TWI476215B - And a cosmetic cosmetic containing a cycloalkyl group-containing acrylic copolymer - Google Patents

Description

Beauty cosmetic containing a cycloalkyl-containing acrylic copolymer

The present invention relates to a cosmetic cosmetic containing a cycloalkyl group-containing acrylic copolymer, and more particularly to a cycloalkyl-containing acrylic copolymer containing a volatile oil agent such as a light liquid isomerized paraffin wax. Beauty cosmetics, preferably lip cosmetics, eyelash cosmetics, eyeliner cosmetics.

1) About acrylic copolymer

The acrylic resin represented by polymethyl methacrylate forms a transparent and hard film and has good processability, and thus is widely used as an organic glass material or a coating material. However, the acrylic resin has a high polarity and is soluble in an organic solvent such as acetone, toluene, butyl acetate or chloroform, but is insoluble in a light liquid isoparaffin or an alkane solvent such as isododecane, which is difficult to be used. An acrylic resin was used as a film forming agent in the system. Particularly in cosmetics, the use of the organic solvent as described above is limited in terms of skin safety or formulation, and it is therefore desired to develop an alkane solvent or a polypeptene which is generally soluble in cosmetics. An acrylic resin of an oxygen solvent.

For example, there has been proposed a cosmetic comprising a dimethylpolysiloxane compound having a radical polymerizable group at a single end of a molecular chain and a radical having acrylate and/or methacrylate as a main component. An acrylic acid-polyoxygenated graft copolymer obtained by radical copolymerization of a polymerizable monomer (for example, see Patent Document 1); or a cosmetic characterized by being 1 to 60% by weight in terms of solid content. An aqueous polymer emulsion containing a monomer having a cycloalkyl group having a polymerizable double bond and a monomer having a double bond copolymerizable with the above monomer, such as 2-ethylhexyl methacrylate, as a constituent component (for example, refer to Patent Document 2); or a block polymer comprising at least one first block and at least one second block, and the method for producing the same, wherein the block polymer is characterized in that the first block system is CH ₂ =CH-COOR ₂ [wherein R ₂ represents a C ₄ to C ₁₂ cycloalkyl group] of at least one acrylate monomer, and a formula CH ₂ =C(CH ₃ )-COOR' ₂ [wherein R' ₂ represents at least one methacrylate monomer of a C ₄ to C ₁₂ cycloalkyl group] Further, the second block is obtained from an acrylic monomer and at least one monomer having a glass transition temperature of 20 ° C or lower (for example, refer to Patent Document 3).

Further, an acrylic lacquer composition containing a vinyl monomer containing a cycloalkyl acrylate and/or a cycloalkyl methacrylate in a ratio of 10% by weight or more to the vinyl monomer is also reported. The (co)polymer (A) obtained by (co)polymerization and an organic solvent (for example, refer to Patent Document 4) and the like.

Further, in recent years, the present applicant has developed a cycloalkyl group-containing acrylic copolymer which is characterized in that it contains (A) a cycloalkyl group-containing acrylate and/or a Acrylate, (B) acrylate and/or methacrylate containing a linear or branched alkyl group having a carbon number of 8 to 12, and/or (C) an organic polymer having a radical polymerizable group at one end The monomer of the siloxane main monomer is obtained by polymerization, and the total amount of the constituting monomers is 50 to 90% by mass of the component (A), and the compounding amount of the component (B) and/or (C) is 10 ~50% by mass, and at least 30% by mass is dissolved in the light isoparaffin at 25 ° C (refer to Patent Document 5). However, this document is filed in Japan before the application date of the patent application which is the basis of the priority claim of the present invention, which is published after February 27, 2009, and is published after February 27, 2009. In this document, a cycloalkyl group-containing acrylic copolymer is described as being useful for cosmetics, but a representative cosmetic such as a lip cosmetic, an eyelash cosmetic, or an eyeliner is not specifically disclosed.

2) About beauty cosmetics

As a cosmetic, there are cosmetics for the lips such as lipsticks and lip glosses, cosmetics for eyelashes, eyeliners, powders, blushers, concealers, etc., in particular, the cosmetics for the lips and the cosmetics for eyelashes which are suitable for the present invention. The prior art of the eyeliner is described.

