JPS63125389A - Thermal recording material - Google Patents
Thermal recording materialInfo
- Publication number
- JPS63125389A JPS63125389A JP61271116A JP27111686A JPS63125389A JP S63125389 A JPS63125389 A JP S63125389A JP 61271116 A JP61271116 A JP 61271116A JP 27111686 A JP27111686 A JP 27111686A JP S63125389 A JPS63125389 A JP S63125389A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- recording material
- particles
- compound
- dye precursor
- 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 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000008049 diazo compounds Chemical class 0.000 claims abstract description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010419 fine particle Substances 0.000 claims description 16
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 239000002245 particle Substances 0.000 abstract description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 8
- 238000010304 firing Methods 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052593 corundum Inorganic materials 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 abstract 1
- 238000010276 construction Methods 0.000 abstract 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 26
- 239000006185 dispersion Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 239000011241 protective layer Substances 0.000 description 16
- -1 S n 02 Inorganic materials 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920000126 latex Polymers 0.000 description 6
- 239000004816 latex Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 3
- 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 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 3
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 235000010216 calcium carbonate Nutrition 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 150000001989 diazonium salts Chemical group 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 3
- 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 2
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical class O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 2
- 244000215068 Acacia senegal Species 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- 229920000084 Gum arabic Polymers 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 229910007541 Zn O Inorganic materials 0.000 description 2
- 239000000205 acacia gum Substances 0.000 description 2
- 235000010489 acacia gum Nutrition 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 2
- 229940063655 aluminum stearate Drugs 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- LRTQWXGNPCHTFW-UHFFFAOYSA-N buta-1,3-diene;methyl prop-2-enoate Chemical compound C=CC=C.COC(=O)C=C LRTQWXGNPCHTFW-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 235000013869 carnauba wax Nutrition 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- 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 2
- 235000021240 caseins Nutrition 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical class C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 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
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N methyl phenyl ether Natural products COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 239000004200 microcrystalline wax Substances 0.000 description 2
- 235000019808 microcrystalline wax Nutrition 0.000 description 2
- JHOKTNSTUVKGJC-UHFFFAOYSA-N n-(hydroxymethyl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCO JHOKTNSTUVKGJC-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 229940037312 stearamide Drugs 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- VGZQXMKOOXTPND-UHFFFAOYSA-N 1-[[naphthalen-1-yl(phenyl)methoxy]-phenylmethyl]naphthalene Chemical compound C=1C=CC=CC=1C(C=1C2=CC=CC=C2C=CC=1)OC(C=1C2=CC=CC=C2C=CC=1)C1=CC=CC=C1 VGZQXMKOOXTPND-UHFFFAOYSA-N 0.000 description 1
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 description 1
- ZRIKQCAGVKAIIB-UHFFFAOYSA-N 2,2-di(octan-3-yl)-3-sulfobutanedioic acid Chemical compound CCCCCC(CC)C(C(O)=O)(C(C(O)=O)S(O)(=O)=O)C(CC)CCCCC ZRIKQCAGVKAIIB-UHFFFAOYSA-N 0.000 description 1
- XXKHDSGLCLCFSC-UHFFFAOYSA-N 2,3-diphenylphenol Chemical compound C=1C=CC=CC=1C=1C(O)=CC=CC=1C1=CC=CC=C1 XXKHDSGLCLCFSC-UHFFFAOYSA-N 0.000 description 1
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 description 1
- DYWBYCYREANRBJ-UHFFFAOYSA-N 2-[(4-chlorophenyl)methoxy]naphthalene Chemical compound C1=CC(Cl)=CC=C1COC1=CC=C(C=CC=C2)C2=C1 DYWBYCYREANRBJ-UHFFFAOYSA-N 0.000 description 1
- YQMNHMHKAZXDGD-UHFFFAOYSA-N 2-[(4-methylphenyl)methoxy]naphthalene Chemical compound C1=CC(C)=CC=C1COC1=CC=C(C=CC=C2)C2=C1 YQMNHMHKAZXDGD-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
- AIVZHIIGMQREQX-UHFFFAOYSA-N 3-(1-phenylethyl)benzene-1,2-diol Chemical class C=1C=CC(O)=C(O)C=1C(C)C1=CC=CC=C1 AIVZHIIGMQREQX-UHFFFAOYSA-N 0.000 description 1
- YHWKEAXOYNKJKZ-UHFFFAOYSA-N 3-(2-phenylpropan-2-yl)benzene-1,2-diol Chemical class C=1C=CC(O)=C(O)C=1C(C)(C)C1=CC=CC=C1 YHWKEAXOYNKJKZ-UHFFFAOYSA-N 0.000 description 1
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 description 1
- UIKUBYKUYUSRSM-UHFFFAOYSA-N 3-morpholinopropylamine Chemical compound NCCCN1CCOCC1 UIKUBYKUYUSRSM-UHFFFAOYSA-N 0.000 description 1
- XRZDIHADHZSFBB-UHFFFAOYSA-N 3-oxo-n,3-diphenylpropanamide Chemical compound C=1C=CC=CC=1NC(=O)CC(=O)C1=CC=CC=C1 XRZDIHADHZSFBB-UHFFFAOYSA-N 0.000 description 1
- NIOAVQYSSKOCQP-UHFFFAOYSA-N 4-hydroxynaphthalene-2-carboxylic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC(O)=C21 NIOAVQYSSKOCQP-UHFFFAOYSA-N 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 229910006130 SO4 Inorganic materials 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- JRLDUDBQNVFTCA-UHFFFAOYSA-N antimony(3+);trinitrate Chemical compound [Sb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JRLDUDBQNVFTCA-UHFFFAOYSA-N 0.000 description 1
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical compound C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 description 1
- 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
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052923 celestite Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 235000019642 color hue Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical group [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 235000018977 lysine Nutrition 0.000 description 1
- 150000002669 lysines Chemical class 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002780 morpholines Chemical class 0.000 description 1
- QEALYLRSRQDCRA-UHFFFAOYSA-N myristamide Chemical compound CCCCCCCCCCCCCC(N)=O QEALYLRSRQDCRA-UHFFFAOYSA-N 0.000 description 1
- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- GJNDMSSZEBNLPU-UHFFFAOYSA-N octadecylurea Chemical compound CCCCCCCCCCCCCCCCCCNC(N)=O GJNDMSSZEBNLPU-UHFFFAOYSA-N 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- XBDNVPPAQQNVBW-UHFFFAOYSA-N phenyl naphthalene-2-carboxylate Chemical compound C=1C=C2C=CC=CC2=CC=1C(=O)OC1=CC=CC=C1 XBDNVPPAQQNVBW-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003216 pyrazines Chemical class 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 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 1
- 229940058287 salicylic acid derivative anticestodals Drugs 0.000 description 1
- 150000003872 salicylic acid derivatives Chemical class 0.000 description 1
- 150000003870 salicylic acids Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003413 spiro compounds Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000004897 thiazines Chemical class 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/52—Compositions containing diazo compounds as photosensitive substances
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の利用分野〕
本発明は感熱記録材料に関するものであり、特に通常無
色乃至淡色の染料前駆体と該染料前駆体と反応して呈色
する化合物（以下１顕色性化合物“という。）の呈色反
応またはジアゾ化合物と該ジアゾ化合物と反応して呈色
する成分との呈色反応を利用した感熱記録材料に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a heat-sensitive recording material. The present invention relates to a heat-sensitive recording material that utilizes the color reaction of a chromatic compound (referred to as "chromic compound") or the color reaction of a diazo compound and a component that reacts with the diazo compound to form a color.
本発明による感熱記録材料は各種の複写シートや記録シ
ートなどとして使用される。The heat-sensitive recording material according to the present invention is used as various copying sheets, recording sheets, etc.
従来、感熱記録材料としては無色乃至淡色の電子供与性
染料前駆体と電子受容性化合物の呈色反応を利用したい
わゆるコ成分系感熱記録材料は特公昭４ｔｊ−／４ｔθ
３り号、特公昭グ３−ｌ／≦θ号、特開昭！？−／りＯ
♂♂６号などの公報に記載されでいるが、これらのコ成
分系感熱記録材料は一次発色性であり、現像処理が不要
である、取シ扱いが容易である、発色濃度が高い、種々
の発色色相のものが容易にできるなどの利点があり、利
用価値も大きいので各種の感熱記録材料のうち最も多く
利用されている。特に近年はファクシミリ、記録計、プ
リンター分野のみならず、ＰＯＳなどラベル分野での利
用にも拡大している。Conventionally, as a heat-sensitive recording material, a so-called co-component heat-sensitive recording material that utilizes a coloring reaction between a colorless or light-colored electron-donating dye precursor and an electron-accepting compound was published in the Japanese Patent Publication No. 4tj-/4tθ.
