wise at said imaging element causes selected particles to coalesce, at least partially, to form an image and the non-coalesced particles are then selectively removed by means of an aqueous alkaline developer. Afterwards a baking step is performed.
- EP-A-800928 discloses a heat sensitive imaging element comprising on a hydrophilic surface of a lithographic base an image forming layer comprising hydrophobic thermoplastic polymer particles dispersed in a water insoluble and alkali soluble or swellable resin and a compound capable of converting light into heat, wherein said alkali swellable or soluble resin comprises phenolic hydroxy groups and/or carboxyl groups.
- EP 1 080 884 discloses a heat sensitive imaging element comprising on a hydrophilic surface of a lithographic base an image forming layer comprising hydrophobic thermoplastic polymer particles with a diameter between 0.2 ⁇ m and 1.4 ⁇ m and a compound capable of converting light into heat.
- EP 0 881 096 discloses an imaging element comprising on a hydrophilic surface a barrier layer and a top layer comprising hydrophobic thermoplastic polymer particles and a compound capable of converting light into heat. Both layers are removable in an aqueous solution with a pH of at least 5.
- EP 0 770 497 discloses a method for making a lithographic printing plate comprising the steps of image-wise exposing of a heat sensitive element comprising on a hydrophilic surface of a lithographic base an image forming layer comprising hydrophobic thermoplastic polymer particles dispersed in a hydrophilic binder and a compound capable of converting light into heat, and developing the imaging element by rinsing it with plain water or an aqueous liquid.
- a method for obtaining a lithographic printing plate with improved ink-uptake comprising the steps of image-wise exposing, using a laser with a pixel dwell time between 0.1 ⁇ s and 50 ⁇ s, of a heat sensitive element comprising on a hydrophilic surface of a lithographic base an image forming layer comprising hydrophobic thermoplastic polymer particles dispersed in a hydrophilic binder and a compound capable of converting light into heat, and developing the imaging element.
- EP 0 773 113 discloses a method for making a lithographic printing plate comprising the steps of (i) image-wise exposing of a heat sensitive element comprising on a hydrophilic surface of a lithographic base an image forming layer comprising hydrophobic thermoplastic polymer particles dispersed in a hydrophilic binder and a compound capable of converting light into heat and, (ii) developing the imaging element and (iii) overall heating the imaging element.
- EP 0 773 112 discloses an imaging element comprising on a hydrophilic surface of a lithographic base an image forming layer comprising a hydrophobic thermoplastic polymer dispersed in a hydrophilic binder, a compound capable of converting light into heat and a cross-linking agent capable of cross-linking the hydrophilic binder upon heating.
- This object is realized by the method defined in claim 1.
- Specific features for preferred embodiments of the invention are set out in the dependent claims.
- the use of a polymer B which has a softening temperature that is lower than the glass transition temperature of the hydrophobic thermoplastic particles of polymer A allows to heat the composition up to a temperature above the softening temperature of polymer B without substantially triggering the image mechanism of heat-induced fusing or coalescence of the particles of polymer A.
- an aqueous dispersion of at least two polymers is prepared, referred to herein as polymer A and polymer B.
- the glass transition temperature of polymer A is higher than the softening temperature of polymer B.
- the softening temperature is the temperature at which the polymer begins to deform from a rigid state to a soft state, which normally occurs at a rapid rate over a narrow temperature interval.
- the softening temperature is near the glass transition temperature, whereas for highly crystalline polymers it is close to the melting point.
- the term "aqueous” shall be understood as meaning that more than 50 wt.% of the solvent is water.
- Organic liquids which are miscible with water can be present, e.g. alcohols, ketones, or derivatives thereof, but preferably only water is used as a solvent.
- Polymer A is a hydrophobic thermoplastic polymer that is not soluble or swellable in an aqueous alkaline developer.
- suitable hydrophobic polymers are e.g. polyethylene, poly(vinyl chloride), poly(methyl (meth)acrylate), poly(ethyl (meth)acrylate), poly(vinylidene chloride), poly(meth)acrylonitrile, poly(vinyl carbazole), polystyrene or copolymers thereof.
