JPH01295885A - Heat-sensitive recording material - Google Patents
Heat-sensitive recording materialInfo
- Publication number
- JPH01295885A JPH01295885A JP63125008A JP12500888A JPH01295885A JP H01295885 A JPH01295885 A JP H01295885A JP 63125008 A JP63125008 A JP 63125008A JP 12500888 A JP12500888 A JP 12500888A JP H01295885 A JPH01295885 A JP H01295885A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- color
- sensitive
- layer
- color developing
- 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 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[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
- 150000002989 phenols Chemical class 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 17
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000011247 coating layer Substances 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 4
- 239000003973 paint Substances 0.000 abstract 2
- 238000006467 substitution reaction Methods 0.000 abstract 2
- 229940079593 drug Drugs 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 239000004033 plastic Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 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 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- -1 p-hydroxybenzoic acid ester Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- YTQYLZXXYHMHBP-UHFFFAOYSA-N 4-[(4-methoxyphenyl)methylsulfanyl]phenol Chemical compound C1=CC(OC)=CC=C1CSC1=CC=C(O)C=C1 YTQYLZXXYHMHBP-UHFFFAOYSA-N 0.000 description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical class O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000004927 clay 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
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 150000003457 sulfones Chemical class 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
- 229940090248 4-hydroxybenzoic acid Drugs 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
- 229930185605 Bisphenol Natural products 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
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 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
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 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
- 239000003963 antioxidant agent Substances 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
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 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
- 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
- 239000010419 fine particle Substances 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
- 229910000040 hydrogen fluoride Inorganic materials 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
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 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
- QHDYIMWKSCJTIM-UHFFFAOYSA-N phenyl 1-hydroxynaphthalene-2-carboxylate Chemical compound C1=CC2=CC=CC=C2C(O)=C1C(=O)OC1=CC=CC=C1 QHDYIMWKSCJTIM-UHFFFAOYSA-N 0.000 description 1
- 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
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000008117 stearic acid 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
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil 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
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
速記録適正および耐薬品性にすぐれ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, to suitability for high-speed recording and chemical resistance of a heat-sensitive recording material containing a leuco dye and a color developer that develops color when the dye is heated. This invention relates to a heat-sensitive recording material with excellent properties.
〈従来の技術〉
−ｍ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> - A heat-sensitive recording material in which m is a colorless or light-colored leuco dye and a color developer that causes the leuco dye to develop color when heated is as follows:
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
く高速記録適正がないばかりでなく、耐薬品性等の画像
安定性が悪い問題を有している。また、これらの問題を
解決するために非常に多くの顕色剤が提案されており、
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５６−１４４１９３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６０−１３８５２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６
０−２０８２８６号）等があるが、まだ十分満足し得る
顕色剤は見いだされていない。Conventionally, bisphenol A has been commonly used as a color developer, but bisphenol A has a high melting point of 157°C, making it unsuitable for high-speed recording, and also has problems with poor image stability such as chemical resistance. ing. In addition, a large number of color developers have been proposed to solve these problems.
Practical examples include p-hydroxybenzoic acid ester (JP-A-56-144193), 4-hydroxyphthalic acid diester (JP-A-58-153692),
-Hydroxyphenyl 4-alkoxyphenyl sulfone (JP-A-60-13852) and bis(4-hydroxy-'3-allylphenyl) sulfone (JP-A-60-13852)
No. 0-208286), but a fully satisfactory color developer has not yet been found.
〈発明が解決しようとする問題点〉
本発明は高速記録性および耐薬品性にすぐれた感熱記録
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 material having excellent high-speed recording properties and chemical resistance.
〈問題点を解決するための手段〉
本発明は、支持体上に無色また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、該顕色剤に下記の一般式
（１）によって表わされる化合物を使用したことを特徴
とする感熱記録材料に関するものである。<Means for Solving the 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 for coloring the leuco dye when heated is provided on a support. The present invention relates to a heat-sensitive recording material characterized in that a compound represented by the following general formula (1) is used as a color developer.
