JP5736277B2 - Planographic printing plate precursor - Google Patents
Planographic printing plate precursor Download PDFInfo
- Publication number
- JP5736277B2 JP5736277B2 JP2011182874A JP2011182874A JP5736277B2 JP 5736277 B2 JP5736277 B2 JP 5736277B2 JP 2011182874 A JP2011182874 A JP 2011182874A JP 2011182874 A JP2011182874 A JP 2011182874A JP 5736277 B2 JP5736277 B2 JP 5736277B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- printing plate
- resin
- core
- lithographic printing
- 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.)
- Active
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- 238000007639 printing Methods 0.000 title claims description 120
- 239000002243 precursor Substances 0.000 title claims description 56
- 239000011347 resin Substances 0.000 claims description 101
- 229920005989 resin Polymers 0.000 claims description 101
- 239000010419 fine particle Substances 0.000 claims description 85
- 150000001875 compounds Chemical class 0.000 claims description 80
- 229920000642 polymer Polymers 0.000 claims description 53
- 239000000178 monomer Substances 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- 239000011258 core-shell material Substances 0.000 claims description 22
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- -1 acrylic acid (Substituted) acrylic acid Chemical class 0.000 description 109
- 239000010410 layer Substances 0.000 description 98
- 239000006185 dispersion Substances 0.000 description 42
- 239000011248 coating agent Substances 0.000 description 35
- 239000000243 solution Substances 0.000 description 35
- 238000000576 coating method Methods 0.000 description 34
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 33
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- 239000000975 dye Substances 0.000 description 32
- 238000000034 method Methods 0.000 description 27
- 239000000976 ink Substances 0.000 description 26
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- 125000002947 alkylene group Chemical group 0.000 description 18
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- 229910052782 aluminium Inorganic materials 0.000 description 16
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
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- 125000001424 substituent group Chemical group 0.000 description 11
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- 125000000524 functional group Chemical group 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 9
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- 125000003277 amino group Chemical group 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 230000002209 hydrophobic effect Effects 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 9
- 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 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 150000002433 hydrophilic molecules Chemical class 0.000 description 8
- 239000003094 microcapsule Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 229920001451 polypropylene glycol Polymers 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 150000001408 amides Chemical class 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 239000000470 constituent Substances 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 229920001519 homopolymer Polymers 0.000 description 7
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical class COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 238000007259 addition reaction Methods 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006392 deoxygenation reaction Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical class C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 4
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine group Chemical group N1=CCC2=CC=CC=C12 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Chemical class CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007788 roughening Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical class CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000005235 azinium group Chemical group 0.000 description 3
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- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
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- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 2
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- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
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- 150000008052 alkyl sulfonates Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- GWVLAXGYZUVAGV-UHFFFAOYSA-N n,n-dimethylmethanamine;methanesulfonic acid Chemical compound C[NH+](C)C.CS([O-])(=O)=O GWVLAXGYZUVAGV-UHFFFAOYSA-N 0.000 description 1
- LMCMWVRJNPJYIZ-UHFFFAOYSA-N n-(2-sulfamoylethyl)prop-2-enamide Chemical compound NS(=O)(=O)CCNC(=O)C=C LMCMWVRJNPJYIZ-UHFFFAOYSA-N 0.000 description 1
- KFAUOAKHHDYZPL-UHFFFAOYSA-N n-(2-sulfamoylphenyl)prop-2-enamide Chemical compound NS(=O)(=O)C1=CC=CC=C1NC(=O)C=C KFAUOAKHHDYZPL-UHFFFAOYSA-N 0.000 description 1
- ATAZOHSLMIURAO-UHFFFAOYSA-N n-(3-sulfamoylphenyl)prop-2-enamide Chemical compound NS(=O)(=O)C1=CC=CC(NC(=O)C=C)=C1 ATAZOHSLMIURAO-UHFFFAOYSA-N 0.000 description 1
- XZSZONUJSGDIFI-UHFFFAOYSA-N n-(4-hydroxyphenyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC1=CC=C(O)C=C1 XZSZONUJSGDIFI-UHFFFAOYSA-N 0.000 description 1
- RINSWHLCRAFXEY-UHFFFAOYSA-N n-(4-sulfamoylphenyl)prop-2-enamide Chemical compound NS(=O)(=O)C1=CC=C(NC(=O)C=C)C=C1 RINSWHLCRAFXEY-UHFFFAOYSA-N 0.000 description 1
- YQCFXPARMSSRRK-UHFFFAOYSA-N n-[6-(prop-2-enoylamino)hexyl]prop-2-enamide Chemical compound C=CC(=O)NCCCCCCNC(=O)C=C YQCFXPARMSSRRK-UHFFFAOYSA-N 0.000 description 1
- CEBFLGHPYLIZSC-UHFFFAOYSA-N n-benzyl-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCC1=CC=CC=C1 CEBFLGHPYLIZSC-UHFFFAOYSA-N 0.000 description 1
- OHLHOLGYGRKZMU-UHFFFAOYSA-N n-benzylprop-2-enamide Chemical compound C=CC(=O)NCC1=CC=CC=C1 OHLHOLGYGRKZMU-UHFFFAOYSA-N 0.000 description 1
- JBLADNFGVOKFSU-UHFFFAOYSA-N n-cyclohexyl-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC1CCCCC1 JBLADNFGVOKFSU-UHFFFAOYSA-N 0.000 description 1
- PMJFVKWBSWWAKT-UHFFFAOYSA-N n-cyclohexylprop-2-enamide Chemical compound C=CC(=O)NC1CCCCC1 PMJFVKWBSWWAKT-UHFFFAOYSA-N 0.000 description 1
- NIRIUIGSENVXCN-UHFFFAOYSA-N n-ethyl-2-methyl-n-phenylprop-2-enamide Chemical compound CC(=C)C(=O)N(CC)C1=CC=CC=C1 NIRIUIGSENVXCN-UHFFFAOYSA-N 0.000 description 1
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 1
- 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
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- FYCBGURDLIKBDA-UHFFFAOYSA-N n-hexyl-2-methylprop-2-enamide Chemical compound CCCCCCNC(=O)C(C)=C FYCBGURDLIKBDA-UHFFFAOYSA-N 0.000 description 1
- GCGQYJSQINRKQL-UHFFFAOYSA-N n-hexylprop-2-enamide Chemical compound CCCCCCNC(=O)C=C GCGQYJSQINRKQL-UHFFFAOYSA-N 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- NXURUGRQBBVNNM-UHFFFAOYSA-N n-nitro-2-phenylprop-2-enamide Chemical compound [O-][N+](=O)NC(=O)C(=C)C1=CC=CC=C1 NXURUGRQBBVNNM-UHFFFAOYSA-N 0.000 description 1
- BPCNEKWROYSOLT-UHFFFAOYSA-N n-phenylprop-2-enamide Chemical compound C=CC(=O)NC1=CC=CC=C1 BPCNEKWROYSOLT-UHFFFAOYSA-N 0.000 description 1
- VILFVXYKHXVYAB-UHFFFAOYSA-L naphthalene-2,7-disulfonate(2-) Chemical group C1=CC(S([O-])(=O)=O)=CC2=CC(S(=O)(=O)[O-])=CC=C21 VILFVXYKHXVYAB-UHFFFAOYSA-L 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012934 organic peroxide initiator Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical class CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical class C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001281 polyalkylene Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 102220217823 rs138107415 Human genes 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-O selenonium Chemical class [SeH3+] SPVXKVOXSXTJOY-UHFFFAOYSA-O 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- KNOGXLBAOQDKTG-UHFFFAOYSA-M sodium;2-ethylhexane-1-sulfonate Chemical compound [Na+].CCCCC(CC)CS([O-])(=O)=O KNOGXLBAOQDKTG-UHFFFAOYSA-M 0.000 description 1
- ZKCDDKBKEBVTKX-UHFFFAOYSA-M sodium;4-[2-(2-butoxyethoxy)ethoxy]butane-1-sulfonate Chemical compound [Na+].CCCCOCCOCCOCCCCS([O-])(=O)=O ZKCDDKBKEBVTKX-UHFFFAOYSA-M 0.000 description 1
- KCOBZRXMFLVGLG-UHFFFAOYSA-M sodium;4-[2-(2-hexoxyethoxy)ethoxy]butane-1-sulfonate Chemical compound [Na+].CCCCCCOCCOCCOCCCCS([O-])(=O)=O KCOBZRXMFLVGLG-UHFFFAOYSA-M 0.000 description 1
- OGBAKVHUIYJANY-UHFFFAOYSA-M sodium;4-[2-[2-(2-decoxyethoxy)ethoxy]ethoxy]butane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCOCCOCCOCCOCCCCS([O-])(=O)=O OGBAKVHUIYJANY-UHFFFAOYSA-M 0.000 description 1
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- IAAKNVCARVEIFS-UHFFFAOYSA-M sodium;4-hydroxynaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(O)=CC=C(S([O-])(=O)=O)C2=C1 IAAKNVCARVEIFS-UHFFFAOYSA-M 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- XQCHMGAOAWZUPI-UHFFFAOYSA-M sodium;butane-1-sulfonate Chemical compound [Na+].CCCCS([O-])(=O)=O XQCHMGAOAWZUPI-UHFFFAOYSA-M 0.000 description 1
- DIIKAKPJAGLSOD-UHFFFAOYSA-M sodium;cyclohexanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1CCCCC1 DIIKAKPJAGLSOD-UHFFFAOYSA-M 0.000 description 1
- QWSZRRAAFHGKCH-UHFFFAOYSA-M sodium;hexane-1-sulfonate Chemical compound [Na+].CCCCCCS([O-])(=O)=O QWSZRRAAFHGKCH-UHFFFAOYSA-M 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- HRQDCDQDOPSGBR-UHFFFAOYSA-M sodium;octane-1-sulfonate Chemical compound [Na+].CCCCCCCCS([O-])(=O)=O HRQDCDQDOPSGBR-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical class S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 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
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CCIYPTIBRAUPLQ-UHFFFAOYSA-M tetrabutylphosphanium;iodide Chemical compound [I-].CCCC[P+](CCCC)(CCCC)CCCC CCIYPTIBRAUPLQ-UHFFFAOYSA-M 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000007944 thiolates Chemical class 0.000 description 1
- 125000005424 tosyloxy group Chemical group S(=O)(=O)(C1=CC=C(C)C=C1)O* 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- KYWVDGFGRYJLPE-UHFFFAOYSA-N trimethylazanium;acetate Chemical compound CN(C)C.CC(O)=O KYWVDGFGRYJLPE-UHFFFAOYSA-N 0.000 description 1
- FBOJXFNZDVRYQZ-UHFFFAOYSA-L triphenyl(7-triphenylphosphaniumylheptyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CCCCCCC[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 FBOJXFNZDVRYQZ-UHFFFAOYSA-L 0.000 description 1
- ZELVAMAIJBWLCX-UHFFFAOYSA-N triphenyl(9-triphenylphosphaniumylnonyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CCCCCCCCC[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 ZELVAMAIJBWLCX-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- RHZZVWTVJHZKAH-UHFFFAOYSA-K trisodium;naphthalene-1,2,3-trisulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(S([O-])(=O)=O)=C(S([O-])(=O)=O)C(S(=O)(=O)[O-])=CC2=C1 RHZZVWTVJHZKAH-UHFFFAOYSA-K 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Printing Plates And Materials Therefor (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
Description
本発明は、平版印刷版原版に関する。詳しくは、レーザーによる画像露光により直接製版可能な機上現像型の平版印刷版原版に関する。 The present invention relates to a lithographic printing plate precursor. More specifically, the present invention relates to an on-press development type lithographic printing plate precursor that can be directly made by laser image exposure.
一般に、平版印刷版は、印刷過程でインキを受容する親油性の画像部と、湿し水を受容する親水性の非画像部とからなる。平版印刷は、水と油性インキが互いに反発する性質を利用して、平版印刷版の親油性の画像部をインキ受容部、親水性の非画像部を湿し水受容部(インキ非受容部)として、平版印刷版の表面にインキの付着性の差異を生じさせ、画像部のみにインキを着肉させた後、紙等の被印刷体にインキを転写して印刷する方法である。
この平版印刷版を作製するため、従来は、親水性の支持体上に親油性の感光性樹脂層(画像記録層)を設けてなる平版印刷版原版(PS版)を用い、PS版にリスフィルムなどのマスクを通した露光を行った後、アルカリ性現像液などによる現像処理を行い、画像部に対応する画像記録層を残存させ、非画像部に対応する不要な画像記録層を溶解除去して、平版印刷版を得ていた。
In general, a lithographic printing plate comprises an oleophilic image area that receives ink in the printing process and a hydrophilic non-image area that receives dampening water. Lithographic printing utilizes the property that water and oil-based inks repel each other, so that the oleophilic image area of the lithographic printing plate is the ink receiving area, and the hydrophilic non-image area is dampened with the water receiving area (ink non-receiving area). In this method, a difference in ink adhesion is caused on the surface of the lithographic printing plate, and after ink is applied only to the image area, the ink is transferred to a printing medium such as paper and printed.
In order to produce this lithographic printing plate, conventionally, a lithographic printing plate precursor (PS plate) in which an oleophilic photosensitive resin layer (image recording layer) is provided on a hydrophilic support is used. After exposure through a mask such as a film, development with an alkaline developer is performed to leave the image recording layer corresponding to the image area, and dissolve and remove the unnecessary image recording layer corresponding to the non-image area. And obtained a lithographic printing plate.
この分野の最近の進歩によって、現在、平版印刷版は、CTP(コンピュータ・トゥ・プレート)技術によって得られるようになっている。すなわち、レーザーやレーザーダイオードを用いて、リスフィルムを介することなく、直接平版印刷版原版を走査露光し、現像して平版印刷版が得られる。 Due to recent advances in this field, lithographic printing plates are now available with CTP (computer to plate) technology. That is, a lithographic printing plate can be obtained by scanning and exposing a lithographic printing plate precursor directly using a laser or a laser diode without a lith film, and developing it.
上記進歩に伴って、平版印刷版原版に関わる課題は、CTP技術に対応した画像形成特性、印刷特性、物理特性などの改良へと変化してきている。また、地球環境への関心の高まりから、平版印刷版原版に関わるもう一つの課題として、現像処理などの湿式処理に伴う廃液に関する環境課題がクローズアップされている。 Along with the above progress, problems related to the lithographic printing plate precursor have been changed to improvements in image formation characteristics, printing characteristics, physical characteristics and the like corresponding to the CTP technology. In addition, due to increasing interest in the global environment, environmental issues related to waste liquids associated with wet processing such as development processing have been highlighted as another issue related to lithographic printing plate precursors.
上記の環境課題に対して、現像あるいは製版の簡易化や無処理化が指向されている。簡易な製版方法の一つとしては、「機上現像」と呼ばれる方法が行われている。すなわち、平版印刷版原版を露光後、従来の現像は行わず、そのまま印刷機に装着して、画像記録層の不要部分の除去を通常の印刷工程の初期段階で行う方法である。 For the above environmental problems, simplification and no processing of development or plate making are directed. As one simple plate making method, a method called “on-press development” is performed. That is, after the exposure of the lithographic printing plate precursor, conventional development is not performed, but it is mounted on a printing machine as it is, and unnecessary portions of the image recording layer are removed at the initial stage of a normal printing process.
上述のような製版作業の簡易化においては、作業のしやすさの点から明室又は黄色灯下で取り扱い可能な平版印刷版原版及び光源を用いるシステムが好ましいので、光源としては、波長760〜1200nmの赤外線を放射する半導体レーザー及びYAGレーザー等の固体レーザーが用いられる。 In the simplification of the plate making operation as described above, a system using a lithographic printing plate precursor and a light source that can be handled in a bright room or under a yellow light is preferable in terms of ease of work. A solid-state laser such as a semiconductor laser or a YAG laser emitting an infrared ray of 1200 nm is used.
この赤外線レーザーで画像記録する機上現像型の平版印刷版原版においては、機上現像で除去された画像記録層成分が湿し水中でカスとなるのを抑止するために、画像記録層に樹脂微粒子を含有させることが一般的である。また、現像性と耐刷性の両立のため、樹脂微粒子の親疎水性の制御が重要である。制御の方法として、樹脂微粒子のポリマーに極性基又はアルキレンオキサイド基を含有させる方法が行われている。 In the on-press development type lithographic printing plate precursor for image recording with this infrared laser, in order to prevent the image recording layer components removed by on-press development from becoming damp in damp water, a resin is used for the image recording layer. It is common to contain fine particles. Further, in order to achieve both developability and printing durability, it is important to control the hydrophilicity / hydrophobicity of the resin fine particles. As a control method, a method in which a polymer of resin fine particles contains a polar group or an alkylene oxide group is performed.
例えば、特許文献1では樹脂微粒子が、疎水性主鎖を有し、そして疎水性主鎖に直接的に結合されたペンダントシアノ基を有する構成ユニット、及び親水性ポリ(アルキレンオキシド)セグメントを含むペンダント基を有する構成ユニットの両方を含む画像形成可能層(画像記録層)を設けた平版印刷版原版が記載されている。
しかし、このような親水性ポリ(アルキレンオキシド)セグメントを含むペンダント基を有する構成ユニットの樹脂微粒子では、微粒子全体が親水的となり、露光部の湿し水の浸透性を向上させてしまい、現像性に良化が見られるが、耐刷性が著しく低下してしまう。
For example, in Patent Document 1, a resin fine particle has a hydrophobic main chain, a pendant containing a structural unit having a pendant cyano group directly bonded to the hydrophobic main chain, and a hydrophilic poly (alkylene oxide) segment A lithographic printing plate precursor provided with an image-formable layer (image recording layer) including both constituent units having groups is described.
However, in the resin fine particles of the structural unit having a pendant group containing such a hydrophilic poly (alkylene oxide) segment, the whole fine particles become hydrophilic, improving the permeability of dampening water in the exposed area, and developability. However, the printing durability is remarkably deteriorated.
また、他の制御方法として、樹脂微粒子の表層を親水的な化合物で化学的に吸着させる方法がある。例えば、特許文献2には相互作用する極性置換基を有する化合物で微粒子の表面に吸着させ自己分散性を付与した微粒子を含有する画像記録層を設けた平版印刷版原版が記載されている。
しかし、このような微粒子では、親水性が不足し、現像性が十分ではなく、また、吸着成分が画像記録層中で遊離し、支持体表面に吸着され汚れ性が劣化してしまう問題があった。
As another control method, there is a method of chemically adsorbing the surface layer of resin fine particles with a hydrophilic compound. For example, Patent Document 2 describes a lithographic printing plate precursor provided with an image recording layer containing fine particles which are adsorbed on the surface of fine particles by a compound having an interacting polar substituent and imparted with self-dispersibility.
However, such fine particles have a problem that hydrophilicity is insufficient and developability is not sufficient, and adsorbing components are liberated in the image recording layer and adsorbed on the surface of the support, resulting in deterioration of stain resistance. It was.
このように従来の単なる樹脂微粒子の親疎水性の制御では、現像性と耐刷性と汚れ性を十分に満たすことができなかった。 Thus, the conventional simple control of the hydrophilicity / hydrophobicity of the resin fine particles could not sufficiently satisfy the developing property, printing durability and stain resistance.
したがって、本発明の目的は、コアが親油性ポリマーであり、シェルがアルキレンオキサイド鎖を有するコアシェル構造の樹脂微粒子を用いることで、特に汚れ難さと耐印刷性に優れた平版印刷版を与え、かつ、機上現像性に優れた平版印刷版原版を提供することである。 Accordingly, an object of the present invention is to provide a lithographic printing plate having particularly excellent resistance to soiling and printing resistance by using resin fine particles having a core-shell structure in which the core is an oleophilic polymer and the shell has an alkylene oxide chain, and Another object is to provide a lithographic printing plate precursor having excellent on-press developability.
本発明は以下のとおりである。
1.支持体上に、(A)ラジカル重合性化合物、(B)赤外線吸収染料、(C)ラジカル発生剤、及び(D)コア部に親油性樹脂、シェル部に下記一般式(I)で表わされる構造単位を有する樹脂を有するコアシェル構造の樹脂微粒子を含有する、インキ及び湿し水の少なくともいずれかにより除去可能な画像記録層を有する平版印刷版原版。
The present invention is as follows.
1. On the support, (A) a radical polymerizable compound, (B) an infrared absorbing dye, (C) a radical generator, and (D) a lipophilic resin in the core part, and the following general formula (I) in the shell part A lithographic printing plate precursor having an image-recording layer that can be removed by at least one of ink and dampening water, which contains fine particles of a core-shell structure having a resin having a structural unit.
一般式(I)中、R1、R2、R3及びR4は、それぞれ独立に水素原子又はメチル基を表し、m及びlは、1≦m+l≦200を満足する0又は正の整数である。 In general formula (I), R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a methyl group, and m and l are 0 or a positive integer satisfying 1 ≦ m + l ≦ 200. is there.
2.一般式(I)で表わされる構造単位において、R2が水素原子であり、R3がメチル基であることを特徴とする前記1に記載の平版印刷版原版。
3.コアシェル構造の樹脂微粒子において、シェル部の樹脂が一般式(I)で表わされる構造単位を有し、更に三次元架橋構造を有していることを特徴とする前記1又は2に記載の平版印刷版原版。
4.コアシェル構造の樹脂微粒子において、コア部の親油性樹脂がエチレン性不飽和化合物の重合によって得られる樹脂であることを特徴とする前記1〜3のいずれか1項に記載の平版印刷版原版。
5.コアシェル構造の樹脂微粒子において、コア部の親油性樹脂がスチレンモノマー及びアクリルモノマーの少なくともいずれかの重合体であることを特徴とする前記4記載の平版印刷版原版。
6.コアシェル構造の樹脂微粒子において、コア部の親油性樹脂がアクリロニトリル及びスチレンを含む共重合体であることを特徴とする前記5記載の平版印刷版原版。
7.(A)ラジカル重合性化合物がウレタン骨格を有するアクリルモノマー又はメタクリルモノマーであることを特徴とする前記1〜6のいずれか1項に記載の平版印刷版原版。
8.(A)ラジカル重合性化合物がアルキレンオキサイド基を有するアクリルモノマー又はメタクリルモノマーであることを特徴とする前記1〜7のいずれか1項に記載の平版印刷版原版。
2. 2. The lithographic printing plate precursor as described in 1 above, wherein in the structural unit represented by formula (I), R 2 is a hydrogen atom, and R 3 is a methyl group.
