EP1359008A1 - Radiation-sensitive mixture and recording material using this mixture - Google Patents
Radiation-sensitive mixture and recording material using this mixture Download PDFInfo
- Publication number
- EP1359008A1 EP1359008A1 EP02100424A EP02100424A EP1359008A1 EP 1359008 A1 EP1359008 A1 EP 1359008A1 EP 02100424 A EP02100424 A EP 02100424A EP 02100424 A EP02100424 A EP 02100424A EP 1359008 A1 EP1359008 A1 EP 1359008A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- meth
- acrylate
- mixture
- mixture according
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 27
- 230000005855 radiation Effects 0.000 title claims description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 238000007639 printing Methods 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- GDIYMWAMJKRXRE-UHFFFAOYSA-N (2z)-2-[(2e)-2-[2-chloro-3-[(z)-2-(1,3,3-trimethylindol-1-ium-2-yl)ethenyl]cyclohex-2-en-1-ylidene]ethylidene]-1,3,3-trimethylindole Chemical compound CC1(C)C2=CC=CC=C2N(C)C1=CC=C1C(Cl)=C(C=CC=2C(C3=CC=CC=C3[N+]=2C)(C)C)CCC1 GDIYMWAMJKRXRE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000012670 alkaline solution Substances 0.000 claims abstract description 4
- 239000000975 dye Substances 0.000 claims description 36
- -1 triazine compound Chemical class 0.000 claims description 32
- 229920001577 copolymer Polymers 0.000 claims description 24
- 150000003254 radicals Chemical class 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 125000000623 heterocyclic group Chemical group 0.000 claims description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 125000004953 trihalomethyl group Chemical group 0.000 claims description 5
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000838 Al alloy Inorganic materials 0.000 claims description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229940081735 acetylcellulose Drugs 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229920002301 cellulose acetate Polymers 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 2
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 claims description 2
- 229920013820 alkyl cellulose Polymers 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 claims description 2
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920001633 poly(α-methyl styrene) Polymers 0.000 claims description 2
- 229920001281 polyalkylene Polymers 0.000 claims description 2
- 229920000129 polyhexylmethacrylate Polymers 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 2
- 235000000346 sugar Nutrition 0.000 claims description 2
- 125000001302 tertiary amino group Chemical group 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims 2
- 239000003791 organic solvent mixture Substances 0.000 claims 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 239000006096 absorbing agent Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 20
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 description 8
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 8
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 7
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 4
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 4
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 4
- 125000005395 methacrylic acid group Chemical group 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 0 CN(C)*N(C)C Chemical compound CN(C)*N(C)C 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- IMHBYKMAHXWHRP-UHFFFAOYSA-N anilazine Chemical compound ClC1=CC=CC=C1NC1=NC(Cl)=NC(Cl)=N1 IMHBYKMAHXWHRP-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229940063557 methacrylate Drugs 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical class C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 2
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 2
- PTHDBHDZSMGHKF-UHFFFAOYSA-N 2-piperidin-2-ylethanol Chemical compound OCCC1CCCCN1 PTHDBHDZSMGHKF-UHFFFAOYSA-N 0.000 description 2
- 241001479434 Agfa Species 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005741 alkyl alkenyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical group NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 1
- 150000000182 1,3,5-triazines Chemical class 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- XUIYVEVRWRRDIR-UHFFFAOYSA-N 2,2,3-tris(hydroxymethyl)-3-methylbutane-1,4-diol Chemical compound OCC(C)(CO)C(CO)(CO)CO XUIYVEVRWRRDIR-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical group OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- UCEYUKWCFYVBKV-UHFFFAOYSA-N C1(CC(C=C2SC3=CC=CC=C3C=C12)=O)=O Chemical compound C1(CC(C=C2SC3=CC=CC=C3C=C12)=O)=O UCEYUKWCFYVBKV-UHFFFAOYSA-N 0.000 description 1
- 125000005915 C6-C14 aryl group Chemical group 0.000 description 1
- SHBTUGJAKBRBBJ-UHFFFAOYSA-N CCN(C(CC(N1CC)=O)=O)C1=S Chemical compound CCN(C(CC(N1CC)=O)=O)C1=S SHBTUGJAKBRBBJ-UHFFFAOYSA-N 0.000 description 1
- RVEPFSQQHDIKRE-UHFFFAOYSA-N CN(C(CC(N1C)=O)O)C1=S Chemical compound CN(C(CC(N1C)=O)O)C1=S RVEPFSQQHDIKRE-UHFFFAOYSA-N 0.000 description 1
- IUVACELPFXBLHY-UHFFFAOYSA-N CSc1nnc(SC)[s]1 Chemical compound CSc1nnc(SC)[s]1 IUVACELPFXBLHY-UHFFFAOYSA-N 0.000 description 1
- RPXUSEGLHQMSIM-UHFFFAOYSA-N CSc1nnn[n]1-c1ccccc1 Chemical compound CSc1nnn[n]1-c1ccccc1 RPXUSEGLHQMSIM-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical group [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical group OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical group C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005399 allylmethacrylate group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 239000011668 ascorbic acid Chemical group 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000386 donor Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002587 enol group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 125000005191 hydroxyalkylamino group Chemical group 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical group OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- DMVQYIHNCKYDDL-UHFFFAOYSA-N thioxanthen-1-one Chemical compound C1=CC=C2C=C3C(=O)C=CC=C3SC2=C1 DMVQYIHNCKYDDL-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- DWWMSEANWMWMCB-UHFFFAOYSA-N tribromomethylsulfonylbenzene Chemical compound BrC(Br)(Br)S(=O)(=O)C1=CC=CC=C1 DWWMSEANWMWMCB-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/04—Negative working, i.e. the non-exposed (non-imaged) areas are removed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/06—Developable by an alkaline solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/12—Developable by an organic solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
- B41C2210/264—Polyesters; Polycarbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
- B41C2210/266—Polyurethanes; Polyureas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
- B41M5/465—Infrared radiation-absorbing materials, e.g. dyes, metals, silicates, C black
Definitions
- the invention relates to a radiation sensitive (photopolymerizable) mixture with a polymeric binder, a radically photopolymerizable component, one Infrared absorber and a triazine. It continues to affect one Recording material with a support and a radiation-sensitive Layer.
- a mixture of the type mentioned is already in EP-A 0 369 645. It includes a radically polymerizable one Monomer and a photoinitiator system soluble therein, the trihalomethyl-substituted 1,3,5-triazine, a sensitizer for the triazine and an electron donor compound with a Oxidation potential greater than zero and less than that of 1,4-dimethoxy-benzene contains.
- sensitizers are coumarin, Xanthene, acridine, thiazole, thiazine, oxazine, azine, aminoketone, Methine and polymethine dyes, porphyrins, aminotriarylmethanes, Merocyanines, squarylium and pyridinium dyes called. they are particularly sensitive to radiation in the range from 350 to 700 nm. For radiation in the near IR range (700 to 1200 nm) is the Sensitivity, on the other hand, is only slight.
- EP-A 0 315 988 also describes a photopolymerizable one Mixture disclosed that for radiation in the range of 600 to 700 nm is sensitive. It includes a polymerizable, ethylenic unsaturated compound, a radical generator and a substituted one 2-phenyl-2H-naphtho [6,5,4-a, m, n] thioxanthene-1,3-dione or a substituted 3-alkoxy-2-phenyl-naphtho [6,5,4-a, m, n] thioxanthen-1-one as a sensitizer.
- EP-A 0 441 542 relates to radiation crosslinking composition with a polymer to which mono-, dioder trihalomethyl-substituted [1,3,5] triazine residues via a Bridge group are covalently bound.
- the base polymer can be made from a variety of polymers can be selected. It can for example a polyamide, a polyester, a polyurethane Polysiloxane, a phenolic resin, a polystyrene, a polyacrylate, a Polyacrylic acid, a polyacrylamide, a polyacrylonitrile Polyethylene, a polybutadiene, polyvinylpyrrolidone, polycaprolactone, Gelatin, starch or a polysaccharide.
- EP-A 0 563 925 describes a photopolymerizable mixture discloses a radically polymerizable monomer substituted 2-phenyl-4-halomethyl (or 4,6-bishalogenmethyl) - [1,3,5] triazine as well as a connection that as Sensitizer for the triazine acts. The mixture will used for the production of negative working printing plates.
- a directly imageable recording material for production of planographic printing plates is described in EP-A 1 106 381. It comprises an electrochemically roughened carrier from a special aluminum alloy and a light-sensitive layer, which is an IR absorber and a water-insoluble but alkali-soluble contains polymeric binder.
- a photosensitive layer comprises the a monomer with one or more polymerizable, substituted acrylate group / s or derivatives thereof and one Contains photopolymerization initiator.
- Preferred initiators are aromatic ketones, aromatic onium salts, organic peroxides, Hexaarylbiimidazoles, borates, metallocenes and compounds with Carbon-halogen bonds.
- the latter also include optionally further substituted [1,3,5] triazines with trihalomethyl groups.
- the light-sensitive layer can also Sensitizer dyes included.
- On the photosensitive Layer can also be a polyvinyl alcohol layer.
- the task is solved with a radiation sensitive Mixture that absorbs in the range of 700 to 1,200 nm Contains heptamethine cyanine dye and acrylate and / or Methacrylate monomers with at least one photooxidizable group.
- the present invention accordingly relates to radiation sensitive mixture which is a radical polymerizable acrylate or methacrylate monomer and / or oligomer with at least two acrylate and / or meth-acrylate groups and at least one photooxidizable group, a photoinitiator, an IR absorbing dye and an organic polymer Contains binders, and is characterized in that the IR-absorbing Dye is a heptamethine cyanine dye.
- Heptamethine cyanine dyes are preferred in which 3 Methine carbon atoms part of a 5- to 7-membered isocyclic or heterocyclic ring.
- the label "Heptamethine cyanine dyes” includes amphoteric as well as ionic Connections.
- the aromatic end groups in the dyes are preferred indole or indolium groups to which, if appropriate other rings, in particular carbocyclic rings, fused could be.
- the binder can be selected from a whole range of organic polymers. Mixtures of different binders can also be used. For example, chlorinated polyalkylenes (in particular chlorinated polyethylene and chlorinated polypropylene), poly (meth) acrylic acid alkyl esters or alkenyl esters (in particular polymethyl (meth) acrylate, polyethyl (meth) acrylate, polybutyl (meth) acrylate, polyisobutyl (meth) acrylate, Polyhexyl (meth) acrylate, poly [(2-ethylhexyl) - (meth) acrylate] and poly [allyl (meth) acrylate]), copolymers of (meth) acrylic acid alkyl esters or alkenyl esters with other copolymerizable monomers (in particular with (meth ) acrylonitrile, vinyl chloride, vinylidene chloride, styrene and / or butadiene), polyviny
- binders are the Contain carboxy groups, particularly suitable. That is in particular Copolymers with units from ⁇ , ⁇ -unsaturated carboxylic acids or Dicarboxylic acids (preferably acrylic acid, methacrylic acid, crotonic acid, Vinyl acetic acid, maleic acid or itaconic acid).
- copolymers with units of (meth) acrylic acid and Units from alkyl (meth) acrylates, allyl methacrylates and / or (Meth) acrylonitrile as well as copolymers with units Crotonic acid and units from alkyl (meth) acrylates and / or (Meth) acrylonitrile, finally also vinyl acetic acid / Alkyl (meth) acrylate copolymers.
- copolymers with units Maleic anhydride and styrene, substituted styrenes, unsaturated ethers or esters or unsaturated aliphatic Hydrocarbons, as well as those obtainable from such copolymers Esterification.
- products that come from the Implementation of hydroxyl-containing polymers with intramolecular ones Dicarboxylic anhydrides arise.
- copolymers here are polymers with units of at least 2 different Monomers are understood, including terpolymers and higher Copolymers. Polymers in which groups with acidic hydrogen atoms occur, some or all of which have activated isocyanates is implemented.
- Polymers with aliphatic or aromatic sulfonyl isocyanates or phosphinic acid isocyanates are well suited finally also polymers with aliphatic or aromatic Hydroxy groups, for example copolymers with units Hydroxyalkyl (meth) acrylates, from allyl alcohol, from hydroxystyrene or from vinyl alcohol, and epoxy resins, if one wear a sufficient number of free OH groups.
- (meth) acrylic acid is related to the present invention for "acrylic acid and / or methacrylic acid”. The same applies to (meth) acrylonitrile, - (meth) acrylate, - (meth) acrylamide etc.
- the organic polymers used as binders generally an average molecular weight Mw of 600 to 200,000, preferably 1,000 to 100,000. Also preferred are polymers that an acid number between 10 and 250, preferably from 20 to 200, or a hydroxyl number from 50 to 750, preferably from 100 to 500, exhibit.
- the proportion of binder (s) is generally 10 to 90% by weight. %, preferably 20 to 80 wt .-%, each based on the total weight of the non-volatile components of the radiation-sensitive Mixture.
