JPS6354280A - Thermal recording material - Google Patents
Thermal recording materialInfo
- Publication number
- JPS6354280A JPS6354280A JP61199600A JP19960086A JPS6354280A JP S6354280 A JPS6354280 A JP S6354280A JP 61199600 A JP61199600 A JP 61199600A JP 19960086 A JP19960086 A JP 19960086A JP S6354280 A JPS6354280 A JP S6354280A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- sensitive recording
- recording material
- color
- color developer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 25
- 150000002989 phenols Chemical class 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 238000004040 coloring Methods 0.000 abstract description 6
- 239000003921 oil Substances 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 18
- 239000010410 layer Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 8
- 238000012546 transfer Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 5
- -1 p-dimethylaminophenyl Chemical group 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 4
- 230000005291 magnetic effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 235000014593 oils and fats Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 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 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- PGAAZCXJMPDCHO-UHFFFAOYSA-N 3-(4-chloro-2-hydroxy-5-methylphenyl)-3-[4-(dimethylamino)-2-methoxyphenyl]-2-benzofuran-1-one Chemical compound COC1=CC(N(C)C)=CC=C1C1(C=2C(=CC(Cl)=C(C)C=2)O)C2=CC=CC=C2C(=O)O1 PGAAZCXJMPDCHO-UHFFFAOYSA-N 0.000 description 1
- WMOULUHRMJQPDK-UHFFFAOYSA-N 3-[4-(diethylamino)-2-hydroxyphenyl]-3-(2-methoxy-5-methylphenyl)-2-benzofuran-1-one Chemical compound OC1=CC(N(CC)CC)=CC=C1C1(C=2C(=CC=C(C)C=2)OC)C2=CC=CC=C2C(=O)O1 WMOULUHRMJQPDK-UHFFFAOYSA-N 0.000 description 1
- KDSOMGJHOISAKK-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptane-4,5-dicarboxylic acid Chemical class OC(=O)C1C(C(=O)O)CCC2OC21 KDSOMGJHOISAKK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- ZKURGBYDCVNWKH-UHFFFAOYSA-N [3,7-bis(dimethylamino)phenothiazin-10-yl]-phenylmethanone Chemical compound C12=CC=C(N(C)C)C=C2SC2=CC(N(C)C)=CC=C2N1C(=O)C1=CC=CC=C1 ZKURGBYDCVNWKH-UHFFFAOYSA-N 0.000 description 1
- 229940117913 acrylamide Drugs 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical compound C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 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
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 239000001993 wax Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
- B41M5/333—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
- B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明は感熱記録材料に関し、特に画像の安定性に優れ
た感熱記録材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a heat-sensitive recording material, and particularly to a heat-sensitive recording material with excellent image stability.
通常無色ないし淡色の発色性無色染料（ロイコ染料）と
フェノール類、有機酸との加熱発色反応を利用した感熱
記録シートは、特公昭４３−４１６０号、特公昭４５−
１４０３９号、特開昭４８−２７７３６号等に発表され
、広く実用化されている。一般に、感熱記録シートは、
ロイコ染料と、フェノール性物質等の顕色剤とをそれぞ
れ微細な粒子に粉砕分散した後。Heat-sensitive recording sheets that utilize a heated color-forming reaction between normally colorless or light-colored colorless dyes (leuco dyes), phenols, and organic acids are disclosed in Japanese Patent Publication No. 4160 of 1972 and Japanese Patent Publication No. 4160 of 1972,
No. 14039, Japanese Patent Application Laid-Open No. 48-27736, etc., and it has been widely put into practical use. Generally, thermal recording sheets are
After leuco dye and color developer such as phenolic substance are crushed and dispersed into fine particles.
両者を混合し、バインダー、充填剤、感度向上剤、滑剤
その他の助剤を添加して得た塗液を、紙およびフィルム
等の支持体に塗工したもので、加熱による瞬時の化学反
応により発色記録を得るものである。A coating liquid obtained by mixing the two and adding binders, fillers, sensitivity improvers, lubricants, and other auxiliary agents is applied to a support such as paper or film. This is to obtain a color record.
