CN100537260C - Printing plate precursor of negative thermal lithographic printing containing smooth aluminium carrier - Google Patents
Printing plate precursor of negative thermal lithographic printing containing smooth aluminium carrier Download PDFInfo
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- CN100537260C CN100537260C CNB2003101026087A CN200310102608A CN100537260C CN 100537260 C CN100537260 C CN 100537260C CN B2003101026087 A CNB2003101026087 A CN B2003101026087A CN 200310102608 A CN200310102608 A CN 200310102608A CN 100537260 C CN100537260 C CN 100537260C
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- lithographic
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- 238000007639 printing Methods 0.000 title claims abstract description 105
- 239000002243 precursor Substances 0.000 title claims abstract description 49
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 title abstract description 10
- 239000004411 aluminium Substances 0.000 title description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 25
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 25
- 230000003746 surface roughness Effects 0.000 claims abstract description 12
- 230000005660 hydrophilic surface Effects 0.000 claims abstract 10
- 238000000034 method Methods 0.000 claims description 49
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 30
- 238000007788 roughening Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000011324 bead Substances 0.000 claims description 10
- 238000003384 imaging method Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- -1 aliphatic aldehydes Chemical class 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 229920001519 homopolymer Polymers 0.000 claims description 8
- 239000000975 dye Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 229940124530 sulfonamide Drugs 0.000 claims description 2
- 150000003456 sulfonamides Chemical class 0.000 claims description 2
- 238000006277 sulfonation reaction Methods 0.000 claims description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000011282 treatment Methods 0.000 claims description 2
- 230000009183 running Effects 0.000 abstract description 6
- 239000000976 ink Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 30
- 239000000463 material Substances 0.000 description 26
- 238000002360 preparation method Methods 0.000 description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- 230000008569 process Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000010410 layer Substances 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- 238000002679 ablation Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000002848 electrochemical method Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 241001479434 Agfa Species 0.000 description 3
- 239000004793 Polystyrene Substances 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
- 230000008021 deposition Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229920001600 hydrophobic polymer Polymers 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 230000010148 water-pollination Effects 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 210000001138 tear Anatomy 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 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
- 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
- 229920000742 Cotton Polymers 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
- 239000004115 Sodium Silicate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical group [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229940053009 ethyl cyanoacrylate Drugs 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical group COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 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
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000767 polyaniline Polymers 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
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000837 restrainer Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004065 semiconductor Substances 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
- 230000003595 spectral effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000008542 thermal sensitivity Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Abstract
The present invention is printing plate precursor for negative planography. The printing plate precursor includes surface roughened and anode oxidized aluminum carrier with hydrophilic surface and thermosensitive coating on the hydrophilic surface. The coating contains hydrophobic thermoplastic polymer grains, which may be heated to coagulate to form hydrophobic in the coating. The carrier features that it has surface roughness expressed with Ra less than 0.45 micron. The smooth surface makes it possible to utilize the printing plate precursor in preparing planography plate with long running period.
Description
Technical field
The present invention relates to the thermal lithographic printing plates precursor of the non-ablation of a kind of negativity, plate precursor contain with the low surface roughness be feature through surface roughening and anodised alumina supporter, the invention still further relates to the method for making lithographic plate and use described precursor to carry out lithographic method.
Background technology
In lithographic printing, so-called printing original edition plate for example galley is installed on the machine barrel of printing machine.Forme carries lithographic image in its surface, by printing ink being coated on the described image, then printing ink being transferred to from master and is accepted material and obtain printing copy, accepts normally paper of material.In common what is called " wets " lithographic printing, provide printing ink and moisture fountain solution (be also referred to as and soak liquid) to lithographic image, image is by (or the hydrophobic of oleophylic, promptly accept printing ink, repel water) zone and hydrophilic (or hate oil, promptly accept water, repel printing ink) the zone composition.In so-called " anhydrous offset lithography " printing, lithographic image by the zone of accepting printing ink and the zone of not gluing printing ink (repulsion printing ink) form, and in anhydrous offset lithography process, only printing ink is offered master.
Printing original edition plate generally obtains to film (CtF) method by so-called computer, step before the wherein various printings, for example font selection, scanning, color separation, screening, collection, layout and justifying are finished with digitizing solution, and use the image setting device that the selection of each color is changed on the film of Plate making printing.After processing, film is used to be called the exposure of the image forming material of plate precursor as mask, has obtained being used as the galley of master after the plate-making.Since about nineteen ninety-five, so-called " computer is to forme " method (CtP) has caused very big interest.This method is also referred to as " direct-to-plate ", walks around the preparation of film, because it directly transfers to plate precursor by so-called version setting apparatus with digital document.
Particularly,, therefore be widely used in the CtP method owing to their sunlight stability to the heat version of heat or infrared ray responsive.This hot material can still, preferably contain the compound that the light that will absorb changes into heat by the exposure of directly being heated of for example thermal print head in the material, and therefore is suitable for use laser instrument, and is special in being that infra-red laser diode exposes.The heat that produces with the formation method exposure causes (physics) chemical process, for example ablation, polymerization, because crosslinked polymer and do not dissolve, the particle of decomposition or thermoplastic polymer latex condenses, behind optional mask-making technology, obtained lithographic image.The ablation that many hot plate materials cause based on heating.The problem of the version of ablating is that the fragment that produces is difficult to remove the exposure optics that this may disturb printing process or may pollute edition setting apparatus.Therefore, this version of ablating need be removed the processing step of fragment from exposing material.
