JP2004148794A - Data recording and display card, image forming and erasing method using the same and image processing apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a data recording and display card having an over sheet comprising a reversible thermal recording material not causing a problem of environmental pollution at disposal treatment and excellent in embossing processability and repeated image erasing durability. <P>SOLUTION: The data recording and display card is constituted by laminating a core sheet and the over sheet. The over sheet is obtained by providing a reversible thermal recording layer, which contains an electron donating color forming compound and an electron acceptive compound and relatively forms a developed color state and an erased state by the difference between a heating temperature and a cooling speed, on a support containing at least an amorphous polyester resin and functions as an image display part. This over sheet satisfies a condition (A): [erasing upper limit temperature of oversheet - 30°C] ≤ [temperature of storage elastic modulus E' (1.0E + 08)Pa] ≤ 200°C and a condition (B): 1.0E + 04Pa ≤ [storage elastic modulus E' at 180°C of over sheet] ≤ 5.0E + 07Pa. <P>COPYRIGHT: (C)2004,JPO

Description

式中、Ｘ_１はヘテロ原子を含む２価の基または直接結合手を示し、Ｘ_２はヘテロ原子を含む２価の基を示す。Ｒ_１は２価の炭化水素基を表わし、Ｒ_２は炭素数１から２２の炭化水素基を表わす。また、ｐは０から４の整数を表わし、ｐが２から４のとき繰り返されるＲ_１およびＸ_２は同一でも、異なっていても良い。また、ｑは１から３を表わす。
具体的には、Ｒ_１およびＲ_２は置換基を有していてもよい炭化水素基を示し、これらは脂肪族炭化水素基でも芳香族炭化水素基でもよく、また、これらの両方から構成される炭化水素基でもよい。また脂肪族炭化水素基は直鎖でも分枝していてもよく、不飽和結合を有していてもよい。炭化水素基につく置換基としては、水酸基、ハロゲン、アルコキシ基等がある。なお、Ｒ_１は直接結合手でも良い。
またＲ_１及びＲ_２の炭素数の和が７以下では発色の安定性や消色性が低下するため、炭素数は８以上が好ましく、１１以上であることがより好ましい。Ｘ_１及びＸ_２はヘテロ原子を含む２価の基を示し、
【００７８】
【表１】

好ましくは表１で表わされる基を少なくとも１個以上有する２価の基を表わす。その具体例としては、下記のものが挙げられる。
【００７９】
【表２】

【００８０】
本発明におけるフェノール化合物の具体的な例を以下に挙げるが、本発明はこれらに限定されるものではない。また、フェノール化合物を単独または混合して用いることもできる。
【００８１】
【表３】

【００８２】
有機リン酸系の顕色剤としては以下のような化合物が例示できる。ドデシルホスホン酸、テトラデシルホスホン酸、ヘキサデシルホスホン酸、オクタデシルホスホン酸、エイコシルホスホン酸、ドコシルホスホン酸、テトラコシルホスホン酸、リン酸ジテトラデシルエステル、リン酸ジヘキサデシルエステル、リン酸ジオクタデシルエステル、リン酸ジエイコシルエステル、リン酸ジベヘニルエステルなど。
脂肪族カルボン化合物としては以下のような化合物が例示できる。２−ヒドロキシテトラデカン酸、２−ヒドロキシヘキサデカン酸、２−ヒドロキシオクタデカン酸、２−ヒドロキシエイコサン酸、２−ヒドロキシドコサン酸、２−ブロモヘキサデカン酸、２−ブロモオクタデカン酸、２−ブロモエイコサン酸、２−ブロモドコサン酸、３−ブロモオクタデカン酸、３−ブロモドコサン酸、２，３−ジブロモオクタデカン酸、２−フルオロドデカン酸、２−フルオロテトラデカン酸、２−フルオロヘキサデカン酸、２−フルオロオクタデカン酸、２−フルオロエイコサン酸、２−フルオロドコサン酸、２−ヨードヘキサデカン酸、２−ヨードオクタデカン酸、３−ヨードヘキサデカン酸、３−ヨードオクタデカン酸、パーフルオロオクタデカン酸など。
【００８３】
脂肪族ジカルボン酸およびトリカルボン酸化合物としては以下のような化合物が例示できる。２−ドデシルオキシこはく酸、２−テトラデシルオキシこはく酸、２−ヘキサデシルオキシこはく酸、２−オクタデシルオキシこはく酸、２−エイコシルオキシこはく酸、２−ドデシルオキシこはく酸、２−ドテシルチオこはく酸、２−テトラデシルチオこはく酸、２−ヘキサデシルチオこはく酸、２−オクタデシルチオこはく酸、２−エイコシルチオこはく酸、２−ドコシルチオこはく酸、２−テトラコシルチオこはく酸、２−ヘキサデシルジチオこはく酸、２−オクタデシルジチオこはく酸、２−エイコシルジチオこはく酸、ドデシルこはく酸、テトラデシルこはく酸、ペンタデシルこはく酸、ヘキサデシルこはく酸、オクタデシルこはく酸、エイコシルこはく酸、ドコシルこはく酸、２，３−ジヘキサデシルこはく酸、２，３−ジオクタデシルこはく酸、２−メチル−３−ヘキサデシルこはく酸、２−メチル−３−オクタデシルこはく酸、２−オクタデシル−３−ヘキサデシルこはく酸、ヘキサデシルマロン酸、オクタデシルマロン酸、エイコシルマロン酸、ドコシルマロン酸、ジヘキサデシルマロン酸、ジオクタデシルマロン酸、ジドコシルマロン酸、メチルオクタデシルマロン酸、２−ヘキサデシルグルタル酸、２−オクタデシルグルタル酸、２−エイコシルグルタル酸、ドコシルグルタル酸、２−ペンタデシルアジピン酸、２−オクタデシルアジピン酸、２−エイコシルアジピン酸、２−ドコシルアジピン酸、２−ヘキサデカノイルオキシプロパン−１，２，３−トリカルボン酸、２−オクタデカノイルオキシプロパン−１，２，３−トリカルボン酸など。
【００８４】
発色剤と顕色剤の割合は、使用する化合物の組合わせにより適切な範囲が変化するが、おおむねモル比で発色剤１に対し顕色剤が０．１から２０の範囲であり、好ましくは０．２から１０の範囲である。この範囲より顕色剤が少なくても多くても発色状態の濃度が低下し問題となる。また、消色促進剤の割合は顕色剤に対し０．１重量％から３００重量％が好ましく、より好ましくは３重量％から１００重量％が好ましい。又、発色剤と顕色剤はマイクロカプセル中に内包して用いることもできる。記録層中の発色成分と樹脂の割合は、発色成分１に対して０．１から１０が好ましく、これより少ないと記録層の熱強度が不足し、これより多い場合には発色濃度が低下して問題となる。
【００８５】
本発明に用いられる可逆性感熱記録材料を構成する可逆性感熱記録層には、通常樹脂を含有させる。
可逆性感熱記録層に含有させる樹脂の具体例としては、アクリルポリオール樹脂、ポリエステルポリオール樹脂、ポリウレタンポリオール樹脂、フェノキシ樹脂、ポリビニルブチラール樹脂、セルロースアセテートプロピオネート、セルロースアセテートブチレートなど架橋剤と反応する基を持つ樹脂、または架橋剤と反応する基を持つモノマーとそれ以外のモノマーを共重合した樹脂などが挙げられるが、本発明はこれらの化合物に限定されるものではない。
更に、これらの樹脂に対してベンゾトリアゾール系紫外線吸収骨格やシロキサン結合骨格をブロック共重合やグラフト共重合させた樹脂などが挙げられる。
【００８６】
本発明のオーバーシートである可逆性感熱記録材料には、必要に応じて可逆性感熱記録層の塗布特性や発色消色特性を改善したり制御するための添加剤を用いることができる。これらの添加剤には、たとえば界面活性剤、導電剤、充填剤、酸化防止剤、光安定化剤、発色安定化剤、消色促進剤などがある。消色促進剤として好ましくは、ヘテロ原子を含む２価の基と炭素数８以上のアルキル鎖を有する化合物であったり、Ｎ，Ｎ’−２置換基を有する化合物であったりするが、本発明はこれらの化合物に限定されるものではない。
【００８７】
本発明においては、可逆性感熱記録層に硬化剤を含有させても良い。
ここで用いられる硬化剤としては、公知のイソシアネート単量体のウレタン変性体、アロファネート変性体、イソシアヌレート変性体、ビュレット変性体、カルボジイミド変性体、ブロックドイソシアネートなどの変性体から選択される。また、変性体を形成するイソシアネート単量体としては、トリレンジイソシアネート（ＴＤＩ）、４，４’−ジフェニルメタンジイソシアネート（ＭＤＩ）、キシリレンジイソシアネート（ＸＤＩ）、ナフチレンジイソシアネート（ＮＤＩ）、パラフェニレンジイソシアネート（ＰＰＤＩ）、テトラメチルキシリレンジイソシアネート（ＴＭＸＤＩ）、ヘキサメチレンジイソシアネート（ＨＤＩ）、ジシクロヘキシルメタンジイソシアネート（ＨＭＤＩ）、イソフォロンジイソシアネート（ＩＰＤＩ）、リジンジイソシアネート（ＬＤＩ）、イソプロピリデンビス（４−シクロヘキシルイソシアネート）（ＩＰＣ）、シクロヘキシルジイソシアネート（ＣＨＤＩ）、トリジンジイソシアネート（ＴＯＤＩ）、等が挙げられるが、本発明はこれらの化合物に限定されるものではない。
【００８８】
更に、可逆性感熱記録層に架橋促進剤硬化剤を含有させても良い。
架橋促進剤としては、例えば１，４−ジアザ−ビシクロ［２，２，２］オクタンなどの３級アミン類、有機すず化合物などの金属化合物などが挙げられる。また、硬化剤は添加した全量が架橋反応をしていても、していなくても良い。すなわち、未反応硬化剤が存在していても良い。
この種の架橋反応は経時的に進行するため、未反応の硬化剤が存在していることは架橋反応が全く進行していないことを示すのではなく、未反応の硬化剤が検出されることにより架橋状態にある樹脂が存在することが示唆されるからである。また、本発明におけるポリマーが架橋状態にあるのか非架橋状態にあるのかを区別する方法として、塗膜を溶解性の高い溶媒中に浸すことによって区別することができる。
すなわち、非架橋状態にあるポリマーは、溶媒中に該ポリマーが溶けだし溶質中には残らなくなるため、溶質のポリマー構造の有無を分析すればよい。そこで、溶質中にポリマー構造の存在が確認できなければ、該ポリマーは非架橋状態にあることがいえ、架橋状態のポリマーと区別することができる。
また、他の層が積層されている場合には、ＴＥＭ（透過型電子顕微鏡）やＳＥＭ（走査型電子顕微鏡）などの断面写真より層構成および膜厚を確認する。そして、無関係な層を全て削り取り、狙いの層を露出させる。次にその層を削り取り、上記方法に従って測定を行なう。
【００８９】
記録層の形成には、前記の顕色剤、発色剤、種々の添加剤、硬化剤及び架橋状態にある樹脂ならびに塗液溶媒よりなる混合物を均一に混合分散させて調製した塗工液を用いる。
塗工液調製に用いられる溶媒の具体例としては水；メタノール、エタノール、イソプロパノール、ｎ−ブタノール、メチルイソカルビノールなどのアルコール類；アセトン、２−ブタノン、エチルアミルケトン、ジアセトンアルコール、イソホロン、シクロヘキサノンなどのケトン類；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミドなどのアミド類；ジエチルエーテル、イソプロピルエーテル、テトラヒドロフラン、１，４−ジオキサン、３，４−ジヒドロ−２Ｈ−ピランなどのエーテル類；２−メトキシエタノール、２−エトキシエタノール、２−ブトキシエタノール、エチレングリコールジメチルエーテルなどのグリコールエーテル類；２−メトキシエチルアセテート、２−エトキシエチルアセテート、２−ブトキシエチルアセテートなどのグリコールエーテルアセテート類；酢酸メチル、酢酸エチル、酢酸イソブチル、酢酸アミル、乳酸エチル、エチレンカーボネートなどのエステル類；ベンゼン、トルエン、キシレンなどの芳香族炭化水素類；ヘキサン、ヘプタン、ｉｓｏ−オクタン、シクロヘキサンなどの脂肪族炭化水素類；塩化メチレン、１、２−ジクロルエタン、ジクロロプロパン、クロルベンゼンなどのハロゲン化炭化水素類；ジメチルスルホキシドなどのスルホキシド類；Ｎ−メチル−２−ピロリドン、Ｎ−オクチル−２−ピロリドンなどのピロリドン類等を例示することができる。
【００９０】
塗工液調製は、ペイントシェーカー、ボールミル、アトライター、三本ロールミル、ケディーミル、サンドミル、ダイノミル、コロイドミル等公知の塗液分散装置を用いて行なうことができる。又、上記塗工液分散装置を用いて各材料を溶媒中に分散しても良いし、各々単独で溶媒中に分散して混ぜ合わせても良い。更に加熱溶解して急冷または除冷によって析出させても良い。
【００９１】
記録層を設ける塗工方法については特に制限はなく、ブレード塗工、ワイヤーバー塗工、スプレー塗工、エアナイフ塗工、ビード塗工、カーテン塗工、グラビア塗工、キス塗工、リバースロール塗工、ディップ塗工、ダイ塗工等公知の方法を用いることができる。
【００９２】
記録層の乾燥・硬化方法は塗布・乾燥後、必要に応じて硬化処理を行なう。高温槽等を用いて比較的高温で短時間でも良く、又比較的低温で長時間かけて熱処理しても良い。架橋反応の具体的な条件としては反応性の面から３０℃〜１３０℃程度の温度条件で１分から１５０時間程度加温することが好ましい。より好ましくは４０℃〜１００℃の温度条件で２分から１２０時間程度加温することが好ましい。また、製造では生産性を重視するので、架橋が充分完了するまで時間をかけるのは困難である。したがって、乾燥過程とは別に架橋工程を設けてもよい。架橋工程の条件としては４０℃〜１００℃の温度条件で２分から１２０時間程度加温することが好ましい。
【００９３】
次に、通常、スティッキング防止や耐久性向上を目的として、可逆性感熱記録層上に任意に設けることができる保護層について説明する。
保護層の膜厚は、０．１〜２０μｍの範囲が好ましく、より好ましくは０．３〜１０μｍである。
また、該保護層中には、地肌かぶりを防止する目的で無機または有機紫外線吸収剤を含有しても良く、その含有量はバインダー１００重量部に対して０．５〜５０重量部の範囲が好ましい。
保護層の塗液に用いられる溶媒、塗液の分散装置、バインダー、塗工方法、乾燥・硬化方法等は上記記録層で用いられた公知の方法を用いることができる。
【００９４】
有機紫外線吸収剤としては、２−（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−５’−ｔ−ブチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’−ｔ−ブチル−５’−メチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−５’−オクトキシフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’−ｔ−ブチル−５’−メチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−５’−エトキシフェニル）ベンゾトリアゾール等のベンゾトリアゾール系紫外線吸収剤、２，４−ジヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノン、２−ヒドロキシ−４−ドデシルオキシベンゾフェノン、２，２’−ジヒドロキシ−４−メトキシベンゾフェノン、２，２’−ジヒドロキシ−４，４’−ジメトキシベンゾフェノン、２，２’，４，４’−テトラヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシ−２’−カルボキシベンゾフェノン、２−ヒドロキシ−４−オキシベンジルベンゾフェノン、２−ヒドロキシ−４−クロロベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン−５−スルホン酸、２−ヒドロキシ−４−メトキシベンゾフェノン−５−スルホン酸ナトリウム、２，２’−ジヒドロキシ−４，４’−ジメトキシベンゾフェノン−スルホン酸ナトリウム等のベンゾフェノン系紫外線吸収剤、フェニルサリシレート、ｐ−オクチルフェニルサリシレート、ｐ−ｔ−ブチルフェニルサリシレート、カルボキシフェニルサリシレート、メチルフェニルサリシレート、ドデシルフェニルサリシレート、２−エチルヘキシルフェニルサリシレート、ホモメンチルフェニルサリシレート等のサリチル酸エステル系紫外線吸収剤、２−エチルヘキシル−２−シアノ−３，３’ジフェニルアクリレート、エチル−２−シアノ−３，３’−ジフェニルアクリレート等のシアノアクリレート系紫外線吸収剤、ｐ−アミノ安息香酸、ｐ−アミノ安息香酸グリセリル、ｐ−ジメチルアミノ安息香酸アミル、ｐ−ジヒドロキシプロピル安息香酸エチル等のｐ−アミノ安息香酸系紫外線吸収剤、ｐ−メトキシケイ皮酸−２−エチルヘキシル、ｐ−メトキシケイ皮酸−２−エトキシエチル等のケイ皮酸系紫外線吸収剤、４−ｔ−ブチル−４’−メトキシ−ジベンゾイルメタン、ウロカニン酸、ウロカニン酸エチル等が挙げられる。
【００９５】
無機紫外線吸収剤としては、硫化亜鉛、酸化チタン、酸化セリウム、酸化スズ、酸化モリブデン、酸化亜鉛、窒化バリウム、シリカ、アルミナ、酸化アンチモン、酸化マグネシウム、酸化ジルコニウム、酸化バリウム、酸化カルシウム、酸化ストロンチウム、窒化珪素、窒化アルミニウム、窒化ホウ素、硫酸バリウム等が挙げられる。
【００９６】
保護層には、紫外線吸収性能または紫外線遮蔽性能を有しない他のフィラーをスティッキング防止や耐久性向上を目的に添加しても良く、フィラーとしては無機フィラーと有機フィラーに分けることができる。
無機フィラーとしては、炭酸カルシウム、炭酸マグネシウム、無水ケイ酸、含水ケイ酸、含水ケイ酸アルミ二ウム、含水ケイ酸カルシウム、アルミナ、酸化鉄、酸化カルシウム、酸化マグネシウム、酸化クロム、酸化マンガン、シリカ、タルク、マイカ、等が挙げられる。
有機フィラーとしては、シリコーン樹脂、セルロース樹脂、エポキシ樹脂、ナイロン樹脂、フェノール樹脂、ポリウレタン樹脂、ユリア樹脂、メラミン樹脂、ポリエステル樹脂、ポリカーボネイト樹脂、スチレン、ポリスチレン、ポリスチレン・イソプレン、スチレンビニルベンゼンなどのスチレン系樹脂、塩化ビニリデンアクリル、アクリルウレタン、エチレンアクリルなどのアクリル系樹脂、ポリエチレン樹脂、ベンゾグアナミンホルムアルデヒド、メラミンホルムアルデヒドなどのホルムアルデヒド系樹脂、ポリメチルメタクリレート樹脂、塩化ビニル樹脂等が挙げらる。本発明ではフィラーを単独で用いることもできるが、２種類以上含まれても良い。複数の場合、無機フィラーと有機フィラーの組み合わせ方について特に限定はされない。また、形状としては球状、粒状、板状、針状等が挙げられる。保護層中のフィラーの含有量は体積分率で５〜５０体積％である。
【００９７】
サーマルヘッドへの融着防止を目的に、保護層に滑剤を添加しても良く、滑剤の具体例としては、エステルワックス、パラフィンワックス、ポリエチレンワックス等の合成ワックス類：硬化ひまし油等の植物性ワックス類：牛脂硬化油等の動物性ワックス類：ステアリルアルコール、ベヘニルアルコール等の高級アルコール類：マルガリン酸、ラウリン酸、ミスチレン酸、パルミチル酸、ステアリン酸、ベヘニン酸、フロメン酸等の高級脂肪酸類：ソルビタンの脂肪酸エステルなどの高級脂肪酸エステル類：ステアリン酸アミド、オレイン酸アミド、ラウリン酸アミド、エチレンビスステアリン酸アミド、メチレンビスステアリン酸アミド、メチロールステアリン酸アミド等のアミド類などが挙げられる。層中の滑剤の含有量は体積分率で０．１〜９５％、より好ましくは１〜７５％である。
【００９８】
本発明において、オーバーシートとして用いられる可逆性感熱記録材料には、記録層と保護層との接着性向上、保護層の塗布による記録層の変質防止、保護層に含まれる添加剤が記録層へ移行する、あるいは、記録層に含まれる添加剤が保護層へ移行することを防止する目的で、両者の間に中間層を設けることができる。
中間層の膜厚は０．１〜２０μｍの範囲が好ましく、より好ましくは０．３〜１０μｍである。中間層の塗液に用いられる溶媒、塗液の分散装置、バインダー、塗工方法、乾燥・硬化方法等は上記記録層で用いられた公知の方法を用いることができる。
また、中間層には、地肌かぶりを防止する目的で、保護層に用いる上記無機または有機紫外線吸収剤を含有させて良く、その含有量はバインダー１００重量部に対して０．５〜５０重量部の範囲が好ましい。
【００９９】
さらに、本発明の情報表示記録カードに用いられる可逆性感熱記録材料には、その可逆性感熱記録層に光電変換物質を含有させるか、該記録層と隣接して光電変換物質を含有する層（光電変換層という）を設けることができる。
このような光電変換物質を含有させた構成にすることによって、低出力の半導体レーザ等を使用した場合でも、記録（発色・消色）を行なうことができる。
光熱変換物質を用いる上記２つのやり方のうち、光熱変換層を可逆性記録層と隣接して設ける場合の方が、光熱変換物質は高価であるというコストの点と、記録層を構成する材料に影響しにくいので、好ましい。
またさらに、本発明においては、光熱変換物質を含有する層を保護するために、可視光透過性の紫外線吸収層をさらに設けることができる。
使用される光熱変換物質としては、例えば赤外吸収色素やカーボンブラック等が挙げられ、使用する半導体レーザ光の発振波長付近に吸収ピークを持つものが選択される。
一般には、波長１００ｎｍ〜１，０００ｎｍ、好ましくは７００〜９００ｎｍの半導体レーザを使用することができ、赤外吸収色素としては、かかる波長領域に吸収ピークを有するシアニン系色素、ポリメチン系色素、アントラキノン系色素等が好ましく用いられる。これらの中では、フタロシアニン系色素又はナフタロシアニン系色素が好ましい。
構造的に、熱や紫外線による分解等の劣化に対して耐久性があるので、リライト回数の向上を図ることができるからである。
耐候性、耐熱性等の化学的安定性の見地からは、特に、各種金属と錯体を形成しているものが好ましい。
また、一重項酸素クエンチャーを添加して化学的安定性を向上させてもよい。
【０１００】
本発明のオーバーシートである可逆性感熱記録材料については、支持体の上に記録層およびその他の必要な層を順次形成して製造するのが一般的であるが、この製造法に限定されるものではなく、次のような製造法も適用できる。
例えば、支持体上に可逆性感熱記録層および保護層を順次設けた可逆性感熱記録材料についていえば、最上層に設ける保護層面と剥離性が高い剥離基材シートを用意し、該剥離基材シート上に塗工液を塗って保護層を先ず形成し、次に該保護層上に塗工法によって感熱記録層を形成した後、感熱記録層に支持体フイルムを接着し、最後に剥離基材シートを剥がして、可逆性感熱記録材料を製造する方法が挙げられる。
【０１０１】
また、本発明のオーバーシートである可逆性感熱記録材料の一部分もしくは全面に、オフセット印刷、グラビア印刷などの印刷、またはインクジェットプリンター、熱転写プリンター、昇華型プリンターなどによって任意の絵柄などを施した着色層を設けても良く、さらに着色層上の一部分もしくは全面に硬化性樹脂を主成分とするＯＰニス層を設けても良い。
【０１０２】
図３及び図４に、本発明の情報記録表示カードの一例である、印刷層を有するＩＣカードを作成する方法の一例について図示した。
図３は、ＩＣカードを形成するためのプレスを行なう前の状態の層構成を示す断面図である。図３に示すＩＣカードは、２枚のコアシート部（Ｂ１）と（Ｂ２）との間に、インレットシート（Ｃ）を挟み込み、その一方のコアシート部（Ｂ１）の外側にオーバーシート支持体（１０３）がコアシート部面と接するようにオーバーシート（Ａ）を重ね、他方のコアシート部（Ｂ２）の外側に外層シート（Ｄ）を重ね、オーバーシート（Ａ）と外層シート部（Ｄ）の外側から加熱加圧プレスを行なって加熱圧着させることによりＩＣカード用積層体が形成される。ここで、インレットシート（Ｃ）はアンテナコイル（１１４）を備えた非接触型ＩＣチップ（１１３）を配置したシート（１１８）である。外層シート部（Ｄ）は、磁気ストライプ層（１１５）が予め仮転写された外層シート（１１９）である。また、コアシート部（Ｂ１）は白色のコアシート（１１６）のオーバーシート側の面に印刷層（１１１）が、コアシート部（Ｂ２）は白色のコアシート（１１７）の外層シート部（Ｄ）側の面に印刷層（１１２）が予め設けられている。
次に、剥離基材（１０１）を除去した後、打抜き刃でカード形状に切断してＩＣカードが形成される。このように剥離基材を最後に剥離する方法によれば、剥離基材（１０１）が可逆性記録層（１０２）の保護フィルムとして機能するので、ＩＣカード製造工程中、傷つきを防ぎ、可逆性記録層からブリード等による熱プレス用鏡面板の汚れを防ぐことができる。
図３においては、加熱圧着後に剥離基材を除去する方法を示したが、剥離基材（１０１）をオーバーシート（Ａ）から予め除去しておいて、これをコアシート（Ｂ１）に重ねて同様に熱プレス等を行ない、ＩＣカードを作成してもよい。かかる構成のオーバーシートは、汎用の厚手オーバーシートと同様に取り扱うことができるので、汎用カードの製造ラインを利用することができる。また、剥離基材を除去した形態でロール状に巻回したオーバーシートを使用することもできる。
本態様において、プレス加工の条件は、プレス温度が１００℃〜１５０℃の範囲内であることが好ましく、プレス圧力が１０ｋｇｆ／ｃｍ^２〜５０ｋｇｆ／ｃｍ^２の範囲内であることが好ましく、プレス時間が５分〜６０分の範囲内であることが好ましい。
図３に示すように、加熱圧着されて形成されたＩＣカードは、カード形状に形成した後、エンボッサーを用いて文字刻印（エンボス）を行なうことができる。エンボス（１２０）が施されたＩＣカード（Ｅ）を図４に示す。
【０１０３】
また、前記アンテナコイルを備えた非接触型ＩＣチップを配置するシートのシート材料としては、上記したコアシートや外層シートと同様の材料やエンジニアリングプラスチック等を使用することができるが、特に耐熱性に優れた材料が好ましい。アンテナコイルは、かかるシートに印刷やエッチングを行なうことにより形成してもよい。なお、図３に示すＩＣカードにおいては、アンテナコイルを備えた非接触型ＩＣチップ等を配置したシートを使用したが、アンテナコイルを配線したＩＣチップを使用してもよい。
【０１０４】
本発明のＩＣカードに搭載された磁気テープやＩＣチップ等の情報は、接触又は非接触による従来公知の方法によって、保存された情報を読み取ったり、新規な情報を書き込んだりすることができる。
【０１０５】
本発明の画像処理方法は、前記本発明の情報記録表示カードの画像表示部表面を加熱することによって画像の表示及び画像の消去の少なくともいずれかを行なう工程を含むものであれば、他にいかなる工程が付加されていてもよい。
【０１０６】
本発明のオーバーシートである可逆性感熱記録材料に、発色画像を形成させるためには、いったん発色温度以上に加熱したのち急冷されるようにすればよい。
具体的には、たとえばサーマルヘッドやレーザー光で短時間加熱すると記録層が局部的に加熱されるため、直ちに熱が拡散し急激な冷却が起こり、発色状態が固定できる。
一方、消色させるためには適当な熱源を用いて比較的長時間加熱し冷却するか、発色温度よりやや低い温度に一時的に加熱すればよい。長時間加熱すると記録媒体の広い範囲が昇温し、その後の冷却は遅くなるため、その過程で消色が起きる。この場合の加熱方法には、熱ローラー、熱スタンプ、熱風、セラミックヒータなどを用いてもよいし、サーマルヘッドを用いて長時間加熱してもよい。記録層を消色温度域に加熱するためには、例えばサーマルヘッドへの印加電圧やパルス幅を調節することによって、印加エネルギーを記録時よりやや低下させればよい。
この方法を用いれば、サーマルヘッドだけで記録・消去ができ、画像の消去と新しい画像の表示によりいわゆるオーバーライトが可能になる。記録装置としては、通常用いられるプリンター以外に熱転写プリンター、昇華型プリンターなどを用いても良い。また、熱ローラー、熱スタンプによって消色温度域に加熱して消去することもできる。
【０１０７】
本発明の画像処理装置は、本発明の情報記録表示カードへの画像の表示を行なうのに用いられる画像表示装置、画像の消去を行なうのに用いられる画像消去装置、画像の表示及び消去を行なうのに用いられる画像表示・消去装置のうちの少なくともいずれかを具備すること以外は、特に制限はない。
画像の表示手段としては、サーマルヘッドやレーザー装置等が挙げられ、画像の消去手段としては、サーマルヘッド、セラミックヒータ、熱ローラー、熱スタンプ、熱風機等が挙げられる。
【０１０８】
【実施例】
以下に、実施例および比較例に基づいて本発明の情報記録表示カードについて、より具体的に説明するが、本発明の情報記録表示カードは、これらの実施例に限定されるものではない。
【０１０９】
（実施例１）
１．オーバーシートを構成する支持体とその上に形成するバリア層の作製
支持体として、１００μｍ厚の芳香族ポリエステル樹脂とポリカーボネート樹脂のポリマーアロイ樹脂を主成分とする非晶質のシート（三菱樹脂株式会社製、商品名：ディアフィクスＰＡ−Ｃ）を用意した。
次に、バリア層として厚さ４．５μｍの延伸ＰＥＴフィルム（三菱化学ポリエステルフィルム株式会社製、商品名：ダイアホイルＫ２３３Ｅ）を用い、その一方の面にウレタン系樹脂とイソシアネート架橋剤の２液タイプの接着剤溶液を塗布し、乾燥させて、１μｍ厚の接着剤層を形成した後、この接着剤層を前記支持体に重ねてドライラミネートし、得られたシートを４０℃雰囲気下で２４時間エージングして、支持体上にバリア層を設けたものを作成した。
２．オーバーシートを構成する可逆性感熱記録層と保護層の作製
（１）可逆性感熱記録層
下記の可逆性記録層用分散液を調整し、この塗布液を、上記のバリア層の上にワイヤーバーを用いて塗布し８０℃５分で乾燥後、６０℃２４時間のキュアーを行なって膜厚約１０μｍの可逆性記録層を形成した。
（可逆性感熱記録層用分散液）
１）下記構造式の顕色剤 ４部
【０１１０】
【化２】

