JPH0664331A - Heat-sensitive recording medium - Google Patents
Heat-sensitive recording mediumInfo
- Publication number
- JPH0664331A JPH0664331A JP4242777A JP24277792A JPH0664331A JP H0664331 A JPH0664331 A JP H0664331A JP 4242777 A JP4242777 A JP 4242777A JP 24277792 A JP24277792 A JP 24277792A JP H0664331 A JPH0664331 A JP H0664331A
- Authority
- JP
- Japan
- Prior art keywords
- phenolic compound
- heat
- positions
- color
- hydroxyl group
- 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.)
- Granted
Links
- 150000002989 phenols Chemical class 0.000 claims abstract description 32
- -1 gallic acid ester Chemical class 0.000 claims abstract description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 28
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 20
- 239000000194 fatty acid Substances 0.000 claims abstract description 20
- 229930195729 fatty acid Natural products 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 8
- LNTHITQWFMADLM-UHFFFAOYSA-N anhydrous gallic acid Natural products OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229940114055 beta-resorcylic acid Drugs 0.000 claims abstract description 3
- UIAFKZKHHVMJGS-UHFFFAOYSA-N beta-resorcylic acid Natural products OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229940074391 gallic acid Drugs 0.000 claims abstract description 3
- 235000004515 gallic acid Nutrition 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910000462 iron(III) oxide hydroxide Inorganic materials 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 10
- 238000003860 storage Methods 0.000 abstract description 6
- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 22
- 238000004040 coloring Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000003232 water-soluble binding agent Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- NENFFQGUGLZPPY-UHFFFAOYSA-N benzyl 2,4-dihydroxybenzoate Chemical compound OC1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 NENFFQGUGLZPPY-UHFFFAOYSA-N 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
- 239000013522 chelant Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004615 ingredient Substances 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
- 229920000126 latex Polymers 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- FBSFWRHWHYMIOG-UHFFFAOYSA-N methyl 3,4,5-trihydroxybenzoate Chemical compound COC(=O)C1=CC(O)=C(O)C(O)=C1 FBSFWRHWHYMIOG-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- BRNPAEUKZMBRLQ-UHFFFAOYSA-N octadecyl 3,4,5-trihydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 BRNPAEUKZMBRLQ-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ASBDAQCANIOGJE-UHFFFAOYSA-N (4-chlorophenyl)methyl 2,4-dihydroxy-6-propylbenzoate Chemical compound CCCC1=CC(O)=CC(O)=C1C(=O)OCC1=CC=C(Cl)C=C1 ASBDAQCANIOGJE-UHFFFAOYSA-N 0.000 description 1
- RPDVYRJSSOONCW-UHFFFAOYSA-N (4-chlorophenyl)methyl 5-chloro-2,4-dihydroxybenzoate Chemical compound C1=C(Cl)C(O)=CC(O)=C1C(=O)OCC1=CC=C(Cl)C=C1 RPDVYRJSSOONCW-UHFFFAOYSA-N 0.000 description 1
- ZDUSFBXQGSXGBR-UHFFFAOYSA-N (4-methylphenyl)methyl 2,4-dihydroxy-6-methoxybenzoate Chemical compound COC1=CC(O)=CC(O)=C1C(=O)OCC1=CC=C(C)C=C1 ZDUSFBXQGSXGBR-UHFFFAOYSA-N 0.000 description 1
- WDLMUXJDQUTTJB-UHFFFAOYSA-N (4-propan-2-ylphenyl)methyl 2,4-dihydroxy-6-methylbenzoate Chemical compound C1=CC(C(C)C)=CC=C1COC(=O)C1=C(C)C=C(O)C=C1O WDLMUXJDQUTTJB-UHFFFAOYSA-N 0.000 description 1
- LFYWZVYONLKULJ-UHFFFAOYSA-N 1-phenylethyl 3,4-dihydroxybenzoate Chemical compound C=1C=CC=CC=1C(C)OC(=O)C1=CC=C(O)C(O)=C1 LFYWZVYONLKULJ-UHFFFAOYSA-N 0.000 description 1
- WCOXQTXVACYMLM-UHFFFAOYSA-N 2,3-bis(12-hydroxyoctadecanoyloxy)propyl 12-hydroxyoctadecanoate Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC(O)CCCCCC)COC(=O)CCCCCCCCCCC(O)CCCCCC WCOXQTXVACYMLM-UHFFFAOYSA-N 0.000 description 1
- UQSRXQMIXSZGLA-UHFFFAOYSA-N 2,4-dihydroxy-6-methylbenzoic acid ethyl ester Chemical compound CCOC(=O)C1=C(C)C=C(O)C=C1O UQSRXQMIXSZGLA-UHFFFAOYSA-N 0.000 description 1
- QKJAZPHKNWSXDF-UHFFFAOYSA-N 2-bromoquinoline Chemical compound C1=CC=CC2=NC(Br)=CC=C21 QKJAZPHKNWSXDF-UHFFFAOYSA-N 0.000 description 1
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 description 1
- ZPJCHSCAVKMOGX-UHFFFAOYSA-N 2-phenylethyl 2,4-dihydroxybenzoate Chemical compound OC1=CC(O)=CC=C1C(=O)OCCC1=CC=CC=C1 ZPJCHSCAVKMOGX-UHFFFAOYSA-N 0.000 description 1
- FMXGOFBFEFAIJZ-UHFFFAOYSA-N 2-phenylethyl 3,4-dihydroxybenzoate Chemical compound C1=C(O)C(O)=CC=C1C(=O)OCCC1=CC=CC=C1 FMXGOFBFEFAIJZ-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- RPXXUXZFSVDPBN-UHFFFAOYSA-N C1(=CC=CC=C1)C(C)OC(C1=C(C=C(C=C1)O)O)=O.ClC1=CC=C(COC(C2=C(C=C(C=C2)O)O)=O)C=C1 Chemical compound C1(=CC=CC=C1)C(C)OC(C1=C(C=C(C=C1)O)O)=O.ClC1=CC=C(COC(C2=C(C=C(C=C2)O)O)=O)C=C1 RPXXUXZFSVDPBN-UHFFFAOYSA-N 0.000 description 1
- LZXYYLANRMWSCV-UHFFFAOYSA-N C1=CC(C)=CC=C1OCCOC(=O)C1=C(C)C=C(O)C=C1O Chemical compound C1=CC(C)=CC=C1OCCOC(=O)C1=C(C)C=C(O)C=C1O LZXYYLANRMWSCV-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RPWFJAMTCNSJKK-UHFFFAOYSA-N Dodecyl gallate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 RPWFJAMTCNSJKK-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- NAELFZKDZWMPBW-UHFFFAOYSA-N benzyl 2,4-dihydroxy-6-methylbenzoate Chemical compound CC1=CC(O)=CC(O)=C1C(=O)OCC1=CC=CC=C1 NAELFZKDZWMPBW-UHFFFAOYSA-N 0.000 description 1
