JP3840351B2 - Fluorescent latent image transfer method and security pattern forming body - Google Patents

Description

【００１９】
蛍光インキ層３に用いられるバインダー樹脂は、エチルセルロース、エチルヒドロキシセルロース、ヒドロキシプロピルセルロース、メチルセルロース、酢酸セルロース等のセルロース系樹脂、ポリビニルアルコール、ポリ酢酸ビニル、ポリビニルブチラール、ポリビニルアセタール、ポリビニルピロリドン等のビニル系樹脂、ポリ（メタ）アクリレート、ポリ（メタ）アクリルアミド等のアクリル系樹脂、ポリウレタン樹脂、ポリアミド樹脂、ポリエステル系樹脂、これらの樹脂の混合物等が挙げられる。バインダー樹脂としては、ポリビニルブチラール、ポリビニルアセタールが、蛍光剤の移行性及び転写フィルムとした場合の保存安定性が良好であることから好ましい。蛍光インキ層３の厚さは０．１〜５．０ｇ／ｍ² に形成するのが好ましい。
【００２０】
蛍光インキ層３は、蛍光剤、バインダー樹脂、その他の添加剤等を添加したインキをグラビアコート等の公知の塗工手段を用いて塗布形成するこことができる。
【００２１】
背面層４は、サーマルヘッド等の加熱素子との融着を防止したり、給紙性を改良するために設けられる。また、背面層４により転写フィルムをロール状に巻とったり、シート状物を積み重ねたりした際に、背面が蛍光インキ層等の表面層に接着するのを防止することができる。背面層４は、耐熱滑性、離型性を有することが好ましい。背面層の材質として、硬化性シリコーンオイル、硬化性シリコーンワックス、シリコーン樹脂、フッ素樹脂、アクリル樹脂等の剥離性を有する材料が挙げられる。背面層４の厚さは通常０．１〜３．０μｍに形成される。
【００２２】
蛍光潜像転写フィルムはシート、連続ロール、リボンのいずれの状態であってもよい。図１に示す蛍光潜像転写フィルムは、蛍光インキ層３が転写層の全面にベタ印刷されて形成されているものであるが、蛍光潜像転写フィルムは、上記蛍光インキ層３以外に、熱昇華性染料層５、熱溶融性インキ層６等の領域をシートの流れ方向に沿って面順次に形成してもよい。また、保護層７の領域を設けてもよい。以下、これらの蛍光潜像転写フィルムの他の態様について説明する。
【００２３】
図２に示す蛍光潜像転写フィルム１は、耐熱性基材フィルム２の蛍光インキ層３が設けられている同じ転写面に、イエロー染料層５Ｙ、マゼンタ染料層５Ｍ、シアン染料層５Ｃ、ブラック染料層５ＢＫなどの熱昇華性染料層５、蛍光インキ層３、ブラック色の熱溶融性インキ層６Ｂの各領域が面順次に形成され、この構成単位の領域がフィルムの流れ方向に繰り返し形成されている。また、耐熱性基材フィルム２の他面側には、背面層４が設けられている。この態様では蛍光インキ層３以外の転写層としては、イエロー染料層５Ｙ、マゼンタ染料層５Ｍ、シアン染料層５Ｃ、ブラック染料層５ＢＫ、ブラック色の熱溶融性インキ層６（熱溶融性ブラックインキ層６ＢＫ）のうちの少なくとも１層以上が、蛍光インキ層３と同一の転写面上に設けられていればよい。
【００２４】
図３（ａ）〜（ｈ）は蛍光潜像転写フィルムの蛍光インキ層以外の層として熱昇華性染料層５、熱溶融性インキ層６を設けた場合の態様を示す平面図である。同図に示すように、蛍光インキ層３、熱昇華性染料層５（５Ｙ、５Ｍ、５Ｃ、５ＢＫ）、熱溶融性インキ層６等の領域（パネルともいう）は任意の順序に形成することができる。また、各領域の長さも、特に限定されず任意の長さの領域として形成することができる。図３（ａ）〜（ｈ）の態様は、各領域の面方向の配列順を以下の通りの構成としたものであり、この領域の構成を基本単位として流れ方向に繰り返し形成されている。
【００２５】
（ａ）蛍光インキ層３のみからなるベタフィルム。
（ｂ）イエロー染料層５Ｙ、マゼンタ染料層５Ｍ、シアン染料層５Ｃ、蛍光インキ層３。
（ｃ）イエロー染料層５Ｙ、マゼンタ染料層５Ｍ、シアン染料層５Ｃ、ブラック染料層５ＢＫ、蛍光インキ層３。
（ｄ）イエロー染料層５Ｙ、マゼンタ染料層５Ｍ、シアン染料層５Ｃ、蛍光インキ層３、熱溶融性ブラックインキ層６ＢＫ。
（ｅ）ブラック染料層５ＢＫ、蛍光インキ層３。
（ｆ）蛍光インキ層３、熱溶融性ブラックインキ層６ＢＫ。
（ｇ）イエロー染料層５Ｙ、マゼンタ染料層５Ｍ、シアン染料層５Ｃ、ブラック染料層５ＢＫ、蛍光インキ層３、熱溶融性ブラックインキ層６ＢＫ。
（ｈ）上記（ｇ）と同じ領域の順序であるが、イエロー染料層５Ｙ、マゼンタ染料層５Ｍ、シアン染料層５Ｃの領域の合計した専有面積を、ブラック染料層５ＢＫ、蛍光インキ層３、熱溶融性ブラックインキ層６ＢＫの領域の専有面積よりも小さく形成した。
【００２６】
熱昇華性染料層５は、イエロー、マゼンタ、シアン又はブラック色のいずれかの昇華性染料、バインダー樹脂、離型剤、その他の添加剤を溶媒に溶かし、染料層用塗布液を調整し、耐熱性基材フィルム上の所定領域に各色の塗布液をそれぞれ、グラビアコート等の各種塗工手段を用いて塗工して乾燥することで形成できる。
【００２７】
イエロー昇華性染料は、フォロンブリリアントイエロー−Ｓ−６ＧＬ（サンド社製ディスパースイエロー２３１の商品名）、マクロレックスイエロー６Ｇ（バイエル社製ディスパースイエロー２０１の商品名）等が挙げられる。マゼンタ昇華性染料は、ＭＳ−ＲＥＤＧ（バイエル社製ディスパースバイオレット２６の商品名）等が挙げられる。シアン昇華性染料としては、カヤセットブルー７１４（日本化薬社製ソルベントブルー６３の商品名）、フォロンブリリアントブルーＳ−Ｒ（サンド社製ディスパースブルー３５４の商品名）、ワクソリンＡＰ−ＦＷ（ＩＣＩ社製ソルベントブルー３６の商品名）、ブラック色の昇華性染料としては、上記イエロー、マゼンタ、シアン染料の混合物等が挙げられる。
【００２８】
熱昇華性染料層５のバインダー樹脂としては、エチルセルロース、エチルヒドロキシセルロース、ヒドロキシプロピルセルロース、メチルセルロース、酢酸セルロース等のセルロース系樹脂、ポリビニルアルコール、ポリ酢酸ビニル、ポリビニルブチラール、ポリビニルアセタール、ポリビニルピロリドン等のビニル系樹脂、ポリ（メタ）アクリレート、ポリ（メタ）アクリルアミド等のアクリル系樹脂〔上記（メタ）はメタアクリレートを意味する〕、ポリウレタン樹脂、ポリアミド樹脂、ポリエステル系樹脂、これらの樹脂の混合物等が挙げられる。バインダー樹脂としては、ポリビニルブチラール、ポリビニルアセタールが染料移行性及び転写フィルムとした場合の保存安定性が良好であることから好ましい。
【００２９】
熱溶融性インキ層６は、着色剤、ビヒクル、及びその他の添加剤等を含有する熱溶融性インクをホットメルトコート、ホットラッカーコート、グラビアコート、グラビアリバースコート、ロールコートのような公知の塗工手段を用いて形成できる。熱溶融性インキ層６の厚さは、通常０．２〜１０μｍに形成される。熱溶融性インキ層は、高濃度で明瞭な文字、記号等の記録に最適な黒色（ブラック）の着色剤を用いるのが好ましい。
【００３０】
熱溶融性インキ層６のビヒクルとしては、例えば、ワックス、ワックスと乾性油、樹脂、鉱油、セルロース、ゴムの誘導体等との混合物が挙げられる。上記ワックスは、マイクロクリスタリンワックス、カルナバワックス、パラフィンワックス、フィッシャートロプシュワックス、低分子ポリエチレン、木ロウ、ミツロウ、鯨ロウ、イボタロウ、羊毛ロウ、セラックワックス、キャンデリラワックス、ペトロラタム、一部変性ワックス、脂肪酸エステル、脂肪酸アミド等が挙げられる。
【００３１】
蛍光潜像転写フィルムは図４（ａ）〜（ｉ）に示すように、蛍光インキ層３以外の層として保護層７を蛍光インキ層３と同じ転写面に面順次に形成してもよい。具体的に図４（ａ）〜（ｉ）の態様は、各領域の面方向の配列順を以下の通りの構成としたものであり、この領域の構成を基本単位として流れ方向に繰り返し形成されている。
（ａ）蛍光インキ層３、保護層７。
（ｂ）イエロー染料層５Ｙ、マゼンタ染料層５Ｍ、シアン染料層５Ｃ、蛍光インキ層３、保護層７。
（ｃ）イエロー染料層５Ｙ、マゼンタ染料層５Ｍ、シアン染料層５Ｃ、ブラック染料層５Ｂ、蛍光インキ層３、保護層７。
（ｄ）イエロー染料層５Ｙ、マゼンタ染料層５Ｍ、シアン染料層５Ｃ、蛍光インキ層３、熱溶融性ブラックインキ層６ＢＫ、保護層７。
（ｅ）ブラック染料層５ＢＫ、蛍光インキ層３、保護層７。
（ｆ）蛍光インキ層３、熱溶融性ブラックインキ層６ＢＫ、保護層７。
（ｇ）イエロー染料層５Ｙ、マゼンタ染料層５Ｍ、シアン染料層５Ｃ、ブラック染料層５ＢＫ、蛍光インキ層３、熱溶融性ブラックインキ層６ＢＫ、保護層７。
（ｈ）上記（ｇ）と同じ領域の順序であるが、イエロー染料層５Ｙ、マゼンタ染料層５Ｍ、シアン染料層５Ｃの領域の合計した専有面積を、ブラック染料層５ＢＫ、蛍光インキ層３、熱溶融性ブラックインキ層６ＢＫ、保護層７の領域の専有面積よりも小さく形成した。
（ｉ）熱溶融性ブラックインキ層６ＢＫ、保護層７、イエロー染料層５Ｙ、マゼンタ染料層５Ｍ、シアン染料層５Ｃ、蛍光インキ層３、熱溶融性ブラックインキ層６ＢＫ、保護層７。
【００３２】
上記図４において、保護層を除くパネルの位置は順不同でも良い。但し、蛍光インキ層３のパネル順序は保護層の後でもよい。保護層７は、転写フィルムから被転写体に直接転写を行う場合、転写後の画像の最表面に位置させて画像を良好に保護する為には、図４（ａ）〜（ｉ）に示す通り、一般的には面順次に設けた領域の一構成単位の中の最後の位置に設けるのが好ましい。また、保護層７は、図４（ｉ）に示す如く、例えば熱溶融性ブラックインキ層６ＢＫの後と領域単位の最後の位置との２箇所に設けたように、一つの面順次の構成単位の中で、２箇所以上の領域に設けてもよい。
【００３３】
保護層７は、この種転写フィルムの保護層形成用樹脂を含む塗工組成物を公知の塗工手段でフィルム基材の表面に塗布して形成することができる。保護層７は無色透明、或いは着色透明等の、転写後にその下層の画像が見える程度の透明に形成される。保護層形成用樹脂として例えば、ポリエステル、ポリスチレン、アクリル、ポリウレタン、アクリルウレタン等の樹脂の単体又は混合物、これらの樹脂をシリコーン変性させた樹脂、これらの変性樹脂の混合物、電離放射線硬化性樹脂、紫外線遮断性樹脂等が挙げられる。保護層７の厚さは、通常は０．５〜１０μｍ程度に形成される。
【００３４】
電離放射線硬化性樹脂を含有する保護層は、耐可塑剤性や耐擦過性が特に優れている。電離放射線硬化性樹脂としては公知のものを使用することができ、例えば、ラジカル重合性のポリマー又はオリゴマーを電離放射線により架橋、硬化させ、必要に応じて光重合開始剤を添加し、電子線や紫外線によって重合架橋させたものを使用できる。
【００３５】
紫外線遮断性樹脂を含有する保護層は、印画物に耐光性を付与することを主目的とする。紫外線遮断性樹脂としては、例えば、反応性紫外線吸収剤を熱可塑性樹脂又は上記の電離放射線硬化性樹脂に反応、結合させて得た樹脂を使用することができる。反応性紫外線吸収剤は、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、置換アクリロニトリル系、ニッケル−キレート系、ヒンダードアミン系のような非反応性の有機系紫外線吸収剤に、付加重合性二重結合（例えばビニル基、アクリロイル基、メタアクリロイル基など）、アルコール性水酸基、アミノ基、カルボキシル基、エポキシ基、イソシアネート基のような反応性基を導入したものである。
【００３６】
また、保護層７にはホログラムのパターン等を形成することができる。ホログラムパターンは、レリーフホログラムの凹凸模様等が挙げられる。またそれ以外のパターンとしては、回折格子の凹凸模様等でもよい。
【００３７】
転写層として蛍光インキ層３以外の層を面順次に設け複数の層の領域を設けた蛍光潜像転写フィルムにおいて、各領域の長さ（又は領域の面積）は、同じ長さに形成して各層の領域が同じ面積となるように転写フィルムを形成してもよいが、図３（ｈ）及び図４（ｈ）の態様に示すように、イエロー、マゼンタ、シアン色の熱昇華性染料層５（５Ｙ、５Ｍ、５Ｃ）の領域の長さを小さくして該染料層５の専有面積が、該染料層以外の層（蛍光インキ層３、熱昇華性ブラック染料層５ＢＫ、熱溶融性ブラックインキ層６ＢＫ、保護層７等）を合計した領域の専有面積よりも小さくなるように形成することもできる。
【００３８】
図５及び図６は、本発明蛍光潜像転写フィルムの形成方法により形成される印画物の態様を示す断面図である。図５に示す印画物９は、被転写体１０の表面に蛍光潜像１１、及び昇華性染料によるカラーの転写画像１２、昇華性染料による単色の転写画像１３、熱溶融性インキによる単色の転写画像１４等の可視画像を設け、その表面を保護層１５により覆って構成したものである。
【００３９】
また図６に示す印画物９は、被転写体の表面に昇華性染料によるカラーの転写画像１２、昇華性染料による単色の転写画像１３、熱溶融性インキによる単色の転写画像１４等の可視画像を設けた後、保護層１５を上記画像表面全体を覆うように形成し、該保護層１５の表面に蛍光潜像１１を設けたものである。
【００４０】
本発明方法において、蛍光潜像１１を形成する時期は、（ａ）可視画像を形成した後、（ｂ）可視画像を形成する前、（ｃ）可視画像を形成する途中、のいずれでもよい。また、蛍光潜像１１を形成する位置は、上記（ａ）の場合は、可視画像と重ならない位置、可視画像と重なる位置のいずれに設けてもよく、上記（ｂ）の場合には、可視画像と重ならない位置であればよい。
【００４１】
また保護層１５を形成する際、図５に示すように、可視画像及び蛍光潜像１１の全体を覆い印画物９の最表面に形成する場合には、印画物の画像の保存性が最も良好であり、例えば耐擦傷性等の耐久性が要求されるカード等には最適である。また、図６に示すように、蛍光潜像１１を保護層１５の表面に設ける場合は、蛍光潜像は上記転写フィルムに形成された蛍光インキ層程度の厚みであれば、下層の可視画像を見ることを何ら妨げない為、可視画像の上方であっても問題なく形成することができ、形成位置に制約がないといった利点が生じる。このように上記印画物の蛍光潜像、可視画像、保護層等の形成位置、形成順序等は、使用される印画物の用途等に応じて適宜選択できる。
【００４２】
上記の可視画像及び保護層は、印刷方法、塗工方法、他の転写シートを用いた転写方法等で形成することも可能であるが、先に説明した、昇華性染料層や熱溶融転写層、或いは保護層等を蛍光インキ層と面順次に設けた転写フィルムを用いることで、蛍光潜像に加え、昇華性染料層による画像や、保護層等を連続的に形成することができるため好ましい。
【００４３】
このような蛍光潜像転写フィルムの昇華性染料層は、フルカラーの写真のような連続階調の画像、単色写真のような連続階調の画像を形成するのに最適に用いられるが、階調のない単色及び多色の画像も形成できる。また、熱溶融性ブラックインキ層は、階調のない文字、符号等の印字に最適に用いられる。
【００４４】
印画物９を形成する被転写体１０としては、熱転写受像シートが好ましく用いられる。熱転写受像シートは、基材の表面に受容層が設けられて構成されるものである。基材は、普通紙、合成紙、合成樹脂又はエマルジョン含浸紙等の紙、ポリエチレンテレフタレート等の飽和ポリエステル、ポリアミド、ポリエチレン、ポリプロピレン、ポリアクリル酸エステル、ポリカーボネート、ポリウレタン、ポリ塩化ビニル、ポリ−酢酸ビニル、ポリスチレン、セルロース系樹脂、ポリサルホン、ポリイミド、等のプラスチックシート（フィルムも含む）が挙げられる。基材は透明でも不透明でもよく、又、基材中に白色顔料等を添加して反射性を有するものであってもよい。また基材はカード状に形成されていてもよい。
【００４５】
熱転写受像シートの受容層は、染料染着性樹脂から形成される。染料染着性樹脂は、例えば、飽和ポリエステル、ポリアミド、ポリアクリル酸エステル、ポリカーボネート、ポリウレタン、ポリビニルアセタール、ポリ塩化ビニル、塩化ビニル−酢酸ビニル共重合体、ポリ酢酸ビニル、ポリスチレン、スチレン−アクリル共重合体、スチレン−ブタジエン共重合体、ビニルトルエン−アクリル共重合体、セルロース系樹脂等が挙げられる。これらの樹脂は単独或いは２種以上を混合してもよい。また受容層には、熱転写シートの融着を防止するための離型剤、各種着色剤等の添加剤を添加してもよい。
【００４６】
また、熱転写受像シートの背面側（受容層と反対の面）にはシリコーンオイル、フッ素系化合物、各種ワックス等からなる離型層を設けてもよい。
【００４７】
これらの熱転写受像シートは、全く印刷されない状態のものであっても、或いは、予め印刷形成された用紙、冊子、帳票等の形態に形成されたものでもよい。
【００４８】
蛍光潜像転写フィルム、或いはその他の昇華性染料転写シート、保護層転写シート等の画像の転写に用いる加熱素子としては、サーマルヘッド、レーザー等の加熱手段が用いられ、転写すべき画像情報に応じた加熱がなされるように形成されている。これらの加熱素子は市販のものが利用できる。
