JPH0156920B2 - - Google Patents
Info
- Publication number
- JPH0156920B2 JPH0156920B2 JP57118482A JP11848282A JPH0156920B2 JP H0156920 B2 JPH0156920 B2 JP H0156920B2 JP 57118482 A JP57118482 A JP 57118482A JP 11848282 A JP11848282 A JP 11848282A JP H0156920 B2 JPH0156920 B2 JP H0156920B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- layer
- weight
- sensitive
- color
- 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
Links
- 238000004040 coloring Methods 0.000 claims description 36
- 239000000126 substance Substances 0.000 claims description 23
- 239000000945 filler Substances 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 15
- 230000002378 acidificating effect Effects 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 14
- 150000001447 alkali salts Chemical class 0.000 claims description 5
- 239000010410 layer Substances 0.000 description 74
- 238000000576 coating method Methods 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 22
- 239000000975 dye Substances 0.000 description 17
- 230000035945 sensitivity Effects 0.000 description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 14
- 239000011241 protective layer Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 229920003169 water-soluble polymer Polymers 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 239000002492 water-soluble polymer binding agent Substances 0.000 description 5
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- -1 biphenyl alkane Chemical class 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000006103 coloring component Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 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
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 229920003086 cellulose ether Polymers 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229940037312 stearamide Drugs 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 2
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- HUOKHAMXPNSWBJ-UHFFFAOYSA-N 2'-chloro-6'-(diethylamino)-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(Cl)=C(C)C=C1OC1=CC(N(CC)CC)=CC=C21 HUOKHAMXPNSWBJ-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZDRSNHRWLQQICP-UHFFFAOYSA-N 2-tert-butyl-4-[2-(3-tert-butyl-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C1=C(O)C(C(C)(C)C)=CC(C(C)(C)C=2C=C(C(O)=CC=2)C(C)(C)C)=C1 ZDRSNHRWLQQICP-UHFFFAOYSA-N 0.000 description 1
- ABJAMKKUHBSXDS-UHFFFAOYSA-N 3,3-bis(6-amino-1,4-dimethylcyclohexa-2,4-dien-1-yl)-2-benzofuran-1-one Chemical compound C1=CC(C)=CC(N)C1(C)C1(C2(C)C(C=C(C)C=C2)N)C2=CC=CC=C2C(=O)O1 ABJAMKKUHBSXDS-UHFFFAOYSA-N 0.000 description 1
- DJRJYWNDMBCUSJ-UHFFFAOYSA-N 3,3-bis[4-(dibutylamino)phenyl]-2-benzofuran-1-one Chemical compound C1=CC(N(CCCC)CCCC)=CC=C1C1(C=2C=CC(=CC=2)N(CCCC)CCCC)C2=CC=CC=C2C(=O)O1 DJRJYWNDMBCUSJ-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- PGAAZCXJMPDCHO-UHFFFAOYSA-N 3-(4-chloro-2-hydroxy-5-methylphenyl)-3-[4-(dimethylamino)-2-methoxyphenyl]-2-benzofuran-1-one Chemical compound COC1=CC(N(C)C)=CC=C1C1(C=2C(=CC(Cl)=C(C)C=2)O)C2=CC=CC=C2C(=O)O1 PGAAZCXJMPDCHO-UHFFFAOYSA-N 0.000 description 1
- RHWGUGLTKRIMRC-UHFFFAOYSA-N 3-(5-chloro-2-methoxyphenyl)-3-[4-(dimethylamino)-2-hydroxyphenyl]-2-benzofuran-1-one Chemical compound COC1=CC=C(Cl)C=C1C1(C=2C(=CC(=CC=2)N(C)C)O)C2=CC=CC=C2C(=O)O1 RHWGUGLTKRIMRC-UHFFFAOYSA-N 0.000 description 1
- WMOULUHRMJQPDK-UHFFFAOYSA-N 3-[4-(diethylamino)-2-hydroxyphenyl]-3-(2-methoxy-5-methylphenyl)-2-benzofuran-1-one Chemical compound OC1=CC(N(CC)CC)=CC=C1C1(C=2C(=CC=C(C)C=2)OC)C2=CC=CC=C2C(=O)O1 WMOULUHRMJQPDK-UHFFFAOYSA-N 0.000 description 1
- LSYHVTSZEQZQNJ-UHFFFAOYSA-N 3-[4-(dimethylamino)-2-hydroxyphenyl]-3-(2-methoxy-5-nitrophenyl)-2-benzofuran-1-one Chemical compound COC1=CC=C([N+]([O-])=O)C=C1C1(C=2C(=CC(=CC=2)N(C)C)O)C2=CC=CC=C2C(=O)O1 LSYHVTSZEQZQNJ-UHFFFAOYSA-N 0.000 description 1
- XJCVRTZCHMZPBD-UHFFFAOYSA-N 3-nitroaniline Chemical compound NC1=CC=CC([N+]([O-])=O)=C1 XJCVRTZCHMZPBD-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical class OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 1
