JP4248166B2 - Silver halide photographic material - Google Patents

Description

【００２４】
ゼラチンの塗布量は、０．０５〜１０ｇ／ｍ²が望ましい。 また、ゼラチン中の超微粒子二酸化チタンの添加量は１〜９０質量％が好ましく、３０〜７０質量％がより好ましい。該添加量は１重量％より少ないと効果が小さく、９０重量％より多いと分散性が不充分であり、いずれも好ましくない。
【００２５】
（超微粒子二酸化チタン）
本発明のハロゲン化銀写真感光材料では、前記水溶性高分子をバインダーとして超微粒子二酸化チタンを共に含有することができる。この超微粒子二酸化チタン含有層を配設したことにより、本発明のハロゲン化銀写真感光材料は、シャープネス（解像度）とブライトネス（輝度）が向上し、奥行き感のある画像が形成できると共に耐光性が改良される。
【００２６】
上記の超微粒子二酸化チタンは、チタニウム塩を加水分解或いは気相酸化するなどして製造されるもので、従来のチタン白として用いられていた顔料とは異なり、その１次粒子径が１桁以上小さい超微粒子で、光散乱が抑制され透明性が高く、紫外線吸収能も大幅に向上されている。尚、該超微粒子二酸化チタンは、ルチル型、ブルッカイト型、及びアナターゼ型の何れの結晶構造でも構わないが、ルチル型が最も好適に使用することができる。
【００２７】
本発明で使用される超微粒子二酸化チタンの平均粒子径は、０．０２μｍ以下であり、０．０１μｍ以下であることが更に効果を発揮する上で好ましい。ここで平均粒子径とは面積平均の粒子径を意味し、個々の粒子の投影面積と等価な円の直径を以て該粒子の径と見なし、その数平均をとったものである。また、それらの粒子径の分布は変動係数（粒子径分布の標準偏差を平均粒子径で除したもの）で２０％以下、好ましくは１５％以下、更に好ましくは１０％以下の所謂単分散であるものが好ましい。
【００２８】
また、超微粒子二酸化チタン含有層に含まれる前記超微粒子二酸化チタンの含有率は、該含有層に対して、５〜９５質量％とすることが好ましく、１０〜９０質量％が更に好ましく、１５〜８５質量％とすることが特に好ましい。超微粒子二酸化チタンの含有率を上記５〜９５質量％の範囲内に設定すると、本発明の記録材料のシャープネス（解像度）、ブライトネス（輝度）、及び耐光性においてより好適な結果が得られる。
【００２９】
また、本発明に使用できる超微粒子二酸化チタンは、分散性及び作業性を改良するために無機化合物や有機化合物で表面処理されていてもよい。表面処理の具体例としては、特開昭５２−３５６２５号、同５５−１０８６５号、同５７−３５８５５号、６２−２５７５３号、６２−１０３６３５号、及び特願平７−２０００９９号等に開示されているものを使用することができる。好ましい表面処理は、酸化アルミニウム水和物、含水酸化亜鉛、二酸化珪素などの無機化合物や、２〜４価のアルコール、トリメチロールアミン、チタネートカップリング剤やシランカップリング剤などの有機化合物が好ましく用いられる。各表面処理剤量はそれぞれの目的に応じて選択できるが、無機の表面処理剤の場合は、超微粒子二酸化チタンに対して約３重量パーセント以下の範囲が一般的であり、０．０１〜１重量パーセントの範囲が好ましい。有機化合物の場合は約５重量パーセント以下の範囲が一般的であり、０．１〜３重量パーセントの範囲が好ましい。
【００３０】
また本発明においては、発明の効果を損なわない範囲において、上記超微粒子二酸化チタンの他に、通常の二酸化チタン、酸化アルミニウム、酸化亜鉛、炭酸カルシウム、硫酸カルシウム等の光反射性物質或いは顔料物質を含有又は分散していてもよい。超微粒子二酸化チタンは、その特殊製法に起因して比較的に高価な素材であるだけに、所望の品質さえ確保できれば、他の通常粒径の顔料を併用することは経済的に有利となる。但し併用する場合も、超微粒子二酸化チタンの使用量は、全顔料の３０質量％以上、好ましくは５０質量％以上であることが望ましい。
【００３１】
（感光性ハロゲン化銀乳剤層）
本発明のハロゲン化銀写真感光材料では、支持体の水溶性高分子と超微粒子二酸化チタンとを含む層の上に、感光性ハロゲン化銀乳剤層が形成される。該感光性ハロゲン化銀乳剤層及び非感光性層の形成には、親水性コロイド、具体的にはゼラチンを結合材として使用することが好ましい。各層にはハロゲン化銀乳剤、発色剤乳化物及び混色防止剤乳化物等の画像形成に必要な化合物が含有される。
【００３２】
本発明のハロゲン化銀写真感光材料は、好ましくは支持体上にイエロー発色性ハロゲン化銀乳剤層、マゼンタ発色性ハロゲン化銀乳剤層、シアン発色性ハロゲン化銀乳剤層を少なくとも一層ずつ塗設して構成することができる。一般のカラー印画紙では、ハロゲン化銀乳剤の感光する光と補色の関係にある色素を形成するカラーカプラーを含有させることで減色法の色再現を行なうことができる。一般的なカラー印画紙では、ハロゲン化銀乳剤粒子は前述の発色層の順に青感性、緑感性、赤感性の分光増感色素によりそれぞれ分光増感され、また支持体上に前出の順で塗設して構成することができる。しかしながら、これと異なる順序であってもよい。又、感光層と発色色相とは、上記の対応を持たない構成としてもよく、赤外感光性ハロゲン化銀乳剤層を少なくとも一層用いることもできる。
【００３３】
本発明ではハロゲン化銀粒子としては、９５モル％以上が塩化銀である塩化銀、塩臭化銀又は塩沃臭化銀粒子を使用することが好ましい。特に、本発明においては現像処理時間を速めるために、実質的に沃化銀を含まない塩臭化銀若しくは塩化銀よりなるものを好適に用いることができる。ここで実質的に沃化銀を含まないとは、沃化銀含有率が１モル％以下、好ましくは０．２モル％以下のことを言う。一方、高照度感度を高める、分光増感感度を高める、或いは感光材料の経時安定性を高める目的で、特開平３−８４５４５号に記載されているように、乳剤表面に０．０１〜３モル％の沃化銀を含有した高塩化銀粒子が好ましく用いられる場合もある。
【００３４】
乳剤のハロゲン組成は粒子間で異なっていても等しくてもよいが、粒子間で等しいハロゲン組成を有する乳剤を用いると、各粒子の性質を均質にすることが容易である。また、ハロゲン化銀乳剤粒子内部のハロゲン組成分布については、ハロゲン化銀粒子のどの部分をとっても組成の等しい所謂均一型構造の粒子や、ハロゲン化銀粒子内部のコア（芯）とそれを取り囲むシェル（殻）〔一層又は複数層〕とでハロゲン組成の異なる所謂積層型構造の粒子或いは、粒子内部若しくは表面に非層状にハロゲン組成の異なる部分を有する構造（粒子表面にある場合は粒子のエッジ、コーナー或いは面上に異組成の部分が接合した構造）の粒子などを適宜選択して用いることができる。高感度を得るには、均一型構造の粒子よりも後二者のいずれかを用いることが有利であり、耐圧力性の面からも好ましい。ハロゲン化銀粒子が上記のような構造を有する場合には、ハロゲン組成において異なる部分の境界部は、明確な境界であっても、組成差により混晶を形成して不明確な境界であってもよく、また積極的に連続的な構造変化を持たせたものであってもよい。
【００３５】
本発明で使用する高塩化銀乳剤においては、臭化銀局在相を前述のような層状若しくは非層状にハロゲン化銀粒子内部及び／又は表面に有する構造のものが好ましい。上記局在相のハロゲン組成は、臭化銀含有率において少なくとも１０モル％のものが好ましく、２０モル％を越えるものがより好ましい。臭化銀局在相の臭化銀含有率は、Ｘ線回折法（例えば、「日本化学会編；新実験化学講座６：構造解析」丸善、に記載されている。）等を用いて分析することができる。そして、これらの局在相は、粒子内部、粒子表面のエッジ、コーナー或いは面上にあることができるが、一つの好ましい例として、粒子のコーナー部にエピタキシャル成長したものを挙げることができる。また、現像処理液の補充量を低減する目的でハロゲン化銀乳剤の塩化銀含有率を更に高めることも有効である。この様な場合には、その塩化銀含有率が９８〜１００モル％であるような、ほぼ純塩化銀の乳剤も好ましく用いられる。
