JP2004042547A - Color image forming method - Google Patents

Abstract

（式中、Ｚは置換基を有していても良い、ベンゼン環又はナフタレン環形成原子群を表し、Ｒはスルホ基又は置換基を有していても良いアミノ基を表す。）
【選択図】　なしAn ink jet system uses an ink that sufficiently satisfies all the properties required for an ink used in an ink jet system in a well-balanced manner. The ink jet system has excellent color images, particularly, excellent light fastness and fastness such as ozone fastness. Form an image.
In a method for forming a color image by ejecting aqueous inks of magenta, yellow, and cyan or magenta, yellow, cyan, and black by an inkjet method, the magenta ink has a free acid type represented by the following general formula [ A compound containing one or more metal-containing azo dyes formed from the compound represented by I] and a salt of Cu, Co or Ni is used.
Embedded image

(In the formula, Z represents a benzene ring or a naphthalene ring-forming atom group which may have a substituent, and R represents a sulfo group or an amino group which may have a substituent.)
[Selection diagram] None

Description

（式中、Ｚは置換基を有していても良い、ベンゼン環又はナフタレン環形成原子群を表し、Ｒはスルホ基又は置換基を有していても良いアミノ基を表す。）
【０００８】
即ち、本発明者らは、インクジェット方式に用いられるインクに要求される前記（１）〜（４）の特性は、インクに含有される水溶性色素の特性に大きく左右され、用いる水溶性色素の特定の組み合わせを選択することにより、前記（１）〜（４）の全ての特性を満足し、かつ得られるカラー画像も優秀であるカラー画像形成方法を与えることができることを見出し、本発明に至った。
【０００９】
インクジェット方式に用いられる水性インクの色素としては、種々の性能が要求されるが、特にカラー画像を形成する場合には、一般的な性能に加えてマゼンタ、イエロー及びシアン或いはマゼンタ、イエロー、シアン及びブラックの各色素の耐光性、耐オゾン性、耐水性等の性能が相互にバランスがとれており、かつ相互の演色関係が良好であることが重要である。従来において、このような特性を備えた３色或いは４色の色素の組合せを得ることは極めて困難なことであったが、本発明によれば、マゼンタインクとして特定の含金属アゾ色素を用いることにより、更に好ましくは、特定の色素の組合せによって、インクジェット方式による最良なカラー画像の形成方法が実現された。
【００１０】
【発明の実施の形態】
以下に本発明のカラー画像の形成方法の実施の形態を詳細に説明する。
【００１１】
本発明においては、インクジェット方式により、マゼンタ、イエロー及びシアン或いはマゼンタ、イエロー、シアン及びブラックの水性インクを吐出してカラー画像を形成するに当たり、マゼンタインクとして、遊離酸の型が下記一般式［Ｉ］、好ましくは下記一般式［Ｉ−Ａ］で表される化合物と、Ｃｕ、Ｃｏ又はＮｉの塩とから形成される含金属アゾ色素の一種以上を含有するものを用いる。
【００１２】
【化２５】

（式中、Ｚは置換基を有していても良い、ベンゼン環又はナフタレン環形成原子群を表し、Ｒはスルホ基又は置換基を有していても良いアミノ基を表す。）
【００１３】
【化２６】

（式中、Ｒ^１は水素原子、−ＳＯ_３Ｈ、−ＣＯＯＨ、ハロゲン原子、又はニトロ基を表し、Ｒ^２は−ＳＯ_３Ｈ、アシルアミノ基を表す。）
【００１４】
上記一般式［Ｉ］、好ましくは上記一般式［Ｉ−Ａ］で表される化合物と、Ｃｕ、Ｃｏ又はＮｉとの塩とからなる含金属アゾ色素としては、特に制限はないが、好ましい具体例としては下記のような化合物と金属塩とで形成されるものが挙げられる。
【００１５】
【表１】

【００１６】
【表２】

【００１７】
【表３】

【００１８】
このような含金属アゾ色素は、公知の方法、例えば、特開昭６３−３０５７２号公報に記載される方法により製造することができる。
【００１９】
本発明においては、マゼンタインクとしては、濃度の異なる２種のインクを用い、色濃度の低い淡色のマゼンタインクとして、上記含金属アゾ色素の一種以上を含有するものを用い、色濃度の高い濃色のマゼンタインクとして、遊離酸の型が下記一般式（Ａ）〜（Ｆ）で表される色素からなる群から選択される色素の一種以上を含有するものを用いることが好ましい。
【００２０】
【化２７】

【００２１】
（式中、Ｒ^Ａ１、Ｒ^Ａ２及びＲ^Ａ３は、それぞれ独立に、置換基を有していても良い炭素数１〜９のアルキル基、炭素数１〜９のアルコキシ基、ハロゲン原子、水素原子、ヒドロキシル基、置換基を有していても良いカルバモイル基、置換基を有していても良いスルファモイル基、置換基を有していても良いアミノ基、ニトロ基、スルホン酸エステルの基、炭素数１〜９のアルキルスルホニル基、炭素数６〜１５のアリールスルホニル基、カルボキシル基、又は、カルボン酸エステルの基を表す。
ａは０、１又は２を表す。
Ｒ^Ａ４、Ｒ^Ａ５及びＲ^Ａ６は、それぞれ独立に、水素原子、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、アリール基、アラルキル基、芳香族炭化水素環基、又は複素環基を表し、これらのうち水素原子以外は置換基を有していても良い。）
【００２２】
【化２８】

【００２３】
（式中、Ｒ^Ｂ１及びＲ^Ｂ２は、−ＯＲ^ｂ１、−ＮＲ^ｂ２Ｒ^ｂ３又は塩素原子を表し、Ｒ^ｂ１、Ｒ^ｂ２及びＲ^ｂ３は、水素原子、炭素数１〜８のアルキル基、炭素数２又は３のアルケニル基、アリール基、アラルキル基、シクロアルキル基、或いは含窒素複素環基を表し、これらのうち水素原子以外の基は更に置換基を有していても良く、またＲ^ｂ２及びＲ^ｂ３は結合される窒素原子と共に５員環又は６員環を形成していても良い。
Ｙ^Ｂ１は下記一般式（１）〜（４）で表される基及び下記構造式（５）〜（８）で表される基から選ばれる二価の結合基を示す。
【化２９】

（式中、Ｙ^１１及びＹ^１２はそれぞれ独立に炭素数１〜８の直鎖状又は分岐鎖状のアルキレン基を表し、Ｙ^１０は炭素数１〜１２の直鎖状又は分岐鎖状のアルキレン基を表し、ｂは０〜２０の整数を表す。）
【化３０】

（式中、Ｙ^１３及びＹ^１４はそれぞれ独立に炭素数１〜８の直鎖状又は分岐鎖状のアルキレン基を表す。）
【化３１】

（式中、Ｒ^１１及びＲ^１２は水素原子又はメチル基を表す。）
【化３２】

（式中、Ｒ^１３及びＲ^１４はそれぞれ独立に水素原子、メチル基又はメトキシ基を表す。）
【化３３】

Ａｒ^Ｂ１及びＡｒ^Ｂ２は、それぞれ独立に、置換基を有していても良いフェニル基又は置換基を有していても良いナフチル基を表す。）
【００２４】
【化３４】

【００２５】
（式中、Ａｒ^Ｃ１、Ａｒ^Ｃ２はそれぞれ独立に置換基を有していても良いアリール基を表し、Ａｒ^Ｃ１、Ａｒ^Ｃ２の少なくとも一つは置換基として−ＣＯＯＨ及び−ＣＯＳＨから選ばれた置換基を少なくとも一つ有する。
Ｒ^Ｃ１及びＲ^Ｃ２はそれぞれ独立に水素原子、置換基を有していても良いアルキル基又は置換基を有していても良いアルケニル基を表す。
Ｙ^Ｃは下記の基を表す。
【化３５】

