JPH05238926A - Emulsified cosmetic - Google Patents

Abstract

PURPOSE:To provide an emulsified cosmetic giving refreshing feeling when applied, with no oily feeling even after applied, giving relieved feeling on its use, also hard to develop makeup falling off due to water or sweat, having high emulsion stability even in the case of a low emulsifier level. CONSTITUTION:The objective cosmetic can be obtained by incorporating a mixture of (A) a silicone oil-contg. oil phase component, (B) water, (C) cosmetic powder with the surface put to water-repelling treatment, and (D) ethyl alcohol, with (E) 0.01-0.5wt.% of an emulsifier containing 50-100wt.% of a compound of formula I [R<1>-R<12> are such that at least one of them is of formula II (Q is 3-20C divalent hydrocarbon group; R<13> and R<14> are each 1-5C hydrocarbon group or H, or being both H), the rest being 3-30C hydrocarbon group or X-R<15> (X is divalent hydrocarbon group containing ether linkage and/or ester linkage; R<15> is 1-30C hydrocarbon group); (l)-(n) are each 0-200; when (l+m+n)=0, at least one of R<1>-R<3> and R<10>-R<12> is of formula II, however, excepting that one of R<1>-R<12> is of formula II (Q is trimethylene; R<13>=R<14>=H), the rest being each CH3].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an emulsified cosmetic which contains ethyl alcohol and has a good feeling of use such as a refreshing feeling and a refreshing feeling and is excellent in emulsion stability even with an extremely small amount of an emulsifier.

[0002]

2. Description of the Related Art W / O type cosmetic / skin external preparations represented by water-in-oil type (W / O type) emulsified cosmetics are
Since water is contained in the ingredients, it gives a refreshing feeling when applied to the skin and further suppresses the oily feeling. In addition, many of them have a creamy shape, and the performance thereof is such that they spread well on the skin and it is easy to obtain a uniform finish without unevenness.

[0003] In particular, W / O type cosmetics have higher microbial resistance than O / W type cosmetics because the oil phase is a continuous phase.
Even when used, it leaves an oil film with low moisture permeability on the skin surface to protect the skin from dryness for a long time,
It has excellent properties such as less re-emulsification even when it comes into contact with water during washing, water work, sweating, etc., and less likely to cause makeup discoloration such as color unevenness and wrinkles.

[0004]

However, the conventional W
/ O type cosmetics are difficult to obtain a stable emulsion system,
In order to achieve stabilization, it is often the case that the amount of water contained for dispersion is limited and that the oil component with high viscosity is used in the continuous phase. In that case, there was a drawback in that it had a strong stickiness and a strong oily feeling.

Therefore, in order to obtain a refreshing feeling in an emulsion system with less stickiness, the amount of the oil component is reduced and a uniform film is formed on the skin to give a smooth feel without stickiness. It has been practiced to use the resulting silicone oil (polysiloxane) as an oil component. However, conventional silicone oils have poor compatibility with ordinary surfactants and other oil components, and the emulsification system formability is extremely poor, so it was extremely difficult to obtain a uniform and stable emulsification system.

In order to solve this, it is considered to add a large amount of an emulsifier, but this method also has a drawback that the refreshing feeling peculiar to silicone oil is lost although the emulsion system is stabilized to some extent. It was

On the other hand, attempts have been made to blend ethyl alcohol into W / O type emulsion cosmetics in order to obtain a good refreshing feeling, but it is extremely possible to obtain an emulsion type excellent in stability. I had the problem of difficulty.

Therefore, it is possible to solve the drawbacks of the conventional water-in-oil type emulsion cosmetics and to develop an emulsion cosmetic having an excellent feeling of use such as a good refreshing feeling and a refreshing feeling and having excellent emulsion stability. Was wanted.

[0009]

Under the circumstances, the inventors of the present invention have conducted intensive studies and as a result, by using a specific siloxane derivative as an emulsifier, an oil phase component containing a silicone oil and a surface water-repellent agent with a trace amount of the emulsifier. We have found that an extremely stable emulsified system can be obtained even when the treated cosmetic powder contains ethyl alcohol and water, and the above problems can be solved, and the present invention has been completed.

