JP4156170B2 - Silver halide color photographic light-sensitive material for movie and image forming method - Google Patents

Description

【００３９】
一般式（IV）中、Ｒ¹は水素原子、アルキル基、アリール基または複素環基を表し、Ｒ²は水素原子、アルキル基、アリール基、複素環基、−ＣＯＲ⁴または−ＳＯ₂Ｒ⁴を表し、Ｒ³は水素原子、シアノ基、水酸基、カルボキシル基、アルキル基、アリール基、−ＣＯ₂Ｒ⁴、−ＯＲ⁴、−ＮＲ⁵Ｒ⁶、−ＣＯＮＲ⁵Ｒ⁶、−ＮＲ⁵ＣＯＲ⁴、−ＮＲ⁵ＳＯ₂Ｒ⁴、または−ＮＲ⁵ＣＯＮＲ⁵Ｒ⁶（ここで、Ｒ⁴はアルキル基、またはアリール基を表し、Ｒ⁵、Ｒ⁶は各々水素原子、アルキル基、またはアリール基を表す。）を表す。Ｌ¹、Ｌ²、Ｌ³は各々メチン基を表す。ｎは１又は２を表す。
【００４０】
一般式（IV）において、Ｒ¹のアルキル基としては炭素数１〜４のアルキル基、２−シアノエチル基、２−ヒドロキシエチル基、カルボキシベンジル基が挙げられ、アリール基としてはフェニル基、２−メチルフェニル基、２−カルボキシフェニル基、３−カルボキシフェニル基、４−カルボキシフェニル基、３，６−ジカルボキシフェニル基、２−ヒドロキシフェニル基、３−ヒドロキシフェニル基、４−ヒドロキシフェニル基、２−クロロ−４−カルボキシフェニル基、４−メチルスルファモイルフェニル基が挙げられ、複素環基としては、５−カルボキシベンゾオキサゾール−２−イル基が挙げられる。
【００４１】
Ｒ²のアルキル基としては炭素数１〜４のアルキル基、カルボキシメチル基、２−ヒドロキシエチル基、２−メトキシエチル基が挙げられ、アリール基としては２−カルボキシフェニル基、３−カルボキシフェニル基、４−カルボキシフェニル基、３，６−ジカルボキシフェニル基が挙げられ、複素環基としてはピリジル基が挙げられ、−ＣＯＲ⁴としてはアセチル基が挙げられ、−ＳＯ₂Ｒ⁴としてはメタンスルホニル基が挙げられる。
【００４２】
Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶のアルキル基としては炭素数１〜４のアルキル基が挙げられる。Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶のアリール基としてはフェニル基、メチルフェニル基が挙げられる。
本発明においては、Ｒ¹がカルボキシル基置換のフェニル基（例えば、２−カルボキシフェニル、３−カルボキシフェニル、４−カルボキシフェニル、３，６−ジカルボキシフェニル）であることが好ましい。
【００４３】
以下に、本発明に好ましく用いられる一般式（Ｉ）ないし（IV）で表される化合物の具体例を記載するが、これらに限定されるものではない。
【００４４】
【化２】

【００４５】
【化３】

【００４６】
【化４】

【００４７】
【化５】

【００４８】
【化６】

【００４９】
【化７】

【００５０】
【表１】

【００５１】
【表２】

【００５２】
一般式（IV）で表される化合物の具体例としては、上記以外に特開平１１−２８２１０６号の段落番号０１０１〜０１０５のIV−１３〜IV−５１が挙げられ、本発明の一般式（IV）で表される化合物として好ましい。
【００５３】
本発明に好ましく用いられる染料は、国際特許ＷＯ８８／０４７９４号、欧州公開特許第２７４，７２３Ａ１号、同第２７６，５６６号、同第２９９，４３５号、特開昭５２−９２７１６号、同５５−１５５３５０号、同５５−１５５３５１号、同６１−２０５９３４号、同４８−６８６２３号、米国特許第２，５２７，５８３号、同第３，４８６，８９７号、同第３，７４６，５３９号、同第３，９３３， ７９８号、同第４，１３０，４２９号、同第４，０４０，８４１号、特開平３−２８２２４４号、同３−７９３１号、同３−１６７５４６号等の明細書あるいは公報に記載されている方法又はその方法に準じて合成できる。
【００５４】
本発明で好ましく用いられる染料の固体微粒子分散物は、公知の方法で調製できる。製造法の詳細は、機能性顔料応用技術（シーエムシー刊、１９９１年）などに記載されている。
メディア分散は一般的な方法の一つである。この方法では染料粉末またはそのウエットケーキと呼ばれる水や有機溶媒で湿った状態の染料を、水性スラリーにし、公知の粉砕機（例えばボールミル、振動ボールミル、遊星ボールミル、縦型サンドミル、ローラーミル、ピンミル、コボールミル、キャディーミル、横型サンドミル、アトライター等）を用いて、分散メディア（スチールボール、セラミックボール、ガラスビーズ、アルミナビーズ、ジルコニアシリケートビーズ、ジルコニアビーズ、オタワサンドなど）の存在下で機械力によって粉砕する。これらのうち、ビーズの平均直径は好ましくは２ｍｍないし０．３ｍｍ、より好ましくは１ｍｍないし０．３ｍｍ、さらに好ましくは０．５ｍｍないし０．３ｍｍのものが用いられる。これらの他にジェットミル、ロールミル、ホモジナイザー、コロイドミルやデゾルバーによって粉砕する方法や、超音波分散機による粉砕方法も用いることができる。
【００５５】
また米国特許第２，８７０，０１２号に開示されているように、均一溶液に溶解した後、貧溶媒を加えて固体微粒子を析出させたり、例えば特開平３−１８２７４３号に開示されているように、アルカリ溶液に溶解した後ｐＨを下げることで、固体微粒子を析出させる方法も用いることが出来る。
【００５６】
これらの固体微粒子分散物を調製するときは、分散助剤を存在させるのが好ましい。従来より開示されてきた分散助剤としては、アルキルフェノキシエトキシスルホン酸塩、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、アルキル硫酸エステル塩、アルキルスルホコハク酸塩、ナトリウムオレイルメチルタウライド、ナフタレンスルホン酸のホルムアルデヒド縮重物、ポリアクリル酸、ポリメタクリル酸、マレイン酸アクリル酸共重合物、カルボキシメチルセルロース、硫酸セルロース等のアニオン系分散剤、ポリオキシエチレンアルキルエーテル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステルなどのノニオン系分散剤、カチオン系分散剤やベタイン系分散剤が挙げられるが、下記一般式（Ｖ−ａ）又は（Ｖ−ｂ）で表されるポリアルキレンオキサイドを用いることが特に好ましい。
【００５７】
【化８】

【００５８】
一般式（Ｖ−ａ）及び（Ｖ−ｂ）中、ａ及びｂはそれぞれ５ないし５００の値を示す。好ましいａとｂの値はそれぞれ１０〜２００、より好ましいａとｂの値はそれぞれ５０〜１５０である。ａとｂの値がこの範囲であると塗布面の均一性良化の点で好ましい。
【００５９】
上記分散助剤において、ポリエチレンオキサイド部の比率は質量比で好ましくは０．３ないし０．９、より好ましくは０．７ないし０．９、更に好ましくは０．８ないし０．９であり、また、上記分散助剤の平均分子量は好ましくは１，０００ないし３０，０００、より好ましくは５，０００ないし４０，０００、更に好ましくは８，０００ないし２０，０００である。更に、上記分散助剤のＨＬＢ（親水性親油性バランス）は好ましくは７ないし３０、より好ましくは１２ないし３０、更に好ましくは１８ないし３０である。数値がこの範囲であると塗布面の均一性良化の点で好ましい。
【００６０】
これらの化合物は市販品として入手可能であり、例えばＢＡＳＦ社のＰｌｕｒｏｎｉｃ等がある。
これらの好ましい化合物としては、特開平１１−２８２１０６号の段落番号０１１５および０１１６に記載のＩ−１〜Ｉ−２３が挙げられ、該段落番号部分は本発明の明細書の一部として本願の明細書に取り込まれる。
【００６１】
本発明において、本発明に好ましく使用される染料に対する上記分散助剤の使用量は質量比で好ましくは０．０５ないし０．５、より好ましくは０．１ないし０．３である。分散助剤の使用量がこの範囲であると塗布面の均一性良化の点で好ましい。
また固体微粒子分散物の調製時に分散物の安定化や低粘度化の目的でポリビニルアルコール、ポリビニルピロリドン、ポリエチレングリコール、多糖類、ゼラチンなどの親水性コロイドを共存させることもできる。これらのうち、本発明においては、特開平１１−２８２１０６号の段落番号０１３０〜０１６７に記載の一般式〔Ｖ〕で表される化合物を共存させることが特に好ましく、該段落部分は本願の明細書の一部として取り込まれる。
【００６２】
本発明に好ましく使用される染料の固体微粒子分散物は、特開平５−２１６１６６号公報に開示されているような方法で、分散前、分散中または分散後に加熱処理されるものが好ましい。
【００６３】
本発明で好ましく使用される染料は、感光材料中に組み込む前に４０℃以上の熱処理を行うのが好ましい。
本発明において染料分散物に好ましく適用される熱処理としては、染料粉体を溶媒中で加熱するなど固体状に微分散する工程の前に行う方法と、染料を分散剤の存在下で水あるいは他の溶媒中に分散する際冷却せず、あるいは温度をかけて分散を行う方法、および分散後の液や塗布液を加熱処理する方法とがあるが、分散後に行なうのが特に好ましい。
【００６４】
一般式（Ｉ）で表される染料を含有する固体微粒子分散物が、特定の層に複数種用いられているときは少なくとも１種が熱処理されていればよい。
【００６５】
分散時及び分散後熱処理中のｐＨは分散物が安定に存在する条件であればよく、好ましくはｐＨ２．０以上８．０以下、より好ましくは２．０以上６．５以下、更に好ましくは２．５以上４．５未満である。熱処理中のｐＨがこの範囲であると塗布物の膜強度改良の点で好ましい。
分散物のｐＨ調整は、例えば硫酸、塩酸、酢酸、クエン酸、リン酸、しゅう酸、炭酸、炭酸水素ナトリウム、炭酸ナトリウム、水酸化ナトリウム、水酸化カリウムやそれらからなる緩衝液を用いることができる。
【００６６】
熱処理をする温度としては熱処理をする工程、粉体ないし粒子の大きさ形状、熱処理条件、溶媒などによって異なるので一概には云えず４０℃以上で染料が分解しない範囲であれば何度でもよいが、粉体で熱処理する場合には４０℃ないし２００℃が適当であり、好ましくは９０℃ないし１５０℃が適当であり、溶媒中で熱処理する場合には４０℃ないし１５０℃、好ましくは９０℃ないし１５０℃、分散中に熱処理する場合には４０℃ないし９０℃が適当であり、好ましくは５０℃ないし９０℃、分散後の分散液を熱処理する場合には４０℃ないし１００℃が適当であり、好ましくは５０℃ないし９５℃である。熱処理の温度が４０℃より低いと効果が乏しい。
【００６７】
熱処理が溶媒中で行われる場合、その溶媒の種類としては、染料を実質的に溶解しないものであれば制限はなく、例えば水、アルコール類（例えば、メタノール、エタノール、イソプロピルアルコール、ブタノール、イソアミルアミルコール、オクタノール、エチレングリコール、ジエチレングリコール、エチルセロソルブ）、ケトン類（例えば、アセトン、メチルエチルケトン）、エステル類（例えば、酢酸エチル、酢酸ブチル）、アルキルカルボン酸類（例えば、酢酸、プロピオン酸）、ニトリル類（例えば、アセトニトリル）、エーテル類（例えば、ジメトキシエタン、ジオキサン、テトラヒドロフラン）、アミド類（例えば、ジメチルホルムアミド）等を挙げることができる。
【００６８】
また、これらの溶媒単独では染料が溶解してしまう場合でも、水や他の溶媒と混合したり、ｐＨを調節することで染料が実質溶解しなければ使用することができる。
【００６９】
熱処理する時間についても一概には云えず、温度が低ければ長時間を要し、高ければ短時間で済む。製造工程上影響のない範囲内で熱処理が実現できるように任意に設定することができるが、通常１時間ないし４日であることが好ましい。
【００７０】
写真感光材料に染料の微粒子を含有してなる層を設けるには、このようにして得た微粒子を適当なバインダー中に分散させることによってほぼ均一な粒子の固体分散物として調製した後、これを所望の支持体上に塗設することによって設けることができる。
上記バインダーは感光性乳剤層や、非感光性層に用いることができる親水性のコロイドであれば特に制限はないが、通常ゼラチンまたはポリビニルアルコールやポリアクリルアミド等の合成ポリマーが用いられる。
【００７１】
固体分散物中の微粒子は、平均粒子径０．００５μｍ〜１０μｍ、好ましくは０．０１μｍ〜１μｍ、より好ましくは０．０１μｍ〜０．７μｍであることが好ましい。この範囲であると微粒子の非凝集性、光の吸収効率の点で好ましい。本発明で用いる一般式（Ｉ）で表される染料の固体微粒子分散物は、単独又は複数の固体微粒子分散物と併用して使用することができる。
【００７２】
さらに、固体微粒子を添加する親水性コロイド層はただ一層でも良いし、複数層であっても良い。たとえば、単独の固体微粒子分散物をただ一層に添加する場合、複数層に分割して添加する場合、複数の固体微粒子分散物をただ一層に同時に添加する場合、それぞれ別層に添加する場合などが例として挙げられるが、上記に限られるものではない。
【００７３】
さらに、固体微粒子分散物は、アンチハレーション層として必要な量を組み込まれたうえ、イラジエーション防止用に感光性ハロゲン化銀乳剤層に必要量を添加されることもできる。
本発明で好ましく用いる一般式（Ｉ）の染料の固体微粒子分散物を含有する親水性コロイド層は、支持体とこれに最も近いハロゲン化銀乳剤層の間に設けられる。ここで、支持体とこれに最も近いハロゲン化銀乳剤層の間には、固体微粒子分散物を含有する親水性コロイド層以外の他の非感光性親水性コロイド層を有していてもよい。
【００７４】
本発明で好ましく用いられる染料の固体微粒子分散物は、ハロゲン化銀写真感光材料において、染料の色相に応じて非感光性親水性コロイド層に含有されるが、該非感光性層が複数層設けられている態様の感光材料においては、これらの複数層に含有させることもできる。
本発明の固体微粒子分散物中の染料濃度は０．１〜５０質量％が適当であり、好ましくは２〜３５質量％、更に好ましくは２〜３０質量％である。染料濃度がこの範囲であると分散物の粘度の点で好ましい。また、固体微粒子染料の好ましい塗布量は、約０．０５〜０．５ｇ／ｍ²である。
【００７５】
本発明のハロゲン化銀カラー写真感光材料は通常行われている現像処理によって処理される。
特に、映画用ハロゲン化銀カラー写真感光材料の処理において、映画用ポジ感光材料は、下記の従来より用いられてきた処理工程で処理できる。また、本発明の映画用ポジ感光材料の場合は、レジンバック層除去のための、（１）プレバス浴及び（２）水洗浴の各工程を削減できる。また、このような短縮された処理工程は処理簡易化に好ましい。
また、サウンドトラックを色素画像で形成する場合、以下の（６）第一定着浴、（７）水洗浴、（１１）サウンド現像および（１２）水洗の各工程を削減でき、処理簡易化において、極めて好ましい態様になる。
本発明の感光材料はこのような処理工程においても優れた性能を発現できる。
【００７６】
従来の映画用ポジ感光材料の標準的な処理工程（乾燥以外）
（１）プレバス浴
（２）水洗浴
（３）発色現像浴
（４）停止浴
（５）水洗浴
（６）第一定着浴
（７）水洗浴
（８）漂白促進浴
（９）漂白浴
（１０）水洗浴
（１１）サウンド現像（塗り付け現像）
（１２）水洗
（１３）第二定着浴
（１４）水洗浴
（１５）安定浴
【００７７】
本発明においては、上記処理工程のうち、発色現像時間（上記の（３）の工程）が２分３０秒以下（下限は６秒以上が好ましく、より好ましくは１０秒以上、更に好ましくは２０秒以上、最も好ましくは３０秒以上）、より好ましくは２分以下（下限は２分３０秒と同じ）である場合に、本発明の効果が著しく、好ましい。
また、第一定着工程は好ましくは２０秒以上４０秒以下、より好ましくは２３秒以上４０秒未満、更に好ましくは２５秒以上３５秒で行うのが好ましい。
【００７８】
次に本発明のハロゲン化銀写真感光材料の写真層等について記載する。
【００７９】
各発色性感光性ハロゲン化銀乳剤層の発色性と感色性の間にも制限はなく、例えば、ある発色性感光性ハロゲン化銀乳剤層が赤外域に感色性を有していてもかまわない。
典型的な層順の例としては支持体から順に非感光性親水性コロイド層（本発明に好ましく用いられる一般式（Ｉ）で表される染料の固体微粒子分散物を含有する非感光性親水性コロイド層が好ましい）、イエロー発色性感光性ハロゲン化銀乳剤層、非感光性親水性コロイド層（混色防止層）、シアン発色性感光性ハロゲン化銀乳剤層、非感光性親水性コロイド層（混色防止層）、マゼンタ発色性感光性ハロゲン化銀乳剤層、非感光性親水性コロイド層（保護層）である。しかし、目的に応じて、上記設置順を変更しても、非感光性親水性コロイド層の数を増減させてもかまわない。
【００８０】
このうち、マゼンタ発色感光性ハロゲン化銀乳剤層は、全感光性ハロゲン化銀乳剤層中で支持体から最も離れた位置にあることが好ましいが、その制限以外の感光性ハロゲン化銀乳剤層及び非感光性親水性コロイド層の層数及び層順に特に制限はない。イエロー、シアン、マゼンタの各発色性感光性ハロゲン化銀乳剤層は各々一つの感光性ハロゲン化銀乳剤層からなっていても、感色性が同じで感度の異なる複数のハロゲン化銀乳剤層からなっていてもよい。また、マゼンタ発色性感光性ハロゲン化銀乳剤層が複数の感光性ハロゲン化銀乳剤層からなっている場合、複数のマゼンタ発色性感光性ハロゲン化銀乳剤層の少なくとも１つが全感光性ハロゲン化銀乳剤層中で支持体から最も離れた位置にあることが好ましい。更に、シアン発色性感光性ハロゲン化銀乳剤層およびイエロー発色性感光性ハロゲン化銀乳剤層は支持体上の近い位置からイエロー発色性感光性ハロゲン化銀乳剤層、シアン発色性感光性ハロゲン化銀乳剤層であっても、その逆であっても構わないが、好ましくは、イエロー発色性感光性ハロゲン化銀乳剤層、シアン発色性感光性ハロゲン化銀乳剤層の順である。
【００８１】
支持体上に設けられた感光性ハロゲン化銀乳剤層や非感光性親水性コロイド層（中間層や保護層など）からなる写真構成層中のいずれかの層、好ましくはハロゲン化銀乳剤層に、１−アリール−５−メルカプトテトラゾール化合物をハロゲン化銀１モル当たり１．０×１０^-5〜５．０×１０^-2モル添加することが好ましく、更には１．０×１０^-4〜１．０×１０^-2モル添加することが好ましい。この範囲で添加することによって、連続処理後の処理済みカラー写真表面への汚れをいっそう少なくすることができる。
【００８２】
このような１−アリール−５−メルカプトテトラゾール化合物としては、１位のアリール基が無置換または置換フェニル基であるものが好ましく、この置換基の好ましい具体例としてはアシルアミノ基（例えば、アセチルアミノ、−ＮＨＣＯＣ₅Ｈ₁₁ ⁽ⁿ⁾など）、ウレイド基（例えば、メチルウレイドなど）、アルコキシ基（例えばメトキシなど）、カルボン酸基、アミノ基、スルファモイル基などであって、これらの基はフェニル基に複数個（２〜３個など）結合していてもよい。また、これの置換基の位置はメタまたはパラ位が好ましい。
【００８３】
これらの具体例としては、１−（ｍ−メチルウレイドフェニル）−５−メルカプトテトラゾールや１−（ｍ−アセチルアミノフェニル）−５−メルカプトテトラゾールが挙げられる。
【００８４】
本発明に使用できる写真用添加剤は以下のリサーチディスクロジャー誌（ＲＤ）に記載されており、下記の表に関連する記載箇所を示した。

