JP3640948B2

JP3640948B2 - Thermal transfer recording method and thermal transfer recording apparatus

Info

Publication number: JP3640948B2
Application number: JP2002299460A
Authority: JP
Inventors: 信義田口; 章博今井; 淳曽我美; 康雄福井; 正紀吉川; 浩之松尾
Original assignee: Panasonic Corp; Matsushita Electric Industrial Co Ltd
Current assignee: Panasonic Corp; Panasonic Holdings Corp
Priority date: 1994-10-20
Filing date: 2002-10-11
Publication date: 2005-04-20
Anticipated expiration: 2015-10-19
Also published as: JP2003136849A

Description

【０００１】
【発明の属する技術分野】
本発明は受像体の基質に関係なく受像体に高画質フルカラー画像を形成する染料熱転写記録を安定に遂行させるための熱記録転写体，及び受像体の全面に高画質フルカラー画像を形成することを可能にした染料熱転写記録方法に関する。
【０００２】
【従来の技術】
染料熱転写記録はカラー写真に匹敵する高画質画像を提供できる唯一の小型・保守・即時性の優れた記録技術である。これは薄いフィルム基材上に昇華性染料を含む色材層をもうけた転写体と合成紙などの厚手フルム基材上に染着層をもうけた受像体を重ね、熱記録ヘッドを用いて昇華性染料を染着層に移行し染料分子の混色画像を記録するものである。記録は、一般的に受像体を駆動し受像体と転写体間の摩擦力で転写体を従動しておこなう。
【０００３】
一方、色々な所に記録画像を添付するため、タックシートを用いる方法が提案されている。タックシートは、上層と下層の２枚構造からなる受像体であって、基材の表面に染着層を形成して得られた上層を、これの前記基材裏面に粘着材を設けて、その上面に離型層が設けられた支持体からなる下層上に固定化したものである。記録後、上層をはがし葉書等に添付して用いている。
【０００４】
前述のように、染料熱転写記録方法による記録画像は特殊紙の上に形成される。そのため、ランニングコストが高く本技術の普及を妨げていた。
【０００５】
また、最近のマルチメディア時代の情報は画像と文字が混在し、それを電子写真法を用いた画像形成装置と同じように普通紙に記録したいという強い要望が出されているが、従来の染料熱転写記録方法では普通紙上に高品質の画像を得ることは不可能であった。
【０００６】
そこで、本発明者らは特願平２−２６５６４１号，特願平２−２８２１１２号特願平２−２８２１１３号等において受像体の基質に関係なく、受像体に高画質フルカラー画像を形成することができる染料熱転写記録方法を提案した。この方法は、第１の基材の裏面に滑性耐熱層を有し，表面に少なくとも染着層を有する染着層転写体と、第２の基材の裏面に滑性耐熱層を有し，表面に少なくとも色材層を有する染料転写体と、第３の基材上に機能層を有する中間媒体と、受像体とを用い、前記染着層転写体の前記滑性耐熱層に熱ヘッドを当接させることにより前記染着層を前記中間媒体の機能層上に熱転写するプロセス，前記染料転写体の前記滑性耐熱層に熱ヘッドを当接させることにより前記機能層上に転写された染着層に前記色材層中の染料を画信号に応じて熱転写記録するプロセス，及びこの染料が記録された染着層を受像体の主面上に熱転写するプロセスをこの順に行って熱転写記録を行うものである。
【０００７】
【発明が解決しようとする課題】
しかるに、前記従来の染料熱転写記録では、受像体の外周部に未記録の余白部が形成され、受像体全体に画像を記録することができないという問題点があった。
【０００８】
本発明の目的は、受像体の全面に画像を記録することができる染料熱転写記録方法を提供することにある。
【０００９】
【課題を解決するための手段】
本発明にかかる熱転写記録方法は、第１の基材の裏面に滑性耐熱層を有し、表面に離型層と染着層をこの順に積層した積層構成を有する染着層転写体と、第２の基材の裏面に滑性耐熱層を有し、表面に接着層と色材層をこの順に積層した積層構成を有する染料転写体と、第３の基材上に機能層を有する中間媒体と、受像体とを用い、前記染着層転写体の前記滑性耐熱層に熱ヘッドを当接させることにより前記染着層を前記中間媒体の機能層上に熱転写するプロセス、前記染料転写体の前記滑性耐熱層に熱ヘッドを当接させることにより前記機能層上に転写された前記染着層に前記色材層中の染料を画信号に応じて熱転写記録するプロセス、及び前記染料が記録された前記染着層を受像体の主面上に熱転写するプロセスをこの順に実行する熱転写記録方法であって、
前記中間媒体の機能層に前記染着層転写体の前記染着層をこれの面積が前記受像体の面積より大きくなるよう転写させ、この染着層に前記染料転写体の色材層中の染料を熱転写記録して前記受像体の面積より大きい面積の画像を形成し、この画素記録染された染着層を前記受像体に転写させると同時に、これの前記受像体の外周からはみ出す部分を前記受像体の外周縁部によって切断することを特徴とする。
【００１０】
本発明にかかる熱転写記録装置は、第１の基材の裏面に滑性耐熱層を有し、表面に離型層と染着層をこの順に積層した積層構成を有する染着層転写体と、第２の基材の裏面に滑性耐熱層を有し、表面に接着層と色材層をこの順に積層した積層構成を有する染料転写体と、第３の基材上に機能層を有する中間媒体と、受像体とを用い、前記染着層転写体の前記滑性耐熱層に熱ヘッドを当接させることにより前記染着層を前記中間媒体の機能層上に熱転写し、前記染料転写体の前記滑性耐熱層に熱ヘッドを当接させることにより前記機能層上に転写された前記染着層に前記色材層中の染料を画信号に応じて熱転写記録し、前記染料が記録された前記染着層を受像体の主面上に熱転写する熱転写記録装置であって、
前記中間媒体の機能層に前記染着層転写体の前記染着層をこれの面積が前記受像体の面積より大きくなるよう転写させ、この染着層に前記染料転写体の色材層中の染料を熱転写記録して前記受像体の面積より大きい面積の画像を形成し、この画素記録染された染着層を前記受像体に転写させると同時に、これの前記受像体の外周からはみ出す部分を前記受像体の外周縁部によって切断されるようにしたことを特徴とする。
【００１１】
【発明の実施の形態】
本発明の熱記録転写体の第１の構成によれば、第１の基材の裏面に滑性耐熱層を有し，表面に離型層と染着層をこの順に積層した積層構成を有する染着層転写体と、第２の基材の裏面に滑性耐熱層を有し，表面に接着層と色材層をこの順に積層した積層構成を有する染料転写体と、第３の基材上に機能層を有する中間媒体と、受像体とを用い、前記染着層転写体の前記滑性耐熱層に熱ヘッドを当接させることにより前記染着層を前記中間媒体の機能層上に熱転写するプロセス，前記染料転写体の前記滑性耐熱層に熱ヘッドを当接させることにより前記機能層上に転写された染着層に前記色材層中の染料を画信号に応じて熱転写記録するプロセス，及びこの染料が記録された染着層を受像体の主面上に熱転写するプロセスをこの順に実行する染料熱転写記録に前記染料転写体として供される熱記録転写体であって、基材と、前記基材の裏面に形成された滑性耐熱層と、前記基材の表面に接着層を介して形成された色材層とを有し、この色材層を構成する樹脂をポリアクリロニトリルスチレン樹脂と、下記の（ａ）（ｂ）（ｃ）の樹脂のうちの少なくとも１つの樹脂とを、混合比が２：８ないし８：２の範囲となるよう混合してなるものとしたから、前記色材層が良好な耐熱性及び柔軟性を示すとともに、十分な接着力によって前記接着層に接着することになり、その結果、高温度下の巻回保存時，及び記録プロセス時の安定性に優れたものとなる。
【００１２】
（ａ）ポリ塩化ビニル樹脂，（ｂ）ポリ塩化ビニル樹脂とポリ酢酸ビニル樹脂の共重合樹脂，（ｃ）ポリ塩化ビニル樹脂とポリ酢酸ビニル樹脂とポリビニルアルコール樹脂の共重合樹脂。
【００１３】
前記第１の構成の好ましい例として、基材表面の接着層を構成する樹脂と，前記色材層との付着力が、５０℃以上で２０ｇ／インチ以上であると、記録プロセスを繰り返し安定に遂行させることができる。
【００１４】
また前記第１の構成の好ましい例として、前記基材表面の接着層を構成する樹脂のガラス転移温度が４０℃以上であると、中間媒体が５０〜６０℃に加熱されるような環境下においても、色材層と接着層のブロッキングを起こすことなく、記録プロセスを繰り返し安定に遂行させることができる。
【００１５】
また前記第１の構成の好ましい例として、前記第１の構成において、前記基材がポリエステルフィルムであり、前記基材表面の接着層を構成する樹脂がガラス転移温度が６０℃以上のランダム共重合ポリエステル樹脂であると、前記よりも更に高温な環境下においても、色材層と接着層のブロッキングを起こすことなく、記録プロセスを繰り返し安定に遂行させることができる。
【００１６】
また前記第１の構成の好ましい例として、前記基材を前記染料転写体が形成される前記第２基材と，前記染着層転写体が形成される前記第１基材の両方に使用されるものであると、染料転写体と染着層転写体を１つの転写体にて構成でき、記録プロセスの遂行を小さい占有空間にて行うことができる。
【００１７】
本発明の熱記録転写体の第２の構成によれば、第１の基材の裏面に滑性耐熱層を有し，表面に離型層と染着層をこの順に積層した積層構成を有する染着層転写体と、第２の基材の裏面に滑性耐熱層を有し，表面に接着層と色材層をこの順に積層した積層構成を有する染料転写体と、第３の基材上に機能層を有する中間媒体と、受像体とを用い、前記染着層転写体の前記滑性耐熱層に熱ヘッドを当接させることにより前記染着層を前記中間媒体の機能層上に熱転写するプロセス，前記染料転写体の前記滑性耐熱層に熱ヘッドを当接させることにより前記機能層上に転写された染着層に前記色材層中の染料を画信号に応じて熱転写記録するプロセス，及びこの染料が記録された染着層を受像体の主面上に熱転写するプロセスをこの順に実行する染料熱転写記録に前記染着層転写体として供される熱記録転写体であって、基材と、前記基材の裏面に形成された滑性耐熱層と、前記基材の表面に離型層を介して形成された染着層とを有し、この染着層を前記離型層から遠い位置にある部分程高い耐熱性を示すものにしたから、記録プロセスにおいて、中間媒体に保持された染着層は、その耐熱性の低い側の表面部が色材層に接着することになり、記録感度を高めることができる。また、高温巻回保存時にはその耐熱性の高い側の表面部が滑性耐熱層と接することになり、両層間の接着等によるトラブルも防止することができる。
【００１８】
