JP4985017B2 - Nonionic surfactant and cosmetic comprising the same - Google Patents

Description

  The present invention relates to a nonionic surfactant obtained by adding an alkylene oxide to a dimer diol, and a cosmetic comprising the same.

There are various types of nonionic surfactants, one of which is an alkylene oxide derivative. The alkylene oxide derivative is a particularly useful surfactant because the balance between hydrophilicity and lipophilicity and molecular weight can be controlled by the number of added moles of an oxyethylene group or an oxypropylene group.
Alkylene oxide derivatives are widely used in pharmaceuticals and cosmetics, and representative examples include pluronic surfactants. The Pluronic type is known as a highly polar surfactant because the entire lipophilic group is a polyoxypropylene group and the hydrophilic group is a polyoxyethylene group, so that the entire molecule has a polyether structure.
On the other hand, non-polar hydrocarbon oils such as squalane, polybutene, and liquid paraffin are widely used in cosmetics in order to improve the feeling of slipping when applied to the skin and the familiarity with the skin. However, it is difficult to solubilize non-polar oils such as hydrocarbon oils in water using the above-mentioned pluronic surfactants. There was a problem of loss of familiarity with the skin.

In order to solve such problems, surfactants into which nonpolar hydrocarbon groups have been introduced have been proposed.
For example, a detergent composition has been proposed in which a derivative obtained by adding ethylene oxide and propylene oxide to dimer diol has been proposed, and it is removed from the dyeing machine and oil, dyes, auxiliaries, alterations, and fibers adhering to the fibers. For example, there is an effect of cleaning stains made of glue, oligomer and the like, and improving the fastness of the fibers (for example, Patent Document 1). However, when blended into cosmetics, propylene oxide alone is not sufficient to impart lipophilicity, but it is insufficient in terms of imparting a feeling of slipping and familiarity to the skin, and further solubilizing the oil in water It was insufficient for this. In order to increase the solubilizing power, it is necessary to increase the addition amount of the surfactant. If the addition amount is increased, the feeling of slipping at the time of application and the familiarity with the skin are further deteriorated.
In addition, as a dimer diol derivative of a cosmetic base, an adduct having a carbon number 12 or 14 epoxy alkane added to dimer diol has been proposed (Patent Document 2). However, although this adduct is excellent in water retention, moisture retention, pigment dispersibility, and compatibility with oil agents, it does not exhibit surface activity, and the solubilizing power of oil agents in water is extremely poor. It was.

For these reasons, there has been a demand for the development of a nonionic surfactant that is excellent in surface active ability and has a good feeling of slipping and familiarity to the skin when blended in cosmetics.
JP2000-282086 JP2003-313149A

  An object of the present invention is to provide a nonionic surfactant having an excellent surface activity ability comprising an alkylene oxide derivative of dimer diol. Another object of the present invention is to provide a cosmetic material that has a good feeling of slipping when applied to the skin and has a good familiarity with the skin.

That is, the present invention is as follows.
(1) A nonionic surfactant comprising an alkylene oxide derivative represented by the following formula (I).
Z- {O-[(AO) _a- (EO) _b ] -H} ₂ (I)
(In the formula, Z is a dimer diol residue, EO is an oxyethylene group, AO is an oxyalkylene group having 3 to 4 carbon atoms, and contains at least 20% by mass of an oxyalkylene group having 4 carbon atoms. AO is 2 In the case of more than seeds, they may be added in block form or randomly, and the addition form of AO and EO is block form, a and b are the oxyalkylene group and oxyethylene group, respectively. 1 ≦ 2 × a ≦ 70, 1 ≦ 2 × b ≦ 150, and the ratio of the oxyethylene group to the total of the oxyethylene group and the oxyalkylene group is 20 to 95% by mass.)
( 2 ) A cosmetic comprising 0.01 to 50% by mass of the nonionic surfactant.
( 3 ) The said cosmetics characterized by containing 0.01-30 mass% of polyhydric alcohol.

  The nonionic surfactant comprising the alkylene oxide derivative of the present invention is excellent in surface activity, and also has a good feeling of slipping and familiarity with the skin when applied to the skin. In addition, by using a polyhydric alcohol in combination, a cosmetic with good moisture retention can be obtained. Cosmetics containing this nonionic surfactant are very useful.

In the alkylene oxide derivative represented by the formula (I), Z is a residue obtained by removing a hydroxyl group from dimer diol. Here, the dimer diol is a diol obtained by reducing dimer acid.
The dimer acid used as a raw material for the dimer diol used in the present invention is mainly composed of a dimer obtained by polymerizing an unsaturated fatty acid or an ester thereof with an alcohol having 1 to 4 carbon atoms. Specifically, it can be synthesized by a method in which an unsaturated fatty acid such as oleic acid, linoleic acid, linolenic acid or the like or a C 1-4 alcohol ester thereof is reacted by thermal polymerization such as Diels-Alder reaction or other reaction methods. . The generated dimer acid may contain unreacted fatty acids as long as the effects of the present invention are not impaired.

The dimer acid is preferably a dimerized unsaturated fatty acid having 12 to 24 carbon atoms or an alcohol ester having 1 to 4 carbon atoms. Such unsaturated fatty acids include myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid and alcohol esters having 1 to 4 carbon atoms. Of these, oleic acid, linoleic acid, linolenic acid, and alcohol esters having 1 to 4 carbon atoms thereof are preferable, and oleic acid and alcohol esters having 1 to 4 carbon atoms are particularly preferable.
The unsaturated fatty acid may be derived from animals or plants, but is preferably derived from plants. Examples of commercially available dimer diols include Sovermol 908 (manufactured by Cognis Japan Co., Ltd.), PRIPOL 2033 (manufactured by Unikema Co., Ltd.), PESPOL HP-1000 (manufactured by Toagosei Co., Ltd.), and the like.

EO is an oxyethylene group. AO is an oxyalkylene group having 3 to 4 carbon atoms, and examples thereof include an oxypropylene group, an oxybutylene group, an oxyisobutylene group, an oxy-2-butylene group, and an oxytetramethylene group.
AO includes an oxyalkylene group having 4 carbon atoms, and the oxyalkylene group having 4 carbon atoms is preferably an oxybutylene group or an oxytetramethylene group, and more preferably an oxybutylene group. The oxyalkylene group having 4 carbon atoms is essential for improving the solubilizing power of the oil in water and the familiarity with the skin. Preferably, when it is contained in an amount of 20% by mass or more based on the total amount of AO, these effects are further enhanced. It will be good. More preferably, it contains 50 mass% or more, and more preferably 70 mass% or more.

The addition form in the case of two or more AOs may be random or block, but is preferably block. In the case of the block form, any oxyalkylene group may be added first to the dimer diol.
The addition form of EO and AO is block-like, and the addition order is bonded to dimer diol in the order of AO and EO. If the order of addition is EO and AO relative to the dimer diol, or if EO and AO are random, the action as a surfactant is reduced, and the solubilizing power of the oil to water is poor. In some cases, a good slip feeling cannot be obtained.

a is an average added mole number of AO and is 1 ≦ 2 × a ≦ 70, preferably 2 ≦ 2 × a ≦ 50. If it is less than 1, it is not preferable because it is inferior in the familiarity with the skin and the water-solubilizing power of the oil. Furthermore, when it exceeds 70, it may be inferior to solubilization power and familiarity with skin, and is not preferable.
b is an average added mole number of EO, 1 ≦ 2 × b ≦ 150, preferably 5 ≦ 2 × b ≦ 100, more preferably 10 ≦ 2 × b ≦ 80. If it is smaller than 1, the solubilizing power of the oil to water and the moisturizing effect may be impaired, which is not preferable. Furthermore, if it exceeds 150, the slipperiness may be inferior, which is not preferable.
The ratio of EO to the total of EO and AO is 20 to 95% by mass, preferably 30 to 90% by mass, and more preferably 40 to 90% by mass. If it is less than 20% by mass, the solubilizing power of the oil to water and the moisturizing effect are inferior, and if it exceeds 95% by mass, the slipping feeling may be inferior.

  The nonionic surfactant represented by the formula (I) of the present invention can be produced by a known method. For example, after addition polymerization of butylene oxide or propylene oxide to dimer diol under an alkali catalyst at 50 to 160 ° C. and 0.5 MPa (gauge pressure) or less, addition polymerization of ethylene oxide is further performed to form hydrochloric acid, phosphoric acid, After neutralizing with an acid such as acetic acid, it can be obtained by removing water and neutralized salts.

The alkylene oxide derivative of the present invention is useful as a base for cosmetics, and a cosmetic containing the same is also useful. The compounding quantity to cosmetics is 0.01-50 mass%, Preferably it is 0.1-30 mass%, More preferably, it is 0.1-20 mass%.
When a polyhydric alcohol is further blended into the cosmetic of the present invention, the familiarity to the skin and the moisture retention will be good, and the blending amount is 0.01 to 30% by mass, preferably 0.1 to 30% by mass, Preferably, it is 0.1-25 mass%. If it exceeds 30% by mass, there is a possibility that the slipperiness and the blending stability may be impaired.

  Examples of the polyhydric alcohol include glycerin, diglycerin, polyglycerin, 1,3-butylene glycol, 3-methyl-1,3-butylene glycol, 1,2-hexanediol, 1,2-pentanediol, ethylene glycol, diethylene glycol And polyethylene glycol, propylene glycol, dipropylene glycol, glucose, methyl glucoside, polypropylene glycol, sorbitol, sorbitan, xylitol, trehalose, maltitol, mannitol and alkylene oxide derivatives thereof. Preferred are glycerin, 1,3-butanediol, propylene glycol, dipropylene glycol, 1,2-hexanediol, 1,2-pentanediol, polyethylene glycol, alkylene oxide derivatives of methyl glucoside, sorbitol, xylitol, and trehalose. .

  In the cosmetics of the present invention, various components generally used in cosmetics, pharmaceuticals, etc., that is, vitamins, UV absorbers, water-soluble substances, as long as they do not impair the effects of the present invention. Polymer, antioxidant, anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant, sequestering agent, ethanol, thickener, preservative, dye, powder Examples include body.

Hereinafter, the present invention will be described specifically by way of examples.
<Synthesis Example 1 Synthesis of Compound 1>
AO: 5 mol of oxypropylene group, 15 mol of oxybutylene group (2 × a = 20), EO; 50 mol (2 × b = 50), EO; 62% by mass
270 g of dimer diol (0.50 mol, trade name: Sovermol 908 manufactured by Cognis Japan Co., Ltd., dimer diol derived from oleic acid) and 7.0 g of potassium hydroxide were charged into an autoclave, and the air in the autoclave was dried nitrogen. After the replacement, the catalyst was completely dissolved at 140 ° C. with stirring. Subsequently, 145 g of propylene oxide was dropped from a dropping device at 120 ° C. and 0.2 to 0.5 MPa (gauge pressure), and the mixture was stirred for 3 hours. Subsequently, 540 g of butylene oxide was dropped from a dropping device at 120 ° C. and 0.2 to 0.5 MPa (gauge pressure), and the mixture was stirred for 4 hours. Further, 1100 g of ethylene oxide was added dropwise at 150 ° C. and 0.2 to 0.5 MPa, 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 salt produced after the treatment, and a base of Compound 1 was obtained.
<Synthesis Example 2 Synthesis of Compound 2>
AO: 15 mol of oxybutylene groups (2 × a = 15), EO; 30 mol (2 × b = 30), EO; 55% by mass
270 g of dimer diol (0.50 mol, trade name: Sovermol 908 manufactured by Cognis Japan Co., Ltd., dimer diol derived from oleic acid) and 5.0 g of potassium hydroxide were charged into an autoclave, and the air in the autoclave was dried nitrogen. After the replacement, the catalyst was completely dissolved at 140 ° C. with stirring. Subsequently, 540 g of oxybutylene was dropped from a dropping device at 120 ° C. and 0.2 to 0.5 MPa (gauge pressure), followed by stirring for 4 hours. Subsequently, 660 g of ethylene oxide was dropped from a dropping device at 120 ° C. and 0.2 to 0.5 MPa (gauge pressure), and stirred 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 salt generated after the treatment, and a base of Compound 2 was obtained.
According to the synthesis example, the alkylene oxide derivatives of compounds 3 to 11 shown in Table 1 were synthesized.

