JP3739980B2 - Photothermographic material for heat development - Google Patents

Description

【００３２】
一般式（１) においてＲ^１ 、Ｒ^２ 、Ｒ^３ は、それぞれ独立に水素原子または置換基を表し、Ｚは電子吸引性基またはシリル基を表す。一般式（１）においてＲ^１ とＺ、Ｒ^２ とＲ^３ 、Ｒ^１ とＲ^２ 、あるいはＲ^３ とＺは、互いに結合して環状構造を形成していてもよい。一般式（２) においてＲ^４ は、置換基を表す。一般式（３) においてＸ、Ｙはそれぞれ独立に水素原子または置換基を表し、Ａ、Ｂはそれぞれ独立に、アルコキシ基、アルキルチオ基、アルキルアミノ基、アリールオキシ基、アリールチオ基、アニリノ基、ヘテロ環オキシ基、ヘテロ環チオ基、またはヘテロ環アミノ基を表す。一般式（３) においてＸとＹ、あるいはＡとＢは、互いに結合して環状構造を形成していてもよい。
【００３３】
一般式（１) で表される化合物の中でより好ましいものは、Ｚがシアノ基、ホルミル基、アシル基、アルコキシカルボニル基、イミノ基、またはカルバモイル基を表し、Ｒ^１ が電子吸引性基またはアリール基を表し、Ｒ^２ またはＲ^３ のどちらか一方が水素原子で、他方がヒドロキシ基( またはその塩) 、メルカプト基( またはその塩) 、アルコキシ基、アリールオキシ基、ヘテロ環オキシ基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基またはヘテロ環基を表す化合物である。さらに好ましいものは、ＺとＲ^１ とが非芳香族の５員〜７員の環状構造を形成していて、Ｒ^２ またはＲ^３ のどちらか一方が水素原子で、他方がヒドロキシ基( またはその塩) 、メルカプト基( またはその塩) 、アルコキシ基、アリールオキシ基、ヘテロ環オキシ基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、またはヘテロ環基を表す化合物である。この時、Ｒ^１ と共に非芳香族の環状構造を形成するＺとしては、アシル基、カルバモイル基、オキシカルボニル基、チオカルボニル基、スルホニル基等が好ましく、またＲ^１ としては、アシル基、カルバモイル基、オキシカルボニル基、チオカルボニル基、スルホニル基、イミノ基、Ｎ原子で置換したイミノ基、アシルアミノ基、カルボニルチオ基等が好ましい。
【００３４】
一般式（２) において、置換基Ｒ^４ は電子吸引性基またはアリール基であり、好ましくは総炭素数０〜３０の置換もしくは無置換のフェニル基、シアノ基、アルコキシカルボニル基、カルバモイル基、ヘテロ環基、最も好ましくはシアノ基、ヘテロ環基またはアルコキシカルボニル基である。
【００３５】
一般式（３) のＸ、Ｙで表される置換基は、好ましくは総炭素数１〜４０の、より好ましくは総炭素数１〜３０の基であり、より好ましくはシアノ基、アルコキシカルボニル基、カルバモイル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アシルチオ基、アシルアミノ基、チオカルボニル基、ホルミル基、イミノ基、Ｎ原子で置換したイミノ基、ヘテロ環基または任意の電子吸引性基で置換されたフェニル基等である。ＸとＹが、互いに結合して非芳香族の炭素環または非芳香族のヘテロ環を形成している場合もまた好ましい。形成される環状構造は５員〜７員環が好ましく、その総炭素数は１〜４０、さらには３〜３０が好ましい。環状構造を形成するＸおよびＹとしては、アシル基、カルバモイル基、オキシカルボニル基、チオカルボニル基、スルホニル基、イミノ基、Ｎ原子で置換したイミノ基、アシルアミノ基、カルボニルチオ基等が好ましい。
一般式（３）においてＡ、Ｂはそれぞれ独立に、アルコキシ基、アルキルチオ基、アルキルアミノ基、アリールオキシ基、アリールチオ基、アニリノ基、ヘテロ環チオ基、ヘテロ環オキシ基またはヘテロ環アミノ基を表し、これらの総炭素数１〜３０である。Ａ、Ｂは互いに結合して環状構造を形成している場合がより好ましく、５員〜７員環の非芳香族のヘテロ環がより好ましい。この場合に、Ａ、Ｂが連結した例( −Ａ−Ｂ−) を挙げれば、例えば−Ｏ−（ＣＨ₂）₂−Ｏ−、−Ｏ−（ＣＨ₂）₃−Ｏ−、−Ｓ−（ＣＨ₂）₂−Ｓ−、−Ｓ−（ＣＨ₂）₃−Ｓ−、−Ｓ−ｐｈ−Ｓ−、−Ｎ（ＣＨ₃）−（ＣＨ₂）₂−Ｏ−、−Ｎ（ＣＨ₃）−（ＣＨ₂）₂−Ｓ−、−Ｏ−（ＣＨ₂）₂−Ｓ−、−Ｏ−（ＣＨ₂）₃−Ｓ−、−Ｎ（ＣＨ₃）−ｐｈ−Ｏ−、−Ｎ（ＣＨ₃）−ｐｈ−Ｓ−、−Ｎ（ｐｈ）−（ＣＨ₂）₂−Ｓ−等である。
【００３６】
一般式（１) 〜一般式（３) で表される化合物は、ハロゲン化銀に対して吸着するアルキルチオ基、アリールチオ基、チオ尿素基、チオアミド基、メルカプト複素環基、トリアゾール基などの基が組み込まれていてもよい。
一般式（１) 〜一般式（３) で表される化合物は、アルキル基、アラルキル基、アルコキシ基、フェニル基、アルキルフェニル基、フェノキシ基、アルキルフェノキシ基などバラスト基が組み込まれているものがより好ましい。
【００３７】
一般式（１) 〜一般式（３) で表される化合物は、その中にカチオン性基（４級のアンモニオ基を含む基、または４級化された窒素原子を含む含窒素ヘテロ環基等）、エチレンオキシ基もしくはプロピレンオキシ基の繰り返し単位を含む基、（アルキル、アリール、またはヘテロ環）チオ基、あるいは塩基により解離しうる解離性基（カルボキシ基、スルホ基、アシルスルファモイル基、カルバモイルスルファモイル基等）が含まれているものがより好ましく、特にエチレンオキシ基もしくはプロピレンオキシ基の繰り返し単位を含む基、あるいは（アルキル、アリール、またはヘテロ環）チオ基が含まれているものが好ましい。
一般式（１) 〜一般式（３) で表される化合物の使用量は、銀１モルに対し１×１０^−６〜１モルが好ましく、１×１０^−５〜５×１０^−１モルがより好ましく、２×１０^−５〜２×１０^−１モルが最も好ましい。
【００３８】
超硬調化剤として下記一般式（Ｈ）によって表わされるヒドラジン誘導体を用いることも好ましい。
Ｒ^１２−ＮＡ^１ −ＮＡ^２ −（Ｇ^１ ）_ｍ１−Ｒ^１１ （Ｈ）
式中、Ｒ^１２は脂肪族基、芳香族基またはヘテロ環基を表す。脂肪族基は好ましくは炭素数1 〜30のアルキル基、アルケニル基、アルキニル基である。芳香族基は単環もしくは縮合環のアリール基で、例えばフェニル基、ナフチル基が挙げられる。ヘテロ環基としては、単環または縮合環の、飽和もしくは不飽和の、芳香族または非芳香族のヘテロ環基である。中でも好ましいものはアリール基もしくはアルキル基である。
【００３９】
Ｒ^１２が有していてもよい置換基として好ましいものは、Ｒ^１２が脂肪族基を表す場合は、アルキル基、アリール基、ヘテロ環基、アミノ基、アシルアミノ基、スルホンアミド基、ウレイド基、スルファモイルアミノ基、イミド基、チオウレイド基、リン酸アミド基、ヒドロキシ基、アルコキシ基、アリールオキシ基、アシルオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、カルボキシ基（その塩を含む）、（アルキル、アリール、またはヘテロ環）チオ基、スルホ基（その塩を含む）、スルファモイル基、ハロゲン原子、シアノ基、ニトロ基が好ましい。Ｒ^１２が芳香族基またはヘテロ環基を表す場合、アルキル基（活性メチレン基を含む）、アラルキル基、ヘテロ環基、置換アミノ基、アシルアミノ基、スルホンアミド基、ウレイド基、スルファモイルアミノ基、イミド基、チオウレイド基、リン酸アミド基、ヒドロキシ基、アルコキシ基、アリールオキシ基、アシルオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、カルボキシ基（その塩を含む）、（アルキル、アリール、またはヘテロ環）チオ基、スルホ基（その塩を含む）、スルファモイル基、ハロゲン原子、シアノ基、ニトロ基等が好ましい。
【００４０】
Ｒ^１１は水素原子またはブロック基を表す。ブロック基とは脂肪族基（具体的にはアルキル基、アルケニル基、アルキニル基）、芳香族基（単環もしくは縮合環のアリール基）、ヘテロ環基、アルコキシ基、アリールオキシ基、アミノ基またはヒドラジノ基を表す。Ｒ^１１は置換されていても良く、置換基の例としてＲ^１２で例示したものがあげられる。
A^１、A^２はともに水素原子、あるいは一方が水素原子で他方が炭素数20以下のアルキルスルホニル基、またはアリールスルホニル基（好ましくはフェニルスルホニル基、またはハメットの置換基定数の和が-0．5 以上となるように置換されたフェニルスルホニル基）、またはアシル基（好ましくはベンゾイル基、またはハメットの置換基定数の和が-0．5 以上となるように置換されたベンゾイル基、あるいは脂肪族アシル基）を表す。m1は0 または1 であり、m1が0 の時、Ｒ^１１は脂肪族基、芳香族基、またはヘテロ環基を表す。A^１、A^２としては水素原子が最も好ましい。
G^１は-CO-、-COCO-、-C( ＝S)- 、-SO₂- 、-SO-、-PO(Ｒ^１３)-基（Ｒ^１３はＲ^１１に定義した基と同じ範囲内より選ばれ、Ｒ^１１と異なっていてもよい。）またはイミノメチレン基を表す。
【００４１】
一般式（Ｈ）のヒドラジン誘導体は、ハロゲン化銀に対して吸着性の基（アルキルチオ基、アリールチオ基、チオ尿素基、チオアミド基、メルカプト複素環基、トリアゾール基など）が組み込まれていてもよい。
一般式（Ｈ）のＲ^１１またはＲ^１２はその中にアルキル基、アラルキル基、アルコキシ基、フェニル基、アルキルフェニル基、フェノキシ基、アルキルフェノキシ基などのバラスト基または特開平1-100530号に記載のポリマーが組み込まれているものでもよい。
一般式（Ｈ）のＲ^１１またはＲ^１２は、その中にカチオン性基（4 級のアンモニオ基を含む基、または4 級化された窒素原子を含む含窒素ヘテロ環基等）、エチレンオキシ基もしくはプロピレンオキシ基の繰り返し単位を含む基、（アルキル、アリール、またはヘテロ環）チオ基、あるいは塩基により解離しうる解離性基（カルボキシ基、スルホ基、アシルスルファモイル基、カルバモイルスルファモイル基等）が含まれていてもよい。
本発明において用いることができるヒドラジン誘導体の添加量は、銀1 モルに対し1 ×10^−６〜1 ×10^−２モルが好ましく、1 ×10^−５〜5 ×10^−３モルがより好ましく、2 ×10^−５〜5 ×10^−３モルが最も好ましい。
【００４２】
また、本発明は超硬調画像形成のために、前記の超硬調化剤とともに硬調化促進剤を併用することができる。例えば、米国特許第5,545,505 号に記載のアミン化合物、同5,545,507 号に記載のヒドロキサム酸類、同5,545,507 号に記載のアクリロニトリル類、同5,558,983 号に記載のヒドラジン化合物、特開平９−２９７３６８号に記載のオニュ−ム塩類などを用いることができる。
【００４３】
本発明における増感色素としてはシアニン色素、メロシアニン色素、コンプレックスシアニン色素、コンプレックスメロシアニン色素、ホロポーラーシアニン色素、スチリル色素、ヘミシアニン色素、オキソノール色素、ヘミオキソノール色素等を用いることができる。
赤色光への分光増感の例としては、He-Ne レーザー、赤色半導体レーザーやLED など赤色光源に対しては特開昭54-18726号、特開平6-75322 号、特開平7-287338号、特公昭55-39818号、特開昭62-284343 号、特開平7-287338号に記載の化合物を用いることができる。
750 〜1400ｎｍの波長領域の半導体レーザー光源に対しては、シアニン、メロシアニン、スチリル、ヘミシアニン、オキソノール、ヘミオキソノールおよびキサンテン色素を含む種々の既知の色素により有利に増感させることができる。
また、J-bandを形成する色素として米国特許5,510,236 号、同3,871,887 号、特開平2-96131 号、特開昭59-48753号が好ましく用いることができる。
本発明における増感色素の使用量としては、感光性層のハロゲン化銀1 モル当たり10^−６〜1 モルが好ましく、10^−４〜10^−１モルがさらに好ましい。
【００４４】
カブリ防止剤、安定剤および安定剤前駆体は、米国特許第2,131,038 号および同第2,694,716 号に記載のチアゾニウム塩、米国特許第2,886,437 号および同第2,444,605 号に記載のアザインデン、米国特許第2,728,663 号に記載の水銀塩、米国特許第3,287,135 号に記載のウラゾール、米国特許第3,235,652 号に記載のスルホカテコール、英国特許第623,448 号に記載のオキシム、ニトロン、ニトロインダゾール、米国特許第2,839,405 号に記載の多価金属塩、米国特許第3,220,839 号に記載のチウロニウム塩、ならびに米国特許第2,566,263 号および同第2,597,915 号に記載のパラジウム、白金および金塩、米国特許第4,108,665 号および同第4,442,202 号に記載のハロゲン置換有機化合物、米国特許第4,128,557 号および同第4,137,079 号、第4,138,365 号および同第4,459,350 号に記載のトリアジンならびに米国特許第4,411,985 号に記載のリン化合物などがある。
また、カブリ防止や高感度化を目的として安息香酸類を含有しても良い。好ましい安息香酸類の構造の例としては、米国特許4,784,939 号、同4,152,160 号、特開平９−３２９８６５号、同９−３２９８６４号、同９−２８１６３７号などに記載の化合物が挙げられれ、有機銀塩含有層に添加することが好ましい。この添加量は、銀1 モル当たり1 μモル以上2 モル以下が好ましく、1mモル以上0.5 モル以下がさらに好ましい。
【００４５】
本発明には現像を抑制あるいは促進させ現像を制御するため、分光増感効率を向上させるため、現像前後の保存性を向上させるためなどにメルカプト化合物、ジスルフィド化合物、チオン化合物を含有させることができる。
メルカプト化合物はメルカプト置換複素芳香族化合物が好ましく、この具体例としては、2-メルカプトベンズイミダゾール、2-メルカプトベンズオキサゾール、2-メルカプトベンゾチアゾール、2-メルカプト-5- メチルベンズイミダゾール、6-エトキシ-2- メルカプトベンゾチアゾール、2,2'- ジチオビス- ベンゾチアゾール、3-メルカプト-1,2,4- トリアゾール、4,5-ジフェニル-2- イミダゾールチオール、2-メルカプトイミダゾール、1-エチル-2- メルカプトベンズイミダゾール、2-メルカプトキノリン、8-メルカプトプリン、2-メルカプト-4(3H)- キナゾリノン、7-トリフルオロメチル-4- キノリンチオール、2,3,5,6-テトラクロロ-4- ピリジンチオール、4-アミノ-6- ヒドロキシ-2- メルカプトピリミジンモノヒドレート、2-アミノ-5- メルカプト-1,3,4- チアジアゾール、3-アミノ-5- メルカプト-1,2,4- トリアゾール、4-ヒドキロシ-2- メルカプトピリミジン、2-メルカプトピリミジン、4,6-ジアミノ-2- メルカプトピリミジン、2-メルカプト-4- メチルピリミジンヒドロクロリド、3-メルカプト-5- フェニル-1,2,4- トリアゾール、2-メルカプト-4- フェニルオキサゾールなどが挙げられる。これらのメルカプト化合物の使用量は乳剤層中に銀1 モル当たり0.0001〜1.0 モルが好ましく、さらに好ましくは0.001 〜0.3 モルの量である。
