JP2004053901A - Silver salt photothermographic dry imaging material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver salt photothermographic dry imaging material in which blocking of a rolled double-side undercoated base is prevented without impairing the adhesiveness of a support to an imaging layer and a dye-containing backing layer and contamination of transfer rolls is prevented in undercoating. <P>SOLUTION: In the silver salt photothermographic dry imaging material having one or more imaging layers comprising an organic silver salt, a photosensitive silver halide, a reducing agent and a binder, formed on a support, two or three non-imaging undercoat layers are formed under the imaging layers and two or three non-imaging undercoat layers are formed under a dye-containing backing layer on a side of the support opposite to the side with the imaging layers. <P>COPYRIGHT: (C)2004,JPO

Description

【００７２】
〈バッキング層の形成〉
先に作製した下引済み試料１−１のバッキング下引層上に、下記のバッキング層塗布液を、乾燥膜厚が３．５μｍになるように押し出しコーターにて塗布、乾燥（乾燥温度１００℃、露点温度１０℃の乾燥風を用いて５分間かけて乾燥）し、バッキング層を形成した。
【００７３】
《バッキング層塗布液の調製》
メチルエチルケトン８３０ｇを攪拌しながら、セルロースアセテートブチレート（Ｅａｓｔｍａｎ　Ｃｈｅｍｉｃａｌ社、ＣＡＢ３８１−２０）８４．２ｇおよびポリエステル樹脂（Ｂｏｓｔｉｃ社、ＶｉｔｅｌＰＥ２２００Ｂ）４．５ｇを添加し、溶解した。次に、溶解した液に、０．３０ｇの赤外染料−１を添加し、さらにメタノール４３．２ｇに溶解したフッ素系界面活性剤（旭硝子社、サーフロンＫＨ４０）４．５ｇとフッ素系界面系活性剤（大日本インク社、メガファッグＦ１２０Ｋ）２．３ｇを添加して、溶解するまで十分に攪拌を行った。最後に、メチルエチルケトンに１質量％の濃度でディゾルバ型ホモジナイザにて分散したシリカ（Ｗ．Ｒ．Ｇｒａｃｅ社、シロイド６４Ｘ６０００）を７５ｇ添加、攪拌しバッキング層塗布液を調製した。
【００７４】
【化２】

【００７５】
〈感光層側の層形成〉
バッキング層を形成した前記写真用支持体の反対側の感光層側である下引上層上に、下記感光層塗布液と表面保護層塗布液を押し出し（エクストルージョン）コーターを用いて同時に重層塗布することにより銀塩光熱写真ドライイメージング材料を作製した。塗布は、感光層は塗布銀量１．９ｇ／ｍ^２、表面保護層は乾燥膜厚で２．５μｍになる様にしておこなった。その後、乾燥温度７５℃、露点温度１０℃の乾燥風を用いて、１０分間乾燥を行い銀塩光熱写真ドライイメージング材料試料１−１を作製した。
【００７６】
（感光性ハロゲン化銀乳剤Ａの調製）
溶液（Ａ１）
フェニルカルバモイル化ゼラチン　　　　　　　　　　　　　　　８８．３ｇ
化合物（Ａ）（１０％メタノール水溶液）　　　　　　　　　　　　１０ｍｌ
臭化カリウム　　　　　　　　　　　　　　　　　　　　　　　　０．３２ｇ
水で５４２９ｍｌに仕上げる
溶液（Ｂ１）
０．６７ｍｏｌ／Ｌ硝酸銀水溶液　　　　　　　　　　　　　　２６３５ｍｌ
溶液（Ｃ１）
臭化カリウム　　　　　　　　　　　　　　　　　　　　　　　５１．５５ｇ
沃化カリウム　　　　　　　　　　　　　　　　　　　　　　　　１．４７ｇ
水で６６０ｍｌに仕上げる
溶液（Ｄ１）
臭化カリウム　　　　　　　　　　　　　　　　　　　　　　　１５４．９ｇ
沃化カリウム　　　　　　　　　　　　　　　　　　　　　　　　４．４１ｇ
塩化イリジウム（１％溶液）　　　　　　　　　　　　　　　　０．９３ｍｌ
水で１９８２ｍｌに仕上げる
溶液（Ｅ１）
０．４ｍｏｌ／Ｌ臭化カリウム水溶液　　　　　　　　　　下記銀電位制御量
溶液（Ｆ１）
水酸化カリウム　　　　　　　　　　　　　　　　　　　　　　　０．７１ｇ
水で２０ｍｌに仕上げる
溶液（Ｇ１）
５６％酢酸水溶液　　　　　　　　　　　　　　　　　　　　　１８．０ｍｌ
溶液（Ｈ１）
無水炭酸ナトリウム　　　　　　　　　　　　　　　　　　　　　１．７２ｇ
水で１５１ｍｌに仕上げる
化合物（Ａ）：
ＨＯ（ＣＨ_２ＣＨ_２Ｏ）ｎ−（ＣＨ（ＣＨ_３）ＣＨ_２Ｏ）_１７−（ＣＨ_２ＣＨ_２Ｏ）ｍＨ　（ｍ＋ｎ＝５〜７）
特公昭５８−５８２８８号公報に記載の混合攪拌機を用いて溶液（Ａ１）に溶液（Ｂ１）の１／４量及び溶液（Ｃ１）全量を温度４５℃、ｐＡｇ８．０９に制御しながら、同時混合法により４分４５秒を要して添加し核形成を行った。１分後、溶液（Ｆ１）の全量を添加した。この間ｐＡｇの調整を溶液（Ｅ１）を用いて適宜行った。６分間経過後、溶液（Ｂ１）の３／４量及び溶液（Ｄ１）の全量を、温度４５℃、ｐＡｇ８．０９に制御しながら、同時混合法により１４分１５秒かけて添加した。
【００７７】
５分間攪拌した後、４０℃に降温し、溶液（Ｇ１）を全量添加し、ハロゲン化銀乳剤を沈降させた。沈降部分２０００ｍｌを残して上澄み液を取り除き、水を１０リットル加え、攪拌後、再度ハロゲン化銀乳剤を沈降させた。沈降部分１５００ｍｌを残し、上澄み液を取り除き、更に水を１０リットル加え、攪拌後、ハロゲン化銀乳剤を沈降させた。沈降部分１５００ｍｌを残し、上澄み液を取り除いた後、溶液（Ｈ１）を加え、６０℃に昇温し、更に１２０分攪拌した。最後にｐＨが５．８になるように調整し、銀量１モル当たり１１６１ｇになるように水を添加し、感光性ハロゲン化銀乳剤Ａを得た。
【００７８】
この乳剤は、平均粒子サイズ０．０５８μｍ、粒子サイズの変動係数１２％、〔１００〕面比率９２％の単分散立方体沃臭化銀粒子であった。
【００７９】
（粉末有機銀塩Ａの調製）
４７２０ｍｌの純水にベヘン酸１３０．８ｇ、アラキジン酸６７．７ｇ、ステアリン酸４３．６ｇ、パルミチン酸２．３ｇを８０℃で溶解した。次に、１．５ｍｏｌ／Ｌの水酸化ナトリウム水溶液５４０．２ｍｌを添加し濃硝酸６．９ｍｌを加えた後、５５℃に冷却して脂肪酸ナトリウム溶液を得た。上記の脂肪酸ナトリウム溶液の温度を５５℃に保ったまま、４５．３ｇの上記の感光性ハロゲン化銀乳剤Ａと純水４５０ｍｌを添加し５分間攪拌した。
【００８０】
次に、１ｍｏｌ／Ｌの硝酸銀溶液７０２．６ｍｌを２分間かけて添加し、１０分間攪拌し有機銀塩分散物を得た。その後、得られた有機銀塩分散物を水洗容器に移し、脱イオン水を加えて攪拌後、静置させて有機銀塩分散物を浮上分離させ、下方の水溶性塩類を除去した。その後、排水の電導度が２μＳ／ｃｍになるまで脱イオン水による水洗、排水を繰り返し、遠心脱水を実施した後、得られたケーキ状の有機銀塩を、気流式乾燥機フラッシュジェットドライヤー（株式会社セイシン企業製）を用いて、窒素ガス雰囲気及び乾燥機入り口熱風温度の運転条件により含水率が０．１％になるまで乾燥して有機銀塩の乾燥済み粉末有機銀塩Ａを得た。
【００８１】
なお、有機銀塩組成物の含水率測定には赤外線水分計を使用した。
（予備分散液Ａの調製）
ポリビニルブチラール粉末（Ｍｏｎｓａｎｔｏ社製、Ｂｕｔｖａｒ　Ｂ−７９）１４．５７ｇをメチルエチルケトン１４５７ｇに溶解し、ＶＭＡ−ＧＥＴＺＭＡＮＮ社製ディゾルバＤＩＳＰＥＲＭＡＴ　ＣＡ−４０Ｍ型にて攪拌しながら粉末有機銀塩Ａ５００ｇを徐々に添加して十分に混合することにより予備分散液Ａを調製した。
【００８２】
（感光性乳剤分散液１の調製）
予備分散液Ａを、ポンプを用いてミル内滞留時間が１．５分間となるように、０．５ｍｍ径のジルコニアビーズ（東レ製トレセラム）を内容積の８０％充填したメディア型分散機ＤＩＳＰＥＲＭＡＴ　ＳＬ−Ｃ１２ＥＸ型（ＶＭＡ−ＧＥＴＺＭＡＮＮ社製）に供給し、ミル周速８ｍ／秒にて分散を行なうことにより感光性乳剤分散液１を調製した。
【００８３】
（安定剤液の調製）
１．０ｇの安定剤−１、０．３１ｇの酢酸カリウムをメタノール４．９７ｇに溶解し安定剤液を調製した。
【００８４】
（赤外増感色素液Ａの調製）
１９．２ｍｇの赤外増感色素ＳＤ−１、１．４８８ｇの２−クロロ−安息香酸、２．７７９ｇの安定剤−２および３６５ｍｇの５−メチル−２−メルカプトベンズイミダゾールを３１．３ｍｌのメチルエチルケトンに暗所にて溶解し赤外増感色素液Ａを調製した。
【００８５】
（添加液ａの調製）
現像剤としての１，１−ビス（２−ヒドロキシ−３，５−ジメチルフェニル）−２−メチルプロパンを２７．９８ｇと１．５４ｇの４−メチルフタル酸、０．４８ｇの前記赤外染料−１を１１０ｇのメチルエチルケトンに溶解し添加液ａとした。
【００８６】
（添加液ｂの調製）
１．５６ｇのカブリ防止剤−２、３．４３ｇのフタラジンを４０．９ｇのメチルエチルケトンに溶解し添加液ｂとした。
【００８７】
【化３】

【００８８】
《感光層塗布液の調製》
不活性気体雰囲気下（窒素９７％）において、前記感光性乳剤分散液１（５０ｇ）およびメチルエチルケトン１５．１１ｇを攪拌しながら２１℃に保温し、化学増感剤Ｓ−５（０．５％メタノール溶液）１０００μｌを加え、２分後にカブリ防止剤−１（１０％メタノール溶液）３９０μｌを加え、１時間攪拌した。さらに臭化カルシウム（１０％メタノール溶液）４９４μｌを添加して１０分撹拌した後、上記の有機化学増感剤の１／２０モル相当の金増感剤Ａｕ−５を添加、更に２０分攪拌した。続いて、安定剤液１６７ｍｌを添加して１０分間攪拌した後、１．３２ｇの前記赤外増感色素液Ａを添加して１時間攪拌した。
【００８９】
その後、温度を１３℃まで降温してさらに３０分攪拌した。１３℃に保温したまま、ポリビニルブチラール（Ｍｏｎｓａｎｔｏ社　Ｂｕｔｖａｒ　Ｂ−７９）１３．３１ｇを添加して３０分攪拌した後、テトラクロロフタル酸（９．４質量％メチルエチルケトン溶液）１．０８４ｇを添加して１５分間攪拌した。さらに攪拌を続けながら、１２．４３ｇの添加液ａ、１．６ｍｌのＤｅｓｍｏｄｕｒＮ３３００／モーベイ社製の脂肪族イソシアネート（１０％メチルエチルケトン溶液）、４．２７ｇの添加液ｂを順次添加し攪拌することにより感光層塗布液を得た。
【００９０】
【化４】

【００９１】
セルロースアセテートブチレート（Ｅａｓｔｍａｎ　Ｃｈｅｍｉｃａｌ社、７．５ｇのＣＡＢ１７１−１５）を４２．５ｇのメチルエチルケトンに溶解し、その中に、炭酸カルシウム（Ｓｐｅｃｉａｌｉｔｙ　Ｍｉｎｅｒａｌｓ社、Ｓｕｐｅｒ−Ｐｆｌｅｘ２００）５ｇを添加、ディゾルバ型ホモジナイザにて８０００ｒｐｍで３０分間分散しマット剤分散液を調製した。
【００９２】
《表面保護層塗布液の調製》
メチルエチルケトン８６５ｇを攪拌しながら、セルロースアセテートブチレート（Ｅａｓｔｍａｎ　Ｃｈｅｍｉｃａｌ社、ＣＡＢ１７１−１５）を９６ｇ、ポリメチルメタクリル酸（ローム＆ハース社、パラロイドＡ−２１）を４．５ｇ、ビニルスルホン化合物ＨＤ−１を１．５ｇ、ベンズトリアゾールを１．０ｇ、Ｆ系活性剤（旭硝子社、サーフロンＫＨ４０）を１．０ｇ、添加し溶解した。次に上記マット剤分散液３０ｇを添加して攪拌し、表面保護層塗布液を調製した。
【００９３】
ビニルスルホン化合物ＨＤ−１：（ＣＨ_２＝ＣＨＳＯ_２ＣＨ_２）_２ＣＨＯＨ
以上のように、下引済み試料１−１にバッキング層、感光層、表面保護層を設けて銀塩光熱写真ドライイメージング材料試料１−１を作製した。又、下引済み試料１−２〜１−４を用いた以外は銀塩光熱写真ドライイメージング材料試料１の作製と同様にして、銀塩光熱写真ドライイメージング材料試料１−１〜１−４を作製した。
【００９４】
評価法は次の通りである。
《下引ＥＣ面（感光面）とＢＣ面（バッキング面）のブロッキング評価》
ロール形状の下引済み試料（紙管の３インチコアに３００ｍを線圧で１３０Ｎ／ｍで巻いたもの）を４５℃３日のサーモに入れた後評価した。
【００９５】
１：くっついており剥がすと支持体が破壊する
２：剥離面の表面を観察すると１００μｍ以上の長さの、下引の破壊が１ｍ^２中１０個以上観測される
３：通常に剥がすことが出来るが、剥離面の表面を観察すると１００μｍ以上の長さの、下引の破壊が１ｍ^２中２〜９個観測される
４：通常に剥がすことが出来問題無いが、剥離面の表面を観察すると１００μｍ以上の長さの、下引の破壊が１ｍ^２中１／１０〜１個観測される
５：通常に剥がすことが出来問題無く、剥離面の表面を観察すると１００μｍ以上の長さの、下引の破壊が観測されない。
【００９６】
《ニップロールの評価》
線圧で１３０Ｎ／ｍ掛かるように調整した表面にウレタン製のゴム加工を施したステンレスロールとクロムメッキされたステンレスロールのニップロールの間をそれぞれＥＣ面がゴムロールに掛かる方向とＢＣ面がゴムロールに掛かるよう２回ラインスピード５０ｍ／分でブロッキング評価と同様のロール形状でサーモ処理したフィルムベースを１０００ｍ搬送し、それぞれＥＣ面の接したときのゴムロールの汚れとＢＣ面が接したときの汚れを評価した。
【００９７】
１：ロールの表面が下引樹脂で汚れているのが目視で判る
２：ロールの表面を観察すると１００μｍ以上の長さの、下引の汚れが１ｃｍ^２中１００個以上観測される
３：ロールの表面を観察すると１００μｍ以上の長さの、下引の汚れが１ｃｍ^２中１０〜１００個未満観測される
４：ロールの表面を観察すると１００μｍ以上の長さの、下引の汚れが１ｃｍ^２中１／１０〜１０個未満観測される
５：ロールの表面を観察すると１００μｍ以上の長さの、下引の汚れが観測されない。
【００９８】
《現像後のＥＣ面の膜付評価》
ヒートドラムを有する熱現像用自動現像機を用いて、１２３℃で１５秒熱現像処理し、熱現像直後（１分以内）の試料に試料面に対して４５°の角度で、カミソリの刃を入れ、切り込みを挟んでセロファン粘着テープを圧着し、急激に４５°と反対方向にほぼ水平方向に引き剥がし熱現像画像形成層の剥離面積を求め、下記に示す評価基準に従って評価した。
【００９９】
１．接着力は非常に弱く、熱現像画像形成層は完全に剥離する
２．剥離面積が５０％以上、１００％未満である
３．剥離面積が２０％以上、５０％未満である
４．接着力は強く、剥離面積は５％以上、２０％未満である
５．接着力は非常に強く、剥離面積は５％未満である。
【０１００】
【表１】

【０１０１】
表１から明らかなように、本発明に係る下引済み試料及び銀塩光熱写真ドライイメージング材料試料は、比較試料に比べて、支持体と、画像形成層及び染料を含むバッキング層のを損なわずに、巻き取られた両面下引済みベースのブロッキング性が良好かつ下引加工時の搬送ロールへの汚染防止が改良されている。
【０１０２】
実施例２
引き続き実施例１で用いた下引塗布液ａ−１を下記ａｓ−１に変更し、乾燥温度と熱処理温度を７０℃にした以外は全く同様にして銀塩光熱写真ドライイメージング材料試料１−１の作製と同様にして、銀塩光熱写真ドライイメージング材料試料２−１〜２−４を作製した。
【０１０３】
《下引塗布液ａｓ−１》
Ｐ−１　　　　　　　　　　　　　　　　　　　　　　　　　　　　　７０ｇ
以上に蒸留水を加えて１０００ｍｌとし、塗布液とした。
【０１０４】
Ｐ−１：Ｌｘ−１をスプレードライにて粉末状に乾燥後ＭＥＫで固形分濃度が３０％になるように仕上げた。
【０１０５】
【表２】

【０１０６】
表２から明らかなように、本発明に係る下引済み試料及び銀塩光熱写真ドライイメージング材料試料は、比較試料に比べて、支持体と、画像形成層及び染料を含むバッキング層のを損なわずに、巻き取られた両面下引済みベースのブロッキング性が良好かつ下引加工時の搬送ロールへの汚染防止が改良されている。
【０１０７】
実施例３
引き続き実施例１で用いた下引済みベース１−１〜１−４に下記画像形成層、中間層、保護層及びハレーション防止バック層を塗設し銀塩光熱写真ドライイメージング材料試料３−１〜３−４を作製した。
【０１０８】
《バック面塗布液の調製》
（１）塩基プレカーサーの固体微粒子分散液（ａ）の調製
塩基プレカーサー化合物１を６４ｇ、ジフェニルスルフォンを２８ｇおよび花王（株）製界面活性剤デモールＮの１０ｇを蒸留水２２０ｍｌと混合し、混合液をサンドミル（１／４　Ｇａｌｌｏｎサンドグラインダーミル、アイメックス（株）製）を用いてビーズ分散し、平均粒子径０．２μｍの、塩基プレカーサー化合物の固体微粒子分散液（ａ）を得た。
【０１０９】
（２）染料固体微粒子分散液の調製
シアニン染料化合物１を９．６ｇおよびｐ−ドデシルベンゼンスルフォン酸ナトリウム５．８ｇを蒸留水３０５ｍｌと混合し、混合液をサンドミル（１／４　Ｇａｌｌｏｎサンドグラインダーミル、アイメックス（株）製）を用いてビーズ分散して平均粒子径０．２μｍの染料固体微粒子分散液を得た。
【０１１０】
（３）ハレーション防止層塗布液の調製
ゼラチン１７ｇ、ポリアクリルアミド９．６ｇ、上記塩基プレカーサーの固体微粒子分散液（ａ）７０ｇ、上記染料固体微粒子分散液５６ｇ、ポリメチルメタクリレート微粒子（平均粒子サイズ６．５μｍ）１．５ｇ、ベンゾイソチアゾリノン０．０３ｇ、ポリエチレンスルフォン酸ナトリウム２．２ｇ、青色染料化合物１を０．２ｇ、水を８４４ｍｌ混合し、ハレーション防止層塗布液を調製した。
【０１１１】
《バック面保護層塗布液の調製》
容器を４０℃に保温し、ゼラチン５０ｇ、ポリスチレンスルフォン酸ナトリウム０．２ｇ、Ｎ，Ｎ−エチレンビス（ビニルスルフォンアセトアミド）２．４ｇ、ｔ−オクチルフェノキシエトキシエタンスルフォン酸ナトリウム１ｇ、ベンゾイソチアゾリノン３０ｍｇ、Ｎ−パーフルオロオクチルスルフォニル−Ｎ−プロピルアラニンカリウム塩３７ｍｇ、ポリエチレングリコールモノ（Ｎ−パーフルオロオクチルスルホニル−Ｎ−プロピル−２−アミノエチル）エーテル［エチレンオキサイド平均重合度１５］０．１５ｇ、Ｃ_８Ｆ_１７ＳＯ_３Ｋ　３２ｍｇ、Ｃ_８Ｆ_１７ＳＯ_２Ｎ（Ｃ_３Ｈ_７）（ＣＨ_２ＣＨ_２Ｏ）（ＣＨ_２）_４−ＳＯ_３Ｎａ　６４ｍｇ、アクリル酸／エチルアクリレート共重合体（共重合質量比５／９５）８．８ｇ、エアロゾールＯＴ（アメリカンサイアナミド社製）０．６ｇ、流動パラフィン乳化物を流動パラフィンとして１．８ｇ、水を９５０ｍｌ混合してバック面保護層塗布液とした。
【０１１２】
《ハロゲン化銀乳剤１の調製》
蒸留水１４２１ｍｌに１質量％臭化カリウム溶液８．０ｍｌを加え、さらに１Ｎ硝酸を８．２ｍｌ、フタル化ゼラチン２０ｇを添加した液をチタンコートしたステンレス製反応壺中で攪拌しながら、３７℃に液温を保ち、硝酸銀３７．０４ｇに蒸留水を加え１５９ｍｌに希釈した溶液Ａと臭化カリウム３２．６ｇを蒸留水にて容量２００ｍｌに希釈した溶液Ｂを準備し、コントロールダブルジェット法でｐＡｇを８．１に維持しながら、溶液Ａの全量を一定流量で１分間かけて添加した。溶液Ｂは、コントロールドダブルジェット法にて添加した。その後３．５質量％の過酸化水素水溶液を３０ｍｌ添加し、さらにベンツイミダゾールの３質量％水溶液を３６ｍｌ添加した。その後、再び溶液Ａを蒸留水で希釈して３１７．５ｍｌにした溶液Ａ２と、溶液Ｂに対して最終的に銀１モル当たり１×１０^−４モルになるよう６塩化イリジウム酸３カリウム塩を溶解し、液量を溶液Ｂの２倍の４００ｍｌまで蒸留水で希釈した溶液Ｂ２を用いて、やはりコントロールドダブルジェット法にて、ｐＡｇを８．１に維持しながら、一定流量で溶液Ａ２を１０分間かけて全量添加した。溶液Ｂ２は、コントロールドダブルジェット法で添加した。その後、５−メチル−２−メルカプトベンズイミダゾールの０．５質量％メタノール溶液を５０ｍｌ添加し、さらに硝酸銀でｐＡｇを７．５に上げてから１Ｎ硫酸を用いてｐＨを３．８に調整し、攪拌を止め、沈降／脱塩／水洗工程を行い、脱イオンゼラチン３．５ｇを加えて１ｍｏｌ／Ｌの水酸化ナトリウムを添加して、ｐＨ６．０、ｐＡｇ８．２に調整してハロゲン化銀分散物を作製した。できあがったハロゲン化銀乳剤中の粒子は、平均球相当径０．０５３μｍ、球相当径の変動係数１８％の純臭化銀粒子であった。粒子サイズ等は、電子顕微鏡を用い１０００個の粒子の平均から求めた。この粒子の［１００］面比率は、クベルカムンク法を用いて８５％と求められた。
【０１１３】
上記乳剤を３８℃に攪拌しながら維持して、ベンゾイソチアゾリノンを０．０３５ｇ（３．５質量％メタノール溶液で添加）加え、４０分後に分光増感色素１の固体分散物（ゼラチン水溶液）を銀１モル当たり５×１０^−３モル加え、１分後に４７℃に昇温し、２０分後にベンゼンチオスルフォン酸ナトリウムを銀１モルに対して３×１０^−５モル加え、さらに２分後にテルル化合物を銀１モル当たり５×１０^−５モル加えて９０分間熟成した。熟成終了間際に、Ｎ，Ｎ−ジヒドロキシ−Ｎ−ジエチルメラミンの０．５質量％メタノール溶液を５ｍｌを加え、温度を３１℃に下げ、フェノキシエタノールの３．５質量％メタノール溶液５ｍｌ、５−メチル−２−メルカプトベンヅイミダゾールを銀１モル当たり７×１０^−３モル及び１−フェニル−２−ヘプチル−５−メルカプト−１，３，４−トリアゾールを銀１モルに対して６．４×１０^−３モルを添加して、ハロゲン化銀乳剤１を作製した。
【０１１４】
《ハロゲン化銀乳剤２の調製》
ハロゲン化銀乳剤１の調製において、粒子形成時の液温３７℃を５０℃に変更する以外は同様にして平均球相当径０．０８μｍ、球相当径の変動係数１５％の純臭化銀立方体粒子乳剤の調製した。ハロゲン化銀乳剤１と同様に沈殿／脱塩／水洗／分散を行った。更に分光増感色素１の添加量を銀１モル当たり４．５×１０^−３モルに変えた以外は乳剤１と同様にして分光増感、化学増感及び５−メチル−２−メルカプトベンヅイミダゾール、１−フェニル−２−ヘプチル−５−メルカプト−１，３，４−トリアゾールの添加を行い、ハロゲン化銀乳剤２を得た。
【０１１５】
《ハロゲン化銀乳剤３の調製》
ハロゲン化銀乳剤１の調製において、粒子形成時の液温３７℃を２７℃に変更する以外は同様にして平均球相当径０．０３８μｍ、球相当径の変動係数２０％の純臭化銀立方体粒子乳剤の調製した。ハロゲン化銀乳剤１と同様に沈殿／脱塩／水洗／分散を行った。更に分光増感色素１の添加量を銀１モル当たり６×１０^−３モルに変えた以外は乳剤１と同様にして分光増感、化学増感及び５−メチル−２−メルカプトベンヅイミダゾール、１−フェニル−２−ヘプチル−５−メルカプト−１，３，４−トリアゾールの添加を行い、ハロゲン化銀乳剤３を得た。
【０１１６】
《塗布液用混合乳剤Ａの調製》
ハロゲン化銀乳剤１を７０質量％、ハロゲン化銀乳剤２を１５質量％、ハロゲン化銀乳剤３を１５質量％溶解し、ベンゾチアゾリウムヨーダイドを１質量％水溶液にて銀１モル当たり７×１０^−３モル添加した。
【０１１７】
【化５】

【０１１８】
《りん片状脂肪酸銀塩の調製》
ヘンケル社製ベヘン酸（製品名Ｅｄｅｎｏｒ　Ｃ２２−８５Ｒ）８７．６ｇ、蒸留水４２３ｍｌ、５ｍｏｌ／ＬのＮａＯＨ水溶液４９．２ｍｌ、ｔｅｒｔ−ブタノール１２０ｍｌを混合し、７５℃にて１時間攪拌し反応させ、ベヘン酸ナトリウム溶液を得た。別に、硝酸銀４０．４ｇの水溶液２０６．２ｍｌ（ｐＨ４．０）を用意し、１０℃にて保温した。６３５ｍｌの蒸留水と３０ｍｌのｔｅｒｔ−ブタノールを入れた反応容器を３０℃に保温し、撹拌しながら先のベヘン酸ナトリウム溶液の全量と硝酸銀水溶液の全量を流量一定でそれぞれ６２分１０秒と６０分かけて添加した。このとき、硝酸銀水溶液添加開始後７分２０秒間は硝酸銀水溶液のみが添加されるようにし、そのあとベヘン酸ナトリウム溶液を添加開始し、硝酸銀水溶液の添加終了後９分３０秒間はベヘン酸ナトリウム溶液のみが添加されるようにした。このとき、反応容器内の温度は３０℃とし、液温度が一定になるように外温コントロールした。また、ベヘン酸ナトリウム溶液の添加系の配管は、スチームトレースにより保温し、添加ノズル先端の出口の液温度が７５℃になるようにスチーム開度を調製した。また、硝酸銀水溶液の添加系の配管は、２重管の外側に冷水を循環させることにより保温した。ベヘン酸ナトリウム溶液の添加位置と硝酸銀水溶液の添加位置は撹拌軸を中心として対称的な配置とし、また反応液に接触しないような高さに調製した。ベヘン酸ナトリウム溶液を添加終了後、そのままの温度で２０分間撹拌放置し、２５℃に降温した。その後、吸引濾過で固形分を濾別し、固形分を濾過水の伝導度が３０μＳ／ｃｍになるまで水洗した。こうして脂肪酸銀塩を得た。得られた固形分は、乾燥させないでウエットケーキとして保管した。
【０１１９】
得られたベヘン酸銀粒子の形態を電子顕微鏡撮影により評価したところ、平均値でａ＝０．１４μｍ、ｂ＝０．４μｍ、ｃ＝０．６μｍ、平均アスペクト比５．２、平均球相当径０．５２μｍ、球相当径の変動係数１５％のりん片状の結晶であった。（ａ，ｂ，ｃは本文の規定）乾燥固形分１００ｇ相当のウエットケーキに対し、ポリビニルアルコール（商品名：ＰＶＡ−２１７、平均重合度約１７００）７．４ｇおよび水を添加し、全体量を３８５ｇとしてからホモミキサーにて予備分散した。次に予備分散済みの原液を分散機（商品名：マイクロフルイダイザーＭ−１１０Ｓ−ＥＨ、マイクロフルイデックス・インターナショナル・コーポレーション製、Ｇ１０Ｚインタラクションチャンバー使用）の圧力を１７５０ｋｇ／ｃｍ^２に調節して、三回処理し、ベヘン酸銀分散物を得た。冷却操作は蛇管式熱交換器をインタラクションチャンバーの前後にそれぞれ装着し、冷媒の温度を調節することで１８℃の分散温度に設定した。
【０１２０】
《還元剤の２５質量％分散物の調製》
１，１−ビス（２−ヒドロキシ−３，５−ジメチルフェニル）−３，５，５−トリメチルヘキサン１０ｋｇと変性ポリビニルアルコール（クラレ（株）製、ポバールＭＰ２０３）の２０質量％水溶液１０ｋｇに、水１６ｋｇを添加して、良く混合してスラリーとした。このスラリーをダイアフラムポンプで送液し、平均直径０．５ｍｍのジルコニアビーズを充填した横型サンドミル（ＵＶＭ−２：アイメックス（株）製）にて３時間３０分分散したのち、ベンゾイソチアゾリノンナトリウム塩０．２ｇと水を加えて還元剤の濃度が２５質量％になるように調製し、還元剤分散物を得た。こうして得た還元剤分散物に含まれる還元剤粒子はメジアン径０．４０μｍ、最大粒子径１．８μｍ以下であった。得られた還元剤分散物は孔径１０．０μｍのポリプロピレン製フィルターにてろ過を行い、ゴミ等の異物を除去して収納した。
【０１２１】
《メルカプト化合物の１０質量％分散物の調製》
１−フェニル−２−ヘプチル−５−メルカプト−１，３，４−トリアゾールを５ｋｇと変性ポリビニルアルコール（クラレ（株）製ポバールＭＰ２０３）の２０質量％水溶液５ｋｇに、水８．３ｋｇを添加して、良く混合してスラリーとした。このスラリーをダイアフラムポンプで送液し、平均直径０．５ｍｍのジルコニアビーズを充填した横型サンドミル（ＵＶＭ−２：アイメックス（株）製）にて６時間分散したのち、水を加えてメルカプト化合物の濃度が１０質量％になるように調製し、メルカプト分散物を得た。こうして得たメルカプト化合物分散物に含まれるメルカプト化合物粒子はメジアン径０．４０μｍ、最大粒子径２．０μｍ以下であった。得られたメルカプト化合物分散物は孔径１０．０μｍのポリプロピレン製フィルターにてろ過を行い、ゴミ等の異物を除去して収納した。また、使用直前に再度孔径１０μｍのポリプロピレン製フィルターにてろ過した。
【０１２２】
《有機ポリハロゲン化合物の２０質量％分散物−１の調製》
トリブロモメチルナフチルスルホン５ｋｇと変性ポリビニルアルコール（クラレ（株）製ポバールＭＰ２０３）の２０質量％水溶液２．５ｋｇと、トリイソプロピルナフタレンスルホン酸ナトリウムの２０質量％水溶液２１３ｇと、水１０ｋｇを添加して、良く混合してスラリーとした。このスラリーをダイアフラムポンプで送液し、平均直径０．５ｍｍのジルコニアビーズを充填した横型サンドミル（ＵＶＭ−２：アイメックス（株）製）にて５時間分散したのち、ベンゾイソチアゾリノンナトリウム塩０．２ｇと水を加えて有機ポリハロゲン化合物の濃度が２０質量％になるように調製し、有機ポリハロゲン化合物分散物を得た。こうして得たポリハロゲン化合物分散物に含まれる有機ポリハロゲン化合物粒子はメジアン径０．３６μｍ、最大粒子径２．０μｍ以下であった。得られた有機ポリハロゲン化合物分散物は孔径３．０μｍのポリプロピレン製フィルターにてろ過を行い、ゴミ等の異物を除去して収納した。
【０１２３】
《有機ポリハロゲン化合物の２５質量％分散物−２の調製》
有機ポリハロゲン化合物の２０質量％分散物−１と同様に、但し、トリブロモメチルナフチルスルホン５ｋｇの代わりにＮ−ブチル−３−トリブロモメタンスルホニルベンズアミド５ｋｇを用い、分散し、この有機ポリハロゲン化合物が２５質量％となるように希釈し、ろ過を行った。こうして得た有機ポリハロゲン化合物分散物に含まれる有機ポリハロゲン化合物粒子はメジアン径０．３９μｍ、最大粒子径２．２μｍ以下であった。得られた有機ポリハロゲン化合物分散物は孔径３．０μｍのポリプロピレン製フィルターにてろ過を行い、ゴミ等の異物を除去して収納した。
【０１２４】
《有機ポリハロゲン化合物の３０質量％分散物−３の調製》
有機ポリハロゲン化合物の２０質量％分散物−１と同様に、但し、トリブロモメチルナフチルスルホン５ｋｇの代わりにトリブロモメチルフェニルスルホン５ｋｇを用い、２０質量％ＭＰ２０３水溶液を５ｋｇとし、分散し、この有機ポリハロゲン化合物が３０質量％となるように希釈し、ろ過を行った。こうして得た有機ポリハロゲン化合物分散物に含まれる有機ポリハロゲン化合物粒子はメジアン径０．４１μｍ、最大粒子径２．０μｍ以下であった。得られた有機ポリハロゲン化合物分散物は孔径３．０μｍのポリプロピレン製フィルターにてろ過を行い、ゴミ等の異物を除去して収納した。また、収納後、使用までは１０℃以下で保管した。
【０１２５】
《フタラジン化合物の５質量％溶液の調製》
８ｋｇのクラレ（株）製変性ポリビニルアルコールＭＰ２０３を水１７４．５７ｋｇに溶解し、次いでトリイソプロピルナフタレンスルホン酸ナトリウムの２０質量％水溶液３．１５ｋｇと６−イソプロピルフタラジンの７０質量％水溶液１４．２８ｋｇを添加し、６−イソプロピルフタラジンの５質量％液を調製した。
【０１２６】
《顔料の２０質量％分散物の調製》
Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　６０を６４ｇと花王（株）製デモールＮを６．４ｇに水２５０ｇを添加し良く混合してスラリーとした。平均直径０．５ｍｍのジルコニアビーズ８００ｇを用意してスラリーと一緒にベッセルに入れ、分散機（１／４Ｇサンドグラインダーミル：アイメックス（株）製）にて２５時間分散し顔料分散物を得た。こうして得た顔料分散物に含まれる顔料粒子は平均粒径０．２１μｍであった。
【０１２７】
《ＳＢＲラテックス４０質量％の調製》
限外濾過（ＵＦ）精製したＳＢＲラテックスは以下のように得た。下記のＳＢＲラテックスを蒸留水で１０倍に希釈したものをＵＦ−精製用モジュールＦＳ０３−ＦＣ−ＦＵＹ０３Ａ１（ダイセン・メンブレン・システム（株））を用いてイオン伝導度が１．５ｍＳ／ｃｍになるまで希釈精製し、三洋化成（株）製サンデット−ＢＬを０．２２質量％になるよう添加した。更にＮａＯＨとＮＨ_４ＯＨを用いてＮａ^＋イオン：ＮＨ_４ ^＋イオン＝１：２．３（モル比）になるように添加し、ｐＨ８．４に調整した。この時のラテックス濃度は４０質量％であった。
（ＳＢＲラテックス：−Ｓｔ（６８）−Ｂｕ（２９）−ＡＡ（３）−のラテックス）平均粒径０．１μｍ、濃度４５％、２５℃相対湿度６０％における平衡含水率０．６質量％、イオン伝導度４．２ｍＳ／ｃｍ（イオン伝導度の測定は東亜電波工業（株）製伝導度計ＣＭ−３０Ｓ使用しラテックス原液（４０％）を２５℃にて測定）、ｐＨ８．２。
【０１２８】
《画像形成層塗布液の調製》
上記で得た顔料の２０質量％水分散物を１．１ｇ、有機酸銀分散物１０３ｇ、ポリビニルアルコールＰＶＡ−２０５（クラレ（株）製）の２０質量％水溶液５ｇ、上記２５質量％還元剤分散物２５ｇ、有機ポリハロゲン化合物分散物−１，−２，−３を２：５：２（質量比）で総量１３．２ｇ、メルカプト化合物１０％分散物６．２ｇ、限外濾過（ＵＦ）精製しｐＨ調整したＳＢＲラテックス４０質量％を１０６ｇ、フタラジン化合物の５質量％溶液を１８ｍｌを添加し、ハロゲン化銀混合乳剤Ａを１０ｇを良く混合し、画像形成層（感光性層、乳剤層）塗布液を調製し、そのままコーティングダイへ７０ｍｌ／ｍ^２となるように送液し、塗布した。
【０１２９】
《乳剤面中間層塗布液の調製》
ポリビニルアルコールＰＶＡ−２０５（クラレ（株）製）の１０質量％水溶液７７２ｇ、顔料の２０質量％分散物５．３ｇ、メチルメタクリレート／スチレン／ブチルアクリレート／ヒドロキシエチルメタクリレート／アクリル酸共重合体（共重合質量比６４／９／２０／５／２）ラテックス２７．５質量％液２２６ｇにエアロゾールＯＴ（アメリカンサイアナミド社製）の５質量％水溶液を２ｍｌ、フタル酸二アンモニウム塩の２０質量％水溶液を１０．５ｍｌ、総量８８０ｇになるように水を加えて中間層塗布液とし、１０ｍｌ／ｍ^２になるようにコーティングダイへ送液した。
【０１３０】
《乳剤面保護層第１層塗布液の調製》
イナートゼラチン６４ｇを水に溶解し、メチルメタクリレート／スチレン／ブチルアクリレート／ヒドロキシエチルメタクリレート／アクリル酸共重合体（共重合質量比６４／９／２０／５／２）ラテックス２７．５質量％液８０ｇ、フタル酸の１０質量％メタノール溶液を２３ｍｌ、４−メチルフタル酸の１０質量％水溶液２３ｍｌ、１Ｎの硫酸を２８ｍｌ、エアロゾールＯＴ（アメリカンサイアナミド社製）の５質量％水溶液を５ｍｌ、フェノキシエタノール０．５ｇ、ベンゾイソチアゾリノン０．１ｇを加え、総量７５０ｇになるように水を加えて塗布液とし、４質量％のクロムみょうばん２６ｍｌを塗布直前にスタチックミキサーで混合したものを１８．６ｍｌ／ｍ^２になるようにコーティングダイへ送液した。
【０１３１】
《乳剤面保護層第２層塗布液の調製》
イナートゼラチン８０ｇを水に溶解し、メチルメタクリレート／スチレン／ブチルアクリレート／ヒドロキシエチルメタクリレート／アクリル酸共重合体（共重合質量比６４／９／２０／５／２）ラテックス２７．５質量％液１０２ｇ、Ｎ−パーフルオロオクチルスルフォニル−Ｎ−プロピルアラニンカリウム塩の５質量％溶液を３．２ｍｌ、ポリエチレングリコールモノ（Ｎ−パーフルオロオクチルスルホニル−Ｎ−プロピル−２−アミノエチル）エーテル［エチレンオキシド平均重合度＝１５］の２質量％水溶液を３２ｍｌ、エアロゾールＯＴ（アメリカンサイアナミド社製）の５質量％溶液を２３ｍｌ、ポリメチルメタクリレート微粒子（平均粒径０．７μｍ）４ｇ、ポリメチルメタクリレート微粒子（平均粒径６．４μｍ）２１ｇ、４−メチルフタル酸１．６ｇ、フタル酸４．８ｇ、１Ｎの硫酸を４４ｍｌ、ベンゾイソチアゾリノン１０ｍｇに総量６５０ｇとなるよう水を添加して、４質量％のクロムみょうばんと０．６７質量％のフタル酸を含有する水溶液４４５ｍｌを塗布直前にスタチックミキサーで混合したものを表面保護層塗布液とし、８．３ｍｌ／ｍ^２になるようにコーティングダイへ送液した。
【０１３２】
《銀塩光熱写真ドライイメージング材料の作製》
上記下塗り支持体のバック面側に、ハレーション防止層塗布液を固体微粒子染料の固形分塗布量が０．０４ｇ／ｍ^２となるように、またバック面保護層塗布液をゼラチン塗布量が１．７ｇ／ｍ^２となるように同時重層塗布し、乾燥し、ハレーション防止バック層を作製した。バック面と反対の面に下塗り面から画像形成層（ハロゲン化銀の塗布銀量０．１４ｇ／ｍ^２）、中間層、保護層第１層、保護層第２層の順番でスライドビード塗布方式にて同時重層塗布し、銀塩光熱写真ドライイメージング材料の試料３−１を作製した。銀塩光熱写真ドライイメージング材料の試料３−１と同様にして表３に示す銀塩光熱写真ドライイメージング材料の試料３−２〜３−４を作製した。
【０１３３】
塗布はスピード１６０ｍ／ｍｉｎで行い、コーティングダイ先端と支持体との間隔を０．１４〜０．２８ｍｍに、また、塗布液の吐出スリット幅に対して塗布幅が左右ともに各０．５ｍｍ広がるように調節し、減圧室の圧力を大気圧に対して３９２Ｐａ低く設定した。その際、支持体は帯電しないようにハンドリング及び温湿度を制御し、更に塗布直前にイオン風で除電した。引き続くチリングゾーンでは、乾球温度が１８℃、湿球温度が１２℃の風を３０秒間吹き当てて、塗布液を冷却した後、つるまき式の浮上方式の乾燥ゾーンにて、乾球温度が３０℃、湿球温度が１８℃の乾燥風を２００秒間吹き当てた後７０℃の乾燥ゾーンを２０秒間通した後、９０℃の乾燥ゾーンを１０秒間通し、その後２５℃に冷却して、塗布液中の溶剤の揮発を行った。チリングゾーンおよび乾燥ゾーンでの塗布液膜面に吹き当たる風の平均風速は７ｍ／ｓｅｃであった。作製された銀塩光熱写真ドライイメージング材料のマット度はベック平滑度で画像形成層面側が５５０秒、バック面が１３０秒であった。
【０１３４】
【表３】

【０１３５】
表３から明らかなように、本発明に係る下引済み試料及び銀塩光熱写真ドライイメージング材料試料は、比較試料に比べて、支持体と、画像形成層及び染料を含むバッキング層のを損なわずに、巻き取られた両面下引済みベースのブロッキング性が良好かつ下引加工時の搬送ロールへの汚染防止が改良されている。
【０１３６】
実施例４
〈下引加工した写真用支持体の作製〉
光学濃度０．１７０（コニカ株式会社製デンシトメータＰＤＡ−６５で測定）に青色着色した２軸延伸熱固定した厚さ１７５μｍのポリエチレンテレフタレートフィルムの両面に８Ｗ／ｍ^２・分のコロナ放電処理を施した写真用支持体に、下引加工を行った。すなわち、この写真用支持体の一方の面に、下引塗布液ａ−１１を乾燥膜厚が０．２μｍになるように塗設し、１２３℃で乾燥して感光層側下引層を形成した（下引層Ｃ−１という）。
【０１３７】
また反対側の面にバッキング層下引層として下記下引塗布液ｂ−１１を乾燥膜厚が０．２４μｍになるように塗設し、１２３℃で乾燥させてバッキング層側に帯電防止機能を持つ下引導電層（下引層Ｄ−１という）塗設した。
【０１３８】
下引層Ｃ−１とＤ−１の上表面に、８Ｗ／ｍ^２・分のコロナ放電を施し、下引層Ｃ−１の上には、下記下引上層塗布液ａ−１２を乾燥膜厚０．０５μｍになる様に塗設し１２３℃で乾燥させて下引上層Ｃ−２−１とし、Ｄ−１の上には下記下引上層塗布液ｂ−１２を乾燥膜厚０．３μｍになる様に塗設し１２３℃で乾燥させて下引上層Ｄ−２−１とし、さらに、１２３℃で２分間支持体を熱処理し、下引済み試料２−１を作製した。
【０１３９】
感光層側下引上層Ｃ−２−１を構成するバインダー（Ｌｘ−１）とＰＶＡ系化合物（Ｐ−２）の比率を表４の様に変更した以外は、下引済み試料４−１の作製と同様にして下引済み試料４−２〜４−６を作製した。
【０１４０】

【０１４１】
《下引塗布液ｂ−１１》
Ｆ−１（固形分８．３％）　　　　　　　　　　　　　　　　　　２２０ｇ
Ｌｘ−２（固形分３０％）　　　　　　　　　　　　　　　　　　　３８ｇ
ＰＶＡ−６１３（（株）クラレ製　ＰＶＡ）５質量％水溶液　　　０．４ｇ
界面活性剤（Ａ）　　　　　　　　　　　　　　　　　　　　　　０．５ｇ
以上に蒸留水を加えて１０００ｍｌとし、塗布液とした。
【０１４２】

【０１４３】
《下引上層塗布液ｂ−１２》
変性水性ポリエステルＬｘ−３溶液（１８質量％）　　　　　　　２１５ｇ
真球状シリカマット剤　日本触媒　シーホスター　ＫＥ−Ｐ５０　０．３ｇ
界面活性剤（Ａ）　　　　　　　　　　　　　　　　　　　　　　０．４ｇ
以上に蒸留水を加えて１０００ｍｌとし、塗布液とした。
【０１４４】
使用した化合物は以下の通り。
Ｆ−１：ＳｎＯ_２　特公昭３５−６６１６号記載の方法で加水分解後、デカンテーションを行ったものを使用した。（固形分８．３％）
Ｌｘ−１：ブチルアクリレート（１０質量％）／ｔ−ブチルアクリレート（３５質量％）／スチレン（２７質量％）／２−ヒドロキシエチルアクリレート（２８質量％）の共重合体ラテックス液（固形分３０％）のラテックス粒子
Ｌｘ−２：アクリル系共重合ラテックス（固形分３０％）
▲１▼ブチルアクリレート（１０質量％）／ｔ−ブチルアクリレート（３５質量％）／スチレン（２７質量％）／２−ヒドロキシエチルアクリレート（２８質量％）の共重合体ラテックス液（固形分３０％）と
▲２▼ブチルアクリレート（４０質量％）／スチレン（３０質量％）／グリシジルメタクリレート（３０質量％）の共重合体ラテックス液（固形分３０％）のラテックス粒子１０％と９０％の混合物
Ｌｘ−３：アクリル変性コポリエステル（固形分　１８％）（合成法を以下に示す）
Ｐ−２：ＲＳ−２１１７　クラレ（株）の水分散物（固形分５％）
Ｌｘ−３の合成
（水性ポリエステル溶液の調製）
テレフタル酸ジメチル３５．４質量部、イソフタル酸ジメチル３３．６３質量部、５−スルホイソフタル酸ジメチルナトリウム塩１７．９２質量部、エチレングリコール６２質量部、酢酸カルシウム一水塩０．０６５質量部、酢酸マンガン四水塩０．０２２質量部を、窒素気流下において、１７０〜２２０℃でメタノールを留去しながらエステル交換反応を行った後、リン酸トリメチル０．０４質量部、重縮合触媒として三酸化アンチモン０．０４質量部及び１，４−シクロヘキサンジカルボン酸６．８質量部を加え、２２０〜２３５℃の反応温度で、ほぼ理論量の水を留去しエステル化を行った。その後、更に反応系内を約１時間かけて減圧、昇温し最終的に２８０℃、１３３Ｐａ以下で約１時間重縮合を行い、水性ポリエステルＡ−１を作製した。得られた水性ポリエステルＡ−１の固有粘度は０．３３であった。
【０１４５】
次いで、攪拌翼、環流冷却管、温度計を付した２Ｌの３つ口フラスコに、純水８５０ｍｌを入れ、攪拌翼を回転させながら、水性ポリエステルＡ−１を１５０ｇ徐々に添加した。室温でこのまま３０分間攪拌した後、１．５時間かけて内温が９８℃になるように加熱し、この温度で３時間加熱溶解した。加熱終了後、１時間かけて室温まで冷却し、一夜放置して、１５質量％の水性ポリエステル溶液を調製した。
【０１４６】
（変性水性ポリエステルＬｘ−３溶液の調製）
攪拌翼、環流冷却管、温度計、滴下ロートを付した３Ｌの４つ口フラスコに、前記１５質量％の水性ポリエステル溶液１９００ｍｌを入れ、攪拌翼を回転させながら、内温度を８０℃まで加熱する。この中に、過酸化アンモニウムの２４％水溶液を６．５２ｍｌ加え、モノマー混合液（アクリル酸エチル３５．７ｇ、メタクリル酸メチル３５．７ｇ）を３０分間かけて滴下し、さらに３時間反応を続ける。その後３０℃以下まで冷却、濾過して、固形分濃度が１８質量％の変性水性ポリエステルＬｘ−３溶液を調製した。
【０１４７】
実施例１と同様に、下引済み試料４−１にバッキング層、感光層、表面保護層を設けて銀塩光熱写真ドライイメージング材料試料４−１を作製した。又、下引済み試料４−２〜４−６を用いた以外は銀塩光熱写真ドライイメージング材料試料４−１の作製と同様にして、銀塩光熱写真ドライイメージング材料試料４−２〜４−６を作製した。
【０１４８】
【表４】

【０１４９】
表４から明らかなように、本発明に係る下引済み試料及び銀塩光熱写真ドライイメージング材料試料は、比較試料に比べて、塗布ハジキ耐性が良好かつ、銀塩光熱写真ドライイメージング材料として処理後の表面比抵抗が優れている。
【０１５０】
【発明の効果】
本発明により、支持体と、画像形成層及び染料を含むバッキング層の接着性を損なわずに、巻き取られた両面下引済みベースのブロッキング性が防止され、かつ、下引加工時の搬送ロールへの汚染が防止された銀塩光熱写真ドライイメージング材料を提供することができた。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a silver salt photothermographic dry imaging material comprising a support provided with a photosensitive layer containing an organic silver salt, a photosensitive silver halide, a reducing agent, and a binder. The present invention relates to a silver salt photothermographic dry imaging material characterized by a support having a formed undercoat layer.
[0002]
[Prior art]
Conventionally, in the fields of medical treatment and printing plate making, the waste liquid due to wet processing of image forming materials has been a problem in terms of workability.In recent years, the amount of treated waste liquid has been strongly reduced from the viewpoint of environmental conservation and space saving. Is desired. Therefore, there is a need for a technique relating to photothermographic materials for photographic technology, which enables efficient exposure with a laser imager or a laser imagesetter and can form a high-resolution and clear black image. Such techniques include, for example, U.S. Patent Nos. 3,152,904 and 3,487,075; As described in Morgan (Dry Silver Photographic Materials) (Handbook of Imaging Imaging Materials, Marcel Dekker, Inc., p. 48, 1991), the organic support is a silver salt as described above. And silver salt photothermographic dry imaging materials containing photosensitive silver halide grains and a reducing agent are known. Since this silver salt photothermographic dry imaging material does not use any solution-based processing chemicals, it is possible to provide the user with a system that is simpler and does not damage the environment.
[0003]
By the way, these silver salt photothermographic dry imaging materials usually use a photosensitive silver halide as an optical sensor on a support, an organic silver salt as a supply source of silver ions, and a built-in reducing agent, usually at 80 to 140 ° C. A photosensitive layer (referred to as an EC layer) for forming an image by thermal development and a backing layer (referred to as a BC layer) containing a dye for absorbing laser light are provided. These layers must be firmly adhered to the support not only before thermal development but also after thermal development. An undercoat layer is provided on the support for the purpose of easy adhesion.
[0004]
When the image forming layer or the backing layer is applied off-line after the undercoat layer is coated on both sides of the support, the undercoat layer is once wound up and stored. The easy adhesion function of the undercoat and the blocking property at the time of storage are contradictory properties, and even if a little blocking occurs, it causes transport failure, causing application failure or repelling when applying the image forming layer or backing layer, It is a serious failure that leads to a misdiagnosis.
[0005]
The design of a silver salt photothermographic dry imaging material requires special considerations for thermal development different from a photosensitive material developed with a conventional developer. In particular, during heat development, compared to processing using a conventional developing solution, heat is usually applied at 80 to 140 ° C., so an easy-adhesion design different from the conventional one is required, and in the direction in which blocking between the sublayers is deteriorated, is there.
[0006]
On the other hand, the application of the undercoat layer has been made more efficient by high-speed application as the production technology has increased year by year. However, since the load on the contact roll also increases, contamination due to abrasion and adhesion on the roll tends to occur. There is a demand for a design that does not cause a serious failure such as a coating failure or coating repelling.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to prevent the blocking property of the wound double-sided undercoated base without impairing the adhesion between the support and the backing layer containing the image forming layer and the dye, and at the time of undercoating. An object of the present invention is to provide a silver salt photothermographic dry imaging material in which contamination of a transport roll is prevented.
[0008]
[Means for Solving the Problems]
The above object of the present invention has been achieved by the following configurations.
[0009]
1. In a silver salt photothermographic dry imaging material comprising one or more image forming layers containing an organic silver salt, a photosensitive silver halide, a reducing agent, and a binder on a support, a non- It has 2 to 3 image forming sublayers, and has 2 to 3 non-image forming sublayers under the backing layer containing a dye on the side of the support opposite to the side having the image forming layer. A silver salt photothermographic dry imaging material characterized by the following.
[0010]
2. In a silver salt photothermographic dry imaging material comprising one or more image forming layers containing an organic silver salt, a photosensitive silver halide, a reducing agent, and a binder on a support, a non-adhesive layer adjacent to the image forming layer The difference in SP value between the imaging subbing layer and the non-imaging subbing layer adjacent to the dye-containing backing layer on the side opposite to the side having the image forming layer of the support is 2.05 to 8.20 ( MPa)^1/2A silver salt photothermographic dry imaging material, characterized in that:
[0011]
The present invention will be described in more detail. The first and second aspects of the present invention will be described.
[0012]
The non-image forming undercoat layer of the present invention has 2 to 3 layers, and may be a conductive undercoat layer. The following are preferably used. For example, as the conductive substance, metal oxide fine particles that easily form nonstoichiometric compounds such as an oxygen-deficient oxide, a metal-excess oxide, a metal-deficient oxide, and an oxygen-excess oxide are preferably used. Among them, the most preferable metal oxides for the present invention are metal oxide fine particles that can be produced in various manners. As the metal oxide, a crystalline metal oxide is generally used, and ZnO, TiO₂, SnO₂, Al₂O₃, In₂O₃, SiO₂, MgO, B₂O, MoO₃And composite oxides thereof. Among them, ZnO, TiO₂, SnO₂Preferably, the composite oxide is made of TiO such as Al, In or the like with respect to ZnO.₂For SnO, Nb, Ta, etc.₂In particular, those containing 0.01 to 30 mol% of different elements such as Sb, Nb and halogen element are preferable, and those containing 0.1 to 10 mol% are particularly preferable.
[0013]
The volume resistivity of the fine particles of these metal oxides is 10⁷Ω · cm or less, especially 10⁵It is preferably Ω · cm or less. It is preferable to use a compound having an oxygen vacancy in the crystal or a small amount of a different kind of atom serving as a so-called donor for the metal oxide because conductivity is improved. The method for producing such metal oxide fine particles is described in detail in, for example, JP-A-56-143430.
[0014]
Although such metal oxide fine particles have high conductivity, it is necessary to consider the particle diameter and the ratio of particle / binder to light scattering, etc., that haze is deteriorated, that it is difficult to disperse, It is more preferable to use an inorganic colloid existing in a colloidal form in water. Inorganic colloids are defined in Kyoritsu Shuppan's Dictionary of Chemistry and contain 10 colloids per particle.⁵-10⁹Contains a number of atoms. Depending on the element, it can be obtained as a metal colloid, oxide colloid, or hydroxide colloid. As the metal colloid, gold, palladium, platinum, silver, sulfur and the like are preferably used. As the oxide colloid, hydroxide colloid, carbonate colloid, and sulfate colloid, zinc, magnesium, silicon, calcium, aluminum, strontium Oxide colloids such as barium, zirconium, titanium, manganese, iron, cobalt, nickel, tin, indium, molybdenum and vanadium, hydroxide colloids, carbonate colloids and sulfate colloids are preferably used in the present invention. Especially ZnO, TiO₂, And SnO₂Is preferable, and SnO₂Is particularly preferred. Further, as an example of doping with a different atom, TiO such as Al, In or the like is used for ZnO.₂For SnO, Nb, Ta, etc.₂, Sb, Nb, halogen elements and the like. The average particle size of the inorganic colloid particles is preferably from 0.001 to 1 μm from the viewpoint of dispersion stability.
[0015]
Metal oxide colloid used in the present invention, particularly colloidal SnO composed of stannic oxide₂Regarding the sol production method, SnO₂Any method may be used, such as a method of manufacturing by dispersing ultrafine particles in an appropriate solvent, or a method of manufacturing from a dispersion reaction of a Sn compound soluble in a solvent in a solvent.
[0016]
SnO₂Regarding the method for producing ultrafine particles, temperature conditions are particularly important, and a method involving heat treatment at a high temperature is not preferable because it causes growth of primary particles and a phenomenon that crystallinity increases, and heat treatment must be performed unavoidably. In some cases, it should be performed at 300 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower. However, heating from 25 ° C. to 150 ° C. is a means that is suitably selected when dispersion in the binder is considered.
[0017]
A method for producing a Sn compound soluble in a solvent from a decomposition reaction in the solvent will be described below. The Sn compound soluble in the solvent is K₂SnO₃・ 3H₂Compounds containing oxo anions such as O, SnCl₄Water-soluble halides such as (R ')₂Sn (R)₂, (R)₃SnX, (R)₂Sn (X)₂(Where R and R 'represent an alkyl group, and X represents a halogen atom or a monovalent organic group), for example, (CH₃)₃SnCl. (Pyridine), (C₄H₉)₂Sn (O₂CC₂H₅)₂Such as organometallic compounds, Sn (SO₄)₂・ 2H₂Oxo salts such as O can be mentioned. Using Sn compounds soluble in these solvents, SnO₂As a method for producing a sol, after dissolving in a solvent, a physical method such as heating and pressurizing, a chemical method such as oxidation, reduction and hydrolysis, or via an intermediate, SnO₂There is a method for producing a sol. SnO described in JP-B-35-6616₂A sol manufacturing method can be applied.
[0018]
Examples of the binder for the non-image forming subbing layer of the present invention include proteins such as gelatin, derivative gelatin, colloidal albumin and casein: cellulose compounds such as carboxymethylcellulose, hydroxyethylcellulose, diacetylcellulose and triacetylcellulose; agar, sodium alginate, Sugar derivatives such as starch derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or derivatives thereof, and partial hydrolysates, polyvinyl acetate, polyacrylonitrile, poly Vinyl polymers such as acrylates and copolymers thereof, natural products such as rosin and shellac and derivatives thereof, and many other synthetic resins are used. Emulsions such as styrene-butadiene copolymer, polyacrylic acid, polyacrylate and derivatives thereof, polyvinyl acetate, vinyl acetate-acrylate copolymer, polyolefin, and olefin-vinyl acetate copolymer are also used. be able to. In addition, organic semiconductors such as carbonate-based, polyester-based, urethane-based, epoxy-based resins, polyvinyl chloride, polyvinylidene chloride, and polypyrrole can also be used. These binders can be used as a mixture of two or more kinds. Acrylic copolymers are preferred.
[0019]
The acrylic copolymer preferably contains, for example, at least 20 mol% or more of alkyl acrylate and alkyl methacrylate. The copolymer component is preferably selected from styrene, styrene derivatives, olefin derivatives, halogenated ethylene derivatives, vinyl ester derivatives, acrylonitrile and the like.
[0020]
The dimension of the solubility parameter SP value is (MPa)^1/2It is. The details of the solubility parameter are described in “Chemistry of paint resin” (written by Takahiro Kakiuchi, published on February 15, 1972), pages 239 to 246.
[0021]
In the present invention, the SP value of the non-image forming sublayer adjacent to the image forming layer and the SP value of the non-image forming sublayer adjacent to the backing layer containing the dye on the side of the support opposite to the side having the image forming layer Is 2.05 to 8.20 (MPa)^1/2But 3.00 to 8.00 (MPa)^1/2Is more preferred.
[0022]
The support (hereinafter referred to as the support according to the present invention) which can be used for the silver salt photothermographic dry imaging material of the present invention includes various polymer materials, glass, wool cloth, cotton cloth, paper, aluminum and the like. A metal or the like can be used, but a material that can be processed into a flexible sheet or roll is preferable. A plastic film (for example, a cellulose acetate film, a polyester film, a polyethylene terephthalate film, a polyethylene naphthalate film, a polyamide film, a polyimide film, a cellulose triacetate film, a polycarbonate film, or the like) is used. In order to use the silver salt photothermographic dry imaging material of the present invention for medical purposes, the support according to the present invention is preferably a blue-colored biaxially stretched heat-fixed polyethylene terephthalate film having a thickness of 70 to 180 μm. In addition, techniques described in paragraph numbers “0030” to “0034” of JP-A-2001-22026 can be used in the present invention. The support according to the present invention is preferably subjected to a corona discharge treatment. As the condition of the discharge amount, 5 to 30 W / m²-Minutes are preferred. It is preferable to apply the undercoat layer according to the present invention to the support subjected to the corona treatment within 1 to 2 months after the corona treatment.
[0023]
The support according to the present invention can be subjected to a plasma surface treatment. In particular, plasma treatment near atmospheric pressure is preferable. As a processing gas for performing plasma discharge, a gas to which a polar functional group such as an amino group, a carboxyl group, a hydroxyl group, or a carbonyl group can be imparted may be used.₂) Gas, hydrogen (H₂) Gas, oxygen (O₂) Gas and carbon dioxide (CO₂) Gas, ammonia (NH₃) Gas, water vapor, etc. In addition, an inert gas such as helium or argon is required in addition to the reaction gas, and a stable discharge condition can be obtained by setting the mixing ratio of the gas to 60% or more. However, when plasma is generated by a pulsed electric field, an inert gas is not always necessary, and it is possible to increase the reaction gas concentration. The frequency of the pulse electric field is preferably in the range of 1 to 100 kHz. The time during which one pulsed electric field is applied is preferably 1 to 1000 μs, and the magnitude of the voltage applied to the electrode is preferably in a range where the electric field intensity is 1 to 100 kV / cm.
[0024]
The organic silver salt that can be used in the silver salt photothermographic dry imaging material of the present invention (hereinafter, referred to as the organic silver salt of the present invention) is a reducible silver source, and silver salts of organic acids and hetero organic acids, particularly Silver salts of long-chain (10 to 30 carbon atoms, preferably 15 to 25 carbon atoms) aliphatic carboxylic acids and nitrogen-containing heterocyclic compounds are preferred. Organic or inorganic complexes described in Research Disclosure 17029, 29963 in which the ligand has a value of 4.0 to 10.0 as the total stability constant for silver ions are also preferable. Examples of these suitable silver salts include silver salts of organic acids, for example, silver salts of gallic acid, oxalic acid, behenic acid, stearic acid, arachidic acid, palmitic acid, lauric acid and the like. As another example, an organic silver salt described in Paragraph No. “0193” of JP-A-2001-83659 can be mentioned. The description of paragraphs “0194” to “0197” of the same publication can also be referred to for the preparation method of the organic silver salt and the particle size of the organic silver salt. Further, as the organic silver salt according to the present invention, techniques described in JP-A-2001-48902, paragraphs “0028” to “0033”, JP-A-2000-72777, paragraphs “0025” to “0041”, etc. Can be used.
[0025]
The photosensitive silver halide that can be used in the silver salt photothermographic dry imaging material of the present invention (hereinafter, referred to as the photosensitive silver halide according to the present invention) is essentially a unique property of silver halide crystals. Or, it can absorb visible light or infrared light by an artificial physicochemical method, and when the visible light or infrared light is absorbed, a physicochemical change occurs in the silver halide crystal or the crystal surface. Means silver halide crystal grains that have been processed and prepared so that the occurrence of silver halide can occur.
[0026]
The light-sensitive silver halide according to the present invention comprises P.I. Glamkides, Chimieet Physique Photographique (published by Paul Montel, 1967); F. Duffin, Photographic Emulsion Chemistry (The Focal Press, 1966); L. The emulsion can be prepared as a silver halide grain emulsion by using a method described in "Making and Coating Photographic Emulsion" by Zelikman et al (published by The Focal Press, 1964). Of these, the so-called controlled double jet method for preparing silver halide grains while controlling the formation conditions is preferred. The halogen composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide, and silver iodide. The formation of silver halide grains according to the present invention is generally divided into two stages of silver halide seed grain (nucleus) generation and grain growth, and a method of continuously performing these steps at once may be used. A method in which particle formation and particle growth are performed separately may be used, and a technique described in paragraph number “0063” of JP-A-2001-83659 can be used.
[0027]
The photosensitive silver halide according to the present invention preferably has a small average grain size in order to suppress white turbidity after image formation and obtain good image quality. The average particle size is preferably 0.2 μm or less, more preferably 0.01 μm to 0.17 μm, and particularly preferably 0.02 μm to 0.14 μm. The term "grain size" as used herein refers to the length of a ridge of a silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case where the silver halide grains are tabular grains, the diameter means a diameter when converted into a circular image having the same area as the projected area of the main surface.
[0028]
The particle size is preferably monodisperse, and more specifically, the technology described in paragraphs “0064” to “0066” of JP-A-2001-83659 can be used. The shape of the grains may be any of cubic, octahedral, tetradecahedral, and tabular silver halide grains. In the case of tabular silver halide grains, the average aspect ratio is generally from 1.5 to 100, preferably from 2 to 50. For these, techniques described in U.S. Patent Nos. 5,264,337, 5,314,798, and 5,320,958 can be applied. Further, as the particle forming technology, the technology described in paragraph numbers “0068” to “0090” of JP-A-2001-83659 can be applied.
[0029]
The photosensitive silver halide according to the present invention preferably contains ions of a transition metal belonging to Groups 6 to 11 of the periodic table of the element for improving illuminance failure. The preferred content is 1 × 10^-9~ 1 × 10^-2Mole, more preferably 1 × 10^-8~ 1 × 10^-4Range. Preferred transition metal complexes or complex ions are those represented by the general formula [ML₆]^m(Where M is a transition metal selected from elements of Groups 6 to 11 of the periodic table, L represents a ligand, and m represents 0,-, 2-, 3- or 4-) You. Specific examples of the ligand represented by L include halogen ions (fluoride ion, chloride ion, etc.), cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide and aquo ligands, nitrosyl, Thionitrosyl and the like are preferred, and preferably, aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. As the transition metal coordination complex ion, those described in paragraph numbers “0094” to “0095” of JP-A-2001-83659 can be used.
[0030]
The photosensitive silver halide according to the present invention is preferably chemically sensitized. Regarding the preferred chemical sensitization, the chemical sensitizers and techniques described in paragraphs “0044” to “0045” of JP-A-2000-11205 can be used.
[0031]
The photosensitive silver halide according to the present invention is preferably spectrally sensitized. Regarding preferable spectral sensitization, sensitizing dyes and techniques described in Paragraph Nos. “0099” to “0144” of JP-A-2001-83659 can be used.
[0032]
The photosensitive silver halide according to the present invention, together with the sensitizing dye, is a dye that does not itself have a spectral sensitizing effect or a substance that does not substantially absorb visible light, and exhibits a supersensitizing effect. A color sensitizer may be used. As the supersensitizer, compounds described in paragraphs “0148” to “0152” of JP-A-2001-83659 can be used.
[0033]
In the present invention, in addition to the supersensitizer described above, at least one compound represented by the general formula (1) described in paragraphs “0022” to “0028” of JP-A-2001-330918 may be used. Macrocycles having different heteroatoms can be used as supersensitizers. Specific examples of the compound represented by the general formula (1) are described in paragraphs “0034” to “0039” of JP-A-2001-330918. The macrocyclic compound having a hetero atom is described in paragraphs “0044” to “0054” of JP-A-2001-330918.
[0034]
The reducing agent that can be used in the silver salt photothermographic dry imaging material of the present invention can be appropriately selected and used from known reducing agents in the technical field of silver salt photothermographic dry imaging materials. In particular, when an aliphatic silver salt of a carboxylic acid is used as the organic silver salt, at least two or more hydroxyphenyl groups at positions adjacent to the hydroxy-substituted positions of the polyphenols, particularly the hydroxyphenyl groups, which are linked by an alkylene group or sulfur, are preferred. Two or more hydroxyphenyl groups substituted by an alkyl group (eg, methyl group, ethyl group, propyl group, t-butyl group, cyclohexyl group, etc.) or an acyl group (eg, acetyl group, propionyl group, etc.) are alkylene groups Or bisphenols linked by sulfur are preferred.
[0035]
For example, hindered phenol type reducing agents described in Paragraph Nos. “0047” to “0048” of JP-A-2000-112057 are preferably used in the present invention. Specific examples of the compounds are described in paragraphs “0050” to “0051” of JP-A-2000-11205. The amount of reducing agent used is 1 × 10^-2-10 mol, preferably 1 × 10^-2１．５1.5 mol.
[0036]
The binder that can be used in the silver salt photothermographic dry imaging material of the present invention (hereinafter, referred to as the binder according to the present invention) is transparent or translucent, generally colorless, and is a natural polymer or a synthetic polymer. Examples of the binder according to the present invention include a natural or synthetic polymer described in paragraph No. “0193” of JP-A-2001-66725. As the binder according to the present invention, polyvinyl acetal is preferable, and polyvinyl butyral is particularly preferable. As for the amount of the binder used, the ratio of the binder to the organic silver salt is preferably 15: 1 to 1: 2, particularly preferably 8: 1 to 1: 1. Further, as the binder according to the present invention, a polymer latex can also be preferably used. As for the polymer latex, the compounds and techniques described in paragraphs “0194” to “0203” of JP-A-2001-66725 can be applied.
[0037]
By using a crosslinking agent, the binder according to the present invention can be expected to have an effect of improving film attachment, reducing development unevenness, and suppressing fog during storage and generation of printout silver after development. Aldehyde-based, epoxy-based, ethyleneimine-based, vinylsulfone-based, sulfonic ester-based, acryloyl-based, carbodiimide-based, and silane compound-based crosslinking agents described in JP-A-50-96216 can be used. Preferred crosslinking agents are isocyanate compounds, silane compounds, epoxy compounds or acid anhydrides.
[0038]
As for the isocyanate-based compound, the compounds and techniques described in paragraphs “0159” to “0168” of JP-A-2001-83659 can be applied. As for the epoxy compound, the compounds and techniques described in paragraphs “0170” to “0180” of JP-A-2001-83659 can be applied. As to the acid anhydride, the compounds and techniques described in paragraphs “0182” to “0187” of JP-A-2001-83659 can be applied. As for the silane compound, the compounds and techniques described in paragraphs “0022” to “0028” of JP-A-2001-264930 can be applied.
[0039]
In the silver salt photothermographic dry imaging material of the present invention, a toning agent can be used if necessary. As the toning agent that can be used in the present invention, the compounds and techniques described in paragraphs “0064” to “0066” of JP-A-2000-198757 can be applied.
[0040]
The silver salt photothermographic dry imaging material of the present invention may be formed with a filter layer on the same side or the opposite side as the photosensitive layer to control the amount or wavelength distribution of light transmitted through the photosensitive layer, or a dye or a dye on the photosensitive layer. It is preferable to include a pigment. As the dye used in the present invention, known compounds that absorb light in various wavelength regions according to the color sensitivity of the light-sensitive material can be used. For example, when the silver salt photothermographic dry imaging material of the present invention is used as an image recording material using infrared light, it is disclosed in paragraphs “0032” to “0034” of JP-A-2001-83655. It is preferable to use a squarylium dye having a thiopyrylium nucleus, a squarylium dye having a pyrylium nucleus, or the like. Further, a croconium dye having a thiopyrylium nucleus similar to a squarylium dye, and a croconium dye having a pyrylium nucleus can also be used.
[0041]
In the silver salt photothermographic dry imaging material of the present invention, since a reducing agent having a proton such as bisphenols or sulfonamidophenols is used as a reducing agent, active species capable of extracting these hydrogens are used. It is preferable that a compound capable of inactivating the reducing agent by generation is included. As the colorless photo-oxidizable substance, a compound capable of generating a free radical as a reactive species upon exposure is preferable. Examples of these compounds include biimidazolyl compounds disclosed in paragraphs “0065” to “0069” of JP-A-2001-249428 and paragraphs “0071” to “0082” of JP-A-2001-249428. Can be used.
[0042]
The silver salt photothermographic dry imaging material of the present invention can use a compound that releases a halogen atom as an active species as a compound that inactivates a reducing agent and prevents the reducing agent from reducing an organic silver salt to silver. . As specific examples of the compound that generates an active halogen atom, the compounds disclosed in paragraphs “0086” to “0102” of JP-A-2001-249428 can be used.
[0043]
The silver salt photothermographic dry imaging material of the present invention can use a silver saving agent. The silver saving agent is a compound capable of reducing the amount of silver required to obtain a certain silver image density. Although there are various possible mechanisms of the function of reducing the function, a compound having a function of improving the covering power of the developed silver is preferable. Here, the covering power of the developed silver means an optical density per unit amount of silver. Examples of the silver saving agent that can be used in the present invention include hydrazine derivative compounds disclosed in paragraphs “0075” to “0081” of JP-A-2001-66726, and paragraphs of JP-A-2001-66726. The vinyl compounds disclosed in “0109” to paragraph number “0132” and the quaternary onium compounds disclosed in paragraph numbers “0150” to “0158” of JP-A-2001-66726 are exemplified.
[0044]
The silver salt photothermographic dry imaging material of the present invention is obtained by providing a photosensitive layer containing an organic silver salt, a photosensitive silver halide, a reducing agent, and a binder on a support provided with an undercoat layer according to the present invention. However, it is preferable to form a non-photosensitive layer on the photosensitive layer. For example, a protective layer is preferably provided on the photosensitive layer, and a backing layer is provided for the purpose of protecting the photosensitive layer, and for preventing sticking to the opposite side of the support. As a binder used for the protective layer or the backing layer, a polymer having a higher glass transition point than the photosensitive layer and less likely to cause abrasion or deformation, for example, a polymer such as cellulose acetate or cellulose acetate butyrate, is selected from the above binders. It is. Further, for adjusting the gradation, two or more photosensitive layers may be provided on one side of the support or one or more layers may be provided on both sides of the support.
[0045]
The silver salt photothermographic dry imaging material of the present invention is formed by preparing a coating solution obtained by dissolving or dispersing the above-described constituent layer materials in a solvent, applying a plurality of these coating solutions simultaneously and then performing a heat treatment. Preferably. Here, “multi-layer coating at the same time” means that a coating solution for each constituent layer (for example, a photosensitive layer and a protective layer) is prepared, and when the coating solution is applied to a support, coating and drying are repeated for each layer individually. In other words, it means that each constituent layer can be formed in a state where the steps of simultaneously performing the multilayer coating and drying can be performed at the same time. That is, it is preferable to provide the upper layer before the remaining amount of all the solvents in the lower layer becomes, for example, 70% by mass or less.
[0046]
There is no particular limitation on the method of simultaneously coating a plurality of the constituent layers, and a known method such as a bar coater method, a curtain coat method, an immersion method, an air knife method, a hopper application method, and an extrusion application method can be used. . Of these, a pre-metering type coating method called an extrusion coating method is more preferable. The extrusion coating method is suitable for precision coating and organic solvent coating because the solvent does not volatilize on the slide surface unlike the slide coating method. Although this coating method has been described on the side having the photosensitive layer, the same applies to the case where the backcoat layer is provided and the coating is performed together with the undercoating. Of course, the silver salt photothermographic dry imaging material of the present invention may be an aqueous solvent.
[0047]
The development conditions of the silver salt photothermographic dry imaging material of the present invention will be described. Development conditions will vary depending on the equipment, equipment, or means used, but will typically involve heating the imagewise exposed photothermographic dry imaging material at a suitable elevated temperature. The latent image obtained after the exposure can be developed, for example, by heating at about 80 to 200 ° C, preferably about 100 to 200 ° C, for about 1 second to 2 minutes. If the heating temperature is 80 ° C. or lower, a sufficient image density cannot be obtained in a short time, and if the heating temperature is 200 ° C. or higher, the binder is melted and transferred to a roller, which adversely affects not only the image itself but also the transportability and the developing machine. . By heating, a silver image is generated by an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent.
[0048]
This reaction process proceeds without external supply of a processing liquid such as water. The equipment, apparatus or means for heating may be performed by a typical heating means such as a hot plate, an iron, a hot roller, a heat generator using carbon or white titanium or the like. If the silver salt photothermographic dry imaging material of the present invention has a protective layer, the heat treatment by contacting the surface having the protective layer with a heating means, in order to perform uniform heating, thermal efficiency, It is preferable from the viewpoint of workability and the like, and it is preferable that the surface is conveyed while being in contact with a heat roller, heated, and developed.
[0049]
At the time of development, the silver salt photothermographic dry imaging material of the present invention contains 5 to 1000 mg / m², Preferably 100 to 500 mg / m²Prepared to be This results in a silver salt photothermographic dry imaging material with high sensitivity, low fog, and high maximum density.
[0050]
Examples of the solvent include ketones such as acetone, methyl ethyl ketone, and isophorone; alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, and benzyl alcohol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and hexylene glycol. Glycols, ether alcohols such as ethylene glycol monomethyl ether and diethylene glycol monoethyl ether, ethers such as isopropyl ether, esters such as ethyl acetate and butyl acetate, chlorides such as methylene chloride and dichlorobenzene, and hydrocarbons And the like. Other examples include water, formamide, dimethylformamide, toluidine, tetrahydrofuran, acetic acid and the like. However, it is not limited to these. These solvents can be used alone or in combination of several kinds.
[0051]
The content of the solvent in the silver salt photothermographic dry imaging material can be adjusted by changing conditions such as temperature conditions in a drying step after the coating step. The content of the solvent can be measured by gas chromatography under conditions suitable for detecting the contained solvent.
[0052]
The exposure conditions of the silver salt photothermographic dry imaging material of the present invention will be described. In the exposure of the silver salt photothermographic dry imaging material of the present invention, it is desirable to use a light source appropriate for the color sensitivity imparted to the silver salt photothermographic dry imaging material. For example, if it is possible to feel infrared light, it can be applied to any light source in the infrared light range, but the laser power is high, and the silver salt photothermographic dry imaging material of the present invention is used. For example, an infrared semiconductor laser (780 nm, 820 nm) is preferably used from the viewpoint that the compound can be made transparent.
[0053]
Exposure of the silver salt photothermographic dry imaging material of the present invention is preferably performed by laser scanning exposure, and various exposure methods can be employed.
[0054]
As a first preferred method, there is a method using a laser scanning exposure machine in which the angle between the exposure surface of the silver salt photothermographic dry imaging material and the scanning laser beam does not become substantially perpendicular. Here, “being substantially not perpendicular” means that the angle is most perpendicular to the laser scanning, preferably 55 to 88 degrees, more preferably 60 to 86 degrees, and still more preferably 65 degrees. Not less than 84 degrees and most preferably not less than 70 degrees and not more than 82 degrees. The beam spot diameter on the photosensitive material exposure surface when the laser light is scanned on the photosensitive material is preferably 200 μm or less, more preferably 100 μm or less. This is preferable because the smaller the spot diameter is, the more the angle of deviation of the laser incident angle from the perpendicular can be reduced. The lower limit of the beam spot diameter is 10 μm. By performing such laser scanning exposure, it is possible to reduce image quality deterioration related to reflected light, such as occurrence of interference fringe-like unevenness.
[0055]
As a second method, it is also preferable to perform exposure using a laser scanning exposure device that emits a scanning laser beam that is a vertical multi. Image quality degradation such as generation of interference fringe-like unevenness is reduced as compared with the scanning laser beam in the longitudinal single mode. To achieve vertical multiplication, a method of using return light by multiplexing, superimposing high frequency, and the like are preferable. Here, the vertical multi means that the exposure wavelength is not single, and the distribution of the exposure wavelength is usually 5 nm or more, preferably 10 nm or more. The upper limit of the exposure wavelength distribution is not particularly limited, but is usually about 60 nm.
[0056]
As a third aspect, it is also preferable to form an image by scanning exposure using two or more lasers. As an image recording method using a plurality of lasers, there is a technique used in an image writing means of a laser printer or a digital copier which writes an image by a plurality of lines in one scan due to a demand for high resolution and high speed. And it is known, for example, from JP-A-60-166916. This is a method in which laser light emitted from a light source unit is deflected and scanned by a polygon mirror to form an image on a photoreceptor via an fθ lens or the like. It is. Image formation of laser light on silver halide photothermographic dry imaging materials in the image writing means of laser printers and digital copiers is performed by writing one laser light for the purpose of writing multiple lines of image in one scan. The next laser beam is imaged shifted by one line from the position. Specifically, the two light beams are close to each other at an interval of several tens of μm on the image plane in the sub-scanning direction, and the print density is 400 dpi (dpi is 1 inch, that is, the number of dots per 2.54 cm). ), The pitch in the sub-scanning direction of the two beams is 63.5 μm, and 42.3 μm at 600 dpi.
[0057]
Unlike the method in which the resolution is shifted by the resolution in the sub-scanning direction, it is also preferable to form an image by focusing two or more lasers at the same location on the exposure surface while changing the incident angle. At this time, if the exposure energy on the exposure surface when writing with one ordinary laser (wavelength λ [nm]) is E, the N lasers used for exposure have the same wavelength (wavelength λ [nm]). When the same exposure energy (En) is set, it is preferable to set the range of 0.9 × E ≦ En × N ≦ 1.1 × E. By doing so, energy is secured on the exposed surface, but the reflection of each laser beam to the image forming layer is reduced because the exposure energy of the laser is low, and thus the generation of interference fringes is suppressed. In the above description, a plurality of lasers have the same wavelength as λ, but lasers having different wavelengths may be used. In this case, it is preferable that (λ-30) <λ1, λ2,... Λn ≦ (λ + 30) with respect to λ [nm].
[0058]
In the above-described exposure methods of the first, second, and third aspects, as a laser used for scanning exposure, a well-known solid laser such as a ruby laser, a YAG laser, or a glass laser; a He-Ne laser; Ar ion laser, Kr ion laser, CO₂Laser, CO laser, He-Cd laser, N₂Gas lasers such as lasers and excimer lasers; InGaP lasers, AlGaAs lasers, GaAsP lasers, InGaAs lasers, InAsP lasers, CdSnP₂Lasers, semiconductor lasers such as GaSb lasers; chemical lasers, dye lasers, and the like can be appropriately selected and used according to the application. Among them, semiconductor lasers having a wavelength of 600 to 1200 nm are used due to maintenance and the size of the light source. Preferably, it is used.
[0059]
In a laser used in a laser imager or a laser imagesetter, the beam spot diameter on the exposure surface when scanning a silver halide photothermographic dry imaging material is generally 5 to 75 μm as a short axis diameter, and a long axis diameter. The diameter is in the range of 5 to 100 μm, and the laser beam scanning speed is set to an optimum value for each silver halide photothermographic dry imaging material by the sensitivity and laser power at the laser oscillation wavelength inherent to the silver halide photothermographic dry imaging material. Can be.
[0060]
【Example】
Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
[0061]
Example 1
<Preparation of undercoated photographic support>
8 W / m on both sides of a biaxially stretched and heat-fixed polyethylene terephthalate film with a thickness of 175 μm colored blue with an optical density of 0.170 (measured with a densitometer PDA-65 manufactured by Konica Corporation)²A subbing process was performed on the photographic support having been subjected to the corona discharge treatment for minutes.
[0062]
That is, an undercoating coating solution a-1 is applied on one surface of the photographic support so that the dry film thickness becomes 0.25 μm, dried at 123 ° C., and dried at 123 ° C. (Referred to as a coating layer A-1).
[0063]
On the opposite surface, a coating liquid a-1 shown below was applied as a backing layer undercoat layer so that the dry film thickness became 0.25 μm, and dried at 123 ° C. to form a backing layer side undercoat layer (lower layer). (Referred to as a subbing layer B-1). Further, the support was heat-treated at 123 ° C. for 2 minutes to prepare a sample 1-1 with a drawdown.
[0064]
The undercoating coating solution a-1 was applied on one surface of the support so as to have a dry film thickness of 0.20 μm, and dried at 123 ° C. in the same manner as in Sample 1-1, and dried at 123 ° C. (Undercoat layer A-1-2) was formed. On the opposite surface, a coating liquid a-1 shown below was applied as a backing layer undercoat layer so that the dry film thickness became 0.25 μm, and dried at 123 ° C. to form a backing layer side undercoat layer (lower layer). A coating layer B-1-2) was formed.
[0065]
8 W / m on the upper surface of the undercoat layer A-1-2²-Apply a corona discharge for 1 minute, apply the following undercoating coating solution a-1 on the undercoating layer A-1 to a dry film thickness of 0.05 μm, and dry at 123 ° C. The sample was designated as A-2-2, and the support was heat-treated at 123 ° C. for 2 minutes to produce a sample 1-2 with a drawdown.
[0066]
In the same manner as described above, an undercoating coating solution a-1 is applied on one surface of the support so that the dry film thickness becomes 0.25 μm, dried at 123 ° C., and dried on the photosensitive layer side (undercoating). The layer A-1-3) was formed. Further, on the opposite side, the following undercoating coating liquid a-1 was applied as a backing layer undercoating layer so as to have a dry film thickness of 0.20 μm, dried at 123 ° C., and dried at 123 ° C. A coating layer B-1-3) was formed.
[0067]
8 W / m on the upper surface of the undercoat layer B-1-3²-Apply a corona discharge for one minute, apply the following undercoating coating solution a-1 on B-1-3 so as to have a dry film thickness of 0.05 μm, and dry at 123 ° C. to form an undercoating upper layer B- Then, the support was heat-treated at 123 ° C. for 2 minutes to prepare a sample 1-3 with a drawdown.
[0068]
In the same manner as described above, an undercoating coating solution a-1 is applied on one surface of the support so that the dry film thickness becomes 0.20 μm, dried at 123 ° C., and dried at 123 ° C. on the photosensitive layer side (undercoating). The layer A-1-4) was formed. Further, on the opposite side, the following undercoating coating liquid a-1 was applied as a backing layer undercoating layer so as to have a dry film thickness of 0.20 μm, dried at 123 ° C., and dried at 123 ° C. A coating layer B-1-4) was formed.
[0069]
8 W / m on the upper surface of the undercoat layers A-1-4 and B-1-4²-Apply a corona discharge for a minute, apply the following undercoating coating solution a-1 on the undercoating layer A-1-4 so as to have a dry film thickness of 0.05 μm, and dry at 123 ° C. The lower coating layer A-2-4 was coated with the following coating liquid a-1 on B-1-4 so as to have a dry film thickness of 0.05 μm and dried at 123 ° C. −2-4, and the support was heat-treated at 123 ° C. for 2 minutes to prepare a sample 1-4 with a drawdown.
<< Undercoating liquid a-1 >>
Lx-1 70g
Surfactant (A) 0.3g
Aqueous dispersion of ethoxylated alcohol and ethylene homopolymer 5.0 g
Distilled water was added to make 1000 ml as described above to obtain a coating solution.
[0070]
Lx-1:
Latex particles of a copolymer latex liquid (solid content 30%) of butyl acrylate (10% by mass) / t-butyl acrylate (35% by mass) / styrene (27% by mass) / 2-hydroxyethyl acrylate (28% by mass)
[0071]
Embedded image

