WO2010098126A1

WO2010098126A1 - Make-up cosmetic containing acrylic copolymer having cycloalkyl group

Info

Publication number: WO2010098126A1
Application number: PCT/JP2010/001319
Authority: WO
Inventors: 淳三井田; 奥山雅樹; 柿沢英美
Original assignee: 株式会社コーセー
Priority date: 2009-02-27
Filing date: 2010-02-26
Publication date: 2010-09-02
Also published as: TWI476215B; TW201035127A; CN102333518B; KR20110130404A; KR101679212B1; HK1165947A1; CN102333518A

Abstract

Disclosed is a make-up cosmetic, preferably a lip cosmetic, an eyelash cosmetic or an eye liner cosmetic, which contains an acrylic copolymer having a cycloalkyl group, has excellent gloss, adherability and water resistance, and also has superior long-lasting performance upon application. The acrylic copolymer having a cycloalkyl group is produced by polymerizing monomers comprising a component (a1) and a component (a2) and/or a component (a3), wherein the component (a1) is an acrylate or methacrylate containing a cycloalkyl group, the component (a2) is an acrylate or methacrylate containing a linear or branched alkyl group having 8 to 12 carbon atoms, and the component (a3) is an organopolysiloxane macromonomer containing a radically polymerizable group at one end. The content of the component (a1) is 50 to 90% by mass and the content of the component (a2) and/or the component (a3) is 10 to 50% by mass, both relative to the total amount of the constituent monomers. The acrylic copolymer is characterized in that at least 30% by mass of the acrylic copolymer can be dissolved in light isoparaffin at 25˚C.

Description

Makeup cosmetics containing a cycloalkyl group-containing acrylic copolymer

The present invention relates to a makeup cosmetic containing a cycloalkyl group-containing acrylic copolymer, and more specifically, contains a cycloalkyl group-containing acrylic copolymer that dissolves in a volatile oil such as light liquid isoparaffin. Makeup cosmetics, preferably, cosmetics for lips, cosmetics for eyelids, and eyeliner cosmetics.

1) Acrylic Copolymer An acrylic resin typified by polymethylmethacrylate forms a transparent and hard film and has good workability, so that it is widely used as an organic glass material and a coating material. However, acrylic resins are highly polar and dissolve in organic solvents such as acetone, toluene, butyl acetate, and chloroform, but are insoluble in paraffinic solvents such as light liquid isoparaffin and isododecane. It was difficult to apply as a forming agent. Especially in cosmetics, the use of organic solvents as described above is restricted due to skin safety and prescription type restrictions, so paraffinic solvents and silicones that can be generally used in cosmetics. It has been desired to develop an acrylic resin that is soluble in a solvent.

For example, an acryl-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. Copolymerizable with cosmetics characterized in containing (for example, see Patent Document 1), cycloalkyl group-containing monomers having a polymerizable double bond, and such monomers such as 2-ethylhexyl methacrylate A cosmetic comprising 1 to 60% by weight in terms of solid content of an aqueous polymer emulsion comprising a monomer having a double bond as a constituent (for example, see Patent Document 2) At least one acrylate of the formula CH ₂ ═CH—COOR ₂ , wherein R ₂ represents a C ₄ to C ₁₂ cycloalkyl group. A rate monomer and at least one methacrylate monomer of the formula CH ₂ ═C (CH ₃ ) —COOR ′ ₂ , wherein R ′ ₂ represents a C ₄ to C ₁₂ cycloalkyl group, A block polymer comprising at least one first block and at least one second block, characterized in that the block is obtained from an acrylic acid monomer and at least one monomer having a glass transition temperature of 20 ° C. or less; The preparation method (for example, refer patent document 3) is proposed.

Moreover, (co) polymer (A) obtained by (co) polymerizing a vinyl monomer containing acrylic acid cycloalkyl ester and / or methacrylic acid cycloalkyl ester in a proportion of 10% by weight or more in the vinyl monomer ) And an organic solvent have also been reported (for example, see Patent Document 4).
Further, in recent years, the applicant has (A) acrylates and / or methacrylates containing cycloalkyl groups and (B) acrylates containing linear or branched alkyl groups having 8 to 12 carbon atoms and / or An acrylic copolymer obtained by polymerizing a monomer containing methacrylate and / or (C) an organopolysiloxane macromonomer containing a radically polymerizable group at one end, wherein the component (A) The blending amount of the component (B) and / or (C) is 10 to 50% by weight, and at least 30% by weight is dissolved in light isoparaffin at 25 ° C. A cycloalkyl group-containing acrylic copolymer was developed (see Patent Document 5). However, this document was filed in Japan before February 27, 2009, which is the filing date of the patent application that is the basis of the priority claim of the present invention, and was published after February 27, 2009. Although the document describes that cycloalkyl group-containing acrylic copolymers can be used in cosmetics, particularly typical makeup cosmetics such as lip cosmetics, eyelid cosmetics, and eyeliners. Is not specifically disclosed.

2) Makeup cosmetics As makeup cosmetics, there are lipsticks, lip gloss and other lip cosmetics, vaginal cosmetics, eyeliner, foundation, face color, spot covers, etc. Of these, The prior arts of the cosmetics for lips, the cosmetics for eyelids and the eyeliner suitable for the present invention will be described below.
2-1) Cosmetics for lips Conventionally, some lip cosmetics that are excellent in water resistance, oil resistance, makeup holding effect and secondary adhesion preventing effect include a combination of an organic silicone resin and a volatile oil. For example, a technology in which an organic silicone resin having a specific structure and average molecular weight and a volatile oil are blended (see, for example, Patent Document 6), a volatile oil, a water-repellent polymer such as a silicone resin dissolved in the volatile oil, and a volatile oil A technique of blending a wax that is dispersed in a non-volatile oil component that is compatible with a volatile oil component (see, for example, Patent Document 7) has been studied.
These technologies are cosmetics that contain organic silicone resin dissolved in volatile oil, and the coating of organic silicone resin is formed by volatilization of volatile oil after application. Although a cosmetic having an excellent secondary adhesion preventing effect can be obtained, the film is hard and the cosmetic film lacks flexibility, so that the skin and the lips are hard to feel, and the coating film is not glossy.
Accordingly, it has been desired to develop a lip cosmetic that is excellent in color retention over time and secondary adhesion prevention effects, and is excellent in glossiness, burdeniness, and smooth use feeling.

2-2) Eyeliner cosmetics Conventionally, eyeliner cosmetics are cosmetics having a cosmetic effect that, when applied to the eyes, make the eyes look larger and the eyes clear. In addition to the ease of application, the required quality of the decorative film requires that the coating film is uniform, has a high gloss and color, and that the decorative film does not peel off or bleed over time. However, in order to maintain each effect, a film forming agent is blended.
In addition, since eyeliner cosmetics are easy to apply at the time of application and it is necessary to form a cosmetic film immediately after application, a volatile solvent is used. Typical examples include water, paraffinic solvents such as light liquid isoparaffin and isododecane, and silicone solvents such as cyclic organopolysiloxane and low molecular weight organopolysiloxane.
Film forming agents are roughly classified into those used by being dissolved in these solvents and those used by being dispersed in a solvent. Here, the film-forming agent dispersed in a solvent is a suspension in which fine particles of a polymer substance are stably dispersed in water or an organic solvent, and is obtained by polymerizing a monomer emulsified with a surfactant. And milky sap that exists in nature.
If a film forming agent dissolved in a solvent is used, it can be uniformly applied to the eyes, and if a film forming agent dispersed in a solvent is used, the formation of a decorative film can be accelerated.
Examples of these blending techniques include a technique for improving the usability and the sustainability of the cosmetic effect by using an oil-soluble film-forming resin and a fluorine compound-treated powder (for example, see Patent Document 8), In water-type makeup cosmetics, the outer phase contains an oil-soluble resin, and the inner phase contains an emulsion resin capable of forming a film, so that it has excellent water resistance, sweat resistance, sebum resistance, and oil resistance. Technology with excellent durability (see, for example, Patent Document 9), including a volatile oil in the fat phase, and dispersing a specific film-forming polymer in the aqueous phase to form a water-in-oil emulsion, making it easy to apply and extend, Examples thereof include a technique that is uniform, non-sticky, and does not transfer or diffuse (see, for example, Patent Document 10).
However, the technique of Patent Document 8 can improve the strength and water resistance of the decorative film and improve the durability of the cosmetic effect by using the oil-soluble film-forming resin and the fluorine compound-treated powder. Due to the lack of transparency of the decorative film, the original color of the colorant cannot be exhibited, resulting in poor color development. Also, when the oil-in-water makeup cosmetic contains an oil-soluble resin and the inner phase contains an emulsion resin capable of forming a film, as in the technique of Patent Document 9, prevent peeling and bleeding of the decorative film. However, in order to ensure stability, a large amount of wax, natural clay mineral, or surfactant must be added, and as a result, makeup can be improved. There was a drawback that the film was fogged and it was difficult to obtain a decorative film with good color. In particular, when the amount of the surfactant is increased, there is a drawback in that the smear of the decorative film is generated. Furthermore, in the technique of Patent Document 10 that forms a uniform cosmetic film without stickiness by containing a volatile oil in the fat phase and dispersing a specific film-forming polymer in the aqueous phase to form a water-in-oil emulsion. Although uniformity of the decorative film was obtained, the decorative film was soft and the adhesion was low.
In the conventional technology, the cosmetic film can be made uniform with good usability, but because of lack of transparency, it is not possible to obtain a glossy feeling and color development. However, over time, it peeled off and sometimes lost its makeup effect. Therefore, there has been a demand for the development of an eyeliner cosmetic that has a uniform cosmetic film, has a good gloss and color, and has a long-lasting cosmetic effect.

2-3) Cosmetics for wrinkles Conventionally, cosmetics for wrinkles, when applied to wrinkles, make wrinkles look curled (curl effect), appear darker or thicker (volume effect) It is a cosmetic that makes it look long (long effect). In order to maintain each effect, a film forming agent is blended to prevent the decorative film from collapsing.
Moreover, since the cosmetics for vaginal are easy to apply | coat to a wrinkle and it is necessary to form a cosmetic film quickly after application | coating, the volatile solvent is used like an eyeliner.
As a technique using a film-forming agent, a technique of blending a film-forming resin and a film-forming polymer emulsion (for example, Patent Document 11), or a technique using trimethylsiloxysilicic acid and an acrylic-silicone graft copolymer (For example, patent document 12) is mentioned and the technique using combining the film formation agent from which a kind differs is examined.
However, recently, it has been difficult to maintain the curl effect and make other effects coexist, even though it has been desired that the cosmetics for acupuncture have multiple effects. It was. For example, if you want to obtain volume effect, long effect and curl effect, it is necessary to make a strong cosmetic film in order to attach more wax, powder, fiber, etc. to the cocoon and prevent the cocoon from becoming heavy and falling . Then, due to movement such as blinking, the decorative film is cracked and peeled off, the volume effect and the long effect are lost, and further, the transparent feeling of the decorative film is lost, and the glossiness of the wrinkles may be lost. In addition, since it becomes a hard decorative film, the feeling of use was not good. In addition, the aqueous dispersion of the film-forming agent and the solvent dispersion can impart a proper strength and maintain the curl effect while the decorative film is flexible, but the uniformity of the decorative film is obtained. Therefore, the glossy feeling is lowered and the color development is felt to be poor, so that the effect of conspicuous eyes may not be sufficiently obtained.
Therefore, it has been desired to develop a vaginal cosmetic that is excellent in curling effect and sustainability, and at the same time has other effects.

Japanese Patent No. 2704730 JP-A-8-231344 JP 2008-31479 A JP 62-84165 A JP 2009-46662 A JP-A-9-124430 JP-A-9-143034 JP 2001-187715 A Japanese Patent No. 3393903 Japanese Patent Laid-Open No. 10-203919 JP-A-8-268841 JP-A-7-196449

The problem of the present invention is that it contains the cycloalkyl group-containing acrylic copolymer described in Patent Document 5 developed by the applicant, and is excellent in gloss, adhesion and water resistance, and extremely excellent in makeup sustainability. It is to provide makeup cosmetics.
In particular, for lip cosmetics, it is an eyeliner that has excellent color retention and secondary adhesion prevention effects over time, and is excellent in glossiness, no burden, and smooth use feeling. For cosmetics, it is to provide eyeliner cosmetics that have a uniform cosmetic film, good gloss and color, and have a long lasting cosmetic effect. It is to provide a vaginal cosmetic that is excellent in its sustainability and has other effects at the same time.

As a result of intensive studies to solve the above problems, the present inventors have found that an acrylic copolymer containing a cycloalkyl group having a specific structure can solve the above problems, and completed the present invention. It came to do.

That is, the present invention
(1) An acrylic copolymer obtained by polymerizing a monomer containing the following component (a1) and component (a2) and / or component (a3), wherein the component (a1) The blending amount of the component (a2) and / or the component (a3) is 10 to 50% by weight, and at least 30% by weight is dissolved in light liquid isoparaffin at 25 ° C. Makeup cosmetics containing a cycloalkyl group-containing acrylic copolymer,
Component (a1): Formula (I)

(Wherein R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents a cycloalkyl group) An acrylate and / or methacrylate component (a2):

An acrylate and / or methacrylate component (a3) represented by the formula (wherein R ₃ represents a hydrogen atom or a methyl group, and R ₄ represents a linear or branched alkyl group having 8 to 12 carbon atoms): one end The above-mentioned (1), wherein an organopolysiloxane macromonomer containing (2) a cycloalkyl group-containing acrylic copolymer is obtained by polymerizing components (a1) and (a2). Make-up cosmetics,
(3) A makeup cosmetic as described in (1) above, wherein the cycloalkyl group-containing acrylic copolymer is obtained by polymerizing the component (a1) and the component (a3),
(4) The make-up makeup as described in (1) above, wherein the cycloalkyl group-containing acrylic copolymer is obtained by polymerizing the component (a1), the component (a2) and the component (a3). Fee,
(5) Component (a3) is represented by the following general formula (III)

(Wherein R ₅ represents a hydrogen atom or a methyl group, R ₆ to R ₁₂ each independently represents an alkyl group having 1 to 5 carbon atoms, m represents any integer of 1 to 10, n The makeup cosmetic according to any one of (1), (3) and (4) above, wherein the organic polysiloxane macromonomer is represented by any one of 0 to 200) ,
(6) The makeup cosmetic according to any one of (1) to (5) above, wherein the component (a1) is cyclohexyl methacrylate,
(7) The weight average molecular weight in terms of polystyrene measured by liquid gel permeation chromatography of the cycloalkyl group-containing acrylic copolymer is 1.0 × 10 ⁴ to 2.0 × 10 ^5. (1) to (6) makeup cosmetics according to any one of
(8) The makeup cosmetic according to any one of (1) to (7), further comprising a volatile oil agent,
(9) The makeup cosmetic as described in (8) above, wherein the volatile oil is light liquid isoparaffin,
(10) The makeup cosmetic according to any one of (1) to (9), further comprising a powder containing or not containing a colorant,
(11) The makeup cosmetic according to any one of (1) to (10) above, which is a lip cosmetic, an eyeliner cosmetic, or a vaginal cosmetic;
(12) A cosmetic for lips, comprising a non-volatile hydrocarbon oil that is liquid at 25 ° C.
(13) The eyeliner cosmetic or vaginal cosmetic, wherein the colorant-containing powder contains silicic anhydride, and the makeup cosmetic according to (10) above.

(1) Cycloalkyl group-containing acrylic copolymer The acrylic copolymer of the present invention is an acrylic polymer obtained by polymerizing monomers containing the following (a1) and component (a2) and / or component (a3). Copolymer.
Component (a1): Formula (I)

An acrylate and / or methacrylate component (a3) represented by the formula (wherein R ₃ represents a hydrogen atom or a methyl group, and R ₄ represents a linear or branched alkyl group having 8 to 12 carbon atoms): one terminal Organopolysiloxane macromonomer containing a radical polymerizable group

The acrylic copolymer of the present invention has a component (a1) content of 50 to 90% by mass (hereinafter simply referred to as “%”), component (a2) and / or component (a3) in the total amount of constituent monomers. Is not particularly limited as long as it is a copolymer that is 10 to 50% and dissolves at least 30% in light liquid isoparaffin at 25 ° C.
In the present invention, the light liquid isoparaffin in the definition of “soluble in light liquid isoparaffin at 25 ° C. at 25%” is a mixture of hydrocarbons mainly composed of isoparaffin, and a petroleum product distillation test method defined in JIS K2254. The initial distillation temperature is 166 ° C., the distillation end point is 202 ° C., and the kinematic viscosity at 37.8 ° C. is 1.28 mm ² / s. As a commercial item, there exists IP solvent 1620 (made by Idemitsu Kosan Co., Ltd.), for example.

The acrylate and / or methacrylate containing the cycloalkyl group of the component (a1) is a lipophilic polymerizable monomer and serves as a skeleton for imparting water resistance, transparency and hardness to the film.
Here, the acrylate and / or methacrylate containing a cycloalkyl group is one or more of an acrylate containing a cycloalkyl group, one or more of a methacrylate containing a cycloalkyl group, and these Includes mixtures.
The cycloalkyl group is usually a cycloalkyl group having 5 to 10 carbon atoms, preferably a cycloalkyl group having 6 to 8 carbon atoms, and particularly preferably a cyclohexyl group.
Specific examples of cycloalkyl group-containing acrylates or methacrylates include cyclohexyl acrylate, cyclohexyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, tricyclodecyl acrylate, tricyclodecyl methacrylate, tricyclodecanyl acrylate, and tricyclodecane. Nyl methacrylate etc. are mentioned, These can be used 1 type or 2 or more types. In particular, cyclohexyl methacrylate is particularly preferable because it has a good radical polymerizability, a high yield, and a copolymer having a suitable glass transition point for forming a hard film.

The acrylate and / or methacrylate containing a linear or branched alkyl group having 8 to 12 carbon atoms as component (a2) is an oleophilic polymerizable monomer, imparts flexibility and adhesion to the film, and has a light flow. It becomes a skeleton that enhances the solubility in isoparaffin.
Here, the acrylate and / or methacrylate containing a linear or branched alkyl group having 8 to 12 carbon atoms is one or more of acrylates containing a linear or branched alkyl group having 8 to 12 carbon atoms. , One or more methacrylates containing a linear or branched alkyl group having 8 to 12 carbon atoms, and mixtures thereof.
Examples of the linear or branched alkyl group having 8 to 12 carbon atoms include octyl, 2-ethylhexyl, nonyl, isononyl, lauryl and the like, preferably 2-ethylhexyl and lauryl, particularly preferably 2-ethylhexyl. is there.
Specific examples of the acrylate or methacrylate containing a linear or branched alkyl group having 8 to 12 carbon atoms include octyl acrylate, octyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isononyl acrylate, isononyl methacrylate, lauryl. Acrylate, lauryl methacrylate and the like can be mentioned, and one or more of these can be used, and 2-ethylhexyl methacrylate and lauryl methacrylate are preferred, and 2-ethylhexyl methacrylate is particularly preferred because it can improve solubility.

Examples of the organopolysiloxane macromonomer containing a radical polymerizable group at one end of the component (a3) include an ester compound in which an organopolysiloxane is linked to acrylic acid or methacrylic acid via a divalent hydrocarbon group. It becomes a skeleton for imparting water resistance to the film and enhancing the solubility in light liquid isoparaffin.
Specifically, the following formula (III)

(Wherein R ₅ represents a hydrogen atom or a methyl group, R ₆ to R ₁₂ each independently represents an alkyl group having 1 to 5 carbon atoms, m represents any integer of 1 to 10, n Represents an integer of 0 to 200), and these can be used singly or in combination of two or more.
Here, examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-pentyl and the like.

More specifically, the general formula (IV)

(Wherein R ₁₃ represents a hydrogen atom or a methyl group, R ₁₄ represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 200). Mention may be made of monomers.

In the formula (III), n representing the repeating unit of the dimethylpolysiloxane group is preferably 0 to 200, since sufficient water resistance can be obtained and a transparent and uniform film can be obtained. n is more preferably from 5 to 150 in terms of water resistance and a uniform film.

Further, the cycloalkyl group-containing acrylic copolymer of the present invention may contain a polymerizable monomer other than the above components (a1) to (a3) as an optional component as long as the effects of the present invention are not impaired. it can. The polymerizable monomer other than the components (a1) to (a3) is not particularly limited, but styrene, substituted styrene, vinyl acetate, acrylic acid, methacrylic acid, maleic anhydride, maleic acid ester, fumaric acid ester, vinyl chloride, Vinylidene chloride, ethylene, propylene, butadiene, acrylonitrile, fluorinated olefins, acrylamide, methacrylamide, methyl acrylamide, methyl methacrylamide, dimethyl methacrylamide, N-isopropyl acrylamide, N-vinyl pyrrolidone, N-vinyl acetamide, t-butyl acrylate , T-butyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl methacrylamide, 2-a It can be mentioned Riruamido 2-dimethyl propane sulfonic acid salts.

The blending ratio of the components (a1) to (a3) and optional monomers is as follows.
The blending amount of component (a1) is 50 to 90%, preferably 50 to 80%, of the total amount of constituent monomers. If it is less than 50%, a film with sufficient hardness cannot be obtained, and if it exceeds 90%, the solubility in light liquid isoparaffin deteriorates.
The amount of component (a2) and / or component (a2) is 10 to 50%, preferably 15 to 45% of the total amount of constituent monomers. If it is less than 10%, the solubility in light liquid isoparaffin becomes poor, and if it exceeds 50%, a film with sufficient hardness cannot be obtained, and there are disadvantages such as stickiness, tackiness, and film non-uniformity. Arise.
The blending amount of the optional component may be within a range of 30% or less of the total amount of the constituent monomers, and is preferably 20% or less, for example, 0.01 to 10%.

Further, the cycloalkyl group-containing acrylic copolymer obtained by polymerizing 10 to 50% of the component (a3) with respect to 50 to 90% of the component (a1) can form a particularly water-resistant film. The cycloalkyl group-containing acrylic copolymer obtained by polymerizing components (a2) and (a3) in a total proportion of 10 to 50% with respect to 50 to 90% of component (a1) is particularly hard and water resistant. It is possible to form a characteristic film.

The weight average molecular weight of the cycloalkyl group-containing acrylic copolymer of the present invention is not particularly limited, but is preferably in the range of 1.0 × 10 ⁴ to 2.0 × 10 ⁵ . Within this range, the ability to form a film that forms a uniform film can be exhibited. The weight average molecular weight is measured by liquid gel permeation chromatography (GPC) using tetrahydrofuran as an eluent and using a calibration curve prepared with a linear polystyrene standard and a refractive index detector.

(2) Method for Producing Cycloalkyl Group-Containing Acrylic Copolymer The cycloalkyl group-containing acrylic copolymer of the present invention contains the above components (a1) to (a3) and other optional monomers as necessary. It is used as a constituent monomer and can be obtained by random polymerization by a known polymerization method in the presence of an organic solvent and in the absence of water. Although not particularly limited, organic peroxides such as benzoyl peroxide and lauroyl peroxide, α, α′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2, The polymerization may be carried out in the presence of a radical polymerization initiator such as an azo compound such as 2′-azobis (2-methylbutyronitrile), a persulfuric acid polymerization initiator such as potassium persulfate or ammonium persulfate. A combination method, suspension polymerization method, bulk polymerization method, precipitation polymerization method and the like can be used. Among these, the solution polymerization method is particularly preferable because it is easy to adjust the molecular weight of the obtained acrylic copolymer to the optimum range.

Examples of the organic solvent used in the polymerization of the cycloalkyl group-containing acrylic copolymer of the present invention include aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate and butyl acetate. Esters, alcohols such as isopropanol, ethanol, methanol, and the like, and one or more of these may be used in combination. Moreover, it can also superpose | polymerize in paraffinic solvents, such as a light liquid isoparaffin, isododecane, and isohexadecane.

The polymerization reaction temperature of the cycloalkyl group-containing acrylic copolymer of the present invention is not particularly limited as long as it is within a temperature range in which a normal radical polymerization initiator can be used, but is usually in the range of 40 to 120 ° C. The reaction time varies depending on the radical polymerization initiator used, the type of monomer, and the reaction temperature, but is usually in the range of 2 to 24 hours. If the polymerization time is too short, the amount of residual monomer is large and the yield is lowered, which is not preferable.

The cycloalkyl group-containing acrylic copolymer of the present invention can be diluted with other hydrocarbons, esters, triglycerides and other oils while being dissolved in the paraffinic solvent when reacted, or other oils It is also possible to perform solvent substitution. The acrylic copolymer composition containing such an oil-soluble cycloalkyl group is also included in the component (A) of the present invention. Moreover, the solvent of the solution can be removed to take out the cycloalkyl group-containing acrylic copolymer as a solid, and the cycloalkyl group-containing acrylic copolymer can be further dissolved in a light liquid isoparaffin to dissolve the cycloalkyl group. It can also be used as a group-containing acrylic copolymer solution. Two or more of the above cycloalkyl group-containing acrylic copolymers and solutions thereof can be used in combination.

(3) Makeup Cosmetics The above cycloalkyl group-containing acrylic copolymers are made up of lip cosmetics such as lipstick and lip gloss, eye makeup cosmetics such as eyeliner and vaginal cosmetics, face colors and foundations. It is suitable as a component of up cosmetics, and in particular, can be suitably used as lip cosmetics, eyeliners, and vaginal cosmetics.
The makeup cosmetic of the present invention usually contains the cycloalkyl group-containing acrylic copolymer and a volatile oil. Furthermore, if necessary, powders (including colorants), oily components other than volatile oils, fibers, film-forming dispersions, surfactants, aqueous components, which are components commonly used in cosmetics, Ultraviolet absorbers, humectants, antifading agents, antioxidants, antifoaming agents, cosmetic ingredients, preservatives, fragrances, and the like can be appropriately blended within a range that does not impair the effects of the present invention.
For example, lip cosmetics, vaginal cosmetics and eyeliner cosmetics are preferably formulated as follows.
(Lip cosmetics)
(A) Cycloalkyl group-containing acrylic copolymer of the present invention (B) Volatile oil agent (C) Powder containing colorant,
And if necessary,
(D) Nonvolatile hydrocarbon oil that is liquid at 25 ° C
(Cosmetic cosmetics and eyeliner)
(A) cycloalkyl group-containing acrylic copolymer of the present invention (B) volatile oil agent, and
(C) Powder with or without colorant
(C) more preferably contains silicic anhydride.

Hereinafter, each component will be described in detail.
(Cycloalkyl group-containing acrylic copolymer)
The cycloalkyl group-containing acrylic copolymer is as described above. The blending amount of the cycloalkyl group-containing acrylic copolymer is usually 0.1 to 40% as a solid content (however, 0.1 to 30% in the case of cosmetics for lips), preferably 1 to 25%. More preferably, it can be about 2 to 20%. Within this range, for example, lip cosmetics are particularly excellent in terms of color retention over time, secondary adhesion prevention effects, and lack of burden. In addition, the cosmetics for wrinkles have no stickiness at the time of finishing, a film having a uniform and high coating strength is formed, and a glossy, curling power and excellent durability can be obtained. In addition, eyeliner cosmetics are easy to draw a line, and a uniform and high-strength cosmetic film is formed, so that a glossy, colored, and excellent sustainability can be obtained.
The cycloalkyl group-containing acrylic copolymer is used by dissolving in a volatile oil, and it is preferable to use it by dissolving in light liquid isoparaffin. The concentration of the cycloalkyl group-containing acrylic copolymer in the volatile oil is preferably 15 to 50%.

(Volatile oil)
Volatile oil acts as a solvent for cycloalkyl group-containing acrylic copolymers, facilitating the blending of cycloalkyl group-containing acrylic copolymers, resulting in less stickiness at the finish and forming a uniform film Is done.
The volatile oil is not particularly limited as long as it is volatile at 1 atm and 25 ° C. and is usually used in cosmetics. Specifically, light liquid isoparaffin, decamethylcyclopentasiloxane, octamethylcyclohexane Examples include tetrasiloxane, dodecamethylcyclohexasiloxane, methyltrimethicone, dimethylpolysiloxane, decamethyltetrasiloxane, and ethyltrisiloxane. Here, the light liquid isoparaffin can be used without being limited to those used as the standard of solubility.
The following are mentioned as a commercial item. As the light liquid isoparaffin, Isopar H (Esso Chemical Co., Ltd.), Isododecane (Bayer Co., Ltd.), Isohexadecane (Unikema Co., Ltd.), IP Solvent 1620MU, IP Solvent 2028MU, IP Solvent 2835 (above, Idemitsu Kosan Co., Ltd.), etc. As decamethylcyclopentasiloxane, TFS405 (manufactured by Toshiba Silicone), SH245, DC345 (manufactured by Dow Corning Toray), KF-995 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. 1.5 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc., as methylpolysiloxane, KF-96L-2CS (manufactured by Shin-Etsu Chemical Co., Ltd.), etc., and as decamethyltetrasiloxane, KF-96L-1.5CS (manufactured by Shin-Etsu Chemical Co., Ltd.) ), Etc., ethyltrisiloxane is SILSO FT ETS (manufactured by Momentive Performance Materials). Among these, light liquid isoparaffin is preferable in that the cycloalkyl group-containing acrylic copolymer of component (A) has good solubility and a uniform decorative film can be obtained. These volatile oils can be used alone or in combination of two or more as required.

The blending amount of the volatile oil is not particularly limited. For example, in the case of lip cosmetics, 10 to 90% is preferable, and 15 to 85% is more preferable. When it mix | blends in this range, it will become the thing especially excellent in the point of makeup lasting, secondary adhesion prevention effect, and usability. In the case of eyeliner cosmetics and vaginal cosmetics, 1 to 80% is preferable, and 1 to 70% is more preferable. Within this range, there is no stickiness at the finish, a uniform and high-strength coating film is formed, and the glossiness is excellent, and eyeliner cosmetics with further excellent color development and sustainability are obtained. In addition, the vaginal cosmetics can be further improved in curling power and durability.

(powder)
By blending the powder, it can be colored, the drying speed can be increased, and the stickiness of the finish can be further suppressed.
The powder may be any powder generally used in cosmetics, such as a plate shape, a spindle shape, a needle shape, a particle size such as a fume shape, a fine particle, or a pigment grade, and a porous or nonporous shape. It is not particularly limited by the particle structure and the like, and inorganic powders, glitter powders, metal powders, organic powders, pigment powders, composite powders, fibers, and the like can be used.

More specifically, for example, one or more of the following can be used.
Conger, ultramarine, bengara, yellow iron oxide, black iron oxide, titanium oxide, zinc oxide, titanium / titanium oxide sintered product, cerium oxide, magnesium oxide, zirconium oxide, antimony oxide, magnesium carbonate, calcium carbonate, chromium oxide, water Chromium oxide, carbon black, aluminum silicate, magnesium silicate, calcium silicate, barium silicate, magnesium aluminum silicate, magnesium magnesium silicate, mica, synthetic mica, synthetic sericite, sericite, talc, silicic anhydride, Inorganic powders such as muscovite, phlogopite, saucite, biotite, kaolin, barium sulfate, bentonite, smectite, siliceous earth, hydroxyapatite, boron nitride;
Bismuth oxychloride, titanium mica, titanium oxide coated bismuth oxychloride, iron oxide coated mica, iron oxide coated mica titanium, bitumen coated mica titanium, carmine coated mica titanium, organic pigment coated mica titanium, iron oxide / titanium oxide coated synthetic phlogopite Luminous powders such as fish phosphorus foil, titanium dioxide coated glass flakes, polyethylene terephthalate / aluminum / epoxy laminated powder, polyethylene terephthalate / polyolefin laminated film powder, polyethylene terephthalate / polymethyl methacrylate laminated film powder;
Polyamide resins, polyethylene resins, polyacrylic resins, polyester resins, fluorine resins, cellulose resins, polystyrene resins, copolymer resins such as styrene-acrylic copolymer resins, polypropylene resins, silicone resins, urethane resins Organic polymer resin powder such as N-acyl lysine;
Natural organic powders such as starch, silk powder, and cellulose powder, organic tar pigments, and pigment powders such as organic pigment lake pigments;
Metal powders such as aluminum powder, gold powder and silver powder;
Composite powders such as fine particle titanium oxide coated mica titanium, fine particle zinc oxide coated mica titanium, barium sulfate coated mica titanium;
Synthetic fibers such as nylon, polypropylene and polyester, artificial fibers such as rayon, natural fibers such as cellulose, semi-synthetic fibers such as acetate silk, and fibers such as composite fibers in which polyethylene terephthalate and nylon are layered.
In addition, these powders may be used in a combination of two or more types, such as fluorine compounds, silicone compounds, metal soaps, lecithin, hydrogenated lecithin, collagen, higher fatty acids, higher alcohols, esters, waxes, The surface treatment may be performed by a known method using one or more of wax, fats and oils, hydrocarbons, surfactants, amino acid compounds, water-soluble polymers and the like. These powders can be used alone or in combination of two or more.

As the colorant, those commonly used in cosmetics, including those that can be used as the colorant in the specific examples of the above powder, are used, and are spherical, plate-like, spindle-like, and needle-like. Etc., particle sizes such as fumes, fine particles, pigment grades, and particle structures such as porous and nonporous, etc., are not particularly limited, white inorganic pigments, colored inorganic pigments, colored organic pigments , Dyes, glitter pigments, metal powders, composite powders, and the like can be used.
More specifically, for example, one or more of the following can be used.
White inorganic pigments such as titanium oxide, zinc oxide, cerium oxide, barium sulfate;
Colored inorganic pigments such as iron oxide, carbon black, chromium oxide, chromium hydroxide, bitumen, ultramarine, bengara;
Mica titanium, bismuth oxychloride, organic pigment-treated mica titanium, titanium dioxide coated mica, titanium dioxide coated synthetic phlogopite, titanium dioxide coated bismuth oxychloride, iron oxide mica titanium, bituminized mica titanium, carmine treated mica titanium, fish scale foil, Bright pigments such as titanium dioxide-coated glass powder, polyethylene terephthalate / aluminum / epoxy laminated powder, polyethylene terephthalate / polyolefin laminated film powder, polyethylene terephthalate / polymethyl methacrylate laminated film powder, etc .;
Organic pigments such as red 201, red 202, red 205, red 226, red 228, orange 203, orange 204, blue 404, yellow 401;
Organic pigments such as zirconium, barium or aluminum lake such as Red No. 3, Red No. 104, Red No. 106, Orange No. 205, Yellow No. 4, Yellow No. 5, Green No. 3, Blue No. 1;
Metal powders such as aluminum powder, gold powder and silver powder;
Composite powder of fine particle titanium oxide-coated mica titanium, fine particle zinc oxide-coated mica titanium, barium sulfate-coated mica titanium, titanium oxide-containing silicon dioxide, zinc oxide-containing silicon dioxide, and the like.
These are one or more of fluorine compounds, silicone compounds, metal soaps, lecithins, hydrogenated lecithins, collagens, hydrocarbons, higher fatty acids, higher alcohols, esters, waxes, waxes, surfactants, etc. Surface treatment may be performed using

Furthermore, by including silicic acid anhydride in the powder, the drying rate is increased, and a good product is obtained in terms of non-stickiness of the finish. Even better in terms of points.
As the silicic anhydride, those commonly used in cosmetics can be used, and those having an amorphous structure, those having a hydrophobic treatment, or those having a crystal structure can be suitably used. The size of the particles is not particularly limited, but is preferably 1 nm to 50 μm, more preferably 3 nm to 30 μm, when measured with a volume average particle diameter laser diffraction particle size distribution analyzer. When the amount is within this range, a material with a better feeling of use can be obtained.
Examples of commercially available products include Cylisia 550, Cylicia 770, Cyrossphere C-1504 (manufactured by Fuji Silysia Chemical), AEROSIL200, AEROSIL300, AEROSILR972 (manufactured by Nippon Aerology Co., Ltd.), Nipsea E-220 (manufactured by Tosoh Silica), and the like. It is done. These silicic anhydrides can be used alone or in combination of two or more.

The blending amount of the powder is not particularly limited. For example, in the case of lip cosmetics, it is 0.01 to 25%, preferably 0.1 to 20%. Within this range, satisfactory results can be obtained in terms of imparting a decorative film with good color without fogging, color retention, and secondary adhesion prevention effects. For eyeliner cosmetics and vaginal cosmetics, the content is preferably 0.1 to 60%, and more preferably 0.5 to 45%. Within this range, coloring is possible, there is no stickiness at the finish, a uniform and high-strength coating film is formed, and the glossiness is excellent. In the eyeliner cosmetic, coloring and sustainability are further excellent. In the cosmetics for vaginal skin, products having further excellent curling power and sustainability can be obtained.
In addition, when silicic acid anhydride is contained in the powder, for example, in an eyeliner cosmetic or a vaginal cosmetic, the blending amount of silicic acid anhydride in the powder is 3 to 100%, preferably 6 to 40 %.

(Non-volatile hydrocarbon oil that is liquid at 25 ° C)
For example, the lip cosmetic can further impart a plastic effect to the cycloalkyl group-containing acrylic copolymer of the present invention by containing a non-volatile hydrocarbon oil that is liquid at 25 ° C. And it is preferable at the point which produces the absence of a feeling of burden. Among these, the non-volatile hydrocarbon oil whose viscosity in 98.9 degreeC is 200 mm < ² > / s is preferable. In particular, heavy liquid isoparaffin, polybutene, and polyisobutene are preferable. Examples of the commercially available products include Pearl Ream 18, Pearl Ream 24, Pearl Ream 46 (Nippon Yushi Co., Ltd.), Polybutene 100R, Polybutene 300R, Polybutene 2000H (Made by Idemitsu Kosan Co., Ltd.), and the like. Moreover, these can use 1 type (s) or 2 or more types as needed.
The blending amount of the non-volatile hydrocarbon oil that is liquid at 25 ° C. is 0.5 to 50%, preferably 1 to 10%. Within this range, satisfactory results can be obtained in terms of color durability and no sense of burden.

(Other ingredients)
Oils other than volatile oils and non-volatile hydrocarbon oils that are liquid at 25 ° C., fibers, film-forming dispersions, surfactants, aqueous components, UV absorbers, humectants, anti-fading agents, antioxidants, antifoaming Agents, cosmetic ingredients, preservatives, fragrances and the like.
This will be specifically described below.

(Oil agents other than volatile oils and non-volatile hydrocarbon oils that are liquid at 25 ° C)
As an oil agent other than a volatile oil agent and a non-volatile hydrocarbon oil that is liquid at 25 ° C., it can be used without particular limitation as long as it is an oil component usually used in cosmetics. The origin of animal oil, vegetable oil, synthetic oil, Regardless of properties such as solid oil, semi-solid oil, liquid oil, etc., hydrocarbons, fats and oils, waxes, hardened oils, ester oils, fatty acids, higher alcohols, silicone oils, fluorine oils, Lanolin derivatives, oily gelling agents and the like can be used.
Specifically, the following 1 type (s) or 2 or more types can be used.
Hydrocarbons such as liquid paraffin, α-olefin oligomer, squalane, petrolatum, ceresin wax, polyethylene wax, Fischer-Tropsch wax, paraffin wax, microcrystalline wax, ozokerite wax, ethylene propylene copolymer;
Oils and fats such as olive oil, castor oil, mink oil, macadamia nut oil, and mole;
Waxes such as beeswax, carnauba wax, candelilla wax, gay wax, montan wax;
Rosin acid pentaerythritol ester, dipentaerythritol fatty acid ester, cholesterol fatty acid ester, N-lauroyl-L-glutamate di (cholesteryl behenyl octyldodecyl), isopropyl myristate, isopropyl palmitate, cetyl 2-ethylhexanoate, Esters such as octyldodecyl myristate, glyceryl trioctanoate, polyglyceryl diisostearate, polyglyceryl triisostearate, diisostearyl malate, neopentyl glycol dioctanoate, jojoba oil;
Fatty acids such as stearic acid, lauric acid, myristic acid, behenic acid, isostearic acid, oleic acid;
Higher alcohols such as stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, behenyl alcohol;
Silicones such as low polymerization dimethylpolysiloxane, high polymerization dimethylpolysiloxane, methylphenylpolysiloxane, alkoxy-modified polysiloxane, cross-linked organopolysiloxane, fluorine-modified polysiloxane;
Fluorinated oils such as perfluorodecane, perfluorooctane, perfluoropolyether;
Lanolin derivatives such as lanolin, lanolin acetate, lanolin fatty acid isopropyl, lanolin alcohol;
12-hydroxystearic acid, dextrin palmitate, dextrin palmitate / 2-ethylhexanoate, dextrin stearate, dextrin palmitate / dextrin stearate, dextrin oleate, dextrin isopalmitate, dextrin fatty acid esters of dextrin isostearate, stearin Oily gelling agents such as acid sucrose, sucrose fatty acid ester of sucrose acetate stearate, aluminum isostearate and calcium stearate.

(Film-forming dispersion)
As the film-forming dispersion, a polymer having film-forming ability is emulsified in an aqueous solvent or a polymer dispersed in an oil-based solvent, and is usually used in cosmetics. There is no particular limitation, and any of them can be used. Examples of emulsions in an aqueous solvent include alkyl acrylate copolymer emulsions, alkyl acrylate / styrene copolymer emulsions, polyvinyl acetate emulsions, and vinylpyrrolidone / styrene copolymer emulsions, which are commercially available. Products include iodosol 32A707, iodosol GH810F, iodosol GH800F (manufactured by NSC Japan), plexitol B-500 (manufactured by ROHM GMBH), iodosol GH41F (manufactured by NSC Japan), vinibran 1080, vinibran 1128C, vinibran 1080M , Vinibrand 1080T, Vinibrand GV-5651, Vinibrand 1108S / W (Nissin Chemical Industry Co., Ltd.), ANTARA430 (produced by ISP). Examples of the dispersion in an oily solvent include an alkyl acrylate / styrene copolymer emulsion, and a commercially available product is Nissetsu U-3700A (manufactured by Nippon Carbide Industries Co., Ltd.).

(Surfactant)
As the surfactant, any surfactant that is generally used in cosmetics can be used. Nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, etc. Is mentioned.
Examples of the nonionic surfactant include glycerin fatty acid ester and its alkylene glycol adduct, polyglycerin fatty acid ester and its alkylene glycol adduct, propylene glycol fatty acid ester and its alkylene glycol adduct, sorbitan fatty acid ester and its alkylene glycol addition. Sorbitol fatty acid ester and its alkylene glycol adduct, polyalkylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyalkylene alkyl ether, glycerin alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene hydrogenated castor oil, lanolin alkylene Glycol adduct, polyoxyalkylene alkyl co-modified silicone, polyether-modified silicone And the like.
Examples of the anionic surfactant include inorganic and organic salts of fatty acids such as stearic acid and lauric acid, alkylbenzene sulfates, alkylsulfonates, α-olefinsulfonates, dialkylsulfosuccinates, α-sulfonated fatty acids. Salt, acylmethyl taurine salt, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate, N-acyl amino acid salt , O-alkyl substituted malates, alkylsulfosuccinates and the like.
Examples of the cationic surfactant include alkylamine salts, polyamines and alkanolamine fatty acid derivatives, alkyl quaternary ammonium salts, and cyclic quaternary ammonium salts.
Examples of amphoteric surfactants include amino acid type and betaine type carboxylic acid types, sulfate ester types, sulfonic acid types, and phosphate ester types, and those that are safe for the human body can be used. For example, N, N-dimethyl-N-alkyl-N-carboxylmethyl ammonium betaine, N, N-dialkylaminoalkylene carboxylic acid, N, N, N-trialkyl-N-sulfoalkylene ammonium betaine, N, N— Examples thereof include dialkyl-N, N-bis (polyoxyethylene sulfate) ammonium betaine, 2-alkyl-1-hydroxyethyl-1-carboxymethylimidazolinium betaine, and lecithin.

(Aqueous component)
The aqueous component may be any component that is soluble in water, for example, alcohols such as ethyl alcohol and isopropyl alcohol; glycols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol, and polyethylene glycol Glycerols such as glycerin, diglycerin, polyglycerin; saccharides such as sorbitol, maltitol, sucrose, starch sugar, lactitol; guar gum, sodium chondroitin sulfate, sodium hyaluronate, gum arabic, sodium alginate, carrageenan, methylcellulose, hydroxy Water-soluble polymers such as ethyl cellulose, carboxymethyl cellulose, carboxyvinyl polymer, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate; Sodium, magnesium chloride, salts such as sodium lactate; aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender, plant extracts, etc. and water rose like.
(Humectant)
As humectants, natural products such as guar gum, sodium chondroitin sulfate, sodium hyaluronate, gum arabic, sodium alginate, carrageenan; semi-synthetic products such as methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose; carboxyvinyl polymer, alkyl addition Synthetic compounds such as carboxyvinyl polymer, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, and the like; other proteins, mucopolysaccharides, collagen, elastin, keratin and the like.

(Others such as UV absorbers and antioxidants)
Examples of ultraviolet absorbers include benzophenone-based, PABA-based, cinnamic acid-based, salicylic acid-based, 4-tert-butyl-4′-methoxydibenzoylmethane, and oxybenzone. Examples of antioxidant include α-tocopherol, Ascorbic acid and the like, cosmetic ingredients such as vitamins, anti-inflammatory agents, herbal medicines and the like, and antiseptics include paraoxybenzoic acid esters, phenoxyethanol, 1,2-pentanediol and the like, for example.

(Dosage form, form, etc.)
The make-up cosmetic of the present invention is not particularly limited as a dosage form, and examples thereof include a water-in-oil type, an oil-in-water type, an oily type, and a powder type. The oily type is a cosmetic having a continuous phase of an oily component that is a liquid, semi-solid or solid oil agent or oil-soluble compound, and is substantially free of water. Moreover, a form etc. can be suitably selected according to a use.
For example, as the lip cosmetic, the dosage form is not particularly limited, but an oily type or a water-in-oil type in which the outer phase is oily is preferable from the viewpoint of color retention and gloss. Shapes include solid, semi-solid, and liquid forms, and can be used as lipsticks, lip glosses, lip treatments, lip balms, lip bases for bases, lipstick overcoats, and the like.
The eyeliner cosmetic is preferably an oily type. Examples of the form include liquid, semi-solid and solid. As the vaginal cosmetic, an oily type is preferable. Examples of the form include liquid, semi-solid and the like, which can be used as mascara, mascara overcoat, mascara base, and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not limited to these illustrations.
I. Production of acrylic copolymer containing cycloalkyl group

[Production Example 1]
[Synthesis of Cycloalkyl Group-Containing Acrylic Copolymer (1)]
A four-necked separable flask (hereinafter simply referred to as “flask”) equipped with a reflux condenser, a thermometer, a nitrogen inlet tube and a stirrer was added 22.5 g of cyclohexyl methacrylate, 7.5 g of 2-ethylhexyl methacrylate and toluene. 70 g was added, nitrogen gas was introduced and the atmosphere was sufficiently nitrogen, then heated to 100 ° C., and 0.15 g of α, α′-azobisisobutyronitrile (hereinafter referred to as AIBN) was added. The mixture was refluxed for 3 hours for polymerization. Methanol was injected into the obtained reaction product to precipitate an acrylic copolymer, and the precipitate was filtered and dried under vacuum to obtain 27.4 g of a solid content of cycloalkyl group-containing acrylic copolymer. The weight average molecular weight in terms of polystyrene was 5.0 × 10 ⁴ .

[Production Example 2]
[Synthesis of Acrylic Copolymer Containing Cycloalkyl Group (2)]
Add 15 g of cyclohexyl methacrylate, 15 g of 2-ethylhexyl methacrylate, and 70 g of toluene to the above flask, introduce nitrogen gas into a nitrogen atmosphere, warm to 100 ° C., add 0.15 g of AIBN, and reflux for 3 hours. And polymerized. Methanol was injected into the obtained reaction product to precipitate an acrylic copolymer, and the precipitate was filtered off and dried under vacuum to obtain 25.5 g of a cycloalkyl group-containing acrylic copolymer solid content. The weight average molecular weight in terms of polystyrene was 3.7 × 10 ⁴ .

[Production Example 3]
[Synthesis of Cycloalkyl Group-Containing Acrylic Copolymer (3)]
To the flask was added 21 g of cyclohexyl methacrylate, 9 g of 2-ethylhexyl methacrylate and 70 g of toluene, and after introducing nitrogen gas to make a sufficient nitrogen atmosphere, the mixture was heated to 100 ° C. and 0.15 g of AIBN was added. The mixture was refluxed for a period of time for polymerization. Methanol was injected into the resulting reaction product to precipitate an acrylic copolymer, and the precipitate was filtered off and dried under vacuum to obtain 23.8 g of a cycloalkyl group-containing acrylic copolymer solid. The weight average molecular weight in terms of polystyrene was 4.7 × 10 ⁴ .

[Production Example 4]
[Synthesis of Cycloalkyl Group-Containing Acrylic Copolymer (4)]
Add 22.5 g of cyclohexyl methacrylate, 7.5 g of methacryl-modified dimethylpolysiloxane macromonomer of the following formula (V) and 70 g of toluene to the above flask, introduce nitrogen gas into a nitrogen atmosphere, and heat up to 80 ° C. Then, 0.15 g of α, α′-azobisisobutyronitrile (hereinafter referred to as AIBN) was added and refluxed for 5 hours for polymerization. Methanol was injected into the obtained reaction product to precipitate an acrylic copolymer, and the precipitate was filtered and dried under vacuum to obtain 13.4 g of a solid content of cycloalkyl group-containing acrylic copolymer. The weight average molecular weight in terms of polystyrene was 5.2 × 10 ⁴ .

[Production Example 5]
[Synthesis of Cycloalkyl Group-Containing Acrylic Copolymer (5)]
After adding 22.5 g of cyclohexyl methacrylate, 7.5 g of methacryl-modified dimethylpolysiloxane macromonomer of the following formula (VI) and 70 g of toluene to the flask and introducing nitrogen gas to make a nitrogen atmosphere sufficiently, up to 100 ° C. The mixture was warmed, 0.15 g of AIBN was added, and the mixture was refluxed for 3 hours for polymerization. Toluene was distilled off from the obtained reaction product by evaporation, followed by vacuum drying to obtain 26.6 g of a cycloalkyl group-containing acrylic copolymer solid content. The weight average molecular weight in terms of polystyrene was 6.7 × 10 ⁴ .

[Production Example 6]
[Synthesis of Cycloalkyl Group-Containing Acrylic Copolymer (6)]
Add 22.5 g of cyclohexyl methacrylate, 7.5 g of methacryl-modified dimethylpolysiloxane macromonomer of the following formula (VII) and 70 g of toluene to the above flask, introduce nitrogen gas into a nitrogen atmosphere, and then heat up to 80 ° C. Warm, 0.15 g of AIBN was added and refluxed for 5 hours for polymerization. Methanol was injected into the obtained reaction product to precipitate an acrylic copolymer, and the precipitate was filtered off and dried under vacuum to obtain 29.1 g of a cycloalkyl group-containing acrylic copolymer solid content.

[Production Example 7]
[Synthesis of Cycloalkyl Group-Containing Acrylic Copolymer (7)]
To the flask, 21 g of cyclohexyl methacrylate, 4.5 g of 2-ethylhexyl methacrylate, 4.5 g of methacryl-modified dimethylpolysiloxane macromonomer of the above formula (VI) and 70 g of toluene were added, and nitrogen gas was introduced to make a sufficient nitrogen atmosphere. Thereafter, the mixture was heated to 80 ° C., 0.15 g of AIBN was added, and the mixture was refluxed for 5 hours for polymerization. Methanol was injected into the obtained reaction product to precipitate an acrylic copolymer, and the precipitate was filtered and dried under vacuum to obtain 11.0 g of a cycloalkyl group-containing acrylic copolymer solid content. The weight average molecular weight in terms of polystyrene was 6.2 × 10 ⁴ .

[Production Example 8]
The following combinations (8) to (12) were used as raw materials for the synthesis according to the synthesis method described above. As a result, a cycloalkyl group-containing acrylic copolymer could be obtained.
(8) 50% cyclohexyl methacrylate and 50% methacryl-modified dimethylpolysiloxane macromonomer of the above formula (VI),
(9) 50% cyclohexyl methacrylate and 50% lauryl methacrylate,
(10) 75% cyclohexyl methacrylate and 25% lauryl methacrylate,
(11) 60% cyclohexyl methacrylate and 40% 2-ethylhexyl methacrylate, and
(12) A methacryl-modified dimethylpolysiloxane macromonomer of formula (IV) wherein cyclohexyl methacrylate and n = 150, R ₁₃ is a CH ₃ group, and R ₁₄ is a C ₄ H ₉ group.

(Production Comparative Example 1)
[Synthesis of poly (cyclohexyl methacrylate)]
To the flask, 30 g of cyclohexyl methacrylate and 70 g of toluene were added, and nitrogen gas was introduced to make a sufficient nitrogen atmosphere. Methanol was injected into the obtained reaction product to precipitate an acrylic polymer, and the precipitate was filtered off and dried under vacuum to obtain 29.9 g of a poly (cyclohexyl methacrylate) solid content.

(Production Comparative Example 2)
[Synthesis of Cycloalkyl Group-Containing Acrylic Copolymer (8)]
Add 15 g of cyclohexyl methacrylate, 15 g of ethyl acrylate, and 70 g of toluene to the above flask, introduce nitrogen gas into a nitrogen atmosphere, heat to 100 ° C., add 0.15 g of AIBN, and reflux for 3 hours for polymerization. I let you. Methanol was injected into the obtained reaction product to precipitate an acrylic polymer, and the precipitate was filtered off and dried under vacuum to obtain a cycloalkyl group-containing acrylic copolymer.

(Production Comparative Example 3)
[Synthesis of Cycloalkyl Group-Containing Acrylic Copolymer (9)]
Add 50 g of cyclohexyl methacrylate, 50 g of n-butyl methacrylate and 70 g of toluene to the above flask, introduce nitrogen gas to make a sufficient nitrogen atmosphere, warm to 100 ° C., add 0.15 g of AIBN and reflux for 3 hours. And polymerized. Methanol was injected into the obtained reaction product to precipitate an acrylic polymer. The precipitate was filtered and dried in vacuo to obtain 22.2 g of a cycloalkyl group-containing acrylic copolymer solid.

(Production Comparative Example 4)
[Synthesis of Cycloalkyl Group-Containing Acrylic Copolymer (10)]
Add 15 g of cyclohexyl methacrylate, 15 g of t-butyl methacrylate and 70 g of toluene to the above flask, introduce nitrogen gas to make a sufficient nitrogen atmosphere, heat to 100 ° C., add 0.15 g of AIBN and reflux for 3 hours. And polymerized. Methanol was injected into the resulting reaction product to precipitate an acrylic copolymer, and the precipitate was filtered off and dried under vacuum to obtain 19.6 g of a cycloalkyl group-containing acrylic copolymer solid content.

(Production Comparative Example 5)
[Synthesis of Cycloalkyl Group-Containing Acrylic Copolymer (11)]
Add 22.5 g of cyclohexyl methacrylate, 7.5 g of t-butyl methacrylate and 70 g of toluene to the above flask, introduce nitrogen gas to make a sufficient nitrogen atmosphere, warm to 100 ° C., and add 0.15 g of AIBN. The mixture was refluxed for 3 hours for polymerization. Methanol was injected into the obtained reaction product to precipitate an acrylic polymer. The precipitate was filtered and dried in vacuo to obtain 23.8 g of a cycloalkyl group-containing acrylic copolymer solid.

(Production Comparative Example 6)
[Synthesis of acrylic-silicone graft polymer]
100 g of toluene was added to a four-necked separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Nitrogen gas is introduced into a reaction solution in which 40 g of a siloxane macromonomer, 50 g of toluene, and 1.5 g of t-butylperoxy-2-ethylhexanoate are uniformly dissolved, and the mixture is added dropwise at 100 ° C. in a nitrogen atmosphere. After completion of the dropwise addition, the mixture was refluxed for 5 hours for polymerization. Methanol was injected into the obtained reaction product to precipitate an acrylic-silicone graft polymer. The precipitate was filtered and dried in vacuo to obtain 78.5 g of a solid content of acrylic-silicone graft polymer.

(Evaluation)
Solubility of acrylic copolymers of Production Examples 1 to 7 and Production Comparative Examples 1 to 6 in light liquid isoparaffin (IP solvent 1620 (manufactured by Idemitsu Kosan Co., Ltd.), flash point 49 ° C.), transparency and strength of the film, etc. Was evaluated according to the following method. The results are shown in Tables 1 and 2.

<Evaluation method>
(1) Solubility in light liquid isoparaffin (IP Solvent 1620 (manufactured by Idemitsu Kosan Co., Ltd.)) The mixture was added and mixed, and the solubility at 25 ° C. was evaluated according to the following evaluation criteria.
A: Transparent dissolution.
○: Slight turbidity is observed but dissolves.
Δ: A partially dissolved but insoluble acrylic copolymer is precipitated.
X: Not dissolved.

(2) Transparency of the film After preparing a thin film with a 100 μm applicator on the glass plate from the 30% by mass acrylic copolymer solution of Production Example and Production Comparative Example dissolved in light fluid isoparaffin, the acrylic copolymer is dried and dried. A combined film was prepared, and the transparency of the film was visually evaluated.
○: Transparent △: Slightly turbid, but translucent ×: Turbid and opaque

(3) Hardness of coating A 30% by weight acrylic copolymer solution of Production Examples 1 to 7 and Production Comparative Examples 1 to 6 dissolved in light liquid isoparaffin was formed on a glass plate with a 100 μm applicator and then dried. Then, an acrylic copolymer film was prepared, and a pencil hardness test was performed according to the method of JIS-K5400.

From the results of Production Examples 1 to 7 in Table 1, the cycloalkyl group-containing acrylic copolymer of the present invention has good solubility in light liquid isoparaffin, and its film is highly transparent and hard, and is a film forming agent. As it turned out to be excellent. In addition, it was confirmed that the five cycloalkyl group-containing acrylic copolymers described in Production Example 8 were also dissolved in light liquid isoparaffin to form a transparent film. On the other hand, it was confirmed that the acrylic copolymers of Production Comparative Examples 1 to 5 did not dissolve in light liquid isoparaffin and were not suitable as a film forming agent. In addition, the acrylic-silicone graft polymer of Production Comparative Example 6 is a polymer described in Patent Document 1, but it is too soft to obtain a film with sufficient hardness, resulting in stickiness, tackiness, and nonuniform film. It was confirmed that there might be defects such as sex.

Lip cosmetic [Examples 1 to 8 and Comparative Examples 1 to 5] Oily liquid lipstick
An oily liquid lipstick having the composition shown in Table 3 was prepared by the following production method. Color retention over time, b. Secondary adhesion prevention effect, c. Shiny feeling, d. No sense of burden, e. The smooth usability was evaluated, and the results are also shown in Table 3.

* 1: Cycloalkyl group-containing acrylic copolymer of Production Example 1 (1)
* 2: Cycloalkyl group-containing acrylic copolymer of Production Example 2 (2)
* 3: Cycloalkyl group-containing acrylic copolymer of Production Example 3 (3)
* 4: Acrylic polymer of Production Comparative Example 1 * 5: Silicon KF-7312 (manufactured by Shin-Etsu Chemical Co., Ltd.), 50% decamethylcyclopentasiloxane solution * 6: Nissetsu U-3700A (manufactured by Nippon Carbide Industries Co., Ltd.) 50% light liquid isoparaffin solution * 7: IP solvent 2028 (manufactured by Idemitsu Kosan Co., Ltd.)
* 8: AEROSIL300 (Nippon Aerosil Co., Ltd.)
* 9: BENTONE 38 (made by Elementis)
* 10: Polybutene 2000H (made by Idemitsu Kosan Co., Ltd.)
(Production method)
A: Components (1) to (8) are uniformly dissolved.
B: Add components (9) to (15) to A and mix and disperse uniformly.
C: After defoaming B, fill the container with the application body.

(Evaluation methods)
Each sample was tested for use by 20 specialist panels. Each panel panel was observed immediately after application for Ha, D, and E, for B, for no color transfer when tissue was turned off 10 minutes after application, and for A for 6 hours after application, The following absolute evaluation criteria were evaluated and graded, and the average value was calculated from the total score of all the panels of each sample. In the table, the determination result and the average value of the score are shown in parentheses.
<Sensory evaluation items>
I. Color retention over time b. Secondary adhesion prevention effect c. Glossy d. There is no burden. Smooth feel <absolute evaluation criteria>
(Score): (Evaluation)
6 points: Very good 5 points: Good 4 points: Slightly good 3 points: Normal 2 points: Slightly bad 1 point: Defect <4 step criteria>
(Judgment): (Average score)
◎: Over 5 points ○: Over 5 points or less △: Over 2 points 3 points or less ×: 2 points or less

As is apparent from the results in Table 3, the oily liquid lipsticks of Examples 1 to 8 of the present invention have a color retention over time, an effect of preventing secondary adhesion, and gloss, compared to the oily liquid lipsticks of Comparative Examples 1 to 5. It was excellent in feeling of feeling, no feeling of burden, and smooth use feeling. In particular, Example 6 in which an olefin polymer and / or polyolefin, which is a liquid non-volatile hydrocarbon oil at 25 ° C., was excellent in terms of color durability and no feeling of burden. On the other hand, in Comparative Example 1 in which the cycloalkyl group-containing acrylic copolymer of the present invention is not blended, no film is formed, so that the color persistence is poor and the secondary adhesion preventing effect is not seen. In Comparative Example 2 in which no volatile oil was blended, the decorative film could not form a sufficient film, and a satisfactory film was not obtained in terms of the effect of preventing secondary adhesion and lack of feeling of burden. Further, in Comparative Example 3 using an acrylic polymer instead of the cycloalkyl group-containing acrylic copolymer of the present invention, the uniformity of the decorative film is lacking. In Comparative Example 4 in which trimethylsiloxysilicic acid was used instead of the acryl-containing copolymer, the cycloalkyl group-containing acryl-based copolymer of the present invention was free from the feeling of burden due to the lack of flexibility of the decorative film. In Comparative Example 5 using a dispersion of an alkyl acrylate / styrene copolymer instead of lacquer, a cosmetic film lacking in flexibility and uniformity, and satisfactory in terms of glossiness and lack of burden is obtained. There wasn't.

[Example 9] Oily stick lipstick (component) (%)
(1) Polyethylene wax * 11 6
(2) Candelilla wax 6
(3) Cetyl tri-2-ethylhexanoate 30
(4) Cycloalkyl group-containing acrylic copolymer * 2 1
(5) Isododecane * 12 Residual amount (6) Trimethylsiloxysilicate solution * 5 1
(7) Decamethylcyclopentasiloxane 5
(8) PEG-9 Polydimethylsiloxyethyl dimethicone 1
(9) Silylated silicic acid * 13 2
(10) Bengala-coated mica titanium * 14 5
(11) Red No. 202 0.1
(12) Yellow No. 4 0.1
(13) Refined avocado oil 0.1
(14) Fragrance 0.5
* 11: PERFORMALENE 500 (manufactured by New Phase Technology)
* 12: Isododecane (manufactured by Bayer)
* 13: AEROSIL R972 (Nippon Aerosil Co., Ltd.)
* 14: Dimethylpolysiloxane 3% treatment (manufacturing method)
A: The component (4) and the component (5) are uniformly dissolved.
B: A, components (1) to (3) and components (6) to (8) are uniformly heated and dissolved at 95 ° C.
C: Components (9) to (14) are added to B and mixed and dispersed uniformly.
D: After defoaming C, fill the container.
(Evaluation)
The oily stick-like lipstick thus obtained was evaluated in the same manner as in Examples 1 to 8. As a result, it was excellent in color retention over time, secondary adhesion prevention effect, glossiness, no burden, and smooth use feeling. It was.

[Example 10] Oily paste lip gloss (component) (%)
(1) Dextrin palmitate 3
(2) Heavy liquid isoparaffin * 15 30
(3) Cycloalkyl group-containing acrylic copolymer solution * 16 50
(4) Isododecane * 11 Remaining amount (5) Titanium oxide-coated glass powder * 17 5
(6) Honey 0.01
* 15: Pearl Dream 18 (Nippon Yushi Co., Ltd.)
* 16: 30% light fluid isoparaffin solution of the cycloalkyl group-containing acrylic copolymer (3) of Production Example 3 * 17: Metashine 1080RC-R (manufactured by Nippon Sheet Glass Co., Ltd.)
(Production method)
A: Components (1) to (4) are uniformly dissolved by heating at 95 ° C.
B: Components (5) to (6) are added to A and mixed and dispersed uniformly.
C: After defoaming B, fill the tube container.
(Evaluation)
The oily paste-like lip gloss thus obtained was evaluated in the same manner as in Examples 1 to 8. As a result, the color persisted over time, the effect of preventing secondary adhesion, a feeling of gloss, no feeling of burden, and a smooth feeling of use. It was excellent.

[Example 11] Oily solid lip balm (component) (%)
(1) Ceresin wax 18
(2) Vaseline 30
(3) Glyceryl 2-ethylhexanoate 5
(4) Polyglyceryl triisostearate 10
(5) Cycloalkyl group-containing acrylic copolymer * 18 1
(6) Acrylic copolymer containing cycloalkyl group * 19 1
(7) Isohexadecane * 20 Residual amount (8) Ethanol 0.5
(9) Polyethylene terephthalate, aluminum, epoxy laminated powder 1
(10) Titanium oxide * 21 0.1
(11) Tocopherol acetate 0.1
* 18: Cycloalkyl group-containing acrylic copolymer of Production Example 4 (4)
* 19: Cycloalkyl group-containing acrylic copolymer of Production Example 5 (5)
* 20: Isohexadecane (manufactured by Unikema)
* 21: 5% perfluoropolyether treatment (production method)
A: Components (1) to (7) are uniformly heated and dissolved at 95 ° C.
B: Components (8) to (11) are added to A and mixed and dispersed uniformly.
C: After defoaming B, fill the jar.
(Evaluation)
The oily solid lip balm thus obtained was evaluated in the same manner as in Examples 1 to 8. As a result, the color persisted over time, the effect of preventing secondary adhesion, a glossy feeling, no feeling of burden, and a smooth feeling of use. It was excellent.

[Example 12] Water-in-oil paste lipstick (component) (%)
(1) Dextrin palmitate 2
(2) α-olefin oligomer remaining amount (3) decamethylcyclopentasiloxane 5
(4) Polyoxyethylene / methylpolysiloxane copolymer 1
(5) Sorbitan sesquioleate 5
(6) Cycloalkyl group-containing acrylic copolymer * 22 0.5
(7) Isododecane * 12 1
(8) Purified water 20
(9) Red No. 226 0.3
(10) Titanium oxide * 21 0.1
* 22: Cycloalkyl group-containing acrylic copolymer of Production Example 6 (6)
(Production method)
A: Components (1) to (7) are uniformly heated and dissolved at 95 ° C.
B: Component (8) is added to A and emulsified. Thereafter, components (9) to (10) are added and mixed uniformly.
C: After defoaming B, fill the tube container.
(Evaluation)
The water-in-oil pasty lipstick thus obtained was evaluated in the same manner as in Examples 1 to 8. As a result, the color persisted over time, the effect of preventing secondary adhesion, a feeling of gloss, no feeling of burden, and smooth use. It was excellent in feeling.

[Example 13] Water-in-oil paste lipstick base (component) (%)
(1) Dextrin palmitate 5
(2) α-olefin oligomer remaining amount (3) sorbitan sesquioleate 5
(4) Cycloalkyl group-containing acrylic copolymer * 23 0.5
(5) Isododecane * 12 1
(6) Purified water 10
(7) Red No. 218 0.05
(8) Nylon fiber 0.1
* 23: Cycloalkyl group-containing acrylic copolymer of Production Example 7 (7)
(Production method)
A: Components (1) to (5) are uniformly dissolved by heating at 95 ° C.
B: Components (6) to (8) are added to A and emulsified.
C: After defoaming B, fill the tube container.
(Evaluation)
The water-in-oil pasty lipstick substrate thus obtained was evaluated in the same manner as in Examples 1 to 8, and was excellent in color retention over time, lack of burden, and smooth use feeling. .

II Eyeliner Cosmetics [Examples 14 to 17, Comparative Examples 6 to 9] Eyeliner (oil-based liquid)
An eyeliner having the formulation shown in Table 4 was prepared by the following method, and the following methods were used for the uniformity of the cosmetic film, the gloss effect as a cosmetic effect, the color development, the persistence of the cosmetic film, the non-bleeding and the no peeling off The sensory evaluation was performed. The results are also shown in Table 4.

* 24: IP solvent 1620 (made by Idemitsu Kosan Co., Ltd.)
* 25: A cycloalkyl group-containing acrylic copolymer (1) of Production Example 1 dissolved in light liquid isoparaffin (IP solvent 1620) to give a 40% solution * 26: Opanol B-100 (manufactured by BASF)
* 27: Silicon KF-9021 (manufactured by Shin-Etsu Chemical Co., Ltd.) (50% solid content decamethylcyclopentasiloxane solution)
* 28: Esther gum HP (Arakawa Chemical Industries)
* 29: Nissetsu U-3700A (Nippon Carbide Industries Co., Ltd.) (light liquid isoparaffin solution with a solid content of 50%)
* 30: Treatment with 3% fluoroalkylalkoxysilane * 31: AEROSIL R976S (Nippon Aerosil Co., Ltd.)
* 32: AEROSIL 300 (Nippon Aerosil Co., Ltd.)

(Manufacturing method)
A: Components (1) to (10) are heated to 110 ° C. and dissolved uniformly.
B: Components (11) to (16) are added to A and mixed uniformly.
C: B is filled into a container to obtain a product.

(Evaluation methods)
Using the sensory evaluation panel of 10 persons, each sample was evaluated in 7 grades using the absolute evaluation criteria for the following evaluation items a to e. Was used to determine. In Table 4, the determination and the average value of the scores are shown in parentheses.
In addition, for the evaluation items d and e, after applying the sample along the contour of the eye, the panel was allowed to live a normal life, and the cosmetic effect after 12 hours was evaluated.
(Evaluation item)
a. Uniformity of decorative film b. Glossy c. Color development d. No blur (sustainability)
e. No peeling off (sustainability)
(1) Absolute evaluation criteria (score): (Evaluation)
6: Very good 5: Good 4: Somewhat good 3: Normal 2: Somewhat bad 1: Bad 0: Very bad (2) Four-step criteria (average point): (Judgment)
More than 5 points: Very good: ◎
3 points to 5 points or less: Good: ○
More than 1 point and 3 points or less: Somewhat bad: △
1 point or less: Defect: ×

As is clear from the results in Table 4, the eye liners of Examples 14 to 17 which are products of the present invention can draw a smooth line compared with the eye liners of Comparative Examples 6 to 9, and thus the cosmetic film is uniform. The cosmetic effect was excellent in that it was glossy and colored, and it did not bleed or peel off after 12 hours. It had much better properties in all aspects.
On the other hand, in Comparative Example 6 in which polyisobutylene is used instead of the cycloalkyl group-containing acrylic copolymer of the present invention, it is difficult to make it evenly applied because of the smoothness during use. A satisfactory film was not obtained in terms of film uniformity and gloss.
Further, in Comparative Example 7 using a trimethylsiloxysilicic acid solution instead of the cycloalkyl group-containing acrylic copolymer of the present invention, the cosmetic film has poor flexibility and cannot follow the movement of the eyes. As a result, a part of the decorative film peels off and the uniformity of the decorative film also deteriorates, so that a satisfactory result is not obtained in terms of gloss and color, and since it is smoother, it is difficult to draw There was a bug.
Further, in Comparative Example 8 using pentaerythritol rosinate instead of the cycloalkyl group-containing acrylic copolymer of the present invention, there is a stickiness of the decorative film at the time of use, and the uniformity of the decorative film is deteriorated. The glossiness also declined and a satisfactory one was not obtained.
Further, in Comparative Example 9 in which a light fluid isoparaffin dispersion of an acrylic-styrene copolymer resin is used instead of the cycloalkyl group-containing acrylic copolymer of the present invention, the decorative film thickness cannot be sufficiently obtained. Because of the lack of smoothness of the decorative film and poor transparency of the decorative film, it is not possible to obtain a satisfactory glossy or colored color. There was a bug.

[Examples 18 to 23]
Instead of the cycloalkyl group-containing acrylic copolymer solution used in Example 14, the cycloalkyl group-containing acrylic copolymers (2) to (7) obtained in Production Examples 2 to 7 were used as light liquid isoparaffins ( When a 40% solution dissolved in IP solvent 1620) was used to evaluate the mascara obtained by the same production method as in Example 14, the cosmetic film was excellent in uniformity and had high gloss and color. It was excellent in durability of makeup effect without peeling or bleeding. Table 5 shows the prescription and the results.

The following Examples 24 and 25 were also evaluated in the same manner as Examples 14 to 17 and Comparative Examples 6 to 9.
[Example 24] Eyeliner (oil-based liquid)
(Ingredient) (%)
(1) Cycloalkyl group-containing acrylic copolymer solution * 33 10
(2) Dextrin palmitate 4
(3) Polyethylene wax 4
(4) Paraffin wax 2
(5) Methyl paraoxybenzoate 0.1
(6) Light liquid isoparaffin * 24 13.5
(7) Dimethyl distearyl ammonium hectorite * 34 2.5
(8) Propylene carbonate 0.5
(9) Decamethylcyclopentasiloxane * 35 Residual amount (10) Silicone compound-treated black iron oxide * 36 15
(11) sericite treated with fluorine compound * 30 5
(12) Fluorine compound treatment talc * 30 8
(13) Silicone compound-treated mica * 36 0.5
(14) Silylated silicic acid * 31 2
(15) Oil-soluble rosemary extract 0.1
* 33: A cycloalkyl group-containing acrylic copolymer (4) of Production Example 4 dissolved in light liquid isoparaffin (IP solvent 1620) to give a 15% solution * 34: Dimethyl distearyl ammonium modified synthetic sodium silicate Magnesium: Lucentite SAN (Coop Chemical Co., Ltd.)
* 35: Silicon KF-995 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 36: Treatment with 4% dimethylpolysiloxane

(Production method)
A: Components (1) to (6) are dissolved by heating.
B: Components (7) to (15) are added to A and mixed uniformly.
C: B was filled in a container to obtain an oily eyeliner.

(Evaluation)
The oily-type liquid eyeliner obtained as described above was excellent in the uniformity of the cosmetic film, had a high gloss and color, and did not peel or bleed, and was excellent in the sustainability of the cosmetic effect.

[Example 25] Eyeliner (water-in-oil liquid)
(Ingredient) (%)
(1) Cycloalkyl group-containing acrylic copolymer solution * 37 20
(2) Light liquid isoparaffin * 24 Residual amount (3) Silylated silica anhydride * 31 7
(4) Silicic anhydride * 32 1
(5) Benzyldimethylstearylammonium-modified synthetic sodium silicate / magnesium * 38 0.5
(6) Dimethyl distearyl ammonium hectorite * 39 0.5
(7) Dimethylpolysiloxane (20cs) 1
(8) PEG-9 polydimethylsiloxyethyl dimethicone * 40 0.1
(9) Silicone compound-treated black iron oxide * 41 15
(10) Purified water 2
(11) Vinylpyrrolidone / styrene copolymer polymer emulsion * 42 5
(12) Phenoxyethanol 0.1
(13) 1,2-pentanediol 0.1
(14) Ethyl alcohol 3
(15) Tocopherol acetate 0.1
(16) Oil-soluble rosemary extract 0.1
* 37: A cycloalkyl group-containing acrylic copolymer (1) of Production Example 1 dissolved in light liquid isoparaffin (IP solvent 1620) to give a 20% solution * 38: Lucentite SSN (manufactured by Corp Chemical)
* 39: Benton 38V BC (made by Elementis)
* 40: KF-6028P (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 41: Methyl hydrogen polysiloxane 2% treatment * 42: ANTARA 430 (manufactured by ISP)

(Manufacturing method)
A: Components (1) to (3) are dissolved by heating at 110 ° C., and (4) to (9) are added and mixed.
B: Add components (10) to (16) and mix and dissolve uniformly.
C: B is added to A and emulsified.
D: A container is filled with C to obtain a product.

(Evaluation)
The water-in-oil type liquid eyeliner obtained as described above was excellent in the uniformity of the cosmetic film, had a high gloss and color development, and did not peel or bleed, and was excellent in the sustainability of the cosmetic effect. .

III Cosmetics for vaginal
[Examples 26 to 30 and Comparative Examples 10 to 12] Mascara (oil-based liquid)
The mascara having the formulation shown in Table 6 was prepared by the following production method, and sensory evaluation was performed by the following method for glossiness, curl-up effect, curl-keep effect, and uniformity of the decorative film. The results are also shown in Table 6.

* 43: IP solvent 1620 (made by Idemitsu Kosan Co., Ltd.)
* 44: A cycloalkyl group-containing acrylic copolymer (1) of Production Example 1 dissolved in light liquid isoparaffin (IP solvent 1620) to give a 40% solution * 45: Silicon KF-9021 (Shin-Etsu Chemical Co., Ltd.) Manufactured) (solid content 50% decamethylcyclopentasiloxane solution)
* 46: Esther gum HP (Arakawa Chemical Industries)
* 47: Nisetsu U-3700A (Nippon Carbide Industries Co., Ltd.) (50% solid liquid isoparaffin solution)
* 48: Benton 38V BC (manufactured by ELEMENTIS)
* 49: AEROSIL 300 (Nippon Aerosil Co., Ltd.)

(Manufacturing method)
A: Heat components (1) to (7) to 110 ° C. and dissolve uniformly.
B: Components (8) to (12) are added to A and mixed uniformly.
C: After cooling B, fill the container to make a product.

(Evaluation methods)
Using the sensory evaluation panel of 10 people, each sample was evaluated on the following evaluation items (i) to (e) by (1) using 7 absolute evaluation criteria, and (2) 4-step criteria Was used to determine. In Table 6, the determination and the average value of the score are shown in parentheses.
The evaluation item B was evaluated immediately after application, and for the evaluation items A, C, D, E, the sample was applied to the bag and the panel was allowed to live a normal life, and the cosmetic effect after 12 hours was evaluated. .
(Evaluation item)
I. Persistence of glossiness b. Curl-up effect c. Curl keep effect d. Persistence of volume effect e. Persistence of cosmetic film uniformity (1) Absolute evaluation criteria (score): (Evaluation)
6: Very good 5: Good 4: Somewhat good 3: Normal 2: Somewhat bad 1: Bad 0: Very bad (2) Four-step criteria (average point): (Judgment)
More than 5 points: Very good: ◎
3 points to 5 points or less: Good: ○
More than 1 point and 3 points or less: Somewhat bad: △
1 point or less: Defect: ×

As is apparent from the results in Table 6, the mascara of Examples 26 to 30 which are the products of the present invention are very easy to apply and have good adhesion, and the cosmetic film is uniform and glossy immediately after application, curling up An effect was also obtained, and these were very excellent in sustainability. In particular, Example 30 had a considerable volume effect.
On the other hand, in Comparative Example 10 using a trimethylsiloxysilicic acid solution instead of the cycloalkyl group-containing acrylic copolymer solution of the present invention, a strong decorative film can be obtained, but flexibility cannot be obtained. However, since the uniformity of the decorative film deteriorates over time, the glossy effect, curl-keep effect, and uniformity of the decorative film cannot be obtained, and the adhesive effect is also low, so the volume effect is also satisfactory. I couldn't get anything.
In Comparative Example 11 in which pentaerythritol rosinate is used instead of the cycloalkyl group-containing acrylic copolymer of the present invention, the cosmetic film has a stickiness. As a result, the uniformity of the film was lowered and the gloss was inferior. In addition, since the adhesive force is too high, the wrinkles are heavier and lower, so that a satisfactory curl-keep effect cannot be obtained.
Further, in Comparative Example 12 in which a light fluid isoparaffin dispersion of an acrylic-styrene copolymer resin is used instead of the cycloalkyl group-containing acrylic copolymer solution of the present invention, since the smooth usability is insufficient, uniform It was difficult to adhere to the film, and satisfactory results were not obtained in terms of uniformity of the decorative film and glossiness. Further, since the strength of the decorative film is insufficient, a satisfactory cosmetic effect such as a curl-up effect and a curl-keep effect and its sustainability cannot be obtained.

