JP2011202063A - Aqueous pigment dispersant and aqueous pigment dispersion including the same - Google Patents
Aqueous pigment dispersant and aqueous pigment dispersion including the same Download PDFInfo
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本発明は、水系顔料分散剤に関する。より詳細には、顔料の初期分散性、顔料分散体の長期保存安定性、低起泡性に優れた水系顔料分散剤に関する。さらには、該顔料分散剤を用いた水性顔料分散体に関する。 The present invention relates to an aqueous pigment dispersant. More specifically, the present invention relates to an aqueous pigment dispersant excellent in initial pigment dispersibility, long-term storage stability of the pigment dispersion, and low foamability. Furthermore, the present invention relates to an aqueous pigment dispersion using the pigment dispersant.
近年、印刷業界や塗料業界では、環境に対する安全性の観点からインクや塗料の水性化が進められている。しかしながら、無機系顔料及び有機系顔料はいずれも水に対する親和性が低く、分散剤を使用した場合にも水へ分散させることは容易ではない。特に有機系顔料分子の多くは高度に共役したπ電子系により安定な結晶構造を有するため、水分子が十分に顔料表面に吸着せず、水への分散はより一層困難となっている。このような背景から、インクや塗料などの顔料分散体組成物においては、顔料の分散性を向上させることのできる分散剤の開発が要求されている。
顔料の分散は、溶媒の顔料への湿潤、機械的解砕及び分散安定化によりなされる。このうち溶媒の顔料への湿潤は顔料の初期分散性に影響を与え、分散安定化は長期保存安定性に影響を与える。
高分子系顔料分散剤としては、スチレン−アクリル酸共重合体、ポリアクリル酸塩、ナフタレンスルホン酸塩のホルマリン縮合物等が知られている。これらの高分子系顔料分散剤は、立体斥力により顔料分散体の長期保存安定性に効果を有するが、分子量が大きいために溶媒の顔料への湿潤効果はほとんど得られない。また、これらの高分子系分散剤は、分子中の複数の吸着基により一つの分子が複数の粒子に吸着するいわゆる橋架け凝集が起こり、顔料粒子の凝集、沈降を引き起こすことがあった。
一方、界面活性剤系顔料分散剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレン・ポリオキシプロピレン・ポリオキシエチレントリブロック共重合体、アルコキシポリオキシエチレン脂肪酸エステル等の非イオン性界面活性剤や、ポリオキシエチレンアルキルエーテルの硫酸エステル塩等の陰イオン性界面活性剤等が知られている。これらの分散剤のうち非イオン性界面活性剤からなる顔料分散剤は、顔料粒子に対する湿潤性を示すため顔料の初期分散性には効果を有するものの、顔料粒子間にはたらく斥力が不十分であり、長期保存下においては顔料粒子の凝集や沈降を引き起こすことがあった。また、ポリオキシエチレンアルキルエーテルの硫酸エステル塩は、顔料の初期分散性及び長期保存安定性に効果を有するものの、起泡性が高いという問題があった。
In recent years, in the printing industry and the paint industry, inks and paints have been made water-based from the viewpoint of environmental safety. However, both inorganic pigments and organic pigments have a low affinity for water, and even when a dispersant is used, it is not easy to disperse in water. In particular, since many organic pigment molecules have a stable crystal structure due to a highly conjugated π-electron system, water molecules are not sufficiently adsorbed on the pigment surface, making it more difficult to disperse in water. Against this background, in pigment dispersion compositions such as inks and paints, development of a dispersant capable of improving the dispersibility of the pigment is required.
The pigment is dispersed by wetting of the solvent into the pigment, mechanical disintegration, and dispersion stabilization. Among these, wetting of the solvent into the pigment affects the initial dispersibility of the pigment, and dispersion stabilization affects the long-term storage stability.
Known polymer pigment dispersants include styrene-acrylic acid copolymers, polyacrylates, and formalin condensates of naphthalenesulfonate. These polymer pigment dispersants have an effect on the long-term storage stability of the pigment dispersion due to steric repulsion, but because the molecular weight is large, the wetting effect of the solvent on the pigment is hardly obtained. In addition, these polymer-based dispersants may cause so-called bridge aggregation in which one molecule is adsorbed to a plurality of particles by a plurality of adsorption groups in the molecule, which may cause aggregation and sedimentation of pigment particles.
On the other hand, surfactant-based pigment dispersants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene / polyoxypropylene / polyoxyethylene triblock copolymers, and alkoxy polyoxyethylene fatty acid esters. Anionic surfactants such as polyoxyethylene alkyl ether sulfates are known. Among these dispersants, pigment dispersants composed of nonionic surfactants have an effect on the initial dispersibility of the pigment because they exhibit wettability to the pigment particles, but the repulsive force acting between the pigment particles is insufficient. Under long-term storage, pigment particles may cause aggregation and sedimentation. In addition, the sulfate ester salt of polyoxyethylene alkyl ether has an effect on the initial dispersibility and long-term storage stability of the pigment, but has a problem of high foamability.
