EP2033799A1 - Heat-sensitive recording material - Google Patents
Heat-sensitive recording material Download PDFInfo
- Publication number
- EP2033799A1 EP2033799A1 EP07017263A EP07017263A EP2033799A1 EP 2033799 A1 EP2033799 A1 EP 2033799A1 EP 07017263 A EP07017263 A EP 07017263A EP 07017263 A EP07017263 A EP 07017263A EP 2033799 A1 EP2033799 A1 EP 2033799A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- methyl
- heat
- anilinofluoran
- sensitive recording
- amino
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 44
- -1 urea-urethane compound Chemical class 0.000 claims abstract description 31
- 239000000370 acceptor Substances 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 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 abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000004014 plasticizer Substances 0.000 claims description 10
- 101710137710 Thioesterase 1/protease 1/lysophospholipase L1 Proteins 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000004202 carbamide Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 56
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000049 pigment Substances 0.000 description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 8
- 238000005507 spraying Methods 0.000 description 8
- 239000001023 inorganic pigment Substances 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- 241000294754 Macroptilium atropurpureum Species 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000012860 organic pigment Substances 0.000 description 5
- 230000000284 resting effect Effects 0.000 description 5
- JWSWULLEVAMIJK-UHFFFAOYSA-N 1-phenylmethoxynaphthalene Chemical compound C=1C=CC2=CC=CC=C2C=1OCC1=CC=CC=C1 JWSWULLEVAMIJK-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- OYQYHJRSHHYEIG-UHFFFAOYSA-N ethyl carbamate;urea Chemical compound NC(N)=O.CCOC(N)=O OYQYHJRSHHYEIG-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- ODCWYMIRDDJXKW-UHFFFAOYSA-N simazine Chemical compound CCNC1=NC(Cl)=NC(NCC)=N1 ODCWYMIRDDJXKW-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 3
- 231100000489 sensitizer Toxicity 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- OAGNKYSIOSDNIG-UHFFFAOYSA-N 1-methyl-3-[2-(3-methylphenoxy)ethoxy]benzene Chemical compound CC1=CC=CC(OCCOC=2C=C(C)C=CC=2)=C1 OAGNKYSIOSDNIG-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical class C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- AGPLQTQFIZBOLI-UHFFFAOYSA-N 1-benzyl-4-phenylbenzene Chemical group C=1C=C(C=2C=CC=CC=2)C=CC=1CC1=CC=CC=C1 AGPLQTQFIZBOLI-UHFFFAOYSA-N 0.000 description 1
- 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
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- JIINFQZEQNJKMR-UHFFFAOYSA-N 3-N,3-N-dibutyl-6-N,6-N-diethyl-9H-fluorene-3,6-diamine Chemical compound C(CCC)N(C=1C=CC=2CC3=CC=C(C=C3C=2C=1)N(CC)CC)CCCC JIINFQZEQNJKMR-UHFFFAOYSA-N 0.000 description 1
- NYMQRLJHQHVCAD-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3,3-bis[2-[4-(dimethylamino)phenyl]-2-(4-methoxyphenyl)ethenyl]-2-benzofuran-1-one Chemical compound C1=CC(OC)=CC=C1C(C=1C=CC(=CC=1)N(C)C)=CC1(C=C(C=2C=CC(OC)=CC=2)C=2C=CC(=CC=2)N(C)C)C(C(Cl)=C(Cl)C(Cl)=C2Cl)=C2C(=O)O1 NYMQRLJHQHVCAD-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004971 Cross linker Substances 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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229940100389 Sulfonylurea Drugs 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive 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
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- BPLKDVGMXNZCQO-UHFFFAOYSA-N benzyl 4-phenylmethoxybenzoate Chemical compound C=1C=C(OCC=2C=CC=CC=2)C=CC=1C(=O)OCC1=CC=CC=C1 BPLKDVGMXNZCQO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 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
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 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
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 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
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003203 everyday effect Effects 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
- 238000007667 floating Methods 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
- 239000011121 hardwood Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 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
- 238000002156 mixing Methods 0.000 description 1
- JHOKTNSTUVKGJC-UHFFFAOYSA-N n-(hydroxymethyl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCO JHOKTNSTUVKGJC-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YROXIXLRRCOBKF-UHFFFAOYSA-N sulfonylurea Chemical class OC(=N)N=S(=O)=O YROXIXLRRCOBKF-UHFFFAOYSA-N 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000007651 thermal printing Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- ZJHHPAUQMCHPRB-UHFFFAOYSA-N urea urea Chemical class NC(N)=O.NC(N)=O ZJHHPAUQMCHPRB-UHFFFAOYSA-N 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
- 239000003232 water-soluble binding agent Substances 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
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
- B41M5/323—Organic colour formers, e.g. leuco dyes
- B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
- B41M5/3275—Fluoran compounds
Definitions
- the present invention relates to a heat-sensitive recording material comprising a substrate, optionally a pigmented intermediate layer applied to the substrate, and a thermosensitive recording layer containing a color former and color acceptors.
- the present invention also relates to the use of the thus proposed heat-sensitive recording material as a ticket or as a ticket.
- Heat-sensitive recording materials of the type described above with, for example, a paper sheet, 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 color-cartridge-free printers, which in their function no longer need to be controlled by anyone, 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.
- thermoformed prints To increase the resistance of thermoformed prints to water, aqueous alcohol solutions and plasticizers suggests the DE 10 2004 044 204 A1 a heat-sensitive recording material, whose heat-sensitive recording layer has conventional dye precursors and the combination of a phenolic color developer and a urea-urethane-based color developer.
- Urea urea compounds as developers which can be used to increase the print density of thermoformed prints also in combination generally with sulfonylurea are known from EP 1 116 793 A1 as well as from the DE 692 04 777 T2 It is not known that these documents refer to the outstanding effect of N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea.
- 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.
- a variety of Sultonylhamstoffen including N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) urea, called in one embodiment in combination with urea urethane compounds can be combined as a second developer.
- a disadvantage of the recording materials according to the writings discussed above is in particular in the first case too low plasticizer resistance and a lack of resistance to sprays of glycolic liquids, associated with very low whiteness of the recording material, and the much too complex manufacturing processes, the use of the proposals in Exclude everyday life often.
- the present invention therefore has the object to provide a suitable in particular as a ticket and / or as a ticket heat-sensitive recording material available, which must be produced due to high sales volumes in a fiercely competitive market at low production costs and therefore has to dispose of a simple structure.
- the new recording material no additional protective layer to cover the require heat-sensitive recording layer, because such a protective layer is too costly both in terms of the necessary raw materials as well as in terms of the necessary machinery and process energies.
- the new recording material should have excellent resistance to ethanol solutions, water, plasticizers, and ideally also to glycol-containing liquid mists.
- the new recording material requirements for good Bestkovbarkarkeit and Entwertraj are made, which is to be understood in the sense of this invention underlying task that stamped Entwerter Schweizer after about 10 seconds neither dry nor wet can be completely wiped away.
- the ratio of the two dye acceptors, based on wt.% In the heat-sensitive recording layer is N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea according to formula (1) the urea-urethane compound of the formula (2) in a range of 1: 1.5 to 1: 2.8.
- the present invention extends to the same extent to the use of such a heat-sensitive recording material described as a ticket or as a ticket.
- each black-and-white checkered Thermoprobeaustike with a device of the type Atlantek 400 made by Viex (USA) created using a thermal head with resolution of 300 dpi and an energy per unit area of 16 mJ / mm 2 is used.
- the percentage resistance of a Thermoprobeaustikes against ethanol or water is first measured at a Thermoprobeaustik at three points, the print density of the black-colored surfaces with the densitometer Gretag MacBeth TYPE D19C NB / U (Fa Gretag MacBeth, 8105 Regensdorf, Switzerland). Subsequently, the respective treatment of the Thermoprobeaus horrs.
- This treatment in the case of percent resistance to a 25% ethanol solution, provides immersion of the Thermoprobertextes in an ethanol bath (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.
- thermoprobe print In the case of percent resistance to water, the thermoprobe print is placed in a water bath (deionized water, 23 ° C) for 20 minutes. Dabing and resting is then carried out as in the ethanol treatment.
- thermoprobeal print is sprayed with the liquid until it forms a closed liquid film on the sample.
- the sample is then sealed airtight by means of a desiccator for 20 minutes and then allowed to rest for 1 hour 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 densitometer Gretag MacBeth TYPE D19C NB / U.
- the respective mean values of the measurements before / after the bath in the ethanol solution or in water or before / after spraying with glycol-containing liquid are formed and the average value after the bath / spraying as a percentage of the mean before the bath / spraying.
- Thermoprobeaustikes against plasticizer For each individual determination of the percentage resistance of a Thermoprobeaustikes against plasticizer is initially on a device made by Atlantek 400 type Viex (USA) produced Thermoprobeaustik a 10 cm piece of TESA ® graphic film 57331 glued. Subsequently, the print density of the black-colored areas is measured immediately at three points using the densitometer Gretag MacBeth TYPE D19C NB / U. The print will then rest for 24 hours at 23 ° and 50% humidity. After resting, the print density is again determined at three points on the black-colored areas using the densitometer Gretag MacBeth TYPE D19C NB / U. The respective mean values of the measurements before / after resting are formed and the average value after resting can be left to rest before the mean value.
