JP3678907B2 - Support for photosensitive material - Google Patents

Description

【００７５】
数式１において、Ｗｘは試料面域のＸ軸方向(抄紙方向)の長さを表わし、Ｗｙは試料面域のＹ軸方向(抄紙方向と垂直な方向)の長さを表わし、Ｓａは試料面域の面積を表す。
【００７６】
本発明の実施に好ましく用いられる、中心面平均粗さＳＲａが１.４５μm以下の基紙を製造する方法としては、具体的には、平滑性の出やすい広葉樹パルプ、好ましくは広葉樹サルファイトパルプを１５重量%以上、好ましくは３０重量%以上用い、湿紙の乾燥途中で多段の緊度プレスを行い、更に基紙を抄造後マシンカレンダー、スーパーカレンダー、熱カレンダー等を用いて少なくとも２系列以上のカレンダー処理、例えば基紙に第１系列のカレンダー処理としてマシンカレンダー処理あるいは／及び熱マシンカレンダー処理を行い、その後第２系列以降のカレンダー処理として必要に応じて更にマシンカレンダー処理を行った後特開平4-110939号公報に記載もしくは例示の熱ソフトカレンダー処理を行って、中心面平均粗さＳＲａが１.４５μm以下の基紙を製造することが出来る。また、基紙中あるいは基紙上に各種の水溶性ポリマーもしくは親水性コロイドあるいはポリマーラテックスをサイズプレスもしくはタブサイズプレスあるいはブレード塗工、エアーナイフ塗工などの塗工によって固形塗布量として１.０g/m²以上、特に２.２g/m²以上含有あるいは塗設せしめるのが好ましい。
【００７７】
本発明における感光材料用支持体の基紙の密度としては、０.９０g/cm³〜１.１５g/cm³の範囲が好ましく、０.９５g/cm³〜１.１５g/cm³の範囲が一層好ましく、１.００g/cm³〜１.１０g/cm³の範囲が特に好ましい。基紙の密度が０.９０g/cm³未満であると面質の良い平滑性に優れた感光材料用支持体が得られないし、基紙の密度が１.１５g/cm³より大きいと感光材料及びそのプリントの腰が弱くなって問題である。また、本発明の実施に用いられる基紙の厚味に関しては、特に期限はないが、その坪量は４０g/m²〜２５０g/m²のものが有用であり、７０g/m²〜２２０g/m²のものが好ましい。
【００７８】
本発明における感光材料用支持体は、各種のハロゲン化銀感光構成層が塗設されてカラー写真印画紙用、白黒写真印画紙用、写植印画紙用、複写印画紙用、反転写真材料用、銀塩拡散転写法ネガ用及びポジ用、印刷材料用等各種の用途に用いることができる。例えば、塩化銀、臭化銀、塩臭化銀、沃臭化銀、塩沃臭化銀乳剤層を設けることができる。ハロゲン化銀写真乳剤層にカラーカプラーを含有せしめて、多層ハロゲン化銀カラー写真構成層を設けることができる。また、銀塩拡散転写法用写真構成層を設けることができる。それらのハロゲン化銀感光構成層の結合剤としては、通常のゼラチンの他に、ポリビニルピロリドン、ポリビニルアルコール、多糖類の硫酸エステル化合物などの親水性高分子物質を用いることができる。また、上記のハロゲン化銀感光構成層には各種の添加剤を含有せしめることができる。例えば、増感色素として、シアニン色素、メロシアニン色素など、化学増感剤として、水溶性金化合物、イオウ化合物など、カブリ防止剤もしくは安定剤として、ヒドロキシートリアゾロピリミジン化合物、メルカプト−複素環化合物など、硬膜剤としてホルマリン、ビニルスルフォン化合物、アジリジン化合物など、塗布助剤として、アルキルベンゼンスルフォン酸塩、スルホコハク酸エステル塩など、汚染防止剤として、ジアルキルハイドロキノン化合物など、そのほか蛍光増白剤、鮮鋭度向上色素、帯電防止剤、ｐＨ調製剤、カブらせ剤、更にハロゲン化銀の生成・分散時に水溶性イリジウム、水溶性ロジウム化合物などを適宜組み合わせて含有せしめることができる。
【００７９】
また、本発明の効果、特にハロゲン化銀感光材料の保存に伴うカブリの発生を顕著に抑制して保存性を顕著に改良出来る効果は、ハロゲン化銀感光層として、ハロゲン化銀が塩化銀主体であるハロゲン化銀感光層、中でもハロゲン化銀の塩化銀含有率が９０モル%以上、特に９５モル%以上であるハロゲン化銀感光層を用いることにより、一層相乗的に、かつ一層顕著に達成される。更に、本発明の効果、特にハロゲン化銀感光材料の保存に伴うカブリの発生を顕著に抑制して保存性を顕著に改良出来る効果は、ハロゲン化銀感光構成層として、ハロゲン化銀カラー写真構成層、中でも青感ハロゲン化銀の塩化銀含有率が９０モル%以上、特に９５%モル以上である青感ハロゲン化銀写真乳剤層を含む多層ハロゲン化銀カラー写真構成層を用いることにより、なお一層相乗的に、かつなお一層顕著に達成される。
【００８０】
本発明における感光材料は、その感光材料に合わせて「写真感光材料と取扱法」(共立出版、宮本五郎著、写真技術講座２)に記載されている様な露光、現像、停止、定着、漂白、安定などの処理を行うことが出来る。また、多層ハロゲン化銀カラー写真材料は、ベンジルアルコール、タリウム塩、フェニドンなどの現像促進剤を含む現像液で処理してもよいし、ベンジルアルコールを実質的に含まない現像液で処理することもできる。
【００８１】
【実施例】
以下、実施例により本発明を詳しく説明するが、本発明の内容は実施例に限られるものではない。
【００８２】
実施例１〜１０及び比較例１〜３
広葉樹漂白クラフトパルプを叩解後のパルプの繊維長(ＪＡＰＡＮ ＴＡＰＰＩ紙パルプ試験方法No.５２−89「紙及びパルプ繊維長試験方法」に準拠して測定した長さ加重平均繊維長で表示して)が０.５６mmになるように叩解後、パルプ１００重量部に対して、カチオン化澱粉３重量部、アニオン化ポリアクリルアミド０.２重量部、アルキルケテンダイマー乳化物(ケテンダイマー分として)０.４重量部、ポリアミドエピクロルヒドリン樹脂０.４重量部、両性ポリアクリルアミド(分子量１００万)１.５重量部及び適当量の蛍光増白剤、青色染料、赤色染料を添加して紙料スラリーを調製した。その後、紙料スラリーを２００m/分で走行している長網抄紙機にのせ適切なタービュレンスを与えつつ紙匹を形成し、ウェットパートで１５〜１００kgf/cmの範囲で線圧が調節された３段のウェットプレスを行った後、スムージングロールで処理し、引き続く乾燥パートで３０〜７０kgf/cmの範囲で線圧が調節された２段の緊度プレスを行った後、乾燥した。その後、乾燥の途中で下記(配合Ａ)〜(配合Ｅ)のサイズプレス液を２５g/m²サイズプレスし、最終的に得られる基紙水分が絶乾水分率で８重量%になるように乾燥し、線圧７０kgf/cmでマシンカレンダー処理して、坪量が１７０g/m²、密度が１.０４g/cm³、中心面平均粗さＳＲａが１.２０μmである感光材料用支持体の基紙を製造した。
【００８３】
サイズプレス液(配合Ａ)：カルボキシ変性ポリビニルアルコール(日本合成化学株式会社製、商品名；ゴーセナールＴ−３３０、以下ＰＶＡ−１と略す)４重量%、蛍光増白剤０.０５重量%、着色染料０.００２重量%、塩化ナトリウム４重量%及び残重量%の水から成るサイズプレス液。
【００８４】
サイズプレス液(配合Ｂ)：カルボキシ変性ポリビニルアルコール(ＰＶＡ−１)３重量%、カルボキシ変性ポリビニルアルコール(クラレ株式会社製、商品名；クラレＫＬ５０６、以下ＰＶＡ−２と略す)２重量%、蛍光増白剤０.０５重量%、着色染料０.００２重量%、塩化ナトリウム４重量%及び残重量%の水から成るサイズプレス液。
【００８５】
サイズプレス液(配合Ｃ)：カルボキシ変性ポリビニルアルコール(ＰＶＡ−１)２重量%、カルボキシ変性ポリビニルアルコール(ＰＶＡ−２)４重量%、蛍光増白剤０.０５重量%、着色染料０.００２重量%、塩化ナトリウム４重量%及び残重量%の水から成るサイズプレス液。
【００８６】
サイズプレス液(配合Ｄ)：カルボキシ変性ポリビニルアルコール(ＰＶＡ−１)１重量%、カルボキシ変性ポリビニルアルコール(ＰＶＡ−２)７重量%、蛍光増白剤０.０５重量%、着色染料０.００２重量%、塩化ナトリウム４重量%及び残重量%の水から成るサイズプレス液。
【００８７】
サイズプレス液(配合Ｅ)：カルボキシ変性ポリビニルアルコール(ＰＶＡ−２)１０重量%、蛍光増白剤０.０５重量%、着色染料０.００２重量%、塩化ナトリウム４重量%及び残重量%の水から成るサイズプレス液。
【００８８】
次に、ハロゲン化銀感光構成層を塗設する側とは反対側の基紙面(裏面)をコロナ放電処理した後、該裏面に低密度ポリエチレン樹脂[密度０.９２４g/cm³、ＭＦＲと＝１g/10分]３０重量部と高密度ポリエチレン樹脂(密度０.９６７g/cm³、ＭＦＲ＝１５g/10分)７０重量部から成るコンパウンド樹脂組成物を樹脂温度３２０℃で２５μmの樹脂厚さに基紙の走行速度２００m/分で、溶融押し出し塗布機を用いて、冷却ロールとプレスロールの線圧４０kgf/cmで溶融押し出しコーティングした。この際、冷却ロールとしては、液体ホーニング法で粗面化された冷却ロールを用い、冷却水温度１２℃で操業した。引き続き、下記のようにして表樹脂層を被覆して、樹脂被覆紙を製造した。
【００８９】
ハロゲン化銀感光構成層を設ける側の基紙面(表面)をコロナ放電処理した後、該表面に下記の配合組成物(ＢＬ−１)を樹脂温度３１５℃で３０μmの厚さに基紙の走行速度２００m/分で、溶融押し出し塗布機を用いて、冷却ロールとプレスロールの線圧４０kgf/cmで溶融押し出しコーティングした。この際、冷却ロールとしては、クロムメッキが施された微粗面のものを用い、冷却水温度１２℃で操業した。また、表、裏の樹脂組成物の溶融押し出しコーティングは、逐次押し出しコーティングが行われる、いわゆるタンデム方式で行われた。
【００９０】
配合組成物(ＢＬ−１)：二酸化チタン顔料を含む下記マスターバッチ(ＭＢ−１Ｗ)のペレット１７重量部と二酸化チタン顔料及び群青を含む下記マスターバッチ(ＭＢ−１Ｂ)のペレット８重量部と下記ポリエチレン樹脂(Ｒ−２)のペレット７５重量部をよく単純混合(ドライブレンド)した配合組成物。
【００９１】
マスターバッチ(ＭＢ−１Ｗ)：二酸化チタン粒子表面が含水酸化アルミニウム(二酸化チタン当たりＡｌ₂Ｏ₃分として０.５重量%)で表面処理され、スチームミル粉砕された、電子顕微鏡による個数平均径で０.１２０μmのアナターゼ型二酸化チタン顔料５０重量%、下記ポリエチレン樹脂(Ｒ−１)４７.５重量%及びステアリン酸亜鉛２.５重量%とを、酸化防止剤として２００ppmの１、３、５−トリス(４−tert−ブチル−３−ヒドロキシ−２、６−ジメチル−ベンジル)シアヌレート(以下、ＡＯ−１と略す)及び２００ppmのトリス(２，４−ジ−tert−ブチルフェニル)フォスファイト(以下、ＡＯ−２と略す)の存在下に、バンバリーミキサーを用いて１５０℃でよく混練し、冷却、ペレット化して製造したマスターバッチ。
【００９２】
マスターバッチ(ＭＢ−１Ｂ)：上記二酸化チタン顔料５０重量%、下記ポリエチレン樹脂(Ｒ−１)４６.２５重量%、群青(第一化成工業株式会社製、＃２０００)１.２５重量%及びステアリン配合亜鉛２.５重量%とを、酸化防止剤(ＡＯ−１)２００ppm及び酸化防止剤(ＡＯ−２)２００ppmの存在下に、バンバリーミキサーを用いて１５０℃でよく混練し、冷却、ペレット化して製造したマスターバッチ。
【００９３】
ポリエチレン樹脂(Ｒ−１)：密度０.９２０g/cm³，ＭＦＲ＝８.５/10分，ヘキサン抽出量＝１.５重量%であるチューブラー法の高圧法低密度ポリエチレン樹脂。
【００９４】
ポリエチレン樹脂(Ｒ−２)：密度０.９２２g/cm³，ＭＦＲ＝４.０/10分，ヘキサン抽出量＝１.３重量%であるオートクレープ法の低密度ポリエチレン樹脂。
【００９５】
更に、表、裏樹脂層を加工後巻き取るまでの間に、樹脂被覆紙の裏樹脂層面にコロナ放電処理後、下記のバック層用塗液(ＢＣ−１)を乾燥重量分として０.３g/m²になる塗布量でオンマシン塗布した。
【００９６】
バック層用塗液(ＢＣ−１)；スチレン：２−エチルヘキシルアクリレート：メタクリル酸：アクリルアミド＝５７：３９：２.５：１.５(重量%)の組成である ポリマーラテックスの５０重量%水性分散液２gとコロイド状シリカ２０重量%液(日産化学株式会社製、商品名スノーテックス２０)３０gとスチレン−無水マレイン酸共重合体(荒川化学株式会社製、商品名ＫＳ−１５７０、分子量約７万、Ｐ Ｈ７.３の２５重量%水溶液)６gと平均粒径１μm、吸油度３５cc/100ｇの水酸化 アルミニウム微結晶を水中に乳化分散して調製した９重量%分散液１２gとエポキシ系硬膜剤(長瀬産業株式会社製、商品名ＮＥＲ−０１０)の１０%メタノール溶 液３.２g及び２−エチルヘキシルスルフォコハク酸エステル塩の５重量%水・メ タノール混溶液０.８gを含み、全量を水で１００gに調製した塗液。
【００９７】
バック層を塗設後、樹脂被覆紙を巻き取るまでの間に、表側の樹脂面に表１に記載のコロナ処理量でコロナ放電処理を施した後、下記の下引層用塗液(ＳＣ−１)をゼラチン塗布量分(乾燥重量分)として０.０６g/m²になる塗布量で均一にオンマシン塗布した。
【００９８】
下引層用塗液(ＳＣ−１)：石灰処理ゼラチン１.２g、低分子量ゼラチン(新田ゼラチン株式会社製、Ｐ−３２２６)０.３g、パラオキシ安息香酸ブチルの１０重量%メタノール溶液０.３g及びスルフォコハク酸−２−エチルヘキシルエステル塩のメタノールと水の５重量%混合液０.４５gを含み、全量を水で１００gに調製した塗液。
【００９９】
次いで、下引層面の表面電位がプラス０.３kVになる様にこれらの支持体に対 してワイヤー加電方式で加電処理を行った。更に、オンマシン方式で、感光材料用支持体の下引層上に隣接して順に下記の黄色発色カプラーを含む青感乳剤層、色混り防止剤を含む中間層、マゼンタ発色カプラーを含む緑感乳剤層、紫外線吸収剤を含む第一紫外線吸収層、シアン発色カプラーを含む赤感乳剤層、紫外線吸収剤を含む第二紫外線吸収層及び保護層用の各塗布液を塗布速度２００m/分で多層塗布用Ｅバーから７層同時塗布してゼラチンの総量が８.５g/m²であるカラー印画紙を作成した。なお、硬膜剤としては、２，４−ジクロロ−６−ヒドロキシ−ｓ−トリアジンナトリウム塩(水溶液として添加)を用い、ゼラチンの総量に対して、１.６５重量%になるように、ハロゲン化銀カラー印画紙の写真特性、保存性等を考慮して各層に適切に配分して含有させた。
【０１００】
青感乳剤層は、適量のヘキサクロロイリジウム(III)酸カリウムの存在下に平均粒子径１.１μmの単分散立方体ホスト塩化銀剤を熟成、調製し、更に該ホスト塩化銀に対して０.０５モル%の比率で０.０５μmの臭化銀微粒子乳剤を添加して第１熟成して製造した最適感度に硫黄増感した中性法積層型ハロゲン化銀乳剤を硝酸銀量で０.４g/m²含み、更にゼラチン１.５g/m²及びイエロー発色カプラーの他、適量の安定剤、青感用増感色素、塗布助剤、硬膜剤、増粘剤等を含む。中間層は、ゼラチン１.０g/m²の他に適量の色混り防止剤、塗布助剤、増粘剤、硬膜剤等を含む。青感乳剤層用と中間層用の塗布液の粘度は、それぞれ５.５cpと１００cpに調節され、湿潤塗布量が、それぞれ３５g/m²と５g/m²で塗設された。
【０１０１】
緑感乳剤層は、適量のヘキサクロロロジウム(III)酸カリウムの存在下に第１熱成して製造した平均粒子径０.４５μmの最適感度に硫黄増感した単分散立方体の塩化銀からなる酸性法ハロゲン化銀乳剤を硝酸銀量で０.５g/m²含み、更にゼラチン１.２g/m²及びマゼンタ発色カプラーの他、適量の安定剤、緑感用増感色素、鮮鋭度向上色素、塗布助剤、硬膜剤、増粘剤等を含む。第一紫外線吸収層は、ゼラチン１.３g/m²の他に適量の紫外線吸収剤、塗布助剤、増粘剤、硬膜剤等を含む。緑感乳剤層用と第一紫外線吸収層用の塗布液の粘度は、それぞれ５０cpと６０cpに調節され、湿潤塗布量が、それぞれ１５g/m²と７g/m²で塗設された。
【０１０２】
赤感乳剤層は、緑感ハロゲン化銀乳剤と全く同様にして製造したハロゲン化銀乳剤を硝酸銀量で０.３５g/m²で含み、更にゼラチン１.１g/m²及びシアン発色カプラーの他、適量の安定剤、赤感用増感色素、鮮鋭度向上色素、塗布助剤、硬膜剤、増粘剤等を含む。第二紫外線吸収層は、ゼラチン０.５g/m²の他に適量の紫外線吸収剤、塗布助剤、増粘剤、硬膜剤等を含む。保護層は、ゼラチン１.４g/m²の他に適量の塗布助剤、増粘剤、硬膜剤等を含む。赤感乳剤層用、第二紫外線吸収層用及び保護層用の塗布液の粘度は、それぞれ３０cp、６０cp及びと９０cpに調節され、湿潤塗布量がそれぞれ１４g/m²、７g/m²及び７g/m²で塗設された。
【０１０３】
以上のようにして製造したカラー印画紙の保存性及び乳剤膜付き評価方法としては、以下の記載の方法で評価した。
【０１０４】
カラー印画紙の保存性の評価方法としては、製造したカラー印画紙を６５℃，５日間ドライサーモした後、未露光のカラー印画紙を発色現像、漂白・定着、安定の発色現像処理をした後乾燥し、イエローカブリの濃度を測定して評価した。なお、発色現像処理は、発色現像(４５秒)→漂白・定着(４５秒)→安定(１分３０秒)→乾燥の手順で行われた。
【０１０５】
写真構成層の乳剤膜付きの評価方法としては、製造したカラー印画紙を４０℃、常温下に５日間保存後グレー濃度１.５以上になるように露光し、発色現像後乳剤膜付きを評価した。乳剤膜付きは、発色現像後釘にて縦横にそれぞれ１cm間隔で乳剤面を引掻き、碁盤目状の傷を付け、その後流水中で指先でその面を擦り、指先で擦った面積に対する乳剤層が剥離しなかった面積の割合(%)(数値が大きい程乳剤膜付きが強いこと、数値が小さい程乳剤膜付きが弱いことを表す)で評価した。評価基準としては以下の通りである。
１００%〜９７% ：乳剤層の剥離が全くあるいはほとんどなく、乳剤膜付きが良好。
９７%未満〜８０%：乳剤層の剥離がわずかあるが、実用上問題ない。
８０%未満〜６０%：乳剤層の剥離がやや多いが、実用上下限。
６０%未満：乳剤層の剥離が多く、乳剤膜付きが実用上問題がある。
【０１０６】
得られた結果を表１に示す。
【０１０７】
【表１】

【０１０８】
なお、表１中の(注１)〜(注４)は、以下の通りである。
【０１０９】
(注１)サイズプレス液の(配合Ａ)〜(配合Ｅ)は、感光材料用支持体の基紙を製造する際に用いた段落００８３〜段落００８７に記載のそれらと同じものを表す。
【０１１０】
(注２)コロナ処理量は、感光材料用支持体を製造する際に下引層を塗設する前の表樹脂層面に施した段落００９７に記載のコロナ放電処理のコロナ出力量(watt・分/m²)を表す。
【０１１１】
(注３)ポリエチレン表面酸化度もしくは支持体表面酸化度は、本明細書で規定されたポリエチレン表面酸化度(%)もしくは支持体表面酸化度(%)を表す。
【０１１２】
(注４)支持体の酸素透過度は、本明細書で規定された支持体の酸素透過度(cc/m²/day)を表す。
【０１１３】
表１の結果から、天然パルプを主成分とする基紙の表側がポリエチレン系樹脂(ａ)を含む樹脂層(Ａ)で被覆され、裏側がフィルム形成能ある樹脂(ｂ)を含む樹脂層(Ｂ)で被覆された感光材料用支持体であって、ポリエチレン表面酸化度が３３%〜５３%であり、かつ支持体の酸素透過度が４５０cc/m²/day以下である本発明における感光材料用支持体(実施例１〜１０)は、イエローカブリの発生が顕著に改良されてハロゲン化銀感光層に対する保存性が顕著に改良された、かつ乳剤膜付きが安定に顕著に改良された、優れた感光材料用支持体であることがよくわかる。
また、天然パルプを主成分とする基紙の表側がポリエチレン系樹脂(ａ)を含む樹脂層(Ａ)で被覆され、裏側がフィルム形成能ある樹脂(ｂ)を含む樹脂層(Ｂ)で被覆された感光材料用支持体の表側にハロゲン化銀感光構成層を塗設したハロゲン化銀感光材料であって、支持体表面酸化度が３３%〜５３%であり、かつ支持体の酸素透過度が４５０cc/m²/day以下である本発明におけるハロゲン化銀感光材料(実施例１〜１０)は、イエローカブリの発生が顕著に改良されて、ハロゲン化銀感光層の保存性が顕著に改良された、かつ乳剤膜付きが安定に顕著に改良された、優れた感光材料用支持体であることがよくわかる。
【０１１４】
また、本発明における感光材料支持体並びにハロゲン化銀感光材料の中でも、ハロゲン化銀感光層に対する保存性ないしはハロゲン化銀感光層の保存性及び乳剤膜付きの改良効果の点から、ポリエチレン表面酸化度もしくは支持体表面酸化度が、３５%〜５０%のものが好ましく、３７%〜４７%のもが特に好ましいことがよくわかる。
更に、本発明のおける感光材料用支持体並びにハロゲン化銀感光材料の中でも、ハロゲン化銀感光層に対する保存性ないしはハロゲン化銀感光層の保存性及び乳剤膜付きの改良効果の点から、支持体の酸素透過度が、４００cc/m²/day以下のものが好ましく、３５０cc/m²/day以下のものが更に好ましく、３００cc/m²/day以下のものが特に好ましいことがよくわかる。
【０１１５】
一方、ポリエチレン表面酸化度もしくは支持体表面酸化度が、３３%未満である場合(比較例１)や５３%より高い場合(比較例２)の本発明外の感光材料用支持体並びにハロゲン化銀感光材料は、乳剤膜付きが弱かったり、イエローカブリの発生が多くハロゲン化銀感光層に対する保存性ないしはハロゲン化銀感光層の保存性が悪くて問題であることがよくわかる。