EP-A 770 494 discloses a kind of exposure image method, wherein image forming material contains the image recording layer of the thermoplastic polymer particles of hydrophilic adhesive, the compound that light can be converted into heat and hydrophobic, cause polymer beads to condense and the exposure area is changed into the hydrophobic phase by imaging exposure, this hydrophobic defines the printing zone of printing original edition plate mutually.Need not any additional treatments after the exposure, printing machine is entry into service immediately, because in the printing machine operation process, by the interaction of fountain solution and printing ink, this layer is developed.In the ten or 20 initial commentaries on classics of printing machine, remove from carrier the non-exposed area, defines the non-printing zone of version thus.Therefore, the plate-making of the wet-chemical of these materials is " hiding " for the user, and plate-making is finished in the printing machine starting process.For example EP-A 770 497 and US 6,001,536 have described the similar material water to other prior art document or liquid, aqueous (machine is outer) develops.
Up to now, it is the imaging mechanism of the non-ablation that triggers of unique heat that the polymer beads that causes of heating condenses, and this imaging mechanism need not the plate-making step of independent use alkali electroless reagent and satisfies all requirement (Agfa that make the high quality printing plate material
).The various improvement of this material are at for example EP-A773 112; 774 364; 802 457; 816 070; 849 090; 849 091; 881 095; With 931 647 in description is arranged.Yet, according to heating cause polymer beads condense the operation the prior art material all be not suitable for making the galley that can be provided high service cycle in printing process.Restriction is generally 25 000 printing copies to maximum service cycle because the printing quality that the image wearing and tearing cause is degenerated.And the limited mechanical robustness of material (scraping sensitivity) and for the chemical reagent of printing machine for example the limited chemical resistance of version cleaning agent, bed course cleaning agent and fountain solution additive caused the above-mentioned low printing durability of this version.
Summary of the invention
The hot stamping brush plate precursor that the purpose of this invention is to provide a kind of non-ablation, this plate precursor does not need the independent step of utilizing the plate-making of alkali electroless reagent, and this plate precursor has high service cycle and satisfies many other requirements of lithographic printing plate material.This purpose is accomplished by coating temperature-sensitive coating on the smooth alumina supporter of for example claim 1 definition.Smooth alumina supporter carries out work for the thermoplastic polymer particles thermic according to hydrophobic condenses version provides higher service cycle, this effect is very surprising: a kind of smooth surface, the arithmetic mean of instantaneous value Ra that it is characterized in that the centre line roughness degree is less than 0.45 μ m, and why it has obviously reduced the wearing and tearing of image in printing process also clearly is not familiar with.Those skilled in the art can think: rough surface can be bonding with the polymer beads of cohesion better than smooth surface.Yet, observed opposite result, comprise having be provided higher service cycle unexpectedly as the material of smooth carrier of the Ra value of definition herein.
Preferable material of the present invention can provide a kind of lithographic printing original, and this lithographic printing original can be used at least 30 000 of printing machine runnings, more preferably at least 60 000 copies, and can't see the wearing and tearing of image.Best embodiment even can make printing machine running more than 100 000 copies.
The concrete feature of the preferred embodiments of the invention is listed in the dependent claims.The present invention further advantage and embodiment will become obvious by following explanation.
Detailed description of the invention
The carrier of plate precursor of the present invention be a kind of have water-wetted surface through surface roughening and anodised alumina supporter, it is characterized in that low surface roughness, surface roughness is expressed as the arithmetic mean of instantaneous value (Ra) of centre line roughness degree, is also referred to as CLA (center line average values) sometimes.Ra used herein has definition in ISO 4287/1 (=DIN 4762) and list of references wherein.Here Bao Gao Ra value is according to ISO 4288 and list of references wherein, use has (optics profile method also be known, with numeric ratio that optical method record with number system ground that ISO method record higher) of the contact gauge head at very thin tip by mechanical profile method measurement.The device that is used for measure R a is the Talysurf 10 of Taylor Hobson Co., Ltd.
The Ra value through the water-wetted surface of surface roughening and anodised alumina supporter that is used for material of the present invention is lower than 0.45 μ m, preferably is lower than 0.40 μ m, even more preferably less than 0.30 μ m.Have water-wetted surface through surface roughening and anodised alumina supporter, surface characteristics is described low Ra value, abbreviates " smooth carrier " here as.The lower limit of Ra value is 0.05 μ m, preferred 0.1 μ m.
Aluminium lithographic support surface roughening and anodized are well-known.The alumina supporter that is used for the surface roughening of material of the present invention preferably carries out the carrier of surface roughening with electrochemical method.The acid that is used for surface roughening can be nitric acid for example.The acid that is used for surface roughening preferably contains hydrochloric acid.Also can use for example mixture of hydrochloric acid and acetate.
