JP2004272161A - Heat developing device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat developing device capable of preventing a heat drum in the heat developing device from being dirtied over a long period, preventing the transfer of dirt on a heat developing photosensitive material which is thermally developed and obtaining images of high quality and having high durability. <P>SOLUTION: In the heat developing device for thermally developing the heat developing photosensitive material having a heat developing photosensitive layer containing silver salt and a reducing agent at least on one face of a support body and a layer for protecting the photosensitive layer, the heat drum of the heat developing device or a counter roller is coated with non-fluorinated polysiloxane and the coat layer is further coated with a fluorinated hydrocarbon polymer. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００４６】
【化５】

【００４７】
上記ポリマーの熱処理後の数平均重合度は、１００〜１００００程度の範囲を適宜選択することができる。上記範囲外でも可能であるが、数平均重合度が１００未満であると充分な機械的強度及び弾性が得られず、数平均重合度が１００００を越えると組成物の加工性が劣化し好ましくない。
【００４８】
非フッ素化ポリシロキサンの合成方法は、例えば、特開平５−１８６７００号の記載を参考にして容易に合成することができる。
【００４９】
非フッ素化ポリシロキサンの分子間架橋は、ケイ素原子に水素原子が結合したシリルハイドロジェン基（Ｓｉ−Ｈ）を持つポリシロキサン分子とビニル基（例えば、ＣＨ_２＝ＣＨ−ＣＯＯ−、ＣＨ_２＝Ｃ（ＣＨ_３）ＣＯＯ−）を持つ非フッ素化ポリシロキサン分子との間を付加反応架橋させることにより硬度を上げることができる。Ｓｉ−Ｈ基を活性化する架橋触媒として金属触媒が好ましく、白金、パラジウム、ルテニウム、イリジウム等のハロゲン化物、或いは配位子としてカルボニル基、水酸基、アミノ基、シアノ基、チオシアン基を持つ錯体化合物等を挙げることができる。また、ビニル基を持つ非フッ素化ポリシロキサン分子同士を分子間架橋させてもよい。ビニル基を活性化する触媒として、有機過酸化物触媒を挙げることができる。
【００５０】
以下に、有機過酸化物触媒として好ましい具体例を挙げるが、本発明はこれらに限定されるものではない。
（Ｕ−１）メチルエチルケトンパーオキサイド
（Ｕ−２）シクロヘキサノンパーオキサイド
（Ｕ−３）２，４−ジクロロベンゾイルパーオキサイド
（Ｕ−４）ビス−３，３，５−トリメチルヘキサノイルパーオキサイド
（Ｕ−５）ラウロイルパーオキサイド
（Ｕ−６）ベンゾイルパーオキサイド
（Ｕ−７）クメンハイドロパーオキサイド
（Ｕ−８）ジクミルパーオキサイド
（Ｕ−９）ジ−ｔ−ブチルパーオキサイド
（Ｕ−１０）３，３，５−トリメチルシクロヘキサノンパーオキサイド
（Ｕ−１１）２，２−ジ−ｔ−ブチルパーオキシブタン
（Ｕ−１２）ｔ−ブチルパーオキシ−２−エチルヘキサノエート
（Ｕ−１３）ｔ−ブチルパーオキシベンゾエート
（Ｕ−１４）ジ−２−エチルヘキシルパーオキシジカーボネート
（Ｕ−１５）ジイソプロピルパーオキシジカーボネート
（Ｕ−１６）ｔ−ブチルパーオキシイソプロピルカーボネート
上記架橋剤としての金属触媒や過酸化物触媒は、非フッ素化ポリシロキサンの塗設前に添加しておき、塗布液の状態で予め数平均重合度を上げておいてもよいし、塗設後８０〜４００℃、好ましくは１２０〜２００℃の熱処理により数平均重合度を上げて、最終的な平均組成の非フッ素化ポリシロキサンとすることもできる。
【００５１】
貴金属触媒や過酸化物触媒は、適当な有機溶媒、例えばトルエン、キシレン、ジオキソラン、アセトン、メチルエチルケトン等に溶かして添加してもよいし、微粒子状態にした固形のまま使用してもよい。
【００５２】
上記化合物の配合量は、一般式（１）で表される化合物の１００質量部に対して０．１〜１０質量部が好ましく、０．１質量部未満では機械的強度が不足し、１０質量部を越えると加工性が劣化する。
【００５３】
上記非フッ素化ポリシロキサンの成型体の膜厚は１００ｎｍ〜１ｍｍの範囲が好ましく、さらに好ましいのは１μｍ〜２００μｍである。１００ｎｍ未満では、非フッ素化ポリシロキサンの被覆において、密着度が不充分になり、現像が不均一となり、１ｍｍを越えると非フッ素化ポリシロキサンの均一な平面を得ることが難しくなる。
（フッ素化炭化水素ポリマー）
次ぎに、本発明に係わる前記一般式（３）で表されるフッ素化炭化水素ポリマーについて述べる。
【００５４】
前記一般式（３）において、Ｘ_１〜Ｘ_４はそれぞれ独立に水素原子、ハロゲン原子（例えば、フッ素、塩素等の原子）、炭素数１〜１６の炭化水素基（例えば、メチル基、エチル基、ブチル基、ヘキシル基、ドデシル基等）を表し、Ｘ_１〜Ｘ_４の少なくとも１つはフッ素原子であり、Ｘ_５〜Ｘ_１０はそれぞれ独立に水素原子、ハロゲン原子、炭素数１〜１６の炭化水素基又は酸素原子を含む炭化水素置換基から選ばれる基を表し、ハロゲン原子は全く含まなくてもよい。ｐは１００〜９０００、ｑは１００〜６００の整数、ｔは０又は１〜４の整数を表す。酸素原子を含む置換基としては、カルボキシル基、カルボキシルアルキルエステル基、ヒドロキシアルキル基、ヒドロキシアルキルオキシ基、ヒドロキシアルキルオキシアルキル基、ヒドロキシアルキル（ポリアルキルオキシ）アルキル基、アルキル（ポリオキシアルキル）オキシ基、グリシジルアルキルオキシ基、グリシジルオキシアルキル基、グリシジルオキシアルキルオキシ基等を挙げることができる。前記Ｘ_１〜Ｘ_１０が同時にすべてフッ素原子であることはない。
【００５５】
前記一般式（３）で表されるフッ素化炭化水素ポリマーの数平均重合度は、１００〜１００００程度の範囲を適宜選択することができる。前記範囲外でも可能であるが、数平均重合度が１００未満では充分な機械的強度及び弾性が得られず、数平均重合度が１００００を越えると、組成物の加工性が劣化し好ましくない。
【００５６】
前記一般式（３）で表されるフッ素化炭化水素ポリマーポリマーの合成法は、例えば、国際出願ＷＯ９８／５０２２９を参考にして合成することができる。
【００５７】
前記一般式（３）で表されるフッ素化炭化水素ポリマー層の被覆膜厚は１００ｎｍ〜１ｍｍの範囲が好ましく、さらに好ましいのは１μｍ〜２００μｍである。被覆膜厚が１００ｎｍ未満では、フッ素化炭化水素ポリマーの被覆において、密着度が不充分になり、現像が不均一となり、１ｍｍを越えるとフッ素化炭化水素ポリマー層の被覆加工が難しくなる。
【００５８】
前記一般式（１）で表される非フッ素化ポリシロキサン層と前記一般式（３）で表されるフッ素化炭化水素ポリマー層の塗膜厚比は、１／１００００〜１００００までが好ましい。前記一般式（３）で表されるフッ素化炭化水素ポリマーの好ましい具体例を下記に示すが、本発明はこれらに限定されるものではない。
【００５９】
【化６】

【００６０】
（プライマー）
本発明のプライマーについて説明する。
【００６１】
本発明において、プライマーとは、熱ドラムの芯金属と一般式（１）で表される非フッ素化ポリシロキサン層との接着性及び非フッ素化ポリシロキサン層とその上のフッ素化炭化水素ポリマー層との接着性を向上させるために使用するもので、前者をプライマー１と呼び、後者をプライマー２と呼ぶ。
〈プライマー１〉
プライマー１は芯金属と一般式（１）で表される非フッ素化ポリシロキサン層との接着であるので、一般式（１）で表される非フッ素化ポリシロキサン中にシランカップリング剤、金属アルコキシド、例えばアルミニウムアルコキシド（アルミニウムイソプロポキシド、アルミニウムエトキシド等）、チタンアルコキシド、例えば、チタンプロポキシド、チタンブトキシド等のカップリング剤を含ませたものをプライマーとして使用できる。シランカップリング剤としては、トリトリアルコキシシラン基を有するシランカップリング剤が好ましく、特に好ましいシランカップリング剤を下記に示す。
【００６２】
【化７】

【００６３】
シランカップリング剤は、一般式（１）で表される非フッ素化ポリシロキサン１００質量部に対して１／１０００〜４０質量部の範囲、より好ましくは１／１０〜１８質量部のまま範囲で使用することが好ましい。この範囲未満では接着性が弱く、膜剥がれし易く、上記範囲を越えると膜が弱くなり膜剥がれし易くなる。
【００６４】
非フッ素化ポリシロキサンの添加方法は、エチルアルコール、メチルアルコール、イソプロピルアルコール等のアルコール類やアセトンやメチルエチルケトン等のケトン類に溶解して添加してもよく、無溶媒で使用してもよい。
【００６５】
塗膜の厚さは、１０ｎｍ〜３００μｍが好ましく、より好ましくは１００ｎｍ〜１００μｍである。上記未満では、プライマー層の接着効果が得にくく、上記範囲を越えると接着性が低下してくるので好ましくない。
〈プライマー２〉
非フッ素化ポリシロキサンとフッ素化炭化水素ポリマーの両者を接着させるプライマー２は、両者の組成分をもつものが好ましく、本発明では、前記一般式（１）で表される非フッ素化ポリシロキサンと前記一般式（３）で表されるフッ素化炭化水素ポリマーを混合した組成が経済的である。更に、好ましい方法としては、下記一般式（４）で表されるフッ素化ポリシロキサンを用いることである。
【００６６】
【化８】

【００６７】
一般式（４）において、Ｒ_５〜Ｒ_９はそれぞれ独立に水素原子、アクロイル基、メタクリロイル基又は炭素数１〜１６の炭化水素基（例えば、メチル基、エチル基ピロピル基、ブチル基、オクチル等）を表し、Ｒｆはフッ素化炭化水素基（パーフロロメチル基、パーフロロエチル基、パーフロロプロピル基（例えば、パーフロロヘキシル基、パーフロロオクチル基、パーフロロノネニル等）、Ｌ_１は２価の連結基（メチレン基、エチレン基、プロピレン基、ブチレン基、ヘキサメチレン基等）、ａ及びｃは０〜１０００の整数、ｂは１〜８０００の整数、ａ及びｃが同時に０になることはない。
【００６８】
上記プライマーの塗膜方法は、前述したアルコール類やケトン類に溶解又は分散して使用してもよいし、無溶媒で加温して液状にして塗設してもよい。塗膜の厚さ等はプライマー１と同様に設定することができる。一般式（４）で表される化合物の好ましい具体例を下記に挙げるが、本発明はこれらに限定されるものではない。
【００６９】
【化９】

【００７０】
本発明では、前記一般式（１）で表される非フッ素化ポリシロキサン又は一般式（３）で表されるフッ素化炭化水素ポリマーの組成物中に必要により無機充填剤を含有せしめることができる。特に一般式（１）で表される非フッ素化ポリシロキサン中に含有させることが好ましい。無機充填剤を添加する目的は、塗膜の強度、熱伝導性、電気抵抗、滑り性調節等である。
【００７１】
無機充填剤としては、一定の強度であれば特に制限されないが、アルミナ、シリカ、チタニア、ジルコニア、マグネシア、酸化亜鉛、酸化カルシウム等の酸化物系無機物、炭化ケイ素、窒化ケイ素、窒化ホウ素、窒化アルミニウム、炭化アルミニウム、ホウ化チタン、窒化チタン、炭化チタン等の非酸化物系無機物等が挙げられる。その中でも、酸化物系無機物、より好ましくはアルミナ、シリカ、チタニアが工業的に多量に製造され入手し易く経済的で好ましい。
【００７２】
本発明で使用する無機充填剤は、その原料、製造方法等は特に限定されず、繊維状、針状（ウィスカーを含む）、粒状、鱗片状等種々の形状のものを用いることができ、各塗膜において、無機充填剤をそれぞれ単独で使用してもよく、或いは２種以上を併用してもよい。また、種々の形状のものを混合して用いてもよい。更に、２種以上の無機充填剤を併用する場合があっても、それらの混合割合は特に限定されず、任意に選択することができる。
【００７３】
塗膜製造において、これらの無機充填剤の分散の均一性を確保するため、また、塗膜中に均一に分散させるために、無機充填剤は１００μｍ以上の粗大径のものを含まないことが望ましい。また、無機充填剤の平均粒径は、塗膜の厚さも考慮して定めればよいが、通常平均２０μｍ以下であり、平均５μｍ以下のものがより好ましい。下限は減退されないが、通常１０ｎｍ程度である。平均粒径が１０ｎｍ未満では、微粒子化のコストが高くなり、１００μｍ以上では成型品の表面の凹凸が大きく現像が不均一になり、画質が損なわれる。
【００７４】
無機充填剤の配合量は、一般式（１）で表される非フッ素化シロキサンの１００質量部に対して０．３〜３００質量部まで任意に設定することができるが、５〜９５質量部が好ましい。
【００７５】
無機充填剤の分散を良好にするために、界面活性剤を使用することが好ましい。界面活性剤は、組成物中の無機充填剤を均一に分散させることのできるものであればよく、アニオン性界面活性剤、カチオン性界面活性剤、非イオン性界面活性剤、両性界面活性剤のいずれも使用できる。例えば、ナトリウムアルキルサルフェート（例えば、ナトリウムラウリルサルフェート、ナトリウムオクチルサルフェート等）、ナトリウムアルキルエーテルサルフェート（例えば、ナトリウムラウリルエーテルサルフェート、ナトリウムドデシルエーテルサルフェート等）、トリエタノールアルキルサルフェート、トリエタノールアミンアルキルエーテルサルフェート、アンモニウムアルキルサルフェート、アンモニウムアルキルエーテルサルフェート、アルキルエーテルリン酸ナトリウム、フルオロアルキルカルボン酸ナトリウム等のアニオン性界面活性剤、アルキルアンモニウム塩、アルキルベンジルアンモニウム塩等のカチオン性界面活性剤、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンフェニルエーテルである。本発明に特に好ましい構造を下記一般式（５）に示す。
【００７６】
【化１０】

