JP2011195522A - Solubilizing agent comprising alkylene oxide derivative and solubilizing composition including the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solubilizing agent which has an excellent solubilization force to a hardly-water-soluble oily ingredient, and in which feeling of use is good, and stickiness after use is little.SOLUTION: The solubilizing agent comprises an alkylene oxide derivative shown by formula (I): HO-(EO)a-(AO)n-(EO)b-H (I), and a solubilizing composition includes the solubilizing agent and the oily ingredient. In the formula, EO denotes an oxyethylene group, AO denotes one sort or two sorts or more of a 8-12C oxyalkylene group, when AO includes two or more sorts, a block form addition or a random-like addition may be possible, the addition configuration of AO and EO is a block form; a and b are the average addition mole numbers of the oxyethylene group, n is the average addition mole number of the oxyalkylene group, and they have the relations: 10≤a+b≤300, 2≤n≤50, and 0.75≤(a+b)/(a+b+n)≤0.99.

Description

  The present invention relates to a solubilizer comprising an alkylene oxide derivative and a solubilized composition comprising the solubilizer.

In recent years, there is an increasing demand for anti-aging and whitening, and medicinal ingredients having an antioxidative action and a whitening action such as tocopherol acetate and coenzyme Q10 are often added to cosmetics. Many of these components are non-polar oily components, and when blended with water-based cosmetics, they become cloudy, thereby impairing the commercial value. In order to solve these problems, it is common to solubilize this oil component with various surfactants.

As various surfactants, nonionic surfactants that can be solubilized at a lower concentration are widely used because CMC is low. Among nonionic surfactants, alkylene oxide derivatives are added depending on the number of added moles. It is possible to adjust the hydrophilic-lipophilic balance freely, which is very useful.

As surfactants of alkylene oxide derivatives with high solubilizing power, polyoxyethylene hydrogenated castor oil (Patent Document 1), sorbitan ester derivatives such as polyoxyethylene sorbitan monooleate (Patent Document 2), and a combination of these two Such a compound (Patent Document 3) is known. However, the surfactant has a problem that it feels sticky.

Further, as ether type nonionic surfactants, alkyl ether type alkylene oxides having a hydrocarbon chain as a lipophilic group, pluronic type alkylene oxide derivatives having a lipophilic group as a polypropylene oxide or polybutylene oxide (Patent Document 4) are available. is there. However, these surfactants cannot exhibit a sufficient effect to solubilize non-polar oily components, and if they are blended at a high level for solubilization, the feeling of use decreases. Therefore, development of a surfactant for cosmetics that satisfies these problems has been demanded.

JP 09-67241 A JP 2001-261579 A JP 2002-020220 A JP 2002-129189 A

  The problem to be solved by the present invention is to provide a solubilizing agent that has excellent solubilizing power for poorly water-soluble oily components such as fragrances and oil-soluble drugs, and has a good feeling of use and less stickiness after use. Is to provide.

As a result of intensive studies on the above problems, the present inventors have found that certain alkylene oxide derivatives have both excellent solubilization power and feeling of use and have completed the present invention.
That is, the present invention is as follows.
(1) A solubilizer comprising an alkylene oxide derivative represented by the formula (I).
HO- (EO) a- (AO) n- (EO) b-H (I)
(In the formula, EO is an oxyethylene group, AO is one or two or more oxyalkylene groups having 8 to 12 carbon atoms, and when AO is two or more, it may be randomly added even if added in a block form. The addition form of AO and EO is in the form of a block, a and b are the oxyethylene groups, n is the average number of moles of oxyalkylene groups, and 10 ≦ a + b ≦ 300, 2 ≦ (n ≦ 50 and 0.75 ≦ (a + b) / (a + b + n) ≦ 0.99)
(2) The above-mentioned solubilizer, wherein AO is an oxyalkylene group having 8 to 10 carbon atoms.
(3) (A) 0.01 to 50% by mass of the alkylene oxide derivative according to claim 1 or 2
(B) 0.001 to 10% by mass of oil component
The solubilized composition which contains and the mass ratio of component (A) and (B) is (A) / (B) = 0.1-20.

The solubilizer comprising the alkylene oxide derivative of the present invention can remarkably improve the solubility of oil-soluble cosmetic and pharmaceutical ingredients, colorants and fragrances, or general fats and oils in aqueous preparations. In addition, the solubilized composition containing the oil component prepared using the solubilizer is remarkably excellent in usability, such as good conformability to the skin and little stickiness. Therefore, the solubilized composition of the present invention is particularly useful as an external preparation for skin, such as cosmetics, quasi-drugs and external medicines, which are directly applied to the skin.