【００４９】
本発明の蛍光潜像転写方法は、ＩＤカード等の身分証明カードやクレジットカード等のカード類、パスポート、免許証等の写真と文字の入った証明書を形成するのに最適に利用できる。
【００５０】
以上の蛍光潜像転写方法は、蛍光インキ層をパターン状に被転写基材（被記録媒体）に転写して蛍光潜像を形成するものである。この方法では、蛍光インキ層に溶融転写可能なバインダーを用いた場合には、バインダー樹脂と上記の特定の蛍光剤とがともに被転写体に移行して蛍光潜像を形成する。また、バインダー樹脂として、溶融転写しないものを用いた場合には、蛍光インキ層の上記の蛍光剤は昇華性を有するため、蛍光剤のみが被転写基材に移行して蛍光潜像を形成する。
【００５１】
一般に昇華転写の場合には階調表現に優れるが、溶融転写と比較して染料や蛍光剤などの転移量が少なく、形成された画像の濃度が低くなるため、鮮明な描写の点では不利である。そこで、上記の転写方法でも階調を重視する場合には昇華転写方式を選択し、蛍光潜像の充分な輝度を得るためには、溶融転写方式により蛍光インキ層を転写する方法が用いられる。
【００５２】
また前記本発明の課題の欄で述べたように、溶融転写方法を選択した場合でも、被転写基材に蛍光潜像転写フィルムの蛍光インキ層をパターン状に転移させて蛍光潜像を形成する方法では、蛍光剤の濃度を増やすことには限界がある。このような場合には、以下の蛍光潜像形成方法を用いることができる。
【００５３】
例えば、図７に示す如き、基材フィルム３１に剥離層３２、紫外線吸収パターン３３、染料インキにより情報を記録可能な受容層３４が順次設けられた中間転写媒体３０、及び、図１１に示す如き、基材フィルムにイエローインキ層２２Ｙ、マゼンタインキ層２２Ｍ、シアンインキ層２２Ｃ、熱昇華性ブラックインキ層２２ＢＫ（これらのインキ層を、染料インキ層２２と云う）、剥離層２３が面順次に設けられ、上記剥離層２３上に蛍光材料を配合した接着剤インキから形成された蛍光接着層２４を形成した染料転写フィルム２０を用いて、図１４（ａ）〜（ｃ）に示す工程を行って、セキュリティパターンが形成された記録媒体（セキュリティパターン形成体５１）を形成することができる。
【００５４】
図１４（ａ）に示すように、中間転写媒体の受容層３４に染料転写フィルムの染料インキ層２２を用いて、所定のパターンに昇華転写し可視画像３５を形成して情報を記録する。次に同図（ｂ）に示すように、上記受容層の上から染料転写フィルムの蛍光接着層２４を溶融転写して全面に積層し、基材フィルム３１に剥離層３２、紫外線吸収パターン３３、受容層３４、可視画像３５が転写層３６として設けられた中間転写媒体３０を形成する。最後に同図（ｃ）に示すように、被転写体５０の表面に上記中間転写媒体３０の転写層３６を転写して、蛍光接着層２４と、該蛍光接着層よりも上方に位置する紫外線吸収パターン３３、可視画像３５からなる蛍光潜像を有するセキュリティパターン形成体５１が得られる。
【００５５】
図１４（ｃ）のセキュリティパターン形成体は、表面上方から紫外線を照射した際に、蛍光接着層２４の上方に位置する紫外線吸収パターン３３によって紫外線が吸収される。その結果、紫外線照射によって得られる蛍光像は、紫外線吸収パターン３３のネガ像である。
【００５６】
上記の蛍光潜像はセキュリティパターンとして用いられるものであり、被転写体に蛍光潜像が設けられたものをセキュリティパターン形成体と云う。被転写体としてはセキュリティの要求されるものが好適に用いられ、例えばパスポート冊子、ＩＤカード、クレジットカードなどの各種カード類、免許証等が挙げられる。
【００５７】
蛍光潜像を構成するための紫外線吸収パターン３３は、中間転写媒体３０の転写層３６において、蛍光接着層２４などの蛍光材料層よりも下方にあれば、被転写体に転写後に蛍光材料層よりも上方に位置することになるため、いずれの層に形成しても良い。紫外線吸収パターンは、有機系紫外線吸収剤を樹脂バインダーに添加したもの、または樹脂バインダーと反応させたもの等から形成することができる。
【００５８】
有機系紫外線吸収剤としては、サリシレート系、ペンゾフェノン系、ペンゾトリアゾール系、置換アクリロニトリル系、ニッケルキレート系、ヒンダートアミン系等の紫外線吸収剤が挙げられる。
【００５９】
また反応性紫外線吸収剤は、上記有機系紫外線吸収剤に、たとえばビニル基やアクリロイル基、メタクロイル基等の付加重合性二重結合、あるいはアルコール性水酸基、アミノ基、カルボキシル基、エポキシ基、イソシアネート基等を導入したものを樹脂バインダーに反応固定して使用する。反応固定する方法として従来公知のモノマー、オリゴマー、または反応性重合体の樹脂成分と上記のような付加重合性二重結合を有する反応性紫外線吸収剤とをラジカル重合することにより共重合体とすることができる。また、反応性紫外線吸収剤が水酸基、アミノ基、カルボキシル基、エボキシ基、イソシアネート基を有する場合には、上記の反応性基と反応性を有する熱可塑性樹脂を使用し、必要に応じて触媒を用いて、熱等によって反応性紫外線吸収剤を熱可塑性樹脂に反応固定することができる。
【００６０】
紫外線吸収パターン３３は、上記の紫外線吸収剤を有するインキを用いた印刷方法あるいは転写方法などのいずれの手段で形成しても良いが、図１３に示す如き、剥離層２３の表面に紫外線吸収剤層２５を設けた染料転写フィルム２０を用いて、可視画像を形成する際に中間転写媒体に転写により形成することが好ましい。
【００６１】
中間転写媒体３０の剥離層３２は、被転写媒体に転写する際に基材フィルム３１から剥離して、転写後に最表面に位置し保護層となるものである。剥離層は公知の転写シートの剥離層に使用される材料を用いることができる。
【００６２】
剥離層は、バインダ樹脂と離型性材料とを含有する組成物から形成することができる。バインダ樹脂としては、熱可塑性樹脂であるポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリアクリル酸ブチル等のアクリル系樹脂、ポリ酢酸ビニル、塩化ビニル−酢酸ビニル共重合体、ポリビニルアルコール、ポリビニルブチラール等のビニル系樹脂、エチルセルロース、ニトロセルロース、酢酸セルロース等のセルロース誘導体、あるいは熱硬化型樹脂である不飽和ポリエステル樹脂、ポリエステル樹脂、ポリウレタン樹脂、アミノアルキッド樹脂等が使用できる。また、離型性材料としては、ワックス類、シリコーンワックス、シリコーン系樹脂、メラミン樹脂、フッ素系樹脂、タルクやシリカの微粉末、界面活性剤や金属セッケン等の潤滑等が使用できる。
【００６３】
剥離層は、上記樹脂を適当な溶剤により溶解または分散させて塗工液を調製し、これを基材フィルム上にグラビア印刷法、スクリーン印刷法またはグラビア版を用いたリバースコーティング法等の手段により塗布、乾燥して形成することができる。剥離層の乾燥後の厚さは、通常０．１〜５μｍである。
【００６４】
図１４（ｂ）の中間転写媒体では、蛍光接着層は接着剤層が蛍光材料層を兼ねるように構成したが、蛍光材料層と接着剤層を別の層として形成しても良い。例えば、図８に示す中間転写フィルム３０のように、基材フィルム３１の表面に、剥離層３２、紫外線吸収パターン３３、蛍光材料層３７、接着剤層を兼ねる受容層３４を順次形成し、該中間転写フィルムの受容層３４に可視画像などの情報を記録して中間転写媒体を構成し、被転写体表面に転写してセキュリティパターン形成体とすることも可能である。
【００６５】
接着剤層を兼ねる受容層は染料染着性樹脂から形成される。具体的には、飽和ポリエステル、ポリアミド、ポリアクリル酸エステル、ポリカーボネート、ポリウレタン、ポリビニルアセタール、ポリ塩化ビニル、塩化ビニル−酢酸ビニル共重合体、ポリ酢酸ビニル、ポリスチレン、スチレン−アクリル共重合体、スチレン−ブタジエン共重合体、ビニルトルエン−アクリル共重合体、セルロース系樹脂等が挙げられる。これらの樹脂は単独或いは２種以上を混合してもよい。
【００６６】
蛍光材料層は例えば図１に示す蛍光潜像転写フィルム、あるいは該フィルムの蛍光インキ層に用いられる（化１）式に示す蛍光剤を含有する材料は好ましく用いられるものであるが、それ以外に、以下の蛍光体を含有する材料を用いることができる。
【００６７】
蛍光体は、ルミネッセンスを発する物質であって、無機蛍光体と有機蛍光体の双方を含む。無機蛍光体としては、Ｃａ、Ｂａ、Ｍｇ、Ｚｎ、Ｃｄなどの酸化物、硫化物、ケイ酸塩、リン酸塩、タングステン酸塩などの結晶を主成分とし、Ｍｎ、Ｚｎ、Ａｇ、Ｃｕ、Ｓｂ、Ｐｂなどの金属元素もしくはランタノイド類などの希土類元素を活性剤として添加して焼成して得られる顔料を用いられ得る。
【００６８】
好ましい蛍光体としてＺｎＯ：Ｚｎ、Ｂｒ（ＰＯ）Ｃｌ：Ｅｕ、ＺｎＧｅＯ：Ｍｎ、ＹＯ：Ｅｕ、Ｙ（Ｐ、Ｖ）Ｏ：Ｂｕ、ＹＯＳｉ：Ｅｕ、ＺｎＧｅＯ：Ｍｎ等を例示できる。有機蛍光体としては、ジアミノスチルベンジスルホン酸誘導体、イミダゾール誘導体、クマリン誘導体、トリアゾール、カルバゾール、ピリジン、ナフタル酸、イミタゾロン等の誘導体、フルオレセイン、エオシン等の色素、アントラセン等のベンゼン環を持つ化合物などが用いられ得る。
【００６９】
耐久性及び耐候性の点においては無機顔料が優れている。一方、有機顔料は、インキビヒクルのぬれ性が良いため、特に表面処理をしなくとも、インキ化適性に優れている。上記顔料の内でも、耐久性、耐候性、特に耐光性あるいは印刷適性の向上を図る上においては、粒径が比較的大きく輝度が大きい、安定な酸化物もしくは酸素酸塩系の無機蛍光体が好ましい。特に、ＺｎＯ：Ｚｎを用いることが、輝度及び耐候性の点で優れている。また、蛍光体として希土類蛍光体を例示することもできる。
【００７０】
また、蛍光体は、輝度などの蛍光特性とインキの印刷特性の向上を図るために、顔料の粒径を調製することが好ましい。このような観点において、蛍光体としては、平均粒径０．７〜４μｍの顔料粒子からなるものを使用することが好ましく、さらに好ましくは平均粒径０．７〜２μｍ、最も好ましくは１〜２μｍの範囲の顔料粒子を使用することが望ましい。一般に、顔料の粒径が小さいほどインキ特性が向上することが予想されるが、粒径が０．７μｍ未満になると、逆に蛍光の輝度が著しく低下する現象が見られる。したがって、０．７μｍ以上の粒径を有する蛍光体を用いることが好ましい。一方、粒径が４μｍを超えると得られる蛍光発光画像の透明性が低下することがあるからである。
【００７１】
蛍光インキを構成する溶剤を除いた組成全体に対する蛍光体の含有量は、輝度と印刷基材への転写性（接着性）の双方の向上を図る上で１５〜８０重量％が適当であり、さらに好ましい範囲は２０〜５０重量％であることが適当である。蛍光体の含有量が１５％未満では、蛍光体の種類によっては、インキ組成物状態での蛍光輝度が極端に低下し、たとえば１２％程度では顔料自体が有する輝度に対して約１／１０程度にまで減少する場合がある。また、蛍光発光画像の厚みは、必要とされる蛍光輝度と蛍光体の含有量等により適宜決定することができ、例えば約１〜１０μｍとすることができる。本発明では、透明性を確保するという観点から、前記のように比較的小さい粒子径の蛍光体を用いるが、粒子径が小さいことによる蛍光強度の不足は、蛍光発光画像の厚みを増すことにより補うことができる。
【００７２】
さらに、蛍光体の性質（隠蔽力、着色力、吸油量、耐久性等）を改善するために表面処理を行うことが好ましい。特に無機顔料を用いた場合、その表面が親水性があり、油性のポリマーとの親和性が乏しいため、表面処理を行って、ポリマーとの親和性を改善することが好ましい。その方法としては、たとえば、コーティング剤、カップリング剤、重合性モノマーなどを用いる方法がある。
【００７３】
また、セキュリティパターン形成体には、図９及び図１０に示すように、転写層３６にホログラム効果層４１、該ホログラム効果層の表面に微細エンボス加工を施してホログラムパターンを形成し、該パターンの上から酸化チタンなどを蒸着して設けた金属薄膜層４２から構成されるホログラムを設けることができる。なお図９に示す態様ではホログラムパターンの上に紫外線吸収パターン３３、受容層３４が設けられている。また、図１０に示す態様ではホログラムパターンの上には、紫外線吸収パターンの上には蛍光材料層３７が設けられ、その上に受容層が設けられて構成される。このように、蛍光潜像をホログラムなどの他のセキュリティ手段と併用することで、更に安全性の高いセキュリティパターン形成体が得られる。
【００７４】
上記ホログラム効果層４１の基材樹脂としては、例えば、不飽和ポリエステル樹脂、アクリルウレタン樹脂、エポキシ変成アクリル樹脂、エポキシ変成不飽和ポリエステル樹脂、アルキッド樹脂、フェノール樹脂等等が挙げられ、又、熱可塑性樹脂としては、アクリル酸エステル樹脂、アクリルアミド樹脂、ニトロセルロース樹脂、ポリスチレン樹脂、等が挙げられる。これらの樹脂は、単独もしくは２種以上を各種イソシアネート樹脂や、ナフテン酸コバルト、ナフテン酸亜鉛等の金属石鹸ベンゾイルパーオキサイド、メチルエチルケトンパーオキサイド、等の過酸化物、ベンゾフェノン、アセトフェノン、アントラキノン、ナフトキノン、アゾビスイソブチロニトリル、ジフェニルスルフィド等の熱あるいは紫外線硬化剤等を配合してもよい。又、電離放射線硬化型樹脂としては、エポキシアクリレート、ウレタンアクリレート、アクリル変成ポリエステル等をオリゴマーとし、これに架橋構造、粘度の調製等を目的としてネオペンチルグリコールアクリレート、トリメチロールプロパントリアクリレート等のモノマー等を適宜混合したものが用いられる。
【００７５】
中間転写媒体を形成するのに、図１１〜図１３に示す染料転写フィルムを用いることができる。これら染料転写フィルムは、各色のインキ層２２及び剥離層２３が面順次に形成され、剥離層２３の上に接着剤層２６、紫外線吸収剤層２７、蛍光材料層２５などの層が単一または複数形成されたインキリボンとして構成されているものである。
【００７６】
【実施例】
〔蛍光潜像転写フィルムの作製例１〕
厚さ６μｍのポリエチレンテレフタレートフィルム（商品名ルミラー：東レ社製）を基材フィルムとし、その一方の面に耐熱スリップ層（背面層）として、シリコーン樹脂を厚さ１μｍとなるようにグラビアコート方式により形成し、もう一方の面に下記組成の蛍光インキ層用塗布液をグラビアコート方式で乾燥時の塗布量が０．６ｇ／ｍ² となるように塗布、乾燥して蛍光潜像転写フィルムを形成した。尚、実施例の蛍光化合物のＮｏ．は前記表１に示すものである。
【００７７】
〔蛍光インキ層用塗布液１〕
・ポリビニルアセタール樹脂（積水化学工業社製） ５重量部
・蛍光化合物Ｎｏ．８ ３重量部
・メチルエチルケトン ６０重量部
・トルエン ２２重量部
・イソプロパノール １０重量部
【００７８】
〔蛍光潜像転写フィルムの作製例２〕
上記蛍光潜像転写フィルムの作製例１において作製した蛍光潜像層を、イエロー、マゼンタ、シアン、ブラック色の昇華性染料層、蛍光インキ層、熱転写性樹脂ブラック層、保護層の順に面順次に、且つ各色（又は各層）のパネル長さが１５ｃｍとなるように繰り返しグラビア印刷し、乾燥させて、４色染料層−樹脂ブラック層−蛍光インキ層−保護層一体型蛍光潜像転写フィルムを形成した。
【００７９】
〔蛍光潜像転写フィルムの作製例３〕
蛍光潜像転写フィルムの作製例２において、蛍光インキ層を保護層のパネルの後の順序に設けた以外はフィルムの作製例２と同様にして一体型蛍光潜像転写フィルムを得た。
【００８０】
〔蛍光潜像転写フィルムの作製例４〕
フィルムの作製例２において、保護層にホログラムパターンを形成した以外はフィルム作製例２と同様にして、蛍光インキ層、ホログラム保護層一体型蛍光潜像転写フィルムを形成した。
【００８１】
実施例１
下記の昇華型熱転写シートと熱転写受像シートを重ね合わせ、顔写真を色分解して得た電気信号に従って作動するプリンターのサーマルヘッドを用いて熱エネルギーを付加し、フルカラー画像を形成した。
次に上記フルカラー画像が形成された受像シートと、蛍光潜像転写フィルムの作製例１の転写フィルムを重ね合わせ、上記顔写真とは異なる階調性に富んだモノカラー画像から得た電気信号に従って、上記プリンターのサーマルヘッドを用いて蛍光潜像を形成し、蛍光潜像を有する印画物を得た。
【００８２】
昇華型熱転写シートは、厚さ６μｍのポリエチレンテレフタレートフィルム（東レ社製：ルミラー）の片面側にウレタン系樹脂からなる厚さ０．５μｍのプライマー層を設け、多面側（背面）に厚さ１μｍの耐熱スリップ層を設け、上記プライマー層の表面に下記のイエローインキ、マゼンタインキ、シアンインキの組成物をポリエステルフィルムの流れ方向に沿って、この順序に面順次に、各長さが１５ｃｍとなるように繰り返しグラビア印刷し、乾燥させて３色の昇華性インキ層を形成し、昇華型熱転写シートを得た。各色の塗布量は、それぞれ約３ｇ／ｍ² （固形分）とした。昇華性染料を含有する３色のインキを以下の通り調整した。
【００８３】

