JP3626005B2 - Spectral sensitizing dye for photography - Google Patents

Description

［式中Ｚ₁は５または６員の含窒素ヘテロ環を形成するのに必要な原子群を表 し、Ｒ₁およびＲ₂は置換もしくは無置換のアルキル基を表す。Ｌ₁〜Ｌ₃は置換もしくは無置換のメチン基を表す。Ｍ₁は該分 子の電荷を中和するのに必要なカウンターイオンを表し、ｌは整数０〜３を表し、ｍは整数０〜２を表す。］
【化７】

［式中Ｑ₁およびＱ₂はオキサゾリジン環、イミダゾリジン環またはチアゾリジン環を形成するのに必要な原子群を表し、Ｒ₃は置換もしくは無置換のアルキル基を表す。Ｌ₄およびＬ₅は置換もしくは無置換のメチン基を表し、ｎは整数０〜２を表す。］
【化８】

［式中Ｚ₂は５または６員の含窒素ヘテロ環を形成するのに必要な原子群を表 し、Ｑ₃およびＱ₄はオキサゾリジン環、イミダゾリジン環またはチアゾリジン環を形成するのに必要な原子群を表す。Ｒ₄およびＲ₅は置換もしくは無置換のアルキル基を表し、Ｌ₆〜 Ｌ₁₀は置換もしくは無置換のメチン基を表し、Ｍ₂は該分子の電荷を中和するためのカウンターイオン を表す。ｐ、ｑおよびｒは整数０〜２を表す。］
【化９】

［式中Ｑ₅〜Ｑ₈はオキサゾリジン環、イミダゾリジン環またはチアゾリジン環を形成するのに必要な原子群を表し、Ｒ₆は置換もしくは無置換のアルキル基を表す。Ｌ₁₁〜Ｌ₁₄は置換もしくは無置換のメチン基を表す。ｓおよびｔはそれぞれ整数０〜２を表し、ｓとｔが共に整数０となることはない。］
【化１０】

［式中Ｒ₇は置換もしくは無置換のアルキル基を表し、Ｒ₈〜Ｒ₁₁は水素原子、アルキル基またはアリール基を表す。Ｌ₁₅およびＬ₁₆は置換もしくは無置換のメチン基を表し、Ｍ₃は該分子の電荷を中和す るためのカウンターイオンを表す。ｕは整数1または２を表す。］
【０００９】
【発明の実施の形態】
以下、本発明について具体的に説明する。上記化６におけるＺ_１の５または６員の含窒素ヘテロ環の例としては、例えば、オキサゾール環、ベンゾオキサゾール環、ベンゾイソオキサゾール環、ナフトオキサゾール環、チアゾール環、ベンゾチアゾール環、ナフトチアゾール環、セレナゾール環、ベンゾセレナゾール環、ナフトセレナゾール環、テルラゾール環、ベンゾテルラゾール環、ナフトテルラゾール環、ピリジン環、ピリド［２，３−ｄ］オキサゾール環、キノリン環、ベンゾキノリン環、インドレニン環、ベンゾインドレニン環、ベンゾイミダゾール環、ナフトイミダゾール環、等があり、これらのヘテロ環および縮合ベンゼン環やナフタレン環は置換基を有していても良い。置換基の例としては、例えば、メチル、エチル基のようなアルキル基、メトキシ、エトキシ基のようなアルコキシ基やメチレンジオキシ基、フェニル、メトキシフェニル基のようなアリール基、ヒドロキシ基、カルボキシ基、メトキシカルボニル、エトキシカルボニル基のようなアルコキシカルボニル基、フッ素、塩素、臭素、沃素のようなハロゲン原子などが挙げられる。Ｒ_１およびＲ_２のアルキル基の例としては、例えば、メチル、エチル、ｎ−プロピル、ｉ−プロピル、ｎ−ブチル、ｎ−アミル、β−ヒドロキシエチル、γ−ヒドロキシプロピル、β−アセトキシエチル、γ−アセトキシプロピル、β−メトキシエチル、γ−メトキシプロピル、カルバモイルメチル、カルバモイルエチル、Ｎ−メチルカルバモイルメチル、Ｎ−エチルカルバモイルメチル、Ｎ−メチルカルバモイルエチル、Ｎ，Ｎ−ジメチルカルバモイルメチル、Ｎ，Ｎ−ジメチルカルバモイルエチル、Ｎ，Ｎ−ジエチルカルバモイルメチル、カルボキシメチル、β−カルボキシエチル、γ−カルボキシプロピル、δ−カルボキシブチル、ω−カルボキシペンチル、メトキシカルボニルメチル、エトキシカルボニルメチル、β−メトキシカルボニルエチル、γ−メトキシカルボニルプロピル、δ−メトキシカルボニルブチル、エトキシカルボニルエタンスルホニルエチル、カルバモイルエタンスルホニルエチル、カルボキシエタンスルホニルエチル、β−スルホエチル、γ−スルホプロピル、γ−スルホブチル、δ−スルホブチル、ベンジル、フェネチル、ｐ−カルボキシベンジル、ｐ−スルホフェネチル、アリル、プロパルギル、トリフルオロエチル基などが挙げられる。これらのうち、炭素数５個以下の置換もしくは無置換のアルキル基が好ましい。Ｌ_１〜Ｌ_３のメチン基は置換基を有していてもよく、置換基の例としては例えば、メチル、エチル、プロピルのようなアルキル基、メトキシ、エトキシ、プロポキシのようなアルコキシ基、メチルチオ、エチルチオのようなアルキルチオ基、フェノキシのようなアリールオキシ基、フェニル、トリルのようなアリール基、フリル、チエニル、ピリジル、テトラヒドロピラニル基のようなヘテロ環基などが挙げられ、また、それぞれがお互いに結合して環を形成しても良い。Ｍ_１の例としては、例えば、メチル硫酸、エチル硫酸、チオシアン酸、トルエンスルホン酸、塩素、臭素、よう素、過塩素酸。カリウム、ナトリウム、トリエチルアンモニウム、ピリジニウムなどが挙げられる。
【００１０】
次に化７について具体的に説明する。式中Ｑ_１およびＱ_２のオキサゾリジン環、イミダゾリジン環およびチアゾリジン環は置換されていてもよく、置換基の例としては、例えば、上記化６のＲ_１、Ｒ_２で述べたものやアリール基（例えば、フェニル）が挙げられる。これらのうち、炭素数５個以下の置換もしくは無置換のアルキル基が好ましく、炭素数３以下のカルボキシ置換アルキル基や無置換のアルキル基が特に好ましい。Ｒ_３で表されるアルキル基としては上記化６のＲ_１、Ｒ_２と同義である。また、Ｌ_４およびＬ_５は同様に上記化６のＬ_１〜Ｌ_３と同義である。
【００１１】
次に化８について具体的に説明する。式中のＺ_２、Ｒ_４、Ｒ_５、Ｌ_６〜Ｌ_１０およびＭ_２はそれぞれ上記化６のＺ_１、Ｒ_１、Ｒ_２、Ｌ_１〜Ｌ_３、Ｍ_１と同義であり、Ｑ_３およびＱ_４は上記化７のＱ_１、Ｑ_２と同義である。
【００１２】
次に化９について具体的に説明する。式中のＱ_５〜Ｑ_８は上記化７のＱ_１、Ｑ_２と同義であり、Ｒ_６、Ｌ_１１〜Ｌ_１４はそれぞれ上記化６のＲ_１、Ｒ_２およびＬ_１〜Ｌ_３と同義である。
【００１３】
次に化１０について具体的に説明する。式中のＲ_７〜Ｒ_１１のアルキル基は上記化６のＲ_１と同義であり、Ｒ_８〜Ｒ_１１のアリール基としてはフェニル基が挙げられるが、該フェニル基には上記化６のＲ_１で述べたような置換基で置換されていても良い。さらに、Ｒ_９とＲ_１０で連結してベンゼン環を形成していても良い。Ｌ_１５およびＬ_１６は上記化６のＬ_１〜Ｌ_３と同義である。
【００１４】
次に本発明で用いられる増感色素の具体例を示す。但し、本発明に用いる増感色素がこれらに限定されるものではない。
【００１５】
【化１１】

