JPH03292186A - Thermal recording material - Google Patents
Thermal recording materialInfo
- Publication number
- JPH03292186A JPH03292186A JP2093085A JP9308590A JPH03292186A JP H03292186 A JPH03292186 A JP H03292186A JP 2093085 A JP2093085 A JP 2093085A JP 9308590 A JP9308590 A JP 9308590A JP H03292186 A JPH03292186 A JP H03292186A
- Authority
- JP
- Japan
- Prior art keywords
- dye precursor
- forming layer
- color forming
- thermal color
- developer
- 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 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 14
- -1 ether compound Chemical class 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000004040 coloring Methods 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 230000002087 whitening effect Effects 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 230000002542 deteriorative effect Effects 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- 239000000975 dye Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000012259 ether extract Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical group ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 2
- MNVMYTVDDOXZLS-UHFFFAOYSA-N 4-methoxyguaiacol Natural products COC1=CC=C(O)C(OC)=C1 MNVMYTVDDOXZLS-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects 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
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001454 recorded image Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- AGPLQTQFIZBOLI-UHFFFAOYSA-N 1-benzyl-4-phenylbenzene Chemical group C=1C=C(C=2C=CC=CC=2)C=CC=1CC1=CC=CC=C1 AGPLQTQFIZBOLI-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- OAGNKYSIOSDNIG-UHFFFAOYSA-N 1-methyl-3-[2-(3-methylphenoxy)ethoxy]benzene Chemical compound CC1=CC=CC(OCCOC=2C=C(C)C=CC=2)=C1 OAGNKYSIOSDNIG-UHFFFAOYSA-N 0.000 description 1
- JWSWULLEVAMIJK-UHFFFAOYSA-N 1-phenylmethoxynaphthalene Chemical compound C=1C=CC2=CC=CC=C2C=1OCC1=CC=CC=C1 JWSWULLEVAMIJK-UHFFFAOYSA-N 0.000 description 1
- HUSIBQLZEMMTCQ-UHFFFAOYSA-N 2'-anilino-6'-[ethyl(3-methylbutyl)amino]-3'-methylspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C=1C(N(CCC(C)C)CC)=CC=C(C2(C3=CC=CC=C3C(=O)O2)C2=C3)C=1OC2=CC(C)=C3NC1=CC=CC=C1 HUSIBQLZEMMTCQ-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
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- BPLKDVGMXNZCQO-UHFFFAOYSA-N benzyl 4-phenylmethoxybenzoate Chemical compound C=1C=C(OCC=2C=CC=CC=2)C=CC=1C(=O)OCC1=CC=CC=C1 BPLKDVGMXNZCQO-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 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
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- RQAQWBFHPMSXKR-UHFFFAOYSA-N n-(4-chlorophenyl)-3-(phosphonooxy)naphthalene-2-carboxamide Chemical compound OP(O)(=O)OC1=CC2=CC=CC=C2C=C1C(=O)NC1=CC=C(Cl)C=C1 RQAQWBFHPMSXKR-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- QHDYIMWKSCJTIM-UHFFFAOYSA-N phenyl 1-hydroxynaphthalene-2-carboxylate Chemical compound C1=CC2=CC=CC=C2C(O)=C1C(=O)OC1=CC=CC=C1 QHDYIMWKSCJTIM-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 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
- 238000002360 preparation method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 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〕
本発明は感熱記録体に関するものであり、特に、白色度
が高く、高速記録適性に優れた感熱記録体に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a heat-sensitive recording medium, and particularly to a heat-sensitive recording medium that has high whiteness and excellent suitability for high-speed recording.
通常無色または淡色のロイコ染料と、フェノール類また
は有機酸との加熱発色反応を利用した感熱記録体は、例
えば特公昭43−4160号、特公昭45−14039
号、及び特公昭48−27736号などに開示されてお
り、広く実用化されている。近年、このような感熱記録
体は、単に加熱するだけで発色画像が形成されること、
記録装置が比較的コンパクトなものにすることができる
こと、などの利点により、各種情報記録材料として広範
囲に使用されている。特に、このような感熱記録体を用
いる感熱ファクシミリ、感熱プリンターなどは、その装
置の改良が進み、従来は難しいとされていた高速の印字
、高速の画像の形成が可能となっている。このような機
器、ハードの分野の高速化に伴い、使用される感熱記録
体も従来よりも大幅な記録感度の向上が要求されている
。Heat-sensitive recording materials that utilize a color-forming reaction under heating between normally colorless or light-colored leuco dyes and phenols or organic acids are disclosed in, for example, Japanese Patent Publication No. 43-4160 and Japanese Patent Publication No. 45-14039.
It is disclosed in Japanese Patent Publication No. 48-27736, etc., and has been widely put into practical use. In recent years, such heat-sensitive recording materials have been known to form colored images simply by heating;
Due to its advantages such as the fact that the recording device can be made relatively compact, it is widely used as a variety of information recording materials. In particular, the devices of thermal facsimiles, thermal printers, etc. that use such thermal recording materials have been improved, and it has become possible to perform high-speed printing and high-speed image formation, which was previously considered difficult. As the speed of such equipment and hardware increases, the heat-sensitive recording media used are required to have significantly improved recording sensitivity than before.
