JP5022531B2 - Organic or inorganic powder dispersion stabilizer in oil - Google Patents

Description

【０００７】
（ただし、式中Ｚは２個の水酸基をもつ化合物の残基、Ｒ^１は炭素数２〜５のアルケニル基、Ｒ^２は炭素数８〜２４の炭化水素基、ＡＯは炭素数３のオキシアルキレン基、ＢＯは炭素数４のオキシアルキレン基であり、ＡＯおよび／またはＢＯが２種類以上の場合ブロック状またはランダム状のどのように結合していてもよい。ａおよびｃは炭素数３のオキシアルキレン基の平均付加モル数、ｂおよびｄは炭素数４のオキシアルキレン基の平均付加モル数で、ａ＋ｂ＋ｃ＋ｄ＝１〜３００、１≦ｂ＋ｄを満たす。）
【０００８】
【発明の実施の形態】
式［Ｉ］においてＺを残基とする２個の水酸基をもつ化合物としては、例えばエチレングリコール、ポリエチレングリコール、プロピレングリコール、ポリプロピレングリコール、ブチレングリコール、ドデシレングリコール、オクタデシレングリコール、ネオペンチルグリコール、スチレングリコールなどの２価アルコール；カテコール、レゾルシン、ヒドロキノンなどの２価フェノールなどがあり、好ましくは炭素数２〜５の化合物である。
【０００９】
式［Ｉ］においてＲ¹で示される炭素数２〜５のアルケニル基としては、例えばビニル基、アリル基、メタリル基、１，１−ジメチル−２−プロペニル基、３−メチル−３−ブテニル基などがあり、好ましくはアリル基、メタリル基である。
【００１０】
式［Ｉ］においてＲ²で示される炭素数４〜２４の炭化水素基としては、例えばブチル基、イソブチル基、第二ブチル基、第三ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、イソトリデシル基、テトラデシル基、ヘキサデシル基、イソセチル基、オクタデシル基、ステアリル基、イソステアリル基、オクチルドデシル基、ドコシル基、デシルテトラデシル基などの脂肪族飽和炭化水素基；メタリル基、オレイル基などの脂肪族不飽和炭化水素基；シクロヘキシル基、メチルシクロヘキシル基などの脂環式飽和炭化水素基；シクロペンテニル基、シクロヘキセニル基などの脂環式不飽和炭化水素基；フェニル基、ベンジル基、クレジル基、ブチルフェニル基、ジブチルフェニル基、オクチルフェニル基、ノニルフェニル基、ドデシルフェニル基、ジオクチルフェニル基、ジノニルフェニル基、α−メチルベンジルフェニル基などの芳香族炭化水素基または置換芳香族炭化水素基があり、これらは１種または２種以上を混合して用いてもよく、好ましくは脂肪族飽和炭化水素基である。炭素数が４〜２４であるのは共重合体の親油性および分散安定性を高めるためであり、炭素数が４未満だと親油性が低くなり、２４を超えると共重合体の粘度が高くなり製造が困難になるため好ましくない。
【００１１】
式［Ｉ］において、ＡＯで示される炭素数２〜３のオキシアルキレン基としては、オキシエチレン基、オキシプロピレン基などがある。
式［Ｉ］において、ＢＯで示される炭素数４〜８のオキシアルキレン基としては、例えば１，２−オキシブチレン基、１，３−オキシブチレン基、２，３−オキシブチレン基、オキシテトラメチレン基、オキシスチレン基などがあり、炭素数４〜８のオキシアルキレン基を必須とするのは、共重合体の親油性および分散安定性を高めるためである。また、オキシアルキレン基が２種類以上のときはブロック状またはランダム状のどのように結合していてもよい。
また、ａおよびｃは炭素数２〜３のオキシアルキレン基の平均付加モル数を表し、ｂおよびｄは炭素数４〜８のオキシアルキレン基の平均付加モル数を表し、ａ＋ｂ＋ｃ＋ｄ＝１〜３００、１≦ｂ＋ｄを満たし、ａ＋ｂ＋ｃ＋ｄ＝１〜５０を満たすことがより好ましい。ａ＋ｂ＋ｃ＋ｄが３００より大きくなると式［Ｉ］で示されるポリオキシアルキレン化合物の粘度が高くなり、製造が困難となるため好ましくない。
【００１２】
（ｂ）のマレイン酸系化合物としては、無水マレイン酸、マレイン酸、マレイン酸塩およびマレイン酸エステルなどがあり、無水マレイン酸であることが好ましい。マレイン酸塩としては、リチウム、ナトリウム、カリウムなどのアルカリ金属塩、アンモニウム塩、メチルアミン、ジメチルアミン、エチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、メチルエタノールアミンなどのアミン塩が挙げられ、塩はモノ体であってもジ体であってもよく、マレイン酸塩としてはアンモニウム塩、アミン塩がより好ましい。
【００１３】
