JPH01206091A - Thermosensitive recording material - Google Patents
Thermosensitive recording materialInfo
- Publication number
- JPH01206091A JPH01206091A JP63028922A JP2892288A JPH01206091A JP H01206091 A JPH01206091 A JP H01206091A JP 63028922 A JP63028922 A JP 63028922A JP 2892288 A JP2892288 A JP 2892288A JP H01206091 A JPH01206091 A JP H01206091A
- Authority
- JP
- Japan
- Prior art keywords
- thermosensitive recording
- heat
- recording material
- overcoat layer
- methyl
- 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
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- 150000003585 thioureas Chemical class 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
- 239000001993 wax Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- MLVWCBYTEFCFSG-UHFFFAOYSA-L zinc;dithiocyanate Chemical compound [Zn+2].[S-]C#N.[S-]C#N MLVWCBYTEFCFSG-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
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/423—Intermediate, backcoat, or covering layers characterised by non-macromolecular compounds, e.g. waxes
-
- 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
Abstract
Description
【発明の詳細な説明】
[技術分野]
本発明は感熱記録材料に関し、更に詳しくはヘッドマツ
チング性が改良された感熱記録材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a heat-sensitive recording material, and more particularly to a heat-sensitive recording material with improved head matching properties.
[従来技術]
感熱記録材料は一般に紙、合成紙、プラスチックフィル
ム等の支持体上に熱発色性組成物を主成分とする感熱発
色層を設けたもので熱ヘツド、熱ペン、レーザー光等で
加熱することにより発色画像が得られる。[Prior Art] Thermosensitive recording materials generally have a thermosensitive coloring layer containing a thermochromic composition as a main component on a support such as paper, synthetic paper, or plastic film, and can be used with a thermal head, thermal pen, laser beam, etc. A colored image can be obtained by heating.
この種の記録材料は他の記録材料に比べて現像定石等の
煩雑な処理を施すことなく比較釣部Illな装置で短時
間に記録が得られること、騒ぎの発生及び環境汚染が少
ないこと、コストが安いことなどの利゛点により、図書
、文書などの複写に用いられる他、電子計算機、ファク
シミリ、券売機、ラベル、レコーダーなど多方面に葺る
記録材料として広く利用されている。このような感熱記
録材料に用いられる熱発色性組成物は一般に発色剤とこ
の発色剤を熱時発色せしめる顕色剤とからなり、発色剤
としては、例えばラクトン、ラクタム又はスピロピラン
環を有する無色又は淡色のロイコ染料が、また顕色剤と
しては各種の酸性物質、例えば有機酸やフェノール性物
質が用いられる。Compared to other recording materials, this type of recording material can be used to obtain records in a short time using simple equipment without the need for complicated processes such as developing stones, and causes less noise and environmental pollution. Due to its low cost and other advantages, it is used not only for copying books and documents, but also as a recording material for a variety of applications such as electronic computers, facsimile machines, ticket vending machines, labels, and recorders. Thermochromic compositions used in such heat-sensitive recording materials generally consist of a color former and a color developer that causes the color former to develop color when heated; Light-colored leuco dyes are used, and various acidic substances such as organic acids and phenolic substances are used as color developers.
この発色剤と顕色剤とを組合せた記録材料は特に得られ
る画像の色調が鮭明であり、かつ地肌の白色度が高く、
しかも画像(染料画像)の耐候性が優れているという利
点を有し広く利用されている。A recording material made by combining this color forming agent and a color developing agent has a particularly bright color tone of the image obtained, and has a high whiteness of the background.
Moreover, it has the advantage that the image (dye image) has excellent weather resistance, and is widely used.
近年、感熱記録材料が従来の他の記録方式にとって代り
、またその需要が増大するにつれて、この感熱記録方式
に用いられる感熱記録材料の品質向上に対する要求も高
まってきており、特にスティッキング、カス付着トラブ
ルがなく、ヘッド寿命に影響を及ぼさないヘッドマツチ
ング性に優れた感熱記録材料が要望されている。In recent years, as heat-sensitive recording materials have replaced other conventional recording methods and their demand has increased, there has been an increasing demand for improving the quality of the heat-sensitive recording materials used in these heat-sensitive recording methods, especially problems such as sticking and residue adhesion. There is a need for a heat-sensitive recording material that has excellent head matching properties and does not affect head life.
ヘッドマツチング性を向上させる方法として、吸油量の
多いフィラー及びステアリン酸亜鉛、ステアリン酸アル
ミニウム等の滑剤を含有させたオーバーコート層を設け
る方法が知られているがオーバーコート層を設けた場合
には印字の際に感熱発色層がオーバーコート層を介して
サーマルヘッドを接触することになる為、熱の伝導が阻
害され発色性が低下してしまう。A known method for improving head matching properties is to provide an overcoat layer containing a filler with high oil absorption and a lubricant such as zinc stearate or aluminum stearate. When printing, the heat-sensitive color forming layer comes into contact with the thermal head through the overcoat layer, which impedes heat conduction and reduces color development.
