JP4306131B2 - Silver halide photographic material for heat development - Google Patents

Description

【０１２２】
【化１】

【０１２３】
次いで、上記下引層１に７Ｗ／ｍ²・分の出力となるようにコロナ放電を施した後、その上に下記下引塗布液２を、乾燥膜厚が９μｍとなるよう塗布した後、１４０℃（露点温度：１２℃）の乾燥風で１０秒間掛けて乾燥させて下引層２を形成し、次いで、１２３℃の乾燥ゾーンを２分間かけて搬送して、絶縁体粒子を含有する下引層２を設けた。
【０１２４】

上記下引塗布液２は、下記の条件にて超音波分散を行った後、塗布に使用した。
【０１２５】
分散条件：周波数＝２５ｋＨｚ、出力＝１００Ｗ、振動子外形寸法＝６４φ×３００ｍｍ、分散時間＝２０分
次いで、上記下引層を、プラスチックフィルムを挟んで反対側に、バック層面側の下引加工を、上記と同様の方法で行った。
【０１２６】
《熱現像感光材料の作製》
上記作製したプラスチックフィルムの試料を用いて、以下に示す方法で調製した各構成層を順次塗布して、それぞれ対応する熱現像感光材料である試料１〜６を作製した。
【０１２７】
（バック面側の塗布）
メチルエチルケトン（ＭＥＫ）８３０ｇを攪拌しながら、セルロースアセテートブチレート（ＥａｓｔｍａｎＣｈｅｍｉｃａｌ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Ｆ系活性剤（旭硝子社、サーフロンＫＨ４０）４．５ｇとＦ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、攪拌しバック面側用の塗布液を調製した。
【０１２８】
【化２】

【０１２９】
このように調製したバック面塗布液を、前記作製した各プラスチックフィルムの下引上層の上に、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、乾燥を行った。乾燥温度１００℃、露点温度１０℃の乾燥風を用いて５分間かけて乾燥した。
【０１３０】
（感光層面側の塗布）
〔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（ＣＨ₂ＣＨ₂Ｏ）_n−（ＣＨ（ＣＨ₃）ＣＨ₂Ｏ）₁₇−
（ＣＨ₂ＣＨ₂Ｏ）_mＨ ｍ＋ｎ＝５〜７
特公昭５８−５８２８８号に示される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の全量を温度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。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。
【０１３１】
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。
【０１３２】
〔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１．５モル／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。
【０１３３】
次に１モル／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。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。
【０１３４】
〔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。
【０１３５】
〔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／ｓ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。
【０１３６】
〔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。
【０１３７】
〔赤外増感色素液Ａの調製〕
１９．２ｍｇの赤外増感色素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ＭＥＫに暗所にて溶解し赤外増感色素液Ａを調製した。
【０１３８】
【化３】

【０１３９】
〔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ＭＥＫ１１０ｇに溶解し添加液ａとした。
【０１４０】
〔添加液ｂの調製〕
３．５６ｇのカブリ防止剤−２、３．４３ｇのフタラジンをＭＥＫ４０．９ｇに溶解し添加液ｂとした。
【０１４１】
【化４】

【０１４２】
〔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ＭＥＫ１５．１１ｇ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分撹拌した後に上記の化学増感剤Ｓ−５の１／２０モル相当の金増感剤Ａｕ−５を添加し、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。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％ＭＥＫ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／モーベイ社社製の脂肪族イソシアネート（１０％ＭＥＫ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。
【０１４３】
【化５】

【０１４４】
〔マット剤分散液の調製〕
セルロースアセテートブチレート（Ｅａｓｔｍａｎ Ｃｈｅｍｉｃａｌ社、７．５ｇのＣＡＢ１７１−１５）をＭＥＫ４２．５ｇに溶解し、その中に、炭酸カルシウム（Ｓｐｅｃｉａｌｉｔｙ Ｍｉｎｅｒａｌｓ社、Ｓｕｐｅｒ−Ｐｆｌｅｘ２００）５ｇを添加し、ディゾルバ型ホモジナイザにて８０００ｒｐｍで３０ｍｉｎ分散しマット剤分散液を調製した。
【０１４５】
〔表面保護層塗布液の調製〕
ＭＥＫ（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（ＶＳＣ）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。
【０１４６】
〔感光層面側塗布〕
前記感光層塗布液と表面保護層塗布液をエクストルージョン型押し出しコーターを用いて、前記作製した各プラスチックフィルムの下引層２の上に、同時に重層塗布することにより感光材料を作製した。塗布は、感光層は塗布銀量１．９ｇ／ｍ²、表面保護層は乾燥膜厚で２．５μｍになる様にして行った。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、熱現像感光材料である試料１〜６を作製した
《熱現像感光材料試料の評価》
以上のようにして作製した試料を、下記に示す評価を行った。
【０１４７】
（露光及び熱現像処理）
上記作製した各試料を、２３℃、５０％ＲＨの環境下で３日間保存した後、感光層面側から、高周波重畳にて波長８００ｎｍ〜８２０ｎｍの縦マルチモード化された半導体レーザを露光源とした露光機によりレーザ走査により濃度１．０になるように露光を与えた。この際に、各試料の露光面と露光レーザ光の角度を７５度として画像を形成した。
【０１４８】
その後、ヒートドラムを有する自動現像機を用いて感光材料の保護層とドラム表面が接触するようにして、１１０℃で１５秒熱現像処理した。その際、露光及び現像は２３℃、５０％ＲＨに調湿した部屋で行った。
【０１４９】
（膜付きの評価）
上記の様に露光、現像した各試料を、２３℃、５０％ＲＨの環境下で３日間放置した後、試料の感光層面側及びバッキング層面側に、かみそりの刃で、支持体に対して４５度の角度で支持体にまで到達するまでのキズを格子状に付け、その上に粘着テープ（セロハン粘着テープ）を圧着した後、該テープを支持体に対して４５度の角度で急速に剥離した。この時、貼り付けたテープ面積に対し、テープと一緒に剥離せずに残った感光層及びバッキング層の面積比率を測定し、下記に示す基準に則り膜付きの評価を行った。
【０１５０】
ランク５：１００％の部分が剥離せず残っている
ランク４：９０〜９９％の部分が剥離せず残っている
ランク３：８０〜８９％の部分が剥離せず残っている
ランク２：５０〜７９％の部分が乖離せず残っている
ランク１：５０％未満の部分しか残っていない。
【０１５１】
なお、上記ランクにおいて、各ランクの中間に位置するものは、例えば３．５の様な表示を行った。
【０１５２】
（塗布故障（白ポチ）の評価）
上記作製した各熱現像処理済み試料の露光部分を光学ルーペを用いて目視観察し、直径０．５ｍｍ〜３ｍｍの周辺よりも濃度の低い点状の故障の発生頻度を計測し、下記に示す基準に則り塗布故障（白ポチ）の評価を行った。
【０１５３】
ランク５：発生なし／１０ｍ²
ランク４：周囲との濃度差が０．０５以内の故障が１個／１０ｍ²
ランク３：周囲との濃度差が０．０５以内の故障が２〜３個／１０ｍ²
ランク２：周囲との濃度差が０．０６以上の故障が発生している
ランク１：周囲との濃度差が０．１以上ある故障が発生している
なお、上記ランクにおいて、各ランクの中間に位置するものは、例えば３．５の様な表示を行った。
【０１５４】
（バッキング層の塗布故障の評価）
ランク５：発生なし／１０ｍ²
ランク４：故障箇所が１〜２個／１０ｍ²
ランク３：故障箇所が３〜５個／１０ｍ²
ランク２：故障箇所が６〜８個／１０ｍ²
ランク１：故障箇所が９個以上／１０ｍ²
なお、上記ランクにおいて、各ランクの中間に位置するものは、例えば３．５の様な表示を行った。
【０１５５】
以上により得られた各評価結果を表１に示す。
【０１５６】
【表１】

【０１５７】
表１より明らかなように、下引層の構成として本発明に係る構成を有する各試料は、比較試料に対し、膜付き特性に優れると共に、白ポチ故障の発生が極めて少ない特性を有していることが判る。
【０１５８】
実施例２
実施例１の下引き塗布液１、２で用いたバインダーの代わりに次に示すバインダー（Ｐ−７）を用い、かつ無機フィラーとして、合成シリカ（平均粒径０．５μｍ）と分子量１万以下の化合物としてポリエチレングリコール（平均分子量６００）を表２に示す量を下引き塗布液１、２に添加する以外は実施例１と同様に試料を作製し、実施例１と同様の評価を行った。
【０１５９】
（Ｐ−７の調製方法）
攪拌翼、環流冷却管、温度計、滴下ロートを付した１Ｌの４つ口フラスコに、純水２５０ｍｌを入れ、攪拌翼を回転させながら、ニューレックスＲ（日本油脂社製界面活性剤）４％水溶液を１５ｍｌ加えたのち、内温度を９０℃まで加熱する。この中に過酸化アンモニウムの２％水溶液を１５ｍｌ加えモノマー混合液（アクリル酸ブチル：４８ｇ、スチレン：２４ｇ、メタクリル酸グリシジル：４８ｇ）を１時間かけて滴下し、さらに４時間反応を続ける。その後３０℃以下まで冷却し濾過した。
【０１６０】
【表２】

