JP2004287136A - Dot area image recording material and dot area image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dot area image recording material capable of reproducing stable color tones independently of variation of dot % from fine dots to coarse dots of a C image in a color proof by which a finish of printing under various printing conditions can be checked by making dot density variable, and to provide a dot area image forming method. <P>SOLUTION: In the dot area image recording material comprising at least one each of yellow (Y), magenta (M) and cyan (C) image forming units which form dots as aggregations of pixels capable of varying density, relation of the expression (1): Δθ12≤8° is established in the C image forming unit. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００９１】
上記一般式（Ｉ）−１中のＲ_１及びＲ_１１の内の少なくとも一つ、（１）−２中のＲ_１及びＲ_１２の内の少なくとも一つはσｐが０．２０以上の電子吸引性基である。
【００９２】
Ｘ_１は一般式（Ｉ）におけるＸ_１と同義であり、又、一般式（Ｉ）−１、一般式（Ｉ）−２において、Ｒ_１及びＲ_１１〜Ｒ_１２の内、σｐが０．２０以上の電子吸引性基でないものは、水素原子又は置換基を表す。
【００９３】
一般式（ＩＩ）において、Ｒ_３及びＲ_４はハメットの置換基定数σｐが０．２０以上の電子吸引性基を表し、これらの電子吸引性基としては、一般式（Ｉ）におけるＲ_１及びＲ_２の電子吸引性基と同様の基を挙げることができる。ただし、Ｒ_３とＲ_４のσｐ値の和は０．６５以上である。
【００９４】
Ｚ_２により形成される含窒素５員複素環としては、ピラゾール環、イミダゾール環又はテトラゾール環等が挙げられる。これらの含窒素５員複素環は置換基を有していてもよい。
【００９５】
一般式（ＩＩ）で表される化合物を更に具体的に記すと、下記一般式（ＩＩ）−１、一般式（ＩＩ）−２により表される。
【００９６】
【化４】

【００９７】
式中、Ｒ_３、Ｒ_４及びＸ_２は、一般式（ＩＩ）におけるそれぞれと同義である。Ｒ_２１は水素原子又は置換基を表す。
【００９８】
下記に一般式（Ｉ）または一般式（ＩＩ）で表される化合物の具体例を示すが本発明はこれに限定されるものではない。
【００９９】
【化５】

【０１００】
【化６】

【０１０１】
【化７】

【０１０２】
【化８】

【０１０３】
特にシアンカプラーの構造を規定しない発明においては、公知のフェノール系、ナフトール系又はイミダゾール系カプラーを用いることができる。例えば、アルキル基、アシルアミノ基、或いはウレイド基などを置換したフェノール系カプラー、５−アミノナフトール骨格から形成されるナフトール系カプラー、離脱基として酸素原子を導入した２当量型ナフトール系カプラーなどが代表される。このうち好ましい化合物としては特開平６−９５２８３号１３ページ記載の一般式［Ｃ−Ｉ］、［Ｃ−ＩＩ］が挙げられる。
【０１０４】
該シアンカプラーは通常ハロゲン化銀乳剤層において、ハロゲン化銀１モル当たり１×１０^−３〜１モル、好ましくは１×１０^−２〜８×１０^−１モルの範囲で用いることができる。
【０１０５】
本発明の特徴の一つは、Ｃ画像形成ユニットにＣ画像形成物質と、Ｍ画像形成物質を含むことにある。ハロゲン化銀感光材料においては、公知のＭカプラーをいずれも好ましく用いることができる。Ｍカプラーは単独の分散物として添加してもよいし、Ｃカプラーと共通の分散液として添加してもよい。
【０１０６】
本発明に係る感光材料においてイエロー画像形成層中に含有されるイエローカプラーとしては、公知のアシルアセトアニリド系カプラー等を好ましく用いることができる。
【０１０７】
該イエローカプラーの具体例としては、例えば特開平３−２４１３４５号の５頁〜９頁に記載の化合物、Ｙ−Ｉ−１〜Ｙ−Ｉ−５５で示される化合物、もしくは特開平３−２０９４６６号の１１〜１４頁に記載の化合物、Ｙ−１〜Ｙ−３０で示される化合物も好ましく使用することができる。更に特開平６−９５２８３号２１ページ記載の一般式〔Ｙ−Ｉ〕で表されるカプラー、特開２００２−３５１０２３号に記載の一般式（Ｉ）、（ＩＩ）の化合物等も挙げることができる。
【０１０８】
本発明に係る感光材料により形成されるイエロー画像の分光吸収のλｍａｘは４２５ｎｍ以上であることが好ましく、λＬ０．２は５１５ｎｍ以下であることが好ましい。
【０１０９】
該イエロー色画像の分光吸収のλＬ０．２とは、特開平６−９５２８３号２１ページ右欄１行〜２４行に記載の内容で定義される値であり、イエロー色素画像の分光吸収特性で長波側の不要吸収の大きさを表す。
【０１１０】
該イエローカプラーは通常ハロゲン化銀乳剤層において、ハロゲン化銀１モル当たり１×１０^−３〜１モル、好ましくは１×１０^−２〜８×１０^−１モルの範囲で用いることができる。
【０１１１】
該マゼンタ色画像、シアン色画像、及びイエロー色画像の分光吸収特性を調整するために、色調調整作用を有する化合物を添加する事が好ましい。このための化合物としては、特開平６−９５２８３号２２ページ記載の一般式［ＨＢＳ−Ｉ］に記載されるリン酸エステル系化合物、［ＨＢＳ−ＩＩ］で示されるホスフィンオキサイド系化合物が好ましく、より好ましくは同号２２ページ記載の一般式［ＨＢＳ−ＩＩ］で示される化合物である。また、特開平４−２６５，９７５号５ページ記載の（ａ−ｉ）〜（ａ−ｘ）を代表とする高級アルコール系化合物を挙げることができる。
【０１１２】
本発明に係る感光材料においてハロゲン化銀乳剤層は支持体上に積層塗布されるが支持体からの順番はどのような順番でもよい。この他に必要に応じ中間層、フィルター層、保護層等を配置することができる。
【０１１３】
前記マゼンタ、シアン、イエローの各カプラーには、形成された色素画像の光、熱、湿度等による褪色を防止するため褪色防止剤を併用することができる。好ましい化合物としては、特開平２−６６５４１号３ページ記載の一般式ＩおよびＩＩで示されるフェニルエーテル系化合物、特開平３−１７４１５０号記載の一般式ＩＩＩＢで示されるフェノール系化合物、特開平６４−９０４４５号記載の一般式Ａで示されるアミン系化合物、特開昭６２−１８２７４１号記載の一般式ＸＩＩ、ＸＩＩＩ、ＸＩＶ、ＸＶで示される金属錯体が特にマゼンタ色素用として好ましい。また特開平１−１９６０４９号記載の一般式Ｉ′で示される化合物および特開平５−１１４１７号記載の一般式ＩＩで示される化合物が特にイエロー、シアン色素用として好ましい。
【０１１４】
本発明に係るハロゲン化銀感光材料に用いられるステイン防止剤やその他の有機化合物を添加するのに水中油滴型乳化分散法を用いる場合には、通常、沸点１５０℃以上の水不溶性高沸点有機溶媒に、必要に応じて低沸点及び／または水溶性有機溶媒を併用して溶解し、ゼラチン水溶液などの親水性バインダー中に界面活性剤を用いて乳化分散する。分散手段としては、撹拌機、ホモジナイザー、コロイドミル、フロージェットミキサー、超音波分散機等を用いることができる。分散後、または、分散と同時に低沸点有機溶媒を除去する工程を入れてもよい。ステイン防止剤等を溶解して分散するために用いることの出来る高沸点有機溶媒としては、トリクレジルホスフェート、トリオクチルホスフェート等のリン酸エステル類、トリオクチルホスフィンオキサイド等のホスフィンオキサイド類が好ましく用いられる。また高沸点有機溶媒の誘電率としては３．５〜７．０である事が好ましい。また二種以上の高沸点有機溶媒を併用することもできる。
【０１１５】
本発明に係る感光材料に用いられる写真用添加剤の分散や塗布時の表面張力調整のため用いられる界面活性剤として好ましい化合物としては、１分子中に炭素数８〜３０の疎水性基とスルホン酸基またはその塩を含有するものが挙げられる。具体的には特開昭６４−２６８５４号記載のＡ−１〜Ａ−１１が挙げられる。またアルキル基に弗素原子を置換した界面活性剤も好ましく用いられる。これらの分散液は通常ハロゲン化銀乳剤を含有する塗布液に添加されるが、分散後塗布液に添加されるまでの時間、および塗布液に添加後塗布までの時間は短いほうがよく各々１０時間以内が好ましく、３時間以内、２０分以内がより好ましい。
【０１１６】
本発明に係るハロゲン化銀感光材料には、現像主薬酸化体と反応する化合物を感光層と感光層の間の層に添加して色濁りを防止したり、またハロゲン化銀乳剤層に添加してカブリ等を改良する事が好ましい。このための化合物としてはハイドロキノン誘導体が好ましく、さらに好ましくは２，５−ジ−ｔ−オクチルハイドロキノンのようなジアルキルハイドロキノンである。特に好ましい化合物は特開平４−１３３０５６号記載の一般式ＩＩで示される化合物であり、同号１３〜１４ページ記載の化合物ＩＩ−１〜ＩＩ−１４および１７ページ記載の化合物１が挙げられる。
【０１１７】
本発明に係る感光材料中には紫外線吸収剤を添加してスタチックカブリを防止したり色素画像の耐光性を改良することが好ましい。好ましい紫外線吸収剤としてはベンゾトリアゾール類が挙げられ、特に好ましい化合物としては特開平１−２５０９４４号記載の一般式ＩＩＩ−３で示される化合物、特開昭６４−６６６４６号記載の一般式ＩＩＩで示される化合物、特開昭６３−１８７２４０号記載のＵＶ−１Ｌ〜ＵＶ−２７Ｌ、特開平４−１６３３号記載の一般式Ｉで示される化合物、特開平５−１６５１４４号記載の一般式（Ｉ）、（ＩＩ）で示される化合物が挙げられる。
【０１１８】
本発明に係る感光材料には、油溶性染料や顔料を含有すると白地性が改良され好ましい。油溶性染料の代表的具体例は、特開平２−８４２号８ページ〜９ページに記載の化合物１〜２７があげられる。
【０１１９】
本発明に係るハロゲン化銀感光材料には、バインダーとしてゼラチンを用いることが有利であるが、必要に応じて他のゼラチン、ゼラチン誘導体、ゼラチンと他の高分子のグラフトポリマー、ゼラチン以外のタンパク質、糖誘導体、セルロース誘導体、単一あるいは共重合体のごとき合成親水性高分子物質等の親水性コロイドも用いることができる。
【０１２０】
これらバインダーの硬膜剤としてはビニルスルホン型硬膜剤やクロロトリアジン型硬膜剤を単独または併用して使用する事が好ましい。特開昭６１−２４９０５４号、同６１−２４５１５３号記載の化合物を使用する事が好ましい。また写真性能や画像保存性に悪影響するカビや細菌の繁殖を防ぐためコロイド層中に特開平３−１５７６４６号記載のような防腐剤および抗カビ剤を添加する事が好ましい。また感光材料または処理後の試料の表面の物性を改良するため保護層に特開平６−１１８５４３号や特開平２−７３２５０号記載の滑り剤やマット剤を添加する事が好ましい。
【０１２１】
本発明に係る感光材料に用いる支持体としては、どのような材質を用いてもよく、ポリエチレンやポリエチレンテレフタレートで被覆した紙、天然パルプや合成パルプからなる紙支持体、塩化ビニルシート、白色顔料を含有してもよいポリプロピレン、ポリエチレンテレフタレート支持体、バライタ紙などを用いることができる。なかでも、原紙の両面に耐水性樹脂被覆層を有する支持体が好ましい。耐水性樹脂としてはポリエチレンやポリエチレンテレフタレートまたはそれらのコポリマーが好ましい。
【０１２２】
紙の表面に耐水性樹脂被覆層を有する支持体は、通常、５０〜３００ｇ／ｍ^２の質量を有する表面の平滑なものが用いられるが、プルーフ画像を得る目的に対しては、取り扱いの感覚を印刷用紙に近づけるため、１３０ｇ／ｍ^２以下の原紙が好ましく用いられ、さらに７０〜１２０ｇ／ｍ^２の原紙が好ましく用いられる。
【０１２３】
本発明に用いられる支持体としては、ランダムな凹凸を有するものであっても平滑なものであっても好ましく用いることができる。
【０１２４】
支持体に用いられる白色顔料としては、無機及び／または有機の白色顔料を用いることができ、好ましくは無機の白色顔料が用いられる。例えば硫酸バリウム等のアルカリ土類金属の硫酸塩、炭酸カルシウム等のアルカリ土類金属の炭酸塩、微粉ケイ酸、合成ケイ酸塩等のシリカ類、ケイ酸カルシウム、アルミナ、アルミナ水和物、酸化チタン、酸化亜鉛、タルク、クレイ等があげられる。白色顔料は好ましくは硫酸バリウム、酸化チタンである。
【０１２５】
支持体の表面の耐水性樹脂層中に含有される白色顔料の量は、鮮鋭性を改良するうえで１３質量％以上が好ましく、さらには１５質量％が好ましい。
【０１２６】
本発明に係る紙支持体の耐水性樹脂層中の白色顔料の分散度は、特開平２−２８６４０号に記載の方法で測定することができる。この方法で測定したときに、白色顔料の分散度が前記公報に記載の変動係数として０．２０以下であることが好ましく、０．１５以下であることがより好ましい。
【０１２７】
本発明に用いられる両面に耐水性樹脂層を有する紙支持体の樹脂層は、１層であってもよいし、複数層からなってもよい。複数層とし、乳剤層と接する方に白色顔料を高濃度で含有させると鮮鋭性の向上が大きく、プルーフ用画像を形成するのに好ましい。
【０１２８】
また支持体の中心面平均粗さ（ＳＲａ）の値が０．１５μｍ以下、さらには０．１２μｍ以下であるほうが光沢性がよいという効果が得られより好ましい。
【０１２９】
本発明に用いられる写真感光材料は、必要に応じて支持体表面にコロナ放電、紫外線照射、火炎処理等を施した後、直接または下塗層（支持体表面の接着性、帯電防止性、寸度安定性、耐摩擦性、硬さ、ハレーション防止性、摩擦特性及び／またはその他の特性を向上するための１または２以上の下塗層）を介して塗布されていてもよい。
【０１３０】
ハロゲン化銀乳剤を用いた写真感光材料の塗布に際して、塗布性を向上させるために増粘剤を用いてもよい。塗布法としては２種以上の層を同時に塗布することの出来るエクストルージョンコーティング及びカーテンコーティングが特に有用である。
【０１３１】
本発明に用いられる露光装置の露光光源は、公知のものをいずれも好ましく用いることが出来るが、レーザーまたは発光ダイオード（以下ＬＥＤと表す）がより好ましく用いられる。４００ｍｍ以上の幅が好ましく用いられる。８００ｍｍあるいはそれ以上の幅の感光材料も好ましく用いられる。
【０１３２】
レーザーとしては半導体レーザー（以下、ＬＤと表す）がコンパクトであること、光源の寿命が長いことから好ましく用いられる。また、ＬＤはＤＶＤ、音楽用ＣＤの光ピックアップ、ＰＯＳシステム用バーコードスキャナ等の用途や光通信等の用途に用いられており、安価であり、かつ比較的高出力のものが得られるという長所を有している。ＬＤの具体的な例としては、アルミニウム・ガリウム・インジウム・ヒ素（６５０ｎｍ）、インジウム・ガリウム・リン（〜７００ｎｍ）、ガリウム・ヒ素・リン（６１０〜９００ｎｍ）、ガリウム・アルミニウム・ヒ素（７６０〜８５０ｎｍ）等を挙げることができる。最近では、青光を発振するレーザーも開発されているが、現状では、６１０ｎｍよりも長波の光源としてＬＤを用いるのが有利である。
【０１３３】
ＳＨＧ素子を有するレーザー光源としては、ＬＤ、ＹＡＧレーザーから発振される光をＳＨＧ素子により半分の波長の光に変換して放出させるものであり、可視光が得られることから適当な光源がない緑〜青の領域の光源として用いられる。この種の光源の例としては、ＹＡＧレーザーにＳＨＧ素子を組み合わせたもの（５３２ｎｍ）等がある。
【０１３４】
ガスレーザーとしては、ヘリウム・カドミウムレーザー（約４４２ｎｍ）、アルゴンイオンレーザー（約５１４ｎｍ）、ヘリウムネオンレーザー（約５４４ｎｍ、６３３ｎｍ）等が挙げられる。
【０１３５】
ＬＥＤとしては、ＬＤと同様の組成をもつものが知られているが、青〜赤外まで種々のものが実用化されている。特開２００２−７２３６７号に記載のような微小面積発光ダイオードの１種である端面発光型ダイオードを、好ましく用いることができる。
【０１３６】
本発明に用いられる露光光源としては、各レーザーを単独で用いてもよいし、これらを組合せ、マルチビームとして用いてもよい。ＬＤの場合には、例えば１０個のＬＤを並べることにより１０本の光束からなるビームが得られる。一方、ヘリウムネオンレーザーのような場合、レーザーから発した光をビームセパレーターで例えば１０本の光束に分割する。
【０１３７】
露光用光源の強度変化は、ＬＤ、ＬＥＤのような場合には、個々の素子に流れる電流値を変化させる直接変調を行うことができる。直接変調の場合には、電流値の調整により発光光量を変化させてもよいし、パルス状に発光させ、パルスの幅（発光時間）を変化させるパルス幅変調方式を用いてもよいし、パルス数を変化させるパルス数変調方式をとってもよい。ＬＤの場合には、ＡＯＭ（音響光学変調子）のような素子を用いて強度を変化させてもよい。ガスレーザーの場合には、ＡＯＭ、ＥＯＭ（電気光学変調子）等のデバイスを用いるのが一般である。
【０１３８】
光源にＬＥＤを用いる場合には、光量が弱ければ、複数の素子で同一の画素を重複して露光する方法を用いてもよい。
【０１３９】
光源の発光波長は、感光材料が十分な感度を有している波長領域であれば好ましく用いることができるが、色濁りを防止する意味で他の感光層と十分な感度差を有する波長領域を用いることが好ましい。感光材料のコントラストにも依存するが露光量の常用対数として０．６以上、好ましくは１．０以上の感度差があることが好ましい。この他に、光源の置かれた環境条件、動作条件などにより発光波長が変動するような場合には、分光感度のピーク波長に合わせることが理論上好ましく、これに関わってくる着色物質の分光吸収との関係も考慮して波長を選択することが好ましい。そのような例としては、特開平６−７５３４２号、特開２００１−８３６６３号などが上げられる。また、発光波長だけでなく発光強度が変動する場合にも、分光感度との関係で発光波長を選択することが好ましく、その例としては、特開２００２−７２３６７号、及び日経ニューマテリアル１９８７年９月１４日号５４ページ等に記載されている。
【０１４０】
画像形成に用いる装置としては、複数の感光材料を予めセットしておき、適宜感光材料を選択して使用する方式を好ましく用いることができる。この場合、２種類の感光材料は、例えば幅の違う感光材料であったり、面質（支持体の凹凸）が異なる感光材料であったりすることができる。感光材料の選択は、画像形成装置のスイッチなどで設定する方式であっても、画像データとともに設定情報を送信し、それに基づいて選択されるのでもよい。また画像データのサイズに応じて最適な感光材料のサイズを自動的に選択する事も有利に用いることができる。特別な場合には、同じ種類の感光材料を装填しておき、一方の感光材料が使い終わったとき、自動的に他方の感光材料を使うようにすることもでき、連続無人運転が可能となり有利に用いることができる。
【０１４１】
本願発明において面積階調画像という言葉を用いているが、これは画像上の濃淡を個々の画素の色の濃淡で表現するのではなく、特定の濃度に発色した部分の面積の大小で表現するものであり、網点と同義と考えてよい。
【０１４２】
通常面積階調露光であればＹ、Ｍ、Ｃ、墨の発色をさせることで目的を達することもできる。より好ましくは、墨に加えてＭ、Ｃ等の単色が発色したことを識別するには、３値以上の露光量を使い分けて露光する事が好ましい。印刷においては、特別な色の版を用いることがあるが、これを再現するためには、４値以上の露光量を使い分けて露光する事が好ましい。
【０１４３】
レーザー光源の場合には、ビーム径は２５μｍ以下であることが好ましく、６〜２２μｍがより好ましい。６μｍより小さいと画質的には好ましいが、調整が困難であったり、処理速度が低下したりする。一方、２５μｍより大きいとムラが大きくなり、画像の鮮鋭性も劣化する。ビーム径を最適化する事によってムラのない高精細の画像の書き込みを高速で行うことができる。
【０１４４】
このような光で画像を描くには、ハロゲン化銀感光材料上を光束が走査する必要があるが、感光材料を円筒状のドラムに巻き付けこれを高速に回転しながら回転方向に直角な方向に光束を動かす円筒外面走査方式をとってもよく、円筒状の窪みにハロゲン化銀感光材料を密着させて露光する円筒内面走査方式も好ましく用いることができる。多面体ミラーを高速で回転させこれによって搬送されるハロゲン化銀感光材料を搬送方向に対して直角に光束を移動して露光する平面走査方式をとってもよい。高画質であり、かつ大きな画像を得るには円筒外面走査方式がより好ましく用いられる。
【０１４５】
円筒外面走査方式での露光を行うには、ハロゲン化銀感光材料は正確に円筒状のドラムに密着されなければならない。これが的確に行われるためには、正確に位置合わせされて搬送される必要がある。本発明に用いられるハロゲン化銀感光材料は露光する側の面が外側に巻かれたものがより的確に位置合わせでき、好ましく用いることができる。同様な観点から、本発明に用いられるハロゲン化銀感光材料に用いられる支持体は適正な剛度があり、テーバー剛度で０．８〜４．０が好ましい。
【０１４６】
ドラム径は、露光するハロゲン化銀感光材料の大きさに適合させて任意に設定することができる。ドラムの回転数も任意に設定できるがレーザー光のビーム径、エネルギー強度、書き込みパターンや感光材料の感度などにより適当な回転数を選択することができる。生産性の観点からは、より高速な回転で走査露光できる方が好ましいが、具体的には１分間に２００〜３０００回転が好ましく用いられる。
【０１４７】
ドラムへのハロゲン化銀感光材料の固定方法は、機械的な手段によって固定させてもよいし、ドラム表面に吸引できる微小な穴を感光材料の大きさに応じて多数設けておき、感光材料を吸引して密着させることもできる。感光材料をドラムにできるだけ密着させることが画像ムラ等のトラブルを防ぐには重要である。
【０１４８】
本発明において用いられる芳香族一級アミン現像主薬としては、公知の化合物を用いることができる。これらの化合物の例として下記の化合物を挙げることができる。
【０１４９】
ＣＤ−１） Ｎ，Ｎ−ジエチル−ｐ−フェニレンジアミン
ＣＤ−２） ２−アミノ−５−ジエチルアミノトルエン
ＣＤ−３） ２−アミノ−５−（Ｎ−エチル−Ｎ−ラウリルアミノ）トルエン
ＣＤ−４） ４−（Ｎ−エチル−Ｎ−（β−ヒドロキシエチル）アミノ）アニリン
ＣＤ−５） ２−メチル−４−（Ｎ−エチル−Ｎ−（β−ヒドロキシエチル）アミノ）アニリン
ＣＤ−６） ４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（β−（メタンスルホンアミド）エチル）−アニリン
ＣＤ−７） Ｎ−（２−アミノ−５−ジエチルアミノフェニルエチル）メタンスルホンアミド
ＣＤ−８） Ｎ，Ｎ−ジメチル−ｐ−フェニレンジアミン
ＣＤ−９） ４−アミノ−３−メチル−Ｎ−エチル−Ｎ−メトキシエチルアニリン
ＣＤ−１０） ４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（β−エトキシエチル）アニリン
ＣＤ−１１） ４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（γ−ヒドロキシプロピル）アニリン
本発明においては、上記は色現像液の任意のｐＨ域で使用できるが、迅速処理の観点からｐＨ９．５〜１３．０であることが好ましく、より好ましくはｐＨ９．８〜１２．０の範囲で用いられる。
【０１５０】
本発明に係る発色現像の処理温度は、３５℃以上７０℃以下が好ましい。温度が高いほど短時間の処理が可能であり好ましいが、処理液の安定性からはあまり高くない方が好ましく、３７℃以上６０℃以下で処理することが好ましい。
【０１５１】
発色現像時間は、従来一般には３分３０秒程度で行われているが、本発明では４０秒以内が好ましく、さらに２５秒以内の範囲で行うことがさらに好ましい。
【０１５２】
発色現像液には、前記の発色現像主薬に加えて、既知の現像液成分化合物を添加することが出来る。通常、ｐＨ緩衝作用を有するアルカリ剤、塩化物イオン、ベンゾトリアゾール類等の現像抑制剤、保恒剤、キレート剤などが用いられる。
【０１５３】
本発明のハロゲン化銀感光材料は、発色現像後、漂白処理及び定着処理を施される。漂白処理は定着処理と同時に行なってもよい。定着処理の後は、通常は水洗処理が行なわれる。また、水洗処理の代替として、安定化処理を行なってもよい。本発明のハロゲン化銀感光材料の現像処理に用いる現像処理装置としては、処理槽に配置されたローラーに感光材料をはさんで搬送するローラートランスポートタイプであっても、ベルトに感光材料を固定して搬送するエンドレスベルト方式であってもよいが、処理槽をスリット状に形成して、この処理槽に処理液を供給するとともに感光材料を搬送する方式や処理液を噴霧状にするスプレー方式、処理液を含浸させた担体との接触によるウェッブ方式、粘性処理液による方式なども用いることができる。大量に処理する場合には、自動現像機を用いてランニング処理されるのが、通常だがこの際、補充液の補充量は少ない程好ましく、環境適性等より最も好ましい処理形態は、補充方法として錠剤の形態で処理剤を添加することであり、公開技報９４−１６９３５に記載の方法が最も好ましい。
【０１５４】
本発明の好ましい実施態様を下記に示すが、本発明はこれに限定されるものではない。
（１）濃度を変更可能な画素の集合体として網点を形成する、少なくとも各々一つのイエロー（Ｙ）画像形成ユニット、マゼンタ（Ｍ）画像形成ユニット、シアン（Ｃ）画像形成ユニットを有する面積階調画像記録材料において、該Ｃ画像形成ユニットにおいて、前記（式１）が成り立つことを特徴とする面積階調画像記録材料。
（２）濃度を変更可能な画素の集合体として網点を形成する、少なくとも一つのＣ画像形成ユニットを有する面積階調画像記録材料において、該Ｃ画像形成ユニットがＣ画像形成物質と、Ｍ画像形成物質を含むことを特徴とする面積階調画像記録材料。
（３）ハロゲン化銀感光材料である（１）、（２）のいずれかに記載の面積階調画像記録材料。
（４）前記Ｍ画像形成物質がＭカプラーであり、Ｃカプラーと独立に分散されたものであることを特徴とする（３）に記載の面積階調画像記録材料。
（５）前記Ｍ画像形成物質がＭカプラーであり、Ｃ画像形成ユニットとＭ画像形成ユニットの中間の層に含有されることを特徴とする（３）に記載の面積階調画像記録材料。
（６）Ｃカプラーが、前記一般式（Ｉ）または一般式（ＩＩ）で表されることを特徴とする（３）〜（５）のいずれか１項に記載の面積階調画像記録材料。
（７）前記Ｃ画像のベタ色調のメトリッククロマが５８以上であることを特徴とする（１）〜（６）のいずれかに記載の面積階調画像記録材料。
（８）Δθ１２が５°以下であることを特徴とする（１）〜（７）のいずれか１項に記載の面積階調画像記録材料。
（９）Δθ１２が３°以下であることを特徴とする（１）〜（７）のいずれか１項に記載の面積階調画像記録材料。
（１０）少なくとも１つずつのＹ、Ｍ、Ｃ、Ｋ（墨）画像データに基づき、濃度を変更可能な画素の集合体として網点を形成する面積階調画像の形成方法において、該Ｃ画像形成に際して、前記（式２）が成り立つことを特徴とする面積階調画像形成方法。
（１１）Δθ３４が５°以下であることを特徴とする（１０）に記載の面積階調画像記録材料。
（１２）Δθ３４が３°以下であることを特徴とする（１０）に記載の面積階調画像記録材料。
（１３）前記一般式（Ｉ）または一般式（ＩＩ）で表される化合物を含有するハロゲン化銀感光材料を用いることを特徴とする（１０）〜（１２）に記載の面積階調画像形成方法。
【０１５５】
【実施例】
以下、実施例により本発明を詳細に説明するが、本発明の態様はこれに限定されない。
【０１５６】
実施例１
片面に高密度ポリエチレンを、もう一方の面にアナターゼ型酸化チタンを１５質量％の含有量で分散して含む溶融ポリエチレンをラミネートした、平米当たりの質量が１１５ｇのポリエチレンラミネート紙反射支持体（テーバー剛度＝３．５、ＰＹ値＝２．７μｍ）上に、下記表１及び２に示す層構成の各層を酸化チタンを含有するポリエチレン層の側に塗設し、更に裏面側にはゼラチン６．００ｇ／ｍ^２、シリカマット剤０．６５ｇ／ｍ^２を塗設した多層ハロゲン化銀感光材料試料Ｎｏ．１０１を作製した。
【０１５７】
カプラーは高沸点溶媒に溶解して超音波分散し、分散物として添加したが、この時、界面活性剤として（ＳＵ−１）を用いた。又、硬膜剤として（Ｈ−１）、（Ｈ−２）を添加した。塗布助剤としては、界面活性剤（ＳＵ−２）、（ＳＵ−３）を添加し、表面張力を調整した。また各層に（Ｆ−１）を全量が０．０４ｇ／ｍ^２となるように添加した。
【０１５８】
【表１】

【０１５９】
【表２】

【０１６０】
ＳＵ−１：トリ−ｉ−プロピルナフタレンスルホン酸ナトリウム
ＳＵ−２：スルホ琥珀酸ジ（２−エチルヘキシル）・ナトリウム塩
ＳＵ−３：スルホ琥珀酸ジ（２，２，３，３，４，４，５，５−オクタフルオロペンチル）・ナトリウム塩
Ｈ−１ ：テトラキス（ビニルスルホニルメチル）メタン
Ｈ−２ ：２，４−ジクロロ−６−ヒドロキシ−ｓ−トリアジン・ナトリウム
ＨＱ−１：２，５−ジ−ｔ−オクチルハイドロキノン
ＨＱ−２：２，５−ジ（（１，１−ジメチル−４−ヘキシルオキシカルボニル）ブチル）ハイドロキノン
ＨＱ−３：２，５−ジ−ｓｅｃ−ドデシルハイドロキノンと２，５−ジ−ｓｅｃ−テトラデシルハイドロキノンと２−ｓｅｃ−ドデシル−５−ｓｅｃ−テトラデシルハイドロキノンの質量比１：１：２の混合物
ＳＯ−１：トリオクチルホスフィンオキサイド
ＳＯ−２：ジ（ｉ−デシル）フタレート
ＳＯ−３：オレイルアルコール
ＳＯ−４：トリクレジルホスフェート
ＰＶＰ ：ポリビニルピロリドン
【０１６１】
【化９】

【０１６２】
【化１０】

【０１６３】
（青感光性ハロゲン化銀乳剤の調製）
４０℃に保温した２％ゼラチン水溶液１リットル中に下記（Ａ液）及び（Ｂ液）をｐＡｇ＝７．３、ｐＨ＝３．０に制御しつつ同時添加し、更に下記（Ｃ液）及び（Ｄ液）をｐＡｇ＝８．０、ｐＨ＝５．５に制御しつつ同時添加した。この時、ｐＡｇの制御は特開昭５９−４５４３７号記載の方法により行い、ｐＨの制御は硫酸又は水酸化ナトリウム水溶液を用いて行った。
（Ａ液）
塩化ナトリウム ３．４２ｇ
臭化カリウム ０．０３ｇ
水を加えて ２００ｍｌ
（Ｂ液）
硝酸銀 １０ｇ
水を加えて ２００ｍｌ
（Ｃ液）
塩化ナトリウム １０２．７ｇ
ヘキサクロロイリジウム（ＩＶ）酸カリウム ４×１０^−８モル
ヘキサシアノ鉄（ＩＩＩ）酸カリウム ２×１０^−５モル
臭化カリウム １．０ｇ
水を加えて ６００ｍｌ
（Ｄ液）
硝酸銀 ３００ｇ
水を加えて ６００ｍｌ
添加終了後、花王アトラス社製デモールＮの５％水溶液と硫酸マグネシウムの２０％水溶液を用いて脱塩を行った後、ゼラチン水溶液と混合して平均粒径０．７１μｍ、粒径分布の変動係数０．０７、塩化銀含有率９９．５モル％の単分散立方体乳剤ＥＭＰ−１０１を得た。
【０１６４】
上記（ＥＭＰ−１０１）に対し、下記化合物を用い６０℃にて最適に化学増感を行い、青感光性ハロゲン化銀乳剤（Ｅｍ−Ｂ１０１）を得た。
【０１６５】
チオ硫酸ナトリウム ０．８ｍｇ／モル ＡｇＸ
塩化金酸 ０．５ｍｇ／モル ＡｇＸ
安定剤 ＳＴＡＢ−１ ３×１０^−４モル／モル ＡｇＸ
安定剤 ＳＴＡＢ−２ ３×１０^−４モル／モル ＡｇＸ
安定剤 ＳＴＡＢ−３ ３×１０^−４モル／モル ＡｇＸ
増感色素 ＢＳ−１ ４×１０^−４モル／モル ＡｇＸ
増感色素 ＢＳ−２ １×１０^−４モル／モル ＡｇＸ
臭化カリウム ０．２ｇ／モル ＡｇＸ
次いでＥＭＰ−１０１の調製において、（Ａ液）と（Ｂ液）の添加時間および（Ｃ液）と（Ｄ液）の添加時間を変更した以外はＥＭＰ−１０１と同様にして平均粒径０．６４μｍ、粒径分布の変動係数０．０７、塩化銀含有率９９．５モル％の単分散立方体乳剤ＥＭＰ−１０２を得た。Ｅｍ−Ｂ１０１の調製においてＥＭＰ−１０１に代えてＥＭＰ−１０２を用いた以外同様にしてＥｍ−Ｂ１０２を得、Ｅｍ−Ｂ１０１と１０２の１：１の混合物を青感光性乳剤として使用した。
【０１６６】
（緑感光性ハロゲン化銀乳剤の調製）
ＥＭＰ−１０１の調製において（Ａ液）及び（Ｂ液）、（Ｃ液）及び（Ｄ液）の添加時間を変更した以外は同様にして平均粒径０．４０μｍ、変動係数０．０８、塩化銀含有率９９．５％の単分散立方体乳剤（ＥＭＰ−１０３）を得た。
【０１６７】
上記ＥＭＰ−１０２に対し、下記化合物を用い５５℃にて最適に化学増感を行い、緑感光性ハロゲン化銀乳剤（Ｅｍ−Ｇ１０１）を得た。
【０１６８】
チオ硫酸ナトリウム １．５ｍｇ／モル ＡｇＸ
塩化金酸 １．０ｍｇ／モル ＡｇＸ
安定剤 ＳＴＡＢ−１ ３×１０^−４モル／モル ＡｇＸ
安定剤 ＳＴＡＢ−２ ３×１０^−４モル／モル ＡｇＸ
安定剤 ＳＴＡＢ−３ ３×１０^−４モル／モル ＡｇＸ
増感色素 ＧＳ−１ ４×１０^−４モル／モル ＡｇＸ
増感色素 ＧＳ−２ ２×１０^−４モル／モル ＡｇＸ
塩化ナトリウム ０．５ｇ／モル ＡｇＸ
次いでＥＭＰ−１０３の調製において、（Ａ液）と（Ｂ液）の添加時間および（Ｃ液）と（Ｄ液）の添加時間を変更した以外はＥＭＰ−１０３と同様にして平均粒径０．５０μｍ、変動係数０．０８、塩化銀含有率９９．５％の単分散立方体乳剤ＥＭＰ−１０４を得た。Ｅｍ−Ｇ１０１の調製においてＥＭＰ−１０３に代えてＥＭＰ−１０４を用いた以外同様にしてＥｍ−Ｇ１０２を得、Ｅｍ−Ｇ１０１と１０２の１：１の混合物を緑感光性乳剤として使用した。
【０１６９】
（赤感光性ハロゲン化銀乳剤の調製）
前記ＥＭＰ−１０３に対し、下記化合物を用い６０℃にて最適に化学増感を行い、赤感光性ハロゲン化銀乳剤（Ｅｍ−Ｒ１０１）を得た。
【０１７０】
チオ硫酸ナトリウム １．８ｍｇ／モル ＡｇＸ
塩化金酸 ２．０ｍｇ／モル ＡｇＸ
安定剤 ＳＴＡＢ−１ ３×１０^−４モル／モル ＡｇＸ
安定剤 ＳＴＡＢ−２ ３×１０^−４モル／モル ＡｇＸ
安定剤 ＳＴＡＢ−３ ３×１０^−４モル／モル ＡｇＸ
増感色素 ＲＳ−１ １×１０^−４モル／モル ＡｇＸ
増感色素 ＲＳ−２ １×１０^−４モル／モル ＡｇＸ
強色増感剤 ＳＳ−１ ２×１０^−４モル／モル ＡｇＸ
次に（Ｅｍ−Ｒ１０１）の調製において下記化合物を用いて６０℃にて最適に化学増感を行い、赤感光性ハロゲン化銀乳剤（Ｅｍ−Ｒ１０２）を得た。
【０１７１】
チオ硫酸ナトリウム １．８ｍｇ／モル ＡｇＸ
塩化金酸 ２．０ｍｇ／モル ＡｇＸ
安定剤 ＳＴＡＢ−１ ３×１０^−４モル／モル ＡｇＸ
安定剤 ＳＴＡＢ−２ ３×１０^−４モル／モル ＡｇＸ
安定剤 ＳＴＡＢ−３ ３×１０^−４モル／モル ＡｇＸ
増感色素 ＲＳ−１ ２×１０^−４モル／モル ＡｇＸ
増感色素 ＲＳ−２ ２×１０^−４モル／モル ＡｇＸ
強色増感剤 ＳＳ−１ ２×１０^−４モル／モル ＡｇＸ
ＳＴＡＢ−１：１−フェニル−５−メルカプトテトラゾール
ＳＴＡＢ−２：１−（４−エトキシフェニル）−５−メルカプトテトラゾール
ＳＴＡＢ−３：１−（３−アセトアミドフェニル）−５−メルカプトテトラゾール
【０１７２】
【化１１】

【０１７３】
【化１２】

【０１７４】
Ｅｍ−Ｒ１０１とＥｍ−Ｒ１０２の１：１の混合物を赤感光性乳剤として使用した。
【０１７５】
試料Ｎｏ．１０１の調製において、第５層の高沸点有機溶媒を下記表３のように置き換えて試料Ｎｏ．１０２〜１０８を調製した。
【０１７６】
光源としてＢのＬＥＤを主走査方向に１０個並べ露光のタイミングを少しづつ遅延させることによって同じ場所を１０個のＬＥＤで露光出来るように調整した。また、副走査方向にも１０個のＬＥＤを並べ隣接する１０画素分の露光が１度に出来る露光ヘッドを準備した。Ｇ、Ｒも同様にＬＥＤを組み合わせて露光ヘッドを準備した。各ビームの径は約１０μｍで、この間隔でビームを配列し、副走査のピッチは約１００μｍとした。１画素当たりの露光時間は約１００ナノ秒であった。
【０１７７】
最初に適宜、光強度を変化させて露光を行い、露光後、下記の現像処理を行った。
【０１７８】

【０１７９】
漂白定着液タンク液及び補充液
ジエチレントリアミン五酢酸第二鉄アンモニウム２水塩 ６５ｇ
ジエチレントリアミン五酢酸 ３ｇ
チオ硫酸アンモニウム（７０％水溶液） １００ｍｌ
２−アミノ−５−メルカプト−１，３，４−チアジアゾール ２．０ｇ
亜硫酸アンモニウム（４０％水溶液） ２７．５ｍｌ
水を加えて全量を１リットルとし、炭酸カリウム又は氷酢酸でｐＨ＝５．０に調整する。
【０１８０】
安定化液タンク液及び補充液
ｏ−フェニルフェノール １．０ｇ
５−クロロ−２−メチル−４−イソチアゾリン−３−オン ０．０２ｇ
２−メチル−４−イソチアゾリン−３−オン ０．０２ｇ
ジエチレングリコール １．０ｇ
蛍光増白剤（チノパールＳＦＰ） ２．０ｇ
１−ヒドロキシエチリデン−１，１−ジホスホン酸 １．８ｇ
塩化ビスマス（４５％水溶液） ０．６５ｇ
硫酸マグネシウム・７水塩 ０．２ｇ
ＰＶＰ（ポリビニルピロリドン） １．０ｇ
アンモニア水（水酸化アンモニウム２５％水溶液） ２．５ｇ
ニトリロ三酢酸・三ナトリウム塩 １．５ｇ
水を加えて全量を１リットルとし、硫酸又はアンモニア水でｐＨ＝７．５に調整する。
【０１８１】
得られた色素画像をミノルタ社製分光測色計ＣＭ−２０２２を用い、照明と受光の幾何条件ｄ−０、キセノンパルス光源を用いて測光し、２°視野補助標準の光Ｄ５０でのＬ^＊ａ^＊ｂ^＊の値を求めた。このカラーパッチから印刷に近似したベタのパッチを選び出し、これを出力した条件で網％を１０〜９０％まで１０％刻みで変化させた試料を作製した。この試料を１０人の被験者に見せ、２０％の網点とベタの色調を比較し、
５：ほとんど色調の差が見られない
４：色調の差は気にならない
３：色調差があることが分かる
２：色調差が気になる
１：色調のずれが大きい
の５段階で評価し、平均値をとって色調の評価値とした。結果を下記表３に示した。
【０１８２】
【表３】

【０１８３】
【化１３】

【０１８４】
Δθ１２が小さい方が色調の評価値は大きくなる傾向が見られるが、試料Ｎｏ．１０１と１０２では、Δθ１２が１．１異なっていて色調評価値が０．１しか違わず、色調の差が気になるレベルであったのに対し、試料Ｎｏ．１０２と１０７ではΔθ１２が１．０異なっていて色調評価値が１．０異なっていた。Δθ１２の値として８°のあたりに評価が大きく分かれるポイントがあることが分かる。
【０１８５】
実施例２
次ぎに、試料Ｎｏ．１０２〜１０４の調製において、シアンカプラー（Ｃ−１１）を等モルのＣ−１２、Ｃ−２２、ＣＣ−１と変更した以外同様にして試料２０１〜２０９を調製した。この試料を用いて実施例１と同様の評価を行った。結果を下記表４に示した。
【０１８６】
【表４】

【０１８７】
【化１４】

【０１８８】
カプラーの種類を変更しても、Δθ１２≦８°という要件を満たす試料は、いずれも色調の評価値が高いことが分かる。試料Ｎｏ．２０９に対し、試料Ｎｏ．２０６、２０２が近いΔθ１２値を与えているが、Ｎｏ．２０９の評価が低めであった。本発明の一般式（Ｉ）、一般式（ＩＩ）で表される化合物を用いた場合に優れた効果が得られ好ましい。
【０１８９】
前記表４に示されたベタ色調のメトリッククロマと色調評価値の関係をみると、Ｎｏ．１０２〜１０４からは、必ずしもメトリッククロマが高ければ色調評価値が高いという相関があるわけではないことがわかる。しかし、Ｃ−２２を用いた試料Ｎｏ．２０６とＣＣ−１を用いた試料Ｎｏ．２０９では、２０６の方がΔθ１２が大きいにも関わらず色相評価点は高く、また、ＣＣ−１を用いた試料は全体にメトリッククロマが低く色相評価点も低いという傾向があることがわかる。試料を目視した結果では、ＣＣ−１を使用した試料では全体にくすんだ印象を与える色調であり、メトリッククロマが５８以上となるような色材の使用が好ましい。
【０１９０】
実施例３
試料Ｎｏ．１０１の調製において、第５層のＣカプラーと一緒にマゼンタカプラー（Ｍ−１）を分散し、塗布量として０．０３ｇ／ｍ^２となるようにして試料Ｎｏ．３０１を、０．０５ｇ／ｍ^２となるようにして試料Ｎｏ．３０２を作製した。この試料を用いて実施例１と同様の評価を行った結果を下記表５に示した。
【０１９１】
【表５】

【０１９２】
Ｃカプラーと一緒にＭカプラーを混合して分散した試料では、ベタ色調は青味にシフトするＭのベタ色調の変動は予想外に小さく、網％の色調変動の改良効果の方が大きいと判断される結果であった。試料Ｎｏ．３０１、３０２ともΔθ１２≦８°の領域にあり、本発明の効果が得られることが確かめられた。試料Ｎｏ．１０１の調製において、第４層に第３層で用いたマゼンタカプラーとイエローカプラーの混合物を量変化して混合した試料を用いて評価したところ、本発明の効果が得られることが確かめられた。
【０１９３】
実施例４
実施例１の試料１０１、１０２、２０４をＣのベタパッチとして濃度が１．４５となるようＧ光の条件を決め、Ｒ光の条件を種々変更してＲ光とＧ光の光量比を一定に保って光量を変化し、濃度が変化した一連のサンプルを作製した。前記定義に従ってΔθ３４を求め、Δθ３４が６．５°、５．５°になる条件を求め、同時に網％を１０〜９０％まで１０％刻みで変化させた試料を作製した。この試料を１０人の被験者に見せ、２０％の網点とベタの色調を比較し実施例１と同じ基準で色調評価値を求めた。結果を下記表６に示した。
【０１９４】
【表６】

【０１９５】
露光量調整を行って色調を調整した場合にも、感光材料として色調を調整した場合と同様に本発明の効果が得られることが分かった。露光条件を種々変更してみた所では、ベタの色調を同じに揃えたところでの色調差は、感光材料として調整した場合の方が僅かに小さく好ましい結果を与えた。一方、露光条件を調整する方法では、ベタ色調の調整が容易であり印刷条件により近似な条件を作りだすことができ、取り扱い性の面では非常に優れたものであった。
【０１９６】
【発明の効果】
本発明により、網点の濃度が可変なカラープルーフにおいて、Ｃ画像の小点から大点まで網％の変化によらず安定した色調を再現することのできる面積階調画像記録材料及び面積階調画像形成方法を提供することができた。
【図面の簡単な説明】
【図１】Δθ１２を求める図である。
【符号の説明】
１ ベタの再現に用いる色
２ Ａ点
３ 露光量変化の順に並べてａ^＊、ｂ^＊平面上にプロットし曲線[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a proof for confirming the finish of a printed matter in advance, and relates to an area gradation image recording material capable of reproducing a stable color tone from a small point to a large point regardless of a change in dot%. .
[0002]
[Prior art]
Silver halide light-sensitive materials are widely used today because of their high sensitivity, excellent color reproducibility, and suitability for continuous processing. Due to these characteristics, silver halide light-sensitive materials have been widely used not only in the field of photography but also in the field of printing, in the field of so-called proofing for checking the state of the finished printed matter in the middle of printing. ing.
[0003]
In the field of proofing, an image edited on a computer is output to a printing film, and the developed film is appropriately replaced and subjected to decomposing exposure to obtain yellow (Y), magenta (M), and cyan (C). By forming an image and forming an image of the final printed matter on color photographic paper, it has been performed to determine the suitability of the layout and color of the final printed matter.
[0004]
Recently, a method of directly outputting an image edited on a computer to a printing plate has gradually become widespread. In such a case, it is desired to obtain a color image directly from the data on the computer without using a film. Had been rare.
[0005]
For this purpose, various methods such as sublimation type / fusion heat transfer method, electrophotographic method, and ink jet method have been tried, but the method of obtaining high quality images is expensive and the productivity is inferior. There is a disadvantage that the system which is low in cost and has high productivity has poor image quality. A system using a silver halide photosensitive material enables high-quality image formation, such as formation of an accurate halftone image, due to excellent sharpness and the like, while continuous processing is possible as described above. In addition, since images can be simultaneously written in a plurality of color image forming units, high productivity can be realized.
[0006]
In recent years, in the field of printing, so-called digitization has progressed, and there has been an increasing demand for obtaining images directly from data in a computer. For the reasons described above, silver halide photosensitive materials have begun to be advantageously used in this field.
[0007]
An apparatus using a silver halide photosensitive material has been proposed as a proof image forming apparatus, and it is disclosed that the density of halftone dots can be changed (for example, see Non-Patent Document 1). An image forming method using a directly modulated LED as a light source and independently adjusting the density and the dot gain has been disclosed (for example, see Patent Document 1), and a proof image having a small difference from a printed image can be easily obtained. Is disclosed. However, there is no mention of the problem of color fluctuation caused by changing the density of halftone dots, and no solution is suggested.
[0008]
It discloses that by including a coupler having two kinds of hues in the same photosensitive silver halide emulsion layer, a preferable color tone as a proof can be reproduced, and a technique using both a magenta coupler and a yellow coupler is disclosed ( For example, see Patent Literature 2.) It is disclosed that when the printing ink is compared with the magenta dye of the color paper, the printing ink has a reddish color tone, and thus such combination is preferable. This is a technique relating to a method of adjusting a solid color tone, and does not mention the problem of the present invention at all and does not suggest any solution. Further, while the subject of the present invention relates to the color tone of C, this publication discloses a technique relating to the color tone of M.
[0009]
The light-sensitive silver halide emulsion layer contains a main coupler, the non-light-sensitive layer adjacent to the light-sensitive silver halide emulsion layer contains an auxiliary coupler, and a color-forming dye obtained from the main coupler and an adjacent non-light-sensitive emulsion layer Halogenation wherein the difference in the maximum absorption wavelength of the coloring dye obtained from the auxiliary coupler contained therein is at least 70 nm or more, and the main coupler and the auxiliary coupler are contained together with the same high-boiling organic solvent. The silver color photographic light-sensitive material is similar to the printed matter, and the variation with time of the magenta color tone after the development processing is improved, and it is disclosed that a black image is reproduced uniformly.As a main coupler, a magenta coupler and an auxiliary coupler are disclosed. An example of a yellow coupler is disclosed (for example, see Patent Document 3). However, the subject of the present invention is not mentioned at all, and no solution is suggested. Further, while the subject of the present invention relates to the color tone of C, this publication discloses a technique relating to the color tone of M.
[0010]
In a silver halide color photographic material having at least a silver halide emulsion layer containing a C, M, and Y dye-forming coupler on a support, at least one layer has a high silver chloride content of 95 mol% or more. The light-sensitive material containing silver halide grains, the light-sensitive material of which at least three wavelengths are exposed to light, the reflection density of the light-sensitive material in the unexposed state at each of the maximum wavelengths is 0.7 or more. A silver halide color photographic light-sensitive material characterized in that the photographic gradation of the dye-forming layer is 2.3 or more, and the maximum color density of the yellow dye-forming layer is 1.8 or less ( For example, Patent Document 4) discloses that a suitable proof image having rapid processability, small processing fluctuation, and excellent whiteness on a white background can be obtained. The examples disclose that the Y image forming layer contains a C coupler. However, the subject of the present invention is not described at all and no solution is suggested.
[0011]
As described above, in a system that forms an area gradation image based on digital data, a halftone dot is divided into smaller units (here, these are expressed as pixels), and the pixels are exposed with an appropriate exposure amount. It is possible to reproduce a halftone dot as a set by the above. As a simple example, if one halftone dot is composed of 100 pixels, halftone dots are formed by exposing 50 pixels so that halftone% can be developed. You can do it. By using a silver halide photosensitive material in such a method, it is possible to change the halftone dot density, thereby confirming the printing finish under various printing conditions (type of printing paper, trapping of printing ink, etc.) Extremely high productivity because it is possible to reproduce spot colors without decomposing them into process colors and to reproduce the overlap between spot colors and process colors in a discernable manner, and to reproduce this with a single exposure However, there is a problem that the color tone of the small point and the large point of the C image are shifted. It has been desired to improve this drawback and utilize high productivity.
[0012]
[Non-patent document 1]
Digital Consensus Pro Brochure;
Konica Graphic Imaging, Tokyo, September 2002
[0013]
[Patent Document 1]
JP 2001-305701 A (Claims)
[0014]
[Patent Document 2]
JP-A-2-139542 (Claims)
[0015]
[Patent Document 3]
JP 2001-324785 A (Claims)
[0016]
[Patent Document 4]
Japanese Patent Application Laid-Open No. 2002-296737 (Claims)
[0017]
[Problems to be solved by the invention]
An object of the present invention is to provide a color proof in which the print quality under various printing conditions can be confirmed by making the density of halftone dots variable. To provide an area gradation image recording material and an area gradation image forming method capable of reproducing a stable color tone.
[0018]
[Means for Solving the Problems]
The above object of the present invention has been achieved by the following configurations.
[0019]
1. Area gradation image recording including at least one yellow (Y) image forming unit, magenta (M) image forming unit, and cyan (C) image forming unit, each forming a halftone dot as an aggregate of pixels whose density can be changed. An area gradation image recording material, wherein a relationship represented by the following (Equation 1) is satisfied in the C image forming unit.
[0020]
(Equation 1) Δθ12 ≦ 8 °
Here, Δθ12 is the metric hue angle θ1 of the solid color tone of the C image forming unit and the color tone of the color patch created by changing the density in the C image forming unit, a in the CIELAB color space. ^* , B ^* It means the absolute value of the difference from the metric hue angle θ2 of the point A on the locus plotted on the plane. Point A represents the color tone of a color patch formed with 70% of the energy required to form a solid color tone. ^* , B ^* A point on a plane.
[0021]
2. An area gradation image recording material having at least one C image forming unit forming a halftone dot as an aggregate of pixels whose density can be changed, wherein the C image forming unit includes a C image forming material and an M image forming material An area gradation image recording material characterized by including:
[0022]
3. Wherein the area gradation image recording material is a silver halide photosensitive material, and the C image forming unit contains at least the compound represented by the general formula (I) or (II). 3. The area gradation image recording material according to item 2.
[0023]
4. 4. A method for forming an area gradation image, wherein a metric chroma of a solid color tone of a C image obtained from the area gradation image recording material according to any one of 1 to 3 is 58 or more.
[0024]
5. An area gradation image forming method for forming a halftone dot as an aggregate of pixels whose density can be changed based on at least one of Y, M, C, and K (black) image data. An area gradation image forming method, wherein the relationship of (Equation 2) is established.
[0025]
(Equation 2) Δθ34 ≦ 8 °
Here, Δθ34 is the metric hue angle θ3 of the solid color tone of the C image in the area gradation image forming method and the color tone of the color patch created by changing the density in the image forming method, as a in the CIELAB color space. ^* , B ^* It means the absolute value of the difference from the metric hue angle θ4 of point B on the locus plotted on the plane. Point B represents the color tone of a color patch formed with 70% of the energy required to form a solid color tone. ^* , B ^* A point on a plane.
[0026]
6. 6. The area gradation image forming method according to the above item 5, wherein a silver halide photosensitive material containing the compound represented by the general formula (I) or (II) is used.
[0027]
The present invention will be described in more detail. Although there is no particular limitation on the recording material used in the present invention, the following description focuses on a system of a silver halide photosensitive material which is particularly useful and in which the effects of the present invention can be particularly effectively utilized. Further, what is called an image forming unit means, in the simplest example of a silver halide photosensitive material, a layer containing a coupler. The image forming units are not always formed as one layer, and in some cases, are not necessarily formed on the same support. For example, in an image forming system using thermal transfer, a sheet of a Y image forming substance and an image receiving unit may be considered to form a Y image forming unit.
[0028]
One of the features of the present invention is that a halftone dot is formed as an aggregate of pixels whose density can be changed. A digital color proof (hereinafter sometimes referred to as DCP) using a silver halide light-sensitive material uses a system using an area in which the density does not change much even when the exposure is changed, and an area in which the density can be controlled by the exposure. Although a system can be made, there was almost no problem that the color tone of the large point and the small point were shifted in the system using the area where the change in density was small. In systems where the density is controlled by the amount of exposure, problems such as differences in color tone between small points and large points may occur due to the influence of the beam shape (distribution of light intensity), contrast of the photosensitive material, sharpness, etc. It seems, but the reason has not yet been elucidated.
[0029]
One of the features of the present invention is that Δθ12 is 8 ° or less. Here, Δθ12 is the absolute value of the difference between θ1 and θ2 defined below, and θ1 represents the metric hue angle of the solid color tone of the C image forming unit. The metric hue angle is a line segment connecting the point plotted in the CIELAB color space and the origin and a ^* Means the angle between the axes. θ2 represents the metric hue angle of point A according to the following definition. How to determine Δθ12 will be described with reference to FIG.
[0030]
The silver halide light-sensitive material is exposed at a known exposure amount and developed to obtain a dye image. Next, the developed sample was measured with a colorimeter. ^* , B ^* Ask for. These are arranged in the order of the change in the exposure amount, and a ^* , B ^* A curve 3 is obtained by plotting on a plane. Here, the color 1 to be used for reproducing the solid color of C of the area gradation image (the portion of 100% of halftone is called solid) is determined. Usually, the color is selected so as to be close to the color C in printing. When the solid color tone of C is determined in this way, the exposure necessary for obtaining the solid color can be calculated from the above measurement result, and the color tone (a ^* , B ^* ) Is obtained. This is point A. Thus, the solid and point A are a ^* b ^* When plotted on a plane, θ1 and θ2 can be calculated, and Δθ12 is determined.
[0031]
Δθ12 is preferably 5 ° or less, more preferably 3 ° or less.
[0032]
Since this evaluation is affected by the contrast of the photosensitive material, it is necessary to use an exposure apparatus for performing image formation, and to perform evaluation using a developing solution for performing image formation and processing conditions.
[0033]
In order to make the above Δθ12 at 8 ° or less, for example, selecting a coupler having a preferable structure, selecting a structure of a color developing agent, selecting a high boiling organic solvent in which the coupler is dispersed, or selecting a sulfonamide-based This can be attained by selecting and using a compound, a compound having a large effect on the spectral absorption of a coloring dye, such as a phosphate ester compound or a phosphine oxide compound.
[0034]
One of the features of the present invention is that the C image forming unit includes a C image forming substance and an M image forming substance. As one of the methods for reducing Δθ12 to 8 ° or less, an M image forming substance can be mixed in a C image forming unit. Usually, when M is mixed with C, the color tone becomes bluish, which is considered to be rather unfavorable from the viewpoint of approaching the color tone of the printed matter. The color tone shift was rather slight, and it was just surprising that an unexpectedly large effect was obtained. In the case of a silver halide photosensitive material, the C coupler may be mixed with the M coupler and dispersed, or a separately dispersed coupler may be mixed. Further, an M coupler may be present in the intermediate layer. When an M coupler is mixed in the intermediate layer, it is preferable because it has an effect of compensating for the color development of M.
[0035]
Mixing the M dye in the C image can also be achieved by controlling the exposure so that a small amount of the M dye is generated corresponding to the data of the C image.
[0036]
One of the features of the present invention resides in that image formation is performed such that Δθ34 ≦ 8 ° during C image formation. Here, Δθ34 is the absolute value of the difference between θ3 and θ4 defined below, and θ3 represents the metric hue angle of the solid color tone of the C image forming unit.
[0037]
How to determine Δθ34 will be described. The maximum light intensity of the light source for forming the C image and the maximum light intensity of the light source for forming the M image are set, and the silver halide photosensitive material is exposed at a known exposure while changing the light intensity at the same ratio, developed, and developed. Get. Next, measure the developed sample with a colorimeter ^* , B ^* Ask for. These are arranged in the order of the change in the exposure amount, and a ^* , B ^* Plot on a plane. Here, the color to be used for reproducing the solid color of C of the area gradation image (the portion of 100% of halftone is called solid) is determined. Usually, the color is selected so as to be close to the color C in printing. When the solid color tone of C is determined in this way, the exposure necessary for obtaining the solid color can be calculated from the above measurement result, and the color tone (a ^* , B ^* ) Is obtained. This is point B. Thus, the solid and point B are a ^* b ^* When plotted on a plane, θ3 and θ4 can be calculated, and Δθ34 is determined.
[0038]
As the coloring material of C used in the present invention, any known coloring materials can be preferably used, but those having a solid color tone and a metallic chroma of 58 or more are particularly preferred. Those having a high metallic chroma can reproduce clear and vivid colors and are preferable in color reproduction, but at the same time, the drawback that the color tone of the small point and the large point easily deviate was conspicuous. Therefore, the effects of the present invention are more useful and preferable.
[0039]
As the silver halide emulsion used in the present invention, a silver halide emulsion comprising 95% by mole or more of silver chloride is preferable, and any halogen such as silver chloride, silver chlorobromide, silver chloroiodobromide and silver chloroiodide can be used. Those having a composition are used. Among them, a silver chlorobromide containing 95 mol% or more of silver chloride, particularly a silver halide emulsion having a portion containing silver bromide in a high concentration is preferably used. Silver chloroiodide containing about 0.5 mol% is also preferably used. In the silver halide emulsion having a portion containing silver bromide at a high concentration, the portion containing silver bromide at a high concentration may be a so-called core-shell emulsion or may be simply formed without forming a complete layer. A so-called epitaxy junction region in which only a region having a partially different composition may exist may be formed. It is particularly preferable that the portion where silver bromide exists at a high concentration is formed at the top of crystal grains on the surface of silver halide grains. Further, the composition may change continuously or may change discontinuously.
[0040]
It is advantageous that the negative working silver halide emulsion used in the present invention contains a heavy metal ion. This is expected to improve so-called reciprocity failure and prevent desensitization in high-illuminance exposure and softening on the shadow side. Examples of heavy metal ions that can be used for such purposes include Group 8 to 10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt; and twelfth metals such as cadmium, zinc, and mercury. Group transition metals and each ion of lead, rhenium, molybdenum, tungsten, gallium, and chromium can be mentioned. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium, and osmium are preferable. These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt. When the heavy metal ion forms a complex, as the ligand, cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, nitrosyl, ammonia, water, pyridine, Pyrrole, pyrazole, imidazole, thiazole, 1,2,4-triazole, 2,2'-biimidazole, 2,2'-bipyridine or 2,2 ': 6', 2 "-terpyridine compound is preferably used. , Cyanide ion, chloride ion, bromide ion, water, nitrosyl, 5-methylthiazole, 1,2,4-triazole, etc. In order to incorporate a heavy metal ion into a silver halide emulsion, the heavy metal compound must be Before the formation of silver halide grains, during the formation of silver halide grains, after the formation of silver halide grains In order to obtain a silver halide emulsion satisfying the above-mentioned conditions, a heavy metal compound is dissolved together with a halide salt and the whole or a part of the grain forming step is obtained. Alternatively, silver halide fine particles containing these heavy metal compounds may be formed in advance and prepared by adding the silver halide fine particles. The amount to be added to the emulsion is 1 × 10 per mol of silver halide. ^-9 1 x 10 or more ^-2 Mol or less, more preferably 1 × 10 ^-8 More than 5 × 10 ^-5 Molar or less is preferred.
[0041]
Any shape can be used for the particles used in the present invention. One preferable example is a cube having a (100) plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,225,666; JP-A-55-26589; JP-B-55-42737; (1973), etc., particles having shapes such as octahedron, tetradecahedron, and dodecahedron can be produced and used. Further, particles having a twin plane may be used.
[0042]
As the grains used in the present invention, grains having a single shape are preferably used, but it is particularly preferable to add two or more kinds of monodispersed silver halide emulsions to the same layer.
[0043]
The particle size of the particles used in the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.2 to 1.2 μm in consideration of other photographic properties such as rapid processing property and sensitivity. １．０1.0 μm.
[0044]
This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are substantially uniform in shape, the particle size distribution can represent this fairly accurately as diameter or projected area.
[0045]
The distribution of the grain size of the silver halide grains used in the present invention is preferably a monodispersed silver halide grain having a variation coefficient of 0.22 or less, more preferably 0.15 or less, and particularly preferably a variation coefficient of 0.1 or less. That is, two or more monodispersed emulsions of 15 or less are added to the same layer. Here, the variation coefficient is a coefficient representing the width of the particle size distribution, and is defined by the following equation.
[0046]
Coefficient of variation = S / R
(Here, S represents the standard deviation of the particle size distribution, and R represents the average particle size.)
This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are substantially uniform in shape, the particle size distribution can represent this fairly accurately as diameter or projected area.
[0047]
As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.
[0048]
The emulsion used in the present invention may be obtained by any of the acidic method, neutral method, and ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method for producing the seed particles and the method for growing the seed particles may be the same or different.
[0049]
The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, and a combination thereof, but a method obtained by the simultaneous mixing method is preferable. Further, as one type of the simultaneous mixing method, a pAg controlled double jet method described in JP-A-54-48521 can be used.
[0050]
JP-A-57-92523 and JP-A-57-92524 disclose an apparatus for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition apparatus disposed in a reaction mother liquor. No. 921,164, etc., a device for continuously changing the concentration of an aqueous solution of a water-soluble silver salt and a water-soluble halide salt, and the reaction mother liquor is taken out of the reactor described in JP-B-56-501776. Alternatively, an apparatus that forms particles while concentrating by ultrafiltration and keeping the distance between silver halide grains constant may be used.
[0051]
If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added during the formation of silver halide grains or after the completion of grain formation.
[0052]
The negative-working silver halide emulsion used in the present invention can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer. As the chalcogen sensitizer, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, or the like can be used, but a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine, inorganic sulfur and the like.
[0053]
The addition amount of the sulfur sensitizer is preferably changed depending on the kind of the silver halide emulsion to be applied, the expected effect size, and the like. ^-10 ~ 5 × 10 ^-5 Molar range, preferably 5 × 10 ^-8 ~ 3 × 10 ^-5 A molar range is preferred.
[0054]
As the gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like. The amount of the gold compound used is not uniform depending on the type of the silver halide emulsion, the type of the compound to be used, the ripening conditions, etc., but usually 1 × 10 5 per mol of the silver halide. ^-4 Mol ~ 1 x 10 ^-8 Preferably it is molar. More preferably 1 × 10 ^-5 Mol ~ 1 x 10 ^-8 Is a mole.
[0055]
The chemical sensitization of the negative silver halide emulsion used in the present invention may be a reduction sensitization.
[0056]
The silver halide emulsion used in the present invention is known for the purpose of preventing fogging generated during the step of preparing a silver halide light-sensitive material, reducing performance fluctuation during storage, and preventing fogging generated during development. Antifoggants and stabilizers can be used. Examples of preferred compounds that can be used for such purposes include the compounds represented by the general formula (II) described in the lower section of page 7 of JP-A-2-14636, and more preferred specific compounds are Are compounds of (IIa-1) to (IIa-8) and (IIb-1) to (IIb-7) described on page 8 of the same publication, and 1- (3-methoxyphenyl) -5-mercaptotetrazole And 1- (4-ethoxyphenyl) -5-mercaptotetrazole, 1- (3-phenylacetamidophenyl) -5-mercaptotetrazole, and the like.
[0057]
These compounds are added in a step of preparing silver halide emulsion grains, a step of chemical sensitization, a step of preparing a coating solution at the end of the step of chemical sensitization or a step of preparing a coating solution according to the purpose. When chemical sensitization is performed in the presence of these compounds, 1 × 10 5 ^-5 Mol to 5 × 10 ^-4 It is preferably used in a molar amount. When added at the end of chemical sensitization, 1 × 10 ^-6 Mol ~ 1 x 10 ^-2 Molar amounts are preferred, and 1 × 10 ^-5 Mol to 5 × 10 ^-3 Molar is more preferred. In the step of preparing a coating solution, when adding to the silver halide emulsion layer, 1 × 10 ^-6 Mol ~ 1 x 10 ^-1 Molar amounts are preferred, and 1 × 10 ^-5 Mol ~ 1 x 10 ^-2 Molar is more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is 1 m ² 1 × 10 per ^-9 Mol ~ 1 x 10 ^-3 Molar amounts are preferred.
[0058]
In the photographic light-sensitive material used in the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of known compounds can be used. In particular, as dyes having absorption in the visible region, dyes of AI-1 to 11 described in JP-A-3-251840, p. The dyes described in JP-A-3770 are preferably used.
[0059]
The silver halide light-sensitive material according to the present invention comprises a hydrophilic colloid colored with at least one layer of a diffusion-resistant compound on the side closer to the support than the silver halide emulsion layer closest to the support among the silver halide emulsion layers. It is preferred to have a layer. As the coloring substance, a dye or another organic or inorganic coloring substance can be used.
[0060]
The silver halide light-sensitive material used in the present invention has at least one colored hydrophilic colloid layer on the side closer to the support than the silver halide emulsion layer closest to the support among the silver halide emulsion layers. And the layer may contain a white pigment. For example, rutile-type titanium dioxide, anatase-type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin, and the like can be used, but among them, titanium dioxide is preferable for various reasons. The white pigment is dispersed in an aqueous binder of a hydrophilic colloid such as gelatin, which allows the processing liquid to penetrate. The coating amount of the white pigment is preferably 0.1 g / m ² ~ 50g / m ² And more preferably 0.2 g / m ² ~ 5g / m ² Range.
[0061]
Between the support and the silver halide emulsion layer closest to the support, a non-photosensitive hydrophilic colloid layer such as an undercoat layer or an intermediate layer may be provided at any position in addition to the white pigment-containing layer, if necessary. Can be provided.
[0062]
It is preferable to add a fluorescent whitening agent to the silver halide light-sensitive material according to the present invention since whiteness can be further improved. The fluorescent whitening agent is not particularly limited as long as it can absorb ultraviolet light and emit visible light fluorescence. One preferred embodiment is a compound having at least one sulfonic acid group in the molecule. And another preferred form is a solid particulate compound having a fluorescent whitening effect.
[0063]
The silver halide light-sensitive material according to the present invention has a layer containing a silver halide emulsion spectrally sensitized to a specific region in a wavelength region of 400 to 900 nm. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.
[0064]
As the spectral sensitizing dye used in the silver halide emulsion used in the present invention, any known compounds can be used. Examples of the blue sensitizing dye include those described in JP-A-3-251840, page 28. BS-1 to BS-8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used. As the red-sensitive sensitizing dye, RS-1 to 8 described on page 29 of the same publication are preferably used.
[0065]
These sensitizing dyes may be added at any time from the formation of silver halide grains to the end of chemical sensitization. In addition, as a method for adding these dyes, water or an organic solvent miscible with water such as methanol, ethanol, fluorinated alcohol, acetone, and dimethylformamide may be added as a solution, or a sensitizing dye may be added. May be added as a solution, emulsion or suspension in a water-miscible solvent having a density of more than 1.0 g / ml.
[0066]
As a method of dispersing the sensitizing dye, a method of mechanically pulverizing and dispersing the sensitizing dye into fine particles of 1 μm or less in an aqueous system using a high-speed stirring type dispersing machine may be used. 8, a method of mechanically pulverizing and dispersing into fine particles of 1 μm or less in an aqueous system at 60 to 80 ° C., the surface tension described in JP-B-60-6496 being 3.8 × 10 ^-4 A method of dispersing in the presence of a surfactant suppressed to not more than N / cm, disclosed in JP-A-50-80826, which is substantially free of water and dissolved in an acid having a pKa not exceeding 5; A method of adding and dispersing in an aqueous liquid and adding this dispersion to a silver halide emulsion can be used.
[0067]
Water is preferable as a dispersion medium used for dispersion, but the solubility may be adjusted by adding a small amount of an organic solvent, or the stability of the dispersion may be increased by adding a hydrophilic colloid such as gelatin.
[0068]
Examples of the dispersing device that can be used to prepare the dispersion include a high-speed stirring type dispersing device shown in FIG. 1 of JP-A-4-125563, a ball mill, a sand mill, an ultrasonic dispersing device, and the like. be able to.
[0069]
When using these dispersing apparatuses, a method of performing a pre-treatment such as dry pulverization in advance and then performing a wet dispersing method as described in JP-A-4-125632 may be employed.
[0070]
The silver halide emulsion used in the present invention may contain one kind or a combination of two or more kinds of sensitizing dyes.
[0071]
As the coupler used in the silver halide light-sensitive material according to the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by coupling reaction with an oxidized form of a color developing agent is used. Although it is also possible to use, particularly typical examples include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, Typical examples are cyan dye-forming couplers having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm.
[0072]
As the magenta coupler used in the light-sensitive material according to the present invention, a compound represented by the general formula [M-1] described in the right column of page 7 of JP-A-6-95283 is preferable because of excellent spectral absorption characteristics of a coloring dye. Specific examples of preferred compounds include compounds M-1 to M-19 described on pages 8 to 11 of the same publication. Still other specific examples include compounds M-1 to M-61 described in EP 273,712, pp. 6-21 and compounds 1-223 described in 235,913, pp. 36-92. Are other than the representative examples described above.
[0073]
The magenta coupler can be used in combination with other types of magenta couplers, and usually 1 × 10 5 per mol of silver halide. ^-3 Mol to 1 mol, preferably 1 × 10 ^-2 Mol ~ 8 x 10 ^-1 It can be used in the molar range.
[0074]
[Lambda] max of the spectral absorption of the magenta image formed in the photosensitive material according to the present invention is preferably 530 to 560 nm, and [lambda] L0.2 is preferably 580 to 635 nm. λL0.2 is a wavelength longer than the wavelength at which the maximum absorbance shows 1.0 and the wavelength at which the absorbance shows 0.2 on the spectral absorbance curve of the magenta image.
[0075]
The magenta image forming layer of the silver halide light-sensitive material according to the present invention preferably contains a yellow coupler in addition to the magenta coupler. The difference in pKa between these couplers is preferably within 2 and more preferably within 1.5. Preferred yellow couplers to be contained in the magenta image forming layer of the present invention are those represented by the general formula [Y-Ia] described in JP-A-6-95283, page 12, right column. Among the couplers represented by the general formula [Y-1] of the same publication, particularly preferred are couplers represented by the general formula [M-1] when combined with the magenta coupler represented by the general formula [M-1]. Is a coupler having a pKa value not lower than 3 or lower than the pKa lower than 3 pKa.
[0076]
Specific examples of the yellow coupler include compounds Y-1 and Y-2 described in JP-A-6-95283, pages 12 to 13, and compounds described in JP-A-2-139542, pages 13 to 17 ( Y-1) to (Y-58) can be preferably used, but are not limited thereto.
[0077]
One of the features of the present invention is that a cyan image-forming silver halide emulsion layer contains at least one compound represented by formula (I) or (II). The compound represented by the formula (I) or (II) will be described.
[0078]
The substituent having a substituent constant σp defined by Hammett of the cyan coupler of the present invention of +0.20 or more is specifically sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, phosphoryl, carbamoyl, acyl, acyloxy, oxycarbonyl, Examples include groups such as carboxyl, cyano, nitro, halogen-substituted alkoxy, halogen-substituted aryloxy, pyrrolyl, and tetrazolyl, and halogen atoms.
[0079]
Sulfonyl groups include alkylsulfonyl, arylsulfonyl, halogen-substituted alkylsulfonyl, halogen-substituted arylsulfonyl and the like; sulfinyl groups include alkylsulfinyl and arylsulfinyl and the like; sulfonyloxy groups include alkylsulfonyloxy and arylsulfonyloxy; and sulfamoyl Groups include N, N-dialkylsulfamoyl, N, N-diarylsulfamoyl, N-alkyl-N-arylsulfamoyl and the like; phosphoryl groups include alkoxyphosphoryl, aryloxyphosphoryl, alkylphosphoryl, aryl Phosphoryl and the like; carbamoyl groups include N, N-dialkylcarbamoyl, N, N-diarylcarbamoyl, N-alkyl-N-arylcarbamoyl and the like; acyl As an acyloxy group, alkylcarbonyloxy, etc .; as an oxycarbonyl group, alkoxycarbonyl, aryloxycarbonyl, etc .; as a halogen-substituted alkoxy group, as α-halogen-substituted alkoxy, etc .; Examples of the aryloxy group include tetrafluoroaryloxy and pentafluoroaryloxy; and examples of the pyrrolyl group include 1-pyrrolyl; and examples of the tetrazolyl group include 1-tetrazolyl.
[0080]
In addition to the above substituents, a trifluoromethyl group, a heptafluoroisopropyl group, a nonylfluoro-t-butyl group, a tetrafluoroaryl group, a pentafluoroaryl group, and the like are also preferably used.
[0081]
In the general formula (I), R ₁ Or R ₂ Among the substituents represented by, substituents other than the electron-withdrawing group include, but are not particularly limited to, alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, and arylthio. , Alkenyl, cycloalkyl, cycloalkenyl, alkynyl, heterocyclic, alkoxy, aryloxy, heterocyclic oxy, siloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl , Aryloxycarbonyl, heterocyclic thio, thioureido, hydroxyl and mercapto groups, spiro compound residues, bridged hydrocarbon compound residues, and the like.
[0082]
The alkyl group preferably has 1 to 32 carbon atoms and may be linear or branched. As the aryl group, a phenyl group is preferable.
[0083]
Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group; examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group; and the alkyl component and the aryl component of the alkylthio group and the arylthio group include the above-described alkyl groups and aryl groups. Can be
[0084]
The alkenyl group is preferably a group having 2 to 32 carbon atoms, and the cycloalkyl group is preferably a group having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. The alkenyl group may be linear or branched. The cycloalkenyl group preferably has 3 to 12 carbon atoms, particularly preferably 5 to 7 carbon atoms.
[0085]
Examples of the ureido group include an alkylureido group and an arylureido group; and examples of the sulfamoylamino group include an alkylsulfamoylamino group and an arylsulfamoylamino group; and a heterocyclic group preferably having 5 to 7 members. Specifically, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group, and the like; a heterocyclic oxy group having a 5- to 7-membered heterocyclic ring is preferable. 6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazol-5-oxy group, etc .; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio group, 2-benzothiathiol Zolylthio group, 2,4-diphenoxy-1,3,5-triazole-6-thio group and the like; siloxy groups include trimethylsiloxy group and triethyl Succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group, etc. as imide group; spiro [3.3] heptane-1- as spiro compound residue Yl and the like; as bridged hydrocarbon compound residues, bicyclo [2.2.1] heptane-1-yl and tricyclo [3.3.1.1] ^3.7 ] Decane-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like.
[0086]
These groups may further contain a substituent such as a long-chain hydrocarbon group or a diffusion-resistant group such as a polymer residue.
[0087]
In the general formula (I), X ₁ Examples of the group capable of leaving by reaction with an oxidized form of a color developing agent represented by the following include a halogen atom (hydrochloric acid, bromine, fluorine and the like) and alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryl Oxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkoxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring linked by N atom, alkoxycarbonylamino, aryloxycarbonylamino, Examples of each group include carboxyl and the like. Of these, preferred are a hydrogen atom and a nitrogen-containing heterocyclic group bonded by an alkoxy, aryloxy, alkylthio, arylthio, or N atom.
[0088]
In the general formula (I), Z ₁ Examples of the nitrogen-containing 5-membered heterocyclic ring formed by the above include a pyrazole ring, an imidazole ring, a benzimidazole ring, a triazole ring, and a tetrazole ring.
[0089]
More specifically, the compound represented by the general formula (I) is represented by the following general formulas (I) -1 and (I) -2.
[0090]
Embedded image

[0091]
R in the above general formula (I) -1 ₁ And R ₁₁ And at least one of R in (1) -2 ₁ And R ₁₂ At least one is an electron-withdrawing group having σp of 0.20 or more.
[0092]
X ₁ Is X in the general formula (I) ₁ And in general formulas (I) -1 and (I) -2, R ₁ And R ₁₁ ~ R ₁₂ Of those, those not having an electron-withdrawing group having σp of 0.20 or more represent a hydrogen atom or a substituent.
[0093]
In the general formula (II), R ₃ And R ₄ Represents an electron-withdrawing group having a Hammett's substituent constant σp of 0.20 or more, and these electron-withdrawing groups include R in the general formula (I). ₁ And R ₂ And the same groups as the electron-withdrawing groups. Where R ₃ And R ₄ Is greater than or equal to 0.65.
[0094]
Z ₂ Examples of the nitrogen-containing 5-membered heterocyclic ring formed by the above include a pyrazole ring, an imidazole ring and a tetrazole ring. These 5-membered nitrogen-containing heterocycles may have a substituent.
[0095]
More specifically, the compound represented by the general formula (II) is represented by the following general formulas (II) -1 and (II) -2.
[0096]
Embedded image

[0097]
Where R ₃ , R ₄ And X ₂ Has the same meaning as in general formula (II). R ₂₁ Represents a hydrogen atom or a substituent.
[0098]
Specific examples of the compound represented by formula (I) or (II) are shown below, but the invention is not limited thereto.
[0099]
Embedded image

[0100]
Embedded image

[0101]
Embedded image

[0102]
Embedded image

[0103]
In particular, in the invention in which the structure of the cyan coupler is not specified, a known phenol type, naphthol type or imidazole type coupler can be used. For example, a phenol coupler substituted with an alkyl group, an acylamino group or a ureido group, a naphthol coupler formed from a 5-aminonaphthol skeleton, a 2-equivalent naphthol coupler having an oxygen atom introduced as a leaving group, and the like are represented. You. Among these, preferred compounds include the general formulas [C-I] and [C-II] described on page 13 of JP-A-6-95283.
[0104]
The cyan coupler is usually used in the silver halide emulsion layer in an amount of 1 × 10 5 per mol of silver halide. ^-3 ~ 1 mol, preferably 1 × 10 ^-2 ~ 8 × 10 ^-1 It can be used in the molar range.
[0105]
One of the features of the present invention resides in that the C image forming unit includes the C image forming substance and the M image forming substance. In the silver halide photosensitive material, any known M coupler can be preferably used. The M coupler may be added as a single dispersion, or may be added as a common dispersion with the C coupler.
[0106]
As the yellow coupler contained in the yellow image forming layer in the light-sensitive material according to the present invention, a known acylacetanilide-based coupler or the like can be preferably used.
[0107]
Specific examples of the yellow coupler include compounds described on pages 5 to 9 of JP-A-3-241345, compounds represented by Y-I-1 to Y-I-55, and JP-A-3-209466. And the compounds represented by Y-1 to Y-30 on pages 11 to 14 can also be preferably used. Further, couplers represented by general formula [Y-I] described in JP-A-6-95283, page 21, and compounds represented by general formulas (I) and (II) described in JP-A-2002-351223 can also be mentioned. .
[0108]
The λmax of the spectral absorption of the yellow image formed by the photosensitive material according to the present invention is preferably 425 nm or more, and λL0.2 is preferably 515 nm or less.
[0109]
The spectral absorption λL0.2 of the yellow color image is a value defined by the contents described in JP-A-6-95283, page 21, right column, lines 1 to 24. Indicates the magnitude of unwanted absorption on the side.
[0110]
The yellow coupler is usually used in the silver halide emulsion layer in an amount of 1 × 10 5 per mole of silver halide. ^-3 ~ 1 mol, preferably 1 × 10 ^-2 ~ 8 × 10 ^-1 It can be used in the molar range.
[0111]
In order to adjust the spectral absorption characteristics of the magenta image, the cyan image, and the yellow image, it is preferable to add a compound having a color tone adjusting action. As the compound for this, a phosphoric ester compound represented by the general formula [HBS-I] described on page 22 of JP-A-6-95283 and a phosphine oxide compound represented by [HBS-II] are preferable. Preferred are compounds represented by the general formula [HBS-II] described on page 22 of the same publication. Also, higher alcohol compounds represented by (ai) to (ax) described on page 5 of JP-A-4-265,975 can be mentioned.
[0112]
In the light-sensitive material according to the present invention, the silver halide emulsion layer is laminated and coated on a support, but the order from the support may be any order. In addition, an intermediate layer, a filter layer, a protective layer, and the like can be provided as necessary.
[0113]
An anti-fading agent can be used in combination with each of the magenta, cyan, and yellow couplers to prevent fading of the formed dye image due to light, heat, humidity, and the like. Preferred compounds include phenyl ether compounds represented by the general formulas I and II described on page 3 of JP-A-2-66541, phenol compounds represented by the general formula IIIB described in JP-A-3-174150, and Amine compounds represented by the general formula A described in JP-A 90445 and metal complexes represented by the general formulas XII, XIII, XIV and XV described in JP-A-62-182741 are particularly preferred for magenta dyes. Compounds represented by the general formula I 'described in JP-A-1-19649 and compounds represented by the general formula II described in JP-A-5-11417 are particularly preferred for yellow and cyan dyes.
[0114]
When an oil-in-water emulsion dispersion method is used to add a stain inhibitor or other organic compound used in the silver halide light-sensitive material according to the present invention, a water-insoluble high-boiling organic compound having a boiling point of 150 ° C or higher is usually used. If necessary, a low-boiling point and / or water-soluble organic solvent is used in combination in the solvent, and the mixture is dissolved and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After or simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added. As the high boiling point organic solvent that can be used for dissolving and dispersing the stain inhibitor and the like, phosphine oxides such as tricresyl phosphate and trioctyl phosphate are preferably used, and phosphine oxides such as trioctyl phosphine oxide are preferably used. Can be The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Two or more high boiling organic solvents can be used in combination.
[0115]
Preferred compounds as a surfactant used for dispersing a photographic additive used in the photosensitive material according to the present invention and adjusting a surface tension at the time of coating include a hydrophobic group having 8 to 30 carbon atoms in one molecule and a sulfone. Those containing an acid group or a salt thereof are mentioned. Specific examples include A-1 to A-11 described in JP-A-64-26854. Further, a surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after the dispersion and the time from the addition to the coating solution to the coating are preferably shorter, each being 10 hours. Preferably within 3 hours, more preferably within 20 minutes.
[0116]
In the silver halide light-sensitive material according to the present invention, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or is added to a silver halide emulsion layer. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula II described in JP-A-4-133056, and include compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17.
[0117]
It is preferable to add an ultraviolet absorber to the light-sensitive material according to the present invention to prevent static fog or improve the light fastness of a dye image. Preferred ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are those represented by the general formula III-3 described in JP-A-1-250944 and those represented by the general formula III described in JP-A-64-66646. Compounds described in JP-A-63-187240, compounds represented by general formula I described in JP-A-4-1633, compounds represented by general formula (I) described in JP-A-5-165144, The compound shown by (II) is mentioned.
[0118]
It is preferable that the light-sensitive material according to the present invention contains an oil-soluble dye or pigment because whiteness is improved. Representative specific examples of oil-soluble dyes include compounds 1 to 27 described in JP-A-2-842, pp. 8-9.
[0119]
In the silver halide light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder.If necessary, other gelatin, a gelatin derivative, a graft polymer of gelatin and another polymer, a protein other than gelatin, A hydrophilic colloid such as a sugar derivative, a cellulose derivative, or a synthetic hydrophilic polymer such as a homopolymer or a copolymer can also be used.
[0120]
As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. It is preferable to use the compounds described in JP-A-61-249054 and JP-A-61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer in order to prevent the growth of mold and bacteria which adversely affect the photographic performance and image storability. It is preferable to add a slipping agent or matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer in order to improve the physical properties of the surface of the photosensitive material or the processed sample.
[0121]
As the support used in the photosensitive material according to the present invention, any material may be used, and paper coated with polyethylene or polyethylene terephthalate, a paper support made of natural pulp or synthetic pulp, a vinyl chloride sheet, a white pigment, Polypropylene, polyethylene terephthalate support, baryta paper and the like which may be contained can be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable. As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.
[0122]
A support having a water-resistant resin coating layer on the surface of paper is usually 50 to 300 g / m2. ² Is used. For the purpose of obtaining a proof image, in order to bring the feeling of handling closer to printing paper, 130 g / m2 is used. ² The following base papers are preferably used, and 70 to 120 g / m ² Base paper is preferably used.
[0123]
The support used in the present invention can be preferably used regardless of whether it has random irregularities or is smooth.
[0124]
As the white pigment used for the support, an inorganic and / or organic white pigment can be used, and an inorganic white pigment is preferably used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silica, silica such as synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.
[0125]
The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by mass or more, and more preferably 15% by mass, in order to improve sharpness.
[0126]
The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as the coefficient of variation described in the above publication.
[0127]
The resin layer of the paper support having a water-resistant resin layer on both sides used in the present invention may be a single layer or a plurality of layers. It is preferable to form a plurality of layers and to include a white pigment at a high concentration in contact with the emulsion layer, because sharpness is greatly improved and a proofing image is formed.
[0128]
Further, it is more preferable that the value of the center plane average roughness (SRa) of the support is 0.15 μm or less, and more preferably 0.12 μm or less, since the effect of good gloss is obtained.
[0129]
The photographic light-sensitive material used in the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, and then directly or undercoating (adhesion, antistatic property, It may be applied via one or more undercoat layers for improving degree stability, friction resistance, hardness, antihalation property, frictional properties and / or other properties.
[0130]
When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.
[0131]
As the exposure light source of the exposure apparatus used in the present invention, any known light source can be preferably used, but a laser or a light emitting diode (hereinafter, referred to as LED) is more preferably used. A width of 400 mm or more is preferably used. A photosensitive material having a width of 800 mm or more is also preferably used.
[0132]
As a laser, a semiconductor laser (hereinafter, referred to as an LD) is preferably used because it is compact and the life of the light source is long. In addition, LDs are used for applications such as optical pickups for DVDs and music CDs, barcode scanners for POS systems, and for applications such as optical communication, and have the advantage of being inexpensive and having a relatively high output. have. Specific examples of LD include aluminum gallium indium arsenide (650 nm), indium gallium phosphorus (リ ン 700 nm), gallium arsenic phosphorus (610 to 900 nm), and gallium aluminum arsenide (760 to 850 nm). ) And the like. Recently, a laser emitting blue light has been developed, but at present, it is advantageous to use an LD as a light source having a longer wavelength than 610 nm.
[0133]
As a laser light source having an SHG element, light emitted from an LD or YAG laser is converted into half-wavelength light by the SHG element and emitted. Since a visible light is obtained, there is no green light source. Used as a light source in the blue region. As an example of this type of light source, there is a combination of a YAG laser and an SHG element (532 nm).
[0134]
Examples of the gas laser include a helium-cadmium laser (about 442 nm), an argon ion laser (about 514 nm), and a helium neon laser (about 544 nm and 633 nm).
[0135]
As an LED, an LED having a composition similar to that of an LD is known, but various LEDs from blue to infrared have been put to practical use. An edge-emitting diode, which is a kind of small-area light-emitting diode described in JP-A-2002-72367, can be preferably used.
[0136]
As an exposure light source used in the present invention, each laser may be used alone, or a combination thereof may be used as a multi-beam. In the case of an LD, for example, by arranging ten LDs, a beam composed of ten light beams can be obtained. On the other hand, in the case of a helium neon laser, the light emitted from the laser is split into, for example, ten light beams by a beam separator.
[0137]
In the case of an LD or LED, the intensity of the exposure light source can be directly modulated by changing the value of the current flowing through each element. In the case of direct modulation, the amount of emitted light may be changed by adjusting the current value, or a pulse width modulation method in which light is emitted in a pulse shape and the pulse width (emission time) is changed may be used. A pulse number modulation method of changing the number may be employed. In the case of an LD, the intensity may be changed using an element such as an AOM (acousto-optic modulator). In the case of a gas laser, a device such as an AOM or an EOM (electro-optic modulator) is generally used.
[0138]
When an LED is used as a light source, a method may be used in which the same pixel is repeatedly exposed by a plurality of elements as long as the amount of light is weak.
[0139]
The emission wavelength of the light source can be preferably used as long as the photosensitive material has a sufficient sensitivity in the wavelength region, but a wavelength region having a sufficient sensitivity difference from other photosensitive layers in order to prevent color turbidity can be used. Preferably, it is used. Although it depends on the contrast of the photosensitive material, there is preferably a sensitivity difference of 0.6 or more, preferably 1.0 or more as a common logarithm of the exposure amount. In addition, if the emission wavelength fluctuates due to the environmental conditions, operating conditions, etc. where the light source is placed, it is theoretically preferable to adjust the wavelength to the peak wavelength of the spectral sensitivity. It is preferable to select the wavelength in consideration of the relationship with the wavelength. Such examples include JP-A-6-75342 and JP-A-2001-83663. Even when the emission intensity fluctuates in addition to the emission wavelength, it is preferable to select the emission wavelength in relation to the spectral sensitivity. For example, Japanese Patent Application Laid-Open No. 2002-72367 and Nikkei New Materials 1987 It is described on page 54 of the issue on March 14th.
[0140]
As a device used for image formation, a method in which a plurality of photosensitive materials are set in advance and a photosensitive material is appropriately selected and used can be preferably used. In this case, the two types of photosensitive materials may be, for example, photosensitive materials having different widths or photosensitive materials having different surface qualities (unevenness of the support). The selection of the photosensitive material may be performed by a method of setting with a switch of the image forming apparatus, or may be performed based on the setting information transmitted with the image data. It is also advantageous to automatically select the optimum size of the photosensitive material according to the size of the image data. In special cases, the same type of photosensitive material can be loaded, and when one photosensitive material is used up, the other photosensitive material can be used automatically, which makes continuous unattended operation possible. Can be used for
[0141]
In the present invention, the term "area gradation image" is used. However, this is not expressed by the density of the color of each pixel but by the size of the area of a portion colored to a specific density. And may be considered synonymous with halftone dots.
[0142]
In the case of normal area gradation exposure, the purpose can be achieved by developing Y, M, C, and black. More preferably, in order to identify that a single color such as M or C has developed in addition to black, it is preferable to use three or more different exposure amounts for exposure. In printing, a plate of a special color may be used, but in order to reproduce this, it is preferable to use four or more values of exposure for different exposures.
[0143]
In the case of a laser light source, the beam diameter is preferably 25 μm or less, more preferably 6 to 22 μm. Although smaller than 6 μm is preferable in terms of image quality, adjustment is difficult and processing speed is reduced. On the other hand, if it is larger than 25 μm, the unevenness increases and the sharpness of the image deteriorates. By optimizing the beam diameter, writing of a high-definition image without unevenness can be performed at high speed.
[0144]
To draw an image with such light, it is necessary for the light beam to scan over the silver halide photosensitive material.However, the photosensitive material is wound around a cylindrical drum and rotated at high speed in a direction perpendicular to the rotation direction. A cylindrical outer surface scanning method in which a light beam is moved may be used, and a cylindrical inner surface scanning method in which a silver halide photosensitive material is brought into close contact with a cylindrical recess and exposed is preferably used. A plane scanning method may be adopted in which the polyhedral mirror is rotated at a high speed and the silver halide light-sensitive material conveyed thereby is exposed by moving a light beam at right angles to the conveying direction. In order to obtain a high quality and large image, a cylindrical outer surface scanning method is more preferably used.
[0145]
In order to perform exposure by the cylindrical outer surface scanning method, the silver halide photosensitive material must be accurately brought into close contact with a cylindrical drum. In order for this to be performed properly, it is necessary that the wafer be transported while being accurately aligned. The silver halide light-sensitive material used in the present invention is preferably used when the surface on the side to be exposed is rolled outward, so that the alignment can be more accurately performed. From the same viewpoint, the support used for the silver halide light-sensitive material used in the present invention has appropriate rigidity, and preferably has a Taber rigidity of 0.8 to 4.0.
[0146]
The drum diameter can be arbitrarily set in accordance with the size of the silver halide photosensitive material to be exposed. The number of rotations of the drum can be set arbitrarily, but an appropriate number of rotations can be selected according to the beam diameter of the laser beam, the energy intensity, the writing pattern, the sensitivity of the photosensitive material, and the like. From the viewpoint of productivity, it is preferable that scanning exposure can be performed at higher rotation speed, but specifically, 200 to 3000 rotations per minute is preferably used.
[0147]
The method of fixing the silver halide photosensitive material to the drum may be fixed by mechanical means, or a large number of fine holes that can be suctioned on the drum surface are provided according to the size of the photosensitive material, and the photosensitive material is fixed. It can also be brought into close contact by suction. It is important to make the photosensitive material as close as possible to the drum in order to prevent troubles such as uneven images.
[0148]
Known compounds can be used as the aromatic primary amine developing agent used in the present invention. The following compounds can be mentioned as examples of these compounds.
[0149]
CD-1) N, N-diethyl-p-phenylenediamine
CD-2) 2-Amino-5-diethylaminotoluene
CD-3) 2-Amino-5- (N-ethyl-N-laurylamino) toluene
CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline
CD-5) 2-Methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline
CD-6) 4-Amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline
CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide
CD-8) N, N-dimethyl-p-phenylenediamine
CD-9) 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline
CD-10) 4-Amino-3-methyl-N-ethyl-N- (β-ethoxyethyl) aniline
CD-11) 4-Amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline
In the present invention, the above can be used in any pH range of the color developer, but from the viewpoint of rapid processing, the pH is preferably from 9.5 to 13.0, more preferably from 9.8 to 12.0. Used in
[0150]
The processing temperature of color development according to the present invention is preferably 35 ° C. or more and 70 ° C. or less. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, the higher the temperature, the more preferable.
[0151]
Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferably within 40 seconds, and more preferably within 25 seconds.
[0152]
A known developer component compound can be added to the color developing solution in addition to the above color developing agent. Usually, an alkali agent having a pH buffering action, a chloride ion, a development inhibitor such as benzotriazoles, a preservative, a chelating agent and the like are used.
[0153]
The silver halide light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed. The developing apparatus used for developing the silver halide light-sensitive material of the present invention is a roller transport type in which the light-sensitive material is conveyed between rollers arranged in a processing tank, and the light-sensitive material is fixed to a belt. An endless belt method may be used, in which the processing tank is formed in a slit shape, and a processing liquid is supplied to the processing tank and the photosensitive material is transported, or a spray method in which the processing liquid is sprayed. Alternatively, a web method by contact with a carrier impregnated with a treatment liquid, a method using a viscous treatment liquid, and the like can be used. When processing in large quantities, it is usual to run using an automatic developing machine, but at this time, the smaller the replenishment amount of the replenisher, the more preferable the replenishment amount is. And the method described in JP-A-94-16935 is most preferable.
[0154]
Preferred embodiments of the present invention are shown below, but the present invention is not limited thereto.
(1) An area floor having at least one yellow (Y) image forming unit, magenta (M) image forming unit, and cyan (C) image forming unit, each forming a halftone dot as an aggregate of pixels whose density can be changed. An area gradation image recording material, wherein the formula (1) is satisfied in the C image forming unit.
(2) An area gradation image recording material having at least one C image forming unit that forms a halftone dot as an aggregate of pixels whose density can be changed, wherein the C image forming unit is a C image forming substance and an M image An area gradation image recording material comprising a forming substance.
(3) The area gradation image recording material according to any one of (1) and (2), which is a silver halide photosensitive material.
(4) The area gradation image recording material according to (3), wherein the M image forming substance is an M coupler and is dispersed independently of a C coupler.
(5) The area gradation image recording material according to (3), wherein the M image forming substance is an M coupler, and is contained in an intermediate layer between the C image forming unit and the M image forming unit.
(6) The area gradation image recording material according to any one of (3) to (5), wherein the C coupler is represented by the general formula (I) or the general formula (II).
(7) The area gradation image recording material according to any one of (1) to (6), wherein the C image has a solid color metric chroma of 58 or more.
(8) The area gradation image recording material according to any one of (1) to (7), wherein Δθ12 is 5 ° or less.
(9) The area gradation image recording material according to any one of (1) to (7), wherein Δθ12 is 3 ° or less.
(10) A method of forming an area gradation image in which halftone dots are formed as a set of pixels whose density can be changed based on at least one of Y, M, C, and K (black) image data. An area gradation image forming method, wherein (Formula 2) is satisfied at the time of formation.
(11) The area gradation image recording material according to (10), wherein Δθ34 is 5 ° or less.
(12) The area gradation image recording material according to (10), wherein Δθ34 is 3 ° or less.
(13) Area gradation image formation according to (10) to (12), wherein a silver halide photosensitive material containing a compound represented by the general formula (I) or (II) is used. Method.
[0155]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples, but embodiments of the present invention are not limited thereto.
[0156]
Example 1
A high-density polyethylene on one side laminated with molten polyethylene containing anatase-type titanium oxide dispersed at a content of 15% by mass on the other side. = 3.5, PY value = 2.7 μm), and each layer having the layer constitution shown in the following Tables 1 and 2 was coated on the side of the polyethylene layer containing titanium oxide, and 6.00 g of gelatin was further formed on the back side. / M ² , Silica matting agent 0.65 g / m ² The multilayer silver halide photosensitive material sample No. 101 was produced.
[0157]
The coupler was dissolved in a high-boiling-point solvent, ultrasonically dispersed, and added as a dispersion. At this time, (SU-1) was used as a surfactant. (H-1) and (H-2) were added as hardeners. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. The total amount of (F-1) was 0.04 g / m in each layer. ² Was added so that
[0158]
[Table 1]

[0159]
[Table 2]

[0160]
SU-1: sodium tri-i-propylnaphthalenesulfonate
SU-2: di (2-ethylhexyl) sulfosuccinate sodium salt
SU-3: di (2,2,3,3,4,4,5,5-octafluoropentyl) sodium salt of sulfosuccinate
H-1: tetrakis (vinylsulfonylmethyl) methane
H-2: sodium 2,4-dichloro-6-hydroxy-s-triazine sodium
HQ-1: 2,5-di-t-octylhydroquinone
HQ-2: 2,5-di ((1,1-dimethyl-4-hexyloxycarbonyl) butyl) hydroquinone
HQ-3: a mixture of 2,5-di-sec-dodecylhydroquinone, 2,5-di-sec-tetradecylhydroquinone and 2-sec-dodecyl-5-sec-tetradecylhydroquinone at a mass ratio of 1: 1: 2.
SO-1: trioctylphosphine oxide
SO-2: di (i-decyl) phthalate
SO-3: Oleyl alcohol
SO-4: tricresyl phosphate
PVP: polyvinylpyrrolidone
[0161]
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[0162]
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[0163]
(Preparation of blue-sensitive silver halide emulsion)
The following (Solution A) and (Solution B) were simultaneously added to one liter of a 2% aqueous gelatin solution kept at 40 ° C. while controlling pAg = 7.3 and pH = 3.0, and the following (Solution C) and (Solution D) was added simultaneously while controlling pAg = 8.0 and pH = 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled using sulfuric acid or an aqueous sodium hydroxide solution.
(A liquid)
3.42 g of sodium chloride
Potassium bromide 0.03g
200 ml with water
(B liquid)
Silver nitrate 10g
200 ml with water
(Liquid C)
Sodium chloride 102.7g
Potassium hexachloroiridate (IV) 4 × 10 ^-8 Mole
Potassium hexacyanoferrate (III) 2 × 10 ^-5 Mole
1.0 g of potassium bromide
600 ml with water
(D liquid)
Silver nitrate 300g
600 ml with water
After completion of the addition, desalting is performed using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd., and then mixed with an aqueous gelatin solution to have an average particle diameter of 0.71 μm and a coefficient of variation of particle diameter distribution. A monodispersed cubic emulsion EMP-101 having a silver chloride content of 0.07 and a silver chloride content of 99.5 mol% was obtained.
[0164]
The above (EMP-101) was optimally chemically sensitized at 60 ° C. using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B101).
[0165]
Sodium thiosulfate 0.8mg / mol AgX
Chloroauric acid 0.5mg / mol AgX
Stabilizer STAB-1 3 × 10 ^-4 Mol / mol AgX
Stabilizer STAB-2 3 × 10 ^-4 Mol / mol AgX
Stabilizer STAB-3 3 × 10 ^-4 Mol / mol AgX
Sensitizing dye BS-1 4 × 10 ^-4 Mol / mol AgX
Sensitizing dye BS-2 1 × 10 ^-4 Mol / mol AgX
Potassium bromide 0.2g / mol AgX
Next, in the preparation of EMP-101, the average particle diameter was adjusted in the same manner as in EMP-101 except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. A monodispersed cubic emulsion EMP-102 having a size of 64 μm, a coefficient of variation in particle size distribution of 0.07 and a silver chloride content of 99.5 mol% was obtained. Em-B102 was obtained in the same manner as in the preparation of Em-B101 except that EMP-102 was used instead of EMP-101, and a 1: 1 mixture of Em-B101 and 102 was used as a blue-sensitive emulsion.
[0166]
(Preparation of green photosensitive silver halide emulsion)
In the preparation of EMP-101, the average particle diameter was 0.40 μm, the variation coefficient was 0.08, and the chloride was changed in the same manner except that the addition time of (Solution A) and (Solution B), (Solution C) and (Solution D) was changed. A monodispersed cubic emulsion (EMP-103) having a silver content of 99.5% was obtained.
[0167]
The above-mentioned EMP-102 was optimally chemically sensitized at 55 ° C. using the following compounds to obtain a green-sensitive silver halide emulsion (Em-G101).
[0168]
Sodium thiosulfate 1.5mg / mol AgX
Chloroauric acid 1.0mg / mol AgX
Stabilizer STAB-1 3 × 10 ^-4 Mol / mol AgX
Stabilizer STAB-2 3 × 10 ^-4 Mol / mol AgX
Stabilizer STAB-3 3 × 10 ^-4 Mol / mol AgX
Sensitizing dye GS-1 4 × 10 ^-4 Mol / mol AgX
Sensitizing dye GS-2 2 × 10 ^-4 Mol / mol AgX
Sodium chloride 0.5g / mol AgX
Next, in the preparation of EMP-103, the average particle size was adjusted in the same manner as in EMP-103 except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. A monodispersed cubic emulsion EMP-104 having a thickness of 50 µm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained. Em-G102 was obtained in the same manner as Em-G101 except that EMP-104 was used in place of EMP-103, and a 1: 1 mixture of Em-G101 and 102 was used as a green photosensitive emulsion.
[0169]
(Preparation of red-sensitive silver halide emulsion)
The EMP-103 was optimally chemically sensitized at 60 ° C. using the following compounds to obtain a red-sensitive silver halide emulsion (Em-R101).
[0170]
Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer STAB-1 3 × 10 ^-4 Mol / mol AgX
Stabilizer STAB-2 3 × 10 ^-4 Mol / mol AgX
Stabilizer STAB-3 3 × 10 ^-4 Mol / mol AgX
Sensitizing dye RS-1 1 × 10 ^-4 Mol / mol AgX
Sensitizing dye RS-2 1 × 10 ^-4 Mol / mol AgX
Supersensitizer SS-1 2 × 10 ^-4 Mol / mol AgX
Next, in the preparation of (Em-R101), the following compounds were optimally chemically sensitized at 60 ° C. to obtain a red-sensitive silver halide emulsion (Em-R102).
[0171]
Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer STAB-1 3 × 10 ^-4 Mol / mol AgX
Stabilizer STAB-2 3 × 10 ^-4 Mol / mol AgX
Stabilizer STAB-3 3 × 10 ^-4 Mol / mol AgX
Sensitizing dye RS-1 2 × 10 ^-4 Mol / mol AgX
Sensitizing dye RS-2 2 × 10 ^-4 Mol / mol AgX
Supersensitizer SS-1 2 × 10 ^-4 Mol / mol AgX
STAB-1: 1-phenyl-5-mercaptotetrazole
STAB-2: 1- (4-ethoxyphenyl) -5-mercaptotetrazole
STAB-3: 1- (3-acetamidophenyl) -5-mercaptotetrazole
[0172]
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[0173]
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[0174]
A 1: 1 mixture of Em-R101 and Em-R102 was used as a red-sensitive emulsion.
[0175]
Sample No. In the preparation of Sample No. 101, the high boiling point organic solvent in the fifth layer was replaced as shown in Table 3 below. 102-108 were prepared.
[0176]
By arranging ten B LEDs as a light source in the main scanning direction and delaying the timing of the exposure little by little, adjustment was made so that the same location could be exposed by the ten LEDs. Also, an exposure head was prepared in which ten LEDs were arranged in the sub-scanning direction, and exposure for ten adjacent pixels could be performed at one time. For G and R, exposure heads were prepared by combining LEDs in the same manner. The diameter of each beam was about 10 μm, the beams were arranged at this interval, and the sub-scanning pitch was about 100 μm. The exposure time per pixel was about 100 nanoseconds.
[0177]
First, exposure was performed by appropriately changing the light intensity, and after the exposure, the following development processing was performed.
[0178]

[0179]
Bleach-fixer tank solution and replenisher
Diethylenetriaminepentaacetic acid ammonium ferric dihydrate 65g
3 g of diethylenetriaminepentaacetic acid
Ammonium thiosulfate (70% aqueous solution) 100ml
2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g
Ammonium sulfite (40% aqueous solution) 27.5ml
The total volume is made up to 1 liter by adding water and adjusted to pH = 5.0 with potassium carbonate or glacial acetic acid.
[0180]
Stabilizing solution tank solution and replenisher solution
1.0 g of o-phenylphenol
5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g
2-methyl-4-isothiazolin-3-one 0.02 g
1.0 g of diethylene glycol
Optical brightener (Tinopearl SFP) 2.0g
1.8 g of 1-hydroxyethylidene-1,1-diphosphonic acid
Bismuth chloride (45% aqueous solution) 0.65g
Magnesium sulfate heptahydrate 0.2g
PVP (polyvinyl pyrrolidone) 1.0 g
Aqueous ammonia (25% ammonium hydroxide aqueous solution) 2.5 g
Nitrilotriacetic acid trisodium salt 1.5g
The total volume is adjusted to 1 liter by adding water and adjusted to pH = 7.5 with sulfuric acid or aqueous ammonia.
[0181]
The obtained dye image is measured using a spectrophotometer CM-2022 manufactured by Minolta Co., using geometric conditions d-0 for illumination and light reception, and using a xenon pulse light source. ^* a ^* b ^* Was determined. A solid patch similar to printing was selected from these color patches, and a sample was prepared in which the halftone percentage was changed from 10 to 90% in 10% increments under the conditions for outputting the solid patch. This sample was shown to 10 subjects, and the halftone dot of 20% was compared with the solid color tone.
5: almost no difference in color tone
4: I don't mind the color difference
3: It turns out that there is a color difference
2: I am worried about the color difference
1: Large color shift
The evaluation was made in five steps, and the average value was taken as the evaluation value of the color tone. The results are shown in Table 3 below.
[0182]
[Table 3]

[0183]
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[0184]
The smaller the value of Δθ12 is, the higher the evaluation value of the color tone tends to be. Samples Nos. 101 and 102 differed in Δθ12 by 1.1 and differed only in the color tone evaluation value by 0.1. In 102 and 107, Δθ12 was different by 1.0 and the color tone evaluation value was different by 1.0. It can be seen that there is a point where the evaluation is largely divided around 8 ° as the value of Δθ12.
[0185]
Example 2
Next, the sample No. Samples 201 to 209 were prepared in the same manner as in the preparation of 102 to 104 except that the cyan coupler (C-11) was changed to equimolar C-12, C-22, and CC-1. The same evaluation as in Example 1 was performed using this sample. The results are shown in Table 4 below.
[0186]
[Table 4]

[0187]
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[0188]
It can be seen that, even when the type of coupler is changed, any sample satisfying the requirement of Δθ12 ≦ 8 ° has a high color tone evaluation value. Sample No. 209, the sample No. Nos. 206 and 202 give close Δθ12 values. 209 was low. When the compounds represented by the general formulas (I) and (II) of the present invention are used, excellent effects are obtained, which is preferable.
[0189]
Looking at the relationship between the solid color metric chroma and the color tone evaluation value shown in Table 4 above, From 102 to 104, it can be seen that there is not always a correlation that the higher the metric chroma, the higher the color tone evaluation value. However, the sample No. Sample No. 206 using CC-1 and CC-1 In 209, it can be seen that the hue evaluation point of 206 is higher in spite of the larger Δθ12, and that the sample using CC-1 generally has a lower metric chroma and a lower hue evaluation point. As a result of visual observation of the sample, the sample using CC-1 has a color tone giving a dull impression as a whole, and it is preferable to use a coloring material having a metric chroma of 58 or more.
[0190]
Example 3
Sample No. In the preparation of 101, the magenta coupler (M-1) was dispersed together with the C coupler of the fifth layer, and the coating amount was 0.03 g / m2. ² The sample No. 301 to 0.05 g / m ² The sample No. 302 was produced. The same evaluation as in Example 1 was performed using this sample, and the results are shown in Table 5 below.
[0191]
[Table 5]

[0192]
In the sample in which the M coupler was mixed and dispersed together with the C coupler, the solid color tone shifted to bluish. The solid color tone variation of M was unexpectedly small, and the improvement effect of the halftone% color tone variation was judged to be larger. Was the result. Sample No. Both 301 and 302 are in the range of Δθ12 ≦ 8 °, and it has been confirmed that the effects of the present invention can be obtained. Sample No. In the preparation of Sample No. 101, the fourth layer was evaluated using a sample in which the mixture of the magenta coupler and the yellow coupler used in the third layer was mixed in varying amounts, and it was confirmed that the effects of the present invention could be obtained.
[0193]
Example 4
Using the samples 101, 102, and 204 of Example 1 as solid patches of C, the conditions of G light are determined so that the density becomes 1.45, and the conditions of R light are variously changed to keep the light amount ratio of R light and G light constant. A series of samples in which the amount of light was changed while maintaining the concentration and the concentration was changed were produced. Δθ34 was determined in accordance with the above definition, the conditions under which Δθ34 was 6.5 ° and 5.5 ° were determined, and at the same time, a sample was prepared in which the screen percentage was changed from 10 to 90% in steps of 10%. This sample was shown to ten subjects, and the halftone dot and the solid color tone were compared with each other to obtain a color tone evaluation value based on the same standard as in Example 1. The results are shown in Table 6 below.
[0194]
[Table 6]

[0195]
It was found that the effects of the present invention can be obtained when the color tone is adjusted by adjusting the exposure amount, similarly to the case where the color tone is adjusted as a photosensitive material. When the exposure conditions were variously changed, the difference in color tone when the solid color tone was adjusted to the same value was slightly smaller when adjusted as a photosensitive material, and a favorable result was obtained. On the other hand, in the method of adjusting the exposure condition, the solid color tone can be easily adjusted, and a condition closer to the printing condition can be created, and the handleability is very excellent.
[0196]
【The invention's effect】
According to the present invention, in a color proof in which the density of halftone dots is variable, an area gradation image recording material and an area gradation capable of reproducing a stable color tone from a small dot to a large dot of a C image regardless of a change in dot%. An image forming method can be provided.
[Brief description of the drawings]
FIG. 1 is a diagram for calculating Δθ12.
[Explanation of symbols]
1 Colors used for solid reproduction
2 Point A
3 In the order of exposure change ^* , B ^* Plot on a plane and curve

Claims (6)

Area gradation image recording including at least one yellow (Y) image forming unit, magenta (M) image forming unit, and cyan (C) image forming unit, each forming a halftone dot as an aggregate of pixels whose density can be changed. An area gradation image recording material, wherein a relationship represented by the following (Equation 1) is satisfied in the C image forming unit.
(Equation 1) Δθ12 ≦ 8 °
Here, Δθ12 is a plot of the metric hue angle θ1 of the solid color tone of the C image forming unit and the color tone of the color patch created by changing the density in the C image forming unit on the a ^* and b ^* planes of the CIELAB color space. Means the absolute value of the difference from the metric hue angle θ2 of the point A on the track. Point A is a point on the a ^* , b ^* plane that represents the color tone of a color patch formed with 70% of the energy required to form a solid color tone. An area gradation image recording material having at least one C image forming unit forming a halftone dot as an aggregate of pixels whose density can be changed, wherein the C image forming unit includes a C image forming material and an M image forming material An area gradation image recording material characterized by including: The area gradation image recording material is a silver halide photosensitive material, and the C image forming unit contains at least a compound represented by the following general formula (I) or (II). Or the area gradation image recording material according to 2.

[Wherein, R ₁ represents a hydrogen atom or a substituent, and R ₂ represents a substituent. m is the number of the substituents _{R 2.} When m is 0, R ₁ represents an electron-withdrawing group having a Hammett's substituent constant σp of 0.20 or more. When m is 1 or 2 or more, at least one of R ₁ and R ₂ is substituted by Hammett. Represents an electron-withdrawing group having a group constant σp of 0.20 or more. Z ₁ represents a group of nonmetallic atoms necessary for forming a nitrogen-containing 5-membered heterocyclic ring which may be condensed with a benzene ring or the like. X ₁ represents a hydrogen atom or a group which is released by a coupling reaction with an oxidized form of a color developing agent. ]

[Wherein, R ₃ and R ₄ represent an electron-withdrawing group having a Hammett's substituent constant σp of 0.20 or more. However, the sum of the σp values of R ₃ and R ₄ is 0.65 or more. Z ₂ represents a group of nonmetallic atoms necessary for forming a nitrogen-containing 5-membered heterocyclic ring, and the 5-membered ring may have a substituent. X ₂ represents a hydrogen atom or a group which is released by a coupling reaction with an oxidized form of a color developing agent. ] A method for forming an area gradation image, wherein a metric chroma of a solid color tone of a C image obtained from the area gradation image recording material according to claim 1 is 58 or more. An area gradation image forming method for forming a halftone dot as an aggregate of pixels whose density can be changed based on at least one of Y, M, C, and K (black) image data. An area gradation image forming method, wherein the relationship of (Equation 2) is established.
(Equation 2) Δθ34 ≦ 8 °
Here, Δθ34 is the metric hue angle θ3 of the solid color tone of the C image in the area gradation image forming method and the color tone of the color patch created by changing the density in the image forming method, a ^* , b in the CIELAB color space. ^{* It} means the absolute value of the difference from the metric hue angle θ4 of point B on the locus plotted on the plane. Point B is a point on the a ^* , b ^* plane that represents the color tone of a color patch formed with 70% of the energy required to form a solid color tone. 6. The area gradation image forming method according to claim 5, wherein a silver halide photosensitive material containing the compound represented by the general formula (I) or (II) is used.

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