JPH0857288A - Dispersant and dispersing element - Google Patents

Abstract

PURPOSE: To obtain a dispersant and a dispersing element suitable for dispersing a fine substance insoluble in an org. medium throughout the org. medium by adding ester obtained by reacting a polymer of hydroxycarboxylic acid with polyhydric alcohol in the presence of a basic catalyst. CONSTITUTION: A polymer a hydroxycarboxylic acid is obtained by heating the hydroxycarboxylic acid to 100-300 deg.C in the presence of a basic catalyst and removing formed water to the outside of the system. A dispersant is obtained by the esterifying reaction of the obtained polymerized hydroxycarboxylic acid with a polyhydric alcohol in the presence of a basic catalyst. As an org. medium to which this dispersant is adapted, there are vehicle of printing ink or paint, plastic and the like. A dispersant compsn. is obtained by both of a method wherein the dispersant is preliminarily adsorbed on the surface of a fine substance insoluble in the org. medium before the fine substance is mixed with the org. medium and a method wherein the dispersant is mixed with and dissolved in the org. medium before the fine substance insoluble in the org. medium is added to and mixed with the org. medium.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention aims to provide a dispersant and a dispersion suitable for dispersing a fine substance insoluble in an organic medium in the organic medium, and the fields of use thereof are inks, paints and plastics. It covers a wide range of materials.

[0002]

2. Description of the Related Art Generally, the surface of pigments, ceramics, fillers, flame retardants, magnetic powders, etc. shows extremely strong hydrophilicity due to the presence of hydrophilic functional groups such as hydroxyl groups and adsorbed water. In this case, the dispersibility in an organic medium such as paint, ink, and plastic is poor, and various problems occur. That is, dispersibility is poor in the process of producing a dispersion containing a fine substance that is insoluble in an organic medium exhibiting strong hydrophilicity, and the viscosity of the mixture is significantly increased during stirring and mixing, making it difficult to handle, or the product quality due to poor dispersion. Problems such as deterioration occur.
Therefore, various methods have been proposed in the prior art, and some of them have been recognized to be effective. For example, Japanese Patent Publication No. 54-34009 describes a dispersant for a polyester having a carboxyl group at the terminal and obtained by dehydrating 2 molecules or more of 12-hydroxystearic acid or a salt thereof. . In addition, JP-A-54-3
Japanese Patent No. 7082 describes a method for preparing a pigment dispersion for ink production, which comprises a reaction product of the polyester and polyimine. Japanese Patent Publication No. 1-270932 describes a dispersant for a powdery or granular substance having a hydrophilic surface, which is composed of a reaction product of a polyester compound of an oxy acid having a carboxyl group at a terminal and a polyhydric alcohol. , Phosphoric acid, phosphorous acid, P-toluenesulfonic acid, as a catalyst at the time of reaction of oxyacid and esterification,
Techniques using tetra-n-butyl titanate and tetraisopropyl titanate are disclosed.

[0003]

Among the conventional dispersants, no dispersant having sufficiently satisfactory performance has been obtained due to problems such as poor fluidity of the dispersion, aggregation and precipitation. A dispersant that forms a highly stable dispersion has been desired.

[0004]

The present inventors have completed the present invention as a result of earnest research in view of the above problems. That is, the present invention is a dispersant for a fine substance insoluble in an organic medium, which is composed of an ester obtained by reacting a polymer of hydroxycarboxylic acid and a polyhydric alcohol under a basic catalyst, and the dispersant and the organic medium, It is a dispersion composed of a fine substance insoluble in the organic medium. More specifically, it is a dispersant composed of an ester obtained by reacting a polymer of a hydroxycarboxylic acid obtained by reacting in the presence of a basic catalyst with a polyhydric alcohol in the presence of a basic catalyst. The hydroxycarboxylic acid of the dispersant of the present invention is a fatty acid having a hydroxyl group in the molecule, and examples thereof include sabinic acid, 2-hydroxytetradecanoic acid, ipro-acid, 2-hydroxyhexadecanoic acid, and yarapino-.
Acid, Yumperic Acid, Amblet-Acid, Aryutritic Acid, 2-Hydroxystearic Acid, 12-Hydroxystearic Acid, 18-Hydroxystearic Acid, Ricino-acid, Camuloleic Acid, Licanoic Acid, Ferronic Acid, Celebrone Acid, 1 of 9,10-dihydroxystearic acid
Examples thereof include two or more, and ricinoleic acid and 12-hydroxystearic acid are preferable.

The basic catalyst of the present invention is a substance that releases hydroxide ion in an aqueous solution, such as metal hydroxide,
Examples thereof include metal alkoxides, metal amides and alkali metal salts. For metal hydroxides, sodium hydroxide, potassium hydroxide, calcium hydroxide, etc .; for metal alkoxides, sodium ethoxide, sodium methoxide, etc.
Examples of the metal amide include lithium diisopropylamide and lithium diethylamide, and examples of the alkali metal salt include sodium acetate, potassium acetate, lithium acetate and the like, but metal hydroxide and alkali metal salt are preferable. The hydroxycarboxylic acid polymer is obtained by heating the hydroxycarboxylic acid in the presence of the basic catalyst at 100 ° C. to 300 ° C., preferably 140 ° C. to 240 ° C., and removing the produced water out of the system. The reaction is preferably carried out in the presence of an inert gas. It may also be carried out in an azeotropic solvent such as toluene or xylene. The progress of these reactions can be confirmed by measuring the amount of distilled water and the acid value of the reaction product. The acid value of the polymerized hydroxycarboxylic acid thus obtained is 10 to 150, preferably 20 to 90. Examples of polyhydric alcohols include alkane polyols, saccharides, saccharide derivatives, polyalkane polyols, and mixtures of two or more thereof. As the alkane polyol, pentaerythritol, glycerin, propylene glycol or the like, sucrose or the like as the saccharide, saccharide alcohols as the saccharide derivative, for example, sorbitol, mannitol or the like, as the polyalkane polyol, di or tripentaerythritol, Examples thereof include polyglycerin such as diglycerin, triglycerin, tetraglycerin, hexaglycerin and decaglycerin. The dispersant of the present invention is obtained by reacting a polymerized hydroxycarboxylic acid and a polyhydric alcohol under a basic catalyst to esterify them.

The esterification reaction of the present invention is carried out in the presence of the above basic catalyst at 100 ° C to 300 ° C, preferably 120 ° C to 2 ° C.
It is obtained by heating in the range of 60 ° C. and removing the produced water out of the system. The reaction is preferably carried out in the presence of an inert gas. It may also be carried out in an azeotropic solvent such as toluene or xylene. The progress of these reactions can be confirmed by measuring the amount of distilled water and the acid value of the reaction product. The basic catalyst of the present invention may be added either at the time of polymerization of hydroxy fatty acid or at the time of both polymerization of hydroxy fatty acid and esterification reaction with polyhydric alcohol. The fine material insoluble in the organic medium to which the dispersant of the present invention is applied includes inorganic pigments, organic pigments, ceramics, fillers, flame retardants, reinforcing materials and magnetic materials, for example, titanium dioxide, kaolin, talc, Bentonite, mica, red iron oxide, clay, calcium carbonate, carbon black, zinc stearate, alumina,
Metal powders such as silica, zirconia, silicon carbide, silicon nitride, boron nitride, barium sulfate, calcium sulfate, aluminum hydroxide, iron oxide, magnesium carbonate, iron, zinc, nickel, copper, aluminum, metal oxides, non-oxides. Ceramics, or cellulosics such as wood flour, fibrous substances such as glass fiber, carbon fiber, aramid fiber, etc., azo, thioindigo, anthraquinone, antrantron, isodibenzanthrone, trifenedioxazine, copper Phthalocyanines and their nuclear halogen-substituted derivatives, phthalocyanine pigments such as copper tetraphenyl and octaphenyl phthalocyanine, quinacridone pigments, lakes, and organic compounds such as toners. 100μ
A spherical shape, a flaky shape, an indefinite shape, a needle shape, or a fibrous shape having a particle diameter of 30 μm or less is preferable.

The organic medium to which the dispersant of the present invention is applied includes vehicles for printing inks and paints, plastics, and the like. Examples of such an organic medium include aromatics such as benzene, toluene and xylene. Hydrocarbons,
Liquid paraffin, hexane, petroleum hydrocarbons such as mineral spirits, chloroform, carbon tetrachloride, halogenated hydrocarbons such as chlorobenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as isophorone, ethyl acetate, acetic acid. Esters such as butyl, dioctyl phthalate, dibutyl phthalate, cutting oil, linseed oil, castor oil, soybean oil, cottonseed oil, coconut oil, safflower oil, plastics such as polyethylene, polypropylene, polystyrene, vinyl chloride resin,
Vinylidene chloride resin, methacrylic resin, polycarbonate
G, saturated polyester, AS resin, ABS resin, phenol resin, urea resin, melamine resin, epoxy resin,
Examples include polyurethane, alkyd resin, and unsaturated polyester. The addition amount of the dispersant of the present invention is 0.01 to 100% by weight, preferably 0.1 to 50% by weight, based on the fine substance insoluble in the organic medium. The content of the fine substance insoluble in the organic medium in the organic medium is 5 to 95% by weight, preferably 10 to 80% by weight. The dispersant composition of the present invention is adsorbed on the surface of a fine substance that is insoluble in an organic medium in advance, and then mixed with the organic medium or mixed with and dissolved in the organic medium and then dissolved in the organic medium. It can be obtained by adding a fine substance and mixing.

