JP4000649B2 - Recording liquid and ink jet recording method - Google Patents

Description

【０００９】
〔式中、Ｒ₁ ，Ｒ₂ ，Ｒ₃ ，Ｒ₄ ，Ｒ₅ 及びＲ₆ は、それぞれ独立に、置換もしくは非置換の炭素数１〜９のアルキル基、置換もしくは非置換の炭素数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、置換もしくは非置換のカルバモイル基、置換もしくは非置換のスルファモイル基、置換もしくは非置換のアミノ基、ニトロ基、スルホン酸エステルの基、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わす。ｍ，ｎはそれぞれ０，１，または２の数をあらわす。Ｒ₇ ，Ｒ₇ ′は、それぞれ独立に水素原子、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、シクロヘキシル基、または含窒素複素環基を表わし、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よい。
Ｙは下記一般式（II）〜（IV）で示される基及びＡ群の基から選ばれる二価の結合基を示す。
一般式（II）
【００１０】
【化８】

【００１１】
（式中、Ｒ₈ 及びＲ₁₀はそれぞれ独立に炭素数１〜８の直鎖状あるいは分岐鎖状のアルキレン基を表わし、Ｒ₉ は炭素数１〜１２の直鎖状もしくは分岐鎖状のアルキレン基、又は、下記（ａ）式を表わし、ｐは０〜２０の数を表わす。
【００１２】
【化９】

【００１３】
一般式（III)
【００１４】
【化１０】

【００１５】
（一般式（III)中、Ｒ₁₁，Ｒ₁₂は水素原子又はメチル基を表わす。）
一般式（IV)
【００１６】
【化１１】

【００１７】
（一般式（IV) 中、Ｒ₁₃，Ｒ₁₄は水素原子、メチル基又はメトキシ基を表わす。）
（Ａ群）
【００１８】
【化１２】

【００１９】
【発明の実施の形態】
以下本発明を詳細に説明する。
本発明で使用される色素は、遊離酸の型が前記請求項１において一般式（Ｉ）で示される色素から選ばれる少なくとも１種の色調の鮮明な色素並びに耐光性に優れた含金属アゾ色素である。
詳しくは前記一般式（Ｉ）において、Ｒ₁ ，Ｒ₂ ，Ｒ₃ ，Ｒ₄ ，Ｒ₅ 及びＲ₆ で表わされる置換基としてはそれぞれ独立に置換もしくは非置換の炭素数１〜９のアルキル基（例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、２−エチルヘキシル基、トリフロロメチル基、ジメチルアミノメチル基等）、置換もしくは非置換の炭素数１〜９のアルコキシ基（例えば、メトキシ基、イソプロポキシ基、ｎ−ブトキシ基、クロロエトキシ基等）、ハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子等）、水素原子、ヒドロキシル基、置換もしくは非置換のカルバモイル基（例えば、カルバモイル基、Ｎ，Ｎ−ジメチルカルバモイル基、フェニルカルバモイル基等）、置換もしくは非置換のスルファモイル基（例えば、スルファモイル基、Ｎ−メチルスルファモイル基、Ｎ−エチルスルファモイル基、Ｎ−エチル−Ｎ−フェニルスルファモイル基、Ｎ，Ｎ−ジメチルスルファモイル基、ｐ−カルボキシフェニルスルファモイル基等）、置換もしくは非置換のアミノ基（例えば、Ｎ−メチルアミノ基、カルバモイルアミノ基、Ｎ，Ｎ−ジエチルアミノ基、アセチルアミノ基、Ｎ−メチル−Ｎ−アセチルアミノ基等）、ニトロ基、スルホン酸エステルの基（例えばフェノキシスルホニル基等）、スルホニル基（例えば、ヒドロキシエチルスルホニル基、ベンジルスルホニル基等）、カルボキシル基及びカルボン酸エステルの基（例えば、メトキシカルボニル基等）が挙げられる。
【００２０】
ｍ，ｎはそれぞれ０，１または２を表す。Ｒ₇ ，Ｒ₇ ′は、それぞれ独立に、水素原子、置換もしくは非置換の炭素数１〜８のアルキル基（例えば、メチル基、エチル基、ｎ−ブチル基、ｎ−オクチル基、エチルヘキシル基、イソプロピル基、ｔｅｒｔ−ブチル基、カルボキシルメチル基）、置換もしくは非置換の炭素数２又は３のアルケニル基（例えば、ビニル基、アリル基等）、アリール基（例えば、フェニル基、４−ニトロフェニル基、４−ブチルフェニル基、４−カルボキシフェニル基等）、アラルキル基（例えば、ベンジル基、フェネチル基等）、シクロヘキシル基、含窒素複素環基（例えば、ピリジル基等）等が挙げられる。
【００２１】
また、Ｙは一般式（II）〜（IV）で示される基及びＡ群から選ばれる二価の結合基をあらわすが、一般式（II）において、Ｒ₈ ，Ｒ₁₀は炭素数１〜８、好ましくは２〜４の直鎖状あるいは分岐鎖状のアルキレン基（例えばエチレン基、プロピレン基、トリメチレン基等）を表わし、Ｒ₉ は炭素数１〜１２、好ましくは２〜８の直鎖状あるいは分岐鎖状のアルキレン基（例えばエチレン基、プロピレン基、ブチレン基、ヘキシレン基等）又は下記（ａ）式を表わし、ｐは好ましくは０〜１０の数を表わす。
【００２２】
【化１３】

