EP2033801B1 - Heat sensitive recording material - Google Patents
Heat sensitive recording material Download PDFInfo
- Publication number
- EP2033801B1 EP2033801B1 EP07017651A EP07017651A EP2033801B1 EP 2033801 B1 EP2033801 B1 EP 2033801B1 EP 07017651 A EP07017651 A EP 07017651A EP 07017651 A EP07017651 A EP 07017651A EP 2033801 B1 EP2033801 B1 EP 2033801B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- heat
- sensitive recording
- recording material
- material according
- recording layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 52
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 13
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004202 carbamide Substances 0.000 claims abstract 3
- 239000010410 layer Substances 0.000 claims description 67
- 239000011241 protective layer Substances 0.000 claims description 32
- 238000000576 coating method Methods 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 29
- 239000011230 binding agent Substances 0.000 claims description 27
- 239000000049 pigment Substances 0.000 claims description 27
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- 238000004132 cross linking Methods 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 10
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- 239000004971 Cross linker Substances 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- XAAILNNJDMIMON-UHFFFAOYSA-N 2'-anilino-6'-(dibutylamino)-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C(N(CCCC)CCCC)=CC=C(C2(C3=CC=CC=C3C(=O)O2)C2=C3)C=1OC2=CC(C)=C3NC1=CC=CC=C1 XAAILNNJDMIMON-UHFFFAOYSA-N 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- 239000004816 latex Substances 0.000 claims description 4
- 229920000126 latex Polymers 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000002174 Styrene-butadiene Substances 0.000 claims description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 239000011115 styrene butadiene Substances 0.000 claims description 3
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 231100000489 sensitizer Toxicity 0.000 claims 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 235000012222 talc Nutrition 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- -1 p-toluenesulphonyl Chemical group 0.000 description 16
- 239000000370 acceptor Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 230000007613 environmental effect Effects 0.000 description 8
- 238000007639 printing Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000001023 inorganic pigment Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000000440 bentonite Substances 0.000 description 5
- 229910000278 bentonite Inorganic materials 0.000 description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 238000007645 offset printing Methods 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- ZTILAOCGFRDHBH-UHFFFAOYSA-N 4-(4-propan-2-yloxyphenyl)sulfonylphenol Chemical compound C1=CC(OC(C)C)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 ZTILAOCGFRDHBH-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 230000001680 brushing effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LROZSPADHSXFJA-UHFFFAOYSA-N 2-(4-hydroxyphenyl)sulfonylphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=CC=C1O LROZSPADHSXFJA-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical class C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 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 2
- 238000005259 measurement Methods 0.000 description 2
- IRWGLNFPSKUEMS-UHFFFAOYSA-N n-(2-hydroxyphenyl)-2-(4-hydroxyphenyl)sulfanylacetamide Chemical compound C1=CC(O)=CC=C1SCC(=O)NC1=CC=CC=C1O IRWGLNFPSKUEMS-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- ODCWYMIRDDJXKW-UHFFFAOYSA-N simazine Chemical compound CCNC1=NC(Cl)=NC(NCC)=N1 ODCWYMIRDDJXKW-UHFFFAOYSA-N 0.000 description 2
- 125000003003 spiro group Chemical group 0.000 description 2
- 238000007651 thermal printing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- WCOXQTXVACYMLM-UHFFFAOYSA-N 2,3-bis(12-hydroxyoctadecanoyloxy)propyl 12-hydroxyoctadecanoate Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC(O)CCCCCC)COC(=O)CCCCCCCCCCC(O)CCCCCC WCOXQTXVACYMLM-UHFFFAOYSA-N 0.000 description 1
- FPIAKQHHSBQHDE-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enamide;prop-2-enoic acid Chemical compound NC(=O)C=C.OC(=O)C=C.CC(=C)C(O)=O FPIAKQHHSBQHDE-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- ZMGMDXCADSRNCX-UHFFFAOYSA-N 5,6-dihydroxy-1,3-diazepan-2-one Chemical compound OC1CNC(=O)NCC1O ZMGMDXCADSRNCX-UHFFFAOYSA-N 0.000 description 1
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 241000294754 Macroptilium atropurpureum Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229940100389 Sulfonylurea Drugs 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical class C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 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
- 238000009499 grossing Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical class CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 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
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
-
- 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
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/337—Additives; Binders
- B41M5/3375—Non-macromolecular compounds
-
- 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
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
Definitions
- the invention relates to a heat-sensitive recording material having a substrate which carries a heat-sensitive recording layer on at least one of its two sides.
- the at least one heat-sensitive recording layer has a dye precursor and a color acceptor which react color-forming with each other under the action of heat.
- the invention also relates to the use of the proposed heat-sensitive recording material as a ticket to the same extent.
- Heat-sensitive recording materials of the type described above with, for example, a sheet of paper, a synthetic paper sheet or a plastic film as a substrate are known since the early years of chemically reactive recording materials and enjoy a constantly growing popularity, which is due, inter alia, that their use in particular as a ticket for the Ticket issuing is associated with great benefits. Because the color-forming components are stuck in the recording material itself in the heat-sensitive recording method, the toner and ink cartridge-free printers, which need no more control in their function, can be set up in large numbers. Thus, this innovative technology has prevailed especially in public passenger transport, buses and trains as well as in air traffic, stadium and museum funds and parking ticket issuers.
- thermosensitive recording material containing at least the components of two color-forming systems to form an irreversible printed image, one being a chelate-type system and the other being a conventional leuco-dye system.
- sulfonylureas including N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) urea, mentioned, which inevitably combined with a second developer to fulfill the task Need to become.
- a disadvantage of the known recording material of the type described above is the complicated use of two color-forming systems, which makes the recording material known in this way cost-intensive. Also, the document mentioned no hint that the known recording material is particularly good to print. However, it is precisely for this purpose that a task aspect for the new heat-sensitive recording material is aimed.
- the inventors recognized that with the intended use of the new recording material as a ticket, there are increased market demands for good printing in flexo and offset printing on the at least one side of the recording material having the thermosensitive recording layer. Further, and of paramount importance to the new recording material, it is said to have excellent resistance to environmental influences such as ethanol, water and plasticizer, as well as excellent lightfastness with sufficient sensitivity to supplied heat in the form of a thermal print image.
- a heat-sensitive recording material which has only one side of a heat-sensitive recording layer.
- a heat-sensitive recording material to be considered which in addition to the good printability and excellent resistance to environmental influences (especially ethanol) and light on the side with the heat-sensitive recording layer also has a very good back-printability
- the front and back coatings of a centrally positioned substrate influence each other.
- the focus of the invention is not only to be directed to the side of the new recording material having the heat-sensitive recording layer but also to its opposite rear side.
- the new recording material should be able to do without any further protective layer coverage as far as possible, but alternatively a recording material is conceivable which manages with a simply constructed protective layer on the recording layer.
- 2- (2H-benzotriazol-2-yl) -p-cresol according to the formula (2) is the sole sensitizer in the heat-sensitive recording layer.
- heat-sensitive recording materials having benzotriazole-based UV-absorbing components from the EP 0 992 363 A1 known without there a sensitizer according to the formula (2) is disclosed.
- Lt According to the known proposal, by ensuring a concentration gradient for UV-absorbing agents in a plurality of coatings applied to a substrate, the problem of photostability of formed thermal printing images is alleviated.
- Possible color acceptors are known and proven components which are known from the prior art and which are also used in part for the present invention as a combination partner for the color acceptor N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) essential to the invention.
- N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) urea is not found in the known document on the other hand. Consequently, this document is also no reference to the inventive combination of N- (p-toluenesulphonyn-N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea according to formula (1) with 2- (2H-benzotriazole-2 yl) -p-cresol according to formula (2) It of the present invention.
- the color acceptor comprises N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxyphenyl) -urea according to formula (1) in combination with other color acceptors, in particular selected from the list, comprising: 2,2 to (4 -hydroxyphenyl) propane, 4 - [(4- (1-methylethoxy) phenyl) sulfonyl] phenol, 4-hydroxy-4'-isopropoxydiphylsulfone, 4,4'-dihydroxy-diphenylsulfone, 2,4'-dihydroxy-diphenylsulfone and N- (2-hydroxyphenyl) -2 - [(4-hydroxyphenyl) thio] acetamide embedded image in the heat-sensitive recording layer, it represents a particularly suitable embodiment when the ratio by weight of (%) of the other color acceptors to N- (p-toluenesulphonyl) -N'-3- (
- ratio of the sensitizer according to formula (2) to the color acceptor according to formula (1) a range from 5:10 to 9:10 is particularly preferred, this ratio being independent of whether the color acceptor of formula (1) is alone or in Combination is set to adjust.
- 3-dibutylamino-6-methyl-7-anilinofluoran is considered to be the most suitable dye precursor used singly or in combination with other dye precursors, preferably selected from the above dye precursors.
- Suitable binders for incorporation into the heat-sensitive recording layer are, for example, water-soluble binders such as starch, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide-acrylate-methacrylate terpolymers, alkali metal salts of styrene.
- water-soluble binders such as starch, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide-acrylate-methacrylate terpolymers, alkali metal salts of styrene.
- binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers are also suitable as binders for incorporation into the heat-sensitive recording layer.
- polyvinyl alcohol in combination with acrylate copolymer are considered to be particularly preferred binders, the combination of which as the sole binder is incorporated into the heat-sensitive recording layer in a proportion of 12 to 27.5% by weight, based on the total weight of the recording layer ,
- the coating composition for forming the thermosensitive recording layer may further contain slip and release agents such as metal salts of higher fatty acids, for example, zinc stearate, calcium stearate and waxes such as paraffin, oxidized paraffin, Polyethylene, polyethylene oxide, stearamides and castor wax.
- Further constituents of the recording layer are, for example, pigments, preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate, in which case in particular calcium carbonate, preferably in an amount of from 10 to 18% by weight, based on the total weight of the recording layer the recording layer is to be included as being preferred.
- a permanent color or typeface image can be formed in the recording layer under the action of heat.
- the basis weight of the heat-sensitive recording layer is preferably between 2.5 and 12 g / m 2 and more preferably between 3 and 6.5 g / m 2 .
- a brush for applying the heat-sensitive recording layer in particular, offer a doctor blade and (roll) doctor blade coater, curtain coater and air brush.
- the coating color used to form the recording layer is aqueous.
- the subsequent drying of the coating color can be done by means of microwave irradiation. Usually and proven it is just as much to supply heat, as happens by hot-air floatation dryer or contact dryer. Also conceivable is a combination of the listed dry processes.
- a pigment-containing intermediate layer between the substrate layer and the recording layer.
- pigments of the intermediate layer both organic void pigments and inorganic pigments have proven useful, the latter preferably selected from the group comprising natural and calcined kaolin, silica and in particular bentonite, calcium carbonate and aluminum hydroxide, in particular boehmite here.
- such an intermediate layer can make a positive contribution to the leveling of the base layer surface, which reduces the amount of coating color necessarily required for the heat-sensitive recording layer. For this reason, offer to coat the intermediate layer leveling strokes, such as roller coater, doctor blade and (roll) doctor blade coating.
- the pigments of this intermediate layer can absorb the heat-liquefied wax constituents of the thermosensitive recording layer in the typeface formation and thus promote a safe and rapid operation of the heat-induced recording.
- the basis weight of the pigmented intermediate layer is preferably between 5 and 20 g / m 2 and more preferably between 7 and 11 g / m 2 .
- the recording material according to the invention may have a protective layer which is applied to the heat-sensitive recording layer and completely or partially covers it.
- the protective layer takes on a task, as it also partially fulfilled by a preferred provided backside coating namely, on the one hand the protection of the recording layer arranged under it against environmental influences such as oils, fats, water and plasticizers and on the other hand a further improvement in the printability, especially in offset and flexographic printing.
- the protective layer itself can be applied by means of conventional brushing, for which, inter alia, a coating color is usable, as described above and for which a surface-related mass in a range of 1.5 to 4.5 g / m 2 is preferred, or the protective layer may alternatively be printed. Processing technology and in terms of their technological properties are particularly suitable such protective layers which are curable by means of actinic radiation.
