JP4792621B2 - Method for producing aqueous recording liquid - Google Patents
Method for producing aqueous recording liquid Download PDFInfo
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- JP4792621B2 JP4792621B2 JP2000196130A JP2000196130A JP4792621B2 JP 4792621 B2 JP4792621 B2 JP 4792621B2 JP 2000196130 A JP2000196130 A JP 2000196130A JP 2000196130 A JP2000196130 A JP 2000196130A JP 4792621 B2 JP4792621 B2 JP 4792621B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、顔料を分散した水性記録液の製造方法に関し、特に、紙に代表されるようなポーラスな被記録材への印刷に適した水性記録液であって、とりわけ、微細なノズルからインク滴を噴射し記録するインクジェット記録用のインクとして用いた時に、効果的な水性記録液の製造方法に関する。
【０００２】
【従来の技術】
着色剤として顔料を用いた記録液は、染料を着色剤とする記録液に比べ耐光性に優れているという長所を有している。しかしながら、溶解系である染料系の記録液が経時安定性に優れているのに比べ、分散系である顔料系の記録液は顔料の沈降のため経時安定性が劣っている。
【０００３】
また、水性記録液用に加工されたＯＨＰフィルムに代表されるような透過原稿への記録においては、染料系記録液は透明性が高く鮮やかな発色を示すが、顔料系記録液は顔料粒子による光散乱が生じるため透明性が低くなり発色もくすんでしまうという短所、欠点をも有している。
【０００４】
これら顔料系記録液の欠点を解決するには、記録液中の顔料粒子をできるだけ微分散させることが必要であり、種々の分散方法が提案されている。中でも、特開平１１−８０６３３号公報のジェットインク及びジェトインク用着色微粒子の分散液の製造方法は、分散安定性に優れ、透明性が高く、発色が鮮やかであるが、固形着色コンパウンドを得る混練工程において、配合によってはコンパウンドがロールに張り付きやすく、ロールへの張り付きが起こりにくい、製造時の作業性の改善された製造方法が求められていた。
【０００５】
【発明が解決しようとする課題】
本発明が解決しようとする課題は、顔料と樹脂とからなる固形着色コンパウンドの製造工程において、コンパウンドのロールへの張り付き易さを改善すると共に、顔料粒子をより微分散可能な水性記録液の製造方法を提供することにある。
【０００６】
【課題を解決するための手段】
本発明者等は、上記の課題を解決するために鋭意研究を重ねた結果、本発明を解決するに至った。
【０００７】
即ち本発明は、顔料と樹脂とを含有する固形着色コンパウンドを用いて、顔料・樹脂・水溶性有機溶剤・水を必須成分とする水性記録液を得る製造方法において、固形着色コンパウンドの混練を、水性記録液に使用される水溶性有機溶剤のうちの一成分と同一の水溶性有機溶剤で、好ましく沸点１００℃以上の水溶性有機溶剤を加えて行うこと、さらに好ましくは水性記録液に使用され、かつ固形着色コンパウンドの混練に用いられる水溶性有機溶剤にプロピレングリコールモノプロピルエーテルを用いることを特徴とする水性記録液の製造方法を提供する。
【０００８】
ここで水性記録液に使用される水溶性有機溶剤とは、固形着色コンパウンドから水性記録液を製造するときに、その水性記録液の主構成成分の一つとして配合される水溶性有機溶剤であって、混練工程等の製造工程に使用され、水性記録液中に残留している水溶性有機溶剤を意味するものではない。
またここで、同一の水溶性有機溶剤とは、水性記録液の含有する少なくとも一種の水溶性有機溶剤と同一の水溶性有機溶剤を混練に用いれば良いという意味であり、必ずしも水性記録液中に数種の水溶性有機溶剤が用いられているときに、それと同一組成の水溶性有機溶剤混合物を混練に用いることを意味するものではない。
【０００９】
しかしより好ましくは、水性記録液に用いられている水溶性有機溶剤混合物と同一組成とまではいかなくても、固形着色コンパウンドの混練に用いられる全ての１００℃以上の水溶性有機溶剤が、全て水性記録液中で用いられた水溶性有機溶剤から選ばれたものであることが好ましく、その中にプロピレングリコールモノプロピルエーテルが含有されることがさらに好ましい。
また、混練に使用される水溶性有機溶剤が１種類のみであるときは、それがプロピレングリコールモノプロピルエーテルであり、かつプロピレングリコールモノプロピルエーテルが水性記録液に使用されていることが最も好ましい。
【００１０】
固形着色コンパウンドは、樹脂に顔料を分散させることにより得ることができる。具体的には従来知られているロールやニーダーやビーズミル等の混練装置を用いて、溶液状や溶剤等により樹脂を膨潤させた半固形状態や樹脂を加熱溶融した状態で、樹脂に顔料を均一に分散させ、最終的に固体混練物（固形着色コンパウンド）として取り出すことにより行うことができる。
樹脂と顔料との割合は、特に制限されるものでは、特に制限されるものではないが、樹脂１００重量部当たり、顔料１０〜５００重量部を混練するのが一般的である。
【００１１】