That is, the present invention comprises the following components (A),
(B), (C), (D) and (E) (A) Oil phase component containing silicone oil (B) Water (C) Surface water repellent cosmetic powder (D) Ethyl alcohol (E) The following general formula (1)

[0011]

[Chemical 2]

(In the formula, Q is a divalent hydrocarbon having 3 to 20 carbon atoms.
Indicates a basic group, R¹³And R¹⁴Are hydrogen atom or carbon respectively
Indicates a hydrocarbon group of the number 1 to 5, at least one of which
Is a hydrogen atom. ) Is the group represented by
Linear, branched or cyclic hydrocarbon group having a prime number of 1 to 30
Or the following formula (3) -X-R¹⁵ (3) (In the formula, X contains an ether bond and / or an ester bond.
A divalent hydrocarbon group ¹⁵Is a straight chain having 1 to 30 carbon atoms,
Indicates a branched or cyclic hydrocarbon group. In the group represented by
Yes, l, m, and n are numbers from 0 to 2000,
R when l + m + n = 0¹~ R³, R^Ten~ R¹²Out of
At least one represents the group (2). However, R¹~ R¹²
One of them is Q, trimethylene and R¹³And R¹⁴Together
It is a group (2) that is a hydrogen atom, and the rest are all methyl.
Except when it is a group. ] A siloxane derivative represented by
0.01 to 50% by weight or more and 100% by weight or less
Characterized by containing at least 0.5% by weight but not more than 0.5% by weight
The present invention provides an emulsified cosmetic composition.

In the present invention, the silicone oil used as the oil phase component (A) may be any one commonly used in cosmetics, such as dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane. , Methylhydrogenpolysiloxane, and the like. Particularly, in the case of reducing oily feeling and sticky feeling, volatile dimethylpolysiloxane, dimethylcyclopolysiloxane and the like can be exemplified as preferable ones. These may be used alone or in combination of two or more. Other oily components include hydrocarbons such as squalane, liquid paraffin and vaseline; waxes such as whale wax and carnauba wax; ester oils such as jojoba oil, octyldodecyl myristate and neopentyl glycol dioctanoate; olive oil and macadamia nuts. Natural animal and vegetable oils and fats such as oils; diglyceride and the like can be mentioned.

The component (A) is preferably added in an amount of 5 to 70% by weight, particularly 10 to 50% by weight, based on the total amount of the emulsified cosmetic composition of the present invention. In addition, the silicone oil is 50 in the oil phase component.
It is preferable to add -100% by weight.

The water as the component (B) in the present invention is 10 to 70% by weight, especially 15 to 50% by weight based on the total amount of the emulsified cosmetic composition of the present invention.
It is preferable to add the composition in a weight percentage.

The component (C) surface-water-repellent treated cosmetic powder used in the present invention is one or two or more kinds of surfaces selected from known cosmetic powders, which are subjected to water-repellent treatment. ..
Here, as the mother powder to be water repellent treated, talc, sericite, mica, kaolin, silica, nylon powder,
Extender pigments such as polyethylene powder, silk powder, cellulose powder; titanium oxide, iron oxide, zinc oxide,
Examples thereof include ultramarine, dark blue, chromium oxide, organic tar dyes, colorants such as lakes, and complex pigments such as titanium mica and iron oxide coated mica. Further, examples of the surface water repellent treatment agent include silicone, higher fatty acid, higher alcohol, fatty acid ester, metal soap, amino acid, alkyl phosphate and the like. Further, as the surface treatment method, for example, an oil and fat treatment method for adsorbing oils and fats on the powder surface or utilizing functional groups such as hydroxyl groups to cause esterification or etherification to make the powders lipophilic, fatty acid Metal soap treatment using zinc salt or magnesium salt, silicone treatment using dimethylpolysiloxane or methylhydrogenpolysiloxane, treatment with the following fluorine compound having a perfluoroalkyl group [here, fluorine compound Means, for example, the following general formula [C _m F _{2m + 1} C _n H _2n O] _y PO (OH) _3-y (wherein m is an integer of 4 to 14, n is an integer of 1 to 12, y
Represents an integer of 1 to 3. ), Polyfluoroalkylphosphoric acid (see US Pat. No. 3,632,744), fluoroalkyldi (oxyethyl) amine phosphate (see JP-A-62-250074), and resin having a perfluoroalkyl group (JP-A-55). No. 167209), tetrafluoroethylene resin, perfluoroalcohol, perfluoroepoxy compound, sulfoamide type fluorophosphoric acid, perfluorosulfate, perfluorocarboxylate, perfluoroalkylsilane (JP-A-2-21).
No. 8603) is applied but not limited to these. ] Etc. are mentioned.

Among these components (C), preferred are cosmetic powders which have been treated to be water repellent with silicone. The cosmetic powder thus obtained has the strongest water repellency, and even when actually applied to an emulsification system, makeup breakage due to water or sweat is most unlikely to occur. In addition, the emulsified particles are dense and have the longest stability. A relatively stable emulsified system can be obtained even when cosmetic powder without surface water repellent treatment is used, but the hydrophilic nature of the powder surface makes it very easy for makeup to break due to water or sweat. Become.

These components (C) can be used alone or in combination of two or more, and it is preferable to add 2 to 50% by weight, especially 3 to 30% by weight to the total amount of the emulsion cosmetic of the present invention. ..