【００３６】
本発明に用いるハロゲン化銀乳剤に含まれるハロゲン化銀粒子の平均粒子サイズ（粒子の投影面積と等価な円の直径を以て粒子サイズとし、その数平均をとったもの）は、０．１μ〜２μが好ましい。また、それらの粒子サイズ分布は変動係数（粒子サイズ分布の標準偏差を平均粒子サイズで除したもの）２０％以下、好ましくは１５％以下、更に好ましくは１０％以下の所謂単分散的なものが好ましい。この際、広いラチチュードを得る目的で上記の単分散乳剤を同一層にブレンドして使用することや、重層塗布することも好ましく行われる。写真乳剤に含まれるハロゲン化銀粒子の形状は、立方体、十四面体或いは八面体のような規則的な（Regular)結晶形を有するもの、球状、板状などのような変則的な（Irregular)結晶形を有するもの、或いはこれらの複合形を有するものを用いることができる。また、種々の結晶形を有するものを混合したものからなっていてもよい。本発明においてはこれらの中でも上記規則的な結晶形を有する粒子を５０％以上、好ましくは７０％以上、より好ましくは９０％以上含有するのがよい。また、これら以外にも平均アスペクト比（円換算直径／厚み）が５以上、好ましくは８以上の平板状粒子が投影面積として全粒子の５０％を越えるような乳剤も好ましく用いることができる。この平板状粒子としては、粒子表面が（１１１）面である平板粒子、（１００）面である平板粒子何れも好ましく使用できる。
【００３７】
本発明に用いる塩（臭）化銀乳剤は、P.Glafkides 著 Chimie et Phisique Photographique（Paul Montel社刊、１９６７年）、G.F.Duffin著 Photographic Emulsion Chemistry（Focal Press社刊、１９６６年）、V.L.Zelikman et al著 Making and Coating Photographic Emulsion（Focal Press 社刊、１９６４年）等に記載された方法を用いて調製することができる。即ち、酸性法、中性法、アンモニア法等のいずれでもよく、また可溶性銀塩と可溶性ハロゲン塩を反応させる形式としては、片側混合法、同時混合法、及びそれらの組合せなどのいずれの方法を用いてもよい。粒子を銀イオン過剰の雰囲気の下において形成させる方法（所謂逆混合法）を用いることもできる。同時混合法の一つの形式としてハロゲン化銀の生成する液相中のｐＡｇを一定に保つ方法、即ち所謂コントロールド・ダブルジェット法を用いることもできる。この方法によると、結晶形が規則的で粒子サイズが均一に近いハロゲン化銀乳剤を得ることができる。
【００３８】
ハロゲン化銀粒子の局在相またはその基質には、異種金属イオン又はその錯イオンを含有させることが好ましい。好ましい金属としては周期律表の第VIII族、第IIｂ族に属する金属イオン或いは金属錯体、及び鉛イオン、タリウムイオン等の中から選ばれる。本発明の感光材料の構成の効果は、金増感された高塩化銀乳剤を用いた際に、より顕著である。
本発明の感光材料は、通常のネガプリンターを用いたプリントシステムに使用される以外に、ガスレーザー、発光ダイオード、半導体レーザー、半導体レーザー或いは半導体レーザーを励起光源に用いた固体レーザーと非線形光学結晶を組合せた第二高調波発生光源、等の単色高密度光を用いたデジタル走査露光に好ましく使用される。システムをコンパクトで、安価なものにするために半導体レーザー、半導体レーザー或いは固体レーザーと非線形光学結晶を組合せた第二高調波発生光源（ＳＨＧ） を使用することが好ましい。特にコンパクトで、安価、更に寿命が長く安定性が高い装置を設計するためには半導体レーザーの使用が好ましく、露光光源の少なくとも一つは半導体レーザーを使用することが望ましい。
【００３９】
このような走査露光光源を使用する場合、本発明の感光材料の分光感度極大は使用する走査露光用光源の波長により任意に設定することが出来る。半導体レーザーを励起光源に用いた固体レーザー或いは半導体レーザーと非線形光学結晶を組合せて得られるＳＨＧ光源では、レーザーの発振波長を半分にできるので、青色光、緑色光が得られる。従って、感光材料の分光感度極大は通常の青、緑、赤の３つの領域に持たせることが可能である。装置を安価で安定性の高い、コンパクトなものにするために光源として半導体レーザーを使用するためには、少なくとも２層が６７０ｎｍ以上に分光感度極大を有していることが好ましい。これは、入手可能な安価で、安定な III−Ｖ族系半導体レーザーの発光波長域が現在赤から赤外領域にしかないためである。しかしながら実験室レベルでは、緑や青域のII−VI族系半導体レーザーの発振が確認されており、半導体レーザーの製造技術が発達すればこれらの半導体レーザーを安価に安定に使用することができるであろうことは十分に予想される。このような場合は、少なくとも２層が６７０ｎｍ以上に分光感度極大を有する必要性は小さくなる。
【００４０】
シアンカプラーとしては、特開平２−３３１４４号公報に記載のジフェニルイミダゾール系シアンカプラー、欧州特許ＥＰ０３３３１８５Ａ２号明細書に記載の３−ヒドロキシピリジン系シアンカプラー、特開昭６４−３２２６０号公報に記載された環状活性メチレン系シアンカプラー、欧州特許ＥＰ０４５６２２６Ａ１号明細書に記載のピロロピラゾール型シアンカプラー、欧州特許ＥＰ０４８４９０９号に記載のピロロイミダゾール型シアンカプラー、欧州特許ＥＰ０４８８２４８号明細書及びＥＰ０４９１１９７Ａ１号明細書に記載のピロロトリアゾール型シアンカプラーの使用が好ましい。その中でもピロロトリアゾール型シアンカプラーの使用が特に好ましい。
【００４１】
本発明に用いられるマゼンタカプラーとしては、５−ピラゾロン系マゼンタカプラーやピラゾロアゾール系マゼンタカプラーが用いられるが、中でも色相や画像安定性、発色性等の点で特開昭６１−６５２４５号に記載されている２級又は３級アルキル基がピラゾロトリアゾール環の２、３又は６位に直結したピラゾロトリアゾールカプラー、特開昭６１−６５２４６号に記載されている分子内にスルホンアミド基を含んだピラゾロアゾールカプラー、特開昭６１−１４７２５４号に記載されているアルコキシフェニルスルホンアミドバラスト基を持つピラゾロアゾールカプラーや欧州特許第２２６,８４９Ａ号や同第２９４,７８５Ａ号に記載されている６位にアルコキシ基やアリーロキシ基をもつピラゾロアゾールカプラーの使用が好ましい。
【００４２】
また、イエローカプラーとしては、欧州特許ＥＰ０４４７９６９Ａ１号明細書に記載のアシル基に３〜５員の環状構造を有するアシルアセトアミド型イエローカプラー、欧州特許ＥＰ０４８２５５２Ａ１号明細書に記載の環状構造を有するマロンジアニリド型イエローカプラー、米国特許第５,１１８,５９９号明細書に記載されたジオキサン構造を有するアシルアセトアミド型イエローカプラーが好ましく用いられる。その中でも、アシル基が１−アルキルシクロプロパン−１−カルボニル基であるアシルアセトアミド型イエローカプラー、アニリドの一方がインドリン環を構成するマロンジアニリド型イエローカプラーの使用が特に好ましい。これらのカプラーは、単独使用或いは併用することができる。
【００４３】
本発明のハロゲン化銀写真感光材料に適用されるハロゲン化銀乳剤やその他の素材（添加剤など）及び写真構成層（層配置など）としては、上記の他、下記の表１〜４に示す特許公報、特に欧州特許ＥＰ０,３５５,６６０Ａ２号（特開平２−１３９５４４号）明細書に記載されているものが好適に用いられる。
【００４４】
【表１】