【００１６】
【化１２】

【００１７】
【化１３】

【００１８】
【化１４】

【００１９】
【化１５】

【００２０】
【化１６】

【００２１】
【化１７】

【００２２】
【化１８】

【００２３】
【化１９】

【００２４】
【化２０】

【００２５】
【化２１】

【００２６】
【化２２】

【００２７】
【化２３】

【００２８】
【化２４】

【００２９】
【化２５】

【００３０】
【化２６】

【００３１】
【化２７】

【００３２】
【化２８】

【００３３】
【化２９】

【００３４】
【化３０】

【００３５】
【化３１】

【００３６】
【化３２】

【００３７】
【化３３】

【００３８】
【化３４】

【００３９】
【化３５】

【００４０】
【化３６】

【００４１】
【化３７】

【００４２】
【化３８】

【００４３】
【化３９】

【００４４】
【化４０】

【００４５】
【化４１】

【００４６】
【化４２】

【００４７】
【化４３】

【００４８】
【化４４】

【００４９】
【化４５】

【００５０】
【化４６】

【００５１】
次に代表的な合成例を挙げるが、他の例示化合物も同様の方法、あるいは、例えば、Ｆｒａｎｃｅｓ Ｍ． Ｈａｍｅｒ著“Ｃｙａｎｉｎｅ Ｄｙｅｓ ａｎｄ Ｒｅｌａｔｅｄ Ｃｏｍｐｏｕｎｄｓ”（１９６４、 Ｉｎｔｅｒｓｃｉｅｎｃｅ Ｐｕｂｌｉｓｈｅｒｓ発刊）等に記載された従来公知の方法を参考に容易に合成することができる。
【００５２】
化１１の合成
２−アミノ−３−ヒドロキシピリジン４９ｇとオルト酢酸トリエチル９４ｇを混合し、浴温９５〜１００℃で２時間加熱還流した。冷却後析出した結晶を濾取し、ｎ−ヘキサンで再結晶した。乾燥後、融点６９．５〜７０．５℃の無色板状晶５５．７ｇを得た。
【００５３】
上記で得た２−メチルピリド［２，３−ｄ］オキサゾール１３．４ｇにヨー化エチル５０ｍｌを加え、４時間加熱還流した。冷却後析出した結晶を濾取し、アセトンで洗浄後乾燥して融点１６３．０〜１６４．０℃の淡黄色の立方晶２６．４ｇを得た。ＮＯＥＳＹ測定により四級化はピリジン環に起こっていることを確認した。
【００５４】
上記で得た四級塩０．５８ｇ、アンヒドロ−２−（３−スルホプロピルチオ）−３−（３−スルホプロピル）ベンゾチアゾリウムヒドロキシド０．８２ｇ、メタノール１０ｍｌを混合後加熱還流する中へトリエチルアミン０．８１ｇを加え、３０分反応させた。冷却後イソプロピルエーテルを加え、上澄みをデカントした。さらに洗浄を繰り返した後アセトンで処理し析晶を濾取した。メタノールで洗浄後乾燥して融点３４８．０℃（分解）の黄色結晶性粉末０．４０ｇを得た。メタノール溶液の吸収極大値は４５６．０ｎｍであった。
【００５５】
化１５の合成
上記化１１と同じ四級塩５．８０ｇにオルトぎ酸エチル３．８４ｇ、アニリン４．８４ｇを混合し、９５〜１００℃で４時間加熱した。冷却後析出した結晶にアセトン２０ｍｌを加え、濾取した。アセトンで洗浄後エタノールで再結晶した。乾燥後融点１８０．０〜１８１．０℃の黄色針状晶３．７０ｇを得た。
【００５６】
上記で得たアニリノビニル体０．３９ｇ、３−エチル−５，６−ジメチル−２−（３，５，５−トリメチル−２−シクロヘキセン−１−イリデン）メチルベンゾチアゾリウムヨージド０．４５ｇ、無水酢酸２．０ｍｌ、トリエチルアミン０．３０ｇを混合後、浴温９５〜１００℃で１５分間加熱した。冷却後アセトンを加え、よくかき混ぜてから濾取した。アセトン次いでエタノールで洗浄後乾燥して黄緑色結晶性粉末０．２６ｇを得た。メタノール溶液の吸収極大値は７８６．５ｎｍであった。
【００５７】
化１７の合成
上記の化１５の合成時で得たアニリノビニル中間体０．３６ｇ、１−〔２−（２−エトキシカルボニルエタンスルホニル）エチル〕−３−フェニル−２−チオヒダントイン０．３８ｇ、無水酢酸１．０ｍｌ、トリエチルアミン０．３０ｇを混合し、９５〜１００℃で３０分間加熱撹拌した。冷却後、イソプロピルエーテルで洗浄を繰り返した後メタノールで処理して析晶を濾取した。メタノールで洗浄後乾燥して融点２２４．０℃（分解）の黒色結晶性粉末０．１８ｇを得た。メタノール溶液の吸収極大値は５４８．０ｎｍであった。
【００５８】
化１９の合成
８５％水酸化カリウム１４．５ｇを水１４０ｍｌに溶かし、これにエタノール２００ｍｌ、二硫化炭素１９．２ｍｌ、２−アミノ−３−ヒドロキシピリジン２２．０ｇを加え、２時間加熱還流した。冷却後、酢酸で酸性にした後溶媒を留去した。析晶を濾取し。水洗後アセトンで洗浄した。乾燥後融点２４５．０℃の灰褐色結晶性粉末１２．４ｇを得た。
【００５９】
上記で得たメルカプトピリド［２，３−ｄ］オキサゾール１２．２ｇを８５％水酸化カリウム５．８１ｇ、水１６．５ｍｌ、エタノール１６５ｍｌのアルカリ液に溶かし、さらにヨウ化メチル１０．０ｍｌを加え、室温で２時間撹拌した。水５００ｍｌ、クロロホルム５００ｍｌを加え、分液ロート中振とうし、クロロホルム層を分取した。硫酸ナトリウムで乾燥後クロロホルムを留去し、残留液をｎ−ヘキサンで処理し、析晶濾取した。乾燥後融点５３．５〜５７．５℃の淡桃色結晶性粉末９．７ｇを得た。
【００６０】
上記で得たＳ−メチル体１．６６ｇをジメチル硫酸１．２６ｇを混合し、発熱がおさまってから浴温９５〜１００℃で３０分加熱した。冷却後イソプロピルエーテルで洗浄後３−カルボキシメチル−５−ｎプロピリデンローダニン２．３１ｇとジメチルホルムアミド５．０ｍｌを加え、加温溶解後トリエチルアミン３．０３ｇを加え、浴温９５〜１００℃で３０分間加熱した。冷却後析晶にアセトン５ｍｌを加え、濾取した。アセトンで洗浄後乾燥して融点２５２．０℃（分解）の青黒色結晶性粉末１．１０ｇを得た。メタノール溶液の吸収極大値は５７１．０ｎｍであった。
【００６１】
化２０の合成
２−メチルチオピリド［２，３−ｄ］オキサゾール１．６６ｇと１，３−プロパンスルトン１．２２ｇを混合し、浴温９５〜１００℃で３０分間加熱した。冷却後固化物を砕き、イソプロピルエーテルで洗浄した。次いで３−カルボキシメチル−５−ｎプロピリデンローダニン２．３１ｇ、ジメチルホルムアミド５．０ｍｌを加え、加温溶解後トリエチルアミン３．０３ｇを加え、９５〜１００℃で３０分間加熱した。冷却後、イソプロピルエーテルで洗浄を繰り返した後酢酸カリウムのエタノール溶液（２．０ｇ／２０ｍｌ）を加え、析晶を濾取した。エタノールで洗浄後乾燥して融点３００．０℃以上の濃紫色結晶性粉末０．７０ｇを得た。メタノール溶液の吸収極大値は５７３．５ｎｍであった。
【００６２】
化２１の合成
２−メチルチオピリド［２、３−ｄ］オキサゾール１．１６ｇ、ジメチル硫酸０．９０ｇを混合し、浴温９０℃に１５分間加熱した。反応後生成した４級塩固化物に、５−（１−エトキシ−エチリデン）−３−エトカルボキシメチルローダニン２．０３ｇとＤＭＦ７ｍｌを加えて浴温７０℃に加熱溶解し、その中へトリエチルアミン２．１２ｇを加え同温にて１時間撹拌した。反応後ＤＭＦを留去しイソプロピルエーテルを数回加えこねて固化させた。濾取後水洗して濃紫色粉末２．５３ｇを得た。メタノール溶液の吸収極大値は５４１．０ｎｍであった。
【００６３】
化２４の合成
２−メチルピリド［２，３−ｄ］オキサゾール１．３４ｇ、１，３−プロパンスルトン１．２２ｇを混合し、浴温９５〜１００℃で１時間加熱した。反応固化物を砕き、イソプロピルエーテルで洗浄後、３−エトキシメタアクロレイン１．１４ｇと無水酢酸１０．０ｍｌを加え、１時間加熱還流した。反応後無水酢酸を留去し、残留物に３−カルボキシメチルローダニン１．９１ｇ、アセトニトリル２０．０ｍｌを加え、加熱還流する中へトリエチルアミン４．０４ｇを加え、１０分間加熱還流した。冷却後析晶を濾取し、アセトニトリル次いでアセトンで洗浄した。エタノールに溶解後酢酸カリウムを加え、析晶濾取した。エタノール次いでアセトンで洗浄後乾燥して融点２４６．０℃の暗黄緑色結晶性粉末０．７８ｇを得た。メタノール溶液の吸収極大値は６５５．５ｎｍであった。
【００６４】
化２６の合成
化１９を０．４６ｇ、ｐ−トルエンスルホン酸メチル０．１９ｇ、ｍ−クレゾール２．０ｍｌを混合し、浴温５０〜５５℃で１時間加熱撹拌した。その後、３−カルボキシメチルローダニン０．１９ｇを加え、加熱撹拌する中へトリエチルアミン０．３０ｇを加え、同温で３０分加熱撹拌を続けた。次いで、酢酸カリウムのエタノール溶液（０．２ｇ／１０．０ｍｌ）を加え、析晶を濾取した。エタノールで洗浄後温湯に溶かし、濾過後エタノールで再沈させた。さらにこの再沈操作を行った後乾燥して融点３００．０℃以上の濃青紫色結晶性粉末０．２７ｇを得た。メタノール溶液の吸収極大値は６２５．５ｎｍであった。