【００７７】
一般式（５）において、Ｒｆはそれぞれ炭素数１〜１２のフッ化アルキル基（例えば、パーフロロメチル基、パーフロロエチル基、パーフロロブチル基、パーフロロオクチル基等）、アルケニル基（例えば、パーフロロプロペニル基、パーフロロブテニル基、パーフロロノネニル基等）を表し、Ｌ_１及びＬ_２は２価の連結基（例えば、メチレン基、エチレン基、ブチレン基、ヘキサメチレン基等）を、Ｙは２〜４価の基を表し、Ａはアニオン基（スルホン酸基又はカルボン酸基）又はその塩（例えば、ナトリウム、カリウム、リチウムの各塩）を表し、ｍ及びｎは０又は１を表し、ｐ及びｑは１〜４の整数を表す。
【００７８】
一般式（５）で表される化合物の合成は、フッ素原子を導入した炭素数１〜１２のアルキル基（例えば、トリフロロメチル基、ペンタフロロエチル基、パーフロロブチル基）、アルケニル基（例えば、パーフロロプロペニル基及びパーフロロブテニル基、パーフロロノネニル基等）を有するアルコール化合物、酸クロリド化合物又は沃化物）とそれぞれフッ素原子を有してもよい３〜６価のアルカノール化合物、水酸基を３又は４個有する芳香族化合物又はヘテロ化合物との縮合反応又は付加反応によって得るこができる。
【００７９】
また、別の合成法としては、非フッ素化構造の化合物を合成し、電解フッ素化して合成することができる。アルカノール化合物を使用する場合は、グリセリン、ペンタエリスリトール、２−メチル−２−ヒドロキシメチル−１，３−プロパンジオール、２，４−ジヒドロキシ−３−ヒドロキシメチルペンテン、１、２、６−ヘキサントリオール、１，１，１−トリス（ヒドロキシメチル）プロパン、２，２−ビス（ブタノール）−３、脂肪族トリオール、テトラメチロールメタン、Ｄソルビトール、キシリトール、Ｄ−マンニトール等が原料として有用である。以下に、一般式（５）で表される化合物の好ましい具体例を示すが、本発明はこれらに限定されない。
【００８０】
【化１１】

