JPS63147683A - High-quality thermal recording sheet and production thereof - Google Patents
High-quality thermal recording sheet and production thereofInfo
- Publication number
- JPS63147683A JPS63147683A JP62146494A JP14649487A JPS63147683A JP S63147683 A JPS63147683 A JP S63147683A JP 62146494 A JP62146494 A JP 62146494A JP 14649487 A JP14649487 A JP 14649487A JP S63147683 A JPS63147683 A JP S63147683A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- sensitive recording
- recording sheet
- layer
- quality
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000007788 liquid Substances 0.000 claims abstract description 56
- 239000011248 coating agent Substances 0.000 claims abstract description 48
- 238000000576 coating method Methods 0.000 claims abstract description 48
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000010410 layer Substances 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 14
- 239000002344 surface layer Substances 0.000 claims description 12
- 239000011241 protective layer Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000003086 colorant Substances 0.000 claims description 2
- 230000035699 permeability Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 23
- 238000009736 wetting Methods 0.000 abstract description 3
- 239000002932 luster Substances 0.000 abstract 1
- 239000011230 binding agent Substances 0.000 description 16
- 239000000975 dye Substances 0.000 description 11
- 238000011282 treatment Methods 0.000 description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000049 pigment Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- -1 polyethylene terephthalate Polymers 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000012546 transfer Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 238000003490 calendering Methods 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000001254 oxidized starch Substances 0.000 description 6
- 235000013808 oxidized starch Nutrition 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000009499 grossing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000005488 sandblasting Methods 0.000 description 3
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 2
- UIAFKZKHHVMJGS-UHFFFAOYSA-N 2,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 description 2
- AKEUNCKRJATALU-UHFFFAOYSA-N 2,6-dihydroxybenzoic acid Chemical compound OC(=O)C1=C(O)C=CC=C1O AKEUNCKRJATALU-UHFFFAOYSA-N 0.000 description 2
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 2
- MOZDKDIOPSPTBH-UHFFFAOYSA-N Benzyl parahydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 MOZDKDIOPSPTBH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 2
- 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
- 238000010586 diagram Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- JJXVDRYFBGDXOU-UHFFFAOYSA-N dimethyl 4-hydroxybenzene-1,2-dicarboxylate Chemical compound COC(=O)C1=CC=C(O)C=C1C(=O)OC JJXVDRYFBGDXOU-UHFFFAOYSA-N 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
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- GSCLSACFHWKTQU-UHFFFAOYSA-N 2'-chloro-6'-(diethylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(Cl)=CC=C1OC1=CC(N(CC)CC)=CC=C21 GSCLSACFHWKTQU-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- ALLSOOQIDPLIER-UHFFFAOYSA-N 2,3,4-trichlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C(Cl)=C1Cl ALLSOOQIDPLIER-UHFFFAOYSA-N 0.000 description 1
- XNWJTQPEGRQQBN-UHFFFAOYSA-N 2,3-dibenzylterephthalic acid Chemical compound C=1C=CC=CC=1CC=1C(C(=O)O)=CC=C(C(O)=O)C=1CC1=CC=CC=C1 XNWJTQPEGRQQBN-UHFFFAOYSA-N 0.000 description 1
- QAOJBHRZQQDFHA-UHFFFAOYSA-N 2,3-dichlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1Cl QAOJBHRZQQDFHA-UHFFFAOYSA-N 0.000 description 1
- GLDQAMYCGOIJDV-UHFFFAOYSA-N 2,3-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1O GLDQAMYCGOIJDV-UHFFFAOYSA-N 0.000 description 1
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 1
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 description 1
- LAUFNCOGSGXOMA-UHFFFAOYSA-N 2-butyl-4-(5-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound C1=C(O)C(CCCC)=CC(SC=2C(=CC(O)=C(CCCC)C=2)C)=C1C LAUFNCOGSGXOMA-UHFFFAOYSA-N 0.000 description 1
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
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- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GKFFBAQBFJBIDR-UHFFFAOYSA-N methyl 2,2-bis(4-hydroxyphenyl)acetate Chemical compound C=1C=C(O)C=CC=1C(C(=O)OC)C1=CC=C(O)C=C1 GKFFBAQBFJBIDR-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 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
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AJCDFVKYMIUXCR-UHFFFAOYSA-N oxobarium;oxo(oxoferriooxy)iron Chemical compound [Ba]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O AJCDFVKYMIUXCR-UHFFFAOYSA-N 0.000 description 1
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 1
- 229950005308 oxymethurea Drugs 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- QHDYIMWKSCJTIM-UHFFFAOYSA-N phenyl 1-hydroxynaphthalene-2-carboxylate Chemical compound C1=CC2=CC=CC=C2C(O)=C1C(=O)OC1=CC=CC=C1 QHDYIMWKSCJTIM-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- WKEDVNSFRWHDNR-UHFFFAOYSA-N salicylanilide Chemical compound OC1=CC=CC=C1C(=O)NC1=CC=CC=C1 WKEDVNSFRWHDNR-UHFFFAOYSA-N 0.000 description 1
- 229950000975 salicylanilide Drugs 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は画質、感度が著しく向上しかつ均質な表面光沢
の優れ又は艶消し副面である高品位感熱記録シートに間
するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention provides a high-quality heat-sensitive recording sheet that has significantly improved image quality and sensitivity, and has an excellent homogeneous surface gloss or a matte surface.
（従来の技術）
一般に感熱記録シートは２紙、フィルム等の支持体上に
熱発色性組成物を主成分とする感熱発色層を設けたもの
であり、熱ヘッド、熱ペン、レーを
ザーなとにより加熱することにより発色画像＃記録する
ものである。感熱記録方式は、他の記録方式と対比して
比較的簡単な装置で短時間に記録が得られること、騒音
の発生と環境汚染が少ないこと、コストが安いことなど
の利点があるため、ファクシミリ、レコーダー、プリン
ター、券売機。(Prior art) In general, a thermosensitive recording sheet is a sheet in which a thermosensitive coloring layer containing a thermochromic composition as a main component is provided on a support such as paper or film, and a thermal head, a thermal pen, or a laser is used. Colored images are recorded by heating. Compared to other recording methods, the thermal recording method has the advantages of being able to obtain records in a short time using relatively simple equipment, generating less noise and environmental pollution, and being inexpensive. , recorder, printer, ticket vending machine.
ラベルなど多くの用途に広く利用されている。It is widely used for many purposes such as labels.
一方２機器の多品種化及び高品位化により機器に適合す
る感熱記録シートの要求も増々高くなりつつある。例え
ば階調画像を出力できるＣＲＴ画面コピー用プリンター
、あるいは高コン−・ラストが要求される計測用プリン
ターあるいはラベルプリンターなどに用いられるもので
は優れた画質（ドツト再現性）が要求されると同時に感
熱記録シートの均質な光沢が好まれる傾向にある。逆に
ファクシミリ−あるいは一般のプリンターのように文字
画像が主であるような機器に対しては文字の読み易さが
主眼となるため表面光沢が少なく画質。On the other hand, with the diversification and higher quality of devices, the demand for heat-sensitive recording sheets that are compatible with the devices is becoming increasingly high. For example, products used in CRT screen copy printers that can output gradation images, measurement printers that require high contrast, or label printers require excellent image quality (dot reproducibility) and are also thermosensitive. There is a tendency for recording sheets to have a uniform gloss. On the other hand, for devices such as facsimile machines or general printers that mainly produce text images, the main focus is on the readability of the text, so the image quality is low and the surface gloss is low.
感度の優れた感熱記録シートが必要とされる。更に、全
ての機器に共通して機器の低電力化及び高解像化が進み
、これら機器に対応するための高感度化、高画質化が必
要とされ、更に外観の上で均質で且つ光沢調あるいは艶
消し副表面を有するものを用途により選択できることが
切望されていた。A heat-sensitive recording sheet with excellent sensitivity is required. Furthermore, as all devices are becoming less power-consuming and have higher resolution, higher sensitivity and higher image quality are required to support these devices. There has been a strong desire to be able to select a material with a textured or matte subsurface depending on the application.
このような感熱記録シートは従来紙等の支持体上に感熱
発色層を塗布し、乾燥後表面平滑性を高め画質、感度が
向上するようにスーパーカレンダーのような平滑化処理
を施して製造されている。Such heat-sensitive recording sheets are conventionally manufactured by coating a heat-sensitive coloring layer on a support such as paper, and after drying, subjecting it to a smoothing process such as a supercalender to increase surface smoothness and improve image quality and sensitivity. ing.
（発明が解決しようとする問題点）
しかしながら、このような製造方法によっては満足され
るような高画質、高感度で均質な表面光沢を有する感熱
記録シートあるいは高画質、高感度で均質な艶消し副表
面を有する感熱記録シートを得ることは困難であった。(Problems to be Solved by the Invention) However, depending on this manufacturing method, a heat-sensitive recording sheet with high image quality, high sensitivity, and uniform surface gloss, or high image quality, high sensitivity, and homogeneous matte surface gloss, which is satisfactory, cannot be produced. It has been difficult to obtain a heat-sensitive recording sheet having a subsurface.
表面平滑性を高めサーマルヘッドとの接触を良くシ２画
質、感度を向上させる万葉として種々提案されている。Various methods have been proposed to improve surface smoothness, improve contact with the thermal head, and improve image quality and sensitivity.