固形着色コンパウンドの混練は、あらかじめ混合した樹脂と顔料を混練装置に仕込み実施する。この時の樹脂・顔料混合物は、混練装置による加熱または混練装置から受けるせん断力により自己発熱し温度が上昇する。この時樹脂が溶融状態となり、混練装置から受けるせん断力で顔料が破砕され樹脂中に分散する。
【００１２】
混練温度は、通常５〜２００℃の範囲で行われるが、個々の樹脂には、良好な顔料分散を実現できる最適な溶融状態があり、この状態となるように混練装置による加熱温度を調整すれば良い。自己発熱により温度上昇する場合は、混練装置を冷却することで温度調整をすれば良い。
【００１３】
樹脂と顔料のみを仕込み混練することでも固形着色コンパウンドを得られるが、コンパウンドがロールへ貼り付きやすいため、より良い分散状態とするためには、混練助剤を添加することが好ましい。混練助剤としては、樹脂を溶かす低沸点の有機溶剤を用いるのが一般的である。
【００１４】
この様な有機溶剤の例としては、アセトン、メチルエチルケトン等のケトン系溶媒、メタノール、エタノール、イソプロピルアルコール等のアルコール系溶媒、クロロホルム、塩化メチレン等の塩素系溶媒、ベンゼン、トルエン等の芳香族系溶媒、等が挙げられる。これらの中から、樹脂の特性に合わせて適宜選択し使われている。
【００１５】
これらの有機溶剤は沸点が低いため、容易に揮発し固形着色コンパウンド中に残留しにくいとの利点がある反面、混練中にも樹脂・顔料混合物中から揮発するため組成が刻々と変化してしまい、分散に最適な樹脂の溶融状態を維持し続けることが難しい問題を有している。
【００１６】
この問題は分散助剤として添加する有機溶剤の揮発性が高いことが原因であり、沸点の高い有機溶剤への変更あるいは併用により解決可能であるとの推定に基づき各種有機溶剤について検討した。その結果、沸点の高い有機溶剤の適用により混練工程での作業性の向上と同時に、得られる水性記録液の微粒子化が確認された。従来使われてきた樹脂を溶かす低沸点の有機溶剤と沸点の高い有機溶剤との組み合わせが、特に有効であった。
【００１７】
しかし、沸点の高い有機溶剤は揮発しにくいため固形着色コンパウンド中に残留しやすく、最終的に得られる水性記録液へ混入してしまう。このため、分散安定性を損なったり凝集・ゲル化を起こしたりといった記録液に対する影響を考慮し、また、沸点の高い有機溶剤の混入が水性記録液の用途に対して要求される特性に関し、悪影響を与えるか否かに注意して、使用する沸点の高い有機溶剤を選択しなければならない。
【００１８】
一方、本発明の水性記録液は必須成分として水溶性有機溶剤を含有している。固形着色コンパウンドの混練時に添加する高沸点の有機溶剤として水性記録液の必須成分である水溶性有機溶剤を適用すると、固形着色コンパウンド中に残留しても水性記録液の構成成分であるため記録液に対する影響、用途上要求される特性に対する悪影響がないため、非常に好ましい。またここで、混練時の揮発を防止する観点から、水溶性有機溶剤の沸点は１００℃以上が好ましい。
もちろん微量であれば、水性記録液に使用されていない水溶性有機溶剤の混練工程への併用も可能であるが、好ましくは水性記録液に使用された水溶性有機溶剤から選択されたもののみを用いることがより望ましい。
【００１９】
水性記録液の必須成分であって、かつ固形着色コンパウンドの混練時に添加する水溶性有機溶剤の種類および使用量や、従来より混合助剤として使用されてきた樹脂を溶かす低沸点の有機溶剤の種類および使用量は、樹脂の種類や特性、混練装置の種類や運転条件により決まるためそれぞれの組み合わせにおいて最適となる条件を適宜選択し適用する必要があるが、水性記録液にも同時に用いる高沸点の水溶性有機溶剤の使用量としては、樹脂、顔料の合計重量に対して０．１〜４０重量％の範囲、低沸点の水溶性有機溶剤としては５〜４０重量％程度の使用量の範囲の中で最適条件に調整すればよい。
【００２０】
樹脂中へ顔料を微分散する場合には、高せん断力下で分散を行うことが好ましく、従来知られている分散方法の中から、相対的に高せん断力がかかる状態が形成される分散手段を採用すれば良い。本発明の水性記録液を微細なノズルからインク滴を噴射し記録するインクジェット記録用のインクに適用する場合は、２本ロールを用いることが好ましい。
【００２１】
固形着色コンパウンドから水性記録液を製造する方法としては、その一例が特開平１１−８０６３３号公報に記載されているが、本公報の方法も含めて種々の方法が採用できる。例えば、固形着色コンパウンドを有機溶剤に溶解させた後に撹拌しながら水を滴下し溶媒を水相に転化し、樹脂に内包された顔料微粒子を作製し、脱溶剤後を行いに水溶性有機溶剤や他の添加剤を加え水性記録液を得る方法。樹脂の酸基をアルカリで中和することで固形着色コンパウンド中の顔料を水性記録液媒体中へ分散させる方法等が挙げられる。
【００２２】
本発明の水性記録液を微細なノズルからインク滴を噴射し記録するインクジェット記録用のインクに適用する場合は、次の方法が特に好ましい。
【００２３】
樹脂に対して良溶媒である有機溶剤と水と塩基、水と有機溶剤が混和しない場合は混和助剤となる有機溶剤を加えた溶媒に固形着色コンパウンドを加えて混合・撹拌し固形着色コンパウンドの懸濁液を得る。得られた懸濁液をビーズレス分散装置にて再分散した後、水を追加するか有機溶剤を蒸留除去することで溶媒組成中の水の比率を高くする。以上の工程により顔料表面が樹脂で被覆された着色樹脂粒子の水分散液を得ることができる。このようにして得られた、樹脂でマイクロカプセル化された着色樹脂粒子の水分散液へ、水性記録液に必須な水溶性有機溶剤を加え混合、フィルターにて濾過し本発明の水性記録液を得ることができる。インクジェット記録用のインクとして、固形着色コンパウンドの懸濁液中に存在する樹脂の良溶媒である有機溶剤、混和助剤となる有機溶剤の残留が好ましくない場合は、溶媒組成中の水の比率を高くする工程で完全に蒸留除去してやれば良い。