【００６５】
化３１の合成
２−メチルチオピリド［２、３−ｄ］オキサゾール０．１６６ｇ、ジメチル硫酸０．１２６ｇを混合し、浴温９０℃に１５分間加熱した。生成した４級塩固化物に、３−カルボキシメチルローダニン０．１９１ｇ、ＤＭＦ２ｍｌを加えて溶解後、トリエチルアミン０．３０ｇを加え浴温７０℃に１時間加熱した。冷却後析出した反応液にイソプロピルアルコールを加えてろ過し、橙色の結晶０．３２ｇを得た。次にこの固体０．３２ｇ、ｐ−トルエンスルホン酸メチル０．１８６ｇ、ｍ−クレゾール２ｍｌを加え浴温７０℃に５時間加熱撹拌し、ｓ−メチル体を得、次いでこれに５−（１−エトキシ−エチリデン）−３−エトカルボキシメチルローダニン０．２１７ｇ、トリエチルアミン０．２３ｇを加えて浴温７０℃で１時間加熱撹拌した。反応液にイソプロピルエーテルを加えてこね、アメ状の沈殿物を得た。この沈殿物をクロロホルム／メタノール混合溶媒を使ってシリカゲル（和光純薬製ワコーゲルＢ−０）のクロマトグラフィー処理により精製して、濃紫色粉末６１ｍｇを得た。メタノール溶液の吸収極大値は５９０ｎｍであった。
【００６６】
化３２の合成
化２１を２．３１ｇ、ｐ−トルエンスルホン酸メチル０．９７ｇ、ｍ−クレゾール８ｍｌを混合し、浴温８０℃に１．５時間加熱撹拌し、反応液にイソプロピルエーテルを数回加えこねてアメ状のｓ−メチル体を得た。次にこのアメ状物に３−カルボキシメチルローダニン０．７７ｇ、ＤＭＦ１０ｍｌを加えて溶解後、トリエチルアミン１．２１ｇを加え浴温７０℃に１０分間加熱した。反応後ＤＭＦを留去し、残留物をイソプロピルエーテルで数回こねて洗浄し、アメ状物にメタノールを加えて結晶化させ、ろ過して中間体色素（エステル体）１．２０ｇを得た。（この色素のメタノール溶液の吸収極大値は５９４．５ｎｍであった。）次にこの中間体色素０．６８ｇをエタノール１０ｍｌ中にて室温下撹拌する中へ１Ｎ−苛性ソーダ３ｍｌと水７ｍｌを添加して１時間撹拌した。反応後１Ｎ−酢酸で中和し生成したナトリウム塩を濾取し、エタノールで数回洗浄して、黒色粉末０．５７ｇを得た。メタノール溶液の吸収極大値は５９８．５ｎｍであった。
【００６７】
化３３の合成
化２１を０．２１１ｇ、ｐ−トルエンスルホン酸メチル０．１４ｇ、ｍ−クレゾール１．５ｍｌを混合し、浴温８０℃に１．５時間加熱撹拌し、反応液にイソプロピルエーテルを数回加えこねてアメ状のｓ−メチル体を得た。次いでこれに５−（１−エトキシ−エチリデン）−３−エトカルボキシメチルローダニン０．１４５ｇ、エタノール３ｍｌ、トリエチルアミン０．１５ｇを加えて浴温７０℃で１０分間加熱した。析出物を濾取しエタノールで洗浄して精製し、中間体色素（エステル体）の濃緑黒色の粉末０．１２２ｇを得た。（この色素のメタノール溶液の吸収極大値は６５５．５ｎｍであった。）
次にこの中間体色素０．１０２ｇをエタノール２ｍｌ、１Ｎ−苛性カリ０．４５ｍｌ、水０．５５ｍｌの混合溶液中で加水分解し、カリウム塩として濃緑黒色粉末を６３ｍｇを得た。メタノール溶液の吸収極大値は６５７ｎｍであった。
【００６８】
化３４の合成
上記化２０を０．２７ｇ、ｐ−トルエンスルホン酸メチル０．０９ｇ、ｍ−クレゾール１．０ｍｌを混合し、浴温５０〜５５℃で１時間加熱した。次にアンヒドロ−２−メチル−３−（２−スルホエチル）ベンゾチアゾリウムヒドロキシド０．１３ｇ、トリエチルアミン０．１５ｇを加え、同温で３０分間加熱した。反応物にエタノールを加え、濾取した。エタノールで洗浄後温湯に溶かし濾過後エタノールで再沈した。再沈操作をさらに２回行い、エタノールで洗浄後乾燥して融点３００．０℃以上の濃紫色結晶性粉末０．１０ｇを得た。メタノール溶液の吸収極大値は６３９．０ｎｍであった。
【００６９】
化３７の合成
化２１を０．４２１ｇ、ｐ−トルエンスルホン酸メチル０．２８ｇ、ｍ−クレゾール３ｍｌを混合し、浴温８０℃に１．５時間加熱撹拌し、反応液にイソプロピルエーテルを数回加えこねてアメ状のｓ−メチル体を得た。次いでこれにアンヒドロ−２−メチル−３−（３−スルホプロピル）ベンゾチアゾリウムヒドロキシド０．２７１ｇ、ＤＭＦ３ｍｌ、トリエチルアミン０．３ｇを加え、浴温６５℃に３０分間加熱撹拌した。反応液にメタノールを加えて濾取し、メタノールで洗浄して精製し、濃紫色粉末０．３５ｇを得た。メタノール溶液の吸収極大値は６０６．５ｎｍであった。
【００７０】
化４５の合成
化１１と同じ四級塩０．６７ｇ、３−ホルミル−１，２−ジメチルインドール０．３５ｇ、無水酢酸４ｍｌを混合し、１５分間加熱還流した。析晶を濾取し、アセトンで洗浄後メタノールで再結晶し乾燥して融点２７３．０℃の黒褐色結晶性粉末０．７５ｇを得た。メタノール溶液の吸収極大値は４７８．０ｎｍであった。
【００７１】
本発明の増感色素が用いられるハロゲン化銀写真乳剤は、通常の方法によって製造された塩化銀、臭化銀、塩臭化銀、沃臭化銀、塩沃臭化銀等のいずれでもよい。
【００７２】
本発明の増感色素をこれらのハロゲン化銀写真乳剤に添加するには、水溶液や水と任意に混和可能なメタノール、エタノール、アセトン、セロソルブ、ピリジン、ジメチルホルムアミド等の有機溶媒の単独または混合溶媒の溶液として添加することができる。また、これらの増感色素をハロゲン化銀写真乳剤に添加する時期は、一般には第２熟成の終了直後が好適である。その添加量は増感色素の種類又はハロゲン化銀写真乳剤の種類によって異なるが、硝酸銀に換算して１００ｇ当りおおよそ４〜１，２００ｍｇの広範囲で使用することができる。
【００７３】
本発明の増感色素が用いられるハロゲン化銀写真乳剤は貴金属増感、硫黄増感、還元増感およびそれらの組み合わせられた増感あるいはポリアルキレンオキサイド系化合物等の添加などが施されていてもよい。
【００７４】
本発明の増感色素が用いられるハロゲン化銀写真乳剤は必要に応じて他の増感色素、例えば、公知のシアニン、メロシアニン色素を併用して分光増感してもよく、さらに公知の方法により安定剤、界面活性剤、硬膜剤、蛍光増白剤、紫外線吸収剤、フィルター染料、イラジエーション防止染料、ハレーション防止染料、防腐剤、可塑剤、マット化剤、カラーカプラー、硬調化剤（例えば、特開平８−６１９３号、同８−２４８５４９号、同８−２６２６０９号等）、硬調化促進剤（例えば、特開平８−１９０１６５号、同８−１７１１６６号、同８−２４８５７９号等）等のような添加剤を含有することができる。さらに、安定化処理用感光材料に用いられる場合には現像主薬やその前駆体を含むことができる。
【００７５】
本発明の増感色素が用いられるハロゲン化銀写真乳剤の保護コロイドとしては、ゼラチンの他にフタル化ゼラチン、マロン化ゼラチンのようなゼラチン誘導体やセルローズ誘導体、可溶性デンプン、水溶性ポリマー等が挙げられる。
【００７６】
本発明の増感色素が用いられるハロゲン化銀写真乳剤の塗布される支持体としては例えば、バライタ紙、プラスチックがラミネートされた紙、合成紙、セルローズトリアセテート、ポリエチレンテレフタレート等の樹脂フイルム等が使用できる。これらの支持体には必要に応じて公知の方法によって下引き層、ハレーション防止層を設けることもできる。
【００７７】
【実施例】
以下、実施例により本発明を具体的に説明するが、本発明がこれらに限定されるものではない。
【００７８】
実施例１
慣用のハロゲン化銀写真乳剤の製法によって調製された塩化銀乳剤に、本発明の増感色素と比較の増感色素化４７、４８、４９の０．０２５％メタノール溶液を１．２ｍｌ／ｇＡｇ添加した。これらの乳剤を４０℃の浴で４５分間経時して分光増感作用を安定化させた。その後、安定剤、界面活性剤、硬膜剤の所定量を添加してから、ポリエチレンをラミネートした紙支持体上に塗布、乾燥し、３５℃で一夜経時した。次いで適当な大きさに裁断し、試験サンプルとした。このようにして得た各サンプルをＩＳＯ法に基づきウエッジ露光し、Ｄ−７２現像液（米国イーストマンコダック社現像液処方）を用い、２０℃で９０秒間現像し、停止、定着をさせ、さらに水洗を行い、乾燥後所定の黒白像をもつストリップスを得た。これを米国マクベス・コーポレーション社製ＭＡＣＨＢＥＴＨ−ＴＤ５０４濃度計を用い濃度測定して、感度、カブリおよび残色を評価した。感度を決定した光学濃度の基準点は［カブリ＋０．７５］の点であった。白光感度は増感色素を投与していない未添加サンプルの感度を１００とした時の相対値、また赤感度はイーストマンコダック社製ラッテンゼラチンフィルターＮｏ．２９を用いて求め、比較の増感色素化４９の感度値を１００とした時の相対値として、それぞれ示した。残色性は未露光部分の色相を視覚的に評価した。「５」が最もよく
、「１」が最も悪い品質を表す。結果を表１に示した。
【００７９】
【化４７】