例えばスーパーカレンダー処理を行いＢ ｅ ｋ ｋ平
滑性を２００秒−１０００秒にする方法（特公昭５２−
２０１４２号）、ワックスを配合したアンダーコート層
を設けた上に感熱記録層を設は更にスーパーカレンダー
処理により表面■さＲｚを２μｍ以下にする方法（特開
昭５９−２０４５９４）、加熱した金属ロールを用いた
スーパーカレンダー処理を行い光学的表面粗さＲｐを３
．５μｍ以下にする方法（特開昭６１−２３７６８３）
、あるいはベント方式のプレートコーティング法で感熱
記録層を塗工し乾燥して表面粗ざ傘Ｒａを１．２ノ１ｍ
以下にする方法（特開昭５５−１５６０８６）などがあ
る。For example, a method of super calendering to achieve B e k k smoothness of 200 seconds to 1000 seconds (Japanese Patent Publication No. 1973-
No. 20142), a method in which a heat-sensitive recording layer is provided on an undercoat layer containing wax, and the surface roughness Rz is reduced to 2 μm or less by supercalender treatment (Japanese Patent Application Laid-Open No. 59-204594), a heated metal roll. The optical surface roughness Rp was reduced to 3 by super calendaring using
．． Method for reducing the thickness to 5 μm or less (Japanese Patent Application Laid-Open No. 61-237683)
Alternatively, apply a heat-sensitive recording layer using a vent plate coating method and dry it to a surface roughness Ra of 1.2 m.
There are the following methods (Japanese Unexamined Patent Publication No. 55-156086).
しかし、これらの方策を用いてもまだ十分な画質、感度
を与えるための平滑性を得ることができず、更に、これ
ら平滑性のための指標もまだ十分には画質に対応してい
なかった。However, even with these measures, it has not yet been possible to obtain smoothness to provide sufficient image quality and sensitivity, and furthermore, these indices for smoothness have not yet adequately corresponded to image quality.
また、感熱記録シートの外観を向上させる試みも多く行
われている。例えば、カレンダー処理時の地肌汚れ及び
光沢ムラを防止するための感熱記録屡の原料処方（特公
昭５０−１４５３１．特公昭５１−５９４７．特開昭５
６−４６７８６．特開昭６０−６４８８８など）、ある
いはカレンダー処理条件（特開昭５９−１５５０９４）
などが提案されているが、カレンダー処理のような平滑
化処理では支持体の地合いのムラあるいは感熱記録層の
塗工ムラによると思える光沢ムラを無くすことは困難で
あり、それ故、均質な光沢の優れた感熱記録シートを得
ることはできなかった。逆に均質な艶消し副面を得るに
は、カレンダーのような平滑化処理を行わないか、ある
いは必要最小限に限定するなどの処°理が用いられるが
、これらの処理では得られた感熱記録シートは逆に平滑
性が低下し９画質、感度が劣ったものとなった。Furthermore, many attempts have been made to improve the appearance of heat-sensitive recording sheets. For example, raw material formulations for heat-sensitive recording materials to prevent background stains and uneven gloss during calendering (Japanese Patent Publication No. 50-14531.
6-46786. JP-A-60-64888, etc.) or calendar processing conditions (JP-A-59-155094)
However, it is difficult to eliminate uneven gloss caused by uneven texture of the support or uneven coating of the heat-sensitive recording layer with smoothing treatments such as calendering. It was not possible to obtain an excellent heat-sensitive recording sheet. On the other hand, in order to obtain a homogeneous matte subsurface, treatments such as calendering or other smoothing treatments are either not performed or are limited to the necessary minimum, but these treatments On the contrary, the smoothness of the recording sheet deteriorated, resulting in poor image quality and sensitivity.
（問題を解決するための手段） 本発明者等は、このような画質、感度が優れ。(Means to solve the problem) The inventors of the present invention have achieved such excellent image quality and sensitivity.
且つ、均質な光沢調あるいは艶消し副面を有する高品位
感熱記録シートを得るため鋭意研究した結果９本発明に
到達したものである。In addition, the present invention was arrived at as a result of extensive research in order to obtain a high-quality thermosensitive recording sheet having a uniform gloss tone or a matte subsurface.
尚９本発明における粗さ曲線及び彌づ１ＨＦｂ東ｉ爆セ
み接触率は以下の方法により求めたものである。Incidentally, the roughness curve and the contact ratio of 1HFb TOI in the present invention were determined by the following method.
粗さ曲線： Ｊ Ｉ ５−Ｂ−０６０１にもとづき。Roughness curve: Based on JI 5-B-0601.
触針先端曲率半径５μｍを用い測定針圧４ｍＮ（２，５
ｍｍ、カットオフｌｉ、、により測定し、チャートに記
録したものであり、測定装置として東京精密（株）社製
サーフコム１５００Ａを使用した。その測定例として別
紙図２が示される。The stylus pressure was 4 mN (2,5
mm, cutoff li, and recorded on a chart, using Surfcom 1500A manufactured by Tokyo Seimitsu Co., Ltd. as the measuring device. Attachment FIG. 2 is shown as an example of the measurement.
が粗さ曲線を横切る長さの割合であり、別紙図２におけ
るＬｌ、Ｌ２． ・・・、Ｌｎ及びＬとから次式であ
られされる。is the ratio of the length that crosses the roughness curve, and Ll, L2 . ..., Ln and L by the following formula.
本発明は
１、支持体上に、加熱により発色する感熱記録層を設け
た感熱記録シートの最外表面層を形成する際、最外表面
層が湿潤状態で他の平滑体表面と接合した状態で乾燥し
２次いで該感熱記録層を平滑体表面から剥離することを
特徴とする高品位感熱記録シートの製造方法。1. When forming the outermost surface layer of a heat-sensitive recording sheet having a heat-sensitive recording layer that develops color upon heating on a support, the outermost surface layer is bonded to the surface of another smooth body in a wet state. 1. A method for producing a high-quality heat-sensitive recording sheet, which comprises drying the heat-sensitive recording layer, and then peeling the heat-sensitive recording layer from the surface of the smooth body.
であり、特に、最外表面層の湿潤状態が半乾燥状態とす
る方法、最外表面層の湿潤状態が乾燥した表面に溶媒を
塗布して再湿潤した状態とする方法。In particular, a method in which the wet state of the outermost surface layer is a semi-dry state, and a method in which a wet state of the outermost surface layer is brought into a dry state by applying a solvent to the dry surface.
壺外表面層の湿潤状態が乾燥した表面に更に感熱記録層
塗液又は保護層塗液を塗布して再湿潤する方法、乾燥し
た最外表面層の表面に更に感熱記録層塗液又は保護層塗
液を塗布する方法として乾燥した表面と接合させる平滑
体表面が接合する入口部に塗液の液溜りが継続して生じ
るように液の供給量を調節する方法、支持体が透気度が
３００秒以下の下塗紙であるもの、感熱記録層が異なっ
た色相に発色する複数の感熱記録層からなるもの、感熱
記録層が一旦他の平滑体表面に塗布し、乾燥した後支持
体又は下塗りされた支持体上に転写されろものが具体的
に示される。A method in which the wet state of the outer surface layer of the vase is re-wetted by further applying a heat-sensitive recording layer coating liquid or a protective layer coating liquid to the dry surface, and a method in which a heat-sensitive recording layer coating liquid or a protective layer is further applied to the surface of the dried outermost surface layer. A method for applying the coating liquid is to adjust the amount of liquid supplied so that a pool of coating liquid continuously forms at the inlet where the dry surface and the smooth surface to be bonded are connected, and the support has air permeability. Undercoated paper for 30 seconds or less, those consisting of multiple heat-sensitive recording layers that develop colors in different hues, the heat-sensitive recording layer once coated on the surface of another smooth body, dried, and then coated on the support or undercoated. What is transferred onto the support is specifically shown.
又、このようなの方法により支持体上に加熱により発色
する一層または二層以上の感熱記録層につ・１′８−
いてその表面平滑痩がＪ Ｉ ５−Ｂ−０６０１法に基
づく粗さ曲線の中心線に平行で且つ粗さ曲線と接触率が
１０％で交わる直線から１．５μｍ内側に中心線に平行
に引いた直線と粗さ曲線との接触率が８０％以上である
平滑面で有ることを特徴とする高品位感熱記録シート、
更に好ましくは、粗さ曲線と接触率が１０％で交わる直
線から１．５／ｊ ｍ内側に中心線と平行に引いた直線
と粗さ曲線％以下の艶消し状の高品位感熱記録シートを
与えるものである。In addition, the surface smoothness of one or more heat-sensitive recording layers that develops color by heating on a support by such a method is determined by the roughness curve based on the JI 5-B-0601 method. A smooth surface where the contact ratio between the roughness curve and a straight line drawn parallel to the center line 1.5 μm inside from the straight line that is parallel to the center line and intersects the roughness curve at a contact ratio of 10% is 80% or more. A high-quality heat-sensitive recording sheet characterized by
More preferably, a matte high-quality heat-sensitive recording sheet with a straight line drawn parallel to the center line 1.5/j inward from a straight line that intersects the roughness curve at a contact ratio of 10% and a roughness curve of % or less. It is something to give.
本発明の感熱記録シートに用いられる支持体としては、
上質紙９片艶紙、コート紙９合成紙等の紙類、ポリエチ
レンテレフタレート、ポリエチレン、ポリプロピレン等
のプラスチックフィルム等があげられる。The support used in the heat-sensitive recording sheet of the present invention includes:
Examples include papers such as high-quality paper (9) glossy paper, coated paper (9) and synthetic paper, and plastic films such as polyethylene terephthalate, polyethylene, and polypropylene.
本発明で用いられる熱発色性材料としては、（１）フル
オラン系、トリフェニルメタン系、スビロビラン系、オ
ーラミン系、フェノチアジン系などのロイコ染料および
加熱時にこれらと反応して発色させる顕色剤との組合せ
、（２）レゾルシンとニトロソ化合物との絹合せのよう
なオキサジン染料を形成するもの、あるいはアゾ染料を
形成するもの、（３）ジアゾニウム塩と力・シブラーに
よリアゾ染料を形成するもの、（４）第２級アルコール
性水酸基を有する化合物と金属無機塩類または金属の酢
酸塩類とを組合せた成分を含有するもの、（５）炭水化
物と脱水剤との絹合せ、（６）長鎖脂肪酸金属塩とフェ
ノール性物質との絹合せ。The thermochromic materials used in the present invention include (1) leuco dyes such as fluorane, triphenylmethane, subirobilane, auramine, and phenothiazine, and color developers that react with these dyes to develop color when heated; combinations, (2) those that form oxazine dyes, such as silk combinations of resorcinol and nitroso compounds, or those that form azo dyes; (3) those that form lyazo dyes with diazonium salts and shiblar; ( 4) Those containing a combination of a compound having a secondary alcoholic hydroxyl group and metal inorganic salts or metal acetates, (5) A silk combination of a carbohydrate and a dehydrating agent, (6) Long-chain fatty acid metal salts and silk combination with phenolic substances.
