JPH05178733A - Water-in-oil type emulsified cosmetic - Google Patents

Abstract

PURPOSE:To provide the subject cosmetic giving a refreshing use feeling by adding a pasty silicone composition to an oil phase component and employing a polyoxyalkylene-modified organopolysiloxane surfactant as an emulsifier. CONSTITUTION:The objective water-in-oil type emulsified cosmetic is obtained by adding a pasty silicone composition to an oil phase component, the pasty silicone composition being produced by enclosing a low viscosity silicone with the structure of a new silicone polymer, and by employing a polyoxyalkylene- modified organopolysiloxane surfactant as an emulsifier. The cosmetic does not have tackiness and an oily property, gives a refreshing use feeling and has a stable emulsion system. The cosmetic further has excellent aging stability and good water repellency and gives a high cosmetic effect.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-in-oil type emulsified cosmetic composition having excellent stability over time and a good feeling in use.

Emulsified compositions are generally oil-in-water type (O / W type)
And water-in-oil type (W / O type). Of these, the water-in-oil type emulsion composition has a better affinity for the skin than the oil-in-water type emulsion composition, and the skin surface is coated with an oil film. As a basic cosmetic due to its properties such as preventing moisture from evaporating, protecting the skin from dryness, and imparting a treatment effect to the skin, it is also excellent in water repellency and cosmetics such as make-up cosmetics because it does not easily lose its makeup. It is widely used as a base for medicines and pharmaceuticals.

In recent years, in a water-in-oil type emulsion composition, a silicone oil is used as an oil agent in order to obtain a refreshing, less sticky and good water repellency. When preparing such an emulsified composition, a lipophilic polyoxyalkylene-modified organopolysiloxane-based surfactant having good compatibility with silicone oil is generally used as an emulsifier.

However, it is difficult to obtain a polyoxyalkylene-modified organopolysiloxane-based surfactant that is sufficiently stable over time by simply blending it with an emulsified composition containing a large amount of silicone oil. There were very few thickening and gelling agents effective in the system.

[0005]

Therefore, an object of the present invention is to obtain a water-in-oil type emulsion cosmetic which is free from stickiness and oiliness, has a refreshing feeling of use, and has a stable emulsion system. To do.

[0006]

Under such circumstances, the present inventors have conducted diligent research and as a result, have found a paste-like silicone composition in which a low-viscosity silicone oil is included in the structure of a novel silicone polymer described below. By including it in the oil phase component and using a polyoxyalkylene-modified organopolysiloxane-based surfactant as an emulsifier,
The present invention has been completed by finding that an excellent water-in-oil emulsion cosmetic having excellent stability over time, good feeling in use, and highly useful as a base material for cosmetics can be obtained.

That is, the present invention comprises the following components (a)-
(C) (a) Oil phase component containing paste-like silicone composition (b) Polyoxyalkylene-modified organopolysiloxane surfactant (c) Water-in-oil emulsion cosmetic characterized by containing water Is provided.

In the present invention, it is contained in the component (a).
The pasty silicone composition is novel and
Formula (1) R¹ _aR² _bH_cSiO_{(4-abc) / 2} (1) {R here¹Is the same or different type of C1-C18 unsubstituted
Or a substituted alkyl group, aryl group, aralkyl group or
Halogenated hydrocarbon group, R²Is the general formula C_nH_2nO (C₂H _FourO)_d(C
₃H₆O)_eR³[R here³Is a hydrogen atom or 1 to 10 carbon atoms
Saturated aliphatic hydrocarbon group or-(CO) -R^Five(R^FiveIs carbon
A group represented by a saturated aliphatic hydrocarbon group of the formulas 1 to 5, d is
2 to 200 integer, e is 0 to 200 integer, and d + e is 3
To an integer of 200, and n is 2 to 6]
Ruylene group, a is 1.0 ≦ a ≦ 2.5, b is 0.001
≦ b ≦ 1.0, c is represented by 0.001 ≦ c ≦ 1.0}
Organohydrogenpolysiloxane, and / or
General formula (2) R¹ _fH_gSiO_{(4-fg) / 2} (2) (R here¹Is the same as above, f is 1.0 ≦ f ≦ 3.0,
g is 0.001 ≤ g ≤ 1.5)
Drogene polysiloxane and general formula (A) C_mH_2m-1O (C₂H_FourO)_h(C₃H₆O)_iC_mH_2m-1 (A) (here
Where h is an integer from 2 to 200, i is an integer from 0 to 200, and h +
i is an integer of 3 to 200, m is a polyoxyalkylene represented by 2 to 6) and
And / or general formula (B) R¹ _jR^Four _kSiO_{(4-jk) / 2} (B) (R here¹Is the same as above, R^FourIs terminally unsaturated
A monovalent hydrocarbon group having 2 to 10 carbon atoms having a group, j is 1.
0 ≦ j ≦ 3.0, k is 0.001 ≦ k ≦ 1.5)
In combination with the organopolysiloxane described above,
The component represented by the general formula (1) and / or the general formula (A) is
A total amount of 100 parts by weight of the composition as an essential component is added at 25 ° C.
Viscosity silicone with a viscosity of 100 cS or less
Presence of 3 to 200 parts by weight of oil and / or polyhydric alcohol or
Is a silicone polymer obtained by addition polymerization in the absence of
100 parts by weight and low viscosity silicone oil 5 to 1,000 parts by weight
What is obtained by kneading a part with shearing force
Is.

