EP2042310A2 - Flachdruckplattenvorläufer - Google Patents
Flachdruckplattenvorläufer Download PDFInfo
- Publication number
- EP2042310A2 EP2042310A2 EP08017057A EP08017057A EP2042310A2 EP 2042310 A2 EP2042310 A2 EP 2042310A2 EP 08017057 A EP08017057 A EP 08017057A EP 08017057 A EP08017057 A EP 08017057A EP 2042310 A2 EP2042310 A2 EP 2042310A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- printing plate
- planographic printing
- plate precursor
- acid
- recording layer
- 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.)
- Granted
Links
- 238000007639 printing Methods 0.000 title claims abstract description 119
- 239000002243 precursor Substances 0.000 title claims abstract description 90
- 229920000642 polymer Polymers 0.000 claims abstract description 157
- 150000001875 compounds Chemical class 0.000 claims abstract description 122
- 229920005989 resin Polymers 0.000 claims abstract description 111
- 239000011347 resin Substances 0.000 claims abstract description 111
- 238000000034 method Methods 0.000 claims abstract description 88
- 239000006185 dispersion Substances 0.000 claims abstract description 77
- 239000003513 alkali Substances 0.000 claims abstract description 48
- 239000006096 absorbing agent Substances 0.000 claims abstract description 38
- 239000011159 matrix material Substances 0.000 claims abstract description 31
- 125000005373 siloxane group Chemical class [SiH2](O*)* 0.000 claims abstract description 15
- 125000001183 hydrocarbyl group Chemical class 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 73
- 239000002253 acid Substances 0.000 claims description 38
- 229920003986 novolac Polymers 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000004090 dissolution Methods 0.000 claims description 23
- 239000004816 latex Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 229920000126 latex Polymers 0.000 claims description 11
- 239000003094 microcapsule Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 description 211
- 238000011282 treatment Methods 0.000 description 60
- 239000000178 monomer Substances 0.000 description 54
- 238000000576 coating method Methods 0.000 description 52
- -1 quinone diazide compound Chemical class 0.000 description 52
- 239000011248 coating agent Substances 0.000 description 50
- 229910052782 aluminium Inorganic materials 0.000 description 48
- 239000000975 dye Substances 0.000 description 46
- 239000002904 solvent Substances 0.000 description 45
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 42
- 239000000049 pigment Substances 0.000 description 39
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 32
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 30
- 239000007788 liquid Substances 0.000 description 28
- 239000000203 mixture Substances 0.000 description 25
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 21
- 229910052731 fluorine Inorganic materials 0.000 description 21
- 239000000463 material Substances 0.000 description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 20
- 239000011737 fluorine Substances 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 150000003839 salts Chemical class 0.000 description 17
- 238000007788 roughening Methods 0.000 description 16
- 239000004094 surface-active agent Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 239000007848 Bronsted acid Substances 0.000 description 14
- 239000011230 binding agent Substances 0.000 description 14
- 238000011161 development Methods 0.000 description 14
- 230000035945 sensitivity Effects 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 13
- 125000001424 substituent group Chemical group 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000005507 spraying Methods 0.000 description 12
- 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 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 235000000346 sugar Nutrition 0.000 description 11
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 125000000129 anionic group Chemical group 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 235000019198 oils Nutrition 0.000 description 10
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 10
- 125000000565 sulfonamide group Chemical group 0.000 description 10
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 125000005462 imide group Chemical group 0.000 description 9
- 239000003999 initiator Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 239000012954 diazonium Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000007743 anodising Methods 0.000 description 7
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 150000001989 diazonium salts Chemical class 0.000 description 7
- 230000003993 interaction Effects 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000035515 penetration Effects 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000008163 sugars Chemical class 0.000 description 5
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 4
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
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- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 239000002280 amphoteric surfactant Substances 0.000 description 4
- VUEDNLCYHKSELL-UHFFFAOYSA-N arsonium Chemical class [AsH4+] VUEDNLCYHKSELL-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
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- 150000001721 carbon Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229930003836 cresol Natural products 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
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- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- JTHNLKXLWOXOQK-UHFFFAOYSA-N hex-1-en-3-one Chemical compound CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
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- 229920001778 nylon Polymers 0.000 description 4
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- 239000001488 sodium phosphate Substances 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
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- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
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- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 3
- 235000013681 dietary sucrose Nutrition 0.000 description 3
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 3
- 210000004209 hair Anatomy 0.000 description 3
- FBPFZTCFMRRESA-UHFFFAOYSA-N hexane-1,2,3,4,5,6-hexol Chemical compound OCC(O)C(O)C(O)C(O)CO FBPFZTCFMRRESA-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229920001542 oligosaccharide Polymers 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 150000003009 phosphonic acids Chemical class 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
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- BNTUIAFSOCHRHV-UHFFFAOYSA-N n-ethyl-n-phenylprop-2-enamide Chemical compound C=CC(=O)N(CC)C1=CC=CC=C1 BNTUIAFSOCHRHV-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- YOOYVODKUBZAPO-UHFFFAOYSA-N naphthalen-1-ylphosphonic acid Chemical compound C1=CC=C2C(P(O)(=O)O)=CC=CC2=C1 YOOYVODKUBZAPO-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
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- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
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- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
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- 230000008092 positive effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 239000008262 pumice Substances 0.000 description 1
- 239000001057 purple pigment Substances 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
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- 229920003987 resole Polymers 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 description 1
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- AWUCVROLDVIAJX-GSVOUGTGSA-N sn-glycerol 3-phosphate Chemical compound OC[C@@H](O)COP(O)(O)=O AWUCVROLDVIAJX-GSVOUGTGSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
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- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
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- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
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- 239000001589 sorbitan tristearate Substances 0.000 description 1
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- 229960004129 sorbitan tristearate Drugs 0.000 description 1
- 229960002920 sorbitol Drugs 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 125000005537 sulfoxonium group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- VTLHPSMQDDEFRU-UHFFFAOYSA-O telluronium Chemical compound [TeH3+] VTLHPSMQDDEFRU-UHFFFAOYSA-O 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
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 150000007944 thiolates Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- ROVRRJSRRSGUOL-UHFFFAOYSA-N victoria blue bo Chemical compound [Cl-].C12=CC=CC=C2C(NCC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 ROVRRJSRRSGUOL-UHFFFAOYSA-N 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
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- 239000001043 yellow dye Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
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
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
- B41C1/1016—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 characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
- B41C2201/02—Cover layers; Protective layers
-
- 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
- B41C2210/14—Multiple imaging layers
-
- 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 planographic printing plate precursor. More specifically, the invention relates to an infrared-laser-applicable planographic printing plate precursor from which a printing plate can be directly formed based on digital signals from a computer or the like.
- Materials which can be used for positive planographic printing plate precursors applicable for infrared lasers include, as essential components, a binder resin soluble in an aqueous alkaline solution (hereinafter referred to where appropriate as an "alkali-soluble resin"), and an infra red dye which absorbs light to generate heat.
- an image is formed in a positive planographic printing plate precursor
- the infra red dye interacts with the binder resin in its unexposed portions (image portions) so as to function as a dissolution inhibitor which can substantially reduce the solubility of the binder resin.
- image portions image portions
- interaction of the infra red dye with the binder resin is weakened by the heat generated. Consequently, an exposed portion can turn into a state in which it can be dissolved in an alkaline developer, so that an image is formed thereon and a planographic printing plate is produced.
- the plate precursor when using an infrared-laser-applicable positive planographic printing plate precursor, if the surface state of the unexposed portions of the plate precursor is slightly changed by human finger touching the surface or some other action, the affected unexposed portions (image portions) are dissolved by development to generate marks like scars. As a result, the plate precursor has problems in that the printing durability thereof deteriorates and the ink-acceptability thereof worsens.
- the positive planographic printing plate material used for plate-making by exposure to UV light comprises a binder resin soluble in an aqueous alkali solution, an onium salt and a quinone diazide compound as essential ingredients.
- the onium salt and quinone diazide compound act, in light-unexposed regions (image regions), as a dissolution inhibitor by interaction with the binder resin.
- non-image regions In light-exposed regions (non-image regions), on the other hand, they act as a dissolution accelerator by generating an acid upon decomposition by light. That is, the onium salt and quinone diazide compound play two roles, that is, the role of dissolution inhibitor and the role of acid generator.
- the infra red dye functions only as a dissolution inhibitor of unexposed portions (image portions), and does not promote the dissolution of exposed portions (non-image portions). Therefore, in order to make distinctive the difference in solubility between the unexposed portion and the exposed portion in the a positive planographic printing plate precursor for infrared laser, it is inevitable to use a that a material having which already has a high solubility in an alkali developing solution is used as the binder resin. There is therefore the case that the state of the plate material before developed becomes unstable.
- an ink-receptive recording layer of such a planographic printing plate precursor is formed on a hydrophilic support, and as a result, adhesion of the recording layer at the interface of the support may become unstable, which may affect printing durability of an unexposed area (image area) of a planographic printing plate formed therefrom.
- planographic printing plate precursor which is provided with a recording layer, comprising a lower recording layer containing a sulfonamide acryl resin, and an upper layer, which contains a water-insoluble and alkali-soluble resin and a light-heat photo-thermo converting agent, and which is improved in solubility in an aqueous alkali solution by exposure to light (see, for example, the publication of JP-A No 11-218914 ).
- This type of planographic printing plate precursor produces the effect that, because the lower recording layer which is highly alkali-soluble is exposed when the recording layer is removed on an exposed portion, an undesired residual film and the like are removed smoothly by an alkali developing agent.
- the lower recording layer also functions as an insulating layer so that thermal diffusion to the support is efficiently suppressed.
