JP3597187B2 - Printing laminate, printing method and printed matter using the same - Google Patents

Description

【００５５】
上記したＳＰ値９．０以上の物質を染料移行防止層として用いる時には膜厚を１μｍ以上１００μｍ以下、好ましくは２μｍ以上８０μｍ以下、さらに好ましくは３μｍ以上６０μｍ以下に設定するのが好適である。１μｍ未満であると染料の移行防止効果が十分でなく、１００μｍを越えるとフィルム強度が高くなりすぎ３次元曲面貼り適性が低下して好ましくなく、また、コストも高くなり好ましくない。さらには染料移行防止層に適用される上記したＳＰ値９．０以上の物質のガラス転移温度（Ｔｇ）を７０℃以上、好ましくは８０℃以上に設定すれば、真夏の屋外での使用時のような高温時でも分子運動が凍結されて染料の移行を防止するにはさらに好適となる。
【００５６】
染料移行防止層の他の有効な形態は、着色性樹脂層に連続させたり、染料移行防止層にさらに連続させて金属の薄膜を形成することにより染料の移行を防止できる。但し、下層に再帰反射層を形成する場合は好ましくない。ここにおいて金属層は下記の金属で形成することができ、その厚さは使用する金属によって異なるが、５〜５００ｎｍ、好ましくは１０〜４００ｎｍ、さらに好ましくは２０〜３００ｎｍである。上記金属層の厚さが５ｎｍ未満の場合は金属層の隠蔽性が十分でないために、染料の移行防止層としての目的が果たせなくなり、その上前記印刷用積層体を曲面等に貼る時には延伸されるため、さらに金属膜が薄くなりより好ましくなくなる。また、逆に５００ｎｍを越える場合は金属層と着色性樹脂層または染料移行防止層との付着性が低下したり、金属膜にクラックが入り易く、その上コスト高になるために好ましくない。上記金属層を設ける方法としては特に限定されるものではなく通常の蒸着法、スパッタリング法、転写法、プラズマ法等が利用できる。とりわけ作業性の面から蒸着法、またはスパッタリング法が好ましく用いられる。かかる金属層を形成するに際し、使用される金属も特に限定されるものではなく、例えばアルミニウム、金、銀、銅、ニッケル、クロム、マグネシウム、亜鉛等の金属を挙げることができるが、これらのうち作業性、金属層の形成し易さ等を考慮するとアルミニウム、クロムまたはニッケルがとくに好ましい。尚、上記金属層は２種以上の金属からなる合金で形成してもよい。
【００５７】
本発明の印刷用積層体の着色性樹脂層上に表面樹脂層を設けることにより、着色性樹脂層の染色剤を紫外線、水等から保護でき、十分な屋外での耐久性を保持させることが可能となる。このような要求特性を満足する材質として、オレフィン系の樹脂、すなわちポリエチレン、ポリプロピレンなど、ビニルアルコール系の樹脂すなわちポリビニルアルコール、エチレン−ビニルアルコール共重合体樹脂など、フッ素系樹脂、シリコン系樹脂、またはこれらの混合物等が挙げられる。
【００５８】
特に屋外耐候性が高く、また、染色剤との非親和性に富んだフッ素系樹脂やシリコン変性アクリル樹脂を主成分とする合成樹脂を使用するのが好ましい。フッ素系樹脂を主成分とする合成樹脂としてはポリテトラフルオロエチレン、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン−ヘキサフルオロプロピレン−パーフルオロアルキルビニルエーテル共重合体、テトラフルオロエチレン−エチレン共重合体、ポリクロロトリフルオロエチレン、クロロトリフルオロエチレン−エチレン共重合体、ポリビニリデンフルオライド、ポリビニルフルオライド等のフッ素系樹脂が挙げられる。これらのフッ素系樹脂を加工するには、主として熱を加えて溶融し、所望する形状に加工してから冷却し製品化するのが一般的手法である。しかしこのような手法で製造されたフィルムは縦方向や横方向に延伸されるので、熱転写時に１５０〜２００℃の温度まで昇温すると収縮する傾向を示し、印刷ブレや印刷模様の不鮮明化等の欠陥が発生しやすくなる。この発生を防止する為に表面樹脂層は前記した溶剤に可溶なフルオロオレフィン系共重合体からなるフッ素系樹脂を溶液流延法（キャスト法）等の加工方法にて製造した未延伸のフッ素系樹脂フィルムで形成されるのが好ましく、さらに好ましくは反応性官能基を有する溶剤に可溶なフルオロオレフィン系共重合体と、この反応性官能基と反応する硬化剤および／または硬化触媒との反応により形成されたものであるのが好適である。これらのうち、汎用溶剤に対する溶解性が良く、フィルムを製造する上での作業上の点からすれば、フルオロオレフィン類の共重合体あるいはフルオロオレフィン類とフルオロオレフィン以外の単量体との共重合体が特に好ましい（以下、これらを「フルオロオレフィン系共重合体」とも称する）。このような、フルオロオレフィン系共重合体を調整するに際して使用されるフルオロオレフィンの具体例は、フッ化ビニル、フッ化ビニリデン、トリフルオロエチレン、テトラフルオロエチレン、クロロトリフルオロエチレン、ヘキサフルオロプロピレン等が挙げられる。これらのフルオロオレフィンを２種以上共重合することによりフルオロオレフィン類のみを単量体成分とする共重合体が得られる。また、前記フルオロオレィン類とこれらと共重合可能な単量体類との共重合により溶剤に可溶なフルオロオレフィン系共重合体を調整することができる。このフルオロオレフィン類と共重合可能なビニル系単量体の具体例は、メチルビニルエーテル、エチルビニルエーテル、ｎ−ブチルビニルエーテル、シクロヘキシルビニルエーテル、シクロペンチルビニルエーテル等のアルキル若しくはシクロアルキルビニルエーテル類、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、ピバリン酸ビニル、バーサティック酸ビニル、安息香酸ビニル、ｐ−ｔ−ブチル安息香酸ビニル、シクロヘキサンカルボン酸ビニル、酢酸イソプロペニル等のカルボン酸ビニルエステル類、２−ヒドロキシエチルビニルエーテル、３−ヒドロキシプロピルビニルエーテル、４−ヒドロキシブチルビニルエーテル、２−ヒドロキシエチルアリルエーテル、２−ヒドロキシエチル（メタ）アクリレート等の水酸基を有する単量体類、アクリル酸、メタアクリル酸の如きカルボキシル基を含有する単量体類、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノエチルビニルエーテルの如きアミノ基を有する単量体類、グリシジルビニルエーテル、グリシジル（メタ）アクリレートの如きエポキシ基を有する単量体類、トリメトキシビニルシラン、トリエトキシビニルシラン、２−トリメトキシエチルビニルエーテル、γ−メタクリロキシプロピルトリメトキシシランの如き加水分解性シリル基を有する単量体類、２−トリメチルシリルオキシエチルビニルエーテル、４−トリメチルシリルオキシブチルビニルエーテルの如きシリルオキシ基を有するビニル系単量体類、トリメチルシリル（メタ）アクリレート、ビニル−５−トリメチルシリルオキシカルボニルペンタノエートの如きシリルオキシカルボニル基を有する単量体類、更にエチレン、プロピレン、塩化ビニル、各種アルキル（メタ）アクリレート等が挙げられる。このような単量体のうち、共重合性、塗膜性能等の点から、官能基を有しないビニルエステルやビニルエーテル類を必須成分として使用することが特に好ましく、更に、必要に応じて前記した如き反応性官能基を有する単量体を共重合すれば良い。
【００５９】
本発明に用いられるフルオロオレフィンとフルオロオレフィン以外の単量体との共重合体として好適なものとしては、フルオロオレフィン約１５〜７０重量％、反応性官能基を含有するビニル系単量体約０〜３０重量％、およびこれらと共重合可能な他の単量体類約５〜８５重量％を共重合したものである。より好適な共重合体としては、フルオロオレフィン約２０〜６５重量％、反応性官能基を含有するビニル系単量体約５〜２５重量％、およびこれらと共重合可能な他の単量体類約１０〜７５重量％を共重合したものである。フルオロオレフィンの使用量が約１５重量％未満では耐久性と防汚効果および昇華性の染色剤の透過性が不充分であるし、約７０重量％を越えると汎用溶剤への溶解性が低下して作業性を悪くするので好ましくない。また、使用される共重合体の重量平均分子量は、作業性とフィルムの耐久性の点から、約５０００〜４０００００、更には、約７０００〜３０００００の範囲内にあることが好ましい。
【００６０】
本発明の印刷用積層体の表面樹脂層であるフッ素系樹脂は、前記の通りフルオロオレフィン系共重合体とアクリル系重合体から調整することもできる。ここにいうアクリル系重合体とは、アクリル酸エステル若しくはメタアクリル酸エステルを必須成分とする単独重合体または共重合体であり、前記した反応性官能基を有するものおよび有しないもののいずれもが使用可能である。アクリル系重合体としては公知の各種のものが使用できるが、耐久性および作業性の点から、重量平均分子量として約５０００〜４０００００さらには約７０００〜３０００００を有するものが特に好ましい。
【００６１】
表面樹脂層用の樹脂として前記したフルオロオレフィン系共重合体とアクリル系重合体を併用する場合には、前者と後者の比率は重量比で、約３０：７０〜約９８：２、更に好ましくは約４０：６０〜約９５：５の範囲内にあることが望まれる。アクリル系重合体の使用量が約２％未満では付与したいアクリル系重合体の特性が発揮されないし、約７０重量％を越えると耐久性と防汚効果および昇華性の染色剤の透過性が不充分となるので好ましくない。
【００６２】
本発明の印刷用積層体の表面樹脂層を形成するに際して、フルオロオレフィン系共重合体およびアクリル系重合体は有機溶剤に溶解した形で使用される。フルオロオレフィン系共重合体もしくはブレンドされるアクリル系重合体が前記した如き反応性官能基を有する場合には、硬化剤として前記反応性官能基と反応する官能基を有するものを配合することもできる。反応性官能基として加水分解性シリル基を有する場合には、酸類、塩基あるいは各種有機錫化合物の硬化触媒を配合できる。また、前記の通り、硬化剤を配合させる場合にも、硬化反応を促進するに適した触媒を添加することもできる。フルオロオレフィン系共重合体の反応性官能基が水酸基若しくはシリルオキシ基の場合には、ポリイソシアネート、ブロックポリイソシアネート、アミノ樹脂、金属アルコキシド若しくは金属キレート化合物等を配合する。また、反応性官能基がエポキシ基の場合には、ポリカルボキシ化合物、ポリシリルオキシカルボニル化合物、ポリアミン化合物等を配合する。更に反応性官能基がカルボキシル基若しくはシリルオキシカルボニル基の場合には、ポリエポキシ化合物、エポキシシラン化合物、金属キレート化合物等を配合する。また、更に反応性官能基がアミノ基の場合には、ポリエポキシ化合物もしくはエポキシシラン化合物を硬化剤として配合する。フルオロオレフィン系共重合体或いはフルオロオレフィン系共重合体とアクリル系共重合体のブレンド物に硬化剤としてアミノ樹脂を配合する場合には、前記ベース樹脂成分約１００重量部に対してアミノ樹脂を約５〜１００重量部、好ましくは約１０〜６０重量部配合すれば良い。
【００６３】
また、アミノ樹脂以外の硬化剤を配合する場合には、フルオロオレフィン系共重合体あるいはフルオロオレフィン共重合体とアクリル系重合体ブレンド物中の反応性官能基１当量に対して硬化剤中の官能基が約０．２〜２．５当量、更に好ましくは約０．５〜１．５当量の範囲内となる様に硬化剤を配合すれば良い。
【００６４】
前記した表面樹脂層を形成するために使用される組成物中に、マット化剤として、シリカ、炭酸カルシウム、水酸化アルミニウム、アクリル樹脂、有機シリコーン樹脂、ポリスチレン、尿素樹脂、ホルムアルデヒド縮合物等の微粒子を添加して表面の６０°光沢を７０以下に下げれば、表面層への蛍光灯などの照明器具等の写り込みが防止できる。好ましくはアクリル樹脂を使用すれば前記フルオロオレフィン系共重合体との相溶性が良好となり好適である。
前記した表面樹脂層を形成するために使用される組成物及び前記した染料移行防止性着色性樹脂層または着色性樹脂層を形成するために使用される組成物には、紫外線吸収剤、光安定剤、酸化防止剤を個別にあるいはそれぞれの組み合わせにて添加して、これらを含有させることにより、長期耐久性をいっそう向上させることができる。このような紫外線吸収剤としては公知のものを使用でき、代表的なものとしては、ベンゾフェノン系、ベンゾトリアゾール系、シアノアクリレート系、サリチレート系およびシュウ酸アニリド系等、光安定化剤としてはヒンダードアミン系化合物等、酸化防止剤としてヒンダードフェノール系化合物、アミン系酸化防止剤、硫黄系酸化防止剤等の既知の化合物を使用することができる。しかし低分子化合物系の紫外線吸収剤、光安定剤、酸化防止剤を使用すれば透明樹脂からの相分離によるフェーズの出現、ブリードアウト、昇華性の染色剤を印刷用積層体内部に浸透させるために実施する加熱処理の際の揮発現象等の問題が顕著に現れるため、高分子量型の紫外線吸収剤、光安定剤、酸化防止剤を使用するのが好ましい。
【００６５】
本発明で使用する紫外線吸収剤としては、例えばフェニルサリシレート、ｐ−ジ−ｔｅｒｔ−ブチル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等のサリチル酸系のもの、２，４−ジヒドロキシベンゾフェノン、２−ヒドロキシベンゾフェノン、２−ヒドロキシ−４−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−ヒドロキシ−４−メトキシ−５−スルホベンゾフェノン等のベンゾフェノン系のもの、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’−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’−ｔｅｒｔ−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−３’，５’−ジ−ｔｅｒｔ−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’，５’−ジ−ｔｅｒｔ−アミルフェニル）ベンゾトリアゾール等のベンゾトリアゾール系のもの、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のもの、酸化チタン、酸化亜鉛、酸化セリウム等の金属酸化物系のもの、その他シュウ酸アニリド系、トリアジン系、ジベンゾイルメタン系、ベンジリデン系等がある。
【００６６】
紫外線吸収剤としては、上記紫外線吸収剤をポリマーの一部に導入した、いわゆる高分子量型紫外線吸収剤がある。
【００６７】
高分子量型紫外線吸収剤としては、公知のものを使用することができ、例えば、［２−ヒドロキシ−４−（メタクリロイルオキシエトキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［２−ヒドロキシ−４−（メタクリロイルオキシメトキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［２−ヒドロキシ−４−（メタクリロイルオキシオクトキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［２−ヒドロキシ−４−（メタクリロイルオキシドデシロキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［２−ヒドロキシ−４−（メタクリロイルオキシベンジロキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［２，２’−ジヒドロキシ−４−（メタクリロイルオキシエトキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［２，２’−ジヒドロキシ−４−（メタクリロイルオキシメトキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［２，２’−ジヒドロキシ−４−（メタクリロイルオキシオクトキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［２，２’−ジヒドロキシ−４−（メタクリロイルオキシベンジロキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［２，２−ジヒドロキシ−４−（メタクリロイルオキシドデシロキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［２，２’，４−トリヒドロキシ−４’−（メタクリロイルオキシエトキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［２，２’，４−トリヒドロキシ−４’−（メタクリロイルオキシメトキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［２，２’，４−トリヒドロキシ−４’−（メタクリロイルオキシオクトキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［２，２’，４−トリヒドロキシ−４’−（メタクリロイルオキシドデシロキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［２，２’，４−トリヒドロキシ−４’−（メタクリロイルオキシベンジロキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［４−ヒドロキシ−４’−（メタクリロイルオキシエトキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［４−ヒドロキシ−４’−（メタクリロイルオキシメトキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［４−ヒドロキシ−４’−（メタクリロイルオキシオクトキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［４−ヒドロキシ−４’−（メタクリロイルオキシドデシロキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［４−ヒドロキシ−４’−（メタクリロイルオキシベンジロキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［２−ヒドロキシ−４’−メチル−４−（メタクリロイルオキシエトキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［２−ヒドロキシ−４’−メチル−４−（メタクリロイルオキシメトキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［２−ヒドロキシ−４’−メチル−４−（メタクリロイルオキシオクトキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［２−ヒドロキシ−４’−メチル−４−（メタクリロイルオキシドデシロキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［２−ヒドロキシ−４’−メチル−４−（メタクリロイルオキシベンジロキシ）ベンゾフェノン］−メタクリル酸メチル共重合体、［２−（２’−ヒドロキシ−４’−メタクリロイルオキシエトキシ）ベンゾトリアゾール］−メタクリル酸メチル共重合体、［２−（２’−ヒドロキシ−４’−メタクリロイルオキシエトキシ）−５−クロロベンゾトリアゾール］−メタクリル酸メチル共重合体等が挙げられる。さらには２，２’−メチレンビス［６−（２Ｈ−ベンゾトリアゾール−２−イル） −４−（１，１，３，３−テトラメチルブチル）フェノール］等の分子量５００以上の高分子量型紫外線吸収剤も好適である。
【００６８】
光安定剤は紫外線によって生じたラジカルを効率良く捕捉（結合）して不活性化し、連鎖反応を阻止することによって染料の劣化を防止するものであり、４−ベンゾイルオキシ−２，２，６，６−テトラメチルピペリジン、ビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジニル）セバケート、２−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）−２−ｎ−ブチルマロン酸ビス（１，２，２，２，６−ペンタメチル−４−ピペリジル）、テトラキス（２，２，６，６−テトラメチル−４−ピペリジル）−１，２，３，４−ブタンテトラカルボキシレート等の各種ヒンダードアミン類、２，４−ジ−ｔｅｒｔ−ブチルフェニル−３，５−ジ−ｔｅｒｔ−ブチル−ヒドロキシベンゾエート等のヒンダードフェノール類、［２，２’−チオビス−（４−ｔｅｒｔ−ブチルフェノラート）］−ｔｅｒｔ−ブチルアミンニッケル（ＩＩ）、［２，２’−チオビス−（４−ｔｅｒｔ−ブチルフェノラート）］−２−エチルヘキシルアミンニッケル（ＩＩ）等のニッケル錯体類、３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジルリン酸モノエチルエステルのニッケル塩等のリン酸エステルのニッケル塩等が例示される。
【００６９】
とりわけＮ，Ｎ，Ｎ’，Ｎ’，−テトラキス−（４、６−ビス−（ブチル−（Ｎ−メチル−２，２，６，６−テトラメチルピペリジン−４−イル）アミノ）−トリアジン−２−イル）−４，７−ジアザデカン−１，１０−ジアミン、ジブチルアミン−１，３，５−トリアジン−Ｎ，Ｎ’−ビス（２，２，６，６−テトラメチル−４−ピペリジル）−１，６−ヘキサメチレンジアミンとＮ−（２，２，６，６テトラメチル−４−ピペリジル）ブチルアミンの重縮合物、ポリ［｛６−（１，１，３，３−テトラメチルブチル）アミノ−１，３，５−トリアジン−２，４−ジイル｝｛（２，２，６，６−テトラメチル−４−ピペリジル）イミノ｝ヘキサメチレン｛（２，２，６，６−テトラメチル−４−ピペリジル）イミノ｝］、コハク酸ジメチルと４−ヒドロキシ−２，２，６，６−テトラメチル−１−ピペリジンエタノールの重合物等の分子量１０００以上の高分子量型のヒンダードアミン系光安定剤がより好適である。
【００７０】
酸化防止剤には生成したラジカルのペルオキシドにプロトンを与えて安定化させるラジカル受容体型のものと、ヒドロペルオキシドを安定なアルコールに変質させる過酸化物分離型の２種類がある。前者としては、フェノール系化合物類、アミン系化合物類が代表的であるがフェノール系化合物類としては、ハイドロキノン、ガレート等の化合物、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール、ステアリル−β−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、２，２’−メチレンビス（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、２，２’−メチレンビス（４−エチル−６−ｔｅｒｔ−ブチルフェノール）、４，４’−チオビス（３−メチル−６−ｔｅｒｔ−ブチルフェノール）、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔｅｒｔ−ブチルフェニル）ブタン、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔｅｒｔ−４−ヒドロキシベンジル）ベンゼン、トリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）イソシアヌレート、テトラキス［メチレン−３（３’，５’−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］メタン等のヒンダードフェノール系化合物が例示され、アミン系化合物類としては、Ｎ，Ｎ’−ジフェニル−ｐ−フェニレンジアミン、フェニル−β−ナフチルアミン、フェニル−α−ナフチルアミン、Ｎ，Ｎ’−β−ナフチル−ｐ−フェニレンジアミン、Ｎ，Ｎ’−ジフェニルエチレンジアミン、フェノチアジン、Ｎ，Ｎ’−ジ−ｓｅｃ−ブチル−ｐ−フェニレンジアミン、４，４’−テトラメチル−ジアミノジフェニルメタン等が例示される。
【００７１】
また、後者としては、硫黄系化合物類、リン系化合物類が代表的であるが、硫黄系化合物としては、ジラウリルチオジプロピオネート、ジステアリルチオジプロピオネート、ラウリルステアリルチオジプロピオネート、ジミリスチルチオジプロピオネート、ジステアリル−β，β’−チオジブチレート、２−メルカプトベンゾイミダゾール、ジラウリルサルファイド等が例示され、リン系化合物類としては、トリフェニルフォスファイト、トリオクタデシルフォスファイト、トリデシルフォスファイト、トリラウリルトリチオフォスファイト、ジフェニルイソデシルフォスファイト、トリノニルフェニルフォスファイト、ジステアリルペンタエリスリトールフォスファイト等が例示される。クエンチャーは紫外線を吸収して励起した励起分子から励起エネルギーを奪い励起分子の反応を抑止する化合物であり、公知の種々の金属錯体等が挙げられる。これら酸化防止剤、クエンチャーのうち、分子量が１０００以上のヒンダードフェノール系化合物はとりわけ好適である。
【００７２】
また、有機溶剤としては従来から知られているものが使用可能であり、具体的には、酢酸エチル、酢酸ブチル、エチルセロソルブアセテート等のエステル系、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素系、ヘキサン、ヘプタン、オクタン、シクロヘキサン、エチルシクロヘキサン等の脂肪族もしくは脂環族系炭化水素、メタノール、エタノール、イソプロパノール、ｎ−ブタノール、イソブタノール等のアルコール系、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンの如きケトン系溶剤類等が挙げられる。これらのうち、硬化剤にポリイソシアネート化合物を使用する場合には、アルコール系溶剤の使用は避けなければならない。イソシアネート基とアルコールが反応してしまうからである。
【００７３】
シリコン変性アクリル樹脂の具体的な代表例を示すにとどめれば、下記のものを挙げることができる。
（１） 加水分解性シリル基を持つビニル系単量体を共重合したビニル系共重合体に、加水分解触媒を加え、硬化フィルムとしたもの。
（２） アミノ基および／またはカルボキシル基を持つビニル系単量体を共重合したビニル系共重合体に、一分子中にエポキシ基と加水分解性シリル基を併せ持った化合物を加え、硬化フィルムとしたもの。
（３） シリコン樹脂をグラフト重合した、水酸基を有するビニル系共重合体に、ポリイソシアネート化合物を加え、硬化フィルムとしたもの。
（４） シリコン樹脂をグラフト重合した、加水分解性シリル基を有するビニル系共重合体に、加水分解触媒を加え、硬化フィルムとしたもの。
【００７４】
なお、本発明で使用される昇華型インク用染色剤としては、大気圧下で、７０〜２６０℃で昇華または蒸発する染料が好ましい。例えば、アゾ、アントラキノン、キノフタロン、スチリル、ジフェニルメタン、トリフェニルメタン、オキサジン、トリアジン、キサンテン、メチン、アゾメチン、アクリジン、ジアジン等の染料があり、これらの内、１，４−ジメチルアミノアントラキノン、臭素化または塩素化１，５−ジヒドロキシ−４，８−ジアミノ−アントラキノン、１，４−ジアミノ−２，３−ジクロロ−アントラキノン、１−アミノ−４−ヒドロキシアントラキノン、１−アミノ−４−ヒドロキシ−２−（β−メトキシエトキシ）アントラキノン、１−アミノ−４−ヒドロキシ−２−フェノキシアントラキノン、１，４−ジアミノアントラキノン−２−カルボン酸のメチル、エチル、プロピル、ブチルエステル、１，４−ジアミノ−２−メトキシアントラキノン、１−アミノ−４−アニリノアントラキノン、１−アミノ−２−シアノ−４−アニリノ（またはシクロヘキシルアミノ）アントラキノン、１−ヒドロキシ−２−（ｐ−アセトアミノフェニルアゾ）−４−メチルベンゼン、３−メチル−４−（ニトロフェニルアゾ）ピラゾロン、３−ヒドロキシキノフタロン等がある。また、塩基性染料としてマラカイトグリーン、メチルバイオレット等を用いることができ、酢酸ナトリウム、ナトリウムエチラート、ナトリウムメチラート等で変性した染料等を用いるのが好適である。
【００７５】
これらの染料を使用した昇華型インクを用いて転写紙や印刷用積層体表面に設けられたインク仮表示表面層に電子写真法、静電記録法、インクジェット法、感熱転写法等によって印刷加工を施し、転写紙の場合は紙の印刷面を印刷用積層体の表面に当て、また、インク仮表示表面層に印刷した場合はそのままの状態で真空加熱圧着機やオーブン乾燥機、遠赤外線加熱装置等を用いて約１００〜約２００℃、数１０秒から数分間加熱することにより昇華性の染色剤が昇華し、印刷画像が着色性樹脂層の内部に拡散染色される。またこの時の印刷方法は、熱転写、静電印刷、グラビア印刷、インクジェット法等の公知慣用の方法による印刷方法を適用することが可能であるが、とりわけ簡便にフルカラー印刷が可能なインクジェットプリンターを使用した印刷方法がより好適であり、特にオンデマンド型がインクの使用効率の点から経済的であり好ましい。
