JP2004302145A - Method for cutting heat developable image recording material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for cutting a heat developable image recording material which suppresses cracking, film peeling and occurrence of chips and can prevent the occurrence of image defects in the heat developable image recording material, when the heat developable image recording material is cut. <P>SOLUTION: In the method for cutting a heat developable image recording material, the heat developable image recording material having on a support at least one image forming layer containing an organic silver salt, a photosensitive silver halide and a reducing agent and at least one protective layer disposed on the top of the image forming layer is cut at a temperature between a glass transition temperature of the protective layer and a glass transition temperature of the support. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【０１１２】
【化２】

【０１１３】
【化３】

【０１１４】
【化４】

【０１１５】
これら導電性ポリマーは単独でも使用することができるが、他のバインダーと併用して塗布されることが好ましい。さらにまた、これらのバインダーと共に硬化剤も併用することができる。
熱現像画像記録材料における導電性ポリマーの含有量は、好ましくは０．００５〜５ｇ／ｍ^２であり、より好ましくは０．０１〜３ｇ／ｍ^２、さらに好ましくは０．０２〜１ｇ／ｍ^２である。
バインダーを併用する場合、導電性ポリマーとバインダーの重量比は９９：１から１０：９０が好ましく、８０：２０から２０：８０がさらに好ましく、７０：３０から３０：７０が特に好ましい。
【０１１６】
熱現像画像記録材料の導電性ポリマー層中には、硬膜剤を含有することが好ましい。
このような硬膜剤としては、例えばホルムアルデヒド、グルタルアルデヒドのようなアルデヒド化合物、米国特許２，７３２，３０３号明細書、同３，２８８，７７５号明細書、英国特許９７４，７２３号明細書、同１，１６７，２０７号明細書等に記載されている反応性ハロゲンを有する化合物、ジアセチル、シクロペンタンジオンの如きケトン化合物、ビス（２−クロロエチル）尿素、２−ヒドキシ−４，６−ジクロロ−１，３，５−トリアジン、ジビニルスルホン、５−アセチル−１，３−ジアクリロイルヘキサヒドロ−１，３，５−トリアジン、米国特許３，２３２，７６３号明細書、同３，６３５，７１８号明細書、英国特許９９４，８０９号明細書等に記載の反応性オレフィンを有する化合物、米国特許３，５３９，６４４号明細書、同３，６４２，４８６号明細書、特公昭４９−１３５６８号公報、同５３−４７２７１号公報、同５６−４８８６０号公報、特開昭５３−５７２５７号公報、同６１−１２８２４０号公報、同６２−４２７５号公報、同６３−５３５４１号公報、同６３−２６４５７２号公報等に記載のビニルスルホン化合物、Ｎ−ヒドロキシメチルフタルイミド、米国特許２，７３２，３１６号明細書、同２，５８６，１６８号明細書等に記載のＮ−メチロール化合物、米国特許３，１０３，４３７号明細書等に記載のイソシアネート化合物、米国特許２，９８３，６１１号明細書、同３，１０７，２８０号明細書等に記載のアジリジン化合物、米国特許２，７２５，２９４号明細書、同２，７２５，２９５号明細書等に記載の酸誘導体類、米国特許３，１００，７０４号等に記載のカルボジイミド系化合物、米国特許３，０９１，５３７号明細書等に記載のエポキシ系化合物、米国特許３，３２１，３１３号明細書、同３，５４３，２９２号明細書等に記載のイソオキサゾール系化合物、ムコクロロ酸のようなハロゲノカルボキシアルデヒド類、ジヒドロキシジオキサン、ジクロロジオキサン等のジオキサン誘導体等の有機硬膜剤およびクロムミョウバン、硫酸ジルコニウム、三塩化クロム等の無機硬膜剤である。またゼラチンに対して比較的硬膜作用が比較的速い硬膜剤としては、特開昭５０−３８５４０号公報に記載のジヒドロキノリン骨格を有する化合物、特開昭５１−５９６２５号公報、同６２−２６２８５４号公報、同６２−２６４０４４号公報、同６３−１８４７４１号公報に記載のＮ−カルバモイルピリジニウム塩類、特公昭５５−３８６５５号公報に記載のアシルイミダゾール類、特公昭５３−２２０８９号公報に記載のＮ−アシルオキシイミダゾール類、特公昭５３−２２０８９号公報に記載のＮ−アシルオキシイミノ基を分子内に２個以上有する化合物、特開昭５２−９３４７０号公報に記載のＮ−スルホニルオキシイミド基を有する化合物、特開昭５８−１１３９２９号公報に記載のリン−ハロゲン結合を有する化合物、特開昭６０−２２５１４８号公報、同６１−２４０２３６号公報、同６３−４１５８０号公報に記載のクロロホルムアミジニウム化合物等を挙げることができる。
これらの添加量は、バインダーに対し質量比で、０．００１〜１であることが好ましい。
【０１１７】
本発明で用いられる界面活性剤について以下に述べる。界面活性剤はその使用目的によって、分散剤、塗布剤、濡れ剤、帯電防止剤、写真性コントロール剤などに分類されるが、以下に述べる界面活性剤を適宜使用することでそれらの目的は達成できる。本発明で使用される界面活性剤は、ノニオン性、イオン性（アニオン、カチオン、ベタイン）いずれも使用できる。さらにフッ素系界面活性剤も好ましく用いられる。
【０１１８】
好ましいノニオン系界面活性剤としては、ポリオキシエチレン、ポリオキシプロピレン、ポリオキシブチレン、ポリグリシジルやソルビタンをノニオン性親水性基とする界面活性剤であり、具体的には、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アルキルフェニールエーテル、ポリオキシエチレン−ポリオキシプロピレングリコール、多価アルコール脂肪酸部分エステル、ポリオキシエチレン多価アルコール脂肪酸部分エステル、ポリオキシエチレン脂肪酸エステル、ポリグリセリン脂肪酸エステル、脂肪酸ジエタノールアミド、トリエタノールアミン脂肪酸部分エステルを挙げることができる。
【０１１９】
アニオン系界面活性剤としてはカルボン酸塩、硫酸塩、スルホン酸塩、リン酸エステル塩であり、代表的なものとしては脂肪酸塩、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、アルキルスルホン酸塩、α−オレフィンスルホン酸塩、ジアルキルスルホコハク酸塩、α−スルホン化脂肪酸塩、Ｎ−メチルーＮオレイルタウリン、石油スルホン酸塩、アルキル硫酸塩、硫酸化油脂、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニールエーテル硫酸塩、ポリオキシエチレンスチレン化フェニールエーテル硫酸塩、アルキルリン酸塩、ポリオキシエチレンアルキルエーテルリン酸塩、ナフタレンスルホン酸塩ホルムアルデヒド縮合物などである。
【０１２０】
カチオン系界面活性剤としてはアミン塩、４級アンモニウム塩、ピリジウム塩などを挙げることができ、第１〜第３脂肪アミン塩、第４級アンモニウム塩（テトラアルキルアンモニウム塩、トリアルキルベンジルアンモニウム塩、アルキルピリジウム塩、アルキルイミダゾリウム塩など）を挙げることができる。
【０１２１】
ベタイン系界面活性剤としてはカルボキシベタイン、スルホベタインなどであり、Ｎ−トリアルキル−Ｎ−カルボキシメチルアンモニウムベタイン、Ｎ−トリアルキル−Ｎ−スルホアルキレンアンモニウムベタインなどである。
【０１２２】
これらの界面活性剤は、「界面活性剤の応用（幸書房、刈米孝夫著、昭和５５年９月１日発行）」に記載されている。本発明においては、好ましい界面活性剤はその使用量において特に限定されず、目的とする界面活性特性が得られる量であればよい。なお、フッ素含有界面活性剤の塗布量は、１ｍ^２当り２５０ｍｇ〜０．０１ｍｇが好ましい。
【０１２３】
以下に界面活性剤の具体例を記すが、これに限定されるものではない（ここで、−Ｃ_６Ｈ_４−はフェニレン基を表わす）。
ＷＡ−１ ：Ｃ_１６Ｈ_３３（ＯＣＨ_２ＣＨ_２）_１０ＯＨ
ＷＡ−２ ：Ｃ_９Ｈ_１９−Ｃ_６Ｈ_４−（ＯＣＨ_２ＣＨ_２）_１２ＯＨ
ＷＡ−３ ：ドデシルベンゼンスルホン酸ナトリウム
ＷＡ−４ ：トリ（イソプロピル）ナフタレンスルホン酸ナトリウム
ＷＡ−５ ：トリ（イソブチル）ナフタレンスルホン酸ナトリウム
ＷＡ−６ ：ドデシル硫酸ナトリウム
ＷＡ−７ ：α−スルファコハク酸ジ（２−エチルヘキシル）エステルナトリウム塩
ＷＡ−８ ：Ｃ_８Ｈ_１７−Ｃ_６Ｈ_４−（ＣＨ_２ＣＨ_２Ｏ）_３（ＣＨ_２）_２ＳＯ_３Ｋ
ＷＡ−１０ ：セチルトリメチルアンモニウムクロライド
ＷＡ−１１ ：Ｃ_１１Ｈ_２３ＣＯＮＨＣＨ_２ＣＨ_２Ｎ^（＋）（ＣＨ_３）_２−ＣＨ_２ＣＯＯ^（−）
ＷＡ−１２ ：Ｃ_８Ｆ_１７ＳＯ_２Ｎ（Ｃ_３Ｈ_７）（ＣＨ_２ＣＨ_２Ｏ）_１６Ｈ
ＷＡ−１３ ：Ｃ_８Ｆ_１７ＳＯ_２Ｎ（Ｃ_３Ｈ_７）ＣＨ_２ＣＯＯＫ
ＷＡ−１４ ：Ｃ_８Ｆ_１７ＳＯ_３Ｋ
ＷＡ−１５ ：Ｃ_８Ｆ_１７ＳＯ_２Ｎ（Ｃ_３Ｈ_７）（ＣＨ_２ＣＨ_２Ｏ）_４（ＣＨ_２）_４ＳＯ_３Ｎａ
ＷＡ−１６ ：Ｃ_８Ｆ_１７ＳＯ_２Ｎ（Ｃ_３Ｈ_７）（ＣＨ_２）_３ＯＣＨ_２ＣＨ_２Ｎ^（＋）（ＣＨ_３）_３−ＣＨ_３・Ｃ_６Ｈ_４−ＳＯ_３ ^（−）
ＷＡ−１７ ：Ｃ_８Ｆ_１７ＳＯ_２Ｎ（Ｃ_３Ｈ_７）ＣＨ_２ＣＨ_２ＣＨ_２Ｎ^（＋）（ＣＨ_３）
ＷＡ−１８ ：Ｃ_８Ｆ_１７ＣＨ_２ＣＨ_２ＳＣＨ_２ＣＨ_２ＣＨ_２ＣＯＯＬｉ
ＷＡ−１９ ：（Ｃ_４Ｆ_９）ＣＯＯＣＨ_２ＣＨ（ＳＯ_３Ｎａ）ＣＯＯＣＨ_２ＣＨ_２（Ｃ_４Ｆ_９）
ＷＡ−２０ ：Ｃ_８Ｈ_１７ＣＯＯＣＨ_２ＣＨ（ＳＯ_３Ｎａ）ＣＯＯＣＨ_２ＣＨ_２（Ｃ_４Ｆ_９）
【０１２４】
本発明において、画像形成層、画像形成層の保護層、下塗層およびバック層には特開平１１−８４５７３号公報の段落番号０２０４〜０２０８、特願２０００−４７０８３号明細書の段落番号０２４０〜０２４１、特開平８−２７８５９５号公報、特開平７−１０２１７９号公報、特表平９−５０９５０３号公報に記載の如くハレーション防止などの目的で、染料を含有することができる。
【０１２５】
画像形成層には色調改良、イラジエーション防止の観点から各種染料や顔料を用いることができる。画像形成層に用いる染料および顔料はいかなるものでもよいが、例えば特開平１１−１１９３７４号公報の段落番号０２９７に記載されている化合物を用いることができる。これらの染料の添加法としては、溶液、乳化物、固体微粒子分散物、高分子媒染剤に媒染された状態などいかなる方法でもよい。これらの化合物の使用量は目的の吸収量によって決められるが、一般的に１ｍ^２当たり１×１０^−６ｇ〜１ｇの範囲で用いることが好ましい。
【０１２６】
本発明でハレーション防止染料を使用する場合、該染料は所望の範囲で目的の吸収を有し、処理後に可視領域での吸収が充分少なく、上記バック層の好ましい吸光度スペクトルの形状が得られればいかなる化合物でもよい。例えば特開平１１−１１９３７４号公報の段落番号０３００、に記載されている化合物を用いることができる。また、ベルギー特許第７３３，７０６号明細書に記載されたように染料による濃度を加熱による消色で低下させる方法、特開昭５４−１７８３３号公報に記載の光照射による消色で濃度を低下させる方法等を用いることができる。
【０１２７】
従来から用いられているハロゲン化銀を含みゼラチンを基体とする粘性液である写真乳剤塗布液は、通常加圧送液するだけで気泡が液中に溶解、消滅してしまい、塗布時大気圧下に戻されても気泡が析出するようなことはほとんどない。ところが、本発明で好ましく用いられる有機銀塩分散物とポリマーラテックスなどを含む画像形成層塗布液の場合は、加圧送液だけでは脱泡が不十分になりやすいため、気液界面が生じないようにして送液しながら超音波振動を与え脱泡することが好ましい。
【０１２８】
本発明において塗布液の脱泡は、塗布液を塗布される前に減圧脱気し、さらに１．５ｋｇ／ｃｍ^２以上の加圧状態に保ち、かつ気液界面が生じないようにして連続的に送液しながら超音波振動を与える方式が好ましい。具体的には、特公昭５５−６４０５号公報（４頁２０行から７頁１１行）に記載されている方式が好ましい。このような脱泡を行う装置として、特開２０００−９８５３４号公報の実施例図３に示される構成のものを好ましく用いることができる。
【０１２９】
加圧条件として１．５ｋｇ／ｃｍ^２以上、好ましくは１．８ｋｇ／ｃｍ^２以上である。その上限に特に制限はないが、通常５ｋｇ／ｃｍ^２程度である。与えられる超音波の音圧は０．２Ｖ以上、好ましくは０．５Ｖ〜３．０Ｖであり、一般的に音圧は高い方が好ましいが、音圧が高すぎるとキャピテーションにより部分的に高温状態になりカブリの発生原因となる。周波数は特に制約はないが、通常１０ｋＨｚ以上、好ましくは２０ｋＨｚ〜２００ｋＨｚである。なお、減圧脱気は、タンク内（通常、調液タンクもしくは貯蔵タンク）を密閉減圧し、塗布液中の気泡径を増大させ、浮力をかせぎ脱気させることを指し、減圧脱気の際の減圧条件は−２００ｍｍＨｇないしそれより低い圧力条件、好ましくは−２５０ｍｍＨｇないしそれより低い圧力条件とし、その最も低い圧力条件は特に制限はないが通常−８００ｍｍＨｇ程度である。減圧時間は３０分以上、好ましくは４５分以上、その上限は特に制限はない。
【０１３０】
本発明の好ましい態様においては、画像形成層および保護層に加えて、必要に応じて中間層を設けてもよいが、生産性の向上などを目的として、これらの複数の層を水系において同時重層塗布する。塗布方式はエクストルージョン塗布、スライドビード塗布、カーテン塗布などがあるが、特開２０００−２９６４号公報の明細書中の図１で開示されているスライドビード塗布方式が特に好ましい。
ゼラチンを主バインダーとして用いる熱現像画像記録材料の場合では、コーティングダイの下流に設けられている第一乾燥ゾーンで急冷され、その結果、ゼラチンのゲル化が起こり、塗布膜は冷却固化される。冷却固化されて流動の止まった塗布膜は続く第二乾燥ゾーンに導かれ、これ以降の乾燥ゾーンで塗布液中の溶媒が揮発され、成膜される。第二乾燥ゾーン以降の乾燥方式としては、Ｕ字型のダクトからローラー支持された支持体に噴流を吹き付けるエアーループ方式や円筒状のダクトに支持体をつるまき状に巻き付けて搬送乾燥する、つるまき方式（エアーフローティング方式）などが挙げられる。
【０１３１】
バインダーの主成分がポリマーラテックスである塗布液では、急冷では塗布液の流動を停止させることができないため、第一乾燥ゾーンのみでは予備乾燥が不十分である場合もある。この場合は、熱現像画像記録材料の様な乾燥方式では流れムラや乾燥ムラが生じ、塗布面状に重大な欠陥を生じやすい。
【０１３２】
本発明における好ましい乾燥方式は、特開２０００−２９６４号公報に記載されているような第一乾燥ゾーン、第二乾燥ゾーンを問わず、少なくとも恒率乾燥期の１／４以上の時間は、水平乾燥ゾーンで乾燥させる方式であることが好ましい。塗布直後から水平乾燥ゾーンに導かれるまでの支持体の搬送は、水平搬送であってもなくてもどちらでもよく、塗布機の水平方向に対する立ち上がり角度としては０〜７０°の間にあればよい。また、本発明における水平乾燥ゾーンとは、支持体が塗布機の水平方向に対して上下に±１５°以内に搬送されればよく、水平搬送を意味するものではない。
恒率乾燥期における乾燥風は、塗布液膜面上で、風速が１〜３０ｍ／ｓ、好ましくは２〜２０ｍ／ｓで乾燥することが好ましい。さらに好ましくは、第一乾燥ゾーンが低速風乾燥域で、この領域での恒率乾燥期の１／２以内の時間は、風速が、支持体面上で１５ｍ／ｓ以下、好ましくは２〜１０ｍ／ｓで、その後の第二乾燥ゾーンは、風速が、５〜３０ｍ／ｓ、好ましくは１０〜２０ｍ／ｓであることが乾燥ムラなどの発生がなく、生産性向上が計れる。
【０１３３】
本発明における恒率乾燥とは、液膜温度が一定で流入する熱量全てが溶媒の蒸発に使用される乾燥過程を意味する。減率乾燥とは、乾燥末期になると種々の要因（水分移動の材料内部拡散が律速になる、蒸発表面の後退など）により乾燥速度が低下し、与えられた熱は液膜温度上昇にも使用される乾燥過程を意味する。恒率乾燥が終了する時には、流動が停止するまで十分乾燥が進むため、熱現像画像記録材料に一般に用いられるような乾燥方式も採用することができる。
【０１３４】
本発明における好ましい乾燥条件は、画像形成層および／または保護層を形成する時の乾燥条件が、恒率乾燥時の液膜表面温度が用いられるポリマーラテックスの最低皮膜形成温度（ＭＦＴ）以上で、通常は製造設備の制限より２５℃〜４５℃である場合が多い。また、減率乾燥時の乾球温度は用いる支持体のＴｇ未満の温度（ＰＥＴの場合通常８０℃以下）が好ましい。本発明における液膜表面温度とは、支持体に塗布された塗布液膜の表面温度を言い、乾球温度とは乾燥ゾーンの乾燥風の温度を意味する。
【０１３５】
恒率乾燥時の液膜表面温度が低くなる条件で乾燥した場合、乾燥が不十分となりやすい。このため特に保護層の造膜性が著しく低下し、膜表面に亀裂が生じやすくなる。また、膜強度も弱くなり、露光機や熱現像機での搬送中に傷がつきやすくなるなどの重大な問題が生じやすくなる。
また、支持体（ベース）のＴｇよりも高い過剰の熱がかかると、熱現像画像記録材料の寸度安定性、耐巻き癖性等が悪化する。
【０１３６】
乾燥後の巻取りは温度２０〜３０℃、相対湿度４５±２０％の条件下で行うことが好ましく、巻き姿はその後の加工形態に合わせ画像形成層側の面を外側にしてもよいし、内側にしてもよい。また、加工形態がロール品の場合は巻き姿で発生したカールを除去するために加工時に巻き姿とは反対側に巻いたロール形態にすることも好ましく用いられる。なお、熱現像画像記録材料の包装時の環境条件は、２０〜３０℃相対湿度２０〜６５％の範囲が好ましく、包袋内湿度が、相対湿度２０〜５５％（２５℃測定）の範囲で制御されることが好ましい。
【０１３７】
本発明の熱現像画像記録材料の切断方法は、熱現像画像記録材料の温度が、保護層のガラス転移温度以上でかつ支持体のガラス転移温度以下で、切断することが好ましい。さらに、保護層のガラス転移温度＋５℃以上支持体のガラス転移温度−１５℃以下が好ましい。支持体のガラス転移温度を超えると支持体の熱収縮が加わり切断による歪応力が大きくなり、亀裂・膜剥がれなど切り屑の発生がしやすくなる。
搬送される熱現像画像記録材料を切断する切断手段の上流側には、熱現像画像記録材料を加熱する加熱手段を設けることが好ましい。加熱手段としては、熱風を吹き付けて加熱する方法、加熱ローラーを用いて加熱する方法、切断装置の部分を覆い加熱温度をコントロールする方法などが挙げられる。具体的には、特開２００１−３３７４１号公報記載の加熱方法が好ましく用いられる。
【０１３８】
熱現像画像記録材料は、特開平６−１７５２９１号公報、特開平６−２１４３５０号公報、特開平７−９２６１８号公報、特開平８−６２７８３号公報、特開平８−２５４７９３号公報、特開平１１−３２７０８９号公報、特開２０００−１８１０１７号公報、特開２０００−１７１９４２号公報、特開平２０００−２０６６５３号公報、特開２００１−１３６３２号公報に記載の包装材料および包装方法を用いて包装することができる。
【０１３９】
画像形成を行なう際には、熱現像画像記録材料は、まず、７５０〜８００ｎｍの波長の光で露光される。露光に用いられる露光装置は露光時間が１０^−７秒以下の露光が可能なレーザーダイオード（ＬＤ）を光源に使用した露光装置が用いられる。これらの光源は目的波長範囲の電磁波スペクトルの光を発生することができるものであればいずれでもよい。例えば、色素レーザー、ガスレーザー、固体レーザー、半導体レーザーなどを用いることができるが、半導体レーザーは省スペース、省コストの観点で特に好ましく用いられる。
【０１４０】
画像形成する際には、光源の光ビームをオーバーラップさせて、前記熱現像画像記録材料を露光するのが好ましい。オーバーラップとは副走査ピッチ幅がビーム径より小さいことをいう。オーバーラップは、例えばビーム径をビーム強度の半値幅（ＦＷＨＭ）で表わしたとき、ＦＷＨＭ／副走査ピッチ幅（オーバーラップ係数）で定量的に表現することができる。本発明ではこのオーバーラップ係数が０．２以上であることが好ましい。
【０１４１】
本発明に使用する露光装置の光源の走査方式は特に限定されず、円筒外面走査方式、円筒内面走査方式、平面走査方式などを用いることができる。また、光源のチャンネルは単チャンネルでもマルチチャンネルでもよいが、高出力が得られ、書き込み時間が短くなるという点でレーザーヘッドを２機以上搭載するマルチチャンネルが好ましい。特に、円筒外面方式の場合にはレーザーヘッドを数機から数十機以上搭載するマルチチャンネルが好ましく用いられる。
【０１４２】
露光の対象となる熱現像画像記録材料が、露光時のヘイズが低い場合は、干渉縞が発生しやすい傾向にあるので、これを防止することが好ましい。干渉縞の発生を防止する技術としては、特開平５−１１３５４８号公報などに開示されているレーザー光を熱現像画像記録材料に対して斜めに入光させる技術や、国際公開ＷＯ９５／３１７５４号公報などに開示されているマルチモードレーザーを利用する方法が知られており、これらの技術を用いることが好ましい。
【０１４３】
本発明に好ましく使用される露光装置の光源の走査方式はインナードラム方式（円筒内面走査方式）である。露光は、レーザーダイオードから発生するレーザー光がポリゴンミラー（プリズム）を介して、インナードラム部に搬送された熱現像画像記録材料面上に走査されて行われる。主走査方向の露光時間は、ポリゴンミラーの回転数とドラムの内径によって決定される。熱現像画像記録材料面上での主走査速度は５００ｍ／秒〜１５００ｍ／秒であることが好ましい。より好ましい主走査速度は６３０ｍ／秒〜１４１０ｍ／秒である。
【０１４４】
露光の対象となる熱現像画像記録材料が、露光時のヘイズが低い場合は、干渉縞が発生しやすい傾向にあるので、これを防止することが好ましい。干渉縞の発生を防止する技術としては、特開平５−１１３５４８号公報などに開示されているレーザー光を熱現像画像記録材料に対して斜めに入光させる技術や、国際公開ＷＯ９５／３１７５４号公報などに開示されているマルチモードレーザーを利用する方法が知られており、これらの技術を用いることが好ましい。
【０１４５】
熱現像画像記録材料は露光され、潜像が形成された後、予備加熱部、熱現像部および徐冷部を備えた熱現像機で現像処理される。熱現像機による現像温度は、８０〜２５０℃であるのが好ましく、１００〜１４０℃であるのが好ましい。前記熱現像機によるトータルの現像時間は１〜１８０秒であるのが好ましく、５〜９０秒であるのがさらに好ましい。また、前記熱現像機による熱現像部の処理速度は、２１〜１００ｍｍ／秒であるのが好ましく、２４〜５０ｍｍ／秒であるのがより好ましい。
【０１４６】
露光された熱現像画像記録材料は、まず、予備加熱部で加熱される。予備加熱部は、熱現像時における熱現像画像記録材料の寸法変化による処理ムラを防止する目的で設けられる。予備加熱部における加熱は、熱現像温度よりも低く（例えば１０〜３０℃程度低く）、熱現像画像記録材料中に残存する溶媒を蒸発させるのに十分な温度および時間に設定することが望ましく、熱現像画像記録材料の支持体のガラス転移温度（Ｔｇ）よりも高い温度で、現像ムラが出ないように設定することが好ましい。一般的には、８０℃以上１１５℃未満で、５秒以上加熱するのが好ましい。
【０１４７】
予備加熱部で加熱された熱現像感光性材料は、引き続き熱現像部にて加熱される。前記熱現像部は、搬送される熱現像画像記録材料に対して、画像形成層側およびバック層側に加熱部材を備えるとともに、画像形成層側のみに搬送ローラを備える。例えば、熱現像画像記録材料が画像形成層を上側にして搬送される場合、熱現像画像記録材料の搬送方向に対し下側（熱現像画像記録材料のバック層側）は搬送ローラがなく、上側（熱現像画像記録材料の画像形成層側）のみに搬送ローラがある構成である。本発明においては、熱現像部を前記構成とすることにより、濃度ムラの発生および物理的な変形を防止している。
【０１４８】
熱現像部において、熱現像画像記録材料は加熱ヒータ等の加熱部材によって加熱される。熱現像部における加熱温度は、熱現像に充分な温度であり、一般的には１１０℃〜１４０℃である。熱現像画像記録材料は、熱現像部において、１１０℃以上の高温にさらされるため、該材料中に含まれている成分の一部、あるいは熱現像による分解成分の一部が揮発する場合がある。これらの揮発成分は現像ムラの原因になったり、熱現像機の構成部材を腐食させたり、温度の低い場所で析出し、異物として画面の変形を引起こしたり、画面に付着した汚れとなったり、等の種々の悪い影響を及ぼすことが知られている。これらの影響を除くための方法として、熱現像機にフィルターを設置し、また熱現像機内の空気の流れを最適に調整する方法が知られている。これらの方法は有効に組み合わせて利用することができる。例えば、国際公開ＷＯ９５／３０９３３号公報、同９７／２１１５０号公報、特表平１０−５００４９６号公報には、結合吸収粒子を有し揮発分を導入する第一の開口部と排出する第二の開口部とを有するフィルターカートリッジを、フィルムと接触して加熱する加熱装置に用いることが記載されている。また、国際公開ＷＯ９６／１２２１３号公報、特表平１０−５０７４０３号公報には、熱伝導性の凝縮捕集器とガス吸収性微粒子フィルターを組合せたフィルターを用いることが記載されている。本発明ではこれらを好ましく用いることができる。また、米国特許第４，５１８，８４５号明細書、特公平３−５４３３１号公報には、フィルムからの蒸気を除去する装置とフィルムを伝熱部材へ押圧する加圧装置と伝熱部材を加熱する装置とを有する構成が記載されている。また、国際公開ＷＯ９８／２７４５８号公報には、フィルムから揮発するカブリを増加させる成分をフィルム表面から取り除くことが記載されている。これらについても本発明では好ましく用いることができる。
【０１４９】
予備加熱部および熱現像部における加熱の温度分布は、各々、±１℃以下であるのが好ましく、±０．５℃以下であるのがより好ましい。
【０１５０】
熱現像部で加熱された熱現像画像記録材料は、次に、徐冷部で冷却される。冷却は、熱現像画像記録材料が物理的に変形しないように、徐々に行うのが好ましく、冷却速度としては０．５〜１０℃／秒が好ましい。
【０１５１】
画像形成に用いられる熱現像機の一構成例は、特開２０００−１７１９３５号公報、特開２０００−２６７２２６号公報、特開２００１−２２０２４号公報等に記載の予備加熱は対向ロ−ラ−で搬送し、熱現像処理部は画像形成層を有する側をロ−ラ−の駆動により、その反対側のバック面を平滑面に滑らせて搬送する熱現像処理装置が好ましく用いられる。
【０１５２】
画像形成を行なう際には、露光装置（プロッター）、オートキャリア、熱現像機（プロセサー）のオンラインシステムで露光、熱現像する。オートキャリアは露光済みの熱現像画像記録材料をプロセサー（熱現像機）に自動で搬送するものであり、搬送機構はベルトコンベア、ロ−ラ−搬送などいずれの方式でもよいが、ロ−ラ−搬送が好ましい。また、オートキャリアは熱現像機側から露光装置側へ熱が入り込まないような機構を設けることが好ましく、例えばオートキャリア中心下部より露光装置および熱現像機に風を送り込む方式などがある。
【０１５３】
前記熱現像画像記録材料は、例えば、幅５５０〜６５０ｍｍおよび長さ１〜６５ｍのシート状のものが用いられ、その一部または全部を円筒形状のコア部材に画像形成層を外側として巻き取られた形態で、熱現像システムに組み込まれる。
【０１５４】
熱現像画像記録材料が熱現像後において、ＰＳ版により刷版を作製する際にマスクとして用いられる場合、熱現像後の熱現像画像記録材料は、製版機においてＰＳ版に対する露光条件を設定するための情報や、マスク原稿およびＰＳ版の搬送条件等の製版条件を設定するための情報を画像情報として担持している。従って、前記のイラジエーション染料、ハレーション染料、フィルター染料の濃度（使用量）は、これらを読み取るために制限される。これら情報はＬＥＤあるいはレーザーによって読み取られるため、センサーの波長域のＤｍｉｎ（最低濃度）が低い必要があり吸光度が０．３以下である必要がある。例えば、富士写真フイルム（株）社製 製版機Ｓ−ＦＮＲＩＩＩはトンボ検出のための検出器およびバーコードリーダーとして６７０ｎｍの波長の光源を使用している。また、清水製作社製 製版機ＡＰＭＬシリーズのバーコードリーダーとして６７０ｎｍの光源を使用している。すなわち６７０ｎｍ付近のＤｍｉｎ（最低濃度）が高い場合にはフィルム上の情報が正確に検出できず搬送不良、露光不良など製版機で作業エラーが発生する。従って、６７０ｎｍの光源で情報を読み取るためには６７０ｎｍ付近のＤｍｉｎが低い必要があり、熱現像後の６６０〜６８０ｎｍの吸光度が０．３以下である必要がある。より好ましくは０．２５以下である。その下限に特に制限はないが、通常、０．１０程度である。
【０１５５】
本発明において、像様露光に用いられる露光装置は露光時間が１０^−７秒未満の露光が可能な装置であればいずれでもよいが、一般的にはＬａｓｅｒ Ｄｉｏｄｅ（ＬＤ）、Ｌｉｇｈｔ Ｅｍｉｔｔｉｎｇ Ｄｉｏｄｅ（ＬＥＤ）を光源に使用した露光装置が好ましく用いられる。特に、ＬＤは高出力、高解像度の点でより好ましい。これらの光源は目的波長範囲の電磁波スペクトルの光を発生することができるものであればいずれでもよい。例えばＬＤであれば、色素レーザー、ガスレーザー、固体レーザー、半導体レーザーなどを用いることができる。
【０１５６】
【実施例】
以下に実施例と比較例を挙げて本発明の特徴をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。
【０１５７】
＜実施例１＞
《ハロゲン化銀乳剤Ａの調製》
水７００ｍｌに、アルカリ処理ゼラチン（カルシウム含有量として２７００ｐｐｍ以下）１１ｇ、臭化カリウム３０ｍｇおよび４−メチルベンゼンスルホン酸ナトリウム１．３ｇを溶解して、４０℃にてｐＨを６．５に調整した。その後、硝酸銀１８．６ｇを含む水溶液１５９ｍｌと、臭化カリウムを１ｍｏｌ／Ｌ、（ＮＨ_４）_２ＲｈＣｌ_５（Ｈ_２Ｏ）を５×１０^−６ｍｏｌ／ＬおよびＫ_３ＩｒＣｌ_６を２×１０^−５ｍｏｌ／Ｌで含む水溶液を、ｐＡｇ７．７に保ちながらコントロールダブルジェット法で６分３０秒間かけて添加した。ついで、硝酸銀５５．５ｇを含む水溶液４７６ｍｌと、臭化カリウムを１ｍｏｌ／ＬおよびＫ_３ＩｒＣｌ_６を２×１０^−５ｍｏｌ／Ｌで含むハロゲン塩水溶液を、ｐＡｇ７．７に保ちながらコントロールダブルジェット法で２８分３０秒間かけて添加した。その後ｐＨを下げて凝集沈降させて脱塩処理をし、平均分子量１５，０００の低分子量ゼラチン（カルシウム含有量として２０ｐｐｍ以下）５１．１ｇ加え、ｐＨ５．９、ｐＡｇ８．０に調整した。得られた粒子は平均粒子サイズ０．０８μｍ、投影面積変動係数９％、（１００）面比率９０％の立方体粒子であった。
【０１５８】
得られたハロゲン化銀粒子を６０℃に昇温して、銀１ｍｏｌ当たりベンゼンチオスルホン酸ナトリウム７６μｍｏｌを添加し、３分後にトリエチルチオ尿素７１μｍｏｌを添加した後、１００分間熟成し、４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデンを５×１０^−４ｍｏｌ、化合物Ａを０．１７ｇ加えた後、４０℃に降温させた。
その後、４０℃に温度を保ち、ハロゲン化銀１ｍｏｌに対して４．７×１０^−２ｍｏｌの臭化カリウム（水溶液として添加）、１２．８×１０^−４ｍｏｌの増感色素Ａ（エタノール溶液として添加）、６．４×１０^−３ｍｏｌの化合物Ｂ（メタノール溶液として添加）を攪拌しながら添加し、２０分後に３０℃に急冷してハロゲン化銀乳剤Ａの調製を終了した。
得られたハロゲン化銀乳剤Ａは、下記の塗布液の調製に用いた。
【０１５９】
【化５】

