JP3691543B2 - Thermal recording material - Google Patents
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- JP3691543B2 JP3691543B2 JP12157395A JP12157395A JP3691543B2 JP 3691543 B2 JP3691543 B2 JP 3691543B2 JP 12157395 A JP12157395 A JP 12157395A JP 12157395 A JP12157395 A JP 12157395A JP 3691543 B2 JP3691543 B2 JP 3691543B2
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Description
【０００１】
【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、感熱記録層に電子供与性無色染料と電子受容性化合物とを含有する感熱記録材料に関する。
【０００２】
【従来の技術】
電子供与性無色染料と電子受容性化合物（顕色剤）とを使用した感熱記録材料は、既によく知られている。たとえば英国特許２，１４０，４４９、米国特許４，４８０，０５２、同４，４３６，９２０、特公昭６０−２３９９２、特開昭５７−１７９８３６、同６０−１２３５５６、同６０−１２３５５７などに詳しい。特に、感熱記録材料は特公昭４３−４１６０号等に詳しく、これら感熱記録システムはファクシミリ、プリンター等の多分野に応用され、ニーズが拡大している。ニーズ拡大の一例に感熱システムを用いて高画質にするため階調性の良好な感熱記録材料が求められている。
【０００３】
しかしながら、これを実現するためにはプリンター等の印加エネルギーが高エネルギーにシフトしているのが現状である。
【０００４】
従来、感熱記録層の透明性及び層の安定化を図るため、染料や顕色剤は乳化分散物の形で層中に含まれ、これらが、例えば、９０ｍｊ／ｍｍ2 以上の高エネルギーの印加を受けると、感熱記録層がただれて画像の鮮鋭度が低下したり、膜が剥がれたりする原因ともなっていた。しかしながら、これらの有効な防止手段は未だ見出されていなかった。
【０００５】
【発明が解決しようとする課題】
本発明の目的は、前記の如く、高エネルギーを印加した場合にも感熱記録層が影響を受けることなく、良好な画像形成を行なうことができる透明な感熱記録材料を提供することにある。
【０００６】
【課題を解決するための手段】
本発明者らは、鋭意検討の結果、感熱記録層に特定の構造を有するフェノール系化合物を添加することによって、高エネルギーの印加による感熱記録層への影響を防止しうるのみならず、感熱記録層に使用する乳化分散物の安定化にも寄与することを見出し、本発明を完成した。
【０００７】
即ち、本発明の感熱記録材料は、支持体上に感熱記録層を設けた感熱記録材料において、感熱記録層が電子供与性無色染料、下記一般式（１）で表される化合物の一種又は二種以上、及び、下記一般式（２）で表される電子受容性化合物を含有し、且つ、さらに、前記感熱記録層に下記一般式（３）、下記一般式（４）及び下記一般式（５）で表される化合物からなる群から選ばれる一種又は二種以上を含有することを特徴とする。
【０００８】
【化７】
式中、Ｒ1 は、メチル基を表し、Ｒ2 は、炭素数３〜８の分岐アルキル基を表し、Ｒ3 は、−（ＣＨ2 ）l −又は−（ＣＨ2 ）m −Ｏ−（ＣＨ2 ）n −を表し、ｌ、ｍ、ｎはそれぞれ１〜５の整数を表す。
【００１０】
本発明の感熱記録材料は、さらに前記電子受容性化合物として下記一般式（２）で表される化合物を含有し、さらに、前記感熱記録層に下記一般式（３）、下記一般式（４）及び下記一般式（５）で表される化合物からなる群から選ばれる一種又は二種以上を含有する。
【００１１】
【化８】
式中、ＭｅはＺｎ、Ｃａ又はＡｌを表し、ｎは２又は３の整数を表す。
【００１３】
【化９】
式中、Ｒ4 及びＲ7 はそれぞれ独立に炭素数３〜８の分岐アルキル基を表し、Ｒ5 及びＲ6 はそれぞれ独立に炭素数１〜８のアルキル基を表し、ｎは０又は１若しくは２の整数を表す。
【００１５】
【化１０】
式中、Ｒ8 及びＲ11はそれぞれ独立に炭素数３〜８の分岐アルキル基を表し、Ｒ9 及びＲ10はそれぞれ独立に炭素数１〜８のアルキル基を表し、ＸはＳ、Ｏ、ＳＯ2 、Ｓ2 又は下記一般式（４Ｂ）を表す。
【００１７】
【化１１】
式中、Ｒ12及びＲ13はそれぞれ独立に、水素原子又は炭素数１〜８のアルキル基を表し、ｎは０又は１〜３の整数を表す。
【００１９】
【化１２】
式中、Ｒ14及びＲ15はそれぞれ独立に炭素数３〜８の分岐アルキル基を表し、Ｒ16は炭素数１〜２０のアルキル基を表す。
【００２１】
請求項２に係る本発明の感熱記録材料は、前記電子供与性無色染料がマイクロカプセルに内包され、前記感熱記録層に含まれる一般式（１）乃至一般式（５）で表される化合物が乳化分散物として存在し、前記感熱記録層が実質的に透明であることを特徴とする。
【００２２】
請求項３に係る本発明の感熱記録材料は、前記電子受容性化合物として含まれる一般式（２）で表される化合物において、式中のＭｅがＺｎであることをを特徴とする。
【００２３】
以下に、本発明を詳細に説明する。
本発明に係る一般式（１）で表される化合物は、フェノール誘導体の２量体であり、式中、Ｒ1 は、メチル基を表し、Ｒ2 は、炭素数３〜８の分岐アルキル基を表し、Ｒ3 は、−（ＣＨ2 ）l −又は−（ＣＨ2 ）m −Ｏ−（ＣＨ2 ）n −を表し、ｌ、ｍ、ｎはそれぞれ１〜５の整数を表す。
【００２５】
Ｒ2 の炭素数３〜８の分岐アルキル基は、イソプロピル基、イソブチル基、sec −ブチル基、tert−ブチル基、２−エチルヘキシル基等が挙げられ、好ましくは、sec −ブチル基、tert−ブチル基、２−エチルヘキシル基等である。
【００２６】
また、Ｒ3 としては、−（ＣＨ2 ）3 −、−（ＣＨ2 ）2 −Ｏ−ＣＨ2 −、−（ＣＨ2 ）3 −Ｏ−ＣＨ2 −等が好ましい。
【００２７】
以下に、本発明の一般式（１）で表される化合物のうち好ましいものを下記式（１−Ｉ）、（１−II）及び（１−III ）として例示するが、これに限定されるものではない。
【００２８】
【化１３】
本発明に用いられる電子供与性無色染料には、特に制限はなく、公知の化合物を目的に応じて任意に選択して用いることができる。電子供与性無色染料の例としては、公知のトリフェニルメタンフタリド系化合物、フルオラン系化合物、フェノチアジン系化合物、インドリルフタリド系化合物、ロイコオーラミン系化合物、ローダミンラクタム系化合物、トリフェニルメタン系化合物、トリアゼン系化合物、スピロピラン系化合物、フルオレン系化合物など各種の化合物を挙げることができる。フタリド類の具体例は米国再発行特許明細書第２３，０２４号、米国特許明細書第３，４９１，１１１号、同第３，４９１，１１２号、同第３，４９１，１１６号および同第３，５０９，１７４号、フルオラン類の具体例は米国特許明細書第３，６２４，１０７号、同第３，６２７，７８７号、同第３，６４１，０１１号、同第３，４６２，８２８号、同第３，６８１，３９０号、同第３，９２０，５１０号、同第３，９５９，５７１号、スピロジピラン類の具体例は米国特許明細書第３，９７１，８０８号、ピリジン系およびピラジン系化合物類は米国特許明細書第３，７７５，４２４号、同第３，８５３，８６９号、同第４，２４６，３１８号、ロイコオーラミン系化合物の具体例は特開平４−１２６２８７号、フルオレン系化合物の具体例は特開昭６３−９４８７８号等に記載されている。
【００３０】
本発明に係る電子供与性無色染料の塗布量は特には限定されないが、０．１〜３．０ｇ／ｍ2 、特には１．０〜２．５ｇ／ｍ2 が好ましい。
【００３１】
本発明に用いられる電子供与性無色染料の顕色剤（即ち、電子受容性化合物）には特に制限はなく、例えば、ビスフェノール類を包含するフェノール誘導体、サリチル酸誘導体、ヒドロキシ安息香酸エステル等の電子受容性化合物を用いることができる。公知の電子受容性化合物としては、フェノール誘導体、サリチル酸誘導体、芳香族カルボン酸の金属塩、酸性白土、ベントナイト、ノボラック樹脂、金属処理ノボラック樹脂、金属錯体などが挙げられる。
【００３２】
これらの例は特公昭４０−９３０９号、特公昭４５−１４０３９号、特開昭５２−１４０４８３号、特開昭４８−５１５１０号、特開昭５７−２１０８８６号、特開昭５８−８７０８９号、特開昭５９−１１２８６号、特開昭６０−１７６７９５号、特開昭６１−９５９８８号等に記載されている。
【００３３】
