JPS6034904A - Hair wash having low irritation - Google Patents

Abstract

PURPOSE:A hair wash having low irritation to the skin, the eyes, the mucosa, etc., containing a di-substituted aliphatic carboxylic acid amide amine as a detergent component. CONSTITUTION:A hair wash containing a compound (e.g., N-(2-hydroxyethyl)- N-[di-(2-carboxyethyl)aminoethyl]octanoic acid amide) shown by the formula (R is 7-17C aliphatic hydrocarbon group; M is H, or alkali metal atom) as a detergent component. This hair wash is made into a form of shampoo or hair rinse, used, and contains at least >=2wt% compound shown by the formula. The compound shown by the formula has extremely lower irritation to the skin, the eyes, and the musoca than an existing surface active agent having a similar structure.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hair wash that is less irritating to the skin, eyes, mucous membranes, and the like. More specifically, the present invention is directed to a link represented by the general formula (wherein R is an aliphatic hydrocarbon group having 7 to 17 carbon atoms, and j and 1 are hydrogen atoms or alkali metal atoms) The present invention relates to a hypoallergenic hair wash containing a di-substituted aliphatic carboxylic acid amide amine as a detergent component.

So far, substituted amidoamine type amphoteric surfactant injection agents have been obtained by reacting linear aliphatic carboxylic acids with aminoetherethanolamine. Compounds having the general formula (in which R' is a long-chain aliphatic hydrocarbon residue and M'' is a hydrogen atom or an alkali metal atom) are known (U.S. Pat. No. 3,262, No. 951 and Specification No. 3,94L817).

Such amphoteric surfactants are used as detergents, fiber treatment agents, antistatic agents, cosmetic bases, and the like. By the way, when a surfactant is used as a detergent component of a hair wash such as shampoo or conditioner, it is required to have no or little irritation to the skin, eyes, mucous membranes, etc. The substituted amidoamine type amphoteric surfactant No. 1 cannot be said to be fully satisfactory in this respect, and was therefore unsuitable for use in hair washes.

As a result of intensive research to develop a hair wash that is less irritating to the skin, eyes, and mucous membranes, the present inventors have found the general formula (
The objective was achieved by using the disubstituted aliphatic carboxylic acid amidoamine represented by 1) as a detergent component.
Based on this knowledge, the present invention was completed.

An example of the compound of the present invention represented by the general formula (1) is -N-(2-hydroxyethyl)-N-[di(2-
carboxyethyl)aminoether]octanoic acid γmide,
N-(2-hydroxyethyl)-N-[C(2-carboxyethyl)aminoethyl]decanoic acid amide, N-
(2-Hydroxyethyl)-↑J-[di(2-carboquinethyl)aminoether]dodecanoic acid amide, If-
(2-Hydroxyethyl)-N-[di(2-calphokidiethyl)ami,noethyl]stearamide, N
-(2-hydroxyethyl)-'N-[di(2-carboquinethyl)aminoether]lauric acid amide, N-
(2-Hydroxyethyl)-N-[di(2-carnoxyethyl)amine ether]yang oil fatty acid amide and their sodium salts, potassium salts, etc. can be used.

These compounds are produced by, for example, reacting an imidacillin derivative represented by the general formula % (R in the formula has the same meaning as above) with an acrylic acid alkyl ester and water, and saponifying the product with an alkali hydroxide. You can get it by doing this.

Examples of the imidacilline derivative represented by the general formula a) include an alkyl group such as an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, or an octenyl group at the 2-position. 1-(2-hydroxyethyl) di-substituted by an alkenyl group such as a decenyl group, a pentadecenyl group, etc.
~I can give you imidacillin.

Further, as the acrylic acid alkyl ester to be reacted with this imidacillin derivative, lower alkyl esters such as methyl acrylate and ethyl acrylate are preferable.

This acrylic acid alkyl ester is used in a ratio of 1.3 to 2.0 moles per mole of imidacillin derivative. If this amount is more than 2.0 moles, there will be a large amount of unreacted sodium acrylate in the final product, and if this amount is less than 1.3 moles, there will be a lot of unreacted amine in the final product. rate decreases.

The amount of water to be reacted simultaneously with the acrylic acid alkyl ester is selected to be at least 1 mol per 1 mol of imidacillin derivative, preferably in the range of 2.0 to 3.0 mol. If this amount is less than 1.0 mol, the amount of secondary amine as a by-product increases.

The yield of the target product decreases.

The imidacillin derivative, acrylic acid alkyl ester, water, and Q reaction are carried out at room temperature to 100°C, preferably at 60 to 80°C.
It is best to carry out at a temperature of 0°C. The time required for the reaction is usually 3
The conversion time ranges from 0 minutes to 4 hours, but in most cases about 99% conversion is achieved in 60 minutes. This reaction can be carried out in the presence of an alkaline catalyst if desired, but a catalyst is not particularly required.

