JP4049632B2 - Thermal transfer recording medium - Google Patents
Thermal transfer recording medium Download PDFInfo
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- JP4049632B2 JP4049632B2 JP2002219240A JP2002219240A JP4049632B2 JP 4049632 B2 JP4049632 B2 JP 4049632B2 JP 2002219240 A JP2002219240 A JP 2002219240A JP 2002219240 A JP2002219240 A JP 2002219240A JP 4049632 B2 JP4049632 B2 JP 4049632B2
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- JP
- Japan
- Prior art keywords
- recording medium
- thermal transfer
- transfer recording
- release layer
- acid
- Prior art date
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Landscapes
- Thermal Transfer Or Thermal Recording In General (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は熱溶融転写記録媒体に関し、詳しくは画像精細性に優れ、さらに得られる転写画像が耐溶剤性に優れる熱転写記録媒体に関する。
【０００２】
【従来の技術】
熱溶融転写記録媒体は、画像精細性が良好で、さらに、その使用環境によっては、熱転写された画像がエタノールのような有機溶剤によって消去しないことが要求される。
【０００３】
良好な転写性能を得るために、熱溶融性バインダーに特定のポリエステル樹脂を用いる方法が例示されている。特開昭６３−５１１８２号公報には水酸基価が１８〜２６０のポリエステル樹脂を用いることが示されているが、転写性能は優れていても、耐溶剤性等の画像耐久性は満足できるものではない。また、特開２００１-１７１２３３号公報には溶剤溶解度を規定したポリエステルを用いることが示されている。特開平１０-１２９１２２号公報には溶解度とパラメーターを規定した樹脂と酸変性ポリエチレンをインクに含有させることが示されている。しかしいずれも画像精細性と画像の耐溶剤性がともに優れたものではない。特に、エッジ型サーマルヘッドを搭載したプリンタでは、サーマルヘッド発熱体から熱転写記録媒体と受容体が剥離するまでの距離が極端に短く、なおかつ印字スピードが速いため、エネルギー印加から剥離までの時間が短くなる。したがって、インクが受容体に充分定着しないため、耐溶剤性に優れる画像を得るのは困難であった。このようなエッジ型サーマルヘッドを搭載したプリンタで使用可能な画像精細性、画像の耐溶剤性を満足する熱転写記録媒体が現状では存在しない。
【０００４】
【発明が解決しようとする課題】
したがって、上記従来技術に鑑みて、本発明の目的は、画像精細性および耐溶剤性に優れた熱転写記録媒体を提供することにある。
【０００５】
【課題を解決するための手段】
上記課題は、本発明の（１）「支持体上に剥離層、着色剤を含有するインク層を順次積層した熱転写記録媒体であって、剥離層がポリエチレンワックスを含有し、かつインク層が水酸基価が２０〜６０ｍｇＫＯＨ／ｇの熱可塑性飽和ポリエステル樹脂および酸価が５ｍｇＫＯＨ／ｇ以下の酸化ポリエチレンを含有することを特徴とする熱転写記録媒体」、（２）「剥離層ポリエチレンワックスの融点が１００〜１２０℃であることを特徴とする前記第（１）項に記載の熱転写記録媒体」、（３）「剥離層ポリエチレンワックスの２５℃における針入度が２未満であることを特徴とする前記第（１）項または第（２）項に記載の熱転写記録媒体」、（４）「熱可塑性飽和ポリエステル樹脂がジカルボン酸成分とグリコール成分との反応生成物であって、少なくとも１種のジカルボン酸成分として芳香族ジカルボン酸を用いたことを特徴とする前記第（１）項乃至第（３）項の何れか１に記載の熱転写記録媒体」、（５）「剥離層がエチレン−酢酸ビニル共重合体樹脂を含有することを特徴とする前記第（１）項乃至第（３）項の何れか１に記載の熱転写記録媒体」、（６）「剥離層がカルナウバワックス及び／又はキャンデリラワックスを含有することを特徴とする前記第（１）項、第（２）項、第（３）項、第（５）項の何れか１に記載の熱転写記録媒体」により達成される。
【０００６】
以下に本発明を詳細に説明する。
上述のように本発明の熱転写記録媒体は、支持体上に剥離層、着色剤を含有するインク層を順次積層した熱転写記録媒体において、剥離層がポリエチレンワックスを含有し、かつインク層が水酸基価が２０〜６０ｍｇＫＯＨ／ｇの熱可塑性飽和ポリエステル樹脂および酸価が５ｍｇＫＯＨ／ｇ以下の酸化ポリエチレンを含有することを特徴とする。
すなわち、このような構成によれば、画像精細性に優れるだけでなく、転写された画像が耐溶剤性に優れた熱転写記録媒体が得られる。
【０００７】