【００８０】
【化４８】

【００８１】
【化４９】

【００８２】
【表１】

【００８３】
実施例２
ハロゲン化銀として臭化銀、本発明の増感色素と比較の増感色素化５０、５１を用い、赤感度を比較の増感色素化５１の感度値を１００とした時の相対値で示した以外は実施例１と同様にして、感度、カブリおよび残色を評価した。結果を表２に示した。
【００８４】
【化５０】

【００８５】
【化５１】

【００８６】
【表２】

【００８７】
実施例３
ハロゲン化銀が塩臭化銀（塩化銀７０モル％）、本発明の増感色素と比較の増感色素化５２の０．０５％メタノール溶液を１．２ｍｌ／ｇＡｇ添加し、赤感度を比較の増感色素化５２の感度値を１００とした時の相対値で示した以外は実施例１と同様にして、感度、カブリおよび残色を評価した。結果を表３に示した。
【００８８】
【化５２】

【００８９】
【表３】

【００９０】
表１、表２および表３より明らかなように、本発明の増感色素は比較の増感色素に比べ、高感度で、カブリや処理後の残色汚染が少なく、良好な写真特性を備えていることが分かる。
実施例４
【００９１】
コントロールダブルジェット法を用いてヨウ臭化銀乳剤（ヨード２モル％）を調製した。この原乳剤は晶癖が立方体で、平均粒子サイズ０．２５μ、平均粒子サイズ３０％以内に９５重量％の粒子を含む単分散乳剤であった。沈殿、水洗後ゼラチンを加え、ｐＨを８．０，ｐＡｇを５．０に調整して、塩化金酸カリウム２ｍｇ／ｍｏｌｅＡｇを加え、６０℃で２時間かぶらせた。その後、ｐＨを５．０、ｐＡｇを８．５に調整して試料分割し、本発明の増感色素と比較の増感色素化５３を３５０ｍｇ／ｍｏｌｅＡｇを添加し、硬膜剤と界面活性剤を加え、下引き加工したポリエチレンをラミネートした紙支持体上に、硝酸銀に換算して３．７ｇ／ｍ^２の塗布量で塗布した。乾燥後、各試料を適当な大きさに裁断し、０．１５の濃度差のあるウエッジを通して露光した後、コダック社処方Ｄ−７２現像液を用いて２０℃で９０秒間現像し、酸性定着液を用いて定着した後、水洗し乾燥した。濃度測定して感度、ガンマおよびカブリを評価した。感度を決定した光学濃度の基準点は［カブリ＋０．７５］の点であった。感度は比較色素化５３の感度値を１００とした相対値で表した。ガンマは濃度０．５と１．５の間の直線部の傾きを表した。結果を表４に示した。
【００９２】
【化５３】

【００９３】
【表４】

【００９４】
表４より明らかなように、本発明の増感色素は比較の増感色素に比べ、増感性に優れていることが分かる。また、現像処理後、残存色素による残色は認められなかった。
【００９５】
【発明の効果】
本発明の増感色素を用いることにより、色素汚染による残色が少なく、かつ高感度でカブリの少ないハロゲン化銀写真感光材料を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photographic spectral sensitizing dye, and more particularly to a dye useful as a sensitizing dye for use in a silver halide photographic light-sensitive material.
[0002]
[Prior art]
The silver halide photographic light-sensitive material is required to have high sensitivity in different specific wavelength ranges depending on the purpose of use. As one of the techniques for producing such a silver halide photographic light-sensitive material, various types of sensitizing dyes are added to a silver halide photographic emulsion, and in a wavelength range longer than the intrinsic photosensitive wavelength range of the silver halide, It is generally well known to increase the sensitivity in a specific wavelength range very effectively.
[0003]
When spectral sensitization is applied to a silver halide photographic emulsion by using a dye, not only the spectral sensitization effect is given and the sensitivity is increased, but also the following requirements must be satisfied. (1) The spectral sensitization range is appropriate. (2) Stable photographic characteristics are maintained during storage of the photosensitive material. (3) Do not leave contamination or fogging due to residual dyes administered for spectral sensitization after development. (4) There is no bad interaction with other photographic additives.
[0004]
In order to satisfy the above requirements, various types of cyanine dyes and merocyanine dyes have been proposed. For example, dyes described in U.S. Pat. Nos. 4,965,183 and 5,116,722 have been proposed for sensitizing dyes corresponding to red light sources such as He-Ne laser, red LD, and red LED. These are listed as one of the features that there is little residual color contamination after development processing.
[0005]
However, even these sensitizing dyes do not completely satisfy the above requirements, and further improvements are required.
[0006]
[Problems to be solved by the invention]
The object of the present invention is to provide an excellent spectral sensitizing dye for photography which has high sensitivity satisfying the above-mentioned requirements and has little residual color contamination after development processing.
[0007]
[Means for Solving the Problems]
As a result of various studies, the present inventors have found that the dye molecular structure Pyrido [2,3-d] oxazole ring-containing dye in which N atom of pyridine ring is quaternized (alkylated) Was found to be a pigment satisfying the above-mentioned purpose, and in particular, the pigments represented by the following chemical formulas 6 to 10 were found to be excellent pigments.
[0008]
[Chemical 6]

[Where Z ₁ Represents a group of atoms necessary to form a 5- or 6-membered nitrogen-containing heterocycle, and R ₁ And R ₂ Is Substituted or unsubstituted Represents an alkyl group. L ₁ ~ L _Three Is Substituted or unsubstituted Represents a methine group. M ₁ Represents a counter ion necessary for neutralizing the charge of the molecule, l represents an integer of 0 to 3, and m represents an integer of 0 to 2. ]
[Chemical 7]

[Q in the formula ₁ And Q ₂ Represents an atomic group necessary to form an oxazolidine ring, an imidazolidine ring or a thiazolidine ring, and R _Three Is Substituted or unsubstituted Represents an alkyl group. L _Four And L _Five Is Substituted or unsubstituted Represents a methine group, and n represents an integer of 0 to 2. ]
[Chemical 8]

[Where Z ₂ Represents the atomic group necessary to form a 5- or 6-membered nitrogen-containing heterocycle, and Q _Three And Q _Four Represents an atomic group necessary for forming an oxazolidine ring, an imidazolidine ring or a thiazolidine ring. R _Four And R _Five Is Substituted or unsubstituted Represents an alkyl group, L ₆ ~ L _Ten Is Substituted or unsubstituted Represents a methine group, M ₂ Represents a counter ion for neutralizing the charge of the molecule. p, q, and r represent the integers 0-2. ]
[Chemical 9]

[Q in the formula _Five ~ Q ₈ Represents an atomic group necessary to form an oxazolidine ring, an imidazolidine ring or a thiazolidine ring, and R ₆ Is Substituted or unsubstituted Represents an alkyl group. L ₁₁ ~ L ₁₄ Is Substituted or unsubstituted Represents a methine group. s and t each represent an integer 0 to 2, and neither s nor t is an integer 0. ]
[Chemical Formula 10]

[Wherein R ₇ Is Substituted or unsubstituted Represents an alkyl group, R ₈ ~ R ₁₁ Represents a hydrogen atom, an alkyl group or an aryl group. L ₁₅ And L ₁₆ Is Substituted or unsubstituted Represents a methine group, M _Three Represents a counter ion for neutralizing the charge of the molecule. u represents an integer 1 or 2; ]
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be specifically described. Z in Chemical Formula 6 above ₁ Examples of 5- or 6-membered nitrogen-containing heterocycles include, for example, oxazole ring, benzoxazole ring, benzisoxazole ring, naphthoxazole ring, thiazole ring, benzothiazole ring, naphthothiazole ring, selenazole ring, benzoselenazole Ring, naphthoselenazole ring, tellurazole ring, benzotelrazole ring, naphthotelrazole ring, pyridine ring, pyrido [2,3-d] oxazole ring, quinoline ring, benzoquinoline ring, indolenine ring, benzoindolenine ring, There are a benzimidazole ring, a naphthimidazole ring, and the like, and these hetero rings, condensed benzene rings and naphthalene rings may have a substituent. Examples of substituents include, for example, alkyl groups such as methyl and ethyl groups, alkoxy groups such as methoxy and ethoxy groups, aryl groups such as methylenedioxy groups, phenyl and methoxyphenyl groups, hydroxy groups, and carboxy groups. , Alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl groups, and halogen atoms such as fluorine, chlorine, bromine and iodine. R ₁ And R ₂ Examples of the alkyl group include, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, n-amyl, β-hydroxyethyl, γ-hydroxypropyl, β-acetoxyethyl, γ-acetoxypropyl, β-methoxyethyl, γ-methoxypropyl, carbamoylmethyl, carbamoylethyl, N-methylcarbamoylmethyl, N-ethylcarbamoylmethyl, N-methylcarbamoylethyl, N, N-dimethylcarbamoylmethyl, N, N-dimethylcarbamoylethyl, N, N-diethylcarbamoylmethyl, carboxymethyl, β-carboxyethyl, γ-carboxypropyl, δ-carboxybutyl, ω-carboxypentyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, β-methoxycarbonylethyl, γ-meth Cycarbonylpropyl, δ-methoxycarbonylbutyl, ethoxycarbonylethanesulfonylethyl, carbamoylethanesulfonylethyl, carboxyethanesulfonylethyl, β-sulfoethyl, γ-sulfopropyl, γ-sulfobutyl, δ-sulfobutyl, benzyl, phenethyl, p-carboxy Examples include benzyl, p-sulfophenethyl, allyl, propargyl, and trifluoroethyl groups. Of these, a substituted or unsubstituted alkyl group having 5 or less carbon atoms is preferable. L ₁ ~ L ₃ The methine group may have a substituent. Examples of the substituent include alkyl groups such as methyl, ethyl, and propyl, alkoxy groups such as methoxy, ethoxy, and propoxy, and methylthio and ethylthio. Examples include alkylthio groups, aryloxy groups such as phenoxy, aryl groups such as phenyl and tolyl, heterocyclic groups such as furyl, thienyl, pyridyl, and tetrahydropyranyl groups. A ring may be formed. M ₁ Examples of are, for example, methyl sulfuric acid, ethyl sulfuric acid, thiocyanic acid, toluene sulfonic acid, chlorine, bromine, iodine, perchloric acid. Examples include potassium, sodium, triethylammonium, pyridinium and the like.
[0010]
Next, the chemical formula 7 will be specifically described. Q in the formula ₁ And Q ₂ The oxazolidine ring, imidazolidine ring, and thiazolidine ring may be substituted, and examples of the substituent include, for example, R in the above formula 6 ₁ , R ₂ And an aryl group (for example, phenyl). Among these, a substituted or unsubstituted alkyl group having 5 or less carbon atoms is preferable, and a carboxy-substituted alkyl group or unsubstituted alkyl group having 3 or less carbon atoms is particularly preferable. R ₃ The alkyl group represented by the formula R ₁ , R ₂ It is synonymous with. L ₄ And L ₅ Is the same as L ₁ ~ L ₃ It is synonymous with.
[0011]
Next, the chemical formula 8 will be specifically described. Z in the formula ₂ , R ₄ , R ₅ , L ₆ ~ L ₁₀ And M ₂ Are Z in the above chemical formula 6 ₁ , R ₁ , R ₂ , L ₁ ~ L ₃ , M ₁ Is synonymous with Q ₃ And Q ₄ Is the Q in Chemical Formula 7 above ₁ , Q ₂ It is synonymous with.
[0012]
Next, the chemical formula 9 will be specifically described. Q in the formula ₅ ~ Q ₈ Is the Q in Chemical Formula 7 above ₁ , Q ₂ Is synonymous with R ₆ , L ₁₁ ~ L ₁₄ Is R in the above chemical formula 6 ₁ , R ₂ And L ₁ ~ L ₃ It is synonymous with.
[0013]
Next, the chemical formula 10 will be specifically described. R in the formula ₇ ~ R ₁₁ The alkyl group of ₁ Is synonymous with R ₈ ~ R ₁₁ Examples of the aryl group include a phenyl group, and the phenyl group includes R ₁ It may be substituted with a substituent as described in 1. In addition, R ₉ And R ₁₀ To form a benzene ring. L ₁₅ And L ₁₆ Is L in Chemical Formula 6 above ₁ ~ L ₃ It is synonymous with.
[0014]
Next, specific examples of the sensitizing dye used in the present invention will be shown. However, the sensitizing dye used in the present invention is not limited to these.
[0015]
Embedded image

[0016]
Embedded image

[0017]
Embedded image

[0018]
Embedded image

[0019]
Embedded image

[0020]
Embedded image

[0021]
Embedded image

[0022]
Embedded image

[0023]
Embedded image

[0024]
Embedded image

[0025]
Embedded image

[0026]
Embedded image

[0027]
Embedded image

[0028]
Embedded image

[0029]
Embedded image

[0030]
Embedded image

[0031]
Embedded image

[0032]
Embedded image

[0033]
Embedded image

[0034]
Embedded image

[0035]
Embedded image

[0036]
Embedded image

[0037]
Embedded image

[0038]
Embedded image

[0039]
Embedded image

[0040]
Embedded image

[0041]
Embedded image

[0042]
Embedded image

[0043]
Embedded image

[0044]
Embedded image

[0045]
Embedded image

[0046]
Embedded image

[0047]
Embedded image

[0048]
Embedded image

[0049]
Embedded image

[0050]
Embedded image

[0051]
Next, typical synthesis examples will be given, but other exemplified compounds may be prepared in the same manner or by, for example, Frances M. et al. It can be easily synthesized with reference to a conventionally known method described in “Cyanine Dies and Related Compounds” by Hamer (1964, published by Interscience Publishers).
[0052]
Synthesis of chemical formula 11
49 g of 2-amino-3-hydroxypyridine and 94 g of triethyl orthoacetate were mixed and heated to reflux at a bath temperature of 95 to 100 ° C. for 2 hours. After cooling, the precipitated crystals were collected by filtration and recrystallized from n-hexane. After drying, 55.7 g of colorless plate crystals having a melting point of 69.5 to 70.5 ° C. were obtained.
[0053]
50 ml of ethyl iodide was added to 13.4 g of 2-methylpyrido [2,3-d] oxazole obtained above, and the mixture was heated to reflux for 4 hours. Crystals precipitated after cooling were collected by filtration, washed with acetone and dried to obtain 26.4 g of pale yellow cubic crystals having a melting point of 163.0 to 164.0 ° C. NOESY measurement confirmed that quaternization occurred in the pyridine ring.
[0054]
While mixing 0.58 g of the quaternary salt obtained above, 0.82 g of anhydro-2- (3-sulfopropylthio) -3- (3-sulfopropyl) benzothiazolium hydroxide and 10 ml of methanol, the mixture was heated to reflux. Hetriethylamine 0.81g was added and it was made to react for 30 minutes. After cooling, isopropyl ether was added and the supernatant was decanted. After further washing, the crystals were treated with acetone and the crystals were collected by filtration. After washing with methanol and drying, 0.40 g of a yellow crystalline powder having a melting point of 348.0 ° C. (decomposition) was obtained. The absorption maximum value of the methanol solution was 456.0 nm.
[0055]
Synthesis of chemical formula 15
Ethyl orthoformate 3.84 g and aniline 4.84 g were mixed with 5.80 g of the same quaternary salt as in the above chemical formula 11, and heated at 95 to 100 ° C. for 4 hours. After cooling, 20 ml of acetone was added to the precipitated crystals, and the crystals were collected by filtration. After washing with acetone, recrystallization was performed with ethanol. After drying, 3.70 g of yellow needle crystals having a melting point of 180.0 to 181.0 ° C. were obtained.
[0056]
0.39 g of the anilinovinyl compound obtained above, 0.45 g of 3-ethyl-5,6-dimethyl-2- (3,5,5-trimethyl-2-cyclohexen-1-ylidene) methylbenzothiazolium iodide, After mixing 2.0 ml of acetic anhydride and 0.30 g of triethylamine, the mixture was heated at a bath temperature of 95 to 100 ° C. for 15 minutes. After cooling, acetone was added, and the mixture was stirred well and collected by filtration. It was washed with acetone and then ethanol and dried to obtain 0.26 g of a yellowish green crystalline powder. The absorption maximum value of the methanol solution was 786.5 nm.
[0057]
Synthesis of Chemical Formula 17
0.36 g of an anilinovinyl intermediate obtained during the synthesis of Chemical Formula 15 above, 0.38 g of 1- [2- (2-ethoxycarbonylethanesulfonyl) ethyl] -3-phenyl-2-thiohydantoin, 1.0 ml of acetic anhydride , 0.30 g of triethylamine was mixed, and the mixture was heated and stirred at 95 to 100 ° C. for 30 minutes. After cooling, washing with isopropyl ether was repeated, followed by treatment with methanol, and the precipitated crystals were collected by filtration. After washing with methanol and drying, 0.18 g of black crystalline powder having a melting point of 224.0 ° C. (decomposition) was obtained. The absorption maximum value of the methanol solution was 548.0 nm.
[0058]
Synthesis of chemical formula 19
14.5 g of 85% potassium hydroxide was dissolved in 140 ml of water, 200 ml of ethanol, 19.2 ml of carbon disulfide and 22.0 g of 2-amino-3-hydroxypyridine were added thereto, and the mixture was heated to reflux for 2 hours. After cooling, the solution was acidified with acetic acid and the solvent was distilled off. The precipitated crystals are collected by filtration. After washing with water, it was washed with acetone. After drying, 12.4 g of a grayish brown crystalline powder having a melting point of 245.0 ° C. was obtained.
[0059]
Mercaptopyrido [2,3-d] oxazole 12.2 g obtained above is dissolved in an alkaline solution of 85% potassium hydroxide 5.81 g, water 16.5 ml, ethanol 165 ml, and methyl iodide 10.0 ml is added. And stirred at room temperature for 2 hours. 500 ml of water and 500 ml of chloroform were added, and the mixture was shaken in a separatory funnel to separate the chloroform layer. Chloroform was distilled off after drying with sodium sulfate, the residual liquid was treated with n-hexane, and the crystals were collected by filtration. After drying, 9.7 g of pale pink crystalline powder having a melting point of 53.5 to 57.5 ° C. was obtained.
[0060]
1.66 g of the S-methyl compound obtained above was mixed with 1.26 g of dimethyl sulfate, and after the exotherm subsided, the mixture was heated at a bath temperature of 95 to 100 ° C. for 30 minutes. After cooling and washing with isopropyl ether, 2.31 g of 3-carboxymethyl-5-npropylidene rhodanine and 5.0 ml of dimethylformamide are added. After dissolution by heating, 3.03 g of triethylamine is added, and the bath temperature is 95-100 ° C. Heated for minutes. After cooling, 5 ml of acetone was added to the precipitated crystals and collected by filtration. After washing with acetone and drying, 1.10 g of blue-black crystalline powder having a melting point of 252.0 ° C. (decomposition) was obtained. The absorption maximum value of the methanol solution was 571.0 nm.
[0061]
Synthesis of Chemical 20
1.66 g of 2-methylthiopyrido [2,3-d] oxazole and 1.22 g of 1,3-propane sultone were mixed and heated at a bath temperature of 95 to 100 ° C. for 30 minutes. After cooling, the solidified product was crushed and washed with isopropyl ether. Subsequently, 2.31 g of 3-carboxymethyl-5-npropylidene rhodanine and 5.0 ml of dimethylformamide were added, and after dissolution by heating, 3.03 g of triethylamine was added and heated at 95-100 ° C. for 30 minutes. After cooling, washing with isopropyl ether was repeated, an ethanol solution of potassium acetate (2.0 g / 20 ml) was added, and the precipitated crystals were collected by filtration. After washing with ethanol and drying, 0.70 g of a deep purple crystalline powder having a melting point of 300.0 ° C. or higher was obtained. The absorption maximum value of the methanol solution was 573.5 nm.
[0062]
Synthesis of Chemical Formula 21
1.16 g of 2-methylthiopyrido [2,3-d] oxazole and 0.90 g of dimethyl sulfate were mixed and heated to a bath temperature of 90 ° C. for 15 minutes. To the quaternary salt solidified product produced after the reaction, 2.03 g of 5- (1-ethoxy-ethylidene) -3-ethocarboxymethylrhodanine and 7 ml of DMF are added and dissolved by heating at a bath temperature of 70 ° C., and triethylamine 2 .12 g was added and stirred at the same temperature for 1 hour. After the reaction, DMF was distilled off, and isopropyl ether was added several times to solidify. After filtration, it was washed with water to obtain 2.53 g of a deep purple powder. The absorption maximum value of the methanol solution was 541.0 nm.
[0063]
Synthesis of Chemical Formula 24
2-methylpyrido [2,3-d] oxazole 1.34 g and 1,3-propane sultone 1.22 g were mixed and heated at a bath temperature of 95 to 100 ° C. for 1 hour. The reaction solidified product was crushed, washed with isopropyl ether, 1.14 g of 3-ethoxymetaacrolein and 10.0 ml of acetic anhydride were added, and the mixture was heated to reflux for 1 hour. After the reaction, acetic anhydride was distilled off, 1.91 g of 3-carboxymethylrhodanine and 20.0 ml of acetonitrile were added to the residue, 4.04 g of triethylamine was added to the mixture under reflux, and the mixture was refluxed for 10 minutes. After cooling, the precipitated crystals were collected by filtration and washed with acetonitrile and then with acetone. After dissolving in ethanol, potassium acetate was added, and the crystals were collected by filtration. It was washed with ethanol and then with acetone and dried to obtain 0.78 g of a dark yellow green crystalline powder having a melting point of 246.0 ° C. The absorption maximum value of the methanol solution was 655.5 nm.
[0064]
Synthesis of Chemical Formula 26
0.46 g of Chemical Formula 19, 0.19 g of methyl p-toluenesulfonate, and 2.0 ml of m-cresol were mixed, and the mixture was heated and stirred at a bath temperature of 50 to 55 ° C. for 1 hour. Thereafter, 0.19 g of 3-carboxymethylrhodanine was added, 0.30 g of triethylamine was added to the mixture while stirring with heating, and stirring was continued for 30 minutes at the same temperature. Then, an ethanol solution of potassium acetate (0.2 g / 10.0 ml) was added, and the precipitated crystals were collected by filtration. After washing with ethanol, it was dissolved in warm water, filtered and reprecipitated with ethanol. This reprecipitation operation was further performed and dried to obtain 0.27 g of a deep blue-violet crystalline powder having a melting point of 300.0 ° C. or higher. The absorption maximum value of the methanol solution was 625.5 nm.
[0065]
Synthesis of Chemical Formula 31
