JP2639685B2 - Composition for cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a cosmetic composition in which an oil phase is stably dispersed in an aqueous phase in the form of small spheres without using a surfactant. Can be used as a water-repellent cosmetic itself, and has a beautiful appearance, no stickiness, and a crisp feel by adding a cosmetic component to its oil phase or / and aqueous phase. I feel a cosmetic composition that can produce a cosmetic with a good feeling of use.

[Prior art] Generally, as a liquid cosmetic comprising an oil phase and an aqueous phase,
Emulsion type, solubilizing type and multilayer type are known. Emulsifying and solubilizing cosmetics are usually prepared by a method in which an oil phase is dispersed as fine droplets in an aqueous phase using a surfactant. The used phases were mixed with shaking at the time of use.

Furthermore, as a small-sphere dispersed type cosmetic in which the oil phase is dispersed in the water phase in the form of small spheres, for example, those using powder (Japanese Patent Publication No.
-11951), a mixture of an ethyl cellulose alcohol solution, a liquid hydrocarbon and water (Japanese Patent Publication No. 60-51446).
No. 2, pp. 1587-1827, which discloses that an oil phase composed of two oil components is dispersed in an aqueous phase to form three layers.

[Problems to be solved by the invention]

However, emulsion type and soluble type cosmetics have a problem of skin irritation due to the use of surfactants,
There is a disadvantage that a surfactant must be selected in order to obtain a stable product.In order to obtain a multi-layer cosmetic which has good uniform miscibility when shaken and exhibits a beautiful separation state when left standing. In addition, it is necessary to select the oil phase component and the aqueous phase component, and it is unavoidable to add a small amount of a surfactant.Moreover, since a constant mixing state cannot be obtained even by shaking, unevenness may occur. In addition, there is a disadvantage that the feel is not good, and it is difficult to obtain a small-sphere dispersion type cosmetic which is stably and uniformly dispersed for a long period of time.

Therefore, a method for easily producing cosmetics having an oil phase that is stably and uniformly dispersed in an aqueous phase for a long period of time without using a surfactant that gives skin irritation, can be selected for a feeling of use, and has a beautiful appearance. The development of was desired.

[Means for solving the problem]

Under such circumstances, the present inventors have conducted intensive studies and found that the above object can be achieved by dispersing a specific silicone composition in an aqueous phase containing a crosslinked polyacrylic thickener, The present invention has been completed.

That is, the present invention provides a cosmetic composition in which a silicone composition comprising a high-viscosity silicone or an organopolysiloxane resin and a low-viscosity silicone oil is dispersed in a small spherical shape in an aqueous phase containing a cross-linkable polyacrylic thickener. It provides things.

In the present invention, the crosslinked polyacrylic thickener forms a gel by neutralization with an alkali agent,
What is called a so-called water-soluble alkali thickening type polymer can be used, and examples thereof include a polymer or copolymer of acrylic acid or methacrylic acid, a carboxyvinyl polymer or a salt thereof. Examples of the neutralizing alkali agent include inorganic bases and organic bases such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, triethanolamine and L-arginine.

The amount of the crosslinked polyacrylic thickener added to the aqueous phase is preferably such that the viscosity of the aqueous phase is in the range of 60 to 2,000,000 cs. For this purpose, cross-linked polyacrylic thickeners vary depending on the type,
It is preferable to add so as to be 0.1 to 2.0% by weight. If the amount of the thickener is less than this, the dispersion stability of the oil phase will be insufficient, and if it exceeds this, the dispersion stability of the oil phase will be reduced and the feel will be poor. The polymer of the cross-linked polyacrylic thickener may be added as a salt, or may be added together with an alkali agent to form a salt in the system. The thickener has a function of forming a gel in the aqueous phase to increase the viscosity of the aqueous phase and stably dispersing the oil phase.

As the highly viscous silicone constituting the silicone composition of the present invention, a commercially available silicone having a viscosity of 1000 cs or more is used. As the alkanopolysiloxane resin, those commercially available under the name of silicone compound and partially crosslinked organopolysiloxane resins are generally used.