No. 3, Tokuko Shogu 3-l/≦θ, Tokukai Sho! ? -/riO
As described in publications such as ♂♂ No. 6, these component-based heat-sensitive recording materials are primary color-forming, do not require development processing, are easy to handle, have high color density, and have various properties. It has the advantage of being able to easily produce color hues of , and has great utility value, so it is the most widely used of the various heat-sensitive recording materials. Particularly in recent years, its use has expanded not only to the facsimile, recorder, and printer fields, but also to the label field such as POS.
しかしながら、近年ファクシミリを軽量化するためにフ
ァクシミリの紙搬送系部材の材質は従来の金属からプラ
スチックに代わってきた。そのため、従来の感熱記録シ
ートはストッカー、ローラー、トレイなどの搬送系と接
触して帯電し、静電気力によってシート同士またはシー
トと搬送系とがくっつき、いわゆる”ジャミング″を起
こし易いという問題があった。However, in recent years, in order to reduce the weight of facsimile machines, the material of the paper conveying system members of facsimile machines has been replaced by plastic instead of the conventional metal. For this reason, conventional heat-sensitive recording sheets become charged when they come into contact with conveyance systems such as stockers, rollers, and trays, and the electrostatic force causes the sheets to stick to each other or the sheets and the conveyance system, making it easy to cause so-called "jamming." .
〔問題点を解決するための手段及び作用〕氷見８Ａは、
上述した従来技術における問題点を解決し、さらにより
優れた特性を有する新規な感熱記録材料を提供すること
を目的とするものであって、その構成は、支持体上に無
色乃至淡色の染料前１駆体及び該染料前駆体と反応して
呈色する化合物を含有する感熱層あるいはジアゾ化合物
及び該ジアゾ化合物と反応して呈色する成分とを含有す
る感熱層が設けられている感熱記録材料において、Ｚｎ
Ｏ，ＴｉＯ２、Ｓ ｎ ０２、Ａｌ２Ｏ３、Ｉ ｎ ２
Ｏ３、Ｓ ｉ ０２、ＭｇＯ，ＢａＯ１Ｍ ｏ Ｏ３の
中から選ばれた少なくともｂ種の結晶性金属酸化物ある
いはこれらの複合酸化物微粒子を含有することを特徴と
する感熱記録材料である。[Means and actions for solving the problem] Himi 8A,
The purpose of the present invention is to solve the above-mentioned problems in the conventional technology and to provide a new heat-sensitive recording material having even more excellent properties. 1 precursor and a compound that develops color by reacting with the dye precursor, or a heat-sensitive layer containing a diazo compound and a component that develops color by reacting with the diazo compound. In, Zn
O, TiO2, S n 02, Al2O3, In 2
The present invention is a heat-sensitive recording material characterized by containing fine particles of at least B crystalline metal oxides selected from O3, Si02, MgO, and BaO1M o O3 or composite oxides thereof.
本発明に使用される結晶性の金属酸化物から成る導電性
微粒子は主として次のような方法により製造される。第
７に金属酸化物微粒子を焼成により作製し、導電性を向
上させる異種原子の存在下で熱処理する方法、第コに焼
成により金属酸化物微粒子を製造するときに導電性を向
上させる為の異種原子を共存させる方法、第３に焼成に
より金属微粒子を製造する際に雰囲気中のＰ素濃度を下
げて、酸素欠陥を導入する方法等が容易である。The conductive fine particles made of crystalline metal oxide used in the present invention are mainly produced by the following method. Seventh, a method in which metal oxide fine particles are produced by firing and then heat-treated in the presence of a different type of atom to improve conductivity; A third method is to allow atoms to coexist, and a third method is to lower the P element concentration in the atmosphere to introduce oxygen defects when producing metal fine particles by firing.
第１の方法では、微粒子表面の導電性を効果的に向上さ
せることができるが、熱処理中に粒子成長が起る可能性
があるので条件を選ぶ必要がある。In the first method, the conductivity of the surface of the fine particles can be effectively improved, but since particle growth may occur during the heat treatment, it is necessary to select the conditions.
また、熱処理は還元雰囲気で行う方が良い場合がある。Further, it may be better to perform the heat treatment in a reducing atmosphere.
第２の方法は、最も製造経費が少くて済むと思われるの
で好ましい。例えば、５ｎ０２の水和物であるβ−スズ
酸コロイド（無定形）を焼成炉中に噴霧してＳ ｎ ０
２微粒子を得る方法において、β−スズ酸コロイド中に
塩化アンチモン、硝酸アンチモン、酸化アンチモンの水
利物等を共存させておくと導電性Ｓ ｎ Ｏ２微粒子を
得ることができる。また別の例として５ｎｃｔ４、Ｔ
１ｃｔ４を酸化分解してＳ ｎ ０２、ＴｉＯ２を作製
する所謂気相法において、酸化分解の時に異種原子の塩
類を共存させると導電性のＳ ｎ Ｏ２、ＴｉＯ２を得
ることができる。また、金属の有機酸塩を加熱分解して
金属酸化物を得る方法において、加熱分解の際に異種金
属の塩類を共存させる方法もある。The second method is preferred because it appears to require the least manufacturing cost. For example, by spraying β-stannic acid colloid (amorphous), which is a hydrate of 5n02, into a firing furnace, S n 0
In the method for obtaining 2 fine particles, conductive SnO2 fine particles can be obtained by allowing antimony chloride, antimony nitrate, antimony oxide water reagents, etc. to coexist in the β-stannic acid colloid. Another example is 5nct4, T
In the so-called gas phase method in which 1ct4 is oxidatively decomposed to produce S n O2 and TiO2, conductive S n O2 and TiO2 can be obtained by allowing salts of different atoms to coexist during the oxidative decomposition. Furthermore, in the method of thermally decomposing an organic acid salt of a metal to obtain a metal oxide, there is also a method in which salts of different metals are allowed to coexist during the thermal decomposition.
第３の方法の例としては、酸素雰囲気中で金属を蒸発さ
せて金属酸化物微粒子を得る真空蒸発法において、酸素
量を不足気味にしておく方法、あるいは酸素を十分に供
給せずに金属、金属塩類を加熱する方法がある。As an example of the third method, in the vacuum evaporation method in which metal oxide particles are obtained by evaporating metal in an oxygen atmosphere, there is a method in which the amount of oxygen is slightly insufficient, or a method in which metal oxide particles are obtained by evaporating metal in an oxygen atmosphere. There is a method of heating metal salts.
本発明に使用される導電性粒子はできるだけ小さい方が
望ましいが、前記の粒子作製法によって得られた微細粒
子は、強く凝集してしまって、粗大粒子となってしまう
ことがある。これを避ける為に、導電性粒子を作る際に
、導電性向上には直接寄与しない微細な粒子を微粒子化
助剤として共存させると効果があることが多い。この目
的に利用される粒子としては、導電性を高める目的で作
られたのではない微細々金属酸化物粒子（たとえばＺｎ
Ｏ，ＴｉＯ２，５１０２、Ａｌ２Ｏ３、ＭｇＯ５Ｂ ａ
Ｏ，ＷＯ３、Ｍ ｏ ０３、Ｐ２Ｏ５等）、Ｂ ａ
Ｓ Ｏ４、ＳｒＳＯ４、ＣａＳＯ４、ＭｇＳＯ４等の硫
酸塩の微粒子、ＭｇＣＯ３、ＣａＣＯ３等の炭酸塩の微
粒子等がある。Although it is desirable that the conductive particles used in the present invention be as small as possible, the fine particles obtained by the above-mentioned particle preparation method may be strongly aggregated and become coarse particles. To avoid this, when producing conductive particles, it is often effective to coexist fine particles that do not directly contribute to improving conductivity as a micronization aid. Particles used for this purpose include fine metal oxide particles (for example, Zn
O, TiO2, 5102, Al2O3, MgO5B a
O, WO3, M o 03, P2O5, etc.), B a
There are fine particles of sulfates such as SO4, SrSO4, CaSO4, and MgSO4, and fine particles of carbonates such as MgCO3 and CaCO3.