- LYCCNHVQBSOODL-UHFFFAOYSA-N 6-(diethylamino)-3,3-bis[4-(dimethylamino)phenyl]-2-benzofuran-1-one Chemical compound C=1C(N(CC)CC)=CC=C2C=1C(=O)OC2(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 LYCCNHVQBSOODL-UHFFFAOYSA-N 0.000 description 1
- KCBLOCLSUSTAMW-UHFFFAOYSA-N 6-chloro-3,3-bis[4-(dimethylamino)phenyl]-2-benzofuran-1-one Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC=C(Cl)C=C2C(=O)O1 KCBLOCLSUSTAMW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- MOZDKDIOPSPTBH-UHFFFAOYSA-N Benzyl parahydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 MOZDKDIOPSPTBH-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- IPAJDLMMTVZVPP-UHFFFAOYSA-N Crystal violet lactone Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C=CC(=CC=2)N(C)C)C2=CC=C(N(C)C)C=C2C(=O)O1 IPAJDLMMTVZVPP-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- DYRDKSSFIWVSNM-UHFFFAOYSA-N acetoacetanilide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1 DYRDKSSFIWVSNM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012164 animal wax Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical compound C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BMOAQMNPJSPXIU-UHFFFAOYSA-N ethyl 2-(3-fluoro-4-nitrophenyl)propanoate Chemical compound CCOC(=O)C(C)C1=CC=C([N+]([O-])=O)C(F)=C1 BMOAQMNPJSPXIU-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- QELSKZZBTMNZEB-UHFFFAOYSA-N propylparaben Chemical compound CCCOC(=O)C1=CC=C(O)C=C1 QELSKZZBTMNZEB-UHFFFAOYSA-N 0.000 description 1
- 229960003415 propylparaben Drugs 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- ZCTQGTTXIYCGGC-UHFFFAOYSA-N salicylic acid benzyl ester Natural products OC1=CC=CC=C1C(=O)OCC1=CC=CC=C1 ZCTQGTTXIYCGGC-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000012178 vegetable wax Substances 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
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Description
本発明は、感熱記録シートに関し、更に詳しく
は通常無色又はやや淡色の発色性ロイコ染料と該
ロイコ染料を熱時発色させうる酸性物質とを発色
成分とし、かつアンダーコート層、感熱発色層、
バツクコート層の３層構成にして発色性向上、ヘ
ツドマツチング性及び感熱発色層の耐溶剤性を向
上させた感熱記録シートのカールの改善に関す
る。
通常無色ないし、淡色の発色性ロイコ染料と有
機酸性物質とが熱時、溶融反応して発色する事は
古くから知られており、この発色反応を記録紙に
応用した例は、特公昭43−4160号公報、特公昭45
−14039号公報等に開示されており公知である。
これらの感熱記録シートは計測用レコーダー、コ
ンピユーター等の端末プリンター、フアクシミ
リ、自動券売機、バーコードラベルなど広範囲の
分野に応用されているが、最近はこれら記録装置
の多様化、高性能化が進められるに従つて、感熱
記録シートに対する要求品質もより高度なものと
なつている。例えば、サーマルヘツドの高速化に
伴い微小な熱エネルギーでも高濃度で鮮明な画像
を記録でき、かつステイツキング、ヘツドカス等
のヘツドマツチング性が良好な感熱記録シートが
要求されている。
感熱記録シートの発色は、発色性ロイコ染料、
酸性物質の両方又はいずれかが、サーマルヘツド
から供給される熱エネルギーによつて溶融し、反
応するものであるが、発色感度を向上する方法の
一つとしては、ロイコ染料と酸性物質よりも低い
温度で溶融し、かつ両者を溶解する能力の高い化
合物（一般に熱可融性物質と呼ばれる）を添加す
る方法が広く知られており、種々の化合物が下記
公報に開示されている。例えば、特開昭49−
34842号公報にはアセトアミド、ステアロアミド、
ｍ−ニトロアニリン、フタル酸ジニトリル等の含
窒素化合物、特開昭52−106746号公報にはアセト
酢酸アニリド、特開昭53−39139号公報にはアル
キル化ビフエニル、ビフエニルアルカン等々であ
る。
しかしながら、近年は特にサーマルフアクシミ
リ分野での高速化が進み、サーマルヘツドを高速
駆動させることが一般化しつつあり、ヘツド周囲
の蓄熱のために感熱記録シートが連続記録中に地
肌部が発色したりして（余熱発色）、不都合があ
るため発色開始温度を低下させることなく、動的
発色感度を高める事が課題となつている。しかし
これらの化合物では、静的発色感度は向上するが
大量に感熱発色層中に添加しないと十分な動的発
色感度が得られず、又、その場合にサーマルヘツ
ドの溶融物の付着（ヘツドカス）が多かつたり、
ステイツキングを生じたり、更には融点が低すぎ
る場合には、感熱記録シートの保存性（地肌のカ
ブリ）を低下させたりして十分満足のいく結果は
得られない。
又、動的発色感熱を向上する方法の一つとし
て、感熱発色層表面の平滑性を向上させたり、或
いは発色層中の発色反応に関与しない成分、例え
ば充填剤や結合剤の含有量を少なくし、発色成分
密度をあげたりする方法もある。表面の平滑性を
向上させるには通常スーパーカレンダー等によ
り、カレンダーがけする事によつて容易に達成し
うるが、地肌が発色したり、表面光沢度が高くな
つたりして記録紙としては外観をはなはだ損ね
る。また、感熱発色層には通常地肌の白さ保持の
ためや、ヘツドへのカス付着防止、ステイツキン
グ防止のために炭酸カルシウム、クレー、尿素−
ホルマリン樹脂微粒子等の充填剤を添加したり、
発色成分やその添加物の支持体への固着のために
水溶性結合剤を添加するが、これらの含有量を少
なくすることは、とりもなおさず上記品質の劣化
を招き、不都合が生じて、かかる方法も十分満足
のいく結果が得られない。
また、近年は、発色性ロイコ染料と酸性物質か
ら成る感熱記録シートは、エタノール、アセトン
等の揮発性有機溶媒がかかると地肌が発色した
り、不揮発性有機溶媒（例えば油、可塑剤、指紋
等）がかかると画像部が消失したりする欠点があ
り、改良が望まれている。
かかる現状に鑑み、本発明者らは種々検討を重
ねた結果、支持体上に充填剤と結合剤とを主成分
とするアンダーコート層、無色又はやや淡色の発
色性ロイコ染料と該ロイコ染料を熱時発色させう
る酸性物質を主成分とする感熱発色層及び水溶性
高分子結合剤と充填剤を主成分とする保護層を、
順次積層することによつて上記問題を改善できる
ことを見い出し、特願昭57−17071号として先に
出願した。
しかしながら、上記構成による感熱記録シート
は、前述の欠点は改善できるが、支持体の表面に
３層塗布していること及びオーバーコート層の水
溶性高分子結合剤の含有量が多いため、塗布時の
フエイス・カール及び低湿（相対湿度50％RH以
下）時のフエイス・カールが大きく、フアクシミ
リに使用した場合など、ジヤムの原因になつたり
して、はなはだ不都合があつた。