Ｙ^Ｃ１は２価の有機結合基を表し、ｃは０又は１であり、Ｙ^Ｃ２はカルボニル基又は下記の式▲１▼〜▲３▼で表される基を表す。
【化３６】

（式中、Ｚ^１１はＮＲ^２１Ｒ^２２、ＳＲ^２３又はＯＲ^２３を表し、Ｚ^１２は水素原子、塩素原子、Ｚ^１１、ＳＲ^２４又はＯＲ^２４を表し、Ｚ^１３は塩素原子又はシアノ基を表す。Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４はそれぞれ独立に水素原子、置換基を有していても良いアルキル基、置換基を有していても良いアルケニル基、置換基を有していても良いアリール基、又は置換基を有していても良いアラルキル基を表すが、Ｒ^２１、Ｒ^２２は結合された窒素原子と共に５員環又は６員環を形成していても良い。））
【００２６】
【化３７】

【００２７】
（式中、Ｒ^Ｄ１は水素原子、メチル基、メトキシ基、アセチルアミノ基、又はニトロ基を表すが、ベンゼン環ｄの３位の炭素原子と共にベンゼン環を形成していても良い。
Ｒ^Ｄ２はアセチル基、ベンゾイル基、パラトルエンスルホニル基、又は４−クロル−６−ヒドロキシ−１，３，５−トリアジン−２−イル基を表す。）
【００２８】
【化３８】

【００２９】
（式中、Ｒ^Ｅ１は水素原子又は炭素数１〜６の脂肪族基を表す。
Ｒ^Ｅ２は水素原子、置換基としてのＣＮ基、ＣＯＯＲ^ｅ基（Ｒ^ｅは水素原子、金属原子、又は置換基を有していても良いアンモニウム基を表す。）、ＯＨ基、ＣＯＯＣＨ_３基、ＣＯＯＣＨ_２ＣＨ_３基で置換基を有していても良い、炭素数１〜６のアルキル基、又はメチル基で置換基を有していても良いアリール基を表す。
ｅは２〜４の整数を表す。
Ｒ^Ｅ３は置換基を有していても良いアミノ基、アルキルチオ基、ヒドロキシル基又はアルコキシ基を表す。）
【００３０】
【化３９】

【００３１】
（式中、Ｒ^Ｆ１は水素原子又は置換基を有していても良いアルキル基を表し、Ｒ^Ｆ２はＣＯＲ^ｆ基、ＳＯ_２Ｒ^ｆ基、又は下記一般式▲４▼で表される基を表す。ここで、Ｒ^ｆは置換基を有していても良いアルキル基又は置換基を有していても良いフェニル基を表す。）
【００３２】
【化４０】

（式中、Ｒ^ｆ１はそれぞれ独立にＣＯＯＨ基又はＳＯ_３Ｈ基を表し、Ｒ^ｆ２はそれぞれ独立に置換基を有していても良いアミノ基を表し、Ｒ^ｆ３はそれぞれ独立にＲ^ｆ１及びＲ^ｆ２で定義した以外の置換基を表し、ｍ，ｎ，ｐはそれぞれ独立に０〜３の整数を表し、（ｍ＋ｎ＋ｐ）は０〜５の整数である。
Ｙ^ｆは−Ｏ−、−Ｓ−、−ＮＲ^ｆ５を表し、Ｙ^ｆ４は−ＯＲ^ｆ６を表す。ここでＲ^ｆ５、Ｒ^ｆ６はそれぞれ独立に置換基を有していても良いアルキル基又は置換基を有していても良いフェニル基を表す。）
【００３３】
遊離酸の型が前記一般式（Ａ）で表される色素としては、次のようなものが挙げられる。
【００３４】
【化４１】

【００３５】
【化４２】

【００３６】
【化４３】

【００３７】
【化４４】

【００３８】
【化４５】

【００３９】
【化４６】

【００４０】
【化４７】

【００４１】
【化４８】

【００４２】
【化４９】

【００４３】
【化５０】

【００４４】
【化５１】

【００４５】
【化５２】

【００４６】
【化５３】

【００４７】
【化５４】

【００４８】
遊離酸の型が前記一般式（Ｂ）で表される色素としては、次のようなものが挙げられる。
【００４９】
【化５５】

【００５０】
【化５６】

【００５１】
【化５７】

【００５２】
【化５８】

【００５３】
【化５９】

【００５４】
【化６０】

【００５５】
【化６１】

【００５６】
【化６２】

【００５７】
【化６３】

【００５８】
【化６４】

【００５９】
【化６５】

【００６０】
【化６６】

【００６１】
【化６７】

【００６２】
【化６８】

【００６３】
【化６９】

【００６４】
【化７０】

【００６５】
【化７１】

【００６６】
【化７２】

【００６７】
遊離酸の型が前記一般式（Ｃ）で表される色素としては、次のようなものが挙げられる。
【００６８】
【化７３】

【００６９】
【化７４】

【００７０】
遊離酸の型が前記一般式（Ｄ）で表される色素としては、次のようなものが挙げられる。
【００７１】
【化７５】

【００７２】
【化７６】

【００７３】
【化７７】

【００７４】
【化７８】

【００７５】
【化７９】

【００７６】
【化８０】

【００７７】
遊離酸の型が前記一般式（Ｅ）で表される色素としては、次のようなものが挙げられる。
【００７８】
【化８１】

【００７９】
【化８２】

【００８０】
【化８３】

【００８１】
【化８４】

【００８２】
【化８５】

【００８３】
前記一般式（Ｆ）で表される色素としては、次のようなものが挙げられる。
【００８４】
【化８６】

【００８５】
【化８７】

【００８６】
【化８８】

【００８７】
本発明においては、かかるマゼンタインク以外のインクとしては特に制限はないが、次のようなものが好ましい。
【００８８】
［イエローインク］
カラーインデックス（Ｃ．Ｉ．）でアシッドイエロー２３、ダイレクトイエロー８６、１３２、１４２及び１７３、並びに遊離酸の型が下記一般式［ＩＩ］で示される色素からなる群から選択される色素の一種以上を含有するもの。
【００８９】
【化８９】

【００９０】
（式中、Ａｒ^２１、Ａｒ^２２はそれぞれ独立に置換基を有していても良いアリール基を表し、Ａｒ^２１、Ａｒ^２２の少なくとも一つはＣＯＯＨ基及びＣＯＳＨ基から選択される置換基を少なくとも一つ有する。
Ｙ^２１、Ｙ^２２はそれぞれ独立に下記一般式（ａ）、（ｂ）又は（ｃ）で表される連結基である。
【００９１】
【化９０】

（式中、Ｒ^３１は水素原子、置換基を有していても良いアルキル基、アルコキシハロゲン基、シアノ基、ウレイド基又はＮＨＣＯＲ^３５基を表し、Ｒ^３５は水素原子、置換基を有していても良いアルキル基、置換基を有していても良いアリール基、又は置換基を有していても良いアラルキル基を表す。
Ｒ^３２はアルキル基であり、Ｒ^３３は水素原子、シアノ基、ＣＯＮＲ^３６Ｒ^３７基（Ｒ^３６、Ｒ^３７はそれぞれ独立に水素原子又は置換基を有していても良いアルキル基を表す。）、ピリジニウム基又はＣＯＯＨ基を表し、Ｙ^３０は炭素数２〜８のアルキレン基を表す。
Ｒ^３４は水素原子、アルキル基又はＣＯＯＨ基を表す。）
Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４はそれぞれ独立に水素原子又は置換基を有していても良いアルキル基を表す。
Ｙ^２３は２価の連結基を表す。
Ｙ^２４、Ｙ^２５はそれぞれ独立にカルボニル基又は下記一般式▲４▼〜▲６▼で表される基を表す。
【００９２】
【化９１】

