JPH01270932A - Dispersant - Google Patents

Abstract

PURPOSE:To improve dispersion stability of a granulated material having a hydrophilic surface by using a reaction product of a polyester compound of an oxyacid having a carboxyl group on the terminal with a specific polyhydric alcohol as a granulated dispersant. CONSTITUTION:A polyester compound of an oxyacid having a carboxyl group on the terminal and a polyhydric alcohol having a formula I (n stands for an integer of 0-15) are reacted each other by a conventional esterification reaction to obtain a dispersant for a granulated material having a hydrophilic surface. Said dispersant and a granulated material having a hydrophilic surface are added to and dispersed in an organic solvent to prepare a dispersion composition. Inorganic or organic pigments, ceramics, etc., are among the examples of the granulated material having hydrophilic surface. The addition amount of said dispersant is 0.1-100wt.% preferably 0.1-50wt.% lased on pigments, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Application The present invention relates to a novel dispersant such as a pigment and a dispersion composition containing the dispersant.

In general, the surfaces of particulate materials such as pigments, ceramics, fillers, flame retardants, and magnetic powders are in a hydrophilic state due to the presence of hydrophilic functional groups such as hydroxyl groups and adsorbed water, so they have poor lipophilicity. If left as is, it will have poor dispersibility and miscibility in organic media such as paints, printing inks, and polymeric compounds, resulting in various problems.

In other words, dispersions containing particulate materials with hydrophilic surfaces (inks, paints, ceramic slurries) often exhibit high viscosity and are difficult to collect when stirring, dispensing the product from the dispersion machine, or transferring the product. In some cases, the viscosity increases significantly during storage, making it difficult to use, and undesirable phenomena such as flooding, floating, loss of gloss, and discoloration over time occur. Also,
Resin compositions containing fillers have problems such as poor appearance and reduced product strength due to poor dispersion of the filler. Furthermore, in the case of ceramic dispersions, if the amount of solvent in the slurry is large, not only is there a large loss of time and energy in the manufacturing process, but also the performance of the ceramic molded body is degraded.

A: To prevent the aggregation of pigments in non-aqueous paints, printing inks, polymer compounds, or ceramic slurries, various methods have been proposed, and they have been shown to be effective to some extent.

For example, Japanese Patent Publication No. 54-34009 discloses a dispersant based on a polyester having a carboxyl group at the terminal or a salt thereof obtained by dehydrating two or more molecules of hydroxycarboxylic acid such as 12-hydroxystearic acid. Are listed.

Alternatively, an ester compound of the polyester and a monohydric alcohol such as n-butanol is disclosed in JP-A-62-161.
It is described in Publication No. 863.

Further, JP-A-54-37082 describes a method for preparing a pigment dispersion for producing ink, which is made of a reaction product of the polyester and poly(lower alkylene)imine.

Furthermore, a dispersant using a compound obtained by converting the terminal carboxyl group of the polyester into a quaternary ammonium was developed in 1973.
It is described in Japanese Patent No. 7-25251.

However, despite the various attempts described above, a dispersant with sufficiently satisfactory performance in dispersing pigments and the like has not been obtained.

The purpose of the present invention is to improve the flow of the dispersion liquid when dispersing a particulate material having a hydrophilic surface in a non-aqueous organic medium. The object of the present invention is to provide a dispersant that has good properties and is effective in preventing agglomeration and forming a stable dispersion.

Means for Solving the Problems The above problems are solved by the present invention. That is, the present invention relates to a polyester compound of an oxyacid having a terminal carboxyl group and a compound having the general formula (I) CH2(OH) CH(OH) (I)
CH2(0-CH2-CH(OH)-CH2) 1l
A dispersant for a particulate material having a hydrophilic surface, characterized in that it is made of a reaction product with a polyhydric alcohol represented by -OH (in the formula, n represents an integer from 0 to 15), and the dispersant The present invention relates to a dispersion composition containing the following.

The oxyacid used as a raw material for the dispersant of the present invention is a carboxylic acid having a hydroxy group, and 12-hydroxystearic acid or ricinoleic acid is preferable. These polyester compounds can be easily obtained by heating and dehydrating 12-hydroxystearic acid and/or ricinoleic acid. This dehydration condensation reaction is carried out in the presence of a known catalyst such as phosphoric acid, phosphorous acid, p-)luenesulfonic acid, tetra-n-butyl titanate, tetraisopropyl titanate, etc., or in the absence of a catalyst, at 120 to 250°C, preferably. 14
This is carried out by removing generated water from the system while heating in the range of 0 to 210°C.

Preferably, the reaction is carried out in an azeotropic solvent such as toluene. The degree of progress of the esterification reaction due to intermolecular dehydration can be determined by the amount of distilled water and the acid value of the reactant.

Industrially, 12-hydroxystearic acid and ricinoleic acid are obtained by hydrolyzing hydrogenated castor oil and purified castor oil, respectively, so they usually contain small amounts of fatty acids such as palmitic acid and stearic acid as impurities. These impurity fatty acids do not pose a problem as raw materials for the dispersant of the present invention.

The polyhydric alcohol of general formula (■), which is the other raw material for the dispersant of the present invention, is glycerin or polyglycerin. Polyglycerol is easily obtained by condensation of glycerol. In the present invention, the general formula (
The polyhydric alcohol of I) is glycerin or a polyglycerin having an average composition of n in general formula (I) of 1 to 15, preferably 1 to 10, such as diglycerin, tetraglycerin, hexaglycerin, decaglycerin, etc. It is.

The dispersant of the present invention is obtained by an esterification reaction between a polyhydric alcohol of maximum (I) and a polyester compound of an oxyacid, and this esterification reaction is carried out by a known method similar to the above-mentioned polyesterification reaction of an oxyacid. It will be held in

-i The reaction ratio between the polyhydric alcohol of formula (I) and the oxyacid polyester compound (polyhydric alcohol/oxyacid polyester compound) is 1.0 or more, and the average value is 0.5 in the dispersant molecule. It is preferable that the above hydroxyl groups exist.

Examples of organic media to which the dispersant of the present invention is applied include vehicles for printing inks and paints, synthetic resins, and the following. For example, aromatic hydrocarbons such as toluene and xylene, mineral spirits,
Petroleum hydrocarbons such as the mineral turpentine, halogenated hydrocarbons such as chloroform, perchloroethylene, trichloroethylene, and chlorobenzene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone, ethyl acetate, and acetic acid. Esters such as butyl, amyl acetate, cellosolve acetate, dioctyl phthalate, dibutyl phthalate, alkyd resins, epoxy ester resins, melamine resins, acrylic resins, polyamide resins, polyurethane resins, vinyl resins, phenolic resins, nitrocellulose resins, etc. It will be done.

The powder or granular material having a hydrophilic surface that is dispersed in an organic medium by the dispersant of the present invention usually has a hydrophilic functional group such as a hydroxyl group or water of crystallization on the surface, or has adsorbed water on the surface. It is. Such particulate materials include inorganic or organic pigments, ceramics, fillers, flame retardants and magnetic materials, such as calcium carbonate, kaolin, mica, aluminum hydroxide, silica, clay, alumina, talc, titanium dioxide, Barium sulfate, calcium sulfate, red and yellow iron oxides, zinc yellow,
Cadmium yellow, red lead, zinc white, magnesium carbonate, asbestos, glass fiber, magnetic iron oxide, lead chromate,
Strontium chromate, carbon black, navy blue, ultramarine, aluminum, iron, zinc, magnesium, brass, nickel, copper, stainless steel and other metal powders, metal oxide ceramics, non-oxide ceramics (silicon nitride,
Inorganic compounds such as aluminum nitride, titanium nitride, titanium boride, zirconium boride, silicon carbide, titanium carbide, tungsten carbide), antimony trioxide, tribasic lead sulfate, magnetic materials, or azo pigments, lakes, toners, Examples include organic compounds such as phthalocyanine pigments, isoindoline pigments, quinacridone pigments, and dioxazine pigments.

The amount of the dispersant of the present invention added is 0°1 to 1% relative to the pigment, etc.
00% by weight, preferably 0.1 to 50% by weight. The content of pigment etc. in the dispersion medium is 5 to 80% by weight,
Preferably it is 10 to 70% by weight.

Examples of preparing dehydrated condensates of oxyacids, which are raw materials for the dispersant of the present invention, are shown in Reference Examples 1 to 4, and preparation examples of the dispersant of the present invention are shown in Production Examples 1 to 5.

Industrial 12-hydroxystearic acid (neutralization value 183,
Mix 335 g of hydroxyl value 156) and 200 g of toluene, add 0.4 g of tetra-n-butyl titanate, reflux at 180°C in a nitrogen stream for 14 hours, and separate 15.0 g of water using a water separator. did. Next, toluene was distilled off under reduced pressure to obtain 306.8 g of dark reddish brown viscous poly(12-hydroxystearic acid). The acid value of this thing is 42
It was 5mgKOH/g. The degree of condensation determined from the acid value was 4.3.

Reference Example 2 Ricinole Acid Water A mixture of 150 g of industrial grade ricinoleic acid (neutralization value 180) and 95 g of xylene was heated at 190 to 200° C. for 20 hours, and the produced water was distilled off. Then 1 xylene was added under reduced pressure.
It was removed at 50°C. 141.1 g of dark reddish brown viscous polyricinoleic acid was obtained. The acid value of this product was 3aO. The degree of condensation determined from the acid value was 4.7.

Reference Example 3 Ricinoleic Acid Dehydration A mixture of 150 g of ricinoleic acid (neutralization value 180) for industrial use and 95 g of xylene was heated at 180 to 190° C. for 10 hours, and the produced water was distilled off. Then 1 xylene was added under reduced pressure.
It was removed at 50°C. A dark reddish brown viscous polyricinoleic acid was obtained. The acid value of this product was 70.3. The degree of condensation determined from the acid value is 2. ．． It was 5.

A mixture of 250 g of the dehydrated condensate of 12-hydroxystearic acid obtained in Reference Example 1 and 7.0 g of calcium hydroxide was stirred at 190° C. for 10 minutes under a nitrogen atmosphere. Upon cooling, a transparent dark reddish brown viscous liquid poly(12-hydroxystearic acid) calcium salt was obtained. The acid value of this product was 0.5.

Reference Example 5 The dehydrated condensate of 12-hydroxystearic acid obtained in Reference Example 1 was reacted with n-butanol to prepare n-butanol ester of poly(12-hydroxystearic acid).

Production Examples 1 to 5 Various oxyacid dehydrated condensates prepared in Reference Examples 1 to 3 and the first
The polyhydric alcohols shown in the table were stirred and mixed at 200° C. for 7 hours under a nitrogen stream to proceed with the esterification reaction, thereby preparing the dispersant of the present invention. Table 1 shows the appearance and physical properties of the obtained dispersant.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples. Note that all "parts" in the examples are based on weight.

Example 1, Comparative Example 1 The dispersing ability of the dispersants of the present invention obtained in Production Examples 1 to 4 for calcium carbonate was evaluated by the following method.

That is, 100 parts of calcium carbonate, 40 parts of a plasticizer (dioctyl terephthalate), and a dispersant were mixed as shown in Table 2, thoroughly mixed in a mortar, peptized and dispersed, and then the viscosity of the system at 20'C was determined. It was measured. Show the results in Table 2. Note that the lower the viscosity of the blended system, the better the dispersion state.

Table 2 (notes) 1: Taiyo Kagaku ■ "Sunsoft" (soybean lecithin) Use Example 2, Comparative Example 2 The dispersing ability of the dispersant of the present invention for titanium oxide was evaluated by the following method.

That is, 100 parts of titanium oxide, 80 parts of a plasticizer (dioctyl terephthalate), and 2 parts of a dispersant were blended as shown in Table 3, thoroughly mixed in a mortar, peptized and dispersed, and then the viscosity of the system at 20°C was determined. It was measured. The results are shown in Table 3. Note that the lower the viscosity of the blended system, the better the dispersion state.

Below is the margin Table 3 (note) 2: Rikemar R200J (lysyl acid monoglyceride) manufactured by Riken Vitamin ■ 3: Manufactured by Riken Vitamin ■
Rikemar 0-7l-DEJ (diglycerin monooleate) use 4: Rikemar L-2 manufactured by Riken Vitamin■
Example 3 using 50J (sorbitan laurate), Comparative Example 3 The ability of the dispersant of the present invention to disperse alumina oxide was evaluated by the following method.

Alumina oxide (“Alumina A-32” manufactured by Nippon Light Metal)
80 parts of xylene, 20 parts of xylene, and a dispersant were mixed thoroughly in a mortar to peptize and disperse.

The appearance and fluidity of the blended product thus obtained were sensory evaluated and the results are shown in Table 4. The appearance and fluidity of the blended products were evaluated on the following four levels.

(Evaluation criteria for appearance and fluidity) ◎ ...... Liquid with high fluidity ○ ...... Slightly viscous liquid Δ ...... Viscous liquid with poor fluidity × ・・
...Paste with poor fluidity Table 4 Example 4, Comparative Example 4 The dispersing ability of the dispersant of the present invention in an alumina oxide-acrylic binder system was evaluated by the following method.

Alumina oxide (Nippon Light Metal ■ "Alumina A-32J")
80 parts, xylene 20 parts, 3 parts of acrylic binder (10% toluene/ethyl acetate solution of acrylic resin rCB-7 manufactured by Sanyo Chemical Industries, Ltd.), and a dispersant were mixed thoroughly in a mortar and then peptized and dispersed. I let it happen. The appearance and fluidity of the thus obtained blended product were sensory evaluated in accordance with Example 3. The results are shown in Table 5.

Table 5 Example 5, Comparative Example 5 The ability of the dispersant of the present invention to disperse white carbon was evaluated by the following method.

5 parts of white carbon (Nip Seal N-220J (wet method ultrafine silicic acid) manufactured by Nippon Silikani Industry), 20 parts of xylene, and a dispersant are mixed as shown in Table 6, and thoroughly mixed in a mortar to deflocculate. The appearance and fluidity of the blended product thus obtained were sensory evaluated in accordance with Example 3. The results are shown in Table 6.

Table 6 Example 6, Comparative Example 6 The ability of the dispersant of the present invention to disperse aluminum hydroxide was evaluated by the following method.

100 parts of aluminum hydroxide (manufactured by Nippon Light Metal Corporation [Alumina Hydroxide B103J]), liquid paraffin (Nippon Oil Corporation)
40 parts of "High White 350J" (manufactured by J.D. Co., Ltd.) and 3 parts of a dispersant were mixed as shown in Table 7, and thoroughly mixed in a mortar to cause peptization and dispersion. Sensory evaluation was performed according to Example 3. The results are shown in Table 7.

Table 7 Example 7, Comparative Example 7 Barium sulfate related to the dispersant of the present invention (manufactured by Sakai Chemical Industry Co., Ltd. [Barifine BF-IJ, Bengara, antimony trioxide (
Sumitomo Metal Mining Co., Ltd. K class), zinc oxide (Wako Pure Chemical Industries, Ltd.)
reagents manufactured by Nippon Talc), talc (talc swJ manufactured by Nippon Talc)
), tribasic lead sulfate (Nitto Kasei Kogyo Co., Ltd.'s "Tribase"), barium ferrite, etc., were evaluated by the following method.

The above various powder dispersoids) and dispersants are blended into dioctyl terephthalate (DOP) in the proportions shown in Table 8,
The mixture was sufficiently mixed in a mortar to peptize and disperse, and the viscosity at 20°C was measured. The results are shown in Table 8.

Below is a blank space Table 8 Example 8, Comparative Example 8 Carbon black related to the dispersant of the present invention (Mitsubishi Kasei ■
rMA-100J), phthalocyanine blue (Blue NRO-2, manufactured by Sumika Color ■), navy blue, ultramarine, pink E (Hostapalm Bink E, manufactured by Hoechst), Carmine 6B (Carmine 6B rNo, manufactured by Daido Chemical ■) , 652J
) was evaluated according to Example 7. The results are shown in Table 9.

Table 9 below: Effects of the invention - By using the dispersant of the invention, the following effects can be obtained.

(1) The dispersant of the present invention allows stable dispersion of pigments, etc., without fear of deterioration, and exhibits the original properties (coloring power, gloss, physical properties) of pigments, etc.

(2) The viscosity of the dispersion liquid is reduced and workability is improved.

(3) Pigments, etc. can be dispersed at high concentrations, saving solvents.
Costs such as storage and transportation can be reduced.

Claims (1)

[Claims] 1. A polyester compound of an oxyacid having a carboxyl group at the terminal and the general formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) (In the formula, n is an integer from 0 to 15. 1. A dispersant for particulate matter having a hydrophilic surface, characterized in that it is made of a reaction product with a polyhydric alcohol represented by: 2. Oxyacid polyester compound having a carboxyl group at the end and the general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, n represents an integer from 0 to 15) A dispersion composition consisting of a reaction product with a polyhydric alcohol, an organic medium and a particulate material having a hydrophilic surface. 3. The dispersant according to claim 2, wherein the particulate material having a hydrophilic surface is an organic or inorganic pigment. 4. The dispersion composition according to claim 2, wherein the particulate material having a hydrophilic surface is a ceramic. 5. The dispersion composition according to claim 2, wherein the granular material having a hydrophilic surface is a filler. 6. The dispersion composition according to claim 2, wherein the granular material having a hydrophilic surface is a flame retardant. 7. The dispersion composition according to claim 2, wherein the particulate material having a hydrophilic surface is a magnetic material.