ここに例として挙げた粒子は導電性微粒子と共にバイン
ダー中に分散させて用いることも可能である。また、大
部分の助剤用粒子及び粗大粒子を除く目的で、物理的あ
るいは化学的処理をすることもできる。すなわち得られ
た粒子を液体中に投入し、ボールミル、サンドミル等に
より粉砕した後、ｆ過、水簸あるいは遠心沈降等により
、極微細導電性粒子を選択的に捕集する方法、あるいは
上記のように粉砕した後、助剤粒子だけを溶解してしま
うという方法が効果的である。これらの操作を繰返した
り、また組合せることにより一段と効果的に極微細導電
性粒子が得られることは言うまでもない。粒子を分散す
る液体中に、分散助剤として界面活性剤、少量の本発明
に使用できるパインダー類あるいは少量のルイス酸、ル
イス塩基を加えておくと更に効果的に極微細導電性粒子
が得られる。The particles mentioned here as examples can also be used by being dispersed in a binder together with conductive fine particles. In addition, physical or chemical treatment can be performed to remove most of the auxiliary particles and coarse particles. That is, a method in which the obtained particles are put into a liquid, pulverized with a ball mill, sand mill, etc., and then ultrafine conductive particles are selectively collected by filtration, elutriation, centrifugal sedimentation, etc., or as described above. An effective method is to dissolve only the auxiliary particles after pulverizing the particles. It goes without saying that ultrafine conductive particles can be obtained even more effectively by repeating or combining these operations. Ultrafine conductive particles can be obtained even more effectively by adding a surfactant, a small amount of binders that can be used in the present invention, or a small amount of Lewis acid or Lewis base as a dispersion aid to the liquid in which the particles are dispersed. .
化学的処理を併用すれば、助剤粒子として使用できる粒
子は更に広い範囲に汎ることは自明のことである。It is obvious that if chemical treatment is used in combination, the range of particles that can be used as auxiliary particles will be wider.
次に、具体的な微粒子の作り方の例をあげる。Next, we will give an example of how to make specific particles.
塩化第二スズ水利物６！重量部と三塩化アンチモン／、
！重量部をエタノール７０００重量部に溶解し均一溶液
を得た。この溶液に／Ｎ水酸化ナトリウム水溶液を前記
溶液のｐＨが３になるまで滴下してコロイド状酸化第二
スズと酸化アンチモンの共沈澱を得た。得られた共沈澱
をｔｏｏｃに、２９時間放置し赤褐色のコロイド状沈澱
を得た。Tinnic chloride water supplies 6! Parts by weight and antimony trichloride/
! Parts by weight were dissolved in 7000 parts by weight of ethanol to obtain a homogeneous solution. A /N aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the solution became 3 to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left to stand for 29 hours to obtain a reddish brown colloidal precipitate.
赤褐色コロイド状沈澱を遠心分離により分離した。過剰
なイオンを除くため沈澱に水を加え遠心分離によって水
洗した。この操作を３回繰り返し過剰イオンを除去した
。A reddish-brown colloidal precipitate was separated by centrifugation. In order to remove excess ions, water was added to the precipitate and the precipitate was washed with water by centrifugation. This operation was repeated three times to remove excess ions.
過剰イオンを除去したコロイド状沈澱１０θ重量部を平
均粒径０．３μの硫酸バリウムｊＯ重量部及び水７００
０重量部に混合し９００°Ｃに加熱された焼成炉中に噴
霧し青味がかった平均粒径０、／μの酸化第二スズと硫
酸バリウムからなる粉末状混合物を得た。10θ parts by weight of the colloidal precipitate from which excess ions have been removed are mixed with 700 parts by weight of barium sulfate jO having an average particle size of 0.3μ and 700 parts by weight of water.
A powder mixture of stannic oxide and barium sulfate with an average particle diameter of 0.00000000000000000000000000000000000000000 parts by weight, which was sprayed into a firing furnace heated to 900°C, was obtained.
このようにして得られたＳ ｎ ０２粉末７０重量部と
ポリビニルアルコール（クランＰＶＡ１０ｔ）１０チ水
溶液５０重量部と水１００重量部からなる混合物をにイ
ンド・シェーカー（東洋精機製作新製）で７時間分散し
微粒子分散物が得られる。A mixture consisting of 70 parts by weight of the S n 02 powder thus obtained, 50 parts by weight of a 10% aqueous solution of polyvinyl alcohol (CranPVA 10t), and 100 parts by weight of water was heated in an India shaker (newly manufactured by Toyo Seiki Seisakusho) for 7 hours. It is dispersed to obtain a fine particle dispersion.
−化合物■
また、酸化亜鉛１００重量部、
ｋｌ （ＮＯ３）３・りＨ２Ｏの７０％水溶液！重量部
、水７００重量部からなる混合物を７０分間超音波照射
し均一分散液を得た。この分散液を／１００Ｃで７時間
乾燥後、／ｘ１０ ４Ｔｏｒｒ、６ｏｏ０Ｃで５分間焼
成し比抵抗−×１０２Ω−ａｍの酸化亜鉛を得た。粒径
はλμであった。この粒子をボールミルによシ粉砕して
平均粒径θ、７μの粒子を得た。- Compound ■ Also, 100 parts by weight of zinc oxide, 70% aqueous solution of kl (NO3)3 and H2O! A mixture consisting of 700 parts by weight of water and 700 parts by weight of water was irradiated with ultrasonic waves for 70 minutes to obtain a uniform dispersion. This dispersion was dried at /100C for 7 hours and then fired at /x104Torr and 6oo0C for 5 minutes to obtain zinc oxide having a specific resistance of -x102Ω-am. The particle size was λμ. These particles were ground in a ball mill to obtain particles with an average particle size θ of 7 μm.
このようにして得られたＺｎＯ粉末７０重量部、水／！
θ重量部からなる混合物をはインド・シェーカーで７時
間分散し均一な分散液を得た。この分散液を１１０００
ｒｐ、３０分遠心分離し粗大粒子を取り除いた。残った
上澄液をコ０ＱＱｒｐｍ、７時間遠心分離し微細粒子か
らなるＺｎＯペーストを得た。70 parts by weight of the ZnO powder thus obtained, water/!
The mixture consisting of θ parts by weight was dispersed in an India shaker for 7 hours to obtain a uniform dispersion. 11,000 ml of this dispersion
rp and centrifuged for 30 minutes to remove coarse particles. The remaining supernatant was centrifuged at 0QQrpm for 7 hours to obtain a ZnO paste consisting of fine particles.
上記ＺｎＯペースト１０重量部をポリビニルアルコール
／θチ水溶液２！重量部、水７００重量部に混合しペイ
ント・シェーカーで７時間分散すると微粒子分散物が得
られる。−微粒子−〇これらの粒子のうち、少なくとも
１種が使用される。これらの化合物は通常支持体／ｍ２
あたり０．００θ／〜／ｇ、好ましくはθ、Ｏ！〜０゜
！ｇ程度の割合の量で使用される。10 parts by weight of the above ZnO paste was mixed with 2 parts of a polyvinyl alcohol/θCH aqueous solution. Part by weight is mixed with 700 parts by weight of water and dispersed in a paint shaker for 7 hours to obtain a fine particle dispersion. -Fine particles- At least one type of these particles is used. These compounds are usually supported/m2
per 0.00θ/~/g, preferably θ, O! ~0°! It is used in an amount of about 100 g.
本発明の感熱記録材料は基本的には紙やプラスチックな
どの支持体、及びその上に設けられる感熱層からなる。The heat-sensitive recording material of the present invention basically consists of a support such as paper or plastic, and a heat-sensitive layer provided thereon.
感熱層の主成分となる無色乃至淡色の染料前駆体として
は、例えばトリアリールメタン系化合物、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、
スピロピラン系化合物、ジアゾ化合物などがある。そし
て各々具体例を挙げると、トリアリールメタン系化合物
としては、３゜３−ビス（ｐ−ジメチルアミノフェニル
）−１−ジメチルアミノフタリド（一般名：クリスタル
バイオレットラクトン）、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−（／、 ！−シメｆルインドール
ー３−イル）フタリド、ｊ −（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
）フタリドなどがあり、ジフェニルメタン系化合物とし
てはＱ、４ｔ−ビス−ジメチルアミノベンズヒドリンベ
ンジルエーテル、Ｎ−ハロフェニルロイコオーラミン、
Ｎ−ｘ、＜ｔ。Examples of colorless to light-colored dye precursors that are the main components of the heat-sensitive layer include triarylmethane compounds, diphenylmethane compounds, xanthine compounds, thiazine compounds,
These include spiropyran compounds and diazo compounds. To give specific examples, triarylmethane compounds include 3゜3-bis(p-dimethylaminophenyl)-1-dimethylaminophthalide (common name: crystal violet lactone), 3.3-bis( p-dimethylaminophenyl)-phthalide, 3-(p-dimethylaminophenyl)-3-(/, !-indol-3-yl)phthalide, j-(p-dimethylaminophenyl)-3-(,2 -methylindol-3-yl) phthalide, etc., and diphenylmethane compounds include Q, 4t-bis-dimethylaminobenzhydrin benzyl ether, N-halophenylleucoolamine,
N-x, <t.
