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JPH0362157B2 - - Google Patents
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JPH0362157B2 - - Google Patents

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Publication number
JPH0362157B2
JPH0362157B2 JP60152177A JP15217785A JPH0362157B2 JP H0362157 B2 JPH0362157 B2 JP H0362157B2 JP 60152177 A JP60152177 A JP 60152177A JP 15217785 A JP15217785 A JP 15217785A JP H0362157 B2 JPH0362157 B2 JP H0362157B2
Authority
JP
Japan
Prior art keywords
heat
sensitive recording
pva
layer
epoxy group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP60152177A
Other languages
Japanese (ja)
Other versions
JPS6213381A (en
Inventor
Tomohiko Nomura
Hitoshi Shimizu
Hiroshi Inoe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Denka Co Ltd
Original Assignee
Denki Kagaku Kogyo KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Denki Kagaku Kogyo KK filed Critical Denki Kagaku Kogyo KK
Priority to JP60152177A priority Critical patent/JPS6213381A/en
Publication of JPS6213381A publication Critical patent/JPS6213381A/en
Publication of JPH0362157B2 publication Critical patent/JPH0362157B2/ja
Granted legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337Additives; Binders
    • B41M5/3372Macromolecular compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Description

【発明の詳細な説明】[Detailed description of the invention]

