JPS5929638B2 - Post-treatment method of amphoteric activator - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for post-treatment of amphoteric activators.

More specifically, the present invention relates to a method for alleviating the irritation of an amphoteric surfactant by contacting a particular compound with an amphoteric surfactant obtained by reacting a higher amine with an amphoteric agent. Amphoteric surfactants obtained by reacting higher amines with amphoteric agents such as monochloroacetic acid are useful as bases for shampoo and hair rinses, fabric softeners, disinfectants, etc.; It is strongly desired that it be less irritating. The reaction between higher amines and an amphoteric agent such as monochloroacetic acid is usually carried out in the presence of a solvent or directly using an excess molar amount of the amphoteric agent because higher amines are extremely irritating to the skin. made by. For this reason, the amphoteric agent remains in the amphoteric surfactant, and skin irritation caused by this agent has become a problem. A known method is to thermally decompose the remaining amphoteric agent with an alkali such as sodium hydroxide, but this method does not completely decompose the agent, and may also cause decomposition of the double-sided surfactant or coloring of the activator. It also has problems such as corrosion of the reaction tank. It is also conceivable to recrystallize and extract the double-sided surfactant, but the yield is low and the process is complicated. As a result of repeated research to improve these drawbacks, the present inventors found that by treating an amphoteric surfactant made by reacting higher amines with an amphoteric agent with a specific compound, the contaminants of the amphoteric agent can be efficiently removed. The present invention has been achieved by discovering that the irritating properties of amphoteric surfactants can be alleviated.

That is, the present invention is a post-treatment method for an amphoteric surfactant, which is characterized by contacting an amphoteric surfactant obtained by reacting a higher amine with a monohalo organic acid type amphoteric agent with a sulfite.

In the present invention, the higher amines have the general formula /R1R
-fX-A-)-N(1)n'--R, and/or (wherein R is a C8-24 alkyl group, a C8-24 alkenyl group, or a C8-24 cedroxyalkyl group, , X is -CONH-, -COO-, -0- or -
N-.

A is an alkylene group and is R3.

R,, R2, R3, R4 are H1 alkyl groups or hydroxyalkyl groups. n is an integer of 0 or 1 or more. ) can be mentioned. In general formula (1) or (2), the alkyl group having 8 to 24 carbon atoms for R is an octyl group, 2-ethylhexyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group. group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group,
Examples include heneicosyl group, docosyl group, tricosyl group and tetracosyl group. Examples of the alkenyl group having 8 to 24 carbon atoms include dodecenyl group, octadecenyl group, and docosenyl group. Examples of the hydroxyalkyl group having 8 to 24 carbon atoms include hydroxyoctyl group, hydroxydecyl group, hydroxyundecyl group, hydroxydodecyl group, hydroxytridecyl group, hydroxytetradecyl group, hydroxypentadecyl group, hydroxyhexadecyl group, and hydroxyhexadecyl group. Examples thereof include butadecyl group, hydroxyoctadecyl group, hydroxynonadecyl group, hydroxyeicosyl group, hydroxyheneicosyl group, hydroxydocosyl group, hydroxytricosyl group and hydroxytetracosyl group. Of R, preferred is carbon number 8-
24 alkyl groups, particularly preferred are alkyl groups having 8 to 18 carbon atoms. Examples of the alkylene group of A include C2-6 alkylene groups such as ethylene group, propylene group, trimethylene group, and hexamethylene group, with ethylene group and trimethylene group being preferred.

The alkyl group in R,,R2,R,,R4 is C
, ~24 alkyl groups such as methyl, ethyl, propyl, butyl groups and C8- as explained in the section of R above.
24 alkyl groups are mentioned.

Among the a]alkyl groups, preferred are methyl and ethyl groups.

Examples of the hydroxyalkyl group include C, -28 hydroxyalkyl groups such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, and C8-24 hydroxyalkyl as explained in the section of R above. Among the hydroxyalkyl groups, preferred are hydroxyethyl and hydroxypropyl groups. n is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 6, particularly preferably O or an integer of 1 to 2.

