JPH0832913B2 - Method for producing amphoteric surfactant - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an amphoteric surfactant having excellent cleaning performance, foam stability, and good storage stability.

2. Description of the Related Art In recent years, surfactants used as a base for kitchen detergents and shampoos have been required to have low toxicity and low irritation. Amideamine type amphoteric surfactants and amidobetaine type amphoteric surfactants are widely used as such agents.

Amidoamine-type amphoteric surfactants and amidobetaine-type amphoteric surfactants have hitherto been produced by using monochloroacetic acid as an amphoteric reaction agent. However, when an amphoteric reaction is carried out using monochloroacetic acid, sodium chloride is inevitably formed as a by-product, which cannot be removed by a normal treatment operation, so that sodium chloride remains in the product. is there. Also, when an amidoamine-type amphoteric surfactant or amidobetaine-type amphoteric surfactant obtained from monochloroacetic acid is compounded in a liquid detergent composition such as shampoo or kitchen detergent, it has low compatibility with other surfactants. ,
There was a drawback that the cold resistance was poor and it was difficult to formulate.

As a method for improving such drawbacks, various salt-free amidoamine-type amphoteric surfactants and amidobetaine-type amphoteric surfactants have been proposed. For example, there is a method of using an acrylic ester such as ethyl acrylate for the amphoteric reaction. When an amphoteric reaction is carried out using an acrylic ester, sodium chloride is not by-produced, but alcohol is by-produced when the acrylic ester is added. As a method for producing other salt-free type amphoteric surfactants, a method in which acrylic acid is directly added to perform amphoteric conversion has been proposed, but there is a problem that it is necessary to remove unreacted acrylic acid. is there.

The object of the present invention is to provide a method for producing an amidoamine-type amphoteric surfactant having good compatibility with other surfactants or auxiliary agents or an amidobetaine-type surfactant having excellent cold resistance. It is to be.

Means for Solving the Problems The above-described object of the present invention is achieved by subjecting a reaction product mixture containing an amidoamine-type amphoteric surfactant or an amidobetaine-type surfactant to a reverse osmosis membrane.

That is, the method for producing the amidoamine-type or amidobetaine-type amphoteric surfactant of the present invention is represented by the following general formula (I) or (II): [Wherein, in the above formula, R ₁ and R ₄ each independently represent an alkyl group or alkylene group having 9 to 19 carbon atoms, and R ₂ and R ₃ each independently represent a hydroxyethyl group or a hydrogen atom. In which R ₅ and R ₆ each independently represent a methyl group, an ethyl group, or a hydroxyethyl group], and an amidoamine compound represented by the following general formula (II
I): ClCH ₂ COOM (III) [wherein M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a cation residue of an alkanolamine or a lower aliphatic amine] or React with the salt,
The reaction product mixture is subjected to reverse osmosis membrane treatment to remove salt together with the membrane permeate and to concentrate the reaction product in the membrane impermeable liquid.

In the method of the present invention, it is preferable to adjust the concentration of the amidoamine-type or amidobetaine-type amphoteric surfactant in the reaction product mixture used for the reverse osmosis membrane treatment to 5 to 45%.

Further, in the method of the present invention, the reverse osmosis membrane treatment is 5 to
It is preferably carried out under a pressure of 40 kg / cm ² .

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the general formula (I) which is a starting material for the reverse osmosis membrane treatment of the composition of the present invention is condensed with a fatty acid or a fatty acid ester and a diamine compound such as aminoethylethanolamine, or It can be easily obtained by hydrolyzing an imidazoline compound such as alkyl-1- (2-hydroxyethyl) -2-imidazoline.

Examples of the amidoamine compound represented by the general formula (I) include N-cocoyl-N '-(2-hydroxyethyl) ethylenediamine and N-lauroyl-N- (2-.
Hydroxyethyl) ethylenediamine, N-caproyl-N '-(2-hydroxyethyl) ethylenediamine,
N-stearoyl-N '-(2-hydroxyethyl) ethylenediamine, N-oleoyl-N'-(2-hydroxyethyl) ethylenediamine, N-cocoyl-N-
(2-hydroxyethyl) ethylenediamine, N-lauroyl-N- (2-hydroxyethyl) ethylenediamine, N-caproyl-N- (2-hydroxyethyl) ethylenediamine, N-stearoyl-N- (2-hydroxyethyl) ethylenediamine, N-oleoyl-N '
Examples thereof include compounds such as-(2-hydroxyethyl) ethylenediamine.