[0008]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. Example 1 500 g of industrial 12-hydroxystearic acid and 0.2 g of sodium hydroxide were added to a 1-liter four-necked flask, and 180 ° C. was added while removing generated water under a nitrogen stream.
Polymerized by reacting for 15 hours 12-hydroxystearic acid 4
75 g was obtained. The acid value of this product was 45.5. Then, the obtained polymerized 12-hydroxystearic acid 40
19 g of hexaglycerin and 0.5 g of sodium hydroxide were mixed with each other in a nitrogen stream while removing the produced water.
The reaction was carried out at 0 ° C. for 8 hours to obtain 520 g of the dispersant of the present invention.
The acid value of this dispersant was 1.1. Example 2 500 g of industrial 12-hydroxystearic acid was added to a 1-liter four-necked flask, and the reaction was carried out at 180 ° C. for 6 hours while removing generated water under a nitrogen stream to polymerize 480 g of 12-hydroxystearic acid. Obtained. The acid value of this product was 66.5. Next, 400 g of polymerized 12-hydroxystearic acid obtained, 300 g of decaglycerin and 0.4 g of sodium hydroxide were mixed and reacted under a nitrogen stream at 190 ° C. for 7 hours while removing the produced water to obtain 650 g of the dispersant of the present invention. Obtained. The acid value of this dispersant was 0.8.

Example 3 Industrial ricinoleic acid 5 was placed in a 1 liter four-necked flask.
Add 00g and remove generated water under nitrogen stream 1
Reaction was carried out at 90 ° C. for 12 hours to obtain 463 g of polymerized ricino-acid. The acid value of this product was 40.2. Then, 400 g of the obtained polymerized ricino-acid and 80 g of sorbitol.
And 0.5 g of lithium hydroxide were mixed and reacted at 190 ° C. for 7 hours while removing generated water under a nitrogen stream to obtain 440 g of the dispersant of the present invention. The acid value of this dispersant was 1.5. Example 4 To a 1-liter four-necked flask, 200 g of industrial 12-hydroxystearic acid, 300 g of ricinoleic acid and 0.2 g of sodium acetate were added, and the generated water was removed under a nitrogen stream at 190 ° C. and 20 ° C. After reaction for a time, 458 g of polymerized mixed hydroxy fatty acid was obtained. The acid value of this product is 35.
It was 2. Then, 400 g of the obtained polymerized mixed hydroxy fatty acid, 200 g of tetraglycerin and 0.3 g of sodium acetate were mixed and reacted at 180 ° C. for 10 hours under a nitrogen stream while removing generated water to obtain 540 g of the dispersant of the present invention. The acid value of this dispersant was 0.2. Example 5 Polymerized hydroxystearic acid 100 obtained in Example 1
g, diglycerin 15g and calcium hydroxide 0.5g
And remove the generated water under nitrogen stream 180
After reacting at 8 ° C. for 8 hours, 104 g of the dispersant of the present invention was obtained. The acid value of this dispersant was 2.0.

Comparative Example 1 500 g of industrial 12-hydroxystearic acid and P-toluenesulfonic acid of 0.1 g were put in a 1-liter four-necked flask.
3 g was added, and while removing the produced water under a nitrogen stream, 19
The reaction was carried out at 0 ° C. for 10 hours to obtain 470 g of polymerized 12-hydroxystearic acid. The acid value of this product was 46.3. Next, 400 g of the polymerized 12-hydroxystearic acid obtained, 150 g of hexaglycerin and 0.5 g of P-toluenesulfonic acid were mixed and reacted at 190 ° C. for 10 hours while removing generated water under a nitrogen stream to obtain 515 g of a dispersant. It was The acid value of this dispersant was 1.4. Comparative Example 2 500 g of industrial 12-hydroxystearic acid and 0.3 g of tetra-n-butyl titanate were added to a 1-liter four-necked flask, and reacted at 180 ° C. for 6 hours while removing generated water under a nitrogen stream. Thus, 481 g of polymerized 12-hydroxystearic acid was obtained. The acid value of this product is 64.2.
Met. Next, 400 g of the polymerized 12-hydroxystearic acid obtained and 300 g of decaglycerin were mixed and reacted at 190 ° C. for 7 hours while removing the produced water under a nitrogen stream to obtain 663 g of a dispersant. The acid value of this dispersant was 0.4. Comparative Example 3 1-liter four-necked flask was charged with industrial ricinoleic acid 5
Add 00g and remove generated water under nitrogen stream 1
The reaction was carried out at 80 ° C. for 8 hours to obtain 475 g of polymerized ricinoleic acid. The acid value of this product was 40.1. Then, 400 g of the polymerized ricinoleic acid thus obtained, 80 g of sorbitol and 0.5 g of phosphoric acid were mixed and reacted at 190 ° C. for 7 hours while removing generated water under a nitrogen stream to obtain 453 g of a dispersant.
The acid value of this dispersant was 1.7.

Comparative Example 4 200 g of industrial 12-hydroxystearic acid and 300 g of ricinoleic acid were added to a 1-liter four-necked flask, and the produced water was removed under a nitrogen stream at 190 ° C. for 24 hours.
After reaction for a time, 460 g of polymerized mixed hydroxy fatty acid was obtained. The acid value of this product was 36.0. Then, 400 g of the polymerized mixed hydroxy fatty acid thus obtained and 200 g of tetraglycerin were mixed and reacted at 180 ° C. for 10 hours while removing generated water under a nitrogen stream to obtain 534 g of a dispersant. The acid value of this dispersant was 1.2. Comparative Example 5 500 g of industrial 12-hydroxystearic acid was added to a 1-liter four-necked flask, and the reaction was carried out at 180 ° C. for 6 hours while removing the produced water under a nitrogen stream to obtain 476 g of polymerized 12-hydroxystearic acid. Obtained. The acid value of this product was 60.1. Next, 400 g of the polymerized 12-hydroxystearic acid thus obtained, 50 g of hexaglycerin and 0.4 g of tetraisopropyl titanate were mixed and reacted at 180 ° C. for 8 hours while removing generated water under a nitrogen stream to obtain 453 g of a dispersant. The acid value of this dispersant was 1.7. Comparative Example 6 The polymerized 12-hydroxystearic acid obtained in Example 1 is used as the dispersant of Comparative Example 6.

Test Example 1 The dispersant of the present invention obtained in Examples 1 to 5 and Comparative Examples 1 to 1
The dispersibility of the dispersant obtained in No. 6 in titanium dioxide was evaluated by the following method. Titanium dioxide 60 parts Organic medium 20 parts Dispersant 1 part The above formulation was thoroughly mixed with a ball mill at 25 ° C., and its properties were confirmed. The results are shown in Table 1.

[0013]

[Table 1]

Test Example 2 Dispersants of the present invention obtained in Examples 1-5 and Comparative Examples 1-
The dispersibility for calcium carbonate obtained in 6 was evaluated by the following method. Calcium carbonate 80 parts Organic medium 20 parts Dispersant 1 part The above formulation was thoroughly mixed with a ball mill at 25 ° C., and its properties were confirmed. Table 2 shows the results.

[0015]

[Table 2]

Test Example 3 The dispersant of the present invention obtained in Examples 1 to 5 and Comparative Examples 1 to 1
The dispersibility of the dispersant obtained in No. 6 in carbon black was evaluated by the following method. Carbon black 60 parts Organic medium 20 parts Dispersant 1 part The above formulation was thoroughly mixed with a ball mill at 25 ° C., and its properties were confirmed. The results are shown in Table 3.

[0017]

[Table 3]

Test Example 4 The dispersant of the present invention obtained in Examples 1 to 5 and Comparative Examples 1 to 1
The dispersibility of the dispersant obtained in No. 6 in alumina was evaluated by the following method. Alumina 60 parts Organic medium 20 parts Dispersant 1 part The above formulation was thoroughly mixed with a ball mill at 25 ° C., and its properties were confirmed. The results are shown in Table 4.

[0019]

[Table 4]

Test Example 5 The dispersant of the present invention obtained in Examples 1 to 5 and Comparative Examples 1 to 1
The dispersibility of the dispersant obtained in No. 6 in copper phthalocyanine was evaluated by the following method. Copper phthalocyanine 20 parts Organic medium 50 parts Dispersant 1 part The above formulation was thoroughly mixed with a ball mill at 25 ° C., and its properties were confirmed. The results are shown in Table 5.

[0021]

[Table 5]

Test Example 6 The dispersant of the present invention obtained in Examples 1 to 5 and Comparative Examples 1 to 1
The dispersibility of the dispersant obtained in No. 6 in aluminum hydroxide was evaluated by the following method. Aluminum hydroxide 60 parts Organic medium 20 parts Dispersant 1 part The above formulation was thoroughly mixed with a ball mill at 25 ° C., and its properties were confirmed. The results are shown in Table 6.

[0023]

[Table 6]

Test Example 7 The dispersant of the present invention obtained in Examples 1 to 5 and Comparative Examples 1 to 1
The dispersibility of the dispersant obtained in No. 6 in iron powder was evaluated by the following method. Iron powder 80 parts Organic medium 30 parts Dispersant 2 parts The above formulation was thoroughly mixed with a ball mill at 25 ° C., and its properties were confirmed. The results are shown in Table 7.

[0025]

[Table 7]

The following can be considered as an embodiment of the present invention. (1) A dispersant for a fine substance insoluble in an organic medium, which is an ester and is obtained by reacting a polymer of a hydroxycarboxylic acid and a polyhydric alcohol in the presence of a basic catalyst. (2) Fine particles insoluble in the organic medium according to (1) above, which consist of an ester obtained by reacting a hydroxycarboxylic acid polymer obtained by reaction in the presence of a basic catalyst with a polyhydric alcohol in the presence of a basic catalyst. A dispersant for substances. (3) The dispersant for a fine substance insoluble in an organic medium according to the above (1) or (2), wherein the hydroxycarboxylic acid is 12-hydroxystearic acid. (4) The dispersant for a fine substance insoluble in an organic medium according to (1) or (2), wherein the hydroxycarboxylic acid is ricinoleic acid. (5) The dispersant for a fine substance insoluble in an organic medium according to (1) or (2), wherein the polyhydric alcohol is polyglycerin. (6) The above (1), wherein the polyhydric alcohol is glycerin,
The dispersant for fine substances insoluble in the organic medium according to (2). (7) The dispersant for a fine substance insoluble in an organic medium according to (1) or (2), wherein the polyhydric alcohol is sorbitol.

(8) The dispersant for a fine substance insoluble in an organic medium as described in (1) or (2) above, wherein the basic catalyst is sodium hydroxide. (9) The above (1), wherein the basic catalyst is potassium hydroxide,
The dispersant for fine substances insoluble in the organic medium according to (2). (10) The above (1), wherein the basic catalyst is potassium acetate,
The dispersant for fine substances insoluble in the organic medium according to (2). (11) The dispersant for a fine substance insoluble in an organic medium according to the above (1) or (2), wherein the basic catalyst is sodium acetate. (12) A dispersion comprising a dispersant for a fine substance insoluble in the organic medium according to (1) and (2), an organic medium, and a fine substance insoluble in the organic medium. (13) The organic medium is vinyl chloride, polyolefin resin,
The above (1) consisting of one or more ABS resins.
The dispersion according to 2). (14) The dispersion as described in (12) above, wherein the organic medium is one or more of phenol resin, urea resin, melamine resin, polyurethane resin and epoxy resin. (15) The dispersion as described in (12) above, wherein the fine substance insoluble in the organic medium is an inorganic pigment or an organic pigment. (16) The dispersion as described in (12) above, wherein the fine substance insoluble in the organic medium is ceramic. (17) The dispersion as described in (12) above, wherein the fine substance insoluble in the organic medium is a filler. (18) The dispersion as described in (12) above, wherein the fine substance insoluble in the organic medium is a magnetic material. (19) Particle size of fine material insoluble in organic medium is 100 μm
The dispersion according to the above (12), which is:

[0028]

As is apparent from the above examples, according to the present invention, a dispersant and a dispersion suitable for dispersing a fine substance insoluble in an organic medium in the organic medium can be obtained.

Claims (3)

[Claims] 1. A dispersant comprising an ester obtained by reacting a hydroxycarboxylic acid polymer with a polyhydric alcohol in the presence of a basic catalyst. 2. An ester obtained by reacting a polymer of hydroxycarboxylic acid obtained by reacting in the presence of a basic catalyst with a polyhydric alcohol in the presence of a basic catalyst. Dispersant. 3. A dispersion comprising the dispersant according to claim 1 or 2, an organic medium and a fine substance insoluble in the organic medium.