このような問題を改善するために種々の分散剤が開発されており、極性有機液体中における顔料の分散剤としてアルコールのエチレンオキシド・アルキレンオキシド付加物を用いる方法（例えば特許文献１）が報告されている。当該特許文献１には、具体例として、アルコールがアリールアルコール又は炭素数が１２以上のアルカノールであり、アルキレンオキシドがプロピレンオキシドである化合物が示されているが、このような化合物では顔料粒子に対する湿潤性により初期分散性を有するものの、立体斥力が十分に働かないために、顔料分散体の長期保存下において顔料粒子の凝集や沈降が起こることがあった。
また、ポリグリセリンのアルキレンオキシド付加物と脂肪酸エステルとの部分エステルの硫酸エステル塩を用いる方法（例えば特許文献２）等が知られているが、顔料の初期分散性及び長期保存安定性に効果を有するものの、起泡性が高いという問題があった。
このように、初期分散性、顔料分散体の長期保存安定性、低起泡性に優れた顔料分散剤は未だ得られていない。
Various dispersants have been developed in order to improve such problems, and a method using an ethylene oxide / alkylene oxide adduct of alcohol as a pigment dispersant in a polar organic liquid (for example, Patent Document 1) has been reported. Yes. As a specific example, Patent Document 1 discloses a compound in which the alcohol is an aryl alcohol or an alkanol having 12 or more carbon atoms, and the alkylene oxide is propylene oxide. Although it has initial dispersibility depending on the property, the steric repulsive force does not work sufficiently, so that pigment particles may aggregate or settle under long-term storage of the pigment dispersion.
In addition, a method using a sulfate ester salt of a partial ester of an alkylene oxide adduct of polyglycerin and a fatty acid ester is known (for example, Patent Document 2), etc., but it is effective for the initial dispersibility and long-term storage stability of the pigment. Although it had, there was a problem that foamability was high.
Thus, a pigment dispersant excellent in initial dispersibility, long-term storage stability of the pigment dispersion, and low foaming property has not been obtained yet.
本発明が解決しようとする課題は、顔料の初期分散性、顔料分散体の長期保存安定性、低起泡性に優れた水系顔料分散剤を提供する点にある。 The problem to be solved by the present invention is to provide an aqueous pigment dispersant excellent in initial dispersibility of the pigment, long-term storage stability of the pigment dispersion, and low foaming property.
本発明者らは、上記課題を解決するために鋭意検討した結果、オキシブチレン基を特定の割合で含有するポリオキシアルキレンアルキルエーテルを用いることにより上記課題が解決し、顔料の初期分散性、顔料分散体の長期保存安定性、低起泡性に優れた水系顔料分散剤が得られることを見出した。
すなわち、本発明は、式（１）で表され、分子量が１０００〜２０００である化合物からなる水系顔料分散剤に関する。
Ｒ１−Ｏ−（ＥＯ）ｍ−（ＢＯ）ｎ−Ｒ２ （１）
（式中、Ｒ１は炭素数１〜４の炭化水素基、Ｒ２は水素原子又は炭素数１〜４の炭化水素基、ＥＯはオキシエチレン基、ＢＯはオキシブチレン基、ｍはオキシエチレン基の平均付加モル数、ｎはオキシブチレン基の平均付加モル数を示し、ｍは８〜２６、ｎは８〜１４、ｍ＋ｎは１６〜３２であって、分子量中に占めるオキシブチレン基部分の割合は４５〜７５質量％である。）
さらに本発明は、該水系顔料分散剤を含有する水性顔料分散体に関する。
As a result of intensive studies to solve the above problems, the present inventors have solved the above problems by using a polyoxyalkylene alkyl ether containing an oxybutylene group in a specific ratio. It was found that an aqueous pigment dispersant excellent in long-term storage stability and low foamability of the dispersion can be obtained.
That is, this invention relates to the water-system pigment dispersant which consists of a compound represented by Formula (1) and whose molecular weight is 1000-2000.
R 1 —O— (EO) m — (BO) n —R 2 (1)
(In the formula, R 1 is a hydrocarbon group having 1 to 4 carbon atoms, R 2 is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, EO is an oxyethylene group, BO is an oxybutylene group, and m is an oxyethylene group. The average addition mole number of n, n shows the average addition mole number of an oxybutylene group, m is 8-26, n is 8-14, m + n is 16-32, The ratio of the oxybutylene group part which occupies in molecular weight Is 45 to 75% by mass.)
Furthermore, the present invention relates to an aqueous pigment dispersion containing the aqueous pigment dispersant.
本発明に係る式（１）で表わされる化合物は、無機及び有機顔料の水系媒体への分散性を顕著に向上させることができる。これを用いて調製した顔料分散体は、初期分散性に優れるのみならず、長期の保存安定性も極めて良好であり、しかも、起泡性が低いことから、安定で実用効果の高い顔料分散体であり、例えば、水性フェルトペン、水性ボールペン、水性塗料、印刷用インク、特に水性インクジェット用インクとして極めて有用である。 The compound represented by the formula (1) according to the present invention can remarkably improve the dispersibility of inorganic and organic pigments in an aqueous medium. The pigment dispersion prepared using this is not only excellent in initial dispersibility, but also has excellent long-term storage stability and low foaming properties, so that it is stable and has a high practical effect. For example, it is extremely useful as a water-based felt pen, water-based ball-point pen, water-based paint, printing ink, particularly water-based inkjet ink.