- samples of the heat-sensitive recording material according to the invention, on which no thermal expression is formed, sprayed with a glycol-containing liquid it comes at the sprayed sites to a reaction of the color former with the two color acceptors, which refers to a visible graying of the samples, here as "background graying" , leads.
- This graying can be detected by measuring, in which the samples without thermal expression are sprayed full enough with the glycol-containing liquid until a closed liquid film forms on the sample.
- the samples are then sealed airtight by means of a desiccator for 20 minutes and then allowed to rest for 1 hour at 23 ° and 50% humidity.
- the recording material of the present invention has such a determined optical density of the background in a range of 0.12 to 0.25 ODU.
- thermoprobauseaustik For metrological detection of the dynamic printing density, a black and white checkered thermoprobauseaustik is created with a device of the type Atlantek 400 from Viex (USA), a thermal head with resolution of 300 dpi and an energy per unit area of 9 mJ / mm 2 for Use comes.
- 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.
- thermosensitive recording layer it is possible for the thermosensitive recording layer to comprise more than one color former, each selected from the color formers listed above in paragraph [0009].
- the recording material according to the invention may, in addition to these substances specified as fabifiers, also contain one or more of the following compounds absorbing in the near infrared range:
- the two color acceptors of the formula (1) and the formula (2) can constitute up to 60% by weight, but preferably within the range of 45 to 55% by weight of the heat-sensitive recording layer.
- the effect that the mixture of the two color acceptors brings about in their entirety is a combination resulting from the peculiarities of the two individual color acceptors: While N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy -phenyl) urea according to formula (1) has been recognized as a color acceptor after numerous individual and cross experiments, which is expected to high sensitivity of the heat-sensitive recording layer to energy exposure, urea-urethane compounds according to the formula (2) may be more such as color acceptors be described in which the induced by energy print image has a high stability against counterfeiting and environmental influences.
- thermosensitive recording material When both color acceptors are used in a compounding ratio in the recording layer as recognized by the present inventors, the result is a fast-response thermosensitive recording material that surprisingly tends to have little background graying and has a heat-induced printed image resistant to environmental influences.
- the recording layer of the thermosensitive recording material of the present invention may also preferably contain sensitisers having a melting point of preferably from 60 ° C to 184 ° C, more preferably having a melting point of from 80 ° C to 140 ° C, to increase the thermal responsiveness.
- Such sensitizers are, for example: benzyl p-benzyloxybenzoate, stearamide, N-methylol stearamide, p-benzylbiphenyl, 1,2-di (phenoxy) ethane, 1,2-di (m-methylphenoxy) ethane, m-terphenyl, dibenzyl, Benzyl naphthyl ether and diphenyl sulfone, with benzyl naphthyl ether, diphenyl sulfone, 1,2-di (m-methylphenoxy) ethane and 9,2-di (phenoxy) ethane being preferred.
- 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 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.
- polyvinyl alcohol in combination with acrylate copolymers are considered to be particularly preferred binders which are incorporated in the heat-sensitive recording layer in a range of 9 to 21% by weight, based on the total weight of the recording layer.
- the coating composition for forming the heat-sensitive recording layer may further contain lubricants 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.
- the recording layer preferably has a whiteness in a range of 79 to 85% when using light with no UV content and a whiteness ranging from 87 to 93% when using UV light. Fraction, measured in each case according to ISO 2469 / ISO 2470, but D65 light is used at an observation angle of 8 °.
- roller coater, knife coater, curtain coater or air brush are particularly suitable as coating apparatus for applying the heat-sensitive recording layer.
- the coating composition used to form the recording layer is aqueous.
- the subsequent drying of the coating composition is usually done by a method in which heat is supplied, as is done by hot-air floating dryer or contact dryer. Proven is also a combination of the listed dry processes.
- the basis weight of the heat-sensitive recording layer is preferably from 2 to 6 g / m 2, and more preferably from 2.3 to 5.8 g / m 2 .
- a pigmented intermediate layer is expediently arranged between the recording layer and the substrate of the heat-sensitive recording material according to the invention.
- the intermediate layer is applied in a preferred embodiment with leveling coating devices, such as, for example, roller coater, doctor blade or doctor blade coaters, the intermediate layer can also make a positive contribution to equalization of the substrate surface, thus increasing the amount of coating material necessarily to be applied to the substrate heat-sensitive recording layer reduced.
- leveling coating devices such as, for example, roller coater, doctor blade or doctor blade coaters
- the intermediate layer can also make a positive contribution to equalization of the substrate surface, thus increasing the amount of coating material necessarily to be applied to the substrate heat-sensitive recording layer reduced.
- For the basis weight of the intermediate layer a preferred range between 5 and 20 g / m 2 and even better between 7 and 12 g / m 2 has proven.
- inorganic oil-absorbing pigments are incorporated in the intermediate layer located between the recording layer and the substrate these pigments absorb the wax components of the heat-sensitive recording layer liquefied by the action of heat of the thermal head in the case of typeface formation and thus promote a still safer and faster functioning of the heat-induced recording, which is why such an embodiment is considered preferable.
- the pigments of the intermediate layer has an oil absorption of at least 80 cm3 / 100 g, and more preferably 100 cm3 / 100 g, determined according to the Japanese standard JIS K 5101, is having.
- Calcined kaolin has proven particularly useful due to its large absorption reservoir in the cavities.
- the following inorganic pigments are also very well suited as constituents of the intermediate layer: silicon oxide, bentonite, calcium carbonate and aluminum oxide and, in particular, boehmite here. Also mixtures of several different types of inorganic pigments are conceivable.
- the ratio between organic and inorganic pigment is a compromise of the effects caused by the two types of pigments, which is particularly advantageously solved when the pigment mixture to 5 to 30 wt .-% or better to 8 to 20 wt .-% of organic and 95 to 70 wt .-% or better to 92 to 80 wt .-% consists of inorganic pigment.
- Pigment mixtures of different organic pigments are conceivable.
- the pigmented intermediate layer contains at least one binder, preferably based on a synthetic polymer, wherein, for example, styrene-butadiene latex gives particularly good results.
- a synthetic binder with the addition of at least one natural polymer, particularly preferably starch, represents a particularly suitable embodiment.
- a binder-pigment ratio within the pigmented intermediate layer between 3 : 7 and 1: 9, each based on wt .-%, a particularly suitable embodiment is present.
- a non-surface treated base paper is to be understood as meaning a base paper which has not been treated in a size press or in a coating device.
- a non-surface-treated, sized in the mass base paper with an inorganic pigment, in particular calcium carbonate is considered suitable in the mass.
- films of, for example, polyolefin and polyolefin-coated papers as a substrate are possible to the same extent, without such an embodiment having an exclusive character.
- the substrate used is on a fourdrinier paper machine made of bleached and ground hardwood and softwood pulps with the addition of 0.6% by weight (atro) rosin size as engine sizing and other conventional additives, based on the total solids content (atro) of the pulp fed to the paper machine, a backing paper having a basis weight of 53 g / m 2 made.
- a calcined kaolin pigment, styrene-butadiene latex as a binder and, in addition to other aids, starch as cobinder-containing intermediate layer having a basis weight of 9 g / m 2 is applied using a doctor blade.
- heat-sensitive recording layer which are not stated in percent and based on the total weight in% by weight (atro) include dispersants, defoamers, optical brighteners, thickeners, waxes and crosslinkers.
- this ratio is 4: 1, which means that too little urea-urethane compound according to formula (2) in relation to N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl) Oxy-phenyl) urea according to formula (1) is used in the heat-sensitive recording layer.
- this ratio is 1: 5, which means that a lot of urea-urethane compound of the formula (2) in proportion to N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea according to formula (1) is used in the heat-sensitive recording layer.
- thermosensitive recording materials Upon completion of patterns of thermosensitive recording materials according to the two Comparative Examples 1 and 3 and Example 2 of the present invention, dynamic pressure densities and percent resistances to a 25% ethanol solution versus water and plasticizer are described in detail in the specification - created black-and-white checkered Thermoprobeaustike with a device of the type Atlantek 400 from Viex (USA), wherein a thermal head with resolution of 300 dpi and an energy per unit area of 9 mJ / mm 2 (dynamic printing densities) and 16 mJ / mm 2 (percent resistances) is used.
- Example 2 of the invention Only heat-sensitive recording materials according to Example 2 of the invention are convincing in terms of sensitivity and resistance to environmental influences. Spraying with glycol-containing liquids leaves a trail in the form of a gray discoloration, which is advantageous in many applications. In the comparative examples, the image can be deleted without a trace. Also, a sufficiently large stampability and Desertability is found.
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 vorliegende Erfindung betrifft ein wärmeemphndliches Aufzeichnungsmaterial mit einem Substrat, optional einer auf das Substrat aufgebrachten pigmentierten Zwischenschicht sowie einer Farbbildner und Farbakzeptoren enthaltenden wärmeempfindlichen Aufzeichnungsschicht. Die vorliegende Erfindung betrifft genauso die Verwendung des derart vorgeschlagenen wärmeempfindlichen Aufzeichnungsmaterials als Ticket bzw. als Fahrschein.The present invention relates to a heat-sensitive recording material comprising a substrate, optionally a pigmented intermediate layer applied to the substrate, and a thermosensitive recording layer containing a color former and color acceptors. The present invention also relates to the use of the thus proposed heat-sensitive recording material as a ticket or as a ticket.