本発明で用いられる熱可塑性飽和ポリエステル樹脂は水酸基価が２０〜６０ｍｇＫＯＨ／ｇのものである。水酸基価が２０ｍｇＫＯＨ／ｇ未満では、混合する酸化ポリエチレンがどのような酸価のものであっても、充分な熱感度や画像精細性が得られず、６０ｍｇＫＯＨ／ｇを超えると耐溶剤性が低下する。本発明の熱可塑性飽和ポリエステル樹脂としてはグリコール成分とジカルボン酸成分から合成されるものが好ましい。グリコール成分の例としては、エチレングリコール、プロパンジオール、１，４−ブタンジオール、１，６−ヘキサンジオール、ジエチレングリコール、ネオペンチルグリコール、ポリエチレングリコール、ポリテトラメチレングリコール、トリメチロールプロパン、ビスフェノールＡ のエチレンオキサイド付加物等がある。またジカルボン酸成分の例としては、テレフタル酸、イソフタル酸、オルトフタル酸、２，６−ナフタレンジカルボン酸、パラフェニレンジカルボン酸、１，４−シクロヘキサンジカルボン酸、コハク酸、グルタル酸、アジピン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカンジオン酸、トリメリット酸、ピロメリット酸等がある。本発明ではジカルボン酸成分の少なくとも１種類にテレフタル酸やイソフタル酸等の芳香族ジカルボン酸を用いると、耐溶剤性に優れた転写画像が得られ、さらに好ましい。
【０００８】
本発明の熱可塑性飽和ポリエステル樹脂としてはガラス転移点温度が１０〜５５℃、数平均分子量が５００〜６０００のものが好ましい。ガラス転移点温度が１０℃未満や分子量が５００未満では転写画像の耐溶剤性に劣り、ブロッキングが発生する恐れもある。またガラス転移点温度が５５℃を超えたり、分子量が６０００を超えると転写画像の熱感度や画像精細性が劣る。
【０００９】
また本発明では熱可塑性飽和ポリエステル樹脂とともに酸価が５ｍｇＫＯＨ ／ｇ以下の酸化ポリエチレンを含有する。酸価が５ｍｇＫＯＨ／ｇを超えると耐溶剤性が低下する。インク層が水酸基価が２０〜６０ｍｇＫＯＨ／ｇの熱可塑性飽和ポリエステル樹脂を含有しない場合には、インク層の受容体への定着性が低下し画像の耐溶剤性が劣る。また酸価が５ｍｇＫＯＨ／ｇ以下の酸化ポリエチレンを含まない場合にはインク層の耐溶剤性が低下し画像の耐溶剤性も低下する。酸価が５ｍｇＫＯＨ／ｇ以下の酸化ポリエチレンと水酸基価が２０〜６０ｍｇＫＯＨ／ｇの熱可塑性飽和ポリエステル樹脂の相乗効果により、耐溶剤性に優れた転写画像が得られる。この組み合わせは低エネルギーでの印字の場合には特に有効である。インク層に添加する酸化ポリエチレンの粒径は０．１〜１０μｍ、好ましくは０．５〜８μｍとするのが良い。１０μｍを超えると画像精細性に劣る。
【００１０】
水酸基価が２０〜６０ｍｇＫＯＨ／ｇの熱可塑性飽和ポリエステル樹脂はインク層中に４０〜８０重量％、好ましくは５０〜７０重量％含有させるのが良い。４０重量％未満では耐溶剤性が低下し、８０重量％を超えると画像精細性に劣る。また５ｍｇＫＯＨ／ｇ以下の酸化ポリエチレンはインク層中に５〜１５重量％含有させるのが好ましい。５重量％未満では耐溶剤性に劣り、１５重量％を超えると画像精細性に劣る。
【００１１】
本発明の剥離層はポリエチレンワックスを含有する。なかでも融点（試験方法ＡＳＴＭ Ｄ１２７）が１００〜１２０℃のものが好ましい。１００℃未満では画像精細性に劣り、１２０℃を超えると熱感度が低下する。更には、２５℃における針入度（試験方法 ＡＳＴＭ Ｄ１３２１）が２未満のものが好ましい。２以上では耐溶剤性に劣る。また使用するポリエチレンワックスは密度が０．９４以上の高密度ポリエチレンが好ましい。
【００１２】
ポリエチレンワックスは、融点が比較的高いので、剥離層に添加するとにじみのない画像精細性の良いシャープな画像が得られるが、熱感度が低くなるという欠点があった。しかし本発明のインク層は水酸基価が２０〜６０ｍｇＫＯＨ／ｇの熱可塑性飽和ポリエステル樹脂を含有しているので定着性に優れ熱感度を高めることができる。したがって、本発明の剥離層とインク層の組み合わせにより、熱感度、画像精細性、耐溶剤性を高度に満足する画像が得られる。
【００１３】
本発明の剥離層のバインダーとしては、エチレン−酢酸ビニル共重合体樹脂、ポリアミド樹脂、ポリエステル樹脂、イソプレンゴム、ブタジエンゴム、エチレンプロピレンゴム、ブチルゴム、ニトリルゴム等が用いられるが、なかでもエチレン−酢酸ビニル共重合体樹脂を用いるのが好ましい。更には、酢酸ビニル含有量（試験方法 ケン化法）が１５〜３５％でメルトフローレート（試験法ＡＳＴＭ Ｄ−１２３８改）が１０〜２００ｄｇ／ｍｉｎのものを用いると精細性の優れた良好な画像が得られる。
【００１４】
本発明では剥離層にポリエチレンワックス以外のワックスを含有させることもできる。例えば、蜜ろう、鯨ろう、木ろう、米ぬかろう、カルナウバワックス、キャンデリラワックス、モンタンワックス等の天然ワックス；マイクロクリスタリンワックス、酸ワックス、オゾケライト、セレシン、エステルワックス等の合成ワックス；マルガリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、フロイン酸、べへニン酸等の高級飽和脂肪酸；ステアリルアルコール、べへニルアルコール等の高級飽和一価アルコール；ソルビタンの脂肪酸エステル等の高級エステル；ステアリン酸アミド、オレイン酸アミド等の高級脂肪酸アミド等が挙げられる。なかでも、カルナウバワックスまたはキャンデリラワックスを添加すると、熱感度の向上が図れ好ましい。これらポリエチレンワックス以外のワックスを添加する場合は、その添加量が剥離層中の全ワックス成分の５０重量％以下となるように添加するのが好ましい。
