JP3807492B2 - Ink absorbent composition - Google Patents

Description

（式中、Ｒ¹及びＲ²はそれぞれ炭素数１〜５のアルキル基を示す。）
で表されるアセチレングリコール及び下記式（２）
【化５】

（式中、Ｒ¹及びＲ²はそれぞれ炭素数１〜５のアルキル基を示し、ｍ、ｎはそれぞれ正数であり、かつｍ＋ｎは１０未満である。）
で表されるアセチレングリコールのエトキシル化体から選ばれる１種又は２種以上
１０〜７５重量％
（Ｂ）下記式（３）
【化６】

（式中、Ｒ³及びＲ⁴はそれぞれ炭素数１〜５のアルキル基を示し、ｐ、ｑは正数であり、かつｐ＋ｑは１０〜４０である。）
で表されるＨＬＢが１０〜１８のアセチレングリコールのエトキシル化体の１種又は２種以上 ２０〜８０重量％
（Ｃ）ポリオキシ（エチレン・プロピレン）ブロックポリマー ５〜２０重量％
を含有し、その０．１重量％水溶液の滴下３０秒後の接触角が７０度以下、１Ｈｚ及び１０Ｈｚ時の動的表面張力がそれぞれ５０ｍＮ／ｍ以下であることを特徴とするインキ吸収剤組成物を提供する。
【０００９】
以下、本発明について更に詳しく説明する。
本発明のインキ吸収剤組成物の成分（Ａ）は、上述したように、下記式（１）で表されるアセチレングリコール及び下記式（２）で表されるアセチレングリコールのエトキシル化体から選ばれる１種又は２種以上のアセチレングリコール類である。
【化７】

（式中、Ｒ¹及びＲ²はそれぞれ炭素数１〜５のアルキル基を示し、ｍ、ｎはそれぞれ正数で、かつｍ＋ｎは１０未満である。）
【００１０】
上記式（１）で表されるアセチレングリコールとしては、例えば、
２，５，８，１１−テトラメチル−６−ドデシン−５，８−ジオール、
５，８−ジメチル−６−ドデシン−５，８−ジオール、
２，４，７，９−テトラメチル−５−デシン−４，７−ジオール、
４，７−ジメチル−５−デシン−４，７−ジオール、
２，３，６，７−テトラメチル−４−オクチン−３，６−ジオール、
３，６−ジメチル−４−オクチン−３，６−ジオール、
２，５−ジメチル−３−ヘキシン−２，５−ジオール
などを挙げることができ、式（２）で表されるアセチレングリコールのエトキシル化体としては、例えば、
２，４，７，９−テトラメチル−５−デシン−４，７−ジオールのエトキシル化体（エチレンオキサイド付加モル数：１．３）、
２，４，７，９−テトラメチル−５−デシン−４，７−ジオールのエトキシル化体（エチレンオキサイド付加モル数：４）、
３，６−ジメチル−４−オクチン−３，６−ジオールのエトキシル化体（エチレンオキサイド付加モル数：４）、
２，５，８，１１−テトラメチル−６−ドデシン−５，８−ジオールのエトキシル化体（エチレンオキサイド付加モル数：６）
などの上記アセチレングリコールのエチレンオキサイド誘導体を挙げることができる。そのアセチレングリコール中のエチレンオキサイド単位の付加モル総数は０＜ｍ＋ｎ＜１０モルである。エチレンオキサイドの付加モル総数が１０モル以上の場合にはインキ配合した際の起泡性がアップし、印字不良などの問題が発生する。
【００１１】
これらのアセチレングリコール類〔成分（Ａ）〕は、その１種を単独で又は２種以上を混合して使用することができ、本発明のインキ吸収剤組成物を調製する際に用いられる量は、組成物全体の１０〜７５重量％である。８０重量％を超えると溶解性が低下し、インキ配合した際、凝集物が発生し、吐出安定性不良による印字不良が発生する。
【００１２】
成分（Ａ）のアセチレングリコール類に配合する成分（Ｂ）のアセチレングリコールのエトキシル化体は、下記式（３）で表されるＨＬＢが１０〜１８のアセチレングリコールのエトキシル化体である。
【化８】