また、支持体の酸素透過度が、４５０cc/m²/dayより多い場合(比較例３)の本発明外の感光材料用支持体並びにハロゲン化銀感光材料は、イエローカブリの発生が多くハロゲン化銀感光層に対する保存性ないしはハロゲン化銀感光層の保存性が悪くて問題であるし、乳剤膜付きが弱くなる傾向があることがよくわかる。
【０１１６】
実施例１１〜２５
実施例９において用いた、基紙の表側被覆用の配合組成物(ＢＬ−１)の代わりに、下記配合組成物(ＢＬ−２)〜(ＢＬ−１６)を用いる以外は、実施例９と同様に実施した。なお、製造したカラー印画紙の支持体の酸素透過度は、各々３５０cc/m²/dayであった。
【０１１７】
配合組成物(ＢＬ−２)：二酸化チタン顔料を含む下記マスターバッチ(ＭＢ−２Ｗ)のペレット１７重量部と二酸化チタン顔料及び群青を含む下記マスターバッチ（ＭＢ−２Ｂ）のペレット８重量部と下記ポリエチレン樹脂(Ｒ−２)のペレット７５重量部をよく単純混合(ドライブレンド)した配合組成物。
【０１１８】
マスターバッチ(ＭＢ−２Ｗ)：二酸化チタン粒子表面が含水酸化アルミニウム(二酸化チタン当たりＡｌ₂Ｏ₃分として０.５重量%)で表面処理され、スチームミル粉砕された、電子顕微鏡による個数平均径で０.１２０μmのアナターゼ型二酸化チタン顔料５０重量%、前記ポリエチレン樹脂(Ｒ−１)４７.５重量%及びステアリン酸亜鉛２.５重量%とを、酸化防止剤(ＡＯ−１)５０ppmの存在下に、バンバリーミキサーを用いて１５０℃でよく混練し、冷却、ペレット化して製造したマスターバッチ。
【０１１９】
マスターバッチ(ＭＢ−２Ｂ)：上記二酸化チタン顔料５０重量%、前記ポリエチレン樹脂(Ｒ−１)４６.２５重量%、群青(第一化成工業株式会社製、＃２０００)１.２５重量%及びステアリン配合亜鉛２.５重量%とを、酸化防止剤(ＡＯ−１)７５ppmの存在下に、バンバリーミキサーを用いて１５０℃でよく混練し、冷却、ペレット化して製造したマスターバッチ。
【０１２０】
ポリエチレン樹脂(Ｒ−２)：密度０.９２２g/cm³，ＭＦＲ＝４.０g/10分、ヘキサン抽出量＝１.３重量%であるオートクレーブ法の低密度ポリエチレン樹脂。
【０１２１】
配合組成物(ＢＬ−３)：配合組成物(ＢＬ−２)の調製に用いたポリエチレン樹脂(Ｒ−２)の代わりに、下記のポリエチレン樹脂(Ｒ−３)を用いる以外は配合組成物(ＢＬ−２)と全く同様にして調製した配合組成物。
【０１２２】
ポリエチレン樹脂(Ｒ−３)：樹脂被覆紙の表樹脂層中の含有量が、ポリエチレン樹脂に対して１０ppmになる量の酸化防止剤(ＡＯ−１)をポリエチレン樹脂(Ｒ−２)中に予め混合・混練して調製したポリエチレン樹脂。
【０１２３】
配合組成物(ＢＬ−４)：配合組成物(ＢＬ−２)の調製に用いたポリエチレン樹脂(Ｒ−２)の代わりに、下記のポリエチレン樹脂(Ｒ−４)を用いる以外は配合組成物(ＢＬ−２)と全く同様にして調製した配合組成物。
【０１２４】
ポリエチレン樹脂(Ｒ−４)：樹脂被覆紙の表樹脂層中の含有量が、ポリエチレン樹脂に対して２０ppmになる量の酸化防止剤(ＡＯ−１)をポリエチレン樹脂(Ｒ−２)中に予め混合・混練して調製したポリエチレン樹脂。
【０１２５】
配合組成物(ＢＬ−５)：配合組成物(ＢＬ−２)の調製に用いたポリエチレン樹脂(Ｒ−２)の代わりに、下記のポリエチレン樹脂(Ｒ−５)を用いる以外は配合組成物(ＢＬ−２)と全く同様にして調製した配合組成物。
【０１２６】
ポリエチレン樹脂(Ｒ−５)：樹脂被覆紙の表樹脂層中の含有量が、ポリエチレン樹脂に対して５０ppmになる量の酸化防止剤(ＡＯ−１)をポリエチレン樹脂(Ｒ−２)中に予め混合・混練して調製したポリエチレン樹脂。
【０１２７】
配合組成物(ＢＬ−６)：配合組成物(ＢＬ−２)の調製に用いたポリエチレン樹脂(Ｒ−２)の代わりに、下記のポリエチレン樹脂(Ｒ−６)を用いる以外は配合組成物(ＢＬ−２)と全く同様にして調製した配合組成物。
【０１２８】
ポリエチレン樹脂(Ｒ−６)：樹脂被覆紙の表樹脂層中の含有量が、ポリエチレン樹脂に対して１００ppmになる量の酸化防止剤(ＡＯ−１)をポリエチレン樹脂(Ｒ−２)中に予め混合・混練して調製したポリエチレン樹脂。
【０１２９】
配合組成物(ＢＬ−７)：配合組成物(ＢＬ−２)の調製に用いたポリエチレン樹脂(Ｒ−２)の代わりに、下記のポリエチレン樹脂(Ｒ−７)を用いる以外は配合組成物(ＢＬ−２)と全く同様にして調製した配合組成物。
【０１３０】
ポリエチレン樹脂(Ｒ−７)：樹脂被覆紙の表樹脂層中の含有量が、ポリエチレン樹脂に対して２００ppmになる量の酸化防止剤(ＡＯ−１)をポリエチレン樹脂(Ｒ−２)中に予め混合・混練して調製したポリエチレン樹脂。
【０１３１】
配合組成物(ＢＬ−８)：配合組成物(ＢＬ−２)の調製に用いたポリエチレン樹脂(Ｒ−２)の代わりに、下記のポリエチレン樹脂(Ｒ−８)を用いる以外は配合組成物(ＢＬ−２)と全く同様にして調製した配合組成物。
【０１３２】
ポリエチレン樹脂(Ｒ−８)：樹脂被覆紙の表樹脂層中の含有量が、ポリエチレン樹脂に対して４００ppmになる量の酸化防止剤(ＡＯ−１)をポリエチレン樹脂(Ｒ−２)中に予め混合・混練して調製したポリエチレン樹脂。
【０１３３】
配合組成物(ＢＬ−９)：配合組成物(ＢＬ−２)の調製に用いたポリエチレン樹脂(Ｒ−２)の代わりに、下記のポリエチレン樹脂(Ｒ−９)を用いる以外は配合組成物(ＢＬ−２)と全く同様にして調製した配合組成物。
【０１３４】
ポリエチレン樹脂(Ｒ−９)：樹脂被覆紙の表樹脂層中の含有量が、ポリエチレン樹脂に対して６００ppmになる量の酸化防止剤(ＡＯ−１)をポリエチレン樹脂(Ｒ−２)中に予め混合・混練して調製したポリエチレン樹脂。
【０１３５】
配合組成物(ＢＬ−１０)：配合組成物(ＢＬ−２)の調製に用いたポリエチレン樹脂(Ｒ−２)の代わりに、下記のポリエチレン樹脂(Ｒ−１０)を用いる以外は配合組成物(ＢＬ−２)と全く同様にして調製した配合組成物。
【０１３６】
ポリエチレン樹脂(Ｒ−１０)：樹脂被覆紙の表樹脂層中の含有量が、ポリエチレン樹脂に対して１０００ppmになる量の酸化防止剤(ＡＯ−１)をポリエチレン樹脂(Ｒ−２)中に予め混合・混練して調製したポリエチレン樹脂。
【０１３７】
配合組成物(ＢＬ−１１)：配合組成物(ＢＬ−２)の調製に用いたポリエチレン樹脂(Ｒ−２)の代わりに、下記のポリエチレン樹脂(Ｒ−１１)を用いる以外は配合組成物(ＢＬ−２)と全く同様にして調製した配合組成物。
【０１３８】
ポリエチレン樹脂(Ｒ−１１)：樹脂被覆紙の表樹脂層中の含有量が、ポリエチレン樹脂に対して１０ppmになる量の酸化防止剤(ＡＯ−１)と９０ppmになる量の酸化防止剤(ＡＯ−２)をポリエチレン樹脂(Ｒ−２)中に予め混合・混練して調製したポリエチレン樹脂。
【０１３９】
配合組成物(ＢＬ−１２)：配合組成物(ＢＬ−２)の調製に用いたポリエチレン樹脂(Ｒ−２)の代わりに、下記のポリエチレン樹脂(Ｒ−１２)を用いる以外は配合組成物(ＢＬ−２)と全く同様にして調製した配合組成物。
【０１４０】
ポリエチレン樹脂(Ｒ−１２)：樹脂被覆紙の表樹脂層中の含有量が、ポリエチレン樹脂に対して２０ppmになる量の酸化防止剤(ＡＯ−１)と８０ppmになる量の酸化防止剤(ＡＯ−２)をポリエチレン樹脂(Ｒ−２)中に予め混合・混練して調製したポリエチレン樹脂。
【０１４１】
配合組成物(ＢＬ−１３)：配合組成物(ＢＬ−２)の調製に用いたポリエチレン樹脂(Ｒ−２)の代わりに、下記のポリエチレン樹脂(Ｒ−１３)を用いる以外は配合組成物(ＢＬ−２)と全く同様にして調製した配合組成物。
【０１４２】
ポリエチレン樹脂(Ｒ−１３)：樹脂被覆紙の表樹脂層中の含有量が、ポリエチレン樹脂に対して５０ppmになる量の酸化防止剤(ＡＯ−１)と５０ppmになる量の酸化防止剤(ＡＯ−２)をポリエチレン樹脂(Ｒ−２)中に予め混合・混練して調製したポリエチレン樹脂。
【０１４３】
配合組成物(ＢＬ−１４)：配合組成物(ＢＬ−２)の調製に用いたポリエチレン樹脂(Ｒ−２)の代わりに、下記のポリエチレン樹脂(Ｒ−１４)を用いる以外は配合組成物(ＢＬ−２)と全く同様にして調製した配合組成物。
【０１４４】
ポリエチレン樹脂(Ｒ−１４)：樹脂被覆紙の表樹脂層中の含有量が、ポリエチレン樹脂に対して８０ppmになる量の酸化防止剤(ＡＯ−１)と２０ppmになる量の酸化防止剤(ＡＯ−２)をポリエチレン樹脂(Ｒ−２)中に予め混合・混練して調製したポリエチレン樹脂。
【０１４５】
配合組成物(ＢＬ−１５)：配合組成物(ＢＬ−２)の調製に用いたポリエチレン樹脂(Ｒ−２)の代わりに、下記のポリエチレン樹脂(Ｒ−１５)を用いる以外は配合組成物(ＢＬ−２)と全く同様にして調製した配合組成物。
【０１４６】
ポリエチレン樹脂(Ｒ−１５)：樹脂被覆紙の表樹脂層中の含有量が、ポリエチレン樹脂に対して９０ppmになる量の酸化防止剤(ＡＯ−１)と１０ppmになる量の酸化防止剤(ＡＯ−２)をポリエチレン樹脂(Ｒ−２)中に予め混合・混練して調製したポリエチレン樹脂。
【０１４７】
配合組成物(ＢＬ−１６)：配合組成物(ＢＬ−２)の調製に用いたポリエチレン樹脂(Ｒ−２)の代わりに、下記のポリエチレン樹脂(Ｒ−１６)を用いる以外は配合組成物(ＢＬ−２)と全く同様にして調製した配合組成物。
【０１４８】
ポリエチレン樹脂(Ｒ−１６)：樹脂被覆紙の表樹脂層中の含有量が、ポリエチレン樹脂に対して１００ppmになる量の酸化防止剤(ＡＯ−１)と１００ppmになる量の酸化防止剤(ＡＯ−２)をポリエチレン樹脂(Ｒ−２)中に予め混合・混練して調製したポリエチレン樹脂。
【０１４９】
なお、樹脂被覆紙の表樹脂層中の酸化防止剤の含有量は、分取液体クロマトグラフィー法により求めた。測定は、具体的には以下のようにして行った。
【０１５０】
(分析試料の調製)：製造した感光材料用支持体を４０℃に保った適当濃度に保ったプロテアーゼ水溶液中に入れてしばらく良く攪拌することで下引層を除去する。その後、超純水を用いて良く洗滌した後自然乾燥する。乾燥後、感光材料用支持体の表樹脂層を基紙より物理的に剥離し、更に附着残留せる基紙を精密に物理的に(鋭利なナイフによる殺ぎ落とし、サンドペーパーによる剥離、湿潤下でのナイロンタワシでの剥離及びこれらの組み合わせ)除去し、その後超純水を用いて良く洗滌した後乾燥する。乾燥後、表樹脂層を約２５mm²の細片に細断したものを分析試料とする。
【０１５１】
(検液の作成)：表樹脂層の分析試料１０gを約２００mlのクロロホルムで約６０℃で５時間抽出(抽出溶剤及びその量抽出温度、抽出時間は、分析対象となる酸化防止剤に合わせて含め検定、選択することが出来る)を行う。抽出後濾過し、抽出液をエバポレーター(水浴６０℃)で約２.５mlに濃縮後２５mlのメタノールを添加して良く攪拌した後濾過し、濾液をエバポレーター(水浴６０℃)で１ml以下に濃縮する。濃縮液にクロロホルムと加えて全量１０ml(必要に応じて適宜全量設定を変更するのが良い)に調製した溶液を検液する。
【０１５２】
(検液の測定)：検液を分取液体クロマトグラフィー法により測定し、２８０nmでの紫外線吸光度のピーク面積により標準サンプルと比較し定量を行う。
(測定装置)；日本分析工業株式会社製ＬＣ−９０８型分取液体クロマトグラフ。
Ｊａｉｇｅｌ２Ｈ、日本分析工業株式会社製ＧＰＣ分取カラム。
(測定条件)ループ容量：３ml。
使用溶媒：クロロホルム。
溶媒流量：３.５ml/分。
測定温度：２３℃。
【０１５３】
得られた結果を表２に示す。
【０１５４】
【表２】

【０１５５】
なお、表２中の(注３)及び(注５)は、以下の通りである。
【０１５６】
(注３)は、表１中のそれと同意義である。
【０１５７】
(注５)酸化防止剤の含有量は、表樹脂層中のポリエチレン樹脂に対する含有量(ppm)を表す。
【０１５８】
表２の結果から、本発明における感光材料用支持体(実施例１１〜２４)並びにハロゲン化銀感光材料(実施例１１〜２５)は、イエローカブリの発生が顕著に改良され、ハロゲン化銀感光層に対する保存性ないしはハロゲン化銀感光層の保存性が顕著に改良された、かつ乳剤膜付きが顕著に安定に改良された、優れた感光材料用支持体並びにハロゲン化銀感光材料であることがよくわかる。
【０１５９】
また、本発明における感光材料用支持体並びにハロゲン化銀感光材料の中でも、ハロゲン化銀感光層に対する保存性ないしはハロゲン化銀感光層の保存性及び乳剤膜付きの改良効果の点から、表樹脂層の酸化防止剤の含有量が、表樹脂層中のポリエチレン樹脂に対する割合として、２０ppm〜６００ppmであるものが好ましく、５０ppm〜４００ppmであるものが特に好ましいことがよくわかる。更に、保存性の改良効果の点から、ヒンダードフェノール系酸化防止剤と分子中にリン原子を含む酸化防止剤を併用したものが好ましく、中でも、それらの全使用量に対して、ヒンダードフェノール系酸化防止剤の使用割合が２０wt%〜８０wt%であり、分子中にリン原子を含む酸化防止剤の使用割合が８０wt%〜２０wt%であるものが特に好ましいことがよくわかる。
【０１６０】
実施例２６〜３５
実施例９で用いた、基紙の表側被覆用の配合組成物(ＢＬ−１)の代わりに、下記の配合組成物(ＢＬ−１７)〜(ＢＬ−２６)を用いること以外は、実施例９と同様に実施した。なお、製造したカラー印画紙の支持体の酸素透過度は、各々３５０cc/m²/dayであった。
【０１６１】
配合組成物(ＢＬ−１７)：二酸化チタン顔料を含む下記マスターバッチ(ＭＢ−１７Ｗ)のペレット１７重量部と二酸化チタン顔料及び群青を含む下記マスターバッチ(ＭＢ−１７Ｂ)のペレット８重量部と前記ポリエチレン樹脂(Ｒ−２)のペレット７５重量部をよく単純混合(ドライブレンド)した配合組成物。
【０１６２】
マスターバッチ(ＭＢ−１７Ｗ)：二酸化チタン粒子表面が含水酸化アルミニウム(二酸化チタン当たりＡｌ₂Ｏ₃分として０.５重量%)で表面処理され、スチームミル粉砕された、電子顕微鏡による個数平均径で０.１２０μmのアナターゼ型二酸化チタン顔料５０重量%、前記ポリエチレン樹脂(Ｒ−１)４７.５重量%及びステアリン酸亜鉛２.５重量%とを、前記酸化防止剤(ＡＯ−１、分子量７００)４００ppmの存在下に、バンバリーミキサーを用いて１５０℃でよく混練し、冷却、ペレット化して製造したマスターバッチ。
【０１６３】
マスターバッチ(ＭＢ−１７Ｂ)：上記二酸化チタン顔料５０重量%、前記ポリエチレン樹脂(Ｒ−１)４６.２５重量%、群青(第一化成工業株式会社製、＃２０００)１.２５重量%及びステアリン配合亜鉛２.５重量%とを、前記酸化防止剤(ＡＯ−１)４００ppmの存在下に、バンバリーミキサーを用いて１５０℃でよく混練し、冷却、ペレット化して製造したマスターバッチ。
【０１６４】
配合組成物(ＢＬ−１８)：二酸化チタン顔料を含む下記マスターバッチ(ＭＢ−１８Ｗ)のペレット１７重量部と二酸化チタン顔料及び群青を含む下記マスターバッチ(ＭＢ−１８Ｂ)のペレット８重量部と前記ポリエチレン樹脂(Ｒ−２)のペレット７５重量部をよく単純混合(ドライブレンド)した配合組成物。
【０１６５】
マスターバッチ(ＭＢ−１８Ｗ)：マスターバッチ(ＭＢ−１７Ｗ)の製造において存在させた酸化防止剤(ＡＯ−１)４００ppmの代わりに、酸化防止剤として、テトラキス[メチレン(３,５−ジ−tert−ブチル−４−ヒドロキシ−ヒドロシンナメート)]メタン(ＡＯ−３，分子量１１７８)４００ppmを存在させること以外は、マスターバッチ(ＭＢ−１７Ｗ)と全く同様にして製造したマスターバッチ。
【０１６６】
マスターバッチ(ＭＢ−１８Ｂ)：マスターバッチ(ＭＢ−１７Ｂ)の製造において存在させた酸化防止剤(ＡＯ−１)４００ppmの代わりに、酸化防止剤(ＡＯ−３，分子量１１７８)４００ppmを存在させること以外は、マスターバッチ(ＭＢ−１７Ｂ)と全く同様にして製造したマスターバッチ。
【０１６７】
配合組成物(ＢＬ−１９)：二酸化チタン顔料を含む下記マスターバッチ(ＭＢ−１９Ｗ)のペレット１７重量部と二酸化チタン顔料及び群青を含む下記マスターバッチ（ＭＢ−１９Ｂ）のペレット８重量部と前記ポリエチレン樹脂(Ｒ−２)のペレット７５重量部をよく単純混合(ドライブレンド)した配合組成物。
【０１６８】
マスターバッチ(ＭＢ−１９Ｗ)：マスターバッチ(ＭＢ−１７Ｗ)の製造において存在させた酸化防止剤(ＡＯ−１)４００ppmの代わりに、酸化防止剤として、３,９−ビス[１.１−ジメチル−２−[β−(３−tert−ブチル−４−ヒドロシキ−５−メチルフェニル)プロピオニルオキシ]エチル]２,４,８,１０−テトラオキサスピロ[５.５]−ウンデカン(ＡＯ−４，分子量７４８)４００ppmを存在させること以外は、マスターバッチ(ＭＢ−１７Ｗ)と全く同様にして製造したマスターバッチ。
【０１６９】
マスターバッチ(ＭＢ−１９Ｂ)：マスターバッチ(ＭＢ−１７Ｂ)の製造において存在させた酸化防止剤(ＡＯ−１)４００ppmの代わりに、酸化防止剤(ＡＯ−４，分子量７４８)４００ppmを存在させること以外は、マスターバッチ(ＭＢ−１７Ｂ)と全く同様にして製造したマスターバッチ。
【０１７０】
配合組成物(ＢＬ−２０)：二酸化チタン顔料を含む下記マスターバッチ(ＭＢ−２０Ｗ)のペレット１７重量部と二酸化チタン顔料及び群青を含む下記マスターバッチ（ＭＢ−２０Ｂ）のペレット８重量部と前記ポリエチレン樹脂(Ｒ−２)のペレット７５重量部をよく単純混合(ドライブレンド)した配合組成物。
【０１７１】
マスターバッチ(ＭＢ−２０Ｗ)：マスターバッチ(ＭＢ−１７Ｗ)の製造において存在させた酸化防止剤(ＡＯ−１)４００ppmの代わりに、酸化防止剤として、１,３,５−トリス(３.５−ジ−tert−ブチル−４−ヒドロキシベンジル)イソシアヌレート(ＡＯ−５，分子量７８３)４００ppmを存在させること以外は、マスターバッチ(ＭＢ−１７Ｗ)と全く同様にして製造したマスターバッチ。
【０１７２】
マスターバッチ(ＭＢ−２０Ｂ)：マスターバッチ(ＭＢ−１７Ｂ)の製造において存在させた酸化防止剤(ＡＯ−１)４００ppmの代わりに、酸化防止剤(ＡＯ−５，分子量７８３)４００ppmを存在させること以外は、マスターバッチ(ＭＢ−１７Ｂ)と全く同様にして製造したマスターバッチ。
【０１７３】
配合組成物(ＢＬ−２１)：二酸化チタン顔料を含む下記マスターバッチ(ＭＢ−２１Ｗ)のペレット１７重量部と二酸化チタン顔料及び群青を含む下記マスターバッチ（ＭＢ−２１Ｂ）のペレット８重量部と前記ポリエチレン樹脂(Ｒ−２)のペレット７５重量部をよく単純混合(ドライブレンド)した配合組成物。
【０１７４】
マスターバッチ(ＭＢ−２１Ｗ)：マスターバッチ(ＭＢ−１７Ｗ)の製造において存在させた酸化防止剤(ＡＯ−１)４００ppmの代わりに、酸化防止剤として、１,３,５−トリメチル−２,４,６−トリス(３.５−ジ−tert−ブチル−４−ヒドロキシベンジル)ベンゼン(ＡＯ−６，分子量７７５)４００ppmを存在させること以外は、マスターバッチ(ＭＢ−１７Ｗ)と全く同様にして製造したマスターバッチ。
【０１７５】
マスターバッチ(ＭＢ−２１Ｂ)：マスターバッチ(ＭＢ−１７Ｂ)の製造において存在させた酸化防止剤(ＡＯ−１)４００ppmの代わりに、酸化防止剤(ＡＯ−６，分子量７７５)４００ppmを存在させること以外は、マスターバッチ(ＭＢ−１７Ｂ)と全く同様にして製造したマスターバッチ。
【０１７６】
配合組成物(ＢＬ−２２)：二酸化チタン顔料を含む下記マスターバッチ(ＭＢ−２２Ｗ)のペレット１７重量部と二酸化チタン顔料及び群青を含む下記マスターバッチ（ＭＢ−２２Ｂ）のペレット８重量部と前記ポリエチレン樹脂(Ｒ−２)のペレット７５重量部をよく単純混合(ドライブレンド)した配合組成物。
【０１７７】
マスターバッチ(ＭＢ−２２Ｗ)：マスターバッチ(ＭＢ−１７Ｗ)の製造において存在させた酸化防止剤(ＡＯ−１)４００ppmの代わりに、酸化防止剤として、ｎ−オクタデシル−３−(３′.５′−ジ−tert−ブチル−４′−ヒドロキシフェニル)プロピオネート(ＡＯ−７，分子量５２０)４００ppmを存在させること以外は、マスターバッチ(ＭＢ−１７Ｗ)と全く同様にして製造したマスターバッチ。
【０１７８】
マスターバッチ(ＭＢ−２２Ｂ)：マスターバッチ(ＭＢ−１７Ｂ)の製造において存在させた酸化防止剤(ＡＯ−１)４００ppmの代わりに、酸化防止剤(ＡＯ−７，分子量５２０)４００ppmを存在させること以外は、マスターバッチ(ＭＢ−１７Ｂ)と全く同様にして製造したマスターバッチ。
【０１７９】
配合組成物(ＢＬ−２３)：二酸化チタン顔料を含む下記マスターバッチ(ＭＢ−２３Ｗ)のペレット１７重量部と二酸化チタン顔料及び群青を含む下記マスターバッチ（ＭＢ−２３Ｂ）のペレット８重量部と前記ポリエチレン樹脂(Ｒ−２)のペレット７５重量部をよく単純混合(ドライブレンド)した配合組成物。
【０１８０】
マスターバッチ(ＭＢ−２３Ｗ)：マスターバッチ(ＭＢ−１７Ｗ)の製造において存在させた酸化防止剤(ＡＯ−１)４００ppmの代わりに、前記酸化防止剤(ＡＯ−１，分子量７００)２００ppmと前記酸化防止剤(ＡＯ−２，分子量６４６)２００ppmを存在させること以外は、マスターバッチ(ＭＢ−１７Ｗ)と全く同様にして製造したマスターバッチ。
【０１８１】
マスターバッチ(ＭＢ−２３Ｂ)：マスターバッチ(ＭＢ−１７Ｂ)の製造において存在させた酸化防止剤(ＡＯ−１)４００ppmの代わりに、前記酸化防止剤(ＡＯ−１，分子量７００)２００ppmと前記酸化防止剤(ＡＯ−２，分子量６４６)２００ppmを存在させること以外は、マスターバッチ(ＭＢ−１７Ｂ)と全く同様にして製造したマスターバッチ。
【０１８２】
配合組成物(ＢＬ−２４)：二酸化チタン顔料を含む下記マスターバッチ(ＭＢ−２４Ｗ)のペレット１７重量部と二酸化チタン顔料及び群青を含む下記マスターバッチ（ＭＢ−２４Ｂ）のペレット８重量部と前記ポリエチレン樹脂(Ｒ−２)のペレット７５重量部をよく単純混合(ドライブレンド)した配合組成物。
【０１８３】
マスターバッチ(ＭＢ−２４Ｗ)：マスターバッチ(ＭＢ−１７Ｗ)の製造において存在させた酸化防止剤(ＡＯ−１)４００ppmの代わりに、前記酸化防止剤(ＡＯ−１，分子量７００)２００ppmと併用する酸化防止剤として、フェニルイソデシルフォスファイト(ＡＯ−８，分子量４３９)２００ppmを存在させること以外は、マスターバッチ(ＭＢ−１７Ｗ)と全く同様にして製造したマスターバッチ。
【０１８４】
マスターバッチ(ＭＢ−２４Ｂ)：マスターバッチ(ＭＢ−１７Ｂ)の製造において存在させた酸化防止剤(ＡＯ−１)４００ppmの代わりに、前記酸化防止剤(ＡＯ−１，分子量７００)２００ppmと酸化防止剤(ＡＯ−８，分子量４３９)２００ppmを存在させること以外は、マスターバッチ(ＭＢ−１７Ｂ)と全く同様にして製造したマスターバッチ。
【０１８５】
配合組成物(ＢＬ−２５)：二酸化チタン顔料を含む下記マスターバッチ(ＭＢ−２５Ｗ)のペレット１７重量部と二酸化チタン顔料及び群青を含む下記マスターバッチ（ＭＢ−２５Ｂ）のペレット８重量部と前記ポリエチレン樹脂(Ｒ−２)のペレット７５重量部をよく単純混合(ドライブレンド)した配合組成物。
【０１８６】
マスターバッチ(ＭＢ−２５Ｗ)：マスターバッチ(ＭＢ−１７Ｗ)の製造において存在させた酸化防止剤(ＡＯ−１)４００ppmの代わりに、前記酸化防止剤(ＡＯ−１，分子量７００)２００ppmと併用する前記酸化防止剤として、テトラキス(２,４−ジ−tert−ブチルフェニル)−４.４′−ビフェニレン−ジ−フォスファイト(ＡＯ−９，分子量１０３５)２００ppmを存在させること以外は、マスターバッチ(ＭＢ−１７Ｗ)と全く同様にして製造したマスターバッチ。
【０１８７】
マスターバッチ(ＭＢ−２５Ｂ)：マスターバッチ(ＭＢ−１７Ｂ)の製造において存在させた酸化防止剤(ＡＯ−１)４００ppmの代わりに、前記酸化防止剤(ＡＯ−１，分子量７００)２００ppmと酸化防止剤(ＡＯ−９，分子量１０３５)２００ppmを存在させること以外は、マスターバッチ(ＭＢ−１７Ｂ)と全く同様にして製造したマスターバッチ。
【０１８８】
配合組成物(ＢＬ−２６)：二酸化チタン顔料を含む下記マスターバッチ(ＭＢ−２６Ｗ)のペレット１７重量部と二酸化チタン顔料及び群青を含む下記マスターバッチ（ＭＢ−２６Ｂ）のペレット８重量部と前記ポリエチレン樹脂(Ｒ−２)のペレット７５重量部をよく単純混合(ドライブレンド)した配合組成物。
【０１８９】
マスターバッチ(ＭＢ−２６Ｗ)：マスターバッチ(ＭＢ−１７Ｗ)の製造において存在させた酸化防止剤(ＡＯ−１)４００ppmの代わりに、前記酸化防止剤(ＡＯ−６，分子量７７５)２００ppmと前記酸化防止剤(ＡＯ−２，分子量６４６)２００ppmを存在させること以外は、マスターバッチ(ＭＢ−１７Ｗ)と全く同様にして製造したマスターバッチ。
【０１９０】
マスターバッチ(ＭＢ−２６Ｂ)：マスターバッチ(ＭＢ−１７Ｂ)の製造において存在させた酸化防止剤(ＡＯ−１)４００ppmの代わりに、前記酸化防止剤(ＡＯ−６，分子量７７５)２００ppmと前記酸化防止剤(ＡＯ−２，分子量６４６)２００ppmを存在させること以外は、マスターバッチ(ＭＢ−１７Ｂ)と全く同様にして製造したマスターバッチ。
【０１９１】
得られた結果を表３に示す。
【０１９２】
【表３】

【０１９３】
なお、表３中の(注３)は、表１中のそれと同意義である。
【０１９４】
表３の結果から、本発明における感光材料用支持体(実施例２６〜３５)並びにハロゲン化銀感光材料(実施例２６〜３５)は、イエローカブリの発生が顕著に改良され、ハロゲン化銀感光層に対する保存性ないしはハロゲン化銀感光層の保存性が顕著に改良された、かつ乳剤膜付きが顕著に安定に改良された、優れた感光材料用支持体並びにハロゲン化銀感光材料であることがよくわかる。
【０１９５】
また、本発明における感光材料用支持体並びにハロゲン化銀感光材料の中でも、ハロゲン化銀感光層に対する保存性ないしはハロゲン化銀感光層の保存性及び乳剤膜付きの改良効果の点から、表樹脂層中に好ましく含有せしめられる酸化防止剤としては、分子量が６００〜１０００の範囲であるヒンダードフェノール系酸化防止剤が一層好ましく、ヒンダードフェノール系酸化防止剤と分子中にリン原子を含む酸化防止剤の併用がなお一層好ましく、更に分子量が６００〜１０００の範囲であるヒンダードフェノール系酸化防止剤と分子量が５００以上である分子中にリン原子を含む酸化防止剤の併用が特に好ましいことがよくわかる。また、実施例２６または実施例２９と実施例２７、実施例２８、実施例３０または実施例３１との比較及び実施例３２と実施例３５との比較より、ヒンダードフェノール系酸化防止剤の中でも、ハロゲン化銀感光層に対する保存性ないしはハロゲン化銀感光層の保存性及び乳剤膜付きの改良効果の点から、イソシアヌレート系化合物が特に好ましいことがよくわかる。
【０１９６】
実施例３６〜３９及び比較例４
実施例５、実施例８、実施例１４、実施例２５及び比較例２で用いた青感乳剤層の代わりに、下記の青感乳剤層を用いること以外は実施例５、実施例８、実施例１４、実施例２５及び比較例２と同様にして実施した(実施例５に対応して実施例３６、実施例８に対応して実施例３７、実施例１４に対応して実施例３８、実施例２５に対応して実施例３９、そして比較例２に対応して比較例４である)。
【０１９７】
青感乳剤層は、適量のヘキサクロロイリジウム(III)酸カリウムの存在下に第１熱成して製造したＡｇＢｒ／ＡｇＣｌ＝９５／５なるハロゲン組成を有する平均粒子径０.８μmの最適感度に硫黄増感した〔１、０、０〕と〔１、１、１〕面の混晶から成る中性法ハロゲン化銀乳剤を硝酸銀量で０.５g/m²含み、更にゼラチン１.５g/m²及びイエロー発色カプラーの他、適量の安定剤、青感用増感色素、塗布助剤、硬膜剤、増粘剤等を含む。青感乳剤層用塗布液の粘度は、５.５cpに調節され、湿潤塗布量が３５g/m²で塗設された。
【０１９８】
得られた結果を表４に示す(なお、結果を比較しやすくするために、表４中に実施例５、実施例８、実施例１４、実施例２４及び比較例２の結果も再掲してある)。
【０１９９】
なお、表４中の(注３)及び(注４)は、表１中のそれらと同意義である。
【０２００】
【表４】

【０２０１】
表４の結果から、本発明の効果、特にハロゲン化銀感光材料の保存に伴うカブリの発生を顕著に抑制して保存性を顕著に改良出来る効果は、ハロゲン化銀感光構成層として、ハロゲン化銀カラー写真構成層、中でも青感ハロゲン化銀の塩化銀含有率が９０モル%以上である青感ハロゲン化銀写真乳剤層を含む多層ハロゲン化銀カラー写真構成層を用いることにより、極めて相乗的に、かつ顕著に達成されることがよくわかる。
【０２０２】
【発明の効果】
本発明により、天然パルプを主成分とする基紙のハロゲン化銀感光層を設ける側がポリエチレン系樹脂を含む樹脂層で被覆され、その反対側がフィルム形成能ある樹脂を含む樹脂層で被覆された、ハロゲン化銀感光層、特にハロゲン化銀が塩化銀主体のものであるハロゲン化銀感光層に対する保存性が顕著に改良された、かつ支持体とハロゲン化銀感光構成層との接着性、特に湿潤時の接着性、いわゆる乳剤膜付きが安定に顕著に改良された樹脂被覆紙型の感光材料用支持体を提供出来る。また、本発明により、天然パルプを主成分とする基紙のハロゲン化銀感光層を設ける側がポリエチレン系樹脂を含む樹脂層で被覆され、その反対側がフィルム形成能ある樹脂を含む樹脂層で被覆された樹脂被覆紙型の感光材料用支持体上にハロゲン化銀感光構成層が塗設された、ハロゲン化銀感光層、特にハロゲン化銀が塩化銀主体のものであるハロゲン化銀感光層の保存性が顕著に改良された、かつ支持体とハロゲン化銀感光構成層、特に湿潤時の接着性、いわゆる乳剤膜付きが安定に顕著に改良されたハロゲン化銀感光材料を提供出来る。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a halogen comprising, as a substrate, a paper mainly composed of natural pulp, at least a silver halide photosensitive layer of a paper substrate (hereinafter sometimes simply referred to as a base paper) and, if necessary, an auxiliary function layer thereof. The side provided with a silver halide photosensitive constituent layer (hereinafter, a silver halide photosensitive constituent layer consisting of at least a silver halide photosensitive layer and, if necessary, its auxiliary function layer may be simply referred to as a silver halide photosensitive constituent layer) Polyethylene resin (a) and At least a hindered phenol antioxidant or an antioxidant containing a phosphorus atom in the molecule A support for a photosensitive material, which is coated with a resin layer (B) containing a resin layer (B) containing a resin (b) capable of forming a film, and a silver halide photosensitive constituent layer on the support. The present invention relates to a silver halide light-sensitive material to which is coated. Specifically, the storage stability (hereinafter sometimes simply referred to as “preservability”) of the silver halide photosensitive layer, particularly the silver halide photosensitive layer in which the silver halide is mainly silver chloride, has been significantly improved, and The present invention relates to a support for a light-sensitive material in which the adhesion between the support and the silver halide photosensitive constituent layer, in particular, the adhesion when wet, that is, with a so-called emulsion film, is remarkably improved.
[0002]
[Prior art]
Usually, the silver halide light-sensitive material is composed of a light-sensitive material support and a silver halide light-sensitive constituent layer provided on the support. For example, silver halide photographic materials, silver halide photosetting paper materials, silver salt diffusion transfer method negative materials, silver salt light-sensitive and heat-sensitive recording materials, Consists of silver halide emulsion layers, silver halide diffusion transfer method negative emulsion layers, silver halide photosensitive layers such as silver salt light-sensitive thermal emulsion layers, and auxiliary functional layers such as subbing layers, protective layers, and back layers as necessary. A silver halide photosensitive constituent layer (in particular, a silver halide photosensitive constituent layer comprising a silver halide photographic emulsion layer and, if necessary, its auxiliary function layer) may be simply referred to as a silver halide photographic constituent layer hereinafter. ) Is painted. In particular, the silver halide photographic constituent layers include a silver halide photographic emulsion layer, a protective layer, an undercoat layer, an intermediate layer or an anti-color mixing layer, an antihalation layer, or a filter layer, an ultraviolet absorbing layer, a back layer and the like. It is comprised from those combinations. For example, a single silver halide photographic material may be halogenated on a photosensitive material support (especially, a photosensitive material support for photographic material use may be simply referred to as a photographic material support hereinafter). A silver photographic emulsion layer and a protective layer thereof are provided. Multilayer silver halide color photographic materials are also provided on a support for photographic materials, such as an undercoat layer, a blue-sensitive silver halide photographic emulsion layer and an intermediate layer, a green-sensitive silver halide photographic emulsion layer and an ultraviolet absorbing layer, and a red-sensitive halogen. A silver halide photographic emulsion layer and a silver halide color photographic constituent layer such as a protective layer are provided in this order to form a multilayer arrangement.
[0003]
2. Description of the Related Art Conventionally, a resin-coated paper type support in which a base paper surface for a support for a photosensitive material is coated with a resin capable of forming a film is well known. As a support for a resin-coated paper type photographic material for use in silver halide photographic material, for example, in Japanese Patent Publication No. 55-12584, the base paper is coated with a film-forming resin, preferably a polyolefin resin. Techniques relating to a photographic material support are disclosed. U.S. Pat. No. 3,501,298 discloses a technique for a photographic material support in which both sides of a base paper are coated with a polyolefin resin, preferably a polyethylene resin. In addition, since the rapid photographic development processing method for silver halide photographic materials has been applied, photographic material supports in which both sides of the base paper are coated with polyethylene resin have been put to practical use mainly for photographic paper. If necessary, the resin layer on the side on which one of the image forming layers is provided usually contains a titanium dioxide pigment in order to impart sharpness.
[0004]
However, the side of the base paper, particularly the base paper mainly composed of natural pulp, on which the silver halide photosensitive layer is provided is coated with a resin layer containing a polyethylene resin, and the opposite side is coated with a resin layer containing a film-forming resin. The coated resin-coated paper support for photosensitive material still has some serious problems, and the actual situation is that satisfactory results have not yet been obtained.
[0005]
First, the side of the base paper, particularly the base paper mainly composed of natural pulp, on which the silver halide photosensitive layer is provided is coated with a resin layer containing a polyethylene resin, and the opposite side is a resin containing a film-forming resin. When a silver halide light-sensitive material having a resin-coated paper coated with a layer as a support is stored after its production, it is referred to as fog when stored for a long period of time, especially when stored under high temperature and high humidity. There is a tendency that unexposed portions of the photosensitive material become developable during the development process, and the tone of the photosensitive material changes to soften. In addition, there is another problem that the sensitivity of the photosensitive material is unduly increased or decreased.
[0006]
So far, various stabilizers or antifoggants have been proposed for improving the storage stability of so-called silver halide photosensitive materials, which prevents changes in photographic characteristics during storage of the silver halide photosensitive materials. For example, proposed are hydroxy-substituted triazolopyrimidine compounds described in US Pat. No. 2,944,900, JP-B 34-5647, mercapto-heterocyclic compounds described in JP-A 48-102621, etc. Has been. However, various stabilizers or antifoggants are contained in the emulsion layer of the silver halide photosensitive material using the resin-coated paper coated with polyethylene resin on the side of the base paper on which the silver halide photosensitive layer is provided. However, not only has a significant photographic adverse effect such as a decrease in sensitivity and softening of the tone, but also the storage stability cannot be effectively and significantly improved.
[0007]
There are also several proposals for improving the storage stability of a silver halide photosensitive material having a resin-coated paper as a support. In Japanese Patent Publication Nos. 49-30446 and 50-33652, a silver halide photosensitive layer is used because the resin decomposition products and oxides generated during melt extrusion coating cause fogging in the emulsion of photographic paper. A support for a resin-coated paper type photographic paper with a low fog is proposed in which the resin layer on the side provided with a two-layer structure and the upper resin layer adjacent to the silver halide photosensitive layer are melt-extruded and coated at a low temperature. Yes. However, even if the support is used, it was considerably insufficient to improve the storage stability of the silver halide light-sensitive material, and it was extremely insufficient to stably improve the emulsion film attachment. . JP-B-54-9884 proposes an antifoggant resin-coated paper-type photosensitive material support in which a base paper is coated with a polyolefin resin containing a hydroxy-substituted triazolopyrimidine compound. However, even when the support is used, it is considerably insufficient to improve the storage stability of the silver halide photosensitive material. Further, JP-A-6-118555 discloses a subbing layer containing a titanium dioxide pigment resin composition having an oxidation induction period of 70 to 1000 seconds in a resin layer and containing a specific polyhydroxybenzene compound. A technique for improving the storage stability of a silver halide photosensitive material by using the provided polyethylene-based resin-coated paper and maintaining the emulsion film is disclosed, but the storage stability of the silver halide photosensitive material is also disclosed using the support. However, it was still insufficient to improve the film thickness, and it was insufficient to stably improve the emulsion coating.
[0008]
In addition, from the surface of the base paper, there are several proposals for improving the storage stability and other characteristics of the silver halide photosensitive material having a resin-coated paper as a support. Adverse effects of additive chemicals for paper described in JP-A-52-65423 and JP-B-58-43730 and techniques for improving them, JP-A-2-96741, JP-A-2-99689, and JP-A-2- There are proposals such as the use of pulp bleached with peroxide described in Japanese Patent Publication No. 58-43732, such as the adverse effects of antifoaming agents described in Japanese Patent No. 99693 and the improvement technology thereof, but these technologies were applied. Even if a resin-coated paper made of a base paper is used as a support, the storage stability of the silver halide light-sensitive material cannot be improved at all or is considerably insufficient, and deterioration of storage stability is described in these specifications. It has become clear that this is caused by a completely different mechanism. Japanese Patent Laid-Open No. 8-106140 proposes a photographic paper containing a low molecular weight polyvinyl alcohol having a low oxygen permeability. However, a resin-coated paper made of a base paper to which the technique is simply applied may be used. It was extremely insufficient to improve the storage stability of the silver halide photosensitive material.
[0009]
Second, the side on which the silver halide photosensitive layer of the base paper based on natural pulp is provided is coated with a resin layer containing a polyethylene resin, and the opposite side is coated with a resin layer containing a film-forming resin. The silver halide photosensitive material using the resin-coated paper as a support has a problem that the adhesion between the support and the silver halide photosensitive constituent layer is insufficient. In particular, the silver halide light-sensitive material is required to have extremely strong adhesion with a support in a wet and swollen state of the silver halide light-sensitive constituent layer, that is, with a so-called emulsion film. If the emulsion film is insufficient, the silver halide photosensitive constituent layer may be peeled off during development of the silver halide photosensitive material, or the emulsion film surface may be wrinkled when dried. However, in the silver halide light-sensitive material using a polyethylene-based resin-coated paper as a substrate as a support, although the cause has not been clarified in the past, this with the emulsion film fluctuates, and the emulsion film with the film is often insufficient. There was a problem that only things could be obtained.
[0010]
For this reason, several proposals have been made to improve the adhesion of the support for resin-coated paper-type photosensitive material to the silver halide photosensitive constituent layer, that is, so-called emulsion film attachment. The simplest method for improving the adhesion between the resin-coated paper mold support and the silver halide photosensitive constituent layer is as described in British Patent Nos. 971,058 and 1,060,526, etc. Electron impact is applied to the resin surface of the resin-coated paper mold support. Electron bombardment is also known as corona discharge treatment. Japanese Patent Application Laid-Open No. 62-260149 proposes to provide an undercoat layer containing gelatin on the surface of a resin-coated paper-type photographic support. However, even if the resin-coated paper-type support for photosensitive material is subjected to a corona discharge treatment or an undercoat layer is applied after the corona discharge treatment, the resin-coated paper-type support for photosensitive material and silver halide Adhesiveness with the photosensitive constituent layer was insufficient, and particularly in wet and swollen state, so-called emulsion film attachment was considerably insufficient. In particular, with an emulsion film, it is estimated that it depends largely on the properties of the resin surface of the resin-coated paper-type support, but even the mechanism is not yet clear. Even when used together with the subbing layer, the emulsion film coating greatly fluctuates, and there is often a problem that only the emulsion film coating is considerably poor. In such a case, even if the strength of the corona discharge treatment is increased. Even if the corona discharge treatment is repeated, there is a problem that the emulsion film is not improved, but rather deteriorates.
[0011]
Furthermore, when the present inventors pursued the problem with the emulsion film, as the intensity of the corona discharge treatment to the surface of the resin-coated paper mold support was increased in order to improve the emulsion film attachment, the corona discharge treatment As the number of repetitions is repeated, the storage stability of the silver halide light-sensitive material having the support is remarkably deteriorated, and further, this deterioration in storage stability is improved only sufficiently even when an undercoat layer is provided on the support surface. It has been found that there is a contradictory relationship between the problems that cannot be achieved, that is, the storage stability of the silver halide light-sensitive material and the problem with the emulsion film. Further, the storability of the silver halide photosensitive material having a resin-coated paper-type support is such that the silver halide of the silver halide photosensitive layer is mainly composed of silver chloride, in particular, the silver chloride content of silver halide is 90 mol% or more. It has been found that there is a problem that it is significantly worsened.
[0012]
As described above, the side on which the silver halide photosensitive layer of the base paper mainly composed of natural pulp is provided is coated with a resin layer containing a polyethylene resin, and the opposite side is coated with a resin layer containing a film-forming resin. The mechanism or cause of deterioration of storage stability of a silver halide photosensitive material having a resin-coated paper-type support for photosensitive material and the adhesion of the silver halide photosensitive constituent layer to the support, particularly with an emulsion film when wet The mechanism and the cause of its deterioration are not known, and the storability of the silver halide photosensitive layer, particularly the silver halide photosensitive layer in which the silver halide is mainly silver chloride, has been significantly improved, and the support and There is no known resin-coated paper-type support for a photosensitive material in which adhesion to a silver halide photosensitive constituent layer, in particular wet adhesion, so-called emulsion film attachment, has been remarkably improved. In addition, the side of the base paper containing natural pulp as the main component on which the silver halide photosensitive layer is provided is coated with a resin layer containing a polyethylene resin, and the other side is coated with a resin layer containing a film-forming resin. The storage stability of a silver halide photosensitive layer, particularly a silver halide photosensitive layer in which the silver halide is mainly composed of silver chloride, with a paper support, and the support and the silver halide photosensitive constituent layer are remarkably improved. No silver halide light-sensitive material has been known in which the adhesiveness to water, particularly when wet, so-called emulsion film attachment, has been significantly improved.
[0013]
[Problems to be solved by the invention]
Therefore, The purpose of the present invention is to A silver halide photosensitive material in which the side on which the silver halide photosensitive layer of the base paper mainly composed of natural pulp is provided is coated with a resin layer containing a polyethylene resin, and the opposite side is coated with a resin layer containing a film-forming resin. Layer, especially the silver halide photosensitive layer in which the silver halide is mainly composed of silver chloride, the storage stability was remarkably improved, and the adhesion between the support and the silver halide photosensitive constituent layer, particularly when wet It is to provide a support for a photosensitive material of a resin-coated paper type in which the so-called emulsion film coating is stably improved remarkably. . Other objects of the present invention will become clear from the description of the following specification.
[0014]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have, as a substrate, a paper mainly composed of natural pulp, and comprise at least a silver halide photosensitive layer of the paper substrate and, if necessary, an auxiliary function layer thereof. Photosensitive material in which the side on which the silver halide photosensitive constituent layer is provided is coated with a resin layer (A) containing a polyethylene resin (a) and the opposite side is coated with a resin layer (B) containing a resin (b) capable of forming a film A support for Contains at least a hindered phenolic antioxidant or an antioxidant containing a phosphorus atom in the molecule The polyethylene surface oxidation degree specified below on the surface of the resin layer (A) is in the range of 33% to 53%, and the oxygen permeability of the support for photosensitive material specified below is 450 cc / m. ² / Day or less, by the support for photosensitive material, Object of the present invention Has been found to achieve the present invention.
Polyethylene surface oxidation degree: after or without applying an appropriate activation treatment to the surface of the resin layer (A), after applying an undercoat layer as required, or without applying an undercoat layer A silver halide photosensitive material is produced by coating a silver halide photosensitive constituent layer. After or after the production period, the silver halide photosensitive material is dry-thermo-dried at 65 ° C. for 5 days, the silver halide photosensitive constituent layer is removed by enzyme treatment, and then washed thoroughly with ultrapure water and then dried. To do. After drying, the O / C ratio (peak area ratio) (%) on the surface of the resin layer (A) obtained by measurement by ESCA (Electron Spectroscopy for Chemical Analysis) method is defined as the polyethylene surface oxidation degree (%).
Oxygen permeability of photosensitive material support: After or without appropriate activation treatment on the surface of the resin layer (A), after or undercoating the undercoat layer as necessary Without producing a silver halide photosensitive material, a silver halide photosensitive constituent layer is coated. After or after the production period, the silver halide photosensitive material is dry-thermo-dried at 65 ° C. for 5 days, the silver halide photosensitive constituent layer is removed by enzyme treatment, and then washed thoroughly with ultrapure water and then dried. To do. After drying, the oxygen permeability of the light-sensitive material support was determined by measuring the oxygen permeability of the light-sensitive material support under the following measurement conditions in accordance with B method (isobaric method) of JIS K 7126. / M ² / Day).
Measurement environment: 23 ° C., 65% relative humidity.
Gas flow rate: oxygen; 20 ml / min, carrier gas (nitrogen / hydrogen gas); 10 ml / min.
Test cell area: 5cm ² (Use aluminum foil mask).
Diffusion direction: Resin layer (B) side (diffusion tank) from resin layer (A) side (oxygen tank).
[0020]
Furthermore, the object of the present invention is to Further, a hindered phenolic antioxidant or an antioxidant containing a phosphorus atom in the molecule is contained in the resin layer (A), and in particular, the hindered phenolic antioxidant and the molecule in the resin layer (A). It has been found that it can be achieved more remarkably by containing an antioxidant containing a phosphorus atom in combination. Further, the object of the present invention can be achieved more remarkably by incorporating an antioxidant in the resin layer (A) in a proportion of 20 ppm to 600 ppm, particularly 50 ppm to 400 ppm, as a proportion relative to the polyethylene resin (a). The Heading The present invention has been achieved.
[0022]
DETAILED DESCRIPTION OF THE INVENTION
The support for the photosensitive material in the present invention is a side on which a silver halide photosensitive layer is provided (hereinafter, the side on which the silver halide photosensitive layer is provided is the front side, the resin layer coated on the front side is the front resin layer, the opposite side is the back side, The resin layer coated on the back side may be referred to as the back resin layer) is a polyethylene resin (a) And at least a hindered phenol antioxidant or an antioxidant containing a phosphorus atom in the molecule Is coated with a resin layer (B) containing a resin (b) having film-forming ability. As a production method thereof, in the case where the resin in the back resin layer is generally a thermoplastic resin, preferably a polyolefin resin, particularly preferably a polyethylene resin on a traveling base paper, a polyethylene resin composition for the front resin layer and It is manufactured by a so-called melt extrusion coating method in which a thermoplastic resin composition for a back resin layer is cast and coated from the slit die into a film using a melt extruder. Usually, using a melt extruder on the traveling base paper, the melted resin composition is extruded from the slit die into a film, coated by casting, and pressure-bonded between a pressure roll and a cooling roll, It is produced in a series of steps of peeling from the cooling roll. In that case, the temperature of a molten film is the range of 270 degreeC-340 degreeC normally. The slit die is preferably a flat die such as a T die, an L die, or a fishtail die, and the slit opening diameter is preferably 0.1 mm to 2 mm. Moreover, it is preferable to subject the base paper to activation treatment such as corona discharge treatment and flame treatment before coating the resin composition on the base paper. Further, as described in JP-B-61-42254, a resin layer may be coated on the base paper that travels after the ozone-containing gas is sprayed on the molten resin composition on the side in contact with the base paper. In addition, the front and back resin layers are preferably coated on the base paper by a so-called tandem extrusion coating method, which is successively, preferably continuously, extrusion-coated. You may coat | cover with the multilayer extrusion coating system made into the multilayer structure more than a layer. Further, the surface resin layer surface of the support for the photosensitive material can be processed into a glossy surface, a fine rough surface described in JP-B-62-19732, a matte surface or a silky surface, and the back resin layer surface is usually matte. It is preferable to process the surface or matte surface.
[0023]
In the present invention, the light-sensitive material support or the light-sensitive material support in the silver halide light-sensitive material has a polyethylene surface oxidation degree or a support surface oxidation degree specified in this specification in the range of 33% to 53%, It is preferably in the range of 35% to 50%, particularly preferably in the range of 37% to 47%. If the polyethylene surface oxidation degree or the support surface oxidation degree is less than 33%, the adhesion between the support and the silver halide photosensitive constituent layer, particularly the adhesion when wet, deteriorates, while 53% If it is higher, the storability of the silver halide light-sensitive material deteriorates, and in particular, the generation of fog is a problem.
In order to make the polyethylene surface oxidation degree or the support surface oxidation degree within a range of 33% to 53%, specifically, by using the following method, preferably two or more of the following methods are more preferable. It has become clear from the study of the present inventors that a combination of three or more can be used.
[0024]
(1) The surface resin layer (A) surface of the image material support is subjected to corona discharge treatment having an appropriate strength by an appropriate corona discharge treatment apparatus.
[0025]
(2) As the polyethylene resin (a) for the surface resin layer, an appropriately selected polyethylene resin is used. As the polyethylene-based resin, one having a hexane extraction amount of 3.0% by weight or less, preferably 2.0% by weight or less, particularly preferably 1.5% by weight or less is used. A polyethylene resin having a hexane extraction amount in this range can be obtained by ordering from a polyethylene resin manufacturer.
[0026]
As used herein, the amount of hexane extracted refers to about 2.5 g of a sample of an about 38 μm-thick inflation film processed at 150 ° C. cut into 15 cm × 2.5 cm strips, and 300 ml of n-hexane maintained at 50 ° C. The film was extracted for 2 hours after immersion, and the ratio of the weight reduced by extraction to the weight before extraction from the change in the weight of the film before and after is defined as the hexane extraction amount (% by weight).
[0027]
(3) A suitable antioxidant is contained in the surface resin layer (A). As the antioxidant, a hindered phenol antioxidant or an antioxidant containing a phosphorus atom in the molecule is preferable, and a hindered phenol antioxidant and an antioxidant containing a phosphorus atom in the molecule are used in combination. It is particularly preferable to let it lie. The hindered phenol antioxidant preferably has a molecular weight in the range of 600 to 1000, and the antioxidant containing a phosphorus atom in the molecule preferably has a molecular weight of 500 or more. Moreover, as a hindered phenolic antioxidant, what is an isocyanurate type compound is especially preferable. Furthermore, as content of antioxidant in a surface resin layer (A), the range of 20 ppm-600 ppm is preferable, and the range of 50 ppm-400 ppm is especially preferable.
[0028]
(4) As the titanium dioxide pigment that is usually contained in the surface resin layer (A), a titanium dioxide pigment with good dispersibility is used, and the titanium dioxide pigment is previously mixed in a polyethylene resin with an appropriate mixing and kneading apparatus. And contained as a master batch containing a constant concentration.
[0029]
(5) As the surface resin layer (A), the surface resin layer (A) composed of at least two layers of the lowermost layer and the uppermost layer is used, and the resin layer composed of at least the lowermost layer and the resin layer composed of at least the uppermost layer are sequentially melted. The surface resin layer (A) consisting of at least two layers is coated by a sequential extrusion coating method by extrusion coating.
[0030]
As the polyethylene resin (a) for the surface resin layer (A) used in the practice of the present invention, a polyethylene resin polymerized by a high pressure method, a polyethylene resin polymerized using a metallocene polymerization catalyst, a metallocene polymerization catalyst And polyethylene resins produced by polymerization using a metal catalyst other than the above, and mixtures thereof.
[0031]
Examples of polyethylene resins polymerized and produced by the high pressure method used in the practice of the present invention include various polyethylene resins having long chain branches produced by a high pressure production method using an autoclave reactor, a tubular reactor, or the like. is there. Polyethylene resins polymerized and produced by these high pressure methods include low density polyethylene resins, medium density polyethylene resins, copolymers with ethylene-based propylene, butylene and other α-olefins, carboxy-modified polyethylene resins, and the like. These mixtures can be used in various densities, melt flow rates, molecular weights, and molecular weight distributions. Usually, the density is 0.90 g / cm. ^Three ~ 0.95g / cm ^Three Range, preferably a density of 0.90 g / cm ^Three ~ 0.925g / cm ^Three The melt flow rate is in the range of 0.1 g / 10 min to 50 g / 10 min, preferably in the range of 0.4 g / 10 min to 50 g / 10 min, either singly or in combination. Can be used. In addition, the melt flow rate of a polyethylene-type resin is prescribed | regulated based on JISK6760 "polyethylene test method".
[0032]
Examples of the polyethylene resin polymerized and produced using the metallocene polymerization catalyst used in the practice of the present invention include Japanese Patent Publication No. 3-502710, Japanese Patent Laid-Open No. 60-3506, Japanese Patent Publication No. 63-501369, As described or disclosed in Kaihei 3-234717, JP-A-3-234718, etc., the catalytic activity was enhanced by combining a metallocene such as zirconium or hafnium and preferably methylaluminoxane. The product is produced by polymerization using a polymerization catalyst. The polyethylene resins polymerized using these metallocene polymerization catalysts include ultra-low density polyethylene resin, low density polyethylene resin, medium density polyethylene resin, high density polyethylene resin, linear low density polyethylene resin, and ethylene as the main component. A copolymer with an α-olefin such as propylene and butylene, a carboxy-modified polyethylene resin and the like, and a mixture thereof, which can be used in various densities, melt flow rates, molecular weights, and molecular weight distributions. Between 0.87 g / cm and 0.97 g / cm ^Three Range, preferably 0.890 g / cm ^Three ~ 0.950g / cm ^Three In particular, the density is preferably 0.905 g / cm ^Three ~ 0.930g / cm ^Three In the range of 0.05 g / 10 min to 500 g / 10 min, preferably 0.08 g / 10 min to 300 g / 10 min, can be used alone or in admixture of two or more.
[0033]
Examples of the polyethylene resin polymerized and produced using a metal polymerization catalyst other than the metallocene polymerization catalyst used in the practice of the present invention include various polyethylene resins polymerized and produced using the Ziegler method, the Philips method, etc. . Examples of polyethylene resins polymerized using metal polymerization catalysts other than those metal metallocene polymerization catalysts include ultra-low density polyethylene resins, low density polyethylene resins, medium density polyethylene resins, high density polyethylene resins, and linear low density polyethylene. Resins, copolymers of ethylene-based propylene, butylene and other α-olefins, or carboxy-modified polyethylene resins, and mixtures thereof, with various densities, melt flow rates, molecular weights, and molecular weight distributions. Can be used but usually has a density of 0.87 g / cm ^Three ~ 0.97g / cm ^Three Range, preferably a density of 0.890 g / cm ^Three ~ 0.950g / cm ^Three In particular, the density is preferably 0.905 g / cm ^Three ~ 0.930g / cm ^Three In the range of 0.05 g / 10 min to 500 g / 10 min, preferably 0.08 g / 10 min to 300 g / 10 min, can be used alone or in admixture of two or more.