これらのなかでも、前記の一般式（２）で表される化合物を電子受容性化合物として用いることが電子受容性化合物を含む乳化物の安定性付与の観点から好ましい。一般式（２）において、ＭｅはＺｎ、Ｃａ又はＡｌを表し、ｎは２又は３の整数を表すが、なかでも亜鉛塩（Ｍｅ＝Ｚｎ）で、ｎが２である下記式（２−Ｉ）で表される化合物が好ましい。
【００３４】
【化１４】
また、本発明の電子受容性化合物においては、前記一般式（２）で表される化合物に加えて、前記の如き公知の電子受容性化合物を併用することができる。
【００３６】
使用される電子供与性無色染料と電子受容性化合物の比は、重量比で１：１０から１：１の間が好ましく、１：５から２：３の間が特に好ましい。
【００３７】
さらに、この前記一般式（２）を電子受容性化合物に用いた場合、前記の一般式（３）乃至一般式（５）で表される化合物からなる群から選択される少なくとも１種の化合物を併用することにより、前記の効果が一層顕著になるため、特に、好ましい。これらの化合物は、記録材料の添加剤として知られているフェノール系の化合物である。
【００３８】
一般式（３）で示される化合物において、Ｒ4 及びＲ7 はそれぞれ独立に炭素数３〜８の分岐アルキル基を表すが、具体的には、イソプロピル基、イソブチル基、sec −ブチル基、tert−ブチル基、２−エチルヘキシル基等が挙げられ、好ましくは、sec −ブチル基、tert−ブチル基、２−エチルヘキシル基等である。また、Ｒ5 及びＲ6 はそれぞれ独立に炭素数１〜８のアルキル基を表し、一般式（１）のＲ1 におけるアルキル基と同様のものが例示されるが、特に、メチル基、エチル基、sec −ブチル基、tert−ブチル基等が好ましい。ｎは０又は１若しくは２の整数を表すが、ｎは０又は１であるものが好ましい。好ましい具体例としては下記式（３−Ｉ）で表されるものが挙げられる。
【００３９】
【化１５】
一般式（４）で示される化合物において、Ｒ8 及びＲ11はそれぞれ独立に炭素数３〜８の分岐アルキル基を表すが、これは前記一般式（３）で示される化合物におけるＲ4 及びＲ7 と同義であり、好ましくはsec −ブチル基、tert−ブチル基等である。また、Ｒ9 及びＲ10はそれぞれ独立に炭素数１〜８のアルキル基を表すが、これは前記一般式（３）で示される化合物におけるＲ5 及びＲ6 と同義であり、メチル基、エチル基、sec −ブチル基、tert−ブチル基等が好ましい。ＸはＳ、Ｏ、ＳＯ2 、Ｓ2 又は前記一般式（４Ｂ）を表すが、好ましくは、Ｓ、−（ＣＨ2 ）−等である。好ましい具体例としては、下記式（４−Ｉ）及び（４−II）で表されるものが挙げられる。
【００４１】
【化１６】
一般式（５）で示される化合物において、Ｒ14及びＲ15はそれぞれ独立に炭素数３〜８の分岐アルキル基を表すが、これは前記一般式（３）で示される化合物におけるＲ4 及びＲ7 と同義であり、好ましくはsec −ブチル基、tert−ブチル基等である。また、Ｒ16は炭素数１〜２０のアルキル基を表すが、具体的には、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、sec −ブチル基、ｎ−ペンチル基、イソペンチル基、ｎ−ヘキシル基、ｎ−オクチル基、２−エチルヘキシル基、ｎ−デシル基、ｎ−ドデシル基、シクロペンチル基、シクロヘキシル基、ベンジル基、２−フェネチル基、１−フェネチル基、フェニル基等が挙げられる。また、好ましい例示化合物としては、下記式（５−Ｉ）で表される化合物が挙げられる。
【００４３】
【化１７】
本発明の感熱記録材料には、前記化合物に加えて従来より公知の紫外線吸収剤、蛍光増白剤、酸化防止剤と併用してもよい。
【００４５】
併用できる紫外線吸収剤として好ましいものは、ベンゾフェノン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤、サリチル酸系紫外線吸収剤、シアノアクリレート系紫外線吸収剤、オキザリックアシッドアニリド系紫外線吸収剤などが挙げられる。これらの例は特開昭４７−１０５３７号、同５８−１１１９４２号、同５８−２１２８４４号、同５９−１９９４５号、同５９−４６６４６号、同５９−１０９０５５号、同６３−５３５４４号、特公昭３６−１０４６６号、同４２−２６１８７号、同４８−３０４９２号、同４８−３１２５５号、同４８−４１５７２号、同４８−５４９６５号、同５０−１０７２６号、米国特許２，７１９，０８６号、同３，７０７，３７５号、同３，７５４，９１９号、同４，２２０，７１１号などに記載されている。
【００４６】
併用できる蛍光増白剤として好ましいものは、クマリン系蛍光増白剤などが挙げられる。これらの例は特公昭４５−４６９９号、同５４−５３２４号などに記載されている。
【００４７】
併用できる酸化防止剤として好ましいものは、ヒンダードアミン系酸化防止剤、ヒンダードフェノール系酸化防止剤、アニリン系酸化防止剤、キノリン系酸化防止剤などが挙げられる。これらの例は特開昭５９−１５５０９０号、同６０−１０７３８３号、同６０−１０７３８４号、同６１−１３７７７０、同６１−１３９４８１号、同６１−１６０２８７などに記載されている。
【００４８】
併用できる紫外線吸収剤、蛍光増白剤、酸化防止剤の使用量としては０．０５〜１．０ｇ／ｍ2 、特には０．１〜０．４ｇ／ｍ2 が好ましい。
【００４９】
電子供与性無色染料および電子受容性化合物の使用量は所望の塗布厚、感圧記録紙の形態、カプセルの製法、その他の条件によるのでその条件に応じて適宜選べばよい。当業者がこの使用量を決定することは容易である。
【００５０】
感熱紙に用いる場合には、特開昭６２−１４４９８９号、特開平１−８７２９１号明細書等に記載されているような形態をとる。具体的には，電子供与性無色染料および電子受容性化合物は分散媒中で１０μ以下、好ましくは３μ以下の粒径まで粉砕分散して用いる。分散媒としては、一般に０．５ないし１０％程度の濃度の水溶高分子水溶液が用いられ分散はボールミル、サンドミル、横型サンドミル、アトライタ、コロイダルミル等を用いて行われる。
【００５１】
その際、熱応答性を改良するために熱可融性物質を感熱発色層に含有させることができる。熱可融性物質としては、芳香族エーテル、チオエーテル、エステル及び又は脂肪族アミド又はウレイドなどがその代表である。
【００５２】
これらの例は特開昭５８−５７９８９号、同５８−８７０９４号、同６１−５８７８９号、同６２−１０９６８１号、同６２−１３２６７４号、同６３−１５１４７８号、同６３−２３５９６１号、特開平２−１８４４８９号、同２−２１５５８５号などに記載されている。
【００５３】
これらは電子供与性無色染料と同時又は電子受容性化合物と同時に微分散して用いられる。これらの使用量、電子受容性化合物に対して、２０％以上３００％以下の重量比で添加され、特に４０％以上１５０％以下が好ましい。
【００５４】
このようにして得られた塗液には、さらに種々の要求を満たす為に必要に応じて添加剤が加えられる。添加剤の例としては記録時の記録ヘッドの汚れを防止するために、バインダー中に無機顔料、ポリウレアフィラー等の吸油性物質を分散させておくことが行われ、さらにヘッドに対する離型性を高めるために脂肪酸、金属石鹸などが添加される。したがって一般には、発色に直接寄与する電子供与性無色染料、電子受容性化合物の他に、熱可融性物質、顔料、ワックス、帯電防止剤、紫外線吸収剤、消泡剤、導電剤、蛍光染料、界面活性剤などの添加剤が支持体上に塗布され、記録材料が構成されることになる。さらに必要に応じて感熱記録層の表面に保護層を設けてもよい。
【００５５】
通常、電子供与性無色染料及び電子受容性化合物は、バインダー中に分散して塗布される。バインダーとしては水溶性のものが一般的であり、ポリビニルアルコ−ル、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、エピクロルヒドリン変性ポリアミド、エチレン−無水マレイン酸共重合体、スチレン−無水マレイン酸共重合体、イソブチレン−無水マレインサリチル酸共重合体、ポリアクリル酸、ポリアクリル酸アミド、メチロール変性ポリアクリルアミド、デンプン誘導体、カゼイン、ゼラチン等があげられる。またこれらのバインダーに耐水性を付与する目的で耐水化剤を加えたり、疎水性ポリマーのエマルジョン、具体的には、スチレン−ブタジエンゴムラテックス、アクリル樹脂エマルジョン等を加えることもできる。これらの使用量としては、０．４〜５ｇ／ｍ2 が好ましく、さらには０．８〜１．６ｇ／ｍ2 が好ましい。
【００５６】
得られた感熱塗液は、上質紙、下塗り層を有する上質紙、合成紙、プラスチックフィルム等に塗布される。この際ＪＩＳ−８１１９で規定される平滑度が５００秒以上特に８００秒以上の支持体を用いるのがドット再現性の点から特に好ましい。