（式中、Ｒ³及びＲ⁴はそれぞれ炭素数１〜５のアルキル基を示し、ｐ、ｑは正数であり、かつｐ＋ｑは１０〜４０である。）
【００１３】
このようなアセチレングリコールのエトキシル化体として、具体的には、
２，４，７，９−テトラメチル−５−デシン−４，７−ジオールのエトキシル化体（エチレンオキサイド付加モル数：１０、ＨＬＢ：１３）、
２，４，７，９−テトラメチル−５−デシン−４，７−ジオールのエトキシル化体（エチレンオキサイド付加モル数：３０、ＨＬＢ：１７）
等を挙げることができ、これらは１種を単独で又は２種以上を混合して使用することができる。
【００１４】
これら成分（Ｂ）のＨＬＢは１０〜１８、好ましくは１４〜１７であり、ＨＬＢが１８を超えると、成分（Ａ）の水不溶性物質を溶解する可溶化性能はアップするものの水溶性が増し、泡の発生による印字不良が発生するし、ＨＬＢが１０未満では、水への溶解性が低下してインキ中に凝集物が発生し、浸透性良好なインキが得られなくなる。
【００１５】
また、上記成分（Ｂ）におけるアセチレングリコール中のエチレンオキサイド単位の付加モル総数は、１０〜４０モル、好ましくは１０〜３０モルであり、エチレンオキサイドの付加モル総数が４０モルを超えると、可溶化性能はアップするものの起泡性もアップし、インキ配合時に泡が発生して印刷不良の原因になるし、１０モル未満では、可溶化性能がなくなると共にそれ自身の水への溶解性がなくなるため、成分（Ａ）の溶解性性能が著しく低下し、凝集物の発生に伴う印刷不良が発生する。
【００１６】
本発明では、インキ吸収剤組成物を調製する際に用いられる成分（Ｂ）の量は、組成物全体の２０〜８０重量％である。９５重量％を超えると、起泡性がアップし、ピンホールが生じて印刷不良が発生するし、２０重量％未満では成分（Ａ）の可溶化性能が低下し、凝集物が発生する。
【００１７】
本発明では、更に第三成分〔成分（Ｃ）〕として、ポリオキシ（エチレン・プロピレン）ブロックポリマーを組成物全体の５〜２０重量％、好ましくは５〜１５重量％の量で用いる。
【００１８】
本発明のインキ吸収剤組成物は、例えば、上記各成分をプロペラ式撹拌機などの公知の混合調製方法によって混合することにより得られる。また、常温にて固体の成分については、必要により加温して混合するものである。
【００１９】
ここで、得られたインキ吸収剤組成物は、その０．１重量％水溶液の滴下３０秒後の接触角が７０度以下、好ましくは１０〜６５度、より好ましくは３５〜６０度、更に０．１重量％水溶液の１Ｈｚ及び１０Ｈｚ時の動的表面張力がそれぞれ５０ｍＮ／ｍ以下、好ましくは２０〜５０ｍＮ／ｍ、より好ましくは３５〜５０ｍＮ／ｍである。
【００２０】
なお、接触角は接触角計ＣＡ−Ｄ型（協和界面科学社製）を用いて０．１重量％水溶液の滴下３０秒後の値を測定したものであり、動的表面張力はバブルプレッシャー型動的表面張力計クルスＢＰ−２（ＫＲＵＳＳ社製）を用いて０．１重量％水溶液の１Ｈｚ及び１０Ｈｚの値を測定したものである。
【００２１】
０．１重量％インキ吸収剤組成物水溶液の滴下３０秒後の接触角が７０度を超えると、インキに配合した際、ハジキの発生や吸収性が悪くなるためインキの滲みが発生するし、同じく０．１重量％水溶液の１Ｈｚ及び１０Ｈｚの動的表面張力が５０ｍＮ／ｍを超えると、高速印刷を実施した際にハジキや浸透力不足による滲みが発生する。
【００２２】
本発明のインキ吸収剤組成物を用いてインキを製造する場合、インキ吸収剤組成物の配合割合としては、インキ全量に対して、好ましくは０．０５〜１０重量％、より好ましくは０．０５〜５重量％の範囲内とすることが望ましい。
【００２３】
その他添加剤としては、防腐剤、ｐＨ調整剤、粘度調整剤、分散剤、酸素吸収剤、酸化防止剤、紫外線吸収剤等を適宜配合することもできる。
【００２４】
インキ吸収剤組成物を用いるインキとしては、フレキソインキ、グラビアインキ、新聞インキ、スクリーンインキ、凸版インキ等が挙げられる。
【００２５】
【実施例】
以下、配合例、実施例及び比較例を示し、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。なお、例中の部及び％は、それぞれ重量部と重量％を示す。
【００２６】
［配合例１］
７０℃に加温した２，４，７，９−テトラメチル−５−デシン−４，７−ジオール（エアプロダクツ社製、商品名サーフィノール１０４）４０部を撹拌機付容器に投入後、撹拌しながら２，４，７，９−テトラメチル−５−デシン−４，７−ジオールのエトキシル化体（エアプロダクツ社製、商品名サーフィノール４８５、ＨＬＢ１７、エチレンオキサイド付加モル数：３０）６０部を徐々に投入混合し、２時間連続撹拌後、室温まで冷却した。冷却後、２００メッシュ濾布にて濾過し、インキ吸収剤組成物（以下、これをＭ−１という）を得た。
更に、組成物Ｍ−１の０．１部をイオン交換水１００部に加え、マグネチックスタラーにて撹拌して０．１％水溶液とし、これを用いて水溶液の外観、接触角、動的表面張力、静的表面張力及び起泡性を測定した。その結果を表２に示す。
なお、各特性の測定は下記のようにして行った。
【００２７】
＜インキ吸収剤組成物の評価＞
１）水溶液の外観
上記水溶液の外観及び不溶解物の有無の確認を行った。
○：水溶液が透明で、不溶解物が認められない。
△：水溶液が白濁しているが、不溶解物は認められない。
×：一部不溶解物が認められる。
××：殆ど溶解せず。
２）接触角
インキ吸収剤組成物の０．１％水溶液を、協和界面科学社製接触角計ＣＡ−Ｄ型を用いて、滴下３０秒後の接触角を測定した。
３）動的表面張力
ＫＲＵＳＳ社製バブルプレッシャー型動的表面張力計クルスＢＰ−２を用いて、インキ吸収剤組成物の０．１％水溶液の１Ｈｚ及び１０Ｈｚ時の動的表面張力を測定した。
４）静的表面張力
インキ吸収剤組成物の０．１％水溶液を、協和界面科学社製表面張力計ＥＳＢ−Ｖ型を用いて、静的な表面張力を測定した。
５）起泡性
インキ吸収剤組成物の０．１％水溶液２０ｍｌを１００ｍｌメスシリンダーに採取し、イワキ産業社製ＫＭシェーカーＶ−ＳＸ型を用いて１８０回／分×４０ｍｍの条件下で１分間振とうした時の直後及び５分後の泡高さを測定した。
【００２８】
［配合例２〜１０］
配合例１と同様にして表１に示される成分（Ａ）〜（Ｃ）の種類及び配合量（部）で撹拌混合し、インキ吸収剤組成物（Ｍ−２〜Ｍ−１０）を得た。なお、配合例１については、成分（Ａ）〜（Ｃ）の配合量を部で再記した。
配合例１と同様にして０．１％水溶液を作り、同様にして水溶液の評価を行った。これらの結果を表２に示した。
【００２９】
また、下記に示す市販品１，２について、配合例１と同様に評価を行い、これらの結果を表２に併記した。
市販品１：ノプコＮＸＺ（サンノプコ社製商品名、鉱物油系）
市販品２：ＳＮデフォーマー５０１６（サンノプコ社製商品名、シリコーン系）
【００３０】
【表１】