The compound of the general formula (II), which is another starting material of the reverse osmosis membrane treated product of the composition of the present invention, is obtained by condensing a fatty acid or a fatty acid ester with a diamine compound such as N, N-dimethylpropanediamine. Can be easily obtained. For example, N-lauroyl-N ', N'-dimethylpropanediamine, N-cocoyl-N', N'-dimethylpropanediamine, N-caproyl-N ', N'-dimethylpropanediamine, N-stearoyl-N', N'-dimethylpropanediamine, N-oleoyl-N ', N'-
Dimethylpropanediamine, N-oleoyl-N ', N'
-Dimethylpropanediamine, N-lauroyl-N ',
N'-diethylpropanediamine, N-lauroyl-
N ', N'-dihydroxyethyl propane diamine etc. are mentioned.

The amphoteric surfactant which is the target of the reverse osmosis membrane treatment of the composition of the present invention is the amidoamine compound represented by the general formula (I) or (II) and 1 to 25 mol of monochloroacetic acid and sodium hydroxide in an aqueous solution at a temperature of Obtained by reacting at 70 to 95 ° C.

The compound produced by the reaction of the amidoamine compound of the general formula (I) or (II) with monochloroacetic acid is
An amphoteric surfactant as shown below as a main product and sodium chloride as a by-product, and unreacted raw materials and the like are mixed.

[Wherein R ₁ and M are the same as defined above, R ₂ ′ and R ₃ ′ are CH ₂ COOM,
Represents a hydroxyethyl group or a hydrogen atom] or the general formula (II ′) [Wherein R ₄ , R ₅ , R ₆ and M are the same as defined above] Examples of the reverse osmosis membrane used in the present invention include a cellulose acetate membrane, a sulfonated polysulfone membrane, a polyamidated sulfone membrane and the like.

In order to treat a reaction product mixture containing the amidoamine-type amphoteric surfactant or the amidobetaine-type amphoteric surfactant using these reverse osmosis membranes, the amidoamine-type amphoteric surfactant or the amidoamine-type amphoteric surfactant in the reaction product mixture is used. The concentration of the amidobetaine type amphoteric surfactant is 5 to 45%, preferably 20 to
The pressure is adjusted to 40%, the pressure is 5 to 40 kg / cm ² , and the temperature varies depending on the type of the reverse osmosis membrane, but generally the treatment is performed at room temperature. Since the amount of the liquid to be treated decreases with the treatment time, the reverse osmosis membrane treatment is performed while replenishing the liquid to be treated with water.

Since the content of sodium oxide in the amphoteric surfactant produced by the method of the present invention is remarkably reduced, another surfactant can be added to the amphoteric surfactant to use it as a detergent composition. Such compounding surfactants include anionic surfactants, cationic surfactants, amphoteric surfactants,
It is selected from nonionic surfactants. These include, for example, fatty acid soap, higher alcohol sulfate ester salts,
Polyoxyethylene higher alcohol ester salt, higher alcohol phosphate ester and salt thereof, polyoxyethylene higher alcohol phosphate ester and salt thereof, polyoxyethylene higher fatty acid phosphate ester and salt thereof, sulfonated higher fatty acid salt, sulfonated higher salt Fatty acid higher alcohol ester salt, higher alcohol sulfosuccinic acid ester acid, α-sulfo higher alcohol acetate, stearic acid diethanolamide, lauric acid diethanolamide, stearic acid monoethanolamide and other condensates of higher fatty acid and alkylolamine, and their Ethylene oxide adduct, polyoxyethylene higher fatty acid monoethanolamide phosphate, N-long chain acyl-glutamate, N-long chain acyl-sarcosine salt, N
N such as long-chain acyl-N-alkyl-β-alanine salt
A long-chain acylamino acid salt, a higher alkylaminopropionate such as laurylaminopropionic acid, a higher alkyliminodiacetic acid salt such as lauryliminodiacetic acid salt, a higher alkyldimethylammonium chloride and a higher alkyltrimethylammonium chloride.

By treating a reaction product mixture containing an amidoamine-type or amidobetaine-type amphoteric surfactant synthesized by a conventional method with a reverse osmosis membrane, it is possible to remove contained inorganic substances and organic low-molecular compounds, thereby improving compatibility and cold resistance. The sex can be improved.

Hereinafter, the present invention will be described in more detail with reference to examples and application examples.