【０１６１】
表２より明らかなように、下引層の構成として本発明に係る構成を有する各試料は、比較試料に対し、膜付き特性に優れると共に、白ポチ故障の発生が極めて少ない特性を有していることが判る。
【０１６２】
【発明の効果】
本発明により、塗布故障（白ポチ故障）、接着強度が共に改良された熱現像感光材料を提供することができた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silver halide photographic light-sensitive material for heat development in which film formation before and after heat development is improved and failure during coating is improved.
[0002]
[Prior art]
Conventionally, a so-called wet processing conventional silver halide photographic light-sensitive material in which a film is immersed in a liquid processing agent such as a developing solution or a fixing solution is processed. Coated supports have been used. However, these subbing coating films were stable in performance against chemical changes such as acid, alkali, and moisture because the film was treated with a liquid treatment agent, but in recent years, sales have expanded rapidly mainly in the medical industry. In the silver halide photographic light-sensitive material for heat development that has been carried out, the development processing is performed by heating the film from 100 ° C. to 150 ° C., so that performance stability during heating has become a problem. For example, in a photosensitive material that is developed by heating a film at 125 ° C. for 30 seconds, the photosensitive layer may be cracked after thermal development due to the difference in thermal expansion between the plastic film used for the photosensitive material, the photosensitive layer, and the undercoat layer. There was a problem that the photosensitive layer peeled off.
[0003]
Furthermore, the silver halide photographic light-sensitive material for heat development (hereinafter also referred to as heat-development light-sensitive material or simply light-sensitive material) must contain a developing agent in the light-sensitive layer at the same time because of its development mechanism. However, it becomes thicker than conventional photosensitizers and is liable to cause failures at the time of application, and improvement from the prescription has been desired.
[0004]
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and its object is to improve silver halide photographic light-sensitive materials for heat development that have improved coating failure and adhesive strength deterioration before and after heat development and do not adversely affect photographic performance and the like. Is to provide.
[0005]
[Means for Solving the Problems]
The above object of the present invention has been achieved by the following constitutions.
[0006]
  1. In a silver halide photographic material for heat development, wherein at least one surface of the plastic film is coated with a silver halide photosensitive layer for heat development, at least one non-light-sensitive layer between the photosensitive layer and the plastic film And the non-photosensitive layerContains polymer fine particles having a repeating unit derived from an ethylenically unsaturated monomer selected from a methacrylic acid ester, an acrylic acid ester, and a maleic acid ester whose glass transition temperature is 35 ° C. or lower. The photosensitive layer contains 5% to 20% of an inorganic filler of the total amount of the polymer fine particles, a plastic organic material having a molecular weight of 100 to 10,000 of 0.5% to 5% of the total amount of the polymer fine particles. Photosensitive layerThe silver halide photographic light-sensitive material for heat development is characterized in that the dynamic elastic modulus thereof has a relationship represented by the following formula (1).
[0007]
30 <En_{twenty five}/ En₁₂₅<5000 (1)
Where En_{twenty five}Represents the dynamic modulus of the non-photosensitive layer at 25 ° C., and En₁₂₅Represents the dynamic elastic modulus of the non-photosensitive layer at 125 ° C. Also, 5.0 × 10⁶Pa ≧ En₁₂₅≧ 1.0 × 10^FivePa.
[0008]
  2. A heat-developable silver halide photographic light-sensitive material in which a heat-developable silver halide light-sensitive layer is coated on at least one surface of a plastic film, wherein at least two layers are opposite to the light-sensitive layer and a support. An intermediate layer coated between the outermost layer and the plastic film.There are polymer fine particles having a repeating unit derived from an ethylenically unsaturated monomer selected from methacrylic acid ester, acrylic acid ester and maleic acid ester having a glass transition temperature of 35 ° C. or less in the homopolymer, and The intermediate layer contains an inorganic filler of 5% to 20% of the total amount of the polymer fine particles, and a plastic organic material having a molecular weight of 100 to 10,000 of 0.5% to 5% of the total amount of the polymer fine particles.The silver halide photographic light-sensitive material for heat development is characterized in that the dynamic elastic modulus of
[0009]
30 <Ei_{twenty five}/ Ei₁₂₅<5000 (2)
Where Ei_{twenty five}Represents the dynamic modulus of the intermediate layer at 25 ° C., and Ei₁₂₅Represents the dynamic modulus of the intermediate layer at 125 ° C. Also, 5.0 × 10⁶Pa ≧ Ei₁₂₅≧ 1.0 × 10^FivePa.
[0012]
The present invention will be described in more detail.
Dynamic elastic modulus
The dynamic modulus can be obtained from the modulus of elasticity when a constant period of strain is applied, and its definition is described in "New edition of the polymer dictionary" edited by the Polymer Dictionary Editing Committee of the Society of Polymer Science, Japan, etc. Has been.
[0013]
Dynamic elastic modulus E of the present invention_tempRepresents a dynamic storage elastic modulus and is a value measured under the following conditions. E_tempTemp indicates the measurement temperature of the dynamic elastic modulus. En represents the dynamic elastic modulus of the non-photosensitive layer on the photosensitive layer side, and Ei represents the dynamic elastic modulus of the intermediate layer on the back surface (the surface opposite to the photosensitive layer with respect to the support). .
Sample: 5mm wide x 35mm long
Applied frequency: 100 rad / sec
Applied strain: 0.0001 (0.01%)
Measurement temperature: 0 to 140 ° C
Measurement interval: 5 ° C. (soaking time = 30 sec)
In the examples, the measurement was performed using an apparatus solid analyzer RSA-II manufactured by Rheometric Scientific F.E.
[0014]
The dynamic elastic modulus of both En and Ei is preferably 2000 kPa or less, and more preferably 1000 kPa or less.
[0015]
The dynamic elastic modulus of the present invention can be changed by a method generally known as a means for controlling the elastic modulus of a polymer. That is, the dynamic elastic modulus can be lowered by mixing with other polymers having lower elastic modulus, plasticizers, lower molecular weight polymers and the like. On the contrary, the dynamic elastic modulus can be increased by mixing with other polymers having higher elastic modulus, fillers, higher molecular weight polymers, cross-linking agents and the like. As means for controlling the elastic modulus in order to obtain the dynamic elastic modulus of the present invention, known means other than the above means can be used.
[0016]
Inorganic filler
The inorganic filler of the present invention refers to particles having a particle size of 0.01 μm or more among inorganic compounds contained in the non-photosensitive layer or the intermediate layer. The particle diameter is represented by the diameter of a circle having the same area as the projected area of the particles.
[0017]
As the inorganic filler used in the present invention, generally well-known fillers can be used. For example, it is described in Taiseisha's “Filler Utilization Dictionary”. For example, calcium carbonate, natural silica, synthetic silica, kaolin, clay, titanium oxide, barium sulfate, zinc oxide, alumina hydroxide, magnesium hydroxide and the like are known as amorphous fillers. Examples of the plate filler include talc, mica, and glass flakes. Examples of the acicular filler include wollastonite, potassium titanate, sepiolite, zonotlite, and aluminum borate.
[0018]
The filler used in the present invention is preferably an amorphous filler.
A preferable addition amount is 3% or more and 30% or less, more preferably 5% or more and 25% or less of the polymer fine particles of the non-photosensitive layer and the intermediate layer.
[0019]
Organic compounds with a molecular weight of 10,000 or less
The organic compound having a molecular weight of 10,000 or less used in the present invention means a compound remaining in the film after coating and drying, and is present at the time of coating like a solvent, but after coating and drying on a film. A compound that does not remain in the film is not a compound of the present invention. However, in the case of a compound which is a so-called solvent and partially evaporates at the time of drying, but the remainder remains in the film, the compound of the present invention is obtained if its molecular weight is 100 to 10,000.
[0020]
As preferred specific examples, for example, phthalic acid esters, adipic acid esters, phosphoric acid esters, and polymers having a molecular weight of 10,000 or less can also be used. For example, about 800 to 8000 polyester, PEG (polyethylene glycol), or the like can be used.
[0021]
A preferable addition amount is 0.3% or more and 7% or less of the polymer fine particles of the non-photosensitive layer and the intermediate layer.
[0022]
Polymer fine particles
For the binder used in the non-photosensitive layer and the intermediate layer of the present invention, polymer fine particles of water-soluble and water-dispersible polymers are preferably used.
[0023]
Examples of the water-soluble polymer include a synthetic water-soluble polymer and a natural water-soluble polymer, and any of them can be preferably used in the present invention. Among these, examples of the synthetic water-soluble polymer include water-soluble polyesters, those having a nonionic group in the molecular structure, those having an anionic group, and those having a nonionic group and an anionic group. Examples of the nonionic group include an ether group, an ethylene oxide group, and a hydroxy group. Examples of the anionic group include a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and the like. Examples of the natural water-soluble polymer include those having a nonionic group, those having an anionic group, and those having a nonionic group and an anionic group in the molecular structure.
[0024]
Here, the water-soluble polymer means a polymer that dissolves in an amount of 0.05 g or more with respect to 100 g of water at 20 ° C. through a heating or cooling step, and preferably a polymer that dissolves in an amount of 0.1 g or more.
[0025]
Among the water-soluble polymers, the water-soluble polyester is a substantially linear polyester obtained by polycondensation reaction between a polybasic acid or an ester-forming derivative thereof and a polyol or an ester-forming derivative thereof. Polyester in which a component having a hydrophilic group, for example, a component having a sulfonate, a diethylene glycol component, a polyalkylene ether glycol component, a polyether dicarboxylic acid component or the like is introduced into the polyester as a copolymer component because it is water-soluble Say. As the component having a hydrophilic group, a dicarboxylic acid having a sulfonate is preferably used.
[0026]
Examples of the polybasic acid component of the water-soluble polyester include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, Trimellitic acid, pyromellitic acid, dimer acid, maleic acid, fumaric acid, itaconic acid, p-hydroxybenzoic acid, p- (β-hydroxyethoxy) benzoic acid and the like can be used. The dicarboxylic acid having a sulfonate is particularly preferably one having an alkali metal sulfonate group, such as 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, Alkali metal salts such as 4-sulfonaphthalene-2,7-dicarboxylic acid and 5- (4-sulfophenoxy) isophthalic acid can be mentioned, among which sodium 5-sulfoisophthalic acid is particularly preferable. The dicarboxylic acid having these sulfonates is preferably used in the range of 5 to 15 mol%, particularly in the range of 6 to 10 mol% with respect to the total dicarboxylic acid component from the viewpoint of water solubility and water resistance.
[0027]
The water-soluble polyester preferably has terephthalic acid and isophthalic acid as main dicarboxylic acid components, and the ratio of terephthalic acid and isophthalic acid used is 30/70 to 70/30 in molar ratio. It is particularly preferable from the viewpoint of applicability to the body and solubility in water. Moreover, it is preferable to contain 50-80 mol% of these terephthalic acid components and isophthalic acid components with respect to all the dicarboxylic acid components, and it is preferable to use alicyclic dicarboxylic acid as a copolymerization component. Examples of these alicyclic dicarboxylic acids include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, Mention may be made of cyclohexyldicarboxylic acid.
[0028]
Furthermore, dicarboxylic acids other than those described above can be used as copolymerization components in water-soluble polyesters using terephthalic acid and isophthalic acid as the main dicarboxylic acid component. Examples of these dicarboxylic acids include aromatic dicarboxylic acids and linear aliphatic dicarboxylic acids. The aromatic dicarboxylic acid is preferably used within a range of 30 mol% or less of the total dicarboxylic acid component. Examples of these aromatic dicarboxylic acid components include phthalic acid, 2,5-dimethylterephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and biphenyldicarboxylic acid. Further, the linear aliphatic dicarboxylic acid is preferably used within a range of 15 mol% or less of the total dicarboxylic acid component. Examples of these linear aliphatic dicarboxylic acid components include adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.
[0029]
Examples of the polyol component include ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, and trimethylol. Propane, poly (ethylene oxide) glycol, poly (tetramethylene oxide) glycol can be used.
[0030]
As the glycol component of the water-soluble polyester, it is preferable to use one having ethylene glycol of 50 mol% or more of the total glycol components.
[0031]
The water-soluble polyester can be synthesized using a dicarboxylic acid or an ester-forming derivative thereof and glycol or an ester-forming derivative thereof as starting materials. Various methods can be used for the synthesis. For example, it can be obtained by a known polyester production method in which an initial condensate of dicarboxylic acid and glycol is formed by transesterification or direct esterification and melt polymerized. be able to. More specifically, for example, an ester exchange reaction between an ester of a dicarboxylic acid, for example, a dimethyl ester of a dicarboxylic acid, and a glycol is performed, and after distilling methanol, the pressure is gradually reduced and polycondensation is performed under a high vacuum. Method of performing, esterification reaction of dicarboxylic acid and glycol, distilling out the generated water, then gradually depressurizing, polycondensation under high vacuum, transesterification reaction between dicarboxylic acid ester and glycol And a method of performing polycondensation under high vacuum after adding an esterification reaction by adding dicarboxylic acid.
[0032]
Known transesterification catalysts and polycondensation catalysts can be used, such as manganese acetate, calcium acetate, and zinc acetate as transesterification catalysts, and antimony trioxide, germanium oxide, and dibutyltin as polycondensation catalysts. Oxides, titanium tetrabutoxide, and the like can be used. However, various conditions such as a polymerization method and a catalyst are not limited to the above examples.
[0033]
Examples of the water-soluble synthetic polymer other than the water-soluble polyester include partially saponified polyvinyl alcohol having a saponification degree of 80 to 98% or completely saponified polyvinyl alcohol having a saponification degree of 98 to 100% or a derivative thereof, or water-soluble acrylamide. Preferred are water-soluble synthetic polymers such as methacrylic acid, methacrylamide, acrylic ester, and methacrylic ester.
[0034]
Examples of the polyvinyl alcohol derivative include a product obtained by modifying a completely saponified polyvinyl alcohol with an acetoacetoxyl group (commercially available from Nippon Synthetic Chemical as Z200 and Z100).
[0035]
Examples of the acrylamide-based, methacrylamide-based, acrylic ester-based and methacrylic ester-based monomer units include acrylamide, p-hydroxyphenyl methacrylamide, hydroxymethyl methacrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate.
[0036]
Copolymers containing acrylic acid, methacrylic acid, or acrylamide, methacrylamide, acrylic ester having a hydroxyl group or methacrylic ester having a hydroxyl group as a monomer unit, at least these monomer units It only has to contain one kind. The ratio of these monomer units in the copolymer is preferably 30% by mass or more.
[0037]
Specific examples of the homopolymer or copolymer containing at least one structural unit include the following. However, the parenthesis represents the mass ratio of the monomer units.
[0038]
A-1: Polyhydroxyethyl methacrylate
A-2: Poly-p-hydroxyphenyl methacrylamide
A-3: Copolymer of hydroxyethyl methacrylate / butyl acrylate / styrene (40:15:35)
A-4: Copolymer of hydroxyethyl methacrylate / butyl acrylate / acrylic acid / styrene (40: 25: 10: 25)
A-5: copolymer of p-hydroxyphenylmethacrylamide / acrylonitrile / butyl acrylate / acrylic acid (20: 20: 40: 20)