近年では感熱記録材料の高速記録化が進み熱応答性の向
上が望まれている為、オーバーコート層を減量しなけれ
ばならなくなっており、十分満足される結果が得られて
いない。In recent years, high-speed recording of heat-sensitive recording materials has progressed and improved thermal responsiveness has been desired, so the overcoat layer has to be reduced in weight, and satisfactorily satisfactory results have not been obtained.
[+1 的]
本発明の目的はスティッキング及びカス付着トラブルが
なく、ヘッド寿命への影響が非常に少ないヘッドマツチ
ング性にも優れた感熱記録材料を提1%することにある
。[+1 target] The object of the present invention is to provide a heat-sensitive recording material that is free from sticking and debris adhesion troubles, has very little influence on head life, and has excellent head matching properties.
[構 成]
本発明によれば、支持体上にロイコ染料と顕色剤とを含
有する感熱記録層を設け、その上にオーバーコート層を
設けた感熱記録材料に於いて該オーバーコート層中にド
記一般式[1]で表わされる化合物を含有させることを
特徴とする感熱記録材料が提供される。[Structure] According to the present invention, in a heat-sensitive recording material in which a heat-sensitive recording layer containing a leuco dye and a color developer is provided on a support, and an overcoat layer is provided thereon, in the overcoat layer: Provided is a heat-sensitive recording material characterized by containing a compound represented by the following general formula [1].
(式中、R1%R2はそれぞれ112 C−Cl−C−
1I
112 C−C−C−1112C−Cl1− C112
−1H3
本発明は上記したように上記一般式[1]で表わされる
化合物をオーバーコート層に含有させることをその主た
る構成とするものである。(In the formula, R1%R2 are each 112 C-Cl-C-
1I 112 C-C-C-1112C-Cl1- C112
-1H3 As described above, the main structure of the present invention is to contain the compound represented by the above general formula [1] in the overcoat layer.
前記一般式[1]で表わされる化合物の具体例としては
ビスフェノールSジアクリレート、ビスフェノールAジ
アクリレート、ビスフェノールSジメタクリレート、ビ
スフェノールAジメタクリレート、ビスフェノールAジ
グリシジルエーテル、ビスフェノールSジグサルシルエ
ーテル、ビスフェノールAジアリルエーテル、ビスフェ
ノールSジアリルエーテル、ビス(4−アリルオキシフ
ェニル)スルフィド、ビス(4−グリシジルオキシフェ
ニル)スルフィド、ビス(4−アクリロイルオキシフェ
ニル)スルフィド等が挙げられる。Specific examples of the compound represented by the general formula [1] include bisphenol S diacrylate, bisphenol A diacrylate, bisphenol S dimethacrylate, bisphenol A dimethacrylate, bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, and bisphenol A. Examples thereof include diallyl ether, bisphenol S diallyl ether, bis(4-allyloxyphenyl) sulfide, bis(4-glycidyloxyphenyl) sulfide, bis(4-acryloyloxyphenyl) sulfide, and the like.
本発明のオーバーコート層は前記一般式[11で表わさ
れる化合物を結合剤と共に感熱発色層上に9 (Ii乾
燥することによって形成しており、オーバーコート層に
用いる結合剤としては、メチルセルロース、メトキシセ
ルロース、ヒドロキシエチルセルロース、カルボキシメ
チルセルロース、ナトリウムカルボキシメチルセルロー
ス、セルロース、ポリビニルアルコール、カルボキシ基
変性ポリビニルアルコール、スルホン酸基変性ポリビニ
ルアルコール、ポリビニルピロリドン、ポリアクリルア
ミド、ポリアクリル酸、デンプン及びその誘導体、カゼ
イン、ゼラチン水溶性イソプレンゴム、スチレン/無水
マレイン酸共重合体のアルカリ塩イソ(又はジイソ)ブ
チレン/無水マレイン酸共重合体のアルカリ塩等の水溶
性のもの或いはポリ酢酸ビニル、塩化ビニル/酢酸ビニ
ル共重合体5、ポリスチレン、ポリアクリル酸エステル
、ポリウレタン、スチレン/ブタジェン共重合体、カル
ボキシル化スチレン/ブタジェン共重合体、スチレン/
ブタジェン/アクリル酸系共重合体等の水溶性エマルジ
ョン等が用いられる。The overcoat layer of the present invention is formed by drying the compound represented by the general formula [11] together with a binder on the heat-sensitive coloring layer. Cellulose, hydroxyethylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, cellulose, polyvinyl alcohol, carboxy group-modified polyvinyl alcohol, sulfonic acid group-modified polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid, starch and its derivatives, casein, gelatin water-soluble Isoprene rubber, alkali salts of styrene/maleic anhydride copolymers, water-soluble ones such as alkali salts of iso(or diiso)butylene/maleic anhydride copolymers, or polyvinyl acetate, vinyl chloride/vinyl acetate copolymers 5 , polystyrene, polyacrylic acid ester, polyurethane, styrene/butadiene copolymer, carboxylated styrene/butadiene copolymer, styrene/
A water-soluble emulsion such as a butadiene/acrylic acid copolymer is used.