【００４５】
【表２】

【００４６】
【表３】

【００４７】
【表４】

【００４８】
【実施例】
以下に本発明を実施例によって具体的に説明するが、本発明はこれに限定されるものではない。尚、本実施例中の「部」及び「％」は、特に断りのない限り、夫々「質量部」及び「質量％」を表す。
【００４９】
［実施例１］
（支持体の調製）
ＬＢＫＰ１００部からなる木材パルプをダブルディスクリファイナーによりカナディアンフリーネス３００ｍｌまで叩解し、エポキシ化ベヘン酸アミド０．５部、アニオンポリアクリルアミド１．０部、ポリアミドポリアミンエピクロルヒドリン０．１部、及びカチオンポリアクリルアミド０．５部を対パルプ絶乾質量比で添加し、長網抄紙機により秤量１５０ｇ／ｍ²の原紙を抄造し、１．０ｇ／ｍ²絶乾重量のポリビニルアルコールで表面サイズし、カレンダー処理によって密度１．０に調製した。
【００５０】
上記原紙のワイヤー面（裏面）にコロナ放電処理を行った後、溶融押出し機にて高密度ポリエチレンを樹脂厚３５μｍとなるようにコーティングし、マット面からなる裏面樹脂層を形成した。
【００５１】
また、原紙のフェルト面（表面）側にコロナ放電処理を行った後、アナターゼ型酸化チタン１０部及び微量の群青を含有した低密度ポリエチレンを熱溶融押出し機にて樹脂厚が３０μｍとなるようにコーティングし、光沢面からなる表面樹脂層を形成した。
（下塗り層の塗布）
酵素分解ゼラチン（平均分子量１００００、ＰＡＧＩ法粘度１５ｍＰ、ＰＡＧＩ法ゼリー強度２０ｇ）４０部に水６０部を加え、温度４０℃で攪拌し、該ゼラチンを溶解した。上記ゼラチン４０％水溶液の１０部に、超微粒子二酸化チタン２０％分散液（触媒化成工業製の「ＥＬＣＯＭ−Ｐ」、平均粒子径０．００８μｍ）２００部を混合し撹拌して、下塗り液を調製した。更に、塗布する前に下記エポキシ系ゼラチン硬膜剤１部を該下塗り液に添加した。
【００５２】
【化２】

【００５３】
上記支持体の表面樹脂層をコロナ放電処理した後、上記下塗り液を乾燥後塗布量が２．０ｇ／ｍ²となるように塗布した。
【００５４】
（写真構成層の形成）
下塗り層上に、特開平９−２０４００１号公報の実施例１の感光材料１０１Ａ〜Ｇと同様に写真構成層を形成して、実施例１に係わるハロゲン化銀写真感光材料を作製した。
【００５５】
［実施例２］
実施例１の下塗り層の塗布において、酵素分解ゼラチン４０％水溶液１０部に超微粒子二酸化チタン２０％分散液（触媒化成工業製の「ＥＬＣＯＭ−Ｐ」）２００部を混合する代わりに、酵素分解ゼラチン４０％水溶液１０部に超微粒子二酸化チタン２０％分散液（触媒化成工業製の「ＥＬＣＯＭ−Ｐ」）２０部を混合したこと以外は、実施例１と同様にして実施例２に係わるハロゲン化銀写真感光材料を作製した。
【００５６】
［実施例３］
実施例１の下塗り層の塗布において、酵素分解ゼラチン４０％水溶液１０部に超微粒子二酸化チタン２０％分散液（触媒化成工業製の「ＥＬＣＯＭ−Ｐ」）２００部を混合する代わりに、酵素分解ゼラチン４０％水溶液１０部に超微粒子二酸化チタン２０％分散液（触媒化成工業製の「ＥＬＣＯＭ−Ｐ」）５部を混合したこと以外は、実施例１と同様にして実施例３に係わるハロゲン化銀写真感光材料を作製した。
【００５７】
［比較例１］
実施例３の下塗り層の塗布において、酵素分解ゼラチン４０％水溶液１０部に超微粒子二酸化チタン２０％分散液（触媒化成工業製の「ＥＬＣＯＭ−Ｐ」）５部を混合する代わりに、酵素分解ゼラチン４０％水溶液１０部に二酸化チタン（石原産業製の「タイペークＡ−２２０」、平均粒子径０．１６μｍ）０．８部を混合したこと以外は、実施例１と同様にして比較例１に係わるハロゲン化銀写真感光材料を作製した。
【００５８】
［比較例２］
実施例１の下塗り層の塗布において、超微粒子二酸化チタン２０％分散液（触媒化成工業製の「ＥＬＣＯＭ−Ｐ」）２００部を混合しなかったこと以外は、実施例１と同様にして比較例２に係わるハロゲン化銀写真感光材料を作製した。
【００５９】
これらのハロゲン化銀写真感光材料について、以下の評価試験を行った。
（１）鮮鋭度（ＣＴＦ）
ハロゲン化銀写真感光材料に解像力チャートを密着し、緑色光で露光し、カラー画像処理した。この処理済のハロゲン化銀写真感光材料の画像部及び背景部の濃度をマイクロデンシトメーターで測定し、常法に従いパーソナルコンピューターで計算してマゼンタ層のＣＴＦ（Ｃｏｎｔｒａｓｔ Ｔｒａｎｓｆｅｒ Ｆｕｎｃｔｉｏｎ：コントラスト伝達関数、１０本／ｍｍにおける値）を求め、これを画像の鮮鋭度とした。ＣＴＦはその数値が大きい程、画像の鮮鋭度が高いことを表す。
【００６０】
（２）光沢感
得られたハロゲン化銀写真感光材料をカラーネガフィルムより露光し、焼き付けし、カラー現像処理をしてカラープリントを得た。該プリント画像の目視比較により、光沢感のあるものから順に◎、○、△、×と評価した。
【００６１】
（３）画像耐光性
ハロゲン化銀写真感光材料に、マゼンタ、イエロー、シアンの濃度階調のついたストリップスチャートを焼き付け、カラー現像処理をして濃度階調ストリップスプリントを得た。このプリントをｗｅａｔｈｅｒｏｍｅｔｅｒ ＣＩ６５（Ａｔｌａｓ Ｅｌｅｃｔｒｉｃ Ｄｅｖｉｃｅ ｃｏ．製）により、０．９Ｗ／ｍ²で４週間照射した。予め照射処理する前のマゼンタ成分の反射濃度を測定しておき、ほぼ反射濃度１．０近辺の処の、照射テスト後の反射濃度を測定し、これらの反射濃度から画像耐光性を常法により百分率で示した。この数字の高い程、画像耐光性が良好であることを表す。
以上の評価結果を、下記の表５に示す。
【００６２】
【表５】