A-6: Copolymer of butyl methacrylate / acrylic acid / styrene (25:50:25)
A-7: Copolymer of methyl methacrylate / butyl acrylate / acrylic acid / styrene (10: 10: 50: 30)
A-8: Copolymer of butyl acrylate / acrylic acid / hydroxyethyl acrylate (30:30:40)
A-9: Copolymer of butyl acrylate / methacrylic acid (50:50)
These may be used alone or in combination of two or more.
[0039]
Examples of the natural water-soluble polymer include those described in detail in the Comprehensive Technical Document on Water-soluble Polymer Water-dispersed Resin (Management Development Center Publishing Department), for example, lignin, starch, pullulan, cellulose , Alginic acid, dextran, dextrin, guar gum, gum arabic, glycogen, laminaran, lichenin, nigeran, and derivatives thereof. In addition, as the derivative of the natural water-soluble polymer, sulfonated, carboxylated, phosphorylated, sulfoalkylenated, carboxyalkylenated, alkyl phosphorylated and salts thereof are particularly preferably used. In the present invention, two or more natural water-soluble polymers may be used in combination.
[0040]
Among natural water-soluble polymers, glucose polymers and derivatives thereof are preferable, and among glucose polymers and derivatives thereof, starch, glycogen, cellulose, lichenin, dextran, nigeran, and the like are preferably used. Representative examples of the cellulose derivative include those having a structure in which at least one hydrogen atom of a hydroxyl group of cellulose is replaced with an alkyl group, a hydroxyalkyl group and / or an acyl group. Specific examples of the cellulose derivative include hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose hexahydrophthalate, methylcellulose, ethylcellulose, propylcellulose and the like.
[0041]
Next, the water-dispersible polymer is a polymer obtained by dispersing and polymerizing a vinyl monomer in water. For example, by dispersing a vinyl monomer in water, emulsion polymerization or suspension polymerization. Can be obtained. A polymerization initiator is used for the polymerization of the vinyl monomer. Examples of the polymerization initiator that can be used include ammonium persulfate, potassium persulfate, sodium persulfate, and benzoyl peroxide. Among these, ammonium persulfate is preferable. In the polymerization, a surfactant can be used as an emulsifier for the purpose of improving the polymerization stability. In this case, both general nonionic and anionic surfactants can be used. Examples of vinyl monomers include acrylic monomers such as alkyl acrylates and alkyl methacrylates (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. Hydroxy group-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc.), 2-ethylhexyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group) Acrylamide, methacrylamide, N-methyl methacrylamide, N-methyl acrylamide, N-methylol acrylamide, N-methylol methacrylamide, N, N-dimethylol acrylamide, N-methoxy Amide group-containing monomers such as til acrylamide, N-methoxymethyl methacrylamide and N-phenyl acrylamide; amino group-containing monomers such as N, N-diethylaminoethyl acrylate and N, N-diethylaminoethyl methacrylate; glycidyl acrylate and glycidyl methacrylate Epoxy group-containing monomers; monomers containing carboxyl groups such as acrylic acid, methacrylic acid and salts thereof (sodium salt, potassium salt, ammonium salt, etc.) or salts thereof. Examples of monomers other than acrylic monomers include epoxy group-containing monomers such as allyl glycidyl ether; sulfonic acid groups such as styrene sulfonic acid, vinyl sulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, etc.) Or a monomer containing a salt thereof; a monomer containing a carboxyl group or a salt thereof such as crotonic acid, itaconic acid, maleic acid, fumaric acid and salts thereof (sodium salt, potassium salt, ammonium salt, etc.); maleic anhydride, Monomers containing acid anhydrides such as itaconic anhydride; vinyl isocyanate; allyl isocyanate; styrene; vinyl trisalkoxysilane; alkyl maleic acid monoester; alkyl fumaric acid monoester; acrylonitrile; methacrylonitrile; Monoester; vinylidene chloride; vinyl acetate; vinyl chloride and the like.
[0042]
The water-dispersible polymer is composed of a repeating unit derived from an ethylenically unsaturated monomer selected from a methacrylic acid ester, an acrylic acid ester, and a maleic acid ester having a glass transition temperature of 35 ° C. or less and an ethylene other than those mentioned above. A polymer latex comprising a repeating unit derived from a polymerizable unsaturated monomer is preferred.
[0043]
The ethylenically unsaturated monomer used in the polymer fine particles of the present invention is a monomer whose homopolymer has a glass transition temperature of 35 ° C. or lower, specifically alkyl acrylate (for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, iso-nonyl acrylate, n-dodecyl acrylate, etc.), alkyl methacrylate (for example, n-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, iso-nonyl methacrylate, n-dodecyl methacrylate, etc.) and dienes (for example, butadiene, isoprene, etc.).
[0044]
More preferable monomers are monomers having a glass transition temperature of 10 ° C. or less of homopolymers. Examples of such monomers include alkyl acrylates having an alkyl side chain having 2 or more carbon atoms (for example, ethyl acrylate, n-butyl acrylate). , 2-ethylhexyl acrylate, iso-nonyl acrylate, etc.), alkyl methacrylates having an alkyl side chain of 6 or more carbon atoms (eg, n-hexyl methacrylate, 2-ethylhexyl methacrylate, etc.), dienes (eg, butadiene, isoprene, etc.) Can be mentioned as a particularly preferred example.
[0045]
Regarding the value of the glass transition temperature of the above polymer, see J.A. Brandrup, E.I. H. Immergut, “Polymer Handbook” 3rd edition (John Wily & Sons, 1989) VI / 209-VI / 277.
[0046]
The repeating unit other than the ethylenically unsaturated monomer whose glass transition temperature of the homopolymer used in the polymer fine particles of the present invention is 35 ° C. or lower is derived from a monomer whose glass transition temperature of the homopolymer exceeds 35 ° C. Preferred is a repeating unit.
[0047]
Specifically, acrylic acid esters (for example, t-butyl acrylate, phenyl acrylate, 2-naphthyl acrylate, etc.), methacrylic acid esters (for example, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, 2 -Hydroxypropyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, cresyl methacrylate, 4-chlorobenzyl methacrylate, ethylene glycol dimethacrylate, etc.), vinyl esters (eg, vinyl benzoate, pivaloyloxyethylene, etc.), acrylamides (For example, acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, butyl acrylamide, tert-butyl alcohol Rilamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, diacetoneacrylamide, etc.), methacrylamides (for example, methacrylamide, Methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, The Methyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, etc.), styrenes (for example, styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chlorostyrene, methoxy styrene, acetoxy styrene, chlorostyrene, Dichlorostyrene, bromostyrene, vinyl benzoic acid methyl ester, etc.), divinylbenzene, acrylonitrile, methacrylonitrile, N-vinylpyrrolidone, N-vinyloxazolidone, vinylidene chloride, phenyl vinyl ketone and the like.
[0048]
In addition, these polymer latices have anionic functional groups (for example, as described in JP-A-60-15935, 45-3822, 53-28086, U.S. Pat. No. 3,700,456). , A carboxyl group or a sulfonic acid group) may be copolymerized for the purpose of improving the stability of the latex.
[0049]
Examples of such monomers include the following compounds. Acrylic acid; methacrylic acid; itaconic acid, maleic acid; monoalkyl itaconate such as monomethyl itaconate, monoethyl itaconate, etc .; monoalkyl maleate such as monomethyl maleate, monoethyl maleate, etc .; citraconic acid; styrene sulfonic acid; vinyl Benzyl sulfonic acid; vinyl sulfonic acid; acryloyloxyalkyl sulfonic acid such as acryloyloxymethyl sulfonic acid, acryloyloxyethyl sulfonic acid, acryloyloxypropyl sulfonic acid, etc .; methacryloyloxyalkyl sulfonic acid such as methacryloyloxymethyl sulfonic acid, methacryloyloxyethyl Sulfonic acid, methacryloyloxypropyl sulfonic acid, etc .; acrylamide alkyl sulfonic acid such as 2-acrylamido-2-methyl Ruethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc .; methacrylamide alkylsulfonic acid, such as 2-methacrylamide-2-methylethanesulfonic acid, 2-methacrylic acid Amido-2-methylpropanesulfonic acid, 2-methacrylamideamido-2-methylbutanesulfonic acid, etc .; these acids may be alkali metal (eg, Na, K, etc.) or ammonium ion salts.
[0050]
In addition, the monomer having an anionic functional group can be used as needed for the stability of the latex regardless of the glass transition temperature of the homopolymer, and when used, A preferred amount is 0.5 to 20% by weight, particularly preferably 1 to 10% by weight, based on the total weight of the polymer.
[0051]
In addition, the polymer latex preferably has a glass transition temperature of −60 ° C. or higher, more preferably −40 ° C. or higher.
[0052]
The polymer latex according to the present invention described above is prepared by an emulsion polymerization method. The dispersed particle diameter is not particularly limited, but a preferable range is 0.01 to 1.0 μm. The monomer is emulsified in water or an organic solvent miscible with water (for example, methanol, ethanol, acetone, etc.), and generally 30 to 100 ° C., preferably 40 to 90 ° C. using a radical polymerization initiator. Done at temperature. The amount of the organic solvent miscible with water is 0 to 100%, preferably 0 to 50% by volume with respect to water.
[0053]
Plastic film of the present invention
The plastic film referred to in the present invention is not particularly limited as long as it is a sheet-like material containing plastic as a component, and may be a single-layer plastic film or a plastic film laminated with the same or different plastic or paper. It may be. The thickness of the plastic film of the present invention is not particularly limited, and may be set so as to have a required strength depending on the purpose of use, but is preferably 60 to 10,000 μm, particularly preferably 60 to 350 μm.
[0054]
Applicable plastic film or plastic film constituting the plastic film laminate includes, for example, polyester, wholly aromatic polyester, polyimide, polyarylene, polyamide, polyphenylene sulfide, polycarbonate, polyolefin such as polyethylene and polypropylene, cellulose triacetate and cellulose diacetate And cellulose plastics such as cellulose nitrate, films of polymethyl methacrylate, polystyrene, polyvinyl chloride, and polyethylene laminated paper.
[0055]
Among these, syndiotactic polystyrene and polyester are preferable, and polyester is particularly preferable in terms of excellent mechanical and optical performance and relatively inexpensive.
[0056]
The polyester film is preferably oriented so that the value of the heat of crystal fusion measured by a scanning differential calorimeter in a nitrogen stream at a heating rate of 10 ° C./min exhibits a value of 17 J / g or more.
[0057]
Although the polyester used for this invention is not specifically limited, It is preferable that it is polyester which has the film formation property which has a dicarboxylic acid component and a diol component as main structural components. The main constituent dicarboxylic acid components are terephthalic acid, isophthalic acid, phthalic acid, 2-6 naphthalene dicarboxylic acid, 2-7 naphthalene dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethane dicarboxylic acid, cyclohexane dicarboxylic acid Examples include acids, diphenyl dicarboxylic acid, diphenyl thioether dicarboxylic acid, diphenyl ketone dicarboxylic acid, and phenylindane dicarboxylic acid. Examples of the diol component include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis ( 4-Hydroxyphenyl) sulfone, bisphenol fluorene hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like.
[0058]
Among the polyesters having these as main components, from the viewpoint of transparency, mechanical strength, dimensional stability, etc., terephthalic acid as the dicarboxylic acid component, ethylene glycol and / or 1-4 cyclohexanedimethanol as the diol component Polyester as the main constituent is preferred. Among them, polyesters mainly composed of polyethylene terephthalate, copolyesters composed of terephthalic acid, 2-6 naphthalenedicarboxylic acid and ethylene glycol, and polyesters composed mainly of a mixture of two or more of these polyesters. Is preferred. Further, when the ethylene terephthalate unit is contained in an amount of 70% by mass or more with respect to the polyester, a film excellent in transparency, mechanical strength, dimensional stability and the like can be obtained.
[0059]
In the present invention, the polyester constituting the biaxially stretched polyester film may be further copolymerized with other copolymer components, or may be mixed with other polyesters. Examples of these include the dicarboxylic acid components and diol components mentioned above, or polyesters composed thereof.
[0060]
The polyester used in the present invention may contain an antioxidant. The effect is particularly remarkable when the polyester contains a compound having a polyoxyalkylene group. There are no particular restrictions on the type of antioxidant to be contained, and various types of antioxidants can be used. Examples include antioxidants such as hindered phenol compounds, phosphite compounds, and thioether compounds. Can do. Among these, an antioxidant of a hindered phenol compound is preferable in terms of transparency. Content of antioxidant is 0.01-2 mass% normally with respect to polyester, Preferably it is 0.1-0.5 mass%. By setting the content of the antioxidant in this range, the density of the unexposed portion of the photothermographic material can be prevented, so-called fogging phenomenon can be prevented, and the haze of the film can be suppressed low, so that the transparency is excellent. An information recording film support is obtained. These antioxidants may be used alone or in combination of two or more.
[0061]
The biaxially stretched polyester film that can be used in the present invention can be provided with easy slipperiness if necessary. The slipperiness imparting means is not particularly limited, but the external particle addition method for adding inert inorganic particles to the polyester, the internal particle precipitation method for precipitating the catalyst to be added at the time of polyester synthesis, or a surfactant is used as a film. A method of applying to the surface is common. Among these, the internal particle precipitation method capable of controlling the precipitated particles to be relatively small is preferable because it can provide easy slipping without impairing the transparency of the film. As the catalyst, various known catalysts can be used, but Ca and Mn are particularly preferable because high transparency can be obtained. These catalysts may be used alone or in combination of two.
[0062]
The method for synthesizing the polyester as a raw material of the biaxially stretched polyester film that can be used in the present invention is not particularly limited, and can be produced according to a conventionally known polyester production method. For example, a direct esterification method in which a dicarboxylic acid component is directly esterified with a diol component. First, a dialkyl ester is used as a dicarboxylic acid component, this is transesterified with the diol component, and this is heated under reduced pressure. A transesterification method of polymerizing by removing excess diol component can be used. At this time, if necessary, a transesterification catalyst or a polymerization reaction catalyst can be used, or a heat-resistant stabilizer can be added. In addition, in each process during synthesis, anti-coloring agent, antioxidant, crystal nucleating agent, slipping agent, stabilizer, anti-blocking agent, ultraviolet absorber, viscosity modifier, antifoaming agent, clearing agent, antistatic agent, You may add a pH adjuster, dye, a pigment, etc.
[0063]
Further, the biaxially stretched polyester film that can be used in the present invention preferably has a haze of 5% or less. More preferably, it is 3% or less. The haze is measured according to ASTM-D1003-52.
[0064]
The Tg of the biaxially stretched polyester film that can be used in the present invention is preferably 60 ° C. or higher. Tg is obtained as an average value of the temperature at which the baseline measured by the differential scanning calorimeter begins to deviate and the temperature at which the baseline returns to the baseline. When Tg is equal to or higher than this value, the film in the drying process of the developing processor is not deformed, and a plastic film having a small curling curl after the developing process is obtained.
[0065]
Next, the manufacturing method of the polyester film which can be used by this invention is demonstrated.
[0066]
A method of obtaining an unstretched sheet and a method of uniaxially stretching in the machine direction can be performed by a conventionally known method. For example, the raw material polyester is formed into pellets, dried with hot air or vacuum, melt-extruded, extruded into a sheet from a T-die, adhered to a cooling drum by an electrostatic application method, etc., cooled and solidified, and unstretched Get a sheet. Next, the obtained unstretched sheet is heated within a range of polyester glass transition temperature (Tg) to Tg + 100 ° C. through a plurality of roll groups and / or a heating device such as an infrared heater, and stretched in one or more stages. It is. The draw ratio is usually in the range of 2.5 to 6 times, and it is necessary to make it a range in which subsequent transverse drawing is possible. When the sheet has a multilayer structure, the stretching temperature is preferably set based on the Tg of the polyester of the thickest layer among the Tg of the polyester of each constituent layer.
