JPH0643597B2 - Method for purifying betaine-type amphoteric surfactant - Google Patents

Description

The present invention relates to a method for purifying a betaine-type amphoteric surfactant,
Specifically, it relates to a method for obtaining a surfactant which does not cause discoloration of coexisting dyes.

[Conventional technology]

Betaine-type amphoteric surfactants are widely used mainly for cosmetics such as shampoos and hair conditioners, and detergents such as kitchen detergents and bath detergents because they have low irritation to the skin and eye mucous membranes. .

Conventionally, betaine-type amphoteric surfactants have been obtained by reacting a tertiary amine with a monohaloorganic acid-type amphoteric agent such as monochloroacetic acid or sodium monochloroacetate.

When commercializing cosmetics and detergents using such betaine-type amphoteric surfactants, it is almost always colored with a dye.

The product thus obtained is often discolored with time, and particularly when exposed to sunlight in a transparent container, the discoloration is remarkable and the commercial value is reduced. Therefore, not only is the amount of betaine-type amphoteric surfactant used limited,
There was no choice but to be constrained, such as having to use an opaque container.

As a method for improving the quality of the amphoteric surfactant, there is known a method of treating the amphoteric surfactant with sulfites to alleviate irritation (Japanese Examined Patent Publication No. 59-29638). There is no known way to improve quality so that it does not happen.

[Problems to be solved by the invention]

The present invention is intended to obtain a betaine-type amphoteric surfactant that does not substantially discolor when a betaine-type amphoteric surfactant is used together with a dye as a cosmetic or a detergent.

[Means for solving problems]

As a result of intensive studies, the present inventors have confirmed that the discoloration of the dye is caused by the oxidizing substance contained in the betaine-type amphoteric surfactant, and that the oxidizing substance is easily treated with a peroxide. The present invention has been completed by discovering that it is decomposed and stabilized.

That is, the present invention is a method for purifying a betaine-type amphoteric surfactant, which comprises treating a betaine-type amphoteric surfactant with a peroxide and then reducing the residual peroxide value to 10 or less.

The betaine-type amphoteric surfactant in the present invention is obtained by reacting a tertiary amine with a monohalo organic acid-type amphoteric agent.

Examples of the tertiary amine include aliphatic tertiary amines such as octyldimethylamine, dodecyldimethylamine, dodecyldiethylamine, octadecyldimethylamine, cocoalkyldimethylamine and tallow alkyldimethylamine; alkylalkylenediamines such as N-dodecyl-N- Methyl-N ', N'-dimethylpropylenediamine, N-octadecyl-N-ethyl-N', N'-diethylethylenediamine, etc .; N-acylalkylenediamines, such as N-dodecanoyl-N ', N'-dimethylpropylenediamine. , N-pentadecanoyl-N ',
N'-bis (2-hydroxyethyl) ethylenediamine, N-heptadecanoyl-N ', N'-diethylethylenediamine, N-cocoalkyloyl-N', N'-dimethylpropylenediamine and the like; ether amines such as dimethylaminopropyl dodecyl ether and the like , Can be given.

Examples of the monohalo organic acid type amphoteric agent include a monohalocarboxylic acid type amphoteric agent and a monohalosulfonic acid type amphoteric agent. Monohalocarboxylic acid type amphoteric agents include monochloroacetic acid, monobromopropionic acid, monochlorobutyric acid,
Examples include monohalocarboxylic acids having 2 to 5 carbon atoms such as monochlorovaleric acid and salts thereof, such as alkali metal salts and ammonium salts such as sodium salt and potassium salt.
Further, the monohalosulfonic acid type amphoteric agent includes monohalosulfonic acid having 2 to 5 carbon atoms such as monochloroethanesulfonic acid, monobromopropanesulfonic acid and monochlorobutanesulfonic acid and salts thereof, for example, sodium salt,
Examples include alkali metal salts such as potassium salts and ammonium salts.

