JP4123312B2 - Water-resistant ink composition - Google Patents

Description

【化１６】

で示される３級アミノ基含有有機基を含有する加水分解性シラン（Ａ）又はその部分加水分解物１００重量部と、下記一般式（２）
Ｒ ³ _n ＳｉＲ ⁴ _4-n （２）
（式中、Ｒ ³ は炭素数１〜８の非置換又は３級アミノ基を含有しない置換の一価炭化水素基、Ｒ ⁴ は炭素数１〜４のアルコキシ基又はアシロキシ基、ｎは０、１又は２である。）で表される加水分解性シラン（Ｂ）又はその部分加水分解物５〜２００重量部とを加水分解することによって得られる有機ケイ素化合物 ２〜６０重量部、
及び
（ＩＩＩ）水 ３０〜１０，０００重量部
を含有することを特徴とする耐水性インク組成物を提供する。
【００１１】
以下、本発明につき更に詳しく説明すると、本発明の（Ｉ）成分である水溶性染料化合物は、一般の水溶性インクの染料成分として使用されるものでよく、特に制限されるものではないが、ブラック、シアン、マゼンタ、イエローなどの色を与える公知の色素成分として用いられるものを好適に使用することができ、具体的にはアシッドイエロー１７、アシッドイエロー２３、アシッドイエロー７３、ダイレクトイエロー８６等のイエロー染料、アシッドレッド１、アシッドレッド８、アシッドレッド１４、アシッドレッド３７、アシッドレッド５２、アシッドレッド８７、アシッドレッド９２、アシッドレッド１０３、アシッドレッド２８９、リアクティブレッド４等のマゼンタ染料、アシッドブルー９、アシッドブルー９２、アシッドブルー８７、リアクティブブルー１５、ダイレクトブルー８６等のシアン染料、アシッドブラック２、ダイレクトブラック２２、ダイレクトブラック１５４等のブラック染料などを挙げることができる。
なお、このような染料は一般的に水溶性を発現させるためにスルホン酸ナトリウムで修飾され、それらを水に溶解させるとアルカリ性を示すものが殆どであるが、そのようなものでも好適に使用し得る。
【００１２】
また、有機顔料としては、アニリンブラック、ファーストイエロー、ジスアゾイエロー、パーマネントオレンジ、リゾールレッド、レーキレッドＣ、パーマネントレッド２Ｂ、ブリリアントカーミン６Ｂ、カーミン３Ｂ、コバルトバイオレット、メチルバイオレットレーキ、フタロシアニンブルー、ファーストスカイブルー、フタロシアニングリーンなどが挙げられる。
【００１３】
次に、本発明の（II）成分として使用する有機ケイ素化合物は、本発明のインク組成物に耐水性を付与させる成分で、この成分は驚くべきことに、水溶液に容易に溶解し、更にはアルカリ水溶液においても高安定性のものである。
更には、染料中のアゾ基などの発色基に影響を与えないため色調安定性の優れたものとなる。
【００１４】
この有機ケイ素化合物は、上述したように、下記一般式（１）
ＹＲ¹ _m ＳｉＲ² _3-m （１）
（式中、Ｒ¹ は炭素数１〜８の非置換又は窒素原子を含有しない置換の一価炭化水素基、Ｒ² は炭素数１〜４のアルコキシ基又はアシロキシ基、Ｙは３級アミノ基含有有機基であり、ｍは０又は１である。）
で表される３級アミノ基含有有機基を含有する加水分解性シラン（Ａ）又はその部分加水分解物１００重量部と、下記一般式（２）
Ｒ³ _n ＳｉＲ⁴ _4-n （２）
（式中、Ｒ³ は炭素数１〜８の非置換又は３級アミノ基を含有しない置換の一価炭化水素基、Ｒ⁴ は炭素数１〜４のアルコキシ基又はアシロキシ基、ｎは０、１又は２である。）
で表される加水分解性シラン（Ｂ）又はその部分加水分解物とを加水分解することによって得られるものである。
【００１５】
ここで、上記一般式（１）で示される３級アミノ基含有有機基を含有する加水分解性シラン（Ａ）は、系を水溶性にするために用いられる成分であり、目的とする有機ケイ素化合物に水溶性を付与させるために、その１種又は２種以上を適宜選定して用いられる。また、その部分加水分解物を用いることもできる。
【００１６】
上記一般式（１）中、Ｒ¹ は炭素数１〜８の非置換又は置換の一価炭化水素基であり、アルキル基、アルケニル基、アリール基、アラルキル基などの非置換一価炭化水素基や、これらの基の水素原子の一部又は全部をハロゲン原子などで置換した例えばハロゲン化アルキル基などの置換一価炭化水素基が挙げられるが、置換基は窒素原子を含まないものである。具体的には、−ＣＨ₃ 、−ＣＨ₂ ＣＨ₃ 、−ＣＨ₂ ＣＨ₂ ＣＨ₃ 、−ＣＨ（ＣＨ₃ ）₂ 、−ＣＨ₂ ＣＨ₂ ＣＨ₂ ＣＨ₃ 、−ＣＨ（ＣＨ₃ ）ＣＨ₂ ＣＨ₃ 、−ＣＨ₂ ＣＨ（ＣＨ₃ ）ＣＨ₃ 、−Ｃ（ＣＨ₃ ）₃ 、−Ｃ₆ Ｈ₅ 、−Ｃ₆ Ｈ₁₁、−Ｃ₆ Ｈ₁₃、−ＣＨ₂ ＣＨ₂ ＣＦ₃ 、−ＣＨ₂ ＣＨ₂ Ｃ₈ Ｆ₁₇などが例示される。
【００１７】
また、Ｒ² は炭素数１〜４のアルコキシ基又はアシロキシ基であり、具体的には、−ＯＣＨ₃ 、−ＯＣＨ₂ ＣＨ₃ 、−ＯＣＨ₂ ＣＨ₂ ＣＨ₃ 、−ＯＣＨ（ＣＨ₃ ）₂ 、−ＯＣＨ₂ ＣＨ₂ ＣＨ₂ ＣＨ₃ 、−ＯＣＨ（ＣＨ₃ ）ＣＨ₂ ＣＨ₃ 、−ＯＣＨ₂ ＣＨ（ＣＨ₃ ）ＣＨ₃ 、−ＯＣ（ＣＨ₃ ）₃ 、−ＯＣＯＣＨ₃ 、−ＯＣＯＣＨ₂ ＣＨ₃ などが例示される。
Ｙは３級アミノ基含有有機基であり、例えば下記式（３）、（５）で示されるものが挙げられる。
【００１８】
【化３】

【００１９】
（式中、Ｒ⁵ 、Ｒ⁶ 、Ｒ⁸ 、Ｒ¹⁰は炭素数１〜８、好ましくは１〜４の一価炭化水素基で、Ｒ⁷ 、Ｒ⁹ 及びＲ¹¹〜Ｒ¹⁴は炭素数１〜８の二価炭化水素基である。ｐは０〜３、好ましくは１〜２の整数である。）
なお、炭素数１〜８の一価炭化水素基は、Ｒ¹ で説明したものと同様である。炭素数１〜８の二価炭化水素基としては、アルキレン基などが挙げられる。
【００２０】
Ｙとして具体的には、下記式で示されるものを挙げることができる。
【化４】
（ＣＨ₃ ）₂ ＮＣＨ₂ −、（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ −、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ −、（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ −、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ ＣＨ₂ −、（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ ＣＨ₂ −、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ −、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ −、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₂ ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ −、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ＣＨ₂ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ −、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ −、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₂ ＣＨ₃ ）ＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₂ ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ −、
【００２１】
【化５】

【００２２】
これらの中で以下のものが特に好ましい。
【００２３】
【化６】

【００２４】
上記式（１）の３級アミノ基含有有機基を含有する加水分解性シラン（Ａ）としては、下記のものが例示することができる。
【００２５】
【化７】
（ＣＨ₃ ）₂ ＮＣＨ₂ Ｓｉ（ＯＣＨ₃ ）₃ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₃ ）₂ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₂ ＣＨ₃ ）₂ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ Ｓｉ（ＯＣＨ₃ ）₃ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₃ ）₂ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₂ ＣＨ₃ ）₂ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₃ ）₃ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₃ ）₂ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₃ ＣＨ₃ ）₂ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₃ ）₃ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₃ ）₂ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₂ ＣＨ₃ ）₂ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₃ ）₃ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₃ ）₂ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₂ ＣＨ₃ ）₂ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₃ ）₃ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₃ ）₂ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₂ ＣＨ₃ ）₂ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₃ ）₃ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₃ ）₂ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₂ ＣＨ₃ ）₂ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₃ ）₃ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₃ ）₂ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₂ ＣＨ₃ ）₂ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₂ ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₃ ）₃ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₂ ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₂ ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₃ ）₂ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₂ ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₂ ＣＨ₃ ）₂ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₂ ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₃ ）₃ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₂ ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₂ ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₃ ）₂ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₂ ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₂ ＣＨ₃ ）₂ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₃ ）₃ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₃ ）₂ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₂ ＣＨ₃ ）₂ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ＣＨ₂ ）ＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ＣＨ₂ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₃ ）₃ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ＣＨ₂ ）ＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ＣＨ₂ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ＣＨ₂ ）ＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ＣＨ₂ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₃ ）₂ 、
（ＣＨ₃ ＣＨ₂ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ＣＨ₂ ）ＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ＣＨ₂ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₂ ＣＨ₃ ）₂ 、
【００２６】
【化８】

【００２７】
【化９】

【００２８】
【化１０】

【００２９】
これらの中で特に好ましくは下記に示すものである。
【００３０】
【化１１】
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₃ ）₂ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₂ ＣＨ₃ ）₂ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₃ ）₃ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₃ ）₂ 、
（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ ＳｉＣＨ₃ （ＯＣＨ₂ ＣＨ₃ ）₂ 、
【００３１】
【化１２】

【００３２】
次に、上記加水分解性シラン（Ａ）又はその部分加水分解物と混合して用いられる加水分解性シラン（Ｂ）は、下記一般式（２）で表され、その１種を単独で又は２種以上を組み合わせて用いることができ、その部分加水分解物を使用してもよい。
【００３３】
Ｒ³ _n ＳｉＲ⁴ _4-n （２）
（式中、Ｒ³ は炭素数１〜８の非置換又は３級アミノ基を含有しない置換の一価炭化水素基、Ｒ⁴ は炭素数１〜４のアルコキシ基又はアシロキシ基、ｎは０、１又は２である。）
ここで、Ｒ³ の炭素数１〜８の非置換又は置換の一価炭化水素基としては、上記Ｒ¹ で説明したものと同様である。具体的には、−ＣＨ₃ 、−ＣＨ₂ ＣＨ₃ 、−ＣＨ₂ ＣＨ₂ ＣＨ₃ 、−ＣＨ（ＣＨ₃ ）₂ 、−ＣＨ₂ ＣＨ₂ ＣＨ₂ ＣＨ₃ 、−ＣＨ（ＣＨ₃ ）ＣＨ₂ ＣＨ₃ 、−ＣＨ₂ ＣＨ（ＣＨ₃ ）ＣＨ₃ 、−Ｃ（ＣＨ₃ ）₃ 、−Ｃ₆ Ｈ₅ 、Ｃ₆ Ｈ₁₁、−Ｃ₆ Ｈ₁₃、ＣＨ₂ ＣＨ₂ ＣＦ₃ 、−ＣＨ₂ ＣＨ₂ Ｃ₈ Ｆ₁₇などが例示される。
【００３４】
また、Ｒ⁴ は炭素数１〜４のアルコキシ基又はアシロキシ基であり、具体的には、−ＯＣＨ₃ 、−ＯＣＨ₂ ＣＨ₃ 、−ＯＣＨ₂ ＣＨ₂ ＣＨ₃ 、−ＯＣＨ（ＣＨ₃ ）₂ 、−ＯＣＨ₂ ＣＨ₂ ＣＨ₂ ＣＨ₃ 、−ＯＣＨ（ＣＨ₃ ）ＣＨ₂ ＣＨ₃ 、−ＯＣＨ₂ ＣＨ（ＣＨ₃ ）ＣＨ₃ 、−ＯＣ（ＣＨ₃ ）₃ 、−ＯＣＯＣＨ₃ 、−ＯＣＯＣＨ₂ ＣＨ₃ などが例示される。
なお、ｎは０、１又は２である。
【００３５】
この式（２）の加水分解性シラン（Ｂ）としては、下記のものを例示することができる。
【００３６】
【化１３】

【００３７】
これらの中で特に好ましくは、Ｓｉ（ＯＣＨ₃ ）₄ 、Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₄ 、ＣＨ₃ Ｓｉ（ＯＣＨ₃ ）₃ 、又はＣＨ₃ Ｓｉ（ＯＣＨ₂ ＣＨ₃ ）₃ 及びこれらの部分加水分解物である。
【００３８】
上記３級アミノ基含有有機基を含有する加水分解性シラン（Ａ）又はその部分加水分解物に式（２）の加水分解性シラン（Ｂ）又はその部分加水分解物を混合して用いる場合、その混合比は、３級アミノ基含有有機基を含有する加水分解性シラン（Ａ）又はその部分加水分解物１００重量部に対し加水分解性シラン（Ｂ）又はその部分加水分解物５〜２００重量部の割合であり、より好ましくは加水分解性シラン（Ｂ）又はその部分加水分解物の量が１０〜１５０重量部である。この量が５重量部未満であるとインクの耐水性が不十分になることがあり２００重量部を超えるとアルカリ領域での安定性が悪化する。
【００３９】
上記加水分解性シラン（Ａ）、（Ｂ）又はそれらの部分加水分解物を用いて加水分解し、本発明の主剤となる有機ケイ素化合物を得る場合、溶媒は主として水を使用するが、必要に応じて、水と溶解する有機溶媒であるアルコール、エステル、ケトン、グリコール類を水に添加する形で用いることができる。有機溶媒としては、メチルアルコール、エチルアルコール、１−プロピルアルコール、２−プロピルアルコール等のアルコール類、酢酸メチル、酢酸エチル、アセト酢酸エチル等のエステル類、アセトン、メチルエチルケトン等のケトン類、グリセリン、ジエチレングリコール等のグリコール類などを挙げることができる。
【００４０】
溶媒の量は原料シラン１００重量部に対して４００〜５，０００重量部が好ましい。更に好ましくは１，０００〜３，０００重量部である。溶媒の量が４００重量部より少ないと反応が進行しすぎ、系が均一にならない場合がある。また液の保存安定性も悪くなる場合がある。一方、５，０００重量部より多いと経済的に不利な場合が生じる。
【００４１】
また、溶媒中の水の量は、水／原料シランのモル比率で５〜５０が好ましい。このモル比率が５より少ないと加水分解が完全に進行しにくく、液の安定性が悪化する場合がある。一方、５０を超えると経済的に不利な場合が生じる。
【００４２】
反応方法としては、（１）混合シランを水中或いは加水分解に必要である以上の量の水を含む有機溶剤中に滴下する方法、（２）混合シラン或いは有機溶剤含有混合シラン中に水を滴下する方法、（３）加水分解性シラン（Ｂ）又はその部分加水分解物を水中或いは加水分解に必要である以上の量の水を含む有機溶剤中に滴下し、その後、３級アミノ基含有有機基を含有する加水分解性シラン（Ａ）又はその部分加水分解物を滴下する方法、（４）３級アミノ基含有有機基を含有する加水分解性シラン（Ａ）又はその部分加水分解物を水中或いは加水分解に必要である以上の量の水を含む有機溶剤中に滴下し、その後、加水分解性シラン（Ｂ）又はその部分加水分解物を滴下する方法などが挙げられるが、耐水性インク組成物の安定性の点から、特に（１）の反応方法が好ましい。
【００４３】
なお、得られた有機ケイ素化合物は水溶液の形で得られるが、必要に応じて、更に水を加えたり、除去したりして、有機ケイ素化合物１００重量部に対して水１０〜２，０００重量部、好ましくは１０〜１，０００重量部の比率に調整することができる。
【００４４】
このようにして得られた（II）成分は水性インク中での保存安定性が高く、特に（Ｉ）成分の染料により系がアルカリ性領域にある場合においても、安定に存在することができ、耐水性を付与することが可能である。更に染料を変色させることがないので、色調安定性にも優れている。
【００４５】
（II）成分の最適添加量は、（Ｉ）成分の水溶性染料化合物及び／又は有機顔料化合物の種類により異なるが、（Ｉ）成分１０重量部に対して２〜６０重量部、特に１０〜４０重量部とする。添加量が２重量部より少ないと、耐水性効果が小さくなり、また６０重量部より多いと、もはやそれ以上の耐水性効果を期待できず、コスト的にも好ましくない。
【００４６】
本発明の組成物（III)成分として水を使用し、上記（Ｉ）及び（II）成分の溶剤として用いるものである。
ここで水の使用量は、（Ｉ）成分１０重量部に対し３０〜１０，０００重量部、特に４０〜１，０００重量部であり、３０重量部よりも少ないと耐水性インク組成物の保存安定性が悪化し、また、１０，０００重量部より多いと画像が乱れ、目的の画像にならない。
【００４７】
本発明のインク組成物は、上記（Ｉ）〜（III)成分を含有してなるもので、耐水性、保存安定性、インク吐出安定性、発色性に優れ、インクジェット記録方法などの水性インクを用いた記録方法に好適に使用することができるものであるが、更に必要に応じて各種添加剤を配合することができる。
例えば、ノズル詰まりを抑制し、インク吐出安定性を高めるために保湿剤を添加することができ、具体的には、グリセリン、ジエチレングリコール、トリエチレングリコール、低分子量ポリエチレングリコール、ポリビニルアルコール、エチルアルコール、イソプロピルアルコールなどを挙げることができ、これらは１種を単独で又は２種以上を混合して用いることができる。
【００４８】
上記保湿剤をインク組成物中に配合する場合には、（Ｉ）成分１０重量部に対し１〜４０重量部、特に５〜３０重量部配合することが好ましい。ここでの配合量が１重量部よりも少ないとインク吐出安定性が悪くなる場合があり、また、４０重量部よりも多いと耐水性が弱くなったり、コスト的にも好ましくない場合がある。
【００４９】
また、安定性などに悪影響を与えない範囲で、任意成分を適宜添加することができる。この任意成分としては、諸性能を付与させるため、ＵＶ吸収剤、消泡剤、界面活性剤などを添加してもよい。また補強用に各種微粒子化無機酸化物あるいはそのゾル、水溶性ポリマーなどを添加することもできる。
【００５０】
以上のように、本発明のインク組成物は印字もしくは筆記画像の耐水性に優れるだけでなく、保存及び色調安定性、インク吐出安定性も高く、更には印字画像の発色性にも優れているという長所を持つインク組成物である。
【００５１】
【実施例】
以下、合成例及び実施例、比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。
［合成例１］
水１２０ｇ（６．６７ｍｏｌ）を撹拌機、温度計及び冷却器を備えた２００ｍｌの反応器に入れ撹拌混合した。ここに（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₃ ）₃ ４１．４ｇ（０．２ｍｏｌ）及びＣＨ₃ Ｓｉ（ＯＣＨ₃ ）₃ １３．６ｇ（０．１ｍｏｌ）を混合したものを室温で１０分間かけて滴下したところ、２５℃から４９℃に内温が上昇した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。次にエステルアダプターを取り付け、内温９６℃まで上げ、副生したメタノールを除去することにより、有機ケイ素化合物水溶液を１４５ｇ得た。このものの不揮発分（１０５℃／３時間）は２８．０％であった。
【００５２】
［合成例２］
水１２０ｇ（６．６７ｍｏｌ）を撹拌機、温度計及び冷却器を備えた２００ｍｌの反応器に入れ撹拌混合した。ここに（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₃ ）₃ ５２．８ｇ（０．２ｍｏｌ）及びＣＨ₃ Ｓｉ（ＯＣＨ₃ ）₃ １３．６ｇ（０．１ｍｏｌ）を混合したものを室温で１０分間かけて滴下したところ、２５℃から４５℃に内温が上昇した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。次にエステルアダプターを取り付け、内温９７℃まで上げ、副生したメタノールを除去することにより、有機ケイ素化合物水溶液を１４８ｇ得た。このものの不揮発分（１０５℃／３時間）は３０．０％であった。
［合成例３］
水１２０ｇ（６．６７ｍｏｌ）を撹拌機、温度計及び冷却器を備えた２００ｍｌの反応器に入れ撹拌混合した。ここに
【００５３】
【化１４】