- WOLNKQJMEVXQKB-UHFFFAOYSA-N benzyl 3,4-dihydroxybenzoate Chemical compound C1=C(O)C(O)=CC=C1C(=O)OCC1=CC=CC=C1 WOLNKQJMEVXQKB-UHFFFAOYSA-N 0.000 description 1
- MZSMDHBGDJISRZ-UHFFFAOYSA-N benzyl 3-chloro-4,5-dihydroxybenzoate Chemical compound ClC1=C(O)C(O)=CC(C(=O)OCC=2C=CC=CC=2)=C1 MZSMDHBGDJISRZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BALHTWIAIZTZCR-UHFFFAOYSA-N butyl 2,4-dihydroxy-6-methoxybenzoate Chemical compound CCCCOC(=O)C1=C(O)C=C(O)C=C1OC BALHTWIAIZTZCR-UHFFFAOYSA-N 0.000 description 1
- XIWYSPAVZJDUMJ-UHFFFAOYSA-N butyl 2,4-dihydroxybenzoate Chemical compound CCCCOC(=O)C1=CC=C(O)C=C1O XIWYSPAVZJDUMJ-UHFFFAOYSA-N 0.000 description 1
- CBDBLXUJRXZQMK-UHFFFAOYSA-N butyl 3,4-dihydroxybenzoate Chemical compound CCCCOC(=O)C1=CC=C(O)C(O)=C1 CBDBLXUJRXZQMK-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 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
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- FSUXPVRZBUVOKI-UHFFFAOYSA-N cyclohexyl 2,4-dihydroxy-6-methylbenzoate Chemical compound CC1=CC(O)=CC(O)=C1C(=O)OC1CCCCC1 FSUXPVRZBUVOKI-UHFFFAOYSA-N 0.000 description 1
- RJOVKPHBGXVSCW-UHFFFAOYSA-N cyclohexyl 2,4-dihydroxybenzoate Chemical compound OC1=CC(O)=CC=C1C(=O)OC1CCCCC1 RJOVKPHBGXVSCW-UHFFFAOYSA-N 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- BJQGLJQMEZUCGL-UHFFFAOYSA-K docosanoate;iron(3+) Chemical compound [Fe+3].CCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCC([O-])=O BJQGLJQMEZUCGL-UHFFFAOYSA-K 0.000 description 1
- FLJAJLOHHVNRHU-UHFFFAOYSA-K dodecanoate;iron(3+) Chemical compound [Fe+3].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O FLJAJLOHHVNRHU-UHFFFAOYSA-K 0.000 description 1
- 235000010386 dodecyl gallate Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- ALCUWNWVZNZFHQ-UHFFFAOYSA-N ethyl 2,4-dihydroxy-6-pentylbenzoate Chemical compound CCCCCC1=CC(O)=CC(O)=C1C(=O)OCC ALCUWNWVZNZFHQ-UHFFFAOYSA-N 0.000 description 1
- FUSZYPVTSGFURY-UHFFFAOYSA-N ethyl 2,4-dihydroxy-6-propan-2-ylbenzoate Chemical compound CCOC(=O)C1=C(O)C=C(O)C=C1C(C)C FUSZYPVTSGFURY-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000011888 foil Substances 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
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- TYCUSKFOGZNIBO-UHFFFAOYSA-N hexadecyl 3,4,5-trihydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 TYCUSKFOGZNIBO-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- LHLBEDGLCWFKLY-UHFFFAOYSA-K iron(3+) nonanoate Chemical compound [Fe+3].CCCCCCCCC([O-])=O.CCCCCCCCC([O-])=O.CCCCCCCCC([O-])=O LHLBEDGLCWFKLY-UHFFFAOYSA-K 0.000 description 1
- XHQSLVIGPHXVAK-UHFFFAOYSA-K iron(3+);octadecanoate Chemical compound [Fe+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XHQSLVIGPHXVAK-UHFFFAOYSA-K 0.000 description 1
- IMRZFEJNJIFRDU-UHFFFAOYSA-K iron(3+);tetradecanoate Chemical compound [Fe+3].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O IMRZFEJNJIFRDU-UHFFFAOYSA-K 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- IBKQQKPQRYUGBJ-UHFFFAOYSA-N methyl gallate Natural products CC(=O)C1=CC(O)=C(O)C(O)=C1 IBKQQKPQRYUGBJ-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 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
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000010387 octyl gallate Nutrition 0.000 description 1
- 239000000574 octyl gallate Substances 0.000 description 1
- NRPKURNSADTHLJ-UHFFFAOYSA-N octyl gallate Chemical compound CCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 NRPKURNSADTHLJ-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000002913 oxalic acids Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- WHFPMVZTSUOBEX-UHFFFAOYSA-N propyl 2,4-dihydroxy-6-methylbenzoate Chemical compound CCCOC(=O)C1=C(C)C=C(O)C=C1O WHFPMVZTSUOBEX-UHFFFAOYSA-N 0.000 description 1
- ZOXKFBKOLWENJR-UHFFFAOYSA-N propyl 2,4-dihydroxybenzoate Chemical compound CCCOC(=O)C1=CC=C(O)C=C1O ZOXKFBKOLWENJR-UHFFFAOYSA-N 0.000 description 1
- 235000010388 propyl gallate Nutrition 0.000 description 1
- 239000000473 propyl gallate Substances 0.000 description 1
- 229940075579 propyl gallate Drugs 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000013053 water resistant agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/32—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers one component being a heavy metal compound, e.g. lead or iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
- B41M5/465—Infrared radiation-absorbing materials, e.g. dyes, metals, silicates, C black
Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は熱記録に付される感熱記
録体に関するものであり、近赤外部に吸収域を有し、か
つ、鮮明でしかも保存安定性にすぐれた黒色の発色画像
が記録される感熱記録体を提供する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive recording material to be subjected to heat recording, and has a black colored image which has an absorption region in the near infrared region and is clear and has excellent storage stability. Provided is a thermosensitive recording medium to be recorded.
