EP1380417B1 - Positive-working lithographic printing plate precursor - Google Patents
Positive-working lithographic printing plate precursor Download PDFInfo
- Publication number
- EP1380417B1 EP1380417B1 EP20030101850 EP03101850A EP1380417B1 EP 1380417 B1 EP1380417 B1 EP 1380417B1 EP 20030101850 EP20030101850 EP 20030101850 EP 03101850 A EP03101850 A EP 03101850A EP 1380417 B1 EP1380417 B1 EP 1380417B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating
- plate precursor
- hydrophilic surface
- precursor according
- printing plate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000007639 printing Methods 0.000 title claims description 32
- 239000002243 precursor Substances 0.000 title claims description 31
- 239000011248 coating agent Substances 0.000 claims description 56
- 238000000576 coating method Methods 0.000 claims description 56
- 238000004090 dissolution Methods 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- 239000003112 inhibitor Substances 0.000 claims description 17
- 230000005660 hydrophilic surface Effects 0.000 claims description 12
- 229920001600 hydrophobic polymer Polymers 0.000 claims description 11
- 239000005871 repellent Substances 0.000 claims description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 230000003746 surface roughness Effects 0.000 claims description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000002894 organic compounds Chemical group 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
- 239000000243 solution Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000000975 dye Substances 0.000 description 12
- 239000000976 ink Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- -1 sulfonated aliphatic aldehyde Chemical class 0.000 description 11
- 239000002253 acid Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000007743 anodising Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000994 contrast dye Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 230000008901 benefit Effects 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
- 229940093915 gynecological organic acid Drugs 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000001003 triarylmethane dye Substances 0.000 description 3
- 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 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 description 2
- 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
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 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
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 150000003013 phosphoric acid derivatives 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
- 238000007788 roughening Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- 238000005063 solubilization Methods 0.000 description 2
- 230000007928 solubilization Effects 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 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
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-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
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- DILXLMRYFWFBGR-UHFFFAOYSA-N 2-formylbenzene-1,4-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(S(O)(=O)=O)C(C=O)=C1 DILXLMRYFWFBGR-UHFFFAOYSA-N 0.000 description 1
- YTFVRYKNXDADBI-SNAWJCMRSA-N 3,4,5-trimethoxycinnamic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC(OC)=C1OC YTFVRYKNXDADBI-SNAWJCMRSA-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
- CXJAFLQWMOMYOW-UHFFFAOYSA-N 3-chlorofuran-2,5-dione Chemical compound ClC1=CC(=O)OC1=O CXJAFLQWMOMYOW-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
- LKVFCSWBKOVHAH-UHFFFAOYSA-N 4-Ethoxyphenol Chemical compound CCOC1=CC=C(O)C=C1 LKVFCSWBKOVHAH-UHFFFAOYSA-N 0.000 description 1
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-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
- 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
- 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
- 206010073306 Exposure to radiation Diseases 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- YTFVRYKNXDADBI-UHFFFAOYSA-N O-Methylsinapic acid Natural products COC1=CC(C=CC(O)=O)=CC(OC)=C1OC YTFVRYKNXDADBI-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-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
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 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
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- ILUAAIDVFMVTAU-UHFFFAOYSA-N cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CC=CCC1C(O)=O ILUAAIDVFMVTAU-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 150000008049 diazo compounds 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
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- PQPVPZTVJLXQAS-UHFFFAOYSA-N hydroxy-methyl-phenylsilicon Chemical class C[Si](O)C1=CC=CC=C1 PQPVPZTVJLXQAS-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 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
- 239000002904 solvent Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/04—Printing plates or foils; Materials therefor metallic
- B41N1/08—Printing plates or foils; Materials therefor metallic for lithographic printing
- B41N1/083—Printing plates or foils; Materials therefor metallic for lithographic printing made of aluminium or aluminium alloys or having such surface layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N3/00—Preparing for use and conserving printing surfaces
- B41N3/03—Chemical or electrical pretreatment
- B41N3/034—Chemical or electrical pretreatment characterised by the electrochemical treatment of the aluminum support, e.g. anodisation, electro-graining; Sealing of the anodised layer; Treatment of the anodic layer with inorganic compounds; Colouring of the anodic layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/02—Positive working, i.e. the exposed (imaged) areas are removed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/06—Developable by an alkaline solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
- B41C2210/262—Phenolic condensation polymers, e.g. novolacs, resols
Definitions
- the present invention relates to a heat-sensitive positive-working lithographic printing plate precursor that requires aqueous alkaline processing.
- Lithographic printing presses use a so-called printing master such as a printing plate which is mounted on a cylinder of the printing press.
- the master carries a lithographic image on its surface and a print is obtained by applying ink to said image and then transferring the ink from the master onto a receiver material, which is typically paper.
- ink as well as an aqueous fountain solution also called dampening liquid
- the lithographic image which consists of oleophilic (or hydrophobic, i.e. ink-accepting, water-repelling) areas as well as hydrophilic (or oleophobic, i.e. water-accepting, ink-repelling) areas.
- so-called driographic printing the lithographic image consists of ink-accepting and ink-abhesive (ink-repelling) areas and during driographic printing, only ink is supplied to the master.
- Printing masters are generally obtained by the image-wise exposure and processing of an imaging material called plate precursor.
- a typical positive-working plate precursor comprises a hydrophilic support and an oleophilic coating which is not readily soluble in an aqueous alkaline developer in the non-exposed state and becomes soluble in the developer after exposure to radiation.
- heat-sensitive printing plate precursors have become very popular. Such thermal materials offer the advantage of daylight stability and are especially used in the so-called computer-to-plate method wherein the plate precursor is directly exposed, i.e. without the use of a film mask.
- the material is exposed to heat or to infrared light and the generated heat triggers a (physico-)chemical process, such as ablation, polymerization, insolubilization by cross-linking of a polymer, heat-induced solubilization, or particle coagulation of a thermoplastic polymer latex.
- a (physico-)chemical process such as ablation, polymerization, insolubilization by cross-linking of a polymer, heat-induced solubilization, or particle coagulation of a thermoplastic polymer latex.
- EP 0,704,320 discloses mechanical roughening of an aluminium or an aluminium alloy substrate by wet brushing the substrate with a cylinder brush whereby the roughened surface of the substrate obtains an average center line roughness of 0.3 ⁇ m to 1.2 ⁇ m.
- a printing plate with a smooth and pore- free metal surface which has a Ra value ⁇ 0.2 ⁇ m and which can directly be provided with an image is disclosed in EP 0,693,371.
- the applied images can repeatedly be erased.
- US 6,374,737 discloses a process for making an ablative printing plate material comprising an aluminium alloy as substrate which is preferably mill finished or finished via roll texturing, chemical texturing, mechanical texturing, electrochemical texturing or combinations thereof.
- Ra values of 5 to 15 microinches are disclosed for substrates rolled with EDT (electron discharge texturing) treated rolls.
- US 4,800,950 describes a process for manufacturing substrates for lithographic printing plates with improved mechanical properties.
