JP3501817B2 - Cosmetics - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powder surface-coated with an acrylic-silicone-based graft copolymer and a cosmetic composition containing the same. More specifically, it has good adhesion to the skin and is smooth and refreshing. The present invention relates to a cosmetic having a good feel, excellent in usability, rich in hydrophobicity, and having a good makeup retention.

[0002]

2. Description of the Related Art Various powders are blended in cosmetics, but the surface of the powder is subjected to a hydrophobic treatment for the purpose of improving the adhesion to the skin and improving the water repellency. Is being carried out.

As a method of this hydrophobic treatment, many methods are known. For example, a method using an oil agent or a method using silicone oil, that is, a method of heat-treating an oil agent on the surface of powder, or methylhydrolysis. A method of baking genpolysiloxane is used alone or in combination depending on the purpose.

[0004]

However, the method using an oil agent has insufficient hydrophobicity, and the method using methylhydrogenpolysiloxane does not sufficiently react on the powder surface in some cases. There was a drawback that the reaction progressed further with time and the hydrophobicity changed.

Therefore, there has been a demand for a surface-treated powder which has sufficient hydrophobicity and which can be incorporated into a cosmetic composition to obtain a cosmetic composition having excellent adhesiveness, feeling of use and cosmetic durability.

[0006]

Under these circumstances, the inventors of the present invention have conducted diligent research and as a result, have found that a specific acrylic resin
The present invention was found to be obtained by using a powder whose surface is coated with a silicone-based graft copolymer, which is excellent in adhesion to the skin and feeling in use, rich in hydrophobicity, and good in makeup lasting. completed.

That is, the present invention is an acrylic-silicone graft obtained by radically copolymerizing a dimethylpolysiloxane compound (A) having a radically polymerizable group at one end of a molecular chain and an alkyl (meth) acrylate (B). Copolymer, by fluidized bed coating, or by
Dissolve in a volatile solvent and mix and disperse slurry with powder
Then, by heating this under reduced pressure to remove the solvent,
The present invention provides a cosmetic powder obtained by coating treatment and a cosmetic containing the same.

The acrylic-silicone graft copolymer used in the present invention is described in, for example, JP-A-2-25411 and is a known one.

Here, the dimethylpolysiloxane compound (A) having a radically polymerizable group at one end of the molecular chain is represented by the following general formula (1).

[0010]

[Chemical 1]

(In the formula, R ₁ represents a methyl group or a hydrogen atom, and R ₂ represents the number of carbon atoms having a linear or branched carbon chain which may be blocked by one or two ether bonds. 1 to
10 divalent saturated hydrocarbon groups are shown, and 1 is 3 to 300
The number of)

In the general formula (1), specific examples of R ₂ are:

[0013]

[Chemical 2]

And the like. Also, l is 3 to 300
The number of 5 to 100 is particularly preferable. If it is less than 3, the water resistance of the powder coated on the surface is not sufficient, and if it exceeds 300, stickiness occurs and the smoothness is insufficient.

The dimethylpolysiloxane compound represented by the general formula (1) is, for example, according to the following reaction formula, the (meth) acrylate-substituted chlorosilane compound represented by the general formula (2) and the terminal hydroxyl group represented by the general formula (3). It can be obtained by subjecting a substituted dimethylpolysiloxane to a dehydrochlorination reaction according to a conventional method, but the synthesis method is not limited thereto.

[0016]

[Chemical 3]

(Wherein R ₁ , R ₂ and l have the same meaning as described above)

However, specific examples of the dimethylpolysiloxane compound (A) having a radically polymerizable group at one end of the molecular chain are as follows.

[0019]

[Chemical 4]

On the other hand, examples of the alkyl (meth) acrylate (B) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like. .

Polymerization ratio of the dimethylpolysiloxane compound (A) having a radical polymerizable group at one end of the molecular chain and the alkyl (meth) acrylate (B) ((A) /
(B)) is preferably in the range of 1/19 to 1/1. If it becomes less than 1/19 and the proportion of (A) becomes too small, the water resistance of the powder coated on the surface becomes insufficient, and conversely, it exceeds 1/1 and the proportion of (B) becomes too small. Then, the obtained coated powder becomes sticky and its smoothness is insufficient, which is not preferable.

Copolymerization of a dimethylpolysiloxane compound (A) having a radically polymerizable group at one end of the molecular chain with an alkyl (meth) acrylate (B) is carried out by benzoyl peroxide, lauroyl peroxide, azobisisobutyrate. It is carried out in the presence of a usual radical polymerization initiator such as ronitrile, and any of a solution polymerization method, an emulsion polymerization method, a suspension polymerization method and a bulk polymerization method can be applied.
Among them, the solution polymerization method is a preferable method because it is easy to adjust the molecular weight of the obtained graft copolymer to the optimum range. As the solvent used, aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and isobutyl acetate,
1 of alcohols such as isopropanol and butanol
Examples include species or a mixture of two or more species.

The polymerization reaction can be carried out usually within a temperature range of 50 to 180 ° C., preferably 60 to 120 ° C., and can be completed under these conditions in about 5 to 10 hours. The acrylic-silicone-based graft copolymer thus produced has a weight average molecular weight in terms of polystyrene of GPC of about 3,000 to about 20.
It is preferably in the range of 30,000, particularly in the range of about 5,000 to about 100,000, and preferably has a glass transition temperature in the range of -30 to + 60 ° C.

In the present invention, the powder coated with the acrylic-silicone graft copolymer is not particularly limited as long as it is one that is usually used in cosmetics, and inorganic powder, organic powder, pearlescent agent and the like can be used. used. Specific examples include talc, mica, kaolin, titanium oxide, aluminum silicate, silicic acid anhydride, zinc oxide, calcium carbonate, magnesium carbonate, red iron oxide, yellow iron oxide, black iron oxide, ultramarine blue, titanium mica, aluminum oxide, and oxy. Examples thereof include bismuth chloride, iron oxide mica, polyethylene, polystyrene, cellulose, nylon, acrylic, Teflon, and silk powder, and these can be used alone or in combination of two or more kinds.

The coated powders of the present invention are produced by coating these powders with an acrylic-silicone graft copolymer, for example, a method by fluidized bed coating or an acrylic-silicone graft copolymer in a volatile solvent. The polymer can be coated by a method of dissolving the polymer to form a mixed dispersion slurry with the powder, heating this under reduced pressure, and distilling off the solvent.

The volatile solvent used here is not particularly limited as long as it can uniformly dissolve the acrylic-silicone graft copolymer, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, methyl ethyl ketone, Examples include ketones such as methyl isobutyl ketone, esters such as ethyl acetate and isobutyl acetate, alcohols such as isopropanol and butanol, and volatile silicone oils such as decamethylcyclopentasiloxane. These may be used alone or in combination of two or more. It can be used in combination. Further, in the coating treatment, other than the acrylic-silicone graft copolymer, a plasticizer, an activator, an oil agent, etc. can be used within a range that does not impair the effects of the present invention.

In the coated powder of the present invention, the powder surface is coated with 0.5 to 30% by weight, especially 1 to 15% by weight of the powder weight, of the acrylic-silicone graft copolymer. Is preferred.

The cosmetic material of the present invention contains the acrylic-silicone graft copolymer-coated powder thus obtained, and these coated powders account for 1 to 99% by weight in the total composition. In particular, it is preferable to add 5 to 70% by weight. Further, in the cosmetic of the present invention, in addition to the coated powder, a commonly used aqueous component, oily component or powder component, for example, moisturizer, preservative, antioxidant, ultraviolet absorber, cosmetic component, fragrance, Water-soluble polymers, extender pigments, color pigments, bright pigments, organic powders, hydrophobized pigments, tar dyes and the like can be added within a range that does not impair the effects of the present invention.