２）ジアルキル尿素（日本化成社製、ハクリーンＳＢ） １部
３）アクリルポリオール５０％溶液 ９部
（三菱レイヨン社製、ＬＲ５０３）
４）メチルエチルケトン ７０部
上記組成物を、ボールミルを用いて平均粒径約１μｍまでなるように粉砕分散した。
５）２−アニリノ−３−メチル−６ジブチルアミノフルオラン １部
６）イソシアネート（日本ポリウレタン社製、コロネートＨＬ） ２部
顕色剤を粉砕分散した分散液に上記組成物を加え、良く攪拌し記録層塗布液を調製した。
【０１１１】
（２）保護層
次に、下記に示す保護層形成用塗布液を調整し、この塗布液を、形成した可逆性記録層の上に、厚みが２μｍとなるように塗布した後、紫外線を１６０Ｗ／ｃｍ×１０ｍ／分の条件で照射して硬化させ、次に６０℃で１６時間エージングを行なうことにより、保護層を形成した。このようにして、オーバーシート基材、バリア層、可逆性感熱記録層及び保護層をこの順に有するオーバーシートを作製した。
【０１１２】
（保護層形成用塗布液）
１）ウレタンアクリレート系紫外線硬化性樹脂 １５部
（大日本インキ社製、Ｃ７−１５７）
２）フィラー（水澤化学社製、Ｐ５２７） ５部
３）酢酸エチル ８５部
上記組成物を、よく溶解攪拌し保護層形成用塗布液を調製した。
【０１１３】
３．情報記録表示カードの作製
１００μｍ厚の芳香族ポリエステル樹脂とポリカーボネート樹脂のポリマーアロイ樹脂を主成分とする非晶質のシート（三菱樹脂株式会社製、商品名：ディアフィクスＰＡ−Ｃ）を外層シートとして、２８０μｍ厚の非晶質ポリエステルシート（三菱樹脂株式会社製、商品名：ディアフィクスＰＧ−ＷＨＩ）をコアシートとして用意した。
これらのコアシートと、上記の得られた各オーバーシートとを３００ｍｍ×３００ｍｍの大きさにそれぞれ切断した。
２枚のコアシートを重ね、これを上下から外層シートとオーバーシートの保護層が外面になるように挟んだ状態にした後、ずれないようにさらにクロムメッキ板の間に挟み、加熱プレスを行なって融着一体化した。
加熱温度は１２０℃、プレス圧力はシート面圧で１５ｋｇ／ｃｍ^２、プレス時間は１０分間である。
融着一体化したシートを冷却し、取り出した後、カード形状に打ち抜き、情報記録表示カードを作製した。
【０１１４】
（実施例２）
オーバーシート作製において、１００μｍ厚の芳香族ポリエステル樹脂とポリカーボネート樹脂のポリマーアロイ樹脂を主成分とする非晶質のシート（三菱樹脂株式会社製、商品名：ディアフィクスＰＡ−Ｃ）上にドライラミネートする延伸ＰＥＴフィルムを厚さ６μｍの延伸ＰＥＴフィルム（商品名：ダイアホイル Ｋ２３０Ｅ）に変更してバリア層とした以外は、実施例１と同様にして情報記録表示カードを作製した。
【０１１５】
（実施例３）
オーバーシート作製において、１００μｍ厚の芳香族ポリエステル樹脂とポリカーボネート樹脂のポリマーアロイ樹脂を主成分とする非晶質のシート（三菱樹脂株式会社製、商品名：ディアフィクスＰＡ−Ｃ）上にドライラミネートする延伸ＰＥＴフィルムを厚さ８μｍの延伸ＰＥＴフィルム（商品名：ダイアホイル Ｃ２３０−８Ｅ）に変更してバリア層とした以外は、実施例１と同様にして情報記録表示カードを作製した。
【０１１６】
（実施例４）
オーバーシート作製において、１００μｍ厚の芳香族ポリエステル樹脂とポリカーボネート樹脂のポリマーアロイ樹脂を主成分とする非晶質のシート（三菱樹脂株式会社製、商品名：ディアフィクスＰＡ−Ｃ）上に、下記に示すバリア層用塗布液をバーコーターを用いて塗布した。
その後、１６０Ｗ／ｃｍ×１０ｍ／ｍｉｎで紫外線を照射して硬化させ、厚み２μｍのバリア層とした以外は、実施例１と同様にして情報記録表示カードを作製した。
【０１１７】

【０１１８】
（実施例５）
オーバーシート作製において、１００μｍ厚の芳香族ポリエステル樹脂とポリカーボネート樹脂のポリマーアロイ樹脂を主成分とする非晶質のシート（三菱樹脂株式会社製、商品名：ディアフィクスＰＡ−Ｃ）上に、下記に示すバリア層用塗布液をバーコーターを用いて塗布した。
その後、１００℃×５分間乾燥して、厚み２μｍのバリア層とした以外は、実施例１と同様にして情報記録表示カードを作製した。
【０１１９】
（バリア層用塗布液）
・水分散ポリエステルポリオール樹脂 ５０重量部
（日華化学株式会社製、商品名「エバフェノールＨＯ−１８」）
・水分散ポリイソシアネート ６重量部
（日華化学株式会社製、商品名「ＮＫアシストＩＳ−１００Ｎ」
・水 ２０重量部
【０１２０】
（実施例６）
支持体として、１００μｍ厚の芳香族ポリエステル樹脂とポリカーボネート樹脂のポリマーアロイ樹脂を主成分とする非晶質のシート（三菱樹脂株式会社製、商品名：ディアフィクスＰＡ−Ｃ）を１００μｍ厚の非晶質の芳香族ポリエステル樹脂とポリカーボネート樹脂のポリマーアロイ樹脂を主成分とするシート（三菱樹脂株式会社製，商品名：ディアフィクスＰＧ−ＣＨＴ）に変更してバリア層とした以外は、実施例１と同様にして情報記録表示カードを作製した。
【０１２１】
（実施例７）
剥離基材として、あらかじめ表面にシリコーン樹脂を塗工したポリエチレンテレフタレートフィルム（３８μｍ厚）を用意した。
このシリコーン処理面に、エポキシアクリレート系紫外線硬化性樹脂を塗布した後、１６０Ｗ／ｃｍの紫外線を１０ｍ／分の条件で照射して硬化させ、厚みが５μｍの保護層を形成した。
次に、実施例１で用いた可逆性記録層用分散液を、剥離基材に設けた保護層面上に塗布し、８０℃で５分間乾燥させた後、６０℃で２４時間エージングを行ない、乾燥後の厚みが１０μｍである可逆性記録層を形成した。
１００μｍ厚の芳香族ポリエステル樹脂とポリカーボネート樹脂のポリマーアロイ樹脂を主成分とする非晶質のシート（三菱樹脂株式会社製、商品名：ディアフィクスＰＡ−Ｃ）上に上記にて得られた剥離基材／保護層／可逆記録層の積層体の記録層面側に、ウレタン系樹脂とイソシアネート架橋剤の２液タイプの接着剤塗布液を用いてドライラミネートにより貼り合わせた。
このようにして、剥離基材／保護層／可逆性記録層／支持体の積層構造を作成した後に、剥離基材を剥離してオーバーシートを得た以外は、実施例１と同様にして情報記録表示カードを作製した。
【０１２２】
（実施例８）
情報記録表示カード作製において、２８０μｍ厚の非晶質ポリエステルシート（三菱樹脂株式会社製、商品名：ディアフィクスＰＧ−ＷＨＩ）からなるコアシートを２８０μｍ厚の非晶質ポリエステルシート（三菱樹脂株式会社製、商品名：ディアフィクスＰＧ−ＷＨＴ）に変更した以外は、実施例１と同様にして情報記録表示カードを作製した。
【０１２３】
（実施例９）
実施例１に用いた可逆性感熱記録層用分散液の顕色剤を下記化合物にした以外は、実施例１と同様にして情報記録表示カードを作製した。
【０１２４】
【化３】

【０１２５】
（比較例１）
オーバーシート作製において、１００μｍ厚の芳香族ポリエステル樹脂とポリカーボネート樹脂のポリマーアロイ樹脂を主成分とする非晶質のシート（三菱樹脂株式会社製、商品名：ディアフィクスＰＡ−Ｃ）上にドライラミネートする延伸ＰＥＴフィルムを厚さ１２μｍの延伸ＰＥＴフィルム（商品名：ダイアホイルＨ１００）に変更してバリア層とした以外は、実施例１と同様にして情報記録表示カードを作製した。
【０１２６】
（比較例２）
オーバーシート作製において、１００μｍ厚の芳香族ポリエステル樹脂とポリカーボネート樹脂のポリマーアロイ樹脂を主成分とする非晶質のシート（三菱樹脂株式会社製、商品名：ディアフィクスＰＡ−Ｃ）上にドライラミネートする延伸ＰＥＴフィルムを厚さ３８μｍの延伸ＰＥＴフィルム（商品名：ダイアホイルＴ１００Ｅ）に変更してバリア層とした以外は、実施例１と同様にして情報記録表示カードを作製した。
【０１２７】
（比較例３）
オーバーシート作製において、１００μｍ厚の芳香族ポリエステル樹脂とポリカーボネート樹脂のポリマーアロイ樹脂を主成分とする非晶質のシート（三菱樹脂株式会社製、商品名：ディアフィクスＰＡ−Ｃ）を１００μｍ厚の非晶質の芳香族ポリエステル樹脂を主成分とするシート（三菱樹脂株式会社製，商品名：ディアフィクスＰＧ−ＣＨＩ）に変更した以外は、実施例１と同様にして情報記録表示カードを作製した。
【０１２８】
（比較例４）
オーバーシート作製において、１００μｍ厚の芳香族ポリエステル樹脂とポリカーボネート樹脂のポリマーアロイ樹脂を主成分とする非晶質のシート（三菱樹脂株式会社製、商品名：ディアフィクスＰＡ−Ｃ）を１２５μｍ厚の延伸（結晶化）ＰＥＴシート（ダイアホイル製，商品名：Ｔ１００Ｅ）に変更した以外は、実施例７と同様にして情報記録表示カードを作製した。
【０１２９】
（比較例５）
オーバーシート作製において、１００μｍ厚の芳香族ポリエステル樹脂とポリカーボネート樹脂のポリマーアロイ樹脂を主成分とする非晶質のシート（三菱樹脂株式会社製、商品名：ディアフィクスＰＡ−Ｃ）を１００μｍ厚の塩化ビニルフィルムのビニホイルＣ−８１９５に変更し、２８０μｍ厚の非晶質ポリエステルシート（三菱樹脂株式会社製、商品名：ディアフィクスＰＧ−ＷＨＩ）からなるコアシートを２８０μｍ厚の塩化ビニルフィルムのビニホイルＣ−４６３６に変更した以外は、実施例７と同様にして情報記録表示カードを作製した。
【０１３０】
上記の各実施例および比較例で作製されたオーバーシートと情報記録表示カードについて、下記の評価方法により評価し、その結果を下記表４に示す。
【０１３１】
試験１：貯蔵弾性率測定
サンプルを板状に切り、岩本製作所製「粘弾性スペクトロメーター」を用いて、引張り法にて試験を行なった。動的粘弾性は、０〜２００℃の範囲で３℃刻み、周波数１Ｈｚの条件で測定し、実数項を貯蔵弾性率（Ｅ’）として算出した。
【０１３２】
試験２：オーバーシートの消去温度測定
東洋精機社製熱傾斜試験機ＨＧ−１００を用い、圧力１Ｋｇｆ／ｃｍ、加圧時間１秒、温度５℃刻みの条件で、飽和濃度に達している印字画像を上記条件で消去させる。このときの発色濃度が「地肌濃度＋０．０２以下」になったときの温度を消去温度とする。
【０１３３】
試験３：リライト特性
カードプリンターＲ２８０００（九州松下社製）を用いて、印字条件：０．７５ｍＪ、ヒーターバー温度条件：１４０℃の条件で消去と印字を行ない、画像ムラの発生しない鮮明な画像が得られ、消し残しが観察されない状態を「○」、画像ムラ・消去ムラが観察される状態を「×」で表わす。
【０１３４】
試験４：繰り返し後の耐久性
カードプリンターＲ２８０００（九州松下社製）を用いて消去と印字を２００回繰り返し、記録媒体表面の状態を目視で観察して下記のランクで評価した。
ランク１：記録媒体表面に打こん・傷・カード変形は発生しなかった。
ランク２：記録媒体表面に打こん・キズは発生しなかったが、カード変形が発生した。
ランク３：記録媒体表面に激しい打こんと傷・カード変形が発生した。
【０１３５】
試験５：エンボス適性
作成したカードを使用して、ハンドエンボッサー ＪＩＫＥＮ ＮＥ−１０００（日本字研社製）を用いてエンボス加工を行なった。得られたエンボスカードのカード反りを測定し、２．５ｍｍを超えるものには、「×」をつけた。エンボス加工は、ＪＩＳ Ｘ６３０１やＸ６３０２に規定されているエンボスを施した。
また、カード反りは、ＪＩＳ Ｘ６３０１，６３０５に規定されている方法で測定した。エンボス外観は、エンボスによりオーバーシートのワレや、オーバーシートのハガレなどがないどうか目視にて確認した。特に問題ないカードは「○」、ワレやハガレが見られるカードには「×」をつけた。
【０１３６】
【表４】