The product obtained with Pi:L is directly subjected to the next saponification treatment with alkali hydroxide without being isolated. This saponification converts the above reaction product into
This is carried out by adding approximately equimolar amount of alkali hydroxide to the acrylic acid alkyl ester used and heating to 50 to 100°C. The time required for saponification is usually about 2 hours at 70°C.

When the reaction product thus obtained is distilled under reduced pressure and the low molecular weight components contained therein are distilled off, the target compound or a reaction product mainly containing it remains as a white solid. When the white solid of the target compound thus obtained was subjected to thin layer chromatography, it showed one spot and was confirmed to be a pure product. Also,
It was confirmed by infrared absorption spectrum, nuclear magnetic resonance spectrum, elemental analysis, etc. that this product has the structure of the general formula ([).

These compounds are characterized by significantly lower irritation to the skin, eyes, and mucous membranes than conventional surfactants with similar structures.

The uninvented hair wash contains the compound represented by the general formula (1) as a detergent component, and is used in the form of shampoo or hair rinse.

The content of the compound in it is not particularly different from the concentration required for detergent ingredients normally used in shampoos and hair rinses.
The concentration is at least 2 parts by weight or more and is appropriately selected depending on the purpose of use. In addition to detergent ingredients, the hair wash of the present invention also contains:
Various additives used in shampoos and hair rinses, such as preservatives, fragrances, and dyes, can also be added, and surfactants can also be used at concentrations that do not cause irritation to the eyes or mucous membranes. You can also.

Next, the present invention will be explained in more detail with reference to Reference Examples and Examples.

Reference Example 1 ■-Hydroxyethyl-2-undecylimidazoli 7268 ii' (1.0 mol) and acrylic acid Cortel 200 F ( 2.0 mol) and
After stirring at 25-35℃ for 30 minutes, add 36℃ of water. (
2.0 mol) is added. At this time, it generated heat and the temperature reached 70℃.
After stirring for 2 hours at this temperature, 400rnl of ethyl alcohol and 80r of thorium hydroxide (2.0mol) were added, and the saponification reaction was continued at 70°C for 3 hours. I do. After the reaction is complete, the reaction product is distilled under reduced pressure to remove ethyl alcohol, resulting in N-(2-hydroxyethyl)-N as a white solid.
The disodium salt 4739 of -C-di(2-carboxyethyl)aminoether]undecanecarboxylic acid amide is obtained. As a result of thin layer chromatography, this product was found to have 1
It was confirmed that it was a single item because it showed several spots. The results of hydrocarbon analysis are 55.62% carbon (theoretical value 55-67%) and 8.39% hydrogen (theoretical value 8.50%).
)Met. Further, the result of nitrogen analysis by Kjeldahl method was 5.78% (theoretical value 5.90%).

Reference Example 2 l-hydroxyethyl-2-alkylimidacillin 268 r (1.0 mol) produced from coconut oil fatty acid (average molecular weight 200, AV 280 ) and ethyl acrylate 200 f (2.0 mol) were Place it in the same flask as in Reference Example 1 and stir for 30 minutes at 25-30°C. Next, when 36 ml of water (2.0 mol) is added, it generates heat and the temperature rises to 70°C. The reaction was carried out at this temperature for 2 hours. and others,
Add 5397 ml of water and add 160 ml of 50% sodium hydroxide aqueous solution. (2.0 mol) was added and heated at 70°C for 2 hours to saponify it. The reaction mixture was distilled under reduced pressure7.
An evaporation residue of 39.4% was obtained. In this way, pH 12,
A disodium salt of N-(2-hydroxyethyl)-u-[cy(2-carboxyeternaminoether) coconut oil fatty acid amide] showing 6 was obtained. It included 0.2 weight ratio and 01 weight ratio.

Reference Example 3 The amount of ethyl acrylate was 150 r (1.5 mol), the amount of water added during the saponification reaction was 4942.50, and the amount of aqueous trifluoride solution to be hydroxylated was 120 r (1.5 mol). By repeating the experiment under the same conditions as in Reference Example 2, a reaction product with a pH of 12.9 was obtained based on the weight of the evaporation residue. This product contains 40% by weight of disodium salt of N-(2-hydroxyethenonone-N-[di(2-carboxyethyl)aminoethyl coconut oil fatty acid amide) and N-(
2-Hydroxyethyl)-N-(2-carpoquinethylaminoethyl coconut oil fatty acid amide sodium salt 60
The mixture contained 0.3% by weight of each of unreacted amine and sodium acrylate.