（７）有機酸重金属塩とアルカリ土類金属硫化物との組
合せ、（８）有機酸重金属塩と有機キレート剤との組合
せ、（９）重金属シュウ酸塩と硫黄化合物との絽合せ、
（１０）脂肪酸金属塩と芳香族ポリヒト′ロキシ化合物
との組合せ、（１１）有機酸貴金属塩と有機ポリヒドロ
キシ化合物との組合せ、（１２）有機酸貴金属塩と芳香
族有機還元剤との組合せ、（１３）高級脂肪酸重金属塩
とジアルキルジチオ力、ルバミン酸亜鉛との紹合せなど
が挙げられるが、これらの矧み合わせに限定されるもの
ではなく加熱により発色する組成物であれば良い。(7) combination of organic acid heavy metal salt and alkaline earth metal sulfide, (8) combination of organic acid heavy metal salt and organic chelating agent, (9) mating of heavy metal oxalate and sulfur compound,
(10) a combination of a fatty acid metal salt and an aromatic polyhydroxy compound, (11) a combination of an organic acid noble metal salt and an organic polyhydroxy compound, (12) a combination of an organic acid noble metal salt and an aromatic organic reducing agent, (13) Examples include combinations of higher fatty acid heavy metal salts, dialkyldithiolytic compounds, and zinc rubamate, but the composition is not limited to these combinations as long as it develops color when heated.
このようなロイコ染料としては、たとえば、３゜３−ビ
ス（ｐ−ジメチルアミノフェニル）フタリド、３，３−
ビス（ｐ−ジメチルアミノフェニル）−６−シメチルフ
タリド、３，３−ビス（ｐ−ジメチルアミノフェニル）
−６−アミノフタリド、３．３−ビス（ｐ−ジメチルア
ミノフェニル）−６−ニトロフタリド、３，３−ビス（
ｐ−ジメチルアミノフェニル）−４，５，６，７−チト
ラクロロフタリド、３−ジメチルアミノ−７−メチルフ
ルオラン、３−ジエチルアミノ−７−クロロフルオラン
、３−ジエチルアミノ−６−メチル−７−フェニルアミ
ノフルオラン、３−Ｎ−エチル−Ｎ−ペンチルアミノ−
６−メチル−７−フェニルアミノフルオラン、３−Ｎ−
メチル−Ｎ−シクロへキシルアミノ−６−メチル−７−
フェニルアミノフルオラン、３−ジブチルアミノ−７−
ｏ−クロロフェニルアミノフルオラン、３−ジエチルア
ミノ−７−０−クロロフェニルアミノフルオラン、３−
Ｎ−エチル−Ｎ−ｐ−トリル−６−メチル−７−フェニ
ルアミノフルオラン、３−ピロリジノ−６−メチル−７
−フェニルアミノフルオラン、３−ジエチルアミノ−６
−メチル−７−ｐ−ｎ−ブチルフェニルアミノフルオラ
ン、３−Ｎ−メチル−Ｎ−プロピルアミノ−６−メチル
−７−フェニルアミノフルオラン、３−ジブチルアミノ
−７−０−フルオロフェニルアミノフルオラン、３−ジ
エチルアミン−７−ドリフルオロメチルフエニルアミノ
フルオラン、３−Ｎ−エチル−ｐ−トルイジノ−７−メ
チルフェニルアミノフルオラン、ローダミンＢラクタム
、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、３−ヘンシルスピロナフトピランなど
があげられる。Examples of such leuco dyes include 3°3-bis(p-dimethylaminophenyl)phthalide, 3,3-
Bis(p-dimethylaminophenyl)-6-dimethylphthalide, 3,3-bis(p-dimethylaminophenyl)
-6-aminophthalide, 3,3-bis(p-dimethylaminophenyl)-6-nitrophthalide, 3,3-bis(
p-dimethylaminophenyl)-4,5,6,7-titrachlorophthalide, 3-dimethylamino-7-methylfluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-6-methyl-7 -phenylaminofluorane, 3-N-ethyl-N-pentylamino-
6-Methyl-7-phenylaminofluorane, 3-N-
Methyl-N-cyclohexylamino-6-methyl-7-
Phenylaminofluorane, 3-dibutylamino-7-
o-chlorophenylaminofluoran, 3-diethylamino-7-0-chlorophenylaminofluoran, 3-
N-ethyl-N-p-tolyl-6-methyl-7-phenylaminofluorane, 3-pyrrolidino-6-methyl-7
-phenylaminofluorane, 3-diethylamino-6
-Methyl-7-p-n-butylphenylaminofluorane, 3-N-methyl-N-propylamino-6-methyl-7-phenylaminofluorane, 3-dibutylamino-7-0-fluorophenylaminofluoran Orane, 3-diethylamine-7-dolifluoromethylphenylaminofluorane, 3-N-ethyl-p-toluidino-7-methylphenylaminofluorane, Rhodamine B lactam, 3-methylspirodinaphthopyran, 3-ethyl Examples include spirodinaphthopyran and 3-hensylspironaphthopyran.
又、前記の顕色剤としては、たとえば４−フェニルフェ
ノール、４−ヒドロキシアセトキノン、２．２′−ジヒ
ドロキシジフェニル、ｎ−ブチルビス（４−ヒドロキシ
フェニル）アセテート、メチルビス（４−ヒドロキシフ
ェニル）アセテート、１ｓｏ−ブチルビス（４−ヒドロ
キシフェニル）アセテート、２．２′−メチレンビス（
４−クロロフェノール）、２．２’−メチレンビス （
４−メチル−６−ｔ−ブチルフェノール）、４．４’−
イソプロピリデンジフェノール（別名ビスフェノールＡ
、以下ＢＰＡと略称する）、４．４′、−イソプロピリ
デンビス（２−クロロフェノール）、４，４“−イソプ
ロピリデンビス（２−メチルフェノール）、１．１−ビ
ス（４−ヒドロキシフェニル）−１−フェニルエタン、
１，３−ジ（２−（４−ヒドロキシフェニル）−２−プ
ロピル）ベンゼン、４，４′−エチレンビス（２−メチ
ルフェノール）、４．４’−チオビス（６−１−ブチル
−３−メチルフェノール）、レゾルシールモノベンゾエ
ート、１，１−ビス（４−ヒドロキシフェニル）−シク
ロヘキサン、２，２′−ビス（４−ヒドロキシフェニル
）−Ｎ−へブタン、４ 。Examples of the color developer include 4-phenylphenol, 4-hydroxyacetoquinone, 2,2'-dihydroxydiphenyl, n-butylbis(4-hydroxyphenyl)acetate, methylbis(4-hydroxyphenyl)acetate, 1so-butylbis(4-hydroxyphenyl)acetate, 2,2'-methylenebis(
4-chlorophenol), 2,2'-methylenebis (
4-methyl-6-t-butylphenol), 4.4'-
Isopropylidene diphenol (also known as bisphenol A)
, hereinafter abbreviated as BPA), 4,4'-isopropylidene bis(2-chlorophenol), 4,4''-isopropylidene bis(2-methylphenol), 1,1-bis(4-hydroxyphenyl) -1-phenylethane,
1,3-di(2-(4-hydroxyphenyl)-2-propyl)benzene, 4,4'-ethylenebis(2-methylphenol), 4,4'-thiobis(6-1-butyl-3- methylphenol), resorcyl monobenzoate, 1,1-bis(4-hydroxyphenyl)-cyclohexane, 2,2'-bis(4-hydroxyphenyl)-N-hebutane, 4.
４′−シクロへキシリデンビス（２−イソプロピルフェ
ノール）、４．４’−ジヒドロキシ−ジフェニルスルポ
ン、４−ヒドロキシ−４’ −１ｓｏ −プロピルオキ
シ−ジフェニルスルホン、４，４′−ジヒドロキシ−３
，３′−ジアリルジフェニルスルホン、サリチル酸アニ
リド、ノボラック型フェノール樹脂、安息香酸、ｐ−ｔ
−ブチル安息香酸、０−クロロ安息香酸、ｐ−クロロ安
息香酸、ジクロロ安息香酸、トリクロロ安息香酸、ｍ−
ヒドロキシ安息香酸、ｐ−ヒドロキシ安息香酸、ｐ−ヒ
ドロキシ安息香酸ベンジルエステル、０−）ルイルａ、
ｍ−）ルイル酸、ｐ−トルイル酸、フタル酸、イソフタ
ル酸、テレフタル酸、没食子酸、トリメリット酸、サリ
チル酸、３−エチルサリチル酸、４−エチルサリチル酸
、３−フェニルサリチル酸、５−フェニルサリチル酸、
３−ヒドロキシサリチル酸、４−ヒドロキシサリチル酸
、５−ヒドロキシサリチル酸、６−ヒドロキシサリチル
酸、４−ヒドロキシフタル酸ジメチル、α−ナフトエ酸
、β−ナフトエ酸、などがあげられる。4'-Cyclohexylidenebis(2-isopropylphenol), 4,4'-dihydroxy-diphenylsulfone, 4-hydroxy-4'-1so-propyloxy-diphenylsulfone, 4,4'-dihydroxy-3
, 3'-diallyldiphenyl sulfone, salicylic acid anilide, novolak type phenolic resin, benzoic acid, p-t
-Butylbenzoic acid, 0-chlorobenzoic acid, p-chlorobenzoic acid, dichlorobenzoic acid, trichlorobenzoic acid, m-
hydroxybenzoic acid, p-hydroxybenzoic acid, p-hydroxybenzoic acid benzyl ester, 0-)ruyl a,
m-) toluic acid, p-toluic acid, phthalic acid, isophthalic acid, terephthalic acid, gallic acid, trimellitic acid, salicylic acid, 3-ethylsalicylic acid, 4-ethylsalicylic acid, 3-phenylsalicylic acid, 5-phenylsalicylic acid,
Examples include 3-hydroxysalicylic acid, 4-hydroxysalicylic acid, 5-hydroxysalicylic acid, 6-hydroxysalicylic acid, dimethyl 4-hydroxyphthalate, α-naphthoic acid, β-naphthoic acid, and the like.