[0067]
At this time, when a polyester is laminated, a conventionally known method may be used. For example, co-extrusion method using multiple extruders and feed block die or multi-manifold die, single layer film constituting laminate or other resin constituting laminate on laminate film is melt extruded from extruder and cooled Examples thereof include an extrusion laminating method for cooling and solidifying on a drum, and a dry laminating method in which a single layer film or a laminated film constituting a laminate is laminated via an anchor agent or an adhesive as necessary. Among them, a coextrusion method that requires few manufacturing steps and good adhesion between the layers is preferable. Next, the polyester film uniaxially stretched in the longitudinal direction obtained as described above is transversely stretched within a temperature range of Tg to Tm-20 ° C. and then heat-set. The transverse draw ratio is usually 3 to 6 times, and the ratio between the longitudinal and transverse draw ratios is appropriately adjusted so as to measure the physical properties of the obtained biaxially stretched film and to have preferable characteristics. Moreover, it is preferable that the elastic modulus in the width direction is larger than the elastic modulus in the longitudinal direction. It may be changed according to the purpose of use. At this time, it is preferable to perform transverse stretching while sequentially raising the temperature difference in the range of 1 to 50 ° C. in the stretching region divided into two or more, because the distribution of physical properties in the width direction can be reduced. Furthermore, when the film after transverse stretching is kept at a temperature of Tg-40 ° C. or higher at the final transverse stretching temperature or lower for 0.01 to 5 minutes, the distribution of physical properties in the width direction can be further reduced, which is preferable.
[0068]
The heat setting is performed at a temperature higher than the final transverse stretching temperature and usually within 0.5 to 300 seconds within a temperature range of Tm-20 ° C. or less. At this time, it is preferable to heat-fix while sequentially raising the temperature difference in the range of 1 to 100 ° C. in the region divided into two or more.
[0069]
The heat-set film is usually cooled to Tg or less, and the clip gripping portions at both ends of the film are cut and wound. At this time, it is preferable to perform a relaxation treatment of 0.1 to 10% in the width direction and / or the longitudinal direction within a temperature range of not more than the final heat setting temperature and not less than Tg. Moreover, it is preferable to cool gradually from the final heat setting temperature to Tg at a cooling rate of 100 ° C. to 10 ° C. per second. The means for cooling and relaxation treatment is not particularly limited and can be performed by a conventionally known means. However, it is preferable to perform these treatments while sequentially cooling in a plurality of temperature ranges, from the viewpoint of improving the dimensional stability of the film. The cooling rate is a value obtained by (T1−Tg) / t, where T1 is the final heat setting temperature and t is the time until the film reaches Tg from the final heat setting temperature.
[0070]
The more optimal conditions of these heat setting conditions, cooling, and relaxation treatment conditions differ depending on the polyester constituting the film, so by measuring the physical properties of the obtained biaxially stretched film and adjusting it appropriately so as to have preferable characteristics. Just decide.
[0071]
When coating the non-photosensitive layer and intermediate layer of the present invention, the surface to be coated is previously treated with chemicals, mechanical roughening, corona discharge, flame treatment, ultraviolet treatment, high frequency treatment, glow treatment. It is preferable to easily wet the coating liquid by performing discharge, active plasma treatment, laser treatment or the like. By these treatments, the surface tension of the surface to be coated is preferably 500 μN / cm.
[0072]
Each of the above-mentioned layers of the present invention preferably uses a hardener to increase the film strength, and such a hardener may be appropriately selected depending on the polymer to be used. Specifically, aldehyde-based, aziridine-based, Isoxazole-based, epoxy-based, vinylsulfone-based, acryloyl-based, carbodiimide-based, triazine-based, polymer-type, other maleimide-based, acetylene-based, and methanesulfonic acid ester-based hardeners are appropriately used alone or in combination. be able to.
[0073]
The non-photosensitive layer and intermediate layer of the present invention are preferably prevented from blocking by using a matting agent. A known matting agent can be used.
[0074]
For example, polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-α-methylstyrene copolymer, polystyrene, styrene-divinylbenzene copolymer, polyvinyl acetate, polyethylene carbonate, polytetrafluoroethylene, etc., and cellulose derivatives such as Gelatin and coacervate hardened microcapsules hardened with known hardeners, such as starch derivatives such as carboxy starch, carboxynitrophenyl starch, urea-formaldehyde-starch reactant, methyl cellulose, cellulose acetate, cellulose acetate propionate, etc. Examples include hardened gelatin made into hollow particles. These details are described in, for example, U.S. Pat. Nos. 1,939,213, 2,701,245, 2,322,037, 3,262,782, and 3,539,344. Nos. 3,767,448, etc., can be used.
[0075]
Examples of the inorganic compound include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide, barium sulfate, calcium carbonate, silver chloride desensitized by a known method, silver bromide, glass, and diatomaceous earth. it can. These details are described in, for example, U.S. Pat. Nos. 1,260,772, 2,192,241, 3,257,206, 3,370,951, and 3,523. No. 022, No. 3,769,020 and the like.
[0076]
As a method for applying the layer of the present invention, various known methods can be applied, for example, roll coating method, gravure roll coating method, spray coating method, air knife coating method, bar coating method, impregnation method and curtain coating method. Etc. can be applied alone or in combination.
[0077]
In the layer of the present invention, it is preferable that the drying process is substantially completed when the liquid film surface temperature during coating and drying is 25 to 70 ° C. and the constant rate drying time is in the range of 0.5 to 40 seconds.
[0078]
Here, the constant rate drying time T is a constant rate drying process in which all of the inflowing heat with a constant liquid film temperature is used for evaporation of the solvent, and indicates the time process. The constant rate drying time T is obtained from the following formula.
[0079]
T = hw · γ / (h + U) (Ta−Tw)
1 / U = 1 / h + t / λ
However, hw: coating liquid film thickness (m), γ: latent heat of vaporization (J / kg), h: surface heat transfer coefficient (J / s · m)²・ K), Ta: dryer air temperature (° C.), U: heat transfer coefficient on the back surface (J / s · m)²K), Tw: wet bulb temperature (° C.), t: base thickness (m), λ: thermal conductivity (J / s · m · K) of PET.
[0080]
The liquid film surface temperature refers to the solvent liquid film surface temperature during the constant rate drying process of the coating liquid film applied to the plastic film and refers to Ta. The temperature of the drying air for drying the coating film is preferably 70 ° C to 160 ° C. Moreover, after drying the coating film of this invention, it is preferable to heat-process between 110 degreeC-160 degreeC for 30 second-240 second. Further, when cooling to room temperature after the heat treatment, it is preferable to slowly cool from the heat treatment temperature to Tg + 5 of the plastic film over 10 to 180 seconds, and the time between Tg ± 5 ° C. of the plastic film is 0.5 to 10 seconds. Rapid cooling is preferred. Furthermore, it is also a preferred embodiment that the plastic film is slowly cooled from Tg-5 ° C. to room temperature over 30 seconds to 3 days.
[0081]
The constitution of the silver halide photographic material for heat development of the present invention will be described.
The photothermographic material of the present invention is usually composed of at least two layers in which at least one photosensitive layer and a layer adjacent to the photosensitive layer are provided on a support, and is necessary on the opposite side of the photosensitive layer. Accordingly, a BC layer, a protective layer, and the like are provided as appropriate. The photosensitive layer of the photothermographic material contains photosensitive silver halide grains that may be sensitized with a spectral sensitizing dye, and the photosensitive layer or an adjacent layer thereof is an organic silver salt serving as a silver source, A reducing agent for developing a silver salt to form a silver image is contained. The photosensitive layer of the photothermographic material and the adjacent layer of the photosensitive layer contain a polymer binder, a hydrophilic binder, a hydrophobic binder, or latex that provides a field for thermal development. In the photothermographic material described above, an AI layer or a BC layer containing a dye for preventing irradiation or preventing halation is provided if necessary. The photosensitive layer of the photothermographic material described above can contain a color tone agent for adjusting the color tone of the silver image, if necessary.
[0082]
In the present invention, the organic silver salt is a reducible silver source, and silver salts of organic acids and heteroorganic acids, particularly long-chain (C10-30, preferably 15-25) aliphatic carboxylic acids and A silver salt of a nitrogen-containing heterocyclic compound is preferred. Organic or inorganic complexes described in Research Disclosure (hereinafter simply referred to as RD) 17029 and 29963 in which the ligand has a value of 4.0 to 10.0 as a total stability constant with respect to silver ions preferable. Examples of these suitable silver salts include the following.
[0083]
Silver salts of organic acids, for example, silver salts of gallic acid, succinic acid, behenic acid, stearic acid, arachidic acid, palmitic acid, lauric acid and the like. Silver carboxyalkylthiourea salts, for example, silver salts such as 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, aldehydes and hydroxy-substituted aromatic carboxylic acids Silver salts or complexes of polymer reaction products, for example, silver salts of reaction products of aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.) and hydroxy-substituted acids (eg, salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid) Thru complexes, silver salts or complexes of thiones, such as 3- (2-carboxyethyl) -4-hydroxymethyl-4-thiazoline-2-thione and 3-carboxymethyl-4-thiazoline-2-thione Silver salt or complex, imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H Complex or salt of nitrogen acid and silver selected from tetrazole, 3-amino-5-benzylthio-1,2,4-triazole and benztriazole, silver salt such as saccharin, 5-chlorosalicylaldoxime, and mercaptides Silver salt. Among these, preferable silver salts include silver behenate, silver arachidate, and silver stearate.
[0084]
Photosensitive silver halide grains that can be used in the present invention will be described. Incidentally, the photosensitive silver halide grain in the present invention can absorb visible light or infrared light by an inherent physicochemical method as an intrinsic property of a silver halide crystal or by an artificial physicochemical method. And silver halide crystal grains produced by treatment so that physicochemical changes can occur in the silver halide crystal and / or on the crystal surface when absorbing visible or infrared light.
[0085]
The silver halide grains themselves used in the present invention are P.I. Chifie et Physique Photographic (published by PaulMontel, 1967) by Glafkides. F. Duffin's Photographic Emission Chemistry (published by The Focal Press, 1966), V.C. L. It can be prepared as a silver halide grain emulsion using the method described in Making and Coating Photographic Emulsion (published by The Focal Press, 1964) by Zelikman et al. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and the formation of reacting a soluble silver salt and a soluble halogen salt may be any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof. However, among the above methods, a so-called controlled double jet method in which silver halide grains are prepared while controlling formation conditions is preferable. 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.
[0086]
The silver halide that can be used in the present invention preferably has a smaller average grain size in order to keep the white turbidity after image formation low and obtain good image quality, and the average grain size is preferably 0.2 μm or less. Is preferably 0.01 μm to 0.17 μm, particularly preferably 0.02 μm to 0.14 μm. The grain size here refers to the length of the edge of the silver halide grain when the silver halide grain is a so-called normal crystal of a cube or octahedron. Further, when the silver halide grain is a tabular grain, it means a diameter when converted into a circular image having the same area as the projected area of the main surface.
[0087]
Examples of the shape of the silver halide grains include cubes, octahedrons, tetradecahedral grains, tabular grains, spherical grains, rod-like grains, and potato grains. Among these, cubic, octahedral, 14 Planar and tabular silver halide grains are preferred.
[0088]
When tabular silver halide grains are used, the average aspect ratio is preferably 1.5 or more and 100 or less, more preferably 2 or more and 50 or less. These are described in US Pat. Nos. 5,264,337, 5,314,798, 5,320,958, etc., and the desired tabular grains can be easily obtained. Further, grains having rounded corners of silver halide grains can be preferably used.
[0089]
The antifogging and image stabilizer that can be used in the present invention will be described.
As will be described later, a reducing agent having a proton such as bisphenols or sulfonamidophenols is mainly used as the reducing agent, so that these active species capable of extracting hydrogen can be generated. It is preferable that a compound capable of inactivating the reducing agent is contained. Preferably, the colorless photo-oxidizing substance is preferably a compound capable of generating free radicals as reactive active species during exposure.
[0090]
Accordingly, any compound having these functions may be used, but an organic free radical composed of a plurality of atoms is preferred. A compound having any structure may be used as long as it has such a function and does not cause any particular adverse effect on the photothermographic material.
[0091]
In addition, as a compound that generates these free radicals, the generated free radicals are carbocyclic or heterocyclic in order to have a stability that allows them to come into contact with the reducing agent for a time sufficient to react and inactivate. Those having the following aromatic group are preferred.
[0092]
Examples of the reducing agent suitable for incorporation in the photothermographic material of the present invention include US Pat. Nos. 3,770,448, 3,773,512, 3,593,863, and RD No. 17029 and 29963, and can be appropriately selected from known reducing agents. When an aliphatic carboxylic acid silver salt is used as the organic silver salt, two or more phenols are used. Polyphenols in which the group is linked by an alkylene group or sulfur, particularly an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a t-butyl group, a cyclohexyl group, etc.) at at least one position adjacent to the hydroxy substitution position of the phenol group ) Or bisphenol in which two or more of the phenol groups substituted with an acyl group (for example, acetyl group, propionyl group, etc.) are connected by an alkylene group or sulfur Louis preferable.
[0093]
The silver halide grains used in the present invention can be chemically sensitized. For example, a compound that releases a chalcogen such as sulfur or a noble metal ion that releases a noble metal ion such as a gold ion by the method disclosed in Japanese Patent Application No. 12-057004 and Japanese Patent Application No. 12-061942 Can be used to form and impart a chemical sensitization center (chemical sensitization nucleus). In the present invention, it is preferably chemically sensitized with an organic sensitizer containing a chalcogen atom. These organic sensitizers containing chalcogen atoms are preferably compounds having groups capable of adsorbing to silver halide and unstable chalcogen atom sites.
[0094]
As these organic sensitizers, organic sensitizers having various structures disclosed in the specifications of JP-A-60-150046, JP-A-4-109240, JP-A-11-218874 and the like are used. Of these, at least one compound having a structure in which a chalcogen atom is bonded to a carbon atom or a phosphorus atom by a double bond is preferable.
[0095]
