JP2004284036A - Biaxially stretched polyester film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a biaxially stretched polyester film having good film manufacturing stability, excellent in tear strength, breaking strength, elongation characteristics at break and film cutting properties and also excellent in perforation aptness in a packaging process, in feed properties within a camera in a photographing process, film editing properties in a developing treatment process, picture motion film and miniature laboratory processing properties, printer feed properties, accumulation properties and printability (focusing properties). <P>SOLUTION: The biaxially stretched polyester film has a multilayered structure wherein at least two polyester layers are laminated. The surface layer contains an aromatic dicarboxylic acid having a metal sulfonate group, a polyalkylene glycol and cyclohexylene dimethylene glycol as copolymer components of a polyester. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明のハロゲン化銀カラー写真感光材料に使用できる公知の写真用添加剤も、上記ＲＤに記載されている。以下に関連のある記載箇所を示す。

本発明に係る感光性層には、種々のカプラーを使用することが出来、その具体例は、上記ＲＤに記載されている。以下に関連のある記載箇所を示す。
【０１０５】

上記各添加剤は、ＲＤ３０８１１９ＸＩＶに記載されている分散法などにより、添加することが出来る。
【０１０６】
本発明に係るハロゲン化銀写真感光材料には、前述ＲＤ３０８１１９ＶＩＩ−Ｋ項に記載されているフィルター層や中間層等の補助層を設けることも出来る。
【０１０７】
本発明に係るハロゲン化銀写真感光材料は、前述ＲＤ３０８１１９ＶＩＩ−Ｋ項に記載されている順層、逆層、ユニット構成等の様々な層構成をとることが出来る。
【０１０８】
本発明に係るハロゲン化銀写真感光材料を現像処理するには、例えば、Ｔ．Ｈ．ジェームズ著、セオリイ オブ ザ ホトグラフィック プロセス第４版（Ｔｈｅ Ｔｈｅｏｒｙ ｏｆ Ｔｈｅ Ｐｈｏｔｏｇｒａｐｈｉｃ Ｐｒｏｃｅｓｓ Ｆｏｒｔｈ Ｅｄｉｔｉｏｎ）第２９１〜３３４頁及びジャーナル オブ ザ アメリカン ケミカル ソサエティ（Ｊｏｕｒｎａｌ ｏｆ ｔｈｅ Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ）第７３巻、Ｎｏ．３、１００頁（１９５１）に記載されている公知の現像剤を使用することができる。また、前述のＲＤ１７６４３の２８〜２９頁、ＲＤ１８７１６の６１５頁及びＲＤ３０８１１９ＸＩＸに記載された通常の方法によって、現像処理することができる。
【０１０９】
【実施例】
以下、実施例を挙げて本発明を詳細に説明するが、本発明の態様はこれに限定されない。
【０１１０】
《ポリエステルの調製》
（ポリエステルＡの調製）
撹拌機、添加剤導入口、窒素ガス導入口、真空流出系を備えた反応器にテレフタル酸ジメチルの１００質量部、エチレングリコールの６４質量部に、酢酸カルシウムの水和物と酢酸マンガンの水和物とを、それぞれテレフタル酸ジメチル１モルに対し２×１０^−４モル相当量添加し、常法によりエステル交換反応を行った。得られた生成物に、５−ナトリウムスルホジ（β−ヒドロキシエチル）イソフタル酸（ＳＩＰ）のエチレングリコール溶液（濃度３５質量％）の３２質量部（５．８モル％／全酸成分）、ポリエチレングリコール（数平均分子量１０００）の８．４質量部（６．７質量％／ポリマー）、三酸化アンチモンの０．０５質量部、リン酸トリメチルエステルの０．１３質量部、酸化防止剤としてイルガノックス１０１０（ＣＩＢＡ−ＧＥＩＧＹ社製）の０．４質量部、酢酸ナトリウムの０．０４質量部及び平均粒径０．２μｍのシリカ粒子の０．００２質量部を添加した。次いで、徐々に昇温、減圧し、２８０℃、６０Ｐａで攪拌トルクをモニターしながら重合を行い共重合ポリエステルを得た。
【０１１１】
この共重合ポリエステルを用いて、バイエル社製の染料を次の配合割合で混練し、染料濃度２０００ｐｐｍのマスターペレットを調製し、染料を含まない共重合ポリエステルとマスターペレットを９：１の割合でブレンドし、ポリエステルＡを得た。このポリエステルＡの固有粘度（ＩＶ）は０．５４であった。
【０１１２】
染料の構成比率；Ｍａｃｒｏｌｅｘ Ｒｅｄ ＥＧ：Ｍａｃｒｏｌｅｘ Ｖｉｏｌｅｔ Ｂ：Ｍａｃｒｏｌｅｘ Ｇｒｅｅｎ Ｇ＝１：１：１
（ポリエステルＢの調製）
市販のポリエチレンテレフタレート（固有粘度０．６５）を用いて、上記と同様の染料を配合割合で混練し、染料濃度を２０００ｐｐｍにしてマスターペレットを調製し、染料を含まないポリエチレンテレフタレート（固有粘度０．６５）とマスターペレットを９：１の割合でブレンドして、ポリエステルＢを調製した。
【０１１３】
（ポリエステルＣの調製）
撹拌機、添加剤導入口、窒素ガス導入口、真空流出系を備えた反応器にテレフタル酸ジメチルの１００質量部、１，４シクロヘキサンジメタノール（ＣＨＤＭ）の１８．６質量部、エチレングリコールの４８質量部に、酢酸カルシウムの水和物と酢酸マンガンの水和物とを、それぞれテレフタル酸ジメチル１モルに対し、２×１０^−４モル相当量添加し、２００℃、窒素雰囲気下でエステル交換反応を行った。その後、三酸化アンチモンの０．０５質量部、リン酸トリメチルエステルの０．１３質量部、酸化防止剤としてイルガノックス１０１０（ＣＩＢＡ−ＧＥＩＧＹ社製）の０．４質量部、酢酸ナトリウムの０．０４質量部及び平均粒径０．２μｍのシリカ粒子の０．００２質量部を添加した。次いで、徐々に昇温、減圧し、２８０℃、６０Ｐａの圧力下で重合を行い、共重合ポリエステルを得た。この共重合ポリエステルに、ポリエステルＡと同様に染料を添加してポリエステルＣとした。このポリエステルＣの固有粘度（ＩＶ）は０．５４であった。
【０１１４】
（ポリエステルＤの調製）
撹拌機、添加剤導入口、窒素ガス導入口、真空流出系を備えた反応器にテレフタル酸ジメチルの１００質量部、１，４シクロヘキサンジメタノール（ＣＨＤＭ）の４１質量部、エチレングリコールの２９質量部に、酢酸カルシウムの水和物と酢酸マンガンの水和物とを、それぞれテレフタル酸ジメチル１モルに対し、２×１０^−４相当量添加し、２００℃、窒素雰囲気下でエステル交換反応を行った。その後、三酸化アンチモンの０．０５質量部、リン酸トリメチルエステルの０．１３質量部、酸化防止剤としてイルガノックス１０１０（ＣＩＢＡ−ＧＥＩＧＹ社製）の０．４質量部、酢酸ナトリウムの０．０４質量部及び平均粒径０．２μｍのシリカ粒子の０．００２質量部を添加した。次いで、徐々に昇温、減圧し、２８０℃、６０Ｐａの圧力下で重合を行い、共重合ポリエステルを得た。この共重合ポリエステルに、ポリエステルＡと同様に染料を添加してポリエステルＤとした。このポリエステルＤの固有粘度（ＩＶ）は０．６４であった。
【０１１５】
（ポリエステルＥの調製）
撹拌機、添加剤導入口、窒素ガス導入口、真空流出系を備えた反応器にテレフタル酸ジメチルの１００質量部、１，４シクロヘキサンジメタノール（ＣＨＤＭ）の５２質量部、エチレングリコールの１６質量部に、酢酸カルシウムの水和物と酢酸マンガンの水和物とを、それぞれテレフタル酸ジメチル１モルに対し２×１０^−４モル相当量添加し、２００℃、窒素雰囲気下でエステル交換反応を行った。その後、三酸化アンチモンの０．０５質量部、リン酸トリメチルエステルの０．１３質量部、酸化防止剤としてイルガノックス１０１０（ＣＩＢＡ−ＧＥＩＧＹ社製）の０．４質量部及び酢酸ナトリウムの０．０４質量部を添加した。次いで、徐々に昇温、減圧し、２８０℃、６０Ｐａの圧力下で重合を行い共重合ポリエステルを得た。この共重合ポリエステルに、ポリエステルＡと同様に染料を添加してポリエステルＥとした。このポリエステルＥの固有粘度（ＩＶ）は０．７２であった。
【０１１６】
（ポリエステルＦの調製）
撹拌機、添加剤導入口、窒素ガス導入口、真空流出系を備えた反応器にテレフタル酸ジメチルの９５質量部、イソフタル酸ジメチルの５質量部、１，４シクロヘキサンジメタノール（ＣＨＤＭ）の７７質量部に酢酸カルシウムの水和物と酢酸マンガンの水和物とを、それぞれテレフタル酸ジメチルとイソフタル酸のモル数の合計に対するモル比で２×１０^−４相当量添加し、２００℃、窒素雰囲気下でエステル交換反応を行った。その後、三酸化アンチモンの０．０５質量部、リン酸トリメチルエステルの０．１３質量部、酸化防止剤としてイルガノックス１０１０（ＣＩＢＡ−ＧＥＩＧＹ社製）の０．４質量部、酢酸ナトリウムの０．０４質量部及び平均粒径０．２μｍのシリカ粒子の０．００２質量部を添加した。次いで、徐々に昇温、減圧し、２８０℃、６０Ｐａの圧力下で重合を行い共重合ポリエステルを得た。この共重合ポリエステルに、ポリエステルＡと同様に染料を添加してポリエステルＦとした。このポリエステルＦの固有粘度（ＩＶ）は０．７７であった。
【０１１７】
（ポリエステルＧの調製）
撹拌機、添加剤導入口、窒素ガス導入口、真空流出系を備えた反応器にテレフタル酸ジメチルの１００質量部、１，４シクロヘキサンジメタノール（ＣＨＤＭ）の５質量部、エチレングリコールの６０質量部に、酢酸カルシウムの水和物と酢酸マンガンの水和物とを、それぞれテレフタル酸ジメチル１モルに対し２×１０^−４モル相当量添加し、２００℃、窒素雰囲気下でエステル交換反応を行った。得られた生成物に、５−ナトリウムスルホジ（β−ヒドロキシエチル）イソフタル酸（ＳＩＰ）のエチレングリコール溶液（濃度３５質量％）の３２質量部（５．８モル％／全酸成分）、ポリエチレングリコール（数平均分子量１０００）の８．４質量部（６．７質量％／ポリマー）、三酸化アンチモンの０．０５質量部、リン酸トリメチルエステルの０．１３質量部、酸化防止剤としてイルガノックス１０１０（ＣＩＢＡ−ＧＥＩＧＹ社製）の０．４質量部、酢酸ナトリウム０．０４質量部及び平均粒径０．２μｍのシリカ粒子の０．００２質量部を添加した。次いで、徐々に昇温、減圧にし、２８０℃、６０Ｐａの圧力下で重合を行い共重合ポリエステルを得た。この共重合ポリエステルに、ポリエステルＡと同様に染料を添加してポリエステルＧとした。このポリエステルＧの固有粘度（ＩＶ）は０．５８であった。
【０１１８】
（ポリエステルＨの調製）
撹拌機、添加剤導入口、窒素ガス導入口、真空流出系を備えた反応器にテレフタル酸ジメチルの１００質量部、１，４シクロヘキサンジメタノール（ＣＨＤＭ）の１８．６質量部、エチレングリコールの４８質量部に、酢酸カルシウムの水和物と酢酸マンガンの水和物とを、それぞれテレフタル酸ジメチル１モルにし２×１０^−４モル相当量添加し、２００℃、窒素雰囲気下でエステル交換反応を行った。得られた生成物に、５−ナトリウムスルホジ（β−ヒドロキシエチル）イソフタル酸（ＳＩＰ）のエチレングリコールと１，４シクロヘキサンジメタノール（ＣＨＤＭ）の混合溶液（濃度３５質量％）の３２質量部（５．８モル％／全酸成分）、ポリエチレングリコール（数平均分子量１０００）の８．４質量部（６．７質量％／ポリマー）、三酸化アンチモンの０．０５質量部、リン酸トリメチルエステルの０．１３質量部、酸化防止剤としてイルガノックス１０１０（ＣＩＢＡ−ＧＥＩＧＹ社製）の０．４質量部、酢酸ナトリウムの０．０４質量部及び平均粒径０．２μｍのシリカ粒子の０．００２質量部を添加した。次いで、徐々に昇温、減圧にし、２８０℃、６０Ｐａの圧力下で重合を行い、共重合ポリエステルを得た。この共重合ポリエステルに、ポリエステルＡと同様に染料を添加してポリエステルＨとした。このポリエステルＨの固有粘度（ＩＶ）は０．５８であった。
【０１１９】
（ポリエステルＩの調製）
８０質量部の上記ポリエステルＡと２０質量部の上記ポリエステルＣとを、タンブラー型混合機でブレンドした後、異方向回転の２軸スクリュー混練機を通過させ、十分な混合を行った。入り口からは乾燥窒素ガスを流しながら、２ヶ所のベントから２０ｈＰａで減圧脱気を行った。混練部のバレル温度は２８０℃であり、混練槽内の滞留時間は１０分であった。流出したストランドを冷水で急冷し、細かく裁断して、乾燥しペレットとして、ポリエステルＩを得た。
【０１２０】
（ポリエステルＪの調製）
上記ポリエステルＩの調製において、８０質量部の上記ポリエステルＡと２０質量部の上記ポリエステルＣに代えて、５０質量部の上記ポリエステルＢと５０質量部の上記ポリエステルＣとを用いた以外は同様にして、ポリエステルＪを得た。
【０１２１】
（ポリエステルＫの調製）
上記ポリエステルＩの調製において、８０質量部の上記ポリエステルＡと２０質量部の上記ポリエステルＣに代えて、３０質量部の上記ポリエステルＡと３５質量部の上記ポリエステルＢと３５質量部の上記ポリエステルＣとを用いた以外は同様にして、ポリエステルＫを得た。
【０１２２】
（ポリエステルＬの調製）
上記ポリエステルＩの調製において、８０質量部の上記ポリエステルＡと２０質量部の上記ポリエステルＣに代えて、９５質量部の上記ポリエステルＡと５質量部の上記ポリエステルＥとを用いた以外は同様にして、ポリエステルＬを得た。
【０１２３】
（ポリエステルＭの調製）
上記ポリエステルＩの調製において、８０質量部の上記ポリエステルＡと２０質量部の上記ポリエステルＣに代えて、２０質量部の上記ポリエステルＡと６０質量部の上記ポリエステルＢと２０質量部の上記ポリエステルＥとを用いた以外は同様にして、ポリエステルＭを得た。
【０１２４】
（ポリエステルＮの調製）
上記ポリエステルＩの調製において、８０質量部の上記ポリエステルＡと２０質量部の上記ポリエステルＣに代えて、９５質量部の上記ポリエステルＡと５質量部の上記ポリエステルＦとを用いた以外は同様にして、ポリエステルＮを得た。
【０１２５】
（ポリエステルＯの調製）
上記ポリエステルＩの調製において、８０質量部の上記ポリエステルＡと２０質量部の上記ポリエステルＣに代えて、６０質量部の上記ポリエステルＥと４０質量部の上記ポリエステルＢとを用いた以外は同様にして、ポリエステルＯを得た。
【０１２６】
（ポリエステルＰの調製）
上記ポリエステルＡの調製において、マット剤（シリカ粒子）を添加せず、２８０℃、６０Ｐａの重合条件とし、トルクをポリエステルＡ調製時の８０％で停止した以外は全く同様にして、５−ナトリウムスルホジ（β−ヒドロキシエチル）イソフタル酸（ＳＩＰ）とポリエチレングリコールを変成成分にもつポリエステルを重合し、乾燥済みペレットとした。これにポリエステルＡの時と同様に染料を添加し、ポリエステルＰとした。このペレットの固有粘度は０．４４であった。
【０１２７】
（ポリエステルＱの調製）
前記ポリエステルＡを、真空回転乾燥機を用いて、窒素気流中で、１７０℃、１時間流動させながら乾燥させた。その後、回転を止め、静置のまま２２０℃、２時間の固相重合を行い、ポリエステルＱとした。このポリエステルＱの固有粘度は０．６２であった。
【０１２８】
（ポリエステルＲの調製）
上記ポリエステルＭの調製において、混練の際にポリエステルＢ（固有粘度０．６５）の代わりに、市販のポリエチレンテレフタレート（固有粘度０．４３）に染料を添加したものを用いた以外は同様にして、３つのポリエステル樹脂を混合した混練乾燥済みペレットとし、ポリエステルＲを得た。
【０１２９】
（ポリエステルＳの調製）
市販のポリエチレンテレフタレート（固有粘度０．７８）を用いて、ポリエステルＡと同様の染料を配合割合で混練し、染料濃度を２０００ｐｐｍとしてマスターペレットを調製し、染料を含まないポリエチレンテレフタレート（固有粘度０．７８）とマスターペレットを９：１の割合でブレンドして、ポリエステルＳとした。
【０１３０】
（ポリエステルＴの調製）
上記ポリエステルＧの調製において、酸化防止剤であるイルガノックス１０１０を添加しない以外は同様にして、ポリエステルＴを得た。
【０１３１】
（ポリエステルＵの調製）
上記ポリエステルＧの調製において、酸化防止剤であるイルガノックス１０１０の添加量を１０質量部に変更した以外は同様にして、ポリエステルＵを得た。
【０１３２】
（ポリエステルＶの調製）
上記ポリエステルＡの調製において、平均粒径０．２μｍのシリカ粒子を除いた以外は同様にして、ポリエステルＶを得た。
【０１３３】
《ポリエステルの調製》
（ポリエステルフィルム１及び試料１の作製：本発明）
〈製膜〉
上記調製したポリエステルＬとポリエステルＭとを、各々１６０℃で１０時間真空乾燥した後、３台の押出機を用いて２８０℃で溶融押出し、それぞれ４０メッシュのフィルターを通過させてから、Ｔダイ内で層状に接合し、４５℃の冷却ドラム上に静電印加しながら密着させて冷却固化し、３層構成の積層未延伸シートを得た。このとき、ポリエステルＬが両面の表層（スキン層）、ポリエステルＭが芯層（コア層）であり、各層の厚さの比が２０（Ｌ）：７０（Ｍ）：３０（Ｌ）となるように各押出機の押出し量を調整した。この未延伸シートを、ロール式縦延伸機を用いて９０℃で縦方向に３．５倍延伸した。得られた１軸延伸フィルムをテンター式横延伸機を用いて、第１延伸ゾーン１００℃で総横延伸倍率の５０％延伸し、更に第２延伸ゾーン１２０℃で総横延伸倍率３．６倍となるように延伸した。次いで１００℃で２秒間熱処理し、更に第１熱固定ゾーン１７０℃で５秒間熱固定し、第２熱固定ゾーン２１０℃で１５秒間熱固定した。次いで、横方向に５％弛緩処理しながら室温まで３０秒かけて徐冷して厚さ１２０μｍ（各層の膜厚２０μｍ／７０μｍ／３０μｍ）の２軸延伸積層のポリエステルフィルム１を得た。両端部をトリミングして、両端に高さ２５μｍ、幅９ｍｍのナーリング加工を施して、５００ｍを直径２２０ｍｍのコアに巻き取った。
【０１３４】
〈ハロゲン化銀写真感光材料の作製〉
上記作製したポリエステルフィルム１の膜厚２０μｍのスキン層面側に、特開２００１−３３９１３号の実施例１１に記載の下引き層、バック層及びハロゲン化銀乳剤を塗布した。この後、１３５サイズ（３５ｍｍ巾）に断裁し、１３５サイズの３６枚撮りフィルムのＩＳＯ規格通りにパーフォレーション加工を施した後、規定のパトローネに装填して、１３５サイズ用のハロゲン化銀カラー写真感光材料である試料１を作製した。
【０１３５】
（ポリエステルフィルム２及び試料２の作製：本発明）
上記ポリエステルフィルム１及び試料１の作製において、ポリエステルＬとポリエステルＭに代えて、ポリエステルＧとポリエステルＢをこの順で用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム２と試料２を作製した。
【０１３６】
（ポリエステルフィルム３及び試料３の作製：本発明）
上記ポリエステルフィルム１及び試料１の作製において、ポリエステルＬとポリエステルＭに代えて、ポリエステルＨとポリエステルＡをこの順で用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム３と試料３を作製した。
【０１３７】
（ポリエステルフィルム４及び試料４の作製：本発明）
上記ポリエステルフィルム１及び試料１の作製において、ポリエステルＭに代えて、ポリエステルＣを用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム４と試料４を作製した。
【０１３８】
（ポリエステルフィルム５及び試料５の作製：本発明）
上記ポリエステルフィルム１及び試料１の作製において、ポリエステルＬとポリエステルＭに代えて、ポリエステルＯとポリエステルＥをこの順で用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム５と試料５を作製した。
【０１３９】
（ポリエステルフィルム６及び試料６の作製：本発明）
上記ポリエステルフィルム１及び試料１の作製において、ポリエステルＬとポリエステルＭに代えて、ポリエステルＨとポリエステルＧをこの順で用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム６と試料６を作製した。
【０１４０】
（ポリエステルフィルム７及び試料７の作製：本発明）
上記ポリエステルフィルム１及び試料１の作製において、ポリエステルＬとポリエステルＭに代えて、ポリエステルＧとポリエステルＣをこの順で用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム７と試料７を作製した。
【０１４１】
（ポリエステルフィルム８及び試料８の作製：本発明）
上記ポリエステルフィルム１及び試料１の作製において、ポリエステルＬに代えて、ポリエステルＡとポリエステルＦとを９５：５の質量比で混ぜたもの、ポリエステルＭに代えて、ポリエステルＢとポリエステルＣを５０：５０の質量比で混ぜたものを用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム８と試料８を作製した。
【０１４２】
（ポリエステルフィルム９及び試料９の作製：本発明）
上記ポリエステルフィルム１及び試料１の作製において、ポリエステルＬとポリエステルＭに代えて、ポリエステルＮとポリエステルＪをこの順で用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム９と試料９を作製した。
【０１４３】
（ポリエステルフィルム１０及び試料１０の作製：本発明）
上記ポリエステルフィルム１及び試料１の作製において、ポリエステルＬとポリエステルＭに代えて、ポリエステルＡとポリエステルＭをこの順で用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム１０と試料１０を作製した。
【０１４４】
（ポリエステルフィルム１１及び試料１１の作製：本発明）
上記ポリエステルフィルム１及び試料１の作製において、ポリエステルＬに代えて、ポリエステルＡとポリエステルＤとを９０：１０の質量比で混ぜたもの、ポリエステルＭに代えて、ポリエステルＢを用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム１１と試料１１を作製した。
【０１４５】
（ポリエステルフィルム１２及び試料１２の作製：本発明）
上記ポリエステルフィルム１及び試料１の作製において、ポリエステルＬとポリエステルＭに代えて、ポリエステルＩとポリエステルＫをこの順で用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム１２と試料１２を作製した。
【０１４６】
（ポリエステルフィルム１３及び試料１３の作製：本発明）
上記ポリエステルフィルム１及び試料１の作製において、ポリエステルＬに代えて、ポリエステルＶを用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム１３と試料１３を作製した。
【０１４７】
（ポリエステルフィルム１４及び試料１４の作製：本発明）