又、必要に応じ補助添加成分、例えば填料、滑剤)を併
用することができる。この場合填料として炭酸カルシウ
ム、シリカ、酸化亜鉛、硫酸バリウム、クレー、タルク
、表面処理されたカルシウムやシリカ等の無機系微粉末
等、滑剤としては例えば高級脂肪酸又はそのエステル、
アミドもしくは金属塩の他、各種ワックス類、芳δ族カ
ルボン酸とアミノとの縮合物、安息香酸フェニルエステ
ル等が挙げられる。Further, auxiliary additive components such as fillers and lubricants may be used in combination as required. In this case, fillers include calcium carbonate, silica, zinc oxide, barium sulfate, clay, talc, surface-treated inorganic fine powders such as calcium and silica, and lubricants include higher fatty acids or their esters,
In addition to amides or metal salts, various waxes, condensates of aromatic δ group carboxylic acids and amino, benzoic acid phenyl esters, and the like can be mentioned.
オーバーコート層構成成分の使用量は結合剤については
20〜70重量%、本発明の前記一般式[1]で表わさ
れる化合物については5〜50重瓜%、好ましくは10
〜30重量%の範囲で用いられる。The amount of the overcoat layer component used is 20 to 70% by weight for the binder, and 5 to 50% by weight for the compound represented by the general formula [1] of the present invention, preferably 10% by weight.
It is used in a range of 30% by weight.
本発明において用いられるロイコ染料は単独又は2種以
上に混合して適用されるがこのようなロイコ染料として
は、この種の感熱記録材料に適用されているものが、任
意に適用され、例えば、トリフェニルメタン系、フルオ
ラン系、フェノチアジン系、オーラミン系、スピロピラ
ン系、インドリノフタリド系等の染料のロイコ化合物が
好ましく用いられる。このようなロイコ染料の具体例と
しては、例えば、以下に示すようなものが挙げられる。The leuco dyes used in the present invention may be applied singly or in combination of two or more types, and as such leuco dyes, those applied to this type of heat-sensitive recording material can be arbitrarily applied, for example, Leuco compounds of triphenylmethane-based, fluoran-based, phenothiazine-based, auramine-based, spiropyran-based, and indolinophthalide-based dyes are preferably used. Specific examples of such leuco dyes include those shown below.
3.3−ビス(p−ジメチルアミノフェニル)−フタリ
ド、
3.8−ビス(p−ジメチルアミノフェニル)−6−シ
メチルアミノフタリド(別名クリスタルバイオレットラ
クトン)、
3.3−ビス(p−ジメチルアミノフェニル)−6−ジ
エチルアミノフェニル、
3.3−ビス(p−ジメチルアミノフェニル)−6−ク
ロルフタリド、
3.3−ビス(p−ジブチルアミノフェニル)フタリド
、
3−シクロへキシルアミノ−6−クロルフルオラン、
3−ジメチルアミノ−5,7−シメチルフルオラン、
3 (N、N−ジエチルアミノ)−5−メチル−7(
N、N−ジベンジルアミノ)フルオラン、ベンゾイルロ
イコメチレンブルー、
6°−クロロ−8°−メトキシ−ベンゾインドリノ−ビ
リロスビラン、
6°−ブロモ−3°−メトキシ−ベンゾインドリノ−ピ
リロスピラン、
3− (2’−ヒドロキシ−4°−ジメチルアミノフェ
ニル) −3−(2’−メトキシ−5°−クロルフェニ
ル)フタリド、
3−(2°−ヒドロキシ−4°−ジメチルアミノフェニ
ル) −3−(2”−メトキシ−5°−ニトロフェニル
)フタリド、
3− (2’−ヒドロキシ−4°−ジエチルアミノフェ
ニル) −3−(2°−メトキシ−5°−メチルフェニ
ル)フタリド、
3−(2°−メトキシ−4°−ジメチルアミノフェニル
) −3−(2°−ヒドロキシ−4°−クロル−5゛−
メチルフェニル)フタリド、
3−そルホリノ−7−(N−プロピル−トリフルオロメ
チルアニリノ)フルオラン、
3−ピロリジノ−7−トリフルオロメチルアニリノフル
オラン、
3−ジエチルアミノ−5−クロロ−7−(N−ベンジル
−トリフルオロメチルアニリノ)フルオラン、
3−ピロリジノ−7−(ジ−p−クロルフェニル)メチ
ルアミノフルオラン、
3−ジエチルアミノ−5−クロル−7−(α−フェニル
エチルアミノ)フルオラン、3−(N−エチル−p−ト
ルイジノ)−7−(α−フェニルエチルアミノ)フルオ
ラン、3−ジエチルアミノ−7−(o−メトキシカルボ
ニルフェニルアミノ)フルオラン、3−ジエチルアミノ
−5−メチル−7−(α−フェニルエチルアミノ)フル
オラン、3−ジエチルアミノ−7−ピペリジノフルオラ