５２．４ｇ（０．２ｍｏｌ）及びＣＨ₃ Ｓｉ（ＯＣＨ₃ ）₃ １３．６ｇ（０．１ｍｏｌ）を混合したものを室温で１０分間かけて滴下したところ、２５℃から４８℃に内温が上昇した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。次にエステルアダプターを取り付け、内温９８℃まで上げ、副生したメタノールを除去することにより、有機ケイ素化合物水溶液を１６０ｇ得た。このものの不揮発分（１０５℃／３時間）は２８．０％であった。
【００５４】
［合成例４］
水１２０ｇ（６．６７ｍｏｌ）を撹拌機、温度計及び冷却器を備えた２００ｍｌの反応器に入れ撹拌混合した。ここに（ＣＨ₃ ）₂ ＮＣＨ₂ ＣＨ₂ Ｎ（ＣＨ₃ ）ＣＨ₂ ＣＨ₂ ＣＨ₂ Ｓｉ（ＯＣＨ₃ ）₃ ５２．８ｇ（０．２ｍｏｌ）及びＳｉ（ＯＣＨ₃ ）₄ １５．２ｇ（０．１ｍｏｌ）を混合したものを室温で１０分間かけて滴下したところ、２５℃から４７℃に内温が上昇した。更にオイルバスにて６０〜７０℃に加熱し、そのまま１時間撹拌を行った。次にエステルアダプターを取り付け、内温９８℃まで上げ、副生したメタノールを除去することにより、有機ケイ素化合物水溶液を１４８ｇ得た。このものの不揮発分（１０５℃／３時間）は２６．０％であった。
【００５５】
［参考例１］
［ブラックインク］
（１）水溶性染料化合物：東京化成株式会社製のクロラゾールブラック／５．０ｇ
（２）合成例１の有機ケイ素化合物／１７．９ｇ（固形分 ５．０ｇ）
（３）水／６７．１ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。
［マゼンタインク］
（１）水溶性染料化合物：アルドリッチ社製のアシッドレッド１４／５．０ｇ
（２）合成例１の有機ケイ素化合物／１７．９ｇ（固形分 ５．０ｇ）
（３）水／６７．１ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。
［イエローインク］
（１）水溶性染料化合物：東京化成株式会社製のアシッドイエロー２３／５．０ｇ
（２）合成例１の有機ケイ素化合物／１７．９ｇ（固形分 ５．０ｇ）
（３）水／６７．１ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。
［シアンインク］
（１）水溶性染料化合物：東京化成株式会社製のアシッドブルー９２／５．０ｇ
（２）合成例１の有機ケイ素化合物／１７．９ｇ（固形分 ５．０ｇ）
（３）水／６７．１ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。これら４色のインク組成物をインクジェットプリンター機（キャノン製 ＢＪＣ−６００Ｓ機）に用いて、通常の紙にインクジェット記録を行った。評価項目は下記の評価を行い、その結果を表１に示す。
【００５６】
耐水性
インクジェット記録を行った紙を水中に浸漬し、水中から引き上げた時の印字画像の変化を観察した。
○：印字画像変化なし
△：やや水によるにじみあり
×：水によるにじみ激しい
画像の発色性
インクジェット記録を行った時の印字画像の発色性を観察した。
○：発色性良好
×：発色性悪い
吐出安定性
１時間連続印字を行った時、ノズル吹き出し口のインクの詰まり等による印字画像のかすれが起こらないか観察した。
○：印字画像のかすれなし
△：印字画像の一部分かすれあり
×：印字画像のかすれ激しい
保存安定性
１日３０分間の連続使用で何日間変化なく印字できるかを観察した。（ノズル詰まり、印字画像のかすれが出るまでの期間）
６０℃下保存安定性
インク組成物を６０℃の環境下に放置し、液の変化を観察した。（液の色変化やゲルなどが発生するまで、安定に存在する期間）
【００５７】
［実施例１］
［ブラックインク］
（１）水溶性染料化合物：東京化成株式会社製のクロラゾールブラック／５．０ｇ
（２）合成例２の有機ケイ素化合物／１６．７ｇ（固形分 ５．０ｇ）
（３）水／６８．３ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。
［マゼンタインク］
（１）水溶性染料化合物：アルドリッチ社製のアシッドレッド１４／５．０ｇ
（２）合成例２の有機ケイ素化合物／１６．７ｇ（固形分 ５．０ｇ）
（３）水／６８．３ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。
［イエローインク］
（１）水溶性染料化合物：東京化成株式会社製のアシッドイエロー２３／５．０ｇ
（２）合成例２の有機ケイ素化合物／１６．７ｇ（固形分 ５．０ｇ）
（３）水／６８．３ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。
［シアンインク］
（１）水溶性染料化合物：東京化成株式会社製のアシッドブルー９２／５．０ｇ
（２）合成例２の有機ケイ素化合物／１６．７ｇ（固形分 ５．０ｇ）
（３）水／６８．３ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。これら４色のインク組成物をインクジェットプリンター機（キャノン製 ＢＪＣ−６００Ｓ機）に用いて、通常の紙にインクジェット記録を行った。評価は参考例１と同様に行った。その結果を表１に示す。
【００５８】
［実施例２］
［ブラックインク］
（１）水溶性染料化合物：東京化成株式会社製のクロラゾールブラック／５．０ｇ
（２）合成例３の有機ケイ素化合物／１７．９ｇ（固形分 ５．０ｇ）
（３）水／６７．１ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。
［マゼンタインク］
（１）水溶性染料化合物：アルドリッチ社製のアシッドレッド１４／５．０ｇ
（２）合成例３の有機ケイ素化合物／１７．９ｇ（固形分 ５．０ｇ）
（３）水／６７．１ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。
［イエローインク］
（１）水溶性染料化合物：東京化成株式会社製のアシッドイエロー２３／５．０ｇ
（２）合成例３の有機ケイ素化合物／１７．９ｇ（固形分 ５．０ｇ）
（３）水／６７．１ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。
［シアンインク］
（１）水溶性染料化合物：東京化成株式会社製のアシッドブルー９２／５．０ｇ
（２）合成例３の有機ケイ素化合物／１７．９ｇ（固形分 ５．０ｇ）
（３）水／６７．１ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。これら４色のインク組成物をインクジェットプリンター機（キャノン製 ＢＪＣ−６００Ｓ機）に用いて、通常の紙にインクジェット記録を行った。評価は参考例１と同様に行った。その結果を表１に示す。
【００５９】
［実施例３］
［ブラックインク］
（１）水溶性染料化合物：東京化成株式会社製のクロラゾールブラック／５．０ｇ
（２）合成例４の有機ケイ素化合物／１９．２ｇ（固形分 ５．０ｇ）
（３）水／６５．８ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。
［マゼンタインク］
（１）水溶性染料化合物：アルドリッチ社製のアシッドレッド１４／５．０ｇ
（２）合成例４の有機ケイ素化合物／１９．２ｇ（固形分 ５．０ｇ）
（３）水／６５．８ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。
［イエローインク］
（１）水溶性染料化合物：東京化成株式会社製のアシッドイエロー２３／５．０ｇ
（２）合成例４の有機ケイ素化合物／１９．２ｇ（固形分 ５．０ｇ）
（３）水／６５．８ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。
［シアンインク］
（１）水溶性染料化合物：東京化成株式会社製のアシッドブルー９２／５．０ｇ
（２）合成例４の有機ケイ素化合物／１９．２ｇ（固形分 ５．０ｇ）
（３）水／６５．８ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。これら４色のインク組成物をインクジェットプリンター機（キャノン製 ＢＪＣ−６００Ｓ機）に用いて、通常の紙にインクジェット記録を行った。評価は参考例１と同様に行った。その結果を表１に示す。
【００６０】
［比較例１］
インクジェットプリンター機（キャノン製 ＢＪＣ−６００Ｓ機）付属のインクを用いて、通常の紙にインクジェット記録を行った。評価項目は参考例１と同様に評価を行い、その結果を表１に示す。
［比較例２］
インクジェットプリンター機（エプソン製 ＭＪ−５００Ｃ機）付属のインクを用いて、通常の紙にインクジェット記録を行った。評価項目は参考例１と同様に評価を行い、その結果を表１に示す。
【００６１】
［比較例３］
［ブラックインク］
（１）水溶性染料化合物：東京化成株式会社製のクロラゾールブラック／５．０ｇ
（２）ペンタエチレンヘキサミン／５．０ｇ
（３）水／８０．０ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。
［マゼンタインク］
（１）水溶性染料化合物：アルドリッチ社製のアシッドレッド１４／５．０ｇ
（２）ペンタエチレンヘキサミン／５．０ｇ
（３）水／８０．０ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。
［イエローインク］
（１）水溶性染料化合物：東京化成株式会社製のアシッドイエロー２３／５．０ｇ
（２）ペンタエチレンヘキサミン／５．０ｇ
（３）水／８０．０ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。
［シアンインク］
（１）水溶性染料化合物：東京化成株式会社製のアシッドブルー９２／５．０ｇ
（２）ペンタエチレンヘキサミン／５．０ｇ
（３）水／８０．０ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。これら４色のインク組成物をインクジェットプリンター機（キャノン製 ＢＪＣ−６００Ｓ機）に用いて、通常の紙にインクジェット記録を行った。評価は参考例１と同様に行った。その結果を表１に示す。
【００６２】
［比較例４］
［ブラックインク］
（１）水溶性染料化合物：東京化成株式会社製のクロラゾールブラック／５．０ｇ
（２）トリエチレンペンタミン／５．０ｇ
（３）水／８０．０ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。
［マゼンタインク］
（１）水溶性染料化合物：アルドリッチ社製のアシッドレッド１４／５．０ｇ
（２）トリエチレンペンタミン／５．０ｇ
（３）水／８０．０ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。
［イエローインク］
（１）水溶性染料化合物：東京化成株式会社製のアシッドイエロー２３／５．０ｇ
（２）トリエチレンペンタミン／５．０ｇ
（３）水／８０．０ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。
［シアンインク］
（１）水溶性染料化合物：東京化成株式会社製のアシッドブルー９２／５．０ｇ
（２）トリエチレンペンタミン／５．０ｇ
（３）水／８０．０ｇ
（４）保湿剤：グリセリン／１０．０ｇ
（１）〜（４）成分を混合し、耐水性インク組成物を調製した。これら４色のインク組成物をインクジェットプリンター機（キャノン製 ＢＪＣ−６００Ｓ機）に用いて、通常の紙にインクジェット記録を行った。評価は参考例１と同様に行った。その結果を表１に示す。
【００６３】
【表１】