<Examples 1-5 and Comparative Examples 1-6>
In order to investigate the solubilizing power, a composition comprising the following substances was prepared, and the appearance after being allowed to stand at 40 ° C. for 1 month was determined according to the following criteria. The results are shown in Table 2.
○: Transparent x: Fluorescent color to white turbidity xx: White turbidity to separation (dispersion)
Compounds 1-10 2.0% by mass
Mineral oil 1.0% by mass
Ethanol 3.0% by mass
Water residue

<Examples 6 to 11 and Comparative Examples 7 to 12>
A cleansing cosmetic comprising the following ingredients was prepared. In the preparation method, each component was heated to 80 ° C., solubilized by stirring, then cooled to 40 ° C., and then an antiseptic and an antioxidant were added to obtain a cleansing cosmetic.
(Cleansing cosmetics)
Compounds 1 to 11 listed in Table 1 Polyhydric alcohol refer to Table 3 Refer to Table 3 Liquid paraffin 15% by mass
Hydrogenated polyisobutene 5% by mass
20% by mass of glycerin tri-2-ethylexanoate
PEG-7 glyceryl cocoate 25% by mass
10% by mass of sorbitan oleate
Preservatives Appropriate amount Antioxidant Appropriate amount of water Remaining 10 expert panelists applied lipstick in a 3 cm diameter circle on the inner side of the upper arm. After 30 minutes in a constant temperature and humidity room at 30 ° C. and a relative humidity of 30 to 40%, use the product of the present invention and the comparative product (about 2 g) for 10 seconds, and then rinse with tap water. The following three items were evaluated, and the results are shown in Table 3. In all items, a score of ○ or higher was accepted.
(1) The feeling of slipping when applied to lipstick was evaluated according to the following criteria.
A: Judged that 8 or more out of 10 people are good.
◯: Judged that 6 to 7 out of 10 people are good.
X: It is judged that 3 to 5 people are good in 10 people.
Xx: It is judged that 2 or less out of 10 people are good.
(2) Familiarity with the skin when familiarized with lipstick was evaluated according to the following criteria.
A: 8 out of 10 people judged that familiarity with skin was good.
○: Among 10 people, 6 to 7 people judged that familiarity with skin was good.
X: Among 5 people, 3 to 5 people judged that familiarity with the skin was good.
XX: Among 10 people, 2 or less people judged that familiarity with the skin was good.
(3) The moisture retention after washing was evaluated according to the following criteria.
A: Judged that 8 or more out of 10 people are moist.
○: It is determined that 6 to 7 of 10 people are moist.
X: It is judged that 3 to 5 people are moistened among 10 people.
XX: It is determined that 2 or less of 10 people are moist.

From Examples 1 to 5, all of the nonionic surfactants of the present invention have good oil solubilizing power in water. On the other hand, in Comparative Example 1, since the oxyethylene group and the oxybutylene group are random, the solubilizing power is inferior. Further, Comparative Examples 2 and 3 are inferior in solubilizing power because no oxyalkylene group and oxyethylene group are imparted respectively, and Comparative Example 4 is inferior in solubilizing power because it is a block but is an oxypropylene group. Furthermore, since both Comparative Examples 5 and 6 do not have a dimer diol skeleton, they have poor solubilizing power.
From Examples 6 to 11, the cosmetic of the present invention satisfies all of the feeling of slipping, familiarity with the skin, and moisture retention after washing. On the other hand, Comparative Examples 7 to 12 do not satisfy these three properties at the same time.

Claims (3)

A nonionic surfactant comprising an alkylene oxide derivative represented by the following formula (I):
Z- {O-[(AO) _a- (EO) _b ] -H} ₂ (I)
(In the formula, Z is a residue obtained by removing a hydroxyl group from dimer diol, EO is an oxyethylene group, AO is an oxyalkylene group having 3 to 4 carbon atoms, and contains at least 20% by mass of an oxyalkylene group having 4 carbon atoms. When two or more kinds of AO are used, they may be added in a block form or randomly, and the addition form of AO and EO is a block form, and a and b are each an oxyalkylene group. The average added mole number of the oxyethylene group is 1 ≦ 2 × a ≦ 70, 1 ≦ 2 × b ≦ 150, and the ratio of the oxyethylene group to the total of the oxyethylene group and the oxyalkylene group is 20 to 95% by mass. .) Cosmetics, characterized in that the nonionic surfactant of claim 1 Symbol placement containing 0.01 to 50 wt%. The cosmetic according to claim 2, comprising 0.01 to 30% by mass of a polyhydric alcohol.