JP2767633B2 - Gel composition and cosmetic containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a semi-solid to solid gel composition comprising a specific acrylic-silicone-based graft copolymer and a low-viscosity silicone oil. And a cosmetic having excellent feel and stability.

[Conventional technology]

Conventionally, cosmetics that are expected to have lubricity, water repellency, etc. have been prepared as solid, gel, or emulsion using solid oils, semi-solid oils, liquid oils, gelling agents and the like as base materials. .

Among such base materials, silicone oil is applied to various products due to its excellent properties, and is widely used as a useful oil component especially in cosmetics. This is because silicone oil has suitable characteristics such as low stickiness, good smoothness, good elongation, refreshing feel, rich lubricity, water repellency, tasteless, odorless and high skin safety. is there. By blending silicone oil, studies are needed to obtain basic cosmetics and hair cosmetics that have a good feeling of use and that can treat and protect the skin and hair, or make-up cosmetics with long lasting makeup. It has been done.

Such silicone oils for cosmetics include linear dimethylpolysiloxanes having different molecular weights and viscosities, as well as cyclic octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane and the like. Is a general one, but various other polymerization and
Copolymers and modified products are commercially available.

These various silicone oils are used alone or in combination depending on the purpose of cosmetics and the effects to be expected.
For example, low-viscosity dimethylpolysiloxane is required for products that require a less sticky and refreshing feel, while high-viscosity dimethylpolysiloxane is required for products that require water repellency that effectively repels water. Oil has the property of volatilizing after application, and is therefore often used for products and the like that require a refreshing feeling. In addition, dimethyl hydrogen polysiloxane is used to improve the make-up of makeup cosmetics by treating the surface of cosmetic powder to make it water-repellent.

As described above, techniques that effectively utilize the properties of silicone oils are known, and research on the development of new uses for cosmetics is also being conducted.

[Problems to be solved by the invention]

As described above, silicone oil is useful as a cosmetic oil agent, but has the following drawbacks in obtaining an excellent product with even higher functionality.

Silicone oils generally have poor compatibility with other cosmetic oils, making it difficult to uniformly dissolve the silicone oils and stably blend them into a base material. That is, when the silicone oil is blended, it is difficult to maintain it safely even when it is made into an emulsion emulsion and is mixed with a wax or other cosmetic oil, especially in a large amount so that the properties of the silicone oil can be effectively exhibited. Phenomena such as separation and drainage over time. This was particularly noticeable when a low-viscosity or volatile silicone oil was used in a large amount in order to impart a refreshing feel and to enhance the makeup of makeup makeup. When a high-viscosity silicone oil is used, the water repellency is improved, but a sticky feeling and a heavy oily feeling are simultaneously felt. As described above, there has been a problem that it is difficult to increase the content of the silicone oil, obtain a sufficient effect, and obtain a stable product.

In addition, since silicone oil does not have a yield value as a flow property, when it is used as a main skeleton of a cosmetic, it is difficult to keep a substance having a specific gravity difference such as a pigment in a state of being stably dispersed with time. Met. From this point, even if a high-viscosity material having a large molecular weight is used, although it has an apparent viscosity, it still shows flow characteristics without a yield value, so that a material having a large specific gravity difference cannot be retained, and sedimentation etc. Is observed, and as described above, a sticky feeling, a heavy oily feeling and the like are generated, which is not preferable in touch.

In addition, when used in combination with waxes, the compatibility is poor, the wax tends to precipitate, and the properties of the wax itself appear, impairing the smooth and refreshing feel that is the characteristic of silicone oil as a cosmetic base. As a result, it has been difficult to obtain a product with good stability that makes full use of the properties of silicone oil.

For this reason, the development of a soft gel material having a yield value or a hard gel material having a structural strength that can be used as a solid skeleton such as wax and has a smooth and refreshing feel like silicone oil is desired. I was

[Means for solving the problem]

Under such circumstances, the present inventors have conducted intensive studies. As a result, if a specific acrylic-silicone-based graft copolymer is mixed with a silicone oil having a viscosity of 50 cs or less (25 ° C.), a smooth and refreshing feel is obtained. A semi-solid to solid gel composition having excellent shape retention and stability can be obtained, and further, by using this gel composition, a cosmetic composition having good stability and excellent feel Were obtained, and the present invention was completed.