【0002】[0002]
【従来の技術】感熱記録体は、一般に、基体と該基体上
に形成されている感熱発色層とからなり、電子供与性の
通常無色ないし淡色のロイコ化合物と該ロイコ化合物を
発色させる電子受容性の顕色剤とを主成分とする感熱発
色層(一般に染料系感熱発色層という)が利用されてお
り、熱ヘッド、熱ペン、レーザ光等で加熱することによ
り、感熱発色層中のロイコ化合物と顕色剤とが瞬時に反
応し、発色画像が形成される(例えば、特公昭43ー4
160号公報、特公昭45ー14039号公報等)。2. Description of the Related Art A thermosensitive recording medium generally comprises a substrate and a thermosensitive coloring layer formed on the substrate, and is an electron-donating, usually colorless or light-colored leuco compound and an electron-accepting layer which develops the leuco compound. The thermosensitive coloring layer mainly composed of the above-mentioned color developing agent (generally called a dye-based thermosensitive coloring layer) is used, and the leuco compound in the thermosensitive coloring layer can be obtained by heating with a thermal head, a heating pen, a laser beam or the like. And the developer react instantaneously to form a color image (for example, Japanese Patent Publication No. 43-4).
No. 160, Japanese Patent Publication No. 45-14039, etc.).
【0003】かかる感熱記録体は、比較的簡単な装置に
よって発色画像が得られ、しかも、保守が容易であり、
また、騒音の発生が無いなどの利点を有するため、例え
ば、計測用記録計、ファクシミリ、プリンター、コンピ
ューターの端末機、ラベル、乗車券等の自動券売機など
の広範囲の分野に利用されている。In such a thermosensitive recording medium, a color-developed image can be obtained by a relatively simple device, and the maintenance is easy.
Further, since it has an advantage that it does not generate noise, it is used in a wide range of fields such as measuring recorders, facsimiles, printers, computer terminals, labels, and automatic ticket vending machines such as tickets.
【0004】特に、感熱記録用ラベルは、POS(販売
時点情報管理)システム用のバーコードラベル、価格表
示ラベル、配送・出荷ラベルなど、印字後に貼付工程を
必要とする用途に利用されており、スーパーマーケット
やデパート等の大型量販店をはじめ、チエーン展開をし
ている専門店やレストラン等において広く普及してい
る。このPOSシステムは、消費者のニーズを明確に把
握して合理的な経営戦略を立てる上での商品の売上情報
を集計,分析するためのものであり、その一つとして店
頭で販売される商品に表示されたバーコードやOCR文
字をスキャナーで光学的に読み取る方法が急速に普及し
てきている。In particular, heat-sensitive recording labels are used in applications requiring a sticking process after printing, such as bar code labels for POS (point-of-sale information management) systems, price display labels, and shipping / shipping labels. It is widely used in large-scale mass retailers such as supermarkets and department stores, as well as specialty stores and restaurants that are developing chains. This POS system is for collecting and analyzing the sales information of products in order to clearly understand the needs of consumers and establish a rational management strategy, and one of them is the products sold in stores. A method of optically reading a bar code or an OCR character displayed on the screen with a scanner is rapidly spreading.
【0005】現在、POSシステム用のラベルにおいて
は様々な印刷方式が試みられているが、その中でも特に
感熱記録体を利用する感熱記録方式は、その印字方式が
加熱による物質の化学的または物理的変化を利用して画
像を形成するもので、現像の定着を必要とせず、また、
印刷インキの補充が不要である等の諸種のメリットを有
する。さらに、感熱記録方式においては、機械の小型
化、簡素化、記録のスピード化が可能であり、インキに
よる手や商品の汚れ、インキのかすれ等がない等のメリ
ットをも有する。At present, various printing methods have been tried for labels for POS systems. Among them, the heat-sensitive recording method using a heat-sensitive recording material, in particular, the printing method is chemical or physical of a substance by heating. An image is formed by utilizing changes, does not require fixing of development, and
It has various merits such as no need to replenish printing ink. Further, the heat-sensitive recording system has advantages that the machine can be downsized, simplified, and the recording speed can be increased, and that there is no stain on the hands or products due to ink, or ink is not scratched.
【0006】他方、感熱記録方式で得られた発色画像の
バーコード等の読み取りには、従来より、波長633n
mの赤色光をもつHe・Neレーザ光が利用されてお
り、最近では半導体レーザが使われるようになってき
た。これは電流で直接変調でき、小型化が可能で、使い
易く、低価格であり、しかも、発振波長が700〜15
00nmの近赤外部にあることから、汚れによる誤動作
が少ないなどの利点があり、広く普及し始めている。従
って、感熱記録用ラベルの分野においても半導体レーザ
での読み取が可能な発色画像が得られるタイプの感熱記
録体が要望されている。On the other hand, for reading a bar code or the like of a color-developed image obtained by the thermal recording system, a wavelength of 633n has been conventionally used.
He.Ne laser light having m red light has been used, and recently, semiconductor lasers have come to be used. It can be directly modulated by current, can be miniaturized, is easy to use, low cost, and has an oscillation wavelength of 700 ~ 15.
Since it is located in the near-infrared region of 00 nm, it has the advantage that there are few malfunctions due to dirt, and it is beginning to be widely used. Therefore, also in the field of heat-sensitive recording labels, there is a demand for a heat-sensitive recording material of the type capable of obtaining a color image readable by a semiconductor laser.
【0007】しかしながら、従来より用いられているロ
イコ化合物と顕色剤とを含有する2成分型感熱発色層を
有する感熱記録体は、黒色の発色系においてさえも発色
画像の吸収波長が長波長側にある、すなわち、吸収波長
が550〜620nmにあることから、He・Neレー
ザ光での読み取りは可能であるものの、近赤外部波長を
もつ半導体レーザでの読み取りが不可能である。However, a heat-sensitive recording material having a two-component heat-sensitive color developing layer containing a leuco compound and a color developer, which have been conventionally used, has a long wavelength absorption wavelength of a color image even in a black color developing system. That is, since the absorption wavelength is in the range of 550 to 620 nm, it is possible to read with a He / Ne laser beam, but it is not possible to read with a semiconductor laser having a near infrared wavelength.
【0008】他方、感熱発色層中の成分の1方または双
方が溶融,反応してキレート化合物を生成して発色する
機構を利用するものとして、有機酸重金属塩または有機
酸貴金属塩からなる一方の成分と、有機還元剤,硫黄化
合物,あるいはアミノ化合物のうちのいずれかの1つか
らなる他方の成分との組み合わせによる発色系が知られ
ている。そして、かかる発色系では近赤外部に吸収波長
を持つ発色画像が得られるものが多く、例えば長鎖脂肪
酸鉄塩と多価フェノールとの組み合わせからなる発色系
による感熱発色層がある。On the other hand, one or both of the components in the thermosensitive color developing layer utilizes a mechanism in which one or both of the components melts and reacts to form a chelate compound to develop a color, and one of an organic acid heavy metal salt or an organic acid noble metal salt is used. A color-developing system is known in which a component is combined with the other component consisting of one of an organic reducing agent, a sulfur compound and an amino compound. In most of such color-developing systems, a color-developed image having an absorption wavelength in the near infrared region can be obtained. For example, there is a thermosensitive color-developing layer of a color-developing system composed of a combination of long-chain fatty acid iron salt and polyhydric phenol.