上記ポリエステルフィルム１及び試料１の作製において、スキン層（ポリエステルＬ）／コア層（ポリエステルＭ）／スキン層（ポリエステルＬ）の膜厚を、３０μｍ／５０μｍ／４０μｍに変更した以外は同様にして、２軸延伸積層であるポリエステルフィルム１４と試料１４を作製した。
【０１４８】
（ポリエステルフィルム１５及び試料１５の作製：本発明）
上記ポリエステルフィルム１及び試料１の作製において、スキン層（ポリエステルＬ）／コア層（ポリエステルＭ）／スキン層（ポリエステルＬ）の膜厚を、５μｍ／１１０μｍ／５μｍに変更した以外は同様にして、２軸延伸積層であるポリエステルフィルム１５と試料１５を作製した。
【０１４９】
（ポリエステルフィルム１６及び試料１６の作製：本発明）
上記ポリエステルフィルム１０及び試料１０の作製において、ポリエステルＡに代えて、ポリエステルＰを用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム１６と試料１６を作製した。
【０１５０】
（ポリエステルフィルム１７及び試料１７の作製：本発明）
上記ポリエステルフィルム１６及び試料１６の作製において、ポリエステルＭに代えて、ポリエステルＲを用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム１７と試料１７を作製した。
【０１５１】
（ポリエステルフィルム１８及び試料１８の作製：本発明）
上記ポリエステルフィルム２及び試料２の作製において、ポリエステルＧに代えて、ポリエステルＴを用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム１８と試料１８を作製した。
【０１５２】
（ポリエステルフィルム１９及び試料１９の作製：本発明）
上記ポリエステルフィルム２及び試料２の作製において、ポリエステルＧに代えて、ポリエステルＵを用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム１９と試料１９を作製した。
【０１５３】
（ポリエステルフィルム２０及び試料２０の作製：比較例）
上記ポリエステルフィルム２及び試料２の作製において、ポリエステルＧとポリエステルＢの配置を入れ替えて、両スキン層にポリエステルＢ、コア層にポリエステルＧとなるように構成した以外は同様にして、２軸延伸積層であるポリエステルフィルム２０と試料２０を作製した。
【０１５４】
（ポリエステルフィルム２１及び試料２１の作製：比較例）
上記ポリエステルフィルム１０及び試料１０の作製において、ポリエステルＭに代えて、ポリエステルＧを用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム２１と試料２１を作製した。
【０１５５】
（ポリエステルフィルム２２及び試料２２の作製：比較例）
上記ポリエステルフィルム２及び試料２の作製において、ポリエステルＧに代えて、ポリエステルＦを用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム２２と試料２２を作製した。
【０１５６】
（ポリエステルフィルム２３及び試料２３の作製：比較例）
上記ポリエステルフィルム１及び試料１の作製において、ポリエステルＬとポリエステルＭに代えて、ポリエステルＱとポリエステルＳをこの順で用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム２３と試料２３を作製した。
【０１５７】
（ポリエステルフィルム２４及び試料２４の作製：比較例）
上記ポリエステルフィルム１及び試料１の作製において、ポリエステルＬとポリエステルＭに代えて、ポリエステルＢとポリエステルＨをこの順で用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム２４と試料２４を作製した。
【０１５８】
（ポリエステルフィルム２５及び試料２５の作製：比較例）
上記ポリエステルフィルム１及び試料１の作製において、ポリエステルＬとポリエステルＭに代えて、ポリエステルＢとポリエステルＤをこの順で用いた以外は同様にして、２軸延伸積層であるポリエステルフィルム２５と試料２５を作製した。
【０１５９】
以上により作製した各ポリエステルフィルムの構成を、まとめて表１に示す。
なお、表１に記載のポリエステル種混合条件の詳細は、以下の通りである。
【０１６０】
イ：異なる組成のポリエステル樹脂を２軸混練機により混練し、ペレット化してから使用
ロ：共重合ポリエステル樹脂をそのまま単独で使用
ハ：異なる組成のポリエステル樹脂を、ペレットのままドライブレンドして使用
ニ：共重合成分を含まない均質のポリエチレンテレフタレートをそのまま単独で使用
【０１６１】
【表１】

【０１６２】
《ポリエステルフィルムの物性値の測定》
上記作製した各ポリエステルフィルムについて、下記の方法に準じて各物性値の測定を行い、得られた結果を表２に記載する。
【０１６３】
（トラウザー引き裂き強度の測定：幅手方向、長手方向）
ＪＩＳ−Ｋ７１２８−１に従って、トラウザー引き裂き強度を、各ポリエステルフィルムの幅手方向及び長手方向について測定した。測定は、１２０μｍの厚さのポリエステルフィルムの引き裂き力（Ｎ）、あるいは膜厚が１２０μｍ以外のものに関しては１２０μｍに換算して引き裂き力（Ｎ）を測定し、これをトラウザー引き裂き強度として表示し、厚さの因子を考慮せずに比較できるようにした。
【０１６４】
（エレメンドルフ引き裂き強度の測定：長手方向）
ＪＩＳ−Ｋ７１２８−２に従って、長手方向のエレメンドルフ引き裂き強度を測定した。測定は、１２０μｍの厚さのポリエステルフィルムを用いた引き裂き力（Ｎ）、あるいはそれ以外の膜厚である場合には、１２０μｍの厚さに換算した引き裂き力（Ｎ）を求め、これをエレメンドルフ引き裂き強度として表示し、厚さの因子を考慮せずに比較できるようにした。
【０１６５】
（平均破断強度及び平均破断伸びの測定：幅手方向、長手方向）
各ポリエステルフィルムを、温度２３℃、相対湿度５５％に調整された部屋に４時間以上放置した後、試料幅１０ｍｍ、長さ１５０ｍｍに切断し、チャック間隔を１００ｍｍとし、引張速度１００ｍｍ／ｍｉｎで引張試験を行った。ポリエステルフィルムの製膜方向のタテ（長手方向）、ヨコ（幅手方向）について計測し得られた荷重−伸び曲線から、長手方向及び幅手方向の破断強度、破断伸びを求め、これを１０サンプルについて測定を行い、それぞれ平均破断強度、平均破断伸びを算出した。
【０１６６】
（アセトアルデヒド（ＡＡ）含有量の測定）
液体窒素中で、各ポリエステルフィルムを微粉末に粉砕し、ガラスバイアル瓶に密閉して、１７０℃、１５分間で発生するＡＡ量を高感度ガスクロマトグラフで定量した。
【０１６７】
（ヘーズの測定）
ＡＳＴＭ−Ｄ１００３−５２に従って、へーズの測定を行った。
【０１６８】
（コアセットカールの評価）
各ポリエステルフィルムを作製した直後に、３５ｍｍ（製造時の横方向）×１２０ｍｍ（製造時の縦方向）の帯状に切断し、温度２３℃、相対湿度５５％の条件下で１日放置した後、直径が１０．８ｍｍであるコアに巻き付けた。なお、試料に幅手カールがあるときはその支持体の凹面が外になるようにして巻いた。その後、温度５５℃、相対湿度２０％の環境下で２４時間熱処理を行った。熱処理後、温度２３℃、相対湿度５５％の環境下で３０分かけて放冷した後、コアから解放し、３０分経過後にポリエステルフィルムのコアセットカール度を測定した。カール度は１／ｒで表し、ｒはカールした試料の曲率半径を表し、単位はｍである。
【０１６９】
【表２】

【０１７０】
《ポリエステルフィルム及び試料の製造工程適性の評価》
（製膜安定性の評価）
各ポリエステルフィルムのフィルム製膜時の状況を目視観察し、下記の基準に則り製膜安定性の評価を行った。
【０１７１】
○：ドラムへのキャスト及び縦延伸へのフィルム先頭部の通過が支障なく行える
△：若干の装置条件の改良で製膜が可能であり、安定してフィルムを得ることができる
×：製膜過程で、高曲率（小径）の搬送ロールで破断が発生しやすく、製膜工程上、安定感に欠けるもの
（横延伸安定性の評価）
各ポリエステルフィルムのフィルム製膜時の状況を目視観察し、下記の基準に則り横延伸安定性の評価を行った。
【０１７２】
○：従来のポリエチレンテレフタレートフィルムの製造条件範囲内で、十分な膜厚均一性が得られる
△：従来のポリエチレンテレフタレートフィルムの製造条件に対し、延伸倍率、延伸温度、熱固定の各条件を見直すことにより、十分な膜厚均一性が得られる
×：延伸倍率、延伸温度、熱固定の各条件を調整しても、幅手方向の厚みの均一性を確保することが難しく、生産安定性と収率に問題がある
（フィルム断裁性の評価）
上記作製した各ポリエステルフィルムを、断裁条件を最適に調整した回転する上刃と下刃で連続的に断裁し、その断裁状況を目視観察し、下記の基準に則りフィルム断裁性の評価を行った。
【０１７３】
○：フィルム切断面がきれいで、バリやダレなどの切断不良の発生が認められず、全く問題がなく断裁できる
△：フィルム切断面には問題ないが、巻き取った際に上刃で押し込まれた側のエッジが伸びて、巻き端部がエッジ高となるものが散発する
×：フィルム切断面がギザギザで、ポリエステルフィルムの積層界面が剥離したり、ヒゲ状の切りくずの発生量が多く、品質上問題となる
《ハロゲン化銀写真感光材料の評価》
上記作製したハロゲン化銀写真感光材料である各試料について、下記の評価を行った。
【０１７４】
（穿孔適性の評価）
各試料を、１３５フィルム３６枚撮りサイズに加工する際、試料の幅手両断部に、穿孔機を用いて規定のパーフォレーションを開け、そのパーフォレーション部を目視観察し、下記の基準に則り穿孔適性の評価を行った。
【０１７５】
◎：現行のＴＡＣベースを用いた製品と同等の穿孔適性を有し、パーフォレーション部にバリや抜け残りの発生が認められない
○：打ち抜いたパーフォレーション部の切れ味の違いが、指先の触感で僅かに認められるが、試料全長にわたって均一に穿孔されている
△：各穿孔部にわずかにバリが観察され、穿孔機の刃の摩耗状態によっては問題を生じると判断される品質である
×：穿孔部周辺に明らかな層間剥離や細い繊維状の切りくずの付着が観察され、実用上問題がある
（カメラ内給送性の評価）
パトローネに装填された１３５フィルム３６枚撮りのカラーネガフィルムの各試料を、温度２３℃、５５％ＲＨの環境下で１日放置した後、温度５５℃、２０％ＲＨの環境下で２４時間の熱処理を行なった。この試料を、カメラ２機種（Ｚ−ｕｐ１５０、コニカ社製、及びＥＯＳ−ＫＩＳＳＩＩＩ、キャノン社製）でフィルム装填、全コマ撮影及び搬送、巻き上げの動作状況を観察し、下記の基準に則りカメラ内でのフィルム給送性の評価を行った。
【０１７６】
○：フィルム給送性に全く問題がない
△：フィルム給送途中で巻戻ったり、撮影が途中で止まるなどの動作異常が、極わずか発生するが、カメラに対する損傷は全くない
×：フィルム給送途中で巻戻ったり、撮影が途中で止まるなどの動作異常が頻発し、カメラ側の駆動に支障が生じ、明らかにカメラ損傷の要因となるもの
（フィルム編集適性の評価）
各試料について、下記の基準に則りフィルム編集適性の評価を行った。
【０１７７】
○：撮影済みの各試料の先頭と後尾を切り落として接合するスプライサー（ＭＳ６５０Ｄ、三友社製）及び指定の撮影コマの片側エッジに半円形の切り欠きを入れるノッチャー（ＫＰＮ１２００ＤＸ、コニカ社製）のいずれにおいても円滑な動作を示し、シネ現像処理前の長尺リール作成工程に支障のないもの
△：スプライサーでの切断不良により接合部が僅かに不安定、またはノッチャーによる打抜き不良による装置の停止が僅かに発生し、調整のための作業工数を必要とするが、最適条件に設定し直すことにより連続的に作業が可能
×：スプライサーでの切断不良により接合部が不安定で、またはノッチャーによる打抜き不良による装置の停止が頻発し、条件の再調整を行ってもスプライサー、ノッチャーの自動操作が行えず、すべて手動操作で対応が必要な品質
（シネ現像処理適性の評価）
上記各試料を撮影した後、シネ型のカラーネガフィルム自動現像処理機であるＮＣＶ２４（ノーリツ鋼機株式会社製）で処理を行い、下記の基準に則りシネ現像処理適性の評価を行った。
【０１７８】
○：シネ現像処理において、全く支障がなく処理が行える
△：処理液中でのカール、乾燥時のカールがやや強く、安定搬送にやや懸念が認められるが、処理は行える
×：フィルム搬送時に、幅手の変形やガイドロールにフィルムエッジ部が接触して折れ込みが発生し、安定した現像処理が行えない
（ミニラボ現像処理適性の評価）
上記各試料を撮影した後、ミニラボタイプのカラーネガフィルム自動現像処理機であるＫＰ５０ＱＡ（コニカ株式会社製）で処理を行い、下記の基準に則りミニラボ現像処理適性の評価を行った。
【０１７９】
○：ＴＡＣベースを用いた現行のカラーフィルムと同様に処理ができる
△：フィルム導入口でフィルムを引き出した後、フィルム後端部を切り落とす工程でカッターの動作が鈍く、切断不良が散発するが、切断条件を調整することにより処理が行える
×：フィルム導入口でフィルムを引き出した後、フィルム後端部を切り落とす工程でカッターの動作が極めて鈍く、切断不良が多発し、毎回手動での切断作業が必要になるもの
（プリンター搬送性の評価）
各試料を、特開平１０−１２３６５２号公報の段落番号〔０２２０〕〜同〔０２２７〕に記載の現像処理方法に準じて発色現像処理を施した後、プリンター（ＣＬＰＰ１７７１、コニカ社製）で露光作業時の搬送性を評価し、下記の基準に則りプリンター搬送性の評価を行った。
【０１８０】
○：プリンター搬送が極めてスムーズで、全く問題がない
△：プリンターのフィルム挿入部で僅かに引っかかる場合があるが、条件を調整することにより対応が可能である
×：現像処理済み試料の変形が大きく、かつ平面性が悪いため、フィルム搬送に支障があり、フィルム面にキズが入る
（集積性の評価）
発色現像処理済みの各試料（３６枚撮り）の全長を束ねて取り扱う際に、幅手に硬くカールして柔軟性に欠けるため極めて取り扱いにくいものを×、長手にカール値は小さいが強く変形が残り、やや螺旋状に絡まりやすいものを△、通常の取り扱いにおいて、違和感なく束ねることができて次の工程へ円滑に送れるものを○として評価した。
【０１８１】
（プリント画像の確認）
上記各試料について、室内及び屋外シーンを撮影し、これをミニラボタイプのカラーネガフィルム自動現像処理機であるＫＰ５０ＱＡ（コニカ株式会社製）でカラープリントを作成し、得られたカラープリント画像のピント性、カブリの発生の有無を目視観察し、現行のＴＡＣフィルムを用いたカラーネガフィルムと同等の特性を○、ピントのずれあるいはカブリの発生が僅かに認められるものを△、現行のＴＡＣフィルムを用いたカラーネガフィルムに対し、明らかにピントのずれあるいはカブリの発生が認められるものを×と判定した。
【０１８２】
（現像処理直後のカール度の測定）
各試料を、ミニラボ現像処理機（コニカ社製、ＫＰ５０ＱＡ、通常のネガ現像と同条件）で処理し、出口から排出後、温度２３℃、相対湿度５５％の条件下で１時間放置した後に、フィルム中央部のカール度（１／ｍ）を測定した。ミニラボの運転条件は、処理工程は発色現像工程（ＣＤ）、漂白工程（ＢＬ）、定着工程（ＦＩＸ）、安定化工程（ＳＴＡＢ）からなり、各処理液の温度はすべて３８℃、各工程の処理時間は各１９６秒、５０秒、１００秒、７０秒であり、その後の６０℃の温風により、６０秒の乾燥を行った。
【０１８３】
（現像処理後の経時カール度の測定）
上記ミニラボ現像処理機を用いて現像処理を行った試料を、直ちに２３℃、５５％ＲＨの環境下で、長手方向が垂直になるようにつり下げて、１日放置後にフィルム中央部のカール度を同様に測定し、現像処理後の経時カール度とした。
【０１８４】
以上により得られた各評価結果を、表３に示す。
【０１８５】
【表３】

【０１８６】
表３より明らかなように、本発明のポリエステルフィルムは、比較例に対し、フィルム製造安定性（製膜安定性、横延伸安定性）に優れ、ＴＡＣフィルムに近似の引き裂き強度、破断強度、破断伸び特性を有し、フィルム断裁性に優れ、それを用いたハロゲン化銀写真感光材料は、包装工程における穿孔適性、撮影工程でのカメラ内給送性、現像処理工程でのフィルム編集適性、シネ及びミニラボ現像処理適性、プリンター搬送性、集積性、プリンター適性（ピント性）に優れていることが分かる。
【０１８７】
【発明の効果】
本発明により、フィルム製造安定性が良好で、引き裂き強度、破断強度、破断伸び特性、フィルム断裁性に優れ、かつ包装工程における穿孔適性、撮影工程でのカメラ内給送性、現像処理工程でのフィルム編集適性、シネ及びミニラボ処理適性、プリンター搬送性、集積性、プリンター適性（ピント性）に優れているポリエステルフィルムを提供することができた。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel biaxially stretched polyester film, specifically, has excellent film production stability, excellent tear strength, breaking strength, breaking elongation characteristics, excellent film cutting property, and is suitable for perforation aptitude in a packaging process and photographing process. The present invention relates to a polyester film having excellent in-camera feedability, film editing suitability in a developing process, suitability for cine and minilab processing, printer transportability, integration, and printer suitability (focusability).
[0002]
[Prior art]
Biaxially oriented polyester films possess various properties in a well-balanced manner and are widely used as industrial materials. In particular, in the field of silver halide photographic materials, medical films for X-ray photography, films for printing, or A silver halide photographic light-sensitive material requiring a relatively large area, such as a display film, and has a proven track record as a support in the field where it is used as a flat surface. On the other hand, as a color film or a monochrome film for general amateurs, a cellulose-based polymer film mainly composed of a cellulose triacetate (hereinafter abbreviated as TAC) film has been used for a long time. As described above, in the current amateur photographic market, photographic films using TAC films are the mainstream, and equipment designs such as a camera used for photographing, a development processing machine used in a photo lab, and a film splicer are based on the TAC film. Various photographic-related devices exist that are designed in accordance with the physical properties of the film and are actually suitable for a large number of TAC films.
[0003]
In general, a TAC film has optical isotropy and excellent transparency, has a suitable moisture permeability and water retention, and has a curling curl generated when stored in a roll. It has a characteristic characteristic of a roll-type photographic film for general consumers which is said to be recovered, and no substitutes satisfying this characteristic existed until now.
[0004]
If the film has a curl, various problems may occur during the wet developing process or after the developing process, for example, folding may occur during transport in the developing machine, or the guide roll of the developing machine may be damaged. If the film is a color negative film, it may cause scratches in the printer and blurred focus due to the curl characteristics held during the printing process on color paper, etc. This causes problems such as jamming and breakage during transport. It is also an advantageous feature of the TAC film that the curl curl is recovered at the time of wet development processing and that a suitable strength and rigidity as a support in a developing solution can be maintained.
[0005]
