JP2004074766A - Thermal transfer sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermal transfer sheet which responds to demands for a higher printing speed of thermal transfer and a higher density and quality of a thermal transfer image and which prevents abnormal transfer, wrinkling, etc. and improves transfer sensitivity in printing. <P>SOLUTION: In the thermal transfer sheet constituted by providing a heat-resistant sliding layer 4 on one side of a base 1 and by forming an adhesive layer 2 and a dye layer 3 sequentially on the other side of the base 1, the adhesive layer 2 contains a polyvinyl pyrrolidone resin. Therefore the transfer sensivity on the occasion of thermal transfer is sharply improved and the thermal transfer image of high density is obtained without impression of high energy. By mixing an adhesive component in the adhesive layer 2 in addition to the polyvinyl pyrrolidone resin, the adhesion between the dye layer 3 and the base 1 can be increased even when the base 1 not treated for adhesion is used, and thereby the abnormal transfer etc. can be prevented. <P>COPYRIGHT: (C)2004,JPO

Description

【００４０】
（実施例７）
実施例１と同条件の易接着処理済みＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の易接着処理面に、下記組成の接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、実施例７の熱転写シートを作製する。
【００４１】
＜接着層組成液Ｂ＞
ポリビニルピロリドン樹脂（Ｋ−９０、ＩＳＰ（株）製）　　　　　　　６部
水　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　４７部
イソプロピルアルコール　　　　　　　　　　　　　　　　　　　　　４７部
【００４２】
（実施例８）
実施例１と同条件の易接着処理済みＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の易接着処理面に、下記組成の接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、実施例８の熱転写シートを作製する。
【００４３】
＜接着層組成液Ｃ＞
ポリビニルピロリドン樹脂（Ｋ−１２０、ＩＳＰ（株）製）　　　　　　６部
水　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　４７部
イソプロピルアルコール　　　　　　　　　　　　　　　　　　　　　４７部
【００４４】
（実施例９）
実施例１と同条件の易接着処理済みＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の易接着処理面に、下記組成の接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、実施例９の熱転写シートを作製する。
【００４５】
＜接着層組成液Ｄ＞
ポリビニルピロリドン樹脂　　　　　　　　　　　　　　　　　　１３．３部
（Ｋ−６０、ＩＳＰ（株）製、固形分４５％）
水　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　４７部
イソプロピルアルコール　　　　　　　　　　　　　　　　　　　　　４７部
【００４６】
（実施例１０）
実施例１と同条件の易接着処理済みＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の易接着処理面に、下記組成の接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、実施例１０の熱転写シートを作製する。
【００４７】
＜接着層組成液Ｅ＞
ポリビニルピロリドン樹脂（Ｋ−９０、ＩＳＰ（株）製）　　　　　５．７部
ポリエステル樹脂（ＲＶ２２０、東洋紡績（株）製）　　　　　　　０．３部
メチルエチルケトン　　　　　　　　　　　　　　　　　　　　　　　４７部
イソプロピルアルコール　　　　　　　　　　　　　　　　　　　　　３０部
トルエン　　　　　　　　　　　　　　　　　　　　　　　　　　　　１７部
【００４８】
（実施例１１）
実施例１と同条件の易接着処理済みＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の易接着処理面に、下記組成の接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、実施例１１の熱転写シートを作製する。
【００４９】
＜接着層組成液Ｆ＞
ポリビニルピロリドン樹脂（Ｋ−９０、ＩＳＰ（株）製）　　　　　５．７部
ポリウレタン樹脂　　　　　　　　　　　　　　　　　　　　　　　０．３部
（スーパーフレックス４６０Ｓ、第一工業製薬（株）製）
水　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　４７部
イソプロピルアルコール　　　　　　　　　　　　　　　　　　　　　４７部
【００５０】
（実施例１２）
実施例１と同条件の易接着処理済みＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の易接着処理面に、下記組成の接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、実施例１２の熱転写シートを作製する。
【００５１】
＜接着層組成液Ｇ＞
ポリビニルピロリドン樹脂（Ｋ−９０、ＩＳＰ（株）製）　　　　　５．７部
アクリル樹脂（ＭＥ−１８、ナガセケムテックス（株）製）　　　　０．３部
水　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　４７部
イソプロピルアルコール　　　　　　　　　　　　　　　　　　　　　４７部
【００５２】
（実施例１３）
実施例１と同条件の易接着処理済みＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の易接着処理面に、下記組成の接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、実施例１３の熱転写シートを作製する。
【００５３】
＜接着層組成液Ｈ＞
ポリビニルピロリドン樹脂（Ｋ−３０、ＩＳＰ（株）製）　　　　　　　３部
水　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　４７部
イソプロピルアルコール　　　　　　　　　　　　　　　　　　　　　４７部
【００５４】
（実施例１４）
基材して、厚さ６μｍの未処理ポリエチレンテレフタレートフィルム（ＰＥＴ）（三菱化学ポリエステルフィルム（株）製、ダイヤホイルＫ８８０）に、コロナ照射処理し、その基材のコロナ照射処理面に、実施例１で使用した接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、実施例１４の熱転写シートを作製する。尚、上記基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。
【００５５】
（実施例１５）
実施例１４と同条件のコロナ照射処理済みＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材のコロナ照射処理面に、実施例７で使用した接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、実施例１５の熱転写シートを作製する。
【００５６】
（実施例１６）
基材して、厚さ６μｍの未処理ポリエチレンテレフタレートフィルム（ＰＥＴ）（三菱化学ポリエステルフィルム（株）製、ダイヤホイルＫ８８０）に、プラズマ照射処理し、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材のプラズマ照射処理面に、実施例１で使用した接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、実施例１６の熱転写シートを作製する。
【００５７】
（実施例１７）
基材して、厚さ６μｍの未処理ポリエチレンテレフタレートフィルム（ＰＥＴ）（三菱化学ポリエステルフィルム（株）製、ダイヤホイルＫ８８０）を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の未処理面に、実施例１０で使用した接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、実施例１７の熱転写シートを作製する。
【００５８】
（実施例１８）
実施例１７と同条件の未処理ＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の未処理面に、下記組成の接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、実施例１８の熱転写シートを作製する。
【００５９】
＜接着層組成液Ｉ＞
ポリビニルピロリドン樹脂（Ｋ−９０、ＩＳＰ（株）製）　　　　　４．５部
ポリエステル樹脂（ＲＶ２２０、東洋紡績（株）製）　　　　　　　１．５部
メチルエチルケトン　　　　　　　　　　　　　　　　　　　　　　　４７部
イソプロピルアルコール　　　　　　　　　　　　　　　　　　　　　３０部
トルエン　　　　　　　　　　　　　　　　　　　　　　　　　　　　１７部
【００６０】
（実施例１９）
実施例１７と同条件の未処理ＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の未処理面に、実施例１１で使用した接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、実施例１９の熱転写シートを作製する。
【００６１】
（実施例２０）
実施例１７と同条件の未処理ＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の未処理面に、下記組成の接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、実施例２０の熱転写シートを作製する。
【００６２】
＜接着層用組成液Ｊ＞
ポリビニルピロリドン樹脂（Ｋ−９０、ＩＳＰ（株）製）　　　　　４．５部
ポリウレタン樹脂　　　　　　　　　　　　　　　　　　　　　　　１．５部
（スーパーフレックス４６０Ｓ、第一工業製薬（株）製）
水　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　４７部
イソプロピルアルコール　　　　　　　　　　　　　　　　　　　　　４７部
【００６３】
（実施例２１）
実施例１７と同条件の未処理ＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の未処理面に、実施例１２で使用した接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、実施例２１の熱転写シートを作製する。
【００６４】
（実施例２２）
実施例１７と同条件の未処理ＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の未処理面に、下記組成の接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、実施例２２の熱転写シートを作製する。
【００６５】
＜接着層組成液Ｋ＞
ポリビニルピロリドン樹脂（Ｋ−９０、ＩＳＰ（株）製）　　　　　４．５部
アクリル樹脂（ＭＥ−１８、ナガセケムテックス（株）製）　　　　１．５部
水　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　４７部
イソプロピルアルコール　　　　　　　　　　　　　　　　　　　　　４７部
【００６６】
（実施例２３）
実施例１７と同条件の未処理ＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の未処理面に、下記組成の接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、実施例２３の熱転写シートを作製する。
