JPH01295887A - Heat-sensitive recording material - Google Patents
Heat-sensitive recording materialInfo
- Publication number
- JPH01295887A JPH01295887A JP63125860A JP12586088A JPH01295887A JP H01295887 A JPH01295887 A JP H01295887A JP 63125860 A JP63125860 A JP 63125860A JP 12586088 A JP12586088 A JP 12586088A JP H01295887 A JPH01295887 A JP H01295887A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- radical
- color
- recording material
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 claims abstract description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005977 Ethylene Substances 0.000 claims abstract description 5
- PRMDDINQJXOMDC-UHFFFAOYSA-N 4-[4,4-bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-cyclohexyl-5-methylphenol Chemical compound C=1C(C2CCCCC2)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C2CCCCC2)C=1)C)C(C(=CC=1O)C)=CC=1C1CCCCC1 PRMDDINQJXOMDC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000002560 nitrile group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- -1 alkyl radical Chemical class 0.000 abstract description 14
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 239000003973 paint Substances 0.000 abstract 2
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 abstract 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 abstract 1
- BLNWTAHYTCHDJH-UHFFFAOYSA-O hydroxy(oxo)azanium Chemical compound O[NH+]=O BLNWTAHYTCHDJH-UHFFFAOYSA-O 0.000 abstract 1
- 150000002989 phenols Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 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 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 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
- 239000001273 butane Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical class C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 150000004897 thiazines Chemical class 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
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- FKIOYBLZUCCLTL-UHFFFAOYSA-N 4-butyl-2-tert-butyl-5-methylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C=C1C FKIOYBLZUCCLTL-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical class O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 1
- ZCTQGTTXIYCGGC-UHFFFAOYSA-N Benzyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OCC1=CC=CC=C1 ZCTQGTTXIYCGGC-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 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
- 229910052570 clay Inorganic materials 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- DWNAQMUDCDVSLT-UHFFFAOYSA-N diphenyl phthalate Chemical compound C=1C=CC=C(C(=O)OC=2C=CC=CC=2)C=1C(=O)OC1=CC=CC=C1 DWNAQMUDCDVSLT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 1
- RPOCFUQMSVZQLH-UHFFFAOYSA-N furan-2,5-dione;2-methylprop-1-ene Chemical compound CC(C)=C.O=C1OC(=O)C=C1 RPOCFUQMSVZQLH-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
- 235000019447 hydroxyethyl cellulose Nutrition 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
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001290 polyvinyl ester 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
- 229940037312 stearamide Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000001993 wax Substances 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
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〉
本発明は感熱記録材料に関し、詳しくはロイコ染料及び
該染料を熱時発色させる顕色剤を含む感熱記録材料の高
速記録適性にすぐれかつ保存性を向上させた感熱記録材
料に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a heat-sensitive recording material, and more specifically, a heat-sensitive recording material containing a leuco dye and a color developer that develops color when the dye is heated, which has excellent suitability for high-speed recording and storage. This invention relates to a heat-sensitive recording material with improved properties.
〈従来の技術〉
一般に無色又は淡色のロイコ染料と該ロイコ染料を熱時
発色させる顕色剤とを発色成分とする感熱記録材料は、
従来実用化された他の感熱記録材料に比べて、得られる
発色像が非常に鮮明であることから、広くコンピュータ
ーのアウトプット、ファクシミリ、レコーダー等の記録
紙として、又切符類、カード類にも使用されている。該
記録紙の記録特性は用途によって異なるが、例えば記録
速度を上げるためには、記録装置の改良とともに記録紙
自身の発色性を促進する必要があり、近年この方向の感
熱紙の開発が求められている。<Prior Art> In general, a heat-sensitive recording material whose coloring components are a colorless or light-colored leuco dye and a color developer that causes the leuco dye to develop color when heated.
Compared to other heat-sensitive recording materials that have been put to practical use, the color image obtained is very clear, so it is widely used as recording paper for computer output, facsimiles, recorders, etc., and also for tickets and cards. It is used. The recording properties of the recording paper differ depending on the application, but for example, in order to increase the recording speed, it is necessary to improve the recording device and promote the color development of the recording paper itself, and in recent years there has been a demand for the development of thermal paper in this direction. ing.