【００８１】
【化１２】

【００８２】
本発明に好ましく用いられる前記一般式（５）で表される化合物の添加方法は水、メタノールやエタノール等のアルコール類、メチルエチルケトンやアセトン等のケトン類、トルエンやキシレン等の芳香族系やノルマルヘキサンやデカン等の芳香族系等の溶媒に溶解又は部粒子分散して添加してもよいし、固体微粉末のまま添加してもよい。添加量は、無機微粒子１ｇ当たり１μｇ〜１３ｇの範囲が好ましく、特に１〜３００ｍｇの範囲が好ましい。この範囲未満では、無機微粒子の分散効果が得られにくく、これを越えると泡沫が発生し易く、生産性が低下する。
【００８３】
本発明で用いるポリマー分散組成物中には、用途によって種々の添加剤を配合することができる。
【００８４】
添加剤としては、例えば、安定剤、顔料、増粘剤、分解促進剤、防錆剤、消泡剤等が挙げられる。
【００８５】
各被覆組成物の溶媒としては、フッ素化ポリマーや無機充填剤を均一に分散させるため、また、加熱処理後に揮散するような有機溶剤が用いられる、例えば、メチルエチルケトン、ジオキサン、ジオキソラン、テトラヒドロフラン、アセトン、メチルセロソルブ、ブチルセロソルブ、エチレングルコール、エタノール、ｎ−メチルピロリドン、ジアセトアルコール、トルエン、ベンゼン、キシレン等が挙げられる。
【００８６】
各被覆組成物の塗膜の塗布方法としては、公知の各種の塗布方法を採用することができる。例えばスプレーコート法、バーコート法、フローコート法、ディップ法、キャスティング法及びスピンコート法等が挙げられる。
【００８７】
特に、スプレート法は、塗膜の膜厚を均一にし易すい点で好適である。スプレート法の場合に用いられる塗布機としいは、公知のものが使用できる。
【００８８】
熱処理は８０〜４００℃程度、より好ましくは１２０〜１８０℃の温度で行うのがよい。熱処理温度が８０℃未満では、熱処理時間を長くする必要があり、一方、４００℃を越える場合には、非フッ素化ポリシロキサン又はフッ素化炭化水素ポリマーが分解する恐れが生じるので好ましくない。熱処理時間は特に限定されるものではないが、通常１０〜６０分程度でよい。
（熱現像材料）
熱現像材料は、支持体上に少なくとも１層の感光層を設け、この感光層の下部（支持体と感光層の間）にＡＨ層、感光層上部に保護層が塗設されている。更に、支持体に対して感光層のある側と反対側にバッキング層（ＢＣ層）、その上部に保護層がそれぞれ塗設されている。感光層中には、ハロゲン化銀、有機銀塩、還元剤及びバインダー（高分子結合剤）が含まれている。ＡＨ層、ＢＣ層には、感光波長に対して吸収効率が高く、残色になりにくい染料をバインダー中に存在させて熱現像材料の構成層界面での乱反射による鮮鋭性の劣化や干渉縞の防止行う。
【００８９】
ＡＨ層、ＢＣ層及び保護層等のバインダーは、感光層と同種や異種の素材を使用することができる。ＢＣ層に染料を使用する場合、ＡＨ層を設けない場合もある。ＡＨ層やＢＣ層の染料に由来する残色を低減させるため、熱により消色する染料を、更に熱消色を促進するために塩基発生前駆体を場合によっては使用することができる。バインダーの硬化は、保護層のみに関わらず感光層、ＡＨ層及びＢＣ層等をエポキシ架橋剤、酸無水物化合物及び塩基発生前駆体を適宜選択することにより、写真性能を損なわない範囲で使用することができる。以下に、熱現像材料に使用する素材について順次詳述する。
（感光性ハロゲン化銀）
本発明の熱現像感光材料に使用される感光性ハロゲン化銀は、シングルジェットもしくはダブルジェット法等の写真技術の分野で公知の任意の方法により、例えばアンモニア法、中性法、酸性法等の何れかの方法で調製できる。この方法で予め調製し、次いで本発明の他の成分と混合して、本発明の組成物中に導入することができる。この場合、感光性ハロゲン化銀と後述の有機銀塩との接触を充分に行わせるため、例えば、感光性ハロゲン化銀を調製するときの保護ポリマーとして米国特許第３，７０６，５６４号、同第３，７０６，５６５号、同第３，７１３，８３３号、同第３，７４８，１４３号、英国特許第１，３６２，９７０号等の各明細書に記載されているポリビニルアセタール類等のゼラチン以外のポリマーを用いる手段や、英国特許第１，３５４，１８６号明細書に記載されているような感光性ハロゲン化銀乳剤のゼラチンを酵素分解する手段又は米国特許第４，０７６，５３９号明細書に記載されているように感光性ハロゲン化銀を界面活性剤の存在下で調製することによって、保護ポリマーの使用を省略する手段等の各手段を適用することが出来る。
【００９０】
ハロゲン化銀は、良好な画質を得るために粒子サイズが小さくて感度の高いものが好ましい。粒子サイズが小さいと粒状性や解像度が良いからである。しかし、感度は低くなるので、分光増感や化学増感により増感され易い結晶形が好ましい。
【００９１】
具体的には、平均粒子サイズは０．１μｍ以下、好ましくは０．０１〜０．１μｍ、特に好ましくは０．０２〜０．０８μｍである。また、ハロゲン化銀の形状としては、特に制限はないが、立方体、八面体の所謂正常晶等の粒子が好ましい。また、ハロゲン化銀組成としては塩化銀、塩臭化銀、塩沃臭化銀、臭化銀、沃臭化銀、沃化銀のいずれであってもよいが沃臭化銀が好ましい。
【００９２】
上記ハロゲン化銀の量は、ハロゲン化銀及び後述の有機銀塩の総量に対し５０質量％以下、好ましくは２５〜０．１質量％、さらに好ましくは１５〜０．１質量％である。
【００９３】
本発明の熱現像感光材料に使用される感光性ハロゲン化銀は、英国特許第１，４４７，４５４号明細書に記載されているように、後述する有機銀塩を調製する際に、ハライドイオン等のハロゲン成分を有機銀塩形成成分と共存させ、これに銀イオンを注入することで、有機銀塩の生成とほぼ同時に生成させることができる。
【００９４】
さらに、他の方法としては、予め調製された有機銀塩の溶液若しくは分散液、又は有機銀塩を含むシート材料にハロゲン化銀形成成分を作用させて、有機銀塩の一部を感光性ハロゲン化銀に変換することもできる。
【００９５】
このようにして形成されたハロゲン化銀は、有機銀塩と有効に接触しており、好ましい作用を呈する。
【００９６】
これらのハロゲン化銀は、有機銀塩に対して化学量論的には少量用いられる。
通常、その範囲は、有機銀塩１モルに対し０．００１〜０．７モル、好ましくは０．０３〜０．５モルある。ハロゲン化銀形成成分は、上記の範囲で２種以上併用されてもよい。上記のハロゲン化銀形成成分を用いて、有機塩の一部をハロゲン化銀に変換させる工程の反応温度、反応時間、反応圧力等の諸条件は、作製の目的に合わせて適宜設定することができる。通常、反応温度は−２３〜７４℃、反応時間は０．１秒〜７２時間であり、その反応圧力は大気圧に設定されるのが好ましい。
【００９７】
この反応は、また、後述するバインダーとして使用されるポリマーの存在下に行われることが好ましい。この際のポリマーの使用量は、有機銀塩１質量部当たり０．０１〜１００質量部、好ましくは０．１〜１０質量部である。
【００９８】
上記、各種の方法によって調製された感光性ハロゲン化銀は、例えば、含硫黄化合物、白金化合物、パラジウム化合物、銀化合物、錫化合物、クロム化合物又はこれらの組み合わせによって化学増感することができる。化学増感の方法及び手順については、例えば米国特許第４，０３６，６５０号、英国特許第１，５１８，８５０号の各明細書、特開昭５１−２２４３０号、同５１−７８３１９号、同５１−８１１２４号に記載されている。
（化学増感剤）
本発明に、好ましい用いられる化学増感剤は、有機カルコーゲン増感剤であり、カルコーゲンとして硫黄原子、セレン原子又はテルル原子を分子内に含む有機化合物が好ましい。化学構造においては、カルコーゲン原子が炭素原子や燐原子に直接結合している化合物であり、即ち、炭素原子の４本の手のうち、２本はカルコーゲンであり、その他の２本は任意の有機の置換基であること、或いは燐原子の５本の結合手のうち、２本はカルコーゲン原子と結合し、その他は、任意の有機の置換基であり、任意の置換基がアリール基であることが好ましい。
【００９９】
アリール基としては、芳香族基又はヘテロ原子を含む複素環化合物が好ましく、最も好ましいものは、フェニル基又はフッ素原子で置換されたフェニル基である。好ましい具体例としては、トリフェニルホスフィンセレナイド、トリフェニルホスフィンオキサイド、トリフェニルホスフィンテルライド等である。
【０１００】
化学増感剤の添加方法は、ハロゲン化銀の分散溶液中に、水や有機溶媒に溶解して添加してもよいし、微粒子や粉末のまま添加してもよい。添加量はハロゲン化銀１モル当たり、１×１０^−９〜１×１０^−２モルが適当であり、好ましくは１×１０^−８〜１×１０^−４モルである。化学増感時の熟成温度は３０〜９０℃、熟成時間は２０分〜８時間、通常は４０〜９０分が好ましい。
【０１０１】
感光性ハロゲン化銀には、照度不軌、階調処理、感度、カブリ及び保存性等のために遷移金属、特に元素周期律表の６〜１０族に属する金属の第４〜第６周期の化合物がドープ（含有）されることが好ましい。
【０１０２】
具体的にはＲｈ、Ｒｕ、Ｒｅ、Ｉｒ、Ｏｓ、Ｆｅ等のイオン、錯体又は錯イオンが好ましい。
【０１０３】
ドープ量は、ハロゲン化銀１モル当たり１×１０^−９〜１×１０^−２モルが適当であり、好ましくは１×１０^−８〜１×１０^−４モルである。これらの金属イオン又は錯体イオンを提供する化合物は、ハロゲン化銀粒子形成時に添加し、ハロゲン化銀粒子中に組み込まれることが好ましく、ハロゲン化銀粒子の調製、つまり、核形成、成長、物理熟成、化学増感の前後のどの段階で添加してもよいが、特に、核形成、成長、物理熟成の段階で添加するのが好ましく、更には核形成、成長、の段階で添加するのが好ましく、最も好ましくは核形成の段階である。
【０１０４】
添加に際しては数回に亙って分割して添加してもよく、ハロゲン化銀粒子中に均一に含有させることもできるし、特開昭６３−２９６０３号、特開平２−３０６２３６号、同３−１６７５４５号、同４−７６５３４号、同６−１１０１４６号、同５−２７３６８３号等に記載されているように粒子内に分布を持たせて含有させることもできる。
（バインダー）
本発明の熱現像感光材料の感光層又は非感光層に用いられるバインダーとしては、ハロゲン化銀、有機銀塩、還元剤が反応する場として好ましい素材、例えば、ヒドロキシメチルセルロース、カルボキシメチルセルロース、メチルセルロース、エチルセルロース等のセルロース誘導体、ポリビニルアルコール、変性ポリビニルアルコール、ポリビニルブチラール、ポリアクリル酸ナトリウム、ポリエチレオキシド、アクリル酸アミド−アクリル酸エステル共重合体、スチレン−無水マレイン酸共重合体、ポリアクリルアミド、ポリ酢酸ビニル、ポリウレタン、ポリアクリル酸、ポリアクリル酸エステル、スチレン−ブタジェン共重合体、アクリロニトリル−ブタジェン共重合体、塩化ビニル−酢酸ビニル共重合体、スチレン−ブタジェン−アクリル酸共重合体などが挙げられる。更に、乾燥後、膜を形成した後、その塗膜の平衡含水率の低いものが好ましい。
（マット剤）
本発明の熱現像感光材料は、感光層上の保護層やＢＣ層にマット剤を含有することが好ましい。本発明に好ましく用いられるマット剤の材質は、有機物又は無機物の何れでもよく、例えば、無機物としては、スイス特許第３３０，１５８号等に記載のシリカ、仏国特許第１，２９６，９９５号等の記載のガラス粉、英国特許第１，１７３，１８１号等に記載のアルカリ金属又はカドミウム、亜鉛等の炭酸塩等をマット剤として用いることができる。有機物としては、米国特許第２，３２２，０３７号等に記載の澱粉、ベルギー特許第６２５，４５１号や英国特許第９８１，１８８号等に記載された誘導体、特公昭４４−３６４３号公報に記載のポリビニルアルコール、スイス特許第３３０，１５８号等に記載のポリスチレン或いはポリメタアクリレート、米国特許第３，０７８，２５７号等に記載のポリアクリロニトリル、同第３，０２２，１６９号等に記載のポリカーボネートのような有機マット剤を用いることができる。
【０１０５】
マット剤の形状は定形、不定形どちらでもよいが、好ましくは定形で、球形が好まう用いられる。
【０１０６】
マット剤の大きさは、マット剤の体積を球形に換算したときの直径で表される。本発明においてマット剤の粒径とは、球形に換算したときの直径のことを示すものとする。
【０１０７】
本発明に用いられるマット剤は、平均粒径が０．５〜１０μｍであることが好ましく、更に好ましくは１．０〜８．０μｍである。また、粒子の単分散度は５０以下であることが好ましく、更に好ましくは４０以下であり、特に好ましくは２０以下であるマット剤である。
【０１０８】
ここで、粒子の単分散度とは、粒子径の標準偏差を粒子径で除した値に１００を乗じた値である。
【０１０９】
マット剤の添加方法は、予め塗布液中に分散させて塗布する方法であってもよいし、塗布液を塗布した後、乾燥が終了する以前にマット剤を噴霧する方法を用いてもよい。また、複数の種類のマット剤を添加する場合は、両方の方法を併用してもよい。
（有機銀塩）
本発明の熱現像感光材料は、熱現像処理にて写真画像を形成するもので、還元可能な銀源（有機銀塩）、触媒活性量のハロゲン化銀、ヒドラジン誘導体、還元剤及び必要に応じて銀の色調を制御する色調剤を、通常有機バインダーマトリックス中に分散した状態で含有している熱現像感光材料であることが好ましい。
【０１１０】
本発明の熱現像感光材料は、常温で安定であるが、露光後、高温（例えば、８０〜２００℃）に加熱することで現像される。加熱は、一定の温度で一定時間加熱する１段階方式と予備加熱、本加熱或いは後加熱のような段階的に加熱する方法等があるが、適宜加熱する方式を選択することができる。
【０１１１】
加熱することで、有機銀塩（酸化剤として機能する）と還元剤との間の酸化還元反応を通じて銀を生成する。
【０１１２】
この酸化還元反応は、露光でハロゲン化銀に発生した潜像の触媒作用によって促進される。露光領域中の有機銀塩の反応によって生成した銀は、黒色画像を提供し、これらは、非露光領域と対照をなし、画像の形成がなされる。この反応過程は、外部から水等の処理液を供給することなく進行する。
【０１１３】
還元可能な銀イオン源を含有する有機酸としては、ヘテロ有機酸及び酸ポリマーの銀塩などが用いられる。また、配位子が４．０〜１０．０の銀イオンに対する総安定定数を有する有機又は無機の銀塩錯体も有用である。これらの銀塩の例は、例えばＲｅｓｅａｒｃｈ Ｄｉｓｃｌｏｓｕｒｅ（以下、単にＲＤ）１７０２９及び２９９６３に記載されており、特に好ましいものとしては、例えば、没食子酸、シュウ酸、ベヘン酸、ステアリン酸、パルミチン酸、ラウリン酸、アラキジン酸、エルカ酸等の銀塩である。
（還元剤）
本発明の熱現像感光材料に含有される還元剤は、米国特許第３，７７０，４４８号、同第３，７７３，５１２号、同第３，５９３，８６３号等に記載されており、好ましい還元剤として次のものが挙げられる。
（Ｋ−１） １，１−ビス（２−ヒドロキシ−３，５−ジメチルフェニル）−３，５，５−トリメチルヘキサン
（Ｋ−２） ビス（２−ヒドロキシ−３−ｔｅｒｔ−ブチル−５−メチルフェニル）メタン
（Ｋ−３） ２，２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン
（Ｋ−４） ４，４−エチリデン−ビス（２−ｔｅｒｔ−ブチル−６−メチルフェノール）
（Ｋ−５） ２，２−ビス（３，５−ジメチル−４−ヒドロキシフェニル）プロパン
前記に示された化合物は、水に分散したり、有機溶媒に溶解して使用する。有機溶媒としては、メタノールやエタノール等のアルコール類やアセトンやメチルエチルケトン等のケトン類、トルエンやキシレン等の芳香族系の溶媒を任意に選択することができる。
【０１１４】
還元剤の使用量は、銀１モル当たり１×１０^−２〜１×１０モル、好ましくは１×１０^−２〜１×１．５モルである。
（色調剤）
本発明のドライイメージング材料には、色調剤を添加することが好ましい。好適な色調剤の例としては、例えば、メロシアニン染料、（例えば、３−エチル−５−（（３−エチル−２−ベンゾチアゾリニリデン（ベンゾチアゾリニリデン））−１−メチルエチリデン）−２−チオ−２，４−オキサゾリジンジオン）；フタラジノン、フタラジノン誘導体又はこれらの誘導体の金属塩（例えば、４−（１−ナフチル）フタラジノン、６−クロロフタラジノン、５，７−ジメチルオキシフタラジノン及び２，３−ジヒドロ−１，４−ポリハロメタン化合物ジオン）；フタラジノンとスルフィン酸誘導体の組み合わせ（例えば、６−クロロフタラジノン＋ベンゼンスルフィン酸ナトリウム又は８−メチルフタラジノン＋ｐ−トリスルホン酸ナトリウム）；ポリハロメタン化合物＋フタル酸の組み合わせ；ポリハロメタン化合物（ポリハロメタン化合物の付加物を含む）とマレイン酸無水物及びフタル酸、２，３−ナフタレンジカルボン酸又はｏ−フェニレン誘導体及びその無水物（例えば、フタル酸、４−メチルフタル酸、４−ニトロフタル酸及びテトラクロロフタル酸無水物）から選択される少なくとも１つの化合物との組み合わせ；キナゾリンキオン類、ベンズオキサジン、ナルトキサジン誘導体；ベンズオキサジン−２，４−ジオン類（例えば、１，３−ベンズオキサジン−２，４−ジオン）；ピリミジン類及び不斉−トリアジン類（例えば、２，４−ジヒドロキシピリミジン）及びテトラアザペンタレン誘導体（例えば、３，６−ジメルカプト−１，４−ジフェニル−１Ｈ、４Ｈ−２，３ａ，５，６ａ−テトラアザペンタレン）等を挙げることができる。
（分光増感色素）
本発明の熱現像感光材料には、例えば、特開昭６３−１５９８４１号、同６０−１４０３３５号、同６３−２３１４３７号、同６３−２５９６５１号、同６３−３０４２４２号、同６３−１５２４５号、米国特許第４，６３９，４１４号、同第４，７４０，４５５号、同第４，７４１，９６６号、同第４，７５１，１７５号、同第４，８３５，０９６号に記載された増感色素が好ましく使用できる。
【０１１５】
本発明に使用される有用な増感色素は、例えば、特開平９−３４０７８号、同９−５４４０９号、同９−８０６７９号に記載の化合物が好ましく用いられる。
（支持体）
本発明の熱現像感光材料に好ましく用いられる支持体としては紙、合成紙、不織布、金属箔、ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル、ポリカーボネートやポリプロピラン等のプラスチック等の支持体が使用可能であり、また、これらを組み合わせて複合シートを任意に用いてもよい。
【０１１６】
【実施例】
以下、実施例を挙げて、本発明を詳細に説明するが、本発明の実施の態様はこれらに限定されるものではない。
【０１１７】
実施例１
（熱ドラムの被覆）
外径１００ｍｍ、長さ４５０ｍｍ、肉厚８ｍｍのアルミニウム製の円筒形熱ドラムを、以下に示す組成で被覆した。対向ローラーはステンレス材を用い無被覆のままとした。
〈プライマー１の塗設〉
表１記載の非フッ素化ポリシロキサン１００ｇ中に表１記載のシランカップリング剤６ｇを添加し、良く混練した後、アルミニウム芯金属上に、厚さ１μｍで塗設し、５０℃で１０分間乾燥した。
〈ポリシロキサンの塗設〉
次に、それぞれ表１記載の非フッ素化ポリシロキサン１種又は２種を３００ｇ（ただし、２種の場合は各１５０ｇ）、表１記載の貴金属触媒１０ｍｇ、過酸化物３ｇ及び無機充填剤（平均粒子径表１記載）５６ｇを加えてニーダーでよく混練した後、プライマー１の上に厚さ３ｍｍになるように均一に塗設し、５０℃で１０分間乾燥した。乾燥膜厚は表１に記載した。
〈プライマー２の塗設〉
各ドラムのそれぞれ表１記載の非フッ素化ポリシロキサン層を塗設した上に、表１記載の同じ非フッ素化ポリシロキサン１００ｇ（２種用いている場合には５０ｇずつ）及び表２記載のフッ素化ポリシロキサンを３ｇ（２種用いている場合はそれぞれ１．５ｇずつ）、表２記載の貴金属触媒１．２ｍｇ、過酸化物３ｇ添加して混練し、前記ポリシロキサン層上に１μｍの厚さで塗設した。
〈フッ素化炭化水素ポリマーの塗設〉
次いで、表２記載のフッ素化炭化水素ポリマー１種又は２種を３００ｇ（ただし、２種の場合は各１５０ｇ）、表２記載の平均粒子径の無機充填剤１０ｇ及び界面活性剤３ｇを加えて、ニーダーでよく混練しながら８０℃で１時間加熱反応させた後、塗設し、５０℃で１０分間乾燥した。乾燥後、表２記載の温度で塗設の完了した熱ドラムをオーブン中で３時間熱処理した。乾燥膜厚は表２に記載した。
【０１１８】
なお、比較１として非フッ素化ポリシロキサンの被覆液は、下記のように調製した。
【０１１９】
ビニル基及びシリルハイドロジェン基のないポリシロキサン（平均重合度３００）を４０ｇに、平均粒子径６μｍのシリカを４３ｇを加え、ニーダーでよく混練しながら１８０℃で１時間加熱反応させた後、熱ドラムに厚さ４００μｍで被覆し乾燥した。
【０１２０】
また、その上に塗設する、比較２としてのフッ素化炭化水素ポリマーの被覆は、下記のように塗設した。
【０１２１】
ポリフッ化エチレン（数平均重合度２２００のテフロン（Ｒ））を被覆し乾燥した。乾燥後１８０℃４時間熱処理をした。
（熱現像用熱現像感光材料の作製）
〈下引済み写真用支持体の作製〉
厚さ１７５μｍのポリエチレンテレフタレート支持体の塗布面に０．８ｍＷ／ｃｍ^２・分のコロナ放電処理を施し、一方の面に、下記下引塗布液ａ−１を乾燥膜厚０．８μｍになるように塗設し、乾燥させて下引層Ａ−１とし、また、反対側の面に、下記、下引塗布液ｂ−１を乾燥膜厚０．８μｍになるように塗設し、乾燥させて下引層Ｂ−１とした。
〈下引塗布液ａ−１〉
ブチルアクリレート（３０質量％）
ｔ−ブチルアクリレート（２０質量％）
スチレン（２５質量％）
２−ヒドロキシエチルアクリレート（２５質量％）
の共重合体ラテックス液（固形分３０％） ２７０ｇ
ヘキサメチレン−１，６−ビス（エチレンウレア） ０．８ｇ
水で１リットルに仕上げる。
〈下引塗布液ｂ−１〉
ブチルアクリレート（４０質量％）
スチレン（２０質量％）
グリシジルアクリレート（４０質量％）
の共重合体ラテックス液（固形分３０％） ２７０ｇ
ヘキサメチレン−１，６−ビス（エチレンウレア） ０．８ｇ
水で１リットルに仕上げる。
【０１２２】
引き続き、下引層Ａ−１及び下引層Ｂ−１の上表面に、８Ｗ／ｍ^２・分のコロナ放電を施し、下記層Ａ−１の上には、下記下引上層塗布液ａ−２を乾燥膜厚０．１μｍになるように下記層Ａ−２として、下引層Ｂ−１の上には下記下引上層塗布液ｂ−２を乾燥膜厚０．８μｍになるように帯電防止機能をもつ下引上層Ｂ−２として塗設した。
〈下引上層塗布液ａ−２〉
ゼラチン ０．４ｇ／ｍ^２
シリカ粒子（平均粒径３μｍ） ０．１ｇ
水で１リットルに仕上げる。
〈下引上層塗布液ｂ−２〉
スチレンブタジェン共重合ラテックス液（固形分２０％） ８０ｇ
ポリエチレングリコール（重量平均分子量６００） ６ｇ
水で１リットルに仕上げる。
（感光性ハロゲン化銀乳剤Ａの調製）
水９００ｍｌ中にイナートゼラチン７．５ｇ及び臭化カリウム１０ｍｇを溶解して温度３５℃、ｐＨ３．０に合わせた後、硝酸銀７４ｇを含む水溶液３７０ｍｌと（９８／２）のモル比の臭化カリウムとヨウ化カリウムを含む水溶液をｐＡｇ７．７に保ちながらコントロールドダブルジェット法で１０分間かけて添加した。その後、４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデン０．３ｇを添加し、ＮａＯＨでｐＨを５に調整して平均粒子サイズ０．０６μｍ、投影直径面積の変動係数８％、〔１００〕面比率８７％の立方体ヨウ臭化銀粒子を得た。この乳剤にゼラチン凝集剤を用いて凝集沈降させ脱塩処理後、フェノキシエタノール０．１ｇを加え、ｐＨ５．９、ｐＡｇ７．５に調整して感光性ハロゲン化銀乳剤Ａを得た。
（分散有機銀塩の調製）
４７２０ｍｌの純水にベヘン酸１１１．４ｇ、アラキジン酸８３．８ｇ、ステアリン酸５４．９ｇを８０℃で溶解した。次に高速で撹拌しながら１．５モルの水酸化ナトリウム水溶液５４０．２ｍｌを添加し、濃硝酸６．９ｍｌを加えた後、５５℃に冷却して有機酸ナトリウム溶液を得た。上記の有機酸ナトリウム溶液の温度を５５℃に保ったまま、上記感光性ハロゲン化銀乳剤Ａ（銀０．０３８モルを含む）と純水４５０ｍｌを添加し５分間撹拌した。次に１モルの硝酸銀溶液７６０．６ｍｌを２分間かけて添加し、さらに２０分間撹拌し、濾過により水溶性塩類を除去した。その後、濾液の電導度が２μＳ／ｃｍになるまで脱イオン水による水洗、濾過を３回繰り返し乾燥させ分散有機銀塩を得た。
〈バック面側塗布〉
バック層及びバック層保護層を、以下の組成物をメチルエチルケトン溶液中に加えて調製した塗布液を、以下の付き量になるように減圧押し出し同時重層塗布した。
【０１２３】
バック層（第１層）
ＰＶＢ−１ １．１ｇ／ｍ^２
染料：Ｃ １２ｍｇ／ｍ^２
コロイダルシリカ １２ｍｇ／ｍ^２
ドデシルベンゼンスルホン酸ナトリウム １３ｍｇ／ｍ^２
バック層保護膜（第２層）
セルロースアセテートブチレート ０．８ｇ／ｍ^２
マット剤（ＰＭＭＡ：平均粒径５μｍ） ０．０２ｇ／ｍ^２
活性剤：Ｎ−プロピルオクチルスルホンアミド酢酸 ０．０２ｇ／ｍ^２
硬膜剤：１，２−ビス（ビニルスルホンアミド）エタン ０．０２ｇ／ｍ^２
〈感光層面塗布〉
ＡＨ層（第１層）
ＰＶＢ−１ ０．３ｇ／ｍ^２
染料：Ｃ ８ｍｇ／ｍ^２
感光層（第２層）
感光層の調製は、以下の組成物のメチルケトン溶解体を加えて塗布液を調製した。この塗布液を３５℃に保ち、以下の付き量になるように塗布乾燥した。
【０１２４】

