JPH02149329A - Emulsifying agent - Google Patents

Abstract

PURPOSE:To produce emulsions which are stable for a long period of time, by using an emulsifying agent containing a specific di(long-chain alkyl) quaternary ammonium salt as an essential component. CONSTITUTION:An emulsifying agent is prepared using dioleyl dialkyl quanternary ammonium salt represented by the general formula I (R1, R2: oleyl group, R3: a 1-3C alkyl group, R4: a 1-3C alkyl group or polyoxyethylene group having 1-50 addition mole number, X: halogen atom, -CH3SO4, or -C2H5SO4) or polyethylene oxide addition compound of dioleyl monoalkyl quaternary ammonium salt as essential components. Said emulsifying agent exhibits an excellent emulsifying effects over a wide range of HLB, providing thereby emulsions which are stable for a long period of time.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to emulsifiers for producing long-term stable emulsions.

[Conventional technology]

When producing an emulsion by emulsifying oil and water, it is common practice to determine the so-called required HL B of the oil and select an emulsifier that matches it. In general, H
A combination of a hydrophilic emulsifier with a high LB and a lipophilic emulsifier with a low HLB is used.

Examples of hydrophilic emulsifiers with high HLB include fatty acid soaps, anionic surfactants such as alkylbenzene sulfonates, and alkyl sulfate salts; Examples include ionic surfactants. Also, H.L.
Examples of lipophilic emulsifiers with low B include nonionic surfactants such as sorbitan fatty acid esters and glycerin fatty acid esters.

The method for determining the HL B of these emulsifiers is described in the Journal of Society of Cosmetic Chemists (J.
Soc, Cosmetic Chem,) Volume 5, No. 24
9 (1954), Science Vol. 23, p. 546 (195
3rd year), Ryohei Oda “Synthesis of surfactants and their applications” (
Shin Shobo), page 501 (1957), etc. In addition, the required HLB for oil can be determined by, for example,
Solubilization Technology” (Engineering Book) pp. 79-81 (197
6 years), etc.

By the way, this HLB was originally determined experimentally through emulsification tests, and there are various calculation methods depending on the type of emulsifier in order to match the experimental value. The existence of various calculation methods makes the application of HLB complicated, and even if the values obtained by calculation are used, it is rare to obtain a stable emulsion, and it is necessary to repeat numerous experiments by trial and error. It won't happen. In this way, it is not easy to obtain a stable emulsion by applying HLB.

[Problem to be solved by the invention]

As mentioned above (in the production of various emulsions, if the type and properties of the oil used change, the required HLB will change, so it is necessary to select the most suitable emulsifier according to this required HLB. The problem was that it was quite difficult.

Therefore, an object of the present invention is to provide an emulsifier that exhibits excellent emulsifying power over a wide range of HLB and can produce emulsions that are stable for a long period of time.

[Means to solve the problem]

As a result of intensive studies to achieve the above object, the present inventors have discovered that this object can be achieved by using a specific di-long chain alkyl quaternary ammonium salt as an essential component, and have completed the present invention. reached.

That is, the present invention is based on the following general formula;
R4 is an alkyl group having 1 to 3 carbon atoms or a polyoxyethylene group having 1 to 50 moles of addition; X is a halogen atom, CH35O, or -C, H, So) The present invention relates to an emulsifier characterized by containing a class ammonium salt as an essential component.

[Structure and operation of the invention]

The quaternary ammonium salt used in the present invention is characterized by having two oleyl groups as long-chain alkyl groups, as represented by the above general formula, and R4 in the general formula is R3
A dioleyldialkyl quaternary ammonium salt having an alkyl group having 1 to 3 carbon atoms similar to the above, and a dioleylmonoalkyl quaternary ammonium salt having R1 in the general formula as a polyoxyethylene group having an additional mole number of 1 to 50. This includes polyethylene oxide adducts of salts.

By using such a specific quaternary ammonium salt, excellent emulsifying power is exhibited in a wide range of HLB, making it possible to produce an emulsion that is stable for a long period of time. If dialkyl dimethyl quaternary ammonium salts such as beef tallow alkyl, hardened beef tallow alkyl, and coconut oil alkyl are used, it is difficult to produce the above-mentioned stable emulsion, and the stability, especially at low temperatures, is significantly impaired. Prone to problems.

Oleic acid, which is a raw material for obtaining the quaternary ammonium salt of the present invention, includes fatty acid mixtures having an oleic acid content of 70% by weight or more, such as fractionated beef tallow fatty acids, partially hydrogenated fatty acids such as soybean oil fatty acids, and tall oil fatty acids. However, if necessary, beef tallow fatty acid, lard fatty acid, or palm oil fatty acid with a high oleic acid content can be used alone or in a mixed system with the above oleic acid, as long as the lipophilic-hydrophilic balance is not disturbed. .

The dioleylamine of the present invention can be obtained by converting such oleic acid into dioleylamine by a known method, and then quaternizing the dioleylamine as it is or after adding ethylene oxide with a reagent consisting of an alkyl halide, dimethyl sulfate, or diethyl sulfate. A polyethylene oxide adduct of a dialkyl quaternary ammonium salt or a dioleyl monoalkyl quaternary ammonium salt can be obtained.

In the latter adduct, the number of moles of ethylene oxide added is 1 to 50, and if it exceeds 50, a wide range of HL
B is not preferable because it becomes difficult to obtain a stable emulsion.

Oils that can be used to produce stable emulsions using the emulsifier of the present invention include mineral oils, animal and vegetable oils, waxes, fatty acid esters, paraffins, higher alcohols, aromatic carboxylic acid esters, chlorinated hydrocarbons, polyolefins, There are silicones and the like, and these materials can be used alone or as a mixture of two or more.

The amount of the emulsifier used in the present invention is usually 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight per 100 parts by weight of oil. If this amount is too small, the stability of the emulsion will not be sufficient, and if it is used in excess of the specified amount, no significant improvement in the effect will be seen, which is economically disadvantageous.

When producing an emulsicon using the emulsifier of the present invention, a polyethylene oxide adduct of a dioleyl dialkyl quaternary ammonium salt or a dioleyl monoalkyl quaternary ammonium salt may be added, depending on the type of oil and emulsification type described above. These quaternary ammonium salts may be used alone or as a mixture of two or more, and if necessary, other surfactants may be used in combination with this quaternary ammonium salt.

Other surfactants include, for example, polyethylene oxide alkyl ether, polyethylene oxide fatty acid ester, polyethylene oxide sorbicun fatty acid ester, sorbitan fatty acid ester, (poly)glycerin fatty acid ester, sea sg fatty acid ester, polyethylene oxide alkyl phenyl ether, polyethylene oxide Nonionic surfactants such as polypropylene oxide block or random adducts, fatty acid alkylolamides or their polyethylene oxide adducts or polyethylene oxide adducts of alkyl amines, alkyl trimethyl ammonium chloride, polyethylene oxide alkyl monomethyl ammonium chloride, alkyl dimethyl benzyl Cationic surfactants such as ammonium chloride, alkylimida 7974 salts, alkylisoquinolinium bromides or carphonates of alkylamines, amphoteric surfactants such as dimethyldialkylhetaines, alkylglycines or alkylamidohetaines, Examples include amine oxide. The proportion of these other surfactants used is preferably 50% by weight or less.

In addition, when producing the emulsion, other polymeric emulsion stabilizers such as methylcellulose, carboxymethylcellulose, polyvinyl alcohol, and starch may be used in combination, as well as commonly used preservatives,
A thickener, anti-sagging agent, rust preventive agent, pH adjuster, etc. can also be used in combination.

〔Effect of the invention〕

By using the emulsifier of the present invention, stable emulsions can be obtained under a wide range of conditions, both in the water-in-oil type (W2C type) and in the oil-in-ice type (0/W type). Therefore, the emulsifier of the present invention can be used as an effective emulsifier in a wide range of fields such as cosmetics, medicine, agricultural chemicals, mold release agents, water repellents, waterproofing agents, emulsion fuels, and emulsion polymerization.

〔Example〕

Hereinafter, the present invention will be explained more specifically by describing examples.

Example 1 Polyethylene oxide adducts of dioleyl dialkyl quaternary ammonium salts or dioleyl monoalkyl quaternary ammonium salts according to Samples 11ml to 7 shown in Table 1 below were used as emulsifiers of the present invention. Further, for reference, the surfactants according to samples Nos. 8 to 1o shown in the same table were used as emulsifiers for comparison.

The oleic acid used as the raw material for the polyethylene oxide adduct of dioleyl dialkyl quaternary ammonium salt or dioleyl monoalkyl quaternary ammonium salt shown in Table 1 is industrial grade with an oleic acid content of about 75% by weight. It is oleic acid.

Furthermore, in the same table, the numbers in parentheses for the polyethylene oxide adduct and polyoxyethylene nonionic surfactant all indicate the number of moles of ethylene oxide added.

Using the above emulsifier, oil (reagents are used unless otherwise specified), moisture, and other additive components listed in Table 1, the following method is used at the blending ratio (wt%) listed in the same table. The preparation of an emulsion and the stability of this emulsion were investigated. The results were as shown in Table 2 below.

<Preparation and evaluation method of emulsions> First, an emulsifier is added to the oil, and the mixture is heated in a homomixer at room temperature for oils that are liquid at room temperature, or at a temperature 10°C or more higher than the melting point of the oil for oils that are solid at room temperature. An emulsion was prepared by stirring the mixture at 5.00 rpm and adding water or warm water little by little while continuing the stirring. In addition, when a polymeric emulsion stabilizer is used as an additive component other than the emulsifier, this additive is added immediately after preparing the emulsion and stirred lightly.

After preparing such an emulsion, it was cooled to room temperature if necessary, transferred to a 100 mff measuring cylinder, and stored at room temperature for one month, and then observed whether the emulsion had separated. A case where no separation occurred at all was evaluated as ○, a case where a slight amount of separation was observed was evaluated as △, and a case where separation was significant was evaluated as ×.

As is clear from the results in Table 2 above, stable emulsions can be obtained using the emulsifier of the present invention, but the emulsion stability is inferior when other emulsifiers are used.

Example 2 Using dioleyldimethyl quaternary ammonium salt (made from the same industrial oleic acid as in Example 1) and dicured beef tallow alkyldimethyl quaternary ammonium salt,
A mixture of carnauba wax and solid paraffin was solubilized.

That is, 10 parts by weight of a mixture of carnauba wax and solid paraffin in a weight ratio of 3, 85 parts by weight of water, and 5 parts by weight each of the above-mentioned dioleyldimethyl quaternary ammonium salt or dicured tallow alkyldimethyl quaternary ammonium salt. Two types of samples were prepared by mixing and dissolving the above, and both samples were placed in a 100ml mayonnaise bottle and left in a cool line at -5°C for 3 months.

As a result, the emulsifier of the present invention, dioleyldimethyl 4
In the case where the grade ammonium salt was used, the condition remained almost unchanged from the initial state, and it remained a transparent solution, but in the case where the dicured tallow alkyl dimethyl quaternary ammonium salt was used, a cloudy liquid settled at the bottom of the bottle. Ta.

This shows that when the emulsifier of the present invention is used, the low-temperature stability can be significantly improved compared to the usual commercially available di-cured beef tallow alkyldimethyl quaternary ammonium salt.

Claims (1)

[Claims] (1) The following general formula; ▲ Numerical formulas, chemical formulas, tables, etc. or a polyoxyethylene group with an additional mole number of 1 to 50,
X is a halogen atom, -CH_3SO_4 or -C_2
An emulsifier characterized by containing a quaternary ammonium salt represented by H_5SO_4 as an essential component.