〔産業上の利用分野〕 本発明は熱的手段によつて記録を行う感熱記録
材料に関する。 〔従来の技術〕 感熱記録材料は、通常加熱によつて発色画像を
記録し得る感熱発色層を紙、プラスチツクフイル
ム又は金属蒸着紙等の支持体上に設けたものであ
り、これは単に加熱するだけで記録が得られる
為、図書、文書などの複写には勿論のこと、電子
計算機、フアクシミリ、各種計算機の出力記録及
び身分証明書、定期券、乗車券等の書込み等に広
く用いられている。中でも支持体上に通常は無色
又は淡色のロイコ染料とフエノール化合物などの
酸性物質とを主成分として用いた感熱記録材料は
画像の色調が鮮明であることから特に有用であ
る。 一般に感熱記録材料には発色成分以外に結着剤
が重要な役割をはたしている。通常該感熱記録材
料は発色剤であるロイコ染料と顕色剤である酸性
物質との両成分を夫々別個に水溶性、水分散性の
結着剤を含んでいる水媒体中で例えばボールミ
ル、サンドグラインダーなどの様な各種分散機に
よつて分散させ微粒子化した後、各分散液を混合
してから支持体に塗布、乾燥してつくられる。 従来、結着剤としてはポリビニルアルコール
(以下PVAと略記)、澱粉またはその変性物及び
誘導体、メチルセルロース、カルボキシメチルセ
ルロース、アラビヤゴム、ゼラチン、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
酸塩、スチレン/無水マレイン酸共重合体塩、イ
ソブチレン/無水マレイン酸共重合体塩などの水
溶性高分子やポリ酢酸ビニル、スチレン/ブタジ
エン共重合体などの高分子エマルジヨン、ラテツ
クス等が提案され使用されている。 〔ペーパーセールスエンジニアリングシリーズ
□4新・情報産業紙P.222(紙業タイムス社編)〕 〔発明が解決しようとする問題点〕 中でもPVAや澱粉(特に酸化澱粉、エーテル
化澱粉等)は結着剤に要求される特性(分散性、
凝集性のないこと、形成皮膜強度、発色性、ステ
イツキングやカス付着性のないこと)において他
の結着剤よりも良好な性能が出せるが、未だ充分
満足のいく性能が得られていない。例えば加熱、
記録を長期間にわたつて続けると、サーマルヘツ
ドとの摩擦によりカスがサーマルヘツドに附着し
記録不良が発生したり、サーマルヘツド自体と感
熱記録紙が高温時に付着するといういわゆるステ
イツキングの問題が生じたりする。更に、印字し
た記録紙が水や可塑剤などに触れるとその印字が
消えたり、層面のベタツキやはがれの生じること
があり、また記録後の画像濃度低下や場合によつ
ては全く画像が判読不可能となること等という耐
水化の問題が残されている。 PVAや澱粉の耐水化剤としてはメラミン−ホ
ルマリン初期縮合物、エポキシ化合物、グリオキ
ザール、クロム明ばん、グルタルアルデヒド等が
知られているが、塗布液が凝集をおこすとか、発
色性を害なうとか、充分な耐水性を得るためには
高温での熱処理を必要とするとか、種々の欠点を
有している。特に高温での熱処理は感熱記録材料
製造においては発色の問題を生じるために不適当
である。 更に、感熱記録層に支障を与える水、可塑剤等
が該層に接触することを防止するため、感熱記録
層の表面、感熱記録層の支持体の面等に保護層を
設けることが知られているが、満足出来る効果を
得るに至つていない。 〔問題点を解決するための手段〕 本発明は、無色又は淡色のロイコ染料、加熱に
より該ロイコ染料を発色せしめる酸性物質及びエ
ポキシ基変性PVAを支持体上に含有してなる感
熱記録材料である。 本発明におけるロイコ染料としてはトリフエニ
ルメタン系、フルオラン系、フエノチアジン系、
オーラミン系、スピロピラン系染料のロイコ体で
あり、これには例えば 3,3−ビス(p−ジメチルアミノフエニル)
−6−ジメチルアミノフタリド、 3,3−ビス(p−ジメチルアミノフエニル)
フタリド、 3,3−ビス(p−ジメチルアミノフエニル)
−6−ジエチルアミノフタリド、 3,3−ビス(p−ジメチルアミノフエニル)
−6−クロロフタリド、 3−(N−p−トリル−N−エチルアミノ)−6
−メチル−7−(N−フエニルアミノ)フルオラ
ン、 3−ジエチルアミノ−6−メチル−7−アニリ
ルフルオラン、 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−7−(3−フルオロメチ
ル)フエニ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
ピリロスピラン、 6′−ブロモ−8′−メトキシ−ベンゾインドリノ
ピリロスピラン、 2−〔3,6−ビス(ジエチルアミン)−9−
(o−クロロアニリノ)キサンチル〕安息香酸ラ
クタム等があげられる。 又前記ロイコ染料と加熱発色反応をおこし、該
ロイコ体を発色せしめる酸性物質としては例えば
フエノール、p−メチルフエノール、α−ナフト
ール、β−ナフトール、2,2−ビス(p−ヒド
ロキシフエニル)プロパン〔別名ビスフエノール
A〕、2,2−ビス(p−ヒドロキシフエニル)
ブタン、4,4′−シクロヘキシリデンジフエノー
ル、安息香酸、サリチル酸、酒石酸、没食子酸等
があげられるが、ロイコ染料及び酸性物質とも特
にこれらに限定されるわけではない。 感熱記録材料において、エポキシ基変性PVA
を感熱発色層の結着剤としておよび/または該層
を保護する保護層を形成するために用いることが
本発明の最大の特徴である。 エポキシ基変性PVAの製造法は既に本出願人
が特願昭59−51158号明細書(特開昭60−195103
号公報)において提案している。即ち本発明で用
いられるエポキシ基変性PVAは、 ビニルエステルと一般式 (R1、R2、R3及びR4は水素原子又はアルキル
基、n1は1又は2、n2は1、2又は3を表わす。)
で表わされるエポキシ基含有不飽和化合物とをラ
ジカル重合開始剤存在下、共重合させた後、アル
コール中アルカリ触媒によりケン化することによ
り得られ、分子内に一般式 (R1、R2、R3、R4、n1及びn2は前記式と同義)
で示される共重合単位を含有する変性PVA系重
合体である。 エポキシ基の含有量は0.01〜10モル%の範囲か
ら選ばれる。エポキシ基の含有量があまり少ない
と本発明の効果は得がたく、逆に必要以上多くて
も使用料の割には期待される効果を得ることがで
きない。重合度は200〜3500、ケン化度はビニル
アルコール単位99.99〜70モル%、ビニルエステ
ル単位0〜29モル%の範囲から選ばれることが望
ましい。 エポキシ変性PVAを結着剤として用いる場合
は単独もしくは他に水溶性高分子としてPVA、
変形PVA、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、
ポリビニルピロリドン、ポリアクリルアミド、ポ
リアクリル酸塩、澱粉、あるいはポリスチレン、
ポリ酢酸ビニル、SBR、ポリブチルメタクリレ
ート等のような水性エマルジヨンを併用すること
もできる。その際結着剤の使用量はロイコ染料及
び酸性物質の総量に対して10〜200重量%が適当
である。該コーテイング液の固形分濃度は作業性
を考慮して10〜40重量%の範囲から選ばれる。 また、エポキシ基変性PVAを用いて感熱発色
層を保護する保護層を形成する場合、該PVA単
独でもしくはポリアミド樹脂、メラミン樹脂、グ
リオキザール、他の水溶性高分子、水性エマルジ
ヨン、顔料、無機物質、滑剤、消泡剤等の公知物
質とともに水系塗布液とし、その液を感熱発色層
の表面、該記録層の支持体面等に塗布乾燥して保
護層を設けることが出来る。 エポキシ基変性PVAを含有する保護層は公知
の物質、例えばポリ酢酸ビニル単独重合体をケン
化して得られる無変性PVA、を結着剤とする感
熱記録層を有効に保護する。 該保護層を形成する塗布液を塗布するにはロー
ルコーター法、エアードクター法、ブレードコー
ター法等任意の公知の方法が採用される。保護層
の塗布量は0.5〜4.0g/m2が好ましく4.0g/m2
越えると感熱発色層の熱感応性を阻害し、0.5
g/m2未満では皮膜形成性が悪くなる。 本発明の感熱記録材料には、感熱発色層中にさ
らに炭酸カルシウム、シリカ、アルミナ、マグネ
シア、タルク、硫酸バリウム、ステアリン酸アル
ミニウムなどの微粉末を含有させて、発色画像の
鮮明性を向上せしめ、またアマニ油、桐油、ロ
ウ、パラフイン、ポリエチレンワツクス、塩化パ
ラフインなどの潤滑剤を添加してサーマルヘツド
の走行性を一層改善することができる。 その他の添加剤、助剤として脂肪族金属塩など
の滑剤・離型剤、多価エポキシ化合物等の耐水化
剤、塩化亜鉛・硫酸亜鉛・クエン酸ソーダ・チオ
ウレア硫酸グアニジン・ソルビトール・サツカロ
ーズ等の地色の発色を防ぐ発色抑制剤や発色補助
剤、アルキル基で置換されたフエノール・複数個