- Polystyrene and poly(meth)acrylonitrile or their derivatives are highly preferred embodiments of polymer A.
- polymer A comprises at least 50 wt.% of polystyrene, and more preferably at least 65 wt.% of polystyrene.
- polymer A preferably comprises at least 5 wt.%, more preferably at least 30 wt.% of nitrogen containing units or of units which correspond to monomers that are characterized by a solubility parameter larger than 20, such as (meth)acrylonitrile.
- polymer A consists of styrene and acrylonitrile units in a weight ratio between 1:1 and 5:1 (styrene:acrylonitrile), e.g. in a 2:1 ratio.
- the weight average molecular weight of the polymer A may range from 5,000 to 1,000,000 g/mol.
- the hydrophobic particles of polymer A preferably have a number average particle diameter below 200 nm, more preferably between 10 and 100 nm.
- the amount of hydrophobic thermoplastic polymer particles contained in the image-recording layer is preferably between 20% by weight and 65% by weight and more preferably between 25% by weight and 55% by weight and most preferably between 30% by weight and 45% by weight.
- the particles of polymer A are present as a dispersion in an aqueous coating liquid of the image forming layer and may be prepared by the methods disclosed in US 3,476,937. Another method especially suitable for preparing an aqueous dispersion of the thermoplastic polymer particles comprises:
- Polymer B is soluble or swellable in an aqueous alkaline developer but not soluble or swellable in water (i.e. at about neutral pH).
- polymer B is also present as particles in the aqueous dispersion because the pH of the dispersion is not sufficiently high to cause dissolution of the particles of polymer B.
- the polymer B comprises preferably a hydrophobic binder such as a phenolic resin, e.g. a novolac or resole resin, and/or a polymer containing a carboxy group, a sulfonamide group, a nitrile group, a maleimide group or a maleimidosulfadimidine group.
- Polymer B preferably has a softening temperature below 100°C, more preferably below 75°C and most preferably below 50°C.
- the weight ratio of the polymers A/B in the aqueous dispersion that is coated on the substrate is preferably larger than 0.5, more preferably larger than 0.6 and most preferably larger than 0.7.
- the dispersion of polymer A and B that, according to the method of the present invention, is applied to the lithographic substrate, may also contain other ingredients such as additional binders, surfactants, colorants, development inhibitors or accelerators, and especially one or more compounds that are capable of converting infrared light into heat.
- additional binders such as sodium carbides, borides, nitrides, carbonitrides, bronze-structured oxides, and conductive polymer dispersions such as polypyrrole, polyaniline or polythiophene-based conductive polymer dispersions.
- the substrate used in the methods of the present invention has a hydrophilic surface.
- the substrate may be a sheet-like material such as a plate or it may be a cylindrical element such as a sleeve which can be slid around a print cylinder of a printing press.
- the substrate can also be the print cylinder itself.
- the image-recording layer is provided on the print cylinder, e.g. by on-press spraying as described below.
- the lithographic substrate may be a hydrophilic support or a support which is provided with a hydrophilic layer.
- the support is a metal support such as aluminum or stainless steel.
- a particularly preferred lithographic substrate is an electrochemically grained and anodized aluminum support.
- the anodized aluminum support may be treated to improve the hydrophilic properties of its surface.
- the aluminum support may be silicated by treating its surface with a sodium silicate solution at elevated temperature, e.g. 95°C.
- a phosphate treatment may be applied which involves treating the aluminum oxide surface with a phosphate solution that may further contain an inorganic fluoride.
- the aluminum oxide surface may be rinsed with a citric acid or citrate solution. This treatment may be carried out at room temperature or may be carried out at a slightly elevated temperature of about 30 to 50°C.
- a further interesting treatment involves rinsing the aluminum oxide surface with a bicarbonate solution.
- the aluminum oxide surface may be treated with polyvinylphosphonic acid, polyvinylmethylphosphonic acid, phosphoric acid esters of polyvinyl alcohol, polyvinylsulfonic acid, polyvinylbenzenesulfonic acid, sulfuric acid esters of polyvinyl alcohol, and acetals of polyvinyl alcohols formed by reaction with a sulfonated aliphatic aldehyde It is further evident that one or more of these post treatments may be carried out alone or in combination.