！−トリクロロフェニルロイコオーラミンなどがあり、
キサンチン系化合物としては、ローダミン−Ｂ−アニリ
ノラクタム、ローダミン（ｐ−ニトリノ）ラクタム、λ
−（ジベンジルアミノ）フルオラン、ノーフェニルアミ
ノ−６−ジエチルアミノフルオラン１．２−（ｏ−クロ
ロアニリノ）−６−ジエチルアミノフルオラン１．２−
（３，４ｔ−ジクロルアニリノ）−６−ジエチルアミノ
フルオラン、ノーアニリノ−３−メチル−６−ピはリジ
ノフルオラン、λ−フェニル−６−ジニチルアミノフル
オランなどかあシ、スピロ化合物としては、３−メチル
−スピロ−ジナフトピラン、３−エチル−スピロ−ジナ
フトピラン、ｊ、Ｊ’−シクロロースビロージナフトピ
ラン、３−ベンジル−スピロ−ジナフトピラン、３−メ
チル−ナフト−（３−メトキ７ベンゾ）−スピロピラン
、３−プロピル−スピロ−ジベンゾピランなどがある。! - Trichlorophenyl leuco auramine, etc.
As xanthine compounds, rhodamine-B-anilinolactam, rhodamine (p-nitrino)lactam, λ
-(dibenzylamino)fluoran, nophenylamino-6-diethylaminofluoran 1.2-(o-chloroanilino)-6-diethylaminofluoran 1.2-
(3,4t-dichloroanilino)-6-diethylaminofluorane, noanilino-3-methyl-6-pi is lysinofluorane, λ-phenyl-6-dinithylaminofluorane, etc., and spiro compounds include 3-methyl -spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, j, J'-cyclolose biro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho-(3-methoxy7benzo)-spiropyran, 3 -Propyl-spiro-dibenzopyran and the like.
これらの化合物は単独で用いられ、あるいは一種以上が
併用される。These compounds may be used alone or in combination of one or more.
本発明において用いられるジアゾ化合物は一般式 Ａ
ｒＮ２ Ｘ
（式中、Ａｒは置換あるいは無置換の芳香族基を、Ｎ２
＋はジアゾニウム基を、Ｘ−は酸アニオンをそれぞれ表
す。）
によって表されるジアゾニウム塩であり、カップリング
成分とカップリング反応を起こして発色することかでき
るし、また光によって分解することができる化合物であ
る。The diazo compound used in the present invention has the general formula A
rN2
+ represents a diazonium group, and X- represents an acid anion. ) It is a diazonium salt represented by: It is a compound that can develop a color by causing a coupling reaction with a coupling component, and can be decomposed by light.
塩を形成するジアゾニウム化合物の具体例としては、ダ
ージアゾー／−ジメチルアミンベンゼン、タージアゾ−
／−ジエチルアミノベンゼン、＜２−シアソー／−ジプ
ロピルアミノベンゼン、ゲージ７ゾー／−メチルベンジ
ルアミノベンゼン、クージアゾ−／−ジエチルアミノベ
ンゼン、グーシアソー／−エチルヒドロキシエチつレア
ミノベンゼン、クージアゾ−７−シエチルアミンー３−
メトキシベンゼン、グージアゾ−／−ジメチルアミノー
コーメチルベンゼン、グーシアソー／−ペンゾイルアミ
ノーコ、！−ジェトキシベンゼン、グーシアソー／−モ
ルホリノベンゼン、ゲージ７：、’−／−モルホリノー
ｓ、ｒ−ジェトキシベンゼン、クージアゾ−／−モルホ
リノ−２，！−ジブトキシベンゼン、ａ−シアソー／−
アニリノベンゼン、グージアゾ−／−トルイルメル力プ
トーコ、！−ジェトキシベンゼン、グージアゾ−／、ク
ーメトキシベンゾイルアミノーコ、ｊ−ジェトキシベン
ゼンなどがある。Specific examples of diazonium compounds that form salts include terdiazo/-dimethylaminebenzene, terdiazo-
/-diethylaminobenzene, <2-thiazo/-dipropylaminobenzene, gauge 7so/-methylbenzylaminobenzene, kudiazo-/-diethylaminobenzene, gusiaso/-ethylhydroxyethylaminobenzene, kudiazo-7-ethylamine-3 −
Methoxybenzene, gousiazo-/-dimethylamino-co-methylbenzene, gousiazo-/-penzoylamino-co,! -jethoxybenzene, gusiazo/-morpholinobenzene, gauge 7:, '-/-morpholinos, r-jethoxybenzene, coudiazo-/-morpholino-2,! -dibutoxybenzene, a-thiaso/-
Anilinobenzene, gudiazo-/-toluylmer force putoko,! Examples include -jethoxybenzene, gudiazo-/, coumethoxybenzoylaminoco, and j-jethoxybenzene.
酸アニオンの具体例としては
ＣｎＦ２１＋ｌ５Ｏ３（ｍは３〜りの整数を表す）、Ｃ
ｎＦ２１＋ｌ５Ｏ３−（ｎは２〜ｌの整数を表す）、（
αＦｚｌ＋ｔＳＯｚ）ｚＣＨ−（ｌは／〜／♂の整数を
表す）、
６Ｈ５
ＢＦ４−１ＰＦ６−などがある。Specific examples of acid anions include CnF21+l5O3 (m represents an integer of 3 to 3), C
nF21+l5O3- (n represents an integer from 2 to l), (
αFzl+tSOz)zCH- (l represents an integer from / to /♂), 6H5BF4-1PF6-, etc.
本発明の感熱層に含有される顕色性感熱層としては下記
の一般式（ＩＶ）〜−一般式■）によって表される化合
物が好オしい。As the color-developing heat-sensitive layer contained in the heat-sensitive layer of the present invention, compounds represented by the following general formulas (IV) to -general formula (2) are preferred.
（式中、Ｘはｓ、ｏ、ＳＯ２、Ｎ２、及びＲ２は各々水
素原子あるいは炭素原子数／〜♂のアルキル基、または
Ｒ１とＲ２が結合して成るシクロアルキル基を、またＲ
は炭素原子数／〜？の直鎖または分岐したアルキル基ま
たはハロゲン原子を表す。）
（式中、Ｙは水素原子、メチル基あるいは水酸基を表し
、Ｒａｔｄ ＋ＣＨ２）ｍ−Ｃ６Ｈｓ−Ｚ、＋ＣＨ２）
ｎ−０−Ｃ６Ｈ５Ｚ、炭素原子数／〜６の直鎖または分
岐したアルキル基を、またｍ及びｎはθ〜３の整数を、
２は水素原子、ハロゲン原子またはメチル基を表す。）
（式中、Ｒ４はベンジル基、ハロゲン原子または炭素原
子数７〜！の直鎖または分岐したアルキル基で置換した
ベンジル基、炭素原子数／〜ｌの直鎖または分岐したア
ルキル基を表す。）（式中、Ｒ６、Ｒ７は炭素原子数７
〜とのアルキル基を表す。）
（式中、Ｒ８はエーテル結合を／〜！個を含むアルキレ
ン基を表す。）
上記一般式（１’／）〜（■）によって表される電子く
容性化合物以外の好ましい例としては、ビス−ヒドロキ
シクミルベンゼン類またはビス−ヒドロキシ−α−メチ
ルベンジルベンゼン類であり、具体例としては、／、４
ｔ−ビス−ｐ−ヒドロキシクミルベンゼン、／、グービ
ス−ｍ−ヒドロキシクミルベンゼン、７．３−ビス−ｐ
−ヒドロキシクミルベンゼン、／、３−ビス−ｍ−ヒド
ロキシクミルベンゼン、／、４ｔ−ビス−ローヒドロキ
シクミルベンゼン、／、４ｔ−ビス−ｐ−ヒドロキシ−
α−メチルベンジルベンゼンなどがあり、またサリチル
酸誘導体としては、３．！−ジーα−メチルベンジルサ
リチル酸、３．！−ジーｔ−ブチルサリチル酸、３−α
、α−ジメチルベンジルサリチル酸などのサリチル酸類
、またはその多価金属塩、特に亜鉛塩、アルミニウム塩
などがあり、その他ｐ−フェニルフェノール、３．！−
ジフェニルフェノール、クミルフェノールなどがある。(In the formula,
is the number of carbon atoms/~? represents a straight-chain or branched alkyl group or a halogen atom. ) (In the formula, Y represents a hydrogen atom, methyl group or hydroxyl group, Ratd +CH2)m-C6Hs-Z, +CH2)
n-0-C6H5Z, a straight chain or branched alkyl group having carbon atoms/~6, and m and n are integers of θ~3,
2 represents a hydrogen atom, a halogen atom, or a methyl group. (In the formula, R4 represents a benzyl group, a benzyl group substituted with a halogen atom or a straight-chain or branched alkyl group having 7 to 1 carbon atoms, or a straight-chain or branched alkyl group having 1 to 1 carbon atoms. ) (In the formula, R6 and R7 have 7 carbon atoms.