【0009】しかるに、この種のキレート化合物の生成
に伴う発色機構を利用する従来の感熱記録体において、
長鎖脂肪酸鉄塩と多価フェノールとの組み合わせによる
ものは得られる発色画像の色相が赤〜紫であり、しかも
地肌かぶりが発生し易いという欠点を有する。なお、感
熱発色層の発色画像の色相が赤〜紫であるということ
は、黒色の発色画像に比較して目視による読み取りに難
点を有する。However, in the conventional thermosensitive recording medium which utilizes the coloring mechanism associated with the formation of this type of chelate compound,
The combination of a long-chain fatty acid iron salt and a polyhydric phenol has the drawbacks that the hue of the resulting color image is red to purple and that background fog is likely to occur. It should be noted that the fact that the hue of the color-developed image of the thermosensitive color-developing layer is red to purple has a difficulty in visual reading compared to the black color-developed image.
【0010】[0010]
【発明が解決しようとする課題】本発明は、地肌が白
く、しかも、近赤外部に吸収波長を有し、かつ、保存性
能の良好な黒色の鮮明な発色画像が得られる感熱記録体
を提供する。DISCLOSURE OF THE INVENTION The present invention provides a thermosensitive recording medium which has a white background and has an absorption wavelength in the near infrared region, and which can obtain a clear black colored image having good storage performance. To do.
【0011】[0011]
【課題を解決するための手段】本発明は、基体上におけ
る感熱発色層を、脂肪酸第2鉄塩と、少なくとも3位及
び4位に水酸基を有するフェノール性化合物と、2位及
び4位のみに水酸基を有するフェノール性化合物とを含
有する塗工剤で形成することにより、前述の目的を達成
する感熱記録体を得るものである。According to the present invention, a thermosensitive coloring layer on a substrate is composed of a ferric acid fatty acid salt, a phenolic compound having a hydroxyl group at at least the 3rd and 4th positions, and 2nd and 4th positions only. By forming a coating material containing a phenolic compound having a hydroxyl group, a heat-sensitive recording material that achieves the above-mentioned object is obtained.
【0012】本発明者らは、脂肪酸第2鉄塩と多価フェ
ノールとの組み合わせによる発色系について検討したと
ころ、脂肪酸第2鉄塩と少なくとも3位及び4位に水酸
基を有するフェノール性化合物との組み合わせによる発
色系の場合には、濃度の高いしかも近紫外部に吸収波長
を有する発色画像が得られるが、この発色画像は色相が
紫色であり、しかも、地肌かぶりを生じ易いことを確認
した。The present inventors have examined a color-developing system by combining a ferric acid fatty acid salt and a polyhydric phenol, and found that a ferric fatty acid salt and a phenolic compound having a hydroxyl group at least at the 3- and 4-positions are used. In the case of the color-developing system by the combination, a color-developed image having a high density and an absorption wavelength in the near-ultraviolet region was obtained, and it was confirmed that the hue of this color-developed image was purple and the background fogging was likely to occur.
【0013】また、脂肪酸第2鉄塩と2位及び4位のみ
に水酸基を有するフェノール性化合物との組み合わせに
よる発色系の場合は、地肌かぶりは生じ難いものの、赤
〜茶褐色の色相を有する濃度の薄い発色画像が得られる
ことを確認した。Further, in the case of a color-developing system in which a fatty acid ferric iron salt is combined with a phenolic compound having a hydroxyl group only at the 2- and 4-positions, although the background fog is unlikely to occur, a concentration of a red to brown hue is obtained. It was confirmed that a light colored image was obtained.
【0014】これらの事実に基づいて、感熱発色層にお
ける発色画像を、脂肪酸第2鉄塩と少なくとも3位及び
4位に水酸基を有するフェノール性化合物との組み合わ
せによるものと、脂肪酸第2鉄塩と2位及び4位のみに
水酸基を有するフェノール性化合物との組み合わせによ
るものとを相乗させることにより、本発明の目的とする
感熱記録体、すなわち、地肌かぶりの無い、しかも、近
赤外部に吸収波長を有し、かつ、保存性能の良好な黒色
の鮮明な発色画像が得られるようになる。On the basis of these facts, a color image in the thermosensitive coloring layer is obtained by combining a fatty acid ferric iron salt and a phenolic compound having a hydroxyl group at at least the 3rd and 4th positions, and a fatty acid ferric iron salt. By synergizing with a combination of a phenolic compound having a hydroxyl group only at the 2- and 4-positions, the object of the present invention is to obtain a heat-sensitive recording material, that is, there is no background fog and the absorption wavelength in the near infrared region. In addition, it is possible to obtain a clear black colored image which has good storage performance.
【0015】本発明の感熱記録体における感熱発色層に
利用される脂肪酸第2鉄塩は、炭素数6〜25、好まし
くは9〜22の直鎖又は分枝鎖の飽和脂肪酸又は不飽和
脂肪酸の第2鉄塩であり、例えば、ステアリン酸第2
鉄、ミリスチン酸第2鉄、ベヘン酸第2鉄、ラウリル酸
第2鉄及びペラルゴン酸第2鉄等からなり、特に飽和脂
肪酸の第2鉄塩が好適である。The fatty acid ferric iron salt used in the thermosensitive coloring layer of the thermosensitive recording medium of the present invention is a straight chain or branched chain saturated or unsaturated fatty acid having 6 to 25 carbon atoms, preferably 9 to 22 carbon atoms. A ferric salt, for example, stearic acid second
Consists of iron, ferric myristate, ferric behenate, ferric laurate, ferric pelargonate, etc., and ferric salts of saturated fatty acids are particularly preferable.
【0016】少なくとも3位及び4位に水酸基を有する
フェノール性化合物は、例えば、没食子酸エステル,
3,4−ジヒドロキシ安息香酸エステル,3,4−ジヒ
ドロキシ−4−メチルジフェニルスルホン等であり、以
下に列記するようなものあるいはこれらの2種以上の混
合物を利用し得る。Phenolic compounds having a hydroxyl group at least at the 3- and 4-positions include, for example, gallic acid esters,
Examples thereof include 3,4-dihydroxybenzoic acid ester and 3,4-dihydroxy-4-methyldiphenyl sulfone, and those listed below or a mixture of two or more thereof can be used.