However, TAC films that are widely used at present have various problems. One of them is pointed out that a chlorine-based hydrocarbon such as methylene chloride (boiling point: 41 ° C.) is used as a solvent when producing a TAC film. Methylene chloride has been conventionally used as a good solvent for cellulose triacetate, and is preferably used because it has a low boiling point and can be easily dried in the film forming and drying steps of the production process. However, in recent years, the amount of methylene chloride used has been limited from the viewpoint of environmental problems and the like. For this reason, measures such as thorough recovery of methylene chloride in the manufacturing process are taken. However, large-scale recovery equipment is required and the burden on costs is large at present.
[0006]
As one of the solutions to the above problems, for example, JP-A-11-310640 discloses a method using cooling and dissolving TAC, and JP-A-11-152342 discloses a method using methylene chloride by a method in which a solvent is changed. A method for producing a cellulose triacetate film that has not been used or can be significantly reduced has been proposed.However, equipment investment for using an organic solvent is still increasing, or equipment for reducing concerns such as flammability and explosiveness has been proposed. At the present time, investment is required, and the solution has not been substantial since organic solvents are used.
[0007]
On the other hand, various attempts have been made to replace the TAC film with another plastic film. For example, in US Pat. No. 4,141,735, annealed polyethylene terephthalate (hereinafter abbreviated as PET), polyethylene 2,6 naphthalate (hereinafter abbreviated as PEN) and the like are being studied for practical use. Of these, the annealed PEN film having a thickness of about 85 μm has already been put to practical use as a photographic film for APS (Advanced Photo System). The annealed PEN film is characterized in that it does not easily form a curl even when it is stored in a roll. However, the thickness of the annealed PEN film is reduced to the 135 format photographic film which is now widely used. If the thickness of the TAC film used is about 120 μm, which is the same as the thickness of the TAC film, the mechanical properties of the support, such as stiffness and breaking strength, are too high. At present, it is not yet used in 135 format compatible systems.
[0008]
On the other hand, JP-A-10-20441, JP-A-2000-206646, and JP-A-2001-98089 propose a film in which the film strength is reduced and the cutting easiness is enhanced, and application to a 135 format is attempted. Although it has been used, it has not yet reached a quality that can be put to practical use. In addition, PEN films are currently used because the raw material cost of the resin is high and the melting point is high, and the aptitude in production is poor due to the load on thermal energy and the energy load during processing due to the high resin strength. There is little economic advantage to replacing with TAC film. In the prior art, there has been studied a method of obtaining a material having a low curl by applying a heat treatment to a resin having high rigidity such as polyethylene terephthalate or polyethylene naphthalate plastic. At present, it is difficult to find a support for photographic film compatible with TAC from the viewpoint of using a high material.
[0009]
Polyethylene terephthalate has been put to practical use as a support for photographic light-sensitive materials used in the form of a sheet, as described above, due to its excellent dimensional stability and mechanical strength. Is poor in curl recovery property (easiness of curl removal), so that a roll film having a small diameter such as 135 format cannot be practically used as a support. Japanese Patent No. 3142571 and Japanese Patent Application Laid-Open No. 8-146558 disclose a method of preventing curling of curl. Polyethylene terephthalate has a Tg of around 80 ° C., and a 135-format photographic film is routinely stored. It has not been put to practical use because it tends to have a curl easily under an environment.
[0010]
Further, a method has been disclosed in which curl recovery after development processing is approximated to TAC by introducing a hydrophilic group into a hydrophobic resin (for example, see Patent Documents 1 to 3). These proposed methods modify the PET or make the resin composition and mechanical strength of the film at the time of lamination specific, but occur in the process of processing a large amount of photographed photographic film in the market. At present, various issues have not been completely solved.
[0011]
Polyethylene terephthalate is particularly difficult to break after being stretched. Therefore, it is a disadvantage that it is difficult to cut polyethylene terephthalate before and after development for processing equipment that has set optimal conditions for a TAC film with good cutability. It is known that a failure occurs in a device for transporting, cutting, and perforating a photographic film. In recent years, photographic films having a length of about 1 m to 2 m, such as 24- or 36-shot film, are often processed individually by mini-lab developing machines in stores in the market. When supplying photographic film products on a large scale, individual undeveloped films like a large lab (wholesale lab) are joined by a tape spurser and processed into a long roll, and then developed. System, for example, since there are still a lot of roll-type automatic developing machines remaining, the workability before development and the film during development are not broken, the handling after development (easiness of winding and bundling), Cutability, perforation (such as making a cutout on one side of a specified image frame), film rigidity, film flatness, etc. are important factors. There is that trouble occurs me. As for cine film for movies, polyester film has already been put to practical use, and even thin film with APS size has been put to practical use. If it is possible to handle various types of existing processing equipment such as 135 size and work that does not require skill, a general-purpose alternative film that can coexist with photographic film of TAC film is still not available. It has not appeared yet.
[0012]
[Patent Document 1]
JP-A-5-210199 (Claims)
[0013]
[Patent Document 2]
Japanese Patent Application Laid-Open No. H6-161035 (Claims)
[0014]
[Patent Document 3]
Japanese Patent Application Laid-Open No. 2000-131800 (Claims)
[0015]
[Problems to be solved by the invention]
The object of the present invention is to provide good film production stability, excellent tear strength, rupture strength, rupture elongation properties, excellent film cutting properties, and suitability for perforation in the packaging process, in-camera feedability in the photographing process, and development processing process. An object of the present invention is to provide a polyester film excellent in film editing suitability, cine and minilab processing suitability, printer transportability, integration property, and printer suitability (focus property).
[0016]
[Means for Solving the Problems]
The above object of the present invention is achieved by the following configurations.
[0017]
1. A biaxially stretched polyester film having a multilayer structure in which two or more polyester layers are laminated, wherein the surface layer is an aromatic dicarboxylic acid having a metal sulfonate group, a polyalkylene glycol, and cyclohexylene dimethylene glycol. A biaxially stretched polyester film, which is contained as a copolymer component.
[0018]
2. A biaxially stretched polyester film having a multilayer structure in which two or more polyester layers are laminated, wherein at least one of the polyesters contained in each layer is a polyester containing cyclohexylene dimethylene glycol as a polyester component. Characteristic biaxially stretched polyester film.
[0019]
3. A biaxially stretched polyester film having a multilayer structure in which two or more polyester layers are laminated, wherein at least one layer has an aromatic dicarboxylic acid having a metal sulfonate group, a polyalkylene glycol, and cyclohexylene dimethylene glycol. Is contained as a copolymer component of the same or different polyester, and the molar fraction of the cyclohexylene dimethylene glycol relative to the total glycol component of the polyester contained as the copolymer component is 50% or more. Stretched polyester film.
[0020]
4. It contains two or more types of polyester resins as components, and has a trouser tear strength in the width direction of 0.2 N or more and 1.5 N or less, a longitudinal Elementendorf tear strength of 0.2-1.1 N, and a long length. The average value of the breaking strength in the direction and the width direction is 140 MPa or less, the average value of the breaking elongation in the longitudinal direction and the width direction is 130% or less, the acetaldehyde (AA) content is 30 ppm or less, and the haze is 1. The biaxially stretched polyester film according to any one of Items 1 to 3, wherein the content is 7% or less.
[0021]
5. A polyester film obtained by laminating a plurality of polyester layers having different compositions by co-extrusion, wherein the average value of the breaking strength in the longitudinal direction and the width direction is 150 MPa or less, and the average value of the elongation at break in the longitudinal direction and the width direction is 120. %, And the total film thickness is 105 μm or more and 130 μm or less. The biaxially stretched polyester film according to any one of the above items 1 to 4, wherein
[0022]
6. Contains a polyester obtained by copolymerizing an aromatic dicarboxylic acid having a metal sulfonate group and polyethylene glycol as a modifying component of the polyester, and has a tear strength by the trouser method of 0.3 N or more and 1.2 N or less in both the longitudinal and width directions. The biaxially stretched polyester film according to any one of the above items 1 to 5, characterized in that:
[0023]
7. A core layer mainly composed of polyethylene terephthalate (A) is laminated on both sides with a skin layer mainly composed of polyethylene terephthalate (B) containing, as a copolymerization component, an aromatic dicarboxylic acid having metal sulfonate and polyethylene glycol. 7. The biaxial as described in any one of 1 to 6, wherein the skin layer contains 0.1 to 3% by mass of a phenolic antioxidant based on the mass of the polyethylene terephthalate (B). Stretched polyester film.
[0024]
8. The biaxial stretching according to claim 7, wherein a ratio (hc / hs) of the thickness hc of the core layer to the total thickness hs of the skin layer is 0.1 or more and 1.2 or less. Polyester film.
