CN1608862B - Positive lithographic printing plate precursor - Google Patents
Positive lithographic printing plate precursor Download PDFInfo
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- CN1608862B CN1608862B CN 200310102607 CN200310102607A CN1608862B CN 1608862 B CN1608862 B CN 1608862B CN 200310102607 CN200310102607 CN 200310102607 CN 200310102607 A CN200310102607 A CN 200310102607A CN 1608862 B CN1608862 B CN 1608862B
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- Prior art keywords
- plate precursor
- coating
- dissolution
- polymer
- hydrophilic surface
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- 239000002243 precursor Substances 0.000 title claims abstract description 40
- 239000011248 coating agent Substances 0.000 claims abstract description 52
- 238000000576 coating method Methods 0.000 claims abstract description 52
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000005660 hydrophilic surface Effects 0.000 claims abstract description 12
- 230000003746 surface roughness Effects 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims description 25
- 238000004090 dissolution Methods 0.000 claims description 22
- -1 siloxanes Chemical group 0.000 claims description 21
- 239000003112 inhibitor Substances 0.000 claims description 16
- 238000007788 roughening Methods 0.000 claims description 16
- 229910052739 hydrogen Chemical group 0.000 claims description 5
- 239000001257 hydrogen Chemical group 0.000 claims description 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000007788 liquid Substances 0.000 abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 15
- 239000000975 dye Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 229920001600 hydrophobic polymer Polymers 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 238000003384 imaging method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
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- 238000011109 contamination Methods 0.000 description 4
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- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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
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- 241001479434 Agfa Species 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- OKJFKPFBSPZTAH-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-(4-hydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O OKJFKPFBSPZTAH-UHFFFAOYSA-N 0.000 description 1
- XXYVCSHZYMXBOT-UHFFFAOYSA-N 1-benzhydryl-2,3,4,5-tetramethylbenzene Chemical compound CC=1C(=C(C(=C(C1)C(C1=CC=CC=C1)C1=CC=CC=C1)C)C)C XXYVCSHZYMXBOT-UHFFFAOYSA-N 0.000 description 1
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 1
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 1
- VLUWLNIMIAFOSY-UHFFFAOYSA-N 2-methylbenzenesulfinic acid Chemical compound CC1=CC=CC=C1S(O)=O VLUWLNIMIAFOSY-UHFFFAOYSA-N 0.000 description 1
- DAUAQNGYDSHRET-UHFFFAOYSA-N 3,4-dimethoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1OC DAUAQNGYDSHRET-UHFFFAOYSA-N 0.000 description 1
- QZYCWJVSPFQUQC-UHFFFAOYSA-N 3-phenylfuran-2,5-dione Chemical compound O=C1OC(=O)C(C=2C=CC=CC=2)=C1 QZYCWJVSPFQUQC-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 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
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- TUMJYQZANJMKGU-UHFFFAOYSA-N OC1(C(CCC(C1)C(C)C)(C(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)O)O Chemical compound OC1(C(CCC(C1)C(C)C)(C(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)O)O TUMJYQZANJMKGU-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 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
- GPVDHNVGGIAOQT-UHFFFAOYSA-N Veratric acid Natural products COC1=CC=C(C(O)=O)C(OC)=C1 GPVDHNVGGIAOQT-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 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
- 230000009471 action Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 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
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 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
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
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- ILUAAIDVFMVTAU-UHFFFAOYSA-N cyclohex-4-ene-1,2-dicarboxylic acid Chemical class OC(=O)C1CC=CCC1C(O)=O ILUAAIDVFMVTAU-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
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- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
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- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical class C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012052 hydrophilic carrier Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
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- 229940070765 laurate Drugs 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
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- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 1
- PHEDXBVPIONUQT-RGYGYFBISA-N phorbol 13-acetate 12-myristate Chemical compound C([C@]1(O)C(=O)C(C)=C[C@H]1[C@@]1(O)[C@H](C)[C@H]2OC(=O)CCCCCCCCCCCCC)C(CO)=C[C@H]1[C@H]1[C@]2(OC(C)=O)C1(C)C PHEDXBVPIONUQT-RGYGYFBISA-N 0.000 description 1
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- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
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- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention is printing plate precursor for positive planography. The printing plate precursor includes surface roughened and anode oxidized aluminum carrier with hydrophilic surface and thermosensitive lipophilic coating on the hydrophilic surface. Inside water-containing alkali developing liquid, the coating has its area exposed in heat or infrared ray with even higher dissolving ratethan un-exposed area. The printing plate precursor features that the hydrophilic surface has surface roughness expressed with Ra less than 0.45 micron and contains alumina more than 3.0 g/sq m. The smooth surface results in longer storage period.