式（１）において、Ｒ１は炭素数１〜４の炭化水素基であり、直鎖であっても分岐であってもよく、具体的にはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基が挙げられ、好ましくはメチル基、エチル基である。炭素数が４より大きくなると起泡性が高くなり、また分子量中に占めるオキシブチレン基の割合が低下して顔料分散体の長期保存安定性が低下する。
Ｒ２は水素原子又は炭素数１〜４の炭化水素基であり、炭化水素基である場合は直鎖であっても分岐であってもよく、具体的にはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基が挙げられ、好ましくはｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基であり、より好ましくはイソプロピル基、イソブチル基、ｔｅｒｔ−ブチル基である。式（１）におけるＲ２が炭素数３〜４の分岐の炭化水素基である場合は、顔料への浸透性が高いために初期分散性に優れた効果を有する。
炭素数が４より大きくなると起泡性が高くなり、また分子量中に占めるオキシブチレン基の割合が低下して顔料分散体の長期保存安定性が低下する。
In the formula (1), R 1 is a hydrocarbon group having 1 to 4 carbon atoms, which may be linear or branched. Specifically, methyl group, ethyl group, n-propyl group, isopropyl Group, n-butyl group, isobutyl group, and tert-butyl group, preferably methyl group and ethyl group. When the carbon number is larger than 4, the foaming property is increased, and the ratio of the oxybutylene group in the molecular weight is lowered, so that the long-term storage stability of the pigment dispersion is lowered.
R 2 is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and when it is a hydrocarbon group, it may be linear or branched, specifically a methyl group, an ethyl group, n- A propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group are exemplified, and an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group are preferable, and more preferably An isopropyl group, an isobutyl group, and a tert-butyl group. When R 2 in the formula (1) is a branched hydrocarbon group having 3 to 4 carbon atoms, it has an excellent initial dispersibility because of its high permeability to the pigment.
When the carbon number is larger than 4, the foaming property is increased, and the ratio of the oxybutylene group in the molecular weight is lowered, so that the long-term storage stability of the pigment dispersion is lowered.
ＥＯはオキシエチレン基、ｍはオキシエチレン基の付加モル数であり、ｍは８〜２６、好ましくは１０〜１８である。ｍが８より小さくなると親水性が低下して水又は水溶性有機溶媒への溶解性が低下し、ｍが２６より大きくなると疎水性が低下して顔料の初期分散性及び長期保存安定性が低下する傾向となる。
ＢＯはオキシブチレン基、ｎはオキシブチレン基の付加モル数であり、ｎは８〜１４、好ましくは９〜１２である。ｎが８より小さくなると分子量中に占めるオキシブチレン基の割合が低下して顔料分散体の長期保存安定性が低下し、ｎが１４より大きくなると親水性が低下する。
ｍ＋ｎは１６〜３２であり、好ましくは２０〜２８である。ｍ＋ｎが１６より小さくなると立体斥力が低下して顔料分散体の長期保存安定性が低下し、ｍ＋ｎが３２より大きくなると分子量が増加して顔料分散体の凝集、沈降が起こり長期保存安定性が低下しやすくなる。
式（１）で表される化合物の分子量中に占めるオキシブチレン基部分の割合は、４５〜７５質量％であり、好ましくは５０〜６０質量％である。分子量中に占めるオキシブチレン基部分の割合が４５質量％より小さくなると立体斥力が低下して顔料分散体の長期保存安定性が不十分となり、７５質量％より大きくなると水への溶解性が低下する傾向となる。
式（１）で表される化合物の分子量は１０００〜２０００である。分子量が１０００より小さいと、顔料粒子間にはたらく斥力が不十分であり、顔料分散体の長期保存安定性が低下し、分子量が２０００を超えると溶媒の顔料への湿潤性が不十分であり、顔料の初期分散性が低下する。
EO is an oxyethylene group, m is the number of added moles of oxyethylene group, and m is 8 to 26, preferably 10 to 18. When m is less than 8, the hydrophilicity is lowered and the solubility in water or water-soluble organic solvent is lowered. When m is more than 26, the hydrophobicity is lowered and the initial dispersibility and long-term storage stability of the pigment are lowered. Tend to.
BO is an oxybutylene group, n is the number of added moles of the oxybutylene group, and n is 8 to 14, preferably 9 to 12. When n is less than 8, the proportion of oxybutylene groups in the molecular weight decreases, and the long-term storage stability of the pigment dispersion decreases. When n is greater than 14, the hydrophilicity decreases.
m + n is 16 to 32, preferably 20 to 28. When m + n is less than 16, the steric repulsion decreases and the long-term storage stability of the pigment dispersion decreases. When m + n is greater than 32, the molecular weight increases and the pigment dispersion agglomerates and settles, reducing the long-term storage stability. It becomes easy to do.
The proportion of the oxybutylene group moiety in the molecular weight of the compound represented by formula (1) is 45 to 75% by mass, preferably 50 to 60% by mass. When the proportion of the oxybutylene group portion in the molecular weight is less than 45% by mass, the steric repulsion is reduced and the long-term storage stability of the pigment dispersion is insufficient, and when it exceeds 75% by mass, the solubility in water is decreased. It becomes a trend.
The molecular weight of the compound represented by Formula (1) is 1000 to 2000. If the molecular weight is less than 1000, the repulsive force acting between the pigment particles is insufficient, the long-term storage stability of the pigment dispersion is reduced, and if the molecular weight exceeds 2000, the wettability of the solvent to the pigment is insufficient, The initial dispersibility of the pigment is reduced.