【００８５】
本発明の感光材料には種々の色素形成カプラーを使用することができるが、以下のカプラーが特に好ましい。
イエローカプラー：EP 502,424A の式(I),(II)で表わされるカプラー；EP 513,496Aの式(1),(2)で表わされるカプラー（特に18頁のY-28);特開平5-307248号公報の請求項１の一般式(I) で表わされるカプラー；US 5,066,576のカラム１の45〜55行の一般式(I)で表わされるカプラー；特開平4-274425号公報の段落0008の一般式(I)で表わされるカプラー；EP 498,381A1の40頁のクレーム１に記載のカプラー（特に18頁のD-35); EP 447,969A1の４頁の式(Y)で表わされるカプラー（特にY-1(17頁),Y-54(41頁)); US 4,476,219のカラム７の36〜58行の式(II)〜(IV)で表わされるカプラー（特にII-17, 19(カラム17), II-24（カラム19））。
【００８６】
マゼンタカプラー；特開平3-39737(L-57（11頁右下), L-68(12頁右下), L-77(13頁右下）); EP 456,257のA-4 -63(134頁), A-4 -73, -75(139頁); EP 486,965のM-4, -6(26頁), M-7(27頁);特開平6-43611の段落0024のM-45, 特開平5-204106の段落0036のM-1;特開平4-362631の段落0237のM-22。
シアンカプラー：特開平4-204843のCX-1, 3, 4, 5, 11, 12, 14, 15(14〜16頁);特開平4-43345のC-7, 10(35頁）, 34, 35（37頁), (I-1), (I-17)(42〜43頁);特開平6-67385の請求項１の一般式(Ia)または(Ib)で表わされるカプラー。
ポリマーカプラー：特開平2-44345のP-1, P-5(11頁）。
サウンドトラック形成用赤外カプラー：特開昭６３−１４３５４６号および該特許に引用されている特許に記載のカプラー。
【００８７】
発色色素が適度な拡散性を有するカプラーとしては、US 4,366,237、GB 2,125570、EP 96,873B、DE 3,234,533に記載のものが好ましい。
発色色素の不要吸収を捕正するためのカプラーは、EP 456,257A1の５頁に記載の式（CI), (CII), (CIII), (CIV）で表わされるイエローカラードシアンカプラー（特に84頁のYC-86)、該EPに記載のイエローカラードマゼンタカプラーExM-7(202頁、EX-1(249頁)、EX-7(251頁)、US 4,833,069に記載のマゼンタカラードシアンカプラーCC-9（カラム８)、CC-13(カラム10)、US 4,837,136の(2)(カラム8)、W092/11575のクレーム１の式〔Ｃ−１〕で表わされる無色のマスキングカプラー（特に36〜45頁の例示化合物）が好ましい。
【００８８】
現像主薬酸化体と反応して写真的に有用な化合物残基を放出する化合物（カプラーを含む）としては、以下のものが挙げられる。現像抑制剤放出化合物：EP 378,236A1の11頁に記載の式(I),(II),(III),(IV)で表わされる化合物（特にT-101 (30頁), T-104(31頁), T-113(36頁), T-131(45頁), T-144(51頁), T-158(58頁)), EP 436,938A2の７頁に記載の式(I) で表わされる化合物（特にD-49(51頁))、特開平5-307248の式(1)で表わされる化合物（特に段落0027の(23))、EP 440,195A2の５〜６頁に記載の式(I),(II),(III)で表わされる化合物（特に29頁のI-(1)); 漂白促進剤放出化合物: EP 310,125A2の５頁の式(I),(I′)で表わされる化合物（特に61頁の(60),(61))及び特開平6-59411の請求項１の式(I)で表わされる化合物（特に段落0022の(7)); リガンド放出化合物：US 4,555,478のクレーム１に記載のLIG-X で表わされる化合物（特にカラム12の21〜41行目の化合物);ロイコ色素放出化合物; US 4,749,641のカラム３〜８の化合物１〜６；蛍光色素放出化合物：US 4,774,181のクレーム１のCOUP-DYEで表わされる化合物（特にカラム７〜10の化合物１〜11);現像促進剤又はカブラセ剤放出化合物：US 4,656,123のカラム３の式(1)、(2)、(3)で表わされる化合物（特にカラム25の(I-22))及びEP 450,637A2の75頁36〜38行目のExZK-2；離脱して初めて色素となる基を放出する化合物: US 4,857,447のクレーム１の式(I) で表わされる化合物（特にカラム25〜36のY-1〜Y-19)。
【００８９】
カプラー以外の添加剤としては、以下のものが好ましい。
油溶性有機化合物の分散媒：特開昭62-215272のP-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93(140〜144頁);油溶性有機化合物の含浸用ラテックス：US 4,199,363に記載のラテックス；現像主薬酸化体スカベンジャー：US 4,978,606のカラム２の54〜62行の式(I)で表わされる化合物（特にI-,(1),(2),(6),(12)(カラム４〜５）、US 4,923,787のカラム２の５〜10行の式（特に化合物１（カラム３);ステイン防止剤：EP 298321Aの４頁30〜33行の式(I)〜(III),特にI-47, 72, III-1, 27(24〜48頁);褪色防止剤：EP 298321AのA-6, 7, 20, 21, 23, 24, 25, 26, 30, 37, 40, 42, 48, 63, 90, 92, 94, 164(69〜118頁), US 5,122,444のカラム25〜38のII-1〜III-23, 特にIII-10, EP 471347Aの８〜12頁のI-1〜III-4,特にII-2, US 5,139,931のカラム32〜40のA-1〜48, 特にA-39, 42；発色増強剤または混色防止剤の使用量を低減させる素材：EP 411324Aの５〜24頁のI-1〜II-15,特にI-46；ホルマリンスカベンジャー：EP 477932Aの24〜29頁のSCV-1〜28, 特にSCV-8；
【００９０】
現像抑制剤プレカーサー：特開昭62-168139のP-24, 37, 39（６〜７頁); US 5,019,492のクレーム１に記載の化合物, 特にカラム７の28〜29； 防腐剤、防黴剤：US 4,923,790のカラム３〜15のI-1〜III-43, 特にII-1, 9, 10,18, III-25；安定剤、かぶり防止剤：US 4,923,793のカラム６〜16のI-1〜(14), 特にI-1, 60, (2),(13), US 4,952,483のカラム25〜32の化合物１〜65, 特に36：化学増感剤：トリフェニルホスフィンセレニド, 特開平5-40324の化合物50；染料：特開平3-156450の15〜18頁のa-1〜b-20, 特にa-1, 12, 18, 27, 35, 36, b-5, 27〜29頁のV-1〜23, 特にV-1, EP 445627Aの33〜55頁のF-I-1〜F-II-43, 特にF-I-11, F-II-8, EP 457153Aの17〜28頁のIII-1〜36, 特にIII-1, 3, W088/04794の８〜26のDye-1〜124の微結晶分散体, EP 319999Aの６〜11頁の化合物1〜22, 特に化合物1, EP 519306Aの式(1)ないし(3)で表わされる化合物D-1〜87(3〜28頁), US 4,268,622の式(I) で表わされる化合物１〜22（カラム３〜10), US 4,923,788の式(I)で表わされる化合物(1)〜(31)（カラム２〜９);ＵＶ吸収剤: 特開昭46-3335の式(1) で表わされる化合物(18b)〜(18r), 101〜427(６〜９頁),EP 520938Aの式(I) で表わされる化合物(3)〜(66)(10〜44頁)及び式(III)で表わされる化合物HBT-1〜HBT-10(14頁), EP 521823Aの式(1)で表わされる化合物(1)〜(31)（カラム２〜９）。
【００９１】
本発明において、写真構成層中の油溶性成分の親水性バインダーに対する比率は、任意に設定できる。保護層以外の写真構成層における好ましい比率は質量比で０．０５〜１．５０、更に好ましくは０．１０〜１．４０、最も好ましくは０．２０〜１．３０である。各層の比率を最適化することで膜強度や耐傷性、カール特性を調節することが出来る。
【００９２】
以下、支持体について説明する。プラスチックフィルム支持体としては、例えばポリエチレンテレフタレート、ポリエチレンナフタレート、セルローストリアセテート、セルロースアセテートブチレート、セルロースアセテートプロピオネート、ポリカーボネート、ポリスチレン、ポリエチレンのフィルムを挙げることができる。
【００９３】
中でも、ポリエチレンテレフタレートフィルムが好ましく、特に２軸延伸、熱固定されたポリエチレンテレフタレートフィルムが、安定性、強靱さなどの点からも特に好ましい。
【００９４】
支持体の厚さに特に制限はないが、１５〜５００μｍの範囲が一般的で、特に４０〜２００μｍの範囲のものが取扱易性、汎用性などの点から有利なため好ましく、８５〜１５０μｍが最も好ましい。
透過型支持体とは、好ましくは可視光が９０％以上透過するものを意味し、光の透過を実質的に妨げない量であれば染料化ケイ素、アルミナゾル、クロム塩、ジルコニウム塩などを含有していても良い。
【００９５】
上記プラスチックフィルム支持体の表面に、感光層を強固に接着させるために、一般に下記の表面処理が行なわれる。帯電防止層（バック層）が形成される側の表面も、一般に同様な表面処理が行なわれる。
（１）薬品処理、機械的処理、コロナ放電処理、火焔処理、紫外線処理、高周波処理、グロー放電処理、活性プラズマ処理、レーザー処理、混酸処理、オゾン酸素処理、などの表面活性処理した後、直接に写真乳剤（感光層形成用塗布液）を塗布して接着力を得る方法と、
（２）一旦これらの表面処理した後、下塗層を設けこの上に写真乳剤層を塗布する方法との二法がある。
【００９６】
これらのうち（２）の方法がより有効であり広く行われている。これらの表面処理はいずれも、本来は疎水性であった支持体表面に、多少とも極性基を形成させること、表面の接着に対してマイナスの要因になる薄層を除去すること、表面の架橋密度を増加させ接着力を増加させるものと思われ、その結果として下塗層用溶液中に含有される成分の極性基との親和力が増加することや、接着表面の堅牢度が増加すること等により、下塗層と支持体表面との接着性が向上すると考えられる。
【００９７】
上記プラスチックフィルム支持体上の感光層が設けられない側の表面には、導電性金属酸化物粒子を含有する非感光性層（帯電防止層）が設けられることが好ましい。
上記の非感光性層のバインダーとしては、アクリル樹脂、ビニル樹脂、ポリウレタン樹脂及びポリエステル樹脂が好ましく使用される。本発明の非感光性層は硬膜されているのが好ましく、硬膜剤としては、アジリジン系、トリアジン系、ビニルスルホン系、アルデヒド系、シアノアクリレート系、ペプチド系、エポキシ系、メラミン系などが用いられるが、導電性金属酸化物粒子を強固に固定する観点からは、メラミン系化合物が特に好ましい。
【００９８】
導電性金属酸化物粒子の材料としては、ＺｎＯ、ＴｉＯ₂、ＳｎＯ₂、Ａｌ₂Ｏ₃、Ｉｎ₂Ｏ₃、ＭｇＯ、ＢａＯ、ＭｏＯ₃およびＶ₂Ｏ₅及びこれらの複合酸化物、そしてこれらの金属酸化物に更に異種原子を含む金属酸化物を挙げることができる。
【００９９】
金属酸化物としては、ＳｎＯ₂、ＺｎＯ、Ａｌ₂Ｏ₃、ＴｉＯ₂、Ｉｎ₂Ｏ₃、ＭｇＯ、およびＶ₂Ｏ₅が好ましく、さらにＳｎＯ₂、ＺｎＯ、Ｉｎ₂Ｏ₃、ＴｉＯ₂およびＶ₂Ｏ₅が好ましく、ＳｎＯ₂およびＶ₂Ｏ₅が特に好ましい。
異種原子を少量含む例としては、ＺｎＯに対してＡｌあるいはＩｎ、ＴｉＯ₂に対してＮｂあるいはＴａ、Ｉｎ₂Ｏ₃に対してＳｎ、及びＳｎＯ₂に対してＳｂ、Ｎｂあるいはハロゲン元素などの異種元素を０．０１〜３０モル％（好ましくは０．１〜１０モル％）ドープしたものを挙げることができる。異種元素の添加量が、０．０１モル％未満の場合は酸化物または複合酸化物に充分な導電性を付与することができず、３０モル％を超えると粒子の黒化度が増し、帯電防止層が黒ずむため感光材料用としては適さない。従って、導電性金属酸化物粒子の材料としては、金属酸化物または複合金属酸化物に対し異種元素を少量含むものが好ましい。また結晶構造中に酸素欠陥を含むものも好ましい。
【０１００】
導電性金属酸化物粒子は、非感光性層全体に対し、体積比率が５０％以下である必要があるが、好ましくは３〜３０％である。塗設量としては特開平１０−６２９０５号に記載の条件に従うことが好ましい。
体積比率が５０％を越えると処理済カラー写真の表面に汚れが付着しやすく、また３％を下回ると帯電防止能が十分に機能しない。
【０１０１】
導電性金属酸化物粒子の粒子径は、光散乱をできるだけ小さくするために小さい程好ましいが、粒子と結合剤の屈折率の比をパラメーターとして決定されるべきものであり、ミー（Ｍｉｅ）の理論を用いて求めることができる。一般に、平均粒子径が０．００１〜０．５μｍの範囲であり、０．００３〜０．２μｍの範囲が好ましい。ここでいう、平均粒子径とは、導電性金属酸化物粒子の一次粒子径だけでなく高次構造の粒子径も含んだ値である。
【０１０２】
上記金属酸化物の微粒子を帯電防止層形成用塗布液へ添加する際は、そのまま添加して分散しても良いが、水等の溶媒（必要に応じて分散剤、バインダーを含む）に分散させた分散液の形で添加することが好ましい。
【０１０３】
上述の帯電防止層の更に詳細は、特開平１１−２８２１０６号の段落番号０２０４〜０２１９に記載され、本願に好ましく適用される。
また、帯電防止層の上には、表面層を設けるのが好ましい。表面層は、主として滑り性及び耐傷性を向上させるため、及び帯電防止層の導電性金属酸化物粒子の脱離防止の機能を補助するために設けられる。該表面層に関しては、同じく特開平１１−２８２１０６号の段落番号０２２０〜０２２４に記載され、本願に好ましく適用される。
従って、特開平１１−２８２１０６号の段落番号０２０４〜０２２４の記載は本願の明細書の一部として取り込まれる。
【０１０４】
本発明の感光材料の被膜ｐＨは、４．６〜６．４が好ましく、更に好ましくは５．５〜６．５の範囲である。経時の長い試料において、被膜ｐＨが６．５を超える場合、セーフライト照射によるシアン画像、マゼンタ画像の増感が大きく、逆に被膜ｐＨが４．５を下回る場合、感光材料を露光してから現像するまでの時間変化に対して、イエロー画像濃度が大きく変化する。いずれの場合も実用上問題である。
【０１０５】
本発明のハロゲン化銀カラー写真感光材料の被膜ｐＨとは、塗布液を支持体上に塗布することによって得られた全写真層のｐＨであり、塗布液のｐＨとは必ずしも一致しない。その被膜ｐＨは特開昭６１−２４５１５３号に記載されているような以下の方法で測定できる。即ち、
（１）ハロゲン化銀乳剤が塗布された側の感光材料表面に純水を０．０５ｍｌ滴下する。次に、
（２）３分間放置後、表面ｐＨ測定電極（東亜電波製ＧＳ−１６５Ｆ）にて被膜ｐＨを測定する。被膜ｐＨの調整は、必要に応じて酸（例えば硫酸、クエン酸）またはアルカリ（例えば水酸化ナトリウム、水酸化カリウム）を用いて行うことができる。
【０１０６】
【実施例】
以下に、実施例により本発明を具体的に説明するが、本発明はこれらに限定されるものではない。
【０１０７】
実施例１
（青感性ハロゲン化銀乳剤粒子Ｙ０１の調製）
石灰処理ゼラチンの２％水溶液に塩化ナトリウム１．０ｇを加え、酸を加えてｐＨ４．５に調整した。この水溶液に硝酸銀０．０３モル含む水溶液と、塩化ナトリウム及び臭化カリウムあわせて０．０３モル含む水溶液とを激しく攪拌しながら４０℃にて添加混合した。続いて臭化カリウム０．００５モル含む水溶液（Ｘ−１）を添加した後、硝酸銀０．１３モル含む水溶液と塩化ナトリウム０．１３モル含む水溶液を添加した。さらに温度を７５℃に上げ、ｐＡｇを７．０に保ちながら、硝酸銀０．９モル含む水溶液と、塩化ナトリウム０．９モル含む水溶液と、総銀量に対して、２×１０^-7モル／銀モルになるようにイリジウム化合物（Ｋ₂ＩｒＣｌ₆）とを添加混合し、更に５分後、硝酸銀０．１モル含む水溶液と塩化ナトリウム０．１モル含む水溶液を添加混合した。４０分放置後、３５℃にて沈降水洗を行い、脱塩を施した。その後、石灰処理ゼラチン１００ｇ加え、ｐＨ６．０、 ｐＡｇ７．０に調整した。こうして、主平面が｛１００｝面の平板状粒子であり、投影面積相当直径０．８０μｍ平均厚さ０．１５μｍ、平均アスペクト比 ４．５、立方体の辺長相当に換算すると、０．３９μｍ、変動係数０．２０の塩化銀含有率９６．５モル％の平板状粒子を調製した。この乳剤粒子に対して下記に示す増感色素（Ａ）、（Ｂ）、（Ｃ）がそれぞれ３．５×１０^-4モル、２．５×１０^-5モル、１．８×１０^-5モルとなるように添加した。その後、硫黄増感剤と金増感剤を添加して化学熟成を最適に行った。
【０１０８】
【化９】