【００１５】
本発明のインク層には、熱感度や画像精細性の向上を目的として、各種の添加物質が添加されてよい。例えば、ワックス状の脂肪酸アミド、各種滑剤、パラフィンワックスのような合成ワックス類、キャンデリラワックスやカルナウバワックス等の天然ワックス類、シリコーン油やパーフロロアルキルエーテル等のオイル類等の添加によって熱感度や画像精細性を向上させることができる。なお、この場合の滑剤にはリン酸エステル等のほか、シリコーン樹脂や四フッ化エチレン樹脂やフロロアルキルエーテル樹脂等の樹脂類、炭化ケイ素やシリカ等の無機滑剤も使用可能である。
【００１６】
本発明で用いられる着色剤としては、要求される色調などに応じて、カーボンブラック、有機顔料、無機顔料または各種染料から適当なものを選択して用いることができる。
【００１７】
支持体は公知のフィルムや紙をそのまま使用すればよく、例えばポリエチレンテレフタレート等のポリエステル、ポリカーボネート、トリアセチルセルロース、ナイロン、ポリイミド等のように比較的耐熱性のよいプラスチックフィルム；セロハン；硫酸紙等が好ましく使用される。
【００１８】
また本発明の熱転写記録媒体には必要に応じて支持体の裏面に保護層を設けてもよい。保護層はサーマルヘッドによる熱印加時に支持体を高温から保護するための層であり、耐熱性の高い熱可塑性樹脂や熱硬化性樹脂のほか、紫外線硬化性樹脂や電子線硬化性樹脂も使用可能である。なお、保護層形成に好適な樹脂はフッ素樹脂、シリコーン樹脂、ポリイミド樹脂、エポキシ樹脂、フェノール樹脂、メラミン樹脂等であり、これらの樹脂を薄膜状で使用すればよい。また、保護層の設置によって支持体の耐熱性を著しく向上させることができるため、該層の設置によって従来は不適とされていた支持体を用いることもできる。
【００１９】
以上に詳記した熱転写層は、ホットメルト塗工法、水性塗工法、有機溶媒を用いた塗工法等で支持体上に積層して設けることができる。このような塗工法で設けられる熱転写層は、全体の厚さを０．１〜１０μｍ、好ましくは０．５〜６．０μｍにすればよい。また、各層の層厚としてインク層は０．５〜６．０μｍ、好ましくは０．８〜３μｍ、剥離層は０．２〜３．０μｍ、好ましくは１．０〜２．０μｍとすれば良い。
【００２０】
【実施例】
次に実施例を挙げて本発明をさらに具体的に説明する。なお、ここでの部は固形分重量基準である。
〔実施例１〕
支持体としては４．５μｍ厚のポリエチレンテレフタレートフィルムを用意し、熱転写記録層を塗工する側の反対側にシリコーンゴム（東レ・ダウコーニング・シリコーン社製ＳＤ７２２６）を乾燥後塗工量が０．２ｇ／ｍ２となるように塗布乾燥して耐熱滑性層を有する支持体を作成した。
＜剥離層処方＞
＜インク層処方＞
【００２１】
〔実施例２〕
実施例１において、インク層ポリエステル樹脂として水酸基価６０ｍｇＫＯＨ／ｇのポリエステル樹脂（テレフタル酸・エチレングリコール・イソフタル酸、ネオペンチルグリコール重縮合物）を用いた以外は、実施例１と同様にして熱転写記録媒体を作成した。
【００２２】
〔実施例３〕
実施例１において、インク液のポリエステル樹脂として水酸基価４５ｍｇＫＯＨ／ｇのポリエステル樹脂（テレフタル酸・エチレングリコール・イソフタル酸、ネオペンチルグリコール重縮合物）を用いた以外は、実施例１と同様にして熱転写記録媒体を作成した。
【００２３】
〔実施例４〕
実施例３において、剥離層ポリエチレンワックスとして融点１１０℃、針入度３．５、密度０．９４のものを用いた以外は、実施例３と同様にして熱転写記録媒体を作成した。
【００２４】
〔実施例５〕
実施例３において、剥離層ポリエチレンワックスとして融点１１３℃、針入度１．０、密度０．９４のものを用いた以外は、実施例３と同様にして熱転写記録媒体を作成した。
【００２５】
〔実施例６〕
実施例３において剥離層処方として下記処方を用いた以外は、実施例３と同様にして熱転写記録媒体を作成した。
＜剥離層処方＞
〔実施例７〕
実施例３において剥離層処方として下記処方を用いた以外は、実施例３と同様にして熱転写記録媒体を作成した。
＜剥離層処方＞
〔比較例１〕
実施例３において、インク層ポリエステル樹脂として水酸基価１８ｍｇＫＯＨ／ｇのポリエステル樹脂（テレフタル酸・エチレングリコール・イソフタル酸、ネオペンチルグリコール重縮合物）を用いた以外は、実施例３と同様にして熱転写記録媒体を作成した。
【００２８】
〔比較例２〕
実施例３において、剥離層を設けなかった以外は、実施例３と同様にして熱転写記録媒体を作成した。
【００２９】
〔比較例３〕
実施例３において剥離層処方として下記処方を用いた以外は、実施例３と同様にして熱転写記録媒体を作成した。
＜剥離層処方＞
カルナウバワックスのトルエン分散体（固形分１０％） ９０部
エチレン−酢酸ビニル共重合体樹脂のトルエン溶液 １０部
（固形分１０％）
【００３０】
〔比較例４〕
実施例３においてインク層処方として下記処方を用いた以外は、実施例３と同様にして熱転写記録媒体を作成した。
＜インク層処方＞
〔比較例５〕
実施例３においてインク層処方として下記処方を用いた以外は、実施例３と同様にして熱転写記録媒体を作成した。
＜インク層処方＞
〔比較例６〕