- a group is said to be related with the present invention a group of the formula> N-CO-N ⁇ are understood, in which the valences on the nitrogen atoms with Hydrogen atoms or hydrocarbon residues are saturated (there should be no more than one valence on each of the two Nitrogen atoms must be saturated with a hydrogen atom). It is however, it is also possible that a valence on a nitrogen atom Binding to a carbamoyl group (i.e. a -CO-NH group) produces so that a biuret structure is created.
- Aryl radicals R are generally mononuclear or dinuclear, but preferably mononuclear. They can be substituted by (C 1 -C 5 ) alkyl or (C 1 -C 5 ) alkoxy groups. If R 1 and R 2 are alkyl or alkoxy groups, then they preferably contain 1 to 5 carbon atoms. R 3 is preferably a hydrogen atom or a methyl group.
- X 1 is preferably a straight-chain or branched aliphatic and / or cycloaliphatic radical with preferably 4 to 10 carbon atoms. In a preferred embodiment, X 2 comprises 2 to 15 carbon atoms.
- X 2 is a saturated, straight-chain or branched aliphatic and / or cycloaliphatic radical with this number of carbon atoms. Up to 5 methylene groups in these residues can be replaced by oxygen atoms.
- X 2 consists of pure hydrocarbon chains, the rest generally comprises 2 to 12, preferably 2 to 6, carbon atoms.
- X 2 can also be a cycloaliphatic group with 5 to 10 carbon atoms, in particular a cyclohexanediyl group.
- the saturated heterocyclic ring formed by D 1 , D 2 and the two nitrogen atoms generally comprises 5 to 10 ring members, in particular 6 ring members.
- the heterocyclic ring is accordingly preferably a piperazine and the radical derived therefrom is a piperazine-1,4-diyl radical.
- the radical E is an alkanediyl group which usually comprises about 2 to 6 carbon atoms.
- the divalent 5- to 7-membered, saturated, isocyclic group E is preferably a cyclohexanediyl, in particular a cyclohexane-1,4-diyl group.
- the divalent, isocyclic, aromatic group E is preferably an ortho-, meta- or para-phenylene group.
- the divalent 5- or 6-membered aromatic heterocyclic group E preferably contains nitrogen and / or sulfur atoms in the heterocyclic ring.
- c is preferably 1, ie each of the radicals in the square bracket generally contains only one polymerizable group, in particular only one (meth) acryloyloxy group.
- hydroxyalkylamines used as starting materials are diethanolamine, triethanolamine, tris- (2-hydroxypropyl) amine, Tris (2-hydroxy-butyl) amine and alkyl bis-hydroxyalkyl amines.
- esters containing are preferably hydroxyethyl (meth) acrylate, Hydroxypropyl (meth) acrylate and hydroxyisopropyl (meth) acrylate used.
- the compounds of formula II are analogous to those of Formula I prepared, being instead of reaction products Hydroxy-alkyl acrylates or alkacrylates and diisocyanates corresponding acrylic acid or alkacrylic acid glycide ester used become. Such compounds and processes for their preparation are otherwise disclosed in EP-A 0 316 706.
- X 1 , R 3 , a and b have the meaning given above in formula IV;
- X 2 represents a divalent hydrocarbon group in which up to 5 methylene groups can be replaced by oxygen atoms.
- the running number a is preferably 0 or 1;
- i is preferably a number from 2 to 10.
- polymerizable compounds with photooxidizable groups are also reaction products of mono- or diisocyanates polyhydric alcohols in which all or part of the Hydroxy groups are esterified with (meth) acrylic acid. Products such as those resulting from the implementation of Hydroxyalkyl (meth) acrylates with diisocyanates are formed.
- Such Monomers are known and for example in DE-A 28 22 190 or DE-A 20 64 079 described.
- the mixture according to the invention can moreover photopolymerizable acrylate and / or alkacrylate compounds with 2 or more, preferably 3 to 6, acrylate and / or alkacrylate, in particular contain methacrylate groups.
- These multifunctional Connections act as crosslinkers.
- Preferred crosslinkers are (Meth) acrylates of saturated aliphatic or alicyclic, trihydric or polyhydric alcohols, such as alkanediols (specifically Ethylene glycol and propylene glycol), bis-phenol-A, trimethylolethane, Trimethylolpropane, pentamethylolpropane, pentaerythritol or Dipentaerythritol.
- ethoxylated and propoxylated trimethylolpropane tri (meth) acrylate ditrimethylolpropane tetra (meth) acrylate, Tris (2-hydroxyethyl) -isocyanurattri (meth) acrylate or glycerol tri (meth) acrylate.
- the Proportion of cross-linking acrylic and / or Alkacrylate compounds are generally up to 20% by weight, preferred 5 to 15 wt .-%, each based on the total weight of the non-volatile components of the radiation-sensitive mixture.
- the proportion of all photopolymerizable monomers or oligomers is generally 10 to 85% by weight, preferably 20 to 75% by weight, each based on the total weight of the non-volatile Components of the radiation sensitive mixture.
- the heptamethine cyanine dye preferably corresponds to one of the general formulas V or VI.
- R 3 methyl, ethyl, propyl or butyl
- R 4 H, Cl
- X - (CH 2 ) 3 - or - (CH 2 ) 2 -
- Y Br - , Cl - , I - , pTosO - , ClO 4 - , BF 4 - or PF 6 -
- the proportion of the heptamethine cyanine dye is general 0.01 to 10.0% by weight, preferably 0.5 to 8.0% by weight, in each case based on the total weight of the non-volatile components of the photopolymerizable mixture.
- Triazine compounds are well suited with at least one photolytically cleavable Trihalomethyl group, especially a trichloro or Tribromomethyl.
- the trihalomethyl groups can directly, via a conjugated double bond or via a chain of conjugated double bonds to an aromatic carbocyclic or heterocyclic ring.
- Compounds are preferred with a triazine base on the 2 Trihalomethyl groups are bound. Such connections are for example in DE 2 718 259, EP-A 0 137 452 and in EP-A 0 563,925. Basically absorb the used Triazine is not the radiation used for imaging.
- Trihalomethyltriazines can also be used, the Self absorption is below 300 nm. Such materials are particularly preferred, because the photoreactivity compared to the usual interior lighting is reduced.
- usable Trihalomethyltriazines are, for example, those which (saturated) aliphatic substituents or unsaturated substituents with only slightly extended es electron systems capable of mesomerization contain. Connections to other frameworks, for example Phenyl-trihalomethyl-sulfones (especially phenyl-tribromomethylsulfone) and phenyl-trihalogen-methyl-ketones, which are in the shorter-wave Absorb UV range can in principle also be used.
- the proportion of photoinitiator (s) is generally 0.1 to 20% by weight. preferably 1.0 to 10% by weight, in each case based on the total weight of the non-volatile components of the photopolymerizable Mixture.
- any pre-dispersed phthalocyanine pigments present primarily serve to color the mixture and the layers created with it. Their proportion is generally about 1 to 20 wt .-%, preferably about 2 to 14 wt .-%.
- Particularly suitable predispersed phthalocyanine pigments are described in DE-A 199 15 717 and DE-A 199 33 139. Are preferred especially metal-free phthalocyanine pigments.
- additives that inhibit thermally induced polymerization, hydrogen donors, Dyes, colored and colorless pigments, color formers, Filter dyes, indicator dyes, plasticizers and / or Chain transfer agent.
- additives that inhibit thermally induced polymerization, hydrogen donors, Dyes, colored and colorless pigments, color formers, Filter dyes, indicator dyes, plasticizers and / or Chain transfer agent.
- Appropriately chosen additives are those which do not absorb the radiation acting on the image.
- the radiation-sensitive mixture is appropriately in one organic solvents dissolved or dispersed and the solution or Dispersion applied to the carrier as a thin film.
- the Can be applied by pouring, spraying, dipping, applying with the help of rollers or similar, known to those skilled in the art Procedure. After drying, this is a Obtain recording material from which, for example Printing forms for high pressure, planographic printing, gravure printing or screen printing have it made. It can also be a material that is made up of Relief copies (e.g. for the production of texts in Braille), single copies, tanned images, pigment images or similar Have products structured according to the image.
- the Mixture according to the invention is also suitable for the production of Etching reserves, for example in the manufacture of PCBs or name tags can be used, as well as for molding etching. However, it is preferably used for Production of photoresist layers and printing plates.
- the present invention accordingly also relates to Recording material for the production of printing plates with a Carrier and a layer of the invention photopolymerizable mixture.
- a carrier material for printing plates are suitable foils, tapes or plates made of metal (in particular Made of aluminum or an aluminum alloy, steel, zinc or Copper) or plastic (especially polyester - especially Polyethylene terephthalate or cellulose acetate), for screen printing supports also pearl gauze.
- the surface of the Carrier of a mechanical, chemical and / or electrochemical To undergo pretreatment to ensure adhesion between the wearer and radiation-sensitive layer to adjust optimally or to achieve that the surface of the support acting imagewise Radiation less reflected (anti-halation).
- the preferred Carrier for offset printing plates is made of aluminum or an Al alloy and is electrochemically roughened on its surface, then anodized, if necessary also with a hydrophilizing agents (for example Polyvinylphosphonic acid) has been treated.
- the IR laser sources between 700 and 1200 nm familiar to the person skilled in the art are used for imagewise irradiation. Laser diodes which emit in the NIR range are preferred.
- the recording material according to the invention has a particularly high imaging performance and is therefore particularly suitable for digital imaging with NIR laser beams. In the subsequent development process, a distinction is then made precisely between non-image areas and image areas, so that the dot gain is surprisingly significantly reduced. Even small negative fonts are therefore clearly reproduced. At the same time, the material has a very high sensitivity in the NIR wavelength range.
- the cover layer can be self-supporting and removed before the subsequent development step. It then consists, for example, of a laminated polyester film. Cover layers made of a material which is soluble or dispersible in the developer liquid (at least in the non-hardened areas) can also be used.
- Suitable materials for a top layer which is completely soluble in aqueous alkaline developers are, for example, polyvinyl alcohol, polyvinyl pyrrolidone, polyphosphates, sugar, etc.
- the thickness of the top layer is generally 0.1 to 10 ⁇ m, preferably 1 to 5 ⁇ m.
- the further processing of the imagewise irradiated Recording materials are made according to the generally accepted and Methods known to those skilled in the art. This can be done imagewise before developing irradiated material can still be reheated for better To achieve networking in the irradiated areas.
- organic solvents or mixtures of organic Solvents are used, but preferred are aqueous alkaline Solutions with a pH of 8 to 14, especially from 9 to 13, up to about 20 wt.%, Preferably up to about 15 wt. %, of water-miscible organic solvents.
- the Developers can also use wetting agents, dyes, salts and / or contain other additives.
- the printing plate thus obtained was imaged with a CREO Trendsetter 3244T (2400 dpi), heated to 100 ° C. for 1 min and then with an aqueous alkaline developer (Agfa EN 231C) at 28 ° C. at a throughput speed of 1 m / min. (Agfa VSP85) developed.
- the sensitivity indicated corresponded to the laser energy in the image plane that was required to make a 50% field formed from 1x1 and 8x8 pixels appear equally bright. The value determined in this way was 18 mJ / cm 2 .
- compositions, layer weights and specific plate sensitivity used are listed in Table 1: component Examples 2 V1 V2 V3 V4 Gt Gt Gt Gt Gt A 6,900 6,904 6,904 6,904 6,904 B 3,770 - - - - C - 3,270 - - - D - - 3,270 - - e - - - 3,270 - F - - - - 3,270 G 0.163 0.163 0.163 0.163 0.163 H 6,870 6.869 6.869 6.869 6.869 6.869 6.869 6.869 6.869 I 0.408 0.408 0.408 0.408 0.408 0.408 J 0,007 0,007 0,007 0,007 K 0,680 0.679 0.679 0.679 0.679 L 20.48 20.98 20.98 20.98 20.98 M 40.72 40.72 40.72 40.72 40.72 40.72 40.72 Layer weight [g / m 2 ] 1.60 1.
- composition used The composition used, the layer weights and the specific plate sensitivities are listed in Table 2: component Examples 4 5 6 7 8 Gt Gt Gt Gt Gt A 6,430 6,430 6,430 8,090 8.110 B 0,095 - - - - C - 0,095 - - - D - - 0,101 - - e - - - 0.130 - F - - - - 0,120 G 3,310 3,310 3,310 4,170 4,170 H 6,390 6,290 6,160 7,760 7,760 I 0,238 0,238 0,238 0,238 0,300 0,300 J 0,018 0,018 0,018 0,020 0,020 K 0,600 0,600 0,600 0,760 0,760 L 17.67 17.67 17,98 51.04 51.02 M 35.35 35.35 35.48 77.74 77.74 Layer weight [g / m 2 ] 1.50 1.50 1.66 1.10 1.10 Energy value [mJ / cm 2 ] 28 38 61 43 57
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Abstract
Description
Die Erfindung betrifft ein strahlungsempfindliches (photopolymerisierbares) Gemisch mit einem polymerem Bindemittel, einer radikalisch photopolymerisierbaren Komponente, einem Infrarotabsorber und einem Triazin. Sie betrifft weiterhin ein Aufzeichnungsmaterial mit einem Träger und einer strahlungsempfindlichen Schicht.The invention relates to a radiation sensitive (photopolymerizable) mixture with a polymeric binder, a radically photopolymerizable component, one Infrared absorber and a triazine. It continues to affect one Recording material with a support and a radiation-sensitive Layer.