- actinic radiation UV or ionizing radiation, such as electron beams to understand.
- a second alternative embodiment which is possible as an alternative to the first embodiment described above, for a protective layer wholly or partially covering the heat-sensitive recording layer contains at least one polyvinyl alcohol and a crosslinking aid. It is preferred that the polyvinyl alcohol of the protective layer is modified with carboxyl or silanol groups.
- a protective layer has a high affinity to the printing ink used in the offset printing process, preferably UV-crosslinking ink, which helps decisively to meet the requirement for improved printability within the offset printing. It is also conceivable to use mixtures of different carboxyl-group- or silanol-modified polyvinyl alcohols.
- Suitable crosslinking aids in the protective layer according to the second embodiment are, in particular, those selected from the group comprising: boric acid, polyamine, epoxy resin, dialdehyde, formaldehyde oligomers, polyamine-epichlorohydrin resin, dimethylurea, melamine-formaldehyde. It is also possible to use mixtures of different crosslinking aids.
- the ratio of the weight% of the modified polyvinyl alcohol to the crosslinking aid is in a range of 20: 1 to 5: 1, and more preferably in a range of 12: 1 to 7: 1 lies. It can be said that a ratio of the modified polyvinyl alcohol to the crosslinking aid of 100 parts by volume to 15 to 30 parts by volume has been proven.
- the protective layer according to the second embodiment additionally contains an inorganic pigment.
- the inorganic pigment is selected from the group comprising silica, aluminum hydroxide, calcium carbonate, kaolin or a mixture of said inorganic pigments.
- the protective layer for economic reasons to be formed as single-layer as possible according to the second embodiment with a basis weight in a range of 1.5 g / m 2 to 6 g / m 2 and especially between 1.7 g / m 2 and 3 g / m 2 apply, without being limited to the Einschhold the protective layer. It has been found to be advantageous to have a smoothness of the protective layer in the range of 500 and preferably from 800 or better still 1,000 Bekk seconds (sec) to less than 3,000 Bekk-sec. In particular, values of 1,000 Bekk-sec to less than 2,500 Bekk-sec and most preferably from 1,200 Bekk-sec to 2,000 Bekk-sec are suitable.
- the appearance of the protective layer is significantly determined by the type of smoothing and the friction in the calender and calender influencing roll surfaces and their materials.
- a preferred range is between 30% and 50%, and most preferably between 40% and 48%, measured according to Tappi 450 or ISO 2813 at a reflection angle of 75 °.
- Another preferred range is between 10% and 15%, determined according to the same rules and parameters.
- a particularly good printability for the offset printing process is present when the protective layer of the new heat-sensitive recording material has the lowest possible polar fraction of the surface tension to be determined as the sum of disperse and polar fraction.
- the determination of the surface tension takes place after Owens Wendt as in Journal of Applied Polymer Science, Vol. 13, 1969, pages 1741-1747 : Estimation of the Surface Free Energy of Polymers; DK Owens, RC Wendt stated.
- a suitable range for the measurements of the polar component of the surface tension is above zero and below 15 mN / m (milli-Newton per meter).
- a polar fraction of the surface tension is particularly preferably less than 10 mN / m.
- the backcoat layer preferably comprises at least one polyurethane-based component acting as a crosslinker, preferably an anionic polyurethane in aqueous solution, for example Eka SP AP 29, Eka Chemicals AB, D-32301 Düren.
- a polyurethane-based component acting as a crosslinker preferably an anionic polyurethane in aqueous solution, for example Eka SP AP 29, Eka Chemicals AB, D-32301 Düren.
- the backcoat preferably comprises binders and in particular starch, styrene-butadiene latex and optionally carboxymethyl cellulose.
- binders and in particular starch, styrene-butadiene latex and optionally carboxymethyl cellulose.
- the mixture of different binders in sometimes highly divergent mixing ratios is possible and preferred.
- Particularly positive results can be achieved with a coating weight for the back coating in a range of 2 to 15 g / m 2 .
- a range for the coating weight of the back coating of 2.5 to 4.5 g / m 2
- a range of 8.5 to 12 g / m 2 is very particularly preferred.
- particularly suitable brushing particularly equalizing application devices such as doctor blade and (roll) doctor blade coater and Walzenstreichwerke into consideration, without being limited in any way.
- both the back coat and the thermosensitive recording layer may be coated and dried in a single operation, for example, including the protective layer completely covering it.
- such a coating machine (a) a rolling device, (b) a first coating, such as a curtain coater, an air brush or a roller blade coating applicator for applying the heat-sensitive recording layer, (c) a first non-contact Schwebetrocknerkanal, (d) a curtain coater or an airbrush for applying the protective layer, (e) optionally and depending on the type, a contactless web guiding system, (f) a film applicator for application of the backside coating, (g) a second non-contact floating dryer channel, (h) an after-dryer section with several drying cylinders, ( i) a remoistening system or a coating installation such as a film applicator for optimizing the flatness or for reducing the roll tendency, (j) an IR drying system, (k) one or more calendering units each having one or more press nips, in particular using zone-controllable and / or shoe press rolls or belt calenders and (I) an A Provide rolling device.
- a further coating unit (b ') for example a doctor blade applicator with associated drying apparatus (b "), which can be a floating dryer channel and / or a drying cylinder, is provided is.
- paper is the substrate that has prevailed on the market with regard to the good environmental compatibility because of good recyclability and is preferred in the context of the invention.
- a paper web of bleached and ground deciduous and softwood pulps with a basis weight of 67 g / m 2 is prepared on a fourdrinier paper machine as the substrate layer with the addition of conventional additives in conventional amounts.
- a mainly calcined kaolin pigment, Styrolbutadienlatex as a binder and starch as Cobinder having intermediate layer of 9 g / m 2 is applied online within the coating machine with a roller blade coating.
- thermosensitive recording layer having a basis weight of 5.4 g / m 2 is applied to the intermediate layer in this order by means of a doctor blade coater, a protective layer of air brush 2.0 g / m 2 and applied by roller coater with downstream roller blade a backcoat of 3 g / m 2 .
- Example 1 of the invention comprises Tinuvin ® P
- Comparative Example 2 includes Tinuvin ® 144
- Comparative Example 3 Tinuvin ® 234
- Comparative example 4 containing Tinuvin ® 312
- Comparative example 5 contains Tinuvin ® 477 DW
- Comparative Example 6 contains GNI.
- Table 1 the formulations of the final recording layer are reproduced, while Example 1 according to the invention and gray background for identification, Examples 2 to 6 are comparative examples.
- This treatment in the case of percent resistance to ethanol, provides immersion of the Thermoprobertextes in a 25% ethanol solution (25 vol .-% solution, 23 ° C) over 20 minutes. The printout is then carefully blotted with blotting paper and allowed to rest for 24 hours at 23 ° and 50% humidity.
- thermoprob expression is carried out until an energy of 64,800 kJ / m 2 has been reached. The print will then rest for 24 hours at 23 ° and 50% humidity.
- the determination of the dynamic print density at three points of the black-colored areas is carried out again with the Gretag MacBeth TYPE D19C NB / U densitometer.
- the respective mean values of the measurements before / after the bath in the ethanol solution and before / after the light irradiation are formed and the mean value after the bath (after the irradiation) as a percentage of the mean value before the bath (before the irradiation).
- ODU Optical Density Units
- ODU Optical Density Units
- Atlantek 400 device from Viex (USA) using a thermal head with a resolution of 300 dpi and an energy per unit area of 11.7 mJ / mm 2 .
- the print density even of the black-colored areas are measured with the densitometer Gretag MacBeth TYPE D19C NB / U (Gretag MacBeth, 8105 Regensdorf, Switzerland), where the dynamic printing densities are measured at three points for each measured value and the arithmetic mean is formed from the three individual values becomes.
- Example 1 On the samples It. Example 1 and It of Comparative Examples 2 to 6, the resistances to ethanol as an example of the resistance to environmental influences, the resistance to light and the sensitivity to supplied heat in the form of a thermal print image were measured according to the above-described specifications. The measured values can be found in the last three columns of Table 1.
- Example 1 fulfills the requirements of excellent resistance to environmental influences as well as excellent light resistance combined with sufficient sensitivity to supplied heat in the form of a thermal printing image. At the same time, a very good printability was observed on the samples of Example 1 according to the invention, and, in view of the offset printability, an outstanding pick resistance was also found.
- Comparative Example 3 has higher resistance to ethanol than Example 1 of the present invention, the measured values of Comparative Example 3 are far too poor in light resistance and dynamic printing density:
- the light resistance should preferably exceed 55%
- the dynamic printing density should preferably exceed 1.0 ODU
- the resistance to ethanol should preferably exceed 80% - particularly preferably at least 81 %, wherein the values mentioned apply with reference to the above definition for metrological detection of the corresponding measured variables.
- Comparative Example 6 has higher dynamic printing density values than Inventive Example 1, Comparative Example 6's measured values are far too poor in light resistance and resistance to ethanol-even the worst in the case of resistance to ethanol test series.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
Die Erfindung betrifft ein wärmeempfindliches Aufzeichnungsmaterial mit einem Substrat, das auf mindestens einer seiner beiden Seiten eine wärmeempfindliche Aufzeichnungsschicht trägt. Die mindestens eine wärmeempfindliche Aufzeichnungsschicht weist einen Farbstoffvorläufer und einen Farbakzeptor auf, die unter Einwirkung von Wärme farbbildend miteinander reagieren. Die Erfindung betrifft im gleichen Maße auch die Verwendung des vorgeschlagenen wärmeempfindlichen Aufzeichnungsmaterials als Ticket.The invention relates to a heat-sensitive recording material having a substrate which carries a heat-sensitive recording layer on at least one of its two sides. The at least one heat-sensitive recording layer has a dye precursor and a color acceptor which react color-forming with each other under the action of heat. The invention also relates to the use of the proposed heat-sensitive recording material as a ticket to the same extent.
Wärmeempfindliche Aufzeichnungsmaterialien der eingangs beschriebenen Art mit beispielsweise einem Papierbogen, einem Synthesepapierbogen oder einer Kunststofffolie als Substrat sind seit den frühen Jahren chemisch reagierender Aufzeichnungsmaterialien bekannt und erfreuen sich einer ständig wachsenden Beliebtheit, was unter anderem darauf zurückzuführen ist, dass ihre Verwendung insbesondere als Ticket für den Ticketausgebenden mit großen Vorteilen verbunden ist. Weil die farbbildenden Komponenten bei dem wärmeempfindlichen Aufzeichnungsverfahren in dem Aufzeichnungsmaterial selbst stecken, können die Toner- und Farbkartuschenfreien Drucker, die in ihrer Funktion von niemandem mehr kontrolliert werden brauchen, in großer Zahl aufgestellt werden. So hat sich diese innovative Technologie insbesondere im öffentlichen Personenverkehr, bei Bussen und Bahnen genauso wie im Flugverkehr, an Stadion- und Museumskassen sowie bei Parkausweisgebern durchgesetzt.Heat-sensitive recording materials of the type described above with, for example, a sheet of paper, a synthetic paper sheet or a plastic film as a substrate are known since the early years of chemically reactive recording materials and enjoy a constantly growing popularity, which is due, inter alia, that their use in particular as a ticket for the Ticket issuing is associated with great benefits. Because the color-forming components are stuck in the recording material itself in the heat-sensitive recording method, the toner and ink cartridge-free printers, which need no more control in their function, can be set up in large numbers. Thus, this innovative technology has prevailed especially in public passenger transport, buses and trains as well as in air traffic, stadium and museum funds and parking ticket issuers.
Mit dem Ziel, die wärmeempfindlichen Aufzeichnungsmaterialien insbesondere in ihrer Verwendung als Tickets hinsichtlich ihrer Resistenz gegenüber Umwelteinflüssen wie Wärme und Feuchtigkeit zu verbessern, flossen immer wieder Neuerungen in die zugrunde liegende Chemie und die Herstellungstechnik zur Erzeugung solcher Aufzeichnungsmaterialien ein.With the aim of improving the heat-sensitive recording materials, especially in their use as tickets, in terms of their resistance to environmental influences such as heat and moisture, innovations in the underlying chemistry and the production technique for producing such recording materials have always been incorporated.