3. 3. The lithographic printing according to 1 or 2 above, wherein the resin in the shell part has a structural unit represented by the general formula (I) and further has a three-dimensional crosslinked structure in the resin fine particles having a core-shell structure Version original edition.
4). 4. The lithographic printing plate precursor as described in any one of 1 to 3 above, wherein in the resin fine particles having a core-shell structure, the lipophilic resin in the core is a resin obtained by polymerization of an ethylenically unsaturated compound.
5. 5. The lithographic printing plate precursor as described in 4 above, wherein in the resin fine particles having a core-shell structure, the lipophilic resin in the core is a polymer of at least one of a styrene monomer and an acrylic monomer.
6). 6. The lithographic printing plate precursor as described in 5 above, wherein in the core-shell resin fine particles, the lipophilic resin in the core is a copolymer containing acrylonitrile and styrene.
7). (A) The lithographic printing plate precursor as described in any one of 1 to 6 above, wherein the radically polymerizable compound is an acrylic monomer or a methacrylic monomer having a urethane skeleton.
8). (A) The lithographic printing plate precursor as described in any one of 1 to 7 above, wherein the radically polymerizable compound is an acrylic monomer or a methacrylic monomer having an alkylene oxide group.
本発明によれば、汚れ難さと耐印刷性に優れた平版印刷版を与え、かつ、機上現像性に優れた平版印刷版原版を提供できる。 According to the present invention, it is possible to provide a lithographic printing plate having excellent stain resistance and printing resistance, and providing a lithographic printing plate precursor having excellent on-press developability.
本発明について、以下に詳細に説明する。
〔コアシェル構造の樹脂微粒子〕
本発明の平版印刷版原版における樹脂微粒子は、コア部に親油性樹脂、シェル部に下記一般式(I)で表わされる構造単位を有する樹脂を有するコアシェル構造であることを特徴とする。
この樹脂微粒子は、少なくとも2段階の乳化重合によって得ることができる。第1段階で疎水性ポリマーの微粒子(これをコア部と称する。)を形成し、最後の重合段階で、下記一般式(I)で表わされる構造単位を有する樹脂を形成する少なくとも1種のアルキレンオキサイド基を有するアクリレートモノマーを重合させることにより、最外層の樹脂層(これをシェル部と称する。)を生成させる。
The present invention will be described in detail below.
[Core-shell resin particles]
The resin fine particles in the lithographic printing plate precursor according to the invention are characterized by having a core-shell structure having a lipophilic resin in the core portion and a resin having a structural unit represented by the following general formula (I) in the shell portion.
The resin fine particles can be obtained by at least two stages of emulsion polymerization. At least one alkylene that forms fine particles of a hydrophobic polymer (referred to as a core portion) in the first stage and forms a resin having a structural unit represented by the following general formula (I) in the final polymerization stage By polymerizing an acrylate monomer having an oxide group, an outermost resin layer (referred to as a shell portion) is generated.
一般式(I)中、R1、R2、R3及びR4は、それぞれ独立に水素原子又はメチル基を表し、m及びlは、1≦m+l≦200を満足する0又は正の整数である。 In general formula (I), R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a methyl group, and m and l are 0 or a positive integer satisfying 1 ≦ m + l ≦ 200. is there.
一般式(I)で表わされる構造単位においては、R2が水素原子で、R3がメチル基であることが好ましい。
また、上記のコアシェル構造の樹脂微粒子においては、シェル部の樹脂が前記一般式(I)で表わされる構造単位を有し、更に三次元架橋構造を有していることが好ましい。
In the structural unit represented by the general formula (I), R 2 is preferably a hydrogen atom and R 3 is preferably a methyl group.
In the resin particles having the core-shell structure described above, it is preferable that the resin in the shell portion has a structural unit represented by the general formula (I) and further has a three-dimensional crosslinked structure.
コア部を構成する親油性樹脂としては、水に不溶な樹脂であり、特にメタノールに不溶な樹脂が好ましい。
これらは、以下の(A)〜(J)から選ばれたモノマーを原料とする、アクリル樹脂、スチレン樹脂、ビニルエステル樹脂及びその他の重合体若しくは共重合体が好ましい。また、エポキシ樹脂、ウレタン樹脂、フェノール樹脂も好ましいものとして挙げられる。更にこれらの樹脂、重合体若しくは共重合体の誘導体も好適である。
The lipophilic resin constituting the core part is a resin insoluble in water, and a resin insoluble in methanol is particularly preferable.
These are preferably acrylic resins, styrene resins, vinyl ester resins, and other polymers or copolymers using monomers selected from the following (A) to (J) as raw materials. Moreover, an epoxy resin, a urethane resin, and a phenol resin are also mentioned as a preferable thing. Furthermore, derivatives of these resins, polymers or copolymers are also suitable.
(A)アクリル酸エステル類。このモノマー群の例には、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸アミル、アクリル酸ヘキシル、アクリル酸シクロヘキシル、アクリル酸オクチル、アクリル酸フェニル、アクリル酸ベンジル、アクリル酸−2−クロロエチル、アクリル酸−2−ヒドロキシエチル、アクリル酸−4−ヒドロキシブチル、グリシジルアクリレート、N−ジメチルアミノエチルアクリレート、o−、m−及びp−ヒドロキシフェニルアクリレートなどの(置換)アクリル酸エステルが挙げられる。 (A) Acrylic acid esters. Examples of this monomer group include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, phenyl acrylate, benzyl acrylate, acrylic acid (Substituted) acrylic acid esters such as 2-chloroethyl, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, o-, m- and p-hydroxyphenyl acrylate Is mentioned.
(B)メタクリル酸エステル類。このモノマー群の例には、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸アミル、メタクリル酸ヘキシル、メタクリル酸シクロヘキシル、メタクリル酸オクチル、メタクリル酸フェニル、メタクリル酸ベンジル、メタクリル酸−2−クロロエチル、メタクリル酸−2−ヒドロキシエチル、メタクリル酸−4−ヒドロキシブチル、グリシジルメタクリレート、N−ジメチルアミノエチルメタクリレート、o−、m−及びp−ヒドロキシフェニルメタクリレートなどの(置換)メタクリル酸エステルが挙げられる。 (B) Methacrylic acid esters. Examples of this monomer group include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylic acid. (Substituted) methacrylate esters such as 2-chloroethyl, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate, o-, m- and p-hydroxyphenyl methacrylate Is mentioned.
(C)スチレン類。このモノマー群の例には、スチレン、メチルスチレン、クロロメチルスチレン、o−、m−及びp−ヒドロキシスチレンなどが挙げられる。 (C) Styrenes. Examples of this monomer group include styrene, methyl styrene, chloromethyl styrene, o-, m-, and p-hydroxystyrene.
(D)ビニルエステル類。このモノマー群の例には、ビニルアセテート、ビニルクロロアセテート、ビニルブチレート、安息香酸ビニルなどが挙げられる。 (D) Vinyl esters. Examples of this monomer group include vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate and the like.
(E)アクリルアミド及びメタクリルアミド類。このモノマー群の例には、アクリルアミド、メタクリルアミド、N−メチロールアクリルアミド、N−メチロールメタクリルアミド、N−エチルアクリルアミド、N−エチルメタクリルアミド、N−ヘキシルアクリルアミド、N−ヘキシルメタクリルアミド、N−シクロヘキシルアクリルアミド、N−シクロヘキシルメタクリルアミド、N−ヒドロキシエチルアクリルアミド、N−ヒドロキシエチルアクリルアミド、N−フェニルアクリルアミド、N−フェニルメタクリルアミド、N−ベンジルアクリルアミド、N−ベンジルメタクリルアミド、N−ニトロフェニルアクリルアミド、N−ニトロフェニルメタクリルアミド、N−エチル−N−フェニルアクリルアミド及びN−エチル−N−フェニルメタクリルアミド、N−(4−ヒドロキシフェニル)アクリルアミド、N−(4−ヒドロキシフェニル)メタクリルアミドなどのアクリルアミド若しくはメタクリルアミドが挙げられる。 (E) Acrylamide and methacrylamide. Examples of this monomer group include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-ethyl acrylamide, N-ethyl methacrylamide, N-hexyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide. N-cyclohexylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitro Phenylmethacrylamide, N-ethyl-N-phenylacrylamide and N-ethyl-N-phenylmethacrylamide, N- (4-hydroxyphenyl) Yl) acrylamide, acrylamide or methacrylamide, such as N-(4-hydroxyphenyl) methacrylamide.
(F)ビニルエーテル類。このモノマー群の例には、エチルビニルエーテル、2−クロロエチルビニルエーテル、ヒドロキシエチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、オクチルビニルエーテル、フェニルビニルエーテルなどが挙げられる。 (F) Vinyl ethers. Examples of this monomer group include ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether and the like.
(G)ビニルケトン類。このモノマー群の例には、メチルビニルケトン、エチルビニルケトン、プロピルビニルケトン、フェニルビニルケトンなどが挙げられる。 (G) Vinyl ketones. Examples of this monomer group include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(H)オレフィン類。このモノマー群の例には、エチレン、プロピレン、イソブチレン、ブタジエン、イソプレンなどが挙げられる。 (H) Olefins. Examples of this monomer group include ethylene, propylene, isobutylene, butadiene, isoprene and the like.
(I)N−含有モノマー。このモノマー群の例には、N−ビニルピロリドン、N−ビニルカルバゾール、4−ビニルピリジン、アクリロニトリル、メタクリロニトリルなどが挙げられる。 (I) N-containing monomers. Examples of this monomer group include N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like.
(J)不飽和スルホンアミド。このモノマー群の例には、N−(o−アミノスルホニルフェニル)アクリルアミド、N−(m−アミノスルホニルフェニル)アクリルアミド、N−(p−アミノスルホニルフェニル)アクリルアミド、N−〔1−(3−アミノスルホニル)ナフチル〕アクリルアミド、N−(2−アミノスルホニルエチル)アクリルアミドなどのアクリルアミド類、N−(o−アミノスルホニルフェニル)メタクリルアミド、N−(m−アミノスルホニルフェニル)メタクリルアミド、N−(p−アミノスルホニルフェニル)メタクリルアミド、N−〔1−(3−アミノスルホニル)ナフチル〕メタクリルアミド、N−(2−アミノスルホニルエチル)メタクリルアミドなどのメタクリルアミド類、及びo−アミノスルホニルフェニルアクリレート、m−アミノスルホニルフェニルアクリレート、p−アミノスルホニルフェニルアクリレート、1−(3−アミノスルホニルフェニルナフチル)アクリレート、o−アミノスルホニルフェニルメタクリレート、m−アミノスルホニルフェニルメタクリレート、p−アミノスルホニルフェニルメタクリレート、1−(3−アミノスルホニルフェニルナフチル)メタクリレートなどのアクリル酸及びメタクリル酸エステル類が挙げられる。 (J) Unsaturated sulfonamides. Examples of this monomer group include N- (o-aminosulfonylphenyl) acrylamide, N- (m-aminosulfonylphenyl) acrylamide, N- (p-aminosulfonylphenyl) acrylamide, N- [1- (3-amino Sulfonyl) naphthyl] acrylamide, acrylamides such as N- (2-aminosulfonylethyl) acrylamide, N- (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p- Aminosulfonylphenyl) methacrylamide, N- [1- (3-aminosulfonyl) naphthyl] methacrylamide, methacrylamides such as N- (2-aminosulfonylethyl) methacrylamide, and o-aminosulfonylphenyl acrylate, m- Ami Sulfonylphenyl acrylate, p-aminosulfonylphenyl acrylate, 1- (3-aminosulfonylphenylnaphthyl) acrylate, o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, 1- (3-amino And acrylic acid and methacrylic acid esters such as sulfonylphenylnaphthyl) methacrylate.
これらの中でもスチレンとアクリロニトリルの共重合体により得られる微粒子が最も好ましい。 Among these, fine particles obtained from a copolymer of styrene and acrylonitrile are most preferable.
シェル部を構成する上記一般式(I)で表わされる構造単位を形成させるアルキレンオキサイド基含有アクリレートモノマーの具体例としては下記が挙げられる。 The following is mentioned as a specific example of the alkylene oxide group containing acrylate monomer which forms the structural unit represented by the said general formula (I) which comprises a shell part.
例えば、エチレングリコール(メタ)アクリレート、ジエチレングリコール(メタ)アクリレート、トリエチレングリコール(メタ)アクリレート等のポリエチレングリコール(メタ)アクリレート類;メトキシエチル(メタ)アクリレート、メトキシジエチレングリコール(メタ)アクリレート等のメトキシポリエチレングリコール(メタ)アクリレート類;エトキシエチル(メタ)アクリレート、エトキシジエチレングリコール(メタ)アクリレート等のエトキシポリエチレングリコール(メタ)アクリレート類;ブトキシエチル(メタ)アクリレート、ブトキシジエチレングリコール(メタ)アクリレート等のブトキシポリエチレングリコール(メタ)アクリレート類等のアルコキシポリエチレングリコール(メタ)アクリレート類;フェノキシエチル(メタ)アクリレート、フェノキシジエチレングリコール(メタ)アクリレート等のフェノキシポリエチレングリコール(メタ)アクリレート類;ノニルフェノキシポリエチレングリコール(メタ)アクリレート等のアルキルフェノキシポリエチレングリコール(メタ)アクリレート類等が挙げられる。 For example, polyethylene glycol (meth) acrylates such as ethylene glycol (meth) acrylate, diethylene glycol (meth) acrylate, and triethylene glycol (meth) acrylate; methoxypolyethylene glycol such as methoxyethyl (meth) acrylate and methoxydiethylene glycol (meth) acrylate (Meth) acrylates; ethoxypolyethylene glycol (meth) acrylates such as ethoxyethyl (meth) acrylate and ethoxydiethylene glycol (meth) acrylate; butoxypolyethylene glycols such as butoxyethyl (meth) acrylate and butoxydiethylene glycol (meth) acrylate (meta ) Alkoxy polyethylene glycol (meth) acrylates such as acrylates; Enokishiechiru (meth) acrylate, phenoxy diethylene glycol (meth) phenoxy polyethylene glycol (meth) acrylates such as acrylate; nonylphenoxy alkylphenoxy polyethylene glycols such as polyethylene glycol (meth) acrylate (meth) acrylates.
これらのものは通常の市販品が使用できるほか、必要に応じて適当なアルコキシポリエチレングリコールと(メタ)アクリリルクロライドとをアセトニトリル等の不活性溶媒中で、トリエチルアミン等の触媒を用いて反応させること等によって製造することもできる(特公昭34−4292号公報参照)。 These products can be used as ordinary commercial products, and if necessary, react with appropriate alkoxy polyethylene glycol and (meth) acrylyl chloride in an inert solvent such as acetonitrile using a catalyst such as triethylamine. Etc. (see Japanese Patent Publication No. 34-4292).
また、アルキレンオキサイド鎖の末端がヒドロキシ基を有する場合、公知の手段を用いて修飾したものを用いてもよい。例えば、アルキレンオキサイド鎖の末端のヒドロキシ基とイソシアネート基を反応させたものを用いてもよい。 Moreover, when the terminal of an alkylene oxide chain has a hydroxy group, you may use what was modified using the well-known means. For example, you may use what made the hydroxyl group and isocyanate group of the terminal of an alkylene oxide chain react.
更に、一般式(I)のm+lは、より好ましくは2〜100の範囲であり、4〜95の範囲が最も好ましい。 Furthermore, m + 1 of the general formula (I) is more preferably in the range of 2 to 100, and most preferably in the range of 4 to 95.
本発明におけるシェル部は一般式(I)で表わされる構成単位のほかに、公知のラジカル重合性化合物と共重合させたものを用いてもよい。前記のアルキレンオキシド基を有するモノマーと共重合するモノマーは、特に使用量に制限はないが、得られる粒子の強度や現像性の点から、下記(a)〜(d)のモノマー又は架橋体の組み合わせが好ましい。 In addition to the structural unit represented by the general formula (I), a shell copolymerized with a known radical polymerizable compound may be used in the present invention. The monomer copolymerized with the monomer having an alkylene oxide group is not particularly limited in the amount used, but from the viewpoint of the strength and developability of the resulting particles, the following monomers (a) to (d) A combination is preferred.
(a)単独重合体のガラス転移温度が0℃未満のアクリル酸エチル、アクリル酸nープロピル、アクリル酸nーブチル、アクリル酸イソブチル、アクリル酸2ーエチルヘキシル、アクリル酸オクチル、アクリル酸ラウリル、アクリル酸トリデシル、アクリル酸ヒドロキシエチル、アクリル酸ヒドロキシプロピル等の、単独重合体のガラス転移温度が0℃未満のアクリル酸アルキルエステル;メタクリル酸ラウリル、メタクリル酸トリデシル等の、単独重合体のガラス転移温度が0℃未満のメタクリル酸アルキルエステル;エチレン、イソブチレン、塩化ビニリデン、ブタジエン等の、単独重合体のガラス転移温度が0℃未満のモノマー。 (A) Ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, tridecyl acrylate having a glass transition temperature of less than 0 ° C. Acrylic acid alkyl ester whose homopolymer glass transition temperature is less than 0 ° C., such as hydroxyethyl acrylate, hydroxypropyl acrylate, etc .; The glass transition temperature of homopolymers such as lauryl methacrylate, tridecyl methacrylate is 0 ° C. A monomer having a glass transition temperature of less than 0 ° C. of a homopolymer such as ethylene, isobutylene, vinylidene chloride, butadiene or the like.
(b)単独重合体のガラス転移温度点が0℃以上のアクリル酸メチル、アクリル酸tーブチル等の、単独重合体のガラス転移温度が0℃以上のアクリル酸アルキルエステル;メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸ヒドロキシエチル等の、単独重合体のガラス転移温度が0℃以上のメタクリル酸アルキルエステル;スチレン、α−メチルスチレン、塩化ビニル、酢酸ビニル、プロピオン酸ビニル、分岐脂肪酸ビニル(バーサチック酸ビニル)、アクリロニトリル、メタクリロニトリル、アクリルアミド、メタクリルアミド等の、単独重合体のガラス転移温度点が0℃以上のその他のモノマー。 (B) Acrylic acid alkyl ester having a glass transition temperature of 0 ° C. or higher, such as methyl acrylate or t-butyl acrylate having a glass transition temperature point of homopolymer of 0 ° C. or higher; methyl methacrylate, methacrylic acid Methacrylic acid alkyl ester whose homopolymer has a glass transition temperature of 0 ° C. or higher, such as ethyl, propyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate; styrene, α-methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate , Other monomers having a glass transition temperature point of homopolymers of 0 ° C. or higher, such as branched fatty acid vinyl (vinyl versatate), acrylonitrile, methacrylonitrile, acrylamide, methacrylamide and the like.
(c)特殊な官能基を有する単量体:アクリル酸、メタクリル酸、クロトン酸、イタコン酸のごとき不飽和カルボン酸、無水マレイン酸のごとき不飽和カルボン酸の無水物、Nーメチロールアクリルアミド、Nーメチロールメタクリルアミド、Nーフェニルマレイミド、Nー(メチル)フェニルマレイミド、Nー(ヒドロキシ)フェニルマレイミド、Nー(メトキシ)フェニルマレイミド、Nー安息香酸マレイミド、Nーメチルマレイミド、Nーエチルマレイミド、Nーnープロピルマレイミド、Nーイソプロピルマレイミド、Nーnーブチルマレイミド、Nーイソブチルマレイミド、Nーtーブチルマレイミドのごとき特殊な官能基を有するその他のモノマー。 (C) Monomers having special functional groups: unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and itaconic acid, anhydrides of unsaturated carboxylic acids such as maleic anhydride, N-methylolacrylamide, N -Methylol methacrylamide, N-phenylmaleimide, N- (methyl) phenylmaleimide, N- (hydroxy) phenylmaleimide, N- (methoxy) phenylmaleimide, N-benzoic acid maleimide, N-methylmaleimide, N-ethylmaleimide, Other monomers having a special functional group such as Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, Nt-butylmaleimide.
(d)架橋体:エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ) アクリレート、ポリエチレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、1、3ーブチレングリコールジ(メタ)アクリレート、1、4ーブチレングリコールジ(メタ)アクリレート、トリメチロールエタントリアクリレート、トリメチロールプロパントリアクリレート、ジビニルベンゼン、共役ジエン化合物等の2個以上の不飽和基を有する多官能体、ブロモトリクロロメタン、ブロモホルム、四塩化炭素、四臭化炭素等の2個以上の引き抜き可能な原子を有する反応体、及び、アリルメルカプタン、メタリルメルカプタン、クロチルメルカプタン、アリル(メタ)アクリレート、メタリル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、N−アリル(メタ)アクリレート、N,Nージアリル(メタ)アクリレート、N−メタリル(メタ)アクリレート、N,Nージメタリル(メタ)アクリレート、N−クロチル(メタ)アクリレート、N,Nージクロチル(メタ)アクリレート等の1個以上の不飽和基と1個以上の引き抜き可能な原子を有する多官能性単量体等の架橋体。 (D) Crosslinked product: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di 2 such as (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, divinylbenzene, conjugated diene compound, etc. A polyfunctional compound having at least one unsaturated group, a reactant having two or more abstractable atoms such as bromotrichloromethane, bromoform, carbon tetrachloride, carbon tetrabromide, and allyl mercap Tan, methallyl mercaptan, crotyl mercaptan, allyl (meth) acrylate, methallyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N-allyl (meth) acrylate, N, N-diallyl (meth) acrylate, N-methallyl It has one or more unsaturated groups such as (meth) acrylate, N, N-dimethallyl (meth) acrylate, N-crotyl (meth) acrylate, N, N-dicrotyl (meth) acrylate and one or more extractable atoms. Cross-linked products such as polyfunctional monomers.