また、前記印刷後の加熱処理温度は、印刷用積層体裏面の離型フィルム等に大きな熱ダメージを与えずに昇華性の染色剤の昇華をより短時間で効率よく行い作業性を良くする点から１５０〜２００℃の範囲であるのが好ましく、さらには前記加熱処理前に印刷表面を指触乾燥レベルまで乾燥させておけば加熱処理時の昇華性染色剤の拡散性が均一となりより好適となる。この時使用される転写用紙は一般に市販されているインクジェット用印刷用紙で良く、インク仮表示表面層には親水性樹脂を使用するのが好ましい。前記仮表示表面層を形成するために使用される親水性樹脂にはポリウレタン系樹脂、アクリル系樹脂、フッ素系樹脂、未変性および変性ポリビニルアルコール、ポリエステル、アクリルウレタン、酢ビ系、無水マレイン酸共重合体、アルキルエステルのＮａ塩、ゼラチン、アルブミン、カゼイン、デンプン、ＳＢＲラッテクス，ＮＢＲラテックス、セルロース系樹脂、アミド系樹脂、メラミン系樹脂、ポリアクリルアミド、ポリビニルピロリドン、これらをカチオン変性したもの、また、親水基を付加したもの等を１種または２種以上使用することも可能である。
【００７６】
また、シリカ、クレー、タルク、珪藻土、ゼオライト、炭酸カルシウム、アルミナ、酸化亜鉛、チタン等のフィラーを添加してもよい。
【００７７】
なお、本発明の印刷用積層体を曲面貼り等の用途に用いる時には、前記積層体には十分な伸びが要求されるが、低分子量の可塑剤等は染料のブリードを誘因するので前記積層体に使用するには不適当である。しかるに、本発明では、前記した染料移行防止層や金属薄膜によって染料のブリードは防止されているので、前記染料移行防止層や金属薄膜の裏面側には、前記した染料移行防止層に適用した樹脂に限定されることなく広く選択が可能であり、伸び率に富んだ樹脂を使用すれば良い。このような要求特性を満足する材質として、具体的には、ウレタン系樹脂、ビニル系樹脂、アクリル系樹脂、アルキッド系樹脂、ポリエステル系樹脂、エポキシ系樹脂、フッ素系樹脂、オレフィン系樹脂、シリコン系樹脂等の合成樹脂が使用可能である。この時の可撓性に富んだ層の乾燥膜厚は１μｍ〜１００μｍ以下、好ましくは３μｍ〜８０μｍ以下、さらに好ましくは５μｍ〜６０μｍ以下に設定されるのが好適である。膜厚が１μｍ未満であると、延伸時の伸びに追随させて、染料移行防止層の破断を防止するには十分ではない。また、膜厚が１００μｍを超えると、フィルムの総膜厚が厚くなり過ぎ、基板へ貼り付ける際の曲面への追随性が低下して好ましくない。これによって、前記積層体の伸び率は飛躍的に向上し、染料移行防止層や金属薄膜の延伸時のクラックも前記樹脂層を積層させることにより防止でき、結果的には柔軟性、伸び率に富み、染料のブリード防止が可能な印刷用積層体が完成される。
【００７８】
図１は本発明の参考例における印刷用積層体の断面図であり、表面から順番に昇華性染色剤と親和性が弱く、かつ前記染色剤を通過させる表面樹脂層（Ａ）１と、前記染色剤と親和性があり、かつ前記染色剤の移行を防止する染料移行防止性着色性樹脂層（Ｂ）１２とで構成される。
【００７９】
図２は本発明の一実施形態における印刷用積層体の断面図であり、表面から順番に表面樹脂層（Ａ）１と、前記染色剤と親和性がある着色性樹脂層（Ｂ１）２と、前記染色剤の移行を防止する染料移行防止層（Ｂ２）３とで構成される。
【００８０】
図３は本発明の別の実施形態における印刷用積層体の断面図であり、表面から順番に表面樹脂層（Ａ）１と、着色性樹脂層（Ｂ１）２と、染料移行防止層（Ｂ２）３と、染料移行防止層（Ｂ２）３よりも伸び率が大なる可撓性樹脂層（Ｃ）４とで構成される。
【００８１】
図４は本発明のさらに別の実施形態における印刷用積層体の断面図であり、表面から順番に表面樹脂層（Ａ）１と、染料移行防止性着色性樹脂層（Ｂ）１２と、染料移行防止性着色性樹脂層（Ｂ）１２の裏面に、さらに粘着剤層５とその下側に離型材６を備え、粘着剤層５または離型材６に帯電防止処理が施されている。
【００８２】
図５は本発明のさらに別の実施形態における印刷用積層体の断面図であり、表面から順番に表面樹脂層（Ａ）１と、着色性樹脂層（Ｂ１）２と、染料移行防止層（Ｂ２）３と、染料移行防止層（Ｂ２）３よりも伸び率が大なる可撓性樹脂層（Ｃ）４と、可撓性樹脂層（Ｃ）４の裏面に、さらに粘着剤層５とその下側に離型材６を備え、粘着剤層５または離型材６に帯電防止処理が施されている。
なお、図１〜３においても、粘着剤層５および離型材６を形成し、粘着剤層５または離型材６に帯電防止処理を施しても良い。
【００８３】
図１に示される印刷用積層体は、第１工程にて、ポリエチレンテレフタレートフィルムや工程紙のごとき支持フィルム上に乾燥膜厚が約０．５〜約３００μｍ、好ましくは約２〜約２００μｍ、さらに好ましくは約３〜約１００μｍとなるように、前記表面樹脂層１の塗料を塗布し、常温もしくは加熱により乾燥する。次に第２工程において、前記表面樹脂層１に続く染料移行防止性着色性樹脂層１２用の塗料を乾燥膜厚約１〜約５００μｍ、好ましくは約２〜約４００μｍ、さらに好ましくは約３〜約３００μｍになるように塗布し、常温もしくは加熱により乾燥して形成する。
【００８４】
図３に示される印刷用積層体は、第１工程にて、ポリエチレンテレフタレートフィルムや工程紙のごとき支持フィルム上に乾燥膜厚が約０．５〜約３００μｍ、好ましくは約２〜約２００μｍ、さらに好ましくは約３〜約１００μｍとなるように、前記表面樹脂層１の塗料を塗布し、常温もしくは加熱により乾燥する。次に第２工程において、前記表面樹脂層１に続く着色性樹脂層２用の塗料を乾燥膜厚約１〜約５００μｍ、好ましくは約２〜約４００μｍ、さらに好ましくは約３〜約３００μｍになるように塗布し、常温もしくは加熱により乾燥して形成する。
第３工程において、前記着色性樹脂層２に続く染料移行防止層３用の塗料を乾燥膜厚約１〜約５００μｍ、好ましくは約２〜約４００μｍ、さらに好ましくは約３〜約３００μｍになるように塗布し、常温もしくは加熱により乾燥する。第４工程において前記染料移行防止層３に続く可撓性樹脂層４の塗料を乾燥膜厚約１μｍ〜約１００μｍ以下、好ましくは約３μｍ〜約８０μｍ以下、さらに好ましくは約５μｍ〜約６０μｍ以下になるように塗布し、常温もしくは加熱により乾燥する。
【００８５】
なお、本工程は第１工程に前記可撓性樹脂層４用の塗料を、第２工程に前記染料移行防止層３用の塗料を、第３工程に前記着色性樹脂層２用の塗料を、第４工程に前記表面樹脂層１用の塗料を塗布して製造することも可能である。また、必要に応じて、前記可撓性樹脂層４を除去した工程も可能である。これらの工程を終了した後にポリエチレンテレフタレートフィルムや工程紙のごとき支持フィルムを前記積層体から剥離除去し、必要に応じて前記積層体の裏面、すなわち表面樹脂層と反対側の層に粘着剤層または接着剤層を形成し、さらに、離型紙または離型フィルム等の離型材を前記粘着剤層または接着剤層に貼り合わせて、印刷用積層体の完成品とすることもできる。但し染料移行防止層３に２軸延伸ポリエステルフィルムを用いた場合は、前記した支持フィルムと前記染料移行防止層３は兼用となるために支持フィルムを前記積層体から剥離除去する工程は省かれる。また、上記第１、第２、第３、第４工程における塗料塗布後の乾燥条件は、塗料原料として使用されるベース樹脂の種類、ベース樹脂中の官能基の種類、ベース樹脂中の反応性官能基の種類、硬化剤の種類、および溶剤の種類に応じて適宜決定される。上記各工程における塗料の塗布は、スプレー塗装によってもよいし、ナイフコーター、コンマコーター、ロールコーター、リバースロールコーター、フローコーター、等の通常用いられる塗装装置を使用して行うこともできる。また、本発明の印刷用積層体の各層を形成するために使用される塗料として顔料を含まないクリヤー塗料を使用することにより着色のない印刷用積層体が得られるが、表面樹脂層およびそれに続く下層を形成する塗料として顔料を含む着色塗料を使用することにより着色した印刷用積層体を得ることもできる。このような着色塗料を得る際に使用される顔料としては、フタロシアニンブルー、フタロシアニングリーン、キナクリドンレッド、もしくはハンザイエローのような有機系顔料や酸化鉄レッド、酸化鉄イエロー、チタンホワイト、コバルトブルー、カーボンブラックの如き無機系顔料等公知のものが適している。さらには顔料自体が５層構造になっており、入射光は表面層で約５０％、残りの約５０％が中央層のオペイク・リフレクター・メタルで反射する分光効果で干渉波長が発生し、視覚化されるクロマフレア顔料（Ｆｌｅｘ Ｐｒｏｄｕｃｔｓ社製）を使用すれば異なった色を視覚化でき、デザイン性に優れた印刷用積層体を得ることが可能となり好適である。同様の効果はアルミニウムフレイク顔料の表面を酸化鉄で被覆した“ＶＡＲＩＯＣＲＯＭ”（ＢＡＳＦ社製商品名）でも得ることが可能である。
前記表面樹脂層１、前記染料移行防止性着色性樹脂層１２、前記染料移行防止層３及びこれらの下層の各層のうち少なくとも１つ以上の層に光拡散性微粒子を配合した光拡散層を作製すれば、本発明の印刷用積層体は内照式フィルム（バックライト用フィルム）として使用可能となり好適である。この場合、着色層より下層側に光拡散性微粒子を配合すると画像の鮮明性、発色性を阻害することなくさらに好適である。
【００８６】
前記光拡散層を構成する光拡散性微粒子としては、シリカ、炭酸カルシウム、二酸化チタン、水酸化アルミニウム、アクリル樹脂、有機シリコーン樹脂、ポリスチレン、尿素樹脂、ホルムアルデヒド縮合物等を挙げることができるが、これらのうちから１種類以上を選べば良く、特に限定されるわけではない。
【００８７】
光拡散性微粒子が分散配合されてなる光拡散層のバインダーとなる光透過性樹脂としては、アクリル系樹脂、ポリウレタン系樹脂、ポリエステル系樹脂、ポリ塩化ビニル系樹脂、ポリ酢酸ビニル系樹脂、セルロース系樹脂、ポリアミド系樹脂、フッ素系樹脂、ポリプロピレン系樹脂、ポリスチレン系樹脂の単体あるいは混合体が好適であり、もしくはそれぞれの樹脂をメラミン樹脂、イソシアネート樹脂、エポキシ樹脂等の硬化剤を使用して当該樹脂の官能基と三次元硬化させた樹脂組成物を適用すればより好適であるが、特に限定されるものではない。光透過性樹脂と光拡散性微粒子との屈折率差は、一般的に０．０２程度以上であると良好である。また、光透過性樹脂のＴｇ（ガラス転移点）としては、５０℃以上が望ましく、Ｔｇが５０℃未満であると、光拡散層と他の部材が接触した場合、ブロッキングにより保存性に問題が生じたりするため好ましくない。
【００８８】
これらのうち、光拡散性微粒子の分散適性（濡れ性）や屈折率差の制御適性などが優れたものとして、アクリル系樹脂、ポリウレタン系樹脂、ポリエステル系樹脂、ポリ塩化ビニル系樹脂、ポリ酢酸ビニル系樹脂の単体あるいは混合体が好適であるが、それぞれの樹脂をメラミン樹脂、イソシアネート樹脂、エポキシ樹脂等の硬化剤を使用して当該樹脂の官能基と三次元硬化させた樹脂組成物がより好適である。
【００８９】
前記光拡散層を作製する方法としては、光透過性樹脂と１種類以上の光拡散性微粒子を適当な有機溶剤（または、水）に溶解または分散させたものを一般的な塗布方式、例えばロールコート法、ナイフコート法等を使用して塗布し、その後に有機溶剤（または、水）を乾燥蒸発させ、さらには必要に応じて当該樹脂と硬化剤の硬化反応を進行させれば良く、光拡散樹脂組成物の粘度、目的とする皮膜厚さ等を考慮して適宜塗布方式を選択すれば良い。光拡散性微粒子の添加量としては、光透過性樹脂に対して各々１〜４０重量％が望ましく、要求特性に合わせて分散配合すれば良い。光拡散層の塗布膜厚は、一般的に３〜５０μｍ程度が望ましいが、それに限られない。
【００９０】
前記光拡散層機能を有した印刷用積層体は前記表面樹脂層と反対側の裏面から照明光が入射した時、バックライトの蛍光灯等の線光源が該光拡散フィルムによって均一に拡散され、明るく輝く面発光体となり、かつ裏面の蛍光灯等の表面への写り込みも防止される。この時着色性樹脂層に昇華染色印刷されたカラー着色層にも光が透過して、内照式看板としての機能が発揮される。しかるに昇華染料は非常に透明性が良いため、所望される濃度まで透過濃度を上げるには多量のインクを印刷する必要があり、印刷作業性が低下し、また印刷後の乾燥性にも問題が発生した。この問題を解決するには、昇華染色される層に白色顔料を使用して白色層としておけば、印刷画像の透過濃度が向上することを見出した。
【００９１】
この際、鮮映性を上げる為には前記染料移行防止性着色性樹脂層１２、前記着色性樹脂層２及び前記染料移行防止層３のうち少なくとも１つ以上の層に白色顔料を使用して白色層を形成すれば印刷画像の透過濃度が向上することを見出した。この際染料移行防止性着色性樹脂層をさらに分割して、上層を透明樹脂層、下層を白色層、また着色性樹脂層と染料移行防止層が構成されている場合は該着色性樹脂層をさらに分割して上層を透明樹脂層、下層を白色層とすれば画像の鮮映性を保持しつつ透過濃度が向上してさらに好適である。この際白色化に使用される白色顔料は通常合成樹脂を白色に着色する為に用いられるものであれば良く、具体的には酸化チタン、亜鉛華、鉛白、硫酸バリウム、硫化亜鉛、酸化アンチモン、ＭＴｉＯ ₃ （ＭはＭｇ，Ｃａ，ＳｒおよびＢａからなる群より選ばれる１種以上の元素である。）で表される特定のチタン酸塩等が挙げられる。この時の白色顔料の使用量は、当該白色層の透過濃度Ｖ（ノーリツ鋼機社製、濃度測定機ＤＭ−２０１使用）が０．１０〜１．７０、好ましくは０．１５〜１．６５、さらに好ましくは０．２０〜１．４０になるようにするのが好適である。白色層の透過濃度Ｖが０．１０未満であれば画像の透過濃度を上げるには充分ではなく、又１．７０を超えれば光の透過性が不十分となり内照式看板の特性が低くなり好ましくない。
【００９２】
前記染料移行防止性着色性樹脂層１２に連続した下層、前記染料移行防止層３に連続した下層または可撓性樹脂層４の下層に、以下に説明する再帰反射構造体を作製すれば、夜間においても車両のヘッドライト等の照明により、光源の方向に正確に光を返し、昼間と同様のフルカラーの画像が車両の運転手等に視認されるので、道路用標識をはじめ各種広告看板に好適である。さらにはオンデマンド方式で画像印刷が可能となるので、従来再帰反射シートに適用されていたシルクスクリーン印刷のように、画像別に版を作製する必要もなく、コスト削減上も極めて有用である。
【００９３】
再帰反射シートの作製方法（１）〜（３）の例について以下に説明する。
（１） 図６に示すように、前記した各樹脂層の下層に高屈折ガラスビーズ１０２を配合した焦点樹脂組成物を焦点層フィルム１０１として最適な乾燥膜厚が得られる様に塗布した後、常乾もしくは加熱により乾燥する。ここで、焦点層の最適な乾燥膜厚はガラスビーズの粒子径によって異なるが概ね１０〜７０μｍ程度である。次に、金属反射膜１０３からなる反射層を形成する。この時使用する焦点樹脂組成物塗料として好適なものとしては、ポリウレタン系樹脂、ポリビニルアセタール系樹脂、アクリル系樹脂、アルキッド樹脂、ポリエステル樹脂等をベースポリマー成分とするものであり、これらは非架橋タイプとして使用できるし、アミノ樹脂、エポキシ樹脂、ポリイソシアネート、ブロックポリイソシアネートの如き硬化剤を配合して熱硬化タイプとしても使用することができる。
【００９４】
また、上記における焦点樹脂組成物塗料塗布後の乾燥条件は、塗料原料として使用されるベース樹脂の種類、ベース樹脂中の反応性官能基の種類、硬化剤の種類および溶剤の種類に応じて適宜決定される。
【００９５】
使用するガラスビーズとして好適なものは屈折率１．９０〜２．４０さらに好ましくは２．１０〜２．３０のものが好適である。粒子径は５〜３００μｍさらに好ましくは２０〜１００μｍのものが好適である。ビーズの粒子径が５μｍ未満になると、必要とされる焦点層の膜厚が極度に薄くなり、膜厚のコントロールが困難となる。一方、３００μｍを越える場合、必要とされる焦点層膜厚が極度に厚くなり、成形時の加熱工程での樹脂の流動が原因して、ガラスビーズの球径と同心円に樹脂を成形するのは困難である。屈折率が１．９未満であると、必要とされる焦点層膜厚が極度に厚くなり、ガラスビーズの球径と同心円に樹脂を成形するのは困難である。また、２．４を超える屈折率のビーズを製造する場合、結晶化を防止して、透明なガラスビーズを精度よく工業的に生産するのは至極困難である。
【００９６】
上記金属反射膜１０３を設ける方法としては、特に限定されるものではなく、通常の蒸着法、スパッタリング法、転写法、プラズマ法等が利用できる。特に作業性の面から蒸着法、スパッタリング法が好ましく用いられる。かかる金属層を形成するに際し使用される金属も特に限定されるものではなく、例えばアルミニウム、金、銀、銅、ニッケル、クロム、マグネシウム、亜鉛等の金属を挙げることができるが、これらのうち、作業性、金属反射膜の形成し易さ、光の反射効率耐久性等を考慮すると、アルミニウム、クロムまたはニッケルが特に好ましい。尚、上記金属反射膜は２種以上の金属から成る合金で形成してもよい。その厚さは、使用する金属によって異なるが５〜２００ｎｍ、好ましくは１０〜１００ｎｍである。上記金属反射膜の厚さが５ｎｍ未満の場合は、金属反射膜の隠ぺい性が十分でないために反射層としての目的が果せなくなり、また、逆に２００ｎｍを超える場合は、金属反射膜にクラックが入り易く、その上コスト高になるために好ましくない。
（２） 図７に示すように、前記した各樹脂層の下層に、ガラスビーズ固着層２０１の乾燥膜厚が、使用するガラスビーズ粒子径の１０％の厚さから１００μｍ好ましくは、使用するガラスビーズ粒子径の２０％の厚さから８０μｍになる様に前記ガラスビーズ固着層形成用塗料を塗布してから、常温乾燥もしくは加熱乾燥により溶剤を揮散させ、次に高屈折ガラスビーズ２０２を埋込む。ガラスビーズ固着層を形成する際に使用される塗料の代表的なものとしては、反応性官能基を含有するフルオロオレフイン系共重合体、ポリエステル樹脂、アルキド樹脂、ポリウレタン樹脂、反応性官能基を有するアクリル系重合体をベース樹脂成分としアミノ樹脂、エポキシ樹脂、ポリイソシアネート、ブロックポリイソシアネートの如き硬化剤及び／又は硬化触媒を配合したものが挙げられる。ここにおいて、前記した各ベース樹脂成分は、単独で使用しても良いし、２種以上の混合物として使用することもできる。塗料形態としては、溶液型、非水分散型、水溶性タイプ、水分散タイプのいずれもが使用可能であるが、溶液型が特に好ましい。
【００９７】
次に上記（１）に記載した焦点樹脂組成物塗料を焦点層フィルム２０３として最適な乾燥膜厚が得られる様に塗布した後、常乾もしくは加熱により乾燥する。
【００９８】
上記した各工程における塗料の塗布は、スプレー塗装によっても良いし、ナイフコーター、コンマコーター、ロールコーター、リバースロールコーター、フローコーターの如き塗装装置を使用して行なうこともできる。
【００９９】
また、本発明の各再帰反射シートの各層を形成するために使用される塗料として顔料を含まないクリヤー塗料を使用することにより着色のない再帰性反射シートが得られるが、第６図及び第７図の各層を形成する塗料として顔料を含む着色塗料を使用することにより着色した再帰性反射シートを得ることもできる。かかる着色塗料を得る際に使用される顔料としては、フタロシアニンブルー、フタロシアニングリーン、キナクリドンレッドもしくはハンザイエローの如き有機系顔料や酸化鉄レッド、酸化鉄イエロー、チタンイエロー、コバルトブルーの如き無機系顔料等公知慣用のものが使用される。
【０１００】
このようにして得られる本発明の再帰性反射シートは、前記の如く金属反射膜２０４が形成された後、該金属反射膜に重ねて粘着剤層または接着剤層を形成し、さらに、必要に応じて該粘着剤層等に剥離紙や離型フィルム等の離型材を貼合わせて最終製品とすることもできる。
（３） 図８Ａに示す通り、ポリエステルフィルム３０８上にラミネートされたポリエチレンのガラス球仮固着層３０７の表面に透明のガラス球３０２を複数平面状に埋め込む。ポリエチレンラミネートフィルム（ガラス球仮固着層３０７及びポリエステルフィルム３０８）を加熱しポリエチレンを軟化させ、上記ガラス球３０２を埋め込む。このガラス球３０２は、粒子径約５〜３００μｍであり、約１．８〜２．１の屈折率を持つ微粒子である。とりわけガラス球として好適なものは、約１．９〜１．９５（特に好適なものは１．９２〜１．９３）の屈折率を持ち、粒子径が約２０〜９０μｍ（特に好適なものは４０〜８０μｍ）程度のものである。
【０１０１】
次に上記ガラス球仮固着層３０７の表面から露出するガラス球３０２の半球面に金属反射膜３０３を蒸着法により形成する。この蒸着は、ガラス球仮固着層３０７の表面全面に行なわれる。そして後述するガラス球仮固着層３０７表面のガラス球３０２以外の部分へ蒸着した金属反射膜３０３は、そのままガラス球仮固着層３０７の表面に残り、その他の金属反射膜３０３はガラス球３０２と共に支持樹脂シート３０４（図８Ｅ）へ移される。上記金属反射膜３０３としては、アルミニウム反射膜が好適であり、また、金、銀、銅、ニッケル、クロム等の他の金属によって形成されるものであっても実施可能である。
【０１０２】
次のステップとして、下記する２種類の構造を有する再帰性反射シートの製造方法がある。
（Ａ）プライマー層３０５があるタイプ
（Ｂ）プライマー層がないタイプ
上記（Ａ）の場合はプライマー層３０５の裏面に、（Ｂ）の場合は支持樹脂シート３０４の裏面に粘着剤が積層される。ガラス球仮固着層のガラスビーズを転写埋設させる支持樹脂フィルムのガラスビーズ転写性能の調整のため、支持樹脂シートに高分子または低分子可塑剤等を使用する場合がある。それら可塑剤等は経時的に粘着剤と支持樹脂シートとの界面または粘着剤層に移行して前記粘着剤の性能を低下させる。すなわち、粘着剤と支持樹脂シートの界面接着力の低下、粘着剤の基板への接着性能の低下等がおこる。この問題点を解消するため、すなわち支持樹脂シートから粘着剤層への可塑剤等の移行を防止するためにプライマー層が積層されることがある。
【０１０３】
前記（Ａ）のプライマー層３０５があるタイプは、前記した官能基を有する樹脂、またはそれらの樹脂及びそれらの樹脂の官能基と反応する官能基を持った硬化剤の中より、支持樹脂シートと層間接着性に優れる樹脂をプライマー層３０５用の樹脂として選択する。そして別途準備されたポリエステルフィルム３０６上にそれらのプライマー層３０５用として選択された樹脂溶液をコートして、熱風乾燥機を使用して乾燥を行なう。この時のプライマー層３０５の膜厚は３μｍ〜１００μｍ好ましくは６μｍ〜５０μｍが好適であり、３μｍ未満であると、可塑剤等の移行防止の効果が低くなって好ましくなく、１００μｍを越えると反射シートの貼り付け等の作業性が低下して好ましくない。
【０１０４】
次に、上記で作成されたプライマー層３０５の上方に、約１０〜３００μｍ、好ましくは約３０〜１００μｍの一定の厚さを有する支持樹脂シート３０４を作製する（図８Ｂ）。この支持樹脂シート３０４に使用することができる樹脂は前記した官能基を有する樹脂が好適である。
【０１０５】
前記（Ｂ）のプライマー層３０５のないタイプは、上記した再帰性反射シートの製造方法において、プライマー層作製の工程を省略して実施することができる。次に図８Ｃに示す通り、前記のような支持樹脂シート３０４をガラス球仮固着層３０７の表面に沿わす。そして図８Ｄに示すように、支持樹脂シート３０４をガラス球仮固着層３０７の表面へ押圧する。この押圧は、ガラス球３０２の金属反射膜３０３を蒸着した半球面が支持樹脂シート３０４内に埋設するよう行なう。この時、支持樹脂シート３０４のガラス球３０２の固着力を上げる為には、さらに支持樹脂シート３０４へのカップリング剤等の添加が効果的である。そして、図８Ｅに示すように、支持樹脂シート３０４表面から、ポリエステルフィルム３０８と共にガラス球仮固着層３０７を剥がす。このとき図８Ｅに示す通りガラス球３０２は、支持樹脂シート３０４に残り、支持樹脂シート３０４によって半球が埋没された状態に保持される。その後、常温で反応が進行する硬化形態（例えばイソシアネート硬化等）をプライマー層及び／又は支持樹脂シートに適用した場合には、次工程の加熱成形加工時の結合部の性能のバラツキをなくしたり、その後の自立形態の安定化を計る為に３０〜４０℃の環境でエージング処理を行ない、実質的に反応を終結しておくのが好ましい。またガラス球と支持樹脂シートの固着性を向上させるために１２０〜１５０℃での熱処理工程も効果的である。
【０１０６】
次に、図８Ｆに示した状態に形成された支持樹脂シート表面を前記印刷用積層体の前記染料移行防止性着色性樹脂層１２または前記染料移行防止層３あるいは可撓性樹脂層４で覆う。図８Ｆは、可撓性樹脂層４で覆った場合である。前記樹脂層が配置された支持樹脂シート３０４の裏面ポリエステルフィルム側３０６より、柄付きエンボスロール３０９で加熱圧着成形を行なう（図８Ｇ）。この加熱圧着の手段として、ロール表面温度が１５０〜２４０℃好ましくは１７０〜２２０℃の加熱ロールを通過させるのが好適である。１５０℃未満の温度で加熱成形が可能で、表面フィルムとの接着性が発現する支持樹脂シートは長期間のシートの自立形態を保持できず好ましくない。また、２４０℃を越えて加熱成形が可能な支持樹脂シートは、加熱成形加工を実施する時に保護フィルムとして使用するポリエステルフィルムが溶融するなど、加熱成形時の作業性の低下を引き起こして好ましくない。
【０１０７】
加熱成形加工の後に裏面ポリエステルフィルム３０６を剥離し、再帰性高輝度反射シート原反を作製する。これにより、支持樹脂シート３０４の裏面側には、例えば幅２００〜８００μｍ、深さ１００〜１５０μｍのエンボス溝３１０が形成される。
【０１０８】
該エンボス溝を埋め込むように粘着剤層または接着剤層を形成し、さらに、必要に応じて該粘着剤層等に剥離紙や離型フィルム等の離型材を貼合わせて最終製品とすることもできる。
【０１０９】
本発明の印刷用積層体の下層に位置する再帰性反射シートは前記した再帰性反射シート原反の他に各種公知の再帰性反射シートを応用することが可能である。
【０１１０】
上記工程を経て得られた本発明に係る印刷用積層体は、上記した再帰反射シート以外の構造体においても表面側とは反対側に染料移行防止層３や可撓性樹脂層４もしくは金属蒸着膜等が形成された後、更に必要に応じてこれらの層に重ねて粘着剤層または接着剤層を形成し、この粘着剤層または接着剤層等に離型紙または離型フィルム等の離型材を貼り合わせて、印刷用積層体の完成品とすることもできる。この時使用する離型材に、離型材表面の電気抵抗を低下させ、静電気の発生を防止するために、帯電防止剤を練り込み法によって添加したり、あるいは離型材表面に帯電防止剤を塗布したりすれば、シートを巻き出す時に発生する静電気やインクジェット印刷機による印刷時に前記印刷用積層体と印刷機との摩擦によって発生する静電気によって、印刷用ノズルから吐出されたインクの吐出方向が狂って、印刷画像に乱れが発生するのを防止することが可能となって好適である。なお、この時使用される帯電防止剤としては、各種界面活性剤、無機塩、多価アルコール、金属化合物、カーボン等が挙げられる。たとえば、界面活性剤としては、アルキルスルホン酸塩、アルキルベンゼンスルホン酸塩、アルキル硫酸エステル塩、アルキルエトキシ硫酸エステル塩、アルキルリン酸エステル塩等のアニオン系帯電防止剤、アルキルトリメチルアンモニウム塩、アシロイルアミドプロピルトリメチルアンモニウムメトサルフェート、アルキルベンジルジメチルアンモニウム塩、アシル塩化コリン等のカチオン系帯電防止剤、アルキルベタイン型、アルキルイミダゾリン型、アルキルアラニン型等の両性系帯電防止剤、脂肪酸アルキロールアミド、ジ−（２−ヒドロキシエチル）アルキルアミン、ポリオキシエチレンアルキルアミン、グリセリン脂肪酸エステル、ポリオキシエチレングリコール脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシソルビタン脂肪酸エステル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンアルキルエーテル等の非イオン系帯電防止剤の各種界面活性剤が挙げられる。離型材６がポリエチレンテレフタレートの場合は、ポリマー合成時に例えばポリエチレングリコールを５重量％程度共重合させることもできる。
【０１１１】
なお、前記離型材はあらかじめ加熱によりアニール加工を実施した２軸延伸ポリエステルフィルムを基材フィルムとして適用するのが好ましく、１５０℃で３０分加熱したときにフィルムの巻き取り方向に１．０％以下、好ましくは０．８％以下、更に好ましくは０．６％以下の収縮率の２軸延伸ポリエステルフィルムを基材フィルムとして適用するのが好ましい。１．０％を超える収縮率の離型材は、本発明の印刷用積層体を加熱して昇華染色するときに、前記離型材側に前記積層体をカールさせて好ましくない。
【０１１２】
また、必要に応じて前記表面樹脂層１を[M²⁺ _1-XM³⁺ _X(OH)₂]^X+[A^n- _X/n・mH₂O]^X-（Ｍ²⁺は２価の金属イオン、Ｍ³⁺は３価の金属イオン、Ａ^n-はｎ価のアニオン、Ｘは０より大きく０．３３以下、０≦m≦２）で示されるハイドロタルサイト類および金属酸化物の微粒子を含む塗膜形成組成物を塗布、乾燥させると親水性を呈する被膜を形成し、水に対して十分に小さい接触角を有する強固な表面になり、親水性による汚染防止を図ることができ、また再帰反射効果を阻害する結露による水滴の付着も防止できるので夜間の充分な再帰反射も確保できるので道路用標識をはじめ各種広告看板に適用すれば好適である。さらに該組成物は１μｍ以下の膜厚で充分な親水性能を発現し、また屋外で長期の親水性能を保持し、その上加熱によって表面樹脂層より昇華性の染色剤を印刷用積層体内部に浸透させる場合に、該染色剤の透過を阻害せず非常に好適である。前記金属酸化物の微粒子としては、酸化チタン粒子、特に酸化チタンのスラリー溶液が最も好ましいが、酸化チタンの代わりに、酸化ジルコニウム、チタン酸ストロンチウム、酸化タングステン、酸化鉄などの遷移金属酸化物やその他の金属酸化物、例えば、酸化亜鉛、酸化ビスマス、酸化スズ、アルミナ、マグネシア、酸化ストロンチウムなどを用いることも可能である。平均粒径としては０．００１〜０．５μｍの範囲内であることが好ましく、特に、０．０１〜０．１μｍの平均粒径を備えていることが望ましい。