With electrochemical surface roughening and anodic oxidation parameter, for example the character of electrode voltage, acidic electrolysis bath and concentration or power consumption are a side, and according to Ra and the anode weight (Al that forms on the aluminium surface
2O
3, g/m
2) the lithographic quality that obtains is well-known for the relation between the opposing party.Can in being published in the article " Management of Change in the Aluminium PrintingIndustry " of ATBMetallurgie Journal, F.R.Mayers find about the more detailed description that concerns between various manufacturing parameters and Ra or the anode weight.Therefore, the technical staff fully knows and is producing the various parameters that smooth surface needs on the alumina supporter of roughening or obtain the setting of the various parameters that given anode weight needs in the alumilite process process.According to the present invention, for given roughness Ra, by forming greater than 2.5g/m at water-wetted surface
2Aluminium oxide, more preferably greater than 3.0g/m
2Or even 3.5g/m
2Aluminium oxide, can reach higher service cycle.
Can carry out post processing to improve its surperficial hydrophily through surface roughening and anodised alumina supporter.For example, alumina supporter can be by, handling its surface with sodium silicate solution and carry out silication for example under 95 ℃ at high temperature.Perhaps, can carry out phosphatization and handle, this relates to phosphate solution handles alumina surface, also can contain inorganic fluoride in the phosphate solution.In addition, alumina surface can use organic acid and/or its salt, as carboxylic acid, hydroxycarboxylic acid, sulfonic acid or phosphonic acids, or their salt, for example succinate, phosphate, phosphonate, sulfate and sulfonate clean.Preferred citric acid or the citrate solution of using cleans.This processing can at room temperature be carried out or carry out under about 30 to 50 ℃ high-temperature slightly.Another post processing relates to bicarbonate solution cleans alumina surface.Further, the alumina surface acetal that can form with the aliphatic aldehydes reaction of the sulfuric ester of polyvinylphosphonic acid, polyvinyl methylphosphonic acid, polyethylene alcohol phosphate, polyvinyl sulfonic acid, polyethylene benzene sulfonic acid, polyvinyl alcohol and polyvinyl alcohol and sulfonation is handled.In addition, obviously one or more of these post processings can carry out separately or in conjunction with carrying out.Handle more detailed description at GB-A-1 084 070 about these, DE-A-4 423 140, and DE-A-4 417 907, and EP-A-659 909, and EP-A-537 633, and DE-A-4001 466, and EP-A-292 801, provide among EP-A-291 760 and the US-P-4 458005.
The coating that provides on the carrier is a thermal sensitivity, has therefore obtained a kind of plate precursor that can operate some hrs in normal operating illumination condition (daylight, fluorescent lamp).Coating comprises image recording layer, and this layer contains the thermoplastics type's of hydrophobic polymer beads.The instantiation of suitable hydrophobic polymer has, for example polyethylene, poly-(vinyl chloride), poly-((methyl) acrylic acid formicester), poly-((methyl) ETHYL CYANOACRYLATE), poly-(1,1-dichloroethylene), poly-(methyl) acrylonitrile, poly-(VCz), polystyrene or its copolymer.According to embodiment preferred, thermoplastics type's polymer contains the polystyrene of at least 50 weight %, more preferably contains the polystyrene of at least 60 weight %.Enough in order to obtain to mechanical failure and printing machine chemical reagent, the resistance of the hydrocarbon that uses in the cleaning agent of version for example, thermoplastic polymer preferably contains at least 5 weight %, the more preferably nitrogenous monomeric unit of at least 30 weight % or to be equivalent to feature be solubility parameter greater than the unit of 20 monomer, for example (methyl) acrylonitrile or contain sulfonamide and/or the monomeric unit of phthalimide side group.
Other suitable example of this nitrogenous monomeric unit is disclosed in the European Patent Application No. 01000657 of application on November 23 calendar year 2001.A kind of instantiation of the thermoplastic polymer of hydrophobic is (methyl) acrylonitrile and/or cinnamic homopolymers or copolymer, for example by styrene and acrylonitrile unit with 1:1 to 5:1 (styrene: the copolymer that weight ratio acrylonitrile) is formed.The ratio of 2:1 or 3:2 has obtained fabulous result.
The weight average molecular weight range of thermoplastic polymer particles can from 5,000 to 1,000,000g/mol.The number average bead diameter of the particle of hydrophobic preferably is lower than 200nm, more preferably from 10 to 100nm.The content of the thermoplastic polymer particles of hydrophobic in image recording layer preferably at 20 weight % between the 65 weight %, more preferably at 25 weight % between the 55 weight %, most preferably at 30 weight % between the 45 weight %.
The thermoplastic polymer particles of hydrophobic can be used as a kind of dispersion and is provided in the aquifer coating liquid of image recording layer, and can be by disclosed method preparation among the US 3,476,937.Another method that is particularly suitable for preparing the aqueous dispersion of thermoplastic polymer particles comprises:
-the thermoplastic polymer of dissolving hydrophobic in water-fast organic solvent,
-disperse in water or in the water-bearing media solution obtain like this and
-remove organic solvent by evaporation.
