EP0767403B1 - Heat-sensitive recording material - Google Patents
Heat-sensitive recording material Download PDFInfo
- Publication number
- EP0767403B1 EP0767403B1 EP96114797A EP96114797A EP0767403B1 EP 0767403 B1 EP0767403 B1 EP 0767403B1 EP 96114797 A EP96114797 A EP 96114797A EP 96114797 A EP96114797 A EP 96114797A EP 0767403 B1 EP0767403 B1 EP 0767403B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- leuco dye
- heat
- binder
- silver salt
- 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.)
- Expired - Lifetime
Links
- 239000000463 material Substances 0.000 title claims description 43
- 239000011230 binding agent Substances 0.000 claims description 28
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 16
- -1 poly(vinyl alcohol) Polymers 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000003384 imaging method Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 230000004888 barrier function Effects 0.000 claims description 6
- 239000000020 Nitrocellulose Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229920001220 nitrocellulos Polymers 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000975 dye Substances 0.000 description 36
- 230000003287 optical effect Effects 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000001931 thermography Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical class OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 229940116224 behenate Drugs 0.000 description 3
- UKMSUNONTOPOIO-UHFFFAOYSA-M behenate Chemical compound CCCCCCCCCCCCCCCCCCCCCC([O-])=O UKMSUNONTOPOIO-UHFFFAOYSA-M 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 150000003378 silver Chemical class 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- MOZDKDIOPSPTBH-UHFFFAOYSA-N Benzyl parahydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 MOZDKDIOPSPTBH-UHFFFAOYSA-N 0.000 description 2
- QFOHBWFCKVYLES-UHFFFAOYSA-N Butylparaben Chemical compound CCCCOC(=O)C1=CC=C(O)C=C1 QFOHBWFCKVYLES-UHFFFAOYSA-N 0.000 description 2
- 239000004801 Chlorinated PVC Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical class OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical class OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- ORYURPRSXLUCSS-UHFFFAOYSA-M silver;octadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCC([O-])=O ORYURPRSXLUCSS-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 238000010023 transfer printing Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 description 1
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- UXTZUUVTGMDXNG-UHFFFAOYSA-N 1,2-benzoxazine-3,4-dione Chemical compound C1=CC=C2C(=O)C(=O)NOC2=C1 UXTZUUVTGMDXNG-UHFFFAOYSA-N 0.000 description 1
- XBYRMPXUBGMOJC-UHFFFAOYSA-N 1,2-dihydropyrazol-3-one Chemical compound OC=1C=CNN=1 XBYRMPXUBGMOJC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QMIYKBFAWPSBQJ-UHFFFAOYSA-N 1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonic acid;silver Chemical compound [Ag].CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC QMIYKBFAWPSBQJ-UHFFFAOYSA-N 0.000 description 1
- NLFKAHRURQOOPN-UHFFFAOYSA-N 1,4-bis(2-phenylpropan-2-yl)benzene Chemical compound C=1C=C(C(C)(C)C=2C=CC=CC=2)C=CC=1C(C)(C)C1=CC=CC=C1 NLFKAHRURQOOPN-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- GFMYLYZAYMLEMK-UHFFFAOYSA-N 1-(2-phenylpropan-2-yl)cyclohexa-3,5-diene-1,3-diol Chemical compound C1C(O)=CC=CC1(O)C(C)(C)C1=CC=CC=C1 GFMYLYZAYMLEMK-UHFFFAOYSA-N 0.000 description 1
- HIAGSPVAYSSKHL-UHFFFAOYSA-N 1-methyl-9h-carbazole Chemical class N1C2=CC=CC=C2C2=C1C(C)=CC=C2 HIAGSPVAYSSKHL-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- DFZVZKUDBIJAHK-UHFFFAOYSA-N 2-hydroxyoctadecanoic acid silver Chemical compound [Ag].OC(C(=O)O)CCCCCCCCCCCCCCCC DFZVZKUDBIJAHK-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- BOTGCZBEERTTDQ-UHFFFAOYSA-N 4-Methoxy-1-naphthol Chemical compound C1=CC=C2C(OC)=CC=C(O)C2=C1 BOTGCZBEERTTDQ-UHFFFAOYSA-N 0.000 description 1
- PZSCUHISJBQKSN-UHFFFAOYSA-N 4-methoxy-1,2-dihydronaphthalen-1-ol Chemical compound C1=CC=C2C(OC)=CCC(O)C2=C1 PZSCUHISJBQKSN-UHFFFAOYSA-N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical class NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical class C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229920000926 Galactomannan Polymers 0.000 description 1
- 241001082241 Lythrum hyssopifolia Species 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Chemical class 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920002125 Sokalan® Chemical class 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- ZKURGBYDCVNWKH-UHFFFAOYSA-N [3,7-bis(dimethylamino)phenothiazin-10-yl]-phenylmethanone Chemical compound C12=CC=C(N(C)C)C=C2SC2=CC(N(C)C)=CC=C2N1C(=O)C1=CC=CC=C1 ZKURGBYDCVNWKH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- CCGGDOVGIDSGQN-UHFFFAOYSA-N benzo[f][1,2]benzoxazine-1,2-dione Chemical compound C1=CC=CC2=C(C(C(=O)NO3)=O)C3=CC=C21 CCGGDOVGIDSGQN-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000004432 carbon atom Chemical group C* 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
- 229920003086 cellulose ether Polymers 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZINJLDJMHCUBIP-UHFFFAOYSA-N ethametsulfuron-methyl Chemical compound CCOC1=NC(NC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)C(=O)OC)=N1 ZINJLDJMHCUBIP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 230000002349 favourable effect Effects 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical compound C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 125000005543 phthalimide group Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004584 polyacrylic acid Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 description 1
- YRSQDSCQMOUOKO-KVVVOXFISA-M silver;(z)-octadec-9-enoate Chemical compound [Ag+].CCCCCCCC\C=C/CCCCCCCC([O-])=O YRSQDSCQMOUOKO-KVVVOXFISA-M 0.000 description 1
- ILTLXKRUPFUFIP-UHFFFAOYSA-M silver;dodecane-1-sulfonate Chemical compound [Ag+].CCCCCCCCCCCCS([O-])(=O)=O ILTLXKRUPFUFIP-UHFFFAOYSA-M 0.000 description 1
- MNMYRUHURLPFQW-UHFFFAOYSA-M silver;dodecanoate Chemical compound [Ag+].CCCCCCCCCCCC([O-])=O MNMYRUHURLPFQW-UHFFFAOYSA-M 0.000 description 1
- LTYHQUJGIQUHMS-UHFFFAOYSA-M silver;hexadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCC([O-])=O LTYHQUJGIQUHMS-UHFFFAOYSA-M 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- QYSXJUFSXHHAJI-YRZJJWOYSA-N vitamin D3 Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-YRZJJWOYSA-N 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
- G03C1/498—Photothermographic systems, e.g. dry silver
- G03C1/4989—Photothermographic systems, e.g. dry silver characterised by a thermal imaging step, with or without exposure to light, e.g. with a thermal head, using a laser
Definitions
- the invention relates to a heat-sensitive recording material based a combination of a heat sensitive silver salt and an acid sensitive Leuco dye.
- Thermography uses materials used, which are essentially not sensitive to light or photos, but are heat sensitive or thermosensitive. The one applied in the image areas Heat is enough to make a visible change in a heat sensitive To produce recording material.
- thermographic recording materials are chemical. When heated to a certain transition temperature, an irreversible takes place chemical reaction instead, which creates a colored image.
- a typical includes heat sensitive Copy paper in the thermosensitive layer a thermoplastic Binders, e.g. Ethyl cellulose, a water-insoluble silver salt, e.g. silver stearate, and a suitable organic reducing agent for 4-methoxy-1-hydroxy-dihydronaphthalene is a representative example.
- a thermoplastic Binders e.g. Ethyl cellulose, a water-insoluble silver salt, e.g. silver stearate, and a suitable organic reducing agent for 4-methoxy-1-hydroxy-dihydronaphthalene is a representative example.
- the local one Heating of the recording material in the thermographic reproduction process to a suitable transition temperature in the range of 90 ° C to 150 ° C causes a visible change in the heat sensitive layer.
- the initially white or slightly colored layer becomes darker and maintains on the heated Have a brownish look.
- the heat-sensitive layer becomes a heterocyclic organic toner substance, e.g. Phthalazinone added.
- Heat-sensitive copier papers that have a recording layer with an im essential light-insensitive organic silver salt and a hydroxylamine-like Reducing agents in a thermoplastic binder such as e.g. Have ethyl cellulose and post-chlorinated polyvinyl chloride are in US patent 4,082,901.