Ein Gemisch der eingangs genannten Art ist bereits in der EP-A 0 369 645 beschrieben. Es umfaßt ein radikalisch polymerisierbares Monomer und ein darin lösliches Photoinitiator-System, das ein trihalogenmethyl-substituiertes 1,3,5-Triazin, einen Sensibilisator für das Triazin und eine Elektronen-Donor-Verbindung mit einem Oxidationspotential von größer als Null und kleiner als dem von 1,4-Dimethoxy-benzol enthält. Als Sensibilisatoren sind Cumarin-, Xanthen-, Acridin-, Thiazol-, Thiazin-, Oxazin-, Azin-, Aminoketon-, Methin- und Polymethinfarbstoffe, Porphyrine, Aminotriarylmethane, Merocyanine, Squarylium- und Pyridiniumfarbstoffe genannt. Sie sind empfindlich insbesondere für Strahlung im Bereich von 350 bis 700 nm. Für Strahlung im nahen IR-Bereich (700 bis 1200 nm) ist die Empfindlichkeit dagegen nur gering.A mixture of the type mentioned is already in EP-A 0 369 645. It includes a radically polymerizable one Monomer and a photoinitiator system soluble therein, the trihalomethyl-substituted 1,3,5-triazine, a sensitizer for the triazine and an electron donor compound with a Oxidation potential greater than zero and less than that of 1,4-dimethoxy-benzene contains. As sensitizers are coumarin, Xanthene, acridine, thiazole, thiazine, oxazine, azine, aminoketone, Methine and polymethine dyes, porphyrins, aminotriarylmethanes, Merocyanines, squarylium and pyridinium dyes called. they are particularly sensitive to radiation in the range from 350 to 700 nm. For radiation in the near IR range (700 to 1200 nm) is the Sensitivity, on the other hand, is only slight.
Auch in der EP-A 0 315 988 ist ein photopolymerisierbares Gemisch offenbart, das für Strahlung im Bereich von 600 bis 700 nm empfindlich ist. Es umfaßt eine polymerisierbare, ethylenisch ungesättigte Verbindung, einen Radikalbildner und ein substituiertes 2-Phenyl-2H-naphtho[6,5,4-a,m,n]thioxanthen-1,3-dion oder ein substituiertes 3-Alkoxy-2-phenyl-naphtho[6,5,4-a,m,n]thioxanthen-1-on als Sensibilisator.EP-A 0 315 988 also describes a photopolymerizable one Mixture disclosed that for radiation in the range of 600 to 700 nm is sensitive. It includes a polymerizable, ethylenic unsaturated compound, a radical generator and a substituted one 2-phenyl-2H-naphtho [6,5,4-a, m, n] thioxanthene-1,3-dione or a substituted 3-alkoxy-2-phenyl-naphtho [6,5,4-a, m, n] thioxanthen-1-one as a sensitizer.
Gegenstand der EP-A 0 441 542 ist eine bei Bestrahlung vernetzende Zusammensetzung mit einem Polymer, an das mono-, dioder trihalogenmethylsubstituierte [1,3,5]Triazin-Reste über eine Brückengruppe kovalent gebunden sind. Das Basispolymer kann aus einer Vielzahl an Polymeren ausgewählt werden. Es kann beispielsweise ein Polyamid, ein Polyester, ein Polyurethan, ein Polysiloxan, ein Phenolharz, ein Polystyrol, ein Polyacrylat, eine Polyacrylsäure, ein Polyacrylamid, ein Polyacrylnitril, ein Polyethylen, ein Polybutadien, Polyvinylpyrrolidon, Polycaprolacton, Gelatine, Stärke oder ein Polysaccharid sein.EP-A 0 441 542 relates to radiation crosslinking composition with a polymer to which mono-, dioder trihalomethyl-substituted [1,3,5] triazine residues via a Bridge group are covalently bound. The base polymer can be made from a variety of polymers can be selected. It can for example a polyamide, a polyester, a polyurethane Polysiloxane, a phenolic resin, a polystyrene, a polyacrylate, a Polyacrylic acid, a polyacrylamide, a polyacrylonitrile Polyethylene, a polybutadiene, polyvinylpyrrolidone, polycaprolactone, Gelatin, starch or a polysaccharide.
In der EP-A 0 563 925 ist ein photopolymerisierbares Gemisch offenbart, das ein radikalisch polymerisierbares Monomer, ein substituiertes 2-Phenyl-4-halogen-methyl- (oder 4,6-bishalogenmethyl)-[1,3,5]triazin sowie eine Verbindung, die als Sensibilisator für das Triazin fungiert, umfaßt. Das Gemisch wird zur Herstellung von negativ-arbeitenden Druckplatten eingesetzt.EP-A 0 563 925 describes a photopolymerizable mixture discloses a radically polymerizable monomer substituted 2-phenyl-4-halomethyl (or 4,6-bishalogenmethyl) - [1,3,5] triazine as well as a connection that as Sensitizer for the triazine acts. The mixture will used for the production of negative working printing plates.
Ein direkt bebilderbares Aufzeichnungsmaterial zur Herstellung von Flachdruckplatten ist in der EP-A 1 106 381 beschrieben. Es umfaßt einen elektrochemisch aufgerauhten Träger aus einer speziellen Aluminiumlegierung und eine lichtempfindliche Schicht, die einen IR-Absorber und ein wasserunlösliches, aber alkalilösliches polymeres Bindemittel enthält.A directly imageable recording material for production of planographic printing plates is described in EP-A 1 106 381. It comprises an electrochemically roughened carrier from a special aluminum alloy and a light-sensitive layer, which is an IR absorber and a water-insoluble but alkali-soluble contains polymeric binder.
Das mit UV-, VIS- oder IR-Laserstrahlen direkt bebilderbare Aufzeichnungs-material für die Herstellung von Offsetdruckplatten gemäß der EP-A 1 091 247 umfaßt eine lichtempfindliche Schicht, die ein Monomer mit einer oder mehreren polymerisierbaren, substituierten Acrylatgruppe/n oder Derivaten davon und einem Photopolymerisationsinitiator enthält. In der α-Position zur polymerisierbaren Doppelbindung des Monomers befindet sich stets ein Heteroatom oder ein Halogenatom. Bevorzugte Initiatoren sind aromatische Ketone, aromatische Oniumsalze, organische Peroxide, Hexaarylbiimidazole, Borate, Metallocene und Verbindungen mit Kohlenstoff-Halogen-Bindungen. Zu den letztgenannten zählen auch ggf. noch weiter substituierte [1,3,5]Triazine mit Trihalogenmethyl-Gruppen. Die lichtempfindliche Schicht kann daneben noch Sensibilisator-Farbstoffe enthalten. Auf der lichtempfindlichen Schicht kann sich zusätzlich eine Polyvinylalkoholschicht befinden. Ein wesentlicher Nachteil dieses Aufzeichnungsmaterials besteht darin, daß die Monomere synthetisch nur schwer zugänglich und damit entsprechend kostspielig sind. Weiterhin ist die Reaktivität und damit die Lichtempfindlichkeit der Schicht vermindert. The one that can be directly imaged with UV, VIS or IR laser beams Recording material for the production of offset printing plates According to EP-A 1 091 247, a photosensitive layer comprises the a monomer with one or more polymerizable, substituted acrylate group / s or derivatives thereof and one Contains photopolymerization initiator. In the α position to there is always a polymerizable double bond of the monomer Hetero atom or a halogen atom. Preferred initiators are aromatic ketones, aromatic onium salts, organic peroxides, Hexaarylbiimidazoles, borates, metallocenes and compounds with Carbon-halogen bonds. The latter also include optionally further substituted [1,3,5] triazines with trihalomethyl groups. The light-sensitive layer can also Sensitizer dyes included. On the photosensitive Layer can also be a polyvinyl alcohol layer. There is a major disadvantage of this recording material in that the monomers are difficult to access synthetically and therefore are correspondingly expensive. Furthermore, the reactivity and thus reducing the light sensitivity of the layer.
Es bestand daher die Aufgabe, ein strahlungsempfindliches Gemisch sowie ein Aufzeichnungsmaterial zur Verfügung zu stellen, das auf einfache Weise zugängliche, möglichst kommerziell verfügbare Monomere enthält und eine gegenüber dem Stand der Technik verbesserte Lichtempfindlichkeit aufweist.There was therefore the task of being a radiation sensitive To provide a mixture and a recording material, that is easily accessible and as commercially available as possible Contains monomers and one compared to the prior art has improved photosensitivity.
Gelöst wird die Aufgabe mit einem strahlungsempfindlichen Gemisch, das einen im Bereich von 700 bis 1.200 nm absorbierenden Heptamethincyanin-Farbstoff enthält sowie Acrylat- und/oder Methacrylat-Monomere mit mindestens einer photooxidierbaren Gruppe.The task is solved with a radiation sensitive Mixture that absorbs in the range of 700 to 1,200 nm Contains heptamethine cyanine dye and acrylate and / or Methacrylate monomers with at least one photooxidizable group.
Gegenstand der vorliegenden Erfindung ist demgemäß ein strahlungsempfindliches Gemisch, das ein radikalisch polymerisierbares Acrylat- oder Methacrylat-Monomer und/oder-Oligomer mit mindestens zwei Acrylat- und/oder Meth-acrylatgruppen und mindestens einer photooxidierbaren Gruppe, einen Photoinitiator, einen IR-absorbierenden Farbstoff und ein organisches polymeres Bindemittel enthält, und dadurch gekennzeichnet ist, daß der IR-absorbierende Farbstoff ein Heptamethincyanin-Farbstoff ist.The present invention accordingly relates to radiation sensitive mixture which is a radical polymerizable acrylate or methacrylate monomer and / or oligomer with at least two acrylate and / or meth-acrylate groups and at least one photooxidizable group, a photoinitiator, an IR absorbing dye and an organic polymer Contains binders, and is characterized in that the IR-absorbing Dye is a heptamethine cyanine dye.
Bevorzugt sind dabei Heptamethincyanin-Farbstoffe, bei denen 3 Methin-Kohlenstoffatome Bestandteil eines 5- bis 7-gliedrigen isocyclischen oder heterocyclischen Rings sind. Die Bezeichnung "Heptamethincyanin-Farbstoffe" schließt amphotere wie auch ionische Verbindungen ein. Die aromatischen Endgruppen in den Farbstoffen sind bevorzugt Indol- bzw. Indoliumgruppen, an die gegebenenfalls noch weitere Ringe, insbesondere carbocyclische Ringe, anelliert sein können.Heptamethine cyanine dyes are preferred in which 3 Methine carbon atoms part of a 5- to 7-membered isocyclic or heterocyclic ring. The label "Heptamethine cyanine dyes" includes amphoteric as well as ionic Connections. The aromatic end groups in the dyes are preferred indole or indolium groups to which, if appropriate other rings, in particular carbocyclic rings, fused could be.
Das Bindemittel kann aus einer ganzen Reihe von organischen Polymeren ausgewählt sein. Auch Gemische verschiedener Bindemittel können zum Einsatz kommen. Geeignet sind beispielsweise chlorierte Polyalkylene (insbesondere chloriertes Polyethylen und chloriertes Polypropylen), Poly(meth)acrylsäure-alkylester oder -alkenylester (insbesondere Polymethyl(meth)acrylat, Polyethyl(meth)acrylat, Polybutyl(meth)acrylat, Polyisobutyl(meth)acrylat, Polyhexyl(meth)acrylat, Poly[(2-ethyl-hexyl)-(meth)acrylat] und Poly[allyl(meth)acrylat]), Copolymere von (Meth)acrylsäurealkylestern oder -alkenylestern mit anderen copolymerisierbaren Monomeren (insbesondere mit (Meth)acrylnitril, Vinylchlorid, Vinylidenchlorid, Styrol und/oder Butadien), Polyvinylchlorid (PVC), Vinylchlorid/Acrylnitril-Copolymere, Polyvinylidenchlorid (PVDC), Vinylidenchlorid/Acrylnitril-Copolymere, Polyvinylacetat, Polyvinylalkohol, Polyacrylnitril, Acrylnitril/Styrol-Copolymere, (Meth)acrylamid/Alkyl(meth)acrylat-Copolymere, Acrylnitril/Butadien/Styrol (ABS)-Terpolymere, Polystyrol, Poly(α-methyl-styrol), Polyamide, Polyurethane, Polyester, Methylcellulose, Ethylcellulose, Acetylcellulose, (Hydroxy-(C1-C4)alkyl)-cellulose, Carboxymethylcellulose, Polyvinylformal und Polyvinylbutyral. Besonders geeignet sind Bindemittel, die in Wasser unlöslich, in wäßrig-alkalischen Lösungen dagegen löslich oder zumindest quellbar sind. Zweckmäßigerweise werden dafür solche Polymere gewählt, die in den üblichen organischen Beschichtungslösemitteln löslich sind.The binder can be selected from a whole range of organic polymers. Mixtures of different binders can also be used. For example, chlorinated polyalkylenes (in particular chlorinated polyethylene and chlorinated polypropylene), poly (meth) acrylic acid alkyl esters or alkenyl esters (in particular polymethyl (meth) acrylate, polyethyl (meth) acrylate, polybutyl (meth) acrylate, polyisobutyl (meth) acrylate, Polyhexyl (meth) acrylate, poly [(2-ethylhexyl) - (meth) acrylate] and poly [allyl (meth) acrylate]), copolymers of (meth) acrylic acid alkyl esters or alkenyl esters with other copolymerizable monomers (in particular with (meth ) acrylonitrile, vinyl chloride, vinylidene chloride, styrene and / or butadiene), polyvinyl chloride (PVC), vinyl chloride / acrylonitrile copolymers, polyvinylidene chloride (PVDC), vinylidene chloride / acrylonitrile copolymers, polyvinyl acetate, polyvinyl alcohol, polyacrylonitrile, acrylonitrile / styrene copolymers, (meth ) acrylamide / alkyl (meth) acrylate copolymers, acrylonitrile / butadiene / styrene (ABS) terpolymers, polystyrene, poly (α-methyl-styrene), polyamides, polyurethanes, polyesters, methyl cellulose, ethyl cellulose, acetyl cellulose, (hydroxy (C 1 -C 4 ) alkyl) cellulose, carboxymethyl cellulose, polyvinyl formal and polyvinyl butyral. Particularly suitable are binders which are insoluble in water but soluble or at least swellable in aqueous alkaline solutions. For this purpose, polymers are expediently chosen which are soluble in the customary organic coating solvents.