Hereinafter, preferred embodiments of the present invention will be described.
In the alkylene oxide derivative represented by the formula (I), EO is an oxyethylene group. a and b are the average addition mole number of an oxyethylene group, and are 10 <= a + b <= 300, Preferably it is 20 <= a + b <= 250, More preferably, it is 30 <= a + b <= 200. If it is less than 10, the solubilizing power tends not to be sufficiently exhibited, and if it exceeds 200, the feeling of use tends to be inferior.

AO is an oxyalkylene group having 8 to 12 carbon atoms, preferably an oxyalkylene group having 8 to 10 carbon atoms. For example, oxyoctamethylene and oxyoctylene groups such as an oxyalkylene group having 8 carbon atoms, oxynonamethylene groups and oxynonylene groups such as an oxyalkylene group having 9 carbon atoms, and oxydecacene as an oxyalkylene group having 10 carbon atoms. Examples of the oxyalkylene group having 11 carbon atoms such as a methylene group and an oxydecylene group include an oxyundecamethylene group and oxyundecylene group, and examples of the oxyalkylene group having 12 carbon atoms include an oxide decamethylene group and an oxydecylene group. An oxyalkylene group having 7 or less carbon atoms tends not to have a sufficient solubilizing power, and when it has 13 or more carbon atoms, the feeling of use tends to be inferior. These oxyalkylene groups may be either linear or branched. In the branched oxyalkylene group, as the oxyalkylene group having 8 carbon atoms, there is an oxyoctylene group derived from octylene oxide. For example, as an oxyalkylene group having 9 carbon atoms such as 1,2-oxyoctylene group, There are oxynonylene groups derived from nonylene oxide, for example, oxydecylene groups having 10 carbon atoms such as 1,2-oxynonylene groups include oxydecylene groups derived from decylene oxide, such as 1,2-oxydecylene groups. As the 11 oxydecylene group, there is an oxydecylene group derived from dodecylene oxide. For example, as an oxydecylene group having 12 carbon atoms such as 1,2-oxide decylene group, an oxyundecylene group derived from undecylene oxide is used. Yes, for example 1,2-oxyundecylene group It is.

The cleavage reaction of the alkylene oxide in the production process of the alkylene oxide derivative represented by the formula (I) may be any of α-cleavage, β-cleavage, or a mixed type thereof. For example, in the case of 1,2-octylene oxide derived from octylene oxide having 8 carbon atoms, an oxy-1-hexylethylene group represented by the following general formula (II) or an oxy represented by the following general formula (III) It becomes either 2-hexylethylene group.

（II）

(II)

（III）

(III)

n is an average addition mole number of the oxyalkylene group, 2 ≦ n ≦ 50, preferably 3 ≦ n ≦ 30.

The ratio of the average added mole number (a + b) of the oxyethylene group to the sum (a + b + n) of the average added mole number of the oxyethylene group and the oxyalkylene group is 0.75 ≦ (a + b) / (a + b + n) ≦ 0.99. If it is smaller than 0.75 or larger than 0.99, a satisfactory solubilizing force cannot be obtained, which is not preferable.

The addition form of the oxyethylene group and the oxyalkylene group is preferably a block form, and the arrangement order is the order of oxyethylene group-oxyalkylene group-oxyethylene group. As long as the oxyalkylene group is in the range of 8 to 12 carbon atoms, one type may be used, two or more types may be used, and the addition form in the case of two or more types may be block or random.

The alkylene oxide derivative of the component (A) used in the solubilized composition of the present invention has a structure represented by the formula (I), and the blending ratio with respect to the entire composition is 0.01 to 50% by mass, preferably 0.02 to 30% by mass, more preferably 0.05 to 10% by mass.

The oil component of the component (B) used in the solubilized composition of the present invention may be either volatile or non-volatile as long as it is an oily substance blended in cosmetics, quasi drugs, and external medicines. Any of solid, paste, and liquid may be used. Examples thereof include water-insoluble substances such as oil-soluble vitamins such as vitamins A, D, E, and K, animal and plant extracts, synthetic and semi-synthetic oil-soluble drugs and cosmetic ingredients, various oils, and fragrances. As oil-soluble vitamins, vitamin A such as retinol, vitamin E such as tocopherol acetate, α-tocopherol, and δ-tocopherol, and vitamin D such as cholecalciferol are synthetic and semi-synthetic oil-soluble drugs. Ubiquinone, etc. includes oils such as olive oil, avocado oil, castor oil, safflower oil, cottonseed oil, cocoa butter, coconut oil and other liquid or solid oils, esters such as isopropyl myristate, cetyl octanoate and stearic acid, alcohol Ethers such as alkyl ethers, hydrocarbons such as liquid paraffin, petrolatum, and microcrystalline wax, waxes such as beeswax, lanolin, and carbanau wax, silicone oil phase components such as dimethylpolysiloxane, lauric acid, myristic acid, palmitic Acid, stearic acid, etc. Higher alcohols such as fatty acids, lauryl alcohol, cetanol, stearyl alcohol, oleyl alcohol and the like, and examples of the fragrance include natural fragrances, synthetic fragrances, blended fragrances, and fragrances isolated from natural fragrances. One or more oily components can be blended.

The blending amount of the oil component (B) in the total composition of the solubilized composition of the present invention is 0.001 to 10% by mass, preferably 0.002 to 5% by mass, more preferably 0.005 to 3% by mass. It is.

From the viewpoint of obtaining excellent solubilization stability, the mass ratio of the component (A) and the component (B) is preferably about (A) / (B) = 0.1 to 20, preferably 0.2 to 15, More preferably, it is 0.5-10.

In the solubilized composition of the present invention, surfactants other than the above components, solvents such as ethanol, carboxymethylcellulose, hydroxypropylmethylcellulose, gum arabic, carrageenan, which are generally blended in cosmetics, quasi-drugs, external medicines, etc. Thickening stabilizers such as other oils, moisturizers such as polyethylene glycol, glycerin, propylene glycol, 1,3-butylene glycol, pH adjusters such as citric acid, acetic acid, tartaric acid, lactic acid, chelating agents, chemicals, ultraviolet rays You may mix | blend other components, such as preservatives, such as an absorber, a ultraviolet-ray scattering agent, phenoxyethanol, and a paraoxybenzoic acid, a fragrance | flavor, a pigment, and dye. These components may be blended one by one or two or more.

The solubilizing agent of the present invention dissolves various oily substances well, and the composition containing the oily substances solubilized by the solubilizing agent has a good feel to the skin. It has technical problems related to solubilization as well as blending needs, and is particularly suitable for blending into cosmetics that require a good feeling on the skin. Similarly, it is also suitable for blending into a pharmaceutical preparation for which good use feeling is desired. Therefore, the solubilized composition of the present invention is suitable as a cosmetic for skin and hair, a quasi-drug, a pharmaceutical for external use, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Examples of Compound 1 (Table 1) are shown as Production Examples 1 and 2.

Production Example 1 (oxyoctylene formation reaction)
After charging 118 g of 1,2-octanediol and 1.7 g of boron trifluoride diethyl ether in a 5 L autoclave and replacing with dry nitrogen, 800 g of 1,2-octylene oxide was added dropwise with stirring and stirring for 3 hours. did. The reaction product was taken out, neutralized with potassium hydroxide to pH 6-7, and the contained water was removed by treating at 100 ° C. for 1 hour, followed by filtration to remove the formed salt, and polyoxyoctylene. 902 g was obtained. The hydroxyl value was 123.9 KOHmg / g.

Production Example 2 (oxyethylenation reaction)
After 450 g of polyoxyoctylene obtained in Production Example 1 and 1.5 g of potassium hydroxide were charged into a 5 L autoclave and replaced with dry nitrogen, potassium hydroxide was completely dissolved at 140 ° C. with stirring. Subsequently, 300 g of ethylene oxide was dropped from a dropping device at 140 ° C. and 0.2 to 0.5 MPa (gauge pressure), followed by stirring for 2 hours. Thereafter, the reaction product was taken out from the autoclave, neutralized with hydrochloric acid to pH 6-7, and the contained water was removed by treating at 100 ° C. for 1 hour. Further, filtration was performed to remove the purified salt after the treatment to obtain Compound 1. The hydroxyl value was 48.6 KOHmg / g.

The present inventors synthesized compounds 2 to 9, which are alkylene oxide derivatives shown in Table 1 below, according to the above production examples.