[0034]
As the polyethylene resin (a) used in the practice of the present invention, particularly when two or more polyethylene resins having different melt flow rates are used in combination, the two or more polyethylene resins to be used are previously melted and mixed. The compound resin composition prepared as described above is preferable. For example, when a polyethylene resin having a melt flow rate of 5 g / 10 min to 40 g / 10 min and a polyethylene resin having a melt flow rate of 0.2 g / 10 min to 4.5 g / 10 min are used in combination. It is preferably used as a compound resin composition prepared by melting and mixing in advance. Use of the compound resin thus prepared is preferable in terms of molding processability, film uniformity, and prevention of non-uniform resin mass called a resin gel. As a method for preparing the compound resin composition, various methods can be used. For example, using a kneading extruder, heated roll kneader, Banbury mixer, pressure kneader, etc., two or more types of polyethylene resins, and if necessary, other thermoplastic resins, antioxidants, mold release agents, etc. A method in which various additives are added, melted and mixed, and then the mixture is pelletized is advantageously used.
[0035]
The total melt flow rate of the polyethylene resin component in the surface resin layer (A) used in the practice of the present invention is not particularly limited, but the melt extrusion coating property and molding of the resin composition In view of processability, the melt flow rate is preferably in the range of 1.5 g / 10 min to 50 g / 10 min, more preferably in the range of 2 g / 10 min to 30 g / 10 min, and 2.5 g / 10 min to 15 g. A range of 10 minutes is even more preferred, and a range of 3 g / 10 minutes to 10 g / 10 minutes is particularly preferred.
[0036]
The polyethylene resin (a) used in the practice of the present invention is a total of all polyethylene resin components in the resin composition (A) from the viewpoint of improving the curled physical properties of the silver halide photosensitive material and its print. Density (calculated density) is 0.940 g / cm ^Three The following are preferred, 0.928 g / cm ^Three More preferred is 0.992 g / cm ^Three The following are particularly preferred.
[0037]
Further, in the surface resin composition (A), other resins other than the polyethylene resin, for example, homopolymers such as polybutene and polypentene, ethylene, and the like within the range satisfying the requirements of the present invention without impairing the effects of the present invention. A copolymer composed of two or more α-olefins such as a butylene copolymer may be contained.
[0038]
The back side of the base paper of the image material support in the present invention is coated with a resin layer (B) containing a resin (b) capable of forming a film. As the resin (b) capable of forming these films, thermoplastic resins such as polyolefin resins, polycarbonate resins, polyester resins, and polyamide resins are preferable. Among them, polyolefin resins are more preferable from the viewpoint of melt extrusion coating properties, and polyethylene resins are preferable. Particularly preferred. Further, it may be coated with an electron beam curable resin described or exemplified in JP-B-60-17104.
[0039]
The polyethylene resin for the back resin layer (B) preferably used in the practice of the present invention has a melt flow rate of 10 g / 10 min to 40 g / 10 min and a density of 0.960 g / cm. ^Three 90 to 50 parts by weight of the above high-density polyethylene resin, a melt flow rate of 0.2 g / 10 min to 3 g / 10 min, and a density of 0.935 g / cm ^Three A compound resin composition obtained by previously melting and mixing 10 parts by weight to 50 parts by weight of the following low density polyethylene resin or medium density polyethylene resin is preferable.
[0040]
The support for a photosensitive material in the present invention preferably has a multilayer structure having two or more surface resin layers, and more preferably has a two-layer structure in order to effectively achieve the object of the present invention. Further, the photosensitive material support having a multilayer structure of two or more surface resin layers is preferably manufactured by a melt extrusion coating method. In the production, a so-called co-extrusion coating method in which two or more multilayer resin layers are simultaneously extrusion coated may be used, or a resin layer consisting of at least the lowermost layer and then a resin consisting of at least the uppermost layer. A so-called sequential extrusion coating system may be used in which the layers are sequentially melt extrusion coated at separate stations. In the present invention, a light-sensitive material support produced using a sequential extrusion coating method is particularly preferred.
[0041]
The multilayer coextrusion die may be any type such as a feed block type, a multi-manifold type, and a multi-slot type. In addition, when performing melt extrusion coating by the sequential extrusion coating method or the coextrusion coating method, the temperature of the molten film is usually in the range of 270 ° C. to 340 ° C., but at that time, the resin composition for the uppermost layer and the lower side thereof You may give the temperature difference of the resin composition which comprises this resin layer. For example, it is preferable to lower the temperature of the resin composition for the uppermost layer by 5 to 10 ° C. lower than the temperature of the resin composition constituting the lower resin layer in order to effectively achieve the object of the present invention. .
[0042]
As the preferred resin layer of the support for a photosensitive material in the present invention, the surface resin layer has a multilayer structure, the uppermost resin layer (hereinafter sometimes simply referred to as the uppermost layer) and the lower resin layer. (Hereinafter, it may be abbreviated as simply the lower resin layer) may have the same physical properties and composition, or may be different. Examples of the polyethylene resin preferably used for the uppermost layer and the lower resin layer include various densities and melt flow rates as described above (hereinafter, the melt flow rate defined by JIS K 6760 is simply abbreviated as MFR). , Molecular weight, molecular weight distribution and the like can be used alone or in combination, and their physical properties may be the same or different.
[0043]
For example, as the polyethylene resin in the uppermost layer, the MFR (MFR as a mixture when two or more types are contained, hereinafter the same meaning) is used as the MFR of the polyethylene resin in the lower resin layer (two In the case of containing more than one species, MFR as a mixture, hereinafter the same meaning), higher, lower or the same can be used. For example, the polyethylene resin in the uppermost layer has an MFR of 5 g / 10 min to 20 g / 10 min, and the polyethylene resin in the lower resin layer has an MFR of 2 g / 10 min to 10 g / 10 min. On the other hand, as the polyethylene resin in the uppermost layer, the MFR is 2 g / 10 min to 10 g / 10 min, and as the polyethylene resin in the lower resin layer, the MFR is 5 g / 10 min to 20 g / 10 min. Can be used, and those having the same MFR can be used.
[0044]
Further, as the polyethylene resin in the uppermost layer, the density (in the case of containing two or more kinds, the density as a mixture, hereinafter the same meaning) is the density of the polyethylene resin in the lower resin layer (two In the case of containing more than one species, the density as a mixture, which is the same meaning below), higher, lower or the same can be used. For example, as a polyethylene resin in the uppermost layer, the density is 0.925 g / cm. ^Three ~ 0.970 g / cm ^Three As a polyethylene resin in the lower resin layer, the density is 0.870 g / cm. ^Three ~ 0.925g / cm ^Three On the other hand, as the polyethylene resin in the top layer, the density is 0.870 g / cm ^Three ~ 0.925g / cm ^Three As a polyethylene resin in the lower resin layer, the density is 0.925 g / cm ^Three ~ 0.970 g / cm ^Three Can be used, and those with the same density can be used.
[0045]
Further, as the polyethylene resin in the uppermost layer, at least one of those whose melting point is higher, lower or the same as that of the polyethylene resin in the lower resin layer can be used. For example, the polyethylene resin in the uppermost layer can have a melting point of 115 ° C. or higher, and the polyethylene resin in the lower resin layer can have a melting point of less than 115 ° C., while the polyethylene resin in the uppermost layer can be used. As the polyethylene resin in the lower resin layer, those having a melting point of 115 ° C. or higher can be used, and those having the same melting point can be used.
[0046]
Various additives can be contained in the surface resin layer of the support for a photosensitive material in the present invention and, if necessary, in the back resin layer. For the purpose of improving the whiteness of the support and the sharpness of the image, it is preferable to contain a titanium dioxide pigment. In addition to titanium dioxide pigments, white pigments such as zinc oxide, talc and calcium carbonate, release agents, fatty acid amides such as stearamide and arachidic acid amide, pigment dispersants and release agents, zinc stearate , Calcium stearate, aluminum stearate, magnesium stearate, zinc palmitate, zinc myristate, calcium palmitate, and other fatty acid metal salts, antioxidants, hindered amines, sulfur-based antioxidants, cobalt blue, etc. , Blue pigments and dyes such as ultramarine blue, ceria blue and phthalocyanine blue, magenta pigments and dyes such as cobalt violet, fast violet and manganese violet, fluorescent whitening agents described or exemplified in JP-A-2-254440 Various additives such as UV absorbers It can be incorporated in combination. These additives are preferably contained as a resin masterbatch or compound. Also, white pigments such as titanium dioxide pigments, fluorescent whitening agents, and coloring pigments from the standpoint of effective improvement in print sharpness or whiteness or heat resistance, light resistance, or releasability of the support for image materials And other additives such as coloring dyes, antioxidants, ultraviolet absorbers or mold release agents are preferably contained in the uppermost layer at a higher concentration than in the lower resin layer. In particular, the content of the titanium dioxide pigment in the uppermost layer (as a proportion of the weight in the uppermost layer) is 7% by weight or more, further 9% by weight or more, still more 12% by weight or more, especially 15% by weight or more. Is preferred.
[0047]
As the titanium dioxide pigment that is usually contained in the surface resin layer (A) of the support for photosensitive material in the present invention, a titanium dioxide pigment having good dispersibility in a polyethylene resin is used. It is preferable to make it contain as a masterbatch or compound contained in the resin based on an appropriate mixing / kneading apparatus. Specifically, a so-called master batch in which a titanium dioxide pigment is previously contained in a polyethylene resin at a constant concentration is prepared, and is diluted and mixed in a desired ratio with a polyethylene resin for dilution, or is contained. It is preferable to prepare and use a so-called compound in which a titanium dioxide pigment is contained in a polyethylene-based resin in a desired composition ratio, particularly preferably as a master batch. In order to prepare these master batches and compounds, a Banbury mixer, a kneader, a kneading extruder, a roll kneader or the like is usually used. These various kneaders may be used in combination of two or more.
[0048]
In the surface resin layer (A) of the support for light-sensitive material in the present invention, the titanium dioxide pigment usually contained is from the viewpoint of effectively improving the effect of the present invention, particularly the storage stability of the silver halide light-sensitive material. A titanium dioxide pigment having good dispersibility in a polyethylene resin is preferred. These titanium dioxide pigments have a particle surface calculated in the form of anhydrous metal oxide per titanium dioxide of 0.25% to 1.8% by weight, in particular 0.35% to 1.5% by weight. Of these, those treated with a hydrous metal oxide containing at least aluminum atoms and not more than 0.4% by weight (including 0) of silicon dioxide are preferable.
[0049]
Moreover, as described in Japanese Patent Publication No. 1-38292, the suspension is appropriately washed and pulverized to have a suspension electrical conductivity of 60 μmho (μΩ ^-1 ) / cm or less, especially 50μmho (μΩ ^-1 ) / cm or less is preferable, and as described in JP-A-3-2749, a particle diameter expressed by a number average diameter in a directional measurement by an electron microscope is preferably from 0.110 μm to 0.150 μm. As described in JP-B-5-71932, those produced by an external seed method are preferable, and in particular, the anatase type produced by the external seed method has a number average diameter in the range of 0.110 μm to 0.150 μm. Titanium dioxide pigment is preferred. Further, as described in JP-B 63-4489, it is preferable that the loss on drying of the titanium dioxide pigment under the condition of 110 ° C. for 2 hours is 0.35% by weight or less.
[0050]
Further, a so-called organic surface-treated titanium dioxide pigment whose surface is treated with an organic material is preferable. Specifically, the silane coupling agent, organopolysiloxane compound, alkanolamine compound, etc. described or exemplified in JP-B-60-3430 and JP-B-61-26652 are 0.05% by weight with respect to titanium dioxide. Titanium dioxide pigments that have been organic surface treated with a throughput in the range of ˜4.0% by weight are preferred.
[0051]
Particularly preferable organic surface treatment agents include γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxy. Silane, γ-methacryloxypropyltris (2-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N Silane coupling agents such as β- (aminoethyl) -γ-aminopropyltrimethoxysilane and γ-ureidopropyltriethoxysilane, alkylpolysiloxanes, alkylarylpolysiloxanes, alkylhydropolyenepolysiloxanes For example, organopolysiloxane compounds such as dimethylpolysiloxane, dimethylphenylpolysiloxane and methylhydropolyenepolysiloxane, polyether-modified siloxane described in JP-B-4-34139, and zircoaluminate described in JP-B-4-76463 Coupling agents, alkanolamine compounds such as triethanolamine and triisopropanolamine, polyhydric alcohol compounds such as trimethylolethane and trimethylolpropane, amide compounds described in JP-B-4-76464, and mixtures thereof. I can give you. The organic surface treatment may be performed by adding an organic surface treatment agent to the titanium dioxide slurry at any stage before drying the titanium dioxide slurry, or finely pulverizing the titanium dioxide pigment after drying. For example, an organic surface treatment agent may be added at the stage of fine pulverization with a fluid energy mill such as an air mill or a steam mill. The organic surface treatment agent may be added by dissolving and diluting in an appropriate solvent such as water, methanol, ethanol, acetone, or may be added without dilution.
[0052]
A method for preparing a masterbatch or compound (hereinafter sometimes simply referred to as a masterbatch of titanium dioxide pigment) comprising at least a titanium dioxide pigment and a polyethylene-based resin, which is preferably used in the practice of the present invention, is the present invention. In particular, in order to effectively and synergistically improve the storage stability of the silver halide light-sensitive material, two or more, particularly three, of the following methods are further performed by using the following methods. It has been clarified by studies by the present inventors that it is preferable to use them in combination.
[0053]
(1) As a polyethylene-based resin used for preparing a master batch or compound of a titanium dioxide pigment, one having an appropriate physical property relating to kneading properties of the titanium dioxide pigment and the polyethylene-based resin is selected. Specifically, the density is 0.917 g / cm. ^Three ~ 0.925g / cm ^Three The MFR is preferably 4.0 g / 10 min to 12 g / 10 min.
[0054]
(2) Use a suitable kneader for preparing a master batch or compound of titanium dioxide pigment. Specifically, for example, it is preferable to use a titanium dioxide pigment and a polyethylene resin having good kneadability as described in JP-A-6-110158.
[0055]
(3) In preparing a master batch or compound of a titanium dioxide pigment, a polyethylene resin composition is prepared in the presence of an appropriate amount of an appropriate antioxidant as described above.
[0056]
(4) In preparing a master batch or compound of titanium dioxide pigment, a polyethylene resin composition is prepared in the presence of an appropriate amount of an appropriate lubricant. Specifically, as the lubricant, it is preferable to use a fatty acid metal salt such as zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, zinc palmitate, zinc myristate, calcium palmitate, and particularly zinc stearate or / And magnesium stearate are preferred. Further, the existing amount is useful in the range of 0.1% by weight to 20% by weight with respect to the titanium dioxide pigment, and preferably in the range of 1% by weight to 7.5% by weight.
[0057]
The content of the titanium dioxide pigment usually contained in the surface resin layer of the support for photosensitive material in the present invention is 5% by weight or less based on the resin layer, and the sharpness of the printed image as the support for photosensitive material. On the other hand, if it is 40% by weight or more, the fluidity of the resin composition is lowered and the molding processability is deteriorated, and the glossiness of the appearance of the photographic print is undesirably decreased, preferably 7.5%. The range is from 30% by weight to 30% by weight, and particularly preferably from 10% by weight to 25% by weight.
[0058]
In addition, as a method for making an antioxidant present during the preparation of a titanium dioxide pigment masterbatch or compound, a so-called compound in which an antioxidant is previously contained in the resin to be used may be used, or a relatively high amount may be used. An appropriate amount of a so-called antioxidant masterbatch may be used, or an antioxidant may be added when producing a masterbatch or compound in a kneader. Also good. Furthermore, depending on the kind and content of the antioxidant to be used, the above methods may be appropriately combined.
[0059]
In the surface resin layer (A) of the support for photosensitive material in the present invention, it is preferable to contain an antioxidant from the viewpoint of remarkably improving the effect of the present invention, in particular, the preservability of the silver halide photosensitive material. . As a method of incorporating an antioxidant into the surface resin layer (A), a method using a titanium dioxide pigment masterbatch or compound containing an antioxidant, or a polyethylene-based resin for dilution previously oxidized to a desired concentration. A method of using a compound containing an inhibitor, a method of using a master batch of an antioxidant, or a method of using them together is preferable. When using a masterbatch or compound of titanium dioxide pigment, a certain proportion of the antioxidant present during the preparation of the masterbatch or compound, or in some cases, most of it is prepared in the preparation of the masterbatch or compound. In view of this point, it is necessary to design the type of antioxidant, the amount added, the method of addition, the timing of addition, and the like.
[0060]
Various antioxidants can be used as the antioxidant contained in the surface resin layer (A) of the support for photosensitive material in the present invention, but it effectively improves the storage stability of the silver halide photosensitive material. From the viewpoint, a hindered phenol antioxidant or an antioxidant containing a phosphorus atom in the molecule is preferable, and an antioxidant using them in combination is particularly preferable. Further, the content of the antioxidant in the surface resin layer (A) is useful in the range of 5 ppm to 1000 ppm as a ratio with respect to the polyethylene resin (a), but the range of 20 ppm to 600 ppm is preferable, and 50 ppm to A range of 400 ppm is particularly preferred. When there is too little content of antioxidant, there exists a tendency for the effect of this invention to be hard to be acquired and for moldability to worsen. On the other hand, when the content of the antioxidant is too large, the adhesion between the base paper and the resin layer tends to be insufficient, or the emulsion film between the silver halide photosensitive layer and the support tends to be insufficient. .
[0061]
Examples of the hindered phenol antioxidant preferably used in the present invention include 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-di-methylbenzyl) isocyanurate, 3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl- 4-hydroxybenzyl) benzene, tetrakis [methylene (3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)] methane, octadecyl-3,5-di-tert-butyl-4-hydroxy-hydrocinna Mate, 3,9-bis [1,1-dimethyl-2- [β-3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5.5] -Unde Cans. Examples of the antioxidant containing a phosphorus atom in the molecule preferably used in the present invention include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene-di-phosphite, tris. (2,4-di-tert-butylphenyl) phosphite, cyclic neopentanetetraylbis (4-methyl-2,6-di-tert-butylphenyl) phosphite, phenyl diisodecyl phosphite and the like. Further, two or more kinds of antioxidants may be used in combination depending on the characteristics of the antioxidant. Among these antioxidants, hindered phenolic oxidations having a molecular weight in the range of 600 to 1000 from the viewpoint of remarkably improving the storage stability of the silver halide photosensitive material and remarkably improving the emulsion film attachment. An antioxidant and an antioxidant containing a phosphorus atom in a molecule having a molecular weight of 500 or more are more preferable, and a hindered phenol antioxidant having a molecular weight in the range of 600 to 1000 and phosphorus in a molecule having a molecular weight of 500 or more. The combined use of an antioxidant containing atoms is particularly preferred. Further, from the viewpoint of remarkably improving the storage stability of the silver halide light-sensitive material, an antioxidant that is an isocyanurate compound is particularly preferable as the phenol-based antioxidant. Moreover, from the viewpoint of remarkably improving the storage stability of the silver halide light-sensitive material, as a ratio when using a hindered phenolic antioxidant and an antioxidant containing a phosphorus atom in the molecule, the total use amount thereof On the other hand, the combination ratio of the hindered phenol antioxidant is 20 wt% to 80 wt%, and the combination ratio of the antioxidant containing a phosphorus atom in the molecule is particularly preferably 80 wt% to 20 wt%.
[0062]
Further, the thickness of the front and back resin layers of the support for a photosensitive material in the present invention is not particularly limited, but the thickness of the front resin layer is useful in the range of 8 μm to 100 μm, from 12 μm to The range of 60 μm is preferable, and the range of 18 μm to 40 μm is particularly preferable. The thickness of the back resin layer is preferably set as appropriate within the range of obtaining the front resin layer and especially the curl balance. Generally, the range of 5 μm to 100 μm is useful, but the range of 8 μm to 60 μm is preferable, and 12 μm to A range of 40 μm is particularly preferred. In addition, the coating amount of the back resin layer is reduced compared to the front resin layer, and the difference in the resin coating amount between the front and back surfaces is 3 g / m. ² It is preferable to make it above.
[0063]
An undercoat layer is preferably provided on the surface resin surface of the photosensitive material support in the present invention. The undercoat layer preferably contains gelatin. Examples of gelatin include lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives such as gelatin reacted with an anhydride of dibasic acid. In addition, other hydrophilic polymers such as polyvinyl alcohol and starch can be used in combination with gelatin. Further, the pH of the undercoat coating solution is not particularly limited, but is preferably pH 8 or less, more preferably pH 7 or less from the viewpoint of storability of the photographic material. Further, it is preferable to use low molecular weight gelatin together as gelatin to be contained in the undercoat layer. The amount of low molecular weight gelatin used is preferably in the range of 20% to 80% by weight relative to the total amount of gelatin in the undercoat layer. The low molecular weight gelatin referred to here is one having a molecular weight of not more than 70,000, preferably 500 to 60,000, particularly preferably 1,000 to 40,000. The viscosity determined by the PAGI method is 1 centipoise (hereinafter simply referred to as cp). (Abbreviated) to 2 cp is preferred.
[0064]
The coating amount of the undercoat layer is not particularly limited, but the gelatin coating amount is 0.1 g% to 10 wt% of an aqueous coating solution of 1 g / m. ² ~ 40g / m ² It is better to apply, and in terms of the effect of improving the adhesion between the support and the silver halide photosensitive constituent layer, the solid weight is 0.005 g / m. ² ~ 2.0g / m ² The range is preferably 0.01 g / m ² ~ 1.0g / m ² Is more preferable, 0.02 g / m ² ~ 0.5g / m ² The range of is particularly preferable.