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 Farbkartuschen-freien 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 paper sheet, 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 color-cartridge-free printers, which in their function no longer need to be controlled by anyone, 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.
Zur Steigerung der Beständigkeiten ausgebildeter Thermoausdrucke gegenüber Wasser, wässerigen Alkohollösungen und Weichmachern schlägt die
Hamstoff-Urethanverbindungen als Entwickler, die zur Steigerung der Druckdichte ausgebildeter Thermoausdrucke auch in Kombination allgemein mit Sulfonylharnstoff verwendet werden können, sind aus der
Gegenstand der
Nachteilig an den Aufzeichnungsmaterialien entsprechend den oben diskutierten Schriften ist insbesondere im ersten Fall eine zu geringe Weichmacherbeständigkeit sowie eine nicht gegebene Beständigkeit gegenüber Sprühnebeln aus glycolhaltigen Flüssigkeiten, verbunden mit sehr geringer Weiße des Aufzeichnungsmaterials, sowie die viel zu aufwändigen Herstellungsprozesse, die den Gebrauch der Vorschläge im Alltag oft ausschließen.A disadvantage of the recording materials according to the writings discussed above is in particular in the first case too low plasticizer resistance and a lack of resistance to sprays of glycolic liquids, associated with very low whiteness of the recording material, and the much too complex manufacturing processes, the use of the proposals in Exclude everyday life often.
Die vorliegende Erfindung hat deshalb die Aufgabe, ein insbesondere als Ticket und/oder als Fahrschein geeignetes wärmeempfindliches Aufzeichnungsmaterial zur Verfügung zu stellen, das aufgrund hoher Absatzmengen in einem heftig umkämpften Markt zu geringen Produktionskosten herstellbar sein muss und deshalb über einen einfachen Aufbau zu verfügen hat. Insbesondere soll das neue Aufzeichnungsmaterial keiner zusätzlichen Schutzschicht zur Abdeckung der wärmeempfindlichen Aufzeichnungsschicht bedürfen, weil eine solche Schutzschicht zu kostenintensiv sowohl hinsichtlich der dafür notwendigen Rohstoffe wie auch hinsichtlich der dafür notwendigen Maschinen und Prozessenergien ist. Gleichzeitig soll das neue Aufzeichnungsmaterial jedoch eine ausgezeichnete Beständigkeit gegenüber Ethanollösungen, Wasser, Weichmacher und idealerweise auch gegenüber glycolhaltigen Flüssigkeitsnebeln aufweisen. Auch werden an das neue Aufzeichnungsmaterial Anforderungen hinsichtlich einer guten Bestempelbarkarkeit und Entwertbarkeit gestellt, worunter im Sinne der dieser Erfindung zugrunde liegenden Aufgabe zu verstehen ist, dass aufgestempelte Entwerterzeichen nach ca. 10 Sekunden weder trocken noch genässt vollständig weggewischt werden können.The present invention therefore has the object to provide a suitable in particular as a ticket and / or as a ticket heat-sensitive recording material available, which must be produced due to high sales volumes in a fiercely competitive market at low production costs and therefore has to dispose of a simple structure. In particular, the new recording material, no additional protective layer to cover the require heat-sensitive recording layer, because such a protective layer is too costly both in terms of the necessary raw materials as well as in terms of the necessary machinery and process energies. At the same time, however, the new recording material should have excellent resistance to ethanol solutions, water, plasticizers, and ideally also to glycol-containing liquid mists. Also, the new recording material requirements for good Bestempelbarkarkeit and Entwertbarkeit are made, which is to be understood in the sense of this invention underlying task that stamped Entwerterzeichen after about 10 seconds neither dry nor wet can be completely wiped away.
Die vorgegebene Aufgabe wird gelöst mit einem wärmeempfindlichen Aufzeichnungsmaterial, umfassend ein Substrat und eine Farbbildner und Farbakzeptoren enthaltende wärmeempfindliche Aufzeichnungsschicht, wobei
- ■ die Farbbildner ausgesucht sind aus der Liste, umfassend: 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,
- ■ die wärmeempfindliche Aufzeichnungsschicht zwei Farbakzeptoren aufweist, das sind: N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-hamstoff gemäß der folgenden Formel (1):
- ■ wobei das auf Gew.-% in der wärmeempfindlichen Aufzeichnungsschicht bezogene Verhältnis der beiden Farbakzeptoren N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-hamstoff gemäß Formel (1) zu der Harnstoff-Urethan-Verbindung gemäß Formel (2) in einem Bereich von (1 : größer 1) bis (1 : 3) liegt.
- ■ the color formers are selected from the list comprising: 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,
- The heat-sensitive recording layer has two dye acceptors which are: N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea according to the following formula (1):
- Wherein the ratio of the two dye acceptors based on wt .-% in the heat-sensitive recording layer N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea according to formula (1) to the urea Urethane compound of formula (2) in a range of (1: greater than 1) to (1: 3).
In einer bevorzugten Ausführungsform liegt das auf Gew.-% in der wärmeempfindlichen Aufzeichnungsschicht bezogene Verhältnis der beiden Farbakzeptoren N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-hamstoff gemäß Formel (1) zu der Harnstoff-Urethan-Verbindung gemäß Formel (2) in einem Bereich von 1 : 1,5 bis 1 : 2,8.In a preferred embodiment, the ratio of the two dye acceptors, based on wt.% In the heat-sensitive recording layer, is N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea according to formula (1) the urea-urethane compound of the formula (2) in a range of 1: 1.5 to 1: 2.8.
Die vorliegende Erfindung erstreckt sich im gleichen Maße auf die Verwendung eines derart beschriebenen wärmeempfindlichen Aufzeichnungsmaterials als Ticket bzw. als Fahrschein.The present invention extends to the same extent to the use of such a heat-sensitive recording material described as a ticket or as a ticket.
Das erfindungsgemäße wärmeempfindliche Aufzeichnungsmaterial weist bevorzugt Werte für die prozentuale Beständigkeit eines Thermoprobeausdruckes
- in einem Bereich von 94,5% bis 98,5% gegenüber einer 25%-tigen Ethanollösung,
- in einem Bereich von 98,5% bis 99,5% gegenüber Wasser,
- in einem Beeich von 93,5% bis 88,5% gegenüber Weichmacher (TESA®-Grafik-Film 57331)
- in a range of 94.5% to 98.5% over a 25% ethanol solution,
- in a range of 98.5% to 99.5% with respect to water,
- in a range from 93.5% to 88.5% compared to plasticizers (TESA ® graphic film 57331)
Zur messtechnischen Erfassung der prozentualen Beständigkeit eines Thermoprobeausdruckes 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 gegenüber Ethanol oder Wasser 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 percentage of a Thermoprobeausdruckes each black-and-white checkered 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 the percentage resistance of a Thermoprobeausdruckes against ethanol or water is first measured at a Thermoprobeausdruck at three points, the print density of the black-colored surfaces with the densitometer Gretag MacBeth TYPE D19C NB / U (Fa Gretag MacBeth, 8105 Regensdorf, Switzerland). Subsequently, the respective treatment of the Thermoprobeausdrucks.
Diese Behandlung sieht im Falle der prozentualen Beständigkeit gegenüber einer 25%-tigen Ethanollösung das Eintauchen des Thermoprobeausdruckes in ein Ethanolbad (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 a 25% ethanol solution, provides immersion of the Thermoprobertextes in an ethanol bath (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 prozentualen Beständigkeit gegenüber Wasser wird der Thermoprobeausdruck über 20 Minuten in ein Wasserbad (entionisiertes Wasser, 23° C) gelegt. Abtupfen und ruhen lassen erfolgt anschließend wie bei der Ethanolbehandlung.In the case of percent resistance to water, the thermoprobe print is placed in a water bath (deionized water, 23 ° C) for 20 minutes. Dabing and resting is then carried out as in the ethanol treatment.
Im Falle der prozentualen Beständigkeit gegenüber glycolhaltiger Flüssigkeit wird der Thermoprobeausdruck satt mit der Flüssigkeit eingesprüht, bis sich ein geschlossener Flüssigkeitsfilm auf der Probe ausbildet. Die Probe wird dann luftdicht mittels Exsikkator für 20 Minuten eingeschlossen und dann über 1 Stunde bei 23° und 50% Luftfeuchte ruhen lassen.In the case of the percentage resistance to glycol-containing liquid, the thermoprobeal print is sprayed with the liquid until it forms a closed liquid film on the sample. The sample is then sealed airtight by means of a desiccator for 20 minutes and then allowed to rest for 1 hour 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. in Wasser bzw. vor/nach dem Besprühen mit glycolhaltiger Flüssigkeit werden gebildet und der Mittelwert nach dem Bad/Besprühen prozentual bezogen auf den Mittelwert vor dem Bad/Besprühen.After resting, the determination of the dynamic print density at three points of the black-colored areas is carried out again with the densitometer Gretag MacBeth TYPE D19C NB / U. The respective mean values of the measurements before / after the bath in the ethanol solution or in water or before / after spraying with glycol-containing liquid are formed and the average value after the bath / spraying as a percentage of the mean before the bath / spraying.