本発明におけるシェル部の樹脂は、エチレンオキサイド基を有する不飽和体を好ましくは0.1〜80質量%、より好ましくは10〜50質量%、最も好ましくは20〜40質量%、前記(a)のモノマーを好ましくは0〜50質量%、より好ましくは5〜30質量%、最も好ましくは20〜30質量%、前記(b)のモノマーを好ましくは0〜50質量%、より好ましくは5〜30質量%、最も好ましくは20〜30質量%、前記(c)のモノマーを好ましくは0〜50質量%、より好ましくは5〜30質量%、最も好ましくは20〜30質量%、前記(d)のモノマーを好ましくは0〜15質量%、より好ましくは0〜10質量%、最も好ましくは0〜5質量%の割合で共重合させるのが好ましい。 The resin of the shell part in the present invention is preferably 0.1 to 80% by mass, more preferably 10 to 50% by mass, and most preferably 20 to 40% by mass of the unsaturated body having an ethylene oxide group. The monomer is preferably 0-50% by mass, more preferably 5-30% by mass, most preferably 20-30% by mass, and the monomer (b) is preferably 0-50% by mass, more preferably 5-30%. % By weight, most preferably from 20 to 30% by weight, preferably from 0 to 50% by weight of the monomer of (c), more preferably from 5 to 30% by weight, most preferably from 20 to 30% by weight. The monomer is preferably copolymerized in a proportion of preferably 0 to 15% by mass, more preferably 0 to 10% by mass, and most preferably 0 to 5% by mass.
乳化重合に用いる乳化剤としては、ジアルキルスルホコハク酸ナトリウム、アルキルスルホン酸のアルカリ塩、オキシアルキル化されたアルコール又はアルキルフェノールのアルカリ金属塩、脂肪酸のアルカリ塩などアニオン性界面活性剤、ノニオン性界面活性剤の各種のものが単独若しくは併用して使用できる。その使用量は、通常樹脂分に対し0.1〜10質量%の割合である。また、目的によっては、カチオン性界面活性剤を単独で、あるいはノニオン性界面活性剤と併用して使用することもできる。 As an emulsifier used for emulsion polymerization, anionic surfactants such as sodium dialkylsulfosuccinate, alkali salts of alkyl sulfonic acids, alkali metal salts of oxyalkylated alcohols or alkylphenols, alkali salts of fatty acids, nonionic surfactants, etc. Various types can be used alone or in combination. The amount used is usually 0.1 to 10% by mass relative to the resin content. Further, depending on the purpose, the cationic surfactant can be used alone or in combination with the nonionic surfactant.
乳化重合において用いる重合開始剤は、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、過酸化水素などの無機過酸化物が好ましいが、その他ベンゾビスイソブチロニトリル、アゾビスバレロニトリルなどのアゾ系開始剤;ベンゾイルパーオキサイド、ラウロイルパーオキサイド、tーブチルパーオキサイドなどの有機過酸化物系開始剤も使用できる。また、これらの開始剤に、ロンガリット、Lーアスコルビン酸、有機アミン、金属塩などの還元剤を併用してレドックス開始剤として用いてもよい。 The polymerization initiator used in the emulsion polymerization is preferably an inorganic peroxide such as potassium persulfate, sodium persulfate, ammonium persulfate or hydrogen peroxide, but other azo initiators such as benzobisisobutyronitrile and azobisvaleronitrile. Agents: Organic peroxide initiators such as benzoyl peroxide, lauroyl peroxide, and t-butyl peroxide can also be used. These initiators may be used as a redox initiator in combination with a reducing agent such as Rongalite, L-ascorbic acid, an organic amine, or a metal salt.
上記のコアシェル型微粒子の平均粒径は、0.01〜3.0μmが好ましい。0.05〜2.0μmが更に好ましく、0.10〜0.5μmが特に好ましい。この範囲内で良好な解像度と経時安定性が得られる。 The average particle diameter of the core-shell type fine particles is preferably 0.01 to 3.0 μm. 0.05-2.0 micrometers is still more preferable, and 0.10-0.5 micrometer is especially preferable. Within this range, good resolution and stability over time can be obtained.
コアシェル型微粒子の画像記録層中の含有量は、画像記録層全固形分に対して、好ましくは5〜90質量%であり、より好ましくは20〜70質量%であり、最も好ましくは30〜60質量%である。この範囲内であるほど、現像性と耐刷性の両立の観点で好ましい。 The content of the core-shell type fine particles in the image recording layer is preferably 5 to 90% by mass, more preferably 20 to 70% by mass, and most preferably 30 to 60% with respect to the total solid content of the image recording layer. % By mass. Within this range, it is preferable from the viewpoint of achieving both developability and printing durability.
〔画像記録層〕
本発明に用いられる画像記録層は、機上現像可能な画像記録層である。画像記録層が含有する機上現像可能な代表的な画像形成態様としては、(A)ラジカル重合性化合物、(B)赤外線吸収染料、及び(C)ラジカル発生剤を含有して、重合反応を利用して画像部を硬化させる態様であり、これに上記(D)のコアシェル構造の樹脂微粒子を含有させるものである。
なお、樹脂微粒子としては、(E)上記(D)のコアシェル型以外の樹脂微粒子を併用することもできる。
以下では、前記コアシェル型樹脂微粒子以外の、画像記録層成分について、順次詳細に説明する。
(Image recording layer)
The image recording layer used in the present invention is an on-press developable image recording layer. A typical image forming mode that can be developed on-press contained in the image recording layer includes (A) a radical polymerizable compound, (B) an infrared-absorbing dye, and (C) a radical generator. This is an embodiment in which the image portion is cured by utilizing the resin fine particles having the core-shell structure (D) described above.
In addition, as resin fine particles, resin fine particles other than (E) the core-shell type of (D) can be used in combination.
Hereinafter, the components of the image recording layer other than the core-shell type resin fine particles will be described in detail sequentially.
(A)ラジカル重合性化合物
本発明における画像記録層に用いるラジカル重合性化合物は、少なくとも一個のエチレン性不飽和二重結合を有する付加重合性化合物であり、末端エチレン性不飽和結合を少なくとも1個、好ましくは2個以上有する化合物から選ばれる。これらは、例えばモノマー、プレポリマー、すなわち2量体、3量体及びオリゴマー、又はそれらの混合物などの化学的形態をもつ。
(A) Radical polymerizable compound The radical polymerizable compound used in the image recording layer in the invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one terminal ethylenically unsaturated bond. , Preferably selected from compounds having two or more. These have chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof.
モノマーの例としては、不飽和カルボン酸(例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸など)や、そのエステル類、アミド類が挙げられ、好ましくは、不飽和カルボン酸と多価アルコール化合物とのエステル、不飽和カルボン酸と多価アミン化合物とのアミド類が用いられる。また、ヒドロキシ基やアミノ基、メルカプト基等の求核性置換基を有する不飽和カルボン酸エステルあるいはアミド類と単官能若しくは多官能イソシアネート類あるいはエポキシ類との付加反応物、及び単官能若しくは、多官能のカルボン酸との脱水縮合反応物等も好適に使用される。また、イソシアネート基や、エポキシ基等の親電子性置換基を有する不飽和カルボン酸エステルあるいはアミド類と単官能若しくは多官能のアルコール類、アミン類、チオール類との付加反応物、更にハロゲン基や、トシルオキシ基等の脱離性置換基を有する不飽和カルボン酸エステルあるいはアミド類と単官能若しくは多官能のアルコール類、アミン類、チオール類との置換反応物も好適である。また、別の例として、上記の不飽和カルボン酸の代わりに、不飽和ホスホン酸、スチレン、ビニルエーテル等に置き換えた化合物群を使用することも可能である。これらは、特表2006−508380号公報、特開2002−287344号公報、特開2008−256850号公報、特開2001−342222号公報、特開平9−179296号公報、特開平9−179297号公報、特開平9−179298号公報、特開2004−294935号公報、特開2006−243493号公報、特開2002−275129号公報、特開2003−64130号公報、特開2003−280187号公報、特開平10−333321号公報、を含む参照文献に記載されている。 Examples of monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, preferably unsaturated carboxylic acids. An ester of an acid and a polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and a polyvalent amine compound are used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional compound. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid. These are disclosed in JP-T-2006-508380, JP-A-2002-287344, JP-A-2008-256850, JP-A-2001-342222, JP-A-9-179296, JP-A-9-179297. JP-A-9-179298, JP-A-2004-294935, JP-A-2006-243493, JP-A-2002-275129, JP-A-2003-64130, JP-A-2003-280187, It is described in references including Kaihei 10-333321.
多価アルコール化合物と不飽和カルボン酸とのエステルのモノマーの具体例としては、アクリル酸エステルとして、エチレングリコールジアクリレート、1,3−ブタンジオールジアクリレート、テトラメチレングリコールジアクリレート、プロピレングリコールジアクリレート、トリメチロールプロパントリアクリレート、ヘキサンジオールジアクリレート、テトラエチレングリコールジアクリレート、ペンタエリスリトールテトラアクリレート、ソルビトールトリアクリレート、イソシアヌール酸エチレンオキシド(EO)変性トリアクリレート、ポリエステルアクリレートオリゴマー等がある。メタクリル酸エステルとしては、テトラメチレングリコールジメタクリレート、ネオペンチルグリコールジメタクリレート、トリメチロールプロパントリメタクリレート、エチレングリコールジメタクリレート、ペンタエリスリトールトリメタクリレート、ビス〔p−(3−メタクリルオキシ−2−ヒドロキシプロポキシ)フェニル〕ジメチルメタン、ビス−〔p−(メタクリルオキシエトキシ)フェニル〕ジメチルメタン等がある。また、多価アミン化合物と不飽和カルボン酸とのアミドのモノマーの具体例としては、メチレンビス−アクリルアミド、メチレンビス−メタクリルアミド、1,6−ヘキサメチレンビス−アクリルアミド、1,6−ヘキサメチレンビス−メタクリルアミド、ジエチレントリアミントリスアクリルアミド、キシリレンビスアクリルアミド、キシリレンビスメタクリルアミド等がある。 Specific examples of the monomer of the ester of a polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, Examples include trimethylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, isocyanuric acid ethylene oxide (EO) -modified triacrylate, and polyester acrylate oligomer. Methacrylic acid esters include tetramethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, pentaerythritol trimethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl ] Dimethylmethane, bis- [p- (methacryloxyethoxy) phenyl] dimethylmethane, and the like. Specific examples of amide monomers of polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylic. Examples include amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.
また、イソシアネートとヒドロキシ基の付加反応を用いて製造されるウレタン系付加重合性化合物も好適であり、そのような具体例としては、例えば、特公昭48−41708号公報に記載されている1分子に2個以上のイソシアネート基を有するポリイソシアネート化合物に、下記一般式(i)で示されるヒドロキシ基を含有するビニルモノマーを付加させた1分子中に2個以上の重合性ビニル基を含有するビニルウレタン化合物等が挙げられる。
CH2=C(R4)COOCH2CH(R5)OH (i)
(ただし、R4及びR5は、H又はCH3を示す。)
In addition, urethane-based addition-polymerizable compounds produced by using an addition reaction between an isocyanate and a hydroxy group are also suitable, and specific examples thereof include, for example, one molecule described in Japanese Patent Publication No. 48-41708. A vinyl containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxy group represented by the following general formula (i) to a polyisocyanate compound having two or more isocyanate groups. A urethane compound etc. are mentioned.
CH 2 = C (R 4) COOCH 2 CH (R 5) OH (i)
(However, R 4 and R 5 represent H or CH 3. )
また、特開昭51−37193号公報、特公平2−32293号公報、特公平2−16765号公報、特開2003−344997号公報、特開2006−65210号公報に記載されているようなウレタンアクリレート類や、特公昭58−49860号公報、特公昭56−17654号公報、特公昭62−39417号公報、特公昭62−39418号公報、特開2000−250211号公報、特開2007−94138号公報記載のエチレンオキサイド系骨格を有するウレタン化合物類や、US7153632号公報、特表平8−505958号公報、特開2007−293221号公報、特開2007−293223号公報記載の親水基を有するウレタン化合物類も好適である。 Also, urethanes described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-A-2003-344997, and JP-A-2006-65210. Acrylates, JP-B 58-49860, JP-B 56-17654, JP-B 62-39417, JP-B 62-39418, JP-A 2000-250211, JP-A 2007-94138 Urethane compounds having an ethylene oxide-based skeleton described in the publication, and urethane compounds having a hydrophilic group described in US Pat. No. 7,153,632, JP-T 8-505958, JP-A 2007-293221, and JP-A 2007-293223. Are also suitable.
上記の中でも、本発明の微粒子との相溶性の観点から、アルキレンオキサイド鎖又は水素結合を形成しうる官能基、例えばウレタン結合などを有することが好ましい。
好ましいウレタンアクリレートモノマーは下記一般式(1)で表される。
Among these, from the viewpoint of compatibility with the fine particles of the present invention, it is preferable to have a functional group capable of forming an alkylene oxide chain or a hydrogen bond, such as a urethane bond.
A preferred urethane acrylate monomer is represented by the following general formula (1).
一般式(1)中、Aは1〜3個のエチレン性不飽和基を含有する基を表す。Lは炭素原子数5〜9のアルキレン基を表す。
Aは下記一般式(2)で表される基が好ましい。
In general formula (1), A represents a group containing 1 to 3 ethylenically unsaturated groups. L represents an alkylene group having 5 to 9 carbon atoms.
A is preferably a group represented by the following general formula (2).
一般式(2)中、Xはアクリロイルオキシ基又はメタクリロイルオキシ基を表わす。
mは1〜3の整数を表し、一般式(2)中に複数存在するXは、それぞれ独立にアクリロイルオキシ基又はメタクリロイルオキシ基を表す。
Mは下記の基を組合せてできる連結基である。特に炭素原子数が2〜6のアルキレン基が好ましい。
In general formula (2), X represents an acryloyloxy group or a methacryloyloxy group.
m represents an integer of 1 to 3, and a plurality of Xs in the general formula (2) each independently represents an acryloyloxy group or a methacryloyloxy group.
M is a linking group formed by combining the following groups. An alkylene group having 2 to 6 carbon atoms is particularly preferable.
Lは下記の基を組合せてできる炭素原子数5〜9のアルキレン基であることが好ましい。 L is preferably an alkylene group having 5 to 9 carbon atoms formed by combining the following groups.
好ましい構造として下記の構造を挙げることができる。 Preferred structures include the following structures.
ここで一般式(3)のnは5〜9の整数である。Lで表されるアルキレン基で特に好ましいのは、一般式(3)でnが6のアルキレン基、及び一般式(4)で表されるアルキレン基である。 Here, n in the general formula (3) is an integer of 5 to 9. Particularly preferred among the alkylene groups represented by L are an alkylene group represented by general formula (3), wherein n is 6, and an alkylene group represented by general formula (4).
以下に、一般式(1)で表される重合性化合物の具体例を示すが、これらに限定されない。 Although the specific example of the polymeric compound represented by General formula (1) below is shown, it is not limited to these.
上記の中でも、機上現像性に関与する親水性と耐刷性に関与する重合能のバランスに優れる点から、ヘキサメチレンジイソシアネート(Bayer Corp、Milford, CTから入手可能)を基剤とする脂肪族ポリイソシアネートを、ヒドロキシアクリレートと反応させることにより調製されたウレタンアクリレートモノマー(U−10)が最も好ましい。 Among these, aliphatics based on hexamethylene diisocyanate (available from Bayer Corp, Milford, CT) are superior in the balance between the hydrophilicity involved in on-press developability and the polymerization ability involved in printing durability. Most preferred is urethane acrylate monomer (U-10) prepared by reacting polyisocyanate with hydroxy acrylate.
これらの重合性化合物の構造、単独使用か併用か、添加量等の使用方法の詳細は、最終的な平版印刷版原版の性能設計にあわせて任意に設定できる。上記の重合性化合物は、画像記録層の全固形分に対して、好ましくは5〜75質量%、更に好ましくは10〜70質量%、特に好ましくは15〜60質量%の範囲で使用される。 Details of the usage method such as the structure of these polymerizable compounds, whether they are used alone or in combination, and the amount added can be arbitrarily set in accordance with the performance design of the final lithographic printing plate precursor. The polymerizable compound is preferably used in the range of 5 to 75% by mass, more preferably 10 to 70% by mass, and particularly preferably 15 to 60% by mass with respect to the total solid content of the image recording layer.
(B)赤外線吸収染料
赤外線吸収染料は、吸収した赤外線を熱に変換する機能と赤外線により励起して後述のラジカル発生剤に電子移動及び/又はエネルギー移動する機能を有する。本発明において使用される赤外線吸収染料は、波長760〜1200nmに吸収極大を有する染料である。
(B) Infrared-absorbing dye The infrared-absorbing dye has a function of converting the absorbed infrared light into heat and a function of being excited by infrared light to transfer electrons and / or energy to a radical generator described later. The infrared absorbing dye used in the present invention is a dye having an absorption maximum at a wavelength of 760 to 1200 nm.
染料としては、市販の染料及び例えば、「染料便覧」(有機合成化学協会編集、昭和45年刊)等の文献に記載されている公知のものが利用できる。具体的には、アゾ染料、金属錯塩アゾ染料、ピラゾロンアゾ染料、ナフトキノン染料、アントラキノン染料、フタロシアニン染料、カルボニウム染料、キノンイミン染料、メチン染料、シアニン染料、スクアリリウム色素、ピリリウム塩、金属チオレート錯体等の染料が挙げられる。
これらの染料のうち特に好ましいものとしては、シアニン色素、スクアリリウム色素、ピリリウム塩、ニッケルチオレート錯体、インドレニンシアニン色素が挙げられる。更に、シアニン色素やインドレニンシアニン色素が好ましく、特に好ましい例として下記一般式(ii)で示されるシアニン色素が挙げられる。
As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as 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 salts, metal thiolate complexes Is mentioned.
Particularly preferred among these dyes are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Further, cyanine dyes and indolenine cyanine dyes are preferred, and particularly preferred examples include cyanine dyes represented by the following general formula (ii).
一般式(ii)中、X1は、水素原子、ハロゲン原子、−N(R9)(R10)、−X2−L1又は以下に示す基を表す。ここで、R9及びR10は、それぞれ同じでも異なっていてもよく、置換基を有していてもよい炭素原子数6〜10の芳香族炭化水素基、炭素原子数1〜8のアルキル基、水素原子を表し、またR9とR10とが互いに結合して環を形成してもよい。なかでもフェニル基が好ましい。X2は酸素原子又は硫黄原子を示し、L1は、炭素原子数1〜12の炭化水素基、ヘテロ原子を有する芳香族環、ヘテロ原子を含む炭素原子数1〜12の炭化水素基を示す。なお、ここでヘテロ原子とは、N、S、O、ハロゲン原子、Seを示す。以下に示す基において、Xa−は後述するZa−と同様に定義され、Raは、水素原子、アルキル基、アリール基、置換又は無置換のアミノ基、ハロゲン原子より選択される置換基を表す。 In General Formula (ii), X 1 represents a hydrogen atom, a halogen atom, —N (R 9 ) (R 10 ), —X 2 -L 1 or a group shown below. Here, R 9 and R 10 may be the same or different, and may have a substituent, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. Represents a hydrogen atom, and R 9 and R 10 may be bonded to each other to form a ring. Of these, a phenyl group is preferred. X 2 represents an oxygen atom or a sulfur atom, and L 1 represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom, or a hydrocarbon group having 1 to 12 carbon atoms including a hetero atom. . In addition, a hetero atom here shows N, S, O, a halogen atom, and Se. In the group shown below, Xa - has Za described later - is defined as for, R a represents a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group, substituted or unsubstituted amino group and a halogen atom .
R1及びR2は、それぞれ独立に、炭素原子数1〜12の炭化水素基を示す。画像記録層塗布液の保存安定性から、R1及びR2は、炭素原子数2個以上の炭化水素基であることが好ましく、またR1とR2は互いに連結し環を形成してもよく、環を形成する際は5員環又は6員環を形成していることが特に好ましい。 R 1 and R 2 each independently represent a hydrocarbon group having 1 to 12 carbon atoms. From the storage stability of the image recording layer coating solution, R 1 and R 2 are preferably hydrocarbon groups having 2 or more carbon atoms, and R 1 and R 2 may be connected to each other to form a ring. Well, when forming a ring, it is particularly preferable to form a 5-membered ring or a 6-membered ring.
Ar1、Ar2は、それぞれ同じでも異なっていてもよく、置換基を有していてもよいアリール基を示す。好ましいアリール基としては、ベンゼン環及びナフタレン環が挙げられる。また、好ましい置換基としては、炭素原子数12個以下の炭化水素基、ハロゲン原子、炭素原子数12個以下のアルコキシ基が挙げられる。Y1、Y2は、それぞれ同じでも異なっていてもよく、硫黄原子又は炭素原子数12個以下のジアルキルメチレン基を示す。R3、R4は、それぞれ同じでも異なっていてもよく、置換基を有していてもよい炭素原子数20個以下の炭化水素基を示す。好ましい置換基としては、炭素原子数12個以下のアルコキシ基、カルボキシ基、スルホ基が挙げられる。R5、R6、R7及びR8は、それぞれ同じでも異なっていてもよく、水素原子又は炭素原子数12個以下の炭化水素基を示す。原料の入手性から、好ましくは水素原子である。また、Za−は、対アニオンを示す。ただし、一般式(ii)で示されるシアニン色素が、その構造内にアニオン性の置換基を有し、電荷の中和が必要ない場合にはZa−は必要ない。好ましいZa−は、画像記録層塗布液の保存安定性から、ハロゲン化物イオン、過塩素酸イオン、テトラフルオロボレートイオン、ヘキサフルオロホスフェートイオン、及びスルホン酸イオンであり、特に好ましくは、過塩素酸イオン、ヘキサフルオロホスフェートイオン、及びアリールスルホン酸イオンである。 Ar 1 and Ar 2 may be the same or different and each represents an aryl group which may have a substituent. Preferred aryl groups include a benzene ring and a naphthalene ring. Moreover, as a preferable substituent, a C12 or less hydrocarbon group, a halogen atom, and a C12 or less alkoxy group are mentioned. Y 1 and Y 2 may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R 3 and R 4 may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include alkoxy groups having 12 or less carbon atoms, carboxy groups, and sulfo groups. R 5 , R 6 , R 7 and R 8 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the availability of raw materials, a hydrogen atom is preferred. Za − represents a counter anion. However, Za − is not necessary when the cyanine dye represented by the general formula (ii) has an anionic substituent in its structure and neutralization of charge is not necessary. Preferred Za − is a halide ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably a perchlorate ion, in view of the storage stability of the image recording layer coating solution. , Hexafluorophosphate ions, and aryl sulfonate ions.
