JP3829462B2 - Recording liquid, inkjet recording method, and water-soluble dye - Google Patents

Description

【００１２】
〔式中、Ａｒ¹ 及びＡｒ² は、それぞれ独立に、置換もしくは非置換のフェニル基又はナフチル基を表わし；Ｘ₁ ，Ｘ₂ は、−ＯＲ ₁ 又は塩素原子を表わし；Ｒ ₁ 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く；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）
【００１３】
【化１５】

【００１４】
（式中、Ｒ₄ 及びＲ₆ 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；Ｒ₅ 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、
【００１５】
【化１６】

一般式（III)
【００１６】
【化１７】

（式中、Ｒ₇ ，Ｒ₈ は水素原子又はメチル基を表わす、）
一般式（IV)
【００１７】
【化１８】

【００１８】
（式中Ｒ₉ ，Ｒ₁₀は水素原子、メチル基又はメトキシ基を表わす、）
（Ａ群）
【００１９】
【化１９】

【００２０】
【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）で表されるものである。
詳しくは前記一般式（１）において、Ａｒ¹ 及びＡｒ² のための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。
【００２１】
Ｘ₁ 及びＸ₂ はそれぞれ−ＯＲ₁ または−ＮＲ₂ Ｒ₃ で示される基または塩素原子を表わし、Ｒ₁ で表される置換基としては、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、Ｒ₂ ，Ｒ₃ で表される置換基としては、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、ヒドロキシエチル基等）、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。
結合される窒素原子と共にＲ₂ およびＲ₃ が、５または６員環を形成する例としては、モルホリン環、ピペラジン環またはピペラジン環等が挙げられる。
【００２２】
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、Ｒ₄ ，Ｒ₆ 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、Ｒ₅ 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。
【００２３】
【化２０】

【００２４】
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。
前記一般式（Ｉ）で示される色素の中、Ａｒ¹ 及びＡｒ² で表わされるナフチル基が置換基としてスルホ基及びカルボキシル基から選ばれる基を有するものが好ましい。
前記一般式（Ｉ）で示される色素は好ましくは下記一般式（Ｉ′）で示される色素である。
【００２５】
【化２１】

【００２６】
（式中、Ｒ₁₁，Ｒ₁₂，Ｒ₁₃，Ｒ₁₄，Ｒ₁₅及びＲ₁₆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し；ｍ，ｎはそれぞれ０，１，または２の数をあらわし；またＸ₁ ，Ｘ₂ 及びＹは一般式（Ｉ）で示されたものと同義である。）
【００２７】
詳しくは前記一般式（１′）において、Ｒ₁₁，Ｒ₁₂，Ｒ₁₃，Ｒ₁₄，Ｒ₁₅及びＲ₁₆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。
【００２８】
一般式（Ｉ′）で示される本発明の色素の中、Ｒ₁₁〜Ｒ₁₆における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。
【００２９】
ｍ及びｎが０又は１の場合、Ｒ₁₁，Ｒ₁₂及びＲ₁₃の少なくとも１つ並びにＲ₁₄，Ｒ₁₅及びＲ₁₆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。
【００３０】
また、前記一般式（Ｉ′）中、ｍ，ｎが０の場合、Ｒ₁₁〜Ｒ₁₃の少なくとも１つ及びＲ₁₄〜Ｒ₁₆の少なくとも１つが水素原子であり、かつＲ₁₁〜Ｒ₁₃の少なくとも１つ及びＲ₁₄〜Ｒ₁₆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。
一方、前記一般式（Ｉ′）中、
【００３１】
【化２２】

【００３２】
また、前記一般式（Ｉ）中のＸ₁ ，Ｘ₂ はＯＨ基が好ましく、
【００３３】
【化２３】

【００３４】
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。
【００３５】
【化２４】

【００３６】
（式中、Ｒ₁₁，Ｒ₁₂，Ｒ₁₃，Ｘ₁ ，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）〜（５２）に示す構造の色素が挙げられる。
【００３７】
【化２５】

【００３８】
【化２６】

【００３９】
【化２７】

【００４０】
【化２８】

【００４１】
【化２９】

【００４２】
【化３０】

【００４３】
【化３１】

【００４４】
【化３２】

【００４５】
【化３３】

【００４６】
【化３４】

【００４７】
【化３５】

【００４８】
【化３６】

【００４９】
【化３７】

【００５０】
【化３８】

【００５１】
【化３９】

【００５２】
【化４０】

【００５３】
【化４１】

【００５４】
【化４２】

【００５５】
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。
【００５６】
（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、目的の色素を得る。
また例えばＮｏ．（２５）で示される色素は上記（Ｂ）の工程の代わりに下記（Ｃ）の工程を行うことにより製造できる。
【００５７】
（Ｃ）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２８％アンモニア水を加え、６０〜７０℃に昇温し、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、目的の色素を得る。
【００５８】
本発明の記録液においては、着色剤として、前記一般式（Ｉ）で示される色素から選ばれる少なくとも１種の色素を含む全色素を、記録液全重量に対して合計０．５〜８重量％、特に２〜５重量％の割合で含有するのが好ましい。
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。
【００５９】
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。
本発明の記録液のｐＨは、好ましくは５〜１１、より好ましくは６〜１０に維持して用いることで記録液の保存安定性をさらに改良することができる。
【００６０】
【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、イソプロピルアルコール３重量部、前記Ｎｏ．（１）の色素（最大吸収波長λmax ＝５１３ｎｍ）３重量部に水を加え、５重量％アンモニア水で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。
【００６１】
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８ＪＣ−６１０ＪＷ、キヤノン社製品）を用いて電子写真用紙（ゼロックス社製品）及び専用コート紙：ＨＲ−１０１（キヤノン社製品）にインクジェット記録を行い、鮮明な色調（彩度）のマゼンタ印字物を得た。また下記に（ａ），（ｂ），（ｃ），（ｄ）及び（ｅ）の評価方法と諸評価の結果を示す。
（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（電子写真用紙にのみ実施）：
（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（ｏｐｔｉｃａｌ ｄｅｎｓｉｔｙ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。
【００６２】
（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、９４．８％であった。
【００６３】
【数１】

【００６４】
（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。
【００６５】
（ｅ）記録画像のマイグレーション性（専用コート紙にのみ実施）
４０℃、９０％ＲＨ槽内に印字物を１Ｈｒ放置し、印字物の字のニジミの程度を目視で判定した。その結果印字物の字のニジミは全く認められなかった。
【００６６】
実施例２
グリセリン５重量部、エチレングリコール１０重量部、前記Ｎｏ．（２）の色素２．５重量部に水を加え、水酸化リチウム水溶液でｐＨを９に調整して全量を１００重量部とし、この組成物を実施例１に記載の方法により処理して記録液を調製した。この記録液を用いて、実施例１と同様に印字を行った結果、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、実施例１の（ａ）〜（ｅ）による諸評価を行った。その結果、実施例１と同様に何れも良好な結果が得られた。
またＯＤ残存率は９５．５％であった。
【００６７】
実施例３及び４
実施例１において用いた前記Ｎｏ．（１）の色素３重量部の代わりに、それぞれ前記Ｎｏ．（３）とＮｏ．（４）の色素を使用した以外は、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）〜（ｅ）による諸評価を行った。その結果、実施例１と同様に何れも良好な結果を得た。
またＯＤ残存率はそれぞれ９０．３％、９２．１％であった。
【００６８】
実施例５
実施例１において用いた前記Ｎｏ．（１）の色素３重量部の代わりに前記Ｎｏ．（１）の色素とＮｏ．（２０）の色素をそれぞれ１．５重量部ずつ混合して使用した以外は、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）〜（ｅ）による諸評価を行った。その結果、実施例１と同様に何れも良好な結果を得た。
またＯＤ残存率はそれぞれ９２．８％であった。
【００６９】
実施例６〜２４
実施例１において用いた前記Ｎｏ．（１）の色素の代わりに、それぞれ、前記Ｎｏ．（５）〜Ｎｏ．（１９）、Ｎｏ．（２１）〜Ｎｏ．（２４）の色素を使用した以外は、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）〜（ｅ）による諸評価を行った。その結果、実施例１と同様に何れも良好な結果を得た。
またＮｏ．（５）の色素を用いた場合（実施例６）のＯＤ残存率は９４．１％であった。
【００７０】
比較例１
実施例１において用いた前記Ｎｏ．（１）の色素の代わりに、下記（Ａ）の構造の色素を使用した以外は、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）〜（ｅ）による諸評価を行った。
【００７１】
【化４３】

【００７２】
比較例２
実施例１において用いた前記Ｎｏ．（１）の色素の代わりに、国際公開ＷＯ
９４／１６０２１のＥｘａｍｐｌｅ２に使用されている下記（Ｂ）の構造の色素を使用した以外は、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）〜（ｅ）による諸評価を行った。
【００７３】
【化４４】

【００７４】
比較例３
実施例１において用いた前記Ｎｏ．（１）の色素の代わりに、特開平４−２７９６７１号公報の例５に記載されている化合物のＺがＯＨ基である下記（Ｃ）の構造の色素を使用した以外は、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）〜（ｅ）による諸評価を行った。
【００７５】
【化４５】

【００７６】
比較例４
実施例１において用いた前記Ｎｏ．（１）の色素の代わりに、特開平８−２１８０２１号公報の実施例に使用されている下記（Ｄ）の構造の色素を使用した以外は、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）〜（ｅ）による諸評価を行った。
【００７７】
【化４６】

【００７８】
比較例５
実施例１において用いた前記Ｎｏ．（１）の色素の代わりに、下記（Ｅ）の構造の色素を使用した以外は、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）〜（ｅ）による諸評価を行った。
【００７９】
【化４７】

【００８４】
実施例２５、２６
実施例１において用いた前記Ｎｏ．（１）の色素の代わりに、それぞれ、前記Ｎｏ．（３６）、Ｎｏ．（４５）の色素を使用した以外は、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）〜（ｅ）による諸評価を行った。その結果、実施例１と同様に何れも良好な結果を得た。上記の実施例１〜６及び比較例１〜５の結果を纏めて下記第１表に示した。
【００８５】
【表１】

【００８７】
【００８８】
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定してＬ^* 、ａ^* 、ｂ^* の値を求め、下式に従い計算し、
【００８９】
【数２】

【００９０】
電子写真用紙では、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。専用コート紙ではその値が、７０以上のものを○、６５以上７０未満のものを△、６５未満のものを×とした。
耐光性においては、○は目視で変退色は殆ど認められない、△は目視で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。
耐水性の滲みにおいては、○は目視で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。
【００９１】
保存安定性においては、記録液を試験管にとり観察して、○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。
記録画像のマイグレーション性においては、○は印字物の字が全っくニジまない状態、△は印刷物の字がややニジむ状態、×は印字物の字がニジむ状態を表わす。
【００９２】
【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、普通紙・専用紙に記録した場合、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、専用紙におけるマイグレーション性に優れている他、記録液としての信頼性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 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 the 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. However, it is difficult to satisfy many of these requirements at the same time.
[0004]
For this reason, various proposals (for example, JP 61-101574, JP 61-101576, JP 61-195176, JP 61-62562, JP 61-247771, JP 62-156168, JP 62-246974, JP 63-63765, JP 63-295665, JP 1-123866, JP 1-240584, JP 2-16171, JP-A-3-122171, JP-A-3-203970, JP-A-4-153272, etc.) have been made, but have not yet fully satisfied market demands.
[0005]
Japanese Patent Application Laid-Open No. 4-279671 and PCT International Publication WO 94/16021 disclose that a dye having a structure in which two molecules of a specific monoazo dye having a triazinyl group are linked via a divalent organic bonding group is inkjet recording. It is described that can be used.
However, in the former case, the divalent organic bonding group as the linking group is not important, and only linking groups such as (substituted) phenylenediamine are exemplified. Since such a linking group is planar in terms of structure, when a dye having such a linking group is used, the printed image is poorly generated and the color density is insufficient.
[0006]
In addition, these groups are conjugated, and when such groups are included, the color tone is deepened, resulting in a strong blue tint. Further, as a group substituted with a triazinyl group (indicated by Z. Corresponding to the group represented by X ₁ or X ₂ in the present application), it is directly bonded to a triazinyl group such as NHC ₂ H ₄ OH or a morpholino group. N atoms are preferred, and the examples are also limited to dyes having such a structure. Such dyes also tend to reduce the color saturation of the image.
[0007]
Furthermore, in the latter, the divalent organic bonding group as a linking group is a group of (substituted) phenylenediamine or substituted piperazine, and among these, the divalent organic bonding group of (substituted) phenylenediamine is as described above. It is not preferable. Moreover, when substituted piperazine is used as a divalent organic bonding group, as specifically shown in Comparative Example 2 described later, it is insufficient in terms of light resistance and water resistance.
JP-A-8-218021 also describes that a dye having a structure in which two molecules of a specific monoazo dye having a triazinyl group are linked via a divalent organic bonding group can be used for inkjet recording.
However, unlike the structure of the present invention, the structure of the linking group is insufficient in reliability, light resistance and color tone.
[0008]
[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.
[0009]
In particular, magenta dyes conventionally used in recording liquids have good water resistance, and since the recording material is mainly paper, commercially available dyes having high affinity for cellulose, that is, high directity ( Direct dyes) were used, but these were unclear in color tone, and conversely, acid dyes with clear color tone were inferior in water resistance, and development of magenta dyes satisfying both color tone and water resistance was desired. .
[0010]
[Means for Solving the Problems]
The present inventors first select a divalent linking group, a substituent of the triazinyl group, and the like for a dye having a structure in which two molecules of a monoazo dye having a triazinyl group are linked via a divalent organic linking group. Thus, a dye that overcomes the above-mentioned drawbacks has been proposed (Japanese Patent Laid-Open No. 8-218021). The present invention has achieved the present invention by confirming that, when a dye having a further improved structure is used as a recording liquid component, both the color tone and the water resistance are satisfied, and the above object is achieved. is there. That is, the gist of the present invention resides in an aqueous medium and a recording liquid containing at least one dye whose free acid type is represented by the following general formula (I).
[0011]
Embedded image

[0012]
Wherein, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted phenyl group or a naphthyl group; X _1, X ₂ is -O R ₁ or represents a chlorine atom; R ₁ is, 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, and of these, other than a hydrogen atom group rather good further have a substituent; Y is a divalent linking group selected from the group of radicals and a group represented by the following general formula (II) ~ (IV),
Formula (II)
[0013]
Embedded image

[0014]
(In the formula, R ₄ and R ₆ each independently represent a linear or branched alkylene group having 1 to 8 carbon atoms; R ₅ represents a linear or branched alkylene group having 1 to 12 carbon atoms. A group or the following formula (a); p represents a number of 0 to 20;
[0015]
Embedded image

General formula (III)
[0016]
Embedded image

(Wherein R ₇ and R ₈ represent a hydrogen atom or a methyl group)
Formula (IV)
[0017]
Embedded image

[0018]
(Wherein R ₉ and R ₁₀ represent a hydrogen atom, a methyl group or a methoxy group)
(Group A)
[0019]
Embedded image

[0020]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
The dye used in the present invention has a free acid type represented by the general formula (I) in claim 1.
Specifically, in the general formula (1), the substituents for Ar ¹ and Ar ² are each independently a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms (eg, methyl group, ethyl group, n-propyl). Group, isopropyl group, n-butyl group, 2-ethylhexyl group, trifluoromethyl group, dimethylaminomethyl group, etc.), substituted or unsubstituted alkoxy group having 1 to 9 carbon atoms (for example, 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 group (eg, carbamoyl group, N, N— Dimethylcarbamoyl group, phenylcarbamoyl group, etc.), substituted or unsubstituted sulfamoyl group (for example, sulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, p-carboxyphenylsulfamoyl group, etc.), substitution Or an unsubstituted amino group (for example, N-methylamino group, carbamoylamino group, N, N-diethylamino group, acetylamino group, N-methyl-N-acetylamino group, etc.), nitro group, sulfonate group (For example, a phenoxysulfonyl group), a sulfonyl group (for example, a hydroxyethylsulfonyl group, a benzylsulfonyl group, etc.), a carboxyl group, and a carboxylate group (for example, a methoxycarbonyl group).
[0021]
X ₁ and X ₂ each represent a group represented by —OR ₁ or —NR ₂ R ₃ or a chlorine atom, and the substituent represented by R ₁ is independently a hydrogen atom, substituted or unsubstituted carbon, A C1-C8 alkyl group (for example, methyl group, ethyl group, n-butyl group, n-octyl group, ethylhexyl group, isopropyl group, tert-butyl group, carboxymethyl group), substituted or unsubstituted carbon number 2 Or 3 alkenyl groups (for example, vinyl group, allyl group, etc.), aryl groups (for example, phenyl group, 4-nitrophenyl group, 4-butylphenyl group, 4-carboxyphenyl group, etc.), aralkyl groups (for example, benzyl group) group, phenethyl group, etc.), a cyclohexyl group, a nitrogen-containing Hajime Tamaki (e.g., pyridyl group) and the like, and the substituent represented by R _2, R _3, its 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) , Hydroxyethyl group, etc.), substituted or unsubstituted alkenyl group having 2 or 3 carbon atoms (eg, vinyl group, allyl group, etc.), aryl group (eg, phenyl group, 4-nitrophenyl group, 4-butylphenyl group) Etc.), aralkyl groups (for example, benzyl group, phenethyl group, etc.), cyclohexyl groups, nitrogen-containing heterocyclic groups (for example, pyridyl group, etc.) and the like.
Examples of R ₂ and R ₃ forming a 5- or 6-membered ring together with the nitrogen atom to be bonded include a morpholine ring, piperazine ring or piperazine ring.
[0022]
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 ₄ and R _{6 each} have 1 to 8 carbon atoms. , Preferably 2 to 4 linear or branched alkylene groups (for example, ethylene group, propylene group, trimethylene group, etc.), and R ₅ 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.
[0023]
Embedded image

[0024]
The dye of the present invention has such a linking group and thus has higher reliability than that of 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.
Among the dyes represented by the general formula (I), those having a naphthyl group represented by Ar ¹ and Ar ² having a group selected from a sulfo group and a carboxyl group as a substituent are preferable.
The dye represented by the general formula (I) is preferably a dye represented by the following general formula (I ′).
[0025]
Embedded image

[0026]
(Wherein R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms, a substituted or unsubstituted carbon group having 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; and X ₁ , X _2, and Y are as defined in formula (I). is there.)
[0027]
Specifically, in the general formula (1 ′), the substituents represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently substituted or unsubstituted alkyl having 1 to 9 carbon atoms. A group (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), a substituted or unsubstituted carbon number of 1 to 9 Alkoxy group (for example, methoxy group, isopropoxy group, n-butoxy group, chloroethoxy group, etc.), halogen atom (for example, fluorine atom, chlorine atom, bromine atom, etc.), hydrogen atom, hydroxyl group, substituted or unsubstituted Carbamoyl group (for example, carbamoyl group, N, N-dimethylcarbamoyl group, phenylcarbamoyl group, etc.), substituted or unsubstituted sulfamoyl Groups (for example, sulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, p-carboxyphenylsulfuryl group) Famoyl group, etc.), substituted or unsubstituted amino group (eg, N-methylamino group, carbamoylamino group, N, N-diethylamino group, acetylamino group, N-methyl-N-acetylamino group, etc.), nitro Groups, sulfonic acid ester groups (for example, phenoxysulfonyl group), sulfonyl groups (for example, hydroxyethylsulfonyl group, benzylsulfonyl group, etc.), carboxyl groups and carboxylic acid ester groups (for example, methoxycarbonyl group). .
[0028]
Among the dyes of the present invention represented by the general formula (I ′), dyes having a structure in which the number of carboxyl groups in R _{11 to} R ₁₆ is 3 or less are generally preferred from the viewpoint of water resistance.
m and n are each preferably 0 or 1.
[0029]
When m and n are 0 or 1, at least one of R ₁₁ , R ₁₂ and R ₁₃ and at least one of R ₁₄ , R ₁₅ and R ₁₆ 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. It is better to use a dye.
[0030]
In the general formula (I ′), when m and n are 0, at least one of R _{11 to} R ₁₃ and at least one of R _{14 to} R ₁₆ are hydrogen atoms, and R _{11 to} R ₁₃ At least one and at least one of R _{14 to} R ₁₆ 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 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 a group selected from each phenyl group. The bonding position is preferably a dye having a structure that is ortho to the bonding position of the azo group.
On the other hand, in the general formula (I ′),
[0031]
Embedded image

[0032]
Further, X ₁ and X ₂ in the general formula (I) are preferably OH groups,
[0033]
Embedded image

[0034]
Among the dyes represented by the general formula (I ′), a dye having a structure of the right and left objects is preferably used via a linking group Y whose free acid type is represented by the following general formula (V). . This pigment is preferable in terms of color tone, water resistance, and practicality.
[0035]
Embedded image

[0036]
(In the formula, R ₁₁ , R ₁₂ , R ₁₃ , X ₁ , 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. Examples thereof include dyes having the structures shown in (1) to (52).
[0037]
Embedded image

[0038]
Embedded image

[0039]
Embedded image

[0040]
Embedded image

[0041]
Embedded image

[0042]
Embedded image

[0043]
Embedded image

[0044]
Embedded image

[0045]
Embedded image

[0046]
Embedded image

[0047]
Embedded image

[0048]
Embedded image

[0049]
Embedded image

[0050]
Embedded image

[0051]
Embedded image

[0052]
Embedded image

[0053]
Embedded image

[0054]
Embedded image

[0055]
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].
[0056]
(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 cause a hydrolysis reaction, followed by cooling and salting out with sodium chloride to obtain the target dye.
Also, for example, No. The pigment | dye shown by (25) can be manufactured by performing the process of the following (C) instead of the process of the said (B).
[0057]
(C) 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, 28% aqueous ammonia is added, the temperature is raised to 60 to 70 ° C., the reaction is performed, and then cooled and salted out with sodium chloride to obtain the target dye.
[0058]
In the recording liquid of the present invention, the total dye containing at least one dye selected from the dyes represented by the general formula (I) as the colorant is 0.5 to 8 weight in total with respect to the total weight of the recording liquid. %, Particularly 2 to 5% by weight.
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.
[0059]
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.
The storage stability of the recording liquid can be further improved by maintaining the pH of the recording liquid of the present invention at preferably 5 to 11, more preferably 6 to 10.
[0060]
【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 isopropyl alcohol, Water was added to 3 parts by weight of the dye (1) (maximum absorption wavelength λmax = 513 nm), and the pH was adjusted to 9 with 5% by weight aqueous ammonia 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.
[0061]
Using the obtained recording liquid, an inkjet printer (product name 8JC-610JW, Canon product) is used to perform inkjet recording on electrophotographic paper (Xerox product) and dedicated coated paper: HR-101 (Canon product). And a magenta printed matter having a clear color tone (saturation) was obtained. The evaluation methods (a), (b), (c), (d) and (e) and the results of various evaluations 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 (implemented only on electrophotographic paper):
(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 (optical density value) of the solid printed part before and after immersion was measured with a Macbeth densitometer (trade name: TR927, Macbeth product).
[0062]
(2) Test results As a result of the above (1), the image was slightly blurred.
Further, the change in density of the solid print portion before and after the immersion in the above (2) was 94.8% when represented by the OD residual ratio according to the following formula.
[0063]
[Expression 1]

[0064]
(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.
[0065]
(E) Recorded image migration (implemented only on special coated paper)
The printed matter was left for 1 hour in a 40 ° C., 90% RH tank, and the degree of blurring of the printed matter was visually determined. As a result, no blurring was observed on the printed matter.
[0066]
Example 2
5 parts by weight of glycerin, 10 parts by weight of ethylene glycol, No. Water is added to 2.5 parts by weight of the dye of (2), the pH is adjusted to 9 with an aqueous lithium hydroxide solution to make the total amount 100 parts by weight, and this composition is processed by the method described in Example 1 and recorded. A liquid was prepared. Using this recording liquid, 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. Further, various evaluations according to (a) to (e) of Example 1 were performed on the recorded matter. As a result, similar to Example 1, good results were obtained.
Further, the residual OD ratio was 95.5%.
[0067]
Examples 3 and 4
The No. 1 used in Example 1 was used. Instead of 3 parts by weight of the dye of (1), each of the above No. (3) and No. A recording liquid was prepared by the method of Example 1 except that the dye of (4) was used, printing was performed, and various evaluations according to (a) to (e) of Example 1 were performed on the recorded matter. . As a result, similar to Example 1, good results were obtained.
Further, the OD residual ratios were 90.3% and 92.1%, respectively.
[0068]
Example 5
The No. 1 used in Example 1 was used. In place of 3 parts by weight of the dye of (1), The dye of (1) and No. A recording liquid was prepared by the method of Example 1 except that 1.5 parts by weight of each of the dyes of (20) were mixed and used, and printing was performed. Various evaluations according to (e) were performed. As a result, similar to Example 1, good results were obtained.
Moreover, the OD residual rate was 92.8%, respectively.
[0069]
Examples 6-24
The No. 1 used in Example 1 was used. Instead of the dye of (1), each of the above-mentioned No. (5) -No. (19), No. (21) -No. A recording liquid was prepared by the method of Example 1 except that the dye of (24) was used, printing was performed, and various evaluations according to (a) to (e) of Example 1 were performed on the recorded matter. . As a result, similar to Example 1, good results were obtained.
No. When the dye (5) was used (Example 6), the OD residual rate was 94.1%.
[0070]
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 a dye having the following structure (A) was used instead of the dye of (1), and printing was performed. Various evaluations by a) to (e) were performed.
[0071]
Embedded image

[0072]
Comparative Example 2
The No. 1 used in Example 1 was used. International publication WO instead of the dye of (1)
A recording liquid was prepared by the method of Example 1 except that the dye having the following structure (B) used in Example 2 of 94/16021 was used, and printing was performed. Various evaluations by (a) to (e) were performed.
[0073]
Embedded image

[0074]
Comparative Example 3
The No. 1 used in Example 1 was used. Instead of the dye of (1), the compound of Example 1 was used except that the compound described in Example 5 of JP-A-4-279671 used a dye having the following structure (C) wherein Z is an OH group. A recording liquid was prepared by the method, printing was performed, and various evaluations according to (a) to (e) of Example 1 were performed on the recorded matter.
[0075]
Embedded image

[0076]
Comparative Example 4
The No. 1 used in Example 1 was used. Instead of the dye of (1), a recording liquid was prepared by the method of Example 1 except that the dye having the following structure (D) used in the examples of JP-A-8-218021 was used. Printing was performed, and various evaluations according to (a) to (e) of Example 1 were performed on the recorded matter.
[0077]
Embedded image

[0078]
Comparative Example 5
The No. 1 used in Example 1 was used. A recording liquid was prepared by the method of Example 1 except that a dye having the following structure (E) was used in place of the dye of (1), and printing was performed. Various evaluations by a) to (e) were performed.
[0079]
Embedded image

[0084]
Examples 25 and 26
The No. 1 used in Example 1 was used. Instead of the dye of (1), each of the above-mentioned No. (36), No. A recording liquid was prepared by the method of Example 1 except that the dye of (45) was used, printing was performed, and various evaluations according to (a) to (e) of Example 1 were performed on the recorded matter. . As a result, similar to Example 1, good results were obtained . Shown in Table 1 below summarizes the above SL results of Examples 1-6 and Comparative Examples 1-5.
[0085]
[Table 1]

[0087]
[0088]
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:
[0089]
[Expression 2]

[0090]
In the electrophotographic paper, the value of 60 or more was evaluated as ◯, 55 or more and less than 60 as Δ, and 55 or less as ×. For the special coated paper, those with a value of 70 or more were marked with ◯, those with a value of 65 or more and less than 70 were marked with Δ, and those with a value less than 65 were marked with ×.
In light resistance, ◯ indicates almost no fading color visually, Δ indicates slightly fading color visually, and x indicates a state where the fading color is remarkable and is not at a practical level.
In water-resistant bleeding, ○ is slightly observed from the state where there is almost no bleeding visually, but the outline of the image is only slightly blurred, almost no decrease in the density of the image is observed, and Δ is bleeding However, the blur range is small and the decrease in the density of the image is small. X indicates that the blur is remarkable and the blur range is large, and it is difficult to identify the original image portion, indicating a state that is not at a practical level.
[0091]
In terms of storage stability, the recording solution was observed in a test tube. ○ represents a state in which no insoluble matter was observed, △ represents a state in which a small amount of insoluble matter was observed, and x represents a state in which insoluble matter was noticeable. Indicates a state that is not.
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 two recovery operations, and Δ indicates a normal state in three to four recovery operations. The state of returning to the printing state is represented, 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 in which the first character is faint and not missing, Δ indicates a portion in which the first character is faint or missing, and × indicates that the first character is completely absent Indicates that printing is not possible.
In the migration property of the recorded image, ◯ indicates a state in which the characters of the printed matter are not completely distorted, Δ indicates a state in which the character of the printed matter is slightly distorted, and x indicates a state in which the character of the printed matter is not compliant.
[0092]
【The invention's effect】
The recording liquid of the present invention is used for ink jet recording and writing instruments, and when recorded on plain paper / special paper, a clear magenta-colored recorded matter can be obtained, and its print density, light resistance, water resistance In addition to the excellent migration property of the special paper, the reliability and storage stability as a recording liquid are also good.

Claims (9)

A recording liquid comprising an aqueous medium and at least one dye selected from dyes represented by the following general formula (I):

Wherein, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted phenyl group or a naphthyl group; X _1, X ₂ is -O R ₁ or represents a chlorine atom; R ₁ is, 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, and of these, other than a hydrogen atom group is rather good 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 ₄ and R ₆ each independently represent a linear or branched alkylene group having 1 to 8 carbon atoms; R ₅ represents a linear or branched alkylene group having 1 to 12 carbon atoms. A group or the following formula (a); p represents a number of 0 to 20;

General formula (III)

(Wherein R ₇ and R ₈ represent a hydrogen atom or a methyl group)
Formula (IV)

(Wherein R ₉ and R ₁₀ represent a hydrogen atom, a methyl group or a methoxy group)
(Group A)

The recording liquid according to claim 1, wherein the dye represented by the general formula (I) is a dye represented by the following general formula (I ′).

(Wherein R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently a substituted or unsubstituted alkyl group having 1 to 9 carbon atoms, a substituted or unsubstituted carbon group having 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; and X ₁ , X _2, and Y are as defined in formula (I). is there.) The recording liquid according to claim 2 , wherein the dye represented by the general formula (I ′) is a dye having a structure in which the number of carboxyl groups (COOH groups) in R _{11 to} R ₁₆ is 3 or less. The dye represented by the general formula (I ′) has a structure in which m and n are 1 and 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. recording liquid according to claim 2 which is a dye. The dye represented by formula (I) is, X _1, recording liquid according to any one of claims 1 to 4 groups represented by X ₂ is a dye of structure is OH group. The recording liquid according to any one of claims 1 to 5, which has a pH of 5 to 11. 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 7. A water-soluble dye characterized in that the type of the free acid is represented by the following general formula (I) .

Wherein, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted phenyl group or a naphthyl group; X _1, X ₂ is -O R ₁ or represents a chlorine atom; R ₁ is, 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, and of these, other than a hydrogen atom group is rather good 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 ₄ and R ₆ each independently represent a linear or branched alkylene group having 1 to 8 carbon atoms; R ₅ represents a linear or branched alkylene group having 1 to 12 carbon atoms. A group or the following formula (a); p represents a number of 0 to 20;

General formula (III)

(Wherein R ₇ and R ₈ represent a hydrogen atom or a methyl group)
Formula (IV)

(Wherein R ₉ and R ₁₀ represent a hydrogen atom, a methyl group or a methoxy group)
(Group A)