フエノール基を有する化合物等の耐光・耐油・耐
可塑性を向上させる保存性改良剤、一般に使用さ
れている消泡剤等を適宜添加することもできる。 本発明の感熱記録材料に用いられる支持体は、
特に制限はなく、紙、板紙及びこれ等の加工紙、
プラスチツクフイルム、金属蒸着紙等多くあり、
支持体の面に感熱記録層、保護層を設けて、感熱
記録材料とすればよい。 また該発色層を塗布するにあたつてはロールコ
ーター法、エアードクター法、ブレードコーター
法等の公知の方法が採用される。その塗布量は1
〜20g/m2、好ましくは3〜10g/m2程度になる
ようにするのが適当である。 〔実施例〕 以下本発明を実施例により具体的に説明する
が、本発明はこれら実施例に限定するものではな
い。特にことわらない限り「部」、「%」は重量
部、重量%を意味する。 実施例 1 (A液) ・クリスタルバイオレツトラクトン 2部 ・エポキシ基変性PVA*10%水溶液(アクリルグ
リシジルエーテル構造単位1モル%含有。ケン
化度98モル%、重合度1100) 20部 ・水 28部 (B液) ・ビスフエノールA 6部 ・A液と同一のエポキシ基変性PVA*の10%水溶
液 20部 ・炭酸カルシウム 5部 ・ステアリン酸アミド 2部 ・水 27部 * 結着剤。酢酸ビニルとアリルグリシジルエ
ーテル共重合体ケン化物。 上記組成を有する混合物をそれぞれボールミル
で24時間粉砕・分散してA液並びにB液を調製
し、A液50部とB液50部を更に混合して感熱発色
層コーテイング液を得た。 該コーテイング液を上質紙(坪量50g/m2)の
片面に塗布・乾燥して塗布量5g/m2)の感熱記
録紙を得た。 実施例 2 エポキシ変性PVAの代わりに電気化学工業(株)
製無変性PVA K−05(ケン化度98モル%、重合
度650)を結着剤として用いた以外は実施例1と
同様にして感熱発色層塗布紙を製作した。次いで
実施例1で結着剤として用いたエポキシ変性
PVAの水溶液を水で希釈して浄化感熱発色層上
に乾燥時の塗布量が2g/m2になるように塗布、
乾燥して保護層を設けて感熱記録紙を得た。 実施例 3〜5 エポキシ基変性PVAを得るのに用いるエポキ
シ基含有単量体の種類及び変性PVAのエポキシ
基含有単位の含有率とケン化度を表に示す通り変
えた以外は実施例1と同様にして感熱記録紙を得
た。 比較例 1 エポキシ基変性PVAの代わりにケン代度98モ
ル%、重合度1100の完全ケン化無変性PVAを結
着剤として用いた以外は実施例1と同様に、感熱
記録紙を得た。 比較例 2 保護層のエポキシ基変性PVAの代わりに、ケ
ン化度98モル%、重合度1100の完全ケン化無変性
PVAを保護層形成剤として用いた以外は実施例
2と同様に感熱記録紙を得た。 こうして得られた感熱紙を次のようにしてステ
イツキング、耐水性等の比較を行つた。 (1) OKI FAX7100(沖電気社製)で記録した際
のステイツキング及びヘツドカス付着の比較 (2) 湿つた指によるベタつきの比較 (3) 水を一滴塗工面に落とし、その部分を指で5
回こすり塗布面のはがれ度合の比較 評価結果を表に示す。
[Industrial Field of Application] The present invention relates to a heat-sensitive recording material that performs recording by thermal means. [Prior Art] A heat-sensitive recording material is a material in which a heat-sensitive coloring layer capable of recording a colored image by heating is provided on a support such as paper, plastic film, or metallized paper; Because records can be obtained with just one hand, it is widely used not only for copying books and documents, but also for recording the output of electronic computers, facsimile machines, various calculators, and writing on ID cards, commuter passes, train tickets, etc. . Among them, a heat-sensitive recording material using a usually colorless or light-colored leuco dye and an acidic substance such as a phenol compound as main components on a support is particularly useful because the color tone of the image is clear. Generally, in addition to the color-forming component, a binder plays an important role in heat-sensitive recording materials. Usually, the heat-sensitive recording material is prepared by separately preparing both the leuco dye as a coloring agent and the acidic substance as a color developer in an aqueous medium containing a water-soluble or water-dispersible binder, for example, by ball milling or sanding. After being dispersed and made into fine particles using various dispersing machines such as a grinder, each dispersion liquid is mixed, and then applied to a support and dried. Conventionally, binders include polyvinyl alcohol (hereinafter abbreviated as PVA), starch or its modified products and derivatives, methylcellulose, carboxymethylcellulose, gum arabic, gelatin, polyvinylpyrrolidone, polyacrylamide, polyacrylate, styrene/maleic anhydride, etc. Water-soluble polymers such as polymer salts, isobutylene/maleic anhydride copolymer salts, and polymer emulsions and latexes such as polyvinyl acetate and styrene/butadiene copolymers have been proposed and used. [Paper Sales Engineering Series □4 New Information Industry Paper P.222 (edited by Shigyo Times)] [Problems that the invention aims to solve] Among them, PVA and starch (especially oxidized starch, etherified starch, etc.) have a tendency to bind. Characteristics required for the agent (dispersibility,
Although it exhibits better performance than other binders in terms of non-cohesive properties, film strength, color development, and non-sticking and scum adhesion properties, it has not yet achieved sufficiently satisfactory performance. For example, heating