（式中、Ｚ^２１はＯＲ^４１、ＳＲ^４１又はＮＲ^４２Ｒ^４３を表し、Ｚ^２２は水素原子、塩素原子又はシアノ基を表し、Ｚ^２３は塩素原子又はシアノ基を表す。Ｒ^４１、Ｒ^４２、Ｒ^４３はそれぞれ独立に水素原子、置換基を有していても良いアルキル基、置換基を有していても良いアルケニル基、置換基を有していても良いアリール基、又は置換基を有していても良いアラルキル基を表すが、Ｒ^４２及びＲ^４３はこれらが結合された窒素原子と共に５員環又は６員環を形成していても良い。）
ｈは０又は１を表す。
ただし、この一般式［ＩＩ］で表される化合物がＳＯ_３Ｈ基を持たない場合は少なくとも２つのＣＯＯＨ基及びＣＯＳＨ基から選ばれた基を有し、一般式（ＩＩ）で表される化合物がＳＯ_３Ｈ基を持つ場合はＣＯＯＨ基及びＣＯＳＨ基から選ばれた基をＳＯ_３Ｈ基と同数以上有する。）
【００９３】
［シアンインク］
カラーインデックス（Ｃ．Ｉ．）でダイレクトブルー８６、及び１９９、アシッドブルー９、並びに遊離酸の型が下記一般式［ＩＩＩ］で示される化合物からなる群から選択される色素の一種以上を含有するもの。
【００９４】
【化９２】

【００９５】
（式中、Ｐｃは金属を含有するフタロシアニン核であり、Ｒ^５１、Ｒ^５２、Ｒ^５３はそれぞれ独立に水素原子、置換基を有していても良いアルキル基、置換基を有していても良いアルケニル基、又は置換基を有していても良いアラルキル基であり、Ｙ^５１は２価の連結基であり、Ｙ^５２はカルボニル基又は下記一般式▲７▼〜▲９▼で表される基を表す。
【化９３】

（式中、Ｚ^３１はＮＲ^６１Ｒ^６２、ＳＲ^６３又はＯＲ^６３を表し、Ｚ^３２は水素原子、塩素原子、Ｚ^３１、ＳＲ^６４又はＯＲ^６４を表し、Ｚ^３３は塩素原子又はシアノ基を表す。Ｒ^６１、Ｒ^６２、Ｒ^６３、Ｒ^６４はそれぞれ独立に水素原子、置換基を有していても良いアルキル基、置換基を有していても良いアリール基、又は置換基を有していても良いアラルキル基を表すが、Ｒ^６１及びＲ^６２はこれらが結合された窒素原子と共に５員環又は６員環を形成していても良い。）
ＧはＣＯＳＨ基及びＣＯＯＨ基から選択された１個又は２個の基によって置換された無色の有機基を表す。
（ｊ＋ｋ）は３又は４である。
ただし、一般式［ＩＩＩ］で表される化合物は少なくとも一つのＳＯ_３Ｈ基を有し、かつＣＯＳＨ基及びＣＯＯＨ基から選択された基をＳＯ_３Ｈ基と同数以上有する。）
【００９６】
［ブラックインク］
カラーインデックス（Ｃ．Ｉ．）でフードブラック２、ダイレクトブラック１７、１９、１５４、１６３、１６８、１７１、１９５、及び２００、アシッドブラック２、リアクティブブラック３１、ポンタミンブラックＳＰリキッド、バスアシッドブラックＸ−３４、並びに遊離酸の型が下記一般式［ＩＶａ］、［ＩＶｂ］及び［ＩＶｃ］で示される色素からなる群から選択される色素の一種以上を含有するもの。なお、ポンタミンブラックＳＰリキッドは、インクジェットインク用色素としてバイエル社が販売している色素の商品名であり、バスアシッドブラックＸ−３４はＢＡＳＦ社が販売している色素の商品名である。
【００９７】
【化９４】

（式中、ｐは１、２又は３を表し、ｑは０又は１を表す。）
【００９８】
【化９５】

（式中、Ａｒ^ａ、Ａｒ^ｂはそれぞれ独立に置換基を有していても良いベンゼン環又は置換基を有していても良いナフタレン環を表し、ｒは０又は１を表す。）
【００９９】
【化９６】

（式中、Ｒ’は水素原子、低級アルキル基又はＳＯ_３Ｈ基で置換基を有していても良いフェニル基を表し、ｔは０又は１を表す。
Ａｒ^ｃ、Ａｒ^ｄ、Ａｒ^ｅはそれぞれ独立に置換基を有していても良いベンゼン環又は置換基を有していても良いナフタレン環を表す。ただし、Ａｒ^ｄとＡｒ^ｅは同時にナフタレン環を表すことはない。）
【０１００】
イエローインクに使用される遊離酸の型が前記一般式（ＩＩ）で示される化合物の具体例として一例を挙げると、以下のものが挙げられる。
【０１０１】
【化９７】

【０１０２】
シアンインクに使用される遊離酸の型が前記一般式（ＩＩＩ）で示される化合物の具体例として一例を挙げると、以下のものが挙げられる。
【０１０３】
【化９８】