Example 1 2-coconut oil fatty acid alkyl-N- (2-hydroxyethyl) imidazoline 1 mol (272 g), sodium hydroxide 20 g, and water 842 g were heated and stirred for 1 hour at a temperature of 80 to 90 ° C., Monochloroacetic acid 2 mol 189g and sodium hydroxide
140g was added and reacted at a temperature of 80 to 90 ° C for 3 hours to obtain N-
1460 g of a reaction product mixture containing an amidoamine type amphoteric surfactant based on lauroyl-N'-hydroxyethyl-N'-carboxymethylethylenediamine was obtained. The salt content of this product was 8%, the dry residue was 38%, and the viscosity at 25 ° C. was 800 cp (this is used as a sample). Next, the pH of the reaction product mixture solution containing an amidoamine type amphoteric surfactant was adjusted to 7 with hydrochloric acid, and 190 g of purified water was added thereto to adjust the solid content concentration to 35%. This solution was placed in a reverse osmosis membrane treatment device (trade name "20 type RO / UF test module": Techno Universe Co., Ltd.) set with a polyamidated sulfone membrane having a membrane area of 0.4a, and pressure was 20 kg / cm ^2.
Water was added so that the amount of the treatment liquid would not decrease due to the removal of the membrane permeate. After the total amount of 2750 g of the permeated liquid was taken, the addition of water was stopped and a further 550 g of the permeated liquid was taken to make the solid concentration of the treatment liquid 30%. The salt concentration in the amphoteric surfactant-containing aqueous solution obtained by this reverse osmosis membrane treatment was 0.5%, and the dry residue was 30%. Its viscosity at 25 ° C was 110 cp (this is used as a sample).

Example 2 1 mol of coconut oil fatty acid (208 g) and 1 mol of N, N-dimethylpropanediamine (102 g) were reacted under reduced pressure at 160 to 200 ° C. for 4 hours to remove 1 mol of water produced. Water 80
Charge 0 g and 2 mol (80 g) of sodium hydroxide, and react with 1 mol (117 g) of monochloroacetic acid for about 5 hours to obtain a dry residue of 36.2%, salt of 5.3% and a viscosity of 10 at 25 ° C.
1260 g of a light yellow transparent solution of 5 cp was obtained (this is used as a sample). Next, 200 g of water was added to this to adjust the solid concentration to 30%, and then a reverse osmosis membrane treatment device (trade name "20 type RO / UF test module": set with a polyamidated sulfone membrane having a membrane area of 0.4 m ² ): Pressure 20kg / c for Techno Universe Co., Ltd.
It was circulated at m ² and water was added so that the amount of the treatment liquid would not decrease by removing the membrane permeate. 2500g in total
After removing the permeate, the addition of water was stopped and an additional 300 g of permeate was taken to make the solid concentration of the treatment liquid 30%. The amidobetaine-type amphoteric surfactant-containing aqueous solution obtained by this reverse osmosis membrane treatment had a dry residue of 30.5% and a salt concentration of 0.8%.
At 25 ° C, the viscosity was 83% (this is used as a sample).

Application Examples 1 to 12 and Comparative Application Examples 1 to 12 The difference between the reverse osmosis membrane-treated product of the amidoamine-type amphoteric surfactant and the amidobetaine-type amphoteric surfactant obtained in Examples 1 and 2 and the untreated product is examined. Therefore, a three-component system (active ingredient 20%, pH 7.0) composition of an anionic surfactant composed of sodium lauryl sulfate, triethanolamine lauryl sulfate and sodium polyoxyethylene lauryl sulfate, and coconut oil fatty acid diethanolamide The first
The composition, the compatibility, the low temperature stability and the viscosity of this composition were measured. Each test method was as follows. The results are shown in Tables 1 to 3.

(Compatibility)

After leaving the test solution at 20 ° C. for 24 hours, its appearance was visually observed and judged according to the following criteria.

○: A uniform and transparent solution as a whole △: Slight turbidity or separation is observed.

X: White turbidity or separation [Low temperature stability] After leaving the test solution at -5 ° C for 3 days, its appearance was visually observed and judged according to the following criteria.

○: A uniform and transparent solution as a whole △: Slight turbidity or separation is observed.

X: White turbidity or separation [Viscosity] The viscosity of the test liquid was measured at 25 ° C using a B type rotational viscometer, and evaluated according to the following criteria.