本発明において、好適に用いることのできる一般式(ii)で示されるシアニン色素の具体例としては、特開2001−133969号公報の段落番号[0017]〜[0019]、特開2002−023360号公報の段落番号[0012]〜[0021]、特開2002−040638号公報の段落番号[0012]〜[0037]に記載された化合物、好ましくは特開2002−278057号公報段落番号[0034]〜[0041]、特開2008−195018号公報段落番号[0080]〜[0086]に記載の化合物、最も好ましくは特開2007−90850号公報段落番号[0035]〜[0043]に記載の化合物が挙げられる。
また特開平5−5005号公報[0008]〜[0009]、特開2001−222101号公報[0022]〜[0025]に記載の化合物も好ましく使用することが出来る。
Specific examples of the cyanine dye represented by formula (ii) that can be suitably used in the present invention include paragraph numbers [0017] to [0019] of JP-A No. 2001-133969 and JP-A No. 2002-023360. Paragraph numbers [0012] to [0021] of JP-A No. 2002-040638, compounds described in paragraph Nos. [0012] to [0037] of JP-A No. 2002-040638, preferably paragraph Nos. [0034] of JP-A No. 2002-278057 [0041], compounds described in JP-A-2008-195018, paragraph numbers [0080] to [0086], most preferably compounds described in JP-A-2007-90850, paragraph numbers [0035] to [0043]. It is done.
Further, compounds described in JP-A-5-5005 [0008] to [0009] and JP-A-2001-222101 [0022] to [0025] can also be preferably used.
また、これらの(B)赤外線吸収染料は、1種のみを用いてもよいし、2種以上を併用してもよく、顔料等の赤外線吸収染料以外の赤外線吸収剤を併用してもよい。顔料としては、特開2008−195018号公報[0072]〜[0076]に記載の化合物が好ましい。 Moreover, only 1 type may be used for these (B) infrared absorption dyes, 2 or more types may be used together, and infrared absorbers other than infrared absorption dyes, such as a pigment, may be used together. As the pigment, compounds described in JP 2008-195018 A [0072] to [0076] are preferable.
本発明における画像記録層中の赤外線吸収染料の含有量は、画像記録層の全固形分の0.1〜10.0質量%が好ましく、より好ましくは0.5〜5.0質量%である The content of the infrared absorbing dye in the image recording layer in the present invention is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 5.0% by mass of the total solid content of the image recording layer.
(C)ラジカル発生剤
本発明に用いられる(C)ラジカル発生剤としては、(A)ラジカル重合性化合物の重合を開始、促進する化合物を示す。本発明において使用しうるラジカル発生剤としては、ラジカル重合開始剤が好ましく、公知の熱重合開始剤、結合解離エネルギーの小さな結合を有する化合物、光重合開始剤などを使用することができる。
本発明におけるラジカル重合開始剤としては、例えば、(a)有機ハロゲン化物、(b)カルボニル化合物、(c)アゾ化合物、(d)有機過酸化物、(e)メタロセン化合物、(f)アジド化合物、(g)ヘキサアリールビイミダゾール化合物、(h)有機ホウ酸塩化合物、(i)ジスルホン化合物、(j)オキシムエステル化合物、(k)オニウム塩化合物、が挙げられる。
(C) Radical generator The (C) radical generator used in the present invention is a compound that initiates and accelerates the polymerization of the (A) radical polymerizable compound. The radical generator that can be used in the present invention is preferably a radical polymerization initiator, and a known thermal polymerization initiator, a compound having a bond with a small bond dissociation energy, a photopolymerization initiator, and the like can be used.
Examples of the radical polymerization initiator in the present invention include (a) an organic halide, (b) a carbonyl compound, (c) an azo compound, (d) an organic peroxide, (e) a metallocene compound, and (f) an azide compound. (G) hexaarylbiimidazole compound, (h) organic borate compound, (i) disulfone compound, (j) oxime ester compound, (k) onium salt compound.
(a)有機ハロゲン化物としては、特開2008−195018号公報の段落番号[0022]〜[0023]に記載の化合物が好ましい。 (A) As the organic halide, compounds described in paragraph numbers [0022] to [0023] of JP-A-2008-195018 are preferable.
(b)カルボニル化合物としては、特開2008−195018号公報の段落番号[0024]に記載の化合物が好ましい。 (B) As the carbonyl compound, compounds described in paragraph [0024] of JP-A-2008-195018 are preferable.
(c)アゾ化合物としては、例えば、特開平8−108621号公報に記載のアゾ化合物等を使用することができる。 (C) As the azo compound, for example, an azo compound described in JP-A-8-108621 can be used.
(d)有機過酸化物としては、例えば、特開2008−195018号公報の段落番号[0025]に記載の化合物が好ましい。 (D) As the organic peroxide, for example, compounds described in paragraph [0025] of JP-A-2008-195018 are preferable.
(e)メタロセン化合物としては、例えば、特開2008−195018号公報の段落番号[0026]に記載の化合物が好ましい。 As the (e) metallocene compound, for example, the compound described in paragraph [0026] of JP-A-2008-195018 is preferable.
(f)アジド化合物としては、2,6−ビス(4−アジドベンジリデン)−4−メチルシクロヘキサノン等の化合物を挙げることができる。
(g)ヘキサアリールビイミダゾール化合物としては、例えば、特開2008−195018号公報の段落番号[0027]に記載の化合物が好ましい。
(F) Examples of the azide compound include 2,6-bis (4-azidobenzylidene) -4-methylcyclohexanone.
(G) As the hexaarylbiimidazole compound, for example, a compound described in paragraph [0027] of JP-A-2008-195018 is preferable.
(h)有機ホウ酸塩化合物としては、例えば、特開2008−195018号公報の段落番号[0028]に記載の化合物が好ましい。 (H) As the organic borate compound, for example, a compound described in paragraph [0028] of JP-A-2008-195018 is preferable.
(i)ジスルホン化合物としては、特開昭61−166544号、特開2002−328465号の各公報に記載の化合物が挙げられる。 (I) Examples of the disulfone compound include compounds described in JP-A Nos. 61-166544 and 2002-328465.
(j)オキシムエステル化合物としては、例えば、特開2008−195018号公報の段落番号[0028]〜[0030]に記載の化合物が好ましい。 (J) As the oxime ester compound, for example, compounds described in paragraph numbers [0028] to [0030] of JP-A-2008-195018 are preferable.
(k)オニウム塩化合物としては、例えば、S.I.Schlesinger,Photogr.Sci.Eng.,18,387(1974)、T.S.Bal et al,Polymer,21,423(1980)、特開平5-158230(NI3のジアゾニウムに対応)に記載のジアゾニウム塩、米国特許第4,069,055号明細書、特開平4−365049号公報等に記載のアンモニウム塩、米国特許第4,069,055号、同4,069,056号の各明細書に記載のホスホニウム塩、欧州特許第104、143号、米国特許出願公開第2008/0311520号の各明細書、特開平2−150848号、特開2008−195018号の各公報、又はJ.V.Crivello et al,Macromolecules,10(6),1307(1977)に記載のヨードニウム塩、欧州特許第370,693号、、同233,567号、同297,443号、同297,442号、米国特許第4,933,377号、同4,760,013号、同4,734,444号、同2,833,827号、独国特許第2,904,626号、同3,604,580号、同3,604,581号の各明細書に記載のスルホニウム塩、J.V.Crivello et al,J.Polymer Sci.,Polymer Chem.Ed.,17,1047(1979)に記載のセレノニウム塩、C.S.Wen et al,Teh,Proc.Conf.Rad.Curing ASIA,p478 Tokyo,Oct(1988)に記載のアルソニウム塩、特開2008−195018号公報に記載のアジニウム塩等のオニウム塩等が挙げられる。 (K) Examples of the onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in JP-A-5-158230 (corresponding to NI3 diazonium), US Pat. No. 4,069,055, JP-A-4-365049 Ammonium salts described in U.S. Pat. Nos. 4,069,055 and 4,069,056, EP 104,143, U.S. Patent Application Publication No. 2008/0311520 Nos. 1-150848, JP-A-2-150848, JP-A-2008-195018, or J. Pat. V. Ivonium salt described in Crivello et al, Macromolecules, 10 (6), 1307 (1977), European Patents 370,693, 233,567, 297,443, 297,442, US Patent 4,933,377, 4,760,013, 4,734,444, 2,833,827, German Patent 2,904,626, 3,604,580 Sulphonium salts described in the respective specifications of U.S. Pat. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as azinium salts described in JP-A-2008-195018.
上記の中でもより好ましいものとして、オニウム塩、なかでもヨードニウム塩、スルホニウム塩及びアジニウム塩が挙げられる。以下に、これらの化合物の具体例を示すが、これに限定されない。 Of these, more preferred are onium salts, especially iodonium salts, sulfonium salts and azinium salts. Although the specific example of these compounds is shown below, it is not limited to this.
ヨードニウム塩の例としては、ジフェニルヨードニウム塩が好ましく、特に電子供与性基、例えばアルキル基又はアルコキシル基で置換されたジフェニルヨードニウム塩が好ましく、更に好ましくは非対称のジフェニルヨードニウム塩が好ましい。具体例としては、ジフェニルヨードニウム=ヘキサフルオロホスファート、4−メトキシフェニル−4−(2−メチルプロピル)フェニルヨードニウム=ヘキサフルオロホスファート、4−(2−メチルプロピル)フェニル−p−トリルヨードニウム=ヘキサフルオロホスファート、4−ヘキシルオキシフェニル−2,4,6−トリメトキシフェニルヨードニウム=ヘキサフルオロホスファート、4−ヘキシルオキシフェニル−2,4−ジエトキシフェニルヨードニウム=テトラフルオロボラート、4−オクチルオキシフェニル−2,4,6−トリメトキシフェニルヨードニウム=1−ペルフルオロブタンスルホナート、4−オクチルオキシフェニル−2,4,6−トリメトキシフェニルヨードニウム=ヘキサフルオロホスファート、ビス(4−t−ブチルフェニル)ヨードニウム=テトラフェニルボラートが挙げられる。 As an example of the iodonium salt, a diphenyl iodonium salt is preferable, and a diphenyl iodonium salt substituted with an electron donating group such as an alkyl group or an alkoxyl group is particularly preferable, and an asymmetric diphenyl iodonium salt is more preferable. Specific examples include diphenyliodonium = hexafluorophosphate, 4-methoxyphenyl-4- (2-methylpropyl) phenyliodonium = hexafluorophosphate, 4- (2-methylpropyl) phenyl-p-tolyliodonium = hexa. Fluorophosphate, 4-hexyloxyphenyl-2,4,6-trimethoxyphenyliodonium = hexafluorophosphate, 4-hexyloxyphenyl-2,4-diethoxyphenyliodonium = tetrafluoroborate, 4-octyloxy Phenyl-2,4,6-trimethoxyphenyliodonium = 1-perfluorobutanesulfonate, 4-octyloxyphenyl-2,4,6-trimethoxyphenyliodonium = hexafluorophosphate, bis ( -t- butylphenyl) iodonium tetraphenylborate and the like.
スルホニウム塩の例としては、トリフェニルスルホニウム=ヘキサフルオロホスファート、トリフェニルスルホニウム=ベンゾイルホルマート、ビス(4−クロロフェニル)フェニルスルホニウム=ベンゾイルホルマート、ビス(4−クロロフェニル)−4−メチルフェニルスルホニウム=テトラフルオロボラート、トリス(4−クロロフェニル)スルホニウム=3,5−ビス(メトキシカルボニル)ベンゼンスルホナート、トリス(4−クロロフェニル)スルホニウム=ヘキサフルオロホスファートが挙げられる。 Examples of sulfonium salts include triphenylsulfonium = hexafluorophosphate, triphenylsulfonium = benzoylformate, bis (4-chlorophenyl) phenylsulfonium = benzoylformate, bis (4-chlorophenyl) -4-methylphenylsulfonium = Examples thereof include tetrafluoroborate, tris (4-chlorophenyl) sulfonium = 3,5-bis (methoxycarbonyl) benzenesulfonate, and tris (4-chlorophenyl) sulfonium = hexafluorophosphate.
アジニウム塩の例としては、1−シクロヘキシルメチルオキシピリジニウム=ヘキサフルオロホスファート、1−シクロヘキシルオキシ−4−フェニルピリジニウム=ヘキサフルオロホスファート、1−エトキシ−4−フェニルピリジニウム=ヘキサフルオロホスファート、1−(2−エチルヘキシルオキシ)−4−フェニルピリジニウム=ヘキサフルオロホスファート、4−クロロ−1−シクロヘキシルメチルオキシピリジニウム=ヘキサフルオロホスファート、1−エトキシ−4−シアノピリジニウム=ヘキサフルオロホスファート、3,4−ジクロロ−1−(2−エチルヘキシルオキシ)ピリジニウム=ヘキサフルオロホスファート、1−ベンジルオキシ−4−フェニルピリジニウム=ヘキサフルオロホスファート、1−フェネチルオキシ−4−フェニルピリジニウム=ヘキサフルオロホスファート、1−(2−エチルヘキシルオキシ)−4−フェニルピリジニウム=p−トルエンスルホナート、1−(2−エチルヘキシルオキシ)−4−フェニルピリジニウム=ペルフルオロブタンスルホナート、1−(2−エチルヘキシルオキシ)−4−フェニルピリジニウム=ブロミド、1−(2−エチルヘキシルオキシ)−4−フェニルピリジニウム=テトラフルオロボラートが挙げられる。 Examples of azinium salts include 1-cyclohexylmethyloxypyridinium = hexafluorophosphate, 1-cyclohexyloxy-4-phenylpyridinium = hexafluorophosphate, 1-ethoxy-4-phenylpyridinium = hexafluorophosphate, 1-cyclohexyl (2-ethylhexyloxy) -4-phenylpyridinium = hexafluorophosphate, 4-chloro-1-cyclohexylmethyloxypyridinium = hexafluorophosphate, 1-ethoxy-4-cyanopyridinium = hexafluorophosphate, 3,4 -Dichloro-1- (2-ethylhexyloxy) pyridinium = hexafluorophosphate, 1-benzyloxy-4-phenylpyridinium = hexafluorophosphate, 1-phenethylo Ci-4-phenylpyridinium = hexafluorophosphate, 1- (2-ethylhexyloxy) -4-phenylpyridinium = p-toluenesulfonate, 1- (2-ethylhexyloxy) -4-phenylpyridinium = perfluorobutanesulfonate 1- (2-ethylhexyloxy) -4-phenylpyridinium bromide, 1- (2-ethylhexyloxy) -4-phenylpyridinium tetrafluoroborate.
ラジカル発生剤は、画像記録層を構成する全固形分に対し、好ましくは0.1〜50質量%、より好ましくは0.5〜30質量%、特に好ましくは0.8〜20質量%の割合で添加することができる。この範囲でより良好な感度と印刷時の非画像部の良好な汚れ難さが得られる。 The radical generator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 0.8 to 20% by mass with respect to the total solid content constituting the image recording layer. Can be added. Within this range, better sensitivity and good stain resistance of the non-image area during printing can be obtained.
(E)コアシェル型以外の樹脂微粒子
本発明では、機上現像性と耐刷性の向上のために、コアシェル微粒子以外の樹脂微粒子を用いることができる。微粒子としては、疎水性熱可塑性樹脂微粒子、熱反応性樹脂微粒子、重合性基を有する樹脂微粒子、疎水性化合物を内包しているマイクロカプセル、及びミクロゲル(架橋樹脂微粒子)から選ばれる少なくともひとつであることが好ましい。なかでも、重合性基を有する樹脂微粒子及びミクロゲルが好ましい。
(E) Resin fine particles other than core-shell type In the present invention, resin fine particles other than core-shell fine particles can be used in order to improve on-press developability and printing durability. The fine particles are at least one selected from hydrophobic thermoplastic resin fine particles, thermally reactive resin fine particles, resin fine particles having a polymerizable group, microcapsules enclosing a hydrophobic compound, and microgel (crosslinked resin fine particles). It is preferable. Of these, resin fine particles and microgels having a polymerizable group are preferred.
疎水性熱可塑性樹脂微粒子としては、1992年1月のResearch Disclosure No.333003、特開平9−123387号公報、同9−131850号公報、同9−171249号公報、同9−171250号公報及び欧州特許第931647号明細書などに記載の疎水性熱可塑性樹脂微粒子を好適なものとして挙げることができる。
このような樹脂微粒子を構成するポリマーの具体例としては、エチレン、スチレン、塩化ビニル、アクリル酸メチル、アクリル酸エチル、メタクリル酸メチル、メタクリル酸エチル、塩化ビニリデン、アクリロニトリル、ビニルカルバゾール、ポリアルキレン構造を有するアクリレート又はメタクリレートなどのモノマーのホモポリマー若しくはコポリマー又はそれらの混合物を挙げることができる。その中で、より好適なものとして、ポリスチレン、スチレン及びアクリロニトリルを含む共重合体、ポリメタクリル酸メチルを挙げることができる。
Hydrophobic thermoplastic resin fine particles include Research Disclosure No. 1 of January 1992. 331,003, JP-A-9-123387, JP-A-9-131850, JP-A-9-171249, JP-A-9-171250 and European Patent No. 931647 are suitable. Can be cited as
Specific examples of polymers constituting such resin fine particles include ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinyl carbazole, and polyalkylene structures. Mention may be made of homopolymers or copolymers of monomers such as acrylates or methacrylates or mixtures thereof. Among them, more preferable examples include a copolymer containing polystyrene, styrene and acrylonitrile, and polymethyl methacrylate.
本発明に用いられる疎水性熱可塑性樹脂微粒子の平均粒径は0.01〜2.0μmが好ましい。 The average particle diameter of the hydrophobic thermoplastic resin fine particles used in the present invention is preferably 0.01 to 2.0 μm.
本発明に用いられる熱反応性樹脂微粒子としては、熱反応性基を有する樹脂微粒子が挙げられ、これらは、熱反応による架橋、及びその際の官能基変化により疎水化領域を形成する。 Examples of the heat-reactive resin fine particles used in the present invention include resin fine particles having a heat-reactive group, and these form a hydrophobized region by cross-linking by a heat reaction and a functional group change at that time.
本発明に用いる熱反応性基を有する樹脂微粒子における熱反応性基としては、化学結合が形成されるならば、どのような反応を行う官能基でもよいが、重合性基であることが好ましく、その例として、ラジカル重合反応を行うエチレン性不飽和基(例えば、アクリロイル基、メタクリロイル基、ビニル基、アリル基など)、カチオン重合性基(例えば、ビニル基、ビニルオキシ基、エポキシ基、オキセタニル基など)、付加反応を行うイソシアナト基又はそのブロック体、エポキシ基、ビニルオキシ基及びこれらの反応相手である活性水素原子を有する官能基(例えば、アミノ基、ヒドロキシ基、カルボキシ基など)、縮合反応を行うカルボキシ基及び反応相手であるヒドロキシ基又はアミノ基、開環付加反応を行う酸無水物及び反応相手であるアミノ基又はヒドロキシ基などを好適なものとして挙げることができる。 The thermally reactive group in the resin fine particles having a thermally reactive group used in the present invention may be any functional group that performs any reaction as long as a chemical bond is formed, but is preferably a polymerizable group, Examples include ethylenically unsaturated groups that undergo radical polymerization reactions (eg, acryloyl groups, methacryloyl groups, vinyl groups, allyl groups, etc.), cationic polymerizable groups (eg, vinyl groups, vinyloxy groups, epoxy groups, oxetanyl groups, etc.) ), An isocyanato group that performs an addition reaction or a block thereof, an epoxy group, a vinyloxy group, and a functional group having an active hydrogen atom that is a reaction partner thereof (for example, an amino group, a hydroxy group, a carboxy group, etc.), and a condensation reaction A carboxyl group and a reaction partner, a hydroxy group or an amino group, an acid anhydride that performs a ring-opening addition reaction, and a reaction partner An amino group or hydroxy group may be mentioned as preferred that.
本発明で用いられるマイクロカプセルとしては、例えば、特開2001−277740号公報、特開2001−277742号公報に記載のごとく、画像記録層の構成成分の全て又は一部をマイクロカプセルに内包させたものである。なお、画像記録層の構成成分は、マイクロカプセル外にも含有させることもできる。更に、マイクロカプセルを含有する画像記録層は、疎水性の構成成分をマイクロカプセルに内包し、親水性の構成成分をマイクロカプセル外に含有することが好ましい態様である。 As the microcapsules used in the present invention, for example, as described in JP-A Nos. 2001-277740 and 2001-277742, all or part of the constituent components of the image recording layer are encapsulated in the microcapsules. Is. The constituent components of the image recording layer can also be contained outside the microcapsules. Furthermore, it is preferable that the image recording layer containing the microcapsule includes a hydrophobic constituent component in the microcapsule and a hydrophilic constituent component outside the microcapsule.
本発明においては、架橋樹脂粒子、すなわちミクロゲルを含有する態様であってもよい。このミクロゲルは、その中又は表面の少なくとも一方に、画像記録層の構成成分の一部を含有することができ、特に、ラジカル重合性基をその表面に有することによって反応性ミクロゲルとした態様が、画像形成感度や耐刷性の観点から特に好ましい。 In this invention, the aspect containing a crosslinked resin particle, ie, a microgel, may be sufficient. This microgel can contain a part of the constituent components of the image recording layer in at least one of the inside and the surface thereof, and in particular, an embodiment in which a reactive microgel is formed by having a radical polymerizable group on the surface thereof, This is particularly preferable from the viewpoint of image formation sensitivity and printing durability.