【０１１３】
また、必要に応じて前記印刷用積層体の表面側に剥離性仮表示表面層を積層することも可能である。この時の仮表示表面層の製造は仮表示表面層用の樹脂を前記した塗装装置を使用して乾燥膜厚が約１μｍ〜約１００μｍ、好ましくは約３μｍ〜約８０μｍ、さらに好ましくは約５μｍ〜約６０μｍになるように調整すればよい。さらに必要に応じて前記仮表示表面層を２層以上の積層フィルムにして作製することも可能であり、その時は下層より順次上層を積層することにより製造される。なお、この場合には仮表示表面層の最上層側は昇華性の染色剤を含有したインクの吸収性があり、かつ前記表面樹脂層（Ａ）と接している面側は、前記昇華性の染色剤に非親和性の樹脂で形成されていることがより好適である。
【０１１４】
とりわけ表面側に仮表示表面層を積層した本発明の印刷用積層体は、市販のデジタルカメラで撮影した画像をインクジェットプリンターを使用して、印刷用積層体の仮表示表面層に直接印刷でき、その後に１５０〜２００℃で数分間加熱処理をすれば、仮表示表面層に印刷された昇華性の染色剤は印刷用積層体内部に拡散浸透されて簡単に画像が形成される。この画像は、従来の銀塩写真並みの高解像度を有し、またＪＩＳ Ｚ ９１１７に記載のサンシャインカーボン式促進耐候性試験機を使用して１０００時間試験を実施した後（屋外南面垂直暴露５年に相当）にも画像に異常は発生せず、また退色も殆ど視認できない程高耐久性を示した。これを屋内保管に置き換えると１００年を大きく上まわる保存安定性が得られた事になり、業務用、家庭用に従来の銀塩写真や一般に普及している水性インクジェットに比し、より大きなサイズの画像が従来よりも安価に作製でき、また銀塩写真において必要となる現像液の廃棄処理などが不要で、非常に環境適性にも優れ、さらには著しく鮮明な高耐久性で高保存性に優れた写真画像が得られる。
【０１１５】
このときの加熱拡散印刷を実施する方法としては、間接加熱方法と直接加熱方法を挙げることができる。間接方法は熱風による加熱や遠赤外線の照射による加熱等があり、直接加熱には加熱板に直接印刷用積層体を接触させたり、熱ロールに巻き付ける等の方法がある。これらのどちらの加熱方法を選択しても良いし、あるいは併用してもよい。拡散染色させるには１５０〜２００℃の高温加熱が必要とされるが、該印刷用積層体自体の温度を急激に前記した高温に昇温すれば、急激なシートの熱膨張が発生し、シートにシワ等の外観異常が発生して好ましくない。この問題を解決すべく本発明者が鋭意検討した結果、初期加熱は７０〜１３０℃、それに続き１２０〜１５０℃、さらに昇温させる場合には１４０〜２００℃の順に加熱し、さらには１２０〜１５０℃、７０〜１３０℃、常温と順次熱勾配を付けて昇温、一定温度での加熱、降温のサイクルで拡散印刷を行なえば熱膨張や降温による収縮を緩和でき、シートにシワ等の外観異常が発生せず好適である。さらに初期昇温加熱は加熱時間全体の１０〜６０％、一定温度での加熱は加熱時間全体の２０〜８０％、降温は加熱時間全体の１０〜４０％にすれば好適であり、さらに好ましくは初期昇温加熱を加熱時間全体の１５〜３５％、一定温度での加熱は加熱時間全体の３０〜７０％、降温は加熱時間全体の１５〜３５％にすればより好適である。また、ロール加熱の場合には降温時に中央部が両端部より太くなっているクラウンロールを使用すれば降温によるシートの収縮が原因となって発生するシワが防止でき好適となる。この時のクラウンロールの勾配は幅１０００mmあたり両端部と中心部の直径差が０．５〜１０mm、好ましくは１〜５mmとするのがさらに好適となる。また、間接加熱の場合には加熱機に入る入口に上下２本のロールでシートを挟み込み、順次駆動の懸かった下部サポートガイドロールにてシートを搬送し、必要に応じて搬送途中にシートのスムーズな搬送を補助すべく上部押さえロールを設けてシートを挟み込むようにすればさらに好適となる。このように間接加熱は当該印刷用積層体をロスすることなく必要数量を加熱処理することができ好適である。単版を加熱処理する場合には必要温度に加温された加熱板の上にシートを放置すればよいが、熱ロールにて連続処理を行なう場合には前記した条件に加え、巻き取り張力を５〜４０kg／ｍ幅、好ましくは１０〜３０kg／ｍ幅とすればシートに発生するシワが防止できて好適である。５kg／ｍ幅未満ではシートの巻き取り時にシワが発生して好ましくなく、４０kg／ｍ幅を超えると不必要な伸びがシートにかかり好ましくない。
【０１１６】
【実施例】
以下実施例を用いて更に具体的に説明する。以下の実施例において「部」は重量部を示す。また「％」は重量％を意味する。
【０１１７】
（実施例１、参考例）
図１に示す表面樹脂層１用の樹脂組成物を調整するに当り、フッ素系樹脂として重量平均分子量約４５０００なるヘキサフルオロプロピレン／エチルビニルエーテル／ベオバ９／アジピン酸モノビニル＝５０／１５／２０／１５（重量比）共重合体の溶液（「ベオバ９」：ジャパン エポキシ レジン社製商品名、分岐脂肪酸のビニルエステル、溶剤はトルエン／ｎ−ブタノール＝７０／３０重量比の混合溶剤、不揮発分約５０％）が約１００部、エポキシ当量１７０なるソルビトールポリグリシジルエーテルが約７．４部、ジアザビシクロオクタンが約０．６部、チヌビン９００（チバ・スペシャルティ・ケミカルズ社製、ベンゾトリアゾール系紫外線吸収剤）が約１部、チヌビン２９２（チバ・スペシャルティ・ケミカルズ社製、ヒンダードアミン系光安定剤）が約１部である樹脂組成物をポリエステルフィルム上に乾燥膜厚が約２０μｍになる様に塗布し、約１４０℃で約１０分間加熱乾燥を行い、表面樹脂層１を得た。続いて上記で作製した表面樹脂層１上に、前記した参考例１で合成されたビニル系重合体（ａ−１）が約１００部、硬化剤としてバーノックＤＮ−９５０（大日本インキ化学工業社製ポリイソシアネートプレポリマー、不揮発分約７５％）を約２５部、配合した樹脂組成物を乾燥膜厚が約３０μｍになるように塗布し、約１４０℃で約１０分間乾燥を行い、染料移行防止性着色性樹脂層１２を作製した。こうして得られた印刷用積層体の染料移行防止性着色性樹脂層１２の表面に、図４に示す通り、アクリル系粘着剤ファインタックＳＰＳ−１０１６（大日本インキ化学工業社製）約１００部と架橋剤ファインタックＴＡ−１０１−Ｋ（大日本インキ化学工業社製、粘着剤用硬化剤キレートタイプ）約２部の混合溶液を塗布し、約１００℃で約５分間加熱乾燥を行い、厚さ約３５μｍの粘着剤層５を形成した。さらに、この粘着剤層５に、片面にシリコンコートした厚さ５０μｍの２軸延伸ポリエステル離型フィルムのシリコンコートを施した反対面に帯電防止加工をして、かつアニール加工を施した離型フィルム６（帝人デュポンフィルム社製、商品名Ａ−３１、１５０℃で３０分加熱した時のフィルムの巻き取り方向の収縮率が０．４％）を貼り合わせ、その後支持フィルムであるポリエステルフィルムを剥離して最終製品とした。
【０１１８】
次に別途準備したインクジェット方式の一種であるピエゾ方式のプリンター（武藤工業社製ＲＪ−６０００）により、転写紙(Gradess S-coat Paper)に画像を印刷した。昇華型インクジェット用インクは昇華性染料を含有する紀和化学工業社製インクジェット用インク（シアン、マゼンタ、イエロー、ブラック、ライトシアン、ライトマゼンタの６色セット）を使用した。上記で作製した印刷用積層体の表面樹脂層１に前記転写紙の印刷面を当て、ヒートバキュームアプリケーター(HUNT EUROPE社製 VacuSeal 4468)を使用して、真空度３．９９×１０³Ｐａ（３０mmｇ）にて設定温度約１７０℃で約７分間加熱圧着処理を実施し、印刷用積層体と前記転写紙を共に加熱することにより、前記転写紙に印刷された画像を印刷用積層体に拡散染色させて染料移行防止性着色性樹脂層１２に画像を転写させた。
【０１１９】
（実施例２）
図２に示す表面樹脂層１用の樹脂組成物を調整するに当り、フッ素系樹脂としてフルオネートＫ−７０３（大日本インキ化学工業社製、重量平均分子量４００００、固形分水酸基価７２、不揮発分約６０％）、硬化剤としてバーノックＤＮ−９５０、紫外線吸収剤としてチヌビン９００、酸化防止剤としてチヌビン２９２を使用した。この実施例２における表面樹脂層１用樹脂組成物の配合割合は、フルオネートＫ−７０３が約１００部、バーノックＤＮ−９５０が約２５部、チヌビン９００が約１部、チヌビン２９２が約１部である。そして、前記組成物をポリエステルフィルム上に乾燥膜厚が約２０μｍになる様に塗布し、約１４０℃で約１０分間加熱乾燥を行い、表面樹脂層１を得た。続いて上記で作製した表面樹脂層１上にポリカーボネート系無黄変型ウレタン樹脂ＮＹ−３３１（大日本インキ化学工業社製、不揮発分約２５％、溶剤ＤＭＦ、１００％モジュラス約５５ｋｇ／ｃｍ^２）を用い、乾燥膜厚が約２０μｍになるように塗布し、約１４０℃で約１０分間加熱乾燥を行い、着色性樹脂層２を作製した。続いて前記着色性樹脂層２上に前記した参考例２で合成されたビニル系重合体（ａ−２）が約１００部、硬化剤としてバーノックＤＮ−９５０を約５０部、配合した樹脂組成物を前記着色性樹脂層２上に乾燥膜厚が約１５μｍになるように塗布し、約１４０℃で約１０分間乾燥を行い、染料移行防止層３を作製した。続いて前記染料移行防止層３上に、アクリル系樹脂としてアクリディック４９−３９４−ＩＭ（大日本インキ化学工業社製、不揮発分約５０％）約１００部、バーノックＤＮ−９５０を約１５部、配合した樹脂組成物を乾燥膜厚が約２０μｍになるように塗布し、約１４０℃で約１０分間乾燥を行い、可撓性樹脂層４を作製した。
【０１２０】
こうして得られた印刷用積層体の可撓性樹脂層４の表面に、図５に示す通り、実施例１と同様の方法で粘着剤層５及び離型フィルム６を形成し最終製品とした。
【０１２１】
次に、実施例１と同様の方法で、表面樹脂層１に転写紙の印刷面を当て着色性樹脂層２に画像を転写させた。
【０１２２】
（実施例３）
表面樹脂層１の樹脂組成物の配合液と着色性樹脂層２の配合液を下記のように変更する以外は、構造、寸法および製造方法等は実施例２の場合と同様である。この実施例での表面樹脂層１用樹脂組成物の配合例は、フルオネートＫ−７００（大日本インキ化学工業社製、重量平均分子量約７００００、固形分水酸基価４８、不揮発分約５０％）が約１００部、硬化剤としてスミマールＭ−１００Ｃ（住友化学工業社製メチル化メラミン樹脂、不揮発分１００％）が約１５部、硬化触媒としてネイキュアー３５２５（ＫＩＮＧ ＩＮＤＵＳＴＲＩＥＳ社製、ジノニルナフタレンジスルフォン酸）が約１．３部、チヌビン９００が約１部、チヌビン２９２が約１部である。
【０１２３】
着色性樹脂層２用の樹脂組成物の配合例は、バーノックＤ６−４３９（大日本インキ化学工業社製アルキッド樹脂、固形分水酸基価１４０、不揮発分８０％）が約１００部、硬化剤としてバーノックＤＮ−９８０（大日本インキ化学工業社製ポリイソシアネートプレポリマー、不揮発分７５％）を約８２部である。
【０１２４】
（実施例４）
表面樹脂層１用の樹脂組成物の配合液を下記のように変更する以外は、構造、寸法および製造方法等は実施例２の場合と同様である。この実施例では、表面樹脂層１用樹脂組成物の配合例は、アクリディックＡ−９５２１（大日本インキ化学工業社製シリコンアクリル樹脂、固形分５０％）が約１００部、硬化剤としてアクリディックＨＺ−１０１８（大日本インキ化学工業社製エポキシ基含有シリコン化合物、固形分５５％）が約２２部である。
【０１２５】
（実施例５）
印刷用積層体の表面に印刷表示が可能な剥離性仮表示表面層を積層する以外は、構造、寸法および製造方法等は実施例２の場合と同様である。本実施例２で作製した印刷用積層体の表面樹脂層１上に水性フッ素樹脂として大日本インキ化学工業社製フルオネートＦＥＭ−６００（固形分４５％）を使用して乾燥膜厚が約１５μｍになるように塗布し、約１１０℃で約５分の加熱乾燥を実施した。続いて前記乾燥膜上に乾燥膜厚が約３０μｍになるようにインクジェット受理剤として高松油脂社製ＭＺ−１００（非晶質二酸化珪素、ポリウレタンおよびビニル系樹脂の混合物、固形分１５％、固形分中の多孔質顔料含有率：約５６％）を塗布し、約１１０℃で約５分の加熱乾燥を実施した。このように作製した仮表示表面層に実施例１と同様の方法にて画像を印刷した。その後熱風乾燥機（ヤマト科学社製Ｆｉｎｅ Ｏｖｅｎ ＤＦ６Ｌ）を約１７０℃に設定し、約７分間加熱処理を実施して昇華性染料を拡散浸透させて、前記印刷用積層体側の着色性樹脂層２に画像を印刷し、その後仮表示表面層をフィルム状態で剥離した。
【０１２６】
（実施例６、参考例）
図２に示す染料移行防止層３として、アニール処理された２軸延伸ポリエステルフィルム（帝人デュポンフィルム社製、商品名ＭＸ５３４、１５０℃で３０分加熱した時のフィルムの巻き取り方向の収縮率が０．３％、膜厚９７μｍ）上に、実施例２と同様の配合からなる着色性樹脂層２用の樹脂組成物を乾燥膜厚が約２０μｍになるように塗布し、約１４０℃で約１０分間加熱乾燥を行い、着色性樹脂層２を作製した。
【０１２７】
続いて前記着色性樹脂層２上に、実施例２に記載した表面樹脂層１用の樹脂組成物を乾燥膜厚が約２０μｍになるように塗布し、約１４０℃で約１０分間加熱乾燥を行い、表面樹脂層１を得た。このようにして得られた印刷用積層体の染料移行防止層である２軸延伸ポリエステルフィルムの裏面に、実施例１と同様の方法で粘着剤層５及び離型フィルム６を形成し最終製品とした。次に、実施例１と同様の方法で、表面樹脂層１に転写紙の印刷面を当て着色性樹脂層２に画像を転写させた。
【０１２８】
（比較例１）
染料移行防止層３の工程を省略する以外は、構造、寸法及び製造方法等は実施例２の場合と同様である。
【０１２９】
（比較例２）
染料移行防止層３及び可撓性樹脂層４の工程を省略する以外は、構造、寸法及び製造方法等は実施例２の場合と同様である。
【０１３０】
（比較例３）
表面樹脂層１の樹脂組成物の配合液と着色性樹脂層２、染料移行防止層３を下記のように変更し、可撓性樹脂層４を省略する以外は、構造、寸法および製造方法等は実施例２の場合と同様である。
【０１３１】
両面易接着処理を行った２軸延伸ポリエステルの支持フィルム（アニール処理なし、染料移行防止層３として使用する。）上にポリウレタン系樹脂溶液バーノックＬ７−９２０（大日本インキ化学工業社製、不揮発分２５±１％、溶剤トルエン、ｓｅｃ−ブタノール）を乾燥膜厚が２０μｍになるように塗布し、約１４０℃で約１０分間加熱処理を行い、着色性樹脂層２を作製した。続いて前記着色性樹脂層２上に下記配合の塩化ビニル系樹脂塗料を乾燥膜厚が約２０μｍになるように塗布し、約１４０℃で約１０分間加熱乾燥を行い、表面樹脂層１を作成した。
（１） 塩化ビニル樹脂 １００部
（２） エチレン／ビニルエステル樹脂 ２５部
（３） ポリエステル可塑剤 １０部
なお上記塩化ビニル樹脂としては、ニカビニルＳＧ−１１００Ｎ（日本カーバイド工業社製）をエチレン／ビニルエステル樹脂としてはエルバロイ（三井・デュポンポリケミカル社製、商品名）をそれぞれ用い、またポリエステル可塑剤としてはプロピレングリコール、ブタンジオール、及びヘキサンジオールからなる混合二価アルコールとアジピン酸とから合成された数平均分子量（Ｍｎ）が約３０００のものを用いた。
【０１３２】
以上の実施例、比較例について画像転写後の結果と試験方法をまとめて次の表２〜５に示す。
【０１３３】
【表２】

【０１３４】
【表３】

【０１３５】
【表４】

【０１３６】
【表５】

【０１３７】
（備考）表２〜５における黒星印１〜７は、（注１）〜（注７）に置き換えて説明する。
（注１）南面４５°屋外暴露試験（試験場所：和歌山県）試験期間は一年
○（鮮明さを保持）＞△（画像にややにじみあり）＞×（画像がぼやけ不鮮明である）
（注２）ユウブコン（米国アトラス社製）促進耐候性試験
１サイクル：ＵＶ照射６０℃×４時間／凝結４０℃×４時間
試験時間：１０００時間
○（鮮明さを保持）＞△（画像にややにじみあり）＞×（画像がぼやけ不鮮明である）
（注３）ＪＩＳ Ｚ ９１１７に記載のサンシャインカーボン式促進耐候性試験の条件に準拠、試験時間は１０００時間。
【０１３８】
○（鮮明さを保持）＞△（画像にややにじみあり）＞×（画像がぼやけ不鮮明である）
（注４）エリクセン試験機（東洋精機製作所製）
貼り付け基板：ＪＩＳ Ｈ ４０００に規定されるＡ５０５０２Ｐの硬度Ｈ２４の１ｍｍ厚さのアルミニウム板。
試験方法：印刷用積層体を基板に貼り付け、常温で４８時間放置後、基板の後面から半径１０ｍｍのポンチを押し当て、６ｍｍ押し込んで曲面を作成する。その後、（注２）のユウブコン促進耐候性試験を１０００時間行う。
○：外観異常なし。
△：押し出した曲面の頂上にクラック発生。
×：シート全体が基板より浮き上がる。
（注５）ヒートバキュームアプリケーター（ＨＵＮＴ ＥＵＲＯＰＥ社製 ＶａｃｕＳｅａｌ ４４６８）を使用して、真空度３．９９×１０^３Ｐａ（３０ｍｍＨｇ）にて設定温度約１７０℃で約７分間加熱圧着処理を実施し、印刷用積層体と前記転写紙を共に加熱することにより、前記転写紙に印刷された画像を印刷用積層体に拡散染色させて画像を転写させた後のフィルムの状態。
○：外観異常なし。
×：シート全体にシワが発生。
（注６）試験方法は（注３）と同じ。色差ΔＥはＪＩＳ Ｚ ８７２２に規定する刺激値直読方式によって測定し、「ＪＩＳ Ｚ ８７３０色差表示方法６」に規定する色差式を用いて求めた。
（注７）試験方法は（注１）と同じ。色差ΔＥは（注６）と同様にして求めた。
【０１３９】
以上の表２〜５のとおり、実施例１は、可撓性樹脂層を形成していないため３次元曲面貼り適性は良くなかったが、画像の鮮明性保持力に優れ、加熱転写後のシートの状態も良好であった。実施例２〜５は、３次元曲面貼りにも適し、画像の鮮明性保持力に優れ、加熱転写後のシートの状態も良好であった。実施例６は、３次元曲面貼り適性は不良であるが、染料移行防止層にアニール処理された２軸延伸ポリエステルフィルムを使用しているため画像の鮮明性保持力に優れ、加熱転写後のシートにシワの発生は認められなかった。比較例１〜２は、染料移行防止層３を形成していないため画像のにじみ等が発生し、画像の鮮明性保持力が劣っていた。比較例３は、染料移行防止層に２軸延伸ポリエステルフィルムを使用しているため、３次元曲面貼り適性が不良で、かつ加熱転写後のシートにシワが発生していた。また、表面樹脂層１に塩化ビニル系樹脂を使用しているため、画像の鮮明性保持力が低く、画像の耐退色性も悪かった。したがって、染料移行防止層３を形成した本発明の印刷用積層体は、長期間の放置条件に対しても画像のにじみやぼやけが発生することなく画像の鮮明性を保つことができ、耐退色性に非常に優れた高耐候性の印刷積層体を実現することができた。また、２軸延伸ポリエステルを使用する場合には、アニール処理を施したフィルムを使用すると加熱によるシワの発生を防止できた。また、曲面貼りに使用する場合には、染料移行防止層３の下部に可撓性樹脂層４を形成すれば、十分に対応できることが分かった。
【０１４０】
【発明の効果】
以上説明したとおり、本発明は、内層に昇華性染色剤と親和性がある着色性樹脂層と、前記染色剤の移行を防止する染料移行防止層を形成したことにより、印刷された昇華性染色剤の移行を防止することが可能な印刷用積層体とこれを用いた印刷方法と印刷物を提供できる。また、本発明は、染料移行防止層のさらに下層に、前記染料移行防止層よりも伸び率が大なる可撓性樹脂層を備えたことにより、曲面の基体に貼ることが可能なフレキシビリティーを有する印刷用積層体とこれを用いた印刷方法と印刷物を提供できる。
【図面の簡単な説明】
【図１】本発明の参考例における印刷用積層体の断面図である。
【図２】本発明の一実施形態における印刷用積層体の断面図である。
【図３】本発明の別の実施形態における印刷用積層体の断面図である。
【図４】本発明のさらに別の実施形態における印刷用積層体の断面図である。
【図５】本発明のさらに別の実施形態における印刷用積層体の断面図である。
【図６】本発明のさらに別の実施形態における印刷用積層体の断面図である。
【図７】本発明のさらに別の実施形態における印刷用積層体の断面図である。
【図８】Ａは本発明のさらに別の実施形態を示す工程図で、ポリエステルフィルム上にガラス球仮固着層を形成し、その表面に透明のガラス球を複数平面上に埋め込み、金属反射膜を形成した部分の断面概略図、Ｂは同、ポリエステルフィルムの上にプライマー層を形成し、その上に支持樹脂シート形成した部分の断面概略図、Ｃは同、支持樹脂シートをガラス球仮固着層の表面に沿わせた部分の断面概略図、Ｄは同、支持樹脂シートをガラス球仮固着層の表面へ押圧した部分の断面概略図、Ｅは同、支持樹脂シート表面からポリエステルフィルムと共にガラス球仮固着層を剥がしている部分の断面概略図、Ｆは同、支持樹脂シート表面を本発明の印刷用積層体で覆い、柄付きエンボスロールで加熱圧着成形を行なう前の部分の断面概略図、Ｇは同、エンボスロールで加熱圧着成形を行っている部分の断面概略図である。
【符号の説明】
１ 表面樹脂層
２ 着色性樹脂層
３ 染料移行防止層
４ 可撓性樹脂層
５ 粘着剤層
６ 離型材
１２ 染料移行防止性着色性樹脂層
１０１ 焦点層フィルム
１０２ 高屈折ガラスビーズ
１０３ 金属反射膜
２０１ ガラスビーズ固着層
２０２ 高屈折ガラスビーズ
２０３ 焦点層フィルム
２０４ 金属反射膜
３０２ ガラス球
３０３ 金属反射膜
３０４ 支持樹脂シート
３０５ プライマー層
３０６ ポリエステルフィルム
３０７ ガラス球仮固着層
３０８ ポリエステルフィルム
３０９ 柄付きエンボスロール
３１０ エンボス溝[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a printing laminate used for sublimation dyeing in which a sublimable dye is penetrated into a resin by heating, a printing method using the same, and a printed material. More specifically, the present invention relates to a printing laminate capable of preventing migration of a sublimable dye that occurs during dyeing or with time after dyeing, a printing method using the same, and a printed material.
[0002]
[Prior art]
Conventionally, when printing an image or the like using a sublimable dye on a printing laminate, once printing on paper using an ink containing a sublimable dye, the printing surface of the paper is laminated for printing. The printing surface of the paper is brought into close contact with the printing laminate by using a vacuum heating and pressing machine or a hot roll, etc., and then subjected to thermocompression to allow the sublimable dye to penetrate into the printing laminate. I was As another method, printing is performed using an ink containing a sublimable dye on a temporary display surface layer that receives the ink provided on the surface of the printing laminate, and thereafter, heating is applied to the inside of the printing laminate. The desired printed image or the like was obtained by diffusing and penetrating the dye. At the time of printing, the dye sublimated to the molecular size penetrates into the resin and the image is colored and printed on the colorable resin layer, but the transfer temperature and transfer time at that time are lower or shorter than the optimum conditions for transfer printing. If the color density is not sufficient if obtained, and if it is more than the optimal condition, sublimation dyeing is performed on the layer continuous to the coloring resin layer, for example, the pressure-sensitive adhesive layer or adhesive layer provided for attaching the substrate. The agent penetrates and spreads and spreads, causing a problem that the sharpness of the image is impaired and the outline of the image is blurred. Moreover, even if sublimation dyeing printing is performed under optimal conditions, the dyeing agent is successively transferred to the layer continuous with the above-described coloring resin layer one after another, and the dyeing agent to be retained in the coloring resin layer is dispersed. As a result, problems such as discoloration and fading of the color and blurring of the outline of the image have occurred. As a conventional example, for example, as proposed in Patent Document 1 below, in manufacturing a printing laminate, a coloring resin layer or a surface resin layer and the like are sequentially laminated on a base film such as polyester, A printing laminate was produced.
[0003]
[Patent Document 1]
JP-A-2002-79751
[0004]
[Problems to be solved by the invention]
However, the technique of Patent Document 1 has a problem that transfer of the dye cannot be prevented if the polyester film used is not stretched. If a biaxially stretched polyester film is used, since the biaxially stretched polyester film increases the crystallinity and intramolecular density of the resin by stretching, the migration of the dyeing agent between layers can be prevented to some extent. Is not sufficient to maintain the sharpness of the image, and the outline of the printed image is blurred in a short time. In addition, if a biaxially stretched polyester film is used as the process base material, the biaxially stretched polyester film shrinks due to heating during sublimation dyeing, causing a problem that wrinkles and streaks are generated in the printing laminate. Was.
