JP2005272429A - Diol, surfactant in which polar groups are introduced to two hydroxy groups of diol, and cosmetic containing the surfactant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an intermediate for an anionic surfactant containing two chains of two hydrophilic groups which can easily be manufactured by using only cheap raw materials, the anionic surfactant containing two chains of two hydrophilic groups which is superior in biogradability, and a cosmetic which contains the surfactant and gives no load onto the skin. <P>SOLUTION: The double bond of an oleic acid alkylamide molecule is epoxidized and then hydroxylated to obtain the diol. To the hydroxy groups of this diol, two sulfate groups or phosphate groups are introduced to obtain a sulfate or a phosphate, or their neutralized substances. The cosmetic containing at least one kind of those is also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a diol, a surfactant in which two polar groups are introduced into two hydroxyl groups of the diol, and a cosmetic containing the surfactant.

Currently, two-chain two-hydrophilic group-containing surfactants in which two molecules of conventional one-chain one-hydrophilic group-containing surfactants are covalently linked to each other need only be formulated at a low concentration due to their excellent surface-active ability. Research and development have been promoted from the viewpoint that the burden on the environment is reduced and there is almost no skin irritation (see Patent Document 1). In fact, the inventor of the present application has revealed that the inclusion of a 2-chain and 2-hydrophilic group is superior to the corresponding “monomer” in terms of skin safety (see Non-Patent Document 1). However, when considering the molecular design of this 2-chain 2-hydrophilic group-containing surfactant on the premise of industrial implementation, it is not always easy to introduce a linking site, a hydrophobic group, or a polar group of two molecules, and the molecular design is limited. In spite of its excellent performance, there are few things that are still in practical use because they are forced to use relatively expensive raw materials. It is a fact. Some recently proposed two-chain two-hydrophilic group-containing surfactants have been devised in molecular design, such as introducing a hydrophobic group into a linking site containing a hydrophilic group to realize a two-chain two-hydrophilic group ( (See Non-Patent Document 2) However, this has left a problem in terms of biodegradation to some extent, but has not yet reached a fundamental solution.
Patent registration No. 3426493 Kazuyuki Tsubone et al., Journal of Surfactant and Detergent (Journal of Surfactant & Detergent, Vol. 6, No. 1, pp. 39-46, 2003) Kazuyuki Tsubone et al., Journal of Surfactant and Detergent (Journal of Surfactant & Detergent, Vol. 7, No. 1, pp. 47-52, 2004)

  Thus, it can be said that a two-chain, two-hydrophilic group-containing anionic surfactant that has sufficiently satisfied the biodegradability, which is an essential requirement as a surfactant, and has economical efficiency that can withstand practical use has not yet been developed. For this reason, cosmetics containing an anionic surfactant that have a low impact on the skin and the environment have not been developed yet.

  In such a background, the problem to be solved by the present invention is an intermediate of a two-chain, two-hydrophilic group-containing anionic surfactant that can be easily produced using only inexpensive raw materials, and easily and inexpensively using this intermediate. The present invention provides a two-chain two-hydrophilic group-containing anionic surfactant excellent in biodegradability and a cosmetic containing the same.

Claim 1 of the present invention is a diol characterized in that it is obtained by hydroxylation after epoxidizing a double bond of an oleic acid alkylamide (wherein the alkyl group has 2 to 18 carbon atoms) in the molecule. .
Further, claim 2 is characterized by comprising a sulfate or phosphate obtained by introducing two sulfate groups or phosphate groups into the two hydroxyl groups of the diol according to claim 1, or a neutralized product thereof. It is a 2 chain 2 hydrophilic group containing anionic surfactant.
A third aspect of the present invention is a cosmetic comprising the two-chain two-hydrophilic group-containing anionic surfactant according to the second aspect.

The diol of the present invention and its sulfated or phosphoric oxide or neutralized product thereof are easily produced from inexpensive raw materials. A cosmetic containing a two-chain, two-hydrophilic group-containing anionic surfactant, which is low in both the load on the skin and the environment, is provided. That is, an anionic surfactant containing a two-chain, two-hydrophilic group is used as a raw material by using an unsaturated fatty acid amide called oleic acid alkylamide (wherein the alkyl group has 2 to 18 carbon atoms), and the double bond portion has an excess amount. Realized using only inexpensive raw materials by epoxidation with hydrogen oxide and formic acid, and dihydroxylation of epoxide with alcoholic potassium hydroxide, by the reaction of sulfation with chlorosulfonic acid or phosphorylation with phosphoric anhydride. . As the alkali used for neutralization, sodium hydroxide, potassium hydroxide, or lithium hydroxide is used.
The oleic acid alkylamide in the present invention is obtained by dropping 1.2 equivalent amount of alkylamine into oleic acid chloride at room temperature in the presence of pyridine, stirring for 5 hours, washing with water and drying. In the present invention, the cosmetic refers to skin cosmetics such as cream, milk, and lotion, hair cosmetics such as a hair set, and makeup cosmetics such as liquid foundation. The present invention also includes shampoos, rinses and hair conditioners. These cosmetics can contain 0.1 to 50% by weight of at least one of the sulfated or phosphoric oxides or neutralized products thereof according to the present invention. Next, it shows in detail in an Example.

Synthesis of Diol of the Invention 35 g (0.26 mol) of 25% hydrogen peroxide is added all at once to a mixture of 91 g of oleic acid hexylamide (0.25 mol) and 500 ml of formic acid at room temperature with stirring. The mixture is heated to 40 ° C. with stirring and stirred for 24 hours. Formic acid is removed under reduced pressure using an evaporator, and the resulting residue is refluxed with excess 3N alcoholic potassium hydroxide for 1 hour. After removing the alcohol, it is washed with water to obtain a white precipitate (diol, about 100 g). The resulting washed product gave 0 as the iodine value. The diol of the present invention was thus obtained.