In addition to the above-described sensitization methods, reduction sensitization methods and the like can also be used. As the reduction-sensitized shell-like compounds, ascorbic acid, thiourea dioxide, stannous chloride, hydrazine derivatives, borane compounds A silane compound, a polyamine compound, or the like can be used. Further, reduction sensitization can be performed by ripening the emulsion while maintaining the pH at 7 or higher or the pAg at 8.3 or lower.
[0096]
The photosensitive silver halide grains that can be used in the present invention are preferably subjected to spectral sensitization by adsorbing a spectral sensitizing dye. As spectral sensitizing dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes and the like can be used. For example, JP-A-63-159841, JP-A-60-140335, JP-A-63-231437, JP-A-63-259651, JP-A-63-304242, JP-A-63-15245, U.S. Pat. Nos. 4,740,455, 4,741,966, 4,751,175, and 4,835,096 can be used. Useful sensitizing dyes used in the present invention are described in, for example, the literature described or cited in RD No. 17643 IV-A (December 1978, p.23) and No. 18431X (August 1978, p.437). Are listed. In particular, it is preferable to use a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various laser imagers and scanners. For example, those described in JP-A Nos. 9-34078, 9-54409, and 9-80679 are used. A compound is preferably used.
[0097]
The emulsion containing silver halide grains or organic silver salt grains used in the photothermographic material of the present invention substantially absorbs dyes having no spectral sensitizing action or visible light, together with sensitizing dyes. A substance that does not exhibit a supersensitization effect may be included in the emulsion, whereby the silver halide grains may be supersensitized. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in RD 17643 (issued in December, 1978), page 23, Section J, or Japanese Patent Publication No. 9-25500. Those described in JP-A-59-19032, JP-A-59-192242, JP-A-5-341432 and the like can be used. In the present invention, in addition to the supersensitizer described above, the supersensitizer comprises a compound represented by the general formula (1) disclosed in Japanese Patent Application No. 12-070296 and a macrocyclic compound. Can be used as
[0098]
The silver saving agent that can be used in the present invention refers to a compound that can reduce the amount of silver necessary to obtain a certain silver image density. Various action mechanisms of the function of decreasing can be considered, but a compound having a function of improving the covering power of developed silver is preferable. Here, the covering power of developed silver refers to the optical density per unit amount of silver. Preferred examples of the silver saving agent include hydrazine derivative compounds, vinyl compounds, and quaternary onium compounds.
[0099]
The binder suitable for the photothermographic material of the present invention is transparent or translucent and generally colorless, and is a natural polymer synthetic resin, polymer and copolymer, or other media for forming a film such as gelatin, gum arabic, poly (vinyl). Alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (Styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)), poly (esters), Poly (urethane) , Phenoxy resins, poly (vinylidene chloride), poly (epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, and polyamides. It may be hydrophilic or non-hydrophilic. Preferred binders for the photosensitive layer of the photothermographic material are polyvinyl acetals, and a particularly preferred binder is polyvinyl butyral. For non-photosensitive layers such as overcoat layers and undercoat layers, especially protective layers and backcoat layers, cellulose esters which are polymers with higher softening temperatures, especially polymers such as triacetyl cellulose and cellulose acetate butyrate preferable. In addition, as needed, said binder can be used in combination of 2 or more type.
[0100]
In the present invention, it is known that the use of a crosslinking agent with respect to the binder improves the film formation and reduces development unevenness. However, it suppresses fogging during storage and produces printed silver after development. There is also an inhibitory effect. As the crosslinking agent used in the present invention, various crosslinking agents conventionally used for photographic materials, for example, aldehyde-based, epoxy-based, ethyleneimine-based, vinyl described in JP-A-50-96216 are used. A sulfone type, a sulfonic acid ester type, an acryloyl type, a carbodiimide type, or a silane compound type cross-linking agent can be used, but an isocyanate type compound, a silane compound, an epoxy compound, or an acid anhydride is preferable.
[0101]
Examples of suitable toning agents for use in the present invention are RD 17029, U.S. Pat. Nos. 4,123,282, 3,994,732, 3,846,136 and 4, For example, there are the followings. Imides (eg, succinimide, phthalimide, naphthalimide, N-hydroxy-1,8-naphthalimide); mercaptans (eg, 3-mercapto-1,2,4-triazole); phthalazinone derivatives or metal salts of these derivatives ( For example, phthalazinone, 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3-dihydro-1,4-phthalazinedione); phthalazine and phthalic acids ( For example, a combination of phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic acid); phthalazine and maleic anhydride, and phthalic acid, 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivative and its anhydride Products (eg, phthalic acid, 4-methylphthalic acid, 4 A combination of at least one compound selected from nitrophthalic acid and tetrachlorophthalic anhydride) and the like. Particularly preferred color tones are phthalazinone or a combination of phthalazine and phthalic acids and phthalic anhydrides.
[0102]
In the present invention, the surface layer of the photosensitive material (the photosensitive layer side or even when a non-photosensitive layer is provided on the opposite side of the photosensitive layer by sandwiching the support) is damaged before handling or after image development by thermal development. It is preferable to contain a matting agent for prevention, and it is preferable to contain 0.1-30% by mass ratio with respect to a binder. The material of the matting agent used in the present invention may be either organic or inorganic. Examples of inorganic substances include silica described in Swiss Patent No. 330,158 and the like, glass powder described in French Patent No. 1,296,995 and the like, and alkali described in British Patent No. 1,173,181 and the like. Earth metals or carbonates such as cadmium and zinc can be used as the matting agent. Examples of organic substances include starch described in U.S. Pat. No. 2,322,037 and the like, starch derivatives described in Belgian Patent 625,451 and British Patent 981,198, and Japanese Patent Publication No. 44-3643. Polyvinyl alcohol described, polystyrene or polymethacrylate described in Swiss Patent No. 330,158, polyacrylonitrile described in US Pat. No. 3,079,257, US Pat. No. 3,022,169 etc. An organic matting agent such as a polycarbonate can be used.
[0103]
In the present invention, a conductive compound such as a metal oxide and / or a conductive polymer can be included in the constituent layer in order to improve the chargeability. These may be contained in any layer, but are preferably contained in an undercoat layer, a backing layer, a layer between the photosensitive layer and the undercoat, and the like. In the present invention, the conductive compounds described in US Pat. No. 5,244,773, columns 14 to 20 are preferably used.
[0104]
The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only the photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. For example, a protective layer is provided on the photosensitive layer, and a back coat layer is provided on the opposite surface of the support to prevent sticking between photosensitive materials or in the photosensitive material roll. It is preferred that
[0105]
In the photothermographic material of the present invention, a filter layer is formed on the same side as or opposite to the photosensitive layer in order to control the amount of light transmitted through the photosensitive layer or the wavelength distribution, or a dye or pigment is added to the photosensitive layer. It is preferable to contain.
[0106]
As the dye used in the present invention, known compounds that absorb light in various wavelength regions can be used depending on the color sensitivity of the photosensitive material. For example, when the photothermographic material according to the present invention is used as an image recording material by infrared light, a squarylium dye having a thiopyrylium nucleus as disclosed in Japanese Patent Application No. 11-255557 (this specification). Used as a thiopyrylium squarylium dye) and a squarylium dye having a pyrylium nucleus (referred to herein as a pyrylium squarylium dye), or a thiopyrylium croconium dye similar to a squarylium dye, or a pyrylium croconium dye. It is preferable to do.
[0107]
The photothermographic material of the present invention may be formed by preparing a coating solution obtained by dissolving or dispersing the above-described constituent layers in a solvent, applying a plurality of these coating solutions simultaneously, and then performing a heat treatment. preferable. Here, "multiple simultaneous multi-layer coating" means that a coating solution for each constituent layer (for example, a photosensitive layer and a protective layer) is prepared, and when coating this onto a support, each layer is individually coated and dried repeatedly. In other words, it means that each constituent layer can be formed in such a state that the multilayer coating and drying can be performed simultaneously. That is, the upper layer is provided before the remaining amount of the total solvent in the lower layer reaches 70% by mass or less. There are no particular restrictions on the method of applying multiple layers of each constituent layer simultaneously, and for example, a known method such as a bar coater method, curtain coating method, dipping method, air knife method, hopper coating method, or extrusion coating method may be used. Can do. Of these, a pre-weighing type coating method called an extrusion coating method is more preferable. Since the extrusion coating method does not volatilize on the slide surface unlike the slide coating method, it is suitable for precision coating and organic solvent coating. This coating method has been described on the side having the photosensitive layer, but the same applies to the case of coating with undercoating when providing the backcoat layer.
[0108]
In the present invention, the development conditions vary depending on the equipment, apparatus, or means to be used, but it is characterized in that the information is fixed by heating and developing the information recording film exposed imagewise at a high temperature. is there. The latent image obtained after exposure is subjected to a photothermographic material at a moderately high temperature (for example, about 80 to 200 ° C., preferably about 100 to 200 ° C.) for a sufficient time (generally about 1 second to about 2 minutes). It can be developed by heating. When the heating temperature is 80 ° C. or lower, sufficient image density cannot be obtained in a short time. When the heating temperature is 200 ° C. or higher, the binder is melted, and not only the image itself, such as transfer to a roller, but also adversely affects the transportability and developing machine. Effect. By heating, a silver image is generated by an oxidation-reduction reaction between an organic silver salt (which functions as an oxidizing agent) and a reducing agent. This reaction process proceeds without any supply of treatment liquid such as water from the outside.
[0109]
In the exposure of the photothermographic material of the present invention, it is desirable to use a light source suitable for the color sensitivity imparted to the photosensitive material. For example, if the photosensitive material is sensitive to infrared light, it can be applied to any light source as long as it is in the infrared light range, but the laser power is high and the photosensitive material can be transparent. In view of the above, an infrared semiconductor laser (780 nm, 820 nm) is more preferably used.
[0110]
In the present invention, the exposure is preferably performed by laser scanning exposure, but various methods can be adopted as the exposure method. For example, as a first preferred method, there is a method using a laser scanning exposure machine in which the angle formed by the exposure surface of the photosensitive material and the scanning laser beam is not substantially perpendicular.
[0111]
Here, “substantially not perpendicular” means that the angle closest to the vertical during laser scanning is preferably 55 ° to 88 °, more preferably 60 ° to 86 °, and even more preferably 65 °. It is at least 84 degrees and most preferably 70 degrees to 82 degrees.
[0112]
As a second method, the exposure in the present invention is also preferably performed using a laser scanning exposure machine that emits a scanning laser beam that is a vertical multi. Compared with a single longitudinal mode scanning laser beam, image quality degradation such as generation of interference fringe-like unevenness is reduced.
[0113]
Furthermore, as a third aspect, it is also preferable to form an image by scanning exposure using two or more lasers.
[0114]
As such an image recording method using a plurality of lasers, it is used in an image writing unit of a laser printer or a digital copying machine which writes an image line by line in one scan in response to a demand for high resolution and high speed. This technique is known, for example, from Japanese Patent Laid-Open No. 60-166916. This is a method in which laser light emitted from a light source unit is deflected and scanned by a polygon mirror and imaged on a photoconductor via an fθ lens or the like. This is a laser scanning optical device that is theoretically the same as a laser imager or the like. It is. In each of the image recording methods described above, as a laser used for scanning exposure, generally known solid lasers such as a ruby laser, a YAG laser, and a glass laser; a He—Ne laser, an Ar ion laser, and a Kr ion laser , CO₂Laser, CO laser, He-Cd laser, N₂Gas laser such as laser and excimer laser; InGaP laser, AlGaAs laser, GaAsP laser, InGaAs laser, InAsP laser, CdSnP₂Lasers, semiconductor lasers such as GaSb lasers; chemical lasers, dye lasers, etc. can be selected and used in a timely manner, but among these, semiconductor lasers with a wavelength of 600-1200 nm are used due to maintenance and light source size problems. It is preferable to use it. In a laser used in a laser imager or a laser image setter, the beam spot diameter on the exposed surface of the material when scanned by a photothermographic material is generally 5 to 75 μm as the minor axis diameter, and the major axis diameter. The laser beam scanning speed can be set to an optimum value for each photosensitive material depending on the sensitivity and laser power at the laser oscillation wavelength unique to the photothermographic material.
[0115]
【Example】
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
Example 1
(Preparation of polymer fine particles (P-1))
Into a 1 L four-necked flask equipped with a stirring blade, a reflux condenser, a thermometer, and a dropping funnel, 450 ml of pure water was added, and while rotating the stirring blade, Newlex R (surfactant manufactured by NOF Corporation) 4% After adding 45 ml of the aqueous solution, the internal temperature is heated to 90 ° C. To this was added 15 ml of a 2% aqueous solution of ammonium peroxide, and a monomer mixture (butyl acrylate: 30 g, t-butyl acrylate: 88 g, styrene: 5.2 g, hydroxyethyl methacrylate: 5.2 g) was added over 1 hour. The reaction is continued for another 4 hours. Thereafter, the mixture was cooled to 30 ° C. or lower and filtered.
[0116]
(Preparation of polymer fine particles (P-2))
When P-1 was prepared, it was prepared in the same manner as P-1 except that the amount of styrene added was increased 1.25 times.
[0117]
(Preparation of polymer fine particles (P-3))
When P-1 was prepared, it was prepared in the same manner as P-1 except that the addition amount of styrene was 1.5 times.
[0118]
(Preparation of polymer fine particles (P-4))
In a 2 L three-necked flask equipped with a stirring blade, a reflux condenser, and a thermometer, 900 ml of pure water was added, and 66 g of partially saponified polyvinyl alcohol (PVA-235: manufactured by Kuraray Co., Ltd.) was gradually added while rotating the stirring blade. Put in. The mixture was stirred at room temperature for 30 minutes, heated to an internal temperature of 68 ° C. over 1 hour, and dissolved at this temperature for 4 hours. After completion of the heating, the mixture was cooled to room temperature over 1 hour, and 34 ml of pure water was added and finished overnight.
[0119]
(Preparation of polymer fine particles (P-5, 6))
A polymer solution in which 0.15 part of P-4 is mixed with 1 part of P-3 is referred to as P-5, and a polymer solution in which 0.3 part of P-4 is mixed with 1 part of P-3 is P. It was set to -6.
[0120]
<Production of support>
12 W / m on a biaxially stretched polyethylene terephthalate film that is 175 μm thick and colored to a blue density of 0.175²-After corona discharge so as to give an output of minutes, the following undercoat coating solution 1 was applied to the photosensitive layer surface side so that the dry film thickness was 9 µm, and then dried at 140 ° C (dew point temperature: 12 ° C). The undercoat layer 1 was formed by drying with wind for 10 seconds.
[0121]

[0122]
[Chemical 1]

[0123]
Next, 7 W / m is applied to the undercoat layer 1.²-After corona discharge was applied so that the output of the minute was applied, the following undercoat coating solution 2 was applied thereon so that the dry film thickness was 9 µm, and then the drying air at 140 ° C (dew point temperature: 12 ° C) The undercoat layer 2 was formed by drying for 10 seconds, and then transported through a drying zone at 123 ° C. over 2 minutes to provide the undercoat layer 2 containing insulator particles.
[0124]

The undercoat coating solution 2 was used for coating after ultrasonic dispersion under the following conditions.
[0125]
Dispersion conditions: frequency = 25 kHz, output = 100 W, vibrator outer dimensions = 64φ × 300 mm, dispersion time = 20 minutes
Next, the undercoat layer was applied to the opposite side of the plastic film, and the back layer surface side was applied in the same manner as described above.
[0126]
<< Preparation of photothermographic material >>
Using the plastic film sample prepared above, each component layer prepared by the following method was sequentially applied to prepare samples 1 to 6, which are corresponding photothermographic materials.
[0127]
(Application on the back side)
While stirring 830 g of methyl ethyl ketone (MEK), 84.2 g of cellulose acetate butyrate (Eastman Chemical Co., CAB381-20) and 4.5 g of a polyester resin (Bostic Co., VitelPE 2200B) were added and dissolved. Next, 0.30 g of infrared dye-1 was added to the dissolved liquid, and 4.5 g of F-type active agent (Asahi Glass Co., Surflon KH40) dissolved in 43.2 g of methanol and F-type active agent (large 2.3 g of Nippon Ink Co., Ltd. (MegaFag F120K) was added and stirred well 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 coating solution for the back surface side.
[0128]
[Chemical formula 2]