The cosmetic of the present invention can be produced by mixing the acrylic-silicone-based graft copolymer-coated powder according to a usual method, and the cosmetic in which the powder has been conventionally mixed, such as a foundation, White powder, cheek red, eye shadow, lipstick, nail treatment, mascara,
It can be applied as an emulsion, lotion and the like.

[0030]

EXAMPLES Next, the present invention will be further described with reference to examples, but the present invention is not limited to these examples.

Reference Example 1 Synthesis of Acrylic-Silicone Graft Copolymer (1): 35 g of dimethylpolysiloxane substituted with methacrylate at one end represented by the following chemical formula:

[0032]

[Chemical 5]

After mixing 45 g of methyl methacrylate, 20 g of 2-ethyl-hexyl acrylate and 100 g of toluene, and subsequently adding and dissolving 1.5 g of azoisobutyronitrile, the mixture was stirred under a temperature range of 80 to 90 ° C. At room temperature for 5 hours to obtain a viscous solution. 2 liters of this solution
Was poured into methanol to precipitate the graft polymer. The precipitate was filtered off and dried to give a white product 88 g
Got This was confirmed by infrared absorption spectrum to be a methacrylic polymer grafted with dimethylpolysiloxane, the polystyrene-converted weight average molecular weight by GPC was about 13,000, and the glass transition temperature was 37 ° C. .

Reference Example 2 Synthesis of Acrylic-Silicone Graft Copolymer (2): Under the same conditions as in Reference Example 1, one-terminal-methacrylate-substituted dimethylpolysiloxane 25 represented by the following chemical formula:
g,

[0035]

[Chemical 6]

A graft polymer was obtained from 50 g of methyl methacrylate, 15 g of n-butyl methacrylate and 10 g of vinyl acetate. This product had a polystyrene substitution weight average molecular weight by GPC of about 11,000 and a glass transition temperature of 26 ° C.

Example 1 The coated powders shown in Table 1 were prepared and the strength, adhesion and water repellency of the coating film were evaluated. The results are shown in Table 2.

[0038]

[Table 1]

(Powder surface coating treatment method) Components (1) to (4) were placed in a mixer together with isopropanol and uniformly dissolved, and then mica was added and isopropanol was distilled off under reduced pressure while heating. Coated powders B to E were obtained. (Film strength test) The powders shown in Table 1 were dispersed in octamethylcyclotetrasiloxane at a concentration of 10% each, a thin film was made on a nylon resin plate with a 6 mil doctor blade, and rubbed with fingers after drying. The strength was evaluated. As a result, ◎ is very good, ○
Was usually marked, and x was marked as bad. (Adhesiveness / Water repellency test) By 20 female panels, the above dispersion was spread on the skin, and the adhesiveness to the skin and the water repellency were rated as 3 points.
Good or normal is evaluated as 2 points, and bad is evaluated as 1 point, and the average points are 2.5 points or more as ◎, 1.5 points or more and less than 2.5 points as ○, and less than 1.5 points as ×. Indicated.

[0040]

[Table 2]

As is clear from Table 2, it was confirmed and demonstrated that the coated powder of the present invention has a very good coating strength and is excellent in adhesion and water repellency.

Examples 2 and 3 Solid white powders shown in Table 3 and pressed foundations shown in Table 4 were produced using various powders, and sensory evaluation was performed. The results are shown in Tables 6 and 7.

[0043]

[Table 3]

Manufacturing method: Components (1) to (11) were uniformly mixed with a mixer, pulverized, and press-molded in a metal plate to obtain a solid white powder.

[0045]

[Table 4]

Manufacturing method: Components (1) to (11) were uniformly mixed in a mixer, pulverized, and press-molded in a metal plate to obtain a pressed foundation.

Sensory evaluation: Twenty expert panels evaluated each sample obtained in Examples 2 and 3 for smoothness of spread, refreshing feeling, adhesiveness, water repellency and makeup retention according to the following criteria. The average score of 20 persons was used for the judgment.