The silicone polymer constituting the pasty silicone composition of the present invention is a silicone oil and / or a polyhydric alcohol in which the organohydrogenpolysiloxane and the compound containing an aliphatic unsaturated group have a viscosity at 25 ° C. of 100 cS or less. Of addition-polymerization in the presence or absence of, but it is essential that either the organohydrogenpolysiloxane or the compound containing an aliphatic unsaturated group contains a polyoxyalkylene group. Is.

Therefore, when the combination of the organohydrogenpolysiloxane and the compound containing an aliphatic unsaturated group is exemplified, first one is a compound represented by the general formula (1) R ¹ _a R ² _b H _c SiO ₍ containing a polyoxyalkylene group). _{4-abc) / 2} (1) an organohydrogenpolysiloxane represented by
R ¹ is bonded to an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an aryl group such as a phenyl group and a tolyl group, an aralkyl group such as a benzyl group and a phenethyl group, or a carbon atom of these groups. Selected from a chloromethyl group, a trifluoropropyl group, etc., in which some or all of the hydrogen atoms are substituted with halogen atoms, and the same or different C 1-18 unsubstituted or substituted alkyl group, aryl group, aralkyl Group or halogenated hydrocarbon group, R
² is represented by the general formula (3) C _n H _2n O (C ₂ H ₄ O) _d (C ₃ H ₆ O) _e -R ³ (3), and R ³ is a hydrogen atom or a methyl group, an ethyl group, Saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms such as propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group, or represented by the formula-(CO) -R ⁵ , wherein R ⁵ is the number of carbon atoms. 1-5 saturated aliphatic hydrocarbon group, d is 2-20
An integer of 0, an integer of 0 to 200, and an integer of d + e of 3 to 200
Is a polyoxyalkylene group in which n is 2 to 6.

Regarding a of the a, b, and c values, 1.
When it is less than 0, the obtained polymer does not swell sufficiently in silicone oil, and when it is more than 2.5, the polymer obtained is kneaded with silicone oil under shearing force to give a paste-like composition with water content. It is necessary to set 1.0 ≦ a ≦ 2.5, preferably 1.0 to 2.0 because b cannot be sufficiently dispersed, and when b is less than 0.001, the obtained polymer is silicone. The paste composition obtained by kneading with oil under shearing force is not sufficiently dispersed in water, and if it is more than 1.0, the swelling property of the obtained polymer into silicone oil becomes insufficient, so 0.001 ≦ b ≦ 1.0, preferably 0.005 to 1.0, and c is 0.0
If it is less than 01, it will be difficult to form a three-dimensional structure in the polymer obtained by addition polymerization, and the viscosity of the silicone oil will be poor. If it is more than 1.0, the cross-linking density of the three-dimensional structure formed by addition polymerization will be poor. Is too high to hold silicone oil stably, so 0.00
1 ≦ c ≦ 1.0, preferably 0.005 to 1.0.

Therefore, the combination with the organohydrogenpolysiloxane represented by the general formula (1) is represented by the general formula (B) R ¹ _j R ⁴ _k SiO _{(4-jk) / 2} (B). R ¹ is the same as above, R ⁴ is a vinyl group at the terminal,
If the monovalent hydrocarbon group having 2 to 10 carbon atoms and having an aliphatic unsaturated group such as an allyl group, j is less than 1.0, the crosslinking density of the three-dimensional structure formed by addition polymerization becomes too high. Therefore, a polymer that stably holds silicone oil cannot be obtained, and if it exceeds 3.0, the formation of a three-dimensional structure in the polymer obtained by addition polymerization becomes insufficient and the viscosity increase of silicone oil is poor. Therefore, 1.0 ≦ d ≦
It is 3.0, preferably 1.0 to 2.5, and when k is less than 0.001, it becomes difficult to form a three-dimensional structure in the target polymer, and the viscosity increase of silicone oil If it is less than 1.5, the cross-linking density of the three-dimensional structure formed by addition polymerization becomes too high, and a polymer capable of stably holding silicone oil cannot be obtained. 001 ≦ k ≦ 1.
The organohydrogenpolysiloxane having an aliphatic unsaturated group of 5, preferably 0.005 to 1.0 is used. The organohydrogenpolysiloxane represented by the general formula (1) and the general formula (B) are used. The mixture with the organopolysiloxane represented by the following is abbreviated as mixture-I hereinafter.

A combination of the organohydrogenpolysiloxane represented by the general formula (1) and the polyoxyalkylene represented by the general formula (A) can also be used.

Another combination of the organohydrogenpolysiloxane and the compound containing an aliphatic unsaturated group is represented by the general formula (2) R ¹ _f H _g SiO _{(4-fg) / 2} (2). When R ¹ is the same as above and f is less than 1.0, the swelling property of the obtained polymer in silicone oil cannot be sufficiently obtained, and when it is more than 3.0, in the polymer obtained by addition polymerization, Since it becomes difficult to form a three-dimensional structure in the above, and the viscosity increase of the silicone oil becomes poor, 1.0 ≦ f ≦ 3.
0, preferably 1.0 to 2.5, and g is 0.001
If it is less than 3, it will be difficult to form a three-dimensional structure in the polymer obtained by addition polymerization, and the viscosity increase of the silicone oil will be poor. Since the cross-linking density becomes too high and the resulting polymer does not retain silicone oil stably, 0.001 ≦ g ≦ 1.5, preferably 0.005
An organohydrogenpolysiloxane of 1.0 and a compound represented by the general formula (A) C _m H _2m-1 (C ₂ H ₄ O) _h (C ₃ H ₆ O) _i C _m H _2m-1 (A) , H is 2 to 200, preferably 5 to 100, i
Is 0 to 200, preferably 0 to 100, and in order to sufficiently disperse water in the obtained polymer, it is desirable that h / i ≧ 1, and m is 2 to 6, preferably 3 to 6. A mixture with a certain polyoxyalkylene (hereinafter abbreviated as mixture-II) is exemplified.

In the present invention, the viscosity at 25 ° C. used in the addition polymerization of the mixture -I or -II is 100.
Examples of low-viscosity silicone oils of cS or less include linear or branched methyl polysiloxane, methylphenyl polysiloxane, ethyl polysiloxane, ethyl methyl polysiloxane, ethyl phenyl polysiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopenta Examples thereof include cyclic dimethyl polysiloxanes such as siloxane, and the viscosity of these is not particularly limited as long as the viscosity at 25 ° C. is 100 cS or less, and the viscosity is preferably 50 cS or less. Is good,
These may be used alone or as a mixture of two or more kinds.

Examples of the polyhydric alcohol include ethylene glycol, 1,3-butylene glycol, propylene glycol, dipropylene glycol, glycerin and diglycerin. These may be used alone or in combination of two or more. You may use together.

The amount of the low-viscosity silicone oil and / or the polyhydric alcohol is preferably 3 to 200 parts by weight based on 100 parts by weight of the above mixture -I or -II. When addition polymerization is carried out in the presence of a low-viscosity silicone oil and / or a polyhydric alcohol, a polymer containing them is obtained, which is higher than that obtained by addition polymerization in the absence thereof It exhibits swelling properties and exhibits excellent thickening properties.