【０１２５】
【化１３】

【０１２６】
表面保護層（第３層）
セルロースアセテートブチレート １．２ｇ／ｍ^２
フタラジン ０．１ｇ／ｍ^２
４−メチルフタル酸 ０．７ｇ／ｍ^２
テトラクロロフタル酸 ０．２ｇ／ｍ^２
シリカマット剤（平均粒径３μｍ） ０．５ｇ／ｍ^２
帯電防止剤：Ｅ ０．１ｇ／ｍ^２
上記の組成物を上記付き量で、塗布速度２６０ｍ／分で同時重層塗布し、４８℃５６秒で乾燥した。
（膜密着力試験）
作製した各々の熱ドラムの４ｃｍ^２相当の最外表面に１ｃｍ^２当たり１００個の碁盤目を入れ、下記の条件下に放置した後、常温に戻し、セロハン粘着テープにより圧着剥離試験を行った。
【０１２７】
２２０℃で２時間放置後、−１０℃で１時間放置×１２サイクルの膜密着力試験結果において、碁盤目の剥離％で評価し、剥離の少ないものほど密着性がよく、例えば、５０％は半分の面積が剥離されたことを示し、２０％以下ならば、実用的に問題ないレベルである。
（膜汚れ評価試験）
作製した熱ドラムの汚れ評価は、濃度１．５に仕上がるように露光した上記熱現像性熱現像材料を幅２ｃｍ、長３０ｃｍに裁断し、熱現像温度１２０℃、熱現像時間１０秒、１時間当たりの処理枚数１００枚、一日１０００枚処理で５日間処理した後、各々の表面の汚れを評価した。
【０１２８】
評価方法は、処理試験後の熱ドラム及び対向ローラーを水：メタノール：アセトンの１：３：１の溶液で表面を洗浄（２ｍｌ／ｃｍ^２）し、この溶液の濃度をデジタル示差濃度計ＤＤ７（アタゴ社製）で測定した。測定値は小さい程（最小０．０００％）汚れが少なく、数値が大きい程（最大２．０００％）汚れが大である。汚れは１％表示であれば、実用的に問題のないレベルである。これらの結果をまとめて表示したが、表１にはプライマー１及びポリシロキサンの塗設内容、表２にはプライマー２及びフッ素化炭化水素ポリマー層の塗設内容、表３には性能試験の結果を示した。
【０１２９】
【表１】