The partially crosslinked organopolysiloxane resin is, for example, an organopolysiloxane polymer having a three-dimensional crosslinked structure which is insoluble in benzene and may contain benzene in the same weight or more as its own weight, and is obtained by crosslinking organopolysiloxane. Object, partially having a three-dimensional crosslinked structure,
R ₂ SiO units and RSiO _1.5 units, and R ₃
It may contain _0.5 units of SiO and / or ₂ units of SiO ₂ .

R in each of the above structural units is exemplified by a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, and a propyl group, an aryl group such as a phenyl group and a tolyl group, and an aliphatic unsaturated group such as a vinyl group. Alternatively, different types may be used.

Organopolysiloxane, it is insoluble in benzene, to take organopolysiloxane polymer structure having a three-dimensional crosslinked structure, which may include its own weight and the weight or more of benzene, and RSiO _1.5 units and / or SiO ₂ units, It is necessary that the ratio of the R ₂ SiO unit and / or the R ₃ SiO _0.5 unit is in an appropriate range, and if the RSiO _1.5 unit and / or the SiO ₂ unit is too small, the organopolysiloxane has a sufficient three-dimensional crosslinked structure. However, it becomes soluble in benzene and cannot be used even if it has an apparently crosslinked structure. In addition, R ₂ SiO unit and / or R
_If there are too many RSiO _1.5 units and / or SiO ₂ units as compared to _0.5 SiO _0.5 units, the organopolysiloxane has a strong crosslinked structure and is insoluble in benzene, but contains less than the benzene of its own weight of the polymer. However, when it is mixed with a low-viscosity silicone oil, it separates and discharges, making it unusable.

The ratio of R ₂ SiO units and RSiO _1.5 units in the organopolysiloxane polymer that is insoluble in benzene and can contain benzene equal to or more than its own weight is greatly affected by the molecular weight of the entire organopolysiloxane polymer. Although difficult to define, a ratio of 1: 1 to 30: 1 gave the desired results.

If RSiO _1.5 units is greater than this ratio, a hard organopolysiloxane polymer will be obtained, which may contain less than the same weight of benzene as its own weight, which will be mixed with the low viscosity silicone oil described below. Since the silicone oil does not swell sufficiently, separation and discharge of the silicone oil occur, and it becomes impossible to maintain stability. Conversely, if the R ₂ SiO unit exceeds the above range, the structural viscosity becomes poor. For this reason, it is not limited to obtain a soft and stable silicone composition, but it is preferably in the above-mentioned ratio of the structural units.

The above-mentioned organopolysiloxane having a three-dimensional crosslinked structure which is insoluble in benzene but can contain benzene in the same weight or more as its own weight can be synthesized by, for example, the following various methods.

A dehydrogenation reaction and a condensation reaction are performed by adding a catalytic amount of an alcoholic aqueous solution of an alkali metal hydroxide to an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule and heating the mixture.

A catalytic amount of an alkali metal hydroxide having an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule and an organopolysiloxane having at least two silicon-bonded hydroxyl groups in the other molecule; Heating in the presence of substances or platinum compounds,
A dehydrocondensation reaction is performed.

An organopolysiloxane having a hydroxyl group directly bonded to at least two silicon atoms in one molecule is heated in the presence of a catalytic amount of an alkali metal hydroxide or an organotin compound to perform a dehydration condensation reaction.

A catalytic amount of an alkali metal hydroxide comprising an organopolysiloxane having at least two hydroxyl groups directly bonded to silicon atoms in one molecule and an organopolysiloxane having at least two alkoxy groups bonded to silicon atoms in the other molecule. And a dealcoholation reaction is performed by heating in the presence of an organic metal tin compound.

In any of these methods, an organopolysiloxane polymer having a three-dimensional crosslinked structure which is insoluble in benzene but can contain benzene in the same weight or more as its own weight can be easily obtained.

Other partially crosslinked organopolysiloxane resins are organopolysiloxane polymers which are insoluble in silicone oil, but swell sufficiently, and (a) an organohydrogenpolysiloxane and (b) an aliphatic unsaturated group. It is a polymer obtained by subjecting a contained organopolysiloxane to addition polymerization, and includes a polymer partially having a three-dimensional crosslinked structure.