【０１６０】
《ベヘン酸銀分散物Ａの調製》
ベヘン酸（ヘンケル社製、ＥｄｅｎｏｒＣ２２−８５Ｒ）８７．６ｋｇ、蒸留水４２３Ｌ、５ｍｏｌ／ＬのＮａＯＨ水溶液４９．２Ｌ、ｔｅｒｔ−ブチルアルコール１２０Ｌを混合し、７５℃にて１時間攪拌して反応させ、ベヘン酸ナトリウム溶液を得た。これとは別に、硝酸銀４０．４ｋｇの水溶液２０６．２Ｌを用意し、１０℃にて保温した。６３５Ｌの蒸留水と３０Ｌのｔｅｒｔ−ブチルアルコールを入れた反応容器を３０℃に保温し、攪拌しながら先のベヘン酸ナトリウム溶液の全量と硝酸銀水溶液の全量を流量一定でそれぞれ６２分１０秒と６０分かけて添加した。この時、硝酸銀水溶液添加開始後７分２０秒間は硝酸銀水溶液のみが添加されるようにし、そのあとベヘン酸ナトリウム溶液を添加開始し、硝酸銀水溶液添加終了後９分３０秒間はベヘン酸ナトリウム溶液のみが添加されるようにした。このとき、反応容器内の温度は３０℃とし、液温が上がらないようにコントロールした。また、ベヘン酸ナトリウム溶液の添加系の配管は、スチームトレースにより保温し、添加ノズル先端の出口の液温が７５℃になるようにスチーム量をコントロールした。また、硝酸銀水溶液の添加系の配管は、２重管の外側に冷水を循環させることにより保温した。ベヘン酸ナトリウム溶液の添加位置と硝酸銀水溶液の添加位置は攪拌軸を中心として対称的な配置とし、また反応液に接触しないような高さに調節した。
ベヘン酸ナトリウム溶液を添加終了後、そのままの温度で２０分間攪拌放置し、２５℃に降温した。その後、遠心ろ過で固形分を濾別し、固形分を濾水の伝導度が３０μＳ／ｃｍになるまで水洗した。こうして得られた固形分は、乾燥させないでウエットケーキとして保管した。
得られたベヘン酸銀の粒子の形態を電子顕微鏡撮影により評価したところ、平均投影面積径０．５２μｍ、平均粒子厚み０．１４μｍ、平均球相当径の変動係数１５％の鱗片状の結晶であった。
【０１６１】
次に、以下の方法でベヘン酸銀の分散物を作製した。乾燥固形分１００ｇ相当のウエットケーキに対し、ポリビニルアルコール（クラレ（株）製、ＰＶＡ−２１７、平均重合度：約１７００）７．４ｇおよび水を添加し、全体量を３８５ｇとしてからホモミキサーにて予備分散した。次に予備分散済みの原液を分散機（マイクロフルイデックス・インターナショナル・コーポレーション製、マイクロフルイダイザーＭ−１１０Ｓ−ＥＨ、Ｇ１０Ｚインタラクションチャンバー使用）の圧力を１７５０ｋｇ／ｃｍ^２に調節して、３回処理し、ベヘン酸銀分散物Ａを得た。このとき、蛇管式熱交換器をインタラクションチャンバーの前後に各々装着して冷媒の温度を調節することにより、所望の分散温度に設定した。
得られたベヘン酸銀分散物Ａに含まれるベヘン酸銀粒子は、体積加重平均直径０．５２μｍ、変動係数１５％の粒子であった。粒子サイズの測定は、ＭａｌｖｅｒｎＩｎｓｔｒｕｍｅｎｔｓ Ｌｔｄ．製ＭａｓｔｅｒＳｉｚｅｒＸにて行った。また電子顕微鏡撮影により評価したところ、長辺と短辺の比は１．５、粒子厚みは０．１４μｍ、平均アスペクト比（粒子の投影面積の円相当径と粒子厚みの比）は５．１であった。
得られたベヘン酸銀分散物Ａは、下記の塗布液の調製に用いた。
【０１６２】
《還元剤の固体微粒子分散物の調製》
還元剤［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］１０ｋｇと変性ポリビニルアルコール（クラレ（株）製、ポバールＭＰ２０３）の２０質量％水溶液１０ｋｇに、サーフィノール１０４Ｅ（日信化学（株）製）４００ｇ、メタノール６４０ｇおよび水１６ｋｇを添加して、よく混合してスラリーとした。このスラリーをダイアフラムポンプで送液し、平均直径０．５ｍｍのジルコニアビーズを充填した横型ビーズミル（アイメックス（株）製、ＵＶＭ−２）にて３時間３０分分散したのち、ベンゾイソチアゾリノンナトリウム塩４ｇと水を加えて還元剤の濃度が２５質量％になるように調整し、還元剤の固体微粒子分散物を得た。得られた分散物に含まれる還元剤粒子は、メジアン径が０．４４μｍ、最大粒子サイズが２．０μｍ以下、平均粒子サイズの変動係数が１９％であった。得られた分散物は、孔径３．０μｍのポリプロピレン製フィルターにてろ過を行いゴミ等の異物を除去したうえで、下記の塗布液の調製に用いた。
【０１６３】
《有機ポリハロゲン化合物Ａの固体微粒子分散物の調製》
有機ポリハロゲン化合物Ａ［トリブロモメチル（４−（２，４，６−トリメチルフェニルスルホニル）フェニル）スルホン］１０ｋｇ、変性ポリビニルアルコール（クラレ（株）製、ポバールＭＰ２０３）の２０質量％水溶液１０ｋｇ、トリイソプロピルナフタレンスルホン酸ナトリウムの２０質量％水溶液６３９ｇ、サーフィノール１０４Ｅ（日信化学（株）製）４００ｇ、メタノール６４０ｇおよび水１６ｋｇを添加して、よく混合してスラリーとした。このスラリーをダイアフラムポンプで送液し、平均直径０．５ｍｍのジルコニアビーズを充填した横型ビーズミル（アイメックス（株）製、ＵＶＭ−２）にて５時間分散したのち、水を加えて有機ポリハロゲン化合物Ａの濃度が２５質量％になるように調整し、有機ポリハロゲン化合物Ａの固体微粒子分散物を得た。得られた分散物に含まれる有機ポリハロゲン化合物粒子は、メジアン径が０．３６μｍ、最大粒子サイズが２．０μｍ以下、平均粒子サイズの変動係数が１８％であった。得られた分散物は、孔径３．０μｍのポリプロピレン製フィルターにてろ過を行いゴミ等の異物を除去したうえで、下記の塗布液の調製に用いた。
【０１６４】
《有機ポリハロゲン化合物Ｂの固体微粒子分散物の調製》
有機ポリハロゲン化合物Ｂ［トリブロモメチルナフチルスルホン］５ｋｇ、変性ポリビニルアルコール（クラレ（株）製、ポバールＭＰ２０３）の２０質量％水溶液２．５ｋｇ、トリイソプロピルナフタレンスルホン酸ナトリウムの２０質量％水溶液２１３ｇおよび水１０ｋｇを添加して、よく混合してスラリーとした。このスラリーをダイアフラムポンプで送液し、平均直径０．５ｍｍのジルコニアビーズを充填した横型ビーズミル（アイメックス（株）製、ＵＶＭ−２）にて５時間分散したのち、ベンゾイソチアゾリノンナトリウム塩２．５ｇと水を加えて有機ポリハロゲン化合物Ｂの濃度が２３．５質量％になるように調整し、有機ポリハロゲン化合物Ｂの固体微粒子分散物を得た。得られた分散物に含まれる有機ポリハロゲン化合物粒子は、メジアン径が０．３８μｍ、最大粒子サイズが２．０μｍ以下、平均粒子サイズの変動係数が２０％であった。得られた分散物は、孔径３．０μｍのポリプロピレン製フィルターにてろ過を行いゴミ等の異物を除去したうえで、下記の塗布液の調製に用いた。
【０１６５】
《有機ポリハロゲン化合物Ｃ水溶液の調製》
室温で攪拌しながら、水７５．０ｍｌ、トリプロピルナフタレンスルホン酸ナトリウム（２０％水溶液）８．６ｍｌ、オルトリン酸二水素ナトリウム・２水和物（５％水溶液）６．８ｍｌ、水酸化カリウム（１ｍｏｌ／Ｌ水溶液）９．５ｍｌを順次添加し、添加終了後５分間攪拌混合した。さらに、攪拌しながら有機ポリハロゲン化合物Ｃ［３−トリブロモメタンスルホニルベンゾイルアミノ酢酸］４．０ｇの粉末を添加し、均一に溶解させて透明溶液１００ｇを得た。得られた水溶液は、２００メッシュのポリエステル製スクリーンにてろ過を行いゴミ等の異物を除去したうえで、下記の塗布液の調製に用いた。
【０１６６】
《化合物Ｚの乳化分散物の調製》
化合物Ｚを８５質量％含有するＲ−０５４（三光（株）製）を１０ｋｇとＭＩＢＫ１１．６６ｋｇを混合した後、窒素置換して８０℃で１時間溶解した。この液に、水２５．５２ｋｇ、変性ポリビニルアルコール（クラレ（株）製、ＭＰ−２０３）の２０質量％水溶液１２．７６ｋｇおよびトリイソプロピルナフタレンスルホン酸ナトリウムの２０質量％水溶液０．４４ｋｇを添加して、２０〜４０℃にて３６００ｒｐｍで６０分間乳化分散した。さらに、この液にサーフィノール１０４Ｅ（日信化学（株）製）０．０８ｋｇと水４７．９４ｋｇを添加して減圧蒸留しＭＩＢＫを除去したのち、化合物Ｚの濃度が１０質量％になるように調整した。こうして得た分散物に含まれる化合物Ｚの粒子は、メジアン径が０．１９μｍ、最大粒子サイズが１．５μｍ以下、粒子サイズの変動係数が１７％であった。得られた分散物は、孔径３．０μｍのポリプロピレン製フィルターにてろ過を行いゴミ等の異物を除去したうえで、下記の塗布液の調製に用いた。
【０１６７】
【化６】

【０１６８】
《６−イソプロピルフタラジン化合物の分散液の調製》
室温で水６２．３５ｇを攪拌しながら変性ポリビニルアルコール（クラレ（株）製、ポバールＭＰ２０３）２．０ｇが塊状にならない様に添加し、１０分間攪拌混合した。その後加熱し、内温が５０℃になるまで昇温した後、内温５０〜６０℃の範囲で９０分間攪拌し均一に溶解させた。内温を４０℃以下に降温して、ポリビニルアルコール（クラレ（株）製、ＰＶＡ−２１７、１０質量％水溶液）２５．５ｇ、トリプロピルナフタレンスルホン酸ナトリウム（２０質量％水溶液）３．０ｇ、６−イソプロピルフタラジン（７０質量％水溶液）７．１５ｇを添加し、３０分攪拌し透明分散液１００ｇを得た。得られた分散物は、孔径３．０μｍのポリプロピレン製フィルターにてろ過を行いゴミ等の異物を除去したうえで、下記の塗布液の調製に用いた。
【０１６９】
《硬調化剤Ｘの固体微粒子分散物の調製》
硬調化剤Ｘを４ｋｇに対して、ポリビニルアルコール（クラレ（株）製、ポバールＰＶＡ−２１７）を１ｋｇと水３６ｋｇとを添加してよく混合してスラリーとした。このスラリーをダイアフラムポンプで送液し、平均直径０．５ｍｍのジルコニアビーズを充填した横型ビーズミル（アイメックス（株）製、ＵＶＭ−２）にて１２時間分散したのち、ベンゾイソチアゾリノンナトリウム塩４ｇと水を加えて硬調化剤濃度が１０質量％になるように調整し、硬調化剤の固体微粒子分散物を得た。こうして得た分散物に含まれる硬調化剤の粒子は、メジアン径が０．３４μｍ、最大粒子サイズが３．０μｍ以下、粒子サイズの変動係数が１９％であった。得られた分散物は、孔径３．０μｍのポリプロピレン製フィルターにてろ過を行いゴミ等の異物を除去したうえで、下記の塗布液の調製に用いた。
【０１７０】
《現像促進剤Ｗの固体微粒子分散物の調製》
現像促進剤Ｗを１０ｋｇ、変性ポリビニルアルコール（クラレ（株）製、ポバールＭＰ２０３）の２０質量％水溶液１０ｋｇおよび水２０ｋｇを添加して、よく混合してスラリーとした。このスラリーをダイアフラムポンプで送液し、平均直径０．５ｍｍのジルコニアビーズを充填した横型ビーズミル（アイメックス（株）製、ＵＶＭ−２）にて５時間分散したのち、水を加えて現像促進剤Ｗの濃度が２０質量％になるように調整し、現像促進剤Ｗの固体微粒子分散物を得た。こうして得た分散物に含まれる現像促進剤粒子は、メジアン径が０．５μｍ、最大粒子サイズが２．０μｍ以下、平均粒子サイズの変動係数が１８％であった。得られた分散物は、孔径３．０μｍのポリプロピレン製フィルターにてろ過を行いゴミ等の異物を除去したうえで、下記の塗布液の調製に用いた。
【０１７１】
《現像促進剤Ｗ−２の固体微粒子分散物の調製》
前記現像促進剤Ｗの固体微粒子分散物の調製において、現像促進剤をＷ−２に換えて、前記分散方法と同様にして現像促進剤Ｗ−２の固体微粒子分散物の調製した。
【０１７２】
《有機ポリハロゲン化合物Ｄの固体微粒子分散物の調製》
有機ポリハロゲン化合物Ｄを６ｋｇと変性ポリビニルアルコール（クラレ（株）製、ポバールＭＰ２０３）の１０質量％水溶液１２ｋｇ、トリイソプロピルナフタレンスルホン酸ナトリウムの２０質量％水溶液２４０ｇ、および水０．１８ｋｇを添加して、よく混合してスラリーとした。このスラリーをダイアフラムポンプで送液し、平均直径０．５ｍｍのジルコニアビーズを充填した横型ビーズミル（アイメックス（株）製、ＵＶＭ−２）にて５時間分散したのち、ベンゾイソチアゾリノンナトリウム塩２ｇと水を加えての有機ポリハロゲン化合物Ｄの濃度が３０質量％になるように調製し、有機ポリハロゲン化合物Ｄの固体微粒子分散物を得た。得られた分散物に含まれる有機ポリハロゲン化合物粒子は、メジアン径が０．４０μｍ、最大粒子サイズが２．０μｍ以下、平均粒子サイズの変動係数が２０％であった。得られた分散物は孔径３．０μｍのポリプロピレン製フィルターにてろ過を行いゴミ等の異物を除去したうえで、下記の塗布液の調製に用いた。
【０１７３】
【化７】