When recording continues for a long period of time, friction with the thermal head causes debris to adhere to the thermal head, resulting in poor recording, and the problem of so-called stagnation, where the thermal head itself and thermal recording paper adhere to each other at high temperatures. or Furthermore, if the printed recording paper comes into contact with water or plasticizers, the print may disappear, the layer surface may become sticky or peel, and the image density may decrease after recording or the image may become completely illegible in some cases. There remains the issue of whether or not it will be possible to make it water resistant. Melamine-formalin initial condensate, epoxy compounds, glyoxal, chromium alum, glutaraldehyde, etc. are known as waterproofing agents for PVA and starch, but they may cause aggregation of the coating solution or impair color development. However, it has various drawbacks, such as requiring heat treatment at high temperatures in order to obtain sufficient water resistance. In particular, heat treatment at high temperatures is inappropriate in the production of heat-sensitive recording materials because it causes color development problems. Furthermore, it is known to provide a protective layer on the surface of the heat-sensitive recording layer, on the surface of the support of the heat-sensitive recording layer, etc., in order to prevent water, plasticizers, etc. that may cause trouble to the heat-sensitive recording layer from coming into contact with the layer. However, satisfactory results have not yet been obtained. [Means for Solving the Problems] The present invention is a heat-sensitive recording material comprising, on a support, a colorless or light-colored leuco dye, an acidic substance that causes the leuco dye to develop color when heated, and an epoxy group-modified PVA. . Leuco dyes in the present invention include triphenylmethane-based, fluoran-based, phenothiazine-based,
It is a leuco form of auramine-based and spiropyran-based dyes, such as 3,3-bis(p-dimethylaminophenyl).
-6-dimethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)
Phthalide, 3,3-bis(p-dimethylaminophenyl)
-6-diethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)
-6-chlorophthalide, 3-(N-p-tolyl-N-ethylamino)-6
-Methyl-7-(N-phenylamino)fluoran, 3-diethylamino-6-methyl-7-anilylfluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-7-(3-fluoromethyl)fluoran Enylaminofluoran, benzoylleucomethylene blue, 6'-chloro-8'-methoxy-benzoindolinopyrillospirane, 6'-bromo-8'-methoxy-benzoindolinopyrillospirane, 2-[3,6- Bis(diethylamine)-9-
Examples include (o-chloroanilino)xantyl]benzoic acid lactam. Examples of acidic substances that cause a heating coloring reaction with the leuco dye and color the leuco substance include phenol, p-methylphenol, α-naphthol, β-naphthol, and 2,2-bis(p-hydroxyphenyl)propane. [Also known as bisphenol A], 2,2-bis(p-hydroxyphenyl)
Examples include butane, 4,4'-cyclohexylidene diphenol, benzoic acid, salicylic acid, tartaric acid, gallic acid, etc., but neither leuco dyes nor acidic substances are particularly limited to these. In heat-sensitive recording materials, epoxy group-modified PVA
The greatest feature of the present invention is that it is used as a binder for the thermosensitive coloring layer and/or to form a protective layer to protect the layer. The method for producing epoxy group-modified PVA has already been disclosed by the applicant in Japanese Patent Application No. 59-51158 (Japanese Unexamined Patent Publication No. 60-195103).
This is proposed in the following publication. That is, the epoxy group-modified PVA used in the present invention has a vinyl ester and a general formula: (R 1 , R 2 , R 3 and R 4 represent a hydrogen atom or an alkyl group, n 1 represents 1 or 2, and n 2 represents 1, 2 or 3.)
