JP3675025B2 - Azomethine compound and ink jet recording liquid containing the compound - Google Patents

Description

【００１５】
式中、Ｒ₁は水素原子、アルキル基、無置換のアルケニル基、無置換のアルキニル基またはアラルキル基を表し、Ｒ₂は水素原子、アルキル基、無置換のアルケニル基、無置換のアルキニル基、アラルキル基、芳香族基または複素環基を表し、Ｒ₁はＲ₂とともに環を形成しても良い。Ｒ₃はハメットのσｐの値が−０．３以上０．５以下のアルキル基を表し、Ｒ₄はアルキル基、アルコキシ基、ハロゲン原子、アシルアミノ基、ウレイド基、アルコキシカルボニル基またはスルホニルアミノ基を表し、ｎは０または１を表す。Ｘ₁およびＸ₂は一方がＣＲ（Ｒは水素原子、アルキル基、アルコキシ基、ハロゲン原子、アシルアミノ基、ウレイド基、アルコキシカルボニル基またはスルホニルアミノ基を表す）基、もう一方が窒素原子を表す。ＹおよびＺは一方がＣＲ′（Ｒ′はアルキル基、アルケニル基、アルキニル基またはアラルキル基を表す）基、もう一方が窒素原子を表す。さらにＲ₁、Ｒ₂、Ｒ₃、Ｒ₄、ＲおよびＲ′で表される置換基の少なくとも１つはスルホン酸基、カルボン酸基またはこれらの塩を含有する基である。
【００１６】
２．前記一般式（１）で表されるアゾメチン系化合物を０．１重量％以上２０．０重量％以下、水を１．０重量％以上９８．９重量％以下及び水溶性有機溶剤を１．０重量％以上９８．９重量％以下含有することを特徴とするインクジェット記録液。
【００１７】
以下、本発明を詳細に述べる。
【００１８】
先ず、本発明の一般式（１）で表される化合物について詳細に説明する。
【００１９】
一般式（１）においてＲ₁は水素原子、アルキル基（例えばメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、ネオペンチル基またはヘキシル基等）、無置換のアルケニル基（例えばアリル基）、無置換のアルキニル基（例えばプロバルギル基等）またはアラルキル基（例えばベンジル基またはフェネチル基等）を表し、Ｒ₂は水素原子、アルキル基（例えばメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、ネオペンチル基またはヘキシル基等）、アルケニル基（例えばアリル基）、アルキニル基（例えばプロパルギル基等）、アラルキル基（例えばベンジル基またはフェネチル基等）、芳香族基（例えばフェニル基またはナフチル基等）または複素環基（例えばピリジル基、ピラジニル基、ピリミジニル基、チエニル基、フリル基、チアゾリル基、オキサゾリル基、イソオキサゾリル基、ピロリル基、ピラゾリル基、イミダゾリル基、テトラヒドロフリル基、ピペラジニル基、ピペリジニル基、モルホリニル基、ベンゾチアゾリル基、ベンゾオキサゾリル基またはベンズイミダゾリル基等）を表す。
【００２０】
Ｒ₁とＲ₂は窒素原子とともに環（例えばピペリジン環、ピロリジン環、ピペラジン環またはモルホリン環等）を形成しても良い。
【００２１】
Ｒ₁およびＲ₂ （水素原子、無置換のアルケニル基または無置換のアルキニル基の場合を除く）はさらに適当な置換基で置換されていても良く、適当な置換基としては例えば脂肪族基（例えば炭素数１〜２０のアルキル基等）、芳香族基（例えば、フェニル基、ナフチル基等）、ヘテロ環基（例えば、少なくとも１つの窒素原子、酸素原子、硫黄原子から選ばれた原子を有する５または６員のヘテロ環基等）、アルコキシ基（例えば、炭素数１〜２０のアルコキシ基等）、アリールオキシ基（例えば、フェノキシ基、ナフチルオキシ基等）、アシルアミノ基（例えば、炭素数１〜２０のアルカノイルアミノ基、ベンゾイルアミノ基等）、アシルオキシ基（例えば、炭素数１〜２０のアルカノイルオキシ基、ベンゾイルオキシ基等）、アシル基（例えば、炭素数１〜２０のアルカノイル基、ベンゾイル基等）、カルバモイル基（例えば、無置換カルバモイル基、炭素数１〜２０のアルキルカルバモイル基、炭素数２〜４０のジアルキルカルバモイル基、フェニルカルバモイル基、炭素数７〜２６のＮ−アルキル−Ｎ−フェニルカルバモイル基等）、アルコキシカルボニル基（例えば、炭素数１〜２０のアルコキシカルボニル等）、スルホニルアミノ基（例えば、炭素数１〜２０のアルカンスルホニルアミノ基、ベンゼンスルホニルアミノ基等）、スルファモイル基（例えば、無置換スルファモイル基、炭素数１〜２０のアルキルスルファモイル基、炭素数２〜４０のジアルキルスルファモイル基、フェニルスルファモイル基、炭素数７〜２６のＮ−アルキル−Ｎ−フェニルスルファモイル基等）、ヒドロキシル基、スルホニル基（例えば、炭素数１〜２０のアルカンスルホニル基、ベンゼンスルホニル基等）、アルキルチオ基（例えば、炭素数１〜２０のアルキルチオ基等）、アリールチオ基（例えば、フェニルチオ基等）、ウレイド基（例えば、無置換ウレイド基、炭素数１〜２０のアルキルウレイド基、炭素数２〜４０のジアルキルウレイド基、フェニルウレイド基等）、ウレタン基（例えば、炭素数１〜２０のアルコキシカルボニルアミノ基等）、シアノ基、スルホ基、カルボキシル基、ニトロ基またはアミノ基（例えば、無置換アミノ基、炭素数１〜２０のアルキルアミノ基、炭素数２〜４０のジアルキルアミノ基、アニリノ基、炭素数７〜２６のＮ−アルキルアニリノ基等）等が挙げられる。
【００２２】
Ｒ₁およびＲ₂としてはアルキル基またはアラルキル基のものが好ましく、アルキル基のものが最も好ましい。
【００２３】
Ｒ₃はハメットのσｐの値が−０．３以上０．５以下のアルキル基を表すが、このようなアルキル基の例としては、例えばメチル基、エチル基、プロピル基、イソプロピル基、シクロプロピル基、ブチル基、イソブチル基、ターシャリーブチル基、ペンチル基、ネオペンチル基、シクロペンチル基、ターシャリーアミル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、２−エチルヘキシル基、ターシャリーオクチル基、ノニル基、置換基（ヒドロキシ基、アシルオキシ基、アルコキシ基、フェノキシ基、アルキルチオ基、フェニルチオ基、アミノ基（例えば無置換アミノ基、モノアルキルアミノ基またはジアルキルアミノ基等）、アシルアミノ基、アルコキシカルボニルアミノ基、ウレイド基またはスルホニルアミノ基等）で置換されたメチル基、または置換基（ヒドロキシ基、アシルオキシ基、アルコキシ基、フェノキシ基、アルキルチオ基、フェニルチオ基、アミノ基（例えば無置換アミノ基、モノアルキルアミノ基またはジアルキルアミノ基等）、アシルアミノ基、アルコキシカルボニルアミノ基、ウレイド基、スルホニルアミノ基、アシル基、スルホニル基、スルホキシ基、シアノ基、カルバモイル基、カルボキシ基、スルホ基、スルファモイル基またはハロゲン原子等）で置換されたエチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ターシャリーブチル基またはペンチル基等が挙げられる。Ｒ₃としては炭素数１〜６の無置換または置換アルキル基が好ましく、炭素数１〜６の無置換アルキル基のものが最も好ましい。
【００２４】
尚、本発明におけるハメットのσｐの値は「化学の領域」増刊１２２号（角江堂１９８０．３．１発行）の８５頁〜１２１頁記載のものを参考にすることができる。
【００２５】
Ｒ₄はアルキル基（例えばメチル基またはエチル基等）、アルコキシ基（例えばメトキシ基またはエトキシ基等）、ハロゲン原子（例えばフッ素原子、塩素原子または臭素原子等）、アシルアミノ基（例えばアセチルアミノ基、トリフルオロアセチルアミノ基またはプロパノイルアミノ基等）、ウレイド基（例えばメチルウレイド基またはエチルウレイド基等）、アルコキシカルボニル基（例えばエトキシカルボニルアミノ基等）またはスルホニルアミノ基（例えばメタンスルホニルアミノ基またはトリフルオロメタンスルホニルアミノ基等）を表す。
【００２６】
Ｒ₄としてはアルキル基またはアシルアミノ基のものが好ましい。
【００２７】
ｎは０または１を表すが、０のものが好ましい。
【００２８】
Ｘ₁およびＸ₂は一方がＣＲ（Ｒは水素原子、アルキル基（例えばメチル基またはエチル基等）、アルコキシ基（例えばメトキシ基またはエトキシ基等）、ハロゲン原子（例えばフッ素原子、塩素原子または臭素原子等）、アシルアミノ基（例えばアセチルアミノ基、トリフルオロアセチルアミノ基またはプロパノイルアミノ基等）、ウレイド基（例えばメチルウレイド基またはエチルウレイド基等）、アルコキシカルボニル基（例えばエトキシカルボニルアミノ基等）またはスルホニルアミノ基（例えばメタンスルホニルアミノ基またはトリフルオロメタンスルホニルアミノ基等）を表す）基、もう一方が窒素原子を表す。
【００２９】
Ｘ₁はＣＲ基、Ｘ₂が窒素原子のものが好ましく、さらにこの場合の好ましいＲとしては水素原子、アルキル基またはアシルアミノ基のものが挙げられ、アルキル基のものが最も好ましい。
【００３０】
ＹおよびＺは一方がＣＲ′（Ｒ′はアルキル基（例えばメチル基、エチル基、プロピル基、イソプロピル基、シクロプロピル基、ブチル基、イソブチル基、ターシャリーブチル基、ペンチル基、ネオペンチル基、ターシャリーアミル基、シクロペンチル基、ヘキシル基、２−エチルブチル基、シクロヘキシル基、ヘプチル基、オクチル基、２−エチルヘキシル基、ターシャリーオクチル基またはノニル基等）、アルケニル基（例えばビニル基またはアリル基等）、アルキニル基（例えばアセチレニル基またはプロバルギル基等）またはアラルキル基（例えばベンジル基またはフェネチル基等）基を表し、もう一方が窒素原子を表す。
【００３１】
上記Ｒ′はさらに適当な置換基で置換されていても良く、適当な置換基の例してはＲ₁またはＲ₂に置換されていても良い適当な置換基の例として上記した基等が挙げられる。
【００３２】
Ｙは窒素原子、ＺがＣＲ′基のものが最も好ましく、この場合のＲ′基としてはアルキル基のものが最も好ましい。
【００３３】
本発明のアゾメチン系化合物は、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、ＲまたはＲ′で表される置換基の少なくとも１つがスルホン酸基、カルボン酸基またはこれらの塩を含有する基であるが、Ｒ₁、Ｒ₂またはＲ′で表される置換基の少なくとも１つがスルホン酸基、カルボン酸基またはこれらの塩を含有する基であるものがより好ましい。
【００３４】
以下に一般式（１）で表される化合物（以下、本発明の色素ともいう）の具体的化合物例を示すが、本発明はこれらに限定されるものではない。
【００３５】
【化３】