【００５７】
本発明の記録材料においてはその必要に応じて、公知のワックス、帯電防止剤、消泡剤、導電剤、蛍光染料、界面活性剤、紫外線吸収剤プレカーサーなど各種添加剤を使用することができる。
【００５８】
本発明の記録材料には必要に応じて記録層の表面に保護層を設けてもよい。保護層は必要に応じて二層以上積層してもよい。保護層に用いる材料としては、ポリビニルアルコール、カルボキシ変性ポリビニルアルコール、酢酸ビニル−アクリルアミド共重合体、ケイ素変性ポリビニルアルコール、澱粉、変性澱粉、メチルセルロース、カルボキシメチルセルロース、ヒドロキシメチルセルロース、ゼラチン類、アラビアゴム、カゼイン、スチレン−マレイン酸共重合体加水分解物、スチレン−マレイン酸共重合物ハーフエステル加水分解物、イソブチレン−無水マレイン酸共重合体加水分解物、ポリアクリルアミド誘導体、ポリビニルピロリドン、ポリスチレンスルホン酸ソーダ、アルギン酸ソーダなどの水溶性高分子化合物、及びスチレン−ブタジエンゴムラテックス、アクリロニトリル−ブタジエンゴムラテックス、アクリル酸メチル−ブタジエンゴムラテックス、酢酸ビニルエマルジョン等のラテックス類が用いられる。保護層の水溶性高分子化合物を架橋してより一層保存安定性を向上させることもでき、その架橋剤としては公知の架橋剤を使用することができる。具体的にはＮ−メチロール尿素、Ｎ−メチロールメラミン、尿素−ホルマリン等の水溶性初期縮合物、グリオキザール、グルタルアルデヒド等のジアルデヒド化合物類、硼酸、硼砂等の無機系架橋剤、ポリアミドエピクロルヒドリンなどが挙げられる。保護層には、さらに公知の顔料、金属石鹸、ワックス、界面活性剤などを使用することもできる。保護層の塗布量は０．２〜５ｇ／ｍ2 が好ましく、さらには１．０〜３．０ｇ／ｍ2 が好ましい。またその膜厚は０．２〜５μｍが好ましく、特に１．０〜３μｍが好ましい。
【００５９】
本発明の記録材料に保護層を使用する場合、保護層中に公知のＵＶ吸収剤やＵＶ吸収剤プレカーサーを含有してもよい。
【００６０】
本発明の記録材料に使用できる支持体としては、酸性紙、中性紙、コート紙、プラスチックフィルムラミネート紙、合成紙、プラスチックフィルムなどを使用することができる。さらにこれら支持体に公知の下塗り層を設けてもよい。この下塗り層は上記保護層と同様にして設けることができる。
【００６１】
支持体のカールバランスを補正するため或いは、裏面からの耐薬品性を向上させる目的で、バックコート層を設けてもよく、また裏面に接着剤層を介して剥離紙を組み合わせてラベルの形態にしてもよい。このバックコート層についても上記保護層と同様にして設けることができる。
【００６２】
【実施例】
以下実施例によって本発明を記述するが本発明はこれにより限定されるものではない。
【００６３】
又、特に断らない限り、以下に記載する部及び％はそれぞれ重量部及び重量％を表す。
（実施例１）
電子供与性無色染料を内包したカプセル液（ＭＣ１）の調製
下記式（Ｅ−１）（Ｅ−２）（Ｅ−３）（Ｅ−４）（Ｅ−５）（Ｅ−６）及び（Ｅ−７）で表わされる化合物、それぞれ１０．０ｇ、１．３ｇ、２．０ｇ、２．７ｇ、１．３ｇ、０．１ｇ及び０．４ｇを酢酸エチル２０ｇ中で加熱溶解させ、４０°Ｃまで徐冷させた後、タケネートＤ１１０Ｎ（商品名：武田薬品製カプセル壁剤）２．０ｇ及びタケネートＤ１２７Ｎ（同上：武田薬品製）１１．６ｇ及びｎ−ブタノール０．４ｇを添加し４０°Ｃで４０分間撹拌させた。
【００６４】
【化１８】
得られた溶液をポリビニルアルコール８％溶液（ＰＶＡ２１７Ｃ：商品名、クラレ製）４０ｇと水１３ｇを混合した水相に添加した後、エースホモジナイザー（商品名：日本精機（株）製）を用い、１００００ｒｐｍで５分間乳化分散を行った。
【００６６】
得られた乳化液に更に水７０ｇ及びテトラエチレンペンタミン０．５ｇを添加した後、６０°Ｃで３時間カプセル化反応を行わせて、平均粒子径が０．６μｍのカプセル液（ＭＣ１）を得た。
【００６７】
なお平均粒子径はレーザー回析粒度分布測定装置（ＬＡ７００：商品名、（株）堀場製作所製）を用いて測定した５０％体積平均粒子径である。
【００６８】
以下において、特に断らない限り、平均粒子径は上記の５０％体積平均粒子径を表す。
電子供与性無色染料を内包したカプセル液（ＭＣ２）の調製
前記式（Ｅ−１）（Ｅ−２）（Ｅ−３）（Ｅ−４）（Ｅ−５）（Ｅ−６）及び（Ｅ−７）の化合物、それぞれ、９．５ｇ、１．２ｇ、１．８ｇ、４．６ｇ、１．０ｇ、１．０ｇ及び０．４ｇを酢酸エチル２０ｇの中で加熱溶解させ５０°Ｃまで徐冷させた後、タケネートＤ１４０Ｎ（商品名：武田薬品製カプセル壁剤）１１．４ｇ及びバーノックＤ７５０（商品名：大日本インキ（株）製カプセル壁剤）１．３ｇを添加し撹拌させた。
【００６９】
得られた溶液を、ポリビニルアルコール８％溶液（ＰＶＡ２１７Ｃ、クラレ製）４０ｇと水１３ｇを混合した水相に添加した後、エースホモジナイザーを用い、１００００ｒｐｍで５分間乳化分散を行った。
【００７０】
得られた乳化液に更に水８０ｇ及びテトラエチレンペンタミン０．８ｇを添加した後、６０°Ｃで３時間カプセル化反応を行わせて平均粒子径が０．６μｍのカプセル液（ＭＣ２）を得た。
電子受容性化合物（顕色剤）乳化分散液（Ａ）の調製
前記式（２−Ｉ）（３−Ｉ）及び（１−Ｉ）で表わされる化合物、それぞれ１８．７ｇ、１３．１ｇ及び５．６ｇをＴＣＰ（商品名：大八化学社製オイル）１．０ｇ、ＤＥＭ（商品名：大八化学社製オイル）０．５ｇ及び酢酸エチル２０ｇを混合した溶液に溶解させた。
【００７１】
得られた溶液をポリビコルアルコール１５％溶液（ＰＶＡ２０５Ｃ：クラレ社製）２５．０ｇ及びポリビニルアルコール８％溶液（ＰＶＡ２１７Ｃ：クラレ社製）４６ｇ、ドデシルスルホン酸ナトリウム０．５ｇ及び水７５．０ｇを混合した水相に投入し、エースホモジナイザーを使用し１００００ｒｐｍで３分間乳化し、平均粒子径が０．６μｍの電子受容性化合物（以下、適宜顕色剤と称する）乳化分散液（Ａ）を得た。
保護層用塗布液の調製
水３０ｇ、ポリビニルアルコール６％水溶液（ＰＶＡ１２４Ｃ：商品名、クラレ株式会社製）２０ｇ、スルホコハク酸ジオクチルのナトリウム塩２％水溶液０．３ｇ、カオリン分散物（ポリビニルアルコール３ｇを水１００ｇに混合した液にカオリン３５ｇをポールミルで分散させたもの）３．０ｇ及びハイドリンＺ（商品名：中京油脂社製）０．５ｇを混合して保護層用塗布液を得た。
下塗層を設けた透明支持体の調製
色度座標（ＪＩＳ Ｚ８７０１）が、Ａ（ｘ＝０．２８０５，ｙ＝０．３００５）、Ｂ（ｘ＝０．２８２０，ｙ＝０．２９７０）、Ｃ（ｘ＝０．２８８５，ｙ＝０．３０１５）、Ｄ（ｘ＝０．２８７０，ｙ＝０．３０４０）の４点を頂点とする四角形の領域内で着色された、厚さ１７５μｍのポリエチレンテレフタレートの一方の面にＳＢＲラテックスを固形分重量で０．３ｇ／ｍ2 となるように塗布した後、下記の下塗層用塗布液を片面当たりの固形分重量が０．１ｇ／ｍ2 となるように塗布して、下塗層を設けた透明支持体を得た。
下塗層用塗布液の調製
ゼラチン５％水溶液（＃８１０：商品名、新田ゼラチン社製）２００ｇ、粒子径２μｍのポリメチルメタクリレート樹脂粒子を５％分散したゼラチン分散物０．５ｇ、１，２−ベンゾチアゾリン−３−オン３％水溶液１．０ｇ、スルフォン酸ジ（２−エチル）ヘキシル２％水溶液１０ｇを混合して下塗り層塗布液を得た。
感熱記録層用塗布液（１）の調製
既に調製したカプセル液（ＭＣ１）１．５ｇ、カプセル液（ＭＣ２）３．５ｇ顕色剤乳化分散液（Ａ）（乳化分散後１日放置したもの）１５ｇ及び水１０ｇを混合して感熱記録用塗布液（１）を得た。
感熱記録材料の調製
既に調製した下塗り層を設けた透明支持体の一方の面に感熱記録用塗布液（１）を固形分重量で１４ｇ／ｍ2 となるように塗布・乾燥した後、その上に調製済の保護層用塗布液を固形分重量で２．５ｇ／ｍ2 となる様に塗布・乾燥して本発明の感熱記録材料を得た。
印字方法及び性能評価
得られた感熱記録材料にサーマルプリンター（ＴＲＴ−１６：商品名、長野日本無線（株）製）を用い、サーマルヘッドの印加熱エネルギーを変えて画像（以下、ステップエッジと呼ぶ）を記録した。
（実施例２）
実施例１で使用した感熱記録様塗布液（１）中の顕色剤乳化分散液（Ａ）を以下に記す（Ｂ）液に変えた以外同様の方法で感熱記録用塗布液（２）を作成した以外同様な方法で本発明の感熱記録材料を得た。
顕色剤乳化分散液（Ｂ）の調製
実施例１中に記載の顕色剤乳化分散液（Ａ）の調製方法において、前記式（３−Ｉ）で表される化合物を前記式（４−Ｉ）で表される化合物に変えた以外同様な方法で平均粒子径０．６μｍの顕色剤乳化分散液（Ｂ）を作成した。
印字方法及び性能評価
実施例２の感熱記録材料も実施例１記載同様の方法、性能評価を行った。