[0129]
The back surface coating solution prepared in this manner was applied and dried by an extrusion coater on the undercoat layer of each of the produced plastic films so that the dry film thickness was 3.5 μm. It dried for 5 minutes using the drying air with a drying temperature of 100 degreeC, and dew point temperature of 10 degreeC.
[0130]
(Coating on the photosensitive layer side)
[Preparation of photosensitive silver halide emulsion A]
<Solution A1>
Phenylcarbamoylated gelatin 88.3g
Compound (A) (10% methanol aqueous solution) 10 ml
Potassium bromide 0.32g
Finish to 5429 ml with water
<Solution B1>
0.67 mol / L silver nitrate aqueous solution 2635 ml
<Solution C1>
Potassium bromide 51.55g
Potassium iodide 1.47g
Finish to 660ml with water
<Solution D1>
Potassium bromide 154.9g
4.41 g of potassium iodide
Iridium chloride (1% solution) 0.93ml
Finish to 1982ml with water
<Solution E1>
0.4 mol / L potassium bromide aqueous solution The following silver potential control amount
<Solution F1>
Potassium hydroxide 0.71g
Finish to 20ml with water
<Solution G1>
56% acetic acid aqueous solution 18.0 ml
<Solution H1>
Anhydrous sodium carbonate 1.72 g
Finish to 151ml with water
Compound (A): HO (CH₂CH₂O)_n-(CH (CH_Three) CH₂O)₁₇−
(CH₂CH₂O)_mH m + n = 5-7
Using a mixing stirrer shown in Japanese Patent Publication No. 58-58288, the solution A1 was controlled to a 1/4 amount of the solution B1 and the total amount of the solution C1 to a temperature of 45 ° C. and a pAg of 8.09. Was added to perform nucleation. After 1 minute, the entire amount of solution F1 was added. During this time, the pAg was appropriately adjusted using the solution E1. After 6 minutes, 3/4 amount of the solution B1 and the whole amount of the solution D1 were added over 14 minutes and 15 seconds by the simultaneous mixing method while controlling the temperature at 45 ° C. and pAg 8.09. After stirring for 5 minutes, the temperature was lowered to 40 ° C., the whole amount of the solution G1 was added, and the silver halide emulsion was precipitated. The supernatant was removed leaving 2000 ml of the sediment, 10 liters of water was added, and after stirring, the silver halide emulsion was sedimented again. The remaining portion of 1500 ml was left, the supernatant was removed, 10 liters of water was further added, and after stirring, the silver halide emulsion was precipitated. After leaving 1500 ml of the sedimented portion and removing the supernatant, 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 that the amount was 1161 g per mole of silver, whereby photosensitive silver halide emulsion A was obtained.
[0131]
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%.
[0132]
[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 sodium hydroxide aqueous solution was added and 6.9 ml of concentrated nitric acid was added, followed by cooling to 55 ° C. to obtain a fatty acid sodium solution. While maintaining the temperature of the fatty acid sodium solution at 55 ° C., 45.3 g of the photosensitive silver halide emulsion A and 450 ml of pure water were added and stirred for 5 minutes.
[0133]
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 and stirred, and then allowed to stand to float and separate the organic silver salt dispersion, thereby removing the lower water-soluble salts. Thereafter, washing with deionized water and drainage were repeated until the electrical conductivity of the drainage reached 2 μS / cm, and centrifugal dehydration was carried out. Then, the resulting cake-like organic silver salt was converted into an airflow dryer flash jet dryer (stock) The product was dried until the water content became 0.1% according to the operating conditions of nitrogen gas atmosphere and dryer inlet hot air temperature to obtain a dried organic silver salt A of organic silver salt. An infrared moisture meter was used to measure the moisture content of the organic silver salt composition.
[0134]
[Preparation of Preliminary Dispersion A]
14.57 g of polyvinyl butyral powder (Monsanto, Butvar B-79) was dissolved in 1457 g of methyl ethyl ketone, and 500 g of powder organic silver salt A was gradually added while stirring with a dissolver DISPERMAT CA-40M manufactured by VMA-GETZMANN. Preliminary dispersion A was prepared by thorough mixing.
[0135]
[Preparation of photosensitive emulsion dispersion 1]
Media type disperser DISPERMAT SL- filled with 80% of the internal volume of 0.5 mm diameter zirconia beads (Torayserum manufactured by Toray) so that the residence time in the mill is 1.5 minutes using a pump. A photosensitive emulsion dispersion 1 was prepared by supplying to a C12EX type (manufactured by VMA-GETZMANN) and dispersing at a mill peripheral speed of 8 m / s.
[0136]
(Preparation of stabilizer solution)
A stabilizer solution was prepared by dissolving 1.0 g of Stabilizer-1 and 0.31 g of potassium acetate in 4.97 g of methanol.
[0137]
[Preparation of infrared sensitizing dye liquid A]
19.2 mg of infrared sensitizing dye 1, 1.488 g 2-chloro-benzoic acid, 2.779 g Stabilizer-2 and 365 mg 5-methyl-2-mercaptobenzimidazole in 31.3 ml MEK Infrared sensitizing dye solution A was prepared by dissolving at this point.
[0138]
[Chemical 3]