【００８４】
【化３】

〔式中、ｎはノルマル系であることを表す。〕
【００８５】
〔マゼンタインキ組成〕
前記のイエローインキにおいて、染料をシーアイディスパースレッド６０（C.I.Disperse Red 60 ) に代えた以外は同様にして、マゼンタインキを得た。
【００８６】
〔シアンインキ組成〕
前記のイエローインキにおいて染料をシーアイソルベントブルー６３（C.I.Solvent Blue 63 ) に代えた以外は同様にして、シアンインキを得た。
【００８７】
熱転写受像シートは、基材シートとして合成紙（ユポＦＰＧ−１５０、厚さ１５０μｍ、王子油化合成紙製）を用い、その一方の面に下記組成の染料受容層用塗布液をバーコーターにより、乾燥時塗布量が４ｇ／ｍ² となるように塗布、乾燥して染料受容層を形成し、熱転写受像シートを作成した。
【００８８】

【００８９】
実施例２
実施例１において、フルカラー画像を形成する前に蛍光潜像を形成した以外は実施例１と同様にして、蛍光潜像を有する印画物を得た。
【００９０】
実施例３
フルカラー画像と蛍光潜像を設けた実施例１の印画物上に保護層を形成した以外は実施例１と同様にして印画物を得た。
【００９１】
実施例４
実施例１においてフルカラー画像を設けた印画物上に、まず保護層を形成し、その後、保護層上に蛍光潜像を設けた以外は実施例１と同様にして印画物を得た。
【００９２】
実施例５
蛍光潜像転写フィルム作製例２の４色染料層−蛍光潜像層−樹脂ブラック層−保護層一体型フィルムを用い、まずイエロー−マゼンタ−シアン３色を用いて実施例１に記載のフルカラー画像を熱転写受像シート上に形成し、次に染料ブラック層を用いて該熱転写受像シート上の顔写真フルカラー画像とは異なる領域にサイン及び指紋情報を印画し、次に蛍光インキ層を用いて実施例１のモノカラー画像から得た電気信号に従って蛍光潜像を形成し、更に樹脂ブラックインキ層を用いて氏名、生年月日、住所、などの文字情報及びバーコードを印字し、最後に熱転写受像シート上に設けられたこれらの画像全体を覆うように保護層を転写して印画物を得た。
【００９３】
実施例６
実施例５において、蛍光潜像転写フィルム作製例２の一体型フィルムを用いて蛍光潜像を形成した後に保護層を設ける代わりに、蛍光潜像転写フィルム作製例３の一体型フィルムを用いて保護層を設けた後に蛍光潜像を形成した以外は実施例５と同様にして印画物を得た。
【００９４】
実施例７
実施例５において、蛍光潜像転写フィルム作製例２の一体型フィルムの代わりに蛍光潜像転写フィルム作製例３の一体型フィルムを用い、ホログラムパターンが形成された保護層を転写した以外は実施例５と同様にして、ホログラムパターンが形成された印画物を得た。
【００９５】
実施例８
熱転写受像シートとしてカードを用いた以外は実施例５と同様にして、カード状の印画物を得た。
【００９６】
実施例９
熱転写受像シートとしてパスポート冊子を用いた以外は実施例５と同様にして、印画物を得た。
【００９７】
実施例１０
熱転写受像シートとして免許証を用いた以外は実施例５と同様にして印画物を得た。
【００９８】
実施例１〜実施例１０の印画物について、蛍光潜像の視認性を評価した。結果を表２に示す。評価方法は、３００〜４００ｎｍの波長の紫外線を照射し、蛍光潜像が明確に認識できるかどうかを目視で観察し、蛍光発色が鮮明に確認できたものを○とし、蛍光潜像の印画パターンを確認できないものを×として評価した。表２に示す通り、実施例１〜１０のいずれも蛍光発色が鮮明に確認できた。
【００９９】
【表２】