【０１０４】
ブラックインクに使用される遊離酸の型が前記一般式［ＩＶａ］で表される色素の具体例としては、以下の色素が挙げられる。
【０１０５】
【化９９】

【０１０６】
ブラックインクに使用される遊離酸の型が前記一般式［ＩＶｂ］で表される色素の具体例としては、以下の色素が挙げられる。
【０１０７】
【化１００】

【０１０８】
ブラックインクに使用される遊離酸の型が前記一般式［ＩＶｃ］で表される色素の具体例としては、以下の色素が挙げられる。
【０１０９】
【化１０１】

【０１１０】
各インク中における上述の特定の色素の含有量としては、インク全量に対して０．１〜８重量％、特に０．５〜５重量％程度が好ましい。
マゼンタインク及びシアンインクについては、好ましくは、濃淡２種のインク、即ち、色濃度の異なる２種のインクが用いられるが、この場合、色濃度の低い淡色インクの全色素濃度はインク全量に対して通常０．１〜２重量％程度であることが好ましく、色濃度の高い濃色インクの全色素濃度はインク全量に対して通常０．５〜８重量％程度であることが好ましく、濃色インクと淡色インクの全色濃度差は０．４〜６重量％程度であることが好ましい。
【０１１１】
本発明で用いられるインクの水性媒体としては、水及び水溶性有機溶剤の混合媒体が好ましく、水と混合する水溶性有機溶剤としては、例えばエチレングリコール、プロピレングリコール、ブチレングリコール、ジエチレングリコール、トリエチレングリコール、１，２，６−ヘキサントリオール、チオジグリコール、ヘキシレングリコール等のアルキレン基が２〜６個の炭素原子を含むアルキレングリコール類；ポリエチレングリコール（重量平均分子量約１９０〜４００）、ポリプロピレングリコール等のポリアルキレングリコール類；グリセリン；Ｎ−メチル−２−ピロリドン、Ｎ−エチルピロリドン；１，３−ジメチル−２−イミダゾリジノン；チオジエタノール；ジメチルスルホキシド；エチレングリコールモノアリルエーテル、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、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エチルエーテル、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等の多価アルコールの低級アルキルエーテル類；２−ピロリドン；スルホラン；メチルアルコール、エチルアルコール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、ｓｅｃ−ブタノール、ｔｅｒｔ−ブタノール、イソブタノール等の炭素数１〜４のアルキルアルコール類；ジメチルホルムアミド、ジメチルアセトアミド等のアミド類；アセトン、ジアセトンアルコール等のケトン又はケトンアルコール類；テトラヒドロフラン、ジオキサン等のエーテル類等を含有していることが好ましい。これらの水溶性有機溶剤の中でも、ジエチレングリコール等の多価アルコール、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等の多価アルコールの低級アルキルエーテルが好ましい。
【０１１２】
これらの水溶性有機溶剤は、通常インクの全量に対して１〜７０重量％の範囲で使用されるが、好ましくは１０〜５０重量％の範囲である。一方、水はインクの全量に対して４５〜９５重量％の範囲で使用される。
【０１１３】
本発明において、インク中にその全量に対して０．１〜１０重量％、好ましくは０．５〜５重量％の尿素、チオ尿素、ビウレット、セミカルバジドから選ばれる化合物を添加したり、また、０．００１〜５．０重量％の界面活性剤、その他ポリビニルアルコール、セルロース類、水溶性樹脂等の粘度調整剤、ジエタノールアミン、トリエタノールアミン等の表面張力調整剤、緩衝液等によるｐＨ調整剤、防黴剤等を添加することによって、インク品質、印字後の速乾性及び印字品位等をより一層改良することができる。
【０１１４】
本発明において、各インクは上記のような使用する色素の条件を満たすものであれば、その調製方法は特に限定されない。
【０１１５】
本発明のカラー画像の形成方法は、このようなインクを用いて、インクジェット方式の常法に従って各インクをオリフィスから吐出させて印刷を行うものであり、上記のような特定のマゼンタの水性インクと、イエロー、シアン或いはイエロー、シアン及びブラックの水性インクとを使用することによって、良好なフルカラー印刷等のカラー画像の形成を行うことができる。
【０１１６】
【実施例】
以下に、実施例及び比較例を挙げて本発明をより具体的にに説明するが、本発明はその要旨を超えない限り、何ら以下の実施例に限定されるものではない。なお、以下において、「部」、「％」は特記しない限りそれぞれ「重量部」、「重量％」を示す。
【０１１７】
実施例１
ジエチレングリコール、ジエチレングリコールモノブチルエーテル及び水からなる混合溶媒に色素を加え、水酸化ナトリウム水溶液でｐＨを９に調整して全量を１００部とし、十分に混合して色素を溶解させた後、孔径１μｍのテフロン（登録商標）フィルターで加圧濾過し、次いで、真空ポンプ及び超音波洗浄機で脱気処理して、それぞれイエロー（Ｙ）、シアン（Ｃ）、ブラック（Ｂｋ）及びマゼンタ（Ｍ）の水性インクを調製した。インクの組成は表４に示す通りであり、また、使用した各色素及びその使用量は表５に示す通りである。なお、マゼンタ色素のＮｏ．は前掲の化合物Ｎｏ．に対応するものである。
【０１１８】
【表４】

【０１１９】
【表５】

【０１２０】
得られたインクを使用してインクジェットプリンター（商品名ＰＭ−７５０Ｃ、セイコーエプソン社製品）を用いて、電子写真用紙（商品名４０２４紙、ゼロックス社製品）、スーパーファイン専用紙（セイコーエプソン社製品）、スーパーファイン専用光沢紙（セイコーエプソン社製品）に各々インクジェット記録を行い、濃色部から淡色部までの階調を有するフルカラー画像印画物を得た。これらの印画物について下記の耐光性及び耐オゾン性の試験を実施した。
【０１２１】
［記録画像の耐光性］
キセノンフェードメーター（アトラス社製品）で印画物を８０時間照射した後、印画物の変退色を観察した。
【０１２２】
［記録画像の耐オゾン性］
オゾン濃度３ｐｐｍの遮光された槽内に印画物を２時間暴露した後、印画物の変退色を観察した。
【０１２３】
その結果、耐光性試験においても、耐オゾン性試験においても、各色の濃色部、淡色部及び混色部における変退色は小さく、耐光性、耐オゾン性はともに良好であった。
【０１２４】
実施例２〜６
実施例１において用いた色素の代わりに、各々下記表６〜１０に記載した色素を用いたこと以外は、実施例１と同様にして各インクを調製し、同様にインクジェット記録を行い、得られた記録物に対して耐光性及び耐オゾン性の試験を実施した。その結果、表１１に示す通り良好な結果が得られた。
【０１２５】
【表６】

【０１２６】
【表７】

【０１２７】
【表８】

【０１２８】
【表９】

【０１２９】
【表１０】

【０１３０】
比較例１
Ｍ（淡色）のインクの色素としてＡ−８の色素を０．６部使用したこと以外は実施例１と同様にして各インクを調製し、同様にインクジェット記録を行い、得られた記録物に対して耐光性及び耐オゾン性の試験を実施し、結果を表１１に示した。
【０１３１】
比較例２
Ｍ（濃色）、Ｍ（淡色）のインクの色素としてＣ．Ｉ．リアクティブレッド１８０を各々２．５部、０．６部使用したこと以外は実施例１と同様にして各インクを調製し、同様にインクジェット記録を行い、得られた記録物に対して耐光性及び耐オゾン性の試験を実施し、結果を表１１に示した。
【０１３２】
比較例３
Ｍ（濃色）、Ｍ（淡色）のインクの色素としてＣ．Ｉ．アシッドレッド３７を各々３．０部、０．７部使用したこと以外は実施例１と同様にして各インクを調製し、同様にインクジェット記録を行い、得られた記録物に対して耐光性及び耐オゾン性の試験を実施し、結果を表１１に示した。
【０１３３】
【表１１】

【０１３４】
【発明の効果】
以上詳述した通り、本発明のカラー画像の形成方法によれば、インクジェット方式による画像形成において、特定の色素を使用したマゼンタの水性インクと、イエロー及びシアン或いはイエロー、シアン及びブラックの水性インクとを使用することにより、耐光性、耐オゾン性においてバランスのとれた、堅牢性の良好なカラー画像記録物を得ることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for forming a color image, and more particularly, to a method for forming a full-color image by ejecting aqueous inks of magenta, yellow, and cyan or magenta, yellow, cyan, and black by an inkjet method.
[0002]
[Prior art]
The ink-jet method is a method in which small droplets of ink are ejected from an orifice by various methods and adhered to a recording material to perform recording. The ink used in such an ink-jet method has the following performance. Required.
[0003]
(1) In addition to papers such as electrophotographic paper, fan hold paper, uncoated paper such as bond paper, art paper or coated paper, polyester film, polyvinyl chloride film, etc. Good recording can be performed on an aqueous resin formed on such a non-porous film, or on a film composed of an aqueous resin and organic or inorganic fine particles.
(2) To give an image excellent in water resistance, light resistance and ozone resistance.
(3) The dissolution or storage stability with respect to the liquid medium component is high, and the discharge orifice is unlikely to be clogged.
(4) To give an image with high optical density, clear color tone and good reproducibility.
[0004]
In order to satisfy such strict requirements, conventionally, for example, JP-A-54-89811, JP-A-55-54367, JP-A-57-164170, JP-A-57-195775, and JP-A-57-195775. 197191, JP-A-58-12786, JP-A-59-106989, JP-A-62-199665, JP-A-62-199666, JP-A-62-199667, JP-A-63-28690 Although a large number of patent applications have been filed, unlike dyes having a specific structural formula as used in the present invention, no satisfactory dyes have yet been proposed.
[0005]
[Problems to be solved by the invention]
The present invention uses an ink that satisfies all of the above requirements (1) to (4) in a well-balanced manner, and uses an ink-jet method to provide an excellent color image, particularly an image having good light fastness and good fastness such as ozone fastness. And a method for forming a color image.
[0006]
[Means for Solving the Problems]
The method of forming a color image of the present invention is a method of forming a color image by ejecting aqueous inks of magenta, yellow and cyan or magenta, yellow, cyan and black by an ink jet method, wherein the magenta ink contains free acid It is characterized in that the mold contains one or more metal-containing azo dyes formed from a compound represented by the following general formula [I] and a salt of Cu, Co or Ni.
[0007]
Embedded image

(In the formula, Z represents a benzene ring or a naphthalene ring-forming atom group which may have a substituent, and R represents a sulfo group or an amino group which may have a substituent.)
[0008]
That is, the present inventors have determined that the characteristics (1) to (4) required for the ink used in the ink-jet method largely depend on the characteristics of the water-soluble dye contained in the ink. It has been found that by selecting a specific combination, it is possible to provide a color image forming method which satisfies all of the above-mentioned characteristics (1) to (4) and provides an excellent color image. Was.
[0009]
Various performances are required as the pigment of the water-based ink used in the ink jet system. In particular, when a color image is formed, magenta, yellow and cyan or magenta, yellow, cyan and It is important that the performance of each dye of black such as light fastness, ozone fastness and water fastness is balanced with each other and that the mutual color rendering relationship is good. Conventionally, it has been extremely difficult to obtain a combination of three or four colors of dyes having such characteristics. However, according to the present invention, a specific metal-containing azo dye is used as a magenta ink. More preferably, the best color image forming method by the ink jet system was realized by a specific dye combination.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the color image forming method of the present invention will be described in detail.
[0011]
In the present invention, when a magenta, yellow, and cyan or magenta, yellow, cyan, and black aqueous inks are ejected to form a color image by an inkjet method, the magenta ink has a free acid type represented by the following general formula [I Preferably, a compound containing at least one metal-containing azo dye formed from a compound represented by the following general formula [IA] and a salt of Cu, Co or Ni is used.
[0012]
Embedded image

(In the formula, Z represents a benzene ring or a naphthalene ring-forming atom group which may have a substituent, and R represents a sulfo group or an amino group which may have a substituent.)
[0013]
Embedded image

(In the formula, R ¹ represents a hydrogen atom, —SO ₃ H, —COOH, a halogen atom, or a nitro group, and R ² represents —SO ₃ H or an acylamino group.)
[0014]
The metal-containing azo dye comprising the compound represented by the general formula [I], preferably the compound represented by the general formula [IA], and a salt of Cu, Co or Ni is not particularly limited, but is preferably a specific example. Examples include those formed from the following compounds and metal salts.
[0015]
[Table 1]

[0016]
[Table 2]

[0017]
[Table 3]

[0018]
Such a metal-containing azo dye can be produced by a known method, for example, a method described in JP-A-63-30572.
[0019]
In the present invention, two types of inks having different densities are used as magenta inks, and those containing one or more of the above-described metal-containing azo dyes are used as light-colored magenta inks having a low color density. As the color magenta ink, it is preferable to use an ink whose free acid type contains one or more dyes selected from the group consisting of the dyes represented by the following general formulas (A) to (F).
[0020]
Embedded image

[0021]
(Wherein, R ^A1 , R ^A2 and R ^A3 each independently represent an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, a halogen atom, a hydrogen atom, , A hydroxyl group, a carbamoyl group which may have a substituent, a sulfamoyl group which may have a substituent, an amino group which may have a substituent, a nitro group, a sulfonic acid ester group, carbon Represents an alkylsulfonyl group having 1 to 9 carbon atoms, an arylsulfonyl group having 6 to 15 carbon atoms, a carboxyl group, or a carboxylate group.
a represents 0, 1 or 2.
R ^A4 , R ^A5 and R ^A6 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group, an aralkyl group, an aromatic hydrocarbon ring group, or a heterocyclic group. Represents a ring group, and among these, a hydrogen atom other than a hydrogen atom may have a substituent. )
[0022]
Embedded image

[0023]
^{(Wherein, R B1} and ^{R B2,} -OR ^b1, represents ^-NR b2 ^{R b3} or chlorine ^atom, R ^{b1, R b2} and ^{R b3} represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, carbon atoms Represents an alkenyl group, an aryl group, an aralkyl group, a cycloalkyl group, or a nitrogen-containing heterocyclic group, wherein a group other than a hydrogen atom may further have a substituent, and R ^b2 and R ^b3 may form a 5- or 6-membered ring together with the nitrogen atom to be bonded.
Y ^B1 represents a divalent bonding group selected from groups represented by the following general formulas (1) to (4) and groups represented by the following structural formulas (5) to (8).
Embedded image

(Wherein, Y ¹¹ and Y ¹² each independently represent a linear or branched alkylene group having 1 to 8 carbon atoms, and Y ¹⁰ represents a linear or branched alkylene group having 1 to 12 carbon atoms. Represents a group, and b represents an integer of 0 to 20.)
Embedded image

(In the formula, Y ¹³ and Y ¹⁴ each independently represent a linear or branched alkylene group having 1 to 8 carbon atoms.)
Embedded image

(In the formula, R ¹¹ and R ¹² represent a hydrogen atom or a methyl group.)
Embedded image

(In the formula, R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a methyl group, or a methoxy group.)
Embedded image

Ar ^B1 and Ar ^B2 each independently represent a phenyl group which may have a substituent or a naphthyl group which may have a substituent. )
[0024]
Embedded image

[0025]
(In the formula, Ar ^C1 and Ar ^C2 each independently represent an aryl group which may have a substituent, and at least one of Ar ^C1 and Ar ^C2 is a substituent selected from —COOH and —COSH as a substituent. It has at least one group.
R ^C1 and R ^C2 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent.
Y ^C represents the following group.
Embedded image

Y ^C1 represents a divalent organic bonding group, c represents 0 or 1, and Y ^C2 represents a carbonyl group or a group represented by the following formulas (1) to (3).
Embedded image

(Wherein, Z ¹¹ represents NR ²¹ R ²² , SR ²³ or OR ²³ , Z ¹² represents a hydrogen atom, a chlorine atom, Z ¹¹ , SR ²⁴ or OR ²⁴ , and Z ¹³ represents a chlorine atom or a cyano group. R ²¹ , R ²² , R ²³ and R ²⁴ each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. Represents an aryl group or an aralkyl group which may have a substituent, and R ²¹ and R ²² may form a 5- or 6-membered ring together with the bonded nitrogen atom.))
[0026]
Embedded image

[0027]
(In the formula, R ^D1 represents a hydrogen atom, a methyl group, a methoxy group, an acetylamino group, or a nitro group, but may form a benzene ring together with the carbon atom at the 3-position of the benzene ring d.
^RD2 represents an acetyl group, a benzoyl group, a paratoluenesulfonyl group, or a 4-chloro-6-hydroxy-1,3,5-triazin-2-yl group. )
[0028]
Embedded image

[0029]
(Wherein, ^{RE 1} represents a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms).
R ^E2 represents a hydrogen atom, a CN group as a substituent, a COOR ^e group (R ^e represents a hydrogen atom, a metal atom, or an ammonium group which may have a substituent), an OH group, a COOCH ₃ group, COOCH ₂ CH _{3 represents an} optionally substituted alkyl group having 1 to 6 carbon atoms, or a methyl group, which represents an optionally substituted aryl group.
e represents an integer of 2 to 4.
^RE3 represents an amino group, an alkylthio group, a hydroxyl group or an alkoxy group which may have a substituent. )
[0030]
Embedded image

[0031]
(In the formula, R ^F1 represents a hydrogen atom or an alkyl group which may have a substituent, and R ^F2 represents a COR ^f group, a SO ₂ R ^f group, or a group represented by the following general formula (4). Here, R ^f represents an alkyl group which may have a substituent or a phenyl group which may have a substituent.)
[0032]
Embedded image

(In the formula, R ^f1 each independently represents a COOH group or an SO ₃ H group, R ^f2 each independently represents an amino group which may have a substituent, and R ^f3 each independently represent R ^f1 and R ^f. represents a substituent other than those defined for ^f2 , m, n, and p each independently represent an integer of 0 to 3, and (m + n + p) is an integer of 0 to 5.
Y ^f is -O -, - S -, - represents ^{NR f5, Y f4} represents ^{-OR f6.} Here, R ^f5 and R ^f6 each independently represent an alkyl group which may have a substituent or a phenyl group which may have a substituent. )
[0033]
Examples of the dye whose free acid type is represented by the general formula (A) include the following.
[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]
Examples of the dye whose free acid type is represented by the general formula (B) include the following.
[0049]
Embedded image

[0050]
Embedded image

[0051]
Embedded image

[0052]
Embedded image

[0053]
Embedded image

[0054]
Embedded image

[0055]
Embedded image

[0056]
Embedded image

[0057]
Embedded image

[0058]
Embedded image

[0059]
Embedded image

[0060]
Embedded image

[0061]
Embedded image

[0062]
Embedded image

[0063]
Embedded image

[0064]
Embedded image

[0065]
Embedded image

[0066]
Embedded image

[0067]
Examples of the dye whose free acid type is represented by the general formula (C) include the following.
[0068]
Embedded image

[0069]
Embedded image

[0070]
Examples of the dye whose free acid type is represented by the general formula (D) include the following.
[0071]
Embedded image

[0072]
Embedded image

[0073]
Embedded image

[0074]
Embedded image

[0075]
Embedded image

[0076]
Embedded image

[0077]
Examples of the dye whose free acid type is represented by the general formula (E) include the following.
[0078]
Embedded image

[0079]
Embedded image

[0080]
Embedded image

[0081]
Embedded image

[0082]
Embedded image

[0083]
Examples of the dye represented by the general formula (F) include the following.
[0084]
Embedded image

[0085]
Embedded image

[0086]
Embedded image

[0087]
In the present invention, the ink other than the magenta ink is not particularly limited, but the following is preferred.
[0088]
[Yellow ink]
One or more dyes having a color index (CI) selected from the group consisting of Acid Yellow 23, Direct Yellow 86, 132, 142 and 173, and a dye having a free acid type represented by the following general formula [II]: Containing.
[0089]
Embedded image

[0090]
(Wherein, Ar ²¹ and Ar ²² each independently represent an aryl group which may have a substituent, and at least one of Ar ²¹ and Ar ²² has at least a substituent selected from a COOH group and a COSH group. I have one.
Y ²¹ and Y ²² are each independently a linking group represented by the following general formula (a), (b) or (c).
[0091]
Embedded image

(Wherein, R ³¹ represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxyhalogen group, a cyano group, a ureido group or an NHCOR ³⁵ group, and R ³⁵ has a hydrogen atom and a substituent. Represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group.
R ³² is an alkyl group, R ³³ is a hydrogen atom, a cyano group, a CONR ³⁶ R ³⁷ group (R ³⁶ and R ³⁷ each independently represent a hydrogen atom or an alkyl group which may have a substituent). , A pyridinium group or a COOH group, and Y ³⁰ represents an alkylene group having 2 to 8 carbon atoms.
R ³⁴ represents a hydrogen atom, an alkyl group or a COOH group. )
R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl group which may have a substituent.
Y ²³ represents a divalent linking group.
Y ²⁴ and Y ²⁵ each independently represent a carbonyl group or a group represented by the following general formulas (4) to (6).
[0092]
Embedded image

^{(Wherein, Z 21} represents ^OR 41, ^{SR 41} or ^NR 42 ^{R 43, Z 22} represents a hydrogen atom, a chlorine atom or a cyano ^{group, Z 23} is ^{.R 41, R 42} representing a chlorine atom or a cyano group , R ⁴³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an aralkyl group which may be possessed, and R ⁴² and R ⁴³ may form a 5- or 6-membered ring together with the nitrogen atom to which they are bonded.)
h represents 0 or 1.
However, when the compound represented by the general formula [II] does not have an SO ₃ H group, the compound represented by the general formula (II) has at least two groups selected from a COOH group and a COSH group. There have groups selected from COOH group and COSH group SO ₃ H groups as many more if with SO ₃ H groups. )
[0093]
[Cyan ink]
Direct Blue 86 and 199 in color index (CI), Acid Blue 9 and one or more dyes whose free acid type is selected from the group consisting of compounds represented by the following general formula [III] thing.
[0094]
Embedded image

[0095]
(In the formula, Pc is a metal-containing phthalocyanine nucleus, and R ⁵¹ , R ⁵² , and R ⁵³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a substituent. A good alkenyl group or an aralkyl group which may have a substituent, Y ⁵¹ is a divalent linking group, and Y ⁵² is a carbonyl group or represented by the following general formulas (7) to (9) Represents a group.
Embedded image

(Wherein, Z ³¹ represents NR ⁶¹ R ⁶² , SR ⁶³ or OR ⁶³ , Z ³² represents a hydrogen atom, a chlorine atom, Z ³¹ , SR ⁶⁴ or OR ⁶⁴ , and Z ³³ represents a chlorine atom or a cyano group. R ⁶¹ , R ⁶² , R ⁶³ , and R ⁶⁴ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. And R ⁶¹ and R ⁶² may form a 5- or 6-membered ring together with the nitrogen atom to which they are bonded.)
G represents a colorless organic group substituted by one or two groups selected from a COSH group and a COOH group.
(J + k) is 3 or 4.
However, the compound represented by the general formula [III] has at least one SO ₃ H group, and has the same number or more of the groups selected from the COSH group and the COOH group as the SO ₃ H group. )
[0096]
[Black ink]
Food Index 2, Direct Black 17, 19, 154, 163, 168, 171, 195, and 200, Acid Black 2, Reactive Black 31, Pontamine Black SP Liquid, Bath Acid Black by Color Index (CI) X-34, and a compound whose free acid type contains one or more dyes selected from the group consisting of dyes represented by the following general formulas [IVa], [IVb] and [IVc]. Note that Ponamine Black SP Liquid is a trade name of a dye sold by Bayer as a dye for inkjet ink, and Bath Acid Black X-34 is a trade name of a dye sold by BASF.
[0097]
Embedded image

(In the formula, p represents 1, 2 or 3, and q represents 0 or 1.)
[0098]
Embedded image

(In the formula, Ar ^a and Ar ^b each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent, and r represents 0 or 1.)
[0099]
Embedded image

(In the formula, R ′ represents a hydrogen atom, a lower alkyl group or a phenyl group which may have a substituent with an SO ₃ H group, and t represents 0 or 1.
Ar ^c , Ar ^d , and Ar ^e each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent. However, Ar ^d and Ar ^e are not simultaneously represent a naphthalene ring. )
[0100]
Specific examples of the compound represented by the general formula (II) in which the type of free acid used in the yellow ink is represented by the general formula (II) include the following.
[0101]
Embedded image

[0102]
Specific examples of the compound in which the type of free acid used in the cyan ink is represented by the general formula (III) include the following.
[0103]
Embedded image

[0104]
Specific examples of the dye whose free acid type used in the black ink is represented by the general formula [IVa] include the following dyes.
[0105]
Embedded image

[0106]
Specific examples of the dye whose free acid type used in the black ink is represented by the general formula [IVb] include the following dyes.
[0107]
Embedded image

[0108]
Specific examples of the dye whose free acid used in the black ink is represented by the general formula [IVc] include the following dyes.
[0109]
Embedded image