Image recording layer can further contain hydrophilic adhesive, for example the homopolymers of vinyl alcohol, acrylamide, NMA, methylol methacrylamide, acrylic acid, methacrylic acid, hydroxyethyl acrylate, methacrylic acid hydroxyethyl ester and copolymer or maleic anhydride/methoxy ethylene copolymer.(being total to) polymer that uses or the hydrophily of (being total to) polymeric blends preferably are equal to or higher than the hydrophily of polyvinyl acetate, this polyvinyl acetate at least hydrolysis to 60 percetages by weight, preferred 80 percetages by weight.The adhesive that preferably has carboxyl side group, for example poly-(methyl) acrylic acid.
Image recording layer can also contain other composition, for example other adhesive, surfactant, colouring agent, development restrainer or promoter, and particularly one or more can transform into infrared ray the compound of heat.
Useful especially light-thermal transition compound is for example to the oxide of the dyestuff of sensitive for infrared radiation, carbon black, metal carbides, boride, nitride, carbonitride, signal bronze structure and conducting polymer dispersion for example polypyrrole, polyaniline or polythiophene dispersion.The preferred anionic cyanine dye.Colouring agent has preferably formed the dyestuff or the pigment of visible image after plate-making.
Coating can also contain one or more extra play near image recording layer.Above-mentioned extra play can be the promotion adhesion layer between image recording layer and the carrier for example; Or contain one or more above-mentioned light-absorption layers that infrared ray can be transformed into the compound of heat; Or protective layer, protective layer is removed in the plate-making process.
Material of the present invention is suitable for exposing outside the machine and on the machine.Plate precursor of the present invention is exposed under heat that for example utilizes thermal print head, LEDs or infrared laser to produce or infrared ray.Preferably, use emission wavelength at about 700 laser instruments, for example semiconductor laser diode, Nd:YAG or Nd:YLF laser instrument to the near infrared light of about 1500nm scope.The laser power that needs depends on the sensitivity of image recording layer, and the pixel time of staying of laser beam, the resolution ratio of sweep speed and exposure instrument (is the number of the addressable pixel of per unit air line distance, represents through dots per inch commonly used or dpi; General value: 1000-4000dPi), the pixel time of staying of laser beam, (modern version setting apparatus was at the 1/e of maximum intensity by spot diameter
2Generally be worth under the condition: 10-25 μ m) determine.General two kinds of laser explosure instruments that use are: interior drum (ITD) and external drum (XTD) version setting apparatus.The general features that is used for the ITD version setting apparatus of heat version is to have up to the very high sweep speed of 500 meter per seconds and the laser power of several watts of needs.About 200 milliwatts of the general laser power of XTD version setting apparatus that are used for the heat version are moved under lower sweep speed, for example the sweep speed of 0.1 to 10 meter per second to about 1 watt.
Owing in the step of exposure process, produce heat, the thermoplastic polymer particles fusion of hydrophobic or condense so that forms corresponding to galley inking hydrophobic phase partly.The condense cohesion that may be caused because of heating by thermoplastic polymer particles, softening or fusing produces.The adiabatic condensation temperature of thermoplasticity hydrophobic polymer particle does not have the concrete upper limit, yet this temperature should fully be lower than the decomposition temperature of polymer beads.Adiabatic condensation temperature is preferably hanged down at least 10 ℃ than the temperature that polymer beads takes place to decompose.Adiabatic condensation temperature preferably is higher than 50 ℃, more preferably is higher than 100 ℃.
After the exposure, material is developed." development " here used as identical term with " plate-making ".Can contain aqueous-favoring liquid and develop by provide a kind of to coating, remove coating from the non-exposed area of carrier thus.Described liquid can be selected from water, moisture liquid, glue, fountain solution and single liquid printing ink.According to a technical scheme, the development of material preferably at first provides fountain solution that printing ink is provided subsequently by fountain solution and/or printing ink are provided.This method preferably is used in combination with step of exposure on the machine.Another kind of developing method also is suitable for developing on the machine, particularly is suitable in anhydrous lithographic offset printing machine, and this method is developed by single liquid printing ink is provided.The single liquid printing ink that is suitable for method of the present invention is at US 4,045,232 and US 4,981,517 in describe.Describe as WO 00/32705, suitable single liquid printing ink comprises the printing ink phase, is also referred to as hydrophobic mutually or the oleophylic phase, with polyalcohol mutually.Can in the EP-A no.01000633 of application on November 15 calendar year 2001, obtain about the more situation of developing with single liquid printing ink.
When the version outside machine was exposed in the setting apparatus, material can be undertaken making a plate on the machine by above-mentioned provide printing ink and/or fountain solution, perhaps for example by providing water, liquid, aqueous or sol solution machine to make a plate outward.Sol solution is normally a kind of liquid, aqueous, and it contains one or more lithographic image that can protect galley in case the surface protection compound that stains or damage.The suitable example of above-claimed cpd has film-forming hydrophilic polymer or surfactant.Can in the EP-Ano.02100226 of application on March 6th, 2002, obtain about the more situation of developing with sol solution.