~ represents an alkyl group. ) (In the formula, R8 represents an alkylene group containing /~! ether bonds.) Preferred examples other than the electron-cavity compounds represented by the above general formulas (1'/) to (■) include: Bis-hydroxycumylbenzenes or bis-hydroxy-α-methylbenzylbenzenes, specific examples include /, 4
t-bis-p-hydroxycumylbenzene, /, goobis-m-hydroxycumylbenzene, 7.3-bis-p
-Hydroxycumylbenzene, /, 3-bis-m-hydroxycumylbenzene, /, 4t-bis-rohydroxycumylbenzene, /, 4t-bis-p-hydroxy-
There are α-methylbenzylbenzene, and salicylic acid derivatives include 3. ! -di-alpha-methylbenzylsalicylic acid, 3. ! -di-t-butylsalicylic acid, 3-α
, salicylic acids such as α-dimethylbenzylsalicylic acid, or polyvalent metal salts thereof, especially zinc salts, aluminum salts, etc., p-phenylphenol, 3. ! −
These include diphenylphenol and cumylphenol.
上記の顕色性化合物は、染色前駆体の！Ｑ〜７０００重
量％使用することが好ましく、さらに好ましくは７００
〜！００重量％である。The above color developing compound is a dye precursor! It is preferable to use Q to 7000% by weight, more preferably 700% by weight.
~! 00% by weight.
そしてこれらの化合物は単独で使用されてもよく、また
ＸＺ以上を併用してもよい。These compounds may be used alone or in combination with XZ or more.
染料前駆体がジアゾ化合物である場合、カップリング成
分としては、塩基性雰囲気でジアゾ化合物（ジアゾニウ
ム塩）とカップリングして色素を形成するものであり、
具体例としてはレゾルシン、フロログルシン、コ、３−
ジヒドロキシナフタレン−６−スルホン酸ナトリウム、
／−ヒドロキシ−２−ナフトエ酸モルホリノプロピルア
ミド、／。When the dye precursor is a diazo compound, the coupling component is one that couples with the diazo compound (diazonium salt) in a basic atmosphere to form a dye,
Specific examples include resorcin, phloroglucin, co, 3-
Sodium dihydroxynaphthalene-6-sulfonate,
/-Hydroxy-2-naphthoic acid morpholinopropylamide, /.
！−ジヒドロキシナフタレン、２．３−ジヒドロキシナ
フタレン、コ、３−ジヒドロキシ−に一スルファニルナ
フタレン、ノーヒドロキシ−３−ナフトエ酸モルホリノ
ゾロピルアミド、コーヒドロキ７−３−ナフトエ酸アニ
リド、２−ヒドロキシ−３−ナフトエ酸−２′−メチル
アニリド、λ−ヒドロキシー３−ナフトエ酸エタノール
アミド、−一ヒドロキシー３−ナフトエ酸オクチルアミ
ド、コーヒドロキシー３−ナフトエｅ−Ｎ−）”デンル
オキシプロピルアミド、コーヒドロキシー３−ナフトエ
酸テトラデシルアミド、アセトアニリド、ベンゾイルア
セトアニリド、／−フェニル−３−メチル−よ一ピラゾ
ロン、／ （−２’ ＋ ４” ＋ ４ ’−トリク
ロロフェニル）−３−ベンズアミド−！−ピラゾロン、
／ （−２’ ＊ ”’ ＋乙′−トリクロロフ
ェニル）−３−アニリノ−よ−ヒラゾロン、／−フェニ
ル−３−フェニルアセトアニリド−！−ピラゾロンなど
がある。さらにこれらのカップリング成分を２種以上併
用することによって任意の色調の画像を得ることができ
る。! -dihydroxynaphthalene, 2,3-dihydroxynaphthalene, co-,3-dihydroxy-mono-sulfanylnaphthalene, non-hydroxy-3-naphthoic acid morpholinozolopyramide, co-hydroxy-7-3-naphthoic acid anilide, 2-hydroxy-3-naphthoic acid Acid-2'-methylanilide, λ-hydroxy-3-naphthoic acid ethanolamide, -monohydroxy-3-naphthoic acid octylamide, co-hydroxy-3-naphthoic acid e-N-)denyloxypropylamide, co-hydroxy-3-naphthoic acid ethanolamide -Naphthoic acid tetradecylamide, acetanilide, benzoylacetanilide, /-phenyl-3-methyl-yoichipyrazolone, / (-2' + 4'' + 4'-trichlorophenyl)-3-benzamide-! -pyrazolone,
/ (-2' * ”' + Otsu'-trichlorophenyl)-3-anilino-yirazolone, /-phenyl-3-phenylacetanilide-!-pyrazolone, etc.Furthermore, two or more of these coupling components are used. By using them together, it is possible to obtain an image of any color tone.
本発明の発色助剤としては、水難溶性乃至水不溶性の塩
基性物質や加熱によりアルカリを発生する物質が用いら
れる。As the color development aid of the present invention, a slightly water-soluble or water-insoluble basic substance or a substance that generates an alkali upon heating is used.
発色助剤としては、無機及び有機アンモニウム塩、有機
アミン、アミド、尿素やチオ尿素及びその誘導体、チア
ゾール類、ピロール類、ピリミジン類、ピはラジン類、
グアニジン類、インドール類、イミダゾール類、イミダ
シリン類、トリアゾール類、モルホリン類、ピはリジン
類、アミジン類、ホルムアジン類、ピリジン類などの含
窒素化合物がある。Coloring aids include inorganic and organic ammonium salts, organic amines, amides, urea and thiourea and their derivatives, thiazoles, pyrroles, pyrimidines, pyrazines,
There are nitrogen-containing compounds such as guanidines, indoles, imidazoles, imidacillines, triazoles, morpholines, lysines, amidines, formazines, and pyridines.
本発明に係る感熱記録材料において、その熱応答性を改
良するために、熱可融性物質を感熱層に含有させること
ができる。In the heat-sensitive recording material according to the present invention, a heat-fusible substance can be contained in the heat-sensitive layer in order to improve its thermal responsiveness.
具体的には、ｐ−ベンジルオキシ安息香酸ベンジル、β
−ナフチルベンジルエーテル、ニアリン酸アミド、パル
ミチン酸アミド、Ｎ−フェニルニアリン酸アミド、Ｎ−
ステアリル尿素、β−ナフトエ酸フェニルエステル、／
−ヒドロキシ−Ｊ −ナフトエ酸フェニルエステル、β
−ナフトール（ｐ−クロロベンジル）エーテル、β−ナ
フトール（ｐ−メチルベンジル）エーテル、α−ナフチ
ルベンジルエーテル、／、Ｑ−７’タンジオ−に−ｐ−
メチルフェニルエーテル、／、クープロノぐフジオール
−ｐ−メチルフェニルエーテル、／、４を一フタンジオ
ールーｐ−イソプロピルフェニルエーテル、７．４ｔ−
ブタンジオール−ｐ−ｔ−オクチルフェニルエーテル、
−一フエノキシー／−ｐ−トリルオキシエタン、／−フ
ェノキシ−λ−（４を一エチルフェノキシ）エタン、／
−フエノキシ−２御（ｇ−クロロフェノキシ）エタン、
／。Specifically, benzyl p-benzyloxybenzoate, β
-Naphthylbenzyl ether, niaric acid amide, palmitic acid amide, N-phenyl niaric acid amide, N-
Stearylurea, β-naphthoic acid phenyl ester, /
-Hydroxy-J-naphthoic acid phenyl ester, β
-naphthol (p-chlorobenzyl) ether, β-naphthol (p-methylbenzyl) ether, α-naphthylbenzyl ether, /, Q-7' tandio-p-
Methyl phenyl ether, /, cupronofufudiol-p-methylphenyl ether, /, 4 to 1 phthanediol-p-isopropylphenyl ether, 7.4t-
butanediol-pt-octylphenyl ether,
-monophenoxy/-p-tolyloxyethane, /-phenoxy-λ-(4 to monoethylphenoxy)ethane, /
-phenoxy-2-(g-chlorophenoxy)ethane,
/.