実施例３においてインク層処方として下記処方を用いた以外は、実施例３と同様にして熱転写記録媒体を作成した。
＜インク層処方＞
【００３３】
（印字条件）
プリンタ：東芝ＴＥＣ社製 Ｂ−３０（フラット型サーマルヘッド搭載）
印字速度：１０ｃｍ／秒
【００３４】
評価した諸特性は以下の通りである。
１．画像精細性
プリンタ標準印加エネルギー下での転写画像を下記の基準にて評価した。
５ ボイド、力スレがなく、画像のエッジが非常にシャープである。
４ ボイド、力スレがなく、画像のエッジがシャープである。
３ ポイド、力スレがほとんどない。
２ ややポイド、カスレがある。
１ ポイド、カスレが多い。
【００３５】
２．耐エタノール性
エタノール０．５ｃｃを綿棒に含ませて転写画像に塗布後、このサンプルについて１０ｇ／ｍｍ２の荷重下に３０ｃｍ／秒のスピードで往復ラブテストを３０回行ない、被転写紙（白ＰＥＴ）面を観察し次の基準で評価した。溶剤はエタノールを用いた。
５ ラブテストの結果、テスト前と変化なし。
４ ラブテストの結果、画像の判読は可能だがやや傷ができる。
３ ラブテストの結果、画像の判読は可能だが傷ができる。
２ ラブテストの結果、画像は残るが判読は不可能になる。
１ ラブテストの結果、画像が消去してしまう。
【００３６】
〔実施例８〕
実施例３で得られた熱転写記録媒体を下記条件で印字した以外は実施例３と同様に評価を行なった。
【００３７】
（印字条件）
プリンタ：東芝ＴＥＣ社製 Ｂ−４７４（ヘッジ型サーマルヘッド搭載）
印字速度：１３ｃｍ／秒
【００３８】
〔比較例７〕
比較例１で得られた熱転写記録媒体を実施例８と同じ条件で印字した以外は実施例８と同様にして評価を行なった。
以上の評価結果を表１に示す。
【００３９】
【表１】
【００４０】
【発明の効果】
以上、詳細かつ具体的な説明から明らかなように、本発明の支持体上に剥離層、着色剤を含有するインク層を順次積層した熱転写記録媒体において、剥離層がポリエチレンワックスを含有し、かつインク層が水酸基価が２０〜６０ｍｇＫＯＨ／ｇの熱可塑性飽和ポリエステル樹脂および酸価が５ｍｇＫＯＨ／ｇ以下の酸化ポリエチレンを含有することにより、画像精細性を損なわずに、かつその転写画像はエタノールのような溶剤に対しての耐性に優れている。特にインクの定着性に劣るヘッジ型サーマルヘッドを搭載したプリンタでも画像精細性と耐溶剤性の両立をはかることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a hot-melt transfer recording medium, and more particularly to a thermal transfer recording medium having excellent image definition and a transfer image obtained having excellent solvent resistance.
[0002]
[Prior art]
The heat-melt transfer recording medium has good image definition, and further, depending on the use environment, it is required that the heat-transferred image is not erased by an organic solvent such as ethanol.
[0003]
In order to obtain good transfer performance, a method using a specific polyester resin for the hot-melt binder is exemplified. Japanese Patent Application Laid-Open No. 63-51182 discloses that a polyester resin having a hydroxyl value of 18 to 260 is used. However, even if transfer performance is excellent, image durability such as solvent resistance is not satisfactory. Absent. Japanese Patent Application Laid-Open No. 2001-171233 discloses the use of a polyester having a prescribed solvent solubility. Japanese Patent Application Laid-Open No. 10-129122 discloses that an ink contains a resin having a prescribed solubility and parameters and acid-modified polyethylene. However, none of them is excellent in both image definition and image solvent resistance. In particular, in printers equipped with edge-type thermal