[0025]
9. The core layer contains 5 to 20% by mass of a polyester having 1,4 cyclohexane dimethanol as a glycol component based on the total resin amount of the core layer, and the two skin layers have a mole number M of the acid component of the entire polyester. ₁ Number M of the aromatic dicarboxylic acid component having a metal sulfonate group with respect to ₂ Ratio (M ₂ / M ₁ 9) is 0.2 to 10; the biaxially stretched polyester film according to the item 7 or 8 above.
[0026]
10. The skin layer contains 0.001 to 0.5% by mass of inert fine particles having an average particle size of 0.05 to 1.5 μm, wherein the skin layer contains 0.001 to 0.5% by mass of inert fine particles. Biaxially stretched polyester film.
[0027]
11. The core layer uses polyethylene terephthalate having an IV (intrinsic viscosity) of 0.45 to 0.75, and the two skin layers use a modified polyester resin having an IV of 0.47 to 0.60. The biaxially stretched polyester film according to any one of the above items 7 to 10, wherein
[0028]
Hereinafter, the present invention will be described in detail.
The biaxially stretched polyester film of the present invention (hereinafter, also referred to as the polyester film of the present invention) is obtained by laminating at least two polyester resin layers. Any number of component layers of the polyester film of the present invention may be laminated, but generally two or three layers are preferable from the viewpoint of complicating production equipment. The term “lamination” in the present invention means that two or more types of molten resins are joined together with fluidity and processed into an integrated sheet film. It is necessary that one layer has a thickness of 2 μm or more in the final photographic support in order to exert the function of the present invention. The so-called laminating process, which is performed after the solid sheets are formed and then bonded together, or the application process using a paint or the like in the course of transporting and winding the raw material is not included in the definition of “lamination” defined in the present invention.
[0029]
The "polyester" in the present invention is a thermoplastic resin that can withstand the above-mentioned sheet processing by heat melting and stretching and heat treatment described below, and has an ester bond in the main chain of the polymer. In the present invention, the term "copolyester" means that either a dibasic acid component or a glycol component constituting the polyester is not a single component, but a plurality of dibasic acid components or glycol components in one molecule from the polymerization stage. A polymer made for the purpose of introduction. Therefore, a polymer obtained by merely melting and mixing polyesters having different components is not included in the definition of “copolymer”.
[0030]
Further, the “surface layer” or “skin layer” in the present invention is a polyester layer located at the outermost layer of the laminated polyester film, and there are two layers on the front side and the back side. It can be distinguished from the surface layer on the front side or the surface layer on the back side by its thickness, thickness, or surface that contacts the air or the surface of the cooling drum during melt casting.
[0031]
The “core layer” or “core layer” in the present invention refers to a layer sandwiched between the two surface layers in the laminated polyester film of the present invention. For example, a general-purpose polyester and a copolymerized polyester are prepared, and two or more layers are laminated, or a layer in which the inert particles are added to the polyester and a layer in which the inert particles are not added are laminated. It may be unevenly distributed. In the case of three or more layers, the surface layer is preferably a copolymerized polyester layer in order to recover curl during development. Furthermore, in order to improve the adhesion between the laminations, for example, as described in JP-A-6-161035, a copolymer polyester can be mixed into the polyester layer. The mixing ratio is preferably from 5 to 70% by mass, more preferably from 10 to 50% by mass.
[0032]
When three or more polyester layers containing a copolymerized polyester are laminated, in order to recover curl curl during development processing, the ratio of hydrophilic copolymerized components such as sulfoisophthalate, polyethylene glycol and polyethylene glycol dicarboxylic acid in the surface layer Is preferably larger than that of the core layer. That is, the surface layer is preferably designed to be relatively hydrophilic than the core layer. The basic configuration is preferably a configuration in which a core layer having excellent stretchability and rigidity is sandwiched between hydrophilic skin layers.
[0033]
When three or more layers are stacked, the surface layer may be a plurality of layers, and the core layer may be a plurality of layers. The total thickness of the layers corresponding to the core is preferably from 60 to 100 μm, and more preferably from 65 to 90 μm. If the thickness is less than 60 μm, the surface layer becomes thick, stretching unevenness tends to occur during film formation, and curl tends to occur. Further, the matting agent used for the surface mainly has a role of forming a roughness and a starting point of cutting on the surface, but since this matting agent cannot be excessively increased from the viewpoint of maintaining transparency, the matting agent for the surface layer is not used. There are necessarily restrictions on the thickness. Further, when the core layer has a thickness of 100 μm or more, the curl recovery property due to the water absorption expansion of the hydrophilic layer of the surface layer is reduced, and the resin is modified to improve the cuttability of the core layer, and the proportion of the copolymer component and the mixed resin is reduced. It is necessary to increase it, which is not preferable in terms of manufacturing cost. When a laminated structure is formed with two layers, the thickness of the polyester layer is preferably 50 to 115 μm, more preferably 55 to 90 μm. In this case, the hydrophilic function for one side of the polyester film is taken over by the photographic emulsion layer or the functional layer to be subsequently applied.
[0034]
Furthermore, one or more adhesive layers may be provided between the core layer and the intermediate layer by directly mixing polyester resins in which some or all of the two or more copolymer components are different from each other in the production line. At this time, in order to improve the adhesion between the laminated layers, the difference in copolymerization components between adjacent layers may be set within a certain range. Specifically, the conditions described in JP-A-6-289534 can be referred to. The layers constituting the polyester film of the present invention each have a thickness of 2 μm or more and do not include an undercoat layer or the like.
[0035]
In the polyester film of the present invention, two or more kinds of copolymerized polyester resins having different copolymerization component ratios are prepared and used in advance as a uniform mixed resin for the core layer or the skin layer, and even if they are laminated. good. As a feature of the present invention, it is preferable to mix a small amount of a resin (for example, 1,4-cyclohexylene terephthalate isophthalate) having low compatibility with polyethylene terephthalate in order to make the breakability of polyethylene terephthalate closer to TAC. By the above combination, the propagation of the fracture of the core layer becomes smooth, and the crack progresses with a stable stress. Also, by synthesizing cyclohexylene dimethylene glycol to the hydrophilic polyester of the skin layer or mixing it as cyclohexylene dimethylene glycol terephthalate resin, the synergistic effect with the matting agent allows the first time of piercing or cutting. Notches are easy to enter. At this time, if a resin having very poor compatibility with polyethylene terephthalate is used at an inappropriate mixing ratio, the polyester film after stretching becomes cloudy and loses transparency, which is not preferable.
[0036]
Next, the polyester used in the present invention will be described.
The polyester used for the polyester film of the present invention is a polyester containing a dicarboxylic acid component and a diol component as main components.
[0037]
Examples of the main component dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfondicarboxylic acid, diphenyletherdicarboxylic acid, and diphenylethanedicarboxylic acid. Examples thereof include acids, cyclohexanedicarboxylic acid, diphenyldicarboxylic acid, diphenylthioether dicarboxylic acid, diphenylketone dicarboxylic acid, phenylindanedicarboxylic acid, polyethylene glycol dicarboxylic acid, and polypropylene glycol dicarboxylic acid. As the diol component, ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis ( 4-hydroxyphenyl) sulfone, 9,9-bis (4,4'-di-β-hydroxyethyl) fluorene, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like.
[0038]
Among polyesters containing these as main components, from the viewpoint of transparency, mechanical strength, dimensional stability, etc., as the dicarboxylic acid component, terephthalic acid, isophthalic acid, or 1,4-cyclohexanedicarboxylic acid, diol component Preferred are polyesters containing ethylene glycol or 1,4-cyclohexylene dimethylene glycol as a main constituent. Among them, a polyester containing a polyethylene terephthalate unit and polycyclohexylene dimethylene terephthalate is preferred. When the ethylene terephthalate unit or polycyclohexylene dimethylene terephthalate is contained in an amount of 70% by mass or more with respect to the polyester, a film having excellent transparency, mechanical strength, dimensional stability, and the like can be obtained.
[0039]
Further, JP-A-1-244446, JP-A-4-234039, JP-A-5-210199, JP-A-6-82969 and the like disclose aromatic dicarboxylic acids and / or poly (carboxylic acids) having a sulfonic acid group or a salt thereof. The polyesters containing an alkylene glycol as a copolymer component are further described in JP-A-4-93937, JP-A-6-11795, JP-A-6-161935, JP-A-6-289534, JP-A-6-240020, Japanese Unexamined Patent Publication No. Hei 6-110154 discloses a polyester obtained by laminating two or more polyester layers. Such a polyester is effective in reducing curl and eliminating curl after development. Can be preferably used in combination with the above polyester film.
[0040]
The copolymerized polyester used in the present invention has an aromatic dicarboxylic acid having at least one metal sulfonate group, at least one polyalkylene glycol, or a polyalkyleneoxydicarboxylic acid as a copolymer component, and an aromatic dibasic acid and a glycol. It is a copolymerized polyester as a main component, and as the dibasic acid, for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid and the like can be mentioned, and as the glycol, for example, ethylene glycol, propylene glycol , Butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, p-xylylene glycol and the like. Among these, copolymerized polyethylene terephthalate containing terephthalic acid and ethylene glycol as main components is preferable.
[0041]
Examples of the aromatic dicarboxylic acid having a metal sulfonate group include dicarboxylic acids having a sulfonic acid group or a salt thereof, for example, 5-sodium sulfoisophthalic acid (5-SIP), 2-sodium sulfoisophthalic acid, and 4-sodium sulfoisophthalate. An acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid or an ester-forming derivative thereof, and a compound obtained by substituting sodium with another metal (for example, potassium or lithium) are used.
[0042]
The copolymerization ratio of the dicarboxylic acid component having a metal sulfonate group is preferably from 0.2 to 20 mol% based on all ester bond units, and if it is less than 0.2 mol%, sufficient curling and curling resolving property is not obtained. If it is not obtained, and if it exceeds 20 mol%, the stretchability is poor and the mechanical strength is poor, which is not preferable. A more preferred copolymerization ratio is 1 to 15 mol%. In particular, in order to adapt the photographic processing conditions to a developing system having a high pH of a fantasy processing solution, for example, a color developing solution for a color negative film, an alkali solution resistance is required. A copolymerization ratio of 12 mol% is preferred.
[0043]
Examples of the polyalkylene glycol include dibasic acids having a polyalkylene group, specifically, polyalkyleneoxydicarboxylic acid, polyethyleneoxydicarboxylic acid, polytrimethyleneoxydicarboxylic acid, and polytetramethyleneoxydicarboxylic acid. And the like. Of these, polyethyleneoxydicarboxylic acid is preferred, and the molecular weight is not particularly limited, but is preferably 300 to 20,000, more preferably 600 to 10,000, and particularly preferably 1,000 to 5,000. The copolymerization ratio of the polyalkylene glycol and / or polyalkyleneoxydicarboxylic acid is preferably 1 to 10% by mass of the copolymerized polyester reaction product.
[0044]
As the polyalkylene glycol, polyethylene glycol, polytetramethylene glycol and the like are used. Of these, polyethylene glycol is preferable, and the molecular weight is not particularly limited, but is preferably 300 to 20,000, more preferably 600 to 10,000, and particularly preferably 600 to 10,000. Those having 800 to 5000 are preferably used. When the molecular weight of the polyethylene glycol is 5,000 or less, the units of the polyethylene glycol are uniformly distributed in the formed polyester film, so that the transparency is good and even if the polyester film is dried again after absorbing water. Good flatness is maintained. When the molecular weight of polyethylene glycol is 800 or less, it is somewhat difficult to make the molecular weight and composition of the copolymerized polyester uniform during polymerization.
[0045]
The polyalkylene glycol is contained in an amount of 1 to 10% by mass, preferably 2 to 8% by mass, based on the total mass of the polyester as the reaction product. If the polyalkylene glycol is less than 1% by mass, sufficient curling and curling resolving properties cannot be obtained. On the other hand, if it exceeds 10% by mass, the Young's modulus immediately after immersion in water, for example, in a developing solution, decreases, which causes a decrease in mechanical strength.
[0046]
The polyester film of the present invention can be preferably used as a support for a silver halide photographic light-sensitive material. In this case, other components are copolymerized with the copolymerized polyester as long as the effects of the present invention are not impaired. Or other polymers may be blended.
[0047]
In the polyester film of the present invention, in addition to the compounds described above, other dibasic acids and glycols can also be used. For example, benzenedicarboxylic acid or a derivative thereof that can be used as a dibasic acid is 2,7. -Aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, diphenyldicarboxylic acid and diphenyletherdicarboxylic acid, and lower alkyl esters thereof (an ester-forming derivative such as anhydride and lower alkyl ester); cyclopropanedicarboxylic acid Alicyclic dicarboxylic acids such as acid, cyclobutanedicarboxylic acid and hexahydroterephthalic acid and derivatives thereof (ester-forming derivatives such as anhydrides and lower alkyl esters); and adipic acid, succinic acid, oxalic acid, azelaic acid, sebacine Acid and Aliphatic dicarboxylic acids and derivatives thereof such as timer acid (anhydride, lower ester formable derivatives such as alkyl esters), or the like, may be used in an amount of 10 mol% or less of the total diacid.
[0048]
Other dihydric alcohols other than the above that can be used in the present invention include propylene glycol, trimethylene glycol, diethylene glycol, triethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, p-xylene glycol, 1,4-cyclohexylene dimethylene glycol, bisphenol A, p, p'-dihydroxyphenylsulfone, 1,4-bis (β-hydroxyethoxyphenyl) propane, polyalkylene (eg, ethylene, propylene) glycol, and p- Phenylenebis (dimethylolcyclohexane) and the like can be mentioned. These may be used in an amount of 10 mol% or less of the dihydric alcohol according to the present invention.
[0049]
For example, the polyester may be one in which a terminal hydroxyl group and / or a carboxyl group is blocked by a monofunctional compound such as benzoic acid, benzoylbenzoic acid, benzyloxybenzoic acid, or methoxypolyalkylene glycol. It may be modified with a very small amount of a trifunctional or tetrafunctional ester-forming compound such as glycerin or pentaerythritol as long as a substantially linear copolymer can be obtained.
[0050]
The polymerization of the copolyester used for the polyester film of the present invention can be carried out by a commonly known method. That is, after transesterification of the dicarboxylic acid component and the glycol component, the polycondensation can be obtained by polycondensation at a high temperature under reduced pressure, and at this time, an aromatic dicarboxylic acid having a metal sulfonate group as a copolymer component can be obtained. And polyethylene glycol are added after the transesterification reaction, and polycondensation is performed. As an example of the catalyst composition for the transesterification reaction, for example, those described in JP-A-10-13041 can be used.
[0051]
In the polyester film of the present invention having a laminated structure, what is called a dry blend in which the polyester of each layer is mixed in advance in the form of resin pellets can be used. That is, instead of using a copolymer composition polyester in which the components of the resin of the specific layer in the final laminated film are the same, a plurality of different polyesters are appropriately combined and the same ratio is obtained in a pellet state. May be supplied from the hopper of the extruder. In addition to mixing the unmelted pellets in this way, before introducing the pellets into an extruder, a pellet having a uniform composition melt-mixed with a twin-screw extruder or the like so as to have a constant composition is used. May be. As described above, when the polyesters having different compositions are kneaded and pelletized by the twin-screw extruder in advance, the haze can be reduced, and the cuttability can be improved, particularly in the case of a resin that is difficult to mix. This is preferable because it has an effect on shape recovery after deformation due to heat or water absorption.
[0052]
As a method for producing a laminated polyester film of the present invention, for example, after the polyester of each layer to be laminated is melt-extruded from a separate extruder, and then bonded and extruded in a laminar flow form in a conduit of a molten polymer or an extrusion die. A co-extrusion method of cooling and solidifying on a cooling drum to produce an unstretched film and then biaxially stretching and heat-setting, or a melt extrusion of polyester from an extruder and cooling and solidifying on a cooling drum After coating the stretched film or the uniaxially oriented film obtained by uniaxially stretching the unstretched film with an anchoring agent, an adhesive or the like, if necessary, extrusion-laminate the copolymerized polyester thereon, and then biaxially stretch There is an extrusion lamination method of heat setting after completion of Extrusion methods are preferred.
[0053]
In the present invention, it is also a preferred embodiment that the obtained polyester film of the present invention is subjected to an annealing treatment. The annealing treatment is a heat treatment applied to the polyester film to reduce the curl of the polyester film. The effect of this heat treatment disappears when exposed to temperatures above the glass transition point.
[0054]
The heat treatment is preferably performed at a temperature of 50 ° C. or higher and a glass transition temperature or lower for 0.1 to 1500 hours, more preferably 0.2 to 72 hours. Among these annealing treatments, a particularly preferred heat treatment method is, for example, when the polyester film is polyethylene terephthalate, the Tg is about 85 ° C., and therefore, at a temperature of 84 ° C. or less, more preferably at 77 ° C. or less for 24 hours. About heat treatment. In particular, in order to perform heat treatment in a short time, it is very efficient and preferable to raise the temperature once to Tg or more and gradually cool it to a temperature near Tg. In the case of polyethylene terephthalate, as an example, the heat treatment time can be significantly reduced by once maintaining the temperature at 85 ° C. or higher and 120 ° C. or lower, cooling to 90 ° C., and then gradually cooling to 70 ° C. for 40 minutes. When a film subjected to such a heat treatment is measured by a differential thermal analyzer, an endothermic peak appears near Tg, and the larger the endothermic peak is, the less likely the winding habit is formed. Further, it is preferable that the heat treatment be performed so as to be 419 mJ / g or more, and more preferably 838 mJ / g or more.