ン、
2−クロロ−3−(N−メチルトルイジノ)−7−(p
−n−ブチルアニリノ)フルオラン、3−(N−メチル
−N−イソプロピルアミノ)−6−メチル−7−アニリ
ノフルオラン、3−ジブチルアミノ−B−メチル−7−
アニリノフルオラン、
3.6−ビス(ジメチルアミノ)フルオレンスピロ(9
,3’)−8°−ジメチルアミノフタリド、3−(N−
ベンジル−N−シクロへキシルアミノ)−5,B−ベン
ゾ−7−α−ナフチルアミノ−4“−ブロモフルオラン
、
3−ジエチルアミノ−6−クロル−7−アニリノフルオ
ラン、
3−N−エチル−N−(2−エトキシプロピル)アミノ
−6−メチル−7−アニリンフルオラン、3−シジエチ
ルアミノー7−りロロフルオラン、
3−ジエチルアミノ−7−メチルフルオラン、3−ジエ
チルアミノ−7,8−ベンズフルオラン、
3−ジエチルアミノ−6−メチル−7−クロルフルオラ
ン、
3−(N−p−トリル−N−エチルアミノ)−ローメチ
ル−7−アニリノフルオラン、3−ピロリジノ−6−メ
チル−7−アニリノフルオラン、
2−IN−(3°−トリフルオルメチルフェニル)アミ
ノ)−6−ジニチルアミノフルオラン、2−13.6−
ビス(ジエチルアミノ) −9−(。3.3-bis(p-dimethylaminophenyl)-phthalide, 3.8-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (also known as crystal violet lactone), 3.3-bis(p- dimethylaminophenyl)-6-diethylaminophenyl, 3.3-bis(p-dimethylaminophenyl)-6-chlorophthalide, 3.3-bis(p-dibutylaminophenyl)phthalide, 3-cyclohexylamino-6-chlor Fluoran, 3-dimethylamino-5,7-dimethylfluoran, 3(N,N-diethylamino)-5-methyl-7(
N,N-dibenzylamino)fluorane, benzoylleucomethylene blue, 6°-chloro-8°-methoxy-benzoindolino-pyrylosvirane, 6°-bromo-3°-methoxy-benzoindolino-pyrylospirane, 3- (2 '-Hydroxy-4°-dimethylaminophenyl) -3-(2'-methoxy-5°-chlorophenyl)phthalide, 3-(2'-hydroxy-4°-dimethylaminophenyl) -3-(2"- Methoxy-5°-nitrophenyl) phthalide, 3-(2′-hydroxy-4°-diethylaminophenyl)-3-(2°-methoxy-5°-methylphenyl)phthalide, 3-(2°-methoxy-4 °-dimethylaminophenyl) -3-(2°-hydroxy-4°-chloro-5゛-
methylphenyl)phthalide, 3-sulfolino-7-(N-propyl-trifluoromethylanilino)fluorane, 3-pyrrolidino-7-trifluoromethylanilinofluorane, 3-diethylamino-5-chloro-7-( N-benzyl-trifluoromethylanilino)fluoran, 3-pyrrolidino-7-(di-p-chlorophenyl)methylaminofluoran, 3-diethylamino-5-chloro-7-(α-phenylethylamino)fluoran, 3-(N-ethyl-p-toluidino)-7-(α-phenylethylamino)fluoran, 3-diethylamino-7-(o-methoxycarbonylphenylamino)fluoran, 3-diethylamino-5-methyl-7-( α-phenylethylamino)fluorane, 3-diethylamino-7-piperidinofluorane, 2-chloro-3-(N-methyltoluidino)-7-(p
-n-butylanilino)fluoran, 3-(N-methyl-N-isopropylamino)-6-methyl-7-anilinofluoran, 3-dibutylamino-B-methyl-7-
Anilinofluorane, 3,6-bis(dimethylamino)fluorene spiro(9
,3')-8°-dimethylaminophthalide, 3-(N-
benzyl-N-cyclohexylamino)-5,B-benzo-7-α-naphthylamino-4″-bromofluorane, 3-diethylamino-6-chloro-7-anilinofluorane, 3-N-ethyl- N-(2-ethoxypropyl)amino-6-methyl-7-aniline fluorane, 3-cydiethylamino-7-lyrolofluorane, 3-diethylamino-7-methylfluorane, 3-diethylamino-7,8-benzfluoran oran, 3-diethylamino-6-methyl-7-chlorofluorane, 3-(N-p-tolyl-N-ethylamino)-rhomethyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7- Anilinofluorane, 2-IN-(3°-trifluoromethylphenyl)amino)-6-dinithylaminofluorane, 2-13.6-
Bis(diethylamino)-9-(.