heads, the distance from the thermal head heating element to the thermal transfer recording medium and the receiver is extremely short and the printing speed is fast, so the time from energy application to peeling is short. Become. Therefore, since the ink is not sufficiently fixed to the receiver, it is difficult to obtain an image having excellent solvent resistance. At present, there is no thermal transfer recording medium that satisfies image definition and image solvent resistance that can be used in a printer equipped with such an edge-type thermal head.
[0004]
[Problems to be solved by the invention]
Therefore, in view of the above prior art, an object of the present invention is to provide a thermal transfer recording medium excellent in image definition and solvent resistance.
[0005]
[Means for Solving the Problems]
The above-described problem is (1) “a thermal transfer recording medium in which a release layer and an ink layer containing a colorant are sequentially laminated on a support, wherein the release layer contains polyethylene wax and the ink layer is a hydroxyl group. A thermal transfer recording medium comprising a thermoplastic saturated polyester resin having a value of 20 to 60 mgKOH / g and an oxidized polyethylene having an acid value of 5 mgKOH / g or less, and (2) “the melting point of the release layer polyethylene wax is 100 to 100”. The thermal transfer recording medium according to item (1) above, characterized in that it is 120 ° C. ”, (3)“ The penetration of the release layer polyethylene wax at 25 ° C. is less than 2 ” (1) or thermal transfer recording medium described in item (2) ”, (4)“ Thermoplastic saturated polyester resin is a reaction product of a dicarboxylic acid component and a glycol component. The thermal transfer recording medium according to any one of items (1) to (3), wherein an aromatic dicarboxylic acid is used as at least one dicarboxylic acid component ”, (5) “The thermal transfer recording medium according to any one of items (1) to (3), wherein the release layer contains an ethylene-vinyl acetate copolymer resin”, (6) “Release layer” The thermal transfer according to any one of the items (1), (2), (3), and (5), characterized in that comprises a carnauba wax and / or a candelilla wax. Achieved by “recording medium”.
[0006]
The present invention is described in detail below.