【０１３０】
【表２】

【０１３１】
【表３】

【０１３２】
表１、２、３より熱ドラムを非フッ素化ポリシロキサンで被覆した上に、フッ素化炭化水素ポリマーを塗設した熱現像装置による現像処理では、汚れが付かないこと、剥離試験で膜剥がれが生じないことが分かる。
【０１３３】
【発明の効果】
本発明により、長期間に亙り、熱現像装置内の熱ドラムの汚れがなく、熱現像された熱現像性感光材料の汚れが転写することなく高品質画像を与える耐久性に優れた熱現像処理装置が得られた。
【図面の簡単な説明】
【図１】熱現像装置の概略断面図である。
【図２】熱現像部の構成を示す概略図である。
【符号の説明】
１ ヒートドラム
２ 対向ローラー
４ ブラケット
５ 長孔
６ 分離ツメ
１１ シャフト
２０ フレーム
２１ シャフト
２２ コイルばね
２３ 回転軸
２５ タイミングベルト
３５ 支持チュ−ブ
３６ プライマー層
３７ 非フッ素化ポリシロキサン層
３８ プライマー層
３９ フッ素化炭化水素ポリマー層
４０ シャフトベアリング
１００ 熱現像装置
１１０ 供給送部
１２０ 露光部
１３０ 熱現像部
１４０ 取り出し装置
１４１ １４２、１４３ 搬送装置
１４４ 供給ローラー対
１４５ 搬送ローラー対
１５０ 冷却部
１６０ 排出トレイ
１７０ 制御手段
Ｆ フィルム
Ｃ ケース
Ｌ レーザ光[0001]
TECHNICAL FIELD OF THE INVENTION
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat developing apparatus for processing a heat developable photosensitive material which forms an image by heat development, and more specifically, develops a large amount of heat developable photosensitive material quickly, uniformly and with high image quality over a long period of time. The present invention relates to a durable heat development processing apparatus.
[0002]
[Prior art]
In the field of medical image diagnosis by X-ray photography, modalities of diagnostic images such as CR (computed radiography) have become widespread, and dry processing has become widespread in this system.
[0003]
This system absorbs X-ray energy transmitted through a subject into a stimulable phosphor on an imaging plate, excites the stimulable phosphor in a time series with ultraviolet rays, visible light or infrared rays, and stores the accumulated X-rays. X-ray energy is emitted as fluorescent light, the fluorescent light is read photoelectrically to obtain an electric signal, and the obtained electric signal is converted into the intensity of laser light, and the laser light is used to immerse the silver halide in the heat-developable photosensitive material. The method is based on forming an image, thermally developing the image, and reproducing an X-ray image of the subject or the subject as a visible image. In the heat development, a black image is obtained by heat treatment on a hot durham at a temperature of 80 to 200 ° C.
[0004]
The photosensitive layer in the heat-developable photosensitive material (hereinafter, also simply referred to as a film) contains, in addition to silver halide, an organic silver salt and a reducing agent, an antifoggant, an antifoggant, a stabilizer, a development accelerator, and a spreading agent. And an additive such as a binder, and the protective layer contains a spreading agent, a matting agent, an antistatic agent, a binder and the like. Some of these are overheated and softened during thermal development, and sometimes volatilization, transpiration or sublimation occurs to a small extent, and adheres to the outermost layer of the thermal drum. Deteriorates.
[0005]
The substance adhering to the heat drum may be caused not only by the heat-developable photosensitive material but also by intrusion of dust from the outside. Deposits such as garbage are charged with static electricity and are treated with an antistatic agent or the like. However, this method cannot completely prevent the contamination, and contamination by such a deposit can be reduced to 100,000 to 100,000 hours. If the operation is performed for a long time, the heat drum is enlarged, and the heat drum is slightly deformed or cracked, and the heat development of the heat-developable photosensitive material conveyed over the heat drum causes non-uniformity to deteriorate the image quality.
[0006]
In addition to providing heat resistance to the heat drum, a method of coating the heat drum with a silicone polymer has been disclosed as a method for avoiding the attachment of foreign substances (described in Patent Document 1). Was impossible to prevent. Also, a method has been proposed in which the surface of the heat drum is made of a fluororesin (described in Patent Document 2). However, the fluororesin has poor adhesion to the substrate immediately below, causes film peeling, and withstands long-term thermal development processing. There was no problem. Therefore, there has been a strong demand for a technique that satisfies both the requirement of reducing the adhesion of dirt over a long period of time and the high film strength.
[0007]
[Patent Document 1]
JP-A-2001-272751
[0008]
[Patent Document 2]
JP-A-2002-296755
[0009]
[Problems to be solved by the invention]
The present invention relates to a heat developing apparatus for quickly and uniformly developing a heat developable photosensitive material. For a long period of time, the heat drum in the heat develop apparatus is free from stains and the heat developed photosensitive material is stained. An object of the present invention is to provide a heat development processing apparatus which does not transfer and has excellent durability to give a high quality image.
[0010]
[Means for Solving the Problems]
The above object of the present invention is achieved by the following means.
[0011]
(1) Thermal development with a thermal drum and a facing roller for thermally developing a thermally developable photosensitive material having a photosensitive layer containing a silver salt and a reducing agent on at least one surface of a support and a layer for protecting the photosensitive layer In the thermal developing apparatus provided with the apparatus, the thermal drum or the opposed roller of the thermal developing apparatus is coated with the non-fluorinated polysiloxane represented by the general formula (1), and A thermal development processing apparatus characterized by being coated with a fluorinated hydrocarbon polymer represented by the formula (3).
[0012]
(2) In the general formula (1), a is an integer of 100 to 9000, c is an integer of 10 to 300, and X represented by the general formula (3)₁~ X₄Is a fluorine atom.
[0013]
(3) In the general formula (1), b is 10 to 500, and in the formula represented by the general formula (3), X is₅~ X₁₀Wherein one of the substituents represented by is a substituent having an oxygen atom.
[0014]
(4) An inorganic filler is contained in the non-fluorinated polysiloxane represented by the general formula (1), and the inorganic filler is alumina, silica, titania, zirconia, magnesia, iron oxide, zinc oxide, calcium oxide. And at least one selected from the group consisting of silicon carbide, boron nitride, boron carbide, aluminum nitride, aluminum carbide, titanium boride, titanium nitride, and titanium carbide. 4. The thermal development processing device according to 1.
[0015]
(5) The thermal development processing apparatus as described in (4) above, wherein the inorganic filler contained in the non-fluorinated polysiloxane has an average particle diameter of 10 to 100 nm.
[0016]
(6) The thermal developing apparatus according to the above (4) or (5), wherein the inorganic filler is contained in the presence of a fluorinated surfactant.
[0017]
(7) The coating thickness of each of the non-fluorinated polysiloxane represented by the general formula (1) and the fluorinated hydrocarbon polymer represented by the general formula (3) is 10 nm to 20 mm. The heat development processing apparatus according to any one of claims 1 to 5.
[0018]
(8) The non-fluorinated polysiloxane represented by the general formula (1) is crosslinked, and the crosslinking is promoted by one or more catalysts selected from a platinum catalyst and an organic peroxide. The heat development processing apparatus according to any one of the above items 1 to 7.
[0019]
(9) The non-fluorinated polysiloxane represented by the general formula (1), wherein the group having a polymerizable vinyl group is an acryloyl group or a methacryloyl group. 4. The thermal development processing device according to 1.
[0020]
(10) The coating film of each coating layer of the non-fluorinated polysiloxane represented by the general formula (1) and the fluorinated hydrocarbon polymer represented by the general formula (3) is simultaneously or separately at 80 to 400 ° C. 9. The thermal development processing apparatus according to any one of 1 to 8, wherein the thermal development processing apparatus is independently heat-treated.
[0021]
(11) A heat drum or an opposing roller coats the core metal with the non-fluorinated polysiloxane represented by the general formula (1), and further forms a fluorinated compound represented by the general formula (3) on the coating layer. Before coating the non-fluorinated polysiloxane on the core metal of the heat drum or the opposed roller, which is coated with a hydrocarbon polymer, applying a primer component treated with an alkoxysilane compound or an alkoxymetal compound. The thermal developing apparatus according to any one of the above items 1 to 10, wherein
[0022]
(12) A heat drum or an opposing roller coats the core metal with the non-fluorinated polysiloxane represented by the general formula (1), and further forms a fluorinated compound represented by the general formula (3) on the coating layer. A non-fluorinated polysiloxane, a primer layer containing a fluorinated polysiloxane, and a fluorinated hydrocarbon polymer represented by the general formula (3). The heat development processing apparatus according to any one of the above items 1 to 11, wherein:
[0023]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments and examples of the present invention will be described.
(Heat development device)
The heat development processing apparatus according to the present invention is based on a digital image signal transmitted from an image transmitting apparatus such as a CR, a radiation CT apparatus, and a scanner. Main scanning, and sub-scanning is performed by moving the film relative to the laser light in a direction substantially perpendicular to the main scanning direction, and a latent image is formed on the film using the laser light. A black image is obtained by heat development.
[0024]
FIG. 1 is a schematic cross-sectional view of a heat developing device of the present invention, and FIG. 2 is a schematic diagram showing a configuration of a heat developing section according to an embodiment of the present invention. FIG. 2A is a schematic perspective view of the developing unit including a partially broken surface of the frame, and FIG. 2B is a schematic cross-sectional view of the heat drum along AA ′. In FIG. 2B, the opposing rollers are omitted to explain the configuration of the heat drum 1 of the present invention.
[0025]
The heat developing apparatus 100 shown in FIG. 1 includes a supply unit 110 that supplies a sheet-like heat developable photosensitive material (hereinafter, also simply referred to as a film) F one by one, an exposure unit 120 that exposes the supplied film F, It has a thermal developing unit 130 for developing the exposed film F and a cooling unit 150 for stopping the development.
[0026]
The supply units 110 are provided in upper and lower two stages, and store the film F stored in the case C together with the case C. The film F is taken out of the case C by the suction device and the conveyance roller of the take-out device 140, and is pulled out in the direction of the arrow in FIG. Further, the film F pulled out of the case C is conveyed in a direction indicated by an arrow in FIG.
[0027]
The film F conveyed below the thermal developing device 100 is conveyed by the conveying device 142 in the direction of the arrow (left) in the figure. From the left side surface of the thermal developing device 100, it is conveyed by the conveying device 143 composed of a pair of rollers in the direction (upward) indicated by the arrow, and at that time, the laser beam L in the infrared region 780 to 860 nm, for example, 810 nm Scan exposure.
[0028]
The film F forms a latent image by receiving the laser beam L. Thereafter, the film F is further transported in the direction indicated by the arrow (upward), and is supplied to the heat drum 1 as it is when the film F reaches the supply roller pair 144. That is, it is of a type that is supplied at random timing. Alternatively, the vehicle may be temporarily stopped at the time of arrival. In this case, the supply roller pair 144 has a function of determining the timing of supplying the film F to the heat drum 1 of the developing unit 130 rotating at a constant rotation speed. When rotated to the position, the supply roller pair 144 starts rotating to supply the film F to a fixed position on the outer periphery of the thermal drum 1.
[0029]
Further, the heat drum 1 rotates in the direction of the arrow while holding the film F on the outer periphery. In this state, the thermal drum 1 heats and thermally develops the film F to form a visible image from a latent image. Thereafter, when the heat drum 1 shown in FIG. 1 rotates to the right, the film F is detached from the heat drum 1 by the separation claw 6, conveyed in the direction of the arrow, and cooled and conveyed by the plurality of conveying roller pairs 145 of the cooling unit 150. After that, the sheet is discharged to a discharge tray 160 so that it can be taken out from the upper portion of the thermal developing device 100.
(Heat drum and opposed roller group)
Examples of the core metal of the heat drum 1 or the opposed roller group 2 preferably used in the present invention include metals and metal compounds such as aluminum, iron, nickel, titanium, molybdenum, magnesium, manganese, copper, silver, tin, chromium, tungsten, and cobalt. And alloys composed of two or more of these. Specific examples of alloys include carbon steel, Ni steel, Cr steel, Ni-Cr steel, Cr-Mo steel, stainless steel, silicon steel, alloy steels such as permalloy, Al-Cl, Al-Mg, Al-Si, Aluminum alloys such as Al-Cu-Ni-Mg and Al-Si-Cu-Ni-Mg; copper alloys such as brass, bronze (bronze), silicon bronze, silicon brass, nickel silver and nickel bronze; nickel manganese (D nickel) ), Nickel-aluminum (Z-nickel), nickel silicon, monel metal, constantan, nichrome inconel, nickel alloys such as Jasteroy and the like. Further, regarding aluminum-based metals, pure aluminum, oxides of aluminum, Al-Cu-based, Al-Si-based, Al-Mg-based and Al-Cu-Ni-Mg-based, Al-Si-Cu-Ni-Mg A cast such as a system, a high-strength aluminum alloy, a corrosion-resistant aluminum alloy, or an aluminum alloy for wrought can be used. Further, as iron-based metals, pure iron, iron oxide, carbon steel, Ni steel, Cr steel, Ni-Cr steel, Cr-Mo steel, Ni-Cr-Mo steel, stainless steel, silicon steel, permalloy, insensitive magnetic Steel, magnet steel, cast irons and the like can be used.
[0030]
Since the heat drum needs to withstand a development temperature of 80 to 200 ° C., the metal used as the support member is preferably stainless steel, aluminum, copper, a magnesium alloy, duralumin, or the like. Similarly, the core metal of the opposing roller 2 is also selected from the above metals.
[0031]
For the purpose of preventing corrosion, etc., the above-mentioned metal is subjected to electroplating, hot-dip plating, chromizing, siliconizing, calorizing, sheradizing, thermal spraying, etc. A phosphate film can be formed by the treatment, a metal oxide can be formed by anodic oxidation or heat oxidation, and electrochemical protection can be applied to the substrate. Further, for the purpose of improving the adhesiveness, the surface of the metal substrate is subjected to a chemical conversion treatment with phosphoric acid, sulfuric acid, chromic acid, oxalic acid, etc., sand blast, shot blast, grid blast, honing, paper scratch, wire scratch. The metal surface may be colored, printed, etched, or the like for the purpose of design.
[0032]
In an embodiment of the present invention, a polymer layer described below is applied to the metal surface for the purpose of improving the adhesiveness.
[0033]
In FIG. 2A, the developing unit 130 has the heat drum 1 as a heating member that can hold the film F in close contact with the outer periphery and can heat the film F. The heat drum 1 has a function of forming the latent image formed on the film F as a visible image by maintaining the film F at a predetermined heat development temperature or higher for a predetermined heat development time. Here, the minimum thermal development temperature is the minimum temperature at which the latent image formed on the film F starts to be thermally developed, and is 100 ° C. or higher in the film of the present embodiment. On the other hand, the term "thermal development time" refers to the time during which the latent image on the film F must be maintained at the minimum thermal development temperature or higher in order to develop it into desired development characteristics. It is preferable that the film F is not substantially thermally developed at 40 ° C. or lower.
[0034]
A plurality of small-diameter opposed rollers 2 are provided on the outer periphery of the heat drum 1 as urging members, and are opposed to the heat drum 1 and arranged at equal intervals in the circumferential direction of the drum 1. At both ends of the heat drum 1, guide brackets 4 supported on a frame 20 are provided on both sides.
[0035]
X and Y indicate detection means. The detection means X and Y are applied to control the heating temperature, heating time and exposure amount of the film on the heat drum 1. The detecting means X is fixed to a frame (not shown) of the developing section main body. On the other hand, the detecting means Y is fixed in the heat drum by a fixing member (not shown).
[0036]
Each guide bracket 4 has a long hole 5 extending radially. The shafts 21 provided at both ends of the opposing roller 2 protrude from the long holes 5. One end of a coil spring 22 is attached to each of the shafts 21, and the other end of the coil spring 22 is attached near the inner edge of the guide bracket 4. Therefore, each opposing roller 2 is urged to the outer periphery of the thermal drum 1 with a predetermined force based on the urging force of the coil spring 22. When the film F enters between the outer periphery of the heat drum 1 and the opposing roller 2, the film F is pressed against the outer peripheral surface of the heat drum 1 by the predetermined force, thereby uniformly heating the film F over the entire surface. it can.
[0037]
The shaft 11 coaxially connected to the heat drum 1 extends outside the end of the frame 20, and is rotatably supported by the frame 20 by a shaft bearing 40. A gear (not shown) is formed on a rotating shaft 23 of a micro step motor (not shown) which is arranged below the shaft 11 and attached to the frame 20. On the other hand, a gear is also formed on the shaft 11. The power of the micro-step motor is transmitted to the shaft 11 via a timing belt (belt on which the gear is cut) 25 connecting the two gears, whereby the heat drum 1 rotates.
[0038]
The transmission of power from the rotating shaft 23 to the shaft 11 may be performed via a chain or a gear train instead of the timing belt 25.
[0039]
In FIG. 2B, the heat drum 1 has an aluminum support tube 35 as a support member, and a plate-like heater (not shown) mounted on the inner circumference of the tube over the entire circumference. The heating is performed under the control of the control means 170 equipped with a memory.
[0040]
Further, in order to make the development uniform, a primer layer 36 is provided on at least one of the aluminum support tube 35 of the heat drum 1 and the core metal (not shown) of the opposing roller 2, and the primer layer 36 is formed thereon by the general formula (1). A non-fluorinated polysiloxane layer 37 is applied, a primer layer 38 is provided on the polymer layer 37, and a fluorinated polymer layer 39 represented by the general formula (3) is coated thereon. Is done.
[0041]
That is, the adhesion performance is provided by providing the primer layers 37 and 39 between the aluminum support tube 35 and the non-fluorinated polysiloxane layer 37, and between the non-fluorinated polysiloxane layer 37 and the fluorinated polymer layer 39. Improve.
[0042]
Hereinafter, the non-fluorinated polysiloxane represented by the general formula (1) and the fluorinated polymer represented by the general formula (3) will be described.
(Non-fluorinated polysiloxane)
In the general formula (1), R₁~ R₄Is a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms, such as methyl, ethyl, butyl, hexyl, dodecyl, etc.₁Is a polymerizable vinyl group, for example, an acroyl group, a methacryloyl group, a vinylsulfonyl group, etc., a is an integer of 10 to 10000, preferably 100 to 9000, b and c are each an integer of 0 to 1000, particularly c is And Z is independently a hydrogen atom or a hydrocarbon having 1 to 16 carbon atoms (the R₁~ R₄Or a group represented by the general formula (2);₅~ R₇Is a hydrocarbon having 1 to 16 carbon atoms (the R₁~ R₄Represents the same group as the group represented by.
[0043]
The non-fluorinated polysiloxane used in the present invention is a polymer having a main chain in which silicon atoms and oxygen atoms are alternately arranged in series, but may be branched. The arrangement of the substituents may be random, alternate, or block type. The high-strength non-fluorinated polysiloxane is prepared by preparing a non-fluorinated polysiloxane having a low average degree of polymerization (average degree of polymerization: 10 to 3000) in advance, coating the non-fluorinated polysiloxane on a core metal, and performing a heat treatment. It can be obtained by increasing the degree of polymerization or promoting intermolecular crosslinking.
[0044]
Preferred specific examples of the non-fluorinated polysiloxane represented by the general formula (1) used in the present invention are shown below, but the present invention is not limited thereto.
[0045]
Embedded image

[0046]
Embedded image

[0047]
The number average degree of polymerization of the above polymer after heat treatment can be appropriately selected from the range of about 100 to 10,000. Although it is possible even outside the above range, sufficient mechanical strength and elasticity cannot be obtained when the number average degree of polymerization is less than 100, and when the number average degree of polymerization exceeds 10,000, the processability of the composition deteriorates, which is not preferable. .
[0048]
The method of synthesizing the non-fluorinated polysiloxane can be easily synthesized with reference to, for example, the description of JP-A-5-186700.
[0049]
The intermolecular crosslinking of the non-fluorinated polysiloxane is carried out by a polysiloxane molecule having a silyl hydrogen group (Si-H) in which a hydrogen atom is bonded to a silicon atom and a vinyl group (for example, CH₂= CH-COO-, CH₂= C (CH₃The hardness can be increased by addition-reaction crosslinking between non-fluorinated polysiloxane molecules having ()) COO-). A metal catalyst is preferable as a cross-linking catalyst for activating the Si-H group, and a halide such as platinum, palladium, ruthenium, or iridium, or a complex compound having a carbonyl group, a hydroxyl group, an amino group, a cyano group, or a thiocyanate group as a ligand And the like. Further, non-fluorinated polysiloxane molecules having a vinyl group may be intermolecularly crosslinked. As the catalyst for activating the vinyl group, an organic peroxide catalyst can be mentioned.
[0050]
Preferred specific examples of the organic peroxide catalyst will be described below, but the present invention is not limited thereto.
(U-1) Methyl ethyl ketone peroxide
(U-2) Cyclohexanone peroxide
(U-3) 2,4-dichlorobenzoyl peroxide
(U-4) bis-3,3,5-trimethylhexanoyl peroxide
(U-5) Lauroyl peroxide
(U-6) benzoyl peroxide
(U-7) Cumene hydroperoxide
(U-8) Dicumyl peroxide
(U-9) di-t-butyl peroxide
(U-10) 3,3,5-trimethylcyclohexanone peroxide
(U-11) 2,2-di-t-butylperoxybutane
(U-12) t-butylperoxy-2-ethylhexanoate
(U-13) t-butyl peroxybenzoate
(U-14) di-2-ethylhexyl peroxydicarbonate
(U-15) diisopropyl peroxydicarbonate
(U-16) t-butyl peroxyisopropyl carbonate
The metal catalyst or the peroxide catalyst as the cross-linking agent may be added before the application of the non-fluorinated polysiloxane, and the number average polymerization degree may be increased in advance in the state of the coating solution, or the coating may be performed. Thereafter, the number average degree of polymerization may be increased by a heat treatment at 80 to 400 ° C., preferably 120 to 200 ° C., to obtain a final non-fluorinated polysiloxane having an average composition.
[0051]
The noble metal catalyst or peroxide catalyst may be added by dissolving it in a suitable organic solvent, for example, toluene, xylene, dioxolan, acetone, methyl ethyl ketone or the like, or may be used as fine particles in a solid state.
[0052]
The compounding amount of the above compound is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the compound represented by the general formula (1). Exceeding the part deteriorates workability.
[0053]
The thickness of the non-fluorinated polysiloxane molded body is preferably in the range of 100 nm to 1 mm, and more preferably 1 μm to 200 μm. When the thickness is less than 100 nm, the degree of adhesion becomes insufficient in the coating of the non-fluorinated polysiloxane, and the development becomes uneven. When the thickness exceeds 1 mm, it is difficult to obtain a uniform plane of the non-fluorinated polysiloxane.
(Fluorinated hydrocarbon polymer)
Next, the fluorinated hydrocarbon polymer represented by the general formula (3) according to the present invention will be described.
[0054]
In the general formula (3), X₁~ X₄Each independently represents a hydrogen atom, a halogen atom (eg, an atom such as fluorine or chlorine), or a hydrocarbon group having 1 to 16 carbon atoms (eg, a methyl group, an ethyl group, a butyl group, a hexyl group, a dodecyl group, etc.). , X₁~ X₄At least one is a fluorine atom, and X₅~ X₁₀Each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 16 carbon atoms or a hydrocarbon substituent containing an oxygen atom, and may not contain a halogen atom at all. p represents 100 to 9000, q represents an integer of 100 to 600, and t represents 0 or an integer of 1 to 4. Examples of the substituent containing an oxygen atom include a carboxyl group, a carboxylalkyl ester group, a hydroxyalkyl group, a hydroxyalkyloxy group, a hydroxyalkyloxyalkyl group, a hydroxyalkyl (polyalkyloxy) alkyl group, and an alkyl (polyoxyalkyl) oxy group. Glycidylalkyloxy group, glycidyloxyalkyl group, glycidyloxyalkyloxy group and the like. The X₁~ X₁₀Are not all fluorine atoms at the same time.
[0055]
The number average polymerization degree of the fluorinated hydrocarbon polymer represented by the general formula (3) can be appropriately selected from the range of about 100 to 10,000. If the number average degree of polymerization is less than 100, sufficient mechanical strength and elasticity cannot be obtained, and if the number average degree of polymerization exceeds 10,000, the processability of the composition deteriorates, which is not preferable.
[0056]
The method for synthesizing the fluorinated hydrocarbon polymer represented by the general formula (3) can be synthesized, for example, with reference to International Application WO98 / 50229.
[0057]
The coating thickness of the fluorinated hydrocarbon polymer layer represented by the general formula (3) is preferably in the range of 100 nm to 1 mm, and more preferably 1 μm to 200 μm. When the coating thickness is less than 100 nm, the degree of adhesion becomes insufficient and the development becomes uneven when coating with the fluorinated hydrocarbon polymer. When the coating thickness exceeds 1 mm, it becomes difficult to coat the fluorinated hydrocarbon polymer layer.
[0058]
The thickness ratio of the non-fluorinated polysiloxane layer represented by the general formula (1) to the fluorinated hydrocarbon polymer layer represented by the general formula (3) is preferably from 1/10000 to 10,000. Preferred specific examples of the fluorinated hydrocarbon polymer represented by the general formula (3) are shown below, but the present invention is not limited thereto.
[0059]
Embedded image

[0060]
(Primer)
The primer of the present invention will be described.
[0061]
In the present invention, the primer means the adhesiveness between the core metal of the heat drum and the non-fluorinated polysiloxane layer represented by the general formula (1), and the non-fluorinated polysiloxane layer and the fluorinated hydrocarbon polymer layer thereon The former is called primer 1 and the latter is called primer 2.
<Primer 1>
Since the primer 1 is an adhesion between the core metal and the non-fluorinated polysiloxane layer represented by the general formula (1), the silane coupling agent and the metal are contained in the non-fluorinated polysiloxane represented by the general formula (1). A primer containing a coupling agent such as an alkoxide, for example, aluminum alkoxide (aluminum isopropoxide, aluminum ethoxide, etc.) and a titanium alkoxide, for example, titanium propoxide, titanium butoxide, can be used as a primer. As the silane coupling agent, a silane coupling agent having a trialkoxysilane group is preferable, and particularly preferable silane coupling agents are shown below.
[0062]
Embedded image

[0063]
The silane coupling agent is used in a range of 1/1000 to 40 parts by mass, more preferably 1/10 to 18 parts by mass, based on 100 parts by mass of the non-fluorinated polysiloxane represented by the general formula (1). It is preferred to use. If it is less than this range, the adhesiveness is weak and the film is easily peeled off, and if it exceeds the above range, the film becomes weak and the film is easily peeled off.
[0064]
The non-fluorinated polysiloxane may be added by dissolving it in an alcohol such as ethyl alcohol, methyl alcohol, or isopropyl alcohol or a ketone such as acetone or methyl ethyl ketone, or may be used without a solvent.
[0065]
The thickness of the coating film is preferably from 10 nm to 300 μm, more preferably from 100 nm to 100 μm. If the amount is less than the above range, it is difficult to obtain the adhesion effect of the primer layer.
<Primer 2>
The primer 2 for adhering both the non-fluorinated polysiloxane and the fluorinated hydrocarbon polymer preferably has a composition of both, and in the present invention, the primer 2 has the same composition as the non-fluorinated polysiloxane represented by the general formula (1). A composition in which the fluorinated hydrocarbon polymer represented by the general formula (3) is mixed is economical. Further, a preferred method is to use a fluorinated polysiloxane represented by the following general formula (4).
[0066]
Embedded image

[0067]
In the general formula (4), R₅~ R₉Each independently represents a hydrogen atom, an acroyl group, a methacryloyl group, or a hydrocarbon group having 1 to 16 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group), and Rf represents a fluorinated hydrocarbon group ( A perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group (for example, a perfluorohexyl group, a perfluorooctyl group, a perfluorononenyl group, etc.), L₁Is a divalent linking group (methylene group, ethylene group, propylene group, butylene group, hexamethylene group, etc.), a and c are integers of 0 to 1000, b is an integer of 1 to 8000, and a and c are simultaneously 0. It will not be.
[0068]
In the method of coating the primer, the primer may be used by dissolving or dispersing it in the above-mentioned alcohols or ketones, or may be applied in a liquid state by heating without a solvent. The thickness of the coating film and the like can be set in the same manner as the primer 1. Preferred specific examples of the compound represented by the general formula (4) are shown below, but the present invention is not limited thereto.
[0069]
Embedded image

[0070]
In the present invention, the composition of the non-fluorinated polysiloxane represented by the general formula (1) or the fluorinated hydrocarbon polymer represented by the general formula (3) can contain an inorganic filler as necessary. . In particular, it is preferable to include it in the non-fluorinated polysiloxane represented by the general formula (1). The purpose of adding the inorganic filler is to control the strength, thermal conductivity, electric resistance, slipperiness and the like of the coating film.
[0071]
The inorganic filler is not particularly limited as long as it has a certain strength. However, alumina, silica, titania, zirconia, magnesia, zinc oxide, oxide oxides such as calcium oxide, silicon carbide, silicon nitride, boron nitride, aluminum nitride And non-oxide inorganic substances such as aluminum carbide, titanium boride, titanium nitride, and titanium carbide. Among them, oxide-based inorganic substances, more preferably alumina, silica and titania, are economically preferable because they are industrially produced in large quantities and are easily available.
[0072]
The inorganic filler used in the present invention is not particularly limited in its raw material, production method and the like, and various shapes such as fibrous, needle-like (including whisker), granular, and scale-like can be used. In the coating film, the inorganic filler may be used alone or in combination of two or more. Further, various shapes may be mixed and used. Furthermore, even when two or more inorganic fillers may be used in combination, their mixing ratio is not particularly limited and can be arbitrarily selected.
[0073]
In the coating film production, in order to ensure the uniformity of dispersion of these inorganic fillers, and to uniformly disperse them in the coating film, it is desirable that the inorganic fillers do not include those having a coarse diameter of 100 μm or more. . The average particle size of the inorganic filler may be determined in consideration of the thickness of the coating film, but is usually 20 μm or less on average, and more preferably 5 μm or less on average. The lower limit is not reduced, but is usually about 10 nm. If the average particle size is less than 10 nm, the cost of fine particles increases, and if the average particle size is 100 μm or more, unevenness on the surface of the molded product is large, development becomes nonuniform, and image quality is impaired.
[0074]
The blending amount of the inorganic filler can be arbitrarily set to 0.3 to 300 parts by mass with respect to 100 parts by mass of the non-fluorinated siloxane represented by the general formula (1), but is preferably 5 to 95 parts by mass. Is preferred.
[0075]
In order to improve the dispersion of the inorganic filler, it is preferable to use a surfactant. Surfactants may be any as long as they can uniformly disperse the inorganic filler in the composition, and include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Either can be used. For example, sodium alkyl sulfate (eg, sodium lauryl sulfate, sodium octyl sulfate, etc.), sodium alkyl ether sulfate (eg, sodium lauryl ether sulfate, sodium dodecyl ether sulfate, etc.), triethanol alkyl sulfate, triethanolamine alkyl ether sulfate, ammonium Anionic surfactants such as alkyl sulfate, ammonium alkyl ether sulfate, sodium alkyl ether phosphate and sodium fluoroalkyl carboxylate; cationic surfactants such as alkyl ammonium salt and alkyl benzyl ammonium salt; polyoxyethylene alkyl ether; Oxyethylene phenyl ether. A particularly preferred structure for the present invention is shown by the following general formula (5).
[0076]
Embedded image

[0077]
In the general formula (5), Rf represents a fluorinated alkyl group having 1 to 12 carbon atoms (for example, a perfluoromethyl group, a perfluoroethyl group, a perfluorobutyl group, a perfluorooctyl group, etc.), an alkenyl group (for example, Perfluoropropenyl group, perfluorobutenyl group, perfluorononenyl group, etc.);₁And L₂Represents a divalent linking group (for example, a methylene group, an ethylene group, a butylene group, a hexamethylene group, etc.), Y represents a divalent to tetravalent group, A represents an anionic group (sulfonic acid group or carboxylic acid group) or Represents a salt thereof (for example, sodium, potassium or lithium salt), m and n represent 0 or 1, and p and q represent an integer of 1 to 4.
[0078]
In the synthesis of the compound represented by the general formula (5), a fluorine atom-introduced alkyl group having 1 to 12 carbon atoms (for example, a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group) and an alkenyl group (for example, , A perfluoropropenyl group, a perfluorobutenyl group, a perfluorononenyl group, etc.), an acid chloride compound or an iodide) and a tri- to hexavalent alkanol compound each having a fluorine atom, and a hydroxyl group. It can be obtained by a condensation reaction or an addition reaction with an aromatic compound or a hetero compound having 3 or 4 aromatic compounds.
[0079]
Further, as another synthesis method, a compound having a non-fluorinated structure can be synthesized, and can be synthesized by electrolytic fluorination. When an alkanol compound is used, glycerin, pentaerythritol, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentene, 1,2,6-hexanetriol, 1,1,1-Tris (hydroxymethyl) propane, 2,2-bis (butanol) -3, aliphatic triol, tetramethylolmethane, D sorbitol, xylitol, D-mannitol and the like are useful as raw materials. Preferred specific examples of the compound represented by the formula (5) are shown below, but the invention is not limited thereto.
[0080]
Embedded image