（実施例３）
実施例１で使用した感熱記録用塗布液（１）中の顕色剤乳化分散液（Ａ）を以下に記す（Ｃ）液に変えた以外同様の方法で感熱記録用塗布液（３）を作成した以外同様な方法で本発明の感熱記録材料を得た。
顕色剤乳化分散液（Ｃ）の調製
実施例１中に記載の顕色剤乳化分散液（Ａ）の調製方法において、前記式（３−Ｉ）で表される化合物を前記式（４−II）で表される化合物に変えた以外同様な方法で平均粒子径０．６μｍの顕色剤乳化分散液（Ｃ）を作成した。
印字方法及び性能評価
実施例３の感熱記録材料も実施例１記載同様の方法、性能評価を行った。
（実施例４）
実施例１で使用した感熱記録用塗布液（１）中の顕色剤乳化分散液（Ａ）を以下に記す（Ｄ）液に変えた以外同様の方法で感熱記録用塗布液（４）を作成した以外同様な方法で本発明の感熱記録材料を得た。
顕色剤乳化分散液（Ｄ）の調製
実施例１中に記載の顕色剤乳化分散液（Ａ）の調製方法において、前記式（３−Ｉ）で表される化合物を前記式（５−Ｉ）で表される化合物に変えた以外同様な方法で平均粒子径０．６μｍの顕色剤乳化分散液（Ｄ）を作成した。
印字方法及び性能評価
実施例４の感熱記録材料も実施例１記載同様の方法、性能評価を行った。
（実施例５）
実施例１で使用した感熱記録用塗布液（１）中の顕色剤乳化分散液（Ａ）を以下に記す（Ｅ）液に変えた以外同様の方法で感熱記録用塗布液（５）を使用した以外同様な方法で本発明の感熱記録材料を得た。
顕色剤乳化分散液（Ｅ）の調製
実施例１中に記載の顕色剤乳化分散液（Ａ）の調製方法において、前記式（２−Ｉ）、（３−Ｉ）及び（１−Ｉ）で表わされる化合物、それぞれ１８．７ｇ、１３．１ｇ及び５．６ｇであるのを、前記式（２−Ｉ）、（３−Ｉ）、（１−Ｉ）、（４−Ｉ）、（４−II）及び（５−Ｉ）、それぞれ１６．２ｇ、１０．４ｇ、３．６ｇ、３．５ｇ、２．２ｇ、及び１．４ｇに変えた以外同様な方法で平均粒子径０．６μｍの顕色剤乳化分散液（Ｅ）を作成した。
印字方法及び性能評価
実施例５の感熱記録材料も実施例１記載同様の方法、性能評価を行った。
（比較例１）
実施例５で使用した感熱記録用塗布液（５）中の顕色剤乳化分散液（Ｅ）を以下に記す（Ｆ）液に変えた以外同様の方法で感熱記録用塗布液（６）を使用した以外同様な方法で本発明の感熱記録材料を得た。
顕色剤乳化分散液（Ｆ）の調製
実施例１中に記載の顕色剤乳化分散液（Ａ）の調製方法において、前記式（２−Ｉ）、（３−Ｉ）及び（１−Ｉ）で表わされる化合物、それぞれ１８．７ｇ、１３．１ｇ及び５．６ｇであるのを、前記式（２−Ｉ）、（３−Ｉ）、（４−Ｉ）、（４−II）及び（５−Ｉ）、それぞれ１７．９ｇ、１１．６ｇ、３．９ｇ、２．４ｇ及び１．６ｇに変えた以外同様な方法で平均粒子径０．６μｍの顕色剤乳化分散液（Ｅ）を作成した。
印字方法及び性能評価
実施例５の感熱記録材料も実施例１記載同様の方法、性能評価を行った。
（比較例２）
実施例１で使用した感熱記録用塗布液（１）中の顕色剤乳化分散液（Ａ）を以下に記す（Ｇ）液に変えて作成した。
顕色剤乳化分散液（Ｇ）の調製
実施例１中に記載の顕色剤乳化分散液（Ａ）の調製方法において、前記式（２−Ｉ）、（３−Ｉ）及び（１−Ｉ）で表わされる化合物、それぞれ１８．７ｇ、１３．１ｇ及び５．６ｇであるのを、前記式（２−Ｉ）及び（３−Ｉ）で表わされる化合物、それぞれ、１８．７ｇ、１８．７ｇに変えた以外同様な方法で平均粒子径０．６μｍの顕色剤乳化分散液（Ｇ）を作成した。
１日経時後の顕色剤乳化分散液の様子
顕色剤乳化分散液（Ｇ）を室温にて１日静置させておいたが１日後この液は析出を生じていた。よってこの（Ｇ）液をカプセル液（ＭＣ１）及び（ＭＣ２）と混ぜ塗布しても透明な感熱記録材料を提供できず、以降の印字及び性能評価を打ち切った。
（比較例３）
実施例１で使用した感熱記録用塗布液（１）中の顕色剤乳化分散液（Ａ）を以下に記す（Ｉ）液に変えて作成した。
顕色剤乳化分散液（Ｉ）の調製
実施例１中に記載の顕色剤乳化分散液の調製方法において、前記式（２−Ｉ）、（３−Ｉ）及び（１−Ｉ）で表わされる化合物、それぞれ、１８．７ｇ、１３．１ｇ及び５．６ｇであるのを、前記式（２−Ｉ）及び（４−Ｉ）で表わされる化合物、それぞれ、１８．７ｇ、１８．７ｇに変えた以外同様な方法で平均粒子径０．６μｍの顕色剤乳化分散液（Ｉ）を作成した。
１日経時後の顕色剤乳化分散液の様子
顕色剤乳化分散液（Ｉ）を室温にて１日静置させておいたが１日後この液は析出を生じていた。よってこの（Ｉ）液をカプセル液（ＭＣ１）及び（ＭＣ２）と混ぜ塗布しても透明な感熱記録材料を提供できず、以降の印字及び性能評価を打ち切った。
（比較例４）
実施例１で使用した感熱記録用塗布液（１）中の顕色剤乳化分散液（Ａ）を以下に記す（Ｊ）液に変えて作成した。
顕色剤乳化分散液（Ｊ）の調製
実施例１中に記載の顕色剤乳化分散液の調製方法において、前記式（２−Ｉ）、（３−Ｉ）及び（１−Ｉ）で表わされる化合物、それぞれ、１８．７ｇ、１３．１ｇ及び５．６ｇであるのを、前記式（２−Ｉ）及び（４−II）で表わされる化合物、それぞれ、１８．７ｇ、１８．７ｇに変えた以外同様な方法で平均粒子径０．６μｍの顕色剤乳化分散液（Ｊ）を作成した。
１日経時後の顕色剤乳化分散液の様子
顕色剤乳化分散液（Ｊ）を室温にて１日静置させておいたが１日後この液は析出を生じていた。よってこの（Ｊ）液をカプセル液（ＭＣ１）及び（ＭＣ２）と混ぜ塗布しても透明な感熱記録材料を提供できず、以降の印字及び性能評価を打ち切った。
（比較例５）
実施例１で使用した感熱記録用塗布液（１）中の顕色剤乳化分散液（Ａ）を以下に記す（Ｋ）液に変えて作成した。
顕色剤乳化分散液（Ｋ）の調製
実施例１中に記載の顕色剤乳化分散液の調製方法において、前記式（２−Ｉ）、（３−Ｉ）及び（１−Ｉ）で表わされる化合物、それぞれ、１８．７ｇ、１３．１ｇ及び５．６ｇであるのを、前記式（２−Ｉ）及び（５−Ｉ）で表わされる化合物、それぞれ、１８．７ｇ、１８．７ｇに変えた以外同様な方法で平均粒子径０．６μｍの顕色剤乳化分散液（Ｋ）を作成した。
１日経時後の顕色剤乳化分散液の様子
顕色剤乳化分散液（Ｋ）を室温にて１日静置させておいたが１日後この液は析出を生じていた。よってこの（Ｋ）液をカプセル液（ＭＣ１）及び（ＭＣ２）と混ぜ塗布しても透明な感熱記録材料を提供できず、以降の印字及び性能評価を打ち切った。
【００７２】
顕色剤乳化分散液の安定性評価
実施例１〜５及び比較例１〜６の顕色剤乳化分散液を作成した後、経時１日における状態を目視で観察した結果を下記表１に示す。
【００７３】
【表１】
表１に明らかなように、本発明の一般式（１）で表される化合物を顕色剤（電子受容性化合物）とともに添加した実施例１〜５の顕色剤乳化物は、乳化安定性が良好で析出を生じなかったが、本発明の一般式（１）で表される化合物を添加していない比較例２〜６の顕色剤乳化物は１日経時後に析出が生じたため、染料含有カプセル液と混ぜて塗布しても透明な感熱記録材料を提供できず、使用に適さないことがわかった。
【００７５】
次に、１日経時した後に析出を生じていない顕色剤乳化分散液（実施例１〜５及び比較例１）を用いた感熱記録材料について、サーマルプリンター（ＴＲＴ−１６）を用いて、印加エネルギー９０又は１００ｍｊ／ｍｍ2 として印字した場合のステップエッジの様子を下記表２に示す。
【００７６】
【表２】
表２に明らかなように、本発明の一般式（１）で表される化合物を電子受容性化合物とともに添加した実施例１〜５の感熱記録材料は、９０ｍｊ／ｍｍ2 で印字したところ塗膜状態は良好であった。また、１００ｍｊ／ｍｍ2 で印字したところ実施例５感熱記録材料の塗膜状態は良好であり、実施例１〜４の感熱記録材料にもほとんどはがれは見られず実用上問題のない印字レベルであったが、比較例１の感熱記録材料は前記いずれの条件においても塗膜にはがれが発生し、良好な印字は得られなかった。
【００７８】
【発明の効果】
本発明の感熱記録材料は、前記の如く、高エネルギーを印加した場合にも感熱記録層が影響を受けることなく、良好な画像形成を行なうことができ、電子受容性化合物の乳化状態が長期間安定であるという優れた効果を示した。[0001]
[Industrial application fields]
The present invention relates to a heat-sensitive recording material, and more particularly to a heat-sensitive recording material containing an electron-donating colorless dye and an electron-accepting compound in a heat-sensitive recording layer.