From the viewpoint of emulsion stability, it is preferred that the component (D) of the present invention, component (D), be contained in an amount of 2 to 20% by weight, particularly 8 to 18% by weight, based on the total amount of the emulsion cosmetic of the present invention. If the blending amount exceeds 20% by weight, the emulsion system becomes unstable and the irritation to the skin becomes strong. On the other hand, if it is less than 2% by weight, a refreshing feeling is not felt and it is not preferable.

In the general formula (1) showing the siloxane derivative used as the emulsifier of the component (E) in the present invention, Q
The divalent hydrocarbon group having 3 to 20 carbon atoms represented by
Linear alkylene groups such as trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene; propylene, 2
-Methyltrimethylene, 2-methyltetramethylene, 2
Examples include branched-chain alkylene groups such as -methylpentamethylene and 3-methylpentamethylene. The hydrocarbon group having 1 to 5 carbon atoms represented by R ¹³ or R ¹⁴ is methyl,
Ethyl, propyl, butyl, pentyl, isopropyl,
Examples thereof include linear, branched or cyclic alkyl groups such as sec-butyl, tert-butyl, neopentyl and cyclopentyl. The divalent hydrocarbon group containing an ether bond and / or an ester bond represented by X is-(CH ₂ ) _r-
(OC ₂ H ₄ ) _p- (OC ₃ H ₆ ) _q -O- (where p and q are numbers from 0 to 50, r is an integer from 3 to 20),-(CH ₂ ) _r -O -CO
_{-, - (CH 2) r} -COO- (r is 3 to 20 integer), and the like. Further, as the linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, doeicosyl, tetra Linear alkyl groups such as eicosyl, hexaeicosyl, octaeicosyl, and triacontyl; isopropyl, sec-butyl, tert-
Examples thereof include branched chain alkyl groups such as butyl, neopentyl, 1-ethylpropyl, 1-heptyldecyl; cyclic alkyl groups such as cyclopentyl, cyclohexyl, abiethyl, cholesteryl and the like. And, l, m, and n are 0 or more and 20 or more from the viewpoints of easy availability of the organohydrogenpolysiloxane as a raw material, operability during production, and the like.
It is preferably in the range of 00 or less.

The siloxane derivative (1) can be produced, for example, according to the following reaction formula. (1) Method for producing siloxane derivative (1a) having no group (3)

[0022]

[Chemical 3]

[In the formula, at least one of R ^{16 to} R ²⁷ is a hydrogen atom, and the remainder is a linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, and l, m and n are 0. More than 20
Indicates a number less than or equal to 00. Q'represents a hydrocarbon group having 3 to 20 carbon atoms having at least one double bond, and R ¹³ and R ¹⁴ have the same meaning as described above. At least one of R ¹ ′ to R ¹² ′ is the group (2), and the rest has 1 carbon atom.
-30 straight-chain, branched-chain or cyclic hydrocarbon groups. However, ^one of R ¹ ′ to R ¹² ′ is a group (2) in which Q is trimethylene and R ¹³ and R ¹⁴ are both hydrogen atoms,
And except when all the rest are methyl groups. ]

That is, an alkenyl glyceryl ether (2 ') is reacted with an organohydrogenpolysiloxane (4) having at least one silicon-hydrogen bond to give a siloxane derivative (1a) having no group (3). ) Is obtained.

(2) Method for producing siloxane derivative (1b) having group (3)

[0026]

[Chemical 4]

[In the formula, at least two of R ¹⁶ ′ to R ²⁷ ′ are hydrogen atoms, and the rest are linear, branched or cyclic hydrocarbon groups having 1 to 30 carbon atoms, l, m and n Has the same meaning as described above. Q ', R ¹³ and R ¹⁴ have the same meanings as described above. X 'has at least one double bond, and the hydrocarbon group containing an ether bond and / or ester bond, R ¹⁵ is as defined above. At least one of R ¹ ″ to R ¹² ″ is a group (2), at least one of the rest is a group (3), and the rest is a straight chain, branched chain or cyclic group having 1 to 30 carbon atoms. Is a hydrocarbon group. ]

That is, the organohydrogenpolysiloxane (4 ') having at least two silicon-hydrogen bonds is reacted with the alkenyl glyceryl ether (2') and the compound (3 ') to form the group (3). A siloxane derivative (1b) having is obtained. here,
Whichever of the compound (2 ′) and the compound (3 ′) is reacted with the compound (4 ′) first, the compound (4 ′) is simultaneously reacted.
May be reacted with.

The starting organohydrogenpolysiloxane (4) or (4 ') has at least 1 in its molecule.
The number of [(4)] or at least two [(4 ′)] silicon-hydrogen bonds is essential, and the viscosity is
There are no particular restrictions on the molecular structure and the like, and various known ones can be used, but l, m, and n are 0 or more and 2000 or less in view of availability of raw materials, operability during production, and the like. Those are preferable.

The compound (2 ') is represented by the general formula (2')
In the above, it is preferable that Q ′ is a ω-alkenyl group. Further, as the compound (3 ′), X ′ in the general formula (3 ′) is

[0031]

[Chemical 5]

The above reactions (1) and (2) are carried out in the presence of a catalyst, and the catalyst generally used for hydrosilylation, for example, a free radical initiator; a photoinitiator;
A complex compound of a metal such as ruthenium, rhodium, palladium, osmium, iridium and platinum; and those obtained by supporting these on silica gel or alumina can be mentioned. Of these, chloroplatinic acid, speier reagent (isopropyl chloride solution of chloroplatinic acid) and the like are particularly preferable.
The catalyst may be used in an amount sufficient to promote the reaction between the organohydrogenpolysiloxane (4) or (4 ') and the alkenyl glyceryl ether (2') and / or compound (3 '), Although not particularly limited, a range of 10 ⁻⁶ to 10 ⁻¹ mol is preferable for ¹ mol of the olefin used.

In this reaction, the use of a reaction solvent is not essential, but the reaction may be carried out in a suitable solvent if necessary. The reaction solvent is not particularly limited as long as it does not inhibit the reaction, and examples thereof include hydrocarbon solvents such as pentane, hexane and cyclohexane; benzene solvents such as benzene, toluene and xylene; ethers such as diethyl ether and diisopropyl ether. Systematic solvents; alcoholic solvents such as methanol, ethanol, isopropyl alcohol, butanol and the like can be mentioned. When an alcohol solvent is used, a pH adjusting agent such as potassium acetate (JP-A-57-149290) is used to prevent or suppress the dehydrogenation reaction between Si-H and -OH. Is preferred.

The ratio of the alkenyl glyceryl ether (2 ') and / or the compound (3') to the organohydrogenpolysiloxane (4) or (4 ') used in this reaction depends on the siloxane derivative (1) obtained. Other proportions are optional, provided that there is a sufficient amount of alkenyl glyceryl ether (2 ') to have at least one or more silicon-bonded glyceryl groups (2) in the molecule.
When the resulting compound (1) is used to emulsify a carbon-based oil agent, the total number of units of the group (2) and the group (3) is set to the same ratio as the number of remaining dimethylsiloxane units or more. When emulsifying a silicon-based oil agent, it is preferable that the total number of units of the group (2) and the group (3) is within 1/5 or less of the number of remaining dimethylsiloxane units.

The hydrosilylation proceeds at 0 to 200 ° C., but considering the reaction rate and the coloring of the product, 0 to 100
It is preferable to carry out at ° C. The reaction time is 0.5 to 24.
It is preferably about time.

Particularly preferable examples of the component (E) of the present invention include those represented by the following structural formula.

[0037]

[Chemical 6]

More particularly preferred are those in which m (average value) = 40 to 80 and n (average value) = 3 to 6.

In the present invention, the emulsifier of the component (E) has an emulsifying power such as sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, and isostearyl glyceryl ether, in addition to the siloxane derivative. Surfactants can be used. It is sufficient that the emulsifier as the component (E) is blended in an amount of 0.01% by weight or more and less than 0.5% by weight based on the total amount of the emulsion cosmetic of the present invention. Further, it is preferable to add 50 to 100% by weight of the siloxane derivative (1) in the emulsifier.

The emulsified cosmetic composition of the present invention may further contain other components used in ordinary cosmetic compositions in an amount of 0 to 40% by weight, as long as the effects of the present invention are not impaired.
Other components include moisturizers (sorbitol, xylitol, glycerin, maltitol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, sodium pyrrolidonecarboxylate, lactic acid,
Sodium lactate, polyoxypropylene fatty acid ester, polyethylene glycol, etc.), glycerin, 1,3
-Butylene glycol, propylene glycol, isoprene glycol, 1,3-butanediol, dipropylene glycol, diglycerin, triglycerin, polyglycerin, trimethylolpropane, erythritol,
Pentaerythritol, sorbitan, sorbitol, glucose, maltitol, saccharose, trehalose, ethylene oxide or propylene oxide adduct of sugar or sugar derivative, polyols such as polyethylene glycol, plant extract (ryokcha, cucumber, clove, etc.), UV absorption Agents {ethyl paraaminobenzoate, octyl paradimethylaminobenzoate [Escalol (E
SCALOL) 507 (VANDYK)], sinoxate, octyl paramethoxycinnamate [Escalol 55
7, Parsol MCX (GIVAUD
AN)], 2- (2-hydroxy-5-methylphenyl) benzotriazole, oxybenzone [escarol 567, Spectra-Sol (Spectra-Sol).
b) UV9 (American Cyanamid)
Company)], urocanic acid, ethyl urocanate, benzophenone, tetrahydroxybenzophenone [eg, Ubinal D50 (BASF)], 4-t-butyl-
4'-methoxybenzoylmethane [Persol 178
9], JP-A-2-212579, JP-A-3-18
The following general formula (5) described in Japanese Patent No. 8041