この要求を満たす為に多くの提案がなされてきたが、そ
れら提案の多く染料前駆体と顕色剤の組み合わせに、特
徴があるか、又は更に熱可融性物質を併用することに特
徴のあるものである。上記熱可融性物質は、増感剤とも
呼ばれ、例えば1−ヒドロキシ−2−ナフトエ酸フェニ
ルエステル(特開昭57−191089号)、p−ベン
ジルビフェニル(特開昭60−82382号)、ベンジ
ルナフチルエーテル(特開昭58−87094号)、ジ
ベンジルテレフタレート(特開昭58−98285号)
、p−ベンジルオキシ安息香酸ベンジル(特開昭57−
201691号)、炭酸ジフェニル、炭酸ジトリル(特
開昭58−136489号)、m−ターフェニル(特開
昭57−89994号)、1.2−ビス(m−トリルオ
キシ)エタン(特開昭60−56588号)l、5−ビ
ス(p−メトキシフェノキシ)−3−オキサペンタン(
特開昭62−181183号)、ペンジルオギザレート
(特開昭64−1583号)などが知られている。Many proposals have been made to meet this requirement, but many of these proposals have a characteristic in the combination of a dye precursor and a color developer, or in the combination of a thermofusible substance. It is something. The above-mentioned thermofusible substance is also called a sensitizer, and examples include 1-hydroxy-2-naphthoic acid phenyl ester (Japanese Patent Application Laid-open No. 191089/1989), p-benzylbiphenyl (Japanese Patent Application Laid-open No. 82382/1982), Benzyl naphthyl ether (JP 58-87094), dibenzyl terephthalate (JP 58-98285)
, benzyl p-benzyloxybenzoate (Japanese Patent Application Laid-open No. 1983-
No. 201691), diphenyl carbonate, ditolyl carbonate (Japanese Patent Publication No. 136489/1989), m-terphenyl (Japanese Patent Application Publication No. 89994/1989), 1,2-bis(m-tolyloxy)ethane (Japanese Patent Application Publication No. 60/1989) No. 56588) l, 5-bis(p-methoxyphenoxy)-3-oxapentane (
Known examples include JP-A-62-181183) and penzyl oxalate (JP-A-64-1583).
〔発明が解決しようとする問題点〕
上記のような熱可融性物質を含む感熱記録体が加熱され
ると、まず該熱可融性物質が融解し、それが染料前駆体
および顕色剤を溶かしこむことによって、両者が分子レ
ベルで混じり合い発色反応が誘起される。従って、これ
ら熱可融性物質は適当な融点(好ましくは60−140
’C)を有しているとともに、染料前駆体および顕色剤
との相溶性に優れているものでなければならない。また
、感熱記録体の白色度を低下させないことも重要で、そ
のためには、熱可融性物質は、水に対して、極めて難溶
性であることが望ましく、更に昇華性が低い等の性質を
もっていることが望ましい。熱可融性物質の昇華性は、
特に、感熱記録体の加熱発色部が、経時的に粉をふいた
ようになる、いわゆる白化という現象に深く関連してい
ると考えられ、感熱記録体の実用上、極めて重要な性質
となる。[Problems to be Solved by the Invention] When a heat-sensitive recording medium containing a thermofusible substance as described above is heated, the thermofusible substance first melts, and then the dye precursor and the color developer are melted. By dissolving the two, they mix at the molecular level and a coloring reaction is induced. Therefore, these thermofusible substances have a suitable melting point (preferably 60-140
'C) and must have excellent compatibility with the dye precursor and color developer. It is also important not to reduce the whiteness of the heat-sensitive recording medium, and for this purpose, it is desirable that the thermofusible substance has extremely low solubility in water, and also has properties such as low sublimation. It is desirable to be present. The sublimability of thermofusible substances is
In particular, it is thought to be closely related to the so-called whitening phenomenon in which the heat-colored portion of a heat-sensitive recording material becomes powdery over time, and is an extremely important property for the practical use of a heat-sensitive recording material.
上記のように熱可融性物質は従来数多く提案されてきた
が、上記の条件を全て満たすものは少なく、従って新し
い材料の出現が求められていた。As mentioned above, many thermofusible materials have been proposed in the past, but there are few that satisfy all of the above conditions, and therefore there has been a demand for new materials.
本発明は、前述の染料前駆体、顕色剤とともに新規な熱
可融性物質を用いて形成された感熱発色層を有し、記録
諸性能を低下させることなく大幅に向上した記録感度を
有する感熱記録体を提供しようとするものである。The present invention has a heat-sensitive coloring layer formed using a novel thermofusible substance together with the dye precursor and color developer described above, and has significantly improved recording sensitivity without deteriorating recording performance. The purpose is to provide a thermosensitive recording medium.
本発明の感熱記録体は、シート状基体とこのシート状基
体の少なくとも1面に形成され、かつ無色ないし淡色の
染料前駆体と、前記染料前駆体と加熱下に反応してこれ
を発色させる顕色剤とを含む感熱発色層を有し、前記感
熱発色層が、下記−紋穴(1):
(但し、式中R+、Rtは炭素数2〜4のアルキル基を
表す。)
で表される少なくとも一種のエーテル化合物を更に含有
していることを特徴とするものである。The heat-sensitive recording material of the present invention comprises a sheet-like substrate, a colorless or light-colored dye precursor formed on at least one surface of the sheet-like substrate, and a developer that reacts with the dye precursor under heating to develop color. and a coloring agent, the thermosensitive coloring layer is represented by the following - Monya (1): (wherein R+ and Rt represent an alkyl group having 2 to 4 carbon atoms.) It is characterized in that it further contains at least one ether compound.