The reaction between the tertiary amine and the amphoteric agent can be performed according to a generally known method. The equivalence ratio of the tertiary amine to the amphoteric agent in the reaction is usually 1: 1 to 3, preferably 1: 1.0 to 1.5, and the reaction temperature is usually 40 to 1
The temperature is 10 ° C., preferably 50 to 90 ° C., and the reaction time is generally 1 to 10 hours, preferably 2 to 8 hours. The reaction is usually performed in an atmosphere of an inert gas such as nitrogen gas. Further, the reaction may be carried out in the presence of a solvent such as water, methanol, isopropanol, propylene glycol, glycerin, chloroform, acetone or a mixture of two or more kinds thereof, or the reaction is carried out directly without using these solvents. You can also

Examples of the peroxide used for treating the betaine-type amphoteric surfactant thus obtained include hydrogen peroxide, peroxycarbonate, perborate, and a mixture of two or more thereof. . The salt mentioned here is an alkali metal salt such as a sodium salt or a potassium salt, an ammonium salt, or a mixed salt of two or more kinds thereof.

The amount of the peroxide used is 0.01% by weight or more as an effective component of the peroxide with respect to the betaine-type amphoteric surfactant solution, and it is determined from the viewpoint of the actual effect, but usually 3
Weight% or less is sufficient.

Treatment of betaine-type amphoteric surfactant with peroxide is a solution of betaine-type amphoteric surfactant dissolved in a solvent such as water, methanol, isopropanol, propylene glycol, glycerin, chloroform, acetone or a mixture of two or more thereof. Is added with a peroxide. The concentration of the betaine-type amphoteric surfactant solution is not particularly limited as long as the viscosity allows stirring treatment, but is practically 5 to 90% by weight, preferably 20 to 80% by weight.
Further, after the reaction of the tertiary amine and the amphoteric agent, it is possible to continuously add and treat a peroxide, and at this time, the solvent is added or removed to adjust the concentration, and then the peroxide is added. Can also be added for processing.

The treatment of the betaine-type amphoteric surfactant with the peroxide is carried out by adding the peroxide as it is or in the form of an aqueous solution. As the treatment conditions, when the temperature is lower than 20 ° C., the treatment becomes insufficient, and when it exceeds 120 ° C., not only is the treatment insufficient due to decomposition of peroxide at one time, but also foaming is severe. The temperature is usually 20 to 120 ° C, preferably 20 to 100 ° C. The treatment time is usually 10 minutes to 5 hours, preferably 3 hours or less. In the case of an aqueous solution, the treatment can be carried out in a wide pH range from the acidic range to the alkaline range, but in the acidic range, the peroxide is stabilized and the treatment time becomes long, so the pH range of 7 to 13 is preferable. Further, it is preferable to discharge the generated gas to the outside of the system during the treatment, and for this reason, it is desirable to perform the treatment under a stream of an inert gas such as nitrogen gas.

A part of the peroxide used after the treatment of the betaine-type amphoteric surfactant with peroxide remains, but the peroxide value of the amphoteric surfactant solution is preferably 10 or less, and further 4 or less. Is more preferable. The treatment temperature, time or pH may be adjusted to reduce the peroxide value, or a reducing agent may be added in an amount equivalent to the peroxide value after the treatment. Examples of the reducing agent used in this case include sodium sulfite and sodium thiosulfate. However, since the reducing agent affects the dye, it is preferable that the reducing agent does not remain in the solution.

The obtained betaine-type amphoteric surfactant can be widely used for usual applications as it is, or after passing through a solvent or solvent removal.

〔The invention's effect〕

By the method of the present invention, a betaine-type amphoteric surfactant which does not cause discoloration of the dye can be easily obtained.

The betaine-type amphoteric surfactant obtained according to the present invention does not cause discoloration of the dye, so that it can be used without being limited to the amount used or the container even when blended in cosmetics and detergent products. It can also be used in a wider range in other fields.

〔Example〕

 The present invention will be described with reference to examples.

In the examples, the discoloration test of the dye with the betaine-type amphoteric surfactant was conducted as follows.