【００３１】
＜成分（Ａ）＞
Ａ−１：２，４，７，９−テトラメチル−５−デシン−４，７−ジオール（エアプロダクツ社製、商品名サーフィノール１０４）
Ａ−２：３，６−ジメチル−４−オクチン−３，６−ジオール（エアプロダクツ社製、商品名サーフィノール８２）
Ａ−３：２，５，８，１１−テトラメチル−６−ドデシン−５，８−ジオール（エアプロダクツ社製、商品名サーフィノールＤＦ−１１０）
Ａ−４：２，４，７，９−テトラメチル−５−デシン−４，７−ジオールのエトキシル化体（エアプロダクツ社製、商品名サーフィノール４２０、エチレンオキサイド付加モル数：１．３、ＨＬＢ４）
Ａ−５：２，４，７，９−テトラメチル−５−デシン−４，７−ジオールのエトキシル化体（日信化学社製、商品名オルフィンＥ−１００４、エチレンオキサイド付加モル数：４、ＨＬＢ８）
【００３２】
＜成分（Ｂ）＞
Ｂ−１：２，４，７，９−テトラメチル−５−デシン−４，７−ジオールのエトキシル化体（日信化学社製、商品名オルフィンＥ−１０１０、エチレンオキサイド付加モル数：１０、ＨＬＢ１４）
Ｂ−２：２，４，７，９−テトラメチル−５−デシン−４，７−ジオールのエトキシル化体（エアプロダクツ社製、商品名サーフィノール４８５、エチレンオキサイド付加モル数：３０、ＨＬＢ１７）
Ｂ−３：２，４，７，９−テトラメチル−５−デシン−４，７−ジオールのエトキシル化体（エアプロダクツ社製、商品名サーフィノール４６５、エチレンオキサイド付加モル数：１０、ＨＬＢ１４）
Ｂ−４：２，４，７，９−テトラメチル−５−デシン−４，７−ジオールのエトキシル化体（エチレンオキサイド付加モル数：５０、ＨＬＢ１９）
【００３３】
＜成分（Ｃ）＞
Ｃ−１：プロピレングリコール
Ｃ−２：ポリエチレングリコール
Ｃ−３：ポリオキシエチレンノニルフェニルエーテル（三洋化成社製、商品名ノニポール１６０）
Ｃ−４：ポリオキシ（エチレン・プロピレン）ブロックポリマー（第一工業製薬社製、商品名エパン７５０）
【００３４】
【表２】