[0005]
In addition, when the biaxially stretched polyester film is stuck on a three-dimensional curved surface such as wrapping of a vehicle, the rigidity of the biaxially stretched polyester film is insufficient in flexibility and elongation, and it is difficult to stick the biaxially stretched polyester film on a curved surface. Therefore, in the market, the color density of an image can be maintained for a long period of time, the sharpness of the image can be maintained, and wrinkles and streaks do not occur at the time of heat transfer. Development of a laminate for printing has been desired.
[0006]
The first object of the present invention is to provide a printing laminate capable of preventing migration of a sublimable dye, a printing method and a printed material using the same, in order to solve the conventional problems. I do.
[0007]
A second object of the present invention is to provide a printing laminate having flexibility that can be attached to a curved substrate, a printing method using the same, and a printed material.
[0008]
[Means for Solving the Problems]
In order to achieve the first object, a printing laminate of the present invention is a printing laminate in which a sublimable dye is penetrated into a resin layer by heating to be colored, and the sublimation is performed in order from the surface. A surface resin layer (A), which has a low affinity for the acidic dye and allows the dye to pass therethrough,As the dye transfer preventing coloring resin layer (B),Affinity with the stainA coloring resin layer (B1) and a dye transfer preventing layer (B2) for preventing transfer of the dye are laminated, and the dye transfer preventing layer (B2) has a glass transition temperature (Tg) of 70. A resin layer mainly composed of a vinyl-based resin having a SP value of 9.0 or more and a SP value of 9.0 or more, and a film thickness of 1 μm or more and 100 μm or less.It is characterized by that.
[0009]
Next, in order to achieve the second object, the printing laminate of the present invention comprisesDye transfer prevention layer (B2)In the further lower layer ofDye transfer prevention layer (B2)It is characterized by having a flexible resin layer (C) having a larger elongation rate.
[0010]
The printing method of the present inventionThe mark of the present inventionA method for printing a printing laminate, comprising printing on a transfer paper using an ink containing a sublimable dye, bringing an image forming surface of the transfer paper into contact with the surface resin layer (A), Thereafter, a heat treatment is performed to sublimate the sublimable dye,WritingIt is characterized in that the color resin layer (B1) is diffused and dyed.
[0011]
The printed matter of the present invention,The markThe printing is performed using a printing method.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present invention, the surface resin layer (A) having a low affinity for the sublimable dye and allowing the dye to pass therethrough, and a dye transfer having an affinity for the dye and preventing the dye from migrating. And a protective coloring resin layer (B). By laminating the surface resin layer (A) on the dye transfer-preventing coloring resin layer (B) as described above, the sublimable dye is easily passed through the surface resin layer (A) by heating and used for printing. It becomes possible to penetrate into the coloring resin layer (B) inside the laminate, and the dye remaining in the coloring resin layer can be protected from ultraviolet rays, water and the like, and the fading resistance and the like can be improved. In addition, by making the colorable resin layer dye transfer-preventing, it is possible to prevent the dye from migrating to the layer not intended for coloring, thereby preventing discoloration of the image and blurring of the outline of the image. Become.
[0013]
The dye transfer preventing coloring resin layer (B) further includes, in order from the surface, a coloring resin layer (B1) having an affinity for the dye and a dye transfer preventing layer (B2) for preventing the transfer of the dye. ) May be formed separately. By providing a dye transfer prevention layer below the colorable resin layer, the dye is more effectively prevented from migrating to an undesired lower layer and causing discoloration of the image and blurring of the outline of the image. Becomes possible.
[0014]
Next, the dye-transfer-preventive coloring resin layer (B) or the dye-transfer-preventive layer (B2) is further below the dye-transfer-preventive colorable resin layer (B) or the dye-transfer preventive layer (B2). When the flexible resin layer (C) having a large elongation is provided, even if the printing laminate of the present invention is stretched when attached to a substrate having a three-dimensional curved surface, cracks occur in the dye transfer prevention layer. Can be prevented, and the dye can be prevented from migrating from the crack to another layer. Thereby, flexibility can be imparted to the printing laminate, so that the printing laminate can be attached to a substrate having a three-dimensional curved surface.
[0015]
In the present invention, it is preferable that the dye-transfer-preventive coloring resin layer (B) or the dye-transfer-preventive layer (B2) is formed of a resin containing a vinyl resin having an SP value of 9.0 or more as a main component. . As described above, by using a resin containing a vinyl resin having a SP value of 9.0 or more as a main component in the dye transfer preventing layer, the transfer of the dye can be more effectively prevented.
[0017]
Further, it is preferable that the surface resin layer (A) is formed of a fluororesin made of a fluoroolefin copolymer soluble in a solvent. By using a fluoroolefin-based copolymer soluble in a solvent for the surface resin layer (A) of the laminate for printing in this manner, the sublimable dye is efficiently heated and colored inside the laminate for printing. It can be penetrated into the conductive resin layer, and the outdoor weather resistance can be further improved.
[0018]
Further, the surface resin layer (A) may be formed of a silicon-modified acrylic resin. By using the silicon-modified acrylic resin for the surface resin layer (A) of the printing laminate, the sublimable dye is efficiently penetrated into the coloring resin layer inside the printing laminate by heating. And the outdoor weather resistance can be further improved.
[0019]
Further, it is preferable that the dye transfer preventing coloring resin layer (B) or the coloring resin layer (B1) does not contain a low molecular weight compound having a molecular weight of about 1300 or less in excess of about 20% by weight. By reducing the amount of the low molecular weight compound contained in the coloring resin layer, the effect of preventing the transfer of the dye is increased.
[0020]
Further, a matting agent is added to the surface resin layer (A), and the surface resin layer has a 60-degree specular gloss (method 3 (60-degree specular gloss) defined in JIS Z8741 (method for measuring specular gloss)). Is preferably set to 70 or less, since reflection of lighting equipment such as a fluorescent lamp can be prevented.
Further, at least one of the surface resin layer (A), the dye transfer preventing coloring resin layer (B) and the coloring resin layer (B1) is used to prevent discoloration and fading of an image and to improve the durability of the resin. For this, it is preferable to use at least one selected from an ultraviolet absorber, a light stabilizer and an antioxidant, but the ultraviolet absorber, light stabilizer and antioxidant used at this time are preferably of high molecular weight type. . By making the UV absorber, light stabilizer, and antioxidant high molecular weight in this way, the appearance of phases due to phase separation from the transparent resin such as the surface layer, defects such as bleed-out, and during the heat sublimation treatment Is reduced, a transparent resin stable over a long period of time can be formed, and an image can be protected from ultraviolet rays or the like for a long period of time.
[0021]
In addition, at least one of the surface resin layer (A), the dye-transfer-preventive coloring resin layer (B), the dye-transfer-preventive layer (B2), and at least one of these lower layers is provided with light diffusing fine particles. Is added to provide a light diffusion function, so that the laminate can be used as a backlight film if illumination is applied from the back side of the laminate.
[0022]
Further, a white layer is formed by using a white pigment for at least one of the dye transfer preventing coloring resin layer (B), the coloring resin layer (B1) and the dye transfer preventing layer (B2). If formed, the transmission density of the printed image can be improved. Further, a layer containing high refractive glass beads is laminated below the dye transfer preventing coloring resin layer (B), the dye transfer preventing layer (B2) or the flexible resin layer (C). If a retroreflective layer on which a metal reflective film is formed is provided below the layer containing the refractive glass beads, the printing laminate is retroreflected by illumination of a vehicle headlight or the like at night, and the printed matter at night is printed. This is preferable because the visibility is improved and the traffic safety and the advertising effect are greatly improved.
[0023]
Similarly, a fixing layer in which a high refractive glass bead is fixed below the dye transfer preventing colored resin layer (B), the dye transfer preventing layer (B2) or the flexible resin layer (C), and a focus resin layer. It is preferable to provide a retroreflective layer in which layers are sequentially stacked and a metal reflective film is formed below the focal resin layer because the same effect as described above can be obtained.
[0024]
Furthermore, a plurality of transparent spheres provided with a metal reflective film in a lower hemisphere, a support resin sheet holding the plurality of transparent spheres, and the plurality of transparent spheres are covered by being disposed on the surface side of the support resin sheet. In a retroreflective sheet made of a transparent cover film, and provided with a joint for holding the cover film on the support resin sheet, when the cover film is the laminate for printing, However, a printing laminate that is much brighter and retroreflected is obtained, which is more preferable.
[0025]
Further, the surface resin layer of the laminate for printing is [M²⁺ _1-XM³⁺ _X(OH)_Two]^{X +}[A^n- _{X / n}・ MH_TwoO]^X-(M²⁺Is a divalent metal ion, M³⁺Is a trivalent metal ion, A^n-Is an n-valent anion, X is greater than 0 and 0.33 or less, 0 ≦ m≤It is preferable to coat with the coating film forming composition containing the fine particles of hydrotalcites and metal oxides as described in 2), since a contaminant does not adhere for a long time and a clear image can be displayed.
[0026]
Further, it is preferable that an antistatic treatment is applied to a release material such as a release film or release paper applied to the pressure-sensitive adhesive layer or the adhesive layer provided on the back surface of the printing laminate. The release material such as the release film or release paper is subjected to an antistatic treatment, and is generated by static electricity generated when the sheet is unwound and friction between the printing laminate and the printing machine during printing by an inkjet printing machine. It is possible to prevent the discharge direction of the ink discharged from the print nozzles from being disturbed due to the static electricity, thereby preventing the printed image from being disturbed. That is, a precise image can be formed.
[0027]
Furthermore, it is the printing laminate in which at least one releasable temporary display layer capable of printing and displaying is provided on the surface resin layer (A), wherein the surface resin layer (A) of the temporary display layer The non-contact surface side has an absorptivity of the ink containing the sublimable dye, and is capable of diffusing and dyeing the printing laminate by sublimating the sublimable dye by heat treatment. After the heat treatment, if the temporary display layer is provided on the surface resin layer of the printing laminate, the temporary display layer is capable of being peeled off in a film state from the surface resin layer of the printing laminate. A desired image or the like can be directly printed on the laminate for use by using a sublimable dye, and then a heat treatment is preferably performed, whereby a clear image or the like having high weather resistance can be easily obtained.