[0041]

[Chemical 7]

[In the formula, R represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, an alkenyloxy group having 1 to 8 carbon atoms, or a (polyoxyalkylene) oxy group, or two R's are α-methylenedi groups. An oxy group may be formed, and n is 1
A benzoylpinacolone derivative or the like], an alcohol, an antioxidant such as a chelating agent,
pH adjusters (buffers such as lactic acid-sodium lactate, citric acid-sodium citrate), preservatives (urea, methylparaben, ethylparaben, propylparaben, butylparaben, sodium benzoate, etc.), thickeners (carboxyvinyl polymers) , Water-soluble polymers such as carboxymethyl cellulose, polyvinyl alcohol, carrageenan, gelatin, electrolytes such as sodium chloride and potassium chloride), dyes and fragrances, and whitening agents (arbutin, kojic acid, ascorbic acid and its derivatives, etc.), etc. , And intracellular lipids (ceramides, ceramide-like structural substances, etc.).

Further, examples of the ceramide-like structural material mentioned here include amide derivatives described in JP-A-62-228048.

The emulsified cosmetics to which the present invention is applied include
Skin care products such as face care creams or emulsions, skin care creams or emulsions; hair cosmetics; quasi drugs;

The emulsion cosmetic of the present invention is prepared, for example, as follows. That is, first, the component (E) is added to the component (A) and stirred. Next, the component (C) is added to and dispersed in this, and then the component (B) and the component (C), which have been mixed in advance with stirring, are added little by little to obtain the intended emulsified cosmetic. In the above preparation, the manufacturing temperature can be selected from any temperature of 5 to 90 ° C., and a stable emulsified cosmetic material can be obtained at any temperature.

The characteristic feature of the emulsified cosmetic composition of the present invention thus obtained lies in the state of its emulsified particles. When the emulsified particles are observed with a microscope, it is observed that the cosmetic powder of the component (C) is adsorbed on the surface of the aqueous phase particles having a particle size of 10 to 50 μm dispersed in the oil phase. When the cosmetic powder is present inside the water phase particles instead of on the surface, long-term emulsion stability is poor. Another feature of the emulsified particles is that they are very stable when standing or shaking, but they are easily destroyed when the solution is made into a thin film to give a light shear. This shows that the same phenomenon occurs when actually applied to the skin, and therefore,
It is considered that even though it is a water-in-oil type, the emulsion is broken immediately upon application, the aqueous phase containing ethyl alcohol penetrates into the skin, and a refreshing feeling is felt.

The emulsion cosmetic of the present invention preferably has a low viscosity and is in a fluid state at room temperature. When the viscosity is high, not only the appearance is unfavorable, but also the refreshing feeling is poor when applied.

When the emulsified cosmetic composition of the present invention is left to stand for a long period of time, the phase of the oil component may be separated to some extent on the upper part. It can also be used as a fee.

[0049]

EXAMPLES The present invention will be further described with reference to production examples and examples, but the present invention is not limited thereto.

Production Example 1 30 g (18.5 mmol) of α, ω-dihydrodimethylpolysiloxane (average chain length 20), 10-undecenyl glyceryl ether were placed in a 100 ml two-necked flask equipped with a cooling tube and a magnetic stirrer. 8 g (48.3 mmol), 0.95 g (0.97 g) of 10% potassium acetate in ethanol
mmol) and 24 g of isopropyl alcohol, and a 2% isopropyl alcohol solution of chloroplatinic acid was added thereto.
26 g (0.010 mmol) was added and heated to raise the temperature. The temperature of the contents was kept at 50 ° C. and stirred for 2 hours. After distilling off the solvent, unreacted 10-undecenyl glyceryl ether was distilled off under reduced pressure to obtain a brown highly viscous substance. This brown highly viscous substance was treated with activated carbon to obtain 35.0 g (yield 89.7%) of a colorless and transparent highly viscous substance. The obtained product was analyzed by IR and NMR spectra to show α,
ω-bis [11- (2,3-dihydroxypropoxy)
Undecyl] dimethylpolysiloxane (average chain length 20)
It was confirmed to be (A).