本発明の熱記録転写体の第３の構成によれば、第１の基材の裏面に滑性耐熱層を有し，表面に離型層と染着層をこの順に積層した積層構成を有する染着層転写体と、第２の基材の裏面に滑性耐熱層を有し，表面に接着層と色材層をこの順に積層した積層構成を有する染料転写体と、第３の基材上に機能層を有する中間媒体と、受像体とを用い、前記染着層転写体の前記滑性耐熱層に熱ヘッドを当接させることにより前記染着層を前記中間媒体の機能層上に熱転写するプロセス，前記染料転写体の前記滑性耐熱層に熱ヘッドを当接させることにより前記機能層上に転写された染着層に前記色材層中の染料を画信号に応じて熱転写記録するプロセス，及びこの染料が記録された染着層を受像体の主面上に熱転写するプロセスをこの順に実行する染料熱転写記録に前記染着層転写体として供される熱記録転写体であって、前記染着層を、前記離型層に接する第１染着層と，この第１染着層を被覆して保護する保護層とからなる２層構成、または前記離型層に接する第１染着層と，この第１染着層を被覆して保護する保護層と，この保護層上に形成された膜強度補強層とからなる３層構成にしたから、印刷形成によって強度的に安定な染着層を形成することができ、特に、３層構成にすることにより、記録プロセスを安定化できる厚みを有する染着層を形成することができる。
【００１９】
また前記第３の構成の好ましい例として、前記第１染着層がガラス転移温度Ｔｇが６０℃未満のポリビニルブチラール樹脂またはポリビニルアセタール樹脂と離型材とを含むものであり、前記保護層が７０℃以上の互いに異なる温度のガラス転移温度Ｔｇを有する複数のポリビニルブチラール樹脂またはポリビニルアセタール樹脂を混合した樹脂を含み、かつ、前記第１染着層の全面を被覆する面積を持つものものであり、前記膜強度補強層がガラス転移温度Ｔｇが１００℃以上のポリビニルブチラール樹脂またはボリビニルアセタール樹脂を含み、前記保護層の外形より小さい面積を持ち、かつ、前記保護層より高い耐熱性を有するものであると、印刷形成によって、強度的に安定で、記録感度を向上でき、しかも、高温巻回保存時における滑性耐熱層との接着を防止できる染着層を形成することができる。
【００２０】
本発明の熱記録転写体の第４の構成によれば、第１の基材の裏面に滑性耐熱層を有し，表面に離型層と染着層をこの順に積層した積層構成を有する染着層転写体と、第２の基材の裏面に滑性耐熱層を有し，表面に接着層と色材層をこの順に積層した積層構成を有する染料転写体と、第３の基材上に機能層を有する中間媒体と、受像体とを用い、前記染着層転写体の前記滑性耐熱層に熱ヘッドを当接させることにより前記染着層を前記中間媒体の機能層上に熱転写するプロセス，前記染料転写体の前記滑性耐熱層に熱ヘッドを当接させることにより前記機能層上に転写された染着層に前記色材層中の染料を画信号に応じて熱転写記録するプロセス，及びこの染料が記録された染着層を受像体の主面上に熱転写するプロセスをこの順に実行する染料熱転写記録の前記染着層転写体として使用される熱記録転写体であって、基材と、前記基材の裏面に形成された滑性耐熱層と、前記基材の表面に離型層を介して形成された染着層とを有し、この染着層の前記色材層に接触する表面領域を構成する樹脂と、前記色材層を構成する樹脂とを互いに非相溶な樹脂で構成したことにより、記録時に染着層が染料転写体の色材層に熱融着せず、記録後これらを容易に剥離することができ、その結果、記録プロセスを繰り返し安定に遂行させることができる。
【００２１】
前記第４の構成の好ましい例として、前記染着層の前記色材層に接触する表面領域を構成する樹脂がポリビニルブチラール，ポリビニルアセタールから選ばれる１種類以上の樹脂であり、前記色材層を構成する樹脂がポリアクリロニトリルスチレン樹脂，ポリ塩化ビニル樹脂，ポリ酢酸ビニル樹脂，ポリビニルアルコール樹脂，ポリエステル樹脂，ポリアミド樹脂，ウレタン樹脂，アクリル樹脂から選ばれる１種類以上の樹脂であると、染着層の色材層に接触する表面領域と、色材層とを確実に相溶しないものにすることができる。
【００２２】
また前記第４の構成の好ましい例として、前記染着層の前記色材層に接触する表面領域を構成する樹脂が、ポリアクリロニトリルスチレン樹脂，ポリ塩化ビニル樹脂，ポリ酢酸ビニル樹脂，ポリビニルアルコール樹脂，ポリエステル樹脂，ポリアミド樹脂，ウレタン樹脂，アクリル樹脂から選ばれる１種類以上の樹脂であり、前記色材層を構成する樹脂がポリビニルブチラール，ポリビニルアセタールから選ばれる１種類以上の樹脂であると、染着層の色材層に接触する表面領域と、色材層とを確実に相溶しないものにすることができる。
【００２３】
また前記第２，第３，及び第４の構成の好ましい例として、前記染着層の前記中間媒体上の機能層に対する付着力が１０ｇ／２５ｍｍ〜１００ｇ／２５ｍｍの範囲にあると、染着層の中間媒体上の機能層への転写が安定に行われ、かつ、染着層への染料転写体からの染料の記録が安定に行われるとともに、受像体への染着層の転写が安定に行われることとなり、記録プロセスの安定化が図られる。
【００２４】
また前記第２，第３，及び第４の構成の好ましい例として、前記基材が前記染着層転写体が形成される前記第１基材と，前記染料転写体が形成される前記第２基材との両方に使用されるものであると、記録プロセスの遂行を小さい占有空間にて行うことができる。
【００２５】
また前記第１，第２，第３，及び第４の構成の好ましい例として、前記基材の裏面に形成された滑性耐熱層が、少なくとも耐熱性樹脂，無機あるいは有機の微粒子，及び液状潤滑性物質を含んでなるものであると、耐熱性樹脂が層に耐熱性を付与し、無機あるいは有機の微粒子が層の表面を粗面化するとともに層の熱ヘッドに対する動摩擦係数を低減化し、液状潤滑性物質が層表面に湧き出して，層の熱ヘッドに対する動摩擦係数をより一層低減化するので、記録プロセスにおいて転写体を安定に走行させることができる。また、前記液状潤滑性物質が側鎖に官能基を有し、分子量が１００００以上の非反応性シリコーンオイルであると、滑性耐熱層中において液状潤滑性物質の自由な動きが束縛されることとなって、転写体を巻回して長時間高温保持しても、基材表面にある染着層または色材層へ液状潤滑性物質が転移することがなくなり、その結果、記録プロセスにおいて、中間媒体の機能層表面及び色材層表面が液状潤滑性物によって汚染されることが防止され、染着層の中間媒体へ保持される保持力を一定に保つことができる。
また、前記非反応性シリコーンオイルが、ポリエーテル基の分子量が６０００で、ポリエーテル基によって挟まれるジメチルポリシロキサン部分の分子量が１２０００のポリエーテル変性シリコーンのような前記官能基部分の分子量が前記官能基によって挟まれるジメチルポリシロキサン部分の分子量より大きいものであると、非反応性シリコーンオイルが滑性耐熱層中でより強く拘束されることになり、記録プロセスでの液状潤滑性物による中間媒体の機能層表面及び色材層表面の汚染を確実に無くすことができ、記録プロセスをより一層安定化させることができる。
【００２６】
本発明の熱転写記録方法によれば、第１の基材の裏面に滑性耐熱層を有し，表面に離型層と染着層をこの順に積層した積層構成を有する染着層転写体と、第２の基材の裏面に滑性耐熱層を有し，表面に接着層と色材層をこの順に積層した積層構成を有する染料転写体と、第３の基材上に機能層を有する中間媒体と、受像体とを用い、前記染着層転写体の前記滑性耐熱層に熱ヘッドを当接させることにより前記染着層を前記中間媒体の機能層上に熱転写するプロセス，前記染料転写体の前記滑性耐熱層に熱ヘッドを当接させることにより前記機能層上に転写された染着層に前記色材層中の染料を画信号に応じて熱転写記録するプロセス，及びこの染料が記録された染着層を受像体の主面上に熱転写するプロセスをこの順に実行する染料熱転写記録であって、前記中間媒体の機能層に前記染着層転写体の前記染着層をこれの面積が前記受像体の面積より大きくなるよう転写させ、この染着層に前記染料転写体の色材層中の染料を熱転写記録して前記受像体の面積より大きい面積の画像を形成し、この画素記録染された染着層を前記受像体に転写させると同時に，これの前記受像体の外周からはみ出す部分を前記受像体の外周縁部によって切断するようにしたから、従来困難であった受像体の全面に画像を形成することが可能となる。
【００２７】
図１に本発明の熱記録転写体を用いた染料熱転写記録の第１の形態を示す。基材２１の裏面に耐熱滑性層１３が形成され、表面に離型層２２と染着層２３がこの順に形成されてなる染着層転写体２が、ドラム状に形成された中間媒体４と熱ヘッド３−１の間に供給ローラ１０と巻取ローラ１０′によって送られ、挟着される。そして、ここで中間媒体４の基材４１上に設けられた機能層４２上に染着層転写体２の染着層２３の熱転写が行われる。ここで中間媒体は閉ループを形成するベルト状，あるいはシ−ト状で形成されたものであってもよい。図中の２′は染着層２３が転写された後の染着層転写体２の状態を示す。次に、基材１１の裏面に耐熱滑性層１３が形成され、表面に接着層１４と色材層１２がこの順に形成されてなる染料転写体１が中間媒体４と熱ヘッド３−２の間に供給ローラ９と巻取ローラ９′によって送られ、ここで、染料転写体１の色材層１２中の昇華性染料が中間媒体４上の染着層２３中に熱拡散転写される。最後に、熱ロ−ラ７を用いて受像体５上に中間媒体４上の染着層２３中に記録された画像が染着層２３と共に熱転写され、受像体５の基質に依存することなく受像体５に高画質画像が形成される。また、図中の６は受像体５上に画像記録がなされた染着層２３′が転写された後の状態を示す。なお、中間媒体４がシ−ト状である場合、染着層２３の転写、色材層１２からの染料の転写毎にシート状の中間媒体をスウィングして使用する。
【００２８】
図２に本発明の熱記録転写体を用いた染料熱転写記録の第２の形態を示す。ここでは、前述の染着層転写体２と染料転写体１とが一体化されて熱記録転写体１００を構成している。即ち、基材１１（２１）の裏面に耐熱滑性層１３を形成し、表面に接着層１４を形成し、この接着層１４上の第１の領域に離型層２２と染着層２３とをこの順に形成し、第２，第３の領域に色相が異なる色材層１２−１，１２−２を形成して転写体１００を構成している。そして、この転写体が中間媒体４と熱ヘッド３−２の間に供給ローラ９と巻取ローラ９′によって送られ、熱ヘッド３−２によって、先ず染着層２３が熱転写され、これに続いて前記熱転写された染着層２３に色材層１２−１，１２−２中の昇華性染料が熱転写される。昇華性染料が染着層２３に記録された後のプロセスは前記図１に示した第１の形態と同じである。
【００２９】
図３に本発明の熱記録転写体を用いた染料熱転写記録の第３の形態を示す。ここでは図４に示す前記第２の形態で用いられた染着層転写体と染料転写体が同一基材に形成された熱記録転写体１００と、ベルト状中間媒体４′を用いる。ベルト状中間媒体４′はプラテン、ガイドロ−ラ等で架張されている。熱記録転写体１００の染着層２３の部分がベルト状に形成された中間媒体４′と熱ヘッド３の間に送られて挟着され、中間媒体４′の基材４１上に設けられた機能層４２上に染着層２３の熱転写が行われる。染着層２３は後で染料が記録される部分だけの選択転写か，または一定の面積全部の転写が行なわれる。次に、熱記録転写体１００の色材層１２の部分が中間媒体４′と熱ヘッド３の間に送られて挟着され、色材層１２中の昇華性染料が中間媒体４′上に転写された染着層２３中に熱拡散転写される。最後に、熱ロ−ラ７によって受像体５上に中間媒体４上の染着層２３中に記録された画像が染着層２３と共に熱転写され、受像体５の基質に依存することなく受像体５に高画質画像が形成される。
【００３０】
前記の本発明の染料熱転写記録において、基材１１は厚み２ないし１０ミクロンの高分子フィルムが用いられる。一般的には、ポリエチレンテレフタレート（ＰＥＴ）フィルムが用いられるが、芳香族ポリアミド（アラミド）、ポリイミド、ポリカーボネート、ポリフェニレンサルファイド、ポリエ−テルケトン、トリアセチルセルロース、セロファン等、成膜可能な樹脂によるフィルムも有用である。また、これらの樹脂にカーボン等の導電性粒子を混入して成膜した低抵抗性フィルムを用いてもよい。
