JPH0611390B2 - Fine powder non-aqueous dispersant - Google Patents

Description

Detailed Description of the Invention [Industrial applications]

The present invention is a fine powder non-aqueous dispersant, and more specifically, it disperses an insoluble fine powder in a non-aqueous liquid in a short time, imparts long-term dispersion stability, and does not form a hard cake. It relates to a dispersant.

[Prior art]

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

[Problems to be Solved by the Invention]

However, such a conventional dispersant cannot provide a sufficient dispersant, stability, etc., and in particular, satisfactory performance such as sedimentation and separation of solid particles during long-term storage cannot be obtained. Therefore, a new dispersant is required.

[Means for Solving the Problems]

The present invention has been made focusing on such conventional problems. The inventors of the present invention have found the present invention as a result of earnest researches for a dispersant having excellent thinning effect in a fine powder non-aqueous dispersion and excellent in long-term stability. That is, (A) general formula (I) (In the formula, R ₁ is —CH ₂ CH (CH ₃ ) OH or —CH ₂
CH _{(C 2} H 5) is _{CH, R 2,} R ₃ is -H, -C
_{H 2 CH 2 OH, -CH 2} CH (CH 3) OH or -C
An alkanolamine compound represented by H ₂ CH (C ₂ H ₅ ) OH) and (B) general formula (II) R ₄ COOH
(II) (In the formula, R ₄ has 7 to 36 carbon atoms which may have a substituent.
Is an alkyl group, an allyl group, an alkenyl group or a polyester residue) and is a fine powder non-aqueous dispersant containing an amine soap consisting of a salt with a carboxylic acid represented by the formula (1) as an essential component. (Requirements Constituting Means) The alkanolamine represented by the general formula (I) used in the present invention is obtained by addition reaction of alkylene oxide with ammonia. Specifically, monoisopropanolamine, diisopropanolamine, triisopropanolamine, monobutanolamine, dibutanolamine,
Examples thereof include tributanolamine and monoethanoldiisopropanolamine, and examples thereof include one kind or a mixture of two or more kinds. On the other hand, examples of the carboxylic acid represented by the general formula (II) include fatty acid and polyester carboxylic acid. Specific examples of fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, saturated fatty acids such as behenic acid, linderic acid, myristoleic acid, oleic acid, elaidic acid, linoleic acid, and linolenic acid. And unsaturated fatty acids such as sabinic acid, ricinoleic acid, hydrogenated castor oil fatty acid, licanoic acid, and fatty acid having a carbonyl group such as 2-hydroxyoctadecanoic acid. These fatty acids may be either synthetic fatty acids or natural fatty acids, but the fatty acids used industrially are often a mixture of two or more of the above fatty acids. Specific examples of the natural fatty acid include coconut oil fatty acid, beef tallow fatty acid, palm oil fatty acid, lanolin fatty acid, naphthenic acid, tall oil fatty acid and the like. As the polyester carboxylic acid, propiolactone,
A lactone ring-opening polymer such as caprolactone, a dehydration condensate of hydroxy fatty acid such as 12-hydroxystearic acid, ricinoleic acid, and 2-hydroxystearic acid can be used. The average molecular weight of these is preferably 300 to 5,000, more preferably 600 to 2,000. If the above alkanolamine compound and carboxylic acid are mixed with stirring in the range of 30 to 100 ° C. and neutralized, a high temperature dehydration reaction at 150 to 200 ° C. under a nitrogen gas stream does not occur, and therefore alkanolamide of fatty acid is not contained. Amine soap, which is a surfactant suitable for the non-aqueous dispersant, can be obtained. At this time, not only neutralization of the reaction molar ratio of 1: 1 but also 1 to
It is also effective if one is in excess at a reaction molar ratio of 3: 3-1. The dispersant of the present invention can be used alone, but other surfactants such as an oil-soluble nonionic surfactant having an ester bond, an ethylene oxide group or an amide bond, or an anionic surfactant can be used. You may use together 1 type or 2 or more types. Examples of such a surfactant include polyhydric alcohol fatty acid ester such as sorbitan fatty acid ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, dialkyl sulfosuccinic acid ester, and petroleum sulfonic acid metal salt. The dispersant of the present invention described above is 0.1 to 0.1% with respect to the entire dispersion.
Used at a rate of 10% by weight. If the amount used is less than 0.1% by weight, the effect is small, and if it exceeds 10% by weight, the effect is not significantly improved and it 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 the inorganic fine powder 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, calcium sulfate, barium sulfate, sulfates such as aluminum sulfate, zirconia, magnesia, alumina, antimony trioxide, titanium oxide, white carbon, diatomaceous earth,
Metal oxides such as iron oxide and zinc oxide, hydroxides such as aluminum hydroxide, magnesium hydroxide, and iron hydroxide, as well as navy blue, silicon carbide, silicon nitride, boron nitride, barium titanate, carbon black, graphite, and nitric oxide. Molybdenum sulfide, carbon fluoride, sintered ceramics powder, carbon fiber powder, sulfur powder, magnetic powder, iron powder, aluminum powder, copper powder,
Examples of the nickel powder, silver powder, gold powder, and the like include fine powders such as solid paraffin, coal, agricultural chemicals, antibacterial agents, antioxidants, ultraviolet absorbers, and flame retardants. The average particle size of these fine powders is preferably 100 μm or less, generally 0.01 to 50 μm. The concentration of the fine powder in the dispersion system may be any concentration as long as the dispersion system can be obtained, but in general, it is often used at 5 to 80% by weight. Further, the non-aqueous dispersion medium for dispersing the solid fine powder is hexane, heptane, cyclohexane, mineral terpene, liquid paraffin, machine oil, aliphatic hydrocarbons such as spindle oil, 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 octanol, ester oils such as ethyl acetate and dioctyl phthalate, halogenated hydrocarbons such as perchlorethylene and trichloroethane, and further methylisobutyl. Ketone, methyl ethyl ketone, acetone, etc.,
These can be used alone or as a mixture of two or more. Particularly preferred dispersion media are aliphatic hydrocarbons and aromatic hydrocarbons. When using the dispersant of the present invention, any disperser may be used, and for example, a ball mill, a sand mill, a viscomill or the like is used. Further, the dispersant may be added by the above-mentioned disperser before or after the step of pulverizing the secondary particles, but generally, the addition before the step provides better dispersion and faster pulverization of the secondary particles. Therefore, it is preferable.

[Action]

The dispersant of the present invention can obtain excellent dispersibility and stability effects of various kinds of inorganic fine powders in various non-aqueous dispersion media because it has an alkanolamine having a lipophilic group and a lipophilic group. The amine soap obtained by the neutralization reaction of the carboxylic acid has further improved solvation and has a weak bond, so that it has a cationic property and an anionic property.
It is considered that this is because the action of adsorbing in a well-balanced manner, the effect of making the surface of the fine powder particles more lipophilic, and the dispersibility to the primary particles and the force (action) for preventing reaggregation become stronger.

【Example】

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. The various dispersants used here are shown in Table 1. further,
The dispersion stability performance was evaluated by the following tests, 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 to make the total amount 1 kg. This mixed solution is pulverized and mixed by a bead mill for 10 minutes to obtain a dispersion. Next, the viscosity of this dispersion liquid is measured at 25 ° C. with a B-type viscometer (rotor NO3). Then, put it in a 500 ml graduated cylinder, seal it tightly, and let it stand in a thermostatic chamber at 25 ° C. The dispersion state (evaluation -1) after 1 and 10 days and the hardness and redispersibility of the precipitate generated after 100 days are easy. (Evaluation-2) was evaluated. (Evaluation-1) Regarding the dispersion state, whether or not the fine particles are dispersed without settling is evaluated by the symbols of the following items. ◎. All powders were dispersed in the liquid, and no precipitation occurred at the bottom of the eyelids. 〇. Most of the powder is dispersed in the liquid, but a slight bottom precipitate occurs. △. About half the powder settles to the bottom. ×. Most of the powder settles to the bottom. (Evaluation-2) The hardness of the precipitate and the ease of redispersibility are evaluated by the following symbols. ◎. The precipitate is easily dispersed by stirring the liquid. 〇. The precipitate is soft and can be easily redispersed by stirring with a glass rod. △. Since the precipitate is hard, it will not be redispersed unless the glass rod is strongly stirred. ×. The precipitate is too hard to redisperse. From the above test results, Test No. 1 using the dispersant of the present invention
In Nos. 27 to 27, different kinds of fine powders could be satisfactorily dispersed in various non-aqueous dispersion media, and a hard sedimentary layer was not recognized even after standing for a long time.

【The invention's effect】

With the dispersant of the present invention, it is possible to disperse in a short time and obtain a long-term stable fine powder non-aqueous dispersion liquid. For example, there is a non-aqueous dispersion slurry of magnesium hydroxide used as a boiler corrosion inhibitor, a non-aqueous alumina dispersion slurry at the time of ceramic production, a sludge generation inhibitor for fuel oil, and the like. In this way, because it is excellent as a dispersant added to a non-aqueous liquid,
It can widely contribute to the progress of non-aqueous fine powder dispersion technology.

Claims (1)

[Claims] 1. (A) General formula (I) (In the formula, R ₁ is —CH ₂ CH (CH ₃ ) OH or —CH ₂
CH _{(C 2} H 5) is _{OH, R 2,} R ₃ is -H, -C
_{H 2 CH 2 OH, -CH 2} CH (CH 3) OH or -C
An alkanolamine compound represented by H ₂ CH (C ₂ H ₅ ) OH, and (B) general formula (II) R ₄ COOH (II) (wherein R ₄ may have a substituent) 7 to 36 carbon atoms
Of an alkyl group, an allyl group, an alkenyl group, or a polyester residue), which is a fine powder of a non-aqueous dispersant, which contains as an essential component an amine soap consisting of a salt with a carboxylic acid.