一般式（１）
（式中Ｚは硫黄原子、−ＳＯ，−、Ｒは置換えされても
よいＣＩ−Ｃｓの低級アルキル基を示す。ｎは０〜３で
あり、ベンゼン環に複数の置換基ＯＲが結合する場合、
それら置換基ＯＲは同一または異なってもよい）
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) (In the formula, Z is a sulfur atom, -SO, -, R is a lower alkyl group of CI-Cs which may be substituted. n is 0 to 3, and multiple substituents are present on the benzene ring. If the ORs combine,
(These substituents OR may be the same or different.) 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Ａ１ビスフエノール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 A1 bisphenol S, 4-
It can also be used in combination with hydroxybenzoic acid benzyl ester, activated clay, etc.
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、その具体例的な化合
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′−ビスージ
メチルアミノヘンズヒドリンベンジルエーテル、Ｎ−へ
ロフェニルー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−ピペリジノ−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−（０−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. ba, crystal violet lactone, 3
, triarylmethane compounds such as 3-bis(P-dimethylaminophenyl) phthalide, diphenylmethane compounds such as 4,4'-bis-dimethylaminohenzhydrin benzyl ether, N-herophenyl leukoolamine, 3 -diethylamino-7-chlorofluorane,
3-diethylamino-6-methyl-7-chlorofluorane, 3-cyclohexylamino-6-chlorofluorane, 3-diethylamino-7-dibenzylaminofluorane, 3-pyrrolidino-6-methyl-7-anilinoflurane Orane, 3-piperidino-6-methyl-7-anilinofluorane, 3-cyclohexylmethylamino-6-methyl-7-anilinofluorane, 3-ethylisoamylamino-6-methyl-7-anilinofluorane , 3-diethylamino-7-(0-chloroanilino)fluoran, 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、本発明の感熱記録材料を構成する感熱層には、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
増感剤、充填剤が適宜使用せられる。Further, in the heat-sensitive layer constituting the heat-sensitive recording material of the present invention, a binder, a sensitizer, 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を構成する
感熱層上の被膜層、あるいは支持体の裏面に設けるバッ
ク層としては、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、ポビニルビロ
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、アルいは、酢酸ビニル、アクリル酸エステル、塩
化ビニル−酢酸ビニル共重合体、ＳＢＲ。As the binder for the heat-sensitive layer, the coating layer on the heat-sensitive layer constituting the heat-sensitive recording material of the present invention, or the back layer provided on the back surface of the support, examples include casein, gelatin, polyvinyl alcohol, modified polyvinyl alcohol, and povinyl. pyrrolidone, starch, isobutylene-maleic anhydride resin,
Styrene-maleic anhydride resin, polyacrylamide,
Carboxymethyl cellulose, hydroxyethyl cellulose, vinyl acetate, acrylic ester, vinyl chloride-vinyl acetate copolymer, SBR.
ＮＢＲ等のエマルジョン、ラテックスなどが用いられる
。Emulsions such as NBR, latex, 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、スタア
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 naphthoate, 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。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.
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。更に必要に応じて、該感熱層上に被膜
層を設けることもでき、又、該感熱記録材料において該
支持体の裏面にバック層並びに感圧接着層を順次設けて
、これに剥離紙を貼付することも出来る。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または被膜層に含有させること
も出来る。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. Furthermore, if necessary, a coating layer may be provided on the heat-sensitive layer, and a back layer and a pressure-sensitive adhesive layer may be sequentially provided on the back surface of the support in the heat-sensitive recording material, and a release paper is attached to this. You can also do that. For the purpose of improving light resistance, antioxidants, ultraviolet absorbers, energy quenchers, etc. can also be included in the heat-sensitive layer or coating layer of the present invention.
〈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.