【００２３】
本発明色素はかかる連結基を有することによって特開平８−２１８０２１に示される色素に較べ信頼性が優れている。就中、前記一般式（II）〜（IV）及びＡ群の連結基の中でも、一般式（II）の連結基は水性媒体中に含まれる水溶性有機溶剤と類似した構造であるため、かかる基で連結された色素は信頼性の点で特に好ましいと考えられる。
一般式（Ｉ）で示される本発明の色素の中、カルボキシル基の数が３個以下である構造の色素は、一般に耐水性の面から好ましい。
ｍ及びｎはそれぞれ０又は１が好ましい。
【００２４】
ｍ及びｎが０又は１の場合、Ｒ₁ ，Ｒ₂ 及びＲ₃ の少なくとも１つ並びにＲ₄ ，Ｒ₅ 及びＲ₆ の少なくとも１つは水素原子以外の基であるのが良い。
さらに好ましくは、前記一般式（Ｉ）中のｍ，ｎが１の場合で、フェニル基に置換するＳＯ₃ Ｈ基が、アゾ基の結合位置に対してオルト位に結合している構造の色素を使用するのが良い。
【００２５】
また、前記一般式（Ｉ）中、ｍ，ｎが０の場合、Ｒ₁ 〜Ｒ₃ の少なくとも１つ及びＲ₄ 〜Ｒ₆ の少なくとも１つが水素原子であり、かつＲ₁ 〜Ｒ₃ の少なくとも１つ及びＲ₄ 〜Ｒ₆ の少なくとも１つが、それぞれトリフルオロメチル基、置換もしくは非置換のスルファモイル基、スルホン酸の低級アルキル（以後、「低級アルキル」とは「炭素数１〜４のアルキル基」を指す）エステルの基、スルホン酸の炭素数６〜１２のアリールエステルの基、ＣＯＯＨ基、又はカルボン酸の低級アルキルエステル基から選ばれる基であり、かつその基がそれぞれのフェニル基に結合する位置は、アゾ基の結合位置に対してオルト位である構造の色素が好ましい。
特に、前記一般式（Ｉ）中、
【００２６】
【化１４】

【００２７】
また、前記一般式（Ｉ）中のＲ₇ ，Ｒ₇ ′は水素原子が好ましい。
【００２８】
【化１５】

【００２９】
また、前記一般式（Ｉ）で示される色素の中でも、遊離酸の型が以下の一般式（Ｖ）で示されるような連結基Ｙを介して左右対象の構造の色素が好ましく使用される。この色素は、色調、耐水性、実用性の面で好ましい。
【００３０】
【化１６】

【００３１】
（式中、Ｒ₁ ，Ｒ₂ ，Ｒ₃ ，Ｒ₇ ，ｍ，Ｙは前記一般式（Ｉ）と同じ定義である）
本発明で使用される前記一般式（Ｉ）で示される色素は、遊離酸型（一般式（Ｉ）の構造）のまま使用してもよいが、塩型で使用してもよい。また該遊離酸基の一部が塩型の構造の色素でもよく、塩型の色素と遊離酸型の色素を併用してもよい。このような塩型の例としてはＮａ，Ｌｉ，Ｋ等のアルカリ金属の塩、アルキル基、ヒドロキシアルキル基で置換されていてもよいアンモニウムの塩、有機アミンの塩があげられる。有機アミンの例としては、低級アルキルアミン、ヒドロキシ置換低級アルキルアミン、カルボキシ置換低級アルキルアミン及び炭素数２〜４のアルキレンイミン単位を２〜１０個有するポリアミン等があげられる。これらの塩型の場合、その種類は１種類に限らず複数種混在していてもよい。
これ等の色素の具体例としては、例えば以下のＮｏ．（１）〜（２４）に示す構造の色素が挙げられる。
【００３２】
【化１７】

【００３３】
【化１８】

【００３４】
【化１９】

【００３５】
【化２０】

【００３６】
【化２１】

【００３７】
【化２２】

【００３８】
【化２３】

【００３９】
【化２４】

【００４０】
一般式（Ｉ）で示される色素は、それ自体周知の方法に従って製造することができる。
例えばＮｏ．（１）で示される色素は下記（Ａ）〜（Ｂ）の工程で製造できる。
（Ａ）２−アミノ安息香酸と１−アミノ−８−ヒドロキシ−３，６−ナフタレンジスルホン酸（Ｈ酸）とから常法〔例えば細田豊著「新染料化学」（昭和４８年１２月２１日技報堂発行）第３９６頁〜４０９頁参照〕に従って、ジアゾ化カップリング工程を経てモノアゾ化合物を製造する。
【００４１】
（Ｂ）得られたモノアゾ化合物を塩化シアヌル懸濁液にｐＨ４〜６、温度０〜５℃を保持しながら加えて数時間反応を行う。次いで室温にて弱アルカリ性でジエチレングリコールビス（３−アミノプロピル）エーテルをモノアゾ化合物に対して０．５モル比加えて縮合反応を行う。
次いで２５％水酸化ナトリウム水溶液を５０〜６０℃で加え、加水分解反応を行った後、冷却して、塩化ナトリウムで塩析することにより、目的の染料を得る。
【００４２】
本発明に用いられる含金属アゾ色素として性能上好ましいものとしては、
Ｃ．Ｉ．ＡＲ−３８，１７８，１７９，１８０，１８２，１８３，１８４，１８６，１８７，１８８，１８９，１９０，１９１，１９４，１９５，１９７，１９８，２００，２０１，２０３，２０４，２０６，２０７，２０９，２１０，２１１，２１２，２１４，２２１，２２３，２４３，２４４，２５１，２５８，２５９，２６２，２６８，２６９，２７０，２７１，２７２，２７３，２７５，２７７，２７８，２７９，２８１，２８７，２９１，２９２，２９５，２９６，２９８，３００，３０４，３０７，３０８，３１２，３１３，３１４，３１５，３１６，３１７，３１８，３２０，３２１，３２８，３２９，３３０，３３１，３３２，３３８，３３９，３４１，３４２，３４５，３４６，３４９，３５５，３５７，３５８，３５９，３６２，３６３，３７３，３８２，３８３，３９９，４０２，４０４，４０５，４０７，４１４，４１６，４２３，４２５，４３０，４３２，４３５，４３６，４３７，４３８，４４２，４４３，４４５、
【００４３】
Ｃ．Ｉ．Ａφ−６０，６１，６２，６２：１，６４，６８，６９，７１，７２，７４，７５，７６，９０，９１，９２，９３，９６，９７，９８，９９，１００，１０３，１０４，１０５，１０７，１０８，１１２，１１３，１１４，１１５，１１８，１２０，１２１，１２２，１２３，１２５，１２６，１２９，１３０，１３３，１３９，１４０，１４１，１４２，１４３，１４４，１４８，１５３，１５４，１５５，１６２，１６３，１６４，１６６，１６７，１６８，１７０，１７２，１７９、
【００４４】
Ｃ．Ｉ．ＡＶ−４０，４４，４６，５６，５８，５９，６０，６１，６２，６４，６５，７９，８１，８２，８３，８７，８８，８９，９０，９１，９２，９３，９４，９５，９８，１００，１０１，１０４，１０５，１０６，１０７，１０８，１１０，１１１，１１２，１１３，１１４，１１５，１１６，１２０，１２１，１２２，１２７，１２８，１２９、
【００４５】
Ｃ．Ｉ．ＤＲ−９９，１０６、
Ｃ．Ｉ．ＤＶ−４６，４９，５６，６０，８９、
Ｃ．Ｉ．ＲＲ−６，７，１４，１８，２３，４７，４８，４９，７２，９８，１７１，１７９，２４７、
Ｃ．Ｉ．Ｒφ−１９，２１，２２，２６，３３，３９，９８、
Ｃ．Ｉ．ＲＶ−１，３，４，５，１１，１５，２５，２７，３５、
等が挙げられる。
【００４６】
（尚「Ｃ．Ｉ．」は「カラーインデックス」を示し、「ＡＲ」は「アシッドレッド」を示し、「Ａφ」は「アシッドオレンジ」を示し、「ＡＶ」は「アシッドバイオレット」を示し、「ＤＲ」は「ダイレクトレッド」を示し、「ＤＶ」は「ダイレクトバイオレット」を示し、「ＲＲ」は「リアクティブレッド」を示し、「Ｒφ」は「リアクティブオレンジ」を示し、「ＲＶ」は「リアクティブバイオレット」を示す。）
記録液中における前記一般式（Ｉ）及び含金属アゾ色素の含有量としては、記録液全量に対して合計で０．５〜５重量％、特に２〜４．５重量％程度が好ましい。
尚前記一般式（Ｉ）の色素と、含金属アゾ色素との配合比率は重量比で１／９〜９／１、好ましくは２／８〜８／２である。
【００４７】
また、本発明に用いられる水性媒体としては、水及び水溶性有機溶剤として、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、ポリエチレングリコール（重量平均分子量約１９０〜４００）、グリセリン、Ｎ−メチルピロリドン、Ｎ−エチルピロリドン、１，３−ジメチルイミダゾリジノン、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、ジエチレングリコールモノメチルエーテル、２−ピロリドン、スルホラン、エチルアルコール、イソプロパノール等を含有しているのが好ましい。これ等の水溶性有機溶剤は、通常記録液の全量に対して１〜５０重量％の範囲で使用される。一方、水は記録液の全量に対して４５〜９５重量％の範囲で使用される。
【００４８】
本発明の記録液に、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、又０．００１〜５．０重量％の界面活性剤を添加することによって、印字後の速乾性及び印字品位をより一層改良することができる。
【００４９】
【実施例】
以下、本発明を実施例について更に詳細に説明するが、本発明はその要旨を越えない限りこれ等の実施例に限定されるものではない。
実施例１
ジエチレングリコール１０重量部、ジエチレングリコールモノブチルエーテル３重量部、前記Ｎｏ．（１）の色素１．５重量部、Ｃ．Ｉ．ＲＲ−２３（含金属色素）１．５重量部に水を加え、水酸化ナトリウム水溶液でｐＨを９に調整して全量を１００重量部とした。この組成物を充分に混合して溶解し、孔径１μｍのテフロン（登録商標）フィルターで加圧濾過した後、真空ポンプ及び超音波洗浄機で脱気処理して記録液を調製した。
【００５０】
得られた記録液を使用し、インクジェットプリンター（商品名ＢＪＣ−６００、キヤノン社製品）を用いて電子写真用紙（商品名４０２４紙、ゼロックス社製品）、高品位専用紙（商品名ＨＲ−１０１、キヤノン社製品）、フォト光沢紙（商品名ＧＰ−２０１、キヤノン社製品）に各々インクジェット記録を行い、鮮明な色調（彩度）のマゼンタ色印字物を得た。また下記に（ａ），（ｂ），（ｃ）及び（ｄ）の方法による諸評価を行った結果を示す。
（ａ）記録画像の耐光性：
キセノンフェードメーター（スガ試験機社製品）を用い、記録紙に１００時間照射したが、照射後の変退色は小さかった。
（ｂ）記録画像の耐水性：
（１）試験方法
水道水中に記録画像を５分間浸漬したのち、
▲１▼目視にて画像の滲みを調べた。
▲２▼浸漬前後のベタ印字部分のＯＤ値をマクベス濃度計（商品名：ＴＲ９２７、マクベス社製品）にて測定した。
【００５１】
（２）試験結果
上記▲１▼の結果画像のにじみはわずかであった。
また上記▲２▼の浸漬前後のベタ印字部分の濃度変化を下記式によるＯＤ残存率で示すと、７５．４％であった。
【００５２】
【数１】

【００５３】
（ｃ）記録液の保存安定性：
記録液をテフロン（登録商標）製容器に密閉し、５℃及び６０℃で１ケ月間保存した後の変化を調べたところ、不溶物の析出は認められなかった。
（ｄ）記録液の信頼性
▲１▼目詰まり性（固着回復性）
プリンターに所定のインクを充填して、３５℃の環境下で１カ月間放置し、その後回復操作（ポンピングによる吸引操作）を行った後、印字させたところ正常な印字状態に戻った。
▲２▼間欠吐出の安定性
プリンターに所定のインクを充填して１分間連続して英数字を印字した後、プリントを停止し、キャップ等をしない状態で１分間放置した後、再び印字した場合の文字のかすれ、欠け等は１文字目から認められなかった。
【００５４】
実施例２〜５
実施例１において用いた色素の代わりに下記第１表に記載した色素を用いた以外は実施例１と同様に記録液を調製し、実施例１と同様に印字を行った。この結果どれも鮮明な色調（彩度）のマゼンタ色記録物を得た。また、この記録物に対して実施例１の（ａ）〜（ｄ）による諸評価を行った。その結果、第１表に示すとおり、良好な結果が得られた。
【００５５】
比較例１
実施例１において用いた前記Ｎｏ．（１）の色素のみを３％使用した以外は、実施例１の方法により記録液を調製し、印字を行い、この記録物に対して実施例１の（ａ）〜（ｄ）による諸評価を行った。結果を第１表に示した。
比較例２
実施例１において用いた前記Ｃ．Ｉ．ＲＲ−２３のみを３％使用した以外は、実施例１の方法により記録液を調製し印字を行い、この記録物に対して実施例１の（ａ）〜（ｄ）による諸評価を行った。結果を第１表に示した。
比較例３〜１０
実施例１において用いた色素の代わりに下記第１表に記載した色素を用いた以外は実施例１と同様に記録液を調製し、印字を行い、この記録物に対して実施例１の（ａ）〜（ｄ）による諸評価を行った、結果を第１表に示した。
【００５６】
【表１】

【００５７】
【表２】

【００５８】
【表３】

【００５９】
上記第１表中、色調の評価は、画像の色の彩度で表し、詳しくはＣＩＥ１９７６（Ｌ^* ａ^* ｂ^* ）表色系を用いた色差計（商品名：ＳＺ−Σ８０、日本電色工業社製品）により、記録画像の色調を測色してＬ^* 、ａ^* 、ｂ^* の値を求め、下式に従い計算し、
【００６０】
【数２】

【００６１】
その値が、６０以上のものを○、５５以上６０未満のものを△、５５以下のものを×とした。
耐光性は、目視で観察し、○は変退色は殆ど認められない、△は変退色がやや認められる、×は変退色が著しく、実用レベルでない状態を示す。
耐水性の滲みは、目視で観察し、○は滲みが殆ど認められない状態から、僅かに認められるが画像の輪郭がややぼけているだけで、画像の濃度の低下は殆ど認められない、△は滲みが認められるが、滲みの範囲は小さく、画像の濃度の低下は小さい、×は滲みが著しく、滲みの範囲も大きく、元の画像部分の識別が困難であり、実用レベルでない状態を示す。
【００６２】
保存安定性は、記録液を試験管にとり目視で観察して、○は不溶分が全く認められない状態を表し、△は不溶分が少量認められる状態を表し、×は不溶分が目立ち、実用レベルでない状態を表す。
記録液の信頼性のうち、▲１▼目詰まり性（固着回復性）においては、○は回復操作２回以内で正常な印字状態に戻る状態を表し、△は回復操作３〜４回で正常な印字状態に戻る状態を表し、×は回復操作５回以上でも不吐出や印字乱れが発生する状態を表す。
▲２▼の間欠吐出の安定性においては、○は１文字目からかすれ、欠けなしの状態を表し、△は１文字目の一部がかすれ、又は欠ける状態を表し、×は１文字目が全く印字できない状態を表す。
【００６３】
【発明の効果】
本発明の記録液は、インクジェット記録用、筆記用具用として用いられ、鮮明なマゼンタ色系の記録物を得ることができ、その印字濃度及び耐光性、耐水性が優れている他、記録液としての保存安定性も良好である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a recording liquid. Specifically, the present invention relates to a magenta recording liquid suitable for ink jet recording.
[0002]
[Prior art]
A so-called ink jet recording method has been put to practical use in which recording is performed by ejecting droplets of a recording liquid containing a water-soluble dye such as a direct dye or an acid dye from a minute ejection orifice.
This recording solution is fast to fix on general-purpose office paper such as PPC (plain paper copier) and fan hold paper (continuous paper for computers, etc.) for electrophotographic paper, and the print quality of printed matter. In other words, it is required to have good printing characteristics, i.e., no blurring and clear outline, and excellent stability when stored as a recording liquid. Limited.
[0003]
On the other hand, the dye for recording liquid has sufficient solubility in the limited solvent as described above, and is stable when stored as a recording liquid for a long period of time. It is required to have high degree and concentration, and excellent water resistance and light resistance.
In particular, the magenta recording liquid has a problem that the image is faded by light irradiation, that is, the light resistance is poor, and a recording liquid that satisfies many of these requirements has been demanded.
[0004]
For this reason, various proposals (for example, Japanese Patent Laid-Open Nos. 57-30773, 61-101574, 61-101576, 61-195176, 61-62562, 61-62562, JP 61-247771, JP 62-156168, JP 62-190275, JP 62-246974, JP 63-46259, JP 63-46260, JP 63- No. 63765, JP-A-63-29585, JP-A-1-123866, JP-A-1-240584, JP-A-2-16171, JP-A-3-122171, JP-A-3-203970, JP-A-4-243 No. 153272, etc.) have been made, but have not yet fully satisfied market demands.
[0005]
In particular, for magenta dyes conventionally used in recording liquids, direct dyes and acid dyes that are not metal-containing dyes, which are commercially available dyes, have been used.
Direct dyes have unclear color tone, and conversely acid dyes with clear color tone tend to have poor light resistance. Conventionally, metal-containing azo dyes have good light resistance, but the development of magenta dyes that are dull and unclear and satisfy both the color and light resistance has been desired.
[0006]
[Problems to be solved by the invention]
The present invention has good print quality even when recorded on plain paper, such as for inkjet recording and writing utensils, etc., and has a high density of recorded images and excellent light resistance, especially water resistance and color tone of recorded images. Therefore, it is an object of the present invention to provide a magenta recording liquid having good stability when stored for a long period of time.
[0007]
[Means for Solving the Problems]
The above object is achieved by the present invention described below.
That is, the gist of the present invention resides in an aqueous medium and a recording liquid containing at least one dye selected from the dyes represented by the following general formula (I) and a metal-containing azo dye.
[0008]
[Chemical 7]

[0009]
[Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms, a substituted or unsubstituted carbon number 1 to 9 alkoxy groups, halogen atoms, hydrogen atoms, hydroxyl groups, substituted or unsubstituted carbamoyl groups, substituted or unsubstituted sulfamoyl groups, substituted or unsubstituted amino groups, nitro groups, sulfonate groups, sulfonyl groups, Represents a carboxyl group or a carboxylate group. m and n each represent a number of 0, 1, or 2. R ₇ and R ₇ ′ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an aryl group, an aralkyl group, a cyclohexyl group, or a nitrogen-containing heterocyclic group, Among these, groups other than a hydrogen atom may further have a substituent.
Y represents a divalent linking group selected from the groups represented by the following general formulas (II) to (IV) and the group A.
Formula (II)
[0010]
[Chemical 8]

[0011]
(In the formula, R ₈ and R ₁₀ each independently represent a linear or branched alkylene group having 1 to 8 carbon atoms, and R ₉ represents a linear or branched alkylene group having 1 to 12 carbon atoms. Represents a group or the following formula (a), and p represents a number of 0 to 20.
[0012]
[Chemical 9]

[0013]
General formula (III)
[0014]
[Chemical Formula 10]

[0015]
(In the general formula (III), R ₁₁ and R ₁₂ represent a hydrogen atom or a methyl group.)
Formula (IV)
[0016]
Embedded image

[0017]
(In the general formula (IV), R ₁₃ and R ₁₄ represent a hydrogen atom, a methyl group or a methoxy group.)
(Group A)
[0018]
Embedded image

[0019]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
The dye used in the present invention is a metal-containing azo dye having a free acid type having a clear tone of at least one color selected from the dye represented by formula (I) in claim 1 and excellent light resistance It is.
Specifically, in the general formula (I), the substituents represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms. (For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-ethylhexyl group, a trifluoromethyl group, a dimethylaminomethyl group, etc.), a substituted or unsubstituted C 1-9 Alkoxy group (eg, methoxy group, isopropoxy group, n-butoxy group, chloroethoxy group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), hydrogen atom, hydroxyl group, substituted or unsubstituted Carbamoyl groups (eg, carbamoyl group, N, N-dimethylcarbamoyl group, phenylcarbamoyl group, etc.), substituted or unsubstituted sulfamoyl groups (eg For example, sulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, p-carboxyphenylsulfamoyl Group), substituted or unsubstituted amino group (for example, N-methylamino group, carbamoylamino group, N, N-diethylamino group, acetylamino group, N-methyl-N-acetylamino group, etc.), nitro group, Examples include a sulfonate group (for example, phenoxysulfonyl group), a sulfonyl group (for example, hydroxyethylsulfonyl group, benzylsulfonyl group), a carboxyl group, and a carboxylate group (for example, methoxycarbonyl group).
[0020]
m and n each represents 0, 1 or 2. R ₇ and R ₇ ′ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, n-butyl group, n-octyl group, ethylhexyl group, Isopropyl group, tert-butyl group, carboxylmethyl group), substituted or unsubstituted alkenyl group having 2 or 3 carbon atoms (for example, vinyl group, allyl group, etc.), aryl group (for example, phenyl group, 4-nitrophenyl group) , 4-butylphenyl group, 4-carboxyphenyl group and the like), aralkyl group (for example, benzyl group, phenethyl group and the like), cyclohexyl group, nitrogen-containing heterocyclic group (for example, pyridyl group and the like) and the like.
[0021]
Y represents a group represented by general formulas (II) to (IV) and a divalent linking group selected from group A. In general formula (II), R ₈ and R _{10 each} have 1 to 8 carbon atoms. Preferably represents a linear or branched alkylene group of 2 to 4 (eg, ethylene group, propylene group, trimethylene group, etc.), and R ₉ is a linear chain having 1 to 12 carbon atoms, preferably 2 to 8 carbon atoms. Alternatively, it represents a branched alkylene group (for example, ethylene group, propylene group, butylene group, hexylene group, etc.) or the following formula (a), and p preferably represents a number of 0 to 10.
[0022]
Embedded image

[0023]
Since the dye of the present invention has such a linking group, it is more reliable than the dye disclosed in JP-A-8-218021. Among them, among the linking groups of the general formulas (II) to (IV) and the group A, the linking group of the general formula (II) has a structure similar to that of the water-soluble organic solvent contained in the aqueous medium. A dye linked by a group is considered particularly preferable in terms of reliability.
Of the dyes of the present invention represented by the general formula (I), dyes having a structure having 3 or less carboxyl groups are generally preferred from the viewpoint of water resistance.
m and n are each preferably 0 or 1.
[0024]
When m and n are 0 or 1, at least one of R ₁ , R ₂ and R ₃ and at least one of R ₄ , R ₅ and R ₆ may be a group other than a hydrogen atom.
More preferably, when m and n in the general formula (I) are 1, the SO ₃ H group substituted on the phenyl group is bonded to the ortho position with respect to the bonding position of the azo group. Good to use.
[0025]
In the general formula (I), when m and n are 0, at least one of R _{1 to} R ₃ and at least one of R _{4 to} R ₆ are hydrogen atoms, and at least one of R _{1 to} R ₃ 1 and at least one of R _{4 to} R ₆ are each a trifluoromethyl group, a substituted or unsubstituted sulfamoyl group, a lower alkyl of a sulfonic acid (hereinafter referred to as “lower alkyl” means “an alkyl group having 1 to 4 carbon atoms”). A group selected from an ester group, an aryl ester group having 6 to 12 carbon atoms of sulfonic acid, a COOH group, or a lower alkyl ester group of carboxylic acid, and the group is bonded to each phenyl group. The dye is preferably a dye having a structure that is ortho to the bonding position of the azo group.
In particular, in the general formula (I),
[0026]
Embedded image

[0027]
In the general formula (I), R ₇ and R ₇ ′ are preferably hydrogen atoms.
[0028]
Embedded image

[0029]
Among the dyes represented by the general formula (I), a dye having a structure of the right and left objects is preferably used through a linking group Y having a free acid type represented by the following general formula (V). This pigment is preferable in terms of color tone, water resistance, and practicality.
[0030]
Embedded image

[0031]
(In the formula, R ₁ , R ₂ , R ₃ , R ₇ , m, and Y have the same definition as in the general formula (I)).
The dye represented by the general formula (I) used in the present invention may be used as it is in the free acid form (structure of the general formula (I)), or may be used in a salt form. Further, a part of the free acid group may be a salt-type dye, or a salt-type dye and a free acid-type dye may be used in combination. Examples of such salt types include salts of alkali metals such as Na, Li and K, ammonium salts optionally substituted with alkyl groups and hydroxyalkyl groups, and salts of organic amines. Examples of organic amines include lower alkylamines, hydroxy-substituted lower alkylamines, carboxy-substituted lower alkylamines, and polyamines having 2 to 10 alkyleneimine units having 2 to 4 carbon atoms. In the case of these salt types, the type is not limited to one type, and a plurality of types may be mixed.
Specific examples of these dyes include, for example, the following No. (1)-The pigment | dye of the structure shown to (24) is mentioned.
[0032]
Embedded image

[0033]
Embedded image

[0034]
Embedded image

[0035]
Embedded image

[0036]
Embedded image

[0037]
Embedded image

[0038]
Embedded image

[0039]
Embedded image

[0040]
The dye represented by the general formula (I) can be produced according to a method known per se.
For example, no. The pigment | dye shown by (1) can be manufactured at the process of following (A)-(B).
(A) From 2-aminobenzoic acid and 1-amino-8-hydroxy-3,6-naphthalenedisulfonic acid (H acid) [for example, Yutaka Hosoda, “New dye chemistry” (December 21, 1973 Mono-azo compound is produced through a diazotization coupling step according to (published by Gihodo) pages 396 to 409].
[0041]
(B) The obtained monoazo compound is added to a cyanuric chloride suspension while maintaining pH 4 to 6 and temperature 0 to 5 ° C., and reacted for several hours. Next, a condensation reaction is carried out by adding 0.5 mole ratio of diethylene glycol bis (3-aminopropyl) ether to the monoazo compound which is weakly alkaline at room temperature.
Next, a 25% aqueous sodium hydroxide solution is added at 50 to 60 ° C. to carry out a hydrolysis reaction, followed by cooling and salting out with sodium chloride to obtain the target dye.
[0042]
As a metal-containing azo dye used in the present invention, preferable in terms of performance,
C. I. AR-38,178,179,180,182,183,184,186,187,188,189,190,191,194,195,197,198,200,201,203,204,206,207,209, 210, 211, 212, 214, 221, 223, 243, 244, 251, 258, 259, 262, 268, 269, 270, 271, 272, 273, 275, 277, 278, 279, 281, 287, 291 292,295,296,298,300,304,307,308,312,313,314,315,316,317,318,320,321,328,329,330,331,332,338,339,341 342, 345, 346, 349, 355, 357, 358, 359, 362 363,373,382,383,399,402,404,405,407,414,416,423,425,430,432,435,436,437,438,442,443,445,
[0043]
C. I. Aφ-60, 61, 62, 62: 1, 64, 68, 69, 71, 72, 74, 75, 76, 90, 91, 92, 93, 96, 97, 98, 99, 100, 103, 104, 105, 107, 108, 112, 113, 114, 115, 118, 120, 121, 122, 123, 125, 126, 129, 130, 133, 139, 140, 141, 142, 143, 144, 148, 153 154, 155, 162, 163, 164, 166, 167, 168, 170, 172, 179,
[0044]
C. I. AV-40, 44, 46, 56, 58, 59, 60, 61, 62, 64, 65, 79, 81, 82, 83, 87, 88, 89, 90, 91, 92, 93, 94, 95, 98, 100, 101, 104, 105, 106, 107, 108, 110, 111, 112, 113, 114, 115, 116, 120, 121, 122, 127, 128, 129,
[0045]
C. I. DR-99, 106,
C. I. DV-46, 49, 56, 60, 89,
C. I. RR-6, 7, 14, 18, 23, 47, 48, 49, 72, 98, 171, 179, 247,
C. I. Rφ-19, 21, 22, 26, 33, 39, 98,
C. I. RV-1, 3, 4, 5, 11, 15, 25, 27, 35,
Etc.
[0046]
(“CI” indicates “color index”, “AR” indicates “acid red”, “Aφ” indicates “acid orange”, “AV” indicates “acid violet”, “ “DR” indicates “Direct Red”, “DV” indicates “Direct Violet”, “RR” indicates “Reactive Red”, “Rφ” indicates “Reactive Orange”, and “RV” indicates “ Reactive violet ".)
The content of the general formula (I) and the metal-containing azo dye in the recording liquid is preferably about 0.5 to 5% by weight, particularly about 2 to 4.5% by weight, based on the total amount of the recording liquid.
The blending ratio of the dye of the general formula (I) and the metal-containing azo dye is 1/9 to 9/1, preferably 2/8 to 8/2, by weight.
[0047]
Examples of the aqueous medium used in the present invention include water and water-soluble organic solvents such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (weight average molecular weight of about 190 to 400), glycerin, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethylimidazolidinone, thiodiethanol, dimethyl sulfoxide, ethylene glycol monoallyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, 2-pyrrolidone, sulfolane, ethyl alcohol, isopropanol Etc. are preferably contained. These water-soluble organic solvents are usually used in the range of 1 to 50% by weight with respect to the total amount of the recording liquid. On the other hand, water is used in the range of 45 to 95% by weight with respect to the total amount of the recording liquid.
[0048]
0.1 to 10% by weight, preferably 0.5 to 5% by weight, of the compound selected from urea, thiourea, biuret and semicarbazide is added to the recording liquid of the present invention. By adding 001 to 5.0% by weight of a surfactant, quick drying after printing and printing quality can be further improved.
[0049]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples, unless the summary is exceeded.
Example 1
10 parts by weight of diethylene glycol, 3 parts by weight of diethylene glycol monobutyl ether, 1.5 parts by weight of the dye of (1), C.I. I. Water was added to 1.5 parts by weight of RR-23 (metal-containing dye), and the pH was adjusted to 9 with an aqueous sodium hydroxide solution to make the total amount 100 parts by weight. This composition was thoroughly mixed and dissolved, filtered under pressure with a Teflon (registered trademark) filter having a pore size of 1 μm, and then degassed with a vacuum pump and an ultrasonic cleaner to prepare a recording liquid.
[0050]
Using the obtained recording liquid, using an inkjet printer (trade name BJC-600, Canon product), electrophotographic paper (trade name 4024 paper, Xerox product), high-quality exclusive paper (trade name HR-101, Canon product) and photo glossy paper (trade name GP-201, Canon product) were each subjected to ink jet recording to obtain a magenta print with a clear color tone (saturation). The results of various evaluations by the methods (a), (b), (c) and (d) are shown below.
(A) Light resistance of recorded image:
Using a xenon fade meter (product of Suga Test Instruments Co., Ltd.), the recording paper was irradiated for 100 hours, but the color fading after irradiation was small.
(B) Water resistance of recorded image:
(1) Test method After immersing the recorded image in tap water for 5 minutes,
(1) The blur of the image was examined visually.
(2) The OD value of the solid printed part before and after immersion was measured with a Macbeth densitometer (trade name: TR927, Macbeth product).
[0051]
(2) Test results As a result of the above (1), the image was slightly blurred.
Further, the change in the density of the solid print portion before and after the immersion of the above (2) was expressed as an OD residual ratio according to the following formula, which was 75.4%.
[0052]
[Expression 1]

[0053]
(C) Storage stability of recording liquid:
When the recording liquid was sealed in a Teflon (registered trademark) container and stored at 5 ° C. and 60 ° C. for 1 month, no change was found.
(D) Reliability of recording liquid (1) Clogging property (fixing recovery property)
The printer was filled with a predetermined ink, left in a 35 ° C. environment for one month, and then after a recovery operation (suction operation by pumping), printing was performed and the printer returned to a normal printing state.
(2) Stability of intermittent discharge When the printer is filled with the specified ink and alphanumeric characters are printed continuously for 1 minute, printing is stopped, the printer is left for 1 minute without caps, and then printed again. No blurring or chipping was observed from the first letter.
[0054]
Examples 2-5
A recording liquid was prepared in the same manner as in Example 1 except that the dyes listed in Table 1 below were used instead of the dyes used in Example 1, and printing was performed in the same manner as in Example 1. As a result, a magenta color recorded product having a clear color tone (saturation) was obtained. Moreover, various evaluations according to (a) to (d) of Example 1 were performed on the recorded matter. As a result, good results were obtained as shown in Table 1.
[0055]
Comparative Example 1
The No. 1 used in Example 1 was used. A recording liquid was prepared by the method of Example 1 except that only 3% of the dye of (1) was used, printing was performed, and various evaluations according to (a) to (d) of Example 1 were performed on this recorded matter. Went. The results are shown in Table 1.
Comparative Example 2
The C.I. used in Example 1 was used. I. Except for using only 3% of RR-23, a recording liquid was prepared and printed by the method of Example 1, and various evaluations according to (a) to (d) of Example 1 were performed on this recorded matter. . The results are shown in Table 1.
Comparative Examples 3-10
A recording solution was prepared and printed in the same manner as in Example 1 except that the dyes listed in Table 1 below were used instead of the dyes used in Example 1. Table 1 shows the results of various evaluations according to a) to (d).
[0056]
[Table 1]

[0057]
[Table 2]

[0058]
[Table 3]

[0059]
In Table 1 above, the evaluation of the color tone is expressed by the color saturation of the image, and more specifically, a color difference meter (trade name: SZ-Σ80, Nippon Denshoku) using the CIE 1976 (L ^* a ^* b ^* ) color system. By measuring the color tone of the recorded image to obtain the values of L ^* , a ^* , b ^* , and calculating according to the following formula:
[0060]
[Expression 2]

[0061]
A value of 60 or more was evaluated as ◯, a value of 55 or more and less than 60 as Δ, and a value of 55 or less as ×.
The light resistance is visually observed, ◯ indicates that almost no fading color is observed, Δ indicates that the fading color is slightly recognized, and × indicates that the fading color is remarkably not practical.
The water-resistant bleeding is visually observed, and ○ is slightly recognized from the state where bleeding is hardly observed, but the outline of the image is slightly blurred, and almost no decrease in the density of the image is observed. Although bleeding is observed, the range of bleeding is small and the decrease in density of the image is small. × indicates that bleeding is remarkable, the range of bleeding is large, the original image portion is difficult to identify, and indicates a state that is not at a practical level. .
[0062]
Storage stability is determined by visually observing the recording solution in a test tube, ◯ indicates a state where no insoluble matter is observed, △ indicates a state where a small amount of insoluble matter is observed, and × indicates that the insoluble matter is noticeable. Represents a non-level state.
Among the reliability of the recording liquid, (1) In the clogging property (fixing recovery property), ◯ indicates a state in which the normal printing state is restored within 2 recovery operations, and △ is normal after 3 to 4 recovery operations. Represents a state of returning to the correct printing state, and x represents a state where non-ejection or printing disturbance occurs even after five or more recovery operations.
In the stability of intermittent ejection of (2), ○ indicates a state where the first character is faint and not missing, Δ indicates a portion where the first character is faint or missing, and × indicates the first character Indicates a state where printing is not possible at all.
[0063]
【The invention's effect】
The recording liquid of the present invention is used for ink-jet recording and writing instruments, and can obtain a clear magenta-colored recording material, and has excellent printing density, light resistance, and water resistance, The storage stability of is also good.

Claims (5)

A recording liquid comprising an aqueous medium, at least one dye selected from dyes represented by the following general formula (I), and a metal-containing azo dye.

[Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms, a substituted or unsubstituted carbon number 1 to 9 alkoxy groups, halogen atoms, hydrogen atoms, hydroxyl groups, substituted or unsubstituted carbamoyl groups, substituted or unsubstituted sulfamoyl groups, substituted or unsubstituted amino groups, nitro groups, sulfonate groups, sulfonyl groups, Represents a carboxyl group or a carboxylate group. m and n each represents a number of 0, 1, or 2. R ₇ and R ₇ ′ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 or 3 carbon atoms, an aryl group, an aralkyl group, a cyclohexyl group, or a nitrogen-containing heterocyclic group, Among these, groups other than a hydrogen atom may further have a substituent.
Y represents a divalent linking group selected from the groups represented by the following general formulas (II) to (IV) and the group A.
Formula (II)

(In the formula, R ₈ and R ₁₀ each independently represents a linear or branched alkylene group having 1 to 8 carbon atoms, and R ₉ represents a linear or branched alkylene group having 1 to 12 carbon atoms. Represents a group or the following formula (a), and p represents a number of 0 to 20.

General formula (III)

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

(In the general formula (IV), R ₁₃ and R ₁₄ represent a hydrogen atom, a methyl group or a methoxy group.)
(Group A)

  At least one dye selected from dyes represented by the general formula (I) and at least one dye selected from metal-containing azo dyes in a total proportion of 0.5 to 5% by weight based on the total weight of the recording liquid. The recording liquid according to claim 1, which is contained.   2. The blending ratio of at least one dye selected from dyes represented by formula (I) and at least one dye selected from metal-containing azo dyes is 1/9 to 9/1 by weight. Or the recording liquid of 2. The recording liquid according to claim 1, wherein the recording liquid is for inkjet recording. An ink jet recording method using the recording liquid according to claim 4.