EP0867278A1 - Radiation sensitive composition and registration materials for lithographic printing plates prepared therewith - Google Patents
Radiation sensitive composition and registration materials for lithographic printing plates prepared therewith Download PDFInfo
- Publication number
- EP0867278A1 EP0867278A1 EP98105080A EP98105080A EP0867278A1 EP 0867278 A1 EP0867278 A1 EP 0867278A1 EP 98105080 A EP98105080 A EP 98105080A EP 98105080 A EP98105080 A EP 98105080A EP 0867278 A1 EP0867278 A1 EP 0867278A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- radiation
- carbon black
- mixture according
- groups
- black pigment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000005855 radiation Effects 0.000 title claims abstract description 35
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 title claims abstract description 23
- 238000007639 printing Methods 0.000 title claims abstract description 12
- 239000006229 carbon black Substances 0.000 claims abstract description 29
- 239000006185 dispersion Substances 0.000 claims abstract description 23
- 239000000049 pigment Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 239000011164 primary particle Substances 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 3
- 230000002378 acidificating effect Effects 0.000 claims description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000012954 diazonium Substances 0.000 claims description 2
- 150000001989 diazonium salts Chemical class 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 125000001841 imino group Chemical group [H]N=* 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 235000019241 carbon black Nutrition 0.000 description 23
- 238000011161 development Methods 0.000 description 12
- 230000018109 developmental process Effects 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- 229920003986 novolac Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- -1 hexafluorophosphates Chemical class 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000004071 soot Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HZBSQYSUONRRMW-UHFFFAOYSA-N (2-hydroxyphenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1O HZBSQYSUONRRMW-UHFFFAOYSA-N 0.000 description 2
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 2
- NQRAOOGLFRBSHM-UHFFFAOYSA-N 2-methyl-n-(4-sulfamoylphenyl)prop-2-enamide Chemical compound CC(=C)C(=O)NC1=CC=C(S(N)(=O)=O)C=C1 NQRAOOGLFRBSHM-UHFFFAOYSA-N 0.000 description 2
- CGEIYOQNYWDIOS-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenyl)-2-methylbut-2-enamide Chemical compound NC(=O)C(C)=CCC1=CC(C)=C(O)C(C)=C1 CGEIYOQNYWDIOS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- POVITWJTUUJBNK-UHFFFAOYSA-N n-(4-hydroxyphenyl)prop-2-enamide Chemical compound OC1=CC=C(NC(=O)C=C)C=C1 POVITWJTUUJBNK-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- GBQZZLQKUYLGFT-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O GBQZZLQKUYLGFT-UHFFFAOYSA-N 0.000 description 1
- IUSXXDHQFMPZQX-UHFFFAOYSA-N (2-hydroxyphenyl) prop-2-enoate Chemical compound OC1=CC=CC=C1OC(=O)C=C IUSXXDHQFMPZQX-UHFFFAOYSA-N 0.000 description 1
- ZRDYULMDEGRWRC-UHFFFAOYSA-N (4-hydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O ZRDYULMDEGRWRC-UHFFFAOYSA-N 0.000 description 1
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- OTUWCEXPLFPTPA-UHFFFAOYSA-N 2-(4-hydroxyphenyl)prop-2-enamide Chemical compound NC(=O)C(=C)C1=CC=C(O)C=C1 OTUWCEXPLFPTPA-UHFFFAOYSA-N 0.000 description 1
- OAMWSNHFGXVRAV-UHFFFAOYSA-N 2-methyl-3-(4-sulfamoylphenyl)prop-2-enamide Chemical compound NC(=O)C(C)=CC1=CC=C(S(N)(=O)=O)C=C1 OAMWSNHFGXVRAV-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- VISOTGQYFFULBK-UHFFFAOYSA-N 3-hydroxy-4-phenylpyrrole-2,5-dione Chemical compound O=C1C(=O)NC(O)=C1C1=CC=CC=C1 VISOTGQYFFULBK-UHFFFAOYSA-N 0.000 description 1
- JCYPECIVGRXBMO-UHFFFAOYSA-N 4-(dimethylamino)azobenzene Chemical compound C1=CC(N(C)C)=CC=C1N=NC1=CC=CC=C1 JCYPECIVGRXBMO-UHFFFAOYSA-N 0.000 description 1
- HAGVXVSNIARVIZ-UHFFFAOYSA-N 4-chlorosulfonyl-2-diazonionaphthalen-1-olate Chemical compound C1=CC=C2C([O-])=C([N+]#N)C=C(S(Cl)(=O)=O)C2=C1 HAGVXVSNIARVIZ-UHFFFAOYSA-N 0.000 description 1
- ZRDSGWXWQNSQAN-UHFFFAOYSA-N 6-diazo-n-phenylcyclohexa-2,4-dien-1-amine Chemical class [N-]=[N+]=C1C=CC=CC1NC1=CC=CC=C1 ZRDSGWXWQNSQAN-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- WFVRYQQSGLPHGF-UHFFFAOYSA-N bis(2,3,4-trihydroxyphenyl)methanone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O WFVRYQQSGLPHGF-UHFFFAOYSA-N 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- OCJGAAJDXODLCX-UHFFFAOYSA-N n,n-dimethyl-2-phenyldiazenylaniline Chemical compound CN(C)C1=CC=CC=C1N=NC1=CC=CC=C1 OCJGAAJDXODLCX-UHFFFAOYSA-N 0.000 description 1
- RINSWHLCRAFXEY-UHFFFAOYSA-N n-(4-sulfamoylphenyl)prop-2-enamide Chemical compound NS(=O)(=O)C1=CC=C(NC(=O)C=C)C=C1 RINSWHLCRAFXEY-UHFFFAOYSA-N 0.000 description 1
- RMWQBWIPOMZVKK-UHFFFAOYSA-N n-[(4-hydroxy-3,5-dimethylphenyl)methyl]prop-2-enamide Chemical compound CC1=CC(CNC(=O)C=C)=CC(C)=C1O RMWQBWIPOMZVKK-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- SQHKKVDREPFJLB-UHFFFAOYSA-N phenyl-(2-propan-2-ylphenyl)methanone Chemical compound CC(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 SQHKKVDREPFJLB-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000002827 triflate group Chemical class FC(S(=O)(=O)O*)(F)F 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Classifications
-
- 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
-
- 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
- B41C2210/02—Positive working, i.e. the exposed (imaged) areas are removed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/04—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
- B41C2210/20—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by inorganic additives, e.g. pigments, salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
- B41C2210/262—Phenolic condensation polymers, e.g. novolacs, resols
Definitions
- the present invention relates to a positive or negative working radiation-sensitive mixture and a recording material with a Carrier and a layer of this mixture.
- the recording material is Particularly suitable for the production of offset printing plates.
- Radiation sources used the radiation in the absorption range of the quinonediazides, i.e. in the range of about 350 to 450 nm.
- developers are aqueous alkaline Alkali silicate-based solutions in the manufacture of printing plates particularly common.
- the developed printing plates can still be used with a appropriate corrective agents are treated. If they are not immediately in the Printing press to be used is preservation with a hydrophilic Medium cheap.
- Diode lasers that emit radiation with a wavelength of approximately 800 nm
- Nd-YAG lasers that emit radiation with a wavelength of approximately 1064 nm.
- carbon as an IR absorbing component known (e.g. from WO 96/20429). Carbon absorbs IR radiation via a wide range of wavelengths.
- the use of carbon or carbon pigments in the radiation-sensitive layer of the recording materials mentioned above has so far failed because the recording materials after imagewise IR radiation not working properly with a let develop aqueous alkaline developer. The development was common incomplete, i.e. residues remained in the irradiated or unirradiated areas the radiation-sensitive layer.
- a positive or negative working radiation-sensitive mixture which is characterized in that it comprises, as an IR-absorbing component, a carbon black pigment with a primary particle size of less than 80 nm, the carbon black pigment being predispersed in a polymer which contains acidic units contains a pK a value of less than. 13
- the acidic units having a pK s of less than 13 are preferred units in which an acidic proton bound to a heteroatom.
- Particularly suitable acidic groups are therefore groups of the formula -NH 2 and -NH- as well as phenolic hydroxyl groups and carboxy groups.
- those are particularly suitable which are bonded directly to an -SO 2 - or a -CO group.
- Sulfonamide groups are particularly worth mentioning here.
- Each gram of the polymer preferably contains at least 1 mmol, particularly preferably at least 1.5 mmol, of acidic groups.
- the weight ratio of polymer with acidic units to carbon black pigment in the disperse is at least 1.
- BET surface area means that the surface area was determined by the method introduced by Brunauer, Emmet and Teller (“BET”).