Für die Zwecke der vorliegenden Erfindung sind Bindemittel, die Carboxygruppen enthalten, besonders geeignet. Das sind insbesondere Copolymere mit Einheiten aus α,β-ungesättigten Carbonsäuren oder Dicarbonsäuren (bevorzugt Acrylsäure, Methacrylsäure, Crotonsäure, Vinylessigsäure, Maleinsäure oder Itaconsäure). Zu nennen sind insbesondere Copolymere mit Einheiten aus (Meth)acrylsäure und Einheiten aus Alkyl(meth)acrylaten, Allylmethacrylaten und/oder (Meth)acrylnitril, daneben auch Copolymere mit Einheiten aus Crotonsäure und Einheiten aus Alkyl(meth)acrylaten und/oder (Meth)acrylnitril, schließlich auch Vinylessigsäure/ Alkyl(meth)acrylat-Copolymere. Geeignet sind daneben Copolymere mit Einheiten aus Maleinsäureanhydrid oder Maleinsäuremonoalkylestern. Dazu gehören beispielsweise Copolymere mit Einheiten aus Maleinsäureanhydrid und Styrol, substituierten Styrolen, ungesättigten Ethern oder Estern oder ungesättigten aliphatischen Kohlenwasserstoffen, sowie die aus solchen Copolymeren erhältlichen Veresterungsprodukte. Zu nennen sind weiterhin Produkte, die aus der Umsetzung von hydroxylgruppenhaltigen Polymeren mit intramolekularen Dicarbonsäureanhydriden entstehen. Unter dem Begriff "Copolymere" sollen hier Polymere mit Einheiten aus mindestens 2 verschiedenen Monomeren verstanden werden, also auch Terpolymere und höhere Mischpolymere. Verwendbar sind auch Polymere, in denen Gruppen mit aciden Wasserstoffatomen vorkommen, von denen ein Teil oder alle mit aktivierten Isocyanaten umgesetzt ist. Hierzu gehören beispielsweise Produkte, wie sie bei der Umsetzung von hydroxylgruppenhaltigen Polymeren mit aliphatischen oder aromatischen Sulfonylisocyanaten oder Phosphinsäure-isocyanaten entstehen. Gut geeignet sind schließlich auch Polymere mit aliphatischen oder aromatischen Hydroxygruppen, beispielsweise Copolymere mit Einheiten aus Hydroxyalkyl(meth)acrylaten, aus Allylalkohol, aus Hydroxystyrol oder aus Vinylalkohol, sowie Epoxyharze, sofern sie eine ausreichende Anzahl an freien OH-Gruppen tragen.For the purposes of the present invention, binders are the Contain carboxy groups, particularly suitable. That is in particular Copolymers with units from α, β-unsaturated carboxylic acids or Dicarboxylic acids (preferably acrylic acid, methacrylic acid, crotonic acid, Vinyl acetic acid, maleic acid or itaconic acid). To be mentioned in particular copolymers with units of (meth) acrylic acid and Units from alkyl (meth) acrylates, allyl methacrylates and / or (Meth) acrylonitrile, as well as copolymers with units Crotonic acid and units from alkyl (meth) acrylates and / or (Meth) acrylonitrile, finally also vinyl acetic acid / Alkyl (meth) acrylate copolymers. Copolymers with are also suitable Units of maleic anhydride or maleic acid monoalkyl esters. These include, for example, copolymers with units Maleic anhydride and styrene, substituted styrenes, unsaturated ethers or esters or unsaturated aliphatic Hydrocarbons, as well as those obtainable from such copolymers Esterification. Also to be mentioned are products that come from the Implementation of hydroxyl-containing polymers with intramolecular ones Dicarboxylic anhydrides arise. Under the term "copolymers" here are polymers with units of at least 2 different Monomers are understood, including terpolymers and higher Copolymers. Polymers in which groups with acidic hydrogen atoms occur, some or all of which have activated isocyanates is implemented. These include, for example Products such as those used in the implementation of hydroxyl groups Polymers with aliphatic or aromatic sulfonyl isocyanates or phosphinic acid isocyanates. Are well suited finally also polymers with aliphatic or aromatic Hydroxy groups, for example copolymers with units Hydroxyalkyl (meth) acrylates, from allyl alcohol, from hydroxystyrene or from vinyl alcohol, and epoxy resins, if one wear a sufficient number of free OH groups.
Der Begriff "(Meth)acrylsäure" steht im Zusammenhang mit der vorliegenden Erfindung für "Acrylsäure und/oder Methacrylsäure". Entsprechendes gilt für (Meth)acrylnitril, -(meth)acrylat,-(meth)acrylamid usw.The term "(meth) acrylic acid" is related to the present invention for "acrylic acid and / or methacrylic acid". The same applies to (meth) acrylonitrile, - (meth) acrylate, - (meth) acrylamide etc.
Die als Bindemittel eingesetzten organischen Polymere haben allgemein ein mittleres Molekulargewicht Mw von 600 bis 200.000, bevorzugt 1.000 bis 100.000. Bevorzugt sind ferner Polymere, die eine Säurezahl zwischen 10 und 250, bevorzugt von 20 bis 200, oder eine Hydroxylzahl von 50 bis 750, bevorzugt von 100 bis 500, aufweisen.The organic polymers used as binders generally an average molecular weight Mw of 600 to 200,000, preferably 1,000 to 100,000. Also preferred are polymers that an acid number between 10 and 250, preferably from 20 to 200, or a hydroxyl number from 50 to 750, preferably from 100 to 500, exhibit.
Der Anteil an Bindemittel(n) beträgt allgemein 10 bis 90 Gew.- %, bevorzugt 20 bis 80 Gew.-%, jeweils bezogen auf das Gesamtgewicht der nichtflüchtigen Bestandteile des strahlungsempfindlichen Gemisches.The proportion of binder (s) is generally 10 to 90% by weight. %, preferably 20 to 80 wt .-%, each based on the total weight of the non-volatile components of the radiation-sensitive Mixture.
Die radikalisch polymerisierbare Acrylat- oder Methacrylat-Verbindung mit mindestens einer photooxidierbaren Gruppe ist beispielsweise eine Verbindung mit einer primären, sekundären und insbesondere tertiären Aminogruppe. Besonders bevorzugt sind polymerisierbare Verbindungen, die neben einer (tertiären) Aminogruppe noch mindestens eine Harnstoff- und/oder Urethangruppe enthalten. Unter dem Begriff "Harnstoffgruppe" soll im Zusammenhang mit der vorliegenden Erfindung eine Gruppe der Formel >N-CO-N< verstanden werden, bei der die Valenzen an den Stickstoffatomen mit Wasserstoffatomen bzw. Kohlenwasserstoffresten abgesättigt sind (dabei sollte nicht mehr als eine Valenz an jedem der beiden Stickstoffatome mit einem Wasserstoffatom abgesättigt sein). Es ist jedoch auch möglich, daß eine Valenz an einem Stickstoffatom die Bindung zu einer Carbamoylgruppe (d.h. einer -CO-NH-Gruppe) herstellt, so daß eine Biuret-Struktur entsteht.The radically polymerizable acrylate or methacrylate compound with at least one photooxidizable group for example connecting to a primary, secondary and especially tertiary amino group. Are particularly preferred polymerizable compounds which, in addition to a (tertiary) Amino group or at least one urea and / or urethane group contain. The term "urea group" is said to be related with the present invention a group of the formula> N-CO-N < are understood, in which the valences on the nitrogen atoms with Hydrogen atoms or hydrocarbon residues are saturated (there should be no more than one valence on each of the two Nitrogen atoms must be saturated with a hydrogen atom). It is however, it is also possible that a valence on a nitrogen atom Binding to a carbamoyl group (i.e. a -CO-NH group) produces so that a biuret structure is created.
Daneben sind Verbindungen geeignet, die eine photooxidierbare
Amino-, Harnstoff- oder Thiogruppe, die auch Bestandteil eines
heterocyclischen Ringes sein kann, aufweisen. Verbindung mit
photooxidierbaren Enolgruppen kommen ebenfalls in Betracht. Konkrete
Beispiele für photooxidierbaren Gruppen sind Triethanolamino-,
Triphenylamino-, Thioharnstoff-, Imidazol-, Oxazol-, Thiazol-,
Acetylacetonyl-, N-Phenyl-glycin- und Ascorbinsäuregruppen.
Besonders geeignete Monomere mit photooxidierbaren Gruppen lassen
sich durch die folgende Formel I
- Q
- für -S-,
- R
- für eine (C2-C8)Alkyl-, (C2-C8)Hydroxyalkyl- oder (C6-C14)-Aryl-gruppe,
- R1 und R2
- unabhängig voneinander für ein Wasserstoffatom, eine Alkyl- oder Alkoxyalkylgruppe und
- R3
- für ein Wasserstoffatom, eine Methyl- oder Ethylgruppe steht,
- X1
- eine geradkettige oder verzweigte, gesättigte Kohlenwasserstoffgruppe mit 1 bis 12 Kohlenstoffatomen ist,
- X2
- eine (c+1)wertige Kohlenwasserstoffgruppe darstellt, in der bis zu 5 Methylengruppen durch Sauerstoffatome ersetzt sein können,
- D1 und D2
- unabhängig voneinander eine gesättigte Kohlenwasserstoffgruppe mit 1 bis 5 Kohlenstoffatomen bedeuten,
- E
- eine zweiwertige gesättigte Kohlenwasserstoffgruppe mit 2 bis 12 Kohlenstoffatomen, eine zweiwertige 5- bis 7- gliedrige, gesättigte, iso- oder heterocyclische Gruppe, wobei die heterocyclische Gruppe bis zu 2 Stickstoff-, Sauerstoff- und/oder Schwefelatome im Ring enthalten kann, eine zweiwertige, aromatische, mono- oder bicyclische, isocyclische Gruppe mit 6 bis 12 Kohlenstoffatomen oder eine zweiwertige 5- oder 6- gliedrige aromatische heterocyclische Gruppe darstellt,
- a
- eine ganze Zahl von 0 bis 4,
- b
- 0 oder 1,
- c
- eine ganze Zahl von 1 bis 3,
- m
- eine ganze Zahl von 2 bis 4 und
- n
- eine ganze Zahl von 1 bis m ist.
- Q
- for -S-,
- R
- for a (C 2 -C 8 ) alkyl, (C 2 -C 8 ) hydroxyalkyl or (C 6 -C 14 ) aryl group,
- R 1 and R 2
- independently for a hydrogen atom, an alkyl or alkoxyalkyl group and
- R 3
- represents a hydrogen atom, a methyl or ethyl group,
- X 1
- is a straight-chain or branched, saturated hydrocarbon group with 1 to 12 carbon atoms,
- X 2
- represents a (c + 1) -valent hydrocarbon group in which up to 5 methylene groups can be replaced by oxygen atoms,
- D 1 and D 2
- independently of one another represent a saturated hydrocarbon group having 1 to 5 carbon atoms,
- e
- a divalent saturated hydrocarbon group with 2 to 12 carbon atoms, a divalent 5- to 7-membered, saturated, iso- or heterocyclic group, where the heterocyclic group can contain up to 2 nitrogen, oxygen and / or sulfur atoms in the ring, a divalent represents aromatic, mono- or bicyclic, isocyclic group having 6 to 12 carbon atoms or a divalent 5- or 6-membered aromatic heterocyclic group,
- a
- an integer from 0 to 4,
- b
- 0 or 1,
- c
- an integer from 1 to 3,
- m
- an integer from 2 to 4 and
- n
- is an integer from 1 to m.