[0051]

[Chemical 8]

IR (liquid film, cm ^-1 ) 3420 (-OH) 2964, 2928, 2860 (CH) 1262 (Si-Me) 1100, 1026, 802 (Si-O-Si) ¹ H-NMR [δppm, in CDCl _3, CHCl ₃ standard (7.28 ppm)] 0.00 (br, about _{132H) Si-C H 3 0.57} (t, 4H) Si-C H 2 - 1.39 (br, 32H) -C H 2 - 1.47-1.70 (m, 4H) C H ₂ -CH ₂ -O 2.22 (br, 2H) -CH ₂ -O H 2.62 (br, 2H) -CH -O H 3.30-3.59 (m, 8H) C H ₂ -O 3.59 -3.80 (m, 4H) C H ₂ -OH 3.80-3.96 (m, 2H) C H -OH ¹³ C-NMR [δppm, in CDCl ₃ , CHCl ₃ standard (77.2ppm)] 0.39, 1.23, 1.36 Si- _{C H 3 18.5 Si- C H 2} - 23.4, 26.3, 29.6, 29.8, 33.7 - C H 2 - 64.7 - C H 2 OH 70.6 - C H-OH 72.0 -CH 2 - C H 2 -O 72.7 -CH- C H ₂ -O

[0053]

[Chemical 9]

Production Example 2 By the same method as in Production Example 1, α, ω-bis [11-
(2,3-Dihydroxypropoxy) undecyl] dimethylpolysiloxane (average chain length 50) (B) was synthesized (yield 95.3%).

[0055]

[Chemical 10]

IR (liquid film, cm ^-1 ) 3420 (-OH) 2968, 2932 (CH) 1264 (Si-Me) 1094, 1020, 866, 802 (Si-O-Si) ¹ H-NMR [δppm, in CDCl _3, CHCl ₃ standard (7.28 ppm)] 0.08 (br, about _{312H) Si-C H 3 0.57} (t, 4H) Si-C H 2 - 1.30 (br, 32H) -C H 2 - 1.48-1.80 (m, 4H) C H ₂ -CH-O 2.20 (br, 2H) CH ₂ -O H 2.63 (br, 2H) CH-O H 3.38-3.60 (m, 8H) C H ₂ -O 3.60-3.81 ( m, 4H) C H ₂ -OH 3.81-3.97 (m, 2H), C H -OH ¹³ C-NMR (δ ppm, in CDCl ₃ , CHCl ₃ standard (77.2 ppm)) 0.38, 1.22, 1.36, 1.96 Si- _{C H 3 18.5 Si- C H 2} 23.4, 26.3, 29.6, 29.8, 33.7 - C H 2 - 64.7 C H 2 OH 70.8 C H-OH 72.1 CH 2 C H 2 -O 72.7 CH C H 2 -O

[0057]

[Chemical 11]

Production Example 3 (1) In a 50 ml two-necked flask equipped with a cooling tube and a magnetic stirrer, 32.8 g (56.6 mmol) of α, ω-dihydrohexadecamethyloctasiloxane and 4.0 g of 1-decene were placed.
(28.5 mmol) was charged and 3.0 mg of chloroplatinic acid was added.
(5.8 × 10 ⁻³ mmol) was added, and the mixture was stirred in a water bath for 6 hours. 11.0 g of colorless transparent liquid (bp 160
C./0.005 Torr) (yield 54%) was obtained. The product obtained is 1-decyl-determined by IR and NMR spectra.
It was confirmed to be 15-hydrohexadecamethyloctasiloxane. (2) In a 50 ml two-necked flask equipped with a cooling tube and a magnetic stirrer, 10 g (13.9 mmo) of 1-decyl-15-hydrohexadecamethyloctasiloxane synthesized in (1).
l) 10-undecenyl glyceryl ether 4.4 g
(18.0 mmol), 0.35 g (0.36 mmol) of 10% ethanol solution of potassium acetate and 10 g of isopropyl alcohol were charged, and 0.093 g (3.6 × 10 ⁻³ ) of a 2% isopropyl alcohol solution of chloroplatinic acid was charged. mmo
l) was added and heated to raise the temperature. The temperature of the contents was kept at 40 ° C, and the mixture was stirred at 40 ° C for 3 hours. After the solvent was distilled off, the reaction product was purified by applying it to a silica gel column to obtain a colorless transparent oil 1
1.8 g (yield 88%) was obtained. The obtained purified product is IR
And NMR spectrum confirmed that it was 15-decylhexadecamethyloctasiloxanil undecyl glyceryl ether (C).