After the development, can dry and baking version.Version can be carried out drying or dry at bake process itself before baking.Bake process can carry out under the temperature of the adiabatic condensation temperature that is higher than thermoplastic polymer particles, for example toasts 5 to 40 minutes between 100 ℃ and 230 ℃.For example can under 230 ℃ of temperature, toast 5 minutes, toast 10 minutes under 150 ℃ of temperature or under 120 ℃ of temperature, toasting 30 minutes through the version of exposure and development.Preferred baking temperature is higher than 60 ℃.Baking can be carried out in common hot-blast oven, perhaps can be undertaken by the light irradiation that is used in the radiation of infrared region or ultra-violet (UV) band spectral region.
Embodiment
Among the embodiment hereinafter, be defined as service cycle (run length) because image weares and teares, the degeneration of 60% panel of high-quality image (200 lpi) surpasses the number of 5% o'clock printing copy.Unless indicate in addition, whole versions hereinafter described are to make a plate on the machine, and plate-making is by in initial ten to 15 the turning in the journey and provide printing ink and fountain solution to carry out to version of printing machine.
Embodiment 1 (contrast) and 2 (the present invention)
Preparation lithographic support 1
Flake aluminum that 0.30mm is thick immerses in 60 ℃ of aqueous solution that contain 40g/l NaOH and to wash for 2 seconds with demineralized water then to remove oil stain 8 seconds.Then 33 ℃ temperature, 130A/dm
2Current density under use alternating current that thin slice is carried out 15 seconds of surface roughening with electrochemical method in the aqueous solution of the aluminum sulfate (18 hydrate) of hydrochloric acid that contains 12g/l and 38g/l.After washing for 2 seconds with demineralized water,, cleaned for 2 seconds down to remove stain with demineralized water at 25 ℃ then with 70 ℃ of 4 seconds of aqueous solution etching that contain 155g/l sulfuric acid.Subsequently at 45 ℃ of temperature and 22A/dm
2In the aqueous solution that contains 155g/l sulfuric acid, carry out 13 seconds of thin slice anodic oxidation under the current density, cleaned for 2 seconds with demineralized water then, continue to handle for 10 seconds with 40 ℃ 4g/l polyvinylphosphonic acid solution again, washed for 2 seconds with 20 ℃ of demineralized waters, then drying.
Obtained carrier like this, it is characterized in that surface roughness Ra is 0.46 μ m, and anode weight has been 2.90g/m
2Al
2O
3
Preparation lithographic support 2
Use above-mentioned identical method, be respectively 90A/dm and preparation condition is a current density in surface roughening and the anode oxidation process
2And 30A/dm
2Obtained carrier like this, it is characterized in that surface roughness Ra is that 0.22 μ m and anode weight are 4.0g/m
2Al
2O
3
Preparation and testing of printed version 1 and 2
Then it is coated on above-mentioned lithographic support 1 and 2 preparation contrast plate precursor 1 and plate precursor of the present invention 2 respectively by the preparation coating composition.
By moisture coating solution image recording layer is coated on the above-mentioned lithographic support, wet thickness is 30g/m
2After the drying, this layer is by 600mg/m
2With the styrene of the stable average grain diameter 65nm of anion wetting agent and copolymer, the 60mg/m of acrylonitrile (weight ratio 60/40)
2Infrared ray absorbing dyestuff I and 120mg/m
2Polyacrylic acid is (available from the Glascol D15 of Allied Colloids, molecular weight 2.7x10
7Gram/mole) forms.
Dyestuff I
The plate precursor that obtains like this is with Creo Trendsetter (available from Creo, Burnaby, the version setting apparatus of Canada) exposure, at 330mJ/cm
2With operate under the 150rpm condition.After the imaging, version is contained on the MO printing machine (available from Heidelberger Druckmaschinen AG), 4% the Combifix XL that uses K+E800 printing ink and contain 10% isopropyl alcohol begins to print as fountain solution.
After finishing 25 000 printed matters, the image of the version that is obtained by plate precursor 1 begins to degenerate, and after the service cycle through 30 000 printed matters, the image wearing and tearing have surpassed standard defined above.The version that is obtained by plate precursor 2 does not show any wearing and tearing, even does not show wearing and tearing when 100 000 printed matters are finished in the printing machine running when stopping after yet.
Embodiment 3 (we are bright) and 4 (contrasts)
Preparation lithographic support 3
Thickness is 0.30mm, and width is that the aluminium matter continuous coiled material of 500mm immerses 38 ℃ and contains in the 10.4g/l sodium hydrate aqueous solution and to remove oil stain 35 seconds, washes for 30 seconds with demineralized water then.Then 29 ℃ temperature, use alternating current that this coiled material is carried out 30 seconds of surface roughening with electrochemical method under the current density of 826A/dm2 in the nitration mixture aqueous solution of the acetate of hydrochloric acid that contains 9.5g/l and 21g/l.The center line average roughness Ra of the carrier that obtains like this is 0.24 μ m.After washing for 30 seconds with demineralized water, remove stain 35 seconds, cleaned for 30 seconds with demineralized water then with 43 ℃ of aqueous solution etchings that contain 124g/l phosphoric acid.Subsequently, use DC voltage in 1173A/m
2In containing 48.5 ℃ of aqueous solution of 137g/l sulfuric acid, carry out 30 seconds of aluminium flake anodic oxidation under the current density condition, up to forming 3.4g/m
2Al
2O
3Anodic oxide coating cleaned for 30 seconds with demineralized water then, handled for 15 seconds with 52 ℃ the 2.2g/l polyvinylphosphonic acid solution continuation that contains again, washed for 30 seconds with demineralized water, and is dry then.