グーブタンジオールフェニルエーテルなどがある。Examples include goobutanediol phenyl ether.
前記熱可融性物質は単独であるいは２種以上を併用して
もよく、十分な熱応答性を得るためには電子受容性化合
物に対して／θ〜λ００重−１ｔ％の量で使用すること
が好ましく、さらに好ましくは２Ｏ〜／ｊＯ重量％で使
用することである。The thermofusible substance may be used alone or in combination of two or more, and in order to obtain sufficient thermal responsiveness, it is used in an amount of /θ to λ00 weight -1 t% relative to the electron-accepting compound. It is preferable to use it in an amount of 2O to /jO weight %.
電子供与性染料前駆体と電子受容性化合物を用いた二成
分系の感熱記録材料においては一般に生成した記録画像
が湿度、熱などの外部条件の影響により消色する傾向が
ある。In a two-component heat-sensitive recording material using an electron-donating dye precursor and an electron-accepting compound, the recorded image generally tends to fade due to the influence of external conditions such as humidity and heat.
本願発明に係る感熱記録材料において、かかる消色を防
止し、生成画像を堅牢化するために感熱層中に消色を防
止する化合物を含有させることが好ましい。In the heat-sensitive recording material according to the present invention, it is preferable to include a compound that prevents color fading in the heat-sensitive layer in order to prevent such color fading and make the generated image more robust.
消色防止剤としては、フェノール誘導体、特にヒンダー
ドフェノール化合物が有効である。Phenol derivatives, especially hindered phenol compounds, are effective as anti-fading agents.
フェノール化合物の使用量は、電子受容性化合物に対し
て７〜２Ｏ０重量％使用することが好ましく、より好ま
しくは！〜よ０重＠Ｓ使用することである。The amount of the phenol compound to be used is preferably 7 to 200% by weight, more preferably! ~Yo 0 weight @S is to be used.
本発明の感熱層の接着剤として用いられるポリマーとし
ては、ポリビニルアルコール、カルボキシ変性ポリビニ
ルアルコール、シリカ変性ポリビニルアルコール、メチ
ルセルロース、カルボキシメチルセルロース、ヒドロキ
シメチルセルロース、澱粉類、ゼラチン、アラビアゴム
、カゼイン、スチレン−無水マレイン酸共重合体加水分
解物、スチレン−無ホマレインｅ共ｘ合体ハーフェステ
ル加水分解物、インブチレン−無水マレイン酸共重合体
加水分解物、ポリアクリルアミド誘導体、ポリビニルピ
ロリドン、ポリスチレンスルホン酸ナトリウム、アルギ
ン酸ナトリウムなどの水溶性高分子及びスチレン−ブタ
ジェンゴムラテックス、アクリロニトリル−ブタジェン
ゴムラテックス、アクリル酸メチル−ブタジェンゴムラ
テックス、ポリ酢酸ビニルエマルジョンなどの水不溶性
ポリマーを併用することができる。Polymers used as adhesives for the heat-sensitive layer of the present invention include polyvinyl alcohol, carboxy-modified polyvinyl alcohol, silica-modified polyvinyl alcohol, methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, starches, gelatin, gum arabic, casein, styrene-maleic anhydride. Acid copolymer hydrolyzate, styrene-anhomalein e co-x combination Hafestel hydrolyzate, inbutylene-maleic anhydride copolymer hydrolyzate, polyacrylamide derivatives, polyvinylpyrrolidone, sodium polystyrene sulfonate, sodium alginate, etc. Water-soluble polymers and water-insoluble polymers such as styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, methyl acrylate-butadiene rubber latex, and polyvinyl acetate emulsion can be used in combination.
本発明の感熱記録材料の感熱１中には必要によシ顔料、
金属石鹸、ワックス、界面活性剤、架橋剤などを添加す
ることができる。In the heat-sensitive recording material of the present invention, the heat-sensitive pigment is necessary.
Metal soaps, waxes, surfactants, crosslinking agents, etc. can be added.
顔料には、酸化亜鉛、炭酸カルシウム、硫酸バリウム、
酸化チタン、リトポン、メルク、蝋石、カオリン、水酸
化アルミニウム、シリカ、非晶質シリカなどがあり、金
属石鹸には、ステアリン酸亜鉛、ステアリン酸カルシウ
ム、ステアリン酸アルミニウムなどの高級脂肪酸金属塩
のエマルジョンなどかあυ、ワックスには、パラフィン
ワックスマイクロクリスタリンワックス、カルナバワッ
クス、メチロールステアロアミド、ポリエチレンワック
スなどのエマルジョンがあり、界面活性剤には、スルホ
こはく酸系のアルカリ金属塩弗素含有界面活性剤などか
あシ、架橋剤には、ポリマーの種類に応じて適宜選択す
ることが必要であるが、ポリエチレンイミンなどのポリ
アミン系、グルタルアルデヒドなどのジアルデヒド類、
メチロールメラミンなどのポリメチロール化合物、エポ
キシ化合物、ジュルニウム塩類、その他の無機塩類があ
る。本発明においては、特にグルタルアルデヒド、グリ
オキザールジメトキシ尿素、コ、３−ジヒドロキシー／
、Ｑ−ジオキサンなどのジアルデヒド類が好ましい。Pigments include zinc oxide, calcium carbonate, barium sulfate,
Titanium oxide, lithopone, Merck, Rouseki, kaolin, aluminum hydroxide, silica, amorphous silica, etc. Metal soaps include emulsions of higher fatty acid metal salts such as zinc stearate, calcium stearate, and aluminum stearate. Waxes include emulsions such as paraffin wax microcrystalline wax, carnauba wax, methylolstearamide, and polyethylene wax, and surfactants include sulfosuccinic acid-based alkali metal salt fluorine-containing surfactants. The crosslinking agent must be selected appropriately depending on the type of polymer, but polyamines such as polyethyleneimine, dialdehydes such as glutaraldehyde,
Examples include polymethylol compounds such as methylol melamine, epoxy compounds, jurnium salts, and other inorganic salts. In the present invention, in particular, glutaraldehyde, glyoxaldimethoxyurea, co-,3-dihydroxy-
, Q-dioxane and other dialdehydes are preferred.
これらの添加剤の添加量は、感熱層のポリマーに対して
０．１〜７１重量％、好ましくは７〜７０重量％である
。The amount of these additives added is 0.1 to 71% by weight, preferably 7 to 70% by weight, based on the polymer of the heat-sensitive layer.
また感熱層の乾燥塗布量は７〜１０ｇ／ｍ２の範囲内の
量であることが好ましい。Further, the dry coating amount of the heat-sensitive layer is preferably within the range of 7 to 10 g/m<2>.
本発明の感熱記録材料の感熱層の上には、所望により保
護層が設けられる。保護層の主成分は皮膜形成性のポリ
マーである。A protective layer may be provided on the heat-sensitive layer of the heat-sensitive recording material of the present invention, if desired. The main component of the protective layer is a film-forming polymer.
かかる保護層に使用されるポリマーとしては、メチルセ
ルロース、カルボキシメチルセルロース、ヒドロキシメ
チルセルロース、澱粉類、ゼラチン、アラビアゴム、カ
ゼイン、スチレン−無水マレイン酸共重合体加水分解物
、スチレン−無水マレイン酸共重合体・・−７工ステル
加水分解物、インブチレン−無水マレイン酸共重合体加
水分解物、ポリビニルアルコール、シリカ変性ポリビニ
ルアルコール、カルボキシ変性ポリビニルアルコーノヘ
ポリアクリルアミド誘導体、ポリビニルピロリドン、ポ
リスチレンスルホン酸ナトリウム、アルギン酸ナトリウ
ムなどの水溶性高分子及びスチレン−ブタジェンゴムラ
テックス、アクリロニトリル−ブタジェンゴムラテック
ス、アクリル酸メチル−ブタジェンゴムラテックス、ポ
リ酢酸ビニルエマルジョンなどの水不溶性ポリマーがあ
り、これらのポリマーは単独で使用され、あるいは２種
以上を併用することもできる。Polymers used in such a protective layer include methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, starches, gelatin, gum arabic, casein, styrene-maleic anhydride copolymer hydrolyzate, styrene-maleic anhydride copolymer, etc.・-7-ester hydrolyzate, inbutylene-maleic anhydride copolymer hydrolyzate, polyvinyl alcohol, silica-modified polyvinyl alcohol, carboxy-modified polyvinylalconohepoxyacrylamide derivative, polyvinylpyrrolidone, sodium polystyrene sulfonate, sodium alginate, etc. There are water-soluble polymers such as styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, methyl acrylate-butadiene rubber latex, polyvinyl acetate emulsion, etc., and these polymers are used alone, Alternatively, two or more types can also be used in combination.