As described above, the thermal transfer recording medium of the present invention is a thermal transfer recording medium in which a release layer and an ink layer containing a colorant are sequentially laminated on a support. The release layer contains polyethylene wax and the ink layer has a hydroxyl value. 20 to 60 mgKOH / g thermoplastic saturated polyester resin and an acid value of 5 mgKOH / g or less of oxidized polyethylene.
That is, according to such a configuration, it is possible to obtain a thermal transfer recording medium not only having excellent image definition but also having a transferred image having excellent solvent resistance.
[0007]
The thermoplastic saturated polyester resin used in the present invention has a hydroxyl value of 20 to 60 mgKOH / g. When the hydroxyl value is less than 20 mgKOH / g, sufficient heat sensitivity and image definition cannot be obtained regardless of the acid value of polyethylene oxide to be mixed. When the hydroxyl value exceeds 60 mgKOH / g, the solvent resistance decreases. To do. The thermoplastic saturated polyester resin of the present invention is preferably synthesized from a glycol component and a dicarboxylic acid component. Examples of glycol components include ethylene glycol, propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, polyethylene glycol, polytetramethylene glycol, trimethylol propane, ethylene oxide of bisphenol A There are additions. Examples of dicarboxylic acid components include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylene dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, and suberic acid. , Azelaic acid, sebacic acid, dodecanedioic acid, trimellitic acid, pyromellitic acid and the like. In the present invention, when an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid is used as at least one of the dicarboxylic acid components, a transfer image excellent in solvent resistance is obtained, which is more preferable.
[0008]
The thermoplastic saturated polyester resin of the present invention preferably has a glass transition temperature of 10 to 55 ° C. and a number average molecular weight of 500 to 6000. If the glass transition temperature is less than 10 ° C. or the molecular weight is less than 500, the transfer image is poor in solvent resistance and may cause blocking. On the other hand, when the glass transition temperature exceeds 55 ° C. or the molecular weight exceeds 6000, the thermal sensitivity and image definition of the transferred image are poor.
[0009]
In the present invention, polyethylene oxide containing an acid value of 5 mg KOH / g or less is contained together with the thermoplastic saturated polyester resin. When the acid value exceeds 5 mgKOH / g, the solvent resistance decreases. When the ink layer does not contain a thermoplastic saturated polyester resin having a hydroxyl value of 20 to 60 mgKOH / g, the fixability of the ink layer to the receptor is lowered and the solvent resistance of the image is inferior. When the oxidized polyethylene does not contain an oxidized polyethylene having an acid value of 5 mgKOH / g or less, the solvent resistance of the ink layer is lowered and the solvent resistance of the image is also lowered. Due to the synergistic effect of the oxidized polyethylene having an acid value of 5 mgKOH / g or less and the thermoplastic saturated polyester resin having a hydroxyl value of 20 to 60 mgKOH / g, a transfer image excellent in solvent resistance can be obtained. This combination is particularly effective for low energy printing. The particle diameter of the oxidized polyethylene added to the ink layer is 0.1 to 10 μm, preferably 0.5 to 8 μm. When it exceeds 10 μm, the image definition is inferior.
[0010]
The thermoplastic saturated polyester resin having a hydroxyl value of 20 to 60 mgKOH / g is contained in the ink layer in an amount of 40 to 80% by weight, preferably 50 to 70% by weight. If it is less than 40% by weight, the solvent resistance is lowered, and if it exceeds 80% by weight, the image definition is inferior. Further, 5 to 15% by weight of polyethylene oxide having a concentration of 5 mgKOH / g or less is preferably contained in the ink layer. If it is less than 5% by weight, the solvent resistance is poor, and if it exceeds 15% by weight, the image definition is poor.
[0011]
The release layer of the present invention contains polyethylene wax. Of these, those having a melting point (test method ASTM D127) of 100 to 120 ° C. are preferred. If it is less than 100 ° C., the image definition is inferior. Furthermore, it is preferable that the penetration at 25 ° C. (test method ASTM D1321) is less than 2. Two or more are inferior to solvent resistance. The polyethylene wax used is preferably high density polyethylene having a density of 0.94 or more.
[0012]
Polyethylene wax has a relatively high melting point, so that when added to the release layer, a sharp image with good image definition without blurring can be obtained, but it has the disadvantage of low thermal sensitivity. However, since the ink layer of the present invention contains a thermoplastic saturated polyester resin having a hydroxyl value of 20 to 60 mgKOH / g, the fixing property is excellent and the thermal sensitivity can be increased. Therefore, the combination of the release layer and the ink layer of the present invention can provide an image highly satisfying thermal sensitivity, image definition, and solvent resistance.