【００３６】
【化４】

【００３７】
【化５】

【００３８】
【化６】

【００３９】
【化７】

【００４０】
【化８】

【００４１】
【化９】

【００４２】
【化１０】

【００４３】
本発明の色素はインクジェット記録液に用いられる。又本発明の色素は他の画像形成記録液用の色素としても有用であり、特に水系記録液（例えば、筆記用インク等）としても有用である。
【００４４】
本発明の色素を含有するインクジェット記録液は、本発明の色素の他に溶媒としての水と湿潤剤としての水溶性有機溶剤を使用する。
【００４５】
本発明のインクジェット記録液の各組成物の各組成比は、本発明の色素である一般式（１）のアゾメチン系化合物を０．１重量％以上２０．０重量％以下、水を１．０重量％以上９８．９重量％以下および水溶性有機溶剤を１．０重量％以上９８．９重量％以下である。
【００４６】
上記水溶性有機溶剤の例としては、アルコール類（例えば、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、イソブタノール、セカンダリーブタノール、ターシャリーブタノール、ペンタノール、ヘキサノール、シクロヘキサノール、ベンジルアルコール等）、多価アルコール類（例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、ポリプロピレングリコール、ブチレングリコール、ヘキサンジオール、ペンタンジオール、グリセリン、ヘキサントリオール、チオジグリコール等）、多価アルコールエーテル類（例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノブチルエーテル、エチレングリコールモノフェニルエーテル、プロピレングリコールモノフェニルエーテル等）、アミン類（例えば、エタノールアミン、ジエタノールアミン、トリエタノールアミン、Ｎ−メチルジエタノールアミン、Ｎ−エチルジエタノールアミン、モルホリン、Ｎ−エチルモルホリン、エチレンジアミン、ジエチレンジアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ポリエチレンイミン、ペンタメチルジエチレントリアミン、テトラメチルプロピレンジアミン等）、アミド類（例えば、ホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等）、複素環類（例えば、２−ピロリドン、Ｎ−メチル−２−ピロリドン、シクロヘキシルピロリドン、２−オキサゾリドン、１，３−ジメチル−２−イミダゾリジノン等）、スルホキシド類（例えば、ジメチルスルホキシド等）、スルホン類（例えば、スルホラン等）、尿素、アセトニトリル、アセトン等が挙げられる。
【００４７】
このような水系インクジェット記録液の具体的調整法については、例えば特開平５−１４８４３６号、同５−２９５３１２号、同７−９７５４１号、同７−８２５１５号、同７−１１８５８４号等に記載の方法を参照することができる。
【００４８】
上記したようなインクジェット記録液は、その飛翔時温度における粘度として２０ｃｐ以下が好ましく、０．５ｃｐ以上１０ｃｐ以下であることがより好ましい。
【００４９】
本発明のインクジェット記録液は、その飛翔時温度における表面張力として１５ｄｙｎ／ｃｍ以上が好ましく、２０ｄｙｎ／ｃｍ以上８０ｄｙｎ／ｃｍ以下であることが、より好ましい。
【００５０】
本発明のインクジェット記録液においては、吐出安定性、プリントヘッドやインクカートリッジ適合性、保存安定性、画像保存性、その他の諸性能向上の目的に応じて、粘度調製剤、表面張力調製剤、比抵抗調製剤、皮膜形成剤、分散剤、界面活性剤、紫外線吸収剤、酸化防止剤、退色防止剤、防黴剤、防錆剤等を添加することもできる。
【００５１】
本発明のインクジェット記録液は、その使用する記録方式に関して特に制約はなく、コンティニュアス方式及びオンデマンド方式のインクジェットプリンタ用のインクジェット記録液として好ましく使用することができる。オンデマンド型方式としては、電気−機械変換方式（例えば、シングルキャビティー型、ダブルキャビティー型、ベンダー型、ピストン型、シェアーモード型、シェアードウォール型等）、電気−熱変換方式（例えば、サーマルインクジェット型、バブルジェット型等）、静電吸引方式（例えば、電界制御型、スリットジェット型等）、放電方式（例えば、スパークジェット型等）などを具体的な例として挙げることができる。
【００５２】
【実施例】
実施例により本発明を更に具体的に説明するが、本発明はこの実施例における形態に限定されるものではない。
【００５３】
合成例１（例示化合物Ｉ−１の合成）
【００５４】
【化１１】

【００５５】
（中間体１ａ）
乾燥トルエン３０００ｍｌ中に６０％水素化ナトリウム１８５ｇを加えた懸濁液を内温６０℃に加温して、これに６−アミノ−２−ピコリン５００ｇとトルエン５００ｍｌによる混合溶液を約２時間で滴下した。さらにこの溶液を内温７０℃に保ちながらエチルブロマイド５５４ｇを約２時間で滴下し、さらに１時間かき混ぜた。この反応混合物を氷水３０００ｍｌ中に加え、有機層を抽出し２度水洗の後、濃縮乾燥することによって６−エチルアミノ−２−ピコリン６３２ｇを得た。
【００５６】
乾燥トルエン３８００ｍｌ中に６０％水素化ナトリウム１８５ｇを加えた懸濁液を内温９０℃に加温して、これに６−エチルアミノ−２−ピコリン６３２ｇとトルエン５００ｍｌによる混合溶液を約２時間で滴下し、さらに内温９３℃で１時間かき混ぜた。この溶液を９０℃に保ちながらエチルブロマイド５５４ｇを約２時間で滴下し、さらに１時間かき混ぜた。この反応混合物を氷水３０００ｍｌ中に加え、有機層を抽出し２度水洗の後、濃縮乾燥した。この粗生成物を減圧蒸留（７ｍｍＨｇ、１０３−１０８℃留分）することによって６−ジエチルアミノ−２−ピコリン６３０ｇを得た。
【００５７】
濃硫酸１９００ｍｌ中に、氷水で冷却しながら６−ジエチルアミノ−２−ピコリン６３０ｇを滴下した。これを内温５℃以下に保ちながら７０％硝酸３４７ｇを約２時間で滴下し、さらに内温５℃で１時間かき混ぜた。反応混合物を４ｋｇの氷中に加え、水酸化ナトリウム水溶液で中和した後、酢酸エチル３０００ｍｌにて２度抽出した。有機層を４０００ｍｌの水２回で水洗した後、有機層を無水硫酸マグネシウムで乾燥し、濃縮乾燥することで６−ジエチルアミノ−３−ニトロ−２−ピコリン７７５ｇを得た。
【００５８】
６−ジエチルアミノ−３−ニトロ−２−ピコリン６７５ｇとメタノール４０００ｍｌの溶液に５％のパラジウム／炭素触媒４０ｇを加え、オートクレーブ中で接触水素還元を行った。触媒を濾別後に反応溶液に濃塩酸６６０ｍｌを加え、溶媒を留去し、残査にアセトン４０００ｍｌを加え懸濁し、減圧濾過、乾燥することによって中間体１ａを７５０ｇ得た。
【００５９】
（中間体１ｃ）
中間体１ｂ３２．６ｇとアセトニトリル３００ｍｌの溶液中へクロロピバロイルクロリド２５．０ｇを滴下した。滴下後２０分間加熱還流した後、減圧にてアセトニトリルを留去した。残査にトルエン２００ｍｌおよびｐ−トルエンスルフォン酸３．０ｇを添加後、Ｄｅａｎ−Ｓｔａｒｋ管をつけて脱水しながら２時間還流した。この混合物から溶媒を減圧留去し、酢酸エチル５００ｍｌ、水３００ｍｌを加え再溶解した。水層をすて、有機層をさらに水洗した後、無水硫酸マグネシウムで乾燥後、溶媒を留去した。ヘキサンを加えて析出した固体を減圧濾取し、乾燥することで中間体１ｃを３５．０ｇ得た。
【００６０】
（中間体１ｄ）
中間体１ｃ３０．０ｇを無水酢酸１５０ｍ中でｌ２時間加熱還流した。反応後、無水酢酸を減圧留去し、メタノール１５０ｍｌと濃塩酸１５ｍｌを加え、２時間加熱還流した。反応後、熱時濾過し、濾液を減圧下で濃縮乾固した。アセトニトリルおよび水を加え分散後濾過し、中間体１ｄを２１．２ｇ得た。
【００６１】
（中間体１ｅ）
中間体１ｄ５．０ｇ、メルカプトエタンスルフォン酸ナトリウム３．６ｇおよび水酸化カリウム１．５ｇをエチレングリコール４０ｍｌ中で１５０℃、２０分間反応させた。反応液に酢酸エチル６０ｍｌを加えかき混ぜた後、静置し、上層を捨てた。この操作を3回行った後、残った下層にイソプロピルアルコールを加え、無機塩を析出、ろ過により除去した。このろ液を減圧濃縮し中間体１ｅを４．２ｇ得た。
【００６２】
（カプラー１ｆ）
中間体１ｅ３．８ｇを酢酸２０ｍｌ中かき混ぜ、少量のタングステン酸ナトリウムを添加後、加温し内温を６０℃とし、３４．５％過酸化水素水９ｍｌを滴下した。滴下後さらに約３０分間かき混ぜ、カプラー１ｆの溶液を得た。
【００６３】
（例示化合物Ｉ−１）
上記１ｆの溶液を水酸化ナトリウム水溶液で中和後、炭酸カリウム８．０ｇおよび中間体１ａ２．６ｇを加え、ここにペルオキソ硫酸アンモニウム５．０ｇの水溶液を滴下した。反応液を２０分間かき混ぜた後、析出した固体を濾取した。この固体を少量のメタノールに溶解後、過剰のジイソプロピルエーテルにて色素を割り出した。析出した固体を濾取して、さらにカラムクロマトグラフィーにて精製し色素Ｉ−１を４．７ｇ得た。例示化合物Ｉ−１のメタノール溶液における可視・紫外分光吸収スペクトルを図１に示す。
【００６４】
合成例２（例示化合物Ｉ−２の合成）
【００６５】
【化１２】