That is, the present invention provides (a) and (b) (a) an ester or acid amide of a higher alcohol or amine having 12 or more carbon atoms and (meth) acrylic acid, and a radical polymerizable group at one end of a molecular chain. Acrylic-silicone graft copolymer obtained by copolymerizing a radical polymerizable monomer mainly composed of a dimethylpolysiloxane compound (b) A gel composition comprising a silicone oil having a viscosity of 50 cs or less (25 ° C), and The present invention provides cosmetics containing the same.

The acrylic-silicone graft copolymer (A) used in the present invention comprises (A) an ester or acid amide of a higher alcohol or amine having 12 or more carbon atoms and (meth) acrylic acid, and (B) a molecular chain. It is synthesized by radical copolymerization of a radically polymerizable monomer mainly composed of a dimethylpolysiloxane compound having a radically polymerizable group at one terminal.

(A) an ester or acid amide of a higher alcohol or amine having 12 or more carbon atoms and (meth) acrylic acid,
For example, a higher alcohol or amine having 12 or more carbon atoms,
(Meth) acrylic acid, glycidyl (meth) acrylate,
It can be easily produced by reacting a (meth) acrylic halide or the like to form an ester or an acid amide. Among these, specific examples of those particularly preferably used include the following.

_{CH 2 = CHCOO (CH 2)} 17 CH 3 CH 2 = C (CH 3) COO (CH 2) 21 CH 3 CH 2 = CHCOOCH 2 CH (OH) CH 2 O (CH 2) 17 CH 3 CH 2 = C (CH ₃ ) COOCH ₂ CH (OH) CH ₂ O (CH ₂ ) ₂₉ CH _{3 CH 2 = C (CH 3)} CONH (CH 2) 17 CH 3 CH 2 = C (CH 3) COO (CH 2) 11 CH 3 CH 2 = CHCONH (CH 2) 21 CH 3 CH 2 = C (CH 3 ) COO (CH ₂ ) ₁₅ CH ₃ The dimethylpolysiloxane compound having a radical polymerizable group at one end of the molecular chain of (B) is represented by, for example, the following general formula (I).

(Wherein, R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents a linear or branched C 1-10 saturated hydrocarbon group which may be interrupted by one or two ether bonds. And n represents a number from 0 to 200, and m represents 0, 1 or 2. This dimethylpolysiloxane compound is, for example, represented by the following general formula (II) (Wherein R ₁ , R ₂ and m have the same meanings as described above), and a methacrylacrylate-substituted chlorosilane compound represented by the general formula (III): (Wherein, n has the same meaning as described above), and can be obtained by subjecting a terminal hydroxyl-substituted dimethylpolysiloxane represented by the following formula to a dehydrochlorination reaction according to a conventional method. Of these dimethylpolysiloxane compounds, specific examples that are particularly preferably used include the following.

(A) Acrylic used in the gel composition of the present invention-
The silicone-based graft copolymer is obtained by copolymerizing one or more of the ester or acid amide (A) and a radically polymerizable monomer mainly composed of a mixture of the dimethylpolysiloxane compound (B). Can be Here, the fact that (A) and (B) are the main constituents depends on the length of the molecular chain, the state of branching, and the like, but is not limited thereto. ~ 95 mol%, meaning that the dimethylpolysiloxane compound of (B) accounts for 2-40 mol%.
If the ester or acid amide of (A) is less than 30 mol%, a semi-solid to solid gel will not be formed even when mixed with a silicone oil having a viscosity of 50 cs or less (25 ° C.) as described below. Poor compatibility with silicone oil having a viscosity of 50cs or less (25 ° C). On the other hand, if the dimethylpolysiloxane compound (B) is less than 2 mol%, the compatibility with the low-viscosity silicone oil will be poor, and if it exceeds 40 mol%, the expected gelling ability will not be exhibited, which is not preferred.

Further, in the acrylic-silicone graft copolymer (a), in addition to the above two components, various radically polymerizable monomers such as styrene, substituted styrene,
Vinyl acetate, (meth) acrylic acid, other (meth)
Acrylic esters, maleic anhydride, maleic esters, fumaric esters, vinyl chloride, vinylidene chloride, ethylene, propylene, butadiene, acrylonitrile, fluorinated olefins and the like can be copolymerized.

The copolymerization of the radical polymerizable monomer may be carried out in the presence of a usual radical polymerization initiator such as benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, and a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method. Any of a polymerization method and a bulk polymerization method may be used. Among these, the solution polymerization method is particularly preferable because it is easy to adjust the molecular weight of the obtained graft copolymer to an optimum range. As the solvent used, for example, benzene, toluene,
Aromatic hydrocarbons such as xylene; methyl ethyl ketone;
Ketones such as methyl isobutyl ketone; ethyl acetate;
Esters such as isobutyl acetate; isopropanol,
Alcohols such as butanol and the like can be mentioned, and these can be used alone or in combination of two or more. The polymerization reaction is preferably carried out at a temperature equal to or higher than the melting point of the ester or acid amide (A), generally in the range of 50 to 180 ° C, particularly preferably in the range of 60 to 130 ° C. Can be done.

On the other hand, the silicone oil (b) used in the present invention can be suitably used as long as it has a viscosity of 50 cs or less (25 ° C.). Examples of the silicone oil having a viscosity of 50 cs or less (25 ° C.) include low-polymerization degree chain dimethylpolysiloxane, methylphenylpolysiloxane, cyclic octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. One or more of these can be used in combination. If the viscosity is higher than about 50 cs, the compatibility with the acrylic-silicone-based graft copolymer (a) is reduced, or an oily feeling is generated,
It is not preferable in terms of usability.

The gel composition of the present invention is obtained by, for example, mixing an acrylic-silicone-based graft copolymer (a) and a silicone oil having a viscosity of 50 cs or less (25 ° C) with (b) and dissolving by heating.
It can be easily manufactured by cooling.
The mixing ratio of (a) and (b) varies depending on these types, but is generally 10:90 to 80:20, preferably 20:80 by weight.
~ 60: 40. If the amount of the acrylic-silicone-based graft copolymer (a) is less than this range, a good semi-solid to solid gel composition cannot be obtained. If the amount is too large, a gel composition having a smooth feel can be obtained. It is not preferable because it becomes difficult to obtain.

The gel composition of the present invention is obtained as a semi-solid to solid form, but has a relatively low melting point as an ester or acid amide of (A) a higher alcohol or amine having 12 or more carbon atoms and (meth) acrylic acid. When a compound is selected, when a compound having a highly branched alkyl chain is selected, or when the concentration at the time of copolymerization is lowered, a silicone oil having a viscosity of 50cs or less (25 ° C) in the gel composition is blended. When the amount is increased, it becomes semi-solid, and when the amount is reversed, it is obtained as solid.

The cosmetic of the present invention contains the gel composition of the present invention in an amount of 1 to 100% by weight, and the gel composition may be used as it is, or may be determined according to the purpose of use. In addition to the gel composition, components used in ordinary cosmetics, such as oils and fats, waxes, hydrocarbons, fatty acids, alcohols, esters, lanolins, and other oils such as silicone oils other than those described above Raw materials; powder raw materials such as white pigments, colored pigments, extenders; metal soaps, surfactants, polyhydric alcohols,
Polymer compounds, water, other antioxidants, ultraviolet absorbers,
Preservatives, tar pigments, cosmetic ingredients, fragrances, and the like can be appropriately compounded according to the product type and cosmetic purpose. The cosmetic of the present invention can be produced by a usual method, for example, creams, emulsions, etc., face cosmetics for limbs, hair styling, hair treatments such as hair treatments, foundations,
It can be applied as a makeup cosmetic such as white powder, blusher, eyeshadow, lipstick, eyeliner and mascara.

〔Example〕

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples.

Example 1 Gel Composition (i) One-terminal methacrylate-substituted dimethylpolysiloxane 15.9 g represented by the following chemical formula 25.3 g of stearyl methacrylate, 50 g of toluene,
After adding and dissolving 0.7 g of azobisisobutyronitrile, a copolymerization reaction was carried out for 5 hours in a temperature range of 105 to 110 ° C. with stirring to obtain a viscous solution. Methanol (1) was poured into this solution to precipitate the graft copolymer, and the precipitate was separated by filtration and dried to obtain 37 g of the graft copolymer.
This was confirmed by an infrared absorption spectrum to be a methacrylate polymer to which dimethylpolysiloxane was grafted.

(Ii) 30 g of the graft copolymer obtained as described above
And 20 g of decamethylcyclopentasiloxane were mixed, heated and dissolved, and then cooled to obtain a uniform solid gel composition.

The gel composition obtained as described above stably blended decamethylcyclopentasiloxane.

Example 2 Gel Composition (i) 35 g of methacrylate-substituted dimethylpolysiloxane having one end represented by the following chemical formula: 24.7 g of methacrylic acid behenyl ester prepared according to a conventional method from methacrylic acid chloride and behenyl alcohol,
Under the same conditions as in Example 1, from 0.9 g of methacrylic acid methyl ester, 1.7 g of 2-ethylhexyl acrylate and 80 g of toluene, a white wax-like graft copolymer 51 was obtained.
g was obtained.

(Ii) 35 g of the graft copolymer obtained as described above
And 40 g of dimethylpolysiloxane (6 cs, 25 ° C.) and 25 g of decamethylcyclopentasiloxane were mixed, heated and dissolved, and then cooled to obtain a uniform solid gel composition.

The gel composition obtained as described above stably contained dimethylpolysiloxane and decamethylcyclopentasiloxane.

Example 3 Gel Composition 40 g of methacrylate-substituted dimethylpolysiloxane having one terminal represented by the following chemical formula: β-sitosterol (manufactured by Sigma) and 38.6 g of an ester of (meth) acrylic acid with a higher alcohol having 12 or more carbon atoms represented by the following chemical formula obtained by a dehydrochlorination reaction from methacryloyl chloride, After uniformly dissolving 120 g of toluene and 1 g of azobisisobutyronitrile, a copolymerization reaction was conducted for 6 hours in a temperature range of 105 to 110 ° C. with stirring, and thereafter, a colorless solid was obtained by operating in the same manner as in Example 1. Thus, 65 g of a graft copolymer was obtained.

35 g of the graft copolymer obtained as described above and 65 g of dimethylpolysiloxane (6cs) were mixed, dissolved by heating, and cooled to obtain a uniform solid gel composition.

Example 4 Gel composition 36 g of methacrylate-substituted dimethylpolysiloxane having one end represented by the following chemical formula: Esters of (meth) acrylic acid with higher alcohol having 12 or more carbon atoms represented by the following chemical formula and prepared from cricidyl methacrylate and behenyl alcohol according to a conventional method: 37.5
g, From 150 g of toluene and 1 g of azobisisobutyronitrile, 62 g of a white waxy graft copolymer was obtained in the same manner as in Example 1.

40 g of the graft copolymer obtained as described above and 60 g of dimethylpolysiloxane (10cs) were mixed and dissolved by heating, followed by cooling to obtain a uniform solid gel composition.

Example 5 Solid Foundation (Components) (parts by weight) (1) Titanium oxide 12.0 (2) Bengala 0.8 (3) Yellow iron oxide 1.8 (4) Black iron oxide 0.6 (5) Liquid paraffin 5.0 (6) Gel composition 79.8 (obtained in Example 1) (Production method) After mixing and homogenizing the components (1) to (5), the component (6) was added, and the mixture was uniformly dispersed with a three-roll mill and melted in a container. The mixture was filled and solidified by cooling to obtain a solid foundation.

Comparative Example 1 Instead of the gel composition which is a component of (6) of Example 5, 13 parts by weight of a starch fatty acid ester and liquid paraffin were used.
A solid foundation was obtained in the same manner as in Example 5, except that 66.8 parts by weight of the product was dissolved by heating.

Comparative Example 2 Solid Foundation (Component) (parts by weight) (1) Titanium oxide 12.0 (2) Bengala 0.8 (3) Yellow iron oxide 1.8 (4) Black iron oxide 0.6 (5) Liquid paraffin 5.0 (6) Gel composition 79.8 (those obtained in the following production example) one end methacrylates represented by the production example following chemical formula substituted dimethylpolysiloxane _{30g CH 2 = C (CH 3} ) COOC 3 H 6 Si (CH 3) 2 O- Si (CH 3 ) ₂ O ₅₀ Si (CH ₃ ) ₃ methyl methacrylate 30 g, n-butyl methacrylate 4
0 g, 100 g of toluene and then 1.5 g of azobisisobutyronitrile were added and dissolved, and then stirred at 80 to 90 ° C.
The reaction was carried out for 5 hours within the temperature range described above to obtain a viscous solution. This solution was poured into methanol (2) to precipitate a graft copolymer. The precipitate was filtered off and dried, yielding 93 g of a white product. Then, 35 g of this graft copolymer
And 65 g of dimethylpolysiloxane (5 cs, 25 ° C.) were dissolved in 150 g of isopropanol, and then isopropanol was distilled off to obtain a uniform solid gel composition.

(Production method) A solid foundation was obtained in the same manner as in Example 3.

Test Example The solid foundations produced in Example 5 and Comparative Examples 1 and 2 were subjected to a use test by 20 female panels and evaluated according to the following criteria. The results are shown in Table 1.

(Evaluation method) Evaluation point Very good 3 points Good or ordinary 2 points Bad 1 point Judgment Average point 2.5 or more ◎ Average point 2.0 or more and less than 2.5 ○ Average point 1.5 or more and less than 2.0 △ Average point less than 1.5 × As is clear from the results in Table 1, the solid foundation of Example 5 in which the gel composition of the present invention was blended was less stretchable, less sticky and water-resistant than the conventional oily solid foundation of Comparative Example 1. Especially excellent. In addition, a foundation prepared by blending a gel composition using a graft copolymer which does not select an ester or acid amide of a higher alcohol or amine having 12 or more carbon atoms and (meth) acrylic acid as a radical polymerizable monomer of Comparative Example 2 It was superior in ease of removal, expansion, and smoothness.

Example 6 Suncut stick (component) (% by weight) (1) Acrylic-silicone graft 55.0 copolymer (obtained in Example 2) (2) Decamethylcyclopentasiloxane 38.0 (3) Isopropyl myristate 1.0 (4) Escalol 507 (manufactured by VAN DYK) 4.0 (5) Fine particle titanium oxide 1.5 (6) Talc 0.5 (7) Fragrance trace (8) Antioxidant trace (manufacturing method) Ingredients (1) to (8) Was mixed and dissolved by heating, kneaded sufficiently with a three-roll mill, and then molded into a stick to obtain a suncut stick.

The suncut stick obtained as above is
It had a light feeling of use, had no stickiness, no squeaky feeling, no sense of film thickness, was excellent in water repellency, and had the strength required for a stick cosmetic.

〔The invention's effect〕

As described in detail above, the gel composition of the present invention has good stability, has no oiliness or stickiness, has a smooth and refreshing feel, and is excellent in usability and usability. Further, it is a semi-solid to solid substance having a structure-retaining property, and has extremely useful properties such as excellent lubricity and water repellency and high skin safety.

Therefore, when the gel composition of the present invention is used as a base material for cosmetics, it can be applied to various cosmetics like conventional silicone oils, and has excellent properties, particularly in terms of ease of removal, expansion and smoothness, and smoothness. Is obtained.

As described above, according to the present invention, a gel composition having extremely high usefulness, particularly as a cosmetic material, can be obtained, and by blending this gel composition, it is possible to provide a cosmetic having excellent characteristics which has never been seen before. It has become.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ identification code FI C08L 83/10 C08L 83/10 (58) Investigated field (Int.Cl. ⁶ , DB name) C08L 51/00-51/10 C08L 83/10

Claims (2)

(57) [Claims] (A) and (b) (a) an ester or acid amide of a higher alcohol or amine having 12 or more carbon atoms and (meth) acrylic acid, and having a radical polymerizable group at one terminal of a molecular chain. Acrylic-silicone graft copolymer obtained by copolymerizing a radical polymerizable monomer mainly composed of a dimethylpolysiloxane compound. (B) A gel composition comprising a silicone oil having a viscosity of 50 cs or less (25 ° C). 2. A cosmetic comprising the gel composition according to claim 1.