なお配合部数は全て重量部を示すものとする。It should be noted that all blended parts 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］液
を調製した。Example 1 A mixture having the following composition was separately ground and dispersed using a dyno mill to prepare liquids [A], [B], and [C].
Ａ液；
４−メトキシベンジル ４−ヒドロキシフェニル スル
フィド ２５部ポリビニルアルコール（
１０％水溶液）２４部水
２８部Ｂ液；
３−（Ｎ−イソアミル−Ｎ−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）１
５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部り液；
水酸化アルミニウム ４０部ポリビニ
ルアルコール（１０％水溶液）４０部水
２０部ついでＡ液１
１．５部、Ｂ液３．７部、Ｃ液９．１部、ポリビニルア
ルコール（１０％水溶液）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 ／ ｍとなるように塗布乾燥し、感熱
層を得た。更にポリビニルアルコール（１０％水溶液）
４０部、Ｄ液１４部を混合して、上記感熱層上に乾燥後
の塗布量が４ｇ／ｒｒｒの被膜層を形成し、本発明の感
熱記録材料を得た。Solution A; 4-methoxybenzyl 4-hydroxyphenyl sulfide 25 parts polyvinyl alcohol (
10% aqueous solution) 24 parts water
28 parts Solution B; 3-(N-isoamyl-N-ethylamino)-6-methyl-7-anilite fluorane
10 parts polyvinyl alcohol (10% aqueous solution) 1
5 parts water
15 parts Solution C: Calcium carbonate 23 parts Polyvinyl alcohol (10% aqueous solution) 23 parts Water
14 parts liquid; aluminum hydroxide 40 parts polyvinyl alcohol (10% aqueous solution) 40 parts water
20 parts followed by 1 part of liquid A
1.5 parts of liquid B, 3.7 parts of liquid C, and 17.8 parts of polyvinyl alcohol (10% aqueous solution) were mixed and stirred to prepare a coating liquid. The coating was coated and dried so that the coating weight after drying was 7 g/m to obtain a heat-sensitive layer. Furthermore, polyvinyl alcohol (10% aqueous solution)
40 parts of liquid D and 14 parts of liquid D were mixed to form a coating layer on the heat-sensitive layer with a coating amount of 4 g/rrr after drying to obtain a heat-sensitive recording material of the present invention.
実施例２
実施例１で用いた４−メトキシベンジル ４−ヒドロキ
シフェニル スルフィドの代ワリに４−メトキシベンジ
ル ４−ヒドロキシフェニル スルホンを用いた以外は
実施例１と同様にして本発明の感熱記録材料を得た。Example 2 The heat-sensitive recording material of the present invention was produced in the same manner as in Example 1 except that 4-methoxybenzyl 4-hydroxyphenyl sulfone was used in place of the 4-methoxybenzyl 4-hydroxyphenyl sulfide used in Example 1. Obtained.
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シートを得た。Comparative Example 1 A comparative heat-sensitive recording sheet 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液；
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ｍｔ＆＞ ２４ 部水
２８部比較
例２
比較例１で用いた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の代わりにビス（４−ヒドロ
キシ−３−アリルフェニル）スルホンを用いた以外は比
較例１と同様にして比較用感熱記録シートを得た。Solution E; 4-hydroxyphenyl 4'-isopropoxyphenylsulfone 25 parts polyvinyl alcohol (10% water mt &> 24 parts water
28 parts Comparative Example 2 Comparison was made in the same manner as Comparative Example 1 except that bis(4-hydroxy-3-allylphenyl) sulfone was used instead of 4-hydroxyphenyl 4'-isopropoxyphenylsulfone used in Comparative Example 1. A heat-sensitive recording sheet for use was obtained.