ここで用いるビーズレス分散装置は、懸濁液同士もしくは懸濁液中の顔料粒子同士を、高圧の液圧で衝突させ分散を行う衝突型の分散装置であることが好ましく、具体的にはナノマイザー（ナノマイザー（株）社製）等が用いられる。
【００２４】
固形着色コンパウンドの懸濁液の組成、再分散後に変更する溶媒組成中の水の比率は、個々の固形着色コンパウンドにより最適な範囲が異なるためそれぞれの固形着色コンパウンドに合わせて適宜決定する必要があるが、固形着色コンパウンドから着色剤懸濁液を作製したときの顔料と樹脂の合計が全懸濁液中１０〜４０重量％程度、イオン交換水は２０〜７０重量％程度、樹脂に対して良溶媒となる有機溶剤が５〜４０重量％から最適数量を適宜調整すればよい。最終的な水性記録液中の顔料と樹脂の合計は全水性記録液中０．５〜２０重量％程度、水溶性有機溶剤の合計は３〜５０重量％程度となり、水の量も２０〜９８重量％程度となるが、およそこれら使用量の範囲の中から各インキ適性に適合した数量に調整する。
【００２５】
固形着色コンパウンド混練時に高沸点有機溶剤として用いることのできる、水性記録液に必須な水溶性有機溶剤は、被記録材への浸透性付与剤、水分蒸発時の乾燥防止剤として用いられ、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、グリセリン等の多価アルコール類、Ｎ−メチル−２−ピロリドン、２−ピロリドン等のピロリドン類、アミド類、エチレングリコールヘキシルエーテルやジエチレングリコールブチルエーテル等のアルキルアルコールのエチレンオキシド付加物やプロピレングリコールプロピルエーテル等のアルキルアルコールのプロピレンオキシド付加物等が挙げられる。
【００２６】
本発明の水性記録液を微細なノズルからインク滴を噴射し記録するインクジェット記録用のインクに適用する場合は、プロピレングリコールモノプロピルエーテルが水溶性有機溶剤として好適である。
【００２７】
本発明に用いる樹脂は、その種類，分子量範囲，分散の用途，顔料との相性等を勘案し適宜選択すれば良い。樹脂の種類としては、天然樹脂や合成樹脂等の中から様々な樹脂を用いることができる。中でも酸価を有する樹脂は好ましく、特に好ましい酸価の範囲は１０〜２８０である。
【００２８】
樹脂の例としては、スチレン系樹脂、アクリル系樹脂、ポリエステル系樹脂、ポリウレタン系樹脂等が挙げられる。当該樹脂は熱依存性のない永久架橋されたものであっても、常温では架橋しているが熱で非架橋状態となる可逆的性質の架橋を有するものであってもよい。本発明の水性記録液を微細なノズルからインクを噴射し記録するインクジェット記録用のインクに適用する場合は、樹脂としてスチレン、置換スチレン、（メタ）アクリル酸エステルからなる群から選ばれる少なくとも１つのモノマーと、（メタ）アクリル酸との共重合体が好ましい。この場合の分子量範囲としては１０００以上１０万以下が好ましい。
【００２９】
本発明に用いる顔料は、色目、用途、樹脂との相性を勘案し公知公用の顔料の中から適宜選択すれば良い。例としては、カーボンブラック、チタンブラック、チタンホワイト、硫化亜鉛、ベンガラ等の無機顔料、フタロシアニン顔料、モノアゾ系、ジスアゾ系等のアゾ顔料、キナクリドン顔料等の有機顔料が挙げられる。
【００３０】
本発明に用いる水は、不純物の混入防止等の観点から、イオン交換水以上の純度が望ましい。
【００３１】
本発明の水性記録液は、樹脂、顔料、水溶性有機溶剤、水を必須成分とするが、これら以外にも、防腐剤やｐＨ調整剤に代表される各種添加剤も使用できる。
添加剤の種類や添加量は、水性記録液の用途に合わせて適宜選択すれば良い。
【００３２】
【発明の実施の形態】
本発明は以下の発明及び実施形態を包含する。
１．顔料と樹脂を含有する固形着色コンパウンドを用いて、顔料と樹脂と水溶性有機溶剤と水とを必須成分とする水性記録液を得る製造方法において、固形着色コンパウンドの混練を、水性記録液に使用される水溶性有機溶剤の一つと同一の水溶性有機溶剤を加えて行うことを特徴とする水性記録液の製造方法。
２．水性記録液に使用される水溶性有機溶剤であって、かつ固形着色コンパウンドの混練に使用される水溶性有機溶剤が、沸点１００℃以上の水溶性有機溶剤であることを特徴とする前記１記載の水性記録液の製造方法。
３．水性記録液に使用される水溶性溶媒であって、かつ固形着色コンパウンドの混練に使用される水溶性有機溶剤が、プロピレングリコールモノプロピルエーテルである前記１記載の水性記録液の製造方法。
４．顔料と樹脂を含有する固形着色コンパウンドを用いて、顔料と樹脂と水溶性有機溶剤と水とを必須成分とする水性記録液を得る製造方法において、固形着色コンパウンドの混練に沸点１００℃以上の水溶性有機溶剤を使用し、かつ該水溶性有機溶剤が、全て水性記録液に使用される水溶性有機溶剤から選ばれたものであることを特徴とする水性記録液の製造方法。
【００３３】
【実施例】
次に実施例及び比較例を挙げて本発明を更に具体的に説明する。本発明はこれらの実施例に限定されるものではない。尚、以下の実施例中における「部」は『重量部』を表わす。
【００３４】
固形着色コンパウンド作製以降の各実施例に共通な操作の詳細は以下の通りである。
【００３５】
＜着色剤懸濁液の作製＞