本発明者らは、上記式(I)の熱可融性物質を増感剤と
して用いると、従来から熱可融性物質の代表的なものと
して提案され(特公昭50−14531号)、かつ実用
化されているステアリン酸アミド、バルミチン酸アミド
等の高級脂肪酸アミドを使用した場合に比較して白色度
の低下をきたすことなく、かつ発色画像の品質を経時的
に悪化させる白化というような現象を経験することなく
、極めて高い記録感度が得られることを見出し、本発明
を完成するに至った。The present inventors discovered that the use of the thermofusible substance of the above formula (I) as a sensitizer has been proposed as a typical thermofusible substance (Japanese Patent Publication No. 14531/1983), and Compared to the use of higher fatty acid amides such as stearic acid amide and balmitic acid amide, which have been put into practical use, there is no reduction in whiteness, and there is a phenomenon called whitening that deteriorates the quality of colored images over time. The present inventors have discovered that extremely high recording sensitivity can be obtained without experiencing the above problems, and have completed the present invention.
本発明は、無色ないし単色の塩基性ロイコ染料(染料前
駆体)と、この染料前駆体と接触して、それを顕色しう
る顕色剤の呈色反応を利用した感熱記録体において、感
熱発色層中に、上記式(I)の化合物を含有せしめた事
を特徴とするものである。上記の如き特定の熱可融性物
質(以後増感剤とよぶ)が、感熱発色層の発色感度を向
上する理由は十分に明確ではないが、この化合物が熔融
状態で粘度が低く、染料前駆体及び顕色剤と適当な相溶
性を有していることなどがその理由の一部と推測される
。また感熱発色層の白色度を低下させないのは、それが
水に対して難溶性のためであり、それが白化等の記録画
像品質を悪化させる現象の極めて少ないのは、その低い
昇華性にあると考えられる。しかし、発明者はこの解釈
に固執するものではない。本発明に用いられる式(I)
の増感剤の具体的な例としては以下のようなものを挙げ
ることがでのる。The present invention provides a thermosensitive recording material that utilizes a color reaction between a colorless or monochromatic basic leuco dye (dye precursor) and a color developer that can develop a color by contacting the dye precursor. It is characterized in that the coloring layer contains the compound of formula (I) above. The reason why a specific thermofusible substance (hereinafter referred to as a sensitizer) as mentioned above improves the coloring sensitivity of a thermosensitive coloring layer is not fully clear, but the reason is that this compound has a low viscosity in the molten state and is a dye precursor. It is assumed that part of the reason for this is that it has appropriate compatibility with the body and color developer. Furthermore, the reason why the whiteness of the heat-sensitive coloring layer does not decrease is because it is poorly soluble in water, and the reason why it rarely causes phenomena such as whitening that deteriorate recorded image quality is due to its low sublimability. it is conceivable that. However, the inventor does not adhere to this interpretation. Formula (I) used in the present invention
Specific examples of the sensitizer include the following.
本発明の化合物は各種合成法によって合成可能であるが
、最も簡便には下記に示す、Wtlliamson反応
を利用して容易に、かつ高収率で合成することができる
。下記反応式中R1,Rtは前記定義に同じである。The compound of the present invention can be synthesized by various synthetic methods, but most conveniently, it can be synthesized easily and in high yield using the Wtlliamson reaction shown below. In the reaction formula below, R1 and Rt are the same as defined above.
130−1;mth
180−L、fiフ
式(I)の増感剤は染料前駆体および顕色剤とともに用
いられる。また、本発明の所望の効果を阻害しないで範
囲内で、他の増感剤と併用して用いることもできる。本
発明の増感剤の使用量は顕色剤重量に対して、10〜1
000重量%であることが好ましく、50〜300重量
%であることがより好ましい。130-1; mth 180-L, fi The sensitizer of formula (I) is used together with a dye precursor and a color developer. Further, it can be used in combination with other sensitizers within a range without inhibiting the desired effects of the present invention. The amount of the sensitizer used in the present invention is 10 to 1
000% by weight, and more preferably 50 to 300% by weight.
本発明の増感剤を含む感熱発色層は、主に染料前駆体、
フェノール類又は有機酸よりなる顕色剤、およびこれら
を結着し、感熱発色層をシート状基体に接合するための
結着剤を含み、更に無機顔料を含んでいることが好ま、
シく、更に必要に応じて、ワックス類を含んでいてよい
。The thermosensitive coloring layer containing the sensitizer of the present invention mainly contains dye precursors,
It preferably contains a color developer made of phenols or organic acids, and a binder for binding these and joining the thermosensitive coloring layer to the sheet-like substrate, and further contains an inorganic pigment,
Furthermore, it may contain waxes if necessary.
