JPH03227689A - Thermal recording material - Google Patents
Thermal recording materialInfo
- Publication number
- JPH03227689A JPH03227689A JP2022143A JP2214390A JPH03227689A JP H03227689 A JPH03227689 A JP H03227689A JP 2022143 A JP2022143 A JP 2022143A JP 2214390 A JP2214390 A JP 2214390A JP H03227689 A JPH03227689 A JP H03227689A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- liquid
- binder
- color
- recording layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- VWGNFIQXBYRDCH-UHFFFAOYSA-N 1,4-diethoxybenzene Chemical compound CCOC1=CC=C(OCC)C=C1 VWGNFIQXBYRDCH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 4
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 35
- 238000004040 coloring Methods 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 13
- 230000035945 sensitivity Effects 0.000 abstract description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 4
- -1 triallyl methane compound Chemical class 0.000 abstract description 4
- 239000000725 suspension Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 2
- 239000007788 liquid Substances 0.000 description 51
- 239000003973 paint Substances 0.000 description 27
- 239000006185 dispersion Substances 0.000 description 26
- 239000000243 solution Substances 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 9
- 239000000975 dye Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 7
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 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 5
- 238000001035 drying Methods 0.000 description 5
- AGPLQTQFIZBOLI-UHFFFAOYSA-N 1-benzyl-4-phenylbenzene Chemical group C=1C=C(C=2C=CC=CC=2)C=CC=1CC1=CC=CC=C1 AGPLQTQFIZBOLI-UHFFFAOYSA-N 0.000 description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 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
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-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
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical class O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000002220 fluorenes Chemical class 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- GKFFBAQBFJBIDR-UHFFFAOYSA-N methyl 2,2-bis(4-hydroxyphenyl)acetate Chemical compound C=1C=C(O)C=CC=1C(C(=O)OC)C1=CC=C(O)C=C1 GKFFBAQBFJBIDR-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 150000004893 oxazines Chemical class 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229940037312 stearamide Drugs 0.000 description 2
- 150000004897 thiazines Chemical class 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical class C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- QWQJPPOEEGYTIW-UHFFFAOYSA-N 1-fluoro-1-phenylhydrazine Chemical compound NN(F)C1=CC=CC=C1 QWQJPPOEEGYTIW-UHFFFAOYSA-N 0.000 description 1
- SJJCQDRGABAVBB-UHFFFAOYSA-N 1-hydroxy-2-naphthoic acid Chemical compound C1=CC=CC2=C(O)C(C(=O)O)=CC=C21 SJJCQDRGABAVBB-UHFFFAOYSA-N 0.000 description 1
- DXYZIGZCEVJFIX-UHFFFAOYSA-N 2'-(dibenzylamino)-6'-(diethylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C(N(CC)CC)=CC=C(C2(C3=CC=CC=C3C(=O)O2)C2=C3)C=1OC2=CC=C3N(CC=1C=CC=CC=1)CC1=CC=CC=C1 DXYZIGZCEVJFIX-UHFFFAOYSA-N 0.000 description 1
- QKJAZPHKNWSXDF-UHFFFAOYSA-N 2-bromoquinoline Chemical compound C1=CC=CC2=NC(Br)=CC=C21 QKJAZPHKNWSXDF-UHFFFAOYSA-N 0.000 description 1
- XBQRPFBBTWXIFI-UHFFFAOYSA-N 2-chloro-4-[2-(3-chloro-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(Cl)=CC=1C(C)(C)C1=CC=C(O)C(Cl)=C1 XBQRPFBBTWXIFI-UHFFFAOYSA-N 0.000 description 1
- XGAYQDWZIPRBPF-UHFFFAOYSA-N 2-hydroxy-3-propan-2-ylbenzoic acid Chemical compound CC(C)C1=CC=CC(C(O)=O)=C1O XGAYQDWZIPRBPF-UHFFFAOYSA-N 0.000 description 1
- WLTCCDHHWYAMCG-UHFFFAOYSA-N 2-phenylmethoxynaphthalene Chemical compound C=1C=C2C=CC=CC2=CC=1OCC1=CC=CC=C1 WLTCCDHHWYAMCG-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
- JSUKRBMPOXGCPR-UHFFFAOYSA-N 4-(benzenesulfonyl)phenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=CC=C1 JSUKRBMPOXGCPR-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- MWRVRCAFWBBXTL-UHFFFAOYSA-N 4-hydroxyphthalic acid Chemical compound OC(=O)C1=CC=C(O)C=C1C(O)=O MWRVRCAFWBBXTL-UHFFFAOYSA-N 0.000 description 1
- XURABDHWIADCPO-UHFFFAOYSA-N 4-prop-2-enylhepta-1,6-diene Chemical class C=CCC(CC=C)CC=C XURABDHWIADCPO-UHFFFAOYSA-N 0.000 description 1
- BXAVKNRWVKUTLY-UHFFFAOYSA-N 4-sulfanylphenol Chemical class OC1=CC=C(S)C=C1 BXAVKNRWVKUTLY-UHFFFAOYSA-N 0.000 description 1
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 1
- KJKQQOHAWQQUDD-UHFFFAOYSA-N 6-hydroxynaphthalene-2-carboxylic acid;zinc Chemical compound [Zn].C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KJKQQOHAWQQUDD-UHFFFAOYSA-N 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
- 229930185605 Bisphenol Natural products 0.000 description 1
- QFOHBWFCKVYLES-UHFFFAOYSA-N Butylparaben Chemical compound CCCCOC(=O)C1=CC=C(O)C=C1 QFOHBWFCKVYLES-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 description 1
- 239000005844 Thymol Substances 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- OUXHZAJDCBMTNQ-UHFFFAOYSA-N bis(4-hydroxy-3-methylphenyl) sulfite Chemical compound C1=C(O)C(C)=CC(OS(=O)OC=2C=C(C)C(O)=CC=2)=C1 OUXHZAJDCBMTNQ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- RFAHZZDUNWEBLG-UHFFFAOYSA-N butyl 2,2-bis(4-hydroxyphenyl)acetate Chemical compound C=1C=C(O)C=CC=1C(C(=O)OCCCC)C1=CC=C(O)C=C1 RFAHZZDUNWEBLG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical class C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 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
- MFGZXPGKKJMZIY-UHFFFAOYSA-N ethyl 5-amino-1-(4-sulfamoylphenyl)pyrazole-4-carboxylate Chemical compound NC1=C(C(=O)OCC)C=NN1C1=CC=C(S(N)(=O)=O)C=C1 MFGZXPGKKJMZIY-UHFFFAOYSA-N 0.000 description 1
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000004403 ethyl p-hydroxybenzoate Substances 0.000 description 1
- 229940043351 ethyl-p-hydroxybenzoate Drugs 0.000 description 1
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- MDQRDWAGHRLBPA-UHFFFAOYSA-N fluoroamine Chemical compound FN MDQRDWAGHRLBPA-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000005165 hydroxybenzoic acids Chemical class 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 235000010232 propyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000004405 propyl p-hydroxybenzoate Substances 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
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- 230000002087 whitening effect Effects 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
- YWUGXWVYRWGTFR-UHFFFAOYSA-L zinc;2-butoxybenzoate Chemical compound [Zn+2].CCCCOC1=CC=CC=C1C([O-])=O.CCCCOC1=CC=CC=C1C([O-])=O YWUGXWVYRWGTFR-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は感熱記録材料に関するものであり、さらに詳細
には、高感度で、耐光性、耐湿性に優れ感熱特性を改良
した感熱記録材料に関するものであり、特に発色感度及
び耐熱性を改良した感熱記録紙に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a heat-sensitive recording material, and more particularly to a heat-sensitive recording material that is highly sensitive, has excellent light resistance and moisture resistance, and has improved heat-sensitive characteristics. In particular, it relates to a heat-sensitive recording paper with improved color development sensitivity and heat resistance.