Description
Technical field
The present invention relates to a kind of positivity Lighographic printing plate precursor of the temperature-sensitive that need handle with aqueous bases.
Background technology
The lithographic printing printing machine uses a kind of so-called printing original edition plate, for example is installed in the galley on the printing machine machine barrel.Surface at master carries lithographic image, by printing ink being coated on the described image, then printing ink being transferred to from master and is accepted material and obtain printed matter, accepts normally paper of material.In common lithographic printing, printing ink and moisture fountain solution (being also referred to as wetting solution) are offered lithographic image, image by oleophylic (or hydrophobic, 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, lithographic image is formed, and in anhydrous offset lithography process, only printing ink is offered master by the zone of accepting printing ink and sticking printing ink (repulsion printing ink) zone.
Generally to be the image forming material that will be called plate precursor obtain through exposure and plate-making with formation method printing original edition plate.Typical positivity plate precursor comprises the coating of hydrophilic carrier and oleophylic, and coating is not soluble in moisture alkaline-based developer under unexposed state, and being exposed to then becomes behind the ray dissolves in developer solution.Pass the photosensitive imaging material that film masks (usually said preceding light sensitive plate) is exposed with ultraviolet ray except well-known being suitable for, it is very universal that the plate precursor of temperature-sensitive has also become.This hot material has the advantage of sunlight stability, is used in particular for so-called computer master making method, and plate precursor directly exposes in this method, does not promptly use film masks.Material is exposed under heat or the infrared ray, and the heat of generation causes (physics) chemical process, for example ablation, polymerization, because crosslinked polymer and do not dissolve, heat the solubilization that causes or the particle of thermoplastic polymer latex condenses.US 6,242,156 and EP-A 884 647 in the example of this heat version is disclosed, the effect of the surface roughness of alumina supporter wherein also has been discussed.
The shelf life that a specific problem relevant with hot plate precursor is coating is limited.When particularly storing at high temperature, this high temperature is inevitably in truck, ship or the like transportation, and version may demonstrate serious harmonious colours (having accepted glossy black in non-pattern area).
Summary of the invention
One aspect of the present invention provides improved positivity thermal lithographic printing plates precursor of a kind of shelf life.This purpose is to realize that by the material of claim 1 characteristics that the material of claim 1 has are through the low surface roughness of surface roughening and anodised alumina supporter with greater than 3.0g/m
2Al
2O
3Anode weight, this has improved the shelf life beyond expectationly.Defined the specific embodiments of invention in the dependent claims.
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=DIN4762) and wherein the list of references at ISO 4287/1.Here Bao Gao Ra value is according to ISO 4288 and list of references wherein, (the optics profile method also is known, and is higher with the number system ground that the ISO method records with the numeric ratio that optical method records) that use has the contact gauge head at very thin tip to measure by mechanical profile method.The device that is used for measure R a is the Talysurf 10 of Taylor Hobos Co., Ltd.
Be used for material of the present invention through surface roughening and anodised alumina supporter, the Ra value of its hydrophilic surface is lower than 0.40 μ m, preferably is lower than 0.30 μ m, even more preferably less than 0.25 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.