[0065]
Moreover, various additives can be contained in the undercoat layer. As preservatives, p-hydroxybenzoic acid ester compounds, benzisothiazolone compounds, isothiazolone compounds and the like described or exemplified in JP-A-1-102551, surfactants such as polyoxyethylene alkylphenyl ether sulfate, polyoxyethylene alkyl Anionic surfactants such as ether sulfates, alkylbenzene sulfonates, sulfosuccinic acid ester salts, nonionic surfactants such as saponins and alkylene oxides, described in Japanese Patent Publication No. 47-9303, US Pat. No. 3,589,906, etc. Fluorinated surfactants, active as amphoteric surfactants, hardening agents such as sulfobetaine-based amphoteric surfactants described in or exemplified in JP-A-1-66035, amino acids, amino alcohol esters, etc. Halogen compounds, vinyl sulfone compounds, aziridines Organic hardeners such as compounds, epoxy compounds, acryloyl compounds, isocyanate compounds, inorganic hardeners such as chromium alum, chromium sulfate, potassium alum, coupling agents disclosed in JP-A-5-66517, Antifoggants or stabilizers such as 1,5-dihydroxybenzoic acid and potassium hydroquinone sulfonate, latexes such as styrene / acrylic copolymer latex and vinylidene chloride copolymer latex, toning agents and fluorescent brightening agents , Matting agents, pH adjusting agents and the like can be contained in appropriate combinations.
[0066]
As a method of providing the undercoat layer on the surface resin layer (A), the resin layer (A) on the side where the silver halide photosensitive constituent layer is provided after the resin layer is coated on the traveling base paper surface and before winding. It is preferable to use a so-called on-machine method in which an undercoating liquid is applied to the surface and dried to provide an undercoating layer. Moreover, after winding up a resin-coated paper, after storing winding as needed, it can also carry out by what is called an off-machine method which provides an undercoat layer anew. Examples of apparatuses for applying the undercoating liquid include air knife coaters, roll coaters, bar coaters, wire bar coaters, blade coaters, slide hopper coaters, curtain coaters, gravure coaters, flexographic gravure coaters, and combinations thereof. Prior to the application of the undercoat layer, the resin surface may be subjected to other activation treatments such as flame treatment in addition to the high-frequency corona treatment. Various drying devices such as straight tunnel dryers, arch dryers, air loop dryers, hot air dryers such as sine curve air float dryers, dryers using infrared rays, heating dryers, microwaves, etc. Can give. Moreover, although drying conditions are arbitrary, generally it is performed at 40 to 150 degreeC for several seconds to 10 minutes.
[0067]
On the back resin layer (B) side of the support for photosensitive material in the present invention, after applying activation treatment such as high-frequency corona treatment and flame treatment, various backcoat layers are coated for antistatic purposes. be able to. For the back layer, inorganic antistatic agents such as colloidal silica, colloidal alumina, hectorite clay colloids and mixtures thereof described or exemplified in JP-A-5-107688, binders, organic antistatic agents or binders and electrification A water-soluble synthetic polymer compound having a carboxyl group or a sulfone group or a salt thereof, or a hydrophilic synthetic polymer colloid substance or a salt thereof described in JP 59-214849 A Polymer latex described or exemplified in JP-A-59-214849, starch described or exemplified in JP-A-58-14131, polyvinylpyrrolidone described or exemplified in JP-A-58-45248, JP-A-62-2 Polymers such as polyvinyl alcohol described or exemplified in 220950 and chitosan described or exemplified in JP-A-63-189859 It can be incorporated in combination curing agent according or exemplified in Japanese Patent Publication No. Sho 58-56859, matting agents according or exemplified in JP-A-59-21849, a surfactant or the like as appropriate.
[0068]
The base paper used in the practice of the present invention is preferably natural pulp paper mainly composed of normal natural pulp. Moreover, the mixed paper which consists of a synthetic pulp and a synthetic fiber by using a natural pulp as a main component may be sufficient. These natural pulps are described or exemplified in JP-A-58-37642, JP-A-60-67940, JP-A-60-69649, JP-A-61-35442, etc. It is advantageous to use such appropriately selected natural pulp. Natural pulp was subjected to normal bleaching treatment of chlorine, hypochlorite, chlorine dioxide bleaching, alkali extraction or alkali treatment, and if necessary, oxidative bleaching treatment with hydrogen peroxide, oxygen, etc., and combinations thereof. Wood pulp of softwood pulp, hardwood pulp, mixed softwood hardwood pulp is advantageously used, and various kinds such as kraft pulp, sulfite pulp, soda pulp can be used, but hardwood bleached craft is particularly advantageously used It is done.
[0069]
Various additives can be incorporated into the base paper used in the practice of the present invention when preparing the paper slurry. Fatty acid metal salt or / and fatty acid, alkyl ketene dimer emulsion or / and epoxidized higher fatty acid amide, alkenyl or alkyl succinic anhydride emulsion, rosin derivative described or exemplified in JP-B-62-7534 As a dry paper strength enhancer, anionic, cationic or amphoteric polyacrylamide, polyvinyl alcohol, cationized starch, vegetable galactomannan, etc., as a wet paper strength enhancer, polyamine polyamide epichlorohydrin resin, etc., as a filler, clay , Kaolin, calcium carbonate, titanium oxide, etc. as fixing agents, water-soluble aluminum salts such as aluminum chloride and sulphated sulfuric acid, etc., pH regulators as caustic soda, sodium carbonate, sulfuric acid, etc., other JP-A-63-204251 In Japanese Patent Laid-Open No. 1-266537, etc. It is advantageously allowed to contain in combination illustrative colored pigments, coloring dyes, fluorescent brightening agents as appropriate.
[0070]
The base paper is coated with a composition comprising various water-soluble polymers or hydrophilic colloids or latexes, antistatic agents and additives, such as size press or tab size press, blade coating, air knife coating, etc. Can be contained. As water-soluble polymers or hydrophilic colloids, starch polymers, polyvinyl alcohol-based polymers, gelatin-based polymers, polyacrylamide-based polymers, cellulose-based polymers, etc. described or exemplified in JP-A No. 1-266537, as emulsions and latexes, Petroleum resin emulsion, emulsion or latex of copolymer comprising at least ethylene and acrylic acid (or methacrylic acid) as described or exemplified in JP-A-55-4027 and JP-A-1-80538, styrene -Emulsions or latexes of butadiene, styrene-acrylic, vinyl acetate-acrylic, ethylene-vinyl acetate, butadiene-methyl methacrylate copolymers and their carboxy-modified copolymers, such as sodium chloride as an antistatic agent , Alkali metal salts such as potassium chloride, alkaline earth metal salts such as calcium chloride and barium chloride, colloidal metal oxides such as colloidal silica, organic antistatic agents such as polystyrene sulfonate, etc., pigments such as clay and kaolin , Calcium carbonate, talc, barium sulfate, titanium oxide, etc., as a pH adjuster, hydrochloric acid, phosphoric acid, citric acid, caustic soda, etc., and other appropriate additives such as the above-mentioned coloring pigments, coloring dyes, fluorescent whitening agents, etc. The inclusion is advantageous.
[0071]
In addition, as the base paper used in the practice of the present invention, the paper thickness non-uniformity index Rpy defined below is preferably 250 mV or less, more preferably 200 mV or less, and most preferably 150 mV or less. . The film thickness nonuniformity index Rpy referred to here is an electronic micrometer using a film thickness measuring instrument that moves a sample between two spherical styluses and measures the thickness variation of the sample as an electrical signal via the electronic micrometer. Under the condition that the sensitivity range is ± 15μm / ± 3V, the thickness variation in the paper making direction of the sample is measured by scanning at a constant speed of 1.5m / min in the paper making direction of the sample after zero adjustment. The signal value is subjected to fast Fourier transform using a Hanning window as a time window using an FFT analyzer, and a power spectrum (unit: mV) obtained by adding and averaging 128 times. ² ) And the power value in the frequency range of 2 Hz to 25 Hz is summed and multiplied by 2/3 to obtain a value (unit: mV).
[0072]
As a method for producing a base paper having a film thickness nonuniformity index Rpy of 250 mV or less, which is preferably used in the practice of the present invention, specifically, appropriately hardened hardwood pulp is 30% by weight or more, preferably 50% by weight or more. Use. Specifically, for example, as a pulp, fiber length of pulp after beating (length-weighted average fiber length measured in accordance with JAPAN TAPPI paper pulp test method No. 52-89 “paper and pulp fiber length test method”) However, it is preferable to use hardwood kraft pulp beaten to 0.45 mm to 0.62 mm, particularly preferably 0.48 mm to 0.59 mm. It is preferable to use a papermaking process using an appropriate papermaking method for the stock slurry to which the internal chemicals are added, and to make a base paper so that a uniform formation can be obtained by a long paper machine. Specifically, for example, using a long web paper machine having an appropriate upper dewatering mechanism as described or exemplified in JP-A-61-284762, which gives an appropriate turbulence to the stock slurry, As a press, a multi-stage wet press, preferably a wet press with three or more stages, and a smooth paper roll at the final stage of the press part can be combined with an appropriate paper making method so that a uniform texture can be obtained. The paper sheet is then subjected to calendering using a machine calendar, super calender, thermal calendar or the like after paper making, whereby a base paper having a film thickness nonuniformity index Rpy of 250 mV or less can be produced.
[0073]
As a base paper mainly composed of natural pulp used in the practice of the present invention, the paper making direction with a cut-off value of 0.8 mm measured using a stylus type three-dimensional surface roughness meter on the front side of the base paper is used. Center plane average roughness SRa (Hereinafter, the nomenclature of center plane average roughness SRa in the paper making direction at a cutoff value of 0.8 mm measured using a stylus type three-dimensional surface roughness meter on the front side of the base paper, The average surface roughness SRa may be abbreviated to 1.45 μm or less, preferably 1.40 μm or less, more preferably 1.35 μm or less, and even more preferably 1.25 μm or less. Is particularly preferred. The center surface average roughness SRa at a cutoff value of 0.8 mm measured using a stylus type three-dimensional surface roughness meter in the present specification is defined by Equation 1.
[0074]
[Expression 1]

[0075]
In Equation 1, Wx represents the length of the sample surface area in the X-axis direction (paper making direction), Wy represents the length of the sample surface area in the Y-axis direction (direction perpendicular to the paper making direction), and Sa represents the sample surface. Represents the area of the area.
[0076]
As a method for producing a base paper having a center surface average roughness SRa of 1.45 μm or less that is preferably used in the practice of the present invention, specifically, a hardwood pulp that is easily smooth, preferably a hardwood sulfite pulp is used. Use 15% by weight or more, preferably 30% by weight or more, perform multi-stage tension pressing in the middle of drying wet paper, and after making the base paper, use machine calendar, super calendar, thermal calendar, etc. After performing calendar processing, for example, machine calendar processing or / and thermal machine calendar processing as the first series of calendar processing on the base paper, and further performing machine calendar processing as necessary for the second and subsequent series of calendar processing, The center surface average roughness SRa is 1.45 μm by performing the thermal soft calender process described or exemplified in Japanese Patent Laid-Open No. 4-110939. It is possible to manufacture the bottom of the base paper. Also, various water-soluble polymers, hydrophilic colloids, or polymer latexes in the base paper or on the base paper are applied in a solid press amount of 1.0 g / kg by size press or tab size press, blade coating, air knife coating or the like. m ² Above, especially 2.2g / m ² It is preferable to contain or coat the above.
[0077]
The density of the base paper of the support for photosensitive material in the present invention is 0.90 g / cm. ^Three ~ 1.15g / cm ^Three Is preferred, 0.95 g / cm ^Three ~ 1.15g / cm ^Three Is more preferable, and 1.00 g / cm ^Three ~ 1.10g / cm ^Three The range of is particularly preferable. The density of the base paper is 0.90 g / cm ^Three If it is less than 1, a surface support with good surface quality and excellent smoothness cannot be obtained, and the density of the base paper is 1.15 g / cm. ^Three If it is larger, the photosensitive material and its print become weak, which is a problem. Further, regarding the thickness of the base paper used in the practice of the present invention, there is no particular deadline, but the basis weight is 40 g / m. ² ~ 250g / m ² Is useful, 70g / m ² ~ 220g / m ² Are preferred.
[0078]
The support for the photosensitive material in the present invention is coated with various silver halide photosensitive constituent layers, for color photographic printing paper, for black and white photographic printing paper, for phototyped printing paper, for copy photographic paper, for reversal photographic material, The silver salt diffusion transfer method can be used for various purposes such as negatives, positives, and printing materials. For example, a silver chloride, silver bromide, silver chlorobromide, silver iodobromide, or silver chloroiodobromide emulsion layer can be provided. Multilayer silver halide color photographic constituent layers can be provided by incorporating color couplers in the silver halide photographic emulsion layer. Further, a photographic constituent layer for silver salt diffusion transfer method can be provided. As binders for these silver halide photosensitive constituent layers, hydrophilic polymer substances such as polyvinyl pyrrolidone, polyvinyl alcohol, and polysaccharide sulfate compounds can be used in addition to ordinary gelatin. The silver halide photosensitive constituent layer may contain various additives. Examples include sensitizing dyes such as cyanine dyes and merocyanine dyes, chemical sensitizers such as water-soluble gold compounds and sulfur compounds, antifoggants or stabilizers such as hydroxy-triazolopyrimidine compounds and mercapto-heterocyclic compounds. Formalin, vinyl sulphone compounds, aziridine compounds as hardening agents, alkylbenzene sulphonate and sulfosuccinic acid ester salts as coating aids, dialkyl hydroquinone compounds as antifouling agents, other fluorescent whitening agents, improved sharpness A dye, an antistatic agent, a pH adjusting agent, a fogging agent, and a water-soluble iridium, a water-soluble rhodium compound, and the like can be contained in appropriate combinations during the formation and dispersion of silver halide.
[0079]
Further, the effect of the present invention, in particular, the effect of remarkably improving the storage stability by remarkably suppressing the generation of fog due to storage of the silver halide photosensitive material, is that the silver halide is mainly composed of silver chloride as the silver halide photosensitive layer. By using a silver halide photosensitive layer, particularly a silver halide photosensitive layer having a silver chloride content of 90 mol% or more, particularly 95 mol% or more, it is achieved more synergistically and more remarkably. Is done. Further, the effect of the present invention, in particular, the effect of remarkably improving the storage stability by remarkably suppressing the occurrence of fog due to the storage of the silver halide light-sensitive material, is that the silver halide color photographic composition By using a multi-layer silver halide color photographic composition layer comprising a layer, particularly a blue-sensitive silver halide photographic emulsion layer having a silver chloride content of blue-sensitive silver halide of 90 mol% or more, particularly 95% mol or more, It is achieved more synergistically and even more markedly.
[0080]
The light-sensitive material in the present invention is exposed, developed, stopped, fixed, and bleached as described in "Photosensitive material and handling method" (Kyoritsu Shuppan, Goro Miyamoto, Photographic Technology Course 2) according to the light-sensitive material. , Stable processing can be performed. The multilayer silver halide color photographic material may be processed with a developer containing a development accelerator such as benzyl alcohol, thallium salt or phenidone, or may be processed with a developer substantially free of benzyl alcohol. it can.
[0081]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the content of this invention is not restricted to an Example.
[0082]
Examples 1 to 10 and Comparative Examples 1 to 3
Fiber length of pulp after beating bleached hardwood bleached kraft pulp (expressed in length-weighted average fiber length measured according to JAPAN TAPPI paper pulp test method No. 52-89 "Paper and pulp fiber length test method") After beating so as to be 0.56 mm, 3 parts by weight of cationized starch, 0.2 part by weight of anionized polyacrylamide, and 0.4 part of alkyl ketene dimer emulsion (as ketene dimer part) per 100 parts by weight of pulp A stock slurry was prepared by adding 0.4 parts by weight of polyamide epichlorohydrin resin, 1.5 parts by weight of amphoteric polyacrylamide (molecular weight 1 million), and appropriate amounts of fluorescent brightener, blue dye and red dye. After that, a paper web was formed while giving appropriate turbulence on a long paper machine running the stock slurry at 200 m / min, and the linear pressure was adjusted in the range of 15-100 kgf / cm in the wet part. After performing a three-stage wet press, it was treated with a smoothing roll, followed by a two-stage tension press in which the linear pressure was adjusted in the range of 30 to 70 kgf / cm in the subsequent drying part, and then dried. Then, during the drying, 25 g / m of size press liquid of the following (Formulation A) to (Formulation E) was added. ² Size-pressed, dried so that the final base paper moisture is 8% by weight in absolute dry moisture, machine calendered at a linear pressure of 70 kgf / cm, and the basis weight is 170 g / m ² , Density is 1.04g / cm ^Three A base paper for a photosensitive material support having a center surface average roughness SRa of 1.20 μm was produced.
[0083]
Size press solution (formulation A): carboxy-modified polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name; Gohsenal T-330, hereinafter abbreviated as PVA-1) 4% by weight, fluorescent whitening agent 0.05% by weight, coloring A size press solution consisting of 0.002% by weight of dye, 4% by weight of sodium chloride and the remaining weight% of water.
[0084]
Size press solution (formulation B): 3% by weight of carboxy-modified polyvinyl alcohol (PVA-1), carboxy-modified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name: Kuraray KL506, hereinafter abbreviated as PVA-2), 2% by weight, fluorescence increase A size press solution comprising 0.05% by weight of whitening agent, 0.002% by weight of coloring dye, 4% by weight of sodium chloride and the remaining weight% of water.
[0085]
Size press solution (formulation C): carboxy-modified polyvinyl alcohol (PVA-1) 2% by weight, carboxy-modified polyvinyl alcohol (PVA-2) 4% by weight, optical brightener 0.05% by weight, colored dye 0.002% by weight A size press solution consisting of 4% by weight of sodium chloride, 4% by weight of sodium chloride and the remaining weight% of water.
[0086]
Size press solution (compound D): 1% by weight of carboxy-modified polyvinyl alcohol (PVA-1), 7% by weight of carboxy-modified polyvinyl alcohol (PVA-2), 0.05% by weight of optical brightener, 0.002% by weight of coloring dye A size press solution consisting of 4% by weight of sodium chloride, 4% by weight of sodium chloride and the remaining weight% of water.
[0087]
Size press solution (formulation E): 10% by weight of carboxy-modified polyvinyl alcohol (PVA-2), 0.05% by weight of optical brightener, 0.002% by weight of coloring dye, 4% by weight of sodium chloride and the remaining weight% of water Size press liquid consisting of.
[0088]
Next, after the corona discharge treatment was performed on the base paper surface (back surface) opposite to the side on which the silver halide photosensitive constituent layer was to be coated, a low-density polyethylene resin [density 0.924 g / cm ^Three , MFR = 1 g / 10 min] 30 parts by weight and high density polyethylene resin (density 0.967 g / cm ^Three , MFR = 15 g / 10 min) A compound resin composition comprising 70 parts by weight with a resin temperature of 320 ° C. and a resin thickness of 25 μm at a running speed of the base paper of 200 m / min, using a melt extrusion coating machine, It was melt extrusion coated at a press roll linear pressure of 40 kgf / cm. At this time, a cooling roll roughened by a liquid honing method was used as a cooling roll, and the cooling roll was operated at a cooling water temperature of 12 ° C. Subsequently, the surface resin layer was coated as described below to produce a resin-coated paper.
[0089]
The base paper surface (surface) on the side where the silver halide photosensitive constituent layer is provided is subjected to corona discharge treatment, and then the following blended composition (BL-1) is applied to the surface at a resin temperature of 315 ° C. to a thickness of 30 μm. Using a melt extrusion coater at a speed of 200 m / min, melt extrusion coating was performed with a linear pressure of 40 kgf / cm between the cooling roll and the press roll. At this time, as a cooling roll, a chrome-plated surface having a fine roughness was used and operated at a cooling water temperature of 12 ° C. Also, the melt extrusion coating of the front and back resin compositions was performed by a so-called tandem method in which sequential extrusion coating is performed.
[0090]
Formulation composition (BL-1): 17 parts by weight of the following masterbatch (MB-1W) pellets containing the titanium dioxide pigment, 8 parts by weight of the following masterbatch (MB-1B) pellets containing the titanium dioxide pigment and ultramarine blue, and the following A blended composition in which 75 parts by weight of polyethylene resin (R-2) pellets are well mixed (dry blended).
[0091]
Masterbatch (MB-1W): The surface of titanium dioxide particles is hydrous aluminum oxide (Al per titanium dioxide) ₂ O _Three 0.5 wt.%) And surface milled and steam mill pulverized, an anatase titanium dioxide pigment 50 wt.% In number average diameter of 0.120 μm by electron microscope, 47.5% of the following polyethylene resin (R-1) Wt% and zinc stearate 2.5 wt% as antioxidant, 200 ppm 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethyl-benzyl) cyanurate (hereinafter, In the presence of 200 ppm of tris (2,4-di-tert-butylphenyl) phosphite (hereinafter abbreviated as AO-2) and kneaded well at 150 ° C. using a Banbury mixer, Master batch produced by cooling and pelletizing.
[0092]
Masterbatch (MB-1B): 50% by weight of the above titanium dioxide pigment, 46.25% by weight of the following polyethylene resin (R-1), 1.25% by weight of ultramarine (Daiichi Kasei Kogyo Co., Ltd., # 2000) and stearin The blended zinc (2.5% by weight) is thoroughly kneaded at 150 ° C. using a Banbury mixer in the presence of 200 ppm of antioxidant (AO-1) and 200 ppm of antioxidant (AO-2), cooled and pelletized. Masterbatch manufactured by
[0093]
Polyethylene resin (R-1): Density 0.920 g / cm ^Three , MFR = 8.5 / 10 min, hexane extraction amount = 1.5 wt%, high pressure low density polyethylene resin of tubular method.
[0094]
Polyethylene resin (R-2): Density 0.992 g / cm ^Three , MFR = 4.0 / 10 min, hexane extraction amount = 1.3 wt%, autoclave low density polyethylene resin.