そこで、本発明者らは、更に検討を重ねた結
果、上記感熱記録シートの裏面に、イソブチレン
−無水マレイン酸共重合体又はジイソブチレン−
無水マレイン酸共重合体のアルカリ塩を含有する
バツクコート層を設けることによつて、上記問題
を改善できることを見い出し、本発明を成すに至
つた。
しかして、本発明の目的は、微小な熱エネルギ
ーでも高濃度で鮮明な画像を記録できる動的発色
濃度の高い感熱記録シートで、かつステイツキン
グ、ヘツドカス等のヘツドマツチング性が良好
で、感熱発色層の耐溶剤性に優れ、更には、低湿
環境においてもカールの少ない高感度感熱記録シ
ートを提供することにある。
本発明の感熱記録シートのアンダーコート層、
感熱発色層、保護層なそれぞれ、次のような機能
を有した層として積層しているため、上記目的を
達成することができる。
第１にアンダーコート層であるが、従来の感熱
記録シートは30〜60ｇ／m2の上質紙上に３〜10
ｇ／m2位の感熱発色層を設けているが、紙の表面
は１〜10μ位の凹凸があり、かつ水性の塗布液は
紙の中に浸透しやすいために、感熱発色層表面と
サーマルヘツドとの接触が均一にならず、又、紙
の深さ方向への熱伝導が少ない為、サーマルヘツ
ドから供給される熱エネルギーを有効に発色反応
に寄与できない。
しかし本発明によれば、アンダーコート層を紙
表面の凹凸をつぶし、かつ上から塗布する感熱発
色層の紙への浸透を適度に抑制する層として形成
することによつて、サーマルヘツドから供給され
る熱エネルギーを発色層が有効に利用しうるよう
になる。つまり、本発明のアンダーコート層は、
上層の感熱発色層の感度を向上させるための層と
して機能する。かかるアンダーコート層は、充填
剤の塗布量が2.0ｇ／m2以上で、かつ、アンダー
コート層中の結合剤が10〜50重量％とすることが
特に好ましい。この場合、充填剤の塗布量が2.0
ｇ／m2以下になると紙表面の凹凸をつぶしにくく
なるため効果が低くなる。又、結合剤の量は10重
量％未満であると感熱発色層が浸透しすぎたり、
又充填剤の結着性が弱くなる。又、50重量％を越
えると発色感度向上の効果が少なくなる。
又、本発明でいうところの充填剤とは、通常製
紙、コーテイング等に用いられる無機及び有機の
フイラーのことで、炭酸カルシウム、クレー、タ
ルク、シリカやポリスチレン微粒子、尿素−ホル
マリン樹脂微粒子等がある。又、アンダーコート
層に用いられる結合剤としては、通常のポリビニ
ルアルコール、セルロースエーテル、デンプン、
ポリカルボン酸アンモニウム、イソブチレン−無
水マレイン酸共重合体のアルカリ塩等の水溶性高
分子やスチレン−ブタジエンラテツクス、スチレ
ン−アクリル酸エステル、酢酸ビニル等の水性エ
マルジヨンが用いられるが、望ましくは、乾燥後
耐水性のよい結合剤系を選択するのが望ましい。
第２に、感熱発色層は加熱によつて発色する層
として機能するが、従来の一層の感熱発色層より
も極度に動的発色感度を向上した層として積層さ
れる。感熱発色層はロイコ染料、酸性物質、充填
剤、結合剤からなり、必要に応じて熱可融性物質
も添加される。特に、充填剤が重量で発色性ロイ
コ染料の３倍量以下であり、かつ結合剤を感熱発
色層の３〜10重量％にすることによつて、目的を
達成することができる。
充填剤は感熱発色層に添加しなくともよいが、
３倍量位までは発色感度を低下させることなく発
色色調の深味を出すことができる。又、結合剤は
感熱発色層の３重量％未満になると結着力が低す
ぎて問題があり、又10重量％を越える量になる
と、動的発色感度が低下してくる。（通常、一層
の感熱記録シートでは15〜30重量％位で用いられ
る。）
又、顕色成分である酸性物質は、通常用いられ
るのと同じようにロイコ染料に対し、２〜６倍量
で用いられる。
本発明に使用される無色又は、やや単色の発色
性ロイコ体としては、トリフエニルメタン系、フ
ルオラン系、フエノチアジン系、オーラミン系、
スピロピラン系のロイコ体が好ましく、以下にこ
れらの具体例を示す。
(イ) 下記一般式で示されるトリフエニルメタン系
染料のロイコ化合物：
（式中、Rx、RyおよびRzは水素、水酸基、ハ
ロゲン、アルキル基、ニトロ基、アミノ基、ジ
アルキルアミノ基、モノアルキル基、アリル基
である。）
上記ロイコ化合物の具体例は次の通りであ
る。
３，３−ビス（ｐ−ジメチルアミノフエニ
ル）−フタリド、３，３−ビス（ｐ−ジメチル
アミノフエニル）−６−ジメチルアミノフタリ
ド（別名クリスタルバイオレツトラクトン）、
３，３−ビス（ｐ−ジメチルアミノフエニル）
−６−ジエチルアミノフタリド、３，３−ビス
（ｐ−ジメチルアミノフエニル）−６−クロルフ
タリド、３，３−ビス（ｐ−ジブチルアミノフ
エニル）フタリド
(ロ) 下記一般式で表わされるフルオラン系染料の
ロイコ化合物：
式中、Rx、RyおよびRzは上記(イ)の場合と同
じである。
上記化合物の具体例は次の通りである。
３−シクロヘキシルアミノ−６−クロルフル
オラン、３−（Ｎ，Ｎ−ジエチルアミノ）−５−
メチル−７−（Ｎ，Ｎ−ジベンジルアミノ）フ
ルオラン、３−ジメチルアミノ−５，７−ジメ
チルフルオラン、３−ジエチルアミノ−７−メ
チルフルオラン、３−ジエチルアミノ−７，８
−ベンズフルオラン
(ハ) フルオラン系染料のロイコ化合物：
３−ジエチルアミノ−６−メチル−７−クロ
ルフルオラン、３−ピロリジノ−６−メチル−
７−アニリノフルオラン、２−｛Ｎ−（３−トリ
フルオルメチルフエニル）アミノ｝−６−ジエ
チルアミノフルオラン、２−｛３，６−ビス
（ジエチルアミノ）−９−（０−クロルアニリノ）
キサンチル安息香酸ラクタム｝
(ニ) 下記一般式で表わされるラクトン化合物：
式中、R1およびR2は水素、低級アルキル基、
置換または非置換アルアルキル基、置換または
非置換のフエニル基、シアノエチル基、または
β−ハロゲン化エチル基を表わすか、または
R1とR2が結合して、（−CH2−）4、（−CH2−）5また
は（−CH2−）2O（−CH2−）3を表わし、
R3およびR4は水素、低級アルキル基、アル
キル基、アミノ基またはフエニル基を表わし、
R3とR4のいずれか１つは水素であり、X1、X2
およびX3は水素、低級アルキル基、低級アル
コキシル基、ハロゲン原子、ハロゲン化メチル
基、ニトロ基、アミノ基、または置換されたア
ミノ基を表わし、X4は水素、ハロゲン、低級
アルキル基または低級アルコキシル基を表わ
し、ｎは０または１〜４の整数を表わす。
上記化合物の具体例は次の通りである。
３−（2′−ヒドロキシ−4′−ジメチルアミノ
フエニル）−３−（2′−メトキシ−5′−クロルフ
エニル）フタリド、３−（2′−ヒドロキシ−
4′−ジメチルアミノフエニル）−３−（2′−メト
キシ−5′−ニトロフエニル）フタリド、３−
（2′−ヒドロキシ−4′−ジエチルアミノフエニ
ル）−３−（2′−メトキシ−5′−メチルフエニ
ル）フタリド、３−（2′−メトキシ−4′−ジメ
チルアミノフエニル）−３−（2′−ヒドロキシ−
4′−クロル−5′−メチルフエニル）フタリド
又、前記ロイコ体と熱時反応して発色させうる
酸性物質としては、フエノール性酸性物質、有機
酸、有機カルボン酸の多価金属塩等が挙げられ、
具体的には以下のようなものが例示される。
α−ナフトール、β−ナフトール、４−ｔ−ブ
チルフエノール、４−フエニルフエノール、２，
2′−ビス（ｐ−ヒドロキシフエニル）プロパン、
２，2′−ビス（ｐ−ヒドロキシフエニル）ブタ
ン、４，4′−シクロヘキシリデンフエノール、
４，4′−イソプロピリデンビス（２−ｔ−ブチル
フエノール）、安息香酸、サリチル酸、３，５−
ジ−ｔ−ブチルサリチル酸亜鉛、３，５−ジ−ｔ
−ブチルサリチル酸錫、ヒドロキシ安息香酸プロ
ピル、ヒドロキシ安息香酸ベンジル等。
又、熱可融性物質は、必須成分である必要はな
いが、発色成分の溶融特性が高い場合に、それを
70〜120℃に低下せしめる目的で添加することが
できる。たとえば、３−ジエチルアミノ−０−ク
ロロアニリノフルオランをロイコ染料として用い
た場合、酸性物質としてｐ−オキシ安息香酸ベン
ジル（m.p.109℃）を用いると、DSCで溶融特性
を測定すると、84〜95℃で溶融することがわか
り、この系の場合には熱可融性物質の添加は必須
ではない。しかし、酸性物質としてビスフエノー
ルＡ（m.p.156℃）を用いると、溶融特性は、
DSCで130〜155℃に現れる。このような場合に
は、例えば、熱可融性物質としてステアリン酸ア
ミドを加えて、70〜80℃に溶融特性を低下させる
事が必要となる。このような構成にしないと、感
熱発色層の動的発色感度は十分なものとならな
い。
かかる熱可融性物質としては、高級脂肪酸アミ
ド、その誘導体、高級脂肪酸金属塩、動植物性ワ
ツクス、ポリエチレン、パラフイン、マイクロク
リスタリン等の石油系ワツクス等が挙げられる。
以上のように本発明のアンダーコート層、感熱
発色層は動的感度の向上を主として考慮された層
として積層されており、ヘツドマツチング性、例
えばヘツドカスは、実用上支障がある程度に多
い。そこで、本発明の保護層は、これらヘツドマ
ツチング性をカバーする保護層及び感熱発色層の
耐溶剤性を向上する保護層として機能する。この