Specific examples of higher amines include aliphatic primary monoamines (
Alkylamines such as octylamine, 2-ethylhexylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine; alkenylamines such as octadecenylamine; hydroxyalkylamines such as β-hydroxyhexadecylamine), aliphatic 2 monoamines (dioctylamine, hexadecylmethylamine, dihexadecylamine, etc.), aliphatic tertiary monoamines [octyldimethylamine, dihexadecylmethylamine, dodecyldimethylamine, tetradecyldimethylamine, hexadecyldimethylamine, octadecyldimethyl Amines, di(β-hydroxyoctadecino(ha)methylamine, etc.), alkylhypolyalkylene polyamines (dodecyldiethylenetriamine, dioctyltriethylenetetramine, etc.), cyclic amines with substituents (2-undecylimidazole, 1-hydroxy ethyl-2-hebutadecenylglyoxalidine, etc.), amidoamines (undecanoylaminoethylamine, undecanoylaminopropyldimethylamine, pentadecanoylaminoethylhydroxyethylamine, heptadecanoylaminoethyldiethylamine, etc.), ester amines (undecanoylaminoethylamine, etc.), Monoesters of oil fatty acids and triethanolamine, esters of oleic acid and diethylaminoethanol, etc.), ether amines (dodecyl ethyl ether, etc.) and alkylene oxides (such as ethylene oxide, propylene oxide, etc.).
Examples include amines to which 2 to 4 alkylene oxides, etc.) have been added (the number of moles of alkylene oxide added is usually 1 to 20, preferably 1 to 10).

Among these higher amines, preferred are aliphatic tertiary monoamines, alkylated polyalkylene polyamines, and amidoamines, and particularly preferred are dodecyldimethylamine, tetradecyldimethylamine, hexadecyldimethylamine, octadecyldimethylamine, and dodecyldiethylenetriamine. Misdioctyltriethylenetetramine, undecanoylaminopropyldimethylamine and hebutadecanoylaminoethyldiethylamine.

In the present invention, examples of the monohaloorganic acid type amphoteric agent (hereinafter sometimes abbreviated as amphoteric agent) include a monohalocarboxylic acid type amphoteric agent and/or a monohalosulfonic acid type amphoteric agent.

Monohalocarboxylic acid type amphoteric agents include monohaloalkanecarboxylic acids having 2 to 5 carbon atoms (monochloroacetic acid, monobromopropionic acid, monochlorobutyric acid, monochlorovaleric acid, etc.), monohalohydroxyalkanecarboxylic acids having 2 to 5 carbon atoms; (2-chloro-3-hydroxypropionic acid,
(3-chloro-2-hydroxypropionic acid, etc.) and their salts, such as alkali metal salts (sodium salts, potassium salts, etc.), ammonium salts, etc. In addition, as a monohalosulfonic acid type amphoteric agent, the carbon number is 2.
~5 monohalosulfonic acids (monochloroethanesulfonic acid, monobromopropanesulfonic acid, monochlorobutanesulfonic acid, etc.), monohalohydroxyalkanesulfonic acids having 2 to 5 carbon atoms (2-chloro-3-hydroxypropanesulfonic acid, 3 -chloro-2-hydroxypropanesulfonic acid, etc.) and salts thereof (salts similar to those described for the monohalocarboxylic acid type amphoteric agent). Among the amphoteric agents, monohalocarboxylic acids (salts) are preferred, and monochloroacetic acid and sodium monochloroacetate are particularly preferred. Regarding the reaction between higher amines and amphoteric agent, the equivalent ratio is usually 1:1 to 1:3, preferably 1:1.
The ratio is 1.1 to 1:2.

When higher amines and an amphoteric agent are reacted, the reaction temperature is usually 40 to 110°C, preferably 50 to 90°C, and the reaction time is usually 1 to 10 hours, preferably 2 to 8 hours. The reaction is usually carried out in an inert gas atmosphere such as nitrogen gas. Further, the reaction may be carried out in the presence of water or an organic solvent such as water, methanol, isopropanol, propylene glycol, glycerin, chloroform, acetone, or a mixture of two or more thereof, or may be carried out directly in the absence thereof. The amphoteric surfactants obtained in this way are amino acid type amphoteric surfactants (primary, primary,
(for secondary amino groups), betaine type amphoteric surfactants (3
(in the case of a class amino group), etc.