画像記録層の構成成分をマイクロカプセル化、若しくはミクロゲル化する方法としては、公知の方法が適用できる。 As a method for microencapsulating or microgelling the constituent components of the image recording layer, known methods can be applied.
上記のマイクロカプセルやミクロゲルの平均粒径は、0.01〜3.0μmが好ましい。0.05〜2.0μmが更に好ましく、0.10〜1.0μmが特に好ましい。この範囲内で良好な解像度と経時安定性が得られる。 The average particle size of the microcapsules or microgel is preferably 0.01 to 3.0 μm. 0.05-2.0 micrometers is still more preferable, and 0.10-1.0 micrometer is especially preferable. Within this range, good resolution and stability over time can be obtained.
コアシェル型以外の樹脂微粒子の含有量としては、画像記録層全固形分の5〜90質量%の範囲であることが好ましい。 The content of resin fine particles other than the core-shell type is preferably in the range of 5 to 90% by mass based on the total solid content of the image recording layer.
(F)その他の成分
本発明における画像記録層には、必要に応じて、更に他の成分を含有することができる。
(F) Other components The image recording layer in the invention may further contain other components as required.
(1)バインダーポリマー
本発明の画像記録層には、画像記録層の膜強度を向上させるため、バインダーポリマーを用いることができる。本発明に用いることができるバインダーポリマーは、従来公知のものを制限なく使用でき、皮膜性を有するポリマーが好ましい。なかでも、アクリル樹脂、ポリビニルアセタール樹脂、ポリウレタン樹脂が好ましい。
(1) Binder polymer In the image recording layer of the present invention, a binder polymer can be used in order to improve the film strength of the image recording layer. As the binder polymer that can be used in the present invention, conventionally known binder polymers can be used without limitation, and polymers having film properties are preferred. Of these, acrylic resins, polyvinyl acetal resins, and polyurethane resins are preferable.
なかでも本発明に好適なバインダーポリマーとしては、特開2008−195018号公報に記載のような、画像部の皮膜強度を向上するための架橋性官能基を主鎖又は側鎖、好ましくは側鎖に有しているものが挙げられる。架橋性基によってポリマー分子間に架橋が形成され、硬化が促進する。 Among them, as a binder polymer suitable for the present invention, as described in JP-A-2008-195018, a crosslinkable functional group for improving the film strength of the image portion is a main chain or a side chain, preferably a side chain. Have the following. Crosslinking is formed between the polymer molecules by the crosslinkable group, and curing is accelerated.
架橋性官能基としては、(メタ)アクリル基、ビニル基、アリル基、スチリル基などのエチレン性不飽和基やエポキシ基等が好ましく、これらの基は高分子反応や共重合によってポリマーに導入することができる。例えば、カルボキシ基を側鎖に有するアクリルポリマーやポリウレタンとグリシジルメタクリレートとの反応、あるいはエポキシ基を有するポリマーとメタクリル酸などのエチレン性不飽和基含有カルボン酸との反応を利用できる。 The crosslinkable functional group is preferably an ethylenically unsaturated group such as a (meth) acryl group, vinyl group, allyl group, or styryl group, or an epoxy group, and these groups are introduced into the polymer by polymer reaction or copolymerization. be able to. For example, a reaction between an acrylic polymer or polyurethane having a carboxy group in the side chain and polyurethane and glycidyl methacrylate, or a reaction between a polymer having an epoxy group and an ethylenically unsaturated group-containing carboxylic acid such as methacrylic acid can be used.
バインダーポリマー中の架橋性基の含有量は、バインダーポリマー1g当たり、好ましくは0.1〜10.0mmol、より好ましくは0.25〜7.0mmol、最も好ましくは0.5〜5.5mmolである。 The content of the crosslinkable group in the binder polymer is preferably 0.1 to 10.0 mmol, more preferably 0.25 to 7.0 mmol, and most preferably 0.5 to 5.5 mmol per 1 g of the binder polymer. .
また、本発明のバインダーポリマーは、更に親水性基を有することが好ましい。親水性基は画像記録層に機上現像性を付与するのに寄与する。特に、架橋性基と親水性基を共存させることにより、耐刷性と現像性の両立が可能になる。 Moreover, it is preferable that the binder polymer of this invention has a hydrophilic group further. The hydrophilic group contributes to imparting on-press developability to the image recording layer. In particular, the coexistence of the crosslinkable group and the hydrophilic group makes it possible to achieve both printing durability and developability.
親水性基としては、たとえば、ヒドロキシ基、カルボキシ基、アルキレンオキシド構造、アミノ基、アンモニウム基、アミド基、スルホ基、リン酸基等などがあり、なかでも、炭素原子数2又は3のアルキレンオキシド単位を1〜9個有するアルキレンオキシド構造が好ましい。バインダーポリマーに親水性基を付与するには親水性基を有するモノマーを共重合すればよい。 Examples of the hydrophilic group include a hydroxy group, a carboxy group, an alkylene oxide structure, an amino group, an ammonium group, an amide group, a sulfo group, and a phosphoric acid group. Among these, an alkylene oxide having 2 or 3 carbon atoms is preferable. An alkylene oxide structure having 1 to 9 units is preferred. In order to impart a hydrophilic group to the binder polymer, a monomer having a hydrophilic group may be copolymerized.
また、本発明のバインダーポリマーには、着肉性を制御するため、アルキル基、アリール基、アラルキル基、アルケニル基などの親油性の基を導入できる。具体的には、メタクリル酸アルキルエステルなどの親油性基含有モノマーを共重合すればよい。 In addition, in the binder polymer of the present invention, an oleophilic group such as an alkyl group, an aryl group, an aralkyl group, or an alkenyl group can be introduced in order to control the inking property. Specifically, a lipophilic group-containing monomer such as an alkyl methacrylate may be copolymerized.
以下に本発明に用いられるバインダーポリマーの具体例(1)〜(11)を示すが、本発明はこれらに限定されるものではない。
なお、下記例示化合物中、各繰り返し単位に併記される数値(主鎖繰り返し単位に併記される数値)は、当該繰り返し単位のモル百分率を表す。側鎖の繰り返し単位に併記される数値は、当該繰り返し部位の繰り返し数を示す。
Specific examples (1) to (11) of the binder polymer used in the present invention are shown below, but the present invention is not limited thereto.
In addition, in the following exemplary compounds, a numerical value written together with each repeating unit (a numerical value written together with the main chain repeating unit) represents a mole percentage of the repeating unit. The numerical value written together with the repeating unit of the side chain indicates the number of repetitions of the repeating site.
なお、本発明におけるバインダーポリマーは質量平均モル質量(Mw)が2000以上であることが好ましく、5000以上であるのがより好ましく、1万〜30万であるのが更に好ましい。 The binder polymer in the present invention preferably has a mass average molar mass (Mw) of 2000 or more, more preferably 5000 or more, and still more preferably 10,000 to 300,000.
本発明では必要に応じて、特開2008−195018号公報に記載のポリアクリル酸、ポリビニルアルコールなどの親水性ポリマーを用いることができる。また、親油的なバインダーポリマーと親水的なバインダーポリマーを併用することもできる。 In the present invention, if necessary, hydrophilic polymers such as polyacrylic acid and polyvinyl alcohol described in JP-A-2008-195018 can be used. Further, a lipophilic binder polymer and a hydrophilic binder polymer can be used in combination.
バインダーポリマーの含有量は、画像記録層の全固形分に対して、5〜90質量%であるのが好ましく、5〜80質量%であるのがより好ましく、10〜70質量%であるのが更に好ましい。 The content of the binder polymer is preferably 5 to 90% by mass, more preferably 5 to 80% by mass, and more preferably 10 to 70% by mass with respect to the total solid content of the image recording layer. Further preferred.
(2)低分子親水性化合物
本発明における画像記録層は、耐刷性を低下させることなく機上現像性を向上させるために、低分子親水性化合物を含有してもよい。
低分子親水性化合物としては、例えば、水溶性有機化合物としては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール等のグリコール類及びそのエーテル又はエステル誘導体類、グリセリン、ペンタエリスリトール、トリス(2−ヒドロキシエチル)イソシアヌレート等のポリオール類、トリエタノールアミン、ジエタノールアミン、モノエタノールアミン等の有機アミン類及びその塩、アルキルスルホン酸、トルエンスルホン酸、ベンゼンスルホン酸等の有機スルホン酸類及びその塩、アルキルスルファミン酸等の有機スルファミン酸類及びその塩、アルキル硫酸、アルキルエーテル硫酸等の有機硫酸類及びその塩、フェニルホスホン酸等の有機ホスホン酸類及びその塩、酒石酸、シュウ酸、クエン酸、リンゴ酸、乳酸、グルコン酸、アミノ酸類等の有機カルボン酸類及びその塩、ベタイン類、等が挙げられる。
(2) Low molecular weight hydrophilic compound The image recording layer in the invention may contain a low molecular weight hydrophilic compound in order to improve the on-press developability without reducing the printing durability.
As the low molecular weight hydrophilic compound, for example, as the water-soluble organic compound, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and the like glycols and ether or ester derivatives thereof, glycerin, Polyols such as pentaerythritol and tris (2-hydroxyethyl) isocyanurate, organic amines such as triethanolamine, diethanolamine and monoethanolamine and salts thereof, organic sulfones such as alkylsulfonic acid, toluenesulfonic acid and benzenesulfonic acid Acids and salts thereof, organic sulfamic acids such as alkylsulfamic acid and salts thereof, organic sulfuric acids such as alkylsulfuric acid and alkylethersulfuric acid and salts thereof, phenylphosphonic acid Organic phosphonic acids and salts thereof, tartaric acid, oxalic acid, citric acid, malic acid, lactic acid, gluconic acid, organic carboxylic acids and salts thereof such as amino acids, betaines, and the like.
本発明においてはこれらの中でも、ポリオール類、有機硫酸塩類、有機スルホン酸塩類、ベタイン類の群から選ばれる少なくとも一つを含有させることが好ましい。 Among these, in the present invention, it is preferable to contain at least one selected from the group consisting of polyols, organic sulfates, organic sulfonates, and betaines.
有機スルホン酸塩の具体的な化合物としては、n−ブチルスルホン酸ナトリウム、n−ヘキシルスルホン酸ナトリウム、2−エチルヘキシルスルホン酸ナトリウム、シクロヘキシルスルホン酸ナトリウム、n−オクチルスルホン酸ナトリウムなどのアルキルスルホン酸塩;5,8,11−トリオキサペンタデカン−1−スルホン酸ナトリウム、5,8,11−トリオキサヘプタデカン−1−スルホン酸ナトリウム、13−エチル−5,8,11−トリオキサヘプタデカン−1−スルホン酸ナトリウム、5,8,11,14−テトラオキサテトラコサン−1−スルホン酸ナトリウムなどのエチレンオキシド鎖を含むアルキルスルホン酸塩;ベンゼンスルホン酸ナトリウム、p−トルエンスルホン酸ナトリウム、p−ヒドロキシベンゼンスルホン酸ナトリウム、p−スチレンスルホン酸ナトリウム、イソフタル酸ジメチル−5−スルホン酸ナトリウム、1−ナフチルスルホン酸ナトリウム、4−ヒドロキシナフチルスルホン酸ナトリウム、1,5−ナフタレンジスルホン酸ジナトリウム、1,3,6−ナフタレントリスルホン酸トリナトリウムなどのアリールスルホン酸塩、特開2007−276454号公報段落番号[0026]〜[0031]、特開2009−154525号公報段落番号[0020]〜[0047]に記載の化合物などが挙げられる。塩は、カリウム塩、リチウム塩でもよい。 Specific examples of organic sulfonates include alkyl sulfonates such as sodium n-butyl sulfonate, sodium n-hexyl sulfonate, sodium 2-ethylhexyl sulfonate, sodium cyclohexyl sulfonate, and sodium n-octyl sulfonate. Sodium 5,8,11-trioxapentadecane-1-sulfonate, sodium 5,8,11-trioxaheptadecane-1-sulfonate, 13-ethyl-5,8,11-trioxaheptadecane-1; Alkyl sulfonates containing ethylene oxide chains such as sodium sulfonate, sodium 5,8,11,14-tetraoxatetracosane-1-sulfonate; sodium benzenesulfonate, sodium p-toluenesulfonate, p-hydroxybenzene Sulfone Sodium, sodium p-styrenesulfonate, sodium dimethyl-5-sulfonate isophthalate, sodium 1-naphthylsulfonate, sodium 4-hydroxynaphthylsulfonate, disodium 1,5-naphthalenedisulfonate, 1,3,6- Aryl sulfonates such as trisodium naphthalene trisulfonate, compounds described in paragraph numbers [0026] to [0031] of JP 2007-276454 A and paragraph numbers [0020] to [0047] of JP 2009-154525 A Etc. The salt may be a potassium salt or a lithium salt.
有機硫酸塩としては、ポリエチレンオキシドのアルキル、アルケニル、アルキニル、アリール又は複素環モノエーテルの硫酸塩が挙げられる。エチレンオキシド単位は1〜4であるのが好ましく、塩は、ナトリウム塩、カリウム塩又はリチウム塩が好ましい。これらの具体例としては、特開2007−276454号公報段落番号[0034]〜[0038]に記載の化合物が挙げられる。 Organic sulfates include sulfates of alkyl, alkenyl, alkynyl, aryl or heterocyclic monoethers of polyethylene oxide. The number of ethylene oxide units is preferably 1 to 4, and the salt is preferably a sodium salt, potassium salt or lithium salt. Specific examples thereof include the compounds described in paragraph numbers [0034] to [0038] of JP-A-2007-276454.
ベタイン類としては、窒素原子への炭化水素置換基の炭素原子数が1〜5である化合物が好ましく、具体例としては、トリメチルアンモニウムアセタート、ジメチルプロピルアンモニウムアセタート、3−ヒドロキシ−4−トリメチルアンモニオブチラート、4−(1−ピリジニオ)ブチラート、1−ヒドロキシエチル−1−イミダゾリオアセタート、トリメチルアンモニウムメタンスルホナート、ジメチルプロピルアンモニウムメタンスルホナート、3−トリメチルアンモニオ−1−プロパンスルホナート、3−(1−ピリジニオ)−1−プロパンスルホナートなどが挙げられる。 As the betaines, compounds having 1 to 5 carbon atoms of the hydrocarbon substituent on the nitrogen atom are preferable. Specific examples include trimethylammonium acetate, dimethylpropylammonium acetate, 3-hydroxy-4-trimethyl. Ammonioobylate, 4- (1-pyridinio) butyrate, 1-hydroxyethyl-1-imidazolioacetate, trimethylammonium methanesulfonate, dimethylpropylammonium methanesulfonate, 3-trimethylammonio-1-propanesulfonate, Examples include 3- (1-pyridinio) -1-propanesulfonate.
上記の低分子親水性化合物は、疎水性部分の構造が小さくて界面活性作用がほとんどないため、湿し水が画像記録層露光部(画像部)へ浸透して画像部の疎水性や皮膜強度を低下させることがなく、画像記録層のインキ受容性や耐刷性を良好に維持できる。 The above low molecular weight hydrophilic compound has a small hydrophobic part structure and almost no surface-active action, so that dampening water penetrates into the exposed part of the image recording layer (image part) and the hydrophobicity and film strength of the image part. Ink acceptability and printing durability of the image recording layer can be maintained satisfactorily.
これら低分子親水性化合物の画像記録層への添加量は、画像記録層全固形分量の0.5質量%以上20質量%以下であることが好ましい。より好ましくは1質量%以上15質量%以下であり、更に好ましくは2質量%以上10質量%以下である。この範囲で良好な機上現像性と耐刷性が得られる。
これらの化合物は単独で用いてもよく、2種以上を混合して用いてもよい。
The amount of these low molecular weight hydrophilic compounds added to the image recording layer is preferably 0.5% by mass or more and 20% by mass or less of the total solid content of the image recording layer. More preferably, they are 1 mass% or more and 15 mass% or less, More preferably, they are 2 mass% or more and 10 mass% or less. In this range, good on-press developability and printing durability can be obtained.
These compounds may be used alone or in combination of two or more.
(3)感脂化剤
本発明の画像記録層には、着肉性を向上させるために、画像記録層にホスホニウム化合物、含窒素低分子化合物、アンモニウム基含有ポリマーなどの感脂化剤を用いることができる。特に、保護層に無機質の層状化合物を含有させる場合、これらの化合物は、無機質の層状化合物の表面被覆剤として機能し、無機質の層状化合物による印刷途中の着肉性低下を防止する。
(3) Grease Sensitizer In the image recording layer of the present invention, a lipid sensitizer such as a phosphonium compound, a nitrogen-containing low molecular weight compound, or an ammonium group-containing polymer is used in the image recording layer in order to improve the inking property. be able to. In particular, when an inorganic layered compound is contained in the protective layer, these compounds function as a surface coating agent for the inorganic layered compound, and prevent a decrease in the inking property during printing by the inorganic layered compound.
好適なホスホニウム化合物としては、特開2006−297907号公報及び特開2007−50660号公報に記載のホスホニウム化合物を挙げることができる。具体例としては、テトラブチルホスホニウムヨージド、ブチルトリフェニルホスホニウムブロミド、テトラフェニルホスホニウムブロミド、1,4−ビス(トリフェニルホスホニオ)ブタン=ジ(ヘキサフルオロホスファート)、1,7−ビス(トリフェニルホスホニオ)ヘプタン=スルファート、1,9−ビス(トリフェニルホスホニオ)ノナン=ナフタレン−2,7−ジスルホナートなどが挙げられる。 Suitable phosphonium compounds include phosphonium compounds described in JP-A-2006-297907 and JP-A-2007-50660. Specific examples include tetrabutylphosphonium iodide, butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, 1,4-bis (triphenylphosphonio) butanedi (hexafluorophosphate), 1,7-bis (tri Phenylphosphonio) heptane sulfate, 1,9-bis (triphenylphosphonio) nonane = naphthalene-2,7-disulfonate, and the like.
上記含窒素低分子化合物としては、アミン塩類、第4級アンモニウム塩類が挙げられる。またイミダゾリニウム塩類、ベンゾイミダゾリニウム塩類、ピリジニウム塩類、キノリニウム塩類も挙げられる。なかでも、第4級アンモニウム塩類、及びピリジニウム塩類が好ましい。具体例としては、テトラメチルアンモニウム=ヘキサフルオロホスファート、テトラブチルアンモニウム=ヘキサフルオロホスファート、ドデシルトリメチルアンモニウム=p−トルエンスルホナート、ベンジルトリエチルアンモニウム=ヘキサフルオロホスファート、ベンジルジメチルオクチルアンモニウム=ヘキサフルオロホスファート、ベンジルジメチルドデシルアンモニウム=ヘキサフルオロホスファート、特開2008−284858号公報段落番号[0021]〜[0037]、特開2009−90645号公報段落番号[0030]〜[0057]に記載の化合物などが挙げられる。 Examples of the nitrogen-containing low molecular weight compound include amine salts and quaternary ammonium salts. Also included are imidazolinium salts, benzoimidazolinium salts, pyridinium salts, and quinolinium salts. Of these, quaternary ammonium salts and pyridinium salts are preferable. Specific examples include tetramethylammonium = hexafluorophosphate, tetrabutylammonium = hexafluorophosphate, dodecyltrimethylammonium = p-toluenesulfonate, benzyltriethylammonium = hexafluorophosphate, benzyldimethyloctylammonium = hexafluorophosphate. Fert, benzyldimethyldodecyl ammonium = hexafluorophosphate, compounds described in paragraph numbers [0021] to [0037] of JP-A-2008-284858, paragraph numbers [0030] to [0057] of JP-A-2009-90645, etc. Is mentioned.
上記アンモニウム基含有ポリマーとしては、その構造中にアンモニウム基を有すれば如何なるものでもよいが、側鎖にアンモニウム基を有する(メタ)アクリレートを共重合成分として5〜80モル%含有するポリマーが好ましい。具体例としては、特開2009−208458号公報段落番号[0089]〜[0105]に記載のポリマーが挙げられる。 The ammonium group-containing polymer may be any polymer as long as it has an ammonium group in its structure, but a polymer containing 5 to 80 mol% of a (meth) acrylate having an ammonium group in the side chain as a copolymerization component is preferable. . Specific examples include polymers described in paragraph numbers [0089] to [0105] of JP2009-208458A.
上記アンモニウム塩含有ポリマーは、下記の測定方法で求められる還元比粘度(単位:ml/g)の値で、5〜120の範囲のものが好ましく、10〜110の範囲のものがより好ましく、15〜100の範囲のものが特に好ましい。上記還元比粘度を質量平均モル質量(Mw)に換算すると、10000〜150000が好ましく、17000〜140000がより好ましく、20000〜130000が特に好ましい。 The ammonium salt-containing polymer has a reduced specific viscosity (unit: ml / g) determined by the following measurement method, preferably in the range of 5 to 120, more preferably in the range of 10 to 110, 15 Those in the range of ~ 100 are particularly preferred. When the said reduced specific viscosity is converted into a mass mean molar mass (Mw), 10,000-150,000 are preferable, 17000-140000 are more preferable, 20000-130000 are especially preferable.
<還元比粘度の測定方法>
30質量%ポリマー溶液3.33g(固形分として1g)を、20mlのメスフラスコに秤量し、N−メチルピロリドンでメスアップする。この溶液を30℃の恒温槽で30分間静置し、ウベローデ還元比粘度管(粘度計定数=0.010cSt/s)に入れて30℃にて流れ落ちる時間を測定する。なお測定は同一サンプルで2回測定し、その平均値を算出する。同様にブランク(N−メチルピロリドンのみ)の場合も測定し、下記式から還元比粘度(ml/g)を算出した。
<Measurement method of reduced specific viscosity>
Weigh 3.33 g of 30% polymer solution (1 g as solid content) into a 20 ml volumetric flask and make up with N-methylpyrrolidone. This solution is allowed to stand for 30 minutes in a thermostatic bath at 30 ° C., put in an Ubbelohde reduced specific viscosity tube (viscosity constant = 0.010 cSt / s), and the time for flowing down at 30 ° C. is measured. The measurement is performed twice with the same sample, and the average value is calculated. Similarly, in the case of a blank (only N-methylpyrrolidone), the reduced specific viscosity (ml / g) was calculated from the following formula.