【００４６】
画像形成層には、可塑剤および潤滑剤として多価アルコール( 例えば、米国特許第2,960,404 号に記載された種類のグリセリンおよびジオール) 、米国特許第2,588,765 号および同第3,121,060 号に記載の脂肪酸またはエステル、英国特許第955,061 号に記載のシリコーン樹脂などを用いることができる。
画像形成層である感光性層には色調改良、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が、好ましい染料としてはアントラキノン染料( 特開平5-341441号、特開平5-165147号記載の化合物など) 、アゾメチン染料( 特開平5-341441号記載の化合物) 、インドアニリン染料( 特開平5-289227号、特開平5-341441号、特開平5-165147号記載の化合物など) およびアゾ染料( 特開平5-341441号記載の化合物など) が挙げられる。これらの化合物の使用量は感材１m^２当たり1 μg 以上1g以下の範囲で用いることが好ましい。
【００４７】
アンチハレーション層を感光性層に対して光源から遠い側に設けることができる。アンチハレーション層は所望の波長範囲での最大吸収が0.3 以上2 以下であることが好ましく、さらに好ましくは0.5 以上2 以下の露光波長の吸収であり、かつ処理後の可視領域においての吸収が0.001 以上0.5 未満であることが好ましく、さらに好ましくは0.001 以上0.3 未満の光学濃度を有する層であることが好ましい。単独の染料としては特開昭59-56458号、特開平2-216140号、同7-13295 号、同7-11432 号、米国特許第5,380,635 号、特開平2-68539 号、同3-24539 号などを用いることができる。処理で消色する染料として特開昭52-139136 号、同53-132334 号、同56-501480 号、同57-16060号、同57-68831号、同57-101835 号、同59-182436 号、特開平7-36145 号、同7-199409号、特公昭48-33692号、同50-16648号、特公平2-41734 号、米国特許第4,088,497 号、同第4,283,487 号、同第4,548,896 号、同第5,187,049 号に記載のものを好ましく用いることができる。
【００４８】
感光層の最外層に保護層を設けることも好ましい。保護層用のバインダーとしてはアクリル系、スチレン系、アクリル／スチレン系、塩化ビニル系、塩化ビニリデン系のポリマーラテックスが好ましく用いられ、具体的にはアクリル樹脂系のVONCORT R3370 、4280、Nipol Lx857 、メチルメタクリレート／２−エチルヘキシルアクリレート／ヒドロキシエチルメタクリレート／スチレン／アクリル酸コポリマー、塩化ビニル樹脂のNipol G576、塩化ビニリデン樹脂のアロンD5071 が好ましく用いられる。これらの層の中にイソシアネート等の架橋剤を添加するのもより好ましい。保護層の好ましい塗布量は０．５〜１０g/m^２、より好ましくは１〜７g/m^２、さらに好ましくは１．５〜５g/m^２である。
さらに保護層中にマット剤を添加するのがより好ましい。無機系のマット剤としては、二酸化ケイ素、チタンおよびアルミニウムの酸化物、亜鉛およびカルシウムの炭酸塩、バリウムおよびカルシウムの硫酸塩、カルシウムおよびアルミニウムのケイ酸塩など、有機系のマット剤としては、セルロースエステル類、ポリメチルメタクリレート、ポリスチレンまたはポリジビニルベンゼンおよびこれらのコポリマーなどの有機重合体のマット剤が挙げられる。これらのマット剤を２種以上併用してもよい。好ましいマット剤の平均粒径は、１〜１０μm 、好ましい添加量は、５〜４００mg／m^２、特に１０〜２００mg／m^２の範囲である。
【００４９】
本発明における熱現像画像記録材料（熱現像感材）は、支持体の一方の側に少なくとも1 層のハロゲン化銀乳剤を含む感光性層のような画像形成層（感光層）を有し、他方の側にバック層（バッキング層）を有する、いわゆる片面画像記録材料であることが好ましい。
本発明においてバック層は、所望の波長範囲での最大吸収が0.3 以上2 以下であることが好ましく、さらに好ましくは0.5 以上2 以下の吸収であり、かつ処理後の可視領域においての吸収が0.001 以上0.5 未満であることが好ましく、さらに好ましくは0.001 以上0.3 未満の光学濃度を有する層であることが好ましい。また、バック層に用いるハレーション防止染料の例としては前述のアンチハレーション層と同じである。
【００５０】
帯電調整剤として導電性の結晶性金属酸化物又はその複合酸化物微粒子を添加して表面抵抗率を１０^１２以下にすることも好ましい。導電性の結晶性酸化物又はその複合酸化物の微粒子としては体積抵抗率が１０^７ Ωcm以下、より好ましくは１０^５ Ωcm以下のものが望ましい。またその粒子サイズは０．０１〜０．７μｍ、特に０．０２〜０．５μｍであることが望ましい。
これらの導電性の結晶性金属酸化物あるいは複合酸化物の微粒子の製造方法については特開昭５６−１４３４３０号公報の明細書に詳細に記載されている。即ち、第１に金属酸化物微粒子で焼成により作製し、導電性を向上させる異種原子の存在下で熱処理する方法、第２に焼成により金属酸化物微粒子を製造するときに導電性を向上させる為の異種原子を共存させる方法、第３に焼成により金属微粒子を製造する際に雰囲気中の酸素濃度を下げて、酸素欠陥を導入する方法等が容易である。金属原子を含む例としてはＺｎＯに対してＡｌ、Ｉｎ等、ＴｉＯ₂ に対してはＮｂ、Ｔａ等、ＳｎＯ₂ に対してはＳｂ、Ｎｂ、ハロゲン元素等があげられる。異種原子の添加量は０．０１〜３０ｍｏｌ％の範囲が好ましいが０．１〜１０ｍｏｌ％であれば特に好ましい。これらのうちＳｂを添加したＳｎＯ₂ 複合金属酸化物微粒子が最も好ましい。
【００５１】
バック面マット化のために微粒子を添加するのも好ましい。微粒子は無機微粒子（シリカ、アルミナ、炭酸カルシウム、チタニア、ジルコニアなど）、有機微粒子（ＰＭＭＡ、ＰＳｔおよびこれらの架橋体など）が挙げられる。本発明では、特開平3-109542号公報２頁左下欄８行目〜３頁右上欄４行目に記載された多孔性のマット剤、特開平4-127142号公報３頁右上欄７行目〜５頁右下欄４行に記載されたアルカリで表面修飾したマット剤、特開平6-118542号公報の段落番号「０００５」から「００２６」に記載された有機重合体のマット剤を用いることがより好ましい。好ましい粒径は０．３μm 以上１０μm 以下、より好ましくは１μm 以上８μm 以下、さらに好ましくは３μm 以上７μm 以下である。好ましい添加量は１〜５０mg／ｍ^２ 、より好ましくは２〜３０mg／ｍ^２ 、さらに好ましくは３〜１５mg／ｍ^２ である。これにより達成される好ましいベック平滑度（ＪＩＳ Ｐ８１１９）は、２０００秒以下であり、より好ましくは１０秒〜２０００秒である。
【００５２】
これらのバック層は親水性コロイドをバインダ−としてもよく、疎水性ポリマーをバインダーとしてもよい。
親水性ポリマーとして最も好ましいものはゼラチンである。親水性ポリマ−を用いる場合、より強固な密着性を付与するために、感光層と同じ下塗を行った上にバック層を塗設することも好ましい。
疎水性ポリマー層のバインダーとしてはポリメチルメタクリレート、エチルアクリレート等の（メタ）アクリル酸エステルポリマー、ポリエチレン等のオレフィン系ポリマー、スチレン系ポリマー、ウレタン系ポリマー、ブタジエン等のゴム系ポリマーなどが用いられる。この層は１層でも２層以上でもよい。さらにバック層には硬膜剤を用いても良い。硬膜剤の例としては、米国特許4,281,060 号、特開平6-208193号などに記載されているポリイソシアネート類、米国特許4,791,042 号などに記載されているエポキシ化合物類、特開昭62-89048号などに記載されているビニルスルホン系化合物類などが用いられる。
【００５３】
バック層の最外層に保護層を設けても良い。保護層用の全バインダー量は０．２〜５．０g ／m^２、より好ましくは０．５〜３．０g ／m^２の範囲が好ましい。バック層用のバインダーとしては、アクリル系、オレフィン系、塩化ビニリデン系のポリマーラテックスが用いられ、具体的にはアクリル樹脂系のジュリマーET-410、セビアンA-4635、ポリゾールF410など、オレフィン樹脂系のケミパールS120、塩化ビニリデン系のL502、アロンD7020 などが好ましい。
【００５４】
バック層にはフッ素系界面活性剤を含有させることが好ましい。好ましい含フッ素界面活性剤としては、炭素数４以上（好ましくは４以上１５以下）のフルオロアルキル基、フルオロアルケニル基、またはフルオロアリール基を有し、イオン性基としてアニオン基（スルホン酸（塩）、硫酸（塩）、カルボン酸（塩）、リン酸（塩））、カチオン基（アミン塩、アンモニウム塩、芳香族アミン塩、スルホニウム塩、ホスホニウム塩）、ベタイン基（カルボキシアミン塩、カルボキシアンモニウム塩、スルホアミン塩、スルホアンモニウム塩、ホスホアンモニウム塩、）またはノニオン基（置換、無置換のポリオキシアルキレン基、ポリグリセリル基またはソルビタン残基）を有する界面活性剤が挙げられる。これらの含フッ素界面活性剤は特開昭49-10722号、英国特許第1,330,356 号、米国特許第4,335,201 号、同4,347,308 号、英国特許第1,417,915 号、特開昭55-149938 号、同58-196544 号、英国特許第1,439,402 号などに記載されている。これらの含フッ素界面活性剤は、２種以上混合してもよい。
含フッ素界面活性剤の使用量は画像記録材料の１m^２当たり０．０００１〜１ｇであればよいが、より好ましくは０．０００２〜０．２５ｇ、特に好ましいのは０．０００３〜０．１ｇである。
【００５５】
バック層の最外層には滑り剤を用いるのがより好ましい。滑り剤の代表的なものとしてはシリコーン系滑り剤、高級脂肪酸系、アルコール系、酸アミド系滑り剤、金属石けん、エステル系、エーテル系滑り剤、タウリン系滑り剤等がある。好ましく用いられる滑り剤の具体例としては、セロゾール５２４（主成分カルナバワックス）、ポリロンＡ，３９３，Ｈ−４８１（主成分ポリエチレンワックス）、ハイミクロンＧ−１１０（主成分エチレンビスステアリン酸アマイド）、ハイミクロンＧ−２７０（主成分ステアリン酸アマイド）（以上、中京油脂（株）製）などがある。
滑り剤の使用量は添加層のバインダー量の０．１〜５０重量％であり、より好ましくは０．５〜３０重量％であることが好ましい。
【００５６】
このようなバック層は、１層でも多層でもよく、各層の厚みは０．０２〜１０μｍ、より好ましくは０．１〜７μｍの範囲が好ましく、これらの層の全厚みは０〜５μｍが好ましい。
これらのバック層、下塗層の塗工は、ディップコート法、エアーナイフコート法、カーテンコート法、ローラーコート法、ワイヤーバーコート法、グラビアコート法、等により塗布することができる。これらは単層ずつ塗布しても２層以上同時塗布しても良い。
このようにして調製した熱現像感材は使用する際に裁断するが、ロール状で使用しても良く、シート状で使用しても良い。いずれの場合も好ましい幅（熱現像機を通過させるときに処理方向と直交する方向）は４０cm以上１５０cm以下、より好ましくは４５cm以上１００cm以下、さらに好ましくは５０cm以上８０cm以下である。
【００５７】
本発明の熱現像画像記録材料はいかなる方法で露光されても良いが、露光光源としてレーザー光が好ましい。本発明によるレーザー光としては、ガスレーザー、YAG レーザー、色素レーザー、半導体レーザーなどが好ましい。また、半導体レーザーと第２高調波発生素子などを用いることもできる。
本発明の熱現像画像記録材料は露光時のヘイズが低く、干渉縞が発生しやすい傾向にある。この干渉縞発生防止技術としては、特開平5-113548号などに開示されているレーザー光を画像記録材料に対して斜めに入光させる技術や、WO95/31754号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。
本発明の熱現像画像記録材料を露光するにはSPIE vol.169 Laser Printing 116-128 頁(1979)、特開平4-51043 号、WO95/31754号などに開示されているようにレーザー光が重なるように露光し、走査線が見えないようにすることが好ましい。
本発明の熱現像画像記録材料はいかなる方法で熱現像されても良いが、通常イメージワイズに露光した熱現像画像記録材料を、上述の方法により昇温して現像される。
【００５８】
以下に本発明において規定する物性の測定法について述べる。なお、測定法（１）及び（２）については、図面に基づいて述べる。
（１) 熱現像後の四辺の端部の各反り量の測定（図１および２参照）
▲１▼４辺を５０ｃｍに裁断した熱現像感材を所定の条件で熱現像した後、図１に示すように、この熱現像後の感材１の４辺の端部を１ｃｍ幅のスリット位置２でスリットする。スリットすると、このスリットによりスリット片４の辺８はたわみ（波打ち）が消失し、図２のように円弧状となる。
▲２▼図２に示すように、スリット片４の辺３の反対側の辺８の一端ａを定規６の一側に合わせ、スリット片の他端ｂと定規との間の隙間（距離）５を計る。同様にｂ端を定規に合わせａ端との隙間を計る。これらの値の平均値を反り量（ｍｍ／５０ｃｍ）とする。これを４辺にわたって測定する。
なお、感材が５０ｃｍ以外の時は、各辺を１ｃｍ幅でスリット後上記方法によって反り量（Ａ）を測定し、下記式に従って補正する。
反り量(mm ／50cm) ＝Ａ(mm)×｛５０／感材の辺長(cm)｝
【００５９】
（２) 熱現像後の四辺の端部の各波打ち量の測定（図３参照）
▲１▼４辺を５０ｃｍに裁断した熱現像感材を所定の条件で熱現像し、この熱現像後の感材１を水平で平滑な台７の上に感光層を上にして置く。
▲２▼３分後に、４辺毎に波打ち量を下記のように測定する。
発生した波打ち１つ毎に、その最大高さ（Ｈ_imm）と幅（Ｗ_imm）を定規、ノギス等を用いて計測する。
下記式に従いＨ_i(mm)×Ｗ_i(mm)を４辺毎に積算し、四辺の端部の各波打ち量（ｍｍ^２ ／５０ｃｍ）とする。
【００６０】
【数１】

【００６１】
なお、感材が５０ｃｍ以外の時は、上記方法によって波打ち量（Ｂ）を測定し、下記式に従って補正する。
波打ち量(mm^２／50cm) ＝Ｂ(mm^２) ×｛５０／感材の辺長(cm)｝
【００６２】
（３) １２０℃３０秒の熱寸法変化
▲１▼幅方向（ＴＤ）５cm×長手方向（ＭＤ）２５cmに熱現像感材を切り出しＭＤ方向用サンプルとする。幅方向（ＴＤ）２５cm×長手方向（ＭＤ）５cmに同様に切り出しＴＤ方向用サンプルとする。
▲２▼これらを２５℃６０％RH下で１２時間調湿後、２０ｃｍ間隔の孔を開けピンゲージを用い測長する（これをＬ₁(mm) とする）。
▲３▼これらを１２０℃に加熱したヒートブロックに３０秒接触させ、無張力下で加熱する。
▲４▼これらを２５℃６０％ＲＨ下に１２時間調湿後、ピンゲージを用いて寸法を測定する( これをＬ₂(mm) とする) 。
▲５▼下記式に従い１２０℃３０秒の熱寸法変化とする。
１２０℃３０秒の熱寸法変化(％)＝１００×（Ｌ₂−Ｌ₁）／Ｌ₁
【００６３】
（４) １２０℃３０秒の熱現像後の吸水寸法変化率
▲１▼幅方向（ＴＤ）５cm×長手方向（ＭＤ）２５cmに熱現像感材を切り出しＭＤ方向用サンプルとする。幅方向（ＴＤ）２５cm×長手方向（ＭＤ）５cmに同様に切り出しＴＤ方向用サンプルとする。
▲２▼これらを２５℃４０％RH下で１２時間調湿し、、２０ｃｍ間隔の孔を開けピンゲージを用い測長する（これをＬ₀(mm) とする）。
▲３▼これらを２５℃７５％RHに設置した熱現像機で、熱現像（１２０℃に加熱したヒートブロックに３０秒接触させ、無張力下で加熱）する。
▲４▼２５℃７５％RHで、熱現像後３分後の寸法（Ｌ₃）と１２０分後の寸法(Ｌ₁₂₀)を、ピンゲージを用いて測定する。
▲５▼下記式に従い１２０℃３０秒の熱現像後の吸水寸法変化を求める。
１２０℃３０秒の熱現像後の吸水寸法変化率（％)
＝｛１００×（Ｌ₁₂₀−Ｌ₀）／Ｌ₀｝−｛１００×（Ｌ₃−Ｌ₀）／Ｌ₀｝
【００６４】
【実施例】
以下、本発明を実施例によってさらに詳細に説明するが、本発明はこれに限定されない。
【００６５】
実施例−１
（１）支持体（ベース）の作製
テレフタル酸とエチレングリコ−ルを用い、常法に従いＩＶ（固有粘度）＝０．６６（フェノ−ル／テトラクロルエタン＝６／４( 重量比) 中２５℃で測定）のＰＥＴを得た。これをペレット化した後１３０℃で４時間乾燥し、３００℃で溶融後Ｔ型ダイから押し出して急冷し、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−ルを用い３．３倍に縦延伸、ついでテンタ−で４．５倍に横延伸を実施した。この時の温度はそれぞれ、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−のチャック部をスリットした後、両端にナ−ル加工を行い、４．８kg/cm^２で巻き取った。このようにして、幅２．４ｍ、長さ３５００ｍ、厚み１２０μm のロ−ルを得た。
【００６６】
（２）下塗層
支持体（ベース）の両面に、表１に示すように下記組成の下塗り層（ａ−１）又は（ａ−２）を塗設後、下塗り層（ｂ）を順次塗布し、それぞれ１８０℃、４分間乾燥した。（ａ−１）又は（ａ−２）の乾燥後の塗布膜厚は表１に記載の値になるように、（ｂ）の塗布膜厚は１．０μm になるように調製した。

【００６７】
(2-２） 下塗り層（ａ−２）
SBR ポリマーラテックス
スチレン／ブタジエン／ヒドロキシエチルメタクリレート／ジビニルベンゼン
＝６７／３０／２．５／０．５（重量％） １６０重量部
２，４−ジクロロ−６−ヒドロキシ−ｓ−トリアジン ４重量部
マット剤（ポリスチレン、平均粒径２．４μm ） ３重量部
(2-３） 下塗り層（ｂ）
アルカリ処理ゼラチン
（Ｃａ++含量３０ppm 、ゼリー強度２３０ｇ） ５０mg/m^２
【００６８】
（３) バック層
上記下塗り層（ａ−１）または（ａ−２）と下塗り層（ｂ）を塗布した上の一方の側に下記導電層と保護層を順次塗布し、それぞれ１８０℃、４分間乾燥して、バック層／下塗り層のついたＰＥＴ支持体を作製した。
(3-１） 導電層（２５℃２５％ＲＨでの表面抵抗率１０^９ Ω）
ジュリマーET-410（日本純薬（株）製）：Tg＝５２℃ ３８mg/m^２
ＳｎＯ_２ ／Ｓｂ（９／１重量比、平均粒子径０．２５μm ） １２０mg/m^２
マット剤（ポリメチルメタクリレート、平均粒子径５μm ） ７mg/m^２
デナコールＥＸ−６１４Ｂ（ナガセ化成工業（株）製） １３mg/m^２
(3-２） 保護層
ケミパールS-120 （三井石油化学（株）製）：Tg＝７７℃ ５００mg/m^２
スノーテックス−Ｃ（日産化学（株）製） ４０mg/m^２
デナコールＥＸ−６１４Ｂ（ナガセ化成工業（株）製） ３０mg/m^２
【００６９】
（４）熱処理
バック層／下塗り層のついたＰＥＴ支持体を表１に記載の温度、張力、時間で加熱ゾーン内を搬送させながら熱処理を行った。
【００７０】
【表１】

【００７１】
【表２】

【００７２】
【表３】

【００７３】
【表４】

【００７４】
（５）画像形成層（感光層）
バック層の反対側の下塗り層の上に下記画像形成層および保護層を順次塗布し、それぞれ６５℃３分間乾燥し熱現像画像感材を得た。
(5-１） ハロゲン化銀粒子の調製
水７００mlにフタル化ゼラチン１１g および臭化カリウム３０mg、チオスルホン酸ナトリウム１０mgを溶解して温度３５℃にてｐＨを５．０に合わせた後、硝酸銀１８．６g を含む水溶液１５９mlと臭化カリウムを１モル／リットルで含む水溶液をpAg ７. ７に保ちながらコントロールドダブルジェット法で６．５分間かけて添加した。ついで、硝酸銀５５．４ｇを含む水溶液４７６mlと臭化カリウムを１モル／リットルで含むハロゲン塩水溶液pAg ７．７に保ちながらコントロールダブルジェット法で３０分間かけて添加した後、４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデン１ｇを添加し、さらにｐＨを下げて凝集沈降させ脱塩処理をした。その後、フェノキシエタノール０. １ｇを加え、ｐＨ５. ９、pAg ８．２に調整し臭化銀粒子（平均サイズ０．１２μｍ、投影面積直径変動係数８％、（100 ）面比率８８％の立方体粒子）の調製を終えた。
こうして得たハロゲン化銀粒子を６０℃に昇温して銀１モル当たりチオスルホン酸ナトリウム８．５×１０^−４モルを添加し、１２０分間熟成した後４０℃に急冷したのち、１×１０^−５モルの色素Ｓ−１、５×１０^−５モルの２- メルカプト- ５- メチルベンゾイミダゾールおよび５×１０^−５モルのＮ−メチル−Ｎ’−｛３−（メルカプトテトラゾリル）フェニル｝ウレアを添加し３０℃に急冷してハロゲン化銀乳剤を得た。
【００７５】
【化２】

【００７６】
(5-２） 有機酸銀分散物の調製
ステアリン酸４．４g 、ベヘン酸３９．４g 、蒸留水７７０mlを９０℃で撹拌しながら1N-NaOH 水溶液１０３mlを添加し２４０分反応させ、７５℃に降温した。次いで、硝酸銀１９．２g の水溶液１１２．５mlを４５秒かけて添加し、そのまま２０分間放置し、３０℃に降温した。その後、吸引濾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。こうして得た固形分にヒドロキシプロピルメチルセルロース１０wt％水溶液１００g を添加し、さらに総重量２７０g となるように水を加えたのち、自動乳鉢にて素分散し有機酸銀粗分散物を得た。この有機酸銀粗分散物をナノマイザー（ナノマイザ（株）製）を用い衝突時の圧力１０００kg/cm^３で分散し有機酸銀分散物を得た。こうして得た有機酸銀分散物に含まれる有機酸銀粒子は平均短径０. ０４μm 、平均長径０．８μm 、変動係数３０％の針状粒子であった。
(5-３） 還元剤分散物の調製
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１００g とヒドロキシプロピルセルロース５０g に水８５０g を添加し良く混合してスラリーとした。平均直径０. ５mmのジルコニアビーズ８４０ｇを用意してスラリーと一緒にベッセルに入れ、分散機（１／４Ｇサンドグラインダーミル：アイメックス（株）製）にて５時間分散し還元剤分散物を得た。
【００７７】
(5-4) 有機ポリハロゲン化物分散物の調製
トリブロモメチルフェニルスルホン５０g とヒドロキシプロピルメチルセルロース１０g に水９４０g を添加し良く混合してスラリーとした。平均直径０. ５nmのジルコニアビーズ８４０ｇを用意してスラリーと一緒にベッセルに入れ、分散機（１／４Ｇサンドグラインダーミル：アイメックス（株）製）にて５時間分散し有機ポリハロゲン化物分散物を得た。
(5-5) 画像形成層塗布液の調製
上記で得た有機酸銀分散物１００g 、還元剤分散物２０g 、有機ポリハロゲン化物分散物１５g 、ＬＡＣＳＴＡＲ3307B(大日本インキ化学工業（株）製；SBR ラテックス；Ｔｇ１３℃）４９wt％ ４０ｇ、ＭＰ−２０３（クラレ（株）製；ポリビニルアルコール）１０wt％水溶液２０ｇ、ハロゲン化銀乳剤２０ｇ、ヒドラジン化合物（一般式（Ｈ）の化合物）１wt% メタノール溶液８ml、さらに水１００ｇを加えてよく混合し画像形成層塗布液を調製した。
この塗布液を塗布銀量１．５g/m^２、ポリマーラテックスの固形分の塗布量が５．７g/m^２になるように塗布した。
【００７８】
（６）保護層
(6-１） 保護層塗布液の調製
下記塗布液をポリマーラテックスの固形分が２g/m^２になるように、上記感光層の上に塗布した。
４０wt% のポリマーラテックス（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／メタアクリル酸＝５９／９／２６／５／１の共重合体；Ｔｇ４７℃）５００ｇに、Ｈ₂Ｏ ２６２ｇを加え、造膜助剤として、ベンジルアルコール１４ｇ、下記化合物−２２．５ｇ、セロゾール５２４（中京油脂（株）製）３．６ｇ、下記化合物−３１２ｇ、下記化合物−４ １ｇ、下記化合物−５ ２ｇ、下記化合物−６ ７．５ｇ、マット剤として、平均粒径３μm のポリメチルメタクリレート微粒子３．４ｇを順次加えて、さらにＨ₂Ｏを加えて、１０００ｇとし、粘度５ｃｐ（２５℃）、ｐＨ＝３．４（２５℃）の塗布液を調製した。
【００７９】
【化３】

【００８０】
（７）感材の熱現像・コンタクト露光・評価
得られた熱現像感材について、上記方法に従って、１２０℃３０秒の熱寸法変化、１２０℃３０秒後の熱現像後の吸水寸法変化率を求めた。
さらに、上記方法で調製した熱現像感材に１０％の平網画像を露光し、５０cm×５０cmに裁断後、表２〜４に示した条件で熱現像を行った。熱現像感材は、各水準とも、それぞれ表２〜４に記載の各条件により、室温から定温まで昇温し、定温部３０秒後、定温から室温まで降温した。熱現像後、４辺の反り量、波打ち量を前記の方法で測定し表２〜４に示した。この後密着露光用プリンターでＰＳ版にコンタクト露光した。定法に従ってＰＳ版を現像し、網点画像のくっつきの発生している箇所（網点がつぶれて連続している所）の面積を目視で測定し、結果を表２及び４に示した（網点不良率）。
【００８１】
表１及び表２において、比較例−１の結果からわかるように、支持体の両面に下塗層としてポリ塩化ビニリデンの層を有さず、本発明に規定する熱処理条件以外で熱処理を行い、熱寸法変化及び吸水寸法変化率が本発明に規定する範囲にない熱現像感光材料を、前記する熱現像条件以外の条件で熱現像すると、熱現像後の反り量、波打ち量がともに大きくなり、高い網点不良率が示すように、焼きボケ故障が発生しており好ましくない。
一方、本発明−１〜８に示すように、本発明に規定する熱現像感光材料を前記する熱現像方法で熱現像すると、熱現像後の反り量、波打ち量がともに小さく、網点不良率が低くなり、焼きボケ故障が発生しないことがわかる。
なお、下塗層にポリ塩化ビニリデンを有さない本発明−２に示す熱現像感光材料を用いて熱現像を行った場合、および本発明−８に示すように昇温と降温の速度が大きい熱現像方法によって熱現像を行った場合は、本発明に規定する熱現像感光材料を前記する熱現像方法によって熱現像を行った場合に比べて、いずれも一部の辺で反り量、波打ち量が若干大きいが、比較例−１と比べると網点不良率には全く問題がなく、焼きボケ故障は発生しない。また、本発明−９〜１４に示すように、熱現像を、前記する搬送張力分布の範囲にすることにより搬送張力を均一にして行うと、熱現像後の反り量、波打ち量とも、さらに小さく、網点不良率が低く、好ましいことがわかる。
【００８２】
【発明の効果】
本発明の熱現像写真感光材料は、通常の用途のみでなく、印刷用感材として用いても、熱現像後の平面性が良好であり焼きボケ故障が発生しないという優れた効果を奏する。
【図面の簡単な説明】
【図１】本発明における四辺の反り及び反り量測定のためのスリット位置を示す模式図である。
【図２】本発明における反り量測定法を示す説明図である。
【図３】本発明における四辺の波打ち状態を感材の端面で示す模式図である。
【符号の説明】
１ 熱現像後の感材
２ スリット位置
３、８ 辺
４ スリット片
５ ａ端で合わせたときの隙間
６ 定規
７ 水平な台
ａ、ｂ 辺８の一端
Ｈ_i 発生したある波打ちｉの最大高さ
Ｈ_i+1 発生したある波打ちｉ＋１の最大高さ
Ｈ_i+2 発生したある波打ちｉ＋２の最大高さ
Ｗ_i 発生したある波打ちｉの幅
Ｗ_i+1 発生したある波打ちｉ＋１の幅
Ｗ_i+2 発生したある波打ちｉ＋２の幅[0001]
BACKGROUND OF THE INVENTION
The present invention is a photothermographic material for heat development.To chargeRelated.
[0002]
[Prior art]
Conventionally, silver halide photographic light-sensitive materials are subjected to wet development using a developer after photographing. However, this method has the following problems and has been desired to be improved.
(1) Since development, bleaching, fixing, and drying are performed, time is required for development processing.
(2) Since a plurality of tanks containing developer are required, the developing machine cannot be reduced in size and weight.
(3) Replenishment of developer, disposal, and cleaning of the developing tank are required.
In order to improve this, development by heat at 80 to 150 ° C. as described in US Pat. No. 3,152,904, US Pat. No. 3,457,075, Japanese Patent Publication No. 43-4921, Japanese Patent Publication No. 43-4924, etc. A photographic material using a method (hereinafter sometimes abbreviated as heat development) is proposed. As an example of this, there is a method in which a precursor of a developer is previously contained in the photosensitive layer, which is decomposed by heat to form a developer, and then developed. In such a thermal development system, the development process can be performed in a short time only by applying heat, and the developing machine can be downsized. Furthermore, there is a feature that there is no worry about replenishment and disposal of the developer.
However, when this type of photosensitive material was used as a printing photosensitive material, image distortion and color misregistration of four plates (blue, green, red, black) occurred due to dimensional changes that occurred during thermal development. In order to solve this problem, Japanese Patent Application Laid-Open No. 8-21547 discloses a technique for heat-treating a support with low tension. However, in this method, after the heat development treatment, after the heat-developable photosensitive material is contact-exposed on the printing plate (PS plate), a failure called “burning” occurs on the PS plate, and improvement is desired. It was. This burn-out failure is a out-of-focus failure that occurs when the surface of the photosensitive material after heat development deteriorates and floats locally. Was significantly generated at 45 cm or more).
[0003]
[Problems to be solved by the invention]
The present invention is a photothermographic material that has good flatness after heat development and does not cause burnout failure.ChargeThe purpose is to provide.
[0004]
[Means for Solving the Problems]
  That is, the present invention
(1)The tension is 0 when the support is 140 ° C or higher and 200 ° C or lower. kg / m More than 5 kg / m It has a polyethylene terephthalate film that has been heat-treated for 20 seconds to 5 minutes at the following.Photothermographic material for heat developmentThe thermal dimensional change at 120 ° C. for 30 seconds is −0.05% or more and + 0.05% or less in the width direction in the longitudinal direction, and depends on the following heat development conditions.Each warp amount at the ends of the four sides after heat development is 0 mm / 50 cm or more and 4 mm / 50 cm or less,TheEach wavy amount at the end of the four sides after heat development is 0 mm²/ 50cm to 500mm²/ 50cm or lessThe heat development conditions are as follows:A heat-developable photographic material.
Thermal development conditions
    Temperature increase rate at the heat developing machine inlet: 1 ° C / second or more and 15 ° C / second or less
    Temperature and time of the constant temperature part: 80 to 140 ° C. and 10 to 120 seconds
    Temperature distribution in the width direction of the constant temperature part: 0 ° C or higher and 10 ° C or lower
    Temperature decreasing rate at the heat developing machine outlet: -8 ° C / second or more and -1 ° C / second or less,
(2) The water absorption dimensional change rate after heat development at 120 ° C. for 30 seconds is 0% / 2 hours or more and 0.025% / 2 hours or less in the longitudinal width direction. Photothermographic material,as well as
(3)SaidEach layer of polyvinylidene chloride resin on both sides of the support is 0.5 μm to 10 μmsoItem (1) characterized by being appliedOr (2)The photothermographic material described in the above item
Is to provide.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
One side of the outer periphery of the heat-developable photographic light-sensitive material after heat development (hereinafter sometimes abbreviated as heat-sensitive material or heat-developable material) is slit with a width of 1 cm, and the opposite side of the slit is a straight ruler. If you place it along the ruler, a gap will be created between it and the ruler. A value obtained by standardizing the gap interval by the length of the slit side is called a warp amount. When the amount of warping is large, the outer periphery of the photosensitive material becomes like an arc, and the deflection becomes longer due to the longer circumference, which causes blurring.
The amount of each warp of the four sides of the heat-developable photosensitive material of the present invention is preferably 0 mm / 50 cm to 4 mm / 50 cm, more preferably 0 mm / 50 cm to 3 mm / 50 cm, and still more preferably 0 mm / 50 cm to 2 mm / 50 cm or less.
[0006]
As a result, each wavy amount at the ends of the four sides after the heat development is 0 mm.² / 50cm to 500mm² / 50 cm or less, more preferably 0 mm² / 50cm or more 400mm² / 50 cm or less, more preferably 0 mm² / 50cm to 300mm² / 50 cm or less. The amount of waviness is the measurement of the wavy raised part that occurs when the heat-developable heat-sensitive material is placed on a flat surface. The height (mm) and width (mm) are measured for each wavy part. Multiplying, adding this for each side, and standardizing by the length of each side.
By controlling the amount of warpage and the amount of waviness, it is possible to satisfactorily perform contact exposure to the PS plate without causing blurring.
[0007]
There are two ways to achieve such a heat-developable heat-developable material: (1) improvement of heat-developable light-sensitive material and (2) improvement of heat-development method. (1) or (2) alone is effective. It is most preferable to carry out a combination of these. This will be described in detail below.
[0008]
(1) Improvement of heat-developable photosensitive material
The point in improving the heat-developable photosensitive material is to reduce the dimensional change during heat development. That is, the thermal dimensional change at 120 ° C. for 30 seconds is preferably −0.05% or more and + 0.05% or less in both the longitudinal direction (hereinafter referred to as MD) and the width direction (hereinafter referred to as TD), and −0.03% or more and +0. 0.04% or less is more preferable, and -0.02% or more and + 0.04% or less is more preferable.
Although the heat-developable photosensitive material is rolled in the heat developing machine, the heat-developable photosensitive material is partially stretched because the nip force of the roll is not uniform over the entire width. Such non-uniformity of the nip force is particularly remarkable at the ends of the four sides of the heat-developable photosensitive material. For this reason, an end part is extended and it is easy to change into a wave shape.
[0009]
In order to produce such a heat-developable photosensitive material having a small thermal dimensional change, it is important to reduce the thermal dimensional change of the support. This is achieved by heat-treating while being conveyed.
The heat treatment temperature of the support is preferably 140 ° C. or higher and 200 ° C. or lower, more preferably 145 ° C. or higher and 180 ° C. or lower, and further preferably 150 ° C. or higher and 165 ° C. or lower. The conveying tension is preferably 0 kg / m or more and 5 kg / m or less, more preferably 0 kg / m or more and 4 kg / m or less, and further preferably 0.5 kg / m or more and 3 kg / m or less. The heat treatment time is preferably from 20 seconds to 5 minutes, more preferably from 30 seconds to 3 minutes, and further preferably from 45 seconds to 2 minutes. Such heat treatment may be carried out anywhere after the support film formation and before the photosensitive layer coating, but more preferably after the back layer coating and before the photosensitive layer coating.
[0010]
Supports are polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), vinyl polymers such as polycarbonate (PC), polyacrylate, syndiotactic polystyrene (SPS), and celluloses such as cellulose triacetate (TAC). A polyethylene terephthalate film in which the polymer is heat-treated with a thermoplastic resin can be used, but PET, PEN, PC, SPS and their composites (laminates, blends) are preferable, and PET is particularly preferable. is there. The preferable thickness of these supports is preferably from 80 μm to 200 μm, more preferably from 95 μm to 180 μm, and even more preferably from 100 μm to 140 μm.
[0011]
Furthermore, it is preferable that the rate of change in water absorption after heat development at 120 ° C. for 30 seconds is 0% / 2 hours or more and 0.025% / 2 hours or less, more preferably 0% / 2 hours or more and 0.020% / 2 hours or less. Hereinafter, it is more preferably 0% / 2 hours or more and 0.015% / 2 hours or less.
The water in the photosensitive layer and the support instantly evaporates with heat development, but when it is left at room temperature, it absorbs water again. As a result, the heat-developable photosensitive material expands in volume and its dimensions increase with time. The water absorption dimensional change rate after heat development at 120 ° C. refers to this change rate. That is, the water absorption speed is obtained from the difference between the dimensions immediately after heat development (after 3 minutes) and the dimensions after a predetermined time (2 hours). If this is too large, it means that water is drastically absorbed, and just like the paper absorbs water and undulations occur, the heat-developable material is likely to generate undulations.
[0012]
In the heat-developable photosensitive material having such a water absorption dimensional change rate, a layer of polyvinylidene chloride resin is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less, more preferably 1 on both sides of the support. This can be achieved by applying 5 μm or more and 3 μm or less. Furthermore, it is preferable to use a copolymer for polyvinylidene chloride, and the amount of vinylidene chloride residue contained is preferably 70 to 99.9% by weight, more preferably 85 to 99% by weight, and still more preferably 90 to 99% by weight. %. Examples of copolymer components other than vinylidene chloride include methacrylic acid and esters thereof, methyl methacrylic acid and esters thereof, and acrylonitrile. The weight average molecular weight of these copolymers is preferably from 5,000 to 100,000, more preferably from 8,000 to 80,000, and even more preferably from 10,000 to 45,000. The method of applying the polyvinylidene chloride resin on the support may be either a method in which the polyvinylidene chloride resin is dissolved in an organic solvent or a method in which an aqueous dispersion latex is applied, but the latter is more preferable.
[0013]
(2) Improvement of heat development method
It is more preferable to improve the heat development method. The point here is to equalize the transport tension in the heat developing machine (to reduce the transport tension distribution). That is, the conveyance tension at the left and right ends and the center is made uniform. The distribution of the conveyance tension can be measured by the following method.
1) The photosensitive material is cut into a heat developing machine width × 50 cm length. This is divided into three equal parts in the width direction.
2) This is simultaneously inserted into the heat developing machine and subjected to heat development processing.
3) Measure the time until the sensitive material is carried out. When there is a distribution in the transport tension, the unloading time of the photosensitive material transported through the portion having a large transport tension is short, and the transport time is long in a weak place.
Therefore, the conveyance time ratio {(longest time−shortest time) / shortest time} is equal to the distribution of conveyance tension ratio (conveyance tension distribution), and the preferable conveyance tension distribution is 0 or more and 0.5 or less, more preferably 0. It is not less than 0.2 and more preferably not less than 0 and not more than 0.1.
[0014]
As a result of the analysis of the present invention, it has become clear that the conveyance tension distribution is generated by the following mechanism. In addition, a conveyance roll consists of two or more rolls, and conveys through a photosensitive material between these rolls.
1) When the transport roll is heated to the heat development temperature, it linearly expands. Both ends of the transport roll are fixed, and this elongation is absorbed by the deflection of the roll.
2) If it bends upwards (in a state where the center of the roll is lifted with respect to the sensitive material), the transport tension at the center is lowered. On the other hand, if it bends downwards (a state where both ends of the roll are lifted with respect to the sensitive material), the conveyance tension at the end is lowered.
[0015]
Therefore, in the present invention, the point is to equalize the transport tension by the following method.
B) Providing stretch absorbers at both ends of the transport roll
-Provide play in the bearings of the roll so that the roll is displaced in the width direction.
A preferable play amount is 0.1 to 1 mm, more preferably 0.2 to 0.9 mm, and still more preferably 0.3 to 0.8 mm.
B) Use deformation rolls to offset roll deformation.
-When a roll deform | transforms convexly upwards, the roll (crown roll) whose diameter of a center part is larger than both ends is used.
A preferable convex amount (increase rate of the diameter of the central portion with respect to both ends of the crown roll) is 1 to 10%, more preferably 2 to 9%, and further preferably 3 to 8%.
-When the roll is deformed downward, use a roll (reverse crown roll) in which the diameters at both ends are larger than the center.
A preferable convex amount (increase rate of the diameter of both end portions with respect to the central portion of the reverse crown roll) is 1 to 10%, more preferably 2 to 9%, and further preferably 3 to 8%.
Such a transfer tension distribution is likely to occur when the transfer width (TD width) is wide as apparent from the above mechanism, and the present invention is effective when the width is 30 cm or more, more effective when the width is 45 cm or more, and 55 cm. This is even more effective.
[0016]
Furthermore, it is also preferable to control the temperature increase / decrease rate at the inlet and outlet of the heat developing machine. That is, rapid thermal expansion of the heat-developable photosensitive material due to rapid temperature increase and rapid contraction of the heat-developable photosensitive material due to rapid temperature decrease tend to cause warping and undulation of the edges of the four sides. The rate of temperature rise at the inlet is preferably 1 ° C./second or more and 15 ° C./second or less, more preferably 2 ° C./second or more and 10 ° C./second or less, and further preferably 2 ° C./second or more and 6 ° C./second or less. Such setting of the temperature raising rate can be achieved by separately providing a heater at the inlet of the heat developing machine and increasing the temperature continuously or stepwise.
[0017]
Thereafter, thermal development is carried out. The preferred thermal development temperature is 80 ° C. or higher and 140 ° C. or lower, more preferably 90 ° C. or higher and 130 ° C. or lower, and further preferably 100 ° C. or higher and 125 ° C. or lower. At this time, the amount of warpage and waviness should be reduced by setting the temperature distribution in the width direction to 0 ° C. or more and 10 ° C. or less, more preferably 0 ° C. or more and 5 ° C. or less, more preferably 0 ° C. or more and 3 ° C. or less. Can do. At this time, the temperature at both ends of the heat developing machine tends to be lower than that at the center, so the set temperature of the heater is 1 to 20 ° C. at the end (1 to 20 cm, more preferably 3 to 15 cm, more preferably 5 to 10 cm). It is preferable to be higher than the central part, more preferably 2 ° C or higher and 15 ° C or lower, more preferably 5 ° C or higher and 15 ° C or lower. The heat development time is preferably from 10 seconds to 120 seconds, more preferably from 14 seconds to 60 seconds, and even more preferably from 18 seconds to 40 seconds. Such heat development may be performed by radiant heat from a panel heater, or may be performed in direct contact with the heater.
[0018]
The temperature lowering at the exit of the heat machine after heat development is preferably performed at -8 ° C / second or more and -1 ° C / second or less, more preferably -5 ° C / second or more and -1.5 ° C / second or less, Preferably, it is -3 ° C / second or more and -1.5 ° C / second or less. Such a temperature decrease can be performed by surrounding the outlet and the like with a heat insulating material or by actively heating with a heater.
[0019]
The method for producing the photosensitive layer and the back layer of the heat-developable photosensitive material of the present invention will be described below. The heat-developable photosensitive material of the present invention has an image forming layer (photosensitive layer) containing an organic silver salt, a reducing agent and a photosensitive silver halide on a support, and at least one protective layer is provided on the image forming layer. Is provided. On the opposite side of the photosensitive layer, a back layer for providing antistatic properties, slip properties, antihalation properties, mat properties, scratch resistance, and the like is provided. If necessary, an undercoat layer may be provided between the back layer, the photosensitive layer and the support.
[0020]
The photosensitive layer is obtained by dispersing silver halide, chemical sensitizer, organic silver salt, reducing agent, ultra-high contrast agent, sensitizing dye, antifoggant, plasticizer and the like in a binder.
As the binder, acrylic resin, vinyl acetate resin, polyester resin, polyurethane resin, rubber resin, vinyl chloride resin, vinylidene chloride resin, and polyolefin resin are preferable, and more specifically, methyl methacrylate / ethyl methacrylate / methacrylic acid. Copolymer, methyl methacrylate / 2-ethylhexyl acrylate / hydroxyethyl methacrylate / styrene / acrylic acid copolymer, styrene / butadiene / acrylic acid copolymer, styrene / butadiene / divinylbenzene / methacrylic acid copolymer, methyl methacrylate / vinyl chloride / acrylic acid copolymer, chloride Examples include vinylidene / ethyl acrylate / acrylonitrile / methacrylic acid copolymers, more preferably styrene / butadiene. Polymer latex (LACSTAR3307B, Nipol Lx430, 435) is preferably used. These weight average molecular weights are preferably 5,000 to 1,000,000, more preferably about 10,000 to 100,000. Further, a hydrophilic polymer such as polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and the like may be added to the binder in the range of 20% by weight or less of the total binder.
The amount of binder applied is 0.2-30 g / m², More preferably 1.0 to 15 g / m²The range of is preferable.
[0021]
The silver halide may be any of silver chloride, silver chlorobromide, and silver iodochlorobromide. The grain size of silver halide is preferably small for the purpose of keeping the cloudiness after image formation low, specifically 0.20 μm or less, more preferably 0.01 μm or more and 0.15 μm or less, and further preferably 0.02 μm or more and 0.12 μm. The following is good. Examples of the shape of the silver halide grains include cubes, octahedrons, tabular grains, spherical grains, rod-shaped grains, and potato grains. In the present invention, cubic grains and tabular grains are particularly preferred. When tabular silver halide grains are used, the average aspect ratio is preferably 100: 1 to 2: 1, more preferably 50: 1 to 3: 1. Further, grains having rounded corners of silver halide grains can be preferably used. The surface index (Miller index) on the outer surface of the photosensitive silver halide grain is not particularly limited, but the spectral sensitizing efficiency when adsorbed by the spectral sensitizing dye is high and the proportion of the {100} surface is high. preferable. The ratio is preferably 50% or more, more preferably 65% or more, and further preferably 80% or more. Methods for forming these silver halides are well known in the art, and for example, the methods described in Research Disclosure No. 17029 of June 1978 and US Pat. No. 3,700,458 can be used.
[0022]
The silver halide grains preferably contain a metal or metal complex of Group VII or Group VIII (Group 7 to Group 10) of the periodic table, more preferably rhodium, rhenium, ruthenium, osnium, iridium. It is. These are described in JP-A-7-225449, JP-A-63-2042, JP-A-1-285941, JP-A-2-20852, JP-A-2-20855, and the like. The amount of these compounds added is 1 × 10 5 per mole of silver halide.^-9Mol ~ 1 × 10^-5The molar range is preferred, particularly preferably 1 × 10^-8Mol ~ 1 × 10^-6Is a mole.
[0023]
The silver halide grains may contain metal atoms such as cobalt, iron, nickel, chromium, palladium, platinum, gold, thallium, copper, lead, and hexacyanogen for cobalt, iron, chromium, and ruthenium compounds. Metal complexes can be preferably used. These addition amounts are 1 x 10 per mole of silver halide.^-9~ 1x10^-4Mole is preferred. In order to contain the above metal, it can be added in the form of a metal salt in the form of a single salt, a double salt or a complex salt at the time of preparing the particles.
[0024]
The silver halide emulsion is preferably chemically sensitized, and sulfur sensitizing method, selenium sensitizing method, tellurium sensitizing method, noble metal sensitizing method and the like can be used. For sulfur sensitization, sulfur compounds, thiosulfates, thioureas, thiazoles, rhodanines, etc. in gelatin can be used, and the addition amount is 10 per mol of silver halide.^-7-10^-2Is a mole. As the selenium sensitizer, compounds described in JP-B Nos. 44-15748, 43-13489, JP-A-4-25832, JP-A-4-109240, JP-A-4-324855 and the like can be used. The tellurium sensitizer is preferably a compound represented by the general formulas (II), (III) and (IV) in JP-A-5-313284. The amount of selenium and tellurium sensitizers used is 10 per mole of silver halide.^-8-10^-2Is a mole. Examples of the noble metal sensitizer include gold, platinum, palladium, iridium and the like, but gold sensitization is particularly preferable, and 10 per mol of silver halide.^-7-10^-2Use moles.
[0025]
In the present invention, reduction sensitization can be used. As specific compounds of the reduction sensitization method, ascorbic acid, thiourea dioxide, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like can be used.
[0026]
The organic silver salt is an arbitrary organic substance containing a source capable of reducing silver ions, and particularly a silver salt of a long-chain fatty carboxylic acid (having 10 to 30 carbon atoms, preferably 15 to 28 carbon atoms). Moreover, the silver salt of a compound containing a mercapto group or a thione group, and these derivatives can also be used. The shape of the organic silver salt is not particularly limited, but needle crystals having a short axis and a long axis are preferred. The minor axis is preferably 0.01 μm or more and 0.20 μm or less, and the major axis is 0.10 μm or more and 5.0 μm or less.
For the purpose of obtaining fine particles having no aggregation, an organic silver salt is used as a solid fine particle dispersion using a dispersant.
[0027]
The method of dispersing the organic silver salt in the form of solid fine particles can be carried out by a known finer means (for example, a ball mill, a sand mill, a jet mill, a high pressure homogenizer) in the presence of a dispersion aid. As a dispersant, polyacrylic acid, acrylic acid copolymer, maleic acid copolymer, maleic acid monoester copolymer, acryloylmethylpropanesulfonic acid copolymer, carboxymethyl starch, carboxymethylcellulose, alginic acid, pectic acid, Polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropylcellulose, hydroxypropylmethylcellulose, gelatin, anionic surfactant described in JP-A-52-92716, WO88 / 04794, and compound described in JP-A-9-179243 are appropriately selected. Can be used. Organic silver salt has a silver content of 0.1 to 5 g / m² Is more preferable, and more preferably 1 to 3 g / m² It is. The amount ratio of silver halide to organic acid silver is preferably 0.01 to 0.5 mol, more preferably 0.02 to 0.3 mol, and more preferably 0.03 to 0.25 mol with respect to 1 mol of the organic silver salt. Particularly preferred.
[0028]
It is preferable to include a reducing agent for the organic silver salt, phenidone, hydroquinone and catechol, and a hindered phenol reducing agent are preferable, a hindered phenol reducing agent is particularly preferable, and specifically, bisphenol and chromanol. The reducing agent is preferably contained in an amount of 5 to 50% (mole), more preferably 10 to 40% (mole), based on 1 mol of silver.
[0029]
In order to improve the image quality, it is preferable to add a toning agent. Preferred toning agents include cyclic imides, cobalt complexes, mercaptans, phthalazinones, phthalazinone derivatives, phthalazines, phthalazine derivatives, more preferred are phthalazinones, phthalazinone derivatives, phthalazines, phthalazine derivatives, and particularly preferred are phthalazines, phthalazine derivatives. It is. The color toning agent is preferably contained in an amount of 0.1 to 50% (mole) per mole of silver, more preferably 0.5 to 20% (mole), on the surface having the image forming layer.
[0030]
In order to obtain a high-contrast image, a substituted alkene derivative represented by the general formula (1), a substituted isoxazole derivative represented by the general formula (2), a specific acetal compound represented by the general formula (3), and A hydrazine derivative is preferably used.
[0031]
[Chemical 1]

[0032]
R in the general formula (1)¹ , R² , R³ Each independently represents a hydrogen atom or a substituent, and Z represents an electron-withdrawing group or a silyl group. In the general formula (1), R¹ And Z, R² And R³ , R¹ And R² Or R³ And Z may be bonded to each other to form a cyclic structure. R in the general formula (2)⁴ Represents a substituent. In the general formula (3), X and Y each independently represent a hydrogen atom or a substituent, and A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, a hetero group A ring oxy group, a heterocyclic thio group, or a heterocyclic amino group is represented. In the general formula (3), X and Y, or A and B may be bonded to each other to form a cyclic structure.
[0033]
More preferable among the compounds represented by the general formula (1) is that Z represents a cyano group, a formyl group, an acyl group, an alkoxycarbonyl group, an imino group, or a carbamoyl group, and R¹ Represents an electron-withdrawing group or an aryl group, and R² Or R³ Any one of these is a hydrogen atom, and the other is a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, or It is a compound representing a heterocyclic group. More preferred are Z and R¹ Form a non-aromatic 5- to 7-membered cyclic structure, and R² Or R³ Any one of these is a hydrogen atom, and the other is a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, Or it is a compound showing a heterocyclic group. At this time, R¹ As Z that forms a non-aromatic cyclic structure together with it, an acyl group, a carbamoyl group, an oxycarbonyl group, a thiocarbonyl group, a sulfonyl group and the like are preferable.¹ Preferred examples include an acyl group, a carbamoyl group, an oxycarbonyl group, a thiocarbonyl group, a sulfonyl group, an imino group, an imino group substituted with an N atom, an acylamino group, and a carbonylthio group.
[0034]
In the general formula (2), the substituent R⁴ Is an electron-withdrawing group or an aryl group, preferably a substituted or unsubstituted phenyl group having 0 to 30 carbon atoms, cyano group, alkoxycarbonyl group, carbamoyl group, heterocyclic group, most preferably cyano group, heterocyclic group Group or alkoxycarbonyl group.
[0035]
The substituent represented by X and Y in the general formula (3) is preferably a group having 1 to 40 carbon atoms, more preferably a group having 1 to 30 carbon atoms, more preferably a cyano group or an alkoxycarbonyl group. , Carbamoyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, acylthio group, acylamino group, thiocarbonyl group, formyl group, imino group, imino group substituted with N atom, heterocyclic group or any electron withdrawing group A substituted phenyl group and the like; It is also preferred when X and Y are bonded to each other to form a non-aromatic carbocycle or non-aromatic heterocycle. The formed cyclic structure is preferably a 5- to 7-membered ring, and the total carbon number is preferably 1 to 40, and more preferably 3 to 30. As X and Y forming the cyclic structure, an acyl group, a carbamoyl group, an oxycarbonyl group, a thiocarbonyl group, a sulfonyl group, an imino group, an imino group substituted with an N atom, an acylamino group, a carbonylthio group and the like are preferable.
In the general formula (3), A and B each independently represent an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, a heterocyclic thio group, a heterocyclic oxy group, or a heterocyclic amino group. These total carbon numbers are 1-30. A and B are more preferably bonded to each other to form a cyclic structure, and a 5- to 7-membered non-aromatic heterocycle is more preferable. In this case, an example in which A and B are linked (-A-B-) is, for example, -O- (CH₂)₂-O-, -O- (CH₂)_Three-O-, -S- (CH₂)₂-S-, -S- (CH₂)_Three-S-, -S-ph-S-, -N (CH_Three)-(CH₂)₂-O-, -N (CH_Three)-(CH₂)₂-S-, -O- (CH₂)₂-S-, -O- (CH₂)_Three-S-, -N (CH_Three) -Ph-O-, -N (CH_Three) -Ph-S-, -N (ph)-(CH₂)₂-S- etc.
[0036]
The compounds represented by the general formula (1) to the general formula (3) have groups such as an alkylthio group, an arylthio group, a thiourea group, a thioamide group, a mercapto heterocyclic group, and a triazole group that adsorb to silver halide. It may be incorporated.
The compounds represented by the general formula (1) to the general formula (3) are those in which a ballast group such as an alkyl group, an aralkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, and an alkylphenoxy group is incorporated. More preferred.
[0037]
The compounds represented by the general formula (1) to the general formula (3) include a cationic group (a group containing a quaternary ammonio group or a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom). ), A group containing an ethyleneoxy group or a propyleneoxy group repeating unit, a (alkyl, aryl, or heterocyclic) thio group, or a dissociable group that can be dissociated by a base (carboxy group, sulfo group, acylsulfamoyl group, Carbamoylsulfamoyl group, etc.) are more preferred, especially those containing a repeating unit of ethyleneoxy group or propyleneoxy group, or (alkyl, aryl, or heterocyclic) thio group Is preferred.
The amount of the compound represented by the general formula (1) to the general formula (3) is 1 × 10 with respect to 1 mol of silver.^-6~ 1 mole is preferred, 1 × 10^-5~ 5x10^-1Mole is more preferred, 2 × 10^-5~ 2x10^-1Mole is most preferred.
[0038]
It is also preferable to use a hydrazine derivative represented by the following general formula (H) as a super-high contrast agent.
R¹²-NA¹ -NA² -(G¹ )_m1-R¹¹     (H)
Where R¹²Represents an aliphatic group, an aromatic group or a heterocyclic group. The aliphatic group is preferably an alkyl group having 1 to 30 carbon atoms, an alkenyl group, or an alkynyl group. The aromatic group is a monocyclic or condensed ring aryl group, and examples thereof include a phenyl group and a naphthyl group. The heterocyclic group is a monocyclic or condensed ring, saturated or unsaturated, aromatic or non-aromatic heterocyclic group. Among these, an aryl group or an alkyl group is preferable.
[0039]
R¹²Preferred as a substituent that may have is R¹²When represents an aliphatic group, an alkyl group, an aryl group, a heterocyclic group, an amino group, an acylamino group, a sulfonamide group, a ureido group, a sulfamoylamino group, an imide group, a thioureido group, a phosphoric acid amide group, a hydroxy group Group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group (including salts thereof), (alkyl, aryl, or heterocyclic) thio group, sulfo group (Including salts thereof), sulfamoyl groups, halogen atoms, cyano groups, and nitro groups are preferred. R¹²Represents an aromatic group or a heterocyclic group, an alkyl group (including an active methylene group), an aralkyl group, a heterocyclic group, a substituted amino group, an acylamino group, a sulfonamide group, a ureido group, a sulfamoylamino group, an imide Group, thioureido group, phosphoric acid amide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group (including salts thereof), (alkyl, An aryl or heterocyclic ring) thio group, sulfo group (including salts thereof), sulfamoyl group, halogen atom, cyano group, nitro group and the like are preferable.
[0040]
R¹¹Represents a hydrogen atom or a blocking group. The blocking group is an aliphatic group (specifically, an alkyl group, an alkenyl group, an alkynyl group), an aromatic group (monocyclic or condensed aryl group), a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, or Represents a hydrazino group. R¹¹May be substituted, and examples of substituents include R¹²And those exemplified above.
A¹, A²Are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group having 20 or less carbon atoms, or an arylsulfonyl group (preferably a phenylsulfonyl group or a sum of Hammett's substituent constants of −0.5 or more. A phenylsulfonyl group substituted with or an acyl group (preferably a benzoyl group, a benzoyl group substituted with a Hammett's sum of substituent constants of -0.5 or more, or an aliphatic acyl group). . m1 is 0 or 1, and when m1 is 0, R1¹¹Represents an aliphatic group, an aromatic group, or a heterocyclic group. A¹, A²Is most preferably a hydrogen atom.
G¹Is -CO-, -COCO-, -C (= S)-, -SO₂-, -SO-, -PO (R¹³) -Group (R¹³Is R¹¹Selected from the same range as defined for¹¹And may be different. ) Or an iminomethylene group.
[0041]
The hydrazine derivative of the general formula (H) may incorporate a group that is adsorptive to silver halide (alkylthio group, arylthio group, thiourea group, thioamide group, mercaptoheterocyclic group, triazole group, etc.). .
R in general formula (H)¹¹Or R¹²May contain a ballast group such as an alkyl group, an aralkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, and an alkylphenoxy group, or a polymer described in JP-A-1-100530.
R in general formula (H)¹¹Or R¹²Is a group containing a cationic group (a group containing a quaternary ammonio group or a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom), an ethyleneoxy group or a propyleneoxy group, A (alkyl, aryl, or heterocycle) thio group or a dissociable group (carboxy group, sulfo group, acylsulfamoyl group, carbamoylsulfamoyl group, etc.) that can be dissociated by a base may be contained.
The addition amount of the hydrazine derivative that can be used in the present invention is 1 × 10 4 per mol of silver.^-6~ 1 x10^-2Moles are preferred, 1 × 10^-5~ 5 x10^-3Mol is more preferred, 2 × 10^-5~ 5 x10^-3Mole is most preferred.
[0042]
Further, in the present invention, in order to form a super high contrast image, a high contrast accelerator can be used in combination with the super high contrast agent. For example, amine compounds described in US Pat. No. 5,545,505, hydroxamic acids described in US Pat. No. 5,545,507, acrylonitriles described in US Pat. No. 5,545,507, hydrazine compounds described in US Pat. No. 5,558,983, and new compounds described in Japanese Patent Application Laid-Open No. 9-297368. -Mu salts and the like can be used.
[0043]
As the sensitizing dye in the present invention, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes and the like can be used.
Examples of spectral sensitization to red light include He-Ne lasers, red semiconductor lasers, and red light sources such as LEDs as disclosed in JP-A-54-18726, JP-A-6-75322, and JP-A-7-287338. The compounds described in JP-B-55-39818, JP-A-62-284343, and JP-A-7-287338 can be used.
For semiconductor laser light sources in the wavelength range of 750-1400 nm, it can be advantageously sensitized by various known dyes including cyanine, merocyanine, styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes.
Further, US Pat. Nos. 5,510,236, 3,871,887, JP-A-2-96131, and JP-A-59-48753 can be preferably used as the dye forming J-band.
The amount of the sensitizing dye used in the present invention is 10 per mole of silver halide in the photosensitive layer.^-6~ 1 mole is preferred, 10^-4~Ten^-1Mole is more preferred.
[0044]
Antifoggants, stabilizers and stabilizer precursors are the thiazonium salts described in U.S. Pat.Nos. 2,131,038 and 2,694,716, Azaindene described in U.S. Pat.Nos. 2,886,437 and 2,444,605, Mercuric salts described in U.S. Pat.No. 3,287,135 Urazole, U.S. Pat.No. 3,235,652 sulfocatechol, British Patent No.623,448 oxime, nitrone, nitroindazole, U.S. Pat. Valent metal salts, thiuronium salts described in US Pat. No. 3,220,839, and palladium, platinum and gold salts described in US Pat. Nos. 2,566,263 and 2,597,915, halogens described in US Pat. Substituted organic compounds such as triazines described in U.S. Pat.Nos. 4,128,557 and 4,137,079, 4,138,365 and 4,459,350. And phosphorus compounds described in US Pat. No. 4,411,985.
Moreover, you may contain benzoic acids for the purpose of fog prevention and high sensitivity. Examples of preferable benzoic acid structures include compounds described in U.S. Pat. Nos. 4,784,939, 4,152,160, JP-A-9-329865, JP-A-9-329864, JP-A-9-281638, and the like. It is preferable to add to the layer. This addition amount is preferably 1 μmol or more and 2 mol or less, and more preferably 1 mmol or more and 0.5 mol or less per 1 mol of silver.
[0045]
In the present invention, a mercapto compound, a disulfide compound, and a thione compound can be contained in order to suppress or promote development and control development, to improve spectral sensitization efficiency, and to improve storage stability before and after development. .
The mercapto compound is preferably a mercapto-substituted heteroaromatic compound, and specific examples thereof 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-pyridine Thiol, 4-amino-6-hydroxy-2-mercaptopyrimidine 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 hydro Examples include chloride, 3-mercapto-5-phenyl-1,2,4-triazole, 2-mercapto-4-phenyloxazole. The amount of these mercapto compounds used is preferably 0.0001 to 1.0 mol, more preferably 0.001 to 0.3 mol, per mol of silver in the emulsion layer.
[0046]
In the image forming layer, polyhydric alcohols (for example, glycerin and diol of the kind described in US Pat. No. 2,960,404), fatty acids or esters described in US Pat. Nos. 2,588,765 and 3,121,060 are used as plasticizers and lubricants. Silicone resins described in British Patent No. 955,061 can be used.
Various dyes and pigments can be used for the photosensitive layer which is an image forming layer from the viewpoint of improving color tone and preventing irradiation, but preferred anthraquinone dyes (Japanese Patent Laid-Open Nos. 5-341441 and 5-165147). And the like), azomethine dyes (compounds described in JP-A-5-341441), indoaniline dyes (compounds described in JP-A-5-289227, JP-A-5-341441, JP-A-5-165147, etc.) and And azo dyes (such as compounds described in JP-A-5-341441). The amount of these compounds used is 1m of sensitive material.²It is preferably used in the range of 1 μg or more to 1 g or less.
[0047]
The antihalation layer can be provided on the side far from the light source with respect to the photosensitive layer. The antihalation layer preferably has a maximum absorption in a desired wavelength range of 0.3 or more and 2 or less, more preferably an absorption of an exposure wavelength of 0.5 or more and 2 or less, and an absorption in the visible region after processing of 0.001 or more. It is preferably less than 0.5, more preferably a layer having an optical density of 0.001 or more and less than 0.3. As a single dye, JP-A-59-56458, JP-A-2-216140, JP-A-7-13295, JP-A-111432, U.S. Pat.No. 5,380,635, JP-A-2-68539, JP-A-3-24539 Etc. can be used. JP-A 52-139136, 53-132334, 56-501480, 57-16060, 57-68831, 57-101835, 59-182436 JP-A-7-36145, JP-A-7-199409, JP-B-48-33692, JP-A-50-16648, JP-B-2-41734, U.S. Pat.Nos. 4,088,497, 4,283,487, 4,548,896, Those described in US Pat. No. 5,187,049 can be preferably used.
[0048]
It is also preferable to provide a protective layer as the outermost layer of the photosensitive layer. As the binder for the protective layer, acrylic, styrene, acrylic / styrene, vinyl chloride, and vinylidene chloride polymer latexes are preferably used. Specifically, acrylic resin-based VONCORT R3370, 4280, Nipol Lx857, methyl A methacrylate / 2-ethylhexyl acrylate / hydroxyethyl methacrylate / styrene / acrylic acid copolymer, a vinyl chloride resin Nipol G576, and a vinylidene chloride resin Aron D5071 are preferably used. It is more preferable to add a crosslinking agent such as isocyanate into these layers. A preferable coating amount of the protective layer is 0.5 to 10 g / m.², More preferably 1-7 g / m²More preferably, 1.5 to 5 g / m²It is.
Furthermore, it is more preferable to add a matting agent in the protective layer. Examples of inorganic matting agents include silicon dioxide, titanium and aluminum oxides, zinc and calcium carbonates, barium and calcium sulfates, calcium and aluminum silicates, and organic matting agents such as cellulose. Mention may be made of organic polymer matting agents such as esters, polymethyl methacrylate, polystyrene or polydivinylbenzene and copolymers thereof. Two or more of these matting agents may be used in combination. The average particle size of the preferable matting agent is 1 to 10 μm, and the preferable addition amount is 5 to 400 mg / m.², Especially 10-200 mg / m²Range.
[0049]
The heat-developable image recording material (heat-developable photosensitive material) in the present invention has an image forming layer (photosensitive layer) such as a photosensitive layer containing at least one silver halide emulsion on one side of the support, A so-called single-sided image recording material having a back layer (backing layer) on the other side is preferable.
In the present invention, the back layer preferably has a maximum absorption in a desired wavelength range of 0.3 or more and 2 or less, more preferably 0.5 or more and 2 or less, and an absorption in the visible region after treatment of 0.001 or more. It is preferably less than 0.5, more preferably a layer having an optical density of 0.001 or more and less than 0.3. Examples of the antihalation dye used for the back layer are the same as those of the antihalation layer described above.
[0050]
A conductive crystalline metal oxide or a composite oxide fine particle thereof is added as a charge control agent to make the surface resistivity 10¹²It is also preferable to make it below. As the conductive crystalline oxide or composite oxide fine particles, the volume resistivity is 10⁷ Ωcm or less, more preferably 10⁵ The thing below Ωcm is desirable. The particle size is preferably 0.01 to 0.7 μm, particularly preferably 0.02 to 0.5 μm.
The method for producing fine particles of these conductive crystalline metal oxides or composite oxides is described in detail in the specification of JP-A-56-143430. That is, firstly, a method in which metal oxide fine particles are produced by firing and heat-treated in the presence of different atoms to improve conductivity, and second, in order to improve conductivity when producing metal oxide fine particles by firing. The method of coexisting these different atoms, and the third method of introducing oxygen defects by reducing the oxygen concentration in the atmosphere when producing metal fine particles by firing are easy. Examples containing metal atoms include Zn, Al, In, etc., TiO₂ Nb, Ta, etc., SnO₂ In contrast, Sb, Nb, halogen elements and the like can be mentioned. The amount of the heteroatom added is preferably in the range of 0.01 to 30 mol%, but particularly preferably 0.1 to 10 mol%. Of these, SnO added with Sb₂ The composite metal oxide fine particles are most preferable.
[0051]
It is also preferable to add fine particles for matting the back surface. The fine particles include inorganic fine particles (silica, alumina, calcium carbonate, titania, zirconia, etc.), and organic fine particles (PMMA, PSt, and cross-linked products thereof). In the present invention, the porous matting agent described in JP-A-3-109542, page 2, lower left column, line 8 to page 3, upper right column, line 4, JP-A-4-127142, page 3, upper right column, line 7 Use the matting agent surface-modified with alkali described in page 4, right lower column, line 4, and the organic polymer matting agent described in paragraphs “0005” to “0026” of JP-A-6-118542. Is more preferable. The preferred particle size is 0.3 μm or more and 10 μm or less, more preferably 1 μm or more and 8 μm or less, and further preferably 3 μm or more and 7 μm or less. A preferred addition amount is 1 to 50 mg / m.² , More preferably 2-30 mg / m² More preferably 3-15 mg / m² It is. The preferable Beck smoothness (JIS P8119) achieved thereby is 2000 seconds or less, more preferably 10 seconds to 2000 seconds.
[0052]
In these back layers, a hydrophilic colloid may be used as a binder, and a hydrophobic polymer may be used as a binder.
The most preferred hydrophilic polymer is gelatin. In the case of using a hydrophilic polymer, it is also preferable to coat the back layer after applying the same undercoat as the photosensitive layer in order to give stronger adhesion.
As the binder of the hydrophobic polymer layer, (meth) acrylic acid ester polymers such as polymethyl methacrylate and ethyl acrylate, olefin polymers such as polyethylene, styrene polymers, urethane polymers, rubber polymers such as butadiene, and the like are used. This layer may be a single layer or two or more layers. Further, a hardener may be used for the back layer. Examples of hardeners include polyisocyanates described in US Pat. No. 4,281,060, JP-A-6-208193, epoxy compounds described in US Pat. No. 4,791,042, and JP-A 62-89048. The vinyl sulfone compounds described in the above are used.
[0053]
A protective layer may be provided on the outermost layer of the back layer. Total binder amount for protective layer is 0.2-5.0 g / m², More preferably 0.5 to 3.0 g / m²The range of is preferable. As the binder for the back layer, acrylic, olefinic, and vinylidene chloride polymer latexes are used. Specifically, acrylic resin-based Julimer ET-410, Sebian A-4635, Polysol F410, and other olefin resin-based latexes are used. Chemipearl S120, vinylidene chloride-based L502, Aron D7020 and the like are preferable.
[0054]
The back layer preferably contains a fluorinated surfactant. Preferred fluorine-containing surfactants have a fluoroalkyl group, fluoroalkenyl group, or fluoroaryl group having 4 or more (preferably 4 or more and 15 or less) carbon atoms, and an anionic group (sulfonic acid (salt)) as an ionic group , Sulfuric acid (salt), carboxylic acid (salt), phosphoric acid (salt), cationic group (amine salt, ammonium salt, aromatic amine salt, sulfonium salt, phosphonium salt), betaine group (carboxyamine salt, carboxyammonium salt) , Sulfoamine salts, sulfoammonium salts, phosphoammonium salts) or nonionic groups (substituted, unsubstituted polyoxyalkylene groups, polyglyceryl groups or sorbitan residues). These fluorine-containing surfactants are disclosed in JP-A-49-10722, British Patent 1,330,356, U.S. Pat.Nos. 4,335,201, 4,347,308, British Patent 1,417,915, JP-A-55-149938, 58-196544. And British Patent No. 1,439,402. Two or more of these fluorine-containing surfactants may be mixed.
The amount of fluorine-containing surfactant used is 1 m of the image recording material.²It may be 0.0001 to 1 g per unit, more preferably 0.0002 to 0.25 g, and particularly preferably 0.0003 to 0.1 g.
[0055]
It is more preferable to use a slipping agent for the outermost layer of the back layer. Typical examples of the slip agent include silicone-based slip agents, higher fatty acid-based, alcohol-based, acid amide-based slip agents, metal soaps, ester-based, ether-based slip agents, and taurine-based slip agents. Specific examples of the slip agent preferably used include cellosol 524 (main component carnauba wax), polylon A, 393, H-481 (main component polyethylene wax), high micron G-110 (main component ethylenebisstearic acid amide), Hymicron G-270 (main component amide of stearic acid) (manufactured by Chukyo Yushi Co., Ltd.).
The amount of the slip agent to be used is 0.1 to 50% by weight, more preferably 0.5 to 30% by weight, based on the amount of the binder in the additive layer.
[0056]
Such a back layer may be a single layer or multiple layers, and the thickness of each layer is preferably 0.02 to 10 μm, more preferably 0.1 to 7 μm, and the total thickness of these layers is preferably 0 to 5 μm.
These back layers and undercoat layers can be applied by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and the like. These may be applied as single layers or simultaneously as two or more layers.
The heat-developable photosensitive material thus prepared is cut when used, but may be used in a roll form or a sheet form. In any case, the preferred width (direction perpendicular to the processing direction when passing through the heat developing machine) is 40 cm or more and 150 cm or less, more preferably 45 cm or more and 100 cm or less, and further preferably 50 cm or more and 80 cm or less.
[0057]
The heat-developable image recording material of the present invention may be exposed by any method, but laser light is preferred as the exposure light source. As the laser beam according to the present invention, a gas laser, a YAG laser, a dye laser, a semiconductor laser and the like are preferable. A semiconductor laser and a second harmonic generation element can also be used.
The heat-developable image recording material of the present invention has a low haze upon exposure and tends to generate interference fringes. As this interference fringe generation prevention technology, a laser beam disclosed in Japanese Patent Laid-Open No. 5-11548 etc. is incident obliquely on the image recording material, and a multimode disclosed in WO95 / 31754 etc. Methods using lasers are known and these techniques are preferably used.
To expose the heat-developable image recording material of the present invention, laser light overlaps as disclosed in SPIE vol. 169 Laser Printing, pages 116-128 (1979), JP-A-4-51043, WO95 / 31754, etc. It is preferable to expose the scanning line so that the scanning line is not visible.
The heat-developable image recording material of the present invention may be heat-developed by any method. Usually, the heat-developable image recording material exposed imagewise is heated and developed by the above-described method.
[0058]
The physical property measuring method defined in the present invention will be described below. Measurement methods (1) and (2) will be described with reference to the drawings.
(1) Measurement of the amount of warpage at the ends of the four sides after heat development (see FIGS. 1 and 2)
(1) After thermally developing a heat-developable photosensitive material having four sides cut to 50 cm under predetermined conditions, as shown in FIG. 1, the edges of the four sides of the photosensitive material 1 after this thermal development are slits having a width of 1 cm. Slit at position 2. When the slit is made, the side 8 of the slit piece 4 is not bent (waved) by the slit, and becomes arcuate as shown in FIG.
(2) As shown in FIG. 2, one end a of the side 8 opposite to the side 3 of the slit piece 4 is aligned with one side of the ruler 6, and the gap (distance) between the other end b of the slit piece and the ruler. Measure 5. Similarly, align the b end with a ruler and measure the gap with the a end. The average value of these values is the amount of warpage (mm / 50 cm). This is measured over four sides.
When the photosensitive material is other than 50 cm, the amount of warpage (A) is measured by the above method after slitting each side with a width of 1 cm, and corrected according to the following formula.
Warpage (mm / 50cm) = A (mm) x {50 / side length of sensitive material (cm)}
[0059]
(2) Measurement of the amount of waviness at the ends of the four sides after heat development (see Fig. 3)
{Circle around (1)} A heat-developable photosensitive material having four sides cut to 50 cm is heat-developed under predetermined conditions, and the heat-sensitive material 1 after heat development is placed on a horizontal and smooth base 7 with the photosensitive layer facing upward.
{Circle around (2)} After 3 minutes, measure the amount of undulation every four sides as follows.
For each wave that occurs, its maximum height (H_imm) and width (W_imm) using a ruler, caliper, etc.
H according to the following formula_i(mm) × W_i(mm) is integrated for every four sides, and each undulation amount (mm² / 50 cm).
[0060]
[Expression 1]

[0061]
When the sensitive material is other than 50 cm, the waving amount (B) is measured by the above method and corrected according to the following formula.
Wave amount (mm²/ 50cm) = B (mm²) X {50 / side length of sensitive material (cm)}
[0062]
(3) Thermal dimension change at 120 ° C for 30 seconds
(1) A heat-developable photosensitive material is cut out in the width direction (TD) 5 cm × longitudinal direction (MD) 25 cm to obtain a sample for MD direction. A sample in the width direction (TD) 25 cm × longitudinal direction (MD) 5 cm is similarly cut out as a sample for the TD direction.
(2) After adjusting the humidity at 25 ° C. and 60% RH for 12 hours, open holes at intervals of 20 cm and measure using a pin gauge (L₁(mm).
(3) These are brought into contact with a heat block heated to 120 ° C. for 30 seconds and heated under no tension.
(4) After adjusting the humidity at 25 ° C. and 60% RH for 12 hours, measure the dimensions using a pin gauge (L₂(mm).
(5) Change in thermal dimension at 120 ° C. for 30 seconds according to the following formula.
Thermal dimensional change (%) at 120 ° C. for 30 seconds = 100 × (L₂-L₁) / L₁
[0063]
(4) Dimensional change rate of water absorption after heat development at 120 ° C for 30 seconds
(1) A heat-developable photosensitive material is cut out in the width direction (TD) 5 cm × longitudinal direction (MD) 25 cm to obtain a sample for MD direction. A sample in the width direction (TD) 25 cm × longitudinal direction (MD) 5 cm is similarly cut out as a sample for the TD direction.
(2) These are conditioned at 25 ° C. and 40% RH for 12 hours, and holes are formed at intervals of 20 cm and measured using a pin gauge (this is L₀(mm).
{Circle around (3)} These are subjected to heat development (contact with a heat block heated to 120 ° C. for 30 seconds and heated under no tension) with a heat developing machine installed at 25 ° C. and 75% RH.
(4) Dimensions at 3 minutes after heat development at 25 ° C. and 75% RH (L_Three) And dimensions after 120 minutes (L₁₂₀) Is measured using a pin gauge.
(5) The change in water absorption dimension after heat development at 120 ° C. for 30 seconds is determined according to the following formula.
Dimensional change rate of water absorption after heat development at 120 ° C for 30 seconds (%)
= {100 × (L₁₂₀-L₀) / L₀}-{100 × (L_Three-L₀) / L₀}
[0064]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this.
[0065]
Example-1
(1) Production of support (base)
Using terephthalic acid and ethylene glycol, PET of IV (inherent viscosity) = 0.66 (measured in phenol / tetrachloroethane = 6/4 (weight ratio) at 25 ° C.) was obtained according to a conventional method. This was pelletized, dried at 130 ° C. for 4 hours, melted at 300 ° C., extruded from a T-die, and rapidly cooled to prepare an unstretched film having a thickness of 120 μm after heat setting.
This was longitudinally stretched 3.3 times using rolls having different peripheral speeds, and then laterally stretched 4.5 times with a tenter. The temperatures at this time were 110 ° C. and 130 ° C., respectively. Thereafter, the film was heat-fixed at 240 ° C. for 20 seconds and relaxed by 4% in the lateral direction at the same temperature. After slitting the tenter chuck, knurling is performed on both ends and 4.8 kg / cm.²I wound up with. In this way, a roll having a width of 2.4 m, a length of 3500 m and a thickness of 120 μm was obtained.
[0066]
(2) Undercoat layer
After coating the undercoat layer (a-1) or (a-2) as shown in Table 1 on both sides of the support (base), the undercoat layer (b) was applied in sequence, 180 ° C, Dry for 4 minutes. The coating film thickness after drying of (a-1) or (a-2) was adjusted to the value shown in Table 1, and the coating film thickness of (b) was adjusted to 1.0 μm.

[0067]
 (2-2) Undercoat layer (a-2)
SBR polymer latex
Styrene / butadiene / hydroxyethyl methacrylate / divinylbenzene
= 67/30 / 2.5 / 0.5 (wt%) 160 parts by weight
2,4-dichloro-6-hydroxy-s-triazine 4 parts by weight
Matting agent (polystyrene, average particle size 2.4 μm) 3 parts by weight
(2-3) Undercoat layer (b)
Alkali-treated gelatin
(Ca ++ content 30ppm, Jelly strength 230g) 50mg / m²
[0068]
(3) Back layer
The following conductive layer and protective layer were sequentially applied on one side on which the undercoat layer (a-1) or (a-2) and the undercoat layer (b) were applied, and dried at 180 ° C. for 4 minutes, respectively. A PET support with a back layer / undercoat layer was prepared.
(3-1) Conductive layer (surface resistivity 10 at 25 ° C. and 25% RH 10⁹ Ω)
Jurimer ET-410 (manufactured by Nippon Pure Chemicals Co., Ltd.): Tg = 52 ° C. 38 mg / m²
SnO₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 120 mg / m²
Matting agent (polymethyl methacrylate, average particle size 5μm) 7mg / m²
Denacor EX-614B (manufactured by Nagase Kasei Kogyo Co., Ltd.) 13mg / m²
(3-2) Protective layer
Chemipearl S-120 (Mitsui Petrochemical Co., Ltd.): Tg = 77 ° C 500mg / m²
Snowtex-C (Nissan Chemical Co., Ltd.) 40mg / m²
Denacor EX-614B (manufactured by Nagase Chemicals Co., Ltd.) 30mg / m²
[0069]
(4) Heat treatment
The PET support with the back layer / undercoat layer was heat-treated while being conveyed in the heating zone at the temperature, tension and time described in Table 1.
[0070]
【table1]

[0071]
【table2]

[0072]
【table3]

[0073]
【table4]

[0074]
(5) Image forming layer (photosensitive layer)
The following image forming layer and protective layer were sequentially coated on the undercoat layer on the side opposite to the back layer, and dried at 65 ° C. for 3 minutes to obtain a heat-developable image-sensitive material.
(5-1) Preparation of silver halide grains
11 g of phthalated gelatin, 30 mg of potassium bromide and 10 mg of sodium thiosulfonate are dissolved in 700 ml of water and the pH is adjusted to 5.0 at a temperature of 35 ° C. Then, 159 ml of an aqueous solution containing 18.6 g of silver nitrate and 1 ml of potassium bromide are added. The aqueous solution containing mol / liter was added over 6.5 minutes by the controlled double jet method while keeping pAg 7.7. Then, 476 ml of an aqueous solution containing 55.4 g of silver nitrate and a halogen salt aqueous solution pAg 7.7 containing 1 mol / liter of potassium bromide were added over 30 minutes by the control double jet method, and then 4-hydroxy-6-6 Methyl-1,3,3a, 7-tetrazaindene (1 g) was added, and the pH was further lowered to cause aggregation and sedimentation, followed by desalting. Thereafter, 0.1 g of phenoxyethanol was added to adjust the pH to 5.9, pAg 8.2, and silver bromide grains (cubic grains having an average size of 0.12 μm, a projected area diameter variation coefficient of 8%, and a (100) plane ratio of 88%). Finished the preparation.
The silver halide grains thus obtained were heated to 60 ° C. and sodium thiosulfonate 8.5 × 10 5 per mole of silver.^-4Mole was added, aged for 120 minutes, then rapidly cooled to 40 ° C. and then 1 × 10^-5Molar dye S-1, 5 × 10^-5Mole of 2-mercapto-5-methylbenzimidazole and 5 × 10^-5Mole of N-methyl-N ′-{3- (mercaptotetrazolyl) phenyl} urea was added and quenched to 30 ° C. to obtain a silver halide emulsion.
[0075]
[Chemical 2]

[0076]
 (5-2) Preparation of organic acid silver dispersion
While stirring 4.4 g of stearic acid, 39.4 g of behenic acid, and 770 ml of distilled water at 90 ° C., 103 ml of 1N-NaOH aqueous solution was added and reacted for 240 minutes, and the temperature was lowered to 75 ° C. Next, 112.5 ml of an aqueous solution containing 19.2 g of silver nitrate was added over 45 seconds, left as it was for 20 minutes, and the temperature was lowered to 30 ° C. Thereafter, the solid content was separated by suction filtration, and the solid content was washed with water until the conductivity of the filtrate reached 30 μS / cm. 100 g of a 10 wt% hydroxypropylmethylcellulose aqueous solution was added to the solid content thus obtained, water was further added to a total weight of 270 g, and then dispersed in an automatic mortar to obtain a crude organic acid silver dispersion. This organic acid silver coarse dispersion is subjected to a collision pressure of 1000 kg / cm using a nanomizer (manufactured by Nanomizer).³To obtain an organic acid silver dispersion. The organic acid silver particles contained in the organic acid silver dispersion thus obtained were needle-like particles having an average minor axis of 0.04 μm, an average major axis of 0.8 μm, and a variation coefficient of 30%.
(5-3) Preparation of reducing agent dispersion
To 100 g of 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and 50 g of hydroxypropylcellulose, 850 g of water was added and mixed well to form a slurry. 840 g of zirconia beads having an average diameter of 0.5 mm were prepared, put in a vessel together with the slurry, and dispersed for 5 hours with a disperser (1/4 G sand grinder mill: manufactured by IMEX Co., Ltd.) to obtain a reducing agent dispersion. .
[0077]
 (5-4) Preparation of organic polyhalide dispersion
940 g of water was added to 50 g of tribromomethylphenylsulfone and 10 g of hydroxypropylmethylcellulose and mixed well to prepare a slurry. Prepare 840 g of zirconia beads having an average diameter of 0.5 nm, put them in a vessel together with the slurry, and disperse the organic polyhalide dispersion in a disperser (1/4 G sand grinder mill: manufactured by IMEX Co., Ltd.) for 5 hours. Obtained.
(5-5) Preparation of image forming layer coating solution
100 g of organic acid silver dispersion obtained above, 20 g of reducing agent dispersion, 15 g of organic polyhalide dispersion, LACSTAR 3307B (manufactured by Dainippon Ink & Chemicals, Inc .; SBR latex; Tg 13 ° C.) 49 wt% 40 g, MP-203 (Kuraray Co., Ltd .; polyvinyl alcohol) 20 g of 10 wt% aqueous solution, 20 g of silver halide emulsion, 1 ml of hydrazine compound (compound of general formula (H)) 1 wt% of methanol solution and 100 g of water and mixed well to form an image forming layer A coating solution was prepared.
This coating solution is coated with 1.5 g / m silver.²The solid content of polymer latex is 5.7 g / m²It applied so that it might become.
[0078]
(6) Protective layer
(6-1) Preparation of protective layer coating solution
The following coating solution has a solid content of polymer latex of 2 g / m²Then, it was coated on the photosensitive layer.
To 500 g of 40 wt% polymer latex (copolymer of methyl methacrylate / styrene / 2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate / methacrylic acid = 59/9/26/5/1; Tg 47 ° C.)₂262 g of O, and 14 g of benzyl alcohol, the following compound-22.5 g, 3.6 g of cellosol 524 (manufactured by Chukyo Yushi Co., Ltd.), the following compound-312 g, the following compound-4 1 g, and the following compound- 52 g, 7.5 g of the following compound-6, and 3.4 g of polymethyl methacrylate fine particles having an average particle size of 3 μm were sequentially added as a matting agent.₂O was added to 1000 g, and a coating solution having a viscosity of 5 cp (25 ° C.) and a pH = 3.4 (25 ° C.) was prepared.
[0079]
[Chemical Formula 3]

[0080]
(7) Thermal development, contact exposure and evaluation of sensitive materials
About the obtained heat-developable photosensitive material, according to the said method, the thermal dimensional change of 120 degreeC for 30 second and the water absorption dimensional change rate after the heat development after 120 degreeC for 30 second were calculated | required.
Further, a 10% flat screen image was exposed to the heat-developable photosensitive material prepared by the above method, cut into 50 cm × 50 cm, and then heat-developed under the conditions shown in Tables 2 to 4. Each level of the heat-developable photosensitive material was heated from room temperature to a constant temperature under the conditions shown in Tables 2 to 4, and after 30 seconds of the constant temperature part, the temperature was lowered from the constant temperature to the room temperature. After thermal development, the warpage amount and the waviness amount on the four sides were measured by the above-mentioned methods and shown in Tables 2 to 4. Thereafter, the PS plate was contact-exposed with a contact exposure printer. The PS plate was developed in accordance with a conventional method, and the area where the halftone dot image was stuck (the halftone dot was crushed and continuous) was visually measured, and the results are shown in Tables 2 and 4 (halftone dot). Point defect rate).
[0081]
As can be seen from the results of Comparative Example-1 in Tables 1 and 2, the support does not have a polyvinylidene chloride layer as an undercoat layer on both sides of the support, and heat treatment is performed under conditions other than those defined in the present invention. A photothermographic material having a thermal dimensional change and a water absorption dimensional change rate not within the range defined in the present invention,SaidIf heat development is performed under conditions other than the heat development conditions, both the warp amount and the wavy amount after heat development increase, and a burnout failure occurs as shown by a high dot defect rate, which is not preferable.
On the other hand, as shown in the present invention-1 to 8, the photothermographic material defined in the present invention is used.SaidIt can be seen that when heat development is performed by the heat development method, both the warp amount and the wavy amount after heat development are small, the dot defect rate is low, and no burnout failure occurs.
It should be noted that when heat development is performed using the photothermographic material shown in the present invention-2 having no polyvinylidene chloride in the undercoat layer, and as shown in the present invention-8.Warm andTemperature dropThe speed ofWhen heat development is performed by the heat development method, the photothermographic material specified in the present invention is used.SaidCompared to the case where heat development is performed by the heat development method, the warpage amount and the waviness amount are slightly larger in some sides, but there is no problem in the dot defect rate compared to Comparative Example-1. No burnout failure occurs. In addition, as shown in the present invention-9 to 14, heat development is performed,SaidIt can be seen that it is preferable to make the transport tension uniform by setting the range of the transport tension distribution to be performed, since both the warpage amount and the wavy amount after heat development are further reduced, and the dot defect rate is low.
[0082]
【The invention's effect】
The heat-developable photographic light-sensitive material of the present invention has an excellent effect that the flatness after heat development is good and no burn-out failure occurs even when it is used as a photosensitive material for printing as well as normal applications..
[Brief description of the drawings]
FIG. 1 is a schematic view showing slit positions for measuring the warpage of four sides and the amount of warpage in the present invention.
FIG. 2 is an explanatory diagram showing a method for measuring the amount of warpage in the present invention.
FIG. 3 is a schematic view showing the wavy state of four sides in the present invention on the end face of the photosensitive material.
[Explanation of symbols]
1 Sensitive material after heat development
2 Slit position
3, 8 sides
4 Slit pieces
5 Clearance when aligned at end a
6 Ruler
7 level stand
a, b One end of side 8
H_i  Maximum height of a certain undulating i
H_{i + 1}  Maximum height of a certain wavy i + 1 generated
H_{i + 2}  Maximum height of a certain wavy i + 2 generated
W_i  The width of the generated wavy i
W_{i + 1}  The width of the generated waved i + 1
W_{i + 2}  The width of the generated wavy i + 2

Claims (3)

A heat-developable photographic material support has a polyethylene terephthalate-based film that is heat treated below 200 ° C. 140 ° C. or higher tension 0 kg / m or more 5 kg / m or less at least 20 seconds 5 minutes or less, 120 ° C. 30 The change in the thermal dimension per second in the longitudinal direction is −0.05% or more and + 0.05% or less, and the warpage amounts at the ends of the four sides after heat development under the following heat development conditions are all 0 mm / in 50cm above 4 mm / 50cm or less, the waving of the end of the four sides after the thermal development, either even ^{0 mm} 2 / 50cm or more 500 mm ² / 50cm or less, the heat development conditions were as follows A heat-developable photographic material characterized by
Thermal development conditions
Temperature increase rate at the heat developing machine inlet: 1 ° C / second or more and 15 ° C / second or less
Temperature and time of the constant temperature part: 80 to 140 ° C. and 10 to 120 seconds
Temperature distribution in the width direction of the constant temperature part: 0 ° C or higher and 10 ° C or lower
Temperature decreasing rate at the heat developing machine outlet: -8 ° C / second or more and -1 ° C / second or less   2. The photothermographic material according to claim 1, wherein the rate of change in water absorption after heat development at 120 ° C. for 30 seconds is from 0% / 2 hours to 0.025% / 2 hours in the longitudinal direction. material. Heat-developable photographic material according to claim 1 or 2, wherein the layer of polyvinylidene chloride-based resin are respectively applied in 0.5μm or 10μm or less on both sides of the support.

Images