- the process involves electrochemical roughening, etching and anodizing of cast aluminium alloys whereby Ra values of 0.23 ⁇ m to 0.37 ⁇ m are obtained.
- a negative-working radiation sensitive imaging element comprising a grained and anodized aluminium substrate with an anodic weight of 3 g/m 2 is disclosed in US 6,140,022.
- thermal plate precursors A specific problem associated with thermal plate precursors is the limited shelf life of the coating. Especially when stored at elevated temperature, which is inevitable during transport by truck, boat, etc. the plates may show significant toning (ink-acceptance in the non-image areas).
- This object is realized by the material of claim 1, having the characterizing feature that a low surface roughness of the grained and anodized aluminum support unexpectedly provides an improved shelf life of the material.
- Specific embodiments of the invention are defined in the dependent claims.
- the support of the plate precursor of the present invention is a grained and anodized aluminum support having a hydrophilic surface that is characterized by a low surface roughness, expressed as arithmetical mean center-line roughness (Ra), sometimes also referred to as CLA (center-line average).
- the apparatus used for measuring Ra was a Talysurf 10 from Taylor Hobson Ltd.
- the Ra value of the hydrophilic surface of the grained and anodized aluminum support used in the material of the present invention is lower than 0.40 ⁇ m, preferably lower than 0.30 ⁇ m and even more preferably lower than 0.25 ⁇ m.
- a grained and anodized aluminum support having a hydrophilic surface characterized by the mentioned low Ra values is briefly referred to herein as a "smooth support".
- the lower limit of the Ra value may be 0.05 ⁇ m, preferably 0.1 ⁇ m.
- the grained aluminum support used in the material of the present invention is preferably an electrochemically grained support.
- the acid used for graining can be e.g. nitric acid.
- the acid used for graining preferably comprises hydrogen chloride. Also mixtures of e.g. hydrogen chloride and acetic acid can be used.
- anodic weight at the hydrophilic surface is more than 3.0 g/m 2 of aluminum oxide, a value above 4.0 g/m 2 being even more preferred.
- the grained and anodized aluminum support may be post-treated to improve the hydrophilic properties of its surface.
- the aluminum support may be silicated by treating its surface with a sodium silicate solution at elevated temperature, e.g. 95°C.
- a phosphate treatment may be applied which involves treating the aluminum oxide surface with a phosphate solution that may further contain an inorganic fluoride.
- the aluminum oxide surface may be rinsed with an organic acid and/or salt thereof, e.g. carboxylic acids, hydroxycarboxylic acids, sulfonic acids or phosphonic acids, or their salts, e.g. succinates, phosphates, phosphonates, sulfates, and sulfonates.
- a citric acid or citrate solution is preferred. This treatment may be carried out at room temperature or may be carried out at a slightly elevated temperature of about 30 to 50°C.
- a further post-treatment involves rinsing the aluminum oxide surface with a bicarbonate solution. Still further, the aluminum oxide surface may be treated with polyvinylphosphonic acid, polyvinylmethylphosphonic acid, phosphoric acid esters of polyvinyl alcohol, polyvinylsulfonic acid, polyvinylbenzenesulfonic acid, sulfuric acid esters of polyvinyl alcohol, and acetals of polyvinyl alcohols formed by reaction with a sulfonated aliphatic aldehyde.
- the coating provided on the support is heat-sensitive, thereby providing a plate precursor which can be handled in normal working lighting conditions (daylight, fluorescent light) for several hours.
- the coating preferably does not contain UV-sensitive compounds which have an absorption maximum in the wavelength range of 200 nm to 400 nm such as diazo compounds, photoacids, photoinitiators, quinone diazides, or sensitizers.
- the coating neither contains compounds which have an absorption maximum in the blue and green visible light wavelength range between 400 and 600 nm.
- the coating may comprise one or more distinct layers. Besides the layers discussed hereafter, the coating may further comprise e.g. a "subbing" layer which improves the adhesion of the coating to the support, a covering layer which protects the coating against contamination or mechanical damage, and/or a light-to-heat conversion layer which comprises an infrared light absorbing compound.
- a "subbing" layer which improves the adhesion of the coating to the support
- a covering layer which protects the coating against contamination or mechanical damage
- a light-to-heat conversion layer which comprises an infrared light absorbing compound.
- the coating is positive-working and capable of heat-induced solubilization, i.e. the coating is resistant to the developer and ink-accepting in the non-exposed state and becomes soluble in the developer upon exposure to heat or infrared light to such an extent that the hydrophilic surface of the support is revealed thereby.
- the coating comprises a hydrophobic polymer that is soluble in an aqueous alkaline developer.
- Preferred polymers are phenolic resins, e.g. novolac, resoles, polyvinyl phenols and carboxy-substituted polymers. Typical examples of such polymers are described in DE-A-4007428, DE-A-4027301 and DE-A-4445820.
- the coating may comprise polymers which improve the run length and/or the chemical resistance of the plate.
- polymers comprising sulfonamido (-SO 2 -NR-) or imido (-CO-NR-CO-) pendant groups, wherein R is hydrogen, optionally substituted alkyl or optionally substituted aryl, such as the polymers described in EP-A 894622, 901902, 933682 and WO99/63407.
- the coating also contains one or more dissolution inhibitors, i.e. one or more materials which reduce the dissolution rate of the hydrophobic polymer in the aqueous alkaline developer at the non-exposed areas of the coating.
- the dissolution inhibiting capability of the inhibitor can easily be tested by coating two samples on a support : a reference sample containing only the hydrophobic polymer and another including both the polymer (in equal amounts as the reference) as well as the inhibitor. A series of unexposed samples is immersed in an aqueous alkaline developer, each sample during a different time period.
- the sample is removed from the developer, immediately rinsed with water, dried and then the dissolution of the coating in the developer is measured by comparing the weight of the sample before and after the development. As soon as the coating is dissolved completely, no more weight loss is measured upon longer immersion time periods, i.e. a curve representing weight loss as a function of immersion time reaches a plateau from the moment of complete dissolution of the layer.
- a material has good inhibiting capability when the coating of the sample without the inhibitor has dissolved completely in the developer before the sample with the inhibitor is attacked by the developer to such an extent that the ink-accepting capability of the coating is affected.
- the dissolution inhibitor(s) can be added to the layer which comprises the alkali-soluble hydrophobic polymer discussed above.
- the dissolution rate of the non-exposed coating in the developer is reduced by interaction between the hydrophobic polymer and the inhibitor, due to e.g. hydrogen bonding between these compounds.
- the dissolution inhibiting capability of the inhibitor is preferably reduced or destroyed by the heat generated during the exposure so that the coating readily dissolves in the developer at exposed areas.
- Such inhibitors are preferably organic compounds which comprise at least one aromatic group and a hydrogen bonding site, e.g.
- Suitable dissolution inhibitors of this type have been disclosed in e.g. EP-A 825927 and 823327.
- Some of the compounds mentioned below, e.g. infrared dyes such as cyanines and contrast dyes such as quaternized triarylmethane dyes can also act as a dissolution inhibitor.