以下に、アンモニウム基含有ポリマーの具体例を示す。
(1)2−(トリメチルアンモニオ)エチルメタクリレート=p−トルエンスルホナート/3,6−ジオキサヘプチルメタクリレート共重合体(モル比10/90 Mw4.5万)
(2)2−(トリメチルアンモニオ)エチルメタクリレート=ヘキサフルオロホスファート/3,6−ジオキサヘプチルメタクリレート共重合体(モル比20/80 Mw6.0万)
(3)2−(エチルジメチルアンモニオ)エチルメタクリレート=p−トルエンスルホナート/ヘキシルメタクリレート共重合体(モル比30/70 Mw4.5万)
(4)2−(トリメチルアンモニオ)エチルメタクリレート=ヘキサフルオロホスファート/2−エチルヘキシルメタクリレート共重合体(モル比20/80 Mw6.0万)
(5)2−(トリメチルアンモニオ)エチルメタクリレート=メチルスルファート/ヘキシルメタクリレート共重合体(モル比40/60 Mw7.0万)
(6)2−(ブチルジメチルアンモニオ)エチルメタクリレート=ヘキサフルオロホスファート/3,6−ジオキサヘプチルメタクリレート共重合体(モル比 25/75 Mw6.5万)
(7)2−(ブチルジメチルアンモニオ)エチルアクリレート=ヘキサフルオロホスファート/3,6−ジオキサヘプチルメタクリレート共重合体(モル比20/80 Mw6.5万)
(8)2−(ブチルジメチルアンモニオ)エチルメタクリレート=13−エチル−5,8,11−トリオキサ−1−ヘプタデカンスルホナート/3,6−ジオキサヘプチルメタクリレート共重合体(モル比20/80 Mw7.5万)
(9)2−(ブチルジメチルアンモニオ)エチルメタクリレート=ヘキサフルオロホスファート/3,6−ジオキサヘプチルメタクリレート/2−ヒドロキシ−3−メタクロイルオキシプロピルメタクリレート共重合体(モル比15/80/5 Mw6.5万)
Specific examples of the ammonium group-containing polymer are shown below.
(1) 2- (Trimethylammonio) ethyl methacrylate = p-toluenesulfonate / 3,6-dioxaheptyl methacrylate copolymer (molar ratio 10/90 Mw 45,000)
(2) 2- (Trimethylammonio) ethyl methacrylate = hexafluorophosphate / 3,6-dioxaheptyl methacrylate copolymer (molar ratio 20/80 Mw 60,000)
(3) 2- (Ethyldimethylammonio) ethyl methacrylate = p-toluenesulfonate / hexyl methacrylate copolymer (molar ratio 30/70 Mw 45,000)
(4) 2- (Trimethylammonio) ethyl methacrylate = hexafluorophosphate / 2-ethylhexyl methacrylate copolymer (molar ratio 20/80 Mw 60,000)
(5) 2- (Trimethylammonio) ethyl methacrylate = methyl sulfate / hexyl methacrylate copolymer (molar ratio 40/60 Mw 7 million)
(6) 2- (Butyldimethylammonio) ethyl methacrylate = hexafluorophosphate / 3,6-dioxaheptyl methacrylate copolymer (molar ratio 25/75 Mw 650,000)
(7) 2- (Butyldimethylammonio) ethyl acrylate = hexafluorophosphate / 3,6-dioxaheptyl methacrylate copolymer (molar ratio 20/80 Mw 65,000)
(8) 2- (butyldimethylammonio) ethyl methacrylate = 13-ethyl-5,8,11-trioxa-1-heptadecanesulfonate / 3,6-dioxaheptyl methacrylate copolymer (molar ratio 20/80 Mw 75,000)
(9) 2- (butyldimethylammonio) ethyl methacrylate = hexafluorophosphate / 3,6-dioxaheptyl methacrylate / 2-hydroxy-3-methacryloyloxypropyl methacrylate copolymer (molar ratio 15/80/5 (Mw 650,000)
上記感脂化剤の含有量は、画像記録層の全固形分に対して0.01〜30.0質量%が好ましく、より好ましくは0.1〜15.0質量%、1〜10質量%が更に好ましい。 The content of the sensitizer is preferably 0.01 to 30.0% by mass, more preferably 0.1 to 15.0% by mass and 1 to 10% by mass with respect to the total solid content of the image recording layer. Is more preferable.
(4)その他
更にその他の成分として、界面活性剤、着色剤、焼き出し剤、重合禁止剤、高級脂肪酸誘導体、可塑剤、無機微粒子、無機層状化合物、及び共増感剤若しくは連鎖移動剤などを添加することができる。具体的には、特開2008−284817号公報の段落番号[0114]〜[0159]、特開2006−091479号公報の段落番号[0023]〜[0027]、米国特許公開2008/0311520号明細書段落番号[0060]に記載の化合物及び添加量が好ましい。
(4) Others Further, as other components, surfactants, colorants, baking-out agents, polymerization inhibitors, higher fatty acid derivatives, plasticizers, inorganic fine particles, inorganic layered compounds, co-sensitizers or chain transfer agents, etc. Can be added. Specifically, paragraph numbers [0114] to [0159] of Japanese Patent Application Laid-Open No. 2008-284817, paragraph numbers [0023] to [0027] of Japanese Patent Application Laid-Open No. 2006-091479, and US Patent Publication No. 2008/0311520. The compounds and addition amounts described in paragraph [0060] are preferred.
(G)画像記録層の形成
本発明における画像記録層は、例えば、特開2008−195018号公報の段落番号[0142]〜[0143]に記載のように、必要な上記各成分を公知の溶剤に分散又は溶解して塗布液を調製し、これを支持体上にバーコーター塗布など公知の方法で塗布し、乾燥することで形成される。塗布、乾燥後に得られる支持体上の画像記録層塗布量(固形分)は、用途によって異なるが、一般的に0.3〜3.0g/m2が好ましい。この範囲で、より良好な感度と画像記録層のより良好な皮膜特性が得られる。
(G) Formation of Image Recording Layer The image recording layer in the present invention may be prepared by using the necessary components described above as described in paragraphs [0142] to [0143] of JP-A-2008-195018, for example. A coating solution is prepared by dispersing or dissolving in a coating solution, which is formed by applying the coating solution on a support by a known method such as bar coater coating and drying. The image recording layer coating amount (solid content) on the support obtained after coating and drying varies depending on the application, but is generally preferably 0.3 to 3.0 g / m 2 . Within this range, better sensitivity and better film properties of the image recording layer can be obtained.
〔下塗り層〕
本発明の平版印刷版原版は、画像記録層と支持体との間に下塗り層(中間層と呼ばれることもある)を設けることが好ましい。下塗り層は、露光部においては支持体と画像記録層との密着を強化し、未露光部においては画像記録層の支持体からのはく離を生じやすくさせるため、耐刷性を損なわず現像性を向上させるのに寄与する。また、赤外線レーザー露光の場合は、下塗り層が断熱層として機能することにより、露光により発生した熱が支持体に拡散して感度が低下するのを防ぐ。
(Undercoat layer)
In the lithographic printing plate precursor according to the invention, an undercoat layer (sometimes referred to as an intermediate layer) is preferably provided between the image recording layer and the support. The undercoat layer enhances the adhesion between the support and the image recording layer in the exposed area, and easily peels off the image recording layer from the support in the unexposed area. Contributes to improvement. In the case of infrared laser exposure, the undercoat layer functions as a heat insulating layer, thereby preventing the heat generated by the exposure from diffusing to the support and reducing the sensitivity.
下塗り層に用いる化合物としては、支持体表面に吸着可能な吸着性基、及び画像記録層と密着性を向上させるために架橋性基を有するものが好ましい。更に、スルホ基などの親水性付与基を有する化合物も好適な化合物として挙げることができる。これらの化合物は、低分子でも高分子ポリマーであってもよい。又、これらの化合物は必要に応じて2種以上を混合して使用してもよい。 As the compound used for the undercoat layer, those having an adsorptive group capable of being adsorbed on the surface of the support and a crosslinkable group for improving the adhesion to the image recording layer are preferable. Furthermore, compounds having a hydrophilicity-imparting group such as a sulfo group can also be mentioned as suitable compounds. These compounds may be low molecular weight or high molecular weight polymers. Moreover, you may use these compounds in mixture of 2 or more types as needed.
高分子ポリマーである場合は、吸着性基を有するモノマー、親水性基を有するモノマー、及び架橋性基を有するモノマーの共重合体が好ましい。支持体表面に吸着可能な吸着性基としては、フェノール性ヒドロキシ基、カルボキシ基、−PO3H2、−OPO3H2、−CONHSO2−、−SO2NHSO2−、−COCH2COCH3が好ましい。親水基としては、スルホ基が好ましい。架橋性基としてはメタクリル基、アリル基などが好ましい。
この高分子ポリマーは、高分子ポリマーの極性置換基と、対荷電を有する置換基及びエチレン性不飽和結合を有する化合物との塩形成で導入された架橋性基を有してもよいし、上記以外のモノマー、好ましくは親水性モノマーが更に共重合されていてもよい。
In the case of a high molecular polymer, a copolymer of a monomer having an adsorptive group, a monomer having a hydrophilic group, and a monomer having a crosslinkable group is preferable. The adsorbable adsorptive group to the surface of the support, a phenolic hydroxy group, a carboxy group, -PO 3 H 2, -OPO 3 H 2, -CONHSO 2 -, - SO 2 NHSO 2 -, - COCH 2 COCH 3 Is preferred. As the hydrophilic group, a sulfo group is preferable. The crosslinkable group is preferably a methacryl group or an allyl group.
This polymer may have a crosslinkable group introduced by salt formation between the polar substituent of the polymer, a substituent having a counter charge and a compound having an ethylenically unsaturated bond, Other monomers, preferably hydrophilic monomers, may be further copolymerized.
具体的には、特開平10−282679号公報に記載されている付加重合可能なエチレン性二重結合反応基を有しているシランカップリング剤、特開平2−304441号公報記載のエチレン性二重結合反応基を有しているリン化合物が好適に挙げられる。特開2005-238816号、特開2005−125749号、特開2006−239867号、特開2006−215263号の各公報記載の架橋性基(好ましくは、エチレン性不飽和結合基)、支持体表面に相互作用する官能基、及び親水性基を有する低分子又は高分子化合物を含有するものも好ましく用いられる。
より好ましいものとして、特開2005−125749号及び特開2006−188038号公報に記載の支持体表面に吸着可能な吸着性基、親水性基、及び架橋性基を有する高分子ポリマーが挙げられる。
Specifically, a silane coupling agent having an addition-polymerizable ethylenic double bond reactive group described in JP-A-10-282679 and an ethylenic compound described in JP-A-2-304441. The phosphorus compound which has a heavy bond reactive group is mentioned suitably. Crosslinkable group (preferably ethylenically unsaturated bond group) described in JP-A-2005-238816, JP-A-2005-12549, JP-A-2006-239867, JP-A-2006-215263, surface of support Those containing a low-molecular or high-molecular compound having a functional group that interacts with each other and a hydrophilic group are also preferably used.
More preferable are polymer polymers having an adsorbable group, a hydrophilic group, and a crosslinkable group that can be adsorbed on the support surface described in JP-A Nos. 2005-125749 and 2006-188038.
下塗り層用高分子樹脂中の不飽和二重結合の含有量は、高分子ポリマー1g当たり、好ましくは0.1〜10.0mmol、最も好ましくは0.2〜5.5mmolである。
下塗り層用の高分子ポリマーは、質量平均モル質量(Mw)が5000以上であるのが好ましく、1万〜30万であるのがより好ましい。
The content of unsaturated double bonds in the polymer resin for the undercoat layer is preferably 0.1 to 10.0 mmol, and most preferably 0.2 to 5.5 mmol per 1 g of the polymer.
The polymer for the undercoat layer preferably has a mass average molar mass (Mw) of 5000 or more, more preferably 10,000 to 300,000.
本発明の下塗り層は、上記下塗り層用化合物の他に、経時における汚れ防止のため、キレート剤、第2級又は第3級アミン、重合禁止剤、アミノ基又は重合禁止能を有する官能基とアルミニウム支持体表面と相互作用する基とを有する化合物等(例えば、1,4−ジアザビシクロ[2,2,2]オクタン(DABCO)、2,3,5,6−テトラヒドロキシ−p−キノン、クロラニル、スルホフタル酸、ヒドロキシエチルエチレンジアミン三酢酸、ジヒドロキシエチルエチレンジアミン二酢酸、ヒドロキシエチルイミノ二酢酸など)を含有することができる。 The undercoat layer of the present invention comprises, in addition to the above undercoat compound, a chelating agent, a secondary or tertiary amine, a polymerization inhibitor, an amino group, or a functional group having a polymerization inhibiting ability, in order to prevent contamination over time. Compounds having a group that interacts with the surface of an aluminum support (for example, 1,4-diazabicyclo [2,2,2] octane (DABCO), 2,3,5,6-tetrahydroxy-p-quinone, chloranil , Sulfophthalic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, hydroxyethyliminodiacetic acid, and the like.
下塗り層は、公知の方法で塗布される。下塗り層の塗布量(固形分)は、0.1〜100mg/m2であるのが好ましく、1〜30mg/m2であるのがより好ましい。 The undercoat layer is applied by a known method. The coating amount (solid content) of the undercoat layer is preferably from 0.1-100 mg / m 2, and more preferably 1 to 30 mg / m 2.
〔支持体〕
本発明の平版印刷版原版に用いられる支持体としては、公知の支持体が用いられる。なかでも、公知の方法で粗面化処理され、陽極酸化処理されたアルミニウム板が好ましい。
また、上記アルミニウム板は必要に応じて、特開2001−253181号公報や特開2001−322365号公報に記載されている陽極酸化皮膜のマイクロポアの拡大処理や封孔処理、及び米国特許第2,714,066号、同第3,181,461号、同第3,280,734号及び同第3,902,734号の各明細書に記載されているようなアルカリ金属シリケートあるいは米国特許第3,276,868号、同第4,153,461号及び同第4,689,272号の各明細書に記載されているようなポリビニルホスホン酸などによる表面親水化処理を適宜選択して行うことができる。
支持体は、中心線平均粗さが0.10〜1.2μmであるのが好ましい。
[Support]
As the support used in the lithographic printing plate precursor according to the invention, a known support is used. Of these, an aluminum plate that has been roughened and anodized by a known method is preferred.
In addition, the above aluminum plate is optionally subjected to micropore enlargement treatment or sealing treatment of an anodized film described in JP-A Nos. 2001-253181 and 2001-322365, and US Pat. 714,066, 3,181,461, 3,280,734 and 3,902,734, or alkali metal silicates as described in U.S. Pat. Surface hydrophilization treatment with polyvinylphosphonic acid or the like as described in each specification of 3,276,868, 4,153,461 and 4,689,272 is appropriately performed and performed. be able to.
The support preferably has a center line average roughness of 0.10 to 1.2 μm.
本発明の支持体には必要に応じて、裏面に、特開平5−45885号公報に記載されている有機高分子化合物、特開平6−35174号公報に記載されているケイ素のアルコキシ化合物を含むバックコート層を設けることができる。 If necessary, the support of the present invention includes an organic polymer compound described in JP-A-5-45885 and a silicon alkoxy compound described in JP-A-6-35174 on the back surface. A backcoat layer can be provided.
〔保護層〕
本発明の平版印刷版原版は、画像記録層の上に保護層(オーバーコート層)を設けることが好ましい。保護層は酸素遮断によって画像形成阻害反応を抑制する機能の他、画像記録層における傷の発生防止、及び高照度レーザー露光時のアブレーション防止の機能を有する。
[Protective layer]
In the lithographic printing plate precursor according to the invention, a protective layer (overcoat layer) is preferably provided on the image recording layer. In addition to the function of suppressing the image formation inhibition reaction by blocking oxygen, the protective layer has a function of preventing scratches in the image recording layer and preventing ablation during high-illuminance laser exposure.
このような特性の保護層については、例えば、米国特許第3,458,311号明細書及び特公昭55−49729号公報に記載されている。保護層に用いられる酸素低透過性のポリマーとしては、水溶性ポリマー、水不溶性ポリマーのいずれをも適宜選択して使用することができ、必要に応じて2種類以上を混合して使用することもできる。具体的には、例えば、ポリビニルアルコール、変性ポリビニルアルコール、ポリビニルピロリドン、水溶性セルロース誘導体、ポリ(メタ)アクリロニトリル等が挙げられる。
変性ポリビニルアルコールとしては、カルボキシ基又はスルホ基を有する酸変性ポリビニルアルコールが好ましく用いられる。具体的には、特開2005−250216号、特開2006−259137号の公報記載の変性ポリビニルアルコールが好適に挙げられる。
The protective layer having such characteristics is described in, for example, US Pat. No. 3,458,311 and Japanese Patent Publication No. 55-49729. As the low oxygen permeability polymer used for the protective layer, either a water-soluble polymer or a water-insoluble polymer can be appropriately selected and used, and two or more types can be mixed and used as necessary. it can. Specific examples include polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble cellulose derivatives, poly (meth) acrylonitrile, and the like.
As the modified polyvinyl alcohol, acid-modified polyvinyl alcohol having a carboxy group or a sulfo group is preferably used. Specifically, modified polyvinyl alcohols described in JP-A-2005-250216 and JP-A-2006-259137 are preferable.
また、保護層には酸素遮断性を高めるため、特開2005−119273号公報に記載のように天然雲母、合成雲母等の無機質の層状化合物を含有することが好ましい。
また、保護層には、可撓性付与のための可塑剤、塗布性を向上させための界面活性剤、表面の滑り性を制御する無機微粒子など公知の添加物を含むことができる。また、画像記録層の説明に記載した感脂化剤を保護層に含有させることもできる。
Further, in order to enhance the oxygen barrier property, the protective layer preferably contains an inorganic layered compound such as natural mica and synthetic mica as described in JP-A-2005-119273.
Further, the protective layer may contain known additives such as a plasticizer for imparting flexibility, a surfactant for improving coating properties, and inorganic fine particles for controlling surface slipperiness. Further, the protective layer can contain the sensitizer described in the description of the image recording layer.
保護層は、公知の方法で塗布される。保護層の塗布量としては、乾燥後の塗布量で、0.01〜10g/m2の範囲であることが好ましく、0.02〜3g/m2の範囲がより好ましく、最も好ましくは0.02〜1g/m2の範囲である。 The protective layer is applied by a known method. The coating amount of the protective layer, the coating amount after drying is preferably in the range of 0.01 to 10 g / m 2, more preferably in the range of 0.02 to 3 g / m 2, and most preferably 0. in the range of 02~1g / m 2.
〔製版方法〕
本発明の平版印刷版原版の製版は機上現像方法で行うことが好ましい。機上現像方法は、平版印刷版原版を画像露光する工程と、露光後の平版印刷版原版になんらの現像処理を施すことなく、油性インキと水性成分とを供給して、印刷する印刷工程とを有し、該印刷工程の途上において平版印刷版原版の未露光部分が除去されることを特徴とする。画像様の露光は平版印刷版原版を印刷機に装着した後、印刷機上で行ってもよいし、プレートセッターなどで別途行ってもよい。後者の場合は、露光済み平版印刷版原版は現像処理工程を経ないでそのまま印刷機に装着される。その後、該印刷機を用い、油性インキと水性成分とを供給してそのまま印刷することにより、印刷途上の初期の段階で機上現像処理、すなわち、未露光領域の画像記録層が除去され、それに伴って親水性支持体表面が露出され非画像部が形成される。油性インキ及び水性成分としては、通常の平版印刷用の印刷インキと湿し水が用いられる。
以下、更に詳細に説明する。
[Plate making method]
The plate making of the lithographic printing plate precursor according to the invention is preferably carried out by an on-press development method. The on-press development method includes an image exposure process for a lithographic printing plate precursor, a printing process in which an oil-based ink and an aqueous component are supplied and printed without performing any development process on the exposed lithographic printing plate precursor. And the unexposed portion of the lithographic printing plate precursor is removed during the printing process. Imagewise exposure may be performed on the printing machine after the lithographic printing plate precursor is mounted on the printing machine, or may be separately performed with a plate setter or the like. In the latter case, the exposed lithographic printing plate precursor is mounted on a printing machine without undergoing a development process. Thereafter, by using the printing machine and supplying the oil-based ink and the aqueous component and printing as it is, an on-press development process, that is, an image recording layer in an unexposed area is removed at an early stage of printing, Accordingly, the surface of the hydrophilic support is exposed to form a non-image part. As the oil-based ink and the aqueous component, ordinary lithographic printing ink and fountain solution are used.
This will be described in more detail below.
本発明において画像露光に用いられる光源としては、レーザーが好ましい。本発明に用いられるレーザーは、特に限定されないが、波長760〜1200nmの赤外線を照射する固体レーザー及び半導体レーザーなどが好適に挙げられる。
赤外線レーザーに関しては、出力は100mW以上であることが好ましく、1画素当たりの露光時間は20マイクロ秒以内であるのが好ましく、また照射エネルギー量は10〜300mJ/cm2であるのが好ましい。レーザーにおいては、露光時間を短縮するためマルチビームレーザーデバイスを用いるのが好ましい。
In the present invention, the light source used for image exposure is preferably a laser. Although the laser used for this invention is not specifically limited, The solid laser and semiconductor laser etc. which irradiate infrared rays with a wavelength of 760-1200 nm are mentioned suitably.
Regarding the infrared laser, the output is preferably 100 mW or more, the exposure time per pixel is preferably within 20 microseconds, and the irradiation energy amount is preferably 10 to 300 mJ / cm 2 . In the laser, it is preferable to use a multi-beam laser device in order to shorten the exposure time.