式（１）における無機性値と有機性値から算出されるＨＬＢは好ましくは７〜１１であり、より好ましくは８〜１０である。ＨＬＢが７より小さいと親水性が低下し、１１より大きいと顔料への吸着性が低下し、顔料の初期分散性及び顔料分散体の長期保存安定性が低下する。ここで、無機性値及び有機性値とは化合物の親水性、親油性の指標であり、ＨＬＢが小さいほど親油性が高く、ＨＬＢが大きいほど親水性が高い。無機性値及び有機性値からＨＬＢは以下の式で算出される（甲田善生著、「有機概念図−基礎と応用−」、三共出版、１９８４年）。
ＨＬＢ＝無機性値／有機性値×１０
The HLB calculated from the inorganic value and the organic value in the formula (1) is preferably 7 to 11, and more preferably 8 to 10. When the HLB is less than 7, the hydrophilicity is lowered, and when it is more than 11, the adsorptivity to the pigment is lowered, and the initial dispersibility of the pigment and the long-term storage stability of the pigment dispersion are lowered. Here, the inorganic value and the organic value are indicators of the hydrophilicity and lipophilicity of the compound. The smaller the HLB, the higher the lipophilicity, and the larger the HLB, the higher the hydrophilicity. The HLB is calculated from the inorganic value and the organic value by the following formula (Yoshio Koda, “Organic Conceptual Diagram-Fundamentals and Applications”, Sankyo Publishing, 1984).
HLB = inorganic value / organic value × 10
式（１）で示される化合物は、従来公知の方法で製造することができる。例えば、炭素数１〜４のアルコールにエチレンオキシド及びブチレンオキシドを順に付加重合させ、さらにその後ハロゲン化アルキルをアルカリ触媒の存在下に反応させることにより得られる。
式（１）で示される化合物は、分子の両端に疎水基を有することにより、起泡性が低い上に被分散物に対する吸着性が高く、顔料の初期分散性が高い。さらにオキシブチレン基を特定の割合で含有することでその分岐のエチル基により立体斥力を付与することができ、顔料分散体の長期保存下での安定性を付与することができる。
本発明の顔料分散剤を用いた顔料分散体は、該顔料分散剤を水及び／又は水溶性有機溶媒からなる液媒体に事前に添加した後、顔料を添加する、あるいは該顔料分散剤と顔料を混合した後、液媒体を添加してボールミル、サンドミルのような分散機により顔料を分散させることにより得られる。
本発明の顔料分散剤の添加量は、顔料に対して、０．０１〜８０質量％であり、１０〜６０質量％が好ましい。添加量が０．０１％より少ないと初期分散性及び長期保存安定性の効果が小さく、８０質量％より大きいと使用量に見合った効果が得られない。
The compound represented by the formula (1) can be produced by a conventionally known method. For example, it can be obtained by addition-polymerizing ethylene oxide and butylene oxide in order to an alcohol having 1 to 4 carbon atoms, and then reacting an alkyl halide in the presence of an alkali catalyst.
Since the compound represented by the formula (1) has hydrophobic groups at both ends of the molecule, the foaming property is low, the adsorptivity to the object to be dispersed is high, and the initial dispersibility of the pigment is high. Furthermore, by containing an oxybutylene group in a specific ratio, steric repulsion can be imparted by the branched ethyl group, and stability of the pigment dispersion under long-term storage can be imparted.
In the pigment dispersion using the pigment dispersant of the present invention, the pigment dispersant is added in advance to a liquid medium composed of water and / or a water-soluble organic solvent, and then the pigment is added, or the pigment dispersant and the pigment are added. After mixing, the liquid medium is added and the pigment is dispersed by a dispersing machine such as a ball mill or a sand mill.
The addition amount of the pigment dispersant of this invention is 0.01-80 mass% with respect to a pigment, and 10-60 mass% is preferable. If the addition amount is less than 0.01%, the effect of initial dispersibility and long-term storage stability is small, and if it is more than 80% by mass, an effect commensurate with the amount used cannot be obtained.
本発明の顔料分散体に適応する顔料は、種類が特に限定されず、有機系顔料であっても無機系顔料であってもよい。有機系顔料としては、例えば、フタロシアニン系顔料、キナクリドン系顔料、キナクリドンキノン系顔料、アントラピリミジン系顔料、アンサンスロン系顔料、インダンスロン系顔料、フラバンスロン系顔料、ペリレン系顔料、ジケトピロロピロール系顔料、ペリノン系顔料、キノフタロン系顔料、アントラキノン系顔料、チオインジゴ系顔料、ベンツイミダゾロン系顔料、イソインドリノン系顔料、アゾメチン系顔料、アゾ系顔料等が挙げられる。また、無機系顔料としては、例えば、カーボンブラック、二酸化チタン、炭酸カルシウム等が挙げられる。本発明で使用する顔料の種類は有機系顔料が好ましく、このうち特に縮合多環系顔料及び金属錯体顔料が好ましい。 The type of the pigment that can be applied to the pigment dispersion of the present invention is not particularly limited, and may be an organic pigment or an inorganic pigment. Examples of organic pigments include phthalocyanine pigments, quinacridone pigments, quinacridone quinone pigments, anthrapyrimidine pigments, ansanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole. Pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, isoindolinone pigments, azomethine pigments and azo pigments. Examples of inorganic pigments include carbon black, titanium dioxide, and calcium carbonate. The pigment used in the present invention is preferably an organic pigment, and among these, a condensed polycyclic pigment and a metal complex pigment are particularly preferable.