染料前駆体として使用されるロイコ染料は従来公知のも
のから選ぶことができ、例えば、クリスタルバイオレッ
トラクトン、3−(N−エチル−N−イソペンチルアミ
ノ)−6−メチル−7−アニリノフルオラン、3−ジエ
チルアミノ−6−メチル−7−アニリノフルオラン、3
−ジエチルアミノ−6メチルー7−(oSp−ジメチル
アニリノ)フルオラン、3−(N−エチル−p−トルイ
ジノ)−6−メチル−7−アニリノフルオラン、3−ピ
ロリジノ−6−メチル−7−アニリノフルオラン、3−
ジブチルアミノ−6−メチル−7−アニリノフルオラン
、3−(N−シクロヘキシン−N−メチルアミン)−6
−メチル−7−アニリノフルオラン、3−ジエチルアミ
ノ−7−(o−クロロアニリノ)フルオラン、3−ジエ
チルアミノ−7−(m−トリフルオロメチルアニリノ)
フルオラン、3−ジエチルアミノ−6−メチル−7−ク
ロロフルオラン、3−ジエチルアミノ−6−メチルフル
オラン、および3−シクロヘキシルアミノ−6−クロロ
フルオラン等から選ばれた1種以上を用いることができ
る。The leuco dye used as a dye precursor can be selected from conventionally known ones, such as crystal violet lactone, 3-(N-ethyl-N-isopentylamino)-6-methyl-7-anilinofluoran. , 3-diethylamino-6-methyl-7-anilinofluorane, 3
-diethylamino-6methyl-7-(oSp-dimethylanilino)fluorane, 3-(N-ethyl-p-toluidino)-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane Linofluorane, 3-
Dibutylamino-6-methyl-7-anilinofluorane, 3-(N-cyclohexine-N-methylamine)-6
-Methyl-7-anilinofluorane, 3-diethylamino-7-(o-chloroanilino)fluoran, 3-diethylamino-7-(m-trifluoromethylanilino)
One or more selected from fluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-diethylamino-6-methylfluoran, 3-cyclohexylamino-6-chlorofluoran, etc. can be used. .
フェノール類又は、有機酸からなる顕色剤としては従来
公知のものを用いることができ、例えば、ビスフェーノ
ルA1p−ヒドロキシ安息香酸ベンジル(特開昭52−
140483号)、ビスフェノールS、4−ヒドロキシ
−4′−イソプロピルオキシジフェニルスルホン(特開
昭60−13852号)、■SL−ジ(4−ヒドロキシ
フェニル)シクロヘキサン、1.7−ジ(4−ヒドロキ
シフェニルチオ)−3,5−ジオキサへブタン(特開昭
59−52694号)などから選ばれた1種以上を用い
ることができる。As the color developer made of phenols or organic acids, conventionally known color developers can be used.
140483), bisphenol S, 4-hydroxy-4'-isopropyloxydiphenyl sulfone (JP-A-60-13852), SL-di(4-hydroxyphenyl)cyclohexane, 1.7-di(4-hydroxyphenyl) One or more types selected from thio)-3,5-dioxahebutane (Japanese Patent Application Laid-Open No. 59-52694) can be used.
ここで本発明の増感剤と併用することのできる他の増感
剤としては、融点60−150℃の熱可融性有機化合物
が用いられるが、これらについてはすでに代表的例をあ
げて説明した通りである。Here, as other sensitizers that can be used in combination with the sensitizer of the present invention, thermofusible organic compounds with a melting point of 60-150°C are used, but these have already been explained with typical examples. That's exactly what I did.
また、感熱発色層中に用いられる有機又は無機の顔料と
しては、炭酸カルシウム、シリカ、酸化亜鉛、酸化チタ
ン、水酸化アルミニウム、水酸化亜鉛、硫酸バリウム、
クレー、焼成りレー、タルク、および表面処理された炭
酸カルシウムやシリカ等の無機系微粉末の他、並びに、
尿素−ホルマリン樹脂、スチレン/メタクリル酸供重合
体、およびポリスチレン樹脂等の有機系の微粉末などを
挙げることができる。In addition, examples of organic or inorganic pigments used in the heat-sensitive coloring layer include calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate,
In addition to clay, fired clay, talc, and surface-treated inorganic fine powders such as calcium carbonate and silica, and
Examples include organic fine powders such as urea-formalin resin, styrene/methacrylic acid donor polymer, and polystyrene resin.
更に本発明の感熱発色層は、種々のワックス類を必要に
応じて含有していてもよい。それらはワックス類として
は、パラフィン、アミド系ワックス、ビスイミド系ワッ
クス、高吸脂肪酸の金属塩など公知のものを用いること
ができる。また、前記接着剤については11種々の分子
量のポリビニルアルコール、デンプン及びその誘導体、
メトキシセルロース、カルボキシメチルセルロース、メ
チルセルロース、エチルセルロース等のセルロース誘導
体、ポリアクリル酸ソーダ、ポリビニルピロリドン、ア
クリル酸アミド/アクリル酸エステル共重合体、アクリ
ル酸アミド/アクリル酸エステル/メタクリル酸3元共
重合体、スチレン/無水マレイン酸共重合体アルカリ塩
、ポリアクリルアミド、アルギン酸ソーダ、ゼラチン、
およびカゼインなどの水溶性高分子材料、並びに、ポリ
酢酸ビニル、ポリウレタン、スチレン/ブタジェン共重
合体、ポリアクリル酸、ポリアクリル酸エステル、塩化
ビニル/酢酸ビニル共重合体、ポリブチルメタクリレー
ト、エチレン/酢酸ビニル共重合体、およびスチレン/
ブタジェン/アクリル系共重合体等の各々のラテックス
を用いることができる。Furthermore, the heat-sensitive coloring layer of the present invention may contain various waxes as required. Known waxes such as paraffin, amide wax, bisimide wax, and metal salts of highly absorbent fatty acids can be used. Regarding the adhesive, 11 types of polyvinyl alcohol of various molecular weights, starch and its derivatives,
Cellulose derivatives such as methoxycellulose, carboxymethylcellulose, methylcellulose, and ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, acrylamide/acrylic acid ester copolymer, acrylamide/acrylic acid ester/methacrylic acid ternary copolymer, styrene /Maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, gelatin,
and water-soluble polymeric materials such as casein, as well as polyvinyl acetate, polyurethane, styrene/butadiene copolymer, polyacrylic acid, polyacrylic acid ester, vinyl chloride/vinyl acetate copolymer, polybutyl methacrylate, ethylene/acetic acid vinyl copolymer, and styrene/
Latexes such as butadiene/acrylic copolymers can be used.