（ｃ）のその他の共重合可能な単量体としては、例えばスチレン、酢酸ビニル、ビニルスルホン酸、アリルスルホン酸、メタリルスルホン酸、アクリル酸、メタクリル酸、アクリル酸エステル、メタクリル酸エステル、アクリロニトリル、メタクリロニトリル、アクリルアミド、メタクリルアミドおよびイソブチレン、ジイソブチレン、ビニルシクロヘキサンなどのオレフィンがあり、塩であってもよく、好ましくはスチレンおよびオレフィンである。これらは、親油性および分散安定性を高めるために必要である。
【００１４】
本発明の有機または無機粉末の油中分散安定剤において、式［１］で表されるポリオキシアルキレン誘導体の単位（ａ）、マレイン酸系化合物の単位（ｂ）およびその他の共重合可能な単量体の単位（ｃ）の組成比は、モル％で（ａ）：（ｂ）：（ｃ）=３５〜６５：３５〜６５：０．１〜３０である。
【００１５】
ポリオキシアルキレン誘導体の単位（ａ）に対してマレイン酸系化合物の単位（ｂ）がこの範囲より多くても少なくても、分散安定性が低下するため好ましくない。また、ポリオキシアルキレン誘導体の単位（ａ）に対して、その他の共重合可能な単量体の単位（ｃ）がこの範囲より多くても少なくても分散安定性が低下するため好ましくない。
【００１６】
本発明の特定の共重合体からなる油中分散安定剤において、共重合体の重量平均分子量は、１，０００〜７０，０００であり、５，０００〜５０，０００であることがより好ましい。重量平均分子量が１，０００より小さいと分散安定性が低下するため好ましくなく、７０，０００を超える共重合体は粘度が高くなり、製造が困難となるので好ましくない。
【００１７】
本発明で分散の対象となる有機粉末は特に限定されないが、例えば不溶性アゾ顔料、フタロシアニンブルー、染色レーキ、イソインドリノン、キナクリドン、ジオキサジンバイオレット、ペリノン、ペリレンなどの有機顔料；ポリアミド系合成樹脂、ポリエステル系合成樹脂、ポリオレフィン系合成樹脂、ポリカーボネート、ポリ塩化ビニル、ポリメチルメタクリレート、フッ素樹脂などの合成樹脂粉末；ステアリン酸アルミニウム、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン酸マグネシウム、ステアリン酸鉛、ステアリン酸カドミウム、ステアリン酸バリウム、ラウリン酸カルシウム、ラウリン酸亜鉛などの金属せっけんの他、木粉などがあげられる。
【００１８】
無機粉末に関しても特に限定されないが、例えばカオリン、ケイ酸アルミニウム、クレー、タルク、マイカ、アスベスト粉、ケイ酸カルシウム、セリサイト、ベントナイトなどのケイ酸塩、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム、ドロマイトなどの炭酸塩、硫酸カルシウム、硫酸バリウムなどの硫酸塩、マグネシア、アルミナ、酸化アンチモン、酸化チタン、ホワイトカーボン、ケイソウ土、酸化鉄などの金属酸化物、水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウム、水酸化鉄、メタチタン酸などの金属水酸化物、その他、炭化ケイ素、窒化ケイ素、窒化ホウ素、ジルコニア、チタン酸バリウム、サチンホワイト、カーボンブラック、グラファイトなどの無機粉末が挙げられる。
なお、これらの有機または無機粉末の平均粒子径としては、その種類によって大きく異なるが、一般的には、１００μｍ以下であり、好ましくは０．１〜５０μｍであるのがよい。
【００１９】
本発明において上記の有機または無機粉末を分散させる分散媒となる油も特に限定されず、例えば灯油、軽油、重油などの燃料油；ヘキサン、シクロヘキサン、イソオクタンなどの脂肪族炭化水素油；ベンゼン、トルエン、キシレンなどの芳香族炭化水素油；酢酸エチル、ジオクチルフタレート、大豆油、アマニ油などのエステル油；１，１，１―トリクロルエタン、トリクロルエチレン、クロルジフルオルメタンなどのハロゲン化炭化水素油；その他流動パラフィン、塗料用液状樹脂、液状ゴムなどがある。
本発明の油中分散安定剤の使用量としては、有機または無機粉末１００重量部に対して０．０１〜１０重量部、好ましくは０．０５〜７重量部とするのがよい。０．０１重量部未満では分散安定性の効果は乏しく、１０重量部より多く使用してもそれほど分散安定性の効果の向上はないので経済的に不利である。
【００２０】
【発明の効果】
本発明において、有機または無機粉末用油中分散安定剤の有効成分として、特定のポリオキシアルキレン誘導体とマレイン酸系化合物とその他共重合可能な単量体からなる共重合体を用いたことにより、分散安定剤の使用量が低濃度かつ有機または無機粉末の高濃度スラリーを短時間で油中に分散させることができるうえに、長時間にわたって安定し、かつ再分散性の優れた有機または無機粉末の油中分散体を得ることができる。
【００２１】
【実施例】
以下、具体例により本発明を説明する。分散安定剤としては第１表に示す本発明例および比較例の化合物を用いた。
【００２２】
【表１】

【００２３】
例１
油中に分散させる有機粉末として有機顔料であるキナクリドン（ヘキスト社製製品名 ＨＯＳＴＡＰＥＲＭ ＲＥＤ Ｅ３Ｂ）を用いた。３Ｌビーカーにキナクリドン３００ｇをとり、これに第１表の分散安定剤（Ａ〜Ｍ）０．５重量％を溶解したトルエン６００ｇを加え、４枚羽根のインペラーを用いて１２０ｒｐｍで３分間撹拌したのち１分間静置し、ビーカー底部のキナクリドンの残存状態からトルエンに対するぬれ性を次の４段階で評価した。
◎ ： すべての粉末が油中に分散し、全く底部に残っていない。
○ ： ほとんどの粉末が油中に分散しているが、わずかに底部に残っている。
△ ： 半分程度の粉末が底部に残っている。
× ： ほとんどの粉末が底部に残っている。
つぎに、△以上の評価のものについて、特殊機化工業（株）製のオートホモミキサーＭ型を用いて４，０００ｒｐｍで５分間撹拌したのち、５００ｍｌのメスシリンダーに入れて３日間静置し、ついで直径５ｍｍ、重量５０ｇのガラス棒をシリンダー上部に設けたガイドを通して分散体に落下させ、沈降状態を観察して分散安定性をつぎの２段階で評価した。
○ ： 棒がシリンダー底部まで到達する。
× ： 棒がシリンダー底部に到達せずに停止し、圧密層が発生している。
これらの試験結果を第２表に示す。
【００２４】
【表２】

【００２５】
例２
油中に分散させる有機粉末として金属せっけんであるステアリン酸アルミニウム４００ｇをとり、これに各分散安定剤（Ａ〜Ｍ）０．８重量％を溶解したトルエン５００ｇを加え、例１と同様な試験を行った。これらの試験結果を第３表に示す。
【００２６】
【表３】

【００２７】
例３
油中に分散させる無機粉末としてチタン酸バリウム（関東化学（株）製）３００ｇをとり、これに各分散安定剤（Ａ〜Ｍ）０．５重量％を溶解したトルエン６００ｇを加え、例１と同様の試験を行った。これらの試験結果を第４表に示す。
【００２８】
【表４】

【００２９】
例４
油中に分散させる無機粉末として酸化チタン粉末（関東化学（株）製）３００ｇを用い、これに各分散安定剤（Ａ〜Ｍ）０．４重量％を溶解した軽油７５０ｇを加え、例１と同様な試験を行った。これらの試験結果を第５表に示す。
【００３０】
【表５】

【００３１】
例５
例１で得られた油中分散体のうち、本発明例のＡ、Ｈおよび比較例のＪを使用したものについて、いったん粉末を圧密層が発生するまで沈降させ、再度３分間撹拌したのち１分間静置し、ビーカー底部のキナクリドンの残存状態から再分散性を例１と同様の方法で評価した。これらの試験結果を第６表に示す。
【００３２】
【表６】

【００３３】
例６
例３で得られた油中分散体のうち、本発明例のＡ、Ｈおよび比較例のＪを使用したものについて、例５と同様に再分散性の試験を行った。これらの試験結果を第７表に示す。
【００３４】
【表７】

【００３５】
第２表〜第５表からも明らかなように、油系での分散安定性は、比較例の分散安定剤に比べて、本発明の分散安定剤の方が優れており、また第６表および第７表から明らかなように、油系での再分散性も比較例の分散安定剤と比べて、本発明の分散安定剤の方が優れていることがわかる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an organic or inorganic powder dispersion stabilizer in oil. More specifically, the organic or inorganic powder having a high concentration is dispersed in the oil in a short time, and long-term dispersion stability is imparted at a low concentration, and the organic or inorganic powder having excellent redispersibility is provided. The present invention relates to a dispersion stabilizer in oil.
[0002]
[Prior art]
Organic powder dispersions in oil are used in various industrial fields. Examples of organic powders include organic pigments for paints and inks, synthetic resin powders, and metal soap as a lubricant for papermaking. In such a dispersion in oil, a dispersion stabilizer for dispersing the organic powder in the oil is generally used. As the dispersion stabilizer, many polymer surfactants such as polyacrylic acid and salts of copolymers thereof, and salts of copolymers of maleic anhydride and α-olefin have been proposed. However, with these dispersion stabilizers, it is difficult to disperse the organic powder at a high concentration and low viscosity that can be applied to various fields, and once the organic powder has settled, it may be redispersed. It was difficult. In order to solve these problems, for example, a copolymer composed of a polyoxyalkylene derivative and maleic anhydride as shown in JP-A-4-122429 has been proposed. The effect has not been obtained.
[0003]
On the other hand, inorganic powder dispersions in oil are used by being dispersed in oil in various industrial fields. As an example, there is a paint in which pigments and fillers are dispersed in a resin solution. In recent years, inorganic powder hydrocarbon oil dispersions have also been used as abrasives and spray cleaners for fuel oil tanks. Inorganic powders often have insufficient dispersibility alone, and therefore dispersion stabilizers are used. As the dispersion stabilizers, inorganic powders are dispersed in oil in a short time, and inorganic powders are used for a long time. The performance is required to stably disperse the powder without settling, or to easily redisperse even if the inorganic powder settles. In order to solve these problems, for example, a copolymer comprising a polyoxyalkylene derivative and maleic anhydride as shown in JP-A-2-149332 has been proposed, but the redispersibility is sufficient. I can't say that.
[0004]
[Problems to be solved by the invention]
The present invention disperses high-concentration organic or inorganic powders in oil in a short time, imparts long-term dispersion stability at a low concentration, and has excellent redispersibility. The object is to provide a medium dispersion stabilizer.
[0005]
[Means for Solving the Problems]
That is, the present invention comprises a (a) formula [I] shown and units of the polyoxyalkylene derivative and (b) units of maleic acid (c) other units copolymerizable monomer, ( The composition ratio of a), (b) and (c) is mol%, and (a) :( b) :( c) = 35-65: 35-65: 0.1-30, and the weight average molecular weight is It is an organic or inorganic powder dispersion stabilizer in oil composed of a copolymer of 1,000 to 70,000.
[0006]
[Chemical 3]

[0007]
(Wherein, Z is a residue of a compound having two hydroxyl groups , R ¹ is an alkenyl group having 2 to 5 carbon atoms, R ² is a hydrocarbon group having 8 to 24 carbon atoms, and AO is an oxy group having 3 carbon atoms. alkylene group, BO represents an oxyalkylene group having 4 carbon atoms, AO and / or BO is two or more when good .a and c be bonded how block form or random form of 3 carbon atoms The average addition mole number of the oxyalkylene group , b and d are the average addition mole number of the oxyalkylene group having 4 carbon atoms, satisfying a + b + c + d = 1 to 300 and 1 ≦ b + d.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the compound having two hydroxyl groups having Z as a residue in the formula [I] include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butylene glycol, dodecylene glycol, octadecylene glycol, and neopentyl glycol. And dihydric alcohols such as styrene glycol; dihydric phenols such as catechol, resorcin, and hydroquinone, and compounds having 2 to 5 carbon atoms are preferred.
[0009]
Examples of the alkenyl group having 2 to 5 carbon atoms represented by R ¹ in the formula [I] include a vinyl group, an allyl group, a methallyl group, a 1,1-dimethyl-2-propenyl group, and a 3-methyl-3-butenyl group. And preferably an allyl group or a methallyl group.
[0010]
Examples of the hydrocarbon group having 4 to 24 carbon atoms represented by R ² in the formula [I] include a butyl group, isobutyl group, secondary butyl group, tertiary butyl group, pentyl group, isopentyl group, neopentyl group, and hexyl group. , Heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, isotridecyl group, tetradecyl group, hexadecyl group, isocetyl group, octadecyl group, stearyl group, isostearyl group, octyldodecyl group, docosyl group, decyltetra Aliphatic saturated hydrocarbon group such as decyl group; Aliphatic unsaturated hydrocarbon group such as methallyl group and oleyl group; Alicyclic saturated hydrocarbon group such as cyclohexyl group and methylcyclohexyl group; Cyclopentenyl group, cyclohexenyl group, etc. An alicyclic unsaturated hydrocarbon group; phenyl group, benzyl group, cresyl group, There are aromatic hydrocarbon groups or substituted aromatic hydrocarbon groups such as tilphenyl group, dibutylphenyl group, octylphenyl group, nonylphenyl group, dodecylphenyl group, dioctylphenyl group, dinonylphenyl group, α-methylbenzylphenyl group, etc. These may be used alone or in combination of two or more, and are preferably aliphatic saturated hydrocarbon groups. The number of carbon atoms is 4 to 24 in order to increase the lipophilicity and dispersion stability of the copolymer. When the carbon number is less than 4, the lipophilicity is lowered, and when it exceeds 24, the viscosity of the copolymer is high. This is not preferable because the manufacturing becomes difficult.
[0011]
In the formula [I], examples of the oxyalkylene group having 2 to 3 carbon atoms represented by AO include an oxyethylene group and an oxypropylene group.
In the formula [I], examples of the oxyalkylene group having 4 to 8 carbon atoms represented by BO include 1,2-oxybutylene group, 1,3-oxybutylene group, 2,3-oxybutylene group, oxytetramethylene. Group, oxystyrene group and the like, and the reason why the oxyalkylene group having 4 to 8 carbon atoms is essential is to improve the lipophilicity and dispersion stability of the copolymer. Further, when two or more kinds of oxyalkylene groups are present, they may be bonded in any form of block or random.
A and c represent the average number of moles of the oxyalkylene group having 2 to 3 carbon atoms; b and d represent the average number of moles of the oxyalkylene group having 4 to 8 carbon atoms; a + b + c + d = 1 to 300; More preferably, 1 ≦ b + d is satisfied, and a + b + c + d = 1 to 50 is satisfied. When a + b + c + d is larger than 300, the viscosity of the polyoxyalkylene compound represented by the formula [I] becomes high and production becomes difficult.
[0012]
Examples of the maleic acid compound (b) include maleic anhydride, maleic acid, maleate and maleate, and maleic anhydride is preferred. Examples of maleates include alkali metal salts such as lithium, sodium and potassium, ammonium salts, amine salts such as methylamine, dimethylamine, ethylamine, monoethanolamine, diethanolamine, triethanolamine and methylethanolamine. May be mono- or di-form, and the maleate is more preferably an ammonium salt or an amine salt.
[0013]
Examples of the other copolymerizable monomer (c) include styrene, vinyl acetate, vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, and acrylonitrile. , Methacrylonitrile, acrylamide, methacrylamide and olefins such as isobutylene, diisobutylene and vinylcyclohexane, and may be a salt, preferably styrene and olefin. These are necessary to increase lipophilicity and dispersion stability.
[0014]
In the organic or inorganic powder dispersion stabilizer of the present invention, the unit (a) of the polyoxyalkylene derivative represented by the formula [1], the unit (b) of the maleic acid compound and other copolymerizable monomers The composition ratio of the unit (c) of the monomer is (a) :( b) :( c) = 35 to 65:35 to 65: 0.1 to 30 in mol%.
[0015]
Even if the amount (b) of the maleic acid compound is more or less than this range relative to the unit (a) of the polyoxyalkylene derivative, the dispersion stability is lowered, which is not preferable. Further, if the amount of other copolymerizable monomer units (c) is more or less than this range with respect to the polyoxyalkylene derivative unit (a), the dispersion stability is lowered.
[0016]
In the oil dispersion stabilizer comprising the specific copolymer of the present invention, the copolymer has a weight average molecular weight of 1,000 to 70,000, and more preferably 5,000 to 50,000. If the weight average molecular weight is less than 1,000, the dispersion stability is lowered, which is not preferable, and a copolymer exceeding 70,000 is not preferable because the viscosity becomes high and the production becomes difficult.
[0017]
The organic powder to be dispersed in the present invention is not particularly limited, and examples thereof include organic pigments such as insoluble azo pigments, phthalocyanine blue, dye lake, isoindolinone, quinacridone, dioxazine violet, perinone, and perylene; polyamide synthetic resins, Synthetic resin powder such as polyester synthetic resin, polyolefin synthetic resin, polycarbonate, polyvinyl chloride, polymethyl methacrylate, fluororesin; aluminum stearate, zinc stearate, calcium stearate, magnesium stearate, lead stearate, cadmium stearate In addition to metal soaps such as barium stearate, calcium laurate, and zinc laurate, wood powder and the like can be mentioned.
[0018]
The inorganic powder is not particularly limited. For example, kaolin, aluminum silicate, clay, talc, mica, asbestos powder, calcium silicate, sericite, bentonite and other silicates, calcium carbonate, magnesium carbonate, barium carbonate, dolomite, etc. Carbonates, sulfates such as calcium sulfate and barium sulfate, metal oxides such as magnesia, alumina, antimony oxide, titanium oxide, white carbon, diatomaceous earth, iron oxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, Examples thereof include metal hydroxides such as iron hydroxide and metatitanic acid, and other inorganic powders such as silicon carbide, silicon nitride, boron nitride, zirconia, barium titanate, satin white, carbon black, and graphite.
The average particle size of these organic or inorganic powders varies greatly depending on the type, but is generally 100 μm or less, preferably 0.1 to 50 μm.
[0019]
In the present invention, the oil that serves as a dispersion medium for dispersing the organic or inorganic powder is not particularly limited. For example, fuel oil such as kerosene, light oil, and heavy oil; aliphatic hydrocarbon oil such as hexane, cyclohexane, and isooctane; benzene, toluene Aromatic hydrocarbon oils such as xylene; ester oils such as ethyl acetate, dioctyl phthalate, soybean oil and linseed oil; halogenated hydrocarbon oils such as 1,1,1-trichloroethane, trichloroethylene and chlorodifluoromethane; Others include liquid paraffin, paint liquid resin, and liquid rubber.
The amount of the dispersion stabilizer in oil of the present invention is 0.01 to 10 parts by weight, preferably 0.05 to 7 parts by weight, based on 100 parts by weight of the organic or inorganic powder. If it is less than 0.01 part by weight, the effect of dispersion stability is poor, and even if it is used in an amount of more than 10 parts by weight, the effect of dispersion stability is not so much improved, which is economically disadvantageous.
[0020]
【Effect of the invention】
In the present invention, by using a copolymer comprising a specific polyoxyalkylene derivative, a maleic acid compound and other copolymerizable monomers as an active ingredient of an organic or inorganic powder dispersion stabilizer in oil, Organic or inorganic powders with low concentration of dispersion stabilizer and high concentration slurry of organic or inorganic powder can be dispersed in oil in a short time, and stable for a long time and excellent in redispersibility A dispersion in oil can be obtained.
[0021]
【Example】
Hereinafter, the present invention will be described by way of specific examples. As the dispersion stabilizer, the compounds of the present invention and the comparative examples shown in Table 1 were used.
[0022]
[Table 1]

[0023]
Example 1
As an organic powder to be dispersed in oil, quinacridone which is an organic pigment (product name HOSTAPERM RED E3B, manufactured by Hoechst) was used. Take 300 g of quinacridone in a 3 L beaker, add 600 g of toluene in which 0.5% by weight of the dispersion stabilizer (A to M) in Table 1 is dissolved, and stir for 3 minutes at 120 rpm using a 4-blade impeller. It left still for 1 minute and evaluated the wettability with respect to toluene from the residual state of quinacridone of the bottom part of a beaker in the following four steps.
A: All powders are dispersed in the oil and do not remain at the bottom.
○: Most of the powder is dispersed in the oil, but remains slightly at the bottom.
Δ: About half of the powder remains at the bottom.
X: Most of the powder remains at the bottom.
Next, about the thing of evaluation more than (triangle | delta), after stirring for 5 minutes at 4,000 rpm using the auto homomixer M type | mold made from a special machine industry, it puts in a 500 ml measuring cylinder, and leaves it still for 3 days. Then, a glass rod having a diameter of 5 mm and a weight of 50 g was dropped onto the dispersion through a guide provided at the top of the cylinder, and the sedimentation state was observed to evaluate the dispersion stability in the following two stages.
○: The rod reaches the bottom of the cylinder.
×: The rod stopped without reaching the bottom of the cylinder, and a consolidated layer was generated.
The test results are shown in Table 2.
[0024]
[Table 2]

[0025]
Example 2
400 g of aluminum stearate, which is a metal soap, is added as organic powder to be dispersed in oil, and 500 g of toluene in which 0.8% by weight of each dispersion stabilizer (A to M) is dissolved is added. went. These test results are shown in Table 3.
[0026]
[Table 3]

[0027]
Example 3
As an inorganic powder to be dispersed in oil, 300 g of barium titanate (manufactured by Kanto Chemical Co., Inc.) is taken, and 600 g of toluene in which 0.5% by weight of each dispersion stabilizer (A to M) is dissolved is added. A similar test was conducted. These test results are shown in Table 4.
[0028]
[Table 4]

[0029]
Example 4
300 g of titanium oxide powder (manufactured by Kanto Chemical Co., Inc.) was used as the inorganic powder to be dispersed in the oil, and 750 g of light oil in which 0.4% by weight of each dispersion stabilizer (A to M) was dissolved was added thereto. A similar test was conducted. These test results are shown in Table 5.
[0030]
[Table 5]

[0031]
Example 5
Of the dispersions in oil obtained in Example 1, those using A and H of the present invention example and J of the comparative example were once allowed to settle until a compacted layer was formed and stirred again for 3 minutes. The mixture was allowed to stand for minutes, and the redispersibility was evaluated in the same manner as in Example 1 from the remaining state of quinacridone at the bottom of the beaker. These test results are shown in Table 6.
[0032]
[Table 6]

[0033]
Example 6
Among the dispersions in oil obtained in Example 3, the redispersibility test was conducted in the same manner as in Example 5 using A and H of the examples of the present invention and J of the comparative example. These test results are shown in Table 7.
[0034]
[Table 7]

[0035]
As is clear from Tables 2 to 5, the dispersion stability in the oil system is superior to the dispersion stabilizer of the comparative example in comparison with the dispersion stabilizer of the comparative example. As is apparent from Table 7, the redispersibility in the oil system is also superior to the dispersion stabilizer of the comparative example.

Claims (4)

(A) a unit of a polyoxyalkylene derivative represented by the formula [I], (b) a unit of maleic anhydride, and (c) a unit of other copolymerizable monomer, (a), (b) And (c) has a composition ratio of mol% (a) :( b) :( c) = 35 to 65:35 to 65: 0.1 to 30 and a weight average molecular weight of 1,000 to 70, A dispersion stabilizer in oil of an organic or inorganic powder comprising a copolymer of 000.

(Wherein, Z is a residue of a compound having two hydroxyl groups , R ¹ is an alkenyl group having 2 to 5 carbon atoms, R ² is a hydrocarbon group having 8 to 24 carbon atoms, and AO is an oxy group having 3 carbon atoms. alkylene group, BO represents an oxyalkylene group having 4 carbon atoms, AO and / or BO is two or more when good .a and c be bonded how block form or random form of 3 carbon atoms The average addition mole number of the oxyalkylene group , b and d are the average addition mole number of the oxyalkylene group having 4 carbon atoms, satisfying a + b + c + d = 1 to 300 and 1 ≦ b + d. The organic or inorganic powder dispersion stabilizer in oil according to claim 1, wherein BO is a 1,2-oxybutylene group. The organic or inorganic powder dispersion stabilizer in oil according to claim 1, wherein the polyoxyalkylene derivative represented by the formula [I] is a compound represented by the following formula [II].

H ₂ C = CHCH ₂ O (CH (CH ₃ ) CH ₂ O) ₇ (CH (C ₂ H ₅ ) CH ₂ O) ₃ C ₁₈ H ₃₇ [II] The organic or inorganic powder dispersion stabilizer in oil according to claim 1, wherein the polyoxyalkylene derivative represented by the formula [I] is a compound represented by the following formula [III].

H ₂ C = CHCH ₂ O [(CH (C ₂ H ₅ ) CH ₂ O) ₆ / (CH ₂ CH ₂ CH ₂ CH ₂ O) ₂ ] C ₁₂ H ₂₅ [III]