The addition polymerization of the mixture -I or -II is carried out in the presence of a known platinum compound catalyst or rhodium compound catalyst such as chloroplatinic acid, alcohol-modified chloroplatinic acid or chloroplatinic acid-vinylsiloxane complex. The reaction may be performed at room temperature or under heating at 50 to 150 ° C.

In this case, an organic solvent may be used if necessary, and examples thereof include aliphatic alcohols such as methanol, ethanol, 2-propanol and butanol, aromatic hydrocarbons such as benzene, toluene and xylene, and n. Examples thereof include aliphatic or alicyclic hydrocarbons such as pentane, n-hexane and cyclohexane, and halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, trichloroethane, trichloroethylene and fluorochlorohydrocarbons.

To 100 parts by weight of the thus obtained silicone polymer, 5 to 1,000 parts by weight, preferably 20 to 500 parts by weight of a low-viscosity silicone oil is dispersed and mixed, and then kneaded under shearing force. A homogeneous silicone composition in the form of a paste is obtained.

When the amount of the silicone polymer is less than this range, a stable and good gel structure cannot be maintained, while when the amount is too much, it feels heavy on the skin and the usability and usability deteriorate. Absent.

The silicone oil used here is linear,
It may be branched, such as methylpolysiloxane, methylphenylpolysiloxane, ethylpolysiloxane, ethylmethylpolysiloxane, ethylphenylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane. Examples thereof include cyclic dimethylpolysiloxane, which may be used alone or as a mixture of two or more kinds.

The paste-like silicone composition thus obtained contains 10 to 90% by weight of the oil phase component (a).
(Hereinafter, simply indicated by%).

In addition to the above-mentioned pasty silicone composition, the oil phase component of the component (a) is blended with an oil agent used in a usual emulsion composition for cosmetics within a range in which the uniformity of the oil phase is not impaired. be able to. As the oil agent, any of natural animal / vegetable oil and synthetic oil can be used, and specifically,
Liquid, paste or solid hydrocarbons such as liquid paraffin and squalane, waxes, higher fatty acids, higher alcohols, esters, glycerides, silicone oils and the like can be mentioned.

The component (a) is incorporated in an amount of 5 to 90% in the total composition. If it is less than 5%, it is difficult to make the composition into a water-in-oil type, and if it exceeds 90%, the feel of the composition itself becomes extremely poor, which is not preferable as a cosmetic base.

The polyoxyalkylene-modified organopolysiloxane which is the component (b) of the present invention is liquid or pasty at room temperature and functions as an emulsifier in the cosmetic of the present invention. Specific examples include those represented by the following general formulas (4) to (6).

[0027]

[Chemical 1]

[In the formula, R ⁶ is an alkyl group having 1 to 5 carbon atoms or a phenyl group, and R ⁷ is a formula-(CH ₂ ) _r- O- (C ₂ H ₄ O) _s- (C ₃ H ₆ O )
_t -R ¹⁰ (R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, r is a number of 1 to 5, s is a number of 1 to 50, and t is 0 to 30.
Group represented by the formula (1), R ⁸ and R ⁹ are the same groups as any one of R ^{6 and} R ⁷ , p is a number of 5 to 300, and q is 1 to
The number of 50 is shown. However, not all of R ⁶ are phenyl groups]

[0029]

[Chemical 2]

[In the formula, R ⁶ , R ⁷ , p and q have the same meanings as described above, R ¹¹ is an alkyl group having 2 to 20 carbon atoms, and R ¹¹ is
¹² and R ¹³ are the same groups as any one of R ⁶ , R ^{7 and} R ¹¹ , and u is a number of 1 to 30. However, not all of R ⁶ are phenyl groups]

[0031]

[Chemical 3]

[Wherein R¹⁴Is an alkyl having 1 to 4 carbon atoms
Group, R¹⁵Is the expression-Q¹-O- (C₂H_FourO)_x-(C₃H₆O)_yR ¹⁹(Q¹Is carbon
Number 1 to 4 hydrocarbon group, R¹⁹Is a hydrogen atom and has 1 to 4 carbon atoms
Alkyl group or acetyl group, x is an integer of 1 or more, and y is
A group represented by an integer of 0 or more), R¹⁶Is the expression-Q²-O-R
²⁰(Q²Is a hydrocarbon group having 1 to 4 carbon atoms, R²⁰Has 8 carbon atoms
A hydrocarbon group of 30 to R, R¹⁷And R¹⁸Is
R¹⁴, R¹⁵Or R¹⁶Same as any one of the above, α is 0 or less
The above integers, β and γ represent integers of 1 or more.] The compound represented by the general formula (4) is a polyether compound.
Which is referred to as a silicone, for example, silicone KF-
945A (Shin-Etsu Chemical Co., Ltd.), Silicon SH-377
2C (Toray Dow Corning Silicone)
Be done.

The compound represented by the general formula (5) is referred to as an alkyl polyether-modified silicone, and examples thereof include Abil WE-09 (manufactured by Gold Schmidt).

The compound represented by the general formula (6) is a polyoxyalkylene alkyl ether co-modified organopolysiloxane, which is a compound not described in the literature. For example, methyl hydrogen It can be easily produced by co-modifying polysiloxane with polyoxyalkylene allyl ether and allyl alkyl ether.

The polyoxyalkylene-modified organopolysiloxane-based surfactant as the component (b) has good compatibility with the pasty silicone composition in the oil phase component, so that good emulsion stability can be obtained. ..

The component (b) is 0.01 to 10 in the total composition.
%, Preferably 0.5 to 5%. If it is less than 0.01%, a sufficient emulsifying ability cannot be exhibited, and if it exceeds 10%, the water-oil interface becomes too strong, and it is unfavorably heavy and sticky to the touch.

Further, the water as the component (c) is 1 to 1 in the whole composition.
90% blended.

In the water-in-oil emulsion cosmetic of the present invention, in addition to the above-mentioned essential components, usually used aqueous components and oil components, such as moisturizers, preservatives, antioxidants, ultraviolet absorbers, cosmetic ingredients, and fragrances are included. A water-soluble polymer, an extender pigment, a coloring pigment, a bright pigment, an organic powder, a hydrophobized pigment, and a tar dye can be added within a range that does not impair the effects of the present invention.

The water-in-oil type emulsified cosmetic composition of the present invention can be produced by emulsification according to a usual method except that the paste silicone composition in the component (a) is prepared in advance and used. And the like can be preferably used.

[0040]

The water-in-oil type emulsion cosmetic of the present invention has excellent stability over time, has no stickiness or oiliness, and has a refreshing feeling of use.

[0041]

The present invention will be described in more detail with reference to Reference Examples and Examples. Reference Example 1 (1) Average composition formula (7) in the reactor

[0042]

[Chemical 4]

68 g of an organohydrogenpolysiloxane represented by, 100 g of ethanol, and an average composition formula of C
H ₂ = CHCH ₂ O (C ₂ H ₄ O) ₁₀ CH ₃ 32 g of polyoxyalkylene and 3% by weight of chloroplatinic acid in ethanol solution.
After charging 3 g and maintaining the internal temperature at 70 to 80 ° C. and stirring for 2 hours, the solvent was removed under reduced pressure, and the average composition formula (8) was obtained.

[0044]

[Chemical 5]

An organohydrogenpolysiloxane of the formula: was obtained. (2) In the reactor, 100 g of the organohydrogenpolysiloxane obtained in (1) above, 100 g of ethanol and the average composition formula (9).

[0046]

[Chemical 6]

28.9 g of dimethylvinylsilyl end-blocked dimethylpolysiloxane represented by and 0.3 g of an ethanol solution containing 3% by weight of chloroplatinic acid were charged and the internal temperature was 70 to
After maintaining at 80 ° C. and stirring for 2 hours, the solvent was removed under reduced pressure to obtain an elastic polymer.

After 20 parts by weight of this polymer and 80 parts by weight of dimethylpolysiloxane (viscosity 6 cS) were dispersed and mixed,
A three-roll mill was sufficiently kneaded under shearing force to prepare a silicone composition. The composition had a smooth feel and was a uniform pasty composition with a viscosity of 32,000 cP.

Reference Example 2 Average composition formula (10)

[0050]

[Chemical 7]

Organohydrogenpolysiloxane 100 g, ethanol 62 g, average composition formula
CH ₂ = CHCH ₂ O- (C ₂ H ₄ O) ₁₀ -CH ₂ CH = CH ₂ 23.6 g of polyoxyalkylene represented by (11) and 0.3 g of an ethanol solution containing 3% by weight of chloroplatinic acid were charged, Inner temperature 70 to 8
After maintaining at 0 ° C. and stirring for 2 hours, the solvent was removed under reduced pressure to obtain a granular polymer.