The surface roughening of aluminium lithographic support and anodized are well-known.What be used for material of the present invention preferably uses the carrier of electrochemical method surface roughening through the alumina supporter of surface roughening.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 that a side and face are 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.In more detail can be at " the Managementof Change in the Alumimium Printing Industry " of document F.R.Mayers about the explanation of the relation between various manufacturing parameters and Ra or the anode weight, ATB Metallurgie 2002,42 (1-2) obtain among the 69-77.Therefore, those skilled in the art can fully know and 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, in the anode weight of water-wetted surface greater than 3.0g/m
2Aluminium oxide, more preferably anode weight is greater than 4.0g/m
2Aluminium oxide.
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, alumina supporter can carry out phosphatization to be handled, and this comprises with phosphate solution handles alumina surface, and phosphate solution also can contain inorganic fluoride.In addition, can also 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 alumina surface.Preferred citric acid or the citrate solution of using.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, EP-A-659 909, EP-A-537633, and DE-A-4 001 466, EP A-292 801 provides among EP A-291 760 and the US-P-4 458 005.
Coating on the carrier is a thermal sensitivity, therefore obtained a kind of can be at several hours plate precursor of normal operating illumination condition (daylight, fluorescent lamp) operation.Coating preferably is not contained in the ultraviolet-sensitive compound that has absorption maximum in the wave-length coverage of 200nm to 400nm, for example diazonium compound, photogenerated acid (photoacids), light trigger, diazonium quinones or sensitizer.Coating preferably is not contained in the compound that absorption maximum is arranged in blueness between the wave-length coverage 400 to 600nm and the green visible light.
Coating can be made up of one or more different layers.Except the layer of hereinafter discussing, coating may further include, and for example increases " glue-line " of viscosity between coating and the carrier, avoids the protective layer of coating contamination or mechanical damage, and/or contains the photo-thermal conversion coating of infrared absorbing compound.
Coating is erect image work, and heating can cause coating dissolving, promptly coating under non-exposure status be anti-developer with accept printing ink, dissolve in developer and be exposed to become under heat or the infrared ray, to such an extent as to the hydrophilic surface of carrier comes out.
Coating preferably contains the hydrophobic polymer that dissolves in aqueous alkaline developer.Preferred polymer is a phenolic resins, for example the polymer of novolaks, resole resin, polyvinyl phenol and carboxyl substituted.The representative instance of this polymer is at DE-A-4007428, and DE-A-027301 and DE-A-4445820 have description.In addition, coating can also contain the service cycle and/or the chemical-resistant polymer of modified version.The example is to comprise sulfonamido (SO
2-NR-) or imide (CO-NR-CO-) polymer of side group, wherein R is hydrogen, the optional alkyl that replaces or the optional aryl that replaces, for example EP-A 894622,901902,933682 and WO99/63407 in the polymer described.
In a preferred embodiment, coating also contains one or more dissolution inhibitors, and promptly one or more reduce the material of the rate of dissolution of hydrophobic polymer in aqueous alkaline developer of coating unexposed area.Can easily test dissolving inhibition ability by two kinds of samples of coating on a carrier: a reference sample that only contains hydrophobic polymer contains the sample of this polymer (with reference equivalent) and inhibitor with another.A series of unexposed samples are immersed in the moisture alkaline-based developer, and each sample soaks the different time therein.Through after the soak time, from developer, take out sample, water flushing immediately, drying is then by the relatively dissolving of gravimetry coating in developer of development front and back sample.In case coating is dissolved fully, then under longer soak time, also can not measure weight saving, the relation curve of promptly representing the loss in weight and soak time reaches terrace part from the consoluet moment of layer.The sample that contains inhibitor in developer when the coating of the sample that does not have inhibitor is dissolved fully also is not developed agent and erodes to the affected degree of ability that coating is accepted printing ink, and then this material has good inhibition ability.