【００６４】
【発明の効果】
本発明の耐水性インク組成物は耐水性に優れるだけでなく、保存安定性、インク吐出安定性も高く、特に色調安定性に優れた耐水性インク組成物に関するものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an ink composition that can be suitably used in a recording method using water-based ink, particularly an ink jet recording method, and a printed image is completely printed even after being dried on a recording material and exposed to water or sewage. The present invention relates to a water-resistant ink composition that is excellent in storage stability, ink ejection stability, color developability, and water resistance without being disturbed.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, various ink (recording liquid) ejection methods have been adopted as inkjet recording methods. For example, an electrostatic suction method, a method of applying mechanical vibration or variation to ink using a piezoelectric element, and heating and foaming ink. In addition, a recording method is known in which ink droplets are generated by a method using the pressure, and a part or all of them are adhered to a recording material such as paper. These are generally employed as excellent recording methods because they generate less noise and can perform high-speed printing and multicolor printing.
By the way, as an ink generally used in an ink jet recording method, an ink mainly containing water is used from the viewpoint of safety and recording characteristics, but it is possible to prevent nozzle clogging and improve discharge stability. Polyhydric alcohol is also added for the purpose.
[0003]
However, with the improvement and popularization of the performance of ink recording apparatuses and the like, improvement of higher characteristics is being demanded for ink agents. Among these, water resistance is a particularly required characteristic. Recently, there is a remarkable spread of inkjet printers for general office use and household use, but in such an environment, the printed matter has more opportunities to come in contact with drinking water such as water, coffee, juice, and sewage, so it is water resistant. Is absolutely necessary.
[0004]
That is, water-soluble dye-based inks with good color developability that are currently on the market have little water resistance, and therefore, when touched with water or the like, the printed image is likely to be strange due to color blur. This means that the dye itself is water-soluble, and the polyhydric alcohol added to improve ejection stability is also water-soluble, so when the printed image comes into contact with water, those components attract water. This is because the image is disturbed.
In this case, it is conceivable to eliminate the polyhydric alcohol component of the dye-based ink.
[0005]
On the other hand, an attempt to make the dye itself reactive and bind to the base material is reported in “Coloring Materials” 67 [6] (356-361 (1994)). This is one in which an alkoxysilyl group is introduced into the dye itself to make it reactive. However, water-soluble dyes usually have —SO—_ThreeNa group, -NH₂Group, -CN group and other polar groups have been introduced, these polar groups react with alkoxysilyl groups, and it is difficult to introduce alkoxysilyl groups well. Has a problem that the stability is poor and the cost is disadvantageous.
[0006]
Further, in “Coloring Material” 66 [9] (517-522 (1993)), a dye is added to tetraethoxysilane or methyltriethoxysilane, and after preparing a sol solution, this is treated on a glass substrate. A method for fixing a dye has been proposed. However, when such a sol solution is added to an aqueous ink that generally shows basicity, it will gel as soon as it is added and cannot be used for an aqueous ink. There is.
[0007]
In addition, silicone compounds are commonly used as water resistance imparting additives, which can impart excellent water resistance in solvent systems, but are not very stable in water. However, most of them have some stability under weak acidity and lose stability when the system is alkaline. Since many water-soluble dyes generally show alkalinity, they cannot be used in such systems.
Recently, water-soluble polyamines have been used in order to give such dyes water resistance, but the reactivity of amino groups, especially primary amino groups or secondary amino groups of polyamines has been used. However, due to the basicity, the azo group in the dye is decomposed, so that there is a problem that the color changes drastically and the color tone changes.
[0008]
Furthermore, Japanese Patent Application Laid-Open No. Hei 6-279678 proposes an aqueous surface treatment composition. This is an aqueous treatment agent mainly composed of a reaction product obtained by reacting and hydrolyzing an aminotrialkoxysilane and an organic compound that reacts with its amino group, or a product obtained by further reacting it with an organometallic compound such as tetraalkoxysilane. is there. However, in this method, since the amino group which is largely involved in water solubility reacts with the organic group, the main agent has poor water solubility. Also, in order to cover it, an anionic surfactant is added as a stabilizer to the treatment liquid, but when used as an additive for aqueous ink, if such an anionic surfactant is contained, Water resistance may deteriorate. In addition, the long-term storage stability of this treatment solution is not very good, and it is unstable in the alkaline region. Therefore, it effectively introduces a xylyl group as an additive to a water-soluble ink composition to make it reactive. It is a thing. However, water-soluble dyes usually have —SO—_ThreeNa group, -NH₂Group, -CN group and other polar groups have been introduced, these polar groups react with alkoxysilyl groups, and it is difficult to introduce alkoxysilyl groups well. Has a problem that the stability is poor and the cost is disadvantageous.
The present invention has been made in view of the above circumstances, and is an ink composition suitably used for a recording method using water-based ink (particularly, an ink jet recording method), and a printed image printed by the ink is completely in water. An object of the present invention is to provide an ink composition excellent in water resistance that is not affected.
[0009]
Means for Solving the Problem and Embodiment of the Invention
As a result of intensive studies to achieve the above object, the present inventors have
(I) a water-soluble dye compound and / or an organic pigment compound,
(II) The following general formula (1)
YR¹ _mSiR² _3-m                            (1)
(Wherein R¹Is a C1-C8 unsubstituted or substituted monovalent hydrocarbon group containing no nitrogen atom, R²Is an alkoxy group having 1 to 4 carbon atoms or an acyloxy group, Y is a tertiary amino group-containing organic group, and m is 0 or 1. )
100 parts by weight of a hydrolyzable silane (A) or a partially hydrolyzed product thereof containing a tertiary amino group-containing organic group represented by the following general formula (2)
R^Three _nSiR^Four _4-n                              (2)
(Wherein R^ThreeIs a monovalent hydrocarbon group having 1 to 8 carbon atoms which is unsubstituted or does not contain a tertiary amino group, R^FourIs an alkoxy group having 1 to 4 carbon atoms or an acyloxy group, and n is 0, 1 or 2. )
It is obtained by hydrolyzing a hydrolyzable silane (B) represented by the formula (1) or a mixture thereof with 5 to 200 parts by weight of a partially hydrolyzed product in water or in an organic solvent containing more water than necessary for hydrolysis. An organosilicon compound, and
(III) Water
The ink composition obtained by blending at a specific ratio can be suitably used in a recording method using water-based ink (especially an inkjet recording method), and the printed image printed with the ink is not affected by moisture at all. In addition to exhibiting excellent water resistance, it has been found that it has excellent storage stability, ink ejection stability, color development properties, and has no color tone change due to the influence of amino groups, and also has excellent color tone stability. Thus, the present invention has been made.
[0010]
  Therefore, the present invention
(I) 10 parts by weight of a water-soluble dye compound and / or organic pigment compound,
(II) The following formula
Embedded image