従来より顕色剤としてはビスフェノールＡが一般的に使
用されてきたがビスフェノールＡは融点が１５７℃と高
く高速記録適性がなく、高速記録適性を上げるため各種
の増感剤を添加することも提案されているもののいまだ
十分効果があるものではない。Bisphenol A has traditionally been commonly used as a color developer, but bisphenol A has a high melting point of 157°C and is not suitable for high-speed recording, so it has also been proposed to add various sensitizers to improve suitability for high-speed recording. Although this has been done, it is still not fully effective.
また高速記録適性を上げるため、より融点の低い顕色剤
の提案も多数なされており、実用可能なものとしてはｐ
−ヒドロキシ安息香酸エステル（特開昭５６−１４４１
９３号）、４−ヒドロキシフタル酸ジエステル（特開昭
５８−１５３６９２号）、４−ヒドロキシフェニル ４
−アルコキシフェニルスルホン（特開昭６０−１３８５
２号）およびビス（４−ヒドロキシ−３−アリルフェニ
ル）スルホン（特開昭６０−２０８２８６号）等が考え
られている。しかしながらこれれらの物質はいずれも得
られた画像の退色性が著しく劣るという欠点を有してい
る。そこで退色性を改良するために酸化防止剤等の各種
薬品の添加も提案されているが記録性と保存性とが満足
できるものは得られていない。In addition, in order to improve suitability for high-speed recording, many proposals have been made for color developers with lower melting points, and p
-Hydroxybenzoic acid ester (JP-A-56-1441
93), 4-hydroxyphthalic acid diester (JP-A-58-153692), 4-hydroxyphenyl 4
-Alkoxyphenylsulfone (JP-A-60-1385
2) and bis(4-hydroxy-3-allylphenyl)sulfone (Japanese Patent Application Laid-open No. 60-208286). However, all of these materials have the disadvantage that the resulting images have significantly poor fading resistance. Therefore, the addition of various chemicals such as antioxidants has been proposed in order to improve the fading resistance, but nothing with satisfactory recording performance and storage stability has been obtained.
〈発明が解決しようとする問題点〉
本発明は高速記録性にすぐれ、かつ保存安定性、特に耐
水性にもすぐれた感熱記録体を得ることを目的とする。<Problems to be Solved by the Invention> An object of the present invention is to obtain a heat-sensitive recording medium that has excellent high-speed recording properties and also has excellent storage stability, particularly water resistance.
く問題を解決するための手段〉
本発明は、支持体上に無色又は淡色のロイコ染料と該ロ
イコ染料を熱時発色させる顕色剤を含有する感熱層を設
けた感熱記録材料において、該顕色剤として下記の一般
式（１）によって表わされる化合物を使用し、かつ１，
１．３−トリ （３−ｔ−ブチル−４−ヒドロキシ−６
−メチルフェニル）ブタン、１，１．３−トリ （３−
シクロへキシル−４−ヒドロキシ−６−メチルフェニル
）ブタンおよび１．２−ビス〔３，３−ビス（３−ｔ−
ブチル−４−ヒドロキシフェニル）ブチリルオキシ〕エ
チレンのうちの少くとも１つの化合物を含有させたこと
を特徴とする感熱記録材料で、高速記録性にすぐれ、か
つ、保存安定性、特に耐水性がすぐれた感熱記録体が得
られることを見いだしたものである。Means for Solving Problems> The present invention provides a heat-sensitive recording material in which a heat-sensitive layer containing a colorless or light-colored leuco dye and a color developer that develops color when heated is provided on a support. A compound represented by the following general formula (1) is used as a coloring agent, and 1,
1.3-tri(3-t-butyl-4-hydroxy-6
-methylphenyl)butane, 1,1,3-tri(3-
cyclohexyl-4-hydroxy-6-methylphenyl)butane and 1,2-bis[3,3-bis(3-t-
A heat-sensitive recording material characterized by containing at least one compound of butyl-4-hydroxyphenyl)butyryloxy]ethylene, which has excellent high-speed recording properties and excellent storage stability, especially water resistance. It has been discovered that a thermosensitive recording material can be obtained.