Verbindungen dieser Art sowie Verfahren zu ihrer Herstellung sind ausführlich in der EP-A 0 287 818 beschrieben. Wenn in einer Verbindung der allgemeinen Formel I mehrere Reste R oder mehrere Reste der in der eckigen Klammer angegebenen Struktur vorhanden sind, d.h. wenn (m - n) > 1 bzw. n > 1 ist, dann können diese Reste untereinander gleich oder verschieden sein. Verbindungen der Formel I, in denen n = m ist, sind besonders bevorzugt. Sämtliche Reste enthalten dann polymerisierbare Gruppen. Vorzugsweise ist die Laufzahl a = 1, bei mehreren Resten sollte a = 0 in nicht mehr als einem Rest vorkommen. Wenn R eine Alkyl- oder Hydroxyalkylgruppe ist, dann umfaßt sie allgemein 2 bis 8, insbesondere 2 bis 4, Kohlenstoffatome. Arylreste R sind allgemein ein- oder zweikernig, bevorzugt jedoch einkernig. Sie können durch (C1-C5)Alkyl- oder (C1-C5)Alkoxygruppen substituiert sein. Wenn R1 und R2 Alkyl- oder Alkoxy-gruppen sind, dann enthalten sie bevorzugt 1 bis 5 Kohlenstoffatome. R3 ist bevorzugt ein Wasserstoffatom oder eine Methylgruppe. X1 ist bevorzugt ein geradkettiger oder verzweigter aliphatischer und/oder cycloaliphatischer Rest mit vorzugsweise 4 bis 10 Kohlenstoffatomen. X2 umfaßt in einer bevorzugten Ausführungsform 2 bis 15 Kohlenstoffatome. Insbesondere handelt es sich um einen gesättigten, geradkettigen oder verzweigten aliphatischen und/oder cycloaliphatischen Rest mit dieser Anzahl an Kohlenstoffatomen. Bis zu 5 Methylengruppen in diesen Resten können durch Sauerstoffatome ersetzt sein. Besteht X2 aus reinen Kohlenwasserstoffketten, so umfaßt der Rest allgemein 2 bis 12, bevorzugt 2 bis 6 Kohlenstoffatome. X2 kann auch eine cycloaliphatische Gruppe mit 5 bis 10 Kohlenstoffatomen, insbesondere eine Cyclohexandiyl-Gruppe sein. Der durch D1, D2 und die beiden Stickstoffatome gebildete gesättigte heterocyclische Ring umfaßt allgemein 5 bis 10 Ringglieder, insbesondere 6 Ringglieder. In dem letztgenannten Fall ist der heterocyclische Ring demgemäß vorzugsweise ein Piperazin und der davon abgeleitete Rest ein Piperazin-1,4-diyl-Rest. Der Rest E ist in einer bevorzugten Ausführungsform eine Alkandiylgruppe, die gewöhnlich etwa 2 bis 6 Kohlenstoffatome umfaßt. Die zweiwertige 5- bis 7-gliedrige, gesättigte, isocyclische Gruppe E ist bevorzugt eine Cyclohexandiyl- , insbesondere eine Cyclohexan-1,4-diyl-Gruppe. Die zweiwertige, isocyclische, aromatische Gruppe E ist bevorzugt eine ortho-, metaoder para-Phenylengruppe. Die zweiwertige 5- oder 6-gliedrige aromatische heterocyclische Gruppe E schließlich enthält bevorzugt Stickstoff- und/oder Schwefelatome im heterocyclischen Ring. c ist bevorzugt 1, d.h. jeder der Reste in der eckigen Klammer enthält allgemein nur eine polymerisierbare Gruppe, insbesondere nur eine (Meth)acryloyloxygruppe.Compounds of this type and processes for their preparation are described in detail in EP-A 0 287 818. If in a compound of the general formula I there are several radicals R or several radicals of the structure given in the square brackets, ie if (m - n)> 1 or n> 1, these radicals can be identical or different from one another. Compounds of the formula I in which n = m are particularly preferred. All of the residues then contain polymerizable groups. The running number is preferably a = 1; if there are several residues, a = 0 should not occur in more than one residue. When R is an alkyl or hydroxyalkyl group, it generally comprises 2 to 8, especially 2 to 4, carbon atoms. Aryl radicals R are generally mononuclear or dinuclear, but preferably mononuclear. They can be substituted by (C 1 -C 5 ) alkyl or (C 1 -C 5 ) alkoxy groups. If R 1 and R 2 are alkyl or alkoxy groups, then they preferably contain 1 to 5 carbon atoms. R 3 is preferably a hydrogen atom or a methyl group. X 1 is preferably a straight-chain or branched aliphatic and / or cycloaliphatic radical with preferably 4 to 10 carbon atoms. In a preferred embodiment, X 2 comprises 2 to 15 carbon atoms. In particular, it is a saturated, straight-chain or branched aliphatic and / or cycloaliphatic radical with this number of carbon atoms. Up to 5 methylene groups in these residues can be replaced by oxygen atoms. If X 2 consists of pure hydrocarbon chains, the rest generally comprises 2 to 12, preferably 2 to 6, carbon atoms. X 2 can also be a cycloaliphatic group with 5 to 10 carbon atoms, in particular a cyclohexanediyl group. The saturated heterocyclic ring formed by D 1 , D 2 and the two nitrogen atoms generally comprises 5 to 10 ring members, in particular 6 ring members. In the latter case, the heterocyclic ring is accordingly preferably a piperazine and the radical derived therefrom is a piperazine-1,4-diyl radical. In a preferred embodiment, the radical E is an alkanediyl group which usually comprises about 2 to 6 carbon atoms. The divalent 5- to 7-membered, saturated, isocyclic group E is preferably a cyclohexanediyl, in particular a cyclohexane-1,4-diyl group. The divalent, isocyclic, aromatic group E is preferably an ortho-, meta- or para-phenylene group. Finally, the divalent 5- or 6-membered aromatic heterocyclic group E preferably contains nitrogen and / or sulfur atoms in the heterocyclic ring. c is preferably 1, ie each of the radicals in the square bracket generally contains only one polymerizable group, in particular only one (meth) acryloyloxy group.
Die Verbindungen der Formel I mit b = 1, die demgemäß zwei Urethangruppen in jedem der in der eckigen Klammer angegebenen Reste aufweisen, können in an sich bekannter Weise hergestellt werden durch Umsetzung von Acrylsäureestern oder Alkacrylsäureestern, die freie Hydroxygruppen enthalten, mit äquimolaren Mengen an Diisocyanaten. Überschüssige Isocyanatgruppen werden dann beispielsweise mit Tris-(hydroxyalkyl)-aminen, N,N'-Bishydroxyalkylpiperazinen oder N,N,N',N'-Tetrakishydroxylalkylalkylendiaminen, wobei jeweils einzelne Hydroxyalkylgruppen durch Alkyl- und/oder Arylgruppen R ersetzt sein können. Im Fall a = 0 liegt eine Harnstoffgruppierung vor. Beispiele für die als Ausgangsmaterialien verwendeten Hydroxyalkylamine sind Diethanolamin, Triethanolamin, Tris-(2-hydroxy-propyl)-amin, Tris-(2-hydroxy-butyl)-amin und Alkyl-bis-hydroxyalkyl-amine. Beispiele für geeignete Diisocyanate sind Hexamethylendiisocyanat, 2,2,4-Trimethyl-hexamethylen-diiso-cyanat, 1,4-Cyclohexylendiisocyanat (= 1,4-Diisocyanato-cyclohexan) und 1,1,3-Trimethyl-3-isocyanatomethyl-5-isocyanato-cyclohexan. Als Hydroxygruppen enthaltende Ester werden bevorzugt Hydroxyethyl-(meth)acrylat, Hydroxypropyl-(meth)acrylat und Hydroxyisopropyl-(meth)acrylat eingesetzt.The compounds of formula I with b = 1, accordingly two Urethane groups in each of the residues indicated in the square brackets can be produced in a manner known per se by reacting acrylic acid esters or alkacrylic acid esters, the contain free hydroxyl groups with equimolar amounts of Diisocyanates. Excess isocyanate groups are then for example with tris (hydroxyalkyl) amines, N, N'-bishydroxyalkylpiperazines or N, N, N ', N'-tetrakishydroxylalkylalkylenediamines, each one Hydroxyalkyl groups can be replaced by alkyl and / or aryl groups R. can. If a = 0, there is a urea grouping. Examples for the hydroxyalkylamines used as starting materials are diethanolamine, triethanolamine, tris- (2-hydroxypropyl) amine, Tris (2-hydroxy-butyl) amine and alkyl bis-hydroxyalkyl amines. Examples of suitable diisocyanates are hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diiso cyanate, 1,4-cyclohexylene diisocyanate (= 1,4-diisocyanatocyclohexane) and 1,1,3-trimethyl-3-isocyanatomethyl-5-isocyanatocyclohexane. As hydroxy groups esters containing are preferably hydroxyethyl (meth) acrylate, Hydroxypropyl (meth) acrylate and hydroxyisopropyl (meth) acrylate used.
Polymerisierbare Verbindungen der Formel I mit b = 0 lassen sich herstellen, indem die bereits beschriebenen Hydroxyalkylaminoverbindungen umgesetzt werden mit Isocyanatgruppen enthaltenden Acryl- oder Alkacrylsäureestern. Als Isocyanatgruppen enthaltender Ester wird dabei bevorzugt (2-Isocyanato-ethyl)-(meth)acrylat eingesetzt.Allow polymerizable compounds of formula I with b = 0 prepare yourself by using the ones already described Hydroxyalkylamino compounds are reacted with isocyanate groups containing acrylic or alkacrylic acid esters. As isocyanate groups Ester containing is preferred (2-isocyanato-ethyl) - (meth) acrylate used.
Die Verbindungen der Formel II werden analog zu denen der Formel I hergestellt, wobei anstelle von Umsetzungsprodukten aus Hydroxy-alkylacrylaten oder -alkacrylaten und Diisocyanaten die entsprechenden Acrylsäure- oder Alkacrylsäure-glycidester eingesetzt werden. Solche Verbindungen sowie Verfahren zu ihrer Herstellung sind im übrigen in der EP-A 0 316 706 offenbart.The compounds of formula II are analogous to those of Formula I prepared, being instead of reaction products Hydroxy-alkyl acrylates or alkacrylates and diisocyanates corresponding acrylic acid or alkacrylic acid glycide ester used become. Such compounds and processes for their preparation are otherwise disclosed in EP-A 0 316 706.
Polymerisierbare Verbindungen mit photooxidierbaren Gruppen der
Formel II
Als polymerisierbare Verbindungen mit photooxidierbaren Gruppen
lassen sich ferner Acryl- und Alkacrylsäureester der Formel IV
- Q' =
-
- X1'
- für -CiH2i - oder -CiH2i-1-O-CO-NH(-X1-NH-CO-O)b-X2-O-CO- CR3=CH2 steht,
- D3
- eine gesättigte Kohlenwasserstoffgruppe mit 4 bis 8 Kohlenstoffatomen, die mit dem Stickstoffatom einen 5- oder 6- gliedrigen Heterocyclus bildet,
- Z
- ein Wasserstoffatom oder einen Rest der Formel CkH2k-O-CO-NH(-X1-NH-CO-O)b-X2-O-CO-CR3=CH2 darstellt,
- i und k
- unabhängig voneinander ganze Zahlen von 1 bis 12 sind und
- n'
- eine ganze Zahl von 1 bis 3 ist,
- Q '=
-
- X 1 '
- represents -C i H 2i - or -C i H 2i-1 -O-CO-NH (-X 1 -NH-CO-O) b -X 2 -O-CO- CR 3 = CH 2 ,
- D 3
- a saturated hydrocarbon group with 4 to 8 carbon atoms, which forms a 5- or 6-membered heterocycle with the nitrogen atom,
- Z
- represents a hydrogen atom or a radical of the formula C k H 2k -O-CO-NH (-X 1 -NH-CO-O) b -X 2 -O-CO-CR 3 = CH 2 ,
- i and k
- are independently integers from 1 to 12 and
- n '
- is an integer from 1 to 3,
X1, R3, a und b haben in der Formel IV die oben angegebene Bedeutung; X2 stellt eine zweiwertige Kohlenwasserstoffgruppe dar, in der bis zu 5 Methylengruppen durch Sauerstoffatome ersetzt sein können. Die Laufzahl a ist in dieser Formel bevorzugt 0 oder 1; i ist bevorzugt eine Zahl von 2 bis 10. Bevorzugte Reste Q sind Piperazin-1,4-diyl (D1=D2= CH2-CH2), Piperidin-1-yl (D3= [CH2]5, Z= H) und 2-(2-Hydroxy-ethyl)-piperidin-1-yl (D3=[CH2]5 , Z= CH2-CH2OH).X 1 , R 3 , a and b have the meaning given above in formula IV; X 2 represents a divalent hydrocarbon group in which up to 5 methylene groups can be replaced by oxygen atoms. In this formula, the running number a is preferably 0 or 1; i is preferably a number from 2 to 10. Preferred radicals Q are piperazin-1,4-diyl (D 1 = D 2 = CH 2 -CH 2 ), piperidin-1-yl (D 3 = [CH 2 ] 5 , Z = H) and 2- (2-hydroxyethyl) piperidin-1-yl (D 3 = [CH 2 ] 5 , Z = CH 2 -CH 2 OH).
