JP3679481B2 - Ink set, ink jet recording method, and ink jet apparatus - Google Patents

Description

（式中、Ｒ₁は炭素数１〜４８のアルキル基又は水素原子を表し、Ｒ₂は（ＣＨ₂）_a−Ｘ₁又は水素原子を表し、ａは１〜４のいずれかの整数とする。Ｒ₃は（ＣＨ₂）_b−Ｘ₂又はＲ₄−Ｙ又は水素原子を表し、ｂは１〜４のいずれかの整数とする。Ｒ₄は炭素数１〜４８のアルキル基又は水素原子を表す。Ｚは（ＮＲ₅ Ｃ_lＨ_2l）_c（ＮＨＣ_nＨ_2n）_dを表し、ｌ及びｎは２〜４のいずれかの整数、ｃ＋ｄは０〜５０のいずれかの整数とする。Ｙは（ＮＲ₆Ｃ_mＨ_2m）_e（ＮＨＣ_pＨ_2P）_fを表し、ｍ及びｐは２〜４のいずれかの整数、ｅ＋ｆは０〜５０のいずれかの整数とする。Ｒ₅は（ＣＨ₂）_g−Ｘ₃を表し、ｇは１〜４のいずれかの整数とする。Ｒ₆は（ＣＨ₂）_h−Ｘ₄を表し、ｈは１〜４のいずれかの整数とする。Ｘ₁、Ｘ₂、Ｘ₃及びＸ₄は、夫々、カルボキシル基、カルボキシル基の塩、スルホン基、スルホン基の塩又は水素原子からなる群から選ばれる。又、Ｒ₂及びＲ₃が夫々水素原子である時、ｃ及びｅが共に０になることはなく、又、Ｘ₁、Ｘ₂、Ｘ₃及びＸ₄ が全て水素原子になることもない。）
【００２６】
本発明のインクセットを構成するインクの成分として用いられるアニオン性染料としては、既存のものでも、又、新規に合成したものでも適度な色調と濃度とを有するものであれば、大抵のものを使用することができる。又、これらのうちのいずれかを混合して用いることもできる。アニオン性染料の具体的なものとしては、例えば、下記のようなものが挙げられる。
Ｃ．Ｉ．ダイレクトイエロー ８、１１、１２、２７、２８、３３、３９、４４、５０、５８、８５、８６、８７、８８、８９、９８、１００、１１０、
Ｃ．Ｉ．ダイレクトレッド ２、４、９、１１、２０、２３、２４、３１、３９、４６、６２、７５、７９、８０、８３、８９、９５、１９７、２０１、２１８、２２０、２２４、２２５、２２６、２２７、２２８、２３０、
Ｃ．Ｉ．ダイレクトブルー １、１５、２２、２５、４１、７６、７７、８０、８６、９０、９８、１０６、１０８、１２０、１５８、１６３、１６８、１９９、２２６、
【００２７】
Ｃ．Ｉ．ダイレクトブラック １７、１９、２２、３１、３２、５１、６２、７１、７４、１１２、１１３、１５４、１６８、１９５、
Ｃ．Ｉ．アシッドイエロー １、３、７、１１、１７、２３、２５、２９、３６、３８、４０、４２、４４、７６、９８、９９、
Ｃ．Ｉ．アシッドレッド ６、８、９、１３、１４、１８、２６、２７、３２、３５、４２、５１、５２、８０、８３、８７、８９、９２、１０６、１１４、１１５、１３３、１３４、１４５、１５８、１９８、２４９、２６５、２８９、
Ｃ．Ｉ．アシッドブルー １、７、９、１５、２２、２３、２５、２９、４０、４３、５９、６２、７４、７８、８０、９０、１００、１０２、１０４、１１７、１２７、１３８、１５８、１６１、
【００２８】
Ｃ．Ｉ．アシッドブラック ２、４８、５１、５２、１１０、１１５、１５６、
Ｃ．Ｉ．リィアクティブイエロー ２、３、１７、２５、３７、４２、
Ｃ．Ｉ．リィアクティブレッド ７、１２、１３、１５、１７、２０、２３、２４、３１、４２、４５、４６、５９、
Ｃ．Ｉ．リィアクティブブルー ４、５、７、１３、１４、１５、１８、１９、２１、２６、２７、２９、３２、３８、４０、４４、１００、
Ｃ．Ｉ．フードイエロー ３、
Ｃ．Ｉ．フードレッド ８７、９２、９４、
Ｃ．Ｉ．フードブラック１、２
【００２９】
本発明のインクセットを構成するインクの成分として用いられるカチオン性染料としては、既存のものでも、又、新規に合成したものでも適度な色調と濃度とを有するものであれば、大抵のものを使用することができる。又、これらのうちのいずれかを混合して用いることもできる。カチオン性染料の具体的なものとしては、例えば、下記のようなものが挙げられる。
Ｃ．Ｉ．ベーシックイエロー １、１１、１３、１９、２５、３３、３６、
Ｃ．Ｉ．ベーシックレッド １、２、９、１２、１３、３８、３９、９２、
Ｃ．Ｉ．ベーシックブルー １、３、５、９、１９、２４、２５、２６、２８、４５、５４、６５、
Ｃ．Ｉ．ベーシックブラック ２、８、
Aizen Cathilon Black ＳＢＨ、ＢＸＨ、ＳＨ、ＡＣＨ、ＭＨ、ＴＨ（保土ケ谷化学製）
Sumiacryl Black Ｂ、Ｒ、ＡＰ、ＢＰ、ＣＰ、ＦＦＰ（住友化学製）、
Diacryl Supra Black ＧＳＬ、ＲＳＬ、ＥＳＬ（三菱化成製）、
【００３０】
本発明のインクセットを構成するインクの成分として用いられる分散染料を含む非水溶性染料としては、既に市販されているもの、又は、新規に合成したものでも適度な色調と濃度を有するものであれば大抵のものを使用することができるし、又、複数の染料を混色させて用いることもできる。本発明に使用し得る非水溶性染料としては、例えば、下記のようなものが挙げられる。
【００３１】
Ｃ．Ｉ．ディスパースイエロー ３、４、５、７、２３、３３、４２、４９、５４、５６、６４、７１、７９、８２、８３、８６、８８、９３、９９、１１６、１１９、１４１、１６０、１６３、１９８、２０４、２１８、２２４、２２６、２３０、
【００３２】
Ｃ．Ｉ．ディスパースレッド １、４、５、７、１１、１２、１３、１５、１７、３０、３３、４３、５０、５２、５３、５４、５５、５６、５８、５９、６０、６５、７２、７３、７４、７５、７６、８２、８６、８８、９０、９１、９２、９６、１０５、１０６、１０７、１１０、１１７、１１８、１２６、１２７、１２８、１３１、１３２、１３４、１３５、１３６、１３７、１４０、１４３、１４５、１４６、１５１ｓ、１５３、１５９、１６４、１６７、１６９、１７７、１８１、１８４、１８８、１９０、１９１、２００、２０３、２０５、２０６、２２１、２２３、２２４、２２５、２２７、２２９、２３９、２４０、２５８、２７７、２７８、２７９、２８３、２８８、３０２、３０９、３１１、３１２、３２３、３２９、３３２、３４０、３４１、３４３、
【００３３】
Ｃ．Ｉ．ディスパースブルー １、３、７、１３、１９、２６、２７、３５、４４、５４、５５、５６、６０、６４、６５、７２、７３、７９、８１、８２、８７、９１、９３、９４、９６、１０２、１０６、１１８、１２０、１２２、１２５、１２８、１３０、１３９、１４２、１４３、１４６、１４８、１４９、１５３、１５４、１６５、１６７、１８１、１８３、１８５、１８６、１８９、１９８、２００、２０１、２０５、２０７、２１４、２２４、２２５、２５７、２５９、２６６、２６８、２７０、２８４、２８５、２８７、２８８、２９１、２９３、３０１、３３０、３３２、３３３、３３７、３４１、３４５、３５１、３５２、３５３、
【００３４】
Ｃ．Ｉ．ディスパースブラック １、９、１０、Ｂｌａｃｋ ＧＬ、ＢｌａｃｋＢ、Ｂｌａｃｋ Ｌ、Ｂｌａｃｋ ２Ｂ、Ｂｌａｃｋ Ｂ−Ｔ、Ｂｌａｃｋ ＯＢＬ、Ｂｌａｃｋ ＲＳＲ、Ｂｌａｃｋ ＴＫ、Ｂｌａｃｋ ＴＧ、Ｂｌａｃｋ Ｓ−ＣＴＬ、Ｂｌａｃｋ Ｈ−ＤＢ、Ｂｌａｃｋ ＲＤ−ＳＧＴ、Ｂｌａｃｋ Ｓ−２ＢＬ、Ｂｌａｃｋ Ｓ−３ＢＬ、Ｂｌａｃｋ Ｓ−５ＢＬ、Ｂｌａｃｋ Ｓ−ＢＮＬ、Ｂｌａｃｋ Ｓ−３ＧＬＮ、Ｂｌａｃｋ Ｓ−ＳＴ、Ｂｌａｃｋ Ｓ−ＦＧＢ、Ｂｌａｃｋ Ｓ−ＳＧＮ、Ｂｌａｃｋ Ｓ−ＷＬＡ、Ｂｌａｃｋ Ｓ−ＷＬＡＴ、Ｂｌａｃｋ Ｂ８２、Ｂｌａｃｋ ＢＴＮＵ８２、Ｂｌａｃｋ ２ＢＬ、Ｂｌａｃｋ ＨＲ−ＦＳ、Ｂｌａｃｋ ＲＢ−ＦＳ、Ｂｌａｃｋ ＨＧ−ＦＳ、Ｂｌａｃｋ ＧＢ−ＦＳ、Ｂｌａｃｋ ＫＮ−ＦＳ。
尚、本発明において好適な非水溶性染料は上記に列挙したものに限定されるものではない。
【００３５】
本発明のインクセットを構成するインクにおいて用いられる、分散型インクの色成分に好適に使用される顔料としては、既存のものでも、又、新規に合成したものでも、インクに適度な色調と濃度を有するものであれば、大抵のものを使用することができる。具体的には、例えば、チタン系、ベンガラ、アルミニウム粉、タルク、クレー、炭酸カルシウム、及びシリカ等の無機顔料；カーボンブラック、アゾ系、フタロシアニン系、キナクリドン系、コチニール、及び紅花色素等の有機顔料等が挙げられる。
【００３６】
又、この他にも分散型インクにおいては、非水溶性染料の分散剤又は可溶化剤として機能し得る高分子物質を使用することができる。このようなものとしては、例えば、ソルビタン脂肪酸誘導体、硫酸エステル誘導体、ポリオキシエチレンアルキレンエーテル型硫酸エステル、隣酸エステル誘導体、第４級アンモニウム塩誘導体、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルエステル類、脂肪酸類、アルケニルコハク酸塩類、高級アルコール硫酸エステル塩類、アルキルベンゼンスルホン酸ソーダ、アルキルジフェニルエーテルジスルホン酸塩類、ナフタレンスルホン酸ホルマリン縮合物等を含む界面活性剤を適宜に使用することができる。
【００３７】
又、特に顔料を使用する場合、必要に応じて分散剤として、例えば、アニオン又はノニオン系界面活性剤、ポリリン酸塩系分散剤、ナフタレンスルホン酸塩のホルマリン縮合物、ポリアクリル酸、ポリスチレンスルホン酸、スチレン−アクリル酸共重合体、スチレン−マレイン酸共重合体、スチレン−メタクリル酸共重合体、ビニルナフタレン−アクリル酸共重合体等のビニル化合物とカルボン酸系樹脂や、カルボキシメチルセルロース、ポリビニルアルコール、ポリアクリル酸部分アルキルエステル、ポリアクリルポリアミン等の樹脂を適宜使用できる。
【００３８】
分散型インクは、以上のような着色剤と分散剤又は可溶化剤の混合体をｐＨ調整した後、ボールミル、ロールミル、及びサンドミル等の分散機を用いて分散処理或いは必要に応じて遠心分離機にて遠心処理や濾過を行うことで予め分散液を調製した後、溶剤、界面活性剤、両性イオン化合物等の添加剤を加えて得ることができる。
【００３９】
以上のようにして調合される本発明で使用される各種のインクは、特に、サイズ度の高い被記録材との親和性に優れ、高速記録性、記録画像の光学濃度、色調、耐水性、耐摩擦性或いは耐光性に特に優れている。又、保存安定性、信号応答性、液滴形成の安定性、吐出安定性或いは連続記録性等に優れた実用的なインクである。
【００４０】
本発明で使用される各種インクには、上記したような各種成分の他に、更にインクの物性値を改善する目的で種々の添加剤を使用してもよい。例えば、ｐＨ調整剤、尿素のような結晶性有機化合物の乾燥防止剤、粘度調整剤、種々の界面活性剤等の表面張力調整剤、防カビ或いは殺菌剤等が挙げられる。或いは又、インクの液滴を帯電させ偏向することによって記録を行う方式が採用される場合には、添加剤として特に比抵抗調整剤を挙げることができる。
本発明は、以上のような優れた特性を有する所望の物性値に調合した各色インクを調製し、少なくとも異なる２色以上のインクを組み合わせたインクセットとし、種々のインクジェット記録方式にこれを適用することによって、高濃度で高品位の画像が形成される。即ち、本発明では、上記で述べた物性を有する２色以上のインクを使用し、インクジェット方式により画像を形成することによって、所期の目的を達成する。
【００４１】
本発明のインクジェット記録方法に適用されるインクジェット方式としては、従来公知の方式を何れも使用することができる。即ち、ピエゾ振動子の機械的振動を利用して液滴を発生させるタイプの記録ヘッドを有する記録装置以外の種々のインクジェット記録装置も好ましく用いられる。例えば、記録ヘッド内のインクに熱エネルギーの形で記録信号を与え、液滴を発生させて記録を行う装置等にも好適に用いられる。
尚、本発明に用いる黒色インク又はカラーのインクは、サインペン、万年筆等の筆記具用のインクに使用されてもよい。但し、筆記具用のインクとして使用する場合には、粘度、表面張力等をはじめ、種々の特性を筆記具用に調整する必要がある。
【００４２】
以下、上記した記録ヘッドの室内のインクに記録信号に対応した熱エネルギーを与え、該エネルギーにより液滴を発生させて記録を行う本発明に適用される記録装置について説明する。その装置の主要部であるヘッド構成例を、図１、図２及び図３に示す。
【００４３】
ヘッド１３は、インクを通す溝１４を有するガラス、セラミック又はプラスチック板等と、感熱記録に用いられる発熱ヘッド１５（図では薄膜ヘッドが示されているが、これに限定されるものではない。）とを接着して得られる。発熱ヘッド１５は、酸化シリコン等で形成される保護膜１６、アルミニウム電極１７−１及び１７−２、ニクロム等で形成される発熱抵抗体層１８、蓄熱層１９、及びアルミナ等の放熱性のよい基板２０より成っている。
【００４４】
インク２１は吐出オリフィス（微細孔）２２まで来ており、圧力Ｐによりメニスカス２３を形成している。
今、アルミニウム電極１７−１及び１７−２に電気信号情報が加わると、発熱ヘッド１５のｎで示される領域が急激に発熱し、ここに接しているインク２１に気泡が発生し、その圧力でメニスカス２３が突出し、インク２１が吐出しインク小滴２４となり、吐出オリフィス２２より被記録材２５に向って飛翔する。
【００４５】
図３には図１に示すヘッドを多数並べたマルチヘッドの外観図を示す。該マルチヘッドはマルチ溝２６を有するガラス板２７と、図１で説明したものと同様の発熱ヘッド２８を密着して作製されている。尚、図１は、インク流路に沿ったヘッド１３の断面図であり、図２は図１のＡ−Ｂ線での断面図である。
【００４６】
図４に、上記ヘッドを組み込んだインクジェット記録装置の一例を示す。図４において、６１はワイピング部材としてのブレードであり、その一端はブレード保持部材によって保持されて固定端となり、カンチレバーの形態をなす。ブレード６１は記録ヘッド６５による記録領域に隣接した位置に配置され、又、本例の場合、記録ヘッド６５の移動経路中に突出した形態で保持される。
６２は記録ヘッド６５の吐出口面のキャップであり、ブレード６１に隣接するホームポジションに配設され、記録ヘッド６５の移動方向と垂直な方向に移動して、インク吐出口面と当接し、キャッピングを行う構成を備える。更に６３はブレード６１に隣接して設けられるインク吸収体であり、ブレード６１と同様、記録ヘッド６５の移動経路中に突出した形態で保持される。
【００４７】
上記ブレード６１、キャップ６２及びインク吸収体６３によって吐出回復部６４が構成され、ブレード６１及びインク吸収体６３によってインク吐出口面の水分、塵挨等の除去が行われる。
６５は吐出エネルギー発生手段を有し、吐出口を配した吐出口面に対向する被記録材にインクを吐出して記録を行う記録ヘッド、６６は記録ヘッド６５を搭載してその移動を行うためのキャリッジである。
キャリッジ６６はガイド軸６７と摺動可能に係合し、キャリッジ６６の一部はモーター６８によって駆動されるベルト６９と接続（不図示）している。これによりキャリッジ６６はガイド軸６７に沿った移動が可能となり、記録ヘッド６５による記録領域及びその隣接した領域の移動が可能となる。
【００４８】
５１は被記録材を挿入するための給紙部、５２は不図示のモーターにより駆動する紙送りローラーである。これらの構成によって記録ヘッド６５の吐出口面と対向する位置へ被記録材が給紙され、記録が進行するにつれて排紙ローラー５３を配した排紙部へ排紙される。
上記構成において記録ヘッド６５が記録終了等でホームポジションに戻る際、吐出回復部６４のキャップ６２は記録ヘッド６５の移動経路から退避しているが、ブレード６１は移動経路中に突出している。この結果、記録ヘッド６５の吐出口面がワイピングされる。尚、キャップ６２が記録ヘッド６５の吐出面に当接してキャッピングを行う場合、キャップ６２は記録ヘッドの移動経路中に突出するように移動する。
【００４９】
記録ヘッド６５がホームポジションから記録開始位置へ移動する場合、キャップ６２及びブレード６１は、上述したワイピング時の位置と同一の位置にある。この結果、この移動においても記録ヘッド６５の吐出口面はワイピングされる。上述の記録ヘッド６５のホームポジションへの移動は、記録終了時や吐出回復時ばかりでなく、記録ヘッド６５が記録のために記録領域を移動する間に所定の間隔で記録領域に隣接したホームポジションへ移動し、この移動に伴って上記ワイピングが行われる。
【００５０】
【実施例】
次に実施例及び比較例を挙げて本発明を具体的に説明する。尚、以下の記載で、部又は％とあるものは特に断りのない限り重量比率を示すものである。
実施例１
（第１のインク成分）
・Ｃ．Ｉ．ダイレクトブラック１９５ ３部
・エチルアルコール １部
・エチレングリコール １０部
・尿素 ５部
・スルホコハク酸ジオクチルナトリウム ０．１部
・イオン交換水 ８０．９部
【００５１】
（第２のインク成分）
・Ｃ．Ｉ．ベーシックイエロー２５ ２．５部
・エチルアルコール １部
・エチレングリコール １０部
・ラウリルジアミノエチルグリシンナトリウム塩 ２部
・イオン交換水 ８４．５部
各インクは、上記第１及び第２のインク成分を容器の中で充分撹拌し、孔径０．４５μｍのテフロンフィルターで加圧濾過して調製した。
【００５２】
実施例２
（第１のインク成分）
・Ｃ．Ｉ．ベーシックレッド９２ ２．５部
・エチルアルコール １部
・エチレングリコール １０部
・尿素 ５部
・塩化セチルトリメチルアンモニウム ０．１部
・イオン交換水 ８１．４部
【００５３】

各インクは、上記第１及び第２のインク成分を容器の中で充分撹拌し、孔径０．４５μｍのテフロンフィルターで加圧濾過して調製した。
【００５４】
実施例３
（第１のインク成分）
・Ｃ．Ｉ．アシッドブルー９ ２部
・エチルアルコール ２部
・ジエチレングリコール ５部
・ポリエチレングリコール（平均分子量４００） ５部
・下記構造式Ａの化合物 １部
・イオン交換水 ８５部
第１のインクは、上記成分を容器の中で充分撹拌し、孔径０．４５μｍのテフロンフィルターで加圧濾過して調製した。
【００５５】
（第２のインク成分）
＜染料分散体成分＞
・Ｃ．Ｉ．ディスパースイエロー２３０ ５部
・ナフタレンスルホン酸ホルムアミド縮合物 １０部
＜染料分散体以外のインク成分＞
・エチルアルコール ５部
・ジエチレングリコール １０部
・尿素 ５部
・イオン交換水 ６５部
第２のインクは、染料分散体の成分を容器の中で充分撹拌し、ジルコニウムビーズを体積換算で５０％充填した後、分散機により約３時間分散した後、孔径２．５μｍのテフロンフィルターで加圧濾過をして粗大粒子を除去し、更に染料分散体以外のインク成分を添加し、水酸化ナトリウム等のｐＨ調整剤でｐＨを７〜９に調整して撹拌した後、孔径１μｍのテフロンフィルターで加圧濾過して調製した。
【００５６】
実施例４
（第１のインク成分）
・Aizen Cathilon Black BXH（保土ケ谷化学） ３部
・エチルアルコール ２部
・エチレングリコール ５部
・ポリエチレングリコール（平均分子量４００） ５部
・下記構造式Ｂの化合物 １部
・イオン交換水 ８４部
第１のインクは、上記成分を容器の中で充分撹拌し、孔径０．４５μｍのテフロンフィルターで加圧濾過して調製した。
【００５７】
（第２のインク成分）
＜染料分散体成分＞
・Ｃ．Ｉ．ディスパースレッド８８ ５部
・ナフタレンスルホン酸ホルムアミド縮合物 １０部
＜染料分散体以外のインク成分＞
・エチルアルコール ５部
・ジエチレングリコール １０部
・尿素 ５部
・イオン交換水 ６５部
第２のインクは、染料分散体の成分を容器の中で充分撹拌し、ジルコニウムビーズを体積換算で５０％充填した後、分散機により約３時間分散した後、孔径２．５μｍのテフロンフィルターで加圧濾過をして粗大粒子を除去し、更に染料分散体以外のインク成分を添加し、水酸化ナトリウム等のｐＨ調整剤でｐＨを７〜９に調整し撹拌した後、孔径１μｍのテフロンフィルターで加圧濾過して調製した。
【００５８】
実施例５
（第１のインク成分）
＜顔料分散体成分＞
・Hostaperm Pink E（着色剤、Hoechst製） １５部
・スチレン−アクリル酸−アクリル酸エチル共重合体 ０．７部
（酸価１７４、平均分子量９，０００）
・モノエタノールアミン ０．４部
・エチレングリコール ５部
・イオン交換水 ７８．９部
【００５９】
上記の顔料分散体成分のうち、着色剤とエチルアルコールを除く成分を容器の中で混合し、ウォーターバスで７０℃で加温して撹拌し、樹脂成分を完全に溶解させた後、着色剤とエチルアルコールを加えて３０分撹拌混合し、ジルコニウムビーズを体積換算で５０％充填した後、分散機により約３時間分散した後、遠心分離処理をして粗大粒子を除去した後、溶剤その他の添加剤を加えて混合し、１時間撹拌して顔料分散体を作製した。
＜顔料分散体を含むインク成分＞
・上記顔料分散体 ４０部
・グリセリン １０部
・エチレングリコール １０部
・エタノール １部
・ポリエチレンラウリル硫酸ナトリウム ０．２部
・イオン交換水 ３８．８部
上記成分を混合し、１時間撹拌して顔料インクを調製した。
【００６０】
（第２のインク成分）
・Ｃ．Ｉ．ベーシックイエロー２５ ２．５部
・エチルアルコール １部
・エチレングリコール １０部
・ラウリルベタイン ２部
・イオン交換水 ８４．５部
第２のインクは、上記成分を容器の中で充分撹拌し、孔径０．４５μｍのテフロンフィルターで加圧濾過して調製した。
【００６１】
比較例１
（第１のインク成分）
・Ｃ．Ｉ．ダイレクトブラック１９５ ３部
・エチルアルコール １部
・エチレングリコール １０部
・尿素 ５部
・イオン交換水 ８１部
（第２のインク成分）
・Ｃ．Ｉ．ベーシックイエロー２５ ２．５部
・エチルアルコール １部
・エチレングリコール １０部
・イオン交換水 ８６．５部
各インクは、上記第１及び第２のインク成分を容器に中で充分撹拌し、孔径０．４５μｍのテフロンフィルターで加圧濾過して調製した。
【００６２】
但し、上記構造式Ａ、Ｂ、ａ、及びｂは、下記に示されるものである。
構造式Ａの化合物
Ｃ₂₅Ｈ₅₁ＮＨ（Ｃ₂Ｈ₄ＮＨ）₃ＣＨ₂ＳＯ₃Ｌｉ
構造式Ｂの化合物
Ｃ₁₅Ｈ₃₁ＮＨ（Ｃ₂Ｈ₄ＮＨ）₂Ｃ₂Ｈ₄ＣＯＯＮＨ₄
【００６３】
構造式ａの染料

【００６４】
構造式ｂの染料

【００６５】
［評価方法］
上記の実施例１〜５及び比較例１の各インクを用いて、以下の市販コピー用紙を含む上質紙に印字を行った。
・キヤノン製コピー用紙：PB PAPER
・ゼロックス製：4024 PAPER
・FOX RIVER製：PLOVER BOND PAPER
【００６６】
▲１▼ 印字画像品位
印字画像は図５に示す通り、１ｃｍ四方の正方形内に、５×５のマス目で仕切り、２色で交互にベタ印字したものにより、２色間のブリーディング画像品位を以下の評価基準によって評価した。その結果を表１に示す。
（評価基準）
○：２色間の境界線が鮮明で、境界部に滲みや混色が見られない。
△：２色間の境界線が存在することが明らかであるが、境界部に多少の滲みや混色が見られる。
×：２色間の境界線が識別不能である。
【００６７】
▲２▼ 文字品位
次に、単色文字品位及び混色文字品位の評価を行った。文字は、Ａ４サイズの上質紙に１５００文字の英数文字及び漢字の文章によるもので、打ち込み比率が、単色で１００％、及び２色混色で２００％で印字した。評価基準は以下の通りである。その結果を表１に示す。
（評価基準）
○：文字のエッジが鮮明で滲みによるフェザリングや線太りが見られない。
△：文字のエッジが多少滲み、均一な線太りが見られる。
×：文字のエッジが滲んでフェザリングが顕著で、不均一な線太りが見られる。
【００６８】
［評価機］
使用したインクジェット記録装置としては、図４に示したと同様の記録装置を用い、図７に示した４つのヘッドを用いてカラー画像を形成した。尚、ここで用いた記録ヘッドとしてはＢＪＣ８２０（商品名、キヤノン社製インクジェットプリンター）に使用されているものと同一の記録ヘッドを用いた。記録ヘッドの駆動条件、即ちヒーターへの通電条件は各ヘッドとも印加電圧２８Ｖ、パルス幅３．２μｓｅｃ、駆動周波数５ｋＨｚとした。
【００６９】
表１：評価結果

【００７０】
【発明の効果】
以上説明したように、本発明によれば、同一の被記録材に対して、異なる２色間の境界部におけるブリーディングのない、鮮明な文字品位の高画質カラー画像を得ることができる。
【図面の簡単な説明】
【図１】インクジェット記録装置のヘッドの縦断面図である。
【図２】インクジェット記録装置のヘッドの横断面図である。
【図３】図１に示したヘッドをマルチ化したヘッドの外観斜視図である。
【図４】インクジェット記録装置の一例を示す斜視図である。
【図５】画像品位評価パターンである。
【符号の説明】
１３：ヘッド
１４：インク溝
１５：発熱ヘッド
１６：保護膜
１７：アルミニウム電極
１８：発熱抵抗体層
１９：蓄熱層
２０：基板
２１：インク
２２：吐出オリフィス（微細孔）
２３：メニスカス
２４：インク小滴
２５：被記録材
２６：マルチ溝
２７：ガラス板
２８：発熱ヘッド
５１：給紙部
５２：紙送りローラー
５３：排紙ローラー
６１：ブレード
６２：キャップ
６３：インク吸収体
６４：吐出回復部
６５：記録ヘッド
６６：キャリッジ
６７：ガイド軸
６８：モーター
６９：ベルト[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an ink set, an ink jet recording method, and an ink jet apparatus that are used when recording a color image on a recording material by using at least two or more primary color inks and combining these primary color inks. The present invention relates to an ink set that is excellent in color developability with respect to plain paper in image recording by an ink jet method, provides a clear and high quality image, and further has excellent water resistance of printed matter, an ink jet recording method using the ink set, and an ink jet apparatus.
[0002]
[Prior art]
Inkjet recording methods include electrostatic attraction by applying a high voltage, a method of applying mechanical vibration or displacement to ink (colored ink) using a piezoelectric element, a method of using pressure that causes ink to foam when heated, etc. Ink droplets are generated by various ink ejection methods, and the ink droplets are ejected to adhere to a recording material such as paper, and ink dots are formed to perform recording. It is a recording system that can perform high-speed printing and multicolor printing.
[0003]
In particular, the method disclosed in Japanese Patent Publication Nos. 61-59911, 61-59912, 61-59914, etc. by the applicant of the present application, that is, an electrothermal converter is used as means for supplying discharge energy. According to the method of ejecting liquid droplets by applying thermal energy to ink and generating bubbles, the recording head can easily realize high-density multi-orifice and record high-resolution and high-quality images at high speed. be able to.
[0004]
[Problems to be solved by the invention]
However, inks used in conventional ink jet recording generally contain water as a main component, and generally contain water-soluble high-boiling solvents such as glycols for the purpose of preventing drying and clogging. When recording is performed on plain paper using such ink, the ink penetrates into the recording material and a sufficient image density cannot be obtained, or the surface of the recording material is filled with a filler or sizing agent. The image density seemed to be uneven due to the uneven distribution.
In particular, when trying to obtain a color image, a plurality of colors of ink are superimposed one after another before the previously recorded ink is fixed. Were mixed non-uniformly (hereinafter referred to as bleeding), and satisfactory images could not be obtained. In recent years, there has been an increasing demand for water resistance of printed matter, and from this point, satisfactory water-resistant printed matter has not been obtained.
[0005]
As means for solving the above problems, Japanese Patent Application Laid-Open No. 55-65269 uses an ink in which a compound that enhances permeability such as a surfactant is added to the ink, or Japanese Patent Application Laid-Open No. 55-66976. Discloses an ink mainly composed of a volatile solvent.
Further, US Pat. No. 5,106,416 discloses an ink containing a cationic dye, an amphoteric surfactant and a nonionic amphiphile. U.S. Pat. No. 5,342,440 discloses an ink containing a water-insoluble dye, a polymer colloid, and a surfactant. JP-A-60-96673 and JP-A-4-139272 disclose inks using a betaine acrylic resin.
[0006]
However, in the ink described in JP-A-55-65269, when an ink containing a compound that enhances permeability such as a surfactant is used, the permeability of the ink to the recording material is improved. Although bleeding is suppressed to some extent, the ink penetrates deep into the recording material, including the colorant, and there is a disadvantage that the image density is lowered. Further, since the wettability with respect to the surface of the recording material is improved, the ink tends to spread on the surface of the recording material, which is not preferable because the resolution is lowered and bleeding occurs.
In addition, when the ink mainly composed of a volatile solvent described in JP-A-55-66976 is used, in addition to the above-described disadvantages, the nozzle eye due to the evaporation of the solvent at the nozzle portion of the recording head. Clogging is likely to occur, which is not preferable.
[0007]
Furthermore, in the ink containing a cationic dye, an amphoteric surfactant and a nonionic amphiphile of US Pat. No. 5,106,416, the diffusion of the colorant is prevented by adding the surfactant at a critical micelle concentration or more. However, basically, the penetrability of the ink itself was increased by the action of the surfactant as in JP-A-55-65269, and a preferable image could not be obtained.
In addition, in the case of an ink containing a water-insoluble dye, a polymer colloid, and a surfactant described in US Pat. No. 5,342,440, in addition to the disadvantages of US Pat. The nozzles may be clogged due to precipitation of water-insoluble dyes and aggregation of colloids, which is not preferable.
[0008]
In Japanese Patent Application Laid-Open Nos. 60-96673 and 4-139272, an ink using a betaine acrylic resin is used for the purpose of preventing bleeding of oil-based ink, and the latter is used for pigment ink. Although it is disclosed that the above acrylic resin is added for the purpose of improving stability, high image quality on plain paper cannot be obtained. Here, the betaine acrylic resin certainly shows amphoteric characteristics, but it is difficult to say that it has a cationic group and an anionic group clearly, and a monomer having an anionic group in the molecule. It is not a copolymer with a monomer having a cationic group and does not have an isoelectric point. Therefore, it is fundamentally different from the zwitterionic compound used in the present invention described later.
[0009]
The present invention has been made in view of the above circumstances, and an object of the present invention is to obtain a sufficient image density and high uniformity of image density in recording of a recording material, particularly plain paper, and particularly a color image. It is an object to provide an ink set composed of an ink that can prevent bleeding in the image, can obtain a clear and uniform high-quality image, and can improve the character quality of printed matter, and an ink jet recording method and an ink jet apparatus using the ink set. .
[0010]
[Means for Solving the Problems]
The above object is achieved by the present invention described below. That is, the present invention is used when a color image is recorded on a recording material by an ink jet recording method.The first ink and the first inkDifferentSecond of colorInkWhen,In the ink set that combinesFirst and secondinkEach ofHowever, the color material and liquid medium are essential components,The firstInn ofTheAnionic or cationic surfactantTheIncludingOnlyAnd theSecondInnTheZwitterionic compoundsTheIncludingInAn ink set, an ink jet recording method using the ink set, and an ink jet apparatus.
[0011]
More specifically, for example, the configuration of the ink set isFirstThe color material contained in the ink is an anionic dye, and the surfactant contained in the ink is an anionic surfactant.SecondThe color material contained in the ink is a cationic dye and simultaneously contains a zwitterionic compound in the ink, orFirstThe color material contained in the ink is a cationic dye, and the surfactant contained in the ink is a cationic surfactant.SecondThe color material contained in the ink is an anionic dye, and at the same time, the ink contains a zwitterionic compound.
[0012]
Other,FirstThe color material contained in the ink is a pigment, and the surfactant contained in the ink is a cationic surfactant.SecondThe color material contained in the ink is an anionic dye, and at the same time, the ink contains a zwitterionic compound.
Similarly,FirstThe color material contained in the ink is a pigment, and the surfactant contained in the ink is an anionic surfactant.SecondThe color material contained in the ink is a cationic dye, and at the same time, the ink contains a zwitterionic compound.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Next, the present invention will be described in more detail with reference to preferred embodiments.
First, the operation of the ink set of the present invention will be described. For example, a preferred embodiment of the ink set according to the present invention will be described as an example. At least one color ink constituting the ink set is described.(First ink)Ink of another color different from the color of the ink using an anionic dye and an anionic surfactant as constituent components(Second ink)By using a cationic dye and a zwitterionic compound in combination as the constituents of the above, two or more different colors of ink are overprinted almost simultaneously, or one of the inks is dried on the recording material When ink of a color different from that color was previously ejected adjacently, color mixing of the ink can be suppressed.
[0014]
As a result, it is possible to reduce feathering due to irregular line thickening of the obtained color image and boundary bleeding between adjacent different colors. That is, when two different color inks having the above-described constituents are driven adjacent to each other, when the anionic dye and the cationic dye, which are the pigments constituting each ink, come into contact with each other. In order to react and form an insoluble salt, rapid color mixing between liquids can be suppressed. However, with this alone, the diffusion rate between the liquids of the two colors of ink exceeds the rate of reaction insolubilization, and if the molecular weight of the insolubilized substance itself due to the reaction is insufficient, In order to diffuse between them, the color mixing suppression effect is insufficient.
[0015]
Therefore, in order to make this effect more satisfactory, it is necessary to further increase the insolubilization reaction rate of the anionic substance and the cationic substance between the two different color inks described above. This can be achieved by increasing the number of reactive groups between the inks. Furthermore, although it is necessary to suppress the diffusion of the insolubilized material between the anionic substance and the cationic substance, this can be realized by increasing the molecular weight of the insolubilized substance to be generated.
Therefore, when the first ink contains an anionic dye, the number of anionic groups that are reactive groups is increased in the ink, and the molecular weight of the salt formation product with the cationic substance of the second ink is increased. Can be realized by simultaneously adding an anionic surfactant having a hydrophobic group having a large number of carbon atoms. Furthermore, if a zwitterionic compound is added together with a cationic dye in the second ink, the reaction product of both the cationic dye and the zwitterionic compound reacts with the anionic substance of the first ink, resulting in a higher molecular weight. A high salt formation product is produced, and border bleeding at the time of fixing of ink between two different color inks and line thickening at the time of color mixing are more effectively prevented.
[0016]
Similarly, in the case opposite to the above case, when the first ink contains a cationic dye, the number of cationic groups as reactive groups is increased in the ink and the anion of the second ink is used. In order to increase the molecular weight of the salt formation with the active substance, it can be realized by simultaneously adding a cationic surfactant having a hydrophobic group having a large number of carbon atoms. Furthermore, if a zwitterionic compound is added to the second ink together with the anionic dye, the reaction product of both the anionic dye and the zwitterionic compound reacts with the cationic substance of the first ink, resulting in a higher molecular weight. A high salt formation product is produced, and border bleeding at the time of fixing ink between two different colors and line thickening at the time of color mixing are more effectively prevented.
[0017]
In addition, when an aqueous dispersion of a water-insoluble dye such as a pigment or an oily or disperse dye is used in the first ink, an anionic surfactant is contained together, and the second ink is cationic. If both a dye and a zwitterionic compound are used, the pigment or water-insoluble dye and the cationic dye do not melt together when they come into contact with each other, but rather repel each other and suppress rapid color mixing between liquids. However, the reaction between the anionic substance and the cationic substance contained in both inks reduces the diffusion between the two inks due to changes in physical properties such as thickening at the contact portion between the two inks. Similar effects can be expected. Or, conversely, when an aqueous dispersion of a water-insoluble dye such as a pigment or an oily or disperse dye is used in the first ink, the second ink contains a cationic surfactant. If both an anionic dye and a zwitterionic compound are used, the same effect can be expected.
[0018]
Next, components constituting the ink set of the present invention will be described.
First, the ink used in the ink set of the present invention dissolves or disperses an anionic dye, a cationic dye and a pigment, an anionic surfactant or a cationic surfactant, and a zwitterionic compound in an appropriate liquid medium. Is obtained.
The concentration of the color material in such ink is appropriately determined as desired, but is usually 0.001 to 20% by weight, preferably 0.01 to 15% by weight, more preferably 0.01 to 10%. The range is wt%. The concentration of the anionic or cationic surfactant or zwitterionic compound in the ink is appropriately determined as desired, but is usually 0.001 to 50% by weight, preferably 0.01 to 25% by weight, More preferably, it is in the range of 0.01 to 10% by weight.
[0019]
The first and second inks constituting the ink set of the present invention as described above are constituted by dissolving or dispersing dyes or pigments in a liquid medium. The liquid medium used in this case is water. It is preferable to use a mixture of an organic solvent. When the liquid medium is in a mixed form, there is an advantage that changes in physical properties or chemical properties (for example, pH value) of the ink are suppressed over an extremely long period (for example, 6 months or 1 year or more).
[0020]
The organic solvent used in the present invention is appropriately selected from the water-soluble organic solvents listed below as desired. Specifically, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, iso-butyl alcohol, amyl alcohol, n-hexanol, Alkyl alcohols having 1 to 7 carbon atoms such as cyclohexanol; ketones or ketone alcohols such as acetone and diacetone alcohol; alkanolamines such as monoethanolamine and diethanolamine; amides such as dimethylformamide and dimethylacetamide; Ethers such as dioxane; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, thiodiglycol, butylene glycol, glycol Polyhydric alcohols in which an alkylene group such as phosphorus contains 2 to 6 carbon atoms; ethylene glycol monomethyl (or ethyl or propyl) ether, diethylene glycol monomethyl (or ethyl or butyl) ether, diethylene glycol dimethyl (or ethyl) ether, polyethylene Lower alkyl mono or diethers derived from alkylene glycols such as glycol monomethyl (or ethyl) ether (3 to 8 carbon atoms); nitrogen-containing 5-membered rings such as 2-pyrrolidone and N-methyl-2-pyrrolidone Ketones; intramolecular esters of oxycarboxylic acids such as α-valero-lactone, ε-caprolactone, and butyl lactone; morpholine, dimethylimidazolidine sulfolane, and the like.
[0021]
The content of the water-soluble organic solvent as described above in the ink is generally in the range of 5 to 90% by weight, preferably 10 to 80% by weight, more preferably 10 to 50% by weight. In general, it is in the range of 10 to 90% by weight, preferably 10 to 70% by weight, more preferably 20 to 70% by weight.
[0022]
The anionic or cationic surfactant and the zwitterionic compound that are preferably used as the components of the ink constituting the ink set of the present invention, whether existing or newly synthesized, are necessary for the ink. As long as the performance capable of achieving the object of the present invention is obtained, most of them can be used.
First, as an anionic surfactant, for example, the hydrophilic group has carboxylate, sulfonate, sulfate ester salt, phosphate ester salt and the like, and the hydrophobic group has 12 to 18 carbon atoms. Paraffin, olefin, benzene having an alkyl group having 11 to 15 carbon atoms, alkyl naphthalene having 1 to 5 carbon atoms, alkylphenol having 12 to 18 carbon atoms, higher alcohol, higher mercaptan, 11 to 18 carbon atoms Higher fatty acid, higher fatty acid ester having a total carbon number of 8 to 21, polyhydric alcohol fatty acid partial ester having 11 to 17 carbon atoms, higher fatty acid amide having 11 to 17 carbon atoms, other oils and fats, wax and the like The thing comprised from what was made is mentioned.
[0023]
Examples of the cationic surfactant include a quaternary ammonium salt, a benzyl halide quaternary ammonium salt, an amine salt, an alkanolamine salt, a pyridinium salt, etc. in the hydrophilic group, and a higher fatty acid in the hydrophobic group. Higher fatty acid amides having 12 to 34 carbon atoms, higher fatty acid amides having 11 to 17 carbon atoms, higher alkyl halides having 11 to 17 carbon atoms, etc. Y higher fatty acids having 11 to 18 carbon atoms, 12 to 34 carbon atoms Examples thereof include those composed of higher amines, higher fatty acid amides having 11 to 17 carbon atoms, higher alkyl halides having 11 to 17 carbon atoms and the like as raw materials.
[0024]
In addition, as the zwitterionic compound used as a component constituting the ink set of the present invention, whether it is an existing compound or a newly synthesized compound, the appropriate physical properties required for the ink and the object of the present invention are achieved. If the performance which can be achieved is obtained, most things can be used conveniently. Zwitterionic compounds include amphoteric surfactants, which are preferably used in the present invention. Specific examples of the amphoteric surfactant include linear and branched alkylamines having 8 to 18 carbon atoms in total, unsaturated alkylamines, alkyl fatty acids, alkyl halides, and the like, and hydrophilic groups are polyamines, Monochloroacetate, acrylic acid, caprolactam, maleic acid, chloroalkylsulfonate, aminosulfonate, ethylene oxide, aminoethylethanolamine, sulfating agent, etc. Examples include imidazoline derivatives, and these can be used alone or in appropriate combination of several kinds.
[0025]
Furthermore, as the zwitterionic compound used in the present invention, in addition to the amphoteric surfactant as described above, a compound represented by the following general formula (I) can also be suitably used.

(Wherein R₁Represents an alkyl group having 1 to 48 carbon atoms or a hydrogen atom, R₂Is (CH₂)_a-X₁Alternatively, it represents a hydrogen atom, and a is an integer of 1 to 4. R_ThreeIs (CH₂)_b-X₂Or R_Four-Y or a hydrogen atom is represented, and b is any integer of 1 to 4. R_FourRepresents an alkyl group having 1 to 48 carbon atoms or a hydrogen atom. Z is (NR_Five  C_lH_2l)_c(NHC_nH_2n)_dWhere l and n are any integer from 2 to 4, and c + d is any integer from 0 to 50. Y is (NR₆C_mH_2m)_e(NHC_pH_2P)_fM and p are any integers of 2 to 4, and e + f is any integer of 0 to 50. R_FiveIs (CH₂)_g-X_ThreeAnd g is any integer from 1 to 4. R₆Is (CH₂)_h-X_FourAnd h is an integer from 1 to 4. X₁, X₂, X_ThreeAnd X_FourAre each selected from the group consisting of a carboxyl group, a carboxyl group salt, a sulfone group, a sulfone group salt or a hydrogen atom. R₂And R_ThreeAre both hydrogen atoms, both c and e are not 0, and X₁, X₂, X_ThreeAnd X_Four  Are not all hydrogen atoms. )
[0026]
As an anionic dye used as a component of the ink constituting the ink set of the present invention, an existing anionic dye or a newly synthesized one may be used as long as it has an appropriate color tone and density. Can be used. Further, any of these can be mixed and used. Specific examples of the anionic dye include the following.
C. I. Direct yellow 8, 11, 12, 27, 28, 33, 39, 44, 50, 58, 85, 86, 87, 88, 89, 98, 100, 110,
C. I. Direct Red 2, 4, 9, 11, 20, 23, 24, 31, 39, 46, 62, 75, 79, 80, 83, 89, 95, 197, 201, 218, 220, 224, 225, 226, 227, 228, 230,
C. I. Direct Blue 1, 15, 22, 25, 41, 76, 77, 80, 86, 90, 98, 106, 108, 120, 158, 163, 168, 199, 226,
[0027]
C. I. Direct black 17, 19, 22, 31, 32, 51, 62, 71, 74, 112, 113, 154, 168, 195,
C. I. Acid Yellow 1, 3, 7, 11, 17, 23, 25, 29, 36, 38, 40, 42, 44, 76, 98, 99,
C. I. Acid Red 6, 8, 9, 13, 14, 18, 26, 27, 32, 35, 42, 51, 52, 80, 83, 87, 89, 92, 106, 114, 115, 133, 134, 145, 158, 198, 249, 265, 289,
C. I. Acid Blue 1, 7, 9, 15, 22, 23, 25, 29, 40, 43, 59, 62, 74, 78, 80, 90, 100, 102, 104, 117, 127, 138, 158, 161,
[0028]
C. I. Acid Black 2, 48, 51, 52, 110, 115, 156,
C. I. Reactive Yellow 2, 3, 17, 25, 37, 42,
C. I. Reactive Red 7, 12, 13, 15, 17, 20, 23, 24, 31, 42, 45, 46, 59,
C. I. Reactive Blue 4, 5, 7, 13, 14, 15, 18, 19, 21, 26, 27, 29, 32, 38, 40, 44, 100,
C. I. Food Yellow 3,
C. I. Food Red 87, 92, 94,
C. I. Food black 1, 2
[0029]
As the cationic dye used as the component of the ink constituting the ink set of the present invention, most of the existing cationic dyes or newly synthesized ones having an appropriate color tone and density can be used. Can be used. Further, any of these can be mixed and used. Specific examples of the cationic dye include the following.
C. I. Basic yellow 1, 11, 13, 19, 25, 33, 36,
C. I. Basic Red 1, 2, 9, 12, 13, 38, 39, 92,
C. I. Basic Blue 1, 3, 5, 9, 19, 24, 25, 26, 28, 45, 54, 65,
C. I. Basic Black 2, 8,
Aizen Cathilon Black SBH, BXH, SH, ACH, MH, TH (made by Hodogaya Chemical)
Sumiacryl Black B, R, AP, BP, CP, FFP (manufactured by Sumitomo Chemical),
Diacryl Supra Black GSL, RSL, ESL (Mitsubishi Kasei),
[0030]
The water-insoluble dye containing a disperse dye used as a component of the ink constituting the ink set of the present invention may be a commercially available one or a newly synthesized one having an appropriate color tone and density. Most of them can be used, and a plurality of dyes can be mixed and used. Examples of water-insoluble dyes that can be used in the present invention include the following.
[0031]
C. I. Disperse Yellow 3, 4, 5, 7, 23, 33, 42, 49, 54, 56, 64, 71, 79, 82, 83, 86, 88, 93, 99, 116, 119, 141, 160, 163 198, 204, 218, 224, 226, 230,
[0032]
C. I. Disperse thread 1, 4, 5, 7, 11, 12, 13, 15, 17, 30, 33, 43, 50, 52, 53, 54, 55, 56, 58, 59, 60, 65, 72, 73, 74, 75, 76, 82, 86, 88, 90, 91, 92, 96, 105, 106, 107, 110, 117, 118, 126, 127, 128, 131, 132, 134, 135, 136, 137, 140, 143, 145, 146, 151s, 153, 159, 164, 167, 169, 177, 181, 184, 188, 190, 191, 200, 203, 205, 206, 221, 223, 224, 225, 227, 229, 239, 240, 258, 277, 278, 279, 283, 288, 302, 309, 311, 312, 323, 329, 332, 40,341,343,
[0033]
C. I. Disperse Blue 1, 3, 7, 13, 19, 26, 27, 35, 44, 54, 55, 56, 60, 64, 65, 72, 73, 79, 81, 82, 87, 91, 93, 94 96, 102, 106, 118, 120, 122, 125, 128, 130, 139, 142, 143, 146, 148, 149, 153, 154, 165, 167, 181, 183, 185, 186, 189, 198 , 200, 201, 205, 207, 214, 224, 225, 257, 259, 266, 268, 270, 284, 285, 287, 288, 291, 293, 301, 330, 332, 333, 337, 341, 345 , 351, 352, 353,
[0034]
C. I. Disperse Black 1, 9, 10, Black GL, Black B, Black L, Black 2B, Black BT, Black OBL, Black RSR, Black TK, Black TG, Black S-CTL, Black H-DB, Black RD- SGT, Black S-2BL, Black S-3BL, Black S-5BL, Black S-BNL, Black S-3GLN, Black S-ST, Black S-FGB, Black S-SGN, Black S-WLA, Black S- WLAT, Black B82, Black BTNU82, Black 2BL, Black HR-FS, Black RB-FS, Black HG-FS, Black GB-FS, Black N-FS.
The water-insoluble dyes suitable in the present invention are not limited to those listed above.
[0035]
As a pigment suitably used for the color component of the dispersed ink used in the ink constituting the ink set of the present invention, whether it is an existing one or a newly synthesized pigment, an appropriate color tone and density for the ink If it has, it can use most things. Specifically, for example, inorganic pigments such as titanium, bengara, aluminum powder, talc, clay, calcium carbonate, and silica; organic pigments such as carbon black, azo, phthalocyanine, quinacridone, cochineal, and safflower pigment Etc.
[0036]
In addition, in the dispersion type ink, a polymer substance that can function as a dispersant or a solubilizer for the water-insoluble dye can be used. Examples of such compounds include sorbitan fatty acid derivatives, sulfate ester derivatives, polyoxyethylene alkylene ether type sulfate esters, phosphate ester derivatives, quaternary ammonium salt derivatives, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters. , Fatty acids, alkenyl succinates, higher alcohol sulfates, alkylbenzene sulfonic acid soda, alkyl diphenyl ether disulfonates, naphthalene sulfonic acid formalin condensate and the like can be used as appropriate.
[0037]
In particular, when a pigment is used, if necessary, for example, an anionic or nonionic surfactant, a polyphosphate dispersant, a formalin condensate of naphthalene sulfonate, polyacrylic acid, polystyrene sulfonic acid , Styrene-acrylic acid copolymer, styrene-maleic acid copolymer, styrene-methacrylic acid copolymer, vinyl naphthalene-acrylic acid copolymer and other vinyl compounds and carboxylic acid resins, carboxymethyl cellulose, polyvinyl alcohol, Resins such as polyacrylic acid partial alkyl esters and polyacrylic polyamines can be used as appropriate.
[0038]
The dispersion-type ink is prepared by adjusting the pH of the colorant-dispersant or solubilizer mixture as described above, and then using a disperser such as a ball mill, a roll mill, or a sand mill, or a centrifugal separator as necessary. After preparing a dispersion in advance by performing centrifugation treatment and filtration in step 1, additives such as a solvent, a surfactant, and a zwitterionic compound can be added.
[0039]
Various inks used in the present invention prepared as described above are particularly excellent in affinity with a recording material having a high degree of sizing, high-speed recording properties, optical density of recorded images, color tone, water resistance, It is particularly excellent in friction resistance or light resistance. Further, it is a practical ink excellent in storage stability, signal responsiveness, droplet formation stability, ejection stability or continuous recording property.
[0040]
In addition to the various components described above, various additives may be used in the various inks used in the present invention for the purpose of further improving the physical properties of the ink. Examples thereof include pH adjusters, anti-drying agents for crystalline organic compounds such as urea, viscosity adjusters, surface tension adjusters such as various surfactants, fungicides or bactericides. Alternatively, in the case where a recording method is employed in which ink droplets are charged and deflected, a specific resistance adjusting agent can be mentioned as an additive.
The present invention prepares each color ink formulated to have the desired physical property values having the above excellent characteristics, forms an ink set combining at least two different inks, and applies this to various ink jet recording systems. As a result, a high-density and high-quality image is formed. That is, in the present invention, the intended purpose is achieved by using two or more colors of ink having the physical properties described above and forming an image by an ink jet method.
[0041]
As the ink jet method applied to the ink jet recording method of the present invention, any conventionally known method can be used. That is, various ink jet recording apparatuses other than a recording apparatus having a recording head of a type that generates droplets by using mechanical vibration of a piezo vibrator are also preferably used. For example, the present invention can be suitably used in an apparatus that performs recording by applying a recording signal to ink in a recording head in the form of thermal energy to generate droplets.
The black ink or color ink used in the present invention may be used as ink for writing instruments such as sign pens and fountain pens. However, when used as ink for writing instruments, it is necessary to adjust various properties such as viscosity and surface tension for writing instruments.
[0042]
Hereinafter, a recording apparatus applied to the present invention that performs recording by applying thermal energy corresponding to a recording signal to the ink in the chamber of the recording head and generating droplets with the energy will be described. An example of a head configuration which is a main part of the apparatus is shown in FIGS.
[0043]
The head 13 includes a glass, ceramic or plastic plate having a groove 14 through which ink passes, and a heat generating head 15 used for thermal recording (though a thin film head is shown in the figure, the present invention is not limited to this). It is obtained by bonding The heat generating head 15 has good heat dissipation such as a protective film 16 formed of silicon oxide or the like, aluminum electrodes 17-1 and 17-2, a heat generating resistor layer 18 formed of nichrome or the like, a heat storage layer 19, and alumina. It consists of a substrate 20.
[0044]
The ink 21 reaches the ejection orifice (fine hole) 22, and a meniscus 23 is formed by the pressure P.
Now, when electrical signal information is applied to the aluminum electrodes 17-1 and 17-2, the region indicated by n of the heat generating head 15 suddenly generates heat, and bubbles are generated in the ink 21 in contact therewith. The meniscus 23 protrudes, the ink 21 is ejected to form ink droplets 24, and fly from the ejection orifice 22 toward the recording material 25.
[0045]
FIG. 3 shows an external view of a multi-head in which a large number of heads shown in FIG. 1 are arranged. The multi-head is manufactured by adhering a glass plate 27 having multi-grooves 26 and a heating head 28 similar to that described in FIG. 1 is a cross-sectional view of the head 13 along the ink flow path, and FIG. 2 is a cross-sectional view taken along the line AB of FIG.
[0046]
FIG. 4 shows an example of an ink jet recording apparatus incorporating the head. In FIG. 4, reference numeral 61 denotes a blade as a wiping member. One end of the blade 61 is held by a blade holding member to become a fixed end, and forms a cantilever. The blade 61 is disposed at a position adjacent to the recording area by the recording head 65, and in this example, is held in a form protruding in the moving path of the recording head 65.
Reference numeral 62 denotes a cap on the ejection port surface of the recording head 65, which is disposed at a home position adjacent to the blade 61, moves in a direction perpendicular to the moving direction of the recording head 65, contacts the ink ejection port surface, and capping. The structure which performs is provided. Further, reference numeral 63 denotes an ink absorber provided adjacent to the blade 61 and, like the blade 61, is held in a form protruding in the moving path of the recording head 65.
[0047]
The blade 61, the cap 62, and the ink absorber 63 constitute a discharge recovery unit 64, and the blade 61 and the ink absorber 63 remove moisture, dust, and the like from the ink discharge port surface.
65 has a discharge energy generating means, and a recording head that performs recording by discharging ink onto a recording material facing the discharge port surface on which the discharge ports are arranged. 66 has a recording head 65 mounted thereon and moves it. The carriage.
The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected to a belt 69 (not shown) driven by a motor 68. As a result, the carriage 66 can move along the guide shaft 67, and the recording area and its adjacent area can be moved by the recording head 65.
[0048]
Reference numeral 51 denotes a paper feed unit for inserting a recording material, and 52 denotes a paper feed roller driven by a motor (not shown). With these configurations, a recording material is fed to a position facing the ejection opening surface of the recording head 65, and is discharged to a paper discharge portion provided with a paper discharge roller 53 as recording progresses.
In the above configuration, when the recording head 65 returns to the home position due to the end of recording or the like, the cap 62 of the ejection recovery unit 64 is retracted from the moving path of the recording head 65, but the blade 61 protrudes into the moving path. As a result, the ejection port surface of the recording head 65 is wiped. When the cap 62 is in contact with the ejection surface of the recording head 65 to perform capping, the cap 62 moves so as to protrude into the moving path of the recording head.
[0049]
When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are at the same position as the above-described wiping position. As a result, the ejection port surface of the recording head 65 is wiped even during this movement. The above-described movement of the recording head 65 to the home position is not only at the end of recording or at the time of ejection recovery, but also at the home position adjacent to the recording area at a predetermined interval while the recording head 65 moves the recording area for recording. The wiping is performed along with this movement.
[0050]
【Example】
Next, the present invention will be specifically described with reference to examples and comparative examples. In the following description, “part” or “%” indicates a weight ratio unless otherwise specified.
Example 1
(First ink component)
・ C. I. Direct Black 195 3 parts
・ Ethyl alcohol 1 part
・ 10 parts of ethylene glycol
・ Urea 5 parts
・ Dioctyl sodium sulfosuccinate 0.1 part
・ Ion exchange water 80.9 parts
[0051]
(Second ink component)
・ C. I. Basic Yellow 25 2.5 parts
・ Ethyl alcohol 1 part
・ 10 parts of ethylene glycol
・ Lauryldiaminoethylglycine sodium salt 2 parts
・ Ion exchange water 84.5 parts
Each ink was prepared by sufficiently stirring the first and second ink components in a container and pressure-filtering with a Teflon filter having a pore diameter of 0.45 μm.
[0052]
Example 2
(First ink component)
・ C. I. Basic Red 92 2.5 parts
・ Ethyl alcohol 1 part
・ 10 parts of ethylene glycol
・ Urea 5 parts
・ Cetyltrimethylammonium chloride 0.1 part
・ Ion exchange water 81.4 parts
[0053]

Each ink was prepared by sufficiently stirring the first and second ink components in a container and pressure-filtering with a Teflon filter having a pore diameter of 0.45 μm.
[0054]
Example 3
(First ink component)
・ C. I. Acid Blue 9 2 parts
・ Ethyl alcohol 2 parts
・ Diethylene glycol 5 parts
-Polyethylene glycol (average molecular weight 400) 5 parts
・ 1 part of the compound of the following structural formula A
・ Ion exchange water 85 parts
The first ink was prepared by sufficiently stirring the above components in a container and pressure-filtering with a Teflon filter having a pore size of 0.45 μm.
[0055]
(Second ink component)
<Dye dispersion component>
・ C. I. Disperse Yellow 230 5 parts
・ Naphthalenesulfonic acid formamide condensate 10 parts
<Ink components other than the dye dispersion>
・ Ethyl alcohol 5 parts
・ 10 parts of diethylene glycol
・ Urea 5 parts
・ Ion exchange water 65 parts
In the second ink, the components of the dye dispersion were sufficiently stirred in a container, filled with 50% of zirconium beads in terms of volume, dispersed with a disperser for about 3 hours, and then passed through a Teflon filter having a pore diameter of 2.5 μm. After filtration under pressure, coarse particles are removed, ink components other than the dye dispersion are added, the pH is adjusted to 7-9 with a pH adjusting agent such as sodium hydroxide, and the mixture is stirred, and then Teflon with a pore size of 1 μm is used. It was prepared by pressure filtration with a filter.
[0056]
Example 4
(First ink component)
・ Aizen Cathilon Black BXH (Hodogaya Chemical) 3 parts
・ Ethyl alcohol 2 parts
・ Ethylene glycol 5 parts
-Polyethylene glycol (average molecular weight 400) 5 parts
・ 1 part of the compound of the following structural formula B
・ 84 parts of ion exchange water
The first ink was prepared by sufficiently stirring the above components in a container and pressure-filtering with a Teflon filter having a pore size of 0.45 μm.
[0057]
(Second ink component)
<Dye dispersion component>
・ C. I. Disper thread 88 5 parts
・ Naphthalenesulfonic acid formamide condensate 10 parts
<Ink components other than the dye dispersion>
・ Ethyl alcohol 5 parts
・ 10 parts of diethylene glycol
・ Urea 5 parts
・ Ion exchange water 65 parts
In the second ink, the components of the dye dispersion were sufficiently stirred in a container, filled with 50% of zirconium beads in terms of volume, dispersed with a disperser for about 3 hours, and then passed through a Teflon filter having a pore diameter of 2.5 μm. After filtering through pressure, coarse particles are removed, ink components other than the dye dispersion are added, pH is adjusted to 7-9 with a pH adjusting agent such as sodium hydroxide, and the mixture is stirred, and then a Teflon filter having a pore size of 1 μm. It was prepared by filtration under pressure.
[0058]
Example 5
(First ink component)
<Pigment dispersion component>
・ 15 parts of Hostaperm Pink E (colorant, manufactured by Hoechst)
・ Styrene-acrylic acid-ethyl acrylate copolymer 0.7 parts
(Acid value 174, average molecular weight 9,000)
・ 0.4 parts of monoethanolamine
・ Ethylene glycol 5 parts
・ 78.9 parts of ion exchange water
[0059]
Among the above pigment dispersion components, the colorant and the components excluding ethyl alcohol are mixed in a container, heated at 70 ° C. in a water bath and stirred to completely dissolve the resin component, and then the colorant. And ethyl alcohol are added and stirred and mixed for 30 minutes. After 50% of the zirconium beads are filled in terms of volume, the particles are dispersed by a disperser for about 3 hours and then centrifuged to remove coarse particles. Additives were added and mixed, and stirred for 1 hour to prepare a pigment dispersion.
<Ink component containing pigment dispersion>
・ 40 parts of the above pigment dispersion
・ 10 parts of glycerin
・ 10 parts of ethylene glycol
・ Ethanol 1 part
・ Polyethylene lauryl sulfate 0.2 parts
・ 38.8 parts of ion-exchanged water
The above components were mixed and stirred for 1 hour to prepare a pigment ink.
[0060]
(Second ink component)
・ C. I. Basic Yellow 25 2.5 parts
・ Ethyl alcohol 1 part
・ 10 parts of ethylene glycol
・ Lauryl betaine 2 parts
・ Ion exchange water 84.5 parts
The second ink was prepared by sufficiently stirring the above components in a container and pressure-filtering with a Teflon filter having a pore size of 0.45 μm.
[0061]
Comparative Example 1
(First ink component)
・ C. I. Direct Black 195 3 parts
・ Ethyl alcohol 1 part
・ 10 parts of ethylene glycol
・ Urea 5 parts
・ 81 parts of ion exchange water
(Second ink component)
・ C. I. Basic Yellow 25 2.5 parts
・ Ethyl alcohol 1 part
・ 10 parts of ethylene glycol
・ Ion exchange water 86.5 parts
Each ink was prepared by sufficiently stirring the first and second ink components in a container and pressure-filtering with a Teflon filter having a pore diameter of 0.45 μm.
[0062]
However, the structural formulas A, B, a, and b are shown below.
Compound of structural formula A
C_{twenty five}H₅₁NH (C₂H_FourNH)_ThreeCH₂SO_ThreeLi
Compound of structural formula B
C₁₅H₃₁NH (C₂H_FourNH)₂C₂H_FourCOONH_Four
[0063]
Dye of structural formula a

[0064]
Dye of structural formula b

[0065]
[Evaluation methods]
Using the inks of Examples 1 to 5 and Comparative Example 1 described above, printing was performed on high-quality paper including the following commercially available copy paper.
・ Canon copy paper: PB PAPER
・ Xerox: 4024 PAPER
-FOX RIVER made: PLOVER BOND PAPER
[0066]
(1) Print image quality
As shown in FIG. 5, the quality of the bleeding image between the two colors is evaluated according to the following evaluation criteria by dividing the square by 5 × 5 in a 1 cm square square and alternately printing two colors. did. The results are shown in Table 1.
(Evaluation criteria)
○: The boundary line between the two colors is clear, and no blur or color mixture is seen at the boundary part.
Δ: It is clear that there is a boundary line between two colors, but some blurring or color mixing is observed at the boundary part.
X: The boundary line between two colors is indistinguishable.
[0067]
▲ 2 ▼ Text quality
Next, single color character quality and mixed color character quality were evaluated. The characters were printed on A4 size high-quality paper with 1500 alphanumeric characters and kanji text, and the printing ratio was printed with a single color of 100% and a mixed color of 200%. The evaluation criteria are as follows. The results are shown in Table 1.
(Evaluation criteria)
○: The character edge is clear and feathering and line thickening due to bleeding are not observed.
Δ: The edges of characters are slightly blurred and uniform line weight is observed.
X: The edge of a character blurs and feathering is remarkable, and uneven line thickness is seen.
[0068]
[Evaluation machine]
As the ink jet recording apparatus used, a recording apparatus similar to that shown in FIG. 4 was used, and a color image was formed using the four heads shown in FIG. As the recording head used here, the same recording head as that used in BJC820 (trade name, an inkjet printer manufactured by Canon Inc.) was used. The recording head drive conditions, that is, the energization conditions for the heaters, were set to an applied voltage of 28 V, a pulse width of 3.2 μsec, and a drive frequency of 5 kHz.
[0069]
Table 1: Evaluation results

[0070]
【The invention's effect】
As described above, according to the present invention, it is possible to obtain a high quality color image with clear character quality without bleeding at the boundary between two different colors on the same recording material.
[Brief description of the drawings]
FIG. 1 is a longitudinal sectional view of a head of an ink jet recording apparatus.
FIG. 2 is a cross-sectional view of the head of the ink jet recording apparatus.
FIG. 3 is an external perspective view of a head in which the head shown in FIG.
FIG. 4 is a perspective view illustrating an example of an ink jet recording apparatus.
FIG. 5 is an image quality evaluation pattern.
[Explanation of symbols]
13: Head
14: Ink groove
15: Heat generating head
16: Protective film
17: Aluminum electrode
18: Heating resistor layer
19: Thermal storage layer
20: Substrate
21: Ink
22: Discharge orifice (fine hole)
23: Meniscus
24: Ink droplet
25: Recording material
26: Multi groove
27: Glass plate
28: Heat generating head
51: Paper feed unit
52: Paper feed roller
53: Paper discharge roller
61: Blade
62: Cap
63: Ink absorber
64: Discharge recovery part
65: Recording head
66: Carriage
67: Guide shaft
68: Motor
69: Belt

Claims (12)

Used in recording a color image by an ink-jet recording method on a recording medium, a first ink, the ink set comprising in combination, a second ink of a color different from the ink of the first, the second 1 and each of the second ink, the coloring material and a liquid medium as essential components, in-click said first, looking contains anionic or cationic surfactant, and the second-in clause amphoteric ink set, characterized by being Nde contains an ionic compound. Coloring material in the ink of the first is a anionic dye, and said first ink see contains an anionic surfactant, colorant of the second ink is, der cationic dye the ink set according to claim 1 that. Coloring material in the ink of the first is a cationic dye, and said first ink saw contains a cationic surfactant, colorant of the second ink is an anionic dye der the ink set according to claim 1 that. Coloring material in the ink of the first is a pigment, and said first ink, see contains a cationic surfactant, colorant of the second ink is Ru der anionic dye The ink set according to claim 1. Coloring material in the ink of the first is a pigment, and said first ink, see contains an anionic surfactant, colorant of the second ink is Ru der cationic dye The ink set according to claim 1. The zwitterionic compound is an amphoteric surfactant or an ink set according to any one of claims 1-5 which is a compound represented by the general formula (I):

(In the formula, R ₁ represents an alkyl group having 1 to 48 carbon atoms or a hydrogen atom, R ₂ represents (CH ₂ ) _a -X ₁ or a hydrogen atom, and a represents an integer of 1 to 4). R ₃ represents (CH ₂ ) _b —X ₂ or R ₄ —Y or a hydrogen atom, and b represents an integer of 1 to _4. R ₄ represents an alkyl group having 1 to 48 carbon atoms or a hydrogen atom. Z represents (NR _{5 Cl ( el )} H _{2l ( el )} ) _c (NHC _n H _2n ) _d , l (el) and n are any integers from 2 to 4, and c + d is 0 to 0 50 represents an integer of 50. Y represents (NR ₆ C _m H _2m ) _e (NHC _p H _2P ) _f , m and p are any integer of 2 to 4, and e + f is any of 0 to 50 R ₅ represents (CH ₂ ) _g —X ₃ , g represents an integer of 1 to 4. R ₆ represents (CH ₂ ) _h —X ₄ , and h represents 1 Any integer of ~ 4 .X _1, X _2, X ₃ and X ₄ which are respectively a carboxyl group, a salt of a carboxyl group, a sulfonic group, selected from the group consisting of salt or a hydrogen atom of the sulfonic group. Further, R ₂ and R ₃ when a respective hydrogen atom, never c and e are both 0, _{and, X 1, X 2, X} 3 and X ₄ does not become all hydrogen atoms.). The ink set according to any one of claims 1 to 6, wherein the first ink and the second ink are inks for inkjet recording. An ink jet comprising a step of applying each of the first ink and the second ink constituting the ink set according to claim 7 onto a recording material by an ink jet recording method. Recording method. The step includes applying the first ink and the second ink so that the first ink and the second ink overlap on the recording material, and adjoining the first ink and the second ink on the recording material. the ink jet recording method according to claim 8 process, the that contain at least one of imparting such. An ink storage unit that stores each of the first ink and the second ink constituting the ink set according to claim 7, and each of the first ink and the second ink is discharged. recording unit, characterized in Tei Rukoto provided an inkjet recording heads for causing. Ink cartridge according to claim Tei Rukoto comprising a first ink and ink container portion containing each of the second ink constituting the ink set according to any one of claims 1 to 7 . The first ink and the ink container portion containing each of the second ink constituting the ink set according to any one of claims 1 to 7, and the first ink and the second an ink jet recording apparatus characterized that you have to have a jet recording heads for ejecting each of the inks.

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