【００３１】
耐熱滑性層１３は、熱ヘッド３，３−１，３−２と，基材１１，２１との間の潤滑性を付与するために設けられており、例えば紫外線硬化樹脂等の耐熱性樹脂、液状潤滑材、及び有機または無機微粒子を少なくとも含んで構成されている。耐熱性樹脂が層に耐熱性を付与する。微粒子が層の表面を粗面化すると共に層の表面の摩擦係数を低減化して、層に安定した走行性を付与する。液状潤滑材が熱ヘッド３，３−１，３−２によって膜内部から微量に膜表面に湧出し、染料転写体１，染着層転写体２，及び熱記録転写体１００の走行安定性を増大させる。前記耐熱性樹脂として熱可塑性樹脂を用いることもできるが、熱・光（紫外線）・電子線等による硬化樹脂（架橋樹脂）を用いた方が安定した耐熱性を得らことができ、好ましい。かかる硬化樹脂としてはシリコーン系、アクリレート系、エポキシ系、不飽和アルデヒド樹脂等を挙げることができるが、中でもエポキシアクリレート系樹脂の硬化物が優れた特性を示す。無機または有機の微粒子としては、無機系では金属、金属の酸化物、硫化物、炭化物、窒化物、フッ化物の微粒子や、黒鉛、カーボンブラック、顔料を挙げることができる。このうち酸化チタン、二硫化モリブデン、疎水性（無水）シリカが好まく、その中でも気相成長法で製造された超微粒子状の疎水性（無水）シリカ，酸化チタン，酸化アルミニウムが特に好ましい。有機系では球形シリコーン樹脂微粒子等を挙げることができる。
【００３２】
液状潤滑性物質としては、各種のジルチルポリシロキサンシリコーンオイル、フッ素系シリコーンオイル、各種変性シリコーンオイル（エポキシ変性、ポリエ−テル変性、アミノ変性、カルボキシル変性等）、有機金属塩、フルオロアルキル化合物等のフッ素系界面活性剤等を用いることができる。液状潤滑性物質が側鎖に官能基を有し，分子量が１００００以上の非反応性シリコーンオイルであると、滑性耐熱層中でのシリコーンオイルの自由な動きが束縛され、転写体を巻回し長時間高温に保持した場合に生ずる，基材表面側の染着層２３表面または色材層１２表面にシリコーンオイルが転移することを抑制することができる。更に、この非反応性シリコーンオイルのジメチルポリシロキサン部に挟まれる側鎖官能基部分の分子量が側鎖官能基部分に挟まれるジメチルポリシロキサン部分の分子量より大きいものであると、滑性耐熱層中でシリコーンオイルの拘束力がより一層高まり、基材表面側の染着層２３表面または色材層１２表面へのシリコ−ンオイルの転移を抑制する効果がより一層強化される。これの具体例としては、シロキサン部分子量６０００、官能基部分子量１２０００の分子量１８０００のポリエーテル変性シリコーンオイル等がある。従って、液状潤滑性物質に分子量が１００００以上の非反応性シリコーンオイルを用いると、記録動作中、中間媒体４，４′の機能層４２表面及び色材層１２表面がシリコーンオイルで汚染されず、染着層２３を中間媒体４，４′上に保持する付着力を一定に保つことができる。特に、非反応性シリコーンオイルがそのジメチルポリシロキサン部に挟まれる側鎖官能基部分の分子量がジメチルポリシロキサン部分の分子量より大きいものであると、染着層２３を中間媒体４，４′上に保持する付着力をより高いレベルで一定に保つことができる。
【００３３】
基材１１，２１上の接着層１４は一般的には基材製膜時において基材と一体的に０．５μｍ以下の厚みに形成される。基材１１にポリエステルフィルムを用いる時には、接着層にランタ゛ム共重合ポリエステル樹脂が用いられる。一般的には室温付近での色材層１２との大きな接着力を保持するために、室温付近にガラス転移温度Ｔｇのあるポリエステル樹脂が用いられる。しかし、本発明の中間媒体を用いた染料熱転写方式では、中間媒体の表面温度をしばしば５０℃〜６０℃に保持される。このため、５０℃以上でも色材層１２を基材１１，２１によく付着させて、記録時に色材層１２と染着層２３との融着によるブロッキング現象等の故障が起こらないように設計しなければならない。そのため、接着層１４を構成する樹脂のガラス転移温度Ｔｇは４０℃以上であることが好ましい。更に６０℃以上のＴｇを有するポリエステル樹脂は装置が高温状態に置かれている時にも安定である。Ｔｇ＝６７℃のポリエステル樹脂（バイロン２００：東洋紡績（株）製）とＴｇ＝６℃のポリエステルホリエステル樹脂（バイロン３００：東洋紡績（株）製）の，ポリエステルフィルムとの剥離力を比較すると、前者は６０℃付近に剥離力の最大があり、後者は室温付近に剥離力の最大があり、それぞれ、温度が高くなると共にその値は低下する。図５に接着層１４にバイロン２００を用いた転写体と，接着層１４にバイロン３００を用いた転写体とにおける色材層１２と接着層１４間の剥離力の温度特性を測定した結果と、前記２つの転写体を６０℃，６０％ＲＨの恒温層に３００時間券回保存した後に，それぞれにおける色材層１２と接着層１４間の剥離力の温度特性を測定した結果を示す。記録部温度がいかなる温度であっても、色材層／接着層間剥離力は色材層／染着層間剥離力より大きいことが、記録プロセスを成立させるために必要である。５０℃において、色材層／染着層間剥離力は２０ｇ／インチ以下であるので、色材層／接着層間剥離力はその値以上が必要である。従って、接着層１４の構成樹脂として４０℃以上にＴｇのある樹脂を用いることにより、転写体を高温に長時間保存したものを用い，記録装置の温度が高温となる環境下においても、記録プロセスを安定に遂行することができる。
【００３４】
色材層１２は少なくとも昇華性染料と結着樹脂から構成される。昇華性染料としては分散染料、油溶染料、塩基性染料、カラーフォーマー等が用いられる。特に、インドアニリン系、キノフタロン系、ジシアノイミダゾール系、ジシアノメチン系、トリシアノビニル系等の分散染料が有効である。結着樹脂としては、ポリエステル、ポリビニルブチラール、ポリアクリロニトリルスチレン樹脂、ポリ塩化ビニル樹脂、ポリ酢酸ビニル樹脂、ポリビニルアルコール樹脂、ポリビニルアセタール樹脂、ポリアミド樹脂、アクリル樹脂、ウレタン樹脂、低分子ポリスチレン樹脂等が用いられる。また、これらの樹脂は染着層２３の構成樹脂としても使用される。この色材層１２の結着樹脂と，染着層２３の構成樹脂とは非相溶の関係が好ましい。これは、記録時に色材層１２と染着層２３が熱融着せず、記録後容易にこれらを剥離できるようにするためである。染着層２３の構成樹脂にポリエステル、ポリビニルブチラール等の樹脂を用いる場合には、色材層１２の結着樹脂としては、ポリアクリロニトリルスチレン（ＡＳ）樹脂、ポリ塩化ビニル樹脂、ポリ酢酸ビニル樹脂、ポリビニルアルコール樹脂のいずれか、あるいはこれらのうちの２つ以上を混合した混合樹脂が用いられる。逆に色材層１２の結着樹脂にポリエステル、ポリビニルブチラール等の樹脂を用いる場合には、染着層２３の構成樹脂としてポリアクリロニトリルスチレン（ＡＳ）樹脂、ポリ塩化ビニル樹脂、ポリ酢酸ビニル樹脂、ポリビニルアルコール樹脂のいずれか、あるいはこれらのうちの２つ以上を混合した混合樹脂が用いられる。樹脂の相溶・非相溶は、溶解性パラメータや臨界表面張力あるいは接触角等によって評価できる。例えば、ポリビニルブチラールの臨界表面張力Ｆが約２４ダイン／ｃｍであるのに対して、本文の他の一般の色材層または染着層樹脂のＦは３０以上が多い。溶解性パラメ−タＳＰ値で評価すると前者が約７でテフロン（登録商標）の６に近く、後者のそれは９以上のものが多い。
【００３５】
色材層１２の結着樹脂としてＡＳ樹脂を用いる場合、ＡＳ樹脂はＴｇ＝１０４℃であり、色材層の耐熱性の点では最適であるが、膜自身が脆く接着層１４との接着力も十分ではない。そこで、これに、接着層１４との接着力も強く膜の柔軟性のあるポリ塩化ビニル樹脂、ポリ酢酸ビニル樹脂、ポリビニルアルコール樹脂の共重合樹脂（Ｔｇ＝６４℃）を混合したものを色材層１２の結着樹脂とすると、転写体１の券回保存性と記録の安定性の両方を満足させることができる。ＡＳと前記共重合樹脂との混合比率は２：８ないし８：２の範囲にあるのが好ましい。
【００３６】
染着層転写体２は基材２１（１１）上に離型層２２と染着層２３を積層して構成される。離型層２２はシリコ−ン樹脂や弗素樹脂等を薄く形成したもの、またはシリコーン樹脂，弗素樹脂以外の樹脂に離型材を混入・分散，あるいは反応させたものが用いられる。シリコーン樹脂としてはコーティング用または剥離紙用または粘着紙用の付加重合あるいは縮合重合して成膜できるものが好ましい。弗素樹脂としはポリテトラフルオロエチレン、テトラフルオロエチレン・パーフルオロアルキルビニルエーテル共重合体、ビニリデンフルオライド・ヘキサフルオロプロピレン系ゴム材料、各種含弗素樹脂等が有効である。樹脂に添加させる離型材としては、各種のシリコーン系潤滑材、弗素系界面活性材、パラフィン及びポリエチレン等のワックス類、高級脂肪族アルコール、高級脂肪酸アミド及びエステル等がある。液状潤滑材としては、ジメチルポリシロキサン、メチルフェニルポリシロキサン、弗素シリコーンオイル、その他の各種変性シリコーンオイル、２種以上の反応性シリコーンオイルの反応物（例えば、エポキシ変性とカルボキシルまたはアミノ変性の反応物等）がある。また、樹脂と潤滑材の反応型でもよく、例えば、ポリシロキサンをアクリル樹脂にグラフト重合させた水溶性ポリシロキサングラフトアクリル樹脂、シロキサンメタクリレートを末端または側鎖に付加したアクリルシリコーン（シリコン）またはアクリルウレタンシリコーン（シリコン）樹脂等も有効である。
【００３７】
染着層２３は、好ましくは、基材２１（１１）表面の離型層２２に接する第１染着層２４と保護層２５の２層構成，または第１染着層２４と保護層２５と膜強度補強層２６の３層構成からなっている。第１染着層２４から上層の保護層２５，補強層２６にゆく程、構成樹脂の耐熱性が高いことが好ましい。これは、記録時に色材層１２に耐熱性の低い第１染着層２４が接して記録感度を高めることができるためであり、また、高温巻回保存時に滑性耐熱層１３に耐熱性の高い保護層２５または補強層２６が接することにより、染着層２３と滑性耐熱層１３との接着が起こることを防止できるためである。また、積層製膜上の観点から、第１染着層２４と保護層２５をこれらに同一樹脂種の樹脂を含ませることにより構成する，または第１染着層２４と保護層２５と補強層２６をこれらに同一樹脂種の樹脂を含ませることにより構成するのが好ましく、これにより、均質な膜性状の積層膜を印刷形成することが可能となる。一般にグラビア印刷で製膜する時、一層の膜厚は高々１．５μｍであり、本プロセスを実現するために必要な染着層部分の厚みは３〜４μｍである。このため、第１染着層２４のみでは膜厚が不足し、プロセス安定化のためには膜強度補強層２６を有する３層構成にするのが好ましい。
【００３８】
染着層２３を前記２層また３層構成にする場合は、以下の構成にするのが好ましい。即ち、前記第１染着層２４をガラス転移温度Ｔｇが６０℃未満のポリビニルブチラール樹脂またはポリビニルアセタ−ル樹脂と離型材と含むものにし、保護層２５を７０℃以上の互いに異なる温度のガラス転移温度Ｔｇを有する複数のポリビニルブチラール樹脂またはポリビニルアセタール樹脂を混合した樹脂を含み、かつ、第１染着層２４の全面を被覆する面積を持つものものにし、膜強度補強層２６をガラス転移温度Ｔｇが１００℃以上のポリビニルブチラール樹脂またはボリビニルアセタール樹脂を含み、保護層２５の外形より小さい面積を持ち、かつ、保護層２５より高い耐熱性を有するものにする。
