JP2005263765A - Diol, surfactant in which polar group is introduced into two hydroxy group of diol and cosmetic containing the same surfactant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an intermediate for two chains and two hydrophilic groups-containing anionic surfactant which is readily produceable by using only inexpensive raw materials and a two chains and two hydrophilic groups-containing anionic surfactant excellent in biodegradability and a cosmetic containing the surfactant. <P>SOLUTION: The diol is obtained by epoxydizing double bond of an alkyl oleate molecule and hydroxylating the resultant epoxy. The anionic surfactant comprises a sulfation product or a phosphorated product obtained by introducing two sulfuric acid groups or phosphoric acid groups into the diol or a neutralized product thereof. The cosmetic comprises at least one of substance selected from these products. <P>COPYRIGHT: (C)2005,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 Kszuyuki 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 obtained by epoxidizing a double bond of an alkyl oleate molecule (wherein the alkyl group has 8 to 16 carbon atoms) and then hydroxylating.
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 alkyl group chain length of the alkyl oleate of the present invention is 8 to 16, and 10 is desirable from the viewpoint of availability. The diol of the present invention and its sulfated or phosphoric acid oxide or neutralized product thereof are easily produced from, for example, dodecyl oleate. 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 2-chain 2-hydrophilic group, an unsaturated fatty acid ester called alkyl oleate as a raw material, epoxidation using hydrogen peroxide and formic acid at its double bond, alcoholic potassium hydroxide It was realized using only inexpensive raw materials by the reaction of dihydroxylation of epoxide used, sulfation using chlorosulfonic acid, or phosphorylation using phosphoric anhydride. As the alkali used for neutralization, sodium hydroxide, potassium hydroxide, or lithium hydroxide is used.
Next, it shows in detail in an Example.
In the present invention, cosmetics are skin cosmetics such as cream, milk and lotion, hair cosmetics such as hair setting agents, and makeup cosmetics such as liquid foundation. The present invention also includes shampoos, rinses and hair conditioners. These cosmetics can contain at least one or more of the sulfated or phosphoric oxides or neutralized products thereof according to the present invention.

Synthesis of Diol of the Present Invention To a mixture of 105.7 g of decyl oleate (0.25 mol) and 500 ml of formic acid, 35 g of 25% hydrogen peroxide is added all at once 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 3N alcoholic potassium hydroxide for 1 hour. After removing the alcohol, when cold, add water to dissolve it uniformly, and adjust the pH to 1 using sulfuric acid. The resulting white precipitate (diol, about 76 g) is washed with water. A recrystallized product using tetrahydrofuran as a recrystallization solvent gave an iodine value of 0 to obtain a diol of the present invention.

Synthesis of sulfate of the present invention To a mixture of 63 g of the diol (0.2 mol) obtained in Example 1 and 250 ml of glacial acetic acid, 46 g of monochlorosulfonic acid (0.4 mol) was added dropwise over 1 hour with stirring at 0 ° C. Then, it is stirred for 1 hour. Glacial acetic acid was 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 95 g) gave sulfate group absorption 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 Invention 34 g of phosphorus oxychloride (0.22 mol) was added dropwise over 30 minutes to a mixture of 63 g of the diol (0.2 mol) obtained in Example 1 and 300 ml of tetrahydrofuran while 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. 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 valid as confirmation of the sulfate of the present invention.

When the biodegradability of the disodium salt of the sulfur oxide and disodium salt of the phosphoric acid according to the present invention was determined according to the biodegradability test method of the synthetic detergent described in JIS-K3363, the disodium salt of the sulfur oxide of the present invention. The biodegradability of the disodium salt of phosphorous oxide was 100%. The biodegradability of (CH ₂ ) ₂ [NCO (C ₁₁ H ₂₃ ) (COOH) CH ₂ COOH] ₂ -2OH (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 sulfate of the present invention 0.2%
9. Water residue

Preparation of Shampoo In accordance with the following formulation, Component 1-6 was added to Component 7 water, stirred and mixed for 1 hour, and then a shampoo was prepared.
1. Sodium polyoxyethylene lauryl sulfate (30% solution) 50%
2. Disodium salt of the sulfate of the present invention 5%
3. Lauric acid diethanolamide 2%
4). Citric acid 0.1%
5). EDTA 0.01
6). Sodium benzoate 0.05%
7). Water residue

  A diol that is an intermediate of an anionic surfactant containing a 2-chain 2-hydrophilic group that can be easily produced using only inexpensive raw materials starting from alkyl oleate, and sulfating or phosphorylating the two hydroxyl groups of this diol The obtained anionic surfactant containing a 2-chain and 2-hydrophilic group excellent in biodegradability and skin safety and a cosmetic containing the same have great industrial applicability.

Claims (3)

  A diol obtained by epoxidizing a double bond of an alkyl oleate molecule (wherein the alkyl group has 8 to 16 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.