[0002]
[Prior art]
A heat-sensitive recording material using an electron-donating colorless dye and an electron-accepting compound (developer) is already well known. For example, it is detailed in British Patent 2,140,449, U.S. Pat. No. 4,480,052, No. 4,436,920, JP-B-60-23939, JP-A-57-179836, JP-A-60-123556, and JP-A-60-123557. In particular, the heat-sensitive recording material is described in detail in Japanese Examined Patent Publication No. 43-4160. These heat-sensitive recording systems are applied to various fields such as facsimiles and printers, and the needs are expanding. As an example of expanding needs, there is a need for a heat-sensitive recording material with good gradation in order to achieve high image quality using a heat-sensitive system.
[0003]
However, in order to realize this, the current situation is that the applied energy of a printer or the like is shifted to high energy.
[0004]
Conventionally, in order to achieve transparency of the heat-sensitive recording layer and stabilization of the layer, a dye and a developer are included in the layer in the form of an emulsified dispersion, and these are, for example, 90 mj / mm.2When the above high energy is applied, the heat-sensitive recording layer is struck and the sharpness of the image is lowered or the film is peeled off. However, these effective prevention means have not yet been found.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a transparent heat-sensitive recording material capable of forming a good image without being affected by the heat-sensitive recording layer even when high energy is applied as described above.
[0006]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have not only been able to prevent the influence of the application of high energy on the thermal recording layer by adding a phenolic compound having a specific structure to the thermal recording layer, but also thermal recording. The present invention was completed by finding that it contributes to the stabilization of the emulsified dispersion used in the layer.
[0007]
That is, the heat-sensitive recording material of the present invention is a heat-sensitive recording material in which a heat-sensitive recording layer is provided on a support, and the heat-sensitive recording layer is an electron donating colorless dye.,underOne or more of the compounds represented by the general formula (1) and the following general formula (2)Electron acceptability1 type or 2 or more types chosen from the group which contains a compound and is further comprised to the said thermosensitive recording layer from the compound represented by following General formula (3), following General formula (4), and following General formula (5) It is characterized by containing.
[0008]
[Chemical 7]
Where R1Represents a methyl group and R2Represents a branched alkyl group having 3 to 8 carbon atoms, and RThreeIs-(CH2)l-Or- (CH2)m-O- (CH2)n-, And l, m, and n each represent an integer of 1 to 5.
[0010]
The heat-sensitive recording material of the present invention further comprisesThe electron-accepting compoundAsA group comprising a compound represented by the following general formula (2), and further comprising a compound represented by the following general formula (3), the following general formula (4) and the following general formula (5) in the thermosensitive recording layer. One or more selected fromContaining.
[0011]
[Chemical 8]
In the formula, Me represents Zn, Ca or Al, and n represents an integer of 2 or 3.
[0013]
[Chemical 9]
Where RFourAnd R7Each independently represents a branched alkyl group having 3 to 8 carbon atoms;FiveAnd R6Each independently represents an alkyl group having 1 to 8 carbon atoms, and n represents 0 or an integer of 1 or 2.
[0015]
[Chemical Formula 10]
Where R8And R11Each independently represents a branched alkyl group having 3 to 8 carbon atoms;9And RTenEach independently represents an alkyl group having 1 to 8 carbon atoms, and X represents S, O, SO.2, S2Or the following general formula (4B) is represented.
[0017]
Embedded image
Where R12And R13Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 0 or 1 to 3.
[0019]
Embedded image
Where R14And R15Each independently represents a branched alkyl group having 3 to 8 carbon atoms;16Represents an alkyl group having 1 to 20 carbon atoms.
[0021]
Claim2In the heat-sensitive recording material of the present invention, the electron-donating colorless dye is encapsulated in microcapsules, and the compounds represented by the general formulas (1) to (5) contained in the heat-sensitive recording layer are emulsified dispersions. And the heat-sensitive recording layer is substantially transparent.
[0022]
The heat-sensitive recording material of the present invention according to claim 3 is the electron-accepting compound.AsIn the compound represented by the general formula (2), Me in the formula is Zn.
[0023]
The present invention is described in detail below.
The compound represented by the general formula (1) according to the present invention is a dimer of a phenol derivative, in which R1IsMethyl groupRepresents R2Represents a branched alkyl group having 3 to 8 carbon atoms, and RThreeIs-(CH2)l-Or- (CH2)m-O- (CH2)n-, And l, m, and n each represent an integer of 1 to 5.
[0025]
R2Examples of the branched alkyl group having 3 to 8 carbon atoms include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, etc., preferably sec-butyl group, tert-butyl group, And 2-ethylhexyl group.
[0026]
RThreeAs-(CH2)Three-,-(CH2)2-O-CH2-,-(CH2)Three-O-CH2-Etc. are preferable.
[0027]
In the following, among the compounds represented by the general formula (1) of the present invention, preferred ones are exemplified as the following formulas (1-I), (1-II) and (1-III), but are not limited thereto. It is not a thing.
[0028]
Embedded image
There is no restriction | limiting in particular in the electron-donating colorless dye used for this invention, A well-known compound can be arbitrarily selected and used according to the objective. Examples of electron-donating colorless dyes include known triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indolyl phthalide compounds, leucooramine compounds, rhodamine lactam compounds, triphenylmethane compounds Various compounds such as compounds, triazene compounds, spiropyran compounds, and fluorene compounds can be exemplified. Specific examples of the phthalides include US Reissue Patent No. 23,024, US Patent Nos. 3,491,111, 3,491,112, 3,491,116 and No. 3,509,174, specific examples of fluoranes are described in U.S. Pat. Nos. 3,624,107, 3,627,787, 3,641,011, and 3,462,828. Nos. 3,681,390, 3,920,510, 3,959,571, specific examples of spirodipyrans are described in U.S. Pat. No. 3,971,808, Examples of pyrazine compounds are US Pat. Nos. 3,775,424, 3,853,869, 4,246,318, and specific examples of leucooramine compounds are described in JP-A-4-126287. Ingredients for fluorene compounds Examples are described in JP-A-63-94878 Patent like.
[0030]
The coating amount of the electron donating colorless dye according to the present invention is not particularly limited, but is 0.1 to 3.0 g / m.2 , Especially 1.0-2.5 g / m2 Is preferred.
[0031]
The electron-donating colorless dye developer (ie, electron-accepting compound) used in the present invention is not particularly limited, and examples thereof include electron acceptors such as phenol derivatives including bisphenols, salicylic acid derivatives, hydroxybenzoic acid esters, and the like. Can be used. Known electron-accepting compounds include phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acidic clay, bentonite, novolac resins, metal-treated novolac resins, metal complexes, and the like.
[0032]
Examples of these are JP-B-40-9309, JP-B-45-14039, JP-A-52-140483, JP-A-48-51010, JP-A-57-210886, JP-A-58-87089, JP-A-59-11286, JP-A-60-176795, JP-A-61-95988 and the like.
