JPH044262A - Fine-powder nonaqueous dispersant - Google Patents

Abstract

PURPOSE:To obtain the subject nonaqueous dispersant containing an amine soap consisting of a salt composed of a specified alkanol amine compound and a carboxylic acid as the essential component, capable of dispersing in a short time in a nonaqueous liquid and providing a long-term dispersion stability. CONSTITUTION:An objective dispersant containing an amine soap consisting of a salt composed of (A) an alkanolamine compound such as a monoisopropanol amine or a diisopropanol amine represented by formula I [R1 is -CH2CH(CH3)OH or -CH2CH(CH2H5)OH; R2 and R3 are -H, -CH2CH2OH, -CH2CH(CH3)OH or -CH2CH(C2H5)OH] and (B) a carboxylic acid such as caprylic acid and lauric acid represented by formula II (R4 is 7-36C alkyl, aryl, alkenyl and polyester residue) as the essential component and free from formation of a hard cake.

Description

[Detailed description of the invention] [Industrial application field]

The present invention aims at non-aqueous dispersion of fine powders, more specifically, non-aqueous dispersion of fine powders that disperses insoluble fine powders in non-aqueous liquids in a short time, provides long-term dispersion stability, and does not produce hard cakes. This is related to drugs.

[Conventional technology]

Fine powder non-aqueous dispersion stabilizers are used in various industrial fields. For example, dispersion of pigments and paints in the field of paints, pigments, and printing inks is an important basic technology, and surfactants called dispersants are used to improve dispersibility. With the diversification of pigments, resins, and solvents, pigments are made into fine powders and various dispersants are used for each solvent. Furthermore, in recent years, we have added lubricants, metal powders, abrasives, corrosion inhibitors, fillers, fillers, sinterable ceramic powders, conductive materials, solid fuel powders, combustion catalyst powders, agricultural chemical powders, disperse dyes, antibacterial agents, etc. The development of products in which fine powder is dispersed in non-aqueous liquids is progressing, and dispersants are often used in both cases. As a conventional fine powder non-aqueous dispersant, for example, JP-A No. 6
1-185326, 61-227826, and 61-227830 disclose fatty acid reaction products of polyether compounds, urethane compounds of fatty acid amines or alkanolamides of fatty acids, and isocyanate compounds, etc. Publications No. 61-167436 and No. 61-227831 disclose ester compounds of alkanolamides of fatty acids and dicarboxylic acids and polycarboxylic acids as non-aqueous dispersants.

[Problem to be solved by the invention]

However, such conventional dispersants cannot provide sufficient dispersibility and stability, and in particular,
For example, solid particles settle and separate during long-term storage, and satisfactory performance has not yet been achieved, so new dispersants are required.

[Means to solve the problem]

This invention was made by focusing on such conventional problems. The present inventors have conducted extensive research in search of a dispersant that has excellent viscosity reducing effects and long-term stability in non-aqueous dispersions of fine powder, and as a result, they have discovered the present invention. That is, (A) - Formula (I) R. R1-N R3...(I) (In the formula, R is -CH2CHTCH, lOH or -CH2
CHfC,H,)OH, and R,,R, is -H, -C
H2CHJH, -CHlCH(CHs)OH or -CH
, CH(C,H,)OH) and (B)-formula (II) R4C0OH...(II
) (in the formula, R4 has 7 to 3 carbon atoms, which may have a substituent)
This is a fine powder non-aqueous dispersant containing as an essential component an amine soap consisting of a salt with a carboxylic acid represented by (6) an alkyl group, an allyl group, an alkenyl group, or a polyester residue. (Requirements constituting the means) The alkanolamine represented by the general formula (I) used in the present invention is obtained by addition reaction of alkylene oxide to ammonia. Specifically, monoisopropanolamine, diisopropanolamine, triisopropanolamine, monobutaturamine, diptanolamine, tributanolamine, monoethanol diisopropanolamine, etc., and one or two of these. Examples include mixtures of more than one species. On the other hand, examples of the carboxylic acid represented by the general formula (II) include fatty acids and polyester carboxylic acids. Specific examples of fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, and palmitic acid. Saturated fatty acids such as stearic acid and behenic acid, unsaturated fatty acids such as lindelic acid, myristoleic acid, oleic acid, elaidic acid, linoleic acid, and lylunic acid, sabinic acid, ricinoleic acid, hydrogenated castor oil fatty acid, lycanic acid, 2 Examples include fatty acids having a hydroxyl group or a carbonyl group such as -hydroxyoctadecanoic acid. These fatty acids may be either synthetic fatty acids or natural fatty acids, but usually industrially used fatty acids are often a mixture of two or more of the above fatty acids. Specific examples of natural fatty acids include coconut oil fatty acids, beef tallow fatty acids, palm oil fatty acids, lanolin fatty acids, naphthenic acids, and tall oil fatty acids. Examples of polyester carboxylic acids include propiolactone,
Examples include lactone ring-opening polymers such as caprolactone, dehydrated condensates of hydroxy fatty acids such as 12-hydroxystearic acid, ricinoleic acid, and 2-hydroxystearic acid. The average molecular weight of these is preferably 300 to 5,000, more preferably 600 to 2,000. If the above-mentioned alkanolamine compound and carboxylic acid are mixed at a temperature of 30-100°C with stirring and neutralized, the alkanolamide of the fatty acid is not contained, and the present invention does not involve the high-temperature dehydration reaction at 150-200°C under a nitrogen gas stream. An amine soap is obtained which is a suitable surfactant for the non-aqueous dispersant of the invention. In this case, not only neutralization of the reaction molar ratio of 1:1 (,1~
It is effective even if one is in excess at a reaction molar ratio of 3:3 to 1. The dispersant of the present invention can be used alone, but it can also be used in combination with other surfactants, such as oil-soluble nonionic surfactants having ester bonds, ethylene oxide groups, or amide bonds, or anionic surfactants. You may use one type or a combination of two or more types. Examples of such surfactants include polyhydric alcohol fatty acid esters such as sorbitan fatty acid esters, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl ethers, dialkyl sulfosuccinates, petroleum sulfonic acid metal salts, and the like. The dispersant of the present invention with ti2 has a concentration of 0.1 to the entire dispersion.
It is used in a proportion of ~10% by weight. If the amount used is less than 0.1% by weight, the effect will be small, and if it exceeds 10% by weight, the improvement in the effect will not be significant, which is economically disadvantageous. The dispersant of the present invention is effective for both inorganic and organic fine powders, but is particularly effective for inorganic fine powders. Examples of inorganic fine powders include kaolin, aluminum silicate, clay, talc, mica, asbestos powder, calcium silicate, sericite, bentonite, ultramarine, silicates such as magnesium silicate, calcium carbonate, magnesium carbonate, barium carbonate, Carbonates such as dolomite, sulfates such as calcium sulfate, barium sulfate, aluminum sulfate, etc., metal oxides such as zirconia, magnesia, alumina, antimony trioxide, titanium oxide, white carbon, diatomaceous earth, iron oxide, zinc oxide, etc. , aluminum hydroxide,
Hydroxides such as magnesium hydroxide and iron hydroxide, as well as navy blue, silicon carbide, silicon nitride, boron nitride, barium titanate, carbon black, graphite, molybdenum disulfide, carbon fluoride, sintered ceramic powder, carbon fiber powder , sulfur powder, magnetic powder, iron powder, aluminum powder, copper powder, nickel powder, silver powder, gold powder, etc., as well as solid paraffin, coal,
Examples include fine powders of agricultural chemicals, antibacterial agents, antioxidants, ultraviolet absorbers, flame retardants, and the like. The average particle size of these fine powders is 10
It is preferable to use a thickness of 0 micron or less, generally about 0.01 to 50 micron. Further, the concentration of the fine powder in the dispersion system may be any concentration as long as a dispersion system can be obtained, but it is generally used at 5 to 80% by weight in many cases. In addition, the non-aqueous dispersion medium for dispersing the solid fine powder is aliphatic hydrocarbons such as hexane, heptane, cyclohexane, mineral turpentine, liquid paraffin, machine oil, and spindle oil, and aromatic hydrocarbons such as benzene, toluene, and xylene. , fuel oils such as kerosene, light oil, and heavy oil; aliphatic alcohols such as ethanol, isopropanol, butanol, and octatool; ester oils such as ethyl acetate and dioctyl phthalate; halogenated hydrocarbons such as perchlorethylene and trichloroethane; Furthermore, there are methyl isobutyl ketone, methyl ethyl ketone, acetone, etc., and these can be used alone or in a mixture of two or more. Particularly preferred dispersion media are aliphatic and aromatic hydrocarbons. When using the dispersant of the present invention, any dispersing machine may be used, such as a ball mill, sand mill, Visco mill, etc. Furthermore, the dispersant may be added before or after the process of pulverizing the secondary particles using the dispersing machine, but generally speaking, adding it before the process will result in better dispersion and faster pulverization of the secondary particles. preferable.

[Effect]

The reason why the dispersant of the present invention can achieve excellent dispersibility and stability effects for various types of inorganic fine powders in various non-aqueous dispersion media is because alkanolamines having lipophilic groups and alkanolamines having lipophilic groups The amine soap obtained by the neutralization reaction of carboxylic acid has improved solvation, and since it is composed of weak bonds, it has cationic and anionic properties, and has cationic and anionic properties.
This is thought to be due to the well-balanced adsorption, the effect of making the surface of the fine powder particles more lipophilic, and the stronger dispersibility into secondary particles and the force (effect) of preventing reagglomeration.

【Example】

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto in any way. Here, the various dispersants used are shown in Table 1. Furthermore, the dispersion stability performance was evaluated by the following test, and the test results are shown in Tables 2 and 3. (Dispersibility test) A predetermined amount of insoluble fine powder is added to a non-aqueous dispersion medium containing a predetermined amount of a dispersant, and the total amount is IKg. This mixture was pulverized and mixed in a bead mill for 10 minutes to obtain a dispersion. Next, the viscosity of this dispersion liquid was measured at 25° C. using a B-type viscometer (rotor N03). After that, it was placed in a 500rnJ2 graduated cylinder, sealed tightly and left to stand in a constant temperature room at 25℃, and the dispersion state after 1 and 10 days (rating -1) and the hardness and redispersibility of the precipitate that occurred after 100 days. (Evaluation -2) was evaluated. (Evaluation-1) The dispersion state is evaluated using the symbols in the following items to determine whether or not the fine particles are dispersed without settling. 0. All the powder is dispersed in the liquid, and no precipitation occurs at the bottom. ○: Most of the powder is dispersed in the liquid, but there is a slight amount of sediment at the bottom. △: Approximately half of the powder settles at the bottom. X, most of the powder settles to the bottom. (Evaluation-2) The hardness of the precipitate and the ease of redispersibility are evaluated using the following symbols. 0. The precipitate is easily dispersed by stirring the liquid. ○: The precipitate is soft and can be easily redispersed by stirring with a glass rod. △: Because the precipitate is hard, it will not be redispersed unless the glass rod is stirred strongly. ×: The precipitate was very hard and could not be redispersed. (Left below) From the above test results, test No. using the dispersant of the present invention,
In samples Nos. 1 to 27, different types of fine powders could be well dispersed in various non-aqueous dispersion media, and no hard sedimentary layer was observed even after standing for a long time.

【Effect of the invention】

By using the dispersant of the present invention, a non-aqueous dispersion of fine powder that can be dispersed in a short time and is stable for a long period of time can be obtained. Examples include a non-aqueous dispersion slurry of magnesium hydroxide used as a boiler corrosion inhibitor, a non-aqueous alumina dispersion slurry used in ceramic production, and a fuel oil sludge prevention agent. In this way, it is excellent as a dispersant added to non-aqueous liquids,
This can widely contribute to the advancement of non-aqueous fine powder dispersion technology. Patent applicant Daiichi Kogyo Seiyaku Co., Ltd.

Claims (1)

[Claims] (A) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I
) (In the formula, R_1 is -CH_2CH(CH_3)OH or -
CH_2CH(C_2H_5)OH, R_2, R
_3 is -H, -CH_2CH_2OH, -CH_2CH
(CH_3)OH or -CH_2CH(C_2H_5)
OH) and (B) general formula (II) R_4COOH...(II) (wherein R_4 has 7 to 3 carbon atoms and may have a substituent)
A fine powder non-aqueous dispersant characterized by containing as an essential component an amine soap consisting of a salt with a carboxylic acid represented by (6) an alkyl group, an allyl group, an alkenyl group, or a polyester residue.