水としてイオン交換水、樹脂に対して良溶媒となる有機溶剤としてメチルエチルケトン、塩基としてトリエタノールアミン、混和剤となる親水性有機溶剤としてイソプロピルアルコール、これらを溶解釜へ仕込みパドル翼を用いて混合した。溶媒が均一になってから、固形着色コンパウンドを加えて２〜３時間撹拌し着色剤懸濁液を得た。
【００３６】
着色剤懸濁液組成
固形着色コンパウンド ９．５ 部
イオン交換水 ２５．５ 部
メチルエチルケトン １０．７ 部
トリエタノールアミン １．０ 部
イソプロピルアルコール ４．７ 部
グリセリン ２．２ 部
合計 ５３．６ 部
【００３７】
＜着色剤粒子分散液の作製＞
得られた着色剤懸濁液に、ビーズレス分散装置であるナノマイザー（ナノマイザー（株）社製）を用いて高せん断力を与えた。ナノマイザーの運転圧力は９８ＭＰａとした。
【００３８】
ナノマイザー処理をした着色剤懸濁液５３．９部に対しグリセリン８％水溶液（グリセリン８部、イオン交換水９２部）４６．１部を加え、溶媒組成中の水の比率を高くした。この操作により懸濁液中に溶解している樹脂成分を顔料表面へ吸着させることができる。その際、着色剤懸濁液をゆっくりと撹拌しながら、イオン交換水を毎分５ｍｌの速度で全量滴下した。
【００３９】
＜水性記録液の作製＞
上記工程を経て得られた着色樹脂粒子水分散液から、メチルエチルケトン、イソプロピルアルコールを蒸留によって除去した。蒸留にはロータリーエバポレーターを用い、着色樹脂粒子水分散液を７０℃まで加熱し減圧下にて蒸留を行い、固形分含有量が２０重量％となるまで濃縮を行った。
【００４０】
濃縮された着色樹脂粒子水分散液にグリセリン、プロピレングリコールモノプロピルエーテル、イオン交換水を加えて均一になるよう撹拌し、ポアサイズ１μｍのテフロン（登録商標）フィルターで濾過し、水性記録液を得た。
【００４１】
水性記録液組成
着色樹脂粒子水分散液 ３０．０ 部
イオン交換水 ５５．０ 部
グリセリン １０．０ 部
プロピレングリコールモノプロピルエーテル ５．０ 部
合計 １００．０ 部
【００４２】
水性記録液の粒径をマイクロトラックＵＰＡ粒度分析計（Ｌｅｅｄｓ ａｎｄＮｏｒｔｈｒｕｐ社製）を用いて測定した。サンプルは測定可能な濃度となるよう、イオン交換水で適宜希釈した。
【００４３】
（実施例１）
着色剤としてＣ．Ｉ．ピグメントレッド２５４を４０部、酸価を有する樹脂としてスチレン−アクリル酸−メタクリル酸樹脂（スチレン／アクリル酸／メタクリル酸＝７７／１０／１３；分子量５万・酸価１６０）を４０部、を混合しプロピレングリコールモノプロピルエーテルを８部、メチルエチルケトン１２部を加えた塊状混合物を二本ロールで混練した。塊状混合物は混練中に自己発熱するためロールに冷却水を流しながら行った。
【００４４】
混練中の固形着色コンパウンドはロールへの張り付きもなく作業性は良好であり、メチルエチルケトンのほとんどが蒸発したシート状の固形着色コンパウンドが得られた。得られた固形着色コンパウンドは粉砕し、４〜５ｍｍ程度の大きさとした。以降、前述の方法により水性記録液を得た。
【００４５】
得られた記録液の体積平均粒径は１８２ｎｍであった。
【００４６】
（実施例２）
実施例１で得られたシート状の固形着色コンパウンドを２本ロールに掛けられる程度の適当な大きさに砕き、再度混練を行った。混練中の固形着色コンパウンドはロールへの張り付きもなく作業性は良好であった。得られた固形着色コンパウンドは粉砕し、４〜５ｍｍ程度の大きさとした。以降、前述の方法により水性記録液を得た。
【００４７】
得られた記録液の体積平均粒径は１５８ｎｍであり、実施例１の記録液よりも更に微粒子化されていた。
【００４８】
（比較例１）
実施例１と同じ顔料４０部、同じ樹脂４０部にメチルエチルケトン２０部を加えた塊状混合物を実施例１と同じ条件の２本ロールで混練した。固形着色コンパウンドはロールに張り付いてしまい、作業性は非常に悪かった。得られた固形着色コンパウンドは粉砕し、４〜５ｍｍ程度の大きさとした。以降、前述の方法により水性記録液を得た。
【００４９】
得られた記録液の体積平均粒径は４０２ｎｍであった。
【００５０】
（比較例２）
比較例１のシート状の固形着色コンパウンドを実施例２と同様に再度混練を行った。固形着色コンパウンドはロールへうまく巻き付かず、混練不可能であった。
【００５１】
【発明の効果】
本発明の水性記録液の製造方法は、顔料と樹脂とからなる固形着色コンパウンドの製造工程における作業性を改善すると共に、顔料粒子をより微分散可能な水性記録液が提供可能となる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing an aqueous recording liquid in which a pigment is dispersed. In particular, the present invention relates to an aqueous recording liquid suitable for printing on a porous recording material such as paper, and particularly an ink from a fine nozzle. The present invention relates to a method for producing an aqueous recording liquid that is effective when used as an ink for ink jet recording in which droplets are ejected and recorded.
