JPS6344077B2 - - Google Patents
Info
- Publication number
- JPS6344077B2 JPS6344077B2 JP55160189A JP16018980A JPS6344077B2 JP S6344077 B2 JPS6344077 B2 JP S6344077B2 JP 55160189 A JP55160189 A JP 55160189A JP 16018980 A JP16018980 A JP 16018980A JP S6344077 B2 JPS6344077 B2 JP S6344077B2
- Authority
- JP
- Japan
- Prior art keywords
- recording
- methyl
- heat
- parts
- compound
- 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.)
- Expired
Links
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000000981 basic dye Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- LZHCVNIARUXHAL-UHFFFAOYSA-N 2-tert-butyl-4-ethylphenol Chemical compound CCC1=CC=C(O)C(C(C)(C)C)=C1 LZHCVNIARUXHAL-UHFFFAOYSA-N 0.000 claims 1
- MOZDKDIOPSPTBH-UHFFFAOYSA-N Benzyl parahydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OCC1=CC=CC=C1 MOZDKDIOPSPTBH-UHFFFAOYSA-N 0.000 description 15
- 239000000975 dye Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000003086 colorant Substances 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- 238000001454 recorded image Methods 0.000 description 6
- -1 phenol compound Chemical class 0.000 description 5
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 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 2
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 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
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- ZCTQGTTXIYCGGC-UHFFFAOYSA-N salicylic acid benzyl ester Natural products OC1=CC=CC=C1C(=O)OCC1=CC=CC=C1 ZCTQGTTXIYCGGC-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OEHNVIAAMXRSIW-UHFFFAOYSA-N 1-N-cyclohexyl-3-N-fluoro-1-N,4-dimethylbenzene-1,3-diamine Chemical compound C1(CCCCC1)N(C)C=1C=C(NF)C(=CC=1)C OEHNVIAAMXRSIW-UHFFFAOYSA-N 0.000 description 1
- GGJWFGAKNZHSIB-UHFFFAOYSA-N 1-butylcyclohexa-2,4-dien-1-ol Chemical compound CCCCC1(O)CC=CC=C1 GGJWFGAKNZHSIB-UHFFFAOYSA-N 0.000 description 1
- IJJMQFOFFIWMNN-UHFFFAOYSA-N 12-oxapentacyclo[12.8.0.02,11.03,8.015,20]docosa-1(14),2(11),3,5,7,9,15,17,19,21-decaene Chemical compound C1=CC=CC2=C3COC4=CC=C(C=CC=C5)C5=C4C3=CC=C21 IJJMQFOFFIWMNN-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 1
- MQJTWPAGXWPEKU-UHFFFAOYSA-N 3-[4-(dimethylamino)phenyl]-3-(1,2-dimethylindol-3-yl)-2-benzofuran-1-one Chemical compound C1=CC(N(C)C)=CC=C1C1(C=2C3=CC=CC=C3N(C)C=2C)C2=CC=CC=C2C(=O)O1 MQJTWPAGXWPEKU-UHFFFAOYSA-N 0.000 description 1