[0028]
In the printing method of the present invention, the transfer paper is printed using an ink containing a sublimable dye, and the image forming surface of the transfer paper is brought into contact with the surface resin layer (A) of the printing laminate. Thereafter, a heat treatment is performed to sublimate the sublimable dye, and the dye-transfer-preventive coloring resin layer (B) or the coloring resin layer (B1) is dyed by diffusion.
[0029]
In addition, by printing on at least one peelable temporary display layer capable of printing and displaying by a known and common method such as an ink jet printer, a thermal transfer printer, or a laser printer, it can be used as a temporary display laminate and becomes unnecessary. For example, when the temporary display layer is peeled off, the substrate on which the printed laminate of the present invention is adhered becomes visible, and can be used as a transparent protective film for the substrate.
[0030]
In addition, the temporary display layer is printed using an ink containing a sublimable dye, and then subjected to a heat treatment to sublimate the sublimable dye, thereby providing a clear image having high weather resistance. Is obtained.
[0031]
In addition, the printing is more preferably performed by an inkjet method using an inkjet printer capable of performing full-color printing easily.
[0032]
Further, the heat treatment temperature after printing is set at 150 from the point of improving the workability by sublimating the sublimable dye in a shorter time without giving a large heat damage to the release film or the like on the back surface of the printing laminate. It is preferably in the range of -200 ° C.
[0033]
Further, if the printing surface is dried before the heat treatment, the diffusibility of the sublimable dye during the heat treatment becomes uniform, which is more preferable.
[0034]
The printing laminate of the present invention will be described in detail below based on embodiments.
[0035]
Figure21 is a configuration diagram of a printing laminate of the present invention. A release paper or a release film may be integrated under the printing laminate via a pressure-sensitive adhesive layer or an adhesive layer. As the substance that can be used for the colorable resin layer, it is preferable to use a synthetic resin having an affinity for the dyeing agent in order to efficiently capture the dye that has sublimated and diffused and to develop a high concentration of color. More preferably, a resin having heat resistance so as not to remarkably soften at a heating temperature of about 150 ° C. to about 200 ° C. at the time of sublimation dyeing or to develop tack (so-called sticky). Just apply. In particular, it is preferable to use a resin that is cured by radiation. Useful forms of radiation include electron beams, ultraviolet radiation, nuclear radiation, microwave radiation, and heat, the materials that cure with radiation are well known in the art. In addition, the coloring resin layer itself is uniformly dispersed and contained in the coloring resin layer an ultraviolet absorber of 70% or more, preferably 80% or more, and more preferably 90% or more. It is preferable for protecting the agent from ultraviolet rays and the like. As a material satisfying such required characteristics, specifically, a synthetic resin such as a vinyl resin, an acrylic resin, an alkyd resin, a polyester resin, a urethane resin, and an epoxy resin can be used.
[0036]
Furthermore, the low-molecular-weight compound in the resin gradually transfers the dye once fixed, and as a result, causes a problem that the outline of an image becomes unclear. For this reason, it is preferable that low-molecular-weight compounds remain in the coloring resin layer or that additives such as plasticizers are not used as much as possible, and that the low-molecular-weight compounds contained in the coloring resin layer be reduced as much as possible. This is an effective means for stably carrying an image. The above-mentioned low molecular weight compound is a compound having a molecular weight of about 1300 or less, and its content is preferably about 20% by weight or less, preferably about 15% by weight or less, and more preferably about 10% by weight or less. When a low molecular weight compound having a molecular weight of about 1300 or less is used in excess of about 20% by weight, the outline of the printed image tends to be blurred in a short time.
[0037]
The laminate for printing colored by the sublimation dyeing method may be used by providing a layer of an adhesive or an adhesive on the back side of the coloring resin layer and attaching it to a base material such as metal, wood, plastic, or glass. Also, it is used by sandwiching it between plastics and the like. However, at this time, the dye gradually diffuses and transfers from the coloring resin layer to the adhesive, the adhesive, or the sandwiched plastic. As a result, problems such as blurring of the image, blurring of the edge of the image, and mixing of the printed hues and blurring of the image occur.
[0038]
In order to solve this problem, a dye transfer preventing property for preventing the transfer of the dye is provided in the colorable resin layer, or a dye transfer for preventing the transfer of the dye continuously to the colorable resin layer. It is effective to provide a prevention layer.
[0039]
One example of a dye-transfer-preventing material or a preferred material for the dye-transfer-preventing layer is a biaxially-stretched film, particularly a biaxially-stretched film in which crystallization has progressed and the intermolecular density has increased. In particular, a biaxially stretched polyester film stretched by 10% or more, preferably 50% or more, more preferably 100% or more, and particularly preferably 200% or more in each of the winding direction and the width direction is suitable. If the stretching ratio is less than 10%, it is insufficient to prevent the transfer of the sublimable dye. Furthermore, there is a problem in that the biaxially stretched polyester film shrinks due to heat generated when a sublimable dye is penetrated into the resin by heating and colored, thereby causing wrinkles and streaks. In order to solve this problem, it is preferable to apply a biaxially stretched polyester film that has been annealed at a temperature equal to or higher than the glass transition temperature by heating to a fixed length or relaxing after heating after biaxial stretching. It is preferable to apply a film having a shrinkage of 1.0% or less, preferably 0.8% or less, more preferably 0.6% or less in the winding direction of the film when heated for 30 minutes. If a biaxially stretched polyester film having a shrinkage ratio of more than 1.0% is used, defects such as wrinkles, streaks, etc., which cause abnormalities in the appearance of wrinkles, streaks, etc. due to the heat generated when a sublimable dye is penetrated into the resin by heating and colored. It is not preferable because it occurs. In the case of a biaxially stretched polyester film, the orientation of the polymer molecules proceeds by stretching, the crystallinity ratio increases, and the surfaces of the polymer molecules in contact with each other increase. As a result, it is considered that the increase in the intramolecular attractive force of the polymer makes it possible to effectively prevent the transfer of the dye from the coloring resin layer. However, when a biaxially stretched polyester film is used for the dye transfer preventing layer when sticking to a three-dimensional curved surface, the rigidity of the film makes the elongation insufficient, making it difficult to stick to a three-dimensional curved surface.
[0040]
The inventor of the present invention has conducted intensive studies to complete a new dye transfer preventing layer capable of maintaining the dye transfer preventing performance in place of the biaxially stretched film. As a result, the dye transfer preventing layer has an SP value (Solubility Parameter). (Solubility parameter) of a resin containing a vinyl resin having a major component of 9.0 or more as a main component, thereby successfully completing a dye transfer preventing layer having excellent dye transfer preventing properties. In the case of preventing the transfer of a sublimable dye with a vinyl resin, it is preferable to use a vinyl resin having an SP value of 9.0 or more, more preferably 9.25 or more, and still more preferably 9. It is 50 or more. Use of these vinyl-based resins as uncured or in combination with a curable substance and as a cross-linked three-dimensional polymer allows for the transfer of sublimable dyes. It is preferable because it can be prevented.
[0041]
Here, the SP value is a parameter indicating the polarity of the resin, and the higher the SP value, the higher the polarity of the resin.
[0042]
The SP value can be measured by the method described below. The SP value of the vinyl copolymer can be predicted by previously measuring the SP value of the homopolymer of the vinyl monomer used. That is, the SP value of the copolymer can be estimated from the sum of the product of the weight fraction of each vinyl monomer constituting the copolymer and the SP value of the homopolymer.
[0043]
An actual measurement example of the SP value of a typical homopolymer is as follows: methyl methacrylate = 10.6, n-butyl methacrylate = 8.4, ethyl methacrylate = 9.5, β-hydroxyethyl methacrylate = 11.5, n- Butyl acrylate = 8.6.
[0044]
For example, the SP value of a copolymer consisting of methyl methacrylate / n-butyl acrylate / β-hydroxyethyl methacrylate = 50/40/10 (weight ratio) is (10.6 × 0.5) + (8.6 × 0 .4) + (11.5 × 0.1) = 9.89, and a value close to 9.92 actually measured by the following method for the SP value of this copolymer can be obtained.
[0045]
The method for measuring the SP value of the vinyl resin is as follows.
[0046]
0.5 g of the resin solid content is weighed into a 100 ml Meyer flask, and 10 ml of tetrahydrofuran (THF) is added to dissolve the resin. While maintaining the solution at a liquid temperature of 25 ° C. and stirring with a magnetic stirrer, hexane was added dropwise using a 50 ml burette, and the amount of drop (V) at the point where the solution became turbid (turbid point) was added._h).
[0047]
Next, when deionized water was used instead of hexane, the drop amount (V_d).
[0048]
V_h, V_dThus, the SP value δ of the resin is
SUH, CLARKE [J. Polym. Sci. A-1, Vol. 5, 1671-1681 (1967)], and can be obtained as follows.
δ = [(V_mh)^(1/2)δ_mh+ (V_md)^(1/2)δ_md] / [(V_mh)^(1/2)+ (V_md)^(1/2)]
here,
V_mh= (V_h・ V_t) / (Φ_h・ V_t+ Φ_t・ V_h),
V_md= (V_d・ V_t) / (Φ_d・ V_t+ Φ_t・ V_d)
δ_mh= Φ_h・ Δ_h+ Φ_t・ Δ_t,
δ_md= Φ_d・ Δ_d+ Φ_t・ Δ_t
φ_h, Φ_d, Φ_tA volume fraction of hexane, deionized water and THF at the cloud point
(Φ_h= V_h/ (V_h+10), φ_d= V_d/ (V_d+10))
δ_h, Δ_d, Δ_t; SP value of hexane, deionized water and THF
V_h, V_d, V_tHexane, deionized water, molecular volume of THF (ml / mol)
Next, various aromatic vinyl monomers such as styrene, α-methylstyrene, pt-butylstyrene or vinyltoluene are used as a vinyl monomer when synthesizing a vinyl resin;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dibromopropyl (meth) acrylate, tribromophenyl (meth) acrylate or alkoxy Various (meth) acrylates, such as alkyl (meth) acrylates;
Diesters of unsaturated dicarboxylic acids and monohydric alcohols, such as maleic acid, fumaric acid or itaconic acid;
Or various vinyl esters such as vinyl acetate, vinyl benzoate, and “Veoba” (a vinyl ester manufactured by Japan Epoxy Resin);
"Biscoat 8F, 8FM, 17FM, 3F or 3FM" (a fluorinated acrylic monomer under the trade name of Osaka Organic Chemical Co., Ltd.), perfluorocyclohexyl (meth) acrylate, di-perfluorocyclohexyl fumarate or Ni- Various fluorine-containing polymerizations such as vinyl esters, vinyl ethers, (meth) acrylates or unsaturated polycarboxylic acid esters containing a (per) fluoroalkyl group such as propyl perfluorooctanesulfonamidoethyl (meth) acrylate Active compound;
Vinyl monomers having no functional group such as olefins, such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, trifluoroethylene or chlorotrifluoropropylene;
Of (meth) acrylamide, dimethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-octyl (meth) acrylamide, diacetoneacrylamide, dimethylaminopropylacrylamide or alkoxylated N-methylolated (meth) acrylamides Such as various amide bond-containing vinyl monomers;
Various dialkylaminoalkyl (meth) acrylates, such as dimethylaminoethyl (meth) acrylate or diethylaminoethyl (meth) acrylate;
(Meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, carboxyl group-containing vinyl monomers such as itaconic acid;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( Hydroxyl-containing (meth) acrylates, such as (meth) acrylates;
Further, other copolymerizable vinyl monomers include (meth) acrylonitrile, glycidyl (meth) acrylate, (β-methyl) glycidyl (meth) acrylate, allyl glycidyl ether, vinylethoxysilane, α-methacryloxypropyl Examples include trimethoxysilane and trimethylsiloxyethyl (meth) acrylate.
[0049]
Preparation of the vinyl resin used in the present invention, using each raw material component of vinyl monomers, under normal pressure or under pressure, a batch system, a semi-batch system or a known system such as a continuous solution polymerization method. It can be carried out by making full use of polymerization (reaction) method, in which case azobisisobutyronitrile, benzoyl peroxide, t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate Various known radical-generating polymerization catalysts such as ate, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide and the like can be used alone or in combination of several depending on the polymerization conditions.
[0050]
As the solvent used for the solution polymerization, aromatic hydrocarbons such as toluene and xylene, and solvents such as ester solvents, ketone solvents, and alcohol solvents may be appropriately selected.
[0051]
Next, a synthesis example of a suitable vinyl resin having an SP value of 9.0 or more will be described.
[0052]
(Reference Example 1)
A four-necked flask equipped with a stirrer, a thermometer, an inert gas inlet, and a condenser is charged with 1000 parts of n-butyl acetate and heated to 110 ° C. Next, a mixture consisting of 650 parts of methyl methacrylate, 245 parts of n-butyl methacrylate, 100 parts of 2-hydroxyethyl methacrylate, 5 parts of methacrylic acid, and 15 parts of t-butyl peroxy-2-ethylhexanoate. Was added dropwise at 110 ° C. over 4 hours, and the reaction was continued for 6 hours while maintaining the temperature at 110 ° C. even after completion of the dropwise addition, to obtain a vinyl copolymer (a-1) having a nonvolatile content of about 50%. The vinyl copolymer (a-1) was dried, and the SP value was measured. As a result, it was 10.16.
[0053]
(Reference Examples 2 to 6)
Vinyl copolymers (a-2) to (a-6) were obtained in the same manner as in Reference Example 1 except that the ratio of the vinyl monomer was changed as shown in Table 1. Further, these were dried and the SP value was measured. The results are shown in Table 1.
[0054]
[Table 1]

[0055]
When a substance having an SP value of 9.0 or more is used as a dye transfer preventing layer, the film thickness is preferably set to 1 μm to 100 μm, preferably 2 μm to 80 μm, more preferably 3 μm to 60 μm. If it is less than 1 μm, the effect of preventing the migration of the dye is not sufficient, and if it exceeds 100 μm, the film strength becomes too high, and the suitability for sticking on a three-dimensional curved surface is unfavorably reduced. Further, the glass transition temperature (Tg) of the substance having an SP value of 9.0 or more applied to the dye transfer prevention layer is determined as follows.70 ° C or higher, preferably 80 ° CWith the above setting, the molecular motion is frozen even at a high temperature, such as when used outdoors in the middle of summer, and it is further preferable to prevent the migration of the dye.
[0056]
Another effective form of the dye transfer preventing layer can prevent dye transfer by forming a metal thin film by connecting the dye resin layer to the coloring resin layer or further connecting the dye transfer preventing layer. However, it is not preferable to form a retroreflective layer as a lower layer. Here, the metal layer can be formed of the following metals, and the thickness thereof varies depending on the metal used, but is 5 to 500 nm, preferably 10 to 400 nm, and more preferably 20 to 300 nm. If the thickness of the metal layer is less than 5 nm, the metal layer does not have sufficient concealing properties, so that the purpose as a dye transfer prevention layer cannot be fulfilled. In addition, when the printing laminate is attached to a curved surface or the like, it is stretched. Therefore, the metal film becomes thinner, which is not preferable. On the other hand, when the thickness exceeds 500 nm, the adhesion between the metal layer and the coloring resin layer or the dye transfer preventing layer is lowered, the metal film is easily cracked, and the cost is increased. The method for providing the metal layer is not particularly limited, and ordinary vapor deposition, sputtering, transfer, plasma, and the like can be used. In particular, a vapor deposition method or a sputtering method is preferably used from the viewpoint of workability. When forming such a metal layer, the metal to be used is not particularly limited, and examples thereof include metals such as aluminum, gold, silver, copper, nickel, chromium, magnesium, and zinc. Considering workability, ease of forming a metal layer, etc., aluminum, chromium or nickel is particularly preferred. The metal layer may be formed of an alloy composed of two or more metals.
[0057]
By providing the surface resin layer on the coloring resin layer of the printing laminate of the present invention, the coloring agent of the coloring resin layer can be protected from ultraviolet rays, water, and the like, and sufficient outdoor durability can be maintained. It becomes possible. As a material satisfying such required characteristics, an olefin resin, that is, polyethylene, polypropylene, or the like, a vinyl alcohol resin, such as polyvinyl alcohol, an ethylene-vinyl alcohol copolymer resin, a fluorine resin, a silicon resin, or These mixtures and the like can be mentioned.
[0058]
In particular, it is preferable to use a synthetic resin containing a fluorine-based resin or a silicon-modified acrylic resin as a main component, which has high outdoor weather resistance and is incompatible with a coloring agent. Examples of the synthetic resin containing a fluororesin as a main component include polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and tetrafluoroethylene-hexafluoropropylene-perfluoro. Fluorinated resins such as alkyl vinyl ether copolymers, tetrafluoroethylene-ethylene copolymers, polychlorotrifluoroethylene, chlorotrifluoroethylene-ethylene copolymers, polyvinylidene fluoride, and polyvinyl fluoride are exemplified. To process these fluorine-based resins, it is a general method to melt them by mainly applying heat, process them into a desired shape, and then cool and commercialize them. However, since the film manufactured by such a method is stretched in the vertical and horizontal directions, it tends to shrink when heated to a temperature of 150 to 200 ° C. during thermal transfer, causing print blur and blurring of a printed pattern. Defects are more likely to occur. In order to prevent this, the surface resin layer is made of unstretched fluorine produced by processing a fluororesin made of a fluoroolefin copolymer soluble in the above-mentioned solvent by a processing method such as a solution casting method (casting method). It is preferably formed of a resin film, more preferably a fluoroolefin copolymer soluble in a solvent having a reactive functional group, and a curing agent and / or a curing catalyst that reacts with the reactive functional group. It is preferably formed by a reaction. Among these, copolymers of fluoroolefins or copolymers of fluoroolefins and monomers other than fluoroolefins have good solubility in general-purpose solvents and are considered from the viewpoint of work in film production. A coalescence is particularly preferred (hereinafter, these are also referred to as “fluoroolefin-based copolymers”). Specific examples of the fluoroolefin used for preparing such a fluoroolefin-based copolymer include vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, and hexafluoropropylene. No. By copolymerizing two or more of these fluoroolefins, a copolymer containing only fluoroolefins as a monomer component can be obtained. Further, the copolymerization of the fluoroolefins and monomers copolymerizable therewith can prepare a fluoroolefin-based copolymer soluble in a solvent. Specific examples of the vinyl monomer copolymerizable with the fluoroolefin include alkyl or cycloalkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, cyclohexyl vinyl ether, and cyclopentyl vinyl ether, vinyl acetate, and vinyl propionate. Vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl benzoate, pt-butyl vinyl benzoate, vinyl carboxylate such as vinyl cyclohexanecarboxylate, isopropenyl acetate, 2-hydroxyethyl vinyl ether, 3-hydroxyethyl vinyl ether Monomers having a hydroxyl group such as hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 2-hydroxyethyl allyl ether, and 2-hydroxyethyl (meth) acrylate , Monomers having a carboxyl group such as acrylic acid and methacrylic acid, and monomers having an amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminoethyl vinyl ether , Glycidyl vinyl ether, monomers having an epoxy group such as glycidyl (meth) acrylate, and hydrolyzable silyl groups such as trimethoxyvinylsilane, triethoxyvinylsilane, 2-trimethoxyethylvinylether, and γ-methacryloxypropyltrimethoxysilane. Monomers having a silyloxy group such as 2-trimethylsilyloxyethyl vinyl ether and 4-trimethylsilyloxybutyl vinyl ether; trimethylsilyl (meth) acrylate; vinyl-5-trimethylsilyl Monomers having a silyloxycarbonyl group such as oxycarbonylpentanoate, and ethylene, propylene, vinyl chloride, and various alkyl (meth) acrylates are also included. Among such monomers, it is particularly preferable to use a vinyl ester or vinyl ether having no functional group as an essential component from the viewpoint of copolymerizability, coating film performance, and the like. A monomer having such a reactive functional group may be copolymerized.
[0059]
Suitable copolymers of fluoroolefins and monomers other than fluoroolefins used in the present invention include about 15 to 70% by weight of a fluoroolefin and about 0 to about 0% of a vinyl monomer containing a reactive functional group. To 30% by weight and about 5 to 85% by weight of other monomers copolymerizable therewith. More preferable copolymers include about 20 to 65% by weight of a fluoroolefin, about 5 to 25% by weight of a vinyl monomer having a reactive functional group, and other monomers copolymerizable therewith. About 10 to 75% by weight is copolymerized. If the amount of the fluoroolefin is less than about 15% by weight, the durability, the antifouling effect and the permeability of the sublimable dye are insufficient, and if it exceeds about 70% by weight, the solubility in general-purpose solvents is reduced. It is not preferable because the workability is deteriorated. The weight average molecular weight of the copolymer used is preferably in the range of about 5,000 to 400,000, more preferably about 7000 to 300,000, from the viewpoints of workability and film durability.
[0060]
The fluororesin, which is the surface resin layer of the laminate for printing of the present invention, can be prepared from a fluoroolefin copolymer and an acrylic polymer as described above. The acrylic polymer referred to here is a homopolymer or a copolymer having an acrylate or methacrylate as an essential component, and any of those having a reactive functional group and those having no reactive functional group are used. It is possible. Various known acrylic polymers can be used, but those having a weight average molecular weight of about 5,000 to 400,000, more preferably about 7000 to 300,000, are particularly preferable from the viewpoint of durability and workability.
[0061]
When the above-mentioned fluoroolefin-based copolymer and acrylic polymer are used in combination as the resin for the surface resin layer, the ratio of the former to the latter is about 30:70 to about 98: 2, more preferably, in weight ratio. Desirably, it is in the range of about 40:60 to about 95: 5. If the amount of the acrylic polymer is less than about 2%, the properties of the acrylic polymer to be imparted will not be exhibited, and if it exceeds about 70% by weight, the durability, the antifouling effect, and the permeability of the sublimable dye will be poor. It is not preferable because it becomes sufficient.
[0062]
In forming the surface resin layer of the printing laminate of the present invention, the fluoroolefin-based copolymer and the acrylic-based polymer are used in a form dissolved in an organic solvent. When the fluoroolefin-based copolymer or the acrylic polymer to be blended has a reactive functional group as described above, a curing agent having a functional group that reacts with the reactive functional group may be blended. . In the case of having a hydrolyzable silyl group as a reactive functional group, a curing catalyst of an acid, a base or various organotin compounds can be blended. Further, as described above, even when a curing agent is blended, a catalyst suitable for accelerating the curing reaction can be added. When the reactive functional group of the fluoroolefin-based copolymer is a hydroxyl group or a silyloxy group, a polyisocyanate, a block polyisocyanate, an amino resin, a metal alkoxide, a metal chelate compound or the like is blended. When the reactive functional group is an epoxy group, a polycarboxy compound, a polysilyloxycarbonyl compound, a polyamine compound and the like are blended. Further, when the reactive functional group is a carboxyl group or a silyloxycarbonyl group, a polyepoxy compound, an epoxysilane compound, a metal chelate compound and the like are blended. Further, when the reactive functional group is an amino group, a polyepoxy compound or an epoxysilane compound is blended as a curing agent. When an amino resin is blended as a curing agent into a fluoroolefin-based copolymer or a blend of a fluoroolefin-based copolymer and an acrylic copolymer, the amino resin is added to the base resin component in an amount of about 100 parts by weight. The amount may be 5 to 100 parts by weight, preferably about 10 to 60 parts by weight.
[0063]
When a curing agent other than an amino resin is blended, the equivalent of the reactive functional group in the fluoroolefin-based copolymer or a blend of the fluoroolefin-based copolymer and the acrylic-based polymer is equivalent to one equivalent of the functional group in the curing agent. The curing agent may be blended so that the group is in the range of about 0.2 to 2.5 equivalents, more preferably about 0.5 to 1.5 equivalents.
[0064]
In the composition used for forming the surface resin layer, as a matting agent, silica, calcium carbonate, aluminum hydroxide, acrylic resin, organic silicone resin, polystyrene, urea resin, fine particles of formaldehyde condensate and the like Is added to reduce the 60 ° gloss of the surface to 70 or less, reflection of lighting equipment such as a fluorescent lamp on the surface layer can be prevented. It is preferable to use an acrylic resin because the compatibility with the fluoroolefin-based copolymer becomes good.