[0002]
[Prior art]
A recording liquid using a pigment as a colorant has an advantage that it is superior in light resistance to a recording liquid using a dye as a colorant. However, the dye-based recording liquid that is a dissolution system is superior in stability over time, whereas the pigment-based recording liquid that is a dispersion system is inferior in stability over time due to precipitation of the pigment.
[0003]
Further, in recording on a transparent original such as an OHP film processed for an aqueous recording liquid, a dye-based recording liquid exhibits a high transparency and vivid color, but a pigment-based recording liquid is formed by pigment particles. Since light scattering occurs, the transparency is low and the color development is also dull.
[0004]
In order to solve the drawbacks of these pigment-based recording liquids, it is necessary to disperse the pigment particles in the recording liquid as finely as possible, and various dispersion methods have been proposed. Among them, the method for producing a dispersion of colored fine particles for jet ink and jet ink described in JP-A-11-80633 is a kneading step for obtaining a solid colored compound having excellent dispersion stability, high transparency, and vivid color development. However, depending on the formulation, there has been a demand for a production method with improved workability during production, in which the compound tends to stick to the roll and hardly sticks to the roll.
[0005]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to improve the ease of sticking of a compound to a roll in the production process of a solid coloring compound comprising a pigment and a resin, and to produce an aqueous recording liquid capable of finer dispersion of pigment particles It is to provide a method.
[0006]
[Means for Solving the Problems]
As a result of intensive studies in order to solve the above problems, the present inventors have come to solve the present invention.
[0007]
That is, the present invention uses a solid coloring compound containing a pigment and a resin, and in the production method for obtaining an aqueous recording liquid containing a pigment, a resin, a water-soluble organic solvent, and water as essential components, kneading the solid coloring compound, It is the same water-soluble organic solvent as the one of the water-soluble organic solvents used in the aqueous recording liquid, preferably by adding a water-soluble organic solvent having a boiling point of 100 ° C. or higher, more preferably used in the aqueous recording liquid. Also provided is a method for producing an aqueous recording liquid, characterized in that propylene glycol monopropyl ether is used as the water-soluble organic solvent used for kneading the solid coloring compound.
[0008]
Here, the water-soluble organic solvent used in the aqueous recording liquid is a water-soluble organic solvent that is blended as one of the main components of the aqueous recording liquid when the aqueous recording liquid is produced from the solid coloring compound. It does not mean a water-soluble organic solvent used in a manufacturing process such as a kneading process and remaining in an aqueous recording liquid.
Further, here, the same water-soluble organic solvent means that the same water-soluble organic solvent as the at least one water-soluble organic solvent contained in the aqueous recording liquid may be used for kneading. When several kinds of water-soluble organic solvents are used, it does not mean that a water-soluble organic solvent mixture having the same composition is used for kneading.
[0009]
However, more preferably, all the water-soluble organic solvents at 100 ° C. or higher used for kneading the solid coloring compound are not necessarily the same in composition as the water-soluble organic solvent mixture used in the aqueous recording liquid. It is preferably one selected from water-soluble organic solvents used in the aqueous recording liquid, and more preferably contains propylene glycol monopropyl ether.
When there is only one type of water-soluble organic solvent used for kneading, it is most preferable that it is propylene glycol monopropyl ether and that propylene glycol monopropyl ether is used in the aqueous recording liquid.
[0010]
The solid coloring compound can be obtained by dispersing a pigment in a resin. Specifically, using a conventionally known kneading device such as a roll, a kneader, or a bead mill, the pigment is uniformly applied to the resin in a semi-solid state in which the resin is swollen with a solution or a solvent, or when the resin is heated and melted. Can be dispersed and finally taken out as a solid kneaded product (solid colored compound).
The ratio of the resin and the pigment is not particularly limited and is not particularly limited, but it is common to knead 10 to 500 parts by weight of the pigment per 100 parts by weight of the resin.
[0011]
The kneading of the solid coloring compound is carried out by charging a premixed resin and pigment into a kneading apparatus. The resin / pigment mixture at this time is heated by the kneading apparatus or shearing force received from the kneading apparatus, and the temperature rises. At this time, the resin is in a molten state, and the pigment is crushed and dispersed in the resin by the shearing force received from the kneading apparatus.
[0012]
The kneading temperature is usually in the range of 5 to 200 ° C., but each resin has an optimal molten state capable of realizing good pigment dispersion, and the heating temperature by the kneading device is adjusted so as to achieve this state. It ’s fine. When the temperature rises due to self-heating, the temperature may be adjusted by cooling the kneading apparatus.
[0013]
A solid colored compound can be obtained by charging and kneading only the resin and the pigment. However, since the compound easily sticks to the roll, it is preferable to add a kneading aid in order to obtain a better dispersion state. As a kneading aid, an organic solvent having a low boiling point that dissolves the resin is generally used.
[0014]
Examples of such organic solvents include ketone solvents such as acetone and methyl ethyl ketone, alcohol solvents such as methanol, ethanol and isopropyl alcohol, chlorine solvents such as chloroform and methylene chloride, and aromatic solvents such as benzene and toluene. , Etc. Among these, it is appropriately selected and used according to the characteristics of the resin.