Für jede Einzelbestimmung der prozentualen Beständigkeit eines Thermoprobeausdruckes gegenüber Weichmacher wird zunächst auf einen mittels Gerät der Type Atlantek 400 der Firma Printrex (USA) erstellten Thermoprobeausdruck ein ca. 10 cm langes Stück TESA®-Grafik-Film 57331 aufgeklebt. Anschließend wird unverzüglich an drei Stellen die Druckdichte der schwarz gefärbten Flächen mit dem Densitometer Gretag MacBeth TYPE D19C NB/U gemessen. Der Ausdruck wird dann über 24 Stunden bei 23° und 50% Luftfeuchte ruhen lassen. Nach dem Ruhen lassen erfolgt erneut die Bestimmung der 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 ruhen lassen werden gebildet und der Mittelwert nach dem ruhen lassen bezogen auf den Mittelwert vor dem ruhen lassen.For each individual determination of the percentage resistance of a Thermoprobeausdruckes against plasticizer is initially on a device made by Atlantek 400 type Printrex (USA) produced Thermoprobeausdruck a 10 cm piece of TESA ® graphic film 57331 glued. Subsequently, the print density of the black-colored areas is measured immediately at three points using the densitometer Gretag MacBeth TYPE D19C NB / U. The print will then rest for 24 hours at 23 ° and 50% humidity. After resting, the print density is again determined at three points on the black-colored areas using the densitometer Gretag MacBeth TYPE D19C NB / U. The respective mean values of the measurements before / after resting are formed and the average value after resting can be left to rest before the mean value.
Werden Proben des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials, auf welchen kein Thermoausdruck ausgebildet ist, besprüht mit einer glycolhaltigen Flüssigkeit, kommt es an den besprühten Stellen zu einer Reaktion der Farbbildner mit den beiden Farbakzeptoren, die zu einer sichtbaren Vergrauung der Proben, hier als "Hintergrundvergrauung" bezeichnet, führt. Diese Vergrauung kann messtechnisch erfasst werden, in dem die Proben ohne Thermoausdruck mit der glycolhaltigen Flüssigkeit satt eingesprüht werden, bis sich ein geschlossener Flüssigkeitsfilm auf der Probe ausbildet. Die Proben werden dann luftdicht mittels Exsikkator für 20 Minuten eingeschlossen und dann über 1 Stunde bei 23° und 50% Luftfeuchte ruhen lassen. Anschließend werden an den Stellen mit einheitlich vergrauten Flächen insgesamt drei Messungen der optischen Dichte mittels Densitometer Gretag MacBeth TYPE D19C NB/U durchgeführt und der Mittelwert aus den drei aufgenommenen Messwerten gebildet. Vorzugsweise weist das erfindungsgemäße Aufzeichnungsmaterial eine derart bestimmte optische Dichte des Hintergrunds in einem Bereich von 0,12 bis 0,25 ODU auf.If samples of the heat-sensitive recording material according to the invention, on which no thermal expression is formed, sprayed with a glycol-containing liquid, it comes at the sprayed sites to a reaction of the color former with the two color acceptors, which refers to a visible graying of the samples, here as "background graying" , leads. This graying can be detected by measuring, in which the samples without thermal expression are sprayed full enough with the glycol-containing liquid until a closed liquid film forms on the sample. The samples are then sealed airtight by means of a desiccator for 20 minutes and then allowed to rest for 1 hour at 23 ° and 50% humidity. Subsequently, at the points with uniformly grayed areas, a total of three measurements of the optical density were carried out by means of the densitometer Gretag MacBeth TYPE D19C NB / U and the mean value was calculated from the three recorded measured values. Preferably, the recording material of the present invention has such a determined optical density of the background in a range of 0.12 to 0.25 ODU.
Die erfindungsgemäßen Aufzeichnungsmaterialien weisen ferner eine Druckdichte eines Thermoprobeausdruckes, ausgeführt mit einem Thermodruckkopf bei einer Auflösung von 300 dpi und einer Energie pro Flächeneinheit von 9 mJ/mm2, in einem Bereich von 0,6 bis 0,95 ODU (= Optical Density Units, gemäß DIN 16536-1, Ausgabe Mai 1997) auf. Werte innerhalb dieses Bereiches sind hinsichtlich des Anwenders noch akzeptabel, will er über ein extrem unempfindliches wärmeempfindliches Aufzeichnungsmaterial gegenüber Ethanollösungen, Wasser und insbesondere Weichmachern verfügen.The recording materials according to the invention also have a print density of a thermal print run carried out with a thermal print head at a resolution of 300 dpi and an energy per unit area of 9 mJ / mm 2 , in a range from 0.6 to 0.95 ODU (= Optical Density Units, according to DIN 16536-1, May 1997 issue). Values within this range are still acceptable to the user if he wants an extremely insensitive one heat-sensitive recording material to ethanol solutions, water and especially plasticizers have.
Zur messtechnischen Erfassung der dynamischen Druckdichte 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 9 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, a black and white checkered thermoprobauseausdruck is created with a device of the type Atlantek 400 from Printrex (USA), a thermal head with resolution of 300 dpi and an energy per unit area of 9 mJ / mm 2 for Use comes. 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.
In einer bevorzugten Ausführungsform ist es möglich, dass die wärmeempfindliche Aufzeichnungsschicht mehr als einen Farbbildner aufweist, jeweils ausgesucht aus den oben in Absatz [0009] aufgelisteten Farbbildnern. Das erfindungsgemäße Aufzeichnungsmaterial kann jedoch neben diesen als Fabbildner angegebenen Substanzen weiterhin auch eine oder mehrere der folgenden, im nahen Infrarot-Bereich absorbierenden Verbindungen enthalten:In a preferred embodiment, it is possible for the thermosensitive recording layer to comprise more than one color former, each selected from the color formers listed above in paragraph [0009]. However, the recording material according to the invention may, in addition to these substances specified as fabifiers, also contain one or more of the following compounds absorbing in the near infrared range:
3,6-Bis(dimethylamino)fluoren-9-spiro-3'-(6'-dimethylaminophthalid), 3-Diethylamino-6-dimethylaminofluoren-9-spiro-3'-(6'-dimethylaminophthalid), 3,6-Bis(diethylamino)-fluoren-9-spiro-3'-(6'-dimethylaminophthalid), 3-Dibutylamino-6-dimethylaminofluoren-9-spiro-3'-(6'-dimethylaminophthalid), 3-Dibutylamino-6-diethylaminofluoren-9-spiro-3'-(6'-dimethylaminophthalid), 3,6-Bis(dimethylamino)fluoren-9-spiro-3'-(6'-diethylamino-phthalid), 3-Diethylamino-6-dimethylaminofluoren-9-spiro-3'-(6'-diethylaminophthalid), 3-Dibutylamino-6-dimethylaminofluoren-9-spiro-3'-(6'-diethylaminophthalid), 3,6-Bis-(di-ethylamino)fluoren-9-spiro-3'-(6'-diethylaminophthalid), 3,6-Bis-(dimethylamino)-fluoren-9-spiro-3'-(6'-dibutylaminophthalid), 3-Dibutylamino-6-di-ethylaminofluoren-9-spiro-3'-(6'-diethylaminophthalid), 3-Diethylamino-6-dimethylaminofluoren-9-spiro-3'-(6'-dibutylaminophthalid), 3,3-Bis[2-(4-dimethylamino-phenyl)-2-(4-methoxyphenyl)-ethenyl]-4,5,6,7-tetrachlorophthalid.3,6-Bis (dimethylamino) fluorene-9-spiro-3 '- (6'-dimethylaminophthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3' - (6'-dimethylaminophthalide), 3.6- Bis (diethylamino) -fluorene-9-spiro-3 '- (6'-dimethylaminophthalide), 3-dibutylamino-6-dimethylaminofluorene-9-spiro-3' - (6'-dimethylaminophthalide), 3-dibutylamino-6-diethylaminofluorene -9-spiro-3 '- (6'-dimethylaminophthalide), 3,6-bis (dimethylamino) fluorene-9-spiro-3' - (6'-diethylamino-phthalide), 3-diethylamino-6-dimethylaminofluorene-9 -spiro-3 '- (6'-diethylaminophthalide), 3-dibutylamino-6-dimethylaminofluorene-9-spiro-3' - (6'-diethylaminophthalide), 3,6-bis (di-ethylamino) fluorene-9- spiro-3 '- (6'-diethylaminophthalide), 3,6-bis (dimethylamino) -fluorene-9-spiro-3' - (6'-dibutylaminophthalide), 3-dibutylamino-6-di-ethylaminofluorene-9- spiro-3 '- (6'-diethylaminophthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3' - (6'-dibutylaminophthalide), 3,3-bis [2- (4-dimethylamino-phenyl) - 2- (4-methoxyphenyl) ethenyl] -4,5,6,7-tetrachlorophthalid.
Zur Erzielung gewünschter Weißegrade der wärmeempfindlichen Aufzeichnungsschicht ist es notwendig, die Harnstoff-Urethan-Verbindungen gemäß Formel (2) vor ihrer Vermischung mit dem anderen Farbakzeptor und/oder mit anderen Komponenten der wärmeempfindlichen Aufzeichnungsschicht auf 60° C zu erwärmen und diese Wärmebehandlung 24 Stunden ununterbrochen fortzusetzen.In order to obtain desired whiteness of the heat-sensitive recording layer, it is necessary to heat the urea-urethane compounds of the formula (2) to 60 ° C before blending with the other color acceptor and / or other components of the heat-sensitive recording layer, and to conduct this heat treatment continuously for 24 hours continue.
Bezogen auf das Gesamtgewicht der Aufzeichnungsschicht, können die beiden Farbakzeptoren der Formel (1) und der Formel (2) bis zu 60 Gew.-%, bevorzugt jedoch einen Anteil in einem Bereich von 45 bis 55 Gew.-% der wärmeempfindlichen Aufzeichnungsschicht ausmachen. Der Effekt, den die Mischung aus den beiden Farbakzeptoren in ihrer Gesamtheit bewirkt, ist eine Kombination, die sich aus den Eigenheiten der beiden einzelnen Farbakzeptoren ergibt: Während N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-harnstoff gemäß Formel (1) als ein Farbakzeptor nach zahlreichen Einzel- und Kreuzversuchen erkannt wurde, der eine hohe Empfindlichkeit der wärmeempfindlichen Aufzeichnungsschicht auf Energieeinwirkung erwarten lässt, können Harnstoff-Urethan-Verbindungen gemäß der Formel (2) eher als solche Farbakzeptoren beschrieben werden, bei denen das durch Energieeinwirkung induzierte Druckbild eine hohe Stabilität gegenüber Fälschungsversuchen und Umwelteinflüssen aufweist. Werden beide Farbakzeptoren in einem Mischungsverhältnis in der Aufzeichnungsschicht eingesetzt, wie es von den Erfindern erkannt wurde, ist das Ergebnis ein schnell ansprechendes wärmeempfindliches Aufzeichnungsmaterial, das überraschenderweise zu wenig Hintergrundvergrauung neigt und ein gegenüber Umwelteinflüssen stabiles Wärme induziertes Druckbild aufweist.Based on the total weight of the recording layer, the two color acceptors of the formula (1) and the formula (2) can constitute up to 60% by weight, but preferably within the range of 45 to 55% by weight of the heat-sensitive recording layer. The effect that the mixture of the two color acceptors brings about in their entirety is a combination resulting from the peculiarities of the two individual color acceptors: While N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy -phenyl) urea according to formula (1) has been recognized as a color acceptor after numerous individual and cross experiments, which is expected to high sensitivity of the heat-sensitive recording layer to energy exposure, urea-urethane compounds according to the formula (2) may be more such as color acceptors be described in which the induced by energy print image has a high stability against counterfeiting and environmental influences. When both color acceptors are used in a compounding ratio in the recording layer as recognized by the present inventors, the result is a fast-response thermosensitive recording material that surprisingly tends to have little background graying and has a heat-induced printed image resistant to environmental influences.
Die Aufzeichnungsschicht des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials kann zur Erhöhung der thermischen Ansprechempfindlichkeit bevorzugt auch Sensibilisatoren mit einem Schmelzpunkt idealerweise von 60°C bis 184°C, besonders bevorzugt mit einem Schmelzpunkt von 80°C bis 140°C, enthalten. Derartige Sensibilisatoren sind beispielsweise: Benzyl-p-benzyloxy-benzoat, Stearamid, N-Methylolstearamid, p-Benzylbiphenyl, 1,2-Di(phenoxy)-ethan, 1,2-Di(m-methylphenoxy)ethan, m-Terphenyl, Dibenzyloxalat, Benzyl-naphthylether und Diphenylsulfon, wobei Benzylnaphthylether, Diphenylsulfon, 1,2-Di(m-methylphenoxy)ethan und 9,2-Di(phenoxy)-ethan als bevorzugt gelten.The recording layer of the thermosensitive recording material of the present invention may also preferably contain sensitisers having a melting point of preferably from 60 ° C to 184 ° C, more preferably having a melting point of from 80 ° C to 140 ° C, to increase the thermal responsiveness. Such sensitizers are, for example: benzyl p-benzyloxybenzoate, stearamide, N-methylol stearamide, p-benzylbiphenyl, 1,2-di (phenoxy) ethane, 1,2-di (m-methylphenoxy) ethane, m-terphenyl, dibenzyl, Benzyl naphthyl ether and diphenyl sulfone, with benzyl naphthyl ether, diphenyl sulfone, 1,2-di (m-methylphenoxy) ethane and 9,2-di (phenoxy) ethane being preferred.
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-Maleinsäure-anhydrid-Copolymeren oder Ethylen-Maleinsäureanhydrid-Copolymeren, wobei die Bindemittel 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-Copolymere als besonders bevorzugte Bindemittel, die zusammen, bezogen auf das Gesamtgewicht der Aufzeichnungsschicht, in einem Bereich von 9 bis 21 Gew.-% in die wärmeempfindliche Aufzeichnungsschicht eingebunden sind.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 binders 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 copolymers are considered to be particularly preferred binders which are incorporated in the heat-sensitive recording layer in a range of 9 to 21% 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 sowie 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.In order to prevent sticking to a thermal head and to avoid excessive wear of the thermal head, the coating composition for forming the heat-sensitive recording layer may further contain lubricants 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.
Zur Gewährleistung eines guten Kontrasts zwischen Schriftbild und unbeschrifteter Aufzeichnungsschicht weist die Aufzeichnungsschicht bevorzugt eine Weiße in einem Bereich von 79 bis 85 % bei Verwendung von Licht ohne UV-Anteil und eine Weiße in einem Bereich von 87 bis 93 % bei Verwendung von Licht mit UV-Anteil, jeweils gemessen nach ISO 2469/ISO 2470, auf, wobei jedoch D65-Licht verwendet wird bei einem Betrachtungswinkel von 8°.To ensure a good contrast between the typeface and the unlabelled recording layer, the recording layer preferably has a whiteness in a range of 79 to 85% when using light with no UV content and a whiteness ranging from 87 to 93% when using UV light. Fraction, measured in each case according to ISO 2469 / ISO 2470, but D65 light is used at an observation angle of 8 °.
Als Beschichtungsvorrichtung zum Auftrag der wärmeempfindlichen Aufzeichnungsschicht bieten sich insbesondere Rollrakelstreichwerk, Messerstreichwerk, Vorhangbeschichter oder Luftbürste an. Entsprechend einer bevorzugten Ausführungsform ist die zur Ausbildung der Aufzeichnungsschicht genutzte Beschichtungsmasse wässerig. Die anschließende Trocknung der Beschichtungsmasse geschieht üblicherweise durch ein Verfahren, bei dem Wärme zugeführt wird, wie es durch Heißluft-Schwebetrockner oder auch Kontakttrockner geschieht. Bewährt ist auch eine Kombination aus den aufgeführten Trockenverfahren. Die flächenbezogene Masse der wärmeempfindlichen Aufzeichnungsschicht liegt bevorzugt zwischen 2 und 6 g/m2 und noch besser zwischen 2,3 und 5,8 g/m2.Roller coater, knife coater, curtain coater or air brush are particularly suitable as coating apparatus for applying the heat-sensitive recording layer. According to a preferred embodiment, the coating composition used to form the recording layer is aqueous. The subsequent drying of the coating composition is usually done by a method in which heat is supplied, as is done by hot-air floating dryer or contact dryer. Proven is also a combination of the listed dry processes. The basis weight of the heat-sensitive recording layer is preferably from 2 to 6 g / m 2, and more preferably from 2.3 to 5.8 g / m 2 .
Zwischen der Aufzeichnungsschicht und dem Substrat des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials ist zweckmäßigerweise eine pigmentierte Zwischenschicht angeordnet. Ist die Zwischenschicht in einer bevorzugten Ausführungsform mit egalisierenden Beschichtungsvorrichtungen aufgetragen, wie sie beispielsweise Walzenstreichwerke, Streichmesser- oder (Roll-) Rakelstreichwerke darstellen, kann die Zwischenschicht ferner einen positiven Beitrag zur Egalisierung der Substratoberfläche leisten, womit sich die Menge an notwendigerweise aufzubringender Beschichtungsmasse für die wärmeempfindliche Aufzeichnungsschicht reduziert. Für die flächenbezogene Masse der Zwischenschicht hat sich ein bevorzugter Bereich zwischen 5 und 20 g/m2 und noch besser zwischen 7 und 12 g/m2 bewährt.Between the recording layer and the substrate of the heat-sensitive recording material according to the invention, a pigmented intermediate layer is expediently arranged. If the intermediate layer is applied in a preferred embodiment with leveling coating devices, such as, for example, roller coater, doctor blade or doctor blade coaters, the intermediate layer can also make a positive contribution to equalization of the substrate surface, thus increasing the amount of coating material necessarily to be applied to the substrate heat-sensitive recording layer reduced. For the basis weight of the intermediate layer, a preferred range between 5 and 20 g / m 2 and even better between 7 and 12 g / m 2 has proven.