[0059]

[Chemical 12]

IR (liquid film, cm ^-1 ) 3400 (-OH) 2964, 2928, 2860 (CH) 1262 (Si-Me) 1096, 1026, 840, 804 (Si-O-Si) ¹ H-NMR [ [delta] ppm, in CDCl _3, CHCl ₃ standard (7.28 ppm)] -0.02-0.10 (m, 48H) Si- C H 3 0.50 (t, 4H) Si-C H 2 - 0.87 (t, 3H) -C H 3 1.24 (br, 32H) -C H 2 - 1.47-1.66 (m, 2H) C H 2 -CH 2 -O 2.32 (t, 1H) CH 2 -O H 2.71 (d, 1H) CH-O H 3.36- 3.57 (m, 4H) -C H ₂ -O 3.57-3.73 (m, 2H) -C H ₂ -OH 3.73-3.90 (m, 1H) C H -OH ¹³ C-NMR (δppm, CHCl in CDCl _{3 3} standards (77.2 ppm)) 0.38, 1.25, 1.35 Si- C H ₃ 14.3- C H ₃ 18.5 Si- C H ₂ 22.9, 23.4, 26.3, 29.5, 29.6, 29.7, 29.8, 29.9, 32.1, 33.6- C H _{2 - 64.5 C H 2 OH 70.7} C HOH 72.1 CH 2 C H 2 O 72.7 CH C H 2 O

Production Example 4 A 100 ml two-necked flask equipped with a cooling tube and a magnetic stirrer was of the formula (D ')

[0062]

[Chemical 13]

15 g (4.4 mmol) of organohydrogensiloxane represented by: 8.1 g (33 mmol) of 10-undecenyl glyceryl ether, 1 part of potassium acetate
0.65 g (0.66 mmol) of a 0% ethanol solution and 50 g of isopropyl alcohol were charged, and 0.17 g (6.
6 × 10 ⁻³ mmol) was added and the temperature was raised by heating. The temperature of the contents was kept at 40 ° C. and stirred for 2.5 hours. After distilling off the solvent and treating with activated carbon, the unreacted 10
-Undecenyl glyceryl ether was distilled off to obtain a brown viscous material. The obtained product was confirmed by IR and NMR spectra to be compound (D) represented by the following formula.

[0064]

[Chemical 14]

IR (liquid film, cm ^-1 ) 3400 (-OH) 2968, 2932, 2860 (CH) 1262 (Si-Me) 1096, 1022, 844 (Si-O-Si) ¹ H-NMR [δppm, in CDCl _3, CHCl ₃ standard (7.28 ppm)] 0.01 (s, about _{273H) Si-C H 3 0.38-0.58} (m, 10H) Si-C H 2 - 1.10-1.41 (br, 80H) -C H 2 -1.44-1.86 (m, 10H) C H ₂ -CH ₂ -O 3.30-3.55 (m, 20H) C H ₂ -O 3.55-3.77 (m, 10H) C H ₂ -OH 3.77-3.90 (m, 5H ) C H -OH

Production Example 5 A compound (E) represented by the following formula was synthesized by the same method as in Production Example 4 (yield 97%).

[0067]

[Chemical 15]

IR (liquid film, cm ^-1 ) 3420 (-OH) 2968, 2932, 2860 (CH) 1264 (Si-Me) 1096, 1026, 802 (Si-O-Si) ¹ H-NMR [δppm, CHCl ₃ standard (7.28 ppm) in CDCl ₃ ) 0.00 (s, about 390H) Si-C H ₃ 0.35-0.50 (m, 8H) Si-C H ₂ 1.08-1.39 (br, 64H) -C H _2- 1.39-1.62 (br, 8H) C H ₂ -CH ₂ -O 1.96-2.29 (br, 4H) CH ₂ -O H 2.43-2.68 (br, 4H) CH-O H 3.38-3.50 (m, 16H) C H ₂ -O 3.50-3.70 (m, 8H) C H ₂ -OH 3.70-3.86 (m, 4H) C H -OH

Production Example 6 A compound (F) represented by the following formula was synthesized by the same method as in Production Example 4 (yield 99%).

[0070]

[Chemical 16]

IR (liquid film, cm ^-1 ) 3424 (-OH) 2964, 2928, 2860 (CH) 1262 (Si-Me) 1090, 1034, 864, 798 (Si-O-Si) ¹ H-NMR [ [delta] ppm, in CDCl _3, CHCl ₃ standard (7.28 ppm)] 0.00 (s, about _{510H) Si-C H 3 0.34-0.55} (m, 8H) Si-C H 2 1.02-1.38 (br, 64H) -C H _{2 - 1.38-1.66 (br, 8H)} C H 2 -CH 2 -O 1.98-2.40 (br, 4H) CH 2 O H 2.40-2.78 (br, 4H) CH-O H 3.26-3.53 (m, 16H) C H ₂ -O 3.53-3.70 (m, 8H) C H ₂ -OH 3.70-3.88 (m, 4H) C H -OH