【００６６】
（中間体２ａ）
α−ニトロフェノキシ酪酸２０．０ｇ、クロロフォルム１００ｍｌおよび塩化チオニル２０ｍｌの混合溶液を３時間加熱還流した。この反応混合物を減圧乾固し、酸クロリド体を合成した。次に中間体１ｂ１８．７ｇをアセトニトリル２００ｍｌ中かき混ぜ、先の酸クロリド体のアセトニトリル溶液を滴下した。滴下後、この反応混合物を２時間加熱還流し、溶媒を減圧留去し、酢酸エチル５００ｍｌおよび水３００ｍｌを加え再溶解した。水層をすて、有機層をさらに水洗した後、有機層を無水硫酸マグネシウムで乾燥後、溶媒を留去した。残査をアセトニトリル中結析し、析出した固体を濾過することにより中間体２ａを２７．２ｇ得た。
【００６７】
（中間体２ｂ）
中間体２ａ１２．０ｇを無水酢酸１５０ｍｌ中で３時間加熱還流した。反応後、無水酢酸を減圧流去し、メタノール１００ｍｌおよび濃塩酸１０ｍｌを加え、さらに２時間加熱還流した。反応後、熱時濾過し、濾液を減圧下濃縮乾固した。この残査に酢酸エチル１５０ｍｌおよび水１００ｍｌを加え再溶解した。水層をすて、有機層をさらに水洗した後、有機層を無水硫酸マグネシウムで乾燥後、溶媒を留去した。残査をアセトニトリル中結析し、析出した固体を濾過することにより中間体２ｂを７．１ｇ得た。
【００６８】
（カプラー２ｃ）
中間体２ｂ１．００ｇをＮ，Ｎ−ジメチルホルムアミド１０ｍｌに溶解し、これに６５％のＮ−メチルタウリンナトリウム水溶液０．８８ｇを添加し、室温で１時間かき混ぜた。これに、酢酸エチル３０ｍｌおよび水３０ｍｌを加え、水層を抽出し、カプラー２ｃの水溶液を得た。
【００６９】
（例示化合物Ｉ−２）
上記の２ｃの水溶液に中間体１ａ（合成例１参照）０．７４ｇと炭酸ナトリウム１．３７ｇを加えた。これにペルオキソ硫酸アンモニウム１．４２ｇを徐々に加え、室温でさらに３０分間かき混ぜた。飽和食塩水５０ｍｌを加えた後、析出した結晶を濾取し、得られた粗結晶をメタノールに溶解した。さらにメタノールと等量のジイソプロピルエーテルを加えてかき混ぜた後、不要物を濾別して、得られた濾液を濃縮、乾固することで例示化合物Ｉ−２を１．１２ｇ得た。
【００７０】
例示化合物Ｉ−２のメタノール溶液における可視・紫外分光吸収スペクトルを図２に示す。
【００７１】
合成例３（例示化合物Ｉ−３の合成）
【００７２】
【化１３】

【００７３】
（カプラー３ａ）
中間体２ｂ（合成例２参照）４．１７ｇを水１００ｍｌおよびＮ，Ｎ−ジメチルホルムアミド２５ｍｌ中に加えてかき混ぜ、亜硫酸ナトリウム３．０７ｇを添加し、１０分間加熱還流することによってカプラー３ａの溶液を得た。
【００７４】
（Ｉ−３）
上記の３ａの溶液に、室温でペルオキソ硫酸アンモニウム５．９０ｇを添加した。次に炭酸ナトリウム９．００ｇを添加し、中間体１ａ（合成例１参照）３．０７ｇの水溶液を滴下した。反応液を２０分かき混ぜた後、ろ過により析出した染料を得た。この固体をメタノールに溶解後、ジイソプロピルエーテルを固体が析出するまで添加した。析出した固体を濾取し、さらにカラムクロマトグラフィーにて精製することにより例示化合物Ｉ−３を３．８１ｇ得た。
【００７５】
例示化合物Ｉ−３のメタノール溶液における可視・紫外分光吸収スペクトルを図３に示す。
【００７６】
合成例４（例示化合物Ｉ−４の合成）
【００７７】
【化１４】

【００７８】
カプラー４ａ４．８０ｇ、中間体１ａ（合成例１参照）５．００ｇおよび酢酸ナトリウム７．００ｇを水２００ｍｌとメタノール５０ｍｌの混合溶液に加え、室温でペルオキソ硫酸アンモニウム９．００ｇを徐々に加えた。室温で１時間かき混ぜた後、反応液を濃塩酸でｐＨを４まで中和、弱酸性化させ、析出した固体を濾取した。これを２００ｍｌの水に添加し、水酸化ナトリウムにてｐＨを９まで弱アルカリ化させて固体を溶解させ、不溶解物を濾別した後、得られた濾液に濃塩酸を加えｐＨを４まで中和、弱酸性化させ、析出した固体を濾取、水洗することにより例示化合物Ｉ−４を５．７５ｇ得た。
【００７９】
例示化合物Ｉ−４のメタノール溶液における可視・紫外分光吸収スペクトルを図４に示す。
【００８０】
合成例５（例示化合物Ｉ−５の合成）
【００８１】
【化１５】

【００８２】
（中間体５ａ）
乾燥トルエン１００ｍｌ中に６０％水素化ナトリウム４．７２ｇを加えた懸濁液を内温９０℃に加温して、これに６−エチルアミノ−２−ピコリン（合成例１参照）１６．０７ｇとトルエン１００ｍｌによる混合溶液を約１時間で滴下し、さらに内温９３℃で１時間かき混ぜた。この溶液に２−ブロモエタンスルホン酸ナトリウム２５．００ｇを加え、内温約１００℃にてＮ，Ｎ−ジメチルホルムアミド１０ｍｌを３０分間で滴下し、さらに１００℃で１時間かき混ぜた。この反応混合物を氷水２００ｍｌ中に加え、水層を抽出し、これに飽和食塩水５０ｍｌを添加しかき混ぜた後、析出した結晶を濾取した。得られた結晶を少量のメタノールに溶解し、同量のエタノールを加えて不溶解物を濾別した後、得られた濾液に過剰のジイソプロピルエーテルを加え、かき混ぜた後、析出した結晶を濾取することにより、中間体５ａを１４．７７ｇ得た。
【００８３】
（中間体５ｂ）
濃硫酸４０ｍｌ中に、氷水で冷却しながら中間体５ａ１２．００ｇを添加した。これを内温５℃以下に保ちながら６０％硝酸４．７７ｇを約４０分間で滴下し、さらに内温５℃で１時間かき混ぜた。反応混合物を２００ｍｌの氷中に加え、水酸化ナトリウム水溶液で中和した後、メタノール２００ｍｌとエタノール１００ｍｌを加え、析出した無機塩を濾別した。得られた濾液を減圧濃縮してメタノール１００ｍｌとエタノール５０ｍｌで残査を溶解し、濾過した濾液を約３０ｍｌまで濃縮後、ジイプロピルエーテル６０ｍｌを加え、冷却下２時間かき混ぜた後、析出結晶を濾取することにより中間体５ｂを１２．４３ｇ得た。
【００８４】
（中間体５ｃ）
中間体５ｂ１１．００ｇとメタノール１００ｍｌの溶液に５％のパラジウム／炭素触媒１．２０ｇを加え、オートクレーブ中で接触水素還元を行った。触媒を濾別後に反応溶液に濃塩酸１０ｍｌを加え、溶媒を留去し、残査にエタノール２００ｍｌを加え懸濁し、減圧濾過、乾燥することによって中間体５ｃを１１．４５ｇ得た。
【００８５】
（Ｉ−５）
カプラー５ｄ１．１６ｇ、中間体５ｃ１．９４ｇおよび酢酸ナトリウム２．０５ｇを水４０ｍｌとメタノール３０ｍｌの混合溶媒中に加え、室温でペルオキソ硫酸アンモニウム２．５０ｇをゆっくりと添加した。添加後、さらに１時間かき混ぜた後、減圧濃縮によりメタノールを留去し水６０ｍｌを加えて不溶解物を濾別した濾液を得た。これに飽和食塩水１０ｍｌを加えかき混ぜた後、析出結晶を濾取した。この粗生成物をアセトンに溶解して不溶解物を濾別し、得られた濾液を濃縮乾固させることにより例示化合物Ｉ−５を１．１２ｇ得た。
【００８６】
例示化合物Ｉ−５のメタノール溶液における可視・紫外分光吸収スペクトルを図５に示す。
【００８７】
合成例６（例示化合物Ｉ−８の合成）
【００８８】
【化１６】