Organohydrogenpolysiloxane here to use (i) is, HSiO _1.5 units, RSiO _1.5 units, RHSiO units, R ₂ SiO units, R ₂ HSiO _0.5 units, consists R ₃ SiO _0.5 units and the like, the molecular structure of this product May be linear, branched or cyclic, and contains at least two hydrogen atoms bonded to a silicon atom in one molecule. Also,
The organohydrogenpolysiloxane is more preferably linear in order to control the organopolysiloxane polymer synthesis reaction. In addition, a hydrogen atom (≡SiH bond) bonded to a silicon atom in this organohydrogenpolysiloxane is generally included in a molecular chain, but may be a molecular terminal.
The amount of the ≡SiH bond is usually 1 to 20 mol% when the molecular structure is linear or branched, and 1 to 20 mol% when the molecular structure is cyclic.
The organic group other than the 有機 SiH bond is desirably 50 mol%, and preferably 50 mol% or more of the organic group is a methyl group.

The organopolysiloxane containing an aliphatic unsaturated group (ii) used at the same time contains at least two aliphatic unsaturated groups bonded to a silicon atom in one molecule. Examples of the organopolysiloxane include a vinyl group and an aryl group, and a vinyl group-containing organovinylpolysiloxane is generally exemplified. Examples of the organovinylpolysiloxane include (CH ₂ 2CH) SiO _1.5 units, RSiO _1.5 unit, R (CH = CH ₂ ) SiO unit, R ₂ SiO unit,
_{R 2 (CH = CH 2)} SiO 0.5 units, consists R ₃ SiO _0.5 units and the like,
Its molecular structure may be linear, branched or cyclic, and the molecule contains at least two aliphatic unsaturated groups bonded to a cerium atom, for example, a vinyl group. . The aliphatic unsaturated group-containing organopolysiloxane used here is more preferably linear in order to control the organopolysiloxane polymer synthesis reaction. The organovinylpolysiloxane is usually a linear one in which both ends of the molecular chain are blocked with a dimethylvinylsilyl group, and the vinyl group may be contained in the chain. Is preferably 1 to 20 mol% when the molecular structure is linear or branched, and 1 to 50 mol% when the molecular structure is cyclic. The organic group other than the vinyl group is preferably at least 50 mol%. Is preferably a methyl group.

And, in each of the organohydrogenpolysiloxane of (a) and the organopolysiloxane containing an aliphatic unsaturated group of (b), for example, a hydrogen atom bonded to a silicon atom which is a reactive group in each molecule of the organovinylpolysiloxane or It is essential that at least two vinyl groups be contained in one molecule in order for both addition polymers to partially form a three-dimensional structure. When the content of each of these reactive groups in the organopolysiloxane is greater than 20 mol% when the molecular structure is linear or branched, and more than 50 mol% when the molecular structure is cyclic, a hard polymer is obtained. And the low-viscosity silicone oil described later tends to be difficult to be included in the three-dimensional crosslinked structure, and it is recognized that separation and discharge occur and the stable holding cannot be performed. Conversely, if the content is less than 1 mol%, the structural viscosity tends to be poor. For this reason, it is not limited to obtain a soft and stable silicone composition, but the content of the reactive group is 1 to 20 mol% when the molecular structure is linear or branched, and In the case of a ring, it is 1 to 50%.

The organic group R of the organohydrogenpolysiloxane (a) may be an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, an aryl group such as a phenyl group or a tolyl group, a cyclohexyl group, or a cyclohexyl group. Unsubstituted or substituted monovalent hydrocarbon groups excluding aliphatic unsaturated groups such as vinyl groups selected from groups in which part or all of the hydrogen atoms bonded to the carbon atoms of the group are substituted with halogen atoms, cyano groups, etc. Is exemplified.

As those these examples representative _{of, (CH 3) 3 SiO -} , (CH 3) 2 SiOp, (CH 3 HSiO
_{q, -Si (CH 3) 3} ( where, p = 10~500, q = 2~50 )
And a suitable material.

