JPS62261479A - Thermal recording material - Google Patents
Thermal recording materialInfo
- Publication number
- JPS62261479A JPS62261479A JP61103771A JP10377186A JPS62261479A JP S62261479 A JPS62261479 A JP S62261479A JP 61103771 A JP61103771 A JP 61103771A JP 10377186 A JP10377186 A JP 10377186A JP S62261479 A JPS62261479 A JP S62261479A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- color
- formula
- heat
- 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 26
- 239000000126 substance Substances 0.000 claims abstract description 14
- 150000004650 carbonic acid diesters Chemical class 0.000 claims abstract description 7
- 150000002989 phenols Chemical class 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 239000003086 colorant Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 20
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical class C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 abstract description 13
- 230000035945 sensitivity Effects 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- -1 fluoran compound Chemical class 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000004014 plasticizer Substances 0.000 description 8
- LNTHITQWFMADLM-UHFFFAOYSA-N anhydrous gallic acid Natural products OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000004040 coloring Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- RPWFJAMTCNSJKK-UHFFFAOYSA-N Dodecyl gallate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 RPWFJAMTCNSJKK-UHFFFAOYSA-N 0.000 description 4
- 235000010386 dodecyl gallate Nutrition 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229940074391 gallic acid Drugs 0.000 description 3
- 235000004515 gallic acid Nutrition 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 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
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 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
- YBMTWYWCLVMFFD-UHFFFAOYSA-N 3-methylbutyl 3,4,5-trihydroxybenzoate Chemical compound CC(C)CCOC(=O)C1=CC(O)=C(O)C(O)=C1 YBMTWYWCLVMFFD-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 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
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate 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
- 239000008139 complexing agent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 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
- 125000000268 heptanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 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
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- BRNPAEUKZMBRLQ-UHFFFAOYSA-N octadecyl 3,4,5-trihydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 BRNPAEUKZMBRLQ-UHFFFAOYSA-N 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GJYCVCVHRSWLNY-UHFFFAOYSA-N ortho-butylphenol Natural products CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 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
-
- 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
- B41M5/323—Organic colour formers, e.g. leuco dyes
- B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
- B41M5/3275—Fluoran compounds
-
- 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
- B41M5/337—Additives; Binders
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、更に詳しく述べるなら
ば、改良された保存性を有し、高速記録特性にも優れた
感熱記録材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a heat-sensitive recording material, and more specifically, to a heat-sensitive recording material that has improved storage stability and excellent high-speed recording characteristics.
シート状支持体に、ロイコ染料と該ロイコ染料を加熱時
にこれと反応して発色させる顔色剤とを含むロイコ系感
熱記録材料はよく知られている。Leuco heat-sensitive recording materials containing a leuco dye and a complexing agent that reacts with the leuco dye to develop color when heated are well known.
感熱記録材料に要求される基本的性能としては、十分な
発色画像濃度および感度をもつこと、経時による発色画
像濃度の劣化がないことなどがある。The basic performances required of a heat-sensitive recording material include sufficient color image density and sensitivity, and no deterioration of color image density over time.
近年、印字記録の高速化が進められ、記録装置自体の高
速化とともに、それに対応できる記録シートの開発、即
ち記録シートの高感度化が望まれている。さらに、感熱
記録材料が広く用いられるようになるとともに、整髪料
や皮膚の汗に含まれる油脂類などの付着に対する画像の
安定性（画像の耐油性〕、塩ビラツブ等に含まれる可塑
剤の付着に対する画像の安定性（耐可塑剤性〕、水が付
着した時の画像の安定性（耐水性）等の徨々の特性が要
求されるようになシ、これらを十分に満足するような感
熱材料が望まれるようになってきた。BACKGROUND ART In recent years, the speed of printing and recording has been increasing, and as well as increasing the speed of the recording apparatus itself, it is desired to develop a recording sheet that can cope with the speed increase, that is, to increase the sensitivity of the recording sheet. Furthermore, as heat-sensitive recording materials became widely used, the stability of images against the adhesion of oils and fats contained in hair products and sweat on the skin (image oil resistance), and the adhesion of plasticizers contained in PVC etc. Increasingly, various characteristics are required, such as image stability when exposed to water (plasticizer resistance) and image stability when exposed to water (water resistance). materials are becoming more desirable.