また、前記したような熱発色性成分の他に、混合してバ
インダーとしてデンプン類、セルロース類、タンパク質
類等の天然組成物系バインダーあるいはポリビニルアル
コール、アクリル系、スチレン系などの合成バインダー
等水溶性又は有機溶媒溶解性の樹脂類が挙げられる。In addition to the above-mentioned thermochromic components, water-soluble binders such as natural composition binders such as starches, celluloses, and proteins, or synthetic binders such as polyvinyl alcohol, acrylic, and styrene binders can be used as a binder. Alternatively, resins soluble in organic solvents may be mentioned.
また白色度、不透明度を増しサーマルヘッドに対する走
行性を向上させるために顔料として炭酸カルシウム、炭
酸マグネシウム、ケイ酸、ケイ酸アルミニウム、ｆａ酸
バリウム、酸化チタン、酸化亜鉛などの無８１顔料ある
いはアクリル系、スチレン系などの有機顔料が用いられ
る。In addition, in order to increase whiteness and opacity and improve runnability against thermal heads, pigments such as calcium carbonate, magnesium carbonate, silicic acid, aluminum silicate, barium ferrite, titanium oxide, zinc oxide, etc., or acrylic-based pigments are used. , organic pigments such as styrenic pigments are used.
更に添加剤としてパラフィンワックス、ステアリン酸ア
ミド、エチレンビスステアロアミド、ステアリン酸亜鉛
、ステアリン酸カルシウムなどの熱可融性物質、ジオク
チルスルホコハク酸ソーダ。Furthermore, as additives, paraffin wax, stearamide, ethylene bisstearamide, zinc stearate, calcium stearate and other thermofusible substances, and sodium dioctyl sulfosuccinate.
ドデシルベンゼンスルホン酸ソーダのよう籠スルホン酸
塩あるいはリン酸エステルのような界面活性剤、ベン゛
シフエノン系、トリアゾール系などの紫外線吸収剤ある
いは蛍光染料などを適宜併用することが出来る。A surfactant such as a sulfonic acid salt such as sodium dodecylbenzenesulfonate or a phosphoric acid ester, an ultraviolet absorber such as a benzyphenone type or a triazole type, or a fluorescent dye can be appropriately used in combination.
更に平滑体からの剥離を良くするためのシリコーン系、
フッ素系、ロート油のような剥離剤も好適に使用するこ
とができる。Furthermore, silicone-based material is used to improve peeling from smooth objects.
A release agent such as fluorine-based or funnel oil can also be suitably used.
本発明に於て用いられる感熱記録層用塗液はこれら熱発
色性材料、バインダー、顔料、その他添加剤を必要に応
じて適宜組合せることができるが。The coating liquid for a heat-sensitive recording layer used in the present invention may contain appropriate combinations of these thermochromic materials, binders, pigments, and other additives as required.
例えば熱発色性材料を５〜５０％、バインダーを３〜４
０％、顔料を５〜６０％、その他添加剤を５０％以下に
することが好ましい。For example, 5-50% thermochromic material and 3-4% binder.
It is preferable that the amount of pigment be 0%, the amount of pigment be 5 to 60%, and the amount of other additives be 50% or less.
又、前記の湿潤に用いられる湿潤液としては。Also, as a wetting liquid used for the above-mentioned wetting.
水、トルエン、ミネラルスピリット、ヘキサン等バイン
ダーを溶解又は湿潤出来るものが適宜選択される。A material capable of dissolving or moistening the binder, such as water, toluene, mineral spirit, and hexane, is appropriately selected.
又、乾燥した感熱記録層の上に更に塗布するのに用いら
れる塗液は前記の感熱記録層塗液と同じ配合のものを使
うことができるが、特に保存性を強調するときには、熱
発色性材料を減らしバインダー成分を多くするとか、耐
保存性の強いバインダーを使う、あるいは紫外線吸収剤
を入れるなどの方策が用いられる。逆に、特に感度を重
視するときには感度の高い熱発色性材料を使い比率を増
やす、などの調節が必要に応じて成される。In addition, the coating liquid used for further coating on the dried heat-sensitive recording layer can have the same composition as the heat-sensitive recording layer coating liquid described above, but when emphasizing preservability in particular, thermochromic Measures such as reducing the amount of materials and increasing the binder component, using a binder with strong storage resistance, or adding ultraviolet absorbers are used. On the other hand, when sensitivity is particularly important, adjustments such as using a highly sensitive thermochromic material and increasing the ratio are made as necessary.
感熱記録層の塗工量としては特に限定されるものではな
いが、転写層あるいは再湿潤層も含めた全体として、乾
燥重量で２〜２５ ｇ ／ ｍ’、好ましくは４〜１５
ｇ ／ ｍ’である。The coating amount of the heat-sensitive recording layer is not particularly limited, but the total dry weight including the transfer layer or rewetting layer is 2 to 25 g/m', preferably 4 to 15 g/m'.
g/m'.
又、感熱発色性材料を含有しない保護層あるいは感熱発
色材料が少ない層は１０ ｇ ／ ｒｎ”以下、特に５
ｇ／−以下の範囲が好ましい。In addition, the protective layer that does not contain a heat-sensitive coloring material or a layer that contains only a small amount of heat-sensitive coloring material has a density of 10 g/rn” or less, especially 5
The range below g/- is preferable.
本発明の感熱記録シート表面を製造する方法として、一
般のキャスト法（塗液が可塑性の有る状態で平滑体と密
着させ可塑性が無くなった後剥離する方法）であるが、
具体的には次の２つの方法が好適に適用できる。The method for producing the surface of the heat-sensitive recording sheet of the present invention is a general casting method (a method in which the coating liquid is brought into close contact with a smooth body in a plastic state and then peeled off after the plasticity is lost).
Specifically, the following two methods can be suitably applied.
（Ａ法）平滑体側に転写層を形成した後、支持体側に該
転写層を転写することにより感熱記録シートを得る方法
である。(Method A) This is a method for obtaining a heat-sensitive recording sheet by forming a transfer layer on the smooth body side and then transferring the transfer layer to the support side.
より具体的には、平滑体上に転写層を塗布し半乾燥状態
あるいは乾燥後、接着性を有する物質を介して支持体表
面あるいは感熱記録層表面に接合し、接合後平滑体表面
から剥離する方法である。More specifically, a transfer layer is applied onto a smooth body, and after it is semi-dry or dried, it is bonded to the support surface or the heat-sensitive recording layer surface via an adhesive substance, and after bonding, it is peeled off from the smooth body surface. It's a method.
このとき転写層は、支持体が既に感熱層を設けてある支
持体を使う場合、必ずしも熱発色成分を含む必要は無い
。最終的に一層中、あるいは各層中に熱発色性成分を含
んでいれば良い。平滑体表面でも使用可能である。At this time, the transfer layer does not necessarily need to contain a thermal color-forming component when a support already provided with a heat-sensitive layer is used. Finally, it is sufficient that the thermochromic component is contained in one layer or in each layer. It can also be used on smooth surfaces.
（Ｂ法）支持体に感熱記録層を塗布し、半乾燥状態、乾
燥後再湿潤した状態あるいは乾燥後感熱記録層塗液また
は保護層塗液を塗布した状態で平滑体表面と接合し、接
合したまま乾燥し、乾燥復線平滑体より剥離することに
より平滑表面を有する感熱記録シートを得る方法である
。これらの方法の中で生産安定性の面からは感熱記録層
を支持体上に塗布し、一旦乾燥した後で再度塗液を塗布
するという方法が好ましく、このとき平滑体と支持体の
接合部入口において、塗液の継続的な液溜まりができる
ように調節することが好適に行われる。(Method B) A heat-sensitive recording layer is coated on a support and bonded to the surface of a smooth body in a semi-dry state, in a re-wetted state after drying, or in a state coated with a heat-sensitive recording layer coating liquid or a protective layer coating liquid after drying. In this method, a heat-sensitive recording sheet having a smooth surface is obtained by drying the sheet while still holding it and peeling it off from the dried rectangular smooth body. Among these methods, from the viewpoint of production stability, it is preferable to apply the heat-sensitive recording layer on the support, dry it, and then apply the coating liquid again. Preferably, the inlet is regulated so that there is a continuous pool of coating liquid.
この方法において支持体は通気性のある紙が適当てあり
、また顔料、バインダーを主成分とし塗布量３〜１５ｇ
／Ｔｒ１″程度のアンダーコート層を、更に希望により
バックコート層を設けたものでも良い。In this method, the support is suitably made of breathable paper, and the main components are pigment and binder, and the coating amount is 3 to 15 g.
An undercoat layer with a thickness of about /Tr1'' may be further provided with a backcoat layer if desired.
前記Ａ法、Ｂ法に用いられる平滑体としてはシート状、
ロール状、無端ベルト状の形状で表面がＪ Ｉ ５−Ｂ
−０６０１法に基く粗さ曲線の中心線と平行で且つ粗さ
曲線と接触率が９０％となる直線から表面側に１．５１
１ｍの位置に中心線に平行に引いた直線との接触率が２
０％以下、好ましくは１０％以下である平滑表面を有す
るものが用いられる。The smooth bodies used in the above methods A and B include sheet-like objects,
Roll-shaped, endless belt-shaped surface with J I 5-B
-1.51 points toward the surface from a straight line that is parallel to the center line of the roughness curve based on the 0601 method and has a contact rate of 90% with the roughness curve.
The contact rate with a straight line drawn parallel to the center line at a distance of 1 m is 2.
A material having a smooth surface of 0% or less, preferably 10% or less is used.