- Water-repellent polymers represent a second type of suitable dissolution inhibitors. Such polymers seem to increase the developer resistance of the coating by repelling the aqueous developer from the coating.
- the water-repellent polymers can be added to the layer comprising the hydrophobic polymer and/or can be present in a separate layer provided on top of the layer with the hydrophobic polymer.
- the water-repellent polymer forms a barrier layer which shields the coating from the developer and the solubility of the barrier layer in the developer or the penetrability of the barrier layer by the developer can be reduced by exposure to heat or infrared light, as described in e.g. EP-A 864420, EP-A 950517 and WO99/21725.
- the water-repellent polymers are polymers comprising siloxane and/or perfluoroalkyl units.
- the coating contains such a water-repellent polymer in an amount between 0.5 and 25 mg/m 2 , preferably between 0.5 and 15 mg/m 2 and most preferably between 0.5 and 10 mg/m 2 .
- the water-repellent polymer is also ink-repelling, e.g. in the case of polysiloxanes, higher amounts than 25 mg/m 2 can result in poor ink-acceptance of the non-exposed areas.
- An amount lower than 0.5 mg/m 2 on the other hand may lead to an unsatisfactory development resistance.
- the polysiloxane may be a linear, cyclic or complex cross-linked polymer or copolymer.
- the term polysiloxane compound shall include any compound which contains more than one siloxane group -Si(R,R')-O-, wherein R and R' are optionally substituted alkyl or aryl groups.
- Preferred siloxanes are phenylalkylsiloxanes and dialkylsiloxanes.
- the number of siloxane groups in the (co)polymer is at least 2, preferably at least 10, more preferably at least 20. It may be less than 100, preferably less than 60.
- the water-repellent polymer is a block-copolymer or a graft-copolymer of a poly(alkylene oxide) block and a block of a polymer comprising siloxane and/or perfluoroalkyl units.
- a suitable copolymer comprises about 15 to 25 siloxane units and 50 to 70 alkylene oxide groups.
- Preferred examples include copolymers comprising phenylmethylsiloxane and/or dimethylsiloxane as well as ethylene oxide and/or propylene oxide, such as Tego Glide 410, Tego Wet 265, Tego Protect 5001 or Silikophen P50/X, all commercially available from Tego Chemie, Essen, Germany.
- Such a copolymer acts as a surfactant which upon coating, due to its bifunctional structure, automatically positions itself at the interface between the coating and air and thereby forms a separate top layer even when the whole coating is applied from a single coating solution. Simultaneously, such surfactants act as a spreading agent which improves the coating quality.
- the water-repellent polymer can be applied in a second solution, coated on top of the layer comprising the hydrophobic polymer. In that embodiment, it may be advantageous to use a solvent in the second coating solution that is not capable of dissolving the ingredients present in the first layer so that a highly concentrated water-repellent phase is obtained at the top of the coating.
- one or more development accelerators are included in the coating, i.e. compounds which act as dissolution promoters because they are capable of increasing the dissolution rate of the non-exposed coating in the developer, which can be tested by the same procedure as described above in relation to dissolution inhibitors.
- Suitable dissolution accelerators are cyclic acid anhydrides, phenols or organic acids.
- cyclic acid anhydride examples include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endoxy- 4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, alpha - phenylmaleic anhydride, succinic anhydride, and pyromellitic anhydride, as described in U.S. Patent No. 4,115,128.
- phenols examples include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxy-benzophenone, 4-hydroxybenzophenone, 4,4',4"-trihydroxy-triphenylmethane, and 4,4',3",4"-tetrahydroxy-3,5,3',5'-tetramethyltriphenyl-methane, and the like.
- organic acids include sulfonic acids, sulfinic acids, alkylsulfuric acids, phosphonic acids, phosphates, and carboxylic acids, as described in, for example, JP-A Nos. 60-88,942 and 2-96,755.
- organic acids include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethylsulfuric acid, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4-cyclohexene-1,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid.
- the amount of the cyclic acid anhydride, phenol, or organic acid contained in the coating is preferably in the range of 0.05 to 20% by weight, relative to the coating as a whole.
- the material can be image-wise exposed directly with heat, e.g. by means of a thermal head, or indirectly by infrared light, which is preferably converted into heat by an infrared light absorbing compound, which may be a dye or pigment having an absorption maximum in the infrared wavelength range.
- an infrared light absorbing compound which may be a dye or pigment having an absorption maximum in the infrared wavelength range.
- concentration of the sensitizing dye or pigment in the coating is typically between 0.25 and 10.0 wt.%, more preferably between 0.5 and 7.5 wt.% relative to the coating as a whole.
- Preferred IR-absorbing compounds are dyes such as cyanine or merocyanine dyes or pigments such as carbon black.
- a suitable compound is the following infrared dye :
- the coating may further contain an organic dye which absorbs visible light so that a perceptible image is obtained upon image-wise exposure and subsequent development.
- a dye is often called contrast dye or indicator dye.
- the dye has a blue color and an absorption maximum in the wavelength range between 600nm and 750 nm.
- the dye absorbs visible light, it preferably does not sensitize the printing plate precursor, i.e. the coating does not become more soluble in the developer upon exposure to visible light.
- Suitable examples of such a contrast dye are the quaternized triarylmethane dyes.
- the infrared light absorbing compound and the contrast dye may be present in the layer comprising the hydrophobic polymer, and/or in the barrier layer discussed above and/or in an optional other layer.
- the infrared light absorbing compound is concentrated in or near the barrier layer, e.g. in an intermediate layer between the layer comprising the hydrophobic polymer and the barrier layer.
- the printing plate precursor of the present invention can be exposed to infrared light with LEDs or a laser.
- a laser emitting near infrared light having a wavelength in the range from about 750 to about 1500 nm is used, such as a semiconductor laser diode, a Nd:YAG or a Nd:YLF laser.
- the required laser power depends on the sensitivity of the image-recording layer, the pixel dwell time of the laser beam, which is determined by the spot diameter (typical value of modern plate-setters at 1/e 2 of maximum intensity : 10-25 pm), the scan speed and the resolution of the exposure apparatus (i.e. the number of addressable pixels per unit of linear distance, often expressed in dots per inch or dpi; typical value : 1000-4000 dpi).
- ITD plate-setters for thermal plates are typically characterized by a very high scan speed up to 500 m/sec and may require a laser power of several Watts.
- the known plate-setters can be used as an off-press exposure apparatus, which offers the benefit of reduced press down-time.
- XTD plate-setter configurations can also be used for on-press exposure, offering the benefit of immediate registration in a multi-color press. More technical details of on-press exposure apparatuses are described in e.g. US 5,174,205 and US 5,163,368.
- the non-image areas of the coating are removed by immersion in an aqueous alkaline developer, which may be combined with mechanical rubbing, e.g. by a rotating brush.
- the developer preferably has a pH above 10, more preferably above 12.
- the development step may be followed by a rinsing step, a gumming step, a drying step and/or a post-baking step.
- the printing plate thus obtained can be used for conventional, so-called wet offset printing, in which ink and an aqueous dampening liquid is supplied to the plate.