In this amphoteric surfactant, the amphoteric agent usually remains in an amount of 0.1 to 5% by weight. When the amphoteric surfactant obtained by reacting higher amines and an amphoteric agent is brought into contact with sulfites, the sulfites include sulfites, acid sulfites, metasulfites, and mixtures of two or more of these. can give.

Examples of the salts include alkali metal salts (sodium salts, potassium salts, etc.), ammonium salts, and mixed salts thereof. Specifically, sulfites include sodium sulfite, potassium sulfite, and ammonium sulfite; acid sulfites include sodium acid sulfite, potassium acid sulfite, and ammonium acid sulfite; metasulfites include sodium metasulfite, potassium metasulfite, and ammonium metasulfite. can be given. Among sulfites, sulfites are preferred, and sodium sulfite is particularly preferred because it is easily available. The amount of sulfites added is generally from equivalent to 1.5 times equivalent, preferably from 1.05 to 1.3 times equivalent, relative to the halogen of the monohalo organic acid type amphoteric agent remaining in the amphoteric surfactant.

If the amount is less than an equivalent amount, the amphoteric agent remains, and if it exceeds 1.5 times the equivalent amount, impurities will increase in the composition. The amount of amphoteric agent remaining in the ampholytic surfactant can be determined, for example, by nuclear magnetic resonance absorption spectroscopy. When bringing the sulfites into contact with the amphoteric surfactant, the sulfites can be brought into contact directly or after being dissolved in water.

The contacting method may be a method in which the higher amines and the amphoteric agent are reacted, and then the activator is added after the reaction has substantially completed, and the contact is carried out by mixing and stirring. A method may also be used in which sulfites are added to an amphoteric surfactant and brought into contact. The former method is preferred.
Contact temperature is usually 40-120℃, preferably 50-90℃
It is. If the contact temperature is less than 40°C, the treatment will be insufficient, and if it exceeds 120°C, coloring will occur or the amphoteric surfactant will partially decompose. The contact time is usually 30 minutes to 6 hours, preferably 1 to 4 hours. In order to prevent coloring, it is preferable to contact in an inert gas atmosphere such as nitrogen gas. The end point of the contact treatment can be confirmed by quantifying the amount of benzyl halide by nuclear magnetic resonance absorption spectroscopy as described above. Further, after the contact treatment, it is desirable to oxidize the remaining sulfites with an oxidizing agent such as hydrogen peroxide to convert them into sulfates (harmless). In addition, the method of the present invention can be applied to conventional methods, such as alkali (sodium hydroxide, etc.).
It can also be carried out in combination with a method of thermally decomposing the amphoteric surfactant (for example, treating the amphoteric surfactant with sodium hydroxide in an amount of twice the amount of halogen in the remaining monohalo organic acid type amphoteric agent at 80 to 100°C).

For example, if the conventional method is thermal decomposition with an alkali,
Examples include a method of carrying out the treatment of the present invention followed by thermal decomposition, and a method of carrying out the treatment of the present invention after thermal decomposition. The latter is preferred. According to the method of the present invention, an amphoteric surfactant in which substantially no amphoteric agent remains can be obtained very easily, and this surfactant is less irritating to the skin and eye mucous membranes.

In addition, since a sufficient effect can be obtained with simple processing, there is no decrease in yield, and light-colored products can be obtained. Because of the above characteristics, it is useful as a base for jump bases, hair rinse bases, fabric softeners, antistatic agents, dyeing aids, kitchen detergents, disinfectants, and the like. The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 1 mol (213 g) of dodecyldimethylamine, 1.2 mol (139.8 g) of sodium monochloroacetate, and 769 g of water were placed in a reactor equipped with a stirrer and a thermometer, and the mixture was heated to 70 to 70 g while bubbling nitrogen into the gas phase. The temperature was raised to 75°C.