ところで、従来の感熱記録材料では、感熱発色層の上に
保護層として水溶性高分子層を設けて、前記保存性を向
上せしめている。しかしながら、このような感熱記録材
料の場合には、可塑剤等に対しての保存性は改良される
ものの、保護層を形成したことにより熱応答性に劣ると
いう欠点が生じる。そのため、ロイコ染料と顕色剤との
組合せに熱可融性物質（増感剤）を併用することＫより
記録感度を向上させる提案が数多くなされている。By the way, in conventional heat-sensitive recording materials, a water-soluble polymer layer is provided as a protective layer on the heat-sensitive coloring layer to improve the storage stability. However, in the case of such a heat-sensitive recording material, although the storage stability against plasticizers and the like is improved, the formation of the protective layer causes a drawback of poor thermal responsiveness. Therefore, many proposals have been made to improve recording sensitivity by using a thermofusible substance (sensitizer) in combination with a leuco dye and a color developer.
しかし、すべての要求性能を満足すべき感熱記録材料は
未だに得られていない。However, a heat-sensitive recording material that satisfies all required performances has not yet been obtained.
〔発明が解決しようとする問題点〕
本発明者らは、このような問題点を解決すべく鋭意検討
を重ねた結果、特定のフルオラン化合物からなる発色剤
と、顕色剤として没食子酸アルキルエステルまたはノ々
う置換フェノールおよび熱可融性物質として炭酸ジエス
テルとを組合せて、感熱発色層に含有させることによシ
、発色感度が向上し、保存性に優れた、保護層を必要と
しない感熱記録材料が得られることを見出し、本発明を
完了するに至ったものである。[Problems to be Solved by the Invention] As a result of intensive studies to solve these problems, the present inventors have developed a color former made of a specific fluoran compound and a gallic acid alkyl ester as a color developer. Alternatively, by combining Nonou-substituted phenol and a carbonic acid diester as a heat-fusible substance and incorporating it into the heat-sensitive coloring layer, the coloring sensitivity is improved and the heat-sensitive material has excellent storage stability and does not require a protective layer. It was discovered that a recording material could be obtained, and the present invention was completed.
〔問題点を解決するための手段〕 。[Means for solving problems].
本発明によれば、即ち、発色剤として下記一般式１１
〔上式中、Ｒ４はメチル基ま九はエチル基を表す〕で示
されるフルオラン誘導体、顕色剤として下記一般式■ま
たは■、
〔上式中、Ｒ２はＣ１〜Ｃ４８のアルキル基を表し、Ｒ
３はＣ３〜Ｃ６のアルキル基またはフェニル基を表す〕
で示されるフェノール性化合物、および増感剤として下
記一般式■、
〔上式中、Ｒ４は水素、Ｃ４〜Ｃ５のアルキル基、メト
キシ基またはエトキシ基を表す〕
で示される炭酸ジエステルを含む感熱記録材料が提供さ
れる。According to the present invention, a fluoran derivative represented by the following general formula 11 [in the above formula, R4 is a methyl group and 9 represents an ethyl group] is used as a color former, and a fluoran derivative represented by the following general formula 1 or 2 is used as a color developer. In the above formula, R2 represents a C1 to C48 alkyl group, and R
3 represents a C3-C6 alkyl group or a phenyl group] A phenolic compound represented by the following general formula (1) and a sensitizer, [wherein R4 is hydrogen, a C4-C5 alkyl group, a methoxy group, or Representing an ethoxy group] A heat-sensitive recording material containing a carbonic acid diester represented by the following is provided.
本発明で用いる顕色剤は、一般式■および■で示される
フェノール性化合物であるが、このものは、前記フルオ
ラン誘導体１重量部に対し１〜５重景部、好ましくは２
〜３重量部の割合で用いられるのが望ましい。また、こ
れらの７工ノール性化合物は、単独でまたは２種以上を
混合して用いることができるだけでなく、公知の他の顕
色剤と併用して用いることもできる。The color developer used in the present invention is a phenolic compound represented by the general formulas (1) and (2).
It is desirable to use it in a proportion of ~3 parts by weight. Moreover, these heptanoyl compounds can be used not only alone or in a mixture of two or more types, but also in combination with other known color developers.
さらに、熱可融性物質（増感剤）は一般式■で示される
炭酸ジエステルであるが、前記フルオラン誘導体１重量
部に対して１〜５重量部、好ましくは３〜５重量部の割
合で用いられるのが望ましい。Further, the thermofusible substance (sensitizer) is a carbonic acid diester represented by the general formula (1), and is used in an amount of 1 to 5 parts by weight, preferably 3 to 5 parts by weight, per 1 part by weight of the fluoran derivative. It is desirable that it be used.
本発明に係る感熱記録材料は、フルオラン系発色剤、顕
色剤および熱可融性物質、並びに所望によシ結合剤など
を含むものであるが、次にこれらのＥ分についてさらに
具体的に説明する。The heat-sensitive recording material according to the present invention contains a fluoran color former, a color developer, a thermofusible substance, and an optional binder, and the E component will be explained in more detail next. .
（１）フルオラン系発色剤 一般式１で示される化合物の具体例としては、以下余白 が挙げられる。(1) Fluorane color former Specific examples of the compound represented by general formula 1 are as follows: can be mentioned.
（２）顕色剤
一般式■および■で示される化合物の具体例としては、
Ｈｏ（没食子酸、−プ、刈 融点、４４゜Ｏ
ＣＩ
（没食子酸イソアミル） 融点１４２℃ＨＯ（没食子酸
ステア１ノル）ｌ＠点１（Ｊ４Ｌ；（ｐ−ｔ−アミル７
ｄ−ル） 融点 ９４℃などが挙げられる。(2) Color developer Specific examples of compounds represented by the general formulas ■ and ■ include: Ho (gallic acid, -p, crystallization point, 44°C CI (isoamyl gallate), melting point 142°C HO (gallic acid stear 1), nor) l @ point 1 (J4L; (p-t-amyl 7
d-R) Melting point: 94°C.
（３） 熱可融性物質
一般式■で示される化合物の具体例としては、す
（ノフェ二ルカーデネート） 融点 ８０℃υ
（４，４’−ジメトキシフェニルカーゴネート） 融点
９５℃す
（４，４’−ジメトキシフェニルカーゴネート） 融
点 ８３℃（４，４’−ツメチルフェニルカーゴネート
〕 融点１１４℃Ｈ３
（２，２’ −ツメチルフェニルカーゴネート） 融点
５７℃などが挙げられる。(3) Thermofusible substances Specific examples of compounds represented by the general formula (■) include Su(nophenyl cardenate) Melting point: 80℃υ (4,4'-dimethoxyphenyl carbonate) Melting point: 95℃su(4,4'-dimethoxyphenyl carbonate) '-Dimethoxyphenylcargonate) Melting point: 83°C (4,4'-tsumethylphenylcargonate) Melting point: 114°C H3 (2,2'-tsumethylphenylcargonate) Melting point: 57°C.
７本発明の感熱記録材料には、所望によフ、いかなる結
着剤を含有させてもよく、有用な結着剤の典型的な例と
しては、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、
ポリアクリルアミド、スチレン−無水マレイン酸５共重
合体塩、スチレン−ブタジェン共３１合体エマルジ璽ン
ナトがあり、これらは通常全固形分の５〜４０重量％、
好ましくは１５〜３０重量−の量で用いられる。7. The heat-sensitive recording material of the present invention may contain any binder if desired, and typical examples of useful binders include starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, gum arabic, polyvinyl alcohol,
There are polyacrylamide, styrene-maleic anhydride 5 copolymer salt, styrene-butadiene co-31 emulsion binder, and these usually have a total solid content of 5 to 40% by weight,
Preferably it is used in an amount of 15 to 30% by weight.
また、記録ヘッドのカス付着防止性を改善し、かつ感熱
記録材料層をさらに白くするためにカオリン、クレー、
メルク、炭酸カルシウム、焼成りレー、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。In addition, in order to improve the property of preventing the adhesion of residue on the recording head and to further whiten the heat-sensitive recording material layer, kaolin, clay, etc.
Inorganic pigments such as Merck, calcium carbonate, calcined clay, titanium oxide, diatomaceous earth, particulate anhydrous silica, and activated clay can also be added.
また、適宜、ステアリン酸亜鉛、ステアリン酸カルシウ
ムなどの分散液を記録ヘッドとの接触に際し、記録材料
層がヌティッキングを生じないように添加することもで
きる。Furthermore, a dispersion of zinc stearate, calcium stearate, or the like may be added as appropriate to prevent the recording material layer from causing nuticking when it comes into contact with the recording head.
前記の各種感熱発色層形成成分を用いて本発明の感熱記
録材料を得るためには、通常知られている方法を用いる
ことができる。即ち、フルオラン系発色剤、顕色剤、熱
可融性物質、充填剤、その他の添加剤を結着剤とともに
、それぞれ別々にまたはフルオラン系発色剤以外はそれ
ぞれ混合して、ポバール水溶液等とともに、水媒体中に
加え、ゴールミル、アトライター等の分散機にて粉砕、
分散させ、塗液として調製される。Generally known methods can be used to obtain the heat-sensitive recording material of the present invention using the various heat-sensitive coloring layer forming components described above. That is, a fluoran color former, a color developer, a thermofusible substance, a filler, and other additives are mixed together with a binder, either separately or except for the fluoran color former, together with a poval aqueous solution, etc. Add it to an aqueous medium and grind it with a dispersing machine such as a Goal Mill or Attritor.
It is dispersed and prepared as a coating liquid.
次に、各分散液を混合して感熱発色層塗液を調製し、こ
れを公知の技術に従って紙などの支持体に塗布し、乾燥
することによって、感熱記録材料が得られる。Next, the respective dispersions are mixed to prepare a heat-sensitive color forming layer coating solution, which is coated on a support such as paper according to a known technique and dried to obtain a heat-sensitive recording material.
本発明の感熱記録材料は、発色感度（記録感度〕が優れ
るとともに、保存性に優れた発色画像を与えることがで
き、従って保護層を設ける必要もない。本発明の記録材
料が記録感度に優れる理由については完全には明らかで
はないけれども、前述の如き特定の熱可融性物質の化学
構造がこの熱可融性物質とともに用いられる発色剤や顕
色剤の化学構造と類似しており、結果として混合系全体
の相容性が高められることが一つの要因として考えられ
る。また、一般式■および■で表わされるフェノール性
化合物は、本発明における前記の如き特定の熱可融性物
質との組合せにおいて、とりわけ優れた記録感度特性を
示すため、よシ好ましく用いられるのである。The heat-sensitive recording material of the present invention has excellent color development sensitivity (recording sensitivity) and can provide a colored image with excellent storage stability, so there is no need to provide a protective layer.The recording material of the present invention has excellent recording sensitivity. Although the reason is not completely clear, the chemical structure of certain thermofusible materials as mentioned above is similar to the chemical structure of color formers and color developers used with these thermofusible materials; One of the factors is considered to be that the compatibility of the entire mixed system is increased.Furthermore, the phenolic compounds represented by the general formulas In combination, they exhibit particularly excellent recording sensitivity characteristics, so they are preferably used.
さらに、一般式ｌで衣わされるフルオラン誘導体は、比
較的分子量が大きく、そのため可塑剤等の有機溶剤に対
する溶解度が従来のフルオラン染料に比べて低いことか
ら、耐可塑剤性等の堅牢性が向上するものと推測される
。Furthermore, the fluoran derivative coated with the general formula l has a relatively large molecular weight, and therefore has a lower solubility in organic solvents such as plasticizers than conventional fluoran dyes, resulting in poor fastness such as plasticizer resistance. It is assumed that this will improve.
以下に実施例を示し、本発明をより具体的に説明するが
、勿論本発明はこれらに限定されるものではない。EXAMPLES The present invention will be described in more detail with reference to Examples below, but the present invention is of course not limited to these.
〔実施例１〕
〔分散液Ａ〕
構造式Ａのフルオラン誘導体 ２５重量部１５％
ポリビニルアルコール水溶液 ３０重量部水
４５重量部〔分散液Ｂ
〕
没食子酸ラクリル ２５重量部１５チ
ポリビニルアルコール水溶液 ３０重量部水
４５重量部〔分散液Ｃ
〕
ジフェニルカーがネート ２５重量部１５
Ｌｓポリビニルアルコール水溶液 ３０重量部
水 ４５重量部これ
らの組成物をそれぞれペイントコンディジ１ナーを用い
て２４時間粉砕、分散させて、分散液Ａ％ＢおよびＣを
調製した。次いでＡ液１０重量部、Ｂ液２５重量部およ
びＣ液３０Ｔｉｆ（部と、５０チ炭酸力ルシウム分散液
３０′ｔＬ量部および１５％ポリビニルアルコール水溶
液５重量部とを混合攪拌し、塗液とした。[Example 1] [Dispersion A] Fluoran derivative of structural formula A 25 parts by weight 15%
Polyvinyl alcohol aqueous solution 30 parts by weight water
45 parts by weight [Dispersion B
] Lacryl gallate 25 parts by weight 15 parts by weight Polyvinyl alcohol aqueous solution 30 parts by weight Water
45 parts by weight [Dispersion C
] Diphenyl carnate 25 parts by weight 15
Ls polyvinyl alcohol aqueous solution: 30 parts by weight Water: 45 parts by weight Each of these compositions was ground and dispersed for 24 hours using a paint conditioner to prepare dispersions A%B and C. Next, 10 parts by weight of liquid A, 25 parts by weight of liquid B, and 30 parts of liquid C were mixed and stirred with 30'tL parts of 50% lucium carbonate dispersion and 5 parts by weight of 15% polyvinyl alcohol aqueous solution to form a coating liquid. did.
得られた塗液を５０５１７ｍ”の原紙にワイヤーパーを
用いて乾燥後の塗布量が１０Ｐ／−となるように塗布し
て乾燥し、ギヤレンダー処理を行い、感熱記録紙を作成
した。The obtained coating liquid was applied onto a 50517 m'' base paper using a wire parser so that the coated amount after drying was 10 P/-, dried, and subjected to gear rendering treatment to prepare a heat-sensitive recording paper.
〔実施例２〕
〔分散液Ｄ〕
４．４′−ジーｔ−プチルフエ二ルカーデネート ２
５重ｆｔ部１５％ポリビニルアルコール水溶液
３０重量部水
４５重量部分散液Ｅを実施例１と同様に調製し
、実施例１と同じＡ液１０重量部およびＢ液２５重量部
と上記Ｈ液３０重量部を用い、その他は実施例１と同様
にして感熱記録紙を作成した。[Example 2] [Dispersion D] 4.4'-di-t-butyl phenyl carbonate 2
5-fold ft part 15% polyvinyl alcohol aqueous solution
30 parts by weight water
A 45 parts by weight dispersion E was prepared in the same manner as in Example 1, using the same 10 parts by weight of liquid A and 25 parts by weight of liquid B as in Example 1, and 30 parts by weight of the above liquid H, and otherwise in the same manner as in Example 1. A thermosensitive recording paper was created.
〔実施例３〕
実施例１の分散液Ｂの没食子酸ラウリルの代わシに没食
子酸グロビ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。[Example 3] A thermosensitive recording paper was obtained in the same manner as in Example 1 except that globil gallate was used in place of lauryl gallate in dispersion B of Example 1.