- Another suitable printing method uses so-called single-fluid ink without a dampening liquid.
- Single-fluid ink consists of an ink phase, also called the hydrophobic or oleophilic phase, and a polar phase which replaces the aqueous dampening liquid that is used in conventional wet offset printing.
- Suitable examples of single-fluid inks have been described in US 4,045,232; US 4,981,517 and US 6,140,392.
- the single-fluid ink comprises an ink phase and a polyol phase as described in WO 00/32705.
- a 0.30 mm thick aluminum foil was degreased by immersing the foil in an aqueous solution containing 40 g/l of sodium hydroxide at 60°C for 8 seconds and rinsed with demineralized water for 2 seconds.
- the foil was then electrochemically grained using an alternating current in an aqueous solution containing 12 g/l of hydrochloric acid and 38 g/l of aluminum sulphate (18 hydrate) at a temperature of 33°C and a current density of 130 A/dm 2 to form a surface topography with an average center-line roughness Ra of 0.5 ⁇ m.
- the aluminum foil was then etched with an aqueous solution containing 155 g/l of sulfuric acid at 70°C for 4 seconds and rinsed with demineralized water at 25°C for 2 seconds.
- the foil was subsequently subjected to anodic oxidation in an aqueous solution containing 155 g/l of sulfuric acid at a temperature of 45°C, at a current density of 22 A/dm 2 to form an anodic oxidation film of 2.90 g/m 2 of Al 2 O 3 , then washed with demineralized water for 2 seconds and posttreated for 10 seconds with a solution containing 4 g/l polyvinylphosphonic acid at 40°C, rinsed with demineralized water at 20°C during 2 seconds and dried.
- the comparative printing plate precursor 1 and the printing plate precursor 2 according to the invention were produced by coating the solution defined in Table 1 onto the above described lithographic substrates 1 and 2.
- the coating solution was applied at a wet coating thickness of 26 ⁇ m on a coating line operating at a speed of 10.8 m/min and then dried at 135°C.
- Table 1 composition of the coating solution Parts (grams) Tetrahydrofuran 209.20 Alnovol SPN452 (1) 102.02 Dowanol PM (2) 332.13 Methyl ethyl ketone 266.20 S0094 (3) 2.10 1 wt.% solution of Basonyl Blue 640 (4) in Dowanol PM 53.00 1 wt.% solution of TegoGlide 410 (5) in Dowanol PM 8.50 1 wt.% solution of TegoWet 265 (5) in Dowanol PM 21.55 3,4,5-trimethoxy cinnamic acid 5.30 (1)Alnovol SPN452 is a 40.5 wt.% solution of novolac in Dowanol PM (commercially available from Clariant).
- S0094 is an IR absorbing cyanine dye commercially available from FEW Chemicals. S0094 has the chemical structure IR-1 shown above.
- Baseonyl Blue 640 is a quaternized triarylmethane dye commercially available from BASF.
- TegoWet 265 and TegoGlide 410 are both block-co-polysiloxane/poly(alkylene oxide) surfactants commercially available from Tego Chemie Service GmbH.
- each printing plate precursor was packaged in an open paper bag and stored during 7 days at ambient temperature. Another part of the printing plate precursor was packaged in an open bag and stored for 7 days at 50°C.
- the printing plate precursors were then exposed on a CreoScitex Trendsetter 3244 operating at a drum rotation speed of 150 rpm and the energy on the plates was varied from 80 mJ/cm 2 up to 200 mJ/cm 2 with steps of 20 mJ/cm 2 .
- the plates were then processed in an Agfa Autolith T processor operating at a speed of 0.96 m/min using Agfa TD5000 developer at 25°C and RC795 as gum. Only the plates obtained with the optimum exposure energy were used in the evaluation, using a Heidelberg GTO52 printing press with K+E 800 Skinnex Black (commercially available from BASF) as ink and ROTA-MATIC (commercially available from Unigraphica GmbH) as fountain.
- both the printing plate precursor 1 and 2 When stored at ambient temperature, both the printing plate precursor 1 and 2 had a very good lithographic behavior and printed without toning.
- the plate obtained from precursor 1 stored at elevated temperature showed severe toning in the non-image areas and was a useless printing plate.
- the plate which was obtained from the precursor 2 that had been stored at elevated temperature printed without toning.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Printing Plates And Materials Therefor (AREA)
- Materials For Photolithography (AREA)
Description
- The present invention relates to a heat-sensitive positive-working lithographic printing plate precursor that requires aqueous alkaline processing.
- Lithographic printing presses use a so-called printing master such as a printing plate which is mounted on a cylinder of the printing press. The master carries a lithographic image on its surface and a print is obtained by applying ink to said image and then transferring the ink from the master onto a receiver material, which is typically paper. In conventional lithographic printing, ink as well as an aqueous fountain solution (also called dampening liquid) are supplied to the lithographic image which consists of oleophilic (or hydrophobic, i.e. ink-accepting, water-repelling) areas as well as hydrophilic (or oleophobic, i.e. water-accepting, ink-repelling) areas. In so-called driographic printing, the lithographic image consists of ink-accepting and ink-abhesive (ink-repelling) areas and during driographic printing, only ink is supplied to the master.
- Printing masters are generally obtained by the image-wise exposure and processing of an imaging material called plate precursor. A typical positive-working plate precursor comprises a hydrophilic support and an oleophilic coating which is not readily soluble in an aqueous alkaline developer in the non-exposed state and becomes soluble in the developer after exposure to radiation. In addition to the well known photosensitive imaging materials which are suitable for UV contact exposure through a film mask (the so-called pre-sensitized plates), also heat-sensitive printing plate precursors have become very popular. Such thermal materials offer the advantage of daylight stability and are especially used in the so-called computer-to-plate method wherein the plate precursor is directly exposed, i.e. without the use of a film mask. The material is exposed to heat or to infrared light and the generated heat triggers a (physico-)chemical process, such as ablation, polymerization, insolubilization by cross-linking of a polymer, heat-induced solubilization, or particle coagulation of a thermoplastic polymer latex. Examples of such thermal plates, wherein also the role of surface roughness of the aluminum support is discussed, are disclosed in US 6,242,156 and EP-A 884 647.
- EP 0,704,320 discloses mechanical roughening of an aluminium or an aluminium alloy substrate by wet brushing the substrate with a cylinder brush whereby the roughened surface of the substrate obtains an average center line roughness of 0.3 µm to 1.2 µm.
- A printing plate with a smooth and pore- free metal surface which has a Ra value < 0.2 µm and which can directly be provided with an image is disclosed in EP 0,693,371. The applied images can repeatedly be erased.
- US 6,374,737 discloses a process for making an ablative printing plate material comprising an aluminium alloy as substrate which is preferably mill finished or finished via roll texturing, chemical texturing, mechanical texturing, electrochemical texturing or combinations thereof. Ra values of 5 to 15 microinches are disclosed for substrates rolled with EDT (electron discharge texturing) treated rolls.