Reference Example 4 As a raw material imidacillin derivative, 1-hydroxyethyl-2-heptadecyl imidacilline 3522 (10 mol)
was used, and the other procedures were carried out in exactly the same manner as in Reference 13il12 to obtain an aqueous solution of the disodium salt of N-(2-hydroxyether)-N-[di(2-carboxyethyl)aminoethyl]stearamide. The pH of this thing is 12,
5, the evaporation residue was 43.3% by weight, and the impurities were 0.2% by weight of unreacted amine and 0.1% of sodium acrylate.
% by weight.

Reference example 5 1-hydroxy-2-undecylimidacilline 26+3
ii' (1,0 mol) and methyl acrylate 172i
(2.0 mol), and the other conditions were exactly the same as in Reference Example 2. A disodium salt of ethyl/decanecarboxylic acid amide was obtained.The pH of this product was 12.5, and the evaporation residue was 40
．． 3% by weight, it contained 702% by weight of unreacted amide and 0.1% by weight of sodium acrylate.

Reference example 6 According to the method of U.S. Pat. No. 3,941,817.

In a 1-volume four-bottle flask equipped with a stirrer, a thermometer, a nitrogen blowing tube, and a condensing tube connected to a vacuum pump, golden oil fatty acid methyl ester (average molecular weight 200, AV
280) 214 r (1,0 mo/lz), aminoetherethanolamine 107 iF (1,03 mole) and 25% sodium methoxy/tomethyl alcohol solution were charged, and the nitrogen pressure was 150 T, Im Hg or less. 312 methyl alcohol was recovered by gradual heating at +100-105°C. As the residue, N-coconut oil unru N-hyaloxyethylethylenediamine 28
I got 62.

Next, the nitrogen blowing pipe was replaced with a dropping funnel, 3751 of water was added, and 94.5 f (1.0 mol) of monochloroacetic acid was added.
was added and cooled to 45°C'. Next, 160 t (2.0 mol) of a 500% by weight aqueous sodium hydroxide solution was added over 10 minutes while being careful not to exceed the external temperature of 55°C. After the addition was completed, the reaction was carried out at 50-60°C for 3 hours, and then at 80-90°C for 2 hours. In this way, N-(2-hydroxyethyl)-N-(
A sodium salt of 2-carboxine methyl)aminoethyl coconut oil fatty acid amide was obtained.

Comparative Example The compound obtained in Reference Example 1 (sample A) - the compound obtained in reference example 2 (sample B) and the compound obtained in reference example 6 (sample C) were made into an aqueous solution of 11 ft8 weight, and the , 1 ml
was administered to a group of three male white rabbits, and an eye irritation test was conducted using the Draize method. The results are shown in Table 1.

Samples A and B, that is, the compounds used in the present invention, did not cause any damage to the cornea, and no iris hyperemia was observed. Although a small amount of conjunctival edema was observed, it was not of any particular concern, and it was found that the eye irritation was extremely low.

Example 1 As a representative example, disodium salt of N-(2-hydroxyethyl)-N-[di(2-carboxyether)-aminoether] coconut oil fatty acid amide (sample B) was used, and a sample was prepared with the composition shown below. A hypoallergenic shampoo was prepared.

This product showed almost no eye irritation.

Sample B 15 Coconut oil fatty acid jetanolamide 3 Citric acid hydrate 2 P-hydroxybenzoic acid ether 0.5 Preservative, fragrance 1
Dye Appropriate amount Deionized water Noxy Rinse Example 2 Using the same compound as in Example 1, an emulsion-like hair rinse was prepared according to the composition shown below.

Sample B2 Distearyldinotylammonium chloride 3 Ethylene glycol monostearate 1 Polyoxygen/ethylene oleyl alcohol 1 Glycerin 5 Fragrance powder Appropriate amount Deionization/Water Balance This product shows almost no eye irritation and is safe for washed hair. The effect of improving combing was confirmed.

Example 3 Using the same compound as in Example 1, a liquid hair wash was prepared according to the composition shown below.

Component weight section Sample J3 18 Lauric acid jetanolamide 5 Citric acid-hydrate salt 1 Fragrance 1 colorant appropriate amount Deionized water balance This product showed no eye irritation.

Patent applicant Lion Corporation Agent Akira Agata

Claims (1)

[Scope of Claims] 1 A disubstituted aliphatic compound represented by the general formula (wherein R is an aliphatic hydrocarbon group having 7 to 17 carbon atoms, and M is a hydrogen atom or an alkali metal atom) A hypoallergenic hair wash characterized by containing carboxylic acid amide amine as a detergent ingredient.