【００６３】
実施例のハロゲン化銀写真感光材料では、比較例の感光材料に比べて、鮮鋭度が高く、光沢感があり、画像耐光性にも優れていること分かった。特に結婚式と人物像などの写真を、比較例のカラープリントと目視評価すると、光沢感のある華やかな画像が得られた。
【００６４】
【発明の効果】
本発明のハロゲン化銀写真感光材料は、超微粒子二酸化チタンを使用することにより、シャープネス及び光沢感を向上させ、これにより奥行き感のある鮮明な画像の形成が可能になると共に画像の耐光性をも向上させることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silver halide photographic light-sensitive material, and more particularly to improvement of sharpness, gloss and image light resistance.
[0002]
[Prior art]
Various kinds of silver halide photographic light-sensitive materials have been widely used so far, but the demand for such light-sensitive materials has become increasingly severe. Under such circumstances, in recent years, sales competition of photographic light-sensitive materials has intensified, and silver halide photographic light-sensitive materials are required to have higher functions that are differentiated from conventional functions. In order to meet such a demand, researches for improving the resolution, brightness, image light fastness, and the like of photographic photosensitive materials have been actively conducted.
[0003]
Conventionally, in a silver halide photographic light-sensitive material, a layer containing inorganic particles such as titanium oxide, aluminum oxide, zinc oxide, calcium carbonate, calcium sulfate as a pigment substance or a light reflecting substance is used as an undercoat layer or an intermediate layer. Although it is used as a layer or an overcoat layer, it has not been possible to obtain all of the quality requirements such as sharpness (resolution), brightness (brightness), image with depth, and light resistance of the image at the same time.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a silver halide photographic light-sensitive material having improved sharpness (resolution) and brightness (brightness), thereby enabling formation of an image having a sense of depth, and improved light resistance.
[0005]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors have searched for a novel pigment substance or light-reflective substance that can be used in a silver halide photographic light-sensitive material, and as a result of earnestly examining its application to the photographic light-sensitive material, The invention has been completed.
[0006]
That is, the present invention is as follows.
<1> When at least one photosensitive silver halide emulsion layer is provided on a support, a resin-coated paper having a resin layer is used as the support, and the support and the photosensitive silver halide emulsion layer are A silver halide photographic light-sensitive material characterized in that a layer containing at least a water-soluble polymer and ultrafine titanium dioxide is disposed therebetween.
<2> The resin layer of the support includes a polyolefin resin. The silver halide photographic light-sensitive material according to <1>.
<3> The above-mentioned water-soluble polymer is gelatin or modified gelatin <1> or The silver halide photographic light-sensitive material as described in <2>.
<4> The average particle size of the ultrafine titanium dioxide is 0.01 μm or less. <1> ~ <3> The silver halide photographic light-sensitive material according to any one of <3>.
<5> The content of the ultrafine titanium dioxide is 5 to 95% by mass with respect to the layer containing the ultrafine titanium dioxide. <1> ~ <4> The silver halide photographic light-sensitive material according to any one of <4>.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In the silver halide photographic light-sensitive material of the present invention, at least one light-sensitive silver halide emulsion layer is provided on a support, and a resin-coated paper having a resin layer is used as the support. A layer containing at least a water-soluble polymer and ultrafine titanium dioxide is disposed between the silver halide emulsion layers.
Hereinafter, the resin-coated paper, water-soluble polymer, ultrafine titanium dioxide, photosensitive silver halide emulsion layer, and the like will be described in detail in order.
[0008]
(Resin coated paper)
In the present invention, a resin-coated paper having a resin layer is used as the support.
As a paper base material used for resin-coated paper, natural pulp paper composed mainly of normal natural pulp, mixed paper composed of natural pulp and synthetic fiber, synthetic fiber paper composed mainly of synthetic fiber, polystyrene, Any of so-called synthetic papers obtained by pseudo-making a synthetic resin film such as polyethylene terephthalate or polypropylene may be used, but natural pulp paper (hereinafter simply referred to as “base paper”) is particularly preferably used. The base paper may be neutral paper (pH 5-9) or acidic paper, but neutral paper is preferred.
[0009]
Base paper includes fillers such as alkyl ketene dimer, clay, talc, calcium carbonate, urea resin fine particles, sizing agents such as rosin, higher fatty acid salts, paraffin wax, alkenyl succinic acid, paper strength enhancers such as polyacrylamide, sulfuric acid A fixing agent such as a band can be added. In addition, dyes, pigments, slime control agents, antifoaming agents, etc. are added as necessary. Moreover, a softening agent can be added as needed. With regard to the softening agent, for example, “New Paper Processing Handbook” (edited by Paper Medicine Time), pages 554 to 555 (issued in 1980), particularly those having a molecular weight of 200 or more are preferable. This softening agent is an amine salt or a quaternary ammonium salt having a hydrophobic group having 10 or more carbon atoms and self-fixing with cellulose. Specific examples of the softening agent include a reaction product of a maleic anhydride copolymer and a polyalkylene polyamine, a reaction product of a higher fatty acid and a polyalkylene polyamine, a reaction product of a urethane alcohol and an alkylating agent, Although the quaternary ammonium salt of a fatty acid etc. are mentioned, the reaction product of a maleic anhydride copolymer and a polyalkylene polyamine and the reaction product of urethane alcohol and an alkylating agent are particularly preferable.
[0010]
The base paper is a pulp slurry containing additives such as the above-mentioned pulp and, if necessary, fillers, sizing agents, paper strength reinforcing agents, fixing agents, etc. And is wound up and manufactured. Surface sizing can be performed either before or after this drying. For the surface sizing treatment, a film-forming polymer such as gelatin, starch, carboxymethylcellulose, polyacrylamide, polyvinyl alcohol, or a modified product of polyvinyl alcohol is used. Examples of modified polyvinyl alcohol include carboxyl group-modified products, silanol-modified products, and copolymers with acrylamide. The coating amount of the film-forming polymer is usually 0.1 to 5.0 g / m. ² , Preferably 0.5 to 2.0 g / m ² Adjusted to Furthermore, an antistatic agent, a fluorescent brightening agent, a pigment, an antifoaming agent, and the like can be added to the film-forming polymer as necessary.
[0011]