Dissolution inhibitor can join above-mentioned contain the alkali solubility hydrophobic polymer the layer in.In this embodiment, the rate of dissolution of unexposed coating in developer be because the polymer of hydrophobic and the interaction between the inhibitor, the hydrogen bond action between these compounds for example, and slow down.The dissolving of inhibitor suppresses ability and preferably reduces or destruction by the heat that produces in exposure process, so that this coating exposure area is dissolved in developer easily.This inhibitor preferably contains the organic compound at least one aryl and hydrogen bond binding site; the example that hydrogen bond links the site has carbonyl, sulfonyl or nitrogen-atoms; nitrogen-atoms can be quaternised, also can be a part or the amino substituent part of described organic compound of heterocycle.Such suitable dissolution inhibitor is for example disclosing among the EP-A 825927 and 823327.Following compounds of touching upon are as for example cyanine and for example quaternised triarylmethane dye of contrast dye also can be used as dissolution inhibitor to the dyestuff of sensitive for infrared radiation.
Refuse the polymer of water and represented second kind of suitable dissolution inhibitor.Thereby this polymer looks the ability that has improved anti-developer by repel aqueous developer from coating.Refusing aqueous polymer can join in the layer that contains hydrophobic polymer and/or may reside in and contain in the separation layer that the hydrophobic polymer layer is provided with above.In the embodiment of back, refuse aqueous polymer and form the barrier layer, this barrier layer separates coating and developer, and by being exposed to heat or infrared ray, solubility or the developer of barrier layer in developer can reduce the permeability on barrier layer, as EP-A864420, EP-A 950517 and WO99/21725 describe.The example of preferably refusing aqueous polymer has the polymer that contains siloxanes and/or perfluoroalkyl unit.In one embodiment, coating contain this amount of refusing aqueous polymer 0.5 to 25mg/m
2Between, preferably 0.5 to 15mg/m
2Between, most preferably 0.5 to 10mg/m
2Between.When this is refused aqueous polymer and also repels printing ink, the situation of polysiloxanes for example, content is higher than 25mg/m
2It is poor to cause unexposed area to accept printing ink.Content is lower than 0.5mg/m on the other hand
2May cause unsafty inhibition development capability.Polysiloxanes can be the polymer or the copolymer of straight chain, ring-type or complex cross-linked.The term polysiloxane compound comprises any compound that contains more than a siloxane group-Si (R, R ')-O-, and wherein R and R ' are the optional alkyl or aryls that replaces.Preferred siloxanes is phenylalkyl siloxanes and dialkylsiloxane.The number of siloxane group is 2 at least in (being total to) polymer, preferably is 10 at least, more preferably is 20 at least.Can be less than 100, preferably less than 60.In another embodiment, refusing aqueous polymer is poly-(alkylene oxide) block and block copolymer or the graft copolymer that contains the polymer blocks of siloxanes and/or perfluoroalkyl unit.Suitable copolymers contains have an appointment 15 to 25 siloxane units and 50 to 70 alkylen groups.Preferred examples comprises the copolymer that contains phenyl methyl siloxanes and/or dimethyl siloxane and oxirane and/or expoxy propane, for example Tego Glide 410, Tego Wet 265, Tego Protect 5001 or Silikophen P50/X, all can be from Tego Chemie, Essen, Germany buys.Because the bifunctional structure of this copolymer, it is as surfactant, though when Bulk coat by the coating of single coating solution, copolymer on the coating also automatically between coating and air at the interface, and form an independent top layer thus.Simultaneously, this surfactant plays a part to improve the spreading agent of coating quality.In addition, refusing aqueous polymer can apply in second solution, is coated in above the one deck that contains hydrophobic polymer.In that embodiment, it is useful using the solvent that can not dissolve the composition in the ground floor in second coating solution, so that obtain the water of refusing of high concentration on coating top.