- BET Brunauer, Emmet and Teller
- the average primary particle size is preferably less than 60 nm.
- the “primary particle size” is the size of the pigments as they are obtained during production (ie before dispersion).
- the radiation sensitive component in the mixture can be a diazonium salt be a combination of a photopolymerization initiator and a polymerizable Monomer (especially a monomer with a polymerizable ethylenically unsaturated group), a combination of a compound that forms acid when irradiated, and one by the photochemically generated acid fissile compound.
- the radiation-sensitive component is preferred however, an ester of a 1,2-naphthoquinone-2-diazide-4- or -5-sulfonic acid and a compound having at least one phenolic hydroxy group.
- the the latter compound preferably has at least 3 phenolic hydroxyl groups on.
- Compounds which are very particularly preferred for the esterification are which have 3 to 6 phenolic hydroxyl groups.
- Examples include 2,3,4-trihydroxy-benzophenone, 2,3,4-trihydroxy-3'-methyl-, propyl- or isopropyl-benzophenone, 2,3,4,4'-tetrahydroxy-benzophenone, 2,3,4,2 ', 4'-pentahydroxy-benzophenone, 2,3,4,2 ', 3', 4'-hexahydroxy-benzophenone and 5,5'-diacyl-2,3,4,2 ', 3', 4'-hexahydroxy-diphenylmethane.
- Amides of 1,2-naphthoquinone-2-diazide-4- or -5-sulfonic acid are also suitable.
- Usable esterification components are also condensation products from pyrogallol and aldehydes or ketones and condensation products from alkylated phenols and formaldehyde.
- the content of radiation-sensitive compounds is about 1 to 50 wt .-%, based on the total weight of the non-volatile components of the Mixture.
- polymers having acidic groups having a pK s value of less than 13 are polycondensates of phenols (such as phenol, resorcinol, a cresol, a xylenol, a trimethylphenol) or sulfamoyl- or carbamoyl-substituted aromatics with aldehydes (such as Formaldehyde) or ketones, furthermore with bismethylol-substituted ureas. Reaction products of diisocyanates with diols or diamines which have acidic units of the type mentioned are also suitable.
- polymers with units made from vinyl aromatics, N-aryl- (meth) acrylamides or aryl (meth) acrylates these units in each case one or more carboxy groups, phenolic hydroxyl groups, sulfamoyl or Have carbamoyl groups.
- polymers with Units made of (2-hydroxyphenyl) acrylate or methacrylate made of N- (4-hydroxyphenyl) acrylamide or methacrylamide, from N- (4-sulfamoylphenyl) acrylamide or -methacrylamide, from N- (4-hydroxy-3,5-dimethyl-benzyl) -acrylamide or -methacrylamide, from 4-hydroxy-styrene or from hydroxyphenyl-maleimide.
- the Polymers can also contain units from other monomers that are not acidic Own units.
- Such units are made up of units, for example Olefins or vinyl aromatics, methyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, Methacrylamide or acrylonitrile.
- (meth) acrylate for acrylate and / or methacrylate.
- the radiation-sensitive mixture also contains a polymeric binder. It is preferably the same as that for predispersion of the carbon black is used.
- the proportion of the average is generally 2 to 90% by weight, preferably 50 to 85 wt .-%, each based on the total weight of the non-volatile Components of the radiation sensitive mixture. That share includes that used for predispersion and also that added later Binder.
- the carbon blacks contained in the radiation-sensitive mixture are preferably flame, furnace or channel blacks with an average primary particle size of 80 nm or less.
- the primary particle size is preferably less than 60 nm, particularly preferably less than 30 nm.
- the BET surface area of the carbon blacks is preferably at least 30 m 2 / g.
- the carbon blacks are oxidized or post-oxidized, as a result of which acidic units form on the carbon black surface, so that the pH of an aqueous dispersion of these carbon blacks is less than 7.
- the carbon blacks predispersed in the manner described can be surprising disperse well in the radiation sensitive mixture.
- the dispersion shows furthermore improved stability.
- the proportion of soot is generally at 0.5 to 30 wt .-%, preferably at 2 to 15 wt .-%, each based on the Total weight of the non-volatile components of the mixture.
- the carbon black dispersions can be produced from the carbon blacks and the binders with acidic groups using well known devices. After a For example, the mixture is predispersed in a dissolver in a Ball mill finely dispersed. The same can be used as the solvent for this which are also used for coating (such as propylene glycol monomethyl ether, Butanone or ⁇ -butyrolactone).
- the total content of total solids in the dispersions is generally 5 to 50 wt .-%, the proportion of carbon black is preferably below the amount of binder.
- the stability of the dispersion by adding surfactants or thickeners improve. For this purpose, surfactants or thickeners are preferably selected which are contained in the aqueous-alkaline developers are soluble.
- the mixture can also contain other recording materials
- Common additives for the production of printing plates contain.
- indicator dyes for example Dialkylaminoazobenzenes
- photochemical acid generators for example trifluoromethanesulfonates or hexafluorophosphates of diazodiphenylamines
- surfactants preferably fluorine-containing surfactants or silicone surfactants
- polyalkylene oxides for control the acidity of the acidic units and small molecules with acidic units to increase the rate of development.
- Part of the present invention is also a recording material with a support and a radiation-sensitive layer, the layer consisting of the mixture according to the invention.
- the radiation sensitive mixture can also be used for other purposes, e.g. as a photoresist.
- the carrier in the recording material according to the invention is preferably one Aluminum foil or a composite of an aluminum foil and a polyester foil.
- the aluminum surface is preferably roughened, anodized and with a Compound containing at least one phosphonic acid or phosphonate unit, hydrophilized. Before roughening, degreasing and pickling with lyes as well as mechanical and / or chemical pre-roughening.
- This Carriers are then exposed to a solution of the radiation sensitive described above Mixture in an (organic) solvent or solvent mixture coated and then dried.
- the subject of the application is a method for producing a Planographic printing form in which the recording material according to the invention with infrared radiation irradiated imagewise and then with an aqueous alkaline Developer is developed at a temperature of 20 to 40 ° C.
- the developer preferably has a ratio of silicon dioxide to alkali oxide of 1 or greater than 1. This ensures that there is no damage to the anodized layer in the development process.
- Preferred alkali oxides are Na 2 0 and K 2 0 and mixtures thereof.
- the developer can contain further constituents (such as buffer substances, complexing agents, defoamers, solvents, corrosion inhibitors, dyes, surfactants and / or hydrotropes).
- Development is preferably carried out at temperatures of 20 to 40 ° C in mechanical processing plants. Alkali silicate solutions with alkali contents of 0.6 to 2.0 mol / l are used for regeneration.
- the developed plates can be briefly heated to elevated temperatures as is known for diazo layers from GB-B 1 154 749.
- the development was carried out in a conventional processor at a throughput speed of 0.4 m / min and a temperature of 28 ° C with a potassium silicate developer, the K 2 SiO 3 (normality 0.8 mol / l in water) and 0.2 wt. -% Polyglykol-1000-dicarboxylic acid and 0.4 wt .-% pelargonic acid contained.
- the recording materials produced with the predispersed carbon blacks 1-1 to 1-8 could be developed without residual layers.
- Example 1 was repeated, but with the difference that the infrared exposure was done with an outer drum imagesetter using a laser diode bar was equipped with an emission maximum at 830 nm (power each individual diode: 40 mW, writing speed: 1 m / s, beam width 10 ⁇ m).
- the development was carried out according to Example 1, the result with regard to residual layer fog was the same.
- Example 3 was repeated, but with the difference that the infrared radiation was made in an outer drum imagesetter using a laser diode bar was equipped with an emission maximum at 830 nm (power each individual diode: 40 mW, writing speed: 1.1 m / s, beam width 10 ⁇ m).
- the development was carried out as in Example 3, the result with regard to residual layer fog was the same.
- Example 3 was repeated, but with the difference that the exposure to UV light was carried out in a conventional copying frame: 5kW metal halide-doped mercury vapor lamp with an emission range of 350-450 nm, exposure dose 700 mJ / cm 2 .
- the development was carried out as in Example 3; the result regarding the residual layer veil was the same.
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
Gegenstand der vorliegenden Erfindung ist ein positiv oder negativ arbeitendes strahlungsempfindliches Gemisch sowie ein Aufzeichnungsmaterial mit einem Träger und einer Schicht aus diesem Gemisch. Das Aufzeichnungsmaterial ist insbesondere zur Herstellung von Offsetdruckplatten geeignet.The present invention relates to a positive or negative working radiation-sensitive mixture and a recording material with a Carrier and a layer of this mixture. The recording material is Particularly suitable for the production of offset printing plates.