本発明の顔料分散剤を用いた顔料分散体は、必要に応じて界面活性剤、有機アミン等のｐＨ調整剤、水溶性高分子等の粘度調整剤、消泡剤、防腐剤等を配合することができる。
本発明の顔料分散体において使用する水溶性有機溶剤としては、例えば、メチルアルコール、エチルアルコール、ｎ−プロピルアルコール、イソプロピルアルコール、ｎ−ブチルアルコール、イソブチルアルコール、ｔｅｒｔ−ブチルアルコール等のアルコール類、エチレングリコール、プロピレングリコール、ブチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、グリセリン、ジグリセリン、ポリグリセリン等の多価アルコール類、アセトン、メチルエチルケトン等のケトン類、テトラヒドロフラン、ジオキサン、エチレングリコールメチルエーテル、エチレングリコールエチルエーテル、ジエチレングリコールメチルエーテル、ジエチレングリコールエチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル等のエーテル類、Ｎ−メチルピロリドン、１，３−ジメチル−２−イミダゾリジノン、プロピレングリコールモノメチルエーテルアセテート等が挙げられる。
本発明の顔料分散体の使用形態は特に限定されず、例えばインクジェット記録用インク、印刷用インク、水性塗料等に用いることができる。
以下、実施例により本発明をさらに詳しく説明するが、本発明はこれに限定されるものではない。
The pigment dispersion using the pigment dispersant of the present invention contains a surfactant, a pH adjuster such as an organic amine, a viscosity adjustor such as a water-soluble polymer, an antifoaming agent, an antiseptic, and the like as necessary. be able to.
Examples of the water-soluble organic solvent used in the pigment dispersion of the present invention include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, and ethylene. Glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polyhydric alcohols such as glycerin, diglycerin, polyglycerin, ketones such as acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, ethylene glycol methyl ether , Ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether Le, triethylene glycol monomethyl ether, ethers such as triethylene glycol monoethyl ether, N- methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, propylene glycol monomethyl ether acetate.
The usage form of the pigment dispersion of the present invention is not particularly limited, and can be used, for example, for ink jet recording ink, printing ink, water-based paint and the like.
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this.
［実施例１］
＜合成例１＞
メタノール３２ｇ（１モル）と触媒として水酸化カリウム６ｇを５Ｌ容量オートクレーブ中に仕込み、オートクレーブ内の空気を窒素で置換した後、撹拌しながら１２０℃にて触媒を完全に溶解させた。次に滴下装置にてエチレンオキシド６１６ｇ（１４モル）を滴下し、２時間撹拌し反応させた。さらに滴下装置にてブチレンオキシド７２０ｇ（１０モル）を滴下し、２時間撹拌し反応させた。次に、水酸化カリウム１０７ｇを仕込み、系内を乾燥窒素で置換した後、塩化イソブチル１０２ｇを温度８０〜１３０℃で圧入し５時間反応させた。その後オートクレーブより反応組成物を取り出し、塩酸で中和してｐＨ６〜７とし、含有する水分を除去するため減圧−０．０９５ＭＰａ(ゲージ圧)、１００℃で１時間処理した。さらに処理後生成した塩を除去するために濾過を行い、化合物ａ−１を得た。
塩化イソブチルを反応させる前にサンプリングし精製したものの水酸基価が４２であり、化合物ａ−１の水酸基価が１であったため、水素原子がほぼメチル基に変換されていることがわかる。
[Example 1]
<Synthesis Example 1>
After charging 32 g (1 mol) of methanol and 6 g of potassium hydroxide as a catalyst into a 5 L-volume autoclave and replacing the air in the autoclave with nitrogen, the catalyst was completely dissolved at 120 ° C. with stirring. Next, 616 g (14 mol) of ethylene oxide was dropped with a dropping device, and the mixture was stirred for 2 hours to be reacted. Further, 720 g (10 mol) of butylene oxide was added dropwise with a dropping device, and the mixture was stirred for 2 hours to be reacted. Next, 107 g of potassium hydroxide was charged and the inside of the system was replaced with dry nitrogen, and then 102 g of isobutyl chloride was injected at a temperature of 80 to 130 ° C. and reacted for 5 hours. Thereafter, the reaction composition was taken out from the autoclave, neutralized with hydrochloric acid to pH 6 to 7, and treated at a reduced pressure of -0.095 MPa (gauge pressure) at 100 ° C for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt produced after the treatment to obtain a compound a-1.
The sample which was sampled and purified before reacting with isobutyl chloride had a hydroxyl value of 42, and since the hydroxyl value of compound a-1 was 1, it can be seen that the hydrogen atom was almost converted to a methyl group.
＜起泡性の評価＞
１００ｍＬ容量スクリュー管に、化合物ａ−１の０．１質量％希釈液３０ｇを入れ、２５℃の恒温槽で１時間静置した。これを、手で１０秒間振とうし、振とう直後及び１０分後における液面からの泡の高さを測定して、以下の基準で評価した。結果は、表２に示す。
○：泡高さ３０ｍｍ未満
×：泡高さ３０ｍｍ以上
＜顔料分散体の吸光度の評価＞
１００ｍＬ容量ビーカーに、フタロシアニンブルー（東京化成工業（株）製ピグメントブルー１５）２ｇ、化合物ａ−１の１０質量％水希釈液１０ｇ、イオン交換水２８ｇを順に仕込み、ディスパー型撹拌機で１時間撹拌し、５質量％顔料分散体を得た。１００ｍＬ容量ビーカーに、イオン交換水４９ｇと５質量％顔料分散体１ｇを入れ、マグネティックスターラーで完全に均一になるまで撹拌して０．１質量％顔料分散体を得た。さらに、１００ｍＬビーカーにイオン交換水９０ｇと０．１質量％顔料分散体１０ｇを入れ、マグネティックスターラーで完全に均一になるまで撹拌して０．０１質量％顔料分散体を得た。
０．０１質量％顔料分散体を５０℃にて３時間及び１０日間静置後、上澄み液を採取し、波長５８５ｎｍにおける吸光度を測定して、以下の基準で評価した。結果は、表２に示す。
○：吸光度０．８以上
×：吸光度０．８未満
<Evaluation of foamability>
In a 100 mL capacity screw tube, 30 g of a 0.1% by weight dilution of compound a-1 was placed and allowed to stand in a thermostatic bath at 25 ° C. for 1 hour. This was shaken by hand for 10 seconds, the height of the bubble from the liquid level immediately after shaking and after 10 minutes was measured, and evaluated according to the following criteria. The results are shown in Table 2.