The composition used to form the surface resin layer and the composition used to form the dye transfer-preventing coloring resin layer or the coloring resin layer described above include an ultraviolet absorber, a light-stable The long-term durability can be further improved by adding an agent and an antioxidant individually or in a combination of each and including them. Known ultraviolet absorbers can be used, and typical examples thereof include benzophenone-based, benzotriazole-based, cyanoacrylate-based, salicylate-based, and oxalic anilide-based light stabilizers, and hindered amine-based light stabilizers. Known compounds such as compounds, such as hindered phenol compounds, amine antioxidants, and sulfur antioxidants, can be used as antioxidants. However, if low molecular compound UV absorbers, light stabilizers, and antioxidants are used, the appearance of phases due to phase separation from the transparent resin, bleed out, and the penetration of sublimable dyes into the printing laminate will result. Since a problem such as a volatilization phenomenon during the heat treatment performed in step (1) appears remarkably, it is preferable to use a high molecular weight type ultraviolet absorber, a light stabilizer and an antioxidant.
[0065]
Examples of the ultraviolet absorber used in the present invention include salicylic acid-based ones such as phenyl salicylate, p-di-tert-butylphenyl salicylate, and p-octylphenyl salicylate; 2,4-dihydroxybenzophenone; 2-hydroxybenzophenone; -Hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy- Benzophenone-based compounds such as 4-methoxy-5-sulfobenzophenone, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole , -(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole Benzotriazoles, such as 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl- Cyanoacrylates such as 2-cyano-3,3'-diphenylacrylate, metal oxides such as titanium oxide, zinc oxide and cerium oxide, anilide oxalate, triazine, dibenzoylmethane, There are benzylidene type and the like.
[0066]
As the ultraviolet absorber, there is a so-called high molecular weight ultraviolet absorber in which the above-mentioned ultraviolet absorber is introduced into a part of the polymer.
[0067]
As the high molecular weight type ultraviolet absorber, known ones can be used. For example, [2-hydroxy-4- (methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4- (Methacryloyloxymethoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4- (methacryloyloxyoctoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4- (methacryloyloxidedecyloxy) ) Benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4- (methacryloyloxybenzyloxy) benzophenone] -methyl methacrylate copolymer, [2,2′-dihydroxy-4- (methacryloyloxyethoxy) benzophenone ] -Meta Methyl acrylate copolymer, [2,2'-dihydroxy-4- (methacryloyloxymethoxy) benzophenone] -methyl methacrylate copolymer, [2,2'-dihydroxy-4- (methacryloyloxyoctoxy) benzophenone] -Methyl methacrylate copolymer, [2,2'-dihydroxy-4- (methacryloyloxybenzyloxy) benzophenone] -Methyl methacrylate copolymer, [2,2-dihydroxy-4- (methacryloyloxidedecyloxy) benzophenone ] -Methyl methacrylate copolymer, [2,2 ', 4-trihydroxy-4'-(methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer, [2,2 ', 4-trihydroxy-4 '-(Methacryloyloxymethoxy) benzophenone] Methyl methacrylate copolymer, [2,2 ', 4-trihydroxy-4'-(methacryloyloxyoctoxy) benzophenone] -methyl methacrylate copolymer, [2,2 ', 4-trihydroxy-4' -(Methacryloyloxidedecyloxy) benzophenone] -methyl methacrylate copolymer, [2,2 ', 4-trihydroxy-4'-(methacryloyloxybenzyloxy) benzophenone] -methyl methacrylate copolymer, [4- Hydroxy-4 ′-(methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer, [4-hydroxy-4 ′-(methacryloyloxymethoxy) benzophenone] -methyl methacrylate copolymer, [4-hydroxy-4 ′ -(Methacryloyloxyoctoxy) benzophenone]- Methyl methacrylate copolymer, [4-hydroxy-4 '-(methacryloyloxidedecyloxy) benzophenone] -methyl methacrylate copolymer, [4-hydroxy-4'-(methacryloyloxybenzyloxy) benzophenone] -methacrylic acid Methyl copolymer, [2-hydroxy-4'-methyl-4- (methacryloyloxyethoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4'-methyl-4- (methacryloyloxymethoxy) benzophenone ] -Methyl methacrylate copolymer, [2-hydroxy-4'-methyl-4- (methacryloyloxyoctoxy) benzophenone] -methyl methacrylate copolymer, [2-hydroxy-4'-methyl-4- ( Methacryloyloxidedecyloxy) benzofe ] -Methyl methacrylate copolymer, [2-hydroxy-4'-methyl-4- (methacryloyloxybenzyloxy) benzophenone] -methyl methacrylate copolymer, [2- (2'-hydroxy-4'-) [Methacryloyloxyethoxy) benzotriazole] -methyl methacrylate copolymer, [2- (2'-hydroxy-4'-methacryloyloxyethoxy) -5-chlorobenzotriazole] -methyl methacrylate copolymer, and the like. Further, high-molecular-weight ultraviolet absorption such as 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] having a molecular weight of 500 or more. Agents are also suitable.
[0068]
The light stabilizer efficiently captures (bonds) and inactivates radicals generated by ultraviolet rays, and prevents a dye from deteriorating by preventing a chain reaction. 4-benzoyloxy-2,2,6,4 6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 2- (3 Bis (1,2,2,2,6-pentamethyl-4-piperidyl) 5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate, tetrakis (2,2,6,6- Various hindered amines such as tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, and 2,4-di-tert-butylphenyl-3,5-di-tert Hindered phenols such as butyl-hydroxybenzoate, [2,2'-thiobis- (4-tert-butylphenolate)]-tert-butylamine nickel (II), [2,2'-thiobis- (4-tert -Butyl phenolate)] nickel complexes such as 2-ethylhexylamine nickel (II) and nickel phosphates such as nickel salt of 3,5-di-tert-butyl-4-hydroxybenzyl phosphoric acid monoethyl ester Salts and the like are exemplified.
[0069]
In particular, N, N, N ′, N ′,-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazine- 2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5-triazine-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) Polycondensate of -1,6-hexamethylenediamine and N- (2,2,6,6 tetramethyl-4-piperidyl) butylamine, poly [{6- (1,1,3,3-tetramethylbutyl) Amino-1,3,5-triazine-2,4-diyl {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene} (2,2,6,6-tetramethyl- 4-piperidyl) imino}], dimethyl succinate 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine hindered amine light stabilizer having a molecular weight of 1000 or more high molecular weight type polymer such as ethanol is more preferable.
[0070]
There are two types of antioxidants: a radical acceptor type which stabilizes the generated peroxide by giving a proton to the peroxide, and a peroxide separated type which converts hydroperoxide into a stable alcohol. Typical examples of the former include phenolic compounds and amine compounds. Examples of phenolic compounds include compounds such as hydroquinone and gallate, 2,6-di-tert-butyl-p-cresol, and stearyl-β. -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6 tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 3,5-trimethyl-2,4,6-tris (3,5-di-tert-4-hydroxybenzyl) benzene, tris Hindered phenols such as 3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and tetrakis [methylene-3 (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane Compounds are exemplified. Examples of the amine compounds include N, N′-diphenyl-p-phenylenediamine, phenyl-β-naphthylamine, phenyl-α-naphthylamine, N, N′-β-naphthyl-p-phenylenediamine, N, N'-diphenylethylenediamine, phenothiazine, N, N'-di-sec-butyl-p-phenylenediamine, 4,4'-tetramethyl-diaminodiphenylmethane and the like are exemplified.
[0071]
As the latter, sulfur-based compounds and phosphorus-based compounds are typical, and as the sulfur-based compound, dilaurylthiodipropionate, distearylthiodipropionate, laurylstearylthiodipropionate, Examples include myristyl thiodipropionate, distearyl-β, β′-thiodibutyrate, 2-mercaptobenzimidazole, dilauryl sulfide, and the like. Examples of phosphorus compounds include triphenyl phosphite, trioctadecyl phosphite, and trioctyl phosphite. Examples include decyl phosphite, trilauryl trithio phosphite, diphenyl isodecyl phosphite, trinonyl phenyl phosphite, distearyl pentaerythritol phosphite and the like. The quencher is a compound that absorbs ultraviolet light and deprives the excited molecule excited by the excited molecule of the excited molecule to inhibit the reaction of the excited molecule, and includes various known metal complexes. Among these antioxidants and quenchers, hindered phenol compounds having a molecular weight of 1,000 or more are particularly suitable.
[0072]
As the organic solvent, those conventionally known can be used, and specifically, esters such as ethyl acetate, butyl acetate and ethyl cellosolve acetate, and aromatic hydrocarbons such as toluene, xylene and ethylbenzene are used. , Aliphatic, alicyclic hydrocarbons such as hexane, heptane, octane, cyclohexane and ethylcyclohexane, alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol, acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. And ketone solvents. When a polyisocyanate compound is used as the curing agent, use of an alcoholic solvent must be avoided. This is because the isocyanate group reacts with the alcohol.
[0073]
The following can be mentioned as examples of the silicon-modified acrylic resin.
(1) A cured film obtained by adding a hydrolysis catalyst to a vinyl copolymer obtained by copolymerizing a vinyl monomer having a hydrolyzable silyl group.
(2) A compound having both an epoxy group and a hydrolyzable silyl group in one molecule is added to a vinyl copolymer obtained by copolymerizing a vinyl monomer having an amino group and / or a carboxyl group to form a cured film. What you did.
(3) A cured film obtained by adding a polyisocyanate compound to a vinyl copolymer having a hydroxyl group obtained by graft-polymerizing a silicone resin.
(4) A cured film obtained by adding a hydrolysis catalyst to a vinyl copolymer having a hydrolyzable silyl group obtained by graft-polymerizing a silicone resin.
[0074]
In addition, as the dye for sublimation type ink used in the present invention, a dye that sublimates or evaporates at 70 to 260 ° C. under atmospheric pressure is preferable. For example, there are dyes such as azo, anthraquinone, quinophthalone, styryl, diphenylmethane, triphenylmethane, oxazine, triazine, xanthene, methine, azomethine, acridine, diazine and the like, and among these, 1,4-dimethylaminoanthraquinone, brominated or Chlorinated 1,5-dihydroxy-4,8-diamino-anthraquinone, 1,4-diamino-2,3-dichloro-anthraquinone, 1-amino-4-hydroxyanthraquinone, 1-amino-4-hydroxy-2- ( β-methoxyethoxy) anthraquinone, 1-amino-4-hydroxy-2-phenoxyanthraquinone, methyl, ethyl, propyl, butyl ester of 1,4-diaminoanthraquinone-2-carboxylic acid, 1,4-diamino-2-methoxy Anthraquinone 1-amino-4-anilinoanthraquinone, 1-amino-2-cyano-4-anilino (or cyclohexylamino) anthraquinone, 1-hydroxy-2- (p-acetoaminophenylazo) -4-methylbenzene, 3- Methyl-4- (nitrophenylazo) pyrazolone, 3-hydroxyquinophthalone and the like. Further, malachite green, methyl violet and the like can be used as the basic dye, and it is preferable to use a dye modified with sodium acetate, sodium ethylate, sodium methylate and the like.
[0075]
Using a sublimation type ink using these dyes, a printing process is performed on an ink temporary display surface layer provided on a transfer paper or a printing laminate surface by an electrophotographic method, an electrostatic recording method, an inkjet method, a thermal transfer method, or the like. In the case of transfer paper, the printing surface of the paper is applied to the surface of the printing laminate, and if it is printed on the temporary display surface layer of ink, the vacuum heating press machine, oven dryer, far infrared heating device is used as it is By heating at about 100 ° C. to about 200 ° C. for several tens of seconds to several minutes, the sublimable dye is sublimated, and the printed image is diffusely dyed inside the colorable resin layer. As a printing method at this time, it is possible to apply a printing method by a known and commonly used method such as thermal transfer, electrostatic printing, gravure printing, or an inkjet method. In particular, an inkjet printer that can easily perform full-color printing is used. The printing method described above is more preferable, and the on-demand type is particularly economical and preferable in terms of ink use efficiency.
Further, the heat treatment temperature after the printing is such that the sublimation of the sublimable dye is efficiently performed in a shorter time and the workability is improved without causing a large thermal damage to the release film or the like on the back surface of the printing laminate. To 150 to 200 ° C. is preferable, and if the printing surface is further dried to the touch drying level before the heat treatment, the diffusibility of the sublimable dye during the heat treatment becomes uniform, which is more preferable. Become. The transfer paper used at this time may be a commercially available ink jet printing paper, and it is preferable to use a hydrophilic resin for the ink temporary display surface layer. The hydrophilic resin used to form the temporary display surface layer includes polyurethane resin, acrylic resin, fluorine resin, unmodified and modified polyvinyl alcohol, polyester, acrylic urethane, vinyl acetate, and maleic anhydride. Polymer, Na salt of alkyl ester, gelatin, albumin, casein, starch, SBR latex, NBR latex, cellulose-based resin, amide-based resin, melamine-based resin, polyacrylamide, polyvinylpyrrolidone; It is also possible to use one or more of those having a hydrophilic group added.
[0076]
Further, fillers such as silica, clay, talc, diatomaceous earth, zeolite, calcium carbonate, alumina, zinc oxide, and titanium may be added.
[0077]
In addition, when the printing laminate of the present invention is used for application to a curved surface or the like, the laminate is required to have sufficient elongation. However, since a low molecular weight plasticizer or the like induces bleeding of a dye, the laminate is used. Unsuitable for use in However, in the present invention, since the bleeding of the dye is prevented by the dye transfer preventing layer or the metal thin film, the resin applied to the dye transfer preventing layer is provided on the back side of the dye transfer preventing layer or the metal thin film. The resin can be widely selected without being limited to, and a resin rich in elongation may be used. As a material satisfying such required characteristics, specifically, urethane resin, vinyl resin, acrylic resin, alkyd resin, polyester resin, epoxy resin, fluorine resin, olefin resin, silicon resin A synthetic resin such as a resin can be used. At this time, the dry thickness of the flexible layer is preferably set to 1 μm to 100 μm, preferably 3 μm to 80 μm, and more preferably 5 μm to 60 μm. When the film thickness is less than 1 μm, it is not enough to follow the elongation at the time of stretching and to prevent the breakage of the dye migration preventing layer. On the other hand, if the thickness exceeds 100 μm, the total thickness of the film becomes too large, and the followability to a curved surface when affixed to a substrate is undesirably reduced. Thereby, the elongation rate of the laminate is dramatically improved, and cracks during stretching of the dye transfer prevention layer and the metal thin film can be prevented by laminating the resin layer. As a result, flexibility and elongation rate are reduced. A rich printing laminate capable of preventing dye bleeding is completed.
[0078]
FIG. 1 shows the present invention.Reference exampleIt is a cross-sectional view of the laminate for printing in, the surface resin layer (A) 1 which has a weak affinity for the sublimable dye in order from the surface and allows the dye to pass therethrough, and has an affinity for the dye. And a dye transfer preventing coloring resin layer (B) 12 for preventing transfer of the dye.
[0079]
FIG.oneIt is sectional drawing of the laminated body for printing in embodiment, It is a surface resin layer (A) 1, the coloring resin layer (B1) 2 which has affinity with the said dye in order from the surface, and the transfer of the said dye. And a dye transfer preventing layer (B2) 3 for preventing the transfer.
[0080]
FIG. 3 shows the present invention.AnotherFIG. 3 is a cross-sectional view of the printing laminate according to the embodiment, in order from the surface, a surface resin layer (A) 1, a coloring resin layer (B1) 2, a dye transfer prevention layer (B2) 3, and a dye transfer prevention. It is composed of a flexible resin layer (C) 4 having a larger elongation than the layer (B2) 3.
[0081]
FIG. 4 is a cross-sectional view of a printing laminate according to yet another embodiment of the present invention. The surface resin layer (A) 1, the dye transfer preventing coloring resin layer (B) 12, and the dye The adhesive layer 5 and the release material 6 below the adhesive layer 5 are further provided on the back surface of the migration-preventive coloring resin layer (B) 12, and the adhesive layer 5 or the release material 6 is subjected to an antistatic treatment.
[0082]
FIG. 5 is a cross-sectional view of a printing laminate according to still another embodiment of the present invention. The surface resin layer (A) 1, the coloring resin layer (B1) 2, and the dye transfer prevention layer ( B2) 3, a flexible resin layer (C) 4 having a larger elongation rate than the dye migration preventing layer (B2) 3, and an adhesive layer 5 on the back surface of the flexible resin layer (C) 4. A release material 6 is provided thereunder, and the pressure-sensitive adhesive layer 5 or the release material 6 is subjected to an antistatic treatment.
1 to 3, the pressure-sensitive adhesive layer 5 and the release material 6 may be formed, and the pressure-sensitive adhesive layer 5 or the release material 6 may be subjected to an antistatic treatment.
[0083]
The printing laminate shown in FIG. 1 has a dry film thickness of about 0.5 to about 300 μm, preferably about 2 to about 200 μm on a support film such as a polyethylene terephthalate film or process paper in the first step, and further, Preferably, the paint for the surface resin layer 1 is applied so as to have a thickness of about 3 to about 100 μm, and dried at room temperature or by heating. Next, in the second step, a paint for the dye transfer-preventive coloring resin layer 12 subsequent to the surface resin layer 1 is coated with a dry film thickness of about 1 to about 500 μm, preferably about 2 to about 400 μm, and more preferably about 3 to about 400 μm. It is applied so as to have a thickness of about 300 μm, and dried at normal temperature or by heating to form a film.
[0084]
The printing laminate shown in FIG. 3 has, in the first step, a dry film thickness of about 0.5 to about 300 μm, preferably about 2 to about 200 μm, on a support film such as a polyethylene terephthalate film or process paper. Preferably, the paint for the surface resin layer 1 is applied so as to have a thickness of about 3 to about 100 μm, and dried at room temperature or by heating. Next, in the second step, the paint for the coloring resin layer 2 subsequent to the surface resin layer 1 is dried to a thickness of about 1 to about 500 μm, preferably about 2 to about 400 μm, and more preferably about 3 to about 300 μm. And dried at room temperature or by heating.
In the third step, the paint for the dye transfer preventing layer 3 subsequent to the coloring resin layer 2 is coated with a dry film thickness of about 1 to about 500 μm, preferably about 2 to about 400 μm, and more preferably about 3 to about 300 μm. And dried at room temperature or by heating. In the fourth step, the coating of the flexible resin layer 4 subsequent to the dye transfer preventing layer 3 is dried to a thickness of about 1 μm to about 100 μm, preferably about 3 μm to about 80 μm, and more preferably about 5 μm to about 60 μm. And then dried at room temperature or by heating.
[0085]
In this step, the paint for the flexible resin layer 4 is used in the first step, the paint for the dye transfer prevention layer 3 is used in the second step, and the paint for the colorable resin layer 2 is used in the third step. It is also possible to apply the paint for the surface resin layer 1 in the fourth step. Further, if necessary, a step of removing the flexible resin layer 4 is also possible. After these steps are completed, a support film such as a polyethylene terephthalate film or process paper is peeled off from the laminate, and a pressure-sensitive adhesive layer or a back surface of the laminate, if necessary, that is, a layer on the side opposite to the surface resin layer. An adhesive layer is formed, and a release material such as a release paper or a release film is attached to the pressure-sensitive adhesive layer or the adhesive layer to obtain a finished printing laminate. However, when a biaxially stretched polyester film is used for the dye transfer preventing layer 3, the step of peeling and removing the support film from the laminate is omitted because the support film and the dye transfer preventing layer 3 are also used. The drying conditions after application of the paint in the first, second, third and fourth steps include the type of base resin used as a paint material, the type of functional group in the base resin, and the reactivity in the base resin. It is appropriately determined according to the type of the functional group, the type of the curing agent, and the type of the solvent. The application of the coating material in each of the above steps may be performed by spray coating, or may be performed using a commonly used coating device such as a knife coater, a comma coater, a roll coater, a reverse roll coater, or a flow coater. Further, by using a clear paint containing no pigment as a paint used to form each layer of the printing laminate of the present invention, a printing laminate without coloring can be obtained, but the surface resin layer and the subsequent By using a colored paint containing a pigment as a paint for forming the lower layer, a colored printing laminate can also be obtained. Pigments used in obtaining such a coloring paint include organic pigments such as phthalocyanine blue, phthalocyanine green, quinacridone red, or Hansa yellow, iron oxide red, iron oxide yellow, titanium white, cobalt blue, and carbon. Known pigments such as inorganic pigments such as black are suitable. Furthermore, the pigment itself has a five-layer structure, and about 50% of the incident light is reflected by the surface layer, and the remaining about 50% is reflected by the opaque reflector metal in the central layer to generate an interference wavelength, which causes visual interference. By using a chroma flare pigment (manufactured by Flex Products), different colors can be visualized, and a printing laminate excellent in design can be obtained, which is preferable. A similar effect can also be obtained with "VARIOCROM" (trade name, manufactured by BASF) in which the surface of an aluminum flake pigment is coated with iron oxide.
Producing a light-diffusing layer in which light-diffusing fine particles are blended in at least one of the surface resin layer 1, the dye-transfer-preventive coloring resin layer 12, the dye-transfer-preventive layer 3, and at least one of these lower layers. Then, the printing laminate of the present invention can be preferably used as an internally illuminated film (backlight film). In this case, it is more preferable to mix light diffusing fine particles below the colored layer without impairing the sharpness and color development of the image.
[0086]
Examples of the light diffusing fine particles constituting the light diffusing layer include silica, calcium carbonate, titanium dioxide, aluminum hydroxide, acrylic resin, organic silicone resin, polystyrene, urea resin, formaldehyde condensate, and the like. One or more types may be selected from among them, and there is no particular limitation.
[0087]
As the light-transmitting resin serving as a binder of the light-diffusing layer in which light-diffusing fine particles are dispersed and blended, acrylic resin, polyurethane resin, polyester resin, polyvinyl chloride resin, polyvinyl acetate resin, cellulose resin A resin, a polyamide resin, a fluorine resin, a polypropylene resin, a polystyrene resin alone or a mixture thereof is preferable, or each resin is formed by using a curing agent such as a melamine resin, an isocyanate resin, or an epoxy resin. It is more preferable to apply the functional group and the resin composition cured three-dimensionally, but it is not particularly limited. Generally, the difference in refractive index between the light transmitting resin and the light diffusing fine particles is preferably about 0.02 or more. Further, the Tg (glass transition point) of the light-transmitting resin is desirably 50 ° C. or higher, and if the Tg is lower than 50 ° C., when the light diffusion layer comes into contact with another member, there is a problem in storage stability due to blocking. It is not preferable because it may occur.
[0088]
Among these, acrylic resin, polyurethane resin, polyester resin, polyvinyl chloride resin, polyvinyl acetate, and the like are excellent in dispersion suitability (wetting property) of light diffusing fine particles and controllability of refractive index difference. A simple substance or a mixture of base resins is preferred, but a resin composition in which each resin is three-dimensionally cured with a functional group of the resin using a curing agent such as a melamine resin, an isocyanate resin, or an epoxy resin is more preferred. It is.
[0089]
As a method for producing the light diffusing layer, a method in which a light transmitting resin and one or more kinds of light diffusing fine particles are dissolved or dispersed in an appropriate organic solvent (or water) is applied by a general coating method, for example, a roll. It may be applied using a coating method, a knife coating method, or the like, and then the organic solvent (or water) is dried and evaporated, and if necessary, the curing reaction between the resin and the curing agent is allowed to proceed. The coating method may be appropriately selected in consideration of the viscosity of the diffusion resin composition, the target film thickness, and the like. The amount of the light diffusing fine particles to be added is preferably 1 to 40% by weight based on the light transmitting resin, and may be dispersed and blended according to the required characteristics. The coating thickness of the light diffusion layer is generally desirably about 3 to 50 μm, but is not limited thereto.