Further, the organic group R of the organovinylpolysiloxane which is the organopolysiloxane containing an aliphatic unsaturated group (ii) is the same as R of the organohydrogenpolysiloxane. Typical examples of such _{examples, (CH 2 = CH) (} CH 3) 2 SiO -, (CH 3) 2 SiOr, -Si
(CH ₃ ) ₂ (CH = CH ₂ ), where r = 10 to 100, or (CH ₃ ) ₃ SiO—, (CH ₃ ) ₂ SiOm,
(CH = CH ₂ ) CH ₃ SiOn, —Si (CH ₃ ) ₃ (where m =
Methyl polysiloxanes containing units of 10 to 500, n = 2 to 50), which may be a mixture and are suitable materials.

Such an addition reaction between the organohydrogenpolysiloxane (a) and the organopolysiloxane containing an aliphatic unsaturated group (b) may be performed by a conventionally known general method. For example, after blending the appropriate organohydrogenpolysiloxane and organovinylpolysiloxane with a hydrogen group bonded to a silicon atom as a reactive group, and a molar ratio of the vinyl group in the range of 1/3 to 3/1, By adding an addition polymerization catalyst such as platinum or palladium and stirring with heating, an intended organopolysiloxane polymer insoluble in silicone oil can be easily obtained. In particular, as the addition polymerization catalyst, it is preferable to use chloroplatinic acid described in JP-B-33-9969.

The low-viscosity silicone oil is not particularly limited, but may be suitably used as long as it has a viscosity of 50 cs or less. This is because, as the viscosity becomes higher, the use of a large amount thereof results in heat-sensitive oiliness, which is unfavorable in the sense of use. Examples of the low-viscosity silicone oil include low-polymerization degree chain dimethylpolysiloxane, methylphenylpolysiloxane, cyclic octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like. Two or more types are appropriately selected and used.

The silicone composition is prepared by sufficiently kneading (A) a high-viscosity silicone or organopolysiloxane resin and (B) a low-viscosity silicone oil. When used in combination, a gel is formed, which is more preferable in terms of feel and stability. In this case, both have a viscosity of 200,000 to 300,000 cs
It is preferable to mix them so that A / B is usually 5/95 to 40/60.

The cosmetic composition of the present invention prepares an aqueous phase and an oil phase silicone composition, respectively, and mechanically mixes them.
It is produced by dispersing the silicone composition into small spheres in the aqueous phase. In this case, the mixing ratio of the aqueous phase and the silicone composition is preferably 99.5: 0.5 to 70:30 (weight ratio).
The size of the oil phase sphere of the silicone composition can be freely adjusted by mechanical force, but is generally preferably about 0.05 to 4 mm.

The aqueous phase and the oil phase of the cosmetic composition of the present invention can contain an aqueous component and an oil component depending on the purpose of the product. These components include, for example, cosmetic powders, pigments, dyes, polyhydric alcohols, antioxidants, ultraviolet absorbers, preservatives, beautiful skin components, medicinal components, fragrances, and the like.

The cosmetic composition of the present invention can be used as a cosmetic itself, and is useful as a base material for liquid cosmetics such as for the face and hair. Cosmetics such as face lotion, hair lotion, body lotion, hand lotion, and hair styling can be obtained.

〔Example〕

 Next, an example will be described.

Example 1 The above components were mixed and dissolved in a conventional manner to obtain an aqueous phase.

(Note 1) Shin-Etsu Chemical Co., Ltd. (Note 2) Trimethylsilyl end-blocked dimethylmethylhydrogenpolysiloxane <molecular weight 2300, CH ₃ HSiO to (CH ₃ ) ₂ SiO = 1: 4 (molar ratio)> 1% potassium hydroxide Add an appropriate amount of solution (ethanol to water = 2 to 1), heat,
The polymerization reaction was carried out under reflux to obtain a reaction product.

Next, the reaction product is washed with water to remove the alkaline agent, and then naturally dried to obtain a partially crosslinked organopolysiloxane resin.

 The above components were kneaded with a three-roll mill to obtain an oil phase.