It is obtained by copolymerizing an epoxy group-containing unsaturated compound represented by the following in the presence of a radical polymerization initiator, and then saponifying it with an alkali catalyst in alcohol. (R 1 , R 2 , R 3 , R 4 , n 1 and n 2 are synonymous with the above formula)
This is a modified PVA-based polymer containing copolymerized units shown in the following. The content of epoxy groups is selected from the range of 0.01 to 10 mol%. If the content of epoxy groups is too small, it is difficult to obtain the effects of the present invention, and conversely, if the content is more than necessary, the expected effects cannot be obtained considering the amount used. It is preferable that the degree of polymerization is selected from the range of 200 to 3500, and the degree of saponification is selected from the range of 99.99 to 70 mol% of vinyl alcohol units and 0 to 29 mol% of vinyl ester units. When using epoxy-modified PVA as a binder, PVA alone or as a water-soluble polymer,
Modified PVA, methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose,
polyvinylpyrrolidone, polyacrylamide, polyacrylate, starch, or polystyrene,
Aqueous emulsions such as polyvinyl acetate, SBR, polybutyl methacrylate, etc. can also be used in combination. In this case, the appropriate amount of the binder used is 10 to 200% by weight based on the total amount of leuco dye and acidic substance. The solid content concentration of the coating liquid is selected from the range of 10 to 40% by weight in consideration of workability. In addition, when forming a protective layer that protects the thermosensitive coloring layer using epoxy group-modified PVA, the PVA alone or polyamide resin, melamine resin, glyoxal, other water-soluble polymers, aqueous emulsion, pigments, inorganic substances, A protective layer can be provided by forming an aqueous coating liquid together with known substances such as a lubricant and an antifoaming agent, and applying and drying the liquid onto the surface of the thermosensitive color forming layer, the support surface of the recording layer, etc. A protective layer containing epoxy group-modified PVA effectively protects a heat-sensitive recording layer whose binder is a known substance, for example, unmodified PVA obtained by saponifying a polyvinyl acetate homopolymer. Any known method such as a roll coater method, an air doctor method, a blade coater method, etc. can be used to apply the coating liquid for forming the protective layer. The coating amount of the protective layer is preferably 0.5 to 4.0 g/ m2 , and if it exceeds 4.0 g/ m2 , the heat sensitivity of the heat-sensitive coloring layer will be inhibited.
If it is less than g/m 2 , film forming properties will be poor. The heat-sensitive recording material of the present invention further contains fine powders such as calcium carbonate, silica, alumina, magnesia, talc, barium sulfate, and aluminum stearate in the heat-sensitive coloring layer to improve the clarity of the colored image. Furthermore, the running properties of the thermal head can be further improved by adding a lubricant such as linseed oil, tung oil, wax, paraffin, polyethylene wax, or chlorinated paraffin. Other additives and auxiliaries include lubricants and mold release agents such as aliphatic metal salts, water-resistant agents such as polyvalent epoxy compounds, zinc chloride, zinc sulfate, sodium citrate, guanidine thiourea sulfate, sorbitol, and sugar rose. Color development inhibitors and color development aids that prevent color development; storage improvers that improve light resistance, oil resistance, and plasticity resistance such as phenols substituted with alkyl groups and compounds with multiple phenol groups; and commonly used erasers. Foaming agents and the like may also be added as appropriate. The support used in the heat-sensitive recording material of the present invention is