【０１３７】
【発明の効果】
以上、詳細かつ具体的な説明より明らかなように、本発明の可逆性感熱記録媒体はエンボス加工が容易にでき、かつ発消色の繰返し画像形成においても変形することなく高耐久性に優れるものである。
【図面の簡単な説明】
【図１】本発明の実施形態に係る情報記録カードを作成する方法を説明するための図であり、（ａ）は本発明の実施形態に係る情報記録カードを加熱プレスする前の状態を示す断面図であり、（ｂ）は加熱プレスした後の状態を示す断面図である。
【図２】本発明の可逆性感熱記録媒体の発色・消色特性を示す図である。
【図３】本発明のＩＣカードを作成する方法を説明するための図であり、ＩＣカードを加熱プレスする前の状態を示す断面図である。
【図４】図３に示すＩＣカードを加熱プレスした後、エンボスを施した状態を示す断面図である。
【符号の説明】
１ 支持体
２ バリア層
３ 可逆性記録層
４ 保護層
５ コアシート
６ 外層シート
１０ オーバーシート
Ａ オーバーシート
Ｂ１ コアシート部
Ｂ２ コアシート部
Ｃ インレットシート
Ｄ 外層シート部
Ｅ ＩＣカード
１０１ 剥離基材
１０２ 可逆性記録層
１０３ オーバーシート支持体
１１１ 印刷層
１１２ 印刷層
１１３ 非接触型ＩＣチップ
１１４ アンテナコイル
１１５ 磁気ストライプ層
１１６ コアシート
１１７ コアシート
１１８ シート
１１９ 外層シート
１２０ エンボス[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an information recording / display card having both a function of displaying and rewriting information by heating and a function of storing and rewriting information, an oversheet made of a reversible thermosensitive recording material used for the card, and an image display / erasing method.
[0002]
[Prior art]
An information recording card such as a member card, an ID card, a credit card, a cash card, or an IC card has an information storage unit such as a magnetic tape or an IC chip arranged in a part of the card. In particular, personal confidential information such as money can be recorded, and it is widely used in various countries in society at present because of its small size and high convenience. This information recording card is used by reading and rewriting the recorded information using a special device, but has a drawback that the card owner cannot directly visually recognize the recorded information. Things.
[0003]
On the other hand, development of a rewritable card capable of forming a temporary image and erasing the image when it is no longer needed, that is, displaying information visually on the surface and rewritable information has been performed. Recently used in the market. Some rewritable cards have a magnetic information storage function.
The function of this rewrite card to visually display and rewrite information as an image is to have a lactone ring in the molecular structure and to open the lactone ring by electron emission to cause a structural change to give a color. Formation of a relatively colored state and a decolored state between an electron-donating compound (so-called leuco dye) and an acid / base compound as a color-developing agent due to a difference in heating temperature and / or cooling rate after heating. A reversible thermosensitive recording layer comprising, for example, such an electron-donating compound and a color-reducing agent as main components in a resin base material is provided on a support. A rewrite card is used as the recording material (for example, see Patent Documents 1 and 2).
[0004]
More specifically, this reversible thermosensitive recording material repeats coloring and decoloring by utilizing the difference in the reaction rate between an acid and a base. A reversible thermosensitive recording material containing a leuco dye and an electron-accepting compound having a long-chain alkyl group as a color developer in a resin base material is disclosed (for example, see Patent Documents 3 and 4). Since the developer has a long-chain alkyl structure, it has a cohesive force, and repeats coloring and decoloring by contacting or separating with a leuco dye.
[0005]
The function of this reversible thermosensitive recording material for visually displaying and rewriting information is attracting attention as being capable of sufficiently compensating for the above-mentioned disadvantages of conventional information recording cards. A card that has both a function of displaying and rewritably displayed and a function of recording and rewritable information as an information storage unit (hereinafter referred to as an information recording and display card) has been developed and recently started to be used in the market. .
This information recording and display card is basically provided with at least a reversible thermosensitive recording layer provided on a support such as a reversible thermosensitive recording material, as an oversheet, or as a conventional information recording card. It is formed by using a material having a function as a core sheet, stacking the support side of the oversheet on the core sheet, and performing thermocompression bonding or the like.
The image display function of the information recording and display card is performed by the oversheet, but the information storage function differs depending on the type. The information storage function using a magnetic material such as a magnetic tape may be provided by either the oversheet or the core sheet. Although it is possible, in the case of an IC chip, an antenna coil, a magnetic stripe, or the like, it is general to arrange it on a thick core sheet.
There are two types of information recording and display cards: a thin type and a thick type. However, since the thickness of the oversheet is small, the thickness of the information recording and display card usually depends on the thickness of the core sheet.
[0006]
The information recording and display cards that have recently begun to be used in the market include an oversheet using a polyethylene terephthalate (PET) film as a support and a polyvinyl chloride (PVC) resin or a polyvinyl chloride / vinyl acetate copolymer. It is a combination of a core sheet made of a vinyl chloride resin or a polycarbonate resin.
The reason why these materials are widely used is that the polyethylene terephthalate (PET) film used for the support of the oversheet has a solvent resistance particularly to a solution obtained by dissolving a composition for forming a reversible recording layer in a solvent. It is considered that the polyvinyl chloride resin (PVC) used for the core sheet material is excellent in physical properties, mechanical properties, and suitability for embossing of a character portion. .
This polyvinyl chloride-based resin is also a material suitable for obtaining image erasing characteristics as a support for an oversheet in that it exhibits a certain degree of flexibility by heat.
[0007]
However, although this polyvinyl chloride resin has such excellent properties as a card material, it generates hydrogen chloride gas at the time of incineration at the time of disposal after use. There is some opinion that this is the cause. Furthermore, although the relationship with dioxin has not been clarified, the movement to remove PVC has been active in various countries, and this polyvinyl chloride resin is used not only for information recording and display cards but also for conventional information recording cards. However, because of their high public nature, there is a demand in Japan for switching from PVC to other materials.
[0008]
Therefore, for information recording and display cards, the use of a halogen-free thermoplastic resin such as a polyethylene resin, a polypropylene resin, a polyester resin, a polycarbonate resin, and a polyacryl resin as a card material has been studied.
Among them, a card base material such as a polycarbonate resin is a material which has high heat resistance, is less deformed by heat, and is excellent in durability quality. Therefore, information recording and display cards using the same are also on the market.
However, polycarbonate resins have low embossability due to low deformability, and in reversible thermosensitive recording materials for writing and erasing by using a thermal head, the head matching property at the time of application is impaired and the sensitivity characteristics are reduced, especially There is a disadvantage that it is difficult to erase, and no material that can be replaced with a polyvinyl chloride resin has been confirmed so far.
[0009]
On the other hand, the presence of the “embossed” marking on the information recording display card, which is formed by embossing the integrated body after the oversheet and the core sheet are bonded, means that personal information is It is important in terms of convenience and ease of use that can be easily recognized.In particular, the provision of “embossed display” on thick cards such as credit cards and bank cards is indispensable in society at present. The demand from users and various related companies is extremely high.
The "embossed display" mainly includes a card number, an expiration date, the owner's name, and the like.For example, a function of inserting the card into a copy slip at the time of settlement in a store and copying the "embossed display" by a roller. It is widely used in Japan and overseas.
[0010]
Polyethylene terephthalate (PET) film used as a support for the oversheet is a material that is rigid, hardly deforms due to pressure, and hardly embossed. Therefore, the polyvinyl chloride resin used for the core sheet is embossed. Even if the material is easy to use, in the case of an oversheet using PET, a satisfactory "embossed display" cannot be obtained even if embossing is performed from above the oversheet. Further, the polyethylene terephthalate (PET) film has a problem that if the thickness is too large, the card is broken during embossing.
In particular, in the case of a thick card which is processed by embedding a non-contact type IC chip, an antenna coil, a magnetic stripe, or the like as described above, the surface of the card is not flat because the unevenness cannot be sufficiently absorbed. There was a difficulty. For this reason, recording rewriting with a thermal head or the like cannot be performed well, and sometimes printing is performed with a high print pressure or temperature.As a result, defects such as scratches, dents, and deformation of the card may occur. This causes the use and the manufacturing method to be limited to specific ones, making it difficult to use the manufacturing process of a general-purpose card.
[0011]
Regarding information recording and display cards that have recently begun to be used in the market, create an embossable space on the surface of the core sheet where there is no oversheet, that is, the size of the oversheet to be attached to the core sheet is determined by the surface area of the core sheet. A narrowed one is prepared and attached to a core sheet, and "embossed display" is provided in a space where there is no overseat.
Such a method has limitations in manufacturing, such as the necessity of attaching an oversheet with a reduced area to the core sheet with high positional accuracy, and the area is limited as an information display card as an image display function of the oversheet. It has the disadvantage that it has been done.
Accordingly, the core sheet with the oversheet adhered to the entire surface cannot be embossed, resulting in an information recording display card without "embossed display".
[0012]
The reversible thermosensitive recording material used as the oversheet is a special material that is sensitive to heat with "heat sensitivity", and the oversheet having such properties is overlaid on the core sheet, pressurized and heated, and integrated. It is quite difficult to produce an information recording / display card without affecting the special property of “reversible heat sensitivity” in each step until the embossing is completed.
[0013]
In addition, when forming or erasing an image on an image display portion of an oversheet, a demand for an information recording / display card which can be performed at a high heating temperature and which can withstand repeated use (repeated durability) is increasing. However, considering that it can satisfy the embossability, conventional products on the market do not meet the requirements.
[0014]
Further, although a considerably high temperature is applied to form or erase an image on the image display portion of the oversheet, there is a demand for an information recording / display card having a performance (repeated durability) that can withstand repeated use. Although it is increasing, considering that it can meet the needs of "embossed display" due to embossability, the above-mentioned information recording and display card in the market does not match naturally, and it still appears as a conventional product I haven't.
[0015]
The present inventors have investigated publicly known materials relating to this type of information recording and display card, and have confirmed that there is no mention or mention of embossability or embossability and its associated repeated durability. did.
A specific example will be described below with reference to a patent document that discloses an information recording / display card.
[0016]
As one of them, a reversible recording film in which a printing layer, a transparent support having a light transmittance of 50% or more, a reversible recording layer and a protective layer are provided on a support is used as an oversheet, and the support side and the core sheet are separated. Although there is a thick information recording and display card integrated with an adhesive, embossing is not mentioned as a problem, and is not considered at all because it is not described at all (for example, see Patent Document 5).
[0017]
Materials that can be used as the support and the transparent support are selected from a statement that “a tough plastic film having excellent heat resistance and tensile strength can be applied” and a range of “a thickness of 8.5 μm to 300 μm”. Is used, and a thickness of about 8.5 μm to about 250 μm is used. ”Specific examples include“ a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, a polyimide (PI) film, and a polyphenylene sulfide (PPS). And the transparent support further includes "PVC film, PET-G film, polycarbonate film".
However, although these exemplified films are described as "a tough plastic film with excellent tensile strength", from the viewpoint of embossing, those which are not tough and those which are too tough, or which are deformed by heat. Some are few and many are obviously impossible to emboss.
Also, in terms of the thickness, for example, in Example 1, although there is no description about the thickness of the polyethylene terephthalate film used as a support, a transparent polyethylene terephthalate film having a thickness of 25 μm is used as a transparent support. It is used, but it is clear that embossing the oversheet is too thick to be possible.
In addition, as the core sheet material, a sheet alone or a mixture of a PVC resin, a polyester resin typified by PET-G, and a polycarbonate resin is mentioned, but there is no description suggesting the possibility of embossing. When examined from the viewpoint of processing, there are some that may and may not.
[0018]
As a next example, a low-crystalline thermoplastic resin sheet having a crystallinity of 5% or less is used as a card base material (core sheet), and a reversible recording layer (leuco compound and developer) is formed on a transparent PET film. (See, for example, Patent Document 6). A thick information recording and display card formed by bonding a reversible thermosensitive recording tape (oversheet) provided with
In this proposal, there is no description suggesting embossing, and since a thick PET film (25 μm in Example 1 and 38 μm in Example 2) is used, the information recording and display card is embossed. Is presumed to be impossible.
[0019]
Next, a sheet (core sheet) incorporating the IC chip module and a reversible thermosensitive recording sheet (oversheet) provided with a reversible recording layer (containing a leuco compound and a color developer) on the film are opposed to each other. There is a proposal for an IC card (thick information recording and display card) in which a resin is injection-molded and bonded in a gap between both sheets, but no embossing is described (for example, see Patent Document 7). .
[0020]
Furthermore, there is a proposal for a recording medium used in a kanban type mass production factory in which a reversible thermosensitive recording layer (containing a leuco compound and a color developer) and a protective layer are provided on a base material. Although a film is illustrated, the white PET as the base material used in each example has a thickness of 188 μm, 250 μm, and 350 μm, and therefore, no consideration is given to embossing ( For example, see Patent Document 8.)
[0021]
In addition, in the above-mentioned Patent Document 6, Patent Document 7, and Patent Document 8, various materials are listed as specific examples of the material for the support constituting the oversheet and the material for the material constituting the core sheet. However, as described in the above-mentioned Patent Document 5, among the exemplified materials, from the viewpoint of embossing, there are those that are less deformed by heat and those that are more deformed, and those that can be embossed. And impossible and various.
[0022]
As is clear from the above description, the information recording and display card that has begun to be used in the market has a reduced image display area for embossing because it cannot be embossed on the overseat surface. In addition, they have insufficient repetitive durability and cause environmental pollution during disposal.
On the other hand, none of the information recording and display cards disclosed in the publicly known materials have been studied from the viewpoint of embossability, and none of them have taken up repeated durability. No suggestion has been made to solve the problem.
In other words, in order to obtain sufficient embossability for the information recording and display card, first, each of the oversheet and the core sheet constituting the card and the integral body of the oversheet and the core sheet must have the embossability. However, there is no known publicly known product and material which has been studied from this viewpoint, and the present situation is the present situation.
[0023]
In addition, regarding the embossing property, a card used to receive and fix the dye contained in the heat transfer film by melting or sublimating the heat by heat in the field of heat melting or heat transfer recording rather than reversible thermosensitive recording. There is a proposal for a thermal transfer card in which a receiving layer is provided on a base material (for example, see Patent Document 9).
This proposal uses a special polyester for the card substrate and a polyester copolymer obtained by copolymerizing a reactive silicone polymer for the receiving layer, thereby improving the molding characteristics such as embossing of the card to be transferred. However, as a matter of course, when an image is formed or erased on the image display portion of the oversheet, such as an information recording display card (reversible thermosensitive recording card), the repetition durability and the “reversible thermosensitive property” No consideration has been given to compatibility between embossing without affecting specialty.
[0024]
Further, although many reversible thermosensitive recording materials have been proposed in the past according to patent documents and the like, none of them suggests embossability and has been taken up as a problem, and furthermore, it has not been mentioned in information recording display cards. There is no suggestion of embossability when used as an oversheet, and none has been taken up as a problem.Therefore, in this technical field, securing embossability and improving the image erasing characteristics associated therewith is a new issue. It is believed that there is.
[0025]
[Patent Document 1]
JP-A-2-188293
[Patent Document 2]
JP-A-2-188294
[Patent Document 3]
JP-A-5-124360
[Patent Document 4]
JP-A-6-210954
[Patent Document 5]
JP 2001-341427 A (pages 2 to 4, Example 1)
[Patent Document 6]
Japanese Patent Application Laid-Open No. 2000-137782 (Examples 1 and 2)
[Patent Document 7]
JP-A-11-154210 (Example)
[Patent Document 8]
JP 2001-88443 A (Example)
[Patent Document 9]
JP-A-11-240262 (Claims)
[0026]
[Problems to be solved by the invention]
An object of the present invention is to provide an information recording and display card which is excellent in embossability and repetition durability, is easy to dispose, and does not cause a problem of environmental pollution during disposal, and has excellent embossability and repetitive image erasing durability. An object of the present invention is to provide an oversheet made of a reversible thermosensitive recording material, a method for forming and / or erasing an image using the information recording / display card, an image processing apparatus, and a method for manufacturing the information recording / display card.
[0027]
[Means for Solving the Problems]
The object of the present invention is to provide (1) the present invention which includes at least a core sheet and an oversheet, wherein the core sheet and the oversheet are laminated,
The oversheet contains an electron-donating color-forming compound and an electron-accepting compound on a support containing at least an amorphous polyester resin, and has a relative temperature depending on at least one of a heating temperature and a cooling rate after heating. It has a reversible thermosensitive recording layer capable of forming a state in which a colored state and a decolored state are formed, functions as an image display unit, and satisfies the following conditions (A) and (B):
Embossing is possible on the oversheet,
An information record display card characterized by the following;
In the following conditions (A) and (B), “1.0E + 08” is 1.0 × 10 ⁸ Means “1.0E + 04” is 1.0 × 10 ⁴ Means “5.0E + 07” is 5.0 × 10 ⁷ Means
(A) [Erase upper limit temperature of oversheet−30 ° C.] ≦ [temperature of storage elastic modulus E ′ (1.0E + 08) Pa] ≦ 200 ° C.
(B) 1.0E + 04Pa ≦ [storage modulus at 180 ° C. of oversheet E ′] ≦ 5.0E + 07Pa ”,
(2) The information recording display card according to the above (1), wherein the storage elastic modulus E ′ (1.0E + 08) temperature of the oversheet is 140 ° C. or higher, (4) The information recording and display card according to the above (1) or (2), wherein an oversheet is attached to almost the entire surface of the core sheet. The information recording according to any one of the above items (1) to (3), wherein the information recording material is any one of an amorphous polyester resin and a polymer alloy resin of an amorphous polyester resin and a polycarbonate resin. (5) The display card according to any one of (1) to (3), wherein the support is a polymer alloy resin composition of a polybutylene terephthalate resin and a polycarbonate resin. (6) The information according to any one of (1) to (5), wherein a barrier layer is provided between the support and the thermosensitive recording layer. (7) "the information recording and displaying card according to the item (6), wherein the barrier layer is formed by attaching a resin film"; (9) The information recording and display card according to the above (7), wherein the resin film has a thickness of 8 μm or less. (7) or (8), wherein the barrier layer is mainly composed of a resin that can be dissolved or dispersed in at least one of an alcohol-based solvent and water. Characterized by the above (6) The information recording / display card according to the item (11), wherein the electron donating color-forming compound is a leuco dye. And (12), wherein the electron accepting compound is a linear hydrocarbon-containing phenol. (13) The information recording display card described above, wherein the core sheet comprises at least one thermoplastic resin sheet having a thickness of 0.05 to 5.00 mm. (14) The information recording display card according to (13), wherein the core sheet is made of the same material as a support constituting the oversheet. Display card ", (15)" information storage " (16) The information storage and display card according to any one of the above (1) to (14), wherein the information storage unit is mainly made of a magnetic material. (15) The information recording and display card according to (15), wherein the core sheet is made of a thermoplastic resin sheet, and wherein the core sheet is made of a thermoplastic resin. (18) The information storage / display card according to (15), wherein the IC chip is embedded in a sheet to form an information storage unit. (19) The information recording and display card according to the above item (15), wherein the information recording and display card is provided with a stamp by embossing. Any of the terms Placing information recording display card ", it is accomplished by (20)" the first (19) information recording display card according to terms that marking by embossing, characterized in that provided on the over sheet. "
The object of the present invention is also characterized in that (21) the present invention is characterized in that the core sheet and the oversheet are bonded by hot pressing at a temperature equal to or lower than the melting point of the electron-accepting compound. (20) The method for producing an information recording / display card according to any one of the above (20) and (22), wherein the core sheet and the oversheet are bonded by hot pressing at a temperature of 150 ° C. or less. The information recording and display card manufacturing method according to any one of the above items 1) to (20) ".
In addition, the above object is achieved by (23) an "overseat characterized by constituting the information recording and displaying card according to any one of the above items (1) to (20)" of the present invention. .
Further, the object is to provide an image display and an image by heating the surface of the image display section of the information recording / display card according to any one of the above items (1) to (20). (25) An image processing method according to the above item (24), wherein the image is displayed using a thermal head for displaying the image. (26) "The image processing method according to the item (24), wherein the image is erased using one of a thermal head and a ceramic heater to erase the image", (27) " The items (24) to (26), wherein the image is overwritten by using a thermal head for displaying and erasing the image, and overwriting is performed by erasing the image and displaying a new image. It is achieved by an image processing method "according to any misalignment.
The above object is also used in (28) of the present invention for displaying and / or erasing an image on the information recording / display card according to any one of the above items (1) to (20). , An image processing apparatus comprising means for displaying and / or erasing an image, and (29) the item (28) wherein the means for displaying an image is a thermal head. (30) The image processing apparatus according to (28), wherein the image erasing means is one of a thermal head and a ceramic heater.
[0028]
In order to solve the above-described problems, the present inventors have repeatedly studied mainly the oversheet among the oversheet and the core sheet constituting the information recording and displaying card, and have reached the present invention.
The main reason for using the oversheet is that it is a heat-sensitive "reversible thermosensitive" recording material that has the special property of oversheet. In the process of embossing the integrated material, thermal or mechanical energy applied during these processes may cause the above-mentioned specialty of the overseat to be reduced or eliminated in its image display function. For this reason, the present inventors have overcome this negative possibility and created the present invention.
Such an information recording and display card of the present invention does not degrade the function of the image display unit even if the “marks that are raised display” are provided by embossing, and further displays the image on the image display unit, Processing can also be performed.
[0029]
The conditions (A) and (B) that the oversheet has in the information recording and display card in which the oversheet and the core sheet of the present invention are adhered will be described.
(A) [Erase upper limit temperature of oversheet−30 ° C.] ≦ [temperature of storage elastic modulus E ′ (1.0E + 08) Pa] ≦ 200 ° C.
(B) 1.0E + 04Pa ≦ [storage elastic modulus E ′ of oversheet at 180 ° C.] ≦ 5.0E + 07Pa
[0030]
The condition of (A) ([the upper limit of erasure of oversheet−30 ° C.] ≦ [temperature of storage elastic modulus E ′ (1.0E + 08) Pa] ≦ 200 ° C.) is such that the information recording and displaying card of the present invention is excellent This is necessary in order to ensure repeated image erasing durability (hereinafter referred to as repeated durability).
[Erase upper limit temperature] is basically determined by the melting point of the color developer of the reversible thermosensitive material. As a measurement method, the oversheet is brought into contact with a hot plate at 180 ° C. and rapidly cooled to form a saturated color image. After that, using a thermal gradient tester HG-100 (manufactured by Toyo Seiki Co., Ltd.), the plate can be erased by pressing a heating plate shaken at 5 ° C. intervals at a pressure of 1 kgf / cm and a pressing time of 1 second. Find the maximum temperature.
[Temperature of storage elastic modulus E '(1.0E + 08)] was obtained by cutting a sample into a plate shape and conducting a test by a tensile method using a "viscoelastic spectrometer" manufactured by Iwamoto Seisakusho. The dynamic viscoelasticity is measured in the range of 0 to 200 ° C. in steps of 3 ° C. at a frequency of 1 Hz, and the real number term is calculated as the storage modulus (E ′).
[0031]
A reversible thermosensitive recording material of the type containing a leuco dye (electron-donating color-forming compound) and a developer (electron-accepting compound) as used in the present invention generally has a specific image erasing temperature. The erasing upper limit temperature is generally caused by the melting point of the developer.
That is, in order to maintain high durability without causing deformation even when image formation and erasure are repeatedly performed, the temperature of the storage elastic modulus E ′ (1.0E + 08) Pa is set to [erasing of the thermoreversible recording medium. It is necessary to be within the range of not less than the upper limit temperature −30 ° C.] and not more than 200 ° C.
When the temperature of the storage elastic modulus E ′ (1.0E + 08) Pa is less than [the maximum erasing temperature of the thermoreversible recording medium−30 ° C.], the oversheet is too soft and easily undergoes thermal deformation when repeated. Become.
Further, when the temperature of the storage elastic modulus E ′ (1.0E + 08) Pa is lower than 140 ° C., it is not preferable because the temperature is too soft and the curl tends to be largely generated from the printing of a few times.
On the other hand, if the temperature of the storage elastic modulus E ′ (1.0E + 08) Pa exceeds 200 ° C., the oversheet is too hard and the contact with the erase bar head or the thermal head during erasure printing becomes poor, resulting in image unevenness / erasure. It tends to cause unevenness.
[0032]
The material used as the support constituting the oversheet in the present invention will be described later. For example, when a material such as PC (polycarbonate) is alloyed with an amorphous polyester resin, the storage elastic modulus E ′ is determined by the mixing ratio. Since the temperature of (1.0E + 08) Pa is affected, it is important to adjust this mixing ratio.
[0033]
(B) (1.0E + 04Pa ≦ [storage modulus E ′ of oversheet at 180 ° C. E ′] ≦ 5.0E + 07Pa) is such that the oversheet constituting the information recording and displaying card of the present invention has excellent embossability. It is necessary to secure.
This embossing is not limited to the case where “embossed display” is formed on the integrated body composed of the over sheet and the core sheet by hot pressing. It is formed in a state where the boundary between it and the so-called cut is not so smooth, and at a predetermined height or depth, so that delamination due to cracks in the oversheet itself does not occur, and on the completed card itself It is necessary that deformation such as remarkable warpage does not occur, and the embossability has a meaning including all of these states.
The value of the condition (B) is calculated as follows. The sample is cut into a plate, and a test is performed by a tension method using a “viscoelastic spectrometer” manufactured by Iwamoto Seisakusho. The dynamic viscoelasticity is measured in the range of 0 to 200 ° C. in increments of 3 ° C. at a frequency of 1 Hz, and the real term is calculated as storage elastic modulus (E ′). At this time, the storage elastic modulus E ′ at 180 ° C. Is read from the data.
Since embossing is usually performed at 180 ° C. or higher, it is necessary for the oversheet to be somewhat flexible at 180 ° C.
According to the examination results based on experiments performed by the present inventors, sufficient embossing can be performed when the storage elastic modulus E ′ at 180 ° C. is 1.0E + 04 Pa or more and 5.0E + 07 Pa or less as an oversheet. It was confirmed.
[0034]
As described above, the fact that a credit card, a cash card, and the like have an inscription "embossed display" formed by embossing is as important as practical requirements now.
Regarding the embossability, each of the oversheet, the core sheet, and the information recording / display card, which is an integral part of the oversheet and the core sheet, has an influence on the possibility of the embossability. In the present invention, the oversheet having a strict requirement to be provided has been particularly focused on, and the conditions have been reached.
Whether or not embossing can be performed, `` softness '' in the processing temperature range of the oversheet is an important factor, and in the present invention, the `` softness '' is represented by the storage elastic modulus of the oversheet, It is necessary to use an oversheet having a storage elastic modulus at 180 ° C. of 5.0E + 07 Pa or less and 1.0E + 04 Pa or more. If this condition is satisfied, embossing can be performed advantageously.
If the storage elastic modulus at 180 ° C. exceeds 5.0E + 07 Pa, the embossing may cause delamination due to cracking of the oversheet itself or cause warping of the completed card. It is easy to become something that does not match the processing conditions.
On the other hand, if the storage elastic modulus E ′ at 180 ° C. is less than 1.0E + 04 Pa, it is not preferable because film formation failure occurs during film formation and the film shape is impaired.
When a barrier layer is provided on a support as described later, care must be taken since the material and thickness of the barrier layer affect the storage elastic modulus.
[0035]
The oversheet used in the present invention is a reversible thermosensitive recording material having at least a reversible thermosensitive recording layer on a support, and the reversible thermosensitive recording layer contains an electron-donating color-forming compound and an electron-accepting compound. Depending on the difference in heating temperature and / or cooling rate after heating, a relatively colored state and a decolored state can be formed.
As for the material constituting the reversible thermosensitive recording layer, and the provision of another layer as necessary, such as providing a protective layer on the reversible thermosensitive recording layer, a known reversible thermosensitive recording material is used. Applicable.
[0036]
With respect to this oversheet, a support that is considered to have the greatest effect on the embossability and repetition durability of the subject of the present invention will be described in detail, and other technical matters will be described later.
[0037]
As a support material used for the oversheet of the present invention, in addition to embossability and repetition durability, an amorphous polyester resin is used in consideration of integration with the core sheet (adhesion or heat fusion). The resin composition is used, and specifically, in addition to the one containing one kind of amorphous polyester resin composition, for example, a polymer alloy resin composition of a plurality of amorphous polyester resins and an amorphous polyester resin And a polymer alloy resin composition of polycarbonate resin and the like.
Here, the amorphous polyester resin in the present invention is obtained from a dehydration condensate of an aromatic dicarboxylic acid component and a diol component, and is used for practical purposes such as press fusion in card production. A material that does not cause actual harm such as clouding or poor fusion due to crystallization even if it is processed. It also includes, for example, PBT (polybutylene terephthalate) before crystallization, in addition to those having low crystallinity in molecular structure. Broadly means.
[0038]
Representative examples of the aromatic dicarboxylic acid component that is preferably used as a raw material of the amorphous polyester resin include terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. It may be substituted with an acid.
Other dicarboxylic acid components include oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, neopentylic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid, p-oxybenzoic acid, and the like. In addition, these other dicarboxylic acid components may be one kind or a mixture of two or more kinds, and the amount of the other dicarboxylic acid to be substituted can be appropriately selected.
[0039]
Typical examples of the diol component preferably used as a raw material of the amorphous polyester resin include ethylene glycol, diethylene glycol, triethylene glycol, cyclohexane dimethanol, and the like. May be substituted.
Other diol components include propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, neopentyl glycol, polyalkylene glycol, 1,4-cyclohexanedimethanol, glycerin, pentaerythritol, trimethylol, and methoxypoly. Alkylene glycol and the like can be mentioned.
These other diol components may be one kind or a mixture of two or more kinds, and the amount of the other diol to be substituted can be appropriately selected.
[0040]
In addition, among the amorphous polyester resins used in the present invention, polyethylene terephthalate formed by condensation polymerization of terephthalic acid and ethylene glycol is preferable from the viewpoint of cost. Use of a copolymerized polyester containing a dicarboxylic acid component and / or a diol component other than ethylene glycol is also effective for achieving the object of the present invention.
As the copolymerized polyester, terephthalic acid accounts for 60% by mole or more of the dicarboxylic acid component, and a dicarboxylic acid component in which the remaining dicarboxylic acid component is replaced by another dicarboxylic acid component; and 60% by mole or more of the diol component includes ethylene glycol. And a copolymerized polyester obtained by subjecting the remaining diol component to condensation polymerization with a diol component substituted by another diol component.
[0041]
Further, as the aromatic polyester resin that can be used in the present invention, a mixture of polyethylene terephthalate and the above-mentioned copolymerized polyester may be used. However, when using a copolymerized polyester, care must be taken because the change in the glass transition temperature or the tensile modulus of the sheet is large depending on the selection and the content of the copolymerized component.
In the case of such a mixture, a copolymer polyester which can be particularly preferably used is a substantially non-copolyester prepared by replacing about 30 mol% of ethylene glycol in polyethylene terephthalate with 1,4-cyclohexanedimethanol. A crystalline aromatic polyester resin is preferable, and for example, one having a trade name of “PETG” manufactured by Eastman Chemical Company can be used.
[0042]
In the polymer alloy resin composition of the amorphous polyester resin and the polycarbonate resin, the polycarbonate resin broadly means a polymer having a carbonate bond (—O—CO—O—) in a main chain.
Polycarbonate resins include those produced from bisphenol A synthesized from phenol and acetone by an interfacial polymerization method, transesterification method, pyridine method, and the like, and bisphenol A and dicarboxylic acid derivatives (for example, tere (iso) phthalic acid dichloride, etc.). ), And those obtained by polymerization of a derivative of bisphenol A (eg, tetramethylbisphenol A or the like).
[0043]
Further, as the support for the oversheet of the present invention, not a single-layer film, if the function required of the support is achieved, for example, an amorphous polyester resin film and other types of different films May be a laminate of two or more layers.
For example, as a laminate having a multilayer structure having an inner layer on the side on which the reversible thermosensitive recording layer is provided and an outer layer on the side to be thermally pressed with the core sheet, the melting temperature of the resin constituting the outer layer is such that the melting temperature of the resin constituting the inner layer is higher. The configuration in which the temperature is lower than the temperature is effective for improving the heat resistance of the card without impairing the low-temperature fusion property.
For example, the outer layer is made of a polyester resin, and the inner layer is made of a two-layer sheet of a polymer alloy resin composition comprising an amorphous polyester resin and a polycarbonate resin. And embossability is excellent.
[0044]
Further, if necessary, a support film containing additives such as a coloring agent, a lubricant, a filler, and an impact modifier can be used. In particular, a support film blended with a plate-like filler such as talc or a polymer having a low tensile strength such as polybutylene terephthalate can be preferably used because the embossability is improved.
[0045]
The thickness of the support constituting the oversheet depends on the thickness of the information recording / display card to be produced, but is generally preferably 50 μm to 250 μm, and more preferably 75 μm to 200 μm.
[0046]
Next, the core sheet used in the present invention will be described.
The core sheet used in the present invention means a sheet used to form an information recording and display card by attaching an oversheet to a surface and integrating the oversheet. Usually, a rectangular plate-like and resinous material is often used, and a plurality of such materials may be used as needed.
The core sheet includes a sheet in which an information storage unit is arranged. In the case of a magnetic information storage unit, there are a sheet attached or embedded in one resin sheet. In the case of an IC chip, an antenna coil, or the like, a thick resin sheet may be inserted into a thick resin sheet with a gap or may be inserted between a plurality of resin sheets.
For a core sheet on which such an information storage unit is arranged, arranging a magnetic tape or the like or positioning with an IC chip or the like is a complicated and time-consuming operation. The technology used is applicable.
The thickness of the core sheet is preferably from 50 μm to 5 mm, and more preferably from 200 μm to 600 μm.
[0047]
The material constituting the core sheet is preferably a thermoplastic resin sheet that is deformed by heating and pressing, and it is important that the core sheet has a fusibility with the support film of the oversheet by heating and pressing. Yes, as a core sheet used to have a high adhesive force with the oversheet, at least the surface layer material in contact with the oversheet, it is preferable to use the same type of resin as the oversheet, for example, amorphous It can be produced by using polyester resins or polycarbonates.
As the thermoplastic resin, amorphous polyester resin, polycarbonate resin, polycarbonate resin / amorphous polyester resin alloy can be preferably used, but not limited thereto, polyolefin resin, crystalline polyester resin, acrylic resin General-purpose resins such as resin, ABS resin, AS resin, and biodegradable resin can be used.
Also, engineering plastics having good heat resistance can be used as the material of the core sheet. Examples of the engineering plastic include polyphenylene sulfide, polyetherimide, polyimide, and polyetheretherketone, and a film or sheet containing one or more of these as a main component is preferably used.
[0048]
Further, in order to provide not only adhesiveness but also a plurality of functions such as heat resistance, it is preferable that the core sheet has two or more layers. In this case, a core sheet composed of two or more layers may be prepared in advance, and the core sheet may be overlaid with the oversheet and then pressed. Alternatively, a plurality of core sheets may be prepared and fused with the oversheet during hot pressing. Can be worn.
Examples of a core sheet having a three-layer structure include amorphous polyester resin / polycarbonate resin / amorphous polyester resin or amorphous polyester resin / polycarbonate resin / amorphous polyester resin alloy / amorphous Polyester resin can be used, and the amorphous polyester resin in the outer layer can have adhesiveness at low temperature, and the middle layer polycarbonate resin or polycarbonate resin / amorphous polyester resin alloy can have heat resistance.
Here, the amorphous polyester resin used for the outer layer is an amorphous polyester resin alone or an alloy mainly composed of the amorphous polyester resin, and the middle layer polycarbonate resin is a polycarbonate resin alone or polycarbonate. An alloy containing a resin as a main component means each of them. The thickness of the outer layer and the middle layer can be freely set according to the intended use.
[0049]
The core sheet may be transparent, translucent, or opaque, may be colored white or chromatic, and is preferably appropriately designed according to the intended use.
When a translucent film or an opaque film is used, an inorganic pigment or an organic pigment can be blended in the resin. In the case of forming a transparent film, an amount of the pigment which does not impair the transparency can be blended.
In the core sheet, various additives such as a plasticizer and an antistatic agent can be blended in addition to the pigment.
Further, the surface of the core sheet is preferably subjected to embossing or the like for deaeration of the joining process.
[0050]
The method for producing the support and the film for the core sheet constituting the oversheet in the present invention is not particularly limited, and a known method can be applied.
When both are a single layer, an extrusion method using a T-die is used for the resin composition, and when one or both layers are a multilayer, a co-extrusion method in which the resin composition of each layer is co-extruded and laminated, or A method of forming each layer in a sheet shape and laminating the same is used, but a method of laminating by a co-extrusion method is preferable in consideration of productivity and cost.
Specifically, in the case of a single layer, the resin composition is blended or, if necessary, formed into a pellet, and is charged into a hopper of a T-die extruder. Then, it is melted and extruded at a temperature in the range of 200 ° C. to 280 ° C. and solidified by cooling with a cooling roll or the like to form a sheet.
In the case of a multi-layer, the resin compositions of the respective layers are individually compounded or, if necessary, formed into pellets, and each is charged into each hopper of a T-die extruder to which a plurality of T dies are connected, and the temperature is 200 ° C. It is melted in the range of 280 ° C., co-extruded, and quenched and solidified by a cooling roll or the like to form a laminated sheet.
[0051]
It is preferable to use the same type of resin as a material of at least a surface layer portion where both the oversheet and the core sheet are in contact with each other in order to give a high adhesive strength to a product obtained by laminating (pressing and laminating) the oversheet and the core sheet.
The thicknesses of the oversheet and the core sheet are selected in consideration of the thickness of the card to be manufactured.
For example, when manufacturing a card having a thickness of 760 μm specified by JIS X 6301, an oversheet having a thickness of 50 to 250 μm and a core sheet having a thickness of 50 to 700 μm can be used in combination so as to have a predetermined card thickness.
In addition, a plurality of core sheets may be used to obtain a predetermined thickness. Further, when an IC chip or an antenna is embedded in a card like a non-contact IC card, the core sheet thickness can be selected in consideration of the size of the IC chip or the antenna.
In this case, it is preferable to use an oversheet having a thickness of 50 to 200 μm and a core sheet having a thickness of 50 to 400 μm. In particular, it is preferable to combine two 280 μm core sheets with a 100 μm oversheet.
[0052]
A method of manufacturing the information recording and displaying card of the present invention by attaching the oversheet to the core sheet as described above will be described.
In the present invention, the term "pasting" means to be integrated, and it can be bonded by an adhesive or can be heat-pressed and heat-sealed.
FIG. 1 is a conceptual diagram showing a state in which an information recording display card is manufactured by heating and pressing an oversheet and a core sheet, and shows an example in which two core sheets and an outer layer sheet are used.
The oversheet (10) has a support (1) on which a barrier layer (2), a reversible recording layer (3), and a protective layer (4) are sequentially provided.
After arranging the two core sheets (5) so as to be sandwiched between the oversheet (10) and the outer layer sheet (6), the surface side of the protective layer (4) of the oversheet (10) and the outer layer sheet (6). The front side is further sandwiched by a pressing plate and the like, and is heated and pressed to perform heat fusion.
In this example, both the outer layer sheet and the two core sheets are integrated and become a part of the information recording and displaying card. However, the information recording and displaying card of the present invention is limited to such a configuration. Not something.
For example, in FIG. 1, a sheet (referred to as an inlet sheet) in which a non-contact type IC chip provided with an antenna coil is further interposed between two core sheets (5), and the outer layer sheet (6) is Using the magnetic stripe layer to which the magnetic stripe layer has been temporarily transferred, heating and pressing can be performed in the same manner as described above to form an IC card laminate in which IC chips are arranged.
The integrated material thus formed is punched into a card shape of a predetermined size using a punching blade or the like, and an information recording / display card is manufactured.
The heating and pressurizing method includes a pressing method and a laminating method. However, the heating and pressurizing method can be selectively used depending on the material of the sheet to be used and is not limited.
That is, a large-sized core sheet is prepared, an oversheet having a predetermined area is arranged on the core sheet, and the sheet can be heated and pressed, or the tape-shaped core sheet and the oversheet are rolled, and both are united. Heating and pressurization can also be performed, and the method for producing the information recording and displaying card is not limited.
[0053]
The outer layer sheet is not particularly limited as long as it has a property of fusing with the core sheet by heating and pressing, but a sheet having a thickness smaller than that of the core sheet is usually used, and a support constituting the oversheet is also used. The material may be selected from the materials, and the same material as the support material constituting the oversheet can be used.
When an information recording card without a conventional reversible thermosensitive recording layer is manufactured by heat fusion, it is common to use an outer layer sheet, and in the present invention, it is selected from the outer layer sheet. Can also be used.
The terms `` oversheet '' and `` core sheet '' in the present invention refer to the respective positions of the state in which the outer sheet is used and the core sheet is interposed and sandwiched between the oversheet and the outer sheet. The outer layer sheet can be omitted in the information recording and displaying card of the present invention by a construction method, and the information recording and displaying card of the present invention includes a card in which the outer layer sheet is omitted.
[0054]
Next, the heating and pressurizing process will be described.
If the temperature at the time of heating and pressing (referred to as press temperature) exceeds the melting point of the color developer, background fogging will occur.
On the other hand, if the pressure at the time of heating and pressurizing (pressing pressure) is too high, there is a problem that the matte tone on the card surface is reduced and a glossy feeling is generated, or the surface layer is broken and a stick is generated.
For this reason, the maximum press temperature for forming a card without impairing the special property of “reversible heat sensitivity” is preferably 160 ° C. or lower, more preferably 150 ° C. or lower, and particularly preferably 140 ° C. or lower. When pressed at a temperature exceeding the melting point of the developer or a temperature exceeding 160 ° C., the background is liable to cause a background fogging or yellowing due to the developer and the dye.
On the other hand, the minimum press temperature is preferably 100 ° C. or higher, and particularly preferably 120 ° C. or higher. If the temperature is lower than 100 ° C., there is a tendency that fusion is insufficient and a problem of peeling occurs.
Press upper limit pressure is 40kg / cm ² Or less, especially 30 kg / cm ² The following is preferred. 40kg / cm ² If it exceeds 2,000, the problem that the base material and the IC chip are destroyed occurs.
On the other hand, the minimum press pressure is 5 kg / cm ² Or more, especially 10 kg / cm ² The above is preferable. 5kg / cm ² If it is less than the above range, the problem of peeling due to insufficient pressure bonding is likely to occur.
The heating and pressing time is preferably 5 to 20 minutes.
[0055]
When manufacturing an information recording and display card having "embossed display" by embossing, the features of the present invention can be utilized as follows.
That is, since the oversheet of the present invention can be embossed, when combined with an embossable core sheet, the advantage that the core sheet and the oversheet having the same size can be used. There is.
That is, an information recording and display card in which an oversheet is stuck on the entire surface of the core sheet is produced. However, since the information recording and display card can be embossed from above the oversheet, the original of the oversheet is formed. The degree of freedom in selecting the size and position of each of the image display unit exhibiting the above function and the "embossed display" by embossing is large, and this advantage cannot be expected from a conventional information recording / display card.
[0056]
The oversheet to be pasted can be made smaller, without having to match the area of the core sheet. In this case, it is necessary to prepare different sizes and to attach the oversheet to a predetermined position on the core sheet. As in the case of manufacturing a card, it has a disadvantage in terms of production efficiency.
However, even for such an information recording display card having a small area of the oversheet, as long as the image display function is not hindered, it is possible to perform embossing without avoiding the oversheet or even over the oversheet. This is an excellent advantage not found in conventional products in terms of the function and production of the information recording / display card itself.
Of course, as the information recording display card of the present invention, as in the case of the conventional product, an oversheet is pasted at a specific position, and a card embossed so as to avoid the oversheet portion is included. It is superior to conventional products in that it has durability.
[0057]
The reversible thermosensitive recording material which is the oversheet of the present invention can form a relatively colored state and a decolored state depending on a heating temperature and / or a cooling rate after heating. The basic coloring / decoloring phenomenon of the composition comprising the color former and the developer used in the present invention will be described.
[0058]
FIG. 2 shows the relationship between the color density and the temperature of the recording medium. When the temperature of the recording medium in the decolored state (A) is raised at first, the melting temperature T ₁ , And a color is formed (B). When the color is rapidly cooled from the molten color developing state (B), the temperature can be lowered to room temperature while maintaining the color developing state, and the solid color developing state (C) is obtained. Whether or not this color-developed state is obtained depends on the rate of temperature decrease from the molten state. In the case of slow cooling, decoloration occurs in the course of temperature decrease, and the same decolored state (A) as in the beginning or a rapidly-cooled colored state ( A state having a relatively lower concentration than that of C) is formed.
On the other hand, when the temperature is raised again in the quenching color developing state (C), the temperature T lower than the coloring temperature becomes lower ₂ Then, the color is erased (from D to E), and when the temperature is lowered from this point, the color returns to the same erased state (A) as at the beginning. The actual color forming temperature and color erasing temperature can be selected according to the purpose because they vary depending on the combination of the color developer and the color developing agent used. Further, the density in the molten color development state and the color development density after quenching are not always the same, and may differ.
[0059]
In the reversible thermosensitive recording material which is the oversheet of the present invention, the color-developed state (C) obtained by quenching from the molten state is a state in which the developer and the color-developing agent are mixed in a state where molecules can contact and react with each other. , Which often form a solid state. This state is a state in which the color developer and the color former are aggregated to maintain the color development, and it is considered that the color formation is stabilized by the formation of this aggregated structure.
On the other hand, the decolored state is a state where both are phase-separated. This state is a state in which the molecules of at least one compound are aggregated to form a domain or crystallized, and it is considered that the color former and the developer are separated and stabilized by aggregation or crystallization. Can be In many cases, the present invention causes more complete decoloration due to phase separation of the two and crystallization of the color developer. In both the decoloring from the molten state by slow cooling and the decoloring by heating from the colored state shown in FIG. 2, the cohesive structure changes at this temperature, and phase separation and crystallization of the developer occur.
[0060]
In order to form a color-developed image on the reversible thermosensitive recording material which is the oversheet of the present invention, the material may be heated to a temperature at which it is melted and mixed once by a thermal head and then rapidly cooled. The decoloring is a method of gradually cooling from a heating state and a method of heating to a temperature slightly lower than a color development temperature. However, they are the same in the sense that they both phase-separate or temporarily hold at a temperature at which at least one crystallizes. The rapid cooling in the formation of the color-developed state is performed so as not to maintain the phase separation temperature or the crystallization temperature. Here, the rapid cooling and the slow cooling are relative to one composition, and the boundary varies depending on the combination of the color former and the developer.
[0061]
Next, the technical contents of the reversible thermosensitive recording material as an oversheet used in the present invention other than the support will be described.
[0062]
The reversible thermosensitive recording layer can be provided directly on the support, but the solvent that constitutes the coating liquid for forming the reversible recording layer causes the support to dissolve and deform, shrink, or reduce the strength. In some cases, the function of the oversheet may be impaired. In such a case, it is preferable to first provide a barrier layer on the support and then form a reversible thermosensitive recording layer thereon.
As a method of forming a barrier layer, there are a method of applying a material having excellent solvent resistance and a method of laminating a film having excellent solvent resistance.
[0063]
1. Method to apply material with excellent solvent resistance
The barrier layer is preferably formed from a material having resistance to the solvent of the coating liquid for forming the reversible thermosensitive recording layer.
In consideration of processability, a resin that can be dissolved or dispersed in an alcohol solvent, water, or the like is more preferable. Further, it is more preferable that when cured by heat, light, or the like, the barrier property against an organic solvent is increased.
Specifically, polyamide resin, polyvinyl alcohol resin, alcohol-soluble phenol resin, polyester resin, acrylic resin and the like are preferable.
[0064]
In addition, it is mainly composed of a thermosetting resin such as a polyurethane resin and an epoxy resin formed by crosslinking an isocyanate with an acrylic polyol, a polyester polyol, or the like, or an oligomer such as a urethane acrylate or an epoxy acrylate. An ultraviolet curable resin or an electron beam curable resin in which additives and the like are appropriately mixed may be used.
These may be in a solution state dissolved in water or an alcohol-based solvent, or may be in a dispersed state.
The thickness of the barrier layer formed by this method is preferably in the range of 0.1 to 10 μm.
[0065]
2. Laminating film with excellent solvent resistance
For imparting solvent resistance to the barrier layer, a crystallization-treated polyester film can be used. As the crystallization treatment, there is a method of stretching at the time of film formation or a method of forming an amorphous polyester into a film and then performing a heat treatment to crystallize the film. Usually, the former stretched polyester film is generally used, and specific examples include a stretched PET film and a stretched PEN film.
It is preferable that an adhesive layer is applied or surface treatment such as corona discharge is performed on the front and back surfaces of the crystallized polyester film in order to improve the adhesion to the support and the recording layer.
[0066]
The barrier layer obtained by the above method has a high solvent resistance and a large tensile strength in many cases, so if the thickness is large, the barrier layer is affected by the tensile strength and the embossability is reduced. Although it depends on the material of the layer, the thickness is preferably in the range of 1.0 to 8 μm.
For example, when a stretched PET film is laminated on a support using an amorphous polyester sheet having a thickness of 100 μm, the storage elastic modulus at 180 ° C. of the stretched PET film is larger than that of the amorphous polyester sheet. , The storage elastic modulus at 180 ° C. is 8.3E + 07 (8.3 × 10 ⁷ ) Pa, and embossing tends to cause problems.
On the other hand, when the thickness is 8 μm or 4.5 μm, 4.9E + 07 (4.9 × 10 ⁷ ) Pa, 2.4E + 07 (2.4 × 10 ⁷ ) Pa, and embossing can be easily and satisfactorily performed.
[0067]
Next, the recording layer of the reversible thermosensitive recording material will be described.
The thickness of the reversible thermosensitive recording layer is preferably in the range of 1 to 20 μm, more preferably 3 to 15 μm.
Further, leuco dyes (electron-donating color-forming compounds) to be contained in the recording layer are exemplified, but the present invention is not limited thereto. Further, leuco dyes can be used alone or in combination.
2-anilino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6-di (n-butylamino) fluoran, 2-anilino-3-methyl-6- (Nn-propyl- N-methylamino) fluoran, 2-anilino-3-methyl-6- (N-isopropyl-N-methylamino) fluoran, 2-anilino-3-methyl-6- (N-isobutyl-N-methylamino) fluoran 2-anilino-3-methyl-6- (Nn-amyl-N-methylamino) fluoran, 2-anilino-3-methyl-6- (N-sec-butyl-N-methylamino) fluoran, 2 -Anilino-3-methyl-6- (Nn-amyl-N-ethylamino) fluoran, 2-anilino-3-methyl-6- (N-iso-amyl-N-ethylamino) Ruoran, 2-anilino-3-methyl -6- (N-n- propyl -N- isopropylamino) fluoran, 2-anilino-3-methyl-6-(N-cyclohexyl--N- methylamino) fluoran,
[0068]
2-anilino-3-methyl-6- (N-ethyl-p-toluidino) fluoran, 2-anilino-3-methyl-6- (N-methyl-p-toluidino) fluoran, 2- (m-trichloromethylani (Lino) -3-methyl-6-diethylaminofluoran, 2- (m-trifluoromethylanilino) -3-methyl-6-diethylaminofluoran, 2- (m-trichloromethylanilino) -3-methyl- 6- (N-cyclohexyl-N-methylamino) fluoran, 2- (2,4-dimethylanilino) -3-methyl-6-diethylaminofluoran, 2- (N-ethyl-p-toluidino) -3- Methyl-6- (N-ethylanilino) fluoran, 2- (N-ethyl-p-toluidino) -3-methyl-6- (N-propyl-p-toluidino) fluora 2-anilino-6- (NN-hexyl-N-ethylamino) fluoran, 2- (o-chloroanilino) -6-diethylaminofluoran, 2- (o-chloroanilino) -6-dibutylaminofluoran, 2- (m-trifluoromethylanilino) -6-diethylaminofluoran, 2,3-dimethyl-6-dimethylaminofluoran,
[0069]
3-methyl-6- (N-ethyl-p-toluidino) fluoran, 2-chloro-6-diethylaminofluoran, 2-bromo-6-diethylaminofluoran, 2-chloro-6-dipropylaminofluoran, 3 -Chloro-6-cyclohexylaminofluoran, 3-bromo-6-cyclohexylaminofluoran, 2-chloro-6- (N-ethyl-N-isoamylamino) fluoran, 2-chloro-3-methyl-6-diethylamino Fluoran, 2-anilino-3-chloro-6-diethylaminofluoran, 2- (o-chloroanilino) -3-chloro-6-cyclohexylaminofluoran, 2- (m-trifluoromethylanilino) -3- Chloro-6-diethylaminofluoran, 2- (2,3-dichloroanilino) -3-chloro-6-die L-aminofluorane, 1,2-benzo-6-diethylaminofluoran, 3-diethylamino-6- (m-trifluoromethylanilino) fluoran, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -7- Azaphthalide, 3- (1-octyl-2-methylindol-3-yl) -3- (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindole-3- Yl) -3- (2-methyl-4-diethylaminophenyl) -4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) 3- (2-methyl-4-diethylaminophenyl) -7-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl) -3- (4-diethylaminophenyl) -4-azaphthalide, 3- ( 1-ethyl-2-methylindol-3-yl) -3- (4-Nn-amyl-N-methylaminophenyl) -4-azaphthalide, 3- (1-methyl-2-methylindole-3- Yl) -3- (2-hexyloxy-4-diethylaminophenyl) -4-azaphthalide, 3,3-bis (2-ethoxy-4-diethylaminophenyl) -4-azaphthalide, 3,3-bis (2-ethoxy) -4-diethylaminophenyl) -7-azaphthalide.
[0070]
As the color former used in the present invention, in addition to the above-mentioned fluoran compound and azaphthalide compound, conventionally known leuco dyes can be used alone or in combination. The coloring agent is shown below.
2- (p-acetylanilino) -6- (Nn-amyl-Nn-butylamino) fluoran, 2-benzylamino-6- (N-ethyl-p-toluidino) fluoran, 2-benzylamino -6- (N-methyl-2,4-dimethylanilino) fluoran, 2-benzylamino-6- (N-ethyl-2,4-dimethylanilino) fluoran, 2-benzylamino-6- (N- Methyl-p-toluidino) fluoran, 2-benzylamino-6- (N-ethyl-p-toluidino) fluoran, 2- (di-p-methylbenzylamino) -6- (N-ethyl-p-toluidino) fluoran , 2- (α-phenylethylamino) -6- (N-ethyl-p-toluidino) fluoran, 2-methylamino-6- (N-methylanilino) fluoran, 2-methyl Mino-6-(N-ethylanilino) fluoran, 2-methylamino-6-(N-propyl anilino) fluoran,
[0071]
2-ethylamino-6- (N-methyl-p-toluidino) fluoran, 2-methylamino-6- (N-methyl-2,4-dimethylanilino) fluoran, 2-ethylamino-6- (N- Ethyl-2,4-dimethylanilino) fluoran, 2-dimethylamino-6- (N-methylanilino) fluoran, 2-dimethylamino-6- (N-ethylanilino) fluoran, 2-diethylamino-6- (N-methyl -P-toluidino) fluoran, 2-diethylamino-6- (N-ethyl-p-toluidino) fluoran, 2-dipropylamino-6- (N-methylanilino) fluoran, 2-dipropylamino-6- (N- Ethylanilino) fluoran, 2-amino-6- (N-methylanilino) fluoran, 2-amino-6- (N-ethylanilino Fluoran, 2-amino-6- (N-propylanilino) fluoran, 2-amino-6- (N-methyl-p-toluidino) fluoran, 2-amino-6- (N-ethyl-p-toluidino) fluoran , 2-amino-6- (N-propyl-p-toluidino) fluoran, 2-amino-6- (N-methyl-p-ethylanilino) fluoran, 2-amino-6- (N-ethyl-p-ethylanilino) Fluoran, 2-amino-6- (N-propyl-p-ethylanilino) fluoran, 2-amino-6- (N-methyl-2,4-dimethylanilino) fluoran, 2-amino-6- (N-ethyl -2,4-dimethylanilino) fluoran, 2-amino-6- (N-propyl-2,4-dimethylanilino) fluoran, 2-amino-6- (N-methyl- -Chloroanilino) fluoran, 2-amino-6- (N-ethyl-p-chloroanilino) fluoran, 2-amino-6- (N-propyl-p-chloroanilino) fluoran, 1,2-benzo-6- (N- Ethyl-N-isoamylamino) fluoran, 1,2-benzo-6-dibutylaminofluoran, 1,2-benzo-6- (N-methyl-N-cyclohexylamino) fluoran, 1,2-benzo-6 (N-ethyl-N-toluidino) fluoran and others.
[0072]
Specific examples of other color formers preferably used in the present invention are as follows.
2-anilino-3-methyl-6- (N-2-ethoxypropyl-N-ethylamino) fluoran, 2- (p-chloroanilino) -6- (Nn-octylamino) fluoran, 2- (p- Chloroanilino) -6- (Nn-palmitylamino) fluoran, 2- (p-chloroanilino) -6- (di-n-octylamino) fluoran, 2-benzoylamino-6- (N-ethyl-p- Toluidino) fluoran, 2- (o-methoxybenzoylamino) -6- (N-methyl-p-toluidino) fluoran, 2-dibenzylamino-4-methyl-6-diethylaminofluoran, 2-dibenzylamino-4 -Methoxy-6- (N-methyl-p-toluidino) fluoran, 2-dibenzylamino-4-methyl-6- (N-ethyl-p-toluidino) Luoran, 2- (α-phenylethylamino) -4-methyl-6-diethylaminofluoran, 2- (p-toluidino) -3- (t-butyl) -6- (N-methyl-p-toluidino) fluoran , 2- (o-methoxycarbonylamino) -6-diethylaminofluoran, 2-acetylamino-6- (N-methyl-p-toluidino) fluoran, 4-methoxy-6- (N-ethyl-p-toluidino) Fluorane, 2-ethoxyethylamino-3-chloro-6-dibutylaminofluoran, 2-dibenzylamino-4-chloro-6- (N-ethyl-p-toluidino) fluoran, 2- (α-phenylethylamino ) -4-Chloro-6-diethylaminofluoran, 2- (N-benzyl-p-trifluoromethylanilino) -4-chloro-6-die L-aminofluorane, 2-anilino-3-methyl-6-pyrrolidinofluoran, 2-anilino-3-chloro-6-pyrrolidinofluoran, 2-anilino-3-methyl-6- (N-ethyl- N-tetrahydrofurfurylamino) fluoran, 2-mesidino-4 ′, 5′-benzo-6-diethylaminofluoran, 2- (m-trifluoromethylanilino) -3-methyl-6-pyrrolidinofluoran, 2- (α-naphthylamino) -3,4benzo-4′-bromo-6- (N-benzyl-N-cyclohexylamino) fluoran, 2-piperidino-6-diethylaminofluoran, 2- (Nn- Propyl-p-trifluoromethylanilino) -6-morpholinofluoran, 2- (di-Np-chlorophenyl-methylamino) -6-pyrrolidinofluora 2- (Nn-propyl-m-trifluoromethylanilino) -6-morpholinofluoran, 1,2-benzo-6- (N-ethyl-NNn-octylamino) fluoran, 1 , 2-benzo-6-diallylaminofluoran, 1,2-benzo-6- (N-ethoxyethyl-N-ethylamino) fluoran,
[0073]
Benzoleucomethylene blue, 2- [3,6-bis (diethylamino) -7- (o-chloroanilino) xanthyl] benzoic acid lactam, 2- [3,6-diethylamino) -9- (o-chloroanilino) xanthyl] benzoic acid Lactam, 3,3-bis (p-dimethylaminophenyl) -phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also known as crystal violet lactone), 3,3-bis- ( p-dimethylaminophenyl) -6-diethylaminophthalide, 3,3-bis- (p-dimethylaminophenyl) -6-chlorophthalide, 3,3-bis- (p-dibutylaminophenyl) phthalide, 3- (2 -Methoxy-4-dimethylaminophenyl) -3- (2-hydroxy-4,5-dichlorophenyl) Talide, 3- (2-hydroxy-4-dimethylaminophenyl) -3- (2-methoxy-5-chlorophenyl) phthalide, 3- (2-hydroxy-4-dimethoxyaminophenyl) -3- (2-methoxy- 5- (chlorophenyl) phthalide, 3- (2-hydroxy-4-dimethylaminophenyl) -3- (2-methoxy-5-nitrophenyl) phthalide, 3- (2-hydroxy-4-diethylaminophenyl) -3- ( 2-methoxy-5-methylphenyl) phthalide, 3- (2-methoxy-4-dimethylaminophenyl) -3- (2-hydroxy-4-chloro-5-methoxyphenyl) phthalide, 3,6-bis (dimethyl Amino) fluorenespiro (9,3 ′)-6′-dimethylaminophthalide, 6′-chloro-8′-methoxy-benzoindolino Spiropyran, 6'-bromo-2'-methoxy - benzoin Dori Bruno - spiropyran, Other.
[0074]
Next, the developer (electron-accepting compound) used in combination with the color former will be described.
The developer is disclosed in Japanese Patent Application Laid-Open No. 5-124360, cited as Patent Document 3, together with typical examples of an organic phosphoric acid compound, an aliphatic carboxylic acid compound or a phenol compound having a long-chain aliphatic hydrocarbon group. As described above, a compound having both a structure having a color developing ability capable of forming a color developing agent in a molecule and a structure controlling a cohesive force between molecules is used. As the structure having color developing ability, acidic groups such as a phenolic hydroxyl group, a carboxyl group, and a phosphoric acid group are used, but not limited thereto, and a group capable of coloring a coloring agent such as a thiourea group or a metal carboxylate group. I just need to bring it.
[0075]
Representative examples of the structure that controls the cohesion between molecules include hydrocarbon groups such as long-chain alkyl groups. It is preferable that the number of carbon atoms of the hydrocarbon group is 8 or more in order to obtain good color-developing and decoloring characteristics. The hydrocarbon group may contain an unsaturated bond, and also includes a branched hydrocarbon group. Also in this case, the main chain portion preferably has 8 or more carbon atoms. As described above, the color developer has a structure in which a structure having a color developing ability and a structure such as a hydrocarbon group that controls cohesion between molecules are connected. A divalent group containing a hetero atom, or a combination of a plurality of these groups may be bonded to the linking portion.
[0076]
Hereinafter, the color developer used in the present invention will be specifically exemplified. The developers may be used alone or in combination of two or more.
[0077]
Embedded image

Where X ₁ Represents a divalent group containing a hetero atom or a direct bond, and X ₂ Represents a divalent group containing a hetero atom. R ₁ Represents a divalent hydrocarbon group; ₂ Represents a hydrocarbon group having 1 to 22 carbon atoms. P represents an integer of 0 to 4, and R is repeated when p is 2 to 4. ₁ And X ₂ May be the same or different. Q represents 1 to 3.
Specifically, R ₁ And R ₂ Represents a hydrocarbon group which may have a substituent, and may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, or may be a hydrocarbon group composed of both of them. Further, the aliphatic hydrocarbon group may be linear or branched, and may have an unsaturated bond. Examples of the substituent attached to the hydrocarbon group include a hydroxyl group, a halogen, and an alkoxy group. Note that R ₁ May be a direct bond.
Also R ₁ And R ₂ If the total number of carbon atoms is 7 or less, the stability of color development and the decoloring property decrease, so the number of carbon atoms is preferably 8 or more, and more preferably 11 or more. X ₁ And X ₂ Represents a divalent group containing a hetero atom,
[0078]
[Table 1]

Preferably, it represents a divalent group having at least one group shown in Table 1. Specific examples include the following.
[0079]
[Table 2]

[0080]
Specific examples of the phenol compound in the present invention will be given below, but the present invention is not limited to these. Further, phenol compounds can be used alone or in combination.
[0081]
[Table 3]