上記の接触率が９０％となる直線から表面側に滑体表面
と接合して乾燥しても高品位の感熱記録シートを得るこ
とができない。A high-quality thermosensitive recording sheet cannot be obtained even if the sheet is bonded to the sliding body surface from the straight line where the contact ratio is 90% and dried.
又、これらの平滑体を用いて感熱記録シートを製造する
際、光沢面を有するものを希望する場合は外観上も光沢
を有する平滑体を用い、艶消し調の感熱記録シートを希
望する場合は表面を化学的な処理あるいはサンドブラス
ト法のような処理により艶消し加工を施したものが用い
られるが、いずれにしても前記の表面平滑性を有するも
のでなければならない。In addition, when manufacturing a heat-sensitive recording sheet using these smooth bodies, if you want one with a glossy surface, use a smooth body that has a glossy appearance, and if you want a matte-like heat-sensitive recording sheet, use a smooth body that has a glossy appearance. A material whose surface has been given a matte finish by chemical treatment or a treatment such as sandblasting is used, but in any case, it must have the above-mentioned surface smoothness.
このような素材としては、ＰＥＴ、ＰＰ、ＰＥ等のプラ
スチックフィルムあるいは金属等であり。Such materials include plastic films such as PET, PP, and PE, or metals.
表面を金属メッキを施したものあるいはテフロンなどの
樹脂加工したものが好ましい。また離型性を良くするた
めシリコーン、フッ素、界面活性剤。Preferably, the surface is plated with metal or treated with a resin such as Teflon. Silicone, fluorine, and surfactants are also used to improve mold release.
ワックスなどで好適に処理される。本発明において操作
性、耐久性、剥離性などの面より表面をクロムメッキし
たロール状の平滑体が好ましく、更にクロムメッキ面上
にテフロン加工処理したものも、剥離性の点より優れて
いる。Suitable for treatment with wax etc. In the present invention, a roll-shaped smooth body whose surface is plated with chromium is preferable in terms of operability, durability, releasability, etc. Furthermore, a smooth body in the form of a roll whose surface is plated with chrome is also superior in terms of releasability.
（作用及び効果）
（ｂ
以上のようにして湿潤状態で平滑体と接合子まま乾燥す
ることにより得られた感熱記録シートの表面は、感熱記
録層の表面平滑性がＪＩＳ−Ｂ−０６０１法に基づく粗
さ曲線の中心線に平行で。(Functions and Effects) (b) The surface of the heat-sensitive recording sheet obtained by drying the smooth body and the zygote in a wet state as described above has a surface smoothness of the heat-sensitive recording layer that meets the JIS-B-0601 method. parallel to the center line of the based roughness curve.
月つ、粗さ曲線と接触率が１０％で交わる直線から１．
５７ｚｍ内側に中心線と平行に引いた直線と粗さ曲線と
の接触率が８０％以上である平滑面にすることができ、
このような平滑面を有する感熱記録シートはサーマルヘ
ッドに対する平滑性が良好であり画質、感度に優れてい
る。平滑体表面を光沢調あるいは艶消し調のものを使う
ことにより、感熱記録シートの画質、感度を低下させな
いで均質な光沢副表面あるいは艶消し副表面の外観を有
する感熱記録シートを得ることができる。1. From the straight line that intersects the roughness curve and the contact ratio at 10%.
It is possible to create a smooth surface with a contact ratio of 80% or more between the straight line drawn parallel to the center line inside the 57zm and the roughness curve,
A heat-sensitive recording sheet having such a smooth surface has good smoothness against a thermal head and has excellent image quality and sensitivity. By using a smooth surface with a glossy or matte finish, it is possible to obtain a heat-sensitive recording sheet that has the appearance of a homogeneous glossy subsurface or matte subsurface without reducing the image quality or sensitivity of the heat-sensitive recording sheet. .
（実施例）
次に本発明を実施例によって更に具体的に説明するが２
本発明はこれらの実施例の記載に限定されるものではな
い。(Example) Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to the description of these examples.
本発明の実施例における測定方法は下記の通りである。The measurement method in Examples of the present invention is as follows.
１、光沢度：住η村上色彩研究所製
光沢計ＧＭ−３角度７５゜
２、画質・感度：松下電子部品■製のテスト俺を用いて
印加電圧１６．ＯＶパルス幅１．０〜３．４．ｍｓで作
画後マクヘス反羽濃度計（ＲＤ−９１４）で画像濃度を
測定した。また画像部について目視及び拡大写真により
ドツト再現性を評価した。1. Glossiness: Gloss meter GM-3 made by Murakami Color Research Institute Angle 75°2 Image quality/sensitivity: Applied voltage 16. OV pulse width 1.0-3.4. After drawing with ms, the image density was measured with a Maches anti-feather densitometer (RD-914). In addition, the dot reproducibility of the image area was evaluated visually and by using enlarged photographs.
３８平滑性：王研式平滑性測定器を使用した。38 Smoothness: An Oken type smoothness measuring device was used.
４、外観二目視により光沢ムラ、地肌汚れを観察し評価
゛した。4. Appearance was evaluated by observing uneven gloss and background stains with a second glance.
５、光学的表面粗さＲｐ：■東洋精機製作所製マイクロ
トポグラフを使用した。5. Optical surface roughness Rp: ■ A microtopograph manufactured by Toyo Seiki Seisakusho was used.
測定条件：印加圧力 １０ ｋｇ ｆ／ ＣＴ／サンプ
リングタイム１００ｍ５
６、平均波長Ｒλａ、中心線平均粗さＲａ及び１０点平
均粗さＲＲＺの値は前記測定Ｂ置す−フコム１５００Ａ
で出力される値を用いた。Measurement conditions: applied pressure 10 kg f/CT/sampling time 100 m5 6, average wavelength Rλa, center line average roughness Ra, and 10-point average roughness RRZ values are based on the measurement B-Fucom 1500A.
I used the value output in .
実施例Ｉ
Ａ液・φロイコ染料１０部（３−Ｎ−エチル−Ｎ−ペン
チルアミノ−６−メチル−７−フエニルアミノフルオラ
ン二山田化学工業−＆１Ｓ−２０５）、Ｐ−ヒドロキシ
安息香酸ベンジルエステル２０部、ジベンジルテレフタ
ル酸５部、ステアリン酸亜鉛１０部、炭酸カルシウム３
０部をそれぞれ平均粒径２μｍ以下になるようにサンド
グラインダーで分散したものと、バインダー２０部（酸
化デンプン１５部、ＰＶＡ５部）とを水に混合して固形
分濃度２３％の感熱Ｎ塗液とした。Example I Solution A/φ leuco dye 10 parts (3-N-ethyl-N-pentylamino-6-methyl-7-phenylaminofluoran Niyamada Kagaku Kogyo-&1S-205), benzyl P-hydroxybenzoate 20 parts of ester, 5 parts of dibenzyl terephthalic acid, 10 parts of zinc stearate, 3 parts of calcium carbonate
A heat-sensitive N coating liquid with a solid content concentration of 23% is prepared by dispersing 0 part of each with a sand grinder so that the average particle size is 2 μm or less, and 20 parts of a binder (15 parts of oxidized starch, 5 parts of PVA) in water. And so.
第１図に示すようなキャストコーターを用い。Use a cast coater as shown in Figure 1.
支持体として米坪４７ ｇ ／ ｔｎ’の片艶紙１の光
沢面上に前記Ａ液を乾燥重量が３ ｇ ／ ｔｎ”にな
るようにエアーナイフ３で塗布した。この後、熱風ドラ
イヤー４に通、して乾燥し、成品−次に硬度９０°のブ
レスロール５を用いてシリンダーロール８の平滑表面と
接合した。この時プレスロール５とシリンダーロール８
の接合入口部において液供給ノズル６から前記Ａ液が供
給され、液溜り７が継続的に形成されるように調整した
。また再湿潤液の塗工量は乾燥重量でＩｇ／ｍ’（下層
と合わせて４ｇ／セ）になるようプレス圧を調節した。The above-mentioned liquid A was applied onto the glossy surface of glossy paper 1 with a weight of 47 g/tn' as a support using an air knife 3 so that the dry weight was 3 g/tn''.Thereafter, it was applied to a hot air dryer 4. The finished product was passed through and dried, and then joined to the smooth surface of a cylinder roll 8 using a press roll 5 with a hardness of 90°.At this time, the press roll 5 and cylinder roll 8
Adjustment was made so that the liquid A was supplied from the liquid supply nozzle 6 at the junction inlet of and a liquid pool 7 was continuously formed. Further, the press pressure was adjusted so that the coating amount of the rewetting liquid was Ig/m' (4 g/m' including the lower layer) in terms of dry weight.
このようにして計量して塗布された感熱記録シートはシ
リンダーロール８の平滑な表面と接合したまま熱風乾燥
機９により乾燥し、乾燥後該シリンダー〇−ル８表面よ
り剥離することにより感熱記録シート１０が得られた。The heat-sensitive recording sheet weighed and applied in this manner is dried in a hot-air dryer 9 while being bonded to the smooth surface of the cylinder roll 8, and after drying, it is peeled off from the surface of the cylinder roll 8 to form a heat-sensitive recording sheet. 10 was obtained.
本実施例におけるシリンダーロール８の表面（平滑体表
面）はクロムメッキ処理しパフ研磨仕上げをした鏡面を
有するものである。得られた感熱記録シートは粗さ曲線
における接触率１０％の直線から１．５μｍ内側の直線
の上記粗さ曲線との接触率は９０％であり１画質及び感
度が優れたものであった。また光沢度は４５％であり光
沢ムラの無い均質な光沢調表面を有していた。評価結果
を表１に示す。The surface (smooth body surface) of the cylinder roll 8 in this embodiment has a mirror surface that is chrome plated and finished with puff polishing. The resulting heat-sensitive recording sheet had a contact ratio of 90% with the roughness curve of a straight line located 1.5 μm inside from the straight line with a contact ratio of 10% in the roughness curve, and was excellent in image quality and sensitivity. The gloss level was 45%, and the surface had a uniform glossy appearance with no uneven gloss. The evaluation results are shown in Table 1.