- YBOBZZSJMAWFBX-UHFFFAOYSA-N 4-[[4-(dimethylamino)phenyl]-phenylmethoxymethyl]-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)OCC1=CC=CC=C1 YBOBZZSJMAWFBX-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-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
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 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
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 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
- 229910052570 clay Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- MGNPLIACIXIYJE-UHFFFAOYSA-N n-fluoroaniline Chemical compound FNC1=CC=CC=C1 MGNPLIACIXIYJE-UHFFFAOYSA-N 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000001016 thiazine dye Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- 239000001993 wax Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—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
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)
Description
本発明は感熱記録体に関し、特に高速記録適性
を備え、且つ記録像が退色し難い感熱記録体に関
するものである。
従来、無色ないしは淡色の塩基性染料と有機な
いし無機呈色剤との呈色反応を利用し、熱により
両発色物質を接触させて記録像を得るようにした
感熱記録体は良く知られている。最近、感熱記録
方式の著しい進歩に伴いサーマルヘツドを利用し
た感熱フアツクス、感熱プリンター等はいずれも
高速化が可能となり感熱フアツクスではA4版サ
イズで20秒、感熱プリンターでは120字／sec以上
の記録スピードが可能となつている。このように
ハード分野の高速化に伴い、使用される感熱記録
体も記録感度が優れていること（動的記録特性）、
低温領域（60〜70℃）における静的記録がないこ
と、カス付着による記録の切れ（パイリング）が
ないこと等の特性が要求されている。
従来公知の高感度の感熱記録体として、染料と
ビスフエノールＡの如きフエノール化合物にステ
アリン酸アミドの如き増感剤を組合せたものがあ
る。このような高感度の感熱記録体は、その記録
層の構成には染料１に対して増感剤、フエノール
化合物を２乃至５の比率で配合させるのが普通で
ある。しかしこのような従来の感熱記録体は、記
録感度がよくなるにつれて逆に低温領域（60〜70
℃）におけるいわゆる静的記録が現われるという
欠点も伴つている。又、増感剤の量が多いためパ
イリングも悪いという欠点もある。このような状
況から高速記録用にマツチした品質的にバランス
のとれた感熱記録体の開発が待たれているのが現
状である。
そこで本発明者等は、高速記録化したハードに
適した感熱記録体を得るため特に呈色剤の分野を
広く検討した結果、下記式〔〕で表わされる４
−ヒドロキシ安息香酸ベンジルを使用すると高速
記録に好適性を発揮することを見出した。
４−ヒドロキシ安息香酸ベンジルが高速記録に
適性を有している理由を的確に把握することはで
きないが、この物質は、それ自身結晶性が良好で
あるためシヤープな溶解呈色性を示すものと考え
られる。
４−ヒドロキシ安息香酸ベンジルは、このよう
な物性を有しているため、これを感熱記録体用の
呈色剤とする場合は、増感剤は不要であり、この
ことから記録時の溶融量はそれだけ少くて済むこ
とになり、パイリング面でも当然効果的である。
しかしこのような特性を備えた４−ヒドロキシ
安息香酸ベンジルも染料との間で、温度との関連
においては、発色反応と消色反応を示すサーモク
ロミズム的性質を呈することから、感熱記録体用
の呈色剤としては直ちに実用するには難点があ
る。
そこで本発明者等は、４−ヒドロキシ安息香酸
ベンジルが備えている前記長所の物性を生かし、
難点を解消することについていろいろの角度から
鋭意研究した結果、先に４−ヒドロキシ安息香酸
ベンジルと染料として３−（Ｎ−シクロヘキシル
−Ｎ−メチルアミン）−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のうち少くとも一種との組
合せから成る記録層を支持体上に設けることを特
徴とする特許出願をした。しかし先願のこの発明