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 ％印字
エネルギー１．２ ｍｊ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１
４０℃、３秒間の条件で発色させた時の発色濃度と、植
物油を添加して２４時間放置した場合（耐油性テスト）
と水に水没させて２４時間放置した場合（耐水性テスト
）の発色部の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評価を行なった
。その結果を表に示す。The thermal recording materials obtained in the above examples and comparative examples were printed at a line density of 7.71 in/min and a % printing energy of 1.2 mj using an MSI thermal head printing device (manufactured by Jyoden Electronics Co., Ltd.). Color development sensitivity is determined by density, and then 1 using a thermal gradient tester (manufactured by Toyo Seiki Co., Ltd.)
Color density when developing at 40℃ for 3 seconds and when vegetable oil is added and left for 24 hours (oil resistance test)
The heat-sensitive recording material of the present invention was evaluated by measuring the density of the colored portion when submerged in water and left for 24 hours (water resistance test) using a Macbeth densitometer RD-100. The results are shown in the table.
表から明らかなように、本発明の感熱記録材料は発色感
度および耐薬品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 excellent color development sensitivity and chemical resistance.
〈発明の効果〉
本発明の感熱記録材料は上記の構成よりなるので、十分
な発色濃度を維持しながら、すぐれた発色感度と耐薬品
性を得ることができる。<Effects of the Invention> Since the heat-sensitive recording material of the present invention has the above-described structure, it is possible to obtain excellent color development sensitivity and chemical resistance while maintaining sufficient color density.
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、該顕色剤に一般式（１）で表わされ
るフェノール誘導体を使用したことを特徴とする感熱記
録材料。 ▲数式、化学式、表等があります▼（１） （式中Ｚは硫黄原子、−ＳＯ＿２−、Ｒは置換されても
よいＣ＿１〜Ｃ＿５の低級アルキル基を示す。ｎは０〜
３であり、ベンゼン環に複数の置換基ＯＲが結合する場
合、それら置換基ＯＲは同一又は異なってもよい）[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, the color developer having a general formula ( A heat-sensitive recording material characterized by using a phenol derivative represented by 1). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (In the formula, Z is a sulfur atom, -SO_2-, R is a lower alkyl group of C_1 to C_5 which may be substituted. n is 0 to
3, and when multiple substituents OR are bonded to the benzene ring, these substituents OR may be the same or different)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63125008A JPH0780360B2 (en) | 1988-05-24 | 1988-05-24 | Thermal recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63125008A JPH0780360B2 (en) | 1988-05-24 | 1988-05-24 | Thermal recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01295885A true JPH01295885A (en) | 1989-11-29 |
| JPH0780360B2 JPH0780360B2 (en) | 1995-08-30 |
Family
ID=14899583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63125008A Expired - Fee Related JPH0780360B2 (en) | 1988-05-24 | 1988-05-24 | Thermal recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0780360B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0559525A2 (en) * | 1992-02-28 | 1993-09-08 | Tomoegawa Paper Co. Ltd. | Thermal printing medium and method for preparing the same |
| US5840991A (en) * | 1997-01-22 | 1998-11-24 | Development Center For Biotechnology | Antiatherosclerosis agents for lipid-lowering and antiperoxidative activity |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6442280A (en) * | 1987-08-11 | 1989-02-14 | Ricoh Kk | Thermal recording material |
-
1988
- 1988-05-24 JP JP63125008A patent/JPH0780360B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6442280A (en) * | 1987-08-11 | 1989-02-14 | Ricoh Kk | Thermal recording material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0559525A2 (en) * | 1992-02-28 | 1993-09-08 | Tomoegawa Paper Co. Ltd. | Thermal printing medium and method for preparing the same |
| EP0559525A3 (en) * | 1992-02-28 | 1995-01-18 | Tomoegawa Paper Co Ltd | |
| US5840991A (en) * | 1997-01-22 | 1998-11-24 | Development Center For Biotechnology | Antiatherosclerosis agents for lipid-lowering and antiperoxidative activity |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0780360B2 (en) | 1995-08-30 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |