JP2700816B2 - Gel composition and cosmetic containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[Industrial Application Field] The present invention relates to an acrylic-silicone-based graft copolymer having a specific organosiloxane as a side chain and a viscosity thereof.
The present invention relates to a solid gel composition comprising a silicone oil of 50 cs or less, and a cosmetic containing the same. More specifically, a soft gel composition having excellent stability and particularly useful as a material for cosmetics. And by having it contained, it has a smooth and crisp feel,
An object of the present invention is to provide cosmetics having excellent usability, usability, and stability over time. [Prior art] Conventionally, cosmetics have been prepared as solids, ointments, and gels using solid oils such as waxes, semisolid oils, liquid oils, gelling agents and the like as base materials. . Silicone oil has been applied to various products due to its excellent properties as a constituent component of such a base material, and is widely used as a useful oil component especially in cosmetics. This means that the silicone oil has favorable characteristics and conditions such as less stickiness, good stretch, good crisp feel, and excellent lubricity, water repellency, tasteless and odorless, and high skin safety. It is because it has. Therefore, the study of commercialization of basic cosmetics and hair cosmetics, which have a good feeling of use by blending and utilizing silicone oil, and treat and protect the skin and hair, or make-up cosmetics with long lasting cosmetics, has been studied. It has been done. Usually, such silicone oil for cosmetics has a molecular weight,
Typical examples include linear dimethylpolysiloxanes having different viscosities, such as cyclic octamethylcyclotetrasiloxane, decamethylcyclopentaxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane. Polymers and modified products are commercially available. These various silicone oils are used separately or in combination in consideration of cosmetic purposes and expected effects. For example, low-viscosity dimethylpolysiloxane is applied to products that require a less sticky and damp feel, and those with higher viscosity are applied to products that repel water effectively,
Further, chain or cyclic volatile silicone oil has a property of volatilizing after application, and thus is often used for products requiring a refreshing feeling. In addition, dimethylhydrogenpolysiloxane has been used to improve the cosmetic stay of makeup cosmetics by using it for hydrophobic treatment of cosmetic powders. In general, techniques that make effective use of the characteristics of such silicone oils are known, and efforts have been made to develop applications for cosmetics. [Problems to be Solved by the Invention] As described above, although silicone oil is important as an oil for cosmetics, it has the following disadvantages in obtaining an expected product with further enhanced functionality. Often seen. That is, silicone oils generally have poor compatibility with other cosmetic oils, and it has been difficult to prepare products based on silicone oils that are uniformly dissolved and stable. When blending silicone oil, it is difficult to maintain a stable emulsion when it is made into an emulsified emulsion or mixed with wax and other cosmetic oils. Phenomena such as separation and discharge. This is particularly noticeable when a low-viscosity or volatile silicone oil is used in a large amount in order to impart a crisp feel and to enhance the makeup feel of the makeup cosmetic. When a high-viscosity silicone oil is used, water repellency is improved, but a sticky feeling and a heavy oily feeling are simultaneously felt. As described above, the content of the silicone oil was increased, and a sufficient effect was expected. Further, it was difficult to obtain a product with good safety. 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. It was. From this point, even if a high-viscosity material having a high molecular weight is used, although it has an apparent viscosity, it still exhibits flow characteristics without a yield value. Phenomenon is seen and sticky feeling,
A heavy oily feeling or the like occurs, which is not preferable in touch. In addition, when used in combination with waxes, the compatibility is poor, and the precipitation of waxes is likely to occur, and the properties of waxes themselves appear, and the smooth, smooth feel that is the characteristic of silicone oil as a cosmetic base. Thus, it was difficult to obtain a product having good stability and making full use of the properties of silicone oil. Further, silicone oil has been generally used as a liquid oil agent in the past, and has a structure-retaining property, that is, a soft gel-like substance having a yield value, or a hard gel-like substance replacing wax having structural strength. The use of was not well known. For this reason, there has been a demand for the development of a soft gel-like material that can use silicone oil as a base material for cosmetics and a hard gel-like material having structural strength that can be used as a solid skeleton such as wax. [Means for Solving the Problems] The present inventors have made intensive studies in view of the above-mentioned circumstances,
By mixing an acrylic-silicone-based graft copolymer having an organosiloxane as a side chain with a silicone oil having a viscosity of 50 cs or less, a solid gel composition that is soft and has excellent shape retention and stability can be obtained. It is found that the cosmetic composition is excellent in stability, smoothness, and usability having a smooth feeling by using the gel composition. The inventors have found and completed the present invention with these findings. That is, the present invention relates to an acrylic-silicone graft copolymer obtained by radical copolymerization of a dimethylpolysiloxane compound having a radical polymerizable group at one end of a molecular chain and a radical polymerizable monomer mainly composed of acrylate and / or methacrylate. An object of the present invention is to provide a gel composition comprising a polymer and a silicone oil having a viscosity of 50 cs or less, and a cosmetic containing the same. Hereinafter, the configuration of the present invention will be described. The gel composition of the present invention is mixed with a) an acrylic-silicone-based graft copolymer and b) a silicone oil having a viscosity of 50 cs or less (hereinafter referred to as “low-viscosity silicone oil”),
It maintains the solid state. A) The acrylic-silicone graft copolymer is
It is synthesized by radical copolymerization of a dimethylpolysiloxane compound (A) having a radical polymerizable group at one end of a molecular chain and a radical polymerizable monomer (B) mainly composed of acrylate and / or methacrylate. is there. The dimethylpolysiloxane compound having a radical polymerizable group at one terminal of the molecular chain of (A) is represented by the following general formula (1)
It is shown by. Me: methyl group R ₁ : methyl group or hydrogen atom R ₂ : carbon atom 1 having a linear or branched carbon chain optionally interrupted by one or two ether bonds
1 to 10 divalent saturated hydrocarbon groups l: 3 to 300 R ₂ is a carbon atom having a linear or branched carbon chain optionally interrupted by one or two ether bonds
Represents up to 10 divalent saturated hydrocarbon groups,
This specific _{-CH 2 -, CH 2 3,} CH 2 5, C
_{H 2 8, CH 2 10,} -CH 2 -CH (CH 3) -CH 2 -, - CH 2 CH 2 OCH 2 CH 2 CH 2 -, - C
_{H 2 CH 2 OCH 2 CH (} CH 3) CH 2 -, -CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 CH 2 - , etc. are exemplified. l
Is in the range of 3 to 300, preferably 5 to 100. If this is less than 3, the compatibility between the obtained acrylic-silicone-based graft copolymer and the low-viscosity silicone oil described below decreases, so that the gel composition It becomes impossible to form things,
On the other hand, when it exceeds 300, the glass transition point of the obtained acrylic-silicone-based graft copolymer is too low, so that a good solid gel composition cannot be obtained. The dimethylpolysiloxane compound represented by the general formula (1) having a radical polymerizable group at one end of the molecular chain is typically a (meth) acrylate-substituted chlorosilane compound represented by the following general formula (2). It can be obtained by subjecting a terminal hydroxyl-substituted dimethylpolysiloxane represented by the formula (3) to a dehydrochlorination reaction according to a conventional method, but the synthesis method is not limited thereto. Me: methyl group R ₁ : methyl group or hydrogen atom R ₂ : carbon atom 1 having a straight or branched carbon chain optionally interrupted by one or two ether bonds
~ 10 divalent saturated hydrocarbon groups Me: methyl group l: 3 to 300 Specific examples of the dimethylpolysiloxane compound having a radically polymerizable group at one end of the molecular chain include the following. Me: methyl group On the other hand, the radically polymerizable monomer mainly composed of acrylate and / or methacrylate of (B) means a compound having one radically polymerizable unsaturated bond in a molecule, and is used acrylate and / or methacrylate. As alkyl (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate
Examples thereof include hydroxyalkyl (meth) acrylates such as acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate, and perproloalkyl (meth) acrylates having 1 to 10 fluorocarbon chains. In the present invention, being mainly composed of acrylate and / or methacrylate means that one or more of acrylate and / or methacrylate in the radical polymerizable monomer is 50% by weight of the total radical polymerizable monomer. It means occupying the above. This is because if the total amount of the acrylate and / or methacrylate is less than 50% by weight, a good solid gel composition cannot be obtained. In the radical polymerizable monomer in the present invention, various compounds other than the above-mentioned acrylate and / or methacrylate can be used as needed. These polymerizable monomers include styrene, substituted styrene, vinyl acetate (meth) acrylic acid, maleic anhydride,
Maleic acid ester, fumaric acid ester, vinyl chloride,
Vinylidene chloride, ethylene, propylene, butadiene,
Acrylonitrile, fluorinated olefin and the like can be exemplified. In the present invention, (A) a dimethylpolysiloxane compound having a radical polymerizable group at one end of a molecular chain;
Polymerization ratio with a radical polymerizable monomer mainly composed of acrylate and / or methacrylate ((A) /
(B)) needs to be in the range of 1/19 to 2/1. If the ratio is less than 1/19, the compatibility between the acrylic-silicone-based graft copolymer and the low-viscosity silicone oil described below decreases, so that it becomes impossible to form a gel composition. If the amount exceeds the above range, the strength of the acrylic-silicone-based graft copolymer decreases, so that it becomes impossible to obtain a good solid gel composition. The copolymerization of (A) a dimethylpolysiloxane compound having a radical polymerizable group at one end of the molecular chain and (B) a radical polymerizable monomer mainly composed of acrylate and / or methacrylate is carried out by benzoyl peroxide or lauroyl peroxide. The reaction is carried out in the presence of a conventional isopolymerization initiator such as azobisisobutyronitrile, a solution polymerization method,
Any of the emulsion polymerization method, suspension polymerization method, and bulk polymerization method can be applied. Among them, the solution polymerization method is more preferable because it is easy to adjust the molecular weight of the obtained graft copolymer to an optimum range. As the solvent to be used, one or two kinds of 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, and alcohols such as isopropanol and butanol are used. A mixture of the above is mentioned. The polymerization reaction can be carried out 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 produced in this way is GP
The weight average molecular weight in terms of polystyrene at C is about 3,000 to about 200,000, more preferably about 5,000 to about 1
Must be in the range of 00,000 and -30 to +60
It preferably has a glass transition temperature in the range of ° C. On the other hand, the low-viscosity silicone oil of b) used in the present invention is not particularly limited, but needs to have a viscosity of about 50 cs or less. This increases as the viscosity increases
As a result of using a large amount thereof, the compatibility with the copolymer (a) is degraded, or oiliness is felt to the touch, which is unfavorable in terms of usability. Examples of the low-viscosity silicone oil include low-polymerization degree chain dimethylpolysiloxane, methylphenylpolysiloxane, cyclic octamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane, and the like. Alternatively, two or more kinds can be appropriately selected and used. The gel composition of the present invention is obtained by mixing the copolymer (a) with the low-viscosity silicone oil (b) and dissolving it by heating, or dissolving the copolymer (a) in a volatile organic solvent. After adding and mixing the low-viscosity silicone oil of b), it can be easily produced by removing the volatile organic solvent. In this case, the mixing ratio of the copolymer (a) and the low-viscosity silicone oil (b) varies depending on the type of the copolymer (a) and is not limited, but is generally 5:95 by weight. 7070: 30, preferably 15:85 to 40:60. When the amount of the copolymer (a) is small, the low-viscosity silicone oil of (b) becomes excessive due to the excess, resulting in a fluid viscosity, and a good solid gel composition cannot be obtained. Alternatively, it is difficult to obtain an elastic solid gel composition. Further, in the present invention, by changing the blend ratio of the copolymer and the low-viscosity silicone oil and the composition of the acrylic chain of the copolymer, the length of the silicone chain, the substitution amount, etc., the resin had a relatively high hardness. It is possible to obtain a solid gel composition having changed physical properties, such as a soft one to a soft one. That is, if it is intended to obtain a solid gel composition having a feeling of moderate hardness, it is sufficient to increase the blending ratio of the copolymer, or to introduce a large amount of methyl methacrylate into the acrylic portion of the copolymer. In order to obtain a highly flexible solid gel composition, a large amount of butyl acrylate, 2-ethylhexyl acrylate, or the like may be introduced into the acrylic portion of the copolymer. The solid gel composition obtained according to the present invention is soft, has good stability, has a smooth and smooth feel, and is excellent in usability. By utilizing this solid gel composition as a cosmetic material, an extremely useful cosmetic material exhibiting its properties can be obtained. As cosmetics in the present invention, cream, milky face and the like,
Basic cosmetics for limbs, hair cosmetics, hair cosmetics such as hair treatment, makeup cosmetics such as foundation, white powder, blusher, eye shadow, lipstick, eyeliner, mascara, etc. It does not matter which gel composition is applicable. At this time, the compounding amount is in the range of 1 to 100% by weight, and it may be used as it is or may be determined according to the purpose of use. In addition, the cosmetic in the present invention is composed of the solid gel composition and a component which is a conventional cosmetic base material. More concrete examples of the conventional cosmetic base components include oils and fats,
Raw materials for waxes, hydrocarbons, fatty acids, higher alcohols, esters, silicone oils, etc., powder materials for white pigments, colored pigments, extenders, etc., metallic soaps, surfactants,
Polyhydric alcohols, polymer compounds, water, other antioxidants, alkali agents, ultraviolet absorbers, preservatives, tar dyes,
Components for beautiful skin, etc., which are appropriately selected according to the product type and the purpose of makeup. Examples Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples. These do not limit the present invention at all. Example [1] Gel composition 30 g of a methacrylate-substituted dimethylpolysiloxane having one terminal represented by the following chemical formula: 30 g of methyl methacrylate, 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 the graft polymer. The precipitate was separated and dried to obtain 93 g of a white substance. The infrared absorption spectrum confirmed that the product was a methacrylate polymer to which dimethylpolysiloxane was grafted. The weight average molecular weight in terms of polystyrene by GPC was about 16,000, and the glass transition temperature was 18 ° C. Subsequently, 35 g of this graft copolymer and 65 g of dimethylpolysiloxane (KF96A (6cs) manufactured by Shin-Etsu Chemical Co., Ltd.) having a viscosity of 6 centistokes (25 ° C.)
And dissolved in 150 g of isopropanol, then 50 mmHg, 60
Isopropanol was distilled off while stirring at a temperature of ° C to obtain a uniform solid gel composition. Example [2] Gel composition 40 g of methacrylate-substituted dimethylpolysiloxane having one end represented by the following chemical formula, A graft copolymer was obtained from 40 g of methyl methacrylate and 20 g of 2-ethyl-hexyl acrylate under the same conditions as in Example [1]. Its weight average molecular weight in terms of polystyrene by GPC was about 15,000, and its glass transition temperature was 25 ° C. Subsequently, a uniform solid gel composition was obtained from 40 g of the graft copolymer and 60 g of decamethylcyclopentanesiloxisan (KF-995 manufactured by Shin-Etsu Chemical Co., Ltd.) in the same manner as in Example [1]. . Example [3] Gel composition 45 g of dimethyl polysiloxane substituted with methacrylate at one end represented by the following chemical formula: 30 g of methyl methacrylate, n-butyl methacrylate 1
A graft copolymer was obtained from 0 g and 15 g of 2-ethylhexyl acrylate under the same conditions as in Example [1]. Its weight average molecular weight in terms of polystyrene by GPC was about 17,000, and its glass transition temperature was 20 ° C. Subsequently, a uniform solid jelly gel composition was obtained from 30 g of the graft copolymer and 70 g of dimethylpolysiloxane (5cs) (KF-96 manufactured by Shin-Etsu Chemical Co., Ltd.) in the same manner as in Example [1]. Was. Example [4] Solid foundation (prescription) (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) 7) Gel composition (obtained in Example [1]) 79.8 (Preparation method) After mixing and homogenizing the components (1) to (5), the component (6) was added, and the mixture was uniformly homogenized with a three-roll mill. It was dispersed, melt-filled in a container, and cooled and solidified to obtain a solid foundation. Comparative Example [1] Solid Foundation In place of the solid gel composition as the component (6) of Example [4], a solution prepared by heating and dissolving 12 parts of starch stearic acid ester and 67.8 parts of liquid paraffin was used. A solid foundation was obtained in the same manner as in Example [4] except that it was used. The solid foundations of Example [4] and Comparative Example [1] obtained as described above were evaluated by conducting a use test with 20 female panels. The evaluation was performed by assigning an evaluation score to each item as described below, and a judgment was made. Table 1 shows the results. Evaluation point Very good 3 points Good or ordinary 2 points Bad 1 point Judgment Average point 2.5 or more ◎ Average point 1.5 or more and less than 2.5 ○ Average point less than 1.5 × From the results in Table 1, the solid foundation in which the solid gel composition of the present invention was blended was compared with the comparative product,
It was proved to be excellent in usability and usability. Example [5] Sticky Eyeshadow (Formulation) (parts by weight) (1) Gel composition (obtained from Example [2]) 75.0 (2) Decamethylcyclopentanesiloxane 10.0 (3) Colored pigment 4.5 (4) Mica 8.5 (5) Mica 2.0 (Preparation method) After mixing the components (1) to (5), they were kneaded with a three-roll mill, made uniform, and dissolved and filled in a container to obtain a product. The thus obtained stick-like dough of Example [5] has a smooth skin contact, has a good spread and spread, has no stickiness or oiliness, has a light feeling of use, and has It had excellent feeling and usability such as good stickiness and water resistance. In place of the component (1) in Example [5], 15 parts of microcrystalline wax and dimethylpolysiloxane ( 5c
s) Those prepared in the same manner as in Example [5] except that 60 parts were used, were inferior to Example [5] due to lack of spreading and spreading to the skin and no stickiness. Was observed, and the stability was poor. That is, according to the present invention, a high quality and extremely useful product was obtained without using a skeleton component such as wax. Example [6] Hand cream (O / W type) (Formulation) (Parts by weight) (1) Stearic acid 2.5 (2) Cetyl alcohol 1.7 (3) Gel composition (obtained in Example [1]) 10.0 (4) Octamethylcyclotetrasiloxane 10.0 (5) Sorbitan sesquioleate 1.0 (6) Polyoxyethylene sorbitan monooleate 2.0 (7) Triethanolamine 7.0 (8) 1,3-butylene glycol 5.0 (9) Carboxyvinyl polymer 0.5 (10) Remaining amount of purified water (Preparation method) Components (1) to (6) are mixed and dissolved by heating at 80 ° C to obtain an oil phase component. Also, mix the components (7) to (10),
In water to form an aqueous phase component. The aqueous phase component was added to the oil phase component with stirring, emulsified and cooled, and then filled into a container to obtain a hand cream. The hand cream of Example [6] obtained as described above does not feel oily to the touch, has a smooth feeling, has a good usability and usability, and is excellent. Atsuta. Example [7] Face cream (W / O type) (Formulation) (parts by weight) (1) Gel composition (obtained in Example [2]) 6.0 (2) Liquid paraffin 20.0 (3) Light flow Isoparaffin 6.0 (4) Dipentaerythritol fatty acid ester 2.0 (5) Vaseline 4.0 (6) Diglycerin diisostearate 2.0 (7) Citric acid 0.3 (8) Citric acid 1.2 (9) 1,3-butylene glycol 8.0 (10) Methyl paraoxybenzoate 0.1 (11) Remaining amount of purified water (Production method) Mix components (1) to (5) and dissolve by heating. A gel emulsion prepared by previously adding a part of the components (7), (8) and (11) to the component (6) is added thereto, and the mixture is heated to 70 ° C.
Then, the remaining components (9), (10) and (11) are mixed, heated and melted to 70 ° C., added while stirring, emulsified, cooled, and filled in a container. I got a cream. The face cream of Example [7] obtained as described above had a good feel upon use and good stability over time, and was suitable for protecting the face. Example [8] Nail treatment (formulation) (parts by weight) (1) Gel composition (obtained in Example [1]) 50.0 (2) Hydrophobic silicic anhydride 2.0 (3) Octamethylcyclotetrasiloxane 38.0 (4) Dimethylpolysiloxane (20cs) 8.0 (5) UV absorber 1.0 (6) Suitable amount of fragrance (7) Suitable amount of colorant (Production method) After mixing components (1) to (7), roll three The mixture was sufficiently kneaded to obtain a nail treatment. The nail treatment of Example [8] obtained as described above is in a creamy state, has a non-greasy feel when used, and can give an appropriate gloss to the nail, which is very useful. It was something. Example

[9] Jelly-like solid eye shadow (prescription) (parts by weight) (1) Gel composition (obtained in Example [3]) 65.0 (2) Decamethylcyclopentasiloxane 10.0 (3) Hydrophobic silicic anhydride 1.0 (4) Colored pigment 3.0 (5) Titanium oxide mica 5.5 (6) Mica 2.0 (7) Dimethyl polysiloxane (10cs) 13.5 (8) Perfume appropriate amount (Production method) After mixing components (1) to (8) Then, the mixture was thoroughly kneaded with a three-roll mill to make the mixture uniform, and the mixture was dissolved and filled in a container to obtain a jelly-like solid eye shadow. Example obtained as described above

The jelly-shaped solid eye shadow of [9] has elasticity, a new appearance, good spread and spread when used, has a non-sticky feel, and has an excellent feel for makeup. Things. [Effects of the Invention] As described above in detail, the gel composition obtained according to the present invention has no oiliness or stickiness, is soft and smooth, and has excellent usability and usability. Further, it is a solid substance having a structure-retaining property, and further, has extremely useful properties such as excellent lubricity and water repellency and high skin safety. Therefore, if the gel composition of the present invention is used as a cosmetic material, it can be applied to various cosmetics in the same manner as the conventional silicone oil, and a novel cosmetic exhibiting its unique performance can be obtained. And, for example, even when used in large quantities, there is no stickiness, there is no oiliness, there is a light feeling of use, it can be a product with a water-repellent cosmetic film, and it can be applied to the skin and hair It can provide an appropriate amount of moisturizing, luster, and protective effects, and can also improve the make-up of the makeup cosmetics. Further, in conventional solid oil-based cosmetics such as waxes, by using the gel composition of the present invention, it is possible to form a solid cosmetic without using a solid oil, the conventional solid oil-based cosmetic In addition, not only can a product with improved usability and usability be obtained, but also a cosmetic having a new taste with a different appearance can be prepared. As described above, according to the present invention, a gel composition having extremely high usefulness, particularly as a material for cosmetics, is obtained. By blending this gel composition, it is possible to provide a cosmetic having excellent characteristics which has not been achieved conventionally. It has become possible.

Claims (2)

(57) [Claims] 1. A dimethylpolysiloxane compound having a radical polymerizable group at one end of a molecular chain, an acrylate and / or
Alternatively, a gel composition comprising an acrylic-silicone-based graft copolymer obtained by radical copolymerization of a radical polymerizable monomer mainly composed of methacrylate, and a silicone oil having a viscosity of 50 cs or less. 2. A cosmetic comprising the gel composition according to claim 1.