- a thermoplastic binder such as e.g. Have ethyl cellulose and post-chlorinated polyvinyl chloride are in US patent 4,082,901.
- Direct thermal recording materials are only suitable if they meet the above mentioned sensitometric properties with regard to optical density and have gradation.
- EP-A-0 680 833 which belongs to the prior art according to Article 54 (3) and (4) EPC, a heat-sensitive recording material on the same side of a carrier material, the so-called heat-sensitive side, one or more layers of binder on which an essentially light-insensitive metal salt in Combination with at least one organic reducing agent and one acid sensitive leuco dye in combination with an acidic Compound that serves as a dye developer.
- the materials according to of EP application EP-A-0 680 833 give images with high optical density and good grayscale reproduction.
- the object of the present invention is to provide a heat-sensitive recording material to provide the images with high optical density, good Grayscale reproduction and good stability.
- Another task of the present The invention is to provide a recording material with a simplified layer structure, which can be produced in a simple manner using casting technology is.
- Thermal action relationship means the possibility that the concern reactive substances which increase the image density when exposed to Heat can come into reactive contact with each other, e.g. B. by thermal induced diffusion or by separating elements such as Barrier layers or the walls of a reaction component enveloping Microcapsules become permeable when exposed to heat.
- the carrier material for the heat-sensitive recording material according to the invention is preferably a thin flexible support e.g. made of paper, polyethylene coated Paper or transparent plastic film, e.g. from a cellulose ester, e.g. Cellulose triacetate, polypropylene, polycarbonate or polyester, e.g. Polyethylene terephthalate.
- the layer support can be in the form of an arch, tape or web have and if necessary be provided with a document to the liability of the to improve applied heat-sensitive recording layer.
- the Layer thickness of the carrier can, for example, between 10 and 2000 microns, preferably are between 50 and 500 ⁇ m.
- the recording material according to the invention can be used to produce see-through material Supervisory images are used.
- the substrate can be transparent or opaque, in the latter case the substrate has one white, light reflecting surface.
- a paper backing which may contain white, light-reflecting pigments, optionally in one Intermediate layer between a receiving layer and the carrier mentioned.
- the support mentioned can be colorless or be colored, e.g. tinted blue.
- Organic silver salts suitable according to the invention are essentially insensitive to light.
- Silver salts of aliphatic carboxylic acids are particularly suitable, the so-called fatty acids, in which the aliphatic carbon chain is preferred has at least 12 carbon atoms, e.g. Silver laurate, silver palmitate, silver stearate, Silver hydroxystearate, silver oleate and silver behenate as well as equally Silver dodecyl sulfonate according to U.S. Patent 4,504,575 and silver di (2-ethylhexyl) sulfosuccinate according to European patent application 227 141.
- Suitable organic reducing agents for the reduction of the silver salt are organic compounds with at least one active hydrogen atom on O, N or C, such as aromatic di- and trihydroxy compounds, e.g. hydroquinone and substituted hydroquinones, catechol, pyrogallol, gallic acid and Gallates, aminophenols, METOL (trade name), p-phenylenediamines, alkoxynaphthols, e.g. 4-methoxy-1-naphthol according to U.S. Patent 3,094,417, pyrazolidin-3-one-like Reducing agents, e.g.
- aromatic di- and trihydroxy compounds e.g. hydroquinone and substituted hydroquinones, catechol, pyrogallol, gallic acid and Gallates, aminophenols, METOL (trade name), p-phenylenediamines, alkoxynaphthols, e.g. 4-methoxy-1-naphthol according to U.S
- PHENIDONE (trade name), pyrazolin-5-one, Indanedione-1,3-derivatives, hydroxytetronic acids, hydroxytetronimides, hydroxylamine derivatives (see e.g. U.S. Patent 4,082,901), hydrazine derivatives, reductones and ascorbic acid; see also U.S. Patents 3,074,809, 3,080,254, 3,094,417 and 3887378. Catechol and polyhydroxy spiro-bis-indan compounds are preferred.
- the reducing agent is preferably in the heat sensitive image layer incorporated, but it can be wholly or partially in an adjacent layer be embedded from where it will diffuse into the layer with the organic silver salt can.
- Natural, modified natural or synthetic resins e.g. Cellulose derivatives such as ethyl cellulose, cellulose esters, Carboxymethyl cellulose, starch ether, galactomannan, polymers from a, b-ethylenic unsaturated compounds such as polyvinyl chloride, post-chlorinated polyvinyl chloride, Copolymers of vinyl acetate and vinylidene chloride, copolymers of Vinyl chloride and vinyl acetate, polyvinyl acetate and partially hydrolyzed polyvinyl acetate, Polyvinyl alcohol, polyvinyl acetals from polyvinyl alcohol, in which only one Part of the repeating vinyl alcohol units with an aldehyde, preferably Polyvinyl butyral, is implemented, copolymers of acrylonitrile and acrylamide, Polyacrylic acid esters, polymethacrylic acid esters and polyethylene or mixtures from that.
- a particularly suitable binder is polyvinyl butyral with a
- the reducible silver salts and the reducing agents are advantageously combined with a so-called toner substance known from thermography or photo-thermography be used.
- Suitable toner substances are the phthalimides and Phthalazinones corresponding to the general ones described in U.S. Patent 4,082,901 Formulas. Further, reference is made to those in U.S. Patents 3,074,809, 3,446,648 and 3,844,797 described toner substances.
- Particularly suitable toner substances are also the heterocyclic toner compounds of benzoxazinedione or naphthoxazinedione type.
- the weight ratio of binder to organic lies in the silver salt layer Silver salt preferably between 0.2 and 6.
- This layer preferably has a thickness between 8 ⁇ m and 32 ⁇ m.
- the layer with the water- or alcohol-soluble polymer has the function of a Barrier layer.
- Suitable polymers are e.g. Polyvinyl alcohol, partially saponified polyvinyl acetate, Polyvinyl pyrrolidone, polyethylene oxide, polyethylene oxide-polypropylene oxide copolymers, Cellulose esters and cellulose ethers. Is particularly well suited Polyvinyl alcohol.
- the thickness of the barrier layer is 0.1 to 10 ⁇ m, preferably 0.2 to 5 ⁇ m.
- leuco dye layer Particularly suitable for the leuco dye layer are leuco dyes which are used for Belong to the class of fluorans, e.g. in EP-A-0 155796, in DE-A-35 34 594 and DE-A-43 29 133 and in U.S. Patents 3,957,288, 4,011,352 and 5.206.118 are described.
- binders are suitable as binders for the leuco dye layer them for the silver salt layer.
- Vinyl chloride and vinylidene chloride are particularly suitable Copolymers, e.g. Poly (vinyl chloride-co-vinyl acetate).
- binders mentioned can be used in conjunction with waxes or "heat solvents”, also referred to as “thermal solvents”, which are used Reaction speed of the dye formation reaction and the image silver producing Improve redox reaction at elevated temperatures.
- heat solvent in the sense of the present invention denotes a non-hydrolyzable organic material that can be used at temperatures below 50 ° C has a solid form, but from around 60 ° C as a plasticizer for the binder serves with which it connects in the heated area and / or then as Solvent acts for at least one of the color-forming reactants.
- suitable e.g. a polyethylene glycol with a medium relative Molecular mass between 1,500 and 20,000 as described in US patent 3,347,675.
- the thickness of the leuco dye layer is 2 to 25 ⁇ m, preferably 4 to 15 ⁇ m.
- Suitable developers for the leuco dye are electron-accepting or acidic compounds. Examples include: 1,3-bis-hydroxycumylbenzene or 1,4-bis-cumylbenzene, p-hydroxybenzoic acid butyl ester (PHBB) and bisphenols such as 4,4'-isopropylidenediphenol (bisphenol A) and analogues Compounds reported in the Journal of Imaging Technology, Vol. 16, No. 6, December 1990, p. 235, as well as in DE-A-35 34 594 and DE-A-43 29 133.
- Other suitable acidic compounds used as developers for leuco dyes serve are monoesters of aromatic ortho-carboxylic acids which e.g. in U.S. Patent 4,011,352, particularly the ethyl half ester of ortho-phthalic acid.
- the developer layer is expediently used using such Solvent produced that for the binder of the leuco dye layer none have a dissolving effect.
- those used in the developer layer Binder soluble in water or alcohol. It can be modified act natural or synthetic polymers. Take cellulose derivatives as an example, Polyvinylpyrrolidone and copolymers of vinylpyrrolidone and Called vinyl acetate. A preferred binder is nitrocellulose.