◎ …… 10000cp <○ …… 5000cp to 10000cp Δ …… 1000cp to 5000cp × …… <1000cp Application Example 13 Weakly acidic shampoo / reverse osmosis membrane-treated amidobetaine type amphoteric surfactant (synthesized by replacing coconut oil in Example 2 with lauric acid) 10.0
% ・ Lauryl sulfate triethanolamine 10.0 ・ Palm oil fatty acid diethanolamide 2.0 ・ Glycerin 5.0 ・ EDTA 0.1 ・ Citric acid pH 6 amount ・ Preservative, perfume appropriate amount ・ Water balance 100 This shampoo has a viscosity (25 ° C) of 1060cp The foaming was good, and the appearance was transparent even when left at −5 ° C. for 3 days, and the stability at extremely low temperature was excellent.

However, in the case of using the amidobetaine-type amphoteric surfactant-containing solution which was not subjected to the reverse osmosis membrane treatment, it became cloudy at -5 ° C for 3 days.

Application Example 14 Kitchen Detergent • Reverse osmosis membrane treated amidoamine type amphoteric surfactant (Example 1-) 10.0% • Sodium lauryl sulfate 3.0 • Sodium alkylbenzene sulfonate 2.0 • Lauric acid diethanolamide 2.0 • Concentrated hydrochloric acid pH8 amount • Antiseptic Agent, fragrance, appropriate amount , water remaining 100 This kitchen detergent has a viscosity (25 ° C) of 530cp and good detergency. It is transparent even when left at -5 ° C for 3 days and has excellent low temperature stability. It was However, when using an amidoamine type amphoteric surfactant that has not been subjected to reverse osmosis membrane treatment,
It became cloudy at -5 ° C for 3 days.

Application Example 15 Conditioning Shampoo-Reverse osmosis membrane-treated amidoamine type amphoteric surfactant (Example 1-) 20.0% -Polyoxyethylene sodium lauryl sulfate 5.0-Propylene glycol 5.0-Hydroxyethyl cellulose hydroxypropylmethylammonium chloride ether 1.0-Preservative, Fragrance Suitable amount / Water remaining 100 This conditioning shampoo has a viscosity (25 ℃).
Had a good detergency of 1000 cp, was transparent even after standing at -5 ° C for 3 days, and was excellent in low-temperature stability.

Application Example 16 Transparent gel detergent / reverse osmosis membrane-treated amidobetaine-type amphoteric surfactant (synthesized by replacing coconut oil in Example 2 with lauric acid) 12.0
% ・ Sodium lauryl sulfate 4.0 ・ Palm oil fatty acid diethanolamide 4.0 ・ Propylene glycol 10.0 ・ Citric acid pH 6 amount ・ Preservative, perfume proper amount ・ Water residue 100 This transparent gel-like detergent has moderate hardness and should be used. When it was quickly dissolved in the palm of the hand, it foamed well and had good detergency, and it was transparent even after standing at -5 ° C for 3 days and was excellent in low-temperature stability.

EFFECTS OF THE INVENTION The amidoamine-type or amidobetaine-type amphoteric surfactant that has been subjected to reverse osmosis membrane treatment by the method of the present invention is excellent in compatibility and cold resistance and is useful as a component of a detergent composition.

Claims (3)

[Claims] 1. The following general formula (I) or (II): [Wherein, in the above formula, R ₁ and R ₄ each independently represent an alkyl group or alkylene group having 9 to 19 carbon atoms, and R ₂ and R ₃ each independently represent a hydroxyethyl group or a hydrogen atom. In which R ₅ and R ₆ each independently represent a methyl group, an ethyl group, or a hydroxyethyl group], and an amidoamine compound represented by the following general formula (II
I): ClCH ₂ COOM (III) [wherein M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a cation residue of an alkanolamine or a lower aliphatic amine] or React with the salt,
This reaction product mixture is subjected to a reverse osmosis membrane treatment to remove salt together with the membrane permeate and to concentrate the reaction product in the membrane impermeable liquid, which is characterized by being an amidoamine type or amidobetaine type amphoteric surfactant. Method of manufacturing agent. 2. The concentration of the amidoamine-type or amidobetaine-type amphoteric surfactant in the reaction product mixture to be subjected to the reverse osmosis membrane treatment is adjusted to 5 to 45%. The method described. 3. The method according to claim 1, wherein the reverse osmosis membrane treatment is performed under a pressure of 5 to 40 kg / cm ² .