○: Bubble height less than 30 mm ×: Bubble height of 30 mm or more <Evaluation of absorbance of pigment dispersion>
A 100 mL beaker was charged with 2 g of phthalocyanine blue (Pigment Blue 15 manufactured by Tokyo Chemical Industry Co., Ltd.), 10 g of 10% by weight water dilution of compound a-1 and 28 g of ion-exchanged water in this order, and stirred for 1 hour with a disper-type stirrer. And a 5 mass% pigment dispersion was obtained. In a 100 mL capacity beaker, 49 g of ion-exchanged water and 1 g of a 5% by mass pigment dispersion were added and stirred with a magnetic stirrer until completely uniform to obtain a 0.1% by mass pigment dispersion. Furthermore, 90 g of ion-exchanged water and 10 g of a 0.1% by mass pigment dispersion were placed in a 100 mL beaker, and stirred until completely uniform with a magnetic stirrer to obtain a 0.01% by mass pigment dispersion.
The 0.01% by mass pigment dispersion was allowed to stand at 50 ° C. for 3 hours and 10 days, and then the supernatant was collected and the absorbance at a wavelength of 585 nm was measured and evaluated according to the following criteria. The results are shown in Table 2.
○: Absorbance 0.8 or more ×: Absorbance less than 0.8
［実施例２〜１０］
実施例１と同様の方法で、表１に示す化合物ａ−２〜ａ−１０を合成し（合成例２〜１０）、０．１％水溶液の起泡性の評価と顔料分散体の調製、評価を行った。
[実施例１１]
＜合成例１１＞
メタノール３２ｇ（１モル）と触媒として水酸化カリウム５ｇを５Ｌ容量オートクレーブ中に仕込み、オートクレーブ内の空気を窒素で置換した後、撹拌しながら１２０℃にて触媒を完全に溶解させた。次に滴下装置にてエチレンオキシド４８４ｇ（１１モル）を滴下し、２時間撹拌し反応させた。さらに滴下装置にてブチレンオキシド７２０ｇ（１０モル）を滴下し、２時間撹拌し反応させた。その後オートクレーブより反応組成物を取り出し、塩酸で中和してｐＨ６〜７とし、含有する水分を除去するため減圧−０．０９５ＭＰａ(ゲージ圧)、１００℃で１時間処理した。さらに処理後生成した塩を除去するために濾過を行い、化合物ａ−１１を得た。この化合物ａ−１１の水酸基価は４６．９であった。
この化合物ａ−１１を用い、実施例１と同様の方法で、０．１％水溶液の起泡性の評価と顔料分散体の調製、評価を行った。
[Examples 2 to 10]
Compounds a-2 to a-10 shown in Table 1 were synthesized in the same manner as in Example 1 (Synthesis Examples 2 to 10), evaluation of foamability of 0.1% aqueous solution and preparation of pigment dispersions, Evaluation was performed.
[Example 11]
<Synthesis Example 11>
32 g (1 mol) of methanol and 5 g of potassium hydroxide as a catalyst were charged into a 5 L autoclave, the air inside the autoclave was replaced with nitrogen, and the catalyst was completely dissolved at 120 ° C. with stirring. Next, 484 g (11 mol) of ethylene oxide was dropped with a dropping device, and the mixture was stirred for 2 hours to be reacted. Further, 720 g (10 mol) of butylene oxide was added dropwise with a dropping device, and the mixture was stirred for 2 hours to be reacted. Thereafter, the reaction composition was taken out from the autoclave, neutralized with hydrochloric acid to pH 6 to 7, and treated at a reduced pressure of -0.095 MPa (gauge pressure) at 100 ° C for 1 hour in order to remove the contained water. Furthermore, it filtered in order to remove the salt produced | generated after a process, and compound a-11 was obtained. The hydroxyl value of this compound a-11 was 46.9.
Using this compound a-11, evaluation of foamability of a 0.1% aqueous solution and preparation and evaluation of a pigment dispersion were performed in the same manner as in Example 1.
［比較例１］
式（１）で示される化合物を添加しない以外は実施例１と同様の方法で、顔料分散体の調製、評価を行った。
［比較例２〜７］
実施例１と同様の方法で、表１に示す化合物ｂ−１〜ｂ−６を合成した。この化合物ｂ−１〜ｂ−６を用い、実施例１と同様の方法で、０．１％水溶液の起泡性の評価と顔料分散体の調製、評価を行った。
[Comparative Example 1]
A pigment dispersion was prepared and evaluated in the same manner as in Example 1 except that the compound represented by the formula (1) was not added.