保護層は、水溶性高分子結合剤と充填剤を主成分
とする。特に水溶性高分子結合剤が50〜90重量％
で、かつ保護層塗布量を１〜６ｇ／m2にすること
によつて、好ましい結果が得られる。水溶性高分
子結合剤が50重量％より少なくなると、感熱記録
シートとして積層した３層の結着力が弱すぎた
り、耐溶剤性向上の効果が十分でなかつたり、動
的感度の低下を招く。又、90重量％より多くなる
と、サーマルヘツドでのステイツキングが生じや
すくなる。又、動的感度の更なる向上、ヘツドマ
ツチング性の向上の為に０〜20重量％の熱可融性
物質を添加することもできる。又、必要に応じて
０〜20重量％の水性エマルジヨンを水溶性高分子
結合剤と共に併用することも可能である。
以上のごとく、アンダーコート層、感熱発色
層、保護層に明確な機能を持たせることによつ
て、それぞれの層の機能が発現し、それらが相乗
して、動的発色感度が高くヘツドマツチング性に
優れ、さらには耐溶剤性の良好な感熱記録シート
が得られる。しかしながら、これらの構成だけで
は、表面に３層塗布しており、かつ、オーバーコ
ート層が水溶性高分子の含有量が多いため、塗布
時のフエイス・カール、低湿でのフエイス・カー
ル（脱湿カール）が大きい。
そこで、本発明のバツクコート層は、少ない塗
布量でフエイス・カールを防止する層として機能
する。一般に表面に塗布した層のカールを改善す
るには、表面に塗布したものと同じ物質を裏面に
塗工してやれば改善できるが、表面が上記のよう
な構成では、通常の水溶性高分子、例えばポリビ
ニルアルコール、メチルセルロース、ヒドロキシ
エチルセルロース、カルボキシメチルセルロース
等のセルロースエーテル、デンプン及びデンプン
誘導体やSBR、ポリアクリル酸エステル等の水
性エマルジヨンでは極めて塗布量を多くしないと
フエイス・カールを改善できず、生産性が悪い。
しかし、本発明において用いられるイソブチレン
−無水マレイン酸共重合体又はジイソブチレン−
無水マレイン酸共重合体のアルカリ塩は、他の水
溶性高分子より固い樹脂であるために、少ない塗
布量でカールを改善することができる。
これらの水溶性高分子は、表面の３層の塗布量
によつて異なるが、0.5〜３ｇ／m2塗布すれば目
的を達成することができ、又、裏面の耐溶剤性向
上のためにポリビニルアルコール、カルボキシル
変成ポリビニルアルコールを加えたり、ブロツキ
ング防止のために炭酸カルシウム、タルク、シリ
カ等の無機填料や、ポリスチレン等の有機フイラ
ーを添加することもできる。
本発明の感熱記録シートを作るには、一般に知
られている方法を用いることができる。第１層の
アンダーコート層は、充填剤、結合剤溶液あるい
はエマルジヨンを混合し、必要によつては分散し
てアンダーコート塗布液を調製する。又、感熱発
色層塗布液は、まずロイコ染料、酸性物質は少な
くとも別々にして、ポリビニルアルコール、ヒド
ロキシエチルセルロース、メチルセルロース、ス
チレン−無水マレイン酸共重合体のアルカリ塩、
デンプン等の水溶性高分子の水溶液を加えて、ボ
ールミル、アトライター、サンドミル等の分散機
により分散粒径が１〜3μになるまで粉砕分散し
た後、必要に応じて充填剤、熱可融性物質分散
液、消泡剤等により一定処方に配合して感熱発色
層塗布液を調製する。さらに、保護層塗布液は、
充填剤、熱可融性物質、水溶性高分子結合剤を混
合、又は分散して調製する。バツクコート層は、
水溶性高分子結合剤、又、必要に応じて充填剤を
加えて、混合又は分散して調製する。
次にこれらの塗布液を、紙、合成紙等の支持体
上に順次塗布積層することによつて本発明の感熱
記録シートを作成する。
本発明の感熱記録シートの動的発色感度を具体
的に示すと、約300Ωの発熱抵抗体を有するフア
クシミリ用サーマルヘツドで、主走査記録時間20
ｍｓ／line、走査線密度８ドツト×3.85ドツト／
mm、プラテン押圧1.4Kg、ヘツド電圧13Vの条件
で、通電時間1.88ｍsecで印字した時の発色濃度
は、従来の一層コートの感熱記録シートでは1.2
以上発色するものはなかつたが（濃度計はマクベ
ス濃度計RD−514、フイルターwratten−106で
1.1以下）、本発明の感熱記録シートは、102以上
の発色濃度が得られる。また、ステイツキングも
なく、ヘツドカスはむしろ従来の感熱記録シート
よりも良好で、ほとんどカスを確認できない程度
である。
以下に本発明を実施例ならびに比較例により詳
細に説明する。
実施例 １、２、３
次の配合からなる混合物をアジテイタで撹拌し
てアンダーコート層塗布液を調整した。
ポリスチレン樹脂の40％分散液 52.5重量部
20％デンプン水溶液 17.5重量部
スチレン−ブタジエンラテツクス（48％）
7.3重量部
水 22.7重量部
次の配合からなる混合物をそれぞれボールミ
ル、アトライタにて体積平均粒径が約1.5μになる
まで粉砕分散して［Ａ］液、［Ｂ］液を調整した。
［Ａ］液組成
３−（Ｎ−シクロヘキシル−Ｎ−メチル）アミノ
−６−メチル−７−アニリノフルオラン20重量部
10％ポリビニルアルコール水溶液 16重量部
水 64重量部
［Ｂ］液組成
ｐ−オキシ安息香酸ベンジル 10重量部
炭酸カルシウム 10重量部
10％ポリビニルアルコール水溶液 16重量部
水 54重量部
ついで［Ａ］液：［Ｂ］液＝１：４の重量比で
混合撹拌して感熱発色層塗布液とした。
また、次の配合からなる混合物をサンドミルに
て分散して、保護層塗布液、バツクコート層塗布
液とした。
［保護層塗布液］
炭酸カルシウム 2.5重量部
10％ポリビニルアルコール水溶液 65重量部
ステアリン酸亜鉛 1.0重量部
水 31.5重量部
［バツクコート層塗布液］
炭酸カルシウム ２重量部
20％イソブチレン−無水マレイン酸共重合体のア
ンモニウム塩水溶液（クラレ社、イソバン−304）
40重量部
水 58重量部
次にこれらの塗布液を50ｇ／m2の市販上質紙に
アンダーコート層、感熱発色層はエアーナイフ
で、保護層は４本リバースコーター、バツクコー
ト層はエアーナイフコーターにて表１に示した塗
布量になるようにそれぞれ塗布乾燥して、本発明
の感熱記録シートを（実施例１、実施例２）作成
した。又、上記バツクコート層におけるイソブチ
レン−無水マレイン酸共重合体のアンモニウム塩
を、ジイソブチレン−無水マレイン酸共重合体の
アンモニウム塩にした他は同様にして実施例３の
感熱記録シートを作成した。
比較例
実施例１、２におけるバツクコート層の20％イ
ソブチレン−無水マレイン酸共重合体のアンモニ
ウム塩水溶液を
20％ポリビニルアルコール水溶液 （比較例１）
20％でんぷん水溶液 （比較例２）
20％SBRラテツクス （比較例３）
にかえた他は実施例２と同様にして、比較例１、
２、３の感熱記録シートを作成した。
The present invention relates to a heat-sensitive recording sheet, and more particularly, the present invention relates to a heat-sensitive recording sheet, and more specifically, the color-forming component is a normally colorless or slightly light-colored color-forming leuco dye and an acidic substance capable of causing the leuco dye to develop color when heated, and an undercoat layer, a heat-sensitive color forming layer,
This invention relates to an improvement in the curling of a heat-sensitive recording sheet in which the three-layer structure of the back coat layer improves color development, head matching properties, and solvent resistance of the heat-sensitive color development layer. It has been known for a long time that color-forming leuco dyes, which are usually colorless or light-colored, and organic acidic substances melt and react with each other when heated, producing color.An example of applying this color-forming reaction to recording paper is Publication No. 4160, Special Publication 1977
-14039, etc., and is publicly known.
These thermal recording sheets are used in a wide range of fields, including measurement recorders, terminal printers for computers, facsimile machines, automatic ticket vending machines, and barcode labels.Recently, these recording devices have become more diversified and more sophisticated. As the demand for heat-sensitive recording sheets increases, the quality required for heat-sensitive recording sheets also becomes higher. For example, as the speed of thermal heads increases, there is a demand for thermal recording sheets that can record high-density, clear images even with minute thermal energy and that have good head matching properties such as stagnation and head dregs. The heat-sensitive recording sheet is colored using chromogenic leuco dye,
Either or both of the acidic substances are melted and reacted by the thermal energy supplied from the thermal head, but one way to improve the coloring sensitivity is to use a leuco dye that is lower than the leuco dye and the acidic substance. A method of adding a compound (generally called a thermofusible substance) that melts at a certain temperature and has a high ability to dissolve both is widely known, and various compounds are disclosed in the following publications. For example, JP-A-49-
Publication No. 34842 describes acetamide, stearamide,
Nitrogen-containing compounds such as m-nitroaniline and dinitrile phthalate, acetoacetanilide in JP-A-52-106746, alkylated biphenyl, biphenyl alkane, etc. in JP-A-53-39139. However, in recent years, speeds have increased particularly in the field of thermal facsimile, and it has become common to drive thermal heads at high speed. (residual heat color development), which is inconvenient, so the challenge is to increase the dynamic color development sensitivity without lowering the color development start temperature. However, although these compounds improve the static coloring sensitivity, sufficient dynamic coloring sensitivity cannot be obtained unless they are added in large quantities to the thermosensitive coloring layer, and in that case, the adhesion of molten matter to the thermal head (head scum) may occur. There are many
If staking occurs or if the melting point is too low, the storage stability (fogging on the background) of the heat-sensitive recording sheet may be reduced, making it impossible to obtain fully satisfactory results. In addition, as a method for improving dynamic color development and heat sensitivity, it is possible to improve the surface smoothness of the heat-sensitive color development layer, or to reduce the content of components that do not participate in the color development reaction in the color development layer, such as fillers and binders. However, there is also a method of increasing the coloring component density. Improving the surface smoothness can be easily achieved by calendering using a super calender, etc., but this can cause the background to develop color and the surface gloss to be high, making the appearance unsuitable for recording paper. It's a huge loss. In addition, the heat-sensitive coloring layer usually contains calcium carbonate, clay, and urea to maintain the whiteness of the background, prevent dirt from adhering to the head, and prevent staining.
Adding fillers such as formalin resin fine particles,
A water-soluble binder is added to fix the coloring component and its additives to the support, but reducing the content of these binders will inevitably lead to the deterioration of the quality mentioned above, causing inconvenience. Such methods also do not provide fully satisfactory results. In addition, in recent years, heat-sensitive recording sheets made of color-forming leuco dyes and acidic substances have been found to cause the background to develop color when exposed to volatile organic solvents such as ethanol and acetone, and to avoid exposure to non-volatile organic solvents (e.g. oil, plasticizers, fingerprints, etc.). ), there is a drawback that the image area may disappear, and an improvement is desired. In view of the current situation, the present inventors have made various studies and have developed an undercoat layer containing a filler and a binder as main components on a support, a colorless or slightly light-colored color-forming leuco dye, and the leuco dye. A heat-sensitive color-forming layer whose main component is an acidic substance that can develop color when heated, and a protective layer whose main components are a water-soluble polymer binder and a filler.
It was discovered that the above problem could be improved by sequentially laminating layers, and the patent was filed as Japanese Patent Application No. 17071-1983. However, although the heat-sensitive recording sheet with the above structure can improve the above-mentioned drawbacks, it has three layers coated on the surface of the support and a high content of water-soluble polymeric binder in the overcoat layer, so the coating process is difficult. The face curl and the face curl at low humidity (relative humidity 50% RH or less) are large, and when used in a fax machine, etc., it can cause jamming, which is very inconvenient. Therefore, as a result of further studies, the present inventors found that isobutylene-maleic anhydride copolymer or diisobutylene-maleic anhydride copolymer was added to the back side of the heat-sensitive recording sheet.
It has been found that the above problems can be improved by providing a back coat layer containing an alkali salt of a maleic anhydride copolymer, and the present invention has been completed. Therefore, an object of the present invention is to provide a thermosensitive recording sheet with high dynamic coloring density that can record clear images with high density even with minute thermal energy, and which has good head matching properties such as staking and head dregs, and has a thermosensitive coloring layer. The object of the present invention is to provide a highly sensitive heat-sensitive recording sheet which has excellent solvent resistance and further exhibits less curling even in a low-humidity environment. The undercoat layer of the heat-sensitive recording sheet of the present invention,
Since the heat-sensitive coloring layer and the protective layer are laminated as layers having the following functions, the above object can be achieved. The first is the undercoat layer, and conventional heat-sensitive recording sheets have a layer of 3 to 10 g/ m2 on high-quality paper of 30 to 60 g/m2.
g/m A heat-sensitive coloring layer is provided, but the surface of the paper has irregularities of about 1 to 10μ, and the water-based coating liquid easily penetrates into the paper, so the surface of the heat-sensitive coloring layer and the thermal Since the contact with the thermal head is not uniform and there is little heat conduction in the depth direction of the paper, the thermal energy supplied from the thermal head cannot effectively contribute to the coloring reaction. However, according to the present invention, by forming the undercoat layer as a layer that flattens the unevenness of the paper surface and moderately suppresses the penetration of the heat-sensitive coloring layer applied from above into the paper, the undercoat layer is formed as a layer that suppresses the penetration of the heat-sensitive coloring layer applied from above into the paper. The coloring layer can effectively utilize the thermal energy generated by the coloring layer. In other words, the undercoat layer of the present invention is
It functions as a layer for improving the sensitivity of the upper heat-sensitive coloring layer. It is particularly preferable that such an undercoat layer has a filler coating amount of 2.0 g/m 2 or more and a binder content of 10 to 50% by weight. In this case, the amount of filler applied is 2.0
If it is less than g/m 2 , it becomes difficult to crush the unevenness of the paper surface, and the effect becomes low. Also, if the amount of binder is less than 10% by weight, the heat-sensitive coloring layer may penetrate too much,
Furthermore, the binding properties of the filler become weaker. Moreover, if it exceeds 50% by weight, the effect of improving color development sensitivity will be reduced. Furthermore, the term "filler" as used in the present invention refers to inorganic and organic fillers commonly used in paper making, coating, etc., such as calcium carbonate, clay, talc, silica, polystyrene fine particles, urea-formalin resin fine particles, etc. . In addition, the binder used for the undercoat layer includes ordinary polyvinyl alcohol, cellulose ether, starch,
Water-soluble polymers such as ammonium polycarboxylate, alkali salts of isobutylene-maleic anhydride copolymers, and aqueous emulsions such as styrene-butadiene latex, styrene-acrylic acid esters, and vinyl acetate are used, but preferably dried. It is desirable to select a binder system that has good post-water resistance. Second, the thermosensitive coloring layer functions as a layer that develops color when heated, and is laminated as a layer with extremely improved dynamic coloring sensitivity compared to a conventional single-layer thermosensitive coloring layer. The thermosensitive coloring layer consists of a leuco dye, an acidic substance, a filler, and a binder, and if necessary, a thermofusible substance is also added. In particular, the objective can be achieved by having the filler in an amount by weight not more than 3 times that of the color-forming leuco dye and by using the binder in an amount of 3 to 10% by weight of the thermosensitive color-forming layer. Fillers do not need to be added to the heat-sensitive coloring layer, but
Up to three times the amount, it is possible to bring out the depth of the color tone without reducing the color sensitivity. Furthermore, if the amount of the binder is less than 3% by weight of the heat-sensitive coloring layer, the binding force is too low, causing a problem, and if the amount exceeds 10% by weight, the dynamic coloring sensitivity will decrease. (Usually, in a single-layer heat-sensitive recording sheet, it is used in an amount of about 15 to 30% by weight.) Also, the acidic substance, which is a color developing component, is used in an amount of 2 to 6 times the amount of leuco dye, as is normally used. used. The colorless or slightly monochromatic color-forming leuco bodies used in the present invention include triphenylmethane-based, fluoran-based, phenothiazine-based, auramine-based,
Spiropyran-based leuco derivatives are preferred, and specific examples thereof are shown below. (a) Leuco compound of triphenylmethane dye represented by the following general formula: (In the formula, Rx, Ry and Rz are hydrogen, hydroxyl group, halogen, alkyl group, nitro group, amino group, dialkylamino group, monoalkyl group, and allyl group.) Specific examples of the above leuco compounds are as follows. be. 3,3-bis(p-dimethylaminophenyl)-phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (also known as crystal violet lactone),
3,3-bis(p-dimethylaminophenyl)
-6-diethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)-6-chlorophthalide, 3,3-bis(p-dibutylaminophenyl)phthalide (b) Fluorane series represented by the following general formula Leuco compounds in dyes: In the formula, Rx, Ry and Rz are the same as in (a) above. Specific examples of the above compounds are as follows. 3-cyclohexylamino-6-chlorofluorane, 3-(N,N-diethylamino)-5-
Methyl-7-(N,N-dibenzylamino)fluoran, 3-dimethylamino-5,7-dimethylfluoran, 3-diethylamino-7-methylfluoran, 3-diethylamino-7,8
-Benzfluorane (c) Leuco compound of fluoran dye: 3-diethylamino-6-methyl-7-chlorofluoran, 3-pyrrolidino-6-methyl-
7-anilinofluorane, 2-{N-(3-trifluoromethylphenyl)amino}-6-diethylaminofluorane, 2-{3,6-bis(diethylamino)-9-(0-chloroanilino)
xantylbenzoic acid lactam} (d) Lactone compound represented by the following general formula: In the formula, R 1 and R 2 are hydrogen, lower alkyl group,
represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted phenyl group, a cyanoethyl group, or a β-halogenated ethyl group, or
R 1 and R 2 combine to represent (−CH 2 −) 4 , (−CH 2 −) 5 or (−CH 2 −) 2 O(−CH 2 −) 3 , and R 3 and R 4 are Represents hydrogen, lower alkyl group, alkyl group, amino group or phenyl group,
Either one of R 3 and R 4 is hydrogen, and X 1 , X 2
and X 3 represents hydrogen, a lower alkyl group, a lower alkoxyl group, a halogen atom, a halogenated methyl group, a nitro group, an amino group, or a substituted amino group, and X 4 represents hydrogen, a halogen, a lower alkyl group, or a lower alkoxyl group. represents a group, and n represents 0 or an integer of 1 to 4. Specific examples of the above compounds are as follows. 3-(2'-hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy-5'-chlorophenyl)phthalide, 3-(2'-hydroxy-
4'-dimethylaminophenyl)-3-(2'-methoxy-5'-nitrophenyl)phthalide, 3-
(2'-hydroxy-4'-diethylaminophenyl)-3-(2'-methoxy-5'-methylphenyl)phthalide, 3-(2'-methoxy-4'-dimethylaminophenyl)-3-(2 '-Hydroxy-
4'-chloro-5'-methylphenyl) phthalide In addition, examples of acidic substances that can react with the leuco compound under heat to develop color include phenolic acidic substances, organic acids, and polyvalent metal salts of organic carboxylic acids. ,
Specifically, the following are exemplified. α-naphthol, β-naphthol, 4-t-butylphenol, 4-phenylphenol, 2,
2'-bis(p-hydroxyphenyl)propane,
2,2'-bis(p-hydroxyphenyl)butane, 4,4'-cyclohexylidenephenol,
4,4'-isopropylidene bis(2-t-butylphenol), benzoic acid, salicylic acid, 3,5-
Zinc di-t-butylsalicylate, 3,5-di-t
-tin butylsalicylate, propyl hydroxybenzoate, benzyl hydroxybenzoate, etc. In addition, the thermofusible substance does not have to be an essential component, but it may be used if the coloring component has high melting properties.
It can be added for the purpose of lowering the temperature to 70 to 120°C. For example, when 3-diethylamino-0-chloroanilinofluorane is used as a leuco dye and benzyl p-oxybenzoate (mp 109°C) is used as the acidic substance, the melting characteristics measured by DSC are 84-95°C. In this system, it is not necessary to add a thermofusible substance. However, when bisphenol A (mp156℃) is used as the acidic substance, the melting characteristics are
Appears at 130-155℃ on DSC. In such a case, for example, it is necessary to add stearamide as a thermofusible substance to lower the melting properties to 70-80°C. Without such a structure, the dynamic coloring sensitivity of the thermosensitive coloring layer will not be sufficient. Examples of such thermofusible substances include higher fatty acid amides, derivatives thereof, higher fatty acid metal salts, animal and vegetable waxes, and petroleum waxes such as polyethylene, paraffin, and microcrystalline. As described above, the undercoat layer and thermosensitive coloring layer of the present invention are laminated as layers mainly taking into consideration the improvement of dynamic sensitivity, and the head matching property, such as head scum, often poses a practical problem to some extent. Therefore, the protective layer of the present invention functions as a protective layer that covers these head matching properties and as a protective layer that improves the solvent resistance of the heat-sensitive coloring layer. This protective layer is mainly composed of a water-soluble polymeric binder and a filler. Especially water-soluble polymer binder is 50-90% by weight
Favorable results can be obtained by setting the protective layer coating amount to 1 to 6 g/m 2 . If the water-soluble polymer binder is less than 50% by weight, the binding force of the three layers laminated as a thermosensitive recording sheet may be too weak, the effect of improving solvent resistance may not be sufficient, or the dynamic sensitivity may be reduced. Furthermore, if the amount exceeds 90% by weight, states king in the thermal head is likely to occur. Furthermore, 0 to 20% by weight of a thermofusible substance may be added to further improve dynamic sensitivity and head matching properties. Further, if necessary, 0 to 20% by weight of an aqueous emulsion can be used together with a water-soluble polymeric binder. As mentioned above, by giving the undercoat layer, thermosensitive coloring layer, and protective layer clear functions, the functions of each layer will be expressed, and these will synergize to achieve high dynamic coloring sensitivity and head matching properties. A heat-sensitive recording sheet with excellent solvent resistance can be obtained. However, with these configurations alone, three layers are coated on the surface, and the overcoat layer has a high content of water-soluble polymer, so face curling at the time of coating and face curling at low humidity (dehumidification) curls) are large. Therefore, the back coat layer of the present invention functions as a layer that prevents face curl with a small coating amount. In general, curling of a layer applied to the front surface can be improved by applying the same material applied to the front surface to the back surface, but if the surface has the structure described above, ordinary water-soluble polymers, e.g. With cellulose ethers such as polyvinyl alcohol, methylcellulose, hydroxyethylcellulose, and carboxymethylcellulose, starch and starch derivatives, and aqueous emulsions such as SBR and polyacrylic acid esters, face and curl cannot be improved unless the application amount is extremely large, resulting in poor productivity. .
However, the isobutylene-maleic anhydride copolymer or diisobutylene-maleic anhydride copolymer used in the present invention
Since the alkali salt of maleic anhydride copolymer is a harder resin than other water-soluble polymers, it can improve curl with a small amount of application. These water-soluble polymers vary depending on the coating amount of the three layers on the surface, but the purpose can be achieved by coating 0.5 to 3 g/m 2 . Alcohol or carboxyl-modified polyvinyl alcohol may be added, or an inorganic filler such as calcium carbonate, talc, silica, etc., or an organic filler such as polystyrene may be added to prevent blocking. Generally known methods can be used to produce the heat-sensitive recording sheet of the present invention. For the first undercoat layer, a filler, a binder solution, or an emulsion is mixed and optionally dispersed to prepare an undercoat coating solution. In addition, the heat-sensitive coloring layer coating solution is prepared by separating at least the leuco dye and the acidic substance, and then adding polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, an alkali salt of styrene-maleic anhydride copolymer,
Add an aqueous solution of a water-soluble polymer such as starch, grind and disperse using a dispersing machine such as a ball mill, attritor, or sand mill until the dispersed particle size is 1 to 3μ, then add fillers and heat-fusible polymers as necessary. A heat-sensitive coloring layer coating solution is prepared by blending a substance dispersion, an antifoaming agent, etc. into a certain recipe. Furthermore, the protective layer coating solution is
It is prepared by mixing or dispersing a filler, a thermofusible substance, and a water-soluble polymer binder. The back coat layer is
It is prepared by adding a water-soluble polymer binder and, if necessary, a filler, and mixing or dispersing it. Next, the heat-sensitive recording sheet of the present invention is prepared by sequentially coating and laminating these coating liquids on a support such as paper or synthetic paper. To specifically demonstrate the dynamic color development sensitivity of the thermal recording sheet of the present invention, a thermal head for facsimile having a heating resistor of about 300 Ω was used for a main scanning recording time of 20 Ω.
ms/line, scanning line density 8 dots x 3.85 dots/
mm, platen pressure of 1.4 kg, head voltage of 13 V, and when printing with a current application time of 1.88 msec, the color density of the conventional single-coat thermal recording sheet is 1.2.
Although nothing produced more color (the densitometer was a Macbeth densitometer RD-514 and a filter Wratten-106)
1.1 or less), the heat-sensitive recording sheet of the present invention can obtain a color density of 102 or more. Furthermore, there is no staking, and the head scum is actually better than that of conventional heat-sensitive recording sheets, with almost no scum being observable. The present invention will be explained in detail below using Examples and Comparative Examples. Examples 1, 2, 3 A mixture consisting of the following formulations was stirred with an agitator to prepare an undercoat layer coating solution. 40% dispersion of polystyrene resin 52.5 parts by weight 20% starch aqueous solution 17.5 parts by weight Styrene-butadiene latex (48%)
7.3 parts by weight Water 22.7 parts by weight Liquids [A] and [B] were prepared by pulverizing and dispersing the following mixtures using a ball mill and an attritor until the volume average particle diameter was approximately 1.5 μm. [A] Liquid composition 3-(N-cyclohexyl-N-methyl)amino-6-methyl-7-anilinofluorane 20 parts by weight 10% polyvinyl alcohol aqueous solution 16 parts by weight Water 64 parts by weight [B] Liquid composition p- Benzyl oxybenzoate 10 parts by weight Calcium carbonate 10 parts by weight 10% polyvinyl alcohol aqueous solution 16 parts by weight Water 54 parts by weight Next, liquid [A]: liquid [B] was mixed and stirred at a weight ratio of 1:4 to apply a thermosensitive coloring layer. It was made into a liquid. Further, a mixture having the following formulation was dispersed in a sand mill to obtain a protective layer coating solution and a back coat layer coating solution. [Protective layer coating solution] Calcium carbonate 2.5 parts by weight 10% polyvinyl alcohol aqueous solution 65 parts by weight Zinc stearate 1.0 parts by weight Water 31.5 parts by weight [Back coat layer coating solution] Calcium carbonate 2 parts by weight 20% isobutylene-maleic anhydride copolymer ammonium salt aqueous solution (Kuraray Co., Ltd., Isoban-304)
40 parts by weight Water 58 parts by weight Next, apply these coating solutions to 50 g/m 2 commercially available high-quality paper for the undercoat layer, the heat-sensitive coloring layer using an air knife, the protective layer using a 4-reverse coater, and the back coat layer using an air knife coater. The coatings were coated and dried so that the coating amounts shown in Table 1 were obtained, thereby producing heat-sensitive recording sheets of the present invention (Example 1 and Example 2). Further, a heat-sensitive recording sheet of Example 3 was prepared in the same manner except that the ammonium salt of the isobutylene-maleic anhydride copolymer in the back coat layer was replaced with the ammonium salt of the diisobutylene-maleic anhydride copolymer. Comparative Examples The ammonium salt aqueous solution of 20% isobutylene-maleic anhydride copolymer of Examples 1 and 2 was mixed with 20% polyvinyl alcohol aqueous solution (Comparative Example 1) 20% starch aqueous solution (Comparative Example 2) 20% SBR latex ( Comparative Example 3) Comparative Example 1,
A few heat-sensitive recording sheets were created.
【表】【table】
【表】
実施例 ４
次の配合から成る混合物をサンドミルにて分散
して、バツクコート層塗布液を調製した。
炭酸カルシウム ２重量部
20％イソブチレン−無水マレイン酸共重合体のア
ンモニウム塩水溶液 20重量部
20％ポリビニルアルコール水溶液 20重量部
水 58重量部
次に、実施例２と同様にして（但し、バツクコ
ート層塗布量は2.0ｇ／m2）、本発明の感熱記録シ
ートを作成した。
次に、上記実施例、比較例の感熱記録シートを
スーパーキヤレンダーにて、光沢度（JIS−
P8142に準拠して測定）が10〜13％になるように
キヤレンダーがけした後、Ｇ−フアツクステス
ト機にて動的発色感度とヘツドマツチングのテス
トを行なつた。又、これらの感熱記録シートの環
境条件をかえた時にカールについてもテストを行
なつた。
テスト機は、松下電子部品(株)の８ドツト／mmの
サーマルヘツドを有し、発熱抵抗体は約300Ω／
ドツトであり、これを主走査記録速度20ｍｓ／
line、副走査3.85l／mm、プラテン押圧1.4Kg、ヘ
ツド電圧13Vの条件で通電時間1.88ｍsecと2.19ｍ
secの２条件でテストを行なつた。又、ステイツ
キングは2.19ｍsec前ベタでテストし、ヘツドカ
スは2.19ｍsecで市松模様を（白黒比50％）、10ｍ
印字して、ヘツドを観察した。
又、環境条件をかえたカールテストは、20℃、
65％RHの常温常湿下、20℃、10％RHの常温常
湿下で、A4サイズにサンプルをカツトして行な
つた。
これらのテスト結果を表２にまとめた。表２か
らわかるように、本発明の感熱記録シートは多層
構成であるにもかかわらず、常温低湿下でもカー
ルが少ないことがわかつた。[Table] Example 4 A back coat layer coating solution was prepared by dispersing a mixture consisting of the following formulation using a sand mill. Calcium carbonate 2 parts by weight 20% ammonium salt aqueous solution of isobutylene-maleic anhydride copolymer 20 parts by weight 20% polyvinyl alcohol aqueous solution 20 parts by weight Water 58 parts by weight Next, in the same manner as in Example 2 (however, a back coat layer was applied. The heat-sensitive recording sheet of the present invention was prepared. Next, the heat-sensitive recording sheets of the above Examples and Comparative Examples were subjected to glossiness (JIS-
After calendering was carried out so that the color difference (measured in accordance with P8142) was 10 to 13%, dynamic color development sensitivity and head matching tests were conducted using a G-Fax test machine. Further, curling was also tested when the environmental conditions of these heat-sensitive recording sheets were changed. The test machine has an 8 dot/mm thermal head manufactured by Matsushita Electronic Components Co., Ltd., and a heating resistor of approximately 300 Ω/mm.
dots at a main scanning recording speed of 20ms/
line, sub-scan 3.85l/mm, platen pressure 1.4Kg, head voltage 13V, energizing time 1.88msec and 2.19m
The test was conducted under two conditions: sec. Also, States King was tested with a solid pattern before 2.19 msec, and Hetsudokasu was tested with a checkered pattern (50% of black and white ratio) at 2.19 msec, 10 m.
I printed it and observed the head. In addition, the curl test with different environmental conditions was performed at 20℃,
Samples were cut to A4 size at room temperature and humidity of 65% RH, and at room temperature and humidity of 20°C and 10% RH. These test results are summarized in Table 2. As can be seen from Table 2, although the heat-sensitive recording sheet of the present invention has a multilayer structure, it was found that there was little curling even at room temperature and low humidity.
Claims (1)
アンダーコート層、無色又はやや淡色の発色性ロ
イコ染料と該ロイコ染料を熱時発色させうる酸性
物質を主成分とする感熱発色層及び水溶性高分子
結合剤と充填剤を主成分とする保護層を順次積層
して成る感熱記録シートの裏面にイソブチレン−
無水マレイン酸共重合体又はジイソブチレン−無
水マレイン酸共重合体のアルカリ塩を含有するバ
ツクコート層を設けた事を特徴とする感熱記録シ
ート。1. An undercoat layer containing a filler and a binder as main components on a support, a heat-sensitive coloring layer containing as a main component a colorless or slightly light-colored leuco dye and an acidic substance capable of coloring the leuco dye when heated; Isobutylene-
1. A heat-sensitive recording sheet comprising a back coat layer containing an alkali salt of a maleic anhydride copolymer or a diisobutylene-maleic anhydride copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57118482A JPS599091A (en) | 1982-07-09 | 1982-07-09 | Heat-sensitive recording sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57118482A JPS599091A (en) | 1982-07-09 | 1982-07-09 | Heat-sensitive recording sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS599091A JPS599091A (en) | 1984-01-18 |
| JPH0156920B2 true JPH0156920B2 (en) | 1989-12-01 |
Family
ID=14737762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57118482A Granted JPS599091A (en) | 1982-07-09 | 1982-07-09 | Heat-sensitive recording sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS599091A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH047988Y2 (en) * | 1984-12-20 | 1992-02-28 | ||
| JPS61125879A (en) * | 1984-11-22 | 1986-06-13 | Hokuetsu Seishi Kk | Thermal recording paper free of discoloration of recording layer surface during preservation and production thereof |
| EP0386262B1 (en) * | 1988-08-31 | 1995-08-09 | Dai Nippon Insatsu Kabushiki Kaisha | Image reception sheet |
| JP2006168319A (en) * | 2004-12-20 | 2006-06-29 | Ricoh Co Ltd | Back layer, thermal recording material and functional form |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54111359A (en) * | 1978-02-20 | 1979-08-31 | Ricoh Co Ltd | Thermographic sheet |
| JPS54128349A (en) * | 1978-03-28 | 1979-10-04 | Kanzaki Paper Mfg Co Ltd | Heattsensitive record |
| JPS5627394A (en) * | 1979-08-13 | 1981-03-17 | Ricoh Co Ltd | Thermorecording material |
| JPS56126193A (en) * | 1980-03-11 | 1981-10-02 | Ricoh Co Ltd | Heat-sensitive recording material |
| JPS56146794A (en) * | 1980-04-17 | 1981-11-14 | Ricoh Co Ltd | Heat sensitive recording material |
| JPS5729491A (en) * | 1980-07-31 | 1982-02-17 | Tomoegawa Paper Co Ltd | Preservation improved thermosensitive recording substance |
-
1982
- 1982-07-09 JP JP57118482A patent/JPS599091A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54111359A (en) * | 1978-02-20 | 1979-08-31 | Ricoh Co Ltd | Thermographic sheet |
| JPS54128349A (en) * | 1978-03-28 | 1979-10-04 | Kanzaki Paper Mfg Co Ltd | Heattsensitive record |
| JPS5627394A (en) * | 1979-08-13 | 1981-03-17 | Ricoh Co Ltd | Thermorecording material |
| JPS56126193A (en) * | 1980-03-11 | 1981-10-02 | Ricoh Co Ltd | Heat-sensitive recording material |
| JPS56146794A (en) * | 1980-04-17 | 1981-11-14 | Ricoh Co Ltd | Heat sensitive recording material |
| JPS5729491A (en) * | 1980-07-31 | 1982-02-17 | Tomoegawa Paper Co Ltd | Preservation improved thermosensitive recording substance |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS599091A (en) | 1984-01-18 |
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