- a planographic printing plate precursor has been proposed in which a polymer is blended in the lower recording layer to provide chemical resistance (see, for example, a leaflet of International Publication (W/O) No. 01/46318).
- planographic printing plate precursor which is provided with a hydrophilic support having provided thereon a first layer which is water-insoluble and alkali-soluble, a second layer that forms a heat-sensitive positive image, and a third layer which suppresses penetration of an alkaline developer, in order to improve a function whereby penetration of developer is suppressed in a planographic printing plate precursor having a recording layer having a multilayer structure (for example, EP1738902A1 ).
- the present invention is made in view of the above circumstances and provides a positive planographic printing plate precursor excellent in sensitivity as well as image reproducibility.
- the invention provides a planographic printing plate precursor comprising, in this order: a support; two or more positive recording layers respectively comprising a resin and an infrared absorber and respectively having a solubility with respect to an aqueous alkali solution that is increased by exposure to infrared laser light; and a layer comprising a polymer compound, wherein: the polymer compound comprises at least one of a fluorine-substituted hydrocarbon group or a siloxane group; of the two or more positive recording layers, a positive recording layer that is nearest to the support comprises two resins; and one of the two resins constitutes a dispersion phase that is dispersed in a matrix phase which serves as a dispersing medium and comprises the other of the two resins.
- Figure 1 is a graph of one example of an alternating current waveform used for electrochemical surface roughening treatment applied for the preparation of a support of a planographic printing plate precursor in the following EXAMPLE.
- Figure 2 is a side view of one example of a radial-type cell used for the electrochemical surface roughening treatment with the alternating current waveform used for the preparation of a support of a planographic printing plate precursor in the following EXAMPLE.
- the positive recording layer nearest to a support is hereinafter referred to as a "lower recording layer” as necessary.
- the layer having the polymer compound having at least one of a fluorine-substituted hydrocarbon group or a siloxane group is hereinafter referred to as an "outermost layer” as necessary.
- planographic printing plate precursor of the invention may be provided to the planographic printing plate precursor of the invention in addition to the plurality of the positive recording layers and the outermost layer as long as the effect of the invention is not hindered.
- the dispersion phase formed by a resin in the lower recording layer which is one of the characteristics of the planographic printing plate precursor of the invention, can be formed by, for example, (1) using a plural kinds of resins that are incompatible with each other in combination, or (2) dispersing, in a resin constituting the matrix phase, the resin constituting the dispersion phase in granular form such as microcapsule or latex form.
- the planographic printing plate precursor of the invention employs a system utilizing change of solubility of the recording layer to an alkaline water. Therefore, in a preferable embodiment, a resin used in the positive recording layer has a water-insoluble and alkaline water-soluble resin.
- the method (1) which is a method including forming a dispersion phase and a matrix phase (a disperse medium) by using a plural kind of resins that are incompatible with each other in combination, is preferable from the standpoint of ease of production.
- the plural kind of resins may be those which are incompatible, or may be those which can be dissolved uniformly in a coating solvent and form a dispersion phase along with the removal of the solvent when forming the recording layer.
- a resin which forms the matrix phase is formed of a polymer compound which is insoluble in water and soluble in an aqueous alkali solution, while the dispersion phase contains a compound which generates an acid or a radical when irradiated with an infrared laser.
- a resin which forms the matrix phase is formed of a polymer compound which is insoluble in water and soluble in an aqueous alkali solution, while the dispersion phase contains a compound having an alkali solubility that is changed by irradiation with an infrared laser.
- the rate of dissolution with respect to an alkaline aqueous solution of the resin constituting the dispersion phase is preferably slower than that of the resin included in the matrix phase.
- a polymer which configures the dispersion phase in the invention can be selected from resins described hereinafter. Among those resins, a novolak resin is particularly preferable as the polymer which configures the dispersion phase.
- the maximum major axis of the dispersion phase is preferably from 0.1 ⁇ m to 0.8 ⁇ m, and the average major axis of the dispersion phase is preferably from 0.05 ⁇ m to 0.6 ⁇ m.
- the size of the dispersion phase can be evaluated by cutting the recording layer with a microtome or the like to give sections of the photosensitive layer, then making the sections electroconductive, taking a photograph thereof with a scanning electron microscope (SEM) and evaluating the size of the circular or elliptical dispersion phase by an image analyzer.
- SEM scanning electron microscope
- the planographic printing plate precursor of the invention has the outermost layer, that is a layer provided over the positive recording layer having the lower recording layer and containing at least a polymer compound having at least one of a fluorine-substituted hydrocarbon group or a siloxane group.
- the resin matrix phase in the lower recording layer of the planographic printing plate precursor of the invention is provided with a dispersion phase, the solubility of which to an aqueous alkali solution is increased by heat or light.
- this configuration results in formation of paths by which an aqueous alkali solution permeates into the matrix phase, whereby accelerates the dissolution of the alkali-soluble resin matrix phase in the lower recording layer to the aqueous alkali solution.
- the solubility of the dispersion phase to an aqueous alkali solution is lower than that of the resin which configurates the matrix phase.
- the permeation of an aqueous alkali solution into the resin matrix phase in the lower recording layer can be efficiently suppressed so as to prevent the image regions from being damaged by the aqueous alkali solution.
- the image regions have excellent adherence to the support. It is expected that these conditions result in the excellent image reproducibility of the planographic printing plate precursor of the invention.
- the planographic printing plate precursor of the invention has the outermost layer containing a specific polymer compound on the multilayered positive recording layer having the structure as described above. In the unexposed regions, this configuration results in further effective suppression of penetration of the alkaline aqueous solution.
- the outermost layer is quickly removed together with the positive recording layer without causing residuals by being coupled with an effect of the positive recording layer, which is provided under the outermost layer and has the specific configuration, to accelerate dissolution thereof into an alkaline aqueous solution. It is expected that these conditions result in prevention of decrease in sensitivity of the planographic printing plate precursor of the invention.
- planographic printing plate precursor of the invention is particularly useful in formation of a high definition image using, for example, a FM screen which increases its use with recent CTP application, and can preferably be used in image formation using commercially available FM screens such as STACCATO (trade name, manufactured by CREO Co., Ltd.), FAIRDOT, RANDOT (both trade names, manufactured by Dainippon Screen Mfg. Co., Ltd.) or Co-Re SCREEN (trade name, manufactured by FUJIFILM Corporation).
- STACCATO trade name, manufactured by CREO Co., Ltd.
- FAIRDOT fluor DOT
- RANDOT both trade names, manufactured by Dainippon Screen Mfg. Co., Ltd.
- Co-Re SCREEN trade name, manufactured by FUJIFILM Corporation
- the outermost layer in the invention contains at least a polymer compound having a fluorine-substituted hydrocarbon group and/or a siloxane group.
- the polymer compound may be hereinafter referred to as a "specific polymer compound”.
- Preferable examples of the specific polymer compound contained in the outermost layer include a polymer compound having a perfluoroalkyl group and/or a siloxane group.
- the polymer compound when the specific polymer compound is a polymer compound having a siloxane group, the polymer compound may be linear, cyclic or complex-crosslinked homopolymer or copolymer.
- the scope of such a specific polymer compound encompasses any compound containing at least one siloxane group.
- siloxane group used herein means a group represented by -Si(R, R')-O-, wherein R and R' respectively represent an alkyl group which may have a substituent or an aryl group which may have a substituent.
- the number of the siloxane group in the specific polymer compound is at least 2, more preferably at least 10, and further preferably at least 20.
- the number of the siloxane group is preferably less than 100, and more preferably less than 60.
- the specific polymer compound may be a block copolymer or a graft copolymer, having a poly(alkylene oxide) block and a block having a structural unit containing siloxane and/or a perfluoroalkyl group.
- the specific polymer include a copolymer having 15 to 25 siloxane groups and 50 to 70 alkylene oxide groups. More preferable examples of the specific polymer compound include copolymers containing an ethylene oxide group and/or a propylene oxide group together with a phenylmethylsiloxane group and/or a dimethylsiloxane group. Those compounds are available as commercial products, such as TEGO ® GLIDE 410, TEGO ® WET 265, TEGO ® PROTECT 5001 or SILIKOPHEN ® P50/X (manufactured by Tego Chemie, Essen, Germany).
- the outermost layer may further contain other components in addition to the specific polymer compound as long as the effects of the invention is not impaired.
- Examples of the solvent that can be used in the coating liquid for forming the outermost layer include an organic solvent, and a mixture of water and a water-miscible organic solvent such as alcohol, glycol, ketone, ether, ester, aliphatic hydrocarbon, aromatic hydrocarbon, lactone or lactam.
- the solvent include methanol, ethanol, isopropanol, butanol, isoamyl alcohol, octanol, cetyl alcohol, ethylene glycol, 1-methoxy-2-propanol, 2-propanone, 2-butanone, tetrahydrofuran, ethyl acetate, propyl acetate, butyl acetate, hexane, heptane, octane, toluene, xylene and N-methylpyrrolidone.
- the solvent include isopropanol, 1-methoxy-2-propanol, 2-butanone and mixtures of any of these, and further preferable specific example of the solvent includes a mixture of 1-methoxy-2-propanol and isopropanol.
- the application amount of the outermost layer after drying is preferably in a range of 5 mg/m 2 to 500 mg/m 2 , and more preferably in a range of 10 mg/m 2 to 200 mg/m 2 from the standpoint of ensuring developability of the non-image regions.
- the positive recording layer of the planographic printing plate precursor of the invention has at least two layers which contain a resin and an infrared absorber and increase its solubility to an alkaline aqueous solution by exposure with infrared laser.
- a positive recording layer which is closest to the support among the at least two positive recording layers contains at least two resins, and at least one resin among these forms a dispersion phase.