Von den Verbindungen der Formel IV werden solche bevorzugt, die neben einer Harnstoffgruppe noch mindestens eine Urethangruppe enthalten. Unter "Harnstoffgruppe" soll wiederum die bereits weiter oben beschriebene Gruppe der Formel >N-CO-N< verstanden werden. Verbindungen der Formel IV sowie Verfahren zu ihrer Herstellung sind in der EP-A 0 355 387 offenbart.Of the compounds of formula IV, preference is given to those which in addition to a urea group, at least one urethane group contain. The "urea group" should in turn continue group of the formula> N-CO-N <described above. Compounds of formula IV and processes for their preparation are in EP-A 0 355 387.
Als polymerisierbare Verbindungen mit photooxidierbaren Gruppen sind auch Umsetzungsprodukte von Mono- oder Diisocyanaten mit mehrwertigen Alkoholen, in denen alle oder ein Teil der Hydroxygruppen mit (Meth)acrylsäure verestert sind, geeignet. Bevorzugt sind Produkte, wie sie aus der Umsetzung von Hydroxyalkyl(meth)acrylaten mit Diisocyanaten entstehen. Solche Monomere sind bekannt und beispielsweise in den DE-A 28 22 190 oder DE-A 20 64 079 beschrieben.As polymerizable compounds with photooxidizable groups are also reaction products of mono- or diisocyanates polyhydric alcohols in which all or part of the Hydroxy groups are esterified with (meth) acrylic acid. Products such as those resulting from the implementation of Hydroxyalkyl (meth) acrylates with diisocyanates are formed. Such Monomers are known and for example in DE-A 28 22 190 or DE-A 20 64 079 described.
Das erfindungsgemäße Gemisch kann darüber hinaus photopolymerisierbare Acrylat- und/oder Alkacrylat-Verbindungen mit 2 oder mehr, bevorzugt 3 bis 6, Acrylat- und/oder Alkacrylat-, insbesondere Methacrylat-Gruppen enthalten. Diese multifunktionellen Verbindungen wirken als Vernetzer. Bevorzugte Vernetzer sind (Meth)acrylate von gesättigten aliphatischen oder alicyclischen, drei- oder mehrwertigen Alkoholen, wie Alkandiolen (speziell Ethylenglykol und Propylenglykol), Bis-phenol-A, Trimethylolethan, Trimethylolpropan, Pentamethylolpropan, Pentaerythrit oder Dipentaerythrit. Das sind beispielsweise ethoxyliertes und propoxyliertes Trimethylolpropantri(meth)acrylat, Ditrimethylolpropantetra(meth)acrylat, Tris(2-hydroxyethyl)-isocyanurattri(meth)-acrylat oder Glycerin-tri(meth)acrylat. Der Anteil der vernetzend wirkenden Acrylat- und/oder Alkacrylatverbindungen beträgt allgemein bis zu 20 Gew.-%, bevorzugt 5 bis 15 Gew.-%, jeweils bezogen auf das Gesamtgewicht der nichtflüchtigen Bestandteile des strahlungsempfindlichen Gemisches.The mixture according to the invention can moreover photopolymerizable acrylate and / or alkacrylate compounds with 2 or more, preferably 3 to 6, acrylate and / or alkacrylate, in particular contain methacrylate groups. These multifunctional Connections act as crosslinkers. Preferred crosslinkers are (Meth) acrylates of saturated aliphatic or alicyclic, trihydric or polyhydric alcohols, such as alkanediols (specifically Ethylene glycol and propylene glycol), bis-phenol-A, trimethylolethane, Trimethylolpropane, pentamethylolpropane, pentaerythritol or Dipentaerythritol. These are, for example, ethoxylated and propoxylated trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, Tris (2-hydroxyethyl) -isocyanurattri (meth) acrylate or glycerol tri (meth) acrylate. The Proportion of cross-linking acrylic and / or Alkacrylate compounds are generally up to 20% by weight, preferred 5 to 15 wt .-%, each based on the total weight of the non-volatile components of the radiation-sensitive mixture.
Der Anteil aller photopolymerisierbaren Monomere oder Oligomere beträgt allgemein 10 bis 85 Gew.-%, bevorzugt 20 bis 75 Gew.-%, jeweils bezogen auf das Gesamtgewicht der nichtflüchtigen Bestandteile des strahlungsempfindlichen Gemisches. Dabei sind allgemein mindestens 40 Gew.-% der photopolymerisierbaren Monomere und/oder Oligomere solche mit photooxidierbaren Gruppen.The proportion of all photopolymerizable monomers or oligomers is generally 10 to 85% by weight, preferably 20 to 75% by weight, each based on the total weight of the non-volatile Components of the radiation sensitive mixture. Are generally at least 40% by weight of the photopolymerizable monomers and / or oligomers those with photooxidizable groups.
Der Heptamethincyanin-Farbstoff entspricht vorzugsweise einer
der allgemeinen Formeln V oder VI.
R3=Methyl, Ethyl, Propyl oder Butyl
R 3 = methyl, ethyl, propyl or butyl
Struktur und Nomenklatur von Cyanin-Farbstoffen sind u. a. bei H. Zollinger, Color Chemistry, VCH, Weinheim 1991 Nomenklatur beschrieben. Structure and nomenclature of cyanine dyes are u. a. at H. Zollinger, Color Chemistry, VCH, Weinheim 1991 nomenclature described.
Der Anteil des Heptamethincyanin-Farbstoffs beträgt allgemein 0,01 bis 10,0 Gew.-%, bevorzugt 0,5 bis 8,0 Gew.-%, jeweils bezogen auf das Gesamtgewicht der nichtflüchtigen Bestandteile des photopolymerisierbaren Gemisches.The proportion of the heptamethine cyanine dye is general 0.01 to 10.0% by weight, preferably 0.5 to 8.0% by weight, in each case based on the total weight of the non-volatile components of the photopolymerizable mixture.
Die in dem erfindungsgemäßen Gemisch eingesetzen Photoinitiatoren sind an sich bekannt. Gut geeignet sind TriazinVerbindungen mit mindestens einer photolytisch spaltbaren Trihalogenmethylgruppe, insbesondere einer Trichlor- oder Tribrommethylgruppe. Die Trihalogenmethylgruppen können dabei direkt, über eine konjugierte Doppelbindung oder über eine Kette von konjugierten Doppelbindungen an einen aromatischen carbocyclischen oder heterocylischen Ring gebunden sein. Bevorzugt sind Verbindungen mit einem Triazin-Grundkörper an den insbesondere 2 Trihalogenmethylgruppen gebunden sind. Solche Verbindungen sind beispielsweise in der DE 2 718 259, EP-A 0 137 452 und in der EP-A 0 563 925 offenbart. Grundsätzlich absorbieren die verwendeten Triazine die zur Bebilderung verwendete Strahlung nicht. Deshalb können auch Trihalogenmethyltriazine zum Einsatz kommen, deren Eigenabsorption unter 300 nm liegt. Solche Materialien sind besonders bevorzugt, weil dadurch die Photoreaktivität gegenüber den üblichen Innenraumbeleuchtungen reduziert ist. Verwendbare Trihalogenmethyltriazine sind beispielsweise solche, die (gesättigte) aliphatische Substituenten oder ungesättigte Substituenten mit nur wenig ausgedehnten mesomeriefähigen Π-Elektronensystemen enthalten. Verbindungen mit anderen Grundgerüsten, beispielsweise Phenyl-trihalogen-methyl-sulfone (insbesondere Phenyl-tribrommethylsulfon) und Phenyl-trihalogen-methyl-ketone, die im kürzerwelligen UV-Bereich absorbieren, sind prinzipiell ebenso verwendbar. Der Anteil an Photoinitiator(en) liegt allgemein bei 0,1 bis 20 Gew.-%, bevorzugt 1,0 bis 10 Gew.-%, jeweils bezogen auf das Gesamtgewicht der nichtflüchtigen Bestandteile des photopolymerisierbaren Gemisches.The used in the mixture according to the invention Photoinitiators are known per se. Triazine compounds are well suited with at least one photolytically cleavable Trihalomethyl group, especially a trichloro or Tribromomethyl. The trihalomethyl groups can directly, via a conjugated double bond or via a chain of conjugated double bonds to an aromatic carbocyclic or heterocyclic ring. Compounds are preferred with a triazine base on the 2 Trihalomethyl groups are bound. Such connections are for example in DE 2 718 259, EP-A 0 137 452 and in EP-A 0 563,925. Basically absorb the used Triazine is not the radiation used for imaging. Therefore trihalomethyltriazines can also be used, the Self absorption is below 300 nm. Such materials are particularly preferred, because the photoreactivity compared to the usual interior lighting is reduced. usable Trihalomethyltriazines are, for example, those which (saturated) aliphatic substituents or unsaturated substituents with only slightly extended es electron systems capable of mesomerization contain. Connections to other frameworks, for example Phenyl-trihalomethyl-sulfones (especially phenyl-tribromomethylsulfone) and phenyl-trihalogen-methyl-ketones, which are in the shorter-wave Absorb UV range can in principle also be used. The The proportion of photoinitiator (s) is generally 0.1 to 20% by weight. preferably 1.0 to 10% by weight, in each case based on the total weight of the non-volatile components of the photopolymerizable Mixture.
Gegebenenfalls vorhandene vordisperigierte Phthalocyanin-Pigmente dienen in erster Linie zum Einfärben des Gemisches und der damit erzeugten Schichten. Ihr Anteil beträgt allgemein etwa 1 bis 20 Gew.-%, bevorzugt etwa 2 bis 14 Gew.-%. Besonders geeignete vordispergierte Phthalocyanin-Pigmente sind in den Schriften DE-A 199 15 717 und DE-A 199 33 139 offenbart. Bevorzugt sind insbesondere metallfreie Phthalocyanin-Pigmente.Any pre-dispersed phthalocyanine pigments present primarily serve to color the mixture and the layers created with it. Their proportion is generally about 1 to 20 wt .-%, preferably about 2 to 14 wt .-%. Particularly suitable predispersed phthalocyanine pigments are described in DE-A 199 15 717 and DE-A 199 33 139. Are preferred especially metal-free phthalocyanine pigments.
Um die Eigenschaften der photopolymerisierbaren Schicht noch besser an die jeweiligen Verwendungszwecke anzupassen, kann diese noch weitere Zusätze enthalten. Das sind beispielsweise Zusätze, die eine thermisch induzierte Polymerisation inhibieren, Wasserstoff-Donatoren, Farbstoffe, gefärbte und farblose Pigmente, Farbbildner, Filterfarbstoffe, Indikatorfarbstoffe, Weichmacher und/oder Kettenüberträger. Als Additive werden zweckmäßig solche gewählt, die die bildmäßig einwirkende Strahlung nicht absorbieren.To the properties of the photopolymerizable layer yet This can be better adapted to the respective purposes contain further additives. For example, these are additives that inhibit thermally induced polymerization, hydrogen donors, Dyes, colored and colorless pigments, color formers, Filter dyes, indicator dyes, plasticizers and / or Chain transfer agent. Appropriately chosen additives are those which do not absorb the radiation acting on the image.
Zur Herstellung des erfindungsgemäßen Aufzeichnungsmaterials wird das strahlungsempfindliche Gemisch zweckmäßig in einem organischen Lösemittel gelöst bzw. dispergiert und die Lösung oder Dispersion als dünner Film auf den Träger aufgebracht. Das Aufbringen kann durch Aufgießen, Sprühen, Tauchen, durch Antragen mit Hilfe von Walzen oder nach ähnlichen, dem Fachmann bekannten Verfahren erfolgen. Nach dem Trocknen wird auf diese Weise ein Aufzeichnungsmaterial erhalten, aus dem sich beispielsweise Druckformen für den Hochdruck, Flachdruck, Tiefdruck oder Siebdruck herstellen lassen. Es kann auch ein Material sein, aus dem sich Reliefkopien (z.B. für die Herstellung von Texten in Blindenschrift), Einzelkopien, Gerbbilder, Pigmentbilder oder ähnliche bildmäßig strukturierte Produkte herstellen lassen. Das erfindungsgemäße Gemisch eignet sich ferner für die Herstellung von Ätzreservagen, die beispielsweise bei der Herstellung von Leiterplatten oder von Namensschildern eingesetzt werden können, sowie für das Formteilätzen. Bevorzugt wird es jedoch eingesetzt zur Herstellung von Photoresistschichten sowie von Druckplatten.For the production of the recording material according to the invention the radiation-sensitive mixture is appropriately in one organic solvents dissolved or dispersed and the solution or Dispersion applied to the carrier as a thin film. The Can be applied by pouring, spraying, dipping, applying with the help of rollers or similar, known to those skilled in the art Procedure. After drying, this is a Obtain recording material from which, for example Printing forms for high pressure, planographic printing, gravure printing or screen printing have it made. It can also be a material that is made up of Relief copies (e.g. for the production of texts in Braille), single copies, tanned images, pigment images or similar Have products structured according to the image. The Mixture according to the invention is also suitable for the production of Etching reserves, for example in the manufacture of PCBs or name tags can be used, as well as for molding etching. However, it is preferably used for Production of photoresist layers and printing plates.
