JPH0225411A - Cosmetic - Google Patents

Abstract

PURPOSE:To provide a cosmetic containing an acryl-silicone graft copolymer having a specific organosiloxane side chain as a film-forming agent, having high cosmetic functionality and good applicability and forming a coating film having excellent water-resistance, oil-resistance and physical properties of the film. CONSTITUTION:The objective cosmetic having the above effects contains a film-forming agent consisting of an acryl-silicone graft copolymer produced by the radical copolymerization of (A) a dimethylpolysiloxane compound having a radically polymerizable group at one terminal of the molecule chain and expressed by formula (Me is CH3; R1 is CH3 or H; R2 is 1-20C bivalent saturated hydrocarbon group having straight or branched carbon chain which may be interrupted with 1-2 ether bonds; l is 3-300) and (B) a radically polymerizable monomer composed mainly of an acrylate and/or a methacrylate at a polymerization ratio (A:B) of 1:(19-1).

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a cosmetic composition containing an acrylic-silicone graft copolymer having a specific organosiloxane side chain as a film forming agent. The object of the present invention is to provide a cosmetic that forms a film with excellent water resistance, oil resistance, and physical properties, has high cosmetic functionality, and is easy to use.

[Prior Art] Cosmetics have traditionally been formulated with various film-forming agents, and typical products that utilize the effective film-forming properties of these film-forming agents include nail enamel, etc. There are eye makeup products such as nail polish, eyeliner, and mascara. These products generally require a strong coating film and use substances that form a continuous coating film. Specifically, in nail enamel, nitrocellulose,
In alkyd resins, acrylic resins, eyeliners, and mascaras, it is known to use synthetic resin emulsions such as polyvinyl acetate emulsion, polyacrylic acid ester emulsion, or copolymers thereof.

In addition, the demands placed on cosmetics have become even higher, and film-forming agents have been applied and developed to provide good properties to the cosmetic film, such as water resistance and oil resistance, and to prevent makeup from fading. It's been coming.

On the other hand, in makeup cosmetics, it has become important that the makeup does not easily come off and that the makeup lasts long, so water-repellent silicone oils and silicone resins have been used.

[Problems to be Solved by the Invention] As mentioned above, film forming agents play an important role in nail enamel, eyeliner, and mascara.
The following points were often found to be inconvenient:

In other words, in nail beauty products, nitrocellulose is used as a film-forming agent, and solvents such as ethyl acetate, butyl acetate,
It is generally used by mixing it with an organic solvent such as acetone or toluene. However, the film formed by nitrocellulose was hard and lacked flexibility, and also had poor gloss and adhesion P#. Therefore, it is necessary to add plasticizers such as camphor and phthalic acid derivatives to impart flexibility to the coating film, and resins such as alkyd resins and saccharide-modified resins to improve gloss and adhesion. It is generally blended as an ingredient. Therefore, it is necessary to design the product in consideration of the influence of the plasticizer and resins added on the physical properties of the film, and the stability of the product system.

In addition, although a water-resistant film is formed in the well-known synthetic resin emulsions used in eyeliners and mascaras, water-soluble active agents mixed in during manufacturing and pigment dispersion during product production are water-soluble. The use of these active agents caused the film itself to peel off due to water, sweat, etc., and the results were unsatisfactory in terms of good adhesion and long-lasting makeup. In addition, eyeliner and mascara products include non-aqueous types that contain volatile solvents such as isoparaffin and silicone oil. This kind of product either has sufficient resistance to water and sweat, that is, it is water resistant, or the coating film formed is mainly made of high-melting wax, and the makeup does not come off when exposed to sebum and oil. However, the oil resistance was not completely satisfactory.

"Means for Solving the Problems" In view of the above-mentioned circumstances, the present inventors conducted extensive research and found that an acrylic-silicone graft copolymer
We discovered that it has excellent film-forming properties, and the film formed thereby has water resistance and oil resistance, and has good physical properties, making it extremely effective as a film-forming agent, and we incorporated it into cosmetics. They completed the invention with the knowledge that if they did so, they could obtain a cosmetic that exhibited its performance, had excellent cosmetic functionality, and was easy to use.

That is, the present invention provides a film-forming agent obtained by radical copolymerization of a dimethylpolysiloxane compound having a radically polymerizable group at one end of its molecular chain and a radically polymerizable polymer mainly composed of acrylate and/or methacrylate. The present invention relates to a cosmetic containing an acrylic-silicone graft copolymer.

The configuration of the present invention will be explained below.

Acrylic used as a film forming agent in the present invention
A silicone-based graft copolymer is a dimethylpolysiloxane compound (A) having a radically polymerizable group at one end of its molecular chain, and a radically polymerizable polymer (B) mainly composed of acrylate and/or methacrylate. It is synthesized by polymerization.

The dimethylpolysiloxane compound (A) having radical polymerizability at one end of its molecular chain is represented by the following general formula (1).

Me: Methyl group R1: Methyl group or hydrogen atom R2: Divalent group of 1 to 10 carbon atoms having a straight or branched carbon chain, optionally interrupted by one or two ether bonds a saturated hydrocarbon group Il,: 3 to 300 R2 is 1 carbon atom with a straight or branched carbon chain optionally interrupted by 1 or 2 ether bonds;
-10 saturated hydrocarbon groups, specifically -CH2-, -CH2+-3, -CH2
-CH(CH3)-C1)2-1(CH2MC1)2G82nd floor, -CH2C1(zOCH2CLCL-1CH
H2-1-CH2G to 2GH20CH2CH (CH3)
I120CH2C) I20CH2CH2CL-, etc. are exemplified. L is in the range of 3 to 300, preferably 5 to 100; if it is less than 3, the water resistance of the formed film may not be sufficient, or the volatile property may be insufficient as a solvent for dissolving the film forming agent of the present invention. The compatibility with silicone oil etc. will decrease, and if it exceeds 300, the glass transition point of the resulting acrylic-silicone graft copolymer will be too low, making it difficult to form a film with sufficient strength. It depends on not being able to do anything.

The dimethylpolysiloxane compound represented by the general formula (1) having a radically polymerizable group at one end of the molecular chain is
Typically, it is obtained by subjecting a (meth)acrylate-substituted chlorosilane compound represented by the following general formula (2) and a terminal hydroxyl group-substituted dimethylpolysiloxane represented by the general formula (3) to a dehydrochloric acid reaction according to a conventional method. However, the synthesis method is not limited to this.

R,Me CH2=C-C-0-R2-5i-CI
(2) 0 Me R1: Methyl group or hydrogen atom (described above) R2 - Interrupted by one or two ether bonds depending on the case. Divalent saturated hydrocarbon group with 1 to 10 carbon atoms having a linear or branched carbon chain (as above) I: 3 to 300 (as above) Therefore, radical polymerization occurs at one end of the molecular chain. Specific examples of dimethylpolysiloxane compounds that are preferably used as the dimethylpolysiloxane compound having a functional group include those described below.

G1)3
M e(:R12-GCOOCH2CH20CH
2CH20CH2CH2CI12Si0e On the other hand, (B) radically polymerizable polymer mainly composed of acrylate and/or methacrylate means a compound having one radically polymerizable unsaturated bond in the molecule, and the acrylate and/or methacrylate used is , methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, alkyl (meth)acrylates such as 2-ethylhexyl (meth)acrylate, 2- and droxyethyl (meth)acrylate, 2-hydroxypropyl ( Examples include hydroxyalkyl (meth)acrylates such as meth)acrylates, and perfluoroalkyl (meth)acrylates having 1 to 10 fluorocarbon chains.In the present invention, the fact that acrylates and/or methacrylates are the main component means that This means that the total amount of one or more acrylates and/or methacrylates accounts for 50% or more by weight of the total radically polymerizable monomers in the radically polymerizable monomers mentioned above. This is because if the total amount of methacrylate is less than 50% by weight, a good film cannot be obtained.

In the radically polymerizable monomer of the present invention, various compounds other than the above-mentioned acrylate and/or methacrylate can be used as necessary. These polymerizable monomers include styrene, substituted styrene,
Examples include vinyl acetate, (meth)acrylic acid, maleic anhydride, maleic esters, fumaric esters, vinyl chloride, vinylidene chloride, ethylene, propylene, butadiene, acrylonitrile, and fluorinated olefins.

In the present invention, the polymerization ratio ((8)/ (B))
must be within the range of 1/19 to I/].

If the ratio of the dimethylpolysiloxane compound having a radically polymerizable group at one end of the molecular chain in (A) becomes too small, the water resistance of the formed film may not be sufficient. The compatibility with volatile silicone oil such as octamethylcyclotetrasiloxane, which is useful as a solvent for dissolving the acrylic-silicone graft copolymer of the present invention, may decrease, and on the other hand, if the acrylic-silicone graft copolymer of the present invention exceeds 171. If the proportion of the radically polymerizable monomer mainly composed of acrylate and/or methacrylate (B) becomes too small, the strength of the acrylic-silicone graft copolymer will decrease, making it impossible to form a film with good strength. This is due to a number of reasons.

The copolymerization of (A), a dimethylpolysiloxane compound having a radically polymerizable group at one end of the molecular chain, and (B), a radically polymerizable monomer mainly composed of acrylate and/or methacrylate, can be performed using benzoyl peroxide or lauroyl peroxide. The polymerization is carried out in the presence of a conventional radical polymerization initiator such as azobisisobutyronitrile, and any of solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization can be applied. Among these, the solution polymerization method is preferred because it allows easy adjustment of the molecular weight of the resulting graft copolymer to an optimal range.

The solvent used is one 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. A mixture of two or more types may be mentioned.

Polymerization reaction at 50-180°C, preferably 60-120°C
This can be carried out within a temperature range of 100 to 100 mL, and precuring can be carried out for about 5 to 10 hours under these conditions. The acrylic-silicone graft copolymer produced in this manner has a weight average molecular weight of about 3,000 to about 200,000, more preferably about 5,000 to about 100,000, as measured by GPC in terms of polystyrene. The glass transition temperature is preferably in the range of -30 to +60°C.

For the copolymer of the present invention described above, various cosmetics that can be used as film-forming agents can be used. For this application, for example, in the case of a nail polish such as nail enamel, the coelectric material may be volatile isoparaffin, ethyl acetate,
Butyl acetate, acetone, toluene, etc. can be blended by dissolving them in a hydrocarbon system, and a continuous coating film is formed after application.

The blending amount is 10 to 70%, preferably 30 to 60%. If the amount of the copolymer is too small, the film will be thin and will not be sufficient for its desired function, and if it is too large, the viscosity of the product will become high and it will be difficult to apply it on the nails.

Furthermore, in this case, film coating properties were mainly controlled by additives such as camphor, phthalic acid derivatives, or alkyd resins in conventional products, whereas in the present invention, the properties of film coating were mainly controlled by additives such as camphor, phthalic acid derivatives, or alkyd resins. Furthermore, the physical properties of the coating film can be controlled by changing the length of the silicon chain. In other words, if a large amount of methyl methacrylate is introduced into the acrylic chain portion, the film formed will be hard, whereas if a large amount of butyl acrylate, 2-ethylhexyl acrylate, etc. is introduced, a soft film will be formed and the film will be more soluble in solvents. It is possible to increase Furthermore, by making the silicone button longer, it is possible to impart lubricity to the coating film.

In addition, non-aqueous eye makeup materials such as eyeliner and mascara can be blended by dissolving the above copolymer in isoparaffin and volatile silicone. After application, the solvent evaporates and a continuous coating film is formed. be done. The blending amount is 5~
60%, preferably 10-40%. In this case, depending on the amount of other ingredients such as waxes or pigments, if the amount of the copolymer is too small, the formed coating will lack continuity, and if it is too large, the formed coating will lack continuity. This is undesirable because the viscosity of the product becomes high, making it difficult to use, and it becomes difficult to remove when removed with a remover, putting a strain on the eye area.

As described above, in the present invention, by utilizing the above-mentioned copolymer in products that require film formation, its properties are exhibited, and extremely useful cosmetics can be obtained.

Cosmetics of the present invention include not only nail polishes and eye makeup cosmetics, but also basic cosmetics such as creams and emulsions, hair cosmetics such as hair styling products, and makeup cosmetics such as foundation, white powder, blush, eye shadow, and lipstick. This includes fees.

This does not matter, as long as the copolymer is used as a film-forming component or as a binder.

Incidentally, the cosmetic composition of the present invention includes, as components other than the above-mentioned copolymer, components that constitute conventional cosmetic bases. More specific examples of cosmetic base components include fats and oils, waxes, oil components such as hydrocarbons, fatty acids, higher alcohols, and esters, powder components such as white pigments, colored pigments, and extender pigments, and metals. Soaps, gelling agents, tar pigments, surfactants, polyhydric alcohols, polymer compounds, water, organic solvents, and other additives such as preservatives, alkaline agents, ultraviolet absorbers, antioxidants, ingredients for beautiful skin, etc. These are appropriately selected and used depending on the product type and cosmetic purpose.

[Example] Hereinafter, the present invention will be further explained by giving reference examples and examples. Note that these do not limit the present invention in any way.

Reference Example [1] Synthesis of acrylic-silicone-based raft copolymer 35 g of dimethyl polysiloxane substituted with methacrylate at one end represented by the chemical formula below, 45 g of methyl methacrylate, 20 g of 2-ethyl-hexyl acrylate, and 100 g of toluene were mixed, and then After adding and dissolving 1.5 g of azoisobutyronitrile, the mixture was allowed to react for 5 hours within a temperature range of 80 to 90° C. while stirring to obtain a viscous solution. This solution was poured into two sides of methanol to precipitate the graft polymer. The precipitate was filtered and dried to obtain 88 g of a white substance. This material was confirmed by infrared absorption spectrum to be a methacrylate polymer obtained by crafting dimethylborisiloxane, and the weight average molecular weight in terms of polystyrene by GPC was approximately 13,000, and the glass transition temperature was 37°C.
Met.

Reference Example [21 Synthesis of Acrylic-Silicone Graft Copolymer Under the same conditions as Reference Example [1], one terminal methacrylate-substituted dimethylpolysiloxane 25 represented by the chemical formula below was synthesized.
A graft polymer was obtained from g, 50 g of methyl methacrylate, 15 g of n-butyl methacrylate, and 10 g of vinyl acetate. The polystyrene-substituted weight average molecular weight of this product by GPC was about 1),000, and the glass transition temperature was 26°.

Give an example.

Example [1] Eyeliner (ingredients) (parts by weight) (1)
Isoparaffin 46.0 (2)
Acrylic-silicone based graphite 30,0 ft copolymer (obtained in Reference Example [1]) (3) Organic bentonite 3.0 (4
) 1,3-butylene glycol 1.0(5)
Fragrance: Appropriate amount (6) Coloring pigment: 20.0 (Production method) Dissolve component (2) in component (1), and add components (3) and (4).
Add the mixture. Add ingredients (5) and (6) to this,
After uniformly dispersing it with a three-piece roll, it was filled into a container to obtain a product.

Comparative Example 1 In the formulation of eyeliner Example 1, 5 parts of microcrystalline wax and 2 parts of pentaerythritol lysinate were used instead of component (2).
A product was obtained in the same manner except for replacing with 5 parts.

Durability tests and sensory evaluations were conducted on the eyeliners of Example 1 and Comparative Example 1 obtained as described above. The results are shown in Table 1.

In the durability test, a thin film was formed using a 6 mil doctor blade on a nylon resin plate, and after drying, the product was subjected to the test. Water resistance was evaluated by soaking in water, and oil resistance was evaluated by soaking in artificial sebum. In addition, the scratch strength was evaluated by rubbing the thin film with fingers. The results were expressed as 0 being good and × being bad.

In addition, the sensory evaluation was conducted using 20 female panels, and the evaluation items listed in Table 1 were given 3 points for very good, 2 points for good or fair, and 1 point for poor, and the average score for each was 2 points. .5 points or more ◎, 1.5-2.5 points O
l Less than 1.5 points were expressed as ×.

Table 1 As is clear from Table 1, the product of the present invention has a coating film with water resistance and
It has been confirmed and demonstrated that it is oil resistant, has good strength against abrasion, does not easily come off, and has excellent makeup retention.

Example [2] Nail enamel (ingredients) (parts by weight) (1)
Isoparaffin 65.0 (2)
Acrylic-silicone-based graphite 35. Loft copolymer (obtained in Reference Example [2]) (3) Color pigment Appropriate amount (manufacturing method) After mixing and dissolving component (2) in component (1), homogeneously dispersing component (3), and then pouring into a container. The product was obtained by filling.

Example [3 mascara (ingredients) (parts by weight) (1)
Isoparaffin 52.0 (2)
Acrylic-silicone graphite 25.0ft copolymer (obtained in Reference Example [1)) (3) Organic bentonite 3.0
(4) Paraffin wax 5.0 (5)
Carnauba wax 4.0 (6) 1
．． 3-Butylene glycol 1.0 ('7)
Fragrance Appropriate amount (8) Pigment
10.0 (Production method) After dissolving component (2) in component (1), components (3) to (6)
was heated and dissolved, the component (8) was added thereto, and the mixture was uniformly dispersed using a three-piece roll, and then filled into a container to obtain a product.

The mascara of Example [3] obtained as described above had a coating film that was water and oil resistant and had a good feel when used.

[Effects of the Invention] As detailed above, the present invention combines a dimethylpolysiloxane compound having a radically polymerizable group at one end of its molecular chain with a radically polymerizable polymer mainly composed of acrylate and/or methacrylate. By blending the polymerized acrylic-silicone-based kraft copolymer as a film-forming agent, its functions are effectively exhibited, imparting water resistance and oil resistance to the decorative coating film, and improving the physical properties of the coating film. ,
This made it possible to provide cosmetics that were even more superior than before.

The thus obtained cosmetic composition of the present invention is resistant to water, sweat, sebum, etc. after use, so that the makeup does not easily come off and the makeup lasts long.

Furthermore, the properties of the copolymer used in the present invention can be changed by adjusting the molecular structure, making it possible to select according to the product and purpose of use, and thereby controlling the physical properties of the product. It is also advantageous in that it allows for

that's all Applicant: Kobayashi Kose Co., Ltd. Procedural amendment (voluntary) Yoshi, Director General of the Tokugawa Agency 1) Takeshi Mata 1゜ 3゜ 4゜ Display of incidents Showa, 1) Name of the invention of 163 year registration number 172967 cosmetics person who makes corrections Relationship to the case: Applicant Name Kobayashi Kose Co., Ltd.

Claims (1)

[Claims] (1) As a film forming agent, an acrylic film obtained by radical copolymerization of a dimethylpolysiloxane compound having a radically polymerizable group at one end of its molecular chain and a radically polymerizable monomer mainly composed of acrylate and/or methacrylate.
A cosmetic containing a silicone-based graft copolymer.