[Comparative Examples 2 to 7]
In the same manner as in Example 1, the compounds b-1 to b-6 shown in Table 1 were synthesized. Using these compounds b-1 to b-6, evaluation of foamability of a 0.1% aqueous solution and preparation and evaluation of a pigment dispersion were performed in the same manner as in Example 1.
[比較例８]
式（１）で示される化合物のかわりにポリオキシエチレン（２０モル）ラウリルエーテル（日油（株）製ノニオンＫ−２２０）（化合物Ａ）を用いた以外は実施例１と同様の方法で、０．１％水溶液の起泡性の評価と顔料分散体の調製、評価を行った。
[比較例９]
式（１）で示される化合物のかわりにポリエチレングリコール−ポリプロピレングリコール−ポリエチレングリコールトリブロック共重合体（平均分子量１６７０、ポリエチレングリコール含有率４０質量％）（化合物Ｂ）を用いた以外は実施例１と同様の方法で、０．１％水溶液の起泡性の評価と顔料分散体の調製、評価を行った。
[比較例１０]
式（１）で示される化合物のかわりにメトキシポリオキシエチレン（２０モル）オレイン酸エステル（化合物Ｃ）を用いた以外は実施例１と同様の方法で、０．１％水溶液の起泡性の評価と顔料分散体の調製、評価を行った。
[比較例１１]
式（１）で示される化合物のかわりにポリオキシエチレン（３０モル）ラウリルエーテルの硫酸エステルナトリウム塩（化合物Ｄ）を用いた以外は実施例１と同様の方法で、０．１％水溶液の起泡性の評価と顔料分散体の調製、評価を行った。
[比較例１２]
式（１）で示される化合物のかわりにポリオキシエチレン（１３モル）ポリオキシプロピレン（１４モル）２−ナフチルエーテル（化合物Ｅ）を用いた以外は実施例１と同様の方法で、０．１％水溶液の起泡性の評価と顔料分散体の調製、評価を行った。
[Comparative Example 8]
In the same manner as in Example 1 except that polyoxyethylene (20 mol) lauryl ether (Nonion K-220 manufactured by NOF Corporation) (compound A) was used instead of the compound represented by the formula (1), Evaluation of foamability of a 0.1% aqueous solution and preparation and evaluation of a pigment dispersion were performed.
[Comparative Example 9]
Example 1 except that a polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer (average molecular weight 1670, polyethylene glycol content 40 mass%) (compound B) was used instead of the compound represented by the formula (1). In the same manner, the foamability of a 0.1% aqueous solution and the preparation and evaluation of a pigment dispersion were performed.
[Comparative Example 10]
In the same manner as in Example 1 except that methoxypolyoxyethylene (20 mol) oleate (Compound C) was used instead of the compound represented by Formula (1), Evaluation and preparation of pigment dispersion and evaluation were performed.
[Comparative Example 11]
A 0.1% aqueous solution was prepared in the same manner as in Example 1 except that polyoxyethylene (30 mol) lauryl ether sulfate sodium salt (compound D) was used instead of the compound represented by formula (1). Evaluation of foamability and preparation and evaluation of a pigment dispersion were performed.
[Comparative Example 12]
In the same manner as in Example 1 except that polyoxyethylene (13 mol) polyoxypropylene (14 mol) 2-naphthyl ether (compound E) was used instead of the compound represented by the formula (1), 0.1 % Foaming property evaluation and pigment dispersion preparation and evaluation were performed.
表２の結果から、実施例１〜１１の化合物は、起泡性が低く、初期分散性及び長期保存安定性に優れた顔料分散体が得られることがわかる。
これに対して、比較例１は、本発明の化合物を用いていないために顔料の初期分散性及び顔料分散体の長期保存安定性が不十分である。
比較例２は、式（１）で示される化合物の炭化水素基の炭素数が本発明の範囲より大きいために起泡性が高く、また分子中に占めるオキシブチレン基の割合が本発明の範囲より小さいために、顔料分散体の長期保存安定性が不十分である。
比較例３は、式（１）で示される化合物の炭化水素基の炭素数が本発明の範囲より大きいために起泡性が高く、また分子中に占めるオキシブチレン基の割合が本発明の範囲より小さいために、顔料分散体の長期保存安定性が不十分である。
比較例４は、式（１）で示される化合物のオキシエチレン基の付加モル数が本発明の範囲より大きく、分子量中に占めるオキシブチレン基の割合が本発明の範囲より小さいために、顔料の初期分散性及び顔料分散体の長期保存安定性が不十分である。
比較例５は、式（１）で示される化合物のオキシブチレン基の付加モル数が本発明の範囲より大きいために水溶性を示さず、顔料の初期分散性及び顔料分散体の長期保存安定性が不十分である。
比較例６は、式（１）で示される化合物のオキシブチレン基の付加モル数が本発明の範囲より小さく、分子量中に占めるオキシブチレン基の割合が本発明の範囲より小さいために、顔料の初期分散性及び顔料分散体の長期保存安定性が不十分である。
比較例７は、式（１）で示される化合物のオキシエチレン基の付加モル数が本発明の範囲より小さく、分子量中に占めるオキシブチレン基の割合が本発明の範囲より大きいために、水溶性を示さず、顔料の初期分散性及び顔料分散体の長期保存安定性が不十分である。
比較例８は、本発明の化合物を用いていないために起泡性が高く、顔料分散体の長期保存安定性が不十分である。
比較例９は、本発明の化合物を用いていないために、顔料の初期分散性及び顔料分散体の長期保存安定性が不十分である。
比較例１０は、本発明の化合物を用いていないために起泡性が高く、顔料分散体の長期保存安定性が不十分である。
比較例１１は、本発明の化合物を用いていないために起泡性が高い。
比較例１２は、本発明の化合物を用いていないために、顔料の初期分散性及び顔料分散体の長期保存安定性が不十分である。
From the results in Table 2, it can be seen that the compounds of Examples 1 to 11 are low in foaming properties, and pigment dispersions excellent in initial dispersibility and long-term storage stability can be obtained.