[0015]
Since these organic solvents have a low boiling point, they have the advantage of being easily volatilized and not easily remaining in the solid coloring compound. However, the composition of the organic solvent changes every moment because it evaporates from the resin / pigment mixture during kneading. Therefore, it is difficult to keep the molten state of the resin optimal for dispersion.
[0016]
This problem is caused by the high volatility of the organic solvent added as a dispersion aid, and various organic solvents were examined based on the assumption that they could be solved by changing to or using in combination with a high boiling point organic solvent. As a result, it was confirmed that application of an organic solvent having a high boiling point improved the workability in the kneading step, and at the same time, the resulting aqueous recording liquid was made fine. A combination of a low-boiling organic solvent that dissolves a resin and a high-boiling organic solvent that has been conventionally used has been particularly effective.
[0017]
However, since the organic solvent having a high boiling point is difficult to volatilize, it tends to remain in the solid coloring compound and is mixed into the finally obtained aqueous recording liquid. For this reason, the influence on the recording liquid, such as dispersion stability deterioration or aggregation / gelation, is taken into consideration, and the mixing of an organic solvent having a high boiling point has an adverse effect on the characteristics required for the use of the aqueous recording liquid. It is necessary to select an organic solvent having a high boiling point to be used.
[0018]
On the other hand, the aqueous recording liquid of the present invention contains a water-soluble organic solvent as an essential component. When a water-soluble organic solvent, which is an essential component of an aqueous recording liquid, is applied as a high-boiling organic solvent added during kneading of the solid coloring compound, it is a constituent of the aqueous recording liquid even if it remains in the solid coloring compound. This is very preferable because it does not have an adverse effect on the characteristics and adverse effects on the properties required for use. Here, from the viewpoint of preventing volatilization during kneading, the boiling point of the water-soluble organic solvent is preferably 100 ° C. or higher.
Of course, if it is a trace amount, it can be used in the kneading step of a water-soluble organic solvent not used in the aqueous recording liquid, but preferably only those selected from the water-soluble organic solvents used in the aqueous recording liquid are used. It is more desirable to use.
[0019]
The type and amount of water-soluble organic solvent that is an essential component of the aqueous recording liquid and is added during kneading of the solid coloring compound, and the type of low-boiling organic solvent that dissolves the resin that has been used as a mixing aid. Since the amount used depends on the type and characteristics of the resin, the type of kneading apparatus and the operating conditions, it is necessary to select and apply the optimum conditions for each combination as appropriate. The amount of the water-soluble organic solvent used is in the range of 0.1 to 40% by weight based on the total weight of the resin and pigment, and the amount of the water-soluble organic solvent having a low boiling point is in the range of about 5 to 40% by weight. It may be adjusted to the optimum condition.
[0020]
When the pigment is finely dispersed in the resin, it is preferable to perform dispersion under a high shearing force, and among the conventionally known dispersion methods, a dispersing means that forms a state where a relatively high shearing force is applied. Should be adopted. When the aqueous recording liquid of the present invention is applied to ink for ink jet recording in which ink droplets are ejected from a fine nozzle and recorded, it is preferable to use two rolls.
[0021]
An example of a method for producing an aqueous recording liquid from a solid coloring compound is described in JP-A-11-80633, but various methods including the method of this publication can be employed. For example, after dissolving a solid coloring compound in an organic solvent, water is added dropwise with stirring to convert the solvent into an aqueous phase to produce pigment fine particles encapsulated in a resin. A method of obtaining an aqueous recording liquid by adding other additives. Examples thereof include a method of dispersing the pigment in the solid coloring compound in the aqueous recording liquid medium by neutralizing the acid group of the resin with an alkali.
[0022]
When the aqueous recording liquid of the present invention is applied to ink for ink jet recording in which ink droplets are ejected from a fine nozzle and recorded, the following method is particularly preferable.
[0023]
If the organic solvent, which is a good solvent for the resin, water and base, and water and the organic solvent are not miscible, add the solid coloring compound to the solvent with the organic solvent that is the mixing aid, and mix and stir to mix the solid coloring compound. A suspension is obtained. After the obtained suspension is redispersed with a beadless dispersion apparatus, water is added or the organic solvent is distilled off to increase the ratio of water in the solvent composition. Through the above steps, an aqueous dispersion of colored resin particles having a pigment surface coated with a resin can be obtained. The water-soluble organic solvent essential for the aqueous recording liquid is added to the aqueous dispersion of colored resin particles microencapsulated with the resin, mixed, and filtered through a filter to obtain the aqueous recording liquid of the present invention. Obtainable. Ink for ink jet recording, if the residual of the organic solvent that is a good solvent for the resin present in the suspension of the solid coloring compound and the organic solvent that becomes the mixing aid is not preferred, the ratio of water in the solvent composition is What is necessary is just to carry out distillation removal completely in the process made high.
The beadless disperser used here is preferably a collision type disperser that disperses the suspensions or the pigment particles in the suspension by colliding with high pressure, and specifically, a nanomizer. (Nanomizer Co., Ltd.) etc. are used.
[0024]
The composition of the suspension of the solid color compound and the ratio of water in the solvent composition to be changed after redispersion need to be determined appropriately according to each solid color compound since the optimum range varies depending on the individual solid color compound. However, when the colorant suspension is prepared from the solid coloring compound, the total of the pigment and the resin is about 10 to 40% by weight in the total suspension, and the ion-exchanged water is about 20 to 70% by weight. What is necessary is just to adjust the optimal quantity suitably from 5 to 40 weight% of organic solvents used as a solvent. The total of the pigment and the resin in the final aqueous recording liquid is about 0.5 to 20% by weight in the total aqueous recording liquid, the total of the water-soluble organic solvent is about 3 to 50% by weight, and the amount of water is also 20 to 98. The amount is about% by weight, but is adjusted to a quantity suitable for each ink suitability from the range of the amount used.
[0025]
A water-soluble organic solvent essential for aqueous recording liquids that can be used as a high-boiling organic solvent during solid color compound kneading is used as an agent that imparts permeability to recording materials and as an anti-drying agent when water evaporates. , Propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, glycerin and other polyhydric alcohols, N-methyl-2-pyrrolidone, 2-pyrrolidone and other pyrrolidones, amides, ethylene glycol hexyl ether and diethylene glycol butyl ether Examples thereof include ethylene oxide adducts of alkyl alcohols such as propylene oxide, and propylene oxide adducts of alkyl alcohols such as propylene glycol propyl ether.
[0026]
When the aqueous recording liquid of the present invention is applied to an ink for ink jet recording in which ink droplets are ejected from a fine nozzle and recorded, propylene glycol monopropyl ether is suitable as a water-soluble organic solvent.
[0027]
The resin used in the present invention may be appropriately selected in consideration of its type, molecular weight range, use of dispersion, compatibility with pigments, and the like. As the type of resin, various resins can be used from natural resins and synthetic resins. Among them, a resin having an acid value is preferable, and a particularly preferable acid value range is 10 to 280.
[0028]
Examples of the resin include styrene resin, acrylic resin, polyester resin, polyurethane resin, and the like. The resin may be permanently crosslinked without heat dependency, or may have a reversible crosslinking that is crosslinked at room temperature but becomes a non-crosslinked state by heat. When the aqueous recording liquid of the present invention is applied to ink for ink jet recording in which ink is ejected from a fine nozzle for recording, at least one selected from the group consisting of styrene, substituted styrene, and (meth) acrylic acid ester as a resin. A copolymer of a monomer and (meth) acrylic acid is preferred. In this case, the molecular weight range is preferably 1000 or more and 100,000 or less.
[0029]
The pigment used in the present invention may be appropriately selected from publicly known pigments in consideration of color, application, and compatibility with the resin. Examples include inorganic pigments such as carbon black, titanium black, titanium white, zinc sulfide, and bengara, azo pigments such as phthalocyanine pigments, monoazo and disazo, and organic pigments such as quinacridone pigments.
[0030]
The water used in the present invention preferably has a purity higher than that of ion-exchanged water from the viewpoint of preventing impurities from being mixed.
[0031]
The aqueous recording liquid of the present invention contains a resin, a pigment, a water-soluble organic solvent, and water as essential components, but besides these, various additives typified by preservatives and pH adjusters can also be used.
What is necessary is just to select suitably the kind and addition amount of an additive according to the use of an aqueous recording liquid.
[0032]
DETAILED DESCRIPTION OF THE INVENTION
The present invention includes the following inventions and embodiments.
1. In the production method of obtaining an aqueous recording liquid containing pigment, resin, water-soluble organic solvent and water as essential components using a solid coloring compound containing pigment and resin, kneading of the solid coloring compound is used for the aqueous recording liquid. A method for producing an aqueous recording liquid, comprising adding a water-soluble organic solvent identical to one of the water-soluble organic solvents.
2. 2. The water-soluble organic solvent used in the aqueous recording liquid and used for kneading the solid coloring compound is a water-soluble organic solvent having a boiling point of 100 ° C. or higher. A method for producing an aqueous recording liquid.
3. 2. The method for producing an aqueous recording liquid as described in 1 above, wherein the water-soluble organic solvent used for the aqueous recording liquid and used for kneading the solid coloring compound is propylene glycol monopropyl ether.
4). In a production method for obtaining an aqueous recording liquid comprising a pigment, a resin, a water-soluble organic solvent and water as essential components using a solid coloring compound containing a pigment and a resin, the aqueous solution having a boiling point of 100 ° C. or higher is used for kneading the solid coloring compound. A method for producing an aqueous recording liquid, characterized in that a water-soluble organic solvent is used, and all of the water-soluble organic solvents are selected from water-soluble organic solvents used in aqueous recording liquids.
[0033]
【Example】
Next, the present invention will be described more specifically with reference to examples and comparative examples. The present invention is not limited to these examples. In the following examples, “part” represents “part by weight”.
[0034]
Details of operations common to the embodiments after the production of the solid coloring compound are as follows.
[0035]
<Preparation of colorant suspension>
Ion exchange water as water, methyl ethyl ketone as an organic solvent that is a good solvent for the resin, triethanolamine as a base, isopropyl alcohol as a hydrophilic organic solvent that is an admixture, these were charged into a melting pot and mixed using a paddle blade . After the solvent became uniform, a solid coloring compound was added and stirred for 2 to 3 hours to obtain a colorant suspension.
[0036]
Colorant suspension composition Solid coloring compound 9.5 parts Ion-exchanged water 25.5 parts Methyl ethyl ketone 10.7 parts Triethanolamine 1.0 part Isopropyl alcohol 4.7 parts Glycerin 2.2 parts Total 53.6 parts ]
<Preparation of colorant particle dispersion>
A high shear force was applied to the obtained colorant suspension using a nanomizer (manufactured by Nanomizer Co., Ltd.) which is a beadless dispersion apparatus. The operating pressure of the nanomizer was 98 MPa.
[0038]
46.1 parts of a glycerin 8% aqueous solution (glycerin 8 parts, ion-exchanged water 92 parts) was added to 53.9 parts of the colorant suspension subjected to nanomizer treatment to increase the ratio of water in the solvent composition. By this operation, the resin component dissolved in the suspension can be adsorbed on the pigment surface. At that time, the whole amount of ion-exchanged water was added dropwise at a rate of 5 ml / min while slowly stirring the colorant suspension.
[0039]
<Preparation of aqueous recording liquid>
Methyl ethyl ketone and isopropyl alcohol were removed by distillation from the colored resin particle aqueous dispersion obtained through the above steps. A rotary evaporator was used for distillation, and the colored resin particle aqueous dispersion was heated to 70 ° C. and distilled under reduced pressure, and concentrated until the solid content was 20% by weight.
[0040]
Glycerin, propylene glycol monopropyl ether, and ion-exchanged water were added to the concentrated colored resin particle aqueous dispersion, stirred uniformly, and filtered through a Teflon (registered trademark) filter having a pore size of 1 μm to obtain an aqueous recording liquid. .
[0041]
Aqueous recording liquid composition Colored resin particle aqueous dispersion 30.0 parts Ion-exchanged water 55.0 parts Glycerol 10.0 parts Propylene glycol monopropyl ether 5.0 parts Total 100.0 parts
The particle size of the aqueous recording liquid was measured using a Microtrac UPA particle size analyzer (Leeds and Northrup). The sample was appropriately diluted with ion-exchanged water so as to have a measurable concentration.
[0043]
Example 1
As a coloring agent, C.I. I. 40 parts of Pigment Red 254 and 40 parts of styrene-acrylic acid-methacrylic acid resin (styrene / acrylic acid / methacrylic acid = 77/10/13; molecular weight 50,000 / acid value 160) as a resin having an acid value Then, a bulk mixture in which 8 parts of propylene glycol monopropyl ether and 12 parts of methyl ethyl ketone were added was kneaded with two rolls. The lump mixture was self-heated during kneading, and thus was performed while flowing cooling water through the roll.
[0044]
The solid colored compound during kneading had good workability without sticking to the roll, and a sheet-like solid colored compound in which most of methyl ethyl ketone was evaporated was obtained. The obtained solid colored compound was pulverized to a size of about 4 to 5 mm. Thereafter, an aqueous recording liquid was obtained by the method described above.
[0045]
The obtained recording liquid had a volume average particle diameter of 182 nm.
[0046]
(Example 2)
The sheet-like solid colored compound obtained in Example 1 was crushed to an appropriate size so that it could be hung on two rolls, and kneaded again. The solid coloring compound during kneading had good workability without sticking to the roll. The obtained solid colored compound was pulverized to a size of about 4 to 5 mm. Thereafter, an aqueous recording liquid was obtained by the method described above.
[0047]
The obtained recording liquid had a volume average particle diameter of 158 nm and was further finely divided as compared with the recording liquid of Example 1.
[0048]
(Comparative Example 1)
A lump mixture in which 40 parts of the same pigment as in Example 1 and 40 parts of the same resin were added with 20 parts of methyl ethyl ketone was kneaded with a two-roll roll under the same conditions as in Example 1. The solid coloring compound stuck to the roll and the workability was very poor. The obtained solid colored compound was pulverized to a size of about 4 to 5 mm. Thereafter, an aqueous recording liquid was obtained by the method described above.
[0049]
The obtained recording liquid had a volume average particle diameter of 402 nm.
[0050]
(Comparative Example 2)
The sheet-like solid colored compound of Comparative Example 1 was kneaded again in the same manner as in Example 2. The solid colored compound did not wind well around the roll and could not be kneaded.
[0051]
【The invention's effect】
The method for producing an aqueous recording liquid of the present invention can improve workability in the production process of a solid coloring compound comprising a pigment and a resin, and can provide an aqueous recording liquid capable of finer dispersion of pigment particles.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000196130A JP4792621B2 (en) | 2000-06-29 | 2000-06-29 | Method for producing aqueous recording liquid |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2000196130A JP4792621B2 (en) | 2000-06-29 | 2000-06-29 | Method for producing aqueous recording liquid |
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| JP2002012798A JP2002012798A (en) | 2002-01-15 |
| JP4792621B2 true JP4792621B2 (en) | 2011-10-12 |
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| JP2000196130A Expired - Lifetime JP4792621B2 (en) | 2000-06-29 | 2000-06-29 | Method for producing aqueous recording liquid |
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| EP1333068B1 (en) * | 2002-02-04 | 2011-12-21 | Canon Kabushiki Kaisha | Aqueous ink, ink jet recording method, ink cartridge, recording unit, and ink jet recording apparatus |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH08143802A (en) * | 1994-11-17 | 1996-06-04 | Canon Inc | Water-base dispersed ink for bubble-jet recording and ink-jet recording and apparatus using the ink |
| JP3882956B2 (en) * | 1997-04-21 | 2007-02-21 | 大日本インキ化学工業株式会社 | Colored microcapsule dispersed water jet ink |
| JP3899581B2 (en) * | 1997-03-27 | 2007-03-28 | 大日本インキ化学工業株式会社 | Colored resin particle aqueous dispersion manufacturing method |
| JP3944616B2 (en) * | 1997-09-12 | 2007-07-11 | 大日本インキ化学工業株式会社 | Method for producing jet ink and dispersion of colored fine particles for jet ink |
| JP2001081390A (en) * | 1999-09-20 | 2001-03-27 | Toyo Ink Mfg Co Ltd | Aqueous pigment dispersion, its production and its use |
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