〔実施例４〕
〔分散液Ｅ〕
構造式Ｂのフルオラン誘導体 ２５重量部１５チ
ポリビニルアルコール水溶液 ３０重量部水
４５重量部〔分散
液Ｆ〕
没食子酸ステアリル ２５重量部１５％ポ
リビニルアルコール水溶液 ３０重葉部水
４５重量部〔分散液Ｇ
〕
４．４′−ジェトキシフェニルカー−ネート ２５重
量部１５饅ポリビニルアルコール水溶液 ３０重
量部水 ４５７を
置部分散液Ｅ、ＦおよびＧを実施例１と同様に調製し、
Ｈ液１０重量部、Ｈ液２５重量部およびＧ液３０重量部
を用い、その他は実施例１と同様にして感熱記録紙を作
成した。[Example 4] [Dispersion E] Fluoran derivative of structural formula B 25 parts by weight 15 parts polyvinyl alcohol aqueous solution 30 parts by weight Water
45 parts by weight [Dispersion F] Stearyl gallate 25 parts by weight 15% polyvinyl alcohol aqueous solution 30 parts by weight Water
45 parts by weight [Dispersion liquid G
4. Dispersions E, F and G were prepared in the same manner as in Example 1 by adding 25 parts by weight of 4'-jethoxyphenyl carnate, 30 parts by weight of aqueous polyvinyl alcohol solution, and dispersion E, F and G.
A thermosensitive recording paper was prepared in the same manner as in Example 1 except that 10 parts by weight of liquid H, 25 parts by weight of liquid H and 30 parts by weight of liquid G were used.
〔実施例５〕
実施例１の分散液Ｂの没食子酸ラウリルの代わシにｐ−
フェニルフェ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。[Example 5] In place of lauryl gallate in dispersion B of Example 1, p-
A thermosensitive recording paper was obtained in the same manner as in Example 1 except that phenylphenol was used.
〔実施例６〕
〔分散液Ｈ〕
没食子酸ラウリル １０重量部ｐ−ｔ−
ブチルフェノール １５重量部１５チポリ
ビニルアルコール水溶液 ３０重置部水
４５重量部分散液Ｈを実
施例１と同様にして調製し、実施例１と同じＡ液１０重
量部、上記Ｈ液２５重量部および実施例１と同じＣ液３
０重量部を用い、その他は実施例１と同様にして感熱記
録紙を作成した。[Example 6] [Dispersion H] Lauryl gallate 10 parts by weight pt-
Butylphenol 15 parts by weight 15 parts Polyvinyl alcohol aqueous solution 30 parts by weight Water
A 45 parts by weight dispersion H was prepared in the same manner as in Example 1, containing 10 parts by weight of the same liquid A as in Example 1, 25 parts by weight of the above liquid H and 3 parts by weight of the liquid C as in Example 1.
A thermosensitive recording paper was prepared in the same manner as in Example 1 except that 0 parts by weight was used.
〔比較例１〕
実施例１において分散液Ｃのジフェニルカーゴネートを
除いた以外は、実施例１と同様にして感熱記録紙を作成
した。[Comparative Example 1] A thermosensitive recording paper was prepared in the same manner as in Example 1 except that diphenyl cargoonate in the dispersion liquid C in Example 1 was omitted.
〔比較例２〕
実施例１の分散液Ｂの没食子酸ラウリルの代わりにビス
フェノールＡを使用した以外は実施例２と同様にして感
熱記録紙を作成した。[Comparative Example 2] A thermosensitive recording paper was prepared in the same manner as in Example 2 except that bisphenol A was used instead of lauryl gallate in Dispersion B of Example 1.
このようにして得られた８糎類の感熱記録紙について、
熱傾斜試験器を用い、１００℃の温度で、１ ｋｇ／ｃ
ｒＩＰの圧力を０．２秒間加え、得られた黒発色の画像
をマクベス濃度計によシ測定した。また、これらの８種
類の感熱記録紙について、熱傾斜試験器を用い、１１８
℃の温度で発色させたサンプルの表面を、可塑剤を含有
する食品包装用軟質塩ビラツブフィルムで被覆し、４０
℃の環境下で２５０２．４−の加重を付加し、２０時間
後の発色画像の消色を目視で評価した。Regarding the 8 types of thermosensitive recording paper obtained in this way,
1 kg/c at a temperature of 100°C using a thermal gradient tester
rIP pressure was applied for 0.2 seconds, and the resulting black colored image was measured using a Macbeth densitometer. In addition, for these eight types of thermal recording paper, using a thermal gradient tester, 118
The surface of the sample developed at a temperature of 40°C was coated with a soft PVC film for food packaging containing a plasticizer, and
A weight of 2502.4- was applied in an environment of 0.degree. C., and the decolorization of the colored image after 20 hours was visually evaluated.