【０１７４】
《画像形成層塗布液の調製》
ベヘン酸銀分散物Ａの銀１ｍｏｌに対して、以下のバインダー、素材、およびハロゲン化銀乳剤Ａを添加して、水を加えて、画像形成層塗布液とした。完成後、減圧脱気を圧力０．５４ａｔｍで４５分間行った。塗布液のｐＨは７．３〜７．７、粘度は２５℃で４０〜５０ｍＰａ・ｓであった。

ｐＨ調整剤としては、ＮａＯＨを用いた。
画像形成層のバインダーに対するその他の固形分の質量比は、バインダー：ＳＢＲラテックスの添加量を変えることにより、表１の様になるように調整した。
【０１７５】
【化８】

【０１７６】
《保護層塗布液の調製》
メチルメタクリレート／スチレン／２−エチルヘキシルアクリレート／２−ヒドロキシエチルメタクリレート／アクリル酸＝５８．９／８．６／２５．４／５．１／２（質量％）のポリマーラテックス溶液（共重合体でガラス転移温度４６℃（計算値）、固形分濃度として２１．５質量％、化合物Ａを１００ｐｐｍ含有させ、さらに造膜助剤として化合物Ｄをラテックスの固形分に対して１５質量％含有させ塗布液のガラス転移温度を２４℃とした、平均粒子サイズ１１６ｎｍ）９４３ｇに水を加え、ポリハロゲン化合物Ｃの水溶液１１４．８ｇ、ポリハロゲン化合物Ａを固形分として１７．０ｇ、オルトリン酸二水素ナトリウム・二水和物を固形分として０．６９ｇ、現像促進剤Ｗを固形分として１０ｇ、現像促進剤Ｗ−２を固形分として１５ｇ、マット剤（ポリスチレン粒子、平均粒子サイズ７μｍ、平均粒子サイズの変動係数８％）１．５８ｇ、ポリビニルアルコール（クラレ（株）製，ＰＶＡ−２３５）２９．３ｇおよび化合物Ｅを０．６２ｇ、化合物Ｉを１．０ｇ加え、さらに水を加えて塗布液（メタノール溶媒を０．８質量％含有）を調製した。完成後、減圧脱気を圧力０．４７ａｔｍで６０分間行った。塗布液のｐＨは５．５、粘度は２５℃で４５ｍＰａ・ｓであった。
【０１７７】
《下層オーバーコート層塗布液の調製》
メチルメタクリレート／スチレン／２−エチルヘキシルアクリレート／２−ヒドロキシエチルメタクリレート／アクリル酸＝５８．９／８．６／２５．４／５．１／２（質量％）のポリマーラテックス溶液（共重合体でガラス転移温度４６℃（計算値）、固形分濃度として２１．５質量％、化合物Ａを１００ｐｐｍ含有させ、さらに造膜助剤として化合物Ｄをラテックスの固形分に対して１５質量％含有させ、塗布液のガラス転移温度を２４℃とした、平均粒子サイズ７４ｎｍ）６２５ｇに水を加え、化合物Ｃを０．２３ｇ、化合物Ｉを０．１３ｇ、化合物Ｆを１１．７ｇ、化合物Ｈを２．７ｇおよびポリビニルアルコール（クラレ（株）製、ＰＶＡ−２３５）１１．５ｇを加え、さらに水を加えて塗布液（メタノール溶媒を０．１質量％含有）を調製した。完成後、減圧脱気を圧力０．４７ａｔｍで６０分間行った。塗布液のｐＨは２．６、粘度は２５℃で３０ｍＰａ・ｓであった。
【０１７８】
《上層オーバーコート層塗布液の調製》
メチルメタクリレート／スチレン／２−エチルヘキシルアクリレート／２−ヒドロキシエチルメタクリレート／アクリル酸＝５８．９／８．６／２５．４／５．１／２（質量％）のポリマーラテックス溶液（共重合体でガラス転移温度４６℃（計算値）、固形分濃度として２１．５質量％、化合物Ａを１００ｐｐｍ含有させ、さらに造膜助剤として化合物Ｄをラテックスの固形分に対して１５質量％含有させ、塗布液のガラス転移温度を２４℃とした、平均粒子サイズ１１６ｎｍ）６４９ｇに水を加え、カルナヴァワックス（中京油脂（株）製、セロゾール５２４：シリコーン含有量として５ｐｐｍ未満）３０質量％溶液１８．４ｇ、化合物Ｃを０．２３ｇ、化合物Ｅを１．０ｇ、化合物Ｇを１．０ｇ、化合物Ｉを０．８７ｇ、マット剤（ポリスチレン粒子、平均粒子サイズ７μｍ、平均粒子サイズの変動係数８％）３．４５ｇおよびポリビニルアルコール（クラレ（株）製，ＰＶＡ−２３５）２６．５ｇを加え、さらに水を加えて塗布液（メタノール溶媒を１．１質量％含有）を調製した。完成後、減圧脱気を圧力０．４７ａｔｍで６０分間行った。塗布液のｐＨは５．３、粘度は２５℃で２５ｍＰａ・ｓであった。
【０１７９】
【化９】

【０１８０】
《バック／下塗り層のついたポリエチレンテレフタレート（ＰＥＴ）支持体の作製》
（１）ＰＥＴ支持体の作製
テレフタル酸とエチレングリコールを用い、常法に従い、固有粘度ＩＶ＝０．６６（フェノール／テトラクロロエタン＝６／４（質量比）中２５℃で測定）のポリエチレンテレフタレートを得た。これをペレット化した後、１３０℃で４時間乾燥した後、３００℃で溶融後Ｔ型ダイから押し出した後急冷し、熱固定後の膜厚が１２０μｍになるような厚みの未延伸フィルムを作製した。
これを周速の異なるロールを用い、３．３倍に縦延伸、ついでテンターで４．５倍に横延伸を実施した。このときの温度はそれぞれ、１１０℃、１３０℃であった。この後、２４０℃で２０秒間熱固定後、これと同じ温度で横方向に４％緩和した。この後、テンターのチャック部をスリットした後、両端にナール加工を行い、４．８ｋｇ／ｃｍ^２で巻きとった。このようにして、幅２．４ｍ、長さ３５００ｍ、厚み１２０μｍのロール状のＰＥＴ支持体を得た。
【０１８１】
（２）下塗り層およびバック層の作製
▲１▼下塗り第一層
以下に示す組成の塗布液を６．２ｍｌ／ｍ^２となる様に支持体上に塗布し、１２５℃で３０秒、１５０℃で３０秒、１８５℃で３０秒乾燥した。

【０１８２】
▲２▼下塗り第二層
以下に示す組成の塗布液を５．５ｍｌ／ｍ^２となる様に下塗り第一層の上に塗布し、１２５℃で３０秒、１５０℃で３０秒、１７０℃で３０秒乾燥した。

【０１８３】
▲３▼バック第一層
前記下塗り層塗布面とは反対側の面に０．３７５ｋＶ・Ａ・分／ｍ^２のコロナ放電処理を施し、その面に以下に示す組成の塗布液を１３．８ｍｌ／ｍ^２となる様に塗布し、１２５℃で３０秒、１５０℃で３０秒、１８５℃で３０秒乾燥した。

【０１８４】
▲４▼バック第二層
以下に示す組成の塗布液を５．５ｍｌ／ｍ^２となる様にバック第一層上に塗布し、１２５℃で３０秒、１５０℃で３０秒、１７０℃で３０秒乾燥した。
【０１８５】
ジュリマーＥＴ４１０ ５７．５ｇ
（３０％水分散物、日本純薬（株）製）
ポリオキシエチレンフェニルエーテル １．７ｇ
水溶性メラミン化合物 １５ｇ
（住友化学工業（株）製、スミテックスレジンＭ−３（８％水溶液））
セロゾール５２４（３０％水溶液、中京油脂（株）製） ６．６ｇ
蒸留水 合計量が１０００ｇとなる量
【０１８６】
▲５▼バック第三層
下塗り第一層と同じ塗布液を６．２ｍｌ／ｍ^２となる様にバック第二層上に塗布し、１２５℃で３０秒、１５０℃で３０秒、１８５℃で３０秒乾燥した。
【０１８７】
▲６▼バック第四層
以下に示す組成の塗布液を１３．８ｍｌ／ｍ^２となる様にバック第三層上に塗布し、１２５℃で３０秒、１５０℃で３０秒、１７０℃で３０秒乾燥した。

【０１８８】
【化１０】

【化１１】

【０１８９】
ラテックス−Ａ：
コア部９０質量％、シェル部１０質量％のコアシェルタイプのラテックス
（重量平均分子量３８０００）
コア部：塩化ビニリデン／メチルアクリレート／メチルメタクリレート／
アクリロニトリル／アクリル酸＝９３／３／３／０．９／０．１（質量％）
シェル部：塩化ビニリデン／メチルアクリレート／メチルメタクリレート／
アクリロニトリル／アクリル酸＝８８／３／３／３／３（質量％）
【０１９０】
（３）搬送熱処理
（３−１）熱処理
このようにして作製したバック／下塗り層のついたＰＥＴ支持体を１６０℃設定した全長２００ｍ熱処理ゾーンに入れ、張力２ｋｇ／ｃｍ^２、搬送速度２０ｍ／分で搬送した。
（３−２）後熱処理
上記熱処理に引き続き、４０℃のゾーンに１５秒間通して後熱処理を行い、巻き取った。この時の巻き取り張力は１０ｋｇ／ｃｍ^２であった。
【０１９１】
《熱現像画像記録材料の作製》
上記の如く、バック層および下塗り層を塗布し、搬送熱処理をしたＰＥＴ支持体の下塗り層の上に、特開２０００−２９６４号公報の図１で開示されているスライドビード塗布方式を用いて、前記の画像形成層塗布液を塗布銀量１．５ｇ／ｍ^２になる様に、その上に、前記の保護層塗布液をポリマーラテックスの固形分塗布量が１．３ｇ／ｍ^２になる様に同時に重層塗布した。次いでその上に、前記の下層オーバーコート層塗布液をポリマーラテックスの固形分塗布量が２．０ｇ／ｍ^２になる様に、上層オーバーコート層塗布液をポリマーラテックスの固形分塗布量が１．０ｇ／ｍ^２になる様に、同時に重層塗布した。
【０１９２】
塗布時の乾燥条件は、第一乾燥ゾーン（低速風乾燥域）が乾球温度７０〜７５℃、露点９〜２３℃、支持体面上での風速８〜１０ｍ／ｓ、液膜表面温度３５〜４０℃の範囲で乾燥し、第二乾燥ゾーン（高速風乾燥域）が、乾球温度６５〜７０℃、露点２０〜２３℃、そして支持体面上での風速が２０〜２５ｍ／ｓで乾燥した。第一乾燥ゾーンの滞在時間は、このゾーンでの恒率乾燥期の２／３の時間で、第二乾燥ゾーンに移行させ、乾燥した。第一乾燥ゾーンは、水平乾燥ゾーン（塗布機の水平方向に対し支持体が１．５°〜３°の角度）である。塗布速度は、６０ｍ／ｍｉｎで行った。乾燥後の巻取りは温度２３±３℃、相対湿度４５±５％の条件下で行った。巻き姿はその後の加工形態（画像形成層面側外巻）に合わせ、画像形成層面側を外にした。なお、熱現像画像記録材料の包袋湿度は相対湿度２０〜４０％（２５℃測定）で、得られた熱現像画像記録材料の画像形成側の膜面ｐＨは５．０、反対側の膜面ｐＨは５．９であった。
ついで、ロール状熱現像画像記録材料の包装体を、２３℃±３℃相対湿度６３±５％の環境条件下で、下記に従って作製した。
【０１９３】
《遮光リーダの製造》
厚みが３０μｍのシュリンクフィルム（グンゼ（株）製、ＴＮＳ）の両面に、遮光性フィルム（カーボンブラックを５質量％混入した厚みが３０μｍの低密度ポリエチレンシート）を貼り合わせて熱収縮性遮光フィルム製細片を製造した。得られた熱収縮性遮光フィルム製細片の熱収縮率は、１００℃において、長さ方向で１３．３％、幅方向で１１．９％であり、長さ方向のエルメンドルフ引裂荷重は０．４３Ｎであった。この熱収縮性遮光フィルム製細片を、厚みが１００μｍのＰＥＴシートの両側表面にカーボンブラックを５質量％混入した厚みが４０μｍの低密度ポリエチレンシートを貼り合わせてなる遮光シートの両側部に、それぞれ幅方向に突き出すように両側端部に沿って貼り合わせて遮光リーダを製造した。
【０１９４】
《遮光性熱現像画像記録材料ロールの製造》
上記の熱現像画像記録材料を遮光リーダを、画像形成層を有する面を外側にして、幅６１０ｍｍ、巻き長さ５９ｍに裁断しながら外径３インチの紙巻芯に巻き付けた。
ついで、円盤状遮光部材を熱現像画像記録材料ロールの両端部に取り付けた。次いで、ロール状熱現像画像記録材料に遮光リーダを粘着テープで貼り付け、熱現像画像記録材料ロールの周囲に巻き付けながら、遮光リーダの熱収縮性遮光フィルム製細片の表面に２７０℃の熱風を吹き付けて、遮光リーダの熱収縮性遮光フィルム製細片を円盤状遮光部材の外周縁部を越えて外側表面に熱収縮した状態で接触させた。そして、遮光リーダの巻き終わりの先端部と該遮光リーダの１周回前の外側表面とを接着テープにより封止した後、円盤状遮光部材の外側表面に密着している熱収縮性遮光フィルム製細片の表面に１３０℃に加熱したヒータを押し当てて、円盤状遮光部材の外側表面と熱収縮性遮光フィルム製細片とを融着させた。
【０１９５】
《切断試験方法》
上記で得られた熱現像画像記録材料を下記の方法に基づいて評価した。
図１、図２に示す切断用ダイセット（上刃刃角α＝９０度、シヤー角β＝１５度）を用いて、プレス機（蛇の目ミシン工業（株） 製、ＥＲＥＣＴＲＯ ＰＲＥＳＳ ＪＰ−５０３型）で、切断速度＝３０ｍｍ／秒で、画像形成層を有する面を上刃側にして切断し、切断部の画像形成層を有する側の塗布膜の亀裂・剥離の発生及びベコの発生を評価した。熱現像画像記録材料の温度は、切断直前に加熱し、切断時の温度を放射温度計にて測定した。
＜亀裂・剥離の度合＞
５…塗布膜の亀裂・剥離無し
３…亀裂有り・剥離無し
１…亀裂有り・剥離あり
「４」は「５」と「３」の中間、「２」は「３」と「１」の中間である。「４」以上が実用上問題のないレベルである。
＜ベコの度合＞
５…ベコ無し
３…ベコやや有り
１…ベコ有り
「４」は「５」と「３」の中間、「２」は「３」と「１」の中間である。「４」以上が実用上問題のないレベルである。
【０１９６】
《実技濃度の評価》
得られた熱現像画像記録材料に対して、ビーム径（ビーム強度の１／２のＦＷＨＭ）１２．５６μｍ、レーザー出力５０ｍＷ、出力波長７８３ｎｍの半導体レーザーを搭載した単チャンネル円筒内面方式のレーザー露光装置を使用し、ミラー回転数６００００ｒｐｍ、露光時間１．２×１０^−８秒の露光を実施した。
この時のオーバーラップ係数は０．４４９にし、熱現像画像記録材料面上のレーザーエネルギー密度は７５μＪ／ｃｍ^２とした。上記のレーザー露光装置を用いて、１７５線／インチで光量を変えながらテストステップを出力し、ドライシステムプロセサ（富士写真フイルム（株）製、ＦＤＳ−６１００Ｘ）を用いて、１２１℃、２０秒の現像条件で熱現像処理を行い、中間網点が５０％になるＬＶ値で露光した際のＤｍａｘ（最高濃度）部を測定し、実技濃度とした。濃度測定はマクベスＴＤ９０４濃度計（可視濃度）により行った。
【０１９７】
得られた結果を表１に示す。表１の結果から本発明の条件を満たす試料は、熱現像画像記録材料の切断時の亀裂・膜剥がれの発生なく、かつ、これらの切り屑などによる画像欠陥がなく写真製版用途に最適な画像を提供し得ることがわかる。
【０１９８】
【表１】