【０１００】
中間転写媒体▲１▼
厚さ１２μｍのポリエチレンテレフタレートの透明基材の表面に剥離層（兼保護層）１．５μｍ、紫外線吸収剤パターン印刷をグラビア印刷で行い１．０μｍ、染料受容層２．０μｍをグラビアコーティングして、図７に示す態様の中間転写媒体を得た。
【０１０１】
中間転写媒体▲２▼
厚さ１２μｍのポリエチレンテレフタレートの透明基材の表面に剥離層（兼保護層）１．５μｍ、紫外線吸収パターン印刷をグラビア印刷で行い、１．０μｍ、さらに蛍光材料層３．０μｍ、染料受容層２．０μｍを順次グラビアコーティングして、図８に示す態様の中間転写媒体を得た。
【０１０２】
中間転写媒体▲３▼
厚さ１２μｍのポリエチレンテレフタレートの透明基材の表面に剥離層（兼保護層）１．５μｍ、ホログラム効果層２．０μｍをグラビアコーティングした。上記ホログラム効果層表面に微細エンボス加工を行いホログラムパターンを形成した。次いでエンボス後のホログラム効果層表面上に酸化チタンを真空蒸着（５００Ａ）した。更にその表面に紫外線吸収パターン印刷を行い１．０μｍ、受容層２．０μｍをグラビアコーティングして、図９に示す態様の中間転写媒体を得た。
【０１０３】
中間転写媒体▲４▼
厚さ１２μｍのポリエチレンテレフタレートの透明基材の表面に剥離層（兼保護層）１．５μｍ、ホログラム効果層２．０μｍをグラビアコーティングした。上記ホログラム効果層表面に微細エンボス加工を行いホログラムパターンを形成した。次いでエンボス後のホログラム効果層表面上に酸化チタンを真空蒸着（５００オングストローム）した。更にその表面に紫外線吸収パターン印刷を行い１．０μｍ、蛍光材料層３．０μｍ、受容層２．０μｍをグラビアコーティングして図１０に示す態様の中間転写媒体を得た。
【０１０４】
なお中間転写媒体及び染料転写フィルムの剥離層、ホログラム効果層、受容層、蛍光材料層、紫外線吸収層、接着層は、それぞれ下記の組成を用いた。
【０１０５】
［剥離層（兼保護層）塗工液]（以下、単位はすべて重量部である）
アクリル樹脂 ４０部
ポリエステル樹脂 ２部
メチルエチルケトン ５０部
トルエン ５０部
【０１０６】
[ホログラム効果層塗工液］
アクリル樹脂 ４０部
メラミン樹脂 １０部
シクロヘキサノン ５０部
メチルエチルケトン ５０部
【０１０７】
［受容層塗工液］
塩化ビニル−酢酸ビニル共重合体 ５０部
アクリルシリコーン １．５部
メチルエチルケトン ５０部
トルエン ５０部
【０１０８】
［蛍光材料用インキ］
バイロン２７０（ポリエステル樹脂） ３０部
ユビテックス ＯＢ １部
トルエン ３５部
メチルエチルケトン ３５部
【０１０９】
［紫外線吸収層インキ１］
反応性紫外線吸収剤を反応結合した共重合樹脂 ４０部
（ＢＡＳＦジャパン社製ＵＶＡ−６３５Ｌ）
アンチモン酸亜鉛 ４０部
メチルエチルケトン ３０部
トルエン ３０部
【０１１０】
［接着層インキ］
塩酢ビ樹脂 ３０部
トルエン ３５部
メチルエチルケトン ３５部
【０１１１】
染料転写フィルム▲１▼
ＰＥＴフィルムの流れ方向に沿ってイエロー、マゼンタ、シアンの各インキをこの順序で面順次にグラビアコートした（塗布量３．０μｍ）。さらに上記フィルムに続けて面順次に剥離層を設け、剥離層上に接着層を設けて染料転写フィルムを得た。
【０１１２】
染料転写フィルム▲２▼
ＰＥＴフィルムの流れ方向に沿ってイエロー、マゼンタ、シアンの各インキをこの順序で面順次にグラビアコートした（塗布量３．０μｍ）。さらに上記フィルムに続けて面順次に剥離層を設け、剥離層上に、接着層インキと蛍光材料用インキを等量配合して接着層兼蛍光材料層を形成して染料転写フィルムを得た。
【０１１３】
染料転写フィルム▲３▼
ＰＥＴフィルムの流れ方向に沿ってイエロー、マゼンタ、シアンの各インキをこの順序で面順次にグラビアコートした（塗布量３．０μｍ）。さらに上記フィルムに続けて面順次に剥離層を設け、剥離層上に、面順次に紫外線吸収剤層を設け、さらに接着層インキと蛍光材料用インキを等量配合して接着層兼蛍光材料層を形成して染料転写フィルムを得た。
【０１１４】
染料転写フィルムの各色のインキは、それぞれ下記の組成を用いた。
〈イエローインキ〉
下記構成式［化４］で表わされるキノフタロン系染料 ５．５重量部
ポリビニルブチラール ４．５重量部
（エスレックＢＸ−１．積水化学工業製）
メチルエチルケトン／トルエン（１／１） ９０．０重量部
【０１１５】
【化４】

【０１１６】
〈マゼンタインキ〉
前記のイエローインキにおいて、染料をシーアイ・ディスパースレッド６０（Ｃ．Ｉ．Ｄｉｓｐｅｒｓｅ Ｒｅｄ ６０）に代えた以外は同様にして、マゼンタインキを得た。
【０１１７】
〈シアンインキ〉
前記のイエローインキにおいて、染料をシーアイ・ソルベンドブルー６３（Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ６３）に代えた以外は同様にして、シアニンキを得た。
【０１１８】
セキュリティパターン形成体▲１▼
中間転写媒体▲１▼と染料転写フィルム▲２▼を用いて、図１４の工程図に示すように、中間転写媒体▲１▼の受容層に昇華染料画像を形成し蛍光材料層兼接着層（蛍光接着層）をベタ柄転写した後、接着層を転写しパスポート冊子に再転写してセキュリテイパターン形成体を得た。
【０１１９】
セキュリティパターン形成体▲２▼
中間転写媒体▲１▼と染料転写フィルム▲３▼を用いて、図１５の工程図に示すように中間転写媒体▲１▼の受容層に昇華染料画像を形成し、紫外線吸収層をサーマルヘッドでパターン転写し蛍光材料層兼接着層をベタ柄転写した後、パスポート冊子に再転写してセキュリテイパターン形成体を得た。
【０１２０】
セキュリティパターン形成体▲３▼
中間転写媒体▲２▼と染料フィルム▲１▼を用いて、図１６の工程図に示すように中間転写媒体▲２▼の受容層に昇華染料画像を形成し接着層転写後パスポートに再転写してセキュリティパターン形成体を得た。
【０１２１】
セキュリティーパターン形成体▲４▼
中間転写媒体▲３▼と染料フィルム▲２▼を用いて、図１７の工程図に示すように中間転写媒体▲３▼の受容層に昇華染料画像を形成し蛍光材料層兼接着層をベタ柄転写した後、接着層を転写しパスポート冊子に再転写してセキュリティパターン形成体を得た。
【０１２２】
セキュリティパターン形成体▲５▼
中間転写媒体▲３▼と染料フィルム▲３▼を用いて、図１８の工程図に示すように中間転写媒体▲３▼の受容層に昇華染料画像を形成し、紫外線吸収層をサーマルヘッドでパターン転写し蛍光材料層兼接着層をベタ柄転写した後、パスポート冊子に再転写してセキュリティパターン形成体を得た。
【０１２３】
セキュリティパターン形成体▲６▼
中間転写媒体▲４▼と染料フィルム▲１▼を用いて、図１９の工程図に示すように中間転写媒体▲４▼の受容層に昇華染料画像を形成し接着層転写後パスポートに再転写してセキュリティパターン形成体を得た。
【０１２４】
比較例▲１▼
厚さ１２μｍのポリエチレンテレフタレートの透明基材の表面に剥離層（兼保護層）１．５μｍ、蛍光発色パターンをグラビア印刷で行い１．０μｍ、染料受容層２．０μｍをグラビアコーティングした。
【０１２５】
比較例▲２▼
厚さ１２μｍのポリエチレンテレフタレートの透明基材の表面に剥離層（兼保護層）１．５μｍ、蛍光発色パターンをグラビア印刷で行い３．０μｍ、染料受容層２．０μｍをグラビアコーティングした。
【０１２６】
比較例▲３▼
厚さ１２μｍのポリエチレンテレフタレートの透明基材の表面に剥離層（兼保護層）１．５μｍ、蛍光発色パターンを下記のインキ組成でグラビア印刷で行い１．０μｍ、染料受容層２．０μｍをグラビアコーティングした。
【０１２７】
比較例▲１▼〜▲３▼の蛍光発色パターンの印刷には下記のインキを用いた。
［蛍光インキ］
バイロン２７０（ポリエステル樹脂） ３０部
ユビテックス ＯＢ １０部
トルエン ３５部
メチルエチルケトン ３５部
【０１２８】
【表３】

【０１２９】
視認性：蛍光潜像の目視での視認性（○：視認しやすい ×：視認しにくい）
情報可変性：蛍光潜像パターンの可変性可否（○：可変可能 ×：可変不可）
隠蔽性：通常光源下（白色光、太陽光）での目視確認の可否（○：通常状態では目視不可能 ×：通常状態でも蛍光潜像パターンが見えてしまう）
再現性：緻密なパターンの印刷再現性（○：再現がよい ×：再現が悪い）
保存性：ロール保存性のブッキング等の発生（○：保存性がよい ×：保存性が悪い）
【０１３０】
本発明は、中間転写媒体▲１▼〜▲４▼、染料フィルム▲１▼〜▲３▼の組み合わせで紫外線吸収パターンと蛍光材料層が同時に形成できる層構成であれば、どのような組み合わせのフィルムを用いて形成してもよい。
【０１３１】
【発明の効果】
以上説明したように本発明蛍光潜像転写方法は、特定の蛍光剤を用いた蛍光インキ層を有する蛍光潜像転写フィルムを用いて転写を行う方法を採用した為、連続階調の蛍光潜像を良好に形成することができる。この蛍光潜像は、可視光では視認できないが、紫外線を照射した場合に、明瞭に確認できる。従って本発明印画物は、蛍光潜像を利用して該印画物が真正なものであることを確認できる為、印画物の複写等による偽造や改竄等を良好に防止できる。上記の特定の蛍光化合物を含有する樹脂バインダーからなる蛍光インキは、蛍光潜像の転写性及び階調性に優れる。
【０１３２】
また本発明セキュリティパターン形成体は、蛍光潜像パターンの十分な発色輝度が得られ、加工時に原反に悪影響を与えることがなく、蛍光潜像の識別が容易に行える。
【図面の簡単な説明】
【図１】蛍光潜像転写フィルムの１例を示す要部縦断面図である。
【図２】蛍光潜像転写フィルムの他の例を示す要部縦断面図である。
【図３】（ａ）〜（ｈ）は蛍光潜像転写フィルムの態様を示す平面図である。
【図４】（ａ）〜（ｉ）は蛍光潜像転写フィルムの態様を示す平面図である。
【図５】本発明印画物の態様を示す断面図である。
【図６】本発明印画物の態様を示す断面図である。
【図７】中間転写媒体の態様を示す断面図である。
【図８】中間転写媒体の態様を示す断面図である。
【図９】中間転写媒体の態様を示す断面図である。
【図１０】中間転写媒体の態様を示す断面図である。
【図１１】染料転写フィルムの態様を示す断面図である。
【図１２】染料転写フィルムの態様を示す断面図である。
【図１３】染料転写フィルムの態様を示す断面図である。
【図１４】セキュリティパターン形成方法を示す工程図である。
【図１５】セキュリティパターン形成方法を示す工程図である。
【図１６】セキュリティパターン形成方法を示す工程図である。
【図１７】セキュリティパターン形成方法を示す工程図である。
【図１８】セキュリティパターン形成方法を示す工程図である。
【図１９】セキュリティパターン形成方法を示す工程図である。
【符号の説明】
１ 蛍光潜像転写フィルム
２ 耐熱性基材フィルム
３ 蛍光インキ層
４ 背面層
５ 熱昇華性染料層
６ 熱溶融性インキ層
７ 保護層
９ 印画物
１０ 印画物
１１ 蛍光潜像
１２、１３、１４ 可視画像
２０ 染料転写フィルム
２１ 基材フィルム
２２ 染料インキ層
２３ 剥離層
２４ 蛍光接着層
２５ 蛍光材料層
２６ 接着剤層
２７ 紫外線吸収層
３０ 中間転写媒体
３１ 基材フィルム
３２ 剥離層
３３ 紫外線吸収パターン
３４ 受容層
３５ 可視画像
３６ 転写層
３７ 蛍光材料層
３８ 接着剤層
４０ 蛍光潜像転写フィルム
４１ ホログラム効果層
４２ 金属薄膜層
５０ 被転写体
５１ セキュリティパターン形成体[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method of forming a fluorescent latent image using a thermal transfer film, and more specifically, forms a fluorescent latent image such as an arbitrary photograph, pattern, or character on a transfer object, and is excellent in falsification prevention and design properties. The present invention relates to a fluorescent latent image transfer method capable of forming an image, and a security pattern forming body provided with a fluorescent latent image.
[0002]
[Prior art]
Conventionally, in order to prevent forgery or falsification of printed materials such as documents, cash vouchers, cards, etc., it cannot be recognized with normal visible light, etc., but it is optional in order to emit fluorescence and identify when irradiated with ultraviolet rays. Means for providing a fluorescent latent image in this pattern is known. In order to form this fluorescent latent image, generally, a printing method using fluorescent coloring ink is generally used.
[0003]
Conventionally, a thermal transfer method has been widely used as a simple printing means. Since various images can be easily formed by this method, it is used to create printed materials with a small number of printed sheets, for example, cards such as ID cards.
[0004]
The fluorescent latent image can be recorded on a transfer medium such as a card by a heating means such as a thermal head or a laser using a thermal transfer film containing a fluorescent agent in the thermal transfer layer. Transfer methods include a sublimation type thermal transfer recording method and a hot melt type thermal recording method. The sublimation thermal transfer recording method uses a sublimable dye, and the dye is sublimated by heating by the heating means to be transferred. The hot-melt recording method uses a hot-melt ink containing a colorant such as a pigment in a vehicle such as wax, and softens the ink of the hot-melt ink layer by heating means. The recording is performed after shifting.
[0005]
The thermal melting type thermal recording method can easily and clearly form images such as letters and numbers, and the sublimation type thermal transfer method is excellent in gradation expression and forms images such as facial photographs precisely and beautifully. Each method has the feature that it can be used.
[0006]
JP-A-2-106359, JP-A-6-316167, JP-A-7-223376, JP-A-7-117366, and the like are used as sublimation thermal transfer films capable of recording and forming a continuous tone fluorescent latent image. Is disclosed. These publications describe various fluorescent agent compounds for forming a fluorescent latent image.
[0007]
[Problems to be solved by the invention]
However, the method for forming a fluorescent latent image using a transfer film using the fluorescent compound described in the above publication has a problem that the transferability and gradation of the fluorescent latent image are still insufficient. .
[0008]
The present invention has been made in view of the above-mentioned problems of the prior art, and provides a fluorescent latent image transfer method capable of forming a fluorescent latent image excellent in transferability and gradation, and a printed material on which the fluorescent latent image is formed. The purpose is to provide.
[0009]
Further, when a fluorescent ink pattern is provided by printing in a predetermined pattern using fluorescent ink, there are the following problems.
(1) Since a fluorescent ink pattern was formed by printing, a sufficient coating amount could not be ensured, and the fluorescence coloring degree was insufficient.
{Circle around (2)} When printing is performed with an increased amount of coating to obtain color brightness, the print reproducibility of fine patterns is degraded. Further, when the thickness is increased, unevenness is generated in the original fabric when printing is performed, and there is a possibility that long sheets may be blocked.
(3) In fluorescent pigment ink, increase the fluorescent pigment (Pigment) component and increase the ratio of fluorescent pigment to binder resin (hereinafter referred to as P / V ratio) to increase the emission intensity of the fluorescent latent image. In this case, since the concentration of the fluorescent pigment is increased, the printed layer is whitened, and the portion printed with the fluorescent ink is easily visually confirmed.
[0010]
Japanese Patent Application Laid-Open No. 6-166264 describes a method of obtaining a fluorescent latent image having a specific pattern by printing on a sheet having a fluorescent latent image using an ink containing an ultraviolet absorber.
However, in this method, it is necessary to preliminarily contain a fluorescent material in a support (recording medium) having a recording layer. For pattern formation with an ultraviolet absorber, a special recording medium containing a fluorescent material must be used. In particular, ordinary paper that is not subjected to such processing cannot be used. Therefore, the recording medium is limited and not versatile.
[0011]
An object of the present invention is to provide a security pattern forming body that can obtain sufficient color luminance of a fluorescent latent image pattern, can easily identify a fluorescent latent image without adversely affecting the original fabric during processing. .
[0012]
[Means for Solving the Problems]
  The present invention
(1)At least on the surface of the transfer object, in a printed matter in which a receiving layer on which information is recorded and a security pattern based on a fluorescent latent image are provided, the security pattern is provided in a pattern above the fluorescent material layer and the fluorescent material layer. A transfer layer of the intermediate transfer medium on the surface of the transfer object using an intermediate transfer medium in which the receiving layer, the ultraviolet absorption pattern and the fluorescent material layer are formed as a transfer layer. A security pattern forming body characterized by being provided by transferring
(2) Using an ultraviolet absorber transfer film with an ultraviolet absorber layer provided for the ultraviolet absorption pattern, the transfer film is heated to an arbitrary pattern by a heating element, and the ultraviolet absorber layer corresponding to the pattern of the heating element is transferred. The above (1) Security pattern forming body according to
(3) The fluorescent material layer is formed by using a fluorescent latent image transfer film having a fluorescent ink layer made of a resin binder containing a fluorescent agent.1) Or (2) Security pattern forming body according to
(4) Using a dye transfer film containing a fluorescent material in the adhesive layer in the thermal transfer medium in which the transfer layer in the intermediate transfer medium is provided with a dye ink layer and an adhesive layer in the surface order on the surface of the base film, The security pattern forming body according to any one of (1) to (3), which is formed through transfer of a dye ink layer and transfer of an adhesive layer of the dye transfer film,
(5) Using an intermediate transfer medium having a transfer layer having a fluorescent latent image composed of an ultraviolet absorption pattern and a fluorescent material layer and a receiving layer on which information is recorded, provided on a substrate film, the transfer of the intermediate transfer medium onto a transfer medium A method of forming a security pattern by transferring a layer, wherein the intermediate transfer medium is configured such that the ultraviolet absorption pattern in the transfer layer after transfer is positioned above the fluorescent ink layer to form a fluorescent latent image. A security pattern forming method, characterized by
(6) An ultraviolet absorber transfer film provided with an ultraviolet absorber layer is used, the transfer film is heated to an arbitrary pattern by a heating element, and an ultraviolet absorber layer corresponding to the pattern of the heating element is transferred to ultraviolet rays. The security pattern forming method according to (5) above, wherein an absorption pattern is formed,
(7) The security pattern forming method according to (5) or (6) above, wherein the fluorescent material layer is formed using a fluorescent latent image transfer film having a fluorescent ink layer made of a resin binder containing a fluorescent agent,
(8) In a thermal transfer medium in which a dye ink layer and an adhesive layer are provided in the surface order on the surface of the base film, a dye transfer film containing a fluorescent material is used for the adhesive layer, and the dye ink of the dye transfer film The security pattern forming method according to any one of (5) to (7), wherein a transfer layer in the intermediate transfer medium is formed through transfer of the layer and transfer of the adhesive layer,
Is the gist.
[0013]
In the present invention, the image includes all images that can be recorded as information, such as a continuous tone image such as a photograph, and monochrome or multicolor printing without gradation such as a character, a symbol, and a pattern. In addition, the fluorescent latent image transferred from the fluorescent ink layer is invisible under normal visible light, but can be seen as an ultraviolet absorption image when irradiated with ultraviolet light. In order to prevent this, a secret code or one that can be used for authentication can be used. Specifically, any of photographic prints with gradation, characters without gradation, illustrations, abstract patterns, and the like can be used. Further, an image in visible ink (sometimes referred to as a visible image) refers to an image that is visible to the fluorescent latent image in a normal state formed by a general printing method or transfer method.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail with reference to the drawings. In the fluorescent latent image transfer method of the present invention, as shown in FIG. 1, a fluorescent latent layer in which a fluorescent ink layer 3 formed from a resin binder containing a fluorescent agent is provided on one surface of a heat-resistant substrate film 2. The image transfer film 1 is used, and the fluorescent latent image transfer film 1 is superposed on the transfer body so that the fluorescent ink layer and the transfer surface are in contact with each other, and the heat-resistant substrate film side of the fluorescent latent image transfer film is used. The heating element is heated to an arbitrary pattern by transferring the fluorescent ink layer 3 of the fluorescent latent image transfer film according to the pattern of the heating element to the transfer target, and the arbitrary fluorescent latent image made of a fluorescent agent is transferred to the transfer target. Is formed.
[0015]
First, the fluorescent latent image transfer film used in the method of the present invention will be described below.
The heat-resistant substrate film 2 of the fluorescent latent image transfer film 1 may be any material as long as it has heat resistance against heat during transfer, a certain degree of strength, and dimensional stability. For example, paper, various processed papers, A plastic film or the like is used. Examples of the material of the plastic film include polyesters such as polyethylene terephthalate, polystyrene, polypropylene, polysulfone, polyphenylene sulfide, polyethylene naphthalate, 1,4-polycyclohexylene dimethyl terephthalate, aramid, polycarbonate, polyvinyl alcohol, and cellophane. The thickness of the heat-resistant substrate film 2 is preferably 0.5 to 50 μm, more preferably 3 to 10 μm. A preferred material is a polyethylene terephthalate film.
[0016]
The heat resistant substrate film 2 may be a single wafer type or a continuous film. Moreover, you may perform the primer process for improving the adhesiveness with the fluorescent ink layer provided on this film, or another layer, etc. on the surface of the heat resistant base film 2. FIG. A back layer 4 is provided on the other surface side of the fluorescent latent image transfer film 1.
[0017]
As the fluorescent agent used for the fluorescent ink layer 3, the compound shown in the formula (1) is used. Specific examples of this compound include the compounds shown in Table 1. Among the above compounds, a compound in which Rl in formula (1) is thiophene, and R2 and R3 are t-butyl groups can form a fluorescent latent image with further excellent transferability and gradation. Particularly preferred.
[0018]
[Table 1]