【０１０９】
（青感性ハロゲン化銀乳剤粒子Ｙ１１の調製）
上記Ｙ０１の調製において、（Ｘ−１）の臭化カリウムを０．０１０モルに変更して投影面積相当直径０．６０μｍ、平均厚さ０．１３μｍ、平均アスペクト比３．８、変動係数０．１９の塩化銀含有率９６．５モル％の平板状粒子を調製した。増感色素（Ａ）、（Ｂ）、（Ｃ）はそれぞれ４．７×１０^-4モル、４．６×１０^-5モル、２．７×１０^-4モル添加し、Ｙ０１と同様にして化学熟成を最適に行った。なお、これらの変更点以外は上記Ｙ０１と同じである。
【０１１０】
（青感性ハロゲン化銀粒子Ｙ２１の調製）
上記Ｙ０１の調製において、（Ｘ−１）の臭化カリウムを０．０１４モルに変更して投影面積相当直径０．４０μｍ、平均厚さ０．１２μｍ、平均アスペクト比３．３、変動係数０．１８の塩化銀含有率９６．５モル％の平板状粒子を調製した。増感色素（Ａ）、（Ｂ）、（Ｃ）をそれぞれ５．３×１０^-4モル、６．３×１０^-5モル、３．８×１０^-4モル添加した。Ｙ０１と同様にして化学熟成を最適に行った。なお、これらの変更点以外は上記Ｙ０１と同じである。
【０１１１】
（比較用青感性ハロゲン化銀粒子Ｙ０２の調製）
上記Ｙ０１の平板状乳剤作成において７５℃以降に添加する塩化ナトリウムの添加において添加の経過時間にしたがって臭化カリウムの混合比率を増加させていくことにより、塩化銀含有率６０モル％の平板状粒子を作成した。粒子形状、変動係数は、Ｙ０１と同等であった。増感色素はＹ０１と同様に添加した。化学熟成はＹ０１と同等の感度となるように行った。なお、これらの変更点以外は上記Ｙ０１と同じである。
【０１１２】
（比較用青感性ハロゲン化銀粒子Ｙ１２及びＹ２２の調製）
上記Ｙ０２の調製において、（Ｘ−１）の臭化カリウムの量をＹ１１、Ｙ２１と同様に変更し、塩化銀含有率６０モル％の比較用青感性ハロゲン化銀平板状粒子Ｙ１２、Ｙ２２を調製した。粒子形状、変動係数は、それぞれＹ１１、Ｙ２１と同等であった。
ハロゲン化銀乳剤Ｙ１はＹ０１、Ｙ１１およびＹ２１を１：３：６の銀モル比で混合して得た。また、ハロゲン化銀乳剤Ｙ２はＹ０２、Ｙ１２およびＹ２２をＹ１と同様に１：３：６の銀モル比で混合して得た。
乳剤 ハロゲン組成Ｂｒ／Ｃｌ
Ｙ１ ３．５／９６．５
Ｙ２ ４０／６０
【０１１３】
（赤感性ハロゲン化銀乳剤粒子の調製）
塩臭化銀乳剤Ｒ１｛立方体、平均粒子サイズ０．２３μｍの大サイズ乳剤粒子Ｒ０１と平均粒子サイズ０．１７４μｍの中サイズ乳剤粒子Ｒ１１と平均粒子サイズ０．１２１μｍの小サイズ乳剤粒子Ｒ２１の２：３：５混合物（銀モル比）。粒子サイズ分布の変動係数は、それぞれ０．１１と０．１２及び０．１３、ハロゲン組成は共にＢｒ／Ｃｌ＝４０／６０｝である乳剤粒子を当業界で知られているコントロールダブルジェット法により硝酸銀と塩化ナトリウムと臭化カリウムの混合物を添加することにより調製した。 Ｋ₂ＩｒＣｌ₆を使用し、イリジウム含有率は２×１０^-7モル／銀モルとなるように調製した。この乳剤粒子には、下記に示す赤感性増感色素(Ｄ)を大サイズ乳剤粒子Ｒ０１、中サイズ乳剤粒子Ｒ１１、小サイズ乳剤粒子Ｒ２１に対してそれぞれ銀１モルあたり、２．１×１０^-5モル、３．３×１０^-5モル、４．５×１０^-5モル、増感色素（Ｅ）をそれぞれ１．８×１０^-5モル、２．３×１０^-5モル、３．６×１０^-5モル、更に、増感色素（Ｆ）をそれぞれ０．８×１０^-5モル、１．４×１０^-5モル、２．１×１０^-5モル添加した。これらの乳剤の化学熟成は、硫黄増感剤と金増感剤を添加して最適に行った。さらに、下記化合物１を、ハロゲン化銀乳剤粒子Ｒ０１、Ｒ１１、Ｒ２１に対し、それぞれ銀１モルあたり９．０×１０^-4モル、１．０×１０^-3モル、１．４×１０^-3モル添加した。
また、下記のように、ハロゲン組成を変更し、その他は同等の粒子サイズと分散性が得られるように適宜条件を変更してサイズの異なる大、中、小乳剤粒子を混合してハロゲン化銀乳剤Ｒ２（Ｒ０２／Ｒ１２／Ｒ２２の混合）とＲ３（Ｒ０３／Ｒ１３／Ｒ２３の混合）を調製した。粒子サイズと変動係数は、大サイズ、中サイズ、小サイズ共に同等の粒子が得られた。化学熟成は上記赤感性乳剤と同等になるように行った。
乳剤 ハロゲン組成Ｂｒ／Ｃｌ
Ｒ１ ４０／６０
Ｒ２ ３．５／９６．５
Ｒ３ ０．５／９９．５
【０１１４】
【化１０】

【０１１５】
（緑感性ハロゲン化銀乳剤粒子の調製）
塩臭化銀乳剤Ｇ１｛立方体、平均粒子サイズ０．２０μｍの大サイズ乳剤粒子Ｇ０１と平均粒子サイズ０．１４６μｍの中サイズ乳剤粒子Ｇ１１と平均粒子サイズ０．１０２μｍの小サイズ乳剤粒子Ｇ２１の１：３：６混合物（銀モル比）。粒子サイズ分布の変動係数は、それぞれ０．１１と０．１２と０．１０、ハロゲン組成は共にＢｒ／Ｃｌ＝４０／６０｝である乳剤粒子を調製した。 Ｋ₂ＩｒＣｌ₆を使用し、イリジウム含有率は、２×１０^-7モル／銀モルになるように調製した。この乳剤粒子に対して、下記に示す緑感性増感色素(Ｇ)を銀１モルあたり、大サイズ乳剤粒子、中サイズ乳剤粒子、小サイズ乳剤粒子に対してそれぞれ２．１×１０^-4モル、３．０×１０^-4モル、３．５×１０^-4モル、増感色素（Ｈ）をそれぞれ０．８×１０^-4モル、１．３×１０^-4モル、１．７×１０^-4モル、増感色素（Ｉ）をそれぞれ１．２×１０^-4モル、１．４×１０^-4モル、１．９×１０^-4モル、増感色素（Ｊ）をそれぞれ０．３×１０^-4モル、０．６×１０^-4モル、０．９×１０^-4モル添加した。これらの乳剤の化学熟成は、硫黄増感剤と金増感剤を添加して最適に行った。
また、下記のように、ハロゲン組成のみを変更し、その他は上記乳剤と同様に調製してハロゲン化銀乳剤Ｇ２（Ｇ０２／Ｇ１２／Ｇ２２の混合）とＧ３（Ｇ０３／Ｇ１３／Ｇ２３の混合）を調製した。粒子サイズと変動係数は、大サイズ、中サイズ、小サイズ共に同等の粒子が得られた。化学熟成は、上記緑感性粒子と同等になるように行った。
乳剤 ハロゲン組成Ｂｒ／Ｃｌ
Ｇ１ ４０／６０
Ｇ２ ３．５／９６．５
Ｇ３ ０．５／９９．５
【０１１６】
【化１１】

【０１１７】
（イエロー感光性層用乳化分散物Ｙの調製）
下記構成の素材を溶解混合し、１０％ドデシルベンゼンスルホン酸ナトリウム８０ｍｌを含む１０％ゼラチン水溶液１０００ｇに乳化分散させて乳化分散物Ｙを調製した。
イエローカプラー（ＥｘＹ） １１６．０ｇ
添加物１ ８．８ｇ
添加物２ ９．０ｇ
添加物３ ４．８ｇ
添加物４ １０．０ｇ
溶媒１ ７９．０ｇ
溶媒２ ４４．０ｇ
溶媒３ ９．０ｇ
溶媒４ ４．０ｇ
酢酸エチル １５０．０ｍｌ
【０１１８】
【化１２】

【０１１９】
【化１３】

【０１２０】
【化１４】

【０１２１】
（マゼンタ感光性層用乳化分散物Ｍ、シアン感光性層用乳化分散物Ｃの調製）
乳化分散物Ｙの調製と同様にして、上記のイエローカプラー（ＥｘＹ）をマゼンタカプラー（ＥｘＭ）、シアンカプラー（ＥｘＣ）にそれぞれ同質量置換えた以外は全く同様にして、マゼンタカプラー（ＥｘＭ）、シアンカプラー（ＥｘＣ）を用いてマゼンタ及びシアン感光性層用乳化分散物Ｍ、Ｃをそれぞれ調製した。
【０１２２】
【化１５】

【０１２３】
（染料固体微粒子分散物の調製）
下記染料１のメタノールウェットケーキを化合物の正味量が２４０ｇになるように秤量し、分散助剤として下記化合物２を４８ｇ秤量し、水を加えて４０００ｇとした。“流通式サンドグラインダーミル（ＵＶＭ−２）“（アイメックスＫ．Ｋ．製）にジルコニアビーズ（０．５ｍｍ径）を１．７リットル充填し、吐出量０．５リットル／ｍｉｎ、周速１０ｍ／ｓｅｃで２時間粉砕した。その後、分散物を化合物濃度が３質量％となるように希釈した。その後、９０℃で１０時間加熱処理を行った。こうして分散物Ａの調製を終了した。この分散物の平均粒子サイズは０．４５μｍであった。
【０１２４】
【化１６】

【０１２５】
（イエロー感光性乳剤層塗布液の調製）
下記乳剤および素材の割合で溶解混合し、イエロー感光性乳剤層塗布液とした。数字はｇ／ｍ²の単位で記載した。乳剤の塗布量は銀換算塗布量とした。
ハロゲン化銀乳剤（Ｙ１） ０．４９
イエローカプラー（ＥｘＹ） １．１８
添加物１ ０．０９
添加物２ ０．０９
添加物３ ０．０５
添加物４ ０．１０
溶媒１ ０．８０
溶媒２ ０．４５
溶媒３ ０．０９
溶媒４ ０．０４
ゼラチン ２．１０
化合物３ ０．０００５
化合物４ ０．０３
化合物５ ０．０４
【０１２６】
【化１７】

【０１２７】
（マゼンタ感光性乳剤層塗布液の調製）
イエロー感光性層塗布液と同様に下記組成の乳剤及び素材を混合溶解してマゼンタ感光性乳剤層とした。
ハロゲン化銀乳剤（Ｇ２） ０．５５
マゼンタカプラー（ＥｘＭ） ０．６８
添加物１ ０．０５
添加物２ ０．０５
添加物３ ０．０３
添加物４ ０．０６
溶媒１ ０．４６
溶媒２ ０．２６
溶媒３ ０．０５
溶媒４ ０．０２
ゼラチン １．２８
【０１２８】
（シアン感光性乳剤層塗布液の調製）
イエロー感光性層塗布液と同様に下記組成の乳剤及び素材を混合溶解してシアン感光性乳剤層とした。
ハロゲン化銀乳剤（Ｒ２） ０．４６
シアンカプラー（ＥｘＣ） ０．７２
添加物１ ０．０５５
添加物２ ０．０５６
添加物３ ０．０３
添加物４ ０．０６
溶媒１ ０．４９
溶媒２ ０．２７
溶媒３ ０．０５６
溶媒４ ０．０２５
ゼラチン ２．４５
【０１２９】
（ハレーション防止層の作成）
上記のごとく調製した染料固体微粒子分散物Ａを０．１１ｇ／ｍ²、ゼラチン塗布量を０．７０ｇ／ｍ²となるように混合溶解してハレーション防止層塗布液とした。
【０１３０】
（中間層の作成）
下記ゼラチン、および薬品を溶解混合して作成した。
ゼラチン ０．６７
化合物６ ０．０４
化合物７ ０．０２
溶媒５ ０．０１
【０１３１】
【化１８】

【０１３２】
（保護層の作成）
下記ゼラチン、および薬品を溶解混合して作成した。
ゼラチン ０．９６
ポリビニルアルコールのアクリル変性共重合体
（変性度１７％） ０．０２
化合物８ ０．０４
化合物９ ０．０１３
【０１３３】
【化１９】

【０１３４】
各層の硬化剤としては、１−オキシ−３，５−ジクロロ−ｓ−トリアジンナトリウム塩を用いた。また、イラジエーション防止を目的として下記染料２〜５を乳剤層に添加して用いた。
【０１３５】
【化２０】

【０１３６】
（支持体の作成）
厚さ１２０μｍの２軸延伸ポリエチレンテレフタレート支持体の片面に下記の導電性ポリマー（０．０５ｇ／ｍ²）と酸化スズ微粒子（０．２０ｇ／ｍ²）を含有するアクリル樹脂層を塗設した。
【０１３７】
【化２１】

【０１３８】
（塗布試料９の調製）
以上のごとく調製した塗布液を同時押し出し法により、ポリエチレンテレフタレート支持体のアクリル層樹脂を塗設した反対側にハレーション防止層を最下層として下記塗布構成となるように塗布、乾燥し、塗布試料９を作成した。
保護層
マゼンタ感光性層
中間層
シアン感光性層
中間層
イエロー感光性層
ハレーション防止層
ポリエチレンテレフタレート支持体
（他の塗布試料の調製）
ハロゲン化銀乳剤種を表３のように変更し、塗布銀量はハロゲン化銀の塗布量を、膜厚に関してはゼラチンを、膨潤率に関しては、硬化剤１−オキシ−３，５−ジクロロ−ｓ−トリアジンナトリウム塩の量を適宜変更して表３の値になるように調製して、残りの試料を作成した。なお、ハロゲン化銀の塗布量はイエロー感光性乳剤層、マゼンタ感光性乳剤層、シアン感光性乳剤層中の各ハロゲン化銀乳剤間の相互の使用質量比率を塗布試料９と同じに保ったまま変更した。
【０１３９】
（膜厚及び膨潤率の評価）
上記のごとく作成した各塗布試料に対して、塗布試料の断面を走査型電子顕微鏡（ＳＥＭ）にて観察し、膜厚を求めた。また、２７℃の純水中に十分な時間膨潤させたときの膨潤膜厚を打点法にて測定した。膨潤率は、本文中に記載した式から計算で求めた。各塗布試料の塗布銀量、膜厚、膨潤率を表３に示した。
【０１４０】
【表３】

【０１４１】
（処理液の準備）
映画用カラーポジフィルムの標準的な処理方法として、イーストマンコダック社から公表されているＥＣＰ−２プロセスに対し、サウンド現像工程および漂白促進処理工程前の定着工程を除いた簡易的な処理プロセスを準備した。作製した全試料について、塗布銀量の約３０％が現像されるような画像を露光した。露光の終了した試料は上記処理プロセスにて発色現像浴の補充液量がタンク容量の２倍となるまで連続処理（ランニングテスト）を実施し、ランニング平衡にある現像処理状態を作製した。
【０１４２】

【０１４３】
＜処理液処方＞
１リットル当たりの組成を示す

なお、上記において、現像工程で使用するＤ−３は現像主薬であり、リンス工程で使用するＤｅａｒｃｉｄｅ７０２は防黴剤である。
【０１４４】
（写真感度の評価）
感光計（富士写真フイルム（株）製ＦＷ型、光源の色温度３２００Ｋ）を用い、イエローとマゼンタの色補正フィルタ及び光学的な楔を介してニュートラルグレーのセンシトメトリ像が得られるように露光を行い、上記のごとく調製した処理液で、発色現像処理時間１８０秒（標準時間）での処理を行い、塗布試料５を基準として、被りよりイエロー、マゼンタ、シアンの各発色濃度が１．０高い濃度を与える露光量の比の逆数を１００倍した値で写真感度を評価した。なお、この値が大きいほど感度が高いことを意味する。
最高濃度（Ｄｍａｘ）は、１２０秒で処理したときの塗布試料の最高濃度部分を、Ｘ−ｒｉｔｅ３１０濃度測定機（Ｘ−ｒｉｔｅ社製）にて測定した視感濃度測定値を記載した。
【０１４５】
（現像進行性の評価）
上記の写真感度の評価において、発色現像処理時間１２０秒で処理したときの写真感度を求め、１８０秒での写真感度を与える露光量と１２０秒処理での写真感度を与える露光量の差について、塗布試料５を１００としたときの相対値として評価した。
【０１４６】
（定着性の評価）
上記のごとく調製した処理液の定着液を用いて、用意した塗布試料の未露光部を用いて定着開始からハロゲン化銀が定着されるまでの時間を膜の透過光濃度で評価し、塗布試料５を１００で表わしたときの相対値で示した。
【０１４７】
（乾燥性の評価）
水洗を完了した塗布試料に対して、４０℃の乾燥風を一定時間（３０秒）吹き付けたときの乾燥状態を下記の官能評価で評価した。
◎ ．．．． 十分に乾燥している。
○ ．．．． 少し湿り気が有るが、気にならない。
△ ．．．． 湿り気が残る。
× ．．．． 乾燥が不十分である。
【０１４８】
（残色の評価）
残色は、上記発色現像処理液において１２０秒で現像処理し、水洗工程の処理時間を６０秒から４０秒として処理した塗布試料を、以下の基準にしたがって官能評価で行った。
◎ ．．．． まったく残色しない。
○ ．．．． 残色あるが、気にならない。
△ ．．．． 残色多いが、実用的に許容される。
× ．．．． 残色多く、不可。
結果を表４に示した。
【０１４９】
【表４】