Gegenstand der vorliegenden Erfindung ist demgemäß auch ein Aufzeichnungsmaterial für die Herstellung von Druckplatten mit einem Träger und einer Schicht aus dem erfindungsgemäßen photopolymerisierbaren Gemisch. Als Trägermaterial für Druckplatten eignen sich Folien, Bänder oder Platten aus Metall (insbesondere aus Aluminium oder einer Aluminiumlegierung, aus Stahl, Zink oder Kupfer) oder Kunststoff (insbesondere Polyester - speziell Polyethylenterephthalat - oder Celluloseacetat), für Siebdruckträger auch Perlongaze. In vielen Fällen ist es günstig, die Oberfläche des Trägers einer mechanischen, chemischen und/oder elektrochemischen Vorbehandlung zu unterziehen um die Haftung zwischen Träger und strahlungsempfindlicher Schicht optimal ein-zustellen oder um zu erreichen, daß die Trägeroberfläche die bildmäßig einwirkende Strahlung weniger stark reflektiert (Lichthofschutz). Der bevorzugte Träger für Offsetdruckplatten besteht aus Aluminium oder einer Al-Legierung und ist auf seiner Oberfläche elektrochemisch aufgerauht, anschließend anodisiert, gegebenenfalls auch noch mit einem hydrophilierend wirkenden Mittel (beispielsweise Polyvinylphosphonsäure) behandelt worden.The present invention accordingly also relates to Recording material for the production of printing plates with a Carrier and a layer of the invention photopolymerizable mixture. As a carrier material for printing plates are suitable foils, tapes or plates made of metal (in particular Made of aluminum or an aluminum alloy, steel, zinc or Copper) or plastic (especially polyester - especially Polyethylene terephthalate or cellulose acetate), for screen printing supports also pearl gauze. In many cases it is convenient to have the surface of the Carrier of a mechanical, chemical and / or electrochemical To undergo pretreatment to ensure adhesion between the wearer and radiation-sensitive layer to adjust optimally or to achieve that the surface of the support acting imagewise Radiation less reflected (anti-halation). The preferred Carrier for offset printing plates is made of aluminum or an Al alloy and is electrochemically roughened on its surface, then anodized, if necessary also with a hydrophilizing agents (for example Polyvinylphosphonic acid) has been treated.
Durch die Empfindlichkeit des erfindungsgemäßen
Aufzeichnungsmaterials im nahen Infrarot(NIR)-Bereich werden zur
bildmäßigen Bestrahlung die dem Fachmann geläufigen IR-Laserquellen
zwischen 700 und 1200 nm eingesetzt. Bevorzugt sind Laserdioden, die
im NIR-Bereich emittieren.
Das erfindungsgemäße Aufzeichnungsmaterial weist eine besonders
hohe Abbildungsleistung auf und ist daher besonders für eine
digitale Bebilderung mit NIR-Laserstrahlen geeignet. Im
nachfolgenden Entwicklungsprozess wird dann exakt zwischen
Nichtbildstellen und Bildstellen differenziert, so daß der Punktzuwachs
überraschend deutlich vermindert ist. Auch kleine Negativ-Schriften
werden daher noch klar wiedergegeben. Gleichzeitig besitzt
das Material eine sehr hohe Empfindlichkeit im NIR-Wellenlängenbereich.Due to the sensitivity of the recording material according to the invention in the near infrared (NIR) range, the IR laser sources between 700 and 1200 nm familiar to the person skilled in the art are used for imagewise irradiation. Laser diodes which emit in the NIR range are preferred.
The recording material according to the invention has a particularly high imaging performance and is therefore particularly suitable for digital imaging with NIR laser beams. In the subsequent development process, a distinction is then made precisely between non-image areas and image areas, so that the dot gain is surprisingly significantly reduced. Even small negative fonts are therefore clearly reproduced. At the same time, the material has a very high sensitivity in the NIR wavelength range.
Es ist praktisch unabdingbar, die strahlungsempfindliche Schicht während der durch NIR-Strahlung induzierten Polymerisation vor der Einwirkung von Luftsauerstoff zu schützen. Das ist am einfachsten zu erreichen durch eine für Sauerstoff undurchlässige oder nur wenig durchlässige Deckschicht ("wenig durchlässig" bedeutet eine Durchlässigkeit von nicht mehr als 100 cm3 O2/m2 * d * bar, bestimmt gemäß DIN 53 380 bei 23°C), die auf die strahlungsempfindliche Schicht aufgebracht ist. Die Deckschicht kann selbsttragend sein und vor dem nachfolgenden Entwicklungsschritt abgezogen werden. Sie besteht dann beispielsweise aus einer auflaminierten Polyesterfolie. Auch Deckschichten aus einem Material, das (mindestens in den nicht gehärteten Bereichen) in der Entwicklerflüssigkeit löslich oder dispergierbar ist, können verwendet werden. Geeignete Materialien für eine in wäßrig-alkalischen Entwicklern vollflächig lösliche Deckschicht sind beispielsweise Polyvinylalkohol, Polyvinylpyrrolidon, Polyphosphate, Zucker usw. Die Dicke der Deckschicht beträgt allgemein 0,1 bis 10 µm, bevorzugt 1 bis 5µm.It is practically essential to protect the radiation-sensitive layer from the effects of atmospheric oxygen during the polymerization induced by NIR radiation. The easiest way to achieve this is to use a top layer that is impermeable to oxygen or only slightly permeable ("less permeable" means a permeability of not more than 100 cm 3 O 2 / m 2 * d * bar, determined according to DIN 53 380 at 23 ° C ), which is applied to the radiation-sensitive layer. The cover layer can be self-supporting and removed before the subsequent development step. It then consists, for example, of a laminated polyester film. Cover layers made of a material which is soluble or dispersible in the developer liquid (at least in the non-hardened areas) can also be used. Suitable materials for a top layer which is completely soluble in aqueous alkaline developers are, for example, polyvinyl alcohol, polyvinyl pyrrolidone, polyphosphates, sugar, etc. The thickness of the top layer is generally 0.1 to 10 μm, preferably 1 to 5 μm.
Die weitere Verarbeitung der bildmäßig bestrahlten Aufzeichnungsmaterialien erfolgt nach allgemein üblichen und dem Fachmann bekannten Verfahren. Vor dem Entwickeln kann das bildmäßig bestrahlte Material noch nacherwärmt werden, um eine bessere Vernetzung in den bestrahlten Bereichen zu erzielen. Zum Entwickeln selbst können organische Lösemittel oder Gemische von organischen Lösemitteln eingesetzt werden, bevorzugt sind jedoch wäßrigalkalische Lösungen mit einem pH-Wert von 8 bis 14, insbesondere von 9 bis 13, die bis zu etwa 20 Gew.-%, bevorzugt bis zu etwa 15 Gew.- %, an wassermischbaren organischen Lösemitteln enthalten können. Die Entwickler können darüber hinaus noch Netzmittel, Farbstoffe, Salze und/oder andere Zusätze enthalten. Beim Entwickeln werden die nichtbestrahlten Bereiche der Schicht entfernt, während die bestrahlten und damit gehärteten Bereiche der Schicht auf dem Träger zurückbleiben.The further processing of the imagewise irradiated Recording materials are made according to the generally accepted and Methods known to those skilled in the art. This can be done imagewise before developing irradiated material can still be reheated for better To achieve networking in the irradiated areas. To develop even organic solvents or mixtures of organic Solvents are used, but preferred are aqueous alkaline Solutions with a pH of 8 to 14, especially from 9 to 13, up to about 20 wt.%, Preferably up to about 15 wt. %, of water-miscible organic solvents. The Developers can also use wetting agents, dyes, salts and / or contain other additives. When developing the non-irradiated areas of the layer removed while the irradiated and thus hardened areas of the layer on the carrier remain.
Die nachfolgenden Beispiele illustrieren die Erfindung. "Gt" steht darin für "Gewichtsteil(e)", "Vt" für "Volumenteil(e)". Prozente sind Gewichtsprozente, soweit nicht anders angegeben oder aus dem Zusammenhang ersichtlich. The following examples illustrate the invention. "Gt" stands for "part by weight", "Vt" for "part by volume". Percentages are percentages by weight unless otherwise stated or evident from the context.
Ein Gemisch aus
- 6,92 Gt
- einer 32,8 %igen Lösung eines Methylmethacrylat-/Methacrylsäure-Copolymers (Molverhältnis von Methylmethacrylat- zu Methacryl-säure-Einheiten 4:1; Säurezahl: 110 mg KOH/g) in 2-Butanon (Viskosität der Lösung: 105 mm2/s mit Kapillarengröße 1,0 bei 25°C),
- 3,77 Gt
- einer 86,8 %igen Lösung eines Reaktionsproduktes aus 1 mol 2,2,4-Trimethyl-hexamethylendiisocyanat und 2 mol Hydroxyethyl-methacrylat (Viskosität: 3,3 mm2/s mit Kapillarengröße 1,0 bei 25°C),
- 0,16 Gt
- IR-Farbstoff FEW S0094 (= Formel VI, R1 und R2 zusammen -CH=CH-CH=CH- bedeuten, wobei R1 gemeinsam mit R2 einen sechgliederigen anellierten Ring bildet, R3 = CH3, R4 = Cl, X = (CH2)3 und Y- = pTosO
- 6,87 Gt
- Heliogenblau D 7490-Farbstoffdispersion (vgl. DE 199 33 139 A1) (9,9 %ig, Viskosität 7,0 mm2/s mit Kapillargröße 1 bei 25°C),
- 0,41 Gt
- 2,4-Bis-trichlormethyl-6-diphenyl-4-yl-[ 1,3,5]triazin,
- 0,68 Gt
- Edaplan™ LA 411 (1 %ig in ®Dowanol PM),
- 20,5 Gt
- 2-Butanon und
- 40,7 Gt
- Propylenglykolmonomethylether (®Dowanol PM)
- 6.92 pbw
- a 32.8% solution of a methyl methacrylate / methacrylic acid copolymer (molar ratio of methyl methacrylate to methacrylic acid units 4: 1; acid number: 110 mg KOH / g) in 2-butanone (viscosity of the solution: 105 mm 2 / s with capillary size 1.0 at 25 ° C),
- 3.77 pbw
- an 86.8% solution of a reaction product of 1 mol of 2,2,4-trimethyl-hexamethylene diisocyanate and 2 mol of hydroxyethyl methacrylate (viscosity: 3.3 mm 2 / s with capillary size 1.0 at 25 ° C.),
- 0.16 pbw
- IR dye FEW S0094 (= formula VI, R 1 and R 2 together mean -CH = CH-CH = CH-, where R 1 together with R 2 forms a six-membered fused ring, R 3 = CH 3 , R 4 = Cl , X = (CH 2 ) 3 and Y - = pTosO
- 6.87 pbw
- Heliogen blue D 7490 dye dispersion (see DE 199 33 139 A1) (9.9%, viscosity 7.0 mm 2 / s with capillary size 1 at 25 ° C),
- 0.41 pbw
- 2,4-bis-trichloromethyl-6-diphenyl-4-yl- [1,3,5] triazine,
- 0.68 pbw
- Edaplan ™ LA 411 (1% in ®Dowanol PM),
- 20.5 pbw
- 2-butanone and
- 40.7 pbw
- Propylene glycol monomethyl ether (®Dowanol PM)
Die so erhaltene Druckplatte wurde mit einem CREO Trendsetter 3244T (2400 dpi) bebildert, 1 min auf 100°C erwärmt und danach mit einem wäßrig-alkalischen Entwickler (Agfa EN 231C) bei 28°C mit einer Durchlaufgeschwindigkeit von 1 m/min. (Agfa VSP85) entwickelt. Die angegebene Empfindlichkeit entsprach derjenigen Laserenergie in der Bildebene, die erforderlich war, um ein 50 %-Feld gebildet aus 1x1- und 8x8-Bildpunkten gleich hell erscheinen zu lassen. Der auf diese Weise bestimmte Wert betrug 18 mJ/cm2.The printing plate thus obtained was imaged with a CREO Trendsetter 3244T (2400 dpi), heated to 100 ° C. for 1 min and then with an aqueous alkaline developer (Agfa EN 231C) at 28 ° C. at a throughput speed of 1 m / min. (Agfa VSP85) developed. The sensitivity indicated corresponded to the laser energy in the image plane that was required to make a 50% field formed from 1x1 and 8x8 pixels appear equally bright. The value determined in this way was 18 mJ / cm 2 .