- US 4,800,950 describes a process for manufacturing substrates for lithographic printing plates with improved mechanical properties. The process involves electrochemical roughening, etching and anodizing of cast aluminium alloys whereby Ra values of 0.23 µm to 0.37 µm are obtained.
- A negative-working radiation sensitive imaging element comprising a grained and anodized aluminium substrate with an anodic weight of 3 g/m2 is disclosed in US 6,140,022.
- A specific problem associated with thermal plate precursors is the limited shelf life of the coating. Especially when stored at elevated temperature, which is inevitable during transport by truck, boat, etc. the plates may show significant toning (ink-acceptance in the non-image areas).
- It is an aspect of the present invention to provide a positive-working thermal lithographic printing plate precursor with improved shelf life. This object is realized by the material of claim 1, having the characterizing feature that a low surface roughness of the grained and anodized aluminum support unexpectedly provides an improved shelf life of the material. Specific embodiments of the invention are defined in the dependent claims.
- The support of the plate precursor of the present invention is a grained and anodized aluminum support having a hydrophilic surface that is characterized by a low surface roughness, expressed as arithmetical mean center-line roughness (Ra), sometimes also referred to as CLA (center-line average). Ra as used herein is defined in ISO 4287/1 (= DIN 4762) and references therein. Ra values reported herein have been measured according to ISO 4288 and references therein by a mechanical profile method using a contact stylus with a very thin tip (also optical profile methods are known; such optical methods systematically provide higher values than the ISO method). The apparatus used for measuring Ra was a Talysurf 10 from Taylor Hobson Ltd.
- The Ra value of the hydrophilic surface of the grained and anodized aluminum support used in the material of the present invention is lower than 0.40 µm, preferably lower than 0.30 µm and even more preferably lower than 0.25 µm. A grained and anodized aluminum support having a hydrophilic surface characterized by the mentioned low Ra values is briefly referred to herein as a "smooth support". The lower limit of the Ra value may be 0.05 µm, preferably 0.1 µm.
- Graining and anodizing of aluminum lithographic supports is well known. The grained aluminum support used in the material of the present invention is preferably an electrochemically grained support. The acid used for graining can be e.g. nitric acid. The acid used for graining preferably comprises hydrogen chloride. Also mixtures of e.g. hydrogen chloride and acetic acid can be used.
- The relation between electrochemical graining and anodizing parameters such as electrode voltage, nature and concentration of the acid electrolyte or power consumption on the one hand and the obtained lithographic quality in terms of Ra and anodic weight (g/m2 of Al2O3 formed on the aluminum surface) on the other hand is well known. More details about the relation between various production parameters and Ra or anodic weight can be found in e.g. the article "Management of Change in the Aluminium Printing Industry" by F. R. Mayers, ATB Metallurgie 2002, 42(1-2),69-77. So the skilled person is well aware of the settings of the various parameters which are required for making a smooth surface on a grained aluminum support or for making a given anodic weight during aluminum anodization. According to the present invention the anodic weight at the hydrophilic surface is more than 3.0 g/m2 of aluminum oxide, a value above 4.0 g/m2 being even more preferred.
- The grained and anodized aluminum support may be post-treated to improve the hydrophilic properties of its surface. For example, the aluminum support may be silicated by treating its surface with a sodium silicate solution at elevated temperature, e.g. 95°C. Alternatively, a phosphate treatment may be applied which involves treating the aluminum oxide surface with a phosphate solution that may further contain an inorganic fluoride. Further, the aluminum oxide surface may be rinsed with an organic acid and/or salt thereof, e.g. carboxylic acids, hydroxycarboxylic acids, sulfonic acids or phosphonic acids, or their salts, e.g. succinates, phosphates, phosphonates, sulfates, and sulfonates. A citric acid or citrate solution is preferred. This treatment may be carried out at room temperature or may be carried out at a slightly elevated temperature of about 30 to 50°C. A further post-treatment involves rinsing the aluminum oxide surface with a bicarbonate solution. Still further, the aluminum oxide surface may be treated with polyvinylphosphonic acid, polyvinylmethylphosphonic acid, phosphoric acid esters of polyvinyl alcohol, polyvinylsulfonic acid, polyvinylbenzenesulfonic acid, sulfuric acid esters of polyvinyl alcohol, and acetals of polyvinyl alcohols formed by reaction with a sulfonated aliphatic aldehyde. It is further evident that one or more of these post-treatments may be carried out alone or in combination. More detailed descriptions of these treatments are given in GB-A- 1 084 070, DE-A- 4 423 140, DE-A- 4 417 907, EP-A- 659 909, EP-A- 537 633, DE-A- 4 001 466, EP-A- 292 801, EP-A- 291 760 and US-P- 4 458 005.
- The coating provided on the support is heat-sensitive, thereby providing a plate precursor which can be handled in normal working lighting conditions (daylight, fluorescent light) for several hours. The coating preferably does not contain UV-sensitive compounds which have an absorption maximum in the wavelength range of 200 nm to 400 nm such as diazo compounds, photoacids, photoinitiators, quinone diazides, or sensitizers. Preferably the coating neither contains compounds which have an absorption maximum in the blue and green visible light wavelength range between 400 and 600 nm.
- The coating may comprise one or more distinct layers. Besides the layers discussed hereafter, the coating may further comprise e.g. a "subbing" layer which improves the adhesion of the coating to the support, a covering layer which protects the coating against contamination or mechanical damage, and/or a light-to-heat conversion layer which comprises an infrared light absorbing compound.
- The coating is positive-working and capable of heat-induced solubilization, i.e. the coating is resistant to the developer and ink-accepting in the non-exposed state and becomes soluble in the developer upon exposure to heat or infrared light to such an extent that the hydrophilic surface of the support is revealed thereby.
- Preferably, the coating comprises a hydrophobic polymer that is soluble in an aqueous alkaline developer. Preferred polymers are phenolic resins, e.g. novolac, resoles, polyvinyl phenols and carboxy-substituted polymers. Typical examples of such polymers are described in DE-A-4007428, DE-A-4027301 and DE-A-4445820. In addition, the coating may comprise polymers which improve the run length and/or the chemical resistance of the plate. Examples thereof are polymers comprising sulfonamido (-SO2-NR-) or imido (-CO-NR-CO-) pendant groups, wherein R is hydrogen, optionally substituted alkyl or optionally substituted aryl, such as the polymers described in EP-A 894622, 901902, 933682 and WO99/63407.
- In a preferred embodiment, the coating also contains one or more dissolution inhibitors, i.e. one or more materials which reduce the dissolution rate of the hydrophobic polymer in the aqueous alkaline developer at the non-exposed areas of the coating. The dissolution inhibiting capability of the inhibitor can easily be tested by coating two samples on a support : a reference sample containing only the hydrophobic polymer and another including both the polymer (in equal amounts as the reference) as well as the inhibitor. A series of unexposed samples is immersed in an aqueous alkaline developer, each sample during a different time period. After the immersion period, the sample is removed from the developer, immediately rinsed with water, dried and then the dissolution of the coating in the developer is measured by comparing the weight of the sample before and after the development. As soon as the coating is dissolved completely, no more weight loss is measured upon longer immersion time periods, i.e. a curve representing weight loss as a function of immersion time reaches a plateau from the moment of complete dissolution of the layer. A material has good inhibiting capability when the coating of the sample without the inhibitor has dissolved completely in the developer before the sample with the inhibitor is attacked by the developer to such an extent that the ink-accepting capability of the coating is affected.