Embedded image

Indicated byHydrolyzable silane (A) containing a tertiary amino group-containing organic group or 100 parts by weight of a partially hydrolyzed product thereof,The following generalFormula (2)
R ^Three _n SiR ^Four _4-n   (2)
(Wherein R ^Three Is a monovalent hydrocarbon group having 1 to 8 carbon atoms which is unsubstituted or does not contain a tertiary amino group, R ^Four Is an alkoxy group having 1 to 4 carbon atoms or an acyloxy group, and n is 0, 1 or 2. )2 to 60 parts by weight of an organosilicon compound obtained by hydrolyzing 5 to 200 parts by weight of a hydrolyzable silane (B) or a partial hydrolyzate thereof
as well as
(III) 30 to 10,000 parts by weight of water
A water-resistant ink composition is provided.
[0011]
Hereinafter, the present invention will be described in more detail. The water-soluble dye compound as the component (I) of the present invention may be used as a dye component of a general water-soluble ink, and is not particularly limited. Those used as known pigment components that give colors such as black, cyan, magenta, and yellow can be suitably used. Specifically, such as acid yellow 17, acid yellow 23, acid yellow 73, and direct yellow 86 Yellow dye, Acid Red 1, Acid Red 8, Acid Red 14, Acid Red 37, Acid Red 52, Acid Red 87, Acid Red 92, Acid Red 103, Acid Red 289, Reactive Red 4, etc. Magenta dye, Acid Blue 9, Acid Blue 92, Acid Bu Over 87, it can be mentioned Reactive Blue 15, cyan dyes such as Direct Blue 86, Acid Black 2, Direct Black 22, and black dyes such as Direct Black 154.
Such dyes are generally modified with sodium sulfonate to develop water solubility, and most of them exhibit alkalinity when dissolved in water, but such dyes are also preferably used. obtain.
[0012]
Organic pigments include aniline black, first yellow, disazo yellow, permanent orange, resol red, lake red C, permanent red 2B, brilliant carmine 6B, carmine 3B, cobalt violet, methyl violet lake, phthalocyanine blue, and first sky blue. And phthalocyanine green.
[0013]
Next, the organosilicon compound used as the component (II) of the present invention is a component that imparts water resistance to the ink composition of the present invention. This component surprisingly dissolves easily in an aqueous solution. Even an alkaline aqueous solution is highly stable.
Furthermore, since the coloring group such as an azo group in the dye is not affected, the tone stability is excellent.
[0014]
As described above, this organosilicon compound has the following general formula (1).
YR¹ _mSiR² _3-m                            (1)
(Wherein R¹Is a C1-C8 unsubstituted or substituted monovalent hydrocarbon group containing no nitrogen atom, R²Is an alkoxy group having 1 to 4 carbon atoms or an acyloxy group, Y is a tertiary amino group-containing organic group, and m is 0 or 1. )
100 parts by weight of a hydrolyzable silane (A) or a partially hydrolyzed product thereof containing a tertiary amino group-containing organic group represented by the following general formula (2)
R^Three _nSiR^Four _4-n                              (2)
(Wherein R^ThreeIs a monovalent hydrocarbon group having 1 to 8 carbon atoms which is unsubstituted or does not contain a tertiary amino group, R^FourIs an alkoxy group having 1 to 4 carbon atoms or an acyloxy group, and n is 0, 1 or 2. )
It is obtained by hydrolyzing the hydrolyzable silane (B) represented by these or its partial hydrolyzate.
[0015]
Here, the hydrolyzable silane (A) containing the tertiary amino group-containing organic group represented by the general formula (1) is a component used for making the system water-soluble, and is intended to be an organic silicon. In order to impart water solubility to the compound, one or more of them are appropriately selected and used. Moreover, the partial hydrolyzate can also be used.
[0016]
In the general formula (1), R¹Is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, an unsubstituted monovalent hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group or an aralkyl group, or one of the hydrogen atoms of these groups. Examples thereof include a substituted monovalent hydrocarbon group such as a halogenated alkyl group in which part or all are substituted with a halogen atom or the like, and the substituent does not contain a nitrogen atom. Specifically, -CH_Three, -CH₂CH_Three, -CH₂CH₂CH_Three, -CH (CH_Three)₂, -CH₂CH₂CH₂CH_Three, -CH (CH_Three) CH₂CH_Three, -CH₂CH (CH_Three) CH_Three, -C (CH_Three)_Three, -C₆H_Five, -C₆H₁₁, -C₆H₁₃, -CH₂CH₂CF_Three, -CH₂CH₂C₈F₁₇Etc. are exemplified.
[0017]
R²Is an alkoxy group having 1 to 4 carbon atoms or an acyloxy group, specifically, —OCH_Three, -OCH₂CH_Three, -OCH₂CH₂CH_Three, -OCH (CH_Three)₂, -OCH₂CH₂CH₂CH_Three, -OCH (CH_Three) CH₂CH_Three, -OCH₂CH (CH_Three) CH_Three, -OC (CH_Three)_Three, -OCOCH_Three, -OCOCH₂CH_ThreeEtc. are exemplified.
Y is a tertiary amino group-containing organic group, and examples thereof include those represented by the following formulas (3) and (5).
[0018]
[Chemical 3]

[0019]
(Wherein R^Five, R⁶, R⁸, R^TenIs a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, R⁷, R⁹And R¹¹~ R¹⁴Is a C1-C8 divalent hydrocarbon group. p is an integer of 0-3, preferably 1-2. )
The monovalent hydrocarbon group having 1 to 8 carbon atoms is R¹This is the same as that described in. An alkylene group etc. are mentioned as a C1-C8 bivalent hydrocarbon group.
[0020]
Specific examples of Y include those represented by the following formula.
[Formula 4]
(CH_Three)₂NCH₂-, (CH_ThreeCH₂)₂NCH₂−,
(CH_Three)₂NCH₂CH₂-, (CH_ThreeCH₂)₂NCH₂CH₂−,
(CH_Three)₂NCH₂CH₂CH₂-, (CH_ThreeCH₂)₂NCH₂CH₂CH₂−,
(CH_Three)₂NCH₂CH₂N (CH_Three) CH₂CH₂CH₂−,
(CH_ThreeCH₂)₂NCH₂CH₂N (CH_Three) CH₂CH₂CH₂−,
(CH_ThreeCH₂)₂NCH₂CH₂N (CH₂CH_Three) CH₂CH₂CH₂−,
(CH_Three)₂NCH₂CH₂N (CH_ThreeCH₂) CH₂CH₂CH₂−,
(CH_Three)₂NCH₂CH₂N (CH_Three) CH₂CH₂N (CH_Three) CH₂CH₂CH₂−,
(CH_ThreeCH₂)₂NCH₂CH₂N (CH₂CH_Three) CH₂CH₂N (CH₂CH_Three) CH₂CH₂CH₂−,
[0021]
[Chemical formula 5]

[0022]
Of these, the following are particularly preferred.
[0023]
[Chemical 6]