- Embodiment (1) a dispersion phase is formed in a matrix phase, i.e., a disperse medium, using at least two resins (polymer compounds) which are incompatible with each other. A dispersion phase formed thereby is formed of a material which is incompatible with a material which forms the disperse medium.
- incompatible means that a combination of the two or more polymers does not outwardly appear as a one-phase solid or liquid, this being confirmed by suitably processing of sections of the recording layer and visually observing the sections or taking photographs of the sections with a scanning electron microscope and observing them.
- Examples of the polymer compound used in the combination of the at least two polymers that are incompatible with each other include a urethane polymer compound, an acrylic polymer compound, a styrene polymer compound, a novolak resin, a diazo resin, an amide polymer compound, and a polyether compound.
- Examples of the preferable combination include: a combination of an acrylic polymer compound and a urethane polymer compound; a combination of an acrylic or urethane polymer compound and a diazo resin; and a combination of a novolak resin and an acylic polymer compound or a urethane polymer compound.
- a combination containing a urethane polymer compound is preferable from the standpoint that it is relatively free from being damaged at the time of development.
- a dispersion phase is formed in the resin matrix phase, and an amount of the infrared absorber in the dispersion phase becomes large.
- a polymer which shows a stronger interaction due to hydrogen bonding, ionic properties etc. easily forms spheres or flat spheres in the binder.
- Such localization occurs because when an infrared absorber is present in a dispersion phase, the infrared absorber, which is generally ionic or a coordination complex, tends to be easily incorporated into the polymer compound showing the stronger interaction in the binder.
- the initiator When an acid generator or a radical generator (polymerization initiator) is made to coexist, the initiator usually has a group having high polarity such as an onium salt structure, triazine or sulfonate ester, and, similar to the infrared absorber, is easily incorporated into the dispersion phase.
- a structure in which a dispersion phase is formed in a polymer matrix phase as the disperse medium is referred to as an island structure.
- the island structure can be observed and evaluated in the following manner: a section of the recording layer obtained by cutting the planographic printing plate precursor by a microtome or the like is made to have conductivity and then a photograph of an image of the section is taken by a scanning electron microscope (SEM) to analyze the size of a circular or elliptic dispersion phase by using an image analyzer.
- SEM scanning electron microscope
- the section of the photosensitive layer can be subjected to, for example, etching with solvent and then a photograph of the section can be taken according to the method described in, for example, "Polymer Alloy and Polymer Blend" (L. A. UTRACKI, translated by Toshio NISHI, Tokyo Kagaku Dojzin), the disclosure of which is incorporated by reference herein, to thereby obtain a highly distinct image.
- Polymer Alloy and Polymer Blend L. A. UTRACKI, translated by Toshio NISHI, Tokyo Kagaku Dojzin
- a size of the dispersion phase present in the polymer binder phase depends on a coating solvent system, drying conditions after application, and the like.
- a dispersion phase having the longest diameter of 0.8 ⁇ m or less, which is preferably 0.6 ⁇ m or less, and an average major diameter of 0.6 ⁇ m or less, which is preferably 0.5 ⁇ m or less, can be formed by controlling those conditions. In this case, it is preferable that the longest diameter and the average major diameter are small.
- the lower limit of the size of a dispersion phase is not particularly limited. In general, the longest diameter is about 0.1 ⁇ m, and the average major diameter is about 0.05 ⁇ m.
- the "major diameter” is obtained by subjecting a dispersion phase to image analysis as described above, and means a diameter when a particle of the dispersion phase is circle, or means a major diameter when a particle of the dispersion phase is ellipse.
- the water-insoluble and aqueous alkali-soluble polymer compound (hereinafter referred to as an "alkali-soluble polymer" as required) which is used in plural positive recording layers includes homopolymers having an acidic group on a main chain and/or a side chain thereof, copolymers having an acidic group on a main chain and/or a side chain thereof, and mixtures of these polymers.
- the polymer layer according to the invention therefore has the characteristics that it is dissolved when being brought into contact with an alkali developing solution.
- the scope of the alkali-soluble polymer contained in the lower recording layer in the planographic printing plate precursor of the invention includes the specific polymer.
- any known alkali-soluble polymer may be used as the alkali-soluble polymer to be used in the lower recording layer and other recording layers (hereinafter referred to as an upper recording layer as required) in the invention without any particular limitation, while the alkali-soluble polymer is preferably a polymer compound having one functional group selected from (1) a phenolic hydroxyl group, (2) a sulfonamide group and (3) an active imide group in its molecule.
- the following compounds are given as examples, while these examples are not intended to be limiting of the invention.
- Examples of the polymer compounds comprising phenolic hydroxyl group may include novolak resin such as condensation polymers of phenol and formaldehyde; condensation polymers of m-cresol and formaldehyde, condensation polymers of p-cresol and formaldehyde, condensation polymers of m-/p-mixed cresol and formaldehyde, and condensation polymers of phenol/cresol (m-, p-, or m-/p-mixture) and formaldehyde; and condensation copolymers of pyrogallol and acetone.
- the polymer compound having a phenolic hydroxyl group it is preferable to use polymer compounds having a phenolic hydroxyl group at their side chains besides the above compounds.
- Examples of the polymer compound having a phenolic hydroxyl group at its side chain include polymer compounds obtained by homopolymerizing a polymerizable monomer comprising a low-molecular compound having one or more phenolic hydroxyl groups and one or more polymerizable unsaturated bonds or copolymerizing this monomer with other polymerizable monomers.
- Examples of the polymerizable monomer having a phenolic hydroxyl group include acrylamides, methacrylamides, acrylates and methacrylates each having a phenolic hydroxyl group or hydroxystyrenes.
- Specific examples of the polymerizable monomer which may be preferably used include N-(2-hydroxyphenyl)acrylamide, N-(3-hydroxyphenyl)acrylamide, N-(4-hydroxyphenyl)acrylamide, N-(2-hydroxyphenyl)methacrylamide, N-(3-hydroxyphenyl)methacrylamide, N-(4-hydroxyphenyl)methacrylamide, o-hydroxyphenylacrylate, m-hydroxyphenylacrylate, p-hydroxyphenylacrylate, o-hydroxyphenylmethacrylate, m-hydroxyphenylmethacrylate, p-hydroxyphenylmethacrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyren
- the alkali-soluble polymer compound having an active imide group is preferably those having an active imide group in its molecule.
- the polymer compound include polymer compounds obtained by homopolymerizing a polymerizable monomer comprising a low-molecular compound having one or more active imide groups and one or more polymerizable unsaturated bonds or copolymerizing this monomer with other polymerizable monomers.
- a compound specifically, N-(p-toluenesulfonyl)methacrylamide, N-(p-toluenesulfonyl)acrylamide and the like are preferably used.
- alkali-soluble polymer compound of the invention polymer compounds obtained by polymerizing two or more types among the polymerizable monomers having a phenolic hydroxyl group, polymerizable monomers having a sulfonamide group and polymerizable monomers having an active imide group, or polymer compounds obtained by copolymerizing these two or more polymerizable monomers with other polymerizable monomers are preferably used.
- the alkali-soluble polymer is a copolymer of the polymerizable monomer having a phenolic hydroxyl group, polymerizable monomer having a sulfonamide group or polymerizable monomer having an active imide group and other polymerizable monomers in the invention, it is preferable to contain a monomer imparting alkali-solubility in an amount of 10 mol% or more and more preferably 20 mol% or more in view of improving the solubility to an alkali solution and the development lalitude of the presursor.
- Examples of the monomer component to be copolymerized with the polymerizable monomer having a phenolic hydroxyl group, the polymerizable monomer having a sulfonamide group and the polymerizable monomer having an active imide group may include, though not particularly limited to, compounds represented by the following (m1) to (m12).
- Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
- the alkali-soluble polymer compound preferably comprises phenolic hydroxyl groups, in terms of the excellent image formability by exposure by infrared laser.
- the alkali-soluble polymer compound comprising phenolic hydroxyl groups include condensed copolymers of phenol and formaldehyde comprising an alkyl group having 3 to 8 carbon atoms as a substitute, such as tert-butylphenol formaldehyde resin and octylphenol formaldehyde resin described in US Patent No. 4,123,279 .
- a method of copolymerizing the aqueous alkali-soluble polymer compound for example, a conventionally known graft copolymerization method, block copolymerization method or random copolymerization method may be used.
- a resin having phenolic hydroxyl group is desirable in the point that it develops strong hydrogen bonding characteristics in an unexposed portion whereas a part of hydrogen bonds are released with ease in an exposed portion.
- the alkali-soluble polymer is more preferably a novolac resin.
- the alkali-soluble resin preferably has a weight average molecular weight of 500 to 20,000 and a number average molecular weight of 200 to 10,000.
- a preferable method of forming a dispersion phase in the lower recording layer will be described.
- selection of a coating solvent is an important factor in order that the dispersion phase forms a sea island structure in the lower recording layer with a maximum major axis of 0.8 ⁇ m or less and average major axis of 0.6 ⁇ m or less.
- a sea island structure having the target size can be formed.
- methyl ethyl ketone, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, ⁇ -butyrolactone and dimethyl sulfoxide are preferable. These solvents may be used either singly or by mixing two or more.
- the condition under which a coating layer that has not yet been dried (after the photosensitive coating liquid is applied) is dried is known as an important factor to make the dispersion phase constituting the island structure in the lower recording layer to have a specified size.
- the descriptions in JP-A No. 9-90610 may be adopted as a reference for the production of such an island structure.
- the polymer compound used to form the dispersion phase in the case of forming the polymer matrix phase and the dispersion phase by using the two or more polymer compounds incompatible with each other are shown below.