【００６７】
＜接着層組成液Ｌ＞
ポリビニルピロリドン樹脂（Ｋ−９０、ＩＳＰ（株）製）　　　　　３．９部
ポリエステル樹脂（ＲＶ２２０、東洋紡績（株）製）　　　　　　　２．１部
メチルエチルケトン　　　　　　　　　　　　　　　　　　　　　　　４７部
イソプロピルアルコール　　　　　　　　　　　　　　　　　　　　　３０部
トルエン　　　　　　　　　　　　　　　　　　　　　　　　　　　　１７部
【００６８】
（実施例２４）
実施例１７と同条件の未処理ＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の未処理面に、下記組成の接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、実施例２４の熱転写シートを作製する。
【００６９】
＜接着層組成液Ｍ＞
ポリビニルピロリドン樹脂（Ｋ−９０、ＩＳＰ（株）製）　　　　　３．９部
ポリウレタン樹脂　　　　　　　　　　　　　　　　　　　　　　　２．１部
（スーパーフレックス４６０Ｓ、第一工業製薬（株）製）
水　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　４７部
イソプロピルアルコール　　　　　　　　　　　　　　　　　　　　　４７部
【００７０】
（実施例２５）
実施例１７と同条件の未処理ＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の未処理面に、下記組成の接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、実施例２５の熱転写シートを作製する。
【００７１】
＜接着層組成液Ｎ＞
ポリビニルピロリドン樹脂（Ｋ−９０、ＩＳＰ（株）製）　　　　　３．９部
アクリル樹脂（ＭＥ−１８、ナガセケムテックス（株）製）　　　　２．１部
水　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　４７部
イソプロピルアルコール　　　　　　　　　　　　　　　　　　　　　４７部
【００７２】
（実施例２６）
実施例１で作製した熱転写シートを用意した。但し、下記の評価方法に示すように、組み合わせて使用する熱転写受像シートは実施例１とは異なり、ポリ塩化ビニル樹脂製（ＰＶＣ製）のカードを使用した。
【００７３】
（実施例２７）
実施例１４で作製した熱転写シートを用意した。但し、下記の評価方法に示すように、組み合わせて使用する熱転写受像シートは実施例１４とは異なり、ポリ塩化ビニル樹脂製（ＰＶＣ製）のカードを使用した。
【００７４】
（比較例１）
実施例１と同条件の易接着処理済みＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の易接着処理面に、接着層なしで、直接、実施例１と同様に染料層を形成し、比較例１の熱転写シートを作製する。
【００７５】
（比較例２）
実施例１と同条件の易接着処理済みＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の易接着処理面に、接着層なしで、直接、実施例４と同様に染料層を形成し、比較例２の熱転写シートを作製する。
【００７６】
（比較例３）
実施例１と同条件の易接着処理済みＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の易接着処理面に、接着層なしで、直接、実施例５と同様に染料層を形成し、比較例３の熱転写シートを作製する。
【００７７】
（比較例４）
実施例１と同条件の易接着処理済みＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の易接着処理面に、接着層なしで、直接、実施例６と同様に染料層を形成し、比較例４の熱転写シートを作製する。
【００７８】
（比較例５）
実施例１４と同条件のコロナ照射処理済みＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材のコロナ照射処理面に、接着層なしで、直接、実施例１と同様に染料層を形成し、比較例５の熱転写シートを作製する。
【００７９】
（比較例６）
実施例１６と同条件のプラズマ照射処理済みＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材のプラズマ照射処理面に、接着層なしで、直接、実施例１と同様に染料層を形成し、比較例６の熱転写シートを作製する。
【００８０】
（比較例７）
実施例１と同条件の易接着処理済みＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の易接着処理面に、下記組成の接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、比較例７の熱転写シートを作製する。
【００８１】
＜接着層組成液Ｏ＞
ポリエステル樹脂（ＲＶ２２０、東洋紡績（株）製）　　　　　　　　　６部
トルエン　　　　　　　　　　　　　　　　　　　　　　　　　　　　４７部
メチルエチルケトン　　　　　　　　　　　　　　　　　　　　　　　４７部
【００８２】
（比較例８）
実施例１と同条件の易接着処理済みＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の易接着処理面に、下記組成の接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、比較例８の熱転写シートを作製する。
【００８３】
＜接着層組成液Ｐ＞
ポリウレタン樹脂　　　　　　　　　　　　　　　　　　　　　　　　　６部
（スーパーフレックス４６０Ｓ、第一工業製薬（株）製）
水　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　４７部
イソプロピルアルコール　　　　　　　　　　　　　　　　　　　　　４７部
【００８４】
（比較例９）
実施例１と同条件の易接着処理済みＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の易接着処理面に、下記組成の接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、比較例９の熱転写シートを作製する。
【００８５】
＜接着層組成液Ｑ＞
アクリル樹脂（ＭＥ−１８、ナガセケムテックス（株）製）　　　　　　６部
水　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　４７部
イソプロピルアルコール　　　　　　　　　　　　　　　　　　　　　４７部
【００８６】
（比較例１０）
実施例１４と同条件のコロナ照射処理済みＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材のコロナ照射処理面に、比較例７と同様に接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、比較例１０の熱転写シートを作製する。
【００８７】
（比較例１１）
実施例１４と同条件のコロナ照射処理済みＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材のコロナ照射処理面に、下記組成の接着層塗工液をグラビアコーティングにより、乾燥塗布量が０．２ｇ／ｍ^２になるように塗布、乾燥して接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、比較例１１の熱転写シートを作製する。
【００８８】
＜接着層組成液Ｒ＞
ポリエステル樹脂（ＭＤ−１２４５、東洋紡績（株）製）　　　　　　　６部
水　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　４７部
イソプロピルアルコール　　　　　　　　　　　　　　　　　　　　　４７部
【００８９】
（比較例１２）
実施例１７と同条件の未処理ＰＥＴフィルムの基材を用い、かつその基材の他方の面に、実施例１と同様の耐熱滑性層を予め形成しておいた。その基材の未処理面に、比較例７と同様に接着層を形成した。さらに、その接着層の上に、実施例１と同様に染料層を形成し、比較例１２の熱転写シートを作製する。
【００９０】
（比較例１３）
比較例１で作製した熱転写シートを用意した。但し、下記の評価方法に示すように、組み合わせて使用する熱転写受像シートは比較例１とは異なり、ポリ塩化ビニル樹脂製（ＰＶＣ製）のカードを使用した。
【００９１】
（比較例１４）
比較例５で作製した熱転写シートを用意した。但し、下記の評価方法に示すように、組み合わせて使用する熱転写受像シートは比較例５とは異なり、ポリ塩化ビニル樹脂製（ＰＶＣ製）のカードを使用した。
【００９２】
上記に作製した各実施例及び比較例の熱転写シートを用いて、濃度評価、印画適性、耐熱接着性の各評価を以下に示す方法で行なった。
（濃度評価）
以下の条件にて、印画を行ない、得られた印画物の最高濃度を測定した。
実施例１〜５、７〜２５及び比較例１〜３、５〜１２で作製した熱転写シートと、オリンパス（株）製、デジタルカラープリンタ　Ｐ−２００専用スタンダードセットの印画紙の組み合わせで、オリンパス（株）製、デジタルカラープリンタ　Ｐ−２００により、黒ベタ（階調値２５５／２５５：濃度マックス）の印画パターンで、印画し、マクベス濃度計ＲＤ−９１８（サカタインクス（株）製）にて、印画部の最高濃度を測定した。
また、実施例６と比較例４で作製した熱転写シートは、コニカ（株）製、フォトキレートプリンタ　Ａ６（ＣＨＣ−Ｓ１０４５−５Ｅ）用スタンダード印画紙（Ｃ−Ａ６−ＰＨ）を用いて、コニカ（株）製、フォトキレートプリンタ　Ａ６（ＣＨＣ−Ｓ１０４５−５Ｅ）により、黒ベタ（階調値２５５／２５５：濃度マックス）の印画パターンで、印画し、マクベス濃度計ＲＤ−９１８（サカタインクス（株）製）にて、印画部の最高濃度を測定した。
さらに、実施例２６、２７及び比較例１３、１４で用意した熱転写シートと、ポリ塩化ビニル樹脂製（ＰＶＣ製）のカードの組み合わせで、Ｅｌｔｒｏｎ社製カードプリンタＰ３１０にて、黒ベタ（階調値２５５／２５５：濃度マックス）の印画パターンで、印画し、マクベス濃度計ＲＤ−９１８（サカタインクス（株）製）にて、印画部の最高濃度を測定した。
【００９３】
＜評価基準＞
基準リボン（接着層を挟んでいないリボン）と最高濃度を比較して、
◎：濃度が１１０％以上
○：濃度が１００％以上１１０％未満
△：濃度が９０％以上１００％未満
×：濃度が９０％未満
尚、基準リボンは染料層の条件が同一で、接着層の無いものであり、被転写体が同一のものである。
すなわち、実施例１、２、３、７〜２５は比較例１を基準とし、実施例４は比較例２を基準、実施例５は比較例３を基準、実施例６は比較例４を基準、さらに比較例５〜１２は比較例１を基準、実施例２６、２７は比較例１３を基準とした。
【００９４】
（印画適性）
上記の濃度評価の方法と同様に、印画を行なった際に、異常転写、転写ムラ、転写抜け等の印画不良の有無を目視にて調べた。
評価は以下の基準にて行なった。
○：異常転写、転写ムラ、転写抜けなどの印画不良がない。
×：異常転写、転写ムラ、転写抜けなどの印画不良がある。
【００９５】
（耐熱接着性）
実施例及び比較例の試料となる熱転写シートを、染料層面を上にして、台紙の上に貼り付ける（台紙と耐熱滑性層とが接する形態である。）。そして、その試料と対応する基準リボン（染料層の条件が同一で、接着層の無いもので、上記濃度評価の際と同様である）を染料層面を上にして、同一台紙の異なる位置に貼り付け、試料と基準リボンの染料層面同士が重ねて接するように、台紙毎、折り返して、温度１００〜１３０℃、圧力２．５ｋｇ／ｃｍ^２、加圧時間２ｓｅｃでヒートシールを行ない、両者を剥離して、試料と基準リボンの各染料層の残存状態（取られた状態）を目視にて調べ、以下の基準にて、評価した。
【００９６】
○：試料側に残った染料層の面積が基準リボン側に残った面積よりも大きい。
×：試料側に残った染料層の面積が基準リボン側に残った面積よりも小さい。
【００９７】
上記の実施例及び比較例の各評価結果を、下記の表１に示す。
【表１】

【００９８】
上記の濃度評価の結果より、接着層にポリビニルピロリドン樹脂を含有している実施例は、印画における転写感度が高く、印画濃度も高くなる。また、上記の耐熱接着性は、染料層と基材との高温下における接着性を調べるもので、熱転写印画における異常転写の防止性と関連した評価であり、実施例の各熱転写シートは耐熱接着性に優れ、異常転写や転写ムラ、転写抜け等の印画不良が生じない。尚、実施例１３で、接着層にポリビニルピロリドンのＫ値が３０のものを単独で使用し、基準リボン（比較例１の熱転写シート）と比べ、最高濃度は少し低下するが、印画適性と耐熱接着性ともに良好である。
また、実施例２３、２４、２５は、ポリビニルピロリドンに接着成分を、接着層全体の固形分に対して、３５重量％の割合で含有し、最高濃度は基準リボン（比較例１の熱転写シート）と比べ、少し低下するが、印画適性と耐熱接着性ともに良好である。
【００９９】
【発明の効果】
以上の通り、基材の一方の面に耐熱滑性層を設け、該基材の他方の面に接着層、染料層を順次形成した熱転写シートにおいて、該接着層にポリビニルピロリドン樹脂を含有しているために、熱転写の際の、転写感度が大幅に向上し、高エネルギーを印加しなくても、高濃度の熱転写画像が得られる。また、接着層に、ポリビニルピロリドン樹脂の他に接着成分を混合させることで、接着処理が施されていない基材を用いても、染料層と基材との接着性を高めることができ、異常転写等を防止できる。
【図面の簡単な説明】