また、発色させたサングルの表面に綿実油を塗布し、４
０℃で２０時間放置後の発色画像の消色を目視で評価し
た。得られた結果を次の表に示す。In addition, cottonseed oil was applied to the surface of the colored sangur, and 4
Discoloration of the colored image after being left at 0° C. for 20 hours was visually evaluated. The results obtained are shown in the following table.
〔注〕耐可塑剤性、耐油性 ○：発色部の消色がなく、非常に良好。[Note] Plasticizer resistance, oil resistance ○: Very good quality with no discoloration in the colored area.
Δ：発色部が若干消色するが、実用上問題なし。Δ: The colored part is slightly discolored, but there is no problem in practical use.
×＝発色部がほとんど消色してしまい、実用上問題あり
。× = Most of the coloring part has faded, causing a practical problem.
本発明によれば、発色部分の可塑剤や油などに対する堅
牢性に極めて優れた発色画像を与えることができ、かつ
、発色感度も良好な感熱記録材料を提供することができ
る。According to the present invention, it is possible to provide a heat-sensitive recording material that can provide a colored image with extremely excellent fastness to plasticizers, oils, etc. in the colored portion, and also has good coloring sensitivity.
Claims (1)
示されるフルオラン誘導体、顕色剤として下記一般式I
IまたはIII、 ▲数式、化学式、表等があります▼（II） ▲数式、化学式、表等があります▼（III） 〔上式中、Ｒ＿２はＣ＿１〜Ｃ＿１＿８のアルキル基を
表し、Ｒ＿３はＣ＿３〜Ｃ＿６のアルキル基またはフェ
ニル基を表す〕 で示されるフェノール性化合物、および増感剤として下
記一般式IV、 ▲数式、化学式、表等があります▼（IV） 〔上式中、Ｒ＿４は水素、Ｃ＿１〜Ｃ＿５のアルキル基
、メトキシ基またはエトキシ基を表す〕 で示される炭酸ジエステルを含む感熱記録材料。[Claims] 1. A fluorane derivative represented by the following general formula I as a coloring agent, ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the above formula, R_1 represents a methyl group or an ethyl group]; As a color developer, the following general formula I
I or III, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) [In the above formula, R_2 represents an alkyl group of C_1 to C_1_8, and R_3 represents a C_3 to C_6 represents an alkyl group or a phenyl group] The following general formula IV, ▲mathematical formula, chemical formula, table, etc. are available as a phenolic compound represented by and a sensitizer▼(IV) [In the above formula, R_4 is hydrogen, C_1 ~C_5 represents an alkyl group, a methoxy group, or an ethoxy group] A heat-sensitive recording material containing a carbonic acid diester represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61103771A JPH0662012B2 (en) | 1986-05-08 | 1986-05-08 | Thermal recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61103771A JPH0662012B2 (en) | 1986-05-08 | 1986-05-08 | Thermal recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62261479A true JPS62261479A (en) | 1987-11-13 |
| JPH0662012B2 JPH0662012B2 (en) | 1994-08-17 |
Family
ID=14362719
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61103771A Expired - Lifetime JPH0662012B2 (en) | 1986-05-08 | 1986-05-08 | Thermal recording material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0662012B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH058548A (en) * | 1991-05-01 | 1993-01-19 | Tomoegawa Paper Co Ltd | Thermal recording medium |
| US11084308B2 (en) | 2015-11-11 | 2021-08-10 | Papierfabrik August Koehler Se | Heat-sensitive recording material |
-
1986
- 1986-05-08 JP JP61103771A patent/JPH0662012B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH058548A (en) * | 1991-05-01 | 1993-01-19 | Tomoegawa Paper Co Ltd | Thermal recording medium |
| US11084308B2 (en) | 2015-11-11 | 2021-08-10 | Papierfabrik August Koehler Se | Heat-sensitive recording material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0662012B2 (en) | 1994-08-17 |
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