- the layer thickness the developer layer is 1 to 15 ⁇ m, preferably 3 ⁇ m to 10 ⁇ m.
- the recording material according to the invention can be used for contain layers known for this purpose. So it can be cheap than Apply a top coat to the top layer.
- a usual thickness this cover layer is 0.05 to 2.5 ⁇ m.
- the cover layer can have non-stick properties, e.g. through the Use of polysiloxanes, polysiloxane-polyether block copolymers or Can achieve fluoropolymers.
- Polyvinyl alcohol is also used as a cover layer suitable.
- thermostable cover layer For the description of the image material with a thermal head it turned out to be proved to be favorable to apply a thermostable cover layer.
- Suitable for this Polymers have a softening point above 100 ° C, preferably above 130 ° C.
- Polycarbonate is particularly suitable, especially homo- and Copolymers of trimetylcyclohexyl bisphenol polycarbonate.
- the latter Polymers lead to image materials with a particularly high gloss and good Focus. Contamination of the thermal head due to the image material as a result of gluing or abrasion does not take place.
- An added benefit of this Polymers are easy to process, e.g. by pouring out organic solution.
- the recording materials according to the invention can be produced using known technologies.
- the layer with the water or alcohol soluble polymer and the Developer layer can easily be made from water, alcohol or water-alcohol mixtures, e.g. cast from methyl alcohol, ethyl alcohol, isopropyl alcohol become.
- For the silver salt layer and the leuco dye layer are in general non-aqueous solvents necessary. Suitable solvents are e.g. Acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, dichloromethane, carbon tetrachloride and ethyl acetate.
- the heat-sensitive recording materials according to the invention can e.g. can be written with a thermal head and provide black and white images with high optical density (D-max> 2), good grayscale reproduction, high Sharpness and good stability.
- the gradation is lower, especially in areas Density, well suited for halftone reproduction, e.g. for portrait reproduction ID documents and medical diagnostics for the Playback of images, e.g. by X-ray, ultrasound or nuclear magnetic resonance (NMR) signals are generated.
- the term "gradation” refers to the slope of a density curve that the optical density (D) as a function value (ordinate) for linearly increasing amounts of heat on the abscissa.
- D optical density
- ordinate a function value for linearly increasing amounts of heat on the abscissa.
- different amounts of heat applied to the thermographic material in adjacent areas analogous to the production of a step wedge.
- the linear heat gain will e.g. by linearly increasing the heating time at various points in the Recording material achieved, the heating power (J) per unit time (s) constant is held. Alternatively, the heating time can remain constant instead of whose heating power can be increased linearly.
- a gradient corresponds to the slope at a single point on the density curve.
- the Gamma value ( ⁇ ) is the maximum gradient of said blackening curve and usually corresponds to the gradient between the end of the foot and the Beginning of the shoulder of the darkness curve.
- the recording material according to the invention is also from an ecological point of view particularly advantageous.
- a silver salt layer with the following composition from a methyl ethyl ketone solution was applied and dried on a subbed polyethylene terephthalate base with a layer thickness of 125 ⁇ m using a doctor blade: behenate 6.63 g / m 2 Polyvinyl butyral (Butvar® B79) - 6.63 g / m 2 3,3,3 ', 3', - tetramethyl-5,6,5 ', 6' - tetrahydroxy-spiro-bis-indane 1.26 g / m 2 3,4-dihydro-2,4-dioxo-1,3,2H-benzoxazine 0.50 g / m 2
- a barrier layer made of polyvinyl alcohol (Moviol® 18/88) was applied from an aqueous solution at a rate of 2.50 g / m 2 .
- a leuco dye layer with the composition specified below was applied from a methyl ethyl ketone solution and dried: Leuco dye, Yamada Black® S 205 1.60 g / m 2 Poly (vinyl chloride-co-vinyl acetate) 9.60 g / m 2
- a developer layer with the following composition from a methanol solution was applied and dried: p-hydroxybenzoic acid benzyl ester 2.25 g / m 2 nitrocellulose 2.25 g / m 2 Tegoglide® 410 0.30 g / m 2
- Example 2 In accordance with the procedure given in Example 1, a recording material was made with the following composition.
- Silver salt layer behenate 6.63 g / m 2 Polyvinyl butyral (Butvar® B79) 6.63 g / m 2 3,3,3 ', 3', - tetramethyl-5,6,5 ', 6' - tetrahydroxy-spiro-bis-indane 1.26 g / m 2 3,4-dihydro-2,4-dioxo-1,3,2H-benzoxazine 0.50 g / m 2 Junction: Polyvinyl alcohol (Moviol® 18/88) 3.50 g / m 2 leuco dye: Leuco dye, Pergascript® 2.40 g / m 2 Poly (vinyl chloride-co-vinyl acetate) 8.80 g / m 2 Developer layer: p-hydroxybenzoic acid benzyl ester 3.75 g / m 2 nitrocellulose 1.25
- Example 2 In accordance with the procedure given in Example 1, a recording material was made with the following composition.
- Silver salt layer behenate 6.63 g / m 2 Polyvinyl butyral (Butvar® B79) 6.63 g / m 2 3,3,3 ', 3', - tetramethyl-5,6,5 ', 6' - tetrahydroxy-spiro-bis-indane 1.26 g / m 2 3,4-dihydro-2,4-dioxo-1,3,2H-benzoxazine 0.50 g / m 2 Top layer: nitrocellulose 1.25 g / m 2 Tegoglide® 410 0.30 g / m 2
- a test image with 16 shades of gray was written onto the recording materials of Examples 1 to 3 using a printer with a thermal head (Hitachi VY 100 video printer).
- the optical densities of the individual stages were measured in transmission and tabulated.
- Optical density step 2 4 6 8th 10 12 14 16 example 1 0.16 0.32 0.48 0.67 1.44 3.67 4.16 4.38
- Example 3 0.04 0.04 0.04 0.07 0.68 2.89 3.08 3.14
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- Heat Sensitive Colour Forming Recording (AREA)
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Description
Die Erfindung betrifft ein wärmeempfindliches Aufzeichnungsmaterial auf Basis einer Kombination aus einem wärmeempfindlichen Silbersalz und einem säureempfindlichen Leukofarbstoff.The invention relates to a heat-sensitive recording material based a combination of a heat sensitive silver salt and an acid sensitive Leuco dye.
Das Wärmebildverfahren bzw. die Thermografie ist ein Aufnahmeprozeß, bei dem
Bilder mit Hilfe von bildmäßig modulierter Wärmeenergie erzeugt werden. In der
Thermografie sind zwei Konzepte bekannt:
Eine Übersicht der "direkt thermischen" Abbildungsverfahren ist z.B. in dem Buch "Imaging Systems" von Kurt I. Jacobson und Ralph E. Jacobson, erschienen bei The Focal Press, London und New York (1976), in Kapitel VII unter der Überschrift "7.1 Thermografie" enthalten. Bei der Thermografie werden Materialien eingesetzt, die im wesentlichen nicht licht- bzw. fotoempfindlich, sondern wärmempfindlich bzw. thermosensitiv sind. Die in den Bildbereichen aufgebrachte Wärme reicht aus, um eine sichtbare Veränderung in einem wärmeempfindlichen Aufnahmematerial hervorzurufen. An overview of the "direct thermal" imaging processes is e.g. in the book "Imaging Systems" by Kurt I. Jacobson and Ralph E. Jacobson, published by The Focal Press, London and New York (1976), in Chapter VII under the Headline "7.1 Thermography" included. Thermography uses materials used, which are essentially not sensitive to light or photos, but are heat sensitive or thermosensitive. The one applied in the image areas Heat is enough to make a visible change in a heat sensitive To produce recording material.
Die meisten direkt thermografischen Aufnahmematerialien sind chemischer Art. Bei Erwärmung auf eine bestimmte Umwandlungstemperatur findet eine irreversible chemische Reaktion statt, wodurch ein farbiges Bild erzeugt wird.Most direct thermographic recording materials are chemical. When heated to a certain transition temperature, an irreversible takes place chemical reaction instead, which creates a colored image.