は、記録像が温度の低下によつて消色する傾向を
改良する効果はあつても、解消するまでには到つ
ていない。
そこで本発明者等は、４−ヒドロキシ安息香酸
ベンジルを前記３種の染料に限らず、無色ないし
淡色の塩基性染料との組合せにおいて、低温にお
いて記録像が消色する傾向があるのを解消し、４
−ヒドロキシ安息香酸ベンジルが備えている長所
の物性を発揮しうる感熱記録体の開発について更
に突込んだ研究をした結果、４−ヒドロキシ安息
香酸ベンジルと、無色ないし淡色の塩基性染料と
の組合せに、更に下記一般式〔〕で表わされる
化合物を併用するとかかる開発目的が達成される
ことを見出したものである。
（式中、R1、R2はそれぞれ水素原子又はC1〜C7
のアルキル基を、R3、ＸはそれぞれC1〜C7のア
ルキル基を、ｍは０〜３の整数を表わす。）
この化合物を併用するこによつて、４−ヒドロ
キシ安息香酸ベンジルがもつサーモクロミズム的
性質が解消される理由は明らかではないが、おそ
らく加熱によつて溶融し発色反応したものが、温
度の低下によつて再結晶化することが消色原因と
考えられ、これが前記化合物の併用によつて再結
晶化するのを阻止する作用があるのではないかと
考えられる。
而して本発明の構成で、感熱記録体の記録層を
形成する無色ないし淡色の塩基性染料としては、
例えば、3.3−ビス（ｐ−ジメチルアミノフエニ
ル）−６−ジメチルアミノフタリド、3.3−ビス
（ｐ−ジメチルアミノフエニル）フタリド、３−
（ｐ−ジメチルアミノフエニル）−３−（1.2−ジメ
チルインドール−３−イル）フタリド等のトリア
リルチタン系染料、4.4′−ビス−ジメチルアミノ
ベンズヒドリルベンジルエーテル、Ｎ−ハロフエ
ニル−ロイコオーラミン、Ｎ−2.4.5−トリクロ
ロフエニルロイコオーラミン等のジフエニルメタ
ン系染料、ベンゾイルロイコメチレンブルー、ｐ
−ニトロベンジルロイコメチレンブルー等のチア
ジン系染料、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−
プロピル−スピロ−ジベンゾピラン等のスピロ系
染料、２−アニリノ−３−メチル−６−（Ｎ−エ
チル−ｐ−トルイジノ）フルオラン、２−ｐ−ト
ルイジノ−３−メチル−６−（Ｎ−エチル−ｐ−
トルイジノ）フルオラン、３−ジエチルアミノ−
６−メチル−７−アニリノフルオラン、３−ジエ
チルアミノ−７−（２−カルボメトキシアニリノ）
フルオラン、３−（Ｎ−シクロヘキシル−Ｎ−メ
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、３−ピペリジノ−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−クロロフルオラン、3.3−ビス
（ｐ−ジメチルアミノフエニル）−６−ジメチルア
ミノフタライド、３−ジエチルアミノ−６−メチ
ル−７−キシリジノフルオラン、３−ジエチルア
ミノ−７−クロロアニリノフルオラン、７−ジエ
チルアミノ−３−クロロフルオラン、７−ジエチ
ルアミノ−３−クロロ−２−メチルフルオラン、
３−メチル−６−（Ｎ−ｐ−トリル−Ｎ−エチル
アミノ）フルオラン、３−ピロジノ−６−メチル
−７−ｐ−ブチルアニリノフルオラン、２−フエ
ニルアミノ−３−メチル−６−（Ｎ−エチル−Ｎ
−ｐ−トリル）アミノフルオラン等のフルオラン
系染料が挙げられる。勿論これらの発色剤のみに
限定するものではない。
一般式〔〕の化合物の具体的物質としては、
2.2′−メチレンビス−（４−メチル−６−ｔ−ブ
チルフエノール）、 mp120℃
2.2′−メチレンビス−（４−エチル−６−ｔーブ
チルフエノール）、 mp119℃
4.4′−ブチリデンビス（６−ｔ−ブチル−ｍ−ク
レゾール）、 mp208℃
などが挙げられる。なお、感熱記録紙として要求
される低温発色カブリ及び白色度を低下させない
でしかも所望の効果が得られるという点からは上
記具体的物質の中でも2.2′−メチレンビス−（４
−エチル−６−ｔ−ブチルフエノール）、2.2′−
メチレンビス（４−エチル−６−ｔ−ブチルフエ
ノール）が好ましい。
記録層中に於ける前記材料の配合比率は、染料
100重量部に対して４−ヒドロキシ安息香酸ベン
ジルを100乃至700重量部配合される。好ましくは
150乃至400重量部の範囲で使用される。
一般式〔〕の化合物の使用量は、４−ヒドロ
キシ安息香酸ベンジル100重量部に対して５乃至
200重量部配合される。好ましくは10乃至100重量
部の範囲で使用される。
これら染料と４−ヒドロキシ安息香酸ベンジル
一般式〔〕の化合物を含む塗液の調整には一般
に水を分散媒体とし、ボールミル、アトライタ
ー、サンドグラインダー等の撹拌、粉砕機により
染料、呈色剤を分散し、塗液として調整される。
かかる塗液中には、通常バインダーとしてデン
プン類、ヒドロキシエチルセルロース、メチルセ
ルロース、カルボキシメチルセルロース、ゼラチ
ン、カゼイン、アラビアゴム、ポリビニルアルコ
ール、スチレン・無水マレイン酸共重合体塩、ス
チレン・アクリル酸共重合体塩、スチレン・ブタ
ジエン共重合体エマルジヨンなどが全固形分の10
乃至40重量％、好ましくは15〜30重量％用いられ
る。
さらに、塗液中には各種の助剤を添加すること
ができる。
例えば、ジオクチルスルフオコハク酸ナトリウ
ム、ドデシルベンゼンスルフオン酸ナトリウム、
ラウリルアルコール硫酸エステル・ナトリウム
塩、脂肪酸金属塩などの分散剤、ベンゾフエノン