0.166 g of 2-methylthiopyrido [2,3-d] oxazole and 0.126 g of dimethyl sulfate were mixed and heated to a bath temperature of 90 ° C. for 15 minutes. To the resulting quaternary salt solidified product, 0.191 g of 3-carboxymethylrhodanine and 2 ml of DMF were added and dissolved, then 0.30 g of triethylamine was added and heated to a bath temperature of 70 ° C. for 1 hour. Isopropyl alcohol was added to the reaction solution precipitated after cooling and filtered to obtain 0.32 g of orange crystals. Next, 0.32 g of this solid, 0.186 g of methyl p-toluenesulfonate, and 2 ml of m-cresol were added, and the mixture was heated and stirred at a bath temperature of 70 ° C. for 5 hours to obtain an s-methyl compound. Ethoxy-ethylidene) -3-ethocarboxymethylrhodanine (0.217 g) and triethylamine (0.23 g) were added, and the mixture was heated and stirred at a bath temperature of 70 ° C. for 1 hour. Isopropyl ether was added to the reaction solution and kneaded to obtain a candy-like precipitate. The precipitate was purified by chromatography on silica gel (Wako Gel B-0 manufactured by Wako Pure Chemical Industries, Ltd.) using a chloroform / methanol mixed solvent to obtain 61 mg of a deep purple powder. The absorption maximum value of the methanol solution was 590 nm.
[0066]
Synthesis of Chemical Formula 32
2.31 g of Chemical Formula 21, 0.97 g of methyl p-toluenesulfonate, and 8 ml of m-cresol were mixed, heated and stirred at a bath temperature of 80 ° C. for 1.5 hours, and isopropyl ether was added several times to the reaction solution to give an candy. A s-methyl derivative was obtained. Next, 0.77 g of 3-carboxymethylrhodanine and 10 ml of DMF were added to this candy and dissolved, 1.21 g of triethylamine was added and heated to a bath temperature of 70 ° C. for 10 minutes. After the reaction, DMF was distilled off, the residue was kneaded several times with isopropyl ether, and the candy-like product was crystallized by adding methanol, followed by filtration to obtain 1.20 g of an intermediate dye (ester). (The absorption maximum of this dye in methanol was 594.5 nm.) Next, 0.6 ml of this intermediate dye was stirred in 10 ml of ethanol at room temperature, and 3 ml of 1N sodium hydroxide and 7 ml of water were added. And stirred for 1 hour. After the reaction, the sodium salt produced by neutralization with 1N-acetic acid was collected by filtration and washed several times with ethanol to obtain 0.57 g of a black powder. The absorption maximum value of the methanol solution was 598.5 nm.
[0067]
Synthesis of Chemical Formula 33
0.211 g of Chemical Formula 21, 0.14 g of methyl p-toluenesulfonate, and 1.5 ml of m-cresol were mixed, heated and stirred at a bath temperature of 80 ° C. for 1.5 hours, and isopropyl ether was added to the reaction solution several times. Thus, a candy-like s-methyl compound was obtained. Next, 0.145 g of 5- (1-ethoxy-ethylidene) -3-ethocarboxymethylrhodanine, 3 ml of ethanol, and 0.15 g of triethylamine were added thereto and heated at a bath temperature of 70 ° C. for 10 minutes. The precipitate was collected by filtration, washed with ethanol and purified to obtain 0.122 g of an intermediate dye (ester) dark green-black powder. (The absorption maximum value of this dye solution in methanol was 655.5 nm.)
Next, 0.102 g of this intermediate dye was hydrolyzed in a mixed solution of 2 ml of ethanol, 0.45 ml of 1N caustic potash and 0.55 ml of water to obtain 63 mg of a dark green black powder as a potassium salt. The absorption maximum value of the methanol solution was 657 nm.
[0068]
Synthesis of Chemical 34
0.27 g of the above chemical compound 20, 0.09 g of methyl p-toluenesulfonate, and 1.0 ml of m-cresol were mixed and heated at a bath temperature of 50 to 55 ° C. for 1 hour. Next, 0.13 g of anhydro-2-methyl-3- (2-sulfoethyl) benzothiazolium hydroxide and 0.15 g of triethylamine were added and heated at the same temperature for 30 minutes. Ethanol was added to the reaction product and collected by filtration. After washing with ethanol, it was dissolved in warm water, filtered and reprecipitated with ethanol. The reprecipitation operation was further performed twice, washed with ethanol and dried to obtain 0.10 g of a deep purple crystalline powder having a melting point of 300.0 ° C. or higher. The absorption maximum value of the methanol solution was 639.0 nm.
[0069]
Synthesis of Chemical Formula 37
0.421 g of Chemical Formula 21, 0.28 g of methyl p-toluenesulfonate, and 3 ml of m-cresol were mixed, heated and stirred at a bath temperature of 80 ° C. for 1.5 hours, and isopropyl ether was added to the reaction solution several times and kneaded. A s-methyl derivative was obtained. Next, 0.271 g of anhydro-2-methyl-3- (3-sulfopropyl) benzothiazolium hydroxide, 3 ml of DMF, and 0.3 g of triethylamine were added thereto, and the mixture was heated and stirred at a bath temperature of 65 ° C. for 30 minutes. Methanol was added to the reaction solution, which was collected by filtration, washed with methanol and purified to obtain 0.35 g of a deep purple powder. The absorption maximum value of the methanol solution was 606.5 nm.
[0070]
Synthesis of Chemical 45
0.67 g of the same quaternary salt as in Chemical Formula 11, 0.35 g of 3-formyl-1,2-dimethylindole and 4 ml of acetic anhydride were mixed and heated to reflux for 15 minutes. The precipitated crystals were collected by filtration, washed with acetone, recrystallized with methanol and dried to obtain 0.75 g of a blackish brown crystalline powder having a melting point of 273.0 ° C. The absorption maximum value of the methanol solution was 478.0 nm.
[0071]
The silver halide photographic emulsion in which the sensitizing dye of the present invention is used may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and the like produced by a usual method. .
[0072]
In order to add the sensitizing dye of the present invention to these silver halide photographic emulsions, an organic solvent such as methanol, ethanol, acetone, cellosolve, pyridine, dimethylformamide or the like, which can be arbitrarily mixed with an aqueous solution or water, is used alone or as a mixed solvent. Can be added as a solution. Further, it is generally preferable that these sensitizing dyes are added to the silver halide photographic emulsion immediately after the completion of the second ripening. The amount of addition varies depending on the type of sensitizing dye or the type of silver halide photographic emulsion, but can be used in a wide range of about 4 to 1,200 mg per 100 g in terms of silver nitrate.
[0073]
The silver halide photographic emulsion in which the sensitizing dye of the present invention is used may be subjected to noble metal sensitization, sulfur sensitization, reduction sensitization, combined sensitization or addition of a polyalkylene oxide compound or the like. Good.
[0074]
The silver halide photographic emulsion in which the sensitizing dye of the present invention is used may be spectrally sensitized with another sensitizing dye, for example, a known cyanine or merocyanine dye, if necessary. Stabilizers, surfactants, hardeners, optical brighteners, UV absorbers, filter dyes, anti-irradiation dyes, antihalation dyes, preservatives, plasticizers, matting agents, color couplers, contrast agents (eg JP-A-8-6193, JP-A-8-248549, JP-A-8-262609, etc.), contrast enhancers (for example, JP-A-8-190165, JP-A-8-171166, JP-A-8-248579, etc.) Such additives can be contained. Further, when used in a photosensitive material for stabilization processing, it can contain a developing agent and its precursor.
[0075]
Examples of protective colloids for silver halide photographic emulsions in which the sensitizing dye of the present invention is used include gelatin derivatives such as phthalated gelatin and malonated gelatin, cellulose derivatives, soluble starch, water-soluble polymers, and the like in addition to gelatin. .
[0076]
As the support on which the silver halide photographic emulsion using the sensitizing dye of the present invention is coated, for example, baryta paper, paper laminated with plastic, synthetic paper, resin film such as cellulose triacetate, polyethylene terephthalate, etc. can be used. . These supports can be provided with an undercoat layer and an antihalation layer by a known method, if necessary.
[0077]
【Example】
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
[0078]
Example 1
1.2 ml / g Ag of 0.025% methanol solution of sensitizing dyes 47, 48 and 49 for comparison with the sensitizing dye of the present invention was added to a silver chloride emulsion prepared by a conventional method for producing a silver halide photographic emulsion. did. These emulsions were aged for 45 minutes in a 40 ° C. bath to stabilize the spectral sensitizing action. Thereafter, predetermined amounts of a stabilizer, a surfactant, and a hardener were added, and then coated on a polyethylene-laminated paper support, dried, and aged at 35 ° C. overnight. Subsequently, it cut | judged to the appropriate magnitude | size and it was set as the test sample. Each sample thus obtained was subjected to wedge exposure based on the ISO method, developed using a D-72 developer (Developer formulation of Eastman Kodak, USA) for 90 seconds at 20 ° C., stopped, fixed, and further After washing, strips having a predetermined black and white image were obtained after drying. The density was measured using a MACHBETH-TD504 densitometer manufactured by Macbeth Corporation, USA, and the sensitivity, fog and residual color were evaluated. The reference point of the optical density that determined the sensitivity was the [fog + 0.75] point. The white light sensitivity is a relative value when the sensitivity of an unadded sample to which no sensitizing dye is administered is 100, and the red sensitivity is a Latin gelatin filter No. manufactured by Eastman Kodak Company. 29, and the relative value when the sensitivity value of the comparative sensitizing dye 49 is 100 is shown. As for the residual color, the hue of the unexposed part was visually evaluated. “5” is the best
, “1” represents the worst quality. The results are shown in Table 1.
[0079]
Embedded image