【０１９９】
【発明の効果】
本発明の方法にしたがって熱現像画像記録材料を切断すれば、亀裂、膜剥がれ、切り屑の発生を効果的に抑えることができ、熱現像画像記録材料の画像欠陥の発生も防ぐことができる。
【図面の簡単な説明】
【図１】切断試験で用いた切断用ダイセットを説明するための斜視図である。
【図２】切断試験で用いた切断用ダイセットを説明するための断面図である。
【符号の説明】
１ 上刃
２ 下刃
３ 熱現像画像記録材料
４ 上刃側切断面
α° 上刃の刃先角
β° シャー角
３ａ_１ 切断された下刃側画像形成層＋保護層
３ｂ_１ 切断された下刃側支持体
３ａ_２ 切断された上刃側画像形成層＋保護層
３ｂ_２ 切断された上刃側支持体[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for cutting a heat-developable image recording material, and more particularly to a method for cutting a heat-developable image recording material for a scanner and an image setter suitable for photolithography. More specifically, the present invention relates to a technique capable of obtaining an optimal image in which generation of chips due to cracks and film peeling is suppressed when the heat-developable image recording material is cut for use in photolithography. Is.
[0002]
[Prior art]
Many image recording materials having a photosensitive layer on a support and forming an image by image exposure are known. However, in the fields of medical treatment and printing plate making, waste liquid from wet processing of image recording materials has become a problem in terms of workability. In recent years, the amount of processing waste liquid has been strongly reduced from the viewpoint of environmental conservation and space saving. It has come to be desired. Therefore, attention is paid to the technology related to heat-developable image recording materials for photoengraving that can be efficiently exposed by a laser scanner or laser imagesetter and can form a clear black image with high resolution and sharpness. Has been. Since the heat-developable image recording material does not use a solution processing chemical, it is possible to provide a heat-development processing system that is simpler and does not impair the environment.
[0003]
Methods for forming an image by thermal development are described in, for example, Patent Document 1, Patent Document 2, and Non-Patent Document 1. Such heat-developable image recording materials typically contain a reducible non-photosensitive silver source (eg, an organic silver salt), a catalytically active amount of a photocatalyst (eg, a silver halide), and a silver reducing agent, usually in an organic binder matrix. Contains in a dispersed state. The heat-developable image recording material is stable at normal temperature, but when heated to a high temperature (for example, 80 ° C. or higher) after exposure, redox between the reducible silver source (which functions as an oxidizing agent) and the reducing agent. Silver is produced through the reaction. This redox reaction is promoted by the catalytic action of the latent image generated by exposure. The silver produced by the reaction of the reducible silver salt in the exposed areas provides a black image that contrasts with the unexposed areas and forms an image.
[0004]
Conventionally, the heat-developable image recording materials are known, but most of them form an image forming layer by applying a coating solution containing an organic solvent such as toluene, methyl ethyl ketone (MEK), or methanol. ing. The use of an organic solvent as a solvent is not only adversely affecting the human body in the production process but also disadvantageous in terms of cost due to recovery of the solvent and the like.
Therefore, a method of forming an image forming layer using a coating solution of an aqueous solvent without such a concern has been considered. For example, Patent Document 3 and Patent Document 4 describe examples using gelatin as a binder. Patent Document 5 describes an example using polyvinyl alcohol as a binder.
Furthermore, Patent Document 6 describes an example in which gelatin and polyvinyl alcohol are used in combination. As another example, Patent Document 7 describes an example of an image forming layer using water-soluble polyvinyl acetal as a binder.
Certainly, when such a binder is used, an image forming layer can be formed using a coating solution of an aqueous solvent, and there are great environmental and cost advantages.
[0005]
However, when polymers such as gelatin, polyvinyl alcohol, and water-soluble polyacetal are used as binders, dehydration shrinkage and thermal expansion of the binder occur at the same time during thermal development, and the thermal expansion behavior of the support is different. Particularly in color printing, there is a drawback that the registration accuracy is deteriorated and color misregistration is likely to occur.
[0006]
Therefore, in order to improve these drawbacks, Patent Document 8 proposes to use a polymer latex as a binder for the image forming layer and protective layer of the heat-developable image recording material and the back layer.
However, these heat-developable image recording materials are extremely fragile because the binder of the image forming layer is extremely small, and problems such as cracking and film peeling occur when the heat-developable image recording material is cut. There is a tendency to generate chips. When these chips adhere to the surface of the heat-developable image recording material, various image defects are caused, so that there is a great practical problem. As countermeasures against this problem, adjust the edge angle of a cutting device that is normally used, adjust the distance between the upper and lower blades, the sandwiching angle, the crossing angle, the pressing force, adjust the cutting speed, etc. However, these adjustments alone did not solve the problem.
[0007]
As a technique for improving the method for cutting a heat-developable image recording material, Patent Document 9 describes a technique for reducing the dynamic friction coefficient between a cutting blade and a film to 0.2 or less, and Patent Document 10 describes an emulsion side. A technique is described in which the surface temperature is cut at or above the glass transition temperature (Tg) of the image forming layer and below the heat development temperature.
However, in the case where the ratio of the other solid content to the binder of the image forming layer is large and the protective layer has a polymer latex, even if these techniques are applied, the above problem cannot be completely solved. There was a strong demand for the development of improved technology.
[0008]
[Patent Document 1] US Pat. No. 3,152,904
[Patent Document 2] US Pat. No. 3,457,075
[Patent Document 3] JP-A-49-52626
[Patent Document 4] JP-A-53-116144
[Patent Document 5] Japanese Patent Laid-Open No. 50-151138
[Patent Document 6] JP-A-60-61747
[Patent Document 7] Japanese Patent Laid-Open No. 58-28737
[Patent Document 8] JP-A-11-84573
[Patent Document 9] Japanese Patent Laid-Open No. 2002-36173
[Patent Document 10] Japanese Patent Laid-Open No. 2001-337411
[Non-Patent Document 1] D.A. Klosterboer “Thermally Processed Silver Systems A” (Imaging Processes and Materials) Nevlett 8th Edition, J. Sturge (Walworth, edited by A. Shepp, Chapter 9, page 279, 1989)
[0009]
[Problems to be solved by the invention]
Therefore, the problem to be solved by the present invention is to suppress the generation of cracks, film peeling and chips when the heat-developable image recording material is cut. That is, an object of the present invention is to provide a heat-developable image recording capable of suppressing the occurrence of cracks, film peeling and chips when the heat-developable image recording material is cut, and preventing the occurrence of image defects in the heat-developable image recording material. It is to provide a method for cutting a material. In particular, it is an object of the present invention to provide a cutting method for a heat-developable image recording material for photoengraving capable of obtaining a high contrast (γ ≧ 10) and obtaining an image optimal for photoengraving.
[0010]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have achieved the problems by setting the temperature of the heat-developable image recording material at the time of cutting to a specific temperature range. That is, the support has at least one image forming layer containing an organic silver salt, a photosensitive silver halide, and a reducing agent, and at least one protective layer provided on the image forming layer. The heat-developable image-recording material is cut by a method for cutting a heat-developable image-recording material, wherein the heat-developable image-recording material is cut at a temperature not lower than the glass transition temperature of the protective layer and not higher than the glass transition temperature of the support.
[0011]
The support of the heat-developable image recording material used in the present invention is treated at 130 ° C. to 185 after treatment for improving adhesion to the image forming layer and / or the back layer (for example, coating of an undercoat layer). It is preferable that the heat treatment is performed at a temperature of ° C. Further, a polymer latex is preferably used as a binder for the image forming layer, the protective layer and the back layer. The heat-developable image recording material used in the present invention preferably has a high contrast (γ ≧ 10) and contains a high contrast agent for the purpose of obtaining an image optimal for photolithography. Moreover, it is preferable that mass ratio of the other solid content with respect to the binder of an image forming layer is 1.0-2.5.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The method for cutting the heat-developable image recording material of the present invention will be described in detail below. In the present specification, “to” indicates a range including numerical values described before and after the values as a minimum value and a maximum value, respectively.
[0013]
The heat-developable image recording material used in the present invention is provided on a support, at least one image forming layer containing an organic silver salt, a photosensitive silver halide, and a reducing agent, and an upper part of the image forming layer. And at least one protective layer. Moreover, it is preferable to have at least one back layer on the opposite side of the support.
[0014]
Polymer latex is preferably used as a binder in the image forming layer of the heat-developable image recording material, the protective layer on the upper side, and the back layer on the side opposite to the side having the image forming layer.
The polymer latex used in the present invention is not limited to a normal polymer latex having a uniform structure, and a so-called core / shell type latex may be used. In this case, the core and shell may preferably have different glass transition temperatures (Tg). In particular, a core / shell type latex in which the core Tg is higher than the shell Tg is preferable in that good film-forming properties can be obtained. The glass transition temperature of the polymer is determined, for example, by the method described in “J. Brandrup, EH Immergut, Polymer Handbook, 2nd Edition, III-139 to III-192 (1975)”.
[0015]
The “polymer latex” referred to in the present specification is a polymer in which a water-insoluble hydrophobic polymer is dispersed as fine particles in a water-soluble dispersion medium. As the dispersion state, the polymer is emulsified in a dispersion medium, the emulsion is polymerized, the micelle is dispersed, or the polymer chain has a partially hydrophilic structure and the molecular chain itself is molecularly dispersed. Any of them may be used. For the polymer latex that can be used in the present invention, “synthetic resin emulsion (Hiraku Okuda, Hiroshi Inagaki, published by Kobunshi Publishing Co., Ltd. (1978))”, “application of synthetic latex (Takaaki Sugimura, Ikuo Kataoka, Junichi Suzuki) , Edited by Keiji Kasahara, published by Kobunshi Publishing Co., Ltd. (1993)), “chemistry of synthetic latex (written by Soichi Muroi, published by Kobunshi Publishing Co., Ltd. (1970))”, and the like. The average particle size of the dispersed particles is preferably in the range of 1 to 50,000 nm, more preferably about 5 to 1,000 nm. The particle size distribution of the dispersed particles is not particularly limited, and may have a wide particle size distribution or a monodispersed particle size distribution.
[0016]
The glass transition temperature of the outermost protective layer is preferably 25 ° C. or higher, and more preferably 30 ° C. to 70 ° C.
The glass transition temperature of the protective layer is determined by differential scanning calorimetry based on the test method of JIS K7121 (transition temperature measurement method) and K7122 (transition heat measurement method) by removing the protective layer of the heat-developable image recording material by a layered cutting method. DSC).
[0017]
In this invention, the minimum film formation temperature of the polymer latex of a protective layer is -30 degreeC-70 degreeC, More preferably, it is 0 degreeC-50 degreeC. Furthermore, the minimum film forming temperature of the polymer latex is preferably not more than the glass transition temperature of the polymer in the latex.
A film-forming aid may be added to control the minimum film formation temperature. A film-forming aid, also called a plasticizer, is an organic compound (usually an organic solvent) that lowers the minimum film-forming temperature of polymer latex. For example, “Synthetic Latex Chemistry (Souichi Muroi, published by Kobunshi Shuppankai (1970)” )"It is described in.
[0018]
Specific examples of the film forming aid include the following compounds.
K-1 benzyl alcohol
K-2 2-dimethylamonoethanol
K-3 2,2,4-trimethylpentanediol-1,3-monoisobutyrate
K-4 Diacetone alcohol
K-5 Ethylene glycol monobutyl ether
K-6 Dietylene glycol monobutyl ether acetate
K-7 Dibutyl phthalate
K-8 Diethylene glycol
[0019]
Polymer species of polymer latex used for the protective layer include acrylic resin, vinyl acetate resin, polyester resin, polyurethane resin, rubber resin, vinyl chloride resin, vinylidene chloride resin, polyolefin resin, or copolymers thereof. . The polymer may be a linear polymer, a branched polymer, or a crosslinked polymer. The polymer may be a so-called homopolymer in which a single monomer is polymerized or a copolymer in which two or more monomers are polymerized. In the case of a copolymer, it may be a random copolymer or a block copolymer. The molecular weight of the polymer is a number average molecular weight of 5,000 to 1,200,000, preferably about 10,000 to 1,000,000. If the molecular weight is too small, the mechanical strength of the image forming layer is insufficient, and if it is too large, the film formability is poor, which is not preferable.
[0020]
Specific examples of the polymer latex used for the protective layer include the following. Methyl methacrylate / ethyl acrylate / methacrylic acid copolymer latex, methyl methacrylate / butadiene / itaconic acid copolymer latex, ethyl acrylate / methacrylic acid copolymer latex, methyl methacrylate / 2-ethylhexyl acrylate / styrene / acrylic acid copolymer latex, styrene Latex of butadiene / butadiene / acrylic acid copolymer, latex of styrene / butadiene / divinylbenzene / methacrylic acid copolymer, latex of methyl methacrylate / vinyl chloride / acrylic acid copolymer, latex of vinylidene chloride / ethyl acrylate / acrylonitrile / methacrylic acid copolymer, and the like. More specifically, copolymer latex of methyl methacrylate / ethyl acrylate / methacrylic acid = 33.5 / 50 / 16.5 (mass%), methyl methacrylate / butadiene / itaconic acid = 47.5 / 47.5 / 5 ( (Mass%) copolymer latex, ethyl acrylate / methacrylic acid = 95/5 (mass%) copolymer latex, and the like.
[0021]
Moreover, such a polymer is also marketed and the following polymers can be utilized. For example, as an example of acrylic resin, Sebian A-4635, 46583, 4601 (manufactured by Daicel Chemical Industries, Ltd.), Nipol LX811, 814, 821, 820, 857 (manufactured by Nippon Zeon Co., Ltd.), VONCORT-R3340, As polyester resins such as R3360, R3370, 4280 (manufactured by Dainippon Ink Chemical Co., Ltd.), FINETEX ES650, 611, 675, 850 (manufactured by Dainippon Ink Chemical Co., Ltd.), WD-size, WMS (and above) Eastman Chemical Co., Ltd.), polyurethane resins such as HYDRAN AP10, 20, 30, 40 (manufactured by Dainippon Ink Chemical Co., Ltd.), and rubber resins such as LACSTAR 7310K, 3307B, 4700H, 7132C (above Dainippon Ink) (Chemical Co., Ltd.) Nipol LX410, 430, 435, 438C (made by Nippon Zeon Co., Ltd.), vinyl chloride resin G351, G576 (made by Nippon Zeon Co., Ltd.), etc., vinylidene chloride resin L502, L513 (above Asahi Kasei Kogyo) (Made by Co., Ltd.), Aron D7020, D504, D5071 (above made by Mitsui Toatsu Co., Ltd.), etc., and olefin resins include Chemipearl S120, SA100 (made by Mitsui Petrochemical Co., Ltd.) and the like. These polymers may be used alone or in combination of two or more as required.
[0022]
In the present invention, the binder preferably used in the protective layer is a polymer having at least one monomer having a solubility in water at 25 ° C. of 0.1% by mass or more, and is based on an organic conceptual diagram. A polymer having an I / O value obtained by dividing the value by the organic value is 0.1 to 1.0, preferably 0.3 to 0.8.
When the protective layer is composed of two or more layers, the polymer I / O value of the protective layer adjacent to the image forming layer is less than 0.55, preferably less than 0.55, and more than 0.10. Furthermore, it is preferable that the I / O value of at least one layer not adjacent to the image forming layer is 0.55 or more and is larger than the protective layer adjacent to the image forming layer.
[0023]
The term “binder for the protective layer” means a main binder, which occupies 60% by mass or more of the total binder. The total binder amount of the protective layer is 0.2-10.0 g / m.², Preferably 0.5 to 6.0 g / m²Range.
[0024]
The solubility of the monomer used to form the polymer used in the protective layer in water at 25 ° C. is determined by the method described in “4th Experimental Chemistry Course 1 Basic Operation I” (1990, issued by Maruzen Co., Ltd.). Can be sought. The solubility in water at 25 ° C. is preferably 0.1% by mass or more, and more preferably 0.1% by mass to 10% by mass.
Specific examples of the monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, methyl methacrylate, vinyl acetate, acrylonitrile, methacrylonitrile, acrylamide, acrylic An acid, methacrylic acid, 2-hydroxylmethacrylic acid, etc. are mentioned.
[0025]
The I / O value of the polymer used for the protective layer, that is, the value obtained by dividing the inorganic group based on the organic conceptual diagram by the organic group is “Organic conceptual diagram-basics and application” (1984 Yoshio Koda, Sankyo It can be obtained by the method described in “Publishing and Publication”.
[0026]
Here, an organic conceptual diagram is an orthogonal coordinate in which the properties of a compound are divided into an organic group that exhibits covalent bonding and an inorganic group that exhibits ionic bonding, and all organic compounds are named organic and inorganic axes. The inorganic value based on this is determined based on the hydroxyl group based on the inorganic value, that is, the boiling point of the linear alcohol. If the distance between the curve and the boiling point curve of the straight-chain paraffin is about 5 ° C., the temperature is about 100 ° C. Therefore, the influence of one hydroxyl group is set to 100 as a numerical value. On the other hand, the organic value is based on the methylene group in the molecule as the unit, and can be measured by the number of carbon atoms that represent the methylene group. The average value of the boiling point increase due to addition of one carbon in the vicinity of 5 to 10 carbon atoms of the linear compound is 20 ° C., and is a value determined as 20 on the basis of this. The inorganic value and the organic value are determined so as to correspond one-to-one on the graph. The I / O value is calculated from these values.
[0027]
As described above, a polymer latex is preferably used as the binder of the image forming layer and the back layer on the side opposite to the side having the image forming layer. The preferable range of the glass transition temperature (Tg) of the polymer latex is different between the image forming layer and the back layer. The image forming layer preferably has a temperature of -30 ° C to 40 ° C in order to promote diffusion of the photographic material during heat development. The back layer is preferably 25 ° C. to 150 ° C. in order to come into contact with various devices.
[0028]
As the polymer species used for the image forming layer and the back layer, a polymer selected from binder species used for the protective layer can be used. Particularly preferred polymers are latex of styrene / butadiene / acrylic acid copolymer for the image forming layer, and Julima-ET410 (manufactured by Nippon Seiyaku Co., Ltd.), Chemipearl S120 (manufactured by Mitsui Petrochemical Co., Ltd.), Pesresin A520 (manufactured by Takamatsu Yushi Co., Ltd.).
[0029]
It is preferable that 50% by mass or more, preferably 70% by mass or more of the total amount of binder used in the image forming layer is polymer latex.
The total binder amount of the image forming layer is 0.2 to 30 g / m.²Preferably, 1.0 to 15 g / m²It is more preferable that
The ratio of the other solid content to the binder of the image forming layer is preferably 1.0 to 2.5, more preferably 1.2 to 2.0 in terms of mass ratio. If the mass ratio is less than 1.0, the darkening density of the image after heat development is low, and if it is 2.5 or more, the coating film becomes extremely fragile and the film strength that can withstand normal handling cannot be obtained. Tend.
[0030]
The total binder amount in the back layer is 0.01-10.0 g / m.²Preferably, 0.05 to 5.0 g / m²It is more preferable that
[0031]
Each of these layers may be provided in two or more layers. When there are two or more image forming layers, it is preferable to use a polymer latex as a binder for all layers. The back layer is a layer provided on the undercoat layer on the back surface of the support and may be present in two or more layers. It is preferable to use a polymer latex for at least one layer, particularly the outermost back layer.
[0032]
In the present invention, each layer is provided with a first polymer latex into which functional groups described in paragraphs 0023 to 0041 of JP-A No. 2000-19678 are introduced and a functional group capable of reacting with the first polymer latex. It can also be formed by using a crosslinking agent and / or a second polymer latex.
Specific examples of the functional group include a carboxyl group, a hydroxyl group, an isocyanate group, an epoxy group, an N-methylol group, an oxazolinyl group, an amino group, and a vinylsulfonyl group. Examples of the crosslinking agent include an epoxy compound, an isocyanate compound, and a blocked isocyanate compound. , Methylol compounds, hydroxy compounds, carboxyl compounds, amino compounds, ethyleneimine compounds, aldehyde compounds, halogen compounds and the like. Specific examples of the crosslinking agent include isocyanate compounds: hexamethylene isocyanate, Duranate WB40-80D, WX-1741 (Asahi Kasei Kogyo Co., Ltd.), Bihijoule 3100 (Sumitomo Bayer Urethane Co., Ltd.), Takenate WD725 (Takeda Pharmaceutical Co., Ltd.) Aquanate 100, 200 (manufactured by Nippon Polyurethane Co., Ltd.), water-dispersed polyisocyanate and amino compound described in JP-A-9-160172: Sumitex Resin M-3 (Sumitomo Chemical Co., Ltd.) Product), epoxy compound: Denacol EX-614B (manufactured by Nagase Kasei Kogyo Co., Ltd.), halogen compound: 2,4 dichloro-6-hydroxy-1,3,5-triazine sodium and the like.
[0033]
In the present invention, a slipping agent can be added to the outermost layer on the side having the image forming layer and / or the opposite side. The kind and amount of the slip agent are not particularly limited. The slip agent may be any compound that, when present on the surface of the object, reduces the coefficient of friction of the object surface compared to when it is not present.
[0034]
As the slipping agent used in the present invention, it is preferable to use compounds described in JP-A No. 11-84573, paragraph numbers 0061 to 0064, and Japanese Patent Application No. 2000-47083, paragraph numbers 0049 to 0062. Specific examples of preferable slipping agents include cellosol 524 (main component carnauba wax), polysiloxane, polylon A, 393, H-481 (main component polyethylene wax), and high micron G-110 (main component ethylenebisstearic acid amide). , High micron G-270 (main component stearic acid amide) (manufactured by Chukyo Yushi Co., Ltd.),
W-1 C₁₆H₃₃-O-SO₃Na,
W-2 C₁₈H₃₇-O-SO₃Na
W-3 C₁₇H₃₃CONH (CH₃) CH₂CH₂SO₃Na
and so on.
The amount of the slip agent used is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, based on the amount of the binder in the additive layer.
[0035]
When the heat-developable image recording material is subjected to heat development processing, as shown in JP-A-2000-171935 and JP-A-2001-22024, the preheating unit is conveyed by a counter roller, and the heat-development processing unit forms an image. In the case of using a heat development processing apparatus that conveys the side having the layer by driving a roller and sliding the back surface on the opposite side to a smooth surface, the side having the image forming layer of the heat development image recording material at the development processing temperature is used. The ratio of the coefficient of friction between the outermost surface layer and the outermost surface layer of the back surface is preferably 1.5 or more. The upper limit is not particularly limited, but is preferably about 30. This value is obtained by the following equation.
Ratio of friction coefficient = dynamic friction coefficient between the roller member of the heat developing machine and the surface having the image forming layer (μe) / dynamic friction coefficient between the smooth surface member of the heat developing machine and the back surface (μb)
The coefficient of dynamic friction (μb) between the smooth surface member and the back surface of the heat developing machine is 1.0 or less, preferably 0.8 to 0.05.
[0036]
As the matting agent to be contained in the outermost layer on the surface having the image forming layer and / or the opposite surface in the present invention, those described in paragraph Nos. 0052 to 0059 of JP-A No. 11-84573 can be used.
At least one of the surface having the image forming layer of the heat-developable image recording material and the surface of the outermost layer on the opposite side, preferably both the Beck smoothness is 5000 seconds or less, more preferably 100 seconds to 4000 seconds. The Beck smoothness can be controlled by appropriately changing the particle size and content of the matting agent. The Beck smoothness in the present invention can be easily determined by Japanese Industrial Standard (JIS) P8119 “Smoothness test method using Beck tester for paper and paperboard” and TAPPI standard method T479.
[0037]