系、トリアゾール系などの紫外線吸収剤、その他
消泡剤、螢光染料、着色染料などが挙げられる。
又、感熱記録体が記録機器あるいは記録ヘツドと
の接触に当つてステツキングを生じないよう塗料
中にステアリン酸、ポリエチレン、カルナバロ
ウ、パラフインワツクス、ステアリン酸亜鉛、ス
テアリン酸カルシウム、エステルワツクスなどの
分散液もしくはエマルジヨンなどを添加すること
もできる。記録ヘツドへのカス付着を改善するた
めにカオリン、クレー、タルク、炭酸カルシウ
ム、焼成クレー、酸化チタン、珪藻土、微粒子状
無水シリカ、活性白土等の無機顔料を添加するこ
ともできる。また必要に応じてステアリン酸アミ
ド、ステアリン酸メチレンビスアミド、オレイン
酸アミド、パルミチン酸アミド、抹香オレイン酸
アミド、ヤシ脂肪酸アミド等を増感剤として添加
することもできる。
支持体としては、紙、プラスチツクフイルム、
合成紙等が用いられるが、価格、塗布適性等の点
で紙が最も好ましく用いられる。また記録層を形
成する塗液の支持体への塗布量は特に限定される
ものではないが、通常乾燥重量で２乃至12ｇ／
m2、好ましくは３乃至10ｇ／m2の範囲である。
かくして得られる本発明の感熱記録体は高速記
録適性を有しており、しかも温度低下に際しても
記録像の消色傾向は解消でき、記録針へのカス付
着（パイリング）の面でも優れた性質を有してい
る。
以下に実施例を示し、本発明をより具体的に説
明するが、勿論これらに限定されるものではな
い。また特に断らない限り例中の部および％はそ
れぞれ重量部および重量％を示す。
実施例 １
Ａ液調成
３−（Ｎ−シクロヘキシル−Ｎ−メチルアミノ）
−６−メチル−アニリノフルオラン 10部
メチルセルロース５％水溶液 5部
水 40部
この組成物をサンドグライダーで平均粒子径
3μｍまで粉砕した。
Ｂ液調成
４−ヒドロキシ安息香酸ベンジル 30部
2.2′−メチレンビス（４−メチル−６−ｔ−ブ
チルフエノール） 10部
メチルセルロース５％水溶液 30部
水 70部
この組成物をサンドグラインダーで平均粒子
径3μｍまで粉砕した。
記録層の形成
Ａ液55部、Ｂ液140部、酸化珪素顔料30部、
20％酸化澱粉水溶液150部、水55部を混合し撹
拌する。得られた塗液を50ｇ／m2の原紙に乾燥
後の塗布量が7.5ｇ／m2となるように塗布乾燥
して感熱記録紙を得た。
実施例 ２
Ｂ液調成において、２，2′−メチレンビス（４
−メチル−６−ｔ−ブチルフエノール）の代わり
に２，2′−メチレンビス（４−エチル−６−ｔ−
ブチルフエノール）を使用した以外は実施例１と
同様にして感熱記録紙を得た。
実施例 ３
Ｂ液調成において、２，2′−メチレンビス（４
−メチル−６−ｔ−ブチルフエノール）の代わり
に４，4′−ブチリデンビス（６−ｔ−ブチル−ｍ
−クレゾール）を使用した以外は実施例１と同様
にして感熱記録紙を得た。
比較例 １
Ｂ液調成において２，2′−メチレンビス（４−
メチル−６−ｔ−ブチルフエノール）を使用しな
い以外は実施例１と同様にして感熱記録紙を得
た。
上記の実施例及び比較例で得た感熱記録紙を感
熱フアクシミリ（東芝KB−4800型）を使用して
記録した。その結果、記録感度及び記録像の消色
状態は以下の如くであつた。
The present invention relates to a heat-sensitive recording medium, and particularly to a heat-sensitive recording medium that is suitable for high-speed recording and that prevents recorded images from fading. Conventionally, heat-sensitive recording materials are well known, which utilize a color reaction between a colorless or light-colored basic dye and an organic or inorganic coloring agent, and obtain a recorded image by bringing both coloring substances into contact with each other using heat. . Recently, with remarkable progress in thermal recording methods, thermal faxes and thermal printers that use thermal heads have become faster, with thermal faxes recording speeds of 20 seconds for A4 size, and thermal printers recording speeds of over 120 characters/sec. is now possible. As the speed of the hardware field increases, the thermal recording media used also have superior recording sensitivity (dynamic recording characteristics).
Characteristics such as no static recording in the low temperature range (60 to 70°C) and no recording breaks (piling) due to adhesion of debris are required. As a conventionally known highly sensitive heat-sensitive recording medium, there is one in which a dye, a phenol compound such as bisphenol A, and a sensitizer such as stearic acid amide are combined. In such a highly sensitive heat-sensitive recording material, the recording layer usually contains a sensitizer and a phenol compound in a ratio of 2 to 5 parts dye to 1 part dye. However, as the recording sensitivity of conventional heat-sensitive recording media improves, the temperature range (60 to 70
The disadvantage is that a so-called static record appears at temperatures (°C). Another disadvantage is that piling is poor due to the large amount of sensitizer. Under these circumstances, there is currently a need for the development of a quality-balanced thermal recording medium suitable for high-speed recording. Therefore, in order to obtain a heat-sensitive recording medium suitable for high-speed recording hardware, the present inventors extensively investigated the field of coloring agents, and found that 4 expressed by the following formula []
It has been found that the use of benzyl hydroxybenzoate is suitable for high-speed recording. Although it is not clear exactly why benzyl 4-hydroxybenzoate is suitable for high-speed recording, it is believed that this substance itself exhibits sharp dissolution coloration due to its good crystallinity. Conceivable. Benzyl 4-hydroxybenzoate has such physical properties, so when it is used as a coloring agent for heat-sensitive recording materials, a sensitizer is not required. This means that the amount required is that much less, which is naturally effective in terms of piling. However, benzyl 4-hydroxybenzoate, which has such characteristics, also exhibits thermochromic properties that exhibit coloring and decolorizing reactions in relation to temperature when it interacts with dyes. There are some difficulties in immediately putting it into practical use as a coloring agent. Therefore, the present inventors took advantage of the above-mentioned advantageous physical properties of benzyl 4-hydroxybenzoate, and
As a result of intensive research from various angles to solve the problems, we first developed benzyl 4-hydroxybenzoate and 3-(N-cyclohexyl-N-methylamine)-6-methyl-7-anilinofluorane as a dye. 3-pyrrolidino-6-methyl-7
- A patent application has been filed which is characterized in that a recording layer comprising a combination of at least one type of anilinofluorane is provided on a support. However, although this invention of the earlier application has the effect of improving the tendency of recorded images to fade due to a decrease in temperature, it has not yet been able to eliminate the tendency. Therefore, the present inventors solved the tendency of recorded images to fade at low temperatures by combining benzyl 4-hydroxybenzoate not only with the above three types of dyes but also with colorless or light-colored basic dyes. , 4
-As a result of further in-depth research into the development of a heat-sensitive recording material that can exhibit the physical properties of benzyl hydroxybenzoate, we found that a combination of benzyl 4-hydroxybenzoate and a colorless or light-colored basic dye was developed. It has been discovered that the above development objective can be achieved when a compound represented by the following general formula [] is used in combination. (In the formula, R 1 and R 2 are each a hydrogen atom or C 1 to C 7
R 3 and X each represent a C 1 to C 7 alkyl group, and m represents an integer of 0 to 3. ) It is not clear why the thermochromic properties of benzyl 4-hydroxybenzoate are eliminated when this compound is used in combination, but it is likely that the thermochromic properties of benzyl 4-hydroxybenzoate are eliminated by the temperature drop. It is believed that recrystallization caused by this is the cause of discoloration, and that the combined use of the above compound may have the effect of inhibiting recrystallization. According to the structure of the present invention, the colorless or light-colored basic dye forming the recording layer of the heat-sensitive recording medium is as follows:
For example, 3.3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3.3-bis(p-dimethylaminophenyl)phthalide, 3-
Triallyl titanium dyes such as (p-dimethylaminophenyl)-3-(1.2-dimethylindol-3-yl) phthalide, 4,4'-bis-dimethylaminobenzhydryl benzyl ether, N-halofenyl-leucoauramine , diphenylmethane dyes such as N-2.4.5-trichlorophenylleucoauramine, benzoylleucomethylene blue, p
- Thiazine dyes such as nitrobenzylleucomethylene blue, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro; dinaphthopyran, 3-
Spiro dyes such as propyl-spiro-dibenzopyran, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluoran, 2-p-toluidino-3-methyl-6-(N-ethyl- p-
toluidino)fluoran, 3-diethylamino-
6-Methyl-7-anilinofluorane, 3-diethylamino-7-(2-carbomethoxyanilino)
Fluoran, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7
-anilinofluorane, 3-diethylamino-6
-Methyl-7-chlorofluorane, 3.3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-diethylamino-6-methyl-7-xylidinofluorane, 3-diethylamino-7-chloro Anilinofluorane, 7-diethylamino-3-chlorofluorane, 7-diethylamino-3-chloro-2-methylfluorane,
3-Methyl-6-(N-p-tolyl-N-ethylamino)fluorane, 3-pyrodino-6-methyl-7-p-butylanilinofluorane, 2-phenylamino-3-methyl-6-(N -ethyl-N
Examples include fluoran dyes such as -p-tolyl)aminofluorane. Of course, it is not limited to these coloring agents. Specific substances of the compound of general formula [] include 2.2'-methylenebis-(4-methyl-6-t-butylphenol), mp120℃ 2.2'-methylenebis-(4-ethyl-6-t-butylphenol) , mp119°C 4.4'-butylidenebis(6-t-butyl-m-cresol), mp208°C, and the like. Among the above-mentioned specific substances, 2.2'-methylenebis-(4
-ethyl-6-t-butylphenol), 2.2'-
Methylenebis(4-ethyl-6-t-butylphenol) is preferred. The blending ratio of the above materials in the recording layer is
100 to 700 parts by weight of benzyl 4-hydroxybenzoate is added to 100 parts by weight. Preferably
It is used in a range of 150 to 400 parts by weight. The amount of the compound of general formula [] to be used is 5 to 5 parts by weight per 100 parts by weight of benzyl 4-hydroxybenzoate.
Contains 200 parts by weight. It is preferably used in an amount of 10 to 100 parts by weight. To prepare a coating solution containing these dyes and a compound of the general formula of benzyl 4-hydroxybenzoate, water is generally used as a dispersion medium, and the dye and coloring agent are mixed using a ball mill, attritor, sand grinder, or other stirring or crushing machine. It is dispersed and prepared as a coating liquid. Such coating liquids usually contain starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, gum arabic, polyvinyl alcohol, styrene/maleic anhydride copolymer salt, styrene/acrylic acid copolymer salt, Styrene-butadiene copolymer emulsion, etc. has a total solid content of 10
It is used in an amount of 40 to 40% by weight, preferably 15 to 30% by weight. Furthermore, various auxiliary agents can be added to the coating liquid. For example, sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate,
Examples include dispersants such as lauryl alcohol sulfate/sodium salt and fatty acid metal salts, ultraviolet absorbers such as benzophenone and triazole, antifoaming agents, fluorescent dyes, and coloring dyes.
In addition, a dispersion of stearic acid, polyethylene, carnauba wax, paraffin wax, zinc stearate, calcium stearate, ester wax, etc. is added to the paint to prevent sticking when the heat-sensitive recording material comes into contact with a recording device or recording head. Alternatively, emulsion or the like may be added. Inorganic pigments such as kaolin, clay, talc, calcium carbonate, calcined clay, titanium oxide, diatomaceous earth, fine particulate anhydrous silica, and activated clay may be added to improve the adhesion of residue to the recording head. If necessary, stearic acid amide, stearic acid methylene bisamide, oleic acid amide, palmitic acid amide, matcha oleic acid amide, coconut fatty acid amide, etc. can also be added as a sensitizer. Supports include paper, plastic film,
Synthetic paper and the like can be used, but paper is most preferably used in terms of cost, applicability, etc. Furthermore, the amount of the coating liquid that forms the recording layer applied to the support is not particularly limited, but is usually 2 to 12 g/dry weight.