[0082]
Examples of the organic phosphoric acid developer include the following compounds. Dodecylphosphonic acid, tetradecylphosphonic acid, hexadecylphosphonic acid, octadecylphosphonic acid, eicosylphosphonic acid, docosylphosphonic acid, tetracosylphosphonic acid, ditetradecyl phosphate, dihexadecyl phosphate, phosphoric acid Dioctadecyl ester, dieicosyl phosphate, dibehenyl phosphate, and the like.
The following compounds can be exemplified as the aliphatic carboxylic compound. 2-hydroxytetradecanoic acid, 2-hydroxyhexadecanoic acid, 2-hydroxyoctadecanoic acid, 2-hydroxyeicosanoic acid, 2-hydroxydocosanoic acid, 2-bromohexadecanoic acid, 2-bromooctadecanoic acid, 2-bromoeicosanoic acid 2-bromodocosanoic acid, 3-bromooctadecanoic acid, 3-bromodocosanoic acid, 2,3-dibromooctadecanoic acid, 2-fluorododecanoic acid, 2-fluorotetradecanoic acid, 2-fluorohexadecanoic acid, 2-fluorooctadecanoic acid, 2 -Fluoroeicosanoic acid, 2-fluorodocosanoic acid, 2-iodohexadecanoic acid, 2-iodooctadecanoic acid, 3-iodohexadecanoic acid, 3-iodooctadecanoic acid, perfluorooctadecanoic acid and the like.
[0083]
The following compounds can be exemplified as the aliphatic dicarboxylic acid and tricarboxylic acid compounds. 2-dodecyloxysuccinic acid, 2-tetradecyloxysuccinic acid, 2-hexadecyloxysuccinic acid, 2-octadecyloxysuccinic acid, 2-eicosyloxysuccinic acid, 2-dodecyloxysuccinic acid, 2-dotesylthiosuccinic acid 2-tetradecylthiosuccinic acid, 2-hexadecylthiosuccinic acid, 2-octadecylthiosuccinic acid, 2-eicosylthiosuccinic acid, 2-docosylthiosuccinic acid, 2-tetracosylthiosuccinic acid, 2-hexadecyldithiosuccinic acid, 2-octadecyldithiosuccinic acid, 2-eicosyldithiosuccinic acid, dodecylsuccinic acid, tetradecylsuccinic acid, pentadecylsuccinic acid, hexadecylsuccinic acid, octadecylsuccinic acid, eicosylsuccinic acid, docosylsuccinic acid, 2,3-dihexadecylsuccinic acid, 2 , 3-Diok Decyl succinic acid, 2-methyl-3-hexadecyl succinic acid, 2-methyl-3-octadecyl succinic acid, 2-octadecyl-3-hexadecyl succinic acid, hexadecylmalonic acid, octadecylmalonic acid, eicosylmalonic acid, docosylmalonic acid , Dihexadecylmalonic acid, dioctadecylmalonic acid, didocosylmalonic acid, methyloctadecylmalonic acid, 2-hexadecylglutaric acid, 2-octadecylglutaric acid, 2-eicosylglutaric acid, docosylglutaric acid, 2-pentadecyladipin Acid, 2-octadecyladipic acid, 2-eicosyladipic acid, 2-docosyladipic acid, 2-hexadecanoyloxypropane-1,2,3-tricarboxylic acid, 2-octadecanoyloxypropane-1,2 , 3-tricarboxylic acid and the like.
[0084]
The appropriate range of the ratio of the color former and the color developer varies depending on the combination of the compounds used, but the color developer is generally in the range of 0.1 to 20 with respect to the color former 1 in a molar ratio, and is preferably. It is in the range of 0.2 to 10. If the amount of the developer is smaller or larger than this range, the density of the color-developed state is reduced, which is problematic. Further, the proportion of the decoloring accelerator is preferably from 0.1% by weight to 300% by weight, more preferably from 3% by weight to 100% by weight, based on the developer. Further, the color former and the developer can be used by being encapsulated in microcapsules. The ratio of the color-forming component and the resin in the recording layer is preferably from 0.1 to 10 with respect to the color-forming component 1. When the ratio is less than this, the thermal strength of the recording layer is insufficient. Problem.
[0085]
The reversible thermosensitive recording layer constituting the reversible thermosensitive recording material used in the present invention usually contains a resin.
Specific examples of the resin contained in the reversible thermosensitive recording layer include, for example, an acrylic polyol resin, a polyester polyol resin, a polyurethane polyol resin, a phenoxy resin, a polyvinyl butyral resin, a cellulose acetate propionate, a cellulose acetate butyrate to react with a crosslinking agent. Examples of the resin include a resin having a group, and a resin obtained by copolymerizing a monomer having a group that reacts with a crosslinking agent with another monomer, but the present invention is not limited to these compounds.
Further, resins obtained by subjecting these resins to block copolymerization or graft copolymerization of a benzotriazole-based ultraviolet absorbing skeleton or a siloxane bonding skeleton may be used.
[0086]
In the reversible thermosensitive recording material which is the oversheet of the present invention, an additive for improving or controlling the coating characteristics and the coloring / decoloring characteristics of the reversible thermosensitive recording layer can be used as necessary. These additives include, for example, surfactants, conductive agents, fillers, antioxidants, light stabilizers, color stabilizers, and decolorization accelerators. Preferred examples of the decolorization accelerator include compounds having a divalent group containing a hetero atom and an alkyl chain having 8 or more carbon atoms, and compounds having an N, N'-2 substituent. Is not limited to these compounds.
[0087]
In the invention, the reversible thermosensitive recording layer may contain a curing agent.
The curing agent used here is selected from known isocyanate monomer modified products such as urethane modified product, allophanate modified product, isocyanurate modified product, buret modified product, carbodiimide modified product, and blocked isocyanate. Examples of the isocyanate monomer that forms the modified product include tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), naphthylene diisocyanate (NDI), and paraphenylene diisocyanate ( PPDI), tetramethylxylylene diisocyanate (TMXDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), lysine diisocyanate (LDI), isopropylidene bis (4-cyclohexyl isocyanate) (IPC ), Cyclohexyl diisocyanate (CHDI), tolidine diisocyanate (TODI), and the like. However, the present invention is not limited to these compounds.
[0088]
Further, the reversible thermosensitive recording layer may contain a crosslinking accelerator curing agent.
Examples of the crosslinking accelerator include tertiary amines such as 1,4-diaza-bicyclo [2,2,2] octane and metal compounds such as organic tin compounds. Also, the curing agent may or may not have undergone a crosslinking reaction in the entire amount added. That is, an unreacted curing agent may be present.
Since this type of crosslinking reaction proceeds over time, the presence of unreacted curing agent does not indicate that the crosslinking reaction has not progressed at all, but that unreacted curing agent is detected. This indicates that the presence of a resin in a cross-linked state. Further, as a method for distinguishing whether the polymer in the present invention is in a crosslinked state or in a non-crosslinked state, it can be distinguished by immersing a coating film in a highly soluble solvent.
That is, since the polymer in a non-crosslinked state dissolves in the solvent and does not remain in the solute, the presence or absence of the polymer structure of the solute may be analyzed. Therefore, if the presence of the polymer structure in the solute cannot be confirmed, the polymer is in a non-crosslinked state, and can be distinguished from a crosslinked polymer.
When other layers are stacked, the layer configuration and the film thickness are confirmed from cross-sectional photographs such as TEM (transmission electron microscope) and SEM (scanning electron microscope). Then, all the extraneous layers are removed to expose the target layer. Next, the layer is scraped off and the measurement is performed according to the above method.
[0089]
For the formation of the recording layer, a coating solution prepared by uniformly mixing and dispersing a mixture of the above-described developer, color former, various additives, a curing agent, a resin in a crosslinked state, and a coating solution solvent is used. .
Specific examples of the solvent used for preparing the coating liquid include water; alcohols such as methanol, ethanol, isopropanol, n-butanol, and methyl isocarbinol; acetone, 2-butanone, ethyl amyl ketone, diacetone alcohol, isophorone, Ketones such as cyclohexanone; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; ethers such as diethyl ether, isopropyl ether, tetrahydrofuran, 1,4-dioxane, 3,4-dihydro-2H-pyran Glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol and ethylene glycol dimethyl ether; 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxye Glycol ether acetates such as ruacetate; esters such as methyl acetate, ethyl acetate, isobutyl acetate, amyl acetate, ethyl lactate and ethylene carbonate; aromatic hydrocarbons such as benzene, toluene and xylene; hexane, heptane and iso- Aliphatic hydrocarbons such as octane and cyclohexane; halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, dichloropropane, and chlorobenzene; sulfoxides such as dimethyl sulfoxide; N-methyl-2-pyrrolidone; Examples thereof include pyrrolidones such as octyl-2-pyrrolidone.
[0090]
The coating liquid can be prepared using a known coating liquid dispersing apparatus such as a paint shaker, a ball mill, an attritor, a three-roll mill, a Keddy mill, a sand mill, a dyno mill, and a colloid mill. In addition, each material may be dispersed in a solvent using the above-mentioned coating liquid dispersion apparatus, or each material may be dispersed alone in the solvent and mixed. Further, it may be dissolved by heating and precipitated by rapid cooling or cooling.
[0091]
There is no particular limitation on the coating method for forming the recording layer. Blade coating, wire bar coating, spray coating, air knife coating, bead coating, curtain coating, gravure coating, kiss coating, reverse roll coating Known methods such as coating, dip coating, and die coating can be used.
[0092]
As for the method of drying and curing the recording layer, after applying and drying, a curing treatment is performed if necessary. The heat treatment may be performed at a relatively high temperature for a short time using a high-temperature bath or the like, or may be performed at a relatively low temperature for a long time. As a specific condition of the crosslinking reaction, it is preferable to heat at a temperature of about 30 ° C. to 130 ° C. for about 1 minute to 150 hours from the viewpoint of reactivity. It is more preferable to heat at a temperature of 40 ° C. to 100 ° C. for about 2 minutes to 120 hours. In addition, since productivity is emphasized in production, it is difficult to take time until crosslinking is sufficiently completed. Therefore, a crosslinking step may be provided separately from the drying step. As a condition of the crosslinking step, it is preferable to heat at a temperature of 40 ° C to 100 ° C for about 2 minutes to 120 hours.
[0093]
Next, a protective layer which can be optionally provided on the reversible thermosensitive recording layer for the purpose of preventing sticking and improving durability will be described.
The thickness of the protective layer is preferably in the range of 0.1 to 20 μm, more preferably 0.3 to 10 μm.
The protective layer may contain an inorganic or organic ultraviolet absorber for the purpose of preventing background fog, and the content thereof is in the range of 0.5 to 50 parts by weight based on 100 parts by weight of the binder. preferable.
As the solvent used for the coating liquid for the protective layer, the dispersing device for the coating liquid, the binder, the coating method, the drying / curing method, and the like, the known methods used for the recording layer can be used.
[0094]
Examples of the organic ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy -3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5 '-Octoxyphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t- Benzotriazole-based ultraviolet absorbers such as butyl-5'-methylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-5'-ethoxyphenyl) benzotriazole; -Dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 '-Dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-oxybenzylbenzophenone, 2-hydroxy-4-chlorobenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 2,2'-dihydroxy-4,4'- Dimethoxybenzofe Benzophenone ultraviolet absorbers such as sodium sulfonic acid, phenyl salicylate, p-octyl phenyl salicylate, pt-butyl phenyl salicylate, carboxyphenyl salicylate, methyl phenyl salicylate, dodecyl phenyl salicylate, 2-ethylhexyl phenyl salicylate, homomenthyl Salicylic acid ester-based ultraviolet absorbers such as phenyl salicylate; cyanoacrylate-based ultraviolet absorbers such as 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate and ethyl-2-cyano-3,3'-diphenylacrylate; P-aminobenzoic acid-based ultraviolet absorbers such as aminobenzoic acid, glyceryl p-aminobenzoate, amyl p-dimethylaminobenzoate and ethyl p-dihydroxypropylbenzoate; Cinnamic acid type ultraviolet absorbers such as methoxycinnamic acid-2-ethylhexyl and p-methoxycinnamic acid-2-ethoxyethyl, 4-t-butyl-4'-methoxy-dibenzoylmethane, urocanic acid, urocanic acid Ethyl and the like.
[0095]
As inorganic ultraviolet absorbers, zinc sulfide, titanium oxide, cerium oxide, tin oxide, molybdenum oxide, zinc oxide, barium nitride, silica, alumina, antimony oxide, magnesium oxide, zirconium oxide, barium oxide, calcium oxide, strontium oxide, Examples include silicon nitride, aluminum nitride, boron nitride, barium sulfate, and the like.
[0096]
To the protective layer, other fillers having no ultraviolet absorbing performance or ultraviolet shielding performance may be added for the purpose of preventing sticking and improving durability, and the fillers can be divided into inorganic fillers and organic fillers.
As inorganic fillers, calcium carbonate, magnesium carbonate, silicic anhydride, hydrous silicic acid, hydrous aluminum silicate, hydrous calcium silicate, alumina, iron oxide, calcium oxide, magnesium oxide, chromium oxide, manganese oxide, silica, Talc, mica, and the like.
Organic fillers include silicone resins, cellulose resins, epoxy resins, nylon resins, phenolic resins, polyurethane resins, urea resins, melamine resins, polyester resins, polycarbonate resins, styrene, polystyrene, styrene-based isoprene, and styrene-vinylbenzene. Resin, acrylic resins such as vinylidene chloride acrylic, acrylic urethane, and ethylene acrylic; polyethylene resins; formaldehyde resins such as benzoguanamine formaldehyde and melamine formaldehyde; polymethyl methacrylate resins; and vinyl chloride resins. In the present invention, the filler can be used alone, but two or more kinds may be contained. In the case of a plurality, the combination of the inorganic filler and the organic filler is not particularly limited. Examples of the shape include a spherical shape, a granular shape, a plate shape, and a needle shape. The content of the filler in the protective layer is 5 to 50% by volume in volume fraction.
[0097]
A lubricant may be added to the protective layer for the purpose of preventing fusion to the thermal head. Specific examples of the lubricant include synthetic waxes such as ester wax, paraffin wax and polyethylene wax: vegetable wax such as hardened castor oil. Classes: Animal waxes such as hardened tallow oil, etc .: Higher alcohols such as stearyl alcohol and behenyl alcohol: Higher fatty acids such as margaric acid, lauric acid, mystyrenic acid, palmitic acid, stearic acid, behenic acid, and formenic acid: Sorbitan Higher fatty acid esters such as fatty acid esters: Examples thereof include amides such as stearic acid amide, oleic acid amide, lauric acid amide, ethylenebisstearic acid amide, methylenebisstearic acid amide, and methylol stearic acid amide. The content of the lubricant in the layer is 0.1 to 95% by volume, more preferably 1 to 75%.
[0098]
In the present invention, the reversible thermosensitive recording material used as the oversheet has improved adhesion between the recording layer and the protective layer, prevents deterioration of the recording layer by applying the protective layer, and additives contained in the protective layer to the recording layer. For the purpose of preventing migration of the additive contained in the recording layer or migration of the additive contained in the recording layer, an intermediate layer can be provided between the two.
The thickness of the intermediate layer is preferably in the range of 0.1 to 20 μm, more preferably 0.3 to 10 μm. As the solvent used for the coating liquid for the intermediate layer, the dispersing device for the coating liquid, the binder, the coating method, the drying / curing method, and the like, the known methods used for the recording layer can be used.
The intermediate layer may contain the inorganic or organic ultraviolet absorber used in the protective layer for the purpose of preventing background fogging, and the content thereof is 0.5 to 50 parts by weight based on 100 parts by weight of the binder. Is preferable.
[0099]
Further, in the reversible thermosensitive recording material used in the information display recording card of the present invention, the reversible thermosensitive recording layer contains a photoelectric conversion substance or a layer containing a photoelectric conversion substance adjacent to the recording layer ( A photoelectric conversion layer).
By adopting a structure containing such a photoelectric conversion material, recording (coloring / decoloring) can be performed even when a low-output semiconductor laser or the like is used.
Of the above two methods using a light-to-heat conversion material, the case where the light-to-heat conversion layer is provided adjacent to the reversible recording layer is more expensive in terms of the cost of the light-to-heat conversion material and the material for forming the recording layer. It is preferable because it is hardly affected.
Furthermore, in the present invention, in order to protect the layer containing the light-to-heat conversion substance, a visible light transmitting ultraviolet absorbing layer can be further provided.
Examples of the photothermal conversion substance to be used include an infrared absorbing dye and carbon black, and a substance having an absorption peak near the oscillation wavelength of the semiconductor laser light to be used is selected.
In general, a semiconductor laser having a wavelength of 100 nm to 1,000 nm, preferably 700 to 900 nm can be used. As the infrared absorbing dye, a cyanine dye, a polymethine dye, an anthraquinone dye having an absorption peak in such a wavelength region can be used. Dyes and the like are preferably used. Of these, phthalocyanine dyes or naphthalocyanine dyes are preferred.
Structurally, it is durable against degradation such as decomposition by heat or ultraviolet rays, so that the number of rewrites can be improved.
From the viewpoint of chemical stability such as weather resistance and heat resistance, those which form a complex with various metals are particularly preferable.
Further, a singlet oxygen quencher may be added to improve the chemical stability.
[0100]
The reversible thermosensitive recording material that is the oversheet of the present invention is generally produced by sequentially forming a recording layer and other necessary layers on a support, but is limited to this production method. Instead, the following manufacturing method can be applied.
For example, regarding a reversible thermosensitive recording material in which a reversible thermosensitive recording layer and a protective layer are sequentially provided on a support, a release substrate sheet having a high releasability with a protective layer surface provided on the uppermost layer is prepared. A protective layer is first formed by applying a coating liquid on the sheet, then a heat-sensitive recording layer is formed on the protective layer by a coating method, and then a support film is adhered to the heat-sensitive recording layer. A method of peeling off the sheet to produce a reversible thermosensitive recording material is exemplified.
[0101]
In addition, a part or the entire surface of the reversible thermosensitive recording material that is the oversheet of the present invention, a printing layer such as offset printing, gravure printing, or an inkjet printer, a thermal transfer printer, a colored layer subjected to any pattern by a sublimation printer or the like May be provided, and an OP varnish layer containing a curable resin as a main component may be provided on a part or the entire surface of the coloring layer.
[0102]
3 and 4 show an example of a method for producing an IC card having a print layer, which is an example of the information recording and display card of the present invention.
FIG. 3 is a cross-sectional view showing a layer structure in a state before a press for forming an IC card is performed. In the IC card shown in FIG. 3, an inlet sheet (C) is sandwiched between two core sheet portions (B1) and (B2), and an oversheet support is provided outside one of the core sheet portions (B1). The oversheet (A) is overlapped so that (103) is in contact with the surface of the core sheet portion, and the outer sheet (D) is overlapped outside the other core sheet portion (B2), and the oversheet (A) and the outer sheet portion (D) are overlapped. The laminate for IC cards is formed by performing a heat-pressing press from the outside of ()) and performing thermocompression bonding. Here, the inlet sheet (C) is a sheet (118) on which a non-contact type IC chip (113) provided with an antenna coil (114) is arranged. The outer layer sheet portion (D) is an outer layer sheet (119) to which the magnetic stripe layer (115) has been temporarily transferred in advance. The core sheet portion (B1) has a printed layer (111) on the surface on the oversheet side of the white core sheet (116), and the core sheet portion (B2) has an outer layer sheet portion (D) of the white core sheet (117). A printing layer (112) is provided in advance on the surface on the side of ()).
Next, after removing the peeling substrate (101), it is cut into a card shape by a punching blade to form an IC card. According to the method of finally peeling the release substrate, the release substrate (101) functions as a protective film for the reversible recording layer (102). It is possible to prevent the mirror plate for hot pressing from being stained by bleed or the like from the recording layer.
FIG. 3 shows a method of removing the release base material after thermocompression bonding. However, the release base material (101) is removed from the oversheet (A) in advance, and the release base material (101) is stacked on the core sheet (B1). Similarly, an IC card may be prepared by performing a heat press or the like. Since the oversheet having such a configuration can be handled in the same manner as a general-purpose thick oversheet, a production line for general-purpose cards can be used. Further, an oversheet wound in a roll shape with the release substrate removed may be used.
In this embodiment, the pressing conditions are preferably such that the pressing temperature is in the range of 100 ° C. to 150 ° C., and the pressing pressure is 10 kgf / cm. ² ~ 50kgf / cm ² And the pressing time is preferably in the range of 5 minutes to 60 minutes.
As shown in FIG. 3, an IC card formed by heat-pressing can be formed into a card shape and then can be embossed using an embosser. FIG. 4 shows the IC card (E) on which the emboss (120) has been applied.
[0103]
As the sheet material of the sheet on which the non-contact type IC chip having the antenna coil is arranged, the same material as the above-described core sheet or outer layer sheet, engineering plastic, or the like can be used. Excellent materials are preferred. The antenna coil may be formed by printing or etching such a sheet. In the IC card shown in FIG. 3, a sheet on which a non-contact type IC chip provided with an antenna coil or the like is used, but an IC chip on which an antenna coil is wired may be used.
[0104]
Information such as a magnetic tape and an IC chip mounted on the IC card of the present invention can read stored information or write new information by a conventionally known method of contact or non-contact.
[0105]
The image processing method of the present invention may include any other steps as long as the method includes a step of performing at least one of displaying an image and erasing an image by heating a surface of an image display unit of the information recording display card of the present invention. A step may be added.
[0106]
In order to form a color-developed image on the reversible thermosensitive recording material which is the oversheet of the present invention, the material may be once heated to a color-developing temperature or higher and then rapidly cooled.
Specifically, for example, when the recording layer is heated for a short time by a thermal head or a laser beam, the recording layer is locally heated, so that the heat is immediately diffused, rapid cooling occurs, and the coloring state can be fixed.
On the other hand, in order to erase the color, heating may be performed for a relatively long time using an appropriate heat source and cooling, or heating may be temporarily performed to a temperature slightly lower than the coloring temperature. If the recording medium is heated for a long time, the temperature of a wide area of the recording medium rises, and the subsequent cooling is slowed down. As a heating method in this case, a hot roller, a hot stamp, hot air, a ceramic heater, or the like may be used, or heating may be performed for a long time using a thermal head. In order to heat the recording layer to the decoloring temperature range, the applied energy may be slightly reduced from that at the time of recording, for example, by adjusting the voltage or pulse width applied to the thermal head.
With this method, recording and erasing can be performed only by the thermal head, and so-called overwriting can be performed by erasing an image and displaying a new image. As a recording device, a thermal transfer printer, a sublimation type printer, or the like may be used in addition to a commonly used printer. Further, it can be erased by heating to a decoloring temperature range by a heat roller or a heat stamp.
[0107]
An image processing apparatus according to the present invention includes an image display apparatus used to display an image on the information recording / display card of the present invention, an image erasing apparatus used to erase an image, and an apparatus for displaying and erasing an image. There is no particular limitation except that at least one of the image display / erase devices used for the above is provided.
Examples of the image display means include a thermal head and a laser device. Examples of the image erasing means include a thermal head, a ceramic heater, a heat roller, a heat stamp, and a hot air blower.
[0108]
【Example】
Hereinafter, the information recording and displaying card of the present invention will be described more specifically based on examples and comparative examples, but the information recording and displaying card of the present invention is not limited to these examples.
[0109]
(Example 1)
1. Preparation of the support constituting the oversheet and the barrier layer formed thereon
As a support, an amorphous sheet (manufactured by Mitsubishi Plastics, Inc., trade name: Diafix PA-C) having a polymer alloy resin of an aromatic polyester resin and a polycarbonate resin having a thickness of 100 μm was prepared.
Next, a 4.5 μm-thick stretched PET film (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., trade name: Diafoil K233E) was used as a barrier layer, and a two-part type of a urethane-based resin and an isocyanate crosslinking agent was used on one surface. Is applied and dried to form an adhesive layer having a thickness of 1 μm. Then, the adhesive layer is laminated on the support and dry-laminated, and the obtained sheet is subjected to an atmosphere at 40 ° C. for 24 hours. After aging, a substrate provided with a barrier layer on a support was prepared.
2. Preparation of reversible thermosensitive recording layer and protective layer constituting oversheet
(1) Reversible thermosensitive recording layer
The following dispersion liquid for a reversible recording layer was prepared, and this coating solution was applied on the above barrier layer using a wire bar, dried at 80 ° C. for 5 minutes, and cured at 60 ° C. for 24 hours to form a film. A reversible recording layer having a thickness of about 10 μm was formed.
(Dispersion for reversible thermosensitive recording layer)
1) 4 parts of a developer having the following structural formula
[0110]
Embedded image