Strahlungs- bzw. lichtempfindliche Gemische auf Basis von Naphthochinon-2-diazid-Verbindungen wie auch deren Verwendung für Aufzeichnungsmaterialien, beispielsweise in Photoresists oder in vorsensibilisierten Offsetdruckplatten, sind vielfach beschrieben. Zur (bildmäßigen) Bestrahlung dieser Materialien werden Strahlungsquellen eingesetzt, die Strahlung im Absorptionsbereich der Chinondiazide, d.h. im Bereich von etwa 350 bis 450 nm, emittieren. Auf die bildmäßige Bestrahlung folgt im allgemeinen eine Entwicklung. Als Entwickler sind wässrig-alkalische Lösungen auf Alkalisilikatbasis bei der Herstellung von Druckplatten besonders verbreitet. Die entwickelten Druckplatten können noch mit einem geeigneten Korrekturmittel behandelt werden. Wenn sie nicht unmittelbar in der Druckmaschine verwendet werden sollen, ist eine Konservierung mit einem hydrophilen Mittel günstig.Radiation- or light-sensitive mixtures based on naphthoquinone-2-diazide compounds as well as their use for recording materials, for example in photoresists or in presensitized offset printing plates described many times. For (imagewise) irradiation of these materials Radiation sources used, the radiation in the absorption range of the quinonediazides, i.e. in the range of about 350 to 450 nm. On the pictorial Irradiation generally follows development. As developers are aqueous alkaline Alkali silicate-based solutions in the manufacture of printing plates particularly common. The developed printing plates can still be used with a appropriate corrective agents are treated. If they are not immediately in the Printing press to be used is preservation with a hydrophilic Medium cheap.
Durch die Fortentwicklung der Technik stehen mittlerweile leistungsstarke und preiswerte Infrarotlichtquellen zur Verfügung, die sich für eine Direktbebilderung von Aufzeichnungsmaterialien grundsätzlich eignen. Zu nennen sind insbesondere Diodenlaser, die Strahlung mit einer Wellenlänge von etwa 800 nm emittieren, und Nd-YAG-Laser, die Strahlung einer Wellenlänge von etwa 1064 nm emittieren. Ferner ist die Verwendung von Kohlenstoff als IR-absorbierender Komponente bekannt (z.B. aus der WO 96/20429). Kohlenstoff absorbiert IR-Strahlung über einen breiten Wellenlängenbereich. Der Einsatz von Kohlenstoff oder Kohlenstoffpigmenten in der strahlungsempfindlichen Schicht der eingangs genannten Aufzeichnungsmaterialien ist bisher daran gescheitert, dass sich die Aufzeichnungsmaterialien nach der bildmäßigen IR-Bestrahlung nicht ordnungsgemäß mit einem wässrig-alkalischen Entwickler entwickeln ließen. Häufig war die Entwicklung unvollständig, d.h. in den bestrahlten bzw. unbestrahlten Bereichen blieben Reste der strahlungsempfindlichen Schicht zurück.Due to the further development of technology, powerful and Inexpensive infrared light sources are available that can be used for direct imaging of recording materials are generally suitable. Worth mentioning in particular Diode lasers that emit radiation with a wavelength of approximately 800 nm, and Nd-YAG lasers that emit radiation with a wavelength of approximately 1064 nm. Furthermore, the use of carbon as an IR absorbing component known (e.g. from WO 96/20429). Carbon absorbs IR radiation via a wide range of wavelengths. The use of carbon or carbon pigments in the radiation-sensitive layer of the recording materials mentioned above has so far failed because the recording materials after imagewise IR radiation not working properly with a let develop aqueous alkaline developer. The development was common incomplete, i.e. residues remained in the irradiated or unirradiated areas the radiation-sensitive layer.
Es bestand daher die Aufgabe, Aufzeichnungsmaterialien der eingangs genannten Art zur Verfügung zu stellen, die sich als sog. "dual-mode" - Materialien sowohl in herkömmlicher Weise (d.h. mit sichtbarem Licht und UV-Strahlung) als auch mit Infrarotstrahlung bebildern lassen. Die Bebilderung soll dabei mit verschiedenen IR-Strahlungsquellen möglich sein. Die bildmäßig bestrahlten Materialien sollen sich zudem problemlos mit üblichen, wässrig-alkalischen Lösungen entwickeln lassen.There was therefore the task of recording materials of the type mentioned Art to make available, which are known as "dual mode" materials both in conventional way (i.e. with visible light and UV radiation) as well as with Let infrared radiation be imaged. The illustration is supposed to use different IR radiation sources may be possible. The imagewise irradiated materials should also develop easily with common aqueous alkaline solutions to let.
Die Aufgabe wird gelöst durch ein positiv oder negativ arbeitendes strahlungsempfindliches Gemisch, das dadurch gekennzeichnet ist, dass es als IR-absorbierende Komponente ein Rußpigment mit einer Primärteilchengröße von weniger als 80 nm umfasst, wobei das Rußpigment vordispergiert ist in einem Polymer, das acide Einheiten mit einem pKS-Wert von kleiner als 13 enthält.The object is achieved by a positive or negative working radiation-sensitive mixture, which is characterized in that it comprises, as an IR-absorbing component, a carbon black pigment with a primary particle size of less than 80 nm, the carbon black pigment being predispersed in a polymer which contains acidic units contains a pK a value of less than. 13
Die aciden Einheiten mit einem pKs von weniger als 13 sind bevorzugt Einheiten, in denen ein saures Proton an ein Heteroatom gebunden ist. Besonders geeignete acide Gruppen sind daher Gruppen der Formel -NH2 und -NH- sowie phenolische Hydroxygruppen und Carboxygruppen. Von den -NH2- und -NH-Gruppen sind besonders solche geeignet, die direkt an eine -SO2- oder eine -CO-Gruppe gebunden sind. Besonders zu erwähnen sind hier Sulfonamidgruppen. In jedem Gramm des Polymers ist bevorzugt mindestens 1 mmol, besonders bevorzugt mindestens 1,5 mmol, an aciden Gruppen enthalten. In einer bevorzugten Ausführungsform beträgt das Gewichtsverhältnis von Polymer mit sauren Einheiten zu Rußpigment im Dispergat mindestens 1.The acidic units having a pK s of less than 13 are preferred units in which an acidic proton bound to a heteroatom. Particularly suitable acidic groups are therefore groups of the formula -NH 2 and -NH- as well as phenolic hydroxyl groups and carboxy groups. Of the -NH 2 - and -NH groups, those are particularly suitable which are bonded directly to an -SO 2 - or a -CO group. Sulfonamide groups are particularly worth mentioning here. Each gram of the polymer preferably contains at least 1 mmol, particularly preferably at least 1.5 mmol, of acidic groups. In a preferred embodiment, the weight ratio of polymer with acidic units to carbon black pigment in the disperse is at least 1.
Besonders gute Ergebnisse werden mit einem Rußpigment erzielt, das eine sogenannte BET-Oberfläche von mindestens 30 m2 pro Gramm besitzt. "BET-Oberfläche" bedeutet dabei, dass die Oberfläche nach dem von Brunauer, Emmet und Teller ("BET") eingeführten Verfahren bestimmt wurde. Die mittlere Primärteilchengröße beträgt bevorzugt weniger als 60 nm. Als "Primärteilchengröße" wird die Größe der Pigmente bezeichnet, so wie sie bei der Herstellung erhalten werden (d.h. vor der Dispergierung).Particularly good results are achieved with a carbon black pigment which has a so-called BET surface area of at least 30 m 2 per gram. "BET surface area" means that the surface area was determined by the method introduced by Brunauer, Emmet and Teller ("BET"). The average primary particle size is preferably less than 60 nm. The "primary particle size" is the size of the pigments as they are obtained during production (ie before dispersion).