- X 1 and X 2 each independently represent -0-, or -NR 7 -;
- R 1 and R 4 each independently represent a hydrogen atom, or -CH 3 ;
- R 2 , R 5 , R 9 , R 12 and R 16 each independently represent an alkylene group, a cycloalkylene group, an arylene group or an aralkylene group which has 1 to 12 carbon atom and may have a substituent;
- R 3 , R 7 and R 13 each independently represent a hydrogen atom, or an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group which has 1 to 12 carbon atom and may have a substituent;
- R 6 and R 17 each independently represent an alkylgroup, a cycloalkyl group, an aryl group or an aralkyl group which has 1 to 12 carbon atom and may have a substituent;
- R 8 , R 10 and R 14 each independently represent a hydrogen atom or
- Examples of the above structural unit also include low-molecular compounds containing at least one active imino group represented by the following Formula (vi) and at least one polymerizable unsaturated bond, for example, N-(p-toluenesulfonyl)methacrylamide and N-(p-toluenesulfonyl)acrylamide.
- Examples of the above structural unit also include styrene compounds, vinyl acetate and vinyl alcohol, for example, o-, m- or p-hydroxystyrene, styrene p-sulfonate and o-, m- or p-carboxylstyrene.
- the monomers corresponding to any one of the above (1) to (5) may be used either singly or in combinations of two or more. Copolymers obtained by combining any one of these monomers (1) to (5) with monomers other than these monomers are more preferable.
- the structural unit derived from any one of the above monomers (1) to (5) is contained in an amount 10 mol% or more, preferably 20 mol% or more and still more preferably 25 mol% or more of such a copolymer.
- Examples of the monomer used in combination with any one of the monomers (1) to (5) include the following compounds (6) to (16).
- (Substituted) alkylacrylates such as methylacrylate, ethylacrylate, propylacrylate, butylacrylate, amylacrylate, hexylacrylate, octylacrylate, benzylacrylate, 2-chloroethylacrylate, glycidylacrylate and N-dimethylaminoethylacrylate.
- alkylmethacrylates such as methylmethacrylate, ethylmethacrylate, propylmethacrylate, butylmethacrylate, amylmethacrylate, hexylmethacrylate, cyclohexylmethacrylate, benzylmethacrylate, glycidylmethacrylate and N-dimethylaminoethylmethacrylate.
- Acrylamide or methacrylic acid amides such as acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide and N-ethyl-N-phenylacrylamide.
- Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether.
- Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
- Styrenes such as styrene, ⁇ -methylstyrene, methylstyrene and chloromethylstyrene.
- Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone.
- Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.
- N-vinylpyrrolidone N-vinylcarbazole
- 4-vinylpyridine acrylonitrile and methacrylonitrile
- Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide and N-(p-chlorobenzoyl)methacrylamide.
- the polymer compound preferably has a weight average molecular weight of 2,000 or more and a number average molecular weight of 1000 or more, and more preferably has a weight average molecular weight of 5,000 to 300,000, a number average molecular weight of 2,000 to 250,000 and a degree of dispersion (the weight average molecular weight/the number average molecular weight) of 1.1 to 10.
- alkali-soluble novolac resin used in the invention may include alkali-soluble novolac resins such as a phenolformaldehyde resin, m-cresolformaldehyde resin, p-cresolformaldehyde resin, m-/p- mixed cresolformaldehyde resin and phenol/cresol (any of m-, p- and m-/p- mixture) mixed formaldehyde resin.
- alkali-soluble novolac resins those having a weight average molecular weight of 500 to 20,000 and a number average molecular weight of 200 to 10,000 are used.
- a condensate of a phenol having an alkyl group having 3 to 8 carbon atoms as a substituent and formaldehyde such as a t-butylphenolformaldehyde resin and octylphenolformaldehyde resin as described in U.S. Patent No. 4,123,279 may be used together.
- the alkali-soluble novolak resin preferably has a high content of a novolak resin, the bonding property of an ortho position thereof being high.
- the novolak resin include a xylenol cresol formaldehyde resin, a m-cresol formaldehyde resin or a p-cresol formaldehyde resin. Any of those specific novolak resins are preferably contained in an amount of preferably 10% by mass or more, and more preferably 30% by mass or more relative to the total amount of the whole novolak resin used in the alkali-soluble novolak resin.
- the lower recording layer having a resin matrix phase containing the thus formed dispersion phase contains, in the dispersion phase, a compound which changes solubility to an alkaline solution by an infrared absorber and heat in a high content in the case that the lower recording layer is a positive recording layer, thereby efficiently improves solubility of the polymer matrix phase to an alkaline solution.
- the resin constituting the dispersion phase in microcapsule form in the invention can be easily prepared by methods described in the examples of JP-A No. 1-145190 or the method described in " NEW EDITION, MICROCAPSULE-ITS PREPARATION, NATURE AND APPLICATION” published by Sankyo Shuppan .
- the resin constituting the dispersion phase in latex form in the invention can be produced by methods shown in JP-ANos. 10-265710 , 10-270233 or 5-2281 or " CHEMISTRY OF POLYMER LATEX” issued from Polymer Publishing Association and " POLYMER LATEX” published by New Polymer Library .
- Examples of materials which can be included in the microcapsule or in the latex include an acid generator, an initiator such as a radical generator, a light-heat converting material and a crosslinking agent.
- Examples of the polymer compound which can be used for the polymer matrix phase for forming the lower recording layer having the dispersion phase include the compounds exemplified for the dispersion phase of an embodiment (2).
- the acid generator examples include a photoinitiator for photo-cationic polymerization, photoinitiator for photo-radical polymerization, photo-achromatizing agent for dyes, photo-discoloring agent, known acid generator used for micro-resist, known compound which is thermally decomposed to generate an acid and a mixture of these compounds.
- the acid which is generated from the acid generator is preferably a strong acid having a pKa of 2 or less such as sulfonic acid and hydrochloric acid.
- the initiator include the triazine compounds described in JP-A No. 11-95415 and the latent Bronsted acid described in JP-A No. 7-20629 .
- the latent Bronsted acid means a precursor that is to be decomposed to generate a Bronsted acid. It is assumed that the Bronsted acid catalyzes a matrix generating reaction between a resol resin and a novolac resin.
- Typical examples of the Bronsted acid fitted to this purpose include trifluoromethanesulfonic acid and hexafluorophosphonic acid.
- An ionic latent Bronsted acid may be preferably used in the invention.
- the ionic latent Bronsted acid include onium salts, particularly, iodonium, sulfonium, phosphonium, selenonium, diazonium and arsonium salts.
- Particularly useful and specific examples of the onium salt include diphenyliodonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, phenylmethyl-ortho-cyanobenzylsulfoniumtrifluoromethane sulfonate and 2-methoxy-4-aminophenyldiazonium hexafluorophosphate.
- Nonionic latent Bronsted acids are also appropriately used in the invention.
- these nonionic latent Bronsted acids include compounds represented by the following formula: RCH 2 X, RCHX 2 , RCX 3 , R(CH 2 X) 2 and R(CH 2 X) 3 (wherein X represents Cl, Br, F or CF 3 SO 3 and R represents an aromatic group, an aliphatic group or a combination of an aromatic group and an aliphatic group).
- Useful ionic latent Bronsted acid is those represented by the following formula.
- W represents BF 4 , CF 3 SO 3 , SbF 6 , CCl 3 CO 2 , ClO 4 , AsF 6 , PF 6 or may be any corresponding acid having a pH less than 3.
- All the onium salts described in U.S. patent No. 4,708,925 may be used as the latent Bronsted acid used in the invention. Examples of these onium salts include indonium, sulfonium, phosphonium, bromonium, chloronium, oxysulfoxonium, oxysulfonium, sulfoxonium, selenonium, telluronium and arsonium.
- diazonium salt as the latent Bronsted acid.
- These diazonium salts provide a sensitivity equivalent to that of other latent Bronsted acids in the infrared region and a higher sensitivity than other latent Bronsted acid in the ultraviolet region.
- the acid generator is added in a proportion of 0.01 to 50% by weight, preferably 0.1 to 25% by weight and more preferably 0.5 to 20% by weight with respect to the total solid content of the lower recording layer from the viewpoint of image forming characteristics and from the viewpoint of preventing a non-image portion from being contaminated.
- the positive recording layer in the invention contains an infrared absorbing agent that is a structural component which develops a light-to-heat converting function.
- This infrared absorbing agent has the ability to convert absorbed infrared rays into heat.
- Laser scanning causes the infrared absorbing agent to lose the interaction, a developing inhibitor to decompose and generates an acid, which significantly improves the solubility of the infrared absorbing agent.
- the infrared absorbing agent itself interacts with the alkali-soluble resin to suppress alkali-solubility.
- the infrared absorbing agent used in the invention is dyes or pigments which efficiently absorb infrared rays having a wavelength from 760 nm to 1,200 nm and is preferably dyes or pigments having an absorption maximum in a wavelength range from 760 nm to 1,200 nm.
- the infrared absorbing agent which can be used preferably for the planographic printing plate precursor of the invention will be hereinafter explained in detail.
- the dyes may be commercially available ones and known ones described in publications such as " Dye Handbook" (edited by the Society of Synthesis Organic Chemistry, Japan, and published in 1970 ). Specific examples thereof include azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium dyes, metal thiolate complexes, and the like.
- the dye include near infrared absorbing sensitizers described in U.S. Patent No. 5,156,938 ; substituted arylbenzo(thio)pyrylium salts described in U.S. Patent No. 3,881,924 ; trimethinethiapyrylium salts described in JP-A No. 57-142645 ( U.S. Patent No. 4,327,169 ); pyrylium type compounds described in JP-ANos. 58-181051 , 58-220143 , 59-41363 , 59-84248 , 59-84249 , 59-146063 , and 59-146061 ; cyanine dyes described in JP-A No.