【００３９】
中間媒体４は金属ドラムまたは高分子フィルムの基材４１上に機能層４２が設けられている。機能層４２はシリコーン樹脂や弗素樹脂等を薄く形成したゴム状のもの、またはシリコーン樹脂や弗素樹脂以外の樹脂に離型材を混入・分散、あるいは反応させたものが用いられる。シリコーン樹脂としてはコーティング用または剥離紙用または粘着材料としての付加重合あるいは縮合重合して成膜できるものが好ましい。弗素樹脂としはポリテトラフルオロエチレン、テトラフルオロエチレン・パーフルオロアルキルビニルエーテル共重合体、ビニリデンフルオライド・ヘキサフルオロプロピレン系ゴム材料、各種含弗素樹脂等が有効である。特に、フッ化ビニリデン・６フッ化プロピレン・４フッ化エチレンの３元系共重合体フッ素ゴム（バイトン：昭和電工デュポン製）は有効である。この３元共重合体フッ素ゴムはカーボンや酸化マグネシウム等の微粒子と共に用いられて製膜される。
【００４０】
受像体５はボンド紙や普通紙等のパルプ系用紙でもよく、乳白ＰＥＴ、ユポ等の合成紙でもよく、パルプ紙とフィルムの接着した基材でもよい。また、テレホンカード、プリペイドカード、ＩＣカード等の各種カード類であってもよい。従来、受像体には受像体周辺に未記録の余白部を残して画像形成されていた。本発明では受像体５が葉書や各種カード類のように固く剛性の強い場合には、以下のようにして、受像体の全面に画像形成をすることができる。即ち、中間媒体４，４′上に染着層２３をこれの面積が受像体５の面積より大きくなるよう転写し、この染着層２３に受像体５の面積より大きな画像を形成した後、転写に要する熱または圧力の条件を最適化して，染着層２３をこれがカード等の受像体５の周辺部によって切断されるように受像体５に転写する。そして、受像体５への染着層２３の転写後、中間媒体４上に残った染着層２３をクリーニング機構等で除去する。
【００４１】
記録ヘッドには、普通の熱（サ−マル）ヘッド、通電ヘッド、レーザーヘッド等が用いられる。ライン型サーマルヘッドを用いた時の記録条件は、ライン記録周期Ｔ：３３ｍｓないし４ｍｓ、印加パルス幅：１６ｍｓないし２ｍｓ、記録エネルギ−Ｅ：８ないし６Ｊ／ｃｍ²でおこなわれる。
【００４２】
記録された染着層の受像体５への熱転写は熱ロール７を用いる時は、温度約１４０゜Ｃ、速度１０ｍｍ／秒、圧力１Ｋｇ／ｃｍ²で行なわれる。
【００４３】
【実施例】
以下、実施例によって本発明をより具体的に説明する。
【００４４】
（実験例１）
・染料転写体（１）の作製
５ミクロンのＰＥＴフィルムの裏面に２ミクロンの後述する滑性耐熱層を設け、表面に０．３ミクロンのＴｇ＝６７度Ｃのランダム共重合ポリエステル樹脂を接着層として塗工した後、接着層上に下記処方からなるインクをグラビアコーターで固形厚み１ミクロンになるように色材層を形成した。ここで、滑性耐熱層は下記処方からなる塗料をマイクログラビアコータで塗布し、６０度Ｃの熱風で溶媒を蒸発させた後、１ＫＷの高圧水銀灯を照射して硬化させることにより行った。
（インク）
インドアニリン系分散染料２．５重量部
アクリルスチレン樹脂２重量部
ポリ塩化ビニル共重合樹脂２重量部
アミド変性シリコ−ン油０．０２重量部
トルエン２０重量部
２−ブタノン２０重量部
（塗料）
エポキシアクリレ−ト樹脂１２重量部
ネオペンチルグリコ−ルジアクリレ−ト３重量部
２−ヒドロキシ−２−メチルプロピオフェノン０．７５重量部
アエロジル（疎水性超微粒子シリカの商品名）２重量部
ポリエ−テル変性ジメチルシリコ−ン０．４重量部
（分子量１８０００）
酢酸エチル１００重量部
・染着層転写体（２）の作製
染料転写体と同じＰＥＴ基材、同じ接着層、同じ滑性耐熱層を用い、接着層上に離型層として脱オキシム型シリコーン樹脂：ＰＲＸ３０５（東レ・ダウコーニング・シリコーン社製商品名）１０重量部、トルエン２０重量部からなる塗料をバーコーターで厚み０．３ミクロンに形成した。この離型層上に第１染着層としてポリビニルブチラ−ル樹脂：ＢＬ−Ｓ（積水化学社製商品名，Ｔｇ＝５５℃）６重量部、シロキサンメタアクリレートを側鎖に有するアクリルシリコーン（シリコン）樹脂：Ｆ−６Ａ（三洋化成工業社製商品名）０．０６重量部、ジ−ｎ−ブチル錫ジラウレート０．００４重量部、トルエン及び２−ブタノンをそれぞれ１３重量部からなる塗料をバーコーターで厚み１ミクロンになるよう製膜した。この上に保護層として、Ｔｇ＝７５度Ｃのポリビニルブチラール樹脂とＴｇ＝１１０度Ｃのアセトアセタール化ポリビニルアルコ−ル樹脂（アセタール樹脂）を６：４の組成で１．５ミクロンになるように製膜した。更にこの上に上記２種類の樹脂を３：７の組成で１．５ミクロン製膜して、合計３層の染着層部を作製した。
【００４５】
・中間媒体（４）の作製
金属ドラム上に、５０ミクロンのポリイミドフィルムをベースとし、下記の機能層塗料を約３０ミクロンに製膜して中間媒体とした。金属ドラムを用いず、機能層を形成したポリイミドをベルトとして用いてもよい。
（機能層塗料）
フッ素ゴム１００重量部
架硫材３重量部
カ−ボン２０重量部
酸化マグネシウム１５重量部
メチルエチルケトン３５０重量部
上記染料転写体（１），染着層転写体（２），及び中間媒体（４）を用い、下記の記録条件にて、受像体（５）としてのボンド紙上に最終画像を得た。
記録ヘッド：ライン型サーマルヘッド
ライン記録速度：８ｍｓ
記録パルス幅：０−４ｍｓ
最大染料記録エネルギ−：６．５Ｊ／ｃｍ²
染着層転写エネルギー：４Ｊ／ｃｍ²
熱ローラー：温度１４０゜Ｃ，送り速度１０ｍｍ／秒、圧力５Ｋｇ
以上のようにしてボンド紙上に得られた画像は最大反射濃度１．８以上の高品位なピクトリアル画像であった。そして、繰り返し画像形成を行ってもこの高品位なピクトリアル画像を得ることができた。
【００４６】
（実験例２）
・染料転写体（１）の作製
４．５ミクロンのＰＥＴフィルムの裏面に１ないし２ミクロンの滑性耐熱層を設け、表面に０．３ミクロンのＴｇ＝６７度Ｃのランダム共重合ポリエステル樹脂を接着層として塗工した後、接着層上に下記処方からなるインクをグラビアコーターで固形厚み０．７ミクロンになるように色材層を形成した。ここで滑性耐熱層は前記実験例１と同様にして形成した。
（インク）
インドアニリン系分散染料２．５重量部
ポリビニルブチラール樹脂４重量部
アミド変性シリコーン油０．０２重量部
トルエン２０重量部
２−ブタノン２０重量部
・染着層転写体（２）の作製
染料転写体１と同じＰＥＴ基材、同じ接着層、同じ滑性耐熱層を用い、接着層上に離型層として脱オキシム型シリコーン樹脂（ＰＲＸ３０５、東レ・ダウコーニング・シリコーン社製）１０重量部、トルエン２０重量部からなる塗料をバーコーターで厚み０．３ミクロンに形成した。この離型層上に最下層の第１染着層としてポリ塩化ビニル・酢酸ビニル共重合体とポリアクリロニトリルスチレン樹脂の混合樹脂６重量部に離型材としてアミノ変成シリコーンとエポキシ変成シリコーンの反応硬化物を０．０６重量部、トルエン及び２−ブタノンをそれぞれ１３重量部からなる塗料をバーコーターで１ミクロンになるよう成膜した。この上に保護層として、Ｔｇ＝７５度Ｃのポリビニルブチラール樹脂とＴｇ＝１１０℃のアセトアセタール化ポリビニルアルコール樹脂（アセタール樹脂）を６：４の組成で１．５ミクロンになるように製膜した。更にこの上に上記アセタ−ル樹脂を１．５ミクロン製膜して、合計３層の染着層部を作製した。
【００４７】
・中間媒体（４）の作製
前記実施例１と同じものを用いた。
上記染料転写体（１），染着層転写体（２），及び中間媒体（４）を用い、前記実施例１と同じ記録条件にて、受像体（５）としてのボンド紙上に最終画像を得たところ、前記実施例１と同様に最大反射濃度１．８以上の高品位なピクトリアル画像を得ることができた。そして、繰り返し画像形成を行ってもこの高品位なピクトリアル画像を得ることができた。
【００４８】
【発明の効果】
以上説明したように、本発明によれば、前記の染料熱転写記録において従来困難であった受像体の全面への画像形成が可能になる。
【図面の簡単な説明】
【図１】本発明の熱記録転写体を用いた染料熱転写記録の第１の形態を示す図である。
【図２】本発明の熱記録転写体を用いた染料熱転写記録の第２の形態を示す図である。
【図３】本発明の熱記録転写体を用いた染料熱転写記録の第３の形態を示す図である。
【図４】図３に示された熱記録転写体を拡大して示した図である。
【図５】色材層と接着層間の剥離力の温度特性を示す図である。
【符号の説明】
１染料転写体
２，２′ 染着層転写体
３−１，３−２熱ヘッド
４中間媒体
５受像体
６染着層が転写された受像体
７熱ローラ
９，１０供給ローラ
９′，１０′ 巻取ローラ
１１，２１，４１基材
１２色材層
１３耐熱滑性層
１４接着層
２２離型層
２３，２３′ 染着層
４２機能層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thermal recording transfer body for stably performing dye thermal transfer recording that forms a high-quality full-color image on the receiver regardless of the substrate of the receiver, and to form a high-quality full-color image on the entire surface of the receiver. The present invention relates to a dye thermal transfer recording method made possible.
[0002]
[Prior art]
Dye thermal transfer recording is the only recording technology with excellent compactness, maintenance, and immediacy that can provide high-quality images comparable to color photographs. This is because a transfer body with a colorant layer containing a sublimation dye on a thin film substrate and an image receptor with a dyeing layer on a thick film substrate such as synthetic paper are superposed and sublimated using a thermal recording head. The dye is transferred to the dyeing layer and a mixed color image of dye molecules is recorded. Recording is generally performed by driving the image receiving member and driving the transfer member with a frictional force between the image receiving member and the transfer member.