[0019]
Binder resins used for the fluorescent ink layer 3 are cellulose resins such as ethyl cellulose, ethyl hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, and cellulose acetate, and vinyl resins such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, and polyvinyl pyrrolidone. Examples include resins, acrylic resins such as poly (meth) acrylate and poly (meth) acrylamide, polyurethane resins, polyamide resins, polyester resins, and mixtures of these resins. As the binder resin, polyvinyl butyral and polyvinyl acetal are preferable because the transferability of the fluorescent agent and the storage stability when used as a transfer film are good. The thickness of the fluorescent ink layer 3 is 0.1 to 5.0 g / m.² It is preferable to form it.
[0020]
The fluorescent ink layer 3 can be formed by applying ink added with a fluorescent agent, a binder resin, other additives, and the like using a known coating means such as gravure coating.
[0021]
The back layer 4 is provided to prevent fusion with a heating element such as a thermal head or to improve paper feedability. Further, when the transfer film is wound into a roll shape by the back surface layer 4 or sheet-like materials are stacked, the back surface can be prevented from adhering to a surface layer such as a fluorescent ink layer. The back layer 4 preferably has heat-resistant slip properties and release properties. Examples of the material of the back layer include materials having releasability such as curable silicone oil, curable silicone wax, silicone resin, fluorine resin, and acrylic resin. The thickness of the back layer 4 is usually 0.1 to 3.0 μm.
[0022]
The fluorescent latent image transfer film may be in any state of a sheet, a continuous roll, and a ribbon. The fluorescent latent image transfer film shown in FIG. 1 is formed by printing the fluorescent ink layer 3 on the entire surface of the transfer layer, but the fluorescent latent image transfer film has a heat transfer layer other than the fluorescent ink layer 3. Regions such as the sublimable dye layer 5 and the hot-melt ink layer 6 may be formed in the surface order along the flow direction of the sheet. Further, a region of the protective layer 7 may be provided. Hereinafter, other embodiments of these fluorescent latent image transfer films will be described.
[0023]
The fluorescent latent image transfer film 1 shown in FIG. 2 has a yellow dye layer 5Y, a magenta dye layer 5M, a cyan dye layer 5C, a black dye on the same transfer surface of the heat-resistant substrate film 2 on which the fluorescent ink layer 3 is provided. Each region of the heat sublimable dye layer 5, such as the layer 5BK, the fluorescent ink layer 3, and the black heat-meltable ink layer 6B is formed in the surface order, and the region of this structural unit is repeatedly formed in the film flow direction. Yes. A back layer 4 is provided on the other surface side of the heat resistant base film 2. In this embodiment, the transfer layer other than the fluorescent ink layer 3 includes a yellow dye layer 5Y, a magenta dye layer 5M, a cyan dye layer 5C, a black dye layer 5BK, and a black heat-meltable ink layer 6 (heat-meltable black ink layer). 6BK) may be provided on the same transfer surface as that of the fluorescent ink layer 3.
[0024]
FIGS. 3A to 3H are plan views showing an embodiment in which a heat sublimable dye layer 5 and a heat meltable ink layer 6 are provided as layers other than the fluorescent ink layer of the fluorescent latent image transfer film. As shown in the figure, areas (also referred to as panels) such as the fluorescent ink layer 3, the heat sublimable dye layer 5 (5Y, 5M, 5C, 5BK), the heat-meltable ink layer 6 and the like are formed in an arbitrary order. Can do. Further, the length of each region is not particularly limited, and the region can be formed as an arbitrary length region. 3 (a) to 3 (h) has the following arrangement in the plane direction of each region, and is repeatedly formed in the flow direction with the configuration of this region as a basic unit.
[0025]
(A) A solid film consisting only of the fluorescent ink layer 3.
(B) Yellow dye layer 5Y, magenta dye layer 5M, cyan dye layer 5C, and fluorescent ink layer 3.
(C) Yellow dye layer 5Y, magenta dye layer 5M, cyan dye layer 5C, black dye layer 5BK, and fluorescent ink layer 3.
(D) Yellow dye layer 5Y, magenta dye layer 5M, cyan dye layer 5C, fluorescent ink layer 3, and heat-meltable black ink layer 6BK.
(E) Black dye layer 5BK and fluorescent ink layer 3.
(F) Fluorescent ink layer 3, hot-melt black ink layer 6BK.
(G) Yellow dye layer 5Y, magenta dye layer 5M, cyan dye layer 5C, black dye layer 5BK, fluorescent ink layer 3, and heat-meltable black ink layer 6BK.
(H) The same area order as in (g) above, except that the total area of the yellow dye layer 5Y, magenta dye layer 5M, and cyan dye layer 5C is the black dye layer 5BK, fluorescent ink layer 3, heat The meltable black ink layer 6BK was formed smaller than the exclusive area of the region.
[0026]
The heat sublimation dye layer 5 is prepared by dissolving a sublimation dye of any of yellow, magenta, cyan or black, a binder resin, a release agent, and other additives in a solvent to prepare a coating solution for the dye layer, The coating liquid of each color can be formed in a predetermined region on the conductive base film by using various coating means such as gravure coating and drying.
[0027]
Examples of the yellow sublimation dye include Foron Brilliant Yellow-S-6GL (trade name of Disperse Yellow 231 manufactured by Sand Corp.), Macrolex Yellow 6G (trade name of Disperse Yellow 201 manufactured by Bayer Corp.), and the like. Examples of the magenta sublimable dye include MS-REDG (trade name of Disperse Violet 26 manufactured by Bayer). As cyan sublimation dyes, Kayaset Blue 714 (trade name of Solvent Blue 63 manufactured by Nippon Kayaku Co., Ltd.), Foron Brilliant Blue SR (trade name of Disperse Blue 354 manufactured by Sand Corp.), Waxolin AP-FW (ICI) The trade name of Solvent Blue 36 manufactured by the company) and black sublimation dyes include the above-mentioned mixtures of yellow, magenta and cyan dyes.
[0028]
Examples of the binder resin for the heat sublimable dye layer 5 include cellulose resins such as ethyl cellulose, ethyl hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, and cellulose acetate, vinyl such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, and polyvinyl pyrrolidone. Acrylic resins such as poly (meth) acrylate and poly (meth) acrylamide (the above (meth) means methacrylate), polyurethane resins, polyamide resins, polyester resins, and mixtures of these resins. It is done. As the binder resin, polyvinyl butyral and polyvinyl acetal are preferable because they have good dye migration and storage stability when used as a transfer film.
[0029]
The hot-melt ink layer 6 is formed by applying a hot-melt ink containing a colorant, a vehicle, and other additives to a known coating such as a hot melt coat, a hot lacquer coat, a gravure coat, a gravure reverse coat, and a roll coat. It can be formed using engineering means. The thickness of the heat-meltable ink layer 6 is usually formed to be 0.2 to 10 μm. The heat-meltable ink layer preferably uses a black colorant that is optimal for recording clear characters and symbols at a high concentration.
[0030]
Examples of the vehicle of the hot-melt ink layer 6 include wax, a mixture of wax and drying oil, resin, mineral oil, cellulose, rubber derivatives, and the like. The above waxes are microcrystalline wax, carnauba wax, paraffin wax, Fischer-Tropsch wax, low molecular polyethylene, wood wax, beeswax, whale wax, ibota wax, wool wax, shellac wax, candelilla wax, petrolatum, partially modified wax, fatty acid Examples include esters and fatty acid amides.
[0031]
As shown in FIGS. 4A to 4I, the fluorescent latent image transfer film may be formed by layer-sequentially forming a protective layer 7 on the same transfer surface as the fluorescent ink layer 3 as a layer other than the fluorescent ink layer 3. Specifically, the modes of FIGS. 4A to 4I are configured in such a manner that the arrangement order in the plane direction of each region is as follows, and this region is repeatedly formed in the flow direction as a basic unit. ing.
(A) Fluorescent ink layer 3 and protective layer 7.
(B) Yellow dye layer 5Y, magenta dye layer 5M, cyan dye layer 5C, fluorescent ink layer 3, and protective layer 7.
(C) Yellow dye layer 5Y, magenta dye layer 5M, cyan dye layer 5C, black dye layer 5B, fluorescent ink layer 3, and protective layer 7.
(D) Yellow dye layer 5Y, magenta dye layer 5M, cyan dye layer 5C, fluorescent ink layer 3, hot-melt black ink layer 6BK, and protective layer 7.
(E) Black dye layer 5BK, fluorescent ink layer 3, and protective layer 7.
(F) Fluorescent ink layer 3, hot-melt black ink layer 6BK, protective layer 7.
(G) A yellow dye layer 5Y, a magenta dye layer 5M, a cyan dye layer 5C, a black dye layer 5BK, a fluorescent ink layer 3, a heat-meltable black ink layer 6BK, and a protective layer 7.
(H) The same area order as in (g) above, except that the total area of the yellow dye layer 5Y, magenta dye layer 5M, and cyan dye layer 5C is the black dye layer 5BK, fluorescent ink layer 3, heat The meltable black ink layer 6BK and the protective layer 7 were formed smaller than the exclusive area.
(I) Hot-melt black ink layer 6BK, protective layer 7, yellow dye layer 5Y, magenta dye layer 5M, cyan dye layer 5C, fluorescent ink layer 3, hot-melt black ink layer 6BK, protective layer 7.
[0032]
In FIG. 4, the positions of the panels excluding the protective layer may be in any order. However, the panel order of the fluorescent ink layer 3 may be after the protective layer. When the protective layer 7 is directly transferred from the transfer film to the transfer target, the protective layer 7 is positioned on the outermost surface of the image after the transfer so as to protect the image satisfactorily as shown in FIGS. As a general rule, it is preferable to provide it at the last position in one constituent unit of the region provided in the frame order. Further, as shown in FIG. 4 (i), the protective layer 7 is composed of one frame sequential structural unit, for example, provided in two places, after the hot-melt black ink layer 6BK and at the last position of the region unit. Of these, two or more regions may be provided.
[0033]
The protective layer 7 can be formed by applying a coating composition containing a protective layer forming resin for this type of transfer film to the surface of the film substrate by a known coating means. The protective layer 7 is formed to be transparent, such as colorless and transparent or colored and transparent, so that an image of the lower layer can be seen after transfer. For example, polyester, polystyrene, acrylic, polyurethane, acrylic urethane, etc., or a mixture of resins, silicone-modified resins, mixtures of these modified resins, ionizing radiation curable resins, ultraviolet rays Examples include a blocking resin. The thickness of the protective layer 7 is usually formed to about 0.5 to 10 μm.
[0034]
The protective layer containing the ionizing radiation curable resin is particularly excellent in plasticizer resistance and scratch resistance. As the ionizing radiation curable resin, known ones can be used. For example, a radically polymerizable polymer or oligomer is crosslinked and cured by ionizing radiation, and a photopolymerization initiator is added as necessary. What was polymerized and cross-linked by ultraviolet rays can be used.
[0035]
The main purpose of the protective layer containing the ultraviolet blocking resin is to impart light resistance to the printed material. As the ultraviolet blocking resin, for example, a resin obtained by reacting and bonding a reactive ultraviolet absorber with a thermoplastic resin or the above ionizing radiation curable resin can be used. Reactive UV absorbers include non-reactive organic UV absorbers such as salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, nickel-chelates, hindered amines, addition polymerizable double bonds (for example, A vinyl group, an acryloyl group, a methacryloyl group, etc.), an alcoholic hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group.
[0036]
Further, a hologram pattern or the like can be formed on the protective layer 7. Examples of the hologram pattern include a relief hologram uneven pattern. In addition, the other pattern may be an uneven pattern of a diffraction grating.
[0037]
In the fluorescent latent image transfer film in which a layer other than the fluorescent ink layer 3 is provided in the surface order as a transfer layer and a plurality of layers are provided, the length of each region (or the area of the region) is the same length. Although the transfer film may be formed so that the areas of the respective layers have the same area, as shown in the embodiments of FIGS. 3 (h) and 4 (h), yellow, magenta, and cyan thermal sublimation dye layers 5 (5Y, 5M, 5C), the area occupied by the dye layer 5 is reduced to a layer other than the dye layer (fluorescent ink layer 3, heat sublimation black dye layer 5BK, heat melt black The ink layer 6BK, the protective layer 7, etc.) can be formed to be smaller than the exclusive area of the total area.
[0038]
FIG. 5 and FIG. 6 are cross-sectional views showing aspects of a printed matter formed by the method for forming a fluorescent latent image transfer film of the present invention. The printed product 9 shown in FIG. 5 has a fluorescent latent image 11 and a color transfer image 12 using a sublimation dye, a single color transfer image 13 using a sublimation dye, and a single color transfer using a hot-melt ink on the surface of the transfer target 10. A visible image such as the image 14 is provided, and the surface thereof is covered with a protective layer 15.
[0039]
6 is a visible image such as a color transfer image 12 with a sublimation dye, a monochrome transfer image 13 with a sublimation dye, and a monochrome transfer image 14 with a hot-melt ink on the surface of the transfer object. Then, the protective layer 15 is formed so as to cover the entire surface of the image, and the fluorescent latent image 11 is provided on the surface of the protective layer 15.
[0040]
In the method of the present invention, the fluorescent latent image 11 may be formed either after (a) the visible image is formed, (b) before the visible image is formed, or (c) during the formation of the visible image. In addition, the position where the fluorescent latent image 11 is formed may be provided in either the position that does not overlap the visible image or the position that overlaps the visible image in the case of (a). Any position that does not overlap the image may be used.
[0041]
Further, when the protective layer 15 is formed, as shown in FIG. 5, when the entire visible image and the fluorescent latent image 11 are covered and formed on the outermost surface of the printed product 9, the storability of the image of the printed product is the best. For example, it is optimal for a card or the like that requires durability such as scratch resistance. In addition, as shown in FIG. 6, when the fluorescent latent image 11 is provided on the surface of the protective layer 15, if the fluorescent latent image is about the thickness of the fluorescent ink layer formed on the transfer film, the visible image in the lower layer is displayed. Since viewing is not hindered, it can be formed without any problem even above the visible image, and there is an advantage that the formation position is not restricted. As described above, the formation position, the formation order, and the like of the fluorescent latent image, visible image, protective layer, and the like of the printed material can be appropriately selected according to the purpose of the printed material used.
[0042]
The visible image and the protective layer can be formed by a printing method, a coating method, a transfer method using another transfer sheet, or the like. Alternatively, it is preferable to use a transfer film in which a protective layer and the like are provided in the surface order with the fluorescent ink layer, so that in addition to the fluorescent latent image, an image by a sublimable dye layer, a protective layer, and the like can be continuously formed. .
[0043]
The sublimation dye layer of such a latent image transfer film is optimally used to form continuous tone images such as full-color photographs and continuous tone images such as single-color photographs. Monochromatic and multicolored images can also be formed. The heat-meltable black ink layer is optimally used for printing characters and codes without gradation.
[0044]
A thermal transfer image receiving sheet is preferably used as the transfer target 10 that forms the printed product 9. The thermal transfer image receiving sheet is configured by providing a receiving layer on the surface of a substrate. The base material is plain paper, synthetic paper, paper such as synthetic resin or emulsion impregnated paper, saturated polyester such as polyethylene terephthalate, polyamide, polyethylene, polypropylene, polyacrylate, polycarbonate, polyurethane, polyvinyl chloride, poly-vinyl acetate , Polystyrene, cellulosic resin, polysulfone, polyimide, and other plastic sheets (including films). The substrate may be transparent or opaque, and may be reflective by adding a white pigment or the like into the substrate. The base material may be formed in a card shape.
[0045]
The receiving layer of the thermal transfer image receiving sheet is formed from a dye dyeable resin. Dye dyeable resins include, for example, saturated polyester, polyamide, polyacrylate, polycarbonate, polyurethane, polyvinyl acetal, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polystyrene, styrene-acrylic copolymer. Examples thereof include a coalescence, a styrene-butadiene copolymer, a vinyl toluene-acrylic copolymer, and a cellulose resin. These resins may be used alone or in combination of two or more. Moreover, you may add additives, such as a mold release agent and various coloring agents for preventing a thermal transfer sheet to melt | fuse.
[0046]
Further, a release layer made of silicone oil, a fluorine-based compound, various waxes, or the like may be provided on the back side of the thermal transfer image-receiving sheet (the surface opposite to the receiving layer).
[0047]
These thermal transfer image receiving sheets may be in a state where they are not printed at all, or may be formed in the form of paper, booklet, form, or the like that has been printed in advance.
[0048]
As a heating element used to transfer an image such as a fluorescent latent image transfer film, or other sublimation dye transfer sheet or protective layer transfer sheet, a heating means such as a thermal head or a laser is used, depending on the image information to be transferred. It is formed so that it can be heated. Commercially available heating elements can be used.
[0049]
The fluorescent latent image transfer method of the present invention can be optimally used for forming a certificate containing a photo card and characters such as an ID card or other ID card or a credit card, a passport or a license card.
[0050]
In the above-described fluorescent latent image transfer method, a fluorescent latent image is formed by transferring a fluorescent ink layer in a pattern onto a substrate to be transferred (recording medium). In this method, when a binder that can be melt-transferred is used for the fluorescent ink layer, the binder resin and the specific fluorescent agent are both transferred to the transfer target to form a fluorescent latent image. Also, when a binder resin that does not melt transfer is used, the fluorescent agent in the fluorescent ink layer has sublimation properties, so that only the fluorescent agent moves to the transfer substrate to form a fluorescent latent image. .
[0051]
In general, sublimation transfer is excellent in gradation expression, but the transfer amount of dyes and fluorescent agents is small compared to melt transfer, and the density of the formed image is low. is there. Therefore, in the above transfer method, when the gradation is regarded as important, a sublimation transfer method is selected, and in order to obtain a sufficient luminance of the fluorescent latent image, a method of transferring the fluorescent ink layer by the melt transfer method is used.
[0052]
Further, as described in the section of the subject of the present invention, even when the melt transfer method is selected, the fluorescent ink layer of the fluorescent latent image transfer film is transferred to the transfer substrate in a pattern to form a fluorescent latent image. In the method, there is a limit to increasing the concentration of the fluorescent agent. In such a case, the following fluorescent latent image forming method can be used.
[0053]
For example, as shown in FIG. 7, an intermediate transfer medium 30 in which a base film 31 is provided with a release layer 32, an ultraviolet absorption pattern 33, and a receiving layer 34 capable of recording information with dye ink in order, and as shown in FIG. 11. The base film is provided with a yellow ink layer 22Y, a magenta ink layer 22M, a cyan ink layer 22C, a heat sublimation black ink layer 22BK (these ink layers are referred to as a dye ink layer 22), and a release layer 23 provided in the surface order. 14 (a) to (c) are performed using the dye transfer film 20 in which the fluorescent adhesive layer 24 formed from the adhesive ink blended with the fluorescent material is formed on the release layer 23. A recording medium (security pattern forming body 51) on which a security pattern is formed can be formed.
[0054]
As shown in FIG. 14 (a), the dye ink layer 22 of the dye transfer film is used for the receiving layer 34 of the intermediate transfer medium, and a visible image 35 is formed by sublimation transfer to a predetermined pattern to record information. Next, as shown in FIG. 4B, the fluorescent adhesive layer 24 of the dye transfer film is melt-transferred and laminated on the entire surface from above the receiving layer, and the release layer 32, the ultraviolet absorption pattern 33, An intermediate transfer medium 30 provided with a receiving layer 34 and a visible image 35 as a transfer layer 36 is formed. Finally, as shown in FIG. 3C, the transfer layer 36 of the intermediate transfer medium 30 is transferred to the surface of the transfer target 50, and the fluorescent adhesive layer 24 and ultraviolet light located above the fluorescent adhesive layer are transferred. A security pattern forming body 51 having a fluorescent latent image composed of the absorption pattern 33 and the visible image 35 is obtained.
[0055]
The security pattern forming body of FIG. 14C absorbs ultraviolet rays by the ultraviolet absorption pattern 33 located above the fluorescent adhesive layer 24 when the ultraviolet rays are irradiated from above the surface. As a result, the fluorescent image obtained by ultraviolet irradiation is a negative image of the ultraviolet absorption pattern 33.
[0056]
The above-described fluorescent latent image is used as a security pattern, and an image in which a fluorescent latent image is provided on a transfer target body is referred to as a security pattern forming body. As the material to be transferred, a material requiring security is suitably used, and examples thereof include various cards such as a passport booklet, an ID card, a credit card, and a license.
[0057]
If the ultraviolet absorption pattern 33 for forming the fluorescent latent image is below the fluorescent material layer such as the fluorescent adhesive layer 24 in the transfer layer 36 of the intermediate transfer medium 30, the ultraviolet absorbing pattern 33 is transferred from the fluorescent material layer after being transferred to the transfer target. Since it is also located above, it may be formed in any layer. The ultraviolet absorption pattern can be formed from a material obtained by adding an organic ultraviolet absorber to a resin binder, or a material reacted with a resin binder.
[0058]
Examples of the organic ultraviolet absorber include salicylate, benzophenone, benzotriazole, substituted acrylonitrile, nickel chelate, hindered amine, and the like.
[0059]
In addition, the reactive ultraviolet absorber is, for example, an addition polymerizable double bond such as a vinyl group, an acryloyl group, or a methacryloyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, an epoxy group, or an isocyanate group. Etc. into which a resin is introduced is used by being reactively fixed to a resin binder. As a method for reaction fixation, a copolymer is obtained by radical polymerization of a resin component of a conventionally known monomer, oligomer, or reactive polymer and a reactive ultraviolet absorber having an addition polymerizable double bond as described above. be able to. When the reactive ultraviolet absorber has a hydroxyl group, an amino group, a carboxyl group, an ethoxy group, or an isocyanate group, a thermoplastic resin having reactivity with the above reactive group is used, and a catalyst is used as necessary. The reactive ultraviolet absorber can be reactively fixed to the thermoplastic resin by heat or the like.
[0060]
The ultraviolet absorption pattern 33 may be formed by any means such as a printing method using an ink having the ultraviolet absorber described above or a transfer method, but the ultraviolet absorber is formed on the surface of the release layer 23 as shown in FIG. The dye transfer film 20 provided with the layer 25 is preferably formed by transfer onto an intermediate transfer medium when forming a visible image.
[0061]
The release layer 32 of the intermediate transfer medium 30 is peeled off from the substrate film 31 when transferred to the transfer medium, and is positioned on the outermost surface after transfer to become a protective layer. As the release layer, a material used for a release layer of a known transfer sheet can be used.
[0062]
The release layer can be formed from a composition containing a binder resin and a release material. As the binder resin, acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, and polybutyl acrylate which are thermoplastic resins, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl butyral, etc. Vinyl resins, cellulose derivatives such as ethyl cellulose, nitrocellulose, and cellulose acetate, unsaturated polyester resins that are thermosetting resins, polyester resins, polyurethane resins, aminoalkyd resins, and the like can be used. As the releasable material, waxes, silicone waxes, silicone resins, melamine resins, fluorine resins, fine powders of talc and silica, lubricants such as surfactants and metal soaps, and the like can be used.
[0063]
The release layer is prepared by dissolving or dispersing the above resin in an appropriate solvent to prepare a coating solution, which is applied to the substrate film by means of a gravure printing method, a screen printing method or a reverse coating method using a gravure plate. It can be formed by coating and drying. The thickness after drying of a peeling layer is 0.1-5 micrometers normally.
[0064]
In the intermediate transfer medium in FIG. 14B, the fluorescent adhesive layer is configured such that the adhesive layer also serves as the fluorescent material layer, but the fluorescent material layer and the adhesive layer may be formed as separate layers. For example, like the intermediate transfer film 30 shown in FIG. 8, a release layer 32, an ultraviolet absorption pattern 33, a fluorescent material layer 37, and a receiving layer 34 also serving as an adhesive layer are sequentially formed on the surface of the base film 31, It is also possible to record information such as a visible image on the receiving layer 34 of the intermediate transfer film to constitute an intermediate transfer medium, and transfer it to the surface of the transfer target to form a security pattern forming body.
[0065]
The receiving layer that also serves as the adhesive layer is formed from a dye-dyeable resin. Specifically, saturated polyester, polyamide, polyacrylate, polycarbonate, polyurethane, polyvinyl acetal, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polystyrene, styrene-acrylic copolymer, styrene- Examples thereof include butadiene copolymers, vinyl toluene-acrylic copolymers, and cellulose resins. These resins may be used alone or in combination of two or more.
[0066]
As the fluorescent material layer, for example, a fluorescent latent image transfer film shown in FIG. 1 or a material containing a fluorescent agent represented by the formula (Formula 1) used in the fluorescent ink layer of the film is preferably used. The following phosphor-containing materials can be used.
[0067]
The phosphor is a substance that emits luminescence, and includes both inorganic phosphors and organic phosphors. Inorganic phosphors mainly include oxides such as Ca, Ba, Mg, Zn, and Cd, crystals such as sulfides, silicates, phosphates, and tungstates, and Mn, Zn, Ag, Cu, A pigment obtained by adding a metal element such as Sb or Pb or a rare earth element such as a lanthanoid as an activator and calcining can be used.
[0068]
Preferred phosphors include ZnO: Zn, Br (PO) Cl: Eu, ZnGeO: Mn, YO: Eu, Y (P, V) O: Bu, YOSi: Eu, ZnGeO: Mn, and the like. Organic phosphors include diaminostilbene disulfonic acid derivatives, imidazole derivatives, coumarin derivatives, derivatives of triazole, carbazole, pyridine, naphthalic acid, imidazolone, dyes such as fluorescein and eosin, compounds having a benzene ring such as anthracene, etc. Can be.
[0069]
In terms of durability and weather resistance, inorganic pigments are excellent. On the other hand, organic pigments have good wettability of the ink vehicle, and are therefore excellent in inkability even without any surface treatment. Among these pigments, in order to improve durability, weather resistance, particularly light resistance or printability, a stable oxide or oxyacid salt inorganic phosphor having a relatively large particle size and high luminance is used. preferable. In particular, using ZnO: Zn is excellent in terms of luminance and weather resistance. Moreover, rare earth phosphors can also be exemplified as the phosphor.
[0070]
In addition, it is preferable that the phosphor has a pigment particle size prepared in order to improve the fluorescence characteristics such as luminance and the printing characteristics of the ink. From such a viewpoint, it is preferable to use a phosphor composed of pigment particles having an average particle size of 0.7 to 4 μm, more preferably an average particle size of 0.7 to 2 μm, and most preferably 1 to 2 μm. It is desirable to use a range of pigment particles. In general, it is expected that the ink characteristics are improved as the pigment particle size is smaller. However, when the particle size is less than 0.7 μm, a phenomenon in which the luminance of fluorescence is significantly reduced is observed. Therefore, it is preferable to use a phosphor having a particle size of 0.7 μm or more. On the other hand, when the particle diameter exceeds 4 μm, the transparency of the obtained fluorescence image may be lowered.
[0071]
The content of the phosphor with respect to the entire composition excluding the solvent constituting the fluorescent ink is suitably 15 to 80% by weight in order to improve both the luminance and the transferability (adhesiveness) to the printing substrate. A more preferred range is 20 to 50% by weight. When the phosphor content is less than 15%, depending on the type of phosphor, the fluorescence brightness in the ink composition state is extremely reduced. For example, when the content is about 12%, the brightness of the pigment itself is about 1/10. It may decrease to. Further, the thickness of the fluorescence emission image can be appropriately determined depending on the required fluorescence brightness, phosphor content, etc., and can be about 1 to 10 μm, for example. In the present invention, from the viewpoint of ensuring transparency, a phosphor having a relatively small particle size is used as described above. However, the lack of fluorescence intensity due to the small particle size is caused by increasing the thickness of the fluorescence emission image. Can be supplemented.
[0072]
Furthermore, it is preferable to perform a surface treatment to improve the properties of the phosphor (hiding power, coloring power, oil absorption, durability, etc.). In particular, when an inorganic pigment is used, since the surface thereof is hydrophilic and has a poor affinity with an oily polymer, it is preferable to improve the affinity with the polymer by performing a surface treatment. Examples of the method include a method using a coating agent, a coupling agent, a polymerizable monomer, and the like.
[0073]
Further, as shown in FIGS. 9 and 10, the security pattern forming body forms a hologram pattern by applying a hologram effect layer 41 to the transfer layer 36 and fine embossing on the surface of the hologram effect layer. A hologram composed of the metal thin film layer 42 provided by depositing titanium oxide or the like from above can be provided. In the embodiment shown in FIG. 9, an ultraviolet absorption pattern 33 and a receiving layer 34 are provided on the hologram pattern. Further, in the embodiment shown in FIG. 10, a fluorescent material layer 37 is provided on the ultraviolet absorption pattern on the hologram pattern, and a receiving layer is provided thereon. Thus, a security pattern forming body with higher safety can be obtained by using the fluorescent latent image together with other security means such as a hologram.
[0074]
Examples of the base resin of the hologram effect layer 41 include unsaturated polyester resins, acrylic urethane resins, epoxy-modified acrylic resins, epoxy-modified unsaturated polyester resins, alkyd resins, phenol resins and the like, and thermoplastics. Examples of the resin include acrylate resin, acrylamide resin, nitrocellulose resin, polystyrene resin, and the like. These resins can be used alone or in combination of two or more kinds of isocyanate resins, metal soaps such as cobalt naphthenate and zinc naphthenate, benzoyl peroxide, methyl ethyl ketone peroxide, benzophenone, acetophenone, anthraquinone, naphthoquinone, azo Thermal or ultraviolet curing agents such as bisisobutyronitrile and diphenyl sulfide may be blended. In addition, as ionizing radiation curable resins, epoxy acrylate, urethane acrylate, acrylic modified polyester, etc. are used as oligomers, and monomers such as neopentyl glycol acrylate, trimethylol propane triacrylate, etc. are used for the purpose of preparing a crosslinked structure and viscosity. Those appropriately mixed are used.
[0075]
The dye transfer film shown in FIGS. 11 to 13 can be used to form the intermediate transfer medium. In these dye transfer films, an ink layer 22 and a release layer 23 of each color are formed in a surface sequence, and a single layer such as an adhesive layer 26, an ultraviolet absorber layer 27, and a fluorescent material layer 25 is formed on the release layer 23. A plurality of ink ribbons are formed.
[0076]
【Example】
[Production Example 1 of fluorescent latent image transfer film]
A 6 μm thick polyethylene terephthalate film (trade name Lumirror: manufactured by Toray Industries, Inc.) is used as a base film, a heat resistant slip layer (back layer) on one side thereof, and a gravure coating method is used so that the silicone resin has a thickness of 1 μm. The coating amount for the fluorescent ink layer having the following composition is formed on the other surface by a gravure coating method, and the coating amount when dried is 0.6 g / m.² It was applied and dried so as to form a fluorescent latent image transfer film. In addition, No. of the fluorescent compound of an Example. Is shown in Table 1 above.
[0077]
[Fluorescent ink layer coating solution 1]
・ 5 parts by weight of polyvinyl acetal resin (manufactured by Sekisui Chemical Co., Ltd.)
-Fluorescent compound No. 8 3 parts by weight
・ Methyl ethyl ketone 60 parts by weight
・ Toluene 22 parts by weight
・ 10 parts by weight of isopropanol
[0078]
[Preparation Example 2 of Fluorescent Latent Image Transfer Film]
The fluorescent latent image layers prepared in Preparation Example 1 of the above-described fluorescent latent image transfer film were sequentially processed in the order of yellow, magenta, cyan, black sublimation dye layer, fluorescent ink layer, thermal transfer resin black layer, and protective layer. In addition, gravure printing is repeatedly performed so that the panel length of each color (or each layer) is 15 cm, followed by drying to form a four-color dye layer-resin black layer-fluorescent ink layer-protective layer integrated fluorescent latent image transfer film did.
[0079]
[Production Example 3 of Fluorescent Latent Image Transfer Film]
In the fluorescent latent image transfer film production example 2, an integrated fluorescent latent image transfer film was obtained in the same manner as in the film production example 2 except that the fluorescent ink layer was provided in the subsequent order of the protective layer panel.
[0080]
[Production Example 4 of Fluorescent Latent Image Transfer Film]
In Film Production Example 2, a fluorescent ink layer and a hologram protective layer integrated fluorescent latent image transfer film were formed in the same manner as in Film Production Example 2 except that a hologram pattern was formed on the protective layer.
[0081]
Example 1
The sublimation type thermal transfer sheet and thermal transfer image receiving sheet described below were superposed, and thermal energy was applied using a thermal head of a printer operating according to an electrical signal obtained by color separation of a face photograph to form a full color image.
Next, the image-receiving sheet on which the full-color image is formed and the transfer film of Preparation Example 1 of the fluorescent latent image transfer film are overlapped, and according to the electrical signal obtained from the monocolor image rich in gradation different from the face photograph. A fluorescent latent image was formed using the thermal head of the printer, and a printed matter having the fluorescent latent image was obtained.
[0082]
The sublimation type thermal transfer sheet is provided with a 0.5 μm thick primer layer made of urethane resin on one side of a 6 μm thick polyethylene terephthalate film (Toray Industries, Inc .: Lumirror) and 1 μm thick on the other side (back). A heat-resistant slip layer is provided, and the composition of the following yellow ink, magenta ink, and cyan ink is provided on the surface of the primer layer so that each length becomes 15 cm in this order along the flow direction of the polyester film. Were repeatedly gravure-printed and dried to form a three-color sublimation ink layer to obtain a sublimation type thermal transfer sheet. The coating amount of each color is about 3 g / m.² (Solid content). Three color inks containing sublimable dyes were prepared as follows.
[0083]