- JP-B Japanese Patent Application Publication
- the dye further include near infrared absorbing dyes represented by formulae (I) or (II) described in U.S. Patent No. 4,756,993 .
- dyes particularly preferable are cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes.
- the pigment which can be used as the infrared absorbent in the invention may be a commercially available pigment or a pigment described in publications such as Color Index (C.I.) Handbook, " Latest Pigment Handbook” (edited by Japan Pigment Technique Association, and published in 1977 ), “ Latest Pigment Applied Technique” (by CMC Publishing Co., Ltd. in 1986 ), and “ Printing Ink Technique” (by CMC Publishing Co., Ltd. in 1984 ).
- C.I. Color Index
- the pigment examples include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and polymer-bonded dyes.
- insoluble azo pigments azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perynone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, dyeing lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, and carbon black.
- the particle size of the pigment is preferably from 0.01 ⁇ m to 10 ⁇ m, more preferably from 0.05 ⁇ m to 1 ⁇ m, and even more preferably from 0.1 ⁇ m to 1 ⁇ m.
- the planographic printing plate precursor of the invention has a positive recording layer.
- the positive recording layer utilizes a positive action, in which solubility of an unexposed portion in an alkali developer is suppressed while the suppression of the solubility is cancelled in an exposed portion.
- an infrared absorbing agent which causes the cancellation by interacting with a binder polymer having a specific functional group.
- the infrared absorbing agent has an onium salt structure.
- cyanine dyes and pyrylium salts are particularly preferable. The details of these cyanine dyes and pyrylium salts are as described above.
- an anionic infrared absorbing agent as described in JP-A No. 11-338131 is also preferably used.
- This anionic infrared absorbing agent represents those having no cationic structure but an anionic structure on the mother nucleus of a dye which substantially absorbs infrared rays.
- the anionic infrared absorbing agent include (a-1) an anionic metal complex and (a-2) an anionic phthalocyanine.
- the anionic metal complex (a-1) denotes a compound in which the core metal and the ligands in the complex part that substantially absorbs light are an anion as a whole.
- the anionic phthalocyanine (a-2) denotes a compound in which an anionic group such as a sulfonic acid, carboxylic acid or phosphonic acid group is bonded as a substituent with a phthalocyanine skeleton to form an anion as a whole.
- the anionic phthalocyanine further include anionic infrared absorbing agents represented by the formula [Ga - -M-Gb] m X m+ (Ga represents an anionic substituent, Gb - represents a neutral substituent, and X m+ represents a cation having a valency of 1 to m (where m denotes an integer from 1 to 6) including a proton) as described in JP-A No. 11-338131 .
- the infrared absorbing agent used in the positive recording layer is preferably a dye.
- the dye include that having an onium salt structure as described in JP-A No. 11-291652 , paragraphs [0018] to [0034].
- infrared absorbing agent such as the cyanine dye, pyrylium salt dye or anionic dye, which exhibit dissolution inhibitive ability
- other dyes or pigments may be used together in the recording layer of the planographic printing plate precursor of the invention in view of further improving sensitivity and developing latitude.
- the infrared absorbing agent is preferably added in an amount of 0.01 to 50% by weight, more preferably 0.1 to 20% by weight and more preferably 0.5 to 15% by weight based on the total solid content in each of the lower recording layer and other layers from the viewpoint of image formation characteristics and from the viewpoint of suppressing generation of contamination to a non-image portion.
- the infrared absorbing agent may be contained in either or both of the matrix phase and the dispersion phase.
- the infrared absorbing agent may be added together with the raw materials when the latex particles are formed or may be introduced after the latex is formed.
- Examples of the method of introducing the infrared absorbing agent into the latex after the latex is formed include a method in which a water system, in which desired components such as the initiator, a coloring material or a crosslinking agent to be introduced in the latex are dissolved in an organic solvent, is added to the disperse medium.
- the recording layer of the planographic printing plate precursor of the invention is resistant to abrasion in relation to an infrared laser irradiation system.
- any polymer material may be used as a binder which forms the recording layer as long as its solubility to an aqueous alkali, namely, an alkali developing solution, is changed by imparting thermal energy
- the ceiling temperature of the polymer is given as an example of an index of the abrasion resistance.
- This ceiling temperature is a temperature at which the rate of a polymerization reaction is equal to the rate of a depolymerization reaction. It is preferable to select polymers having a high ceiling temperature to obtain high abrasion resistance.
- a proper polymer may be selected using the decomposition temperature thereof as an index.
- the polymer constituting the recording layer is a polymer having a decomposition temperature of preferably 150°C or more and more preferably 200°C or more. When the decomposition temperature is less than 150°C, this may not be preferable because the possibility of abrasion can be increased.
- Each component other than the polymer compound contained in the recording layer preferably has a decomposition temperature of 150°C or more, while a small amount of a component having a decomposition temperature less than 150°C may also be contained as long as it gives substantially no problem.
- the lower recording layer should have a configuration to achieve the dispersion phase.
- Additives which can be used in the other recording layers may basically be used in the lower recording layer as long as the requirement of the lower recording layer is satisfied.
- Each recording layer of the invention is preferably compounded of a fluorine-containing polymer for the purpose of improving the resistance to development in an image region.
- fluorine-containing polymer used in an image recording layer include copolymers formed from fluorine-containing monomers as described in each of JP-A Nos. 11-288093 and 2000-187318 .
- fluorine-containing polymer examples include fluorine-containing acryl polymers P-1 to P-13 as described in JP-A No. 11-288093 and fluorine-containing polymers obtained by copolymerizing fluorine-containing acryl monomers A-1 to A-33 with arbitrary acryl monomers.
- the fluorine-containing polymer exemplified above preferably has a weight average molecular weight of 2,000 or more and a number average molecular weight of 1,000 or more. It is more preferable that the weight average molecular weight is 5,000 to 300,000 and the number average molecular weight is 2,000 to 250,000.
- fluorine surfactants having the preferable molecular weight may be used as the fluorine-containing polymer.
- Specific examples of such surfactants include MEGAFAC F-171, F-173, F-176, F-183, F-184, F-780 and F-781 (all are trade names, manufactured by DIC Corporation).
- fluorine-containing polymers may be used either singly or combinations of two or more. It is necessary that the amount of the fluorine-containing polymer is 1.4 mass% or more based on the solid content of the image recording layer to meet the requirements in the invention. The amount is preferably 1.4 to 5.0 mass%. When the amount is below 1.4 mass%, the purpose of the addition of the fluorine-containing polymer, namely, the effect of improving the developing latitude of the image recording layer may become insufficient.
- a dissolution inhibitor which is a thermally decomposable material and substantially reduces the solubility of the aqueous alkali-soluble polymer compound in an decomposed state, may be additionally used in the lower recording layer or other layers of the precursor of the invention according to the need.
- the dissolution inhibitor include an onium salt, an o-quinonediazide compound, an aromatic sulfone compound and an aromatic sulfonate compound.
- the addition of the dissolution inhibitor makes it possible not only to improve the dissolution resistance of the image portion in a developing solution but also to use, as the infrared absorbing agent, a compound which does not interact with the alkali-soluble resin.
- the onium salt include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts and arsonium salts.
- onium salt used in the invention include diazonium salts described in S. I. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974 ), T. S. Bal et al., Polymer, 21, 423 (1980 ), and JP-A No. 5-158230 ; ammonium salts described in U.S. Patent Nos. 4,069,055 and 4,069,056 , and JP-ANo. 3-140140 ; phosphonium salts described in D. C. Necker et al., Macromolecules, 17, 2468 (1984 ), C. S. Wen et al., Teh, Proc. Conf. Rad.
- a diazonium salt is particularly preferably used as the dissolution inhibitor.
- Particularly preferable examples of the diazonium salt include those described in JP-A No. 5-158230 .
- Examples of the counter ion of the onium salt include tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 5-sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benz
- hexafluorophosphoric acid, and alkylaromatic sulfonic acids such as triisopropylnaphthalenesulfonic acid and 2,5-dimethylbezenesulfonic acid are particularly preferable.
- the quinonediazide is preferably an o-quinonediazide compound.
- the o-quinonediazide compound used in the invention is a compound having at least one o-quinonediazide group and having an alkali-solubility increased by being thermally decomposed.
- the compound may be any one of compounds having various structures.
- the o-quinonediazide compound assists the solubilization property of the photosensitive material from the effects of losing the function of suppressing the dissolution of the binder by being thermally decomposed as well as the effect that the o-quinonediazide itself is changed into an alkali-soluble material.
- the amount of the o-quinonediazide compound is preferably in a range from 1 mass% to 50 mass%, more preferably in a range from 5 mass% to 30 mass%, and particularly preferably in a range from 10 mass% to 30 mass% based on the total solid content of each recording layer. These compounds may be used singly or as a mixture of plural kinds thereof.
- the amount of the additives except for the o-quinonediazide compound is preferably 1 mass% to 50 mass%, more preferably 5 mass% to 30 mass%, and particularly preferably 10 mass% to 30 mass%.
- the additives and binder used in the invention are preferably compounded in the same layer.
- the recording layer may further contain a cyclic acid anhydride, a phenolic compound, an organic acid or the like.
- a cyclic acid anhydride examples include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy- ⁇ 4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, ⁇ -phenylmaleic anhydride, succinic anhydride, and pyromellitic anhydride which are described in U.S. Patent No. 4,115,128 .
- Specific examples thereof 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 content thereof is preferably from 0.05 to 20%, more preferably from 0.1 to 15%, and even more preferably from 0.1 to 10% by mass in terms to the total solid content of the recording layer.
- a dye having an absorption in the visible light region may be added to each recording layer according to the invention as a colorant for an image to be formed.