一般式（１）
（式中Ｚは硫黄原子、−５ｏｚ−、Ｒ’ は低級アルキ
い低級アルキル基、フェニル基、ベンジル基を示し、こ
こにＲ３は水素原子、置換されてもよい低級アルキル基
、ハロゲン原子、ニトリル基、ニトロ基又はアルコキシ
基を示す）
次に一般式（１）によって表わされる化合物の具体例と
しては
などがあるが、本発明はこれらに限定されるものではな
い。General formula (1) (wherein Z is a sulfur atom, -5oz-, R' is a lower alkyl group, a phenyl group, or a benzyl group, where R3 is a hydrogen atom or a lower alkyl group that may be substituted) , a halogen atom, a nitrile group, a nitro group, or an alkoxy group) Next, specific examples of the compound represented by the general formula (1) include the following, but the present invention is not limited thereto.
これらは必要に応じて単独もしくは混合又は他の顕色剤
、例えば、ビスフェノールＡ、ビスフェノールＳ、４−
ヒドロキシ安息香酸ベンジルエステル、活性白土などと
混合して用いることもできる。These may be used alone or in combination or with other color developers, such as bisphenol A, bisphenol S, 4-
It can also be used in combination with hydroxybenzoic acid benzyl ester, activated clay, etc.
本発明の感熱記録材料は、本発明の感熱層上に皮膜層を
設けて更に保存性を高め、切符やカード類に好適に使用
することができる。更に、この皮膜層を設けた本発明の
感熱記録材料の支持体の裏面にバック層並びに感圧接着
層を順次設け、これに剥離紙を貼付してラベル用等の感
熱記録材料として使用することもできる。The heat-sensitive recording material of the present invention can be suitably used for tickets and cards by providing a film layer on the heat-sensitive layer of the present invention to further improve its preservability. Furthermore, a back layer and a pressure-sensitive adhesive layer are sequentially provided on the back side of the support of the heat-sensitive recording material of the present invention provided with this film layer, and a release paper is attached to this to use it as a heat-sensitive recording material for labels, etc. You can also do it.
本発明で用いられる無色又は淡色のロイコ染料の例とし
てはトリアリールメタン系化合物、ジフェニルメタン系
化合物、キサンチン系化合物、チアジン系化合物、スピ
ロピラン系化合物などが用いられ、その具体的な化合物
を例示すれば、クリスタルバイオレットラクトン、３，
３−ビス（Ｐ−ジメチルアミノフェニル）フタリドなど
のトリアリールメタン系化合物、４，４′−ビス−ジメ
チルアミノベンズヒドリンベンジルエーテル、Ｎ−ハロ
フェニル−ロイコオーラミン等のジフェニルメタン系化
合物、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−クロロフルオラン
、３−シクロヘキシルアミノ−６−クロロフルオラン、
３−ジエチルアミノ−７−ジベンジルアミノフルオラン
、３−ピロリジノ−６−メチル−７−アニリノフルオラ
ン、３−ビペリジノ−６−メチル−７−アニリノフルオ
ラン、３−シクロヘキシルメチルアミノ−６−メチル−
７−アニリノフルオラン、３−エチルイソアミルアミノ
−６−メチル−７−アニリノフルオラン、３−ジエチル
アミノ−７−（ｏ−クロロアニリノ）フルオラン、３−
ジブチルアミノ−７−（０−クロロアニリノ）フルオラ
ン等のキサンチン系化合物、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
チアジン系化合物、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、３，３′−
シクロロースピロージナフトピラン等のスピロピラン系
化合物などがあげられる。又これらは単独もしくは混合
して用いることができる。Examples of the colorless or light-colored leuco dye used in the present invention include triarylmethane compounds, diphenylmethane compounds, xanthine compounds, thiazine compounds, and spiropyran compounds. , crystal violet lactone, 3,
Triarylmethane compounds such as 3-bis(P-dimethylaminophenyl)phthalide, diphenylmethane compounds such as 4,4'-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leucoauramine, 3-diethylamino -7-chlorofluorane, 3
-diethylamino-6-methyl-7-chlorofluorane, 3-cyclohexylamino-6-chlorofluorane,
3-diethylamino-7-dibenzylaminofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-biperidino-6-methyl-7-anilinofluorane, 3-cyclohexylmethylamino-6- Methyl-
7-anilinofluorane, 3-ethylisoamylamino-6-methyl-7-anilinofluorane, 3-diethylamino-7-(o-chloroanilino)fluorane, 3-
Xanthine compounds such as dibutylamino-7-(0-chloroanilino)fluoran, thiazine compounds such as benzoylleucomethylene blue and p-nitrobenzylleucomethylene blue, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3 ,3'-
Examples include spiropyran compounds such as cyclorosespirodinaphthopyran. Moreover, these can be used alone or in combination.