So ist Gegenstand der
Nachteilig an dem bekannten Aufzeichnungsmaterial der oben beschriebenen Art ist die aufwendige Nutzung zweier farbbildender Systeme, was das derart bekannte Aufzeichnungsmaterial kostenintensiv macht. Auch ist der genannten Schrift keinerlei Hinweis zu entnehmen, dass das bekannte Aufzeichnungsmaterial besonders gut zu bedrucken sei. Gerade dahingehend zielt jedoch ein Aufgabenaspekt für das neue wärmeempfindliche Aufzeichnungsmaterial.A disadvantage of the known recording material of the type described above is the complicated use of two color-forming systems, which makes the recording material known in this way cost-intensive. Also, the document mentioned no hint that the known recording material is particularly good to print. However, it is precisely for this purpose that a task aspect for the new heat-sensitive recording material is aimed.
Die Erfinder erkannten nämlich, dass mit der beabsichtigten Nutzung des neuen Aufzeichnungsmaterials als Ticket verstärkte Marktanforderungen hinsichtlich einer guten Bedruckung im Flexo- und Offsetdruck auf der mindestens einen Seite des Aufzeichnungsmaterials, die die wärmeempfindliche Aufzeichnungsschicht aufweist, bestehen. Ferner und von größter Bedeutung für das neue Aufzeichnungsmaterial soll dieses über eine hervorragende Beständigkeit gegenüber Umwelteinflüssen wie beispielsweise Ethanol, Wasser und Weichmacher sowie über eine hervorragende Lichtbeständigkeit bei gleichzeitig ausreichender Empfindlichkeit gegenüber zugeführter Wärme in Form eines Thermodruckbildes verfügen.Namely, the inventors recognized that with the intended use of the new recording material as a ticket, there are increased market demands for good printing in flexo and offset printing on the at least one side of the recording material having the thermosensitive recording layer. Further, and of paramount importance to the new recording material, it is said to have excellent resistance to environmental influences such as ethanol, water and plasticizer, as well as excellent lightfastness with sufficient sensitivity to supplied heat in the form of a thermal print image.
Bevorzugt ist ein wärmeempfindliches Aufzeichnungsmaterial, das nur einseitig über eine wärmeempfindliche Aufzeichnungsschicht verfügt. Soll, wie hier gegeben, bei der Aufgabenstellung in bevorzugter Weise ein wärmeempfindliches Aufzeichnungsmaterial berücksichtigt werden, das neben der guten Bedruckbarkeit und hervorragenden Beständigkeit gegenüber Umwelteinflüssen (insbesondere Ethanol) und Licht auf der Seite mit der wärmeempfindlichen Aufzeichnungsschicht auch eine sehr gute rückseitige Bedruckbarkeit aufweist, muss bedacht werden, dass die front- und rückseitigen Beschichtungen eines mittig positionierten Substrates gegenseitig aufeinander Einfluss nehmen. Zur Lösung einer derart gestalteten Aufgabe ist der Fokus der Erfindung nicht nur auf die Seite des neuen Aufzeichnungsmaterials mit der wärmeempfindlichen Aufzeichnungsschicht, sondern auch auf seine gegenüberliegende Rückseite zu richten.Preferred is a heat-sensitive recording material which has only one side of a heat-sensitive recording layer. Should, as given here, in the task in a preferred manner, a heat-sensitive recording material to be considered, which in addition to the good printability and excellent resistance to environmental influences (especially ethanol) and light on the side with the heat-sensitive recording layer also has a very good back-printability It should be borne in mind that the front and back coatings of a centrally positioned substrate influence each other. To solve such a problem, the focus of the invention is not only to be directed to the side of the new recording material having the heat-sensitive recording layer but also to its opposite rear side.
Aus wirtschaftlichen Überlegungen soll zwar das neue Aufzeichnungsmaterial möglichst ohne jede weitere Schutzschichtabdeckung auskommen, jedoch ist alternativ dazu auch ein Aufzeichnungsmaterial denkbar, das mit einer einfach konstruierten Schutzschicht auf der Aufzeichnungsschicht auskommt.For economic reasons, the new recording material should be able to do without any further protective layer coverage as far as possible, but alternatively a recording material is conceivable which manages with a simply constructed protective layer on the recording layer.
Zur Lösung dieser anstehenden Aufgaben wird ein wärmeempfindliches Aufzeichnungsmaterial mit einem Substrat vorgeschlagen,
- das auf mindestens einer Seite eine wärmeempfindliche Aufzeichnungsschicht mit einem Farbstoffvorläufer und einem Farbakzeptor aufweist, wobei Farbstoffvorläufer und Farbakzeptor unter Einwirkung von Wärme farbbildend miteinander reagieren,
- und wobei das wärmeempfindliche Aufzeichnungsmaterial dadurch gekennzeichnet ist, dass die wärmeempfindliche Aufzeichnungsschicht als Farbakzeptor N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-harnstoff gemäß der folgenden Formel (1):
- having on at least one side a heat-sensitive recording layer with a dye precursor and a color acceptor, wherein dye precursor and color acceptor react with each other in a color-forming manner under the action of heat,
- and wherein the thermosensitive recording material is characterized in that the thermosensitive recording layer as the color acceptor is N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) urea according to the following formula (1):
Als besonders bevorzugt gilt es, wenn 2-(2H-benzotriazol-2-yl)-p-cresol gemäß der Formel (2) alleiniger Sensibilisator in der wärmeempfindlichen Aufzeichnungsschicht ist.It is particularly preferable that 2- (2H-benzotriazol-2-yl) -p-cresol according to the formula (2) is the sole sensitizer in the heat-sensitive recording layer.
Grundsätzlich sind wärmeempfindliche Aufzeichnungsmaterialien, die UV-absorbierende Komponenten auf Benzotriazol-Basis aufweisen, aus der
Der Farbakzeptor N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-harnstoff gemäß Formel (1) kann
- entweder in Kombination mit anderen Farbakzeptoren, insbesondere ausgesucht aus der Liste, umfassend: 2,2 bis (4-hydroxyphenyl)-Propan, 4-[(4-(1-methylethoxy)phenyl)sulfonyl]-Phenol, 4-hydroxy-4'-isopropoxydiphylsulfon, 4,4'-Dihydroxy-Diphenylsulfon, 2,4'-Dihydroxy-Diphenylsulfon, N-(2-hydroxyphenyl)-2-[(4-hydroxyphenyl)thio]-Acetamid,
- oder ganz besonders bevorzugt als alleiniger Farbakzeptor
- either in combination with other color acceptors, in particular selected from the list, comprising: 2,2 bis (4-hydroxyphenyl) propane, 4 - [(4- (1-methylethoxy) phenyl) sulfonyl] phenol, 4-hydroxy-4 '-isopropoxydiphylsulfone, 4,4'-dihydroxy-diphenylsulfone, 2,4'-dihydroxy-diphenylsulfone, N- (2-hydroxyphenyl) -2 - [(4-hydroxyphenyl) thio] -acetamide,
- or most preferably as the sole color acceptor
Wird der Farbakzeptor N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxyphenyl)-harnstoff gemäß Formel (1) in Kombination mit anderen Farbakzeptoren, insbesondere ausgesucht aus der Liste, umfassend: 2,2 bis (4-hydroxyphenyl)-Propan, 4-[(4-(1-methylethoxy)phenyl)sulfonyl]-Phenol, 4-hydroxy-4'-isopropoxydiphylsulfon, 4,4'-Dihydroxy-Diphenylsulfon, 2,4'-Dihydroxy-Diphenylsulfon und N-(2-hydroxyphenyl)-2-[(4-hydroxyphenyl)thio]-Acetamid
in der wärmeempfindlichen Aufzeichnungsschicht eingebunden, stellt es eine besonders geeignete Ausführungsform dar, wenn das auf Gew.-% (atro) bezogene Verhältnis der anderen Farbakzeptoren zu N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxyphenyl)-harnstoff gemäß Formel (1) in einem Bereich von 1 : 2 bis 1 : 25, noch besser in einem Bereich von 1 : 10 bis 1 : 25 und ganz besonders bevorzugt von 1 : 17,5 bis 1 : 25 liegt.When the color acceptor comprises N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxyphenyl) -urea according to formula (1) in combination with other color acceptors, in particular selected from the list, comprising: 2,2 to (4 -hydroxyphenyl) propane, 4 - [(4- (1-methylethoxy) phenyl) sulfonyl] phenol, 4-hydroxy-4'-isopropoxydiphylsulfone, 4,4'-dihydroxy-diphenylsulfone, 2,4'-dihydroxy-diphenylsulfone and N- (2-hydroxyphenyl) -2 - [(4-hydroxyphenyl) thio] acetamide
embedded image in the heat-sensitive recording layer, it represents a particularly suitable embodiment when the ratio by weight of (%) of the other color acceptors to N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxyphenyl) urea according to formula (1) in a range from 1: 2 to 1: 25, more preferably in a range from 1:10 to 1:25, and most preferably from 1: 17.5 to 1: 25.
Als Verhältnis des Sensibilisators gemäß Formel (2) zum Farbakzeptor gemäß Formel (1) gilt ein Bereich von 5 : 10 bis 9 : 10 als besonders bevorzugt, wobei dieses Verhältnis unabhängig von der Tatsache, ob der Farbakzeptor gemäß Formel (1) allein oder in Kombination eingesetzt ist, einzustellen ist.As the ratio of the sensitizer according to formula (2) to the color acceptor according to formula (1), a range from 5:10 to 9:10 is particularly preferred, this ratio being independent of whether the color acceptor of formula (1) is alone or in Combination is set to adjust.
Hinsichtlich der wärmeempfindlichen Aufzeichnungsschicht erkannten die Erfinder mit Bezug auf die gestellte Aufgabe, dass die Aufzeichnungsschicht praktisch alle bekannten Farbstoffvorläufer beinhalten kann, wobei auch Kombinationen mehrerer Farbstoffvorläufer möglich sind. Als Farbstoffvorläufer sind insbesondere bevorzugt:
- 6'-(dipentylamino)-3'-methyl-2'-(phenylamino)-spiro[isobenzofuran-1(3H),9'-[9H]xanthen]-3-one sowie
- Spiro[isobenzofuran-1(3H),9'-[9H]xanthen]-3-one-6'-(diethylamino)-3'-methy;-2'-(3-tolylamino)
und solche, ausgewählt aus der Gruppe der Fluoranverbindungen, wie insbesondere - 3-diethylamino-6-methyl-7-Anilinofluoran,
- 3-dibutylamino-6-methyl-7-Anilinofluoran,
- 3-(N-methyl-N-propyl)amino-6-methyl-7-Anilinofluoran,
- 3-(N-ethyl-N-isoamyl)amino-6-methyl-7-Anilinofluoran,
- 3-(N-methyl-N-cyclohexyl)amino-6-methyl-7-Anilinofluoran,
- 3-(N-ethyl-N-tolyl)amino-6-methyl-7-Anilinofluoran und
- 3-(N-ethyl-N-tetrahydrofuryl)-amino-6-methyl-7-Anilinofluoran.
- 6 '- (dipentylamino) -3'-methyl-2' - (phenylamino) -spiro [isobenzofuran-1 (3H), 9 '- [9H] xanthene] -3-one and
- Spiro [isobenzofuran-1 (3H), 9 '- [9H] xanthene] -3-one 6' - (diethylamino) -3'-methyl-2 '- (3-tolylamino)
and those selected from the group of fluoran compounds, in particular - 3-diethylamino-6-methyl-7-anilinofluoran,
- 3-dibutylamino-6-methyl-7-anilinofluoran,
- 3- (N-methyl-N-propyl) amino-6-methyl-7-anilinofluoran,
- 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluoran,
- 3- (N-methyl-N-cyclohexyl) amino-6-methyl-7-anilinofluoran,
- 3- (N-ethyl-N-tolyl) amino-6-methyl-7-anilinofluoran and
- 3- (N-ethyl-N-tetrahydrofuryl) amino-6-methyl-7-anilinofluoran.
