JPH0373332B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a non-aqueous stable solid dispersant, particularly a solid dispersant containing a mixture of an alkanolamide or alkylene oxide adduct of a fatty acid and a phosphoric acid ester or a salt thereof as an active ingredient. [Prior Art] Conventionally, as this type of non-aqueous stable solid dispersant, for example, as disclosed in Japanese Patent Application Laid-open No. 57-92518 and US Pat. No. 4,354,872,
Known examples include alkanolamides of fatty acids, fatty alcohols, alkanolamines, magnesium lauryl sulfate, and imidazoline type amphoteric surfactants. [Problems to be Solved by the Invention] However, the conventional dispersants as described above have several problems such as stability, and for example, solid particles settle and separate during long-term storage. No, no. Therefore, an object of the present invention is to obtain a dispersant that can improve the dispersion stability of solid particles in a non-aqueous system. [Means for Solving the Problems] As a result of intensive studies to achieve the above object, the inventors have found that alkanolamide of a specific fatty acid or its alkylene oxide adduct and a specific phosphorus are used as active ingredients of a dispersant. When using a mixture with an acid ester or its salt in a specific ratio,
The inventors have discovered that a nonaqueous solid dispersion can be obtained that suppresses sedimentation and separation of solid particles and has excellent long-term storage stability, leading to the present invention. That is, this invention provides (a) a fatty acid alkanolamide or an alkylene oxide adduct thereof consisting of one or a mixture of two or more saturated or unsaturated fatty acids having a carbon chain length of 6 to 22 carbon atoms; ) The following general formula; (In the formula, R is an alkyl group or alkenyl group having 1 to 30 carbon atoms, or an alkylphenyl group having an alkyl group having 1 to 30 carbon atoms, AO is an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide, n is the number of moles of alkylene oxide added, and k is 1 or 2. The above a component and b
The proportion of component b in the total amount of components is 1 to 90
This relates to a non-aqueous solid dispersant characterized in that it is % by weight. [Structure and operation of the invention] The fatty acid alkanolamide according to the present invention is obtained by reacting a fatty acid or a derivative such as a lower alkyl ester thereof with an alkanolamine. , preferably one or a mixture of two or more saturated or unsaturated fatty acids having a chain length of 10 to 18 carbon atoms. Further, examples of the above-mentioned alkanolamine include monoethanolamine, diethanolamine, monoisopropanolamine, diisopropanolamine, aminoethylethanolamine, etc., and one type or a mixture of two or more of these may be used. The alkylene oxide adduct in this invention can be obtained by adding an alkylene oxide to the fatty acid alkanolamide obtained by the above method according to a known method. The alkylene oxide used to obtain the above adduct is preferably ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc., and these may be used alone or as a mixture of two or more, but as a mixture of two or more. When used, the addition polymerization can be either block or random copolymerization. The number of moles of alkylene oxide added is usually 1 to 100 moles, preferably 1 to 70 moles. If the number of moles added is too large, the affinity for solid particles due to the alkanolamide structure will be insufficient, making it difficult to obtain the effect of highly improving dispersion stability as the object of the present invention. The phosphoric acid ester used in this invention has the following general formula; (In the formula, R is an alkyl group or alkenyl group having 1 to 30 carbon atoms, or an alkylphenyl group having an alkyl group having 1 to 30 carbon atoms, and AO is an alkylene oxide selected from ethylene oxide, propylene oxide, and butylene oxide. , n is the number of moles of alkylene oxide added, from 0 to 100, and k is 1 or 2), and is one or a mixture of two or more of these. Examples of these phosphate esters include mono 2
-Ethylhexyl phosphate, di-2-ethylhexyl phosphate, mono-n-octyl phosphate, di-n-octyl phosphate, monooleyl phosphate, diocheyl phosphate, monolauryl phosphate, dilauryl phosphate , monopolyethylene oxide [40 moles] octyl phenyl ether phosphate, dipolyethylene oxide [40 moles] octyl phenyl ether phosphate, monopolyethylene oxide [10 moles] nonylphenyl ether phosphate, dipolyethylene oxide [10
mole] nonyl phenyl ether phosphate ester,
Monopolypropylene oxide [10 moles] dodecyl phenyl ether phosphate, dipolypropylene oxide [10 moles] dodecylphenyl ether phosphate, monopolyethylene oxide [30
mol] lauryl ether phosphate ester, dipolyethylene oxide [30 mol] lauryl ether phosphate ester, etc. In addition, when forming a salt of phosphoric acid ester, the salt is an alkali metal salt, an alkaline earth metal salt, an ammonium salt, or a lower amine salt, such as potassium, sodium, calcium, magnesium, ammonia, diethanolamine, triethanolamine. These salts may be used alone or as a mixture of two or more thereof. In this invention, it is important to use the above-mentioned fatty acid alkanolamide or alkylene oxide adduct in combination with phosphoric acid ester or its salt, and this combination allows solid particles in the slurry to settle and separate during long-term storage. Such problems can be effectively avoided. The reason why the dispersion stability of solid particles is significantly improved by the above-mentioned combination is not necessarily clear, but it is speculated as follows. That is, when a fatty acid alkanolamide or its alkylene oxide adduct is used as a mixture with a phosphoric acid ester or its salt, a complex is formed by the structure of the alkanolamide and the structure of the anion, as is well known. It is thought that this increases the thickness of the adsorption layer of the dispersant on the solid particles, and that the electrostatic repulsive force due to the anion structure also contributes to stability. The mixing ratio of the mixture of fatty acid alkanolamide or its alkylene oxide adduct and phosphoric acid ester or its salt in order to exhibit such an effect is determined by the proportion of the phosphoric acid ester or its salt in the total amount of both. 1-90% by weight,
The content is preferably 1 to 50% by weight. The dispersant of the present invention contains a mixture of such a fatty acid alkanolamide or its alkylene oxide adduct and a phosphoric acid ester or its salt as an active ingredient. A known surfactant may also be included. The amount of this surfactant used is preferably 50% by weight or less based on the total amount of the above-mentioned active ingredients. Examples of the above surfactants include polycarboxylate, naphthalene sulfonate, dodecylbenzene sulfonate, fatty acid soap, higher alcohol sulfate, polyoxyethylene alkyl phenyl ether, dialkyl sulfosuccinate, polyoxyethylene Fatty acid ester, polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene/polyoxypropylene block or random copolymer, as well as pentaerythritol, trimethylolpropane, and Polyoxyethylene/polyoxypropylene blocks or random adducts of polyols such as sugars, polyoxyethylene/polyoxypropylene blocks or random adducts of polyamines such as ethylene diamine and diethylene triamine, and polyoxyethylene of polyimines such as polyethylene imine and polypropylene imine.・Polyoxypropylene blocks or random adducts may be mentioned. Examples of solids that can be dispersed using the dispersant of the present invention include titanium oxide, iron oxide, zinc oxide,
Sachin white, white carbon, navy blue, ultramarine blue, carbon black, phthalocyanine pigments,
Inorganic or organic dyes and pigments such as perylene pigments, graphite, charcoal, coal, coke, petroleum coke, mica, molybdenum disulfide, tungsten disulfide, calcium carbonate, alumina, silicates,
silicon nitride, silicon carbide, boron nitride, boron oxide,
Examples include zirconium oxide. Non-aqueous oils for dispersing the above solids include mineral oils, animal and vegetable oils, waxes, fatty acid esters, paraffins, aromatic carboxylic acid esters, lower to higher alcohols, chlorinated hydrocarbons, polyolefins, silicones, Examples include ketones, and these can be used alone or as a mixture of two or more. The above-mentioned solid to be dispersed in the oil is usually used as a powder with a particle size of 200 μm or less, preferably 100 μm or less, and the amount used varies depending on the type of solid, but generally 80 μm or less by weight. % or less, preferably 50% or less by weight. In order to create a stable non-aqueous solid dispersion using the dispersant of this invention, depending on the type of solid, the carbon chain length of the fatty acid, the type of alkanolamine, or the type of alkylene oxide and its addition in the active ingredient must be determined. This can be achieved by simply changing the combination of the number of moles, the type of phosphoric acid ester, and the type of its salt. In this case, the amount of the dispersant to be used is such that the active ingredient is 0.01 to 10% by weight, preferably 0.1% by weight of the entire dispersion.
It is preferable to adjust the amount to 5% by weight. If this amount is too small, the dispersion stability of the solid particles will be poor, and if it is used in excess of a certain amount, there will be no significant improvement in the effect, which is economically disadvantageous. [Effects of the Invention] By using the dispersant of the present invention, it is possible to easily obtain a stable non-aqueous solid dispersion in which solid particles do not settle and separate during long-term storage. Therefore, the dispersant of the present invention can be used as an effective dispersant in a wide range of fields such as paints, dyes, pigments, printing inks, lubricants, noncombustible materials for construction, and fuels. [Examples] Hereinafter, examples of the present invention will be described in more detail. Example A mixture of a fatty acid alkanolamide or its alkylene oxide adduct and a phosphoric acid ester or a salt thereof, or a mixture of these and other surfactants according to Samples Nos. 1 to 7 shown in Table 1 below was prepared. This was the solid dispersant of the present invention. In addition, for reference, the surfactants according to Sample Nos. 8 to 10 shown in the same table were used as solid dispersants for comparison. In Table 1, the numbers in parentheses for ethylene oxide adducts and propylene oxide adducts indicate the number of moles of each alkylene oxide added. Using the above-mentioned dispersant and the various solids and oils listed in Table 1, a non-aqueous solid dispersion is prepared using the following method at the blending ratio (wt%) listed in Table 1. Stability was investigated. It should be noted that the various solids used were powders each having a particle size of 100 μm or less. <Preparation and evaluation method of solid dispersion> Add a predetermined amount of oil, solid, and dispersant to a magnetic ball mill with a capacity of 3 for a total of 500 g,
A solid dispersion was prepared by mixing and stirring for a predetermined time. The mixing and stirring time was 30 minutes for Samples No. 1, 4, 6, 9, and 10, 40 minutes for Sample No. 7, and 60 minutes for all others. After preparing the solid dispersion, it was transferred to a 100 ml graduated cylinder and stored in a constant temperature bath at room temperature (25°C) for one month, and then the dispersion was taken out by tilting the graduated cylinder. At this time, those that came out in their entirety by simply tilting them were rated as ○, those that came out when lightly poked with a glass rod etc. were rated as △, and those that did not come out unless scraped out with a spatula or the like were rated as ×.

【table】

[Table] According to the above test results, the solid dispersions of samples No. 1 to 7 using the dispersant of the present invention all showed good fluidity, but the samples using the dispersant for comparison All of the solid dispersions Nos. 8 to 10 had very poor fluidity. As is clear from these results, it can be seen that the dispersant of the present invention provides a long-term stable non-aqueous solid dispersion.

Claims (1)

[Scope of Claims] 1 (a) A fatty acid alkanolamide or its alkylene oxide adduct consisting of one or a mixture of two or more saturated or unsaturated fatty acids having a carbon chain length of 6 to 22 carbon atoms; b) The following general formula; (In the formula, R is an alkyl group or alkenyl group having 1 to 30 carbon atoms, or an alkylphenyl group having an alkyl group having 1 to 30 carbon atoms, and AO is an alkylene oxide selected from ethylene oxide, propylene oxide, and butylene oxide. , n is the number of moles of alkylene oxide added and k is 1 or 2) as an active ingredient. and the above a component and b
The proportion of component b in the total amount of components is 1 to 90
% by weight of a non-aqueous solid dispersant. 2 The alkanolamide of component a is one or two of monoethanolamine, diethanolamine, monoisopropanolamine, diisopropanolamine, and aminoethylethanolamine.
The non-aqueous solid dispersant according to claim 1, which is an amide of a mixture of more than one species. 3. The nonaqueous system according to claim 1 or 2, wherein the alkylene oxide in the alkylene oxide adduct of component a is one or a mixture of two or more of ethylene oxide, propylene oxide, butylene oxide, and styrene oxide. solid dispersant. 4. The nonaqueous solid dispersant according to any one of claims 1 to 3, wherein the number of moles of alkylene oxide added in the alkylene oxide adduct of component a is 1 to 100. 5. Claims 1 to 4, wherein the phosphoric acid ester salt of component b is one or a mixture of two or more of alkali metal salts, alkaline earth metal salts, ammonium salts, or lower amine salts. Any of the non-aqueous solid dispersants.