本発明の感熱記録体に用いるシート状基体は、紙、表面
に粘土プラスチックなどを塗工したコーテツド紙、主に
プラスチックから作られる合成紙、あるいはプラスチッ
クフィルムなどから選ぶことができる。このようなシー
ト状基体の少なくとも1面上に、上記所要成分の混合物
を含む塗布液を塗布し、乾燥して感熱記録体を製造する
。塗布量は、塗布液が乾燥した状態で1−15g/rr
rが好ましく、2〜10g/−が特に好ましい。The sheet-like substrate used in the heat-sensitive recording medium of the present invention can be selected from paper, coated paper whose surface is coated with clay plastic, synthetic paper made mainly from plastic, or plastic film. A coating liquid containing a mixture of the above-mentioned necessary components is applied onto at least one surface of such a sheet-like substrate and dried to produce a heat-sensitive recording material. The coating amount is 1-15g/rr when the coating liquid is dry.
r is preferred, and 2 to 10 g/- is particularly preferred.
このようにして、得られた本発明の感熱記録体は、高速
記録適性に優れ、白色度が高く、記録画像部における白
化のような好ましくない現象を発生することのないもの
である。The heat-sensitive recording material of the present invention thus obtained has excellent high-speed recording suitability, high whiteness, and does not cause undesirable phenomena such as whitening in the recorded image area.
以下に実施例により、本発明を具体的に説明する。尚、
特に断らない限り、「部」および「%」は、それぞれ「
重量部」および「重量%」をあられす。The present invention will be specifically explained below with reference to Examples. still,
Unless otherwise specified, "part" and "%" respectively refer to "part" and "%".
Parts by weight and % by weight.
35、0 gのα、α′−ジクロローp−キシレンと5
3.7 gの2,4−ジメチルフェノールと60.7g
の炭欺カリウムを500ccのアセトンに加え攪拌する
。浴温を85℃に加熱してアセトンを還流させる。還流
を一昼夜続けた後、アセトンを留去する。この残留物に
エーテルを加えエーテル抽出を行ない、エーテル抽出液
をアルカリと酸で洗浄した後、エーテルを留去すること
により淡黄色の固体を得た。これをエチルアルコールよ
り2回再結晶し58.8 gの白色固体を得た。その融
点は124〜126℃であった。質量分析、および核磁
気共鳴スペクトル測定により、この固体生成物がα、α
′−ビス(2,4−ジメチルフェノキシ)−p−キシレ
ンであることを確認した。35.0 g of α,α′-dichloro-p-xylene and 5
3.7 g of 2,4-dimethylphenol and 60.7 g
Add potassium carbonate to 500 cc of acetone and stir. Heat the bath temperature to 85°C to reflux the acetone. After continuing refluxing for a day and night, acetone was distilled off. Ether was added to this residue to perform ether extraction, and the ether extract was washed with alkali and acid, and the ether was distilled off to obtain a pale yellow solid. This was recrystallized twice from ethyl alcohol to obtain 58.8 g of white solid. Its melting point was 124-126°C. Mass spectrometry and nuclear magnetic resonance spectroscopy revealed that this solid product was α, α
It was confirmed that it was '-bis(2,4-dimethylphenoxy)-p-xylene.
35、0 gのα、α′−ジクロローp−キシレンと5
3.7 gの2,4−ジメチルフェノール)と60、7
gの炭酸カリウムを500ccのアセトンに加え攪拌
する。浴温を85℃に加熱してアセトンを還流させる。35.0 g of α,α′-dichloro-p-xylene and 5
3.7 g of 2,4-dimethylphenol) and 60,7
g of potassium carbonate is added to 500 cc of acetone and stirred. Heat the bath temperature to 85°C to reflux the acetone.
還流を一昼夜続けた後、アセトンを留去する。この残留
物にエーテルを加えエーテル抽出を行ない、エーテル抽
出液をアルカリと酸で洗浄した後、エーテルを留去する
ことにより淡褐色の固体を得た。これをエチルアルコー
ルより2回再結晶し52.2 gの白色固体を得た。そ
の融点は123〜125℃であった。質量分析、および
核磁気共鳴スペクトル測定により、この固体生成物がα
、α′−ビス(2,6−ジメチルフェノキシ)−p−キ
シレンであることを確認した。After continuing refluxing for a day and night, acetone was distilled off. Ether was added to this residue to perform ether extraction, and the ether extract was washed with alkali and acid, and the ether was distilled off to obtain a pale brown solid. This was recrystallized twice from ethyl alcohol to obtain 52.2 g of white solid. Its melting point was 123-125°C. Mass spectrometry and nuclear magnetic resonance spectrometry revealed that this solid product was α
, α'-bis(2,6-dimethylphenoxy)-p-xylene.
35、0 gのα、α′−ジクロローp−キシレンと7
8.3 gの2,6−ジ−1so−プロピルフェノール
と60.7 gの炭酸カリウムを600ccのアセトン
に加え攪拌する。浴温を85℃に加熱してアセトンを還
流させる。還流を=昼夜続けた後、アセトンを留去する
。この残留物にエーテルを加えエーテル抽出を行ない、
エーテル抽出液をアルカリと酸で洗浄した後、エーテル
を留去することにより淡黄色の固体を得た。これをエチ
ルアルコールより2回再結晶し61.0 gの白色固体
を得た。35.0 g of α,α′-dichloro-p-xylene and 7
8.3 g of 2,6-di-1so-propylphenol and 60.7 g of potassium carbonate are added to 600 cc of acetone and stirred. Heat the bath temperature to 85°C to reflux the acetone. After continuing reflux for a day and night, the acetone is distilled off. Add ether to this residue and perform ether extraction.
After washing the ether extract with alkali and acid, the ether was distilled off to obtain a pale yellow solid. This was recrystallized twice from ethyl alcohol to obtain 61.0 g of white solid.
その融点は116〜117℃であった。質量分析、およ
び核磁気共鳴スペクトル測定により、この固体生成物が
α、α′−ビス(2,6−ジーis。Its melting point was 116-117°C. Mass spectrometry and nuclear magnetic resonance spectroscopy revealed that this solid product was α,α′-bis(2,6-diis.
−プロピルフェノキシ)−p−キシレンであることを確
認した。-propylphenoxy)-p-xylene.
43、6 gのα、α′−ジクロローp−キシレンと5
9.1 gのp−クレゾールと75.5 gの炭酸カリ
ウムを600ccのアセトンに加え攪拌する。43.6 g of α,α′-dichlorop-xylene and 5
9.1 g of p-cresol and 75.5 g of potassium carbonate are added to 600 cc of acetone and stirred.
浴温を85℃に加熱してアセトンを還流させる。Heat the bath temperature to 85°C to reflux the acetone.
還流を一昼夜続けた後、アセトンを留去する。この残留
物にエーテルを加えエーテル抽出を行ない、エーテル抽
出液をアルカリと酸で洗浄した後、エーテルを留去する
ことにより淡黄色の固体を得た。After continuing refluxing for a day and night, acetone was distilled off. Ether was added to this residue to perform ether extraction, and the ether extract was washed with alkali and acid, and the ether was distilled off to obtain a pale yellow solid.
これをエチルアルコールより2回再結晶し59、9 g
の白色固体を得た。その融点は170〜172℃であっ
た。質量分析、および核磁気共鳴スペクトル測定により
、この固体生成物がα、α′−ビス(4−メチルフェノ
キシ)−p−キシレンであることを確認した。This was recrystallized twice from ethyl alcohol to yield 59.9 g.
A white solid was obtained. Its melting point was 170-172°C. This solid product was confirmed to be α,α'-bis(4-methylphenoxy)-p-xylene by mass spectrometry and nuclear magnetic resonance spectroscopy.
実施例 1 下記操作により感熱記録紙を作成した。Example 1 A thermosensitive recording paper was prepared by the following procedure.
■ 分散液A調製
成 分 量(部)3−(N−
イソペンチル−N−エチル
アミノ)−6−メチル−7−アニリツ
フルオラン 20ポリビ
ニルアルコール 10%液10
水 7
0上記組威物をサンドグラインダーに供し、平均粒径が
1μmになるまで粉砕した。■ Ingredients for preparing dispersion A Amount (parts) 3-(N-
Isopentyl-N-ethylamino)-6-methyl-7-anilite fluorane 20 Polyvinyl alcohol 10% liquid 10 Water 7
0 The above-mentioned composite material was subjected to a sand grinder and ground until the average particle size became 1 μm.
■ 分散液B調製
11里と
4.4′−イソプロビリデンビフェルノール
10α、α′−ビス(2,4−
ジメチルフェノキシ)−p−キシレン
lOポリビニルアルコール 10% 10
水
70上記組成物をサンドグラインダーに供し、平均粒径
が1μmになるまで粉砕した。■ Dispersion B preparation 11ri and 4,4'-isopropylidene bifernol
10α, α′-bis(2,4-
dimethylphenoxy)-p-xylene
lO polyvinyl alcohol 10% 10
water
70 The above composition was subjected to a sand grinder and ground until the average particle size was 1 μm.
翅−登豆厘坐亘夏
上記A液40部、B液160部、炭酸カルシウム顔料4
0部、30%パラフィン分散液20部、およびlO%ポ
リビニルアルコール水溶液180部を混合、攪拌し、塗
布液とした。この塗布液を、坪量50 g/nfの原紙
の片面に、乾燥後の塗布量が7.0g/fflとなるよ
うに塗布乾燥して感熱発色層を形威し、感熱記録紙を作
成した。Tsubasa - Tozurinzawaka 40 parts of the above liquid A, 160 parts of liquid B, 4 parts of calcium carbonate pigment
0 parts, 20 parts of 30% paraffin dispersion, and 180 parts of 10% polyvinyl alcohol aqueous solution were mixed and stirred to prepare a coating liquid. This coating liquid was coated on one side of base paper with a basis weight of 50 g/nf so that the coated amount after drying was 7.0 g/ffl, and dried to form a thermosensitive coloring layer, thereby producing thermosensitive recording paper. .
上記の様にして得られた感熱記録紙をスーパーカレンダ
ーによって処理し、その表面の平滑度を600〜100
0秒とした。こうして得られた試料について、下記テス
トによって記録感度の測定、記録層面未発色部の色濃度
の測定、および白化の比較試験を行いその結果を第1表
に示した。The heat-sensitive recording paper obtained as described above is treated with a supercalender, and its surface smoothness is adjusted to 600 to 100.