Aus kommerziellen Gründen gilt 3-dibutylamino-6-methyl-7-Anilinofluoran als der am meisten geeignete Farbstoffvorläufer, der einzeln oder in Kombination mit anderen Farbstoffvorläufern, bevorzugt ausgesucht aus den oben genannten Farbstoffvorläufern, eingesetzt wird.For commercial reasons, 3-dibutylamino-6-methyl-7-anilinofluoran is considered to be the most suitable dye precursor used singly or in combination with other dye precursors, preferably selected from the above dye precursors.
Geeignete Bindemittel zur Einbindung in die wärmeempfindliche Aufzeichnungsschicht sind beispielsweise wasserlösliche Bindemittel wie Stärke, Hydroxyethylzellulose, Methylzellulose, Carboxymethylzellulose, Gelatine, Kasein, Polyvinylalkohole, modifizierte Polyvinylalkohole, Natriumpolyacrylate, Acrylamid-Acrylat-Copolymere, Acrylamid-Acrylat-Methacrylat-Terpolymere, Alkalisalze von Styrol-Maleinsäureanhydrid-Copolymeren oder Ethylen-Maleinsäureanhydrid-Copolymeren, die allein oder in Kombination untereinander eingesetzt werden können; auch wasserunlösliche Latexbinder wie Styrol-Butadiene-Copolymere, Acrylnitril-Butadien-Copolymere und Methyl-Acrylat-Butadien-Copolymere bieten sich als Bindemittel zur Einbindung in die wärmeempfindliche Aufzeichnungsschicht an. Im Sinne der vorliegenden Erfindung gelten Polyvinylalkohol in Verbindung mit Acrylat-Copolymer als besonders bevorzugte Bindemittel, deren Kombination als alleiniges Bindemittel zu einen Anteil von 12 bis 27,5 Gew.-%, bezogen auf das Gesamtgewicht der Aufzeichnungsschicht, in die wärmeempfindliche Aufzeichnungsschicht eingebunden ist.Suitable binders for incorporation into the heat-sensitive recording layer are, for example, water-soluble binders such as starch, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide-acrylate-methacrylate terpolymers, alkali metal salts of styrene. Maleic anhydride copolymers or ethylene-maleic anhydride copolymers which may be used alone or in combination with one another; Water-insoluble latex binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers are also suitable as binders for incorporation into the heat-sensitive recording layer. For the purposes of the present invention, polyvinyl alcohol in combination with acrylate copolymer are considered to be particularly preferred binders, the combination of which as the sole binder is incorporated into the heat-sensitive recording layer in a proportion of 12 to 27.5% by weight, based on the total weight of the recording layer ,
Zur Vermeidung des Klebens an einem Thermokopf und zur Vermeidung einer übermäßigen Abnutzung des Thermokopfes kann die Beschichtungsmasse zur Ausbildung der wärmeempfindlichen Aufzeichnungsschicht weiterhin Gleit- und Trennmittel enthalten wie Metallsalze höherer Fettsäuren, zum Beispiel Zinkstearat, Kalziumstearat und Wachse, wie zum Beispiel Paraffin, oxidiertes Paraffin, Polyethylen, Polyethylenoxid, Stearamide und Kastorwachs. Weitere Bestandteile der Aufzeichnungsschicht sind beispielsweise Pigmente, bevorzugt anorganische Pigmente wie beispielsweise Aluminium(hydr)oxid, Kieselsäure und Kalziumkarbonat, wobei hier insbesondere Kalziumkarbonat, das bevorzugt in einer Menge von 10 bis 18 Gew.-%, bezogen auf das Gesamtgewicht der Aufzeichnungsschicht, in die Aufzeichnungsschicht eingebunden sein soll, als bevorzugt gilt.To avoid sticking to a thermal head and avoiding excessive wear of the thermal head, the coating composition for forming the thermosensitive recording layer may further contain slip and release agents such as metal salts of higher fatty acids, for example, zinc stearate, calcium stearate and waxes such as paraffin, oxidized paraffin, Polyethylene, polyethylene oxide, stearamides and castor wax. Further constituents of the recording layer are, for example, pigments, preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silica and calcium carbonate, in which case in particular calcium carbonate, preferably in an amount of from 10 to 18% by weight, based on the total weight of the recording layer the recording layer is to be included as being preferred.
Als bevorzugt gilt, wenn in der Aufzeichnungsschicht unter Einwirkung von Wärme ein permanentes Farb- bzw. Schriftbild ausgebildet werden kann.It is preferred if a permanent color or typeface image can be formed in the recording layer under the action of heat.
Die flächenbezogene Masse der wärmeempfindlichen Aufzeichnungsschicht liegt bevorzugt zwischen 2,5 und 12 g/m2 und besonders bevorzugt zwischen 3 und 6,5 g/m2. Als Streichwerk zum Auftrag der wärmeempfindlichen Aufzeichnungsschicht bieten sich insbesondere Streichmesser- und (Roll-) Rakelstreichwerk, Curtain-Coater und Luftbürste an.The basis weight of the heat-sensitive recording layer is preferably between 2.5 and 12 g / m 2 and more preferably between 3 and 6.5 g / m 2 . As a brush for applying the heat-sensitive recording layer, in particular, offer a doctor blade and (roll) doctor blade coater, curtain coater and air brush.
Als bevorzugt gilt, wenn die zur Ausbildung der Aufzeichnungsschicht genutzte Streichfarbe wässrig ist. Die anschließende Trocknung der Streichfarbe kann mittels Mikrowellenbestrahlung geschehen. Üblicherweise und bewährt ist es genauso, Wärme zuzuführen, wie es durch Heißluft-Schwebetrockner oder auch Kontakttrockner geschieht. Auch denkbar ist eine Kombination aus den aufgeführten Trockenverfahren.It is preferred if the coating color used to form the recording layer is aqueous. The subsequent drying of the coating color can be done by means of microwave irradiation. Usually and proven it is just as much to supply heat, as happens by hot-air floatation dryer or contact dryer. Also conceivable is a combination of the listed dry processes.
Als weiterhin bevorzugt gilt die Ausbildung einer pigmenthaltigen Zwischenschicht zwischen der Substratschicht und der Aufzeichnungsschicht. Als Pigmente der Zwischenschicht haben sich sowohl organische Hohlraum-Pigmente wie auch anorganische Pigmente bewährt, letztere bevorzugt ausgewählt aus der Gruppe, umfassend natürliches wie kalziniertes Kaolin, Siliziumoxid und hier besonders Bentonit, Kalziumkarbonat sowie Aluminiumhydroxid und hier besonders Böhmit. Eine solche Zwischenschicht kann zum einen einen positiven Beitrag zur Egalisierung der Grundschichtoberfläche leisten, womit sich die Menge an notwendigerweise aufzubringender Streichfarbe für die wärmeempfindliche Aufzeichnungsschicht reduziert. Aus diesem Grund bieten sich zum Auftrag der Zwischenschicht egalisierende Streichwerke an, wie beispielsweise Walzenstreichwerke, Streichmesser- und (Roll-) Rakelstreichwerke. Zum anderen können die Pigmente dieser Zwischenschicht die durch Hitzeeinwirkung verflüssigten Wachsbestandteile der wärmeempfindlichen Aufzeichnungsschicht bei der Schriftbildausbildung aufnehmen und begünstigen so eine sichere und schnelle Funktionsweise der wärmeinduzierten Aufzeichnung. Die flächenbezogene Masse der pigmentierten Zwischenschicht liegt bevorzugt zwischen 5 und 20 g/m2 und noch besser zwischen 7 und 11 g/m2.Further preferred is the formation of a pigment-containing intermediate layer between the substrate layer and the recording layer. As pigments of the intermediate layer, both organic void pigments and inorganic pigments have proven useful, the latter preferably selected from the group comprising natural and calcined kaolin, silica and in particular bentonite, calcium carbonate and aluminum hydroxide, in particular boehmite here. On the one hand, such an intermediate layer can make a positive contribution to the leveling of the base layer surface, which reduces the amount of coating color necessarily required for the heat-sensitive recording layer. For this reason, offer to coat the intermediate layer leveling strokes, such as roller coater, doctor blade and (roll) doctor blade coating. On the other hand, the pigments of this intermediate layer can absorb the heat-liquefied wax constituents of the thermosensitive recording layer in the typeface formation and thus promote a safe and rapid operation of the heat-induced recording. The basis weight of the pigmented intermediate layer is preferably between 5 and 20 g / m 2 and more preferably between 7 and 11 g / m 2 .
Das erfindungsgemäße Aufzeichnungsmaterial kann eine Schutzschicht aufweisen, die auf die wärmeempfindliche Aufzeichnungsschicht aufgetragen ist und diese ganz oder teilweise abdeckt. Die Schutzschicht nimmt dabei eine Aufgabe wahr, wie sie auch teilweise von einer bevorzugt vorgesehenen Rückseitenbeschichtung erfüllt werden muss, nämlich zum einen den Schutz der unter ihr angeordneten Aufzeichnungsschicht vor Umwelteinflüssen wie Öle, Fette, Wasser und Weichmacher und zum anderen eine nochmalige Verbesserung der Bedruckbarkeit insbesondere im Offset- und Flexodruck.The recording material according to the invention may have a protective layer which is applied to the heat-sensitive recording layer and completely or partially covers it. The protective layer takes on a task, as it also partially fulfilled by a preferred provided backside coating namely, on the one hand the protection of the recording layer arranged under it against environmental influences such as oils, fats, water and plasticizers and on the other hand a further improvement in the printability, especially in offset and flexographic printing.
In einer ersten Ausführungsvariante weist eine solche Schutzschicht als Bindemittel ein wasserunlösliches, selbstvemetzendes Acrylpolymer, ein Vernetzungsmittel und als Pigment überwiegend einen alkalisch aufbereiteten Bentonit auf, wobei
- das Pigment der Schutzschicht aus einem oder mehreren anorganischen Pigmenten besteht und mindestens 80 Gew.-% aus einem hoch gereinigten alkalisch aufbereiteten Bentonit gebildet sind,
- das Bindemittel der Schutzschicht aus einem oder aus mehreren wasserunlöslichen, selbstvernetzenden Acrylpolymeren besteht,
- und das Bindemittel-/Pigmentverhältnis in einem Bereich zwischen 7 : 1 und 9 : 1 liegt.
- the pigment of the protective layer is composed of one or more inorganic pigments and at least 80% by weight is formed from a highly purified, alkaline-treated bentonite,
- the binder of the protective layer consists of one or more water-insoluble, self-crosslinking acrylic polymers,
- and the binder / pigment ratio ranges between 7: 1 and 9: 1.
Als selbstvernetzendes Acrylpolymer innerhalb der Schutzschicht gemäß hier beschriebener erster Ausführungsvariante ist ein selbstvemetzendes Bindemittel zu verstehen, ausgewählt aus der Gruppe umfassend Styrol-Acrylsäureester-Copolymerisat, ein Acrylamidgruppen enthaltendes Copolymerisat aus StyrollAcrylsäureester sowie ganz bevorzugt ein Copolymer auf Basis von Acrylnitril, Methacrylamid und Acrylester. Neben dem alkalisch aufbereiteten Bentonit kann als Pigment auch natürliches oder gefälltes Kalziumkarbonat, Kaolin, Kieselsäure, Aluminiumhydroxid oder Titanoxid in die Schutzschicht eingebunden sein. Hinsichtlich der Vernetzungsmittel sind insbesondere solche bevorzugt, die ausgewählt sind aus der Gruppe umfassend
- zyklischen Harnstoff,
- Methylolhamstoff,
- Amoniumzirkoniumkarbonat und
- besonders bevorzugt Polyamidepichlorhydrinharz.
- cyclic urea,
- Methylolhamstoff,
- Amonium zirconium carbonate and
- more preferably polyamide-epichlorohydrin resin.