露光された平版印刷版原版は、印刷機の版胴に装着される。レーザー露光装置付きの印刷機の場合は、平版印刷版原版を印刷機の版胴に装着したのち画像露光される。 The exposed lithographic printing plate precursor is mounted on a plate cylinder of a printing press. In the case of a printing press equipped with a laser exposure device, image exposure is performed after a lithographic printing plate precursor is mounted on a plate cylinder of the printing press.
画像様に露光した平版印刷版原版に湿し水と印刷インキとを供給して印刷すると、画像記録層の露光部においては、露光により硬化した画像記録層が、親油性表面を有する印刷インキ受容部を形成する。一方、未露光部においては、供給された湿し水及び/又は印刷インキによって、未硬化の画像記録層が溶解又は分散して除去され、その部分に親水性の表面が露出する。その結果、湿し水は露出した親水性の表面に付着し、印刷インキは露光領域の画像記録層に着肉して印刷が開始される。 When printing is performed by supplying dampening water and printing ink to the lithographic printing plate precursor exposed imagewise, the image recording layer cured by exposure has a printing ink acceptance having an oleophilic surface in the exposed portion of the image recording layer. Forming part. On the other hand, in the unexposed area, the uncured image recording layer is removed by dissolution or dispersion by the supplied dampening water and / or printing ink, and a hydrophilic surface is exposed in that area. As a result, the fountain solution adheres to the exposed hydrophilic surface, and the printing ink is deposited on the image recording layer in the exposed area and printing is started.
ここで、最初に版面に供給されるのは、湿し水でもよく、印刷インキでもよいが、湿し水が除去された画像記録層成分によって汚染されることを防止する点で、最初に印刷インキを供給するのが好ましい。
このようにして、本発明の平版印刷版原版はオフセット印刷機上で機上現像され、そのまま多数枚の印刷に用いられる。
Here, dampening water or printing ink may be supplied to the printing plate first, but printing is first performed in order to prevent the dampening water from being contaminated by the removed image recording layer components. It is preferable to supply ink.
In this way, the lithographic printing plate precursor according to the invention is developed on the machine on an offset printing machine and used as it is for printing a large number of sheets.
以下、実施例により本発明を詳細に説明するが、本発明はこれらに限定されるものではない。なお、高分子化合物において、特別に規定したもの以外は、分子量は質量平均モル質量(Mw)であり、繰り返し単位の比率はモル百分率である。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. In the polymer compound, the molecular weight is a mass average molar mass (Mw), and the ratio of repeating units is a mole percentage, except for those specifically defined.
〔I〕樹脂微粒子水分散液の製造例 [I] Production example of resin fine particle aqueous dispersion
(樹脂微粒子水分散液(1)の製造)
1000mlの4つ口フラスコに撹拌機、温度計、滴下ロート、窒素導入管、還流冷却器を施し、窒素ガスを導入して脱酸素を行いつつ、蒸留水200g及びn−プロパノール200gを加えて内温が70℃となるまで加熱した。次に予め混合されたスチレン(St)10g、アクリロニトリル(AN)80g及び2,2´−アゾビスイソブチロニトリル0.8g、ドデシルベンセンスルホン酸1質量%の混合物を1時間かけて滴下した。滴下終了後5時間そのまま反応を続けた後、2,2´−アゾビスイソブチロニトリル0.4gを添加し、内温を80℃まで上昇させた。続いて、0.5gの2,2´−アゾビスイソブチロニトリルを6時間かけて添加した。合計で20時間反応させた段階でポリマー化は98%以上進行した。次に第2段目の樹脂を構成するために、予め混合されたアクリルアミド10g、エチレングリコールジメタクリレート5g、ポリエチレングリコールーポリプロピレングリコールモノメタクリレート(ブレンマーPEP−550B 日本油脂製)20g、蒸留水40g、及び2,2´−アゾビスイソブチロニトリル0.8gの混合物を1時間かけて滴下した。滴下終了後5時間そのまま反応を続けた後、2,2´−アゾビスイソブチロニトリル0.4gを添加し、内温を80℃まで上昇させ有機溶剤並びに余剰の水を減圧除去することによって樹脂微粒子の水分散体(固形分:35質量%)が得られた。
(Production of resin fine particle aqueous dispersion (1))
A 1000 ml four-necked flask is equipped with a stirrer, thermometer, dropping funnel, nitrogen inlet tube, reflux condenser, nitrogen gas is introduced for deoxygenation, and 200 g of distilled water and 200 g of n-propanol are added. Heated until the temperature reached 70 ° C. Next, a premixed mixture of 10 g of styrene (St), 80 g of acrylonitrile (AN), 0.8 g of 2,2′-azobisisobutyronitrile and 1% by mass of dodecyl benzene sulfonic acid was added dropwise over 1 hour. After the completion of the dropwise addition, the reaction was continued for 5 hours, and then 0.4 g of 2,2′-azobisisobutyronitrile was added to raise the internal temperature to 80 ° C. Subsequently, 0.5 g of 2,2′-azobisisobutyronitrile was added over 6 hours. Polymerization progressed 98% or more at the stage of reaction for a total of 20 hours. Next, 10 g of acrylamide, 5 g of ethylene glycol dimethacrylate, 20 g of polyethylene glycol-polypropylene glycol monomethacrylate (Blenmer PEP-550B made by Nippon Oil & Fats), 40 g of distilled water, and A mixture of 0.8 g of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour. By continuing the reaction for 5 hours after the completion of the dropping, 0.4 g of 2,2′-azobisisobutyronitrile was added, the internal temperature was raised to 80 ° C., and the organic solvent and excess water were removed under reduced pressure. An aqueous dispersion of resin fine particles (solid content: 35% by mass) was obtained.
(樹脂微粒子水分散液(2)の製造)
樹脂微粒子水分散液(1)の製造における第2段目用のポリエチレングリコールーポリプロピレングリコールモノメタクリレートの代わりにポリエチレングリコールモノメタクリレート(ブレンマーPE-350 日本油脂製)を用いた以外は樹脂微粒子水分散液(1)の製造と同様にして樹脂微粒子水分散液(2)(固形分:35質量%)を得た。
(Production of resin fine particle aqueous dispersion (2))
Resin fine particle aqueous dispersion, except that polyethylene glycol monomethacrylate (Blenmer PE-350 manufactured by NOF Corporation) was used in place of the second stage polyethylene glycol-polypropylene glycol monomethacrylate in the production of resin fine particle aqueous dispersion (1) In the same manner as in the production of (1), an aqueous resin fine particle dispersion (2) (solid content: 35% by mass) was obtained.
(樹脂微粒子水分散液(3)の製造)
樹脂微粒子水分散液(1)の製造における第2段目用のポリエチレングリコールーポリプロピレングリコールモノメタクリレートの代わりにポリプロピレングリコールモノメタクリレート(ブレンマーPP-800 日本油脂製)を用いた以外は樹脂微粒子水分散液(1)の製造と同様にして樹脂微粒子水分散液(3)(固形分:35質量%)を得た。
(Production of resin fine particle aqueous dispersion (3))
Resin fine particle aqueous dispersion, except that polypropylene glycol monomethacrylate (Blenmer PP-800 made by NOF Corporation) was used in place of the second stage polyethylene glycol-polypropylene glycol monomethacrylate in the production of resin fine particle aqueous dispersion (1) In the same manner as in the production of (1), an aqueous resin fine particle dispersion (3) (solid content: 35% by mass) was obtained.
(樹脂微粒子水分散液(4)の製造)
樹脂微粒子水分散液(1)の製造における第2段目用のポリエチレングリコールーポリプロピレングリコールモノメタクリレートの代わりにポリエチレングリコールモノメタクリレート(ブレンマーPE-200 日本油脂製)を用いた以外は樹脂微粒子水分散液(1)の製造と同様にして樹脂微粒子水分散液(4)(固形分:35質量%)を得た。
(Production of resin fine particle aqueous dispersion (4))
Resin fine particle aqueous dispersion, except that polyethylene glycol monomethacrylate (Blenmer PE-200, manufactured by NOF Corporation) was used in place of the second stage polyethylene glycol-polypropylene glycol monomethacrylate in the production of resin fine particle aqueous dispersion (1) In the same manner as in the production of (1), an aqueous resin fine particle dispersion (4) (solid content: 35% by mass) was obtained.
(樹脂微粒子水分散液(5)の製造)
樹脂微粒子水分散液(1)の製造における第2段目用のポリエチレングリコールーポリプロピレングリコールモノメタクリレートの代わりにメトキシポリエチレングリコールモノメタクリレート(ブレンマーPME-1000 日本油脂製)を用いた以外は樹脂微粒子水分散液(1)の製造と同様にして樹脂微粒子水分散液(5)(固形分:35質量%)を得た。
(Production of resin fine particle aqueous dispersion (5))
Resin fine particle water dispersion except that methoxypolyethylene glycol monomethacrylate (Blenmer PME-1000 manufactured by NOF Corporation) was used instead of polyethylene glycol-polypropylene glycol monomethacrylate for the second stage in the production of resin fine particle water dispersion (1) Resin fine particle aqueous dispersion (5) (solid content: 35% by mass) was obtained in the same manner as in the production of liquid (1).
(樹脂微粒子水分散液(6)の製造)
樹脂微粒子水分散液(1)の製造における第2段目用のポリエチレングリコールーポリプロピレングリコールモノメタクリレートの代わりにメトキシポリエチレングリコールモノメタクリレート(ブレンマーPME-4000 日本油脂製)を用いた以外は樹脂微粒子水分散液(1)の製造と同様にして樹脂微粒子水分散液(6)(固形分:35質量%)を得た。
(Production of resin fine particle aqueous dispersion (6))
Dispersion of fine resin particles in water except that methoxypolyethylene glycol monomethacrylate (Blenmer PME-4000 manufactured by NOF Corporation) was used in place of the second stage polyethylene glycol-polypropylene glycol monomethacrylate in the production of fine resin particle water dispersion (1) Resin fine particle aqueous dispersion (6) (solid content: 35% by mass) was obtained in the same manner as in the preparation of liquid (1).
(樹脂微粒子水分散液(7)の製造)
1000mlの4つ口フラスコに撹拌機、温度計、滴下ロート、窒素導入管、還流冷却器を施し、窒素ガスを導入して脱酸素を行いつつ、蒸留水200g及びn−プロパノール200gを加えて内温が70℃となるまで加熱した。次に予め混合されたアクリロニトリル(AN)90g及び2,2´−アゾビスイソブチロニトリル0.8g、ドデシルベンセンスルホン酸1質量%の混合物を1時間かけて滴下した。滴下終了後5時間そのまま反応を続けた後、2,2´−アゾビスイソブチロニトリル0.4gを添加し、内温を80℃まで上昇させた。続いて、0.5gの2,2´−アゾビスイソブチロニトリルを6時間かけて添加した。合計で20時間反応させた段階でポリマー化は98%以上進行した。次に第2段目の樹脂を構成するために、予め混合されたアクリルアミド10g、エチレングリコールジメタクリレート5g、メトキシポリエチレングリコールモノメタクリレート(ブレンマーPME-200 日本油脂製)20g、蒸留水40g、及び2,2´−アゾビスイソブチロニトリル0.8gの混合物を1時間かけて滴下した。滴下終了後5時間そのまま反応を続けた後、2,2´−アゾビスイソブチロニトリル0.4gを添加し、内温を80℃まで上昇させ有機溶剤並びに余剰の水を減圧除去することによって樹脂微粒子の水分散体(固形分:35質量%)が得られた。
(Production of resin fine particle aqueous dispersion (7))
A 1000 ml four-necked flask is equipped with a stirrer, thermometer, dropping funnel, nitrogen inlet tube, reflux condenser, nitrogen gas is introduced for deoxygenation, and 200 g of distilled water and 200 g of n-propanol are added. Heated until the temperature reached 70 ° C. Next, a premixed mixture of 90 g of acrylonitrile (AN), 0.8 g of 2,2′-azobisisobutyronitrile and 1% by mass of dodecyl benzene sulfonic acid was added dropwise over 1 hour. After the completion of the dropwise addition, the reaction was continued for 5 hours, and then 0.4 g of 2,2′-azobisisobutyronitrile was added to raise the internal temperature to 80 ° C. Subsequently, 0.5 g of 2,2′-azobisisobutyronitrile was added over 6 hours. Polymerization progressed 98% or more at the stage of reaction for a total of 20 hours. Next, 10 g of premixed acrylamide, 5 g of ethylene glycol dimethacrylate, 20 g of methoxypolyethylene glycol monomethacrylate (Blenmer PME-200 manufactured by NOF Corporation), 40 g of distilled water, and 2, A mixture of 0.8 g of 2'-azobisisobutyronitrile was added dropwise over 1 hour. By continuing the reaction for 5 hours after the completion of the dropping, 0.4 g of 2,2′-azobisisobutyronitrile was added, the internal temperature was raised to 80 ° C., and the organic solvent and excess water were removed under reduced pressure. An aqueous dispersion of resin fine particles (solid content: 35% by mass) was obtained.
(樹脂微粒子水分散液(8)の製造)
1000mlの4つ口フラスコに撹拌機、温度計、滴下ロート、窒素導入管、還流冷却器を施し、窒素ガスを導入して脱酸素を行いつつ、蒸留水200g及びn−プロパノール200gを加えて内温が70℃となるまで加熱した。次に予め混合されたアクリロニトリル(AN)90g及び2,2´−アゾビスイソブチロニトリル0.8g、ドデシルベンセンスルホン酸1質量%の混合物を1時間かけて滴下した。滴下終了後5時間そのまま反応を続けた後、2,2´−アゾビスイソブチロニトリル0.4gを添加し、内温を80℃まで上昇させた。続いて、0.5gの2,2´−アゾビスイソブチロニトリルを6時間かけて添加した。合計で20時間反応させた段階でポリマー化は98%以上進行した。次に第2段目の樹脂を構成するために、予め混合されたアクリルアミド15g、メトキシポリエチレングリコールモノメタクリレート(ブレンマーPME-200 日本油脂製)20g、蒸留水40g、及び2,2´−アゾビスイソブチロニトリル0.8gの混合物を1時間かけて滴下した。滴下終了後5時間そのまま反応を続けた後、2,2´−アゾビスイソブチロニトリル0.4gを添加し、内温を80℃まで上昇させ有機溶剤並びに余剰の水を減圧除去することによって樹脂微粒子の水分散体(固形分:35質量%)が得られた。
(Production of resin fine particle aqueous dispersion (8))
A 1000 ml four-necked flask is equipped with a stirrer, thermometer, dropping funnel, nitrogen inlet tube, reflux condenser, nitrogen gas is introduced for deoxygenation, and 200 g of distilled water and 200 g of n-propanol are added. Heated until the temperature reached 70 ° C. Next, a premixed mixture of 90 g of acrylonitrile (AN), 0.8 g of 2,2′-azobisisobutyronitrile and 1% by mass of dodecyl benzene sulfonic acid was added dropwise over 1 hour. After the completion of the dropwise addition, the reaction was continued for 5 hours, and then 0.4 g of 2,2′-azobisisobutyronitrile was added to raise the internal temperature to 80 ° C. Subsequently, 0.5 g of 2,2′-azobisisobutyronitrile was added over 6 hours. Polymerization progressed 98% or more at the stage of reaction for a total of 20 hours. Next, 15 g of premixed acrylamide, 20 g of methoxypolyethylene glycol monomethacrylate (Blenmer PME-200 manufactured by Nippon Oil & Fats), 40 g of distilled water, and 2,2′-azobisiso to form the second stage resin A mixture of 0.8 g of butyronitrile was added dropwise over 1 hour. By continuing the reaction for 5 hours after the completion of the dropping, 0.4 g of 2,2′-azobisisobutyronitrile was added, the internal temperature was raised to 80 ° C., and the organic solvent and excess water were removed under reduced pressure. An aqueous dispersion of resin fine particles (solid content: 35% by mass) was obtained.
(樹脂微粒子水分散液(9)(比較例1用)の製造)
1000mlの4つ口フラスコに撹拌機、温度計、滴下ロート、窒素導入管、還流冷却器を施し、窒素ガスを導入して脱酸素を行いつつ、ポリエチレングリコールメチルエーテルメタクリレート(PEGMA エチレングリコールの平均の繰返し単位は50)10g、蒸留水200g及びn−プロパノール200gを加えて内温が70℃となるまで加熱した。次に予め混合されたスチレン(St)10g、アクリロニトリル(AN)80g及び2,2´−アゾビスイソブチロニトリル0.8gの混合物を1時間かけて滴下した。滴下終了後5時間そのまま反応を続けた後、2,2´−アゾビスイソブチロニトリル0.4gを添加し、内温を80℃まで上昇させた。続いて、0.5gの2,2´−アゾビスイソブチロニトリルを6時間かけて添加した。合計で20時間反応させた段階でポリマー化は98%以上進行しており、質量比でPEGMA/St/AN=10/10/80の樹脂微粒子水分散液(固形分:35質量%)が得られた。
(Production of resin fine particle aqueous dispersion (9) (for Comparative Example 1))
A 1000 ml four-necked flask is equipped with a stirrer, thermometer, dropping funnel, nitrogen inlet tube, reflux condenser, and nitrogen gas is introduced to perform deoxygenation, while polyethylene glycol methyl ether methacrylate (average of PEGMA ethylene glycol) The repeating unit was 50) 10 g, distilled water 200 g and n-propanol 200 g were added and heated until the internal temperature reached 70 ° C. Next, a mixture of 10 g of styrene (St), 80 g of acrylonitrile (AN), and 0.8 g of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour. After the completion of the dropwise addition, the reaction was continued for 5 hours, and then 0.4 g of 2,2′-azobisisobutyronitrile was added to raise the internal temperature to 80 ° C. Subsequently, 0.5 g of 2,2′-azobisisobutyronitrile was added over 6 hours. Polymerization has progressed over 98% at the stage of reaction for a total of 20 hours, and an aqueous dispersion of resin fine particles (solid content: 35% by mass) with a mass ratio of PEGMA / St / AN = 10/10/80 is obtained. It was.
(樹脂微粒子水分散液(10)(比較例2用)の製造)
油相成分として、ポリメチルメタクリレート(質量平均モル質量120,000)5.0g、グリシジルメタクリレート10g、2−ブタノン25.0g、界面活性剤パイオニンA41C(竹本油脂(株)製)0.3gの溶液を調製し、水相成分として、平均繰返し単位数が50のポリエチレングリコール 20g、水150gの溶液を調製し、両者を混合した後、ホモジナイザーにて12,000rpm、10分間激しく攪拌混合して、水相中に油滴を分散した乳化分散物を得た。次に、ステンレス製ポットに乳化分散物を投入し、60℃3時間攪拌して溶剤成分を除去することによって、粒径0.32μmの疎水性樹脂微粒子の水分散液(固形分:35質量%)を得た。
(Production of resin fine particle aqueous dispersion (10) (for Comparative Example 2))
As an oil phase component, a solution of 5.0 g of polymethyl methacrylate (mass average molar mass 120,000), 10 g of glycidyl methacrylate, 25.0 g of 2-butanone, and 0.3 g of a surfactant Pionine A41C (manufactured by Takemoto Yushi Co., Ltd.) As a water phase component, a solution of 20 g of polyethylene glycol having an average number of repeating units of 50 and 150 g of water was prepared. After mixing both, the mixture was vigorously stirred and mixed with a homogenizer at 12,000 rpm for 10 minutes. An emulsified dispersion having oil droplets dispersed in the phase was obtained. Next, the emulsified dispersion was put into a stainless steel pot, and the solvent component was removed by stirring at 60 ° C. for 3 hours, whereby an aqueous dispersion of hydrophobic resin fine particles having a particle size of 0.32 μm (solid content: 35% by mass) )
(樹脂微粒子水分散液(11)(比較例3用)の製造)
攪拌装置、還流装置、窒素導入管、滴下装置及び温度計を備えた1Lの四つ口フラスコにメチルエチルケトンの300gを仕込み、75℃に昇温した。スチレンの60g、メタクリル酸メチルの320g、メタクリル酸の30g、2,2´−アゾビス(イソ酪酸)ジメチル(V−601和光純薬工業(株)製の重合開始剤)6gをよく混合した溶液を3時間かけて滴下した。10時間攪拌後、V−601の0.8gを加え、更に、10時間撹拌することによって、乾燥固形分比が35質量%、酸価29.6、質量平均モル質量(Mw)が45000のアクリルポリマーが得られた。上記のアクリルポリマーの溶液200gをトリエチルアミン6gで中和し、攪拌しながら水を滴下した。溶液は徐々に増粘し、約250gの水を滴下した辺りから著しく粘度が低下して転相が完了した。更に200gの水を加えた後、得られた分散液を45℃に加熱して、有機溶剤並びに余剰の水を減圧除去することによって樹脂微粒子の水分散体(固形分:45質量%)が得られた。
(Production of resin fine particle aqueous dispersion (11) (for Comparative Example 3))
300 g of methyl ethyl ketone was charged into a 1 L four-necked flask equipped with a stirrer, a reflux device, a nitrogen inlet tube, a dropping device and a thermometer, and the temperature was raised to 75 ° C. A solution in which 60 g of styrene, 320 g of methyl methacrylate, 30 g of methacrylic acid, and 6 g of 2,2′-azobis (isobutyric acid) dimethyl (polymerization initiator manufactured by V-601 Wako Pure Chemical Industries, Ltd.) was mixed well. The solution was added dropwise over 3 hours. After stirring for 10 hours, 0.8 g of V-601 was added, and the mixture was further stirred for 10 hours, whereby an acrylic having a dry solid content ratio of 35% by mass, an acid value of 29.6, and a mass average molar mass (Mw) of 45,000. A polymer was obtained. 200 g of the above acrylic polymer solution was neutralized with 6 g of triethylamine, and water was added dropwise with stirring. The solution gradually increased in viscosity, and the viscosity was remarkably lowered from the point where about 250 g of water was dropped to complete the phase inversion. Further, 200 g of water was added, and the resulting dispersion was heated to 45 ° C., and the organic solvent and excess water were removed under reduced pressure to obtain an aqueous dispersion of resin fine particles (solid content: 45 mass%). It was.