[0095]
Further, after the front and back resin layers are processed and wound up, the back resin layer surface of the resin-coated paper is subjected to a corona discharge treatment, and the following back layer coating solution (BC-1) is 0.3 g as dry weight. / m ² On-machine coating was performed with a coating amount of
[0096]
Back layer coating solution (BC-1); styrene: 2-ethylhexyl acrylate: methacrylic acid: acrylamide = 57: 39: 2.5: 1.5 (% by weight) composition 50% by weight aqueous dispersion of polymer latex 2 g of liquid and 30% by weight of colloidal silica (trade name Snowtex 20 manufactured by Nissan Chemical Co., Ltd.) and styrene-maleic anhydride copolymer (trade name KS-1570, manufactured by Arakawa Chemical Co., Ltd., molecular weight of about 70,000) 12 g of a 9 wt% dispersion prepared by emulsifying and dispersing aluminum hydroxide microcrystals having a mean particle size of 1 μm and an oil absorption of 35 cc / 100 g, and an epoxy hardener. Including 3.2 g of 10% methanol solution (trade name NER-010, manufactured by Nagase Sangyo Co., Ltd.) and 0.8 g of 5% water / methanol mixed solution of 2-ethylhexylsulfosuccinate, Coating solution prepared in 100g in.
[0097]
After coating the back layer and before winding the resin-coated paper, the front side resin surface was subjected to corona discharge treatment with the corona treatment amount shown in Table 1, and then the undercoat layer coating liquid (SC -1) as the gelatin coating amount (dry weight), 0.06 g / m ² The on-machine coating was uniformly applied at a coating amount to become.
[0098]
Undercoat layer coating solution (SC-1): 1.2 g of lime-processed gelatin, 0.3 g of low molecular weight gelatin (manufactured by Nitta Gelatin Co., Ltd., P-3226), 0.3% of 10% by weight methanol solution of butyl paraoxybenzoate. A coating solution containing 3 g and 0.45 g of a 5 wt% mixture of methanol and water of sulfosuccinic acid-2-ethylhexyl ester salt, and the total amount was adjusted to 100 g with water.
[0099]
Next, the support was subjected to an electrification treatment by a wire electrification method so that the surface potential of the undercoat layer surface became plus 0.3 kV. Furthermore, in an on-machine system, a blue-sensitive emulsion layer containing the following yellow coloring couplers, in order, adjacent to the undercoat layer of the photosensitive material support, an intermediate layer containing a color mixing inhibitor, and a green containing a magenta coloring coupler. Each coating solution for the emulsion layer, the first ultraviolet absorbing layer containing an ultraviolet absorber, the red sensitive emulsion layer containing a cyan coloring coupler, the second ultraviolet absorbing layer containing an ultraviolet absorber, and the protective layer was applied at a coating speed of 200 m / min. Seven layers from E-bar for multi-layer coating are applied simultaneously, and the total amount of gelatin is 8.5 g / m. ² A color photographic paper was created. As a hardening agent, 2,4-dichloro-6-hydroxy-s-triazine sodium salt (added as an aqueous solution) was used, and halogenated so as to be 1.65% by weight based on the total amount of gelatin. The silver color photographic paper was appropriately distributed and contained in each layer in consideration of photographic characteristics, storage stability and the like.
[0100]
The blue-sensitive emulsion layer was prepared by ripening and preparing a monodispersed cubic host silver chloride agent having an average grain size of 1.1 μm in the presence of an appropriate amount of potassium hexachloroiridium (III), and further 0.05 A neutral layered silver halide emulsion prepared by first ripening and adding a 0.05 μm silver bromide fine grain emulsion at a mol% ratio and sulfur-sensitized to the optimum sensitivity was 0.4 g / m in terms of silver nitrate. ² Contains 1.5g / m of gelatin ² In addition to a yellow color coupler, it contains an appropriate amount of a stabilizer, a blue-sensitive sensitizing dye, a coating aid, a hardener, a thickener and the like. The intermediate layer is gelatin 1.0g / m ² In addition, an appropriate amount of color mixing inhibitor, coating aid, thickener, hardener and the like are included. The viscosities of the coating solutions for the blue-sensitive emulsion layer and the intermediate layer were adjusted to 5.5 cp and 100 cp, respectively, and the wet coating amount was 35 g / m, respectively. ² And 5g / m ² It was painted with.
[0101]
The green-sensitive emulsion layer is an acid composed of monodisperse cubic silver chloride, which is sulfur-sensitized to an optimum sensitivity of 0.45 μm in average grain size, prepared by the first thermal process in the presence of an appropriate amount of potassium hexachlororhodium (III). Method Silver halide emulsion in silver nitrate amount 0.5g / m ² Contains 1.2g / m of gelatin ² In addition to a magenta color coupler, an appropriate amount of a stabilizer, a green sensitizing dye, a sharpness improving dye, a coating aid, a hardener, a thickener and the like are included. The first UV absorbing layer is 1.3g / m of gelatin. ² In addition, an appropriate amount of an ultraviolet absorber, a coating aid, a thickener, a hardener, and the like are included. The viscosities of the coating solutions for the green emulsion layer and the first UV absorbing layer are adjusted to 50 cp and 60 cp, respectively, and the wet coating amount is 15 g / m, respectively. ² And 7g / m ² It was painted with.
[0102]
The red emulsion layer is a silver halide emulsion produced in exactly the same manner as the green-sensitive silver halide emulsion. The silver nitrate amount is 0.35 g / m. ² In addition, gelatin 1.1g / m ² In addition to a cyan coloring coupler, an appropriate amount of a stabilizer, a red sensitizing dye, a sharpness improving dye, a coating aid, a hardener, a thickener and the like are included. The second UV absorbing layer is 0.5g / m gelatin. ² In addition, an appropriate amount of an ultraviolet absorber, a coating aid, a thickener, a hardener, and the like are included. The protective layer is gelatin 1.4g / m ² In addition, an appropriate amount of coating aids, thickeners, hardeners and the like are included. The viscosities of the coating solutions for the red emulsion layer, the second ultraviolet absorbing layer and the protective layer are adjusted to 30 cp, 60 cp and 90 cp, respectively, and the wet coating amount is 14 g / m. ² , 7g / m ² And 7 g / m ² It was painted with.
[0103]
The storability of the color photographic paper produced as described above and the evaluation method with an emulsion film were evaluated by the methods described below.
[0104]
As a method for evaluating the storability of color photographic paper, the produced color photographic paper is dry-thermo-heated at 65 ° C. for 5 days, and then the unexposed color photographic paper is subjected to color development, bleaching / fixing, and stable color development processing. After drying, the density of yellow fog was measured and evaluated. The color development processing was performed in the order of color development (45 seconds) → bleaching / fixing (45 seconds) → stable (1 minute 30 seconds) → drying.
[0105]
As an evaluation method for emulsion layers of photographic constituent layers, the produced color photographic paper was stored at 40 ° C. at room temperature for 5 days, exposed to a gray density of 1.5 or more, and evaluated with emulsion film after color development. did. With emulsion film, the surface of the emulsion is scratched at 1 cm intervals vertically and horizontally with a nail after color development, and scratches are made in a grid pattern. Evaluation was based on the percentage (%) of the area where peeling did not occur (the larger the value, the stronger the emulsion film, and the smaller the value, the weaker the emulsion film). The evaluation criteria are as follows.
100% to 97%: There is no or almost no peeling of the emulsion layer, and the emulsion film is good.
Less than 97% to 80%: There is slight peeling of the emulsion layer, but there is no practical problem.
Less than 80% to 60%: Peeling of emulsion layer is slightly high, but practically lower limit.
Less than 60%: There is much peeling of the emulsion layer, and there is a practical problem with the emulsion film.
[0106]
The obtained results are shown in Table 1.
[0107]
[Table 1]

[0108]
In Table 1, (Note 1) to (Note 4) are as follows.
[0109]
(Note 1) (Composition A) to (Composition E) of the size press solution represent the same as those described in paragraphs 0083 to 0087 used when producing the base paper for the photosensitive material support.
[0110]
(Note 2) The corona treatment amount is the corona output amount (watt · minute) of the corona discharge treatment described in paragraph 0097 applied to the surface resin layer surface before coating the undercoat layer when manufacturing the photosensitive material support. / m ² ).
[0111]
(Note 3) The degree of polyethylene surface oxidation or support surface oxidation represents the degree of polyethylene surface oxidation (%) or the degree of support surface oxidation (%) specified in this specification.
[0112]
(Note 4) The oxygen permeability of the support is the oxygen permeability (cc / m) of the support specified in this specification. ² / day).
[0113]
From the results of Table 1, the front side of the base paper mainly composed of natural pulp is coated with a resin layer (A) containing a polyethylene resin (a), and the back side is a resin layer containing a resin (b) capable of forming a film ( B) a photosensitive material support coated with B), having a polyethylene surface oxidation degree of 33% to 53% and an oxygen permeability of the support of 450 cc / m ² The support for light-sensitive materials (Examples 1 to 10) in the present invention, which is less than / day, has significantly improved yellow fog generation and remarkably improved storage stability with respect to a silver halide photosensitive layer. It can be clearly seen that this is an excellent support for a photosensitive material in which the adhesion is remarkably improved.
Further, the front side of the base paper mainly composed of natural pulp is covered with a resin layer (A) containing a polyethylene resin (a), and the back side is covered with a resin layer (B) containing a resin (b) capable of forming a film. A silver halide light-sensitive material in which a silver halide light-sensitive constituent layer is coated on the front side of the support for the light-sensitive material, the surface oxidation degree of the support is 33% to 53%, and the oxygen permeability of the support is 450cc / m ² The silver halide light-sensitive materials (Examples 1 to 10) of the present invention that are less than / day are significantly improved in yellow fog generation and markedly improved in the storage stability of the silver halide light-sensitive layer. It can be clearly seen that the film support is an excellent support for a light-sensitive material in which the film is stably improved remarkably.
[0114]
Further, among the photosensitive material support and silver halide photosensitive material in the present invention, the degree of polyethylene surface oxidation from the viewpoint of the storage stability for the silver halide photosensitive layer or the storage stability of the silver halide photosensitive layer and the effect of improving the emulsion film attachment. Alternatively, it is well understood that the support surface oxidation degree is preferably 35% to 50%, particularly preferably 37% to 47%.
Further, among the support for light-sensitive material and the silver halide light-sensitive material of the present invention, from the viewpoint of storage stability for the silver halide light-sensitive layer, storage stability of the silver halide light-sensitive layer, and improvement effect with emulsion film. Oxygen permeability is 400cc / m ² / day or less is preferable, 350cc / m ² / day or less is more preferable, 300cc / m ² It can be clearly seen that those below / day are particularly preferred.
[0115]
On the other hand, when the polyethylene surface oxidation degree or the support surface oxidation degree is less than 33% (Comparative Example 1) or higher than 53% (Comparative Example 2), the support for light-sensitive materials other than the present invention and silver halide It can be seen that the light-sensitive material is problematic because it is weak in emulsion film formation, has a lot of yellow fog, and has poor storage stability with respect to the silver halide photosensitive layer or storage stability of the silver halide photosensitive layer.
The oxygen permeability of the support is 450 cc / m ² In the case of more than / day (Comparative Example 3), the support for the light-sensitive material and the silver halide light-sensitive material other than the present invention generate a lot of yellow fog, and the storability to the silver halide light-sensitive layer or the silver halide light-sensitive layer It is well understood that this is a problem due to poor properties and that the emulsion film tends to be weakened.
[0116]
Examples 11-25
Example 9 except that the following blending compositions (BL-2) to (BL-16) were used instead of the blending composition (BL-1) for covering the front side of the base paper used in Example 9 It carried out similarly. The oxygen permeability of the produced color photographic paper support is 350 cc / m each. ² / day.
[0117]
Formulation composition (BL-2): 17 parts by weight of the following master batch (MB-2W) containing titanium dioxide pigment, 8 parts by weight of the following master batch (MB-2B) containing titanium dioxide pigment and ultramarine blue, and the following A blended composition in which 75 parts by weight of polyethylene resin (R-2) pellets are well mixed (dry blended).
[0118]
Masterbatch (MB-2W): The surface of titanium dioxide particles is hydrous aluminum oxide (Al per titanium dioxide) ₂ O _Three 0.5 wt.%) And surface milled and steam mill pulverized, an anatase titanium dioxide pigment having a number average diameter of 0.120 μm with an electron microscope of 50 wt.%, The polyethylene resin (R-1) 47.5 A masterbatch produced by kneading, at 150 ° C., with a Banbury mixer in the presence of 50 ppm by weight and zinc stearate in the presence of 50 ppm of antioxidant (AO-1), cooling and pelletizing.
[0119]
Master batch (MB-2B): 50% by weight of the titanium dioxide pigment, 46.25% by weight of the polyethylene resin (R-1), 1.25% by weight of ultramarine (Daiichi Kasei Kogyo Co., Ltd., # 2000) and stearin A master batch prepared by kneading 2.5% by weight of blended zinc well at 150 ° C. using a Banbury mixer in the presence of 75 ppm of antioxidant (AO-1), cooling and pelletizing.
[0120]
Polyethylene resin (R-2): Density 0.992 g / cm ^Three , MFR = 4.0 g / 10 min, hexane extraction amount = 1.3 wt%, autoclave low density polyethylene resin.
[0121]
Formulation composition (BL-3): Formulation composition except that the following polyethylene resin (R-3) is used instead of the polyethylene resin (R-2) used for the preparation of the formulation composition (BL-2) ( Formulation composition prepared in exactly the same manner as BL-2).
[0122]
Polyethylene resin (R-3): An antioxidant (AO-1) in an amount of 10 ppm with respect to the polyethylene resin is added in advance to the polyethylene resin (R-2). Polyethylene resin prepared by mixing and kneading.
[0123]
Formulation composition (BL-4): Formulation composition except that the following polyethylene resin (R-4) is used instead of the polyethylene resin (R-2) used for the preparation of the formulation composition (BL-2) ( Formulation composition prepared in exactly the same manner as BL-2).
[0124]
Polyethylene resin (R-4): An antioxidant (AO-1) in an amount of 20 ppm with respect to the polyethylene resin is added in advance to the polyethylene resin (R-2). Polyethylene resin prepared by mixing and kneading.
[0125]
Formulation composition (BL-5): Formulation composition except that the following polyethylene resin (R-5) is used instead of the polyethylene resin (R-2) used for the preparation of the formulation composition (BL-2) ( Formulation composition prepared in exactly the same manner as BL-2).
[0126]
Polyethylene resin (R-5): An antioxidant (AO-1) in an amount of 50 ppm with respect to the polyethylene resin is added in advance to the polyethylene resin (R-2). Polyethylene resin prepared by mixing and kneading.
[0127]
Formulation composition (BL-6): Instead of the polyethylene resin (R-2) used for the preparation of the formulation composition (BL-2), the formulation composition except for using the following polyethylene resin (R-6) ( Formulation composition prepared in exactly the same manner as BL-2).
[0128]
Polyethylene resin (R-6): An antioxidant (AO-1) in an amount such that the content in the surface resin layer of the resin-coated paper is 100 ppm relative to the polyethylene resin is previously added to the polyethylene resin (R-2). Polyethylene resin prepared by mixing and kneading.
[0129]
Formulation composition (BL-7): Instead of the polyethylene resin (R-2) used for the preparation of the formulation composition (BL-2), the formulation composition except for using the following polyethylene resin (R-7) ( Formulation composition prepared in exactly the same manner as BL-2).
[0130]
Polyethylene resin (R-7): An antioxidant (AO-1) in an amount of 200 ppm with respect to the polyethylene resin is added in advance to the polyethylene resin (R-2). Polyethylene resin prepared by mixing and kneading.
[0131]
Formulation composition (BL-8): A formulation composition except that the following polyethylene resin (R-8) was used instead of the polyethylene resin (R-2) used in the preparation of the formulation composition (BL-2) ( Formulation composition prepared in exactly the same manner as BL-2).
[0132]
Polyethylene resin (R-8): An amount of antioxidant (AO-1) in the surface resin layer of the resin-coated paper is 400 ppm with respect to the polyethylene resin in advance in the polyethylene resin (R-2). Polyethylene resin prepared by mixing and kneading.
[0133]
Formulation composition (BL-9): Instead of the polyethylene resin (R-2) used in the preparation of the formulation composition (BL-2), the formulation composition (R-9) was used except that the following polyethylene resin (R-9) was used. Formulation composition prepared in exactly the same manner as BL-2).
[0134]
Polyethylene resin (R-9): An antioxidant (AO-1) in an amount of 600 ppm with respect to the polyethylene resin is added in advance to the polyethylene resin (R-2). Polyethylene resin prepared by mixing and kneading.
[0135]
Formulation composition (BL-10): Formulation composition except that the following polyethylene resin (R-10) is used instead of the polyethylene resin (R-2) used for the preparation of the formulation composition (BL-2) ( Formulation composition prepared in exactly the same manner as BL-2).
[0136]
Polyethylene resin (R-10): An antioxidant (AO-1) in an amount of 1000 ppm with respect to the polyethylene resin is added in advance to the polyethylene resin (R-2). Polyethylene resin prepared by mixing and kneading.
[0137]
Formulation Composition (BL-11): Formulation composition except that the following polyethylene resin (R-11) is used instead of the polyethylene resin (R-2) used for the preparation of the formulation composition (BL-2) ( Formulation composition prepared in exactly the same manner as BL-2).
[0138]
Polyethylene resin (R-11): The amount of antioxidant (AO-1) in the surface resin layer of the resin-coated paper is 10 ppm relative to the polyethylene resin, and the amount of antioxidant (AO is 90 ppm). -2) is a polyethylene resin prepared by mixing and kneading the polyethylene resin (R-2) in advance.
[0139]
Formulation composition (BL-12): Formulation composition except that the following polyethylene resin (R-12) is used instead of the polyethylene resin (R-2) used for the preparation of the formulation composition (BL-2) ( Formulation composition prepared in exactly the same manner as BL-2).
[0140]
Polyethylene resin (R-12): The amount of antioxidant (AO-1) in the surface resin layer of the resin-coated paper is 20 ppm with respect to the polyethylene resin, and the amount of antioxidant (AO is 80 ppm). -2) is a polyethylene resin prepared by mixing and kneading the polyethylene resin (R-2) in advance.
[0141]
Formulation composition (BL-13): Formulation composition except that the following polyethylene resin (R-13) is used instead of the polyethylene resin (R-2) used for the preparation of the formulation composition (BL-2) ( Formulation composition prepared in exactly the same manner as BL-2).
[0142]
Polyethylene resin (R-13): The amount of antioxidant (AO-1) in the surface resin layer of the resin-coated paper is 50 ppm with respect to the polyethylene resin, and the amount of antioxidant (AO) is 50 ppm. -2) is a polyethylene resin prepared by mixing and kneading the polyethylene resin (R-2) in advance.
[0143]
Formulation composition (BL-14): Formulation composition except that the following polyethylene resin (R-14) was used instead of the polyethylene resin (R-2) used for the preparation of the formulation composition (BL-2) ( Formulation composition prepared in exactly the same manner as BL-2).
[0144]
Polyethylene resin (R-14): The amount of antioxidant (AO-1) in the surface resin layer of the resin-coated paper is 80 ppm relative to the polyethylene resin, and the amount of antioxidant (AO is 20 ppm). -2) is a polyethylene resin prepared by mixing and kneading the polyethylene resin (R-2) in advance.
[0145]
Formulation composition (BL-15): Instead of the polyethylene resin (R-2) used in the preparation of the formulation composition (BL-2), the formulation composition ( Formulation composition prepared in exactly the same manner as BL-2).
[0146]
Polyethylene resin (R-15): the amount of antioxidant (AO-1) in the surface resin layer of the resin-coated paper is 90 ppm with respect to the polyethylene resin, and the amount of antioxidant (AO is 10 ppm). -2) is a polyethylene resin prepared by mixing and kneading the polyethylene resin (R-2) in advance.
[0147]
Formulation composition (BL-16): Formulation composition except that the following polyethylene resin (R-16) is used instead of the polyethylene resin (R-2) used for the preparation of the formulation composition (BL-2) ( Formulation composition prepared in exactly the same manner as BL-2).
[0148]
Polyethylene resin (R-16): The amount of the antioxidant (AO-1) in the surface resin layer of the resin-coated paper is 100 ppm with respect to the polyethylene resin, and the antioxidant (AO) is 100 ppm. -2) is a polyethylene resin prepared by mixing and kneading the polyethylene resin (R-2) in advance.
[0149]
The content of the antioxidant in the surface resin layer of the resin-coated paper was determined by a preparative liquid chromatography method. Specifically, the measurement was performed as follows.
[0150]
(Preparation of analysis sample): The produced support for photosensitive material is placed in an aqueous protease solution maintained at an appropriate concentration kept at 40 ° C. and stirred for a while to remove the undercoat layer. Then, after thoroughly washing with ultrapure water, it is naturally dried. After drying, the surface resin layer of the support for photosensitive material is physically peeled off from the base paper, and the base paper that remains attached is also physically physically removed (killed with a sharp knife, peeled off with sandpaper, wet) Peel off with nylon scrubbing and a combination thereof), and then wash thoroughly with ultrapure water and then dry. After drying, the surface resin layer is about 25mm ² Samples cut into pieces are used as analysis samples.