【図１】本発明の熱転写シートである一つの実施形態を示す概略断面図である。
【図２】本発明の熱転写シートである他の実施形態を示す概略断面図である
【符号の説明】
１　　　基材
２　　　接着層
３　　　染料層
４　　　耐熱滑性層
５　　　プライマー層[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a thermal transfer sheet in which a heat-resistant lubricating layer is provided on one surface of a substrate, and an adhesive layer and a dye layer are sequentially formed on the other surface of the substrate. The present invention relates to a thermal transfer sheet capable of preventing abnormal transfer such as transfer of the entire dye layer during printing on a transfer body.
[0002]
[Prior art]
Conventionally, various thermal transfer recording methods are known, and among them, a thermal transfer sheet having a dye layer in which a dye for sublimation transfer is used as a recording material and this is supported on a base material such as a polyester film with a suitable binder. From, to the transfer material dyeable with a sublimation dye, for example, a method of thermally transferring the sublimation dye on a thermal transfer image receiving sheet having a dye receiving layer formed on paper or plastic film, to form various full-color images has been proposed. I have. In this case, as the heating means, by heating with a thermal head of a printer, a large number of color dots of three or four colors whose heat amounts are adjusted are transferred to a receiving layer of a thermal transfer image receiving sheet, and the multicolor color dots are transferred. To reproduce the full color of the original. The image formed in this way is very clear and excellent in transparency because the coloring material used is a dye, so the resulting image is excellent in reproducibility and gradation of intermediate colors. It is possible to form a high-quality image which is similar to an image by offset printing or gravure printing, and is comparable to a full-color photographic image.
[0003]
In such a thermal transfer recording method using sublimation transfer, as the printing speed of a thermal transfer printer has increased, a problem has arisen that a sufficient print density cannot be obtained with a conventional thermal transfer sheet. In addition, higher density and sharpness of printed matter of images by thermal transfer have been demanded, and a thermal transfer sheet and a thermal transfer image receiving sheet on which an image is formed by receiving a sublimation dye transferred from the thermal transfer sheet have been improved. There have been many attempts to do so.
For example, attempts have been made to improve the transfer sensitivity in printing by making the thermal transfer sheet thinner, but when manufacturing the thermal transfer sheet, or during thermal transfer recording, wrinkles may occur due to heat or pressure, etc. Causes the problem of cutting.
[0004]
Further, an attempt was made to increase the ratio of dye / resin (Dye / Binder) in the dye layer of the thermal transfer sheet to improve the printing density and the transfer sensitivity in the printing. The dye is transferred to the heat-resistant lubricating layer, and when the transferred dye is unwound, it is re-transferred to another color dye layer (kickback), and the contaminated layer is thermally transferred to the image receiving sheet. Color or a so-called background stain.
In the thermal transfer printer, rather than on the thermal transfer sheet side, high energy was applied during thermal transfer during image formation. However, the dye layer and the receiving layer fused, so-called abnormal transfer was likely to occur. If a large amount of release agent is added to the receiving layer in order to prevent the abnormal transfer, bleeding of the image, background contamination, etc. will occur.
[0005]
Further, as a prior art, Japanese Patent Publication No. Hei 7-102746 discloses that a hydrophilic barrier / undercoat layer containing polyvinylpyrrolidone as a main component and mixing and using polyvinyl alcohol as a component for enhancing dye transfer efficiency is provided between the dye layer and the support. A thermal transfer sheet is disclosed. This polyvinylpyrrolidone is to prevent abnormal transfer, to prevent adhesion at the time of printing, polyvinyl alcohol has a function to improve the transfer sensitivity, about that polyvinylpyrrolidone improves the transfer sensitivity, There is no description.
[0006]
As described above, the thermal transfer recording material for the thermal transfer printer and the thermal transfer sheet and thermal transfer image receiving sheet to be used in response to the increase in the printing speed of thermal transfer and the demand for high density and high quality thermal transfer images. However, sufficient print density could not be obtained, abnormal transfer occurred during thermal transfer, and other problems occurred, and a print of satisfactory quality could not be obtained.
[0007]
[Problems to be solved by the invention]
Therefore, in order to solve the above problems, the present invention is to increase the printing speed of thermal transfer, high density of the thermal transfer image, in response to the demand for high quality, to prevent the occurrence of abnormal transfer and wrinkles, An object of the present invention is to provide a thermal transfer sheet having improved transfer sensitivity in printing.
[0008]
[Means for Solving the Problems]
In order to achieve the above object, the present invention provides a thermal transfer sheet according to claim 1, wherein a heat-resistant lubricating layer is provided on one surface of a substrate, and an adhesive layer and a dye layer are sequentially formed on the other surface of the substrate. And the adhesive layer is made of polyvinylpyrrolidone resin.
According to a second aspect of the present invention, the polyvinylpyrrolidone resin has a K value of 60 or more in Fickencher's formula.
According to a third aspect, the adhesive layer according to the first or second aspect is characterized in that an adhesive component is mixed in addition to the polyvinylpyrrolidone resin.