実施例２
実施例１において、平滑体として艶消し副表面を有する
シリンダーロールを用いた以外は実施例１と全く同様に
して感熱記録シートを得た。このシリンダーロールは、
表面をクロムメッキした後パフ研磨仕上げを行い更にサ
ンドブラスト処理により艶消し副表面にしたものであり
る。得られた感熱記録シートは粗さ曲線における接触率
１０％の直線から１．５μｍ内側の直線の上記粗さ曲線
との接触率は９３％であり２画質及び感度が優れたもの
であった。また光沢度は１７％であり光沢ムラの無い均
質な艶消し副表面を有していた。評価結果を表１に示す
。Example 2 A thermosensitive recording sheet was obtained in exactly the same manner as in Example 1 except that a cylinder roll having a matte subsurface was used as the smooth body. This cylinder roll is
After the surface is chrome-plated, it is puff-polished and sandblasted to give it a matte subsurface. The resulting heat-sensitive recording sheet had a contact ratio of 93% with the roughness curve of a straight line located 1.5 μm inside from the straight line with a contact ratio of 10% in the roughness curve, and was excellent in image quality and sensitivity. Moreover, the gloss level was 17%, and it had a homogeneous matte subsurface with no uneven gloss. The evaluation results are shown in Table 1.
比較例１
実施例１と同じように、Ａ液を支持体上に乾燥重量６
ｇ ／ Ｔｎ″になるように塗工し熱風乾燥機で乾燥し
、そのまま巻取った。この感熱記録シート上に更にＡ液
を乾燥重量２ｇ／ｙｎ”（下と合せて８ｇ／イ）になる
ように塗工し熱風乾燥機で乾燥した。Comparative Example 1 In the same manner as in Example 1, liquid A was placed on the support at a dry weight of 6
g/Tn", dried in a hot air dryer, and rolled up as it was. On top of this heat-sensitive recording sheet, liquid A was further added to give a dry weight of 2 g/yn" (8 g/y in total). It was coated and dried in a hot air dryer.
得られた感熱記録シートは平滑性が低かったためスーパ
ーカレンダー処理を行い平滑性を高めたが画質、感度共
不十分であった。光沢度は２８％でありカレンダー処理
により発生したと思える地肌汚町光沢ムラが存在した。The obtained heat-sensitive recording sheet had low smoothness, so a supercalender treatment was performed to improve the smoothness, but the image quality and sensitivity were insufficient. The gloss level was 28%, and there was uneven gloss on the background, which appeared to be caused by the calendering process.
感熱記録シートは粗さ曲線における接触率１０％の直線
から１．５μｍ内側の直線の上記粗さ曲線との接触率は
５３％であった。８“平価結果を表１に示す。The heat-sensitive recording sheet had a contact ratio of 53% with the roughness curve of a straight line located 1.5 μm inside from the straight line with a contact ratio of 10% in the roughness curve. 8" average results are shown in Table 1.
実施例３
Ｂ液（転写層塗液）・・ロイコ染料（Ｓ−２０５）５部
、ビスフェノールＡ２０部、エチレンビスステアロアミ
ド２５部を、各々平均粒径２μｍ以下になるようにアト
ライターで分散したものを混合しバインダーとして１０
％水溶液のＰＶＡを３０部及び１０％水溶液の酸化デン
プンを７０部及びスチレンマレイン酸共重合体エマルジ
ョン（３５％濃度）を４０部加えた。この混合液に更に
顔料として２０％濃度のシリカ分散液を６０部添加し、
固形分濃度２２％の塗液を調製した。Example 3 Liquid B (transfer layer coating liquid): 5 parts of leuco dye (S-205), 20 parts of bisphenol A, and 25 parts of ethylene bisstearamide were each dispersed with an attritor so that the average particle size was 2 μm or less. 10 as a binder by mixing the
30 parts of PVA in 10% aqueous solution, 70 parts of oxidized starch in 10% aqueous solution and 40 parts of styrene-maleic acid copolymer emulsion (35% concentration) were added. Further, 60 parts of a 20% concentration silica dispersion liquid was added as a pigment to this mixed liquid,
A coating liquid with a solid content concentration of 22% was prepared.
Ｂ液をＢ−４サイズにカットした光沢面を有する平滑体
（ＰＥＴ７５μｍ厚：束し■製ルミラー）上にワイヤー
バーを使いＷＥＴて１０ｇ／ｍ”になるように塗工した
。塗工後熱風により半乾燥状態（目視及び指触によりは
んだんした。）にし、片ツヤ紙（米坪４７ ｇ／Ｔ＋１
２＞上にＡ液を乾燥重量で６ ｇ ／ ７ｎ”塗工しで
ある支持体とゴムローラーを用いて接合させ接合したま
ま乾燥した。乾燥後フィルムから転写層を剥離すること
により感熱記録紙が得られた。得られた感熱記録紙は表
面性に優れ画質、感度共良好であった。また光沢度は８
５％てあり均質であった。Liquid B was coated using a wire bar on a smooth body with a glossy surface (PET 75 μm thick: Lumirror manufactured by Tsushishi ■) cut into B-4 size at a coating weight of 10 g/m. After coating, hot air was applied. It was made into a semi-dry state (soldered by visual inspection and touch), and then coated with single gloss paper (47 g/T+1
2> The film was bonded to a support coated with 6 g/7n" of liquid A by dry weight using a rubber roller and dried while bonded. After drying, the transfer layer was peeled from the film to form a thermosensitive recording paper. The resulting thermal recording paper had excellent surface properties and good image quality and sensitivity.The gloss level was 8.
It was 5% and homogeneous.
実施例４
実施例３て用いた平滑体をサンドブラスト処理し艶消し
副表面を持つ平滑体を使用した。この平滑体はＪ ｌ５
−Ｂ−０６０１法に基く粗さ曲線の中心線と平行で且つ
粗さ曲線と接触率が９０％となる直線から表面側に１．
５μｍの位置に中心線に平行に引いた直線との接触率が
１５％であった。Example 4 The smooth body used in Example 3 was subjected to sandblasting treatment to obtain a smooth body having a matte subsurface. This smooth body is J l5
1. From the straight line parallel to the center line of the roughness curve based on the B-0601 method and at which the contact rate with the roughness curve is 90%, toward the surface side.
The contact rate with a straight line drawn parallel to the center line at a position of 5 μm was 15%.
その池の条件は実施例３と全く同様にして感熱記録シー
トを作製した。得られた感熱記録シートは光沢度１５％
の均質な艶消し副表面を有し画質、感度共良好であった
。A thermosensitive recording sheet was prepared using the same pond conditions as in Example 3. The resulting heat-sensitive recording sheet has a gloss level of 15%.
It had a homogeneous matte subsurface, and both image quality and sensitivity were good.
比較例２
実施例３で用いた平滑体をサンドブラスト処理して艶消
し副表面を持つ平滑体を使用した。この平滑体はＪ’１
Ｓ−Ｂ−０６０１法に基く粗さ曲線の中心線と平行で且
つ粗さ曲線と接触率が９０％となる直線から表面側に１
．５μｍの位置に中心線に平行に引いた直線との接触率
が４３％であった。その他の条件は実施例３と全く同様
にして感熱記録シートを作製した。得られた感熱記録シ
ートの性能評価結果からも判るように光沢度１３％の均
質な艶消し副表面を有していたが、所々剥離不良による
と思える転写層の抜けが存在し、画質、感度共やや劣っ
た結果となった。Comparative Example 2 The smooth body used in Example 3 was subjected to sandblasting treatment to obtain a smooth body having a matte subsurface. This smooth body is J'1
1 on the surface side from a straight line that is parallel to the center line of the roughness curve based on the S-B-0601 method and has a contact rate of 90% with the roughness curve.
．． The contact rate with a straight line drawn parallel to the center line at a position of 5 μm was 43%. A thermosensitive recording sheet was produced under the same conditions as in Example 3 except for the following conditions. As can be seen from the performance evaluation results of the resulting heat-sensitive recording sheet, it had a homogeneous matte subsurface with a gloss level of 13%, but there were some gaps in the transfer layer that seemed to be due to poor peeling, and the image quality and sensitivity were poor. Both results were slightly inferior.
実施例５
Ｃ液：ロイコ染料１０部（３−Ｎ−エチル−Ｎ−ペンチ
ルアミノ−６−メチル−７−フエニルアミノフルオラン
二山田化学工業＠Ｉ製Ｓ−２０５）、ｐ−ヒドロキシ安
息香酸ベンジルエステル２５部、ジベンジルテレフタレ
ート５部、ステアリン酸亜鉛１５部、ケイ酸アルミニウ
ム３０部をそれぞれ平均粒径２μｍ以下になるようにサ
ンドグラインダーで分散したものとバインダー２０部（
Ｐ ＶＡ１０部、酸化デンプン１０部）とを水に混合し
て固形分濃度２２％の感熱層塗液を調製した。Example 5 Solution C: 10 parts of leuco dye (3-N-ethyl-N-pentylamino-6-methyl-7-phenylaminofluoran S-205 manufactured by Niyamada Kagaku Kogyo @I), p-hydroxybenzoic acid 25 parts of benzyl ester, 5 parts of dibenzyl terephthalate, 15 parts of zinc stearate, and 30 parts of aluminum silicate were each dispersed using a sand grinder so that the average particle size was 2 μm or less, and 20 parts of a binder (
A heat-sensitive layer coating solution having a solid content concentration of 22% was prepared by mixing 10 parts of PVA and 10 parts of oxidized starch with water.