【0017】一般式C6 H2 (OH)3 (COOR)に
おいて、Rが炭素数1〜28のアルキル基,フェニル基
あるいはベンジル基及びそれらの誘導体からなる没食子
酸エステル、例えば、没食子酸メチル,没食子酸プロピ
ル,没食子酸オクチル,没食子酸ラウリル,没食子酸セ
チル,没食子酸ステアリル,没食子酸ベヘニル等、3,
4−ジヒドロキシ安息香酸ブチルエステル、3,4−ジ
ヒドロキシ安息香酸ベンジルエステル、3,4−ジヒド
ロキシ安息香酸−β−フェニルエチルエステル、3,4
−ジヒドロキシ−5−クロロ安息香酸ベンジルエステ
ル、3,4−ジヒドロキシ安息香酸−α−フェニルエチ
ルエステル、3,4−ジヒドロキシ−4−メチルジフェ
ニルスルホン、In the general formula C 6 H 2 (OH) 3 (COOR), a gallic acid ester in which R is an alkyl group having 1 to 28 carbon atoms, a phenyl group or a benzyl group and derivatives thereof, for example, methyl gallate, Propyl gallate, octyl gallate, lauryl gallate, cetyl gallate, stearyl gallate, behenyl gallate, etc., 3,
4-dihydroxybenzoic acid butyl ester, 3,4-dihydroxybenzoic acid benzyl ester, 3,4-dihydroxybenzoic acid-β-phenylethyl ester, 3,4
-Dihydroxy-5-chlorobenzoic acid benzyl ester, 3,4-dihydroxybenzoic acid-α-phenylethyl ester, 3,4-dihydroxy-4-methyldiphenyl sulfone,
【0018】2位及び4位のみに水酸基を有するフェノ
ール性化合物は、例えば、2,4−ジヒドロキシベンゾ
フェノンや2,4−ジヒドロキシ安息香酸エステル等で
あり、以下に列記するようなものあるいはこれらの2種
以上の混合物を利用し得る。2,4−ジヒドロキシ安息
香酸プロピルエステル、2,4−ジヒドロキシ安息香酸
ブチルエステル、2,4−ジヒドロキシ安息香酸シクロ
ヘキシルエステル、2,4−ジヒドロキシ安息香酸ベン
ジルエステル2,4−ジヒドロキシ安息香酸−p−メチ
ルベンジルエステル2,4−ジヒドロキシ安息香酸−p
−クロロベンジルエステル2,4−ジヒドロキシ安息香
酸−α−フェニルエチルエステル、2,4−ジヒドロキ
シ安息香酸−β−フェニルエチルエステル、2,4−ジ
ヒドロキシ−6−メチル安息香酸エチルエステル、2,
4−ジヒドロキシ−6−メチル安息香酸プロピルエステ
ル、2,4−ジヒドロキシ−6−イソプロピル安息香酸
エチルエステル、2,4−ジヒドロキシ−6−ペンチル
安息香酸エチルエステル、2,4−ジヒドロキシ−6−
メトキシ安息香酸ブチルエステル、2,4−ジヒドロキ
シ−6−メチル安息香酸シクロヘキシルエステル、2,
4−ジヒドロキシ−6−メチル安息香酸ベンジルエステ
ル、2,4−ジヒドロキシ−6−プロピル安息香酸p−
クロロベンジルエステル、2,4−ジヒドロキシ−6−
メトキシ安息香酸p−メチルベンジルエステル、2,4
−ジヒドロキシ−6−メチル安息香酸p−イソプロピル
ベンジルエステル、2,4−ジヒドロキシ−6−メチル
安息香酸p−メチルフェノキシエチルエステル、2,4
−ジヒドロキシ−5−クロロ安息香酸−p−クロロベン
ジルエステル、2,4−ジヒドロキシベンゾフェノン、The phenolic compound having a hydroxyl group only at the 2- and 4-positions is, for example, 2,4-dihydroxybenzophenone, 2,4-dihydroxybenzoic acid ester, etc., and those listed below or those 2 Mixtures of more than one species can be utilized. 2,4-dihydroxybenzoic acid propyl ester, 2,4-dihydroxybenzoic acid butyl ester, 2,4-dihydroxybenzoic acid cyclohexyl ester, 2,4-dihydroxybenzoic acid benzyl ester 2,4-dihydroxybenzoic acid-p-methyl ester Benzyl ester 2,4-dihydroxybenzoic acid-p
-Chlorobenzyl ester 2,4-dihydroxybenzoic acid-α-phenylethyl ester, 2,4-dihydroxybenzoic acid-β-phenylethyl ester, 2,4-dihydroxy-6-methylbenzoic acid ethyl ester, 2,
4-Dihydroxy-6-methylbenzoic acid propyl ester, 2,4-dihydroxy-6-isopropylbenzoic acid ethyl ester, 2,4-dihydroxy-6-pentylbenzoic acid ethyl ester, 2,4-dihydroxy-6-
Methoxybenzoic acid butyl ester, 2,4-dihydroxy-6-methylbenzoic acid cyclohexyl ester, 2,
4-Dihydroxy-6-methylbenzoic acid benzyl ester, 2,4-dihydroxy-6-propylbenzoic acid p-
Chlorobenzyl ester, 2,4-dihydroxy-6-
Methoxybenzoic acid p-methylbenzyl ester, 2,4
-Dihydroxy-6-methylbenzoic acid p-isopropylbenzyl ester, 2,4-dihydroxy-6-methylbenzoic acid p-methylphenoxyethyl ester, 2,4
-Dihydroxy-5-chlorobenzoic acid-p-chlorobenzyl ester, 2,4-dihydroxybenzophenone,
【0019】脂肪酸第2鉄塩と、少なくとも3位及び4
位に水酸基を有するフェノール性化合物と、2位及び4
位のみに水酸基を有するフェノール性化合物とを含有す
る感熱発色層において、脂肪酸第2鉄塩の量が少ないと
発色画像の保存特性及び近赤外線部での吸収特性が低下
し、逆に、脂肪酸第2鉄塩が多過ぎると地肌濃度が高く
なり発色画像が鮮明性に欠けるようになる。このため、
通常は、脂肪酸第2鉄塩100重量部に対して、少なく
とも3位及び4位に水酸基を有するフェノール性化合物
と、2位及び4位のみに水酸基を有するフェノール性化
合物との合計量が、50〜500重量部の混合比率で配
合されるのが好ましい。Ferric acid fatty acid salt and at least the 3rd and 4th positions
A phenolic compound having a hydroxyl group at the 2-position and 2- and 4-positions
In the thermosensitive coloring layer containing a phenolic compound having a hydroxyl group only at the position, when the amount of the fatty acid ferric salt is small, the storage property of the color image and the absorption property in the near infrared region are deteriorated, and conversely, the fatty acid If the amount of diiron salt is too large, the background density becomes high and the color image lacks sharpness. For this reason,
Usually, the total amount of the phenolic compound having hydroxyl groups at at least the 3rd and 4th positions and the phenolic compound having hydroxyl groups at only the 2nd and 4th positions is 50 with respect to 100 parts by weight of the ferric acid fatty acid salt. It is preferable to mix them in a mixing ratio of about 500 parts by weight.