このような感熱記録シートの発色のための加熱には、熱
ヘッドを内蔵したサーマルプリンター。A thermal printer with a built-in thermal head is used to heat such heat-sensitive recording sheets to develop color.
ファクシミリ等が用いられる。そして、このような記録
シートは、他の記録材料に比較して、現像、定着等の煩
雑な処理を施すことなく、比較的短時間で記録が得られ
ること、騒音の発生がないこと、比較的安価であること
等の利点により、図書、文書などの複写は勿論のこと、
電子計算機、ファクシミリ、テレックス、医療計測機等
の情報並びに計測機器の記録材料として広く用いられて
いる。A facsimile or the like is used. Compared to other recording materials, such recording sheets can produce records in a relatively short time without complex processes such as development and fixing, and do not generate noise. Due to its advantages such as being inexpensive, it can be used not only for copying books and documents, but also for copying books, documents, etc.
It is widely used as a recording material for information and measuring equipment such as electronic computers, facsimiles, telex machines, and medical measuring instruments.
しかしながら、このような従来のロイコ染料とフェノー
ル性物質の組み合せになる感熱記録シートは、その発色
部が油脂類により濃渡が低下したり。However, in such a conventional heat-sensitive recording sheet made of a combination of a leuco dye and a phenolic substance, the density of the color developing area is reduced due to oils and fats.
消色したりするという欠点を有している。It has the disadvantage of fading.
一方、従来の感熱記録シートにおけるこのような点を改
良したものとして、感熱発色層上に水溶性高分子オーバ
ーコート層を設けたものが提案されているが、このもの
はオーバーコート層が熱伝導を妨げるため、熱感度が悪
くなり、しかも、オーバーコート層の塗布工程が必要な
ため、コスト高になるという欠点があった。On the other hand, as an improvement over these points in conventional heat-sensitive recording sheets, it has been proposed that a water-soluble polymer overcoat layer is provided on the heat-sensitive coloring layer. This has disadvantages in that the heat sensitivity is poor because of this, and the process of applying an overcoat layer is required, resulting in high costs.
本発明者は、前記従来技術に見られる欠点を克服すべく
鋭意研究を重ねた結果、下記一般式（１）で表わされる
フェノール性化合物を顕色剤として使用した場合、油脂
類により発色部の濃度が低下したり消色したりしない感
熱記録シートを提供し得ることを見い出し１本発明をな
すに到った。As a result of extensive research in order to overcome the drawbacks seen in the prior art, the present inventor has found that when a phenolic compound represented by the following general formula (1) is used as a color developer, the coloring part is The inventors have discovered that it is possible to provide a heat-sensitive recording sheet that does not decrease in density or fade, leading to the present invention.
即ち、本発明によれば、ロイコ染料とその顕色剤との間
の発色反応を利用した感熱記録材料において、該顕色剤
として一般式（１）
（式中、Ｒは炭素数１〜１２のアルキレン基を表わす）
で表わされるフェノール性化合物を用いることを特徴と
する感熱記録材料が提供される。That is, according to the present invention, in a heat-sensitive recording material that utilizes a color-forming reaction between a leuco dye and its color developer, the color developer is represented by the general formula (1) (wherein R is a carbon number of 1 to 12 (represents an alkylene group)
A heat-sensitive recording material characterized by using a phenolic compound represented by the following is provided.
本発明において用いるロイコ染料は単独又は２種以上混
合して適用されるが、このようなロイコ染料としては、
この種の感熱材料に適用されているものが任意に適用さ
れ、例えば、トリフェニルメタン系、フルオラン系、フ
ェノチアジン系、オーラミン系、スピロピラン系等の各
種染料のロイコ化合物が好ましく用いられる。このよう
なロイコ染料の具体例としては、例えば、以下に示すよ
うなものが挙げられる。The leuco dyes used in the present invention can be applied singly or in combination of two or more types, but such leuco dyes include:
Any dye that has been applied to this type of heat-sensitive material may be used. For example, leuco compounds of various dyes such as triphenylmethane, fluoran, phenothiazine, auramine, and spiropyran dyes are preferably used. Specific examples of such leuco dyes include those shown below.