【０１５０】
表４に示されているごとく、感光材料のハロゲン化銀組成、塗布銀量、膜厚、膨潤率が本発明の範囲内にあるとき、現像進行性が非常に優れており、同時に定着性、乾燥性に優れ、残色がほとんどないことが確認され、迅速処理適性を有し、従来の処理に対して、現像、定着、水洗、乾燥のそれぞれの処理時間を短縮できることが確認された。
【０１５１】
実施例２
（青感性ハロゲン化銀平板状粒子の調製）
実施例１にて調製したＹ０１、Ｙ１１、Ｙ２１の調製において、イリジウム化合物（Ｋ₂ＩｒＣｌ₆）を表５に示すごとく変更した以外は全て乳剤Ｙ１と同様にしてイリジウム化合物の含有量のみ異なる乳剤を調製した。粒子サイズ、アスペクト比、分散性は、実施例１の乳剤Ｙ１に含まれるハロゲン化銀粒子と同等であった。
【０１５２】
（青感性ハロゲン化銀立方体粒子の調製）
塩臭化銀乳剤｛立方体、平均粒子サイズ０．７μｍの大サイズ乳剤粒子Ｙ０３と平均粒子サイズ０．５μｍの中サイズ乳剤粒子Ｙ１３及び平均粒子サイズ０．３６μｍの小サイズ乳剤粒子Ｙ２３との１：５：４混合物（銀モル比）。粒子サイズ分布の変動係数は、それぞれ９％と１０％と１２％、ハロゲン組成は共にＢｒ／Ｃｌ＝１．５／９８．５｝である乳剤粒子を当業界で知られているコントロールダブルジェット法により硝酸銀と塩化ナトリウムと臭化カリウムの混合物を添加することにより調製した。イリジウム含有率は表５に示した値となるように添加した。これらの乳剤粒子に対して、実施例１で使用した増感色素を添加して分光増感を施した。これらの乳剤の化学熟成は実施例１で用いたＹ０１、Ｙ１１、Ｙ２１と同じとなるように硫黄増感剤と金増感剤を添加して最適に行った。
このようにして表５に示すようにイリジウム化合物の含有量のみ異なる各乳剤を調製した。
【０１５３】
（赤、緑感性ハロゲン化銀乳剤粒子の調製）
実施例１と同様にして、青感性ハロゲン化銀乳剤の調製においてイリジウム化合物の添加量を同じ塗布試料で使用する青感光性乳剤と同様に変更し、その他はすべて実施例１と同様にして、赤感光性乳剤粒子、緑感光性乳剤粒子を調製した。
【０１５４】
（塗布試料の調製）
実施例１で調製した固体分散染料の加熱処理を行わない染料分散物を調製し、表５に示したごとく固体分散染料を変更した。また、乳剤粒子もイリジウム化合物の量を示した乳剤にそれぞれ変更した。また、青感光性乳剤粒子は、平板状粒子、あるいは、立方体粒子を用いて、表５に示したごとく塗布試料を調製した。
【０１５５】
（写真感度の評価）
実施例１の写真感度評価において、現像工程の処理温度を１℃上げて、１４０秒の処理時間で処理したときの感度を評価した。被りより発色濃度が１．０高い濃度を与える露光量の比の逆数で写真感度を評価し、塗布試料１７を１００としたときの相対値として評価した。
【０１５６】
（相反則性の評価）
上記の写真感度評価において、露光時間を、１秒と、１／１０００秒としてそれぞれ露光し、現像処理した。露光量はそれぞれの照度において同等となるように調節した。露光時間の相違する上記両露光間の階調の変化を以下に示す基準にて評価した。
○ ．．．．． 階調の変化少なく良好
△ ．．．．． 階調の変化少しあるが許容される。
× ．．．．． 階調の変化大きい。
【０１５７】
（粒状性の評価）
実施例１で行った露光を、濃度１．０となるように光学的な楔の濃度を調節して一様な露光を行い、写真感度の評価と同様に現像処理を行った。現像処理した試料を３００倍に拡大投影して観察し、以下の基準で官能評価した。
○ ．．．．． 粒状目立たず、気にならない。
△ ．．．．． 粒状目に付くが、実用的に許容される。
× ．．．．． 粒状性悪く、不可。
【０１５８】
（鮮鋭性の評価）
鮮鋭性の評価は視覚上影響の大きいマゼンタ色像、及びシアン色像に対して行った。各試料に対して、緑色フィルタ及び赤色フィルタ及び鮮鋭度測定用ウェッジを通して露光を与え、写真感度の評価と同様に現像処理を行い、ＣＴＦ測定の評価を行った。ＣＴＦ０．８を与える空間周波数（本／ｍｍ）をもって鮮鋭度を評価した。値が大きいほど鮮鋭度が高いことを示す。
【０１５９】
（現像進行性の評価）
写真感度の評価において、１００秒処理と１４０秒処理の写真感度（前記と同様（被り＋１．０）の濃度に基づく評価）を求め、１４０秒での写真感度を与える露光量と１００秒処理での写真感度を与える露光量の差について、塗布試料１７を１００としたときの相対値として評価した。
結果を表５に示した。
【０１６０】
【表５】

【０１６１】
表５より明らかなように、イリジウム化合物が１．０×１０^-8モル以上５．０×１０^-6モル以下である場合、相反則性が良好で現像進行性が非常に早いことがわかる。また、４０℃以上の熱処理工程を経て調製された固体微粒子分散物を含有することにより鮮鋭性が良好であり、また、イエロー乳剤層に平板状粒子を用いた場合に、粒状性が良く、しかも現像進行性が非常に早く迅速処理適性があり、実施例１と同様に処理時間短縮が可能であることがわかった。
【０１６２】
【発明の効果】
請求項１及び７記載の発明によれば、高感度で処理後の残色がない、迅速処理可能な映画用ハロゲン化銀カラー感光材料、並びに画像形成方法を提供することができる。
また請求項２〜７記載の発明によれば、高画質、特に、粒状性が良く、高い鮮鋭度であって、さらには相反則性が良好で現像進行性が速く、迅速処理可能な映画用ハロゲン化銀カラー感光材料、並びに画像形成方法を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silver halide color photographic light-sensitive material for movies, and in particular, a movie color having high image quality and suitability for rapid processing (especially, shortening of processing time during each processing step such as color development processing time). The present invention relates to a photographic material and an image forming method.
[0002]
[Prior art]
Photosensitive materials used for movies are enlarged and projected at the time of projection, so they have very good graininess and high sharpness compared to photosensitive materials used in each stage of shooting, editing, and projection. It has been demanded. On the other hand, in the movie processing process, two pieces of information, that is, video information by a color former and sound information mainly by a silver image are woven into one film in a film for film development, fixing, The water washing process is characterized in that it is performed independently, and when the drying process is excluded, the number of conventional process steps is as many as 15 processes. In addition, since the processing time of each process is long, there is a demand for simplification of the processing process and shortening of the processing time in order to reduce the number of processing processes and reduce the environmental load.
In response to these demands, from the viewpoint of reducing processing steps, Japanese Patent Application Laid-Open No. 11-95371 discloses a black antihalation layer by using a solid fine particle dispersion that can be removed by processing after a color developing bath. A technique capable of omitting the step of removing the resin back layer containing carbon fine particles is disclosed. Furthermore, in JP-A-11-282106, in addition to omitting the resin back layer removing step containing carbon fine particles, an infrared-absorbing dye with little residual color is formed in the color development processing step as sound track information. A technique that can omit the sound track development process is disclosed. These techniques are excellent techniques for reducing the number of processing steps.
However, even if the number of processing steps can be reduced in this way, a larger amount of processing is performed than before, that is, there is a strong demand for further rapid processing. In particular, not only the number of steps is reduced, but also the processing time in each processing step. Therefore, there is a demand for shortening the processing time by increasing the processing speed of each process.
[0003]
[Problems to be solved by the invention]
An object of the present invention is first to provide a silver halide color light-sensitive material for movie which can be processed quickly and has high sensitivity and no residual color after processing, and an image forming method.
A second object of the present invention is to provide a silver halide color light-sensitive material for movies and an image forming method which can be processed quickly, with high image quality, in particular, good graininess and high sharpness.
A third object of the present invention is to provide a silver halide color light-sensitive material for movies and an image forming method which have good reciprocity and fast development progress in addition to the above.
[0004]
[Means for Solving the Problems]
  As a result of intensive studies, the present inventors have found that the above problems can be achieved by the following method.
(1) On a support, a yellow color-sensitive photosensitive silver halide emulsion layer, a magenta color-sensitive silver halide emulsion layer, a cyan color-sensitive silver halide emulsion layer, a non-photosensitive non-color-forming hydrophilic colloid layer In the silver halide color photographic light-sensitive material having at least one layer of each of the above-mentioned layers, the yellow color-sensitive silver halide emulsion layer, the magenta color-sensitive silver halide emulsion layer, and the cyan color-sensitive silver halide emulsion layer are contained in the photosensitive layer. Silver chloride content of the silver halide grains is 95 mol% or more,The photosensitive silver halide grains are 1.0 × 10 ^-8 Mol / silver mol or more 5.0 × 10 ^-6 Containing iridium compounds in moles / silver moles or less,Total applied silver amount is 1.7 g / m²The film having a layer having the photosensitive silver halide-containing layer relative to the support has a film thickness of 12.0 μm or less and a swelling ratio with respect to water of 200% or less. Silver halide color photographic material.
(2) At least one of the light-sensitive silver halide emulsion layers contains tabular light-sensitive silver halide grains having an aspect ratio of 2 or more with the {100} plane as the main plane.In (1)The silver halide color photographic light-sensitive material for movie described.
(3) A layer containing tabular photosensitive silver halide grains having an aspect ratio of 2 or more with the {100} plane as the main plane is a yellow color developing photosensitive silver halide emulsion layer.In (2)The silver halide color photographic light-sensitive material for movie described.
(4) A solid fine particle dispersion of a dye represented by the following general formula (I) is included in at least one of the non-photosensitive hydrophilic colloid layers (1)To any one of items (3) to (3)The silver halide color photographic light-sensitive material for movie described.
  Formula (I)
        D- (X) y
  In general formula (I), D represents a compound residue having a chromophore, X represents a dissociative hydrogen or a group having a dissociative hydrogen, and y represents an integer of 1 to 7.
(5) The maximum density of neutral gray consisting of yellow color density, magenta color density and cyan color density obtained after development processing is 3.3 or more (1)To any one of items (4) to (4)The silver halide color photographic light-sensitive material for movie described.
(6(1)To any one of items (5) to (5)DescriptionThe projectionA method for forming an image of a silver halide color photographic light-sensitive material for movies, characterized in that after the exposure, the silver halide color photographic light-sensitive material for image development is developed with a color development time of 2 minutes 30 seconds or less.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The present invention relates to a technique for realizing rapid processing suitability.
The ECP-2 process published by Eastman Kodak Company for the processing of color photographic materials for movies, especially positive films, is developed at 36.7 ° C. for 3 minutes, first fixing at 27 ° C. for 40 seconds, and thereafter It is recommended that the water washing step is 40 seconds at 27 ° C., the water washing time after sound development is 1 minute at 27 ° C., and the drying time is 3 minutes to 5 minutes at 57 ° C.
In order to shorten the processing time up to the recommended value of the developing process, it is often performed to increase the developing temperature by several degrees C to shorten the processing time. However, there is an adverse effect that increasing the temperature accelerates the deterioration of the developing solution. In the present invention, as will be described later, the present invention relates to a technique for making development progress very fast, and it is possible to shorten the development processing time without substantially raising the development temperature and causing deterioration of the development processing solution. Become. Similarly, the time can be shortened for the fixing process and the drying process.
In the present invention, high image quality, in particular, good graininess, high sharpness, and quick processing suitability are imparted.
[0006]
First, the silver halide emulsion used in the present invention will be described.
The halogen composition of the silver halide grains used in the present invention is characterized by containing silver halide having a high silver chloride content and a high development processing speed and a fast fixing speed. Specifically, the silver halide content of all silver halide grains is preferably 95 mol% or more, more preferably 96 mol% or more, and still more preferably 97 mol% or more and 100% or less (ie, silver chloride). Silver chlorobromide, silver chloroiodide, or silver chloroiodobromide). As the photosensitive layer used in the silver halide color photographic light-sensitive material, there are a cyan color developing layer, a magenta color developing layer, and a yellow color developing layer. When the total silver halide content is in the above range, all the color developing layers are not necessarily included. The silver chloride content need not be in the above preferred range, but more preferably, the silver chloride content of the silver halide in each photosensitive layer is preferably contained in the above preferred range. Further, each color-forming layer often contains at least two types of silver halide grains having a different silver halide grain size or light absorption rate (sensitivity) for the purpose of obtaining a desired gradation. The silver chloride content of all silver halide grains in the same coloring layer with different grain size or light absorption rate (sensitivity) need not be in the above range, but more preferably the same in the same coloring layer. It is preferable that all the silver chloride contents of the silver halide grains having the same particle size or the same light absorption rate (sensitivity) are included in the above range.
[0007]
The halogen composition of the photosensitive silver halide grains used in the present invention is preferably silver chloride as described above. However, when the halogen composition is within the scope of the present invention, silver chlorobromide, silver chloroiodide Silver chloroiodobromide may also be used. There is no particular limitation on the use of halogen other than silver chloride, and silver halide grains having a so-called core / shell structure may be used during silver halide grain formation. During precipitation aggregation, during the dispersion step, Different halogen composition phases can also be formed on the particle surface by causing halogen conversion due to the difference in solubility product during the chemical sensitization process or after the chemical sensitization and before coating.
[0008]
Examples of the shape of the silver halide grains include cubes, octahedrons, tabular grains, spherical grains, rod-shaped grains, potato grains, etc., but in the present invention, cubic grains and tabular grains are preferred, Tabular grains are preferably used for the purpose of imparting high sensitivity and performance with good graininess.
In the present invention, tabular grains refer to grains having an aspect ratio (diameter / thickness) greater than 1, and average aspect ratio refers to the average of the aspect ratios of individual tabular grains. The diameter refers to the diameter of a circle having an area equal to the projected area of the tabular grains, and the thickness refers to the distance between two main planes. The main plane means a surface having the largest area of tabular grains.
[0009]
In the present invention, tabular silver halide grains are 50% or more, more preferably 60% or more, more preferably 80%, more preferably 80% or more of the projected area of all silver halide grains contained in at least the same silver halide emulsion layer. More preferably, it is 90% or more, and most preferably 95% or more and 100% or less. Further, the tabular silver halide grains are more preferably contained in all silver halide emulsion layers.
In the present invention, the average aspect ratio when tabular silver halide grains are used is preferably 2 or more and 100 or less, more preferably 3 or more and 50 or less. Further, grains having rounded corners of silver halide grains can be preferably used.
The surface index (Miller index) of the surface of the photosensitive silver halide grain is not particularly limited, but it is preferable that the ratio of the {100} plane having high spectral sensitizing efficiency when the spectral sensitizing dye is adsorbed is high. . The ratio is preferably 50% or more, more preferably 65% or more, and still more preferably 80% or more and 100% or less. The ratio of the Miller index was determined by T. using the adsorption dependency of the {111} face and the {100} face in the adsorption of the sensitizing dye. Tani; Imaging Sci. 29, 165 (1985).
[0010]
The tabular grains that can be used in the present invention are preferably tabular grains having {100} as the main plane, which has high spectral sensitization efficiency. The shape of a tabular grain having a {100} plane as a main plane is a right-angled parallelogram shape, or a 3-5 pentagon shape where one corner of the right-angled parallelogram is missing. As a vertex and a right-angled triangle portion formed by sides forming the corners thereof), or a 4-8 octagonal shape having two or more and four or less missing portions. If a right-angled parallelogram shape that compensates for the missing portion is a supplementary quadrilateral, the ratio of adjacent sides (long side length / short side length) of the right-angled parallelogram and the supplemental quadrilateral is 1-6. , Preferably 1-4, more preferably 1-2.
[0011]
Tabular silver halide emulsion grains having a {100} major plane may be used in any emulsion layer, but a yellow color developing light-sensitive silver halide emulsion layer is particularly preferred. Further, it is also preferable to use it for all photosensitive silver halide emulsion layers including a yellow color-forming photosensitive silver halide emulsion layer.
[0012]
The method for forming tabular silver halide emulsion grains having {100} major planes is to add and mix an aqueous silver salt solution and an aqueous halide salt solution in a dispersion medium such as an aqueous gelatin solution while stirring. At this time, for example, in JP-A-6-301129, 6-347929, 9-34045, and 9-96881, silver iodide or iodide ion, or silver bromide or bromide ion is present. And a method of introducing a crystal defect that imparts anisotropic growth properties such as screw dislocations by causing strain in the nucleus due to the difference in the size of the crystal lattice from silver chloride. When the screw dislocation is introduced, the formation of two-dimensional nuclei on the surface is no longer promoted under low supersaturation conditions, so that crystallization proceeds on this surface, and by introducing the screw dislocation, tabular grains are formed. It is formed. Here, the low supersaturation condition is preferably 35% or less, more preferably 2 to 20% at the time of critical addition. Although the crystal defects are not determined to be screw dislocations, it is considered that there is a high possibility of screw dislocations because the direction in which the dislocations are introduced or because anisotropic growth is imparted to the grains. In order to make the tabular grains thinner, it is disclosed in JP-A-8-122954 and JP-A-9-189977 that the introduced dislocation retention is preferable.
[0013]
Further, in JP-A-6-347928, imidazoles and 3,5-diaminotriazoles are used, and in JP-A-8-339044, polyvinyl alcohols are used to add a {100} surface formation accelerator. A method of forming tabular grains having a {100} major plane is disclosed. Furthermore, it is disclosed in US Pat. Nos. 5,320,935, 5,264,337, 5,292,632, 5,314,798, 5,413,904, WO94 / 22051, and the like. It can be prepared by the method. However, the present invention is not limited to these.
[0014]
The particles of the present invention may have a so-called core / shell structure consisting of a core part and a shell part surrounding the core part. When having a core / shell structure, 90 mol% or more of the core portion is preferably silver chloride. The core portion may further comprise two or more portions having different halogen compositions. The shell portion is preferably 50% or less, particularly preferably 20% or less of the total particle volume. The shell portion is preferably silver iodochloride or silver bromochloride. The shell part preferably contains 0.5 mol% to 10 mol% of silver bromide, particularly preferably 1 mol% to 5 mol%, and the silver bromide content in all grains is preferably 5 mol%. The following are preferable, and 3 mol% or less is especially preferable.
[0015]
The grain size of the photosensitive silver halide may be fine grains having a size of 0.2 μm or less, or may be large grains having a projected diameter area of 10 μm or more. However, in order to obtain good graininess, the fine grains may be fine grains. preferable. The silver halide grains of the present invention are preferably monodispersed for the purpose of speeding development, and the variation coefficient of the grain size of each silver halide grain is 0.3 or less (preferably 0.3 to 0.00). 05), more preferably 0.25 or less (preferably 0.25 to 0.05). The variation coefficient here is represented by a ratio (s / d) between a statistical standard deviation value (s) and an average particle size (d).
[0016]
  In the present invention, an iridium compound, that is, an iridium complex or an iridium ion-containing compound is added.use. The iridium ion-containing compound is a trivalent or tetravalent salt or complex salt, and a complex salt is particularly preferable. For example, primary iridium (III) chloride, primary iridium (III) bromide, secondary iridium chloride (IV), sodium hexachloroiridium (III), potassium hexachloroiridium (IV), hexaammine iridium (IV) salt , Halogens such as trioxalatoiridium (III) salt and trioxalatoiridium (IV) salt, amines, and oxalato complex salts are preferable.In the present invention,The amount of iridium complex or iridium ion-containing compound used is based on the amount of silver halide.1. 0x10^-8Mol / silver mol or more 5.0 × 10^-6Mol / silver mol or less, more preferably 2.0 × 10^-8Mol / silver mol or more 2.5 × 10^-6It is preferably less than mol / silver mol.
[0017]
The iridium complex or the iridium ion-containing compound may be contained in the core part, the shell part, or the uniform part of the silver halide grains, and a portion having a different halogen composition is grown at the corner part by heterojunction. Although it can also be selectively contained, it is not particularly limited.
[0018]
The photosensitive silver halide grain of the present invention may contain at least one metal complex selected from rhodium, rhenium, ruthenium, osnium, cobalt, mercury, or iron in addition to the iridium complex or the iridium ion-containing compound. it can. One kind of these metal complexes may be used, or two or more kinds of complexes of the same metal and different metals may be used in combination. The preferred metal content is 1 × 10 5 per mole of silver.^-9Mol / silver mol to 1 × 10^-3The mole / silver mole range is preferred, 1 × 10^-9Mol / silver mol to 1 × 10^-FourThe range of mole / silver mole is more preferred. As a specific metal complex structure, for example, a metal complex having a structure described in JP-A-7-225449 can be used. As the cobalt and iron complex, a 6-cyano metal complex can be preferably used.
[0019]
The photosensitive silver halide grain of the present invention is preferably chemically sensitized. Preferred chemical sensitization methods include chalcogen compound (sulfur compounds, selenium compounds, tellurium compounds) sensitization methods, gold compounds, and noble metal sensitization methods such as platinum, palladium, and iridium compounds, as is well known in the art. Or reduction sensitization can be used. Furthermore, spectral sensitization can also be used. The additive used in this step is RD No. No. 17643, ibid. No. 18716 and No. 1 of the same. The compounds described in No. 307105 can be preferably used.
[0020]
The silver coating amount of the silver halide color light-sensitive material for cinema of the present invention is preferably small for the purpose of reducing development and / or fixing load, and is 1.7 g / m.²Or less, more preferably 1.65 g / m.²Or less, more preferably 1.6 g / m.²The following is preferred. The lower limit is not particularly limited as long as the desired maximum concentration and granularity can be obtained, but preferably 1.2 g / m.²The above is preferable.
[0021]
The film thickness and swelling rate of the silver halide color photographic material for movies of the present invention are preferably small values for the purpose of reducing the drying load. The film thickness is preferably 12 μm or less, more preferably 11.5 μm or less, still more preferably 10.8 μm or less and 8 μm or more. The swelling rate is preferably 200% or less, more preferably 185% or less and 100% or more. Here, the film thickness is the total film thickness of the photographic composition layer on the support, and the swelling rate mentioned here is the film thickness when immersed in distilled water at 27 ° C. and allowed to swell for a sufficient time. The maximum swelling film thickness can be obtained by the following formula.
Swelling rate = 100 × (maximum swollen film thickness−film thickness) ÷ film thickness (%)
[0022]
The swelling ratio can be adjusted to the above range by adjusting the amount of gelatin hardener added.
There are no particular restrictions on the type of gelatin hardener, but it is represented by the formula (6) at the lower right of page 8 of JP-A-1-214845, page 17, H-1, 46, 8, 14, and JP-A-2-214852. The compound (H-1 to 76) represented by the formulas (VII to XII) described in the columns 13 to 23 of US Pat. No. 4,618,573 are preferably used. it can.
[0023]
The silver halide color light-sensitive material for cinema of the present invention preferably has a neutral gray maximum density of 3.3 or more obtained from the yellow color density, magenta color density and cyan color density obtained after development processing. Furthermore, 3.3 or more and 4.5 or less are more preferable, 3.0 or more and 4.3 or less are still more preferable, and 3.5 or more and 4.1 or less are the most preferable.
The neutral gray is obtained by performing an exposure process so as to realize a transmission neutral gray defined by the International Lighting Association. The concentration can be measured by a concentration meter known in the art, for example, a concentration meter such as Macbeth or X-rite.
[0024]
In the present invention, it is preferable that at least one layer of the non-photosensitive hydrophilic colloid layer contains a dye solid fine particle dispersion, and more preferably, the dye is represented by the general formula (I). It is.
Since the solid fine particle dispersion of the dye represented by the general formula (I) shown below tends to stay in the hydrophilic colloid layer and easily dissolves during processing, it is possible to achieve both improvement of sharpness and reduction of coloring on a white background. Moreover, the stability over time in the hydrophilic colloid layer is high.
Hereinafter, the dye represented by formula (I) will be described.
Formula (I)
D- (X) y
In the general formula (I), D represents a compound residue having a chromophore, X represents a dissociative hydrogen or a group having a dissociative hydrogen, and y represents an integer of 1 to 7. The dye represented by the general formula (I) of the present invention is characterized in that it has dissociative hydrogen or the like in its molecular structure.
The compound residue having a chromophore in D can be selected from a number of well-known dyes.
Examples of these compounds include oxonol dyes, merocyanine dyes, cyanine dyes, arylidene dyes, azomethine dyes, triphenylmethane dyes, azo dyes, anthraquinone dyes, and indoaniline dyes.
[0025]
X represents a group having a dissociative hydrogen or a dissociative hydrogen bonded to D directly or via a divalent linking group.
The divalent linking group between X and D is an alkylene group, an arylene group, a heterocyclic residue, -CO-, -SO._n-(N = 0, 1, 2), -NR- (R represents a hydrogen atom, an alkyl group, an aryl group), -O-, and a divalent group obtained by combining these linking groups, and further May have a substituent such as an alkyl group, aryl group, alkoxy group, amino group, acylamino group, halogen atom, hydroxyl group, carboxy group, sulfamoyl group, carbamoyl group, sulfonamide group. -(CH₂)_n-(N = 1,2,3), -CH₂CH (CH_Three) CH₂-, 1,2-phenylene, 5-carboxy-1,3-phenylene, 1,4-phenylene, 6-methoxy-1,3-phenylene, -CONHC₆H_Four-Etc. can be mentioned.
[0026]
The dissociative hydrogen represented by X or the group having dissociable hydrogen is non-dissociated when the dye represented by the general formula (I) is added to the silver halide photographic light-sensitive material of the present invention. The dye having the general formula (I) is substantially water-insoluble, and in the step of developing the photosensitive material, it is dissociated to make the compound of the general formula (I) substantially water-soluble. Has characteristics. Examples of the group having a dissociable hydrogen represented by X include groups having a carboxylic acid group, a sulfonamide group, a sulfamoyl group, a sulfonylcarbamoyl group, an acylsulfamoyl group, a phenolic hydroxyl group, and the like. Examples of the dissociable hydrogen represented by X include hydrogen of an enol group of an oxonol dye.
[0027]
A preferred range for y is 1-5, and a particularly preferred range is 1-3.
Among the compounds represented by the general formula (I), a compound having a dissociative hydrogen in X is a group having a carboxylic acid group, and particularly a compound having an aryl group substituted with a carboxyl group. preferable.
Of the compounds represented by the general formula (I), more preferred are compounds represented by the following general formula (II) or general formula (III).
Formula (II)
A¹= L¹-(L²= L^Three)_m-Q
In general formula (II), A¹Represents an acidic nucleus, Q represents an aryl group or a heterocyclic group, L¹, L², L^ThreeEach represents a methine group, and m represents 0, 1 or 2. However, the compound of the general formula (II) has a carboxylic acid group, sulfonamide group, sulfamoyl group, sulfonylcarbamoyl group, acylsulfamoyl group and phenolic hydroxyl group as a group having a dissociative hydrogen in the molecule, and a dissociative property. It has 1 to 7 groups (preferably carboxylic acid groups) selected from the group consisting of enol groups of oxonol dyes as hydrogen.
[0028]
General formula (III)
A¹= L¹-(L²= L^Three)_n-A²
In general formula (III), A¹And A²Represents an acidic nucleus, L¹, L², L^ThreeEach represents a methine group, and n represents 0, 1, 2 or 3. However, the compound of the general formula (III) has a carboxylic acid group, a sulfonamido group, a sulfamoyl group, a sulfonylcarbonyl group, an acylsulfamoyl group and a phenolic hydroxyl group as a group having a dissociative hydrogen in the molecule. And 1 to 7 groups (preferably carboxylic acid groups) selected from the group consisting of enol groups of oxonol dyes as dissociative hydrogen.
[0029]
Hereinafter, the general formulas (II) and (III) will be described in detail.
A¹And A²The acidic nucleus represented by is preferably derived from a cyclic ketomethylene compound or a compound having a methylene group sandwiched between electron-withdrawing groups. Examples of cyclic ketomethylene compounds include 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolone, barbituric acid, thiobarbituric acid, indandione, dioxopyrazolo Mention may be made of pyridine, hydroxypyridone, pyrazolidinedione, 2,5-dihydrofuran. These may have a substituent.
[0030]
A compound having a methylene group sandwiched between electron-withdrawing groups is represented by Z¹CH₂Z²It can be expressed as. Where Z¹And Z²Are -CN and -SO, respectively.₂R¹¹, -COR¹¹, -COOR¹², -CONHR¹², -SO₂NHR¹²Or -C [= C (CN)₂] R¹¹Represents. R¹¹Represents an alkyl group, an aryl group, or a heterocyclic group, and R¹²Is a hydrogen atom or R¹¹And each of these may have a substituent.
[0031]
Examples of the aryl group represented by Q include a phenyl group and a naphthyl group. Each of these may have a substituent. Examples of the heterocyclic group represented by Q include pyrrole, indole, furan, thiophene, imidazole, pyrazole, indolizine, quinoline, carbazole, phenothiazine, phenoxazine, indoline, thiazole, pyridine, pyridazine, thiadiazine, pyran, thiopyran. And oxodiazole, benzoquinoline, thiadiazole, pyrrolothiazole, pyrrolopyridazine, tetrazole, oxazole, coumarin, and coumarone. Each of these may have a substituent.
[0032]
L¹, L²And L^ThreeThe methine group represented by may have a substituent, and the substituents may be linked to each other to form a 5- or 6-membered ring (for example, cyclopentene, cyclohexene).
[0033]
The substituents that each of the above-described groups may have are not particularly limited unless they are compounds that substantially dissolve the compounds represented by the general formulas (I) to (III) in water at pH 5 to pH 7. There is no. For example, the following substituents can be mentioned.
[0034]
Carboxylic acid group, C1-C10 sulfonamide group (for example, methanesulfonamide, benzenesulfonamide, butanesulfonamide, n-octanesulfonamide), C0-10 unsubstituted or alkyl- or aryl-substituted sulfamoyl group (Eg, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl, naphthylsulfamoyl, butylsulfamoyl), sulfonylcarbamoyl groups having 2 to 10 carbon atoms (eg, methanesulfonylcarbamoyl, propanesulfonylcarbamoyl, benzene) Sulfonylcarbamoyl), acylsulfamoyl groups having 1 to 10 carbon atoms (for example, acetylsulfamoyl, propionylsulfamoyl, pivaloylsulfamoyl, benzoylsulfamoyl),
[0035]
A linear or cyclic alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, isopropyl, butyl, hexyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl, benzyl, Phenethyl, 4-carboxybenzyl, 2-diethylaminoethyl), an alkenyl group having 2 to 8 carbon atoms (for example, vinyl, allyl), an alkoxy group having 1 to 8 carbon atoms (for example, methoxy, ethoxy, butoxy), a halogen atom ( For example, F, Cl, Br), an amino group having 0 to 10 carbon atoms (for example, unsubstituted amino, dimethylamino, diethylamino, carboxyethylamino), an ester group having 2 to 10 carbon atoms (for example, methoxycarbonyl), An amide group having 1 to 10 carbon atoms (for example, acetylamino, Amide), a carbamoyl group having 1 to 10 carbon atoms (for example, unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl), an aryl group having 6 to 10 carbon atoms (for example, phenyl, naphthyl, hydroxyphenyl, 4-carboxyphenyl, 3 -Carboxyphenyl, 3,5-dicarboxyphenyl, 4-methanesulfonamidophenyl, 4-butanesulfonamidophenyl), aryloxy groups having 6 to 10 carbon atoms (for example, phenoxy, 4-carboxyphenoxy, 3-methylphenoxy, Naphthoxy),
[0036]
C1-C8 alkylthio group (for example, methylthio, ethylthio, octylthio), C6-C10 arylthio group (for example, phenylthio, naphthylthio), C1-C10 acyl group (for example, acetyl, benzoyl, propanoyl) ), A sulfonyl group having 1 to 10 carbon atoms (for example, methanesulfonyl, benzenesulfonyl), a ureido group having 1 to 10 carbon atoms (for example, ureido, methylureido), and a urethane group having 2 to 10 carbon atoms (for example, methoxycarbonyl). Amino, ethoxycarbonylamino), cyano group, hydroxyl group, nitro group, heterocyclic group (for example, 5-carboxybenzoxazole ring), pyridine ring, sulfolane ring, pyrrole ring, pyrrolidine ring, morpholine ring, piperazine ring, pyrimidine ring, Franc ring).
[0037]
Of the compounds represented by the general formula (III), more preferred are compounds represented by the following general formula (IV). The compound represented by the general formula (IV) has enol group hydrogen as dissociative hydrogen.
[0038]
[Chemical 1]

[0039]
In general formula (IV), R¹Represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R²Is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, -COR^FourOr -SO₂R^FourRepresents R^ThreeIs a hydrogen atom, cyano group, hydroxyl group, carboxyl group, alkyl group, aryl group, -CO₂R^Four, -OR^Four, -NR^FiveR⁶, -CONR^FiveR⁶, -NR^FiveCOR^Four, -NR^FiveSO₂R^FourOr -NR^FiveCONR^FiveR⁶(Where R^FourRepresents an alkyl group or an aryl group, R^Five, R⁶Each represents a hydrogen atom, an alkyl group, or an aryl group. ). L¹, L², L^ThreeEach represents a methine group. n represents 1 or 2.
[0040]
In general formula (IV), R¹Examples of the alkyl group include an alkyl group having 1 to 4 carbon atoms, a 2-cyanoethyl group, a 2-hydroxyethyl group, and a carboxybenzyl group, and the aryl group includes a phenyl group, a 2-methylphenyl group, and a 2-carboxyphenyl group. 3-carboxyphenyl group, 4-carboxyphenyl group, 3,6-dicarboxyphenyl group, 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2-chloro-4-carboxyphenyl group, A 4-methylsulfamoylphenyl group is exemplified, and examples of the heterocyclic group include a 5-carboxybenzoxazol-2-yl group.
[0041]
R²Examples of the alkyl group include an alkyl group having 1 to 4 carbon atoms, a carboxymethyl group, a 2-hydroxyethyl group, and a 2-methoxyethyl group, and the aryl group includes a 2-carboxyphenyl group, a 3-carboxyphenyl group, and 4 -Carboxyphenyl group and 3,6-dicarboxyphenyl group are mentioned, and the heterocyclic group is pyridyl group, -COR^FourAs the acetyl group, -SO₂R^FourExamples thereof include a methanesulfonyl group.
[0042]
R^Three, R^Four, R^Five, R⁶Examples of the alkyl group include an alkyl group having 1 to 4 carbon atoms. R^Three, R^Four, R^Five, R⁶Examples of the aryl group include a phenyl group and a methylphenyl group.
In the present invention, R¹Is preferably a carboxyl group-substituted phenyl group (for example, 2-carboxyphenyl, 3-carboxyphenyl, 4-carboxyphenyl, 3,6-dicarboxyphenyl).
[0043]
Specific examples of the compounds represented by the general formulas (I) to (IV) preferably used in the present invention are described below, but are not limited thereto.
[0044]
[Chemical 2]

[0045]
[Chemical 3]

[0046]
[Formula 4]

[0047]
[Chemical formula 5]

[0048]
[Chemical 6]

[0049]
[Chemical 7]

[0050]
[Table 1]

[0051]
[Table 2]

[0052]
Specific examples of the compound represented by the general formula (IV) include, in addition to the above, IV-13 to IV-51 in paragraph numbers 0101 to 0105 of JP-A No. 11-282106. It is preferable as a compound represented by.
[0053]
The dyes preferably used in the present invention are International Patent WO 88/04794, European Published Patent Nos. 274,723A1, 276,566, 299,435, JP-A-52-92716, and 55-. 155350, 55-155351, 61-205934, 48-68623, U.S. Pat.Nos. 2,527,583, 3,486,897, 3,746,539, Specifications or publications such as 3,933,798, 4,130,429, 4,040,841, JP-A-3-282244, 3-7931, and 3-167546 Or can be synthesized according to the method described in the above.
[0054]
The solid fine particle dispersion preferably used in the present invention can be prepared by a known method. Details of the production method are described in functional pigment application technology (published by CMC, 1991).
Media distribution is one of the common methods. In this method, the dye powder or its wet cake called wet cake is made into an aqueous slurry, and a known pulverizer (for example, ball mill, vibration ball mill, planetary ball mill, vertical sand mill, roller mill, pin mill, Using a coball mill, caddy mill, horizontal sand mill, attritor, etc.), grinding with mechanical force in the presence of dispersion media (steel balls, ceramic balls, glass beads, alumina beads, zirconia silicate beads, zirconia beads, Ottawa sand, etc.) To do. Among these, beads having an average diameter of preferably 2 mm to 0.3 mm, more preferably 1 mm to 0.3 mm, and still more preferably 0.5 mm to 0.3 mm are used. In addition to these, a method of pulverizing with a jet mill, a roll mill, a homogenizer, a colloid mill or a dissolver, and a pulverizing method with an ultrasonic disperser can also be used.
[0055]
Further, as disclosed in U.S. Pat. No. 2,870,012, after dissolving in a uniform solution, a poor solvent is added to precipitate solid fine particles. For example, as disclosed in JP-A-3-182743. In addition, a method of precipitating solid fine particles by lowering the pH after dissolving in an alkaline solution can also be used.
[0056]
When preparing these solid fine particle dispersions, it is preferable that a dispersion aid is present. Dispersing aids that have been disclosed in the past include alkyl phenoxy ethoxy sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfate ester salt, alkyl sulfosuccinate, sodium oleyl methyl taurate, naphthalene sulfonic acid. Denatured formaldehyde, polyacrylic acid, polymethacrylic acid, maleic acid acrylic acid copolymer, anionic dispersants such as carboxymethyl cellulose and cellulose sulfate, polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. Nonionic dispersants, cationic dispersants and betaine dispersants are particularly preferable, and polyalkylene oxides represented by the following general formula (Va) or (Vb) are particularly used. Masui.
[0057]
[Chemical 8]

[0058]
In the general formulas (Va) and (Vb), a and b each represent a value of 5 to 500. Preferable values of a and b are 10 to 200, respectively, and more preferable values of a and b are 50 to 150, respectively. A value of a and b within this range is preferable from the viewpoint of improving the uniformity of the coated surface.
[0059]
In the dispersion aid, the ratio of the polyethylene oxide part is preferably 0.3 to 0.9, more preferably 0.7 to 0.9, and still more preferably 0.8 to 0.9 by mass ratio. The average molecular weight of the dispersion aid is preferably 1,000 to 30,000, more preferably 5,000 to 40,000, and still more preferably 8,000 to 20,000. Further, the HLB (hydrophilic / lipophilic balance) of the dispersion aid is preferably 7 to 30, more preferably 12 to 30, and still more preferably 18 to 30. A numerical value within this range is preferable in terms of improving the uniformity of the coated surface.
[0060]
These compounds are available as commercial products, such as Pluronic from BASF.
Examples of these preferable compounds include I-1 to I-23 described in paragraph Nos. 0115 and 0116 of JP-A No. 11-282106, and the paragraph No. part is the specification of the present application as a part of the specification of the present invention. Captured in the book.
[0061]
In the present invention, the amount of the dispersion aid used with respect to the dye preferably used in the present invention is preferably 0.05 to 0.5, more preferably 0.1 to 0.3, by mass ratio. When the amount of the dispersion aid is within this range, it is preferable from the viewpoint of improving the uniformity of the coated surface.
In addition, hydrophilic colloids such as polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polysaccharides and gelatin can be coexisted for the purpose of stabilizing the dispersion and reducing the viscosity when preparing the solid fine particle dispersion. Among these, in the present invention, it is particularly preferable that the compound represented by the general formula [V] described in paragraph Nos. 0130 to 0167 of JP-A No. 11-282106 coexist, and the paragraph portion is the specification of the present application. As part of
[0062]
The solid fine particle dispersion of the dye preferably used in the present invention is preferably one that is heat-treated before, during or after dispersion by the method disclosed in JP-A-5-216166.
[0063]
The dye preferably used in the present invention is preferably subjected to heat treatment at 40 ° C. or higher before being incorporated into the light-sensitive material.
The heat treatment preferably applied to the dye dispersion in the present invention includes a method performed before the step of finely dispersing in a solid state such as heating the dye powder in a solvent, and water or other in the presence of a dispersant. There are a method in which the dispersion is carried out without cooling, or a temperature is applied, and a method in which the liquid after dispersion and the coating liquid are heat-treated, but it is particularly preferable to carry out the dispersion after dispersion.
[0064]
When a plurality of solid fine particle dispersions containing the dye represented by the general formula (I) are used in a specific layer, it is sufficient that at least one of them is heat-treated.
[0065]
The pH during the dispersion and the heat treatment after the dispersion may be any conditions as long as the dispersion is stably present, preferably pH 2.0 or more and 8.0 or less, more preferably 2.0 or more and 6.5 or less, and still more preferably 2. .5 or more and less than 4.5. The pH during the heat treatment is preferably in this range from the viewpoint of improving the film strength of the coated product.
For adjusting the pH of the dispersion, for example, sulfuric acid, hydrochloric acid, acetic acid, citric acid, phosphoric acid, oxalic acid, carbonic acid, sodium hydrogen carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide or a buffer solution thereof can be used. .
[0066]
The temperature for the heat treatment varies depending on the heat treatment process, the size and shape of the powder or particles, the heat treatment conditions, the solvent, and so on. In the case of heat treatment with powder, 40 ° C to 200 ° C is suitable, preferably 90 ° C to 150 ° C. In the case of heat treatment in a solvent, 40 ° C to 150 ° C, preferably 90 ° C to When heat treatment is performed at 150 ° C. and during dispersion, 40 ° C. to 90 ° C. is appropriate, preferably 50 ° C. to 90 ° C., and when heat is applied to the dispersion after dispersion, 40 ° C. to 100 ° C. is appropriate, Preferably it is 50 to 95 degreeC. If the heat treatment temperature is lower than 40 ° C., the effect is poor.
[0067]
When the heat treatment is performed in a solvent, the type of the solvent is not limited as long as it does not substantially dissolve the dye. For example, water, alcohols (for example, methanol, ethanol, isopropyl alcohol, butanol, isoamyl amyl) Coal, octanol, ethylene glycol, diethylene glycol, ethyl cellosolve), ketones (eg, acetone, methyl ethyl ketone), esters (eg, ethyl acetate, butyl acetate), alkyl carboxylic acids (eg, acetic acid, propionic acid), nitriles ( For example, acetonitrile), ethers (for example, dimethoxyethane, dioxane, tetrahydrofuran), amides (for example, dimethylformamide) and the like can be mentioned.
[0068]
Further, even when these solvents alone dissolve the dye, they can be used if the dye does not substantially dissolve by mixing with water or other solvents or adjusting the pH.
[0069]
The time for the heat treatment is not general, and it takes a long time if the temperature is low, and a short time if the temperature is high. Although it can be set arbitrarily so that the heat treatment can be realized within a range that does not affect the manufacturing process, it is usually preferably 1 hour to 4 days.
[0070]
In order to provide a layer containing dye fine particles in a photographic light-sensitive material, the fine particles thus obtained are dispersed in a suitable binder to prepare a substantially uniform solid dispersion of particles. It can be provided by coating on a desired support.
The binder is not particularly limited as long as it is a hydrophilic colloid that can be used in a photosensitive emulsion layer or a non-photosensitive layer, but usually a gelatin or a synthetic polymer such as polyvinyl alcohol or polyacrylamide is used.
[0071]
The fine particles in the solid dispersion preferably have an average particle size of 0.005 μm to 10 μm, preferably 0.01 μm to 1 μm, more preferably 0.01 μm to 0.7 μm. This range is preferable in terms of the non-aggregation property of the fine particles and the light absorption efficiency. The solid fine particle dispersion of the dye represented by the general formula (I) used in the present invention can be used alone or in combination with a plurality of solid fine particle dispersions.
[0072]
Furthermore, the hydrophilic colloid layer to which the solid fine particles are added may be a single layer or a plurality of layers. For example, when adding a single solid fine particle dispersion to only one layer, dividing and adding to a plurality of layers, adding a plurality of solid fine particle dispersions to only one layer at a time, adding to separate layers, etc. As an example, it is not limited to the above.
[0073]
Further, the solid fine particle dispersion can be incorporated in a necessary amount as an antihalation layer and added to the photosensitive silver halide emulsion layer for preventing irradiation.
The hydrophilic colloid layer containing the solid fine particle dispersion of the dye of the general formula (I) preferably used in the present invention is provided between the support and the silver halide emulsion layer closest thereto. Here, a non-photosensitive hydrophilic colloid layer other than the hydrophilic colloid layer containing the solid fine particle dispersion may be provided between the support and the silver halide emulsion layer closest thereto.
[0074]
The solid fine particle dispersion of the dye preferably used in the present invention is contained in the non-photosensitive hydrophilic colloid layer in the silver halide photographic light-sensitive material according to the hue of the dye, and a plurality of the non-photosensitive layers are provided. In the light-sensitive material of the present embodiment, it can be contained in these plural layers.
0.1-50 mass% is suitable for the dye density | concentration in the solid fine particle dispersion of this invention, Preferably it is 2-35 mass%, More preferably, it is 2-30 mass%. A dye concentration within this range is preferred from the viewpoint of the viscosity of the dispersion. The preferred coating amount of the solid fine particle dye is about 0.05 to 0.5 g / m.²It is.
[0075]
The silver halide color photographic light-sensitive material of the present invention is processed by a usual development process.
In particular, in the processing of a silver halide color photographic light-sensitive material for movies, the positive light-sensitive material for movies can be processed by the following processing steps conventionally used. In the case of the positive photosensitive material for movies of the present invention, the steps of (1) prebath bath and (2) water washing bath for removing the resin back layer can be reduced. Further, such a shortened processing step is preferable for simplification of processing.
In addition, when the sound track is formed with a dye image, the following steps (6) first fixing bath, (7) water washing bath, (11) sound development and (12) water washing can be reduced. This is a very preferable embodiment.
The photosensitive material of the present invention can exhibit excellent performance even in such processing steps.
[0076]
Standard processing (excluding drying) for conventional film positive photosensitive materials
(1) Pre-bath bath
(2) Washing bath
(3) Color development bath
(4) Stop bath
(5) Washing bath
(6) First fixing bath
(7) Washing bath
(8) Bleaching acceleration bath
(9) Bleaching bath
(10) Washing bath
(11) Sound development (painting development)
(12) Washing with water
(13) Second fixing bath
(14) Washing bath
(15) Stable bath
[0077]
In the present invention, among the processing steps, the color development time (step (3) above) is 2 minutes 30 seconds or less (the lower limit is preferably 6 seconds or more, more preferably 10 seconds or more, still more preferably 20 seconds). Above, most preferably 30 seconds or more), more preferably 2 minutes or less (lower limit is the same as 2 minutes 30 seconds), the effect of the present invention is remarkably preferable.
The first fixing step is preferably performed for 20 seconds to 40 seconds, more preferably 23 seconds to less than 40 seconds, and further preferably 25 seconds to 35 seconds.
[0078]
Next, the photographic layer of the silver halide photographic light-sensitive material of the present invention will be described.
[0079]
There is no limitation on the color developability and color sensitivity of each color-sensitive photosensitive silver halide emulsion layer. For example, even if a color developable light-sensitive silver halide emulsion layer has color sensitivity in the infrared region. It doesn't matter.
Examples of typical layer order include a non-photosensitive hydrophilic colloid layer in order from the support (non-photosensitive hydrophilic containing a solid fine particle dispersion of a dye represented by formula (I) preferably used in the present invention) Colloidal layer is preferred), yellow color-sensitive photosensitive silver halide emulsion layer, non-photosensitive hydrophilic colloid layer (color mixing prevention layer), cyan color-forming photosensitive silver halide emulsion layer, non-photosensitive hydrophilic colloid layer (color mixing) Prevention layer), magenta color-forming photosensitive silver halide emulsion layer, and non-photosensitive hydrophilic colloid layer (protective layer). However, the number of the non-photosensitive hydrophilic colloid layers may be increased or decreased depending on the purpose.
[0080]
Of these, the magenta color-sensitive photosensitive silver halide emulsion layer is preferably located at the position farthest from the support in the total photosensitive silver halide emulsion layer. There is no restriction | limiting in particular in the number of layers and layer order of a non-photosensitive hydrophilic colloid layer. Each of the yellow, cyan, and magenta color-sensitive photosensitive silver halide emulsion layers is composed of a single photosensitive silver halide emulsion layer, but from a plurality of silver halide emulsion layers having the same color sensitivity and different sensitivities. It may be. In the case where the magenta color-forming photosensitive silver halide emulsion layer is composed of a plurality of light-sensitive silver halide emulsion layers, at least one of the plurality of magenta color-sensitive light-sensitive silver halide emulsion layers is a total light-sensitive silver halide. It is preferable to be in the position farthest from the support in the emulsion layer. Further, the cyan color developing light-sensitive silver halide emulsion layer and the yellow color developing light-sensitive silver halide emulsion layer are arranged in the yellow color forming light-sensitive silver halide emulsion layer, the cyan color developing light-sensitive silver halide layer from a position close to the support. Although it may be an emulsion layer or vice versa, it is preferably in the order of a yellow color-forming photosensitive silver halide emulsion layer and a cyan color-forming photosensitive silver halide emulsion layer.
[0081]
In any one of the photographic constituent layers composed of a photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer (intermediate layer, protective layer, etc.) provided on the support, preferably a silver halide emulsion layer 1-aryl-5-mercaptotetrazole compound at 1.0 × 10 5 per mole of silver halide^-Five~ 5.0 × 10^-2It is preferable to add a molar amount, and further 1.0 × 10^-Four~ 1.0 × 10^-2It is preferable to add a molar amount. By adding in this range, the stain on the processed color photographic surface after the continuous processing can be further reduced.
[0082]
As such a 1-aryl-5-mercaptotetrazole compound, an aryl group at the 1-position is preferably an unsubstituted or substituted phenyl group, and preferred specific examples of this substituent include acylamino groups (for example, acetylamino, -NHCOC_FiveH₁₁ ⁽ⁿ⁾Etc.), ureido groups (for example, methylureido), alkoxy groups (for example, methoxy), carboxylic acid groups, amino groups, sulfamoyl groups, and the like. ) May be bonded. Further, the position of the substituent is preferably the meta or para position.
[0083]
Specific examples thereof include 1- (m-methylureidophenyl) -5-mercaptotetrazole and 1- (m-acetylaminophenyl) -5-mercaptotetrazole.
[0084]
The photographic additives that can be used in the present invention are described in the following Research Disclosure Journal (RD), and the description locations related to the following table are shown.

[0085]
Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable.
Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (especially Y-28 on page 18); A coupler represented by the general formula (I) in claim 1 of the 307248 publication; a coupler represented by the general formula (I) in columns 45 to 55 of US Pat. No. 5,066,576; paragraph 0008 of JP-A-4-74425 Couplers represented by general formula (I); couplers according to claim 1 on page 40 of EP 498,381A1 (especially D-35 on page 18); couplers represented by formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y-54 (page 41)); couplers represented by formulas (II) to (IV) in columns 36 to 58 of column 7, US 4,476,219 (particularly II-17, 19 (column 17 ), II-24 (column 19)).
[0086]
Magenta coupler; JP-A-3-9737 (L-57 (lower right of page 11), L-68 (lower right of page 12), L-77 (lower right of page 13)); EP 456,257 A-4 -63 (134 P.), A-4 -73, -75 (p.139); EP 486,965, M-4, -6 (p.26), M-7 (p.27); JP-A-6-43611, paragraph 0024, M-45 , M-1 of paragraph 0036 of JP-A-5-204106; M-22 of paragraph 0237 of JP-A-4-362631.
Cyan coupler: CX-1, 3, 4, 5, 11, 12, 14, 15 (pages 14 to 16) of JP-A-4-204843; C-7, 10 (page 35) of JP-A-4-43345, 34 35 (page 37), (I-1), (I-17) (pages 42 to 43); a coupler represented by the general formula (Ia) or (Ib) of claim 1 of JP-A-6-67385.
Polymer coupler: P-1, P-5 (page 11) of JP-A-2-44345.
Infrared coupler for forming a sound track: a coupler described in JP-A-63-143546 and the patent cited therein.
[0087]
As couplers in which the coloring dye has an appropriate diffusibility, those described in US 4,366,237, GB 2,125570, EP 96,873B, DE 3,234,533 are preferable.
A coupler for correcting unwanted absorption of the coloring dye is a yellow colored cyan coupler represented by the formula (CI), (CII), (CIII), (CIV) described on page 5 of EP 456,257A1 (especially page 84). YC-86), yellow colored magenta coupler ExM-7 described in EP, page 202, EX-1 (page 249), EX-7 (page 251), magenta colored cyan coupler CC-9 described in US 4,833,069 (Column 8), CC-13 (Column 10), US 4,837,136 (2) (Column 8), colorless masking coupler represented by the formula [C-1] of claim 1 of W092 / 11575 (particularly pages 36 to 45) Are preferred).
[0088]
Examples of the compounds (including couplers) that release a photographically useful compound residue by reacting with oxidized developing agent include the following. Development inhibitor releasing compounds: compounds represented by formulas (I), (II), (III), and (IV) described on page 11 of EP 378,236A1 (particularly T-101 (page 30), T-104 (31 ), T-113 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP 436, 938A2 Compounds represented (especially D-49 (page 51)), compounds represented by formula (1) of JP-A-5-307248 (especially paragraph (23) of paragraph 0027), formulas described on pages 5-6 of EP 440,195A2 Compounds represented by (I), (II), (III) (especially I- (1) on page 29); Bleach accelerator releasing compounds: EP 310, 125A2 on page 5, formulas (I), (I ') Compounds represented by formula (I) of claim 1 of JP-A-6-59411 (especially (7) of paragraph 0022); ligand-releasing compounds: US Compound represented by LIG-X according to claim 1 of 4,555,478 (particularly the compound in columns 21 to 41 of column 12); leuco dye releasing compound; compounds 1 to 6 of columns 3 to 8 of US 4,749,641; fluorescent dye releasing compound : US 4,774,18 1. Compound 1 represented by COUP-DYE of claim 1 (particularly compounds 1 to 11 in columns 7 to 10); development accelerator or fogging agent releasing compound: Formula (1), (2), (column 3 of US 4,656,123) 3) (especially (I-22) in column 25) and ExZK-2 on page 75, lines 36 to 38 of EP 450,637A2; a compound that releases a group that becomes a dye only after leaving: US 4,857,447 A compound represented by formula (I) of claim 1 (particularly Y-1 to Y-19 in columns 25 to 36).
[0089]
As additives other than couplers, the following are preferable.
Oil-soluble organic compound dispersion medium: P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93 (140-144) of JP-A-62-215272 Page); Latex for impregnation of oil-soluble organic compound: Latex described in US 4,199,363; Oxidant scavenger for developing agent: Compound represented by formula (I) in columns 2 to 54 of US 4,978,606 (particularly I-, ( 1), (2), (6), (12) (columns 4-5), US 4,923,787, column 2, line 5 to 10 (especially compound 1 (column 3); stain inhibitor: EP 298321A 4 Pages 30-33, formulas (I)-(III), in particular I-47, 72, III-1, 27 (pages 24-48); antifading agents: EP 298321A A-6, 7, 20, 21 , 23, 24, 25, 26, 30, 37, 40, 42, 48, 63, 90, 92, 94, 164 (pages 69-118), US 5,122,444 columns 25-38 II-1 to III-23 , Especially III-10, EP 471347A, pages 8-12, I-1 to III-4, especially II-2, US 5,139,931, columns 32 to 40, A-1 to 48, especially A-39, 42; For reducing the amount of colorant or color mixing inhibitor used: EP 411324A, pages 5-24, I-1 II-15, especially I-46; formalin scavenger: EP 477932A, pages 24-29, SCV-1 to 28, especially SCV-8;
[0090]
Development inhibitor precursor: P-24, 37, 39 of JP-A-62-168139 (pages 6 to 7); US Pat. No. 5,019,492 claim 1, especially 28 to 29 of column 7, preservatives, fungicides : US 4,923,790 columns 3-15 I-1 to III-43, especially II-1, 9, 10, 18, III-25; stabilizers, antifoggants: US 4,923,793 columns 6-16 I-1 To (14), especially I-1, 60, (2), (13), US Pat. No. 4,952,483, columns 1 to 65, especially 36: chemical sensitizer: triphenylphosphine selenide, JP-A-5 Compound No. -40324; Dye: a-1 to b-20 on pages 15 to 18 of JP-A-3-156450, especially a-1, 12, 18, 27, 35, 36, b-5, pages 27 to 29 V-1 to 23, especially V-1, EP 445627A, pages 33 to 55, FI-1 to F-II-43, especially FI-11, F-II-8, EP 457153A, pages 17 to 28 III -1 to 36, especially III-1, 3, W088 / 04794 8 to 26 Dye-1 to 124 microcrystalline dispersion, EP 319999A, pages 6 to 11 compounds 1 to 22, especially compound 1, EP 519306A Of the compounds of formulas (1) to (3) D-1 to 87 (pages 3 to 28), US 4,268,622 Compounds 1 to 22 represented by formula (I) (columns 3 to 10), compounds (1) to (31) represented by formula (I) of US 4,923,788 (columns 2 to 9); UV absorber: Compounds (18b) to (18r) represented by formula (1) of 46-3335, 101 to 427 (pages 6 to 9), compounds (3) to (66) (10) represented by formula (I) of EP 520938A -44) and compounds HBT-1 to HBT-10 (page 14) represented by formula (III), compounds (1) to (31) represented by formula (1) of EP 521823A (columns 2 to 9).
[0091]
In the present invention, the ratio of the oil-soluble component in the photographic composition layer to the hydrophilic binder can be arbitrarily set. A preferable ratio in the photographic constituent layer other than the protective layer is 0.05 to 1.50, more preferably 0.10 to 1.40, and most preferably 0.20 to 1.30 in terms of mass ratio. The film strength, scratch resistance, and curl characteristics can be adjusted by optimizing the ratio of each layer.
[0092]
Hereinafter, the support will be described. Examples of the plastic film support include polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, polycarbonate, polystyrene, and polyethylene.
[0093]
Among them, a polyethylene terephthalate film is preferable, and a biaxially stretched and heat-set polyethylene terephthalate film is particularly preferable from the viewpoint of stability and toughness.
[0094]
The thickness of the support is not particularly limited, but is generally in the range of 15 to 500 μm, and particularly preferably in the range of 40 to 200 μm because it is advantageous in terms of ease of handling and versatility, and is preferably 85 to 150 μm. Most preferred.
The transmissive support preferably means a substrate that transmits 90% or more of visible light, and contains dyed silicon, alumina sol, chromium salt, zirconium salt, etc. as long as it does not substantially interfere with light transmission. May be.
[0095]
In order to firmly adhere the photosensitive layer to the surface of the plastic film support, the following surface treatment is generally performed. The same surface treatment is generally performed on the surface on which the antistatic layer (back layer) is formed.
(1) Directly after surface activation treatment such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxygen treatment, etc. A method for obtaining adhesive strength by coating a photographic emulsion (photosensitive layer forming coating solution) on
(2) After these surface treatments, there are two methods: a method in which an undercoat layer is provided and a photographic emulsion layer is applied thereon.
[0096]
Of these, the method (2) is more effective and widely used. Each of these surface treatments forms a somewhat polar group on the originally hydrophobic support surface, removes a thin layer that causes negative adhesion to the surface, and crosslinks the surface. It seems to increase the density and the adhesive strength, and as a result, the affinity of the components contained in the undercoat layer solution with the polar group increases, the fastness of the adhesive surface increases, etc. This is considered to improve the adhesion between the undercoat layer and the support surface.
[0097]
A non-photosensitive layer (antistatic layer) containing conductive metal oxide particles is preferably provided on the surface of the plastic film support on which the photosensitive layer is not provided.
As the binder for the non-photosensitive layer, acrylic resin, vinyl resin, polyurethane resin and polyester resin are preferably used. The non-photosensitive layer of the present invention is preferably hardened, and examples of the hardener include aziridines, triazines, vinyl sulfones, aldehydes, cyanoacrylates, peptides, epoxies, and melamines. Although used, a melamine compound is particularly preferable from the viewpoint of firmly fixing the conductive metal oxide particles.
[0098]
Examples of the conductive metal oxide particles include ZnO and TiO.₂, SnO₂, Al₂O_Three, In₂O_Three, MgO, BaO, MoO_ThreeAnd V₂O_FiveAnd composite oxides thereof, and metal oxides further containing different atoms in these metal oxides.
[0099]
As the metal oxide, SnO₂, ZnO, Al₂O_ThreeTiO₂, In₂O_Three, MgO, and V₂O_FiveIs preferred, and SnO₂, ZnO, In₂O_ThreeTiO₂And V₂O_FiveIs preferred, SnO₂And V₂O_FiveIs particularly preferred.
As an example containing a small amount of different atoms, Zn, Al, In, TiO₂Nb or Ta, In₂O_ThreeSn and SnO₂On the other hand, there may be mentioned those doped with 0.01 to 30 mol% (preferably 0.1 to 10 mol%) of a different element such as Sb, Nb or a halogen element. When the added amount of the different element is less than 0.01 mol%, sufficient conductivity cannot be imparted to the oxide or the composite oxide. Since the prevention layer is darkened, it is not suitable for a photosensitive material. Accordingly, the material of the conductive metal oxide particles is preferably a material containing a small amount of different elements with respect to the metal oxide or the composite metal oxide. Also preferred are those containing an oxygen defect in the crystal structure.
[0100]
The conductive metal oxide particles should have a volume ratio of 50% or less with respect to the entire non-photosensitive layer, but preferably 3 to 30%. The coating amount is preferably in accordance with the conditions described in JP-A-10-62905.
When the volume ratio exceeds 50%, dirt is likely to adhere to the surface of the processed color photograph. When the volume ratio is less than 3%, the antistatic ability does not function sufficiently.
[0101]
The particle diameter of the conductive metal oxide particles is preferably as small as possible in order to reduce light scattering as much as possible, but should be determined using the ratio of the refractive index of the particles to the binder as a parameter, and Mie's theory Can be obtained using In general, the average particle size is in the range of 0.001 to 0.5 μm, preferably in the range of 0.003 to 0.2 μm. Here, the average particle size is a value including not only the primary particle size of the conductive metal oxide particles but also the particle size of the higher order structure.
[0102]
When the metal oxide fine particles are added to the coating solution for forming the antistatic layer, they may be added and dispersed as they are, but they are dispersed in a solvent such as water (including a dispersant and a binder as necessary). It is preferably added in the form of a dispersion.
[0103]
Further details of the above-described antistatic layer are described in paragraph Nos. 0204 to 0219 of JP-A No. 11-282106, and are preferably applied to the present application.
A surface layer is preferably provided on the antistatic layer. The surface layer is provided mainly for improving the slipperiness and scratch resistance and for assisting the function of preventing the detachment of the conductive metal oxide particles of the antistatic layer. The surface layer is also described in paragraph Nos. 0220 to 0224 of JP-A No. 11-282106, and is preferably applied to the present application.
Accordingly, the description of paragraph numbers 0204 to 0224 of JP-A-11-282106 is incorporated as part of the specification of the present application.
[0104]
The coating pH of the light-sensitive material of the present invention is preferably from 4.6 to 6.4, more preferably from 5.5 to 6.5. When the coating pH is higher than 6.5 in a long-time sample, the sensitization of the cyan image and the magenta image due to safelight irradiation is large. Conversely, when the coating pH is lower than 4.5, the photosensitive material is exposed. The yellow image density changes greatly with respect to the time change until development. Either case is a practical problem.
[0105]
The film pH of the silver halide color photographic light-sensitive material of the present invention is the pH of all photographic layers obtained by coating the coating solution on the support and does not necessarily match the pH of the coating solution. The coating pH can be measured by the following method as described in JP-A-61-245153. That is,
(1) 0.05 ml of pure water is dropped on the surface of the light-sensitive material coated with the silver halide emulsion. next,
(2) After standing for 3 minutes, the coating pH is measured with a surface pH measuring electrode (GS-165F manufactured by Toa Denpa). The coating pH can be adjusted using an acid (for example, sulfuric acid or citric acid) or an alkali (for example, sodium hydroxide or potassium hydroxide) as necessary.
[0106]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[0107]
Example 1
(Preparation of blue-sensitive silver halide emulsion grains Y01)
To a 2% aqueous solution of lime-processed gelatin, 1.0 g of sodium chloride was added, and an acid was added to adjust the pH to 4.5. An aqueous solution containing 0.03 mol of silver nitrate and an aqueous solution containing 0.03 mol of sodium chloride and potassium bromide were added and mixed at 40 ° C. with vigorous stirring. Subsequently, after adding an aqueous solution (X-1) containing 0.005 mol of potassium bromide, an aqueous solution containing 0.13 mol of silver nitrate and an aqueous solution containing 0.13 mol of sodium chloride were added. Further, the temperature was raised to 75 ° C., and while maintaining the pAg at 7.0, an aqueous solution containing 0.9 mol of silver nitrate, an aqueous solution containing 0.9 mol of sodium chloride, and a total silver amount of 2 × 10^-7Iridium compound (K₂IrCl₆5 minutes later, an aqueous solution containing 0.1 mol of silver nitrate and an aqueous solution containing 0.1 mol of sodium chloride were added and mixed. After leaving for 40 minutes, it was washed with settled water at 35 ° C. to perform desalting. Thereafter, 100 g of lime-processed gelatin was added, and the pH was adjusted to 6.0 and pAg 7.0. Thus, the main plane is a {100} plane tabular grain, the projected area equivalent diameter is 0.80 μm, the average thickness is 0.15 μm, the average aspect ratio is 4.5, and the equivalent to the side length of the cube is 0.39 μm, Tabular grains having a variation coefficient of 0.20 and a silver chloride content of 96.5 mol% were prepared. The sensitizing dyes (A), (B) and (C) shown below are 3.5 × 10 5 for the emulsion grains.^-FourMol, 2.5 × 10^-FiveMol, 1.8 × 10^-FiveIt added so that it might become a mole. Thereafter, sulfur sensitizer and gold sensitizer were added for optimal chemical ripening.
[0108]
[Chemical 9]

[0109]
(Preparation of blue-sensitive silver halide emulsion grains Y11)
In the preparation of Y01, the potassium bromide of (X-1) was changed to 0.010 mol, the projected area equivalent diameter was 0.60 μm, the average thickness was 0.13 μm, the average aspect ratio was 3.8, the coefficient of variation was 0.8. 19 tabular grains having a silver chloride content of 96.5 mol% were prepared. The sensitizing dyes (A), (B), and (C) are each 4.7 × 10^-FourMol, 4.6 × 10^-FiveMol, 2.7 × 10^-FourMole addition was performed, and chemical ripening was optimally performed in the same manner as in Y01. Except for these changes, this is the same as Y01.
[0110]
(Preparation of blue-sensitive silver halide grains Y21)
In the preparation of Y01, the potassium bromide of (X-1) was changed to 0.014 mol, the projected area equivalent diameter was 0.40 μm, the average thickness was 0.12 μm, the average aspect ratio was 3.3, the variation coefficient was 0.00. 18 tabular grains having a silver chloride content of 96.5 mol% were prepared. The sensitizing dyes (A), (B), and (C) are each 5.3 × 10 5^-FourMol, 6.3 × 10^-FiveMol, 3.8 × 10^-FourMole was added. Chemical aging was optimally performed in the same manner as Y01. Except for these changes, this is the same as Y01.
[0111]
(Preparation of comparative blue-sensitive silver halide grains Y02)
Tabular grains having a silver chloride content of 60 mol% are obtained by increasing the mixing ratio of potassium bromide according to the elapsed time of addition in the addition of sodium chloride added after 75 ° C. in the preparation of the Y01 tabular emulsion. It was created. The particle shape and coefficient of variation were equivalent to Y01. A sensitizing dye was added in the same manner as Y01. Chemical ripening was performed so as to have the same sensitivity as Y01. Except for these changes, this is the same as Y01.
[0112]
(Preparation of comparative blue-sensitive silver halide grains Y12 and Y22)
In the preparation of Y02, the amount of potassium bromide in (X-1) was changed in the same manner as in Y11 and Y21 to prepare comparative blue-sensitive silver halide tabular grains Y12 and Y22 having a silver chloride content of 60 mol%. did. The particle shape and variation coefficient were equivalent to Y11 and Y21, respectively.
Silver halide emulsion Y1 was obtained by mixing Y01, Y11 and Y21 in a silver molar ratio of 1: 3: 6. Further, the silver halide emulsion Y2 was obtained by mixing Y02, Y12 and Y22 in the same molar ratio of 1: 3: 6 as Y1.
Emulsion Halogen composition Br / Cl
Y1 3.5 / 96.5
Y2 40/60
[0113]
(Preparation of red-sensitive silver halide emulsion grains)
Silver chlorobromide emulsion R1 {cube, large-size emulsion grain R01 with an average grain size of 0.23 μm, medium-size emulsion grain R11 with an average grain size of 0.174 μm, and small-size emulsion grain R21 with an average grain size of 0.121 μm: 3: 5 mixture (silver molar ratio). Coefficients of variation in grain size distribution were 0.11, 0.12 and 0.13, respectively, and emulsion grains having halogen compositions of both Br / Cl = 40/60} were obtained by the control double jet method known in the art. Prepared by adding a mixture of silver nitrate, sodium chloride and potassium bromide. K₂IrCl₆And the iridium content is 2 × 10^-7It was prepared to be mol / silver mol. In this emulsion grain, the red sensitive sensitizing dye (D) shown below is 2.1 × 10 2 per mol of silver for each of the large emulsion grains R01, medium emulsion grains R11 and small emulsion grains R21.^-FiveMol, 3.3 × 10^-FiveMol, 4.5 × 10^-FiveMole and sensitizing dye (E) 1.8 × 10 respectively^-FiveMol, 2.3 × 10^-FiveMol, 3.6 × 10^-FiveMol, and further, a sensitizing dye (F) of 0.8 × 10^-FiveMol, 1.4 × 10^-FiveMol, 2.1 × 10^-FiveMole was added. The chemical ripening of these emulsions was optimally performed by adding a sulfur sensitizer and a gold sensitizer. Further, the following compound 1 is 9.0 × 10 6 per silver mole with respect to silver halide emulsion grains R01, R11 and R21.^-FourMol, 1.0 × 10^-3Mol, 1.4 × 10^-3Mole was added.
In addition, the silver halide was prepared by changing the halogen composition as described below, and changing the other conditions so that the equivalent grain size and dispersibility were obtained, and mixing large, medium and small emulsion grains of different sizes. Emulsions R2 (mixed R02 / R12 / R22) and R3 (mixed R03 / R13 / R23) were prepared. As for the particle size and coefficient of variation, particles having the same size were obtained for all of the large, medium and small sizes. Chemical ripening was carried out so as to be equivalent to the above red-sensitive emulsion.
Emulsion Halogen composition Br / Cl
R1 40/60
R2 3.5 / 96.5
R3 0.5 / 99.5
[0114]
[Chemical Formula 10]

[0115]
(Preparation of green sensitive silver halide emulsion grains)
Silver chlorobromide emulsion G1 {cube, large-size emulsion grains G01 having an average grain size of 0.20 μm, medium-size emulsion grains G11 having an average grain size of 0.146 μm, and small-size emulsion grains G21 having an average grain size of 0.102 μm 3: 6 mixture (silver molar ratio). Emulsion grains having a grain size distribution variation coefficient of 0.11, 0.12, and 0.10, and a halogen composition of Br / Cl = 40/60} were prepared. K₂IrCl₆The iridium content is 2 × 10^-7It was prepared to be mol / silver mol. The following green-sensitive sensitizing dye (G) is added to the emulsion grains in an amount of 2.1 × 10 2 per mole of silver, respectively for large-sized emulsion grains, medium-sized emulsion grains, and small-sized emulsion grains.^-FourMol, 3.0 × 10^-FourMol, 3.5 × 10^-FourMolar and sensitizing dye (H) 0.8 × 10 respectively^-FourMol, 1.3 × 10^-FourMol, 1.7 × 10^-FourMolar and sensitizing dye (I) 1.2 × 10 respectively^-FourMol, 1.4 × 10^-FourMol, 1.9 × 10^-FourMolar and sensitizing dye (J) 0.3 × 10 respectively^-FourMol, 0.6 × 10^-FourMol, 0.9 × 10^-FourMole was added. The chemical ripening of these emulsions was optimally performed by adding a sulfur sensitizer and a gold sensitizer.
Also, as described below, only the halogen composition was changed, and the others were prepared in the same manner as the above emulsion, and silver halide emulsions G2 (mixed G02 / G12 / G22) and G3 (mixed G03 / G13 / G23) were prepared. Prepared. As for the particle size and coefficient of variation, particles having the same size were obtained for all of the large, medium and small sizes. Chemical ripening was performed so as to be equivalent to the green sensitive particles.
Emulsion Halogen composition Br / Cl
G1 40/60
G2 3.5 / 96.5
G3 0.5 / 99.5
[0116]
Embedded image

[0117]
(Preparation of emulsion dispersion Y for yellow photosensitive layer)
A material having the following constitution was dissolved and mixed, and emulsified and dispersed in 1000 g of a 10% gelatin aqueous solution containing 80 ml of 10% sodium dodecylbenzenesulfonate to prepare an emulsified dispersion Y.
Yellow coupler (ExY) 116.0g
Additive 1 8.8g
Additive 2 9.0g
Additive 3 4.8 g
Additive 4 10.0g
Solvent 1 79.0 g
Solvent 2 44.0 g
Solvent 3 9.0g
Solvent 4 4.0 g
Ethyl acetate 150.0ml
[0118]
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[0119]
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[0120]
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[0121]
(Preparation of emulsion dispersion M for magenta photosensitive layer and emulsion dispersion C for cyan photosensitive layer)
In the same manner as in the preparation of the emulsified dispersion Y, except that the same amount of the yellow coupler (ExY) was replaced with the magenta coupler (ExM) and the cyan coupler (ExC), respectively, the magenta coupler (ExM), cyan Emulsified dispersions M and C for magenta and cyan photosensitive layers were prepared using a coupler (ExC), respectively.
[0122]
Embedded image

[0123]
(Preparation of dye solid fine particle dispersion)
The methanol wet cake of the following dye 1 was weighed so that the net amount of the compound was 240 g, 48 g of the following compound 2 was weighed as a dispersion aid, and water was added to make 4000 g. “Flow-through sand grinder mill (UVM-2)” (manufactured by IMEX KK) is filled with 1.7 liters of zirconia beads (0.5 mm diameter), discharge amount is 0.5 liter / min, and peripheral speed is 10 m / minute. Milled for 2 hours at sec. Thereafter, the dispersion was diluted so that the compound concentration was 3% by mass. Thereafter, heat treatment was performed at 90 ° C. for 10 hours. Thus, the preparation of Dispersion A was completed. The average particle size of this dispersion was 0.45 μm.
[0124]
Embedded image

[0125]
(Preparation of yellow photosensitive emulsion layer coating solution)
The yellow emulsion layer coating solution was prepared by dissolving and mixing at the following emulsion and material ratios. Number is g / m²It was described in units of. The coating amount of the emulsion was a silver conversion coating amount.
Silver halide emulsion (Y1) 0.49
Yellow coupler (ExY) 1.18
Additive 1 0.09
Additive 2 0.09
Additive 3 0.05
Additive 4 0.10
Solvent 1 0.80
Solvent 2 0.45
Solvent 3 0.09
Solvent 4 0.04
Gelatin 2.10
Compound 3 0.0005
Compound 4 0.03
Compound 5 0.04
[0126]
Embedded image

[0127]
(Preparation of magenta photosensitive emulsion layer coating solution)
In the same manner as the yellow photosensitive layer coating solution, an emulsion and a material having the following composition were mixed and dissolved to obtain a magenta photosensitive emulsion layer.
Silver halide emulsion (G2) 0.55
Magenta coupler (ExM) 0.68
Additive 1 0.05
Additive 2 0.05
Additive 3 0.03
Additive 4 0.06
Solvent 1 0.46
Solvent 2 0.26
Solvent 3 0.05
Solvent 4 0.02
Gelatin 1.28
[0128]
(Preparation of cyan photosensitive emulsion layer coating solution)
In the same manner as the yellow photosensitive layer coating solution, emulsions and materials having the following composition were mixed and dissolved to form a cyan photosensitive emulsion layer.
Silver halide emulsion (R2) 0.46
Cyan coupler (ExC) 0.72
Additive 1 0.055
Additive 2 0.056
Additive 3 0.03
Additive 4 0.06
Solvent 1 0.49
Solvent 2 0.27
Solvent 3 0.056
Solvent 4 0.025
Gelatin 2.45
[0129]
(Create an antihalation layer)
0.11 g / m of the dye solid fine particle dispersion A prepared as described above²Gelatin coating amount is 0.70 g / m²The resulting solution was mixed and dissolved to obtain an antihalation layer coating solution.
[0130]
(Middle layer creation)
The following gelatin and chemicals were dissolved and mixed.
Gelatin 0.67
Compound 6 0.04
Compound 7 0.02
Solvent 5 0.01
[0131]
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[0132]
(Create a protective layer)
The following gelatin and chemicals were dissolved and mixed.
Gelatin 0.96
Acrylic-modified copolymer of polyvinyl alcohol
(Degree of modification 17%) 0.02
Compound 8 0.04
Compound 9 0.013
[0133]
Embedded image

[0134]
As a curing agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. The following dyes 2 to 5 were added to the emulsion layer for the purpose of preventing irradiation.
[0135]
Embedded image

[0136]
(Create support)
On one side of a biaxially stretched polyethylene terephthalate support having a thickness of 120 μm, the following conductive polymer (0.05 g / m²) And tin oxide fine particles (0.20 g / m²) Containing an acrylic resin layer.
[0137]
Embedded image

[0138]
(Preparation of coating sample 9)
The coating solution prepared as described above was coated and dried by the simultaneous extrusion method so that the anti-halation layer was the bottom layer on the opposite side of the polyethylene terephthalate support on which the acrylic layer resin was coated, and dried. It was created.
Protective layer
Magenta photosensitive layer
Middle class
Cyan photosensitive layer
Middle class
Yellow photosensitive layer
Antihalation layer
Polyethylene terephthalate support
(Preparation of other coated samples)
The silver halide emulsion type was changed as shown in Table 3, the coating silver amount was the silver halide coating amount, the film thickness was gelatin, and the swelling ratio was 1-oxy-3,5-dichloro- The amount of s-triazine sodium salt was appropriately changed to prepare the values shown in Table 3, and the remaining samples were prepared. The coating amount of silver halide is the same as that of the coated sample 9 while the mutual use mass ratio between the silver halide emulsions in the yellow photosensitive emulsion layer, the magenta photosensitive emulsion layer, and the cyan photosensitive emulsion layer is maintained. changed.
[0139]
(Evaluation of film thickness and swelling rate)
For each coated sample prepared as described above, the cross section of the coated sample was observed with a scanning electron microscope (SEM) to determine the film thickness. Moreover, the swelling film thickness when it swelled for a sufficient time in 27 degreeC pure water was measured with the dot method. The swelling rate was calculated from the formula described in the text. Table 3 shows the amount of coated silver, film thickness, and swelling rate of each coated sample.
[0140]
[Table 3]

[0141]
(Preparation of processing solution)
As a standard processing method for color positive films for movies, a simple processing process is prepared for the ECP-2 process announced by Eastman Kodak Co., excluding the sound development process and the fixing process before the bleach acceleration process. did. For all the prepared samples, an image was developed so that about 30% of the applied silver amount was developed. The exposed sample was subjected to continuous processing (running test) in the above-described processing process until the replenisher amount in the color developer bath doubled the tank capacity, and a development processing state in running equilibrium was prepared.
[0142]

[0143]
<Processing liquid formulation>
Indicates the composition per liter

In the above, D-3 used in the development process is a developing agent, and Deercide 702 used in the rinse process is an antifungal agent.
[0144]
(Evaluation of photographic sensitivity)
Using a sensitometer (FW type manufactured by Fuji Photo Film Co., Ltd., light source color temperature 3200K), exposure is performed so that a neutral gray sensitometric image can be obtained through yellow and magenta color correction filters and an optical wedge. The processing solution prepared as described above was processed with a color development processing time of 180 seconds (standard time), and each color density of yellow, magenta, and cyan was 1.0 higher than the covering with reference to the coated sample 5 The photographic sensitivity was evaluated by a value obtained by multiplying the reciprocal of the ratio of the exposure amount giving the value by 100. In addition, it means that a sensitivity is so high that this value is large.
As the maximum density (Dmax), a measured value of luminous density obtained by measuring the highest density portion of the coated sample when processed in 120 seconds with an X-rite 310 density measuring device (manufactured by X-rite) was described.
[0145]
(Evaluation of development progress)
In the evaluation of the photographic sensitivity described above, the photographic sensitivity is obtained when the color development processing time is 120 seconds, and the difference between the exposure amount that gives the photographic sensitivity at 180 seconds and the exposure amount that gives the photographic sensitivity at 120 seconds processing, Evaluation was made as a relative value when the coated sample 5 was taken as 100.
[0146]
(Evaluation of fixability)
Using the fixing solution of the processing solution prepared as described above, the time from the start of fixing to the fixing of the silver halide using the unexposed part of the prepared coated sample was evaluated by the transmitted light density of the film, and the coated sample The relative value when 5 is represented by 100 is shown.
[0147]
(Drying evaluation)
The dried state when 40 ° C. dry air was sprayed for a predetermined time (30 seconds) on the coated sample that had been washed with water was evaluated by the following sensory evaluation.
◎. . . . It is sufficiently dry.
○. . . . I feel a little moist but I don't care.
Δ. . . . Moisture remains.
×. . . . Insufficient drying.
[0148]
(Evaluation of remaining color)
The remaining color was developed in the above color developing solution for 120 seconds and subjected to sensory evaluation according to the following criteria for a coated sample treated with a water washing process time of 60 seconds to 40 seconds.
◎. . . . There is no residual color at all.
○. . . . There is a residual color, but I do not care.
Δ. . . . Although there are many remaining colors, it is practically acceptable.
×. . . . Many remaining colors, not possible.
The results are shown in Table 4.
[0149]
[Table 4]

[0150]
As shown in Table 4, when the silver halide composition, the amount of coated silver, the film thickness, and the swelling ratio of the photosensitive material are within the scope of the present invention, the development progress is very excellent, and at the same time, the fixability, It was confirmed that it had excellent drying properties and almost no residual color, had rapid processing suitability, and could shorten the processing time of development, fixing, washing and drying with respect to conventional processing.
[0151]
Example 2
(Preparation of blue-sensitive silver halide tabular grains)
In the preparation of Y01, Y11, and Y21 prepared in Example 1, the iridium compound (K₂IrCl₆) Were changed as shown in Table 5, and emulsions differing only in the content of the iridium compound were prepared in the same manner as in the emulsion Y1. The grain size, aspect ratio, and dispersibility were equivalent to the silver halide grains contained in the emulsion Y1 of Example 1.
[0152]
(Preparation of blue-sensitive silver halide cubic grains)
Silver chlorobromide emulsion {Cubic, 1: large emulsion grains Y03 with an average grain size of 0.7 μm, medium emulsion grains Y13 with an average grain size of 0.5 μm, and small emulsion grains Y23 with an average grain size of 0.36 μm 5: 4 mixture (silver molar ratio). The variation coefficient of grain size distribution is 9%, 10% and 12%, respectively, and emulsion grains having both halogen compositions of Br / Cl = 1.5 / 98.5} are controlled double jet methods known in the art. By adding a mixture of silver nitrate, sodium chloride and potassium bromide. The iridium content was added so as to be the value shown in Table 5. These emulsion grains were spectrally sensitized by adding the sensitizing dye used in Example 1. The chemical ripening of these emulsions was carried out optimally by adding a sulfur sensitizer and a gold sensitizer so as to be the same as Y01, Y11, and Y21 used in Example 1.
Thus, as shown in Table 5, emulsions differing only in the content of the iridium compound were prepared.
[0153]
(Preparation of red and green sensitive silver halide emulsion grains)
In the same manner as in Example 1, the amount of the iridium compound added in the preparation of the blue-sensitive silver halide emulsion was changed in the same manner as in the blue-sensitive emulsion used in the same coated sample, and all others were the same as in Example 1. Red photosensitive emulsion grains and green photosensitive emulsion grains were prepared.
[0154]
(Preparation of coated sample)
A dye dispersion not subjected to the heat treatment of the solid disperse dye prepared in Example 1 was prepared, and the solid disperse dye was changed as shown in Table 5. The emulsion grains were also changed to emulsions showing the amount of iridium compound. As the blue-sensitive emulsion grains, tabular grains or cubic grains were used, and coating samples were prepared as shown in Table 5.
[0155]
(Evaluation of photographic sensitivity)
In the evaluation of the photographic sensitivity of Example 1, the sensitivity when the processing temperature in the development process was increased by 1 ° C. and the processing time was 140 seconds was evaluated. The photographic sensitivity was evaluated by the reciprocal of the ratio of the exposure amount that gives a density 1.0 higher than the covering density, and the relative value when the coated sample 17 was 100 was evaluated.
[0156]
(Evaluation of reciprocity)
In the above photographic sensitivity evaluation, the exposure time was 1 second and 1/1000 second, respectively, and development processing was performed. The exposure amount was adjusted so as to be the same at each illuminance. The change in gradation between the two exposures with different exposure times was evaluated according to the following criteria.
○. . . . . Good with little change in gradation
Δ. . . . . There is a slight change in gradation, but it is acceptable.
×. . . . . Large gradation change.
[0157]
(Evaluation of graininess)
The exposure performed in Example 1 was performed uniformly by adjusting the optical wedge density so that the density was 1.0, and the development process was performed in the same manner as the evaluation of photographic sensitivity. The developed sample was observed by magnifying and magnifying it 300 times, and sensory evaluation was performed according to the following criteria.
○. . . . . The grain is not noticeable and not bothering.
Δ. . . . . It is grainy but practically acceptable.
×. . . . . Poor graininess, not possible.
[0158]
(Evaluation of sharpness)
The evaluation of sharpness was performed on a magenta color image and a cyan color image having a large visual influence. Each sample was exposed through a green filter, a red filter and a sharpness measurement wedge, developed in the same manner as the evaluation of photographic sensitivity, and evaluated for CTF measurement. Sharpness was evaluated with the spatial frequency (lines / mm) giving CTF 0.8. A larger value indicates higher sharpness.
[0159]
(Evaluation of development progress)
In the evaluation of photographic sensitivity, the photographic sensitivity of 100-second processing and 140-second processing (evaluation based on the density of (covering +1.0) as described above) is obtained, and the exposure amount giving the photographic sensitivity in 140 seconds and the 100-second processing The difference in exposure amount giving the photographic sensitivity was evaluated as a relative value when the coated sample 17 was 100.
The results are shown in Table 5.
[0160]
[Table 5]

[0161]
As is apparent from Table 5, the iridium compound was 1.0 × 10^-8Molar or more 5.0 × 10^-6When the amount is less than or equal to the mole, it can be seen that the reciprocity is good and the development progress is very fast. In addition, by containing a solid fine particle dispersion prepared through a heat treatment step of 40 ° C. or more, sharpness is good, and when using tabular grains in the yellow emulsion layer, the graininess is good, It has been found that the development progress is very fast and that rapid processing is suitable, and that the processing time can be shortened as in Example 1.
[0162]
【The invention's effect】
According to the first and seventh aspects of the present invention, it is possible to provide a silver halide color light-sensitive material for movie which can be processed quickly and has high sensitivity and no residual color after processing, and an image forming method.
According to the invention described in claims 2 to 7, the image quality is high, particularly the graininess is good, the sharpness is high, the reciprocity is good, the development progress is fast, and the movie can be processed quickly. A silver halide color light-sensitive material and an image forming method can be provided.

Claims (6)

On the support, yellow color-sensitive photosensitive silver halide emulsion layer, magenta color-sensitive silver halide emulsion layer, cyan color-sensitive silver halide emulsion layer, non-photosensitive non-color-forming hydrophilic colloid layer In the silver halide color photographic light-sensitive material having at least one layer, the light-sensitive halogenation contained in the yellow color-sensitive silver halide emulsion layer, the magenta color-sensitive silver halide emulsion layer, and the cyan color-sensitive silver halide emulsion layer Iridium compound having a silver chloride content of 95 mol% or more and silver halide grains of 1.0 × 10 ⁻⁸ mol / silver mol to 5.0 × 10 ⁻⁶ mol / silver mol The total coating silver amount is 1.7 g / m ² or less, the film thickness on the side having the layer containing the photosensitive silver halide with respect to the support is 12.0 μm or less, A silver halide color photographic light-sensitive material for cinema, having a swelling rate of 200% or less. 2. The cinematographic film according to claim 1, wherein at least one of the photosensitive silver halide emulsion layers contains tabular photosensitive silver halide grains having an aspect ratio of 2 or more having a {100} plane as a main plane. Silver halide color photographic material. The silver halide color for movies according to claim 2, wherein the layer containing tabular photosensitive silver halide grains having an aspect ratio of 2 or more having a {100} plane as a main plane is a yellow color developing photosensitive silver halide emulsion layer. Photosensitive material. 4. The movie halogen according to claim 1, wherein a solid fine particle dispersion of a dye represented by the following general formula (I) is contained in at least one of the non-photosensitive hydrophilic colloid layers. 5. Silver halide color photographic material.
Formula (I)
D- (X) y
In general formula (I), D represents a compound residue having a chromophore, X represents a dissociative hydrogen or a group having a dissociative hydrogen, and y represents an integer of 1 to 7. The maximum density of neutral gray consisting of yellow color density, magenta color density, and cyan color density obtained after the development processing is 3.3 or more, according to any one of claims 1 to 4 . Silver halide color photographic material for movies. After exposure the claims 1-5 or movies for silver halide color photographic material of the mounting serial to one of movies for silver halide, characterized in that the developing treatment with 2 minutes 30 seconds of the color developing time Image forming method for color photographic light-sensitive material.