The reaction system was maintained at 7 to 9 with an aqueous sodium hydroxide solution and reacted at the same temperature for 5 hours. The sodium monochloroacetate content of this amphoteric surfactant was 1.6% by weight, and the hue was 20 by APHA method. Then 70-75 phase C
Then, 0.18 mol (22.7 g) of sodium sulfite was added to this activator, and stirring was continued at the same temperature for 2 hours for post-treatment. The content of sodium monochloroacetate in this product was 0% by weight, and the hue was 20. Comparative Example 1 Dodecyldimethylamine and sodium monochloroacetate were reacted in the same manner as in Example 1, and then an aqueous solution of 0.3 mol (12 g) of sodium hydroxide dissolved in 28 g of water was added.
When stirring was continued for 2 hours at ~95°C, the sodium monochloroacetate content of this amphoteric surfactant was 0.2% by weight, and the hue was 80.

Test Example 1 The resistance of the post-treated product obtained in Example 1 and the active agent of Comparative Example 1 was adjusted to 6.0 with hydrochloric acid, and a 1% aqueous solution thereof was used to conduct a skin irritation test using a patch test.

Specifically, a lint cloth coated with the sample was applied to the inner side of the upper arm of 10 men and 10 men, and the presence or absence of any changes was examined 48 hours later. The results are shown in Table 1, and it can be seen that the active agent obtained by the method of the present invention is particularly mild. Example 2 Same as Example 1, 1 mol (382 g) of heptadecanoylaminoethyldiethylamine and 1.3 mol (1.3 mol) of sodium monochloroacetate (
151.5 g), 945 g of water, and 300 g of isopropyl alcohol were charged and reacted at 80 to 85°C for 6 hours. The content of sodium monochloroacetate in the obtained amphoteric surfactant was 1.3% by weight. Then sodium sulfite 0.
An aqueous solution of 22 mol (27.7 g) dissolved in 110 g of water was added to the activator and stirred for 2 hours at 80-85°C for post-treatment. The sodium monochloroacetate content of this treated product was 0% by weight. Example 3 1 mol (271 g) of dodecyldiethylenetriamine and 620 g of water were placed in a reactor equipped with a stirrer, a thermometer, and a dropping load, and 1.5 mol (141 .8 g) was added dropwise over 1 hour, and then aged at the same temperature for 3 hours.

The monochloroacetic acid content of the obtained amphoteric surfactant was 0.9
It was in weight%. Next, an aqueous solution of 0.13 mol (16.4 g) of sodium sulfite dissolved in 150 g of water was added and stirring was continued for 3 hours at 50-60°C for post-treatment.

After this treatment, no residual monochloroacetic acid was observed. Example 4 Similarly to Example 1, 1 mol of hexadecyldimethylamine (
269 g) and 1.2 mol (1.2 mol) of sodium monochloroacetate
39.8g), 200g of water, and 75g of propylene glycol.
0g was charged and reacted at 75-80C for 5 hours.

The content of sodium monochloroacetate in the obtained amphoteric surfactant was 1.3% by weight. Then, an aqueous solution of 0.18 mol (22.7 g) of sodium sulfite dissolved in 200 g of water was added to the activator, and stirring was continued for 2 hours at 75-80°C for post-treatment.

Claims (1)

[Scope of Claims] 1. A method for post-treatment of an amphoteric surfactant, which comprises contacting an amphoteric surfactant obtained by reacting a higher amine with a monohalo organic acid type amphoteric agent with a sulfite. 2. The method according to claim 1, wherein the monohalo organic acid type amphoteric agent is a monohalocarboxylic acid type amphoteric agent and/or a monohalosulfonic acid type amphoteric agent. 3. Claim 1 or 2, wherein the sulfites are sulfites, acid sulfites and/or metasulfites.
The method described in section. 4. The method according to any one of claims 1 to 3, wherein the sulfites are alkali metal salts and/or ammonium salts. 5. The method according to any one of claims 1 to 4, wherein the contact treatment is performed at 40 to 120°C. 6. The method according to any one of claims 1 to 5, wherein the equivalent ratio of sulfites to the monohalo organic acid type amphoteric agent remaining in the amphoteric surfactant is 1 to 1.5. .