JP3845894B2 - Photothermal conversion type heat mode image receiving material - Google Patents

Description

【０１４０】
（受像材料の作成）
厚さ１００μｍの透明ＰＥＴ（前出：Ｔ−１００）に、下記組成のクッション層塗工液を乾燥膜厚約３０μｍになるようアプリケーターにて塗工し、その上に下記組成の剥離層塗工液を乾燥膜厚約２．０μｍになるようワイヤーバーにて塗工し、更にその上に下記組成の受像層塗工液を乾燥膜厚約０．４μｍになるようワイヤーバーにて塗工して受像材料とした。
【０１４１】
クッション層塗工液
アクリル系ラテックス（カネボウＮＳＣ製：Ａ５８０１）
剥離層塗工液
メチルセルロース（信越化学工業社製：Ｎ１０Ｇ） ５．０部
イソプロピルアルコール ９５．０部
受像層塗工液
アクリル系ラテックス（前出：Ａ５８０１）
上記受像材料において、クッション層及び受像層の素材を異にする試料を作成し、これらと前記記録材料を用いて以下のようなヒートモード転写を行い、以下に示す評価方法に基づいて感度、カブリ及び保存性を評価した。
【０１４２】
（ヒートモード転写）
波長８３０ｎｍの半導体レーザーを、１／ｅ²のスポット径を８μｍとした光学系に対し、ドラム状減圧機に４００ｔｏｒｒで減圧密着された記録材料と受像材料を６００ｃｍ／秒の線速度で回転させ、露光ピッチ６μｍとして露光面におけるパワーを３０〜１００ｍＷに可変とした露光を与えて転写を行った。
【０１４３】
〈感度〉
露光面のレーザーパワーを変化させて転写したベタ画像の濃度を測定し、濃度が一定となるパワーを求めた。
【０１４４】
パワー数値：評価可能試料
−：評価不能試料（ブロッキングが生じる、カブリ測定不能、マット剤過剰）〈カブリ〉
５０％網点パターンを露光し、得られた転写画像の未露光部が転写して了った部分をカブリとして目視で６段階評価した。
【０１４５】
○ ：カブリなし
○△：画像の約２５％にカブリあり
△ ：画像の約５０％にカブリあり
△×：画像の約７５％にカブリあり
× ：画像全面にカブリ
− ：ブロッキングして了ってカブリ測定不能
〈異物〉
受像材料と記録材料の間に２０μｍの繊維（糸ゴミ）を挟んだ後に露光し、繊維周辺の画像の転写抜けを観察し、４段階評価した。
【０１４６】
○ ：糸ゴミ周辺の画像転写抜けがない
○△：糸ゴミの形に沿って５０μｍ程度の画像転写抜けがある
△ ：糸ゴミの形に沿って周辺の転写濃度が下がる
× ：糸ゴミを中心として円く２ｍｍ位の画像転写抜けが起こる
〈保存性〉
受像材料の受像層面とバッキング層面を重ね合わせ、荷重５０ｇ／ｃｍ²を掛けて５５℃・７日間の熱加速試験を行い、試験後のブロッキング、転写性（カブリ、感度）を評価した。転写性については前出の方法で評価し、ブロッキングについては以下の４段階で評価した。
【０１４７】
◎ ：１００ｇ／ｃｍ²の荷重を掛けてもブロッキングなし
○ ：ブロッキングなし
△ ：一部受像層剥がれが生じる
× ：完全にブロッキングを起こす
比較例１
（受像材料の作成）
実施例１の受像材料において、受像層塗工液を下記組成に変えた以外は同様にして受像材料を作成した。
【０１４８】
受像層塗工液
アクリル樹脂（三菱レーヨン製：ＢＲ１１３） １０部
メチルエチルケトン ４５部
イソプロピルアルコール ４５部
受像層の軟化点の相違による感度の評価を表１に示す。
【０１４９】
【表１】

【０１５０】
受像層が柔らかい方が感度が高いことが判る。
【０１５１】
実施例２
（記録材料の作成）
実施例１の記録材料において、インク層塗工液を下記組成に変えた以外は同様にして記録材料を作成した。
【０１５２】
インク層塗工液
マゼンタ顔料メチルエチルケトン分散物 ３．０部
（前出：ブリリアントカーミン６Ｂ）
スチレン／アクリル樹脂（前出：ハイマーＳＢＭ４３Ｆ） ７．５部
エチレン／酢酸ビニル樹脂（前出：ＥＶ４０Ｙ） ０．５部
シリコン樹脂粒子（前出：トスパール１２０） ２．０部
メチルエチルケトン ９０．０部
（受像材料の作成）
実施例１の受像材料において、剥離層迄を塗布したものの上に、以下の素材から成る受像層塗工液の組成比率を変化させて乾燥膜厚約０．４μｍの厚さになるよう塗布した。
【０１５３】
受像層塗工液
アクリル系ラテックス（前出：Ａ５８０１）固形分５５％
マット材（綜研化学製ＰＭＭＡ微粒子：ＭＲ２ＨＧ，平均粒径２．２μｍの２倍以上の平均重量１３％）
上記記録材料、受像材料を用いて以下のようにヒートモード転写を行い、実施例１と同様に評価した。結果を表２に示す。
【０１５４】
（ヒートモード転写）
ドラム状減圧機に１２０ｔｏｒｒで減圧密着された記録材料と受像材料を、波長１０６４ｎｍのＹＡＧレーザーの１／ｅ²のスポット径を１２μｍ、露光ピッチ１０μｍとした光学系を用い、２００００ｃｍ／秒の線速度で露光面におけるパワーを２〜４Ｗ迄変化させて転写を行った。
【０１５５】
【表２】

【０１５６】
マット剤を含有したものの方がカブリが少なく、更に低軟化点のものの方が感度が高い。
【０１５７】
実施例３
実施例２と同じ受像材料の受像層のマット剤を以下の如く変化させ、マット材が存在しない部分の乾燥膜厚が約１．５μｍになるよう塗布してた受像材料を作成した。実施例２に記載の記録材料を用いて実施例２と同様にヒートモード転写を行い評価した。
【０１５８】
Ａ：ＰＭＭＡ粒子（平均粒径５．６μｍ，平均粒径の２倍以上の平均重量３０％）
Ｂ：ＭＲ２ＨＧ（前出，綜研化学製：ＭＲ２ＨＧ，平均粒径２．２μｍ，平均粒径の２倍以上の平均重量１３％）
Ｃ：ＭＸ−２１Ｓ（綜研化学製：平均粒径２．１μｍ，平均粒径の２倍以上の平均重量１％以下）
Ｄ：ＭＰ−１４００（綜研化学製：平均粒径１．５μｍ，平均粒径の２倍以上の平均重量１％以下）
受像層のマット材の平均粒径及び平均粒径の２倍以上の平均重量（以下、粒度分布と記す）の違いによる感度、カブリ、保存性の評価結果を表３に示す。
【０１５９】
【表３】

【０１６０】
受像層の膜厚よりも粒径が若干大きく、粒径分布も小さいマット材を用いた方が感度が高く、カブリも少ない。
【０１６１】
実施例４
剥離層バインダーのガラス転移点、引張り強度を以下の如く変化させ、クッション層バインダーとしてＥＶ４０Ｙ、Ａ５８０１及びＡＤ９２（いずれもＴＭＡ軟化点６０℃以下）を用いる以外は実施例２と同じであり、マット材としてＭＲ２ＨＧ（前出）を用いた受像材料と実施例２の記録材料を用いて、実施例２と同様にヒートモード転写を行い評価した。
【０１６２】
Ｅ：ポリカーボネート（三菱瓦斯化学製：ＰＣＺ２００）
Ｆ：ポリビニルアセタール（積水化学製：エスレックＫＳ−１）
Ｇ：エチルセルロース（信越化学工業製：Ｎ１０Ｇ）
Ｈ：ポリエステル（ユニチカ製：ＵＥ３３００）
剥離層の物性、膜厚、保存性の関係を表４、５及び６に示す。
【０１６３】
【表４】

【０１６４】
【表５】

【０１６５】
【表６】

【０１６６】
剥離層のバインダーの物性とその膜厚に応じてカブリ、感度、保存性の最適点が得られることが判る。
【０１６７】
実施例５
受像層の膜厚を以下の如く変化させた以外は実施例２と同じ受像材料と、実施例２の記録材料を用いて以下のようにヒートモード転写を行い評価した。
【０１６８】
受像層膜厚と二次転写後の画像部、非画像部の光沢を測定した結果を表７に示す。
【０１６９】
【表７】

【０１７０】
受像層の膜厚を変えることで、二次転写後の画像の光沢を用途に応じて変えることができる。
【０１７１】
実施例６
本実施例は構成Ｂに対応する。
【０１７２】
（記録材料の作成）
厚さ２５μｍの透明ＰＥＴ（ダイヤホイルヘキスト製：Ｔ１００Ｇ，＃２５）を支持体として、その上に下記組成の離型層塗工液をリバースロールコーターにて塗布・乾燥し、乾燥膜厚０．３μｍの離型層を形成した。
【０１７３】
離型層塗工液
離型層バインダー液＊ ２９部
架橋剤（住友化学製：スミレーズレジン６１３） ０．３部
水 ７０．７部
＊離型層バインダー液は、ポリビニルアルコール水溶液（日本合成化学製：ゴーセノールＥＧ−３０の９．５％水溶液）９７．２部、架橋促進剤（住友化学製：スミレーズレジンＡＣＸ−Ｐ）１．３部、弗素系界面活性剤（住友化学製：スミレーズレジンＦＰ−１５０）０．３部及び水１．２部により固形分９．５％のバインダー液を調製した。
【０１７４】
上記離型層の上に、下記組成のインク層塗工液をワイヤーバーコーティングで塗布・乾燥しインク層を形成した。
【０１７５】
イエロー記録材料（インク層塗工液）
イエロー顔料分散物１ １６．９部
（ジスアゾエローＡＡＡ１０部を分散剤２部で
メチルエチルケトン８８部に分散したもの）
イエロー顔料分散物２ １．９部
（ジスアゾエローＨＲの１０部を分散剤３部で
メチルエチルケトン８７部に分散したもの）
スチレン／アクリル樹脂 ２．４部
（前出：ハイマーＳＢＭ７３Ｆ）
エチレン／酢酸ビニル樹脂（前出：ＥＶ４０Ｙ） ０．２部
弗素系界面活性剤（旭硝子製：サーフロンＳ−３８２） ０．１部
メチルエチルケトン ４８．１部
シクロヘキサノン ３０．４部
乾燥膜厚は０．５５μｍとした。
【０１７６】
マゼンタ記録材料（インク層塗工液）
マゼンタ顔料分散物 １２部
（ブリリアントカーミン６Ｂの１５部を分散剤４．５部で
メチルエチルケトン２０．５部に分散したもの）
スチレン／アクリル樹脂 ２．４部
（前出：ハイマーＳＢＭ７３Ｆ）
エチレン／酢酸ビニル樹脂（前出：ＥＶ４０Ｙ） ０．２部
弗素系界面活性剤（前出：サーフロンＳ−３８２） ０．１部
メチルエチルケトン ６０．５部
メチルイソブチルケトン ２４．８部
乾燥膜厚は０．５６μｍとした。
【０１７７】
シアン記録材料（インク層塗工液）
シアン顔料分散物 ５．１部
（フタロシアニンブルーの３０部を分散剤５部で
メチルエチルケトン６５部に分散したもの）
スチレン／アクリル樹脂 ２．９部
（前出：ハイマーＳＢＭ７３Ｆ）
エチレン／酢酸ビニル樹脂（前出：ＥＶ４０Ｙ ０．２部
弗素系界面活性剤（前出：サーフロンＳ−３８２） ０．１部
メチルエチルケトン ５０．３部
メチルイソブチルケトン ４２部
乾燥膜厚は０．５４μｍとした。
【０１７８】
ブラック記録材料（インク層塗工液）
ブラック顔料分散物 ４．９部
（カーボンブラック ３３部を分散剤６．６部で
メチルエチルケトン６０．４部に分散したもの）
シアン顔料分散物（前出） ０．９部
バイオレット顔料分散物 １．２部
（ジオキサジンバイオレットの１０部を分散剤５部で
メチルエチルケトン８５部に分散したもの）
スチレン／アクリル樹脂 ３．９部
（前出：ハイマーＳＢＭ７３Ｆ）
エチレン／酢酸ビニル樹脂（前出：ＥＶ４０Ｙ） ０．３部
弗素系界面活性剤（前出：サーフロンＳ−３８２） ０．１部
メチルエチルケトン ５７．９部
メチルイソブチルケトン ３０．８部
乾燥膜厚は０．７２μｍとした。
【０１７９】
上記各インク層の上に、下記組成の光熱変換層塗工液をワイヤーバーコーティングにて塗布・乾燥して、波長８３０ｎｍの透過吸収率が０．８の光熱変換層を形成した。この光熱変換層の付量は０．６ｇ／ｍ²であった。
【０１８０】
光熱変換層塗布液
ポリビニルアルコール ６部
（日本合成化学製：ゴーセノールＥＧ−３０）
カーボンブラック分散物 ４部
（大日本インキ製：ＳＤ−９０２０）
界面活性剤 ０．２部
水 ４９０部
一方、厚さ１００μｍの透明ＰＥＴ（前出：Ｔ１００Ｇ，♯１００）フィルム上に、下記組成のバックコート層塗工液をワイヤーバーコーティングにて塗布、乾燥膜厚０．６μｍのバックコート層を形成した。
【０１８１】
バックコート層塗工液
ポリビニルアルコール ７９部
（日本合成化学製：ゴーセノールＥＧ−０５）
弗素系界面活性剤 ５部
（住友化学製：スミレーズレジンＦＰ−１５０）
帯電防止剤（松本油脂製：エフコール２１４） １０部
マット材（体積平均粒径５．６μｍのＰＭＭＡ粒子） ６部
水 ９０部
上記バックコート層の裏面に、下記組成の中間層塗工液をワイヤーバーコーティング塗布し、乾燥膜厚６μｍの中間層を形成した。
【０１８２】
中間層塗布液
ＳＥＢＳ（シェル化学製：クレイトンＧ１６５７） １４部
タッキファイヤー（荒川化学製：スーパーエステルＡ１００） ６部
メチルエチルケトン １０部
トルエン ８０部
次に、前記インク層と光熱変換層を設けた各シートの光熱変換層を、上記中間層と合わせてロールタッチで両者を貼り合わせた後、離型層付きフィルムを剥離して、イエロー、マゼンタ、シアン、ブラックの各記録材料を得た。
【０１８３】
（受像材料１〜９の作成）
厚さ１００μｍのＰＥＴ（前出：Ｔ−１００）に、上記中間層の作成に用いたのと同じ組成のバックコート層（乾燥膜厚０．６μｍ）を設けた。
【０１８４】
このバックコート層とは反対面にアクリル系エマルジョン（ゼネカ製：ネオクリルＡ−１０５２）を乾燥膜厚が約３５μｍになるようアプリケーターにて塗工してクッション層とした。その上に、下記組成の剥離層塗工液をワイヤーバーコーティングにて塗布・乾燥して、膜厚約１．５μｍの剥離層を形成した。
【０１８５】
剥離層塗工液
ポリエステル（ユニチカ製：ＵＥ−３３００） ８部
イソプロピルアルコール ９２部
受像層塗工液は、ポリアクリル酸ラテックス（カネボウＮＳＣ製：ヨドゾールＡ５８０１，樹脂分５５％）に対し、前出の界面活性剤（スミレーズレジンＦＰ−１５０）をラテックスの固形分に対し４％となるよう添加し、更に所望の比率でマット材を添加し、固形分１２％の液としてワイヤーバーコーティングにて塗工して受像材料を作成した。
【０１８６】
（受像材料１０〜２４の作成）
受像材料１〜９と同様にバックコート層を設けた厚さ１００μｍのＰＥＴ（前出：Ｔ−１００）に、アクリル系ラテックス（カネボウＮＳＣ製：ヨドゾールＡＤ９２）を乾燥膜厚約３０μｍになるようアプリケーターにて塗工してクッション層とした。
【０１８７】
その上に、下記組成の剥離層塗工液をワイヤーバーコーティングにて塗布・乾燥して、膜厚約１．７μｍの剥離層を形成した。
【０１８８】
剥離層塗工液
エチルセルロース（ダウ・ケミカル製：エトセル７） １０部
イソプロピルアルコール ９０部
更に、バインダーとして、ポリアクリル酸ラテックス（カネボウＮＳＣ製：ヨドゾールＡ５８０５，樹脂分５５％）を用い、所望の比率でマット材を添加し、固形分１２％の液としてワイヤーバーコーティングにて塗工し受像シートを作成した。
【０１８９】
これらの受像材料と前記記録材料を用いて、以下のようにヒートモード転写を行った。
【０１９０】
（レーザー熱転写による画像形成）
ドラム表面に、受像材料を裏面が接するように巻き付けた後、受像層とインク層が接するように記録材料を重ねて巻き付け、ドラム表面の吸引孔、吸引溝より吸引することで真空密着させ、記録材料の裏面からレーザー露光を与えて受像層上に画像を転写させた。
【０１９１】
レーザー露光は、４色分解された網点画像データを用いて変調され、記録材料はＹ，Ｍ，Ｃ，Ｋ（イエロー，マゼンタ，シアン，ブラック）の順に交換しながら対応する色分解データにより変調されたレーザーを用い、最終的に受像層上にフルカラーの画像を得た。
【０１９２】
（ラミネーターによる画像転写）
４色画像が転写された受像材料の受像層を印刷用紙（三菱製紙製：特菱アート）に重ね、圧力２ｋｇ、ロール温度１５０℃、ロール周速２０ｍｍ／秒で加圧・加熱して画像を転写した。
【０１９３】
転写画像について、各特性を以下の評価方法に基づいて評価した。
【０１９４】
〈カブリ〉
５０％網点パターンを露光し、得られた転写画像の未露光部が転写した部分をカブリとして目視で評価した。
【０１９５】
◎：カブリがない
○：画像印象に悪影響のない、極く薄い測定不能のカブリが僅かにある
△：２ｍｍ以下のカブリがある
×：５ｍｍ以上のカブリがある
〈エア抜け欠陥〉
受像材料と記録材料の間の空気抜け不十分による浮きに起因する欠陥発生の有無を評価した。
【０１９６】
◎：欠陥がない
○：１ｍｍ以下の欠陥があるが、画像印象には影響が少ない
△：５ｍｍ以下の欠陥がある
×：１ｃｍ以上の欠陥がある
〈黄色味〉
印刷用紙に転写後の非画像部の色味を目視で評価した。
【０１９７】
◎：全く黄色味が認められない
○：殆ど黄色味が認められない
△：僅かに黄色味が認められる
×：明らかに黄色味が認められる
〈光沢〉
ＪＩＳ Ｚ−８７４１−１９８３に規定されている鏡面光沢度測定方法の方法３に基づき６０度鏡面光沢を測定した。印刷物に近似する光沢は４０〜５５程度である。
【０１９８】
〈アブレート〉
転写した画像に、記録材料の光熱変換層の転写による汚れの有無を目視で評価した。
【０１９９】
◎：アブレートが全くない
○：アブレートが殆どない
△：アブレートがあるが、非常に量が少ない
×：アブレートがあり、色調が再現されない
〈インク転写率〉
記録材料のインク層の透過濃度と、受像材料への画像形成転写後のベタ部の透過濃度の割合（転写濃度／インク層濃度）を％で示す。
【０２００】
結果を表８〜表１２に示す。
【０２０１】
【表８】

【０２０２】
【表９】

【０２０３】
【表１０】

【０２０４】
【表１１】

【０２０５】
【表１２】

【０２０６】
尚、表８、表１１の結果はマゼンタ記録材料を用いての評価、表９の結果はイエロー記録材料を用いての評価、表１０の結果はシアン記録材料を用いての評価である。又、表１２はブラック記録材料を用いての評価を示した。
【０２０７】
尚、マット材の体積平均粒径は、コールターカウンターＴＡ−II（日科機製）を用い、試料約１ｇを純水２００ｍｌで希釈した後、超音波分散機で１５分間分散させ測定した。一方、数平均粒径は、マット材分散液をプレパラートに極く少量採り、乾燥させた後、電子顕微鏡にて観察し測定した。
【０２０８】
又、マット材の個数は、塗布試料を光学顕微鏡で観察・写真撮影し、２００μｍ×２００μｍの面積内に存在する個数から算出した。
【０２０９】
表８〜１２から明らかなように、本発明の内容に沿うマット材を用いることで性能の良い受像材料が得られた。又、反射率の異なるマット材として、５９８ｎｍでの屈折率が１．４８〜１．４９のポリメチルメタクリレート粒子と、１．４６である合成シリカ粒子、１．６７であるガラスビーズから、粒径の近似したものを選択して受像材料を作成したところ、ガラスビーズでは転写画像の中に不要な反射が見られ、最終画像の印象は好ましくなかった。用いたアクリル酸ラテックス樹脂の層形成時の屈折率は１．４〜１．５であった。
【０２１０】
合成シリカ粒子は不定形であるため、添加率に対する光沢低下が著しく、諸性能を満足させられる範囲が著しく狭かった。又、転写画像の彩度も低下する傾向にあった。
【０２１１】
ベタ転写部を観察すると、マット材の存在する部分が微小な転写抜けになった部分も多く見られた。
【０２１２】
更に、受像材料３、５、７、１８、２０について、全色の記録材料を用いて網点画像を重ね記録し、フルカラーの画像を得た。
【０２１３】
いずれも、カブリや欠陥がなく、印刷物に非常に近似した画像を得ることができた。重ね記録は、イエロー、マゼンタ、シアン、ブラックの順に行ったが、後から記録したものが転写率が下がることもなく、紙上にラミネートした後の下層の色調を過剰に隠蔽することなく、優れた２次色再現性が得られた。
【０２１４】
【発明の効果】
本発明の受像材料を用いる記録方法によれば、真空密着により十分な密着が可能であり、かつ搬送性に優れ、転写性の良好な、高速記録可能な光熱変換型ヒートモード記録ができる。更に、本発明の受像材料により、平滑度の低い永久支持体にも鮮明な画像転写ができ、かつ転写画像の光沢を印刷物と同程度まで上げることができる。
【図面の簡単な説明】
【図１】本発明の光熱変換型ヒートモード受像材料を記録材料と重ねてドラム状減圧器に巻き付けることを示す斜視図。
【図２】ドラム状減圧器の基本的構成を示す断面図。
【図３】受像材料と記録材料が平板状減圧器で密着されることを示す断面図。
【図４】ドラム状減圧器及び減圧器の周辺を示す全体構成図。
【図５】本発明の光熱変換型ヒートモード受像材料の層構成の一例を示す断面図。
【符号の説明】
１ 圧力ロール
２ 減圧孔（２−１は開いた状態、２−２は閉じた状態を示す）
３ ヒートモード記録材料（３−１はイエロー、３−２はマゼンタ、３−３はシアン、３−４はブラック記録材料を示す）
４ ヒートモード受像材料
５ ヒートモード記録材料補給手段
６ ヒートモード受像材料補給手段
７ 減圧器保持部分
８ 光学的書込み手段
９ 筐体
１０ 減圧孔弁
１１ 支持体
１２ クッション層
１３ 剥離層
１４ 受像層
１５ バックコート層（必ずしも必要としない）[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an image receiving material used for a photothermal conversion type heat mode recording method capable of converting light into heat and transferring the heat by this heat. In particular, the present invention relates to a photothermal conversion heat mode image receiving material capable of creating a high-definition and / or full-color image by digital dry processing.
[0002]
[Prior art]
Conventionally, as an image forming system by thermal transfer, a pressurizing / heating system using a thermal head has been put into practical use, and has excellent features in terms of noiselessness, simple mechanism, maintenance-free, and dry processing.
[0003]
Moreover, the density of thermal heads has increased in terms of resolution, and in recent years, a resolution of 400 to 600 DPI or more has been obtained. However, it is difficult to increase the density of the thermal head, and the resolution of the conventional thermal transfer recording system is limited.
[0004]
Therefore, a heat mode laser thermal transfer method has been proposed in which an image is exposed to a photothermal conversion type recording material with a laser beam. In this method, since the laser beam can be condensed to about several μm, the resolution can be dramatically improved.
[0005]
However, since the image receiving material used in the photothermal conversion type heat mode recording method can perform high-definition recording, a sufficient transferred image cannot be obtained if the surface unevenness and “undulation” are large. Therefore, when an image is formed on a transfer medium having a low surface smoothness, the image is transferred once to an intermediate transfer medium having a smooth image receiving surface, and further transferred to a desired transfer medium by lamination or the like. Can be considered.
[0006]
Also in the photothermal conversion type heat mode recording method, there are a case where an image is formed by transferring a fusible ink and a case where an image is formed by transferring a sublimable dye, and the configuration required for the image receiving material is different. That is, in the transfer of the sublimable dye, the adhesion between the recording material and the image receiving material at the time of transfer is not so important, and it is preferable to take a fixed interval. On the other hand, in the transfer of the meltable ink image, sufficient adhesion between the recording material and the image receiving material is required.
[0007]
Japanese Patent Application Laid-Open No. 6-126993 discloses a method of forming a sublimable dye image on an intermediate transfer medium with a laser beam, and further re-transferring the image to a final transfer material by pressure heat treatment. When heat recording is performed using a photothermal conversion type heat mode recording material composed of a fusible ink layer, uneven transfer and transfer (fogging) of the ink layer in the unexposed area occur. Further, when silicon resin or the like is used as the release layer, there is a problem that the transfer sensitivity of the meltable ink layer is remarkably lowered with time.
[0008]
As a result of various studies, we added a small amount of matting material to the image-receiving layer of the image-receiving material to improve the adhesion between the recording material and the image-receiving material by adhesion under reduced pressure, and good meltable ink by the photothermal conversion type heat mode recording method The transfer of the image and the retransfer to the transfer material with low smoothness could be performed uniformly.
[0009]
On the other hand, shortening of processing time is demanded in the photothermal conversion type heat mode recording system. It is effective to use a plurality of exposure lasers in parallel as countermeasures in the recording apparatus, and to increase the laser scanning speed by increasing the laser output, but it is also desired to improve the sensitivity of the recording material and the image receiving material. Has been.
[0010]
In order to increase the sensitivity of the image receiving material, it is conceivable to lower the glass transition point (Tg) and softening point of the image receiving layer binder. However, transfer (fogging) of the ink layer in the unexposed area occurs when the image receiving material is in close contact with the recording material. . In order to suppress this fogging, it is conceivable to add fine particles (mat material) to the image receiving layer, but there is a problem that fogging with storage increases. Therefore, it is awaited to provide an image receiving material having high sensitivity and good storage stability.
[0011]
Further, when the image is retransferred to the final transfer target after the image is formed on the intermediate transfer medium, the gloss of the final image becomes a problem. In particular, in order to use for printing proofing, an image gloss similar to that of a printed material is required.
[0012]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and an object thereof is to provide a photothermal conversion type heat mode image receiving material having high sensitivity and excellent storage stability.
[0013]
Another object of the present invention is to provide a heat-sensitive laser-recording image-receiving sheet that has high sensitivity and does not cause fogging. Further, the image can be clearly retransferred to a permanent support having low smoothness, and the transferred image can be transferred. An object of the present invention is to provide a photothermal conversion type heat mode image-receiving material that increases the glossiness of the image.
[0014]
[Means for Solving the Problems]
As a result of intensive studies on the solution of the above problems, the present inventors have found that the above object of the present invention is achieved by the following configuration.
[0015]
(1) In a photothermal conversion heat mode image receiving material having a cushion layer, a release layer, and an image receiving layer on a support, the cushion layer and the image receiving layer have a TMA softening point of 60 ° C. or less, and from the following material group: Selected photothermal conversion type heat mode image receiving material.
  Ethylene-vinyl acetate resin (EVA), acrylic resin.
[0016]
(2) The binder of the release layer is selected from the following material group, the glass transition point is 75 ° C. or higher, or the tensile strength is 3.5 kg / mm.²The photothermal conversion heat mode image receiving material according to (1), wherein the release layer has a thickness of 0.2 to 3.0 μm.
  Polyester resins, polyvinyl acetal resins, polycarbonate resins, ethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, and cured products of these resins.
[0017]
(3) Matte on the image receiving layerMaterialContainsAnd the number average particle diameter of the mat member is 0.3 to 2.0 μm larger than the average film thickness of the portion of the image receiving layer where the mat member does not exist.The photothermal conversion heat mode image receiving material according to (2).
[0018]
(4) of cushion layerBinderTMA softening point is 40 ° C or less,BinderGlass transition point is 140 ° C or higher or tensile strength is 5.0kg / mm²The film thickness is 0.3 to 1.0 μm, the glass transition point is 80 to 140 ° C., or the tensile strength is 3.5 to 5.0 kg / mm.²The photothermal conversion heat mode image-receiving material according to (1) or (3), wherein the film thickness is 1.0 to 3.0 μm.
[0019]
(5) of cushion layerBinderTMA softening point is 40-50 ° C.BinderGlass transition point is 140 ° C or higher or tensile strength is 5.0kg / mm²The film thickness is 0.3 to 0.8 μm, the glass transition point is 80 to 140 ° C., or the tensile strength is 3.5 to 5.0 kg / mm.²The photothermal conversion heat mode image-receiving material according to (1) or (3), wherein the film thickness is 0.8 to 2.5 μm.
[0020]
(6) of cushion layerBinderThe TMA softening point is 50-60 ° C.BinderGlass transition point is 140 ° C or higher or tensile strength is 5.0kg / mm²The film thickness is 0.2 to 0.6 μm, the glass transition point is 80 to 140 ° C., or the tensile strength is 3.5 to 5.0 kg / mm.²The photothermal conversion type heat mode image-receiving material according to (1) or (3), wherein the film thickness is 0.6 to 2.2 μm.
[0023]
(7) It has a particle size distribution in which the particle weight that is at least twice the number average particle size of the mat material is 20% or less (3) To (6). The photothermal conversion heat mode image-receiving material according to any one of the above.
[0025]
(8) The thickness of the image receiving layer is0.4 ~3.0μmThere are (1) to (7The photothermal conversion type heat mode image receiving material according to any one of the above.
[0045]
Hereinafter, the present invention will be described in more detail.
[0047]
As a typical process of the photothermal conversion type heat mode recording method (hereinafter also referred to as heat mode recording method) in the present invention, there is a heat mode recording method described in JP-A-6-122280.
[0048]
As a result of the study by the present inventors, the use of an image receiving material in which an image receiving layer is formed on a sufficiently elastic support as the image receiving material used in the heat mode recording method improves the adhesion between the recording material and the image receiving material. It was found that a good transfer image without omission could be obtained. This is presumably because the support has deformability and adhesion necessary for transfer is achieved. However, in such a material in which the support itself is deformable, the strength and dimensional stability of the support are insufficient, and it is difficult to form a highly accurate image.
[0049]
As a result of further studies, it has been found that the adhesiveness is improved by providing an appropriate cushion layer on the image receiving material to impart deformability. In addition, when the image formed on the image receiving material is superimposed on a material to be transferred such as art paper, coated paper, high quality paper, etc., and re-transferred by heating and / or pressurizing to obtain a final image, the image receiving material is If the cushion layer is not provided, sufficient contact cannot be obtained due to “swelling” of the surface of the paper to be retransferred, and the retransfer image is missing or missing. For this reason, it has been clarified that the image can be transferred to the final recording medium by sufficiently increasing the thickness of the cushion layer of the image receiving material.
[0050]
It is preferable that the cushion layer of the image receiving material has good adhesion, and has deformability that can sufficiently follow the “waviness” of the final recording medium such as art paper, coated paper, and high-quality paper during retransfer.
[0051]
Further, it is preferable that the cushion layer be deformed so that the foreign matter is embedded when the foreign material is caught when the recording material and the image receiving material are overlapped. As a result, even if there is a foreign object, it is possible to prevent an image defect from occurring in that part.
[0052]
Furthermore, the image receiving material needs a certain degree of rigidity in order to enable automatic conveyance within the apparatus and automatic winding of the material around a holding member that holds the recording material and the image receiving material. For this purpose, it is preferable that the support of the image receiving material itself has rigidity.
[0053]
  As described above, the image receiving material was able to obtain a preferable performance as the image receiving material by providing the cushion layer. However, it has been found that if the image receiving layer of the image receiving material is made of a material having a low softening point, high sensitivity can be obtained. It was. However, the use of a material having a low softening point increases the sensitivity, but tends to cause fogging. As a result, the storage stability is significantly deteriorated. Therefore, as a result of the study, it was found that further deterioration of storage stability can be eliminated by providing a release layer between the cushion layer and the image receiving layer, leading to the present invention.It was.
[0054]
  Further, by further studying the adjustment of the average particle size, particle size distribution, addition amount, shape, and material of the mat material added to the image receiving layer, a printed image required for use in color proofing color proofs can be obtained. Satisfies characteristics such as gloss of reproduced images, haze required for use in medical images, etc., and further ensures sensitivity, fog, and adhesion between the image receiving material and the recording material during image recording, and images generated during recording Confirm that an excellent image-receiving material with extremely few defects is obtained.It was.
[0055]
Hereinafter, representative processes of the photothermal conversion type heat mode recording method will be described with reference to the drawings.
[0056]
As shown in FIG. 1, as shown in FIG. 1, the image receiving layer surface of the image receiving material and the ink surface of the recording material having a larger vertical and horizontal dimension than the image receiving material are superimposed on a decompressor having micropores, and protruded from the periphery of the image receiving material. By reducing the pressure from the recording material through the micropores, the image receiving material and the recording material are brought into close contact with each other, and conversely, the ink surface of the recording material is superposed on the image receiving surface of the image receiving material whose longitudinal and horizontal dimensions are larger than the recording material. It is also possible to bring the image receiving material and the recording material into close contact with each other by reducing the pressure from the portion of the image receiving material protruding from the periphery of the material through the micro holes.
[0057]
According to this contact method, it is easy to automate the conveyance and winding of the recording material and the image receiving material, and heat mode recording is possible by performing light irradiation after completion of the contact. The decompressor may be in the form of a drum as shown in FIG. 2 or a flat plate as shown in FIG. 3, but when high-speed recording is required, a flat decompressor and a polygon mirror or galvanometer mirror The cylindrical scanning using a drum-shaped decompressor can reduce the loss of the optical system, compared with the plane scanning according to FIG.
[0058]
Using such a decompressor, the ink surface of the recording material and the image receiving surface of the image receiving material are completely in close contact with each other or close to each other (this state is hereinafter referred to as the close contact state), and is in accordance with the recording information. Thermal transfer recording is performed by irradiating light.
[0059]
FIG. 4 shows the decompressor and the periphery of the decompressor in the present invention.
[0060]
Here, the case where the decompressor is in the form of a drum is illustrated, but the basic configuration is the same in the case of a flat plate. For example, when the image receiving material and the recording material having the configuration shown in FIG. 5 are wound around a pressure reducer, the image receiving material is first depressurized with the pressure reducing hole valve closed, and then wound and fixed. Next, the recording material is wound, and at this time, the decompression holes are sequentially opened. Thereby, shortening of pressure reduction time and a close contact state are easily obtained. It is more effective to open the pressure reducing valve while pressing with the squeeze roller.
[0061]
Next, the image receiving material according to the present invention will be described.
[0062]
The image receiving material of the present invention basically has a cushion layer, a release layer and an image receiving layer on a support, and receives an ink layer peeled off imagewise from a recording material to form an image.
[0063]
When the softening point of the image receiving layer is lowered, a highly sensitive image receiving material can be obtained. However, when the image receiving layer has a low softening point, fogging occurs. As a method for suppressing the fogging, it is known to add a mat material to the ink layer or the image receiving layer, but satisfactory results have not been obtained. However, an unexpected result was obtained that fog was suppressed when a release layer was provided between the cushion layer and the image receiving layer.
[0064]
It is desirable that the image receiving material has an appropriate heat resistance and is excellent in dimensional stability so that an image is properly formed.
[0065]
As the support for the image receiving material, any material can be used as long as it has good dimensional stability and can withstand the heat during image formation. Specifically, it is described in JP-A 63-193886, page 2, lower left column, lines 12 to 18. A film or sheet can be used. A preferable film thickness is 25-200 micrometers, More preferably, it is 25-100 micrometers.
[0066]
A backing layer can be provided on the back surface of the support (the surface opposite to the surface on which the image receiving layer is provided) in order to provide functions such as running stability, heat resistance, and antistatic properties. The backing layer is formed by applying a backing layer coating solution in which a resin such as nitrocellulose or the like is dissolved in a solvent, or a binder resin and 20 to 30 μm fine particles are dissolved or dispersed in a solvent, to the back surface of the support. Can be formed.
[0067]
The cushion layer provided in the image receiving material of the present invention is a layer having cushioning properties. As a guideline representing the cushioning property referred to here, an elastic modulus or a penetration can be used. For example, the elastic modulus at 25 ° C. is 1 to 250 kg / mm²It is confirmed that a layer having a penetration degree of about 15 to 500 specified in JIS K2530-1976 exhibits a more suitable cushioning property for forming a color proof image for color calibration. However, the required level varies depending on the intended use of the image.
[0068]
A more preferable cushion layer has a TMA softening point (softening point measured by Thermomechanical Analysis) of preferably 60 ° C. or lower, more preferably 45 ° C. or lower.
[0069]
The TMA softening point is obtained by heating the measuring object while applying a constant heating rate and a constant load, and observing the phase of the measuring object.
[0070]
In the present invention, the TMA softening point is defined as the temperature at which the phase of the measurement object starts to change. Measurement of the softening point by TMA can be performed using an apparatus such as Thermoflex (manufactured by Rigaku Corporation). For example, when Thermoflex is used, the measurement temperature range is 25 ° C. to 200 ° C., and the rate of temperature rise is 5 ° C./min. Let it be a point.
[0071]
Preferred properties of the cushion layer of the present invention are not necessarily specified by the type of material, but preferred properties of the material itself include ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polybutadiene resin. , Styrene-butadiene copolymer (SBR), styrene-ethylene-butene-styrene copolymer (SEBS), acrylonitrile-butadiene copolymer (NBR), polyisoprene resin (IR), styrene-isoprene copolymer (SIS) ), Acrylate copolymer, polyester resin, polyurethane resin, acrylic resin, butyl rubber, polynorbornene and the like.
[0072]
Among these, those having a relatively low molecular weight easily satisfy the requirements of the present invention, but are not necessarily limited in relation to the material.
[0073]
Moreover, even if it is a raw material other than the above, the characteristic preferable for a cushion layer is acquired by adding various additives.
[0074]
Examples of the additive include a low melting point material such as wax, a plasticizer, and the like. Specific examples include phthalic acid esters, adipic acid esters, glycol esters, fatty acid esters, phosphoric acid esters, chlorinated paraffins, and the like. In addition, various additives described in, for example, “Practical Handbook for Additives for Plastics and Rubber”, Chemical Industry Co., Ltd. (published in 1970) can be added.
[0075]
The additive amount and the like of these additives may be selected in an amount necessary for expressing desirable physical properties in combination with the base cushion layer material, and is not particularly limited, but generally 10 weight of the cushion layer material amount. % Or less, more preferably 5% by weight or less.
[0076]
As a method for forming the cushion layer, a solution obtained by dissolving the material in a solvent or dispersed in a latex form, a coating method such as a blade coater, a roll coater, a bar coater, a curtain coater, or a gravure coater, an extrusion lamination method using hot melt, etc. Applicable.
[0077]
The preferred film thickness of the cushion layer is 10 μm or more, more preferably 20 μm or more. Further, when retransferring to another transfer target (for example, paper such as coated paper or high-quality paper), a film thickness of 30 μm or more is preferable. When the thickness of the cushion layer is 10 μm or less, missing or chipping may occur during retransfer to the final transfer target.
[0078]
Conventionally, when a material having a low softening point is used as the binder material of the image receiving layer, it can cope with foreign matters and is highly sensitive. However, it has been difficult to use because the mat material sinks after storage and the fog suppression property deteriorates. However, if a release layer having a high Tg (glass transition point) or tensile strength is provided, the matting material can be prevented from sinking even if the binder material of the image receiving layer has a low softening point, so that the storage stability is improved. Remarkably improved. Further, by defining the film thickness according to the material of the binder for the release layer, an image receiving material having good sensitivity and fog could be obtained.
[0079]
  When the TMA softening point of the cushion layer is 40 ° C. or lower, the Tg of the release layer binder is 140 ° C. or higher, or the tensile strength is 5.0.kg / mm ² At the above time, the film thickness is preferably 0.3 to 1.0 μm, and the material Tg is 80 to 140 ° C. or the tensile strength is 3.5 to 5.0.kg / mm ² In this case, the film thickness is preferably 1.0 to 3.0 μm.
[0080]
  When the TMA softening point of the cushion layer is 40 to 50 ° C., the Tg of the material is 140 ° C. or higher or the tensile strength is 5.0.kg / mm ² At the above time, the film thickness is preferably 0.3 to 0.8 μm, and the material Tg is 80 to 140 ° C. or the tensile strength is 3.5 to 5.0.kg / mm ² In this case, the film thickness is preferably 0.8 to 2.5 μm.
[0081]
  Furthermore, when the TMA softening point of the cushion layer is 50 to 60 ° C., the Tg of the material is 140 ° C. or higher or the tensile strength is 5.0.kg / mm ² At the above time, the film thickness is preferably 0.2 to 0.6 μm and the Tg of the material is 80 to 140 ° C. or the tensile strength is 3.5 to 5.0.kg / mm ² In this case, the film thickness is preferably 0.6 to 2.2 μm.
[0082]
If the film thickness is small, fogging and storage stability deteriorate, and if it is large, image defects due to foreign matter are likely to occur. A material having a higher Tg or higher tensile strength can be made thinner, and a lower material requires a thicker film.
[0083]
Specific examples of binders for the release layer include polyester, polyvinyl acetal, polyvinyl formal, polyparabanic acid, polymethyl methacrylate, polycarbonate, ethyl cellulose, nitrocellulose, methyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl chloride, and polystyrene. , Styrenes such as acrylonitrile styrene and those obtained by crosslinking these resins, polyamides, polyimides, polyetherimides, polysulfones, polyethersulfones, aramids and other thermosetting resins having a Tg of 65 ° C. or higher, and cured products of these resins. It is done. As the curing agent, general curing agents such as isocyanate and melamine can be used.
[0084]
When the binder for the release layer is selected according to the above physical properties, polycarbonate, acetal, and ethyl cellulose are preferable from the viewpoint of storage stability. When an acrylic resin is used for the image receiving layer, the release property is improved when the image after laser thermal transfer is retransferred. Particularly preferred.
[0085]
Separately, a layer whose adhesion to the image receiving layer becomes extremely low during cooling can be used as a release layer by adjusting the average particle size, particle size distribution, addition amount, shape and material of the mat material contained in the image receiving layer. can do. Specifically, it can be a layer mainly composed of a heat-melting compound such as waxes and a binder, or a thermoplastic resin.
[0086]
Examples of the hot-melt compound include substances described in JP-A-63-193886. In particular, microcrystalline wax, paraffin wax, carnauba wax and the like are preferably used. As the thermoplastic resin, an ethylene copolymer such as an ethylene-vinyl acetate resin, a cellulose resin, or the like is preferably used.
[0087]
Higher fatty acids, higher alcohols, higher fatty acid esters, amides, higher amines and the like can be added to such a release layer as necessary.
[0088]
Another structure of the release layer is a layer having releasability by melting or softening when heated to cause cohesive failure. Such a release layer preferably contains a supercooling substance.
[0089]
Examples of the supercooled substance include poly-ε-caprolactone, polyoxyethylene, benzotriazole, tribenzylamine, and vanillin.
[0090]
Furthermore, in the peelable layer having another configuration, a compound that decreases the adhesion to the image receiving layer is included. Examples of such compounds include silicone resins such as silicone oil; fluorine resins such as Teflon and fluorine-containing acrylic resins; polysiloxane resins; acetal resins such as polyvinyl butyral, polyvinyl acetal and polyvinyl formal; polyethylene wax and amide wax And solid waxes such as fluorine-based and phosphate-based surfactants.
[0091]
Examples of the method for forming the release layer include a blade coater, a roll coater, a bar coater, a curtain coater, a gravure coater, and other coating methods in which the above materials are dissolved in a solvent or dispersed in a latex form, an extrusion lamination method using hot melt, and the like. It can be applied and formed on the cushion layer. Alternatively, there is a method in which a material obtained by dissolving the raw material in a solvent or dispersed in a latex form on a temporary base is bonded to the cushion layer and the material applied by the above method, and then the temporary base is peeled off.
[0092]
The image receiving layer is composed of a binder, a mat material, and various additives added as necessary.
[0093]
The image receiving layer used in the image receiving material of the present invention preferably has a softening point of 60 ° C. or less by TMA measurement.
[0094]
Specific examples of the image receiving layer binder include adhesives such as polyvinyl acetate emulsion adhesive, chloroprene adhesive, epoxy resin adhesive, natural rubber, chloroprene rubber, butyl rubber, polyacrylate ester, nitrile rubber , Polysulfide, silicone rubber, petroleum resin, etc., recycled rubber, vinyl chloride resin, SBR, polybutadiene resin, polyisoprene, polyvinyl butyral resin, polyvinyl ether, ionomer resin, SIS, SEBS, acrylic resin, Examples thereof include ethylene-vinyl chloride copolymer, ethylene-acrylic copolymer, ethylene-vinyl acetate resin (EVA), vinyl chloride graft EVA resin, EVA graft vinyl chloride resin, vinyl chloride resin, various modified olefins, polyvinyl butyral, and the like.
[0095]
The above resin having a softening point measured by TMA of 60 ° C. or lower is used alone, but may be used by adding an additive to 60 ° C. or lower.
[0096]
  When the ink layer of the recording material does not contain a mat material, the glass transition point is 75 ° C. or higher or the tensile strength is 3.5 kg / mm as the release layer.²When the above materials are selected, it is effective to add a mat material to the image receiving layer. Of the mat materialnumberThe average particle diameter is preferably 0.3 to 2.0 [mu] m larger than the average film thickness of the portion of the image receiving layer where the mat material is not present, and more preferably 0.3 to 1.0 [mu] m larger. If it is 0.3 μm or less, fog is likely to occur, and if it is 2.0 μm or more, the sensitivity is deteriorated. In addition,numberThose having a distribution in which the particle weight of at least twice the average particle diameter is 20% or less are preferable,numberIt is more preferable to have a distribution in which the particle weight that is twice or more the average particle diameter is 5% or less.
[0097]
  As mat materialnumberWhen the particle weight is 20% or less, which is twice or more the average particle diameter, the pressure is uniformly relieved, so that deterioration in storage stability such as blocking can be suppressed.numberIt is more preferable from the viewpoint of storage stability to use a particle having a particle weight of 2% or more of the average particle diameter and 5% or less.
[0098]
When such a mat material is selected, if the film thickness of the image receiving layer is set to 3.0 μm or more, an appropriate mat material is added in accordance with the thickness of the image receiving layer. Therefore, the film thickness of the image receiving layer is preferably 3.0 μm or less. Furthermore, by setting the thickness to 0.5 μm or less, a difference in gloss can be imparted between the image portion and the non-image portion of the image, and when a proof image for printing is formed, a texture similar to that of the printed matter can be imparted. .
[0099]
If the properties are further selected as the mat material, the film thickness limit of the image receiving layer is reduced. A mat material whose volume average particle size is 1.5 to 5.5 μm larger than the average film thickness of the portion of the image receiving layer where the mat material does not exist is effective. Further, the volume average particle size is not present of the mat material of the image receiving layer. It is preferable that it is 2-4 micrometers larger than the average film thickness of a part. The fact that the mat material contains particles having a particle size of 1 μm or less larger than the average film thickness of the portion of the image receiving layer where the mat material does not exist is only 25% or less of the total volume. This is particularly effective for suppressing an increase in yellowness more than necessary.
[0100]
If such a mat material is selected, the material selection range of the release layer is expanded as described above.
[0101]
When a mat material having a particularly large particle diameter is used, a phenomenon called so-called ablation is likely to occur, in which the photothermal conversion layer of the recording material is transferred to the image receiving material due to the heat insulation effect due to the distance between the image receiving material and the recording material being increased. . This phenomenon of ablation is undesirable because it adversely affects the reproduction of the color and fine lines of the image. Occurrence of this phenomenon can be improved by suppressing particles having a particle size of 5.5 μm or more larger than the average film thickness of the mat material where no mat material exists in the image receiving layer to 25% or less of the total volume. By suppressing the particle size of the mat material to a desired particle size distribution, the above effects can be achieved at the same time. Preferably, particles having a particle size 1.5 to 5.5 μm larger than the average film thickness of the portion where the mat material of the image receiving layer is not present are 40% or more of the total volume, and the particle size is 1 μm or less larger than the average film thickness of the image receiving layer By having a particle size distribution that contains no more than 25% of particles and no more than 25% of particles having a particle size that is 5 μm or more larger than the average film thickness of the image receiving layer, the mat material is the average of the portions of the image receiving layer where no mat material exists Particles having a particle size of 2 to 4 μm larger than the film thickness include 50% or more of the total volume, particles having a particle diameter of 1 μm or more larger than the image receiving layer average film thickness are 15% or less, and particles 5 μm or more larger than the average film thickness of the image receiving layer The effect is further increased by having a particle size distribution containing only 15% or less of the diameter particles.
[0102]
The volume average particle size of the mat material is 1.5 to 5 μm larger than the average film thickness of the portion of the image receiving layer where the mat material does not exist, and 15% or less of particles having a particle size 1 μm or more smaller than the volume average particle size, Having a particle size distribution containing only 15% or less of particles having a particle size 1 μm or more larger than the volume average particle size shows particularly good results. In this case, the addition amount of the mat material is 0.02 to 0.2 g / m.²It is preferable that
[0103]
A more preferable mat material is a mat material having a number average particle size 1.5 to 5.5 μm larger than the average film thickness of the portion of the image receiving layer where no mat material exists, and 70% by number of particles having a number average particle size in this range. More preferably, it is contained. In particular, it is desirable that the number average particle diameter is 2 to 4 μm larger than the average film thickness of the portion of the image receiving layer where the mat material does not exist, and 70% by number or more of particles having a number average particle diameter in this range are included.
[0104]
The distribution of the mat material on the surface of the image receiving layer is also important. The number of mat members on the image receiving layer is 200 to 2400 / mm.²It is preferable that Further, the fact that the mat material is spherical makes it possible to effectively improve the performance by adding the mat material. The true spherical shape referred to in the present invention means that the shape of the mat material particles observed with a microscope or the like is almost spherical, and the difference between the major axis and the minor axis is about 20% or less. The mat material is preferably organic fine particles from the viewpoint of sensitivity, and is particularly effective in terms of gloss and haze. Inorganic fine particles having a desired average particle size and particle size distribution are also preferably used for the purpose of securing the adhesion between the recording material and the image receiving material and preventing fogging of the non-image area. However, the ink is transferred onto the particles. Since the rate is much lower than that of organic particles, those having a large particle size often appear as pinhole-shaped defects, particularly in the printed portion of fine lines.
[0105]
Also, the surface reflection is large, which may lead to haze degradation. It is further effective that the relative refractive index of the mat material particles with respect to the binder forming the image receiving layer is 0.9 to 1.1. The refractive index is usually measured by irradiating light of a certain wavelength, and light having a spectral wavelength of sodium of 598 nm is generally used.
[0106]
The binder film thickness of the image receiving layer, which is effective when the above mat material is used, is preferably 0.8 to 3.5 μm.
[0107]
As a material for the mat material, known organic fine particles such as acrylic resin such as PMMA (polymethyl methacrylate), fluorine resin, and silicon resin can be used. In order to increase the strength and solvent resistance of the particles, crosslinked organic fine particles are more preferable.
[0108]
Next, a recording material for heat mode laser thermal transfer used in combination with the image receiving material of the present invention will be described.
[0109]
The recording material has at least an ink layer having a photothermal conversion function on the support, or has a photothermal conversion layer and an ink layer, and a cushion layer between these layers and the support, if necessary. And a release layer.
[0110]
The support is the same as that used for the image receiving material. If an image is formed by irradiating laser light from the recording material side, the support of the recording material is preferably transparent. If the image is formed by irradiating laser light from the image receiving material side, the recording material support need not be transparent.
[0111]
The cushion layer is provided for the purpose of increasing the adhesion between the recording material and the image receiving material. The cushion layer is a layer having heat softening property or elasticity, and a material that can be sufficiently softened and deformed by heating, a material having a low elastic modulus, or a material having rubber elasticity may be used. Specifically, the same polymer as that used for the cushion layer of the image receiving material can be used.
[0112]
The cushion layer can be applied by coating, laminating, or laminating a film to give a certain thickness, and can be finished by coating to obtain surface smoothness.
[0113]
As a method for forming the cushion layer, a method similar to the method for forming the image receiving layer of the image receiving material can be used. It is also possible to use a void-structure resin layer obtained by foaming a heat softening or thermoplastic resin as a special cushion layer. In the case of further forming a sealing cushion layer in which surface smoothness is essential, it is desirable to perform coating by various coating methods. The total thickness of the preferred cushion layer is 2 μm or more, preferably 4 μm or more.
[0114]
If a light-to-heat conversion substance can be added to the ink layer, a light-to-heat conversion layer is not particularly required, but if the light-to-heat conversion substance is not substantially transparent, considering the color reproducibility of the transferred image, light-to-heat conversion is performed separately from the ink layer. It is desirable to provide a layer. The photothermal conversion layer can be provided adjacent to the ink layer.
[0115]
When using a photothermal conversion substance, although it depends on the light source, a substance that absorbs light and efficiently converts it into heat is good.For example, when using a semiconductor laser as a light source, a substance having an absorption band in the near infrared is preferable. Near-infrared light absorbers include, for example, carbon black, cyanine-based, polymethine-based, azulenium-based, squalium-based, thiopyrylium-based, naphthoquinone-based, anthraquinone-based organic compounds, phthalocyanine-based, azo-based, and thioamide-based organic metals. Complexes and the like are preferably used, and specifically, JP-A-63-139191, JP-A-64-33547, JP-A-1-160683, JP-A-1-280750, JP-A-1-293342, and JP-A-2-2074. 3-26593, 3-30991, 3-34891, 3-36093, 3-36 94 items, the 3-36095 JP, same 3-42281 JP, same 3-97589 Patent, compounds described in the 3-103476 Patent and the like. These can be used alone or in combination of two or more.
[0116]
As a binder in the photothermal conversion layer, a resin having a high Tg and a high thermal conductivity, such as polymethyl methacrylate, polycarbonate, polystyrene, ethyl cellulose, nitrocellulose, polyvinyl alcohol, polyvinyl chloride, polyamide, polyimide, polyetherimide, polysulfone, Common heat resistant resins such as polyethersulfone and aramid can be used.
[0117]
Moreover, a water-soluble polymer can also be used as a binder in a photothermal conversion layer. The water-soluble polymer is preferable in that it has good releasability from the ink layer, good heat resistance during light irradiation, and less so-called scattering even when excessively heated. When a water-soluble polymer is used, it is desirable that the photothermal conversion substance is modified to be water-soluble (for example, by introduction of a sulfo group) or dispersed in water. Among water-soluble resins, gelatin is preferable because it hardly causes aggregation of water-soluble infrared absorbing dyes and does not cause stable coating of a light-to-heat conversion layer, storage of a recording medium, color turbidity due to aggregation of infrared absorbing dyes, and sensitivity reduction. Further, increasing the peelability between the photothermal conversion layer and the ink layer leads to an improvement in sensitivity, and therefore it is effective to incorporate various release agents into the photothermal conversion layer. Examples of release agents include silicone release agents (polyoxyalkylene-modified silicone oil, alcohol-modified silicone oil, etc.), fluorine-based surfactants (perfluorophosphate ester-based surfactants), and other various surfactants. Etc. are effective.
[0118]
The film thickness of the photothermal conversion layer is preferably from 0.1 to 3 μm, more preferably from 0.2 to 1.0 μm. The content of the photothermal conversion substance in the photothermal conversion layer is usually determined such that the absorbance at the wavelength of the light source used for image recording is 0.3 to 3.0, more preferably 0.7 to 2.5. it can.
[0119]
If the light-to-heat conversion layer is inferior in adhesion to the cushion layer, it may cause film peeling and color turbidity when peeling off the ink sheet from the image receiving sheet during light irradiation or after thermal transfer. It is also possible to provide an adhesive layer.
[0120]
As the adhesive layer, it is necessary to select materials so that the adhesive strength between the photothermal conversion layer and the adhesive layer and the cushion layer at the time of ink transfer is larger than the ink peel strength at the time of ink transfer. Generally, conventionally known adhesives such as polyester, urethane, and gelatin can be used. In order to obtain the same effect, a tackifier and an adhesive can be added to the cushion layer instead of providing the adhesive layer. If the adhesive layer is poor in cushioning properties and heat softening properties, the effect of the cushion layer is reduced. Therefore, it is preferable that the adhesive layer is as thin as possible. The preferred film thickness is 0.5 μm or less, but there is no limitation as long as the adhesive layer can fulfill the purpose of the cushion layer.
[0121]
In addition to this, a vapor deposition film can also be used as the photothermal conversion layer. Carbon black, gold, silver, aluminum, chromium, nickel, antimony, tellurium, bismuth described in JP-A No. 52-20842, A vapor deposition layer of metal black such as selenium can be used. The photothermal conversion material may be the color material itself of the ink layer, and is not limited to the above, and various materials can be used.
[0122]
The ink layer means a layer which can be transferred for each layer containing a colorant, a binder and the like by being melted or softened when heated, and may not be transferred in a completely melted state.
[0123]
Examples of the colorant include inorganic pigments (titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, cadmium sulfide, iron oxide and lead, zinc, barium and calcium chromates) and organic pigments (azo, Pigments and dyes (acid dyes, direct dyes, disperse dyes, oil-soluble dyes) such as thioindigo, anthraquinone, anthanthrone, triphendioxazine pigments, vat dye pigments, phthalocyanine pigments and derivatives thereof, quinacridone pigments, Metal-containing oil-soluble dyes or sublimable dyes).
[0124]
For example, when a color proof material is used, yellow, magenta, and cyan are C.I. I. 21095 or C.I. I. 21090, C.I. I. 15850: 1, C.I. I. 74160 pigment is preferably used.
[0125]
The content of the color material in the ink layer is not particularly limited, but is usually in the range of 5 to 70% by weight, preferably 10 to 60% by weight.
[0126]
Examples of the binder for the ink layer include a heat-meltable substance, a heat-softening substance, and a thermoplastic resin. The hot-melt material is usually a solid or semi-solid material having a melting point measured using Yanagimoto MJP-2 type in the range of 40 to 150 ° C. Specifically, plant waxes such as carnauba wax, wood wax, aucuric wax and espal wax; animal waxes such as beeswax, insect wax, shellac wax and whale wax; paraffin wax, microcrystal wax, polyethylene wax, ester wax, acid Petroleum waxes such as waxes; and waxes such as mineral waxes such as montan wax, ozokerite, and ceresin. In addition to these waxes, palmitic acid, stearic acid, margaric acid, behenic acid, etc. Higher fatty acids; higher alcohols such as palmityl alcohol, stearyl alcohol, behenyl alcohol, marganyl alcohol, myricyl alcohol, eicosanol; higher fatty acid esters such as cetyl palmitate, myricyl palmitate, cetyl stearate, myricyl stearate; acetamide Amides propionic acid, palmitic acid amide, stearic acid amides such as amide wax; and stearylamine, behenylamine, like higher amines such as palmityl amine.
[0127]
Thermoplastic resins include ethylene copolymers, polyamide resins, polyester resins, polyurethane resins, polyolefin resins, acrylic resins, vinyl chloride resins, cellulose resins, rosin resins, polyvinyl alcohol resins. Resins such as resins, polyvinyl acetal resins, ionomer resins, petroleum resins; elastomers such as natural rubber, styrene butadiene rubber, isoprene rubber, chloroprene rubber, diene copolymer; ester gum, rosin maleic resin, rosin phenol resin And rosin derivatives such as hydrogenated rosin; and polymer compounds such as phenol resin, terpene resin, cyclopentadiene resin, and aromatic hydrocarbon resin.
[0128]
A thermal transfer layer having a desired thermal softening point or thermal melting point can be formed by appropriately selecting the above-mentioned hot-melt material and thermoplastic material.
[0129]
In order to secure the dispersibility of the pigment and obtain a good color reproduction, it is effective to use various dispersants.
[0130]
Other additives include a plasticizer that increases the sensitivity by plasticizing the ink layer, a surfactant that improves the coatability of the ink layer, and submicron to micron order particles that prevent blocking of the ink layer. (Matte material) can be added.
[0131]
A preferable thickness of the ink layer is 0.2 to 2 μm, and more preferably 0.3 to 1.5 μm. In particular, high sensitivity can be obtained when the thickness is 0.8 μm or less.
[0132]
As an exposure method for heat mode recording, there are a method in which the recording material and the image receiving material are in close contact with each other, and a method in which the recording material is exposed from the support side, and a method in which the exposure is performed through the image receiving material.
[0133]
When exposure is performed from the support side of the recording material, a colorant capable of absorbing heat rays is added to the image receiving layer and / or cushion layer so that light that cannot be absorbed by the recording material is absorbed by the image receiving layer and / or cushion layer. Also, efficient use of heat is effective in improving transferability.
[0134]
In the latter case, in order to make the ink layer absorb the energy of the light source without waste, the transmittance with respect to the wavelength of the light source through the image receiving material is preferably 70% or more, more preferably 80% or more. For this purpose, it is necessary to use a support and cushion layer having good transparency and to reduce reflection at the back coat surface of the support and the interface between the support and the cushion layer. As a method for reducing the reflection at the interface between the support and the cushion layer, it is preferable to reduce the refractive index of the cushion layer by 0.1 or more relative to that of the support.
[0135]
【Example】
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the aspect of this invention is not limited to this. First, the invention of configuration A will be described.
[0136]
Example 1
(Creation of recording material)
Apply a toluene solution of SEBS (manufactured by Shell Chemical: EV-250) to a transparent PET (polyethylene terephthalate: T-100 manufactured by Diafoil Hoechst) with a thickness of 75 μm with a wire bar. The photothermal conversion layer coating liquid having the following composition is applied on the wire bar so that the absorbance at 830 nm is 1.0 because the dry film thickness is about 0.25 μm, and further the ink layer coating having the following composition is applied thereon. The liquid was coated with a wire bar so as to have a dry film thickness of about 0.5 μm to obtain a recording material.
[0137]
In addition, the part in an Example shows the weight part of raw material solid content.
[0138]
Photothermal conversion layer coating solution
7.0 parts of polyvinyl alcohol (Kuraray: C-506)
IR absorbing dye (IR-1) 3.0 parts
90.0 parts of water
Ink layer coating liquid
Magenta pigment methyl ethyl ketone dispersion 3.0 parts
(Daiichi Seika: Brilliant Carmine 6B)
Styrene / acrylic resin (manufactured by Sanyo Kasei: Hymer SBM43F) 6.0 parts
Ethylene / vinyl acetate resin 0.5 parts
(Mitsui Deyupon Poly Chemicals: EV40Y)
Silicon resin particles (Toshiba Silicone: Tospearl 120) 0.5 parts
Methyl ethyl ketone 90.0 parts
[0139]
[Chemical 1]

[0140]
(Creation of image receiving material)
Apply a cushion layer coating solution having the following composition to 100 μm thick transparent PET (supra: T-100) with an applicator so as to have a dry film thickness of about 30 μm. Apply the liquid with a wire bar so that the dry film thickness is about 2.0 μm, and then apply the image receiving layer coating liquid with the following composition on the wire bar so that the dry film thickness is about 0.4 μm. To obtain an image receiving material.
[0141]
Cushion layer coating solution
Acrylic latex (manufactured by Kanebo NSC: A5801)
Release layer coating solution
Methylcellulose (Shin-Etsu Chemical Co., Ltd .: N10G) 5.0 parts
Isopropyl alcohol 95.0 parts
Image-receiving layer coating solution
Acrylic latex (supra: A5801)
In the image receiving material, samples having different materials for the cushion layer and the image receiving layer are prepared, and the following heat mode transfer is performed using these and the recording material, and sensitivity and fog are evaluated based on the evaluation method described below. And storage stability was evaluated.
[0142]
(Heat mode transfer)
1 / e of a semiconductor laser with a wavelength of 830 nm²In contrast to an optical system having a spot diameter of 8 .mu.m, the recording material and the image receiving material, which are brought into close contact with a drum-like decompressor at 400 torr, are rotated at a linear velocity of 600 cm / sec. Transfer was performed with exposure variable to 100 mW.
[0143]
<sensitivity>
The density of the solid image transferred by changing the laser power on the exposed surface was measured, and the power at which the density was constant was determined.
[0144]
Power figures: Evaluable samples
-: Sample that cannot be evaluated (blocking occurs, fog cannot be measured, matting agent is excessive) <fog>
A 50% halftone dot pattern was exposed, and the untransferred portion of the obtained transferred image was transferred and evaluated for visual evaluation on a 6-point scale.
[0145]
○: No fogging
○ △: About 25% of the image has fog
Δ: About 50% of the image is fogged
Δ: fogging is present in about 75% of the image
×: fog on the entire image
-: Fogging is impossible after blocking.
<Foreign matter>
A 20 μm fiber (yarn dust) was sandwiched between the image receiving material and the recording material, and then exposure was performed. The image transfer around the fiber was observed and evaluated in four stages.
[0146]
○: No image transfer omission around thread dust
○ △: Image transfer missing about 50 μm along the shape of yarn dust
Δ: The transfer density at the periphery decreases along the shape of the thread dust.
×: Image transfer omission of about 2 mm occurs around the thread dust
<Preservability>
The image receiving material surface and the backing layer surface of the image receiving material are overlapped, and the load is 50 g / cm.²And subjected to a thermal acceleration test at 55 ° C. for 7 days to evaluate blocking and transferability (fogging, sensitivity) after the test. The transferability was evaluated by the method described above, and the blocking was evaluated by the following four stages.
[0147]
A: 100 g / cm²No blocking even with a load of
Y: No blocking
Δ: Partial peeling of the image receiving layer occurs
X: Completely blocking
Comparative Example 1
(Creation of image receiving material)
In the image receiving material of Example 1, an image receiving material was prepared in the same manner except that the image receiving layer coating solution was changed to the following composition.
[0148]
Image-receiving layer coating solution
10 parts acrylic resin (Mitsubishi Rayon: BR113)
45 parts of methyl ethyl ketone
45 parts isopropyl alcohol
Table 1 shows the evaluation of sensitivity according to the difference in softening point of the image receiving layer.
[0149]
[Table 1]

[0150]
It can be seen that the softer the image receiving layer, the higher the sensitivity.
[0151]
Example 2
(Creation of recording material)
A recording material was prepared in the same manner as in the recording material of Example 1, except that the ink layer coating liquid was changed to the following composition.
[0152]
Ink layer coating liquid
Magenta pigment methyl ethyl ketone dispersion 3.0 parts
(Previous: Brilliant Carmine 6B)
Styrene / acrylic resin (supra: Heimer SBM43F) 7.5 parts
Ethylene / vinyl acetate resin (supra: EV40Y) 0.5 part
Silicone resin particles (supra: Tospearl 120) 2.0 parts
Methyl ethyl ketone 90.0 parts
(Creation of image receiving material)
In the image receiving material of Example 1, the composition up to the release layer was applied and the composition ratio of the image receiving layer coating solution composed of the following materials was changed so that the dry film thickness was about 0.4 μm. .
[0153]
Image-receiving layer coating solution
Acrylic latex (supra: A5801) Solid content 55%
Mat material (PMMA fine particles made by Soken Chemical: MR2HG, average weight 13% more than twice the average particle size 2.2μm)
Using the recording material and the image receiving material, heat mode transfer was performed as follows, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.
[0154]
(Heat mode transfer)
A recording material and an image receiving material, which are closely attached to a drum-like decompressor at 120 torr, are made up of 1 / e of a YAG laser having a wavelength of 1064 nm.²Using an optical system with a spot diameter of 12 μm and an exposure pitch of 10 μm, transfer was performed by changing the power on the exposed surface from 2 to 4 W at a linear velocity of 20000 cm / sec.
[0155]
[Table 2]

[0156]
Those containing a matting agent have less fogging, and those having a low softening point have higher sensitivity.
[0157]
Example 3
The matting agent of the image-receiving layer of the same image-receiving material as in Example 2 was changed as follows to prepare an image-receiving material coated so that the dry film thickness of the portion where no mat material was present was about 1.5 μm. Using the recording material described in Example 2, heat mode transfer was performed in the same manner as in Example 2 for evaluation.
[0158]
A: PMMA particles (average particle size 5.6 μm, average weight 30% more than twice the average particle size)
B: MR2HG (supra, Soken Chemicals: MR2HG, average particle size 2.2 μm, average weight 13% more than twice the average particle size)
C: MX-21S (manufactured by Soken Chemical Co., Ltd .: average particle diameter 2.1 μm, average weight 2% or more of average particle diameter 1% or less)
D: MP-1400 (manufactured by Soken Chemical Co., Ltd .: average particle size of 1.5 μm, average weight of 2% or more and 1% or less of average weight)
Table 3 shows the evaluation results of sensitivity, fogging, and storage stability due to differences in the average particle size of the mat material of the image-receiving layer and the average weight (hereinafter referred to as particle size distribution) of at least twice the average particle size.
[0159]
[Table 3]

[0160]
Using a mat material having a particle size slightly larger than the image receiving layer and having a small particle size distribution provides higher sensitivity and less fogging.
[0161]
Example 4
  Change the glass transition point and tensile strength of the release layer binder as follows:, EV40Y, A5801 and AD92 (all TMA softening point 60 ° C. or less) are used as a cushion layer binder.Example 2 was the same as Example 2, except that the image receiving material using MR2HG (described above) as the mat material and the recording material of Example 2 were used and evaluated in the same manner as in Example 2.
[0162]
E: Polycarbonate (Mitsubishi Gas Chemicals: PCZ200)
F: Polyvinyl acetal (manufactured by Sekisui Chemical: ESREC KS-1)
G: Ethylcellulose (Shin-Etsu Chemical Co., Ltd .: N10G)
H: Polyester (Unitika: UE3300)
Tables 4, 5 and 6 show the relationship between the physical properties, film thickness, and storage stability of the release layer.
[0163]
[Table 4]

[0164]
[Table 5]

[0165]
[Table 6]

[0166]
It can be seen that the optimum point of fog, sensitivity, and storage stability can be obtained according to the physical properties of the binder of the release layer and the film thickness.
[0167]
Example 5
Using the same image receiving material as in Example 2 and the recording material of Example 2 except that the film thickness of the image receiving layer was changed as follows, heat mode transfer was performed and evaluated as follows.
[0168]
Table 7 shows the results obtained by measuring the film thickness of the image receiving layer and the gloss of the image area and non-image area after secondary transfer.
[0169]
[Table 7]

[0170]
By changing the film thickness of the image receiving layer, the gloss of the image after the secondary transfer can be changed according to the application.
[0171]
Example 6
This embodiment corresponds to configuration B.
[0172]
(Creation of recording material)
A transparent PET (Diafoil Hoechst: T100G, # 25) having a thickness of 25 μm was used as a support, and a release layer coating solution having the following composition was applied and dried thereon with a reverse roll coater. A 3 μm release layer was formed.
[0173]
Release layer coating solution
Release layer binder liquid * 29 parts
Cross-linking agent (Sumitomo Chemical: Sumire's Resin 613) 0.3 parts
70.7 parts of water
* The release layer binder solution is a polyvinyl alcohol aqueous solution (manufactured by Nippon Gosei Kagaku: 9.5% aqueous solution of Gohsenol EG-30), 97.2 parts, a crosslinking accelerator (manufactured by Sumitomo Chemical: Sumirez Resin ACX-P). A binder liquid having a solid content of 9.5% was prepared from 3 parts, 0.3 part of a fluorosurfactant (manufactured by Sumitomo Chemical Co., Ltd .: Sumirez Resin FP-150) and 1.2 parts of water.
[0174]
On the release layer, an ink layer coating liquid having the following composition was applied and dried by wire bar coating to form an ink layer.
[0175]
Yellow recording material(Ink layer coating solution)
Yellow Pigment Dispersion 1 16.9 parts
(10 parts of Disazo Yellow AAA with 2 parts of dispersant
Dispersed in 88 parts of methyl ethyl ketone)
Yellow pigment dispersion 2 1.9 parts
(10 parts of Disazo Yellow HR with 3 parts dispersant
Dispersed in 87 parts of methyl ethyl ketone)
Styrene / acrylic resin 2.4 parts
(Previous: Heimer SBM73F)
0.2 parts of ethylene / vinyl acetate resin (supra: EV40Y)
Fluorine-based surfactant (Asahi Glass: Surflon S-382) 0.1 part
Methyl ethyl ketone 48.1 parts
Cyclohexanone 30.4 parts
The dry film thickness was 0.55 μm.
[0176]
Magenta recording material(Ink layer coating solution)
12 parts of magenta pigment dispersion
(15 parts of Brilliant Carmine 6B with 4.5 parts dispersant)
Dispersed in 20.5 parts of methyl ethyl ketone)
Styrene / acrylic resin 2.4 parts
(Previous: Heimer SBM73F)
0.2 parts of ethylene / vinyl acetate resin (supra: EV40Y)
Fluorine-based surfactant (supra: Surflon S-382) 0.1 part
Methyl ethyl ketone 60.5 parts
Methyl isobutyl ketone 24.8 parts
The dry film thickness was 0.56 μm.
[0177]
Cyan recording material(Ink layer coating solution)
Cyan pigment dispersion 5.1 parts
(30 parts phthalocyanine blue with 5 parts dispersant
Dispersed in 65 parts of methyl ethyl ketone)
2.9 parts of styrene / acrylic resin
(Previous: Heimer SBM73F)
Ethylene / vinyl acetate resin (supra: EV40Y 0.2 parts
Fluorine-based surfactant (supra: Surflon S-382) 0.1 part
Methyl ethyl ketone 50.3 parts
Methyl isobutyl ketone 42 parts
The dry film thickness was 0.54 μm.
[0178]
Black recording material(Ink layer coating solution)
4.9 parts of black pigment dispersion
(33 parts of carbon black with 6.6 parts of dispersant
Dispersed in 60.4 parts of methyl ethyl ketone)
Cyan pigment dispersion (supra) 0.9 parts
Violet pigment dispersion 1.2 parts
(10 parts of dioxazine violet with 5 parts dispersant
Dispersed in 85 parts of methyl ethyl ketone)
Styrene / acrylic resin 3.9 parts
(Previous: Heimer SBM73F)
Ethylene / vinyl acetate resin (supra: EV40Y) 0.3 parts
Fluorine-based surfactant (supra: Surflon S-382) 0.1 part
Methyl ethyl ketone 57.9 parts
Methyl isobutyl ketone 30.8 parts
The dry film thickness was 0.72 μm.
[0179]
On each of the ink layers, a photothermal conversion layer coating solution having the following composition was applied and dried by wire bar coating to form a photothermal conversion layer having a wavelength 830 nm transmittance of 0.8. The application amount of this photothermal conversion layer is 0.6 g / m.²Met.
[0180]
Photothermal conversion layer coating solution
Polyvinyl alcohol 6 parts
(Nippon GOHSEI: Gohsenol EG-30)
4 parts of carbon black dispersion
(Dai Nippon Ink: SD-9020)
0.2 parts of surfactant
490 parts of water
On the other hand, a backcoat layer coating solution having the following composition is applied by wire bar coating on a transparent PET (previously: T100G, # 100) film having a thickness of 100 μm to form a backcoat layer having a dry film thickness of 0.6 μm. did.
[0181]
Backcoat layer coating solution
79 parts of polyvinyl alcohol
(Nippon GOHSEI: Gohsenol EG-05)
Fluorine surfactant 5 parts
(Sumitomo Chemical: Sumires resin FP-150)
Antistatic agent (Matsumoto Yushi: Fcol 214) 10 parts
Matt material (PMMA particles having a volume average particle diameter of 5.6 μm) 6 parts
90 parts of water
An intermediate layer coating solution having the following composition was applied to the back surface of the back coat layer by wire bar coating to form an intermediate layer having a dry film thickness of 6 μm.
[0182]
Intermediate layer coating solution
SEBS (Shell Chemical: Clayton G1657) 14 parts
Tackie Fire (Arakawa Chemical: Superester A100) 6 parts
Methyl ethyl ketone 10 parts
80 parts of toluene
Next, after the light-to-heat conversion layer of each sheet provided with the ink layer and the light-to-heat conversion layer is combined with the intermediate layer by roll touch, the film with the release layer is peeled off, and yellow, magenta , Cyan and black recording materials were obtained.
[0183]
(Creation of image receiving materials 1 to 9)
A backcoat layer (dry film thickness: 0.6 μm) having the same composition as that used in the preparation of the intermediate layer was provided on PET (thickness: T-100) having a thickness of 100 μm.
[0184]
On the opposite side of the back coat layer, an acrylic emulsion (manufactured by Zeneca: Neokrill A-1052) was applied with an applicator so that the dry film thickness was about 35 μm to form a cushion layer. On top of this, a release layer coating solution having the following composition was applied and dried by wire bar coating to form a release layer having a thickness of about 1.5 μm.
[0185]
Release layer coating solution
Polyester (Unitika: UE-3300) 8 parts
92 parts isopropyl alcohol
For the image-receiving layer coating solution, 4% of the above-mentioned surfactant (Smileze Resin FP-150) is 4% of the solid content of the latex with respect to polyacrylic acid latex (manufactured by Kanebo NSC: Yodosol A5801, resin content 55%). Further, a mat material was added at a desired ratio, and a liquid having a solid content of 12% was applied by wire bar coating to prepare an image receiving material.
[0186]
(Creation of image receiving materials 10 to 24)
  Similar to the image receiving materials 1 to 9, a 100 μm-thick PET (previously: T-100) provided with a backcoat layer was coated with acrylic latex (manufactured by Kanebo NSC: Yodosol AD).92) Was applied with an applicator to a dry film thickness of about 30 μm to form a cushion layer.
[0187]
On top of that, a release layer coating solution having the following composition was applied and dried by wire bar coating to form a release layer having a thickness of about 1.7 μm.
[0188]
Release layer coating solution
10 parts of ethylcellulose (Dow Chemical: Etcel 7)
90 parts isopropyl alcohol
Furthermore, using polyacrylic acid latex (manufactured by Kanebo NSC: Yodosol A5805, resin content 55%) as a binder, mat material is added at a desired ratio, and coating is performed by wire bar coating as a liquid with a solid content of 12%. An image receiving sheet was prepared.
[0189]
Using these image receiving materials and the recording material, heat mode transfer was performed as follows.
[0190]
(Image formation by laser thermal transfer)
After the image receiving material is wound around the drum surface so that the back surface is in contact, the recording material is wrapped so that the image receiving layer and the ink layer are in contact with each other, and vacuum-adhered by sucking from the suction holes and suction grooves on the drum surface for recording. Laser exposure was applied from the back side of the material to transfer the image onto the image receiving layer.
[0191]
Laser exposure is modulated using halftone dot image data separated into four colors, and the recording material is modulated by corresponding color separation data while changing the order of Y, M, C, K (yellow, magenta, cyan, black). Finally, a full-color image was obtained on the image receiving layer using the prepared laser.
[0192]
(Image transfer by laminator)
The image-receiving layer of the image-receiving material onto which the four-color image has been transferred is layered on the printing paper (Mitsubishi Paper: Tohoku Art), and the image is obtained by applying pressure and heating at a pressure of 2 kg, a roll temperature of 150 ° C., and a roll peripheral speed of 20 mm / sec. Transcribed.
[0193]
Each characteristic of the transferred image was evaluated based on the following evaluation method.
[0194]
<Fog>
A 50% halftone dot pattern was exposed, and the portion where the unexposed portion of the obtained transferred image was transferred was visually evaluated as fog.
[0195]
A: No fogging
○: Slightly unmeasurable fog that does not adversely affect the image impression
Δ: There is fog of 2 mm or less
X: There is fog of 5 mm or more
<Air leakage defect>
The presence or absence of defects due to floating due to insufficient air escape between the image receiving material and the recording material was evaluated.
[0196]
A: No defect
○: There is a defect of 1mm or less, but there is little influence on the image impression
Δ: There is a defect of 5 mm or less
×: There is a defect of 1cm or more
<Yellow taste>
The color of the non-image area after transfer to the printing paper was visually evaluated.
[0197]
A: No yellowish color is observed
○: Almost no yellowish color
Δ: Slightly yellowish color is observed
×: Clearly yellowish
<Glossy>
The 60-degree specular gloss was measured based on Method 3 of the specular gloss measurement method defined in JIS Z-8741-1983. The gloss approximating the printed material is about 40 to 55.
[0198]
<Ablate>
The transferred image was visually evaluated for the presence or absence of contamination due to the transfer of the photothermal conversion layer of the recording material.
[0199]
A: No ablation
○: Almost no ablation
Δ: Ablated but very small
×: Ablation is present and color tone is not reproduced
<Ink transfer rate>
The ratio (transmission density / ink layer density) of the transmission density of the ink layer of the recording material and the transmission density of the solid part after image formation transfer to the image receiving material is shown in%.
[0200]
The results are shown in Tables 8-12.
[0201]
[Table 8]

[0202]
[Table 9]

[0203]
[Table 10]

[0204]
[Table 11]

[0205]
[Table 12]

[0206]
The results in Tables 8 and 11 are evaluations using a magenta recording material, the results in Table 9 are evaluations using a yellow recording material, and the results in Table 10 are evaluations using a cyan recording material. Table 12 shows the evaluation using the black recording material.
[0207]
The volume average particle size of the mat material was measured using a Coulter Counter TA-II (manufactured by Nikka Kikai Co., Ltd.) after diluting about 1 g of the sample with 200 ml of pure water and then dispersing it with an ultrasonic disperser for 15 minutes. On the other hand, the number average particle size was measured by observing with an electron microscope after taking a very small amount of the mat material dispersion in a preparation and drying it.
[0208]
Further, the number of mat members was calculated from the number of coated samples observed and photographed with an optical microscope and existing within an area of 200 μm × 200 μm.
[0209]
As is apparent from Tables 8 to 12, an image receiving material having good performance was obtained by using a mat material in accordance with the contents of the present invention. Further, as mat materials having different reflectivities, from polymethyl methacrylate particles having a refractive index of 1.48 to 1.49 at 598 nm, synthetic silica particles having 1.46, and glass beads having 1.67, When an image receiving material was prepared by selecting an approximate material, unnecessary reflections were observed in the transferred image with glass beads, and the impression of the final image was not preferable. The refractive index during layer formation of the acrylic acid latex resin used was 1.4 to 1.5.
[0210]
Since the synthetic silica particles are amorphous, the gloss reduction with respect to the addition rate is remarkable, and the range in which various performances can be satisfied is extremely narrow. Also, the saturation of the transferred image tends to decrease.
[0211]
When the solid transfer portion was observed, there were many portions where the portions where the mat material existed were minute transfer omissions.
[0212]
Further, with respect to the image receiving materials 3, 5, 7, 18, and 20, halftone images were overlaid and recorded using recording materials of all colors to obtain full color images.
[0213]
In either case, there was no fog or defect, and an image very close to the printed matter could be obtained. Overlapping recording was performed in the order of yellow, magenta, cyan, and black, but the recordings made later did not decrease the transfer rate, and it was excellent without excessively hiding the color tone of the lower layer after being laminated on paper. Secondary color reproducibility was obtained.
[0214]
【The invention's effect】
According to the recording method using the image receiving material of the present invention, photothermal conversion heat mode recording capable of high-speed recording capable of sufficient adhesion by vacuum adhesion, excellent transportability, good transferability, and the like can be performed. Furthermore, the image-receiving material of the present invention enables clear image transfer even on a permanent support having low smoothness, and the gloss of the transferred image can be increased to the same level as that of a printed matter.
[Brief description of the drawings]
FIG. 1 is a perspective view showing that a photothermal conversion type heat mode image receiving material of the present invention is overlapped with a recording material and wound around a drum-shaped decompressor.
FIG. 2 is a cross-sectional view showing a basic configuration of a drum-shaped decompressor.
FIG. 3 is a cross-sectional view showing that an image receiving material and a recording material are brought into close contact with a flat plate decompressor.
FIG. 4 is an overall configuration diagram showing the periphery of a drum-like decompressor and a decompressor.
FIG. 5 is a cross-sectional view showing an example of a layer structure of the photothermal conversion heat mode image receiving material of the present invention.
[Explanation of symbols]
1 Pressure roll
2 Depressurization hole (2-1 indicates open state, 2-2 indicates closed state)
3 Heat mode recording material (3-1 is yellow, 3-2 is magenta, 3-3 is cyan, 3-4 is black recording material)
4 Heat mode image-receiving material
5 Heat mode recording material supply means
6 Heat mode image receiving material supply means
7 Pressure reducer holding part
8 Optical writing means
9 Case
10 Pressure reducing hole valve
11 Support
12 Cushion layer
13 Release layer
14 Image receiving layer
15 Backcoat layer (not necessarily required)

Claims (8)

In the photothermal conversion heat mode image receiving material having a cushion layer, a release layer, and an image receiving layer on a support, the binder of the cushion layer and the image receiving layer has a TMA softening point of 60 ° C. or less and is selected from the following material group: Photothermal conversion type heat mode image receiving material characterized by
Ethylene-vinyl acetate resin (EVA), acrylic resin. The binder of the release layer is selected from the following material group, the glass transition point is 75 ° C. or higher, the tensile strength is 3.5 kg / mm ² or more, and the thickness of the release layer is 0.2 to 3.0 μm. The photothermal conversion type heat mode image-receiving material according to claim 1.
Polyester resins, polyvinyl acetal resins, polycarbonate resins, ethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, and cured products of these resins.   3. A mat material is contained in the image receiving layer, and the number average particle diameter of the mat material is 0.3 to 2.0 [mu] m larger than the average film thickness of the portion of the image receiving layer where the mat material does not exist. Photothermal conversion type heat mode image receiving material. The TMA softening point of the binder of the cushion layer is 40 ° C. or lower, the glass transition point of the binder of the release layer is 140 ° C. or higher, or the tensile strength is 5.0 kg / mm ² or higher, and the film thickness is 0.3 to 1.0 μm. The glass transition point is 80 to 140 ° C., the tensile strength is 3.5 to 5.0 kg / mm ² , and the film thickness is 1.0 to 3.0 μm. Photothermal conversion type heat mode image receiving material. The TMA softening point of the binder of the cushion layer is 40-50 ° C., the glass transition point of the binder of the release layer is 140 ° C. or higher, or the tensile strength is 5.0 kg / mm ² or higher, and the film thickness is 0.3-0. The glass transition point is 80 to 140 ° C, the tensile strength is 3.5 to 5.0 kg / mm ² , and the film thickness is 0.8 to 2.5 µm. Photothermal conversion type heat mode image receiving material. The cushion layer binder has a TMA softening point of 50-60 ° C., the release layer binder has a glass transition point of 140 ° C. or higher, or a tensile strength of 5.0 kg / mm ² or higher, and a film thickness of 0.2-0. 4. A glass transition point of 80 to 140 [deg.] C., a tensile strength of 3.5 to 5.0 kg / mm < ² >, and a film thickness of 0.6 to 2.2 [mu] m. Photothermal conversion type heat mode image receiving material. The photothermal conversion heat mode image-receiving material according to any one of claims 3 to 6, which has a particle size distribution in which a particle weight that is at least twice the number average particle size of the mat material is 20% or less.   The photothermal conversion heat mode image receiving material according to claim 1, wherein the image receiving layer has a thickness of 0.4 to 3.0 μm.

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