[0151]
(Preparation of test solution): 10 g of an analytical sample of the surface resin layer is extracted with about 200 ml of chloroform at about 60 ° C. for 5 hours (the extraction solvent and the amount of extraction temperature and extraction time are matched to the antioxidant to be analyzed) Can be tested and selected). After extraction, the mixture is filtered, and the extract is concentrated to about 2.5 ml with an evaporator (water bath 60 ° C.), then 25 ml of methanol is added and stirred well, filtered, and the filtrate is concentrated to 1 ml or less with an evaporator (water bath 60 ° C.). . A solution prepared by adding chloroform to the concentrated solution to a total volume of 10 ml (the total volume setting may be changed as necessary) is examined.
[0152]
(Measurement of test solution): The test solution is measured by a preparative liquid chromatography method, and quantified by comparison with a standard sample by the peak area of ultraviolet absorbance at 280 nm.
(Measurement device); LC-908 preparative liquid chromatograph manufactured by Nihon Analytical Industries
Jagel 2H, a GPC preparative column manufactured by Nippon Analytical Industrial Co., Ltd.
(Measurement conditions) Loop volume: 3 ml.
Solvent used: chloroform.
Solvent flow rate: 3.5 ml / min.
Measurement temperature: 23 ° C.
[0153]
The obtained results are shown in Table 2.
[0154]
[Table 2]

[0155]
(Note 3) and (Note 5) in Table 2 are as follows.
[0156]
(Note 3) is equivalent to that in Table 1.
[0157]
(Note 5) The content of the antioxidant represents the content (ppm) relative to the polyethylene resin in the surface resin layer.
[0158]
From the results shown in Table 2, the substrate for light-sensitive materials (Examples 11 to 24) and the silver halide light-sensitive materials (Examples 11 to 25) in the present invention are remarkably improved in the occurrence of yellow fog, and silver halide light-sensitive materials. It is an excellent support for a light-sensitive material and a silver halide light-sensitive material in which the shelf life of the layer or the silver halide light-sensitive layer is remarkably improved and the emulsion film is remarkably improved. I understand well.
[0159]
Further, among the support for photosensitive material and the silver halide photosensitive material in the present invention, the surface resin layer from the viewpoint of the storage stability for the silver halide photosensitive layer or the storage stability of the silver halide photosensitive layer and the improvement effect with the emulsion film. It is well understood that the content of the antioxidant is preferably 20 ppm to 600 ppm, particularly preferably 50 ppm to 400 ppm, as a ratio to the polyethylene resin in the surface resin layer. Furthermore, from the viewpoint of the effect of improving storage stability, a combination of a hindered phenol-based antioxidant and an antioxidant containing a phosphorus atom in the molecule is preferable. It can be seen that it is particularly preferable that the ratio of the antioxidant used is 20 wt% to 80 wt%, and that the ratio of the antioxidant containing a phosphorus atom in the molecule is 80 wt% to 20 wt%.
[0160]
Examples 26-35
Example except that the following blending compositions (BL-17) to (BL-26) were used instead of the blending composition (BL-1) for covering the front side of the base paper used in Example 9. It carried out like 9. The oxygen permeability of the produced color photographic paper support is 350 cc / m each. ² / day.
[0161]
Formulation composition (BL-17): 17 parts by weight of the following master batch (MB-17W) containing titanium dioxide pigment, 8 parts by weight of the following master batch (MB-17B) containing titanium dioxide pigment and ultramarine blue, and the above A blended composition in which 75 parts by weight of polyethylene resin (R-2) pellets are well mixed (dry blended).
[0162]
Masterbatch (MB-17W): Titanium dioxide particle surface is hydrous aluminum oxide (Al per titanium dioxide) ₂ O _Three 0.5 wt.%) And surface milled and steam mill pulverized, an anatase titanium dioxide pigment having a number average diameter of 0.120 μm with an electron microscope of 50 wt.%, The polyethylene resin (R-1) 47.5 In the presence of 400 ppm by weight of the antioxidant (AO-1, molecular weight 700), 150% by weight of zinc stearate and zinc stearate are well kneaded at 150 ° C., cooled and pelletized. Masterbatch.
[0163]
Master batch (MB-17B): 50% by weight of the titanium dioxide pigment, 46.25% by weight of the polyethylene resin (R-1), 1.25% by weight of ultramarine (Daiichi Kasei Kogyo Co., Ltd., # 2000) and stearin A master batch prepared by kneading 2.5 wt% of blended zinc well at 150 ° C. using a Banbury mixer in the presence of 400 ppm of the antioxidant (AO-1), cooling and pelletizing.
[0164]
Formulation composition (BL-18): 17 parts by weight of the following master batch (MB-18W) containing titanium dioxide pigment, 8 parts by weight of the following master batch (MB-18B) containing titanium dioxide pigment and ultramarine blue, and the above A blended composition in which 75 parts by weight of polyethylene resin (R-2) pellets are well mixed (dry blended).
[0165]
Masterbatch (MB-18W): Tetrakis [methylene (3,5-di-tert.) As an antioxidant instead of 400 ppm of antioxidant (AO-1) present in the production of masterbatch (MB-17W). -Butyl-4-hydroxy-hydrocinnamate)] A masterbatch produced exactly as in the masterbatch (MB-17W) except that 400 ppm of methane (AO-3, molecular weight 1178) was present.
[0166]
Masterbatch (MB-18B): Instead of 400 ppm of antioxidant (AO-1) present in the production of masterbatch (MB-17B), 400 ppm of antioxidant (AO-3, molecular weight 1178) should be present. Except for the above, a master batch produced in exactly the same manner as the master batch (MB-17B).
[0167]
Formulation composition (BL-19): 17 parts by weight of the following master batch (MB-19W) containing titanium dioxide pigment, 8 parts by weight of the following master batch (MB-19B) containing titanium dioxide pigment and ultramarine blue, and the above A blended composition in which 75 parts by weight of polyethylene resin (R-2) pellets are well mixed (dry blended).
[0168]
Masterbatch (MB-19W): 3,9-bis [1.1-dimethyl as an antioxidant instead of 400 ppm of antioxidant (AO-1) present in the production of masterbatch (MB-17W) -2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5.5] -undecane (AO-4, A master batch produced in exactly the same manner as the master batch (MB-17W) except that the molecular weight 748) 400 ppm was present.
[0169]
Masterbatch (MB-19B): Instead of 400 ppm of antioxidant (AO-1) present in the production of masterbatch (MB-17B), 400 ppm of antioxidant (AO-4, molecular weight 748) should be present. Except for the above, a master batch produced in exactly the same manner as the master batch (MB-17B).
[0170]
Formulation composition (BL-20): 17 parts by weight of the following master batch (MB-20W) containing titanium dioxide pigment, 8 parts by weight of the following master batch (MB-20B) containing titanium dioxide pigment and ultramarine blue, and the above A blended composition in which 75 parts by weight of polyethylene resin (R-2) pellets are well mixed (dry blended).
[0171]
Masterbatch (MB-20W): Instead of 400 ppm of antioxidant (AO-1) present in the production of masterbatch (MB-17W), 1,3,5-Tris (3.5 -A masterbatch produced exactly as in the masterbatch (MB-17W) except that 400 ppm of di-tert-butyl-4-hydroxybenzyl) isocyanurate (AO-5, molecular weight 783) is present.
[0172]
Masterbatch (MB-20B): Instead of 400 ppm of antioxidant (AO-1) present in the production of masterbatch (MB-17B), 400 ppm of antioxidant (AO-5, molecular weight 783) should be present. Except for the above, a master batch produced in exactly the same manner as the master batch (MB-17B).
[0173]
Formulation composition (BL-21): 17 parts by weight of the following master batch (MB-21W) containing the titanium dioxide pigment, 8 parts by weight of the following master batch (MB-21B) containing the titanium dioxide pigment and ultramarine blue, and the above A blended composition in which 75 parts by weight of polyethylene resin (R-2) pellets are well mixed (dry blended).
[0174]
Masterbatch (MB-21W): 1,3,5-trimethyl-2,4 as an antioxidant instead of 400 ppm of antioxidant (AO-1) present in the production of masterbatch (MB-17W) , 6-tris (3.5-di-tert-butyl-4-hydroxybenzyl) benzene (AO-6, molecular weight 775) Except for the presence of 400 ppm, prepared exactly as in the masterbatch (MB-17W) Masterbatch.
[0175]
Masterbatch (MB-21B): 400 ppm of antioxidant (AO-6, molecular weight 775) should be present instead of 400 ppm of antioxidant (AO-1) present in the production of masterbatch (MB-17B). Except for the above, a master batch produced in exactly the same manner as the master batch (MB-17B).
[0176]
Formulation composition (BL-22): 17 parts by weight of the following master batch (MB-22W) containing titanium dioxide pigment, 8 parts by weight of the following master batch (MB-22B) containing titanium dioxide pigment and ultramarine blue, and the above A blended composition in which 75 parts by weight of polyethylene resin (R-2) pellets are well mixed (dry blended).
[0177]
Masterbatch (MB-22W): n-octadecyl-3- (3'1.5) as antioxidant instead of 400 ppm antioxidant (AO-1) present in the production of masterbatch (MB-17W) A masterbatch prepared exactly as in the masterbatch (MB-17W) except that 400 ppm of '-di-tert-butyl-4'-hydroxyphenyl) propionate (AO-7, molecular weight 520) is present.
[0178]
Masterbatch (MB-22B): Instead of 400 ppm of antioxidant (AO-1) present in the production of masterbatch (MB-17B), 400 ppm of antioxidant (AO-7, molecular weight 520) should be present. Except for the above, a master batch produced in exactly the same manner as the master batch (MB-17B).
[0179]
Formulation composition (BL-23): 17 parts by weight of the following master batch (MB-23W) containing titanium dioxide pigment, 8 parts by weight of the following master batch (MB-23B) containing titanium dioxide pigment and ultramarine blue, and the above A blended composition in which 75 parts by weight of polyethylene resin (R-2) pellets are well mixed (dry blended).
[0180]
Master batch (MB-23W): In place of 400 ppm of antioxidant (AO-1) present in the production of master batch (MB-17W), the antioxidant (AO-1, molecular weight 700) 200 ppm and the oxidation A masterbatch produced in exactly the same manner as the masterbatch (MB-17W) except that 200 ppm of inhibitor (AO-2, molecular weight 646) was present.
[0181]
Master batch (MB-23B): In place of 400 ppm of antioxidant (AO-1) present in the production of master batch (MB-17B), the antioxidant (AO-1, molecular weight 700) 200 ppm and the oxidation A masterbatch produced in exactly the same manner as the masterbatch (MB-17B) except that 200 ppm of inhibitor (AO-2, molecular weight 646) was present.
[0182]
Formulation composition (BL-24): 17 parts by weight of the following master batch (MB-24W) containing titanium dioxide pigment, 8 parts by weight of the following master batch (MB-24B) containing titanium dioxide pigment and ultramarine blue, A blended composition in which 75 parts by weight of polyethylene resin (R-2) pellets are well mixed (dry blended).
[0183]
Masterbatch (MB-24W): Instead of 400 ppm of antioxidant (AO-1) present in the production of masterbatch (MB-17W), 200 ppm of antioxidant (AO-1, molecular weight 700) is used in combination. A masterbatch produced in exactly the same manner as the masterbatch (MB-17W) except that 200 ppm of phenylisodecyl phosphite (AO-8, molecular weight 439) is present as an antioxidant.
[0184]
Master batch (MB-24B): In place of 400 ppm of antioxidant (AO-1) present in the production of master batch (MB-17B), the antioxidant (AO-1, molecular weight 700) 200 ppm and antioxidant A master batch produced in exactly the same manner as the master batch (MB-17B) except that 200 ppm of the agent (AO-8, molecular weight 439) was present.
[0185]
Formulation composition (BL-25): 17 parts by weight of the following master batch (MB-25W) containing titanium dioxide pigment, 8 parts by weight of the following master batch (MB-25B) containing titanium dioxide pigment and ultramarine blue, and the above A blended composition in which 75 parts by weight of polyethylene resin (R-2) pellets are well mixed (dry blended).
[0186]
Masterbatch (MB-25W): In combination with 200 ppm of the antioxidant (AO-1, molecular weight 700) instead of 400 ppm of the antioxidant (AO-1) present in the production of the masterbatch (MB-17W) A masterbatch except that 200 ppm of tetrakis (2,4-di-tert-butylphenyl) -4.4'-biphenylene-diphosphite (AO-9, molecular weight 1035) is present as the antioxidant. MB-17W). Master batch produced in exactly the same way.
[0187]
Masterbatch (MB-25B): In place of 400 ppm of antioxidant (AO-1) present in the production of masterbatch (MB-17B), the antioxidant (AO-1, molecular weight 700) 200 ppm and antioxidant A master batch produced in exactly the same manner as the master batch (MB-17B) except that 200 ppm of the agent (AO-9, molecular weight 1035) was present.
[0188]
Formulation composition (BL-26): 17 parts by weight of the following master batch (MB-26W) containing titanium dioxide pigment, 8 parts by weight of the following master batch (MB-26B) containing titanium dioxide pigment and ultramarine blue, and the above A blended composition in which 75 parts by weight of polyethylene resin (R-2) pellets are well mixed (dry blended).
[0189]
Master batch (MB-26W): In place of 400 ppm of antioxidant (AO-1) present in the production of master batch (MB-17W), the antioxidant (AO-6, molecular weight 775) 200 ppm and the oxidation A masterbatch produced in exactly the same manner as the masterbatch (MB-17W) except that 200 ppm of inhibitor (AO-2, molecular weight 646) was present.
[0190]
Master batch (MB-26B): In place of 400 ppm of the antioxidant (AO-1) present in the production of the master batch (MB-17B), the antioxidant (AO-6, molecular weight 775) 200 ppm and the oxidation A masterbatch produced in exactly the same manner as the masterbatch (MB-17B) except that 200 ppm of inhibitor (AO-2, molecular weight 646) was present.
[0191]
The obtained results are shown in Table 3.
[0192]
[Table 3]

[0193]
Note that (Note 3) in Table 3 is the same as that in Table 1.
[0194]
From the results shown in Table 3, the light-sensitive material support (Examples 26 to 35) and the silver halide light-sensitive material (Examples 26 to 35) in the present invention are remarkably improved in the occurrence of yellow fog, and silver halide light-sensitive. It is an excellent support for a light-sensitive material and a silver halide light-sensitive material in which the shelf life of the layer or the silver halide light-sensitive layer is remarkably improved and the emulsion film is remarkably improved. I understand well.
[0195]
Further, among the support for photosensitive material and the silver halide photosensitive material in the present invention, the surface resin layer from the viewpoint of the storage stability for the silver halide photosensitive layer or the storage stability of the silver halide photosensitive layer and the improvement effect with the emulsion film. As the antioxidant preferably contained in the hindered phenolic antioxidant having a molecular weight in the range of 600 to 1000, a hindered phenolic antioxidant and an antioxidant containing a phosphorus atom in the molecule are more preferred. It is well understood that the combined use of a hindered phenolic antioxidant having a molecular weight in the range of 600 to 1000 and an antioxidant containing a phosphorus atom in the molecule having a molecular weight of 500 or more is particularly preferable. . In addition, from comparison of Example 26 or Example 29 with Example 27, Example 28, Example 30 or Example 31 and comparison with Example 32 and Example 35, among the hindered phenolic antioxidants, It is well understood that isocyanurate compounds are particularly preferred from the viewpoints of storage stability with respect to the silver halide photosensitive layer, storage stability of the silver halide photosensitive layer, and improvement effect with the emulsion film.
[0196]
Examples 36 to 39 and Comparative Example 4
Instead of the blue-sensitive emulsion layer used in Example 5, Example 8, Example 14, Example 25 and Comparative Example 2, the following Example 5 and Example 8 were carried out except that the following blue-sensitive emulsion layer was used. Example 14, Example 25 and Comparative Example 2 were carried out (Example 36 corresponding to Example 5, Example 37 corresponding to Example 8, Example 38 corresponding to Example 14, Example 39 corresponds to Example 25, and Comparative Example 4 corresponds to Comparative Example 2.
[0197]
The blue-sensitive emulsion layer is sulfur for optimum sensitivity with an average grain size of 0.8 μm having a halogen composition of AgBr / AgCl = 95/5, which is produced by the first thermal process in the presence of an appropriate amount of potassium hexachloroiridium (III). Neutralized silver halide emulsion consisting of sensitized [1, 0, 0] and [1, 1, 1] mixed crystals with a silver nitrate content of 0.5 g / m ² Contains 1.5g / m of gelatin ² In addition to a yellow color coupler, it contains an appropriate amount of a stabilizer, a blue-sensitive sensitizing dye, a coating aid, a hardener, a thickener and the like. The viscosity of the blue emulsion layer coating solution is adjusted to 5.5 cp, and the wet coating amount is 35 g / m. ² It was painted with.
[0198]
The results obtained are shown in Table 4 (in order to make the results easier to compare, the results of Example 5, Example 8, Example 14, Example 24 and Comparative Example 2 are also shown in Table 4 again. is there).
[0199]
Note that (Note 3) and (Note 4) in Table 4 are the same as those in Table 1.
[0200]
[Table 4]

[0201]
From the results shown in Table 4, the effects of the present invention, particularly the effect of remarkably suppressing the occurrence of fog associated with storage of the silver halide light-sensitive material and remarkably improving the storage stability, are as follows. By using a multi-layer silver halide color photographic composition layer including a silver color photographic composition layer, particularly a blue-sensitive silver halide photographic emulsion layer having a silver chloride content of 90 mol% or more of blue-sensitive silver halide It can be seen that this is achieved significantly and remarkably.
[0202]
【The invention's effect】
According to the present invention, the side on which the silver halide photosensitive layer of the base paper based on natural pulp is provided is coated with a resin layer containing a polyethylene resin, and the opposite side is coated with a resin layer containing a film-forming resin. The storage stability of the silver halide photosensitive layer, particularly the silver halide photosensitive layer in which the silver halide is mainly composed of silver chloride, is remarkably improved, and the adhesion between the support and the silver halide photosensitive constituent layer is particularly wet. It is possible to provide a support for a photosensitive material of a resin-coated paper type in which the adhesion at the time, so-called emulsion film attachment, is remarkably improved. Further, according to the present invention, the side on which the silver halide photosensitive layer of the base paper mainly composed of natural pulp is provided is coated with a resin layer containing a polyethylene-based resin, and the opposite side is coated with a resin layer containing a film-forming resin. Storage of a silver halide photosensitive layer, in particular a silver halide photosensitive layer mainly composed of silver chloride, in which a silver halide photosensitive constituent layer is coated on a resin-coated paper-type support for photosensitive material It is possible to provide a silver halide light-sensitive material having significantly improved properties and having a support and a silver halide light-sensitive constituent layer, particularly wet adhesion, so-called emulsion film, which has been remarkably improved.

Claims (4)

Using a paper mainly composed of natural pulp as a substrate, the side of the paper substrate on which a silver halide photosensitive constituent layer comprising at least a silver halide photosensitive layer and, if necessary, an auxiliary functional layer is provided contains a polyethylene resin (a) A support for a photosensitive material coated with a resin layer (A) and coated on the opposite side with a resin layer (B) containing a resin (b) capable of forming a film, and at least a hindered phenolic antioxidant or molecule The surface of the resin layer (A) containing an antioxidant containing a phosphorus atom therein has a polyethylene surface oxidation degree as defined below in the range of 33% to 53%, and a photosensitive material support as defined below. The support for a photosensitive material is characterized by having an oxygen permeability of 450 cc / m ² / day or less.
Polyethylene surface oxidation degree: after or without applying an appropriate activation treatment to the surface of the resin layer (A), after applying an undercoat layer as required, or without applying an undercoat layer A silver halide photosensitive material is produced by coating a silver halide photosensitive constituent layer. After or after the production period, the silver halide photosensitive material is dry-thermo-dried at 65 ° C. for 5 days, the silver halide photosensitive constituent layer is removed by enzyme treatment, and then washed thoroughly with ultrapure water and then dried. To do. After drying, the O / C ratio (peak area ratio) (%) on the surface of the resin layer (A) obtained by measurement by ESCA (Electron Spectroscopy for Chemical Analysis) method is defined as the polyethylene surface oxidation degree (%).
Oxygen permeability of photosensitive material support: After or without appropriate activation treatment on the surface of the resin layer (A), after or undercoating the undercoat layer as necessary Without producing a silver halide photosensitive material, a silver halide photosensitive constituent layer is coated. After or after the production period, the silver halide photosensitive material is dry-thermo-dried at 65 ° C. for 5 days, the silver halide photosensitive constituent layer is removed by enzyme treatment, and then washed thoroughly with ultrapure water and then dried. To do. After drying, the oxygen transmission rate of the photosensitive material support was determined by measuring the oxygen transmission rate of the photosensitive material support in accordance with JIS K 7126 method B (isobaric method) under the following measurement conditions. cc / m ² / day).
Measurement environment: 23 ° C., 65% relative humidity.
Gas flow rate: oxygen; 20 ml / min, carrier gas (nitrogen / hydrogen gas); 10 ml / min.
Test cell area: 5 cm ² (uses aluminum foil mask).
Diffusion direction: Resin layer (B) side (diffusion tank) from resin layer (A) side (oxygen tank). 2. The support for photosensitive material according to claim 1, wherein the resin layer (A) contains a hindered phenolic antioxidant and an antioxidant containing a phosphorus atom in the molecule. 3. The support for photosensitive material according to claim 1, wherein the hindered phenol-based antioxidant is an isocyanurate-based compound. The support for a photosensitive material according to any one of claims 1 to 3, wherein the content of the antioxidant in the resin layer (A) is in the range of 50 ppm to 400 ppm as a ratio to the polyethylene resin (a).