[0081]
Embedded image

[0082]
The method of adding the compound represented by formula (5) preferably used in the present invention includes water, alcohols such as methanol and ethanol, ketones such as methyl ethyl ketone and acetone, aromatic compounds such as toluene and xylene, and normal hexane. It may be added by dissolving or partially dispersing in a solvent such as aromatic solvent such as decane or decane, or may be added as a solid fine powder. The amount added is preferably in the range of 1 μg to 13 g per 1 g of inorganic fine particles, and particularly preferably in the range of 1 to 300 mg. If it is less than this range, the effect of dispersing the inorganic fine particles is hardly obtained, and if it exceeds this, foams are easily generated, and the productivity is reduced.
[0083]
Various additives can be blended in the polymer dispersion composition used in the present invention depending on the use.
[0084]
Examples of the additive include a stabilizer, a pigment, a thickener, a decomposition accelerator, a rust inhibitor, an antifoaming agent, and the like.
[0085]
As a solvent of each coating composition, an organic solvent is used to uniformly disperse the fluorinated polymer and the inorganic filler, and also volatilize after the heat treatment, for example, methyl ethyl ketone, dioxane, dioxolan, tetrahydrofuran, acetone, Methyl cellosolve, butyl cellosolve, ethylene glycol, ethanol, n-methylpyrrolidone, diacet alcohol, toluene, benzene, xylene and the like.
[0086]
As a coating method of the coating film of each coating composition, various known coating methods can be adopted. For example, a spray coating method, a bar coating method, a flow coating method, a dip method, a casting method, a spin coating method and the like can be mentioned.
[0087]
In particular, the splat method is suitable in that the film thickness of the coating film can be easily made uniform. As the coating machine used in the case of the splat method, a known coating machine can be used.
[0088]
The heat treatment is preferably performed at a temperature of about 80 to 400C, more preferably 120 to 180C. When the heat treatment temperature is lower than 80 ° C., the heat treatment time needs to be lengthened. On the other hand, when the heat treatment temperature exceeds 400 ° C., the non-fluorinated polysiloxane or fluorinated hydrocarbon polymer may be decomposed, which is not preferable. The heat treatment time is not particularly limited, but may be generally about 10 to 60 minutes.
(Heat developing material)
In the heat developing material, at least one photosensitive layer is provided on a support, and an AH layer is provided below the photosensitive layer (between the support and the photosensitive layer) and a protective layer is provided above the photosensitive layer. Further, a backing layer (BC layer) is provided on the side opposite to the side having the photosensitive layer with respect to the support, and a protective layer is provided thereon. The photosensitive layer contains silver halide, an organic silver salt, a reducing agent, and a binder (polymer binder). The AH layer and the BC layer have a high absorption efficiency with respect to the photosensitive wavelength, and a dye that does not easily remain in the binder is present in the binder to deteriorate sharpness due to irregular reflection at the interface between constituent layers of the heat developing material and to reduce interference fringes. Prevent.
[0089]
As the binder for the AH layer, the BC layer, the protective layer, and the like, the same or different material as the photosensitive layer can be used. When a dye is used for the BC layer, the AH layer may not be provided. In order to reduce the residual color derived from the dyes in the AH layer and the BC layer, a dye capable of being decolorized by heat may be used, and a base generating precursor may be used in some cases in order to further promote the thermal decolorization. Regarding the curing of the binder, the photosensitive layer, the AH layer, the BC layer, etc. are used in the range which does not impair the photographic performance by appropriately selecting the epoxy crosslinking agent, the acid anhydride compound and the base generating precursor irrespective of the protective layer alone. be able to. Hereinafter, the materials used for the heat development material will be sequentially described in detail.
(Photosensitive silver halide)
The photosensitive silver halide used in the photothermographic material of the present invention may be produced by any method known in the field of photographic technology such as a single jet or double jet method, for example, an ammonia method, a neutral method, an acid method, or the like. It can be prepared by any method. It can be prepared in this way in advance and then mixed with other components of the invention and introduced into the composition of the invention. In this case, in order to sufficiently bring the photosensitive silver halide into contact with an organic silver salt described later, for example, US Pat. No. 3,706,564, US Pat. No. 3,706,565, No. 3,713,833, No. 3,748,143, and British Patent No. 1,362,970. Means using a polymer other than gelatin, means for enzymatically decomposing gelatin in a light-sensitive silver halide emulsion as described in British Patent No. 1,354,186, or US Pat. No. 4,076,539. By preparing the photosensitive silver halide in the presence of a surfactant as described in the specification, each means such as a means for omitting the use of the protective polymer can be applied.
[0090]
The silver halide preferably has a small grain size and high sensitivity in order to obtain good image quality. This is because when the particle size is small, the granularity and the resolution are good. However, since the sensitivity is low, a crystal form which is easily sensitized by spectral sensitization or chemical sensitization is preferable.
[0091]
Specifically, the average particle size is 0.1 μm or less, preferably 0.01 to 0.1 μm, and particularly preferably 0.02 to 0.08 μm. The shape of the silver halide is not particularly limited, but cubic or octahedral grains such as so-called normal crystals are preferred. The silver halide composition may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide, but silver iodobromide is preferred.
[0092]
The amount of the silver halide is 50% by mass or less, preferably 25 to 0.1% by mass, more preferably 15 to 0.1% by mass, based on the total amount of the silver halide and the organic silver salt described below.
[0093]
The photosensitive silver halide used in the photothermographic material of the present invention can be used, as described in British Patent No. 1,447,454, when preparing an organic silver salt described later. By coexisting a halogen component with the organic silver salt-forming component and injecting silver ions into the component, it is possible to generate the organic silver salt almost simultaneously.
[0094]
Further, as another method, a silver halide forming component is allowed to act on a solution or dispersion of an organic silver salt prepared in advance or a sheet material containing the organic silver salt, so that a part of the organic silver salt is converted into a photosensitive halogen. It can also be converted to silver halide.
[0095]
The silver halide thus formed is in effective contact with the organic silver salt and exhibits a favorable effect.
[0096]
These silver halides are used in a small amount stoichiometrically with respect to the organic silver salt.
Usually, the range is 0.001 to 0.7 mol, preferably 0.03 to 0.5 mol, per 1 mol of the organic silver salt. Two or more silver halide forming components may be used in combination within the above range. Various conditions such as a reaction temperature, a reaction time, and a reaction pressure in the step of converting a part of the organic salt into silver halide using the above-mentioned silver halide forming component can be appropriately set according to the purpose of production. it can. Usually, the reaction temperature is -23 to 74 ° C, the reaction time is 0.1 second to 72 hours, and the reaction pressure is preferably set to the atmospheric pressure.
[0097]
This reaction is preferably performed in the presence of a polymer used as a binder described below. The amount of the polymer used at this time is 0.01 to 100 parts by mass, preferably 0.1 to 10 parts by mass per 1 part by mass of the organic silver salt.
[0098]
The photosensitive silver halide prepared by the above-mentioned various methods can be chemically sensitized with, for example, a sulfur-containing compound, a platinum compound, a palladium compound, a silver compound, a tin compound, a chromium compound, or a combination thereof. Methods and procedures for chemical sensitization are described in, for example, U.S. Pat. No. 4,036,650, British Patent No. 1,518,850, JP-A-51-2430, JP-A-51-78319, and JP-A-51-78319. No. 51-81124.
(Chemical sensitizer)
The chemical sensitizer preferably used in the present invention is an organic chalcogen sensitizer, and an organic compound containing a sulfur atom, a selenium atom, or a tellurium atom as a chalcogen in a molecule is preferable. In the chemical structure, a compound in which a chalcogen atom is directly bonded to a carbon atom or a phosphorus atom, that is, of the four hands of a carbon atom, two are chalcogens and the other two are any organic Or two of the five bonds of a phosphorus atom are bonded to a chalcogen atom, and the other is an optional organic substituent and an arbitrary substituent is an aryl group Is preferred.
[0099]
The aryl group is preferably an aromatic group or a heterocyclic compound containing a hetero atom, and most preferably a phenyl group or a phenyl group substituted with a fluorine atom. Preferred specific examples include triphenylphosphine selenide, triphenylphosphine oxide, and triphenylphosphine telluride.
[0100]
The chemical sensitizer may be added by dissolving it in water or an organic solvent in a silver halide dispersion solution, or may be added as fine particles or powder. The addition amount is 1 × 10 5 per mol of silver halide.^-9~ 1 × 10^-2Mol is suitable, preferably 1 × 10^-8~ 1 × 10^-4Is a mole. The ripening temperature at the time of chemical sensitization is preferably 30 to 90 ° C., and the ripening time is preferably 20 to 8 hours, usually 40 to 90 minutes.
[0101]
Photosensitive silver halides include transition metals, particularly compounds belonging to Groups 4 to 6 of the Periodic Table of the Elements, in order to prevent illuminance failure, gradation processing, sensitivity, fog, and storage stability. Is preferably doped (contained).
[0102]
Specifically, ions, complexes or complex ions such as Rh, Ru, Re, Ir, Os, and Fe are preferable.
[0103]
The doping amount is 1 × 10 5 per mol of silver halide.^-9~ 1 × 10^-2Mol is suitable, preferably 1 × 10^-8~ 1 × 10^-4Is a mole. The compound providing these metal ions or complex ions is preferably added during silver halide grain formation and incorporated into silver halide grains. Preparation of silver halide grains, that is, nucleation, growth, and physical ripening It may be added at any stage before and after chemical sensitization, but it is particularly preferable to add at the stage of nucleation, growth and physical ripening, and it is more preferable to add at the stage of nucleation and growth. , Most preferably the nucleation stage.
[0104]
During the addition, it may be added in several portions, may be added uniformly in the silver halide grains, or may be added uniformly to the silver halide grains, as disclosed in JP-A-63-29603, JP-A-2-306236, and JP-A-2-306236. As described in JP-A-167545, JP-A-4-76534, JP-A-6-110146, JP-A-5-273683 and the like, the particles can be contained in the particles with a distribution.
(binder)
As the binder used in the photosensitive layer or the non-photosensitive layer of the photothermographic material of the present invention, a silver halide, an organic silver salt, a material which is preferable as a place where a reducing agent reacts, for example, hydroxymethylcellulose, carboxymethylcellulose, methylcellulose, ethylcellulose Such as cellulose derivatives, polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl butyral, sodium polyacrylate, polyethylene oxide, acrylamide-acrylate copolymer, styrene-maleic anhydride copolymer, polyacrylamide, polyvinyl acetate, Polyurethane, polyacrylic acid, polyacrylate, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, vinyl chloride-vinyl acetate copolymer, styrene-butadiene-a Such as acrylic acid copolymer. Further, after drying and forming a film, the coating film preferably has a low equilibrium moisture content.
(Mat agent)
The photothermographic material of the invention preferably contains a matting agent in the protective layer and the BC layer on the photosensitive layer. The material of the matting agent preferably used in the present invention may be either an organic substance or an inorganic substance. Examples of the inorganic substance include silica described in Swiss Patent No. 330,158 and French Patent No. 1,296,995. And alkali metals described in British Patent No. 1,173,181 and carbonates such as cadmium and zinc can be used as a matting agent. Examples of organic substances include starch described in U.S. Pat. No. 2,322,037, derivatives described in Belgian Patent 625,451 and British Patent No. 981,188, and Japanese Patent Publication No. 44-3643. Polyvinyl alcohol, polystyrene or polymethacrylate described in Swiss Patent No. 330,158, etc., polyacrylonitrile described in U.S. Pat. No. 3,078,257, polycarbonate described in 3,022,169 and the like. Organic matting agents such as
[0105]
The shape of the matting agent may be either regular or irregular, but is preferably regular and preferably spherical.
[0106]
The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere. In the present invention, the particle size of the matting agent indicates a diameter when converted into a spherical shape.
[0107]
The matting agent used in the present invention preferably has an average particle size of 0.5 to 10 μm, more preferably 1.0 to 8.0 μm. Further, the matting agent preferably has a monodispersity of 50 or less, more preferably 40 or less, and particularly preferably 20 or less.
[0108]
Here, the monodispersity of the particles is a value obtained by multiplying the value obtained by dividing the standard deviation of the particle diameter by the particle diameter by 100.
[0109]
The method for adding the matting agent may be a method in which the matting agent is dispersed in the coating solution in advance, or a method in which the matting agent is sprayed before the drying is completed after the coating solution is applied. When a plurality of types of matting agents are added, both methods may be used in combination.
(Organic silver salt)
The photothermographic material of the present invention forms a photographic image by a heat development process, and includes a reducible silver source (organic silver salt), a catalytically active amount of silver halide, a hydrazine derivative, a reducing agent and optionally It is preferable that the photothermographic material generally contains a color tone agent for controlling the color tone of silver in a state of being dispersed in an organic binder matrix.
[0110]
The photothermographic material of the present invention is stable at room temperature, but is developed by heating to a high temperature (for example, 80 to 200 ° C.) after exposure. The heating includes a one-step method of heating at a constant temperature for a fixed time and a method of stepwise heating such as preheating, main heating or post-heating, and the method of heating can be appropriately selected.
[0111]
By heating, silver is generated through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent.
[0112]
This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated on the silver halide upon exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas and is imaged. This reaction process proceeds without supplying a processing liquid such as water from the outside.
[0113]
As the organic acid containing a reducible silver ion source, a hetero organic acid and a silver salt of an acid polymer are used. Further, an organic or inorganic silver salt complex whose ligand has a total stability constant of 4.0 to 10.0 for silver ions is also useful. Examples of these silver salts are described in, for example, Research Disclosure (hereinafter simply referred to as RD) 17029 and 29996, and particularly preferred are, for example, gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid. Silver salts of acids, arachidic acid, erucic acid and the like.
(Reducing agent)
The reducing agent contained in the photothermographic material of the present invention is described in U.S. Pat. Nos. 3,770,448, 3,773,512, and 3,593,863, and is preferable. The following are mentioned as a reducing agent.
(K-1) 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane
(K-2) bis (2-hydroxy-3-tert-butyl-5-methylphenyl) methane
(K-3) 2,2-bis (4-hydroxy-3-methylphenyl) propane
(K-4) 4,4-ethylidene-bis (2-tert-butyl-6-methylphenol)
(K-5) 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane
The compounds shown above are used by dispersing in water or dissolving in an organic solvent. As the organic solvent, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, and aromatic solvents such as toluene and xylene can be arbitrarily selected.
[0114]
The amount of the reducing agent used is 1 × 10^-2~ 1 × 10 mol, preferably 1 × 10^-2１1 × 1.5 mol.
(Color tone agent)
It is preferable to add a toning agent to the dry imaging material of the present invention. Examples of suitable toning agents include, for example, merocyanine dyes (e.g., 3-ethyl-5-((3-ethyl-2-benzothiazolinylidene (benzothiazolinylidene))-1-methylethylidene). Phthalazinone, phthalazinone derivatives or metal salts of these derivatives (eg, 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazi) Non and 2,3-dihydro-1,4-polyhalomethane compound dione); a combination of phthalazinone and a sulfinic acid derivative (for example, 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate) ); A combination of a polyhalomethane compound and phthalic acid; a polyhalomethane compound (Including adducts of polyhalomethane compounds) and maleic anhydride and phthalic acid, 2,3-naphthalenedicarboxylic acid or o-phenylene derivatives and anhydrides thereof (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and Combinations with at least one compound selected from tetrachlorophthalic anhydride); quinazoline quinones, benzoxazine, naltoxazine derivatives; benzoxazine-2,4-diones (eg, 1,3-benzoxazine-2, 4-dione); pyrimidines and asymmetric-triazines (eg, 2,4-dihydroxypyrimidine) and tetraazapentalene derivatives (eg, 3,6-dimercapto-1,4-diphenyl-1H, 4H-2, 3a, 5,6a-tetraazapentalene) and the like.
(Spectral sensitizing dye)
The photothermographic material of the present invention includes, for example, JP-A-63-159841, JP-A-60-140335, JP-A-63-231437, JP-A-63-259651, JP-A-63-304242, JP-A-63-15245, U.S. Pat. Nos. 4,639,414, 4,740,455, 4,741,966, 4,751,175, and 4,835,096. A dye can be preferably used.
[0115]
As useful sensitizing dyes for use in the invention, for example, compounds described in JP-A-9-34078, JP-A-9-54409, and JP-A-9-80679 are preferably used.
(Support)
As the support preferably used in the photothermographic material of the present invention, a support such as paper, synthetic paper, nonwoven fabric, metal foil, polyester such as polyethylene terephthalate and polyethylene naphthalate, and plastic such as polycarbonate and polypropylene can be used. Yes, and a composite sheet may be optionally used by combining these.
[0116]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples, but embodiments of the present invention are not limited thereto.
[0117]
Example 1
(Coating of thermal drum)
A cylindrical heat drum made of aluminum having an outer diameter of 100 mm, a length of 450 mm, and a thickness of 8 mm was coated with the following composition. The opposite roller was made of stainless steel and left uncoated.
<Coating of primer 1>
6 g of the silane coupling agent shown in Table 1 was added to 100 g of the non-fluorinated polysiloxane shown in Table 1 and kneaded well, and then applied on an aluminum core metal at a thickness of 1 μm and dried at 50 ° C. for 10 minutes. did.
<Polysiloxane coating>
Next, 300 g of one or two of the non-fluorinated polysiloxanes shown in Table 1 (150 g for each of the two types), 10 mg of the noble metal catalyst shown in Table 1, 3 g of peroxide, and an inorganic filler (average) After adding 56 g (described in Table 1 of particle diameter) and kneading well with a kneader, the mixture was uniformly coated on the primer 1 so as to have a thickness of 3 mm, and dried at 50 ° C. for 10 minutes. The dry film thickness is described in Table 1.
<Coating of primer 2>
Each of the drums was coated with the non-fluorinated polysiloxane layer shown in Table 1 and then 100 g of the same non-fluorinated polysiloxane shown in Table 1 (50 g each when two types were used) and the fluorine shown in Table 2 3 g (1.5 g each when two types are used), 1.2 mg of the noble metal catalyst and 3 g of peroxide shown in Table 2 were added and kneaded, and a 1 μm thick layer was formed on the polysiloxane layer. It was applied.
<Coating of fluorinated hydrocarbon polymer>
Next, 300 g of one or two kinds of the fluorinated hydrocarbon polymers shown in Table 2 (however, 150 g in the case of two kinds), 10 g of an inorganic filler having an average particle diameter shown in Table 2, and 3 g of a surfactant were added. The mixture was heated and reacted at 80 ° C. for 1 hour while kneading well in a kneader, then coated, and dried at 50 ° C. for 10 minutes. After drying, the coated heat drum at the temperature shown in Table 2 was heat-treated in an oven for 3 hours. The dry film thickness is described in Table 2.
[0118]
As a comparative example 1, a coating solution of a non-fluorinated polysiloxane was prepared as follows.
[0119]
After adding 43 g of silica having an average particle diameter of 6 μm to 40 g of polysiloxane having no vinyl group and silyl hydrogen group (average polymerization degree: 300), the mixture was heated and reacted at 180 ° C. for 1 hour while kneading well in a kneader, and then heated. The drum was coated at a thickness of 400 μm and dried.
[0120]
The coating of the fluorinated hydrocarbon polymer as Comparative 2 to be applied thereon was applied as follows.
[0121]
It was coated with polyfluoroethylene (Teflon (R) having a number average degree of polymerization of 2200) and dried. After drying, heat treatment was performed at 180 ° C. for 4 hours.
(Preparation of photothermographic material for thermal development)
<Preparation of undercoated photographic support>
0.8 mW / cm on the coated surface of a polyethylene terephthalate support having a thickness of 175 μm²・ A corona discharge treatment is performed for one minute, on one surface, the following undercoating coating liquid a-1 is applied so as to have a dry film thickness of 0.8 μm, and dried to form an undercoating layer A-1, On the opposite side, an undercoating coating solution b-1 described below was applied so as to have a dry film thickness of 0.8 μm, and dried to obtain an undercoating layer B-1.
<Undercoat coating liquid a-1>
Butyl acrylate (30% by mass)
t-butyl acrylate (20% by mass)
Styrene (25% by mass)
2-hydroxyethyl acrylate (25% by mass)
270 g of a copolymer latex solution (solid content: 30%)
Hexamethylene-1,6-bis (ethylene urea) 0.8 g
Make up to 1 liter with water.
<Undercoat coating solution b-1>
Butyl acrylate (40% by mass)
Styrene (20% by mass)
Glycidyl acrylate (40% by mass)
270 g of a copolymer latex solution (solid content: 30%)
Hexamethylene-1,6-bis (ethylene urea) 0.8 g
Make up to 1 liter with water.
[0122]
Subsequently, 8 W / m was formed on the upper surfaces of the undercoat layer A-1 and the undercoat layer B-1.²・ The following undercoating layer coating solution a-2 is applied to the following layer A-1 as a layer A-2 below so as to have a dry film thickness of 0.1 μm. The lower undercoating layer B-2 having an antistatic function was coated on top of No. 1 so as to have a dry film thickness of 0.8 μm.
<Undercoat upper layer coating solution a-2>
Gelatin 0.4g / m²
Silica particles (average particle size 3 μm) 0.1 g
Make up to 1 liter with water.
<Undercoat upper layer coating solution b-2>
Styrene butadiene copolymer latex liquid (solid content 20%) 80g
6 g of polyethylene glycol (weight average molecular weight 600)
Make up to 1 liter with water.
(Preparation of photosensitive silver halide emulsion A)
After dissolving 7.5 g of inert gelatin and 10 mg of potassium bromide in 900 ml of water and adjusting the temperature to 35 ° C. and pH 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and potassium bromide in a molar ratio of (98/2) are added. The aqueous solution containing potassium iodide was added over 10 minutes by a controlled double jet method while maintaining the pAg at 7.7. Thereafter, 0.3 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 5 with NaOH, and the average particle size was 0.06 μm, and the variation coefficient of the projected diameter area. Cubic silver iodobromide grains of 8% and [100] face ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, desalting treatment, and then adjusted to pH 5.9 and pAg 7.5 with 0.1 g of phenoxyethanol to obtain photosensitive silver halide emulsion A.
(Preparation of dispersed organic silver salt)
111.4 g of behenic acid, 83.8 g of arachidic acid and 54.9 g of stearic acid were dissolved in 4720 ml of pure water at 80 ° C. Next, while stirring at a high speed, 540.2 ml of a 1.5 mol sodium hydroxide aqueous solution was added, 6.9 ml of concentrated nitric acid was added, and the mixture was cooled to 55 ° C. to obtain a sodium organic acid solution. With the temperature of the organic acid solution maintained at 55 ° C., the photosensitive silver halide emulsion A (containing 0.038 mol of silver) and 450 ml of pure water were added and stirred for 5 minutes. Next, 760.6 ml of a 1 molar silver nitrate solution was added over 2 minutes, and the mixture was further stirred for 20 minutes, and water-soluble salts were removed by filtration. Thereafter, washing with deionized water and filtration were repeated three times until the conductivity of the filtrate reached 2 μS / cm, and dried to obtain a dispersed organic silver salt.
<Back side coating>
The back layer and the back layer protective layer were simultaneously coated with a coating solution prepared by adding the following composition to a methyl ethyl ketone solution and extruded under reduced pressure so as to have the following amounts.
[0123]
Back layer (first layer)
PVB-1 1.1 g / m²
Dye: C 12 mg / m²
Colloidal silica 12mg / m²
Sodium dodecylbenzenesulfonate 13mg / m²
Back layer protective film (second layer)
Cellulose acetate butyrate 0.8 g / m²
Matting agent (PMMA: average particle size 5 μm) 0.02 g / m²
Activator: N-propyloctylsulfonamidoacetic acid 0.02 g / m²
Hardener: 1,2-bis (vinylsulfonamido) ethane 0.02 g / m²
<Coating of photosensitive layer>
AH layer (first layer)
PVB-1 0.3 g / m²
Dye: C 8 mg / m²
Photosensitive layer (second layer)
For the preparation of the photosensitive layer, a coating solution was prepared by adding a methyl ketone solution of the following composition. The coating solution was kept at 35 ° C. and dried by coating so that the following amount was obtained.
[0124]