[0024]
Examples of the hydrolyzable silane (A) containing the tertiary amino group-containing organic group of the above formula (1) include the following.
[0025]
[Chemical 7]
(CH_Three)₂NCH₂Si (OCH_Three)_Three,
(CH_Three)₂NCH₂Si (OCH₂CH_Three)_Three,
(CH_Three)₂NCH₂SiCH_Three(OCH_Three)₂,
(CH_Three)₂NCH₂SiCH_Three(OCH₂CH_Three)₂,
(CH_ThreeCH₂)₂NCH₂Si (OCH_Three)_Three,
(CH_ThreeCH₂)₂NCH₂Si (OCH₂CH_Three)_Three,
(CH_ThreeCH₂)₂NCH₂SiCH_Three(OCH_Three)₂,
(CH_ThreeCH₂)₂NCH₂SiCH_Three(OCH₂CH_Three)₂,
(CH_Three)₂NCH₂CH₂Si (OCH_Three)_Three,
(CH_Three)₂NCH₂CH₂Si (OCH₂CH_Three)_Three,
(CH_Three)₂NCH₂CH₂SiCH_Three(OCH_Three)₂,
(CH_Three)₂NCH₂CH₂SiCH_Three(OCH_ThreeCH_Three)₂,
(CH_ThreeCH₂)₂NCH₂CH₂Si (OCH_Three)_Three,
(CH_ThreeCH₂)₂NCH₂CH₂Si (OCH₂CH_Three)_Three,
(CH_ThreeCH₂)₂NCH₂CH₂SiCH_Three(OCH_Three)₂,
(CH_ThreeCH₂)₂NCH₂CH₂SiCH_Three(OCH₂CH_Three)₂,
(CH_Three)₂NCH₂CH₂CH₂Si (OCH_Three)_Three,
(CH_Three)₂NCH₂CH₂CH₂Si (OCH₂CH_Three)_Three,
(CH_Three)₂NCH₂CH₂CH₂SiCH_Three(OCH_Three)₂,
(CH_Three)₂NCH₂CH₂CH₂SiCH_Three(OCH₂CH_Three)₂,
(CH_ThreeCH₂)₂NCH₂CH₂CH₂Si (OCH_Three)_Three,
(CH_ThreeCH₂)₂NCH₂CH₂CH₂Si (OCH₂CH_Three)_Three,
(CH_ThreeCH₂)₂NCH₂CH₂CH₂SiCH_Three(OCH_Three)₂,
(CH_ThreeCH₂)₂NCH₂CH₂CH₂SiCH_Three(OCH₂CH_Three)₂,
(CH_Three)₂NCH₂CH₂N (CH_Three) CH₂CH₂CH₂Si (OCH_Three)_Three,
(CH_Three)₂NCH₂CH₂N (CH_Three) CH₂CH₂CH₂Si (OCH₂CH_Three)_Three,
(CH_Three)₂NCH₂CH₂N (CH_Three) CH₂CH₂CH₂SiCH_Three(OCH_Three)₂,
(CH_Three)₂NCH₂CH₂N (CH_Three) CH₂CH₂CH₂SiCH_Three(OCH₂CH_Three)₂,
(CH_ThreeCH₂)₂NCH₂CH₂N (CH_Three) CH₂CH₂CH₂Si (OCH_Three)_Three,
(CH_ThreeCH₂)₂NCH₂CH₂N (CH_Three) CH₂CH₂CH₂Si (OCH₂CH_Three)_Three,
(CH_ThreeCH₂)₂NCH₂CH₂N (CH_Three) CH₂CH₂CH₂SiCH_Three(OCH_Three)₂,
(CH_ThreeCH₂)₂NCH₂CH₂N (CH_Three) CH₂CH₂CH₂SiCH_Three(OCH₂CH_Three)₂,
(CH_Three)₂NCH₂CH₂N (CH₂CH_Three) CH₂CH₂CH₂Si (OCH_Three)_Three,
(CH_Three)₂NCH₂CH₂N (CH₂CH_Three) CH₂CH₂CH₂Si (OCH₂CH_Three)_Three,
(CH_Three)₂NCH₂CH₂N (CH₂CH_Three) CH₂CH₂CH₂SiCH_Three(OCH_Three)₂,
(CH_Three)₂NCH₂CH₂N (CH₂CH_Three) CH₂CH₂CH₂SiCH_Three(OCH₂CH_Three)₂,
(CH_ThreeCH₂)₂NCH₂CH₂N (CH₂CH_Three) CH₂CH₂CH₂Si (OCH_Three)_Three,
(CH_ThreeCH₂)₂NCH₂CH₂N (CH₂CH_Three) CH₂CH₂CH₂Si (OCH₂CH_Three)_Three,
(CH_ThreeCH₂)₂NCH₂CH₂N (CH₂CH_Three) CH₂CH₂CH₂SiCH_Three(OCH_Three)₂,
(CH_ThreeCH₂)₂NCH₂CH₂N (CH₂CH_Three) CH₂CH₂CH₂SiCH_Three(OCH₂CH_Three)₂,
(CH_Three)₂NCH₂CH₂N (CH_Three) CH₂CH₂N (CH_Three) CH₂CH₂CH₂Si (OCH_Three)_Three,
(CH_Three)₂NCH₂CH₂N (CH_Three) CH₂CH₂N (CH_Three) CH₂CH₂CH₂Si (OCH₂CH_Three)_Three,
(CH_Three)₂NCH₂CH₂N (CH_Three) CH₂CH₂N (CH_Three) CH₂CH₂CH₂SiCH_Three(OCH_Three)₂,
(CH_Three)₂NCH₂CH₂N (CH_Three) CH₂CH₂N (CH_Three) CH₂CH₂CH₂SiCH_Three(OCH₂CH_Three)₂,
(CH_ThreeCH₂)₂NCH₂CH₂N (CH_ThreeCH₂) CH₂CH₂N (CH_ThreeCH₂) CH₂CH₂CH₂Si (OCH_Three)_Three,
(CH_ThreeCH₂)₂NCH₂CH₂N (CH_ThreeCH₂) CH₂CH₂N (CH_ThreeCH₂) CH₂CH₂CH₂Si (OCH₂CH_Three)_Three,
(CH_ThreeCH₂)₂NCH₂CH₂N (CH_ThreeCH₂) CH₂CH₂N (CH_ThreeCH₂) CH₂CH₂CH₂SiCH_Three(OCH_Three)₂,
(CH_ThreeCH₂)₂NCH₂CH₂N (CH_ThreeCH₂) CH₂CH₂N (CH_ThreeCH₂) CH₂CH₂CH₂SiCH_Three(OCH₂CH_Three)₂,
[0026]
[Chemical 8]

[0027]
[Chemical 9]

[0028]
Embedded image

[0029]
Among these, the following are particularly preferable.
[0030]
Embedded image
(CH_Three)₂NCH₂CH₂CH₂SiCH_Three(OCH_Three)₂,
(CH_Three)₂NCH₂CH₂CH₂SiCH_Three(OCH₂CH_Three)₂,
(CH_Three)₂NCH₂CH₂N (CH_Three) CH₂CH₂CH₂Si (OCH_Three)_Three,
(CH_Three)₂NCH₂CH₂N (CH_Three) CH₂CH₂CH₂Si (OCH₂CH_Three)_Three,
(CH_Three)₂NCH₂CH₂N (CH_Three) CH₂CH₂CH₂SiCH_Three(OCH_Three)₂,
(CH_Three)₂NCH₂CH₂N (CH_Three) CH₂CH₂CH₂SiCH_Three(OCH₂CH_Three)₂,
[0031]
Embedded image

[0032]
Next, the hydrolyzable silane (B) used by mixing with the hydrolyzable silane (A) or a partial hydrolyzate thereof is represented by the following general formula (2), one of which is used alone or 2 Two or more species can be used in combination, and a partial hydrolyzate thereof may be used.
[0033]
R^Three _nSiR^Four _4-n                              (2)
(Wherein R^ThreeIs a monovalent hydrocarbon group having 1 to 8 carbon atoms which is unsubstituted or does not contain a tertiary amino group, R^FourIs an alkoxy group having 1 to 4 carbon atoms or an acyloxy group, and n is 0, 1 or 2. )
Where R^ThreeAs the unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, R¹This is the same as that described in. Specifically, -CH_Three, -CH₂CH_Three, -CH₂CH₂CH_Three, -CH (CH_Three)₂, -CH₂CH₂CH₂CH_Three, -CH (CH_Three) CH₂CH_Three, -CH₂CH (CH_Three) CH_Three, -C (CH_Three)_Three, -C₆H_Five, C₆H₁₁, -C₆H₁₃, CH₂CH₂CF_Three, -CH₂CH₂C₈F₁₇Etc. are exemplified.
[0034]
R^FourIs an alkoxy group having 1 to 4 carbon atoms or an acyloxy group, specifically, —OCH_Three, -OCH₂CH_Three, -OCH₂CH₂CH_Three, -OCH (CH_Three)₂, -OCH₂CH₂CH₂CH_Three, -OCH (CH_Three) CH₂CH_Three, -OCH₂CH (CH_Three) CH_Three, -OC (CH_Three)_Three, -OCOCH_Three, -OCOCH₂CH_ThreeEtc. are exemplified.
N is 0, 1 or 2.
[0035]
As the hydrolyzable silane (B) of the formula (2), the following can be exemplified.
[0036]
Embedded image

[0037]
Of these, Si (OCH) is particularly preferable._Three)_Four, Si (OCH₂CH_Three)_Four, CH_ThreeSi (OCH_Three)_ThreeOr CH_ThreeSi (OCH₂CH_Three)_ThreeAnd partial hydrolysates thereof.
[0038]
When using the hydrolyzable silane (B) or the partial hydrolyzate of the formula (2) mixed with the hydrolyzable silane (A) or the partial hydrolyzate thereof containing the tertiary amino group-containing organic group, The mixing ratio is 5 to 200 weights of hydrolyzable silane (B) or partial hydrolyzate thereof with respect to 100 parts by weight of hydrolyzable silane (A) or tertiary hydrolyzate containing a tertiary amino group-containing organic group. More preferably, the amount of hydrolyzable silane (B) or its partial hydrolyzate is 10 to 150 parts by weight. If this amount is less than 5 parts by weight, the water resistance of the ink may be insufficient. If it exceeds 200 parts by weight, the stability in the alkaline region is deteriorated.
[0039]
When hydrolyzing using the hydrolyzable silane (A), (B) or a partial hydrolyzate thereof to obtain an organosilicon compound as a main component of the present invention, water is mainly used as a solvent. Accordingly, alcohols, esters, ketones, and glycols, which are organic solvents that dissolve in water, can be used by adding them to water. Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, 1-propyl alcohol, and 2-propyl alcohol, esters such as methyl acetate, ethyl acetate, and ethyl acetoacetate, ketones such as acetone and methyl ethyl ketone, glycerin, and diethylene glycol. And the like.
[0040]
The amount of the solvent is preferably 400 to 5,000 parts by weight based on 100 parts by weight of the raw material silane. More preferably, it is 1,000 to 3,000 parts by weight. If the amount of the solvent is less than 400 parts by weight, the reaction may proceed excessively and the system may not be uniform. In addition, the storage stability of the liquid may deteriorate. On the other hand, when the amount is more than 5,000 parts by weight, an economical disadvantage may occur.
[0041]
The amount of water in the solvent is preferably 5 to 50 in terms of a water / raw material silane molar ratio. When this molar ratio is less than 5, hydrolysis hardly proceeds completely, and the stability of the liquid may be deteriorated. On the other hand, if it exceeds 50, an economical disadvantage may occur.
[0042]
As a reaction method, (1) a method of dropping mixed silane into water or an organic solvent containing water in an amount more than necessary for hydrolysis, (2) dropping water into mixed silane or organic solvent-containing mixed silane (3) The hydrolyzable silane (B) or a partial hydrolyzate thereof is dropped into water or an organic solvent containing water in an amount more than necessary for hydrolysis, and then a tertiary amino group-containing organic A method of dropping a hydrolyzable silane (A) containing a group or a partial hydrolyzate thereof, (4) hydrolyzable silane (A) containing a tertiary amino group-containing organic group or a partial hydrolyzate thereof in water Alternatively, there may be mentioned a method in which a hydrolyzable silane (B) or a partial hydrolyzate thereof is added dropwise to an organic solvent containing water in an amount more than that required for hydrolysis. In terms of the stability of things , In particular the reaction method (1) preferred.
[0043]
In addition, although the obtained organosilicon compound is obtained in the form of an aqueous solution, water is added or removed as necessary, so that water is 10 to 2,000 weight with respect to 100 weight parts of the organosilicon compound. Parts, preferably 10 to 1,000 parts by weight.
[0044]
The component (II) thus obtained has high storage stability in water-based inks, and can be present stably even when the system is in the alkaline region due to the dye of component (I). It is possible to impart sex. Furthermore, since the dye is not discolored, the color tone stability is also excellent.
[0045]
The optimum addition amount of component (II) varies depending on the type of water-soluble dye compound and / or organic pigment compound of component (I), but is 2 to 60 parts by weight, particularly 10 to 10 parts by weight of component (I). 40 parts by weight. When the addition amount is less than 2 parts by weight, the water resistance effect is reduced. When the addition amount is more than 60 parts by weight, a further water resistance effect cannot be expected any more, which is not preferable in terms of cost.
[0046]
Water is used as the component (III) of the composition of the present invention and used as a solvent for the above components (I) and (II).
Here, the amount of water used is 30 to 10,000 parts by weight, particularly 40 to 1,000 parts by weight with respect to 10 parts by weight of component (I), and if it is less than 30 parts by weight, the water-resistant ink composition is stored. The stability deteriorates, and if it exceeds 10,000 parts by weight, the image is disturbed and the intended image is not obtained.
[0047]
The ink composition of the present invention comprises the above components (I) to (III) and is excellent in water resistance, storage stability, ink ejection stability, color development, and water-based ink such as an ink jet recording method. Although it can use suitably for the recording method used, various additives can be mix | blended as needed.
For example, a humectant can be added to suppress nozzle clogging and improve ink ejection stability. Specifically, glycerin, diethylene glycol, triethylene glycol, low molecular weight polyethylene glycol, polyvinyl alcohol, ethyl alcohol, isopropyl An alcohol etc. can be mentioned, These can be used individually by 1 type or in mixture of 2 or more types.
[0048]
When the humectant is blended in the ink composition, it is preferably blended in an amount of 1 to 40 parts by weight, particularly 5 to 30 parts by weight per 10 parts by weight of component (I). If the blending amount is less than 1 part by weight, the ink ejection stability may be deteriorated. If the blending amount is more than 40 parts by weight, the water resistance may be weakened or the cost may be unfavorable.
[0049]
Further, optional components can be added as appropriate within a range that does not adversely affect stability and the like. As this optional component, a UV absorber, an antifoaming agent, a surfactant or the like may be added in order to impart various performances. Further, various finely divided inorganic oxides or sols thereof, water-soluble polymers and the like can be added for reinforcement.
[0050]
As described above, the ink composition of the present invention not only has excellent water resistance for printing or writing images, but also has high storage and color tone stability, ink ejection stability, and also excellent color development of printed images. It is an ink composition having such advantages.
[0051]
【Example】
Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
[Synthesis Example 1]
120 g (6.67 mol) of water was placed in a 200 ml reactor equipped with a stirrer, a thermometer and a condenser, and mixed with stirring. (CH_Three)₂NCH₂CH₂CH₂Si (OCH_Three)_Three41.4 g (0.2 mol) and CH_ThreeSi (OCH_Three)_ThreeWhen a mixture of 13.6 g (0.1 mol) was added dropwise at room temperature over 10 minutes, the internal temperature rose from 25 ° C to 49 ° C. Furthermore, it heated to 60-70 degreeC with the oil bath, and stirred as it was for 1 hour. Next, an ester adapter was attached, the internal temperature was raised to 96 ° C., and methanol produced as a by-product was removed to obtain 145 g of an organic silicon compound aqueous solution. The nonvolatile content (105 ° C./3 hours) of this product was 28.0%.
[0052]
[Synthesis Example 2]
120 g (6.67 mol) of water was placed in a 200 ml reactor equipped with a stirrer, a thermometer and a condenser, and mixed with stirring. (CH_Three)₂NCH₂CH₂N (CH_Three) CH₂CH₂CH₂Si (OCH_Three)_Three52.8 g (0.2 mol) and CH_ThreeSi (OCH_Three)_ThreeWhen a mixture of 13.6 g (0.1 mol) was added dropwise at room temperature over 10 minutes, the internal temperature rose from 25 ° C to 45 ° C. Furthermore, it heated to 60-70 degreeC with the oil bath, and stirred as it was for 1 hour. Next, an ester adapter was attached, the internal temperature was raised to 97 ° C., and methanol by-produced was removed to obtain 148 g of an organic silicon compound aqueous solution. The non-volatile content (105 ° C./3 hours) of this product was 30.0%.
[Synthesis Example 3]
120 g (6.67 mol) of water was placed in a 200 ml reactor equipped with a stirrer, a thermometer and a condenser, and mixed with stirring. here
[0053]
Embedded image

52.4 g (0.2 mol) and CH_ThreeSi (OCH_Three)_ThreeWhen a mixture of 13.6 g (0.1 mol) was added dropwise at room temperature over 10 minutes, the internal temperature rose from 25 ° C to 48 ° C. Furthermore, it heated to 60-70 degreeC with the oil bath, and stirred as it was for 1 hour. Next, an ester adapter was attached, the internal temperature was raised to 98 ° C., and methanol produced as a by-product was removed to obtain 160 g of an organic silicon compound aqueous solution. The nonvolatile content (105 ° C./3 hours) of this product was 28.0%.
[0054]
[Synthesis Example 4]
120 g (6.67 mol) of water was placed in a 200 ml reactor equipped with a stirrer, a thermometer and a condenser, and mixed with stirring. (CH_Three)₂NCH₂CH₂N (CH_Three) CH₂CH₂CH₂Si (OCH_Three)_Three52.8 g (0.2 mol) and Si (OCH_Three)_FourWhen a mixture of 15.2 g (0.1 mol) was added dropwise at room temperature over 10 minutes, the internal temperature rose from 25 ° C. to 47 ° C. Furthermore, it heated to 60-70 degreeC with the oil bath, and stirred as it was for 1 hour. Next, an ester adapter was attached, the internal temperature was raised to 98 ° C., and methanol by-produced was removed to obtain 148 g of an organic silicon compound aqueous solution. The nonvolatile content (105 ° C./3 hours) of this product was 26.0%.
[0055]
[referenceExample 1]
[Black ink]
(1) Water-soluble dye compound: Chlorazole black / 5.0 g manufactured by Tokyo Chemical Industry Co., Ltd.
(2) Organosilicon compound of Synthesis Example 1 / 17.9 g (solid content 5.0 g)
(3) Water / 67.1g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition.
[Magenta ink]
(1) Water-soluble dye compound: Acid Red 14 / 5.0 g made by Aldrich
(2) Organosilicon compound of Synthesis Example 1 / 17.9 g (solid content 5.0 g)
(3) Water / 67.1g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition.
[Yellow ink]
(1) Water-soluble dye compound: Acid Yellow 23 / 5.0 g manufactured by Tokyo Chemical Industry Co., Ltd.
(2) Organosilicon compound of Synthesis Example 1 / 17.9 g (solid content 5.0 g)
(3) Water / 67.1g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition.
[Cyan ink]
(1) Water-soluble dye compound: Acid Blue 92 / 5.0 g manufactured by Tokyo Chemical Industry Co., Ltd.
(2) Organosilicon compound of Synthesis Example 1 / 17.9 g (solid content 5.0 g)
(3) Water / 67.1g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition. These four color ink compositions were used in an inkjet printer machine (BJC-600S machine manufactured by Canon) to perform inkjet recording on ordinary paper. Evaluation items were evaluated as follows, and the results are shown in Table 1.
[0056]
water resistant
The paper on which the ink jet recording was performed was immersed in water, and the change in the printed image was observed when the paper was pulled up from the water.
○: No change in printed image
△: Slightly blurred by water
×: Severe bleeding with water
Color development of images
The color development of the printed image when ink jet recording was performed was observed.
○: Good color development
×: Poor color development
Discharge stability
When continuous printing was performed for 1 hour, it was observed whether the printed image was blurred due to ink clogging at the nozzle outlet.
○: No blurring of printed image
Δ: Part of the printed image is blurred
×: Severely blurred print image
Storage stability
It was observed how many days of continuous printing for 30 minutes per day could be printed without change. (Period until nozzle clogging and print image fading)
Storage stability at 60 ° C
The ink composition was left in an environment of 60 ° C., and the change of the liquid was observed. (Period that exists stably until liquid color change or gel occurs)
[0057]
[Example1]
[Black ink]
(1) Water-soluble dye compound: Chlorazole black / 5.0 g manufactured by Tokyo Chemical Industry Co., Ltd.
(2) Organosilicon compound of Synthesis Example 2 / 16.7 g (5.0 g solid content)
(3) Water / 68.3g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition.
[Magenta ink]
(1) Water-soluble dye compound: Acid Red 14 / 5.0 g made by Aldrich
(2) Organosilicon compound of Synthesis Example 2 / 16.7 g (5.0 g solid content)
(3) Water / 68.3g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition.
[Yellow ink]
(1) Water-soluble dye compound: Acid Yellow 23 / 5.0 g manufactured by Tokyo Chemical Industry Co., Ltd.
(2) Organosilicon compound of Synthesis Example 2 / 16.7 g (5.0 g solid content)
(3) Water / 68.3g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition.
[Cyan ink]
(1) Water-soluble dye compound: Acid Blue 92 / 5.0 g manufactured by Tokyo Chemical Industry Co., Ltd.
(2) Organosilicon compound of Synthesis Example 2 / 16.7 g (5.0 g solid content)
(3) Water / 68.3g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition. These four color ink compositions were used in an inkjet printer machine (BJC-600S machine manufactured by Canon) to perform inkjet recording on ordinary paper. EvaluationreferencePerformed as in Example 1. The results are shown in Table 1.
[0058]
[Example2]
[Black ink]
(1) Water-soluble dye compound: Chlorazole black / 5.0 g manufactured by Tokyo Chemical Industry Co., Ltd.
(2) Organosilicon compound of Synthesis Example 3 / 17.9 g (solid content 5.0 g)
(3) Water / 67.1g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition.
[Magenta ink]
(1) Water-soluble dye compound: Acid Red 14 / 5.0 g made by Aldrich
(2) Organosilicon compound of Synthesis Example 3 / 17.9 g (solid content 5.0 g)
(3) Water / 67.1g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition.
[Yellow ink]
(1) Water-soluble dye compound: Acid Yellow 23 / 5.0 g manufactured by Tokyo Chemical Industry Co., Ltd.
(2) Organosilicon compound of Synthesis Example 3 / 17.9 g (solid content 5.0 g)
(3) Water / 67.1g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition.
[Cyan ink]
(1) Water-soluble dye compound: Acid Blue 92 / 5.0 g manufactured by Tokyo Chemical Industry Co., Ltd.
(2) Organosilicon compound of Synthesis Example 3 / 17.9 g (solid content 5.0 g)
(3) Water / 67.1g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition. These four color ink compositions were used in an inkjet printer machine (BJC-600S machine manufactured by Canon) to perform inkjet recording on ordinary paper. EvaluationreferencePerformed as in Example 1. The results are shown in Table 1.
[0059]
[Example3]
[Black ink]
(1) Water-soluble dye compound: Chlorazole black / 5.0 g manufactured by Tokyo Chemical Industry Co., Ltd.
(2) Organosilicon compound of Synthesis Example 4 / 19.2 g (solid content 5.0 g)
(3) Water / 65.8g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition.
[Magenta ink]
(1) Water-soluble dye compound: Acid Red 14 / 5.0 g made by Aldrich
(2) Organosilicon compound of Synthesis Example 4 / 19.2 g (solid content 5.0 g)
(3) Water / 65.8g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition.
[Yellow ink]
(1) Water-soluble dye compound: Acid Yellow 23 / 5.0 g manufactured by Tokyo Chemical Industry Co., Ltd.
(2) Organosilicon compound of Synthesis Example 4 / 19.2 g (solid content 5.0 g)
(3) Water / 65.8g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition.
[Cyan ink]
(1) Water-soluble dye compound: Acid Blue 92 / 5.0 g manufactured by Tokyo Chemical Industry Co., Ltd.
(2) Organosilicon compound of Synthesis Example 4 / 19.2 g (solid content 5.0 g)
(3) Water / 65.8g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition. These four color ink compositions were used in an inkjet printer machine (BJC-600S machine manufactured by Canon) to perform inkjet recording on ordinary paper. EvaluationreferencePerformed as in Example 1. The results are shown in Table 1.
[0060]
[Comparative Example 1]
  Ink jet recording was performed on ordinary paper using ink attached to an ink jet printer (BJC-600S manufactured by Canon). Evaluation itemsreferenceEvaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.
[Comparative Example 2]
  Ink jet recording was performed on ordinary paper using ink attached to an ink jet printer (MJ-500C manufactured by Epson). Evaluation itemsreferenceEvaluate in the same way as in Example 11Shown in
[0061]
[Comparative Example 3]
[Black ink]
(1) Water-soluble dye compound: Chlorazole black / 5.0 g manufactured by Tokyo Chemical Industry Co., Ltd.
(2) Pentaethylenehexamine / 5.0g
(3) Water / 80.0g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition.
[Magenta ink]
(1) Water-soluble dye compound: Acid Red 14 / 5.0 g made by Aldrich
(2) Pentaethylenehexamine / 5.0g
(3) Water / 80.0g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition.
[Yellow ink]
(1) Water-soluble dye compound: Acid Yellow 23 / 5.0 g manufactured by Tokyo Chemical Industry Co., Ltd.
(2) Pentaethylenehexamine / 5.0g
(3) Water / 80.0g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition.
[Cyan ink]
(1) Water-soluble dye compound: Acid Blue 92 / 5.0 g manufactured by Tokyo Chemical Industry Co., Ltd.
(2) Pentaethylenehexamine / 5.0g
(3) Water / 80.0g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition. These four color ink compositions were used in an inkjet printer machine (BJC-600S machine manufactured by Canon) to perform inkjet recording on ordinary paper. EvaluationreferencePerformed as in Example 1. The results are shown in Table 1.
[0062]
[Comparative Example 4]
[Black ink]
(1) Water-soluble dye compound: Chlorazole black / 5.0 g manufactured by Tokyo Chemical Industry Co., Ltd.
(2) Triethylenepentamine / 5.0g
(3) Water / 80.0g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition.
[Magenta ink]
(1) Water-soluble dye compound: Acid Red 14 / 5.0 g made by Aldrich
(2) Triethylenepentamine / 5.0g
(3) Water / 80.0g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition.
[Yellow ink]
(1) Water-soluble dye compound: Acid Yellow 23 / 5.0 g manufactured by Tokyo Chemical Industry Co., Ltd.
(2) Triethylenepentamine / 5.0g
(3) Water / 80.0g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition.
[Cyan ink]
(1) Water-soluble dye compound: Acid Blue 92 / 5.0 g manufactured by Tokyo Chemical Industry Co., Ltd.
(2) Triethylenepentamine / 5.0g
(3) Water / 80.0g
(4) Moisturizer: Glycerol / 10.0g
Components (1) to (4) were mixed to prepare a water-resistant ink composition. These four color ink compositions were used in an inkjet printer machine (BJC-600S machine manufactured by Canon) to perform inkjet recording on ordinary paper. EvaluationreferencePerformed as in Example 1. The results are shown in Table 1.
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[Table 1]

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【The invention's effect】
The water-resistant ink composition of the present invention relates to a water-resistant ink composition having not only excellent water resistance but also high storage stability and ink ejection stability, and particularly excellent color tone stability.

Claims (4)

(I) 10 parts by weight of a water-soluble dye compound and / or an organic pigment compound,
(II) The following formula

In a hydrolyzable silane (A) or a partial hydrolyzate 100 parts by weight containing INDICATED the tertiary amino group-containing organic group represented by the following general formula (2)
R ³ _n SiR ⁴ _4-n (2)
(In the formula, R ³ is an unsubstituted or substituted monovalent hydrocarbon group not containing a tertiary amino group, R ⁴ is an alkoxy group or an acyloxy group having 1 to ⁴ carbon atoms, n is 0, 2 to 60 parts by weight of an organosilicon compound obtained by hydrolyzing 5 to 200 parts by weight of a hydrolyzable silane (B) or a partial hydrolyzate thereof represented by 1 or 2.
And (III) a water-resistant ink composition comprising 30 to 10,000 parts by weight of water. Hydrolyzable silane (B) is _{Si (OCH 3) 4, Si} (OC 2 H 5) 4, CH 3 Si (OCH 3) 3, or _{CH 3 Si (OC 2 H 5} ) according to claim 1 which is ₃ The water-resistant ink composition as described. The water-resistant ink composition according to claim 1 or 2 , comprising 1 to 40 parts by weight of a humectant. The water-resistant ink composition according to any one of claims 1 to 3 , which is for inkjet recording.