[0090]
The printing laminate having the light diffusion layer function, when illumination light is incident from the back surface opposite to the surface resin layer, a linear light source such as a fluorescent lamp of a backlight is uniformly diffused by the light diffusion film, It becomes a bright surface illuminant, and is prevented from being reflected on the front surface of a fluorescent lamp or the like on the back surface. At this time, light also passes through the color coloring layer obtained by sublimation dyeing printing on the coloring resin layer, and the function as an internally illuminated signboard is exhibited. However, since the sublimation dye has very good transparency, it is necessary to print a large amount of ink to increase the transmission density to a desired density, and the printing workability is reduced, and the drying property after printing has a problem. Occurred. In order to solve this problem, it has been found that the transmission density of a printed image is improved by using a white pigment in a layer to be sublimated and used as a white layer.
[0091]
At this time, a white pigment is used for at least one or more of the dye transfer preventing colorable resin layer 12, the color resin layer 2, and the dye transfer preventing layer 3 in order to enhance the sharpness. It has been found that forming a white layer improves the transmission density of a printed image. At this time, the dye transfer-preventive coloring resin layer is further divided, and the upper layer is a transparent resin layer, the lower layer is a white layer, and the color resin layer and the dye-transfer-preventing layer are formed when the color resin layer and the dye transfer prevention layer are formed. It is more preferable to further divide the upper layer into a transparent resin layer and the lower layer as a white layer because the transmission density is improved while maintaining the sharpness of the image. At this time, the white pigment used for whitening may be any pigment that is usually used to color a synthetic resin white, and specifically, titanium oxide, zinc white, lead white, barium sulfate, zinc sulfide, antimony oxide ,MTiO _Three (Where M is at least one element selected from the group consisting of Mg, Ca, Sr and Ba). At this time, the amount of the white pigment used is such that the transmission density V of the white layer (using a density measuring device DM-201, manufactured by Noritz Kogyo Co., Ltd.) is 0.10 to 1.70, preferably 0.15 to 1.65. , More preferably 0.20 to 1.40. If the transmission density V of the white layer is less than 0.10, it is not enough to increase the transmission density of the image, and if it exceeds 1.70, the light transmittance becomes insufficient and the characteristics of the internally illuminated signboard deteriorate. Not preferred.
[0092]
If a retroreflective structure described below is produced in the lower layer continuous with the dye transfer preventing coloring resin layer 12, the lower layer continuous with the dye transfer preventing layer 3, or the lower layer of the flexible resin layer 4, it can be used at night. Also, the lighting such as the headlights of the vehicle returns the light accurately in the direction of the light source, and the full-color image similar to that in the daytime can be visually recognized by the driver of the vehicle, etc., so it is suitable for various advertising signs including road signs. It is. Further, since image printing can be performed by an on-demand method, there is no need to prepare a plate for each image unlike silk screen printing conventionally applied to a retroreflective sheeting, which is extremely useful in cost reduction.
[0093]
Examples of the retroreflective sheeting methods (1) to (3) will be described below.
(1) As shown in FIG. 6, after applying a focal resin composition in which high refractive glass beads 102 are blended under each of the above resin layers so as to obtain an optimal dry film thickness as the focal layer film 101, Dry at room temperature or by heating. Here, the optimum dry film thickness of the focal layer depends on the particle size of the glass beads, but is generally about 10 to 70 μm. Next, a reflection layer made of the metal reflection film 103 is formed. Preferred as the focal resin composition coating used at this time are polyurethane resins, polyvinyl acetal resins, acrylic resins, alkyd resins, polyester resins and the like as base polymer components, and these are non-crosslinked type And a curing agent such as an amino resin, an epoxy resin, a polyisocyanate and a blocked polyisocyanate can be blended and used as a thermosetting type.
[0094]
In addition, the drying conditions after application of the focal resin composition paint in the above are appropriately determined according to the type of the base resin used as the coating material, the type of the reactive functional group in the base resin, the type of the curing agent, and the type of the solvent. It is determined.
[0095]
Suitable glass beads for use have a refractive index of 1.90 to 2.40, more preferably 2.10 to 2.30. The particle diameter is preferably 5 to 300 μm, more preferably 20 to 100 μm. If the particle diameter of the beads is less than 5 μm, the required thickness of the focusing layer becomes extremely thin, making it difficult to control the thickness. On the other hand, if it exceeds 300 μm, the required focal layer film thickness becomes extremely thick, and the resin is molded concentrically with the spherical diameter of the glass beads due to the flow of the resin in the heating step during molding. Have difficulty. If the refractive index is less than 1.9, the required thickness of the focal layer becomes extremely large, and it is difficult to mold the resin concentrically with the spherical diameter of the glass beads. Moreover, when producing beads having a refractive index exceeding 2.4, it is extremely difficult to industrially produce transparent glass beads with high precision while preventing crystallization.
[0096]
The method for providing the metal reflection film 103 is not particularly limited, and a normal vapor deposition method, a sputtering method, a transfer method, a plasma method, or the like can be used. In particular, a vapor deposition method and a sputtering method are preferably used from the viewpoint of workability. The metal used in forming such a metal layer is not particularly limited, and examples thereof include metals such as aluminum, gold, silver, copper, nickel, chromium, magnesium, and zinc. Aluminum, chromium or nickel is particularly preferable in consideration of workability, ease of forming a metal reflection film, durability of light reflection efficiency, and the like. The metal reflection film may be formed of an alloy composed of two or more metals. The thickness varies depending on the metal used, but is 5 to 200 nm, preferably 10 to 100 nm. When the thickness of the metal reflection film is less than 5 nm, the concealing property of the metal reflection film is not sufficient, so that the purpose as the reflection layer cannot be fulfilled. This is not preferable because it is easy to enter and the cost increases.
(2) As shown in FIG. 7, the dry film thickness of the glass bead fixing layer 201 is 100 μm or less from the thickness of 10% of the glass bead particle diameter to be used below the resin layer. The above-mentioned coating material for forming a glass bead fixing layer is applied so that the thickness becomes 20 μm from the thickness of 20% of the bead particle diameter, and then the solvent is volatilized by drying at room temperature or by heating, and then the high refractive glass beads 202 are embedded. . Representative paints used for forming the glass bead fixing layer include fluoroolefin copolymers containing reactive functional groups, polyester resins, alkyd resins, polyurethane resins, and reactive functional groups. Examples thereof include those obtained by blending a curing agent and / or a curing catalyst such as an amino resin, an epoxy resin, a polyisocyanate, and a blocked polyisocyanate with an acrylic polymer as a base resin component. Here, each of the above base resin components may be used alone or as a mixture of two or more. As the form of the paint, any of a solution type, a non-aqueous dispersion type, a water-soluble type and an aqueous dispersion type can be used, but the solution type is particularly preferred.
[0097]
Next, the focus resin composition paint described in the above (1) is applied as the focus layer film 203 so as to obtain an optimum dry film thickness, and then dried by ordinary drying or heating.
[0098]
The application of the paint in each of the above steps may be performed by spray coating, or may be performed using a coating device such as a knife coater, a comma coater, a roll coater, a reverse roll coater, or a flow coater.
[0099]
Further, by using a clear paint containing no pigment as a paint used for forming each layer of each retroreflective sheet of the present invention, a retroreflective sheet without coloring can be obtained. A colored retroreflective sheet can also be obtained by using a colored paint containing a pigment as a paint for forming each layer in the figure. Examples of the pigment used for obtaining such a colored paint include organic pigments such as phthalocyanine blue, phthalocyanine green, quinacridone red and Hansa yellow, and inorganic pigments such as iron oxide red, iron oxide yellow, titanium yellow and cobalt blue. Known and commonly used ones are used.
[0100]
The thus-obtained retroreflective sheet of the present invention, after the metal reflective film 204 is formed as described above, forms an adhesive layer or an adhesive layer on the metal reflective film, If necessary, a release material such as a release paper or a release film may be attached to the pressure-sensitive adhesive layer or the like to obtain a final product.
(3) As shown in FIG. 8A, a plurality of transparent glass spheres 302 are embedded in the surface of the polyethylene glass sphere temporary fixing layer 307 laminated on the polyester film 308 in a plane. The polyethylene laminated film (temporarily fixed glass sphere layer 307 and polyester film 308) is heated to soften the polyethylene, and the glass sphere 302 is embedded. The glass sphere 302 is a fine particle having a particle diameter of about 5 to 300 μm and a refractive index of about 1.8 to 2.1. Particularly preferred as glass spheres have a refractive index of about 1.9 to 1.95 (particularly preferred is 1.92 to 1.93) and a particle diameter of about 20 to 90 μm (particularly preferred are 40 to 80 μm).
[0101]
Next, a metal reflection film 303 is formed on the hemispherical surface of the glass sphere 302 exposed from the surface of the glass sphere temporary fixing layer 307 by a vapor deposition method. This vapor deposition is performed on the entire surface of the glass ball temporary fixing layer 307. Then, the metal reflection film 303 deposited on a portion other than the glass sphere 302 on the surface of the glass sphere temporary fixing layer 307 described later remains on the surface of the glass sphere temporary fixing layer 307 as it is, and the other metal reflection films 303 are supported together with the glass sphere 302. Transferred to resin sheet 304 (FIG. 8E). As the above-mentioned metal reflection film 303, an aluminum reflection film is preferable, and even if it is formed of another metal such as gold, silver, copper, nickel, and chromium, the present invention can be implemented.
[0102]
As a next step, there is a method for manufacturing a retroreflective sheeting having the following two types of structures.
(A) Type with primer layer 305
(B) Type without primer layer
In the case of the above (A), the adhesive is laminated on the back surface of the primer layer 305, and in the case of (B), the adhesive is laminated on the back surface of the support resin sheet 304. In order to adjust the glass bead transfer performance of the support resin film in which the glass beads of the glass ball temporary fixing layer are transferred and embedded, a polymer or a low-molecular plasticizer may be used for the support resin sheet in some cases. These plasticizers and the like migrate over time to the interface between the pressure-sensitive adhesive and the support resin sheet or to the pressure-sensitive adhesive layer, and deteriorate the performance of the pressure-sensitive adhesive. That is, the interfacial adhesive strength between the pressure-sensitive adhesive and the supporting resin sheet is reduced, and the adhesive performance of the pressure-sensitive adhesive to the substrate is lowered. In order to solve this problem, that is, to prevent migration of a plasticizer or the like from the supporting resin sheet to the pressure-sensitive adhesive layer, a primer layer may be laminated.
[0103]
The type having the primer layer 305 of the above (A) is made of a resin having a functional group as described above, or a resin having a functional group which reacts with a functional group of the resin. A resin having excellent interlayer adhesion is selected as a resin for the primer layer 305. Then, a resin solution selected for the primer layer 305 is coated on a separately prepared polyester film 306 and dried using a hot-air dryer. At this time, the thickness of the primer layer 305 is preferably 3 μm to 100 μm, more preferably 6 μm to 50 μm, and if it is less than 3 μm, the effect of preventing migration of a plasticizer or the like is reduced. This is not preferable because the workability such as sticking of the resin decreases.
[0104]
Next, a support resin sheet 304 having a constant thickness of about 10 to 300 μm, preferably about 30 to 100 μm is formed above the primer layer 305 formed above (FIG. 8B). As the resin that can be used for the support resin sheet 304, a resin having the above-described functional group is preferable.
[0105]
The type (B) without the primer layer 305 can be carried out by omitting the step of preparing the primer layer in the above-described method for manufacturing a retroreflective sheet. Next, as shown in FIG. 8C, the supporting resin sheet 304 as described above is placed along the surface of the glass ball temporary fixing layer 307. Then, as shown in FIG. 8D, the support resin sheet 304 is pressed against the surface of the glass ball temporary fixing layer 307. This pressing is performed so that the hemispherical surface of the glass sphere 302 on which the metal reflection film 303 is deposited is embedded in the supporting resin sheet 304. At this time, it is effective to further add a coupling agent or the like to the supporting resin sheet 304 in order to increase the fixing force of the supporting resin sheet 304 to the glass balls 302. Then, as shown in FIG. 8E, the glass ball temporary fixing layer 307 is peeled off together with the polyester film 308 from the surface of the supporting resin sheet 304. At this time, as shown in FIG. 8E, the glass sphere 302 remains on the supporting resin sheet 304, and the hemisphere is held by the supporting resin sheet 304 in a buried state. Thereafter, when a curing mode in which the reaction proceeds at room temperature (for example, isocyanate curing) is applied to the primer layer and / or the supporting resin sheet, it is possible to eliminate the variation in the performance of the bonding portion at the time of the heat molding processing in the next step, In order to stabilize the self-sustained form thereafter, it is preferable to perform an aging treatment in an environment at 30 to 40 ° C. to substantially terminate the reaction. Further, a heat treatment step at 120 to 150 ° C. is also effective to improve the adhesion between the glass sphere and the supporting resin sheet.
[0106]
Next, the surface of the supporting resin sheet formed in the state shown in FIG. 8F is covered with the dye transfer preventing coloring resin layer 12 or the dye transfer preventing layer 3 or the flexible resin layer 4 of the printing laminate. . FIG. 8F shows a case where the flexible resin layer 4 is used. From the back side polyester film side 306 of the support resin sheet 304 on which the resin layer is disposed, heat compression molding is performed with a patterned embossing roll 309 (FIG. 8G). As a means for the thermocompression bonding, it is preferable to pass through a heating roll having a roll surface temperature of 150 to 240 ° C, preferably 170 to 220 ° C. A supporting resin sheet that can be heat-formed at a temperature of less than 150 ° C. and exhibits adhesiveness to a surface film is not preferable because it cannot maintain the self-standing form of the sheet for a long time. Further, a support resin sheet that can be heat-formed at a temperature exceeding 240 ° C. is not preferable because the workability at the time of heat-forming is lowered, for example, a polyester film used as a protective film is melted when the heat-forming process is performed.
[0107]
After the heat molding, the backside polyester film 306 is peeled off, and a raw material of a high-reflection reflective sheet is produced. As a result, an embossed groove 310 having a width of, for example, 200 to 800 μm and a depth of 100 to 150 μm is formed on the back surface side of the supporting resin sheet 304.
[0108]
A pressure-sensitive adhesive layer or an adhesive layer is formed so as to fill the embossed groove, and if necessary, a release material such as a release paper or a release film may be attached to the pressure-sensitive adhesive layer or the like to form a final product. it can.
[0109]
As the retroreflective sheet located below the printing laminate of the present invention, various known retroreflective sheets can be applied in addition to the above-mentioned original retroreflective sheet.
[0110]
The laminate for printing according to the present invention obtained through the above-mentioned steps is the same as the above-mentioned structure except for the retroreflective sheet. After the film or the like is formed, a pressure-sensitive adhesive layer or an adhesive layer is further formed on these layers as necessary, and a release material such as a release paper or a release film is formed on the pressure-sensitive adhesive layer or the adhesive layer. Can be bonded to form a finished product of a printing laminate. In order to reduce the electric resistance of the release material surface and prevent the generation of static electricity, an antistatic agent is added to the release material used at this time by a kneading method, or an antistatic agent is applied to the release material surface. If it does, the discharge direction of the ink discharged from the printing nozzle is disturbed by the static electricity generated when the sheet is unwound or the static electricity generated by the friction between the printing laminate and the printing machine at the time of printing by the inkjet printing machine. This is preferable because it is possible to prevent the occurrence of disturbance in the printed image. In addition, examples of the antistatic agent used at this time include various surfactants, inorganic salts, polyhydric alcohols, metal compounds, carbon, and the like. For example, surfactants include anionic antistatic agents such as alkyl sulfonates, alkyl benzene sulfonates, alkyl sulfates, alkyl ethoxy sulfates, alkyl phosphates, alkyltrimethylammonium salts, and acyloylamides. Cationic antistatic agents such as propyltrimethylammonium methosulfate, alkylbenzyldimethylammonium salt, and acylcholine chloride; amphoteric antistatic agents such as alkylbetaine type, alkylimidazoline type and alkylalanine type; fatty acid alkylolamide; 2-hydroxyethyl) alkylamine, polyoxyethylene alkylamine, glycerin fatty acid ester, polyoxyethylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxysol Fatty acid ester, polyoxyethylene alkyl phenyl ethers, various surfactants of the nonionic antistatic agent of polyoxyethylene alkyl ether, and the like. When the release material 6 is polyethylene terephthalate, for example, about 5% by weight of polyethylene glycol can be copolymerized at the time of polymer synthesis.
[0111]
In addition, it is preferable to apply a biaxially stretched polyester film which has been previously annealed by heating as the base film, and the release material is 1.0% or less in the winding direction of the film when heated at 150 ° C. for 30 minutes. It is preferable to apply a biaxially stretched polyester film having a shrinkage of preferably 0.8% or less, more preferably 0.6% or less, as the base film. A release material having a shrinkage ratio of more than 1.0% is not preferable because the laminate is curled toward the release material when the printing laminate of the present invention is heated and dyed by sublimation.
[0112]
Further, if necessary, the surface resin layer 1 may be [M²⁺ _1-XM³⁺ _X(OH)_Two]^{X +}[A^n- _{X / n}・ MH_TwoO]^X-(M²⁺Is a divalent metal ion, M³⁺Is a trivalent metal ion, A^n-Is an n-valent anion, X is greater than 0 and 0.33 or less, 0 ≦ m≤When a coating film-forming composition containing fine particles of hydrotalcites and metal oxides shown in 2) is applied and dried, a hydrophilic coating film is formed, and a strong contact angle with a sufficiently small contact angle with water is obtained. The surface is used to prevent contamination due to hydrophilicity, and it is also possible to prevent the adhesion of water droplets due to condensation that inhibits the retroreflective effect, so that sufficient retroreflection at night can be secured, so it can be used on road signs and various advertising signs. It is preferable to apply. Further, the composition exhibits sufficient hydrophilicity at a film thickness of 1 μm or less, maintains long-term hydrophilicity outdoors, and furthermore, sublimates a dye which is more sublimable than the surface resin layer by heating inside the printing laminate. When penetrating, it is very suitable because it does not inhibit the permeation of the dye. As the fine particles of the metal oxide, titanium oxide particles, particularly a slurry solution of titanium oxide is most preferable, but instead of titanium oxide, zirconium oxide, strontium titanate, tungsten oxide, transition metal oxide such as iron oxide and the like. , For example, zinc oxide, bismuth oxide, tin oxide, alumina, magnesia, strontium oxide, and the like. The average particle size is preferably in the range of 0.001 to 0.5 μm, and particularly preferably 0.01 to 0.1 μm.
[0113]
Further, if necessary, it is possible to laminate a releasable temporary display surface layer on the surface side of the printing laminate. The production of the temporary display surface layer at this time is performed by using the above-mentioned coating apparatus to coat the resin for the temporary display surface layer with a dry film thickness of about 1 μm to about 100 μm, preferably about 3 μm to about 80 μm, and more preferably about 5 μm to What is necessary is just to adjust so that it may be set to about 60 micrometers. Further, if necessary, the temporary display surface layer can be formed into a laminated film of two or more layers, and in this case, the temporary display surface layer is manufactured by sequentially laminating an upper layer from a lower layer. In this case, the uppermost layer side of the temporary display surface layer is capable of absorbing ink containing a sublimable dye, and the surface side in contact with the surface resin layer (A) is the sublimable dye. More preferably, it is formed of a resin that has no affinity for the dye.
[0114]
In particular, the printing laminate of the present invention in which the temporary display surface layer is laminated on the front side can directly print an image taken by a commercially available digital camera on the temporary display surface layer of the printing laminate using an inkjet printer, After that, if a heat treatment is performed at 150 to 200 ° C. for several minutes, the sublimable dye printed on the temporary display surface layer is diffused and penetrated into the inside of the laminate for printing to easily form an image. This image has a high resolution comparable to that of a conventional silver halide photograph, and is subjected to a 1000-hour test using a sunshine carbon-accelerated accelerated weathering tester described in JIS Z 9117 (outdoor southern surface vertical exposure of 5 years). (Corresponding to the above), no abnormalities occurred in the image, and the durability was so high that almost no fading was visually recognized. If this is replaced with indoor storage, storage stability of more than 100 years has been obtained, and the size is larger than conventional silver halide photography and commonly used aqueous inkjet for business and home use. Image can be produced at a lower cost than before, and it is not necessary to dispose of the developing solution required for silver halide photography, it is extremely environmentally friendly, and it has extremely sharp high durability and high storage stability. Excellent photographic images are obtained.
[0115]
At this timeExamples of the method for performing the heat diffusion printing include an indirect heating method and a direct heating method. Indirect methods include heating by hot air and heating by irradiation with far-infrared rays. Direct heating includes a method in which a printing laminate is brought into direct contact with a heating plate, or a method in which the printing laminate is wound around a hot roll. Either of these heating methods may be selected, or may be used in combination. Although high-temperature heating of 150 to 200 ° C. is required for diffusion dyeing, if the temperature of the printing laminate itself is rapidly raised to the above-mentioned high temperature, rapid thermal expansion of the sheet occurs, and the sheet is expanded. Undesirably, appearance abnormalities such as wrinkles occur. As a result of intensive studies by the present inventors to solve this problem, the initial heating is 70 to 130 ° C., followed by 120 to 150 ° C., and when the temperature is further increased, heating is performed in the order of 140 to 200 ° C. If diffusion printing is performed in a cycle of temperature rise, heating at a constant temperature, and cooling at a constant temperature gradient of 150 ° C, 70 to 130 ° C, and normal temperature, thermal expansion and shrinkage due to temperature drop can be mitigated, and the sheet has external appearance such as wrinkles. It is preferable because no abnormality occurs. Further, it is preferable that the initial heating and heating be 10 to 60% of the entire heating time, the heating at a constant temperature is 20 to 80% of the entire heating time, and the temperature lowering is 10 to 40% of the entire heating time. It is more preferable that the initial heating and heating are 15 to 35% of the entire heating time, the heating at a constant temperature is 30 to 70% of the entire heating time, and the temperature lowering is 15 to 35% of the entire heating time. Further, in the case of roll heating, it is preferable to use a crown roll whose central portion is thicker than both end portions when the temperature is lowered, because wrinkles generated due to contraction of the sheet due to the temperature decrease can be prevented. At this time, it is more preferable that the gradient of the crown roll is such that the difference in diameter between both ends and the center is about 0.5 to 10 mm, preferably 1 to 5 mm per 1000 mm in width. In the case of indirect heating, the sheet is sandwiched between the upper and lower rolls at the entrance to the heating machine, and the sheet is conveyed by the lower support guide roll, which has been driven in sequence. It is more preferable that an upper pressing roll is provided to assist in proper conveyance so as to sandwich the sheet. As described above, indirect heating is preferable because a required number of heat treatments can be performed without losing the printing laminate. When a single plate is subjected to heat treatment, the sheet may be left on a heating plate heated to a required temperature, but when performing continuous treatment with a hot roll, in addition to the above conditions, the winding tension is increased. A width of 5 to 40 kg / m, preferably 10 to 30 kg / m, is suitable because wrinkles generated in the sheet can be prevented. When the width is less than 5 kg / m, wrinkles are generated when the sheet is wound, and when the width is more than 40 kg / m, unnecessary elongation is applied to the sheet, which is not preferable.
[0116]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. In the following examples, "parts" indicates parts by weight. "%" Means% by weight.