Werden in die zwischen der Aufzeichnungsschicht und Substrat gelegene Zwischenschicht anorganische ölabsorbierende Pigmente eingebunden, können diese Pigmente die durch Hitzeeinwirkung des Thermokopfes verflüssigten Wachsbestandteile der wärmeempfindlichen Aufzeichnungsschicht bei der Schriftbildausbildung aufnehmen und begünstigen damit eine noch sichere und schnellere Funktionsweise der wärmeinduzierten Aufzeichnung, weshalb eine solche Ausführungsform als bevorzugt gilt.If inorganic oil-absorbing pigments are incorporated in the intermediate layer located between the recording layer and the substrate these pigments absorb the wax components of the heat-sensitive recording layer liquefied by the action of heat of the thermal head in the case of typeface formation and thus promote a still safer and faster functioning of the heat-induced recording, which is why such an embodiment is considered preferable.
Besonders vorteilhaft ist es, wenn die Pigmente der Zwischenschicht eine Ölabsorption von mindestens 80 cm3/100 g und noch besser von 100 cm3/100 g, bestimmt nach der japanischen Norm JIS K 5101, aufweisen. Kalziniertes Kaolin hat sich aufgrund seines großen Absorptionsreservoirs in den Hohlräumen besonders bewährt. Jedoch auch folgende anorganische Pigmente sind als Bestandteile der Zwischenschicht sehr gut geeignet: Siliziumoxid, Bentonit, Kalziumkarbonat sowie Aluminiumoxid und hier besonders Böhmit. Auch Mischungen aus mehreren verschiedenartigen anorganischen Pigmenten sind vorstellbar.It is particularly advantageous if the pigments of the intermediate layer has an oil absorption of at least 80 cm3 / 100 g, and more preferably 100 cm3 / 100 g, determined according to the Japanese standard JIS K 5101, is having. Calcined kaolin has proven particularly useful due to its large absorption reservoir in the cavities. However, the following inorganic pigments are also very well suited as constituents of the intermediate layer: silicon oxide, bentonite, calcium carbonate and aluminum oxide and, in particular, boehmite here. Also mixtures of several different types of inorganic pigments are conceivable.
In Versuchen zeigte sich, dass auch die Einbindung von organischen Pigmenten in die pigmentierte Zwischenschicht sehr vorteilhaft sein kann, was damit begründet wird, dass solche organischen Pigmente in einem besonderen Maße einem hohen Wärmereflexionsvermögen der Zwischenschicht zuträglich sind. Die in einer Zwischenschicht eines wärmeempfindlichen Aufzeichnungsmaterials angeordneten organischen, so genannten Hohlkörperpigmente weisen in ihrem Inneren Luft auf, die einen guten Wärmeisolator darstellt. Die so als Wärmereflexionsschicht optimierte Zwischenschicht erhöht das Ansprechverhalten der Aufzeichnungsschicht gegenüber Wärme, was das Auflösungsvermögen des wärmeempfindlichen Aufzeichnungsmaterials deutlich erhöht und ferner die Druckgeschwindigkeit im Thermodrucker nach oben zu setzen vermag.Experiments have shown that the incorporation of organic pigments into the pigmented intermediate layer can also be very advantageous, which is justified by the fact that such organic pigments are to a particular extent conducive to a high heat reflectivity of the intermediate layer. The arranged in an intermediate layer of a heat-sensitive recording material organic, so-called hollow body pigments have in their interior air, which is a good heat insulator. The intermediate layer thus optimized as the heat reflection layer increases the response of the recording layer to heat, which remarkably increases the resolving power of the thermosensitive recording material and further raises the printing speed in the thermal printer.
Das Mengenverhältnis zwischen organischem und anorganischem Pigment ist ein Kompromiss der von den beiden Pigmentarten bewirkten Effekte, der besonders vorteilhaft gelöst wird, wenn die Pigmentmischung zu 5 bis 30 Gew.-% bzw. besser zu 8 bis 20 Gew.-% aus organischem und zu 95 bis 70 Gew.-% bzw. besser zu 92 bis 80 Gew.-% aus anorganischem Pigment besteht. Pigmentmischungen aus unterschiedlichen organischen Pigmenten sind vorstellbar.The ratio between organic and inorganic pigment is a compromise of the effects caused by the two types of pigments, which is particularly advantageously solved when the pigment mixture to 5 to 30 wt .-% or better to 8 to 20 wt .-% of organic and 95 to 70 wt .-% or better to 92 to 80 wt .-% consists of inorganic pigment. Pigment mixtures of different organic pigments are conceivable.
Neben den anorganischen und gegebenenfalls auch organischen Pigmenten enthält die pigmentierte Zwischenschicht mindestens ein Bindemittel bevorzugt auf Basis eines synthetischen Polymers, wobei beispielsweise Styrol-Butadien-Latex besonders gute Ergebnisse liefert. Die Verwendung eines synthetischen Bindemittels unter Beimischung mindestens eines natürlichen Polymers, wie besonders bevorzugt Stärke, ,stellt eine besonders geeignete Ausführungsform dar. Im Rahmen von Versuchen mit anorganischen Pigmenten wurde ferner festgestellt, dass mit einem Bindemittel-Pigment-Verhältnis innerhalb der pigmentierten Zwischenschicht zwischen 3:7 und 1:9, jeweils bezogen auf Gew.-%, eine besonders geeignete Ausführungsform vorliegt.In addition to the inorganic and optionally also organic pigments, the pigmented intermediate layer contains at least one binder, preferably based on a synthetic polymer, wherein, for example, styrene-butadiene latex gives particularly good results. The use of a synthetic binder with the addition of at least one natural polymer, particularly preferably starch, represents a particularly suitable embodiment. In the context of experiments with inorganic pigments, it has also been found that with a binder-pigment ratio within the pigmented intermediate layer between 3 : 7 and 1: 9, each based on wt .-%, a particularly suitable embodiment is present.
Auch wenn nicht auf Papier als Substrat beschränkt, ist Papier und hier speziell ein nicht oberflächenbehandeltes Streichrohpapier bevorzugt in einem Bereich für die flächenbezogene Masse zwischen 45 und 130 g/m2 das Substrat, das sich am Markt auch mit Blick auf die gute Umweltverträglichkeit wegen der guten Recyclingfähigkeit durchgesetzt hat und das im Sinne der Erfindung bevorzugt ist. Unter einem nicht oberflächen behandelten Streichrohpapier ist ein nicht in einer Leimpresse oder in einer Beschichtungsvorrichtung behandeltes Streichrohpapier zu verstehen. Im Sinne der vorliegenden Erfindung wird dabei insbesondere ein nicht oberflächenbehandeltes, in der Masse geleimtes Streichrohpapier mit einem anorganischem Pigment, insbesondere Kalziumkarbonat, in der Masse als geeignet angesehen. Für die Erfindung sind im gleichen Maße Folien beispielsweise aus Polyolefin und mit Polyolefin beschichtete Papiere als Substrat möglich, ohne dass eine solche Ausführung ausschließenden Charakter aufweist.Although not limited to paper as a substrate, paper and especially a non-surface treated base paper preferred in a range for the basis weight between 45 and 130 g / m 2, the substrate, which is also in the market with regard to the good environmental performance because of Good recycling ability has prevailed and is preferred for the purposes of the invention. A non-surface treated base paper is to be understood as meaning a base paper which has not been treated in a size press or in a coating device. For the purposes of the present invention, in particular a non-surface-treated, sized in the mass base paper with an inorganic pigment, in particular calcium carbonate, is considered suitable in the mass. For the invention, films of, for example, polyolefin and polyolefin-coated papers as a substrate are possible to the same extent, without such an embodiment having an exclusive character.
Die in der Beschreibung und in den Ansprüchen gemachten Angaben zur flächenbezogenen Masse, zu Gew.-% (Gewichts-%) beziehen sich jeweils auf das "atro"-Gewicht, d.h. absolut trockene Gewichtsteile.The information given in the description and in the claims on basis weight,% by weight (% by weight) in each case refer to the "atro" weight, ie absolutely dry parts by weight.
Die Erfindung soll anhand des folgenden Beispiels 2 und der beiden Vergleichsbeispiele 1 und 3 weiter verdeutlicht werden:The invention will be further illustrated by the following example 2 and the two comparative examples 1 and 3:
Als Substrat wird auf einer Langsieb-Papiermaschine aus gebleichten und gemahlenen Laub- und Nadelholzzellstoffen unter Zugabe von 0,6 Gew.-% (atro) Harzleim als Masseleimung sowie weiterer üblicher Zuschlagstoffe, bezogen auf den Gesamtfeststoffgehalt (atro) der der Papiermaschine zugeführten Pulpe, ein Trägerpapier mit einer flächenbezogenen Masse von 53 g/m2 hergestellt. Frontseitig wird eine kalziniertes Kaolin als Pigment, Styrol-Butadien-Latex als Bindemittel und neben weiteren Hilfsmitteln Stärke als Cobinder aufweisende Zwischenschicht mit einer flächenbezogenen Masse von 9 g/m2 unter Nutzung eines Streichmessers aufgebracht.The substrate used is on a fourdrinier paper machine made of bleached and ground hardwood and softwood pulps with the addition of 0.6% by weight (atro) rosin size as engine sizing and other conventional additives, based on the total solids content (atro) of the pulp fed to the paper machine, a backing paper having a basis weight of 53 g / m 2 made. On the front side, a calcined kaolin pigment, styrene-butadiene latex as a binder and, in addition to other aids, starch as cobinder-containing intermediate layer having a basis weight of 9 g / m 2 is applied using a doctor blade.