- the substrate can also be a flexible support, which is provided with a hydrophilic layer, hereinafter called 'base layer'.
- the flexible support is e.g. paper, plastic film or aluminum.
- plastic film are polyethylene terephthalate film, polyethylene naphthalate film, cellulose acetate film, polystyrene film, polycarbonate film, etc.
- the plastic film support may be opaque or transparent.
- the base layer is preferably a cross-linked hydrophilic layer obtained from a hydrophilic binder cross-linked with a hardening agent such as formaldehyde, glyoxal, polyisocyanate or a hydrolyzed tetra-alkylorthosilicate.
- a hardening agent such as formaldehyde, glyoxal, polyisocyanate or a hydrolyzed tetra-alkylorthosilicate.
- the thickness of the hydrophilic base layer may vary in the range of 0.2 to 25 ⁇ m and is preferably 1 to 10 ⁇ m.
- the hydrophilic binder for use in the base layer is e.g. a hydrophilic (co)polymer such as homopolymers and copolymers of vinyl alcohol, acrylamide, methylol acrylamide, methylol methacrylamide, acrylate acid, methacrylate acid, hydroxyethyl acrylate, hydroxyethyl methacrylate or maleic anhydride/vinylmethylether copolymers.
- the hydrophilicity of the (co)polymer or (co)polymer mixture used is preferably the same as or higher than the hydrophilicity of polyvinyl acetate hydrolyzed to at least an extent of 60% by weight, preferably 80% by weight.
- the amount of hardening agent, in particular tetraalkyl orthosilicate, is preferably at least 0.2 parts per part by weight of hydrophilic binder, more preferably between 0.5 and 5 parts by weight, most preferably between 1 parts and 3 parts by weight.
- the hydrophilic base layer may also contain substances that increase the mechanical strength and the porosity of the layer.
- colloidal silica may be used.
- the colloidal silica employed may be in the form of any commercially available water dispersion of colloidal silica for example having an average particle size up to 40 nm, e.g. 20 nm.
- inert particles of larger size than the colloidal silica may be added e.g. silica prepared according to Stöber as described in J. Colloid and Interface Sci., Vol. 26, 1968, pages 62 to 69 or alumina particles or particles having an average diameter of at least 100 nm which are particles of titanium dioxide or other heavy metal oxides.
- the surface of the hydrophilic base layer is given a uniform rough texture consisting of microscopic hills and valleys, which serve as storage places for water in background areas.
- hydrophilic base layers for use in accordance with the present invention are disclosed in EP-A- 601 240, GB-P- 1 419 512, FR-P- 2 300 354, US-P- 3 971 660, and US-P- 4 284 705.
- the amount of silica in the adhesion improving layer is between 200 mg/m 2 and 750 mg/m 2 .
- the ratio of silica to hydrophilic binder is preferably more than 1 and the surface area of the colloidal silica is preferably at least 300 m 2 /gram, more preferably at least 500 m 2 /gram.
- the imaging layer can be applied on the lithographic substrate before or after mounting the substrate on the print cylinder of a printing press, unless the lithographic substrate is the print cylinder itself, as described above.
- the dispersion is coated, sprayed or jetted on-press onto the substrate and exposed on-press by means of an integrated exposure apparatus.
- the dispersion is coated on the substrate in an off-press apparatus and then mounted on the print cylinder.
- the above compositions are also suitable for on-press cleaning after the press-run, e.g. by spraying or jetting a cleaning composition on the master, thereby removing the printing areas from the substrate which can then be reused in a next cycle of coating, exposing, printing and cleaning.
- the image-recording layer After the image-recording layer has been applied on the substrate, it is heated to a temperature above the softening temperature of polymer B and preferably below the glass transition temperature of polymer A. Depending on the time and temperature of the heating step, it may result in a slight, a partial or complete fusing of the particles of polymer B which may lead to the formation of a film matrix wherein the particles of polymer A are dispersed.