In the present invention, the coating film on the surface having the image forming layer and / or the opposite surface has a Vickers hardness at 40 ° C. of 30 N / mm.²Or more, preferably 40 to 300 N / mm²It is more preferable that In particular, the Vickers hardness of the surface having the image forming layer preferably takes these values.
The Vickers hardness can be obtained by a Vickers hardness test method described in JIS Z2244, B 7725. Specifically, using a diamond square pyramid indenter with a face angle of 136 degrees, the test force F (N) and the surface area (mm²) And the following equation (2).
Formula (2) HV = 0.1891F / d²
In the formula, HV is Vickers hardness, F is a test force (N), and d is an average (mm) of diagonal lengths in two directions of the depression.
The Vickers hardness in this specification is determined by measuring the hardness when the sample temperature is 40 ° C., the test force is 300 mmN, and the indentation depth is 2 μm, using a Fischerscope H100VP.
[0038]
The image forming layer coating solution or protective layer coating solution in the present invention is preferably a so-called pseudoplastic fluid. Pseudoplasticity refers to the property of decreasing viscosity with increasing shear rate.
[0039]
The image forming layer coating solution in the present invention has a shear rate of 0.1 s.^-1Is 100 mPa · s or more, preferably 100 mPa · s to 10000 mPa · s, and more preferably 200 mPa · s to 5000 mPa · s. And shear rate 1000s^-11 mPa · s to 100 mPa · s is preferable.
The protective layer coating liquid in the present invention has a shear rate of 0.1 s.^-110 mPa · s to 5000 mPa · s, preferably 20 mPa · s to 3000 mPa · s.
[0040]
The viscosity and shear rate in the present invention are defined as follows.
Consider a model fluid that exists between two parallel planes. One of the two planes is fixed, the other is movable, and the distance between them is x. If force F acts on the moving surface (upper surface) and the upper surface slides at a speed v relative to the lower surface, the fluid layer between the two planes will have the same lateral displacement. The top fluid moves the fastest and the bottom fluid moves the slowest. Layers in the middle move at an intermediate speed. However, the velocity gradient dv / dx is the same for any part of the fluid. This velocity gradient γ is defined as the shear rate in the present invention. The total force acting on the upper surface (area A) is F, and the stress is F / A. When this force is defined as the shear stress τ, the viscosity η in the present invention is defined by the ratio τ / η of the shear stress and the shear rate.
[0041]
Although any apparatus may be used for the viscosity measurement in the present invention, an RFS fluid spectrometer manufactured by Rheometrics Far East Co., Ltd. is preferably used and measured at 25 ° C.
[0042]
In the present invention, a water-soluble polymer is preferably used as a viscosity modifier for imparting coatability to each layer, and it may be either a natural product or a synthetic polymer, and is not limited. As natural products, they are starches (corn starch, starch, etc.), seaweed (agar, sodium alginate, carrageenan, etc.), vegetable stickies (arabic gum, etc.), animal proteins (dish, casein, gelatin, egg white, etc.) , Fermentation adhesives (pullulan, dextrin, etc.), semi-synthetic polymers such as starch (soluble starch, carboxyl starch, dextran, etc.), cellulose (viscose, methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropyl) Cellulose, hydroxypropylmethylcellulose, etc.), and synthetic polymers (polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, polyethylene glycol, poly Maleic acid copolymers such as propylene glycol, polyvinyl ether, polyethyleneimine, polystyrene sulfonic acid or copolymers thereof, polyvinyl sulfinic acid or copolymers thereof, polyacrylic acid or copolymers thereof, acrylic acid or copolymers thereof, etc. Maleic acid monoester copolymer, acryloylmethylpropanesulfonic acid or a copolymer thereof, and the like.
These compounds are described in detail in “Application and Market of New Water-Soluble Polymer (Published by CMC Co., Ltd., edited by Shinji Nagatomo, published on November 4, 1988)”.
[0043]
Among these, water-soluble polymers preferably used are gelatin, polyvinyl alcohol (for example, PVA-205, PVA-217, PVA-224, PVA-235 manufactured by Kuraray Co., Ltd.), κ-carrageenan, xanthan gum, locust bean gum, Methyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxypropyl methyl cellulose, polycarboxylic acid, polystyrene sulfonic acid, modified polyacryl sulfonic acid (for example, SN thickener A-818 manufactured by SAN NOPCO LIMITED), modified polyacryl carboxylic acid (for example, SAN) SN thickener A-815 manufactured by NOPCCO LIMITED), poly N-vinylacetamide (Biac GE-191, GE-167 manufactured by Showa Denko KK), etc. And the like.
[0044]
The amount of the water-soluble polymer used as the viscosity modifier is not particularly limited as long as the viscosity increases when added to the coating solution. In general, the concentration in the liquid is 0.01 to 30% by mass, more preferably 0.05 to 20% by mass, and particularly preferably 0.1 to 10% by mass. The viscosity obtained by these is measured with a B-type rotational viscometer (No. 1 rotor, rotation speed: 60 rpm). The coating solution viscosity of the image forming layer is preferably 15 to 100 mPa · s at 25 ° C., more preferably 30 ~ 70 mPa · s. On the other hand, the coating solution viscosity of the protective layer is preferably 5 to 75 mPa · s at 25 ° C., more preferably 20 to 50 mPa · s. In addition to the coating solution, it is generally desirable to add the viscosity modifier as a diluted solution as much as possible. Moreover, it is preferable to perform sufficient stirring at the time of addition.
[0045]
The organic silver salt that can be used in the present invention is relatively stable to light, but is 80 ° C. or higher in the presence of an exposed photocatalyst (such as a latent image of photosensitive silver halide) and a reducing agent. It is a silver salt that forms a silver image when heated above. The organic silver salt may be any organic material containing a source capable of reducing silver ions. Silver salts of organic acids, particularly silver salts of long-chain fatty carboxylic acids (having 10 to 30, preferably 15 to 28 carbon atoms) are preferred. Also preferred are organic or inorganic silver salt complexes in which the ligand has a complex stability constant in the range of 4.0 to 10.0. The silver-providing substance can preferably constitute about 5 to 70% by weight of the image forming layer. Preferred organic silver salts include silver salts of organic compounds having a carboxyl group. Examples of these include, but are not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. Preferred examples of the aliphatic carboxylic acid silver salt include silver behenate, silver arachidate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate and fumarate. Silver acid, silver tartrate, silver linoleate, silver butyrate and silver camphorate, mixtures thereof, and the like.
[0046]
In the present invention, among the organic acid silver or organic acid silver mixture mentioned above, it is preferable to use organic acid silver having a silver behenate content of 75 mol% or more, and more preferably 85 mol% or more. Here, the silver behenate content indicates the molar fraction of silver behenate relative to the organic acid silver used. As the organic acid silver other than the silver behenate contained in the organic acid silver used in the present invention, those listed above can be preferably used.
[0047]
The organic acid silver preferably used in the present invention is prepared by reacting a silver nitrate with a solution or suspension of an alkali metal salt (including Na salt, K salt, Li salt, etc.) of the organic acid shown above. . About these preparation methods, the method of Paragraph Nos. 0019-0021 of Unexamined-Japanese-Patent No. 2000-292882 can be used.
[0048]
In the present invention, a method of preparing organic acid silver by adding an aqueous silver nitrate solution and an organic acid alkali metal salt solution into a means for mixing a sealed liquid can be preferably used. About these preparation methods, the method of Unexamined-Japanese-Patent No. 2001-33907 can be used.
[0049]
In the present invention, a water-soluble dispersant can be added to the silver nitrate aqueous solution and the organic acid alkali metal salt solution used in the preparation of the organic acid silver or the reaction liquid. Specific examples of the type and amount of dispersant used are described in paragraph No. 0052 of JP-A No. 2000-305214.
[0050]
The organic acid silver used in the present invention is preferably prepared in the presence of a tertiary alcohol. The tertiary alcohol is preferably one having a total carbon number of 15 or less, particularly preferably 10 or less. Examples of preferred tertiary alcohols include tert-butanol, but the present invention is not limited thereto.
[0051]
The addition timing of the tertiary alcohol used in the present invention may be any timing at the time of preparing the organic acid silver, but it is preferably added at the time of preparing the organic acid alkali metal salt to dissolve and use the organic acid alkali metal salt. . Moreover, although the usage-amount of a tertiary alcohol can be arbitrarily used in the range of 0.01-10 by mass ratio with respect to the water as a solvent at the time of organic-acid silver preparation, the range of 0.03-1 is used. preferable.
[0052]
The shape and size of the organic silver salt that can be used in the present invention are not particularly limited, but those described in paragraph No. 0024 of JP-A No. 2000-292882 can be used. The method for measuring the shape of the organic silver salt can be determined from a transmission electron microscope image of the organic silver salt dispersion. As another method for measuring monodispersity, there is a method for obtaining the standard deviation of the volume weighted average diameter of the organic silver salt, and the percentage (variation coefficient) of the value divided by the volume weighted average diameter is preferably 80% or less, more Preferably it is 50% or less, More preferably, it is 30% or less. As a measuring method, for example, it is obtained from the particle size (volume weighted average diameter) obtained by irradiating an organic silver salt dispersed in a liquid with laser light and obtaining an autocorrelation function with respect to the temporal change of the fluctuation of the scattered light. Can do. The average particle size in this measurement method is preferably a solid fine particle dispersion of 0.05 μm to 10.0 μm. More preferably, the average particle size is 0.1 μm to 5.0 μm, and still more preferably the average particle size is 0.1 μm to 2.0 μm.
[0053]
The organic silver salt that can be used in the present invention can be preferably desalted. There is no particular limitation on the method for performing desalting, and a known method can be used, but a known filtration method such as centrifugal filtration, suction filtration, ultrafiltration, and flock-forming water washing by agglomeration method can be preferably used. As the ultrafiltration method, the method described in JP-A-2000-305214 can be used.
[0054]
In the present invention, for the purpose of obtaining an organic silver salt solid dispersion having a high S / N, a small particle size, and no aggregation, the organic silver salt as an image forming medium is contained, and the photosensitive silver salt is substantially contained. It is preferable to use a dispersion method in which a pressure drop is performed after converting a non-aqueous dispersion into a high-speed flow. Regarding these dispersing methods, the methods described in JP-A-2000-292882, paragraph numbers 0027 to 0038 can be used.
[0055]
The particle size (volume-weighted average diameter) of the organic silver salt solid fine particle dispersion is obtained, for example, by irradiating the solid fine particle dispersion dispersed in the liquid with laser light and obtaining the autocorrelation function with respect to the time variation of the fluctuation of the scattered light. Can be determined from the particle size (volume load average diameter) or transmission electron microscopic image obtained. A solid fine particle dispersion having an average particle size of 0.05 μm to 10.0 μm is preferred. More preferably, the average particle size is 0.1 μm to 5.0 μm, and still more preferably the average particle size is 0.1 μm to 2.0 μm.
[0056]
The particle size distribution of the organic silver salt solid fine particle dispersion is preferably monodispersed. Specifically, the percentage (coefficient of variation) of the value obtained by dividing the standard deviation of the volume load average diameter by the volume load average diameter is 80% or less, more preferably 50% or less, and even more preferably 30% or less.
[0057]
The organic silver salt solid fine particle dispersion used in the present invention comprises at least an organic silver salt and water. The ratio of the organic silver salt to water is not particularly limited, but the ratio of the organic silver salt to the entire organic silver salt is preferably 5 to 50% by mass, and particularly preferably 10 to 30% by mass. It is preferable to use the above-mentioned dispersing aid, but it is preferable to use the minimum amount in a range suitable for minimizing the particle size, and 0.5 to 30% by weight, particularly 1 to 15%, based on the organic silver salt. A range of mass% is preferred.
[0058]
In the present invention, an organic silver salt can be used in a desired amount, but the silver amount is 0.1 to 5 g / m.²Is more preferable, and more preferably 1 to 3 g / m.²It is.
[0059]
In the present invention, it is preferable to add a metal ion selected from Ca, Mg, Zn and Ag to the non-photosensitive organic silver salt. As for the addition of a metal ion selected from Ca, Mg, Zn and Ag to the non-photosensitive organic silver salt, it is preferable to add it in the form of a water-soluble metal salt which is not a halide, and specifically, nitrate or sulfuric acid. It is preferable to add in the form of a salt or the like. Addition with a halide is not preferable because it deteriorates image storability by so-called light (indoor light, sunlight, etc.) of the heat-developable image recording material after processing, particularly the heat-developable image recording material. For this reason, in this invention, it is preferable to add in the form of the water-soluble metal salt which is not a halide.
[0060]
The addition time of the metal ion selected from Ca, Mg, Zn and Ag that is preferably used in the present invention includes, after the formation of the non-photosensitive organic silver salt particles, immediately after the formation of the particles, before the dispersion, after the dispersion, and before and after the preparation of the coating solution. Any timing may be used as long as it is just before coating, and preferably after coating and before and after preparation of the coating solution.
[0061]
In the present invention, the addition amount of a metal ion selected from Ca, Mg, Zn and Ag is 10 per mol of non-photosensitive organic silver.^-3-10^-1mol is preferred, in particular 5 × 10^-3~ 5x10^-2mol is preferred.
[0062]
The photosensitive silver halide used in the present invention is not particularly limited as a halogen composition, and silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodochlorobromide can be used. Grain formation of the photosensitive silver halide emulsion can be carried out by the method described in paragraph Nos. 0217 to 0224 of JP-A No. 11-119374, but is not particularly limited to this method. .
Examples of the shape of the silver halide grains include cubes, octahedrons, tetradecahedrons, tabular shapes, spherical shapes, rod shapes, potato shapes, and the like. In the present invention, cubic grains or tabular grains are particularly preferred. The characteristics of the particle shape such as the aspect ratio and the surface index of the particles are the same as those described in paragraph No. 0225 of JP-A-11-119374. Further, the distribution of the halogen composition may be uniform inside and on the surface of the silver halide grains, the halogen composition may be changed stepwise, or may be continuously changed. Further, silver halide grains having a core / shell structure can be preferably used. As the structure, core / shell particles having a preferably 2- to 5-fold structure, more preferably a 2- to 4-fold structure can be used. A technique of localizing silver bromide on the surface of silver chloride or silver chlorobromide grains can also be preferably used.
[0063]
The grain size distribution of the silver halide grains used in the present invention has a monodispersity value of 30% or less, preferably 1 to 20% or less, and further 5 to 15%. Here, the monodispersity is defined as a percentage (%) (coefficient of variation) of a value obtained by dividing the standard deviation of the particle size by the average particle size. For convenience, the grain size of the silver halide grains is represented by a ridge length in the case of cubic grains, and the other grains (octahedral, tetradecahedral, tabular, etc.) are calculated by a projected area equivalent circle diameter.
[0064]
The photosensitive silver halide grains contain a group VII or group VIII metal or metal complex of the periodic table. As the central metal of the group VII or VIII metal or metal complex of the periodic table, rhodium, rhenium, ruthenium, osnium and iridium are preferable. Particularly preferred metal complexes are (NH₄)₃Rh (H₂O) Cl₅, K₂Ru (NO) Cl₅, K₃IrCl₆, K₄Fe (CN)₆It is. One kind of these metal complexes may be used, or two or more kinds of complexes of the same metal and different metals may be used in combination. The preferred content is 1 x 10 per 1 mol of silver.^-9mol to 1 × 10^-3The range of mol is preferred, 1 × 10^-8mol to 1 × 10^-4A range of mol is more preferable. As a specific metal complex structure, a metal complex having a structure described in JP-A-7-225449 can be used. The types and addition methods of these heavy metals are described in paragraph numbers 0227 to 0240 of JP-A-11-119374.
[0065]
The photosensitive silver halide grains can be desalted by washing with water by a method known in the art such as a noodle method or a flocculation method, but in the present invention, it may or may not be desalted.
The photosensitive silver halide emulsion is preferably chemically sensitized. For chemical sensitization, the method described in paragraph Nos. 0242 to 0250 of JP-A-11-119374 is used.
A thiosulfonic acid compound may be added to the silver halide emulsion by the method shown in EP 293,917.
[0066]
As the gelatin contained in the photosensitive silver halide used in the present invention, low molecular weight gelatin may be used in order to maintain a good dispersion state of the photosensitive silver halide emulsion in the organic silver salt-containing coating solution. preferable. The molecular weight of the low molecular weight gelatin is 500 to 60,000, preferably 1,000 to 40,000. These low molecular weight gelatins may be used at the time of particle formation or dispersion after desalting, but are preferably used at the time of dispersion after desalting. Ordinary gelatin (molecular weight of about 100,000) may be used during grain formation, and low molecular weight gelatin may be used during dispersion after desalting.
[0067]
The concentration of the dispersion medium can be 0.05 to 20% by mass, but a concentration range of 5 to 15% by mass is preferable for handling. As the type of gelatin, alkali-treated gelatin is usually used, but modified gelatin such as acid-treated gelatin and phthalated gelatin can also be used.
[0068]
The silver halide emulsion in the heat-developable image recording material used in the present invention may be only one type, or two or more types (for example, those having different average grain sizes, those having different halogen compositions, those having different crystal habits, Those having different chemical sensitization conditions) may be used in combination.
[0069]
The amount of photosensitive silver halide used is preferably 0.01 mol to 0.5 mol, more preferably 0.02 mol to 0.3 mol, and 0.03 mol to 0.25 mol relative to 1 mol of the organic silver salt. Is particularly preferred. Regarding the mixing method and mixing conditions of the photosensitive silver halide and organic silver salt prepared separately, the silver halide grains and organic silver salt that were prepared separately were mixed with a high-speed stirrer, ball mill, sand mill, colloid mill, vibration mill, homogenizer, respectively. Etc., or a method of preparing an organic silver salt by mixing photosensitive silver halide that has been prepared at any timing during the preparation of the organic silver salt, etc., but the effect of the present invention is sufficient As long as it appears in, there is no particular limitation. Moreover, mixing two or more organic silver salt aqueous dispersions and two or more photosensitive silver salt aqueous dispersions when mixing is a method preferably used for adjusting photographic characteristics.
[0070]
As a sensitizing dye that can be applied to the present invention, it can spectrally sensitize silver halide grains in a desired wavelength region when adsorbed on silver halide grains, and has a spectral sensitivity suitable for the spectral characteristics of the exposure light source. The dye can be advantageously selected. For example, as a dye that spectrally sensitizes a wavelength region of 550 nm to 750 nm, a dye represented by the general formula (II) of JP-A-10-186572 can be mentioned, and specifically, II-6 and II-7. II-14, II-15, II-18, II-23, and II-25. Examples of the dye that spectrally sensitizes the wavelength region of 750 to 1400 nm include dyes represented by the general formula (I) in JP-A No. 11-119374. Specifically, (25) and (26) , (30), (32), (36), (37), (41), (49), (54). Furthermore, as a dye forming J-band, the dye described in Example 5 of US Pat. Nos. 5,510,236 and 3,871,887, JP-A-2-96131, Examples thereof include dyes disclosed in Japanese Utility Model Publication No. 59-48753. These sensitizing dyes may be used alone or in combination of two or more.
[0071]
The addition of these sensitizing dyes can be carried out by the method described in paragraph No. 0106 of JP-A No. 11-119374, but is not particularly limited to this method.
The addition amount of the sensitizing dye in the present invention may be a desired amount according to the sensitivity and fogging performance, but it is 10 per 1 mol of silver halide in the photosensitive layer.^-6~ 1 mol is preferred, more preferably 10^-4-10^-1mol.
[0072]
In the present invention, a supersensitizer can be used to improve spectral sensitization efficiency. Supersensitizers used in the present invention are compounds disclosed in European Patent Nos. 587,338, U.S. Pat. Nos. 3,877,943 and 4,873,184. , Heteroaromatic or aliphatic mercapto compounds, heteroaromatic disulfide compounds, compounds selected from stilbene, hydrazine, and triazine.
Particularly preferred supersensitizers are heteroaromatic mercapto compounds, heteroaromatic disulfide compounds disclosed in JP-A-5-341432, and general formula (I) or (II) in JP-A-4-18239. A stilbene compound represented by general formula (I) of JP-A-10-111543, and a compound represented by general formula (I) of JP-A-11-109547. Specifically, compounds of M-1 to M-24 of JP-A-5-341432, compounds of d-1) to d-14) of JP-A-4-18239, and JP-A-10-111543. Compounds of SS-01 to SS-07, compounds of 31, 32, 37, 38, 41 to 45, 51 to 53 of JP-A-11-109547.
[0073]
The amount of these supersensitizers added is 10 per mol of silver halide in the emulsion layer.^-4The range of ˜1 mol is preferable, and the amount is more preferably 0.001 to 0.3 mol per mol of silver halide.
[0074]
Next, the high contrast agent that can be used in the present invention will be described.
The type of the contrast enhancer used in the present invention is not particularly limited, but as a well known contrast enhancer, a hydrazine derivative represented by the formula (H) described in JP-A No. 2000-284399 (specifically, The hydrazine derivatives listed in Tables 1 to 4 of the publication), JP-A-10-10672, JP-A-10-161270, JP-A-10-62898, JP-A-9-304870, JP-A-9. No. -304872, JP-A-9-304871, JP-A-10-31282, US Pat. No. 5,496,695, European Patent Publication EP741,320A, all hydrazine derivatives are listed. be able to. Further, there are substituted alkene derivatives, substituted isoxazole derivatives and specific acetal compounds represented by the formulas (1) to (3) described in JP-A No. 2000-284399, and further, the formula (A ) Or a cyclic compound represented by formula (B), specifically, compounds 1 to 72 described in Chemical Formulas 8 to 12 of the same publication, general formula (H) described in JP-A-2001-133924, ( Compounds represented by G) and (P), specifically, [Chemical Formula 3] to [Chemical Formula 9] and [Chemical Formula 11] to [Chemical Formula 53] of the same publication can be mentioned. A plurality of these high contrast agents may be used in combination.
[0075]
The high contrast agent particularly preferably used in the present invention is represented by the general formulas (H-1), (H-2), (H-3), (H-4), (H -5), hydrazine derivatives represented by (H-1-1) (specifically, compounds H-1-1 to H-1-28 and compounds H-2-1 to H-2 described in the publication) -9, compounds H-3-1 to H-3-12, compounds H-4-1 to H-4-21, compounds H-5-1 to H-5-5), JP-A-2001-125224 The substituted alkene derivatives represented by the general formula (1) described in (specifically, [Chemical Formula 10] to [Chemical Formula 55] described in the same publication).
[0076]
The thickening agent is water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide. It can be used by dissolving in methyl cellosolve.
In addition, by using a well-known emulsification dispersion method, it is dissolved using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone. Then, an emulsified dispersion can be mechanically prepared and used. Alternatively, it is possible to use a thickener powder dispersed in a suitable solvent such as water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.
[0077]
The thickening agent may be added to any layer on the image forming layer side with respect to the support, but is preferably added to the image forming layer or a layer adjacent thereto. The addition amount varies depending on the grain size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of inhibitor, etc., and is not uniform.^-6~ 1 mol, especially 10^-5-10^-1A range of mol is preferred.
[0078]
In the present invention, in order to form a super high contrast image, a high contrast accelerator can be used in combination with the above high contrast agent. For example, amine compounds described in US Pat. No. 5,545,505, specifically AM-1 to AM-5, hydroxamic acids described in US Pat. No. 5,545,507, specific examples HA-1 to HA-11, acrylonitriles described in US Pat. No. 5,545,507, specifically CN-1 to CN-13, US Pat. No. 5,558,983 Hydrazine compounds, specifically CA-1 to CA-6, Onum salts described in JP-A-9-297368, specifically A-1 to A-42, B-1 to B -27, C-1 to C-14, and the like can be used.