Preparation lithographic support 4
Use the method identical, but current density is 2125A/dm in the process of surface roughening with carrier 3
2The carrier that obtains like this is characterised in that surface roughness Ra is 0.53 μ m.Anode weight is identical with carrier 3.
Preparation and testing of printed version 3 and 4
The same combination that is used to prepare plate precursor 1 and 2 by coating as mentioned above prepares plate precursor 3 and 4.Exposure, plate-making also is identical with printing process on the machine.
Version 4 service cycle is 30 000 copies, and version 3 is when service cycle, test stopped, and does not show any image wearing and tearing after having finished 50 000 copies.
Embodiment 5-9
Preparation lithographic support 5-9
Thickness is 0.30mm, and width is that the aluminium matter continuous coiled material of 500mm immerses in 39 ℃ of aqueous solution that contain 10g/l NaOH and to remove oil stain 35 seconds, washes for 30 seconds with demineralized water then.
Then 30 ℃ temperature, use alternating current that this aluminium flake is carried out 30 seconds of surface roughening with electrochemical method under the current density shown in the table 1 in the nitration mixture aqueous solution of the acetate of hydrochloric acid that contains 8.1g/l and 21.7g/l.After washing for 30 seconds with demineralized water, remove stain 35 seconds, cleaned for 30 seconds with demineralized water then with 43 ℃ of aqueous solution etchings that contain 128g/l phosphoric acid.Subsequently, use DC voltage under the current density shown in the table 1, in containing 50 ℃ of aqueous solution of 154g/l sulfuric acid, carry out 30 seconds of aluminium flake anodic oxidation, cleaned for 30 seconds with demineralized water then, handled for 15 seconds with 53 ℃ the 2.45g/l polyvinylphosphonic acid solution continuation that contains again, washed for 30 seconds with demineralized water, dry then.
Preparation and testing of printed version 5-9
To be coated to respectively with the above-mentioned same combination that is used to prepare plate precursor 1 and 2 and prepare plate precursor 5-9 on the carrier 5-9.Exposure, plate-making also is identical with printing process on the machine.
Table 1 has provided the current density that is used for surface roughening (GR) and anodic oxidation (AN), the surface roughness Ra of lithographic support 5-9 and anode weight (AW) and edition 5-9 service cycles that reach.
Table 1
| Embodiment number | Electric current GR (A/m 2) | Ra (μm) | Electric current AN (A/m 2) | AW (g/m 2) | Service cycle |
| 5 (contrasts) | 2740 | 0.53 | 2350 | 4.8 | 11 000 |
| 6 (inventions) | 1300 | 0.28 | 2350 | 4.8 | 55 000 |
| 7 (inventions) | 1300 | 0.28 | 1750 | 3.5 | 50 000 |
| 8 (inventions) | 1300 | 0.28 | 2900 | 6.3 | 70 000 |
| 9 (inventions) | 1000 | 0.21 | 2350 | 4.8 | >90 000 |
Embodiment 5,6 and 9 digital proof are for certain anode weight (4.8g/m in the last table
2), Ra reduces, and increase service cycle significantly.For certain Ra value (embodiment 6-8:0.28 μ m), improve anode weight and obtained further to improve.Version 9 also shows when printing machine shuts down, still do not have image to wear and tear after having finished 90 000 copies.
Embodiment 10-12
Preparation plate precursor 10-11
Use lithographic support and the coating identical with embodiment 1 and 2 respectively, condition is that thermoplastic polymer is that particle mean size is the styrene homopolymers of 70nm.
Preparation and testing of printed version 10-12
Exposure of describing with the foregoing description and method for platemaking be respectively by precursor 10 and 11 preparation versions 10 and 11, and condition is to go up 4% the Combifix XL that uses K+E800 printing ink and contain 10% isopropyl alcohol at GTO printing machine (Heidelberger Druckmaschinen) to carry out on the machine plate-making as fountain solution and test service cycle.Version 12 is used the same procedure preparation of version 10 and 11 by precursor 2.
Table 2
| Embodiment number | Ra(μm) | Polymer | Service cycle |
| 10 (contrasts) | 0.46 | Styrene homopolymers | 21 500 |
| 11 (inventions) | 0.22 | Styrene homopolymers | 85 000 |
| 12 (inventions) | 0.22 | Styrene/acrylonitrile copolymer | >10 0000 |
Above-mentioned digital proof by with nitrogenous unit for example acrylonitrile introduce in the thermoplastic polymer of hydrophobic and can further improve service cycle.
Embodiment 13-15
The chemical resistance test of galley 10-12
The version 10-12 of preparation is as mentioned above carried out three chemical resistance tests.Test 1: the version of imaging method exposure is installed on the GTO printing machine (Heidelberger Druckmaschinen), and 4% the Combifix XL that uses K+E800 printing ink and contain 10% isopropyl alcohol starts printing machine as fountain solution, 500 copies of printing machine operation.(Meter-X=is available from ABCChemicals ComP.Ltd., the cylinder washing lotion based on hydrocarbon of UK to use two kinds of typical printing machine liquid then; Normakleen=is available from the version cleaning agent based on petroleum distillate of Agfa) handle the Printing Zone of each edition, use the cotton yarn sheet to immerse corresponding liquid, rub from the teeth outwards then; Damage to processing region is assessed (does not have the image corrosion referring to table 3:0=; The strong image corrosion of X=; The XX=image is removed fully).