- the heating may be performed during the drying of the coated layer, or otherwise the drying may be carried out at a lower temperature, e.g. room temperature, and then the heating may be performed as a separate step after the drying.
- the imaging materials used in the present invention are exposed to heat or to infrared light, e.g. by means of a thermal head, LEDs or an infrared laser.
- a laser emitting near infrared light having a wavelength in the range from about 700 to about 1500 nm is used, e.g. a semiconductor laser diode, a Nd:YAG or a Nd:YLF laser.
- the required laser power depends on the sensitivity of the image-recording layer, the pixel dwell time of the laser beam, which is determined by the spot diameter (typical value of modern plate-setters at 1/e 2 of maximum intensity : 10-25 ⁇ m), the scan speed and the resolution of the exposure apparatus (i.e.
- ITD plate-setters for thermal plates are typically characterized by a very high scan speed up to 500 m s -1 and may require a laser power of several Watts.
- the known plate-setters can be used as an off-press exposure apparatus in the present invention. This offers the benefit of reduced press down-time.
- XTD plate-setter configurations can also be used for on-press exposure, offering the benefit of immediate registration in a multi-color press. More technical details of on-press exposure apparatuses are described in e.g. US 5,174,205 and US 5,163,368.
- the particles of polymer A fuse or coagulate so as to form a hydrophobic phase which corresponds to the printing areas of the plate precursor. Coagulation may result from heat-induced coalescence, softening or melting of the thermoplastic polymer particles.
- the coagulation temperature of the thermoplastic hydrophobic polymer particles there is no specific upper limit to the coagulation temperature of the thermoplastic hydrophobic polymer particles, however the temperature should be sufficiently below the decomposition of the polymer particles.
- the coagulation temperature is at least 10°C below the temperature at which the decomposition of the polymer particles occurs.
- the coagulation temperature is preferably higher than 50°C, more preferably above 100°C.
- the non-exposed areas of the image-recording layer are removed by supplying an aqueous alkaline developer, which may be combined with mechanical,rubbing, e.g. by a rotating brush.
- the development step may be followed by a drying step, a rinsing step and/or a gumming step.
- the exposed and developed plates can be baked at a temperature of 230°C for 5 minutes, at a temperature of 150°C for 10 minutes or at a temperature of 120°C for 30 minutes.
- a 0.30 mm thick aluminum foil was degreased by immersing the foil in an aqueous solution containing 5 g/l of sodium hydroxide at 50°C and rinsed with demineralized water.
- the foil was then electrochemically grained using an alternating current in an aqueous solution containing 4 g/l of hydrochloric acid, 4 g/l of hydroboric acid and 5 g/l of aluminum ions at a temperature of 35°C and a current density of 1200 A/m 2 to form a surface topography with an average centre-line roughness Ra of 0.5 ⁇ m.
- the aluminum foil was then etched with an aqueous solution containing 300 g/l of sulfuric acid at 60°C for 180 seconds and rinsed with demineralized water at 25°C for 30 seconds.
- the foil was subsequently subjected to anodic oxidation in an aqueous solution containing 200 g/l of sulphuric acid at a temperature of 45°C, a voltage of about 10 V and a current density of 150 A/m 2 for about 300 seconds to form an anodic oxidation film of 3.00 g/m 2 of Al 2 O 3 then washed with demineralized water, post-treated with a solution containing polyvinylphosphonic acid and subsequently with a solution containing aluminum trichloride, rinsed with demineralized water at 20°C during 120 seconds and dried.
- High quality prints were obtained with the method according to the invention (1-4).
- the coating was not completely removed from the substrate in the unexposed areas, resulting in toning during printing.
- the coating was removed in both the exposed and the unexposed areas (no image).
- Composition 7 was adjusted to a high pH, so that the novolac particles could dissolve in the coating solution. The material thereby obtained provided low quality prints with some ink uptake in the exposed areas.