[0003]
On the other hand, a method using a tack sheet has been proposed in order to attach recorded images to various places. The tack sheet is an image receiver composed of a two-layer structure of an upper layer and a lower layer, the upper layer obtained by forming a dyeing layer on the surface of the base material, and an adhesive material provided on the back surface of the base material, It is immobilized on a lower layer made of a support having a release layer on its upper surface. After recording, the upper layer is attached to a peel-off postcard.
[0004]
As described above, a recorded image by the dye thermal transfer recording method is formed on special paper. For this reason, the running cost is high, which has prevented the spread of this technology.
[0005]
In addition, there is a strong demand for recording information on plain paper in the same way as an image forming apparatus using electrophotography, as information in the recent multimedia era is a mixture of images and characters. With the thermal transfer recording method, it was impossible to obtain a high-quality image on plain paper.
[0006]
Therefore, the present inventors form a high-quality full-color image on the image receiving body in Japanese Patent Application Nos. 2-265641 and 2-282112 and Japanese Patent Application No. 2-282113. A dye thermal transfer recording method was proposed. This method has a sliding heat-resistant layer on the back surface of the first substrate and a dyed layer transfer body having at least a dyeing layer on the surface, and a sliding heat-resistant layer on the back surface of the second substrate. , A dye transfer body having at least a color material layer on the surface, an intermediate medium having a functional layer on a third substrate, and an image receiver, and a thermal head on the sliding heat-resistant layer of the dyed layer transfer body A process in which the dyed layer is thermally transferred onto the functional layer of the intermediate medium by bringing the dye layer into contact, and a thermal head is brought into contact with the slippery heat-resistant layer of the dye transfer body to be transferred onto the functional layer Thermal transfer recording by performing the process of thermally transferring and recording the dye in the color material layer on the dyed layer in accordance with the image signal and the process of thermally transferring the dyed layer on which the dye is recorded onto the main surface of the image receptor in this order. Is to do.
[0007]
[Problems to be solved by the invention]
However, the conventional dye thermal transfer recording has a problem in that an unrecorded blank portion is formed on the outer peripheral portion of the image receiving body and an image cannot be recorded on the entire image receiving body.
[0008]
An object of the present invention is to provide a dye thermal transfer recording method capable of recording an image on the entire surface of an image receptor.
[0009]
[Means for Solving the Problems]
A thermal transfer recording method according to the present invention includes a dyed layer transfer body having a sliding heat-resistant layer on the back surface of the first substrate and having a laminated structure in which a release layer and a dyed layer are laminated in this order on the surface, A dye transfer body having a laminated structure in which a back surface of the second base material has a sliding heat-resistant layer and an adhesive layer and a color material layer are laminated in this order on the surface, and an intermediate having a functional layer on the third base material A process of thermally transferring the dyed layer onto the functional layer of the intermediate medium by bringing a thermal head into contact with the sliding heat-resistant layer of the dyed layer transfer body using a medium and an image receptor; A process of thermally transferring and recording the dye in the color material layer on the dyeing layer transferred onto the functional layer by bringing a thermal head into contact with the sliding heat-resistant layer of the body, and the dye The process of thermally transferring the dyed layer on which the image is recorded onto the main surface of the image receiver is performed in this order. A recording method,
The dye layer of the dye layer transfer body is transferred to the functional layer of the intermediate medium so that the area of the dye layer is larger than the area of the image receiver, and the dye layer contains the dye layer in the color material layer of the dye transfer body. An image having an area larger than the area of the image receiver is formed by thermal transfer recording of the dye, and the dye recording layer dyed by pixel recording is transferred to the image receiver, and at the same time, a portion that protrudes from the outer periphery of the image receiver. The image receiving member is cut by an outer peripheral edge portion.
[0010]
The thermal transfer recording apparatus according to the present invention has a sliding heat-resistant layer on the back surface of the first substrate, and a dyed layer transfer body having a laminated structure in which a release layer and a dyeing layer are laminated in this order on the surface, A dye transfer body having a laminated structure in which a back surface of the second base material has a sliding heat-resistant layer and an adhesive layer and a color material layer are laminated in this order on the surface, and an intermediate having a functional layer on the third base material Using the medium and an image receiver, the dye transfer layer is thermally transferred onto the functional layer of the intermediate medium by bringing a thermal head into contact with the sliding heat-resistant layer of the dye transfer layer transfer body, and the dye transfer body The dye in the color material layer is thermally transferred and recorded on the dyeing layer transferred onto the functional layer by bringing a thermal head into contact with the sliding heat-resistant layer according to the image signal, and the dye is recorded. A thermal transfer recording apparatus for thermally transferring the dyed layer onto the main surface of the image receiver,
The dye layer of the dye layer transfer body is transferred to the functional layer of the intermediate medium so that the area of the dye layer is larger than the area of the image receiver, and the dye layer contains the dye layer in the color material layer of the dye transfer body. An image having an area larger than the area of the image receiver is formed by thermal transfer recording of the dye, and the dye recording layer dyed by pixel recording is transferred to the image receiver, and at the same time, a portion that protrudes from the outer periphery of the image receiver. The image receiving member is cut by an outer peripheral edge portion.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
According to the first configuration of the thermal recording transfer body of the present invention, the first base material has a sliding heat-resistant layer on the back surface, and a laminated structure in which a release layer and a dyeing layer are stacked in this order on the surface. A dye transfer layer, a dye transfer body having a laminated structure in which a back surface of the second substrate has a sliding heat-resistant layer, and an adhesive layer and a color material layer are stacked in this order on the surface; and a third substrate Using an intermediate medium having a functional layer thereon and an image receiver, the dyeing layer is placed on the functional layer of the intermediate medium by bringing a thermal head into contact with the sliding heat-resistant layer of the dyeing layer transfer body. Thermal transfer recording process in which the dye in the color material layer is transferred to the dyed layer transferred onto the functional layer by bringing a thermal head into contact with the sliding heat-resistant layer of the dye transfer body according to an image signal And a process of thermally transferring the dyed layer on which the dye is recorded onto the main surface of the image receptor in this order. A thermal recording transfer body provided as the dye transfer body for thermal transfer recording, formed with a base material, a slipping heat-resistant layer formed on the back surface of the base material, and an adhesive layer on the surface of the base material The color material layer is composed of a polyacrylonitrile styrene resin and at least one of the following resins (a), (b), and (c): In this case, the colorant layer exhibits good heat resistance and flexibility, and adheres to the adhesive layer with sufficient adhesive strength. As a result, the stability during winding and storage at high temperatures and during the recording process is excellent.
[0012]
(A) polyvinyl chloride resin, (b) copolymer resin of polyvinyl chloride resin and polyvinyl acetate resin, (c) copolymer resin of polyvinyl chloride resin, polyvinyl acetate resin and polyvinyl alcohol resin.
[0013]
As a preferred example of the first configuration, when the adhesive force between the resin constituting the adhesive layer on the base material surface and the color material layer is 50 g or more and 20 g / inch or more, the recording process can be repeated repeatedly and stably. Can be carried out.
[0014]
Moreover, as a preferable example of the first configuration, when the glass transition temperature of the resin constituting the adhesive layer on the substrate surface is 40 ° C. or higher, the environment is such that the intermediate medium is heated to 50 to 60 ° C. However, the recording process can be repeatedly and stably performed without blocking the color material layer and the adhesive layer.
[0015]
As a preferred example of the first configuration, in the first configuration, the base material is a polyester film, and the resin constituting the adhesive layer on the base material surface is a random copolymer having a glass transition temperature of 60 ° C. or higher. When the polyester resin is used, the recording process can be repeatedly and stably performed without blocking the color material layer and the adhesive layer even in a higher temperature environment than the above.
[0016]
As a preferred example of the first configuration, the base material is used for both the second base material on which the dye transfer body is formed and the first base material on which the dyed layer transfer body is formed. In this case, the dye transfer body and the dyed layer transfer body can be constituted by one transfer body, and the recording process can be performed in a small occupied space.
[0017]
According to the second configuration of the thermal recording transfer body of the present invention, it has a laminated configuration in which the back surface of the first base material has a sliding heat-resistant layer, and the release layer and the dyeing layer are laminated on the surface in this order. A dye transfer layer, a dye transfer body having a laminated structure in which a back surface of the second substrate has a sliding heat-resistant layer, and an adhesive layer and a color material layer are stacked in this order on the surface; and a third substrate Using an intermediate medium having a functional layer thereon and an image receiver, the dyeing layer is placed on the functional layer of the intermediate medium by bringing a thermal head into contact with the sliding heat-resistant layer of the dyeing layer transfer body. Thermal transfer recording process in which the dye in the color material layer is transferred to the dyed layer transferred onto the functional layer by bringing a thermal head into contact with the sliding heat-resistant layer of the dye transfer body according to an image signal And a process of thermally transferring the dyed layer on which the dye is recorded onto the main surface of the image receptor in this order. A thermal recording transfer body provided as the dyed layer transfer body for thermal transfer recording, wherein a base material, a sliding heat-resistant layer formed on the back surface of the base material, and a release layer on the surface of the base material In the recording process, the dyeing layer held on the intermediate medium has a higher heat resistance in a portion farther from the release layer. The surface layer on the low heat resistance side of the adhesion layer adheres to the color material layer, so that the recording sensitivity can be increased. Further, the surface portion on the side having high heat resistance is in contact with the sliding heat-resistant layer during high-temperature winding storage, and troubles due to adhesion between both layers can be prevented.
[0018]
According to the third configuration of the thermal recording transfer body of the present invention, it has a laminated configuration in which the back surface of the first base material has a sliding heat-resistant layer, and the release layer and the dyeing layer are laminated on the surface in this order. A dye transfer layer, a dye transfer body having a laminated structure in which a back surface of the second substrate has a sliding heat-resistant layer, and an adhesive layer and a color material layer are stacked in this order on the surface; and a third substrate Using an intermediate medium having a functional layer thereon and an image receiver, the dyeing layer is placed on the functional layer of the intermediate medium by bringing a thermal head into contact with the sliding heat-resistant layer of the dyeing layer transfer body. Thermal transfer recording process in which the dye in the color material layer is transferred to the dyed layer transferred onto the functional layer by bringing a thermal head into contact with the sliding heat-resistant layer of the dye transfer body according to an image signal And a process of thermally transferring the dyed layer on which the dye is recorded onto the main surface of the image receptor in this order. A thermal recording transfer member provided as the dyed layer transfer member for thermal transfer recording, wherein the dyeing layer is coated with a first dyeing layer in contact with the release layer and the first dyeing layer. A two-layer structure comprising a protective layer to be protected, or a first dyeing layer in contact with the release layer, a protective layer covering and protecting the first dyeing layer, and a film formed on the protective layer Since it has a three-layer structure composed of a strength reinforcing layer, a dyeing layer that is stable in strength can be formed by printing, and in particular, a three-layer structure has a thickness that can stabilize the recording process. A dyeing layer can be formed.
[0019]
As a preferred example of the third configuration, the first dyeing layer includes a polyvinyl butyral resin or polyvinyl acetal resin having a glass transition temperature Tg of less than 60 ° C. and a release material, and the protective layer is 70 ° C. The resin contains a mixture of a plurality of polyvinyl butyral resins or polyvinyl acetal resins having glass transition temperatures Tg of different temperatures, and has an area covering the entire surface of the first dyeing layer, The film strength reinforcing layer includes a polyvinyl butyral resin or a polyvinyl acetal resin having a glass transition temperature Tg of 100 ° C. or more, has an area smaller than the outer shape of the protective layer, and has higher heat resistance than the protective layer. With printing formation, it is stable in strength and can improve recording sensitivity. It is possible to form a color developing layer capable of preventing the adhesion of the lubricating heat-resistant layer.