更に、本発明の感熱層を構成するためには結着剤、ある
いは本発明の効果を阻害しない限りにおいて増悪剤、充
填剤が適宜使用せられる。Furthermore, in order to constitute the heat-sensitive layer of the present invention, a binder, an aggravating agent, and a filler may be appropriately used as long as they do not impede the effects of the present invention.
感熱層の結着剤、更に本発明の感熱記録材料における被
膜層、バック層として使用される材料としては、例えば
カゼイン、ゼラチン、ポリビニルアルコール、変性ポリ
ビニルアルコール、ポリビニルピロリドン、でん粉、イ
ソブチレン−無水マレイン酸樹脂、スチレン−無水マレ
イン酸樹脂、ポリアクリルアミド、カルボキシメチルセ
ルロース、ヒドロキシエチルセルロース、あるいは、酢
酸ビニル樹脂、アクリル酸エステル樹脂、塩化ビニル−
酢酸ビニル共重合体、ＳＢＲ，ＮＢＲ等のエマルジョン
、ラテックスなどが用いられる。Examples of materials used as the binder for the heat-sensitive layer, and also for the coating layer and back layer in the heat-sensitive recording material of the present invention include casein, gelatin, polyvinyl alcohol, modified polyvinyl alcohol, polyvinylpyrrolidone, starch, and isobutylene-maleic anhydride. Resin, styrene-maleic anhydride resin, polyacrylamide, carboxymethyl cellulose, hydroxyethyl cellulose, or vinyl acetate resin, acrylic ester resin, vinyl chloride
Emulsions, latex, etc. of vinyl acetate copolymers, SBR, NBR, etc. are used.
増感剤としては、例えばエルカ酸、ステアリン酸、フタ
ル酸ジフェニルエステル、１−ヒドロキシ−２ナフトエ
酸フエニルエステル、更にパラフィンワックス、ステア
リン酸アマイド等のワックス類などが用いられる。As the sensitizer, for example, erucic acid, stearic acid, diphenyl phthalate, phenyl 1-hydroxy-2-naphthoic acid ester, and waxes such as paraffin wax and stearamide are used.
更に充填剤としては、例えば炭酸カルシウム、水酸化ア
ルミニウム、酸化チタン、酸化亜鉛、硫酸バリウム、タ
ルク、クレー、カオリナイト、ポリオレフィン粒子、ポ
リスチレン粒子、尿素−ホルマリン樹脂粒子等の吸油性
顔料などが必要に応じて加えられる。更に必要に応じて
、耐光性向上の目的に酸化防止剤、紫外線吸収剤、エネ
ルギークエンチャ−等を本発明の感熱層又は被膜層に含
有させることも出来る。Furthermore, as fillers, oil-absorbing pigments such as calcium carbonate, aluminum hydroxide, titanium oxide, zinc oxide, barium sulfate, talc, clay, kaolinite, polyolefin particles, polystyrene particles, urea-formalin resin particles, etc. are required. Added accordingly. Further, if necessary, an antioxidant, an ultraviolet absorber, an energy quencher, etc. can be included in the heat-sensitive layer or coating layer of the present invention for the purpose of improving light resistance.
本発明の感熱記録材料は、ロイコ染料と顕色剤を各々微
粒子に分散化後両者を混合し前記の各成分を必要に応じ
て添加して得た感熱層用塗料を紙、プラスチックシート
、樹脂コーテツド紙等の支持体に塗布することにより得
ることができる。The heat-sensitive recording material of the present invention is produced by dispersing a leuco dye and a color developer into fine particles, mixing the two, and adding the above-mentioned components as necessary. It can be obtained by coating on a support such as coated paper.
さらには感圧接着層に用いられる粘着剤は、アクリル酸
エステル樹脂、エチレン／酢酸ビニル系共重合樹脂等の
エマルジョン型で用いるものと、天然ゴム系、合成ゴム
系、ポリアクリル酸エステル系、ポリビニルアルコール
系等の溶液型、ポリビニルアルコールやデキストリン澱
粉等の感湿性接着剤等を用いることが出来る。Furthermore, the adhesives used in the pressure-sensitive adhesive layer include emulsion-type adhesives such as acrylic ester resins and ethylene/vinyl acetate copolymer resins, natural rubber-based, synthetic rubber-based, polyacrylic ester-based, and polyvinyl ester resins. Solution type adhesives such as alcohol-based adhesives, moisture-sensitive adhesives such as polyvinyl alcohol and dextrin starch, etc. can be used.
剥離紙としては紙等の支持体にシリコーン樹脂や弗素系
樹脂の離型剤を塗布含浸したもの、又は、シリコーン樹
脂や弗素系樹脂等の離型作用のすぐれたプラスチックテ
ープ等が用いられる。As the release paper, a support such as paper coated and impregnated with a mold release agent such as a silicone resin or a fluorine resin, or a plastic tape made of a silicone resin or a fluorine resin having an excellent mold release effect may be used.
〈実施例〉 以下実施例、比較例にて本発明の詳細な説明する。<Example> The present invention will be explained in detail below using Examples and Comparative Examples.
なお各実施例、比較例における部数は全て重量部を示す
ものとする。Note that all parts in each Example and Comparative Example indicate parts by weight.
実施例１
下記の組成からなる混合物をそれぞれ別個にダイノミル
を用いて粉砕・分散して［Ａ］液、［Ｂ］液、［Ｃコ液
を調製した。Example 1 Mixtures having the following compositions were separately ground and dispersed using a dyno mill to prepare liquids [A], [B], and [C].
Ａ液；
ベンジル−４−ヒドロキシフェニルスルホニル酢酸エス
テル ２５部ポリビニルアルコール（
１０％水溶液）２４部１．１．３− ）リ （３−ｔ−
ブチル−４−ヒドロキシ−６−メチルフェニル）ブタン
４部水
２８部ＢＹ夜 ；
３−（Ｎ−イソアミル−Ｎ−一エチルアミノ）−６−メ
チル−７−アニリツフルオラン
１０部ポリビニルアルコール（１０％水溶液）
１５部水
１５部Ｃ液；
炭酸カルシウム ２３部ポリビニ
ルアルコール（１０％水溶液）２３部水
１４部ついでＡ液
１１．５部、Ｅ液３．７部、Ｃ液９．１部、ポリビニル
アルコール（１０％水溶？ＦＬ）１７．８部、を混合撹
拌して塗液をつくり、つぎに該塗料を上質紙の表面に乾
燥後の塗布量が７ ｇ／ｒｒｒとなるように塗布乾燥し
、本発明の感熱記録材料を得た。Solution A: Benzyl-4-hydroxyphenylsulfonylacetate 25 parts Polyvinyl alcohol (
10% aqueous solution) 24 parts 1.1.3- ) li (3-t-
Butyl-4-hydroxy-6-methylphenyl)butane 4 parts water
28 parts BY night; 3-(N-isoamyl-N-monoethylamino)-6-methyl-7-anilite fluorane
10 parts polyvinyl alcohol (10% aqueous solution)
15 parts water
15 parts Solution C: Calcium carbonate 23 parts Polyvinyl alcohol (10% aqueous solution) 23 parts Water
14 parts, then 11.5 parts of liquid A, 3.7 parts of liquid E, 9.1 parts of liquid C, and 17.8 parts of polyvinyl alcohol (10% water-soluble? FL) were mixed and stirred to prepare a coating liquid. The coating material was coated on the surface of a high-quality paper so that the coated amount after drying was 7 g/rrr and dried to obtain a heat-sensitive recording material of the present invention.
実施例２
実施例１で用いた１、１．３−トリ （３−ｔ−ブチル
−４−ヒドロキシ−６−メチルフェニル）ブタンの代わ
りに１．１．３−）リ （３−シクロへキシル−４−ヒ
ドロキシル６−メチルフェニル）ブタンを用いた以外は
実施例１と同様にして本発明の感熱記録材料（感熱記録
紙）を得た。Example 2 1,1,3-tri(3-t-butyl-4-hydroxy-6-methylphenyl)butane used in Example 1 was replaced with 1,1,3-)li(3-cyclohexyl). A heat-sensitive recording material (thermal recording paper) of the present invention was obtained in the same manner as in Example 1 except that -4-hydroxyl-6-methylphenyl)butane was used.
実施例３
実施例１で用いた１、Ｌ３−１−リ （３−ｔ−ブチル
−４−ヒドロキシ−６−メチルフェニル）ブタンの代わ
りに１，２−ビス〔３，３−ビス（３−ｔ−ブチル−４
−ヒドロキシフェニル）ブチリルオキシ〕エチレンを用
いた以外は実施例１と同様にして本発明の感熱記録材料
（感熱記録紙）を得た。Example 3 1,2-bis[3,3-bis(3- t-butyl-4
A heat-sensitive recording material (heat-sensitive recording paper) of the present invention was obtained in the same manner as in Example 1 except that -hydroxyphenyl)butyryloxy]ethylene was used.
比較例１
実施例１で用いたＡ液の代わりにＥ液を用いた以外は実
施例１と同様にして比較用感熱記録材料を得た。Comparative Example 1 A comparative heat-sensitive recording material was obtained in the same manner as in Example 1 except that Liquid E was used instead of Liquid A used in Example 1.
Ｅ）′夜；
４−ヒドロキシフェニル−４′−イソ
プロポキシフェニルスルホン ２５部ポリビニ
ルアルコール（１０％水溶液）２４部Ｌｌ、３− ）リ
（３−ｔ−ブチル−４−ヒドロキシ−６−メチルフェ
ニル）ブタン ４部水
２８部比較例２
比較例１で用いた１、１．３−トリ （３−ｔ−ブチル
−４−ヒドロキシ−６−メチルフェニル）ブタンを除い
た以外は比較例１と同様にして比較用感熱記録材料を得
た。E) 'Night;4-Hydroxyphenyl-4'-isopropoxyphenylsulfone 25 parts Polyvinyl alcohol (10% aqueous solution) 24 parts Butane 4 parts water
28 parts Comparative Example 2 A comparative thermosensitive material was prepared in the same manner as in Comparative Example 1 except that the 1,1,3-tri(3-t-butyl-4-hydroxy-6-methylphenyl)butane used in Comparative Example 1 was removed. Obtained recording materials.
比較例３
比較例２で用いた４−ヒドロキシフェニル−４′−イソ
プロボキシフエニルスルホンの代わりにベンジル−４−
ヒドロキシフェニルスルホン酢酸エステル以外は比較例
１と同様にして比較用感熱記録材料を得た。Comparative Example 3 Benzyl-4-
A comparative heat-sensitive recording material was obtained in the same manner as in Comparative Example 1 except for the hydroxyphenylsulfone acetate.
以上各実施例および各比較例で得た感熱記録材料につい
てＭＳＩサーマルヘッド印字装置（投下電子部品−社製
）を用いてライン密度７．７１ｉｎｅ／ｍｉｎ ｓ印字
エネルギー０．８ｍｊで印字したときの濃度で発色感度
を、更に熱傾斜試験機（東洋精機−社製）を用いて１１
０℃、３秒間の条件で発色させた後、４０℃、９０％Ｒ
Ｈで７日間保存した後、また水中で２４時間保存した後
の画像濃度および地肌濃度を各々マクベス濃度計ＲＤ−
１００を用いて測定し、本発明の感熱記録材料の保存性
の評価を行なった。Densities when printed on the thermal recording materials obtained in the above Examples and Comparative Examples using an MSI thermal head printing device (manufactured by Hiroshi Electronic Components Co., Ltd.) at a line density of 7.71 in/min s and a printing energy of 0.8 mj. 11 using a thermal gradient tester (manufactured by Toyo Seiki Co., Ltd.).