[0033]
Among these, it is preferable to use the compound represented by the general formula (2) as the electron-accepting compound from the viewpoint of imparting stability of the emulsion containing the electron-accepting compound. In the general formula (2), Me represents Zn, Ca or Al, and n represents an integer of 2 or 3. Among them, a zinc salt (Me = Zn) in which n is 2, the following formula (2-I ) Is preferred.
[0034]
Embedded image
Moreover, in the electron-accepting compound of the present invention, a known electron-accepting compound as described above can be used in combination with the compound represented by the general formula (2).
[0036]
The ratio of the electron-donating colorless dye and the electron-accepting compound used is preferably 1:10 to 1: 1 by weight, particularly preferably 1: 5 to 2: 3.
[0037]
Further, when the general formula (2) is used as an electron-accepting compound, at least one compound selected from the group consisting of the compounds represented by the general formula (3) to the general formula (5) is used. The combined use is particularly preferable because the above effect becomes more remarkable. These compounds are phenolic compounds known as additives for recording materials.
[0038]
In the compound represented by the general formula (3), RFourAnd R7Each independently represents a branched alkyl group having 3 to 8 carbon atoms, and specific examples include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, etc. sec-butyl group, tert-butyl group, 2-ethylhexyl group and the like. RFiveAnd R6Each independently represents an alkyl group having 1 to 8 carbon atoms, and R in the general formula (1)1Examples of the alkyl group are the same as those described above, and a methyl group, an ethyl group, a sec-butyl group, a tert-butyl group and the like are particularly preferable. n represents 0 or an integer of 1 or 2, and n is preferably 0 or 1. Preferable specific examples include those represented by the following formula (3-I).
[0039]
Embedded image
In the compound represented by the general formula (4), R8And R11Each independently represents a branched alkyl group having 3 to 8 carbon atoms, and this represents R in the compound represented by the general formula (3).FourAnd R7And preferably a sec-butyl group, a tert-butyl group, or the like. R9And RTenEach independently represents an alkyl group having 1 to 8 carbon atoms, and this represents R in the compound represented by the general formula (3).FiveAnd R6And a methyl group, an ethyl group, a sec-butyl group, a tert-butyl group and the like are preferable. X is S, O, SO2, S2Or the general formula (4B), preferably S, — (CH2)-Etc. Preferable specific examples include those represented by the following formulas (4-I) and (4-II).
[0041]
Embedded image
In the compound represented by the general formula (5), R14And R15Each independently represents a branched alkyl group having 3 to 8 carbon atoms, and this represents R in the compound represented by the general formula (3).FourAnd R7And preferably a sec-butyl group, a tert-butyl group, or the like. R16Represents an alkyl group having 1 to 20 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, n-pentyl group, Isopentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, cyclopentyl group, cyclohexyl group, benzyl group, 2-phenethyl group, 1-phenethyl group, phenyl group, etc. Is mentioned. Moreover, as a preferable example compound, the compound represented by a following formula (5-I) is mentioned.
[0043]
Embedded image
The heat-sensitive recording material of the present invention may be used in combination with conventionally known ultraviolet absorbers, fluorescent brighteners and antioxidants in addition to the above compounds.
[0045]
Preferred examples of the UV absorber that can be used in combination include benzophenone UV absorbers, benzotriazole UV absorbers, salicylic acid UV absorbers, cyanoacrylate UV absorbers, and oxalic acid anilide UV absorbers. Examples of these are JP-A-47-10537, 58-111942, 58-21284, 59-19945, 59-46646, 59-109055, 63-53544, and SHOKO. 36-10466, 42-26187, 48-30492, 48-31255, 48-41572, 48-54965, 50-10726, U.S. Pat.No. 2,719,086, No. 3,707,375, No. 3,754,919, No. 4,220,711 and the like.
[0046]
Preferable examples of the fluorescent whitening agent that can be used in combination include a coumarin fluorescent whitening agent. Examples of these are described in JP-B Nos. 45-4699 and 54-5324.
[0047]
Preferable antioxidants that can be used in combination include hindered amine antioxidants, hindered phenol antioxidants, aniline antioxidants, quinoline antioxidants, and the like. Examples of these are described in JP-A Nos. 59-155090, 60-107383, 60-107384, 61-137770, 61-139481, 61-160287, and the like.
[0048]
The amount of UV absorber, fluorescent brightener, and antioxidant that can be used in combination is 0.05 to 1.0 g / m.2 , Especially 0.1-0.4 g / m2 Is preferred.
[0049]
The amount of the electron-donating colorless dye and the electron-accepting compound used depends on the desired coating thickness, pressure-sensitive recording paper form, capsule manufacturing method, and other conditions, and may be appropriately selected according to the conditions. It is easy for those skilled in the art to determine this amount.
[0050]
When used for thermal paper, it takes the form described in JP-A-62-144989, JP-A-1-87291, and the like. Specifically, the electron-donating colorless dye and the electron-accepting compound are used after being pulverized and dispersed in a dispersion medium to a particle size of 10 μm or less, preferably 3 μm or less. As the dispersion medium, a water-soluble polymer aqueous solution having a concentration of about 0.5 to 10% is generally used, and the dispersion is performed using a ball mill, a sand mill, a horizontal sand mill, an attritor, a colloidal mill or the like.
[0051]
At that time, a heat-fusible substance can be contained in the heat-sensitive color developing layer in order to improve the thermal response. Representative examples of the heat-fusible substance include aromatic ethers, thioethers, esters, and aliphatic amides or ureidos.
[0052]
Examples of these are disclosed in JP-A-58-57989, JP-A-58-87094, JP-A-61-58789, JP-A-62-109681, JP-A-62-132673, JP-A-63-151478, JP-A-63-235961, 2-184489, 2-215585, and the like.
[0053]
These are used at the same time as the electron donating colorless dye or finely dispersed simultaneously with the electron accepting compound. They are added in a weight ratio of 20% or more and 300% or less, and particularly preferably 40% or more and 150% or less, based on the amount used and the electron accepting compound.
[0054]
Additives are added to the coating liquid obtained in this manner as necessary in order to satisfy various requirements. As an example of the additive, an oil absorbing material such as an inorganic pigment or a polyurea filler is dispersed in a binder in order to prevent the recording head from being soiled during recording, and the releasability to the head is further improved. For this purpose, fatty acids and metal soaps are added. Therefore, in general, in addition to electron-donating colorless dyes and electron-accepting compounds that directly contribute to color development, heat-fusible substances, pigments, waxes, antistatic agents, ultraviolet absorbers, antifoaming agents, conductive agents, fluorescent dyes Then, an additive such as a surfactant is applied on the support to constitute a recording material. Further, if necessary, a protective layer may be provided on the surface of the heat-sensitive recording layer.
[0055]
Usually, the electron-donating colorless dye and the electron-accepting compound are dispersed and applied in a binder. Water-soluble binders are generally used, such as polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-anhydrous. Examples thereof include maleic salicylic acid copolymer, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch derivative, casein, and gelatin. Further, for the purpose of imparting water resistance to these binders, a water-proofing agent may be added, or a hydrophobic polymer emulsion, specifically, a styrene-butadiene rubber latex, an acrylic resin emulsion, or the like may be added. As these usage-amounts, 0.4-5 g / m2 Is preferable, and further 0.8 to 1.6 g / m2 Is preferred.
[0056]
The obtained heat-sensitive coating liquid is applied to high-quality paper, high-quality paper having an undercoat layer, synthetic paper, plastic film, and the like. At this time, it is particularly preferable from the viewpoint of dot reproducibility to use a support having a smoothness defined by JIS-8119 of 500 seconds or more, particularly 800 seconds or more.
[0057]
In the recording material of the present invention, various additives such as a known wax, an antistatic agent, an antifoaming agent, a conductive agent, a fluorescent dye, a surfactant, and an ultraviolet absorber precursor can be used as necessary.
[0058]
In the recording material of the present invention, a protective layer may be provided on the surface of the recording layer as necessary. Two or more protective layers may be laminated as necessary. As a material used for the protective layer, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, vinyl acetate-acrylamide copolymer, silicon-modified polyvinyl alcohol, starch, modified starch, methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, gelatins, gum arabic, casein, Styrene-maleic acid copolymer hydrolyzate, styrene-maleic acid copolymer half ester hydrolyzate, isobutylene-maleic anhydride copolymer hydrolyzate, polyacrylamide derivative, polyvinylpyrrolidone, polystyrene sulfonic acid soda, alginate soda Water-soluble polymer compounds such as styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, methyl acrylate-butadiene rubber latex Latex such as a vinyl acetate emulsion is used. It is possible to further improve the storage stability by crosslinking the water-soluble polymer compound of the protective layer, and a known crosslinking agent can be used as the crosslinking agent. Specifically, water-soluble initial condensates such as N-methylolurea, N-methylolmelamine, urea-formalin, dialdehyde compounds such as glyoxal and glutaraldehyde, inorganic cross-linking agents such as boric acid and borax, polyamide epichlorohydrin, etc. Can be mentioned. For the protective layer, known pigments, metal soaps, waxes, surfactants and the like can also be used. The coating amount of the protective layer is 0.2-5 g / m2 Is preferable, and further 1.0 to 3.0 g / m2 Is preferred. The film thickness is preferably 0.2 to 5 μm, particularly preferably 1.0 to 3 μm.