- the dye include Oil Yellow #101, Oil Yellow #103, Oil Pink #312, Oil Green BG, Oil Blue BOS, Oil Blue #603, Oil Black BY, Oil Black BS and Oil Black T-505 (these products are manufactured by Orient Chemical Industries, Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI52015), AIZEN SPIROL BLUE C-RH (manufactured by Hodogaya Chemical Co., Ltd.), and dyes as described in JP-A No. 62-293247 .
- Nonionic surfactants as described in JP-A Nos. 62-251740 and 3-208514 , amphoteric surfactants as described in JP-A Nos. 59-121044 and 4-13149 , siloxane compounds as described in EP No. 950517 , and/or copolymers made from a fluorine-containing monomer as described in JP-A No. 11-288093 can be added to the image recording layer of the planographic printing plate precursor of the invention in order to make processes more stable upon development conditions in processes.
- nonionic surfactants include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, monoglyceride stearate, and polyoxyethylene nonyl phenyl ether.
- amphoteric surfactants include alkyldi(aminoethyl)glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N,N'-betaine type surfactants (trade name: "AMOGEN K", manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).
- a printing-out agent which is a material for obtaining a visible image immediately after the photosensitive composition of the invention has been heated by exposure to light, or a dye or pigment as an image coloring agent, may be added to the photosensitive composition of the invention.
- a typical example of the printing-out agent is a combination of a photo acid-generating agent (a compound which is heated by exposure to light, thereby generating an acid), and an organic dye which can form salts.
- the combination include combinations of an o-naphthoquinonediazide-4-sulfonic acid halogenide with a salt-formable organic dye, described in JP-A Nos. 50-36209 and 53-8128 ; and combinations of a trihalomethyl compound with a salt-formable organic dye, described in each of JP-A Nos. 53-36223 , 54-74728 , 60-3626 , 61-143748 , 61-151644 and 63-58440 .
- the trihalomethyl compound is classified into an oxazol compound or a triazine compound. Both of the compounds provide excellent stability over the passage of time and produce a clear printed-out image.
- a plasticizer may be added to a coating liquid for forming the recording layer of the precursor of the invention to give flexibility to a coating film made from the coating liquid.
- the plasticizer include oligomers and polymers of butyl phthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl olete, and acrylic acid and/or methacrylic acid.
- planographic printing plate precursor of the invention may be usually produced by sequentially applying, to an appropriate support, coating liquids for forming respective recording layers which contain the components.
- Examples of a solvent appropriate for applying the recording layer include, though not limited to, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N,N-dimethylacetamide, N,N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, ⁇ -butyrolactone and toluene. These solvents may be used either singly or as a mixture of two or more of them.
- the concentration of the above components (total solid content including additives) in the solvent is preferably 1 mass% to 50 mass%.
- the lower recording layer and upper recording layers are preferably formed so as to form two layers separate from each other in principle.
- Examples of the method of forming the separate two layers include, though not limited to: a method utilizing a difference between the solubility of the components contained in the lower recording layer to a solvent and that of the components contained in the upper layer; and a method in which a solvent is vaporized and removed quickly by drying after the upper layer is applied.
- Examples of the method utilizing the difference between the solubility of the components contained in the lower recording layer to a solvent and that of the components contained in the upper layer include a method which uses a solvent which does not dissolve the alkali-soluble resin contained in the lower recording layer when an upper layer coating liquid is applied. This makes it possible to separate each layer clearly to form coating films even if two-layer coating is carried out.
- components insoluble in solvents such as methyl ethyl ketone and 1-methoxy-2-propanol which dissolve the alkali-soluble resin which is the upper layer component, are selected as the lower recording layer components; the lower recording layer is applied by using a solvent which contain the lower recording layer components dissolved therein and dried; the upper layer components, which have the alkali-soluble resins as a primary component, are dissolved in methyl ethyl ketone, 1-methoxy-2-propanol or the like; and the upper layer coating liquid is applied and dried, whereby the formation of two layers can be attained.
- solvents such as methyl ethyl ketone and 1-methoxy-2-propanol
- a solvent which dissolves the alkali-soluble resin contained in the lower recording layer may be mixed with a solvent which doe not dissolve this alkali-soluble resin.
- Mixing of components which causes between the upper layer and the lower recording layer can be arbitrarily controlled by changing the mixing ratio of both solvents. If the ratio of the solvent that dissolves the alkali-soluble resin contained in the lower recording layer is increased, a part of the lower recording layer is dissolved when applying the upper layer and the dissolved component becomes to be contained in the upper layer as a particle-shape component after the upper layer is dried.
- the particle-shape component forms projections provided on the surface of the upper layer, which increases damage resistance.
- the dissolution of the lower recording layer components tends to deteriorate the quality of the lower recording layer and hence tends to deteriorate resistance of the lower recording layer against chemicals.
- controlling of the mixing ratio with taking the characteristics of each solvent into account enables exhibition of various characteristics as well as making layers being partially compatible therebetween, which is explained below.
- the amount of a solvent which can dissolve the alkali-soluble resin in the lower recording layer is preferably 80 mass% or less relative to the amount of the solvent used to the upper layer coating liquid from the viewpoint of resistance to chemicals, and taking resistance to damage into account, it is more preferably in a range from 10 mass% to 60 mass%.
- Examples of a method of drying a solvent very quickly after the second layer (upper layer) is applied include a method including spraying high pressure air from a slit nozzle located at almost a right angle with respect to the running direction of a web, a method including supplying, to a web, thermal energy as conductive heat from the underside of the web through a roll (heating roll) to which a heating medium such as steam is supplied, and a combination of these methods.
- Various methods may be used as a method of applying each of the layers such as the image recording layer.
- Examples of the coating method may include bar coater coating, rotation coating, spray coating, curtain coating, dip coating, air knife coating, blade coating and roll coating.
- the coating method used to form the upper recording layer is preferably carried out in a non-contact system to prevent damages to the lower recording layer when applying the upper recording layer. While bar coater coating, though it is a contact system, may be used as the method generally used in a solvent system coating, it is desirable to carry out the coating in forward driving to prevent damages to the lower recording layer.
- the coating amount of the lower recording layer after the layer is dried in the planographic printing plate precursor of the invention is preferably in a range from 0.5 g/m 2 to 1.5 g/m 2 and more preferably in a range from 0.7 g/m 2 to 1.0 g/m 2 from the viewpoint of suppressing generation of a residual film during developing of the precursor and ensuring printing durability of a printing plate formed from the precursor.
- the amount of other recording layer (upper recording layer) after drying is preferably in the range of 0.05 g/m 2 to 1.0 g/m 2 , more preferably in the range of 0.07 g/m 2 to 0.7 g/m 2 .
- a surfactant such as a fluorine surfactant as described in JP-A No. 62-170950 may be added to the coating liquid for the lower recording layer or the coating liquids of other recording layers to improve coating characteristics.
- the amount of the surfactant is preferably 0.01 mass% to 1 mass% and more preferably 0.05 mass% to 0.5 mass% based on the total solid content of the coating liquid.
- the support used in the planographic printing plate precursor of the invention is a plate-shape material having dimensional stability.
- examples thereof include paper, papers laminated with plastic (such as polyethylene, polypropylene or polystyrene), metal plates (such as aluminum plates, zinc plates or copper plates), plastic films (such as cellulose biacetate films, cellulose triacetate films, cellulose propionate films, cellulose lactate films, cellulose acetate lactate films, cellulose nitrate films, polyethylene terephthalate films, polyethylene films, polystyrene films, polypropylene films, polycarbonate films, or polyvinyl acetate films), and papers or plastic films on which a metal such as aluminum, zinc or copper is laminated or vapor-deposited.
- plastic such as polyethylene, polypropylene or polystyrene
- metal plates such as aluminum plates, zinc plates or copper plates
- plastic films such as cellulose biacetate films, cellulose triacetate films, cellulose propionate films, cellulose lactate films,
- the support is preferably a polyester film or an aluminum plate, and more preferably an aluminum plate, since an aluminum plate is excellent in terms of dimensional stability and is also relatively inexpensive.
- Preferable examples of the aluminum plate include a pure aluminum plate and alloy plates made of aluminum as a main component with a very small amount of other elements.
- a plastic film on which aluminum is laminated or vapor-deposited may also be used.
- other elements which may be contained in the aluminum alloys include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content by percentage of different elements in the alloy is at most 10% by mass.
- a particularly preferable aluminum plate in the invention is a pure aluminum plate; however, since from the viewpoint of refining a completely pure aluminum cannot be easily produced, a very small amount of other elements may also be contained in the plate.
- the aluminum plate used as the support is not specified in terms of the composition thereof. Thus, aluminum plates which are conventionally known can be appropriately used.
- the thickness of the aluminum plate used in the invention is from about 0.1 mm to 0.6 mm, preferably from 0.15 mm to 0.4 mm, and more preferably from 0.2 mm to 0.3 mm.
- the aluminum plate may be arbitrarily subjected to degreasing treatment prior to the surface-roughening treatment, in order to remove rolling oil or the like on the surface, with a surfactant, an organic solvent, an aqueous alkaline solution or the like.
- the surface-roughening treatment of the aluminum surface can be performed by various methods such as a mechanical surface-roughening method, a method of dissolving and roughening the surface electrochemically, or a method of dissolving the surface selectively in a chemical manner.
- Mechanical surface-roughening methods which can be used may be known methods, such as a ball polishing method, a brush polishing method, a blast polishing method or a buff polishing method.
- An electrochemical surface-roughening method may be a method of performing surface-roughening in an electrolyte of hydrochloric acid or nitric acid, by use of an alternating current or a direct current. As disclosed in JP-A No. 54-63902 , a combination of the two kinds of methods may be used.