この塗液Ｃを第１図に示すようなコーターのコーターヘ
ッド３のところで乾燥重量が７ ｇ ／ ｙｎ’になる
ように片面艶出し紙（米坪４７ ｇ ／ ｔｎ’ ）の
光沢面上に塗布し水分が５０％程度になるように熱風ド
ライヤー４に通して乾燥し、得られた感熱記録シートの
塗布面を、シリンダーロール８に接合させ接合させた状
態で乾燥し、乾燥後ロールより剥離して感熱記録シート
が得られた。This coating liquid C was applied onto the glossy side of single-sided glossy paper (weighing 47 g/tn') at the coater head 3 of a coater as shown in Figure 1 so that the dry weight was 7 g/yn'. The heat-sensitive recording sheet is then dried by passing it through a hot air dryer 4 to reduce the moisture content to about 50%, and the coated surface of the obtained heat-sensitive recording sheet is bonded to a cylinder roll 8 and dried in the bonded state, and after drying, it is peeled off from the roll. A thermosensitive recording sheet was obtained.
ここで、シリンダーロール７は表面に剥離性を向上させ
るためフッ素樹脂加工されている。またロールの表面温
度は５０〜６０°Ｃに調節されていて、更にロールの外
側に乾燥を促進するため熱風機９が設置されている。Here, the surface of the cylinder roll 7 is treated with fluororesin to improve releasability. Further, the surface temperature of the roll is adjusted to 50 to 60°C, and a hot air blower 9 is installed outside the roll to promote drying.
このようにして得られた感熱記録シートについて各種の
評価を行い、その結果を表１に示した。Various evaluations were performed on the heat-sensitive recording sheet thus obtained, and the results are shown in Table 1.
その結果からもわかるように、平滑性が３０００秒であ
り地肌カブリが無く、画質、感度も優れたものであった
。As can be seen from the results, the smoothness was 3000 seconds, there was no background fog, and the image quality and sensitivity were excellent.
実施例６
Ｂ液：（感熱記録層塗液の調製）
ロイコ染料ＰＳＤ−１５０（新日曹加工（株））１０部
、ビスフェノールＡ３０部、エチレンビスステアリルア
マイド１０部、ステアリン酸カルシウム、４０部をそれ
ぞれ平均粒径２μｍ以下になろようにサンドミルで分散
したものとバインダー（（ポリビニルアルコール）２５
部とを水に混合して感熱記録層塗液りを得た。Example 6 Liquid B: (Preparation of heat-sensitive recording layer coating liquid) 10 parts of leuco dye PSD-150 (Shin Nisso Kako Co., Ltd.), 30 parts of bisphenol A, 10 parts of ethylene bisstearylamide, and 40 parts of calcium stearate, respectively. Dispersed with a sand mill so that the average particle size is 2 μm or less and a binder ((polyvinyl alcohol) 25
A heat-sensitive recording layer coating liquid was obtained by mixing the following parts with water.
（感熱記録層の形成）
得られた塗液りを６０ ｇ／ｌｒｉ’の原紙に乾燥塗布
量６ｇ／ｄになるように塗布乾燥して感熱記録シートを
得た。(Formation of Heat-Sensitive Recording Layer) The obtained coating liquid was coated on a base paper of 60 g/lri' to a dry coating amount of 6 g/d and dried to obtain a heat-sensitive recording sheet.
Ｆ液：（保護層塗液の調！り
アクリル系コート剤（Ｆ−８４６１５％水溶液；昭和電
工製）６０部と酸化澱粉（ＭＳ−３６００１５％水溶液
、日本食品製）２０部とクレー５０％水分散液１０部と
ステアリン酸亜鉛３０％水分散液１０部とジメチロール
尿素１部とを水に混合して保ｖｉＰｉ塗液Ｅ液を調製し
た。F solution: (Preparation of protective layer coating solution) 60 parts of acrylic coating agent (F-846 15% aqueous solution; manufactured by Showa Denko), 20 parts of oxidized starch (MS-3600 15% aqueous solution, manufactured by Nippon Shokuhin), and 50% clay water. A viPi coating liquid E was prepared by mixing 10 parts of the dispersion, 10 parts of a 30% zinc stearate aqueous dispersion, and 1 part of dimethylol urea in water.
上記のように得られた感熱記録シートの記録層上に前記
組成の保護層塗液Ｅを乾燥後の塗布量が３ｇ／ｄとなる
ように塗布した後、塗布面をクロムメッキしたシリンダ
ードライヤーに接合させ、接合した状態で乾燥し、乾燥
後ロールより剥離してベック平滑性１０００秒の保護層
被覆感熱記録シートを得た。After coating the protective layer coating liquid E having the above composition on the recording layer of the heat-sensitive recording sheet obtained as above so that the coating amount after drying was 3 g/d, the coated surface was placed in a chrome-plated cylinder dryer. They were bonded together, dried in the bonded state, and peeled off from the roll after drying to obtain a protective layer-coated heat-sensitive recording sheet with Bekk smoothness of 1000 seconds.
得られたシートの性能評価結果を別紙表１に示した。The performance evaluation results of the obtained sheets are shown in Appendix Table 1.
実施例７
Ｆ）夜（黒色発色第１層感熱記録層成分）ロイコ染料１
０部（３−Ｎ−メチル−Ｎ−シクロへキシルアミノ−６
−メチル−７−フエニルアアミノフルオラン：新日曹化
工（株）ＰＪｉＰＳＤ−１５０）、ビスフェノールＡ３
０部、ステアリン酸亜鉛２０部を各々平均粒径２μｍ以
下になるようにサンドグラインダーで分散したものを混
合し。Example 7 F) Night (black coloring first layer heat-sensitive recording layer component) Leuco dye 1
0 parts (3-N-methyl-N-cyclohexylamino-6
-Methyl-7-phenylaaminofluorane: Nippon Sokako Co., Ltd. PJiPSD-150), bisphenol A3
0 parts of zinc stearate and 20 parts of zinc stearate were each dispersed using a sand grinder so that the average particle size was 2 μm or less.
次ぎに３０％濃度のケイ酸アルミニウム分散液を１００
部添加し、更にバスンダーとして１０％水溶液のＰＶＡ
を８０部及び１０％水溶液の酸化デンプンを７０部添加
することによりＦ液を作製した。尚、この塗液濃度は２
０％にして用いた。Next, 100% aluminum silicate dispersion with a concentration of 30% was added.
10% aqueous solution of PVA as bathunder.
Solution F was prepared by adding 80 parts of oxidized starch and 70 parts of a 10% aqueous solution of oxidized starch. The concentration of this coating liquid is 2
It was used at 0%.
Ｇ液（青色発色第２層感熱層成分）
ロイコ染料１０部（クリスタルバイオレットラクトン（
ＣＶＬ））ビスフェノールＡ２０部、１−ヒドロキシ−
２−ナフトエ酸フェニルエステル（大日本インキ−８！
Ｈ５−１０９４）１０部、ステアリン酸亜鉛２０部を各
々平均粒径２μｍ以下になるようにサンドグラインダー
で分散したものを混合し、次に４０％濃度の炭酸カルシ
ウム分散液を１００部添加し、更にバインダーとしてＰ
ｖＡＩＯ％水溶液を２００部添加することによりＤ液を
調製した。尚、この塗液濃度は２２％とした。G liquid (blue coloring second layer heat-sensitive layer component) leuco dye 10 parts (crystal violet lactone (
CVL)) 20 parts of bisphenol A, 1-hydroxy-
2-naphthoic acid phenyl ester (Dainippon Ink-8!
10 parts of H5-1094) and 20 parts of zinc stearate were each dispersed using a sand grinder so that the average particle size was 2 μm or less, and then 100 parts of a 40% concentration calcium carbonate dispersion was added, and then P as a binder
Solution D was prepared by adding 200 parts of vAIO% aqueous solution. The concentration of this coating liquid was 22%.
Ｆ液を上質紙（米坪５３ ｇ／ｌ／）に乾燥重量で８ｇ
／ｄになるようエアーナイフコーターにより塗工し黒色
発色層を得た。次に、第２層としてＧ液を第１層上に乾
燥重量で４ｇ／ｌ／になるようエアーナイフコーターに
より塗工し、塗工後半乾燥状態でクロムメッキした金属
ロールにプレスロールを用いて接合した。この感熱層は
、金属ロールと接合された状態で乾燥され、乾燥後金属
ロールより剥離して多色発色感熱記録紙かえられた。得
られた感熱記録紙は平滑性は３５０秒であり、地肌カブ
リは観察されなかった。8 g dry weight of liquid F on high-quality paper (53 g/l/)
/d using an air knife coater to obtain a black colored layer. Next, as the second layer, liquid G was applied onto the first layer using an air knife coater to give a dry weight of 4 g/l/, and in the latter half of the coating, when it was dry, it was coated on a chrome-plated metal roll using a press roll. Joined. This heat-sensitive layer was dried while being bonded to a metal roll, and after drying, it was peeled off from the metal roll and used as a multicolor heat-sensitive recording paper. The resulting thermal recording paper had a smoothness of 350 seconds, and no background fogging was observed.
次に青色発色画像として印加電圧１２．ＯＶ、パルス幅
３．０ｍｓ及び黒色発色画像として印加電圧１６．ＯＶ
、パルス幅２．５ｍｓで作画した結果、青色画像濃度は
０．５５、黒色画像濃度は１．３７と高濃度であり、ま
たドツト再現性も良く、色の混色もみられなかった。Next, as a blue colored image, apply voltage 12. OV, pulse width 3.0 ms, and applied voltage 16.0 ms for a black colored image. O.V.
As a result of drawing with a pulse width of 2.5 ms, the blue image density was as high as 0.55 and the black image density was as high as 1.37, and the dot reproducibility was also good and no color mixing was observed.