In coating, also preferably contain one or more development accelerants, promptly as the compound of dissolution accelerator, because these compounds can improve the rate of dissolution of unexposed coating in developer, this can test the described same procedure of dissolution inhibitor by above.The dissolution properties of coating can be finely tuned accurately.Suitable dissolution accelerator has cyclic acid anhydride, phenol or organic acid.The example of cyclic acid anhydride comprises as United States Patent (USP) 4,115,128 phthalic anhydride, tetrabydrophthalic anhydride, the hexahydrophthalic anhydrides of describing, 3,6-bridging oxygen-4-tetrabydrophthalic anhydride, tetrachlorophthalic tetrachlorophthalic anhydrid, maleic anhydride, chloromaleic acid acid anhydride, α-phenyl maleic anhydride, succinyl oxide and PMA.The example of phenol comprises bisphenol-A, p-nitrophenol, to thanatol, 2,4,4 '-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-dihydroxy benaophenonel, 4,4 ', 4 " trihydroxy triphenylmenthane and 4; 4 ', 3 ", 4 " tetrahydroxy-3; 5; 3 ', 5 '-the tetramethyl triphenyl methane, or the like.The organic acid example comprises sulfonic acid, sulfinic acid, alkylsurfuric acid, phosphonic acids, phosphate and carboxylic acid, JP-A 60-88 for example, and 942 and 2-96, described in 755.These organic acid instantiations comprise p-methyl benzenesulfonic acid, DBSA, to toluenesulfinic acid, ethyl sulfuric acid, phenyl-phosphonic acid, phenyl-phosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, right-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid (TPA), 4-cyclohexene-1,2-dicarboxylic acids, erucic acid, laurate, just-hendecanoic acid and ascorbic acid.Cyclic acid anhydride, phenol or the organic acid content in coating is preferably in the scope of 0.05 to 20% (weight) that is coated with stratum total.
The method imaging that material can directly expose with heat, for example pass through thermal print head, the perhaps method imaging that exposes by infrared ray indirectly, preferably change infrared ray into heat with infrared absorbing compound, infrared absorbing compound can be dyestuff or the pigment that absorption maximum is arranged in infrared wavelength range.With respect to being coated with stratum total, sensitizing dye or the pigment concentration in coating is generally 0.25 to 10.0 weight %, more preferably 0.5 to 7.5 weight %.Preferred infrared absorbing compound is a for example cyanine dye or merocyanine dyes or pigment carbon black for example of dyestuff.The following dyestuff to sensitive for infrared radiation is a suitable compound:
Coating can also contain the organic dyestuff that absorbs visible light so that obtain visible image in imaging method exposure and developing process subsequently.This dyestuff often is called contrast dye or indicator dye.Dyestuff is preferably blueness and in the wave-length coverage of 750nm absorption maximum is arranged at 600nm.Though dyestuff absorbs visible light, preferred its do not make plate precursor have photonasty, and promptly coating is exposed to can not become under the visible light and more is soluble in developer.The example that this contrast dye is suitable has quaternised triarylmethane dye.
Infrared absorbing compound and contrast dye may reside in and contain in the hydrophobic polymer layer, and/or are present in the barrier layer of discussing when above-mentioned, and/or are present in other optional layer.According to a highly preferred embodiment, infrared absorbing compound is enriched in the barrier layer or near the barrier layer, for example in the intermediate layer between layer that contains hydrophobic polymer and barrier layer.
Plate precursor of the present invention can be exposed to be utilized under the infrared ray that light emitting diode or laser instrument send.The preferred emission wavelength that uses is at about 750 laser instruments to the near infrared light of about 1500nm scope, for example semiconductor laser diode, Nd:YAG or Nd:YLF laser instrument.The laser power that needs depends on the sensitivity of image recording layer, and the resolution of the pixel time of staying of laser beam, 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.
Two kinds of laser explosure instruments of general use: interior drum (ITD) version setting apparatus 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 sweep speed of 500 meter per seconds and the laser power of several watts of needs.The XTD version setting apparatus that is used for the heat version generally has about 200 milliwatts to about 1 watt laser power, moves under lower sweep speed, for example the sweep speed of 0.1 to 10 meter per second.
Known version setting apparatus can be as the machine instrument that exposes outward, and this helps reducing the downtime of printing machine.The structure of XTD version setting apparatus also can be used for exposing on the machine, and this helps rapid registering in chromatic printing machine.About the more ins and outs of exposure instrument on the machine at US 5,174,205 and US 5,163,368 in describe.