A calendar process can be performed during winding after drying. When the surface treatment is performed after drying, the calender treatment can be carried out before or after the surface treatment, but it is preferable to carry out the calender treatment in the final finishing step after performing various treatments. As the metal roll and the elastic roll used for the calendering process, known ones used for the production of ordinary paper are used. The base paper is finally adjusted to a film thickness of 50 to 250 μm by the calendar process described above. The density (unit mass) of the base paper is usually 0.8 to 1.3 g / m. ² , Preferably 1.0 to 1.2 g / m ² It is.
[0012]
In the present invention, a resin layer is provided on at least one surface of the paper base. Applying a treatment to activate the substrate surface, such as corona discharge treatment, flame treatment, glow discharge treatment, plasma treatment, etc. to the paper substrate before coating the resin on the paper substrate has good adhesion on the surface It is preferable to obtain
[0013]
Polyolefin is preferable as the resin constituting the coating resin layer of the paper substrate, but an electron beam cured product of an unsaturated organic compound that can be cured by electron beam irradiation is also effective. The resin layer may be a single layer or a multilayer. Moreover, in the case of a multilayer, lamination | stacking of a polyolefin layer, lamination | stacking of an electron beam cured material layer, lamination | stacking of a polyolefin layer and an electron beam cured material layer, etc. can be used.
[0014]
Among the above polyolefins, polyethylene is particularly preferable, but polyester is also effective. As the polyester, polyester of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), polyester of NDCA, terephthalic acid and EG, polyethylene terephthalate, and the like are preferable.
[0015]
Examples of unsaturated organic compounds that can be cured by an electron beam include (1) aliphatic, alicyclic, and aromatic acrylate compounds of 1 to 6-valent alcohols and polyalkylene glycols, and (2) aliphatics and fats. Cyclic and aromatic acrylate compounds obtained by adding alkylene oxide to 1 to 6 valent alcohols, (3) polyacryloylalkyl phosphate esters, (4) reaction products of carboxylic acid, polyol and acrylic acid (5) reaction product of isocyanate, polyol and acrylic acid, (6) reaction product of epoxy compound and acrylic acid, (7) reaction product of epoxy compound, polyol and acrylic acid, etc. .
[0016]
Specifically, polyoxyethylene epichlorohydrin modified bisphenol A diacrylate, dicyclohexyl acrylate, epichlorohydrin modified polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, hydroxybivalate ester neopentyl glycol diacrylate, nonylphenoxy polyethylene glycol acrylate , Ethylene oxide modified phenoxylated phosphate acrylate, ethylene oxide modified phthalate acrylate, polybutadiene acrylate, caprolactam modified tetrahydrofurfuryl acrylate, tris (acryloxyethyl) isocyanurate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetra Ak Rate, dipentaerythritol hexaacrylate, polyethylene glycol diacrylate, 1,4-butadiene diol diacrylate, neopentyl glycol Gia
For example, acrylate, neopentyl glycol-modified trimethylolpropane diacrylate, and the like can be used. In the present invention, these compounds can be used alone or in combination of two or more thereof.
[0017]
(Water-soluble polymer and gelatin)
In the silver halide photographic light-sensitive material of the present invention, a layer containing at least a water-soluble polymer and ultrafine titanium dioxide is disposed between the support and a photosensitive silver halide emulsion layer described later.
[0018]
As the water-soluble polymer, all known polymers used for silver halide photographic materials can be used. Examples of the water-soluble polymer include gelatin and modified gelatin, starch, polyvinyl pyrrolidone, polyvinyl alcohol and derivatives thereof, acrylic resin, styrene-maleic anhydride copolymer, styrene-acrylic acid copolymer and the like. Of these, gelatin and modified gelatin are particularly preferable from the viewpoint of obtaining strong adhesiveness because the binders commonly used in the light-sensitive material layer are usually gelatin and modified gelatin.
[0019]
Examples of gelatin used in the present invention include phthalated gelatin and lime-processed gelatin. Further, gelatin having a PAGI viscosity of 10 to 30 mP and a PAGI jelly strength of 15 to 70 g can also be suitably used. When the viscosity of the PAGI method is less than 10 mP, the viscosity of the coating solution is too low, and precipitation of ultrafine titanium dioxide and other inorganic pigments in the coating solution may easily occur, whereas the PAGI method may cause poor dispersion. If the viscosity of the coating liquid is larger than 30 mP, the viscosity of the coating liquid is too high, and it becomes easy to cause problems and failures in the coating operation. Moreover, when the jelly strength of the PAGI method is less than 15 g, the coating strength is insufficient and the adhesive strength with the support may be reduced. On the other hand, when the jelly strength of the PAGI method is more than 70 g, The curl tends to become larger due to environmental changes.
[0020]
Here, the viscosity of the PAGI method and the jelly strength of the PAGI method are measured based on the test described in “Pagii Method: Photographic Gelatin Test Method” 7th edition (1992 edition) issued by the Joint Review Board for Photographic Gelatin Test Methods. it can. Gelatin satisfying the above physical properties can be obtained by reducing the molecular weight of a known gelatin (ordinary gelatin) produced by an ordinary method. “Normal gelatin” as used herein refers to, for example, cow bone, cow skin, pork skin, etc., as described in “Niwa and gelatin” (edited by Yoshihiro Abiko, published by Nippon Niwa & Gelatin Industries Association, 1987). It is manufactured by treating raw materials with lime, acid, etc., and has a much larger viscosity and jelly strength than the above (low molecular weight) gelatin.
[0021]
Ordinary gelatin is characterized by conditions such as raw materials, processing method (for example, lime treatment or acid treatment) and extraction conditions (temperature and number of extractions). Any gelatin may be used to lower the molecular weight, but those having a low extraction temperature and a small number of extraction are preferred because both low viscosity and jelly strength can be achieved. As a method for reducing the molecular weight of gelatin, there is a method using an enzyme or heat, among which a method using an enzyme is preferable. For example, papain is preferable as the enzyme. Lowering the molecule by heat is disadvantageous because the jelly strength is lowered when the viscosity is lowered to a preferred value.
[0022]
The gelatin reduced in molecular weight may be cross-linked using a hardener as necessary. As the hardener, a known hardener used as a hardener for gelatin can be used. Specific examples of these include vinyl sulfone compounds, active halogen compounds, isocyanate compounds, epoxy compounds and the like, among which epoxy compounds are particularly preferred. The following are mentioned as an epoxy compound suitable as a hardener.
[0023]
[Chemical 1]