[0048]

[Table 5] (Standard) Very good 5 Good 4 Usually 3 Bad 2 Very bad 1 (Average score) 4.5 or more to 5.0 ◎ 3.5 or more and less than 4.5 2.5 or more and less than 3.5 △ 1.5 or more and less than 2.5 × Less than 1.5 × ×

[0049]

[Table 6]

[0050]

[Table 7]

As is apparent from Tables 6 and 7, the products 2-2 and 3-2 of the present invention have smooth spreadability and refreshing feeling,
The items of adhesion, water repellency, and makeup lasting were all satisfactory, whereas the comparative product was unsatisfactory in any of the items.

Example 4 Eye shadow:

[Table 8] component:                                                             (weight%) (1) Talc coated with acrylic-silicone graft copolymer       (Acrylic-silicone graft copolymer of Reference Example 1       (Coated in the same manner as in Example 1 using (1)) 50.5 (2) Kaolin 15.0 (3) Mica titanium 20.0 (4) Coloring pigment 4.5 (5) Liquid paraffin 7.0 (6) Lanolin 3.0 (7) Suitable amount of fragrance (8) Preservative suitable amount

Production method: (A) Components (1) to (4) are uniformly mixed with a mixer, and then components (5) to (8) are added to make them uniform. (B) (A) was crushed and press-molded in a gold dish to obtain an eye shadow.

Example 5 Mascara:

[Table 9] component:                                                             (weight%) (1) Stearic acid 4.0 (2) Beeswax 5.0 (3) Carnauba wax 3.0 (4) Paraffin wax 3.0 (5) Water 59.5 (6) Propylene glycol 10.0 (7) Triethanolamine 3.5 (8) Black iron oxide coated with acrylic-silicone graft copolymer       (Acrylic-silicone graft copolymer of Reference Example 1       (Coated in the same manner as in Example 1 using (1)) 8.0 (9) Ultramarine coated with acrylic-silicone graft copolymer       (Acrylic-silicone graft copolymer of Reference Example 2       (Coated in the same manner as in Example 1 using (2)) 2.0 (10) Sorbitan sesquioleate 2.0 (11) Preservative suitable amount

Production method: Components (1) to (4) (A) are uniformly heated and dissolved. (B) Components (6), (8), (9) and (10) are uniformly mixed. (C) Components (5), (7), and (11) are uniformly heated and dissolved. (A) is added to (D) and (C) to emulsify. (E) After adding (B) to (D) and mixing uniformly, it was filled in a container to obtain a mascara.

[0056]

The cosmetic containing the powder surface-coated with the acrylic-silicone-based graft copolymer of the present invention has good adhesion to the skin and has a smooth and refreshing feel,
It has excellent usability, is highly hydrophobic, and has a long-lasting makeup.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satsuki Kuribayashi 48-18 Sakaemachi, Kita-ku, Tokyo Kose Research Institute Co., Ltd. (56) Reference JP-A-3-76713 (JP, A) JP-A-3- 81311 (JP, A) JP-A-2-247110 (JP, A) JP-A-2-25411 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) A61K 7/02 A61K 7 / 027 A61K 7/032

Claims (4)

(57) [Claims] 1. An acrylic-silicone graft copolymer obtained by radically copolymerizing a dimethylpolysiloxane compound (A) having a radically polymerizable group at one end of a molecular chain and an alkyl (meth) acrylate (B). ,flow
By layer coating or by dissolving the copolymer in a volatile solvent
To form a mixed dispersion slurry with the powder, and add this under reduced pressure.
Obtained by coating treatment by heating to distill off the solvent
The cosmetic powder. 2. The polymerization ratio of (A) and (B) is 1/19.
The powder for cosmetics according to claim 1, wherein the powder content is from 1/1. 3. The surface coating amount of the acrylic-silicone graft copolymer is 0.5 to 30% by weight of the powder weight.
The powder for cosmetics according to claim 1 or 2. 4. A cosmetic containing the powder for cosmetics according to claim 1.