- An aluminum plate whose surface is roughened as described above is if necessary subjected to alkali-etching treatment and neutralizing treatment. Thereafter, an anodizing treatment is arbitrarily applied in order to improve the water holding capacity and wear resistance of the surface.
- the electrolyte used in the anodizing treatment of the aluminum plate is any one selected from various electrolytes which can form a porous oxide film. Among which in general use are electrolytes of sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof.
- the concentration of the electrolyte may be appropriately decided depending on the kind of electrolyte selected.
- Treatment conditions for anodization cannot be specified as a general rule since conditions vary depending on the electrolyte used; however, the following range of conditions are generally suitable: an electrolyte concentration of 1% to 80% by mass, a solution temperature of 5°C to 70°C, a current density of 5 A/dm 2 to 60 A/dm 2 , a voltage of 1 V to 100 V, and an electrolyzing time of 10 seconds to 5 minutes. If the amount of anodic oxide film is less than 1.0 g/m 2 , printing durability is inadequate or non-image portions of the planographic printing plate tend to become easily damaged and the so-called "blemish stains", resulting from ink adhering to damaged portions at the time of printing, are easily generated.
- Example of the hydrophilicity treatment include a method using an alkali metal silicate (for example, an aqueous sodium silicate solution) as disclosed in U.S. Patent Nos. 2,714,066 , 3,181,461 , 3,280,734 , and 3,902,734 .
- the support is subjected to an immersing treatment or an electrolyzing treatment with an aqueous sodium silicate solution.
- the following methods may also be used: a method of treating the support with potassium fluorozirconate, as disclosed in JP-B No. 36-22063 , or with polyvinyl phosphonic acid, as disclosed in U.S. Patent Nos. 3,276,868 , 4,153,461 , and 4,689,272 .
- planographic printing plate precursor of the invention has at least two layers including the lower recording layer and other layer(s) (upper recording layer(s)) which are provided on the support, the planographic printing plate precursor may further has an undercoat layer provided between the support and the lower recording layer according to the need.
- organic compounds can be used as components of the undercoat layer.
- examples thereof include carboxymethylcellulose, dextrin, gum arabic, phosphonic acids having an amino group, such as 2-aminoethylphosphonic acid, organic phosphonic acids which may have a substituent, such as phenyl phosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, organic phosphoric acids which may have a substituent, such as phenylphosphoric acid, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid, organic phosphinic acids which may have a substituent, such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and ⁇ -alanine, and hydrochlorides of amines having a
- Examples of the method for forming the organic undercoat layer include: a method including applying, onto the aluminum plate, a solution in which the above-mentioned organic compound is dissolved in water, or an organic solvent such as methanol, ethanol or methyl ethyl ketone, or a mixed solvent thereof and then drying the resultant aluminum plate; and a method including immersing the aluminum plate into a solution in which the above-mentioned organic compound is dissolved in water or an organic solvent such as methanol, ethanol, methyl ethyl ketone or a mixed solvent thereof so as to adsorb the compound, washing the aluminum plate with water or the like, and then drying the resultant aluminum plate.
- the solution of the organic compound having a concentration of 0.05 to 10% by mass may be applied in various ways.
- the concentration of the organic compound in the solution is from 0.01 to 20%, preferably from 0.05 to 5%
- the temperature for the immersion is from 20 to 90°C, preferably from 25 to 50°C
- the time taken for immersion is from 0.1 second to 20 minutes, preferably from 2 seconds to 1 minute.
- the pH of the solution used in the above-mentioned methods can be adjusted into a range of 1 to 12 with a basic material such as ammonia, triethylamine or potassium hydroxide, or an acidic material such as hydrochloric acid or phosphoric acid.
- a yellow dye may be added to the solution, in order to improve the tone reproducibility of the recording layer.
- the amount of the organic undercoat layer applied is suitably from 2 mg/m 2 to 200 mg/m 2 , and is preferably from 5 mg/m 2 to 100 mg/m 2 .
- the positive planographic printing plate precursor produced as described above is usually subjected to image exposure and developing treatment.
- the planographic printing plate precursor is exposed to light from a light source which preferably has an emitting wavelength in the near-infrared region to the infrared region.
- the planographic printing plate precursor is preferably exposed imagewise to light from a solid laser or a semiconductor laser radiating infrared rays having a wavelength of 760 nm to 1,200 nm.
- Any conventionally known aqueous alkali solution may be used as a developing solution and replenishing solution to be used for plate-making of the planographic printing plate of the invention.
- the developing solution which may be applied to the developing treatment of the planographic printing plate precursor of the invention is a developing solution having a pH range from 9.0 to 14.0 and preferably a pH range from 12.0 to 13.5.
- a conventionally known aqueous alkali solution may be used as the developing solution (hereinafter referred to as a developing solution including a replenishing solution).
- an aqueous alkali solution having a non-reducing sugar and a base may also be used.
- the non-reducing sugar denotes a sugar having no reducing ability due to lack of a free aldehyde group, a ketone group and the like, and is classified into trehalose oligosaccharides in which reducing groups are combined with other, glycosides in which reducing groups of sugars are combined with non-sugars, or sugar alcohols in which sugars are reduced by hydrogenation. Any of these non-reducing sugars may be preferably used.
- Examples of the trehalose oligosaccharides include saccharose and trehalose.
- Examples of the glucosides include alkylglucosides, phenolglucosides, and mustard seed oil glucoside.
- Examples of the sugar alcohols include D, L-arabite, ribitol, xylitol, D, L-sorbitos, D, L-mannitol, D, L-iditol, D, L-talitol, dulcitol, and allodulcitol.
- maltitol obtained by hydrogenating a disaccharide, and a reductant obtained by hydrogenating an oligosaccharide (i.e., reduced starch syrup) are preferable.
- sugar alcohol and saccharose are more preferable.
- D-sorbitol, saccharose, and reduced starch syrup are even more preferable since they have buffer effect within an appropriate pH range and are inexpensive.
- nonreducing sugars may be used alone or in combination of two or more thereof.
- the content of the nonreducing sugar in the developer is preferably from 0.1 % to 30% by mass, more preferably from 1%to 20% by mass with respect to the total amount of the developer.
- the base combined with the nonreducing sugar(s) may be an alkali agent that has been conventionally known.
- Examples thereof include inorganic alkali agents such as sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, tripotassium phosphate, triammonium phosphate, disodium phosphate, dipotassium phosphate, diammonium phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogencarbonate, sodium borate, potassium borate or ammonium borate; and organic alkali agents such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, or pyridine.
- inorganic alkali agents such as sodium hydroxide,
- the bases may be used singly or in combination of two or more.
- sodium hydroxide and potassium hydroxide are preferable.
- the reason is that pH adjustment can be made in a wide pH range by regulating the amount of the alkali agent to be added to the non-reducing sugar.
- trisodium phosphate, sodium carbonate, potassium carbonate or the like itself have a buffer action and are hence preferable.
- an aqueous solution having a higher alkali intensity than that of the developer can be added to the developer. It is known that this enables to treat a great number of photosensitive plates without recourse to replacing the developer in the developing tank over a long period of time.
- This replenishing manner is also preferably used in the invention.
- various surfactants or organic solvents can be incorporated into the developer and the replenisher in order to promote and suppress development capacity, disperse scum generated during development, and enhance the ink-affinity of image portions of the printing plate.
- the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants.
- a reducing agent such as hydroquinone, resorcin, a sodium or potassium salt of an inorganic acid such as sulfurous acid or hydrogen sulfite acid
- an organic carboxylic acid such as sulfurous acid or hydrogen sulfite acid
- an antifoaming agent such as sodium or potassium salt of an inorganic acid such as sulfurous acid or hydrogen sulfite acid
- a water softener such as sodium or potassium salt of an inorganic acid such as sulfurous acid or hydrogen sulfite acid
- the printing plate developed with the developer and replenisher described above is subsequently subjected to treatments with washing water, a rinse solution containing a surfactant and other components, and a desensitizing solution containing gum arabic and a starch derivative.
- Various combinations of these treatments may be employed for after treatment when the photosensitive composition precursor of the invention is to be used for forming a planographic printing plate.
- automatic developing machines for printing plate precursors have been widely used in order to rationalize and standardize plate-making processes in the plate-making and printing industries.
- These automatic developing machines are generally made up of a developing section and a post-processing section, and include a device for carrying printing plate precursors, various treating solution tanks, and spray devices.
- These machines are machines for spraying respective treating solutions, which are pumped up, onto an exposed printing plate through spray nozzles, for development, while the printing plate is transported horizontally.
- a method has also attracted attention in which a printing plate precursor is immersed in treating solution tanks filled with treating solutions and conveyed by means of in-liquid guide rolls.
- Such automatic processing can be performed while replenishers are being replenished into the respective treating solutions in accordance with the amounts to be treated, operating times, and other factors.
- a so-called use-and-dispose processing manner can also be used, in which treatments are conducted with treating solutions which in practice have yet been used.
- a method of treating the heat-sensitive planographic printing plate precursor of the invention will be explained.
- unnecessary image portions for example, a film edge mark of an original picture film
- unnecessary image portions can be erased.
- the erasing is preferably performed by applying an erasing solution to unnecessary image portions, leaving the printing plate as it is for a given time, and washing the plate with water, as described in, for example, JP-B No. 2-13293 .
- This erasing may also be performed by a method of radiating active rays introduced through an optical fiber onto the unnecessary image portions, and then developing the plate, as described in JP-A No. 59-174842 .
- planographic printing plate obtained as described above is, if desired, coated with a desensitizing gum, and subsequently the plate can be made available for printing.
- burning treatment can be applied to the planographic printing plate.
- the planographic printing plate is subjected to the burning treatment, it is preferable that the plate is treated with a surface-adjusting solution before the burning treatment takes place as described in JP-B No. 61-2518 , or JP-A Nos. 55-28062 , 62-31859 or 61-159655 .