[0084]
[Chemical Formula 3]

[Wherein n represents a normal system. ]
[0085]
[Magenta ink composition]
A magenta ink was obtained in the same manner as in the yellow ink except that the dye was replaced with C.I. Disperse Red 60.
[0086]
[Cyan ink composition]
A cyan ink was obtained in the same manner except that the dye was replaced with C.I. Solvent Blue 63 in the yellow ink.
[0087]
The thermal transfer image-receiving sheet uses synthetic paper (YUPO FPG-150, thickness 150 μm, made by Oji Oil Chemical Co., Ltd.) as a base sheet, and a coating liquid for the dye-receiving layer having the following composition is applied to one side thereof by a bar coater. The coating amount when dried is 4 g / m² Then, a dye-receiving layer was formed by coating and drying to prepare a thermal transfer image-receiving sheet.
[0088]

[0089]
Example 2
In Example 1, a printed matter having a fluorescent latent image was obtained in the same manner as in Example 1 except that a fluorescent latent image was formed before forming a full-color image.
[0090]
Example 3
A print was obtained in the same manner as in Example 1 except that a protective layer was formed on the print of Example 1 provided with a full-color image and a fluorescent latent image.
[0091]
Example 4
A printed matter was obtained in the same manner as in Example 1 except that a protective layer was first formed on the printed matter provided with the full-color image in Example 1, and then a fluorescent latent image was provided on the protective layer.
[0092]
Example 5
Using the four-color dye layer-fluorescent latent image layer-resin black layer-protective layer integrated film of Preparation Example 2 of a fluorescent latent image transfer film, first, a full-color image described in Example 1 using three colors of yellow-magenta-cyan On a thermal transfer image-receiving sheet, and then, using a dye black layer, a sign and fingerprint information are printed in a region different from the full-color image of the face photograph on the thermal transfer image-receiving sheet, and then a fluorescent ink layer is used to implement A fluorescent latent image is formed in accordance with the electrical signal obtained from the mono-color image of 1 and further printed with character information such as name, date of birth, address, etc. and barcode using a resin black ink layer, and finally a thermal transfer image receiving sheet A protective layer was transferred so as to cover the entire image provided above, and a printed matter was obtained.
[0093]
Example 6
In Example 5, instead of providing a protective layer after forming the fluorescent latent image using the integrated film of the fluorescent latent image transfer film preparation example 2, the protective film is protected using the integrated film of the fluorescent latent image transfer film preparation example 3. A printed matter was obtained in the same manner as in Example 5 except that a fluorescent latent image was formed after providing the layer.
[0094]
Example 7
Example 5 In Example 5, except that the integral film of the fluorescent latent image transfer film production example 3 was used instead of the integral film of the fluorescent latent image transfer film production example 2, and the protective layer on which the hologram pattern was formed was transferred. In the same manner as in No. 5, a printed material on which a hologram pattern was formed was obtained.
[0095]
Example 8
A card-like printed matter was obtained in the same manner as in Example 5 except that a card was used as the thermal transfer image-receiving sheet.
[0096]
Example 9
A printed matter was obtained in the same manner as in Example 5 except that a passport booklet was used as the thermal transfer image receiving sheet.
[0097]
Example 10
A printed matter was obtained in the same manner as in Example 5 except that a license was used as the thermal transfer image receiving sheet.
[0098]
About the printed matter of Example 1- Example 10, the visibility of the fluorescence latent image was evaluated. The results are shown in Table 2. The evaluation method is to irradiate ultraviolet rays with a wavelength of 300 to 400 nm, visually observe whether or not the fluorescent latent image can be clearly recognized, and mark that the fluorescent color development is clearly confirmed as ○, and the printing pattern of the fluorescent latent image Those that could not be confirmed were evaluated as x. As shown in Table 2, in all of Examples 1 to 10, the fluorescent color development was clearly confirmed.
[0099]
[Table 2]

