JPH038427A - Water-in-oil type emulsifier - Google Patents

Abstract

PURPOSE:To obtain an emulsifier having effective emulsifying power in a wide HLB range by using an amidation product obtd. by condensing higher fatty acid and a specified diamine or polyamine and the acidic phosphoric ester of an org. compd. as essential components. CONSTITUTION:8-24C higher fatty acid such as caprylic acid or capric acid and a diamine or polyamine represented by formula I or II (where R is H, 1-24C alkyl or alkenyl, a is an integer of 1-4 and b is an integer of 1-8) are used as starting materials for an amidation reaction and condensed by dehydration to obtain an amidation product. This product and the acidic phosphoric ester and/or the acidic sulfuric ester of an org. compd. such as acidic alkylphosphoric ester are used as essential components to obtain an emulsifier. Stable water-in-oil type emulsions can be prepd. by emulsifying various oily components with the emulsifier under various conditions.

Description

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

The present invention relates to a novel water-in-oil emulsifier,
More specifically, the present invention relates to a water-in-oil emulsifier that has excellent emulsifying power and can provide a stable emulsion even when using alkaline water.

[Conventional technology]

When producing an emulsion by emulsifying oil and water,
It is common practice to determine the so-called required HLB of the oil content and select an emulsifier that matches it. In general, H.L.B.
A combination of a hydrophilic emulsifier with a high HLB and a lipophilic emulsifier with a low HLB is used. The method for determining the HLB of these emulsifiers is, for example, "Synthesis and Concentric J of Surfactants (
Published by Maki Shoten in 1957) on pages 492-494. In addition, the required HLB for oil is 1. For example, "Emulsification and Solubilization Technology J (1976, published by Kogaku Tosho), pp. 79-8
It is written on page 1 etc. This HLB is determined experimentally through emulsification tests, and emulsification is attempted using a surfactant having a value close to the HLB. However, in reality, stable emulsions are rarely obtained, and it is not easy to obtain a compatible emulsifier by applying HLB. Furthermore, as water-in-oil emulsifiers, non-containing substances such as sorbitan fatty acid esters, glycerin or polyglycerin fatty acid esters, polyethylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, and ethylene oxide adducts of fatty acid furcaramides can be used. Ionic surfactants and mixtures thereof are known and have been used in the past.

[Problem to be solved by the invention]

However, such conventional water-in-oil emulsifiers have several drawbacks. That is, although ether type nonionic surfactants have the advantage of being chemically stable and are particularly resistant to hydrolysis, stable water-in-oil emulsions cannot be obtained. Ester-type nonionic surfactants can relatively easily form water-in-oil emulsions, but they are chemically unstable and subject to hydrolysis, especially in alkaline environments, resulting in problems such as the inability to obtain stable emulsions. Ta. In addition, in the production of various emulsions, the required HLB changes as the type of oil changes, so it is necessary to select a compatible emulsifier according to the required HLB, but this selection is quite difficult. was there. The purpose of J is to provide an emulsifier that has effective emulsifying power in a wide range of HLBs, that is, various oils, and forms stable emulsions, and in particular, can form stable emulsions even when using alkaline water. be.

[Means to solve the problem]

This invention has focused on the above-mentioned conventional problems and has made it possible to overcome them as a result of intensive research. That is, higher fatty acids having 8 to 24 carbon atoms and the following general formulas (1), (2)% formula % (2) (wherein R is H or an alkyl group or alkenyl group having 1 to 24 carbon atoms, and a is an integer from 1 to 4, and b is an integer from 1 to 4.
It is an integer of 8. ) in an oil containing as essential components an acidic phosphoric acid ester and/or acidic sulfuric acid ester of an organic compound (component B) and a 7-amidation reaction product obtained by dehydration condensation of a diamine or polyamine represented by (component B). It is a water emulsifier. (Requirements constituting the means) Fatty acids that are raw materials for the amidation reaction of component A used in the present invention include higher fatty acids having 8 to 24 carbon atoms. Specifically, caprylic acid and capric acid. Saturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, unsaturated fatty acids such as lindelic acid, myristoleic acid, oleic acid, elaidic acid, linoleic acid, linuric acid, sabinic acid, ricinoleic acid,
Examples include fatty acids having a hydroxyl group or a carbonyl group, such as hydrogenated castor oil fatty acids, lycanic acid, and 2-hydroxyoctadecanoic acid. These fatty acids may be either synthetic or natural products. Fatty acids made from natural oils and fats used industrially are essentially a mixture of the above-mentioned fatty acids, but these natural fatty acids can be used, specifically coconut oil fatty acids, beef tallow fatty acids, palm oil fatty acids, etc. can be mentioned. The other raw material diamine or polyamine used in the amidation reaction of A component 7 is the following general / (CH2
)a NH2 RN”...
・・・・・・・・・・・・・・・・・・(2)＼ (CH2
) a N H2 (wherein, R is H or alkylene having 1 to 24 carbon atoms, (
or alkenyl group, a is an integer of 1 to 4, b is 1 to 8
is an integer. ). Specifically, the compounds represented by formula (1) include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, butylenediamine, dimethylaminoethylamine, ethylaminoethylamine, diethylaminoethylamine, diethylamino Examples include probylamine, lauryl aminopropylamine, stearyl aminopropylamine, oleylaminopropylamine, tallow aminopropylamine, and the like. Further, examples of the compound represented by formula (2) include iminobispropylamine, methyliminobispropylamine, iminobisbutylamine, lauryliminobispropylamine, palmityliminobispropylamine, oleliminobispropylamine, etc. I can do it. The dehydration condensation reaction between higher fatty acids and diamines or polyamines (hereinafter referred to as amine compounds) can be carried out by a normal amidation reaction using a catalyst if necessary.
The amide compound related to the present invention can be easily obtained by stirring under a nitrogen stream, heating to 160-220''C, and distilling off the water produced by the condensation reaction. The reaction molar ratio with the amine compound may be within a range sufficient to generate 0.5 to 2 amide bonds on average, and is 0.5/1 to 2°4/1, preferably 0.7/1 to 2. 2.1/l. The amidation reaction process can be confirmed by measuring the oxidation of the reactant. The acidic phosphoric acid esters of component B include acidic alkyl phosphoric esters and acidic alkyl ether phosphoric esters. Examples of acidic alkyl phosphate esters include monoesters, diesters, triesters, and mixtures thereof obtained by phosphoricating an aliphatic alcohol using a phosphorylating agent, and the number of carbon atoms in the alkyl group is preferably is 4 to 22. In addition to aliphatic alcohols, olefins, oxyfatty acids, etc. are also used. Acidic alkyl ether phosphates are produced by, for example, converting polyalkylene glycol-covered nonionic surfactants into phosphate esters using a phosphorylating agent. Polyalkylene gellicol type nonionic surfactants used for phosphoric acid esterification include phenol, alkylphenol, aliphatic alcohol, and fatty acid. Examples of alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc. etc., and by a known method, 1
It can be obtained by addition reaction of one species or two or more species. 2
When adding more than one species, any method such as random addition reaction or block addition reaction may be used.Acidic sulfuric esters are also effective as the B component. Acidic sulfuric acid esters include those obtained by converting an organic compound having a hydroxyl group or double bond into a sulfuric acid ester with a sulfating agent such as sulfuric acid, oleum, chlorosulfone, acetyl sulfuric acid, etc. Compounds having double bonds include: 1. Olefins having 4 to 22 carbon atoms, saturated aliphatic alcohols, unsaturated aliphatic alcohols, synthetic alcohols, oxyfatty acids 2, unsaturated fatty acids such as oleic acid, lactic acid, and ricinoleic acid. , esterified products of hydroxycarboxylic acids or oxyfatty acids with alcohols and amidated products with monoalkanolamines, primary and secondary aliphatic amines, and aromatic amines 3 , fats and oils such as castor oil 4 , the above polyalkylene gelicols Examples include type nonionic surfactants. Also, the above acidic phosphate ester and acidic! Each of the M esters may be used alone or both may be used in combination. The water-in-oil emulsifier of the present invention is characterized by containing the above-mentioned amide compound as component A and an acidic phosphate ester and/or resistant sulfate ester as component B as essential components. The weight ratio of component A and component B is 9,510,5-3/
7 is preferably 8/2 to 4/6; outside this range, it is necessary to increase the addition rate as an emulsifier, which is economically disadvantageous. Furthermore, those containing higher fatty acids having 8 to 24 carbon atoms are also effective. Specific examples of higher fatty acids include higher fatty acids used as raw materials for the above-mentioned component A. When blending higher fatty acids, 1 cup of higher fatty acids is A component by weight,
It accounts for 60% or less, preferably 50% or less, of the total of component B and higher fatty acids. In this case, at the stage of the amidation reaction of component A, an excess amount of higher fatty acids is added in advance.
At the end of the reaction, the higher fatty acids may remain as unreacted components, and then the acidic phosphoric acid ester and/or the acidic sulfuric acid ester may be blended, or the higher fatty acids may be further added, and the blending ratio may be 60% of the total of the three components. % or less, preferably 50% or less. Oils that can form water-in-oil emulsions using the emulsifier of the present invention include aromatic hydrocarbons, mineral oils, animal and vegetable oils, and waxes. fatty acid ester, paraffin,
Examples include aromatic carboxylic acid esters, higher alcohols, chlorinated hydrocarbons, polyolefins, silicone oils, etc., but mixtures of two or more of these are also effective. The amount of the emulsifier of the present invention to be used is component A and component B, or component A and B.
The total amount of the components and the higher fatty acid is 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, per 100 parts of oil. Further, other surfactants and known emulsifiers may be added as necessary within a range that does not impair the effects of the present invention. Specifically, sucrose fatty acid ester, sorbitan fatty acid ester, glycerin or polyglycerin fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, ethylene oxide adduct of fatty acid alkanolamide, polyoxy Ethylene polyoxypropylene block polymer, polyoxypropylene polyoxyethylene block polymer of ethylene diamine, polyoxypropylene polyoxyethylene block polymer of polyamine compound such as polyethylene polyamine or preethyleneimine, alkylbenzene sulfonate 1 right oil sulfonate, etc. Can be mentioned. Furthermore, in addition to the emulsifier of the present invention, if necessary, a polymeric emulsion stabilizer, an alkaline substance, a preservative, a thickener, an anti-sag agent,
Even if rust preventive agents, PH adjusters, antifoaming agents, etc. are used together, the effect will not be impaired.

[Effect]

The water-in-oil emulsifier of the present invention is characterized in that it contains an amide compound and an acidic phosphoric acid ester and/or an acidic sulfuric acid ester of an organic compound. Both of these are compounds with large hydrophobic groups, and the neutralized product of the amide compound cation and acidic phosphoric acid ester and/or acidic sulfuric ester obtained by blending also has strong lipophilicity. It has excellent solubility, and the combination of higher fatty acids provides a good balance of hydrophobicity, making it suitable for making water-in-oil emulsions.

【Example】

Hereinafter, the present invention will be described in more detail by describing examples, but the present invention is not limited to these examples. All parts and percentages shown in the examples are based on weight. . Ami' An example of the production of the amide compound of sample Not shown in Table 1 is shown below. 160.0 g of lauric acid (0.8
mol), and after purging with nitrogen, the temperature was raised to 50°C and diethylenetriamine 103. og (1 mol) was added dropwise over 10 minutes,
Dewood condensation was carried out for 6 hours while maintaining the temperature at 180℃, and the acid value was 1.
, 5mg-KO)I/H amidation reaction product was obtained. This reaction product was called diethylenetriamine/lauric acid amide (l: 0.8), and amide compounds of Samples Nos. 2 to 12 in Table 1 were obtained using the same manufacturing method. Samples NO, 1-NO, and 12 were used as emulsifiers of the present invention at the blending ratios shown in Table 1. For reference, surfactants related to samples No. 13 to 15 shown in the same table were used as emulsifiers for comparison. Emulsions were prepared and the stability of the emulsions was evaluated by the following method using the emulsifier shown in Table L and the oil and water shown in Table 2 at the mixing ratios shown in Table 2. The results were as shown in the same table. 2. Preparation and evaluation method of emulsion> Add an emulsifier to the oil and mix at room temperature using a homomixer. OOOr
An emulsion was prepared by adding water little by little while continuing to stir the mixture. After preparing the emulsion, cool it to room temperature if necessary, transfer it to a 100ml graduated cylinder, and store it at room temperature for 60 days. Observe whether the emulsion has separated. 0 If no separation has occurred, O1. Those in which a very small amount of Δ1 separation was observed were evaluated as X, and those in which Δ1 separation was significant were evaluated. (Left below) As is clear from the results in Table 2, stable water-in-oil emulsions can be obtained with various oils when the emulsifier of the present invention is used. A stable emulsion can also be obtained when alkaline water is used as the water. On the other hand, when other emulsifiers are used, the stability of the emulsion is poor.

【Effect of the invention】

By using the emulsifier of the present invention, stable water-in-oil emulsions with a wide range of oil components can be obtained under various conditions. Furthermore, a stable emulsion can be obtained even when strongly alkaline water having a pH of 10 or higher is used. Therefore, the emulsifier of the present invention can be used in cosmetics, medicines, agricultural chemicals, as well as emulsion fuels, water repellents, and waterproofing agents. It can be used as an effective emulsifier in a wide range of fields such as mold release agents and emulsion inks.

Claims (1)

[Claims] 1. Higher fatty acid having 8 to 24 carbon atoms and the following general formula (1),
(2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2) (In the formula, R is H or alkyl having 1 to 24 carbon atoms. group or alkenyl group, a is an integer of 1 to 4, and b is an integer of 1 to 4.
It is an integer of 8. ) An amidation reaction product obtained by dehydration condensation of a diamine or polyamine represented by (component A) and an acidic phosphoric acid ester and/or acidic sulfuric acid ester of an organic compound (component B) as essential components. A water-in-oil emulsifier. 2. The weight ratio of component A and component B is A/B=9.5/0.
The water-in-oil emulsifier according to claim 1, which has a molecular weight of 5 to 3/7. 3. A water-in-oil emulsifier, characterized in that the emulsifier according to claim 1 or 2 contains a higher fatty acid having 8 to 24 carbon atoms. 4. The blending ratio of the higher fatty acids according to claim 3 is A in weight ratio.
4. The water-in-oil emulsifier according to claim 3, wherein the amount is 60% or less based on the total amount of component B, component B, and higher fatty acid. 5. The water-in-oil emulsifier according to claims 1 to 4, wherein the reaction molar ratio of the higher fatty acid according to claim 1 and the diamine or polyamine is 0.5/1 to 2.4/1.