（従来の技術）
感熱記録紙の記録層として具備すべき性能は耐自己発色
性、耐圧力発色性、耐光性、耐熱消色性、消色性、およ
び耐水性などの感熱特性に優れていることであるが、現
在これらを完全に満足するものは得られていない。一方
、社会の要請による記録の高速伝送化に伴い、記録装置
自体の高速化は勿論であるがこれに対応し得る高感度、
即ち低エネルギーで濃度高く発色する感熱記録材料が要
求されている。(Prior art) The recording layer of thermosensitive recording paper should have excellent heat-sensitive properties such as self-coloring resistance, pressure coloring resistance, light fastness, heat decoloring resistance, color erasing property, and water resistance. However, there is currently no product that completely satisfies these requirements. On the other hand, as society demands higher speed transmission of recording, not only the speed of the recording device itself has to be increased, but also high sensitivity and
That is, there is a need for a heat-sensitive recording material that can develop colors with high density and low energy.
従来、発色感度を向上させるため、特開昭５７−１１６
６９０、特開昭５７−６４５９２、特開昭５８−１１２
７８８、特公昭５９−３０５５７、特開昭６０−５６５
８８、特開昭６０−８２３８２、特開昭６１−２７２１
８９、特開昭６３−１２６７８４、および特開昭６４−
４０３７３などの化合物を感熱記録層中に加える提案が
ある。Conventionally, in order to improve color development sensitivity, Japanese Patent Application Laid-Open No. 57-116
690, JP-A-57-64592, JP-A-58-112
788, JP 59-30557, JP 60-565
88, JP 60-82382, JP 61-2721
89, JP-A No. 63-126784, and JP-A No. 64-
There are proposals to add compounds such as 40373 into the thermosensitive recording layer.
（発明が解決しようとする問題点）
本発明者らは、既知の電子供与性無色染料を発色剤とし
て用いて、従来公知の方法および上記した各特許公報に
記載されている方法に従い、感熱記録紙を製造し、感熱
記録紙として具備すべき性能について試験したところ、
発色感度が優れ、かつ、画像の安定性に優れた化合物は
地肌カブリおよび画像保存性試験後の地肌カブリが大き
く、感熱記録材料の高感度化の目的には不十分なもので
あった。(Problems to be Solved by the Invention) The present inventors used a known electron-donating colorless dye as a coloring agent to produce a thermosensitive recording medium according to a conventionally known method and the method described in each of the above-mentioned patent publications. When paper was manufactured and tested for the performance it should have as a thermal recording paper,
Compounds with excellent color development sensitivity and excellent image stability had large background fog and background fog after image storage stability tests, and were unsatisfactory for the purpose of increasing the sensitivity of heat-sensitive recording materials.
Ｃ問題点を解決するための手段）
本発明者らは、既知の電子供与性無色染料を用いた感熱
記録材料について、上記の欠点を改良すべく鋭意研究し
た結果、本発明を完成したものであり、画像保存性試験
後の地肌を汚すことなく発色感度、及び耐熱性を改良し
た感熱記録紙を提供するものである。Means for Solving Problem C) The present inventors have completed the present invention as a result of intensive research to improve the above-mentioned drawbacks of heat-sensitive recording materials using known electron-donating colorless dyes. The present invention provides a heat-sensitive recording paper that has improved color development sensitivity and heat resistance without staining the background after an image preservation test.
すなわち本発明は、
無色またはやや淡色を帯びた電子供与性無色染料と該電
子供与性無色染料を熱時発色させる酸性物質と結着剤と
を基本的に有する記録層を支持体上に設けてなる感熱記
録紙において、前記記録層中に１，４−ジエトキシベン
ゼンを含有することを特徴とする感熱記録材料である。That is, the present invention provides a recording layer on a support that basically includes a colorless or slightly pale colorless electron-donating dye, an acidic substance that causes the colorless electron-donating dye to develop color when heated, and a binder. The heat-sensitive recording paper is characterized in that the recording layer contains 1,4-diethoxybenzene.
本発明に使用する電子供与性無色染料としては、トリア
リルメタン系化合物、ジフェニルメタン系化合物、キサ
ンチン系化合物、チアジン系化合物、オキサジン系化合
物、スピロピラン系化合物、フルオレン系化合物などが
知られている。Known electron-donating colorless dyes used in the present invention include triallylmethane compounds, diphenylmethane compounds, xanthine compounds, thiazine compounds, oxazine compounds, spiropyran compounds, and fluorene compounds.