−クロルアニリノ)キサンチル安息香酸ラクタム)、
3−ジエチルアミノ−6−メチル−7−(rn−トリク
ロロメチルアニリノ)フルオラン、3−ジエチルアミノ
−7−(0−クロルアニリノ)フルオラン、
3−ジブチルアミノ−7−(O−クロルアニリノ)フル
オラン、
3−N−メチル−N−アミルアミノ−6−メチル−7−
アニリノフルオラン、
3−N−メチル−N−シクロへキシルアミノ−6−メチ
ル−7−アニリノフルオラン、3−ジエチルアミノ−6
−メチル−7−アニリノフルオラン、
3−N−エチル−N−テトラヒドロフルフリルアミノ−
6−メチル−7−アニリノフルオラン、
3−ジエチルアミノ−6−メチル−7−メシチジノー4
゛、5°−ベンゾフルオラン等。3-diethylamino-6-methyl-7-(rn-trichloromethylanilino)fluoran, 3-diethylamino-7-(0-chloroanilino)fluoran, 3-dibutylamino-7-( O-chloroanilino)fluoran, 3-N-methyl-N-amylamino-6-methyl-7-
Anilinofluorane, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6
-Methyl-7-anilinofluorane, 3-N-ethyl-N-tetrahydrofurfurylamino-
6-Methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-mesitidino 4
゛, 5°-benzofluorane, etc.
3−N−メチル−N−イソブチル−6−メチル−7−ア
ニリノフルオラン、
3−N−エチル−N−イソアミル−6−メチル−7−ア
ニリノフルオラン、
3−ジエチルアミノ−6−メチル−7−(2°。3-N-methyl-N-isobutyl-6-methyl-7-anilinofluorane, 3-N-ethyl-N-isoamyl-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl- 7-(2°.
4°−ジメチルアニリノ)フルオラン、また、本発明に
おいては顕色剤として電子受容性の種々の化合物、例え
ばフェノール性化合物、チオフェノール性化合物、チオ
尿素誘導体、有機酸及びその金属塩等を必要に応じて併
用することができ、以下にその具体例を示す。4°-dimethylanilino)fluoran, and in the present invention, various electron-accepting compounds such as phenolic compounds, thiophenolic compounds, thiourea derivatives, organic acids and metal salts thereof are required as color developers. They can be used in combination depending on the conditions, and specific examples thereof are shown below.
4.4゛−イソプロピリデンビスフェノール、4.4“
−イソプロピリデンビス(0−メチルフェノール)、
4.4゛−セカンダリ−ブチリデンビスフェノール、
4.4°−イソプロピリデンビス(2−ターシャリ−ブ
チルフェノール)、
4.4°−シクロへキシリデンジフェノール、4.4°
−イソプロピリデンビス(2−クロロフェノール)、
2.2°−メチレンビス(4−メチル−6−ターシャリ
−ブチルフェノール)、
2.2°−メチレンビス(4−エチル−6−ターシャリ
ブチルフェノール)、
4.4°−ブチリデンビス(G−tOrtブチル−2−
メチル)フェノール、
1.1.3− )リス(2−メチル−4−ヒドロキシ−
5−tart−ブチルフェニル)ブタン、1.1.3−
)リス(2−メチル−4,−ヒドロキシ−5−ヒドロ
キシ−5−シクロヘキシルフェニル)ブタン、
4.4°−チオビス(6−tartブチル−2−メチル
)フェノール、
4.4“−ジフェノールスルホン、
4−イソプロポキシ−4°−ヒドロキシジフェニルスル
ホン、
4−ベンジロキシ−4゛−ヒドロキシジフェニルスルホ
ン、
4.4°−ジフェノールスルホキシド、p−ヒドロキシ
安息6酸イソプロピル、p−ヒドロキシ安息6酸ベンジ
ル、
プロトカテキュ酸ベンジル、
没食子酸ステアリル、
没食子酸ラウリル、
没食子酸オクチル、
1.7−ビス(4−ヒドロキシフェニルチオ)−3.5
−ジオキサへブタン、
1.5−ビス(4−ヒドロキシフェニルチオ)−3−オ
キサペンタン、
1.3−ビス(4−ヒドロキシフェニルチオ)−プロパ
ン、
1.3−ビス(4−ヒドロキシフェニルチオ)−2−ヒ
ドロキシプロパン、
N、N’−ジフェニルチオ尿素、
N、N’−ジ(I−クロロフェニル)チオ尿素、サリチ
ルアニリド′、
5−クロロ−サリチルアニリド、
2−ヒドロキシ−3−ナフトエ酸、
2−ヒドロキシ−1−ナフトエ酸、
l−ヒドロキシ−2−ナフトエ酸、
ヒドロキシナフトエ酸の亜鉛、アルミニウム、カルシウ
ム等の金属塩等。4.4"-isopropylidene bisphenol, 4.4"
-isopropylidene bis(0-methylphenol), 4.4°-secondary-butylidene bisphenol, 4.4°-isopropylidene bis(2-tert-butylphenol), 4.4°-cyclohexylidene diphenol, 4 .4°
-isopropylidene bis(2-chlorophenol), 2.2°-methylenebis(4-methyl-6-tert-butylphenol), 2.2°-methylenebis(4-ethyl-6-tert-butylphenol), 4.4 °-Butylidene bis(G-tOrtbutyl-2-
methyl)phenol, 1.1.3-)lis(2-methyl-4-hydroxy-
5-tart-butylphenyl)butane, 1.1.3-