Die strahlungsempfindliche Komponente in dem Gemisch kann ein Diazoniumsalz sein, eine Kombination aus einem Photopolymerisationsinitiator und einem polymerisierbaren Monomer (insbesondere ein Monomer mit einer polymerisierbaren ethylenisch ungesättigten Gruppe), eine Kombination aus einer Verbindung, die bei Bestrahlung Säure bildet, und einer durch die photochemisch erzeugte Säure spaltbaren Verbindung. Bevorzugt ist die strahlungsempfindliche Komponente jedoch ein Ester aus einer 1,2-Naphthochinon-2-diazid-4- oder -5-sulfonsäure und einer Verbindung mit mindestens einer phenolischen Hydroxygruppe. Die letztgenannte Verbindung weist bevorzugt mindestens 3 phenolische Hydroxygruppen auf. Ganz besonders bevorzugt für die Veresterung sind Verbindungen, die 3 bis 6 phenolische Hydroxygruppen besitzen. Beispiele hierfür sind 2,3,4-Trihydroxy-benzophenon, 2,3,4-Trihydroxy-3'-methyl-, -propyl- oder -isopropyl-benzophenon, 2,3,4,4'-Tetrahydroxy-benzophenon, 2,3,4,2',4'-Pentahydroxy-benzophenon, 2,3,4,2',3',4'-Hexahydroxy-benzophenon und 5,5'-Diacyl-2,3,4,2',3',4'-hexahydroxy-diphenylmethan. Amide der 1,2-Naphthochinon-2-diazid-4- oder -5-sulfonsäure sind ebenfalls geeignet. Brauchbare Veresterungskomponenten sind auch Kondensationsprodukte aus Pyrogallol und Aldehyden oder Ketonen sowie Kondensationsprodukte aus alkylierten Phenolen und Formaldehyd. Der Gehalt an strahlungsempfindlichen Verbindungen liegt bei etwa 1 bis 50 Gew.-%, bezogen auf das Gesamtgewicht der nichtflüchtigen Bestandteile des Gemisches.The radiation sensitive component in the mixture can be a diazonium salt be a combination of a photopolymerization initiator and a polymerizable Monomer (especially a monomer with a polymerizable ethylenically unsaturated group), a combination of a compound that forms acid when irradiated, and one by the photochemically generated acid fissile compound. The radiation-sensitive component is preferred however, an ester of a 1,2-naphthoquinone-2-diazide-4- or -5-sulfonic acid and a compound having at least one phenolic hydroxy group. The the latter compound preferably has at least 3 phenolic hydroxyl groups on. Compounds which are very particularly preferred for the esterification are which have 3 to 6 phenolic hydroxyl groups. Examples include 2,3,4-trihydroxy-benzophenone, 2,3,4-trihydroxy-3'-methyl-, propyl- or isopropyl-benzophenone, 2,3,4,4'-tetrahydroxy-benzophenone, 2,3,4,2 ', 4'-pentahydroxy-benzophenone, 2,3,4,2 ', 3', 4'-hexahydroxy-benzophenone and 5,5'-diacyl-2,3,4,2 ', 3', 4'-hexahydroxy-diphenylmethane. Amides of 1,2-naphthoquinone-2-diazide-4- or -5-sulfonic acid are also suitable. Usable esterification components are also condensation products from pyrogallol and aldehydes or ketones and condensation products from alkylated phenols and formaldehyde. The content of radiation-sensitive compounds is about 1 to 50 wt .-%, based on the total weight of the non-volatile components of the Mixture.
Beispiele für Polymere mit aciden Gruppen, die einen pKs-Wert von weniger als 13 besitzen, sind Polykondensate aus Phenolen (wie Phenol, Resorcin, einem Kresol, einem Xylenol, einem Trimethylphenol) oder sulfamoyl- oder carbamoyl-substituierten Aromaten mit Aldehyden (wie Formaldehyd) oder Ketonen, ferner mit bismethylol-substituerten Harnstoffen. Geeignet sind auch Umsetzungsprodukte von Diisocyanaten mit Diolen oder Diaminen, die acide Einheiten der genannten Art besitzen. Examples of polymers having acidic groups having a pK s value of less than 13, are polycondensates of phenols (such as phenol, resorcinol, a cresol, a xylenol, a trimethylphenol) or sulfamoyl- or carbamoyl-substituted aromatics with aldehydes (such as Formaldehyde) or ketones, furthermore with bismethylol-substituted ureas. Reaction products of diisocyanates with diols or diamines which have acidic units of the type mentioned are also suitable.
Weiterhin sind zu nennen Polymere mit Einheiten aus Vinylaromaten, N-Aryl-(meth)acrylamide oder Aryl-(meth)acrylate, wobei diese Einheiten jeweils noch eine oder mehrere carboxygruppen phenolische Hydroxygruppen, Sulfamoyl- oder Carbamoylgruppen aufweisen. Spezifische Beispiele sind Polymere mit Einheiten aus (2-Hydroxy-phenyl)-acrylat oder -methacrylat, aus N-(4-Hydroxy-phenyl)-acrylamid oder -methacrylamid, aus N-(4-Sulfamoyl-phenyl)-acrylamid oder -methacrylamid, aus N-(4-Hydroxy-3,5-dimethyl-benzyl)-acrylamid oder -methacrylamid, aus 4-Hydroxy-styrol oder aus Hydroxyphenyl-maleimid. Die Polymere können zusätzlich Einheiten aus anderen Monomeren, die keine aciden Einheiten besitzen, enthalten. Solche Einheiten sind beispielsweise Einheiten aus Olefinen oder Vinylaromaten, Methyl(meth)acrylat, Phenyl(meth)acrylat, Benzyl(meth)acrylat, Methacrylamid oder Acrylnitril. In diesem Zusammenhang steht die Bezeichnung "(Meth)acrylat" für Acrylat und/oder Methacrylat.Also to be mentioned are polymers with units made from vinyl aromatics, N-aryl- (meth) acrylamides or aryl (meth) acrylates, these units in each case one or more carboxy groups, phenolic hydroxyl groups, sulfamoyl or Have carbamoyl groups. Specific examples are polymers with Units made of (2-hydroxyphenyl) acrylate or methacrylate, made of N- (4-hydroxyphenyl) acrylamide or methacrylamide, from N- (4-sulfamoylphenyl) acrylamide or -methacrylamide, from N- (4-hydroxy-3,5-dimethyl-benzyl) -acrylamide or -methacrylamide, from 4-hydroxy-styrene or from hydroxyphenyl-maleimide. The Polymers can also contain units from other monomers that are not acidic Own units. Such units are made up of units, for example Olefins or vinyl aromatics, methyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, Methacrylamide or acrylonitrile. In this context stands the term "(meth) acrylate" for acrylate and / or methacrylate.
Das strahlungsempfindliche Gemisch enthält darüber hinaus ein polymeres Bindemittel. Vorzugsweise ist es das gleiche, das auch zur Vordispergierung des Rußes eingesetzt wird. Der Anteil des Sindemittels beträgt allgemein 2 bis 90 Gew.-%, bevorzugt 50 bis 85 Gew.-%, jeweils bezogen auf das Gesamtgewicht der nichtflüchtigen Bestandteile des strahlungsempfindlichen Gemisches. Dieser Anteil umfasst das zum Vordispergieren verwendete und auch das später zugesetzte Bindemittel.The radiation-sensitive mixture also contains a polymeric binder. It is preferably the same as that for predispersion of the carbon black is used. The proportion of the average is generally 2 to 90% by weight, preferably 50 to 85 wt .-%, each based on the total weight of the non-volatile Components of the radiation sensitive mixture. That share includes that used for predispersion and also that added later Binder.
Die in dem strahlungsempfindlichen Gemisch enthaltenen Ruße sind bevorzugt Flamm-, Furnace- oder Channelruße mit einer mittleren Primärteilchengröße von 80 nm oder weniger. Bevorzugt liegt die Primärteilchengröße bei weniger als 60 nm, besonders bevorzugt bei weniger als 30 nm. Die BET-Oberfläche der Ruße liegt bevorzugt bei mindestens 30 m2/g. In einer bevorzugten Ausführungsform sind die Ruße oxidiert oder nachoxidiert, wodurch saure Einheiten an der Rußoberfläche entstehen, so dass der pH-Wert einer wässrigen Dispersion dieser Ruße bei weniger als 7 liegt.The carbon blacks contained in the radiation-sensitive mixture are preferably flame, furnace or channel blacks with an average primary particle size of 80 nm or less. The primary particle size is preferably less than 60 nm, particularly preferably less than 30 nm. The BET surface area of the carbon blacks is preferably at least 30 m 2 / g. In a preferred embodiment, the carbon blacks are oxidized or post-oxidized, as a result of which acidic units form on the carbon black surface, so that the pH of an aqueous dispersion of these carbon blacks is less than 7.
Die in der beschriebenen Weise vordispergierten Ruße lassen sich überraschend gut in dem strahlungsempfindichen Gemisch dispergieren. Die Dispersion zeigt darüber hinaus eine verbesserte Stabilität. Der Anteil an Ruß liegt im allgemeinen bei 0,5 bis 30 Gew.-%, bevorzugt bei 2 bis 15 Gew.-%, jeweils bezogen auf das Gesamtgewicht der nichtflüchtigen Komponenten des Gemisches.The carbon blacks predispersed in the manner described can be surprising disperse well in the radiation sensitive mixture. The dispersion shows furthermore improved stability. The proportion of soot is generally at 0.5 to 30 wt .-%, preferably at 2 to 15 wt .-%, each based on the Total weight of the non-volatile components of the mixture.
Herstellen lassen sich die Rußdispersionen aus den Rußen und den Bindemitteln mit aciden Gruppen mit Hilfe von allgemein bekannten Vorrichtungen. Nach einer Vordispergierung in einem Dissolver wird die Mischung beispielsweise in einer Kugelmühle feindispergiert. Hierfür können als Lösemittel dieselben eingesetzt werden, die auch zur Beschichtung verwendet werden (wie Propylenglykol-monomethylether, Butanon oder γ-Butyrolacton). Der Gesamtgehalt an Gesamtfeststoff in der Dispersionen liegt allgemein bei 5 bis 50 Gew.-%, wobei der Anteil an Ruß bevorzugt unter der Menge an Bindemittel liegt. In manchen Fällen lässt sich durch Zugabe von Tensiden oder Verdickungsmitteln die Stabilität der Dispersion verbessern. Bevorzugt werden dazu Tenside bzw. Verdicker gewählt, die in den wässrig-alkalischen Entwicklern löslich sind.The carbon black dispersions can be produced from the carbon blacks and the binders with acidic groups using well known devices. After a For example, the mixture is predispersed in a dissolver in a Ball mill finely dispersed. The same can be used as the solvent for this which are also used for coating (such as propylene glycol monomethyl ether, Butanone or γ-butyrolactone). The total content of total solids in the dispersions is generally 5 to 50 wt .-%, the proportion of carbon black is preferably below the amount of binder. In some cases, the stability of the dispersion by adding surfactants or thickeners improve. For this purpose, surfactants or thickeners are preferably selected which are contained in the aqueous-alkaline developers are soluble.
Neben den genannten Komponenten kann das Gemisch weitere, in Aufzeichnungsmaterialien für die Herstellung von Druckplatten allgemein übliche Zusätze enthalten. Insbesondere sind zu nennen: Indikatorfarbstoffe (beispielsweise Dialkylaminoazobenzole), photochemische Säurebildner (beispielsweise Trifluormethansulfonate oder Hexafluorphosphate von Diazodiphenylaminen), Tenside (bevorzugt fluorhaltige Tenside oder Silikon-Tenside), Polyalkylenoxide zur Steuerung der Acidität der aciden Einheiten und niedermolekulare Verbindungen mit aciden Einheiten zur Erhöhung der Entwicklungsgeschwindigkeit.In addition to the components mentioned, the mixture can also contain other recording materials Common additives for the production of printing plates contain. The following should be mentioned in particular: indicator dyes (for example Dialkylaminoazobenzenes), photochemical acid generators (for example trifluoromethanesulfonates or hexafluorophosphates of diazodiphenylamines), surfactants (preferably fluorine-containing surfactants or silicone surfactants), polyalkylene oxides for control the acidity of the acidic units and small molecules with acidic units to increase the rate of development.
Teil der vorliegenden Erfindung ist darüber hinaus ein Aufzeichnungsmaterial mit einem Träger und einer strahlungsempfindlichen Schicht, wobei die Schicht aus dem erfindungsgemäßen Gemisch besteht. Das strahlungsempfindliche Gemisch lässt sich jedoch auch für andere Zwecke einsetzen, z.B. als Photoresist.Part of the present invention is also a recording material with a support and a radiation-sensitive layer, the layer consisting of the mixture according to the invention. The radiation sensitive mixture can also be used for other purposes, e.g. as a photoresist.
Der Träger in dem erfindungsgemäßen Aufzeichnungsmaterial ist bevorzugt eine Aluminiumfolie oder ein Verbund aus einer Aluminiumfolie und einer Polyesterfolie. Die Aluminiumoberfläche ist bevorzugt aufgerauht, eloxiert und mit einer Verbindung, die mindestens eine Phosphonsäure- oder Phosphonateinheit enthält, hydrophiliert. Vor der Aufrauhung kann eine Entfettung und Beizung mit Laugen sowie eine mechanische und/oder chemische Voraufrauhung erfolgen. Diese Träger werden dann mit einer Lösung des oben beschriebenen strahlungsempfindlichen Gemisches in einem (organischen) Lösemittel oder Lösemittelgemisch beschichtet und anschließend getrocknet.The carrier in the recording material according to the invention is preferably one Aluminum foil or a composite of an aluminum foil and a polyester foil. The aluminum surface is preferably roughened, anodized and with a Compound containing at least one phosphonic acid or phosphonate unit, hydrophilized. Before roughening, degreasing and pickling with lyes as well as mechanical and / or chemical pre-roughening. This Carriers are then exposed to a solution of the radiation sensitive described above Mixture in an (organic) solvent or solvent mixture coated and then dried.
Gegenstand der Anmeldung ist schließlich ein Verfahren zur Herstellung einer Flachdruckform, in dem das erfindungsgemäße Aufzeichnungsmaterial mit Infrarotstrahlung bildmäßig bestrahlt und anschließend mit einem wässrig-alkalischen Entwickler bei einer Temperatur von 20 bis 40 °C entwickelt wird.Finally, the subject of the application is a method for producing a Planographic printing form in which the recording material according to the invention with infrared radiation irradiated imagewise and then with an aqueous alkaline Developer is developed at a temperature of 20 to 40 ° C.
Der Entwickler weist bevorzugt ein Verhältnis von Siliciumdioxid zu Alkalioxid von 1 oder größer als 1 auf. Dadurch ist sichergestellt, dass keine Schädigung der Eloxalschicht im Entwicklungsprozess erfolgt. Bevorzugte Alkalioxide sind Na20 und K20 sowie Mischungen davon. Neben Alkalisilikaten kann der Entwickler weitere Bestandteile enthalten (wie Puffersubstanzen, Komplexbildner, Entschäumer, Lösemittel, Korrosionsinhibitoren, Farbstoffe, Tenside und/oder Hydrotrope). Die Entwicklung wird bevorzugt bei Temperaturen von 20 bis 40 °C in maschinellen Verarbeitungsanlagen durchgeführt. Zur Regenerierung werden Alkalisilikatlösungen verwendet mit Alkaligehalten von 0,6 bis 2,0 mol/l. Diese Lösungen können das gleiche Sliciumdioxid/Alkalioxid-Verhältnis wie der Entwickler besitzen (in der Regel ist es jedoch niedriger) und ebenfalls weitere Zusätze enthalten. Die erforderlichen Mengen an Regenerat müssen auf die verwendeten Entwicklungsgeräte, täglichen Plattendurchsätze, Bildanteile etc. abgestimmt werden und liegen im allgemeinen bei 1 bis 50 ml pro Quadratmeter Aufzeichnungsmaterial. Eine Regelung der Zugabe kann beispielsweise über die Leitwertmessung erfolgen ( vgl. EP-A 556 690).The developer preferably has a ratio of silicon dioxide to alkali oxide of 1 or greater than 1. This ensures that there is no damage to the anodized layer in the development process. Preferred alkali oxides are Na 2 0 and K 2 0 and mixtures thereof. In addition to alkali silicates, the developer can contain further constituents (such as buffer substances, complexing agents, defoamers, solvents, corrosion inhibitors, dyes, surfactants and / or hydrotropes). Development is preferably carried out at temperatures of 20 to 40 ° C in mechanical processing plants. Alkali silicate solutions with alkali contents of 0.6 to 2.0 mol / l are used for regeneration. These solutions can have the same silicon dioxide / alkali oxide ratio as the developer (but it is usually lower) and can also contain other additives. The required quantities of regrind have to be matched to the developing devices used, daily plate throughputs, image proportions etc. and are generally 1 to 50 ml per square meter of recording material. The addition can be regulated, for example, by measuring the conductance (cf. EP-A 556 690).
Zur Erhöhung der Widerstandsfähigkeit beim Drucken sowie zur Erhöhung der Resistenz gegen Auswaschmittel, Korrekturmittel und UV-härtbare Druckfarben können die entwickelten Platten kurzzeitig auf erhöhte Temperaturen erwärmt werden, wie es für Diazoschichten aus der GB-B 1 154 749 bekannt ist. To increase the resistance when printing and to increase the Resistance to detergents, correction agents and UV-curable printing inks the developed plates can be briefly heated to elevated temperatures as is known for diazo layers from GB-B 1 154 749.
Die nachfolgenden Beispiele erläutern im Detail den Gegenstand der Erfindung. Vergleichsbeispiele bzw. -substanzen sind mit Sternchen (*) gekennzeichnet. Prozente sind Gewichtsprozente und Verhältnisse sind Gewichtsverhältnisse, soweit nicht anders angegeben.The following examples explain the subject matter of the invention in detail. Comparative examples or substances are marked with an asterisk (*). Percentages are percentages by weight and ratios are ratios by weight, if not stated otherwise.
Ein nachoxidierter Gasruß mit einer mittleren Primärteilchengröße von 20 nm (die wässrige Dispersion dieses Rußes weist einen pH-Wert von 3 auf) und einer BET-Oberfläche von 300 m2/g wird mit den nachfolgend aufgeführten Harzen
- 1-1:
- meta-/para-Kresol-Formaldehyd-Novolak
(Gehalt an phenolischen Hydroxygruppen : 8,3 mmol/g) - 1-2:
- Copolymer aus Methacrylsäure und (2-Hydroxy-ethyl)-methacrylat
(Gehalt an Carboxygruppen: 1,6 mmol/g) - 1-3:
- Homopolymer aus (4-Hydroxy-3,5-dimethyl-benzyl)-methacrylamid
(Gehalt an phenolischen Hydroxygruppen: 4,5 mmol/g) - 1-4:
- Copolymer aus (2-Hydroxy-phenyl)-methacrylat und Methylmethacrylat
(Gehalt an phenolischen Hydroxygruppen: 4,7 mmol/g) - 1-5:
- Homopolymer aus 4-Sulfamoylphenyl-methacrylamid
(Gehalt an Sulfamoylgruppen: 4,1 mmol/g) - 1-6:
- Homopolymer aus (4-Hydroxy-phenyl)-acrylamid
(Gehalt an phenolischen Hydroxygruppen: 6,1 mmol/g ) - 1-7:
- Kondensationsprodukt aus Pyrrogallol und Aceton
(Gehalt an phenolischen Hydroxygruppen: 18,1 mmol/g ) - 1-8:
- Poly(4-Hydroxy-styrol)
(Gehalt an phenolischen Hydroxygruppen: 8,3 mmol/g) - 1-9*:
- Polyvinylbutyral
(enthält keine aciden Gruppen mit einem pKs von weniger als 13)
- 1-1:
- meta / para cresol formaldehyde novolak
(Content of phenolic hydroxyl groups: 8.3 mmol / g) - 1-2:
- Copolymer of methacrylic acid and (2-hydroxy-ethyl) methacrylate
(Content of carboxy groups: 1.6 mmol / g) - 1-3:
- Homopolymer of (4-hydroxy-3,5-dimethyl-benzyl) methacrylamide
(Content of phenolic hydroxyl groups: 4.5 mmol / g) - 1-4:
- Copolymer of (2-hydroxyphenyl) methacrylate and methyl methacrylate
(Content of phenolic hydroxyl groups: 4.7 mmol / g) - 1-5:
- Homopolymer from 4-sulfamoylphenyl methacrylamide
(Content of sulfamoyl groups: 4.1 mmol / g) - 1-6:
- Homopolymer from (4-hydroxy-phenyl) acrylamide
(Content of phenolic hydroxyl groups: 6.1 mmol / g) - 1-7:
- Condensation product from pyrrogallol and acetone
(Content of phenolic hydroxyl groups: 18.1 mmol / g) - 1-8:
- Poly (4-hydroxystyrene)
(Content of phenolic hydroxyl groups: 8.3 mmol / g) - 1-9 *:
- Polyvinyl butyral
(contains no acidic groups having a pK s of less than 13)
Es wurden Beschichtungslösungen hergestellt aus
- 20 Gew.-%
- eines Veresterungsprodukts aus 1 mol 2,3,4-Trihydroxybenzophenon und 1,5 mol 1,2-Naphthochinon-2-diazid-5-sulfonylchlorid,
- 20 Gew.-%
- (bezogen auf den Feststoff) der jeweiligen Rußdispersion (1-1 bis 1-9*),
- 3 Gew.-%
- 2,4-Dihydroxy-benzophenon,
- ad 100 Gew.-%
- Novolak aus Dispersion 1-1
- 20% by weight
- an esterification product of 1 mol of 2,3,4-trihydroxybenzophenone and 1.5 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride,
- 20% by weight
- (based on the solid) of the respective carbon black dispersion (1-1 to 1-9 *),
- 3% by weight
- 2,4-dihydroxy-benzophenone,
- ad 100% by weight
- Novolak from dispersion 1-1
Diese Lösungen wurden auf in Salzsäure aufgerauhte, in Schwefelsäure anodisierte und mit Polyvinylphosphonsäure hydrophilierte Aluminiumfolien aufgebracht. Nach 2 min Trocknen bei 100 °C lag die Schichtdicke bei 2 µm.These solutions were roughened in hydrochloric acid, anodized in sulfuric acid and aluminum foils hydrophilized with polyvinylphosphonic acid. After drying for 2 minutes at 100 ° C., the layer thickness was 2 μm.
Diese Aufzeichnungsmaterialien wurden dann in einem Innentrommelbelichter mit Infrarotstrahlung belichtet. Dabei wurde ein Nd-YAG-Laser mit einer Leistung von 8,0 W, einer Schreibgeschwindigkeit von 367 m/s und einer Strahlbreite von 10 µm eingesetzt.These recording materials were then exposed in an inner drum imagesetter Infrared radiation exposed. An Nd-YAG laser with a power of 8.0 W, a write speed of 367 m / s and a beam width of 10 µm used.
Die Entwicklung erfolgte in einem herkömmlichen Prozessor bei einer Durchlaufgeschwindigkeit von 0,4 m/min und einer Temperatur von 28°C mit einem Kaliumsilikatentwickler, der K2SiO3 (Normalität 0,8 mol/l in Wasser) sowie 0,2 Gew.-% Polyglykol-1000-dicarbonsäure und 0,4 Gew.-% Pelargonsäure enthielt.The development was carried out in a conventional processor at a throughput speed of 0.4 m / min and a temperature of 28 ° C with a potassium silicate developer, the K 2 SiO 3 (normality 0.8 mol / l in water) and 0.2 wt. -% Polyglykol-1000-dicarboxylic acid and 0.4 wt .-% pelargonic acid contained.
Die mit den vordispergierten Rußen 1-1 bis 1-8 hergestellten Aufzeichnungsmaterialien ließen sich restschichtfrei entwickeln. Das mit dem Ruß 1-9* hergestellte Aufzeichnungsmaterial zeigte Restschichtschleier, die in der Druckmaschine zum Tonen führten. The recording materials produced with the predispersed carbon blacks 1-1 to 1-8 could be developed without residual layers. The one made with carbon black 1-9 * Recording material showed residual layer haze in the printing press led to toning.
Beispiel 1 wurde wiederholt, jedoch mit dem Unterschied, dass die Infrarotbelichtung mit einem Außentrommelbelichter vorgenommen wurde, der mit einer Laserdiodenleiste mit einem Emissionsmaximum bei 830 nm ausgestattet war (Leistung jeder einzelnen Diode: 40 mW, Schreibgeschwindigkeit: 1 m/s, Strahlbreite 10 µm). Die Entwicklung erfolgte gemäß Beispiel 1, das Resultat bezüglich Restschichtschleier war dasselbe.Example 1 was repeated, but with the difference that the infrared exposure was done with an outer drum imagesetter using a laser diode bar was equipped with an emission maximum at 830 nm (power each individual diode: 40 mW, writing speed: 1 m / s, beam width 10 µm). The development was carried out according to Example 1, the result with regard to residual layer fog was the same.
Wie in Beispiel 1 beschrieben, werden Dispersionen der folgenden Rußtypen
hergestellt :
In 5-Tages-Standtests wurde die Stabilität der Dispersionen ermittelt. Folgende Ergebnisse wurden erhalten:
- 3-1 bis 3-4:
- gute Stabilität,
- 3-5:
- noch akzeptable Stabilität,
- 3-6*:
- erkennbare Sedimentation
- 3-1 to 3-4:
- good stability,
- 3-5:
- still acceptable stability,
- 3-6 *:
- recognizable sedimentation
Es wurden Beschichtungslösungen hergestellt aus
- 13 Gew.-%
- eines Esters aus 1 mol 2,3,4-Trihydroxy-benzophenon und 1,5 mol 1,2-Naphthochinon-2-diazid-5-sulfonylchlorid,
- 2 Gew.-%
- eines Esters aus 1 mol p-Cumylphenol und 1 mol 1,2- Naphthochinon-2-diazid-4-sulfonylchlorid,
- 30 Gew.-%
- (bezogen auf den Feststoff ) der jeweiligen Rußdispersion (3-1 bis 3-6*),
- 0,5 Gew.-%
- Dimethylaminoazobenzol,
- 15 Gew.-%
- Poly(4-hydroxy-styrol),
- ad 100 Gew.-%
- des Novolaks aus Dispersion 1-1
- 13% by weight
- an ester of 1 mol of 2,3,4-trihydroxy-benzophenone and 1.5 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride,
- 2% by weight
- an ester of 1 mol of p-cumylphenol and 1 mol of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride,
- 30% by weight
- (based on the solid) of the respective carbon black dispersion (3-1 to 3-6 *),
- 0.5% by weight
- Dimethylaminoazobenzene,
- 15% by weight
- Poly (4-hydroxy-styrene),
- ad 100% by weight
- of the novolak from dispersion 1-1
Diese Lösungen wurden auf eine in Salpetersäure aufgerauhte, in Schwefelsäure
anodisierte und mit Polyvinylphosphonsäure hydrophilierte Aluminiumfolie aufgebracht.
Nach 2 min Trocknen bei 100 °C betrug die Schichtdicke 1,5 µm.
Mit den vordispergierten Rußtypen 3-1 bis 3-5 wurde eine einwandfreie Beschichtung
erhalten. Der vordispergierte Rußtyp 3-6* führte dagegen zu Defekten in der
Beschichtung.
Die Druckplatten wurden in einem Innentrommelbelichter mit der Infrarotstrahlung
eines Nd-YAG-Lasers mit 6,5 W Leistung, einer Schreibgeschwindigkeit von
367 m/s und einer Strahlbreite von 10 µm bestrahlt.These solutions were applied to an aluminum foil roughened in nitric acid, anodized in sulfuric acid and hydrophilized with polyvinylphosphonic acid. After drying for 2 minutes at 100 ° C., the layer thickness was 1.5 μm.
A perfect coating was obtained with the predispersed carbon black types 3-1 to 3-5. In contrast, the predispersed soot type 3-6 * led to defects in the coating.
The printing plates were irradiated in an inner drum imagesetter with the infrared radiation of an Nd-YAG laser with a power of 6.5 W, a writing speed of 367 m / s and a beam width of 10 μm.
Die Entwicklung erfolgte in einem herkommlichen Prozessor bei 0,8 m/min bei einer Entwicklertemperatur von 25 °C mit folgendem Entwickler: Na2SiO3 (Normalität 0,8 mol/l), Polyglykol-2000-dicarbonsäure: 0,1 Gew.-%, Caprylsäure: 0,4 Gew.-%. In allen Fällen war eine restschichtfreie Entwicklung möglich.Development took place in a conventional processor at 0.8 m / min at a developer temperature of 25 ° C. with the following developer: Na 2 SiO 3 (normality 0.8 mol / l), polyglycol-2000-dicarboxylic acid: 0.1% by weight. -%, Caprylic acid: 0.4% by weight. In all cases, development without residual layers was possible.
Beispiel 3 wurde wiederholt, jedoch mit dem Unterschied, dass die Infrarotstrahlung in einem Außentrommelbelichter vorgenommen wurde, der mit einer Laserdiodenleiste mit einem Emissionsmaximum bei 830 nm ausgestattet war (Leistung jeder einzelnen Diode: 40 mW, Schreibgeschwindigkeit: 1,1 m/s, Strahlbreite 10 µm). Die Entwicklung erfolgte wie in Beispiel 3, das Resultat bezüglich Restschichtschleier war das gleiche.Example 3 was repeated, but with the difference that the infrared radiation was made in an outer drum imagesetter using a laser diode bar was equipped with an emission maximum at 830 nm (power each individual diode: 40 mW, writing speed: 1.1 m / s, beam width 10 µm). The development was carried out as in Example 3, the result with regard to residual layer fog was the same.
Beispiel 3 wurde wiederholt, jedoch mit dem Unterschied, dass die Belichtung mit UV-Licht in einem konventionellen Kopierrahmen erfolgte: 5kW-Metallhalogeniddotierte Quecksilberdampflampe mit einem Emissionsbereich von 350-450 nm, Belichtungsdosis 700 mJ/cm2. Die Entwicklung erfolgte wie in Beispiel 3; das Resultat bezüglich Restschichtschleier war das gleiche.Example 3 was repeated, but with the difference that the exposure to UV light was carried out in a conventional copying frame: 5kW metal halide-doped mercury vapor lamp with an emission range of 350-450 nm, exposure dose 700 mJ / cm 2 . The development was carried out as in Example 3; the result regarding the residual layer veil was the same.
Claims (11)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19712323 | 1997-03-24 | ||
DE19712323A DE19712323A1 (en) | 1997-03-24 | 1997-03-24 | Radiation-sensitive mixture and recording material for offset printing plates produced therewith |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0867278A1 true EP0867278A1 (en) | 1998-09-30 |
EP0867278B1 EP0867278B1 (en) | 2001-11-21 |
Family
ID=7824448
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98105080A Expired - Lifetime EP0867278B1 (en) | 1997-03-24 | 1998-03-20 | Radiation-sensitive mixture and recording material made thereof for offset printing plates |
Country Status (4)
Country | Link |
---|---|
US (1) | US6100004A (en) |
EP (1) | EP0867278B1 (en) |
JP (1) | JPH10293398A (en) |
DE (2) | DE19712323A1 (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0900652A2 (en) * | 1997-09-08 | 1999-03-10 | Agfa-Gevaert AG | White-light insensitive material for thermal registration and process for the fabrication of lithographic printing plates |
EP0900653A1 (en) * | 1997-09-08 | 1999-03-10 | Agfa-Gevaert AG | Positive working IR sensitive mixture, thermal imageable recording material and method of producing lithographic printing plate for offset printing using said composition |
US6060217A (en) | 1997-09-02 | 2000-05-09 | Kodak Polychrome Graphics Llc | Thermal lithographic printing plates |
US6063544A (en) * | 1997-03-21 | 2000-05-16 | Kodak Polychrome Graphics Llc | Positive-working printing plate and method of providing a positive image therefrom using laser imaging |
US6090532A (en) * | 1997-03-21 | 2000-07-18 | Kodak Polychrome Graphics Llc | Positive-working infrared radiation sensitive composition and printing plate and imaging method |
US6117610A (en) | 1997-08-08 | 2000-09-12 | Kodak Polychrome Graphics Llc | Infrared-sensitive diazonaphthoquinone imaging composition and element containing non-basic IR absorbing material and methods of use |
US6124425A (en) * | 1999-03-18 | 2000-09-26 | American Dye Source, Inc. | Thermally reactive near infrared absorption polymer coatings, method of preparing and methods of use |
US6218083B1 (en) | 1997-07-05 | 2001-04-17 | Kodak Plychrome Graphics, Llc | Pattern-forming methods |
US6280899B1 (en) | 1996-04-23 | 2001-08-28 | Kodak Polychrome Graphics, Llc | Relation to lithographic printing forms |
EP1156371A2 (en) * | 2000-05-15 | 2001-11-21 | Fuji Photo Film Co., Ltd. | Replenishing method of planographic printing plate developer |
US6352814B1 (en) | 1998-03-13 | 2002-03-05 | Kodak Polychrome Graphics Llc | Method of forming a desired pattern |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19803564A1 (en) | 1998-01-30 | 1999-08-05 | Agfa Gevaert Ag | Polymers with units of N-substituted maleimide and their use in radiation-sensitive mixtures |
US6569594B2 (en) * | 1998-04-15 | 2003-05-27 | Agfa-Gevaert | Heat mode sensitive imaging element for making positive working printing plates |
DE19933139A1 (en) * | 1999-07-19 | 2001-01-25 | Agfa Gevaert Ag | Stable pigment dispersion and radiation-sensitive recording material made with it |
US6884561B2 (en) | 2000-01-12 | 2005-04-26 | Anocoil Corporation | Actinically imageable and infrared heated printing plate |
JP4190167B2 (en) * | 2000-09-26 | 2008-12-03 | 富士フイルム株式会社 | Positive resist composition |
AUPR857301A0 (en) * | 2001-10-29 | 2001-11-29 | Kirk Engineering Services Australia Pty Ltd | Printing elements and methods of construction |
KR101222947B1 (en) | 2005-06-30 | 2013-01-17 | 엘지디스플레이 주식회사 | Solvent for printing, pattern composition for printing, and pattering method using the same |
JP4713262B2 (en) * | 2005-07-22 | 2011-06-29 | 昭和電工株式会社 | Photosensitive resin composition |
JP4849362B2 (en) * | 2008-03-14 | 2012-01-11 | ナガセケムテックス株式会社 | Radiation sensitive resin composition |
JP5140540B2 (en) * | 2008-09-30 | 2013-02-06 | 富士フイルム株式会社 | Preparation of lithographic printing plate precursor and lithographic printing plate |
JP6196877B2 (en) * | 2013-10-21 | 2017-09-13 | サカタインクス株式会社 | Active energy ray-curable offset printing ink composition and printing method using the composition |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0562952A1 (en) * | 1992-03-23 | 1993-09-29 | Minnesota Mining And Manufacturing Company | Ablative imageable element |
WO1994001280A1 (en) * | 1992-07-06 | 1994-01-20 | Du Pont (U.K.) Limited | Image formation |
WO1996020429A1 (en) * | 1994-12-23 | 1996-07-04 | Horsell P.L.C. | Lithographic plate |
WO1997000175A2 (en) * | 1995-06-13 | 1997-01-03 | Scitex Corporation Ltd. | Ir ablateable driographic printing plates and methods for making same |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5658708A (en) * | 1995-02-17 | 1997-08-19 | Fuji Photo Film Co., Ltd. | Image recording material |
JP3589365B2 (en) * | 1996-02-02 | 2004-11-17 | 富士写真フイルム株式会社 | Positive image forming composition |