Auf diese pigmentierte Zwischenschicht wird mittels Rollrakel-Streicheinrichtung jeweils eine von drei verschiedenen wärmeempfindlichen Aufzeichnungsschichten mit einer jeweiligen flächenbezogenen Masse von 5,4 g/m2 aufgetragen. Die dazu verwendeten wässerigen Streichmassen enthalten die folgenden Komponenten nach den in Tabelle 1 wiedergegebenen Rezepturen:
- Farbbildner (Fb): 3-dibutylamino-6-methyl-7-Anilinofluoran,
- Farbakzeptor (Fa) 1: N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-harnstoff gemäß Formel (1),
- Farbakzeptor (Fa) 2: Harnstoff-Urethan-Verbindung gemäß Formel (2),
- Sensibilisator (Sb): Benzyl-naphthylether,
- Bindemittel (Bm): Polyvinylalkohol,
- Cobinder (Cb): Acrylat-Copolymere,
- Pigment (Pm): Kalziumkarbonat
- Color former (Fb): 3-dibutylamino-6-methyl-7-anilinofluoran,
- Color acceptor (Fa) 1: N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea according to formula (1),
- Color acceptor (Fa) 2: urea-urethane compound according to formula (2),
- Sensitizer (Sb): benzyl naphthyl ether,
- Binder (Bm): polyvinyl alcohol,
- Cobinder (Cb): acrylate copolymers,
- Pigment (Pm): calcium carbonate
Weitere nicht prozentual und bezogen auf das Gesamtgewicht in Gew.-% (atro) angegebene Bestandteile der wärmeempfindlichen Aufzeichnungsschicht sind unter anderem Dispergiermittel, Entschäumer, optische Aufheller, Verdicker, Wachse und Vernetzer.Other components of the heat-sensitive recording layer which are not stated in percent and based on the total weight in% by weight (atro) include dispersants, defoamers, optical brighteners, thickeners, waxes and crosslinkers.
Bei dem erfindungsgemäßen Beispiel 2 liegt das auf die Gew.-% (atro) bezogene Verhältnis Farbakzeptor (Fa) 1 = N-(p-toluensulphonyl)-N'-3-(p-toluen-sulphonyl-Oxy-phenyl)-hamstoff gemäß Formel (1) : Farbakzeptor (Fa) 2 = Harnstoff-Urethan-Verbindung gemäß Formel (2) innerhalb der wärmeempfindlichen Aufzeichnungsschicht bei 1 : 2 und somit inmitten des hier besonders bevorzugten Bereichs. Bei dem Vergleichsbeispiel 1 liegt dieses Verhältnis bei 4 : 1, was bedeutet, das zu wenig an Harnstoff-Urethan-Verbindung gemäß Formel (2) im Verhältnis zu N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-harnstoff gemäß Formel (1) in der wärmeempfindlichen Aufzeichnungsschicht eingesetzt wird. Bei dem Vergleichsbeispiel 3 liegt dieses Verhältnis bei 1 : 5, was bedeutet, das sehr viel an Harnstoff-Urethan-Verbindung gemäß Formel (2) im Verhältnis zu N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-hamstoff gemäß Formel (1) in der wärmeempfindlichen Aufzeichnungsschicht eingesetzt wird.In Example 2 according to the invention, the ratio (% by weight) of the color acceptor (Fa) 1 = N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) urea according to formula (1): color acceptor (Fa) 2 = urea-urethane compound according to formula (2) within the heat-sensitive recording layer at 1: 2, and thus in the range particularly preferred here. In Comparative Example 1, this ratio is 4: 1, which means that too little urea-urethane compound according to formula (2) in relation to N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl) Oxy-phenyl) urea according to formula (1) is used in the heat-sensitive recording layer. In Comparative Example 3, this ratio is 1: 5, which means that a lot of urea-urethane compound of the formula (2) in proportion to N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) -urea according to formula (1) is used in the heat-sensitive recording layer.
Nach Fertigstellung von Mustern wärmeempfindlicher Aufzeichnungsmaterialien gemäß der zwei Vergleichsbeispiele 1 und 3 und des erfindungsgemäßen Beispiels 2 werden zur Bestimmung der dynamischen Druckdichten und der prozentualen Beständigkeiten gegenüber einer 25%-tigen Ethanollösung, gegenüber Wasser und gegenüber Weichmacher - wie weiter oben in der Beschreibung ausführlich beschrieben - 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 9 mJ/mm2 (dynamische Druckdichten) bzw. von 16 mJ/mm2 (prozentuale Beständigkeiten) zum Einsatz kommt. Die jeweilige Druckdichte selbst der schwarz gefärbten Flächen werden mit dem Densitometer Gretag MacBeth TYPE D19C NB/U (Fa Gretag MacBeth, 8105 Regensdorf, Schweiz) gemessen. Es ergeben sich die folgenden Messwerte It. Tabelle 2.
In aufwendigen Marktanalysen zeigt sich, dass wärmeempfindliche Aufzeichnungsmaterialien gemäß Vergleichsbeispiel 1 als zu wenig lagerbeständig innerhalb von Einsteckhüllen mit extrem hohem Anteil an Weichmachern, aber auch als zu wenig beständig gegenüber längerfristigen Ethanolbädem oder gegenüber dem Besprühen mit glycolhaltigen Flüssigkeiten, die als Sprays frei im Markt verfügbar sind, angesehen werden, während die dynamische Druckdichte als hervorragend angesehen wird. Auf der anderen Seite wird die dynamische Druckdichte von wärmeempfindlichen Aufzeichnungsmaterialien gemäß Vergleichsbeispiel 3 als eindeutig zu gering charakterisiert.Extensive market analyzes show that heat-sensitive recording materials according to Comparative Example 1 as too low storage stability within Einsteckhüllen with extremely high content of plasticizers, but also as too little resistant to long-term Ethanolbädem or spraying with glycol-containing liquids available as sprays freely on the market are considered while the dynamic print density is considered excellent. On the other hand, the dynamic printing density of heat-sensitive recording materials according to Comparative Example 3 is characterized as clearly too low.
Einzig wärmeempfindliche Aufzeichnungsmaterialien gemäß des erfindungsgemäßen Beispiels 2 überzeugen hinsichtlich Empfindlichkeit und Beständigkeit gegenüber Umwelteinflüssen. Durch das Besprühen mit glycolhaltigen Flüssigkeiten wird eine Spur in Form einer grauen Verfärbung hinterlassen, was in vielen Anwendungen von Vorteil ist. In den Vergleichsbeispielen kann das Bild spurlos gelöscht werden. Auch wird eine ausreichend große Bestempelbarkeit und Entwertbarkeit festgestellt.Only heat-sensitive recording materials according to Example 2 of the invention are convincing in terms of sensitivity and resistance to environmental influences. Spraying with glycol-containing liquids leaves a trail in the form of a gray discoloration, which is advantageous in many applications. In the comparative examples, the image can be deleted without a trace. Also, a sufficiently large stampability and Desertability is found.
Das obige erfindungsgemäße Beispiel sowie die beiden Vergleichsbeispiele belegen, dass erfindungsgemäße wärmeempfindliche Aufzeichnungsmaterialien die an sie gestellten Anforderungen überzeugend erfüllen können.The above example according to the invention and the two comparative examples show that heat-sensitive recording materials according to the invention can convincingly meet the requirements placed on them.