) Lis(2-methyl-4,-hydroxy-5-hydroxy-5-cyclohexylphenyl)butane, 4.4°-thiobis(6-tartbutyl-2-methyl)phenol, 4.4"-diphenolsulfone, 4-isopropoxy-4°-hydroxydiphenylsulfone, 4-benzyloxy-4°-hydroxydiphenylsulfone, 4.4°-diphenolsulfoxide, isopropyl p-hydroxybenzoate, benzyl p-hydroxybenzoate, protocatechuic acid Benzyl, stearyl gallate, lauryl gallate, octyl gallate, 1.7-bis(4-hydroxyphenylthio)-3.5
-Dioxahebutane, 1.5-bis(4-hydroxyphenylthio)-3-oxapentane, 1.3-bis(4-hydroxyphenylthio)-propane, 1.3-bis(4-hydroxyphenylthio) -2-hydroxypropane, N,N'-diphenylthiourea, N,N'-di(I-chlorophenyl)thiourea, salicylanilide', 5-chloro-salicylanilide, 2-hydroxy-3-naphthoic acid, 2 -Hydroxy-1-naphthoic acid, l-hydroxy-2-naphthoic acid, metal salts of hydroxynaphthoic acid such as zinc, aluminum, calcium, etc.
ビス−(4−ヒドロキシフェニル)酢酸メチルエステル
、
ビス−(4−ヒドロキシフェニル)酢酸ベンジルエステ
ル、
1.3−ビス(4−ヒドロキシクミル)ベンゼン、1.
4−ビス−(4−ヒドロキシクミル)ベンゼン、
2.4°−ジフェノールスルホン、
3.3°−ジアリル−4,4°−ジフェノールスルホン
、
α、α−ビス−(4−ヒドロキシフェニル)−α−メチ
ルトルエンチオシアン酸亜鉛のアンチピリン錯体、
テトラブロモビスフェノールA。Bis-(4-hydroxyphenyl)acetic acid methyl ester, bis-(4-hydroxyphenyl)acetic acid benzyl ester, 1.3-bis(4-hydroxycumyl)benzene, 1.
4-bis-(4-hydroxycumyl)benzene, 2.4°-diphenolsulfone, 3.3°-diallyl-4,4°-diphenolsulfone, α,α-bis-(4-hydroxyphenyl) Antipyrine complex of -α-methyltoluene zinc thiocyanate, tetrabromobisphenol A.
テトラブロモビスフェノールS1
3.4−ジヒドロキシ−4°−メチルジフェニルスルホ
ン、
本発明においては、前記ロイコ染料、顕色剤及び補助成
分を支持体上に結合支持されるために、慣用の種々の結
合剤を適宜用いることができ、例えば、ポリビニルアル
コール、デンプン及びその誘導体、メトキシセルロース
、ヒドロキシエチルセルロース、カルボキシメチルセル
ロース、メチルセルロース、エチルセルロース等のセル
ロース、″A誘導体ポリアクリル酸ソーダ、ポリビニル
ピロリドン、アクリル酸アミド/アクリル酸エステル共
重合体、アクリル酸アミド/アクリル酸エステル/メタ
クリル酸3元共重合体、スチレン/無水マレイン酸共重
合体アルカリ塩、イソブチレン/無水マレイン酸共重合
体アルカリ塩、ポリアクリルアミド、アルギン酸ソーダ
、ゼラチン、カゼイン等の水溶性高分子の他、ポリ酢酸
ビニル、ポリウレタン、スチレン/ブタジェン共重合体
、ポリクリル酸、ポリアクリル酸エステル、塩化ビニル
/酢酸ビニル共重合体、ポリブチルメタクリレート、エ
チレン/酢酸ビニル共重合体、スチレン/ブタジェン/
アクリル系共重合体等のラテックスを用いることができ
る。Tetrabromobisphenol S1 3,4-dihydroxy-4°-methyldiphenylsulfone In the present invention, various conventional binders are used to bind and support the leuco dye, color developer, and auxiliary components on a support. For example, polyvinyl alcohol, starch and its derivatives, cellulose such as methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, ethylcellulose, "A derivative sodium polyacrylate, polyvinylpyrrolidone, acrylic acid amide/acrylic acid. Ester copolymer, acrylic amide/acrylic ester/methacrylic acid ternary copolymer, styrene/maleic anhydride copolymer alkali salt, isobutylene/maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, gelatin In addition to water-soluble polymers such as , casein, polyvinyl acetate, polyurethane, styrene/butadiene copolymer, polyacrylic acid, polyacrylic acid ester, vinyl chloride/vinyl acetate copolymer, polybutyl methacrylate, ethylene/vinyl acetate copolymer, etc. Polymer, styrene/butadiene/
Latex such as acrylic copolymer can be used.
又、本発明においては前記ロイコ染料、顕色剤及び補助
成分と共に、必要に応じ更に、この種の感熱記録材料に
慣用される補助添加成分、例えば填料、界面活性剤、熱
可融性物質(又は滑剤)等を併用することができる。こ
の場合、填料としては、例えば、炭酸カルシウム、シリ
カ、酸化亜鉛、酸化チタン、水酸化アルミニウム、水酸
化亜鉛、硫酸バリウム、クレー、タルク、表面処理され
たカルシウムやシリカ等の無機系微粉末の他、尿素−ホ
ルマリン樹脂、スチレン/メタクリル酸共重合体、ポリ
スチレン樹脂等の有機系の微粉末を挙げることができる
。In addition, in the present invention, in addition to the leuco dye, color developer, and auxiliary components, auxiliary additive components commonly used in this type of heat-sensitive recording material, such as fillers, surfactants, thermofusible substances ( or lubricant), etc. can be used in combination. In this case, fillers include, for example, calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, talc, and surface-treated inorganic fine powders such as calcium and silica. , urea-formalin resin, styrene/methacrylic acid copolymer, polystyrene resin, and other organic fine powders.
[実施例]
次に本発明を実施例によりさらに詳細に説明する。なお
、以下に示す部及び%はいずれも重量基準である。[Example] Next, the present invention will be explained in more detail with reference to Examples. Note that all parts and percentages shown below are based on weight.
実施例1
〔A液]
8−(N−メチル−N−シクロへキシルアミノ)−8−
メチル−7
一アニリツフルオラン 20部
ポリビニルアルコール1026水溶液 20部水
80部[
B液]
2.2°−ビス(4−ヒドロキシフェニル)プロパン
20部
ポリビニルアルコール10%水溶液 20部水
(i0m二
[C液]
ビスフェノールSジアクリレート 20部ポリビニルア
ルコールlO%水溶液 20部水
60=[D液]
ビスフェノールAジアクリレート 20部ポリビニルア
ルコールlO%水溶液 20部水
60部[E液]
ビス(4−グリシジルオキシ
フェニル)スルフィド 20部
ポリビニルアルコール10%水溶液20部水
60部上記組
成からなる混合物をそれぞれサンドグラインダーで2〜
4時間粉砕分散してA液、B液を:A整した。更にA液
、B液のfff量比が1:3となるように混合撹拌して
感熱発色層塗布液を調製し市販の坪量約47g/m 2
の上質紙に乾燥後塗布量が4.5g/+”となるように
塗布乾燥した。Example 1 [Liquid A] 8-(N-methyl-N-cyclohexylamino)-8-
Methyl-7 monoanilifluorane 20 parts polyvinyl alcohol 1026 aqueous solution 20 parts water
80 copies [
B liquid] 2.2°-bis(4-hydroxyphenyl)propane
20 parts polyvinyl alcohol 10% aqueous solution 20 parts water
(i0m2 [Liquid C] Bisphenol S diacrylate 20 parts Polyvinyl alcohol lO% aqueous solution 20 parts Water
60 = [Liquid D] Bisphenol A diacrylate 20 parts Polyvinyl alcohol 10% aqueous solution 20 parts Water
60 parts [Liquid E] Bis(4-glycidyloxyphenyl) sulfide 20 parts Polyvinyl alcohol 10% aqueous solution 20 parts Water
60 parts of each of the mixtures having the above composition were ground in a sand grinder for 2~
The mixture was pulverized and dispersed for 4 hours to prepare liquids A and B. Further, a heat-sensitive coloring layer coating solution was prepared by mixing and stirring so that the fff amount ratio of A and B was 1:3, and a commercially available basis weight of about 47 g/m 2 was prepared.
It was coated and dried on high-quality paper so that the coating amount after drying was 4.5 g/+''.
次に
〔C液〕20部
10%ポリビニルアルコール水溶液 30部炭酸カルシ
ウム 3部30%ステアリン酸亜鉛
分散液 3部水
60部の割合でオーバーコート層塗布
液を調製し乾燥塗布量が1.Og/m’となるように該
感熱発色層上に塗布乾燥しスーパーキャレンダーにて平
滑度が500〜1000秒となるようにキャレンダーが
けして本発明の感熱記録材料を得た。Next [Liquid C] 20 parts 10% polyvinyl alcohol aqueous solution 30 parts calcium carbonate 3 parts 30% zinc stearate dispersion 3 parts water
An overcoat layer coating solution was prepared at a ratio of 60 parts, and the dry coating amount was 1. The heat-sensitive recording material of the present invention was obtained by coating and drying the heat-sensitive coloring layer on the heat-sensitive coloring layer to a smoothness of 500 to 1000 seconds.
実施例2
実施例1の[C液]の代りに[D液]を用いた以外はす
べて実施例1と同様にして感熱記録材料を作成した。Example 2 A heat-sensitive recording material was prepared in the same manner as in Example 1 except that [Liquid D] was used instead of [Liquid C] in Example 1.
実施例3
実施例1の[C液]の代りに[E液]を用いた以外はす
べて実施例1と同様にして感熱記録材料を作成した。Example 3 A heat-sensitive recording material was prepared in the same manner as in Example 1 except that [Liquid E] was used instead of [Liquid C] in Example 1.
比較例1
実施例1のオーバーコート液中から[C液]を除いた以
外は実施例1と同様にして感熱記録材料を作成した。Comparative Example 1 A heat-sensitive recording material was prepared in the same manner as in Example 1 except that [Liquid C] was removed from the overcoat liquid in Example 1.
以上のようにして得られた各感熱記録材料をリコー製感
熱ファクシミリRIFAX130で印字しスティッキン
グ及びカス付着状態を調べると共に、同ファクシミリで
1万回印字テストを行い、小板研究所製表面粗さ計によ
りヘッドの摩耗状態を測定した。Each of the heat-sensitive recording materials obtained as described above was printed using a Ricoh thermal facsimile RIFAX130 to check for sticking and residue adhesion, and a printing test was conducted 10,000 times using the same facsimile. The wear condition of the head was measured.
それらの結果を次に示す。The results are shown below.
表−1
[効 果]
本発明の感熱記録材料はスティッキング及びカス何首ト
ラブルがなく、ヘッド寿命への影響が非常に少ないヘッ
ドマツチング性にも優れたものである。Table 1 [Effects] The heat-sensitive recording material of the present invention is free from sticking and scrap troubles and has excellent head matching properties with very little effect on head life.
Claims (1)
を設け、その上にオーバーコート層を設けた感熱記録材
料において、該オーバーコート層中に下記一般式[ I
]で表わされる化合物を含有させる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▼[ I ] (式中、R_1、R_2はそれぞれ▲数式、化学式、表
等があります▼、 ▲数式、化学式、表等があります▼、H_2C=CH−
CH_2−、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼、XはSO_2、S、▲数式、化学式
、表等があります▼を示す)[Scope of Claims] A heat-sensitive recording material in which a heat-sensitive recording layer containing a leuco dye and a color developer is provided on a support, and an overcoat layer is provided thereon, in which the overcoat layer contains the following general formula [ I
] A heat-sensitive recording material characterized by containing a compound represented by the following. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (In the formula, R_1 and R_2 are respectively ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, H_2C=CH-
CH_2−, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc.▼, X indicates SO_2, S, ▲There are mathematical formulas, chemical formulas, tables, etc.▼)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63028922A JP2752364B2 (en) | 1988-02-12 | 1988-02-12 | Thermal recording material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63028922A JP2752364B2 (en) | 1988-02-12 | 1988-02-12 | Thermal recording material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01206091A true JPH01206091A (en) | 1989-08-18 |
JP2752364B2 JP2752364B2 (en) | 1998-05-18 |
Family
ID=12261896
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63028922A Expired - Fee Related JP2752364B2 (en) | 1988-02-12 | 1988-02-12 | Thermal recording material |
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Country | Link |
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JP (1) | JP2752364B2 (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4936343A (en) * | 1972-08-05 | 1974-04-04 | ||
JPS6068990A (en) * | 1983-09-27 | 1985-04-19 | Sanyo Kokusaku Pulp Co Ltd | Thermal recording material |
JPS6259080A (en) * | 1985-09-09 | 1987-03-14 | Ricoh Co Ltd | Thermal recording material |
JPS62263086A (en) * | 1986-05-10 | 1987-11-16 | Nippon Shokubai Kagaku Kogyo Co Ltd | Thermal recording paper |
JPS62270382A (en) * | 1986-05-19 | 1987-11-24 | Mitsubishi Paper Mills Ltd | Thermal recording sheet |
-
1988
- 1988-02-12 JP JP63028922A patent/JP2752364B2/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4936343A (en) * | 1972-08-05 | 1974-04-04 | ||
JPS6068990A (en) * | 1983-09-27 | 1985-04-19 | Sanyo Kokusaku Pulp Co Ltd | Thermal recording material |
JPS6259080A (en) * | 1985-09-09 | 1987-03-14 | Ricoh Co Ltd | Thermal recording material |
JPS62263086A (en) * | 1986-05-10 | 1987-11-16 | Nippon Shokubai Kagaku Kogyo Co Ltd | Thermal recording paper |
JPS62270382A (en) * | 1986-05-19 | 1987-11-24 | Mitsubishi Paper Mills Ltd | Thermal recording sheet |
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JP2752364B2 (en) | 1998-05-18 |
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