[0020]
According to the 4th structure of the thermal recording transfer body of this invention, it has a laminated structure which has a sliding heat-resistant layer in the back surface of the 1st base material, and laminated | stacked the mold release layer and the dyeing | staining layer on the surface in this order. A dye transfer layer, a dye transfer body having a laminated structure in which a back surface of the second substrate has a sliding heat-resistant layer, and an adhesive layer and a color material layer are stacked in this order on the surface; and a third substrate Using an intermediate medium having a functional layer thereon and an image receiver, the dyeing layer is placed on the functional layer of the intermediate medium by bringing a thermal head into contact with the sliding heat-resistant layer of the dyeing layer transfer body. Thermal transfer recording process in which the dye in the color material layer is transferred to the dyed layer transferred onto the functional layer by bringing a thermal head into contact with the sliding heat-resistant layer of the dye transfer body according to an image signal And a process of thermally transferring the dyed layer on which the dye is recorded onto the main surface of the image receptor in this order. A thermal recording transfer body used as the dyed layer transfer body of thermal transfer recording, comprising a base material, a slipping heat-resistant layer formed on the back surface of the base material, and a release layer on the surface of the base material A resin that forms a surface region in contact with the colorant layer of the dyeing layer and a resin that constitutes the colorant layer are incompatible with each other. Due to the construction, the dyeing layer does not thermally bond to the color material layer of the dye transfer body during recording, and these can be easily peeled off after recording, and as a result, the recording process can be repeatedly and stably performed. .
[0021]
As a preferred example of the fourth configuration, the resin constituting the surface region in contact with the color material layer of the dyeing layer is one or more kinds of resins selected from polyvinyl butyral and polyvinyl acetal, and the color material layer is When the constituent resin is at least one resin selected from polyacrylonitrile styrene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinyl alcohol resin, polyester resin, polyamide resin, urethane resin, acrylic resin, It is possible to ensure that the surface region in contact with the color material layer and the color material layer are not compatible with each other.
[0022]
As a preferred example of the fourth configuration, the resin constituting the surface region of the dyeing layer that contacts the color material layer is a polyacrylonitrile styrene resin, a polyvinyl chloride resin, a polyvinyl acetate resin, a polyvinyl alcohol resin, It is one or more kinds of resins selected from polyester resins, polyamide resins, urethane resins and acrylic resins, and the resin constituting the color material layer is one or more kinds of resins selected from polyvinyl butyral and polyvinyl acetal. It is possible to ensure that the surface area in contact with the color material layer and the color material layer are not compatible with each other.
[0023]
As a preferable example of the second, third, and fourth configurations, when the adhesion force of the dyeing layer to the functional layer on the intermediate medium is in the range of 10 g / 25 mm to 100 g / 25 mm, the dyeing layer Is stably transferred to the functional layer on the intermediate medium, and dye recording from the dye transfer body to the dyeing layer is stably performed, and transfer of the dyeing layer to the image receptor is stable. As a result, the recording process is stabilized.
[0024]
Further, as a preferred example of the second, third, and fourth configurations, the base material is the first base material on which the dyed layer transfer body is formed, and the second base material on which the dye transfer body is formed. When used for both the substrate and the substrate, the recording process can be performed in a small occupied space.
[0025]
Further, as a preferable example of the first, second, third, and fourth configurations, the sliding heat-resistant layer formed on the back surface of the substrate has at least a heat-resistant resin, inorganic or organic fine particles, and liquid lubrication. If the material contains a heat-resistant material, the heat-resistant resin imparts heat resistance to the layer, and the inorganic or organic fine particles roughen the surface of the layer and reduce the dynamic friction coefficient of the layer against the thermal head. Since the lubricant material springs up on the surface of the layer and the dynamic friction coefficient of the layer with respect to the thermal head is further reduced, the transfer member can be stably run in the recording process. In addition, when the liquid lubricating material is a non-reactive silicone oil having a functional group in a side chain and a molecular weight of 10,000 or more, free movement of the liquid lubricating material is restricted in the sliding heat-resistant layer. Thus, even when the transfer body is wound and kept at a high temperature for a long time, the liquid lubricating substance is not transferred to the dyed layer or the color material layer on the surface of the base material. The surface of the functional layer and the surface of the color material layer of the medium are prevented from being contaminated by the liquid lubricant, and the holding force of the dyed layer held on the intermediate medium can be kept constant.
Further, the non-reactive silicone oil has a molecular weight of the functional group portion such as a polyether-modified silicone in which the molecular weight of the polyether group is 6000 and the molecular weight of the dimethylpolysiloxane portion sandwiched between the polyether groups is 12000. If the molecular weight is larger than the molecular weight of the dimethylpolysiloxane portion sandwiched between the groups, the non-reactive silicone oil is more strongly constrained in the sliding heat-resistant layer, and the intermediate medium due to the liquid lubricant in the recording process Contamination on the surface of the functional layer and the surface of the color material layer can be reliably eliminated, and the recording process can be further stabilized.
[0026]
According to the thermal transfer recording method of the present invention, there is provided a dyed layer transfer body having a laminated structure in which a back surface of the first base material has a sliding heat-resistant layer and a release layer and a dyed layer are laminated on the surface in this order. A dye transfer body having a layered structure in which a back surface of the second base material has a sliding heat-resistant layer and an adhesive layer and a color material layer are laminated in this order on the surface; and a functional layer on the third base material A process of thermally transferring the dyed layer onto the functional layer of the intermediate medium by using an intermediate medium and an image receiver and bringing a thermal head into contact with the sliding heat-resistant layer of the dyed layer transfer body; A process of thermally transferring and recording a dye in the color material layer on a dyeing layer transferred onto the functional layer by bringing a thermal head into contact with the sliding heat-resistant layer of the transfer body, and the dye Dye thermal transfer recording, in which the process of thermally transferring the dyed layer on which the ink is recorded onto the main surface of the image receiving member The dye layer of the dye layer transfer body is transferred to the functional layer of the intermediate medium so that the area thereof is larger than the area of the image receiver, and the color of the dye transfer body is transferred to the dye layer. The dye in the material layer is recorded by thermal transfer to form an image having an area larger than the area of the image receiver, and the dye recording layer dyed by pixel recording is transferred to the image receiver, and at the same time the outer periphery of the image receiver Since the protruding portion is cut by the outer peripheral edge of the image receiver, an image can be formed on the entire surface of the image receiver, which has been difficult in the past.
[0027]
FIG. 1 shows a first embodiment of dye thermal transfer recording using the thermal recording transfer member of the present invention. An intermediate medium 4 in which a dyed layer transfer body 2 in which a heat resistant slipping layer 13 is formed on the back surface of a substrate 21 and a release layer 22 and a dyed layer 23 are formed on the surface in this order is formed in a drum shape. And the thermal head 3-1 are fed by a supply roller 10 and a take-up roller 10 ′ and sandwiched. Then, thermal transfer of the dyeing layer 23 of the dyeing layer transfer body 2 is performed on the functional layer 42 provided on the base material 41 of the intermediate medium 4. Here, the intermediate medium may be formed in a belt shape or a sheet shape forming a closed loop. 2 'in the figure indicates the state of the dyed layer transfer body 2 after the dyed layer 23 is transferred. Next, the dye transfer body 1 in which the heat-resistant slip layer 13 is formed on the back surface of the substrate 11 and the adhesive layer 14 and the color material layer 12 are formed on the surface in this order is formed between the intermediate medium 4 and the thermal head 3-2. The sublimation dye in the color material layer 12 of the dye transfer body 1 is transferred to the dyeing layer 23 on the intermediate medium 4 by thermal diffusion. Finally, the image recorded in the dyed layer 23 on the intermediate medium 4 is thermally transferred onto the image receiver 5 using the thermal roller 7 and is not dependent on the substrate of the image receptor 5. A high quality image is formed on the image receiver 5. Further, 6 in the figure shows a state after the dyed layer 23 ′ on which image recording has been performed is transferred onto the image receiver 5. In the case where the intermediate medium 4 has a sheet shape, the sheet-like intermediate medium is swung and used for each transfer of the dyeing layer 23 and each dye transfer from the color material layer 12.
[0028]
FIG. 2 shows a second embodiment of dye thermal transfer recording using the thermal recording transfer member of the present invention. Here, the above-mentioned dyed layer transfer body 2 and the dye transfer body 1 are integrated to form a thermal recording transfer body 100. That is, the heat-resistant slip layer 13 is formed on the back surface of the substrate 11 (21), the adhesive layer 14 is formed on the surface, and the release layer 22 and the dyeing layer 23 are formed in the first region on the adhesive layer 14. Are formed in this order, and color material layers 12-1 and 12-2 having different hues are formed in the second and third regions to constitute the transfer body 100. Then, the transfer body is sent between the intermediate medium 4 and the thermal head 3-2 by the supply roller 9 and the take-up roller 9 ', and the dyeing layer 23 is first thermally transferred by the thermal head 3-2. Then, the sublimation dye in the color material layers 12-1 and 12-2 is thermally transferred to the dyed layer 23 that has been thermally transferred. The process after the sublimation dye is recorded on the dyeing layer 23 is the same as that of the first embodiment shown in FIG.
[0029]
FIG. 3 shows a third embodiment of dye thermal transfer recording using the thermal recording transfer member of the present invention. Here, the thermal recording transfer body 100 in which the dyed layer transfer body and the dye transfer body used in the second embodiment shown in FIG. 4 are formed on the same substrate, and the belt-like intermediate medium 4 ′ are used. The belt-like intermediate medium 4 'is stretched by a platen, a guide roller or the like. The portion of the dyed layer 23 of the thermal recording transfer body 100 is sent and sandwiched between the intermediate medium 4 ′ formed in a belt shape and the thermal head 3, and provided on the base material 41 of the intermediate medium 4 ′. The dye transfer layer 23 is thermally transferred onto the functional layer 42. The dyeing layer 23 is subjected to selective transfer of only a portion where the dye is recorded later, or transfer of the entire fixed area. Next, the portion of the color material layer 12 of the thermal recording transfer body 100 is sent and sandwiched between the intermediate medium 4 'and the thermal head 3, and the sublimation dye in the color material layer 12 is placed on the intermediate medium 4'. It is transferred by thermal diffusion into the dyed layer 23 that has been transferred. Finally, the image recorded in the dyed layer 23 on the intermediate medium 4 is thermally transferred onto the image receptor 5 by the thermal roller 7 together with the dyed layer 23, and the image receptor is not dependent on the substrate of the image receptor 5. 5, a high-quality image is formed.
[0030]
In the dye thermal transfer recording of the present invention, a polymer film having a thickness of 2 to 10 microns is used as the substrate 11. In general, polyethylene terephthalate (PET) films are used, but films made of resins that can be formed, such as aromatic polyamide (aramid), polyimide, polycarbonate, polyphenylene sulfide, polyetherketone, triacetylcellulose, cellophane, etc. are also useful. It is. Alternatively, a low resistance film formed by mixing conductive particles such as carbon into these resins may be used.
[0031]
The heat-resistant slip layer 13 is provided in order to provide lubricity between the thermal heads 3, 3-1, 3-2 and the base materials 11, 21, for example, a heat-resistant resin such as an ultraviolet curable resin. , Liquid lubricant, and organic or inorganic fine particles. A heat resistant resin imparts heat resistance to the layer. The fine particles roughen the surface of the layer and reduce the coefficient of friction on the surface of the layer, thereby imparting stable running properties to the layer. A small amount of liquid lubricant springs from the inside of the film to the film surface by the thermal heads 3, 3-1, 3-2, and the running stability of the dye transfer body 1, the dyed layer transfer body 2, and the thermal recording transfer body 100 is improved. Increase. A thermoplastic resin can also be used as the heat resistant resin, but it is preferable to use a cured resin (crosslinked resin) by heat, light (ultraviolet rays), an electron beam or the like because stable heat resistance can be obtained. Examples of such cured resins include silicone-based, acrylate-based, epoxy-based, and unsaturated aldehyde resins. Among these, cured products of epoxy acrylate-based resins exhibit excellent characteristics. Examples of inorganic or organic fine particles include inorganic fine particles of metals, metal oxides, sulfides, carbides, nitrides, fluorides, graphite, carbon black, and pigments. Of these, titanium oxide, molybdenum disulfide, and hydrophobic (anhydrous) silica are preferred, and among these, ultrafine hydrophobic (anhydrous) silica, titanium oxide, and aluminum oxide produced by vapor phase growth are particularly preferred. Examples of the organic system include spherical silicone resin fine particles.
[0032]
Examples of liquid lubricants include various dityl polysiloxane silicone oils, fluorine silicone oils, various modified silicone oils (epoxy modified, polyether modified, amino modified, carboxyl modified, etc.), organometallic salts, fluoroalkyl compounds, etc. Fluorine-based surfactants and the like can be used. If the liquid lubricating substance is a non-reactive silicone oil having a functional group in the side chain and a molecular weight of 10,000 or more, free movement of the silicone oil in the sliding heat-resistant layer is constrained and the transfer body is wound. It is possible to suppress the transfer of silicone oil to the surface of the dyeing layer 23 or the color material layer 12 on the substrate surface side, which occurs when kept at a high temperature for a long time. Furthermore, if the molecular weight of the side chain functional group part sandwiched between the dimethylpolysiloxane parts of this non-reactive silicone oil is larger than the molecular weight of the dimethylpolysiloxane part sandwiched between the side chain functional group parts, Thus, the restraining force of the silicone oil is further increased, and the effect of suppressing the transfer of the silicone oil to the surface of the dyeing layer 23 or the color material layer 12 on the substrate surface side is further strengthened. Specific examples thereof include a polyether-modified silicone oil having a molecular weight of 18000 with a molecular weight of 6000 and a molecular weight of 12,000. Therefore, when a non-reactive silicone oil having a molecular weight of 10,000 or more is used for the liquid lubricating substance, the surface of the functional layer 42 and the surface of the color material layer 12 of the intermediate medium 4, 4 'are not contaminated with silicone oil during the recording operation. The adhesion force that holds the dyed layer 23 on the intermediate medium 4, 4 'can be kept constant. In particular, if the molecular weight of the side chain functional group part of the non-reactive silicone oil sandwiched between the dimethylpolysiloxane parts is larger than the molecular weight of the dimethylpolysiloxane part, the dyeing layer 23 is placed on the intermediate medium 4, 4 '. The adhesion force to be held can be kept constant at a higher level.
[0033]
The adhesive layer 14 on the base materials 11 and 21 is generally formed to have a thickness of 0.5 μm or less integrally with the base material when forming the base material. When a polyester film is used for the substrate 11, a random copolymerized polyester resin is used for the adhesive layer. In general, a polyester resin having a glass transition temperature Tg near room temperature is used in order to maintain a large adhesive force with the color material layer 12 near room temperature. However, in the dye thermal transfer system using the intermediate medium of the present invention, the surface temperature of the intermediate medium is often maintained at 50 ° C to 60 ° C. For this reason, the color material layer 12 is well adhered to the base materials 11 and 21 even at 50 ° C. or more, and is designed so that a failure such as a blocking phenomenon due to the fusion of the color material layer 12 and the dyeing layer 23 does not occur during recording. Must. Therefore, the glass transition temperature Tg of the resin constituting the adhesive layer 14 is preferably 40 ° C. or higher. Furthermore, a polyester resin having a Tg of 60 ° C. or higher is stable even when the apparatus is placed in a high temperature state. When the peel strength between a polyester film of Tg = 67 ° C. polyester resin (Byron 200: manufactured by Toyobo Co., Ltd.) and Tg = 6 ° C. polyester polyester resin (Byron 300: manufactured by Toyobo Co., Ltd.) is compared. The former has a maximum peel force near 60 ° C., and the latter has a maximum peel force near room temperature, and the value decreases as the temperature increases. FIG. 5 shows the results of measuring the temperature characteristics of the peeling force between the color material layer 12 and the adhesive layer 14 in the transfer body using Byron 200 for the adhesive layer 14 and the transfer body using Byron 300 for the adhesive layer 14. The following shows the results of measuring the temperature characteristics of the peeling force between the color material layer 12 and the adhesive layer 14 after storing the two transfer bodies in a constant temperature layer of 60 ° C. and 60% RH for 300 hours. In order to establish the recording process, it is necessary that the color material layer / adhesive delamination force is larger than the color material layer / dye delamination force regardless of the recording portion temperature. At 50 ° C., the color material layer / dye delamination force is 20 g / inch or less, so the color material layer / adhesive delamination force needs to be greater than that value. Therefore, by using a resin having a Tg of 40 ° C. or more as a constituent resin of the adhesive layer 14, a recording process is used even in an environment where the temperature of the recording apparatus is high, using a transfer member stored at a high temperature for a long time. Can be carried out stably.
[0034]
The color material layer 12 is composed of at least a sublimable dye and a binder resin. As the sublimation dye, a disperse dye, an oil-soluble dye, a basic dye, a color former or the like is used. In particular, disperse dyes such as indoaniline, quinophthalone, dicyanoimidazole, dicyanomethine, and tricyanovinyl are effective. As the binder resin, polyester, polyvinyl butyral, polyacrylonitrile styrene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyamide resin, acrylic resin, urethane resin, low molecular polystyrene resin, etc. are used. It is done. These resins are also used as the constituent resin of the dyeing layer 23. The binder resin of the color material layer 12 and the constituent resin of the dye layer 23 are preferably incompatible. This is because the color material layer 12 and the dyeing layer 23 are not thermally fused at the time of recording, and can be easily separated after recording. When a resin such as polyester or polyvinyl butyral is used as the constituent resin of the dyeing layer 23, the binder resin of the color material layer 12 includes a polyacrylonitrile styrene (AS) resin, a polyvinyl chloride resin, a polyvinyl acetate resin, Either polyvinyl alcohol resin or a mixed resin in which two or more of these are mixed is used. Conversely, when a resin such as polyester or polyvinyl butyral is used as the binder resin of the color material layer 12, polyacrylonitrile styrene (AS) resin, polyvinyl chloride resin, polyvinyl acetate resin, Either polyvinyl alcohol resin or a mixed resin in which two or more of these are mixed is used. The compatibility / incompatibility of the resin can be evaluated by solubility parameters, critical surface tension, contact angle, and the like. For example, while the critical surface tension F of polyvinyl butyral is about 24 dynes / cm, the F of other general color material layers or dyeing layer resins in the text is more than 30. When evaluated by the solubility parameter SP value, the former is about 7, which is close to 6 of Teflon (registered trademark), and that of the latter is 9 or more.
[0035]
When an AS resin is used as the binder resin for the color material layer 12, the AS resin has Tg = 104 ° C., which is optimal in terms of the heat resistance of the color material layer, but the film itself is brittle and also has an adhesive force with the adhesive layer 14. Not enough. Therefore, a color material layer obtained by mixing a polyvinyl chloride resin, a polyvinyl acetate resin, and a polyvinyl alcohol resin copolymer resin (Tg = 64 ° C.) having a strong adhesive force with the adhesive layer 14 and a flexible film. If the binder resin is 12, both the sheet storage stability of the transfer body 1 and the recording stability can be satisfied. The mixing ratio of AS and the copolymer resin is preferably in the range of 2: 8 to 8: 2.
[0036]
The dyed layer transfer body 2 is formed by laminating a release layer 22 and a dyed layer 23 on a base material 21 (11). The release layer 22 is formed by thinly forming a silicone resin, a fluorine resin, or the like, or by mixing, dispersing, or reacting a release material with a resin other than silicone resin or fluorine resin. The silicone resin is preferably one that can be formed by addition polymerization or condensation polymerization for coating, release paper, or adhesive paper. As the fluorine resin, polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, vinylidene fluoride / hexafluoropropylene rubber material, various fluorine-containing resins and the like are effective. Examples of the release material added to the resin include various silicone lubricants, fluorine surfactants, waxes such as paraffin and polyethylene, higher aliphatic alcohols, higher fatty acid amides and esters. Examples of liquid lubricants include dimethylpolysiloxane, methylphenylpolysiloxane, fluorine silicone oil, other various modified silicone oils, and two or more reactive silicone oil reactants (for example, epoxy-modified and carboxyl- or amino-modified reactants). Etc.). Also, a reaction type of resin and lubricant may be used. For example, water-soluble polysiloxane graft acrylic resin obtained by graft polymerization of polysiloxane to acrylic resin, acrylic silicone (silicon) or acrylic urethane having siloxane methacrylate added to the terminal or side chain. Silicone (silicon) resin is also effective.
[0037]
The dyeing layer 23 is preferably a two-layer configuration of a first dyeing layer 24 and a protective layer 25 in contact with the release layer 22 on the surface of the substrate 21 (11), or the first dyeing layer 24 and the protective layer 25. The film strength reinforcing layer 26 is composed of three layers. It is preferable that the heat resistance of the constituent resin increases as it goes from the first dyeing layer 24 to the upper protective layer 25 and the reinforcing layer 26. This is because the first dyeing layer 24 having low heat resistance is in contact with the color material layer 12 at the time of recording, so that the recording sensitivity can be increased, and the heat resistant layer 13 has heat resistance at the time of high temperature winding storage. This is because adhesion between the dyeing layer 23 and the sliding heat-resistant layer 13 can be prevented by contacting the high protective layer 25 or the reinforcing layer 26. Further, from the viewpoint of laminated film formation, the first dyeing layer 24 and the protective layer 25 are constituted by containing them with a resin of the same resin type, or the first dyeing layer 24, the protective layer 25, and the reinforcing layer. 26 is preferably formed by including a resin of the same resin type, thereby enabling a multilayer film having a uniform film property to be formed by printing. In general, when a film is formed by gravure printing, the thickness of one layer is 1.5 μm at most, and the thickness of the dyed layer portion necessary for realizing this process is 3 to 4 μm. For this reason, the film thickness is insufficient with only the first dyeing layer 24, and a three-layer structure having the film strength reinforcing layer 26 is preferable for process stabilization.
[0038]
When the dyeing layer 23 has the two-layer or three-layer structure, the following structure is preferable. That is, the first dyeing layer 24 includes a polyvinyl butyral resin or polyvinyl acetal resin having a glass transition temperature Tg of less than 60 ° C. and a release material, and the protective layer 25 is made of glass having different temperatures of 70 ° C. or more. A resin containing a mixture of a plurality of polyvinyl butyral resins or polyvinyl acetal resins having a transition temperature Tg and having an area covering the entire surface of the first dyeing layer 24 is used, and the film strength reinforcing layer 26 is a glass transition temperature. A polyvinyl butyral resin or a poly (vinyl acetal) resin having a Tg of 100 ° C. or higher is included, has an area smaller than the outer shape of the protective layer 25, and has higher heat resistance than the protective layer 25.
[0039]
In the intermediate medium 4, a functional layer 42 is provided on a metal drum or polymer film base 41. The functional layer 42 is made of a rubber-like material in which a silicone resin, a fluorine resin, or the like is thinly formed, or a material obtained by mixing, dispersing, or reacting with a release material in a resin other than the silicone resin or the fluorine resin. The silicone resin is preferably one that can be formed by addition polymerization or condensation polymerization for coating, release paper, or adhesive material. As the fluorine resin, polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, vinylidene fluoride / hexafluoropropylene rubber material, various fluorine-containing resins and the like are effective. In particular, a terpolymer copolymer fluororubber (Viton: Showa Denko DuPont) of vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene is effective. This ternary copolymer fluororubber is used together with fine particles such as carbon and magnesium oxide to form a film.