33 parts by weight of the obtained polymer and 67 parts by weight of dimethylpolysiloxane (viscosity 6 cS) were dispersed and mixed, and then thoroughly kneaded under a shearing force by a three-roll mill and swollen to prepare a silicone composition. did. The composition had a smooth feel and was a uniform pasty composition with a viscosity of 24,800 cP.

Reference Example 3 The average compositional formula (7) obtained in (1) of Reference Example 1 was placed in a reactor.
Organohydrogenpolysiloxane 10 represented by
0 g, ethanol 75 g, polyoxyalkylene 49.4 g represented by the average composition formula (11) used in Reference Example 2
Then, 0.3 g of an ethanol solution containing 3% by weight of chloroplatinic acid was charged, the mixture was stirred for 2 hours while maintaining the internal temperature at 70 to 80 ° C., and then the solvent was removed under reduced pressure to obtain a granular polymer.

After 33 parts by weight of this polymer and 67 parts by weight of dimethylpolysiloxane (viscosity 6 cS) were dispersed and mixed,
The mixture was sufficiently kneaded by a three-roll mill under shearing force and swollen to prepare a silicone composition. The composition had a smooth feel and was in the form of a uniform paste with a viscosity of 10,600 cP.

Reference Example 4 In the reactor, the average composition formula (12) was used.

[0056]

[Chemical 8]

100 g of the organohydrogenpolysiloxane represented by the formula, 57 g of ethanol, 13.5 g of the polyoxyalkylene represented by the average composition formula (11) used in Reference Example 2 and 0.3 g of an ethanol solution containing 3% by weight of chloroplatinic acid. Was charged, the internal temperature was maintained at 70 to 80 ° C., and the mixture was stirred for 2 hours, then, the solvent was removed under reduced pressure to obtain a granular polymer.

20 parts by weight of this polymer and 80 parts by weight of dimethylpolysiloxane (viscosity 6 cS) were dispersed and mixed, and then sufficiently kneaded under a shearing force by a three-roll mill and swollen to prepare a silicone composition. The composition had a smooth feel and was in the form of a uniform paste with a viscosity of 22,800 cP.

Reference Example 5 100 g of the organohydrogenpolysiloxane of the average composition formula (10) used in Reference Example 2, 103 g of ethanol, and the average composition formula (1) used in Reference Example 2 were placed in a reactor.
13.6) polyoxyalkylene 23.6g, 25
Dimethyl polysiloxane 8 whose viscosity at 6 ° C is 6 cS
An ethanol solution of 2.4 g and chloroplatinic acid 3% by weight.
After charging 3 g and maintaining the internal temperature at 70 to 80 ° C. and stirring for 2 hours, the solvent was removed under reduced pressure to obtain a silicone polymer.

Then, 100 parts by weight of this silicone polymer was dispersed and mixed with 100 parts by weight of dimethylpolysiloxane having a viscosity of 6 cS at 25 ° C., and the mixture was sufficiently kneaded under a shearing force with a three-roll mill to swell to give a silicone composition. I made things. This was a homogeneous paste-like composition with a smooth feel and a viscosity of 82,800 cP.

Reference Example 6 Organohydrogenpolysiloxane 100 represented by the average composition formula (12) used in Reference Example 4 was placed in a reactor.
g, ethanol 95 g, polyoxyalkylene 13.5 g of the average compositional formula (11) used in Reference Example 2, and dimethylpolysiloxane having a viscosity of 5 cS at 25 ° C. 75.
0.3 g of ethanol solution of 7 g and chloroplatinic acid 3% by weight
Was charged and treated in the same manner as in Reference Example 5 to prepare a polymer.

Next, 100 parts by weight of this polymer and 200 parts by weight of octamethylcyclotetrasiloxane were dispersed and mixed, and then sufficiently kneaded under shearing force with a three-roll mill to prepare a swollen silicone composition. This was a uniform paste-like composition having a smooth feel and a viscosity of 44,000 cP.