- Examples of the method of the surface-adjusting treatment include: a method of applying the surface-adjusting solution onto the planographic printing plate with a sponge or absorbent cotton infiltrated with the solution; a method of immersing the planographic printing plate in a vat filled with the surface-adjusting solution; and a method of applying the surface-adjusting solution to the planographic printing plate with an automatic coater.
- a better result may be obtained.
- the amount of surface-adjusting solution applied is suitably from 0.03 g/m 2 to 0.8 g/m 2 (dry mass).
- the planographic printing plate onto which the surface-adjusting solution is applied can be dried, and then the plate is heated to a high temperature by means of a burning processor (for example, a burning processor BP-1300 (trade name, available from FUJIFILM Corporation)) or the like.
- the heating temperature and the heating time which depend on the kind of components forming the image, are preferably from 180°C to 300°C and from 1 minute to 20 minutes, respectively.
- a planographic printing plate subjected to burning treatment can be further subjected to treatments which have been conventionally conducted, such as a water-washing treatment and gum coating.
- An aluminum alloy which contains 0.06 wt% Si, 0.30 wt% Fe, 0.025 wt% Cu, 0.001 wt% Mn, 0.001 wt% Mg, 0.001 wt% Zn and 0.03 wt% Ti, the balance being Al and inevitable impurities, was used to prepare a molten metal.
- the molten metal was then subjected to molten metal treatment, filtered and formed into an ingot of 500 mm in thickness and 1,200 mm in width by a DC casting method.
- the ingot was soaked at 550°C for about 5 hours, and when the temperature decreased to 400°C, the ingot was formed into a rolled plate of 2.7 mm in thickness with a hot rolling mill. Then, the plate was subjected to heat treatment at 500°C with a continuous annealing device and finished with cold rolling to give a plate of 0.24 mm in thickness as an aluminum plate. This aluminum plate was formed into a plate of 1030 mm in width and then subjected to the following surface treatment.
- the surface of the aluminum plate was subjected to mechanical surface roughening treatment with a rotating roller-shaped nylon brush while it was supplied with an aqueous suspension of an abrasive (Pumice) having a specific gravity of 1.12 as an abrasive slurry.
- the average particle diameter of the abrasive was 8 ⁇ m, and the maximum particle diameter was 50 ⁇ m.
- the nylon brush was made of 6 ⁇ 10 nylon, the length of the brush hair was 50 mm, and the diameter of the brush hair was 0.3 mm.
- the nylon brush had hairs arranged densely in holes in a stainless steel cylinder of ⁇ 300 mm. Three rotating brushes were used. The distance between two supporting rollers ( ⁇ 200 nm) under the brushes was 300 mm.
- the brush roller was pressed against the aluminum plate until the load of a driving motor for rotating the brush was increased by 7 kW relative to the load before the brush roller was pressed against the aluminum plate.
- the direction of rotation of the brush was the same as the direction of movement of the aluminum plate.
- the number of revolutions of the brush was 200 rpm.
- the aluminum plate obtained above was subjected to etching treatment by spraying with an aqueous solution of sodium hydroxide at a concentration of 2.6 wt% and aluminum ions at a concentration of 6.5 wt% at a temperature of 70°C, whereby the aluminum plate was dissolved in an amount of 10 g/m 2 . Thereafter, the aluminum plate was washed by spraying with water.
- the aluminum plate was subjected to desmut treatment with an aqueous solution (containing 0.5 wt% aluminum ion) of 1 wt% nitric acid at a temperature of 30°C and then washed by spraying with water.
- the aqueous solution of nitric acid used in the desmut treatment was waste liquid resulted from the process of electrochemical surface roughening treatment with an alternating current in an aqueous solution of nitric acid.
- the plate was subjected to continuous electrochemical surface roughening treatment with an alternating voltage of 60 Hz.
- the electrolyte used was 10.5 g/L aqueous nitric acid solution (containing 5 g/L aluminum ion and 0.007 wt% ammonium ion) at a temperature of 80°C.
- the electrochemical surface roughening treatment was carried out with a carbon electrode as a counter electrode wherein the alternating current power source waveform had a waveform as shown in Fig. 1 , the time required for the electric current to reach from 0 to the peak was 0.8 msec., the duty ratio was 1 : 1, and a trapezoidal rectangular wave alternating current was used. Ferrite was used as an auxiliary anode.
- the electrolyte chamber used was as shown in Fig. 2 .
- the current density was 30 A/dm 2 in terms of the electric current peak, and the electrical quantity was 220 C/dm 2 in terms of the total electrical quantity when the aluminum plate was an anode. 5% of the electric current from the power source was fed through the auxiliary anode. Thereafter, the plate was washed by spraying with water.
- the aluminum plate was subjected to etching treatment by spraying with an aqueous solution of sodium hydroxide at a concentration of 26 wt% and aluminum ions at a concentration of 6.5 wt% at a temperature of 32°C, whereby the aluminum plate was dissolved in an amount of 0.20 g/m 2 .
- Smut components composed in the main of aluminum hydroxide formed by the electrochemical surface roughening treatment using the alternating current in the previous stage, were removed, and the edges of the pits formed were dissolved to smooth the edge. Thereafter, washing by spraying with water was carried out.
- the aluminum plate was subjected to desmut treatment with an aqueous solution of 25 wt% nitric acid (containing 0.5 wt% aluminum ions) at a temperature of 30°C and then washed by spraying with water.
- Anodizing treatment was carried out with an anodizing apparatus for two-step current feeding which has a structure with first and second electrolyte zones of 6 m in length each, first and second current feeding zones of 3 m in length, and first and second current feeding zones of 2.4 m in length.
- the electrolytes supplied to the first and second electrolytic zones were sulfuric acid. Both the electrolytes were 170 g/L sulfuric acid (containing 0.5 wt% aluminum ions) at a temperature of 43°C. Thereafter, washing by spraying with water was carried out. The final anodized coating was 2.7 g/m 2 .
- the aluminum support obtained by the anodizing treatment was subjected to alkali metal silicate treatment (silicate treatment) by dipping it in a treatment bath of 1 wt% aqueous sodium silicate No. 3 at a temperature of 30 °C for 10 seconds. Thereafter, the aluminum support was washed by spraying with water
- the resulting aluminum support was coated with an undercoat liquid having the following formulation and then dried at 80 °C for 15 seconds, to form a coating thereon.
- the amount of the coating (undercoat layer) after drying was 15 mg/m 2 .
- the coating liquid for the lower recording layer having the following formulation was applied to the thus obtained support such that the application amount thereof was 0.85 g/m 2 , and then dried at 140°C for 50 seconds with PERFECT OVEN PH200 (trade name, manufactured by TABAI) by setting the level of wind control thereof to seven. Thereafter, the following coating liquid for the upper recording layer having the following formulation was applied to the resulting coating film such that the application amount thereof was 0.15 g/m 2 , and then dried at 120°C for 1 minute, so as to provide planographic printing plate precursors of Examples 1 to 5 and Comparative Examples 1 to 3.
- Polymer 1 was synthesized using three monomers of 4-(2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl)-N-(4,6-dimethyl-2-pyrimidinyl)-benzenesulfone amide (hereinafter referred to as "monomer 1”), benzyl maleimide (hereinafter referred as to “monomer 2”) and (4-hydroxy-3,5-dimethylbenzyl)methacrylamide (hereinafter referred to as "monomer 3").
- 50 wt% solution of 2,2-di(t-butylperoxy)butane in sododecane/methyl ethyl ketone was used as an initiator.
- the initiator was available as TRIGONOX D-C50 (trade name) from Akzo Nobel (Amersfoort, Netherlands).
- a coating liquid for forming the outermost layer having the following formulation was applied to the surface of the upper recording layer formed as above by wet coating in a thickness of 10 ⁇ m and dried at 135°C.
- a solvent used in the coating liquid is a mixture of 50% of isopropanol (IPA)/50% of 1-methoxy-2-propanol (DOWANOL PM: described above). The application amount after drying was 0.004 g/m 2 .
- the TEGO ® GLIDE 410 and TEGO ® WET 265 used in the coating liquid for forming the outermost layer are a polysiloxane and a poly (alkylene oxide) copolymer, and were obtained from TEGO CHELIE SERVICE.
- the planographic printing plate precursors of Examples 1 to 5 and Comparative examples 1 to 3 were respectively cut with a microtome.
- the resulting section of the recording layer of each was made electroconductive, and then photographs thereof were taken with a scanning electron microscope (SEM) and observed.
- SEM scanning electron microscope
- the size of the dispersion phase was in the range of 0.05 to 0.55 ⁇ m.
- the lower recording layers of Comparative examples 1 to 3 has uniform phases which lack a dispersion phase.
- a test pattern was drawn to each of the resulting planographic printing plate precursors of Examples 1 to 5 and Comparative examples 1 to 3 by imagewise exposure using TRENDSETTER (described above) with varying a beam intensity at a drum revolution of 250 rpm.
- the thus exposed precursors were then developed by using a developing solution DT-2 (described above: diluted with water to provide an electrical conductivity of 43 ms/cm).
- the smallest exposure energy which provided a developable non-image region with the above development condition was evaluated as the index of the sensitivity. The smaller the exposure energy value is, the better in the sensitivity.
- Table 2 The results of this test are shown in Table 2.
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EP2644379A1 (de) * | 2012-03-30 | 2013-10-02 | FUJIFILM Corporation | Verfahren zur Herstellung einer Flachdruckplatte |
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EP2644379A1 (de) * | 2012-03-30 | 2013-10-02 | FUJIFILM Corporation | Verfahren zur Herstellung einer Flachdruckplatte |
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