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Printing Plates And Materials Therefor (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
Claims (10)
- Procédé de fabrication d'un précurseur de cliché d'impression lithographique thermosensible à traitement négatif, le procédé comprenant les étapes consistant à(a) préparer une dispersion aqueuse comprenant des particules d'un polymère thermoplastique hydrophobe A qui n'est pas soluble ou apte à gonfler dans un révélateur alcalin aqueux et des particules d'un polymère B qui est soluble ou apte à gonfler dans un révélateur alcalin aqueux, mais qui n'est pas soluble ou apte à gonfler dans l'eau, dans lequel la température de transition vitreuse du polymère A est supérieure à la température de ramollissement du polymère B ;(B) appliquer la dispersion aqueuse sur un substrat lithographique possédant une surface hydrophile pour ainsi obtenir une couche d'enregistrement d'image ;(c) chauffer globalement la couche d'enregistrement d'image à une température qui est supérieure à la température de ramollissement du polymère B sans induire une coalescence des particules du polymère A.
- Procédé selon la revendication 1, dans lequel, au cours de l'étape (c), la couche d'enregistrement d'image est chauffée à une température qui est inférieure à la température de ramollissement du polymère A.
- Procédé selon la revendication 1, dans lequel, au cours de l'étape (c), la couche d'enregistrement d'image est chauffée à une température qui est inférieure à la température de transition vitreuse du polymère A.
- Procédé selon l'une quelconque des revendications précédentes, dans lequel les particules du polymère B comprennent une résine phénolique et/ou un polymère contenant un groupe carboxyle, un groupe sulfonamide, un groupe nitrile, un groupe maléimide ou un groupe maléidosulfadimidine.
- Procédé selon l'une quelconque des revendications précédentes, dans lequel le rapport pondéral des polymères A/B est supérieur à 0,5.
- Procédé selon l'une quelconque des revendications précédentes, dans lequel le polymère A comprend des unités possédant un paramètre de solubilité supérieur à 20 à concurrence d'au moins 5 %.
- Procédé selon l'une quelconque des revendications précédentes, dans lequel le polymère A comprend des unités de (méth)acrylonitrile à concurrence d'au moins 5 %.
- Procédé selon l'une quelconque des revendications précédentes, dans lequel les particules du polymère A possèdent un diamètre moyen en nombre inférieur à 200 nm.
- Procédé de fabrication d'un cliché d'impression lithographique comprenant les étapes consistant à :exposer en forme d'image un précurseur de cliché d'impression lithographique, que l'on obtient via un procédé selon l'une quelconque des revendications précédentes, à de la chaleur ou à de la lumière infrarouge ;éliminer les zones non exposées de la couche d'enregistrement d'image avec une solution alcaline aqueuse.
- Procédé de fabrication d'un cliché d'impression lithographique selon la revendication 9, le procédé comprenant en outre l'étape consistant à soumettre le cliché d'impression à une cuisson à une température qui est supérieure à la température de transition vitreuse du polymère A.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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EP20020100128 EP1243413B1 (fr) | 2001-03-20 | 2002-02-12 | Procédé pour la fabrication d'un précurseur de type négatif d'une plaque d'impression lithographique thermosensible |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01000059A EP1243410A1 (fr) | 2001-03-20 | 2001-03-20 | Méthode pour la fabrication d'un précurseur thermosensible pour une plaque lithographique |
EP01000059 | 2001-03-20 | ||
EP20020100128 EP1243413B1 (fr) | 2001-03-20 | 2002-02-12 | Procédé pour la fabrication d'un précurseur de type négatif d'une plaque d'impression lithographique thermosensible |
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EP1243413A1 EP1243413A1 (fr) | 2002-09-25 |
EP1243413B1 true EP1243413B1 (fr) | 2004-05-26 |