It was set to 0 seconds. The samples thus obtained were subjected to the following tests to measure the recording sensitivity, measure the color density of the uncolored area on the recording layer surface, and compare whitening, and the results are shown in Table 1.
」互と星羞里眞
東洋精機製熱傾斜試験器を用い、温度120℃、圧力2
.5 kg / crjの条件下で試料を100ミリ秒
間加熱し、その際の発色濃度をマクベス濃度計RD−9
14で測定した。この測定値をもって感熱紙の記録感度
を表した。記録層面の未発色部(白紙部)の濃度を上記
濃度計で測定し、その測定値をもって白色度を表した。” Using a Toyo Seiki thermal gradient tester, the temperature was 120°C and the pressure was 2.
.. The sample was heated for 100 milliseconds under the condition of 5 kg/crj, and the color density was measured using a Macbeth densitometer RD-9.
Measured at 14. This measured value represents the recording sensitivity of the thermal paper. The density of the uncolored area (blank area) on the surface of the recording layer was measured using the above densitometer, and the measured value was expressed as the degree of whiteness.
工互と虹亘北立
上記試験機で、温度]50℃で試料を発色させた後、印
字部を40℃、90%の環境に24時間放置し、その表
面の変化を官能的に評価した。第1表において、「良好
」は発色印字部の変化が認められないことを示し、「不
良」は印字表面が粉をふいたようになる、いわゆる白化
が発生した事を示す。After developing the sample at a temperature of 50°C using the above testing machine, the printed area was left in an environment of 90% at 40°C for 24 hours, and changes in the surface were sensory evaluated. . In Table 1, "Good" indicates that no change was observed in the colored printed area, and "Poor" indicates that so-called whitening, in which the printed surface becomes powdery, has occurred.
テスト結果を第1表に示す。The test results are shown in Table 1.
莱施旦ヱ 下記操作により感熱記録紙を作成した。Rise Dane A thermosensitive recording paper was prepared by the following procedure.
l 塗 紙の一製
焼成クレイ(商品名アンシレックス)85部を水320
部に分散して得られた分散液にスチレン−ブタジェン共
重合エマルジョン(固形分50%)を40部、10%酸
化でんぷん水溶液を50部混合し、得られた塗布液を、
坪量48g/rrrの原紙の片面上に、乾燥後の塗布量
が7.0g/rrrになるよう塗布して、顔料下塗り紙
を作成した。l Coating: 85 parts of baked clay made of paper (trade name: Ansilex) and 320 parts of water.
40 parts of a styrene-butadiene copolymer emulsion (solid content 50%) and 50 parts of a 10% oxidized starch aqueous solution were mixed into the resulting dispersion, and the resulting coating liquid was
A pigment undercoated paper was prepared by applying the pigment to one side of a base paper having a basis weight of 48 g/rrr so that the coating amount after drying was 7.0 g/rrr.
盗−里艶且亘屋坐彪處
A分散液50部、B分散液200部、炭酸カルシウム2
5部、30%パラフィン分散液20部、および10%ポ
リビニルアルコール水溶液180部を混合、攪拌し、塗
布液とした。得られた塗液を、上記顔料下塗り紙の顔料
塗布面上に、乾燥後の塗布量が5.0g/rrrとなる
ように塗布乾燥して感熱発色層を形成し、感熱記録紙を
作成した。50 parts of the dispersion A, 200 parts of the dispersion B, 2 parts of calcium carbonate
5 parts of a 30% paraffin dispersion, and 180 parts of a 10% polyvinyl alcohol aqueous solution were mixed and stirred to prepare a coating liquid. The obtained coating liquid was applied and dried on the pigment-coated surface of the pigment undercoated paper so that the coating amount after drying was 5.0 g/rrr to form a thermosensitive coloring layer, thereby producing thermosensitive recording paper. .
この感熱記録紙を用いて、実施例1と同じテストを行な
った。The same test as in Example 1 was conducted using this thermosensitive recording paper.
その結果を第1表に示す。The results are shown in Table 1.
夾旌図−1
実施例2と同じ操作を行なった。但し感熱発色層の形成
に用いたB液の調成に当たり、α、α′ビス(2,4−
ジメチルフェノキシ)−p−キシレンのかわりに、α、
α′−ビス(2I 6−ジメチルフェノキシ)−p−キ
シレンを用いた。Figure-1 The same operation as in Example 2 was performed. However, in preparing the B solution used for forming the thermosensitive coloring layer, α, α' bis(2,4-
α, instead of dimethylphenoxy)-p-xylene,
α'-bis(2I 6-dimethylphenoxy)-p-xylene was used.
テスト結果を第1表に示す。The test results are shown in Table 1.
寒皇思−ま
実施例2と同じ操作を行なった。但し、感熱発色層の形
成に用いたB液の調成に当たり、α、α′−ビス(2,
4−ジメチルフェノキシ)−p−キシレンのかわりに、
α、α′−ビス(2,6−ジ−1so−プロピルフェノ
キシ)−p−キシレンを用いた。The same operation as in Example 2 was carried out. However, in preparing the B solution used for forming the thermosensitive coloring layer, α,α'-bis(2,
Instead of 4-dimethylphenoxy)-p-xylene,
α,α′-bis(2,6-di-1so-propylphenoxy)-p-xylene was used.
テスト結果を第1表に示す。The test results are shown in Table 1.