[0009]
According to a fourth aspect of the present invention, the adhesive component contained in the adhesive layer according to the third aspect is contained at a ratio of 1 to 30% by weight based on the solid content of the entire adhesive layer. I do.
According to a fifth aspect, the surface of the substrate according to any one of the first to fourth aspects on which the dye layer is formed has been subjected to an adhesive treatment.
A sixth aspect of the present invention is characterized in that the surface of the substrate according to the third or fourth aspect on which the dye layer is formed is not subjected to an adhesive treatment.
[0010]
The present invention provides a heat transfer sheet in which a heat-resistant lubricating layer is provided on one surface of a base material, and an adhesive layer and a dye layer are sequentially formed on the other surface of the base material, since the adhesive layer is made of polyvinylpyrrolidone resin. In addition, the transfer sensitivity at the time of thermal transfer is greatly improved, and a high-density thermal transfer image can be obtained without applying high energy. Further, by mixing an adhesive component in the adhesive layer in addition to the polyvinylpyrrolidone resin, the adhesiveness between the dye layer and the substrate can be increased, and abnormal transfer and the like can be prevented.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
Next, embodiments of the invention will be described in detail.
FIG. 1 shows one embodiment of the thermal transfer sheet of the present invention, in which a heat-resistant lubricating layer 4 for improving the slipperiness of a thermal head and preventing sticking is provided on one surface of a substrate 1. Has an adhesive layer 2 made of polyvinylpyrrolidone resin and a dye layer 3 sequentially formed on the other surface.
FIG. 2 shows another embodiment of the thermal transfer sheet of the present invention, in which a heat-resistant lubricating layer 4 for improving the slipperiness of a thermal head and preventing sticking is provided on one surface of a substrate 1. In this configuration, a primer layer 5, an adhesive layer 2 made of polyvinylpyrrolidone resin, and a dye layer 3 are sequentially formed on the other surface of the material 1.
Hereinafter, each layer constituting the thermal transfer sheet of the present invention will be described in detail.
[0012]
(Base material)
As the substrate 1 of the thermal transfer sheet used in the present invention, any substrate may be used as long as it has a conventionally known degree of heat resistance and strength, for example, a thickness of 0.5 to 50 μm, preferably about 1 to 10 μm. Sano polyethylene terephthalate film, 1,4-polycyclohexylene dimethylene terephthalate film, polyethylene naphthalate film, polyphenylene sulfide film, polystyrene film, polypropylene film, polysulfone film, aramid film, polycarbonate film, polyvinyl alcohol film, cellophane, acetic acid Examples include cellulose derivatives such as cellulose, polyethylene films, polyvinyl chloride films, nylon films, polyimide films, ionomer films, and the like.
[0013]
In the above substrate, the surface on which the adhesive layer and the dye layer are formed is often subjected to an adhesive treatment. In the case where the plastic film of the base material is formed by applying an adhesive layer thereon, the wettability and adhesiveness of the coating liquid are apt to be insufficient, so that the adhesive treatment is performed. The adhesive treatment includes known resin surface modification such as corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, surface roughening treatment, chemical treatment, plasma treatment, low-temperature plasma treatment, primer treatment, and grafting treatment. Quality technology can be applied as it is. In addition, two or more of these treatments can be used in combination. The above-mentioned primer treatment can be performed, for example, by applying a primer liquid to an unstretched film at the time of forming a film by melt extrusion of a plastic film, and then stretching the film.
[0014]
Furthermore, it is also possible to apply and coat the primer layer 5 between the base material and the adhesive layer as the above-mentioned base material bonding treatment. The primer layer can be formed from the following resins. Polyester resin, polyacrylate resin, polyvinyl acetate resin, polyurethane resin, styrene acrylate resin, polyacrylamide resin, polyamide resin, polyether resin, polystyrene resin, polyethylene resin, polypropylene resin Resins, vinyl resins such as polyvinyl chloride resins and polyvinyl alcohol resins, and polyvinyl acetal resins such as polyvinyl acetoacetal and polyvinyl butyral. Further, in a thermal transfer sheet in which an adhesive layer and a dye layer are sequentially formed on the substrate of the present invention, if an adhesive component is mixed into the adhesive layer in addition to the polyvinylpyrrolidone resin, a substrate that has not been subjected to an adhesive treatment may be used. Is possible.
[0015]
(Adhesive layer)
The adhesive layer 2 provided between the base material and the dye layer in the thermal transfer sheet of the present invention is composed mainly of a polyvinylpyrrolidone resin, and if necessary, contains 1 adhesive component with respect to the solid content of the entire adhesive layer. -30% by weight.
Examples of the polyvinylpyrrolidone resin include homopolymers or copolymers of vinylpyrrolidone such as N-vinyl-2-pyrrolidone and N-vinyl-4-pyrrolidone.
As the polyvinylpyrrolidone resin used in the adhesive layer in the present invention, it is preferable to use those having a K value in the formula of Fickenture of 60 or more, and in particular, grades of K-60 to K-120 can be used, and the number average molecular weight can be used. Is about 30,000 to 280,000. When a polyvinylpyrrolidone resin having a K value of less than 60 is used, the effect of improving the transfer sensitivity in printing is reduced.
[0016]
Further, a copolymer of the above-mentioned vinylpyrrolidone and another copolymerizable monomer can also be used. Examples of copolymerizable monomers other than vinylpyrrolidone include vinyl monomers such as styrene, vinyl acetate, acrylate, acrylonitrile, maleic anhydride, vinyl chloride (fluoride) and vinylidene chloride (fluoride, cyanide). No. Copolymers obtained by radical copolymerization of the vinyl monomer and vinylpyrrolidone can be used. Further, a block copolymer, a graft copolymer, or the like of a polyvinylpyrrolidone with a polyester resin, a polycarbonate resin, a polyurethane resin, an epoxy resin, an acetal resin, a butyral resin, a formal resin, a phenoxy resin, a cellulose resin, or the like can also be used.
[0017]
In addition, the adhesive layer may be mixed with an adhesive component in addition to the polyvinylpyrrolidone resin to improve the adhesiveness between the substrate and the dye layer. The adhesive components include polyester resin, polyacrylate resin, polyvinyl acetate resin, polyurethane resin, styrene acrylate resin, polyacrylamide resin, polyamide resin, polyether resin, polystyrene resin, polyethylene resin, polypropylene resin, and polyvinyl chloride. Resins, vinyl resins such as vinyl chloride-vinyl acetate copolymer resins and ethylene-vinyl acetate copolymer resins, and polyvinyl acetal resins such as polyvinyl acetoacetal and polyvinyl butyral. As the above-mentioned adhesive component, polyester resin, polyurethane resin and acrylic resin are particularly preferable because they have strong adhesiveness. Such an adhesive component is preferably used by adding it at a ratio of 1 to 30% by weight based on the solid content of the entire adhesive layer. If the added amount of the adhesive component is small, sufficient adhesiveness cannot be exhibited, and if the added amount of the adhesive component is too large, the effect of improving the dye transfer sensitivity from the dye layer of polyvinylpyrrolidone cannot be sufficiently exhibited.
[0018]
The adhesive layer is prepared by dissolving or dispersing the above-mentioned polyvinylpyrrolidone and, if necessary, an adhesive component and other additives in an organic solvent or an aqueous solvent, to prepare a gravure printing method. It can be formed using a known coating means such as a screen printing method, a reverse roll coating method using a gravure plate, or the like. When an organic solvent is used in the coating solution, a type in which polyvinylpyrrolidone and the adhesive component are easily dissolved in the solvent is used. When an aqueous solvent is used in the coating liquid, a water-soluble or aqueous emulsion-type resin is used for polyvinylpyrrolidone and the adhesive component.
The adhesive layer thus formed has a thickness of 0.01 to 3.0 g / m. ² This is the amount of coating when drying.
[0019]
(Dye layer)
The thermal transfer sheet of the present invention has a base material provided with a heat-resistant lubricating layer on one surface, and a dye layer 3 provided on the other surface via an adhesive layer. The dye layer may be composed of a single layer of one color, or a plurality of dye layers containing dyes having different hues may be repeatedly formed on the same surface of the same substrate in a face-to-face manner.
The dye layer is a layer in which a heat transferable dye is supported by an optional binder. The dye used is a dye that melts, diffuses or sublimates due to heat, and any dye used in a conventionally known sublimation transfer type thermal transfer sheet can be used in the present invention. Selection is made in consideration of printing sensitivity, light resistance, storage stability, solubility in a binder, and the like.
[0020]
Examples of the dye include azomethine represented by diarylmethane, triarylmethane, thiazole, methine such as merocyanine and pyrazolone methine, indoaniline, acetophenone azomethine, pyrazoloazomethine, imidazole azomethine, imidazoazomethine, and pyridone azomethine. System, xanthene system, oxazine system, dicyanostyrene, cyanomethylene system represented by tricyanostyrene, thiazine system, azine system, acridine system, benzeneazo system, pyridoneazo, thiophenazo, isothiazoleazo, pyrroleazo, pyralazo, imidazoleazo, Azo series such as thiadiazole azo, triazole azo, and diazo, spiropyran series, indolinospyropyran series, fluoran series, rhodamine lactam series, naphthoquinone series, and Rakinon system include the quinophthalone like.
[0021]
As the binder for the dye layer, any of the conventionally known resin binders can be used. Preferred examples thereof include ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxycellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, and cellulose resin such as cellulose butyrate. And vinyl resins such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl pyrrolidone and polyacrylamide, polyester resins, and phenoxy resins. Among them, cellulose resins, acetal resins, butyral resins, polyester resins, phenoxy resins, and the like are particularly preferable from the viewpoints of heat resistance, dye transferability, and the like.
[0022]
In the present invention, the following releasable graft copolymer can be used as a release agent or a binder instead of the above resin binder. The releasable graft copolymer is obtained by graft-polymerizing at least one releasable segment selected from a polysiloxane segment, a fluorocarbon segment, a fluorohydrocarbon segment, or a long-chain alkyl segment onto a polymer main chain. Things. Among them, particularly preferred is a graft copolymer obtained by grafting a polysiloxane segment to a main chain composed of a polyvinyl acetal resin.
[0023]
The dye layer may contain the above-mentioned dyes and binders and, if necessary, various additives similar to those conventionally known. Examples of the additive include organic fine particles and inorganic fine particles such as polyethylene wax, a phosphate ester-based surfactant, and a fluorine-based compound in order to improve the releasability from the image-receiving sheet and the applicability of the ink. Can be Such a dye layer is usually prepared by adding the above-mentioned dye, binder and additives as needed in an appropriate solvent, and dissolving or dispersing each component to prepare a coating solution. It can be formed by applying a liquid on a substrate and drying it. As this coating method, known means such as a gravure printing method, a screen printing method, and a reverse roll coating method using a gravure plate can be used. The dye layer thus formed has a thickness of 0.2 to 6.0 g / m2. ² , Preferably 0.3 to 3.0 g / m ² This is the amount of coating when drying.
[0024]
(Heat-resistant lubricating layer)
The heat transfer sheet of the present invention is provided with a heat-resistant lubricating layer 4 on one surface of the substrate in order to prevent adverse effects such as sticking and printing wrinkles due to the heat of the thermal head. As the resin forming the heat-slippery layer, any conventionally known resin may be used, for example, polyvinyl butyral resin, polyvinyl acetoacetal resin, polyester resin, vinyl chloride-vinyl acetate copolymer, polyether resin, Polybutadiene resin, styrene-butadiene copolymer, acrylic polyol, polyurethane acrylate, polyester acrylate, polyether acrylate, epoxy acrylate, urethane or epoxy prepolymer, nitrocellulose resin, cellulose nitrate resin, cellulose acetate propionate resin, cellulose Acetate butyrate resin, cellulose acetate hydrodiene phthalate resin, cellulose acetate resin, aromatic polyamide resin, polyimide resin, polyamideimide resin, poly Boneto resins, and chlorinated polyolefin resins.
[0025]
Phosphoric acid esters, silicone oils, graphite powders, silicone-based graft polymers, fluorine-based graft polymers, acrylic silicone-grafted polymers, acrylic siloxanes, aryl Examples thereof include silicone polymers such as siloxane. Preferably, the layer is a layer composed of a polyol, for example, a polyalcohol polymer compound, a polyisocyanate compound, and a phosphate compound, and more preferably a filler is added.
[0026]
The heat-resistant lubricating layer is prepared by dissolving or dispersing the above-described resin, slipperiness imparting agent, and filler with a suitable solvent on the base sheet to prepare a heat-resistant lubricating layer coating liquid. This can be formed by applying and drying by a forming means such as a gravure printing method, a screen printing method, and a reverse roll coating method using a gravure plate. The coating amount of the heat-resistant lubricating layer is 0.1 g / m ² ~ 3.0 g / m ² Is preferred.
[0027]
【Example】
Next, the present invention will be described more specifically with reference to examples. In the following description, “parts” or “%” is based on weight unless otherwise specified.
(Example 1)
As a base material, an adhesive layer coating solution having the following composition is gravure coated on a 6 μm-thick easily treated polyethylene terephthalate film (PET) (diafoil K203E, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.). 0.2g / m dry coating weight due to coating ² And dried to form an adhesive layer. Further, on the adhesive layer, a dye layer coating solution having the following composition was gravure coated to a dry coating amount of 0.8 g / m 2. ² To form a dye layer, and the thermal transfer sheet of Example 1 is prepared. On the other surface of the base material, a heat-resistant lubricating layer coating solution having the following composition was previously applied by gravure coating to a dry coating amount of 1.0 g / m 2. ² And dried to form a heat-resistant lubricating layer.
[0028]
<Adhesive layer composition liquid A>
Polyvinylpyrrolidone resin (K-90, manufactured by ISP) 6 parts
Methyl ethyl ketone 47 parts
47 parts of isopropyl alcohol
[0029]
<Dye layer composition liquid (1)>
C. I. Solvent Blue 22 5.5 parts
Polyvinyl acetal resin 3.0 parts
(Eslec KS-5 Sekisui Chemical Co., Ltd.)
22.5 parts of methyl ethyl ketone
68.2 parts of toluene
[0030]
<Heat-resistant lubricating layer composition liquid a>
13.6 parts of polyvinyl butyral resin
(Eslec BX-1 Sekisui Chemical Co., Ltd.)
0.6 parts of polyisocyanate curing agent
(Takenate D218 Takeda Pharmaceutical Co., Ltd.)
Phosphate ester 0.8 parts
(Plysurf A208S manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
42.5 parts of methyl ethyl ketone
42.5 parts of toluene
[0031]
(Example 2)
A heat-resistant lubricating layer similar to that of Example 1 was formed in advance on the other surface of the base material of the PET film subjected to the easy adhesion treatment under the same conditions as in Example 1. The adhesive layer coating solution used in Example 1 was gravure coated on the easily-adhesive treated surface of the base material to a dry coating amount of 0.03 g / m. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Example 2 is manufactured.
[0032]
(Example 3)
A heat-resistant lubricating layer similar to that of Example 1 was formed in advance on the other surface of the base material of the PET film subjected to the easy adhesion treatment under the same conditions as in Example 1. The adhesive layer coating solution used in Example 1 was gravure coated on the easily-adhered surface of the base material by gravure coating so that the dry coating amount was 0.7 g / m2. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Example 3 is manufactured.
[0033]
(Example 4)
A heat-resistant lubricating layer similar to that of Example 1 was formed in advance on the other surface of the base material of the PET film subjected to the easy adhesion treatment under the same conditions as in Example 1. The adhesive layer coating solution used in Example 1 was gravure coated on the easily-adhesive treated surface of the base material to a dry coating amount of 0.2 g / m 2. ² And dried to form an adhesive layer. Further, on the adhesive layer, a dye layer coating solution having the following composition was gravure coated to a dry coating amount of 0.8 g / m 2. ² Then, a dye layer is formed by coating and drying to prepare a thermal transfer sheet of Example 4.
[0034]
<Dye layer composition liquid (2)>
C. I. Solvent Blue 22 6.0 parts
Phenoxy resin (PKHH, manufactured by Union Carbide) 3.0 parts
45.5 parts of methyl ethyl ketone
45.5 parts of toluene
[0035]
(Example 5)
A heat-resistant lubricating layer similar to that of Example 1 was formed in advance on the other surface of the base material of the PET film subjected to the easy adhesion treatment under the same conditions as in Example 1. The adhesive layer coating solution used in Example 1 was gravure coated on the easily-adhesive treated surface of the base material to a dry coating amount of 0.2 g / m 2. ² And dried to form an adhesive layer. Further, on the adhesive layer, a dye layer coating solution having the following composition was gravure coated to a dry coating amount of 0.8 g / m 2. ² To form a dye layer, and a thermal transfer sheet of Example 5 is produced.
[0036]
<Dye layer composition liquid (3)>
C. I. Solvent Blue 22 6.0 parts
3.0 parts of cellulose acetate butyrate (CAB381-20, manufactured by Eastman Chemical)
45.5 parts of methyl ethyl ketone
45.5 parts of toluene
[0037]
(Example 6)
A heat-resistant lubricating layer similar to that of Example 1 was formed in advance on the other surface of the base material of the PET film subjected to the easy adhesion treatment under the same conditions as in Example 1. The adhesive layer coating solution used in Example 1 was gravure coated on the easily-adhesive treated surface of the base material to a dry coating amount of 0.2 g / m 2. ² And dried to form an adhesive layer. Further, on the adhesive layer, a dye layer coating solution having the following composition was gravure coated to a dry coating amount of 0.8 g / m 2. ² Then, a dye layer is formed by coating and drying to prepare a thermal transfer sheet of Example 6.
[0038]
<Dye layer composition liquid (4)>
2.5 parts of C-1 dye (the following structural formula)
3.5 parts of polyvinyl acetal resin
(Eslec KS-5 Sekisui Chemical Co., Ltd.)
Methyl ethyl ketone 47 parts
Toluene 47 parts
[0039]
Embedded image

[0040]
(Example 7)
A heat-resistant lubricating layer similar to that of Example 1 was formed in advance on the other surface of the base material of the PET film subjected to the easy adhesion treatment under the same conditions as in Example 1. An adhesive layer coating solution having the following composition is gravure coated on the easily-adhesive treated surface of the base material to a dry coating amount of 0.2 g / m 2. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Example 7 is manufactured.
[0041]
<Adhesive layer composition liquid B>
Polyvinylpyrrolidone resin (K-90, manufactured by ISP) 6 parts
47 parts of water
47 parts of isopropyl alcohol
[0042]
(Example 8)
A heat-resistant lubricating layer similar to that of Example 1 was formed in advance on the other surface of the base material of the PET film subjected to the easy adhesion treatment under the same conditions as in Example 1. An adhesive layer coating solution having the following composition is gravure coated on the easily-adhesive treated surface of the base material to a dry coating amount of 0.2 g / m 2. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Example 8 is manufactured.
[0043]
<Adhesive layer composition liquid C>
Polyvinylpyrrolidone resin (K-120, manufactured by ISP) 6 parts
47 parts of water
47 parts of isopropyl alcohol
[0044]
(Example 9)
A heat-resistant lubricating layer similar to that of Example 1 was formed in advance on the other surface of the base material of the PET film subjected to the easy adhesion treatment under the same conditions as in Example 1. An adhesive layer coating solution having the following composition is gravure coated on the easily-adhesive treated surface of the base material to a dry coating amount of 0.2 g / m 2. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Example 9 is manufactured.
[0045]
<Adhesive layer composition liquid D>
13.3 parts of polyvinylpyrrolidone resin
(K-60, manufactured by ISP, solid content 45%)
47 parts of water
47 parts of isopropyl alcohol
[0046]
(Example 10)
A heat-resistant lubricating layer similar to that of Example 1 was formed in advance on the other surface of the base material of the PET film subjected to the easy adhesion treatment under the same conditions as in Example 1. An adhesive layer coating solution having the following composition is gravure coated on the easily-adhesive treated surface of the base material to a dry coating amount of 0.2 g / m 2. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Example 10 is manufactured.
[0047]
<Adhesive layer composition liquid E>
5.7 parts of polyvinylpyrrolidone resin (K-90, manufactured by ISP)
0.3 parts of polyester resin (RV220, manufactured by Toyobo Co., Ltd.)
Methyl ethyl ketone 47 parts
30 parts of isopropyl alcohol
17 parts of toluene
[0048]
(Example 11)
A heat-resistant lubricating layer similar to that of Example 1 was formed in advance on the other surface of the base material of the PET film subjected to the easy adhesion treatment under the same conditions as in Example 1. An adhesive layer coating solution having the following composition is gravure coated on the easily-adhesive treated surface of the base material to a dry coating amount of 0.2 g / m 2. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Example 11 is manufactured.
[0049]
<Adhesive layer composition liquid F>
5.7 parts of polyvinylpyrrolidone resin (K-90, manufactured by ISP)
0.3 parts of polyurethane resin
(Superflex 460S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
47 parts of water
47 parts of isopropyl alcohol
[0050]
(Example 12)
A heat-resistant lubricating layer similar to that of Example 1 was formed in advance on the other surface of the base material of the PET film subjected to the easy adhesion treatment under the same conditions as in Example 1. An adhesive layer coating solution having the following composition is gravure coated on the easily-adhesive treated surface of the base material to a dry coating amount of 0.2 g / m 2. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Example 12 is manufactured.
[0051]
<Adhesive layer composition liquid G>
5.7 parts of polyvinylpyrrolidone resin (K-90, manufactured by ISP)
Acrylic resin (ME-18, manufactured by Nagase ChemteX Corporation) 0.3 part
47 parts of water
47 parts of isopropyl alcohol
[0052]
(Example 13)
A heat-resistant lubricating layer similar to that of Example 1 was formed in advance on the other surface of the base material of the PET film subjected to the easy adhesion treatment under the same conditions as in Example 1. An adhesive layer coating solution having the following composition is gravure coated on the easily-adhesive treated surface of the base material to a dry coating amount of 0.2 g / m 2. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Example 13 is manufactured.
[0053]
<Adhesive layer composition liquid H>
Polyvinylpyrrolidone resin (K-30, manufactured by ISP) 3 parts
47 parts of water
47 parts of isopropyl alcohol
[0054]
(Example 14)
As a substrate, an untreated polyethylene terephthalate film (PET) (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., Diafoil K880) having a thickness of 6 μm was subjected to corona irradiation treatment. The coating amount of the adhesive layer used in 1 was gravure coated to a dry coating amount of 0.2 g / m. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Example 14 is manufactured. The same heat-resistant lubricating layer as in Example 1 was previously formed on the other surface of the substrate.
[0055]
(Example 15)
A substrate of a PET film subjected to corona irradiation treatment under the same conditions as in Example 14 was used, and a heat-resistant lubricating layer similar to that of Example 1 was previously formed on the other surface of the substrate. The adhesive layer coating liquid used in Example 7 was gravure-coated on the corona-irradiated surface of the base material by a gravure coating so that the dry coating amount was 0.2 g / m2. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Example 15 is manufactured.
[0056]
(Example 16)
As a base material, an untreated polyethylene terephthalate film (PET) (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., Diafoil K880) having a thickness of 6 μm was subjected to plasma irradiation treatment, and the other surface of the base material was treated with an example. The same heat-resistant lubricating layer as in No. 1 was formed in advance. The coating amount of the adhesive layer used in Example 1 was gravure-coated on the plasma irradiation-treated surface of the base material by a gravure coating, so that the dry coating amount was 0.2 g / m2. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Example 16 is manufactured.
[0057]
(Example 17)
An untreated polyethylene terephthalate film (PET) (Diafoil K880, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) having a thickness of 6 μm was used as the base material, and the other surface of the base material was the same as in Example 1. A heat-resistant lubricating layer was formed in advance. On the untreated surface of the substrate, the adhesive layer coating solution used in Example 10 was gravure coated to a dry coating amount of 0.2 g / m 2. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Example 17 is manufactured.
[0058]
(Example 18)
A substrate of an untreated PET film under the same conditions as in Example 17 was used, and a heat-resistant lubricating layer similar to that of Example 1 was formed on the other surface of the substrate in advance. On the untreated surface of the base material, a coating weight of 0.2 g / m2 was applied by gravure coating with an adhesive layer coating solution having the following composition. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Example 18 is manufactured.
[0059]
<Adhesive layer composition liquid I>
4.5 parts of polyvinylpyrrolidone resin (K-90, manufactured by ISP)
1.5 parts of polyester resin (RV220, manufactured by Toyobo Co., Ltd.)
Methyl ethyl ketone 47 parts
30 parts of isopropyl alcohol
17 parts of toluene
[0060]
(Example 19)
A substrate of an untreated PET film under the same conditions as in Example 17 was used, and a heat-resistant lubricating layer similar to that of Example 1 was formed on the other surface of the substrate in advance. On the untreated surface of the base material, the adhesive layer coating solution used in Example 11 was gravure coated to a dry coating amount of 0.2 g / m 2. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Example 19 is manufactured.
[0061]
(Example 20)
A substrate of an untreated PET film under the same conditions as in Example 17 was used, and a heat-resistant lubricating layer similar to that of Example 1 was formed on the other surface of the substrate in advance. On the untreated surface of the base material, a coating weight of 0.2 g / m2 was applied by gravure coating with an adhesive layer coating solution having the following composition. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Example 20 is manufactured.
[0062]
<Composition liquid J for adhesive layer>
4.5 parts of polyvinylpyrrolidone resin (K-90, manufactured by ISP)
1.5 parts of polyurethane resin
(Superflex 460S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
47 parts of water
47 parts of isopropyl alcohol
[0063]
(Example 21)
A substrate of an untreated PET film under the same conditions as in Example 17 was used, and a heat-resistant lubricating layer similar to that of Example 1 was formed on the other surface of the substrate in advance. On the untreated surface of the substrate, the adhesive layer coating liquid used in Example 12 was gravure coated to a dry coating amount of 0.2 g / m 2. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Example 21 is manufactured.
[0064]
(Example 22)
A substrate of an untreated PET film under the same conditions as in Example 17 was used, and a heat-resistant lubricating layer similar to that of Example 1 was formed on the other surface of the substrate in advance. On the untreated surface of the base material, a coating weight of 0.2 g / m2 was applied by gravure coating with an adhesive layer coating solution having the following composition. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Example 22 is manufactured.
[0065]
<Adhesive layer composition liquid K>
4.5 parts of polyvinylpyrrolidone resin (K-90, manufactured by ISP)
Acrylic resin (ME-18, manufactured by Nagase ChemteX Corporation) 1.5 parts
47 parts of water
47 parts of isopropyl alcohol
[0066]
(Example 23)
A substrate of an untreated PET film under the same conditions as in Example 17 was used, and a heat-resistant lubricating layer similar to that of Example 1 was formed on the other surface of the substrate in advance. On the untreated surface of the base material, a coating weight of 0.2 g / m2 was applied by gravure coating with an adhesive layer coating solution having the following composition. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1 to produce a thermal transfer sheet of Example 23.
[0067]
<Adhesive layer composition liquid L>
3.9 parts of polyvinylpyrrolidone resin (K-90, manufactured by ISP)
Polyester resin (RV220, manufactured by Toyobo Co., Ltd.) 2.1 parts
Methyl ethyl ketone 47 parts
30 parts of isopropyl alcohol
17 parts of toluene
[0068]
(Example 24)
A substrate of an untreated PET film under the same conditions as in Example 17 was used, and a heat-resistant lubricating layer similar to that of Example 1 was formed on the other surface of the substrate in advance. On the untreated surface of the base material, a coating weight of 0.2 g / m2 was applied by gravure coating with an adhesive layer coating solution having the following composition. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Example 24 is manufactured.
[0069]
<Adhesive layer composition liquid M>
3.9 parts of polyvinylpyrrolidone resin (K-90, manufactured by ISP)
Polyurethane resin 2.1 parts
(Superflex 460S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
47 parts of water
47 parts of isopropyl alcohol
[0070]
(Example 25)
A substrate of an untreated PET film under the same conditions as in Example 17 was used, and a heat-resistant lubricating layer similar to that of Example 1 was formed on the other surface of the substrate in advance. On the untreated surface of the base material, a coating weight of 0.2 g / m2 was applied by gravure coating with an adhesive layer coating solution having the following composition. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Example 25 is manufactured.
[0071]
<Adhesive layer composition liquid N>
3.9 parts of polyvinylpyrrolidone resin (K-90, manufactured by ISP)
Acrylic resin (ME-18, manufactured by Nagase ChemteX Corporation) 2.1 parts
47 parts of water
47 parts of isopropyl alcohol
[0072]
(Example 26)
The thermal transfer sheet produced in Example 1 was prepared. However, as shown in the evaluation method below, the thermal transfer image-receiving sheet used in combination was different from that in Example 1, and a card made of polyvinyl chloride resin (made of PVC) was used.
[0073]
(Example 27)
The thermal transfer sheet prepared in Example 14 was prepared. However, as shown in the following evaluation method, the thermal transfer image-receiving sheet used in combination was different from that in Example 14, and a card made of polyvinyl chloride resin (made of PVC) was used.
[0074]
(Comparative Example 1)
A heat-resistant lubricating layer similar to that of Example 1 was formed in advance on the other surface of the base material of the PET film subjected to the easy adhesion treatment under the same conditions as in Example 1. A dye layer is directly formed on the easily adhesive-treated surface of the base material without an adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Comparative Example 1 is produced.
[0075]
(Comparative Example 2)
A heat-resistant lubricating layer similar to that of Example 1 was formed in advance on the other surface of the base material of the PET film subjected to the easy adhesion treatment under the same conditions as in Example 1. A dye layer is directly formed on the easily adhesive-treated surface of the base material without an adhesive layer in the same manner as in Example 4, and a thermal transfer sheet of Comparative Example 2 is produced.
[0076]
(Comparative Example 3)
A heat-resistant lubricating layer similar to that of Example 1 was formed in advance on the other surface of the base material of the PET film subjected to the easy adhesion treatment under the same conditions as in Example 1. A dye layer is formed directly on the easily-adhered surface of the base material without an adhesive layer in the same manner as in Example 5 to produce a thermal transfer sheet of Comparative Example 3.
[0077]
(Comparative Example 4)
A heat-resistant lubricating layer similar to that of Example 1 was formed in advance on the other surface of the base material of the PET film subjected to the easy adhesion treatment under the same conditions as in Example 1. A dye layer is formed directly on the easily-adhered surface of the base material without an adhesive layer in the same manner as in Example 6, to produce a thermal transfer sheet of Comparative Example 4.
[0078]
(Comparative Example 5)
A substrate of a PET film subjected to corona irradiation treatment under the same conditions as in Example 14 was used, and a heat-resistant lubricating layer similar to that of Example 1 was previously formed on the other surface of the substrate. A dye layer is formed directly on the corona-irradiated surface of the base material without an adhesive layer in the same manner as in Example 1 to produce a thermal transfer sheet of Comparative Example 5.
[0079]
(Comparative Example 6)
A substrate of a PET film subjected to plasma irradiation treatment under the same conditions as in Example 16 was used, and a heat-resistant lubricating layer similar to that of Example 1 was previously formed on the other surface of the substrate. A dye layer is formed directly on the plasma irradiation-treated surface of the base material without an adhesive layer in the same manner as in Example 1 to produce a thermal transfer sheet of Comparative Example 6.
[0080]
(Comparative Example 7)
A heat-resistant lubricating layer similar to that of Example 1 was formed in advance on the other surface of the base material of the PET film subjected to the easy adhesion treatment under the same conditions as in Example 1. An adhesive layer coating solution having the following composition is gravure coated on the easily-adhesive treated surface of the base material to a dry coating amount of 0.2 g / m 2. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Comparative Example 7 is manufactured.
[0081]
<Adhesive layer composition liquid O>
6 parts of polyester resin (RV220, manufactured by Toyobo Co., Ltd.)
Toluene 47 parts
Methyl ethyl ketone 47 parts
[0082]
(Comparative Example 8)
A heat-resistant lubricating layer similar to that of Example 1 was formed in advance on the other surface of the base material of the PET film subjected to the easy adhesion treatment under the same conditions as in Example 1. An adhesive layer coating solution having the following composition is gravure coated on the easily-adhesive treated surface of the base material to a dry coating amount of 0.2 g / m 2. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Comparative Example 8 is manufactured.
[0083]
<Adhesive layer composition liquid P>
6 parts of polyurethane resin
(Superflex 460S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
47 parts of water
47 parts of isopropyl alcohol
[0084]
(Comparative Example 9)
A heat-resistant lubricating layer similar to that of Example 1 was formed in advance on the other surface of the base material of the PET film subjected to the easy adhesion treatment under the same conditions as in Example 1. An adhesive layer coating solution having the following composition is gravure coated on the easily-adhesive treated surface of the base material to a dry coating amount of 0.2 g / m 2. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Comparative Example 9 is manufactured.
[0085]
<Adhesive layer composition liquid Q>
Acrylic resin (ME-18, manufactured by Nagase ChemteX Corporation) 6 parts
47 parts of water
47 parts of isopropyl alcohol
[0086]
(Comparative Example 10)
A substrate of a PET film subjected to corona irradiation treatment under the same conditions as in Example 14 was used, and a heat-resistant lubricating layer similar to that of Example 1 was previously formed on the other surface of the substrate. An adhesive layer was formed on the corona-irradiated surface of the substrate in the same manner as in Comparative Example 7. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Comparative Example 10 is manufactured.
[0087]
(Comparative Example 11)
A substrate of a PET film subjected to corona irradiation treatment under the same conditions as in Example 14 was used, and a heat-resistant lubricating layer similar to that of Example 1 was previously formed on the other surface of the substrate. On the corona-irradiated surface of the base material, a gravure coating of an adhesive layer coating solution having the following composition was performed, so that the dry coating amount was 0.2 g / m2. ² And dried to form an adhesive layer. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Comparative Example 11 is manufactured.
[0088]
<Adhesive layer composition liquid R>
Polyester resin (MD-1245, manufactured by Toyobo Co., Ltd.) 6 parts
47 parts of water
47 parts of isopropyl alcohol
[0089]
(Comparative Example 12)
A substrate of an untreated PET film under the same conditions as in Example 17 was used, and a heat-resistant lubricating layer similar to that of Example 1 was formed on the other surface of the substrate in advance. An adhesive layer was formed on the untreated surface of the substrate in the same manner as in Comparative Example 7. Further, a dye layer is formed on the adhesive layer in the same manner as in Example 1, and a thermal transfer sheet of Comparative Example 12 is manufactured.
[0090]
(Comparative Example 13)
A thermal transfer sheet prepared in Comparative Example 1 was prepared. However, as shown in the evaluation method below, the thermal transfer image-receiving sheet used in combination was different from that in Comparative Example 1, and a card made of polyvinyl chloride resin (made of PVC) was used.
[0091]
(Comparative Example 14)
A thermal transfer sheet prepared in Comparative Example 5 was prepared. However, as shown in the following evaluation method, the thermal transfer image-receiving sheet used in combination was different from that in Comparative Example 5, and a card made of polyvinyl chloride resin (made of PVC) was used.
[0092]
Using the thermal transfer sheets of Examples and Comparative Examples produced above, each of the density evaluation, printability, and heat resistance adhesion was evaluated by the following methods.
(Concentration evaluation)
Printing was performed under the following conditions, and the maximum density of the obtained print was measured.
The combination of the thermal transfer sheets prepared in Examples 1 to 5 and 7 to 25 and Comparative Examples 1 to 3 and 5 to 12 and a photographic paper of a standard set for digital color printer P-200 manufactured by Olympus Corporation was used. Co., Ltd., using a digital color printer P-200, printing with a black solid (gradation value 255/255: density max) printing pattern, and printing with a Macbeth densitometer RD-918 (manufactured by Sakata Inx Co., Ltd.). The highest concentration in parts was measured.
The thermal transfer sheets produced in Example 6 and Comparative Example 4 were manufactured using Konica Corporation (C-A6-PH), a standard photographic paper for photo chelate printer A6 (CHC-S1045-5E). Co., Ltd., a photo chelate printer A6 (CHC-S1045-5E) is used to print with a black solid (gradation value 255/255: density max) print pattern, and a Macbeth densitometer RD-918 (manufactured by Sakata Inx Co., Ltd.) ), The maximum density of the print portion was measured.
Further, the combination of the thermal transfer sheets prepared in Examples 26 and 27 and Comparative Examples 13 and 14 and a card made of polyvinyl chloride resin (manufactured by PVC) was applied to a black solid (gradation value) by an Eltron card printer P310. 255/255: Density Max), and the maximum density of the printed portion was measured with a Macbeth densitometer RD-918 (manufactured by Sakata Inx Co., Ltd.).
[0093]
<Evaluation criteria>
Compare the maximum density with the reference ribbon (ribbon that does not sandwich the adhesive layer),
：: concentration of 110% or more
：: 100% or more and less than 110%
Δ: concentration is 90% or more and less than 100%
×: concentration less than 90%
The reference ribbon has the same conditions for the dye layer, has no adhesive layer, and has the same object to be transferred.
That is, Examples 1, 2, 3, and 7 to 25 are based on Comparative Example 1, Example 4 is based on Comparative Example 2, Example 5 is based on Comparative Example 3, and Example 6 is based on Comparative Example 4. Further, Comparative Examples 5 to 12 were based on Comparative Example 1, and Examples 26 and 27 were based on Comparative Example 13.
[0094]
(Printability)
Similarly to the above-described density evaluation method, when printing was performed, the presence or absence of printing defects such as abnormal transfer, transfer unevenness, and transfer omission were visually inspected.
The evaluation was performed according to the following criteria.
：: No printing defects such as abnormal transfer, transfer unevenness, and missing transfer.
×: Printing defects such as abnormal transfer, transfer unevenness, and transfer omission are present.
[0095]
(Heat resistant adhesive)
The thermal transfer sheets as the samples of the examples and the comparative examples are stuck on the backing paper with the dye layer side up (the backing paper is in contact with the heat-resistant lubricating layer). Then, a reference ribbon corresponding to the sample (having the same dye layer conditions and no adhesive layer, which is the same as in the above density evaluation) is attached to the same mount at different positions with the dye layer face up. The sheet was folded back on each mount so that the dye layer surfaces of the sample and the reference ribbon were in contact with each other, and the temperature was 100 to 130 ° C. and the pressure was 2.5 kg / cm. ² Heat sealing was performed for 2 seconds under a pressurizing time, the two were peeled off, and the remaining state (taken state) of each dye layer of the sample and the reference ribbon was visually inspected and evaluated according to the following criteria.
[0096]
：: The area of the dye layer remaining on the sample side is larger than the area remaining on the reference ribbon side.
X: The area of the dye layer remaining on the sample side is smaller than the area remaining on the reference ribbon side.
[0097]
The evaluation results of the above Examples and Comparative Examples are shown in Table 1 below.
[Table 1]

[0098]
From the results of the above density evaluation, the examples in which the adhesive layer contains a polyvinylpyrrolidone resin have a high transfer sensitivity in printing and a high printing density. In addition, the above-mentioned heat-resistant adhesiveness is a test for examining the adhesiveness between the dye layer and the substrate under high temperature, and is an evaluation related to the prevention of abnormal transfer in thermal transfer printing. It is excellent in printing properties and does not cause printing defects such as abnormal transfer, transfer unevenness, and transfer omission. In Example 13, the adhesive layer used was a polyvinylpyrrolidone having a K value of 30 alone, and the maximum density was slightly lower than that of the reference ribbon (the thermal transfer sheet of Comparative Example 1). Good adhesiveness.
In Examples 23, 24, and 25, polyvinylpyrrolidone contained an adhesive component at a ratio of 35% by weight based on the solid content of the entire adhesive layer, and the highest concentration was the reference ribbon (the thermal transfer sheet of Comparative Example 1). Although slightly reduced as compared with, both printability and heat-resistant adhesiveness are good.
[0099]
【The invention's effect】
As described above, a heat-resistant lubricating layer is provided on one surface of a base material, and an adhesive layer and a dye layer are sequentially formed on the other surface of the base material, wherein the adhesive layer contains a polyvinylpyrrolidone resin. Therefore, the transfer sensitivity during thermal transfer is greatly improved, and a high-density thermal transfer image can be obtained without applying high energy. In addition, by mixing an adhesive component in addition to the polyvinylpyrrolidone resin in the adhesive layer, the adhesiveness between the dye layer and the substrate can be enhanced even when a substrate that has not been subjected to an adhesive treatment is used. Transfer and the like can be prevented.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing one embodiment of a thermal transfer sheet of the present invention.
FIG. 2 is a schematic sectional view showing another embodiment of the thermal transfer sheet of the present invention.
[Explanation of symbols]
1 Substrate
2 adhesive layer
3 Dye layer
4 Heat-resistant lubricating layer
5 Primer layer

Claims (6)

A heat transfer sheet in which a heat-resistant lubricating layer is provided on one surface of a substrate and an adhesive layer and a dye layer are sequentially formed on the other surface of the substrate, wherein the adhesive layer is made of polyvinylpyrrolidone resin. Sheet. 2. The thermal transfer sheet according to claim 1, wherein the polyvinylpyrrolidone resin has a K value of 60 or more in Fickenture formula. 3. The thermal transfer sheet according to claim 1, wherein an adhesive component is mixed in the adhesive layer in addition to the polyvinylpyrrolidone resin. 4. The thermal transfer sheet according to claim 3, wherein the adhesive component mixed in the adhesive layer is contained at a ratio of 1 to 30% by weight based on the solid content of the entire adhesive layer. The thermal transfer sheet according to any one of claims 1 to 4, wherein the surface of the substrate on which the dye layer is formed has been subjected to an adhesive treatment. The thermal transfer sheet according to claim 3, wherein the surface of the substrate on which the dye layer is formed is not subjected to an adhesive treatment.

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