Durch die Wahl eines wasserunlöslichen, selbstvernetzenden Acrylpolymers als Bindemittel und dessen Verhältnis einerseits zum Pigment in einem Bereich zwischen 7 : 1 und 9 : 1, andererseits und besonders bevorzugt zum Vernetzungsmittel größer als 5 : 1 ist schon bei einer Schutzschicht mit relativ geringer flächenbezogener Masse eine hohe Umweltresistenz des vorgeschlagen Aufzeichnungsmaterials gegeben.The choice of a water-insoluble, self-crosslinking acrylic polymer as a binder and its ratio on the one hand to the pigment in a range between 7: 1 and 9: 1, on the other hand and particularly preferably to the crosslinking agent greater than 5: 1, is already relatively low in area with a protective layer Mass given a high environmental resistance of the proposed recording material.
Die Schutzschicht selbst kann mittels üblicher Streichwerke aufgetragen sein, wofür unter anderem eine Streichfarbe nutzbar ist, wie sie oben beschrieben ist und für die eine flächenbezogene Masse in einem Bereich von 1,5 bis 4,5 g/m2 bevorzugt ist, oder die Schutzschicht kann alternativ auch aufgedruckt sein. Verarbeitungstechnisch und hinsichtlich ihrer technologischen Eigenschaften besonders geeignet sind solche Schutzschichten, die mittels aktinischer Strahlung härtbar sind. Unter dem Begriff "aktinische Strahlung" sind UV- oder ionisierende Strahlungen, wie Elektronenstrahlen, zu verstehen.The protective layer itself can be applied by means of conventional brushing, for which, inter alia, a coating color is usable, as described above and for which a surface-related mass in a range of 1.5 to 4.5 g / m 2 is preferred, or the protective layer may alternatively be printed. Processing technology and in terms of their technological properties are particularly suitable such protective layers which are curable by means of actinic radiation. The term "actinic radiation" UV or ionizing radiation, such as electron beams to understand.
Eine alternativ zur oben beschriebenen ersten Ausführungsvariante mögliche zweite Ausführungsvariante für eine die wärmeempfindliche Aufzeichnungsschicht ganz oder teilweise abdeckenden Schutzschicht enthält mindestens einen Polyvinylalkohol und ein Vernetzungshilfsmittel. Es ist bevorzugt, dass der Polyvinylalkohol der Schutzschicht mit Carboxyl- oder Silanolgruppen modifiziert ist. Eine solche Schutzschicht besitzt eine hohe Affinität gegenüber der im Offset-Druckprozeß eingesetzten, bevorzugt UV-vemetzenden Druckfarbe, was entscheidend mithilft, die Forderung nach einer verbesserten Bedruckbarkeit innerhalb des Offset-Drucks zu erfüllen. Es ist weiterhin vorstellbar, Mischungen verschiedener Carboxylgruppen- oder Silanol-modifizierter Polyvinylalkohole einzusetzen.A second alternative embodiment, which is possible as an alternative to the first embodiment described above, for a protective layer wholly or partially covering the heat-sensitive recording layer contains at least one polyvinyl alcohol and a crosslinking aid. It is preferred that the polyvinyl alcohol of the protective layer is modified with carboxyl or silanol groups. Such a protective layer has a high affinity to the printing ink used in the offset printing process, preferably UV-crosslinking ink, which helps decisively to meet the requirement for improved printability within the offset printing. It is also conceivable to use mixtures of different carboxyl-group- or silanol-modified polyvinyl alcohols.
Als Vernetzungshilfsmittel in der Schutzschicht gemäß zweiter Ausführungsvariante bieten sich insbesondere solche an, die ausgewählt sind aus der Gruppe umfassend: Borsäure, Polyamin, Epoxyharz, Dialdehyd, Formaldehydoligomere, Polyaminepichlorhydrinharz, Dimethylharnstoff, Melaminformaldehyd. Auch Mischungen verschiedener Vernetzungshilfsmittel sind möglich.Suitable crosslinking aids in the protective layer according to the second embodiment are, in particular, those selected from the group comprising: boric acid, polyamine, epoxy resin, dialdehyde, formaldehyde oligomers, polyamine-epichlorohydrin resin, dimethylurea, melamine-formaldehyde. It is also possible to use mixtures of different crosslinking aids.
Es ist bevorzugt, wenn innerhalb der Schutzschicht gemäß der zweiten Ausführungsvariante das Verhältnis der Gew.-% des modifizierten Polyvinylalkohols zu dem Vernetzungshilfsmittel in einem Bereich von 20 : 1 bis 5 : 1 und besonders bevorzugt in einem Bereich von 12 : 1 bis 7 : 1 liegt. Es kann gesagt werden, dass sich dabei sich ein Verhältnis des modifizierten Polyvinylalkohols zu dem Vernetzungshilfsmittel von 100 Volumenteile zu 15 bis 30 Volumenteile bewährt hat.It is preferable if, within the protective layer according to the second embodiment, the ratio of the weight% of the modified polyvinyl alcohol to the crosslinking aid is in a range of 20: 1 to 5: 1, and more preferably in a range of 12: 1 to 7: 1 lies. It can be said that a ratio of the modified polyvinyl alcohol to the crosslinking aid of 100 parts by volume to 15 to 30 parts by volume has been proven.
Besonders gute Ergebnisse wurden erzielt, wenn die Schutzschicht gemäß der zweiten Ausführungsvariante zusätzlich ein anorganisches Pigment enthält. Dabei empfiehlt es sich besonders, wenn das anorganische Pigment ausgewählt ist aus der Gruppe umfassend Siliziumdioxid, Aluminiumhydroxid, Kalziumkarbonat, Kaolin oder einer Mischung aus den genannten anorganischen Pigmenten.Particularly good results have been achieved if the protective layer according to the second embodiment additionally contains an inorganic pigment. It is particularly recommended that the inorganic pigment is selected from the group comprising silica, aluminum hydroxide, calcium carbonate, kaolin or a mixture of said inorganic pigments.
Es ist bevorzugt, die aus wirtschaftlichen Gründen möglichst einlagig auszubildende Schutzschicht gemäß der zweiten Ausführungsvariante mit einer flächenbezogenen Masse in einem Bereich von 1,5 g/m2 bis 6 g/m2 und besonders zwischen 1,7 g/m2 und 3 g/m2 aufzutragen, ohne auf die Einlagigkeit der Schutzschicht beschränkt zu sein. Als vorteilhaft hat sich eine Glätte der Schutzschicht im Bereich von 500 und bevorzugt von 800 oder noch besser 1.000 Bekk-Sekunden (sec) bis kleiner 3.000 Bekk-sec gezeigt. Insbesondere sind Werte von 1.000 Bekk-sec bis kleiner 2.500 Bekk-sec und ganz besonders bevorzugt von 1.200 Bekk-sec bis 2.000 Bekk-sec geeignet.It is preferred that the protective layer for economic reasons to be formed as single-layer as possible according to the second embodiment with a basis weight in a range of 1.5 g / m 2 to 6 g / m 2 and especially between 1.7 g / m 2 and 3 g / m 2 apply, without being limited to the Einschichtigkeit the protective layer. It has been found to be advantageous to have a smoothness of the protective layer in the range of 500 and preferably from 800 or better still 1,000 Bekk seconds (sec) to less than 3,000 Bekk-sec. In particular, values of 1,000 Bekk-sec to less than 2,500 Bekk-sec and most preferably from 1,200 Bekk-sec to 2,000 Bekk-sec are suitable.
Das Erscheinungsbild der Schutzschicht wird maßgeblich durch die Art der Glättung und der die Friktion im Glättwerk und Kalander beeinflussenden Walzenoberflächen und deren Materialien bestimmt. Insbesondere wegen bestehender Marktanforderungen liegt ein bevorzugter Bereich zwischen 30 % und 50 %, und ganz besonders bevorzugt zwischen 40 % und 48 %, gemessen nach Tappi 450 oder ISO 2813 bei einem Reflexionswinkel von 75°. Ein weiterer bevorzugter Bereich liegt zwischen 10 % und 15 %, bestimmt nach gleichen Vorschriften und Parametern.The appearance of the protective layer is significantly determined by the type of smoothing and the friction in the calender and calender influencing roll surfaces and their materials. In particular, because of existing market requirements, a preferred range is between 30% and 50%, and most preferably between 40% and 48%, measured according to Tappi 450 or ISO 2813 at a reflection angle of 75 °. Another preferred range is between 10% and 15%, determined according to the same rules and parameters.
Besonders bewährt hat sich im Rahmen der dieser Erfindung vorausgegangenen Versuchsarbeiten die Verwendung von Glättwerken, bei denen NipcoFlex™- oder zonengeregelte Nipco-P™-Walzen zum Einsatz kommen, ohne darauf in irgendeiner Art und Weise beschränkt zu sein.Particularly useful in the context of experimental work preceding this invention has been the use of calenders that employ NipcoFlex ™ or zone controlled Nipco-P ™ rollers without being limited in any way.
Eine besonders gute Bedruckbarkeit für das Offset-Druckverfahren liegt vor, wenn die Schutzschicht des neuen wärmeempfindlichen Aufzeichnungsmaterials einen möglichst geringen polaren Anteil der als Summe aus dispersem und polarem Anteil zu bestimmenden Obenflächenspannung aufweist. Die Bestimmung der Oberflächenspannung erfolgt dabei nach
In einer bevorzugten Ausführungsform weist das erfindungsgemäße Aufzeichnungsmaterial eine nicht wärmeempfindliche, rückseitige Pigmentbeschichtung auf. Als Pigmente in der Rückseitenbeschichtung haben sich insbesondere Calciumcarbonat - bevorzugt mit einer Teilchengröße in einem kolloidalen Bereich von 60% < 2 µm bis 90% < 2 µm - und/oder Magnesiumcarbonat als geeignet erwiesen. Auch die folgenden Pigmente konnten mit positiven Ergebnisse überzeugen:
- natürliches wie kalziniertes Kaolin, bevorzugt im kolloidalen Teilchengrößen-Bereich von 60% bis 90% < 2 µm,
- Clay, Kieselsäure, Siliziumoxid, letzteres mit einer bevorzugten mittleren Teilchengröße in einem Bereich von 1 bis 6 µm,
- Aluminiumhydroxid und Böhmit, letzteres mit möglichen mittleren Teilchengrößen bis hin zu 0,5 bis 3 µm, wobei jedoch ganz besonders bevorzugt solche Böhmitprodukte sind, die eine mittlere Teilchengröße in einem Bereich von 10 bis 100 nm aufweisen,
- sowie in einem besonderen Maße Talkum mit einer bevorzugten mittleren Teilchengröße in einem Bereich von 1 bis 10 µm.
- natural and calcined kaolin, preferably in the colloidal particle size range from 60% to 90% <2 μm,
- Clay, silica, silica, the latter having a preferred average particle size in a range of 1 to 6 μm,
- Aluminum hydroxide and boehmite, the latter having possible average particle sizes up to 0.5 to 3 μm, but very particular preference is given to boehmite products having an average particle size in the range from 10 to 100 nm,
- and, to a particular extent, talc having a preferred average particle size in a range of 1 to 10 microns.
Bevorzugt enthält die Rückseitenbeschichtung mindestens eine als Vernetzer wirkende Komponente auf Polyurethanbasis, bevorzugt ist ein anionisches Polyurethan in wässriger Lösung, beispielsweise Eka SP AP 29, Eka Chemicals AB, 32301 Düren.The backcoat layer preferably comprises at least one polyurethane-based component acting as a crosslinker, preferably an anionic polyurethane in aqueous solution, for example Eka SP AP 29, Eka Chemicals AB, D-32301 Düren.
Neben den Pigmenten und der vernetzend wirkenden Komponente auf Polyurethanbasis umfasst die Rückseitenbeschichtung bevorzugt Bindemittel und hier insbesondere Stärke, Styrolbutadienlatex und gegebenenfalls Carboxy-Methyl-Cellulose. Auch die Mischung verschiedener Bindemittel in mitunter stark divergierenden Mischungsverhältnissen ist möglich und bevorzugt. Ferner sind optische Aufheller, Entschäumer sowie Komponenten zur Viskositätsregelung nach den jeweiligen Erfordernissen übliche Zuschlagstoffe.In addition to the pigments and the crosslinking component based on polyurethane, the backcoat preferably comprises binders and in particular starch, styrene-butadiene latex and optionally carboxymethyl cellulose. The mixture of different binders in sometimes highly divergent mixing ratios is possible and preferred. Furthermore, optical brighteners, defoamers and components for controlling the viscosity according to the respective requirements of conventional additives.
Es ist bevorzugt, dass die Rückseitenbeschichtung
- ■ zu 75 bis 90 Gew.-% und ganz besonders bevorzugt zu 77 bis 85 Gew.-% Pigmente,
- ■ zu 5 bis 25 Gew.-% Bindemittel,
- ■ sowie zu 0,5 bis 8 Gew.-% und ganz besonders bevorzugt zu 1,5 bis 3,5 Gew.-% Vernetzer auf Polyurethanbasis enthält.
- From 75% to 90% by weight and most preferably from 77% to 85% by weight of pigments,
- ■ from 5 to 25% by weight of binder,
- ■ and to 0.5 to 8 wt .-% and most preferably to 1.5 to 3.5 wt .-% crosslinking agent based on polyurethane.
In den dieser Erfindung zugrunde liegenden Versuchsreichen wurde herausgefunden, dass ein Rückseitenstrich mit
- ■ einem Pigment-Bindemittel-Verhältnis von 10:1 bis 2:1 und besser zwischen 7,5:1 bis 3:1 sowie
- ■ einem Bindemittel-Vernetzer-Verhältnis von 20:1 bis 1:1 und besser zwischen 10,5:1 bis 5:1
- ■ a pigment to binder ratio of 10: 1 to 2: 1 and better between 7.5: 1 to 3: 1 and
- ■ a binder to crosslinker ratio of 20: 1 to 1: 1, and more preferably between 10.5: 1 to 5: 1
Besonders positive Ergebnisse lassen sich mit einem Auftragsgewicht für die Rückseitenbeschichtung in einem Bereich von 2 bis 15 g/m2 erreichen. Je nach verfügbaren Streichwerken und avisierten Einsatzzwecken des erfindungsgemäßen Aufzeichnungsmaterials ist einerseits ein Bereich für das Auftragsgewicht der Rückseitenbeschichtung von 2,5 bis 4,5 g/m2, andererseits auch ein Bereich von 8,5 bis 12 g/m2 ganz besonders bevorzugt. Als zum Auftrag der Rückseitenbeschichtung besonders geeignete Streichwerke kommen insbesondere egalisierende Auftragsvorrichtungen wie Streichmesser- und (Roll-) Rakelstreichwerke sowie Walzenstreichwerke in Betracht, ohne darauf in irgendeiner Art und Weise beschränkt zu sein.Particularly positive results can be achieved with a coating weight for the back coating in a range of 2 to 15 g / m 2 . Depending on the available brushing and intended use of the recording material according to the invention, on the one hand a range for the coating weight of the back coating of 2.5 to 4.5 g / m 2 , on the other hand also a range of 8.5 to 12 g / m 2 is very particularly preferred. As the order of the backside coating particularly suitable brushing particularly equalizing application devices such as doctor blade and (roll) doctor blade coater and Walzenstreichwerke into consideration, without being limited in any way.
Die Erfinder erkannten, dass sich ein besonders hochwertiges Druckbild auf der Rückseite des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials gewinnen lässt, wenn die Rückseitenbeschichtung in zwei Lagen ausgebildet ist, von denen die erste, zur Substratschicht hin orientierte Lage als reiner Bindemittel-Pigmentstrich ausgebildet sein kann, während die zweite außen liegende Lage die als Vernetzer wirkende Komponente auf Polyurethanbasis enthält. In diesem Fall ist es möglich, dass nur eine Lage mit einer egalisierenden Auftragsvorrichtung aufgetragen ist, während sich für die zweite Lage als Auftragsvorrichtung auch Luftbürste und Curtain-Coater anbietet.The inventors recognized that a particularly high-quality printed image on the back of the heat-sensitive recording material according to the invention can win if the backside coating is formed in two layers, of which the first layer oriented towards the substrate layer can be formed as a pure binder pigment coating, while the second outer layer containing the crosslinking agent acting component based on polyurethane. In this case, it is possible that only one layer is applied with a leveling applicator, while the airbrush and curtain coater is available for the second layer as an applicator device.
Da die erfindungswesentliche wärmeempfindliche Aufzeichnungsschicht genauso wie die vorgeschlagene Rückseitenbeschichtung des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials sehr gut zu trocknen sind, kann in einem einzigen Arbeitsgang beispielsweise innerhalb einer Streichmaschine sowohl die Rückseitenbeschichtung wie auch die wärmeempfindlichen Aufzeichnungsschicht gegebenenfalls einschließlich der sie vollständig abdeckenden Schutzschicht aufgetragen und getrocknet werden.Since the heat-sensitive recording layer essential to the invention is very easy to dry, as well as the proposed backcoat of the thermosensitive recording material of the present invention, both the back coat and the thermosensitive recording layer may be coated and dried in a single operation, for example, including the protective layer completely covering it.
Zu diesem Zweck kann eine solche Streichmaschine (a) eine Abrollvorrichtung, (b) ein erstes Streichwerk, beispielsweise ein Curtain Coater, eine Luftbürste oder ein Rollrakel-Streichwerk zur Auftragung der wärmeempfindlichen Aufzeichnungsschicht, (c) einen ersten kontaktlosen Schwebetrocknerkanal, (d) ein Curtain Coater oder eine Luftbürste zur Auftragung der Schutzschicht, (e) optional und je nach Bauart ein kontaktloses Bahnführungssystem, (f) ein Filmaufragswerk zur Auftragung der Rückseitenbeschichtung, (g) einen zweiten kontaktlosen Schwebetrocknerkanal, (h) eine Nachtrockenpartie mit mehreren Trockenzylindern, (i) eine Rückbefeuchtungsanlage bzw. eine Beschichtungsanlage wie ein Filmauftragswerk zur Optimierung der Planlage bzw. zur Reduzierung der Roll-Neigung, (j) ein IR-Trocknungssystem, (k) ein oder mehrere Glättwerke mit jeweils einem oder mehreren Pressnips insbesondere unter Verwendung von zonenregelbaren- und/oder Schuhpresswalzen bzw. Bandkalander sowie (I) eine Aufrollvorrichtung vorsehen.For this purpose, such a coating machine (a) a rolling device, (b) a first coating, such as a curtain coater, an air brush or a roller blade coating applicator for applying the heat-sensitive recording layer, (c) a first non-contact Schwebetrocknerkanal, (d) a Curtain coater or an airbrush for applying the protective layer, (e) optionally and depending on the type, a contactless web guiding system, (f) a film applicator for application of the backside coating, (g) a second non-contact floating dryer channel, (h) an after-dryer section with several drying cylinders, ( i) a remoistening system or a coating installation such as a film applicator for optimizing the flatness or for reducing the roll tendency, (j) an IR drying system, (k) one or more calendering units each having one or more press nips, in particular using zone-controllable and / or shoe press rolls or belt calenders and (I) an A Provide rolling device.
Ferner ist es vorstellbar, wenn zwischen der Abrollvorrichtung und dem ersten Streichwerk (a, b) ein weiteres Streichwerk (b'), ausgeführt beispielsweise als Streichmesser-Auftragswerk mit zugeordneter Trocknungsapparatur (b"), das können Schwebetrocknerkanal und/oder Trockenzylinder sein, vorgesehen ist.Furthermore, it is conceivable if between the unwinding device and the first coating unit (a, b) a further coating unit (b '), for example a doctor blade applicator with associated drying apparatus (b "), which can be a floating dryer channel and / or a drying cylinder, is provided is.
Auch wenn nicht auf Papier als Substrat beschränkt, ist Papier das Substrat, die sich am Markt auch mit Blick auf die gute Umweltverträglichkeit wegen der guten Recyclingfähigkeit durchgesetzt hat und die im Sinne der Erfindung bevorzugt ist.Although not limited to paper as a substrate, paper is the substrate that has prevailed on the market with regard to the good environmental compatibility because of good recyclability and is preferred in the context of the invention.
Die in Beschreibung und Patentansprüchen gemachten Angaben zur flächenbezogenen Masse, zu Gew.-% (Gewichts-%), zu Gew.-Teilen (Gewichts-Teilen) und zu Komponentenverhältnissen beziehen sich, soweit nicht ausdrücklich anders vermerkt, jeweils auf das "atro"-Gewicht, d.h. absolut trockene Gewichtsteile. Die Abkürzung "lutro" steht für lufttrocken, und bedeutet, sofern genutzt, dass die so gekennzeichneten Komponenten in ihrer handelsüblichen Lieferform beschrieben werden.The details given in the description and patent claims relating to basis weight,% by weight (% by weight), parts by weight (parts by weight) and component ratios, unless expressly stated otherwise, refer to the "atro" -Weight, ie absolutely dry parts by weight. The abbreviation "lutro" stands for air-dry, and means, if used, that the so marked components are described in their commercial delivery form.
Das nachfolgende Beispiel und die nachfolgenden Vergleichsbeispiele werden die Erfindung weiter verdeutlichen:The following example and the following comparative examples will further illustrate the invention:
Auf einer Langsieb-Papiermaschine wird als Substratschicht eine Papierbahn aus gebleichten und gemahlenen Laub- und Nadelholzzellstoffen mit einer flächenbezogenen Masse von 67 g/m2 unter Zusatz üblicher Zuschlagstoffe in üblichen Mengen hergestellt. Frontseitig wird online innerhalb der Streichmaschine mit einem Rollrakel-Streichwerk eine hauptsächlich kalziniertes Kaolin als Pigment, Styrolbutadienlatex als Bindemittel und Stärke als Cobinder aufweisende Zwischenschicht von 9 g/m2 aufgebracht.A paper web of bleached and ground deciduous and softwood pulps with a basis weight of 67 g / m 2 is prepared on a fourdrinier paper machine as the substrate layer with the addition of conventional additives in conventional amounts. On the front, a mainly calcined kaolin pigment, Styrolbutadienlatex as a binder and starch as Cobinder having intermediate layer of 9 g / m 2 is applied online within the coating machine with a roller blade coating.
Unter Verwendung einer Streichmaschine, wie sie in Absatz [0044] in ihrem Aufbau beschrieben ist, werden auf die Zwischenschicht in dieser Reihenfolge mittels Rollrakel-Streichwerk eine wärmeempfindliche Aufzeichnungsschicht mit einer flächenbezogenen Masse von 5,4 g/m2, mittels Luftbürste eine Schutzschicht von 2,0 g/m2 und mittels Walzenstreichwerk mit nachgeschaltetem Rollrakel eine Rückseitenbeschichtung von 3 g/m2 aufgetragen.Using a coater as described in paragraph [0044] in its construction, a thermosensitive recording layer having a basis weight of 5.4 g / m 2 is applied to the intermediate layer in this order by means of a doctor blade coater, a protective layer of air brush 2.0 g / m 2 and applied by roller coater with downstream roller blade a backcoat of 3 g / m 2 .