Reference Example 7 In the reactor, the average compositional formula (13)

[0064]

[Chemical 9]

Organohydrogenpolysiloxane of 100 g, ethanol 74 g, average composition formula
CH ₂ = CHCH ₂ O (C ₂ H ₄ O) ₃₀ CH ₂ CH = CH ₂ 18.5 g of polyoxyalkylene represented by (14), 29.6 g of dimethylpolysiloxane having a viscosity of 6 cS at 25 ° C. and platinum chloride 0.3 g of an ethanol solution containing 3% by weight of acid was charged and treated in the same manner as in Reference Example 5 to prepare a polymer.

Then, 100 parts by weight of this polymer and 200 parts by weight of phenyltris (trimethylsiloxy) silane were dispersed and mixed, and then sufficiently kneaded and swelled by a three-roll mill under a shearing force to prepare a silicone composition. .. This was a uniform paste-like composition having a smooth feel and a viscosity of 25,500 cP.

Reference Example 8 The average compositional formula (8) obtained in (1) of Reference Example 1 was placed in a reactor.
Organohydrogenpolysiloxane 10 represented by
0 g, ethanol 72 g, average composition formula (15)

[0068]

[Chemical 10]

28.9 g, 25 of dimethylpolysiloxane end-capped with a dimethylvinylsilyl group represented by
A polymer was prepared by charging 14.3 g of dimethylpolysiloxane having a viscosity of 30 cS at 0 ° C. and 0.3 g of an ethanol solution containing 3% by weight of chloroplatinic acid and treating in the same manner as in Reference Example 5.

Then, 22.2 parts by weight of this polymer and 25 ° C.
Dimethylpolysiloxane 7 having a viscosity of 6 cS at
7.8 parts by weight were dispersed and mixed, and then sufficiently kneaded with a three-roll mill under shearing force to prepare a silicone composition.
This product has a smooth feel and a viscosity of 48,000 cP
Was a uniform paste composition.

Reference Example 9 100 g of the organohydrogenpolysiloxane of the average composition formula (10) used in Reference Example 2 and 103 g of ethanol in the reactor, and the average composition formula (1
23.6 g of polyoxyalkylene of 1), 82.4 g of 1,3-butylene glycol and 0.3 g of an ethanol solution containing 3% by weight of chloroplatinic acid were charged, and the mixture was stirred for 2 hours while maintaining the internal temperature at 70 to 80 ° C. After that, the solvent was removed under reduced pressure to obtain a silicone polymer.

Then, 100 parts by weight of this silicone polymer was dispersed and mixed with 100 parts by weight of dimethylpolysiloxane having a viscosity of 50 cS at 25 ° C., and then sufficiently kneaded by a three-roll mill under a shearing force to swell to give a silicone composition. I made things. This was a homogeneous pasty composition with a smooth feel and a viscosity of 65,000 cP.

Reference Example 10 Average compositional formula (16)

[0074]

[Chemical 11]

Organohydrogenpolysiloxane of 100 g, ethanol 160 g, average composition formula
CH ₂ = CHCH ₂ O (C ₂ H ₄ O) _30- (C ₃ H ₆ O) ₁₀ -CH ₂ CH = CH ₂ Polyoxyalkylene represented by (17) 34.7 g, ethylene glycol 20 g, at 25 ° C 13.7 g of dimethylpolysiloxane having a viscosity of 10 cS and 3% by weight of chloroplatinic acid
Then, 0.3 g of the ethanol solution was charged and treated in the same manner as in Reference Example 5 to prepare a polymer.

Next, 100 parts by weight of this polymer and 300 parts by weight of decamethylcyclopentasiloxane were dispersed and mixed, and then sufficiently kneaded and swelled by a three-roll mill under shearing force to prepare a silicone composition. This was a homogeneous paste-like composition with a smooth feel and a viscosity of 52,000 cP.

Reference Example 11 The average structural formula is

[0078]

[Chemical 12]

183 g (0.1 mol) of methyl hydrogen polysiloxane represented by: and allyl oleyl ether 3
08 g (1 mol), the average structural formula is CH ₂ = CHCH ₂ O (CH ₂ CH ₂ O) ₉
136 g (0.3 mol) of allylated polyether represented by H
And 500 g of ethanol were weighed into a 2 l flask, and a chloroneutralized product of chloroplatinic acid as a catalyst (platinum concentration
0.5%, ethanol solution) (2 g) was added, and the mixture was reacted under reflux of ethanol for 5 hours. After the reaction, the solvent was distilled off under reduced pressure, and the non-volatile matter was filtered to give an oily polyoxyethylene oleyl ether co-modified organopolysiloxane 57 having the structure shown below.
0 g (yield 91%) was obtained.