[0024]
The coating amount of gelatin is 0.05 to 10 g / m ² Is desirable. Moreover, 1-90 mass% is preferable, and, as for the addition amount of the ultrafine particle titanium dioxide in gelatin, 30-70 mass% is more preferable. If the amount added is less than 1% by weight, the effect is small, and if it is more than 90% by weight, the dispersibility is insufficient.
[0025]
(Ultrafine titanium dioxide)
In the silver halide photographic light-sensitive material of the present invention, ultrafine titanium dioxide can be contained together with the water-soluble polymer as a binder. By providing this ultrafine titanium dioxide-containing layer, the silver halide photographic light-sensitive material of the present invention has improved sharpness (resolution) and brightness (brightness), can form an image with a sense of depth, and has light resistance. Improved.
[0026]
The ultrafine titanium dioxide is produced by hydrolyzing or vapor-phase oxidizing a titanium salt. Unlike the conventional pigment used as titanium white, the primary particle diameter is one digit or more. Small ultrafine particles, light scattering is suppressed, transparency is high, and ultraviolet absorbing ability is greatly improved. The ultrafine titanium dioxide may have any crystal structure of rutile type, brookite type, and anatase type, but the rutile type can be most preferably used.
[0027]
The average particle diameter of the ultrafine titanium dioxide used in the present invention is 0.02 μm or less, and 0.01 μm or less is preferable for further exhibiting the effect. Here, the average particle diameter means an area average particle diameter. The diameter of a circle is equivalent to the diameter of a circle equivalent to the projected area of each particle, and the number average is taken. Further, the particle size distribution is a so-called monodispersion having a coefficient of variation (the standard deviation of the particle size distribution divided by the average particle size) of 20% or less, preferably 15% or less, more preferably 10% or less. Those are preferred.
[0028]
The content of the ultrafine titanium dioxide contained in the ultrafine titanium dioxide-containing layer is preferably 5 to 95% by mass, more preferably 10 to 90% by mass with respect to the content layer. It is especially preferable to set it as 85 mass%. When the content of ultrafine titanium dioxide is set within the range of 5 to 95% by mass, more favorable results can be obtained in sharpness (resolution), brightness (brightness), and light resistance of the recording material of the present invention.
[0029]
The ultrafine titanium dioxide that can be used in the present invention may be surface-treated with an inorganic compound or an organic compound in order to improve dispersibility and workability. Specific examples of the surface treatment are disclosed in JP-A Nos. 52-35625, 55-10865, 57-35855, 62-25553, 62-103635, and Japanese Patent Application No. 7-200099. You can use what you have. The preferred surface treatment is preferably an inorganic compound such as aluminum oxide hydrate, hydrous zinc oxide or silicon dioxide, or an organic compound such as a divalent to tetravalent alcohol, trimethylolamine, titanate coupling agent or silane coupling agent. It is done. The amount of each surface treatment agent can be selected according to the purpose, but in the case of an inorganic surface treatment agent, a range of about 3 weight percent or less with respect to ultrafine titanium dioxide is generally used, and 0.01 to 1 A weight percent range is preferred. In the case of organic compounds, a range of about 5 weight percent or less is common, and a range of 0.1 to 3 weight percent is preferred.
[0030]
Further, in the present invention, within the range not impairing the effects of the invention, in addition to the above ultrafine titanium dioxide, a light reflecting substance or pigment substance such as ordinary titanium dioxide, aluminum oxide, zinc oxide, calcium carbonate, calcium sulfate, etc. It may be contained or dispersed. Since ultrafine titanium dioxide is a relatively expensive material due to its special manufacturing method, it is economically advantageous to use a pigment having another normal particle size in combination as long as the desired quality can be ensured. However, when used in combination, the amount of ultrafine titanium dioxide used is 30% by mass or more, preferably 50% by mass or more of the total pigment.
[0031]
(Photosensitive silver halide emulsion layer)
In the silver halide photographic light-sensitive material of the present invention, a light-sensitive silver halide emulsion layer is formed on a layer containing a water-soluble polymer and ultrafine titanium dioxide as a support. For the formation of the photosensitive silver halide emulsion layer and the non-photosensitive layer, it is preferable to use a hydrophilic colloid, specifically gelatin, as a binder. Each layer contains a compound necessary for image formation, such as a silver halide emulsion, a color former emulsion and a color mixing inhibitor emulsion.
[0032]
In the silver halide photographic light-sensitive material of the present invention, preferably, at least one yellow color-forming silver halide emulsion layer, magenta color-forming silver halide emulsion layer, and cyan color-producing silver halide emulsion layer are coated on a support. Can be configured. In general color photographic paper, the color reproduction of the subtractive color method can be performed by including a color coupler that forms a dye having a complementary color relationship with the light to which the silver halide emulsion is sensitive. In general color photographic paper, the silver halide emulsion grains are spectrally sensitized with the blue-sensitive, green-sensitive, and red-sensitive spectral sensitizing dyes in the order of the color-developing layers described above, and on the support in the order described above. It can be configured by coating. However, a different order may be used. Further, the photosensitive layer and the color hue may not have the above correspondence, and at least one infrared-sensitive silver halide emulsion layer can be used.
[0033]
In the present invention, it is preferable to use silver chloride, silver chlorobromide, or silver chloroiodobromide grains in which 95 mol% or more is silver chloride. In particular, in the present invention, in order to speed up the development processing time, a silver chlorobromide or silver chloride substantially free of silver iodide can be preferably used. Here, “substantially free of silver iodide” means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. On the other hand, for the purpose of increasing the sensitivity to high illuminance, increasing the spectral sensitization sensitivity, or increasing the temporal stability of the light-sensitive material, as described in JP-A-3-84545, 0.01-3 mol is added to the emulsion surface. High silver chloride grains containing 1% silver iodide may be preferably used.
[0034]
The halogen composition of the emulsion may be different or the same between the grains, but when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. As for the halogen composition distribution inside the silver halide emulsion grains, the so-called uniform type grains having the same composition regardless of the portion of the silver halide grains, the core inside the silver halide grains and the shell surrounding them. (Shell) Particles having a so-called laminated structure with different halogen composition in [single layer or multiple layers] or a structure having a non-layered portion with different halogen composition inside or on the surface (in the case of the particle surface, the edge of the particle, Particles having a structure in which different composition portions are joined on corners or surfaces can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use one of the latter two rather than the particles having a uniform structure, which is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the structure as described above, even if the boundary portion of the different portion in the halogen composition is a clear boundary, a mixed crystal is formed due to a composition difference and is an unclear boundary. Alternatively, it may be positively given a continuous structural change.
[0035]
The high silver chloride emulsion used in the present invention preferably has a structure having a silver bromide localized phase in the inside and / or on the surface of silver halide grains in the form of a layer or non-layer as described above. The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, more preferably more than 20 mol%. The silver bromide content of the silver bromide localized phase is analyzed using an X-ray diffraction method (for example, described in “The Chemical Society of Japan; New Experimental Chemistry Course 6: Structural Analysis” Maruzen). can do. These localized phases can be inside the particle, on the edge, corner or surface of the particle surface. As one preferable example, one grown epitaxially at the corner of the particle can be cited. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, an almost pure silver chloride emulsion having a silver chloride content of 98 to 100 mol% is also preferably used.
[0036]
The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grains and the number average thereof) is 0.1 μ to 2 μ. Is preferred. The particle size distribution is a so-called monodispersed one having a coefficient of variation (the standard deviation of the particle size distribution divided by the average particle size) of 20% or less, preferably 15% or less, more preferably 10% or less. preferable. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion blended in the same layer, or to apply multiple layers. The shape of silver halide grains contained in photographic emulsions is irregular (Irregular) such as those having regular crystal shapes such as cubes, tetradecahedrons or octahedrons, spheres, plates, etc. ) Those having a crystal form or those having a composite form thereof can be used. Moreover, you may consist of what mixed the thing which has various crystal forms. In the present invention, among these, the particles having the above-mentioned regular crystal form should be contained in an amount of 50% or more, preferably 70% or more, more preferably 90% or more. In addition to these, emulsions in which tabular grains having an average aspect ratio (equivalent diameter / thickness in terms of circle) of 5 or more, preferably 8 or more, exceed 50% of the total grains as a projected area can also be preferably used. As the tabular grains, both tabular grains whose grain surfaces are (111) faces and tabular grains whose (100) faces are preferably used.
[0037]
The silver salt (smell) emulsion used in the present invention is described by P. Glafkides, Chimie et Phisique Photographique (Paul Montel, 1967), GFDuffin, Photographic Emulsion Chemistry (Focal Press, 1966), VLZelikman et al. It can be prepared using a method described in Making and Coating Photographic Emulsion (published by Focal Press, 1964). That is, any method such as an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof. It may be used. A method (so-called back mixing method) in which particles are formed in an atmosphere containing excess silver ions can also be used. As one type of the simultaneous mixing method, a method in which pAg in a liquid phase produced by silver halide is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.
[0038]
The localized phase of the silver halide grains or the substrate thereof preferably contains a different metal ion or complex ion thereof. Preferred metals are selected from metal ions or metal complexes belonging to Group VIII and Group IIb of the periodic table, lead ions, thallium ions, and the like. The effect of the constitution of the light-sensitive material of the present invention is more remarkable when a gold-sensitized high silver chloride emulsion is used.
In addition to being used in a printing system using a normal negative printer, the photosensitive material of the present invention comprises a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a solid state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal. It is preferably used for digital scanning exposure using monochromatic high-density light such as a combined second harmonic generation light source. In order to make the system compact and inexpensive, it is preferable to use a second harmonic generation light source (SHG) that combines a semiconductor laser, a semiconductor laser, or a solid-state laser and a nonlinear optical crystal. In particular, in order to design a compact, inexpensive, long-life and high-stability device, it is preferable to use a semiconductor laser, and it is desirable to use a semiconductor laser as at least one of the exposure light sources.
[0039]
When such a scanning exposure light source is used, the spectral sensitivity maximum of the photosensitive material of the present invention can be arbitrarily set depending on the wavelength of the scanning exposure light source used. In a solid state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the light-sensitive material can be given to the usual three regions of blue, green, and red. In order to use a semiconductor laser as a light source in order to make the device inexpensive, highly stable, and compact, it is preferable that at least two layers have a spectral sensitivity maximum of 670 nm or more. This is because the cheap and stable III-V group semiconductor lasers that can be obtained are presently only in the red to infrared region. However, at the laboratory level, the oscillation of II-VI group semiconductor lasers in the green and blue regions has been confirmed, and if semiconductor laser manufacturing technology is developed, these semiconductor lasers can be used stably at low cost. It is fully expected. In such a case, the necessity that at least two layers have a spectral sensitivity maximum at 670 nm or more is reduced.
[0040]
Examples of cyan couplers include diphenylimidazole cyan couplers described in JP-A-2-33144, 3-hydroxypyridine cyan couplers described in EP 0333185A2, and JP-A 64-32260. Cyclic active methylene-based cyan coupler, pyrrolopyrazole type cyan coupler described in European Patent EP 0456226A1, pyrroloimidazole type cyan coupler described in European Patent EP 0484909, pyrrolo described in European Patent EP 0488248 and EP 0491197A1 The use of a triazole type cyan coupler is preferred. Of these, the use of a pyrrolotriazole type cyan coupler is particularly preferred.
[0041]
As the magenta coupler used in the present invention, a 5-pyrazolone-based magenta coupler or a pyrazoloazole-based magenta coupler is used, and among them, described in JP-A-61-65245 in terms of hue, image stability, color developability and the like. A pyrazolotriazole coupler in which the secondary or tertiary alkyl group is directly linked to the 2, 3 or 6 position of the pyrazolotriazole ring, and contains a sulfonamide group in the molecule described in JP-A-61-65246 Pyrazoloazole couplers, pyrazoloazole couplers having alkoxyphenylsulfonamide ballast groups described in JP-A-61-147254, and European Patent Nos. 226,849A and 294,785A Pyrazoloazole couplers with an alkoxy group or aryloxy group at the 6-position are preferred .
[0042]
Examples of yellow couplers include acylacetamide type yellow couplers having a 3- to 5-membered cyclic structure in the acyl group described in EP 0447969A1, and malondianilides having a cyclic structure described in EP 0482552A1. Type yellow couplers, acylacetamide type yellow couplers having a dioxane structure described in US Pat. No. 5,118,599 are preferably used. Among them, the use of an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilides constitutes an indoline ring is particularly preferred. These couplers can be used alone or in combination.
[0043]
In addition to the above, the silver halide emulsion and other materials (additives, etc.) and photographic composition layers (layer arrangement, etc.) applied to the silver halide photographic light-sensitive material of the present invention are shown in the following Tables 1 to 4. Those described in patent gazettes, particularly European Patent EP 0,355,660A2 (Japanese Patent Laid-Open No. 2-139544) are preferably used.
[0044]
[Table 1]

[0045]
[Table 2]

[0046]
[Table 3]

[0047]
[Table 4]

[0048]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by mass” and “mass%”, respectively, unless otherwise specified.
[0049]
[Example 1]
(Preparation of support)
Wood pulp consisting of 100 parts of LBKP was beaten to 300 ml Canadian freeness with a double disc refiner, 0.5 parts of epoxidized behenamide, 1.0 part of anionic polyacrylamide, 0.1 part of polyamide polyamine epichlorohydrin, and 0. 5 parts are added at an absolute dry weight ratio to pulp, and weighed 150 g / m with a long net paper machine. ² Paper made of 1.0 g / m ² The surface was sized with an absolutely dry weight of polyvinyl alcohol and adjusted to a density of 1.0 by calendering.
[0050]
After the corona discharge treatment was performed on the wire surface (back surface) of the base paper, high-density polyethylene was coated with a melt extruder so as to have a resin thickness of 35 μm to form a back surface resin layer composed of a mat surface.
[0051]
In addition, after the corona discharge treatment is performed on the felt surface (front surface) side of the base paper, low density polyethylene containing 10 parts of anatase type titanium oxide and a small amount of ultramarine blue is heat melt extruded so that the resin thickness becomes 30 μm. Coating was performed to form a surface resin layer having a glossy surface.
(Application of undercoat layer)
60 parts of water was added to 40 parts of enzyme-degraded gelatin (average molecular weight 10,000, PAGI method viscosity 15 mP, PAGI method jelly strength 20 g), and stirred at a temperature of 40 ° C. to dissolve the gelatin. To 10 parts of the above 40% gelatin aqueous solution, 200 parts of an ultrafine titanium dioxide 20% dispersion (“ELCOM-P” manufactured by Catalyst Kasei Kogyo Co., Ltd., average particle diameter: 0.008 μm) is mixed and stirred to prepare an undercoat liquid. did. Further, before coating, 1 part of the following epoxy gelatin hardener was added to the undercoat liquid.
[0052]
[Chemical formula 2]

[0053]
After the surface resin layer of the support is subjected to corona discharge treatment, the undercoat liquid is dried and the coating amount is 2.0 g / m. ² It applied so that it might become.
[0054]
(Formation of photographic composition layer)
On the undercoat layer, a photographic constituent layer was formed in the same manner as the photosensitive materials 101A to 101G of Example 1 of JP-A-9-204001 to prepare a silver halide photographic photosensitive material according to Example 1.
[0055]
[Example 2]
In the application of the undercoat layer of Example 1, instead of mixing 200 parts of an ultrafine titanium dioxide 20% dispersion (“ELCOM-P” manufactured by Catalytic Chemical Industry Co., Ltd.) with 10 parts of a 40% aqueous solution of enzyme-decomposed gelatin, enzyme-decomposed gelatin Silver halide according to Example 2 in the same manner as in Example 1 except that 20 parts of an ultrafine titanium dioxide 20% dispersion (“ELCOM-P” manufactured by Catalytic Chemical Industry) was mixed with 10 parts of a 40% aqueous solution. A photographic material was prepared.
[0056]
[Example 3]
In the application of the undercoat layer of Example 1, instead of mixing 200 parts of an ultrafine titanium dioxide 20% dispersion (“ELCOM-P” manufactured by Catalytic Chemical Industry Co., Ltd.) with 10 parts of a 40% aqueous solution of enzyme-decomposed gelatin, enzyme-decomposed gelatin A silver halide according to Example 3 in the same manner as in Example 1 except that 10 parts of 40% aqueous solution was mixed with 5 parts of an ultrafine titanium dioxide 20% dispersion (“ELCOM-P” manufactured by Catalytic Chemical Industry). A photographic material was prepared.
[0057]
[Comparative Example 1]
Instead of mixing 5 parts of an ultrafine titanium dioxide 20% dispersion (“ELCOM-P” manufactured by Catalytic Kasei Kogyo Co., Ltd.) with 10 parts of 40% aqueous solution of enzyme-decomposed gelatin in the application of the undercoat layer of Example 3, enzyme-decomposed gelatin Comparative Example 1 was carried out in the same manner as in Example 1 except that 10 parts of 40% aqueous solution was mixed with 0.8 parts of titanium dioxide (“Typaque A-220” manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.16 μm). A silver halide photographic light-sensitive material was prepared.
[0058]
[Comparative Example 2]
Comparative Example as in Example 1 except that in the application of the undercoat layer of Example 1, 200 parts of an ultrafine titanium dioxide 20% dispersion (“ELCOM-P” manufactured by Catalyst Kasei Kogyo Co., Ltd.) was not mixed. A silver halide photographic light-sensitive material according to 2 was prepared.
[0059]
The following evaluation tests were conducted on these silver halide photographic light-sensitive materials.
(1) Sharpness (CTF)
A resolution chart was adhered to the silver halide photographic light-sensitive material, exposed with green light, and processed for color images. The density of the image portion and the background portion of this processed silver halide photographic light-sensitive material is measured with a microdensitometer, and calculated with a personal computer in accordance with a conventional method to calculate the CTF (Contrast Transfer Function: 10) of the magenta layer. Value in mm / mm), and this was defined as the sharpness of the image. CTF indicates that the larger the value, the higher the sharpness of the image.
[0060]
(2) Glossy
The obtained silver halide photographic light-sensitive material was exposed from a color negative film, baked, and subjected to color development to obtain a color print. By visual comparison of the printed images, the glossy images were evaluated as ◎, ○, Δ, and × in order.
[0061]
(3) Image light resistance
A strips chart with magenta, yellow, and cyan density gradations was baked on the silver halide photographic light-sensitive material, and color development processing was performed to obtain density gradation strip sprints. This print was printed with a weatherometer CI65 (manufactured by Atlas Electric Device co.) At 0.9 W / m. ² For 4 weeks. The reflection density of the magenta component before the irradiation treatment is measured in advance, the reflection density after the irradiation test is measured in the vicinity of the reflection density of about 1.0, and the image light resistance is determined from the reflection density by a conventional method. Expressed as a percentage. The higher this number, the better the image light resistance.
The above evaluation results are shown in Table 5 below.
[0062]
[Table 5]

[0063]
It was found that the silver halide photographic light-sensitive materials of the examples had higher sharpness, glossiness and excellent image light resistance than the light-sensitive materials of the comparative examples. In particular, when photographs such as weddings and portraits were visually evaluated as color prints of comparative examples, glossy and gorgeous images were obtained.
[0064]
【The invention's effect】
The silver halide photographic light-sensitive material of the present invention improves sharpness and glossiness by using ultrafine titanium dioxide, thereby enabling the formation of a clear image with a sense of depth and improving the light resistance of the image. Can also be improved.

Claims (5)

In a silver halide photographic light-sensitive material in which at least one photosensitive silver halide emulsion layer is provided on a support, a resin-coated paper having a resin layer is used as the support, and the support and the photosensitive silver halide emulsion are used. A silver halide photographic light-sensitive material, wherein a layer containing at least a water-soluble polymer and ultrafine titanium dioxide is disposed between the layers. The silver halide photographic light-sensitive material according to claim 1, wherein the resin layer of the support contains a polyolefin resin. The silver halide photographic light-sensitive material according to claim 1 or 2, wherein the water-soluble polymer is gelatin or modified gelatin. The silver halide photographic light-sensitive material according to claim 1, wherein the ultrafine particle titanium dioxide has an average particle diameter of 0.01 μm or less. 5. The silver halide photographic light-sensitive material according to claim 1, wherein a content of the ultrafine titanium dioxide is 5 to 95% by mass with respect to a layer containing the ultrafine titanium dioxide.