[0059]
When a protective layer is used in the recording material of the present invention, a known UV absorber or UV absorber precursor may be contained in the protective layer.
[0060]
As the support that can be used in the recording material of the present invention, acid paper, neutral paper, coated paper, plastic film laminated paper, synthetic paper, plastic film, and the like can be used. Further, a known undercoat layer may be provided on these supports. This undercoat layer can be provided in the same manner as the protective layer.
[0061]
In order to correct the curl balance of the support or to improve the chemical resistance from the back side, a back coat layer may be provided, and a release paper is combined on the back side through an adhesive layer to form a label. May be. This back coat layer can also be provided in the same manner as the protective layer.
[0062]
【Example】
Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto.
[0063]
Unless otherwise specified, parts and% described below represent parts by weight and% by weight, respectively.
Example 1
Preparation of capsule liquid (MC1) encapsulating electron-donating colorless dye
Compounds represented by the following formulas (E-1), (E-2), (E-3), (E-4), (E-5), (E-6) and (E-7), 10.0 g and 1. 3 g, 2.0 g, 2.7 g, 1.3 g, 0.1 g, and 0.4 g were dissolved in 20 g of ethyl acetate by heating and gradually cooled to 40 ° C., and then Takenate D110N (trade name: Takeda Pharmaceutical) (Capsule wall agent) 2.0 g and Takenate D127N (same as Takeda Pharmaceutical) 11.6 g and n-butanol 0.4 g were added and stirred at 40 ° C. for 40 minutes.
[0064]
Embedded image
The obtained solution was added to an aqueous phase obtained by mixing 40 g of a polyvinyl alcohol 8% solution (PVA217C: trade name, manufactured by Kuraray Co., Ltd.) and 13 g of water, and then 10000 rpm using an ace homogenizer (trade name: manufactured by Nippon Seiki Co., Ltd.). For 5 minutes.
[0066]
After adding 70 g of water and 0.5 g of tetraethylenepentamine to the obtained emulsion, an encapsulation reaction was performed at 60 ° C. for 3 hours to obtain a capsule liquid (MC1) having an average particle diameter of 0.6 μm. Obtained.
[0067]
The average particle size is a 50% volume average particle size measured using a laser diffraction particle size distribution analyzer (LA700: trade name, manufactured by Horiba, Ltd.).
[0068]
In the following, unless otherwise specified, the average particle diameter represents the 50% volume average particle diameter.
Preparation of capsule liquid (MC2) containing electron-donating colorless dye
Compounds of formula (E-1) (E-2) (E-3) (E-4) (E-5) (E-6) and (E-7), 9.5 g and 1.2 g, respectively. 1.8 g, 4.6 g, 1.0 g, 1.0 g, and 0.4 g were heated and dissolved in 20 g of ethyl acetate and gradually cooled to 50 ° C., and then Takenate D140N (trade name: Takeda Pharmaceutical Capsule) 11.4 g (wall agent) and 1.3 g Vernock D750 (trade name: capsule wall agent manufactured by Dainippon Ink Co., Ltd.) were added and stirred.
[0069]
The obtained solution was added to an aqueous phase obtained by mixing 40 g of a polyvinyl alcohol 8% solution (PVA217C, manufactured by Kuraray Co., Ltd.) and 13 g of water, and then emulsified and dispersed at 10,000 rpm for 5 minutes using an ace homogenizer.
[0070]
After adding 80 g of water and 0.8 g of tetraethylenepentamine to the obtained emulsion, an encapsulation reaction was performed at 60 ° C. for 3 hours to obtain a capsule liquid (MC2) having an average particle diameter of 0.6 μm. It was.
Preparation of electron-accepting compound (developer) emulsified dispersion (A)
18.7 g, 13.1 g and 5.6 g of the compounds represented by the formulas (2-I), (3-I) and (1-I), respectively, are TCP (trade name: Oil manufactured by Daihachi Chemical Co., Ltd.) 0 g, 0.5 g of DEM (trade name: Oil manufactured by Daihachi Chemical Co., Ltd.) and 20 g of ethyl acetate were dissolved in a mixed solution.
[0071]
Polyvinyl alcohol 15% solution (PVA205C: manufactured by Kuraray Co., Ltd.) 25.0 g and polyvinyl alcohol 8% solution (PVA217C: manufactured by Kuraray Co., Ltd.) 46 g, sodium dodecyl sulfonate 0.5 g, and water 75.0 g were obtained. The mixture is charged into the mixed aqueous phase and emulsified at 10,000 rpm for 3 minutes using an ace homogenizer to obtain an electron-accepting compound (hereinafter referred to as a color developer) emulsified dispersion (A) having an average particle size of 0.6 μm. It was.
Preparation of coating solution for protective layer
Water 30g, polyvinyl alcohol 6% aqueous solution (PVA124C: trade name, manufactured by Kuraray Co., Ltd.) 20g, dioctyl sulfosuccinate sodium salt 2% aqueous solution 0.3g, kaolin dispersion (polyvinyl alcohol 3g mixed with water 100g kaolin 35 g was dispersed with a pole mill) 3.0 g and Hydrin Z (trade name: manufactured by Chukyo Yushi Co., Ltd.) 0.5 g were mixed to obtain a protective layer coating solution.
Preparation of transparent support with subbing layer
The chromaticity coordinates (JIS Z8701) are A (x = 0.25005, y = 0.3005), B (x = 0.2820, y = 0.2970), C (x = 0.2885, y = 0). .3015), D (x = 0.2870, y = 0.04040) SBR latex is solidified on one side of a 175 μm thick polyethylene terephthalate that is colored in a rectangular area having four vertices. 0.3g / m by weight2Then, the following undercoat layer coating solution was applied at a solid content weight of 0.1 g / m on one side.2Thus, a transparent support having an undercoat layer was obtained.
Preparation of coating solution for undercoat layer
200 g of a 5% gelatin aqueous solution (# 810: trade name, manufactured by Nitta Gelatin), 0.5 g of a gelatin dispersion in which 5% of polymethyl methacrylate resin particles having a particle diameter of 2 μm are dispersed, 1,2-benzothiazolin-3-one An undercoat layer coating solution was obtained by mixing 1.0 g of a 3% aqueous solution and 10 g of a 2% aqueous solution of di (2-ethyl) hexyl sulfonate.
Preparation of coating solution (1) for thermal recording layer
For thermal recording, 1.5 g of capsule liquid (MC1) already prepared, 3.5 g of capsule liquid (MC2), 15 g of developer emulsified dispersion (A) (one day left after emulsification dispersion) and 10 g of water were mixed. A coating solution (1) was obtained.
Preparation of thermal recording material
The coating liquid (1) for thermal recording was applied to one side of the transparent support provided with an undercoat layer already prepared at a solid content weight of 14 g / m.2After coating and drying to obtain a coating weight of 2.5 g / m in terms of solid content,2Thus, the heat-sensitive recording material of the present invention was obtained by coating and drying.
Printing method and performance evaluation
A thermal printer (TRT-16: trade name, manufactured by Nagano Japan Radio Co., Ltd.) was used for the obtained thermal recording material, and an image (hereinafter referred to as “step edge”) was recorded by changing the thermal energy applied to the thermal head.
(Example 2)
The thermal recording coating liquid (2) was prepared in the same manner as described above except that the developer emulsified dispersion (A) in the thermal recording-like coating liquid (1) used in Example 1 was changed to the liquid (B) described below. A heat-sensitive recording material of the present invention was obtained in the same manner as described above.
Preparation of developer emulsified dispersion (B)
In the method for preparing the developer emulsified dispersion (A) described in Example 1, except that the compound represented by the formula (3-I) was changed to the compound represented by the formula (4-I). A developer emulsified dispersion (B) having an average particle size of 0.6 μm was prepared in the same manner.
Printing method and performance evaluation
The heat-sensitive recording material of Example 2 was subjected to the same method and performance evaluation as described in Example 1.
(Example 3)
The thermal recording coating liquid (3) was prepared in the same manner except that the developer emulsified dispersion (A) in the thermal recording coating liquid (1) used in Example 1 was changed to the following (C) liquid. A heat-sensitive recording material of the present invention was obtained in the same manner as described above.
Preparation of developer emulsified dispersion (C)
In the method for preparing the developer emulsion dispersion (A) described in Example 1, except that the compound represented by the formula (3-I) was changed to the compound represented by the formula (4-II). A developer emulsified dispersion (C) having an average particle diameter of 0.6 μm was prepared in the same manner.
Printing method and performance evaluation
The thermosensitive recording material of Example 3 was subjected to the same method and performance evaluation as described in Example 1.
Example 4
The thermal recording coating liquid (4) was prepared in the same manner except that the developer emulsified dispersion (A) in the thermal recording coating liquid (1) used in Example 1 was changed to the liquid (D) described below. A heat-sensitive recording material of the present invention was obtained in the same manner as described above.
Preparation of developer emulsified dispersion (D)
In the method for preparing the developer emulsified dispersion (A) described in Example 1, except that the compound represented by the formula (3-I) was changed to the compound represented by the formula (5-I). A developer emulsified dispersion (D) having an average particle size of 0.6 μm was prepared in the same manner.
Printing method and performance evaluation
The thermal recording material of Example 4 was subjected to the same method and performance evaluation as described in Example 1.