[0055]
The polyester film of the present invention preferably contains an antioxidant. It is particularly effective when the polyester contains a compound having a polyoxyalkylene group. The antioxidant that can be used in the present invention is not particularly limited in its type, and various antioxidants can be used, for example, hindered phenol compounds, phosphite compounds, thioether compounds, and the like. Antioxidants. Above all, hindered phenolic antioxidants are preferred in terms of transparency. The content of the antioxidant in the present invention is usually 0.1 to 3.0% by mass, preferably 0.2 to 2.0% by mass based on the polyester resin. If the content of the antioxidant is low, decomposition products such as aldehydes are generated due to thermal degradation of the polymer during melting or drawing film formation. When this is used as a support for silver halide photographic materials, The so-called fogging phenomenon is apt to occur when the density of the exposed portion becomes high, and when it is too high, the haze of the polyester film becomes high and the transparency may be poor. Further, when the polyester film is provided with a silver halide emulsion layer and then subjected to a developing treatment, the flatness is deteriorated. These antioxidants may be used alone or in combination of two or more.
[0056]
In the present invention, the phenolic antioxidant is preferably contained in an amount of 0.1 to 3% by mass based on the mass of the polyester film. In particular, so-called hindered phenols having a molecular weight per phenolic hydroxyl group of 110 or more and 500 or less and having steric hindrance such as alkyl substituents at the 2- and 6-positions of the aromatic ring of the phenolic hydroxyl group are preferred. When the above-mentioned numerical value is 110 or less, the antioxidant itself tends to be thermally decomposed or deteriorated, and when it is 500 or more, the effect of suppressing the oxidative decomposition of the polymer chain of the copolymerized polyester becomes small, and the addition amount must be increased.
[0057]
In the polyester film of the present invention, a resin having a polyether chain, such as polyethylene glycol (hereinafter abbreviated as PEG), is liable to be thermally decomposed, so that an aldehyde is generated. When used as a support for a photographic light-sensitive material, photographic performance deterioration such as fogging is more likely to occur than ordinary PET or PEN. In a film containing a hydrophilic group, the generated aldehyde is easily diffused. This is a different mechanism from conventional PET, and in order to suppress this phenomenon, it is necessary to select an antioxidant and adjust the amount of addition. While suppressing the presence of oxygen at the time of resin synthesis, suppressing oxidative decomposition of PEG, strictly controlling the pressure reduction conditions, and setting the polymerization temperature and melting temperature as low as possible, for example, 290 ° C to 240 ° C, It is preferable that the generated amount be 100 ppm or less at the stage of the raw material chips. As a result of examining various conditions by appropriately selecting film forming conditions, raw materials, and antioxidants, it was found that there was no problem if the concentration of acetaldehyde was 30 ppm or less.
[0058]
The polyester film of the present invention preferably contains a dye as a colorant for the purpose of preventing the light piping phenomenon. Dyes to be blended for such purposes are not particularly limited in type, but it is necessary to have excellent heat resistance in film production, and anthraquinone-based and perinone-based dyes are used. No. Further, as the color tone, gray dyeing is preferable as seen in general photographic light-sensitive materials. Examples of these dyes include MACROLEX series manufactured by Bayer, SUMIPLAST series manufactured by Sumitomo Chemical Co., Ltd., and Diaresin series manufactured by Mitsubishi Kasei. These may be used alone or in a color tone requiring two or more dyes. It can be used by mixing so that At this time, the dye is adjusted so that the spectral transmittance of the film is 60% or more and 85% or less in the wavelength range of 400 to 700 nm, and the difference between the maximum and minimum of the spectral transmittance in the wavelength range of 600 to 700 nm is 10% or less. Is preferred in order to prevent the light piping phenomenon and obtain a good photographic print.
[0059]
The method of adding the colorant to the polyester film is not particularly limited, and a necessary amount of the colorant may be added at any stage from the polymerization of the polyester to the melt extrusion, and may be colored. The method of preparing so-called master pellets, appropriately diluting them and extruding them, is preferably used because the colorant concentration can be easily controlled. This method is effective when fine adjustment of the concentration is required, for example, when the recovered polyester is contained. The concentration of the dye in the master pellet is preferably 100 to 10000 ppm.
[0060]
When the dye is used at the same concentration with respect to the polyester, the total dye is increased and the transmittance is reduced in the case of a support having a large film thickness compared to a film having a small film thickness. If this increase in concentration is a problem, the concentration of layers other than the polyester layer located on the surface on the side where the silver halide emulsion layer is coated can be set lower.
[0061]
The thickness of the polyester film of the present invention is preferably from 95 to 130 μm, more preferably from 105 to 130 μm. If the film is thicker or thinner than this, there is a problem in that defocusing occurs in existing cameras and exposure machines. When the thickness is more than 130 μm, when a silver halide photographic light-sensitive material is loaded on a conventional 135 patrone, for example, the winding diameter of 36 shots is too large to be wound, or conversely, it is too thin at 105 μm. In such a case, a gap is generated in a state where the leading end of the film is exposed at the entrance of the cartridge, which is not preferable because it causes fogging due to light leakage.
[0062]
In the polyester film of the present invention, the haze is preferably 2.0% or less, more preferably 1% or less. If the haze is greater than 2.0%, for example, when the polyester film of the present invention is used as a support for a color negative film, when printed on color paper using this, the printed image becomes blurred and unclear. The haze in the present invention is measured according to ASTM-D1003-52.
[0063]
In the polyester film of the present invention, the polyethylene terephthalate resin of the core layer used preferably has an intrinsic viscosity (IV) in the range of 0.45 to 0.75. If the intrinsic viscosity is below the range specified above, the brittle resistance will be insufficient, and if it is above the range, the mechanical strength will be too strong. The intrinsic viscosity (IV) can be measured for the polyester film or each polyester resin using an Ubbelohde viscometer. Specifically, a mixed solvent of phenol and 1,1,2,2-tetrachloroethane (mixing mass ratio: about 55:45, and adjusting the falling time to 42.0 ± 0.1 seconds) as the solvent. Is used to prepare a solution (temperature: 20 ° C.) having a sample concentration of 0.2 g / dl, 0.6 g / dl, and 1.0 g / dl. Using an Ubbelohde viscometer, the specific viscosity (ηsp) at each concentration (C) is obtained, ηsp / c is plotted against c, and the obtained straight line is extrapolated to zero concentration to obtain the intrinsic viscosity. The unit is indicated by dl / g.
[0064]
In particular, in the present invention, the intrinsic viscosity (IV) of polyethylene terephthalate in the core layer is 0.45 to 0.75, and the intrinsic viscosity (IV) of the modified polyester used in the skin layer is 0.47 to 0.75. It is preferable to use a plurality of polyester resins having a ratio of 0.60. If the polyethylene terephthalate has an intrinsic viscosity of more than 0.75, the film after film formation becomes tough and the cutability becomes poor. On the other hand, if the intrinsic viscosity of polyethylene terephthalate is smaller than 0.47, the film becomes brittle, and it becomes difficult to stretch during film formation. On the other hand, if the intrinsic viscosity of the modified polyester is larger than 0.60, the fluidity during melt extrusion is poor, and if it is smaller than 0.47, the surface properties of the film deteriorate.
[0065]
The polyester film of the present invention may be provided with lubricity as required. In particular, when laminating a length of 1000 m or more on a single roll (original roll) and winding it, there is a means for forming appropriate unevenness on the surface to prevent wrinkles and deformation due to tightening of the finished original roll. Required. Since the polyester film of the present invention has a different mechanical strength from the conventional polyethylene terephthalate or polyethylene naphthalate film, the flatness is improved if the means for imparting slipperiness is formed during winding, and the yield is 95%. The above is preferable. The means for imparting lubricity is not particularly limited, but a method of adding external particles for adding inert inorganic particles to the polyester, a method of depositing internal particles for depositing a catalyst to be added at the time of synthesis of the polyester, or a method such as a surfactant is used. A method of applying to a surface is common.
[0066]
Among these, the method of depositing internal particles, which can control the particles to be deposited relatively small, is preferred because lubricity can be imparted without impairing the transparency of the film. As the catalyst, various known catalysts can be used, but use of Ca and Mn is particularly preferable because high transparency can be obtained. These catalysts may be used alone or in combination of two or more.
[0067]
The polyester film of the present invention is characterized in that it has a multilayer structure, and the above-described antioxidation, light piping prevention, imparting functions such as slipperiness, or the addition of various additives other than the above are added to all layers. However, it is preferable that it is added to at least the surface layer (skin layer). Further, the transparency of the polyester film can be increased by reducing or not adding the amount of the other layer (for example, the core layer). In particular, a matting agent for imparting lubricity is preferred in the present invention, since the film is easily distributed in the surface layer to control the rupture of the film.
[0068]
In the polyester film of the present invention, inert inorganic particles can be used as a matting agent. ₂ , TiO ₂ , BaSO ₄ , CaCO ₃ , Talc, kaolin and the like.
[0069]
The means for imparting lubricity is not particularly limited, but as a support for a silver halide photographic light-sensitive material, transparency is an important requirement. SiO with ₂ Although lubricity imparting by an external particle system using is well known, in the present invention, in particular, from the viewpoint of cutability, a layer containing a polyester in which cyclohexylene dimethylene glycol is copolymerized has an average particle size. Is present in an amount of 0.001 to 0.5% by mass of silica particles having a thickness of 0.05 to 1.5 μm, and this layer is provided on the outermost layer, for example, when cutting and perforating a polyester film having a thickness of 120 μm. It has been found that the ease with which the initial cut can be made is dramatically improved. In particular, when a mixture of polyethylene terephthalate containing sulfoisophthalic acid and polyethylene glycol as copolymerization components and polycyclohexylene dimethylene terephthalate containing cyclohexylene dimethylene glycol at a copolymerization ratio of 50% or more is easily mixed. The improvement in the resilience is significant.
[0070]
In addition, the average particle diameter referred to in the present invention is a value obtained by measuring the diameter of a powder as it is, or a powder dispersed in a liquid or a solid one by one, and averaging all the particles. In actual measurement, when the shape of one particle is not a true sphere, the average value is the average of the diameter of the virtual sphere circumscribing the particle and the diameter of the virtual sphere inscribed therein. A large number of photographs are taken at a constant magnification under an electron microscope, and the average value of the diameters of particles at 500 or more different places is determined, and this is defined as the average particle diameter. When a histogram is created by statistically processing the above data, a distribution of a single peak is usually obtained.However, when a histogram having multiple peaks is obtained by counting particles of the same type, multiple histograms are obtained. It is considered that particles having different average particle sizes are mixed, and the mode particle size of each peak is defined as each average particle size.
[0071]
Furthermore, even in a layer of a copolymerized polyester alone or a polyethylene terephthalate film, the cutability is improved by including organic particles having an average particle size of 0.1 to 2.5 μm in a range of 0.001 to 5% by mass. It was also found to be improved.
[0072]
When organic particles are used, those which do not melt or decompose at 280 ° C., which is the melt extrusion temperature of polyester, are desirable. It is preferable to use those having a mass reduction rate of 10% or less at 300 ° C. when the temperature is raised from normal temperature to 300 ° C. at a rate of 10 ° C./min in a nitrogen stream. The organic particles having good binding between the surface of the organic particles and the polyester resin in the formed polyester film are preferable from the viewpoint of the transparency of the film. Preference is given to three-dimensionally crosslinked polymethyl methacrylate (PMMA), styrene-divinylbenzene copolymer particles, melamine formaldehyde particles and the like. It is more preferable that the particles are monodisperse particles containing the above particles. In addition to the above, in imparting lubricity by the internal particle system, lubricity can be controlled by adjusting the amount of P added with metals such as Ca, Mn, and Mg, and it is preferable to use them together.
[0073]
In the polyester film of the present invention, the skin layer preferably contains 0.001 to 0.5% by mass of inert fine particles having an average particle size of 0.05 to 1.5 μm. The inert fine particles referred to in the present invention are particles that can maintain transparency while appropriately reducing the tear strength of the film after forming the film by adding it to the resin, including the slippery particles. Which means that cutting and perforating properties can be improved. In this case, it is needless to say that the inert fine particles need to be uniform in the polyester and can be dispersed in the primary particles. The cutting property in the present invention means, for example, the ease of cutting when cutting with scissors or a cutter, and the smoothness of the cut edge is good. It refers to the state when the contact point of the blade advances. The perforation property means, for example, the sharpness when a film or a silver halide photographic light-sensitive material provided with a silver halide emulsion layer is punched out with a mold. That is, it refers to a state in which breaks of a certain length occur almost simultaneously. The ease of incision refers to the ease of forming an initial cut (a trigger for breaking). Although it is difficult to express these indices with a single measurement of mechanical properties, cutter units, punches, and cutter units built in the actual process of manufacturing silver halide photographic light-sensitive materials, , A cutter mounted on a film splicer that edits undeveloped film, a notcher that punches a notch on a photographic film after processing (a machine that punches a semicircle to detect a frame), etc. It was found that several evaluation methods corresponded to the quality of film cutability in actual machines. In other words, the trouser tear strength in the width direction for the cutting property, the tear strength in the longitudinal direction or the average value of the breaking elongation in the longitudinal direction and the transverse direction in the piercing property, and the ease of incision is the average or the longitudinal strength in the longitudinal direction and the transverse direction. And the average of the elongation at break in the width can be used as the index. However, the cutting property when passing through an actual camera, a minilab processing machine, a processing machine of a large lab, and a subsequent processing machine (for example, a sliver that cuts a developed film into several frames and inserts it into a sleeve) ( The cutting property, the perforation property, the ease of making a cut, and the various operations and the occurrence of troubles on the machine cannot all be explained by the above-mentioned physical property measurement. Therefore, it is preferable that the silver halide photographic light-sensitive material actually studied and manufactured is passed through several representative models, the state thereof is observed, and the result is judged as the final judgment.
[0074]
The biaxially stretched polyethylene terephthalate usually has a breaking strength of 140 MPa or more and a breaking elongation of 130% or more, and is used as a substitute for cellulose triacetate (TAC) used for a photographic support because of its mechanical strength characteristics. Turned out to be very difficult. Therefore, by adding a modifying component to the polyester itself, reducing the strength, and further including an inert fine particle in the skin layer, the TAC film is more easily broken than the conventional polyethylene terephthalate film, and particularly has a reduced trouser tear strength. A polyester film having a tear strength close to the above was obtained.
[0075]
The width direction trouser tear strength is 1.5 N (Newton = kg · m / s) when converted to a thickness of 120 μm. ² ) Or less, more preferably 0.2N or more and 1.3N. The TAC film has a thickness of from 0.2 N to 0.4 N at a thickness of 120 μm, and the polyester film of the present invention can be sufficiently substituted.
[0076]
What is particularly noticed is that the same thickness as that of the TAC, that is, the total thickness of 95 to 130 μm, can achieve the tear strength and the rigidity equivalent to that of the TAC. Also, by adding inert fine particles, the details of the mechanism by which the tear strength is controlled are unknown, but because the hydrophilic polyester and the polyester containing a large amount of cyclohexylene dimethylene glycol are not compatible with each other, It is considered that the inert fine particles promote the propagation of fracture at the interface between both resin phases. Thereby, it is considered that the ease of notching is improved and the values of the breaking strength and the breaking elongation are reduced. Even in the absence of inert fine particles, the terephthalate polymer containing cyclohexylene dimethylene glycol in a large amount (50% or more in the molecule) has a lower density than the homopolymer of polyethylene terephthalate due to the steric effect of the cyclohexane ring. Since the cohesive force acting between molecules is presumed to be low, the breaking strength is considered to be lower than that of polyethylene terephthalate.
[0077]
In the present invention, when a layer formed by mixing a plurality of polyesters having different compositions is replaced with a single layer of a copolymerized polyester having the same composition as this layer, the haze is slightly improved, but the mechanical strength of the entire film is improved, Cutability will be far from the original TAC film approximation.
[0078]
It is presumed that the non-uniformity of the resin in the polyester layer improves the cutting property. However, if the non-uniformity is too high, the scattering of light becomes remarkable due to the difference in the refractive index of the resin, and the haze deteriorates. Further, if uneven resin is distributed in the layer, the flatness during film formation is impaired.
[0079]
Regarding the trouser tear strength and the Elmendorf tear strength according to the present invention, it is considered that the trouser tear strength detects the mechanical strength at the time of steady breakage progress, as is clear from the measurement method. The Dorf tear strength detects the energy of the instantaneous break and represents a different mode of cutting.