【００３５】
［実施例１］
染料（商品名Ｃｉｂａｆｉｘダイレクトブラック１９、日本チバガイギー社製）５部をイオン交換水７０部にプロペラ式撹拌機で撹拌しながら徐々に添加した後、インキ吸収剤組成物Ｍ−３を１部、ポリエチレングリコールを１０部、グリセリンを１５部添加し、１時間撹拌して、ブラック（Ｂ）（以下このインキをＫ−３という）を得た。これを用いて印字濃度、ドット径、印字画像の解像度及びインキ吸収性を測定し、その結果を表３に示した。
【００３６】
＜インキ評価＞
１）印字濃度
キャノンプリンターＢＪＣ４５５Ｊでブラック（Ｂ）を用いて印字したドットに関し、サクラマイクロデンシトメーターＰＤＭ−５型（サクラ製機社製）でドットの濃度を測定した。
２）ドット径
キャノンプリンターＢＪＣ４５５Ｊでブラック（Ｂ）を用いて印字し、１００倍に拡大してドット径を測定した。
３）印字画像の解像度
キャノンプリンターＢＪＣ４５５Ｊでブラック（Ｂ）をベタ印刷し、マクベス濃度計ＲＤ−９１８型（マクベス社製）で測定した。
更に、マゼンタ（Ｍ）、シアン（Ｃ）、イエロー（Ｙ）を同様に処理した。なお、印刷に使用したマゼンタ、シアン、イエローインキは実施例１で使用した染料の代わりにそれぞれＣｉｂａｆｉｘダイレクトレッド９、Ｃｉｂａｆｉｘダイレクトブルー８６、Ｃｉｂａｆｉｘダイレクトイエロー２３を用いることにより得た。
４）インキ吸収性
キャノンプリンターＢＪＣ４５５Ｊでブラック、マゼンタ、シアン、イエローを同時に同一場所に噴射し、１秒後に紙押さえ板でこすり、インクによる汚れを測定した。
○：白色部分の汚れのないもの
△：微かに汚れるもの
×：汚れがひどいもの
【００３７】
［比較例１〜７］
実施例１と同様にして、表１に示される配合例６〜１０のインキ吸収剤組成物（Ｍ−６〜Ｍ−１０）及び市販品１，２を用いて、ブラック（Ｂ）（Ｋ−６〜Ｋ−１２）を得た。これらを用いて、実施例１と同様の測定を行い、結果を表３に示した。
【００３８】
【表３】

【００３９】
【発明の効果】
本発明のインキ吸収剤組成物は、滴下直後の接触角や動的表面張力が低く、優れた吸収性を発揮するため、高速印刷にも対応でき、しかも環境問題にも適合した優れたインキとなり得る。この特性により、本発明のインキ吸収剤組成物は実用的にきわめて有利である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an ink absorbent composition used for recording characters and graphics on the surface of a recording medium, and particularly to an ink absorbent composition excellent in permeability and defoaming properties.
[0002]
[Prior art and problems to be solved by the invention]
A printer for office automation equipment such as a personal computer is a method of recording characters and figures on the surface of a recording medium by ejecting ink as small droplets from a fine nozzle having a diameter of several tens of μm. The market for these printers has grown rapidly in recent years and competition has intensified as the OA equipment environment has been improved. As for printer technology, it is expected that multi-nozzles will be made to reduce the nozzle diameter and increase the number of discharges to increase the recording speed aiming for higher resolution in the future. Correspondence to is desired.
[0003]
However, water-based inks have problems such as slow drying, and since the drying mechanism is mainly penetrating into the recording medium, there is a drawback that bleeding occurs when the penetrating is slow. Against this background, the ink and water-based paint industry requires a surfactant that imparts an excellent surface tension reducing ability for wetting and penetrating the substrate. When selecting a surfactant, the static surface tension is excellent when the system is in a static state, and the dynamic surface tension is reduced during high-speed use because of the need to increase the printing speed to improve productivity. Indicators are very important.
[0004]
Acetylene glycol surfactants such as acetylene glycol, such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol and its ethylene oxide adduct, have static surface tension and dynamic surface tension. It has been used as a wetting agent and a dispersion aid for inks and paints because it has a good balance with its lowering ability and has antifoaming properties. However, on the other hand, these surfactants have problems such as low solubility in water and solids at room temperature. Polyoxyethylene nonyl is used to eliminate inconvenience during use. A surfactant such as phenyl ether must be used in combination as a solubilizer.
[0005]
In addition, in the situation where legal regulations are becoming stricter due to environmental problems in recent years, there is an increasing demand for surfactants corresponding to the environment, and substitutes for polyethylene nonylphenyl ether are provided by various companies. However, some of these alternatives have the same static surface tension but have a large effect on the dynamic surface tension, and some have a high contact angle. They are formulated as solubilizers for acetylene glycol surfactants. However, the same performance was not always obtained.
[0006]
The present invention was made in order to improve the above circumstances, has a low dynamic surface tension, exhibits excellent wettability, permeability, antifoaming properties, dispersibility, can also support high-speed printing, It is another object of the present invention to provide an ink absorbent composition containing a surfactant in consideration of solubility in water and environmental problems.
[0007]
Means for Solving the Problem and Embodiment of the Invention
As a result of intensive studies to solve the above-mentioned problems, the present inventors have formulated a specific acetylene glycol and a specific range of HLB and an ethoxylated acetylene glycol having an ethylene oxide addition mole number. However, especially when used as an ink absorber, it has been found that it can solve the above-mentioned conventional problems because it has excellent compatibility with water-based inks, and also has excellent ink absorption and antifoaming properties. The present invention has been made.
[0008]
That is, the present invention
(A) The following formula (1)
[Formula 4]

(In the formula, R ¹ and R ² each represent an alkyl group having 1 to 5 carbon atoms.)
And acetylene glycol represented by the following formula (2):
[Chemical formula 5]

(In the formula, R ¹ and R ² each represent an alkyl group having 1 to 5 carbon atoms, m and n are each a positive number, and m + n is less than 10.)
1 type or 2 types or more chosen from the ethoxylated form of acetylene glycol represented by
10 to 75% by weight
(B) Following formula (3)
[Chemical 6]

(In the formula, R ³ and R ⁴ each represent an alkyl group having 1 to 5 carbon atoms, p and q are positive numbers, and p + q is 10 to 40.)
One or two or more of ethoxylated acetylene glycols having an HLB of 10 to 18 represented by 20 to 80 % by weight
(C) 5-20% by weight of polyoxy (ethylene / propylene) block polymer
An ink absorbent composition characterized in that the contact angle after 30 seconds of dropping the 0.1 wt% aqueous solution thereof is 70 degrees or less, and the dynamic surface tension at 1 Hz and 10 Hz is 50 mN / m or less, respectively. Offer things.
[0009]
Hereinafter, the present invention will be described in more detail.
As described above, component (A) of the ink absorbent composition of the present invention is selected from acetylene glycol represented by the following formula (1) and ethoxylated acetylene glycol represented by the following formula (2). One or more acetylene glycols.
[Chemical 7]

(In the formula, R ¹ and R ² each represent an alkyl group having 1 to 5 carbon atoms, m and n are each a positive number, and m + n is less than 10.)
[0010]
As the acetylene glycol represented by the above formula (1), for example,
2,5,8,11-tetramethyl-6-dodecin-5,8-diol,
5,8-dimethyl-6-dodecin-5,8-diol,
2,4,7,9-tetramethyl-5-decyne-4,7-diol,
4,7-dimethyl-5-decyne-4,7-diol,
2,3,6,7-tetramethyl-4-octyne-3,6-diol,
3,6-dimethyl-4-octyne-3,6-diol,
2,5-dimethyl-3-hexyne-2,5-diol and the like. Examples of the ethoxylated acetylene glycol represented by the formula (2) include:
Ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (ethylene oxide addition mole number: 1.3),
2,4,7,9-tetramethyl-5-decyne-4,7-diol ethoxylated compound (ethylene oxide addition mole number: 4),
Ethoxylated form of 3,6-dimethyl-4-octyne-3,6-diol (ethylene oxide addition moles: 4),
Ethoxylated product of 2,5,8,11-tetramethyl-6-dodecin-5,8-diol (number of moles of ethylene oxide added: 6)
And ethylene oxide derivatives of the above acetylene glycol. The total number of moles of ethylene oxide units added in the acetylene glycol is 0 <m + n <10 moles. When the total number of moles of ethylene oxide added is 10 moles or more, the foamability when ink is blended is increased, and problems such as printing defects occur.
[0011]
These acetylene glycols [component (A)] can be used singly or in combination of two or more, and the amount used when preparing the ink absorbent composition of the present invention is as follows. 10 to 75% by weight of the total composition. If it exceeds 80% by weight, the solubility is lowered, and when ink is blended, agglomerates are generated, resulting in poor printing due to poor ejection stability.
[0012]
The ethoxylated product of the acetylene glycol of the component (B) to be blended with the acetylene glycols of the component (A) is an ethoxylated product of acetylene glycol having an HLB of 10 to 18 represented by the following formula (3).
[Chemical 8]

(In the formula, R ³ and R ⁴ each represent an alkyl group having 1 to 5 carbon atoms, p and q are positive numbers, and p + q is 10 to 40.)
[0013]
As such an ethoxylated acetylene glycol, specifically,
Ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (ethylene oxide addition moles: 10, HLB: 13),
Ethoxylated product of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (ethylene oxide addition moles: 30, HLB: 17)
These may be used alone or in combination of two or more.
[0014]
The HLB of these components (B) is 10 to 18, preferably 14 to 17. If the HLB exceeds 18, the solubilization performance for dissolving the water-insoluble substance of the component (A) is improved, but the water solubility increases. If the HLB is less than 10 due to the generation of bubbles, the solubility in water decreases and aggregates are generated in the ink, making it impossible to obtain ink with good permeability.
[0015]
In addition, the total number of added moles of ethylene oxide units in the acetylene glycol in the component (B) is 10 to 40 moles, preferably 10 to 30 moles. When the total number of moles of added ethylene oxide exceeds 40 moles, solubilization occurs. Although the performance is improved, the foaming property is also improved, and bubbles are generated at the time of blending the ink, resulting in poor printing. If it is less than 10 moles, the solubilization performance is lost and the solubility in water itself is lost. , The solubility performance of the component (A) is remarkably lowered, and a printing defect accompanied by the generation of aggregates occurs.
[0016]
In this invention, the quantity of the component (B) used when preparing an ink absorber composition is 20 to 80 weight% of the whole composition. If it exceeds 95% by weight, foamability is improved, pinholes are generated and printing defects occur, and if it is less than 20% by weight, the solubilization performance of the component (A) is lowered and aggregates are generated.
[0017]
In the present invention, as a further in the third component [component (C)], polyoxyl 5-20 wt% of the total (ethylene-propylene) block polymer composition is preferably used in an amount of 5 to 15 wt%.
[0018]
The ink absorbent composition of the present invention can be obtained, for example, by mixing the above components by a known mixing preparation method such as a propeller type stirrer. Moreover, about a solid component at normal temperature, it heats and mixes as needed.
[0019]
Here, the obtained ink absorbent composition has a contact angle of 70 ° or less, preferably 10 to 65 °, more preferably 35 to 60 °, and further 0 after 30 seconds of dropping the 0.1 wt% aqueous solution. The dynamic surface tension of 1 wt% aqueous solution at 1 Hz and 10 Hz is 50 mN / m or less, preferably 20 to 50 mN / m, and more preferably 35 to 50 mN / m.
[0020]
The contact angle is a value measured 30 seconds after dropping a 0.1 wt% aqueous solution using a contact angle meter CA-D type (manufactured by Kyowa Interface Science Co., Ltd.), and the dynamic surface tension is a bubble pressure type. 1 Hz and 10 Hz values of a 0.1 wt% aqueous solution were measured using a dynamic surface tension meter Cruz BP-2 (manufactured by KRUS).
[0021]
When the contact angle after 30 seconds of dropping of the 0.1 wt% ink absorbent composition aqueous solution exceeds 70 degrees, when blended into the ink, ink bleeding occurs due to poor repellency and absorbability, Similarly, if the dynamic surface tension of 1 Hz and 10 Hz of a 0.1 wt% aqueous solution exceeds 50 mN / m, bleeding due to repelling or insufficient penetrating power occurs when high-speed printing is performed.
[0022]
When the ink is produced using the ink absorbent composition of the present invention, the blending ratio of the ink absorbent composition is preferably 0.05 to 10% by weight, more preferably 0.05, based on the total amount of the ink. It is desirable to be in the range of ˜5% by weight.
[0023]
As other additives, preservatives, pH adjusters, viscosity adjusters, dispersants, oxygen absorbers, antioxidants, ultraviolet absorbers, and the like can be appropriately blended.
[0024]
Examples of the ink using the ink absorbent composition include flexographic ink, gravure ink, newspaper ink, screen ink, letterpress ink, and the like.
[0025]
【Example】
Hereinafter, although a compounding 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. In addition, the part and% in an example show a weight part and weight%, respectively.
[0026]
[Formulation Example 1]
40 parts of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (trade name Surfinol 104, manufactured by Air Products) heated to 70 ° C. was put into a vessel equipped with a stirrer and stirred. 60 parts of an ethoxylated product of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (produced by Air Products, trade name Surfinol 485, HLB17, ethylene oxide addition mole number: 30) Were gradually added and mixed, and after continuous stirring for 2 hours, the mixture was cooled to room temperature. After cooling, the mixture was filtered through a 200 mesh filter cloth to obtain an ink absorbent composition (hereinafter referred to as M-1).
Further, 0.1 part of the composition M-1 was added to 100 parts of ion-exchanged water and stirred with a magnetic stirrer to make a 0.1% aqueous solution. Using this, the appearance, contact angle, and dynamic surface of the aqueous solution were used. Tension, static surface tension and foamability were measured. The results are shown in Table 2.
Each characteristic was measured as follows.
[0027]
<Evaluation of ink absorbent composition>
1) Appearance of aqueous solution The appearance of the aqueous solution and the presence or absence of insoluble matter were confirmed.
○: The aqueous solution is transparent, and no insoluble matter is observed.
(Triangle | delta): Although aqueous solution is cloudy, an insoluble matter is not recognized.
X: A partly insoluble matter is recognized.
XX: Almost no dissolution.
2) Contact angle 30 seconds after dropping of a 0.1% aqueous solution of the contact angle ink absorbent composition using a contact angle meter CA-D type manufactured by Kyowa Interface Science Co., Ltd. was measured.
3) Dynamic surface tension The dynamic surface tension of a 0.1% aqueous solution of the ink absorbent composition at 1 Hz and 10 Hz was measured using a bubble pressure type dynamic surface tension meter Cruz BP-2 manufactured by KRUSS.
4) Static surface tension The static surface tension of a 0.1% aqueous solution of the ink absorbent composition was measured using a surface tension meter ESB-V manufactured by Kyowa Interface Science Co., Ltd.
5) 20 ml of a 0.1% aqueous solution of the foamable ink absorbent composition was collected in a 100 ml graduated cylinder and used for 1 minute under the conditions of 180 times / minute × 40 mm using a KM shaker V-SX type manufactured by Iwaki Sangyo Co., Ltd. The foam height was measured immediately after shaking and after 5 minutes.
[0028]
[Composition Examples 2 to 10]
In the same manner as in Formulation Example 1, the components (A) to (C) shown in Table 1 and the mixing amount (parts) were stirred and mixed to obtain ink absorbent compositions (M-2 to M-10). . In addition, about the compounding example 1, the compounding quantity of component (A)-(C) was rewritten in the part.
A 0.1% aqueous solution was prepared in the same manner as in Formulation Example 1, and the aqueous solution was evaluated in the same manner. These results are shown in Table 2.
[0029]
Moreover, the commercial products 1 and 2 shown below were evaluated in the same manner as in Formulation Example 1, and the results are also shown in Table 2.
Commercial product 1: Nopco NXZ (trade name, manufactured by San Nopco, mineral oil)
Commercial product 2: SN deformer 5016 (trade name, silicone type, manufactured by San Nopco)
[0030]
[Table 1]

[0031]
<Component (A)>
A-1: 2,4,7,9-tetramethyl-5-decyne-4,7-diol (product name Surfinol 104, manufactured by Air Products)
A-2: 3,6-dimethyl-4-octyne-3,6-diol (manufactured by Air Products, trade name Surfynol 82)
A-3: 2,5,8,11-tetramethyl-6-dodecin-5,8-diol (manufactured by Air Products, trade name Surfinol DF-110)
A-4: Ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (manufactured by Air Products, trade name Surfynol 420, number of moles of ethylene oxide added: 1.3, HLB4)
A-5: Ethoxylated product of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (manufactured by Nisshin Chemical Co., Ltd., trade name Olphine E-1004, ethylene oxide addition mole number: 4, HLB8)
[0032]
<Component (B)>
B-1: Ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (manufactured by Nisshin Chemical Co., Ltd., trade name: Orphine E-1010, ethylene oxide addition moles: 10, HLB14)
B-2: Ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (Air Products, trade name Surfynol 485, ethylene oxide addition moles: 30, HLB17)
B-3: Ethoxylated form of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (Air Products, trade name Surfinol 465, ethylene oxide addition moles: 10, HLB14)
B-4: Ethoxylated product of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (ethylene oxide addition mole number: 50, HLB19)
[0033]
<Ingredient (C)>
C-1: Propylene glycol C-2: Polyethylene glycol C-3: Polyoxyethylene nonyl phenyl ether (manufactured by Sanyo Chemical Co., Ltd., trade name Nonipol 160)
C-4: Polyoxy (ethylene propylene) block polymer (Daiichi Kogyo Seiyaku Co., Ltd., trade name Epan 750)
[0034]
[Table 2]

[0035]
[Example 1]
After gradually adding 5 parts of a dye (trade name Cibafix Direct Black 19, manufactured by Ciba-Geigy Japan) to 70 parts of ion-exchanged water while stirring with a propeller-type stirrer, 1 part of ink absorbent composition M- 3 , polyethylene 10 parts of glycol and 15 parts of glycerin were added and stirred for 1 hour to obtain black (B) (hereinafter this ink is referred to as K- 3 ). Using this, the print density, the dot diameter, the resolution of the print image, and the ink absorptivity were measured, and the results are shown in Table 3.
[0036]
<Ink evaluation>
1) Print density Regarding the dots printed with black (B) by Canon printer BJC455J, the density of the dots was measured with Sakura Microdensitometer PDM-5 (manufactured by Sakura Kikai Co., Ltd.).
2) Printed with a Canon printer BJC455J using black (B), enlarged by 100 times, and measured the dot diameter.
3) Resolution of printed image Black (B) was solid-printed with a Canon printer BJC455J and measured with a Macbeth densitometer RD-918 (manufactured by Macbeth).
Further, magenta (M), cyan (C), and yellow (Y) were similarly processed. The magenta, cyan and yellow inks used for printing were obtained by using Cibafix Direct Red 9, Cibafix Direct Blue 86 and Cibafix Direct Yellow 23, respectively, instead of the dye used in Example 1.
4) Black, magenta, cyan, and yellow were simultaneously jetted to the same place with an ink-absorbing canon printer BJC455J, and rubbed with a paper presser plate after 1 second, and ink stains were measured.
○: White portion without dirt △: Slightly dirty ×: Severely dirty [0037]
[Ratio Comparative Examples 1 to 7]
In the same manner as in Example 1, using the ink absorbent compositions (M- 6 to M-10) of Formulation Examples 6 to 10 shown in Table 1 and the commercial products 1 and 2, black (B) (K- 6 to K-12). Using these, the same measurements as in Example 1 were performed, and the results are shown in Table 3.
[0038]
[Table 3]

[0039]
【The invention's effect】
The ink absorbent composition of the present invention has a low contact angle and dynamic surface tension immediately after dropping, and exhibits excellent absorbency, so that it can cope with high-speed printing and is also an excellent ink suitable for environmental problems. obtain. Due to this characteristic, the ink absorbent composition of the present invention is extremely advantageous practically.

Claims (2)

(A) The following formula (1)

(In the formula, R ¹ and R ² each represent an alkyl group having 1 to 5 carbon atoms.)
And acetylene glycol represented by the following formula (2):

(In the formula, R ¹ and R ² each represent an alkyl group having 1 to 5 carbon atoms, m and n are each a positive number, and m + n is less than 10.)
1 type or 2 types or more chosen from the ethoxylated form of acetylene glycol represented by
10 to 75% by weight
(B) Following formula (3)

(In the formula, R ³ and R ⁴ each represent an alkyl group having 1 to 5 carbon atoms, p and q are positive numbers, and p + q is 10 to 40.)
One or two or more of ethoxylated acetylene glycols having an HLB of 10 to 18 represented by 20 to 80 % by weight
(C) 5-20% by weight of polyoxy (ethylene / propylene) block polymer
An ink absorbent composition characterized in that the contact angle after 30 seconds of dropping the 0.1 wt% aqueous solution thereof is 70 degrees or less, and the dynamic surface tension at 1 Hz and 10 Hz is 50 mN / m or less, respectively. object. The ink absorbent composition according to claim 1, wherein the component (A) is an ethoxylated acetylene glycol represented by the following formula (2).

(Wherein R ¹ , R ² , m and n are as defined in claim 1).