(Example 5)
The thermal recording coating solution (5) was prepared in the same manner except that the developer emulsified dispersion (A) in the thermal recording coating solution (1) used in Example 1 was changed to the following (E) solution. A heat-sensitive recording material of the present invention was obtained in the same manner except that it was used.
Preparation of developer emulsified dispersion (E)
In the method for preparing the developer emulsified dispersion (A) described in Example 1, the compounds represented by the formulas (2-I), (3-I) and (1-I), 18.7 g, 13.1 g and 5.6 g are represented by the formulas (2-I), (3-I), (1-I), (4-I), (4-II) and (5-I), A developer emulsified dispersion (E) having an average particle size of 0.6 μm was obtained in the same manner except that the amounts were changed to 16.2 g, 10.4 g, 3.6 g, 3.5 g, 2.2 g, and 1.4 g. Created.
Printing method and performance evaluation
The thermal recording material of Example 5 was subjected to the same method and performance evaluation as described in Example 1.
(Comparative Example 1)
The thermal recording coating liquid (6) was prepared in the same manner as described above except that the developer emulsified dispersion (E) in the thermal recording coating liquid (5) used in Example 5 was changed to the liquid (F) described below. A heat-sensitive recording material of the present invention was obtained in the same manner except that it was used.
Preparation of developer emulsified dispersion (F)
In the method for preparing the developer emulsified dispersion (A) described in Example 1, the compounds represented by the formulas (2-I), (3-I) and (1-I), 18.7 g, 13.1 g and 5.6 g represent the above formulas (2-I), (3-I), (4-I), (4-II) and (5-I), respectively, 17.9 g, 11 A developer emulsified dispersion (E) having an average particle size of 0.6 μm was prepared in the same manner except that the amount was changed to 0.6 g, 3.9 g, 2.4 g, and 1.6 g.
Printing method and performance evaluation
The thermal recording material of Example 5 was subjected to the same method and performance evaluation as described in Example 1.
(Comparative Example 2)
The developer emulsified dispersion (A) in the thermal recording coating solution (1) used in Example 1 was changed to the following (G) solution.
Preparation of developer emulsified dispersion (G)
In the method for preparing the developer emulsified dispersion (A) described in Example 1, the compounds represented by the formulas (2-I), (3-I) and (1-I), 18.7 g, The average particle size was changed in the same manner except that 13.1 g and 5.6 g were changed to the compounds represented by the above formulas (2-I) and (3-I), respectively 18.7 g and 18.7 g. A 0.6 μm developer emulsified dispersion (G) was prepared.
Developer emulsion dispersion after 1 day
The developer emulsified dispersion (G) was allowed to stand at room temperature for 1 day, but after 1 day, this liquid had precipitated. Therefore, even if this (G) liquid was mixed and applied with the capsule liquids (MC1) and (MC2), a transparent heat-sensitive recording material could not be provided, and the subsequent printing and performance evaluation were discontinued.
(Comparative Example 3)
The developer emulsified dispersion (A) in the thermal recording coating liquid (1) used in Example 1 was changed to the liquid (I) described below.
Preparation of developer emulsified dispersion (I)
In the method for preparing the developer emulsified dispersion described in Example 1, the compounds represented by the formulas (2-I), (3-I), and (1-I), 18.7 g and 13. The average particle size of 0.1 g and 5.6 g was changed in the same manner except that the compounds represented by the formulas (2-I) and (4-I) were changed to 18.7 g and 18.7 g, respectively. A developer emulsified dispersion (I) of 6 μm was prepared.
Developer emulsion dispersion after 1 day
The developer emulsified dispersion (I) was allowed to stand at room temperature for 1 day, but after 1 day, this liquid had precipitated. Therefore, even if this (I) liquid was mixed with the capsule liquids (MC1) and (MC2) and applied, a transparent heat-sensitive recording material could not be provided, and the subsequent printing and performance evaluation were discontinued.
(Comparative Example 4)
The developer emulsified dispersion (A) in the thermal recording coating solution (1) used in Example 1 was changed to the following (J) solution.
Preparation of developer emulsified dispersion (J)
In the method for preparing the developer emulsified dispersion described in Example 1, the compounds represented by the formulas (2-I), (3-I), and (1-I), respectively, 18.7 g and 13. 1 g and 5.6 g were changed to the compounds represented by the formulas (2-I) and (4-II), respectively, 18.7 g and 18.7 g, respectively. A 6 μm developer emulsified dispersion (J) was prepared.
Developer emulsion dispersion after 1 day
The developer emulsified dispersion (J) was allowed to stand at room temperature for 1 day, but after 1 day, this liquid had precipitated. Therefore, even if this (J) liquid was mixed and applied with the capsule liquids (MC1) and (MC2), a transparent heat-sensitive recording material could not be provided, and the subsequent printing and performance evaluation were discontinued.
(Comparative Example 5)
The developer emulsified dispersion (A) in the thermal recording coating solution (1) used in Example 1 was changed to the following (K) solution.
Preparation of developer emulsified dispersion (K)
In the method for preparing the developer emulsified dispersion described in Example 1, the compounds represented by the formulas (2-I), (3-I), and (1-I), respectively, 18.7 g and 13. The average particle size of 0.1 g and 5.6 g was changed in the same manner except that the compounds represented by the formulas (2-I) and (5-I) were changed to 18.7 g and 18.7 g, respectively. A 6-μm developer emulsified dispersion (K) was prepared.
Developer emulsion dispersion after 1 day
The developer emulsified dispersion (K) was allowed to stand at room temperature for 1 day, but after 1 day, this liquid had precipitated. Therefore, even if this (K) liquid was mixed with the capsule liquids (MC1) and (MC2) and applied, a transparent heat-sensitive recording material could not be provided, and the subsequent printing and performance evaluation were discontinued.
[0072]
Stability evaluation of developer emulsified dispersion
Table 1 below shows the results of visually observing the state over 1 day after the preparation of the developer emulsified dispersions of Examples 1 to 5 and Comparative Examples 1 to 6.
[0073]
[Table 1]
As is apparent from Table 1, the developer emulsions of Examples 1 to 5 in which the compound represented by the general formula (1) of the present invention was added together with the developer (electron-accepting compound) were emulsion stability. Since the developer emulsions of Comparative Examples 2 to 6 in which the compound represented by the general formula (1) of the present invention was not added, the precipitation occurred after lapse of 1 day. It was found that a transparent heat-sensitive recording material could not be provided even when mixed and applied with the contained capsule solution, and was not suitable for use.
[0075]
Next, with respect to the thermosensitive recording material using the developer emulsified dispersion (Examples 1 to 5 and Comparative Example 1) in which no precipitation occurred after lapse of one day, application was performed using a thermal printer (TRT-16). Energy 90 or 100 mj / mm2Table 2 shows the state of the step edge when printed as.
[0076]
[Table 2]
As is apparent from Table 2, the heat-sensitive recording materials of Examples 1 to 5 in which the compound represented by the general formula (1) of the present invention was added together with the electron accepting compound were 90 mj / mm.2When printed with, the coating state was good. Also, 100mj / mm2In Example 5, the heat-sensitive recording material of Example 5 was in a good coating state, and the heat-sensitive recording material of Examples 1 to 4 showed almost no peeling and was a printing level that had no practical problem. The heat-sensitive recording material No. 1 peeled off the coating film under any of the above conditions, and good printing was not obtained.
[0078]
【The invention's effect】
As described above, the heat-sensitive recording material of the present invention can form a good image without being affected by the heat-sensitive recording layer even when high energy is applied, and the emulsified state of the electron-accepting compound is long-term. The excellent effect of being stable was shown.
Claims (3)
感熱記録層が電子供与性無色染料、下記一般式（１）で表される化合物の一種又は二種以上、及び、下記一般式（２）で表される電子受容性化合物を含有し、且つ、さらに、前記感熱記録層に下記一般式（３）、下記一般式（４）及び下記一般式（５）で表される化合物からなる群から選ばれる一種又は二種以上を含有することを特徴とする感熱記録材料。
Heat-sensitive recording layer is an electron-donating colorless dye, under following general formula (1) of the compound represented by one or two or more, and contains an electron-accepting compound represented by the following general formula (2), and Furthermore, the thermosensitive recording layer contains one or more selected from the group consisting of compounds represented by the following general formula (3), the following general formula (4) and the following general formula (5). Thermal recording material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12157395A JP3691543B2 (en) | 1995-05-19 | 1995-05-19 | Thermal recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12157395A JP3691543B2 (en) | 1995-05-19 | 1995-05-19 | Thermal recording material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08310117A JPH08310117A (en) | 1996-11-26 |
| JP3691543B2 true JP3691543B2 (en) | 2005-09-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12157395A Expired - Fee Related JP3691543B2 (en) | 1995-05-19 | 1995-05-19 | Thermal recording material |
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| Country | Link |
|---|---|
| JP (1) | JP3691543B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR3063082B1 (en) * | 2017-02-17 | 2019-04-05 | Societe Bic | NOVEL THERMOCHROME PIGMENT COMPOSITION COMPRISING A COMPOUND OF FORMULA (I) AS A REACTIONAL MEDIUM |
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| Publication number | Publication date |
|---|---|
| JPH08310117A (en) | 1996-11-26 |
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