In einer Versuchsreihe werden verschiedenen Streichfarben zur Ausbildung wärmeempfindlicher Aufzeichnungsschichten aufgetragen, bei denen jeweils der Sensibilisator ausgetauscht und alle anderen Komponenten gleich gelassen werden (nur das erfindungsgemäße Beispiel 1 enthält Tinuvin® P, nur das Vergleichsbeispiel 2 enthält Tinuvin® 144, nur das Vergleichsbeispiel 3 enthält Tinuvin® 234, nur das Vergleichsbeispiel 4 enthält Tinuvin® 312, nur das Vergleichsbeispiel 5 enthält Tinuvin® 477 DW, nur das Vergleichsbeispiel 6 enthält BNE). In der folgenden Tabelle 1 werden die Rezepturen der fertigen Aufzeichnungsschicht wiedergegeben, dabei ist Beispiel 1 erfindungsgemäß und zur Kennzeichnung grau hinterlegt, die Beispiele 2 bis 6 sind Vergleichsbeispiele.In a series of experiments various coating colors for forming heat-sensitive recording layers are applied in each of which the sensitizer is replaced and all other components are left the same (only Example 1 of the invention comprises Tinuvin ® P, only the Comparative Example 2 includes Tinuvin ® 144, contains only the Comparative Example 3 Tinuvin ® 234, only the Comparative example 4 containing Tinuvin ® 312, only the Comparative example 5 contains Tinuvin ® 477 DW, only Comparative Example 6 contains GNI). In the following Table 1, the formulations of the final recording layer are reproduced, while Example 1 according to the invention and gray background for identification, Examples 2 to 6 are comparative examples.
Zur Ausbildung der Schutzschicht wird eine Rezeptur verwendet, die
- als Pigment einen hoch gereinigten alkalisch aufbereiteten Bentonit mit Plättchenstruktur,
- als Bindemittel die wässrige Dispersion eines selbstvernetzenden Copolymers aus Acrylnitril, Methacrylamid und Acrylester
- und als Vernetzungsmittel Polyamidepichlorbydrinharz
- as a pigment a highly purified, alkaline treated bentonite with platelet structure,
- as binder, the aqueous dispersion of a self-crosslinking copolymer of acrylonitrile, methacrylamide and acrylic ester
- and as a crosslinking agent, polyamide-pichlorobydrin resin
Zur messtechnischen Erfassung der Beständigkeit, genauer der prozentualen Beständigkeit eines Thermoprobeausdruckes gegenüber Ethanol bzw. gegenüber Licht werden jeweils schwarz/weiß kariert-gestaltete Thermoprobeausdrucke mit einem Gerät der Type Atlantek 400 der Firma Printrex (USA) erstellt, wobei ein Thermokopf mit Auflösung von 300 dpi und einer Energie pro Flächeneinheit von 16 mJ/mm2 zum Einsatz kommt. Für jede Einzelbestimmung der prozentualen Beständigkeit eines Thermoprobeausdruckes wird zunächst bei einem Thermoprobeausdruck an drei Stellen die Druckdichte der schwarz gefärbten Flächen mit dem Densitometer Gretag MacBeth TYPE D19C NB/U gemessen (Fa Gretag MacBeth, 8105 Regensdorf, Schweiz). Anschließend erfolgt die jeweilige Behandlung des Thermoprobeausdrucks.To measure the durability, more precisely the percentage resistance of a Thermoprobausdruckes against ethanol or light respectively black and white checkered-designed Thermoprobeausdrucke with a device of the type Atlantek 400 made by Printrex (USA) created using a thermal head with resolution of 300 dpi and an energy per unit area of 16 mJ / mm 2 is used. For each individual determination of the percentage stability of a Thermoprobeausdruckes first, the print density of the black-colored surfaces with the densitometer Gretag MacBeth TYPE D19C NB / U measured at a Thermoprobeausdruck (Fa Gretag MacBeth, 8105 Regensdorf, Switzerland). Subsequently, the respective treatment of the Thermoprobeausdrucks.
Diese Behandlung sieht im Falle der prozentualen Beständigkeit gegenüber Ethanol das Eintauchen des Thermoprobeausdruckes in eine 25%-tige Ethanollösung (25 Vol.-% Lösung, 23° C) über 20 Minuten vor. Der Ausdruck wird anschließend mit Löschpapier vorsichtig abgetupft und dann über 24 Stunden bei 23° und 50% Luftfeuchte ruhen lassen.This treatment, in the case of percent resistance to ethanol, provides immersion of the Thermoprobertextes in a 25% ethanol solution (25 vol .-% solution, 23 ° C) over 20 minutes. The printout is then carefully blotted with blotting paper and allowed to rest for 24 hours at 23 ° and 50% humidity.
Im Falle der Untersuchung der Lichtbeständigkeit eines Thermoprobeausdrucks sieht die Behandlung des Thermoprobeausdrucks dessen Bestrahlung mit Xenonlicht vor, wofür das Gerät Suntest CPS+ der Firma Atlas (63589 Linsengericht, Deutschland) unter Verwendung eines Filters mit UV-Durchlass (290 nm), was die Bestrahlung mit Sonnenlicht simuliert, benutzt wird. Die Bestrahlung des Thermoprobeausdrucks erfolgt solange, bis eine Energie von 64.800 kJ/m2 erreicht worden ist. Anschließend wird der Ausdruck über 24 Stunden bei 23° und 50% Luftfeuchte ruhen lassen.In the case of examining the light resistance of a Thermoprobeausdrucks the treatment of Thermoprobeausdrucks its irradiation with xenon light before, for which the device Suntest CPS + Atlas (63589 Linsengericht, Germany) using a filter with UV transmission (290 nm), which irradiation with Sunlight simulated, used. The irradiation of the thermoprob expression is carried out until an energy of 64,800 kJ / m 2 has been reached. The print will then rest for 24 hours at 23 ° and 50% humidity.
Nach dem Ruhen lassen erfolgt erneut die Bestimmung der dynamischen Druckdichte an drei Stellen der schwarz gefärbten Flächen mit dem Densitometer Gretag MacBeth TYPE D19C NB/U. Die jeweiligen Mittelwerte der Messungen vor/nach dem Bad in der Ethanollösung bzw. vor/nach der Lichtbestrahlung werden gebildet und der Mittelwert nach dem Bad (nach der Bestrahlung) prozentual bezogen auf den Mittelwert vor dem Bad (vor der Bestrahlung).After resting, the determination of the dynamic print density at three points of the black-colored areas is carried out again with the Gretag MacBeth TYPE D19C NB / U densitometer. The respective mean values of the measurements before / after the bath in the ethanol solution and before / after the light irradiation are formed and the mean value after the bath (after the irradiation) as a percentage of the mean value before the bath (before the irradiation).
Zur messtechnischen Erfassung der dynamischen Druckdichte in ODU ( = Optical Density Units, gemäß DIN 16536-1, Ausgabe Mai 1997) wird ein schwarz/weiß kariert-gestalteter Thermoprobeausdruck mit einem Gerät der Type Atlantek 400 der Firma Printrex (USA) erstellt, wobei ein Thermokopf mit Auflösung von 300 dpi und einer Energie pro Flächeneinheit von 11,7 mJ/mm2 zum Einsatz kommt. Die Druckdichte selbst der schwarz gefärbten Flächen werden mit dem Densitometer Gretag MacBeth TYPE D19C NB/U gemessen (Fa Gretag MacBeth, 8105 Regensdorf, Schweiz), wobei für jeden Messwert die dynamischen Druckdichten an drei Stellen gemessen und aus den drei Einzelwerten das arithmetische Mittel gebildet wird.For metrological detection of the dynamic printing density in ODU (= Optical Density Units, according to DIN 16536-1, May 1997 issue) is a black and white checkered thermoprobe print-out using an Atlantek 400 device from Printrex (USA) using a thermal head with a resolution of 300 dpi and an energy per unit area of 11.7 mJ / mm 2 . The print density even of the black-colored areas are measured with the densitometer Gretag MacBeth TYPE D19C NB / U (Gretag MacBeth, 8105 Regensdorf, Switzerland), where the dynamic printing densities are measured at three points for each measured value and the arithmetic mean is formed from the three individual values becomes.
An den Proben It. Beispiel 1 und It der Vergleichsbeispiele 2 bis 6 wurden gemäß der vorstehend beschriebenen Vorgaben die Beständigkeiten gegenüber Ethanol als Beispiel für die Beständigkeit gegenüber Umwelteinflüssen, die Beständigkeiten gegenüber Licht und die Empfindlichkeit gegenüber zugeführter Wärme in Form eines Thermodruckbildes gemessen. Die Messwerte sind den letzten drei Spalten der Tabelle 1 zu entnehmen.On the samples It. Example 1 and It of Comparative Examples 2 to 6, the resistances to ethanol as an example of the resistance to environmental influences, the resistance to light and the sensitivity to supplied heat in the form of a thermal print image were measured according to the above-described specifications. The measured values can be found in the last three columns of Table 1.
Aus den Messwerten der Tabelle 1 ist zu erkennen, dass die Proben des erfindungsgemäßen Beispiels 1 eine sehr gute Beständigkeit gegenüber Ethanol, eine sehr gute dynamische Empfindlichkeit und eine überlegene Lichtbeständigkeit aufweisen. Damit erfüllt nur das erfindungsgemäße Beispiel 1 die Anforderungen einer hervorragenden Beständigkeit gegenüber Umwelteinflüssen sowie einer hervorragende Lichtbeständigkeit bei gleichzeitig ausreichender Empfindlichkeit gegenüber zugeführter Wärme in Form eines Thermodruckbildes. Gleichzeitig wurde an den Proben des erfindungsgemäßen Beispiels 1 eine sehr gute Bedruckbarkeit, mit Blick auf die Offset-Bedruckbarkeit zudem eine hervorragende Rupffestigkeit festgestellt.It can be seen from the measured values in Table 1 that the samples of Inventive Example 1 have a very good resistance to ethanol, a very good dynamic sensitivity and a superior light stability. Thus, only Example 1 according to the invention fulfills the requirements of excellent resistance to environmental influences as well as excellent light resistance combined with sufficient sensitivity to supplied heat in the form of a thermal printing image. At the same time, a very good printability was observed on the samples of Example 1 according to the invention, and, in view of the offset printability, an outstanding pick resistance was also found.
Das Vergleichsbeispiel 3 weist zwar eine höhere Beständigkeit gegenüber Ethanol als das erfindungsgemäße Beispiel 1 auf, jedoch sind die Messwerte von Vergleichsbeispiel 3 hinsichtlich der Lichtbeständigkeit und der dynamische Druckdichte viel zu schlecht:
im Sinne der Erfindung soll dabei die Lichtbeständigkeit bevorzugt einen Wert von 55 % übersteigen, die dynamische Druckdichte soll bevorzugt einen Wert von 1,0 ODU übersteigen und die Beständigkeit gegenüber Ethanol soll bevorzugt einen Wert von 80 % übersteigen - besonders bevorzugt einen Wert von mindestens 81 % aufweisen, wobei die genannten Werte mit Bezug auf die obigen Definition zur messtechnischen Erfassung der entsprechenden Messgrößen gelten.Although Comparative Example 3 has higher resistance to ethanol than Example 1 of the present invention, the measured values of Comparative Example 3 are far too poor in light resistance and dynamic printing density:
For the purposes of the invention, the light resistance should preferably exceed 55%, the dynamic printing density should preferably exceed 1.0 ODU and the resistance to ethanol should preferably exceed 80% - particularly preferably at least 81 %, wherein the values mentioned apply with reference to the above definition for metrological detection of the corresponding measured variables.
Das Vergleichsbeispiel 6 weist zwar höhere Werte für die dynamische Druckdichte als das erfindungsgemäße Beispiel 1 auf, jedoch sind die Messwerte von Vergleichsbeispiel 6 hinsichtlich der Lichtbeständigkeit und der Beständigkeit gegenüber Ethanol viel zu schlecht - mit Blick auf die Beständigkeit gegenüber Ethanol sogar der schlechteste Wert in der Versuchsreihe.Although Comparative Example 6 has higher dynamic printing density values than Inventive Example 1, Comparative Example 6's measured values are far too poor in light resistance and resistance to ethanol-even the worst in the case of resistance to ethanol test series.
Die vorstehend beschriebenen Versuche schildern so in anschaulicher Weise die überlegenen Eigenschaften des erfindungsgemäßen Aufzeichnungsmaterials.The experiments described above thus illustratively describe the superior properties of the novel recording material.