比較例３
Ｈ液・・顔料として酸化ケイ素（ミズカシルＰ−８３２
：水沢化学工業■製平均粒径２．７μｍ）５０部及び有
機中空顔料（ローベークＯＰ −８ｌＬＪ：日本アクリ
ル化学■製平均粒径０．５５μｍ）５０部、及びバイン
ダーとしてスチレン−ブタジェン共重合体ラッテクス（
固形分４８％）３０部を混合して固形分濃度３０％の塗
液を調製しアンダーコート層塗液Ｅ液とした。Ｈ液を米
坪４５ｇ／ｍ’の上質紙上に乾燥重量で７ ｇ ／ ｔ
ｎ”になるよう塗工したものを支持体として用いた以外
は比較例１と同じ条件で作成した。Comparative example 3 H liquid...Silicon oxide (Mizukasil P-832) as a pigment
50 parts of organic hollow pigment (Low Bake OP-8lLJ: average particle size 0.55 μm, manufactured by Nippon Acrylic Chemical Co., Ltd.), and styrene-butadiene copolymer latex as a binder. (
A coating liquid having a solid content concentration of 30% was prepared by mixing 30 parts (solid content: 48%), and was designated as undercoat layer coating liquid E. 7 g/t dry weight of liquid H on high-quality paper of 45 g/m'
It was prepared under the same conditions as Comparative Example 1, except that the support was coated so as to be n''.
得られたシートの性能評価結果を別表１に示した。The performance evaluation results of the obtained sheets are shown in Attached Table 1.
尚、べっひょう１の結果からも判るように平均波長が６
０μｍ以下のものは画質・感度及び外観が優れていた。Furthermore, as can be seen from the results of Bechyou 1, the average wavelength is 6.
Those with a diameter of 0 μm or less had excellent image quality, sensitivity, and appearance.
第１図は本発明の実施例に於て使用した感熱記録シート
の製造装置の概念図である。
第２図は粗さ曲線及び接触率算出方法の説明図である。
第１図
篤 ２１FIG. 1 is a conceptual diagram of a heat-sensitive recording sheet manufacturing apparatus used in an example of the present invention. FIG. 2 is an explanatory diagram of a roughness curve and a contact rate calculation method. Figure 1 Atsushi 21
Claims (1)
た感熱記録シートの最外表面層を形成する際、最外表面
層が湿潤状態で他の平滑体表面と接合した状態で乾燥し
、次いで該感熱記録層を平滑体表面から剥離することを
特徴とする高品位感熱記録シートの製造方法。 ２、最外表面層の湿潤状態が半乾燥状態であることを特
徴とする特許請求の範囲第１項記載の高品位感熱記録シ
ートの製造方法。 ３、最外表面層の湿潤状態が乾燥した表面に溶媒を塗布
して再湿潤した状態であることを特徴とする特許請求の
範囲第１項記載の高品位感熱記録シートの製造方法。 ４、最外表面層の湿潤状態が乾燥した表面に更に感熱記
録層塗液又は保護層塗液を塗布して再湿潤した状態であ
ることを特徴とする特許請求の範囲第１項記載の高品位
感熱記録シートの製造方法。 ５、乾燥した最外表面層の表面に更に感熱記録層塗液又
は保護層塗液を塗布する方法が、乾燥した表面と、接合
させる平滑体表面が接合する入口部に塗液の液溜りが継
続して生じるように液の供給量を調節するものであるこ
とを特徴とする特許請求の範囲第４項記載の高品位感熱
記録シートの製造方法。 ６、支持体が透気度が３００秒以下の下塗紙であること
を特徴とする特許請求の範囲第１項記載の高品位感熱記
録シートの製造方法。 ７、感熱記録層が異なった色相に発色する複数の感熱記
録層からなることを特徴とする特許請求の範囲第１項記
載の高品位感熱記録シートの製造方法。 ８、感熱記録層が一旦他の平滑体表面に塗布し、乾燥し
た後支持体又は下塗りされた支持体上に転写されること
を特徴とする特許請求の範囲第１項記載の高品位感熱記
録シートの製造方法。 １０、支持体上に加熱により発色する一層または二層以
上の感熱記録層において、感熱記録層の表面平滑性がＪ
ＩＳ−Ｂ−０６０１法に基づく粗さ曲線において、中心
線に平行で、且つ、粗さ曲線と接触率が１０％で交わる
直線から１．５μｍ内側に中心線と平行に引いた直線と
粗さ曲線との接触率が８０％以上である平滑面で有るこ
とを特徴とする高品位感熱記録シート。 １１、粗さ曲線と接触率が１０％で交わる直線から１．
５μｍ内側に中心線と平行に引いた直線と粗さ曲線との
接触率が９０％以上である平滑面で有ることを特徴とす
る特許請求の範囲第１０項記載の高品位感熱記録シート
。 １２、得られた感熱記録シート表面の光沢度が３０％以
下の艶消し状であることを特徴とする特許請求の範囲第
１０項記載の高品位感熱記録シート。[Scope of Claims] 1. When forming the outermost surface layer of a heat-sensitive recording sheet in which a heat-sensitive recording layer that develops color upon heating is provided on a support, the outermost surface layer is wetted with the surface of another smooth material. A method for producing a high-quality heat-sensitive recording sheet, which comprises drying the bonded state, and then peeling the heat-sensitive recording layer from the surface of the smooth body. 2. The method for producing a high-quality thermosensitive recording sheet according to claim 1, wherein the outermost surface layer is in a semi-dry state. 3. The method for producing a high-quality thermosensitive recording sheet according to claim 1, wherein the wet state of the outermost surface layer is a state obtained by applying a solvent to a dry surface and rewetting it. 4. The wet state of the outermost surface layer is a state in which a heat-sensitive recording layer coating liquid or a protective layer coating liquid is further applied to the dry surface to re-wet it. A method for producing a quality heat-sensitive recording sheet. 5. The method of further applying a heat-sensitive recording layer coating liquid or a protective layer coating liquid to the surface of the dried outermost surface layer may cause a pool of coating liquid at the entrance where the dried surface and the smooth surface to be bonded are joined. 5. The method of manufacturing a high-quality thermosensitive recording sheet according to claim 4, wherein the amount of liquid supplied is adjusted so that the liquid is continuously produced. 6. The method for producing a high-quality heat-sensitive recording sheet according to claim 1, wherein the support is a subbing paper having an air permeability of 300 seconds or less. 7. The method for producing a high-quality heat-sensitive recording sheet according to claim 1, wherein the heat-sensitive recording layer is comprised of a plurality of heat-sensitive recording layers that develop colors in different hues. 8. High-quality thermosensitive recording according to claim 1, characterized in that the thermosensitive recording layer is once coated on the surface of another smooth body, dried, and then transferred onto a support or an undercoated support. Method of manufacturing sheets. 10. In one or more heat-sensitive recording layers that develop color by heating on a support, the surface smoothness of the heat-sensitive recording layer is J
In the roughness curve based on the IS-B-0601 method, the roughness is a straight line drawn parallel to the center line 1.5 μm inside from the straight line that is parallel to the center line and intersects the roughness curve at a contact rate of 10%. A high-quality thermosensitive recording sheet characterized by having a smooth surface having a contact rate with a curved line of 80% or more. 11. From the straight line that intersects the roughness curve and the contact ratio at 10%, 1.
11. A high-quality thermosensitive recording sheet according to claim 10, characterized in that the sheet has a smooth surface having a contact ratio of 90% or more between a straight line drawn parallel to the center line 5 μm inward and a roughness curve. 12. The high-quality heat-sensitive recording sheet according to claim 10, wherein the surface of the heat-sensitive recording sheet has a matte finish with a gloss level of 30% or less.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13483086 | 1986-06-12 | ||
| JP61-134830 | 1986-06-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63147683A true JPS63147683A (en) | 1988-06-20 |
| JP2543702B2 JP2543702B2 (en) | 1996-10-16 |
Family
ID=15137461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62146494A Expired - Lifetime JP2543702B2 (en) | 1986-06-12 | 1987-06-12 | High-quality heat-sensitive recording sheet and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2543702B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02169292A (en) * | 1988-12-23 | 1990-06-29 | Ricoh Co Ltd | Thermal recording material |
| JPH0369390A (en) * | 1989-08-10 | 1991-03-25 | Oji Paper Co Ltd | Production of thermal recording material |
| JPH05177940A (en) * | 1991-12-27 | 1993-07-20 | Oji Paper Co Ltd | Thermal recording material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55156086A (en) * | 1979-05-23 | 1980-12-04 | Kanzaki Paper Mfg Co Ltd | Thermosensitive recording means |
| JPS5865694A (en) * | 1981-10-16 | 1983-04-19 | Fuji Photo Film Co Ltd | Heat sensitive recording paper |
| JPS58208091A (en) * | 1982-05-28 | 1983-12-03 | Ricoh Co Ltd | Heat sensitive recording sheet |
| JPS59143681A (en) * | 1983-02-05 | 1984-08-17 | Mitsubishi Paper Mills Ltd | Manufacture of development sheet for image recording |
| JPS59204594A (en) * | 1983-05-09 | 1984-11-19 | Ricoh Co Ltd | Thermal recording material |
| JPS61237683A (en) * | 1985-04-15 | 1986-10-22 | Fuji Photo Film Co Ltd | Thermal recording paper |
-
1987
- 1987-06-12 JP JP62146494A patent/JP2543702B2/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55156086A (en) * | 1979-05-23 | 1980-12-04 | Kanzaki Paper Mfg Co Ltd | Thermosensitive recording means |
| JPS5865694A (en) * | 1981-10-16 | 1983-04-19 | Fuji Photo Film Co Ltd | Heat sensitive recording paper |
| JPS58208091A (en) * | 1982-05-28 | 1983-12-03 | Ricoh Co Ltd | Heat sensitive recording sheet |
| JPS59143681A (en) * | 1983-02-05 | 1984-08-17 | Mitsubishi Paper Mills Ltd | Manufacture of development sheet for image recording |
| JPS59204594A (en) * | 1983-05-09 | 1984-11-19 | Ricoh Co Ltd | Thermal recording material |
| JPS61237683A (en) * | 1985-04-15 | 1986-10-22 | Fuji Photo Film Co Ltd | Thermal recording paper |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02169292A (en) * | 1988-12-23 | 1990-06-29 | Ricoh Co Ltd | Thermal recording material |
| JPH0369390A (en) * | 1989-08-10 | 1991-03-25 | Oji Paper Co Ltd | Production of thermal recording material |
| JPH05177940A (en) * | 1991-12-27 | 1993-07-20 | Oji Paper Co Ltd | Thermal recording material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2543702B2 (en) | 1996-10-16 |
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