[0100]
Intermediate transfer medium (1)
The surface of a 12 μm thick polyethylene terephthalate transparent substrate is 1.5 μm release layer (also protective layer), UV absorber pattern printing is performed by gravure printing, 1.0 μm, and dye receiving layer 2.0 μm is gravure coated, An intermediate transfer medium having an embodiment shown in FIG. 7 was obtained.
[0101]
Intermediate transfer medium (2)
A 12 μm thick polyethylene terephthalate transparent substrate surface is peeled layer (also protective layer) 1.5 μm, UV absorption pattern printing is performed by gravure printing, 1.0 μm, fluorescent material layer 3.0 μm, dye receiving layer 2 Gravure coating of 0.0 μm was sequentially performed to obtain an intermediate transfer medium having an embodiment shown in FIG.
[0102]
Intermediate transfer medium (3)
The surface of a 12 μm thick polyethylene terephthalate transparent substrate was gravure coated with a release layer (also protective layer) of 1.5 μm and a hologram effect layer of 2.0 μm. The hologram effect layer surface was finely embossed to form a hologram pattern. Subsequently, titanium oxide was vacuum-deposited (500 A) on the surface of the hologram effect layer after embossing. Further, an ultraviolet absorption pattern was printed on the surface, and 1.0 μm and a receiving layer 2.0 μm were gravure coated to obtain an intermediate transfer medium having an embodiment shown in FIG.
[0103]
Intermediate transfer medium (4)
The surface of a 12 μm thick polyethylene terephthalate transparent substrate was gravure coated with a release layer (also protective layer) of 1.5 μm and a hologram effect layer of 2.0 μm. The hologram effect layer surface was finely embossed to form a hologram pattern. Next, titanium oxide was vacuum-deposited (500 Å) on the surface of the hologram effect layer after embossing. Further, an ultraviolet absorption pattern was printed on the surface, and 1.0 μm, a fluorescent material layer 3.0 μm, and a receiving layer 2.0 μm were gravure coated to obtain an intermediate transfer medium having an embodiment shown in FIG.
[0104]
The intermediate transfer medium and dye transfer film release layer, hologram effect layer, receptor layer, fluorescent material layer, ultraviolet absorption layer, and adhesive layer had the following compositions, respectively.
[0105]
[Peeling layer (also protective layer) coating solution] (Hereinafter, all units are parts by weight)
Acrylic resin 40 parts
2 parts polyester resin
50 parts of methyl ethyl ketone
50 parts of toluene
[0106]
[Hologram effect layer coating solution]
Acrylic resin 40 parts
Melamine resin 10 parts
50 parts of cyclohexanone
50 parts of methyl ethyl ketone
[0107]
[Receptive layer coating solution]
50 parts of vinyl chloride-vinyl acetate copolymer
Acrylic silicone 1.5 parts
50 parts of methyl ethyl ketone
50 parts of toluene
[0108]
[Ink for fluorescent materials]
Byron 270 (polyester resin) 30 parts
Ubitex OB 1 part
Toluene 35 parts
Methyl ethyl ketone 35 parts
[0109]
[UV absorbing layer ink 1]
40 parts of copolymer resin reactively bonded with reactive UV absorber
(UVA-635L manufactured by BASF Japan)
40 parts of zinc antimonate
30 parts of methyl ethyl ketone
30 parts of toluene
[0110]
[Adhesive layer ink]
30 parts vinyl chloride resin
Toluene 35 parts
Methyl ethyl ketone 35 parts
[0111]
Dye transfer film (1)
The yellow, magenta, and cyan inks were gravure coated in this order in the order of flow along the flow direction of the PET film (coating amount: 3.0 μm). Further, a release layer was provided in the surface order following the film, and an adhesive layer was provided on the release layer to obtain a dye transfer film.
[0112]
Dye transfer film (2)
The yellow, magenta, and cyan inks were gravure coated in this order in the order of flow along the flow direction of the PET film (coating amount: 3.0 μm). Further, a release layer was provided in the surface order after the above film, and an adhesive layer ink and a fluorescent material ink were blended in equal amounts on the release layer to form an adhesive layer / fluorescent material layer to obtain a dye transfer film.
[0113]
Dye transfer film (3)
The yellow, magenta, and cyan inks were gravure coated in this order in the order of flow along the flow direction of the PET film (coating amount: 3.0 μm). Further, a release layer is provided in the surface sequence following the film, an ultraviolet absorber layer is provided in the surface sequence on the release layer, and an adhesive layer ink and a fluorescent material ink are blended in equal amounts to form an adhesive layer / fluorescent material layer. To obtain a dye transfer film.
[0114]
The following compositions were used for the respective color inks of the dye transfer film.
<Yellow ink>
Quinophthalone dye represented by the following structural formula [Chemical Formula 4] 5.5 parts by weight
Polyvinyl butyral 4.5 parts by weight
(ESREC BX-1. Sekisui Chemical Co., Ltd.)
Methyl ethyl ketone / toluene (1/1) 90.0 parts by weight
[0115]
[Formula 4]

[0116]
<Magenta ink>
A magenta ink was obtained in the same manner as in the yellow ink except that the dye was replaced with C.I. Disperse Red 60.
[0117]
<Cyan ink>
Cyanink was obtained in the same manner as in the above yellow ink except that the dye was replaced with CI Solvent Blue 63 (CI Solvent Blue 63).
[0118]
Security pattern forming body (1)
Using the intermediate transfer medium (1) and the dye transfer film (2), a sublimation dye image is formed on the receiving layer of the intermediate transfer medium (1) as shown in the process diagram of FIG. After transferring the solid pattern (fluorescent adhesive layer), the adhesive layer was transferred and transferred again to a passport booklet to obtain a security pattern forming body.
[0119]
Security pattern forming body (2)
Using the intermediate transfer medium (1) and the dye transfer film (3), a sublimation dye image is formed on the receiving layer of the intermediate transfer medium (1) as shown in the process diagram of FIG. After transferring the pattern and transferring the solid pattern of the fluorescent material layer / adhesive layer, it was transferred again to a passport booklet to obtain a security pattern forming body.
[0120]
Security pattern forming body (3)
Using the intermediate transfer medium (2) and the dye film (1), as shown in the process diagram of FIG. 16, a sublimation dye image is formed on the receiving layer of the intermediate transfer medium (2) and transferred again to the passport after transferring the adhesive layer. A security pattern forming body was obtained.
[0121]
Security pattern forming body (4)
Using the intermediate transfer medium (3) and the dye film (2), as shown in the process diagram of FIG. 17, a sublimation dye image is formed on the receiving layer of the intermediate transfer medium (3), and the fluorescent material layer / adhesive layer is a solid pattern. After the transfer, the adhesive layer was transferred and transferred again to a passport booklet to obtain a security pattern forming body.
[0122]
Security pattern forming body (5)
Using the intermediate transfer medium (3) and the dye film (3), as shown in the process diagram of FIG. 18, a sublimation dye image is formed on the receiving layer of the intermediate transfer medium (3), and the ultraviolet absorbing layer is patterned with a thermal head. After transferring and solid pattern transfer of the fluorescent material layer / adhesive layer, it was transferred again to a passport booklet to obtain a security pattern formed body.
[0123]
Security pattern forming body (6)
Using the intermediate transfer medium (4) and the dye film (1), as shown in the process diagram of FIG. 19, a sublimation dye image is formed on the receiving layer of the intermediate transfer medium (4) and transferred again to the passport after transferring the adhesive layer. A security pattern forming body was obtained.
[0124]
Comparative example (1)
The surface of a 12 μm-thick polyethylene terephthalate transparent substrate was subjected to gravure coating with a release layer (also a protective layer) of 1.5 μm, a fluorescence coloring pattern by gravure printing, and a dye receiving layer of 2.0 μm.
[0125]
Comparative example (2)
The surface of a transparent substrate of polyethylene terephthalate having a thickness of 12 μm was subjected to gravure coating with a release layer (also protective layer) of 1.5 μm, a fluorescence coloring pattern by gravure printing, and 3.0 μm and a dye receiving layer of 2.0 μm.
[0126]
Comparative example (3)
Gravure coating with a release layer (cum protective layer) of 1.5 μm on the surface of a 12 μm thick polyethylene terephthalate transparent substrate, 1.0 μm of the fluorescent coloring pattern by gravure printing with the following ink composition, and 2.0 μm of the dye receiving layer did.
[0127]
The following inks were used for printing the fluorescent coloring patterns of Comparative Examples (1) to (3).
[Fluorescent ink]
Byron 270 (polyester resin) 30 parts
Ubitex OB 10 parts
Toluene 35 parts
Methyl ethyl ketone 35 parts
[0128]
[Table 3]

[0129]
Visibility: Visibility of fluorescent latent images visually (○: easy to visually recognize ×: difficult to visually recognize)
Information variability: Fluorescence latent image pattern variability (○: variable) ×: variable)
Concealability: Whether visual confirmation is possible under a normal light source (white light, sunlight) (○: not visible in normal state ×: visible fluorescent latent image pattern in normal state)
Reproducibility: Print reproducibility of dense patterns (○: good reproduction ×: poor reproduction)
Preservability: Occurrence of booking of roll preservability (○: good preservability ×: poor preservability)
[0130]
The present invention is not limited to any combination of films as long as the layer structure can form an ultraviolet absorption pattern and a fluorescent material layer simultaneously by combining the intermediate transfer medium (1) to (4) and the dye film (1) to (3). You may form using.
[0131]
【The invention's effect】
As described above, since the fluorescent latent image transfer method of the present invention employs a method of transferring using a fluorescent latent image transfer film having a fluorescent ink layer using a specific fluorescent agent, a continuous tone fluorescent latent image is used. Can be formed satisfactorily. This fluorescent latent image is not visible with visible light, but can be clearly confirmed when irradiated with ultraviolet rays. Therefore, since the printed matter of the present invention can confirm that the printed matter is authentic by using the fluorescent latent image, forgery or falsification due to copying or the like of the printed matter can be well prevented. The fluorescent ink comprising the resin binder containing the specific fluorescent compound is excellent in the transferability and gradation of the fluorescent latent image.
[0132]
In addition, the security pattern forming body of the present invention can obtain a sufficient color luminance of the fluorescent latent image pattern, and can easily identify the fluorescent latent image without adversely affecting the original fabric during processing.
[Brief description of the drawings]
FIG. 1 is a longitudinal sectional view of an essential part showing an example of a fluorescent latent image transfer film.
FIG. 2 is a longitudinal sectional view of an essential part showing another example of a fluorescent latent image transfer film.
FIGS. 3A to 3H are plan views showing aspects of a fluorescent latent image transfer film. FIGS.
FIGS. 4A to 4I are plan views showing aspects of a fluorescent latent image transfer film. FIGS.
FIG. 5 is a cross-sectional view showing an embodiment of the printed matter of the present invention.
FIG. 6 is a cross-sectional view showing an embodiment of the printed matter of the present invention.
FIG. 7 is a cross-sectional view showing an embodiment of an intermediate transfer medium.
FIG. 8 is a cross-sectional view showing an embodiment of an intermediate transfer medium.
FIG. 9 is a cross-sectional view showing an embodiment of an intermediate transfer medium.
FIG. 10 is a cross-sectional view showing an embodiment of an intermediate transfer medium.
FIG. 11 is a cross-sectional view showing an embodiment of a dye transfer film.
FIG. 12 is a cross-sectional view showing an embodiment of a dye transfer film.
FIG. 13 is a cross-sectional view showing an embodiment of a dye transfer film.
FIG. 14 is a process diagram showing a security pattern forming method.
FIG. 15 is a process diagram showing a security pattern forming method.
FIG. 16 is a process diagram showing a security pattern forming method.
FIG. 17 is a process diagram showing a security pattern forming method.
FIG. 18 is a process diagram showing a security pattern forming method.
FIG. 19 is a process diagram showing a security pattern forming method.
[Explanation of symbols]
1 Fluorescent latent image transfer film
2 heat resistant substrate film
3 Fluorescent ink layer
4 Back layer
5 Thermal sublimation dye layer
6 Hot-melt ink layer
7 Protective layer
9 Prints
10 Prints
11 Fluorescent latent image
12, 13, 14 Visible image
20 Dye transfer film
21 Base film
22 Dye ink layer
23 Release layer
24 fluorescent adhesive layer
25 Fluorescent material layer
26 Adhesive layer
27 UV absorbing layer
30 Intermediate transfer media
31 Base film
32 Release layer
33 UV absorption pattern
34 Receptor layer
35 Visible images
36 Transfer layer
37 Fluorescent material layer
38 Adhesive layer
40 Fluorescent latent image transfer film
41 Hologram effect layer
42 Metal thin film layer
50 Transferee
51 Security pattern forming body

Claims (8)

  At least on the surface of the transfer object, in a printed matter in which a receiving layer on which information is recorded and a security pattern based on a fluorescent latent image are provided, the security pattern is provided in a pattern above the fluorescent material layer and the fluorescent material layer. A transfer layer of the intermediate transfer medium on the surface of the transfer object using an intermediate transfer medium in which the receiving layer, the ultraviolet absorption pattern and the fluorescent material layer are formed as a transfer layer. A security pattern forming body characterized in that it is provided by being transferred. An ultraviolet absorber transfer film provided with an ultraviolet absorber layer is used as an ultraviolet absorption pattern, and the transfer film is heated to an arbitrary pattern by a heating element to transfer the ultraviolet absorber layer according to the pattern of the heating element. The security pattern forming body according to claim 1 , wherein the security pattern forming body is formed. The security pattern forming body according to claim 1 or 2 , wherein the fluorescent material layer is formed using a fluorescent latent image transfer film having a fluorescent ink layer made of a resin binder containing a fluorescent agent. The transfer layer in the intermediate transfer medium uses a dye transfer film containing a fluorescent material in the adhesive layer in the thermal transfer medium in which the dye ink layer and the adhesive layer are provided in the surface order on the surface of the base film. The security pattern forming body according to any one of claims 1 to 3, wherein the security pattern forming body is formed through transfer of a dye ink layer of a film and transfer of an adhesive layer.   A transfer layer having a fluorescent latent image composed of an ultraviolet absorption pattern and a fluorescent material layer and a transfer layer having a receiving layer on which information is recorded is provided on a base film, and the transfer layer of the intermediate transfer medium is used as a transfer target. The intermediate transfer medium is configured such that the ultraviolet absorption pattern in the transfer layer after transfer is positioned above the fluorescent ink layer to form a fluorescent latent image. A security pattern forming method characterized by being a thing. Using an ultraviolet absorber transfer film provided with an ultraviolet absorber layer, the transfer film is heated to an arbitrary pattern by a heating element, and an ultraviolet absorber layer corresponding to the pattern of the heating element is transferred to form an ultraviolet absorption pattern. The security pattern forming method according to claim 5, which is formed. 7. The security pattern forming method according to claim 5, wherein the fluorescent material layer is formed using a fluorescent latent image transfer film having a fluorescent ink layer made of a resin binder containing a fluorescent agent. In a thermal transfer medium in which a dye ink layer and an adhesive layer are provided in the surface order on the surface of a base film, a dye transfer film containing a fluorescent material is used for the adhesive layer, and the dye ink layer of the dye transfer film is transferred. The method for forming a security pattern according to claim 5, wherein a transfer layer in the intermediate transfer medium is formed through transfer of the adhesive layer.

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