-
1997
- 1997-03-24 DE DE19712323A patent/DE19712323A1/en not_active Withdrawn
-
1998
- 1998-03-11 US US09/038,162 patent/US6100004A/en not_active Expired - Fee Related
- 1998-03-17 JP JP10066828A patent/JPH10293398A/en not_active Withdrawn
- 1998-03-20 DE DE59802188T patent/DE59802188D1/en not_active Expired - Fee Related
- 1998-03-20 EP EP98105080A patent/EP0867278B1/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0562952A1 (en) * | 1992-03-23 | 1993-09-29 | Minnesota Mining And Manufacturing Company | Ablative imageable element |
WO1994001280A1 (en) * | 1992-07-06 | 1994-01-20 | Du Pont (U.K.) Limited | Image formation |
WO1996020429A1 (en) * | 1994-12-23 | 1996-07-04 | Horsell P.L.C. | Lithographic plate |
WO1997000175A2 (en) * | 1995-06-13 | 1997-01-03 | Scitex Corporation Ltd. | Ir ablateable driographic printing plates and methods for making same |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6280899B1 (en) | 1996-04-23 | 2001-08-28 | Kodak Polychrome Graphics, Llc | Relation to lithographic printing forms |
US6090532A (en) * | 1997-03-21 | 2000-07-18 | Kodak Polychrome Graphics Llc | Positive-working infrared radiation sensitive composition and printing plate and imaging method |
US6063544A (en) * | 1997-03-21 | 2000-05-16 | Kodak Polychrome Graphics Llc | Positive-working printing plate and method of providing a positive image therefrom using laser imaging |
US6218083B1 (en) | 1997-07-05 | 2001-04-17 | Kodak Plychrome Graphics, Llc | Pattern-forming methods |
US6117610A (en) | 1997-08-08 | 2000-09-12 | Kodak Polychrome Graphics Llc | Infrared-sensitive diazonaphthoquinone imaging composition and element containing non-basic IR absorbing material and methods of use |
US6060217A (en) | 1997-09-02 | 2000-05-09 | Kodak Polychrome Graphics Llc | Thermal lithographic printing plates |
EP0900652A2 (en) * | 1997-09-08 | 1999-03-10 | Agfa-Gevaert AG | White-light insensitive material for thermal registration and process for the fabrication of lithographic printing plates |
US6165685A (en) * | 1997-09-08 | 2000-12-26 | Agfa-Gevaert N.V. | Thermally recordable material insensitive to white light |
EP0900652A3 (en) * | 1997-09-08 | 1999-03-17 | Agfa-Gevaert AG | White-light insensitive material for thermal registration and process for the fabrication of lithographic printing plates |
EP0900653A1 (en) * | 1997-09-08 | 1999-03-10 | Agfa-Gevaert AG | Positive working IR sensitive mixture, thermal imageable recording material and method of producing lithographic printing plate for offset printing using said composition |
US6352814B1 (en) | 1998-03-13 | 2002-03-05 | Kodak Polychrome Graphics Llc | Method of forming a desired pattern |
US6124425A (en) * | 1999-03-18 | 2000-09-26 | American Dye Source, Inc. | Thermally reactive near infrared absorption polymer coatings, method of preparing and methods of use |
US6177182B1 (en) | 1999-03-18 | 2001-01-23 | American Dye Source, Inc. | Thermally reactive near infrared absorption polymer coatings, method of preparing and methods of use |
EP1156371A2 (en) * | 2000-05-15 | 2001-11-21 | Fuji Photo Film Co., Ltd. | Replenishing method of planographic printing plate developer |
EP1156371A3 (en) * | 2000-05-15 | 2002-12-11 | Fuji Photo Film Co., Ltd. | Replenishing method of planographic printing plate developer |
Also Published As
Publication number | Publication date |
---|---|
US6100004A (en) | 2000-08-08 |
DE59802188D1 (en) | 2002-01-03 |
DE19712323A1 (en) | 1998-10-01 |
EP0867278B1 (en) | 2001-11-21 |
JPH10293398A (en) | 1998-11-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0867278B1 (en) | Radiation-sensitive mixture and recording material made thereof for offset printing plates | |
EP0978376B1 (en) | Radiation-sensitive recording material comprising IR-absorbing cyanine dyes having a betaine structure or having a betaine structure and containing an anion, and recording material prepared therewith | |
EP0978375B1 (en) | Radiation-sensitive mixture comprising IR-absorbing, anionic cyanine dyes and recording material prepared therewith | |
DE60028505T2 (en) | OBJECT WITH COATINGS IN WHICH A PICTURE CAN BE RECORDED | |
DE69818421T2 (en) | METHOD FOR PRODUCING LITHOGRAPHIC PRINTING PLATES | |
DE602004007007T2 (en) | Thermally reactive near infrared absorbing polymers and their use in heat sensitive lithographic printing plates | |
DE69310103T2 (en) | Imaging improvements | |
DE60218005T2 (en) | A radiation-sensitive product, a process for making a radiation-sensitive product and methods of printing or forming an image with the product | |
DE69826396T2 (en) | Photosensitive composition and image recording material | |
EP0933682A2 (en) | Polymers comprising N-substituted maleimide units and their use in radiation-sensitive compositions | |
DE60314168T2 (en) | POLYMER FOR HEAT-sensitive LITHOGRAPHIC PRINTER PAD | |
DE10239505A1 (en) | Heat sensitive positive working lithographic printing plate precursor with high chemical resistance | |
EP0900652B1 (en) | White-light insensitive material for thermal registration and process for the fabrication of lithographic printing plates | |
DE3222485A1 (en) | POSITIVE IMAGING, RADIATION-SENSITIVE AND SENSIBLE DIMENSIONS TO AQUEOUS ALKALI | |
DE3007212A1 (en) | LIGHT SENSITIVE DIMENSIONS | |
DE60315491T2 (en) | THERMAL SENSITIVE PRELIMINARY TO A LITHOGRAPHIC PRESSURE PLATE | |
DE60320436T2 (en) | POLYMER FOR HEAT-SENSITIVE LITHOGRAPHIC PRINTED PANELS | |
DE60017531T2 (en) | Objects with imageable coatings | |
DE69818447T2 (en) | IMPROVEMENT IMPROVEMENTS | |
EP0900653B1 (en) | Thermal imageable recording material comprising a layer of a positive working IR sensitive mixture and method of producing lithographic printing plate for offset printing | |
DE10337506A1 (en) | Heat-sensitive positive-working lithographic printing plate precursor | |
DE60214803T2 (en) | Lithographic printing plate and lithographic process | |
DE19910363B4 (en) | Positive photosensitive imageable element | |
DE4002397A1 (en) | Positive photosensitive mixt. contg. hydroxy-aralkyl acrylate polymer - and sensitiser, useful in printing plate mfr. and as photoresist | |
DE60317394T2 (en) | Process for the preparation of a lithographic printing plate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE FR GB IT NL |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
17P | Request for examination filed |
Effective date: 19990330 |
|
AKX | Designation fees paid |
Free format text: DE FR GB IT NL |
|
17Q | First examination report despatched |
Effective date: 19991214 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: AGFA-GEVAERT N.V. |
|
RTI1 | Title (correction) |
Free format text: RADIATION-SENSITIVE MIXTURE AND RECORDING MATERIAL MADE THEREOF FOR OFFSET PRINTING PLATES |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB IT NL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20011121 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20011121 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
REF | Corresponds to: |
Ref document number: 59802188 Country of ref document: DE Date of ref document: 20020103 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20020130 |
|
RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: AGFA-GEVAERT |
|
ET | Fr: translation filed | ||
NLT2 | Nl: modifications (of names), taken from the european patent patent bulletin |
Owner name: AGFA-GEVAERT |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20060320 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20060322 Year of fee payment: 9 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20070320 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20071130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20071002 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070320 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070402 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20060322 Year of fee payment: 9 |