JPH0699707B2 - 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, as a surfactant composition, a composition containing a sulfosuccinic acid type surfactant, a sodium borohydride and a water-soluble salt of citric acid, and 2,6-di-tert-butyl-paracresol ( For example, JP-A-55-151097) is known.

[Problems to be Solved by the Invention] However, these surfactant compositions have a problem that they are inferior in stability over time and heat resistance.

[Means for Solving the Problems] The present inventors have arrived at the present invention as a result of investigations to develop a surfactant composition having good stability over time and heat resistance.

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), X ₁ and X ₂ are hydrogen atoms or SO ₃ M ₂ , and X is
_One of X ₁ and X ₂ is always a hydrogen atom and the other is SO ₃ M ₂ .
M ₁ and M ₂ are hydrogen atom, alkali metal, alkaline earth metal,
It is an ammonium or lower alkanolamine cation. n is 0-20. ] 2.5% to 1 based on the weight of the sulfosuccinic acid type surfactants (A) and (A)
5% general formula (Wherein M ₃ is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a lower alkanolamine cation), and 0.5% to 5% of a citric acid based on the weight of the compounds (B) and (A). A surfactant composition comprising a compound (C) selected from the group consisting of an acid, an alkali metal salt thereof and an inorganic phosphoric acid (salt).

In the general formula (1) showing the sulfosuccinic acid type surfactant in the present invention, the alcohol constituting the residue of the fatty acid primary alcohol having 8 to 22 carbon atoms of R ₁ is a linear or branched saturated or unsaturated alcohol. For example, 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. As the synthetic alcohol, "Dovanol" (manufactured by Shell Chemical Co., Ltd.), "Oxocol" (manufactured by Nissan Chemical Industry Co., Ltd.), "Dia Doll" (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.), "LIAL"
(Made by Kimika Augusta) and the like. 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, preferably, the content of the alcohol having 10 to 16 carbon atoms and the alcohol having an alkyl branch is 0 to 70.
% By weight of alcohol, particularly preferably dodecyl alcohol, tetradecyl alcohol and 12 to 14 carbon atoms.
And the content of the alcohol having an alkyl branch is 20 to 85% by weight.

The higher fatty acid constituting the residue of the higher fatty acid having 8 to 22 carbon atoms of R ₂ is saturated or unsaturated, such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, Examples thereof include 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. Examples of alkaline earth metals include magnesium and calcium. Alkanolamines forming lower alkanolamine cations include mono-, di- or tri-ethanolamine,
Examples include n- or iso-propanolamine.

Of M ₁ and M ₂ , sodium, potassium 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 hydrogen atom, alkali metal, alkaline earth metal, ammonium or lower alkanolamine cation represented by M ₃ in the general formula (2) is the same as the _one described in the section of M ₁ and M ₂ in the compound of the general formula (1). And the preferred ones are also the same.

Specific examples of the compound represented by the general formula (2) include sodium sulfosuccinate, potassium sulfosuccinate and triethanol sulfosuccinate.

The compound of the general formula (2) can be obtained by sulfating maleic acid by a conventional method and neutralizing it with an alkali.

Examples of the alkali metal salt of citric acid in the compound (C) include lithium salt, sodium salt, potassium salt of citric acid and the like. Preferred are sodium and potassium salts of citric acid.

Inorganic phosphoric acid (salt) [refers to inorganic phosphoric acid and / or inorganic phosphate], inorganic phosphoric acid is orthophosphoric acid,
Examples thereof include phosphoric acid such as hypophosphoric acid, phosphorous acid and hypophosphorous acid, condensed phosphoric acid such as pyrophosphoric acid and tripolyphosphoric acid. Orthophosphoric acid is preferable. Examples of salts of inorganic phosphoric acids include salts of alkali metals, alkaline earth metals, ammonium and amines. Preferred are sodium salts and potassium salts of orthophosphoric acid.

The amount of (A) in the composition of the present invention is usually 20 to 80% based on the weight of the composition, and the amount can change the appearance and morphology of the composition.

The amount of (B) is 2.5% to 15%, preferably 5% to 10%, based on the weight of (A). If the amount of (B) is less than 2.5%, the stability over time and the heat resistance will decrease, and if it exceeds 20%, the creamy foam quality of the composition will be impaired.

The amount of (C) is 0.5% to 5%, preferably 2% to 3%, based on the weight of (A). If the amount of (C) is less than 0.5%, the stability over time and the heat resistance will decrease, and if it exceeds 5%, the creamy foam quality of the composition will be impaired.

The composition of the present invention comprises a maleic acid monoester obtained by an esterification reaction of a primary alcohol constituting R ₁ of the general formula (1) or an ethylene oxide adduct thereof and maleic anhydride with citric acid, an alkali metal salt thereof and an inorganic salt. It can be obtained by sulfonation with sulfite and / or bisulfite in the presence of compound (C) selected from the group consisting of phosphoric acid (salt). Examples of the sulfite and bisulfite include sodium salt, potassium salt, magnesium salt and ammonium salt. If one of these sulfites and / or bisulfites is used, M _{1 of} the general formula (1), The same M ₂ and M ₃ can be made. 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 If you use the one neutralized with amine)
Different ones of M ₁ , M ₂ and M ₃ are possible.

In the above, the molar ratio of the primary alcohol constituting R ₁ or its ethylene oxide adduct to maleic anhydride is usually 1: 1.05 to 1: 1.3, preferably 1: 1.1 to 1: 1.2.
The esterification temperature is usually 40 to 80 ° C, preferably 45 to 70 ° C. If necessary, an organic acid salt such as sodium acetate is used as a catalyst during the esterification, usually in an amount of 0.1 to 2% by weight, preferably 0.1 to 2% by weight based on the primary alcohol constituting R ₁ of the general formula (1) or an ethylene oxide adduct thereof. Add 0.2 to 1% by weight. The sulfite and / or bisulfite is usually 1 to 1.5 times the molar amount of maleic anhydride used, preferably 1.0
2 to 1.2 times mole used, usually 40 to 90 ℃, preferably 50 to 70
Perform temperature sulfonation at ° C.

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 may be added to the dissolved solution. A production method other than the above, for example, esterification of the primary alcohol constituting R ₁ of the general formula (1) or its ethylene oxide adduct with substantially equimolar maleic anhydride, if necessary, in the presence of a catalyst or in the absence of a catalyst. The compound (B) and / or the composition obtained by further sulfonation.
Alternatively, the composition of the present invention can be obtained by the method of adding the compound (C).

The form of the composition of the present invention usually has a concentration of 30 to 50% by weight.
Liquid or paste.

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, usually 5 to 8, preferably
It is 6.0 to 7.0. 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. The amount used is usually 1
It is 50% by weight (active ingredient equivalent), 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 surfactant, sarcosinate-based surfactant, isethionate-based surfactant, N-acyl acidic amino acid-based surfactant, monoalkyl phosphate ester salt,
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) Activators, amino acid type surfactants such as sodium laurylaminopropionate), 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 surfactant (stearyl trimethyl ammonium chloride, disteare chloride Dimethylammonium, 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 Show, magnesium chloride, magnesium sulfate, etc.), chelating agent [1-hydroxy-ethane-1,1-diphosphonate,
Nitrilotriacetate, ethylenediaminetetraacetate, citrate, oxalate, etc. (as salts are alkali metal salts such as sodium and potassium)], thickeners (polyethylene glycol fatty acid diester, propylene glycol fatty acid ester, polyoxyethylene methyl Glucoside fatty acid ester, etc.), polymer compound (carboxymethyl cellulose, hydroxyethyl cellulose, cationized cellulose, etc.), perfume, colorant, preservative, usual base such as water, auxiliary agent and the like. The method of using the cleaning agent may be the same as the conventional method.

[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 A glass autoclave was charged with 1 mol of synthetic alcohol II and 0.06 g of potassium hydroxide. After substituting the gas phase with nitrogen, 2 mol of ethylene oxide was reacted at 180 ° C.
1 mol of the obtained synthetic alcohol ethylene oxide adduct and 1.1 mol of maleic anhydride were reacted in a reaction vessel at 50-60 ° C. for 5 hours under a nitrogen atmosphere at atmospheric pressure. This maleic acid monoester under nitrogen atmosphere, 1.2 mol of sodium sulfite,
Sulfonation was carried out by adding sodium citrate (1% based on the total amount charged) to a solution in which water was calculated so that the weight of (A) was 40% in the composition for 1 hour. The pH during the reaction was adjusted to 6 to 7 with citric acid or caustic soda. The sulfonation was carried out at 60 to 65 ° C. for 5 hours to obtain a composition of the present invention (Table-2 Example 1).

Example 2 A composition was obtained in the same manner as in Example 1 except that 1.15 mol of maleic anhydride and 1.2 mol of sodium sulfite were used.

Example 3 Example 1 was repeated except that 1.15 mol of maleic anhydride and 1.2 mol of sodium sulfite were used, and sodium dihydrogen phosphate (1% by weight based on the total charged amount) was used instead of sodium citrate. A composition was obtained in the same manner as in Example 1.

Example 4 Similar to Example 1 except that 1 mol of dodecyl alcohol was added instead of 1 mol of synthetic alcohol II and 1 mol was added instead of 2 mol of ethylene oxide, and 1.15 maleic anhydride and 1.2 mol of sodium sulfite were used. To obtain a composition.

Comparative Example 1 A composition was obtained in the same manner as in Example 1 except that 1 mol of maleic anhydride and 1 mol of sodium sulfite were used in Example 1 and 0.4% by weight of sodium citrate was used based on the total charged amount. A composition was obtained by adding sodium borohydride to 0.02% by weight and 2,6-di-tert-butyl-para-cresol to 0.04% by weight.

Comparative Example 2 A composition was obtained in the same manner as in Example 1 except that 1.02 mol of maleic anhydride, 1.1 mol of sodium sulfite, and sodium citrate (0.4% by weight based on the total amount charged) were used in Example 1. .

Comparative Example 3 A composition was obtained in the same manner as in Example 1 except that 1.4 mol of maleic anhydride, 1.5 mol of sodium sulfite and sodium citrate (2.4% by weight based on the total amount charged) were used in Example 1. .

[Effect of the Invention] The composition of the present invention has better stability over time and heat resistance than a composition comprising a conventional sulfosuccinic acid type surfactant. Further, a cleaning composition containing the composition of the present invention,
It is possible to obtain a detergent composition which has good defoaming and feeling after washing and is gentle on the skin and hair.

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), X ₁ and X ₂ are hydrogen atoms or SO ₃ M ₂ , and X is
_One of X ₁ and X ₂ is always a hydrogen atom and the other is SO ₃ M ₂ .
M ₁ and M ₂ are hydrogen atom, alkali metal, alkaline earth metal,
It is an ammonium or lower alkanolamine cation. n is 0-20. ] 2.5% to 1 based on the weight of the sulfosuccinic acid type surfactants (A) and (A)
5% general formula (Wherein M ₃ is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a lower alkanolamine cation), and 0.5% to 5% of a citric acid based on the weight of the compounds (B) and (A). A surfactant composition comprising a compound (C) selected from the group consisting of an acid, an alkali metal salt thereof and an inorganic phosphoric acid (salt).