- The dissolution inhibitor(s) can be added to the layer which comprises the alkali-soluble hydrophobic polymer discussed above. In this embodiment, the dissolution rate of the non-exposed coating in the developer is reduced by interaction between the hydrophobic polymer and the inhibitor, due to e.g. hydrogen bonding between these compounds. The dissolution inhibiting capability of the inhibitor is preferably reduced or destroyed by the heat generated during the exposure so that the coating readily dissolves in the developer at exposed areas. Such inhibitors are preferably organic compounds which comprise at least one aromatic group and a hydrogen bonding site, e.g. a carbonyl group, a sulfonyl group, or a nitrogen atom which may be quaternized and which may be part of a heterocyclic ring or which may be part of an amino substituent of said organic compound. Suitable dissolution inhibitors of this type have been disclosed in e.g. EP-A 825927 and 823327. Some of the compounds mentioned below, e.g. infrared dyes such as cyanines and contrast dyes such as quaternized triarylmethane dyes can also act as a dissolution inhibitor.
- Water-repellent polymers represent a second type of suitable dissolution inhibitors. Such polymers seem to increase the developer resistance of the coating by repelling the aqueous developer from the coating. The water-repellent polymers can be added to the layer comprising the hydrophobic polymer and/or can be present in a separate layer provided on top of the layer with the hydrophobic polymer. In the latter embodiment, the water-repellent polymer forms a barrier layer which shields the coating from the developer and the solubility of the barrier layer in the developer or the penetrability of the barrier layer by the developer can be reduced by exposure to heat or infrared light, as described in e.g. EP-A 864420, EP-A 950517 and WO99/21725. Preferred examples of the water-repellent polymers are polymers comprising siloxane and/or perfluoroalkyl units. In one embodiment, the coating contains such a water-repellent polymer in an amount between 0.5 and 25 mg/m2, preferably between 0.5 and 15 mg/m2 and most preferably between 0.5 and 10 mg/m2. When the water-repellent polymer is also ink-repelling, e.g. in the case of polysiloxanes, higher amounts than 25 mg/m2 can result in poor ink-acceptance of the non-exposed areas. An amount lower than 0.5 mg/m2 on the other hand may lead to an unsatisfactory development resistance. The polysiloxane may be a linear, cyclic or complex cross-linked polymer or copolymer. The term polysiloxane compound shall include any compound which contains more than one siloxane group -Si(R,R')-O-, wherein R and R' are optionally substituted alkyl or aryl groups. Preferred siloxanes are phenylalkylsiloxanes and dialkylsiloxanes. The number of siloxane groups in the (co)polymer is at least 2, preferably at least 10, more preferably at least 20. It may be less than 100, preferably less than 60. In another embodiment, the water-repellent polymer is a block-copolymer or a graft-copolymer of a poly(alkylene oxide) block and a block of a polymer comprising siloxane and/or perfluoroalkyl units. A suitable copolymer comprises about 15 to 25 siloxane units and 50 to 70 alkylene oxide groups. Preferred examples include copolymers comprising phenylmethylsiloxane and/or dimethylsiloxane as well as ethylene oxide and/or propylene oxide, such as Tego Glide 410, Tego Wet 265, Tego Protect 5001 or Silikophen P50/X, all commercially available from Tego Chemie, Essen, Germany. Such a copolymer acts as a surfactant which upon coating, due to its bifunctional structure, automatically positions itself at the interface between the coating and air and thereby forms a separate top layer even when the whole coating is applied from a single coating solution. Simultaneously, such surfactants act as a spreading agent which improves the coating quality. Alternatively, the water-repellent polymer can be applied in a second solution, coated on top of the layer comprising the hydrophobic polymer. In that embodiment, it may be advantageous to use a solvent in the second coating solution that is not capable of dissolving the ingredients present in the first layer so that a highly concentrated water-repellent phase is obtained at the top of the coating.
- Preferably, also one or more development accelerators are included in the coating, i.e. compounds which act as dissolution promoters because they are capable of increasing the dissolution rate of the non-exposed coating in the developer, which can be tested by the same procedure as described above in relation to dissolution inhibitors. The simultaneous application of dissolution inhibitors and accelerators allows a precise fine tuning of the dissolution behavior of the coating. Suitable dissolution accelerators are cyclic acid anhydrides, phenols or organic acids. Examples of the cyclic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endoxy- 4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, alpha - phenylmaleic anhydride, succinic anhydride, and pyromellitic anhydride, as described in U.S. Patent No. 4,115,128. Examples of the phenols include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxy-benzophenone, 4-hydroxybenzophenone, 4,4',4"-trihydroxy-triphenylmethane, and 4,4',3",4"-tetrahydroxy-3,5,3',5'-tetramethyltriphenyl-methane, and the like. Examples of the organic acids include sulfonic acids, sulfinic acids, alkylsulfuric acids, phosphonic acids, phosphates, and carboxylic acids, as described in, for example, JP-A Nos. 60-88,942 and 2-96,755. Specific examples of these organic acids include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethylsulfuric acid, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4-cyclohexene-1,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid. The amount of the cyclic acid anhydride, phenol, or organic acid contained in the coating is preferably in the range of 0.05 to 20% by weight, relative to the coating as a whole.
- The material can be image-wise exposed directly with heat, e.g. by means of a thermal head, or indirectly by infrared light, which is preferably converted into heat by an infrared light absorbing compound, which may be a dye or pigment having an absorption maximum in the infrared wavelength range. The concentration of the sensitizing dye or pigment in the coating is typically between 0.25 and 10.0 wt.%, more preferably between 0.5 and 7.5 wt.% relative to the coating as a whole. Preferred IR-absorbing compounds are dyes such as cyanine or merocyanine dyes or pigments such as carbon black. A suitable compound is the following infrared dye :
- The coating may further contain an organic dye which absorbs visible light so that a perceptible image is obtained upon image-wise exposure and subsequent development. Such a dye is often called contrast dye or indicator dye. Preferably, the dye has a blue color and an absorption maximum in the wavelength range between 600nm and 750 nm. Although the dye absorbs visible light, it preferably does not sensitize the printing plate precursor, i.e. the coating does not become more soluble in the developer upon exposure to visible light. Suitable examples of such a contrast dye are the quaternized triarylmethane dyes.
- The infrared light absorbing compound and the contrast dye may be present in the layer comprising the hydrophobic polymer, and/or in the barrier layer discussed above and/or in an optional other layer. According to a highly preferred embodiment, the infrared light absorbing compound is concentrated in or near the barrier layer, e.g. in an intermediate layer between the layer comprising the hydrophobic polymer and the barrier layer.
- The printing plate precursor of the present invention can be exposed to infrared light with LEDs or a laser. Preferably, a laser emitting near infrared light having a wavelength in the range from about 750 to about 1500 nm is used, such as a semiconductor laser diode, a Nd:YAG or a Nd:YLF laser. The required laser power depends on the sensitivity of the image-recording layer, the pixel dwell time of the laser beam, which is determined by the spot diameter (typical value of modern plate-setters at 1/e2 of maximum intensity : 10-25 pm), the scan speed and the resolution of the exposure apparatus (i.e. the number of addressable pixels per unit of linear distance, often expressed in dots per inch or dpi; typical value : 1000-4000 dpi).
- Two types of laser-exposure apparatuses are commonly used: internal (ITD) and external drum (XTD) plate-setters. ITD plate-setters for thermal plates are typically characterized by a very high scan speed up to 500 m/sec and may require a laser power of several Watts. XTD plate-setters for thermal plates having a typical laser power from about 200 mW to about 1 W operate at a lower scan speed, e.g. from 0.1 to 10 m/sec.
- The known plate-setters can be used as an off-press exposure apparatus, which offers the benefit of reduced press down-time. XTD plate-setter configurations can also be used for on-press exposure, offering the benefit of immediate registration in a multi-color press. More technical details of on-press exposure apparatuses are described in e.g. US 5,174,205 and US 5,163,368.
- In the development step, the non-image areas of the coating are removed by immersion in an aqueous alkaline developer, which may be combined with mechanical rubbing, e.g. by a rotating brush. The developer preferably has a pH above 10, more preferably above 12. The development step may be followed by a rinsing step, a gumming step, a drying step and/or a post-baking step.
- The printing plate thus obtained can be used for conventional, so-called wet offset printing, in which ink and an aqueous dampening liquid is supplied to the plate. Another suitable printing method uses so-called single-fluid ink without a dampening liquid. Single-fluid ink consists of an ink phase, also called the hydrophobic or oleophilic phase, and a polar phase which replaces the aqueous dampening liquid that is used in conventional wet offset printing. Suitable examples of single-fluid inks have been described in US 4,045,232; US 4,981,517 and US 6,140,392. In a most preferred embodiment, the single-fluid ink comprises an ink phase and a polyol phase as described in WO 00/32705.
- A 0.30 mm thick aluminum foil was degreased by immersing the foil in an aqueous solution containing 40 g/l of sodium hydroxide at 60°C for 8 seconds and rinsed with demineralized water for 2 seconds. The foil was then electrochemically grained using an alternating current in an aqueous solution containing 12 g/l of hydrochloric acid and 38 g/l of aluminum sulphate (18 hydrate) at a temperature of 33°C and a current density of 130 A/dm2 to form a surface topography with an average center-line roughness Ra of 0.5 µm. After rinsing with demineralized water for 2 seconds, the aluminum foil was then etched with an aqueous solution containing 155 g/l of sulfuric acid at 70°C for 4 seconds and rinsed with demineralized water at 25°C for 2 seconds. The foil was subsequently subjected to anodic oxidation in an aqueous solution containing 155 g/l of sulfuric acid at a temperature of 45°C, at a current density of 22 A/dm2 to form an anodic oxidation film of 2.90 g/m2 of Al2O3, then washed with demineralized water for 2 seconds and posttreated for 10 seconds with a solution containing 4 g/l polyvinylphosphonic acid at 40°C, rinsed with demineralized water at 20°C during 2 seconds and dried.
- The same procedure was used as described for lithographic support 1 with the proviso that the current density during graining and anodizing was 90 A/dm2 and 30 A/dm2 respectively. As a result, the Ra value was 0.2 µm and the anodic weight was 4.0 g/m2.
- The comparative printing plate precursor 1 and the printing plate precursor 2 according to the invention were produced by coating the solution defined in Table 1 onto the above described lithographic substrates 1 and 2. The coating solution was applied at a wet coating thickness of 26 µm on a coating line operating at a speed of 10.8 m/min and then dried at 135°C.
Table 1 : composition of the coating solution Parts (grams) Tetrahydrofuran 209.20 Alnovol SPN452 (1) 102.02 Dowanol PM (2) 332.13 Methyl ethyl ketone 266.20 S0094 (3) 2.10 1 wt.% solution of Basonyl Blue 640 (4) in Dowanol PM 53.00 1 wt.% solution of TegoGlide 410 (5) in Dowanol PM 8.50 1 wt.% solution of TegoWet 265 (5) in Dowanol PM 21.55 3,4,5-trimethoxy cinnamic acid 5.30 (1)Alnovol SPN452 is a 40.5 wt.% solution of novolac in Dowanol PM (commercially available from Clariant). (2)1-methoxy-2-propanol from Dow Chemical Company. (3) S0094 is an IR absorbing cyanine dye commercially available from FEW Chemicals. S0094 has the chemical structure IR-1 shown above. (4)Basonyl Blue 640 is a quaternized triarylmethane dye commercially available from BASF. (5) TegoWet 265 and TegoGlide 410 are both block-co-polysiloxane/poly(alkylene oxide) surfactants commercially available from Tego Chemie Service GmbH. - One part of each printing plate precursor was packaged in an open paper bag and stored during 7 days at ambient temperature. Another part of the printing plate precursor was packaged in an open bag and stored for 7 days at 50°C.
- The printing plate precursors were then exposed on a CreoScitex Trendsetter 3244 operating at a drum rotation speed of 150 rpm and the energy on the plates was varied from 80 mJ/cm2 up to 200 mJ/cm2 with steps of 20 mJ/cm2. The plates were then processed in an Agfa Autolith T processor operating at a speed of 0.96 m/min using Agfa TD5000 developer at 25°C and RC795 as gum. Only the plates obtained with the optimum exposure energy were used in the evaluation, using a Heidelberg GTO52 printing press with K+E 800 Skinnex Black (commercially available from BASF) as ink and ROTA-MATIC (commercially available from Unigraphica GmbH) as fountain. When stored at ambient temperature, both the printing plate precursor 1 and 2 had a very good lithographic behavior and printed without toning. The plate obtained from precursor 1 stored at elevated temperature showed severe toning in the non-image areas and was a useless printing plate. The plate which was obtained from the precursor 2 that had been stored at elevated temperature printed without toning.
Claims (9)
- A positive-working lithographic printing plate precursor comprising (i) a grained and anodized aluminum support having a hydrophilic surface and (ii) a heat-sensitive oleophilic coating provided on the hydrophilic surface, wherein said coating is capable of dissolving in an aqueous alkaline developer at a higher dissolution rate in areas of said coating which are exposed to heat or infrared light than in unexposed areas, characterized in that the hydrophilic surface has a surface roughness, expressed as arithmetical mean center-line roughness Ra, which is less than 0.40 µm and comprises more than 3.0 g/m2 of aluminum oxide.
- A plate precursor according to claim 1 wherein the hydrophilic surface has a surface roughness, expressed as arithmetical mean center-line roughness Ra, which is less than 0.3 µm.
- A plate precursor according to any preceding claim wherein the aluminum support comprises more than 4.0 g/m2 of aluminum oxide at the hydrophilic surface.