[0080]

[Chemical 13]

Reference Example 12 308 g of allyl oleyl ether used in Reference Example 11
Allyl myristyl ether 25 instead of (1 mol)
4 g (1 mol) was used and reacted and treated in the same manner as in Reference Example 11 to obtain 527 g (yield 92%) of an oily polyoxyethylene myristyl ether co-modified organopolysiloxane having the following structure.

[0082]

[Chemical 14]

Reference Example 13 308 g of allyl oleyl ether used in Reference Example 11
Instead of (1 mol), 310 g (1 mol) of allyl isostearyl ether was used and the reaction was carried out in the same manner as in Reference Example 11,
Treated to be an oily polyoxyethylene isostearyl ether co-modified organopolysiloxane 61 of the following structure
0 g (97% yield) was obtained.

[0084]

[Chemical 15]

Example 1 Cream: Creams having the formulations shown in Table 1 were prepared by the following production methods, and the stability with time and the feeling of use were evaluated according to the following methods, and the color of the appearance and the particle size of water droplets in the system. Was measured. The results are shown in Table 2.

[0086]

[Table 1]

(Production Method) A. A part of the components (7), (8) and the component (12) is gradually added to the components (4) to (6) and mixed by stirring to obtain a gel composition. B. After mixing the components (1) to (3), A is added to 70
℃. C. The components (9), (10) and the rest of the component (12) are mixed and dissolved by heating to 70 ° C. D. After adding C to B and emulsifying, the component (11) was added and cooled to obtain a water-in-oil cream. (Evaluation method) Stability over time: The emulsion composition was allowed to stand in a constant temperature bath at 50 ° C for 4 hours.
The state after a week was observed and evaluated according to the following criteria. ◯: Good with no change in state Δ: Slight separation and aggregation occurrence X: Clear separation and aggregation occurrence Sensory evaluation of usability: The items shown in Table 2 were evaluated according to the following criteria. ◎: Very good ○: Good △: Normal ×: Bad

[0088]

[Table 2]

As is clear from the results shown in Table 2, the cream of the present invention was very stable, had a good feeling in use, and had a white appearance and a finely emulsified state. On the other hand, the cream of Comparative Product 1 which did not use a surfactant had good stability over time, but the particle size of water droplets was large, and the appearance was different from that of the product of the present invention. The smoothness at the time of application was slightly inferior. The cream of Comparative Product 2, which did not use the pasty silicone composition, had an emulsified state similar to that of the product of the present invention, but was not satisfactory in terms of temporal stability and usability.

Example 2 Creamy foundation: (Formulation) (% by weight) (1) Paste-like silicone composition (obtained in Reference Example 5) 8.0 (2) Dimethylpolysiloxane (viscosity 6 cS) 7. 0 (3) Glyceryl trioctanoate 14.0 (4) Neopentyl glycol diisooctanoate 5.0 (5) Jojoba oil 2.0 (6) Polyoxyalkylene-modified organopolysiloxane compound (in Reference Example 11) Obtained) 1.0 (7) Titanium oxide 8.0 (8) Colored pigment 4.0 (9) Mica 3.0 (10) Talc 3.0 (11) 1,3-Butylene glycol 4.8 (12) Preservative 0.1 (13) Perfume 0.1 (14) Purified water Remaining amount (Manufacturing method) A. After mixing the components (1) to (6), the components (7) to (1
0) is added and uniformly dispersed. B. The components (11), (12) and (14) are heated and dissolved,
In addition to A, emulsified, and the component (13) is added thereto and cooled. The creamy foundations of the examples obtained as described above were excellent in stability over time, had a refreshing feeling of use and did not give a sticky feeling, and had good water repellency and a high cosmetic effect. ..

Claims (1)

[Claims] 1. An oil phase component containing the following components (a) to (c) (a) a pasty silicone composition (b) a polyoxyalkylene-modified organopolysiloxane-based surfactant (c) water: A water-in-oil type emulsified cosmetic characterized in that