[0139]
[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, 0.48 g of the infrared dye-1 Was dissolved in 110 g of MEK to obtain an additive solution a.
[0140]
[Preparation of additive liquid b]
3.56 g of antifoggant-2 and 3.43 g of phthalazine were dissolved in 40.9 g of MEK to obtain additive liquid b.
[0141]
[Formula 4]

[0142]
[Preparation of photosensitive layer coating solution]
In an inert gas atmosphere (97% nitrogen), the photosensitive emulsion dispersion 1 (50 g) and 15.11 g of MEK were kept at 21 ° C. with stirring, and the chemical sensitizer S-5 (0.5% methanol solution) was kept. ) 1000 μl was added, and after 2 minutes, 390 μl of antifoggant-1 (10% methanol solution) was added and stirred for 1 hour. Further, 494 μl of calcium bromide (10% methanol solution) was added and stirred for 10 minutes, and then a gold sensitizer Au-5 corresponding to 1/20 mole of the chemical sensitizer S-5 was added, and further 20 minutes. Stir. Subsequently, 167 ml of a stabilizer solution was added and stirred for 10 minutes, and then 1.32 g of the infrared sensitizing dye solution A was added and stirred for 1 hour. Thereafter, the temperature was lowered to 13 ° C., and the mixture was further stirred for 30 minutes. While keeping the temperature at 13 ° C., 13.31 g of polyvinyl butyral (Monsanto Butvar B-79) was added and stirred for 30 minutes, and then 1.084 g of tetrachlorophthalic acid (9.4 mass% MEK solution) was added. Stir for 15 minutes. While further stirring, 12.43 g of additive liquid a, 1.6 ml of Desmodur N3300 / Mobey aliphatic isocyanate (10% MEK solution), 4.27 g of additive liquid b were sequentially added and stirred. A photosensitive layer coating solution was obtained.
[0143]
[Chemical formula 5]

[0144]
(Preparation of matting agent dispersion)
Cellulose acetate butyrate (Eastman Chemical Co., 7.5 g CAB171-15) was dissolved in 42.5 g of MEK, and 5 g of calcium carbonate (Speciality Minerals, Super-Pflex 200) was added thereto, and a dissolver type homogenizer was used. A matting agent dispersion was prepared by dispersing at 8000 rpm for 30 minutes.
[0145]
(Preparation of surface protective layer coating solution)
While stirring 865 g of MEK (methyl ethyl ketone), 96 g of cellulose acetate butyrate (Eastman Chemical, CAB171-15), 4.5 g of polymethylmethacrylic acid (Rohm & Haas, Paraloid A-21), vinylsulfone compound ( 1.5 g of VSC), 1.0 g of benztriazole, and 1.0 g of F-type activator (Asahi Glass Co., Surflon KH40) were added and dissolved. Next, 30 g of the above matting agent dispersion was added and stirred to prepare a surface protective layer coating solution.
[0146]
(Photosensitive layer side coating)
The photosensitive material was prepared by simultaneously applying the photosensitive layer coating solution and the surface protective layer coating solution on the undercoat layer 2 of each of the produced plastic films using an extrusion type extrusion coater. For coating, the photosensitive layer has a coated silver amount of 1.9 g / m.²The surface protective layer was formed so as 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., and Samples 1 to 6 as photothermographic materials were produced.
<< Evaluation of Photothermographic Material Sample >>
The samples prepared as described above were evaluated as follows.
[0147]
(Exposure and heat development processing)
Each of the prepared samples was stored for 3 days in an environment of 23 ° C. and 50% RH, and then exposed from a photosensitive layer surface side to a longitudinal multimode semiconductor laser having a wavelength of 800 nm to 820 nm by high frequency superposition. Exposure was performed by an exposure machine so that the density was 1.0 by laser scanning. At this time, an image was formed by setting the angle between the exposure surface of each sample and the exposure laser beam to 75 degrees.
[0148]
Thereafter, an automatic developing machine having a heat drum was used for heat development at 110 ° C. for 15 seconds so that the protective layer of the photosensitive material was in contact with the drum surface. At that time, exposure and development were performed in a room adjusted to 23 ° C. and 50% RH.
[0149]
(Evaluation with film)
Each sample exposed and developed as described above was allowed to stand for 3 days in an environment of 23 ° C. and 50% RH, and then the sample was exposed to the support with a razor blade on the photosensitive layer surface side and backing layer surface side. Scratches to reach the support at an angle of degree are applied in a grid, and after pressure-bonding an adhesive tape (cellophane adhesive tape) on it, the tape is rapidly peeled off at an angle of 45 degrees with respect to the support did. At this time, the area ratio of the photosensitive layer and the backing layer that remained without being peeled off together with the tape was measured with respect to the applied tape area, and evaluation with a film was performed according to the following criteria.
[0150]
Rank 5: 100% portion remains without peeling
Rank 4: 90-99% of the part remains without peeling
Rank 3: 80-89% of the part remains without peeling
Rank 2: 50-79% of the part remains intact
Rank 1: Only less than 50% remains.
[0151]
In addition, in the above rank, the one located in the middle of each rank was displayed as, for example, 3.5.
[0152]
(Evaluation of coating failure (white spot))
The exposed part of each of the heat-development-treated samples prepared above was visually observed using an optical loupe, and the frequency of occurrence of point-like failures having a density lower than that of the periphery having a diameter of 0.5 mm to 3 mm was measured. The coating failure (white spot) was evaluated according to the above.
[0153]
Rank 5: No occurrence / 10m²
Rank 4: 1 failure / 10m failure with density difference within 0.05²
Rank 3: 2 to 10 failures with a density difference of less than 0.05²
Rank 2: A fault with a density difference of 0.06 or more has occurred.
Rank 1: A fault with a density difference of 0.1 or more from the surrounding area has occurred.
In addition, in the above rank, the one located in the middle of each rank was displayed as, for example, 3.5.
[0154]
(Evaluation of coating failure of backing layer)
Rank 5: No occurrence / 10m²
Rank 4: 1-2 faults / 10m²
Rank 3: 3-5 failures / 10m²
Rank 2: 6-8 failures / 10m²
Rank 1: 9 or more failure points / 10m²
In addition, in the above rank, the one located in the middle of each rank was displayed as, for example, 3.5.
[0155]
Table 1 shows the evaluation results obtained as described above.
[0156]
[Table 1]

[0157]
As is apparent from Table 1, each sample having the structure according to the present invention as the structure of the undercoat layer has excellent characteristics with a film and a characteristic that the occurrence of white spot failure is extremely small compared to the comparative sample. I know that.
[0158]
Example 2
The binder (P-7) shown below is used in place of the binder used in the undercoat coating solutions 1 and 2 of Example 1, and synthetic silica (average particle size 0.5 μm) and a molecular weight of 10,000 or less are used as inorganic fillers. A sample was prepared in the same manner as in Example 1 except that the amount of polyethylene glycol (average molecular weight 600) shown in Table 2 was added to the undercoating liquids 1 and 2 as the compound of Example 1, and the same evaluation as in Example 1 was performed. .
[0159]
(Preparation method of P-7)
Into a 1 L four-necked flask equipped with a stirring blade, a reflux condenser, a thermometer, and a dropping funnel, 250 ml of pure water was added, and while rotating the stirring blade, Newlex R (surfactant manufactured by Nippon Oil & Fats Co., Ltd.) 4% After adding 15 ml of aqueous solution, the internal temperature is heated to 90 ° C. 15 ml of a 2% aqueous solution of ammonium peroxide is added thereto, and a monomer mixture (butyl acrylate: 48 g, styrene: 24 g, glycidyl methacrylate: 48 g) is added dropwise over 1 hour, and the reaction is continued for another 4 hours. Thereafter, the mixture was cooled to 30 ° C. or lower and filtered.
[0160]
[Table 2]

[0161]
As is apparent from Table 2, each sample having the configuration according to the present invention as the configuration of the undercoat layer is superior to the comparative sample in the characteristics with a film and has a characteristic that the occurrence of white spot failure is extremely small. I know that.
[0162]
【The invention's effect】
According to the present invention, a photothermographic material improved in both coating failure (white spot failure) and adhesive strength can be provided.

Claims (2)

In a silver halide photographic material for heat development, wherein at least one surface of the plastic film is coated with a silver halide photosensitive layer for heat development, at least one non-light-sensitive layer is provided between the photosensitive layer and the plastic film. And the non-photosensitive layer is a repeating unit derived from an ethylenically unsaturated monomer selected from methacrylic acid ester, acrylic acid ester and maleic acid ester whose homopolymer has a glass transition temperature of 35 ° C. or lower. The non-photosensitive layer further comprises an inorganic filler of 5% or more and 20% or less of the total amount of the polymer particles, and a molecular weight of 100% or more of 0.5% or more and 5% or less of the total amount of the polymer particles. containing 10000 plasticity organics heat further dynamic elastic modulus of the non-light-sensitive layer, characterized in that a relation of the following formula (1) The silver halide photographic light-sensitive material for image.
30 <En ₂₅ / En ₁₂₅ <5000 (1)
In the formula, En ₂₅ represents the dynamic elastic modulus of the non-photosensitive layer at 25 ° C., and En ₁₂₅ represents the dynamic elastic modulus of the non-photosensitive layer at 125 ° C. Further, 5.0 × 10 ⁶ Pa ≧ En ₁₂₅ ≧ 1.0 × 10 ⁵ Pa. A heat-developable silver halide photographic light-sensitive material in which a heat-developable silver halide light-sensitive layer is coated on at least one surface of a plastic film, wherein at least two layers are opposite to the light-sensitive layer and a support. The intermediate layer coated between the outermost layer and the plastic film is coated with methacrylic acid ester, acrylic acid ester, maleic acid ester whose homopolymer has a glass transition temperature of 35 ° C. or lower. There are polymer fine particles having a repeating unit derived from an ethylenically unsaturated monomer selected, and the intermediate layer has an inorganic filler of 5% to 20% of the total amount of the polymer fine particles and 0% of the total amount of the polymer fine particles. contains .5% to 5% or less of the thermoplastic organic material with a molecular weight of 100 to 10000, further Seki dynamic elastic modulus of the intermediate layer is the following formula (2) It characterized that, the silver halide photographic light-sensitive material for heat development to be in.
30 <Ei ₂₅ / Ei ₁₂₅ <5000 (2)
In the formula, Ei ₂₅ represents the dynamic elastic modulus of the intermediate layer at 25 ° C., and Ei ₁₂₅ represents the dynamic elastic modulus of the intermediate layer at 125 ° C. Further, 5.0 × 10 ⁶ Pa ≧ Ei ₁₂₅ ≧ 1.0 × 10 ⁵ Pa.