Table 3
Test 2: the version of imaging method exposure is installed on the GTO printing machine (Heidelberger Druckmaschinen), and 4% the Combifix XL that uses K+E800 printing ink and contain 10% isopropyl alcohol starts printing machine as fountain solution, 500 copies of printing machine operation.Then the same liquid that uses in the test 1 is placed on the printing zone of version dry 4 minutes then.And then begin in addition 200 copies (in test 2, replacing testing 1 friction) of printing with printing.For the second time behind the operating printing machine, the zone of crossing with liquid handling assessed (does not have the image corrosion referring to table 4:0=; The strong image corrosion of X=; The XX=image is removed fully).
Table 4
Test 3: the coating of the version of the imaging method of mechanically swiping in non-exposed area exposure.Version is installed in as testing on 1 and 2 printing machines of describing then, prints 1000 copies.Stop printing machine, be evaluated at whether to see scratch (because scraping causes China ink on non-image part) on the last printing copy
Table 5
| The version number | Ra(μm) | Polymer | Scratch |
| 10 (contrasts) | 0.46 | Styrene homopolymers | Seriously |
| 11 (inventions) | 0.22 | Styrene homopolymers | Tiny |
| 12 (inventions) | 0.22 | Styrene/acrylonitrile copolymer | Do not have |
Embodiment 16 and 17
Preparation lithographic support 16
Except the surface roughening step, Overall Steps is identical with embodiment 2: use alternating current at 36A/dm
2Current density under, flake aluminum is carried out 4 seconds of surface roughening with electrochemical method in 40 ℃ of aqueous solution that contain the nitric acid of 12.4g/l and the aluminum nitrate of 67g/l (9 hydrate).The Ra value through the carrier of nitric acid surface roughening that obtains like this is 0.38 μ m.
Galley 16 and 17 preparation and test
Prepare plate precursor 16 by coating on above-mentioned carrier 16 as the same composition that embodiment 2 describes.Respectively plate precursor 16 and 2 exposures are prepared version 16 and 17, utilize Creo Trendsetter (available from Creo, Burnaby, the version setting apparatus of Canada) at 330mJ/cm
2With operate under 150 rev/mins of conditions.Version is installed on the MO printing machine (available from Heidelberger Druckmaschinen AG) after 16 and 17 imagings, and 4% the Combifix XL that uses K+E800 printing ink and contain 10% isopropyl alcohol begins printing as fountain solution.The same sample of version 16 and 17 is installed on Speedmaster 74 printing machines (SM-74 is available from Heidelberger DruckmaschinenAG), uses the Varnfount of K+E700 Novavit Speed printing ink and 4% to begin printing as fountain solution.
Table 6
| The version number | The acid that surface roughening uses | Printing machine | Ink deposition on the bed course |
| 16 (inventions) | Hydrochloric acid | MO | Do not have |
| 17 (inventions) | Nitric acid | MO | Do not have |
| 16 (inventions) | Hydrochloric acid | SM-74 | Do not have |
| 17 (inventions) | Nitric acid | SM-74 | Have |
In the running of 100 000 copies of printing machine, there is not version to demonstrate the image wearing and tearing.Version 17 (with the nitric acid surface roughening) shows ink deposition on the bed course of SM-74 in printing process, and editions 16 (with the hydrochloric acid surface roughening) are moved on SM-74, do not have ink deposition in the running of whole printing machine on bed course.
Embodiment 18 and 19
Press embodiment 2 described preparation versions 18, condition is that the version of exposure is made a plate outward with the sol solution machine, uses the RC520 oven dry glue (HWP450 processor, soak time 1 minute, room temperature) of Agfa.
Preparation version similarly 19, but after the plate-making version was toasted 2 minutes at 270 ℃.
Go up two kinds of versions of assessment at MO printing machine (Heidelberger Druckmaschinen AG), 4% the Combifix XL that uses K+E800 printing ink and contain 10% isopropyl alcohol is as fountain solution.
After finishing 150 000 printed matters, version 18 the image of baking does not begin to degenerate and the version 19 of toasting does not have the display image wearing and tearing fully.Even after finishing 300 000 printed matters, not observing version 19 has image wearing and tearing, the test of off-cycle then.
Claims (20)
1, a kind of negativity Lighographic printing plate precursor, contain:
-possess hydrophilic property surface through surface roughening and anodised alumina supporter;
-temperature-sensitive the coating that on hydrophilic surface, forms, described coating contains the thermoplastic polymer particles of hydrophobic, the condensing of the described polymer beads that causes by heating, thermoplastic polymer particles can form the hydrophobic phase in described coating;
Its characteristic is that surface roughness that hydrophilic surface represents with the arithmetic mean of instantaneous value Ra of centre line roughness degree is less than 0.45 μ m.