[0013]
As the binder of the release layer of the present invention, ethylene-vinyl acetate copolymer resin, polyamide resin, polyester resin, isoprene rubber, butadiene rubber, ethylene propylene rubber, butyl rubber, nitrile rubber, etc. are used, and among them, ethylene-acetic acid It is preferable to use a vinyl copolymer resin. Furthermore, if the vinyl acetate content (test method saponification method) is 15 to 35% and the melt flow rate (test method ASTM D-1238 modified) is 10 to 200 dg / min, excellent fineness is obtained. An image is obtained.
[0014]
In the present invention, the release layer may contain a wax other than polyethylene wax. For example, natural wax such as beeswax, whale wax, wood wax, rice bran wax, carnauba wax, candelilla wax, montan wax; synthetic wax such as microcrystalline wax, acid wax, ozokerite, ceresin, ester wax; margaric acid, Higher saturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, furonic acid, and behenic acid; higher saturated monohydric alcohols such as stearyl alcohol and behenyl alcohol; higher esters such as sorbitan fatty acid ester; stearin And higher fatty acid amides such as acid amides and oleic acid amides. Among these, it is preferable to add carnauba wax or candelilla wax because heat sensitivity can be improved. When a wax other than these polyethylene waxes is added, it is preferably added so that the amount added is 50% by weight or less of the total wax components in the release layer.
[0015]
Various additive substances may be added to the ink layer of the present invention for the purpose of improving thermal sensitivity and image definition. For example, heat sensitivity by adding waxy fatty acid amides, various lubricants, synthetic waxes such as paraffin wax, natural waxes such as candelilla wax and carnauba wax, oils such as silicone oil and perfluoroalkyl ether, etc. And image definition can be improved. In this case, as the lubricant, in addition to phosphoric acid ester, resins such as silicone resin, tetrafluoroethylene resin and fluoroalkyl ether resin, and inorganic lubricants such as silicon carbide and silica can be used.
[0016]
As the colorant used in the present invention, an appropriate one can be selected from carbon black, an organic pigment, an inorganic pigment, or various dyes according to a required color tone.
[0017]
For the support, a known film or paper may be used as it is. For example, a plastic film having relatively high heat resistance such as polyester such as polyethylene terephthalate, polycarbonate, triacetyl cellulose, nylon, polyimide, cellophane, sulfate paper, etc. Preferably used.
[0018]
Further, the thermal transfer recording medium of the present invention may be provided with a protective layer on the back surface of the support, if necessary. The protective layer is a layer to protect the support from high temperature when heat is applied by the thermal head. In addition to high heat resistance thermoplastic resin and thermosetting resin, UV curable resin and electron beam curable resin can also be used. It is. In addition, resin suitable for protective layer formation is a fluororesin, a silicone resin, a polyimide resin, an epoxy resin, a phenol resin, a melamine resin, etc., What is necessary is just to use these resin in a thin film form. Further, since the heat resistance of the support can be remarkably improved by installing the protective layer, a support that has been conventionally unsuitable by installing the layer can also be used.
[0019]
The thermal transfer layer described in detail above can be provided by laminating on a support by a hot melt coating method, an aqueous coating method, a coating method using an organic solvent, or the like. The thermal transfer layer provided by such a coating method may have a total thickness of 0.1 to 10 μm, preferably 0.5 to 6.0 μm. The thickness of each layer is 0.5 to 6.0 μm, preferably 0.8 to 3 μm, and the release layer is 0.2 to 3.0 μm, preferably 1.0 to 2.0 μm. .
[0020]
【Example】
Next, the present invention will be described more specifically with reference to examples. In addition, a part here is a solid content weight reference | standard.
[Example 1]
A 4.5 μm-thick polyethylene terephthalate film was prepared as a support, and silicone rubber (SD7226 manufactured by Toray Dow Corning Silicone Co., Ltd.) was dried on the side opposite to the side to which the thermal transfer recording layer was applied. A support having a heat-resistant slip layer was prepared by coating and drying so as to be 2 g / m 2 .
<Release layer formulation>
<Ink layer prescription>
[0021]
[Example 2]
In Example 1, thermal transfer recording was performed in the same manner as in Example 1 except that a polyester resin having a hydroxyl value of 60 mgKOH / g (terephthalic acid / ethylene glycol / isophthalic acid, neopentyl glycol polycondensate) was used as the ink layer polyester resin. Created media.
[0022]
Example 3
Thermal transfer in the same manner as in Example 1 except that a polyester resin (terephthalic acid / ethylene glycol / isophthalic acid, neopentyl glycol polycondensate) having a hydroxyl value of 45 mgKOH / g was used as the polyester resin of the ink liquid in Example 1. A recording medium was created.