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
メチルアミノフタリド（別名クリスタルバイオレットラ
クトン）。3.3-bis(p-dimethylaminophenyl)-phthalide, 3.3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (also known as crystal violet lactone).
３．３−ビス（Ｐ−ジメチルアミノフェニル）−６−ジ
ブチルアミノフェニル、
３．３−ビス（ｐ−ジメチルアミノフェニル）−６−ク
ロルフタリド、
３．３−ビス（Ｐ−ジブチルアミノフェニル）フタリド
、
３−シクロへキシルアミノ−６−クロルフルオラン、
３−ジメチルアミノ−５，７−シメチルフルオラン。3.3-bis(P-dimethylaminophenyl)-6-dibutylaminophenyl, 3.3-bis(p-dimethylaminophenyl)-6-chlorophthalide, 3.3-bis(P-dibutylaminophenyl) phthalide, 3-cyclohexylamino-6-chlorofluorane, 3-dimethylamino-5,7-dimethylfluorane.
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−７−メチルフルオラン、３−ジエチルアミ
ノ−７，８−ベンズフルオラン。3-diethylamino-7-chlorofluorane, 3-diethylamino-7-methylfluorane, 3-diethylamino-7,8-benzfluorane.
３−ジエチルアミノ−６−メチル−７−クロルフルオラ
ン。3-diethylamino-6-methyl-7-chlorofluorane.
３−（Ｎ−ｐ−）−ツルーＮ−エチルアミノ）−６−メ
チル−７−アニリノフルオラン、
３−ピロリジノ−６−メチル−７−アニリノフルオラン
、
２− （Ｎ−（３’ −トリフルオルメチルフェニル）
アミノ）−６−ジニチルアミノフルオラン。3-(N-p-)-True N-ethylamino)-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 2-(N-(3' -trifluoromethylphenyl)
amino)-6-dinithylaminofluorane.
２− （３，６−ビス（ジエチルアミノ）−９−（ｏ−
クロルアニリノ）キサンチル安息香酸ラクタム）。2-(3,6-bis(diethylamino)-9-(o-
Chloranilino)xantylbenzoic acid lactam).
３−ジエチルアミノ−６−メチル−７−クロロメチルア
ニリノ）フルオラン、
３−ジエチルアミノ−７−（Ｏ−クロルアニリノ）フル
オラン、
３−ジブチルアミノ−７−（ｏ−クロルアニリノ）フル
オラン。3-diethylamino-6-methyl-7-chloromethylanilino)fluoran, 3-diethylamino-7-(O-chloroanilino)fluoran, 3-dibutylamino-7-(o-chloroanilino)fluoran.
３−Ｎ−メチル−Ｎ−アミルアミノ−６−メチル−７−
アニリノフルオラン。3-N-methyl-N-amylamino-6-methyl-7-
Anilinofluorane.
３−Ｎ−メチル−Ｎ−シクロヘキシルアミノ−６−メチ
ル−７−アニリノフルオラン、
３−ジエチルアミノ−６−メチル−７−アニリノフルオ
ラン、
３−（Ｎ，Ｎ−ジエチルアミノ）−５−メチル−７−（
Ｎ。3-N-Methyl-N-cyclohexylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-5-methyl -7-(
N.
Ｎ−ジベンジルアミノ）フルオラン、
ベンゾイルロイコメチレンブルー、
６′−クロロ−８′−メトキシ−ベンゾインドリノ−ピ
リロスピラン、
６′−ブロモ−３′−メトキシ−ベンゾインドリノ−ピ
リロスピラン、
３−（２’ −ヒドロキシ−４′−ジメチルアミノフェ
ニル）−３−（２’ −メトキシ−５′−クロルフェニ
ル）フタリド、
３−（２’ −ヒドロキシ−４′−ジメチルアミノフェ
ニル）−３−（２’ −メトキシ−５′−二トロフェニ
ル）フタリド、
３−（２’ −ヒドロキシ−４′−ジエチルアミノフェ
ニル）−３−（２’ −メトキシ−５′−メチルフェニ
ル）フタリド、
３−（２’ −メトキシ−４′−ジメチルアミノフェニ
ル）−３−（２’ −ヒドロキシ−４′−クロル−５′
−メチルフェニル）フタリド、
３−モルホリノ−７−（Ｎ−プロピル−トリフルオロメ
チルアニリノ）フルオラン、
３−ピロリジノ−７−トリフルオロメチルアニリノフル
オラン。N-dibenzylamino)fluoran, benzoylleucomethylene blue, 6'-chloro-8'-methoxy-benzoindolino-pyrylospirane, 6'-bromo-3'-methoxy-benzoindolino-pyrylospirane, 3-(2'- 3-(2'-hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy- 5'-nitrophenyl) phthalide, 3-(2'-hydroxy-4'-diethylaminophenyl)-3-(2'-methoxy-5'-methylphenyl) phthalide, 3-(2'-methoxy-4'-dimethylaminophenyl)-3-(2'-hydroxy-4'-chloro-5'
-methylphenyl)phthalide, 3-morpholino-7-(N-propyl-trifluoromethylanilino)fluorane, 3-pyrrolidino-7-trifluoromethylanilinofluorane.
３−ジエチルアミノ−５−クロロ−７−（Ｎ−ベンジル
−トリフルオロメチルアニリノ）フルオラン。3-Diethylamino-5-chloro-7-(N-benzyl-trifluoromethylanilino)fluoran.
３−ピロリジノ−７−（ジ−ｐ−クロルフェニル）メチ
ルアミノフルオラン。3-pyrrolidino-7-(di-p-chlorophenyl)methylaminofluorane.
３−ジエチルアミノ−５−クロル−７−（α−フェニル
エチルアミノ）フルオラン、
３−（Ｎ−エチル−ｐ−トルイジノ）−７−（α−フェ
ニルエチルアミノ）フルオラン
３−ジエチルアミノ−７−（０−メトキシカルボニルフ
ェニルアミノ）フルオラン。3-diethylamino-5-chloro-7-(α-phenylethylamino)fluoran, 3-(N-ethyl-p-toluidino)-7-(α-phenylethylamino)fluoran 3-diethylamino-7-(0- methoxycarbonylphenylamino)fluorane.
３−ジエチルアミノ−５−メチル−７−（α−フェニル
エチルアミノ）フルオラン、
３−ジエチルアミノ−７−ピペリジノフルオラン、２−
クロロ−３−（Ｎ−メチルトルイジノ）−７−（ｐ−ｎ
−ブチルアニリノ）フルオラン、
３−（Ｎ−ベンジル−シクロへキシルアミノ）−５，６
−ペンゾー７−α−ナフチルアミノ−４１−ブロモフル
オラン、
３−ジエチルアミノ−６−メチル−７−メシチジノー４
’ 、５’−ベンゾフルオラン等、これらは単独で又は
２種以上が混合されて使用される。3-diethylamino-5-methyl-7-(α-phenylethylamino)fluorane, 3-diethylamino-7-piperidinofluorane, 2-
Chloro-3-(N-methyltoluidino)-7-(p-n
-butylanilino)fluorane, 3-(N-benzyl-cyclohexylamino)-5,6
-Penzo 7-α-naphthylamino-41-bromofluorane, 3-diethylamino-6-methyl-7-mesitidino 4
', 5'-benzofluorane, etc., these may be used alone or in combination of two or more.
前記一般式（１）で表わされたフェノール性物質の具体
例としては、以下に示すものが挙げられる。Specific examples of the phenolic substance represented by the general formula (1) include those shown below.
化籠魔 構造式
本発明で用いるフェノール性化合物はこれらに限定され
るものではなく、またこれらも単独で又は２種以上が混
合されて使用される。なお、これら上記の一般式で表わ
されたフェノール性物質は感熱記録シート用素材として
、これまでは全く用いられていなかったものである０本
発明においては、上記したフェノール性化合物からなる
顕色性物質はロイコ染料１重量部に対し一般に１〜１０
重量部、好ましくは２〜６重量部の範囲で用いられる。Phenolic compounds used in the present invention are not limited to these compounds, and these compounds may be used alone or in combination of two or more. It should be noted that these phenolic substances represented by the above general formula have not been used at all as materials for heat-sensitive recording sheets. Generally, the amount of the leuco dye is 1 to 10% by weight of the leuco dye.
It is used in parts by weight, preferably in the range of 2 to 6 parts by weight.
本発明においては、前記ロイコ染料及び顕色剤を支持体
上に結合支持させるために、慣用の種々の結合剤を適宜
用いることができ、例えば、ポリビニルアルコール、デ
ンプン及びその誘導体、メトキシセルロース、ヒドロキ
シエチルセルロース。In the present invention, in order to bind and support the leuco dye and color developer on the support, various commonly used binders can be used as appropriate, such as polyvinyl alcohol, starch and its derivatives, methoxycellulose, hydroxyl, etc. Ethyl cellulose.
カルボキシメチルセルロース、メチルセルロース、エチ
ルセルロース等のセルロース誘導体、ポリアクリル酸ソ
ーダ、ポリビニルピロリドン、アクリル酸アミド／アク
リル酸エステル共重合体、アクリル酸アミド／アクリル
酸エステル／メタクリル酸３元共重合体、スチレン／無
水マレイン酸共重合体アルカリ塩、イソブチレン／無水
マレイン酸共重合体アルカリ塩、ポリアクリルアミド、
アルギン酸ソーダ、ゼラチン、カゼイン等の水溶性高分
子の他、ポリ酢酸ビニル、ポリウレタン、スチレン／ブ
タジェン共重合体、ポリアクリル酸、ポリアクリル酸エ
ステル、塩化ビニル／酢酸ビニル共重合体、ポリブチル
メタクリレート、エチレンｌ酢酸ビニル共重合体、スチ
レン／ブタジェンｌアクリル系共重合体等のラテックス
を用いることができる。Cellulose derivatives such as carboxymethylcellulose, methylcellulose, and ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, acrylic amide/acrylic ester copolymer, acryl amide/acrylic ester/methacrylic acid ternary copolymer, styrene/maleic anhydride Acid copolymer alkali salt, isobutylene/maleic anhydride copolymer alkali salt, polyacrylamide,
In addition to water-soluble polymers such as sodium alginate, gelatin, and casein, polyvinyl acetate, polyurethane, styrene/butadiene copolymer, polyacrylic acid, polyacrylic acid ester, vinyl chloride/vinyl acetate copolymer, polybutyl methacrylate, Latexes such as ethylene/vinyl acetate copolymer, styrene/butadiene/acrylic copolymer, etc. can be used.
また１本発明においては、前記ロイコ染料及び顕色剤と
共に、必要に応じ、更に、この種の感熱記録材料に慣用
される補助添加成分、例えば、填料、界面活性剤、熱可
融性物質（又は滑剤）等を併用することができる。この
場合、填料としては、例えば、炭酸カルシウム、シリカ
、酸化亜鉛、酸化チタン、水酸化アルミニウム、水酸化
亜鉛、硫酸バリウム、クレー、タルク、表面処理された
炭酸カルシウムやシリカ等の無機系微粉末の他、尿素−
ホルマリン樹脂、スチレン／メタクリル酸共重合体、ポ
リスチレン樹脂等の有機系の微粉末を挙げることができ
、熱可融性物質としては、例えば、高級脂肪酸又はその
エステル、アミドもしくは金属塩の他、各種ワックス類
、芳香族カルボン酸とアミンとの縮合物、安息香酸フェ
ニルエステル、高級直鎖グリコール、３，４−エポキシ
−へキサヒドロフタル酸ジアルキル、高級ケトン、その
他の熱可融性有機化合物等の５０〜２００℃の程度の融
点を持つものが挙げられる。In addition, in the present invention, in addition to the leuco dye and color developer, if necessary, auxiliary additive components commonly used in this type of heat-sensitive recording material, such as fillers, surfactants, thermofusible substances ( or lubricant), etc. can be used in combination. In this case, fillers include, for example, calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, talc, and surface-treated inorganic fine powders such as calcium carbonate and silica. Others, urea-
Organic fine powders such as formalin resin, styrene/methacrylic acid copolymer, and polystyrene resin can be mentioned. Examples of thermofusible substances include higher fatty acids or their esters, amides, or metal salts, as well as various Waxes, condensates of aromatic carboxylic acids and amines, phenyl benzoate, higher linear glycols, dialkyl 3,4-epoxy-hexahydrophthalates, higher ketones, other thermofusible organic compounds, etc. Examples include those having a melting point of about 50 to 200°C.
本発明の感熱記録材料は、種々の構造のものとすること
ができ、ロイコ染料と顕色剤との間の発色反応を利用す
る従来知られている構造のものは全て包含される０例え
ば１本発明の感熱記録材料は、支持体上に、ロイコ染料
と顕色剤とを同一の塗布層又は別個の塗布層として支持
させた構造の感熱記録材料や、ロイコ染料を転写層とし
て支持体に支持させて形成した転写シートと、顕色剤を
受容層として支持体に支持させた受容シートとからなる
熱転写型の感熱記録材料として利用することができる。The heat-sensitive recording material of the present invention can have various structures, including all conventionally known structures that utilize a color-forming reaction between a leuco dye and a color developer. The heat-sensitive recording material of the present invention includes a heat-sensitive recording material having a structure in which a leuco dye and a color developer are supported on a support as the same coating layer or separate coating layers, and a leuco dye is supported on a support as a transfer layer. It can be used as a thermal transfer type heat-sensitive recording material consisting of a transfer sheet formed by supporting it and a receptor sheet supported by a support with a color developer as a receptor layer.
熱転写型の感熱記録材料の場合、転写シートに対して、
受容シートをその受容層が転写シートの転写層に接する
ようにして重ね、その重合シートの表面又は裏面から熱
印字することにより受容シートの受容層面に所望の発色
画像を形成させることができる。In the case of thermal transfer type thermal recording materials, the transfer sheet is
A desired colored image can be formed on the receiving layer surface of the receiving sheet by overlapping the receiving sheets so that the receiving layer is in contact with the transfer layer of the transfer sheet and thermally printing from the front or back surface of the polymerized sheet.
本発明の感熱記録材料は１例えば、前記した各成分を含
む感熱層形成用塗液を、紙、合成紙、プラスチックフィ
ルムなどの適当な支持体上に塗布し、乾燥することによ
って製造され、各種の記録分野、殊に、高い画像安定性
を必要とする高速記録用の感熱記録材料として利用され
る。The heat-sensitive recording material of the present invention can be manufactured by applying a coating liquid for forming a heat-sensitive layer containing the above-mentioned components onto a suitable support such as paper, synthetic paper, or plastic film, and drying it. It is used in the field of recording, especially as a heat-sensitive recording material for high-speed recording that requires high image stability.
本発明の感熱記録材料は、種々の分野において利用され
るが、殊に、前記した優れた発色画像安定性に利用し、
感熱記録型ラベルシートや、感熱記録型磁気券紙として
有利に利用することができる。感熱記録型ラベルシート
の場合、支持体の一方の面に、前記したフルオラン化合
物とフェノール性化合物を含有する感熱発色層を設け、
支持体の他方の面に、接着剤層を介して剥離台紙を設け
ればよく、磁気券紙の場合は、この剥離台紙に代えて、
強磁性体と結着剤とを主成分とする磁気記録層を設けれ
ばよい。The heat-sensitive recording material of the present invention is used in various fields, but in particular, it is used for the above-mentioned excellent color image stability,
It can be advantageously used as a heat-sensitive recording type label sheet or a heat-sensitive recording type magnetic ticket paper. In the case of a heat-sensitive recording type label sheet, a heat-sensitive coloring layer containing the above-mentioned fluoran compound and phenolic compound is provided on one side of the support,
A release mount may be provided on the other side of the support via an adhesive layer, and in the case of magnetic ticket paper, instead of this release mount,
A magnetic recording layer containing a ferromagnetic material and a binder as main components may be provided.
本発明によれば、前記一般式（１）で示されるフェノー
ル性化合物の使用によって、以下に挙げるような優れた
特性を示す感熱記録材料を得ることができる。According to the present invention, by using the phenolic compound represented by the general formula (1), it is possible to obtain a heat-sensitive recording material exhibiting the excellent properties listed below.
（１）発色画像が経時的に消色したり、白粉現象をおこ
したりしないで非常に安定している。(1) The colored image is extremely stable without fading over time or causing white powder phenomenon.
（２）発色画像が油脂等の接触によって濃渡が低下した
り消色したりしない。(2) Colored images do not deteriorate in density or fade due to contact with oils and fats.
以下に本発明の実施例を示す。なお、部、％はそれぞれ
重量部、重量％である。Examples of the present invention are shown below. Note that parts and % are parts by weight and % by weight, respectively.
実施例１
下記組成よりなる混合物を各々別々に磁性ボールミルを
用いて２日間粉砕、分散して（Ａ）液、〔Ｂ〕液、〔Ｃ
〕液を調製した。Example 1 A mixture having the following composition was separately ground and dispersed for two days using a magnetic ball mill to obtain liquid (A), liquid [B], and liquid [C].
] A solution was prepared.
（Ａ）液
３−（Ｎ−シクロヘキシル−Ｎ−メチルアミノ）−６−
メチル−７−アニリツフルオラン ２０部１０％ヒ
ドロキシエチルセルロース水溶液 ２０〃水
６０〃（Ｂ
）液
ｐ−ヒドロキシ安息香酸−２−（ｏ−ヒドロキシフェニ
ルチオ）エチルエステル
（化合物具体例（２）の物質、融点１００〜１０１℃）
２０部
１０％ヒドロキシエチルセルロース
水溶液 ２０〃水
６０
〃〔Ｃ〕液
炭酸カルシウム ２０部５％メ
チルセルロース水溶液 ２０〃水
６０〃以上
のようにして得られた（Ａ）〜〔Ｃ〕液を用い、下記組
成の感熱発色層液を調製し、基準坪量５０ｇ／ｒｒｒの
市販上質紙に乾燥塗布量４〜５ｇ／−となるようにワイ
ヤーバーを選んで塗布、乾燥し１次いで、感熱発色層表
面の平滑度が、ベック平滑度で５００〜６００秒になる
よう、カレンダーがけし、本発明の感熱記録シート（ａ
）を作った。(A) Liquid 3-(N-cyclohexyl-N-methylamino)-6-
Methyl-7-anirite fluorane 20 parts 10% hydroxyethyl cellulose aqueous solution 20 parts water
60〃(B
) Liquid p-hydroxybenzoic acid-2-(o-hydroxyphenylthio)ethyl ester (substance of specific compound example (2), melting point 100-101°C)
20 parts 10% hydroxyethylcellulose aqueous solution 20 water
60
[C] Liquid calcium carbonate 20 parts 5% methylcellulose aqueous solution 20 Water
60 Using the solutions (A) to [C] obtained as above, a heat-sensitive coloring layer solution having the following composition was prepared, and a dry coating amount of 4 to 5 g/ The heat-sensitive recording sheet of the present invention (a
)made.
感熱発色層液
（Ａ）液 ｉｏ部ＣＢｌ
液 ３０〃（Ｃ）液
３０〃イソブチレン−無水マレ
イン酸共重合体の２０％アルカリ水溶液
１０〃比較例１
実施例１の（Ｂ）液のかわりに下記（Ｄ）液を使用する
以外はすべて実施例１と同様にして感熱記録シート（ｂ
）を作った。Thermosensitive coloring layer liquid (A) liquid io part CBl
Liquid 30〃(C) Liquid
30 20% alkaline aqueous solution of isobutylene-maleic anhydride copolymer
10 Comparative Example 1 A thermosensitive recording sheet (b
)made.
（Ｄ）液
ビスフェノールＡ ２０部１
０％ヒドロキシエチルセルロース水溶液 ２０＃水
６
０＃比較例２
実施例１の［Ｂ）液のかわりに下記（Ｅ］液を使用する
以外はすべて実施例１と同様にして感熱記録シート（ｃ
）を作った。(D) Liquid bisphenol A 20 parts 1
0% hydroxyethyl cellulose aqueous solution 20# water
6
0# Comparative Example 2 A thermosensitive recording sheet (c
)made.
（Ｅ’ｌ液
１０％ヒドロキシエチルセルロース水溶液 ２０〃水
６０〃以上のようにして得た感熱記録シート（ａ）〜（
ｃ）を熱傾斜試験機（東洋精機層）にて圧力２ｋｇ、接
触時間１秒で１５０℃で印字した。 （ａ）（ｃ）の感
熱記録シートの発色部と地肌部に綿実油を薄く塗布し、
６０℃、ｄｒｙの保存性試験室に２４時間保存し、発色
部と地肌部の変化を見た。その結果を表−１に示す。(E'l liquid 10% hydroxyethylcellulose aqueous solution 20〃water
60 Thermal recording sheets (a) to (a) obtained as above
c) was printed at 150° C. using a thermal gradient tester (Toyo Seiki Layer) under a pressure of 2 kg and a contact time of 1 second. Apply a thin layer of cottonseed oil to the colored part and background part of the heat-sensitive recording sheet of (a) and (c),
The sample was stored in a dry storage test room at 60°C for 24 hours, and changes in the colored area and background area were observed. The results are shown in Table-1.
表−１ ×： 消色する。Table-1 ×: Discolored.
以上より、本発明の感熱記録材料は、油脂類の接触に対
しても高い画像安定性を有していることがわかる。From the above, it can be seen that the heat-sensitive recording material of the present invention has high image stability even when it comes into contact with oils and fats.
Claims (1)
した感熱記録材料において、該顕色剤として、一般式 ▲数式、化学式、表等があります▼ （式中、Ｒは炭素数１〜１２のアルキレン基を表わす）
で表わされるフェノール性化合物を用いることを特徴と
する感熱記録材料。 物を用いることを特徴とする感熱記録材料。(1) In heat-sensitive recording materials that utilize a color reaction between a leuco dye and its color developer, the color developer has a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (where R is the number of carbon atoms) 1 to 12 alkylene groups)
A heat-sensitive recording material characterized by using a phenolic compound represented by: A heat-sensitive recording material characterized by using a material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61199600A JPS6354280A (en) | 1986-08-26 | 1986-08-26 | Thermal recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61199600A JPS6354280A (en) | 1986-08-26 | 1986-08-26 | Thermal recording material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6354280A true JPS6354280A (en) | 1988-03-08 |
Family
ID=16410549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61199600A Pending JPS6354280A (en) | 1986-08-26 | 1986-08-26 | Thermal recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6354280A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8676239B2 (en) | 2009-02-23 | 2014-03-18 | Mitsubishi Electric Corporation | Wireless communication system, wireless communication device, and wireless communication method |
-
1986
- 1986-08-26 JP JP61199600A patent/JPS6354280A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8676239B2 (en) | 2009-02-23 | 2014-03-18 | Mitsubishi Electric Corporation | Wireless communication system, wireless communication device, and wireless communication method |
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