(Iii) Cosmetic composition While stirring the aqueous phase of (i) (water dilution of A to D) 97.5% (by weight) with a pestle mixer, the oil phase of (ii) (a to
b) 2.3% of fragrance and 0.2% of fragrance were added, and the particle size of oil phase globules was 1
A 用 2 mm cosmetic composition was prepared.

(Iv) The composition for cosmetics obtained in (iii) was evaluated for its oil phase spheroid dispersion formation property and its dispersion stability after standing for 7 days. The results are shown in Table 1 together with the results of measuring the viscosity of the aqueous phase and the oil phase at that time (B-type rotational viscometer).

After preparing the aqueous phase and the oil phase by previously mixing them uniformly, the oil phase was added to the aqueous phase with stirring to produce the aqueous phase. In the case of Example 2, the obtained cosmetic exhibited a state in which small spherical oil droplets having a particle diameter of about 1 mm were dispersed, and in the case of Comparative Example 1, the cosmetic was in a slightly cloudy state.

In comparison of the sensory evaluations of Example 2 and Comparative Example 1, stickiness was felt in Comparative Example 1, whereas stickiness was not felt in Example 2, and the feeling was very crisp. Had.

Further, in Example 1, a large number of white spherical oil droplets were dispersed in the transparent external phase gel, and the appearance was interesting and new. Further, the eye stability was good.

Example 3 Lotion (Formulation) (%) (1) Carboxyvinyl polymer 0.15 (2) Glycerin 6.75 (3) Sodium hydroxide 0.03 (4) Preservative appropriate amount (5) Refined water residue (6) Part Crosslinked organopolysiloxane resin (same as in Example 1) 0.25 (7) Dimethylpolysiloxane (6cs) 2.25 Water phase [components (1) to (5)] and oil phase [component (6) to
(7)] was uniformly mixed in advance, and the oil phase was added to the aqueous phase with stirring to obtain a small spherical oil dispersion type lotion having a particle size of about 1.5 to 2 mm.

Example 4 Hairdressing (Prescription) (%) (1) Carboxyvinyl polymer 0.4 (2) Polyvinylpyrrolidone 2.0 (3) Methylcellulose 0.001 (4) 1,3-butylene glycol 10.0 (5) Sodium hydroxide 0.08 (6) Ethanol 10.0 (7) Refined water residue (8) Dimethylpolysiloxane (5000cs) 3.0 (9) Dimethylpolysiloxane (10cs) 2.0 Water phase [components (1) to (7)] and oil phase [component (8) to
(9)] was uniformly mixed and prepared in advance, and the oil phase was added to the aqueous phase with stirring to obtain a small spherical oil-dispersed hair styling having a particle size of about 0.5 to 1 mm.

Example 5 Hand lotion (prescription) (%) (1) Sodium polyacrylate 0.24 (2) Carboxyvinyl polymer 0.8 (3) Preservatives appropriate amount (4) Glycerin 50.0 (5) Refined water balance (6) ) Partially crosslinked organopolysiloxane resin (same as in Example 1) 3.0 (7) Dimethylpolysiloxane (6cs) 17.0 Water phase [components (1) to (5)] and oil phase [component (6) to
(7)] was uniformly prepared in advance, and the oil phase was added to the aqueous phase with stirring to obtain a small oil dispersion type hand lotion having a particle size of about 0.2 mm.

〔The invention's effect〕

 The cosmetic composition of the present invention has the following advantages.

Since no surfactant is used, there is no problem such as skin irritation.

The production is simple, and the particle size of the oil phase can be easily controlled.

Extremely good dispersion stability.

It has no stickiness, has a crisp feel, and has a good feeling of use.

It has a beautiful appearance over a long period of time.

It can be used as a wide range of cosmetic base materials, and can contain various cosmetic components according to the purpose of makeup.

Claims (1)

(57) [Claims] 1. A cosmetic composition in which a silicone composition comprising a high-viscosity silicone or organopolysiloxane resin and a low-viscosity silicone oil is dispersed in a spherical form in an aqueous phase containing a crosslinkable polyacrylic thickener. .