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EP20020100128 Expired - Lifetime EP1243413B1 (fr) | 2001-03-20 | 2002-02-12 | Procédé pour la fabrication d'un précurseur de type négatif d'une plaque d'impression lithographique thermosensible |
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Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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US20050153239A1 (en) * | 2004-01-09 | 2005-07-14 | Fuji Photo Film Co., Ltd. | Lithographic printing plate precursor and lithographic printing method using the same |
US7348126B2 (en) | 2004-04-27 | 2008-03-25 | Agfa Graphics N.V. | Negative working, heat-sensitive lithographic printing plate precursor |
US7354696B2 (en) | 2004-07-08 | 2008-04-08 | Agfa Graphics Nv | Method for making a lithographic printing plate |
US7195861B2 (en) | 2004-07-08 | 2007-03-27 | Agfa-Gevaert | Method for making a negative working, heat-sensitive lithographic printing plate precursor |
US7425405B2 (en) | 2004-07-08 | 2008-09-16 | Agfa Graphics, N.V. | Method for making a lithographic printing plate |
EP1904305B1 (fr) | 2005-06-17 | 2009-06-24 | Agfa Graphics Nv | Procédé de fabrication d'un précurseur de plaque d'impression lithographique en négatif |
DE602005008434D1 (de) * | 2005-09-27 | 2008-09-04 | Agfa Graphics Nv | Verfahren zur Herstellung einer lithographischen Druckplatte |
EP3121008B1 (fr) * | 2015-07-23 | 2018-06-13 | Agfa Nv | Précurseur de plaque d'impression lithographique comprenant de l'oxyde de graphite |
WO2019039074A1 (fr) * | 2017-08-25 | 2019-02-28 | 富士フイルム株式会社 | Plaque originale d'impression lithographique négative et procédé de fabrication d'une plaque d'impression lithographique |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1084070A (en) | 1960-08-05 | 1967-09-20 | Kalle Ag | Process and material for the preparation of planographic printing plates |
DE3717654A1 (de) | 1987-05-26 | 1988-12-08 | Hoechst Ag | Verfahren zur elektrochemischen aufrauhung von aluminium fuer druckplattentraeger |
DE4001466A1 (de) | 1990-01-19 | 1991-07-25 | Hoechst Ag | Verfahren zur elektrochemischen aufrauhung von aluminium fuer druckplattentraeger |
GB9110417D0 (en) | 1991-05-14 | 1991-07-03 | Du Pont Howson Ltd | Improvements in or relating to the formation of images |
DE4134143A1 (de) | 1991-10-16 | 1993-06-24 | Hoechst Ag | Verfahren zur herstellung von flachdruckformen und danach hergestellte flachdruckformen |
GB9326150D0 (en) | 1993-12-22 | 1994-02-23 | Alcan Int Ltd | Electrochemical roughening method |
DE4417907A1 (de) | 1994-05-21 | 1995-11-23 | Hoechst Ag | Verfahren zur Nachbehandlung von platten-, folien- oder bandförmigem Material, Träger aus derartigem Material und seine Verwendung für Offsetdruckplatten |
DE4423140A1 (de) | 1994-07-01 | 1996-01-04 | Hoechst Ag | Hydrophiliertes Trägermaterial und damit hergestelltes Aufzeichnungsmaterial |
EP0770497B1 (fr) * | 1995-10-24 | 2002-04-03 | Agfa-Gevaert | Procédé pour la fabrication d'une plaque lithographique avec développement à l'eau |
EP0773113B1 (fr) * | 1995-11-09 | 2000-05-24 | Agfa-Gevaert N.V. | Elément d'enregistrement thermosensible et méthode pour la fabrication d'un cliché lithographique utilisant cet élément |
EP0773112B1 (fr) * | 1995-11-09 | 2001-05-30 | Agfa-Gevaert N.V. | Elément d'enregistrement thermosensible et méthode pour la fabrication d'un cliché pour l'imprimerie utilisant cet élément |
EP0839647B2 (fr) * | 1996-10-29 | 2014-01-22 | Agfa Graphics N.V. | Procédé de fabrication d'une plaque d'impression lithographique à prise d'encre améliorée |
EP0881096B1 (fr) * | 1997-05-27 | 2001-10-17 | Agfa-Gevaert N.V. | Elément d'enregistrement thermosensible et procédé pour la fabrication de plaques lithographiques utilisant cet élément |
EP1080884B1 (fr) * | 1999-08-31 | 2003-11-12 | Agfa-Gevaert | Plaque lithographique sans traitement avec une nanostructure bien définie |
-
2002
- 2002-02-12 EP EP20020100128 patent/EP1243413B1/fr not_active Expired - Lifetime
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