In development step, remove by soaking in moisture alkaline-based developer in the no image area territory of coating, can for example use rotary brush in conjunction with mechanical friction, removes the no image area territory of coating.The pH value of developer preferably is higher than 10, more preferably is higher than 12.After the development step can be cleaning step, gluing step, drying steps and/or back baking step.
The galley that obtains like this can be used for common so-called wet hectographic printing, wherein printing ink and the moisture liquid that soaks is offered version.The another kind of printing process that is fit to is used so-called single liquid printing ink and need not be soaked liquid.Single liquid printing ink is also referred to as the polarity phase composition that contains water-soaked liquid that hydrophobic or oleophylic phase and replacement are used by the printing ink phase in common wet hectographic printing.The example of suitable single liquid printing ink is in US 4,045,232; US 4,981,517 and US 6,140,392 in describe.In most preferred embodiment, as describing among the WO 00/32705, single liquid printing ink contain printing ink mutually with polyalcohol mutually.
Embodiment
Preparation lithographic support 1 (comparative example)
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 use the electrochemical method surface roughening in the aqueous solution of the aluminum sulfate (18 hydrate) of hydrochloric acid that contains 12g/l and 38g/l, Ra is the surface topography of 0.5 μ m with formation center line average roughness.After washing for 2 seconds with demineralized water, with 4 seconds of aqueous solution etching that contain 155g/l sulfuric acid, cleaned for 2 seconds down at 25 ℃ with demineralized water then at 70 ℃ of aluminum slices.Subsequently at 45 ℃ of temperature and 22A/dm
2In the aqueous solution that contains 155g/l sulfuric acid, carry out the thin slice anodic oxidation under the current density, form 2.90g/m
2Al
2O
3Anodic oxidation film cleaned for 2 seconds with demineralized water then, continued to handle for 10 seconds with the solution that contains the 4g/l polyvinylphosphonic acid again at 40 ℃, washed for 2 seconds at 20 ℃ with demineralized water, and is dry then.
Preparation lithographic support 2 (the present invention)
Except the current density in surface roughening and the anode oxidation process is respectively 90A/dm
2And 30A/dm
2Use and prepare lithographic support 1 described identical method and prepare lithographic support 2 outward.As a result, the Ra value is that 0.2 μ m and anode weight are 4.0g/m
2
Preparation plate precursor 1 and 2
Solution with regulation in the table 1 is coated on the above-mentioned lithographic printing substrate 1 and 2, preparation contrast plate precursor 1 and plate precursor of the present invention 2.Apply coating solution on the coating line that moves with the speed of 10.8m/min, wet coating layer thickness is 26 μ m, and is dry down at 135 ℃ then.
Table 1: the composition of coating solution
(1) Alnovol SPN452 is the novolaks solution (can available from Clariant) of 40.5 weight % among the Dowanol PM.
(2) available from 1-methoxyl group-2-propyl alcohol of Dow Chemical Company.
(3) S0094 is the infrared ray absorbing cyanine dye, can be available from FEW Chemicals.S0094 has the chemical constitution of the IR-1 that as above shows.
(4) Basonyl Blue 640 is quaternised triarylmethane dyes, can be available from BASF.
(5) TegoWet 265 and TegoGlide 410 are polysiloxanes/poly-(alkylene oxide) surfactants of block copolymerization, can be available from Tego Chemie Service GmbH.
Estimate and the result
The some of every kind of plate precursor is packaged in the paper bag of opening and at room temperature stored 7 days.Another of plate precursor partly is packaged in the sack of opening and at 50 ℃ of storages 7 days down.