Wie in Beispiel 1 beschrieben wurden weitere Druckplatten hergestellt, wobei für die IR-empfindliche Schicht folgende Komponenten verwendet wurden:
- A
- eine 32,8 %ige Lösung eines Methylmethacrylat/Methacrylsäure-Copolymers (Molverhältnis von Methylmethacrylat- zu Methacrylsäure-Einheiten 4:1; Säurezahl: 110 mg KOH/g) in 2-Butanon (Viskosität 105 mm2/s bei Kapillarengröße 1,0 und 25°C)
- B
- eine 86,8 %ige Lösung eines Reaktionsproduktes aus 1 mol 2,2,4-Trimethyl-hexamethylendiisocyanat und 2 Mol Hydroxyethylmethacrylat (Viskosität 3,3 mm2/s bei Kapillarengröße 1,0 und 25°C)
- C
- Dipentaerythritpentaacrylat (Cray Valey SR 399)
- D
- ethoxyliertes Trimethylolpropantriacrylat (Cray Valey SR 454)
- E
- Trimethylolpropantriacrylat
- F
- Bisphenol-A-dimethacrylat
- G
- R-Farbstoff FEW S0094 (= Formel VI, R und R zusammen -CH=CH-CH=CH- bedeuten, wobei R1 gemeinsam mit R2 einen sechgliederigen anellierten Ring bildet, R3 = CH3, R4 = Cl, X = (CH2)3 und Y =pTosO (= para-toluolsulfonat))
- H
- Heliogenblau D 7490-Farbstoffdispersion (vgl. DE 199 33 139 A1) (9,9 %ig, Viskosität 7,0 mm2/s mit Kapillargröße 1,0 bei 25°C)
- I
- 2,4-Bis-trichlormethyl-6-diphenyl-4-yl-[1,3,5]triazin
- J
- 2-Mercapto-benzothiazol
- K
- Edaplan™ LA 411 (1 %ig in ®Dowanol PM)
- L
- 2-Butanon
- M
- Propylenglykol-monomethylether (®Dowanol PM)
- A
- a 32.8% solution of a methyl methacrylate / methacrylic acid copolymer (molar ratio of methyl methacrylate to methacrylic acid units 4: 1; acid number: 110 mg KOH / g) in 2-butanone (viscosity 105 mm 2 / s with capillary size 1.0 and 25 ° C)
- B
- an 86.8% solution of a reaction product of 1 mol 2,2,4-trimethyl-hexamethylene diisocyanate and 2 mol hydroxyethyl methacrylate (viscosity 3.3 mm 2 / s with capillary size 1.0 and 25 ° C)
- C
- Dipentaerythritol pentaacrylate (Cray Valey SR 399)
- D
- ethoxylated trimethylolpropane triacrylate (Cray Valey SR 454)
- e
- trimethylolpropane
- F
- Bisphenol A dimethacrylate
- G
- R dye FEW S0094 (= formula VI, R and R together mean -CH = CH-CH = CH-, where R 1 together with R 2 forms a six-membered fused ring, R 3 = CH 3 , R 4 = Cl, X = (CH 2 ) 3 and Y = pTosO (= para-toluenesulfonate))
- H
- Heliogen blue D 7490 dye dispersion (see DE 199 33 139 A1) (9.9%, viscosity 7.0 mm 2 / s with capillary size 1.0 at 25 ° C)
- I
- 2,4-bis-trichloromethyl-6-diphenyl-4-yl- [1,3,5] triazine
- J
- 2-mercaptobenzothiazole
- K
- Edaplan ™ LA 411 (1% in ®Dowanol PM)
- L
- 2-butanone
- M
- Propylene glycol monomethyl ether (®Dowanol PM)
Die jeweils verwendete Zusammensetzung, Schichtgewichte und
bestimmte Plattenempfindlichkeit sind in Tabelle 1 aufgelistet:
Aus einem Gemisch von
- 2,92 Gt
- einer 32,8 %igen Lösung eines Methylmethacrylat/Methacrylsäure-Copolymers (Molverhältnis von Methylmethacrylat- zu Methacrylsäure-Einheiten 4:1; Säurezahl: 110 mg KOH/g) in 2- Butanon (Viskosität 105 mm2/s bei Kapillarengröße 1,0 und 25°C),
- 6,99 Gt
- einer 28,9 %igen Lösung eines Reaktionsproduktes aus 1 mol Hexamethylendiisocyanat, 1 mol Hydroxyethylmethacrylat und 0,5 mol 2-(2- Hydroxyethyl)-piperidin (Viskosität 1.7 mm2/s mit Kapillarengröße 1,0 bei 25°C),
- 0,10 Gt
- IR-Farbstoff FEW S0094 (= Formel VI, R1 und R2 zusammen -CH=CH-CH=CH- bedeuten, wobei R1 gemeinsam mit R2 einen sechgliederigen anellierten Ring bildet, R3 = CH3, R4=Cl, X=(CH2)3 und Y- = pTosO-),
- 3,37 Gt
- Heliogenblau D 7490-Farbstoffdispersion (vgl. DE 199 33 139 A1) (9,9 %ig, Viskosität 7,0 mm2/s mit Kapillargröße 1,0 bei 25°C),
- 0,41 Gt
- 2,4-Bis-trichlormethyl-6-diphenyl-4-yl- [1,3,5]triazin,
- 0,67 Gt
- Edaplan™ LA 411 (1 %ig in ®Dowanol PM),
- 19,4 Gt
- 2-Butanon und
- 36,1 Gt
- Propylenglykolmonomethylether (®Dowanol PM)
- 2.92 Gt
- a 32.8% solution of a methyl methacrylate / methacrylic acid copolymer (molar ratio of methyl methacrylate to methacrylic acid units 4: 1; acid number: 110 mg KOH / g) in 2-butanone (viscosity 105 mm 2 / s with capillary size 1.0 and 25 ° C),
- 6.99 pbw
- a 28.9% solution of a reaction product consisting of 1 mol of hexamethylene diisocyanate, 1 mol of hydroxyethyl methacrylate and 0.5 mol of 2- (2-hydroxyethyl) piperidine (viscosity 1.7 mm 2 / s with capillary size 1.0 at 25 ° C.),
- 0.10 pbw
- IR dye FEW S0094 (= formula VI, R 1 and R 2 together mean -CH = CH-CH = CH-, where R 1 together with R 2 forms a six-membered fused ring, R 3 = CH 3 , R 4 = Cl , X = (CH 2 ) 3 and Y - = pTosO - ),
- 3.37 pbw
- Heliogen blue D 7490 dye dispersion (see DE 199 33 139 A1) (9.9%, viscosity 7.0 mm 2 / s with capillary size 1.0 at 25 ° C),
- 0.41 pbw
- 2,4-bis-trichloromethyl-6-diphenyl-4-yl- [1,3,5] triazine,
- 0.67 pbw
- Edaplan ™ LA 411 (1% in ®Dowanol PM),
- 19.4 pbw
- 2-butanone and
- 36.1 pbw
- Propylene glycol monomethyl ether (®Dowanol PM)
Wie im Beispiel 1 beschrieben wurden aus den folgenden Komponenten IR-empfindliche Druckplatten hergestellt:
- A
- eine 32,8 %ige Lösung eines Methylmethacrylat/Methacrylsäure-Copolymers (Molverhältnis von Methylmethacrylat- zu Methacrylsäure-Einheiten 4:1; Säurezahl: 110 mg KOH/g) in 2-Butanon (Viskosität 105 mm2/s mit Kapillarengröße 1,0 bei 25°C)
- B
- IR-Farbstoff FEW S0325 (= Formel V, R1 und R2 zusammen - CH=CH-CH=CH- bedeuten, wobei R1 gemeinsam mit R2 einen sechgliederigen anellierten Ring bildet, R = CH3, Y = N- Methylbarbituryl, X = (CH2)2)
- C
- IR-Farbstoff FEW S0507 (= Formel VI, R1, R2 = H, R3 = CH3, R4 = 1-Phenyl-5-thio-[1,2,3,4]tetrazolyl, X = (CH2)3 und Y = Chlorid
- D
- IR-Farbstoff FEW S0331 (= Formel V, R1 und R2 zusammen - CH=CH-CH=CH- bedeuten, wobei R1 gemeinsam mit R2 einen sechgliederigen anellierten Ring bildet, R = CH3, Y = N- Ethylthiobarbituryl, X = (CH2)2)
- E
- IR-Farbstoff FEW S0382 (= Formel VI, R1, R2 = H, R3 = CH3, R4 = 5-methylsulfanyl-[1,3,4]thiadiazol-2ylsulfanyl, X = (CH2)2 und Y- = ClO4-
- F
- IR-Farbstoff FEW S0367 (= Formel VI, R1, R2 = H, R3 = CH3, R = 5-methyl-sulfanyl-[1,3,4]thiadiazol-2ylsulfanyl, X = (CH2)3 und Y- = ClO4-
- G
- eine 86,8 %ige Lösung eines Reaktionsproduktes aus 1 mol 2,2,4-Trimethyl-hexamethylendiisocyanat und 2 Mol 2- Hydroxyethyl-methacrylat (Viskosität 3,3 mm2/s mit Kapillarengröße 1,0 bei 25°C)
- H
- Heliogenblau D 7490-Farbstoffdispersion (vgl. DE 199 33 139 A1) (9,9 %ig, Viskosität 7,0 mm2/s mit Kapillargröße 1,0 bei 25°C)
- I
- 2,4-Bis-trichlormethyl-6-diphenyl-4-yl-[1,3,5]triazin
- J
- 2-Mercapto-benzothiazol
- K
- ®Edaplan LA 411 (1 %ig in ®Dowanol PM)
- L
- 2-Butanon
- M
- Propylenglykolmonomethylether (®Dowanol PM)
- A
- a 32.8% solution of a methyl methacrylate / methacrylic acid copolymer (molar ratio of methyl methacrylate to methacrylic acid units 4: 1; acid number: 110 mg KOH / g) in 2-butanone (viscosity 105 mm 2 / s with capillary size 1.0 at 25 ° C)
- B
- IR dye FEW S0325 (= formula V, R 1 and R 2 together - CH = CH-CH = CH- mean, where R 1 together with R 2 forms a six-membered fused ring, R = CH 3 , Y = N-methylbarbituryl , X = (CH 2 ) 2 )
- C
- IR dye FEW S0507 (= formula VI, R 1 , R 2 = H, R 3 = CH 3 , R 4 = 1-phenyl-5-thio- [1,2,3,4] tetrazolyl, X = (CH 2 ) 3 and Y = chloride
- D
- IR dye FEW S0331 (= formula V, R 1 and R 2 together - CH = CH-CH = CH- mean, where R 1 together with R 2 forms a six-membered fused ring, R = CH 3 , Y = N-ethylthiobarbituryl , X = (CH 2 ) 2 )
- e
- IR dye FEW S0382 (= formula VI, R 1 , R 2 = H, R 3 = CH 3 , R 4 = 5-methylsulfanyl- [1,3,4] thiadiazol-2ylsulfanyl, X = (CH 2 ) 2 and Y - = ClO4 -
- F
- IR dye FEW S0367 (= formula VI, R 1 , R 2 = H, R 3 = CH 3 , R = 5-methyl-sulfanyl- [1,3,4] thiadiazol-2ylsulfanyl, X = (CH 2 ) 3 and Y - = ClO4 -
- G
- an 86.8% solution of a reaction product of 1 mol of 2,2,4-trimethyl-hexamethylene diisocyanate and 2 mol of 2-hydroxyethyl methacrylate (viscosity 3.3 mm 2 / s with capillary size 1.0 at 25 ° C.)
- H
- Heliogen blue D 7490 dye dispersion (see DE 199 33 139 A1) (9.9%, viscosity 7.0 mm 2 / s with capillary size 1.0 at 25 ° C)
- I
- 2,4-bis-trichloromethyl-6-diphenyl-4-yl- [1,3,5] triazine
- J
- 2-mercaptobenzothiazole
- K
- ®Edaplan LA 411 (1% in ®Dowanol PM)
- L
- 2-butanone
- M
- Propylene glycol monomethyl ether (®Dowanol PM)
Die jeweils verwendete Zusammensetzung, die Schichtgewichte und
die bestimmten Plattenempfindlichkeiten sind in Tabelle 2
aufgelistet:
Claims (20)
dadurch gekennzeichnet, daß der Heptamethincyanin-Farbstoff der Formel V entspricht
characterized in that the heptamethine cyanine dye corresponds to formula V.
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|---|---|---|---|
| DE50204080T DE50204080D1 (en) | 2002-04-29 | 2002-04-29 | Radiation-sensitive mixture, recording material produced therewith, and method of making a printing plate |
| EP20020100424 EP1359008B1 (en) | 2002-04-29 | 2002-04-29 | Radiation-sensitive mixture, recording material using this mixture, and method for preparing a printing plate |
| US10/425,158 US7314699B2 (en) | 2002-04-29 | 2003-04-29 | Radiation-sensitive mixture and recording material produced therewith |
| JP2003125528A JP2003344997A (en) | 2002-04-29 | 2003-04-30 | Radiation-sensitive mixture and recording material produced therewith |
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| EP20020100424 EP1359008B1 (en) | 2002-04-29 | 2002-04-29 | Radiation-sensitive mixture, recording material using this mixture, and method for preparing a printing plate |
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|---|---|
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| EP1359008B1 EP1359008B1 (en) | 2005-08-31 |
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| Country | Link |
|---|---|
| EP (1) | EP1359008B1 (en) |
| JP (1) | JP2003344997A (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| DE50204080D1 (en) | 2005-10-06 |
| EP1359008B1 (en) | 2005-08-31 |
| JP2003344997A (en) | 2003-12-03 |
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