[0072]
<Formation of backing layer>
The following backing layer coating solution was applied on the backing undercoat layer of the previously prepared undercoating sample 1-1 by an extrusion coater so that the dry film thickness was 3.5 μm, and dried (drying temperature: 100 ° C.) And drying using a drying air having a dew point of 10 ° C. for 5 minutes) to form a backing layer.
[0073]
<< Preparation of backing layer coating solution >>
While stirring 830 g of methyl ethyl ketone, 84.2 g of cellulose acetate butyrate (Eastman Chemical Co., CAB381-20) and 4.5 g of a polyester resin (Bostic, Vitel PE2200B) were added and dissolved. Next, 0.30 g of infrared dye-1 was added to the dissolved solution, and 4.5 g of a fluorinated surfactant (Surflon KH40, Asahi Glass Co., Ltd.) dissolved in 43.2 g of methanol was added thereto. 2.3 g of an agent (Dainippon Ink Co., Ltd., Megafag F120K) was added and sufficiently stirred until dissolved. Finally, 75 g of silica (WR Grace, Syloid 64X6000) dispersed in methyl ethyl ketone at a concentration of 1% by mass with a dissolver-type homogenizer was added and stirred to prepare a backing layer coating solution.
[0074]
Embedded image

[0075]
<Layer formation on photosensitive layer side>
The following coating solution for the photosensitive layer and the coating solution for the surface protective layer are simultaneously coated on the undercoating upper layer on the photosensitive layer side opposite to the photographic support having the backing layer formed thereon using an extrusion (extrusion) coater. Thus, a silver salt photothermographic dry imaging material was prepared. For coating, the photosensitive layer was coated with 1.9 g / m of silver.²The surface protective layer was formed to have a dry film thickness of 2.5 μm. Thereafter, drying was performed for 10 minutes using a drying air having a drying temperature of 75 ° C. and a dew point temperature of 10 ° C. to prepare a silver salt photothermographic dry imaging material sample 1-1.
[0076]
(Preparation of photosensitive silver halide emulsion A)
Solution (A1)
Phenylcarbamoylated gelatin 88.3g
Compound (A) (10% aqueous methanol solution) 10 ml
Potassium bromide 0.32g
Finish to 5429ml with water
Solution (B1)
0.67mol / L silver nitrate aqueous solution 2635ml
Solution (C1)
Potassium bromide @ 51.55 g
Potassium iodide @ 1.47g
Finish to 660ml with water
Solution (D1)
Potassium bromide @ 154.9 g
Potassium iodide @ 4.41 g
Iridium chloride (1% solution) 0.93ml
Finish to 1982ml with water
Solution (E1)
0.4 mol / L aqueous potassium bromide solution the following silver potential control amount
Solution (F1)
Potassium hydroxide 0.71g
Finish with water to 20ml
Solution (G1)
56% acetic acid aqueous solution 18.0 ml
Solution (H1)
Anhydrous sodium carbonate 1.72g
Finish to 151ml with water
Compound (A):
HO (CH₂CH₂O) n- (CH (CH (CH₃) CH₂O)₁₇− (CH₂CH₂O) mH (m + n = 5-7)
Simultaneous mixing of the solution (A1) while controlling the 1/4 amount of the solution (B1) and the total amount of the solution (C1) at 45 ° C. and pAg 8.09 using a mixing stirrer described in JP-B-58-58288. It took 4 minutes and 45 seconds to add and nucleate. One minute later, the entire amount of the solution (F1) was added. During this time, pAg was appropriately adjusted using the solution (E1). After a lapse of 6 minutes, the 量 amount of the solution (B1) and the entire amount of the solution (D1) were added over 14 minutes and 15 seconds by a double jet method while controlling the temperature at 45 ° C. and the pAg at 8.09.
[0077]
After stirring for 5 minutes, the temperature was lowered to 40 ° C., and the whole amount of the solution (G1) was added to precipitate a silver halide emulsion. The supernatant was removed except for the 2,000 ml sedimented portion, 10 liters of water was added, and after stirring, the silver halide emulsion was sedimented again. The supernatant was removed, leaving 1500 ml of the sedimented portion, and 10 liters of water was further added. After stirring, the silver halide emulsion was sedimented. After removing the supernatant liquid leaving 1500 ml of the sedimented portion, the solution (H1) was added, the temperature was raised to 60 ° C., and the mixture was further stirred for 120 minutes. Finally, the pH was adjusted to 5.8, and water was added so as to be 1161 g per 1 mol of silver, whereby photosensitive silver halide emulsion A was obtained.
[0078]
This emulsion was monodisperse cubic silver iodobromide grains having an average grain size of 0.058 μm, a grain size variation coefficient of 12%, and a [100] face ratio of 92%.
[0079]
(Preparation of powdered organic silver salt A)
130.8 g of behenic acid, 67.7 g of arachidic acid, 43.6 g of stearic acid and 2.3 g of palmitic acid were dissolved in 4720 ml of pure water at 80 ° C. Next, 540.2 ml of a 1.5 mol / L aqueous sodium hydroxide solution was added, 6.9 ml of concentrated nitric acid was added, and the mixture was cooled to 55 ° C. to obtain a fatty acid sodium solution. While maintaining the temperature of the above-mentioned sodium fatty acid solution at 55 ° C., 45.3 g of the above-mentioned photosensitive silver halide emulsion A and 450 ml of pure water were added and stirred for 5 minutes.
[0080]
Next, 702.6 ml of a 1 mol / L silver nitrate solution was added over 2 minutes and stirred for 10 minutes to obtain an organic silver salt dispersion. Thereafter, the obtained organic silver salt dispersion was transferred to a water washing container, deionized water was added thereto, and the mixture was stirred and allowed to stand. Then, the organic silver salt dispersion was floated and separated to remove lower water-soluble salts. Thereafter, washing with deionized water and draining are repeated until the conductivity of the waste water becomes 2 μS / cm, and centrifugal dehydration is performed. The obtained organic silver salt in the form of a cake is then washed with an air-flow dryer flash jet dryer (stock). (Manufactured by Seishin Enterprise Co., Ltd.) to dry the organic silver salt to obtain a dried organic silver salt A of organic silver salt under a nitrogen gas atmosphere and operating conditions of hot air temperature at the dryer entrance until the water content becomes 0.1%.
[0081]
Note that an infrared moisture meter was used for measuring the water content of the organic silver salt composition.
(Preparation of Preliminary Dispersion A)
14.57 g of polyvinyl butyral powder (manufactured by Monsanto, Butvar @ B-79) is dissolved in 1457 g of methyl ethyl ketone, and 500 g of powdered organic silver salt A is gradually added while stirring with a dissolver DISPERMAT @ CA-40M manufactured by VMA-GETZMANN. A preliminary dispersion A was prepared by sufficiently mixing.
[0082]
(Preparation of photosensitive emulsion dispersion liquid 1)
A media type disperser DISPERMAT @ SL in which the pre-dispersion liquid A is filled with 0.5% zirconia beads (Toray Torayceram) having an inner volume of 80% so that the residence time in the mill is 1.5 minutes using a pump. -C12EX type (manufactured by VMA-GETZMANN) and dispersed at a mill peripheral speed of 8 m / sec to prepare a photosensitive emulsion dispersion liquid 1.
[0083]
(Preparation of stabilizer liquid)
1.0 g of Stabilizer-1 and 0.31 g of potassium acetate were dissolved in 4.97 g of methanol to prepare a stabilizer solution.
[0084]
(Preparation of infrared sensitizing dye solution A)
19.2 mg of infrared sensitizing dye SD-1, 1.488 g of 2-chloro-benzoic acid, 2.779 g of stabilizer-2 and 365 mg of 5-methyl-2-mercaptobenzimidazole in 31.3 ml of methyl ethyl ketone Was dissolved in a dark place to prepare an infrared sensitizing dye solution A.
[0085]
(Preparation of additive liquid a)
27.98 g of 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -2-methylpropane as a developer, 1.54 g of 4-methylphthalic acid, and 0.48 g of the infrared dye-1 Was dissolved in 110 g of methyl ethyl ketone to obtain an additive liquid a.
[0086]
(Preparation of additive liquid b)
1.56 g of antifoggant-2 and 3.43 g of phthalazine were dissolved in 40.9 g of methyl ethyl ketone to obtain an additive liquid b.
[0087]
Embedded image

[0088]
<< Preparation of photosensitive layer coating solution >>
In an inert gas atmosphere (nitrogen 97%), the photosensitive emulsion dispersion liquid 1 (50 g) and methyl ethyl ketone 15.11 g were kept at 21 ° C. while stirring, and the chemical sensitizer S-5 (0.5% methanol Solution) (1000 μl), and 2 minutes later, 390 μl of antifoggant-1 (10% methanol solution) was added, followed by stirring for 1 hour. Furthermore, after adding 494 μl of calcium bromide (10% methanol solution) and stirring for 10 minutes, a gold sensitizer Au-5 corresponding to 1/20 mol of the above-mentioned organic chemical sensitizer was added and further stirred for 20 minutes. . Then, after adding 167 ml of stabilizer liquids and stirring for 10 minutes, 1.32 g of the said infrared sensitizing dye liquid A was added and stirred for 1 hour.
[0089]
Thereafter, the temperature was lowered to 13 ° C., and the mixture was further stirred for 30 minutes. While maintaining the temperature at 13 ° C., 13.31 g of polyvinyl butyral (Butvar B-79, manufactured by Monsanto) was added, and the mixture was stirred for 30 minutes. Then, 1.084 g of tetrachlorophthalic acid (9.4 mass% methyl ethyl ketone solution) was added. Stir for 15 minutes. While further stirring, 12.43 g of additive solution a, 1.6 ml of Desmodur N3300 / Mobay's aliphatic isocyanate (10% methyl ethyl ketone solution), and 4.27 g of additive solution b were sequentially added and stirred, followed by exposure. A layer coating solution was obtained.
[0090]
Embedded image

[0091]
Cellulose acetate butyrate (Eastman Chemical Company, 7.5 g of CAB171-15) was dissolved in 42.5 g of methyl ethyl ketone, and 5 g of calcium carbonate (Specialty Minerals, Super-Pflex 200) was added thereto, and the mixture was added to a dissolver-type homogenizer. And dispersed at 8000 rpm for 30 minutes to prepare a matting agent dispersion.
[0092]
<< Preparation of coating solution for surface protective layer >>
While stirring 865 g of methyl ethyl ketone, 96 g of cellulose acetate butyrate (Eastman Chemical Company, CAB171-15), 4.5 g of polymethyl methacrylic acid (Rohm & Haas Company, Paraloid A-21), and vinyl sulfone compound HD-1 were added. 1.5 g, benzotriazole (1.0 g) and F-based activator (Asahi Glass Co., Ltd., Surflon KH40) (1.0 g) were added and dissolved. Next, 30 g of the matting agent dispersion was added and stirred to prepare a coating solution for the surface protective layer.
[0093]
Vinyl sulfone compound HD-1: (CH₂= CHSO₂CH₂)₂CHOH
As described above, a silver salt photothermographic dry imaging material sample 1-1 was prepared by providing the backing layer, the photosensitive layer, and the surface protective layer on the undercoated sample 1-1. In addition, except that Subtracted Samples 1-2 to 1-4 were used, the silver salt photothermographic dry imaging material samples 1-1 to 1-4 were prepared in the same manner as in the preparation of the silver salt photothermographic dry imaging material sample 1. Produced.
[0094]
The evaluation method is as follows.
<< Evaluation of blocking on EC surface (photosensitive surface) and BC surface (backing surface) >>
A roll-drawn sample (rolled 300 m at a linear pressure of 130 N / m around a 3-inch core of a paper tube) was placed in a thermostat at 45 ° C. for 3 days and evaluated.
[0095]
1: sticks and breaks when peeled off
2: Observation of the surface of the peeled surface shows that the length of 100 μm or more and the destruction of the undercoat is 1 m.²10 or more are observed
3: The film can be peeled off normally, but when the surface of the peeled surface is observed, the destruction of the undercoat having a length of 100 μm or more is 1 m.²2 to 9 of them are observed
4: There is no problem because it can be peeled off normally, but when the surface of the peeled surface is observed, the destruction of the undercoat having a length of 100 μm or more is 1 m.²1/10 to 1 observed
5: No destruction of the undercoating with a length of 100 μm or more was observed when the surface of the peeled surface was observed without any problem without any problem.
[0096]
<< Evaluation of nip roll >>
The direction in which the EC surface is applied to the rubber roll and the BC surface are applied to the rubber roll between the nip rolls of a stainless steel roll and a chrome-plated stainless steel roll whose surfaces are adjusted so as to apply a linear pressure of 130 N / m and made of urethane rubber. The film base thermo-treated in the same roll shape as the blocking evaluation was transported 1000 m twice at a line speed of 50 m / min, and the dirt on the rubber roll when the EC surface came into contact and the dirt when the BC surface came into contact were evaluated. .
[0097]
1: The surface of the roll is stained with the undercoat resin visually.
2: When observing the surface of the roll, the length of 100 μm or more was found to be 1 cm under dirt.²More than 100 are observed
3: When the surface of the roll is observed, the length of 100 μm or more and the length of the undercoat is 1 cm.²10 to less than 100 are observed
4: When the surface of the roll is observed, the length of the undercoat is 100 cm or more, and the stain of the undercoat is 1 cm.²Medium 1/10 to less than 10 observed
5: When observing the surface of the roll, no dirt of undercoat having a length of 100 μm or more was observed.
[0098]
<Evaluation of EC surface after development>
Using a heat developing automatic developing machine having a heat drum, heat developing at 123 ° C. for 15 seconds, and apply a razor blade to the sample immediately after the heat developing (within 1 minute) at an angle of 45 ° to the sample surface. The cellophane pressure-sensitive adhesive tape was pressed in between the cuts, and the tape was rapidly peeled off in an almost horizontal direction in a direction opposite to 45 ° to obtain a peeled area of the heat-developable image forming layer, which was evaluated according to the following evaluation criteria.
[0099]
1. Adhesion is very weak, and the heat-developable image forming layer completely peels off
2. Peeling area is 50% or more and less than 100%
3. Peeling area is 20% or more and less than 50%
4. Adhesive strength is strong, peeling area is 5% or more and less than 20%
5. The adhesion is very strong and the peel area is less than 5%.
[0100]
[Table 1]

[0101]
As is apparent from Table 1, the subbed sample and the silver salt photothermographic dry imaging material sample according to the present invention did not impair the support, the image forming layer and the backing layer containing the dye, as compared with the comparative sample. In addition, the rolled-up double-sided base has good blocking properties and is improved in preventing contamination of the transport rolls during the subbing process.
[0102]
Example 2
Subsequently, the undercoating coating solution a-1 used in Example 1 was changed to as-1 below, and the drying temperature and the heat treatment temperature were set to 70 ° C., and the silver salt photothermographic dry imaging material sample 1-1 was exactly the same. The silver salt photothermographic dry imaging material samples 2-1 to 2-4 were produced in the same manner as in the production of
[0103]
<< Coating liquid as-1 >>
P-1 70g
Distilled water was added to make 1000 ml as described above to obtain a coating solution.
[0104]
P-1: Lx-1 was dried in a powder form by spray drying and then finished with MEK so that the solid content concentration became 30%.
[0105]
[Table 2]

[0106]
As is clear from Table 2, the subbed sample and the silver salt photothermographic dry imaging material sample according to the present invention did not impair the support and the backing layer containing the image forming layer and the dye as compared with the comparative sample. In addition, the rolled-up double-sided base has good blocking properties and is improved in preventing contamination of the transport rolls during the drawing.
[0107]
Example 3
Subsequently, the following image forming layer, intermediate layer, protective layer and antihalation back layer were coated on the subbed bases 1-1 to 1-4 used in Example 1 to prepare silver salt photothermographic dry imaging material samples 3-1 to 3-1. 3-4 was produced.
[0108]
<< Preparation of back surface coating solution >>
(1) Preparation of solid precursor dispersion (a) of base precursor
64 g of the base precursor compound 1, 28 g of diphenylsulfone and 10 g of the surfactant Demol N manufactured by Kao Corporation were mixed with 220 ml of distilled water, and the mixture was subjected to a sand mill (1/4 Gallon Sand Grinder Mill, manufactured by Imex Co., Ltd.). ) To obtain a dispersion of solid fine particles (a) of a base precursor compound having an average particle diameter of 0.2 μm.
[0109]
(2) Preparation of Dye Solid Fine Particle Dispersion
9.6 g of cyanine dye compound 1 and 5.8 g of sodium p-dodecylbenzenesulfonate are mixed with 305 ml of distilled water, and the mixture is beaded using a sand mill (1/4 Gallon Sand Grinder Mill, manufactured by Imex Co., Ltd.). The dispersion was performed to obtain a dye solid fine particle dispersion having an average particle diameter of 0.2 μm.
[0110]
(3) Preparation of antihalation layer coating solution
17 g of gelatin, 9.6 g of polyacrylamide, 70 g of the solid fine particle dispersion (a) of the above base precursor, 56 g of the above solid fine particle dispersion, 1.5 g of polymethyl methacrylate fine particles (average particle size 6.5 μm), 1.5 g of benzoisothiazolinone 0.03 g, 2.2 g of sodium polyethylene sulfonate, 0.2 g of blue dye compound 1 and 844 ml of water were mixed to prepare a coating solution for an antihalation layer.
[0111]
<< Preparation of coating solution for back surface protective layer >>
The container was kept warm at 40 ° C., gelatin 50 g, polystyrene sodium sulfonate 0.2 g, N, N-ethylenebis (vinylsulfone acetamide) 2.4 g, sodium t-octylphenoxyethoxyethaneethanesulfonate 1 g, benzoisothiazolinone 30 mg 37 mg of potassium salt of N-perfluorooctylsulfonyl-N-propylalanine, 0.15 g of polyethylene glycol mono (N-perfluorooctylsulfonyl-N-propyl-2-aminoethyl) ether [average degree of polymerization of ethylene oxide 15] C,₈F₁₇SO₃K 32mg, C₈F₁₇SO₂N (C₃H₇) (CH₂CH₂O) (CH₂)₄-SO₃Na @ 64 mg, 8.8 g of acrylic acid / ethyl acrylate copolymer (copolymerization mass ratio 5/95), 0.6 g of Aerosol OT (manufactured by American Cyanamid Co.), 1.8 g of liquid paraffin emulsion as liquid paraffin And 950 ml of water were mixed to obtain a back surface protective layer coating solution.
[0112]
<< Preparation of silver halide emulsion 1 >>
A solution obtained by adding 8.0 ml of a 1% by weight potassium bromide solution to 1421 ml of distilled water, further adding 8.2 ml of 1N nitric acid, and 20 g of phthalated gelatin was stirred at 37 ° C. in a titanium-coated stainless steel reaction bottle. While maintaining the liquid temperature, a solution A in which distilled water was added to 37.04 g of silver nitrate to dilute to 159 ml and a solution B in which 32.6 g of potassium bromide was diluted to a volume of 200 ml with distilled water were prepared, and pAg was prepared by a control double jet method. While maintaining at 8.1, the entire amount of solution A was added at a constant flow rate over 1 minute. Solution B was added by a controlled double jet method. Thereafter, 30 ml of a 3.5% by mass aqueous solution of hydrogen peroxide was added, and further 36 ml of a 3% by mass aqueous solution of benzimidazole were added. Thereafter, the solution A was again diluted with distilled water to 317.5 ml, and the solution A was finally mixed with 1 × 10 5 per mol of silver.^-4Using a solution B2 diluted with distilled water to 400 ml, twice the volume of the solution B, to dissolve the potassium trichloride iridate 3 so as to give a molar amount, the pAg was also adjusted to 8. by the controlled double jet method. While maintaining the value of 1, the solution A2 was added at a constant flow rate over 10 minutes. Solution B2 was added by a controlled double jet method. Thereafter, 50 ml of a 0.5% by mass methanol solution of 5-methyl-2-mercaptobenzimidazole was added, the pAg was further increased to 7.5 with silver nitrate, and the pH was adjusted to 3.8 with 1N sulfuric acid. The stirring is stopped, the sedimentation / desalting / washing step is performed, 3.5 g of deionized gelatin is added, and 1 mol / L sodium hydroxide is added to adjust the pH to 6.0 and the pAg to 8.2 to disperse the silver halide. Object was produced. The grains in the completed silver halide emulsion were pure silver bromide grains having an average equivalent sphere diameter of 0.053 μm and a variation coefficient of equivalent sphere diameter of 18%. The particle size and the like were determined from the average of 1000 particles using an electron microscope. The [100] plane ratio of the particles was determined to be 85% using the Kubelka-Munk method.
[0113]
The emulsion was maintained at 38 ° C. with stirring, and 0.035 g of benzoisothiazolinone (added with a 3.5% by mass methanol solution) was added. After 40 minutes, a solid dispersion of spectral sensitizing dye 1 (aqueous gelatin solution) Is 5 × 10^-31 minute later, the temperature was raised to 47 ° C., and 20 minutes later, sodium benzenethiosulfonate was added to 3 × 10^-5Mole, and 2 minutes later, the tellurium compound was added in an amount of 5 × 10 5 per mole of silver.^-5Mol was added and the mixture was aged for 90 minutes. Immediately before the completion of ripening, 5 ml of a 0.5% by mass methanol solution of N, N-dihydroxy-N-diethylmelamine was added, the temperature was lowered to 31 ° C., and 5 ml of a 3.5% by mass methanol solution of phenoxyethanol and 5-methyl- 2-mercaptobenzimidazole in an amount of 7 × 10^-3Mol and 1-phenyl-2-heptyl-5-mercapto-1,3,4-triazole in 6.4 × 10^-3A mole was added to prepare a silver halide emulsion 1.
[0114]
<< Preparation of silver halide emulsion 2 >>
Pure silver bromide cube having an average equivalent sphere diameter of 0.08 μm and a variation coefficient of equivalent sphere diameter of 15% in the same manner as in preparation of silver halide emulsion 1 except that the liquid temperature during grain formation was changed from 37 ° C. to 50 ° C. A grain emulsion was prepared. Precipitation / desalting / washing / dispersion was carried out in the same manner as in silver halide emulsion 1. Further, the addition amount of the spectral sensitizing dye 1 was 4.5 × 10 5 per mol of silver.^-3Spectral sensitization, chemical sensitization, and 5-methyl-2-mercaptobenzimidazole, 1-phenyl-2-heptyl-5-mercapto-1,3,4-triazole in the same manner as in Emulsion 1, except that the molar ratio was changed. Was added to obtain a silver halide emulsion 2.
[0115]
<< Preparation of silver halide emulsion 3 >>
Pure silver bromide cube having an average equivalent sphere diameter of 0.038 μm and a variation coefficient of equivalent sphere diameter of 20% in the same manner as in preparation of silver halide emulsion 1 except that the liquid temperature during grain formation was changed from 37 ° C. to 27 ° C. A grain emulsion was prepared. Precipitation / desalting / washing / dispersion was carried out in the same manner as in silver halide emulsion 1. Further, the addition amount of the spectral sensitizing dye 1 was set to 6 × 10^-3Spectral sensitization, chemical sensitization, and 5-methyl-2-mercaptobenzimidazole, 1-phenyl-2-heptyl-5-mercapto-1,3,4-triazole in the same manner as in Emulsion 1, except that the molar ratio was changed. Was added to obtain a silver halide emulsion 3.
[0116]
<< Preparation of mixed emulsion A for coating solution >>
70% by weight of silver halide emulsion 1, 15% by weight of silver halide emulsion 2 and 15% by weight of silver halide emulsion 3 were dissolved in a 1% by weight aqueous solution of benzothiazolium iodide in an amount of 7 per mole of silver. × 10^-3Mole was added.
[0117]
Embedded image

[0118]
<< Preparation of scaly fatty acid silver salt >>
87.6 g of behenic acid manufactured by Henkel (product name: Edenor @ C22-85R), 423 ml of distilled water, 49.2 ml of a 5 mol / L NaOH aqueous solution, and 120 ml of tert-butanol were mixed and stirred at 75 ° C. for 1 hour to react. A sodium behenate solution was obtained. Separately, 206.2 ml (pH 4.0) of an aqueous solution of 40.4 g of silver nitrate was prepared and kept at 10 ° C. A reaction vessel containing 635 ml of distilled water and 30 ml of tert-butanol was kept at 30 ° C., and while stirring, the whole amount of the sodium behenate solution and the whole amount of the silver nitrate aqueous solution were kept at a constant flow rate for 62 minutes, 10 seconds and 60 minutes, respectively. And added. At this time, only the silver nitrate aqueous solution was added for 7 minutes and 20 seconds after the start of the silver nitrate aqueous solution addition, and then the sodium behenate solution was started to be added. After 9 minutes and 30 seconds after the completion of the silver nitrate aqueous solution, only the sodium behenate solution was added. Was added. At this time, the temperature inside the reaction vessel was set at 30 ° C., and the external temperature was controlled so that the liquid temperature became constant. The piping of the addition system of the sodium behenate solution was kept warm by steam tracing, and the steam opening was adjusted so that the liquid temperature at the outlet of the tip of the addition nozzle became 75 ° C. The piping of the silver nitrate aqueous solution addition system was kept warm by circulating cold water outside the double pipe. The addition position of the sodium behenate solution and the addition position of the aqueous silver nitrate solution were arranged symmetrically with respect to the stirring axis, and were adjusted to a height such that they did not come into contact with the reaction solution. After the completion of the addition of the sodium behenate solution, the mixture was allowed to stir at the same temperature for 20 minutes, and the temperature was lowered to 25 ° C. Thereafter, the solid content was separated by suction filtration, and the solid content was washed with water until the conductivity of the filtered water became 30 μS / cm. Thus, a fatty acid silver salt was obtained. The obtained solid was stored as a wet cake without drying.
[0119]
The morphology of the obtained silver behenate particles was evaluated by electron microscopic photographing. The average values were a = 0.14 μm, b = 0.4 μm, c = 0.6 μm, average aspect ratio 5.2, and average sphere equivalent diameter. It was a scaly crystal having a sphere equivalent diameter of 0.52 μm and a coefficient of variation of 15%. (A, b, c are prescribed in the text) To a wet cake equivalent to 100 g of dry solid content, 7.4 g of polyvinyl alcohol (trade name: PVA-217, average degree of polymerization of about 1700) and water are added, and the total amount is adjusted. After 385 g, it was predispersed with a homomixer. Next, the preliminarily dispersed stock solution was subjected to a pressure of 1750 kg / cm using a dispersing machine (trade name: Microfluidizer M-110S-EH, manufactured by Microfluidics International Corporation, using a G10Z interaction chamber).²And treated three times to obtain a silver behenate dispersion. In the cooling operation, a coiled heat exchanger was mounted before and after the interaction chamber, and the temperature of the refrigerant was adjusted to set the dispersion temperature to 18 ° C.
[0120]
<< Preparation of 25% by mass dispersion of reducing agent >>
Water was added to 10 kg of 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and 10 kg of a 20% by mass aqueous solution of modified polyvinyl alcohol (Poval MP203, manufactured by Kuraray Co., Ltd.). 16 kg was added and mixed well to form a slurry. The slurry was sent by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 3 hours and 30 minutes, and then benzoisothiazolinone sodium salt was used. 0.2 g and water were added to adjust the concentration of the reducing agent to 25% by mass to obtain a reducing agent dispersion. The reducing agent particles contained in the thus obtained reducing agent dispersion had a median diameter of 0.40 μm and a maximum particle diameter of 1.8 μm or less. The resulting reducing agent dispersion was filtered through a polypropylene filter having a pore size of 10.0 μm to remove foreign substances such as dust, and stored.
[0121]
<< Preparation of 10% by mass dispersion of mercapto compound >>
8.3 kg of water was added to 5 kg of 1-phenyl-2-heptyl-5-mercapto-1,3,4-triazole and 5 kg of a 20% by mass aqueous solution of a modified polyvinyl alcohol (Poval MP203 manufactured by Kuraray Co., Ltd.). And mixed well to form a slurry. The slurry was sent by a diaphragm pump, and dispersed in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 6 hours. Was adjusted to 10% by mass to obtain a mercapto dispersion. The mercapto compound particles contained in the thus obtained mercapto compound dispersion had a median diameter of 0.40 μm and a maximum particle diameter of 2.0 μm or less. The resulting mercapto compound dispersion was filtered through a polypropylene filter having a pore size of 10.0 μm to remove foreign substances such as dust, and stored. Immediately before use, the mixture was filtered again with a polypropylene filter having a pore size of 10 μm.
[0122]
<< Preparation of 20% by mass dispersion of organic polyhalogen compound-1 >>
5 kg of tribromomethylnaphthyl sulfone, 2.5 kg of a 20% by mass aqueous solution of modified polyvinyl alcohol (Poval MP203 manufactured by Kuraray Co., Ltd.), 213 g of a 20% by mass aqueous solution of sodium triisopropylnaphthalenesulfonate, and 10 kg of water were added. The slurry was mixed well to form a slurry. The slurry was sent by a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by IMEX Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 5 hours, and then sodium benzoisothiazolinone sodium salt was added. 2 g and water were added to adjust the concentration of the organic polyhalogen compound to 20% by mass to obtain an organic polyhalogen compound dispersion. Organic polyhalogen compound particles contained in the polyhalogen compound dispersion thus obtained had a median diameter of 0.36 μm and a maximum particle diameter of 2.0 μm or less. The obtained organic polyhalogen compound dispersion was filtered with a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.
[0123]
<< Preparation of 25% by mass dispersion of organic polyhalogen compound-2 >>
This organic polyhalogen compound was dispersed in the same manner as in the dispersion 1 of 20% by mass of the organic polyhalogen compound, except that 5 kg of N-butyl-3-tribromomethanesulfonylbenzamide was used instead of 5 kg of tribromomethylnaphthyl sulfone. Was adjusted to 25% by mass, followed by filtration. The organic polyhalogen compound particles contained in the organic polyhalogen compound dispersion thus obtained had a median diameter of 0.39 μm and a maximum particle diameter of 2.2 μm or less. The obtained organic polyhalogen compound dispersion was filtered with a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored.
[0124]
<< Preparation of 30% by Mass Dispersion-3 of Organic Polyhalogen Compound >>
Similar to 20% by mass of organic polyhalogen compound dispersion-1, except that 5 kg of tribromomethylphenylsulfone was used in place of 5 kg of tribromomethylnaphthylsulfone, 5 kg of a 20% by mass aqueous solution of MP203 was dispersed and dispersed. The polyhalogen compound was diluted to 30% by mass and filtered. The organic polyhalogen compound particles contained in the organic polyhalogen compound dispersion thus obtained had a median diameter of 0.41 μm and a maximum particle diameter of 2.0 μm or less. The obtained organic polyhalogen compound dispersion was filtered with a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust, and stored. After storage, it was stored at 10 ° C. or lower until use.
[0125]
<< Preparation of 5% by mass solution of phthalazine compound >>
8 kg of modified polyvinyl alcohol MP203 manufactured by Kuraray Co., Ltd. was dissolved in 174.57 kg of water, and then 3.15 kg of a 20% by weight aqueous solution of sodium triisopropylnaphthalenesulfonate and 14.28 kg of a 70% by weight aqueous solution of 6-isopropylphthalazine were added. This was added to prepare a 5% by mass solution of 6-isopropylphthalazine.
[0126]
<< Preparation of 20% by mass dispersion of pigment >>
C. I. Pigment Blue 60 and 6.4 g of Demol N manufactured by Kao Corporation were added to 250 g of water and mixed well to form a slurry. 800 g of zirconia beads having an average diameter of 0.5 mm was prepared, put into a vessel together with the slurry, and dispersed with a dispersing machine (1 / 4G sand grinder mill: manufactured by IMEX Co., Ltd.) for 25 hours to obtain a pigment dispersion. The pigment particles contained in the pigment dispersion thus obtained had an average particle size of 0.21 μm.
[0127]
<< Preparation of SBR latex 40% by mass >>
Ultrafiltration (UF) purified SBR latex was obtained as follows. The following SBR latex diluted 10-fold with distilled water was used until the ion conductivity reached 1.5 mS / cm using UF-purification module FS03-FC-FUY03A1 (Daisen Membrane System Co., Ltd.). After purification by dilution, Sandet-BL manufactured by Sanyo Kasei Co., Ltd. was added to a concentration of 0.22% by mass. NaOH and NH₄Na with OH⁺Ion: NH₄ ⁺The ions were added so that the ions became 1: 2.3 (molar ratio), and the pH was adjusted to 8.4. The latex concentration at this time was 40% by mass.
(SBR latex: -St (68) -Bu (29) -AA (3)-latex) Average particle size 0.1 μm, concentration 45%, equilibrium water content 0.6% by mass at 25 ° C. and 60% relative humidity, Ion conductivity 4.2 mS / cm (Ion conductivity was measured using a conductivity meter CM-30S manufactured by Toa Denpa Kogyo Co., Ltd. at 25 ° C. on latex stock solution (40%)), pH 8.2.
[0128]
<< Preparation of image forming layer coating solution >>
1.1 g of a 20% by mass aqueous dispersion of the pigment obtained above, 103 g of an organic acid silver dispersion, 5 g of a 20% by mass aqueous solution of polyvinyl alcohol PVA-205 (manufactured by Kuraray Co., Ltd.), and a dispersion of the 25% by mass reducing agent 25g, organic polyhalogen compound dispersion-1, -2, -3 in 2: 5: 2 (mass ratio) 13.2g in total, 6.2% 10% dispersion of mercapto compound, ultrafiltration (UF) purification Then, 106 g of 40% by mass of the SBR latex whose pH has been adjusted and 18 ml of a 5% by mass solution of a phthalazine compound are added, and 10 g of the silver halide mixed emulsion A is mixed well, and the image forming layer (photosensitive layer, emulsion layer) is coated. Prepare the solution and put it directly on the coating die at 70ml / m²And then applied.
[0129]
<< Preparation of emulsion layer intermediate layer coating solution >>
772 g of a 10% by mass aqueous solution of polyvinyl alcohol PVA-205 (manufactured by Kuraray Co., Ltd.), 5.3 g of a 20% by mass dispersion of a pigment, methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymer) (Weight ratio 64/9/20/5/2) 2 ml of a 5% aqueous solution of aerosol OT (manufactured by American Cyanamid Co.) in 226 g of a 27.5% by weight latex solution, and a 20% aqueous solution of a diammonium phthalate salt To 10.5 ml, and water was added to make the total amount 880 g to obtain a coating solution for the intermediate layer.²To the coating die.
[0130]
<< Preparation of Coating Solution for First Layer of Emulsion Surface Protective Layer >>
64 g of inert gelatin was dissolved in water, and 80 g of a 27.5% by mass liquid of a methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymer mass ratio of 64/9/20/5/2) latex was obtained. 23 ml of a 10% by weight methanol solution of phthalic acid, 23 ml of a 10% by weight aqueous solution of 4-methylphthalic acid, 28 ml of 1N sulfuric acid, 5 ml of a 5% by weight aqueous solution of aerosol OT (manufactured by American Cyanamid Co.), and 0.1 ml of phenoxyethanol. 5 g and 0.1 g of benzoisothiazolinone were added, and water was added to make a total amount of 750 g to prepare a coating liquid, and 18.6 ml / m 2 of 26% of 4% by mass chromium alum was mixed with a static mixer immediately before coating.²To the coating die.
[0131]
<< Preparation of coating solution for second layer of emulsion surface protective layer >>
80 g of inert gelatin was dissolved in water, and 102 g of a 27.5% by mass liquid of methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymer mass ratio: 64/9/20/5/2) latex, 3.2 ml of a 5% by mass solution of potassium salt of N-perfluorooctylsulfonyl-N-propylalanine, polyethylene glycol mono (N-perfluorooctylsulfonyl-N-propyl-2-aminoethyl) ether [average degree of polymerization of ethylene oxide = 15], 32 ml of a 5% by weight solution of aerosol OT (manufactured by American Cyanamid Co.), 4 g of polymethyl methacrylate fine particles (average particle diameter 0.7 μm), and polymethyl methacrylate fine particles (average particle Diameter 6.4 μm) 21 g, 4 -1.6 g of methylphthalic acid, 4.8 g of phthalic acid, 44 ml of 1N sulfuric acid, water to 10 mg of benzoisothiazolinone so that the total amount becomes 650 g, 4% by mass of chrome alum and 0.67% by mass of phthalic acid A solution prepared by mixing 445 ml of an aqueous solution containing an acid with a static mixer immediately before coating was used as a coating solution for the surface protective layer, and 8.3 ml / m 2²To the coating die.
[0132]
<< Preparation of silver salt photothermographic dry imaging material >>
On the back side of the undercoating support, the antihalation layer coating solution was coated with a solid particulate dye in an amount of 0.04 g / m2.²And the coating amount of the gelatin for the back surface protective layer was 1.7 g / m2.²Was applied simultaneously and dried to prepare an antihalation back layer. An image forming layer (a silver halide coating amount of 0.14 g / m 2)²), An intermediate layer, a protective layer first layer, and a protective layer second layer in this order by simultaneous slide coating using a slide bead coating method to prepare a sample 3-1 of a silver salt photothermographic dry imaging material. Samples 3-2 to 3-4 of the silver salt photothermographic dry imaging material shown in Table 3 were produced in the same manner as in the sample 3-1 of the silver salt photothermographic dry imaging material.
[0133]
The coating is performed at a speed of 160 m / min. The distance between the tip of the coating die and the support is set to 0.14 to 0.28 mm. And the pressure in the decompression chamber was set 392 Pa lower than the atmospheric pressure. At that time, the handling and the temperature and humidity were controlled so that the support was not charged, and the charge was removed by ion wind immediately before coating. In the subsequent chilling zone, a dry-bulb temperature of 18 ° C. and a wet-bulb temperature of 12 ° C. are blown for 30 seconds to cool the coating solution. After blowing dry air at 30 ° C. and a wet bulb temperature of 18 ° C. for 200 seconds, pass through a dry zone of 70 ° C. for 20 seconds, pass through a dry zone of 90 ° C. for 10 seconds, and then cool to 25 ° C. to apply. The solvent in the liquid was volatilized. The average wind speed of the wind blowing on the coating liquid film surface in the chilling zone and the drying zone was 7 m / sec. The matte degree of the produced silver salt photothermographic dry imaging material was Beck's smoothness: 550 seconds on the image forming layer side and 130 seconds on the back side.
[0134]
[Table 3]

[0135]
As is clear from Table 3, the subbed sample and the silver salt photothermographic dry imaging material sample according to the present invention did not impair the support and the backing layer containing the image forming layer and the dye, as compared with the comparative sample. In addition, the rolled-up double-sided base has good blocking properties and is improved in preventing contamination of the transport roll during the subbing process.
[0136]
Example 4
<Preparation of undercoated photographic support>
8 W / m on both sides of a biaxially stretched and heat-fixed polyethylene terephthalate film with a thickness of 175 μm colored blue with an optical density of 0.170 (measured with a densitometer PDA-65 manufactured by Konica Corporation)²A subbing process was performed on the photographic support having been subjected to the corona discharge treatment for minutes. That is, an undercoating coating solution a-11 is applied on one surface of this photographic support so that the dry film thickness becomes 0.2 μm, and dried at 123 ° C. to form a photosensitive layer side undercoating layer. (Referred to as undercoat layer C-1).
[0137]
Further, on the opposite side, an undercoating coating solution b-11 shown below was applied as a backing layer undercoating layer so as to have a dry film thickness of 0.24 μm, and dried at 123 ° C. to provide an antistatic function on the backing layer side. A subbing conductive layer (referred to as subbing layer D-1) was provided.
[0138]
8 W / m on the upper surfaces of the undercoat layers C-1 and D-1²-Apply a corona discharge for a minute and apply the following undercoating upper layer coating solution a-12 on the undercoating layer C-1 so as to have a dry film thickness of 0.05 μm and dry at 123 ° C. The upper layer C-2-1 was coated with the following lower coating layer coating solution b-12 on D-1 to a dry film thickness of 0.3 μm and dried at 123 ° C. The sample was further heat-treated at 123 ° C. for 2 minutes to prepare a sample 2-1 with a drawdown.
[0139]
Except for changing the ratio of the binder (Lx-1) and the PVA-based compound (P-2) constituting the photosensitive layer-side undercoating upper layer C-2-1 as shown in Table 4, the undercoated sample 4-1 Subtracted samples 4-2 to 4-6 were produced in the same manner as the production.
[0140]

[0141]
<< Undercoating coating solution b-11 >>
F-1 (8.3% solids) @ 220 g
Lx-2 (solid content 30%) @ 38g
PVA-613 (manufactured by Kuraray Co., Ltd. {PVA) 5% by mass aqueous solution} 0.4 g
Surfactant (A) 0.5g
Distilled water was added to make 1000 ml as described above to obtain a coating solution.
[0142]

[0143]
<< Undercoat upper layer coating solution b-12 >>
Modified aqueous polyester Lx-3 solution (18% by mass) @ 215 g
Spherical silica matting agent Nippon Shokubai Seahoster KE-P50 0.3g
Surfactant (A) 0.4g
Distilled water was added to make 1000 ml as described above to obtain a coating solution.
[0144]
The compounds used are as follows.
F-1: SnO₂加 水 After hydrolysis by the method described in JP-B-35-6616, decantation was used. (Solid content 8.3%)
Lx-1: Copolymer latex liquid of butyl acrylate (10% by mass) / t-butyl acrylate (35% by mass) / styrene (27% by mass) / 2-hydroxyethyl acrylate (28% by mass) (solid content: 30% ) Latex particles
Lx-2: Acrylic copolymer latex (solid content 30%)
(1) Copolymer latex liquid of butyl acrylate (10% by mass) / t-butyl acrylate (35% by mass) / styrene (27% by mass) / 2-hydroxyethyl acrylate (28% by mass) (solid content: 30%) When
{Circle around (2)} A mixture of 10% and 90% latex particles of a copolymer latex liquid (solid content: 30%) of butyl acrylate (40% by mass) / styrene (30% by mass) / glycidyl methacrylate (30% by mass)
Lx-3: Acrylic-modified copolyester (solid content: 18%) (synthesis method is shown below)
P-2: RS-2117 @ Kuraray Co., Ltd. aqueous dispersion (solid content 5%)
Synthesis of Lx-3
(Preparation of aqueous polyester solution)
35.4 parts by mass of dimethyl terephthalate, 33.63 parts by mass of dimethyl isophthalate, 17.92 parts by mass of dimethyl sodium 5-sulfoisophthalate, 62 parts by mass of ethylene glycol, 0.065 parts by mass of calcium acetate monohydrate, acetic acid After subjecting 0.022 parts by mass of manganese tetrahydrate to transesterification while distilling off methanol at 170 to 220 ° C. under a nitrogen stream, 0.04 parts by mass of trimethyl phosphate and trioxide as a polycondensation catalyst were used. 0.04 parts by mass of antimony and 6.8 parts by mass of 1,4-cyclohexanedicarboxylic acid were added, and at a reaction temperature of 220 to 235 ° C., almost the theoretical amount of water was distilled off to carry out esterification. Thereafter, the pressure inside the reaction system was further reduced and the temperature was raised over about 1 hour, and finally polycondensation was performed at 280 ° C. and 133 Pa or lower for about 1 hour to produce an aqueous polyester A-1. The intrinsic viscosity of the obtained aqueous polyester A-1 was 0.33.
[0145]
Next, 850 ml of pure water was put into a 2 L three-necked flask equipped with a stirring blade, a reflux condenser and a thermometer, and 150 g of aqueous polyester A-1 was gradually added while rotating the stirring blade. After stirring at room temperature for 30 minutes, the mixture was heated to an internal temperature of 98 ° C. over 1.5 hours, and heated and dissolved at this temperature for 3 hours. After the completion of the heating, the mixture was cooled to room temperature over 1 hour, and left overnight to prepare a 15% by mass aqueous polyester solution.
[0146]
(Preparation of modified aqueous polyester Lx-3 solution)
Into a 3 L four-necked flask equipped with a stirring blade, a reflux condenser, a thermometer, and a dropping funnel, 1900 ml of the 15% by mass aqueous polyester solution is placed, and the inner temperature is heated to 80 ° C. while rotating the stirring blade. . 6.52 ml of a 24% aqueous solution of ammonium peroxide was added thereto, and a monomer mixture (ethyl acrylate 35.7 g, methyl methacrylate 35.7 g) was added dropwise over 30 minutes, and the reaction was continued for another 3 hours. Thereafter, the mixture was cooled to 30 ° C. or lower and filtered to prepare a modified aqueous polyester Lx-3 solution having a solid content of 18% by mass.
[0147]
As in Example 1, a silver salt photothermographic dry imaging material sample 4-1 was prepared by providing a backing layer, a photosensitive layer, and a surface protective layer on the undercoated sample 4-1. Further, except that the subsampled samples 4-2 to 4-6 were used, the silver salt photothermographic dry imaging material samples 4-2 to 4--6 were prepared in the same manner as in the preparation of the silver salt photothermographic dry imaging material sample 4-1. No. 6 was produced.
[0148]
[Table 4]

[0149]
As is evident from Table 4, the subbed sample and the silver salt photothermographic dry imaging material sample according to the present invention have better coating repellency and a silver salt photothermographic dry imaging material as compared with the comparative sample. Has excellent surface resistivity.
[0150]
【The invention's effect】
According to the present invention, the blocking property of the wound double-sided undercoated base is prevented without impairing the adhesiveness between the support, the image forming layer and the backing layer containing the dye, and the transport roll during the undercoating process Thus, it was possible to provide a silver salt photothermographic dry imaging material which was prevented from being contaminated.

Claims (2)

In a silver salt photothermographic dry imaging material comprising one or more image forming layers containing an organic silver salt, a photosensitive silver halide, a reducing agent, and a binder on a support, a non- It has 2 to 3 image forming sublayers, and has 2 to 3 non-image forming sublayers under the backing layer containing a dye on the side of the support opposite to the side having the image forming layer. A silver salt photothermographic dry imaging material characterized by the following. A silver salt photothermographic dry imaging material comprising one or more image forming layers containing an organic silver salt, a photosensitive silver halide, a reducing agent, and a binder on a support. The difference in SP value between the imaging subbing layer and the non-imaging subbing layer adjacent to the dye-containing backing layer on the side of the support opposite to the side having the imaging layer is 2.05 to 8.20 ( (MPa) A silver salt photothermographic dry imaging material characterized by being ^1/2 .