【0020】また、少なくとも3位及び4位に水酸基を
有するフェノール性化合物と、2位及び4位のみに水酸
基を有するフェノール性化合物との間で、少なくとも3
位及び4位に水酸基を有するフェノール性化合物の量が
少なすぎると得られる発色画像の濃度が低下することが
あり、逆に多過ぎると地肌かぶりが発生し易くなる。こ
のため、少なくとも3位及び4位に水酸基を有するフェ
ノール性化合物と2位及び4位のみに水酸基を有するフ
ェノール性化合物とは、80〜20重量%:20〜80
重量%の混合比率で配合されるのが好ましい。Further, between the phenolic compound having a hydroxyl group at least at the 3rd and 4th positions and the phenolic compound having a hydroxyl group at only the 2nd and 4th positions, at least 3
If the amount of the phenolic compound having hydroxyl groups at the 4th and 4th positions is too small, the density of the color image obtained may decrease, and if too large, background fog tends to occur. Therefore, the phenolic compound having a hydroxyl group at least at the 3rd and 4th positions and the phenolic compound having a hydroxyl group at only the 2nd and 4th positions are 80 to 20% by weight: 20 to 80% by weight.
It is preferable to mix them in a mixing ratio of wt%.
【0021】次に、本発明の感熱記録体の感熱発色層に
利用される前記成分以外の任意成分の主なものについて
以下に具体的に説明する。Next, the main components of the optional components other than the above components used in the thermosensitive coloring layer of the thermosensitive recording medium of the present invention will be specifically described below.
【0022】水溶性結着剤としては、デンプン類、ヒド
ロキシエチルセルロース、メチルセルロース、カルボキ
シメチルセルロース、ゼラチン、カゼイン、ポリビニル
アルコール、変性ポリビニルアルコール、スチレン−無
水マレイン酸共重合体、エチレン−無水マレイン酸共重
合体などの水溶性バインダー、スチレン−ブタジエン共
重合体、アクリロニトリル−ブタジエン共重合体、アク
リル酸メチル−ブタジエン共重合体などのラテックス系
水溶性バインダーなどが利用される。As the water-soluble binder, starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, styrene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer. Water-soluble binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, and latex-based water-soluble binders such as methyl acrylate-butadiene copolymers are used.
【0023】顔料としては、ケイソウ土、タルク、カオ
リン、焼成カオリン、炭酸カルシウム、炭酸マグネシウ
ム、酸化チタン、酸化亜鉛、酸化ケイ素、水酸化アルミ
ニウム、尿素−ホルマリン樹脂などが利用される。As the pigment, diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, urea-formalin resin and the like are used.
【0024】さらに、ヘッド摩耗防止、スティッキング
防止などの目的で、ステアリン酸亜鉛、ステアリン酸カ
ルシウム等の高級脂肪酸金属塩、パラフィン、酸化パラ
フィン、ポリエチレン、酸化ポリエチレン、ステアリン
酸アミド、カスターワックス等のワックス類が、また、
感度向上剤として、メタタールフェニル、パラベンジル
ビスフェニル、ヒドロキシナフトエ酸のエステル類、ス
テアリン酸アミド、トリベンジルアミン、ナフタレン誘
導体、ジベンジルテレフタレート、蓚酸ジベンジル、蓚
酸ビス(パラメチルベンジル)などの各種蓚酸エステル
等が利用される。Further, for the purpose of preventing head wear and sticking, higher fatty acid metal salts such as zinc stearate and calcium stearate, waxes such as paraffin, oxidized paraffin, polyethylene, polyethylene oxide, stearic acid amide and castor wax are used. ,Also,
Various oxalic acids such as metatarphenyl, parabenzylbisphenyl, esters of hydroxynaphthoic acid, stearic acid amide, tribenzylamine, naphthalene derivative, dibenzyl terephthalate, dibenzyl oxalate, bis (paramethylbenzyl oxalate), etc. Esters and the like are used.
【0025】さらにまた、ジオクチルスルホコハク酸ナ
トリウム等の分散剤、ベンゾフェノン系、ベンゾトリア
ゾール系などの紫外線吸収剤、また、界面活性剤、蛍光
染料などが所望に応じて利用される。Furthermore, a dispersant such as sodium dioctylsulfosuccinate, a UV absorber such as a benzophenone type or a benzotriazole type, a surfactant, a fluorescent dye and the like are used as desired.
【0026】また、発色画像の濃度をさらに高める目的
で従来公知の染料系感熱発色剤を添加することもでき
る。Further, a conventionally known dye-based heat-sensitive color former may be added for the purpose of further increasing the density of the color image.
【0027】本発明の感熱記録体における基体として
は、紙が主として利用されるが、各種の不織布、プラス
チックフィルム、合成紙、金属箔等、あるいはこれらを
組合わせた複合シート等が任意に用いられる。Paper is mainly used as the substrate in the thermosensitive recording medium of the present invention, but various non-woven fabrics, plastic films, synthetic papers, metal foils, etc., or composite sheets combining these are optionally used. .
【0028】以上の通りの構成による本発明の感熱記録
体は、一般的に、通常のファクシミリ、プリンター等を
はじめ近赤外光を検知する特殊用途にも利用され、特に
発色画像の高保存性が所望される場合には感熱発色層を
被覆する保護層を形成することにより未発色部及び発色
画像部を外部環境から保護することが好ましい。なお、
保護層の主成分としては、各種の水溶性樹脂、ラテック
ス、紫外線や電子線による電離放射線硬化型樹脂等が利
用され、さらに、必要に応じて、顔料、耐水化剤、撥水
剤、消泡剤、紫外線吸収剤等を添加することができる。The thermal recording material of the present invention having the above-mentioned constitution is generally used for ordinary facsimiles, printers and other special applications for detecting near-infrared light, and particularly has high storability of color images. If desired, it is preferable to protect the uncolored portion and the colored image portion from the external environment by forming a protective layer covering the thermosensitive coloring layer. In addition,
As the main component of the protective layer, various water-soluble resins, latex, ionizing radiation curable resin by ultraviolet rays or electron beams, etc. are used, and further, if necessary, pigments, water resistant agents, water repellents, defoamers. Agents, ultraviolet absorbers and the like can be added.