Claims (6)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES07017263T ES2366451T3 (en) | 2007-09-04 | 2007-09-04 | THERMOSENSIBLE REGISTRATION MATERIAL. |
| AT07017263T ATE508883T1 (en) | 2007-09-04 | 2007-09-04 | HEAT SENSITIVE RECORDING MATERIAL |
| EP07017263A EP2033799B1 (en) | 2007-09-04 | 2007-09-04 | Heat-sensitive recording material |
| US12/231,658 US20090082202A1 (en) | 2007-09-04 | 2008-09-04 | Heat-sensitive recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07017263A EP2033799B1 (en) | 2007-09-04 | 2007-09-04 | Heat-sensitive recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2033799A1 true EP2033799A1 (en) | 2009-03-11 |
| EP2033799B1 EP2033799B1 (en) | 2011-05-11 |
Family
ID=38921716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP07017263A Not-in-force EP2033799B1 (en) | 2007-09-04 | 2007-09-04 | Heat-sensitive recording material |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20090082202A1 (en) |
| EP (1) | EP2033799B1 (en) |
| AT (1) | ATE508883T1 (en) |
| ES (1) | ES2366451T3 (en) |
Cited By (7)
| 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 |
| EP2765007A1 (en) | 2013-02-08 | 2014-08-13 | Mitsubishi HiTec Paper Europe GmbH | Heat-sensitive recording material |
| EP3141397A4 (en) * | 2014-06-16 | 2017-08-23 | Nippon Paper Industries Co., Ltd. | Heat-sensitive recording medium |
| EP3312018A4 (en) * | 2015-06-16 | 2019-03-06 | Nippon Paper Industries Co., Ltd. | Thermal recording material |
| US10464362B2 (en) | 2015-10-23 | 2019-11-05 | Nippon Paper Industries Co., Ltd. | Thermosensitive recording medium |
| WO2020127675A1 (en) * | 2018-12-20 | 2020-06-25 | Papierfabrik August Koehler Se | Heat-sensitive recording material |
| KR20220097539A (en) * | 2019-11-28 | 2022-07-07 | 쾰러 페이퍼 에스이 | Polymorphic form of N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl)benzenesulfonamide |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105939867B (en) * | 2014-01-27 | 2018-05-11 | 三菱制纸株式会社 | Thermal recording medium |
| DE102016113203B4 (en) * | 2016-07-18 | 2018-05-30 | Papierfabrik August Koehler Se | HEAT-SENSITIVE RECORDING MATERIAL |
| DE102017111439B4 (en) * | 2017-05-24 | 2019-08-22 | Papierfabrik August Koehler Se | HEAT-SENSITIVE RECORDING MATERIAL |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0526072A1 (en) * | 1991-08-02 | 1993-02-03 | New Oji Paper Co., Ltd. | Thermosensitive recording material |
| EP1116713A1 (en) * | 1998-09-04 | 2001-07-18 | Asahi Kasei Kabushiki Kaisha | Novel color-developing compound and recording material |
| EP1243437A1 (en) * | 2001-03-23 | 2002-09-25 | Ricoh Company, Ltd. | Leuco dye dispersion liquid and thermosensitive recording material using the same |
| US20050148467A1 (en) * | 2001-10-12 | 2005-07-07 | Jouko Makitalo | Heat-sensitive recording material |
| DE102004004204A1 (en) | 2004-01-27 | 2005-08-11 | Mitsubishi Hitec Paper Bielefeld Gmbh | Heat-sensitive recording material for fax machines and thermal printers, has recording layer with sensitiser, pigment, binder, color formers and a color developer comprising Bisphenol A and a urea-urethane compound |
-
2007
- 2007-09-04 EP EP07017263A patent/EP2033799B1/en not_active Not-in-force
- 2007-09-04 ES ES07017263T patent/ES2366451T3/en active Active
- 2007-09-04 AT AT07017263T patent/ATE508883T1/en active
-
2008
- 2008-09-04 US US12/231,658 patent/US20090082202A1/en not_active Abandoned
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0526072A1 (en) * | 1991-08-02 | 1993-02-03 | New Oji Paper Co., Ltd. | Thermosensitive recording material |
| EP1116713A1 (en) * | 1998-09-04 | 2001-07-18 | Asahi Kasei Kabushiki Kaisha | Novel color-developing compound and recording material |
| EP1243437A1 (en) * | 2001-03-23 | 2002-09-25 | Ricoh Company, Ltd. | Leuco dye dispersion liquid and thermosensitive recording material using the same |
| US20050148467A1 (en) * | 2001-10-12 | 2005-07-07 | Jouko Makitalo | Heat-sensitive recording material |
| DE102004004204A1 (en) | 2004-01-27 | 2005-08-11 | Mitsubishi Hitec Paper Bielefeld Gmbh | Heat-sensitive recording material for fax machines and thermal printers, has recording layer with sensitiser, pigment, binder, color formers and a color developer comprising Bisphenol A and a urea-urethane compound |
Cited By (13)
| 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 |
| EP2765007A1 (en) | 2013-02-08 | 2014-08-13 | Mitsubishi HiTec Paper Europe GmbH | Heat-sensitive recording material |
| EP3141397A4 (en) * | 2014-06-16 | 2017-08-23 | Nippon Paper Industries Co., Ltd. | Heat-sensitive recording medium |
| US10000083B2 (en) | 2014-06-16 | 2018-06-19 | Nippon Paper Industries Co., Ltd. | Thermosensitive recording medium |
| US10513137B2 (en) | 2015-06-16 | 2019-12-24 | Nippon Paper Industries Co., Ltd. | Thermosensitive recording medium |
| EP3312018A4 (en) * | 2015-06-16 | 2019-03-06 | Nippon Paper Industries Co., Ltd. | Thermal recording material |
| US10464362B2 (en) | 2015-10-23 | 2019-11-05 | Nippon Paper Industries Co., Ltd. | Thermosensitive recording medium |
| WO2020127675A1 (en) * | 2018-12-20 | 2020-06-25 | Papierfabrik August Koehler Se | Heat-sensitive recording material |
| KR20210093363A (en) * | 2018-12-20 | 2021-07-27 | 파피에르패브릭 어거스트 쾰러 에스이 | thermal recording material |
| CN113260517A (en) * | 2018-12-20 | 2021-08-13 | 奥古斯特科勒纸厂欧洲公司 | Thermosensitive recording material |
| CN113260517B (en) * | 2018-12-20 | 2022-04-22 | 奥古斯特科勒纸厂欧洲公司 | Thermosensitive recording material |
| US11407935B2 (en) | 2018-12-20 | 2022-08-09 | Papierfabrik August Koehler Se | Heat-sensitive recording material |
| KR20220097539A (en) * | 2019-11-28 | 2022-07-07 | 쾰러 페이퍼 에스이 | Polymorphic form of N-(4-((4-(3-phenylureido)phenyl)sulfonyl)phenyl)benzenesulfonamide |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2033799B1 (en) | 2011-05-11 |
| ATE508883T1 (en) | 2011-05-15 |
| ES2366451T3 (en) | 2011-10-20 |
| US20090082202A1 (en) | 2009-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2033799B1 (en) | Heat-sensitive recording material | |
| EP3352991B1 (en) | Heat sensitive recording material | |
| EP3625058B1 (en) | Layered composite comprising a carrier layer and a finishing layer, and method for the production thereof | |
| WO2011067004A1 (en) | Heat-sensitive recording material with barrier coating | |
| DE202017006776U1 (en) | Heat-sensitive recording material | |
| EP2279877B1 (en) | Heat sensitive recording material | |
| DE60216456T2 (en) | HEAT-SENSITIVE RECORDING MATERIAL | |
| DE60222210T2 (en) | Heat-sensitive recording material | |
| EP2033801B1 (en) | Heat sensitive recording material | |
| DE102004004204A1 (en) | Heat-sensitive recording material for fax machines and thermal printers, has recording layer with sensitiser, pigment, binder, color formers and a color developer comprising Bisphenol A and a urea-urethane compound | |
| EP2112000B1 (en) | Heat sensitive recording material | |
| EP2329955B1 (en) | Heat-sensitive recording material with authenticity characteristic | |
| EP2033800B1 (en) | Heat-sensitive recording material | |
| EP2765007B1 (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 | |
| DE202020005616U1 (en) | A thermosensitive recording material comprising phenol-free organic color developers | |
| EP1925459B1 (en) | Method of producing a heat-sensitive recording material with authentification feature | |
| EP2505374B1 (en) | Heat-sensitive recording material, method for its manufacture and application | |
| DE102016219569A1 (en) | Heat-sensitive recording material | |
| DE60123722T2 (en) | Heat-sensitive recording material | |
| EP2414173B1 (en) | Heat-sensitive recording material | |
| DE102016219567A1 (en) | Heat-sensitive recording material | |
| EP1527900B1 (en) | Thermosensitive recording material, its' use and its' method of preparation. | |
| EP2480415B1 (en) | Heat-sensitive recording material with reverse face coating | |
| DE102011114129A1 (en) | Recording material for offset printing |
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 |
|
| 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 |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: DR. STORK, GERHARD Inventor name: SCHREIBER, ANNETTE |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: MITSUBISHI HITEC PAPER EUROPE GMBH |
|
| 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 |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: T3 Ref country code: DE Ref legal event code: R096 Ref document number: 502007007184 Country of ref document: DE Effective date: 20110622 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2366451 Country of ref document: ES Kind code of ref document: T3 Effective date: 20111020 |
|
| 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: 20110511 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: 20110511 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: 20110912 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20110812 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: 20110511 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: 20110511 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: 20110511 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: 20110911 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: 20110511 |
|
| 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: 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: 20110511 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: 20110511 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: 20110511 |
|
| 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: 20110511 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: 20110511 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: 20110511 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: 20110511 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed |
Effective date: 20120214 |
|
| 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: 20110930 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502007007184 Country of ref document: DE Effective date: 20120214 |
|
| 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: 20110511 |
|
| 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: 20110904 |
|
| 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: 20110811 |
|
| 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: 20110511 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20110511 |
|
| 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: FR Ref legal event code: PLFP Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20200923 Year of fee payment: 14 Ref country code: NL Payment date: 20200924 Year of fee payment: 14 Ref country code: FR Payment date: 20200925 Year of fee payment: 14 Ref country code: GB Payment date: 20200924 Year of fee payment: 14 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20200922 Year of fee payment: 14 Ref country code: BE Payment date: 20200924 Year of fee payment: 14 Ref country code: CH Payment date: 20200925 Year of fee payment: 14 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20201001 Year of fee payment: 14 Ref country code: IT Payment date: 20200930 Year of fee payment: 14 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 502007007184 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: MM Effective date: 20211001 |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 508883 Country of ref document: AT Kind code of ref document: T Effective date: 20210904 |
|
| REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20210930 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20210904 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20211001 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210904 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210930 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220401 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210930 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210930 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210930 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210904 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20221027 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210904 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210905 |