Example 1 Liquid emulsified cosmetics: Liquid emulsified cosmetics having the compositions shown in Table 1 were produced, and the emulsion stability immediately after the production was evaluated.
Are also shown. (Manufacturing method) Components (1) to (5) were mixed, and the components (6) to (8), which had been mixed in advance, were gradually added to the mixture while stirring with an emulsifying machine to emulsify the mixture to obtain a liquid emulsion cosmetic. .. (Emulsification stability evaluation method) By visually observing the state of each liquid emulsion cosmetic immediately after its production, the emulsion stability was evaluated according to the following criteria. ◯: Good with no change in condition Δ: Slight separation / aggregation X: Separation / aggregation, poor emulsification

[0073]

[Table 1]

As is clear from Table 1, the product of the present invention has an extremely good emulsified state after production, whereas the comparative product is inferior in stability due to separation of the oil agent into the upper layer over time. there were. In place of the siloxane derivative (E) of the product 7 or 8 of the present invention, siloxane derivatives (A), (B),
The emulsion composition produced using (C), (D) or (F) also showed superior stability to the comparative product.

Example 2 Hand Cream: (Component) (wt%) (1) Siloxane derivative (E) 0.3 (2) Methylphenylpolysiloxane 5.0 (3) Decamethylcyclopentasiloxane 5.0 (4) ) Dimethylpolysiloxane (50cs) 10.0 (5) Perfume 0.2 (6) Fluorine-coated zinc 15.0 (7) Ethyl alcohol 15.0 (8) Glycerin 15.0 (9) Purified water balance (production method) The components (1) to (6) were mixed, and the components (7) to (9), which had been mixed in advance, were gradually added to the mixture while stirring with an emulsifier to emulsify to obtain a hand cream.

Example 3 Moisturizing Cream: (Component) (wt%) (1) Dimethylpolysiloxane (50cs) 10.0 (2) Decamethylcyclopentasiloxane 5.0 (3) Squalane 8.0 (4) Amide Derivative ^{* 2} 2.0 (5) Siloxane derivative (B) 0.3 (6) Isostearyl glyceryl ether 1.0 (7) Perfume 0.2 (8) Silicone-coated zinc 15.0 (9) Ethyl alcohol 15. 0 (10) Glycerin 15.0 (11) Purified water balance * 2: Amide derivative of Example 1 of JP-A-62-228048 (manufacturing method) Components (1) to (8) are mixed and mixed by an emulsifier While stirring, the premixed components (9) to (11) were gradually added and emulsified to obtain a moisturizing cream.

The emulsified cosmetics of Examples 2 to 3 were all excellent in stability, feeling of use and the like, and had a refreshing feeling.

[0078]

EFFECT OF THE INVENTION The emulsified cosmetic composition of the present invention has a refreshing feeling when applied, has no oily feeling even after application, has a refreshing feeling of use, and is unlikely to cause makeup discoloration due to water or sweat. Further, it has excellent emulsification stability even though a small amount of emulsifier was used.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location A61K 7/02 P 9165-4C B01F 17/54 6345-4G B01J 13/00 A 7310-4G (72 ) Inventor Yuji Suzuki 3-28-1-102 Nakashizu, Sakura City, Chiba Prefecture

Claims (1)

[Claims] 1. The following components (A), (B), (C),
(D) and (E) (A) Oil phase component containing silicone oil (B) Water (C) Surface water repellent cosmetic powder (D) Ethyl alcohol (E) General formula (1) Chemical 1](In the formula, Q represents a divalent hydrocarbon group having 3 to 20 carbon atoms,
R¹³And R¹⁴Are hydrogen atoms or carbons having 1 to 5 carbon atoms, respectively.
A hydrogen atom group, at least one of which is a hydrogen atom
is there. ) Is a group represented by
A linear, branched or cyclic hydrocarbon group of
(3) -X-R¹⁵ (3) (In the formula, X contains an ether bond and / or an ester bond.
A divalent hydrocarbon group ¹⁵Is a straight chain having 1 to 30 carbon atoms,
Indicates a branched or cyclic hydrocarbon group. In the group represented by
Yes, l, m, and n are numbers from 0 to 2000,
R when l + m + n = 0¹~ R³, R^Ten~ R¹²Out of
At least one represents the group (2). However, R¹~ R¹²
One of them is Q, trimethylene and R¹³And R¹⁴Together
It is a group (2) that is a hydrogen atom, and the rest are all methyl.
Except when it is a group. ] A siloxane derivative represented by
0.01 to 50% by weight or more and 100% by weight or less
Characterized by containing at least 0.5% by weight but not more than 0.5% by weight
Emulsified cosmetics.