Then, plate precursor is exposed on the CreoScitex Trendsetter3244 with the operation of 150 rev/mins drum rotation speed, and the energy on the version is from 80mJ/cm
2To 200mJ/cm
2Not etc., energy is differential is 20mJ/cm
2Version is made a plate in Agfa Autolith T platemaking machine then, platemaking machine speed of service 0.96m/min, 25 ℃ use Agfa TD5000 developers with, and with RC795 as glue.Only estimate the version that obtains by the optimum exposure energy, use Heidelberg GTO52 printing machine, its with K+E 800 Skinnex Black (can available from BASF) as printing ink and ROTA-MATIC (can available from Unigraphica GmbH) as fountain solution.When at room temperature storing, two kinds of plate precursor 1 and 2 all have good lithographic performance, and printing does not have colour contamination.The version that storage precursor 1 at high temperature obtains has shown serious colour contamination at non-imaging area, becomes otiose galley.The version printing that storage precursor 2 at high temperature obtains does not have colour contamination.
Claims (12)
1. positivity Lighographic printing plate precursor, the oleophylic coating that comprises (i) possess hydrophilic property surface through surface roughening and anodised alumina supporter and the temperature-sensitive that (ii) on hydrophilic surface, forms, wherein in moisture alkaline-based developer, described coating exposed areas under heat or infrared ray is dissolved with higher rate of dissolution than unexposed zone, this plate precursor is characterised in that: the surface roughness that hydrophilic surface is represented with the arithmetic mean of instantaneous value Ra of centre line roughness degree is less than 0.40 μ m, and hydrophilic surface contains 3.0g/m
2To 4.0g/m
2But do not comprise 3.0g/m
2Aluminium oxide.
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 0.3 μ m.
3. the plate precursor of claim 1, its floating coat contain polymer and (b) dissolution inhibitor that (a) dissolves in the hydrophobic of developer.
4. the plate precursor of claim 3, wherein dissolution inhibitor is a kind of aqueous polymer of refusing.
5. the plate precursor of claim 4 is wherein refused aqueous polymer and is
-contain the polymer of siloxanes and/or perfluoroalkyl unit; Or
-poly-(alkylene oxide) block and the block copolymer or the graft copolymer that contain the block of siloxanes and/or perfluoroalkyl unit.
6. the plate precursor of claim 3, wherein dissolution inhibitor is to contain the organic compound that aryl and hydrogen bond link the site.
7. the plate precursor of claim 1, its floating coat also contains dissolution accelerator.
8. possess hydrophilic property surface and in the positivity Lighographic printing plate precursor, be used to improve the purposes of the shelf life of this printing plate precursor through surface roughening and anodised alumina supporter, this alumina supporter hydrophilic surface is characterised in that: the surface roughness of representing with the arithmetic mean of instantaneous value Ra of centre line roughness degree is less than 0.40 μ m, and hydrophilic surface contains 3.0g/m
2To 4.0g/m
2But do not comprise 3.0g/m
2Aluminium oxide, plate precursor has the oleophylic coating of the temperature-sensitive that forms on hydrophilic surface, wherein in moisture alkaline-based developer, described coating under heat or infrared ray exposed areas than unexposed zone with higher rate of dissolution dissolving.
9. the plate precursor of claim 2, its floating coat contain polymer and (b) dissolution inhibitor that (a) dissolves in the hydrophobic of developer.
10. the plate precursor of claim 3, its floating coat also contains dissolution accelerator.
11. the plate precursor of claim 5, its floating coat also contains dissolution accelerator.
12. the plate precursor of claim 6, its floating coat also contains dissolution accelerator.
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|---|---|---|---|
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|---|---|---|---|---|
| CN1317724A (en) * | 2000-04-07 | 2001-10-17 | 富士胶片株式会社 | Original plate of lithographic plate galley |
| CN1392060A (en) * | 2001-06-20 | 2003-01-22 | 富士胶片株式会社 | Lithographic printing plate front body and method for producing lithographic printing plate |
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| CN1317724A (en) * | 2000-04-07 | 2001-10-17 | 富士胶片株式会社 | Original plate of lithographic plate galley |
| CN1392060A (en) * | 2001-06-20 | 2003-01-22 | 富士胶片株式会社 | Lithographic printing plate front body and method for producing lithographic printing plate |
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