  About the compounds 1-11 of Table 1, it mix | blended like Table 2 and the solubilization state was confirmed.

<Confirmation of solubilized state>
It was confirmed according to the following method that the system was in a solubilized state. That is, using a spectrophotometer (JASCO) V-530, the transmittance% of a 1 cm cell of visible light having a wavelength of 25 ° C. and 600 nm was measured, and a transmittance of 90% or more was determined to be good.
◎: Transmittance 95% or more ○: Transmittance 90% or more and less than 95% Δ: Transmittance 80% or more and less than 90% ×: Transmittance 50% or more and less than 80% XX: Transmittance less than 50% <Composition>
d-δ-tocopherol 0.05 mass%
Solubilizer See Table 2 Ethanol 5.0% by mass
Water balance

In Table 2, compounds 5-7 and 9 could not solubilize tocopherol even when (A) / (B) = 20, and compound 8 solubilized when (A) / (B) = 20 However, when (A) / (B) = 10, a good solubilized state was not obtained.
This is because compound 5 is a random addition, and compounds 6 and 7 do not have both a hydrophilic group and a lipophilic group, and compound 9 has a hydrophilic group and a lipophilic group, but the lipophilic group is not an oxypropylene group. It was enough. Moreover, since the compound 8 also has a weak solubilizing power, the amount added must be increased in order to obtain a good solubilized state. On the other hand, the compounds 1 to 4 and the compounds 10 and 11 which are the products of the present invention were in a good solubilized state at (A) / (B) = 10.

A lotion formulated as shown in Tables 3 and 4 was prepared for the compounds 1 to 4, 8, 10, and 11 in Table 1 in which the solubilized state was good, and sensory evaluation (feel and use during production) Later stickiness) and stability evaluation. The blending ratio of the alkylene oxide derivative and tocopherol was in accordance with the ratio at which the solubilized state was confirmed. The solubilization stability of the examples was all good. The evaluation results are also shown in Tables 3 and 4.

<Feel when using>
About the lotion immediately after manufacture, the touch at the time of use was performed in accordance with the following method. That is, 20 professional female panelists judge the feel when using lotion after washing their face in five stages as follows, and find the average value of 20 people, when using an average value of 3.5 or more It was judged that the lotion had a good touch.
5: Familiarity with the skin is very good during use, and the feel is very light.
4: Familiarity to skin during use and light feel.
3: Familiarity to skin during use is slightly good and feels slightly light.
2: Familiarity to skin during use is slightly good, and feels slightly heavy.
1: The skin feels bad when used and has a heavy feel.

<Stickiness after use>
About the lotion immediately after preparation, the stickiness 10 minutes after use was determined by the following method. That is, 20 professional female panelists use a lotion after washing their face, and after 10 minutes, the stickiness after 10 minutes is judged in 5 stages as follows, and the average value of 20 people is obtained. .5 or more were judged to be non-sticky lotions.
5: I feel that my skin is not sticky at all.
4: Feels that the skin is not sticky.
3: I feel that my skin is slightly sticky.
2: Feels that the skin is sticky.
1: It feels clear when the skin is sticky.

  As shown in Table 3, in Examples 1 to 4, good results were obtained in all sensory evaluations. In Table 4, the touch of Comparative Example 1 was lowered due to the high blending for solubilization. In Comparative Examples 2 and 3, the feeling during use was inferior or sticky.

Claims (3)

A solubilizer comprising an alkylene oxide derivative represented by the following formula (I):

HO- (EO) a- (AO) n- (EO) b-H (I)

(In the formula, EO is an oxyethylene group, AO is one or more oxyalkylene groups having 8 to 12 carbon atoms, and when AO is two or more, block addition or random addition The addition form of AO and EO is in the form of a block, a and b are the oxyethylene groups, n is the average number of moles of oxyalkylene groups, and 10 ≦ a + b ≦ 300, 2 ≦ n ≦ 50, and (It has a relationship of 0.75 ≦ (a + b) / (a + b + n) ≦ 0.99). The solubilizer according to claim 1, wherein AO is an oxyalkylene group having 8 to 10 carbon atoms. (A) 0.01 to 50% by mass of the alkylene oxide derivative according to claim 1 or 2
(B) 0.001 to 10% by mass of oil component
The solubilized composition which contains and the mass ratio of component (A) and (B) is (A) / (B) = 0.1-20.