【0029】本発明の感熱記録体は、従来の染料系の感
熱記録体とほぼ同じ製造法で製造される。具体的には、
脂肪酸第2鉄塩とフェノール性化合物とのそれぞれを別
々に、サンドグラインダー、アトライター、ボールミル
を利用し水系で粉砕・分散後混合することによって得ら
れる水系の塗工剤を利用する方法、あるいは、脂肪酸第
2鉄塩とフェノール性化合物とのいずれかをマイクロカ
プセル化したものを利用して得られる水系の塗工剤を利
用する方法等である。The heat-sensitive recording material of the present invention is manufactured by substantially the same manufacturing method as that of the conventional dye-based heat-sensitive recording material. In particular,
A method of using a water-based coating agent obtained by separately pulverizing and dispersing each of the ferric fatty acid ferric salt and the phenolic compound separately in a water system using a sand grinder, attritor, or ball mill, or A method using a water-based coating agent obtained by microcapsulating either a ferric acid fatty acid salt or a phenolic compound.
【0030】[0030]
【発明の作用】本発明の感熱記録体は、その発色画像を
近赤外光を含む半導体レーザ光により読み取ることがで
き、しかも、発色性及び保存性において優れた作用を奏
する黒色の画像が得られる。The heat-sensitive recording material of the present invention can obtain a black image whose color image can be read by a semiconductor laser beam containing near-infrared light and which has an excellent function in color development and storability. To be
【0031】[0031]
【実施例】本発明の感熱記録体の具体的な構成を実施例
に基づいて説明する。EXAMPLES The specific constitution of the thermosensitive recording medium of the present invention will be explained based on examples.
【0032】実施例1 下記の組成によるA液およびB液を各々別々にサンドグ
ラインダーで分散させた。Example 1 Solution A and solution B having the following compositions were separately dispersed by a sand grinder.
【0033】 A液 ステアリン酸第2鉄(脂肪酸第2鉄塩)・・・・・・・・・・・・・・10重量部 軽質炭酸カルシウム・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・20重量部 ポリビニルアルコール12重量%水溶液・・・・・・・・・・・・・・40重量部 水・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・50重量部Liquid A Ferric stearate (ferric fatty acid ferric salt): 10 parts by weight Light calcium carbonate: 20 parts by weight Polyvinyl alcohol 12% by weight aqueous solution ... 40 parts by weight Water ... ........................................ 50 parts by weight
【0034】 B液 没食子酸ステアリル(少なくとも3位及び4位に水酸基を有するフェノール性 化合物)・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・20重量部 2,4−ジヒドロキシ安息香酸ベンジルエステル(2位及び4位のみに水酸基 を有するフェノール性化合物)・・・・・・・・・・・・・・・・・・・・・・・・20重量部 軽質炭酸カルシウム・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・20重量部 ポリビニルアルコール12重量%水溶液・・・・・・・・・・・・・・70重量部 水・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・70重量部Liquid B Stearyl gallate (a phenolic compound having a hydroxyl group at least at the 3- and 4-positions) ... 20 parts by weight 2,4-dihydroxybenzoic acid benzyl ester (phenolic compound having a hydroxyl group only at the 2- and 4-positions) 20 parts by weight light calcium carbonate 20 parts by weight 12% by weight aqueous solution of polyvinyl alcohol ... 70 parts by weight water ... 70 parts by weight
【0035】次に、A液120重量部とB液200重量
部とポリビニルアルコール12重量%水溶液50重量部
とを混合して撹拌し、感熱発色層用の水系塗工液を調製
した。Next, 120 parts by weight of solution A, 200 parts by weight of solution B and 50 parts by weight of a 12% by weight aqueous solution of polyvinyl alcohol were mixed and stirred to prepare an aqueous coating solution for the thermosensitive color developing layer.
【0036】続いて、この感熱発色層用の塗工液を、5
0g/m2 の上質紙からなる基体上に塗布量7g(dr
y)/m2 の割合に塗工,乾燥し、さらにキャレンダー
処理を施すことにより、ベック平滑度が500秒の感熱
発色層を有する感熱記録体を得た。Then, the coating solution for the thermosensitive coloring layer was added to 5
0 g / m 2 of the substrate on the coating weight 7g made of woodfree paper (dr
A thermosensitive recording material having a thermosensitive color developing layer having a Beck smoothness of 500 seconds was obtained by applying the composition at a ratio of y) / m 2 , followed by drying and calendering.
【0037】実施例2〜5 実施例1で利用した感熱発色層用の水性塗工液のA液に
おける脂肪酸第2鉄塩、B液における少なくとも3位及
び4位に水酸基を有するフェノール性化合物と2位及び
4位のみに水酸基を有するフェノール性化合物として、
それぞれ[表1]の所定欄に表示されているものを利用
し、それ以外の成分については実施例1で利用したA液
及びB液と同一の組成成分による各液を調製し、以下前
記実施例1の対応する工程と同様にして処方した塗工液
を、同じく実施例1の対応する工程と同様にして塗工
し、ベック平滑度が500秒の感熱発色層を有する各感
熱記録体を得た。なお、[表1]の各欄における( )
内の数字は重量部である。Examples 2 to 5 A fatty acid ferric iron salt in solution A of the aqueous coating solution for the thermosensitive color developing layer used in Example 1 and a phenolic compound having a hydroxyl group at at least the 3rd and 4th positions in solution B were used. As a phenolic compound having a hydroxyl group only at the 2- and 4-positions,
Each of the liquids listed in the predetermined column of [Table 1] was used, and for the other components, liquids having the same compositional components as those of the liquids A and B used in Example 1 were prepared. A coating solution formulated in the same manner as in the corresponding step of Example 1 was applied in the same manner as in the corresponding step of Example 1 to obtain each thermosensitive recording material having a thermosensitive color developing layer having a Bekk smoothness of 500 seconds. Obtained. () In each column of [Table 1]
The numbers inside are parts by weight.
【0038】[0038]
【表1】 [Table 1]
【0039】比較例1〜2 実施例1で利用した感熱発色層用の塗工液のA液におけ
る脂肪酸第2鉄塩及びB液におけるフェノール性化合物
として、[表2]の所定欄に表示されているものを利用
し、それ以外の成分については、実施例1で利用したA
液及びB液と同一の組成成分による各液を利用し、以下
前記実施例1の対応する工程と同様にして処方した塗工
液を、実施例1の対応する工程と同様にして塗工し、ベ
ック平滑度が500秒の感熱発色層を有する各感熱記録
体を得た。なお、[表2]の各欄内における数字は重量
部を表示する。Comparative Examples 1 to 2 As the fatty acid ferric iron salt in the solution A and the phenolic compound in the solution B of the coating solution for the thermosensitive color developing layer used in Example 1, the compounds are displayed in the predetermined columns of [Table 2]. The ingredients used in Example 1 were used for the other ingredients.