Claims (14)
- Heat-sensitive recording material having a substrate, which has on at least one side a heat-sensitive recording layer having a colour precursor and a colour acceptor, the colour precursor and the colour acceptor reacting with one another under the action of heat to form a colour,
characterised in that
the heat-sensitive recording layer comprises as colour acceptor N-(p-toluenesulphonyl)-N'-3-(p-toluenesulphonyl-oxy-phenyl)-urea in accordance with the following formula (1): - Heat-sensitive recording material according to claim 1, characterised in that 2-(2H-benzotriazol-2-yl)-p-cresol according to formula (2) is the sole sensitiser in the heat-sensitive recording layer.
- Heat-sensitive recording material according to either one of claims 1 and 2, characterised in that N-(p-toluenesulphonyl)-N'-3-(p-toluenesulphonyl-oxyphenyl)-urea according to formula (1) is the sole colour acceptor in the heat-sensitive recording layer.
- Heat-sensitive recording material according to any one of claims 1 to 3, characterised in that the ratio of sensitiser according to formula (2) to colour acceptor according to formula (1) is in a range of from 5 : 10 to 9 : 10.
- Heat-sensitive recording material according to any one of claims 1 to 4, characterised in that the heat-sensitive recording layer comprises 3-dibutylamino-6-methyl-7-anilinofluoran as colour precursor.
- Heat-sensitive recording material according to any one of claims 1 to 5, characterised in that the heat-sensitive recording layer comprises as binder exclusively polyvinyl alcohol in conjunction with an acrylate copolymer.
- Heat-sensitive recording material according to any one of claims 1 to 6, characterised in that the recording material comprises a pigmented intermediate layer between substrate and heat-sensitive recording layer.
- Heat-sensitive recording material according to any one of claims 1 to 7, characterised in that the heat-sensitive recording layer is entirely or partially covered by a protective layer, the protective layer comprising as binder polyvinyl alcohols modified by carboxy groups or by silanol.
- Heat-sensitive recording material according to claim 8, characterised in that the protective layer comprises cross-linking auxiliaries which are selected from the group consisting of: boric acid, polyamine, epoxy resin, dialdehyde, formaldehyde oligomers, epichlorohydrin resin, dimethylurea, melamineformaldehyde.
- Heat-sensitive recording material according to any one of claims 1 to 9, characterised in that the recording material comprises a non-heat-sensitive, rear-side pigment coating.
- Heat-sensitive recording material according to claim 10, characterised in that the rear-side coating comprises at least one polyurethane-based component acting as cross-linker.
- Heat-sensitive recording material according to either one of claims 10 and 11, characterised in that the rear-side coating- comprises a pigment, selected from the list consisting of calcium carbonate, natural kaolin such as calcined kaolin, clay, silicic acid, silicon oxide, aluminium hydroxide, boehmite and talcum,- and also comprises a binder selected from the list consisting of starch, styrene-butadiene latex and optionally carboxymethyl cellulose.
- Heat-sensitive recording material according to claim 12, characterised in that the rear-side coating comprises■ from 75 to 90 % by weight and more especially from 77 to 85 % by weight pigments,■ from 5 to 25 % by weight binder,■ and from 0.5 to 8 % by weight and more especially from 1.5 to 3.5 % by weight polyurethane-based cross-linker.
- Heat-sensitive recording material according to either one of claims 12 and 13, characterised in that the rear-side coating has- a pigment to binder ratio of from 10 : 1 to 2 : 1 and better from 7.5 : 1 to 3 : 1 and- a binder to cross-linker ratio of from 20 : 1 to 1 : 1 and better from 10.5 : 1 to 5 : 1.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT07017651T ATE458621T1 (en) | 2007-09-10 | 2007-09-10 | HEAT SENSITIVE RECORDING MATERIAL |
| EP07017651A EP2033801B1 (en) | 2007-09-10 | 2007-09-10 | Heat sensitive recording material |
| ES07017651T ES2339167T3 (en) | 2007-09-10 | 2007-09-10 | HEAT SENSITIVE RECORDING MATERIAL. |
| DE502007002945T DE502007002945D1 (en) | 2007-09-10 | 2007-09-10 | Heat-sensitive recording material |
| PCT/EP2008/007150 WO2009033589A1 (en) | 2007-09-10 | 2008-09-02 | Thermosensitive recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07017651A EP2033801B1 (en) | 2007-09-10 | 2007-09-10 | Heat sensitive recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2033801A1 EP2033801A1 (en) | 2009-03-11 |
| EP2033801B1 true EP2033801B1 (en) | 2010-02-24 |
Family
ID=38691915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP07017651A Active EP2033801B1 (en) | 2007-09-10 | 2007-09-10 | Heat sensitive recording material |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP2033801B1 (en) |
| AT (1) | ATE458621T1 (en) |
| DE (1) | DE502007002945D1 (en) |
| ES (1) | ES2339167T3 (en) |
| WO (1) | WO2009033589A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2505374A1 (en) | 2011-04-01 | 2012-10-03 | Mitsubishi HiTec Paper Europe GmbH | Heat-sensitive recording material, method for its manufacture and application |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008057270A1 (en) * | 2008-11-13 | 2010-05-20 | Kanzan Spezialpapiere Gmbh | Recording material, preferably thermal recording material and ink-jet recording material, comprises substrate and coating having polyurethane, where coating is applied to one side of substrate |
| DE102009016108A1 (en) * | 2009-04-03 | 2010-10-07 | Mitsubishi Hitec Paper Flensburg Gmbh | Heat-sensitive recording material |
| DE102011114129A1 (en) * | 2011-09-23 | 2013-03-28 | Mitsubishi Hitec Paper Europe Gmbh | Recording material for offset printing |
| EP2574645B1 (en) * | 2011-09-30 | 2014-06-25 | Mitsubishi HiTec Paper Europe GmbH | Dye acceptor which reacts with a dye precursor to form a colour and heat-sensitive recording material with such a dye acceptor |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1236299A (en) * | 1984-04-16 | 1988-05-10 | Minnesota Mining And Manufacturing Company | Prevention of spotting in thermal imaging compositions |
| FI110677B (en) * | 2001-10-12 | 2003-03-14 | Jujo Thermal Oy | Heat-sensitive recording material for use in, e.g. stickers, has coating layer comprising chelate-type color forming system and leuco dye with urea-based developer |
| JP4229944B2 (en) * | 2003-06-25 | 2009-02-25 | ケミプロ化成株式会社 | Developer for recording materials |
| US20080194403A1 (en) * | 2004-01-13 | 2008-08-14 | Junpei Natsui | Laser Recording Thermally Sensitive Recording Medium |
| US7846870B2 (en) * | 2004-04-22 | 2010-12-07 | Oji Paper Co., Ltd. | Heat-sensitive recording body |
| CN100548706C (en) * | 2005-01-28 | 2009-10-14 | 王子制纸株式会社 | Thermal recording medium |
| JP2006297840A (en) * | 2005-04-22 | 2006-11-02 | Nippon Soda Co Ltd | Recording material and recording sheet |
-
2007
- 2007-09-10 AT AT07017651T patent/ATE458621T1/en active
- 2007-09-10 DE DE502007002945T patent/DE502007002945D1/en active Active
- 2007-09-10 EP EP07017651A patent/EP2033801B1/en active Active
- 2007-09-10 ES ES07017651T patent/ES2339167T3/en active Active
-
2008
- 2008-09-02 WO PCT/EP2008/007150 patent/WO2009033589A1/en active Application Filing
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2505374A1 (en) | 2011-04-01 | 2012-10-03 | Mitsubishi HiTec Paper Europe GmbH | Heat-sensitive recording material, method for its manufacture and application |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE458621T1 (en) | 2010-03-15 |
| EP2033801A1 (en) | 2009-03-11 |
| WO2009033589A1 (en) | 2009-03-19 |
| DE502007002945D1 (en) | 2010-04-08 |
| ES2339167T3 (en) | 2010-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2033799B1 (en) | Heat-sensitive recording material | |
| EP3109059A1 (en) | Heat sensitive recording material | |
| EP2033801B1 (en) | Heat sensitive recording material | |
| WO2016102076A1 (en) | Heat-sensitive recording material for offset printing | |
| WO2011067004A1 (en) | Heat-sensitive recording material with barrier coating | |
| EP2112000B1 (en) | Heat sensitive recording material | |
| EP2033802B1 (en) | Heat sensitive recording material with reverse coating | |
| EP2329955B1 (en) | Heat-sensitive recording material with authenticity characteristic | |
| DE69007984T2 (en) | Heat sensitive recording paper. | |
| EP1543984B1 (en) | Heat-sensitive recording material for double-sided printing | |
| EP2505374B1 (en) | Heat-sensitive recording material, method for its manufacture and application | |
| EP2033800B1 (en) | Heat-sensitive recording material | |
| DE102006050420B3 (en) | Heat-sensitive recording material, useful for printing tickets, has recording layer containing fluoran derivative color former and sulfonyl-urea and diphenyl sulfone derivative dye acceptors | |
| EP2487043B1 (en) | Method for producing a heat-sensitive recording material | |
| EP1925459B1 (en) | Method of producing a heat-sensitive recording material with authentification feature | |
| DE10392446T5 (en) | Thermal recording material for offset printing | |
| EP1527900B1 (en) | Thermosensitive recording material, its' use and its' method of preparation. | |
| EP2414173B1 (en) | Heat-sensitive recording material | |
| EP2480415B1 (en) | Heat-sensitive recording material with reverse face coating | |
| EP2636533B1 (en) | Method for producing a recording material with an authentication feature | |
| EP2758249B1 (en) | Recording material for offset printing | |
| EP1813436A2 (en) | Heat sensitive recording material comprising a feature for authentification |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR |
|
| AX | Request for extension of the european patent |
Extension state: AL BA HR MK RS |
|
| 17P | Request for examination filed |
Effective date: 20090911 |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| AKX | Designation fees paid |
Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
| REF | Corresponds to: |
Ref document number: 502007002945 Country of ref document: DE Date of ref document: 20100408 Kind code of ref document: P |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: T3 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2339167 Country of ref document: ES Kind code of ref document: T3 |
|
| LTIE | Lt: invalidation of european patent or patent extension |
Effective date: 20100224 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS 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: 20100624 Ref country code: PT 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: 20100625 Ref country code: LT 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: 20100224 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL 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: 20100224 Ref country code: LV 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: 20100224 Ref country code: FI 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: 20100224 Ref country code: SI 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: 20100224 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE 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: 20100224 Ref country code: RO 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: 20100224 Ref country code: GR 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: 20100525 Ref country code: EE 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: 20100224 Ref country code: CY 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: 20100224 Ref country code: IE 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: 20100224 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG 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: 20100524 Ref country code: SK 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: 20100224 Ref country code: CZ 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: 20100224 |
|
| 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 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK 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: 20100224 |
|
| 26N | No opposition filed |
Effective date: 20101125 |
|
| BERE | Be: lapsed |
Owner name: MITSUBISHI HITEC PAPER FLENSBURG G.M.B.H. Effective date: 20100930 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100930 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100930 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT 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: 20100224 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110930 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110930 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100910 Ref country code: HU 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: 20100825 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR 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: 20100224 |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 458621 Country of ref document: AT Kind code of ref document: T Effective date: 20120910 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120910 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 10 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 11 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R081 Ref document number: 502007002945 Country of ref document: DE Owner name: MITSUBISHI HITEC PAPER EUROPE GMBH, DE Free format text: FORMER OWNER: MITSUBISHI HITEC PAPER FLENSBURG GMBH, 24941 FLENSBURG, DE |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 12 |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: PD Owner name: MITSUBISHI HITEC PAPER EUROPE GMBH; DE Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), MERGE; FORMER OWNER NAME: MITSUBISHI HITEC PAPER FLENSBURG GMBH Effective date: 20180914 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: PC2A Owner name: MITSUBISHI HITEC PAPER EUROPE GMBH Effective date: 20181108 |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E Free format text: REGISTERED BETWEEN 20181105 AND 20181107 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20231002 Year of fee payment: 17 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240926 Year of fee payment: 18 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20240922 Year of fee payment: 18 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20240924 Year of fee payment: 18 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20240925 Year of fee payment: 18 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20240926 Year of fee payment: 18 |