[0079]
In the heat-developable image recording material having a non-photosensitive silver salt, a photosensitive silver halide and a binder, formic acid or formate is a strong fogging substance. In the present invention, the content of formic acid or formate on the side having the image forming layer containing the photosensitive silver halide of the heat-developable image recording material is preferably 5 mmol or less, more preferably 1 mmol or less per 1 mol of silver.
[0080]
In the heat-developable image recording material, it is preferable to use an acid formed by hydration of diphosphorus pentoxide or a salt thereof in combination with a high contrast agent. Acids or salts thereof formed by hydration of diphosphorus pentoxide include metaphosphoric acid (salt), pyrophosphoric acid (salt), orthophosphoric acid (salt), triphosphoric acid (salt), tetraphosphoric acid (salt), hexametalin Acid (salt) and the like. The acid or salt thereof formed by hydrating diphosphorus pentoxide particularly preferably used is orthophosphoric acid (salt), hexametaphosphoric acid (salt), and specific salts include sodium orthophosphate, sodium dihydrogen orthophosphate, Examples include sodium hexametaphosphate and ammonium hexametaphosphate.
The acid or salt thereof formed by hydrating diphosphorus pentoxide, which can be preferably used in the present invention, is added to the image forming layer or a binder layer adjacent thereto from the viewpoint that a desired effect is exhibited in a small amount.
Amount of acid or salt thereof formed by hydration of diphosphorus pentoxide (1 m of heat-developable image recording material²The coating amount per unit) may be a desired amount according to the performance such as sensitivity and fog, but is 0.1 to 500 mg / m.²Is preferably 0.5 to 100 mg / m²Is more preferable.
[0081]
The heat-developable image recording material preferably contains a reducing agent for the organic silver salt. The reducing agent for the organic silver salt is any substance, preferably an organic substance, that reduces silver ions to metallic silver. Conventional photographic developers such as phenidone, hydroquinone and catechol are useful, but hindered phenol reducing agents are preferred. The reducing agent is preferably contained in an amount of 0.1 to 50 mol, more preferably 0.2 to 40 mol, relative to 1 mol of silver on the surface having the image forming layer. The addition layer of the reducing agent may be any layer on the side having the image forming layer. When adding to layers other than an image forming layer, it is preferable to use 0.5-50 mol with respect to 1 mol of silver. The reducing agent may be a so-called precursor that is derivatized so as to have an effective function only during development.
[0082]
In a heat-developable image recording material using an organic silver salt, a wide range of reducing agents are disclosed in JP-A Nos. 46-6074, 47-1238, 47-33621, 49-46427, 49. No. 115540, No. 50-14334, No. 50-36110, No. 50-147711, No. 51-32632, No. 51-32324, No. 51-51933, No. 52-. 84727, 55-108654, 56-146133, 57-82828, 57-82829, JP-A-6-3793, US Pat. No. 3,679,426 No. 3,751,252, No. 3,751,255, No. 3,761,270, No. 3,782,94 No. 3,839,048, No. 3,928,686, No. 5,464,738, German Patent No. 2,321,328, It is disclosed in European Patent No. 692,732. For example, amide oximes such as phenylamidooxime, 2-thienylamidooxime and p-phenoxyphenylamidooxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehyde azine; 2,2′-bis (hydroxymethyl) propionyl A combination of an aliphatic carboxylic acid aryl hydrazide and ascorbic acid, such as a combination of β-phenylhydrazine and ascorbic acid; a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine (eg hydroquinone and bis (ethoxy Ethyl) hydroxylamine, piperidinohexose reductone or a combination of formyl-4-methylphenylhydrazine); phenylhydroxamic acid, p-hydroxyphenylhydroxa Acids and hydroxamic acids such as β-arinin hydroxamic acid; combinations of azine and sulfonamidophenol (eg, phenothiazine and 2,6-dichloro-4-benzenesulfonamidophenol); ethyl-α-cyano-2-methyl Α-cyanophenylacetic acid derivatives such as phenylacetate and ethyl-α-cyanophenylacetate; 2,2′-dihydroxy-1,1′-binaphthyl, 6,6′-dibromo-2,2′-dihydroxy-1,1 Bis-β-naphthol as exemplified by '-binaphthyl and bis (2-hydroxy-1-naphthyl) methane; bis-β-naphthol and 1,3-dihydroxybenzene derivatives (eg, 2,4-dihydroxybenzophenone or 2 ′, 4′-dihydroxyacetophenone, etc.) combinations; 3- 5-pyrazolones, such as methyl-1-phenyl-5-pyrazolone; reductones as exemplified by dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone; 2 Sulfonamide phenol reducing agents such as 1,6-dichloro-4-benzenesulfonamidophenol and p-benzenesulfonamidophenol; 2-phenylindane-1,3-dione and the like; 2,2-dimethyl-7-tert-butyl- Chroman such as 6-hydroxychroman; 1,4-dihydropyridine such as 2,6-dimethoxy-3,5-dicarboethoxy-1,4-dihydropyridine; bisphenol (eg, bis (2-hydroxy-3-tert-butyl) -5-methylphenyl Methane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4-ethylidene-bis (2-tert-butyl-6-methylphenol), 1,1, -bis (2-hydroxy-) 3,5-dimethylphenyl) -3,5,5-trimethylhexane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane); ascorbic acid derivatives (eg 1-ascorbyl palmitate, Ascorbyl stearate); and aldehydes and ketones such as benzyl and biacetyl; 3-pyrazolidone and certain indan-1,3-diones; chromanol (such as tocopherol). Particularly preferred reducing agents are bisphenol and chromanol.
[0083]
When a reducing agent is used in the present invention, it may be added by any method such as an aqueous solution, an organic solvent solution, a powder, a solid fine particle dispersion, and an emulsified dispersion. The solid fine particle dispersion is performed by a known finer means (for example, ball mill, vibration ball mill, sand mill, colloid mill, jet mill, roller mill, etc.). A dispersion aid may be used when dispersing the solid fine particles.
[0084]
In the present invention, a phenol derivative represented by the formula (A) described in JP-A No. 2000-267222 is preferably used as a development accelerator. The phenol derivative represented by the formula (A) exhibits a strong development accelerating effect when used in combination with the reducing agent. Specifically, A-1 to A-54 described in the publication are preferably used. The phenol derivative represented by the formula (A) is preferably used in the range of 0.01 to 100 mol, more preferably in the range of 0.1 to 20 mol, with respect to 1 mol of the reducing agent.
[0085]
The phenol derivative represented by the formula (A) may be added to the layer on the image forming layer side with respect to the support, that is, the image forming layer or any other layer on this layer side. It is preferable to add to. The phenol derivative represented by the formula (A) may be added by any method such as an aqueous solution, an organic solvent solution, a powder, a solid fine particle dispersion, and an emulsified dispersion. The solid fine particle dispersion is performed by a known finer means (for example, ball mill, vibration ball mill, sand mill, colloid mill, jet mill, roller mill, etc.). A dispersion aid may be used when dispersing the solid fine particles.
[0086]
Inclusion of an additive known as a “toning agent” that improves the image may increase the optical density. The toning agent may also be advantageous in forming a black silver image. The color tone agent is preferably contained in an amount of 0.1 to 50 mol per mol of silver on the side having the image forming layer, and more preferably 0.5 to 20 mol. The toning agent may be a so-called precursor that is derivatized so as to have an effective function only during development.
In a heat-developable image recording material using an organic silver salt, a wide range of color toning agents are disclosed in JP-A-46-6077, 47-10282, 49-5019, 49-5020, 49. -91215, 49-91215, 50-2524, 50-32927, 50-67132, 50-66761, 50-114217, 51- No. 3223, No. 51-27923, No. 52-14788, No. 52-99813, No. 53-1020, No. 53-76020, No. 54-156524, No. 54-156525. No. 61-183642, JP-A-4-56848, JP-B 49-10727, 54-20333, Japanese Patent Nos. 3,080,254, 3,446,648, 3,782,941, 4,123,282, 4,510 No. 236, British Patent No. 1,380,795, Belgian Patent No. 841,910, and the like. Examples of toning agents are phthalimide and N-hydroxyphthalimide; succinimide, pyrazolin-5-one, and quinazolinone, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione Cyclic imides such as: naphthalimide (eg, N-hydroxy-1,8-naphthalimide); cobalt complex (eg, cobalt hexamine trifluoroacetate); 3-mercapto-1,2,4-triazole, 2,4 -Mercaptans exemplified by dimercaptopyrimidine, 3-mercapto-4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; N- (aminomethyl) aryldi Carboximide, (for example, (N, N-dimethyl) Aminomethyl) phthalimide and N, N- (dimethylaminomethyl) -naphthalene-2,3-dicarboximide); and blocked pyrazoles, isothiuronium derivatives and certain photobleaching agents (eg, N, N′-hexamethylene) Bis (1-carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6-diazaoctane) bis (isothiuronium trifluoroacetate) and 2-tribromomethylsulfonyl)-(benzothiazole)); 3-ethyl-5-[(3-ethyl-2-benzothiazolinylidene) -1-methylethylidene] -2-thio-2,4-oxazolidinedione; phthalazinone, phthalazinone derivatives or metal salts, or 4- ( 1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5, Derivatives such as dimethoxyphthalazinone and 2,3-dihydro-1,4-phthalazinedione; phthalazinone and phthalic acid derivatives (eg phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride) Phthalazine, phthalazine derivatives (for example, 4- (1-naphthyl) phthalazine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine, 6-isobutylphthalazine, 6-tert-butylphthalazine, 5, 7-dimethylphthalazine and derivatives such as 2,3-dihydrophthalazine) or metal salts; phthalazine and its derivatives and phthalic acid derivatives (eg, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachloroanhydride) Combination with phthalic acid, etc .; quinazolinedione, benzo Xazine or naphthoxazine derivatives; rhodium complexes that function not only as color modifiers but also as a source of halide ions for in situ silver halide formation, such as ammonium hexachlororhodium (III), rhodium bromide, rhodium nitrate and Potassium hexachlororhodium (III) and the like; inorganic peroxides and persulfates, such as ammonium disulfide and hydrogen peroxide; 1,3-benzoxazine-2,4-dione, 8-methyl-1,3 Benzoxazine-2,4-diones such as benzoxazine-2,4-dione and 6-nitro-1,3-benzoxazine-2,4-dione; pyrimidines and asymmetric-triazines (for example 2,4- Dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine, etc.), aza Lasil and tetraazapentalene derivatives (eg, 3,6-dimercapto-1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene, and 1,4-di (o-chlorophenyl) ) -3,6-dimercapto-1H, 4H-2,3a, 5,6a-tetraazapentalene).
[0087]
In the present invention, a phthalazine derivative represented by the general formula (F) described in JP-A No. 2000-35631 is preferably used as a color tone agent. Specifically, A-1 to A-10 described in the publication are preferably used.
[0088]
When using the toning agent in the present invention, it may be added by any method such as solution, powder, solid fine particle dispersion and the like. The solid fine particle dispersion is performed by a known finer means (for example, ball mill, vibration ball mill, sand mill, colloid mill, jet mill, roller mill, etc.). A dispersion aid may be used when dispersing the solid fine particles.
[0089]
The film surface pH of the heat-developable image recording material before heat development is preferably 6.0 or less, and more preferably 5.5 or less. The lower limit is not particularly limited, but is about 3.
The film surface pH is preferably adjusted using an organic acid such as a phthalic acid derivative, a non-volatile acid such as sulfuric acid, or a volatile base such as ammonia from the viewpoint of reducing the film surface pH. In particular, ammonia is volatile and is preferable for achieving a low film surface pH because it can be removed before the coating process or heat development. A method for measuring the film surface pH is described in paragraph No. 0123 of JP-A No. 2000-284399.
[0090]
In heat-developable image recording materials, silver halide emulsions and / or organic silver salts are further protected against the formation of additional fog by antifoggants, stabilizers and stabilizer precursors, and sensitivity during inventory storage. It is possible to stabilize against a decrease in. Suitable antifoggants, stabilizers and stabilizer precursors that can be used alone or in combination are the thiazonium described in US Pat. Nos. 2,131,038 and 2,694,716. Salt, azaindene described in U.S. Pat. Nos. 2,886,437 and 2,444,605, mercury salt described in U.S. Pat. No. 2,728,663, U.S. Pat. , 287,135, sulfocatechol described in US Pat. No. 3,235,652, oxime described in British Patent 623,448, nitrone, nitroindazole, US patent No. 2,839,405, polyvalent metal salts, U.S. Pat. No. 3,220,839, thulonium salts, and U.S. Pat. No. 2,5. Palladium, platinum and gold salts described in US Pat. Nos. 6,263 and 2,597,915, US Pat. Nos. 4,108,665 and 4,442,202 Halogen-substituted organic compounds described, U.S. Pat. Nos. 4,128,557 and 4,137,079, 4,138,365 and 4,459,350. And the phosphorus compounds described in US Pat. No. 4,411,985.
[0091]
The heat-developable image recording material may contain benzoic acids for the purpose of increasing sensitivity and preventing fogging. The benzoic acid used in the present invention may be any benzoic acid derivative. Examples of preferred structures include U.S. Pat. Nos. 4,784,939 and 4,152,160, and JP-A-9-329863. And the compounds described in JP-A-9-329864, JP-A-9-281638, and the like.
Benzoic acids may be added to any layer of the heat-developable image recording material, but are preferably added to the layer having the image forming layer, and more preferably to the organic silver salt-containing layer. The benzoic acid may be added at any step in the coating solution preparation, and when added to the organic silver salt-containing layer, any step from the preparation of the organic silver salt to the preparation of the coating solution may be performed. To immediately before coating. The benzoic acid may be added by any method such as powder, solution, fine particle dispersion and the like. Moreover, you may add as a solution mixed with other additives, such as a sensitizing dye, a reducing agent, and a color toning agent. The amount of benzoic acid added may be any amount, but is 1 × 10 5 per mol of silver.^-6mol to 2 mol are preferred, 1 × 10^-3More preferably, mol to 0.5 mol.
[0092]
Although not essential for practicing the present invention, it may be advantageous to add a mercury (II) salt as an antifoggant to the image forming layer. Preferred mercury (II) salts for this purpose are mercury acetate and mercury bromide. The amount of mercury used in the present invention is preferably 1 × 10 per 1 mol of applied silver.^-9mol ~ 1 × 10^-3mol, more preferably 1 × 10^-8mol ~ 1 × 10^-4The range is mol.
[0093]
The antifoggant particularly preferably used in the present invention is an organic halide, for example, U.S. Pat. Nos. 3,874,946, 4,756,999, 5,340,712. No. 5,369,000, No. 5,464,737, JP-A-50-120328, JP-A-50-137126, 50-89020, JP-A-50-119624, JP-A-59-57234, JP-A-7-2781, JP-A-7-5621, JP-A-9-160164, JP-A-9-160167, JP-A-10-197988, 9-244177, 9-244178, 9-160167, 9-319022, 9-258367, 9-265150 9-319022, 10-197989, 11-242304, JP-A 2000-2963, JP-A 2000-112070, JP-A 2000-284212, JP-A 2000-. Examples thereof include compounds described in 284399, JP-A 2000-284410, JP-A 2001-33911, JP-A 2001-5144, and the like. Among these, particularly preferred organic halides are 2-tribromomethylsulfonylquinoline described in JP-A-7-2781, 2-tribromomethylsulfonylpyridine described in JP-A-2001-5144, Compounds P-1 to P-31 described in JP 2000-112070 A, compounds P-1 to P-73 described in JP 2000-284410 A, P- 1 to P-25, P′-1 to P′-27, P-1 to P-118 described in JP-A No. 2000-284399, phenyltribromomethylsulfone, 2-naphthyltribromomethyl Sulfone.
The addition amount of the organic halide is expressed as a mol amount (mol / mol Ag) relative to 1 mol of Ag, preferably 1 × 10.^-5˜2 mol / mol Ag, more preferably 5 × 10^-5˜1 mol / mol Ag, more preferably 1 × 10^-4~ 5x10^-1mol / mol Ag. These may use only 1 type or may use 2 or more types together.
[0094]
A salicylic acid derivative represented by the formula (Z) described in JP-A No. 2000-284399 is preferably used as an antifoggant. Specifically, (A-1) to (A-60) described in the publication are preferably used. The addition amount of the salicylic acid derivative represented by the formula (Z) is expressed as a mol amount (mol / mol Ag) relative to 1 mol of Ag, and preferably 1 × 10.^-5~ 5x10^-1mol / mol Ag, more preferably 5 × 10^-5~ 1x10^-1mol / mol Ag, more preferably 1 × 10^-4~ 5x10^-2mol / mol Ag. These may use only 1 type or may use 2 or more types together.
[0095]
As an antifoggant preferably used in the present invention, a formalin scavenger is effective. For example, a compound represented by the formula (S) described in JP-A No. 2000-221634 and exemplified compounds (S-1) to ( S-24).
[0096]
The antifoggant used in the present invention is water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc. It can be dissolved in
In addition, using a well-known emulsification dispersion method, it is dissolved using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be made and used. Alternatively, the powder can be dispersed and used in water by a ball mill, a colloid mill, a sand grinder mill, a manton gourin, a microfluidizer or ultrasonic waves by a method known as a solid dispersion method.
[0097]
The antifoggant used in the present invention may be added to the layer on the image forming layer side with respect to the support, that is, the image forming layer or any other layer on this layer side. It is preferable to add to the layer. The image forming layer is a layer containing a reducible silver salt (organic silver salt), preferably an image forming layer further containing a photosensitive silver halide.
[0098]
The heat-developable image recording material may contain a mercapto compound, a disulfide compound, or a thione compound in order to suppress or promote development to control development and to improve storage stability before and after development.
When a mercapto compound is used in the present invention, it may have any structure, but those represented by Ar-SM and Ar-SS-Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotelrazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine , Pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring can be, for example, halogen (eg, Br and Cl), hydroxy, amino, carboxy, alkyl (eg, having one or more carbon atoms, preferably 1 to 4 carbon atoms), alkoxy ( For example, those having one or more carbon atoms, preferably those having 1 to 4 carbon atoms) and those selected from the substituent group consisting of aryl (which may have a substituent) Good. Examples of mercapto-substituted heteroaromatic compounds include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, 6-ethoxy-2-mercaptobenzothiazole, 2, 2′-dithiobis- (benzothiazole), 3-mercapto-1,2,4-triazole, 4,5-diphenyl-2-imidazolethiol, 2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2- Mercaptoquinoline, 8-mercaptopurine, 2-mercapto-4 (3H) -quinazolinone, 7-trifluoromethyl-4-quinolinethiol, 2,3,5,6-tetrachloro-4-pyridinethiol, 4-amino- 6-hydroxy-2-mercap Pyrimidine monohydrate, 2-amino-5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto-1,2,4-triazole, 4-hydroxy-2-mercaptopyrimidine, 2-mercaptopyrimidine 4,6-diamino-2-mercaptopyrimidine, 2-mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole, 1-phenyl-5-mercaptotetrazole, 3- Examples include (5-mercaptotetrazole) -sodium benzenesulfonate, N-methyl-N ′-{3- (5-mercaptotetrazolyl) phenyl} urea, 2-mercapto-4-phenyloxazole, and the like. Is not limited to these.
The addition amount of these mercapto compounds is preferably in the range of 0.0001 to 1.0 mol per mol of silver in the image forming layer, and more preferably 0.001 to 0.3 mol per mol of silver.
[0099]
The image forming layer is preferably prepared by applying an aqueous coating solution and then drying it. However, “aqueous” as used herein means that 60% by mass or more of the solvent (dispersion medium) of the coating solution is water.
[0100]
Various supports can be used for the heat-developable image recording material. Typical supports include polyesters such as polyethylene terephthalate, polyethylene naphthalate, cellulose nitrate, cellulose esters, polyvinyl acetal, syndiotactic polystyrene, polycarbonate, paper supports coated on both sides with polyethylene, and the like. Of these, biaxially stretched polyester, particularly polyethylene terephthalate (PET), is preferable from the viewpoint of strength, dimensional stability, chemical resistance, and the like. The thickness of the support is preferably 50 to 200 μm as the base thickness excluding the undercoat layer.
The support used for the heat-developable image recording material is disclosed in JP-A-10-48772, JP-A-10-10676, JP-A-10-10777, JP-A-11-65025, and JP-A-11-138648. Polyester, especially polyethylene terephthalate, which has been heat-treated in a temperature range of 130 to 185 ° C. in order to alleviate internal strain remaining in the film during biaxial stretching and to eliminate thermal shrinkage strain generated during heat development processing Is preferably used.
[0101]
The dimensional change rate of the support after such heat treatment at 120 ° C. for 30 seconds is −0.03% to + 0.01% in the machine direction (MD) and 0 to 0.04% in the transverse direction (TD). Preferably there is.
[0102]
On both sides of the support, JP-A 64-20544, JP-A-1-180537, JP-A-1-209443, JP-A-1-285939, JP-A-1-296243, JP-A-1 JP-A-2-24649, JP-A-2-24648, JP-A-2-184844, JP-A-3-109545, JP-A-3-137737, JP-A-3-141346, and JP-A-3- No. 141347, JP-A-4-96055, US Pat. No. 4,645,731, JP-A-4-68344, Registration No. 2,557,641 P2 right column, line 20 to P3 right Column 30, PVC numbers described in JP-A No. 2000-39684, paragraph numbers 0020 to 0037, and Japanese Patent Application No. 2000-47083, paragraph numbers 0063 to 0080. It is preferable to provide a layer containing a dibenzylidene monomer vinylidene chloride copolymer repeating units containing at least 70 wt% of.
[0103]
When the vinylidene chloride monomer is less than 70% by mass, sufficient moisture resistance cannot be obtained, and the dimensional change over time after heat development becomes large. Moreover, it is preferable that a vinylidene chloride copolymer contains the repeating unit of a carboxyl group-containing vinylene monomer as another structural repeating unit of a vinylidene chloride monomer. Such a constitutional repeating unit is contained only with a vinylidene chloride monomer, the polymer (polymer) is crystallized, and it becomes difficult to form a uniform film when a moisture-proof layer is applied. This is because a carboxyl group-containing vinylene monomer is indispensable for stabilizing the (polymer).
The molecular weight of the vinylidene chloride copolymer is preferably 45,000 or less, more preferably 10,000 to 45,000 in terms of weight average molecular weight. When the molecular weight increases, the adhesion between the vinylidene chloride copolymer layer and the support layer such as polyester deteriorates.
[0104]
The content of the vinylidene chloride copolymer is 0.3 μm or more, preferably in the range of 0.3 μm to 4 μm, as the total film thickness per one side of the layer containing the vinylidene chloride copolymer.
[0105]
The vinylidene chloride copolymer layer can also be provided on the undercoat layer as the first undercoat layer or the undercoat layer directly provided on the support. Usually, one layer is provided for each side, but two or more layers may be provided in some cases. When a multilayer structure having two or more layers is used, the total amount of the vinylidene chloride copolymer may be within the above range.
In addition to the vinylidene chloride copolymer, such a layer may contain a crosslinking agent, a matting agent, and the like.
[0106]
In addition to the vinylidene chloride copolymer layer, the support may be coated with an undercoat layer containing SBR, polyester, gelatin or the like as a binder. These undercoat layers may have a multilayer structure, and may be provided on one side or both sides with respect to the support. The general thickness (per layer) of the undercoat layer is 0.01 to 5 μm, more preferably 0.05 to 1 μm.
[0107]
In the heat-developable image recording material, the conductive properties described in paragraph Nos. 0040 to 0051 of JP-A No. 11-84573 are used for the purpose of reducing the adhesion of dust, preventing the generation of static marks, and preventing the conveyance failure in the automatic conveyance process. Antistatic treatment can be performed using a metal oxide and / or a fluorosurfactant. Examples of the conductive metal oxide include acicular conductive tin oxide doped with antimony described in US Pat. No. 5,575,957, paragraphs 0012 to 0020 of JP-A-11-223901, Fibrous tin oxide doped with antimony described in JP-A-4-29134 is preferably used.
[0108]
The heat-developable image recording material has a surface resistivity of 1 × 10 in an environment of 25 ° C. and a relative humidity of 25% for the purpose of reducing dust adhesion, preventing static mark generation, and preventing conveyance failure in the automatic conveyance process.¹²Ω or less, preferably 10¹¹Less than Ω is good. Thereby, good antistatic properties can be obtained. The lower limit of the surface resistivity at this time is not particularly limited, but is usually 10⁷It is about Ω.
The conductive layer may be formed on one side of the support, or may be formed on both sides. When formed on one side, it is preferably formed on the back surface. Two or more conductive layers may be formed on one side.
[0109]
Examples of the conductive substance include conductive metal oxides described in paragraph Nos. 0040 to 0051 of JP-A No. 11-84573, US Pat. No. 5,575,957, and paragraph Nos. Of JP-A No. 11-223901. The needle-shaped conductive tin oxide doped with antimony described in 0012 to 0020 and the fibrous tin oxide doped with antimony described in JP-A-4-29134 are preferably used. Examples of the conductive polymer include an anionic polymer or latex described in JP-B-52-25251, JP-A-51-29923, JP-B-60-48024, JP-B-57-18176, and 57-. Examples thereof include cationic polymers or latexes described in JP-A Nos. 56059 and 58-56856, and US Pat. No. 4,118,231.
[0110]
Specific examples of the conductive polymer include the following, but the conductive polymer that can be used in the present invention is not limited to the following specific examples.
[0111]
[Chemical 1]

[0112]
[Chemical 2]

[0113]
[Chemical 3]

[0114]
[Formula 4]

[0115]
These conductive polymers can be used alone, but are preferably applied in combination with other binders. Furthermore, a curing agent can be used in combination with these binders.
The content of the conductive polymer in the heat-developable image recording material is preferably 0.005 to 5 g / m.²More preferably, 0.01-3 g / m²More preferably, 0.02 to 1 g / m²It is.
When the binder is used in combination, the weight ratio of the conductive polymer to the binder is preferably 99: 1 to 10:90, more preferably 80:20 to 20:80, and particularly preferably 70:30 to 30:70.
[0116]
The conductive polymer layer of the heat-developable image recording material preferably contains a hardener.
Examples of such hardeners include aldehyde compounds such as formaldehyde and glutaraldehyde, U.S. Pat. Nos. 2,732,303, 3,288,775, British Patent 974,723, No. 1,167,207 and the like, compounds having reactive halogen, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethyl) urea, 2-hydroxy-4,6-dichloro- 1,3,5-triazine, divinylsulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, U.S. Pat. Nos. 3,232,763 and 3,635,718 Specification, compounds having reactive olefins described in British Patent 994,809, etc., US Pat. No. 3,539,644 No. 3,642,486, JP-B-49-13568, 53-47271, 56-48860, JP-A-53-57257, 61-128240, No. 62-4275, No. 63-53541, No. 63-264572, etc., vinyl sulfone compounds, N-hydroxymethylphthalimide, US Pat. No. 2,732,316, No. 2,586, 168, etc., N-methylol compounds described in US Pat. No. 3,103,437, etc., isocyanate compounds described in US Pat. No. 3,983,611, US Pat. No. 3,107,280, etc. Aziridine compounds described in U.S. Pat. No. 2,725,294, acid derivatives described in U.S. Pat. No. 2,725,295, etc. Carbodiimide compounds described in US Pat. No. 3,100,704, epoxy compounds described in US Pat. No. 3,091,537, US Pat. Nos. 3,321,313, and 3,543,292. Isoxazole compounds, halogenocarboxaldehydes such as mucochloro acid, organic hardeners such as dioxane derivatives such as dihydroxydioxane and dichlorodioxane, and inorganic hardeners such as chromium alum, zirconium sulfate and chromium trichloride It is an agent. Further, as a hardening agent having a relatively fast hardening action with respect to gelatin, compounds having a dihydroquinoline skeleton described in JP-A No. 50-38540, JP-A Nos. 51-59625 and 62- N-carbamoylpyridinium salts described in JP-A-262854, JP-A-62-264044, and JP-A-63-184741, acylimidazoles described in JP-B-55-38655, and JP-A-53-22089 N-acyloxyimidazoles, compounds having two or more N-acyloxyimino groups in the molecule described in JP-B-53-22089, and N-sulfonyloxyimide groups described in JP-A-52-93470 Compounds, compounds having a phosphorus-halogen bond described in JP-A-58-113929, JP-A-6-6 -225148, JP same 61-240236, JP-can be mentioned chloroform amidinium compounds described in JP same 63-41580.
These addition amounts are preferably 0.001-1 in terms of mass ratio with respect to the binder.
[0117]
The surfactant used in the present invention is described below. Surfactants are classified into dispersants, coating agents, wetting agents, antistatic agents, photographic control agents, etc., depending on the purpose of use, but these purposes can be achieved by appropriately using the surfactants described below. it can. As the surfactant used in the present invention, either nonionic or ionic (anion, cation, betaine) can be used. Further, a fluorosurfactant is also preferably used.
[0118]
Preferred nonionic surfactants are surfactants having nonionic hydrophilic groups such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyglycidyl and sorbitan, specifically, polyoxyethylene alkyl ethers, Polyoxyethylene alkyl phenyl ether, polyoxyethylene-polyoxypropylene glycol, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, fatty acid diethanolamide, triethanol Mention may be made of amine fatty acid partial esters.
[0119]
Examples of the anionic surfactant include carboxylate, sulfate, sulfonate, and phosphate ester salt. Representative examples include fatty acid salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfonates, α-olefin sulfonate, dialkyl sulfosuccinate, α-sulfonated fatty acid salt, N-methyl-N oleyl taurine, petroleum sulfonate, alkyl sulfate, sulfated oil, polyoxyethylene alkyl ether sulfate, polyoxyethylene Alkyl phenyl ether sulfate, polyoxyethylene styrenated phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, naphthalene sulfonate formaldehyde condensate, and the like.
[0120]
Examples of the cationic surfactant include amine salts, quaternary ammonium salts, pyridium salts, etc., and primary to tertiary fatty amine salts, quaternary ammonium salts (tetraalkyl ammonium salts, trialkylbenzyl ammonium salts, Alkyl pyridium salt, alkyl imidazolium salt, etc.).
[0121]
Examples of betaine surfactants include carboxybetaine and sulfobetaine, and examples include N-trialkyl-N-carboxymethylammonium betaine and N-trialkyl-N-sulfoalkyleneammonium betaine.
[0122]
These surfactants are described in “Application of Surfactant (Shoshobo, Takao Karie, Issued on September 1, 1980)”. In the present invention, the preferred surfactant is not particularly limited in the amount used, and may be any amount that provides the desired surface active characteristics. The coating amount of the fluorine-containing surfactant is 1 m²250 mg to 0.01 mg per unit is preferable.
[0123]
Although the specific example of surfactant is described below, it is not limited to this (Here, -C₆H₄-Represents a phenylene group.
WA-1: C₁₆H₃₃(OCH₂CH₂)₁₀OH
WA-2: C₉H₁₉-C₆H₄-(OCH₂CH₂)₁₂OH
WA-3: Sodium dodecylbenzenesulfonate
WA-4: Sodium tri (isopropyl) naphthalenesulfonate
WA-5: Sodium tri (isobutyl) naphthalenesulfonate
WA-6: Sodium dodecyl sulfate
WA-7: α-Sulfasuccinic acid di (2-ethylhexyl) ester sodium salt
WA-8: C₈H₁₇-C₆H₄-(CH₂CH₂O)₃(CH₂)₂SO₃K
WA-10: Cetyltrimethylammonium chloride
WA-11: C₁₁H₂₃CONHCH₂CH₂N⁽⁺⁾(CH₃)₂-CH₂COO^(-)
WA-12: C₈F₁₇SO₂N (C₃H₇) (CH₂CH₂O)₁₆H
WA-13: C₈F₁₇SO₂N (C₃H₇) CH₂COOK
WA-14: C₈F₁₇SO₃K
WA-15: C₈F₁₇SO₂N (C₃H₇) (CH₂CH₂O)₄(CH₂)₄SO₃Na
WA-16: C₈F₁₇SO₂N (C₃H₇) (CH₂)₃OCH₂CH₂N⁽⁺⁾(CH₃)₃-CH₃・ C₆H₄-SO₃ ^(-)
WA-17: C₈F₁₇SO₂N (C₃H₇) CH₂CH₂CH₂N⁽⁺⁾(CH₃)
WA-18: C₈F₁₇CH₂CH₂SCH₂CH₂CH₂COOLi
WA-19: (C₄F₉) COOCH₂CH (SO₃Na) COOCH₂CH₂(C₄F₉)
WA-20: C₈H₁₇COOCH₂CH (SO₃Na) COOCH₂CH₂(C₄F₉)
[0124]
In the present invention, the image forming layer, the protective layer of the image forming layer, the undercoat layer, and the back layer have paragraph numbers 0204 to 0208 of JP-A No. 11-84573, and paragraph numbers of 0240 to 0240 of the specification of Japanese Patent Application No. 2000-47083. A dye may be contained for the purpose of preventing halation as described in Japanese Patent Application Publication No. 0241, JP-A-8-278595, JP-A-7-102179, and JP-A-9-509503.
[0125]
Various dyes and pigments can be used for the image forming layer from the viewpoint of improving the color tone and preventing irradiation. Any dye and pigment may be used for the image forming layer. For example, compounds described in paragraph No. 0297 of JP-A No. 11-119374 can be used. As a method for adding these dyes, any method such as a solution, an emulsion, a solid fine particle dispersion, or a state mordanted in a polymer mordant may be used. The amount of these compounds to be used is determined by the target absorption, but generally 1 m²1 × 10 per^-6It is preferable to use in the range of g to 1 g.
[0126]
When the antihalation dye is used in the present invention, the dye has a desired absorption in a desired range, and has a sufficiently small absorption in the visible region after the treatment, so that any desired absorbance spectrum shape of the back layer can be obtained. It may be a compound. For example, compounds described in paragraph No. 0300 of JP-A-11-119374 can be used. Further, as described in Belgian Patent No. 733,706, a method of reducing the concentration by dye by decoloring by heating, the concentration is decreased by decoloring by light irradiation described in JP-A No. 54-17833. Or the like can be used.
[0127]
Conventionally used photographic emulsion coating solution, which is a viscous liquid containing silver halide and containing gelatin as a base, usually dissolves and disappears in the liquid just by feeding under pressure. Even if it is returned to, bubbles are hardly deposited. However, in the case of an image-forming layer coating liquid containing an organic silver salt dispersion and polymer latex preferably used in the present invention, degassing tends to be insufficient only by pressurized liquid feeding, so that a gas-liquid interface does not occur. It is preferable to defoam by applying ultrasonic vibration while feeding.
[0128]
In the present invention, the defoaming of the coating solution is degassed under reduced pressure before the coating solution is applied, and further 1.5 kg / cm²A method in which ultrasonic vibration is applied while the liquid is continuously fed while maintaining the above-described pressurized state and without causing a gas-liquid interface is preferable. Specifically, the system described in JP-B-55-6405 (page 4, line 20 to page 7, line 11) is preferable. As an apparatus for performing such defoaming, an apparatus having the structure shown in FIG. 3 in Example of Japanese Patent Laid-Open No. 2000-98534 can be preferably used.
[0129]
1.5kg / cm as pressure condition²Or more, preferably 1.8 kg / cm²That's it. The upper limit is not particularly limited, but usually 5 kg / cm²Degree. The sound pressure of the applied ultrasonic wave is 0.2 V or more, preferably 0.5 V to 3.0 V. Generally, it is preferable that the sound pressure is high. It becomes a state and causes fogging. The frequency is not particularly limited, but is usually 10 kHz or higher, preferably 20 kHz to 200 kHz. Note that vacuum degassing means that the inside of the tank (usually a liquid preparation tank or storage tank) is hermetically depressurized, the bubble diameter in the coating liquid is increased, the buoyancy is increased, and degassing is performed. The pressure reducing condition is -200 mmHg or lower pressure condition, preferably -250 mmHg or lower pressure condition, and the lowest pressure condition is not particularly limited but is usually about -800 mmHg. The decompression time is 30 minutes or more, preferably 45 minutes or more, and the upper limit is not particularly limited.
[0130]
In a preferred embodiment of the present invention, an intermediate layer may be provided as necessary in addition to the image forming layer and the protective layer. However, for the purpose of improving productivity, these plural layers are simultaneously laminated in an aqueous system. Apply. Examples of the coating method include extrusion coating, slide bead coating, curtain coating, and the like, but the slide bead coating method disclosed in FIG. 1 of the specification of Japanese Patent Application Laid-Open No. 2000-2964 is particularly preferable.
In the case of a heat-developable image recording material using gelatin as a main binder, it is rapidly cooled in a first drying zone provided downstream of the coating die. As a result, gelatin is gelled and the coating film is cooled and solidified. The coating film that has been cooled and solidified and stopped flowing is guided to the subsequent second drying zone, and the solvent in the coating solution is volatilized and formed in the subsequent drying zone. As a drying method after the second drying zone, an air loop method in which a jet is blown from a U-shaped duct to a roller-supported support, or a support is wound around a cylindrical duct in a spiral shape to carry and dry. A firewood method (air floating method) can be used.
[0131]
In the coating liquid in which the main component of the binder is polymer latex, the flow of the coating liquid cannot be stopped by rapid cooling, and thus preliminary drying may be insufficient only in the first drying zone. In this case, in a drying method such as a heat-developable image recording material, flow unevenness and drying unevenness are generated, and a serious defect tends to occur on the coated surface.
[0132]
A preferable drying method in the present invention is at least a quarter or more of the constant rate drying period regardless of the first drying zone and the second drying zone as described in JP-A-2000-2964. A method of drying in a drying zone is preferable. The transport of the support from immediately after coating to the horizontal drying zone may or may not be horizontal transport, and the rising angle of the coating machine with respect to the horizontal direction may be between 0 and 70 °. . Further, the horizontal drying zone in the present invention is not limited to horizontal transport as long as the support is transported within ± 15 ° up and down with respect to the horizontal direction of the coating machine.
The drying air in the constant rate drying period is preferably dried at a wind speed of 1 to 30 m / s, preferably 2 to 20 m / s on the coating liquid film surface. More preferably, the first drying zone is a low-speed wind drying zone, and the wind speed is 15 m / s or less on the support surface, preferably 2 to 10 m / sec. In s, the subsequent second drying zone has a wind speed of 5 to 30 m / s, preferably 10 to 20 m / s, so that there is no occurrence of drying unevenness and the like, and productivity can be improved.
[0133]
The constant rate drying in the present invention means a drying process in which the liquid film temperature is constant and all the inflowing heat is used for evaporation of the solvent. Decreasing drying means that at the end of drying, the drying rate decreases due to various factors (such as the internal diffusion of moisture in the material, rate of receding evaporation surface), and the applied heat is also used to increase the liquid film temperature. Means drying process. When the constant rate drying is completed, the drying proceeds sufficiently until the flow stops, so that a drying method generally used for heat-developable image recording materials can also be adopted.
[0134]
The preferred drying conditions in the present invention are such that when the image forming layer and / or protective layer is formed, the drying condition is equal to or higher than the minimum film forming temperature (MFT) of the polymer latex in which the liquid film surface temperature at constant rate drying is used. Usually, it is often 25 ° C. to 45 ° C. due to the limitation of production equipment. Further, the dry bulb temperature at the rate of drying is preferably a temperature lower than Tg of the support to be used (normally 80 ° C. or less in the case of PET). In the present invention, the liquid film surface temperature means the surface temperature of the coating liquid film applied to the support, and the dry bulb temperature means the temperature of the drying air in the drying zone.
[0135]
When drying is performed under conditions where the liquid film surface temperature during constant rate drying is low, drying tends to be insufficient. For this reason, especially the film forming property of a protective layer falls remarkably, and it becomes easy to produce a crack on the film | membrane surface. In addition, the film strength is weakened, and serious problems such as easy damage to the film during transportation with an exposure machine or a heat development machine tend to occur.
Further, when excessive heat higher than the Tg of the support (base) is applied, the dimensional stability and curling resistance of the heat-developable image recording material are deteriorated.
[0136]
The winding after drying is preferably performed under the conditions of a temperature of 20 to 30 ° C. and a relative humidity of 45 ± 20%, and the winding shape may be the outer side of the image forming layer side according to the subsequent processing form, It may be inside. Moreover, when the processing form is a roll product, in order to remove the curl generated in the winding form, it is also preferable to use a roll form wound on the opposite side to the winding form at the time of processing. The environmental conditions at the time of packaging the heat-developable image recording material are preferably in the range of 20 to 30 ° C. relative humidity of 20 to 65%, and the humidity in the packaging is in the range of relative humidity of 20 to 55% (measured at 25 ° C.). Preferably it is controlled.
[0137]
In the method for cutting the heat-developable image recording material of the present invention, it is preferable that the heat-developable image recording material is cut when the temperature of the heat-developable image recording material is not lower than the glass transition temperature of the protective layer and not higher than the glass transition temperature of the support. Furthermore, the glass transition temperature of the protective layer + 5 ° C. or higher and the glass transition temperature of the support −15 ° C. or lower are preferred. When the glass transition temperature of the support is exceeded, thermal contraction of the support is added, strain stress due to cutting increases, and chips such as cracks and film peeling are likely to occur.
It is preferable to provide a heating means for heating the heat-developable image recording material on the upstream side of the cutting means for cutting the heat-developable image recording material being conveyed. Examples of the heating means include a method of heating by blowing hot air, a method of heating using a heating roller, a method of covering the part of the cutting device and controlling the heating temperature. Specifically, the heating method described in JP 2001-33741 A is preferably used.
[0138]
The heat-developable image recording materials are disclosed in JP-A-6-175291, JP-A-6-214350, JP-A-7-92618, JP-A-8-62783, JP-A-8-254793, JP-A-11. Packaging is carried out using the packaging materials and packaging methods described in JP-A No. 327089, JP-A No. 2000-181017, JP-A No. 2000-171942, JP-A No. 2000-206653, JP-A No. 2001-13632. Can do.
[0139]
In forming an image, the heat-developable image recording material is first exposed with light having a wavelength of 750 to 800 nm. The exposure apparatus used for exposure has an exposure time of 10^-7An exposure apparatus using a laser diode (LD) capable of exposure for less than a second as a light source is used. Any of these light sources may be used as long as they can generate light having an electromagnetic spectrum in a target wavelength range. For example, a dye laser, a gas laser, a solid laser, a semiconductor laser, and the like can be used. The semiconductor laser is particularly preferably used from the viewpoint of space saving and cost saving.
[0140]
When forming an image, it is preferable to expose the heat-developable image recording material by overlapping light beams from a light source. Overlap means that the sub-scanning pitch width is smaller than the beam diameter. The overlap can be expressed quantitatively by FWHM / sub-scanning pitch width (overlap coefficient), for example, when the beam diameter is expressed by the half width (FWHM) of the beam intensity. In the present invention, this overlap coefficient is preferably 0.2 or more.
[0141]
The light source scanning method of the exposure apparatus used in the present invention is not particularly limited, and a cylindrical outer surface scanning method, a cylindrical inner surface scanning method, a planar scanning method, and the like can be used. The channel of the light source may be a single channel or a multi-channel, but a multi-channel equipped with two or more laser heads is preferable in that a high output is obtained and a writing time is shortened. In particular, in the case of the cylindrical outer surface type, a multichannel equipped with several to several tens of laser heads is preferably used.
[0142]
When the heat-developable image recording material to be exposed has a low haze at the time of exposure, interference fringes tend to be generated. Therefore, it is preferable to prevent this. As a technique for preventing the occurrence of interference fringes, a technique for making laser light incident obliquely on a heat-developable image recording material as disclosed in Japanese Patent Application Laid-Open No. 5-113548, or International Publication WO95 / 31754 Are known, and it is preferable to use these techniques.
[0143]
The light source scanning method of the exposure apparatus preferably used in the present invention is an inner drum method (cylindrical inner surface scanning method). The exposure is performed by scanning the surface of the heat-developable image recording material conveyed to the inner drum portion through a polygon mirror (prism) with laser light generated from a laser diode. The exposure time in the main scanning direction is determined by the number of rotations of the polygon mirror and the inner diameter of the drum. The main scanning speed on the surface of the heat-developable image recording material is preferably 500 m / second to 1500 m / second. A more preferable main scanning speed is 630 m / sec to 1410 m / sec.
[0144]
When the heat-developable image recording material to be exposed has a low haze at the time of exposure, interference fringes tend to be generated. Therefore, it is preferable to prevent this. As a technique for preventing the occurrence of interference fringes, a technique for making laser light incident obliquely on a heat-developable image recording material as disclosed in Japanese Patent Application Laid-Open No. 5-113548, or International Publication WO95 / 31754 Are known, and it is preferable to use these techniques.
[0145]
After the heat-developable image recording material is exposed and a latent image is formed, it is developed by a heat developing machine having a preheating part, a heat developing part and a slow cooling part. The development temperature by the heat developing machine is preferably 80 to 250 ° C, and preferably 100 to 140 ° C. The total development time by the heat developing machine is preferably 1 to 180 seconds, and more preferably 5 to 90 seconds. Further, the processing speed of the heat developing section by the heat developing machine is preferably 21 to 100 mm / second, and more preferably 24 to 50 mm / second.
[0146]
The exposed heat-developable image recording material is first heated in a preheating unit. The preheating unit is provided for the purpose of preventing processing unevenness due to a dimensional change of the thermally developed image recording material during thermal development. The heating in the preheating unit is preferably set to a temperature and time that are lower than the heat development temperature (for example, about 10 to 30 ° C.) and low enough to evaporate the solvent remaining in the heat developed image recording material. It is preferable to set so that development unevenness does not occur at a temperature higher than the glass transition temperature (Tg) of the support of the heat-developable image recording material. Generally, it is preferable to heat at 80 ° C. or higher and lower than 115 ° C. for 5 seconds or longer.
[0147]
The photothermographic material heated in the preheating unit is subsequently heated in the thermal development unit. The heat developing unit includes a heating member on the image forming layer side and the back layer side of the heat developed image recording material to be transported, and a transport roller only on the image forming layer side. For example, when the heat-developable image recording material is conveyed with the image forming layer facing upward, the lower side (backside of the heat-developable image recording material) with respect to the direction of conveyance of the heat-developable image recording material has no conveying roller, and the upper side Only the (heat-developable image recording material image forming layer side) has a conveying roller. In the present invention, occurrence of density unevenness and physical deformation are prevented by adopting the above-described configuration of the heat development section.
[0148]
In the heat developing section, the heat developed image recording material is heated by a heating member such as a heater. The heating temperature in the heat development section is a temperature sufficient for heat development, and is generally 110 ° C to 140 ° C. Since the heat-developable image recording material is exposed to a high temperature of 110 ° C. or higher in the heat-development part, a part of the component contained in the material or a part of the decomposition component by heat development may volatilize. . These volatile components may cause uneven development, corrode heat developing machine components, precipitate at low temperatures, cause deformation of the screen as a foreign object, or become dirty on the screen. It is known to have various adverse effects such as. As a method for removing these influences, a method is known in which a filter is installed in the heat developing machine and the air flow in the heat developing machine is optimally adjusted. These methods can be used effectively in combination. For example, International Publication Nos. WO95 / 30933, 97/21150, and JP-T-10-500496 disclose a first opening that has bound absorbent particles and introduces volatile matter and a second that discharges. It is described that a filter cartridge having an opening is used in a heating device that heats in contact with a film. In addition, International Publication WO 96/12213 and Japanese National Publication No. 10-507403 describe that a filter in which a heat conductive condensing collector and a gas absorbing fine particle filter are combined is used. In the present invention, these can be preferably used. In US Pat. No. 4,518,845 and Japanese Patent Publication No. 3-54331, a device for removing steam from a film, a pressure device for pressing the film against a heat transfer member, and a heat transfer member are heated. A device having a device to perform is described. In addition, International Publication No. WO98 / 27458 describes that a component that increases fogging volatilization from a film is removed from the film surface. These can also be preferably used in the present invention.
[0149]
The heating temperature distribution in the preheating part and the thermal development part is preferably ± 1 ° C. or less, and more preferably ± 0.5 ° C. or less.
[0150]
The heat-developable image recording material heated in the heat developing portion is then cooled in the slow cooling portion. Cooling is preferably performed gradually so that the heat-developable image recording material is not physically deformed, and the cooling rate is preferably 0.5 to 10 ° C./second.
[0151]
One configuration example of a heat developing machine used for image formation is pre-heating described in JP 2000-171935 A, JP 2000-267226 A, JP 2001-22024 A, etc. using an opposing roller. A heat development processing apparatus is preferably used in which the heat development processing unit conveys the side having the image forming layer by sliding a roller and sliding the back surface on the opposite side to a smooth surface.
[0152]
When image formation is performed, exposure and heat development are performed by an online system of an exposure apparatus (plotter), an auto carrier, and a heat developing machine (processor). The auto carrier automatically conveys the exposed heat-developable image recording material to a processor (heat developing machine), and the conveyance mechanism may be any system such as a belt conveyor or a roller conveyance. Transport is preferred. The auto carrier is preferably provided with a mechanism that prevents heat from entering from the heat developing machine side to the exposure apparatus side. For example, there is a system in which air is sent from the lower part of the center of the auto carrier to the exposure apparatus and the heat developing machine.
[0153]
The heat-developable image recording material is, for example, a sheet-like material having a width of 550 to 650 mm and a length of 1 to 65 m, and a part or all of the heat-developable image recording material is wound around a cylindrical core member with the image forming layer outside. And incorporated into a thermal development system.
[0154]
When the heat-developable image recording material is used as a mask when producing a printing plate with a PS plate after heat development, the heat-developable image recording material after heat development is for setting exposure conditions for the PS plate in a plate making machine. And information for setting the plate making conditions such as the conveying conditions of the mask original and the PS plate are carried as image information. Accordingly, the concentration (use amount) of the above-mentioned irradiation dye, halation dye, and filter dye is limited to read them. Since these pieces of information are read by an LED or a laser, it is necessary that the Dmin (minimum concentration) in the wavelength region of the sensor is low and the absorbance is 0.3 or less. For example, the plate making machine S-FNRIII manufactured by Fuji Photo Film Co., Ltd. uses a light source having a wavelength of 670 nm as a detector and a barcode reader for detecting a registration mark. A 670 nm light source is used as a barcode reader for the plate making machine APML series manufactured by Shimizu. That is, when the Dmin (minimum density) near 670 nm is high, information on the film cannot be accurately detected, and work errors such as poor conveyance and poor exposure occur. Therefore, in order to read information with a light source of 670 nm, Dmin near 670 nm needs to be low, and the absorbance at 660 to 680 nm after heat development needs to be 0.3 or less. More preferably, it is 0.25 or less. Although there is no restriction | limiting in particular in the lower limit, Usually, it is about 0.10.
[0155]
In the present invention, the exposure apparatus used for imagewise exposure has an exposure time of 10.^-7Any apparatus capable of exposing in less than a second may be used, but in general, an exposure apparatus using a laser diode (LD) or a light emitting diode (LED) as a light source is preferably used. In particular, LD is more preferable in terms of high output and high resolution. Any of these light sources may be used as long as they can generate light having an electromagnetic spectrum in a target wavelength range. For example, in the case of LD, a dye laser, a gas laser, a solid laser, a semiconductor laser, or the like can be used.
[0156]
【Example】
The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.
[0157]
<Example 1>
<< Preparation of silver halide emulsion A >>
In 700 ml of water, 11 g of alkali-treated gelatin (calcium content of 2700 ppm or less), 30 mg of potassium bromide and 1.3 g of sodium 4-methylbenzenesulfonate were dissolved, and the pH was adjusted to 6.5 at 40 ° C. Thereafter, 159 ml of an aqueous solution containing 18.6 g of silver nitrate, 1 mol / L of potassium bromide, (NH₄)₂RhCl₅(H₂O) 5 × 10^-6mol / L and K₃IrCl₆2 × 10^-5An aqueous solution containing mol / L was added over 6 minutes 30 seconds by the control double jet method while maintaining pAg 7.7. Then, 476 ml of an aqueous solution containing 55.5 g of silver nitrate, 1 mol / L of potassium bromide and K₃IrCl₆2 × 10^-5A halogen salt aqueous solution containing mol / L was added over 28 minutes and 30 seconds by the control double jet method while maintaining pAg 7.7. Thereafter, the pH was lowered to cause coagulation sedimentation, followed by desalting, and 51.1 g of low molecular weight gelatin having an average molecular weight of 15,000 (calcium content of 20 ppm or less) was added to adjust the pH to 5.9 and pAg 8.0. The obtained particles were cubic particles having an average particle size of 0.08 μm, a projected area variation coefficient of 9%, and a (100) plane ratio of 90%.
[0158]
The obtained silver halide grains were heated to 60 ° C., 76 μmol of sodium benzenethiosulfonate was added per 1 mol of silver, 71 μmol of triethylthiourea was added after 3 minutes, and then ripened for 100 minutes. 6 × Methyl-1,3,3a, 7-tetrazaindene 5 × 10^-4After adding 0.17 g of mol and Compound A, the temperature was lowered to 40 ° C.
Thereafter, the temperature was kept at 40 ° C., and 4.7 × 10 4 mol per 1 mol of silver halide.^-2mol potassium bromide (added as an aqueous solution), 12.8 × 10^-4mol of sensitizing dye A (added as ethanol solution), 6.4 × 10^-3Mol of Compound B (added as a methanol solution) was added with stirring, and after 20 minutes, it was rapidly cooled to 30 ° C. to complete the preparation of silver halide emulsion A.
The obtained silver halide emulsion A was used for the preparation of the following coating solution.
[0159]
[Chemical formula 5]

[0160]
<< Preparation of silver behenate dispersion A >>
Behenic acid (produced by Henkel, Edenor C22-85R) 87.6 kg, distilled water 423 L, 5 mol / L NaOH aqueous solution 49.2 L, tert-butyl alcohol 120 L were mixed and stirred at 75 ° C. for 1 hour to react. A sodium behenate solution was obtained. Separately, 206.2 L of an aqueous solution containing 40.4 kg of silver nitrate was prepared and kept warm at 10 ° C. A reaction vessel containing 635 L of distilled water and 30 L of tert-butyl alcohol was kept at 30 ° C., and while stirring, the total amount of the previous sodium behenate solution and the total amount of the aqueous silver nitrate solution were 62 minutes 10 seconds and 60 at a constant flow rate, respectively. Added over minutes. At this time, only the silver nitrate aqueous solution was added for 7 minutes and 20 seconds after the start of the addition of the silver nitrate aqueous solution, and then the addition of the sodium behenate solution was started. After the addition of the silver nitrate aqueous solution, only the sodium behenate solution was added for 9 minutes and 30 seconds. To be added. At this time, the temperature in the reaction vessel was set to 30 ° C. and controlled so that the liquid temperature did not rise. The piping of the sodium behenate solution addition system was kept warm by steam tracing, and the amount of steam was controlled so that the liquid temperature at the outlet of the addition nozzle tip was 75 ° C. Moreover, the piping of the addition system of the silver nitrate aqueous solution was kept warm by circulating cold water outside the double pipe. The addition position of the sodium behenate solution and the addition position of the aqueous silver nitrate solution were arranged symmetrically around the stirring axis, and adjusted to a height that did not contact the reaction solution.
After completion of the addition of the sodium behenate solution, the mixture was left stirring for 20 minutes at the same temperature, and the temperature was lowered to 25 ° C. Thereafter, the solid content was separated by centrifugal filtration, and the solid content was washed with water until the filtrate had a conductivity of 30 μS / cm. The solid content thus obtained was stored as a wet cake without drying.
When the morphology of the obtained silver behenate particles was evaluated by electron microscopic photography, it was a scaly crystal having an average projected area diameter of 0.52 μm, an average particle thickness of 0.14 μm, and an average sphere equivalent diameter variation coefficient of 15%. It was.
[0161]
Next, a dispersion of silver behenate was prepared by the following method. 7.4 g of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-217, average degree of polymerization: about 1700) and water are added to the wet cake corresponding to 100 g of dry solid content, and the total amount is adjusted to 385 g. Pre-dispersed. Next, the pre-dispersed stock solution is subjected to a pressure of 1750 kg / cm of a disperser (manufactured by Microfluidics International Corporation, using Microfluidizer M-110S-EH, G10Z interaction chamber).²And the mixture was treated three times to obtain a silver behenate dispersion A. At this time, serpentine heat exchangers were installed before and after the interaction chamber, respectively, and the temperature of the refrigerant was adjusted to set the desired dispersion temperature.
The silver behenate particles contained in the obtained silver behenate dispersion A were particles having a volume weighted average diameter of 0.52 μm and a coefficient of variation of 15%. Particle size measurements were taken from Malvern Instruments Ltd. This was carried out using a master sizer X manufactured by the manufacturer. When evaluated by electron microscope photography, the ratio of the long side to the short side was 1.5, the particle thickness was 0.14 μm, and the average aspect ratio (ratio of the equivalent circle diameter of the projected area of the particle to the particle thickness) was 5.1. Met.
The obtained silver behenate dispersion A was used for the preparation of the following coating solution.
[0162]
<< Preparation of solid fine particle dispersion of reducing agent >>
20% by mass aqueous solution of reducing agent [1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane] 10 kg and modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203) To 10 kg, 400 g of Surfinol 104E (manufactured by Nissin Chemical Co., Ltd.), 640 g of methanol and 16 kg of water were added and mixed well to obtain a slurry. This slurry was fed with a diaphragm pump, dispersed in a horizontal bead mill (IMM Co., Ltd., UVM-2) filled with zirconia beads having an average diameter of 0.5 mm for 3 hours 30 minutes, and then benzoisothiazolinone sodium salt 4 g and water were added to adjust the concentration of the reducing agent to 25% by mass to obtain a solid fine particle dispersion of the reducing agent. The reducing agent particles contained in the obtained dispersion had a median diameter of 0.44 μm, a maximum particle size of 2.0 μm or less, and an average particle size variation coefficient of 19%. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust, and used for the preparation of the following coating solution.
[0163]
<< Preparation of solid fine particle dispersion of organic polyhalogen compound A >>
10 kg of organic polyhalogen compound A [tribromomethyl (4- (2,4,6-trimethylphenylsulfonyl) phenyl) sulfone], 10 kg of 20% by weight aqueous solution of modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203), tri 639 g of a 20% by mass aqueous solution of sodium isopropyl naphthalenesulfonate, 400 g of Surfynol 104E (manufactured by Nissin Chemical Co., Ltd.), 640 g of methanol and 16 kg of water were added and mixed well to obtain a slurry. This slurry is fed with a diaphragm pump and dispersed for 5 hours in a horizontal bead mill (IMM Co., Ltd., UVM-2) filled with zirconia beads having an average diameter of 0.5 mm. Then, water is added to the organic polyhalogen compound. The concentration of A was adjusted to 25% by mass to obtain a solid fine particle dispersion of organic polyhalogen compound A. The organic polyhalogen compound particles contained in the obtained dispersion had a median diameter of 0.36 μm, a maximum particle size of 2.0 μm or less, and an average particle size variation coefficient of 18%. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust, and used for the preparation of the following coating solution.
[0164]
<< Preparation of solid fine particle dispersion of organic polyhalogen compound B >>
5 kg of organic polyhalogen compound B [tribromomethyl naphthyl sulfone], 2.5 kg of 20 wt% aqueous solution of modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203), 213 g of 20 wt% aqueous solution of sodium triisopropylnaphthalenesulfonate and water 10 kg was added and mixed well to make a slurry. This slurry was fed with a diaphragm pump and dispersed for 5 hours in a horizontal bead mill filled with zirconia beads having an average diameter of 0.5 mm (manufactured by Imex Co., Ltd., UVM-2), and then benzoisothiazolinone sodium salt2. 5 g and water were added to adjust the concentration of the organic polyhalogen compound B to 23.5% by mass to obtain a solid fine particle dispersion of the organic polyhalogen compound B. The organic polyhalogen compound particles contained in the obtained dispersion had a median diameter of 0.38 μm, a maximum particle size of 2.0 μm or less, and an average particle size variation coefficient of 20%. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust, and used for the preparation of the following coating solution.
[0165]
<< Preparation of organic polyhalogen compound C aqueous solution >>
While stirring at room temperature, 75.0 ml of water, sodium tripropylnaphthalenesulfonate (20% aqueous solution) 8.6 ml, sodium dihydrogen orthophosphate dihydrate (5% aqueous solution) 6.8 ml, potassium hydroxide (1 mol) / L aqueous solution) 9.5 ml was sequentially added, and the mixture was stirred and mixed for 5 minutes after the addition. Further, 4.0 g of the organic polyhalogen compound C [3-tribromomethanesulfonylbenzoylaminoacetic acid] powder was added with stirring and dissolved uniformly to obtain 100 g of a transparent solution. The obtained aqueous solution was filtered through a 200-mesh polyester screen to remove foreign matters such as dust, and then used for the preparation of the following coating solution.
[0166]
<< Preparation of Emulsion Dispersion of Compound Z >>
10 kg of R-054 (manufactured by Sanko Co., Ltd.) containing 85% by mass of compound Z and 11.66 kg of MIBK were mixed and then purged with nitrogen and dissolved at 80 ° C. for 1 hour. To this solution, 25.52 kg of water, 12.76 kg of a 20% by weight aqueous solution of modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., MP-203) and 0.44 kg of a 20% by weight aqueous solution of sodium triisopropylnaphthalenesulfonate were added. The mixture was emulsified and dispersed at 20 to 40 ° C. and 3600 rpm for 60 minutes. Furthermore, 0.08 kg of Surfynol 104E (manufactured by Nissin Chemical Co., Ltd.) and 47.94 kg of water were added to this solution and distilled under reduced pressure to remove MIBK, so that the concentration of compound Z was 10% by mass. It was adjusted. The particles of compound Z contained in the dispersion thus obtained had a median diameter of 0.19 μm, a maximum particle size of 1.5 μm or less, and a particle size variation coefficient of 17%. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust, and used for the preparation of the following coating solution.
[0167]
[Chemical 6]

[0168]
<< Preparation of 6-isopropylphthalazine compound dispersion >>
While stirring 62.35 g of water at room temperature, 2.0 g of modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203) was added so as not to be agglomerated, and the mixture was stirred for 10 minutes. Thereafter, the mixture was heated and heated up until the internal temperature reached 50 ° C., and then stirred for 90 minutes in the range of the internal temperature of 50 to 60 ° C. to be uniformly dissolved. The internal temperature was lowered to 40 ° C. or lower, polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-217, 10% by mass aqueous solution) 25.5 g, sodium tripropylnaphthalenesulfonate (20% by mass aqueous solution) 3.0 g, 6 -7.15g of isopropyl phthalazine (70 mass% aqueous solution) was added, and it stirred for 30 minutes, and obtained 100 g of transparent dispersion liquids. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust, and used for the preparation of the following coating solution.
[0169]
<< Preparation of Solid Fine Particle Dispersion of Hardener X
To 4 kg of the thickening agent X, 1 kg of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval PVA-217) and 36 kg of water were added and mixed well to obtain a slurry. This slurry was fed with a diaphragm pump, and dispersed for 12 hours in a horizontal bead mill (IMM Co., Ltd., UVM-2) filled with zirconia beads having an average diameter of 0.5 mm. Then, 4 g of benzoisothiazolinone sodium salt and Water was added to adjust the concentration of the thickening agent to 10% by mass to obtain a solid fine particle dispersion of the thickening agent. The particles of the thickening agent contained in the dispersion thus obtained had a median diameter of 0.34 μm, a maximum particle size of 3.0 μm or less, and a particle size variation coefficient of 19%. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust, and used for the preparation of the following coating solution.
[0170]
<< Preparation of solid fine particle dispersion of development accelerator W >>
10 kg of the development accelerator W, 10 kg of a 20% by weight aqueous solution of modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203) and 20 kg of water were added and mixed well to obtain a slurry. This slurry is fed with a diaphragm pump, dispersed in a horizontal bead mill (IMM Co., UVM-2) filled with zirconia beads having an average diameter of 0.5 mm for 5 hours, and then added with water to develop accelerator W. The concentration of the toner was adjusted to 20% by mass to obtain a solid fine particle dispersion of the development accelerator W. The development accelerator particles contained in the dispersion thus obtained had a median diameter of 0.5 μm, a maximum particle size of 2.0 μm or less, and an average particle size variation coefficient of 18%. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust, and used for the preparation of the following coating solution.
[0171]
<< Preparation of Solid Fine Particle Dispersion of Development Accelerator W-2 >>
In preparing the solid fine particle dispersion of the development accelerator W, the development accelerator was changed to W-2, and a solid fine particle dispersion of the development accelerator W-2 was prepared in the same manner as the dispersion method.
[0172]
<< Preparation of solid fine particle dispersion of organic polyhalogen compound D >>
6 kg of organic polyhalogen compound D, 12 kg of 10 wt% aqueous solution of modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203), 240 g of 20 wt% aqueous solution of sodium triisopropylnaphthalenesulfonate, and 0.18 kg of water were added. , Well mixed to make a slurry. This slurry was fed with a diaphragm pump and dispersed for 5 hours in a horizontal bead mill (IMM Co., Ltd., UVM-2) filled with zirconia beads having an average diameter of 0.5 mm. Then, 2 g of benzoisothiazolinone sodium salt and Preparation was made so that the concentration of the organic polyhalogen compound D by adding water was 30% by mass to obtain a solid fine particle dispersion of the organic polyhalogen compound D. The organic polyhalogen compound particles contained in the obtained dispersion had a median diameter of 0.40 μm, a maximum particle size of 2.0 μm or less, and an average particle size variation coefficient of 20%. The obtained dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign matters such as dust, and used for the preparation of the following coating solution.
[0173]
[Chemical 7]

[0174]
<Preparation of image forming layer coating solution>
The following binder, raw material, and silver halide emulsion A were added to 1 mol of silver of silver behenate dispersion A, and water was added to prepare an image forming layer coating solution. After completion, vacuum degassing was performed at a pressure of 0.54 atm for 45 minutes. The pH of the coating solution was 7.3 to 7.7, and the viscosity was 40 to 50 mPa · s at 25 ° C.

NaOH was used as a pH adjuster.
The mass ratio of the other solid content of the image forming layer to the binder was adjusted as shown in Table 1 by changing the amount of binder: SBR latex added.
[0175]
[Chemical 8]

[0176]
<< Preparation of coating solution for protective layer >>
Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 58.9 / 8.6 / 25.4 / 5.1 / 2 (mass%) polymer latex solution (copolymer and glass A transition temperature of 46 ° C. (calculated value), a solid content concentration of 21.5% by mass, 100 ppm of compound A, and further 15% by mass of compound D as a film-forming aid with respect to the solid content of the latex Water was added to 943 g of glass transition temperature of 24 ° C., average particle size 116 nm), 114.8 g of an aqueous solution of polyhalogen compound C, 17.0 g of polyhalogen compound A as a solid content, sodium dihydrogen orthophosphate · dihydrate 0.69 g of Japanese as solid, 10 g of development accelerator W as solid, and development accelerator W-2 as solid 5 g, matting agent (polystyrene particles, average particle size 7 μm, average particle size variation coefficient 8%) 1.58 g, polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-235) 29.3 g and compound E 0.62 g, 1.0 g of Compound I was added, and water was further added to prepare a coating solution (containing 0.8% by mass of methanol solvent). After completion, vacuum degassing was performed at a pressure of 0.47 atm for 60 minutes. The coating solution had a pH of 5.5 and a viscosity of 45 mPa · s at 25 ° C.
[0177]
<< Preparation of lower overcoat layer coating liquid >>
Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 58.9 / 8.6 / 25.4 / 5.1 / 2 (mass%) polymer latex solution (copolymer and glass A transition temperature of 46 ° C. (calculated value), a solid content concentration of 21.5% by mass, compound A of 100 ppm is contained, and a compound D as a film-forming aid is incorporated by 15% by mass with respect to the solid content of the latex. Water was added to 625 g of an average particle size of 74 nm with a glass transition temperature of 24 ° C., 0.23 g of Compound C, 0.13 g of Compound I, 11.7 g of Compound F, 2.7 g of Compound H and polyvinyl. 11.5 g of alcohol (PVA-235, manufactured by Kuraray Co., Ltd.) was added, water was further added, and coating solution (containing 0.1% by mass of methanol solvent) ) Was prepared. After completion, vacuum degassing was performed at a pressure of 0.47 atm for 60 minutes. The coating solution had a pH of 2.6 and a viscosity of 30 mPa · s at 25 ° C.
[0178]
<< Preparation of coating solution for upper overcoat layer >>
Methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / acrylic acid = 58.9 / 8.6 / 25.4 / 5.1 / 2 (mass%) polymer latex solution (copolymer and glass A transition temperature of 46 ° C. (calculated value), a solid content concentration of 21.5% by mass, 100 ppm of compound A, and further 15% by mass of compound D as a film-forming aid with respect to the solid content of the latex. Water was added to 649 g of an average particle size of 116 nm having a glass transition temperature of 24 ° C., and 18.4 g of a 30% by mass solution of Carnava wax (manufactured by Chukyo Yushi Co., Ltd., Cerozol 524: less than 5 ppm as a silicone content), 0.23 g of Compound C, 1.0 g of Compound E, 1.0 g of Compound G, 0.87 g of Compound I, matting agent (Polymer) 3.45 g of styrene particles, average particle size 7 μm, coefficient of variation of average particle size 8%) and 26.5 g of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-235) are added, and water is added to the coating solution (methanol solvent) Containing 1.1 mass%). After completion, vacuum degassing was performed at a pressure of 0.47 atm for 60 minutes. The coating solution had a pH of 5.3 and a viscosity of 25 mPa · s at 25 ° C.
[0179]
[Chemical 9]

[0180]
<< Preparation of polyethylene terephthalate (PET) support with back / undercoat layer >>
(1) Production of PET support
Using terephthalic acid and ethylene glycol, polyethylene terephthalate having an intrinsic viscosity of IV = 0.66 (measured at 25 ° C. in phenol / tetrachloroethane = 6/4 (mass ratio)) was obtained according to a conventional method. After pelletizing this, it was dried at 130 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die, and then rapidly cooled to produce an unstretched film having a thickness such that the film thickness after heat setting was 120 μm. did.
This was stretched 3.3 times in the longitudinal direction using rolls having different peripheral speeds, and then stretched 4.5 times in the tenter. The temperatures at this time were 110 ° C. and 130 ° C., respectively. Then, after heat setting at 240 ° C. for 20 seconds, the film was relaxed 4% in the lateral direction at the same temperature. Then, after slitting the chuck part of the tenter, knurling is performed on both ends, and 4.8 kg / cm.²I rolled it up. Thus, a roll-shaped PET support having a width of 2.4 m, a length of 3500 m, and a thickness of 120 μm was obtained.
[0181]
(2) Preparation of undercoat layer and back layer
(1) Undercoat first layer
The coating solution having the composition shown below was 6.2 ml / m.²Then, it was coated on a support and dried at 125 ° C. for 30 seconds, 150 ° C. for 30 seconds, and 185 ° C. for 30 seconds.

[0182]
(2) Undercoat second layer
A coating solution having the following composition is 5.5 ml / m²Then, it was applied onto the first undercoat layer and dried at 125 ° C. for 30 seconds, 150 ° C. for 30 seconds, and 170 ° C. for 30 seconds.

[0183]
▲ 3 ▼ Back first layer
0.375 kV · A · min / m on the surface opposite to the surface coated with the undercoat layer²The coating liquid having the composition shown below was applied to the surface at 13.8 ml / m.²And then dried at 125 ° C. for 30 seconds, 150 ° C. for 30 seconds, and 185 ° C. for 30 seconds.

[0184]
▲ 4 ▼ Back second layer
A coating solution having the following composition is 5.5 ml / m²It was coated on the back first layer so as to be dried at 125 ° C. for 30 seconds, 150 ° C. for 30 seconds, and 170 ° C. for 30 seconds.
[0185]
Jurimar ET410 57.5g
(30% aqueous dispersion, manufactured by Nippon Pure Chemicals Co., Ltd.)
Polyoxyethylene phenyl ether 1.7g
Water-soluble melamine compound 15g
(Sumitomo Chemical Co., Ltd., Sumitex Resin M-3 (8% aqueous solution))
Cerosol 524 (30% aqueous solution, manufactured by Chukyo Yushi Co., Ltd.) 6.6 g
Distilled water Amount that makes the total amount 1000g
[0186]
▲ 5 ▼ Back third layer
6.2 ml / m of the same coating solution as the undercoat first layer²It was coated on the back second layer so that the following was obtained, and dried at 125 ° C. for 30 seconds, 150 ° C. for 30 seconds, and 185 ° C. for 30 seconds.
[0187]
▲ 6 ▼ Back fourth layer
13.8 ml / m of a coating solution having the following composition²Then, it was applied onto the back third layer and dried at 125 ° C. for 30 seconds, 150 ° C. for 30 seconds, and 170 ° C. for 30 seconds.

[0188]
Embedded image

Embedded image

[0189]
Latex-A:
Core-shell type latex with 90 mass% core and 10 mass% shell
(Weight average molecular weight 38000)
Core: Vinylidene chloride / methyl acrylate / methyl methacrylate /
Acrylonitrile / acrylic acid = 93/3/3 / 0.9 / 0.1 (mass%)
Shell part: Vinylidene chloride / methyl acrylate / methyl methacrylate /
Acrylonitrile / acrylic acid = 88/3/3/3/3 (mass%)
[0190]
(3) Transport heat treatment
(3-1) Heat treatment
The PET support with the back / undercoat layer thus prepared was put in a heat treatment zone with a total length of 200 m set at 160 ° C., and the tension was 2 kg / cm.², And conveyed at a conveyance speed of 20 m / min.
(3-2) Post heat treatment
Subsequent to the above heat treatment, the film was passed through a 40 ° C. zone for 15 seconds, followed by heat treatment, and wound up. The winding tension at this time is 10 kg / cm²Met.
[0191]
<Production of heat-developable image recording material>
As described above, using the slide bead coating method disclosed in FIG. 1 of Japanese Patent Application Laid-Open No. 2000-2964, on the undercoat layer of the PET support that has been applied with the back layer and the undercoat layer and subjected to the conveyance heat treatment, A coating silver amount of 1.5 g / m was applied to the image forming layer coating solution.²On top of that, the above-mentioned protective layer coating solution is coated with a solid content of polymer latex of 1.3 g / m.²At the same time, multiple layers were applied. Next, the lower layer overcoat layer coating solution is coated thereon with a polymer latex solid content coating amount of 2.0 g / m.²So that the coating amount of the polymer overcoat layer is 1.0 g / m.²At the same time, multiple layers were applied.
[0192]
The drying conditions at the time of coating are as follows: the first drying zone (slow wind drying area) has a dry bulb temperature of 70 to 75 ° C., a dew point of 9 to 23 ° C., a wind speed of 8 to 10 m / s on the support surface, and a liquid film surface temperature of 35 to 35 ° C. It dried in the range of 40 degreeC, and the 2nd drying zone (high-speed wind drying area) dried with the dry-bulb temperature of 65-70 degreeC, the dew point of 20-23 degreeC, and the wind speed on a support surface of 20-25 m / s. . The residence time in the first drying zone was 2/3 of the constant-rate drying period in this zone, and it was transferred to the second drying zone for drying. The first drying zone is a horizontal drying zone (an angle at which the support is 1.5 ° to 3 ° with respect to the horizontal direction of the coating machine). The coating speed was 60 m / min. Winding after drying was performed under conditions of a temperature of 23 ± 3 ° C. and a relative humidity of 45 ± 5%. The winding form was adjusted to the subsequent processing mode (image forming layer surface side outer winding), and the image forming layer surface side was removed. The heat-developable image recording material has a packaging humidity of 20 to 40% relative humidity (measured at 25 ° C.), and the obtained heat-developable image recording material has a film surface pH of 5.0 and an opposite film. The surface pH was 5.9.
Subsequently, a roll-shaped heat-developable image recording material package was produced in the following manner under an environmental condition of 23 ± 3 ° C. and a relative humidity of 63 ± 5%.
[0193]
<Manufacture of light-shielding reader>
A heat-shrinkable light-shielding film made by bonding a light-shielding film (a low-density polyethylene sheet with a thickness of 30 μm mixed with 5% by mass of carbon black) on both sides of a 30 μm-thick shrink film (manufactured by Gunze Co., Ltd., TNS) Strips were produced. The heat-shrinkable light-shielding film strips obtained had a thermal shrinkage rate of 13.3% in the length direction and 11.9% in the width direction at 100 ° C., and the Elmendorf tear load in the length direction was 0.00. 43N. The heat-shrinkable light-shielding film strips are respectively attached to both sides of a light-shielding sheet obtained by laminating a low-density polyethylene sheet having a thickness of 40 μm mixed with 5% by mass of carbon black on both surfaces of a PET sheet having a thickness of 100 μm. A light-shielding reader was manufactured by sticking along both side edges so as to protrude in the width direction.
[0194]
<< Manufacture of light-shielding heat-developable image recording material roll >>
The above heat-developable image recording material was wound around a paper core having an outer diameter of 3 inches while cutting to a width of 610 mm and a winding length of 59 m with a light-shielding reader facing out and the surface having the image forming layer on the outside.
Next, disk-shaped light shielding members were attached to both ends of the heat-developable image recording material roll. Next, a light-shielding leader is attached to the roll-shaped heat-developable image recording material with an adhesive tape, and hot air at 270 ° C. is applied to the surface of the heat-shrinkable light-shielding film strip of the light-shielding reader while being wrapped around the heat-developable image recording material roll. By spraying, the heat-shrinkable light-shielding film strip of the light-shielding reader was brought into contact with the outer surface beyond the outer peripheral edge of the disk-shaped light-shielding member in a thermally contracted state. Then, after sealing the end portion of the light-shielding reader at the end of winding and the outer surface of the light-shielding reader one turn before, a thin film made of a heat-shrinkable light-shielding film that is in close contact with the outer surface of the disk-shaped light-shielding member. A heater heated to 130 ° C. was pressed against the surface of the piece to fuse the outer surface of the disk-shaped light shielding member and the heat-shrinkable light-shielding film strip.
[0195]
<Cut test method>
The heat-developable image recording material obtained above was evaluated based on the following method.
1 and FIG. 2, using a die set for cutting (upper blade angle α = 90 degrees, shear angle β = 15 degrees), press machine (manufactured by Janome Sewing Machine Co., Ltd., ERETRO PRESS JP-503 type) Then, with the cutting speed = 30 mm / sec, the surface having the image forming layer was cut with the upper blade side, and the occurrence of cracks / peeling and the occurrence of sag in the coated film on the side having the image forming layer in the cut portion was evaluated. . The temperature of the heat-developable image recording material was heated immediately before cutting, and the temperature at the time of cutting was measured with a radiation thermometer.
<Degree of crack / peeling>
5 ... No cracking / peeling of coating film
3 ... cracks and no peeling
1 ... with cracks and peeling
“4” is between “5” and “3”, and “2” is between “3” and “1”. “4” or higher is a level that causes no problem in practical use.
<Degree of Beco>
5 ... No bevel
3 ... There is a little bit
1 ... Beco
“4” is between “5” and “3”, and “2” is between “3” and “1”. “4” or higher is a level that causes no problem in practical use.
[0196]
<Evaluation of practical concentration>
A single channel cylindrical inner surface type laser exposure apparatus equipped with a semiconductor laser having a beam diameter (FWHM ½ of beam intensity) of 12.56 μm, a laser output of 50 mW, and an output wavelength of 783 nm for the obtained heat-developable image recording material. , Mirror rotation speed 60000 rpm, exposure time 1.2 × 10^-8Second exposure was performed.
The overlap coefficient at this time is 0.449, and the laser energy density on the heat-developable image recording material surface is 75 μJ / cm.²It was. Using the above laser exposure apparatus, a test step is output while changing the light intensity at 175 lines / inch, and using a dry system processor (FDS-6100X, manufactured by Fuji Photo Film Co., Ltd.), 121 ° C. for 20 seconds. Thermal development processing was performed under the development conditions, and the Dmax (maximum density) part when exposed at an LV value at which the halftone dot was 50% was measured to obtain the practical density. Density measurement was performed with a Macbeth TD904 densitometer (visible density).
[0197]
The obtained results are shown in Table 1. From the results shown in Table 1, samples satisfying the conditions of the present invention are images that are optimal for photolithography without cracks or film peeling during the cutting of heat-developable image recording materials and without image defects due to these chips. Can be provided.
[0198]
[Table 1]

[0199]
【The invention's effect】
If the heat-developable image recording material is cut according to the method of the present invention, the generation of cracks, film peeling and chips can be effectively suppressed, and the occurrence of image defects in the heat-developable image recording material can also be prevented.
[Brief description of the drawings]
FIG. 1 is a perspective view for explaining a cutting die set used in a cutting test.
FIG. 2 is a cross-sectional view for explaining a cutting die set used in a cutting test.
[Explanation of symbols]
1 Upper blade
2 Lower blade
3 Heat-developable image recording material
4 Upper blade side cut surface
α ° Blade angle of upper blade
β ° shear angle
3a₁  Cut lower blade side image forming layer + protective layer
3b₁  Cut lower blade side support
3a₂  Cut upper blade side image forming layer + protective layer
3b₂  Cut upper blade side support

Claims (5)

Thermal development having, on a support, at least one image forming layer containing an organic silver salt, photosensitive silver halide, and a reducing agent, and at least one protective layer provided on the image forming layer A method for cutting a heat-developable image recording material, characterized in that the image recording material is cut at a temperature not lower than the glass transition temperature of the protective layer and not higher than the glass transition temperature of the support. The support of the heat-developable image recording material is obtained by performing a heat treatment at a temperature of 130 ° C. to 185 ° C. after performing a treatment for improving adhesion to the image forming layer and / or the back layer. The method for cutting a heat-developable image recording material according to claim 1. The method for cutting a heat-developable image recording material according to claim 1 or 2, wherein the heat-developable image recording material contains a high contrast agent. The method for cutting a heat-developable image recording material according to any one of claims 1 to 3, wherein a polymer latex is used as a binder for the image forming layer, the protective layer and the back layer. The cutting ratio of the heat-developable image recording material according to any one of claims 1 to 4, wherein the mass ratio of the other solid content to the binder of the image forming layer of the heat-developable image recording material is 1.0 to 2.5. Method.

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