【００８９】
カプラー６ａ１．１８ｇ、中間体５ｃ（合成例５参照）１．９４ｇおよび酢酸ナトリウム２．０５ｇを水４０ｍｌとメタノール３０ｍｌの混合溶媒中に加え、室温でペルオキソ硫酸アンモニウム２．５０ｇをゆっくりと添加した。添加後、さらに１時間かき混ぜた後、減圧濃縮によりメタノールを留去し水６０ｍｌを加えて不溶解物を濾別した濾液を得た。これに飽和食塩水１０ｍｌを加えかき混ぜた後、静置して上澄みを捨て、沈降した油状物を集めた。これを水３０ｍｌに溶解して氷水で冷却しながら飽和食塩水１０ｍｌを加えて１時間かき混ぜた後、析出結晶を濾取した。この粗生成物をメタノール２０ｍｌに溶解してジイソプロピルエーテル１００ｍｌを加えた後、不溶解物を濾別し、得られた濾液を濃縮後、ジイソプロピルエーテルで冷却しながら結晶を乾固、分散させ、濾取することにより例示化合物Ｉ−８を０．９８ｇ得た。
【００９０】
例示化合物Ｉ−８のメタノール溶液における可視・紫外分光吸収スペクトルを図６に示す。
【００９１】
合成例７（例示化合物Ｉ−１６の合成）
【００９２】
【化１７】

【００９３】
カプラー７ａ１．６２ｇ、中間体５ｃ（合成例５参照）２．１１ｇおよび酢酸ナトリウム２．８７ｇを水４０ｍｌとメタノール３０ｍｌの混合溶媒中に加え、室温でペルオキソ硫酸アンモニウム１．２６ｇをゆっくりと添加した。添加後、さらに１時間かき混ぜた後、減圧濃縮によりメタノールを留去し水６０ｍｌを加えて不溶解物を濾別した濾液を得た。これに飽和食塩水１０ｍｌを加えかき混ぜた後、析出結晶を濾取した。この粗生成物をアセトンに溶解して不溶解物を濾別し、得られた濾液を濃縮乾固させることにより例示化合物Ｉ−１６を１．０９ｇ得た。
【００９４】
例示化合物Ｉ−１６のメタノール溶液における可視・紫外分光吸収スペクトルを図７に示す。
【００９５】
上記図１〜７中の縦軸は吸光度（Ａｂｓ．）を横軸は波長（ｗａｖｅｌｅｎｇｔｈ（ｎｍ））を表す。
【００９６】
実施例１
表１に記載の組成を有する各インク組成物を用いて、インクジェットプリンタＭＪ−５０００Ｃ（セイコーエプソン株式会社製、電気−機械変換方式）によって、インクジェット用専用コート紙上に記録したマゼンタ画像サンプルを作成した。このサンプルを用いて、下記のように定義した耐光性、色調、の評価を行った結果を表１に示す。
【００９７】
耐光性：ＰＤＡ−６５（コニカ（株）製）の緑色光による反射濃度の測定から算出したキセノンフェードメーターにて２４時間爆射した後のサンプルの未爆射サンプルに対する画像の残存率。
【００９８】
耐光性（％）＝（爆射試料の緑色光反射濃度／未爆射試料の緑色光反射濃度）×１００
色調：ＰＤＡ−６５（コニカ（株）製）を用いて青色、緑色、赤色光における反射濃度を測定し、緑色光における反射濃度を１に規格化した場合の相対青色光反射濃度および相対赤色光反射濃度を算出して下記基準にて評価。すなわち○は青色光および赤色光の波長領域に不正吸収が少ない良好な色調のマゼンタ画像を表す。
【００９９】
○：相対青色光反射濃度０．３０未満かつ相対赤色光反射濃度０．１０未満の場合
△ｂ：相対青色光反射濃度０．３０以上で相対赤色光反射濃度０．１０未満の場合
△ｒ：相対青色光反射濃度０．３０未満で相対赤色光反射濃度０．１０以上の場合
×：相対青色光反射濃度０．３０以上かつ相対赤色光反射濃度０．１０以上の場合。
【０１００】
尚、表１の各化合物量の単位は全インクジェット記録液に対する重量％である。表中に記載の比較−１、比較−２および界面活性剤−１の構造を下記に示す。
【０１０１】
【化１８】

【０１０２】
【表１】

【０１０３】
表１の結果から明らかなように、本発明の色素及び該色素を含有するインクジェット記録液は比較色素及び該比較色素を含有するインクジェット記録液を使用した場合に比較して耐光性に優れ、かつ緑色光領域の反射濃度に対する青色光および赤色光領域の不正吸収が少ない色調が良好のものであることがわかる。
【０１０４】
さらに、本プリンタにおける連続吐出試験においても問題なく使用でき、本発明のインクジェット記録液の電気−機械変換方式に対する高い信頼性を確認した。
【０１０５】
実施例２
表２に記載の組成を有する各インク組成物を用いて、インクジェットプリンタＢＪＣ−６００Ｊ（キャノン社製、電気−熱変換方式）によって、インクジェット用専用光沢紙上に記録したサンプルを得た。このサンプルを用いて、実施例１と同様に耐光と色調の評価を行った結果を表２に示す。尚、表２の各化合物量の単位はインクジェット記録液における重量％であり、比較−１、比較−２および評価項目の定義は各々実施例１と同様である。
【０１０６】
【表２】