[0110]
The content of the above-mentioned specific dye in each ink is preferably 0.1 to 8% by weight, particularly preferably about 0.5 to 5% by weight based on the total amount of the ink.
For the magenta ink and the cyan ink, preferably, two types of dark and light inks, that is, two types of inks having different color densities are used. In this case, the total dye density of the light color ink having a low color density is based on the total amount of the ink. Is preferably about 0.1 to 2% by weight, and the total dye density of the dark color ink having a high color density is preferably about 0.5 to 8% by weight based on the total amount of the ink. The total color density difference between the ink and the light color ink is preferably about 0.4 to 6% by weight.
[0111]
The aqueous medium of the ink used in the present invention is preferably a mixed medium of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent to be mixed with water include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, and triethylene glycol. , 1,2,6-hexanetriol, thiodiglycol, hexylene glycol and the like, alkylene glycols having an alkylene group containing 2 to 6 carbon atoms; polyethylene glycol (weight average molecular weight about 190 to 400), polypropylene glycol and the like Glycerin; N-methyl-2-pyrrolidone, N-ethylpyrrolidone; 1,3-dimethyl-2-imidazolidinone; thiodiethanol; dimethyl sulfoxide; ethylene glycol monoallyl ether; Lower alkyl ethers of polyhydric alcohols such as tylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; 2-pyrrolidone; sulfolane; methyl Alcohols having 1 to 4 carbon atoms such as alcohol, ethyl alcohol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol and isobutanol; amides such as dimethylformamide and dimethylacetamide; Contains ketones or ketone alcohols such as acetone alcohol; ethers such as tetrahydrofuran and dioxane It is preferred that. Among these water-soluble organic solvents, polyhydric alcohols such as diethylene glycol and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether are preferred.
[0112]
These water-soluble organic solvents are generally used in the range of 1 to 70% by weight, preferably 10 to 50% by weight, based on the total amount of the ink. On the other hand, water is used in the range of 45 to 95% by weight based on the total amount of the ink.
[0113]
In the present invention, a compound selected from urea, thiourea, biuret and semicarbazide is added to the ink in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the total amount of the ink. 0.0001-5.0% by weight of a surfactant, other viscosity modifiers such as polyvinyl alcohol, celluloses, and water-soluble resins, surface tension regulators such as diethanolamine and triethanolamine, pH regulators with a buffer solution and the like, By adding a fungicide or the like, ink quality, quick drying after printing, printing quality, and the like can be further improved.
[0114]
In the present invention, the preparation method of each ink is not particularly limited as long as it satisfies the above-described conditions of the dye to be used.
[0115]
The method of forming a color image of the present invention is to perform printing by discharging each ink from an orifice according to a conventional method of an ink jet system using such an ink, and the specific magenta aqueous ink as described above. By using yellow, cyan, or yellow, cyan, and black aqueous inks, it is possible to form a good color image such as full-color printing.
[0116]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples unless it exceeds the gist thereof. In the following, “parts” and “%” indicate “parts by weight” and “% by weight”, respectively, unless otherwise specified.
[0117]
Example 1
The dye is added to a mixed solvent consisting of diethylene glycol, diethylene glycol monobutyl ether and water, the pH is adjusted to 9 with an aqueous sodium hydroxide solution to make the total amount 100 parts, and the dye is sufficiently mixed to dissolve the dye. (R) filters, and then degassed with a vacuum pump and an ultrasonic cleaner to obtain aqueous inks of yellow (Y), cyan (C), black (Bk) and magenta (M), respectively. Was prepared. The composition of the ink is as shown in Table 4, and the dyes used and the amounts used are as shown in Table 5. In addition, the magenta dye No. Is the compound No. described above. It corresponds to.
[0118]
[Table 4]

[0119]
[Table 5]

[0120]
Using the obtained ink, an electrophotographic paper (product name: 4024 paper, product of Xerox Co., Ltd.), super fine paper (product of Seiko Epson Co., Ltd.) using an ink jet printer (product name: PM-750C, product of Seiko Epson) Ink jet recording was performed on glossy paper for exclusive use of Super Fine (manufactured by Seiko Epson Corporation) to obtain a full-color image print having gradations from dark to light. The following light fastness and ozone fastness tests were performed on these prints.
[0121]
[Light resistance of recorded images]
After the print was irradiated with a xenon fade meter (manufactured by Atlas) for 80 hours, discoloration and fading of the print were observed.
[0122]
[Ozone resistance of recorded images]
After exposing the print to a light-shielded tank having an ozone concentration of 3 ppm for 2 hours, discoloration and fading of the print were observed.
[0123]
As a result, in both the light fastness test and the ozone fastness test, the discoloration and fading of the dark, light and mixed color portions of each color were small, and both the light fastness and the ozone fastness were good.
[0124]
Examples 2 to 6
Each ink was prepared in the same manner as in Example 1 except that the dyes described in Tables 6 to 10 were used instead of the dyes used in Example 1, and ink jet recording was performed in the same manner. Light resistance and ozone resistance tests were performed on the recorded matter. As a result, good results were obtained as shown in Table 11.
[0125]
[Table 6]

[0126]
[Table 7]

[0127]
[Table 8]

[0128]
[Table 9]

[0129]
[Table 10]

[0130]
Comparative Example 1
Each ink was prepared in the same manner as in Example 1 except that 0.6 part of the dye of A-8 was used as the dye of the M (light color) ink, and ink-jet recording was performed in the same manner. A light resistance and ozone resistance test was performed on the test, and the results are shown in Table 11.
[0131]
Comparative Example 2
C. M (dark) and M (light) dyes of C.I. I. Each ink was prepared in the same manner as in Example 1 except that 2.5 parts and 0.6 parts of Reactive Red 180 were used, respectively, and ink jet recording was similarly performed. And an ozone resistance test was conducted. The results are shown in Table 11.
[0132]
Comparative Example 3
C. M (dark) and M (light) dyes of C.I. I. Each ink was prepared in the same manner as in Example 1 except that 3.0 parts and 0.7 parts of Acid Red 37 were used, respectively, and ink-jet recording was similarly performed. An ozone resistance test was performed, and the results are shown in Table 11.
[0133]
[Table 11]

[0134]
【The invention's effect】
As described in detail above, according to the color image forming method of the present invention, in image formation by an inkjet method, a magenta aqueous ink using a specific dye, and yellow and cyan or yellow, cyan and black aqueous inks By using, a color image recorded matter having good fastness, which is well balanced in light resistance and ozone resistance, can be obtained.

Claims (4)

In a method of forming a color image by ejecting aqueous inks of magenta, yellow and cyan or magenta, yellow, cyan and black by an inkjet method,
The magenta ink contains one or more metal-containing azo dyes in which the type of free acid is a compound represented by the following general formula [I] and a salt of Cu, Co or Ni. A method for forming a color image.

(In the formula, Z represents a benzene ring or a naphthalene ring-forming atom group which may have a substituent, and R represents a sulfo group or an amino group which may have a substituent.) 2. A color image forming method according to claim 1, wherein the magenta ink and the cyan ink eject two kinds of inks having different color densities to form a color image. 3. The magenta ink according to claim 2, wherein the magenta ink having a low color density contains at least one of the metal-containing azo dyes, and the magenta ink having a high color density has a free acid type represented by the following general formulas (A) to (F). A method for forming a color image, comprising one or more dyes selected from the group consisting of dyes to be formed.

(Wherein, R ^A1 , R ^A2 and R ^A3 each independently represent an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, a halogen atom, a hydrogen atom, , A hydroxyl group, a carbamoyl group which may have a substituent, a sulfamoyl group which may have a substituent, an amino group which may have a substituent, a nitro group, a sulfonic acid ester group, carbon Represents an alkylsulfonyl group having 1 to 9 carbon atoms, an arylsulfonyl group having 6 to 15 carbon atoms, a carboxyl group, or a carboxylate group.
a represents 0, 1 or 2.
R ^A4 , R ^A5 and R ^A6 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group, an aralkyl group, an aromatic hydrocarbon ring group, or a heterocyclic group. Represents a ring group, and among these, a hydrogen atom other than a hydrogen atom may have a substituent. )

^{(Wherein, R B1} and ^{R B2,} -OR ^b1, represents ^-NR b2 ^{R b3} or chlorine ^atom, R ^{b1, R b2} and ^{R b3} represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, carbon atoms Represents an alkenyl group, an aryl group, an aralkyl group, a cycloalkyl group, or a nitrogen-containing heterocyclic group, wherein a group other than a hydrogen atom may further have a substituent, and R ^b2 and R ^b3 may form a 5- or 6-membered ring together with the nitrogen atom to be bonded.
Y ^B1 represents a divalent bonding group selected from groups represented by the following general formulas (1) to (4) and groups represented by the following structural formulas (5) to (8).

(Wherein, Y ¹¹ and Y ¹² each independently represent a linear or branched alkylene group having 1 to 8 carbon atoms, and Y ¹⁰ represents a linear or branched alkylene group having 1 to 12 carbon atoms. Represents a group, and b represents an integer of 0 to 20.)

(In the formula, Y ¹³ and Y ¹⁴ each independently represent a linear or branched alkylene group having 1 to 8 carbon atoms.)

(In the formula, R ¹¹ and R ¹² represent a hydrogen atom or a methyl group.)

(In the formula, R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a methyl group, or a methoxy group.)

Ar ^B1 and Ar ^B2 each independently represent a phenyl group which may have a substituent or a naphthyl group which may have a substituent. )

(In the formula, Ar ^C1 and Ar ^C2 each independently represent an aryl group which may have a substituent, and at least one of Ar ^C1 and Ar ^C2 is a substituent selected from —COOH and —COSH as a substituent. It has at least one group.
R ^C1 and R ^C2 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent.
Y ^C represents the following group.

Y ^C1 represents a divalent organic bonding group, c represents 0 or 1, and Y ^C2 represents a carbonyl group or a group represented by the following formulas (1) to (3).

(Wherein, Z ¹¹ represents NR ²¹ R ²² , SR ²³ or OR ²³ , Z ¹² represents a hydrogen atom, a chlorine atom, Z ¹¹ , SR ²⁴ or OR ²⁴ , and Z ¹³ represents a chlorine atom or a cyano group. R ²¹ , R ²² , R ²³ and R ²⁴ each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. Represents an aryl group or an aralkyl group which may have a substituent, and R ²¹ and R ²² may form a 5- or 6-membered ring together with the bonded nitrogen atom.))

(In the formula, R ^D1 represents a hydrogen atom, a methyl group, a methoxy group, an acetylamino group, or a nitro group, but may form a benzene ring together with the carbon atom at the 3-position of the benzene ring d.
^RD2 represents an acetyl group, a benzoyl group, a paratoluenesulfonyl group, or a 4-chloro-6-hydroxy-1,3,5-triazin-2-yl group. )

(Wherein, ^{RE 1} represents a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms).
R ^E2 represents a hydrogen atom, a CN group as a substituent, a COOR ^e group (R ^e represents a hydrogen atom, a metal atom, or an ammonium group which may have a substituent), an OH group, a COOCH ₃ group, COOCH ₂ CH _{3 represents an} optionally substituted alkyl group having 1 to 6 carbon atoms, or a methyl group, which represents an optionally substituted aryl group.
e represents an integer of 2 to 4.
^RE3 represents an amino group, an alkylthio group, a hydroxyl group or an alkoxy group which may have a substituent. )

(In the formula, R ^F1 represents a hydrogen atom or an alkyl group which may have a substituent, and R ^F2 represents a COR ^f group, a SO ₂ R ^f group, or a group represented by the following general formula (4). Here, R ^f represents an alkyl group which may have a substituent or a phenyl group which may have a substituent.)

(In the formula, R ^f1 each independently represents a COOH group or an SO ₃ H group, R ^f2 each independently represents an amino group which may have a substituent, and R ^f3 each independently represent R ^f1 and R ^f. represents a substituent other than those defined for ^f2 , m, n, and p each independently represent an integer of 0 to 3, and (m + n + p) is an integer of 0 to 5.
Y ^f is -O -, - S -, - represents ^{NR f5, Y f4} represents ^{-OR f6.} Here, R ^f5 and R ^f6 each independently represent an alkyl group which may have a substituent or a phenyl group which may have a substituent. ) The yellow ink according to any one of claims 1 to 3, wherein the yellow ink has a color index (CI) of acid yellow 23, direct yellow 86, 132, 142, or 173, and a free acid type represented by the following general formula [ II] containing at least one dye selected from the group consisting of dyes represented by
The cyan ink has a color index (CI) of Direct Blue 86 and 199, Acid Blue 9, and a dye whose free acid type is selected from the group consisting of compounds represented by the following general formula [III]. Contains more than one kind,
Black inks are Food Index 2, Direct Black 17, 19, 154, 163, 168, 171, 195, and 200, Color Black (CI), Acid Black 2, Reactive Black 31, and Pontamine Black SP Liquid. , Bath Acid Black X-34, and the type of free acid contains one or more dyes selected from the group consisting of dyes represented by the following general formulas [IVa], [IVb] and [IVc]. Color image forming method.

(Wherein, Ar ²¹ and Ar ²² each independently represent an aryl group which may have a substituent, and at least one of Ar ²¹ and Ar ²² has at least a substituent selected from a COOH group and a COSH group. I have one.
Y ²¹ and Y ²² are each independently a linking group represented by the following general formula (a), (b) or (c).

(Wherein, R ³¹ represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxyhalogen group, a cyano group, a ureido group or an NHCOR ³⁵ group, and R ³⁵ has a hydrogen atom and a substituent. Represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group.
R ³² is an alkyl group, R ³³ is a hydrogen atom, a cyano group, a CONR ³⁶ R ³⁷ group (R ³⁶ and R ³⁷ each independently represent a hydrogen atom or an alkyl group which may have a substituent). , A pyridinium group or a COOH group, and Y ³⁰ represents an alkylene group having 2 to 8 carbon atoms.
R ³⁴ represents a hydrogen atom, an alkyl group or a COOH group. )
R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl group which may have a substituent.
Y ²³ represents a divalent linking group.
Y ²⁴ and Y ²⁵ each independently represent a carbonyl group or a group represented by the following general formulas (4) to (6).

^{(Wherein, Z 21} represents ^OR 41, ^{SR 41} or ^NR 42 ^{R 43, Z 22} represents a hydrogen atom, a chlorine atom or a cyano ^{group, Z 23} is ^{.R 41, R 42} representing a chlorine atom or a cyano group , R ⁴³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an aralkyl group which may be possessed, and R ⁴² and R ⁴³ may form a 5- or 6-membered ring together with the nitrogen atom to which they are bonded.)
h represents 0 or 1.
However, when the compound represented by the general formula [II] does not have an SO ₃ H group, the compound represented by the general formula (II) has at least two groups selected from a COOH group and a COSH group. There have groups selected from COOH group and COSH group SO ₃ H groups as many more if with SO ₃ H groups. )

(In the formula, Pc is a metal-containing phthalocyanine nucleus, and R ⁵¹ , R ⁵² , and R ⁵³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a substituent. A good alkenyl group or an aralkyl group which may have a substituent, Y ⁵¹ is a divalent linking group, and Y ⁵² is a carbonyl group or represented by the following general formulas (7) to (9) Represents a group.

(Wherein, Z ³¹ represents NR ⁶¹ R ⁶² , SR ⁶³ or OR ⁶³ , Z ³² represents a hydrogen atom, a chlorine atom, Z ³¹ , SR ⁶⁴ or OR ⁶⁴ , and Z ³³ represents a chlorine atom or a cyano group. R ⁶¹ , R ⁶² , R ⁶³ , and R ⁶⁴ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. And R ⁶¹ and R ⁶² may form a 5- or 6-membered ring together with the nitrogen atom to which they are bonded.)
G represents a colorless organic group substituted by one or two groups selected from a COSH group and a COOH group.
(J + k) is 3 or 4.
However, the compound represented by the general formula [III] has at least one SO ₃ H group, and has the same number or more of the groups selected from the COSH group and the COOH group as the SO ₃ H group. )

(In the formula, p represents 1, 2 or 3, and q represents 0 or 1.)

(In the formula, Ar ^a and Ar ^b each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent, and r represents 0 or 1.)

(In the formula, R ′ represents a hydrogen atom, a lower alkyl group or a phenyl group which may have a substituent with an SO ₃ H group, and t represents 0 or 1.
Ar ^c , Ar ^d , and Ar ^e each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent. However, Ar ^d and Ar ^e are not simultaneously represent a naphthalene ring. )