A betaine-type amphoteric surfactant 30% by weight aqueous solution, ion-exchanged water and a 300 ppm concentration dye aqueous solution were added at 75:24:
Mix at a weight ratio of 1 and adjust the pH to 6-7 with citric acid.
After adjusting to, cylindrical glass container (φ35mm × 65mm)
What was put in was used as a sample. This sample was measured with a YM type light deterioration tester (Miyamoto Riken Kogyo Co., Ltd.) at a temperature of 60 ° C.
It was irradiated with light at 000 lux for 100 hours. The test conditions correspond to the exposure storage conditions of 6 months in summer.

Separately, a sample having a dye concentration of 1/2 was prepared as a control sample. When the color tone of the light-irradiated sample was darker than that of the control sample, it was judged as ◯ (usable), when it was almost equivalent, it was judged as Δ (difficult to use), and when it was light, it was judged as x (not usable).

Example 1. A reactor equipped with a stirrer and a thermometer was charged with 1 mol (290 g) of N-cocoalkyloyl-N ′, N′-dimethylpropylenediamine, 1.2 mol (139.8 g) of sodium monochloroacetate and 730 g of water, and a gas phase was prepared. The temperature was raised to 75 to 85 ° C. while passing nitrogen through the parts. While maintaining the pH of the reaction system at 7 to 9 with an aqueous sodium hydroxide solution, the reaction was carried out at the same temperature for 6 hours. Then, cool to a temperature of 35 to 50 ° C.,
Adjust the pH to 8-9, 102g of 35% hydrogen peroxide solution
(3.0 wt% of the total reaction system) was added. 70-90
The temperature was raised to 0 ° C., and the treatment was carried out for about 2 hours with stirring until the peroxide value became 10 or less. After cooling below 40 ° C, 3
The pH was adjusted to 5-7 with 5% hydrochloric acid. The final peroxide value of the reaction system was 9.1. A color change test was conducted on various dyes using the obtained aqueous solution of betaine type amphoteric surfactant. The results are as shown in Table 1.

Comparative Example 1. And 2. Example 1. The discoloration test of the dye was carried out using a sample having a high peroxide value among the aged samples treated with hydrogen peroxide solution. The results obtained are shown in Table 1. It was as shown in.

Comparative Example 3. Example 1. The dye discoloration test was carried out for those that were not treated with hydrogen peroxide. The results obtained are shown in Table 1.
As shown in.

Example 2. The same treatment as in Example 1 was carried out except that 35% hydrogen peroxide solution was used in an amount of 0.5% by weight (active ingredient) of the entire reaction system. Using the obtained aqueous solution of betaine-type amphoteric surfactant, a color change test was carried out for Yellow No. 4, which is likely to change color in the dye.
The results are summarized in Table 2.

Comparative Example 4. To the aqueous solution of betaine-type amphoteric surfactant obtained in Example 2, 0.1% by weight of hydrogen peroxide was added as an active ingredient. Using this, a yellow 4 color change test was conducted. The results are summarized in Table 2.

Example 3. And 4. The same treatment as in Example 1 was carried out except that sodium hydrogen peroxide or sodium hydrogen borate was used instead of the hydrogen peroxide solution. Using the obtained aqueous solution of betaine-type amphoteric surfactant, a color change test of four yellow colors was conducted. The results are summarized in Table 2.

Examples 5 to 10 Various betaine-type amphoteric surfactants were treated with peroxide in the same manner as in Example 1 and yellow 4 color change test was conducted. The results obtained are summarized in Table 2.

Comparative Examples 5 to 10 In Examples 5 to 10, the discoloration test was performed on the samples not subjected to the peroxide treatment. The results are summarized in Table 2.

From the above results, it is understood that a betaine-type amphoteric surfactant which does not actually cause discoloration of the dye can be obtained very easily by the present invention.

Claims (1)

[Claims] 1. A method for purifying a betaine-type amphoteric surfactant, which comprises treating a betaine-type amphoteric surfactant with a peroxide and then reducing the residual peroxide value to 10 or less.