上記の保護層中には印字時のサーマルヘッドとのマツチ
ング性の向上、保護層の耐水性の向上などの目的で顔料
、金属石鹸、ワックス、架橋剤などが添加される。Pigments, metal soaps, wax, crosslinking agents, etc. are added to the above-mentioned protective layer for the purpose of improving the matching property with the thermal head during printing and improving the water resistance of the protective layer.
顔料には、酸化亜鉛、炭酸カルシウム、硫酸バリウム、
酸化チタン、リトポン、タルク、蝋石、カオリン、水酸
化アルミニウム、シリカ、非晶質シリカなどがあり、そ
れらの添加量は、ポリマーの総重量のＯ，Ｓ〜ｑ倍、特
に好ましくはθ、！〜３．夕倍の量である。上記の範囲
の下限以下の量ではヘッドマツチング性の向上に無効で
あり、上限以上の量では感熱記録材料の感度の低下が著
しくその商品価値を損ねる。Pigments include zinc oxide, calcium carbonate, barium sulfate,
Examples include titanium oxide, lithopone, talc, Rouseki, kaolin, aluminum hydroxide, silica, amorphous silica, etc., and the amount of addition thereof is O, S to q times the total weight of the polymer, particularly preferably θ,! ~3. It is the amount of Yube. If the amount is below the lower limit of the above range, it is ineffective in improving head matching properties, and if the amount is above the upper limit, the sensitivity of the heat-sensitive recording material will be significantly reduced, impairing its commercial value.
金属石鹸にはステアリン酸亜鉛、ステアリン酸カルシウ
ム、ステアリン酸アルミニウムなどの高級脂肪酸金属塩
のエマルジョンなどがあシ、保護層全重量の０．３〜２
Ｏ重量％、好ましくは／〜１０ＭＵｋ％の割合の量で添
加される。ワックスには、パラフィンワックス、マイク
ロクリスタリンワックス、カルナバワックス、メチロー
ルステアロアミド、ポリエチレンワックスなどのエマル
ジョンがあり、保護層全重量の７〜２Ｏ重量％、好まし
くは／〜１０１Ｊ（量チの割合の量で添加される。Metal soaps include emulsions of higher fatty acid metal salts such as zinc stearate, calcium stearate, and aluminum stearate, and contain 0.3 to 2 of the total weight of the protective layer.
O is added in an amount of % by weight, preferably a proportion of /~10 MUk%. Waxes include emulsions such as paraffin wax, microcrystalline wax, carnauba wax, methylolstearamide, polyethylene wax, etc., and the amount is 7 to 20% by weight of the total weight of the protective layer, preferably / to 101J (amount of It is added in
また感熱層上に保ｉ層を形成させるに際して、均一な塗
布層とするため保護層形成用塗布液には界面活性剤が添
加される。界面活性剤にはスルホこはく酸系のアルカリ
金属塩、弗素含有界面活性剤などがあシ、具体的には、
ジー（−一エチルヘキシル）スルホこはく酸、ジー（ｎ
−ヘキシル）スルホこはく酸などのナトリウム塩または
アンモニウム塩などがあるが、一般にアニオン系界面活
性剤であればいかなるものでも有効である。Further, when forming the i-retaining layer on the heat-sensitive layer, a surfactant is added to the coating solution for forming the protective layer in order to form a uniform coating layer. Surfactants include sulfosuccinic acid-based alkali metal salts, fluorine-containing surfactants, etc. Specifically,
Di(-monoethylhexyl)sulfosuccinic acid, Di(n
Examples include sodium salts or ammonium salts such as -hexyl)sulfosuccinic acid, but generally any anionic surfactant is effective.
保護層の乾燥塗布量はＯ１！〜／θｇ／ ｍ２程度が好
ましく、特に／〜！ ｇ ／ ｍ ２程度の量が好まし
い。The dry coating amount of the protective layer is O1! ~/θg/m2 is preferable, especially /~! Amounts of the order of g/m2 are preferred.
また、支持体の反対側にバック層を設けることもできる
。バック層には、保護層の場合と同様の類のものが塗布
される。Moreover, a back layer can also be provided on the opposite side of the support. The back layer is coated with the same kind of material as the protective layer.
本発明による結晶性金属酸化物又は複合酸化物粒子は、
支持体、感熱層、保護層、バンク層のいづれに含有せし
めてもよい。The crystalline metal oxide or composite oxide particles according to the present invention are
It may be contained in any of the support, heat-sensitive layer, protective layer, and bank layer.
以下、本発明をその実施例に基づいてより詳細にかつ具
体的に説明する。なお、各実施例中の”チ″は“重量％
”、“部”は“重量部″である。Hereinafter, the present invention will be described in more detail and specifically based on examples thereof. In addition, "chi" in each example means "weight%"
”, “parts” are “parts by weight”.
実施例／
クリスタルバイオレットラクトン、パラヒドロキシ安息
香酸ベンジル、ステアリン酸アミド、／。Examples/Crystal violet lactone, benzyl parahydroxybenzoate, stearamide,/.
／、！−トリス（２−メチル−グーヒドロキシ−５−ｔ
−ブチルフェニル）ブタン各々コθｇを！チポリビニル
アルコール（クラレ■製、商品名：ＰＶＡ／Ｑｊ）水溶
液７００ｇとともに一昼夜ポールミルで分散処理し、そ
れぞれ固形成分の体積平均粒径が３μ以下の分散液を調
製した。/,! -tris(2-methyl-guhydroxy-5-t
-butylphenyl)butane each θg! Dispersion treatment was carried out with 700 g of an aqueous solution of tipolyvinyl alcohol (manufactured by Kuraray ■, trade name: PVA/Qj) in a Pall mill overnight to prepare dispersions in which the volume average particle size of the solid components was 3 μm or less.
他方、顔料１０／ｇをヘキサメタ燐酸ンーダＯ０ｊ％溶
液／ｌＯｇと共にホモジナイザーで分散し、顔料分散液
を調製した。On the other hand, a pigment dispersion liquid was prepared by dispersing 10/g of pigment with a 0j% hexametaphosphoric acid solution/lOg using a homogenizer.
上述のように調製した各分散液、クリスタルバイオレッ
トラクトン分散液ｊ ｇ ％バラヒドロキシ安息香酸ベ
ンジル分散液／θｇ、ステアリン酸アミド分散液！ｇ、
／、／、３−トリス（２−メチル−ｑ−ヒドロキシ−ｔ
−ｔ−ブチルフェニル）ブタン分散液２ｇ、顔料分散液
！ｇの割合で混合し、さらに２／チステアリン酸亜鉛の
エマルジョン３ｇと、４ｔ％２．３−ジヒドロキシー！
−メチル−７，４ｔ−ジオギサン／θｇ、２％ジ（２−
エチルヘキシル）−スルホこはく酸ナトリウム水溶液！
ｇを添加して得られた塗布液を坪ｆｉ６０ｇ／ｍ２の上
質紙上にワイヤーバーで乾燥塗布量！ｇ／ｍ２となるよ
うに塗布し、温度ｊ０°Ｃのオーブン内で乾燥して感熱
層を形成させた。Each dispersion prepared as described above, crystal violet lactone dispersion j g% rose hydroxybenzoate benzyl dispersion/θg, stearamide dispersion! g,
/, /, 3-tris(2-methyl-q-hydroxy-t
-t-butylphenyl)butane dispersion 2g, pigment dispersion! g of 2/zinc stearate emulsion and 4t% 2.3-dihydroxy!
-Methyl-7,4t-diogysan/θg, 2% di(2-
ethylhexyl)-sodium sulfosuccinate aqueous solution!
Dry coating amount of the coating solution obtained by adding g with a wire bar on high-quality paper with a tsubo fi of 60 g/m2! g/m2 and dried in an oven at a temperature of 0°C to form a heat-sensitive layer.