これらの一部を例示すれば、トリアリルメタン系化合物
として、３．３−ビス（Ｐ−ジメチルアミノフェニル）
−６−シメチルアミノフタリド（ＣＶＬＩ、３．３−ビ
ス（Ｐ−ジメチルアミノフェニルフタリド）、３−（Ｐ
−ジメチルアミノフェニル）−３（ｌ、３−ジメチルイ
ンドール−３−イル）フタリド、３−（Ｐ−ジメチルア
ミノフェニル）−３−（２−メチルインドール−３−イ
ル）フタリド、３．３−ビス（（２−（４−メトキシフ
ェニル）２−（４−ジメチルアミノフェニル）エチニル
））−４，５，６，７テトラクロロフタリド、３，３−
ビス（（１，１−ビス（４−ビロリジロノフェニル）エ
チレン−２−イル） ）−４，５，６，７テトラクロロ
フタリド等があり、キサンチン化合物としては、ローダ
ミンＢ−アニリノラクタム、ローダミンＢ（Ｐ−ニトロ
アニリノ）ラクタム、ローダミンＢ（Ｐ−クロロアニリ
ノ）ラクタム、２−ジベンジルアミノ−６−ジエチルア
ミノフルオラン、２−アニリノー６−ジエチルアミノフ
ルオラン、２−アニリツー３−メチル−６−ジエチルア
ミノフルオラン、２−アニリノ−３−メチル−６−（Ｎ
−シクロへキシル−Ｎ−メチル）アミノフルオラン、２
−０−クロロアニリノ−６−ジエチルアミノフルオラン
、２−０−クロロアニリノ−６−ジブチルアミノフルオ
ラン、２−ｐ−クロロアニリノ−６−ジエチルアミノフ
ルオラン、２−オクチルアミノ−６−ジエチルアミノフ
ルオラン、２−Ｐ−アセチルアニリノ−６−ジエチルア
ミノフルオラン、２−エトキシエチルアミノ−３−クロ
ロ−６−ジエチルアミノフルオラン、２−アニリノ−３
クロロ−６−ジエチルアミノフルオラン、２−ジフェニ
ルアミノ−６−ジエチルアミノフルオラン、２−アニリ
ノ−６−（Ｎ−エチル−Ｎ−トリル）アミノフルオラン
、２−アニリノ−３−メチル−６−（Ｎ−エチル−Ｎ−
）リル）アミノフルオラン、２−アニリノ−３−メチル
−６−（Ｎ−メチル−Ｎ−ｎ−プロピル）アミノフルオ
ラン、２−アニリノ−３−メトキン−６−ジブチルアミ
ノフルオラン、２−アニリノ−３−メチル−６−Ｎ、Ｎ
−ジブチルアミノフルオラン、２−アニリノ−３−メチ
ル−６−（Ｎ−エチル−Ｎ−テトラヒドロフルフリル）
アミノフルオラン、２−アニリノ−３−メチル−６−（
Ｎ−ｎブチル−Ｎ−テトラヒドロフルフリル）アミノフ
ルオラン、２−アニリノ−３−メチル−６−（Ｎ−エチ
ル−Ｎ−イソアミル）アミノフルオラン、２−クロロ−
３−メチル−６−ｐ−（ｐ−フェニルアミノフェニル）
アミノアニリノフルオラン、２−Ｐ−フェニルウレイド
アニリノ−６−Ｎ−シクロヘキシル−Ｎ−メチルアミノ
フルオラン、等があり、フルオレン系化合物としては、
３”、６゛ビスジエチルアミノ５−ジエチルアミノスピ
ロ（イソベンゾフラン−１，９−フルオレン）−３゛−
オン、３′、６゛ビスジエチルアミノ−５−ジブチルア
ミノスピロ（イソベンゾフラン−１，９−フルオレン）
−３“−オン、等があり、ペンタジェン系化合物として
は、１−（α−メトキシ（４−Ｎ、Ｎ−ジメチルアミノ
）ベンジル） −３−（４−Ｎ、Ｎ−ジメチルアミノベ
ンジリデン）−５−メチル−シクロヘキセン等があり、
チアジン系化合物としては、ペンゾイルリューコメチレ
ンブルー、ｐ−ニトロベンジルリューコメチレンブルー
等があり、オキサジン系化合物としては、３．７−ビス
（ジエチルアミノ） −１０−ペンシイルーフエノキサ
シン、３，７−ビス（ジエチルアミノ）−１０−アセチ
ルフェノキサジン等があり、スピロ系化合物としては、
３−メチルスピロジナフトピラン、３−ベンジルスピロ
−ジナフトピラン、３−プロピルスピロ−ジベンゾピラ
ン等がある。Some examples of these include 3,3-bis(P-dimethylaminophenyl) as a triallylmethane compound.
-6-dimethylaminophthalide (CVLI, 3.3-bis(P-dimethylaminophenyl phthalide), 3-(P
-dimethylaminophenyl)-3(l,3-dimethylindol-3-yl)phthalide, 3-(P-dimethylaminophenyl)-3-(2-methylindol-3-yl)phthalide, 3,3-bis ((2-(4-methoxyphenyl)2-(4-dimethylaminophenyl)ethynyl))-4,5,6,7tetrachlorophthalide, 3,3-
Bis((1,1-bis(4-pyrrolidylonophenyl)ethylene-2-yl))-4,5,6,7 tetrachlorophthalide, etc., and xanthine compounds include rhodamine B-anilino lactam, Rhodamine B (P-nitroanilino)lactam, Rhodamine B (P-chloroanilino)lactam, 2-dibenzylamino-6-diethylaminofluorane, 2-anilino-6-diethylaminofluorane, 2-anili2-3-methyl-6- Diethylaminofluorane, 2-anilino-3-methyl-6-(N
-cyclohexyl-N-methyl)aminofluorane, 2
-0-chloroanilino-6-diethylaminofluorane, 2-0-chloroanilino-6-dibutylaminofluorane, 2-p-chloroanilino-6-diethylaminofluorane, 2-octylamino-6-diethylaminofluorane, 2-P -acetylanilino-6-diethylaminofluorane, 2-ethoxyethylamino-3-chloro-6-diethylaminofluorane, 2-anilino-3
Chloro-6-diethylaminofluorane, 2-diphenylamino-6-diethylaminofluorane, 2-anilino-6-(N-ethyl-N-tolyl)aminofluorane, 2-anilino-3-methyl-6-(N -ethyl-N-
)lyl)aminofluorane, 2-anilino-3-methyl-6-(N-methyl-N-n-propyl)aminofluorane, 2-anilino-3-methquin-6-dibutylaminofluorane, 2-anilino -3-methyl-6-N,N
-dibutylaminofluorane, 2-anilino-3-methyl-6-(N-ethyl-N-tetrahydrofurfuryl)
Aminofluorane, 2-anilino-3-methyl-6-(
N-n-butyl-N-tetrahydrofurfuryl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-N-isoamyl)aminofluorane, 2-chloro-
3-Methyl-6-p-(p-phenylaminophenyl)
Examples of fluorene compounds include aminoanilinofluorane, 2-P-phenylureidoanilino-6-N-cyclohexyl-N-methylaminofluorane, and the like.
3", 6"bisdiethylamino5-diethylaminospiro(isobenzofuran-1,9-fluorene)-3"-
1,3',6'bisdiethylamino-5-dibutylaminospiro(isobenzofuran-1,9-fluorene)
-3"-one, etc., and pentadiene compounds include 1-(α-methoxy(4-N,N-dimethylamino)benzyl)-3-(4-N,N-dimethylaminobenzylidene)-5 -Methyl-cyclohexene, etc.
Examples of thiazine compounds include penzoylleucomethylene blue and p-nitrobenzylleucomethylene blue, and examples of oxazine compounds include 3,7-bis(diethylamino)-10-pensyylfuenoxacin and 3,7-bis(diethylamino). )-10-acetylphenoxazine, etc., and spiro-based compounds include:
Examples include 3-methylspirodinaphthopyran, 3-benzylspiro-dinaphthopyran, and 3-propylspiro-dibenzopyran.
これらは、単独または、混合して用いられる。These may be used alone or in combination.
本発明は、これら電子供与性無色染料に限定されるもの
ではない。The present invention is not limited to these electron-donating colorless dyes.
本発明に用いられる電子受容性化合物（顕色剤）として
は、フェノール系化合物、有機酸あるいはその金属塩、
ヒドロキシ安息香酸エステル等が好ましく、具体的には
次のようなものがあげられる。Examples of the electron-accepting compound (developer) used in the present invention include phenolic compounds, organic acids or metal salts thereof,
Hydroxybenzoic acid esters are preferred, and specific examples include the following.
サルチル酸、３−イソプロピルサリチル酸、３゜５−ジ
ーｔｅｒ、−ブチルサリチル酸、３．５−ジ−αメチル
ベンジルサリチル酸、４，４°−イソプロピリデンジフ
ェノール、４．４’−イソプロピリデンビス（２−クロ
ロフェノール） 、４．４’−イソプロピリデンビス（
２，６−ジクロロフェノール） 、４．４°−イソプロ
ピリデンビス（２，６−シメチルフエノール）、４．４
゛−イソプロピリデンビス（２−ｔｅｒ、−ブチルフェ
ノール） 、４．４°−シクロヘキシリデンビスフェノ
ール、４．４′−シクロヘキシリデンビス（２−メチル
フェノール）、４ｔｅｒ、−ブチルフェノール、４−フ
ェニルフェノール、４−ヒト′ロキシジフェノキシド、
α−ナフトール、β−ナフトール、３．５−キシレノー
ル、チモール、メチル−ビス（４−ヒドロキシフェニル
）アセテート、ｎ−ブチル−ビス（４−ヒドロキシフェ
ニル）アセテート、４，４゛−チオジフェノール、ビス
（４−ヒドロキシ−３−メチルフェニル）スルフイツト
、４゜４”−ジフェノールスルホン、４−イソプロポキ
シ４゛−ヒドロキシジフェニルスルホン、１．７−ジ（
４〜ヒドロキシフエニルチオ） ３＋５−ジオキサ
へブタン、フロログリシンカルボン酸、４−ｔｅｒ、−
オクチルカテコール、２．２′−メチレンビス（４−ク
ロロフェノール） 、２．２’〜メチレンビス（４−メ
チル−５−ｔｅｒ、−ブチルフェノール）、２．２′−
ジヒドロキシジフェニル、ｐ−ヒドロキシ安息香酸エチ
ル、ｐ−ヒドロキシ安息香酸プロピル、ｐ−ヒドロキシ
安息香酸ブチル、ｐ−ヒドロキシ安息香酸ベンジル、ｐ
−ヒドロキシ安息香酸−ｐ−クロロベンジル、ｐ−ヒド
ロキシ安息ｉＭ−〇−クロロベンジル、ｐ−ヒドロキシ
安息香酸ｐ−メチルベンジル、ｐ−ヒドロキシ安息香酸
−ｎ−オクチル、安息香酸、サリチル酸亜鉛、１−ヒド
ロキシ−２−ナフトエ酸、２−ヒドロキシ６−ナフトエ
酸、２−ヒドロキシ−６−ナフトエ酸亜鉛、４−ヒドロ
キシジフェニルスルホン、４−ヒドロキシ−４′ −ク
ロロジフェニルスルホン、２−ヒドロキシ−ｐ−１−ル
イル酸、３＋５ ｔｅｒ。Salicylic acid, 3-isopropylsalicylic acid, 3°5-di-ter,-butylsalicylic acid, 3,5-di-α-methylbenzylsalicylic acid, 4,4°-isopropylidene diphenol, 4,4′-isopropylidene bis(2 -chlorophenol), 4,4'-isopropylidene bis(
2,6-dichlorophenol), 4.4°-isopropylidene bis(2,6-dimethylphenol), 4.4
゛-isopropylidene bis(2-ter,-butylphenol), 4.4°-cyclohexylidene bisphenol, 4.4'-cyclohexylidene bis(2-methylphenol), 4ter,-butylphenol, 4-phenylphenol, 4-human'roxydiphenoxide,
α-naphthol, β-naphthol, 3,5-xylenol, thymol, methyl-bis(4-hydroxyphenyl) acetate, n-butyl-bis(4-hydroxyphenyl) acetate, 4,4゛-thiodiphenol, bis (4-Hydroxy-3-methylphenyl)sulfite, 4゜4''-diphenolsulfone, 4-isopropoxy 4゛-hydroxydiphenylsulfone, 1,7-di(
4-hydroxyphenylthio) 3+5-dioxahebutane, phloroglycine carboxylic acid, 4-ter, -
Octylcatechol, 2.2'-methylenebis(4-chlorophenol), 2.2'-methylenebis(4-methyl-5-ter,-butylphenol), 2.2'-
Dihydroxydiphenyl, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate, benzyl p-hydroxybenzoate, p
-Hydroxybenzoic acid-p-chlorobenzyl, p-hydroxybenzoic acid-p-chlorobenzyl, p-hydroxybenzoic acid p-methylbenzyl, p-hydroxybenzoic acid-n-octyl, benzoic acid, zinc salicylate, 1-hydroxy -2-naphthoic acid, 2-hydroxy-6-naphthoic acid, zinc 2-hydroxy-6-naphthoic acid, 4-hydroxydiphenylsulfone, 4-hydroxy-4'-chlorodiphenylsulfone, 2-hydroxy-p-1-ruyl Acid, 3+5 ter.
ブチルサリチル酸亜鉛、３．５−ｔｅｒ、−ブチルサリ
チル酸錫、酒石酸、しゅう酸、マレイン酸、クエン酸、
コハク酸、ステアリン酸、４−ヒドロキシフタル酸、は
う酸、チオ尿素誘導体、４−ヒドロキシチオフェノール
誘導体等がある。Zinc butylsalicylate, 3.5-ter, -tin butylsalicylate, tartaric acid, oxalic acid, maleic acid, citric acid,
Examples include succinic acid, stearic acid, 4-hydroxyphthalic acid, oxalic acid, thiourea derivatives, and 4-hydroxythiophenol derivatives.
発色剤と顕色剤との混合物を支持体シート上に結着させ
る結着剤としては水溶性または非水溶性の結着剤を用い
る。代表的なものとしてはポリビニルアルコール、メチ
ルセルローズ、ヒドロキシエチルセルローズ、カルボキ
シメチルセルローズ、アラビアゴム、でん粉、ゼラチン
、カゼイン、ポリビニルピロリドン、スチレン−無水マ
レイン酸共重合物、ポリアクリル酸アミド、ポリアクリ
ル酸塩、テルペン樹脂および石油樹脂等があるが、本発
明で特に好適に使用しうる結着剤は水溶性結着剤であり
、その代表的なものはポリビニルアルコールである。A water-soluble or water-insoluble binder is used as the binder for binding the mixture of color former and color developer onto the support sheet. Typical examples include polyvinyl alcohol, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, gum arabic, starch, gelatin, casein, polyvinylpyrrolidone, styrene-maleic anhydride copolymer, polyacrylic acid amide, and polyacrylate. , terpene resins, petroleum resins, etc., but the binder that can be particularly preferably used in the present invention is a water-soluble binder, and a typical example thereof is polyvinyl alcohol.
次に本発明の感熱記録材料を用いた感熱記録紙の具体的
な製造例を示す。Next, a specific example of manufacturing a heat-sensitive recording paper using the heat-sensitive recording material of the present invention will be shown.
感熱記録紙を製造する際に記録層中における上記した各
成分および結着剤のそれぞれの重量比は、発色剤に対し
本発明化合物の１．４−ジエトキシベンゼンの総量は０
．５〜１０倍、好ましくは１〜４倍であり、結着剤は０
．３〜３倍、好ましくは０．５〜２倍である。発色剤お
よび顕色剤は、好ましくはそれぞれ別々にボールミル、
ダイノーミル、サンドミルまたはペイントコンディショ
ナーなどの分散機を用いて分散し、また、本発明にかか
わる１、４−ジエトキシベンゼンは単独、または発色剤
と共に、または顕色剤と共に分散してもよく、結着剤を
含有する水あるいは有機媒体中で、好ましくは結着剤が
溶解している水を媒体として分散し、粉砕して１〜６μ
、好ましくは１〜３μの粒押とした懸濁液をつくる。必
要ならば消泡剤、分散剤または増白剤などを加えて分散
し、粒砕してもよい。When producing heat-sensitive recording paper, the weight ratio of each of the above-mentioned components and binder in the recording layer is such that the total amount of 1,4-diethoxybenzene of the present compound relative to the color former is 0.
．． 5 to 10 times, preferably 1 to 4 times, and the binder is 0
．． It is 3 to 3 times, preferably 0.5 to 2 times. The color forming agent and the color developer are preferably each separately ball milled,
It is dispersed using a dispersing machine such as a dyno mill, a sand mill, or a paint conditioner, and the 1,4-diethoxybenzene used in the present invention may be dispersed alone, together with a color former, or together with a color developer. The binder is dispersed in water or an organic medium containing the binder, preferably water in which the binder is dissolved, and pulverized to a size of 1 to 6 μm.
, preferably a suspension with particles of 1 to 3 μm in size. If necessary, an antifoaming agent, dispersant, or brightener may be added for dispersion and pulverization.
次に上記したそれぞれを別々に分散し、粉砕した各成分
の懸濁液を記録層中における各成分の重量比が上記した
ように混合して熱感記録層を形成させるための塗料とす
る。この塗料を紙の表面にワイヤーバー階６〜Ｎα２０
を用い、乾燥後の固形物の重量が３〜Ｌｏｇ／ｒｒｆに
なるように塗布し、室温〜７０°Ｃの送風乾燥機中で乾
燥することにより感熱記録紙を製造する。必要に応じ熱
ヘツドの対融着性、筆記性などを改善するために無機ま
たは有機充填剤を塗料に加えてもよい。Next, each of the above-mentioned components is separately dispersed, and a suspension of the pulverized components is mixed so that the weight ratio of each component in the recording layer is as described above to prepare a paint for forming a heat-sensitive recording layer. Apply this paint to the surface of the paper with a wire bar level 6~Nα20.
A heat-sensitive recording paper is produced by applying the mixture so that the weight of the solid after drying is 3 to Log/rrf, and drying it in a blow dryer at room temperature to 70°C. If necessary, an inorganic or organic filler may be added to the paint to improve the anti-fusing properties of the thermal head, the writability, etc.
（発明の効果）
このようにして得られた感熱記録紙は、感熱特性のうち
、特に発色感度が極めて優れており、さらには感熱記録
紙としての商品価値を損ねる白化現象もなく、耐熱性お
よび耐熱地肌のカブリも優れた、従来既知の感熱記録紙
の欠点を良（克服するものであった。(Effects of the Invention) The heat-sensitive recording paper thus obtained has excellent heat-sensitive properties, particularly color development sensitivity, and also has no whitening phenomenon that impairs its commercial value as a heat-sensitive recording paper, and has excellent heat resistance and It also has excellent heat-resistant surface fog, which overcomes the drawbacks of conventional heat-sensitive recording paper.
（実施例）
以下に本発明を実施例により具体的に説明するが、本発
明はこれらの実施例によって限定されるものではない。(Examples) The present invention will be specifically explained below using Examples, but the present invention is not limited by these Examples.
実施例Ｉ
Ａ液（染料分散液）
２−アニリノ−３−メチル−６−
シブチルアミノフルオラン ８ 部ステアリン
酸アマイド ４１０％ポリビニルアルコー
ル ４０水
２８Ｂ液（Ｕ色剤分散液）
ＢＰＡ ５部
ステアリン酸亜鉛 ３１．４−ジエト
キシベンゼン ６４．４”−ブチリデンビス−
（３−メチル６−ｔｅｒ、ブチル）フェノール １
．５１０％ポリビニルアルコール ｌＯ水
５４．５Ｃ液（フ
ィラー分散液）
３０％カルシウムカーボネート水溶液
り液（結着剤液）
１０％ポリビニルアルコール水溶液
上記組成物の各液、Ａ、ＢおよびＣをダイノーミルＫＤ
Ｌ分散機で粒ｔ！ｌ！ １．５〜３μまで粉砕する。Example I Solution A (dye dispersion) 2-anilino-3-methyl-6-sibutylaminofluorane 8 parts Stearamide 410% polyvinyl alcohol 40 Water
28B solution (U colorant dispersion) BPA 5 parts Zinc stearate 31.4-Diethoxybenzene 64.4”-Butylidene bis-
(3-methyl 6-ter, butyl)phenol 1
．． 510% polyvinyl alcohol lO water
54.5C liquid (filler dispersion) 30% calcium carbonate aqueous solution Liquid (binder liquid) 10% polyvinyl alcohol aqueous solution
Grain T with L disperser! l! Grind to 1.5-3μ.
次に下記の割合で各液を混合して感熱塗料とする。Next, each liquid is mixed in the following proportions to form a heat-sensitive paint.
この混合塗料を上質紙の表面に阻１８のワイヤーバーを
用い、乾燥後の固形分重量が７ｇ／ｍになるように塗布
し、送風乾燥機中に入れ乾燥した。This mixed paint was applied to the surface of high-quality paper using a wire bar of 18 mm so that the solid content weight after drying was 7 g/m, and the mixture was placed in a blow dryer to dry.
このようにして感熱記録紙を得た。A thermosensitive recording paper was thus obtained.
実施例２
実施例１中のＡ液中の２−アニリノ−３−メチル−６−
シブチルアミノフルオランを２−アニリノ−３−メチル
−６−ジニチルアミノフルオランをに変えた他は、Ａ液
作成と全（同じに行いＥ液分散液を得た。Example 2 2-anilino-3-methyl-6- in solution A in Example 1
A dispersion of Solution E was obtained in the same manner as in the preparation of Solution A, except that 2-anilino-3-methyl-6-dinithylaminofluorane was replaced with 2-anilino-3-methyl-6-dinithylaminofluorane.
次に下記の割合で各液を混合して感熱塗料とする。Next, each liquid is mixed in the following proportions to form a heat-sensitive paint.
Ｅ液 以下上記塗料を用い、 い、感熱記録紙を得た。E liquid Below, using the above paint, A thermosensitive recording paper was obtained.
実施例３
実施例１中のＡ液中の
４部
６
０
実施例１と全く同様に行
２−アニリノ−３−メチ
ルー６−シブチルアミノフルオランを２−アニリノ−３
−メチル−６−Ｎ−エチル−６−Ｎ−テトラヒドロフル
フリルアミノフルオランに変えた他は、Ａ液作成と全く
同じに行いＨ液分散液を得た。Example 3 4 parts in solution A in Example 1 60 In exactly the same manner as in Example 1, 2-anilino-3-methyl-6-sibutylaminofluorane was converted to 2-anilino-3
-Methyl-6-N-ethyl-6-N-tetrahydrofurfurylaminofluorane was used, but the same procedure as in the preparation of Liquid A was carried out to obtain a Liquid H dispersion.
次に下記の割合で各法を混合して感熱塗料とする。Next, each method is mixed in the following proportions to prepare a heat-sensitive paint.
Ｆ液 ４ 部８
１６
Ｃ１０
４
以下上記塗料を用い、実施例１と全く同様に行い、感熱
記録紙を得た。F liquid 4 parts 8
16 C10 4 The following procedure was carried out in exactly the same manner as in Example 1 using the above paint to obtain thermal recording paper.
実施例４
実施例１中のＡ液中の２−アニリノ−３−メチル−６−
シブチルアミノフルオランを２−アニリノ−３−メチル
−６−Ｎ−エチル−６−Ｎ−イソアミルアミノフルオラ
ンをに変えた他は、Ａ液作成と全く同じに行いＧ液分散
液を得た。次に下記の割合で各法を混合して感熱塗料と
する。Example 4 2-anilino-3-methyl-6- in solution A in Example 1
A dispersion of liquid G was obtained in exactly the same manner as in the preparation of liquid A, except that 2-anilino-3-methyl-6-N-ethyl-6-N-isoamylaminofluorane was replaced with sibutylaminofluorane. . Next, each method is mixed in the following proportions to prepare a heat-sensitive paint.
Ｇ液 ４ 部８
１６Ｃ１０
４
以下上記塗料を用い、実施例１と全く同様に行い、感熱
記録紙を得た。G liquid 4 parts 8
16C10 4 Using the above coating material, the same procedure as in Example 1 was carried out to obtain heat-sensitive recording paper.
実施例５
実施例１中のＡ液中の２−アニリノ−３−メチル−６−
シブチルアミノフルオランを２−アニリノ−３−メチル
−６−Ｎ−エチル−６−Ｎ−シクロヘキシルアミノフル
オランに変えた他は、Ａ液作成と全く同じに行いＨ液分
散液を得た。Example 5 2-anilino-3-methyl-6- in solution A in Example 1
A dispersion of liquid H was obtained in exactly the same manner as in the preparation of liquid A, except that 2-anilino-3-methyl-6-N-ethyl-6-N-cyclohexylaminofluorane was used.
次に下記の割合で各法を混合して感熱塗料とする。Next, each method is mixed in the following proportions to prepare a heat-sensitive paint.
Ｈ液 ４ 部８
１６
Ｃ１０
４
以下上記塗料を用い、実施例１と全く同様に行い、感熱
記録紙を得た。H liquid 4 parts 8
16 C10 4 The following procedure was carried out in exactly the same manner as in Example 1 using the above paint to obtain thermal recording paper.
実施例６
実施例１中のＡ液と実施例３中のＦ液を等量混ぜ合わせ
１分散液を得た。Example 6 Equal amounts of Solution A in Example 1 and Solution F in Example 3 were mixed to obtain 1 dispersion.
次に下記の割合で各法を混合して感熱塗料とする。Next, each method is mixed in the following proportions to prepare a heat-sensitive paint.
Ｉ液 ４ 部
８ １６
Ｃ１０
４
以下上記塗料を用い、実施例１と全く同様に行い、感熱
記録紙を得た。Liquid I 4 parts 8 16 C10 4 Using the above coating material, the same procedure as in Example 1 was carried out to obtain a heat-sensitive recording paper.
実施例７
実施例１中のＢ液中の顕色剤ＢＰＡ（ビスフェノール−
Ａ）をメチルビス（４−ヒドロキシフェニル）アセテー
トに変えた他は、Ｂ液作成と全く同じに行いＪ液分散液
を得た。次に下記の割合で各法を混合して感熱塗料とす
る。Example 7 Color developer BPA (bisphenol-
A liquid dispersion of liquid J was obtained in exactly the same manner as liquid B except that A) was changed to methylbis(4-hydroxyphenyl) acetate. Next, each method is mixed in the following proportions to prepare a heat-sensitive paint.
Ａ液 ４ 部Ｊ
１６Ｃ１０
４
以下上記塗料を用い、実施例１と全く同様に行い、感熱
記録紙を得た。A liquid 4 parts J
16C10 4 Using the above coating material, the same procedure as in Example 1 was carried out to obtain heat-sensitive recording paper.
実施例８
実施例１中のＢ液中の顕色剤ＢＰＡ（ビスフェノール−
Ａ）をブチルビス（４−ヒドロキシフェニル）アセテー
トに変えた他は、Ｂ液作成と全く同じに行いＸ液分散液
を得た。次に下記の割合で各法を混合して感熱塗料とす
る。Example 8 Color developer BPA (bisphenol-
A dispersion of liquid X was obtained in exactly the same manner as in the preparation of liquid B, except that A) was changed to butyl bis(4-hydroxyphenyl) acetate. Next, each method is mixed in the following proportions to prepare a heat-sensitive paint.
Ａ液 ４ 部Ｘ
１６Ｃ１０
４
以下上記塗料を用い、実施例１と全く同様に行い、感熱
記録紙を得た。A liquid 4 parts
16C10 4 Using the above coating material, the same procedure as in Example 1 was carried out to obtain heat-sensitive recording paper.
実施例９
実施例７中のＡ液を実施例４中のＧ液分散液に変えた他
は、実施例７と全く同じに行った。すなわち、下記の割
合で各法を混合して感熱塗料とした。Example 9 The same procedure as in Example 7 was carried out except that the liquid A in Example 7 was replaced with the liquid G dispersion in Example 4. That is, each method was mixed in the following proportions to prepare a heat-sensitive paint.
Ｇ液 ４ 部Ｊ
１６Ｃ１０
４
以下上記塗料を用い、実施例１と全く同様に行い、感熱
記録紙を得た。G liquid 4 parts J
16C10 4 Using the above coating material, the same procedure as in Example 1 was carried out to obtain heat-sensitive recording paper.
実施例１０
実施例６中のＢ液を実施例７中のＪ液分散液に変えた他
は、実施例６と全く同じに行った。すなわち、下記の割
合で各法を混合して感熱塗料とした。Example 10 The same procedure as Example 6 was carried out except that the B solution in Example 6 was changed to the J solution dispersion in Example 7. That is, each method was mixed in the following proportions to prepare a heat-sensitive paint.
Ｉ液 ４ 部
Ｊ １６
Ｃ１０
４
以下上記塗料を用い、実施例１と全く同様に行い、感熱
記録紙を得た。Liquid I 4 parts J 16 C10 4 Using the above coating material, the same procedure as in Example 1 was carried out to obtain a heat-sensitive recording paper.
実施例１１
Ｋ液（染料分散液）
２−アニリノ−３−メチル−６
ジブチルアミノフルオラン ８ 部ステアリン
酸アマイド ８１０％ポリビニルアルコー
ル ２０水
４４Ｌ液（顕色剤分散液）
ＢＰＡ ８部
１．４−ジエトキシベンゼン １２４．４゛−ブ
チリデンビス−（３−メチル−５−ｔｅｒ、ブチル）フ
ェノール ２１０％ポリビニルアルコール ４
０水 １８上
記組成物の各法、ＫおよびＬをダイノーミルＫＤＬ分散
機で粒梗１．５〜３μまで粉砕する。Example 11 Liquid K (dye dispersion) 2-anilino-3-methyl-6 dibutylaminofluorane 8 parts stearamide 810% polyvinyl alcohol 20 water
44L liquid (developer dispersion) BPA 8 parts 1,4-diethoxybenzene 124.4'-butylidenebis-(3-methyl-5-ter, butyl)phenol 210% polyvinyl alcohol 4
0 Water 18 Each method of the above composition, K and L are ground to grain size of 1.5 to 3 μm using a Dyno Mill KDL disperser.
次に下記の割合で各法を混合して感熱塗料とする。Next, each method is mixed in the following proportions to prepare a heat-sensitive paint.
Ｋ液 ４ 部４
４
Ｄ９．３
この混合塗料を上質紙の表面にＮα１８のワイヤーバー
を用い、乾燥後の固形分重量が１ｇ／ｒｒＴになるよう
に塗布し、送風乾燥機中に入れ乾燥した。K liquid 4 parts 4 D9.3 This mixed paint was applied to the surface of high-quality paper using a Nα18 wire bar so that the solid content weight after drying was 1 g/rrT, and the mixture was placed in a blower dryer to dry. .
このようにして感熱記録紙を得た。A thermosensitive recording paper was thus obtained.
実施例１２
実施例１１中のＬ液を下記のＹ液分散液に変えた他は、
実施例１１と全く同じに行った。すなわち、
Ｙ液（顕色剤分散液）
ＢＰＡ ８部
１．４−ジエトキシベンゼン １２１０％ポリビ
ニルアルコール ４０水
２０上記組成物のＹ液をダイノーミル
ＫＤＬ分散機で粒ｔｉ １．５〜３μまで粉砕する。Example 12 Except for changing the L liquid in Example 11 to the following Y liquid dispersion,
The same procedure as in Example 11 was carried out. That is, Y liquid (color developer dispersion) BPA 8 parts 1,4-diethoxybenzene 1210% polyvinyl alcohol 40 water
20 Pulverize the Y solution of the above composition using a Dyno Mill KDL disperser to particles ti of 1.5 to 3μ.
次に下記の割合で各法を混合して感熱塗料とする。Next, each method is mixed in the following proportions to prepare a heat-sensitive paint.
Ｋ液 ４ 部４
４
Ｄ９．３
この混合塗料を上質紙の表面にＮ１１１８のワイヤーバ
ーを用い、乾燥後の固形分重量が７ｇ／ｒｒｆになるよ
うに塗布し、送風乾燥機中に入れ乾燥した。K liquid 4 parts 4 D9.3 This mixed paint was applied to the surface of high-quality paper using an N1118 wire bar so that the solid content weight after drying was 7 g/rrf, and the mixture was placed in a blower dryer to dry. .
このようにして感熱記録紙を得た。A thermosensitive recording paper was thus obtained.
対照例Ｉ
Ｂ液中の本発明化合物１．４−ジエトキシベンゼンヲ１
．４−ジメトキシベンゼンに変えた他は、Ｂ液作成と全
く同じに行いＭ液分散液を得た。Control Example I Compound of the present invention 1,4-diethoxybenzene in solution B
．． A dispersion of liquid M was obtained in exactly the same manner as liquid B except that 4-dimethoxybenzene was used.
次に下記の割合で各法を混合して感熱塗料とする。Next, each method is mixed in the following proportions to prepare a heat-sensitive paint.
Ａ液 ４ 部Ｍ
１６Ｃ１０
４
以下上記塗料を用い、実施例１と全く同様に行い、感熱
記録紙を得た。A liquid 4 parts M
16C10 4 Using the above coating material, the same procedure as in Example 1 was carried out to obtain heat-sensitive recording paper.
Ｂ液中の本発明化合物１．４−ジエトキシベンゼンを以
下の化合物（表１に記載）に変え、Ｂ液作成と全く同じ
に行いＮ液分散液からＲ液分散液までの５分散液を得た
。The present invention compound 1,4-diethoxybenzene in Solution B was replaced with the following compound (listed in Table 1), and the process was carried out in exactly the same manner as in the preparation of Solution B to prepare 5 dispersions from N solution dispersion to R solution dispersion. Obtained.
次にこれらのＮ液分散液からＲ液分散液を下記の割合で
各法を混合して感熱塗料とする。Next, these N liquid dispersions and R liquid dispersions are mixed by each method in the proportions shown below to prepare a thermal paint.
Ａ液 ４ 部Ｎ、Ｏ，Ｐ、
Ｑ、Ｒ１６
Ｃ１０
４
以下上記塗料を用い、実施例１と全く同様に行い、感熱
記録紙を得た。A liquid 4 parts N, O, P,
Q, R16 C10 4 Using the above coating material, the same procedure as in Example 1 was carried out to obtain a thermal recording paper.
表１ 対照側化合物
対照例２ Ｎ液 ４−ベンジルビフェニル対照例３
０液 ３−ターフェニル
対Ｈ例４ ｐ液 ２−ベンジルオキシナフタレン
対照例５ Ｑ液 ジベンジルオキザレート対照例６
Ｒ液 ジ（４−メチルヘンシル）オキザレート
対照例７
実施例１１中のＬ液中の本発明化合物１．４−ジエトキ
シベンゼンを４−ベンジルビフェニルに変えた他は、Ｌ
液作成と全く同じに行いＳ液分散液を得た。Table 1 Comparison Compound Control Example 2 N Solution 4-Benzylbiphenyl Control Example 3
0 liquid 3-terphenyl vs H example 4 P liquid 2-benzyloxynaphthalene control example 5 Q liquid dibenzyl oxalate control example 6
R liquid di(4-methylhensyl)oxalate control example 7 The present compound in Example 11, except that 4-diethoxybenzene in L liquid was changed to 4-benzylbiphenyl.
An S liquid dispersion was obtained in exactly the same manner as the liquid preparation.
次に下記の割合で各法を混合して感熱塗料とする。Next, each method is mixed in the following proportions to prepare a heat-sensitive paint.
Ｋ液 ４ 部４
４
Ｄ９．３
対照例日
実施例７中のＪ液中の本発明化合物１．４−ジエトキシ
ベンゼンを４−ベンジルビフェニルに変えた他は、Ｊ液
作成と全く同じに行いＴ液分散液を得た。Solution K 4 parts 4 4 D9.3 Control Example Day The process was carried out in exactly the same manner as the preparation of Solution J, except that the present invention compound 1,4-diethoxybenzene in Solution J in Example 7 was changed to 4-benzylbiphenyl. A T liquid dispersion was obtained.
次に下記の割合で各法を混合して感熱塗料とする。Next, each method is mixed in the following proportions to prepare a heat-sensitive paint.
Ａ液 ４ 部４
４
Ｄ９．３
対照例９
実施例１２中のＹ液中の本発明化合物１．４−ジエトキ
シベンゼンを４−ベンジルビフェニルに変えた他は、Ｙ
液作成と全く同じに行いＺ液分散液を得た。Solution A 4 parts 4 4 D9.3 Control example 9 The present invention compound 1.4-diethoxybenzene in Solution Y in Example 12 was changed to 4-benzylbiphenyl.
A Z liquid dispersion was obtained in exactly the same manner as the liquid preparation.
次に下記の割合で各法を混合して感熱塗料とする。Next, each method is mixed in the following proportions to prepare a heat-sensitive paint.
Ｋ液 ４ 部４
４
Ｄ９．３
実施例１〜実施例１２、対照例１〜対照例９で得られた
感熱記録紙について、それぞれ２０ｃｍ幅の所定用紙に
カットして、ユリロール製ミニカレンダーで平滑度が３
００秒になるようにカレンダー処理を行い、性能試験を
行った。K liquid 4 parts 4 D9.3 The heat-sensitive recording papers obtained in Examples 1 to 12 and Comparative Examples 1 to 9 were cut into 20 cm wide sheets and smoothed using a mini calender manufactured by YURI ROLL. degree is 3
A performance test was performed by calendering to obtain a time of 0.00 seconds.
結果を表−２中の実施例および表−３中の対照例の欄に
示す。The results are shown in the Examples column in Table 2 and the Control Example column in Table 3.
：発色濃度を縦軸に、発色エネルギーを横軸にグラフ化
した発色濃度−発色エネルギー曲線において、松下電子
部品側製、動的発色試験機条件で感熱記録紙を発色させ
た。発色部分をマクベス反射濃度計ＲＤ−９１８で測定
し、反射濃度１．０を示す発色エネルギーをＪｌ、０と
し、このときのエネルギー（ｍＤを発色感度と名称した
。: The thermosensitive recording paper was colored under the conditions of a dynamic coloring tester manufactured by Matsushita Electronic Components in a coloring density-coloring energy curve graphed with coloring density on the vertical axis and coloring energy on the horizontal axis. The colored portion was measured with a Macbeth reflection densitometer RD-918, and the coloring energy indicating a reflection density of 1.0 was defined as Jl, 0, and the energy (mD) at this time was designated as coloring sensitivity.
注−２＝上記注−１の条件下の未発色部分を地肌ＤＯと
した。Note-2 = The uncolored area under the conditions of Note-1 above was defined as background DO.
注−３：印字発色後の耐熱保存性を表し、上記性１の条
件で発色したＪｌ、０の部分を６０℃、２４時間後の発
色濃度Ｄ２を測定し、発色残存率＝ （Ｄ２／１．０）
＊ １００を求め、これを耐熱性とした。また、上記未
発色部分を６０℃、２４時間後の発色濃度を測定し、こ
れを耐熱地肌Ｄ３と名称した。Note-3: Indicates the heat-resistant storage stability after coloring of the printed image. The coloring density D2 of the Jl, 0 part that was colored under the conditions of property 1 above was measured at 60°C for 24 hours, and the residual rate of coloring = (D2/1 .0)
*100 was determined and this was defined as heat resistance. Further, the color density of the uncolored portion was measured after 24 hours at 60° C., and this was named heat-resistant background D3.
本発明の感熱記録材料は表２及び表３から明か注−１
なように従来公知の増感剤を含有した感熱記録紙と比較
し、地肌カブリが白く良好で、発色感度および耐熱保存
性の向上が著しい、感熱記録紙として優れた性能が得ら
れた。As can be seen from Tables 2 and 3, the heat-sensitive recording material of the present invention has whiter background fog and better color development sensitivity and heat-resistant storage stability than the heat-sensitive recording paper containing conventionally known sensitizers. Excellent performance as a thermal recording paper was obtained, with remarkable improvement.
保土谷化学工業株式会社 手続補正書 （自発） 平成２年３月１９ 日Hodogaya Chemical Industry Co., Ltd. Procedural amendment (spontaneous) March 19, 1990 Day
Claims (1)
該電子供与性無色染料を熱時発色させる酸性物質と結着
剤とを基本的に有する記録層を支持体上に設けてなる感
熱記録紙において、前記記録層中に１，４−ジエトキシ
ベンゼンを含有することを特徴とする感熱記録材料。1. A heat-sensitive recording comprising a recording layer provided on a support, which basically includes a colorless or slightly pale electron-donating colorless dye, an acidic substance that causes the electron-donating colorless dye to develop color when heated, and a binder. A heat-sensitive recording material comprising paper containing 1,4-diethoxybenzene in the recording layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022143A JPH03227689A (en) | 1990-02-02 | 1990-02-02 | Thermal recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022143A JPH03227689A (en) | 1990-02-02 | 1990-02-02 | Thermal recording material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03227689A true JPH03227689A (en) | 1991-10-08 |
Family
ID=12074653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2022143A Pending JPH03227689A (en) | 1990-02-02 | 1990-02-02 | Thermal recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03227689A (en) |
-
1990
- 1990-02-02 JP JP2022143A patent/JPH03227689A/en active Pending
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