2, the plate precursor of claim 1, wherein the surface roughness represented with the arithmetic mean of instantaneous value Ra of centre line roughness degree of hydrophilic surface is less than 0.4 μ m.
3, the plate precursor of claim 1, wherein the surface roughness represented with the arithmetic mean of instantaneous value Ra of centre line roughness degree of hydrophilic surface is less than 0.3 μ m.
4, the plate precursor of claim 1, wherein alumina supporter contains greater than 2.5g/m at hydrophilic surface
2Aluminium oxide.
5, the plate precursor of claim 1, wherein alumina supporter contains greater than 3.5g/m at hydrophilic surface
2Aluminium oxide.
6, the plate precursor of claim 1, wherein the thermoplastic polymer of hydrophobic is (methyl) acrylonitrile and/or cinnamic homopolymers or copolymer.
7, the plate precursor of claim 1, wherein the thermoplastic polymer of hydrophobic contains sulfonamide and/or phthalimide side group.
8, the plate precursor of claim 1, wherein the temperature-sensitive coating further contains the hydrophilic polymer adhesive of being with carboxyl side group.
9, the plate precursor of claim 1, wherein the temperature-sensitive coating further contains anionic and absorbs ultrared cyanine dye.
10, the plate precursor of claim 1, wherein the temperature-sensitive coating further contains dyestuff or the pigment that absorbs visible light.
11, the plate precursor of claim 1, wherein hydrophilic surface is by with (i) organic acid and/or its salt or with (ii) polymer treatment, make its surface hydrophilic, polymer is selected from the product of the aliphatic aldehydes reaction of the sulfuric ester of polyvinylphosphonic acid, polyvinyl methylphosphonic acid, polyethylene alcohol phosphate, polyvinyl sulfonic acid, polyethylene benzene sulfonic acid, polyvinyl alcohol and polyvinyl alcohol and sulfonation.
12, the plate precursor of claim 1, wherein said hydrophobic can be accepted printing ink at least 60000 printings of offset press operation copy procedure.
13, the plate precursor of claim 1, wherein said hydrophobic can be accepted printing ink at least 100000 printings of offset press operation copy procedure.
14, a kind of method of making lithographic plate comprises step:
The plate precursor of-claim 1 is the imaging method exposure under heat or infrared ray, thereby the thermoplastic polymer particles that causes the exposure area hydrophobic condenses;
-contain aqueous-favoring liquid exposed plate is developed by providing to coating, thus remove the coating of unexposed area from carrier, and described liquid is selected from water, moisture liquid, glue, fountain solution and single liquid printing ink.
15, the method for claim 14, wherein exposure and step of developing are that plate precursor is installed on the machine barrel of offset press and carries out.
16, the method for claim 14 comprises also that wherein the plate precursor that will develop is being higher than the step of toasting processing under 60 ℃ the condition.
17, a kind of lithographic method comprises step:
-make lithographic plate according to the method for claim 14;
At least 60000 copies of lithographic plate printing that-usefulness obtains like this.
18, a kind of lithographic method comprises step:
-make lithographic plate according to the method for claim 14;
At least 100000 copies of lithographic plate printing that-usefulness obtains like this.
19, a kind of lithographic method comprises step:
-make lithographic plate according to the method for claim 16;
At least 300000 copies of lithographic plate printing that-usefulness obtains like this.
20, a kind of surface roughening and the purposes of anodised alumina supporter in the negativity Lighographic printing plate precursor, this carrier possess hydrophilic property surface and the surface roughness of representing with centre line roughness degree arithmetic mean of instantaneous value Ra less than 0.45 μ m, described purposes is to be used to improve by described plate precursor being exposed and the service cycle of the galley that obtains of developing, described plate precursor comprises a temperature-sensitive coating that forms at hydrophilic surface, this coating contains the thermoplastic polymer particles of hydrophobic, condensing of the described polymer beads that causes by heating, thermoplastic polymer particles can form the hydrophobic phase in described coating.
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|---|---|---|---|
| CNB2003101026087A CN100537260C (en) | 2003-10-25 | 2003-10-25 | Printing plate precursor of negative thermal lithographic printing containing smooth aluminium carrier |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101026087A CN100537260C (en) | 2003-10-25 | 2003-10-25 | Printing plate precursor of negative thermal lithographic printing containing smooth aluminium carrier |
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| ES2411697T3 (en) * | 2005-11-21 | 2013-07-08 | Agfa Graphics N.V. | Method of manufacturing a lithographic printing plate |
| EP2420383B1 (en) * | 2010-08-20 | 2013-10-16 | Agfa Graphics N.V. | Digital system for creating a flexographic printmaster |
| EP2871057B1 (en) * | 2013-11-07 | 2016-09-14 | Agfa Graphics Nv | Negative working, heat-sensitive lithographic printing plate precursor |
| CN108329412B (en) * | 2017-01-20 | 2019-07-02 | 中国科学院化学研究所 | A kind of polyvinyl alcohol ester benzene sulfonate and its synthetic method, printing hydrophilic version and application and galley |
| EP3441223B1 (en) | 2017-08-07 | 2024-02-21 | Eco3 Bv | A lithographic printing plate precursor |
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