After developing color at 0°C for 3 seconds, at 40°C and 90% R.
The image density and background density were measured using a Macbeth densitometer RD-H after being stored for 7 days in water and after being stored in water for 24 hours.
100 to evaluate the storage stability of the heat-sensitive recording material of the present invention.
表から明らかなように、本発明の感熱記録材料は発色感
度が高く、かつ、保存安定性に優れていることが確認さ
れた。As is clear from the table, it was confirmed that the heat-sensitive recording material of the present invention has high color development sensitivity and excellent storage stability.
〈発明の効果〉
本発明は上記の構成よりなるのですぐれた画像濃度を継
続しながら、かつ、十分な発色感度と保存性を得ること
ができる。<Effects of the Invention> Since the present invention has the above-described configuration, it is possible to maintain excellent image density and obtain sufficient color development sensitivity and storage stability.
特許出願人 株式会社巴川製紙所Patent applicant Tomogawa Paper Mills Co., Ltd.
Claims (1)
を熱時発色させる顕色剤を含有する感熱層を設けた感熱
記録材料において、該顕色剤として一般式（１） ▲数式、化学式、表等があります▼（１） （式中Ｚは硫黄原子、−ＳＯ＿２−、Ｒ＾１は低級アル
キル基又は基▲数式、化学式、表等があります▼、Ｒ＾
２は置換されてもよい低級アルキル基、フェニル基、ベ
ンジル基を示し、ここにＲ＾３は水素原子、置換されて
もよい低級アルキル基、ハロゲン原子、ニトリル基、ニ
トロ基又はアルコキシ基を示す）で表わされるフェノー
ル誘導体を使用し、かつ１，１，３−トリ（３−ｔ−ブ
チル−４−ヒドロキシ−６−メチルフェニル）ブタン、
１，１，３−トリ（３−シクロヘキシル−４−ヒドロキ
シ−６−メチルフェニル）ブタンおよび１，２−ビス〔
３，３−ビス（３−ｔ−ブチル−４−ヒドロキシフェニ
ル）ブチリルオキシ〕エチレンのうちの少くとも１つの
化合物を含有させたことを特徴とする感熱記録材料。[Scope of Claims] A heat-sensitive recording material in which a heat-sensitive layer containing a colorless or light-colored leuco dye and a color developer that causes the leuco dye to develop color when heated is provided on a support, wherein the color developer has the general formula ( 1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (In the formula, Z is a sulfur atom, -SO_2-, R^1 is a lower alkyl group or group ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R^
2 represents an optionally substituted lower alkyl group, phenyl group, or benzyl group, where R^3 represents a hydrogen atom, an optionally substituted lower alkyl group, a halogen atom, a nitrile group, a nitro group, or an alkoxy group. ), and 1,1,3-tri(3-t-butyl-4-hydroxy-6-methylphenyl)butane,
1,1,3-tri(3-cyclohexyl-4-hydroxy-6-methylphenyl)butane and 1,2-bis[
1. A heat-sensitive recording material containing at least one compound of 3,3-bis(3-t-butyl-4-hydroxyphenyl)butyryloxy]ethylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63125860A JPH0771873B2 (en) | 1988-05-25 | 1988-05-25 | Thermal recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63125860A JPH0771873B2 (en) | 1988-05-25 | 1988-05-25 | Thermal recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01295887A true JPH01295887A (en) | 1989-11-29 |
| JPH0771873B2 JPH0771873B2 (en) | 1995-08-02 |
Family
ID=14920734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63125860A Expired - Fee Related JPH0771873B2 (en) | 1988-05-25 | 1988-05-25 | Thermal recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0771873B2 (en) |
-
1988
- 1988-05-25 JP JP63125860A patent/JPH0771873B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0771873B2 (en) | 1995-08-02 |
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|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |