JPH0699706B2 - Surfactant composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a surfactant composition.

[Prior Art] Conventionally, a composition containing a sulfosuccinic acid type surfactant, a sodium borohydride and a water-soluble salt of citric acid as a surfactant composition (Japanese Patent Publication No. 62-5200, etc.).
It has been known.

[Problems to be Solved by the Invention] However, these surfactant compositions have problems such as poor foaming power in neutral to weakly acidic conditions.

[Means for Solving Problems] The present inventors have arrived at the present invention as a result of investigations to develop a detergent composition having a good foaming power in neutral to weakly acidic conditions.

That is, the present invention has the general formula [Wherein R ₁ is an aliphatic primary alcohol residue having 8 to 22 carbon atoms, or (R ₂ is a residue of a higher fatty acid having 8 to 22 carbon atoms, R ₃ is hydrogen or a methyl group), n is 0 to 20, M ₁ and M ₂ are hydrogen atoms, alkali metals, alkaline earth metals, ammonium or It is a lower alkanolamine cation. ] The total amount of the sulfosuccinic acid type surfactant (A) represented by the formula (A) is 2% or less based on the weight of the general formula R ₁ O (CH ₂ CH ₂ O) nH (2) (wherein R ₁ , N are the same as R ₁ and n in the general formula (1). A surfactant composition characterized in that it consists of diester (C) represented by (R _1, the same. As n in the formula in R _1, n of the general formula (1)).

In the general formula (1) showing the sulfosuccinic acid type surfactant in the present invention, the alcohol constituting the residue of the aliphatic primary alcohol having 8 to 22 carbon atoms of R ₁ is a linear or branched saturated or unsaturated alcohol. Alcohols such as octyl alcohol, decyl alcohol, dodecyl alcohol,
Examples thereof include tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, eicosyl alcohol, docosyl alcohol, and oleyl alcohol.
It is also possible to use a synthetic alcohol having a branched structure produced from an olefin by the oxo method.

Examples of the synthetic alcohol include “Dovanol” (manufactured by Shell Chemical Co., Ltd.), “Oxocol” (manufactured by Nissan Chemical Industry Co., Ltd.),
"Dia Doll" (manufactured by Mitsubishi Kasei), "Real (LI
AL) ”(manufactured by Kimika Augusta).

These synthetic alcohols are a mixture of a branched alcohol and a straight-chain alcohol, and the ratio and structure thereof vary depending on the reaction conditions, the catalyst used and the type of the starting material. The content is usually 10 to 70% by weight. Of these, alcohols having 10 to 16 carbon atoms and an alkyl branched alcohol content of 0 to 70% by weight are preferable, and dodecyl alcohol, tetradecyl alcohol, and C 12 to 14 alkyl branched alcohols are particularly preferable. An alcohol having an alcohol content of 20 to 65% by weight.

The higher fatty acid constituting the residue of the higher fatty acid having 8 to 22 carbon atoms of R ₂ is caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, oleic acid, erucic acid. , Linoleic acid, ricinolenic acid and coconut oil fatty acid. Of these, lauric acid and myristic acid are preferred.

n is preferably 0-7.

Examples of the alkali metal of M ₁ and M ₂ include lithium, sodium and potassium. Alkaline earth metals include magnesium, calcium, etc.Alkanolamines forming lower alkanolamine cations are mono-, di- or tri-ethanolamine as alkanolamines,
(N-, iso-) propanolamine etc. are mentioned.

Of M ₁ and M ₂ , sodium, magnesium and ammonium are preferable.

Specific examples of the sulfosuccinic acid-type surfactant represented by the general formula (1) include R ₁ , n, and
Examples of the surfactant include compounds (a-1) to (a-9) in which M ₁ and M ₂ have the groups and numerical values shown in Table 1 and a mixture of two or more thereof.

The alcohol (B) represented by the general formula (2) and the diester (C) represented by the general formula (3) are present in the composition as an unreacted product, a by-product or a decomposed product in the step of synthesizing (A). However, their total amount is 2.0% or less, preferably 1.3% or less, based on the weight of (A). (B)
When the total amount of (C) and (C) exceeds 2.0%, the foaming power decreases as the amount increases.

The composition of the present invention can be obtained as follows. By sulfonating a primary alcohol constituting R ₁ of the general formula (1) or a maleic acid monoester obtained by an esterification reaction of an ethylene oxide adduct thereof and maleic anhydride with a sulfite and / or a bisulfite. The target sulfosuccinic acid type surfactant is obtained. R ₁
The molar ratio of the primary alcohol or its ethylene oxide adduct and maleic anhydride constituting 1.00: 1.04 to 1.0
It is 0: 1.25, preferably 1.00: 1.05 to 1.00: 1.15, and the esterification temperature is 40 to 70 ° C, preferably 45 to 60 ° C. During esterification, an organic acid salt such as sodium acetate is added as a catalyst in an amount of 0.1 to 2% by weight, preferably 0.2 to 1% by weight. Sulfite and / or bisulfite are used in an amount of 1.0 to 1.5 times, preferably 1.02 to 1.2 times the molar amount of maleic anhydride used, and sulfonation is carried out at a temperature of 40 to 90 ° C, preferably 50 to 70 ° C.

Examples of the sulfite and bisulfite include sodium salt, potassium salt, magnesium salt and ammonium salt. If one of these sulfites is used, the same M ₁ and M _{2 in} the general formula (1) can be obtained. it can. Further, two or more kinds of these sulfites are mixed, or bisulfite and an alkali having a cation portion different from that of bisulfite (hydroxide such as sodium, potassium or magnesium; carbonate or bicarbonate; ammonia, alkanol Different ones of M ₁ and M ₂ can be obtained by using the one neutralized with (such as amine).

Any of the raw materials may be charged at the time of sulfonation, and water and sulfite and / or bisulfite may be added to maleic acid monoester, or sulfite and / or bisulfite may be added to water. The maleic acid monoester immediately after preparation or separately prepared and cooled to room temperature may be added to the dissolved solution. A production method other than the above, for example, esterification of a primary alcohol constituting R ₁ of the general formula (1) or an ethylene oxide adduct thereof with substantially equimolar maleic anhydride in the presence of a catalyst or without a catalyst,
Further, the composition of the present invention can be obtained by extracting and removing the alcohol (B) and the diester (C) from the composition obtained by sulfonation with an organic solvent such as petroleum ether.

The contents of the alcohol (B) and the diester (C) in the composition of the present invention can be determined by gas chromatography or by extracting the composition with petroleum ether and from the nuclear magnetic resonance spectrum of the extract.

The form of the composition according to the invention is usually a liquid or paste with a concentration of 30 to 50%, a dewatered powder, a frame or a block.

The pH of the composition of the present invention is a value measured by diluting it with water so that (A) is 1% by weight, and is usually 4 to 8, preferably
It is 5.5 to 7. When necessary, the pH can be adjusted with normal alkali (caustic soda, triethanolamine, etc.) or acid (hydrochloric acid, citric acid, etc.).

The composition of the present invention can be used as a base for skin cleansing agents such as body shampoos, facial cleansers and hand washing detergents; hair washing agents such as shampoos and household detergents such as dish washing detergents.

When used as a base material for such a detergent, the composition of the present invention is diluted with water before use. Usually the amount used is 1
It is 50% by weight (active ingredient conversion), preferably 5 to 30% by weight. In the above, other components can be used in combination, and as such a usable substance, a general anionic surfactant (alkyl sulfate ester salt, alkyl ether sulfate ester salt, α-olefin sulfonate, alkyl sulfonate, Taurine-based surfactants, sarcosinate-based surfactants, isethionate-based surfactants, N-acyl acidic amino acid-based surfactants, monoalkyl phosphate ester salts, higher fatty acid salts and acylated polypeptides, etc.),
Amphoteric surfactants (alkyl betaine-type surfactants, amidopropyl betaine-type surfactants and imidazolinium betaine-type surfactants, sulfobetaine-type surfactants, phosphobetaine-type surfactants, amino acids such as sodium laurylaminopropionate Type surfactants, nonionic surfactants (coconut oil fatty acid diethanolamide, stearic acid monoglyceride, lauryl dimethylamine oxide, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, fatty acid sorbitan ester, polyoxyethylene fatty acid sorbitan ester) , Polyoxyethylene polypropylene glycol, etc., cationic surfactants (stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lanolin ethyl sulfate) Fatty acid aminopropylethyldimethylammonium, etc.), moisturizers (sodium pyrrolidone carboxylic acid, polyethylene glycol, etc.), lower alcohols (ethanol, propylene glycol, hexylene glycol, glycerin, etc.), inorganic salts (salt, bow pepper, magnesium chloride, Magnesium sulfate, etc., xylating agent [1-hydroxy-ethane-1,1-diphosphonate, nitrilotriacetic acid salt, ethylenediaminetetraacetic acid hydrochloric acid, citrate, oxalate, etc. (as salts, alkali metals such as sodium and potassium) Salt)], thickener (polyethylene glycol fatty acid diester, propylene glycol fatty acid ester, polyoxyethylene methyl glucoside fatty acid ester, etc.), polymer compound (carboxymethyl cellulose, hydroxyethyl cell) Over scan, such as cationized cellulose), flavoring, coloring agents, preservatives, conventional bases such as water, such as auxiliary agents.

[Examples] Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto.

Examples 1 to 4 and Comparative Examples 1 to 2 Example 1 186 g (1 mol) of lauryl alcohol and maleic anhydride 10
2.9 g (1.05 mol) and 1.4 g of anhydrous sodium acetate were reacted in a reaction vessel at atmospheric pressure under a nitrogen atmosphere at 50 to 60 ° C. for 5 hours. The obtained maleic acid monoester had an acid value of 215.1 (theoretical value: 212.6) and a half-esterified acid value of 203.5 (theoretical value: 202.
9), melting point 49 ° C. After cooling this to room temperature to a solid, under a nitrogen atmosphere, sodium sulfite 138.
9 g (1.1 mol) was dissolved in 570 g of water and gradually poured into a solution kept at 60 to 65 ° C. for sulfonation. PH during the reaction is 6
Adjusted to ~ 7 with citric acid or caustic soda. The sulfonation was carried out at 60 to 65 ° C for 5 hours to obtain the composition of the present invention. (Compounds in Table 1, a-1) Comparative Example 1 Lauryl alcohol 186 g (1 mol) and maleic anhydride 98
A surfactant composition was obtained in the same manner as in Example 1 except that g (1 mol) and sodium sulfite 126 g (1 mol) were used.

Example 2 A composition of the present invention was obtained in the same manner as in Example 1 except that ammonium sulfite was used instead of sodium sulfite.
(Compounds in Table 1, a-2) Example 3 The composition of the present invention was the same as in Example 1 except that a mixture of sodium bisulfite and magnesium hydroxide (molar ratio 1: 0.5) was used instead of sodium sulfite. I got a thing. (Compounds in Table 1 and a-3) Example 4 Maleic acid was obtained by half-esterifying in the same manner as in Example 1 using 281 g (1 mol) of alcohol obtained by adding 2 mol of ethylene oxide to synthetic alcohol I (molecular weight 193). A monoester was obtained. Next, add 1080 g of water, 138.9 g of sodium sulfite, and 12 g of sodium chloride to the mixture, and in a nitrogen atmosphere at 55 to 65 ° C.
Sulfonation was carried out for 5 hours to obtain a composition of the present invention. (Compounds in Table 1 and a-8) Comparative Example 2 Surfactant composition in the same manner as in Example 4 except that an alcohol prepared by adding 3 mol of ethylene oxide to a synthetic secondary alcohol having 12 to 14 carbon atoms was used. Got

Test Example 1 The contents of the alcohol (B) and the diester (C) and the foaming power in the compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were examined.

The contents of alcohol (B) and diester (C) were determined by gas chromatography and nuclear magnetic resonance spectrum of petroleum ether extract, and expressed as% by weight based on the amount of active ingredient.

The foaming power is 30 ppm of 200 ml of solution prepared by adjusting the concentration of active ingredient to 0.3% and pH to 6.0 using 15 ppm hard water (calculated as CaO).
30 ° C at a juicer mixer (Toshiba MX-390GN)
The mixture was stirred for 2 seconds and the foamability was evaluated by the foam height (mm) at that time.

Example 5 Composition of the present invention obtained in Example 2 32% by weight (effective concentration 40%) Polyoxyethylene (2) sodium lauryl ether sulfate 10% by weight Coconut oil fatty acid diethanolamide 1-3% by weight Water remaining amount Adjust the total 100 wt% pH to 6.

Example 6 composition 28 wt% of the present invention obtained in Example 4 (effective concentration 40%) Polyoxyethylene (2) Sodium lauryl ether sulphate 6% by weight coconut oil fatty acid diethanolamide 4% by weight water balance Total Adjust the 100 wt% pH to 6.

The shampoo compositions blended in the formulations shown in Examples 5 and 6 had good foaming and good feel after washing hair.

Example 7 composition 70 wt% of the present invention obtained in Example 1 (effective concentration 40%) Polyethylene glycol 4000 15% by weight water balance Total 100 wt% The above composition consists cleanser adjusted to pH 6.5 The composition had a good foaming power, and had a good feel of the skin after washing the face and no feeling of sliminess.

[Effects of the Invention] The composition of the present invention has a pH value of neutral to weakly acidic as compared with a composition comprising a conventional sulfosuccinic acid type surfactant, because components that hinder the foaming power are reduced. Has foaming power.
In addition, the detergent composition containing the composition of the present invention provides a detergent composition which has good defoaming and feeling after washing and is gentle on the skin and hair.

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Claims (1)

[Claims] 1. A general formula [Wherein R ₁ is an aliphatic primary alcohol residue having 8 to 22 carbon atoms, or (R ₂ is a residue of a higher fatty acid having 8 to 22 carbon atoms, R ₃ is hydrogen or a methyl group), n is 0 to 20, M ₁ and M ₂ are hydrogen atoms, alkali metals, alkaline earth metals, ammonium or It is a lower alkanolamine cation. ] The total amount of the sulfosuccinic acid type surfactant (A) represented by the formula (A) is 2% or less based on the weight of the general formula R ₁ O (CH ₂ CH ₂ O) nH (2) (wherein R ₁ , N are the same as R ₁ and n in the general formula (1). (Wherein R _1, n is R _1, n and the same. Formula (1)) surfactant composition characterized in that it consists of diester (C) represented by.