On the other hand, since the comparative example 1 does not use the compound of the present invention, the initial dispersibility of the pigment and the long-term storage stability of the pigment dispersion are insufficient.
In Comparative Example 2, since the number of carbon atoms of the hydrocarbon group of the compound represented by the formula (1) is larger than the range of the present invention, the foaming property is high, and the ratio of the oxybutylene group in the molecule is within the range of the present invention. Since it is smaller, the long-term storage stability of the pigment dispersion is insufficient.
In Comparative Example 3, since the number of carbon atoms of the hydrocarbon group of the compound represented by the formula (1) is larger than the range of the present invention, the foamability is high, and the ratio of the oxybutylene group in the molecule is within the range of the present invention. Since it is smaller, the long-term storage stability of the pigment dispersion is insufficient.
In Comparative Example 4, since the number of added oxyethylene groups of the compound represented by the formula (1) is larger than the range of the present invention and the proportion of oxybutylene groups in the molecular weight is smaller than the range of the present invention, The initial dispersibility and the long-term storage stability of the pigment dispersion are insufficient.
Comparative Example 5 shows no water solubility because the number of moles of oxybutylene groups added to the compound represented by formula (1) is larger than the range of the present invention, and the initial dispersibility of the pigment and the long-term storage stability of the pigment dispersion. Is insufficient.
In Comparative Example 6, the number of moles of oxybutylene groups added to the compound represented by formula (1) is smaller than the range of the present invention, and the proportion of oxybutylene groups in the molecular weight is smaller than the range of the present invention. The initial dispersibility and the long-term storage stability of the pigment dispersion are insufficient.
In Comparative Example 7, the number of moles of oxyethylene groups added to the compound represented by formula (1) is smaller than the range of the present invention, and the proportion of oxybutylene groups in the molecular weight is larger than the range of the present invention. The initial dispersibility of the pigment and the long-term storage stability of the pigment dispersion are insufficient.
Since Comparative Example 8 does not use the compound of the present invention, the foaming property is high, and the long-term storage stability of the pigment dispersion is insufficient.
Since Comparative Example 9 does not use the compound of the present invention, the initial dispersibility of the pigment and the long-term storage stability of the pigment dispersion are insufficient.
Since Comparative Example 10 does not use the compound of the present invention, the foaming property is high, and the long-term storage stability of the pigment dispersion is insufficient.
Since Comparative Example 11 does not use the compound of the present invention, the foaming property is high.
Since Comparative Example 12 does not use the compound of the present invention, the initial dispersibility of the pigment and the long-term storage stability of the pigment dispersion are insufficient.
本発明によれば、起包性が低く、顔料の初期分散性及び顔料分散体の長期保存安定性に優れた顔料分散剤、及び顔料分散体が提供される。このような顔料分散体は、水性フェルトペン、水性ボールペン、水性塗料、特に水性インクジェット用インクとして好適に用いることができる。 ADVANTAGE OF THE INVENTION According to this invention, the pigment dispersant and pigment dispersion which were low in the packing property and excellent in the initial dispersibility of a pigment and the long-term storage stability of a pigment dispersion are provided. Such a pigment dispersion can be suitably used as a water-based felt pen, a water-based ball-point pen, a water-based paint, particularly a water-based inkjet ink.
Claims (2)
Ｒ１−Ｏ−（ＥＯ）ｍ−（ＢＯ）ｎ−Ｒ２ （１）
（式中、Ｒ１は炭素数１〜４の炭化水素基、Ｒ２は水素原子又は炭素数１〜４の炭化水素基、ＥＯはオキシエチレン基、ＢＯはオキシブチレン基、ｍはオキシエチレン基の平均付加モル数、ｎはオキシブチレン基の平均付加モル数を示し、ｍは８〜２６、ｎは８〜１４、ｍ＋ｎは１６〜３２であって、分子量中に占めるオキシブチレン基部分の割合は４５〜７５質量％である。） An aqueous pigment dispersant comprising a compound represented by the formula (1) and having a molecular weight of 1000 to 2000.
R 1 —O— (EO) m — (BO) n —R 2 (1)
(In the formula, R 1 is a hydrocarbon group having 1 to 4 carbon atoms, R 2 is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, EO is an oxyethylene group, BO is an oxybutylene group, and m is an oxyethylene group. The average addition mole number of n, n shows the average addition mole number of an oxybutylene group, m is 8-26, n is 8-14, m + n is 16-32, The ratio of the oxybutylene group part which occupies in molecular weight Is 45 to 75% by mass.)
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| JP2010071730A JP2011202063A (en) | 2010-03-26 | 2010-03-26 | Aqueous pigment dispersant and aqueous pigment dispersion including the same |
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| JP2010071730A JP2011202063A (en) | 2010-03-26 | 2010-03-26 | Aqueous pigment dispersant and aqueous pigment dispersion including the same |
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| JP2011202063A true JP2011202063A (en) | 2011-10-13 |
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