Eine große Vielzahl chemischer Systeme ist vorgeschlagen worden, von denen einige Beispiele auf Seite 138 des vorstehend genannten Buches von Kurt I. Jacobson et al. angegeben sind. An dieser Stelle wird die Herstellung eines Silbermetallbildes mit Hilfe einer thermisch induzierten Reduktion einer Silberseife beschrieben. Laut dem US-Patent 3.080.254 umfaßt ein typisches wärmeempfindliches Kopierpapier in der wärmeempfindlichen Schicht ein thermoplastisches Bindemittel, z.B. Ethylcellulose, ein wasserunlösliches Silbersalz, z.B. Silberstearat, sowie ein geeignetes organisches Reduktionsmittel, für das 4-Methoxy-1-hydroxy-dihydronaphthalin ein repräsentatives Beispiel ist. Die örtlich begrenzte Erwärmung des Aufzeichnungsmaterials im thermografischen Reproduktionsprozeß auf eine geeignete Umwandlungstemperatur im Bereich von 90 °C bis 150 °C verursacht eine sichtbare Veränderung in der wärmeempfindlichen Schicht. Die anfänglich weiße oder leicht farbige Schicht wird dunkler und erhält an der erwärmten Stelle ein bräunliches Aussehen. Zur Erzielung eines neutraleren Farbtons wird der wärmeempfindlichen Schicht eine heterocyclische organische Tonersubstanz, z.B. Phthalazinon, zugegeben.A wide variety of chemical systems have been proposed, of which some examples on page 138 of the above-mentioned book by Kurt I. Jacobson et al. are specified. At this point, the creation of a silver metal picture described with the help of a thermally induced reduction of a silver soap. According to U.S. Patent 3,080,254, a typical includes heat sensitive Copy paper in the thermosensitive layer a thermoplastic Binders, e.g. Ethyl cellulose, a water-insoluble silver salt, e.g. silver stearate, and a suitable organic reducing agent for 4-methoxy-1-hydroxy-dihydronaphthalene is a representative example. The local one Heating of the recording material in the thermographic reproduction process to a suitable transition temperature in the range of 90 ° C to 150 ° C causes a visible change in the heat sensitive layer. The initially white or slightly colored layer becomes darker and maintains on the heated Have a brownish look. To achieve a more neutral shade the heat-sensitive layer becomes a heterocyclic organic toner substance, e.g. Phthalazinone added.
Wärmeempfindliche Kopierpapiere, die eine Aufnahmeschicht mit einem im wesentlichen lichtunempfindlichen organischen Silbersalz und einem hydroxylaminartigen Reduktionsmittel in einem thermoplastischen Bindemittel wie z.B. Ethylcellulose und nachchloriertes Polyvinylchlorid aufweisen, sind in US-Patent 4.082.901 beschrieben. Bei Verwendung in thermografischen Aufnahmeverfahren mit Thermodruckköpfen sind die genannten Kopierpapiere nicht zur Reproduktion von Bildern mit einer relativ großen Anzahl von Graustufen geeignet, wie sie für die Halbtonreproduktion erforderlich sind.Heat-sensitive copier papers that have a recording layer with an im essential light-insensitive organic silver salt and a hydroxylamine-like Reducing agents in a thermoplastic binder such as e.g. Have ethyl cellulose and post-chlorinated polyvinyl chloride are in US patent 4,082,901. When used in thermographic recording processes With thermal print heads, the copy papers mentioned are not for reproduction suitable for images with a relatively large number of grayscale as for the halftone reproduction is required.
Laut dem vorstehend erwähnten Handbuch für Abbildungsmaterialien (Seiten 499 - 501) werden direkte Wärmeaufnahmeverfahren mit einem Leukofarbstoffsystem heute kommerziell genutzt.According to the imaging materials guide mentioned above (pages 499 - 501) are direct heat absorption processes with a leuco dye system used commercially today.
In einer von T. Usami und A. Shimura im Journal of Imaging Technology, Jg. 16, Nr. 6, Dezember 1990, S. 234 bis 237, beschriebenen Ausführungsform arbeitet ein bestimmtes Leukofarbstoffsystem auf einem transparenten Filmträger mit gekapselten Leukofarbstoffen in einer Aufnahmeschicht, die einen sog. "Entwickler" enthält (z.B. eine sauer reagierende Bisphenolverbindung, die in einem organischen Lösemittel gelöst und in einem wasserlöslichen Bindemittel dispergiert ist). Aus der Kurve der optischen Dichte in Abhängigkeit von der Temperatur (Bild 11 auf Seite 236) ist zu ersehen, daß die optische Dichte bei Temperaturen von etwa 130 °C nicht höher als 1,5 ist und nicht weiter ansteigt.In one of T. Usami and A. Shimura in the Journal of Imaging Technology, vol. 16, No. 6, December 1990, pp. 234 to 237 a certain leuco dye system on a transparent film carrier encapsulated leuco dyes in a recording layer, the so-called "developer" contains (e.g. an acidic bisphenol compound, which in one dissolved organic solvents and dispersed in a water-soluble binder is). From the curve of the optical density as a function of temperature (Figure 11 on page 236) it can be seen that the optical density at temperatures of about 130 ° C is not higher than 1.5 and does not rise further.
Weder direkte thermische Monoblatt-Aufnahmematerialien noch Zweiblatt-Thermofarbstofftransfer-Aufnahmematerialien (Farbstoffdonator- und Rezeptormaterialien), wie sie heute auf dem Markt sind, verfügen über die Fähigkeit, Bilder mit maximalen optischen Dichten über 2,5 und einer für die Halbtonreproduktion erforderlichen Gradation zu liefern.Neither direct mono-sheet thermal receivers nor two-sheet thermal dye transfer receivers (Dye donor and receptor materials), as they are on the market today have the ability Images with maximum optical densities over 2.5 and one for halftone reproduction to deliver required gradation.
Bei bestimmten Anwendungen, z.B. im Bereich der medizinischen Diagnostik, müssen jedoch die vorstehenden Abbildungsmöglichkeiten gegeben sein, und direkt thermische Aufnahmematerialien sind dafür nur geeignet, wenn sie die vorstehend genannten sensitometrischen Eigenschaften hinsichtlich optischer Dichte und Gradation aufweisen.In certain applications, e.g. in the field of medical diagnostics, However, the above illustration options must be available, and Direct thermal recording materials are only suitable if they meet the above mentioned sensitometric properties with regard to optical density and have gradation.
Nach der EP-Anmeldung EP-A-0 680 833, die zum Stand der Technik nach Artikel 54(3) und (4) EPÜ gehört, weist ein wärmeempfindliches Aufzeichnungsmaterial auf der gleichen Seite eines Trägermaterials, der sogenannten wärmeempfindlichen Seite, eine oder mehrere Bindemittelschichten auf, die ein im wesentlichen lichtunempfindliches Metallsalz in Kombination mit mindestens einem organischen Reduktionsmittel sowie einen säureempfindlichen Leukofarbstoff in Kombination mit einer sauer reagierenden Verbindung, die als Farbstoffentwickler dient, enthalten. Die Materialien gemäß der EP-Anmeldung EP-A-0 680 833 ergeben Bilder mit hoher optischer Dichte und guter Graustufenwiedergabe.According to EP application EP-A-0 680 833, which belongs to the prior art according to Article 54 (3) and (4) EPC, a heat-sensitive recording material on the same side of a carrier material, the so-called heat-sensitive side, one or more layers of binder on which an essentially light-insensitive metal salt in Combination with at least one organic reducing agent and one acid sensitive leuco dye in combination with an acidic Compound that serves as a dye developer. The materials according to of EP application EP-A-0 680 833 give images with high optical density and good grayscale reproduction.
Aufgabe der vorliegenden Erfindung ist es, ein wärmeempfindliches Aufzeichnungsmaterial bereitzustellen, das Abbildungen mit hoher optischer Dichte, guter Graustufenwiedergabe und guter Stabilität liefert. Eine weitere Aufgabe der vorliegenden Erfindung ist die Bereitstellung eines Aufzeichnungsmaterials mit einem vereinfachtem Schichtaufbau, das in einfacher Weise durch Gießtechnologie herstellbar ist. The object of the present invention is to provide a heat-sensitive recording material to provide the images with high optical density, good Grayscale reproduction and good stability. Another task of the present The invention is to provide a recording material with a simplified layer structure, which can be produced in a simple manner using casting technology is.
Gegenstand der Erfindung ist ein wärmeempfindliches Bildaufzeichnungsmaterial,
das auf einem Trägermaterial
Unter "thermischer Wirkungsbeziehung" ist die Möglichkeit zu verstehen, daß die betreffenden die Bilddichte erhöhenden reaktiven Substanzen bei Einwirkung von Wärme miteinander in reaktiven Kontakt treten können, z. B. durch thermisch induzierte Diffusion oder dadurch, daß trennende Elemente wie beispielsweise Sperrschichten oder die Wände von eine Reaktionskomponente einhüllenden Mikrokapseln bei Einwirkung von Wärme durchlässig werden."Thermal action relationship" means the possibility that the concern reactive substances which increase the image density when exposed to Heat can come into reactive contact with each other, e.g. B. by thermal induced diffusion or by separating elements such as Barrier layers or the walls of a reaction component enveloping Microcapsules become permeable when exposed to heat.