[0117]
(Example 1, Reference example)
In preparing the resin composition for the surface resin layer 1 shown in FIG. 1, hexafluoropropylene / ethyl vinyl ether / veova 9 / monovinyl adipate having a weight average molecular weight of about 45,000 as a fluorine-based resin = 50/15/20/15 (Weight ratio) Copolymer solution ("Vova 9": trade name of Japan Epoxy Resin Co., Ltd., vinyl ester of branched fatty acid, solvent: toluene / n-butanol = 70/30 weight ratio mixed solvent, nonvolatile content about 50 %), About 7.4 parts of sorbitol polyglycidyl ether having an epoxy equivalent of 170, about 0.6 parts of diazabicyclooctane, tinuvin 900 (manufactured by Ciba Specialty Chemicals, benzotriazole ultraviolet absorber) ) Is about 1 part, Tinuvin 292 (manufactured by Ciba Specialty Chemicals, Hinder) A resin composition containing about 1 part of an amine-based light stabilizer) is applied on a polyester film so as to have a dry film thickness of about 20 μm, and heated and dried at about 140 ° C. for about 10 minutes to form a surface resin layer 1. Obtained. Subsequently, on the surface resin layer 1 prepared above, about 100 parts of the vinyl polymer (a-1) synthesized in Reference Example 1 described above was used as a curing agent, Vernock DN-950 (Dai Nippon Ink Chemical Industry Co., Ltd.). About 25 parts by weight of a polyisocyanate prepolymer (non-volatile content: about 75%) and a dry film thickness of about 30 μm, and dried at about 140 ° C. for about 10 minutes to prevent dye transfer. A coloring resin layer 12 was prepared. As shown in FIG. 4, about 100 parts of an acrylic pressure-sensitive adhesive Finetack SPS-1016 (manufactured by Dainippon Ink and Chemicals, Inc.) on the surface of the dye transfer-preventive coloring resin layer 12 of the printing laminate thus obtained. A mixed solution of about 2 parts of a cross-linking agent Fine Tack TA-101-K (manufactured by Dainippon Ink and Chemicals, Inc., a curing agent chelating type for an adhesive) is applied, and heated and dried at about 100 ° C. for about 5 minutes. An adhesive layer 5 of about 35 μm was formed. Further, a release film obtained by applying an antistatic treatment to the opposite surface of the pressure-sensitive adhesive layer 5 to which the biaxially stretched polyester release film having a thickness of 50 μm, which is silicon-coated on one side, and annealing the release surface. 6 (manufactured by Teijin Dupont Film Co., Ltd., trade name: A-31, shrinkage in the film winding direction when heated at 150 ° C. for 30 minutes is 0.4%), and then the polyester film as the support film is peeled off To obtain the final product.
[0118]
Next, an image was printed on transfer paper (Gradess S-coat Paper) by a piezo-type printer (RJ-6000 manufactured by Mutoh Kogyo Co., Ltd.), which is a type of ink jet system separately prepared.. RiseAs the ink for ink jetting for sintering, ink for ink jetting (a set of six colors of cyan, magenta, yellow, black, light cyan and light magenta) manufactured by Kiwa Chemical Industry Co., Ltd. containing a sublimable dye was used. The printing surface of the transfer paper was applied to the surface resin layer 1 of the printing laminate prepared above, and the degree of vacuum was 3.99 × 10 3 using a heat vacuum applicator (VacuSeal 4468 manufactured by HUNT EUROPE).^ThreeAn image printed on the transfer paper is printed by heating and pressing the print laminate and the transfer paper together at a set temperature of about 170 ° C. for about 7 minutes at Pa (30 mmg). The image was transferred to the dye transfer preventing coloring resin layer 12 by diffusion dyeing.
[0119]
(Example 2)
In preparing the resin composition for the surface resin layer 1 shown in FIG. 2, Fluoronate K-703 (manufactured by Dainippon Ink and Chemicals, weight average molecular weight 40000, solid content hydroxyl value 72, non-volatile content) was used as a fluorine-based resin. 60%), Vernock DN-950 as a curing agent, Tinuvin 900 as an ultraviolet absorber, and Tinuvin 292 as an antioxidant. The compounding ratio of the resin composition for the surface resin layer 1 in Example 2 was such that Fluoronate K-703 was about 100 parts, Barnock DN-950 was about 25 parts, Tinuvin 900 was about 1 part, and Tinuvin 292 was about 1 part. is there. Then, the composition was applied on a polyester film so as to have a dry film thickness of about 20 μm, and was heated and dried at about 140 ° C. for about 10 minutes to obtain a surface resin layer 1. Subsequently, a polycarbonate-based non-yellowing urethane resin NY-331 (manufactured by Dainippon Ink & Chemicals, Inc., about 25% nonvolatile, solvent DMF, 100% modulus about 55 kg / cm) was formed on the surface resin layer 1 prepared above.²) And dried by heating at about 140 ° C. for about 10 minutes to produce a colored resin layer 2. Subsequently, about 100 parts of the vinyl polymer (a-2) synthesized in Reference Example 2 described above and about 50 parts of Vernock DN-950 as a curing agent were blended on the coloring resin layer 2. Was applied onto the colorable resin layer 2 so that the dry film thickness became about 15 μm, and dried at about 140 ° C. for about 10 minutes to prepare a dye transfer prevention layer 3. Subsequently, on the dye transfer preventing layer 3, about 100 parts of Acrydic 49-394-IM (manufactured by Dainippon Ink and Chemicals, Inc., nonvolatile content of about 50%) as an acrylic resin, about 15 parts of Burnock DN-950, The blended resin composition was applied so as to have a dry film thickness of about 20 μm, and dried at about 140 ° C. for about 10 minutes to produce a flexible resin layer 4.
[0120]
As shown in FIG. 5, the pressure-sensitive adhesive layer 5 and the release film 6 were formed on the surface of the flexible resin layer 4 of the printing laminate thus obtained in the same manner as in Example 1 to obtain a final product.
[0121]
Next, in the same manner as in Example 1, the printed surface of the transfer paper was applied to the surface resin layer 1 to transfer an image to the colorable resin layer 2.
[0122]
(Example 3)
The structure, dimensions, manufacturing method, and the like are the same as in Example 2 except that the formulation of the resin composition for the surface resin layer 1 and the formulation of the coloring resin layer 2 are changed as described below. The compounding example of the resin composition for the surface resin layer 1 in this example is Fluonate K-700 (manufactured by Dainippon Ink and Chemicals, weight average molecular weight: about 70,000, solid content hydroxyl value: 48, nonvolatile content: about 50%). Approximately 100 parts, Sumimar M-100C (Methylated melamine resin, Sumitomo Chemical Co., Ltd., nonvolatile content 100%) as a curing agent, and Nailure 3525 (KING INDUSTRIES, dinonylnaphthalenedisulfonic acid) as a curing catalyst. Are about 1.3 parts, Tinuvin 900 is about 1 part, and Tinuvin 292 is about 1 part.
[0123]
The compounding example of the resin composition for the coloring resin layer 2 is about 100 parts of Vernock D6-439 (alkyd resin manufactured by Dainippon Ink and Chemicals, Inc., solid content hydroxyl value 140, nonvolatile content 80%), and Vernock as a curing agent. About 82 parts of DN-980 (a polyisocyanate prepolymer manufactured by Dainippon Ink and Chemicals, 75% nonvolatile).
[0124]
(Example 4)
The structure, dimensions, manufacturing method, and the like are the same as in Example 2 except that the formulation of the resin composition for the surface resin layer 1 is changed as described below. In this example, the compounding example of the resin composition for the surface resin layer 1 is about 100 parts of Acridic A-9521 (silicon acrylic resin manufactured by Dainippon Ink and Chemicals, Inc., solid content 50%), and Acridic as a curing agent. About 22 parts of HZ-1018 (epoxy group-containing silicon compound manufactured by Dainippon Ink and Chemicals, 55% solids).
[0125]
(Example 5)
The structure, dimensions, manufacturing method, and the like are the same as in Example 2 except that a release temporary display surface layer capable of printing and displaying is laminated on the surface of the printing laminate. A dry film thickness of about 15 μm was formed on the surface resin layer 1 of the printing laminate prepared in Example 2 by using Fluorate FEM-600 (45% solid content) manufactured by Dainippon Ink and Chemicals, Ltd. as an aqueous fluororesin. The coating was performed as described above, and the coating was dried by heating at about 110 ° C. for about 5 minutes. Subsequently, MZ-100 (mixture of amorphous silicon dioxide, polyurethane and vinyl resin, solid content of 15%, solid content of Takamatsu Yushi Co., Ltd.) was used as an ink jet receiving agent so that the dry film thickness was about 30 μm on the dried film. (Porous pigment content: about 56%), and dried by heating at about 110 ° C. for about 5 minutes. An image was printed on the temporary display surface layer thus produced in the same manner as in Example 1. After that, a hot air dryer (Fine Oven DF6L manufactured by Yamato Scientific Co., Ltd.) is set at about 170 ° C., and a heat treatment is performed for about 7 minutes to diffuse and infiltrate the sublimable dye, so that the coloring resin layer 2 on the printing laminate side Then, the temporary display surface layer was peeled off in a film state.
[0126]
(Example 6, Reference example)
As the dye transfer preventing layer 3 shown in FIG. 2, an annealed biaxially stretched polyester film (manufactured by Teijin DuPont Films, trade name: MX534; shrinkage in the winding direction of the film when heated at 150 ° C. for 30 minutes is 0). .3%, a film thickness of 97 μm) and a resin composition for the colorable resin layer 2 having the same composition as in Example 2 was applied so that the dry film thickness became about 20 μm. Heating and drying was performed for a minute, thereby producing a coloring resin layer 2.
[0127]
Subsequently, the resin composition for the surface resin layer 1 described in Example 2 was applied on the coloring resin layer 2 so that the dry film thickness was about 20 μm, and was heated and dried at about 140 ° C. for about 10 minutes. Then, a surface resin layer 1 was obtained. The pressure-sensitive adhesive layer 5 and the release film 6 were formed on the back surface of the biaxially stretched polyester film as the dye transfer preventing layer of the printing laminate thus obtained in the same manner as in Example 1 to obtain a final product. did. Next, in the same manner as in Example 1, the printed surface of the transfer paper was applied to the surface resin layer 1 to transfer an image to the colorable resin layer 2.
[0128]
(Comparative Example 1)
Except for omitting the step of the dye transfer prevention layer 3, the structure, dimensions, manufacturing method, and the like are the same as in Example 2.
[0129]
(Comparative Example 2)
Except for omitting the steps of the dye transfer prevention layer 3 and the flexible resin layer 4, the structure, dimensions, manufacturing method, and the like are the same as in Example 2.
[0130]
(Comparative Example 3)
Structure, dimensions, manufacturing method, etc., except that the compounding solution of the resin composition of the surface resin layer 1, the colorable resin layer 2, and the dye transfer preventing layer 3 are changed as follows and the flexible resin layer 4 is omitted. Is the same as in the second embodiment.
[0131]
Polyurethane-based resin solution Burnock L7-920 (manufactured by Dainippon Ink and Chemicals, Ltd., non-volatile content) 25 ± 1%, solvent toluene, sec-butanol) was applied so as to have a dry film thickness of 20 μm, and a heat treatment was performed at about 140 ° C. for about 10 minutes to produce a coloring resin layer 2. Subsequently, a vinyl chloride resin paint having the following composition is applied on the colorable resin layer 2 so that the dry film thickness becomes about 20 μm, and is heated and dried at about 140 ° C. for about 10 minutes to form the surface resin layer 1. did.
(1) 100 parts of vinyl chloride resin
(2) Ethylene / vinyl ester resin 25 parts
(3) 10 parts of polyester plasticizer
As the vinyl chloride resin, Nikavinyl SG-1100N (manufactured by Nippon Carbide Industrial Co., Ltd.) was used. As the ethylene / vinyl ester resin, Elvaloy (manufactured by DuPont Mitsui Polychemicals, Inc., trade name) was used. As the polyester plasticizer, A resin having a number average molecular weight (Mn) of about 3000 synthesized from a mixed dihydric alcohol composed of propylene glycol, butanediol, and hexanediol and adipic acid was used.
[0132]
The results and test methods after image transfer for the above Examples and Comparative Examples are summarized in Tables 2 to 5 below.
[0133]
[Table 2]

[0134]
[Table 3]

[0135]
[Table 4]

[0136]
[Table 5]

[0137]
(Remarks) The black stars 1 to 7 in Tables 2 to 5 are replaced with (Note 1) to (Note 7).
(Note 1) 45 ° outdoor exposure test on the south side (test site: Wakayama Prefecture) The test period is one year
○ (Keep sharpness)> △ (Slightly blurred image)> × (Image is blurry and unclear)
(Note 2) Yubucon (Atlas, USA) accelerated weathering test
1 cycle: UV irradiation 60 ° C × 4 hours / coagulation 40 ° C × 4 hours
Test time: 1000 hours
○ (Keep sharpness)> △ (Slightly blurred image)> × (Image is blurry and unclear)
(Note 3) The test time is 1000 hours according to the conditions of the sunshine carbon accelerated weathering test described in JIS Z 9117.
[0138]
○ (Keep sharpness)> △ (Slightly blurred image)> × (Image is blurry and unclear)
(Note 4) Erichsen tester (manufactured by Toyo Seiki Seisakusho)
Adhered substrate: 1 mm thick aluminum plate with hardness H24 of A50502P specified in JIS H 4000.
Test method: The printing laminate was attached to a substrate, left at room temperature for 48 hours, and then a punch having a radius of 10 mm was pressed from the rear surface of the substrate and pressed into the substrate by 6 mm to form a curved surface. Thereafter, the Yubucon accelerated weathering test (Note 2) is performed for 1000 hours.
：: No abnormal appearance.
Δ: Cracks occurred at the top of the extruded curved surface.
×: The entire sheet rises from the substrate.
(Note 5) The degree of vacuum was 3.99 × 10 using a heat vacuum applicator (VacuSeal 4468 manufactured by HUNT EUROPE).³An image printed on the transfer paper is printed by heating and press-bonding at a set temperature of about 170 ° C. for about 7 minutes at Pa (30 mmHg) and heating the transfer paper and the transfer paper together. The state of the film after the image is transferred by diffusion dyeing to
：: No abnormal appearance.
×: Wrinkles occurred on the entire sheet.
(Note 6) The test method is the same as (Note 3). The color difference ΔE was measured by a stimulus value direct reading method specified in JIS Z 8722, and determined using a color difference expression specified in “JIS Z 8730 color difference display method 6”.
(Note 7) The test method is the same as (Note 1). The color difference ΔE was determined in the same manner as in (Note 6).
[0139]
As shown in Tables 2 to 5 above, in Example 1, the suitability for attaching a three-dimensional curved surface was not good because the flexible resin layer was not formed, but the sheet after heat transfer was excellent in sharpness retention of the image. Was also good. Examples 2 to 5 were also suitable for three-dimensional curved surface sticking, were excellent in image clarity holding power, and were in good condition after heat transfer. In Example 6, although the suitability for sticking on a three-dimensional curved surface was poor, the sheet after heat transfer was excellent because the biaxially stretched polyester film annealed for the dye transfer prevention layer was used, and thus the image retention property was excellent. No wrinkles were observed. In Comparative Examples 1 and 2, since the dye transfer preventing layer 3 was not formed, bleeding of the image and the like occurred, and the sharpness retention of the image was poor. In Comparative Example 3, since the biaxially stretched polyester film was used for the dye transfer preventing layer, the suitability for sticking on a three-dimensional curved surface was poor, and the sheet after heat transfer had wrinkles. Further, since a vinyl chloride resin was used for the surface resin layer 1, the ability to maintain the sharpness of the image was low, and the fading resistance of the image was poor. Therefore, the printing laminate of the present invention, on which the dye transfer preventing layer 3 is formed, can maintain image clarity without causing blurring or blurring of the image even when left for a long period of time, and is resistant to fading. It was possible to realize a highly weather-resistant printed laminate having very excellent properties. When biaxially stretched polyester was used, the use of an annealed film prevented generation of wrinkles due to heating. In addition, it was found that if the flexible resin layer 4 was formed below the dye transfer preventing layer 3 when used on a curved surface, it could be adequately dealt with.
[0140]
【The invention's effect】
As described above, the present invention has an affinity for the sublimable dye in the inner layer.A coloring resin layer,Dye migration prevention to prevent migration of the dyeStop layerBy forming the above, it is possible to provide a printing laminate capable of preventing migration of a printed sublimable dye, a printing method using the same, and a printed material. Further, the present invention provides a method for preventing dye migration.Stop layerIn the further lower layer, the dye transfer preventionStop layerBy providing a flexible resin layer having a higher elongation rate, it is possible to provide a printing laminate having flexibility that can be attached to a curved substrate, a printing method using the laminate, and a printed material.
[Brief description of the drawings]
FIG. 1 of the present invention.Reference exampleFIG. 3 is a cross-sectional view of the printing laminate in FIG.
FIG. 2 of the present invention.oneIt is sectional drawing of the laminated body for printing in embodiment.
FIG. 3 shows the present invention.AnotherIt is sectional drawing of the laminated body for printing in embodiment.
FIG. 4 is a cross-sectional view of a printing laminate according to still another embodiment of the present invention.
FIG. 5 is a cross-sectional view of a printing laminate according to still another embodiment of the present invention.
FIG. 6 is a sectional view of a printing laminate according to still another embodiment of the present invention.
FIG. 7 is a cross-sectional view of a printing laminate according to still another embodiment of the present invention.
FIG. 8A is a process chart showing still another embodiment of the present invention, in which a glass ball temporary fixing layer is formed on a polyester film, transparent glass balls are embedded on a plurality of planes on the surface thereof, and a metal reflection film is formed. B is a schematic cross-sectional view of a portion in which a primer layer is formed on a polyester film and a support resin sheet is formed thereon, and C is a temporary fixation of a support resin sheet to a glass ball. D is a schematic cross-sectional view of a portion along the surface of the layer, D is a schematic cross-sectional view of a portion where the supporting resin sheet is pressed against the surface of the glass ball temporary fixing layer, and E is a glass with a polyester film from the supporting resin sheet surface. FIG. 4F is a schematic cross-sectional view of a portion where the sphere temporary fixing layer is removed, and FIG. 4F is a schematic cross-sectional view of a portion before the support resin sheet surface is covered with the printing laminate of the present invention and subjected to thermocompression molding with a patterned embossing roll. , The same, a cross-sectional schematic view of the portion subjected to thermocompression bonding molded with an embossing roll.
[Explanation of symbols]
1 Surface resin layer
2 Colorable resin layer
3 Dye transfer prevention layer
4 Flexible resin layer
5 Adhesive layer
6 Release material
12 Dye transfer prevention coloring resin layer
101 Focus layer film
102 High refractive glass beads
103 Metal reflective film
201 Glass bead fixing layer
202 High refractive glass beads
203 Focus layer film
204 Metal reflective film
302 glass sphere
303 Metal reflective film
304 support resin sheet
305 primer layer
306 polyester film
307 Temporary adhesion layer of glass sphere
308 polyester film
309 Embossed roll with pattern
310 Emboss groove

Claims (24)

It is a printing laminate for coloring by infiltrating the sublimable dye into the resin layer by heating, in order from the surface,
A surface resin layer (A) having a low affinity for the sublimable dye and allowing the dye to pass therethrough,
As the dye transfer preventing coloring resin layer (B), a coloring resin layer (B1) having an affinity for the dye and a dye transfer preventing layer (B2) for preventing transfer of the dye are laminated. Yes,
The dye transfer prevention layer (B2) is a resin layer mainly composed of a vinyl resin having a glass transition temperature (Tg) of 70 ° C. or more and an SP value of 9.0 or more, and a film thickness of 1 μm or more and 100 μm or less. printing laminate according to claim Rukoto Oh. Further lower pre Kisome charge migration preventive layer (B2), printing according to claim 1 elongation rate with a large becomes flexible resin layer (C) from the previous Kisome charge migration preventive layer (B2) Laminate. The dye transfer prevention layer (B2) is a tertiary resin obtained by crosslinking a resin mainly composed of a vinyl copolymer having a glass transition temperature (Tg) of 70 ° C. or more and an SP value of 9.0 or more together with a curable substance. The printing laminate according to claim 1, which is a layer containing an original polymer. The printing laminate according to any one of claims 1 to 3 , wherein the surface resin layer (A) is formed of a fluororesin made of a fluoroolefin copolymer soluble in a solvent. The printing laminate according to any one of claims 1 to 3 , wherein the surface resin layer (A) is formed of a silicon-modified acrylic resin. Before Symbol wearing color resin layer (B1) is a printing laminate according to any one of claims 1 to 5 molecular weight 1300 or less of a low molecular weight compound is a resin containing 20 wt% or less. The printing laminate according to any one of claims 1 to 6 , wherein a matting agent is added to the surface resin layer (A) so that the surface layer has a 60 ° gloss of 70 or less. At least one or more layers of the surface resin layer (A) 及 beauty the colored resin layer (B1) is a high molecular weight type ultraviolet absorber, a high molecular weight type hindered amine light stabilizer and a high molecular weight type hindered phenol The printing laminate according to any one of claims 1 to 7 , further comprising at least one selected from a series of antioxidants. The surface resin layer (A), by adding a light diffusing fine particles in at least one or more layers of the prior SL dye migration preventive layer (B2) and their underlying layers, the light diffusing function is added A printing laminate according to any one of claims 1 to 8 . Before SL colored resin layer (B1) and claims with improved transmission density of the printed image to form a white layer using a white pigment in at least one or more layers of said dye migration preventive layer (B2) 10. The printing laminate according to any one of 1 to 9 . The printing laminate according to any one of claims 1 to 10, wherein a metal layer is formed below the coloring resin layer (B1) or the dye transfer preventing layer (B2). Metal reflection film to be the lower layer of the prior SL dye migration preventive layer (B2) or a layer including high refractive glass beads is laminated on the lower layer of the flexible resin layer (C), the layer further comprising a high-refractive glass beads The printing laminate according to any one of claims 1 to 8 , further comprising a retroreflective layer formed thereon. Metal reflection under the prior SL dye migration preventive layer (B2) or sticking layer high refractive glass beads are fixed to the lower layer of the flexible resin layer (C), focusing layer are sequentially stacked, further focusing layer The printing laminate according to any one of claims 1 to 8 , further comprising a retroreflective layer having a film formed thereon. A plurality of transparent spheres provided with a metal reflective film in a lower hemisphere, a support resin sheet holding the plurality of transparent spheres, and a transparent cover covering the plurality of transparent spheres by being disposed on the surface side of the support resin sheet The printing according to any one of claims 1 to 8 , wherein the cover film is the printing laminate in a retroreflective sheet comprising a film, and the supporting resin sheet having a joining portion for holding the cover film. For laminate. The surface resin layer (A) is composed of [M 2 ⁺ _{1 -X} M ³⁺ _X (OH) ₂ ] ^{X +} [A ⁿ⁻ _{X / n} · mH ₂ O] ^X− (where M ²⁺ is a divalent A metal ion, M ³⁺ is a trivalent metal ion, A ⁿ⁻ is an n-valent anion, X is greater than 0 and 0.33 or less, and 0 ≦ m ≦ 2). The printing laminate according to any one of claims 1 to 14 , which is coated with a coating film forming composition containing fine particles. The back surface of the printing laminate, further comprising a pressure-sensitive adhesive layer and a release material on the outside thereof, wherein the pressure-sensitive adhesive layer or the release material is subjected to an antistatic treatment, according to any one of claims 1 to 15 . Printed laminate. At least one releasable temporary display layer capable of printing and displaying is further provided on the surface resin layer (A), and the side of the temporary display layer that is not in contact with the surface resin layer (A) is a sublimable dye. It has an absorptivity of the ink containing the agent, and it is possible to sublimate the sublimable dyeing agent by heat treatment to diffuse-dye the laminate for printing, and after the heat treatment, the temporary display layer is The printing laminate according to any one of claims 1 to 16 , which can be peeled off from the surface resin layer (A) of the printing laminate in a film state. A method for printing the printing laminate according to any one of claims 1 to 16 ,
The transfer paper is printed using an ink containing a sublimable dye, and the image forming surface of the transfer paper is brought into contact with the surface resin layer (A). the subliming, printing method characterized by diffuse staining before Symbol wearing color resin layer (B1). A method for printing the printing laminate according to claim 17 ,
A printing method, wherein the temporary display layer is printed using an ink containing a sublimable dye. A method for printing the printing laminate according to claim 17 ,
Diffuse staining the the temporary display layer ink containing a sublimable dye to be printed using the sublimation SL previous a sublimating dye wearing color resin layer by performing a subsequent heat treatment (B1) A printing method characterized by causing a printing operation. The printing method according to any one of claims 18 to 20 , wherein the printing is printing by an inkjet method. The printing method according to claim 18 , wherein the heat treatment temperature is in a range of 150 to 200 ° C. 21 . The printing method according to claim 18 or 20 , further comprising a step of drying the printing ink between the printing and the heat treatment. A printed matter printed using the printing method according to any one of claims 18 to 23 .

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