[0080]
In the polyester film of the present invention, recovered polyester can be used. Recovered polyester is a product obtained by collecting and pulverizing film debris generated as edge debris or defective winding in the film forming process of a photographic polyester support, or a silver halide photograph made using a polyester support. This is a material obtained by collecting waste (tip processing, perforated waste, defective winding, etc.) of the photosensitive material and a film that is no longer required by the user, peeling off layers other than the support, and grinding. The recovered polyester is preferably mixed with a layer other than the outermost layer (skin layer) of the support on the surface on which the silver halide emulsion is coated, and when three or more layers are used, it is mixed with at least one of the intermediate layers. Is preferred. The mixing ratio is preferably 40% by mass or less. If it is 40% by mass or more, strength, transparency and the like become problems. Further, the methods described in JP-B-7-332 and JP-B-7-333 can also be used. In addition, as the collected polyester, collected waste such as a PET bottle can be considered, but it is not preferable because of problems such as impurities and influence on photographic performance. However, such debris can be mixed within a range that does not affect the performance, which is preferable from the viewpoint of resource recycling.
[0081]
In the polyester film of the present invention, as a method of laminating the polyester, a conventionally known method can be used. For example, a co-extrusion method using a plurality of extruders and a feed block die or a multi-manifold die, on a single-layer film or a laminated film constituting a laminate, melt-extruding other resins constituting the laminate from the extruder, Examples include an extrusion lamination method of cooling and solidifying on a cooling drum, and a dry lamination method of laminating a single-layer film or a laminated film constituting a laminate via an anchoring agent or an adhesive as necessary. Among them, a co-extrusion method in which the number of production steps is small and adhesion between layers is good is preferable.
[0082]
A method for obtaining an unstretched sheet and a method for uniaxially stretching in the longitudinal direction can be performed by a conventionally known method. For example, the raw material polyester is formed into pellets, and dried by hot air or vacuum while applying heat. The drying temperature is preferably high as long as it does not undergo oxidative decomposition by heat, and is usually 100 to 200 ° C, preferably 140 to 180 ° C. Vacuum drying is preferably used because it can reduce oxygen and moisture and prevent oxidation. Drying is performed so that the water content is 100 ppm, preferably 30 ppm or less. Then, it is melt-extruded, extruded into a sheet shape from a T-die, brought into close contact with a cooling drum by an electrostatic application method or the like, and cooled and solidified to obtain an unstretched sheet.
[0083]
Then, the obtained unstretched sheet is heated in a range from the glass transition temperature (Tg) of the polyester to Tg + 100 ° C. through a plurality of roll groups and / or a heating device such as an infrared heater, and subjected to single-stage or multi-stage longitudinal stretching. It is. The stretching ratio usually needs to be in a range of 2.5 to 6 times, and a range in which subsequent transverse stretching is possible. The setting of the stretching temperature is preferably based on the highest Tg of the polyester of each constituent layer.
[0084]
In the present invention, the longitudinally uniaxially stretched polyester film obtained as described above is heated in a stretched region divided into two or more within a temperature range of Tg to Tm (melting point) -20 ° C. It is preferable that the film is stretched in the transverse direction while being heat-set. The transverse stretching ratio is usually 3 to 6 times, and the ratio between the longitudinal and transverse stretching ratios is determined by measuring the physical properties of the obtained biaxially stretched film and appropriately adjusting it to have preferable characteristics. It is preferable that the stretching temperature is divided into at least two stages, more preferably three stages. More than that is acceptable, but problems such as the increase in equipment will arise. It is preferable that the temperature of each region is set so as to be sequentially higher, and the temperature difference is in the range of 1 to 50 ° C. In addition, non-contact stretching such as simultaneous biaxial stretching can also be preferably used because failure such as a scratch hardly occurs.
[0085]
Next, heat setting is performed. Before this, the biaxially stretched film is preferably kept at a temperature not higher than the final transverse stretching temperature and at a temperature not lower than Tg-40 ° C. for 0.01 to 5 minutes. When the biaxially stretched film in the longitudinal and transverse directions is heat-set, the temperature is higher than the final transverse stretching temperature, and the temperature is raised in a region divided into two or more within a temperature range of Tm-20 ° C or lower. It is preferable to heat-fix while heating. The heat setting time is usually 0.5 to 300 seconds. The heat-fixed film is usually cooled to Tg or less, cut off the clip gripping portions at both ends of the film, and wound up. At this time, it is preferable to perform the relaxation treatment in the lateral direction by 0.1 to 10% within the temperature range of not more than the final heat setting temperature and not less than Tg. Further, it is preferable that the cooling is performed gradually from the final heat setting temperature to Tg at a cooling rate of 100 ° C. or less per second. The means for cooling and relaxation treatment is not particularly limited, and can be performed by a conventionally known means. In particular, it is preferable to perform these treatments while sequentially cooling in a plurality of temperature regions from the viewpoint of improving the dimensional stability of the film. The cooling rate is calculated by (T1−Tg) / t, where T1 is the final heat setting temperature and t is the time required for the film to reach the Tg from the final heat setting temperature. Since these heat setting conditions, cooling, and more optimal conditions for the relaxation treatment vary depending on the polyester constituting the film, the physical properties of the obtained biaxially stretched film are measured and appropriately adjusted to have preferable characteristics. You only have to decide.
[0086]
In the production of the polyester film of the present invention, a functional layer such as an antistatic layer, a slippery layer, an adhesive layer, and a barrier layer may be applied before and / or after stretching. At this time, various surface treatments such as corona discharge treatment and chemical treatment can be performed as necessary. For example, the methods described in Japanese Patent No. 2649457 and JP-A-5-169592 can be used. Further, for the purpose of improving the strength, stretching used for known stretched films such as multi-stage longitudinal stretching, re-longitudinal stretching, re-longitudinal-horizontal stretching, and horizontal / longitudinal stretching can be performed. The polyester film obtained as described above has a small thickness unevenness, is excellent in flatness, and has very little quality unevenness, so that the effects of the present invention can be maximized.
[0087]
Next, the physical properties of the polyester film of the present invention will be described.
The polyester film of the present invention preferably has the following physical properties for the purpose of preventing poor conveyance by a camera or a development processing machine or occurrence of scratches due to poor conveyance.
[0088]
Curling degree after heat treatment is 135m ^-1 Or less, more preferably 130 m ^-1 It is as follows. When the degree of curl is higher than this, there is a case where trouble occurs in which a camera or a developing processor causes abrasion due to poor transport or poor transport.
[0089]
Curling degree in warm water is 50m ^-1 Or less, more preferably 45 m ^-1 It is as follows. If the degree of curl in warm water is greater than this, problems may occur when developing a large amount of film in a large laboratory such as a cine-type automatic developing machine.
[0090]
Curling degree after development is 50m ^-1 The following is preferred. If it is less than this, troubles of the apparatus are reduced at the time of the printing operation on the photographic paper after the development processing, the cutting of the developed photographic film, or the insertion into the sleeve.
[0091]
If the curl degree exceeds the above-specified curl degree, for example, when using a miniaturized high-speed processing minilab (automatic developing machine) having a complicated transport path, the photographic film may be broken or scratched during the developing process. Or unevenness in development occurs.
[0092]
Wide curl degree is 3-20m ^-1 It is preferable that In the case of more or less than the above, the lateral curl after the application of the hydrophilic colloid layer becomes large, which may cause a problem of causing abrasion during transportation of a camera or the like.
[0093]
The Young's modulus is preferably from 2.0 to 3.4 Gpa. Further, the loop stiffness is preferably 0.1 to 0.3N. Outside this range, troubles may occur during the drive loading and automatic winding of the film onto the camera, the developing process, the printing paper printing process operation, and the like.
[0094]
The Young's modulus immediately after immersion in water is preferably 1.8 Gpa or more. Below this, a problem that the film breaks during the developing process may occur.
[0095]
It is preferable that the heat shrinkage in the longitudinal and transverse directions is both -1.0 to + 2.0%. Exceeding this range may cause a coating failure when applying the adhesive layer or the conductive layer, or may deteriorate the flatness.
[0096]
Each of the physical property values described above is the case where the hydrophilic colloid layer applied to the polyester film of the present invention is 25 μm or less, and if it exceeds this, the preferable range of the physical property values naturally changes.
[0097]
Further, impurities such as oligomers and diethylene glycol (DEG) contained in the polyester film of the present invention may affect photographic performance such as fog, so that it is preferable to reduce the amount. For example, the oligomer amount is 3% or less, preferably 1% or less. DEG is at most 5 mol%, preferably at most 3 mol%.
[0098]
Next, details of the silver halide photographic light-sensitive material using the polyester film of the present invention will be described.
[0099]
The polyester film of the present invention has at least one silver halide emulsion layer on at least one surface side to constitute a silver halide photographic light-sensitive material. The silver halide emulsion layer may be coated directly on the support, or may be coated via another layer, for example, a hydrophilic colloid layer containing no silver halide emulsion.
[0100]
At this time, when the polyester film of the present invention is used as a photographic support, a corona discharge treatment, a glow discharge treatment, an ultraviolet treatment, a flame treatment, a discharge plasma treatment in an atmospheric pressure gas, a chemical treatment, for the purpose of improving the adhesiveness. Various surface treatments such as can be performed as needed. Further, an undercoat layer may be applied to improve the adhesiveness.
[0101]
Further, in addition to the silver halide emulsion layer and the undercoat layer, a conductive layer, a back coat layer, a sliding layer, a transparent magnetic layer, a protective layer, and the like can be provided. In particular, the conductive layer and the sliding layer are preferably used for preventing static and abrasion. Examples of the conductive agent include cross-linked copolymer particles having a quaternary ammonium group in the side chain described in JP-B-60-51693, JP-A-61-223736 and JP-A-62-9346. 7-28194, a cationic antistatic agent such as an ionene polymer crosslinked type or a copolymer particle having an ionene polymer in a side chain, the one containing alumina sol described in JP-B-35-6616 as a main component; ZnO and SnO described in JP-A-57-104931 ₂ , TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , ZiO ₂ And metal oxides described in JP-B-55-5982. ₂ O ₅ And the like can be used. As the slipping agent, for example, the slipping agent described in JP-A-2000-19682 can be used.
[0102]
In the silver halide photographic light-sensitive material according to the present invention, the silver halide constituting the silver halide emulsion layer may have any composition. For example, there are silver chloride, silver chlorobromide, silver chloroiodobromide, pure silver bromide and silver iodobromide.
[0103]
The silver halide emulsion is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643, pp. 22-23 (Dec. 1979), “1. Emulsion preparation and types”, and RD No. 18716, p. 648, "Physics and Chemistry of Photography" by Grakid, published by Paul Montell (P. Glkides, Chimie et Physique Photographique, Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, Focal Press (GF Daufin, Photographic Emulsion Chemistry Focal Press 1966), "Manufacture and Coating of Photographic Emulsions" by Zerikunman et al., Published by Focal Press (V.L. Zelikman et al., Marking and Coating Photographic Photography, etc.) Can be prepared. As the emulsion, monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,665,394 and British Patent 1,413,748 are also preferable.
[0104]
The silver halide emulsion can be subjected to physical ripening, chemical ripening and spectral sensitization. The additive used in such a process is RDNo. 17643, RDNo. 18716 and RDNo. 308119 (hereinafter abbreviated as RD17643, RD18716, and RD308119, respectively). The following shows the location of the description.

Known photographic additives that can be used in the silver halide color photographic light-sensitive material of the present invention are also described in RD. The relevant sections are described below.

Various couplers can be used in the photosensitive layer according to the present invention, and specific examples are described in the above RD. The relevant sections are described below.
[0105]

Each of the above additives can be added by a dispersion method described in RD308119XIV or the like.
[0106]
The silver halide photographic light-sensitive material according to the present invention may be provided with an auxiliary layer such as a filter layer or an intermediate layer described in RD308119VII-K.
[0107]
The silver halide photographic light-sensitive material according to the present invention can have various layer constitutions such as a forward layer, a reverse layer, and a unit constitution described in the aforementioned RD308119VII-K.
[0108]
To develop the silver halide photographic light-sensitive material according to the present invention, for example, T.I. H. James, Theory of the Photographic Process Forth Edition, pp. 291-334, and the Journal of the American Chemical Society, Vol. 73, Journal of the American Chemical Society. A known developer described on pages 3, 100 (1951) can be used. Further, development processing can be carried out by a usual method described in RD17643, pages 28 to 29, RD18716, page 615 and RD308119XIX.
[0109]
【Example】
Hereinafter, the present invention will be described in detail with reference to Examples, but embodiments of the present invention are not limited thereto.
[0110]
<< Preparation of polyester >>
(Preparation of Polyester A)
Hydration of calcium acetate hydrate and manganese acetate to 100 parts by mass of dimethyl terephthalate and 64 parts by mass of ethylene glycol in a reactor equipped with a stirrer, additive inlet, nitrogen gas inlet, and vacuum outflow system And dimethyl terephthalate in an amount of 2 × 10 ^-4 Equivalent amounts were added, and a transesterification reaction was performed by a conventional method. To the obtained product, 32 parts by mass (5.8 mol% / total acid component) of an ethylene glycol solution (concentration: 35% by mass) of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (SIP), polyethylene 8.4 parts by mass of glycol (number average molecular weight 1000) (6.7 parts by mass / polymer), 0.05 parts by mass of antimony trioxide, 0.13 parts by mass of trimethyl phosphate, Irganox as an antioxidant 0.410 parts by mass of 1010 (manufactured by CIBA-GEIGY), 0.04 parts by mass of sodium acetate, and 0.002 parts by mass of silica particles having an average particle size of 0.2 μm were added. Then, the temperature was gradually raised and the pressure was reduced, and polymerization was performed while monitoring the stirring torque at 280 ° C. and 60 Pa to obtain a copolymerized polyester.
[0111]
Using this copolymerized polyester, a Bayer dye is kneaded at the following mixing ratio to prepare a master pellet having a dye concentration of 2000 ppm, and the copolymerized polyester containing no dye and the master pellet are blended in a ratio of 9: 1. Thus, polyester A was obtained. The intrinsic viscosity (IV) of this polyester A was 0.54.
[0112]
Constituent ratio of dye: Macrolex Red EG: Macrolex Violet B: Macrolex Green G = 1: 1: 1
(Preparation of Polyester B)
Using commercially available polyethylene terephthalate (intrinsic viscosity 0.65), the same dye as described above was kneaded at the compounding ratio, and the dye concentration was set to 2000 ppm to prepare a master pellet. Polyester B was prepared by blending 65) with the master pellets at a ratio of 9: 1.
[0113]
(Preparation of Polyester C)
100 parts by mass of dimethyl terephthalate, 18.6 parts by mass of 1,4-cyclohexanedimethanol (CHDM), and 48 parts of ethylene glycol were placed in a reactor equipped with a stirrer, an additive inlet, a nitrogen gas inlet, and a vacuum outflow system. In a part by mass, a hydrate of calcium acetate and a hydrate of manganese acetate were added in an amount of 2 × 10 4 per 1 mol of dimethyl terephthalate. ^-4 Equivalent amounts were added, and a transesterification reaction was performed at 200 ° C. under a nitrogen atmosphere. Thereafter, 0.05 parts by mass of antimony trioxide, 0.13 parts by mass of trimethyl phosphate, 0.4 parts by mass of Irganox 1010 (manufactured by CIBA-GEIGY) as an antioxidant, and 0.04 parts by mass of sodium acetate Parts by mass and 0.002 parts by mass of silica particles having an average particle size of 0.2 μm were added. Subsequently, the temperature was gradually increased and the pressure was reduced, and polymerization was carried out at 280 ° C. and a pressure of 60 Pa to obtain a copolymerized polyester. A dye was added to this copolymerized polyester in the same manner as polyester A to obtain polyester C. The intrinsic viscosity (IV) of this polyester C was 0.54.
[0114]
(Preparation of polyester D)
100 parts by mass of dimethyl terephthalate, 41 parts by mass of 1,4 cyclohexanedimethanol (CHDM), 29 parts by mass of ethylene glycol in a reactor equipped with a stirrer, an additive inlet, a nitrogen gas inlet, and a vacuum outflow system. Then, a hydrate of calcium acetate and a hydrate of manganese acetate were each added to 2 mol / l of 1 mol of dimethyl terephthalate. ^-4 A considerable amount was added, and a transesterification reaction was performed at 200 ° C. under a nitrogen atmosphere. Thereafter, 0.05 parts by mass of antimony trioxide, 0.13 parts by mass of trimethyl phosphate, 0.4 parts by mass of Irganox 1010 (manufactured by CIBA-GEIGY) as an antioxidant, and 0.04 parts by mass of sodium acetate Parts by mass and 0.002 parts by mass of silica particles having an average particle size of 0.2 μm were added. Subsequently, the temperature was gradually increased and the pressure was reduced, and polymerization was carried out at 280 ° C. and a pressure of 60 Pa to obtain a copolymerized polyester. A dye was added to this copolymerized polyester in the same manner as polyester A to obtain polyester D. The intrinsic viscosity (IV) of this polyester D was 0.64.
[0115]
(Preparation of Polyester E)
100 parts by mass of dimethyl terephthalate, 52 parts by mass of 1,4 cyclohexanedimethanol (CHDM), 16 parts by mass of ethylene glycol in a reactor equipped with a stirrer, an additive inlet, a nitrogen gas inlet, and a vacuum outflow system. Then, a hydrate of calcium acetate and a hydrate of manganese acetate were each added to 2 × 10 ^-4 Equivalent amounts were added, and a transesterification reaction was performed at 200 ° C. under a nitrogen atmosphere. Thereafter, 0.05 parts by mass of antimony trioxide, 0.13 parts by mass of trimethyl phosphate, 0.4 parts by mass of Irganox 1010 (manufactured by CIBA-GEIGY) as an antioxidant, and 0.04 parts by mass of sodium acetate were used. Parts by weight were added. Subsequently, the temperature was gradually increased and the pressure was reduced, and polymerization was performed at 280 ° C. and a pressure of 60 Pa to obtain a copolymerized polyester. A dye was added to the copolymerized polyester in the same manner as polyester A to obtain polyester E. The intrinsic viscosity (IV) of this polyester E was 0.72.
[0116]
(Preparation of Polyester F)
95 parts by mass of dimethyl terephthalate, 5 parts by mass of dimethyl isophthalate, 77 parts by mass of 1,4 cyclohexanedimethanol (CHDM) in a reactor equipped with a stirrer, an additive inlet, a nitrogen gas inlet, and a vacuum outflow system. The hydrate of calcium acetate and the hydrate of manganese acetate were added to a part in a molar ratio of 2 × 10 2 to the total number of moles of dimethyl terephthalate and isophthalic acid, respectively. ^-4 A considerable amount was added, and a transesterification reaction was performed at 200 ° C. under a nitrogen atmosphere. Thereafter, 0.05 parts by mass of antimony trioxide, 0.13 parts by mass of trimethyl phosphate, 0.4 parts by mass of Irganox 1010 (manufactured by CIBA-GEIGY) as an antioxidant, and 0.04 parts by mass of sodium acetate Parts by mass and 0.002 parts by mass of silica particles having an average particle size of 0.2 μm were added. Subsequently, the temperature was gradually increased and the pressure was reduced, and polymerization was performed at 280 ° C. and a pressure of 60 Pa to obtain a copolymerized polyester. A dye was added to this copolymerized polyester in the same manner as polyester A to obtain polyester F. The intrinsic viscosity (IV) of this polyester F was 0.77.
[0117]
(Preparation of Polyester G)
100 parts by mass of dimethyl terephthalate, 5 parts by mass of 1,4 cyclohexanedimethanol (CHDM), and 60 parts by mass of ethylene glycol in a reactor equipped with a stirrer, an additive inlet, a nitrogen gas inlet, and a vacuum outflow system. Then, a hydrate of calcium acetate and a hydrate of manganese acetate were each added to 2 × 10 ^-4 Equivalent amounts were added, and a transesterification reaction was performed at 200 ° C. under a nitrogen atmosphere. To the obtained product, 32 parts by mass (5.8 mol% / total acid component) of an ethylene glycol solution (concentration: 35% by mass) of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (SIP), polyethylene 8.4 parts by mass of glycol (number average molecular weight 1000) (6.7 parts by mass / polymer), 0.05 parts by mass of antimony trioxide, 0.13 parts by mass of trimethyl phosphate, Irganox as an antioxidant 0.410 parts by mass of 1010 (manufactured by CIBA-GEIGY), 0.04 parts by mass of sodium acetate and 0.002 parts by mass of silica particles having an average particle size of 0.2 μm were added. Subsequently, the temperature was gradually raised and the pressure was reduced, and polymerization was performed at 280 ° C. and a pressure of 60 Pa to obtain a copolymerized polyester. A dye was added to this copolymerized polyester in the same manner as polyester A to obtain polyester G. The intrinsic viscosity (IV) of this polyester G was 0.58.
[0118]
(Preparation of Polyester H)
100 parts by mass of dimethyl terephthalate, 18.6 parts by mass of 1,4-cyclohexanedimethanol (CHDM), and 48 parts of ethylene glycol were placed in a reactor equipped with a stirrer, an additive inlet, a nitrogen gas inlet, and a vacuum outflow system. In a part by mass, a hydrate of calcium acetate and a hydrate of manganese acetate were each added to 1 mol of dimethyl terephthalate to give 2 × 10 ^-4 Equivalent amounts were added, and a transesterification reaction was performed at 200 ° C. under a nitrogen atmosphere. To the obtained product, 32 parts by mass of a mixed solution of ethylene glycol of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (SIP) and 1,4 cyclohexane dimethanol (CHDM) (concentration of 35% by mass) ( 5.8 mol% / total acid component), 8.4 parts by mass of polyethylene glycol (number average molecular weight 1000) (6.7 mass% / polymer), 0.05 parts by mass of antimony trioxide, trimethyl phosphate 0.13 parts by mass, 0.4 parts by mass of Irganox 1010 (manufactured by CIBA-GEIGY) as an antioxidant, 0.04 parts by mass of sodium acetate, and 0.002 parts by mass of silica particles having an average particle size of 0.2 μm. Parts were added. Subsequently, the temperature was gradually increased and the pressure was reduced, and polymerization was performed at 280 ° C. and a pressure of 60 Pa, to obtain a copolymerized polyester. A dye was added to this copolymerized polyester in the same manner as polyester A to obtain polyester H. The intrinsic viscosity (IV) of this polyester H was 0.58.
[0119]
(Preparation of Polyester I)
After 80 parts by mass of the polyester A and 20 parts by mass of the polyester C were blended by a tumbler-type mixer, the mixture was passed through a biaxial screw kneader rotating in a different direction to perform sufficient mixing. Vacuum deaeration was performed at 20 hPa from two vents while flowing dry nitrogen gas from the entrance. The barrel temperature of the kneading section was 280 ° C., and the residence time in the kneading tank was 10 minutes. The strands that flowed out were quenched with cold water, cut into small pieces, and dried to obtain polyester I as pellets.
[0120]
(Preparation of polyester J)
In the preparation of the polyester I, in the same manner as above except that the polyester A of 50 parts by mass and the polyester C of 50 parts by mass were used instead of the polyester A of 80 parts by mass and the polyester C of 20 parts by mass. And polyester J.
[0121]
(Preparation of polyester K)
In the preparation of the polyester I, instead of 80 parts by mass of the polyester A and 20 parts by mass of the polyester C, 30 parts by mass of the polyester A, 35 parts by mass of the polyester B, and 35 parts by mass of the polyester C Polyester K was obtained in the same manner except for using.
[0122]
(Preparation of polyester L)
In the preparation of the polyester I, the same procedure was carried out except that the polyester A of 95 parts by mass and the polyester E of 5 parts by mass were used instead of the polyester A of 80 parts by mass and the polyester C of 20 parts by mass. And polyester L.
[0123]
(Preparation of Polyester M)
In the preparation of the polyester I, instead of 80 parts by weight of the polyester A and 20 parts by weight of the polyester C, 20 parts by weight of the polyester A, 60 parts by weight of the polyester B, and 20 parts by weight of the polyester E Polyester M was obtained in the same manner except that was used.
[0124]
(Preparation of Polyester N)
In the preparation of the polyester I, the same procedure was carried out except that 95 parts by mass of the polyester A and 5 parts by mass of the polyester F were used instead of 80 parts by mass of the polyester A and 20 parts by mass of the polyester C. And polyester N.
[0125]
(Preparation of polyester O)
In the preparation of the polyester I, the same procedure was carried out except that the polyester A of 60 parts by mass and the polyester B of 40 parts by mass were used in place of the polyester A of 80 parts by mass and the polyester C of 20 parts by mass. To obtain polyester O.
[0126]
(Preparation of polyester P)
In the preparation of polyester A, 5-sodium sulfo was prepared in exactly the same manner except that a matting agent (silica particles) was not added, the polymerization conditions were 280 ° C. and 60 Pa, and the torque was stopped at 80% of that of polyester A preparation. Polyester having di (β-hydroxyethyl) isophthalic acid (SIP) and polyethylene glycol as denaturing components was polymerized to obtain dried pellets. A dye was added to this in the same manner as in the case of polyester A, to give polyester P. The intrinsic viscosity of the pellet was 0.44.
[0127]
(Preparation of Polyester Q)
The polyester A was dried while flowing at 170 ° C. for 1 hour in a nitrogen stream using a vacuum rotary dryer. Thereafter, the rotation was stopped, and solid state polymerization was performed at 220 ° C. for 2 hours while standing, to obtain polyester Q. The intrinsic viscosity of this polyester Q was 0.62.
[0128]
(Preparation of Polyester R)
In the preparation of the polyester M, a kneading process was performed in the same manner as described above, except that, instead of polyester B (intrinsic viscosity 0.65), a commercially available polyethylene terephthalate (intrinsic viscosity 0.43) to which a dye was added was used. Polyester R was obtained by kneading and drying pellets obtained by mixing three polyester resins.
[0129]
(Preparation of Polyester S)
Using commercially available polyethylene terephthalate (intrinsic viscosity 0.78), the same dye as polyester A was kneaded at the compounding ratio to prepare a master pellet with a dye concentration of 2000 ppm, and polyethylene terephthalate containing no dye (intrinsic viscosity of 0.18). 78) and master pellets were blended at a ratio of 9: 1 to obtain polyester S.
[0130]
(Preparation of polyester T)
A polyester T was obtained in the same manner as in the preparation of the polyester G, except that Irganox 1010 as an antioxidant was not added.
[0131]
(Preparation of polyester U)
Polyester U was obtained in the same manner as in the preparation of the polyester G, except that the addition amount of the antioxidant Irganox 1010 was changed to 10 parts by mass.
[0132]
(Preparation of Polyester V)
Polyester V was obtained in the same manner as in Preparation of Polyester A, except that silica particles having an average particle size of 0.2 μm were excluded.
[0133]
<< Preparation of polyester >>
(Preparation of polyester film 1 and sample 1: the present invention)
<Film formation>
The above-prepared polyester L and polyester M were vacuum-dried at 160 ° C. for 10 hours, respectively, and then melt-extruded at 280 ° C. using three extruders. To form a laminated unstretched sheet having a three-layer structure. At this time, polyester L is a surface layer (skin layer) on both sides, polyester M is a core layer (core layer), and the thickness ratio of each layer is 20 (L): 70 (M): 30 (L). The extrusion amount of each extruder was adjusted. This unstretched sheet was stretched 3.5 times in the machine direction at 90 ° C. using a roll-type longitudinal stretching machine. The obtained uniaxially stretched film is stretched by a tenter-type transverse stretching machine in a first stretching zone at 100 ° C. by 50% of the total transverse stretching ratio, and further in a second stretching zone at 120 ° C. by a total transverse stretching ratio of 3.6 times. It was stretched so that Next, heat treatment was performed at 100 ° C. for 2 seconds, heat setting was performed at 170 ° C. in the first heat setting zone for 5 seconds, and heat setting was performed at 210 ° C. in the second heat setting zone for 15 seconds. Next, the film was gradually cooled to room temperature over 30 seconds while being relaxed in the transverse direction by 5% to obtain a biaxially stretched laminated polyester film 1 having a thickness of 120 μm (the thickness of each layer was 20 μm / 70 μm / 30 μm). Both ends were trimmed, and both ends were subjected to knurling with a height of 25 μm and a width of 9 mm, and 500 m was wound around a core having a diameter of 220 mm.
[0134]
<Preparation of silver halide photographic material>
The undercoat layer, the back layer and the silver halide emulsion described in Example 11 of JP-A-2001-33913 were applied to the side of the 20 μm-thick skin layer of the polyester film 1 prepared above. After that, it is cut into 135 size (35 mm width), subjected to perforation processing according to ISO standard of 135 size 36-shot film, and then loaded into a prescribed patrone, and is set to a silver halide color photographic photosensitive material for 135 size. Sample 1 as a material was produced.
[0135]
(Preparation of polyester film 2 and sample 2: the present invention)
In the preparation of the polyester film 1 and the sample 1, the polyester film 2 and the sample 2 which are biaxially stretched laminates were similarly prepared except that the polyester G and the polyester B were used in this order instead of the polyester L and the polyester M. Produced.
[0136]
(Preparation of polyester film 3 and sample 3: the present invention)
In the preparation of the polyester film 1 and the sample 1, the polyester film 3 and the sample 3 which are biaxially stretched laminates were similarly prepared except that the polyester H and the polyester A were used in this order instead of the polyester L and the polyester M. Produced.
[0137]
(Preparation of polyester film 4 and sample 4: the present invention)
In the production of the polyester film 1 and the sample 1, a polyester film 4 and a biaxially stretched laminated polyester film 4 and a sample 4 were produced in the same manner except that the polyester C was used instead of the polyester M.
[0138]
(Preparation of polyester film 5 and sample 5: the present invention)
In the preparation of the polyester film 1 and the sample 1, the polyester film 5 and the sample 5 which were biaxially stretched and laminated were similarly prepared except that the polyester O and the polyester E were used in this order instead of the polyester L and the polyester M. Produced.
[0139]
(Preparation of polyester film 6 and sample 6: the present invention)
In the preparation of the polyester film 1 and the sample 1, the polyester film 6 and the sample 6 which are biaxially stretched laminates were similarly prepared except that the polyester L and the polyester M were used instead of the polyester L and the polyester M in this order. Produced.
[0140]
(Preparation of polyester film 7 and sample 7: the present invention)
In the preparation of the polyester film 1 and the sample 1, the polyester film 7 and the sample 7 which are biaxially stretched laminates were similarly prepared except that the polyester G and the polyester C were used in this order instead of the polyester L and the polyester M. Produced.
[0141]
(Preparation of polyester film 8 and sample 8: the present invention)
In the preparation of the polyester film 1 and the sample 1, a mixture of the polyester A and the polyester F in a mass ratio of 95: 5 instead of the polyester L, and the polyester B and the polyester C instead of the polyester M were 50:50. In the same manner, a polyester film 8 which is a biaxially stretched laminate and a sample 8 were prepared except that a mixture having a mass ratio of 2 was used.
[0142]
(Preparation of polyester film 9 and sample 9: the present invention)
In the preparation of the polyester film 1 and the sample 1, the polyester film 9 and the sample 9 which are biaxially stretched laminates were similarly prepared except that the polyester N and the polyester J were used in this order instead of the polyester L and the polyester M. Produced.
[0143]
(Preparation of polyester film 10 and sample 10: the present invention)
In the preparation of the polyester film 1 and the sample 1, the polyester film 10 and the sample 10 which were biaxially stretched and laminated were similarly prepared except that the polyester A and the polyester M were used in this order instead of the polyester L and the polyester M. Produced.
[0144]
(Preparation of polyester film 11 and sample 11: the present invention)
In the preparation of the polyester film 1 and the sample 1, the same procedure was carried out except that polyester A and polyester D were mixed at a mass ratio of 90:10 instead of polyester L, and polyester B was used instead of polyester M. Thus, a polyester film 11 and a sample 11 which were biaxially stretched and laminated were produced.
[0145]
(Preparation of polyester film 12 and sample 12: the present invention)
In the preparation of the polyester film 1 and the sample 1, the polyester film 12 and the sample 12 which are biaxially stretched laminates were similarly prepared except that the polyester I and the polyester K were used in this order instead of the polyester L and the polyester M. Produced.
[0146]
(Preparation of polyester film 13 and sample 13: the present invention)
In the production of the polyester film 1 and the sample 1, a polyester film 13 and a biaxially stretched laminated polyester film 13 and a sample 13 were produced in the same manner except that polyester V was used instead of polyester L.
[0147]
(Preparation of polyester film 14 and sample 14: the present invention)
In the preparation of the polyester film 1 and the sample 1, in the same manner except that the film thickness of the skin layer (polyester L) / core layer (polyester M) / skin layer (polyester L) was changed to 30 μm / 50 μm / 40 μm, A biaxially stretched polyester film 14 and a sample 14 were produced.
[0148]
(Preparation of polyester film 15 and sample 15: the present invention)
In the preparation of the polyester film 1 and the sample 1, in the same manner except that the thickness of the skin layer (polyester L) / core layer (polyester M) / skin layer (polyester L) was changed to 5 μm / 110 μm / 5 μm, A biaxially stretched polyester film 15 and sample 15 were prepared.
[0149]
(Preparation of polyester film 16 and sample 16: the present invention)
In the production of the polyester film 10 and the sample 10, a polyester film 16 which is a biaxially stretched laminate and a sample 16 were produced in the same manner except that polyester P was used instead of polyester A.
[0150]
(Preparation of polyester film 17 and sample 17: the present invention)
In the production of the polyester film 16 and the sample 16, a polyester film 17 and a biaxially stretched laminated polyester film 17 and a sample 17 were produced in the same manner except that polyester R was used instead of the polyester M.
[0151]
(Preparation of polyester film 18 and sample 18: the present invention)
In the production of the polyester film 2 and the sample 2, a polyester film 18 and a biaxially stretched laminated polyester film 18 and a sample 18 were produced in the same manner except that the polyester T was used instead of the polyester G.
[0152]
(Preparation of polyester film 19 and sample 19: the present invention)
In the preparation of the polyester film 2 and the sample 2, a polyester film 19 and a sample 19, which are biaxially stretched and laminated, were prepared in the same manner except that the polyester U was used instead of the polyester G.
[0153]
(Production of Polyester Film 20 and Sample 20: Comparative Example)
In the preparation of the polyester film 2 and the sample 2, biaxially stretched lamination was performed in the same manner except that the arrangement of the polyester G and the polyester B was exchanged, and both the skin layers were formed of the polyester B and the core layer was formed of the polyester G. And a sample 20 was prepared.