There are no particular restrictions; paper, paperboard, and other processed papers;
There are many types such as plastic film and metallized paper.
A heat-sensitive recording material may be obtained by providing a heat-sensitive recording layer and a protective layer on the surface of the support. Further, in applying the coloring layer, known methods such as a roll coater method, an air doctor method, a blade coater method, etc. are employed. The amount of application is 1
It is appropriate to adjust the amount to about 20 g/m 2 , preferably about 3 to 10 g/m 2 . [Examples] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "parts" and "%" mean parts by weight and % by weight. Example 1 (Liquid A) - 2 parts of crystal violet lactone - 10% aqueous solution of epoxy group-modified PVA * (contains 1 mol% of acrylic glycidyl ether structural unit. Degree of saponification 98 mol%, degree of polymerization 1100) 20 parts - Water 28 Part (Liquid B) - 6 parts of bisphenol A - 20 parts of a 10% aqueous solution of the same epoxy group-modified PVA * as Liquid A - 5 parts of calcium carbonate - 2 parts of stearic acid amide - 27 parts of water * Binder. Saponified vinyl acetate and allyl glycidyl ether copolymer. The mixtures having the above compositions were each ground and dispersed in a ball mill for 24 hours to prepare liquids A and B, and 50 parts of liquid A and 50 parts of liquid B were further mixed to obtain a heat-sensitive coloring layer coating liquid. The coating liquid was coated on one side of high-quality paper (basis weight: 50 g/m 2 ) and dried to obtain thermal recording paper with a coating weight of 5 g/m 2 ). Example 2 Denki Kagaku Kogyo Co., Ltd. instead of epoxy modified PVA
A paper coated with a heat-sensitive coloring layer was prepared in the same manner as in Example 1, except that unmodified PVA K-05 (Saponification degree: 98 mol %, Polymerization degree: 650) was used as the binder. Next, the epoxy modification used as a binder in Example 1
An aqueous solution of PVA is diluted with water and applied onto the purified heat-sensitive coloring layer so that the dry coating amount is 2 g/m2.
After drying and providing a protective layer, a thermosensitive recording paper was obtained. Examples 3 to 5 Same as Example 1 except that the type of epoxy group-containing monomer used to obtain epoxy group-modified PVA, the content of epoxy group-containing units of modified PVA, and the degree of saponification were changed as shown in the table. A thermosensitive recording paper was obtained in the same manner. Comparative Example 1 A thermosensitive recording paper was obtained in the same manner as in Example 1, except that a completely saponified unmodified PVA with a degree of hydrogen content of 98 mol % and a degree of polymerization of 1100 was used as a binder instead of epoxy group-modified PVA. Comparative Example 2 Instead of epoxy group-modified PVA in the protective layer, completely saponified and unmodified with a saponification degree of 98 mol% and a polymerization degree of 1100
A thermosensitive recording paper was obtained in the same manner as in Example 2 except that PVA was used as the protective layer forming agent. The thermal paper thus obtained was compared in terms of staking, water resistance, etc., as follows. (1) Comparison of state king and head residue adhesion when recording with OKI FAX7100 (manufactured by Oki Electric Co., Ltd.) (2) Comparison of stickiness caused by wet fingers (3) Drop a drop of water on the coated surface and touch the area with your finger.
Comparison of the degree of peeling of the surface coated with repeated rubbing The evaluation results are shown in the table.