塩艶思工
実施例1と同じ操作を行なった。但し、B液調製におい
て、α、α′−ビス(2,4−ジメチルフェノキシ)−
p−キシレンのかわりに、ステアリン豫アミドを用いた
。The same operation as in Example 1 was carried out. However, in preparing liquid B, α,α'-bis(2,4-dimethylphenoxy)-
Stearin amide was used instead of p-xylene.
テスト結果を第1表に示す。The test results are shown in Table 1.
止藍亘又
実施例1と同じ操作を行なった。但し、B液調製におい
て、α、α′−ビス(2,4−ジメチルフェノキシ)−
p−キシレンのかわりに、α、α−ビス(4−メチルフ
ェノキシ)−p−キシレンを用いた。The same operation as in Example 1 was carried out. However, in preparing liquid B, α,α'-bis(2,4-dimethylphenoxy)-
α,α-bis(4-methylphenoxy)-p-xylene was used instead of p-xylene.
テスト結果を第1表に示す。The test results are shown in Table 1.
里艶思1
実施例2と同じ操作を行なった。但し、B液調製におい
て、α、α′−ビス(2,4−ジメチルフェノキシ)−
p−キシレンのかわりに、ステアリン酸アミドを用いた
。Satoshi 1 The same operation as in Example 2 was performed. However, in preparing liquid B, α,α'-bis(2,4-dimethylphenoxy)-
Stearamide was used instead of p-xylene.
テスト結果を第1表に示す。The test results are shown in Table 1.
里校剋工
実施例2と同じ操作を行なった。但し、B液調製におい
て、α、α′−ビス(2,4−ジメチルフェノキシ)−
p−キシレンのかわりに、α、α′−ビス(4−メチル
フェノキシ)−p−キシレンを用いた。The same operations as in Example 2 were performed. However, in preparing liquid B, α,α'-bis(2,4-dimethylphenoxy)-
α,α′-bis(4-methylphenoxy)-p-xylene was used instead of p-xylene.
テスト結果を第1表に示す。The test results are shown in Table 1.
里艶史上
実施例2と同じ操作を行なった。但し、B液調製におい
て、α、α′−ビス(2,4−ジメチルフェノキシ)−
p−キシレンのかわりに、l−ヒドロキシ−2−ナフト
エ酸フェニルエステルを用いた。The same operation as in Example 2 was carried out. However, in preparing liquid B, α,α'-bis(2,4-dimethylphenoxy)-
l-hydroxy-2-naphthoic acid phenyl ester was used instead of p-xylene.
テスト結果を第1表に示す。The test results are shown in Table 1.
第1表
したα、α −ビス(4−メチルフェノキシ)−p−キ
シレンを用いた例である。α、α −ビス(4−メチル
フェノキシ)−p−キシレンは本発明の化合物に対して
化学構造上は、置換基がパラ位のメチル基1個だけであ
るという違いであるが、融点がかなり高く、比較例より
あきらかなごとく、増感剤としての性能は本発明の化合
物よりずっと劣るものであることがわかる。This is an example using α,α-bis(4-methylphenoxy)-p-xylene shown in Table 1. The chemical structure of α,α-bis(4-methylphenoxy)-p-xylene differs from the compound of the present invention in that the substituent is only one methyl group at the para position, but it has a considerably higher melting point. As is clear from the comparative example, the performance as a sensitizer is much inferior to that of the compound of the present invention.
本発明の感熱記録体は、新規な熱可融性材料からなる増
感剤を含む感熱発色層を有しているため、高速記録適性
に優れ、白色度も高く、かつ白化のような好ましくない
現象を誘起せず、品質面で極めてバランスのとれた性質
を有しており、実用的価値の極めて高いものである。Since the heat-sensitive recording material of the present invention has a heat-sensitive coloring layer containing a sensitizer made of a new thermofusible material, it has excellent high-speed recording suitability, high whiteness, and undesirable problems such as whitening. It does not induce any phenomena, has extremely well-balanced properties in terms of quality, and has extremely high practical value.
Claims (1)
成され、かつ無色ないし淡色の染料前駆体と、前記染料
前駆体と加熱下に反応してこれを発色させる顕色剤とを
含む感熱発色層を有し、前記感熱発色層が、下記一般式
( I ): ▲数式、化学式、表等があります▼( I ) (但し、式中R_1、R_2、は炭素数2〜4のアルキ
ル基を表す。) で表される少なくとも一種のエーテル化合物を更に含有
していることを特徴とする感熱記録体。[Scope of Claims] A sheet-like substrate, a colorless or light-colored dye precursor formed on at least one surface of the sheet-like substrate, and a color developer that reacts with the dye precursor under heating to develop color. The thermosensitive coloring layer has the following general formula (I): ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) (However, in the formula, R_1 and R_2 have 2 to 2 carbon atoms. A thermosensitive recording material further comprising at least one ether compound represented by:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2093085A JPH03292186A (en) | 1990-04-10 | 1990-04-10 | Thermal recording material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2093085A JPH03292186A (en) | 1990-04-10 | 1990-04-10 | Thermal recording material |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03292186A true JPH03292186A (en) | 1991-12-24 |
Family
ID=14072690
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2093085A Pending JPH03292186A (en) | 1990-04-10 | 1990-04-10 | Thermal recording material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03292186A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0532049A (en) * | 1991-07-30 | 1993-02-09 | Nikka Chem Co Ltd | Thermal recording material |
-
1990
- 1990-04-10 JP JP2093085A patent/JPH03292186A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0532049A (en) * | 1991-07-30 | 1993-02-09 | Nikka Chem Co Ltd | Thermal recording material |
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