[0154]
(Production of Polyester Film 21 and Sample 21: Comparative Example)
In the production of the polyester film 10 and the sample 10, a polyester film 21 and a sample 21 which are biaxially stretched and laminated were produced in the same manner except that the polyester G was used instead of the polyester M.
[0155]
(Production of Polyester Film 22 and Sample 22: Comparative Example)
In the production of the polyester film 2 and the sample 2, a polyester film 22 and a sample 22 which were biaxially stretched and laminated were produced in the same manner except that the polyester F was used instead of the polyester G.
[0156]
(Production of Polyester Film 23 and Sample 23: Comparative Example)
In the preparation of the polyester film 1 and the sample 1, the polyester film 23 and the sample 23, which are biaxially stretched and laminated, were similarly prepared except that the polyester Q and the polyester S were used in this order instead of the polyester L and the polyester M. Produced.
[0157]
(Production of Polyester Film 24 and Sample 24: Comparative Example)
In the preparation of the polyester film 1 and the sample 1, the polyester film 24 and the sample 24, which are biaxially stretched and laminated, were similarly prepared except that the polyester B and the polyester H were used in this order instead of the polyester L and the polyester M. Produced.
[0158]
(Production of Polyester Film 25 and Sample 25: Comparative Example)
In the preparation of the polyester film 1 and the sample 1, the polyester film 25 and the sample 25, which are biaxially stretched and laminated, were similarly prepared except that the polyester B and the polyester D were used in this order instead of the polyester L and the polyester M. Produced.
[0159]
Table 1 summarizes the constitution of each of the polyester films produced as described above.
The details of the polyester species mixing conditions shown in Table 1 are as follows.
[0160]
B: Polyester resin of different composition is kneaded by a twin-screw kneader and pelletized before use
B: Use the copolyester resin alone
C: Dry blending of polyester resin with different composition as pellets
D: Uniform polyethylene terephthalate containing no copolymer component is used alone
[0161]
[Table 1]

[0162]
<< Measurement of physical properties of polyester film >>
For each of the polyester films produced above, physical property values were measured according to the following methods, and the obtained results are shown in Table 2.
[0163]
(Measurement of trouser tear strength: width direction, longitudinal direction)
According to JIS-K7128-1, the trouser tear strength was measured in the width direction and the longitudinal direction of each polyester film. For the measurement, the tearing force (N) of a polyester film having a thickness of 120 μm, or the tearing force (N) was converted to 120 μm for a film having a thickness other than 120 μm, and this was displayed as a trouser tearing strength. Comparisons can be made without considering the thickness factor.
[0164]
(Measurement of Elmendorf tear strength: longitudinal direction)
The Elmendorf tear strength in the longitudinal direction was measured according to JIS-K7128-2. In the measurement, a tearing force (N) using a polyester film having a thickness of 120 μm, or a tearing force (N) converted to a thickness of 120 μm when the film thickness is other than the above, was determined, and this was determined as Elmendorf. It was expressed as tear strength so that it could be compared without considering the thickness factor.
[0165]
(Measurement of average breaking strength and average breaking elongation: width direction, longitudinal direction)
After leaving each polyester film in a room adjusted to a temperature of 23 ° C. and a relative humidity of 55% for 4 hours or more, the sample is cut into a sample width of 10 mm and a length of 150 mm, the chuck interval is set to 100 mm, and the tensile speed is set to 100 mm / min. The test was performed. From the load-elongation curve measured for the length (longitudinal direction) and the width (lateral direction) in the film forming direction of the polyester film, the breaking strength and elongation at break in the longitudinal direction and the width direction were obtained, and 10 samples were obtained. The average breaking strength and the average breaking elongation were calculated respectively.
[0166]
(Measurement of acetaldehyde (AA) content)
Each polyester film was pulverized into fine powder in liquid nitrogen, sealed in a glass vial, and the amount of AA generated at 170 ° C. for 15 minutes was quantified by a high-sensitivity gas chromatograph.
[0167]
(Haze measurement)
The haze was measured according to ASTM-D1003-52.
[0168]
(Evaluation of core set curl)
Immediately after each polyester film was produced, it was cut into a band of 35 mm (horizontal direction at the time of manufacture) x 120 mm (vertical direction at the time of manufacture), left at a temperature of 23 ° C and a relative humidity of 55% for 1 day, It was wound around a core having a diameter of 10.8 mm. When the sample had a lateral curl, the support was wound so that the concave surface of the support was outside. Thereafter, heat treatment was performed for 24 hours in an environment of a temperature of 55 ° C. and a relative humidity of 20%. After the heat treatment, the film was allowed to cool in an environment of a temperature of 23 ° C. and a relative humidity of 55% for 30 minutes, and then released from the core. After 30 minutes, the core set curl degree of the polyester film was measured. The degree of curl is represented by 1 / r, where r is the radius of curvature of the curled sample, and the unit is m.
[0169]
[Table 2]

[0170]
<< Evaluation of suitability for polyester film and sample manufacturing process >>
(Evaluation of film formation stability)
The state of each polyester film during film formation was visually observed, and the film formation stability was evaluated according to the following criteria.
[0171]
○: Casting to the drum and passing of the film head to longitudinal stretching can be performed without any trouble.
Δ: Film formation is possible with a slight improvement in equipment conditions, and a film can be obtained stably.
×: Breakage is likely to occur on the transport roll having a high curvature (small diameter) during the film forming process, and the film lacks a sense of stability in the film forming process.
(Evaluation of transverse stretching stability)
The state of each polyester film during film formation was visually observed, and the transverse stretching stability was evaluated according to the following criteria.
[0172]
：: Sufficient film thickness uniformity can be obtained within the range of conventional polyethylene terephthalate film production conditions
Δ: Sufficient film thickness uniformity can be obtained by reviewing each of the conditions of stretching ratio, stretching temperature, and heat setting with respect to the conventional polyethylene terephthalate film production conditions.
×: It is difficult to ensure uniformity of the thickness in the width direction even when the conditions of the stretching ratio, the stretching temperature, and the heat setting are adjusted, and there is a problem in production stability and yield.
(Evaluation of film cutting property)
Each of the produced polyester films was continuously cut with a rotating upper blade and a lower blade with cutting conditions optimally adjusted, the cutting state was visually observed, and the film cutting property was evaluated based on the following criteria. .
[0173]
：: The cut surface of the film is clean, no cutting defects such as burrs and sagging are observed, and cutting can be performed without any problem.
Δ: There is no problem with the cut surface of the film, but when the film is wound up, the edge pushed in by the upper blade expands, and the film with a winding end having an edge height sporadically scatters.
×: The cut surface of the film is jagged, the lamination interface of the polyester film is peeled off, and a large amount of whisker-like chips is generated, which is a problem in quality.
《Evaluation of silver halide photographic materials》
The following evaluations were performed on each sample as the silver halide photographic light-sensitive material prepared above.
[0174]
(Evaluation of drilling suitability)
When processing each sample to the size of taking 135 films of 135 films, a perforation is opened at both cut portions of the sample using a punch, and the perforated portion is visually observed, and the punching suitability is determined according to the following criteria. An evaluation was performed.
[0175]
：: Same drilling suitability as the current product using TAC base, and no burrs or missing in perforation part
：: A slight difference in the sharpness of the perforated portion punched out is slightly recognized by the tactile sensation of the fingertip, but the hole is uniformly perforated over the entire length of the sample.
Δ: Slight burrs are observed at each perforated portion, and the quality is judged to cause a problem depending on the wear condition of the blade of the drilling machine.
×: Clear delamination and adhesion of fine fibrous chips are observed around the perforated portion, and there is a problem in practical use
(Evaluation of feedability in camera)
Each sample of the color negative film of 36 135 films taken in the patrone was left for 1 day in an environment of a temperature of 23 ° C. and 55% RH, and then heat-treated for 24 hours in an environment of a temperature of 55 ° C. and 20% RH. Was performed. This sample was observed with two cameras (Z-up150, manufactured by Konica Corporation and EOS-KISSIII, manufactured by Canon Inc.) to observe the film loading, all-frame shooting, transport, and winding operation conditions. Of the film feedability was evaluated.
[0176]
：: There is no problem in film feedability
Δ: Operational abnormalities, such as rewinding during film feeding or stopping halfway, occur very little, but there is no damage to the camera
×: Frequent operation abnormalities, such as rewinding during film feeding or stopping during filming, hindering the driving of the camera and obviously causing camera damage.
(Evaluation of film editing suitability)
Each sample was evaluated for film editing suitability according to the following criteria.
[0177]
：: Any of a splicer (MS650D, manufactured by Mitomo) that cuts off the head and tail of each photographed sample and a notcher (KPN1200DX, manufactured by Konica) that forms a semicircular cutout on one side edge of a specified photographing frame Also exhibits smooth operation and does not hinder the long reel production process before cine development.
△: The joint is slightly unstable due to poor cutting by the splicer, or the device is slightly stopped due to poor punching due to the notcher, requiring work man-hours for adjustment, but resetting to the optimal condition Enables continuous operation
×: The joint was unstable due to poor cutting at the splicer, or the device stopped frequently due to poor punching due to the notcher. Even if the conditions were readjusted, the splicer and notcher could not be automatically operated. Quality that needs to be addressed
(Evaluation of suitability for cine development)
After photographing each of the above samples, the samples were processed by NCV24 (manufactured by Noritz Koki Co., Ltd.), which is a cine-type color negative film automatic development processor, and cine development suitability was evaluated according to the following criteria.
[0178]
：: Processing can be performed without any hindrance in cine development processing
Δ: Curling in the treatment liquid and curling during drying were slightly strong, and there was some concern about stable transport, but processing could be performed.
×: When the film is transported, the film edge portion comes into contact with the guide roll and the width of the film is deformed, and the film is broken, so that stable development processing cannot be performed.
(Evaluation of suitability for minilab development)
After photographing each of the above samples, the samples were processed with KP50QA (manufactured by Konica Corporation), which is a minilab type color negative film automatic development processor, and the suitability for minilab development was evaluated according to the following criteria.
[0179]
：: Can be processed in the same manner as the current color film using TAC base
Δ: After the film was drawn out at the film introduction port, the operation of the cutter was dull in the step of cutting off the rear end of the film, and poor cutting occurred sporadically, but the processing can be performed by adjusting the cutting conditions.
×: The operation of the cutter is extremely slow in the process of cutting off the rear end of the film after the film is pulled out at the film introduction port, and cutting failures occur frequently, requiring manual cutting work every time.
(Evaluation of printer transportability)
After subjecting each sample to color development processing according to the development processing method described in paragraphs [0220] to [0227] of JP-A-10-123652, exposure work was performed with a printer (CLPP1771, manufactured by Konica Corporation). The transportability at the time was evaluated, and the printer transportability was evaluated according to the following criteria.
[0180]
：: The printer transport is extremely smooth and there is no problem at all
Δ: There is a case where the film is slightly caught in the film insertion part of the printer, but it can be handled by adjusting the conditions.
×: The developed sample was greatly deformed and the flatness was poor, so there was an obstacle to film transport and the film surface was scratched.
(Evaluation of integration)
When the entire length of each color-developed sample (36 shots) is bundled and handled, it is hard to handle because it is hard to curl wide and lacks flexibility. Those that were easily entangled somewhat in a spiral shape were rated as Δ, and those that could be bundled without discomfort in normal handling and could be sent to the next step smoothly were evaluated as ○.
[0181]
(Confirmation of print image)
For each of the above samples, indoor and outdoor scenes were photographed, and color prints were created using KP50QA (manufactured by Konica Corporation), which is a minilab-type automatic color negative film processing machine. Visually observe the presence or absence of fogging, and show the same characteristics as the color negative film using the current TAC film as 、, the ones with slight out-of-focus or fogging as Δ, and the color negative using the current TAC film. When the film was clearly defocused or fogged, it was judged as x.
[0182]
(Measurement of curl degree immediately after development processing)
Each sample was processed with a minilab developing machine (Konica Corporation, KP50QA, same conditions as ordinary negative development), discharged from the outlet, left at a temperature of 23 ° C. and a relative humidity of 55% for 1 hour, The curl degree (1 / m) at the center of the film was measured. The operating conditions of the minilab were such that the processing steps consisted of a color development step (CD), a bleaching step (BL), a fixing step (FIX), and a stabilization step (STAB). The processing time was 196 seconds, 50 seconds, 100 seconds, and 70 seconds, respectively, and then drying was performed for 60 seconds with 60 ° C. warm air.
[0183]
(Measurement of time-dependent curl degree after development processing)
A sample that was developed using the above minilab development processor was immediately suspended in a 23 ° C., 55% RH environment so that the longitudinal direction was vertical, and after standing for one day, the degree of curl at the center of the film was measured. Was measured in the same manner as the degree of curl over time after the development processing.
[0184]
Table 3 shows the evaluation results obtained as described above.
[0185]
[Table 3]

[0186]
As is clear from Table 3, the polyester film of the present invention is superior to the comparative example in film production stability (film formation stability and transverse stretching stability), and has tear strength, break strength, and breakage similar to TAC films. It has elongation characteristics and excellent film cutting properties, and silver halide photographic materials using it are suitable for perforation in the packaging process, in-camera feeding in the photographing process, film editing in the development process, Further, it can be seen that the composition is excellent in minilab development processing suitability, printer transportability, integration property, and printer suitability (focus property).
[0187]
【The invention's effect】
According to the present invention, the film production stability is good, the tear strength, the breaking strength, the breaking elongation characteristics, the film cutting property is excellent, and the perforation suitability in the packaging process, the in-camera feeding property in the photographing process, and the development processing process. A polyester film having excellent film editing aptitude, cine and minilab processing aptitude, printer transportability, integration, and printer aptitude (focusability) could be provided.

Claims (11)

A biaxially stretched polyester film having a multilayer structure in which two or more polyester layers are laminated, wherein the surface layer is an aromatic dicarboxylic acid having a metal sulfonate group, a polyalkylene glycol, and cyclohexylene dimethylene glycol. A biaxially stretched polyester film, which is contained as a copolymer component. A biaxially stretched polyester film having a multilayer structure in which two or more polyester layers are laminated, wherein at least one of the polyesters contained in each layer is a polyester containing cyclohexylene dimethylene glycol as a polyester component. Characteristic biaxially stretched polyester film. A biaxially stretched polyester film having a multilayer structure in which two or more polyester layers are laminated, wherein at least one layer has an aromatic dicarboxylic acid having a metal sulfonate group, a polyalkylene glycol, and cyclohexylene dimethylene glycol. Is contained as a copolymer component of the same or different polyester, and the molar fraction of the cyclohexylene dimethylene glycol relative to the total glycol component of the polyester contained as the copolymer component is 50% or more. Stretched polyester film. It contains two or more types of polyester resins as components, and has a trouser tear strength in the width direction of 0.2N or more and 1.5N or less, a longitudinal Elementendorf tear strength of 0.2-1.1N, and a longitudinal direction. The average value of the breaking strength in the width direction is 140 MPa or less, the average value of the breaking elongation in the longitudinal direction and the width direction is 130% or less, the acetaldehyde (AA) content is 30 ppm or less, and the haze is 1.7%. The biaxially stretched polyester film according to any one of claims 1 to 3, wherein: A polyester film obtained by laminating a plurality of polyester layers having different compositions by co-extrusion, wherein the average value of the breaking strength in the longitudinal direction and the width direction is 150 MPa or less, and the average value of the elongation at break in the longitudinal direction and the width direction is 120. % Or less, and the total film thickness is 105 μm or more and 130 μm or less, the biaxially stretched polyester film according to any one of claims 1 to 4. Contains a polyester obtained by copolymerizing an aromatic dicarboxylic acid having a metal sulfonate group and polyethylene glycol as a modifying component of the polyester, and has a tear strength by the trouser method of 0.3 N or more and 1.2 N or less in both the longitudinal and width directions. The biaxially stretched polyester film according to any one of claims 1 to 5, characterized in that: A core layer mainly composed of polyethylene terephthalate (A) is laminated on both sides with a skin layer mainly composed of polyethylene terephthalate (B) containing, as a copolymerization component, an aromatic dicarboxylic acid having metal sulfonate and polyethylene glycol. The biaxial according to any one of claims 1 to 6, wherein the skin layer contains 0.1 to 3% by mass of a phenolic antioxidant based on the mass of the polyethylene terephthalate (B). Stretched polyester film. The biaxial stretching according to claim 7, wherein a ratio (hc / hs) of a thickness hc of the core layer to a total thickness hs of the skin layer is 0.1 or more and 1.2 or less. Polyester film. The core layer contains 5 to 20% by mass of a polyester having 1,4 cyclohexane dimethanol as a glycol component based on the total resin amount of the core layer, and the two skin layers have a mole number M of the acid component of the entire polyester. biaxial stretching of claim 7 or 8 ratio of the molar number _{M 2} of the aromatic dicarboxylic acid component _(M 2 / _{M 1)} is characterized in that 0.2 to 10 having a metal sulfonate group to the ₁ Polyester film. The skin layer contains 0.001 to 0.5% by mass of inert fine particles having an average particle size of 0.05 to 1.5 µm. Biaxially stretched polyester film. The core layer uses polyethylene terephthalate having an IV (intrinsic viscosity) of 0.45 to 0.75, and the two skin layers use a modified polyester resin having an IV of 0.47 to 0.60. The biaxially stretched polyester film according to any one of claims 7 to 10, wherein: