JP2704730B2 - Cosmetics - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a cosmetic prepared by blending an acrylic-silicone graft copolymer having a specific organosiloxane side chain as a film-forming agent. To form a film with excellent water and oil resistance and film properties,
The purpose is to provide cosmetics having high cosmetic functionality and good usability.

[Prior art] Conventionally, various film-forming agents are blended in cosmetics, and products utilizing the effective film-forming properties of these film-forming agents are typically represented by nail enamel and the like. There are eye make-ups such as nail polish, eye liner and mascara. In these products, the strength of the coating film is generally required, and a substance that forms a continuous coating film is used. Specifically, for nail enamel, nitrocellulose, alkyd resin, acrylic resin, and eyeliner, and for mascara, synthetic resin emulsion such as polyvinyl acetate emulsion, polyacrylate emulsion, or a combination thereof. The use of polymers and the like is known.

In addition, the demands for cosmetics have become even higher, and application and development of film-forming agents have been carried out in order to impart good properties to cosmetic films, for example, they have water resistance and oil resistance, and to prevent makeup loss. I have been.

On the other hand, in makeup cosmetics, it is especially important that makeup is not easily disintegrated and that it has excellent makeup persistence.
Water repellent silicone oils and silicone resins have been used.

[Problems to be Solved by the Invention] As described above, in a nail enamel, an eyeliner, and a mascara, the role of a film-forming agent is important, but it is often found that it is disadvantageous in the following points. .

That is, in the case of a beautiful nail material, nitrocellulose is generally used as a film-forming agent, and is mixed with an organic solvent such as ethyl acetate, butyl acetate, acetone or toluene to be used. However, the film formed by nitrocellulose was hard, lacked flexibility, and was poor in gloss and adhesion. Therefore, it is necessary to add a camphor or a phthalic acid derivative plasticizer in order to impart flexibility to the coating film.In addition, resins such as alkyd resin and sucrose-modified resin are used to improve gloss and adhesion. It is generally compounded as Therefore, it is necessary to design in consideration of the influence of the blended plasticizer and resin on the film properties or the stability of the product system.

In the case of known synthetic resin emulsions used for eyeliners and mascaras, although water-resistant films are formed, they are used for dispersing water-soluble activators mixed in during production and pigments during commercialization. Water-soluble activator
A phenomenon in which the film itself peels off due to water, sweat, etc. occurs, and it is not satisfactory in terms of good adhesion and good persistence of makeup. In the case of eyeliner and mascara products, there are non-aqueous types containing volatile solvents such as isoparaffin and silicone oil. This type of product has sufficient resistance to water and sweat, that is, water resistance, but the coating film formed is mainly due to the high melting point wax, and it loses makeup to sebum and oil. It was not easy to be satisfied with oil resistance.

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above-mentioned circumstances, and as a result, the acrylic-silicone-based graft copolymer has excellent film-forming properties and was formed by the same. The film has water resistance, oil resistance, good film properties,
It was found to be extremely effective as a film forming agent,
If it is blended into cosmetics, its performance will be demonstrated,
The invention was completed with the knowledge that a cosmetic having excellent cosmetic functionality and good usability could be obtained.

That is, in the present invention, a film-forming agent is 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. The present invention relates to a cosmetic containing an acrylic-silicone-based graft copolymer.

 Hereinafter, the configuration of the present invention will be described.

The acrylic-silicone graft copolymer used as a film-forming agent in the present invention mainly comprises a dimethylpolysiloxane compound (A) having a radical polymerizable group at one end of a molecular chain, and acrylate and / or methacrylate. It is synthesized by radical copolymerization with the radical polymerizable monomer (B).

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

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
Up to 10 divalent saturated hydrocarbon radicals 1: 3-300 R ₂ is a carbon atom 1 having a linear or branched carbon chain optionally interrupted by one or two ether linkages
But is represented a 10 or saturated hydrocarbon group, to this specific _{-CH 2 -, CH 2 3,} CH 2 6, CH 2
₈ , CH _{2 10} , -CH ₂ -CH (CH ₃ ) -CH _2- , -CH ₂ CH ₂ OC
H ₂ CH ₂ CH ₂ −, −CH ₂ CH ₂ OCH ₂ CH (CH ₃ ) CH ₂ −, −CH ₂ CH ₂ OC
_{H 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 it is less than 3, the water resistance of the film after formation is not sufficient or the volatile property useful as a solvent for dissolving the film forming agent of the present invention. Compatibility with silicone oil and the like will be reduced, and if it exceeds 300, the glass transition point of the obtained acrylic-silicone graft copolymer will be too low, so that a film having sufficient strength will be formed. Because they can no longer do it.

A dimethyl siloxane compound represented by the general formula (1) having a radical 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) to a dimethylpolysiloxane substituted with a terminal hydroxyl group represented by the following general formula (3) by dehydrochlorination according to a conventional method. However, the synthesis method is not limited to this.

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
~ 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 those described below.
In the following formula, Me represents a methyl group.

On the other hand, the radically polymerizable monomer mainly composed of acrylate and / or methacrylate (B) means a compound having one radically polymerizable unsaturated bond in a molecule, and the acrylate and / or methacrylate used is methyl. Alkyl (meth) such as (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 perfluoroalkyl (meth) acrylates having a fluorocarbon chain of 1 to 10. In the present invention, the fact that acrylate and / or methacrylate is the main component means that the total amount of one or more of acrylate and / or methacrylate in the radical polymerizable monomer is 50% by weight or more of the entire radical polymerizable monomer. Means to occupy. This is because if the total amount of acrylate and / or methacrylate is less than 50% by weight, a good film 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 ester, fumaric ester, vinyl chloride, vinylidene chloride, ethylene, propylene, butadiene, acrylonitrile, fluoride 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 and the proportion of the dimethylpolysiloxane compound having a radical polymerizable group at one end of the molecular chain of (A) is too small, the water resistance of the decorative film may not be sufficient, Of acryl-silicone-based graft copolymers, such as octamethylcyclotetrasiloxane, which is useful as a solvent for dissolving the volatile silicone oils, and the like. When the proportion of the radical polymerizable monomer mainly composed of acrylate and / or methacrylate is too small, the strength of the acryl-silicone graft copolymer is reduced, so that a film having good strength cannot be formed. Things.

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 polymerization is carried out in the presence of a usual radical polymerization initiator such as azobisisobutyronitrile, 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 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.

The copolymer of the present invention described above can be used for various cosmetics utilized as a film forming agent. In this application, for example, in the case of a nail enamel such as nail enamel, the copolymer can be dissolved in volatile isoparaffin, ethyl acetate, butyl acetate, acetone, toluene, etc., and blended. A coating is formed.

The compounding amount is 10 to 70%, preferably 30 to 60%. If the blending amount of the copolymer is too small, the film becomes thin, which is insufficient for expecting its function, and if it is too large, the viscosity of the product becomes high and it becomes difficult to apply it on nails. Also, in this case, the physical properties of the coating film were conventionally controlled by additives such as camphor, phthalic acid derivatives, or alkyd resins, whereas in the present invention,
The physical properties of the coating film can be controlled by changing the composition of the acrylic chain or the length of the silicon chain. That is, if a large amount of, for example, methyl methacrylate is introduced into the acrylic chain portion, the formed film becomes hard. On the other hand, if the amount of butyl acrylate, 2-ethylhexyl acrylate, and the like is increased, a soft film can be formed and the solubility in a solvent is increased. I can do things. In addition, lubrication can be imparted to the coating film by lengthening the silicone chain.

Also, in eyeliner and mascara non-aqueous eye makeup agents, the copolymer can be dissolved and blended in isoparaffin and volatile silicone, and after application, the solvent evaporates and a continuous coating film is formed. You. The amount is 5
6060%, preferably 10-40%. In this case, depending on the amount of other components, such as waxes or pigments, if the amount of the copolymer is small, the continuity of the formed coating film is lost, and if the amount is too large, the product is too large. It is not preferable because the viscosity at the time becomes high and it becomes difficult to use it, and it does not fall off when removed with a remover and places a burden on the eyes.

As described above, in the present invention, the properties are exhibited by using the copolymer for a product requiring film formation, and an extremely useful cosmetic is obtained.

Examples of the cosmetics of the present invention include beauty cosmetics, eye makeup cosmetics, basic cosmetics such as creams and emulsions, hair cosmetics such as hair styling, makeup cosmetics such as foundation, white powder, blush, eye shadow, and lipstick. Fees. This means that using the copolymer as a film-forming component,
Alternatively, any material may be used as long as it can be used as a binder, and it does not matter.

In addition, the cosmetic of the present invention comprises, as a component other than the copolymer, a component constituting a conventional cosmetic base. More specifically, cosmetic base components include oils and fats, waxes, oil components such as hydrocarbons, fatty acids, higher alcohols and esters, powder components such as white pigments, coloring pigments and extender pigments,
Metal soap, gelling agent, tar dye, surfactant, polyhydric alcohol, polymer compound, water, organic solvent, other additives such as preservatives, alkali agents, ultraviolet absorbers, antioxidants, and ingredients for beautiful skin These are appropriately selected and used according to the product type and the purpose of makeup.

[Examples] Hereinafter, the present invention will be further described with reference to Reference Examples and Examples. These do not limit the present invention at all.

Reference Example [1] Synthesis of acrylic-silicone-based graft copolymer 35 g of methacrylate-substituted dimethylpolysiloxane having one terminal represented by the following chemical formula After mixing 45 g of methyl methacrylate, 20 g of 2-ethyl-hexyl acrylate and 100 g of toluene, and then adding and dissolving 1.5 g of azobisisobutyronitrile, the mixture was stirred and stirred at a temperature in the range of 80 to 90 ° C. for 5 hours. The reaction was performed 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 88 g of a white substance. This was confirmed by infrared absorption spectrum to be a methacrylate polymer to which dimethylpolysiloxane was grafted,
The weight average molecular weight in terms of polystyrene by C was about 13,000, and the glass transition temperature was 37 ° C.

Reference Example [2] Synthesis of Acrylic-Silicone Graft Copolymer One-terminal methacrylate-substituted dimethylpolysiloxane 25 represented by the following chemical formula under the same conditions as in Reference Example [1].
g, 50 g of methyl methacrylate, 15 g of n-butyl methacrylate, and 10 g of vinyl acetate to obtain a graft polymer.
Its weight average molecular weight in terms of polystyrene by GPC was about 11,000, and its glass transition temperature was 26 ° C.

Next, examples of cosmetics using the copolymer obtained in the present invention will be shown.

Example [1] Eyeliner (Component) (parts by weight) (1) Isoparaffin 46.0 (2) Acrylic-silicone graft 30.0 copolymer (obtained in Reference Example [1]) (3) Organically modified bentonite 3.0 ( 4) 1,3-butylene glycol 1.0 (5) Appropriate amount of perfume (6) Color pigment 20.0 (Production method) Dissolve component (2) in component (1) and add a mixture of components (3) and (4). Components (5) and (6) were added to the mixture, and the mixture was uniformly dispersed with a three-roll mill and then filled into a container to obtain a product.

Comparative Example 1 Eyeliner In the formulation of Example 1, 5 parts of microcrystalline wax and pentaerythritol rosinate were used instead of component (2).
A product was obtained in the same manner except that the product was replaced with 25 parts.

The eyeliners of Example 1 and Comparative Example 1 obtained as described above were subjected to a durability test and a sensory evaluation. Table 1 shows the results.

In the durability test, a product was formed into a thin film on a nylon resin plate with a 6-mil doctor blade, dried, and then subjected to the test. Water resistance was evaluated by immersion in water, and oil resistance was evaluated by immersion in artificial sebum. The rubbing strength was evaluated by rubbing the thin film with fingers. The results are indicated by ○ as good and X as bad.

For the sensory evaluation, 20 female panels were used, and the evaluation items shown in Table 1 were rated as 3 points for very good, 2 points for good or ordinary, and 1 point for bad, and the average score was 2.5 for each. A point or more was represented by ◎, 1.5 to less than 2.5 points as ○, and less than 1.5 points as ×.

As is clear from Table 1, the product of the present invention was confirmed and demonstrated that the coating film had water resistance and oil resistance, had good abrasion resistance, did not easily lose makeup, and had excellent makeup.

Example [2] Nail enamel (component) (parts by weight) (1) Isoparaffin 65.0 (2) Acrylic-silicone graft 35.0 copolymer (obtained in Reference Example [2]) (3) Color pigment appropriate amount (production method) After mixing and dissolving the component (2) in the component (1), the component (3) was homogeneously dispersed and then filled in a container to obtain a product.

Example [3] Mascara (Component) (parts by weight) (1) Isoparaffin 52.0 (2) Acrylic-silicone graft 25.0 copolymer (obtained in Reference Example [1]) (3) Organically modified bentonite 3.0 (4) ) Paraffin wax 5.0 (5) Carnauba wax 4.0 (6) 1,3-butylene glycol 1.0 (7) Flavor appropriate amount (8) Color pigment 10.0 (Production method) After dissolving component (2) in component (1), dissolve component (3) ) ~
Add (6) and heat to dissolve. Add components (7) and (8)
Was added, and the mixture was uniformly dispersed with three rolls, and then filled into a container to obtain a product.

Example [4] Eyeliner (emulsion type) (Component) (parts by weight) (1) Stearic acid 2.0 (2) Cetanol 0.5 (3) Beeswax 5.0 (4) Sorbitan sesquioleate 0.5 (5) Sorbitan monooleate 0.5 (6) Triethanolamine 1.2 (7) Color pigment 14.0 (8) Polymethacrylic acid 0.5 (9) Acrylic-silicone graft copolymer 12.5 polymer (obtained in Reference Example [1]) (10) Isoparaffin 12.5 (11) Methyl paraoxybenzoate 0.2 (12) Remaining purified water (Preparation method) Components (1) to (5) and (9) to (10) are mixed and dissolved by heating. Components (6) to (8) and (11) to
After mixing (12), heating and adding, emulsify,
After cooling, the product was filled in a container to obtain a product.

Examples [2], [3] and [4] obtained as described above
In the product of No. 1, the coating film had water resistance and oil resistance, and the use feeling was good.

[Effects of the Invention] As described in detail above, the present invention provides a radical copolymerization of a dimethylpolysiloxane compound having a radical polymerizable group at one end of a molecular chain with a radical polymerizable monomer mainly composed of acrylate and / or methacrylate. By blending the obtained acrylic-silicone-based graft copolymer as a film-forming agent, its function is effectively exhibited, water resistance and oil resistance are imparted to the decorative coating film, and the coating film physical properties are also improved, It has made it possible to provide extremely excellent cosmetics compared to the past.

The cosmetic of the present invention thus obtained is resistant to water, sweat, sebum, and the like after use, so that the makeup is not easily dislodged,
It has excellent makeup durability.

In addition, the copolymer used in the present invention can be changed in properties by adjusting the molecular structure, can be selected according to the product or purpose of use, and can thereby control the physical properties of the product. It is also advantageous in point.

Claims (1)

(57) [Claims] Acrylic obtained by radical copolymerization of a dimethylpolysiloxane compound having a radical polymerizable group at one end of a molecular chain with a radical polymerizable monomer mainly composed of acrylate and / or methacrylate as a film-forming agent. -A cosmetic comprising a silicone-based graft copolymer.