【０１０７】
表２の結果から明らかなように、本発明の色素及び該色素を含有するインクジェット記録液は比較色素及び該比較色素を含有するインクジェット記録液を使用した場合に比較して耐光性に優れ、かつ緑色光領域の反射濃度に対する青色光および赤色光領域の不正吸収が少ない色調が良好のものであることがわかる。また、本プリンタの系において本発明のインクジェット記録液の熱時変質によるヘッドの異常等は確認されず、電気−熱変換方式に対する適合性を持ち合わせていることを確認した。
【０１０８】
【発明の効果】
本発明による色素、該色素を含有するインクジェット記録液及び特に主な対象としてはマゼンタ色のインクジェット記録液は、色画像の耐光性に優れ、良好な色再現性のための色調に優れた効果を有する。
【図面の簡単な説明】
【図１】例示化合物Ｉ−１のメタノール溶液における可視・紫外分光吸収スペクトルを示す。
【図２】例示化合物Ｉ−２のメタノール溶液における可視・紫外分光吸収スペクトルを示す。
【図３】例示化合物Ｉ−３のメタノール溶液における可視・紫外分光吸収スペクトルを示す。
【図４】例示化合物Ｉ−４のメタノール溶液における可視・紫外分光吸収スペクトルを示す。
【図５】例示化合物Ｉ−５のメタノール溶液における可視・紫外分光吸収スペクトルを示す。
【図６】例示化合物Ｉ−８のメタノール溶液における可視・紫外分光吸収スペクトルを示す。
【図７】例示化合物Ｉ−１６のメタノール溶液における可視・紫外分光吸収スペクトルを示す。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an azomethine compound, and more particularly to a novel compound useful as a dye for an ink jet recording liquid and an ink jet recording liquid containing the compound.
[0002]
[Prior art]
In general, an image forming recording liquid, particularly an ink jet recording liquid, conforms to the recording method used, has a high recording image density and good color tone, and has a color image such as light resistance, heat resistance and water resistance. Excellent fastness, fast fixing on recording media, no bleed after recording, excellent storability as ink, no safety problems such as toxicity and flammability, low cost, etc. From this point of view, various recording dye compounds and recording liquids have been proposed and studied, but those that satisfy many of the requirements simultaneously are extremely limited.
[0003]
In color image recording using yellow, magenta, cyan, and black, for example, C.I. I. The conventionally known C.I. described in the index. I. Numbered dyes and pigments have been widely studied.
[0004]
In particular, for magenta inks, xanthene-based (for example, CI Acid Red 52) and azo-based (for example, CI Reactive Red 180) water-soluble dyes are known. In general, the former is light-resistant. The latter has a problem of spectral absorption characteristics related to color reproducibility, such as lack of clearness of magenta color tone.
[0005]
A dye compound using a pyrazole fused ring compound as a coupler is particularly effective as a dye for image formation with less unnecessary absorption compared with a dye compound using a pyrazolone compound known in the past as a coupler. JP-A-58-23434, 58-45512, and 58-142801 disclose their excellent characteristics as magenta couplers for silver halide photographic light-sensitive materials.
[0006]
Further, the usefulness of the dye compound itself is disclosed in JP-A-60-186567, JP-A-4-9341, JP-A-4-202261, and the like. Further, the application of these dye compounds to an ink jet recording method is disclosed in JP-A-3-231975.
[0007]
However, when the above compounds obtained by the coupling reaction of the pyrazole fused ring compound and the oxidized paraphenylenediamine compound disclosed in these documents are used as a dye for image formation, unnecessary side absorption and light resistance are eliminated. The level of sex was not always satisfactory.
[0008]
Under such circumstances, it has recently been found that a novel dye obtained by converting the benzene ring portion of paraphenylenediamine of the above dye compound into a corresponding pyridine ring skeleton is particularly effective for image formation in a thermal transfer material. JP-A-4-89287, JP-A-5-239367 and JP-A-6-80638, which are known to have improved absorption characteristics and image storage stability.
[0009]
However, when these known compounds are applied to an aqueous recording liquid that is preferable from the viewpoints of environmental suitability and safety, unnecessary absorption is undesirable in terms of color reproducibility due to its low solubility and interaction with the recording medium. The researchers have shown that it has increased and, unexpectedly, its lightfastness also tends to deteriorate.
[0010]
In order to solve this problem, a magenta dye compound having excellent color tone and light fastness and an ink jet recording liquid using the compound have been actively developed, but still satisfactory compounds and ink jet recording liquids have been achieved. There is no current situation.
[0011]
[Problems to be solved by the invention]
An object of the present invention is to provide a dye compound having excellent light resistance for color images and excellent color tone for good color reproducibility, an ink jet recording liquid containing the compound, and a magenta ink jet recording liquid as a main object. Is to provide.
[0012]
[Means for Solving the Problems]
The above object of the present invention is achieved by the following configurations.
[0013]
1. An azomethine compound represented by the following general formula (1):
[0014]
[Chemical 2]

[0015]
  Where R₁Is a hydrogen atom, an alkyl group,UnsubstitutedAn alkenyl group,UnsubstitutedRepresents an alkynyl group or an aralkyl group, R₂Is a hydrogen atom, an alkyl group,UnsubstitutedAn alkenyl group,UnsubstitutedRepresents an alkynyl group, an aralkyl group, an aromatic group or a heterocyclic group, R₁Is R₂A ring may be formed together. R_ThreeRepresents an alkyl group having a Hammett σp value of −0.3 or more and 0.5 or less, and R_FourRepresents an alkyl group, an alkoxy group, a halogen atom, an acylamino group, a ureido group, an alkoxycarbonyl group or a sulfonylamino group, and n represents 0 or 1. X₁And X₂Is a CR group (R represents a hydrogen atom, alkyl group, alkoxy group, halogen atom, acylamino group, ureido group, alkoxycarbonyl group or sulfonylamino group), and the other represents a nitrogen atom. One of Y and Z represents a CR ′ (R ′ represents an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group) group, and the other represents a nitrogen atom. R₁, R₂, R_Three, R_Four, R and R ′ are at least one substituent containing a sulfonic acid group, a carboxylic acid group or a salt thereof.
[0016]
2. The azomethine compound represented by the general formula (1) is 0.1 wt% or more and 20.0 wt% or less, water is 1.0 wt% or more and 98.9 wt% or less, and the water-soluble organic solvent is 1.0 wt%. An ink jet recording liquid, comprising at least 9% by weight and no more than 98.9% by weight.
[0017]
The present invention will be described in detail below.
[0018]
First, the compound represented by the general formula (1) of the present invention will be described in detail.
[0019]
  In the general formula (1), R₁Is a hydrogen atom, an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, neopentyl group or hexyl group),UnsubstitutedAn alkenyl group (eg allyl group),UnsubstitutedRepresents an alkynyl group (such as a provalgyl group) or an aralkyl group (such as a benzyl group or a phenethyl group);₂Is a hydrogen atom, an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, neopentyl group or hexyl group), alkenyl group (for example allyl group), alkynyl group (for example propargyl group) Group), aralkyl group (eg benzyl group or phenethyl group), aromatic group (eg phenyl group or naphthyl group) or heterocyclic group (eg pyridyl group, pyrazinyl group, pyrimidinyl group, thienyl group, furyl group, thiazolyl). Group, oxazolyl group, isoxazolyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, tetrahydrofuryl group, piperazinyl group, piperidinyl group, morpholinyl group, benzothiazolyl group, benzoxazolyl group or benzimidazolyl group).
[0020]
R₁And R₂May form a ring (for example, a piperidine ring, a pyrrolidine ring, a piperazine ring or a morpholine ring) with a nitrogen atom.
[0021]
  R₁And R₂ (Except for hydrogen atom, unsubstituted alkenyl group or unsubstituted alkynyl group)May be further substituted with a suitable substituent. Examples of suitable substituents include aliphatic groups (for example, alkyl groups having 1 to 20 carbon atoms) and aromatic groups (for example, phenyl groups, naphthyl groups, etc.). A heterocyclic group (for example, a 5- or 6-membered heterocyclic group having an atom selected from at least one nitrogen atom, oxygen atom or sulfur atom), an alkoxy group (for example, an alkoxy group having 1 to 20 carbon atoms, etc.) ), Aryloxy group (for example, phenoxy group, naphthyloxy group, etc.), acylamino group (for example, alkanoylamino group having 1 to 20 carbon atoms, benzoylamino group, etc.), acyloxy group (for example, alkanoyl having 1 to 20 carbon atoms) Oxy group, benzoyloxy group, etc.), acyl group (eg, alkanoyl group having 1 to 20 carbon atoms, benzoyl group, etc.), carbamoyl group (eg, none) A substituted carbamoyl group, an alkylcarbamoyl group having 1 to 20 carbon atoms, a dialkylcarbamoyl group having 2 to 40 carbon atoms, a phenylcarbamoyl group, an N-alkyl-N-phenylcarbamoyl group having 7 to 26 carbon atoms), an alkoxycarbonyl group ( For example, a C1-C20 alkoxycarbonyl etc.), a sulfonylamino group (for example, a C1-C20 alkanesulfonylamino group, a benzenesulfonylamino group, etc.), a sulfamoyl group (for example, unsubstituted sulfamoyl group, carbon number 1) -20 alkylsulfamoyl group, C2-C40 dialkylsulfamoyl group, phenylsulfamoyl group, C7-26 N-alkyl-N-phenylsulfamoyl group, etc.), hydroxyl group, A sulfonyl group (for example, an alkanesulfonyl group having 1 to 20 carbon atoms) Benzenesulfonyl group, etc.), alkylthio group (eg, alkylthio group having 1 to 20 carbon atoms), arylthio group (eg, phenylthio group etc.), ureido group (eg, unsubstituted ureido group, alkylureido having 1 to 20 carbon atoms) Group, dialkylureido group having 2 to 40 carbon atoms, phenylureido group, etc.), urethane group (for example, alkoxycarbonylamino group having 1 to 20 carbon atoms, etc.), cyano group, sulfo group, carboxyl group, nitro group or amino group. (For example, an unsubstituted amino group, an alkylamino group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, an anilino group, and an N-alkylanilino group having 7 to 26 carbon atoms).
[0022]
R₁And R₂Are preferably an alkyl group or an aralkyl group, and most preferably an alkyl group.
[0023]
R_ThreeRepresents an alkyl group having a Hammett σp value of −0.3 or more and 0.5 or less. Examples of such an alkyl group include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, Butyl group, isobutyl group, tertiary butyl group, pentyl group, neopentyl group, cyclopentyl group, tertiary amyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, tertiary octyl group, nonyl group, Substituent (hydroxy group, acyloxy group, alkoxy group, phenoxy group, alkylthio group, phenylthio group, amino group (for example, unsubstituted amino group, monoalkylamino group or dialkylamino group), acylamino group, alkoxycarbonylamino group, ureido Group or sulfonylamino group) Methyl groups or substituents (hydroxy groups, acyloxy groups, alkoxy groups, phenoxy groups, alkylthio groups, phenylthio groups, amino groups (eg unsubstituted amino groups, monoalkylamino groups or dialkylamino groups), acylamino groups, An alkoxycarbonylamino group, a ureido group, a sulfonylamino group, an acyl group, a sulfonyl group, a sulfoxy group, a cyano group, a carbamoyl group, a carboxy group, a sulfo group, a sulfamoyl group, or a halogen atom) An isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, etc. are mentioned. R_ThreeIs preferably an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, and most preferably an unsubstituted alkyl group having 1 to 6 carbon atoms.
[0024]
In addition, the value of Hammett's σp in the present invention can be referred to that described in pages 85 to 121 of “Area of Chemistry” No. 122 (published by Kakuedo 1980.3.1).
[0025]
R_FourIs an alkyl group (for example, methyl group or ethyl group), an alkoxy group (for example, methoxy group or ethoxy group), a halogen atom (for example, fluorine atom, chlorine atom or bromine atom), an acylamino group (for example, acetylamino group, trifluoro) Acetylamino group or propanoylamino group), ureido group (eg methylureido group or ethylureido group etc.), alkoxycarbonyl group (eg ethoxycarbonylamino group etc.) or sulfonylamino group (eg methanesulfonylamino group or trifluoromethanesulfonyl) Represents an amino group or the like.
[0026]
R_FourThe alkyl group is preferably an alkyl group or an acylamino group.
[0027]
n represents 0 or 1, with 0 being preferred.
[0028]
X₁And X₂Is one of CR (R is a hydrogen atom, an alkyl group (such as a methyl group or an ethyl group), an alkoxy group (such as a methoxy group or an ethoxy group), a halogen atom (such as a fluorine atom, a chlorine atom or a bromine atom), an acylamino Group (for example, acetylamino group, trifluoroacetylamino group or propanoylamino group), ureido group (for example, methylureido group or ethylureido group), alkoxycarbonyl group (for example, ethoxycarbonylamino group) or sulfonylamino group ( For example, a methanesulfonylamino group or a trifluoromethanesulfonylamino group), and the other represents a nitrogen atom.
[0029]
X₁Is CR group, X₂Is preferably a nitrogen atom, and preferred R in this case includes a hydrogen atom, an alkyl group or an acylamino group, and an alkyl group is most preferred.
[0030]
One of Y and Z is CR ′ (R ′ is an alkyl group (eg, methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, tertiary butyl, pentyl, neopentyl, tertiary Liamyl group, cyclopentyl group, hexyl group, 2-ethylbutyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, tertiary octyl group or nonyl group), alkenyl group (for example, vinyl group or allyl group) Represents an alkynyl group (for example, acetylenyl group or provalgyl group) or an aralkyl group (for example, benzyl group or phenethyl group), and the other represents a nitrogen atom.
[0031]
R ′ may be further substituted with a suitable substituent. Examples of suitable substituents are R₁Or R₂Examples of suitable substituents that may be substituted are those mentioned above.
[0032]
Y is most preferably a nitrogen atom and Z is a CR ′ group. In this case, the R ′ group is most preferably an alkyl group.
[0033]
The azomethine compound of the present invention is R₁, R₂, R_Three, R_FourAt least one of the substituents represented by R or R ′ is a sulfonic acid group, a carboxylic acid group or a group containing a salt thereof.₁, R₂Alternatively, at least one of the substituents represented by R ′ is more preferably a sulfonic acid group, a carboxylic acid group or a group containing a salt thereof.
[0034]
Specific examples of the compound represented by the general formula (1) (hereinafter also referred to as the dye of the present invention) are shown below, but the present invention is not limited thereto.
[0035]
[Chemical 3]

[0036]
[Formula 4]

[0037]
[Chemical formula 5]

[0038]
[Chemical 6]

[0039]
[Chemical 7]

[0040]
[Chemical 8]

[0041]
[Chemical 9]

[0042]
[Chemical Formula 10]

[0043]
The dye of the present invention is used in an ink jet recording liquid. The coloring matter of the present invention is also useful as a coloring matter for other image forming recording liquid, and particularly useful as an aqueous recording liquid (for example, writing ink).
[0044]
The ink jet recording liquid containing the dye of the present invention uses water as a solvent and a water-soluble organic solvent as a wetting agent in addition to the dye of the present invention.
[0045]
The composition ratio of each composition of the ink jet recording liquid of the present invention is such that the azomethine compound of the general formula (1), which is the dye of the present invention, is 0.1 wt% to 20.0 wt% and water is 1.0 wt%. The water-soluble organic solvent is 1.0% by weight or more and 98.9% by weight or less.
[0046]
Examples of the water-soluble organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), polyvalent Alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyhydric alcohol Ethers (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Tylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol mono Butyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, etc.), amines (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine) , Ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.) ), Heterocyclic rings (for example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone), sulfoxides (for example, dimethyl sulfoxide) , Sulfones (for example, sulfolane), urea, acetonitrile, acetone and the like.
[0047]
Specific methods for adjusting such an aqueous ink jet recording liquid are described in, for example, JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, and 7-118584. You can refer to the method.
[0048]
The ink jet recording liquid as described above has a viscosity at the time of flight of preferably 20 cp or less, and more preferably 0.5 cp or more and 10 cp or less.
[0049]
In the ink jet recording liquid of the present invention, the surface tension at the time of flight is preferably 15 dyn / cm or more, more preferably 20 dyn / cm or more and 80 dyn / cm or less.
[0050]
In the inkjet recording liquid of the present invention, the viscosity adjusting agent, the surface tension adjusting agent, the ratio according to the purpose of improving the ejection stability, the compatibility with the print head and the ink cartridge, the storage stability, the image storage stability, and other various performances. Resistance adjusting agents, film forming agents, dispersants, surfactants, UV absorbers, antioxidants, fading inhibitors, antifungal agents, rust inhibitors, and the like can also be added.
[0051]
The ink jet recording liquid of the present invention is not particularly limited with respect to the recording method used, and can be preferably used as an ink jet recording liquid for a continuous type and an on-demand type ink jet printer. As an on-demand type, an electro-mechanical conversion type (for example, a single cavity type, a double cavity type, a bender type, a piston type, a shear mode type, a shared wall type, etc.), an electro-thermal conversion type (for example, a thermal type) Specific examples include an ink jet type, a bubble jet type, and the like, an electrostatic suction type (for example, an electric field control type, a slit jet type, etc.), a discharge type (for example, a spark jet type, etc.), and the like.
[0052]
【Example】
EXAMPLES The present invention will be described more specifically with reference to examples. However, the present invention is not limited to the embodiments in these examples.
[0053]
Synthesis Example 1 (Synthesis of Exemplary Compound I-1)
[0054]
Embedded image

[0055]
(Intermediate 1a)
A suspension obtained by adding 185 g of 60% sodium hydride in 3000 ml of dry toluene was heated to an internal temperature of 60 ° C., and a mixed solution of 500 g of 6-amino-2-picoline and 500 ml of toluene was added dropwise thereto in about 2 hours. did. Further, 554 g of ethyl bromide was added dropwise over about 2 hours while maintaining the internal temperature at 70 ° C., and the mixture was further stirred for 1 hour. This reaction mixture was added to 3000 ml of ice water, the organic layer was extracted, washed twice with water, and concentrated to dryness to obtain 632 g of 6-ethylamino-2-picoline.
[0056]
A suspension obtained by adding 185 g of 60% sodium hydride in 3800 ml of dry toluene was heated to an internal temperature of 90 ° C., and a mixed solution of 632 g of 6-ethylamino-2-picoline and 500 ml of toluene was added in about 2 hours. The solution was added dropwise and further stirred at an internal temperature of 93 ° C. for 1 hour. While maintaining this solution at 90 ° C., 554 g of ethyl bromide was added dropwise over about 2 hours, and the mixture was further stirred for 1 hour. This reaction mixture was added to 3000 ml of ice water, the organic layer was extracted, washed twice with water, and then concentrated to dryness. This crude product was distilled under reduced pressure (7 mmHg, 103-108 ° C. fraction) to obtain 630 g of 6-diethylamino-2-picoline.
[0057]
In 1900 ml of concentrated sulfuric acid, 630 g of 6-diethylamino-2-picoline was added dropwise while cooling with ice water. While maintaining this at an internal temperature of 5 ° C. or lower, 347 g of 70% nitric acid was added dropwise in about 2 hours, and the mixture was further stirred at an internal temperature of 5 ° C. for 1 hour. The reaction mixture was added to 4 kg of ice, neutralized with an aqueous sodium hydroxide solution, and extracted twice with 3000 ml of ethyl acetate. The organic layer was washed twice with 4000 ml of water, and then the organic layer was dried over anhydrous magnesium sulfate and concentrated to obtain 775 g of 6-diethylamino-3-nitro-2-picoline.
[0058]
To a solution of 675 g of 6-diethylamino-3-nitro-2-picoline and 4000 ml of methanol was added 40 g of 5% palladium / carbon catalyst, and catalytic hydrogen reduction was performed in an autoclave. After removing the catalyst by filtration, 660 ml of concentrated hydrochloric acid was added to the reaction solution, the solvent was distilled off, and 4000 ml of acetone was suspended in the residue, followed by filtration, drying under reduced pressure, and 750 g of intermediate 1a was obtained.
[0059]
(Intermediate 1c)
25.0 g of chloropivaloyl chloride was added dropwise to a solution of 32.6 g of intermediate 1b and 300 ml of acetonitrile. After dropwise addition, the mixture was heated to reflux for 20 minutes, and then acetonitrile was distilled off under reduced pressure. To the residue, 200 ml of toluene and 3.0 g of p-toluenesulfonic acid were added, followed by refluxing for 2 hours while dehydrating with a Dean-Stark tube. The solvent was distilled off from this mixture under reduced pressure, and 500 ml of ethyl acetate and 300 ml of water were added and redissolved. The aqueous layer was washed, and the organic layer was further washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off. Hexane was added and the precipitated solid was collected by filtration under reduced pressure and dried to obtain 35.0 g of Intermediate 1c.
[0060]
(Intermediate 1d)
Intermediate 1c (30.0 g) was heated to reflux in acetic anhydride (150 m) for l2 hours. After the reaction, acetic anhydride was distilled off under reduced pressure, 150 ml of methanol and 15 ml of concentrated hydrochloric acid were added, and the mixture was heated to reflux for 2 hours. After the reaction, it was filtered while hot, and the filtrate was concentrated to dryness under reduced pressure. Acetonitrile and water were added and dispersed, followed by filtration to obtain 21.2 g of intermediate 1d.
[0061]
(Intermediate 1e)
Intermediate 1d 5.0 g, mercaptoethane sodium sulfonate 3.6 g, and potassium hydroxide 1.5 g were reacted in ethylene glycol 40 ml at 150 ° C. for 20 minutes. 60 ml of ethyl acetate was added to the reaction mixture and stirred, and then allowed to stand, and the upper layer was discarded. After performing this operation three times, isopropyl alcohol was added to the remaining lower layer, and an inorganic salt was precipitated and removed by filtration. The filtrate was concentrated under reduced pressure to obtain 4.2 g of intermediate 1e.
[0062]
(Coupler 1f)
3.8 g of intermediate 1e was stirred in 20 ml of acetic acid, a small amount of sodium tungstate was added, and the mixture was heated to an internal temperature of 60 ° C., and 9 ml of 34.5% aqueous hydrogen peroxide was added dropwise. After the addition, the mixture was further stirred for about 30 minutes to obtain a coupler 1f solution.
[0063]
(Exemplary Compound I-1)
After neutralizing the 1f solution with an aqueous sodium hydroxide solution, 8.0 g of potassium carbonate and 2.6 g of intermediate 1a were added, and an aqueous solution of 5.0 g of ammonium peroxosulfate was added dropwise thereto. The reaction solution was stirred for 20 minutes, and the precipitated solid was collected by filtration. The solid was dissolved in a small amount of methanol, and the dye was determined with excess diisopropyl ether. The precipitated solid was collected by filtration and further purified by column chromatography to obtain 4.7 g of dye I-1. A visible / ultraviolet spectral absorption spectrum of Example Compound I-1 in a methanol solution is shown in FIG.
[0064]
Synthesis Example 2 (Synthesis of Exemplified Compound I-2)
[0065]
Embedded image

[0066]
(Intermediate 2a)
A mixed solution of 20.0 g of α-nitrophenoxybutyric acid, 100 ml of chloroform and 20 ml of thionyl chloride was heated to reflux for 3 hours. This reaction mixture was dried under reduced pressure to synthesize an acid chloride form. Next, 18.7 g of intermediate 1b was stirred in 200 ml of acetonitrile, and the acetonitrile solution of the acid chloride was added dropwise. After the dropwise addition, the reaction mixture was heated to reflux for 2 hours, the solvent was distilled off under reduced pressure, and 500 ml of ethyl acetate and 300 ml of water were added and redissolved. The aqueous layer was rinsed and the organic layer was further washed with water. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The residue was precipitated in acetonitrile, and the precipitated solid was filtered to obtain 27.2 g of intermediate 2a.
[0067]
(Intermediate 2b)
12.0 g of intermediate 2a was heated to reflux in 150 ml of acetic anhydride for 3 hours. After the reaction, acetic anhydride was removed under reduced pressure, 100 ml of methanol and 10 ml of concentrated hydrochloric acid were added, and the mixture was further heated under reflux for 2 hours. After the reaction, it was filtered while hot, and the filtrate was concentrated to dryness under reduced pressure. To this residue, 150 ml of ethyl acetate and 100 ml of water were added and redissolved. The aqueous layer was rinsed and the organic layer was further washed with water. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The residue was precipitated in acetonitrile, and the precipitated solid was filtered to obtain 7.1 g of Intermediate 2b.
[0068]
(Coupler 2c)
1.00 g of intermediate 2b was dissolved in 10 ml of N, N-dimethylformamide, 0.88 g of 65% aqueous solution of sodium N-methyltaurine was added thereto, and the mixture was stirred at room temperature for 1 hour. To this was added 30 ml of ethyl acetate and 30 ml of water, and the aqueous layer was extracted to obtain an aqueous solution of coupler 2c.
[0069]
(Exemplary Compound I-2)
To the aqueous solution of 2c, 0.74 g of intermediate 1a (see Synthesis Example 1) and 1.37 g of sodium carbonate were added. To this, 1.42 g of ammonium peroxosulfate was gradually added, and the mixture was further stirred at room temperature for 30 minutes. After adding 50 ml of saturated brine, the precipitated crystals were collected by filtration, and the resulting crude crystals were dissolved in methanol. Furthermore, after adding methanol and an equivalent amount of diisopropyl ether and stirring, unnecessary substances were filtered off, and the obtained filtrate was concentrated and dried to obtain 1.12 g of Exemplified Compound I-2.
[0070]
FIG. 2 shows a visible / ultraviolet spectral absorption spectrum of Example Compound I-2 in a methanol solution.
[0071]
Synthesis Example 3 (Synthesis of Exemplified Compound I-3)
[0072]
Embedded image

[0073]
(Coupler 3a)
4.17 g of intermediate 2b (see Synthesis Example 2) was added to 100 ml of water and 25 ml of N, N-dimethylformamide and mixed. 3.07 g of sodium sulfite was added, and the solution of coupler 3a was heated to reflux for 10 minutes. Obtained.
[0074]
(I-3)
To the solution of 3a above, 5.90 g ammonium peroxosulfate was added at room temperature. Next, 9.00 g of sodium carbonate was added, and an aqueous solution of 3.07 g of intermediate 1a (see Synthesis Example 1) was added dropwise. The reaction solution was stirred for 20 minutes, and then a dye deposited by filtration was obtained. This solid was dissolved in methanol, and diisopropyl ether was added until the solid precipitated. The precipitated solid was collected by filtration and further purified by column chromatography to obtain 3.81 g of Exemplified Compound I-3.
[0075]
FIG. 3 shows a visible / ultraviolet spectral absorption spectrum of Example Compound I-3 in a methanol solution.
[0076]
Synthesis Example 4 (Synthesis of Exemplified Compound I-4)
[0077]
Embedded image

[0078]
4.80 g of coupler 4a, 5.00 g of intermediate 1a (see Synthesis Example 1) and 7.00 g of sodium acetate were added to a mixed solution of 200 ml of water and 50 ml of methanol, and 9.00 g of ammonium peroxosulfate was gradually added at room temperature. After stirring at room temperature for 1 hour, the reaction solution was neutralized with concentrated hydrochloric acid to pH 4 and weakly acidified, and the precipitated solid was collected by filtration. This was added to 200 ml of water, the pH was weakly alkalinized with sodium hydroxide to 9 to dissolve the solid, the insoluble material was filtered off, concentrated hydrochloric acid was added to the resulting filtrate, and the pH was adjusted to 4. Neutralization and weak acidification were performed, and the precipitated solid was collected by filtration and washed with water to obtain 5.75 g of Exemplified Compound I-4.
[0079]
A visible / ultraviolet spectral absorption spectrum of Example Compound I-4 in a methanol solution is shown in FIG.
[0080]
Synthesis Example 5 (Synthesis of Exemplified Compound I-5)
[0081]
Embedded image

[0082]
(Intermediate 5a)
A suspension obtained by adding 4.72 g of 60% sodium hydride in 100 ml of dry toluene was heated to an internal temperature of 90 ° C., and was then added with 16.07 g of 6-ethylamino-2-picoline (see Synthesis Example 1). A mixed solution of 100 ml of toluene was dropped in about 1 hour, and the mixture was further stirred for 1 hour at an internal temperature of 93 ° C. To this solution, 25.00 g of sodium 2-bromoethanesulfonate was added, 10 ml of N, N-dimethylformamide was added dropwise at an internal temperature of about 100 ° C. over 30 minutes, and the mixture was further stirred at 100 ° C. for 1 hour. This reaction mixture was added to 200 ml of ice water, the aqueous layer was extracted, 50 ml of saturated brine was added and stirred, and the precipitated crystals were collected by filtration. The obtained crystals are dissolved in a small amount of methanol, the same amount of ethanol is added and insoluble matters are filtered off, excess diisopropyl ether is added to the obtained filtrate and the mixture is stirred, and the precipitated crystals are collected by filtration. As a result, 14.77 g of Intermediate 5a was obtained.
[0083]
(Intermediate 5b)
12.00 g of intermediate 5a was added to 40 ml of concentrated sulfuric acid while cooling with ice water. While maintaining this at an internal temperature of 5 ° C. or lower, 4.77 g of 60% nitric acid was added dropwise over about 40 minutes, and the mixture was further stirred at an internal temperature of 5 ° C. for 1 hour. The reaction mixture was added to 200 ml of ice and neutralized with an aqueous sodium hydroxide solution, 200 ml of methanol and 100 ml of ethanol were added, and the precipitated inorganic salt was separated by filtration. The obtained filtrate was concentrated under reduced pressure, and the residue was dissolved with 100 ml of methanol and 50 ml of ethanol. The filtrate was concentrated to about 30 ml, 60 ml of dipropyl ether was added, and the mixture was stirred for 2 hours with cooling. This yielded 12.43 g of intermediate 5b.
[0084]
(Intermediate 5c)
1.20 g of 5% palladium / carbon catalyst was added to a solution of 11.00 g of intermediate 5b and 100 ml of methanol, and catalytic hydrogen reduction was performed in an autoclave. After the catalyst was filtered off, 10 ml of concentrated hydrochloric acid was added to the reaction solution, the solvent was distilled off, 200 ml of ethanol was suspended in the residue, suspended under reduced pressure, and dried to obtain 11.45 g of Intermediate 5c.
[0085]
(I-5)
Coupler 5d (1.16 g), intermediate 5c (1.94 g) and sodium acetate (2.05 g) were added to a mixed solvent of 40 ml of water and 30 ml of methanol, and 2.50 g of ammonium peroxosulfate was slowly added at room temperature. After the addition, the mixture was further stirred for 1 hour, methanol was distilled off by concentration under reduced pressure, 60 ml of water was added, and a filtrate obtained by separating insolubles by filtration was obtained. To this was added 10 ml of saturated brine and the mixture was stirred, and the precipitated crystals were collected by filtration. This crude product was dissolved in acetone, insoluble matters were filtered off, and the obtained filtrate was concentrated to dryness to obtain 1.12 g of Exemplified Compound I-5.
[0086]
FIG. 5 shows a visible / ultraviolet spectral absorption spectrum of Example Compound I-5 in a methanol solution.
[0087]
Synthesis Example 6 (Synthesis of Exemplified Compound I-8)
[0088]
Embedded image

[0089]
1.18 g of coupler 6a, 1.94 g of intermediate 5c (see Synthesis Example 5) and 2.05 g of sodium acetate were added to a mixed solvent of 40 ml of water and 30 ml of methanol, and 2.50 g of ammonium peroxosulfate was slowly added at room temperature. After the addition, the mixture was further stirred for 1 hour, methanol was distilled off by concentration under reduced pressure, 60 ml of water was added, and a filtrate obtained by separating insolubles by filtration was obtained. To this was added 10 ml of saturated brine, and the mixture was stirred and allowed to stand. The supernatant was discarded, and the precipitated oil was collected. This was dissolved in 30 ml of water, 10 ml of saturated brine was added while cooling with ice water, and the mixture was stirred for 1 hour, and the precipitated crystals were collected by filtration. This crude product is dissolved in 20 ml of methanol and 100 ml of diisopropyl ether is added, insoluble matter is filtered off, the filtrate obtained is concentrated, and the crystals are dried and dispersed while cooling with diisopropyl ether. As a result, 0.98 g of Exemplified Compound I-8 was obtained.
[0090]
FIG. 6 shows a visible / ultraviolet spectral absorption spectrum of Example Compound I-8 in a methanol solution.
[0091]
Synthesis Example 7 (Synthesis of Exemplified Compound I-16)
[0092]
Embedded image

[0093]
1.62 g of coupler 7a, 2.11 g of intermediate 5c (see Synthesis Example 5) and 2.87 g of sodium acetate were added to a mixed solvent of 40 ml of water and 30 ml of methanol, and 1.26 g of ammonium peroxosulfate was slowly added at room temperature. After the addition, the mixture was further stirred for 1 hour, methanol was distilled off by concentration under reduced pressure, 60 ml of water was added, and a filtrate obtained by separating insolubles by filtration was obtained. To this was added 10 ml of saturated brine and the mixture was stirred, and the precipitated crystals were collected by filtration. This crude product was dissolved in acetone, insoluble matters were filtered off, and the obtained filtrate was concentrated to dryness to obtain 1.09 g of Exemplified Compound I-16.
[0094]
FIG. 7 shows a visible / ultraviolet spectral absorption spectrum of Example Compound I-16 in a methanol solution.
[0095]
1 to 7, the vertical axis represents absorbance (Abs.) And the horizontal axis represents wavelength (wavelength (nm)).
[0096]
Example 1
Using each ink composition having the composition shown in Table 1, a magenta image sample recorded on a special coated paper for inkjet was prepared by an inkjet printer MJ-5000C (manufactured by Seiko Epson Corporation, electro-mechanical conversion method). . Table 1 shows the results of evaluation of light resistance and color tone defined as follows using this sample.
[0097]
Light resistance: The residual ratio of an image with respect to an unexploded sample of a sample after being bombarded for 24 hours with a xenon fade meter calculated from the measurement of reflection density with green light of PDA-65 (manufactured by Konica)
[0098]
Light resistance (%) = (green light reflection density of explosive sample / green light reflection density of unexploded sample) × 100
Color tone: The reflection density in blue, green, and red light is measured using PDA-65 (manufactured by Konica Corporation), and the reflection density in relative blue light and the relative red light when the reflection density in green light is normalized to 1. The reflection density is calculated and evaluated according to the following criteria. That is, ◯ represents a magenta image having a good color tone with less illegal absorption in the wavelength regions of blue light and red light.
[0099]
○: When the relative blue light reflection density is less than 0.30 and the relative red light reflection density is less than 0.10
Δb: When the relative blue light reflection density is 0.30 or more and the relative red light reflection density is less than 0.10
Δr: When the relative blue light reflection density is less than 0.30 and the relative red light reflection density is 0.10 or more
X: When the relative blue light reflection density is 0.30 or more and the relative red light reflection density is 0.10 or more.
[0100]
The unit of the amount of each compound in Table 1 is% by weight with respect to the total ink jet recording liquid. The structures of Comparative-1, Comparative-2 and Surfactant-1 described in the table are shown below.
[0101]
Embedded image

[0102]
[Table 1]

[0103]
As is apparent from the results of Table 1, the dye of the present invention and the ink jet recording liquid containing the dye are superior in light resistance as compared to the case of using the comparative dye and the ink jet recording liquid containing the comparative dye, and It can be seen that the color tone with less irregular absorption in the blue light and red light regions with respect to the reflection density in the green light region is good.
[0104]
Furthermore, it could be used without any problem in the continuous discharge test in this printer, and the high reliability of the ink jet recording liquid of the present invention for the electro-mechanical conversion method was confirmed.
[0105]
Example 2
Using each ink composition having the composition shown in Table 2, an ink jet printer BJC-600J (manufactured by Canon, electro-thermal conversion method) was used to obtain a sample recorded on glossy paper for exclusive use for ink jet. Table 2 shows the results of evaluating light resistance and color tone using this sample in the same manner as in Example 1. The unit of each compound amount in Table 2 is% by weight in the ink jet recording liquid, and the definitions of Comparative-1, Comparative-2 and evaluation items are the same as in Example 1.
[0106]
[Table 2]

[0107]
As is apparent from the results of Table 2, the dye of the present invention and the ink jet recording liquid containing the dye are superior in light resistance as compared to the case where the comparative dye and the ink jet recording liquid containing the comparative dye are used, and It can be seen that the color tone with less irregular absorption in the blue light and red light regions with respect to the reflection density in the green light region is good. Further, in the printer system, no abnormality of the head due to thermal alteration of the ink jet recording liquid of the present invention was confirmed, and it was confirmed that it had compatibility with the electro-thermal conversion method.
[0108]
【The invention's effect】
The dye according to the present invention, the ink jet recording liquid containing the dye, and particularly the magenta ink jet recording liquid as a main object are excellent in light resistance of color images and excellent in color tone for good color reproducibility. Have.
[Brief description of the drawings]
FIG. 1 shows a visible / ultraviolet spectral absorption spectrum of Example Compound I-1 in a methanol solution.
FIG. 2 shows a visible / ultraviolet spectral absorption spectrum of Exemplified Compound I-2 in a methanol solution.
FIG. 3 shows a visible / ultraviolet spectral absorption spectrum of Example Compound I-3 in a methanol solution.
FIG. 4 shows a visible / ultraviolet spectral absorption spectrum of Exemplified Compound I-4 in a methanol solution.
FIG. 5 shows a visible / ultraviolet spectral absorption spectrum of Exemplified Compound I-5 in a methanol solution.
FIG. 6 shows a visible / ultraviolet spectral absorption spectrum of Example Compound I-8 in a methanol solution.
FIG. 7 shows a visible / ultraviolet spectral absorption spectrum of Exemplified Compound I-16 in a methanol solution.

Claims (2)

An azomethine compound represented by the following general formula (1):

[Wherein, R ₁ represents a hydrogen atom, an alkyl group, an unsubstituted alkenyl group, an unsubstituted alkynyl group or an aralkyl group, and R ₂ represents a hydrogen atom, an alkyl group, an unsubstituted alkenyl group, or an unsubstituted alkynyl group. Represents an aralkyl group, an aromatic group or a heterocyclic group, and R ₁ may form a ring together with R ₂ . R ₃ represents an alkyl group having a Hammett σp value of −0.3 or more and 0.5 or less, and R ₄ represents an alkyl group, an alkoxy group, a halogen atom, an acylamino group, a ureido group, an alkoxycarbonyl group or a sulfonylamino group. N represents 0 or 1. One of X ₁ and X ₂ represents CR (R represents a hydrogen atom, alkyl group, alkoxy group, halogen atom, acylamino group, ureido group, alkoxycarbonyl group or sulfonylamino group), and the other represents a nitrogen atom. One of Y and Z represents a CR ′ (R ′ represents an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group) group, and the other represents a nitrogen atom. Furthermore, at least one of the substituents represented by R ₁ , R ₂ , R ₃ , R ₄ , R and R ′ is a group containing a sulfonic acid group, a carboxylic acid group or a salt thereof. ] The azomethine compound represented by the general formula (1) is 0.1 wt% or more and 20.0 wt% or less, water is 1.0 wt% or more and 98.9 wt% or less, and the water-soluble organic solvent is 1.0 wt%. An ink jet recording liquid, comprising at least 9% by weight and no more than 98.9% by weight.

Images