m 2 , preferably in the range 3 to 10 g/m 2 . The heat-sensitive recording material of the present invention thus obtained has suitability for high-speed recording, can eliminate the tendency of recorded images to fade even when the temperature decreases, and has excellent properties in terms of dust adhesion to the recording needle (piling). have. The present invention will be described in more detail with reference to Examples below, but it is of course not limited thereto. Further, unless otherwise specified, parts and percentages in the examples indicate parts by weight and percentages by weight, respectively. Example 1 Preparation of liquid A 3-(N-cyclohexyl-N-methylamino)
-6-Methyl-anilinofluorane 10 parts Methyl cellulose 5% aqueous solution 5 parts Water 40 parts This composition was mixed using a sand glider with an average particle size of
It was ground to 3 μm. Preparation of Solution B Benzyl 4-hydroxybenzoate 30 parts 2.2'-methylenebis(4-methyl-6-t-butylphenol) 10 parts Methylcellulose 5% aqueous solution 30 parts Water 70 parts This composition was ground with a sand grinder to an average particle diameter of 3 μm. crushed to. Formation of recording layer: 55 parts of liquid A, 140 parts of liquid B, 30 parts of silicon oxide pigment,
Mix 150 parts of 20% oxidized starch aqueous solution and 55 parts of water and stir. The obtained coating liquid was applied to a base paper of 50 g/m 2 so that the coated amount after drying was 7.5 g/m 2 and dried to obtain heat-sensitive recording paper. Example 2 In preparing liquid B, 2,2'-methylenebis(4
-methyl-6-t-butylphenol) instead of 2,2'-methylenebis(4-ethyl-6-t-
A thermosensitive recording paper was obtained in the same manner as in Example 1, except that 1-butylphenol was used. Example 3 In preparing liquid B, 2,2'-methylenebis(4
-methyl-6-t-butylphenol) instead of 4,4'-butylidenebis(6-t-butyl-m
A thermosensitive recording paper was obtained in the same manner as in Example 1, except that 1-cresol) was used. Comparative Example 1 In preparing liquid B, 2,2'-methylenebis(4-
A thermosensitive recording paper was obtained in the same manner as in Example 1 except that methyl-6-t-butylphenol was not used. The thermal recording papers obtained in the above Examples and Comparative Examples were recorded using a thermal facsimile (Toshiba KB-4800 model). As a result, the recording sensitivity and decolorization state of the recorded image were as follows.
【表】
〓× 殆んど消色する〓
[Table] 〓× Almost erased〓
Claims (1)
〔〕の化合物 及び下記一般式〔〕の化合物 （式中、R1、R2はそれぞれ水素原子又はC1〜C7
のアルキル基を、R3、ＸはそれぞれC1〜C7のア
ルキル基を、ｍは０〜３の整数を表わす。） を含有する記録層を支持体上に設けたことを特徴
とする感熱記録体。 ２ 一般式〔〕の化合物が２，2′−メチレン−
ビス（４−エチル−６−ターシヤリ−ブチルフエ
ノール）である請求の範囲第１項記載の感熱記録
体。 ３ 一般式〔〕の化合物が２，2′−メチレン−
ビス−（４−メチル−６−ターシヤリ−ブチルフ
エノール）である請求の範囲第１項記載の感熱記
録体。[Claims] 1. A colorless or light-colored basic dye and a compound of the following formula [] and a compound of the following general formula [] (In the formula, R 1 and R 2 are each a hydrogen atom or C 1 to C 7
R 3 and X each represent a C 1 to C 7 alkyl group, and m represents an integer of 0 to 3. ) A heat-sensitive recording material, characterized in that a recording layer containing the following is provided on a support. 2 The compound of general formula [] is 2,2'-methylene-
The heat-sensitive recording material according to claim 1, which is bis(4-ethyl-6-tertiary-butylphenol). 3 The compound of general formula [] is 2,2'-methylene-
The heat-sensitive recording material according to claim 1, which is bis-(4-methyl-6-tertiary-butylphenol).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55160189A JPS5783495A (en) | 1980-11-13 | 1980-11-13 | Thermosensitive recording body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55160189A JPS5783495A (en) | 1980-11-13 | 1980-11-13 | Thermosensitive recording body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5783495A JPS5783495A (en) | 1982-05-25 |
| JPS6344077B2 true JPS6344077B2 (en) | 1988-09-02 |
Family
ID=15709740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55160189A Granted JPS5783495A (en) | 1980-11-13 | 1980-11-13 | Thermosensitive recording body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5783495A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02115695A (en) * | 1988-10-24 | 1990-04-27 | Daikin Ind Ltd | Heat exchanger |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5783495A (en) * | 1980-11-13 | 1982-05-25 | Kanzaki Paper Mfg Co Ltd | Thermosensitive recording body |
| JPS57116689A (en) * | 1981-01-12 | 1982-07-20 | Jujo Paper Co Ltd | Thermal recording sheet |
| JPS592891A (en) * | 1982-06-30 | 1984-01-09 | Honshu Paper Co Ltd | Heat-sensitive recording material |
| JPS59165684A (en) * | 1983-03-10 | 1984-09-18 | Ricoh Co Ltd | Thermal recording material |
| JPS59194891A (en) * | 1983-04-20 | 1984-11-05 | Fuji Photo Film Co Ltd | Thermal recording material |
| JPS61130085A (en) * | 1984-11-29 | 1986-06-17 | Fuji Photo Film Co Ltd | Thermal recording paper |
| JPS61134292A (en) * | 1984-12-04 | 1986-06-21 | Tomoegawa Paper Co Ltd | Thermal recording material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4945747A (en) * | 1972-09-04 | 1974-05-01 | Mitsubishi Paper Mills Ltd | Anteisei o kairyoshita kannetsukirokuyoshiito |
| JPS5143386A (en) * | 1974-10-11 | 1976-04-14 | Mitsubishi Electric Corp | CHIKUNET SUZAI |
| JPS52140483A (en) * | 1976-05-19 | 1977-11-24 | Fuji Photo Film Co Ltd | Thermochromism material |
| JPS5418752A (en) * | 1977-07-13 | 1979-02-13 | Hitachi Ltd | Heat sensitive recording paper |
| JPS56136389A (en) * | 1980-03-28 | 1981-10-24 | Asahi Chem Ind Co Ltd | Thermosensitive coloring sheet |
| JPS56144193A (en) * | 1980-04-10 | 1981-11-10 | Jujo Paper Co Ltd | Heat-sensitive recording sheet |
| JPS5783495A (en) * | 1980-11-13 | 1982-05-25 | Kanzaki Paper Mfg Co Ltd | Thermosensitive recording body |
-
1980
- 1980-11-13 JP JP55160189A patent/JPS5783495A/en active Granted
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4945747A (en) * | 1972-09-04 | 1974-05-01 | Mitsubishi Paper Mills Ltd | Anteisei o kairyoshita kannetsukirokuyoshiito |
| JPS5143386A (en) * | 1974-10-11 | 1976-04-14 | Mitsubishi Electric Corp | CHIKUNET SUZAI |
| JPS52140483A (en) * | 1976-05-19 | 1977-11-24 | Fuji Photo Film Co Ltd | Thermochromism material |
| JPS5418752A (en) * | 1977-07-13 | 1979-02-13 | Hitachi Ltd | Heat sensitive recording paper |
| JPS56136389A (en) * | 1980-03-28 | 1981-10-24 | Asahi Chem Ind Co Ltd | Thermosensitive coloring sheet |
| JPS56144193A (en) * | 1980-04-10 | 1981-11-10 | Jujo Paper Co Ltd | Heat-sensitive recording sheet |
| JPS5783495A (en) * | 1980-11-13 | 1982-05-25 | Kanzaki Paper Mfg Co Ltd | Thermosensitive recording body |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02115695A (en) * | 1988-10-24 | 1990-04-27 | Daikin Ind Ltd | Heat exchanger |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5783495A (en) | 1982-05-25 |
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