[0040]
The image receptor 5 may be a pulp paper such as bond paper or plain paper, may be a synthetic paper such as milk white PET or YUPO, or may be a base material on which pulp paper and a film are bonded. Moreover, various cards, such as a telephone card, a prepaid card, and an IC card, may be used. Conventionally, an image is formed on the image receiver leaving an unrecorded blank area around the image receptor. In the present invention, when the image receptor 5 is hard and rigid like a postcard or various cards, an image can be formed on the entire surface of the image receptor as follows. That is, after the dyeing layer 23 is transferred onto the intermediate medium 4, 4 ′ so that the area thereof is larger than the area of the image receiver 5, an image larger than the area of the image receiver 5 is formed on the dyeing layer 23. The conditions of heat or pressure required for the transfer are optimized, and the dyed layer 23 is transferred to the image receiver 5 so that it is cut by the peripheral portion of the image receiver 5 such as a card. After the dye layer 23 is transferred to the image receiver 5, the dye layer 23 remaining on the intermediate medium 4 is removed by a cleaning mechanism or the like.
[0041]
As the recording head, an ordinary thermal (thermal) head, energizing head, laser head, or the like is used. The recording conditions when the line-type thermal head is used are: line recording period T: 33 ms to 4 ms, applied pulse width: 16 ms to 2 ms, recording energy E: 8 to 6 J / cm²Is done.
[0042]
When the heat roller 7 is used for the thermal transfer of the recorded dyed layer to the image receptor 5, the temperature is about 140 ° C., the speed is 10 mm / second, and the pressure is 1 kg / cm.²Is done.
[0043]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples.
[0044]
(Experimental example 1)
-Preparation of dye transfer body (1)
A 2 micron slip heat-resistant layer, which will be described later, is provided on the back side of a 5 micron PET film, and a random copolyester resin of 0.3 micron Tg = 67 degrees C is coated on the surface as an adhesive layer. A colorant layer was formed using a gravure coater so that the solid thickness was 1 micron. Here, the sliding heat-resistant layer was formed by applying a paint having the following formulation with a micro gravure coater, evaporating the solvent with hot air at 60 ° C., and then irradiating it with a 1 KW high-pressure mercury lamp.
(ink)
Indian aniline-based disperse dye 2.5 parts by weight
Acrylic styrene resin 2 parts by weight
Polyvinyl chloride copolymer resin 2 parts by weight
Amide-modified silicone oil 0.02 parts by weight
20 parts by weight of toluene
2-butanone 20 parts by weight
(paint)
12 parts by weight of epoxy acrylate resin
3 parts by weight of neopentyl glycol diacrylate
0.75 parts by weight of 2-hydroxy-2-methylpropiophenone
Aerosil (trade name of hydrophobic ultrafine silica) 2 parts by weight
Polyether-modified dimethyl silicone 0.4 parts by weight
(Molecular weight 18000)
100 parts by weight of ethyl acetate
・ Production of dyed layer transfer body (2)
Using the same PET base material, the same adhesive layer, and the same sliding heat-resistant layer as the dye transfer body, a deoxime type silicone resin as a release layer on the adhesive layer: PRX305 (trade name, manufactured by Toray Dow Corning Silicone) 10 weight Part and 20 parts by weight of toluene were formed to a thickness of 0.3 microns with a bar coater. On this release layer, as a first dyeing layer, polyvinyl butyral resin: BL-S (trade name, manufactured by Sekisui Chemical Co., Ltd., Tg = 55 ° C.) 6 parts by weight, acrylic silicone having siloxane methacrylate in the side chain ( Silicon) Resin: F-6A (trade name, manufactured by Sanyo Chemical Industries Co., Ltd.) 0.06 parts by weight, di-n-butyltin dilaurate 0.004 parts by weight, toluene and 2-butanone 13 parts each by weight The film was formed with a coater to a thickness of 1 micron. As a protective layer, a polyvinyl butyral resin having a Tg = 75 ° C. and an acetoacetalized polyvinyl alcohol resin (acetal resin) having a Tg = 110 ° C. having a composition of 6: 4 so as to be 1.5 microns. A film was formed. Further, the above two types of resins were formed into a 1.5 micron film with a composition of 3: 7 to produce a total of three dyed layer portions.
[0045]
-Production of intermediate medium (4)
A 50-micron polyimide film was used as a base on a metal drum, and the following functional layer coating was formed to a thickness of about 30 microns to form an intermediate medium. A polyimide having a functional layer formed thereon may be used as a belt without using a metal drum.
(Functional layer paint)
Fluoro rubber 100 parts by weight
3 parts by weight of suspension material
20 parts by weight of carbon
Magnesium oxide 15 parts by weight
350 parts by weight of methyl ethyl ketone
Using the dye transfer body (1), the dyed layer transfer body (2), and the intermediate medium (4), a final image was obtained on bond paper as the image receiving body (5) under the following recording conditions.
Recording head: Line type thermal head
Line recording speed: 8ms
Recording pulse width: 0-4ms
Maximum dye recording energy: 6.5 J / cm²
Dyeing layer transfer energy: 4 J / cm²
Heat roller: temperature 140 ° C, feed rate 10mm / sec, pressure 5Kg
The image obtained on the bond paper as described above was a high-quality pictorial image having a maximum reflection density of 1.8 or more. Even if image formation was repeated, this high-quality pictorial image could be obtained.
[0046]
(Experimental example 2)
-Preparation of dye transfer body (1)
A 1 to 2 micron sliding heat-resistant layer is provided on the back side of a 4.5 micron PET film, and a 0.3 micron Tg = 67 degree C random copolymer polyester resin is applied as an adhesive layer on the surface, followed by adhesion. On the layer, a color material layer was formed by using a gravure coater with an ink having the following formulation so that the solid thickness was 0.7 microns. Here, the sliding heat-resistant layer was formed in the same manner as in Experimental Example 1.
(ink)
Indian aniline-based disperse dye 2.5 parts by weight
4 parts by weight of polyvinyl butyral resin
Amide-modified silicone oil 0.02 parts by weight
20 parts by weight of toluene
2-butanone 20 parts by weight
・ Production of dyed layer transfer body (2)
Using the same PET base material, the same adhesive layer, and the same sliding heat-resistant layer as the dye transfer body 1, 10 parts by weight of a deoxime type silicone resin (PRX305, manufactured by Toray Dow Corning Silicone) as a release layer on the adhesive layer A paint consisting of 20 parts by weight of toluene was formed with a bar coater to a thickness of 0.3 microns. On this release layer, as the first dyeing layer of the lowermost layer, 6 parts by weight of a mixed resin of polyvinyl chloride / vinyl acetate copolymer and polyacrylonitrile styrene resin, a reaction cured product of amino-modified silicone and epoxy-modified silicone as a release material Was formed to a thickness of 1 micron with a bar coater. The coating was composed of 0.06 part by weight and 13 parts by weight each of toluene and 2-butanone. As a protective layer, a polyvinyl butyral resin having a Tg of 75 ° C. and an acetoacetalized polyvinyl alcohol resin (acetal resin) having a Tg of 110 ° C. were formed to a thickness of 1.5 microns with a composition of 6: 4. . Further, the above-mentioned acetal resin was formed into a 1.5 micron film thereon to produce a total of three dyed layer portions.
[0047]
-Production of intermediate medium (4)
The same one as in Example 1 was used.
Using the above dye transfer body (1), dyed layer transfer body (2), and intermediate medium (4), a final image is formed on the bond paper as the image receiving body (5) under the same recording conditions as in Example 1. As a result, a high-quality pictorial image having a maximum reflection density of 1.8 or more could be obtained as in Example 1. Even if image formation was repeated, this high-quality pictorial image could be obtained.
[0048]
【The invention's effect】
As described above, according to the present invention, it is possible to form an image on the entire surface of the image receiving member, which has been difficult in the conventional dye thermal transfer recording.
[Brief description of the drawings]
FIG. 1 is a diagram showing a first embodiment of dye thermal transfer recording using a thermal recording transfer member of the present invention.
FIG. 2 is a diagram showing a second embodiment of dye thermal transfer recording using the thermal recording transfer member of the present invention.
FIG. 3 is a diagram showing a third embodiment of dye thermal transfer recording using the thermal recording transfer member of the present invention.
FIG. 4 is an enlarged view of the thermal recording transfer member shown in FIG.
FIG. 5 is a graph showing temperature characteristics of peeling force between a color material layer and an adhesive layer.
[Explanation of symbols]
1 Dye transfer material
2,2 'dyed layer transfer body
3-1, 3-2 Thermal head
4 Intermediate media
5 Receiver
6 Image receptor with dyed layer transferred
7 Heat roller
9,10 Supply roller
9 ', 10' Winding roller
11, 21, 41 Base material
12 Color material layer
13 Heat resistant slipping layer
14 Adhesive layer
22 Release layer
23,23 'dyed layer
42 functional layers

Claims

A dyed layer transfer member having a sliding heat-resistant layer on the back surface of the first substrate and having a laminate structure in which a release layer and a dyed layer are laminated in this order on the surface, and a slipping layer on the back surface of the second substrate. A dye transfer body having a heat-resistant heat-resistant layer and having a laminated structure in which an adhesive layer and a color material layer are laminated in this order on the surface, an intermediate medium having a functional layer on a third substrate, and an image receiver, A process of thermally transferring the dyed layer onto the functional layer of the intermediate medium by bringing a thermal head into contact with the sliding heat resistant layer of the dyed layer transfer body; A process of thermally transferring and recording a dye in the color material layer on the dyeing layer transferred onto the functional layer by contacting a head according to an image signal, and the dyeing layer on which the dye is recorded A thermal transfer recording method for performing a thermal transfer process in this order on a main surface of a receiver,
The dye layer of the dye layer transfer body is transferred to the functional layer of the intermediate medium so that the area of the dye layer is larger than the area of the image receiver, and the dye layer contains the dye layer in the color material layer of the dye transfer body. An image having an area larger than the area of the image receiver is formed by thermal transfer recording of the dye, and the dye recording layer dyed by pixel recording is transferred to the image receiver, and at the same time, a portion that protrudes from the outer periphery of the image receiver. A thermal transfer recording method comprising cutting the outer periphery of the image receiver.

A dyed layer transfer member having a sliding heat-resistant layer on the back surface of the first substrate and having a laminate structure in which a release layer and a dyed layer are laminated in this order on the surface, and a slipping layer on the back surface of the second substrate. A dye transfer body having a heat-resistant heat-resistant layer and having a laminated structure in which an adhesive layer and a color material layer are laminated in this order on the surface, an intermediate medium having a functional layer on a third substrate, and an image receiver, The dyeing layer is thermally transferred onto the functional layer of the intermediate medium by bringing a thermal head into contact with the sliding heat resistant layer of the dyeing layer transfer body, and the thermal head is applied to the sliding heat resistant layer of the dye transfer body. The dye in the colorant layer is thermally transferred and recorded on the dyed layer transferred onto the functional layer by contacting the dye according to the image signal, and the dyed layer on which the dye is recorded is transferred to the image receiving member. A thermal transfer recording apparatus that thermally transfers onto a main surface,
The dye layer of the dye layer transfer body is transferred to the functional layer of the intermediate medium so that the area of the dye layer is larger than the area of the image receiver, and the dye layer contains the dye layer in the color material layer of the dye transfer body. An image having an area larger than the area of the image receiver is formed by thermal transfer recording of the dye, and the dye recording layer dyed by pixel recording is transferred to the image receiver, and at the same time, a portion that protrudes from the outer periphery of the image receiver. A thermal transfer recording apparatus, wherein the thermal transfer recording apparatus is cut by an outer peripheral edge of the image receiving member.