〔II〕平版印刷版原版 (1)〜(8)の作製
(1)支持体の作製
厚み0.3mmのアルミニウム板(材質JIS A 1050)の表面の圧延油を除去するため、10質量%アルミン酸ソーダ水溶液を用いて50℃で30秒間、脱脂処理を施した後、毛径0.3mmの束植ナイロンブラシ3本とメジアン径25μmのパミス−水懸濁液(比重1.1g/cm3)を用いアルミニウム表面を砂目立てして、水でよく洗浄した。この板を45℃の25質量%水酸化ナトリウム水溶液に9秒間浸漬してエッチングを行い、水洗後、更に60℃で20質量%硝酸水溶液に20秒間浸漬し、水洗した。この時の砂目立て表面のエッチング量は約3g/m2であった。
[II] Preparation of lithographic printing plate precursors (1) to (8) (1) Preparation of support 10% by weight aluminum to remove rolling oil on the surface of a 0.3 mm thick aluminum plate (material JIS A 1050) After degreasing at 50 ° C. for 30 seconds using an aqueous acid soda solution, three bundle-planted nylon brushes having a bristle diameter of 0.3 mm and a pumice-water suspension having a median diameter of 25 μm (specific gravity of 1.1 g / cm 3) ), And the aluminum surface was grained and washed thoroughly with water. This plate was etched by being immersed in a 25 mass% aqueous sodium hydroxide solution at 45 ° C for 9 seconds, washed with water, further immersed in a 20 mass% nitric acid aqueous solution at 60 ° C for 20 seconds, and washed with water. At this time, the etching amount of the grained surface was about 3 g / m 2 .
次に、60Hzの交流電圧を用いて連続的に電気化学的な粗面化処理を行った。このときの電解液は、硝酸1質量%水溶液(アルミニウムイオンを0.5質量%含む)、液温50℃であった。交流電源波形は、電流値がゼロからピークに達するまでの時間TPが0.8msec、duty比1:1、台形の矩形波交流を用いて、カーボン電極を対極として電気化学的な粗面化処理を行った。補助アノードにはフェライトを用いた。電流密度は電流のピーク値で30A/dm2、補助陽極には電源から流れる電流の5%を分流させた。硝酸電解における電気量はアルミニウム板が陽極時の電気量175C/dm2であった。その後、スプレーによる水洗を行った。 Next, an electrochemical roughening treatment was performed continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a 1% by mass nitric acid aqueous solution (containing 0.5% by mass of aluminum ions) and a liquid temperature of 50 ° C. The AC power source waveform is electrochemical roughening treatment using a trapezoidal rectangular wave alternating current with a time ratio TP of 0.8 msec until the current value reaches a peak from zero, a duty ratio of 1: 1, and a trapezoidal rectangular wave alternating current. Went. Ferrite was used for the auxiliary anode. The current density was 30 A / dm 2 at the peak current value, and 5% of the current flowing from the power source was shunted to the auxiliary anode. The amount of electricity in nitric acid electrolysis was 175 C / dm 2 when the aluminum plate was the anode. Then, water washing by spraying was performed.
続いて、塩酸0.5質量%水溶液(アルミニウムイオンを0.5質量%含む)、液温50℃の電解液にて、アルミニウム板が陽極時の電気量50C/dm2の条件で、硝酸電解と同様の方法で、電気化学的な粗面化処理を行い、その後、スプレーによる水洗を行った。
疎面化処理されたアルミニウム支持体に、 二段給電電解処理法の陽極酸化装置(第一及び第二電解部長各6m、第一及び第二給電部長各3m、第一及び第二給電極部長各2.4m)を用いて陽極酸化処理を行った。第一及び第二電解部に供給した電解液は、いずれも、リン酸濃度50g/L(アルミニウムイオンを0.5重量%含む。)、温度20℃であった。
その後、スプレーによる水洗を行い得られたアルミニウム支持体(A)に下記下塗り層塗布液を20g/m2になるように塗布乾燥し、その上に下記の画像記録層塗布液(1〜8)をバー塗布した後、70℃、60秒でオーブン乾燥し、乾燥塗布量0.6g/m2の画像記録層を作製し、平版印刷版原版(1)〜(8)〔実施例1〜8用〕を得た。
Subsequently, nitric acid electrolysis was performed with an aqueous solution of 0.5% by mass of hydrochloric acid (containing 0.5% by mass of aluminum ions) and an electrolytic solution having a liquid temperature of 50 ° C. under the condition of an electric quantity of 50 C / dm 2 when the aluminum plate was the anode. In the same manner as above, an electrochemical surface roughening treatment was performed, followed by washing with water by spraying.
Two-stage feed electrolytic treatment method anodizing device (first and second electrolysis part length 6m, first and second feed part length 3m, first and second feed electrode part length) Anodization was performed using 2.4 m each. The electrolytes supplied to the first and second electrolysis parts were both phosphoric acid concentration 50 g / L (containing 0.5 wt% aluminum ions) and temperature 20 ° C.
Thereafter, the following undercoat layer coating solution was applied and dried to 20 g / m 2 on the aluminum support (A) obtained by washing with water, and the following image recording layer coating solutions (1 to 8) were further formed thereon. And then dried in an oven at 70 ° C. for 60 seconds to prepare an image recording layer having a dry coating amount of 0.6 g / m 2. The planographic printing plate precursors (1) to (8) [Examples 1 to 8] Obtained].
<下塗り層塗布液>
・下記構造の下塗り層用化合物(1) 0.18g
・ヒドロキシエチルイミノ二酢酸 0.10g
・メタノール 55.24g
・水 6.15g
<Undercoat layer coating solution>
-Undercoat layer compound (1) having the following structure: 0.18 g
・ Hydroxyethyliminodiacetic acid 0.10g
・ Methanol 55.24g
・ Water 6.15g
<画像記録層塗布液(1〜8)>
・樹脂微粒子水分散液(1〜8)(表1に記載) 20.0g
・赤外線吸収染料(2)[下記構造] 0.2g
・ラジカル発生剤 Irgacure250(チバスペシャリティケミカルズ製) 0.5g
・ラジカル重合性化合物 SR-399(サートマー社製) 1.50g
・メルカプト−3−トリアゾール 0.2g
・Byk336(Byk Chimie社製) 0.4g
・KlucelM(Hercules社製) 4.8g
・ELVACITE4026(Ineos Acrylica社製) 2.5g
・n−プロパノール 55.0g
・2−ブタノン 17.0g
<Image recording layer coating solution (1-8)>
・ Resin fine particle aqueous dispersion (1 to 8) (described in Table 1) 20.0 g
・ Infrared absorbing dye (2) [The following structure] 0.2g
-Radical generator Irgacure250 (Ciba Specialty Chemicals) 0.5g
・ Radically polymerizable compound SR-399 (Sartomer) 1.50 g
・ Mercapto-3-triazole 0.2g
・ Byk336 (Byk Chimie) 0.4g
・ KlucelM (Hercules) 4.8g
・ ELVACITE4026 (Ineos Acrylica) 2.5g
・ N-propanol 55.0g
・ 2-butanone 17.0g
なお、上記組成中の商品名で記載の化合物は下記の通りである。
・IRGACURE 250:(4−メトキシフェニル)[4−(2−メチルプロピル)フェニル]ヨードニウム=ヘキサフルオロホスファート(75質量%プロピレンカーボナート溶液)
・SR-399:ジペンタエリスリトールペンタアクリレート
・BYK 336:変性ジメチルポリシロキサン共重合体(25質量%キシレン/メトキシプロピルアセテート溶液)
・KLUCEL M:ヒドロキシプロピルセルロース(2質量%水溶液)
・ELVACITE 4026:高分岐ポリメチルメタクリレート(10質量%2−ブタノン溶液)
In addition, the compounds described by trade names in the above composition are as follows.
IRGACURE 250: (4-methoxyphenyl) [4- (2-methylpropyl) phenyl] iodonium = hexafluorophosphate (75% by mass propylene carbonate solution)
・ SR-399: Dipentaerythritol pentaacrylate
BYK 336: modified dimethylpolysiloxane copolymer (25% by mass xylene / methoxypropyl acetate solution)
・ KLUCEL M: Hydroxypropyl cellulose (2 mass% aqueous solution)
ELVACITE 4026: Hyperbranched polymethyl methacrylate (10% by mass 2-butanone solution)
〔III〕平版印刷版原版 (9)〜(16)の作製
前記画像記録層塗布液(1〜8)のラジカル重合性化合物SR−399を上記(U−10)に代えた画像記録層塗布液(9〜16)を用いた。それ以外は前記平版印刷版原版(1)〜(8)の作製と同様にして、平版印刷版原版(9)〜(16)〔実施例9〜16用〕を得た。
[III] Preparation of lithographic printing plate precursors (9) to (16) Image recording layer coating solution in which radically polymerizable compound SR-399 in the image recording layer coating solution (1 to 8) is replaced with (U-10) above (9-16) was used. Other than that was carried out similarly to preparation of the said lithographic printing plate precursors (1)-(8), and obtained the lithographic printing plate precursors (9)-(16) [for Examples 9-16].
〔IV〕平版印刷版原版 (17)の作製
前記平版印刷版原版(1)と同じ下塗り層を有する支持体に、下記の画像記録層塗布液(17)をバー塗布した後、70℃、60秒でオーブン乾燥し、乾燥塗布量0.6g/m2の画像記録層を作製し、次に下記保護層塗布液(1)をバー塗布した後、100℃、60秒でオーブン乾燥し、乾燥塗布量0.2g/m2の保護層を作製し平版印刷版原版(17)〔実施例17用〕を得た。
[IV] Preparation of lithographic printing plate precursor (17) The following image recording layer coating solution (17) was applied to a support having the same undercoat layer as the lithographic printing plate precursor (1) by bar coating, followed by 70 ° C, 60 ° C. After oven drying in seconds, an image recording layer having a dry coating amount of 0.6 g / m 2 was prepared, and then the following protective layer coating solution (1) was bar coated, followed by oven drying at 100 ° C. for 60 seconds and drying. A protective layer having a coating amount of 0.2 g / m 2 was prepared to obtain a lithographic printing plate precursor (17) [for Example 17].
<画像記録層塗布液(17)>
・バインダーポリマー(1)〔下記構造〕 10g
・赤外線吸収染料(1)〔下記構造〕 0.30g
・ラジカル発生剤(1)〔下記構造〕 1.62g
・ラジカル重合性化合物
トリス(アクリロイルオキシエチル)イソシアヌレート
(NKエステルA−9300、新中村化学(株)製) 1.92g
・トリス(2−ヒドロキシエチル)イソシアヌレート 0.62g
・低分子親水性化合物(1)〔下記構造〕 0.50g
・感脂化剤 ホスホニウム化合物(1)〔下記構造〕 0.55g
・感脂化剤
ベンジル−ジメチル−オクチルアンモニウム・PF6塩 0.18g
・感脂化剤 アンモニウム基含有ポリマー〔下記構造〕 1.0g
・フッ素系界面活性剤(1)〔下記構造〕 0.08g
・2−ブタノン 10.91g
・1−メトキシ−2−プロパノール 55.09g
・樹脂微粒子水分散液(1) 20.0g
<Image recording layer coating solution (17)>
-Binder polymer (1) [The following structure] 10g
・ Infrared absorbing dye (1) [the following structure] 0.30 g
Radical generator (1) [following structure] 1.62 g
-Radical polymerizable compound Tris (acryloyloxyethyl) isocyanurate (NK ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.) 1.92 g
・ Tris (2-hydroxyethyl) isocyanurate 0.62 g
・ Low molecular weight hydrophilic compound (1) [following structure] 0.50 g
・ Grease sensitizer Phosphonium compound (1) [the following structure] 0.55 g
・ Sensitizer benzyl-dimethyl-octylammonium ・ PF 6 salt 0.18g
-Sensitizing agent Ammonium group-containing polymer [structure shown below] 1.0 g
・ Fluorosurfactant (1) [The following structure] 0.08g
・ 2-butanone 10.91g
・ 55-09g of 1-methoxy-2-propanol
・ Resin fine particle aqueous dispersion (1) 20.0 g
上記の、バインダーポリマー(1)、赤外線吸収染料(1)、ラジカル発生剤(1)、ホスホニウム化合物(1)、低分子親水性化合物(1)、アンモニウム基含有ポリマー、及びフッ素系界面活性剤(1)の構造は、以下に示す通りである。 The binder polymer (1), infrared absorbing dye (1), radical generator (1), phosphonium compound (1), low molecular weight hydrophilic compound (1), ammonium group-containing polymer, and fluorosurfactant ( The structure of 1) is as shown below.
<保護層塗布液(1)>
・無機質層状化合物分散液(1) 1.5g
・ポリビニルアルコール(日本合成化学工業(株)製CKS50、スルホン酸変性、
けん化度99モル%以上、 重合度300)6質量%水溶液 0.55g
・ポリビニルアルコール((株)クラレ製PVA−405、
けん化度81.5モル%重合度500)6質量%水溶液 0.03g
・日本エマルジョン(株)製界面活性剤
(エマレックス710)1質量%水溶液 8.60g
・イオン交換水 6.0g
<Protective layer coating solution (1)>
・ Inorganic layered compound dispersion (1) 1.5 g
-Polyvinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd. CKS50, sulfonic acid modification,
Saponification degree 99 mol% or more, polymerization degree 300) 6% by mass aqueous solution 0.55 g
・ Polyvinyl alcohol (PVA-405 manufactured by Kuraray Co., Ltd.)
Degree of saponification 81.5 mol% degree of polymerization 500) 6% by weight aqueous solution 0.03 g
・ Nippon Emulsion Co., Ltd. surfactant (Emalex 710) 1 mass% aqueous solution 8.60 g
・ Ion-exchanged water 6.0g
(無機質層状化合物分散液(1)の調製)
イオン交換水193.6gに合成雲母ソマシフME−100(コープケミカル(株)製)6.4gを添加し、ホモジナイザーを用いて平均粒径(レーザー散乱法)が3μmになるまで分散した。得られた分散粒子のアスペクト比は200以上であった。
(Preparation of inorganic layered compound dispersion (1))
6.4 g of synthetic mica Somasif ME-100 (manufactured by Coop Chemical Co., Ltd.) was added to 193.6 g of ion-exchanged water, and dispersed using an homogenizer until the average particle size (laser scattering method) became 3 μm. The aspect ratio of the obtained dispersed particles was 200 or more.
〔V〕平版印刷版原版 (18)の作製
実施例1と同様に疎面化処理されたアルミニウム支持体に、 二段給電電解処理法の陽極酸化装置(第一及び第二電解部長各6m、第一及び第二給電部長各3m、第一及び第二給電極部長各2.4m)を用いて陽極酸化処理を行った。第一及び第二電解部に供給した電解液は、いずれも、硫酸濃度50g/L(アルミニウムイオンを0.5重量%含む。)、温度20℃であった。その後、スプレーによる水洗を行い得られたアルミニウム支持体(B)に実施例1と同様に下塗り層塗布液を20g/m2になるように塗布乾燥した。上記の画像記録層塗布液(1)をバー塗布した後、70℃、60秒でオーブン乾燥し、乾燥塗布量0.6g/m2の画像記録層を作製し、平版印刷版原版(18)〔実施例18用〕を得た。
[V] Preparation of lithographic printing plate precursor (18) An aluminum support subjected to a surface-roughening treatment in the same manner as in Example 1 was applied to an anodizing apparatus (first and second electrolysis section length 6 m, Anodization was performed using a length of 3 m for each of the first and second feeding portions and a length of 2.4 m for each of the first and second feeding electrode portions. The electrolytes supplied to the first and second electrolysis sections were both sulfuric acid concentration 50 g / L (containing 0.5 wt% aluminum ions) and temperature 20 ° C. Thereafter, the undercoat layer coating solution was applied and dried at 20 g / m 2 in the same manner as in Example 1 on the aluminum support (B) obtained by washing with water by spraying. The above image recording layer coating solution (1) is bar-coated, and then oven-dried at 70 ° C. for 60 seconds to produce an image recording layer having a dry coating amount of 0.6 g / m 2. The planographic printing plate precursor (18) [For Example 18] was obtained.
〔VI〕平版印刷版原版 (19)〜(21)の作製
リン酸を電解浴として陽極酸化されたアルミニウム支持体(A)に実施例1と同様に下塗り層塗布液を20g/m2になるように塗布乾燥し、下記の画像記録層塗布液(18〜20)をバー塗布した後、70℃、60秒でオーブン乾燥し、乾燥塗布量0.6g/m2の画像記録層を作製し、平版印刷版原版(19)〜(21)〔比較例1〜3用〕を得た。
[VI] Preparation of lithographic printing plate precursors (19) to (21) An undercoat layer coating solution of 20 g / m 2 is applied to an aluminum support (A) anodized using phosphoric acid as an electrolytic bath in the same manner as in Example 1. After coating and drying as described above, the following image recording layer coating solution (18 to 20) was bar coated and then oven dried at 70 ° C. for 60 seconds to produce an image recording layer having a dry coating amount of 0.6 g / m 2. The lithographic printing plate precursors (19) to (21) [for Comparative Examples 1 to 3] were obtained.
<画像記録層塗布液(18〜20)>
・樹脂微粒子水分散液(9〜11) (表1に記載) 20.0g
・赤外線吸収染料(2) 0.2g
・ラジカル発生剤 Irgacure250(チバスペシャリティケミカルズ製)
0.5g
・ラジカル重合性化合物 SR-399(サートマー社製) 1.50g
・メルカプト−3−トリアゾール 0.2g
・Byk336(Byk Chimie社製) 0.4g
・KlucelM(Hercules社製) 4.8g
・ELVACITE4026(Ineos Acrylica社製) 2.5g
・n−プロパノール 55.0g
・2−ブタノン 17.0g
<Image recording layer coating solution (18-20)>
・ Resin fine particle aqueous dispersion (9 to 11) (described in Table 1) 20.0 g
・ Infrared absorbing dye (2) 0.2g
・ Radical generator Irgacure250 (Ciba Specialty Chemicals)
0.5g
・ Radically polymerizable compound SR-399 (Sartomer) 1.50 g
・ Mercapto-3-triazole 0.2g
・ Byk336 (Byk Chimie) 0.4g
・ KlucelM (Hercules) 4.8g
・ ELVACITE4026 (Ineos Acrylica) 2.5g
・ N-propanol 55.0g
・ 2-butanone 17.0g
〔VII〕平版印刷版原版の評価 [VII] Evaluation of planographic printing plate precursor
(1)機上現像性
得られた平版印刷版原版を赤外線半導体レーザー搭載の富士フイルム(株)製Luxel PLATESETTER T−6000IIIにて、外面ドラム回転数1000rpm、レーザー出力70%、解像度2400dpiの条件で露光した。露光画像にはベタ画像及び20μmドットFMスクリーンの50%網点チャートを含むようにした。
得られた露光済み原版を現像処理することなく、(株)小森コーポレーション製印刷機LITHRONE26の版胴に取り付けた。Ecolity−2(富士フイルム(株)製)/水道水=2/98(容量比)の湿し水とValues−G(N)墨インキ(大日本インキ化学工業(株)製)とを用い、LITHRONE26の標準自動印刷スタート方法で湿し水とインキとを供給して機上現像した後、毎時10000枚の印刷速度で、特菱アート(76.5kg)紙に印刷を100枚行った。
画像記録層の未露光部の印刷機上での機上現像が完了し、非画像部にインキが転写しない状態になるまでに要した印刷用紙の枚数を機上現像性として計測した。結果を表1に示す。
(1) On-machine developability The obtained lithographic printing plate precursor was subjected to the conditions of an external drum rotation speed of 1000 rpm, a laser output of 70%, and a resolution of 2400 dpi on a Fujifilm Corp. Luxel PLANETTER T-6000III equipped with an infrared semiconductor laser. Exposed. The exposure image included a solid image and a 50% halftone dot chart of a 20 μm dot FM screen.
The obtained exposed original plate was attached to a plate cylinder of a printing machine LITHRONE 26 manufactured by Komori Corporation without developing. Equality-2 (manufactured by FUJIFILM Corporation) / tap water = 2/98 (volume ratio) dampening water and Values-G (N) black ink (manufactured by Dainippon Ink & Chemicals, Inc.) After dampening water and ink were supplied by the standard automatic printing start method of LITHRONE 26 and developed on the machine, 100 sheets were printed on Tokuhishi Art (76.5 kg) paper at a printing speed of 10,000 sheets per hour.
The number of print sheets required until the on-press development on the printing press of the unexposed portion of the image recording layer was completed and the ink was not transferred to the non-image portion was measured as on-press developability. The results are shown in Table 1.
(2)汚れ難さ
上述した機上現像性の評価を行った後、更に印刷を500枚続けた。
印刷機を一旦停止させ、1時間後に再びインキ、及び湿し水を供給して印刷を再開した時、非画像部にインキが転写しない状態になるまでに要した印刷用紙の枚数を汚れ難さとして計測した。結果を表1に示す。
(2) Stain resistance After the above-described evaluation of on-press developability, printing was continued for 500 sheets.
When the printing press is stopped once and ink and dampening water are supplied again after 1 hour and printing is resumed, it is difficult to smudge the number of print sheets required until the ink is not transferred to the non-image area. As measured. The results are shown in Table 1.
(3)耐刷性
上述した汚れ性の評価を行った後、更に印刷を続けた。印刷枚数を増やしていくと徐々に画像記録層が磨耗するため印刷物上のインキ濃度が低下した。印刷物におけるFMスクリーン50%網点の網点面積率をグレタグ濃度計で計測した値が印刷100枚目の計測値よりも5%低下したときの印刷部数を刷了枚数として耐刷性を評価した。結果を表1に示す。
(3) Printing durability After the above-described evaluation of stain resistance, printing was further continued. As the number of printed sheets was increased, the image recording layer was gradually worn out, so that the ink density on the printed material decreased. Printing durability was evaluated using the number of printed copies when the value measured by the Gretag densitometer for the 50% halftone dot area ratio of the FM screen in the printed material was 5% lower than the measured value for the 100th printed sheet. . The results are shown in Table 1.
Claims (7)
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