Synthesis of Sulfur Oxide of the Present Invention Monochlorosulfonic acid (0.5 mol) was stirred in a mixture of 78 g of diol (0.2 mol) obtained in Example 1 and 250 ml of glacial acetic acid at 0 ° C. in the presence of 12 g of sodium hydride. 59 g is added dropwise over 1 hour and stirred for 1 hour. A white powder precipitates in the process of removing glacial acetic acid using an evaporator under reduced pressure. This gave an absorption of sulfate groups at 1200 cm ⁻¹ in the infrared absorption spectrum. In this way, the sulfate of the present invention was obtained. The white residue obtained by adding 2 equivalents of sodium hydroxide to water and removing the water is the disodium salt of the sulfate of the present invention. Incidentally, 12 g of sulfuric acid was gradually added to 500 ml of water, and after cooling, 0.03 g of methylene blue and 50 g of anhydrous sodium sulfate were dissolved, and 15 ml of methylene blue solution prepared to 1 L by adding water to a test tube, 5 ml of chloroform, When several drops of a 1% aqueous solution of a disodium sulfate salt was added and shaken, the chloroform phase turned blue. This is also valid as confirmation of the sulfate of the present invention.

Synthesis of Phosphorus Oxide of the Present Invention To a mixture of 78 g of the diol (0.2 mol) obtained in Example 1 and 500 ml of tetrahydrofuran, 64 g of phosphorus oxychloride (0.42 mol) was added dropwise over 30 minutes with stirring at 0 ° C. Then, after stirring for 1 hour, 20 g of water is added and stirred for 1 hour. Volatiles were removed using an evaporator under reduced pressure, and the resulting residue was purified by silica gel column chromatography (chloroform / methanol = 2: 3). The resulting white powder (about 80 g) gave phosphate group absorption at 1200 cm ⁻¹ in the infrared absorption spectrum. Thus, the phosphor oxide of the present invention was obtained. The white residue obtained by adding twice the equivalent amount of sodium hydroxide in water and removing the water is the disodium salt of the phosphate of the present invention. Incidentally, 12 g of sulfuric acid was gradually added to 500 ml of water, and after cooling, 0.03 g of methylene blue and 50 g of anhydrous sodium sulfate were dissolved, and 15 ml of methylene blue solution prepared to 1 L by adding water to a test tube, 5 ml of chloroform, When several drops of a 1% aqueous solution of disodium salt of phosphoric acid was added and shaken, the chloroform phase turned blue. This is also valid as confirmation of the sulfate of the present invention.

The biodegradability of the above-described disodium salt of the present invention and the disodium salt of phosphoric acid was determined according to the biodegradability test method of a synthetic detergent described in JIS-K3363. The biodegradability of the disodium salt of phosphorous oxide was 100%. The biodegradability of (CH2) 2 [NCO (C11H23) (COOH) CH2COOH] .2NaOH (abbreviated as GA), which is the compound of Non-Patent Document 2, is 75%.
Further, the skin safety of the disodium sulfate and the disodium phosphate of the present invention was compared with GA in the method described in Non-Patent Document 1, that is, the 48-hour occlusion patch test by a panel of 20 healthy persons. did. As a result, the average irritation score after 48 hours was 0, and the skin safety of the disodium sulfate and disodium phosphates of the present invention was the same as that expected for GA. It turns out that safety is high.
As described above, it was found that the disodium salt of the sulfate of the present invention and the disodium salt of phosphoric acid which are easily obtained from inexpensive raw materials are excellent in biodegradability and skin safety.

Preparation of skin cream In accordance with the following formulation, component 1-4 was stirred and mixed at 70 ° C. as an oil phase component, and this was added to the mixed aqueous phase component of component 5-9 with stirring. A skin cream was prepared.
1. Squalane 10%
2. Cetanol 3%
3.2-ethylhexyl palmitate 20%
4). Butylparaben 0.2%
5). Methylparaben 0.2%
6). Glycerin 3%
7.1,3-butanediol 5%
8). Disodium salt of the oxide of Example 2 0.2%
9. Water residue

Comparative Example 1

Preparation of skin cream In accordance with the following formulation, component 1-4 was stirred and mixed at 70 ° C. as an oil phase component, and this was added to the mixed aqueous phase component of component 5-9 with stirring. A skin cream was prepared.
1. Squalane 10%
2. Cetanol 3%
3.2-ethylhexyl palmitate 20%
4). Butylparaben 0.2%
5). Methylparaben 0.2%
6). Glycerin 3%
7.1,3-butanediol 5%
8). Cetyl sulfate sodium salt 0.2%
9. Water The remaining 20 female panels conducted practical tests on the creams of Example 4 and Comparative Example 1 over a half year, and it was found that the cream of Example 4 had a low load on the skin.

  A diol that is an intermediate of an anionic surfactant containing a 2-chain 2-hydrophilic group that can be easily produced using only oleic acid alkylamide as a starting material, and sulfating or phosphorylating two hydroxyl groups of this diol. The two-chain, two-hydrophilic group-containing anionic surfactants excellent in biodegradability and skin safety and the cosmetics containing the same have great industrial applicability.

Claims (3)

  A diol obtained by epoxidizing a double bond in an oleic acid alkylamide molecule (wherein the alkyl group has 2 to 18 carbon atoms), followed by hydroxylation.   A two-chain two-hydrophilic group comprising a sulfate or phosphate obtained by introducing two sulfate groups or phosphate groups into the two hydroxyl groups of the diol according to claim 1, or a neutralized product thereof. Contains anionic surfactant.   A cosmetic comprising the two-chain two-hydrophilic group-containing anionic surfactant according to claim 2.