- A plate precursor according any preceding claim wherein the coating comprises (a) a hydrophobic polymer which is soluble in the developer and (b) a dissolution inhibitor.
- A plate precursor according to claim 4 wherein the dissolution inhibitor is a water-repellent polymer.
- A plate precursor according to 5 wherein the water-repellent polymer is- a polymer comprising siloxane and/or perfluoroalkyl units; or- a block- or graft-copolymer of a poly(alkylene oxide) block and a block comprising siloxane and/or perfluoroalkyl units.
- A plate precursor according to claim 4 wherein the dissolution inhibitor is an organic compound comprising an aromatic group and a hydrogen bonding site.
- A plate precursor according to any preceding claim wherein the coating further comprises a dissolution accelerator.
- Use of a grained and anodized aluminum support having a hydrophilic surface which is characterized by a surface roughness, expressed as arithmetical mean center-line roughness Ra, which is less than 0.40 µm and which comprises more than 3.0 g/m2 of aluminum oxide,
in a positive-working lithographic printing plate precursor comprising a heat-sensitive oleophilic coating provided on the hydrophilic surface, wherein said coating is capable of dissolving in an aqueous alkaline developer at a higher dissolution rate in areas of said coating which are exposed to heat or infrared light than in unexposed areas,
for increasing the shelf life of said printing plate precursor.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20030101850 EP1380417B1 (en) | 2002-07-03 | 2003-06-24 | Positive-working lithographic printing plate precursor |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02100778 | 2002-07-03 | ||
EP02100778 | 2002-07-03 | ||
EP20030101850 EP1380417B1 (en) | 2002-07-03 | 2003-06-24 | Positive-working lithographic printing plate precursor |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1380417A1 EP1380417A1 (en) | 2004-01-14 |
EP1380417B1 true EP1380417B1 (en) | 2006-08-23 |
Family
ID=29737946
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20030101850 Expired - Lifetime EP1380417B1 (en) | 2002-07-03 | 2003-06-24 | Positive-working lithographic printing plate precursor |
Country Status (1)
Country | Link |
---|---|
EP (1) | EP1380417B1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070077513A1 (en) | 2003-12-18 | 2007-04-05 | Agfa-Gevaert | Positive-working lithographic printing plate precursor |
EP1588847B1 (en) * | 2004-04-21 | 2007-05-09 | Agfa Graphics N.V. | Method for accurate exposure of small dots on a heat-sensitive positive-working lithographic plate material |
US7467587B2 (en) | 2004-04-21 | 2008-12-23 | Agfa Graphics, N.V. | Method for accurate exposure of small dots on a heat-sensitive positive-working lithographic printing plate material |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0223737B1 (en) * | 1985-10-30 | 1989-12-27 | Schweizerische Aluminium Ag | Support for a lithographic printing plate |
DE4428661B4 (en) * | 1993-08-13 | 2004-07-01 | Mitsubishi Paper Mills Limited | Lithographic printing plate |
DE4426012C2 (en) * | 1994-07-22 | 1998-05-20 | Roland Man Druckmasch | Erasable printing form, its use and methods for erasing and regenerating the printing form |
DE4435221A1 (en) * | 1994-09-30 | 1996-04-04 | Hoechst Ag | Method for mechanically roughening the surface of a printing plate support and brush roller for carrying out the method |
US6140022A (en) * | 1996-07-19 | 2000-10-31 | Agfa-Gevaert, N.V. | Radiation sensitive imaging element and a method for producing lithographic plates therewith |
US6374737B1 (en) * | 2000-03-03 | 2002-04-23 | Alcoa Inc. | Printing plate material with electrocoated layer |
-
2003
- 2003-06-24 EP EP20030101850 patent/EP1380417B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP1380417A1 (en) | 2004-01-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1826021B1 (en) | Positive working lithographic printing plates | |
EP1904305B1 (en) | Method for making a negative-working lithographic printing plate precursor. | |
EP1594696B1 (en) | Heat-sensitive lithographic printing plate precursor. | |
EP1834764B1 (en) | Negative working, heat-sensitive lithographic printing plate precursor | |
EP1738901B1 (en) | Heat-sensitive lithographic printing plate precursor | |
US6983694B2 (en) | Negative-working thermal lithographic printing plate precursor comprising a smooth aluminum support | |
EP1826022A1 (en) | A method for making a lithographic printing plate support | |
EP1738902A1 (en) | Method for preparing a lithographic printing plate precursor | |
US7348126B2 (en) | Negative working, heat-sensitive lithographic printing plate precursor | |
EP1738900B1 (en) | Heat-sensitive lithographic printing plate precursor | |
EP1380417B1 (en) | Positive-working lithographic printing plate precursor | |
US6846613B2 (en) | Positive-working lithographic printing plate precursors | |
EP1256444B1 (en) | Positive-working lithographic printing plate precursor | |
US20040048195A1 (en) | Heat-sensitive lithographic printing plate precursor | |
US7294447B2 (en) | Positive-working lithographic printing plate precursor | |
US20050260934A1 (en) | Positive-working lithographic printing plate precursor | |
US20070077513A1 (en) | Positive-working lithographic printing plate precursor | |
EP1249341A1 (en) | Lithographic printing plate precursor | |
EP1604818B1 (en) | Negative working, heat-sensitive lithographic printing plate precursor | |
JP4359455B2 (en) | Positive acting lithographic printing plate precursor | |
EP1295717B1 (en) | Heat-sensitive positive-working lithographic printing plate precursor | |
US20070003875A1 (en) | Method for preparing a lithographic printing plate precursor | |
US20070003869A1 (en) | Heat-sensitive lithographic printing plate-precursor | |
EP1396338B1 (en) | Heat-sensitive lithographic printing plate precursor | |
EP2098376B1 (en) | A method for making a lithographic printing plate support |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK |
|
17P | Request for examination filed |
Effective date: 20040714 |
|
AKX | Designation fees paid |
Designated state(s): DE FR GB NL |
|
17Q | First examination report despatched |
Effective date: 20041015 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB NL |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 60307738 Country of ref document: DE Date of ref document: 20061005 Kind code of ref document: P |
|
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E |
|
NLS | Nl: assignments of ep-patents |
Owner name: AGFA GRAPHICS N.V. Effective date: 20070321 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20070524 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 14 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 15 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R081 Ref document number: 60307738 Country of ref document: DE Owner name: AGFA NV, BE Free format text: FORMER OWNER: AGFA GRAPHICS N.V., MORTSEL, BE |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: HC Owner name: AGFA NV; BE Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), CHANGE OF OWNER(S) NAME; FORMER OWNER NAME: AGFA GRAPHICS N.V. Effective date: 20180126 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 16 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: CD Owner name: AGFA NV, BE Effective date: 20180628 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20200330 Year of fee payment: 18 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20200428 Year of fee payment: 18 Ref country code: DE Payment date: 20200505 Year of fee payment: 18 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20200428 Year of fee payment: 18 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 60307738 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MM Effective date: 20210701 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20210624 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210624 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210701 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210630 |