In einer bevorzugten Ausführungsform der Erfindung enthält das erfindungsgemäße
wärmeempfindliche Aufzueichnungsmaterial auf einem Trägermaterial
mindestens vier Schichten, nämlich
Das Trägermaterial für das erfindungsgemäße wärmeempfindliche Aufnahmematerial ist vorzugsweise ein dünner flexibler Träger z.B. aus Papier, polyethylenbeschichtetem Papier oder transparenter Kunststoffolie, z.B. aus einem Celluloseester, z.B. Cellulosetriacetat, Polypropylen, Polycarbonat oder Polyester, z.B. Polyethylenterephthalat. Der Schichtträger kann Bogen-, Band- oder Bahnform haben und bei Bedarf mit einer Unterlage versehen sein, um die Haftung der darauf aufgebrachten wärmeempfindlichen Aufnahmeschicht zu verbessern. Die Schichtdicke des Trägers kann beispielsweise zwischen 10 und 2000 µm, vorzugsweise zwischen 50 und 500 µm liegen.The carrier material for the heat-sensitive recording material according to the invention is preferably a thin flexible support e.g. made of paper, polyethylene coated Paper or transparent plastic film, e.g. from a cellulose ester, e.g. Cellulose triacetate, polypropylene, polycarbonate or polyester, e.g. Polyethylene terephthalate. The layer support can be in the form of an arch, tape or web have and if necessary be provided with a document to the liability of the to improve applied heat-sensitive recording layer. The Layer thickness of the carrier can, for example, between 10 and 2000 microns, preferably are between 50 and 500 µm.
Das erfindungsgemäße Aufnahmematerial kann zur Herstellung von Durchsichtsund Aufsichtsbildern verwendet werden. Dies bedeutet, daß der Schichtträger transparent oder opak sein kann, im letzteren Fall weist der Schichtträger eine weiße, lichtreflektierende Oberfläche auf. Es wird z.B. ein Papierträger verwendet, der weiße, lichtreflektierende Pigmente enthalten kann, optional auch in einer Zwischenschicht zwischen einer Aufnahmeschicht und dem genannten Träger. Wird ein transparenter Schichtträger verwendet, kann der genannte Träger farblos oder farbig sein, z.B. blau getönt. Im Bereich der Hardcopy-Herstellung werden Aufnahmematerialien auf einem weißen, opaken Träger verwendet, während im Bereich der medizinischen Diagnostik vielfach Schwarzbild-Dias für die Betrachtung mit einem Lichtkasten angewandt werden.The recording material according to the invention can be used to produce see-through material Supervisory images are used. This means that the substrate can be transparent or opaque, in the latter case the substrate has one white, light reflecting surface. For example used a paper backing which may contain white, light-reflecting pigments, optionally in one Intermediate layer between a receiving layer and the carrier mentioned. If a transparent layer support is used, the support mentioned can be colorless or be colored, e.g. tinted blue. In the field of hard copy manufacturing Recording materials used on a white, opaque support, while in Medical diagnostics in the field of black screen slides for viewing can be used with a light box.
Erfindungsgemäß geeignete organische Silbersalze sind im wesentlichen lichtunempfindlich. Besonders geeignet sind Silbersalze von aliphatischen Carbonsäuren, die sogenannten Fettsäuren, bei denen die aliphatische Kohlenstoffkette vorzugsweise mindestens 12 C-Atome aufweist, z.B. Silberlaurat, Silberpalmitat, Silberstearat, Silberhydroxystearat, Silberoleat und Silberbehenat sowie gleichermaßen Silberdodecylsulfonat gemäß US-Patent 4.504.575 und Silberdi-(2-ethylhexyl)-sulfosuccinat gemäß der Europäischen Patentanmeldung 227 141.Organic silver salts suitable according to the invention are essentially insensitive to light. Silver salts of aliphatic carboxylic acids are particularly suitable, the so-called fatty acids, in which the aliphatic carbon chain is preferred has at least 12 carbon atoms, e.g. Silver laurate, silver palmitate, silver stearate, Silver hydroxystearate, silver oleate and silver behenate as well as equally Silver dodecyl sulfonate according to U.S. Patent 4,504,575 and silver di (2-ethylhexyl) sulfosuccinate according to European patent application 227 141.
Geeignete organische Reduktionsmittel für die Reduktion des Silbersalzes sind organische Verbindungen mit mindestens einem aktiven Wasserstoffatom an O, N oder C, wie etwa bei aromatischen Di- und Trihydroxyverbindungen, z.B. Hydrochinon und substituierten Hydrochinonen, Catechol, Pyrogallol, Gallussäure und Gallate, Aminophenole, METOL (Handelsname), p-Phenylendiamine, Alkoxynaphthole, z.B. 4-Methoxy-1-naphthol gemäß US-Patent 3.094.417, Pyrazolidin-3-on-artige Reduktionsmittel, z.B. PHENIDONE (Handelsname), Pyrazolin-5-one, Indandion-1,3-Derivate, Hydroxytetronsäuren, Hydroxytetronimide, HydroxylaminDerivate (siehe z.B. US-Patent 4.082.901), Hydrazin-Derivate, Reductone und Ascorbinsäure; siehe auch US-Patente 3.074.809, 3.080.254, 3.094.417 und 3.887.378. Bevorzugt werden Catechol und Polyhydroxy-spiro-bis-indan-Verbindungen. Das Reduktionsmittel wird vorzugsweise in die wärmeempfindliche Bildschicht eingearbeitet, es kann aber ganz oder teilweise in eine angrenzende Schicht eingebettet sein, von wo es in die Schicht mit dem organischen Silbersalz diffundieren kann.Suitable organic reducing agents for the reduction of the silver salt are organic compounds with at least one active hydrogen atom on O, N or C, such as aromatic di- and trihydroxy compounds, e.g. hydroquinone and substituted hydroquinones, catechol, pyrogallol, gallic acid and Gallates, aminophenols, METOL (trade name), p-phenylenediamines, alkoxynaphthols, e.g. 4-methoxy-1-naphthol according to U.S. Patent 3,094,417, pyrazolidin-3-one-like Reducing agents, e.g. PHENIDONE (trade name), pyrazolin-5-one, Indanedione-1,3-derivatives, hydroxytetronic acids, hydroxytetronimides, hydroxylamine derivatives (see e.g. U.S. Patent 4,082,901), hydrazine derivatives, reductones and ascorbic acid; see also U.S. Patents 3,074,809, 3,080,254, 3,094,417 and 3887378. Catechol and polyhydroxy spiro-bis-indan compounds are preferred. The reducing agent is preferably in the heat sensitive image layer incorporated, but it can be wholly or partially in an adjacent layer be embedded from where it will diffuse into the layer with the organic silver salt can.
Als Bindemittel eignen sich in erster Linie natürliche, modifizierte natürliche oder synthetische Harze. z.B. Cellulosederivate wie etwa Ethylcellulose, Celluloseester, Carboxymethylcellulose, Stärke-Ether, Galactomannan, Polymere aus a,b-ethylenisch ungesättigten Verbindungen wie Polyvinylchlorid, nachchloriertes Polyvinylchlorid, Copolymere von Vinylacetat und Vinylidenchlorid, Copolymere aus Vinylchlorid und Vinylacetat, Polyvinylacetat und teilhydrolyisiertes Polyvinylacetat, Polyvinylalkohol, Polyvinylacetale aus Polyvinylalkohol, bei denen nur ein Teil der sich wiederholenden Vinylalkoholeinheiten mit einem Aldehyd, vorzugsweise Polyvinylbutyral, umgesetzt ist, Copolymere von Acrylnitril und Acrylamid, Polyacrylsäureester, Polymethacrylsäureester und Polyethylen oder Mischungen davon. Ein besonders geeignetes Bindemittel ist Polyvinylbutyral mit einer geringen Menge Vinylalkoholeinheiten, das unter der Handelsbezeichnung BUTVAR B79 von Monsanto USA vertrieben wird.Natural, modified natural or synthetic resins. e.g. Cellulose derivatives such as ethyl cellulose, cellulose esters, Carboxymethyl cellulose, starch ether, galactomannan, polymers from a, b-ethylenic unsaturated compounds such as polyvinyl chloride, post-chlorinated polyvinyl chloride, Copolymers of vinyl acetate and vinylidene chloride, copolymers of Vinyl chloride and vinyl acetate, polyvinyl acetate and partially hydrolyzed polyvinyl acetate, Polyvinyl alcohol, polyvinyl acetals from polyvinyl alcohol, in which only one Part of the repeating vinyl alcohol units with an aldehyde, preferably Polyvinyl butyral, is implemented, copolymers of acrylonitrile and acrylamide, Polyacrylic acid esters, polymethacrylic acid esters and polyethylene or mixtures from that. A particularly suitable binder is polyvinyl butyral with a low Amount of ethanol units sold under the trade name BUTVAR B79 is distributed by Monsanto USA.
Um einen neutralschwarzen Bildton mit Silber in den Bereichen höherer optischer Dichte und Neutralgrau in den Bereichen geringerer Dichte zu erhalten, können die reduzierbaren Silbersalze und die Reduktionsmittel vorteilhaft in Verbindung mit einer aus der Thermografie oder Foto-Thermografie bekannten sog. Tonersubstanz verwendet werden. Geeignete Tonersubstanzen sind die Phthalimide und Phthalazinone entsprechend den in US-Patent 4.082.901 beschriebenen allgemeinen Formeln. Weiterhin wird auf die in den US-Patenten 3.074.809, 3.446.648 und 3.844.797 beschriebenen Tonersubstanzen verwiesen. Besonders geeignete Tonersubstanzen sind auch die heterozyclischen Tonerverbindungen des Benzoxazindion- oder Naphthoxazindion-Typs.To achieve a neutral black image tone with silver in the areas of higher optical Can get density and neutral gray in the areas of lower density the reducible silver salts and the reducing agents are advantageously combined with a so-called toner substance known from thermography or photo-thermography be used. Suitable toner substances are the phthalimides and Phthalazinones corresponding to the general ones described in U.S. Patent 4,082,901 Formulas. Further, reference is made to those in U.S. Patents 3,074,809, 3,446,648 and 3,844,797 described toner substances. Particularly suitable toner substances are also the heterocyclic toner compounds of benzoxazinedione or naphthoxazinedione type.
In der Silbersalzschicht liegt das Gewichtsverhältnis von Bindemittel zu organischem Silbersalz vorzugsweise zwischen 0,2 und 6. Diese Schicht hat vorzugsweise eine Dicke zwischen 8 µm und 32 µm.The weight ratio of binder to organic lies in the silver salt layer Silver salt preferably between 0.2 and 6. This layer preferably has a thickness between 8 µm and 32 µm.
Die Schicht mit dem wasser- oder alkohollöslichen Polymer hat die Funktion einer Sperrschicht. Geeignete Polymere sind z.B. Polyvinylalkohol, teilverseiftes Polyvinylacetat, Polyvinylpyrrolidon, Polyethylenoxid, Polyethylenoxid-Polypropylenoxid-Copolymere, Celluloseester und Celluloseether. Besonders gut geeignet ist Polyvinylalkohol. Die Dicke der Sperrschicht beträgt 0,1 bis 10 µm, vorzugsweise 0,2 bis 5 µm.The layer with the water- or alcohol-soluble polymer has the function of a Barrier layer. Suitable polymers are e.g. Polyvinyl alcohol, partially saponified polyvinyl acetate, Polyvinyl pyrrolidone, polyethylene oxide, polyethylene oxide-polypropylene oxide copolymers, Cellulose esters and cellulose ethers. Is particularly well suited Polyvinyl alcohol. The thickness of the barrier layer is 0.1 to 10 μm, preferably 0.2 to 5 µm.
Für die Leukofarbstoffschicht besonders geeignet sind Leukofarbstoffe, die zur Klasse der Fluorane gehören, wie sie z.B. in EP-A-0 155796, in DE-A-35 34 594 und DE-A-43 29 133 sowie in den US-Patenten 3.957.288, 4.011.352 und 5.206.118 beschrieben sind.Particularly suitable for the leuco dye layer are leuco dyes which are used for Belong to the class of fluorans, e.g. in EP-A-0 155796, in DE-A-35 34 594 and DE-A-43 29 133 and in U.S. Patents 3,957,288, 4,011,352 and 5.206.118 are described.
Die bevorzugten fluoranartigen Leukofarbstoffe haben die folgende allgemeine Formel (A): wobei
- R1
- eine Mono- oder Dialkylaminogruppe in substituierter Form ist, z.B. substituiert mit einer Tetrahydrofurylgruppe,
- R2
- Wasserstoff, F, Cl, C1-C5-Alkyl, C1-C5-Alkoxy, Phenyl oder Benzyl ist,
- R3
- Wasserstoff, eine C1-C4-Alkylgruppe, eine Alkarylgruppe, eine Cycloalkylgruppe oder eine Arylgruppe ist, z.B. eine Phenylgruppe, und
- R4
- eine C1-C4-Alkylgruppe, eine Alkarylgruppe, eine Cycloalkylgruppe oder eine Arylgruppe ist, z.B. eine Phenylgruppe.
- R 1
- is a mono- or dialkylamino group in substituted form, for example substituted with a tetrahydrofuryl group,
- R 2
- Is hydrogen, F, Cl, C1-C5-alkyl, C1-C5-alkoxy, phenyl or benzyl,
- R 3
- Is hydrogen, a C1-C4 alkyl group, an alkaryl group, a cycloalkyl group or an aryl group, for example a phenyl group, and
- R 4
- is a C1-C4 alkyl group, an alkaryl group, a cycloalkyl group or an aryl group, for example a phenyl group.
Andere Leukofarbstoffe, die durch Reaktion mit einer Säure eine farbige Verbindung ergeben, sind Leuko-Kristallviolett, Leuko-Malachitgrün, Kristallviolettlakton, Benzoyl-Leuko-Methylenblau und die säureempfindlichen Leukofarbstoffverbindungen in der Klasse der Bisindophthalide und Carbazolylmethane, die in US-Patent 5.206.118 beschrieben sind.Other leuco dyes that are a colored compound by reaction with an acid are leuko crystal violet, leuko malachite green, crystal violet lactone, Benzoyl-leuco-methylene blue and the acid-sensitive leuco dye compounds in the class of bisindophthalides and carbazolylmethanes, which in U.S. Patent 5,206,118.
Als Bindemittel für die Leukofarbstoffschicht eignen sich die gleichen Bindemittel sie für die Silbersalzschicht. Besonders gut geeignet sind Vinylchlorid und Vinylidenchlorid Copolymerisate, wie z.B. Poly(Vinylchlorid-co-Vinylacetat).The same binders are suitable as binders for the leuco dye layer them for the silver salt layer. Vinyl chloride and vinylidene chloride are particularly suitable Copolymers, e.g. Poly (vinyl chloride-co-vinyl acetate).
Die genannten Bindemittel können in Verbindung mit Wachsen oder "Wärmelösemitteln", auch als "Thermo-Lösemittel" bezeichnet, eingesetzt werden, die die Reaktionsgeschwindigkeit der Farbstoffbildungsreaktion und der Bildsilber erzeugenden Redox-Reaktion bei erhöhten Temperaturen verbessern.The binders mentioned can be used in conjunction with waxes or "heat solvents", also referred to as "thermal solvents", which are used Reaction speed of the dye formation reaction and the image silver producing Improve redox reaction at elevated temperatures.
Der Begriff "Wärmelösemittel" im Sinne der vorliegenden Erfindung bezeichnet ein nicht hydrolysierbares organisches Material, das bei Temperaturen unter 50 °C eine feste Form hat, aber ab etwa 60 °C als Weichmacher für das Bindemittel dient, mit dem es sich in dem erwärmten Bereich verbindet und/oder dann als Lösemittel für mindestens einen der farbbildenden Reaktionspartner wirkt. Für diesen Zweck geeignet ist z.B. ein Polyethylenglykol mit einer mittleren relativen Molekülmasse zwischen 1.500 und 20.000 gemäß Beschreibung in US-Patent 3.347.675.Die Dicke der Leukofarbstoffschicht beträgt 2 bis 25 µm, vorzugsweise 4 bis 15 µm.The term "heat solvent" in the sense of the present invention denotes a non-hydrolyzable organic material that can be used at temperatures below 50 ° C has a solid form, but from around 60 ° C as a plasticizer for the binder serves with which it connects in the heated area and / or then as Solvent acts for at least one of the color-forming reactants. For this purpose is suitable e.g. a polyethylene glycol with a medium relative Molecular mass between 1,500 and 20,000 as described in US patent 3,347,675. The thickness of the leuco dye layer is 2 to 25 µm, preferably 4 to 15 µm.
Geeignete Entwickler für den Leukofarbstoff sind elektronenaufnehmende oder sauer reagierende Verbindungen. Beispielhaft seien genannt: 1,3-bis-p-Hydroxycumylbenzol oder 1,4-bis-Cumylbenzol, p-Hydroxybenzoesäure-Butylester (PHBB) und Bisphenole wie z.B. 4,4'-Isopropylidendiphenol (Bisphenol A) sowie analoge Verbindungen, die im Journal of Imaging Technology, Jg. 16, Nr. 6, Dezember 1990, S. 235, sowie in DE-A- 35 34 594 und DE-A-43 29 133 beschrieben sind. Andere geeignete sauer reagierende Verbindungen, die als Entwickler für Leukofarbstoffe dienen, sind Monoester von aromatischen ortho-Carbonsäuren, die z.B. in US-Patent 4.011.352 beschrieben sind, insbesondere der Ethylhalbester der ortho-Phthalsäure.Suitable developers for the leuco dye are electron-accepting or acidic compounds. Examples include: 1,3-bis-hydroxycumylbenzene or 1,4-bis-cumylbenzene, p-hydroxybenzoic acid butyl ester (PHBB) and bisphenols such as 4,4'-isopropylidenediphenol (bisphenol A) and analogues Compounds reported in the Journal of Imaging Technology, Vol. 16, No. 6, December 1990, p. 235, as well as in DE-A-35 34 594 and DE-A-43 29 133. Other suitable acidic compounds used as developers for leuco dyes serve are monoesters of aromatic ortho-carboxylic acids which e.g. in U.S. Patent 4,011,352, particularly the ethyl half ester of ortho-phthalic acid.
Die Entwicklerschicht wird zweckmäßigerweise unter Verwendung solcher Lösungsmittel hergestellt, die für das Bindemittel der Leukofarbstoffschicht keine lösende Wirkung haben. Dementsprechend sind die in der Entwicklerschichtverwendeten Bindemittel wasser- oder alkohollöslich. Es kann sich dabei um modifizierte natürliche oder synthetische Polymere handeln. Als Beispiel seien Cellulosederivate, Polyvinylpyrrolidon und Copolymerisate aus Vinylpyrrolidon und Vinylacetat genannt. Ein bevorzugtes Bindemittel ist Nitrocellulose. Die Schichtdiche der Entwicklerschicht beträgt 1 bis 15 µm, vorzugsweise 3 µm bis 10 µm.The developer layer is expediently used using such Solvent produced that for the binder of the leuco dye layer none have a dissolving effect. Accordingly, those used in the developer layer Binder soluble in water or alcohol. It can be modified act natural or synthetic polymers. Take cellulose derivatives as an example, Polyvinylpyrrolidone and copolymers of vinylpyrrolidone and Called vinyl acetate. A preferred binder is nitrocellulose. The layer thickness the developer layer is 1 to 15 µm, preferably 3 µm to 10 µm.
Selbstverständlich kann das erfindungsgemäße Aufzeichnungsmaterial weitere für diesen Einsatzzweck bekannte Schichten enthalten. So kann es günstig sein, als oberste Schicht eine Abdeckschicht (topcoat) anzubringen. Eine übliche Dicke dieser Abdeckschicht beträgt 0.05 bis 2.5 µm.Of course, the recording material according to the invention can be used for contain layers known for this purpose. So it can be cheap than Apply a top coat to the top layer. A usual thickness this cover layer is 0.05 to 2.5 µm.
Die Abdeckschicht kann Antihafteigenschaften haben, was sich z.B. durch die Verwendung von Polysiloxanen, Polysiloxan-Polyether-Blockcopolymerisaten oder Fluorpolymeren erreichen läßt. Auch Polyvinylalkohol ist als Abdeckschicht geeignet.The cover layer can have non-stick properties, e.g. through the Use of polysiloxanes, polysiloxane-polyether block copolymers or Can achieve fluoropolymers. Polyvinyl alcohol is also used as a cover layer suitable.
Für das Beschreiben des Bildmaterials mit einem Thermokopf hat es sich als günstig erwiesen, eine thermostabile Abdeckschicht anzubringen. Hierfür geeignete Polymere haben einen Erweichungspunkt oberhalb von 100 °C, vorzugsweise oberhalb von 130 °C. Gut geeignet ist Polycarbonat, insbesondere Homo- und Copolymere des Trimetylcyclohexylbisphenolpolycarbonats. Die letztgenannten Polymere führen zu Bildmaterialien mit besonders hohem Glanz und guter Bildschärfe. Eine Verschmutzung des Thermokopfes durch das Bildmaterial infolge von Verklebung oder Abrieb findet nicht statt. Ein zusätzlicher Vorteil dieser Polymere besteht in ihrer einfachen Verarbeitbarkeit, z.B. durch Gießen aus organischer Lösung. For the description of the image material with a thermal head it turned out to be proved to be favorable to apply a thermostable cover layer. Suitable for this Polymers have a softening point above 100 ° C, preferably above 130 ° C. Polycarbonate is particularly suitable, especially homo- and Copolymers of trimetylcyclohexyl bisphenol polycarbonate. The latter Polymers lead to image materials with a particularly high gloss and good Focus. Contamination of the thermal head due to the image material as a result of gluing or abrasion does not take place. An added benefit of this Polymers are easy to process, e.g. by pouring out organic solution.
Die Herstellung der erfindungsgemäßen Aufzeichnungsmaterialien kann mittels bekannter Technologien erfolgen. Günstig ist die Herstellung durch Gießen oder Rakeln. Die Schicht mit dem wasser- oder alkohollöslichen Polymer und die Entwicklerschicht können in einfacher Weise aus Wasser, Alkohol oder Wasser-Alkohol-Gemischen, z.B. aus Methylalkohol, Ethylalkohol, Isopropylalkohol gegossen werden. Für die Silbersalzschicht und die Leukofarbstoffschicht sind im allgemeinen nichtwäßrige Lösungsmittel notwendig. Geeignete Lösemittel sind z.B. Aceton, Methylethylketon, Tetrahydrofuran, Dioxan, Dichlormethan, Tetrachlormethan und Ethylacetat.The recording materials according to the invention can be produced using known technologies. The production by casting or Squeegees. The layer with the water or alcohol soluble polymer and the Developer layer can easily be made from water, alcohol or water-alcohol mixtures, e.g. cast from methyl alcohol, ethyl alcohol, isopropyl alcohol become. For the silver salt layer and the leuco dye layer are in general non-aqueous solvents necessary. Suitable solvents are e.g. Acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, dichloromethane, carbon tetrachloride and ethyl acetate.
Die erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterialien können z.B. mit einem Thermokopf beschrieben werden und liefern Schwarz-Weiß-Bilder mit hoher optischer Dichte (D-max > 2), guter Graustufenwiedergabe, hoher Schärfe und guter Stabilität. Die Gradation ist, vor allem in Bereichen geringerer Dichte, für die Halbtonreproduktion gut geeignet, z.B. für die Porträt-reproduktion bei Ausweisdokumenten und im Bereich der medizinischen Diagnostik für die Wiedergabe von Bildern, die z.B. durch Röntgen-, Ultraschall- oder Kernspinresonanz- (NMR-) Signale erzeugt werden.The heat-sensitive recording materials according to the invention can e.g. can be written with a thermal head and provide black and white images with high optical density (D-max> 2), good grayscale reproduction, high Sharpness and good stability. The gradation is lower, especially in areas Density, well suited for halftone reproduction, e.g. for portrait reproduction ID documents and medical diagnostics for the Playback of images, e.g. by X-ray, ultrasound or nuclear magnetic resonance (NMR) signals are generated.
Der Begriff "Gradation" bezieht sich auf die Steigung einer Schwärzungskurve, die die optische Dichte (D) als Funktionswert (Ordinate) zu linear steigenden Wärmemengen auf der Abszisse darstellt. Hierbei werden unterschiedliche Wärmemengen in aneinander angrenzenden Bereichen auf das thermografische Material aufgebracht, analog zur Herstellung eines Stufenkeils. Die lineare Wärmezunahme wird z.B. durch lineare Erhöhung der Erwärmungszeit an verschiedenen Stellen des Aufnahmematerials erzielt, wobei die Heizleistung (J) pro Zeiteinheit (s) konstant gehalten wird. Alternativ kann die Erwärmungszeit konstant bleiben und statt dessen die Heizleistung linear erhöht werden.The term "gradation" refers to the slope of a density curve that the optical density (D) as a function value (ordinate) for linearly increasing amounts of heat on the abscissa. Here, different amounts of heat applied to the thermographic material in adjacent areas, analogous to the production of a step wedge. The linear heat gain will e.g. by linearly increasing the heating time at various points in the Recording material achieved, the heating power (J) per unit time (s) constant is held. Alternatively, the heating time can remain constant instead of whose heating power can be increased linearly.
Definitionsgemäß ergeben alle Gradienten oder Steigungen der besagten Schwärzungskurve zusammen die Gradation des thermografischen Bildes. Ein Gradient entspricht der Steigung an einem einzelnen Punkt auf der Schwärzungskurve. Der Gammawert (γ) ist der maximale Gradient der besagten Schwärzungskurve und entspricht in der Regel dem Gradienten zwischen dem Ende des Fußes und dem Anfang der Schulter der Schwärzungskurve. By definition, all gradients or slopes of said blackening curve result together the gradation of the thermographic image. A gradient corresponds to the slope at a single point on the density curve. The Gamma value (γ) is the maximum gradient of said blackening curve and usually corresponds to the gradient between the end of the foot and the Beginning of the shoulder of the darkness curve.
Auch das Einschreiben mit einem Infrarot-Laser ist möglich, in diesem Falle wird dem Aufzeichnungsmaterial ein Infrarotabsorber zugesetzt.It is also possible to write with an infrared laser, in this case an infrared absorber is added to the recording material.
Das erfindungsgemäße Aufzeichnungsmaterial ist auch aus ökologischer Sicht besonders vorteilhaft. The recording material according to the invention is also from an ecological point of view particularly advantageous.
Auf einer substrierten Polyethylenterephthalatunterlage mit einer Schichtdicke von
125 µm wurde mit Hilfe einer Rakel eine Silbersalzschicht mit nachfolgend angegebener
Zusammensetzung aus einer Methylethylketon-Lösung aufgetragen und
getrocknet:
Anschließend wurde aus wäßriger Lösung eine Sperrschicht aus Polyvinylalkohol (Moviol® 18/88) mit einem Auftrag von 2,50 g/m2 aufgebracht.Then a barrier layer made of polyvinyl alcohol (Moviol® 18/88) was applied from an aqueous solution at a rate of 2.50 g / m 2 .
Darüber wurde eine Leukofarbstoffschicht mit der nachfolgend angegebenen Zusammensetzung
aus einer Methylethylketon-Lösung aufgetragen und getrocknet:
Darüber wurde eine Entwicklerschicht mit nachfolgend angegebener Zusammensetzung
aus einer Methanol-Lösung aufgetragen und getrocknet:
Entsprechend der in Beispiel 1 angegebenen Arbeitsweise wurde ein Aufnahmematerial mit nachfolgender Zusammensetzung angefertigt. In accordance with the procedure given in Example 1, a recording material was made with the following composition.
Unterlage: substrierte Polyethylenterephthalatfolie mit einer Schichtdicke von
100 µm
Entsprechend der in Beispiel 1 angegebenen Arbeitsweise wurde ein Aufnahmematerial mit nachfolgender Zusammensetzung angefertigt.In accordance with the procedure given in Example 1, a recording material was made with the following composition.
Unterlage: substrierte Polyethylenterephthalatfolie mit einer Schichtdicke von
100 µm
Auf die Aufnahmematerialien der Beispiele 1 bis 3 wurden mit Hilfe eines Printers
mit Thermokopf (Hitachi VY 100 videoprinter) ein Testbild mit 16 Graustufen
eingeschrieben. Die optischen Dichten der einzelnen Stufen wurden in Transmission
gemessen und tabelliert.
Die Tabelle läßt klar erkennen, daß die erfindungsgemäßen Materialien, besonders im Bereich niedriger Dichten zur Wiedergabe von Graustufen gut geeignet sind.The table clearly shows that the materials of the invention, especially in the area of low densities are well suited for the reproduction of grayscale.
Claims (6)
- A heat-sensitive image recording material comprising on a base materialat least one binder layer or a sequence of binder layers comprising a heat-sensitive imaging combination of an organic silver salt and an organic reducing agent for the organic silver salt, andat least one binder layer or a sequence of binder layers comprising a heat-sensitive imaging combination of an acid-sensitive leuco dye and a compound being acidic in reaction and acting as a developer for the leuco dye,
- The image recording material according to claim 1, characterised in that it comprises at least four layers on a base material, namely1. a binder layer comprising a heat-sensitive imaging combination of an organic silver salt and an organic reducing agent for the organic silver salt (silver salt layer),2. a layer comprising a water- or alcohol-soluble polymer (barrier layer),3. a layer comprising a leuco dye and a binder for the leuco dye (leuco dye layer) and4. a layer comprising a developer for the leuco dye and a water- or alcohol-soluble binder (developer layer).
- The image recording material according to claim 2, characterised in that the silver salt layer is 8 to 32 µm thick, the layer comprising the water- or alcohol-soluble polymer is 0.1 to 10 µm thick, the leuco dye layer is 2 to 25 µm thick and the developer layer is 0.1 to 10 µm thick.
- The image recording material according to any of claims 2 to 3, characterised in that the barrier layer consists of poly(vinyl alcohol).
- The image recording material according to any of claims 2 to 3, characterised in that the binder of the developer layer is nitrocellulose.
- Process for manufacturing a heat-sensitive image recording material according to any of claims 1 to 2, characterised in that all layers are coated consecutively from solutions.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19536045 | 1995-09-28 | ||
DE19536045A DE19536045A1 (en) | 1995-09-28 | 1995-09-28 | Heat-sensitive recording material |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0767403A2 EP0767403A2 (en) | 1997-04-09 |
EP0767403A3 EP0767403A3 (en) | 1997-07-30 |
EP0767403B1 true EP0767403B1 (en) | 2002-04-17 |
Family
ID=7773390
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96114797A Expired - Lifetime EP0767403B1 (en) | 1995-09-28 | 1996-09-16 | Heat-sensitive recording material |
Country Status (4)
Country | Link |
---|---|
US (1) | US5753587A (en) |
EP (1) | EP0767403B1 (en) |
JP (1) | JPH09109550A (en) |
DE (2) | DE19536045A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998012053A1 (en) | 1996-09-23 | 1998-03-26 | Media Solutions, Inc. | Direct thermal printable film and laminate |
US6090747A (en) * | 1996-12-17 | 2000-07-18 | Labelon Corporation | Thermosensitive direct image-recording material |
US6409328B1 (en) * | 1999-03-31 | 2002-06-25 | Fuji Photo Film Co., Ltd. | Method of forming images and material for image formation |
CN101594999B (en) * | 2006-12-07 | 2011-10-12 | 爱克发-格法特公司 | Method of producing an information carrier |
US8871994B2 (en) | 2010-12-10 | 2014-10-28 | Kimberly-Clark Worldwide, Inc. | Wetness sensor for use in an absorbent article |
US12046162B2 (en) | 2017-12-12 | 2024-07-23 | Gourgen AMBARTSOUMIAN | Shielded direct thermal label and methods |
US11472214B1 (en) * | 2017-12-12 | 2022-10-18 | Gourgen AMBARTSOUMIAN | Shielded direct thermal label and methods |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5581194A (en) * | 1978-12-14 | 1980-06-18 | Ricoh Co Ltd | Polychromic heat sensitive recording material |
DE3540627A1 (en) * | 1984-11-15 | 1986-05-22 | Ricoh Co., Ltd., Tokio/Tokyo | TWO-COLOR HEAT-SENSITIVE RECORDING MATERIAL |
US5196297A (en) * | 1985-12-16 | 1993-03-23 | Polaroid Corporation | Recording material and process of using |
JP2681907B2 (en) * | 1992-11-20 | 1997-11-26 | 日本製紙株式会社 | Thermal recording medium |
EP0680833B1 (en) * | 1994-05-02 | 1997-09-10 | Agfa-Gevaert N.V. | Recording material for direct thermal imaging |
-
1995
- 1995-09-28 DE DE19536045A patent/DE19536045A1/en not_active Withdrawn
-
1996
- 1996-09-16 EP EP96114797A patent/EP0767403B1/en not_active Expired - Lifetime
- 1996-09-16 DE DE59609086T patent/DE59609086D1/en not_active Expired - Fee Related
- 1996-09-18 US US08/715,196 patent/US5753587A/en not_active Expired - Fee Related
- 1996-09-25 JP JP8272874A patent/JPH09109550A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
EP0767403A3 (en) | 1997-07-30 |
DE59609086D1 (en) | 2002-05-23 |
DE19536045A1 (en) | 1997-04-03 |
EP0767403A2 (en) | 1997-04-09 |
US5753587A (en) | 1998-05-19 |
JPH09109550A (en) | 1997-04-28 |
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