In addition, when the mascara of Examples 26 to 30 were overlaid (applied continuously with the applicator 10 times), the volume effect could be obtained without impairing the uniformity of the decorative film and the curl keeping effect. When the comparative examples 10 to 12 are overlaid, the stickiness of the decorative film is too strong, the heels are bundled together, the uniformity of the decorative film is not obtained, and the flexibility of the decorative film is low, so the feeling of use is also good It was bad.

[Examples 31 to 36]
Instead of the cycloalkyl group-containing acrylic copolymer solution used in Example 26, the cycloalkyl group-containing acrylic copolymers (2) to (7) obtained in Production Examples 2 to 7 were used as light liquid isoparaffins ( When a mascara obtained by dissolving in IP solvent 1620) to give a 40% solution and evaluating the same production method as in Example 26 was evaluated, the uniformity of the cosmetic film was high, and the glossy feeling was also good. It was obtained and excellent in sustainability. Table 7 shows the prescription and the results.

The following Examples 37 to 40 were also evaluated in the same manner as Examples 26 to 30 and Comparative Examples 10 to 12.
[Example 37] Mascara (oil-in-water emulsified liquid)
(Ingredient) (%)
(1) Stearic acid 3
(2) Carnauba wax 1
(3) Beeswax 1
(4) Paraffin wax 1
(5) Cycloalkyl group-containing acrylic copolymer solution * 50 10
(6) Light liquid isoparaffin * 43 0.5
(7) Self-emulsifying glyceryl monostearate 1
(8) Sucrose fatty acid ester * 51 2
(9) Polyoxyethylene sorbitan monooleate (20EO) 1.3
(10) Sorbitan sesquioleate 0.5
(11) Black iron oxide 5
(12) Silicic anhydride * 52 0.1
(13) Silicic anhydride * 53 0.1
(14) Triethanolamine 1.2
(15) 1,3-butylene glycol 8
(16) 1,2-pentanediol 0.1
(17) Methyl paraoxybenzoate 0.2
(18) Polyalkyl acrylate copolymer emulsion * 54 10
(19) Polyvinyl acetate emulsion * 55 0.5
(20) Beauty agent (peony extract) 0.03
(21) Purified water Residual amount * 50: Dissolved cycloalkyl group-containing acrylic copolymer (4) of Production Example 4 in light liquid isoparaffin (IP solvent 1620) to give a 20% solution * 51: Sugar wax S-10E (Daiichi Kogyo Seiyaku Co., Ltd.)
* 52: Silysia 550 (Fuji Silysia Chemical)
* 53: Nip seal E-220 (manufactured by Nippon Silica Industry Co., Ltd.)
* 54: YODOZOL GH810F (solid content 50%) (made by NSC Japan)
* 55: Vinibrand GV-5651 (solid content 40%) (manufactured by Nissin Chemical Industry Co., Ltd.)
(Manufacturing method)
A: Components (1) to (10) are dissolved by heating at 110 ° C., and component (11) is added and mixed uniformly.
B: Ingredients (12) to (21) are heated and mixed uniformly.
C: B is added to A and emulsified at 80 ° C.
D: C is cooled and filled into a container to obtain a product.
(Evaluation)
The oil-in-water emulsified mascara obtained as described above was excellent in the uniformity of the cosmetic film, and was excellent in the cosmetic effect of glossiness, curl effect and volume feeling and its sustainability.

[Example 38] Mascara (oil-based liquid) (long rush type)
(Ingredient) (%)
(1) Cycloalkyl group-containing acrylic copolymer solution * 44 48.6
(2) Candelilla resin * 56 3
(3) Light liquid isoparaffin * 43 Residual amount (4) Dextrin palmitate 1.4
(5) Microcrystalline wax 2
(6) Ceresin 3
(7) Beeswax 2
(8) Trimethylsiloxysilicate solution * 45 1
(9) Dimethyl distearyl ammonium hectorite * 48 10
(10) Silicic anhydride * 52 7
(11) Silicic anhydride * 53 3
(12) Fluorine compound-treated black iron oxide * 57 5
(13) Fluorine compound-treated talc * 57 5
(14) Nylon fiber * 58 3
* 56: Candelilla resin E-1 (Nippon Natural Products)
* 57: Treatment with 3% fluoroalkylalkoxysilane * 58: Nylon fiber 6.3T-2MM (manufactured by Chubu Pile)
(Manufacturing method)
A: Components (4) to (8) are heated and mixed at 90 ° C., components (1) to (3) are added, and heated and dissolved at 110 ° C.
B: Add component (9) to A and mix.
C: Components (10) to (14) are added to B and mixed uniformly.
D: C is cooled and filled into a container to obtain a product.
(Evaluation)
The oily mascara obtained as described above was excellent in the uniformity of the cosmetic film, and was excellent in the cosmetic effect such as gloss, curl effect, long rush effect, and volume effect and its sustainability.

[Example 39] Mascara (water-in-oil emulsified liquid)
(Ingredient) (%)
(1) Decamethylcyclopentasiloxane 5
(2) Light liquid isoparaffin * 43 5
(3) Cycloalkyl group-containing acrylic copolymer solution * 44 12.5
(4) PEG-9 polydimethylsiloxyethyl dimethicone * 59 2
(5) Dimethyl distearyl ammonium hectorite * 48 5
(6) Silicic anhydride * 52 3
(7) Black iron oxide treated with silicone compound * 60 5
(8) Talc 5
(9) Polyalkyl acrylate copolymer emulsion * 54 10
(10) Polyvinyl acetate emulsion * 55 10
(11) 1,3-butylene glycol 7
(12) Methyl paraoxybenzoate 0.1
(13) Purified water remaining amount * 59: KF-6028P (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 60: Treatment with 4% dimethylpolysiloxane (production method)
A: Components (1) to (4) are mixed uniformly.
B: Components (5) to (8) are added to A and mixed.
C: Components (9) to (13) are added to B and emulsified at room temperature.
D: C is cooled and filled into a container to obtain a product.
(Evaluation)
The water-in-oil emulsified mascara obtained as described above was excellent in the uniformity of the cosmetic film, and was excellent in the cosmetic effect such as gloss, curl effect, and volume effect and its sustainability.

[Example 40] Mascara substrate (oil-based liquid)
(Ingredient) (%)
(1) Dextrin palmitate 6
(2) Light liquid isoparaffin * 43 Residual amount (3) Isododecane 5
(4) Cycloalkyl group-containing acrylic copolymer solution * 61 50
(5) Mica titanium 3
(6) Dimethyl distearyl ammonium hectorite * 46 5
(7) Fumed silicic acid * 62 2
(8) Mica 3
(9) Titanium oxide coated glass powder 1
(10) Talc 20
* 61: A cycloalkyl group-containing acrylic copolymer (1) of Production Example 1 dissolved in light liquid isoparaffin (IP solvent 1620) to give a 15% solution * 62: AEROSIL R972 (manufactured by Aerosil Japan)
(Manufacturing method)
A: Components (1) to (4) are uniformly mixed and dissolved at 110 ° C., and components (5) to (10) are added and mixed uniformly.
B: A is filled into a container and cooled to obtain a product.
(Evaluation)
The oily-type mascara substrate obtained as described above is excellent in the uniformity of the cosmetic film, easy to apply overlaid with commercially available mascara, and has excellent cosmetic effects such as curl effect and volume effect and its sustainability. there were.

The cycloalkyl group-containing acrylic copolymer of the present invention is characterized by being dissolved in a volatile oil such as light liquid isoparaffin, and the film has high film strength and is excellent in transparency, adhesion and water resistance. .
Therefore, when the cycloalkyl group-containing acrylic copolymer of the present invention is blended in cosmetics, cosmetics having excellent gloss, adhesion, water resistance and extremely long-lasting makeup can be obtained, especially makeup cosmetics. It is suitable as.
For example, as an eyeliner cosmetic, the cosmetic film is excellent in uniformity, has a high gloss and color, and is excellent in the sustainability of the makeup effect without bleeding or peeling.
Moreover, as a cosmetic for wrinkles, it is excellent in the curl effect and its sustainability, and is excellent in the uniformity and glossiness of the cosmetic film. Moreover, as a lip cosmetic, it is excellent in the color retention with time and the secondary adhesion preventing effect, and is excellent in a feeling of gloss, a feeling of burden and a smooth feeling of use.

Claims

An acrylic copolymer obtained by polymerizing a monomer containing the following component (a1) and component (a2) and / or component (a3), and the amount of component (a1) in the total amount of constituent monomers Is 50 to 90% by mass, the amount of component (a2) and / or component (a3) is 10 to 50% by mass, and at least 30% by mass is dissolved in light liquid isoparaffin at 25 ° C. A makeup cosmetic containing a cycloalkyl group-containing acrylic copolymer.
Component (a1): Formula (I)

(Wherein R 1 represents a hydrogen atom or a methyl group, and R 2 represents a cycloalkyl group) An acrylate and / or methacrylate component (a2): Formula (II)

An acrylate and / or methacrylate component (a3) represented by the formula (wherein R 3 represents a hydrogen atom or a methyl group, and R 4 represents a linear or branched alkyl group having 8 to 12 carbon atoms): one terminal Organopolysiloxane macromonomer containing a radical polymerizable group
The makeup cosmetic according to claim 1, wherein the cycloalkyl group-containing acrylic copolymer is obtained by polymerizing the components (a1) and (a2).
The makeup cosmetic according to claim 1, wherein the cycloalkyl group-containing acrylic copolymer is obtained by polymerizing the component (a1) and the component (a3).
The makeup cosmetic according to claim 1, wherein the cycloalkyl group-containing acrylic copolymer is obtained by polymerizing the component (a1), the component (a2) and the component (a3).
Component (a3) is represented by the following general formula (III)

(Wherein R 5 represents a hydrogen atom or a methyl group, R 6 to R 12 each independently represents an alkyl group having 1 to 5 carbon atoms, m represents any integer of 1 to 10, n The makeup cosmetic according to any one of claims 1, 3 and 4, characterized in that is an organopolysiloxane macromonomer represented by any one of 0 to 200.
The makeup cosmetic according to any one of claims 1 to 5, wherein the component (a1) is cyclohexyl methacrylate.
The weight average molecular weight in terms of polystyrene measured by liquid gel permeation chromatography of a cycloalkyl group-containing acrylic copolymer is 1.0 × 10 4 to 2.0 × 10 5 , Makeup cosmetics according to any one of 6
The makeup cosmetic according to any one of claims 1 to 7, further comprising a volatile oil.
The makeup cosmetic according to claim 8, wherein the volatile oil is light liquid isoparaffin.
The makeup cosmetic according to any one of claims 1 to 9, further comprising a powder containing or not containing a colorant.
The makeup cosmetic according to any one of claims 1 to 10, wherein the makeup cosmetic is a lip cosmetic, an eyeliner cosmetic, or a vaginal cosmetic.
The makeup cosmetic according to claim 10, wherein the makeup cosmetic is a lip cosmetic containing a non-volatile hydrocarbon oil that is liquid at 25 ° C.
11. The makeup cosmetic according to claim 10, wherein the cosmetic is an eyeliner cosmetic or a vaginal cosmetic, and the powder containing a colorant contains silicic anhydride.