2) 1 part of dialkyl urea (Nippon Kasei Co., Ltd., Hakclean SB)
3) Acrylic polyol 50% solution 9 parts
(LR503, manufactured by Mitsubishi Rayon Co., Ltd.)
4) 70 parts of methyl ethyl ketone
The above composition was pulverized and dispersed using a ball mill so as to have an average particle size of about 1 μm.
5) 2-anilino-3-methyl-6-dibutylaminofluorane 1 part
6) 2 parts of isocyanate (Coronate HL, manufactured by Nippon Polyurethane Co., Ltd.)
The above composition was added to a dispersion obtained by pulverizing and dispersing a developer, and the mixture was thoroughly stirred to prepare a recording layer coating liquid.
[0111]
(2) Protective layer
Next, the following coating liquid for forming a protective layer was prepared, and the coating liquid was applied on the formed reversible recording layer so that the thickness became 2 μm, and then ultraviolet rays were applied at 160 W / cm × 10 m / m. The coating was cured by irradiation under the conditions of minutes, and then aged at 60 ° C. for 16 hours to form a protective layer. Thus, an oversheet having an oversheet base material, a barrier layer, a reversible thermosensitive recording layer, and a protective layer in this order was produced.
[0112]
(Coating solution for forming protective layer)
1) Urethane acrylate UV curable resin 15 parts
(C7-157, manufactured by Dainippon Ink and Chemicals, Inc.)
2) Filler (Mizusawa Chemical Co., Ltd., P527) 5 parts
3) Ethyl acetate 85 parts
The above composition was thoroughly dissolved and stirred to prepare a coating liquid for forming a protective layer.
[0113]
3. Production of information record display card
An amorphous sheet (Diafix PA-C, manufactured by Mitsubishi Plastics Co., Ltd., trade name: Diafix PA-C) whose main component is a polymer alloy resin of an aromatic polyester resin and a polycarbonate resin having a thickness of 100 μm is used as an outer layer sheet and an amorphous sheet having a thickness of 280 μm. Polyester sheet (manufactured by Mitsubishi Plastics, Inc., trade name: Diafix PG-WHI) was prepared as a core sheet.
Each of these core sheets and each of the obtained oversheets was cut into a size of 300 mm × 300 mm.
After stacking two core sheets, sandwiching the outer layer from above and below so that the outer layer and the protective layer of the oversheet are on the outer surface, sandwich the core sheet further between the chrome-plated plates so that they do not shift, and perform hot pressing to melt. Wearing integrated.
Heating temperature is 120 ° C and pressing pressure is 15kg / cm in sheet pressure. ² The pressing time is 10 minutes.
After cooling and taking out the fused and integrated sheet, it was punched into a card shape to produce an information recording / display card.
[0114]
(Example 2)
In preparing the oversheet, dry lamination is performed on an amorphous sheet (manufactured by Mitsubishi Plastics, trade name: Diafix PA-C) having a polymer alloy resin of an aromatic polyester resin and a polycarbonate resin having a thickness of 100 μm as main components. An information recording display card was produced in the same manner as in Example 1 except that the stretched PET film was changed to a 6 μm-thick stretched PET film (trade name: Diafoil K230E) to form a barrier layer.
[0115]
(Example 3)
In preparing the oversheet, dry lamination is performed on an amorphous sheet (manufactured by Mitsubishi Plastics, trade name: Diafix PA-C) having a polymer alloy resin of an aromatic polyester resin and a polycarbonate resin having a thickness of 100 μm as main components. An information recording and display card was produced in the same manner as in Example 1, except that the stretched PET film was changed to an 8 μm thick stretched PET film (trade name: Diafoil C230-8E) to form a barrier layer.
[0116]
(Example 4)
In the preparation of the oversheet, an amorphous sheet (manufactured by Mitsubishi Plastics Co., Ltd., trade name: Diafix PA-C) having a polymer alloy resin of an aromatic polyester resin and a polycarbonate resin having a thickness of 100 μm as a main component is formed as follows. The coating solution for a barrier layer shown below was applied using a bar coater.
Thereafter, an information recording and display card was produced in the same manner as in Example 1 except that the coating was cured by irradiating ultraviolet rays at 160 W / cm × 10 m / min to form a barrier layer having a thickness of 2 μm.
[0117]

[0118]
(Example 5)
In the preparation of the oversheet, an amorphous sheet (manufactured by Mitsubishi Plastics Co., Ltd., trade name: Diafix PA-C) having a polymer alloy resin of an aromatic polyester resin and a polycarbonate resin having a thickness of 100 μm as a main component is formed as follows. The coating solution for a barrier layer shown below was applied using a bar coater.
Thereafter, an information recording / display card was produced in the same manner as in Example 1 except that drying was performed at 100 ° C. for 5 minutes to form a barrier layer having a thickness of 2 μm.
[0119]
(Coating solution for barrier layer)
・ 50 parts by weight of water-dispersed polyester polyol resin
(Product name "Evaphenol HO-18" manufactured by Nichika Chemical Co., Ltd.)
・ 6 parts by weight of water-dispersed polyisocyanate
(Product name "NK Assist IS-100N" manufactured by Nichika Chemical Co., Ltd.)
・ 20 parts by weight of water
[0120]
(Example 6)
As a support, an amorphous sheet (manufactured by Mitsubishi Plastics, Inc., trade name: Diafix PA-C) having a polymer alloy resin of a 100 μm thick aromatic polyester resin and a polycarbonate resin as a main component is made of a 100 μm thick amorphous sheet. Example 1 except that the sheet was changed to a sheet (manufactured by Mitsubishi Plastics, Inc., trade name: Diafix PG-CHT) mainly composed of a polymer alloy resin of a high quality aromatic polyester resin and a polycarbonate resin to form a barrier layer. An information recording display card was produced in the same manner.
[0121]
(Example 7)
As a release substrate, a polyethylene terephthalate film (38 μm thick) having a surface coated with a silicone resin in advance was prepared.
After applying an epoxy acrylate ultraviolet curable resin to the silicone-treated surface, it was cured by irradiating it with 160 W / cm ultraviolet light at a rate of 10 m / min to form a protective layer having a thickness of 5 μm.
Next, the dispersion liquid for a reversible recording layer used in Example 1 was applied on the protective layer surface provided on the release substrate, dried at 80 ° C. for 5 minutes, and then aged at 60 ° C. for 24 hours. A reversible recording layer having a thickness of 10 μm after drying was formed.
The release group obtained above on an amorphous sheet (manufactured by Mitsubishi Plastics, Inc., trade name: Diafix PA-C) having a polymer alloy resin of an aromatic polyester resin and a polycarbonate resin having a thickness of 100 μm as main components. A two-component adhesive coating solution of a urethane-based resin and an isocyanate crosslinking agent was attached to the recording layer side of the laminate of the material / protective layer / reversible recording layer by dry lamination.
The information was prepared in the same manner as in Example 1 except that after forming a laminate structure of the release substrate / protective layer / reversible recording layer / support, the release substrate was peeled off to obtain an oversheet. A record display card was prepared.
[0122]
(Example 8)
In the production of an information recording display card, a core sheet made of an amorphous polyester sheet having a thickness of 280 μm (manufactured by Mitsubishi Plastics, Inc., trade name: Diafix PG-WHI) is replaced with an amorphous polyester sheet having a thickness of 280 μm (manufactured by Mitsubishi Plastics, Inc.). An information recording and display card was produced in the same manner as in Example 1 except that the trade name was changed to Diafix PG-WHT.
[0123]
(Example 9)
An information recording display card was produced in the same manner as in Example 1 except that the following compound was used as a developer of the dispersion for a reversible thermosensitive recording layer used in Example 1.
[0124]
Embedded image

[0125]
(Comparative Example 1)
In preparing the oversheet, dry lamination is performed on an amorphous sheet (manufactured by Mitsubishi Plastics, trade name: Diafix PA-C) having a polymer alloy resin of an aromatic polyester resin and a polycarbonate resin having a thickness of 100 μm as main components. An information recording and display card was produced in the same manner as in Example 1, except that the stretched PET film was changed to a stretched PET film having a thickness of 12 μm (trade name: Diafoil H100) to form a barrier layer.
[0126]
(Comparative Example 2)
In preparing the oversheet, dry lamination is performed on an amorphous sheet (manufactured by Mitsubishi Plastics, trade name: Diafix PA-C) having a polymer alloy resin of an aromatic polyester resin and a polycarbonate resin having a thickness of 100 μm as main components. An information recording display card was produced in the same manner as in Example 1 except that the stretched PET film was changed to a stretched PET film having a thickness of 38 μm (trade name: Diafoil T100E) to form a barrier layer.
[0127]
(Comparative Example 3)
In the production of the oversheet, an amorphous sheet (manufactured by Mitsubishi Plastics, Inc., trade name: Diafix PA-C) having a polymer alloy resin of a 100 μm-thick aromatic polyester resin and a polycarbonate resin as a main component is coated with a 100 μm-thick non-woven sheet. An information recording and display card was produced in the same manner as in Example 1, except that a sheet containing a crystalline aromatic polyester resin as a main component (manufactured by Mitsubishi Plastics, Inc., trade name: Diafix PG-CHI) was used.
[0128]
(Comparative Example 4)
In the production of the oversheet, an amorphous sheet (manufactured by Mitsubishi Plastics, Inc., trade name: Diafix PA-C) having a polymer alloy resin of an aromatic polyester resin and a polycarbonate resin having a thickness of 100 μm is stretched to a thickness of 125 μm. (Crystallization) An information recording and display card was produced in the same manner as in Example 7, except that the PET sheet (manufactured by Diafoil, trade name: T100E) was changed.
[0129]
(Comparative Example 5)
In preparing the oversheet, an amorphous sheet (manufactured by Mitsubishi Plastics, Inc., trade name: Diafix PA-C) having a polymer alloy resin of an aromatic polyester resin and a polycarbonate resin having a thickness of 100 μm was converted into a 100 μm thick chloride. Instead of vinyl film C-8195 of vinyl film, a core sheet made of an amorphous polyester sheet having a thickness of 280 μm (trade name: Diafix PG-WHI, manufactured by Mitsubishi Plastics, Inc.) was replaced with vinyl foil C- of a 280 μm thickness vinyl chloride film. An information recording and display card was produced in the same manner as in Example 7, except that the number was changed to 4636.
[0130]
The oversheet and the information recording and display card produced in each of the above Examples and Comparative Examples were evaluated by the following evaluation methods, and the results are shown in Table 4 below.
[0131]
Test 1: Storage elastic modulus measurement
The sample was cut into a plate shape, and a test was performed by a tensile method using a “viscoelastic spectrometer” manufactured by Iwamoto Seisakusho. The dynamic viscoelasticity was measured in the range of 0 to 200 ° C. in steps of 3 ° C. at a frequency of 1 Hz, and the real term was calculated as the storage elastic modulus (E ′).
[0132]
Test 2: Measurement of over-sheet erasing temperature
Using a thermal gradient tester HG-100 manufactured by Toyo Seiki Co., Ltd., the print image reaching the saturation density is erased under the above conditions under the conditions of a pressure of 1 kgf / cm, a pressing time of 1 second, and a temperature of 5 ° C. The temperature when the color density at this time becomes “background density + 0.02 or less” is defined as the erasing temperature.
[0133]
Test 3: Rewrite characteristics
Using a card printer R28000 (manufactured by Kyushu Matsushita), erasing and printing were performed under the conditions of printing conditions: 0.75 mJ and heater bar temperature conditions: 140 ° C., and a clear image without image unevenness was obtained, and the unerased image was left. Is indicated by “○”, and a state where image unevenness / erasing unevenness is observed is indicated by “x”.
[0134]
Test 4: Durability after repetition
Erasing and printing were repeated 200 times using a card printer R28000 (manufactured by Kyushu Matsushita), and the state of the recording medium surface was visually observed and evaluated according to the following ranks.
Rank 1: No dent, scratch, or card deformation occurred on the recording medium surface.
Rank 2: No dents or scratches occurred on the surface of the recording medium, but card deformation occurred.
Rank 3: Severe dents, scratches, and card deformations occurred on the recording medium surface.
[0135]
Test 5: Embossability
Using the created card, embossing was performed using a hand embosser JIKEN NE-1000 (manufactured by Nipponjiken Co., Ltd.). The card warpage of the obtained embossed card was measured, and those exceeding 2.5 mm were marked with “x”. The embossing was performed according to JIS X6301 and X6302.
The card warpage was measured by a method specified in JIS X6301 and 6305. The embossed appearance was visually checked for embossing to check for cracks in the oversheet or peeling of the oversheet. Cards with no particular problems are marked with "O", and cards with cracks or peeling are marked with "X".
[0136]
[Table 4]

[0137]
【The invention's effect】
As apparent from the detailed and specific description, the reversible thermosensitive recording medium of the present invention can be easily embossed and has excellent durability without being deformed even in repeated image formation of coloring and erasing. It is.
[Brief description of the drawings]
FIG. 1 is a diagram for explaining a method for producing an information recording card according to an embodiment of the present invention, wherein (a) shows a state before the information recording card according to the embodiment of the present invention is heated and pressed; It is sectional drawing, (b) is sectional drawing which shows the state after heat press.
FIG. 2 is a diagram showing color development / decoloration characteristics of the reversible thermosensitive recording medium of the present invention.
FIG. 3 is a diagram for explaining a method of producing an IC card of the present invention, and is a cross-sectional view showing a state before the IC card is heated and pressed.
FIG. 4 is a cross-sectional view showing a state where the IC card shown in FIG. 3 is hot-pressed and then embossed.
[Explanation of symbols]
1 Support
2 Barrier layer
3 Reversible recording layer
4 Protective layer
5 core sheet
6 outer layer sheet
10 Overseat
A over sheet
B1 core seat
B2 core seat
C inlet sheet
D Outer sheet
E IC card
101 release base material
102 Reversible recording layer
103 overseat support
111 printing layer
112 printing layer
113 Non-contact IC chip
114 antenna coil
115 Magnetic Stripe Layer
116 core sheet
117 core sheet
118 sheets
119 outer layer sheet
120 emboss

Claims (30)

At least including a core sheet and an over sheet, the core sheet and the over sheet are laminated,
The oversheet contains an electron-donating color-forming compound and an electron-accepting compound on a support containing at least an amorphous polyester resin, and has a relative temperature depending on at least one of a heating temperature and a cooling rate after heating. It has a reversible thermosensitive recording layer capable of forming a state in which a colored state and a decolored state are formed, functions as an image display unit, and satisfies the following conditions (A) and (B):
Embossing is possible on the oversheet,
An information record display card, characterized in that:
(A) [Erase upper limit temperature of oversheet−30 ° C.] ≦ [temperature of storage elastic modulus E ′ (1.0E + 08) Pa] ≦ 200 ° C.
(B) 1.0E + 04Pa ≦ [storage elastic modulus E ′ of oversheet at 180 ° C.] ≦ 5.0E + 07Pa The information recording and displaying card according to claim 1, wherein the storage elastic modulus E '(1.0E + 08) temperature of the oversheet is 140C or more. 3. The information recording and displaying card according to claim 1, wherein an oversheet is attached to substantially the entire surface of the core sheet. 4. The information recording and displaying card according to claim 1, wherein the support is one of an amorphous polyester resin and a polymer alloy resin of an amorphous polyester resin and a polycarbonate resin. 4. The information recording and display card according to claim 1, wherein the support is a polymer alloy resin composition of a polybutylene terephthalate resin and a polycarbonate resin. The information recording / display card according to any one of claims 1 to 5, wherein a barrier layer is provided between the support and the thermosensitive recording layer. The information recording display card according to claim 6, wherein the barrier layer is formed by attaching a resin film. 8. The information recording and displaying card according to claim 7, wherein the resin film has a thickness of 8 μm or less. 9. The information recording and displaying card according to claim 7, wherein the resin film is a crystallization treated polyester film. The information recording display card according to claim 6, wherein the barrier layer is mainly composed of a resin that can be dissolved or dispersed in at least one of an alcohol-based solvent and water. The information recording / display card according to any one of claims 1 to 10, wherein the electron-donating color-forming compound is a leuco dye. The information recording display card according to any one of claims 1 to 11, wherein the electron accepting compound is a phenol containing a straight chain hydrocarbon. 13. The information recording and displaying card according to claim 1, wherein the core sheet is made of at least one thermoplastic resin sheet having a thickness of 0.05 to 5.00 mm. 14. The information recording and displaying card according to claim 13, wherein the core sheet is made of the same material as a support constituting the oversheet. 15. The information recording and display card according to claim 1, further comprising an information storage unit. 16. The information recording and displaying card according to claim 15, wherein the information storage unit is one of a device mainly made of a magnetic material and an IC chip. 16. The information recording and displaying card according to claim 15, wherein the core sheet is made of a thermoplastic resin sheet, and an IC chip is embedded in the thermoplastic resin sheet to form an information storage unit. The information recording and display card according to claim 15, wherein the oversheet has an information storage section mainly composed of a magnetic material. 19. The information recording and display card according to claim 1, wherein an embossing mark is provided. 20. The information recording and displaying card according to claim 19, wherein an embossed stamp is provided on the oversheet. 21. The method for producing an information recording display card according to claim 1, wherein the core sheet and the oversheet are bonded by hot pressing at a temperature equal to or lower than the melting point of the electron-accepting compound. The method for producing an information recording / display card according to any one of claims 1 to 20, wherein the core sheet and the oversheet are bonded by hot pressing at a temperature of 150 ° C or lower. An overseat comprising the information recording and display card according to any one of claims 1 to 20. 21. An image processing method, wherein at least one of displaying an image and erasing an image is performed by heating a surface of an image display section of the information recording / display card according to claim 1. The image processing method according to claim 24, wherein the image is displayed using a thermal head for displaying the image. The image processing method according to claim 24, wherein the image is erased using one of a thermal head and a ceramic heater. 27. The image processing method according to claim 24, wherein the image is overwritten by using a thermal head for displaying and erasing the image, and the overwriting is performed by erasing the image and displaying a new image. . 21. An image display and / or erasure means for displaying and / or erasing an image on the information recording / display card according to any one of claims 1 to 20. Image processing device. 29. The image processing apparatus according to claim 28, wherein the image display means is a thermal head. 29. The image processing apparatus according to claim 28, wherein the image erasing means is one of a thermal head and a ceramic heater.

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