さらに得られた感熱層上に下記の組成の塗布液をワイヤ
ーバーで乾燥型ｉ−ｊ ｇ ／ｍ ２となるように塗布
し、温度！０°Ｃのオープン内で乾燥し、保護層を形成
させた。Furthermore, a coating solution having the composition shown below was applied onto the obtained heat-sensitive layer using a wire bar so as to give a dry coating of i-j g/m 2 , and the temperature was determined. It was dried in an open chamber at 0°C to form a protective layer.
さらに支持体の裏面に下記の組成の混合溶液をワイヤー
バーで乾燥重量がｊｇ／ｍ２となるように塗布し、温度
！００Ｃのオープンで乾燥してバック層を形成させた。Furthermore, a mixed solution of the following composition was applied to the back side of the support using a wire bar so that the dry weight was jg/m2, and the temperature was determined. A back layer was formed by drying in the open at 00C.
以上のようにして感熱記録材料試料屋／が得られた。A heat-sensitive recording material sample was obtained as described above.
実施例コ
実施例／におけるバック層の塗布液組成を下記の組成と
し、塗布乾燥重量を３ｇ／ｍ２とし、他は実施例／の場
合と同様にして実施し、感熱記録材料試料屋λを作成し
た。Example The coating liquid composition of the back layer in Example / was as shown below, the coating dry weight was 3 g/m2, and the rest was carried out in the same manner as in Example / to create a heat-sensitive recording material sample λ. did.
実施例３
実施例／における保護層の塗布液組成を下記の組成とし
、かつその塗布乾燥重量をＪｇ／ｍ２とし、さらにバッ
ク層を塗設せず、他は実施例／の場合と同様にして実施
し、感熱記録材料盃３を作成した。Example 3 The coating liquid composition of the protective layer in Example 1 was as follows, and the coating dry weight was Jg/m2, and the back layer was not coated, and the other conditions were the same as in Example 3. A thermosensitive recording material cup 3 was prepared.
実施例ｑ
実施例コにおける保護層を塗布せず、他は実施例−の場
合と同様にして実施し、感熱記録材料試料を作成した。Example q A heat-sensitive recording material sample was prepared in the same manner as in Example 1, except that the protective layer in Example 1 was not applied.
比較例／
実施例／中のバック層の塗布液組成における本発明によ
る成分を除き、他は実施例／の場合と同様にして実施し
、感熱記録材料試料＆！を作成した。Comparative Example/Example/A thermosensitive recording material sample &! It was created.
比較例２
実施例／におけるバンク層を塗設せず、他は実施例／の
場合と同様にして実施し、感熱記録材料試料乙を作成し
た。Comparative Example 2 A thermosensitive recording material sample B was prepared in the same manner as in Example 2, except that the bank layer in Example 2 was not applied.
比較例３
実施例／におけるバック層及び保護層を塗設せず、他は
実施例／の場合と同様にして実施し、感熱記録材料試料
７を作成した。Comparative Example 3 Heat-sensitive recording material sample 7 was prepared in the same manner as in Example 1, except that the back layer and protective layer in Example 1 were not applied.
比較例り
実施例／中のバック層の塗布液組成における本発明によ
るコ成分を除いてバック層を塗設し、かつ保護層は塗設
せず、他は実施例／の場合と同様にして実施し、感熱記
録材料試料洗♂を作成した。Comparative Example: A back layer was coated except for the co-component according to the present invention in the coating solution composition of the back layer in Example/, and a protective layer was not coated, and the other conditions were the same as in Example/. The test was carried out, and a sample of heat-sensitive recording material was prepared.
以上各実施例、各比較例において作成された試料につい
て市販のファクシミリのうち特にジャミングを起こし易
いファクシミリ、機種Ｊ／及び機種Ｊ２を使用し、画面
のコ！チが黒色のテスト・耐ターンを１００枚を連続し
て印字して何枚ジャミングを起こすかを調べた。印字は
温度１００ｃ、相対湿度／！チの条件で行い、ジャミン
グが生じた場合はその用紙を除去して印字テストを続け
た。For the samples created in each of the Examples and Comparative Examples above, we used commercially available facsimile machines, Model J/ and Model J2, which are particularly prone to jamming, and the following screen images were used: We printed 100 sheets of a black test/turn resistant sheet in succession to find out how many sheets jammed. Printing is at a temperature of 100c and relative humidity/! If jamming occurred, the paper was removed and the printing test continued.
その結果、第１表に記載されているような結果が得られ
た。As a result, the results shown in Table 1 were obtained.
第１表
第１表に示された結果から、本発明になる感熱記録材料
である各実施例における試料は、比較例における試料に
比べて５７機種及び５２機種の両方でジャミングの発生
枚数が少ないことが明瞭であった。Table 1 From the results shown in Table 1, the samples in each example, which are the heat-sensitive recording materials of the present invention, had fewer jammed sheets than the samples in the comparative example in both 57 models and 52 models. That was clear.
Claims (1)
と反応して呈色する化合物を含有する感熱層あるいはジ
アゾ化合物及び該ジアゾ化合物と反応して呈色する成分
とを含有する感熱層が設けられている感熱記録材料にお
いて、ＺｎＯ、ＴｉＯ＿２、ＳｎＯ＿２、Ａｌ＿２Ｏ＿
３、Ｉｎ＿２Ｏ＿３、ＳｉＯ＿２、ＭｇＯ、ＢａＯ、Ｍ
ｏＯ＿３の中から選ばれた少なくとも１種の結晶性金属
酸化物あるいはこれらの複合酸化物微粒子を含有するこ
とを特徴とする感熱記録材料。A heat-sensitive layer containing a colorless to light-colored dye precursor and a compound that develops a color by reacting with the dye precursor, or a heat-sensitive layer containing a diazo compound and a component that develops a color by reacting with the diazo compound on a support. In the heat-sensitive recording material provided with ZnO, TiO_2, SnO_2, Al_2O_
3, In_2O_3, SiO_2, MgO, BaO, M
A heat-sensitive recording material characterized by containing at least one crystalline metal oxide selected from oO_3 or fine particles of a composite oxide thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61271116A JPS63125389A (en) | 1986-11-14 | 1986-11-14 | Thermal recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61271116A JPS63125389A (en) | 1986-11-14 | 1986-11-14 | Thermal recording material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63125389A true JPS63125389A (en) | 1988-05-28 |
Family
ID=17495554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61271116A Pending JPS63125389A (en) | 1986-11-14 | 1986-11-14 | Thermal recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63125389A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110511024A (en) * | 2019-09-05 | 2019-11-29 | 昆明理工大学 | A kind of MoO based on thermo-chromic effects3The application of ceramics |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS544142A (en) * | 1977-06-13 | 1979-01-12 | Tomoegawa Paper Co Ltd | Heat sensitive recording medium |
| JPS57156292A (en) * | 1981-03-24 | 1982-09-27 | Fuji Xerox Co Ltd | Heat-sensitive recording sheet |
| JPS57172345A (en) * | 1981-04-17 | 1982-10-23 | Mitsubishi Paper Mills Ltd | Improved electrostatic type clay paper |
| JPS57208294A (en) * | 1981-06-19 | 1982-12-21 | Ricoh Co Ltd | Diazo base heat-sensitive recording material |
| JPS59174389A (en) * | 1983-03-23 | 1984-10-02 | Ricoh Co Ltd | Thermal recording material |
| JPS6233467B2 (en) * | 1978-11-09 | 1987-07-21 | Kyoshi Urushibata |
-
1986
- 1986-11-14 JP JP61271116A patent/JPS63125389A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS544142A (en) * | 1977-06-13 | 1979-01-12 | Tomoegawa Paper Co Ltd | Heat sensitive recording medium |
| JPS6233467B2 (en) * | 1978-11-09 | 1987-07-21 | Kyoshi Urushibata | |
| JPS57156292A (en) * | 1981-03-24 | 1982-09-27 | Fuji Xerox Co Ltd | Heat-sensitive recording sheet |
| JPS57172345A (en) * | 1981-04-17 | 1982-10-23 | Mitsubishi Paper Mills Ltd | Improved electrostatic type clay paper |
| JPS57208294A (en) * | 1981-06-19 | 1982-12-21 | Ricoh Co Ltd | Diazo base heat-sensitive recording material |
| JPS59174389A (en) * | 1983-03-23 | 1984-10-02 | Ricoh Co Ltd | Thermal recording material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110511024A (en) * | 2019-09-05 | 2019-11-29 | 昆明理工大学 | A kind of MoO based on thermo-chromic effects3The application of ceramics |
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