〔発明の効果〕〔Effect of the invention〕

本発明の感熱記録材料はステイツキングやカス
付着の発生がなく、水分による層面のベタつきや
はがれの生じることがないという従来の感熱記録
材料の欠点が大幅に改善されたという点で極めて
優れている。
The heat-sensitive recording material of the present invention is extremely superior in that it does not cause statesking or residue adhesion, and does not cause stickiness or peeling of the layer surface due to moisture, which is a major improvement over the drawbacks of conventional heat-sensitive recording materials. .

Claims (1)

【特許請求の範囲】[Claims] 1 無色又は淡色のロイコ染料、加熱によつて該
ロイコ染料を発色せしめる酸性物質及びエポキシ
基変性ポリビニルアルコールを支持体上に含有し
てなる感熱記録材料。
1. A heat-sensitive recording material comprising, on a support, a colorless or light-colored leuco dye, an acidic substance that causes the leuco dye to develop color when heated, and an epoxy group-modified polyvinyl alcohol.
JP60152177A 1985-07-12 1985-07-12 Thermal recording material Granted JPS6213381A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP60152177A JPS6213381A (en) 1985-07-12 1985-07-12 Thermal recording material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60152177A JPS6213381A (en) 1985-07-12 1985-07-12 Thermal recording material

Publications (2)

Publication Number Publication Date
JPS6213381A JPS6213381A (en) 1987-01-22
JPH0362157B2 true JPH0362157B2 (en) 1991-09-25

Family

ID=15534731

Family Applications (1)

Application Number Title Priority Date Filing Date
JP60152177A Granted JPS6213381A (en) 1985-07-12 1985-07-12 Thermal recording material

Country Status (1)

Country Link
JP (1) JPS6213381A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62264990A (en) * 1986-05-13 1987-11-17 Honshu Paper Co Ltd Heatsensitive recording sheet

Also Published As

Publication number Publication date
JPS6213381A (en) 1987-01-22

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