[0080]
Embedded image

[0081]
Embedded image

[0082]
[Table 1]

[0083]
Example 2
Using silver bromide as the silver halide and sensitizing dyes 50 and 51 for comparison with the sensitizing dye of the present invention, the red sensitivity is shown as a relative value when the sensitivity value of the comparative sensitizing dye 51 is set to 100. Except for the above, sensitivity, fog and residual color were evaluated in the same manner as in Example 1. The results are shown in Table 2.
[0084]
Embedded image

[0085]
Embedded image

[0086]
[Table 2]

[0087]
Example 3
Silver halide is silver chlorobromide (silver chloride 70 mol%), and a 0.05% methanol solution of sensitizing dye 52 compared with the sensitizing dye of the present invention is added at 1.2 ml / gAg, and the red sensitivity is compared. The sensitivity, fog and residual color were evaluated in the same manner as in Example 1 except that the sensitizing dye 52 was expressed as a relative value when the sensitivity value was 100. The results are shown in Table 3.
[0088]
Embedded image

[0089]
[Table 3]

[0090]
As is clear from Tables 1, 2 and 3, the sensitizing dyes of the present invention have higher sensitivity, less fog and residual color contamination after processing, and better photographic characteristics than the comparative sensitizing dyes. I understand that
Example 4
[0091]
A silver iodobromide emulsion (iodine 2 mol%) was prepared using the control double jet method. This original emulsion was a monodispersed emulsion having a cubic crystal habit, an average grain size of 0.25 μm, and containing 95% by weight of grains within an average grain size of 30%. After precipitation and washing with water, gelatin was added, pH was adjusted to 8.0, pAg was adjusted to 5.0, potassium chloroaurate 2 mg / moleAg was added, and the mixture was fogged at 60 ° C. for 2 hours. Thereafter, the sample is divided by adjusting the pH to 5.0 and pAg to 8.5, and 350 mg / moleAg of sensitizing dye 53 for comparison with the sensitizing dye of the present invention is added, and the hardening agent and the surfactant are added. 3.7 g / m in terms of silver nitrate on a paper support laminated with undercoated polyethylene. ² It applied with the application quantity of. After drying, each sample is cut into an appropriate size, exposed through a wedge having a density difference of 0.15, and then developed at 20 ° C. for 90 seconds using a Kodak prescription D-72 developer. After fixing using, washed with water and dried. Density was measured to evaluate sensitivity, gamma and fog. The reference point of the optical density that determined the sensitivity was the [fog + 0.75] point. Sensitivity was expressed as a relative value with the sensitivity value of comparative dyed 53 as 100. Gamma represents the slope of the linear portion between densities 0.5 and 1.5. The results are shown in Table 4.
[0092]
Embedded image

[0093]
[Table 4]

[0094]
As is clear from Table 4, it can be seen that the sensitizing dye of the present invention is superior in sensitization compared to the comparative sensitizing dye. Further, no residual color due to the residual dye was observed after the development processing.
[0095]
【The invention's effect】
By using the sensitizing dye of the present invention, it is possible to obtain a silver halide photographic light-sensitive material with little residual color due to dye contamination, high sensitivity and low fog.

Claims (1)

A spectral sensitizing dye for photography, wherein the spectral sensitizing dye for photography is represented by the following general formulas 1 to 5.

[Wherein Z ₁ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, and R ₁ and R _{2 each} represents a substituted or unsubstituted alkyl group. L _{1 to} L ₃ represent a substituted or unsubstituted methine group. M ₁ represents a counter ion necessary for neutralizing the charge of the molecule, l represents an integer 0 to 3, and m represents an integer 0 to 2. ]

[Wherein Q ₁ and Q ₂ represent an atomic group necessary for forming an oxazolidine ring, an imidazolidine ring or a thiazolidine ring, and R ₃ represents a substituted or unsubstituted alkyl group. L ₄ and L ₅ represent a substituted or unsubstituted methine group, and n represents an integer of 0 to 2. ]

[Wherein Z ₂ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, and Q ₃ and Q ₄ are necessary for forming an oxazolidine ring, an imidazolidine ring, or a thiazolidine ring. Represents an atomic group. R ₄ and R ₅ represent a substituted or unsubstituted alkyl group, L ₆ to L ₁₀ represent a substituted or unsubstituted methine group, and M ₂ represents a counter ion for neutralizing the charge of the molecule. p, q, and r represent the integers 0-2. ]

[Wherein Q _{5 to} Q ₈ represent an atomic group necessary for forming an oxazolidine ring, an imidazolidine ring or a thiazolidine ring, and R ₆ represents a substituted or unsubstituted alkyl group. L _{11 to} L ₁₄ represent a substituted or unsubstituted methine group. s and t each represent an integer 0 to 2, and neither s nor t is an integer 0. ]

[Wherein R ₇ represents a substituted or unsubstituted alkyl group, and R _{8 to} R ₁₁ represent a hydrogen atom, an alkyl group, or an aryl group. L ₁₅ and L ₁₆ represent a substituted or unsubstituted methine group, and M ₃ represents a counter ion for neutralizing the charge of the molecule. u represents an integer 1 or 2; ]