[0125]
Embedded image

[0126]
Surface protective layer (third layer)
Cellulose acetate butyrate 1.2 g / m²
Phthalazine 0.1g / m²
0.7 g / m of 4-methylphthalic acid²
Tetrachlorophthalic acid 0.2 g / m²
Silica matting agent (average particle size 3 μm) 0.5 g / m²
Antistatic agent: E 0.1 g / m²
The above composition was simultaneously and multi-layer coated at the coating amount described above at a coating speed of 260 m / min and dried at 48 ° C. for 56 seconds.
(Film adhesion test)
4cm of each heat drum made²1cm on the outermost surface²After 100 pieces per square were placed and left under the following conditions, the temperature was returned to room temperature, and a pressure-bonding peeling test was performed using a cellophane adhesive tape.
[0127]
After leaving at 220 ° C. for 2 hours, leaving at -10 ° C. for 1 hour × 12 cycles, the film adhesion test results were evaluated in terms of the percentage of cross-cut peeling. The less peeling, the better the adhesion. For example, 50% This indicates that half of the area has been peeled off, and if it is 20% or less, it is a practically acceptable level.
(Film contamination evaluation test)
Evaluation of dirt on the produced heat drum was performed by cutting the heat-developable heat-developable material exposed to have a density of 1.5 to a width of 2 cm and a length of 30 cm. After processing for 100 days per sheet and 1,000 sheets per day for 5 days, the stain on each surface was evaluated.
[0128]
The evaluation method is that the surface of the heat drum and the opposed roller after the treatment test are washed with a 1: 3: 1 solution of water: methanol: acetone (2 ml / cm).²), And the concentration of this solution was measured with a digital differential densitometer DD7 (manufactured by Atago). The smaller the measured value (minimum 0.000%), the less the stain, and the larger the numerical value (maximum 2.000%), the greater the stain. If the stain is displayed at 1%, it is practically no problem. Table 1 summarizes the results, Table 1 shows the coating contents of primer 1 and polysiloxane, Table 2 shows the coating contents of primer 2 and the fluorinated hydrocarbon polymer layer, and Table 3 shows the results of the performance test. showed that.
[0129]
[Table 1]

[0130]
[Table 2]

[0131]
[Table 3]

[0132]
According to Tables 1, 2, and 3, the heat drum was coated with a non-fluorinated polysiloxane and then coated with a fluorinated hydrocarbon polymer. It turns out that it does not occur.
[0133]
【The invention's effect】
Advantageous Effects of Invention According to the present invention, a heat developing process excellent in durability that gives a high quality image without a stain on a heat drum in a heat developing device for a long period of time and without transferring a stain on a heat-developable heat-developable photosensitive material. The device was obtained.
[Brief description of the drawings]
FIG. 1 is a schematic sectional view of a heat developing device.
FIG. 2 is a schematic diagram illustrating a configuration of a heat developing unit.
[Explanation of symbols]
1 Heat drum
2 Opposed rollers
4 Bracket
5 Slot
6 Separation claws
11 shaft
20 frames
21 shaft
22 coil spring
23 Rotation axis
25 Timing belt
35 Support tube
36 Primer layer
37 Non-fluorinated polysiloxane layer
38 Primer layer
39 Fluorinated hydrocarbon polymer layer
40 shaft bearing
100 Thermal development device
110 Feeding unit
120 Exposure unit
130 Thermal development section
140 Extraction device
141 142, 143 Transport device
144 Supply Roller Pair
145 transport roller pair
150 Cooling unit
160 output tray
170 control means
F film
C case
L laser light

Claims (12)

A heat developing device having a heat drum and a facing roller for heat developing a heat developable photosensitive material having a photosensitive layer containing a silver salt and a reducing agent on at least one surface of the support and a layer for protecting the photosensitive layer; In the heat development processing apparatus, the heat drum or the opposed roller of the heat development processing apparatus is coated with a non-fluorinated polysiloxane represented by the following general formula (1). A thermal development processing apparatus characterized by being coated with a fluorinated hydrocarbon polymer represented by the formula (1).

(Wherein, R _{1 to} R ₄ are a hydrogen atom or a hydrocarbon group having _{1 to} 16 carbon atoms, W ₁ is a group having a polymerizable vinyl group, a is an integer of 10 to 10000, and b and c are 0 to 1000. And Z is a hydrogen atom, a hydrocarbon group having 1 to 16 carbon atoms, or a group represented by the following general formula (2).

(In the formula, R ₅ , R ₆ and R ₇ each represent a hydrocarbon group having 1 to 16 carbon atoms.)

(Wherein, X _{1 to} X ₄ each independently represent a hydrogen atom, a halogen atom, or a group selected from a hydrocarbon group having 1 to 16 carbon atoms, at least one of which is a fluorine atom, and X _{5 to} X ₁₀ represent Each independently represents a hydrogen atom, a halogen atom or a group selected from a hydrocarbon group having 1 to 16 carbon atoms, t represents 0 or 1, p represents an integer of 10 to 8000, and q represents a positive integer of 1 to 3000; However, X _{1 to} X ₁₀ are not all fluorine atoms.) In the general formula (1), a is 100 to 9000, c is an integer of 10 to 300, and X _{1 to} X ₄ represented by the general formula (3) are all fluorine atoms. The heat development processing apparatus according to claim 1. In the general formula (1), b is 10 to 500, and in the formula represented by the general formula (3), one of the substituents represented by X _{5 to} X ₁₀ is a substituent having an oxygen atom. 3. The thermal development processing apparatus according to claim 1, wherein: The non-fluorinated polysiloxane represented by the general formula (1) contains an inorganic filler, and the inorganic filler is alumina, silica, titania, zirconia, magnesia, iron oxide, zinc oxide, calcium oxide, silicon carbide. And at least one member selected from the group consisting of boron nitride, boron carbide, aluminum nitride, aluminum carbide, titanium boride, titanium nitride, and titanium carbide. Thermal processing equipment. The thermal developing apparatus according to claim 4, wherein the inorganic filler contained in the non-fluorinated polysiloxane has an average particle diameter of 10 to 100 nm. The thermal development processing apparatus according to claim 4, wherein the inorganic filler is contained in the presence of a fluorinated surfactant. The coating thickness of each of the non-fluorinated polysiloxane represented by the general formula (1) and the fluorinated hydrocarbon polymer represented by the general formula (3) is 100 nm to 1 mm. 6. The thermal development processing apparatus according to any one of items 5 to 5. 2. The non-fluorinated polysiloxane represented by the general formula (1) is cross-linked, and the cross-linking is promoted by one or more catalysts selected from a platinum catalyst and an organic peroxide. The thermal development processing apparatus according to any one of claims 1 to 7. The group having a polymerizable vinyl group of the non-fluorinated polysiloxane represented by the general formula (1) is an acryloyl group or a methacryloyl group. Thermal processing equipment. The coating films of the respective coating layers of the non-fluorinated polysiloxane represented by the general formula (1) and the fluorinated hydrocarbon polymer represented by the general formula (3) are simultaneously or independently heat-treated at 80 to 400 ° C. The heat development processing apparatus according to claim 1, wherein the heat development processing is performed. A heat drum or a facing roller coats the core metal with the non-fluorinated polysiloxane represented by the general formula (1), and further forms a fluorinated hydrocarbon polymer represented by the general formula (3) on the coating layer. Prior to coating the non-fluorinated polysiloxane on the core metal of the heat drum or the opposed roller, a primer component treated with an alkoxysilane compound or an alkoxy metal compound is applied. The heat development processing apparatus according to claim 1. A heat drum or a facing roller coats the core metal with the non-fluorinated polysiloxane represented by the general formula (1), and further forms a fluorinated hydrocarbon polymer represented by the general formula (3) on the coating layer. After coating with the non-fluorinated polysiloxane, applying a primer layer containing the fluorinated polysiloxane, and then coating with a fluorinated hydrocarbon polymer represented by the general formula (3). The thermal development processing apparatus according to any one of claims 1 to 11, wherein

Images