Using each liquid having the same composition components as the liquid and the liquid B, a coating liquid formulated in the same manner as in the corresponding step of Example 1 was applied in the same manner as in the corresponding step of Example 1. A thermosensitive recording material having a thermosensitive coloring layer having a Bekk smoothness of 500 seconds was obtained. The numbers in each column of [Table 2] indicate parts by weight.
【0040】[0040]
【表2】 [Table 2]
【0041】評価 実施例1〜5及び比較例1〜2で得られた各感熱記録体
について、次の(1) 〜(5) の評価を行なった。その結果
を[表3]に示す。 (1) 地肌濃度 地肌の光学濃度をマクベスRD918を用いて測定し
た。 (2) 発色濃度 ラベルプリンターXP6250(日清紡製)で印字し、
発色画像の光学濃度をマクベスRD918を用いて測定
した。 (3) 画像保存性 発色画像を50℃,90%の環境下に1週間保存した後
の光学濃度を、マクベスRD918を用いて測定した。 (4) 近赤外光読み取り 780nmでの反射スペクトルの値が30%以下であると
きに、GaAs半導体レーザー(780nm)での読み取
りが可能であることから、発色部における780nmで
の反射スペクトルの値が30%以下であるときを・・・・
○、30%を超えるときを・・・・×でそれぞれ表示した。
なお、発色部の反射スペクトルは、 (株) 日立製作所製
の自記分光光度計U−3400を利用し、積分球を用い
る測定方法によって測定した。 (5) 色相 発色画像の色相を目視で判定した。Evaluation The thermal recording materials obtained in Examples 1 to 5 and Comparative Examples 1 to 2 were evaluated in the following (1) to (5). The results are shown in [Table 3]. (1) Background density The optical density of the background was measured using Macbeth RD918. (2) Color density Print with label printer XP6250 (manufactured by Nisshinbo),
The optical density of the color image was measured using Macbeth RD918. (3) Image storability A color image was stored for 1 week in an environment of 50 ° C. and 90%, and the optical density was measured using Macbeth RD918. (4) Near-infrared light reading When the reflectance spectrum value at 780 nm is 30% or less, it is possible to read with a GaAs semiconductor laser (780 nm), so the reflectance spectrum value at 780 nm in the color development part When is less than 30% ...
◯, when more than 30% was indicated by ... ×.
The reflection spectrum of the color-developing part was measured by a measuring method using an integrating sphere using a self-recording spectrophotometer U-3400 manufactured by Hitachi, Ltd. (5) Hue The hue of the developed image was visually determined.
【0042】[0042]
【表3】 [Table 3]
【0043】[0043]
【効果】本発明の感熱記録体は、近赤外部に吸収域を有
し、かつ、鮮明でしかも保存安定性にすぐれた黒色の発
色画像が記録されるものであることから、半導体レーザ
での読み取りができ、例えば、感熱記録用ラベルの分野
等における感熱記録体として極めて実用性が高く、高度
の利用価値を有する。[Effect] The thermosensitive recording medium of the present invention has an absorption region in the near infrared region and is capable of recording a black colored image which is clear and has excellent storage stability. It is readable and has extremely high practical value as a thermal recording material in the field of thermal recording labels and the like, and has a high utility value.
Claims (3)
が、脂肪酸第2鉄塩と、少なくとも3位及び4位に水酸
基を有するフェノール性化合物と、2位及び4位のみに
水酸基を有するフェノール性化合物とを含有しているこ
とを特徴とする感熱記録体。1. A thermosensitive color forming layer formed on a substrate, a ferric acid salt of fatty acid, a phenolic compound having a hydroxyl group at least at the 3rd and 4th positions, and a phenol having a hydroxyl group at only the 2nd and 4th positions. A heat-sensitive recording material containing a thermosensitive compound.
するフェノール性化合物が、没食子酸エステル、3,4
−ジヒドロキシ安息香酸エステルまたは3,4−ジヒド
ロキシ−4−メチルジフェニルスルホンあるいはこれら
の混合物からなる請求項1記載の感熱記録体。2. A phenolic compound having a hydroxyl group at at least the 3- and 4-positions is a gallic acid ester, 3,4.
A thermosensitive recording medium according to claim 1, which comprises a dihydroxybenzoic acid ester, 3,4-dihydroxy-4-methyldiphenyl sulfone, or a mixture thereof.
ェノール性化合物が、2,4−ジヒドロキシベンゾフェ
ノンまたは2,4−ジヒドロキシ安息香酸エステルある
いはこれらの混合物からなる請求項1または請求項2記
載の感熱記録体。3. The phenolic compound having a hydroxyl group only at the 2- and 4-positions comprises 2,4-dihydroxybenzophenone, 2,4-dihydroxybenzoic acid ester or a mixture thereof. Thermal recording material.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP04242777A JP3118978B2 (en) | 1992-08-19 | 1992-08-19 | Thermal recording medium |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP04242777A JP3118978B2 (en) | 1992-08-19 | 1992-08-19 | Thermal recording medium |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0664331A true JPH0664331A (en) | 1994-03-08 |
JP3118978B2 JP3118978B2 (en) | 2000-12-18 |
Family
ID=17094132
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP04242777A Expired - Fee Related JP3118978B2 (en) | 1992-08-19 | 1992-08-19 | Thermal recording medium |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0727320A1 (en) * | 1995-02-17 | 1996-08-21 | Eastman Kodak Company | 2-Hydroxybenzophenone UV dyes for laser recording element |
US7968142B2 (en) | 2003-06-24 | 2011-06-28 | Yazaki Corporation | Method and apparatus for coloring electric wire |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014151374A (en) * | 2013-02-05 | 2014-08-25 | Vessel Industrial Co Ltd | Bit with flat plate-shaped shock cushioning region |
-
1992
- 1992-08-19 JP JP04242777A patent/JP3118978B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0727320A1 (en) * | 1995-02-17 | 1996-08-21 | Eastman Kodak Company | 2-Hydroxybenzophenone UV dyes for laser recording element |
US7968142B2 (en) | 2003-06-24 | 2011-06-28 | Yazaki Corporation | Method and apparatus for coloring electric wire |
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JP3118978B2 (en) | 2000-12-18 |
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