[0023]
Example 4
In Example 3, a thermal transfer recording medium was prepared in the same manner as in Example 3 except that a release layer polyethylene wax having a melting point of 110 ° C., a penetration of 3.5, and a density of 0.94 was used.
[0024]
Example 5
In Example 3, a thermal transfer recording medium was prepared in the same manner as in Example 3 except that the release layer polyethylene wax had a melting point of 113 ° C., a penetration of 1.0, and a density of 0.94.
[0025]
Example 6
A thermal transfer recording medium was prepared in the same manner as in Example 3 except that the following formulation was used as the release layer formulation in Example 3.
<Release layer formulation>
Example 7
A thermal transfer recording medium was prepared in the same manner as in Example 3 except that the following formulation was used as the release layer formulation in Example 3.
<Release layer formulation>
[Comparative Example 1]
In Example 3, thermal transfer recording was performed in the same manner as in Example 3 except that a polyester resin (terephthalic acid / ethylene glycol / isophthalic acid, neopentyl glycol polycondensate) having a hydroxyl value of 18 mgKOH / g was used as the ink layer polyester resin. Created media.
[0028]
[Comparative Example 2]
In Example 3, a thermal transfer recording medium was prepared in the same manner as in Example 3 except that the release layer was not provided.
[0029]
[Comparative Example 3]
A thermal transfer recording medium was prepared in the same manner as in Example 3 except that the following formulation was used as the release layer formulation in Example 3.
<Release layer formulation>
Carnauba wax toluene dispersion (solid content 10%) 90 parts Ethylene-vinyl acetate copolymer resin toluene solution 10 parts (solid content 10%)
[0030]
[Comparative Example 4]
A thermal transfer recording medium was prepared in the same manner as in Example 3 except that the following formulation was used as the ink layer formulation in Example 3.
<Ink layer prescription>
[Comparative Example 5]
A thermal transfer recording medium was prepared in the same manner as in Example 3 except that the following formulation was used as the ink layer formulation in Example 3.
<Ink layer prescription>
[Comparative Example 6]
A thermal transfer recording medium was prepared in the same manner as in Example 3 except that the following formulation was used as the ink layer formulation in Example 3.
<Ink layer prescription>
[0033]
(Printing conditions)
Printer: Toshiba TEC B-30 (with flat thermal head)
Printing speed: 10 cm / sec
The various characteristics evaluated are as follows.
1. The transfer image under the standard applied energy of the image definition printer was evaluated according to the following criteria.
5 There are no voids and force threads, and the edges of the image are very sharp.
4 There are no voids or force threads, and the edges of the image are sharp.
3 Poid, almost no power thread.
2 There are some voids and blurring.
1 There are a lot of voids and scrapes.
[0035]
2. After applying 0.5 cc of ethanol-resistant ethanol to the cotton swab and applying it to the transfer image, this sample was subjected to a reciprocating rub test 30 times at a speed of 30 cm / sec under a load of 10 g / mm 2 to obtain a paper to be transferred (white PET ) The surface was observed and evaluated according to the following criteria. Ethanol was used as the solvent.
5 As a result of the love test, there is no change from before the test.
4 As a result of the love test, the image can be read but slightly damaged.
3 As a result of the love test, the image can be read but can be damaged.
2 As a result of the love test, the image remains but cannot be read.
1 The image is erased as a result of the love test.
[0036]
Example 8
Evaluation was performed in the same manner as in Example 3 except that the thermal transfer recording medium obtained in Example 3 was printed under the following conditions.
[0037]
(Printing conditions)
Printer: Toshiba TEC B-474 (equipped with a hedge type thermal head)
Printing speed: 13 cm / sec
[Comparative Example 7]
Evaluation was performed in the same manner as in Example 8 except that the thermal transfer recording medium obtained in Comparative Example 1 was printed under the same conditions as in Example 8.
The above evaluation results are shown in Table 1.
[0039]
[Table 1]
[0040]
【The invention's effect】
As described above, as is clear from the detailed and specific description, in the thermal transfer recording medium in which the release layer and the ink layer containing the colorant are sequentially laminated on the support of the present invention, the release layer contains polyethylene wax, and Since the ink layer contains a thermoplastic saturated polyester resin having a hydroxyl value of 20 to 60 mgKOH / g and an oxidized polyethylene having an acid value of 5 mgKOH / g or less, the transferred image is like ethanol. Excellent resistance to various solvents. In particular, even a printer equipped with a hedge-type thermal head that is inferior in ink fixability can achieve both image definition and solvent resistance.
Claims (6)
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