2-1) Cosmetics for the lips

Conventionally, as a lip cosmetic which is excellent in water resistance, oil resistance, makeup lasting effect, or secondary adhesion prevention effect, there are several types in which an organic polysiloxane resin and a volatile oil component are blended. For example, a technique has been developed in which a technique of formulating an organic polyoxynoxy resin having a specific structure and an average molecular weight and a volatile oil component (for example, refer to Patent Document 6); and blending a volatile oil component and dissolving the polyoxyl oxygen in the volatile oil component A water-repellent polymer such as a resin, a wax dispersed in a volatile oil component, and a non-volatile oil component which is compatible with a volatile oil component (for example, refer to Patent Document 7).

These technologies are formulated by dissolving organic polyoxyl resin in volatile oils, and the volatile oil agent volatilizes after application, thereby forming a film of organic polyoxyl resin, thereby obtaining a makeup lasting effect or A cosmetic that is excellent in secondary adhesion, but the film is hard, and the cosmetic film lacks softness, so the burden on the skin or the lips is strong, and the gloss of the applied film is insufficient.

Therefore, it has been desired to develop a lip cosmetic which is excellent in color retention and secondary adhesion prevention, and which is excellent in gloss, no burden, and smooth feeling of use.

2-2) Eyeliner cosmetics

Previously, eyeliner cosmetics have cosmetics that make the eyes look larger and make the eyes clear by applying them to the eye. As a required quality, in addition to the ease of application of the smear, the uniformity, high gloss, or color development of the coating film is required for the cosmetic film, and the cosmetic film is not peeled off or smeared over time, in order to achieve various effects. The film former is continuously formulated.

Moreover, the eyeliner cosmetics must be easily applied to the eye and quickly form a cosmetic film after application, and therefore a volatile solvent is used. Typical examples thereof include water, a light liquid, a paraffin wax, an alkane solvent such as isododecane, a polyorganosiloxane such as a cyclic organopolysiloxane or a low molecular weight organic polyoxyalkylene.

The film forming agent is roughly divided into a user dissolved in the solvent and dispersed in a solvent. Here, the film forming agent dispersed in a solvent means a suspension of fine particles in which a polymer substance is stably dispersed in water or an organic solvent, and includes a liquid obtained by polymerizing a monomer emulsified by a surfactant. Or milky sap present in nature.

When a film forming agent dissolved in a solvent is used, it can be uniformly applied to the eye, and if a film forming agent dispersed in a solvent is used, a cosmetic film can be formed quickly.

As an example of such a compounding technique, a technique of improving the usability and the persistence of a cosmetic effect by using an oil-soluble film-forming resin and a fluorine compound-treated powder (for example, refer to Patent Document 8); or In the water-in-oil cosmetic, the oil-soluble resin is contained in the outer phase, and the emulsion resin having the film forming ability is contained in the inner phase, whereby the water resistance, the sweat resistance, the sebum resistance, the oil resistance, and the makeup are continued. A technique excellent in properties (for example, refer to Patent Document 9); a volatile oil is contained in a fat phase, and a specific film is dispersed in an aqueous phase to form a water-in-oil emulsion, thereby being easy to apply, easy to extend, and uniform. A technique that does not stick, does not transfer or spread (for example, refer to Patent Document 10).

However, the technique of Patent Document 8 can improve the strength or water resistance of the cosmetic film by using the oil-soluble film-forming resin and the fluorine compound-treated powder, thereby improving the persistence of the cosmetic effect, but the cosmetic film lacks transparency. There is a disadvantage that the original color tone of the coloring agent cannot be exhibited, and the color rendering degree is insufficient. Further, as in the case of the technique of Patent Document 9, when the oil-in-water cosmetic resin contains an oil-soluble resin and the inner phase contains an emulsion resin having a film forming ability, peeling or blooming of the cosmetic film can be prevented. Further, the makeup removal effect of the makeup remover can be improved, but in order to ensure stability, it is necessary to mix a large amount of wax or natural clay mineral or a surfactant, and as a result, the makeup film is turbid, and it is difficult to obtain a cosmetic film having a good color rendering property. In particular, if the amount of the surfactant is increased, there is also a disadvantage that the makeup film is smeared. Further, in the technique of Patent Document 10, in which a volatile oil is contained in a fat phase, and a specific film is formed in an aqueous phase to form a polymer to form a water-in-oil emulsion, thereby forming a non-tacky and uniform cosmetic film, Although the uniformity of the cosmetic film can be obtained, the cosmetic film is soft and the adhesion is low, so that the cosmetic continuity over time cannot be obtained.

Although the prior art has good usability and can form a cosmetic film uniformly, it lacks transparency, and therefore, glossiness and color development cannot be obtained, and even if the strength of the cosmetic film is increased, the part where the activity is large will be peeled off over time and the makeup is lost. effect. Therefore, it has been desired to develop an eyeliner cosmetic which has uniformity of a cosmetic film, is excellent in glossiness or color rendering, and is excellent in persistence of a makeup effect.

2-3) Cosmetics for eyelashes

Previously, eyelash cosmetics used to make the eyelashes appear curled (curl effect) by applying them to the eyelashes, or appear thick, or look thicker (full effect), or look longer (slim effect). cosmetic. In order to maintain various effects, the film forming agent is formulated to prevent the cosmetic film from being sampled.

Further, since the cosmetic for eyelashes must be easily applied to the eyelashes and the cosmetic film is quickly formed after application, a volatile solvent is used in the same manner as the 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 using trimethyl alkoxy citric acid and acrylic-polyoxygen grafting may be mentioned. A technique of a copolymer (for example, Patent Document 12), and a technique of using a combination of different types of film forming agents has been studied.

However, recently, although it is desired that the mascara cosmetic can reliably obtain various effects, it is difficult to continue the curling effect and to coexist other effects. For example, in order to obtain a full-bodied effect or a long-lasting effect and a curling effect, it is necessary to form a firm cosmetic film by attaching more wax, powder, fiber, etc. to the eyelashes to prevent the eyelashes from becoming heavy and drooping. If this happens, the makeup film may be cracked and peeled off due to activities such as blinking, and the effect of fullness or slenderness may disappear, and the cosmetic film may lose its transparency, so that the gloss of the eyelashes disappears. In addition, the make-up film becomes hard and the feeling of use is also poor. Further, the aqueous dispersion or the solvent dispersion of the film forming agent can impart appropriate strength and impart a curling effect when the cosmetic film is soft, but the uniformity of the cosmetic film cannot be obtained, so that the gloss is lowered and the color is developed. The degree is also poor, so sometimes it is not possible to fully obtain a striking effect.

Therefore, it is desired to develop a cosmetic for eyelashes which has an excellent curling effect and its durability and also has other effects.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 2704730

[Patent Document 2] Japanese Patent Laid-Open No. Hei 8-231344

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-31479

[Patent Document 4] Japanese Patent Laid-Open No. 62-84165

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2009-46662

[Patent Document 6] Japanese Patent Laid-Open No. Hei 9-124430

[Patent Document 7] Japanese Patent Laid-Open No. Hei 9-143034

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2001-187715

[Patent Document 9] Japanese Patent No. 3393903

[Patent Document 10] Japanese Patent Laid-Open No. Hei 10-203919

[Patent Document 11] Japanese Patent Laid-Open No. Hei 8-268841

[Patent Document 12] Japanese Patent Laid-Open No. Hei 7-194349

An object of the present invention is to provide a cosmetic cosmetic which is excellent in gloss, adhesion, and water resistance, and which is excellent in makeup durability, in the cycloalkyl group-containing acrylic copolymer described in Patent Document 5 developed by the present applicant.

In particular, the lip cosmetics are provided with a lip cosmetic which is excellent in color retention and secondary adhesion prevention, has a glossy feeling, a no-load feeling, and a smooth feeling of use, and provides a cosmetic film with respect to eyeliner cosmetics. An eyeliner cosmetic which is excellent in uniformity, glossiness, and color rendering, and excellent in the persistence of a cosmetic effect, and an eyelash cosmetic which is excellent in curling effect and durability and which has other effects.

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.

That is, the invention relates to:

(1) A cosmetic cosmetic containing a cycloalkyl group-containing acrylic copolymer, wherein the cycloalkyl group-containing acrylic copolymer is characterized in that it comprises the following component (a1), component (a2), and/or The monomer of the component (a3) is obtained by polymerization, and the compounding amount of the component (a1) is 50 to 90% by mass, and the compounding amount of the component (a2) and/or the component (a3) is 10 in the total amount of the constituent monomers. ~50% by mass, and dissolved in light liquid isoparaffin at least 30% by mass at 25 ° C;

Ingredient (a1): acrylate and/or methacrylate represented by formula (I)

[Chemical 1]

(wherein R1 represents a hydrogen atom or a methyl group, and R2 represents a cycloalkyl group);

Ingredient (a2): acrylate and/or methacrylate represented by formula (II)

[Chemical 2]

(wherein R3 represents a hydrogen atom or a methyl group, and R4 represents a linear or branched alkyl group having a carbon number of 8 to 12);

Component (a3): an organopolyoxyalkylene macromonomer having a radical polymerizable group at one end.

(2) The cosmetic preparation of (1) above, wherein the cycloalkyl group-containing acrylic copolymer is obtained by polymerizing the components (a1) and (a2).

(3) The cosmetic preparation according to (1) above, wherein the cycloalkyl group-containing acrylic copolymer is obtained by polymerizing the component (a1) and the component (a3).

(4) The cosmetic preparation according to (1) above, wherein the cycloalkyl group-containing acrylic copolymer is obtained by polymerizing the component (a1), the component (a2), and the component (a3).

(5) The cosmetic cosmetic according to any one of the above (1), wherein the component (a3) is an organopolysiloxane main monomer represented by the following formula (III).

[Chemical 3]

(wherein R ₅ represents a hydrogen atom or a methyl group, R ₆ to R ₁₂ each independently represent an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 to 10, and n represents an integer of 0 to 200; ).

(6) The cosmetic preparation according to any one of the above (1) to (5) wherein the component (a1) is cyclohexyl methacrylate.

(7) The cosmetic preparation according to any one of the above (1) to (6), wherein the polyalkylene-equivalent weight average of the cycloalkyl-containing acrylic copolymer is determined by liquid phase gel permeation chromatography The molecular weight is 1.0 × 10 ⁴ ~ 2.0 × 10 ⁵ .

(8) The cosmetic preparation according to any one of the above (1) to (7), wherein the volatile oil agent is further formulated.

(9) The cosmetic preparation according to (8) above, wherein the volatile oil agent is a light liquid isomerized paraffin.

(10) The cosmetic preparation according to any one of the above (1) to (9), wherein the powder containing or not containing a coloring agent is further formulated.

(11) The cosmetic preparation according to any one of the above (1) to (10), which is a lip cosmetic, an eyeliner cosmetic or an eyelash cosmetic.

(12) The cosmetic of the above (10), which is a lip cosmetic, and is formulated as a liquid non-volatile hydrocarbon oil at 25 °C.

(13) The cosmetic of the above (10), which is a cosmetic for eyeliner or mascara, and the powder containing the colorant contains anhydrous citric acid.

(1) Cyclic alkyl group-containing acrylic copolymer

The acrylic copolymer of the present invention is obtained by polymerizing a monomer comprising the following (a1), component (a2) and/or component (a3).

Ingredient (a1): acrylate and/or methacrylate represented by formula (I)

[Chemical 4]

(wherein R1 represents a hydrogen atom or a methyl group, and R2 represents a cycloalkyl group)

Ingredient (a2): acrylate and/or methacrylate represented by formula (II)

[Chemical 5]

(wherein R3 represents a hydrogen atom or a methyl group, and R4 represents a linear or branched alkyl group having a carbon number of 8 to 12)

Ingredient (a3): an organopolysiloxane main monomer having a radical polymerizable group at one end

In the acrylic copolymer of the present invention, the blending amount of the component (a1) in the total amount of the constituent monomers is 50 to 90% by mass (hereinafter referred to as "%"), and the blending of the component (a2) and/or the component (a3). The amount of the copolymer is 10 to 50%, and at least 30% of the copolymer dissolved in the light liquid isomerized paraffin at 25 ° C is not particularly limited.

In the present invention, the light liquid isomerized paraffin in the definition of "at least 30% dissolved in light liquid isomerized paraffin at 25 ° C" means a mixture of hydrocarbons mainly comprising isoparaffin, having a JIS The petroleum product distillation test method specified by K2254 has an initial boiling temperature of 166 ° C and a distillation end point of 202 ° C. The dynamic viscosity at 37.8 ° C is 1.28 mm ² /s. As a commercial item, for example, IP Solvent 1620 (manufactured by Idemitsu Kosan Co., Ltd.) is available.

The cycloalkyl group-containing acrylate and/or methacrylate-based lipophilic polymerizable monomer of the component (a1) serves as a skeleton for imparting water resistance, transparency, and hardness to the film.

Here, the cycloalkyl group-containing acrylate and/or methacrylate includes one or two or more kinds of cycloalkyl group-containing acrylates, and one or two or more kinds of cycloalkyl group-containing methacrylates. And mixtures of such.

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 the cycloalkyl group-containing acrylate or methacrylate include cyclohexyl acrylate, cyclohexyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, and tricyclopentadienyl acrylate. Tricyclodecyl acrylate, tricyclodecyl methacrylate, tricyclodecanyl acrylate, tricyclodecanyl methacrylate, etc., one or two of these may be used. the above. In particular, cyclohexyl methacrylate has a good radical polymerizability and a high yield, and a copolymer having a suitable glass transition point for forming a hard coat film can be obtained, and thus is particularly preferable.

The acrylate and/or methacrylate containing a linear or branched alkyl group having 8 to 12 carbon atoms in the component (a2) is a lipophilic polymerizable monomer, and imparts flexibility or adhesion to the film. A skeleton that enhances the solubility in light liquid isomerized paraffin.

Here, the acrylate and/or methacrylate containing a linear or branched alkyl group having 8 to 12 carbon atoms contains one or more kinds of linear or branched chains having a carbon number of 8 to 12. The alkyl acrylate, one or two or more kinds of methacrylates having a linear or branched alkyl group having a carbon number of 8 to 12, and a mixture thereof.

Examples of the linear or branched alkyl group having a carbon number of 8 to 12 include an octyl group, a 2-ethylhexyl group, a decyl group, an isodecyl group, a lauryl group, etc., and a 2-ethylhexyl group is preferred. Lauryl, particularly preferred is 2-ethylhexyl.

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, and 2-ethylhexyl acrylate. 2-ethylhexyl methacrylate, isodecyl acrylate, isodecyl methacrylate, lauryl acrylate, lauryl methacrylate, etc., may be used alone or in combination of two or more, preferably methyl 2-Ethylhexyl acrylate and lauryl methacrylate, wherein 2-ethylhexyl methacrylate is particularly excellent in solubility.

The organopolyoxyalkylene macromonomer having a radical polymerizable group at a single terminal of the component (a3) is, for example, an ester compound in which an organopolyoxane is bonded to a divalent hydrocarbon group on acrylic acid or methacrylic acid, and is used. A skeleton that imparts water resistance to the film and improves solubility in a light liquid isomerized paraffin.

Specifically, an organopolyoxyalkylene macromonomer represented by the following formula (III) can be exemplified.

[Chemical 6]

(wherein R ₅ represents a hydrogen atom or a methyl group, R ₆ to R ₁₂ each independently represent an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 to 10, and n represents an integer of 0 to 200; These may be used alone or in combination of two or more.

Here, examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a t-butyl group, and a n-pentyl group.

More specifically, a dimethyl polyoxyalkylene macromonomer represented by the general formula (IV) can be cited.

[Chemistry 7]

(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).

When n in the repeating unit of the dimethyl polyphosphoalkyl group in the formula (III) is from 0 to 200, sufficient water resistance can be obtained, and a transparent and uniform film can be obtained, which is preferable. If n is from 5 to 150, it is more preferable in terms of obtaining a water-resistant or uniform film.

In addition, the cycloalkyl group-containing acrylic copolymer of the present invention contains a polymerizable monomer other than the above components (a1) to (a3) as an optional component insofar as the effects of the present invention are not impaired. The polymerizable monomer other than the components (a1) to (a3) is not particularly limited, and examples thereof include styrene, substituted styrene, vinyl acetate, acrylic acid, methacrylic acid, maleic anhydride, and cis-butene. Diester, fumarate, vinyl chloride, vinylidene chloride, ethylene, propylene, butadiene, acrylonitrile, fluorinated olefin, acrylamide, methacrylamide, methacryl Methyl acrylamide, methyl methacrylamide, dimethyl methacrylamide, N-isopropyl acrylamide, N-vinyl pyrrolidone, N-vinyl acetamide, acrylic acid Tributyl ester, butyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl methacrylamide, 2-propenylamine-2-dimethylpropane sulfonate and the like.

The ratio of the above components (a1) to (a3) or any of the monomers is as follows.

The compounding amount of the component (a1) is 50 to 90%, preferably 50 to 80%, based on the total amount of the monomers. If it is less than 50%, a film having sufficient hardness cannot be obtained, and if it exceeds 90%, solubility in a light liquid isomerized paraffin is deteriorated.

The blending amount of the component (a2) and/or the component (a3) is 10 to 50%, preferably 15 to 45%, based on the total amount of the monomers. When it is less than 10%, the solubility in the light liquid isomerized paraffin is deteriorated, and if it exceeds 50%, a film having sufficient hardness cannot be obtained, and defects such as stickiness or viscosity, film unevenness, and the like are caused.

The amount of the optional component is preferably 30% or less of the total amount of the monomers, preferably 20% or less, and for example, 0.01 to 10%.

Further, the cycloalkyl group-containing acrylic copolymer obtained by polymerizing 10 to 50% of the component (a3) with 50 to 90% of the component (a1) can particularly form a film having a good water resistance, relative to the component (a1). 50 to 90% of the cycloalkyl group-containing acrylic copolymer obtained by polymerizing the components (a2) and (a3) in a total amount of 10 to 50% can form a film having hardness and water resistance.

The weight average molecular weight of the cycloalkyl group-containing acrylic copolymer of the present invention is not particularly limited, and is preferably in the range of 1.0 × 10 ⁴ to 2.0 × 10 ⁵ . When it is this range, the film formation ability of the film which produces a uniform can be exhibited. The above weight average molecular weight is obtained by using tetrahydrofuran as a dissolving solution, using a calibration curve made of a linear polystyrene standard, and a gel-permeation chromatography (GPC) of a refractive index detector. Determination.

(2) Method for producing a cycloalkyl-containing acrylic copolymer

The cycloalkyl group-containing acrylic copolymer of the present invention can use the above components (a1) to (a3) or any other monomer as needed as a constituent monomer, in the presence of an organic solvent and in the absence of water, It is obtained by random polymerization using a known polymerization method. It is not particularly limited as long as it is an organic peroxide such as benzamidine peroxide or lauric acid peroxide, α,α'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethyl An azo compound such as valeronitrile or 2,2'-azobis(2-methylbutyronitrile), a radical polymerization initiator such as a persulfate polymerization initiator such as potassium persulfate or ammonium persulfate The polymerization may be carried out in the presence of a solution polymerization method, a suspension polymerization method, a bulk polymerization method, a precipitation polymerization method, or the like. Among these, in particular, the solution polymerization method is preferred because the molecular weight of the obtained acrylic copolymer is easily adjusted to an optimum range.

The organic solvent used in the polymerization of the cycloalkyl group-containing acrylic copolymer of the present invention may, for example, be an aromatic hydrocarbon such as benzene, toluene or xylene, or methyl ethyl ketone or methyl isobutyl ketone. The ketones, esters such as ethyl acetate and butyl acetate, and alcohols such as isopropyl alcohol, ethanol, and methanol may be used alone or in combination of two or more. Further, the polymerization may be carried out in an alkane solvent such as a light liquid isomerized paraffin, isododecane or 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 the usable temperature range of the usual radical polymerization initiator, and is usually in the range of 40 to 120 °C. The reaction time varies depending on the radical polymerization initiator to be used, the type of the monomer, and the reaction temperature, and is usually in the range of 2 to 24 hours. If the polymerization time is too short, the amount of residual monomers is large and the yield is low, which is not preferable.

The cycloalkyl group-containing acrylic copolymer of the present invention may be diluted with an oil agent such as another hydrocarbon or ester or triglyceride in a state of being dissolved in an alkane solvent at the time of the reaction, or the solvent may be replaced with another oil. Agent. The cycloalkyl group-containing acrylic copolymer composition in such an oil-soluble form is also included in the component (A) of the present invention. Further, the cycloalkyl group-containing acrylic copolymer may be taken out as a solid by removing the solvent of the solution, and the obtained cycloalkyl group-containing acrylic copolymer may be dissolved in the light liquid isomerized paraffin. It is used as a solution of an acrylic copolymer containing a cycloalkyl group. The cycloalkyl group-containing acrylic copolymer and the solution thereof may be used in combination of two or more kinds.

(3) Beauty cosmetics

The cycloalkyl group-containing acrylic copolymer is suitable as a lip cosmetic such as a lipstick or a lip gloss, an eye makeup cosmetic such as an eyeliner or an eyelash cosmetic, a cosmetic component such as a blush or a powder, and is particularly preferably used as a cosmetic component. Cosmetics for lip makeup, eyeliner and eyelashes.

The cosmetic preparation of the present invention usually contains the above-mentioned cycloalkyl group-containing acrylic copolymer and a volatile oil agent. Furthermore, it is possible to appropriately mix a powder (containing a colorant) which is a component used in a general cosmetic, an oily component other than a volatile oil agent, a fiber, a film-forming dispersion, or the like, within a range that does not impair the effects of the present invention, Surfactants, aqueous components, UV absorbers, humectants, anti-fading agents, antioxidants, defoamers, cosmetic ingredients, preservatives, perfumes, and the like.

For example, for lip cosmetics, eyelash cosmetics, and eyeliner cosmetics, it is preferred to formulate the following composition.

(lip cosmetics)

(A) a cycloalkyl-containing acrylic copolymer of the present invention

(B) volatile oil agent

(C) a powder containing a colorant,

And, as needed,

(D) Liquid non-volatile hydrocarbon oil at 25 ° C

(eyelash cosmetics and eyeliner)

(A) a cycloalkyl-containing acrylic copolymer of the present invention

(B) a volatile oil agent, and

(C) Powder with or without colorants

As (C), it is further preferred to contain anhydrous citric acid.

Hereinafter, each component will be described in detail.

(cycloalkyl-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% in terms of the solid content (in the case of a lip cosmetic, 0.1 to 30%), preferably 1 to 30%. 25%, more preferably 2~20%. In this range, for example, the cosmetic for lips is particularly excellent in color retention, secondary adhesion prevention, and no burden. Further, in the cosmetic for eyelashes, it is possible to obtain a film which is not sticky when finished, and which can form a film having a high uniform coating film strength, a gloss feeling or a curling force, and which is excellent in durability. Further, in the eyeliner cosmetic, it is possible to obtain a cosmetic film which is easy to draw a line, has a uniform coating film strength, a glossy feeling or a color development degree, and is excellent in durability.

The cycloalkyl group-containing acrylic copolymer is used by being dissolved in a volatile oil agent, and it is preferably used by being dissolved in a light liquid isomerized paraffin. It is preferred to set the concentration of the cycloalkyl group-containing acrylic copolymer in the volatile oil agent to 15 to 50%.

(volatile oil agent)

The volatile oil agent functions as a solvent of the cycloalkyl group-containing acrylic copolymer, and the cycloalkyl group-containing acrylic copolymer is easily prepared. As a result, the tackiness at the time of makeup is suppressed, and a uniform film is formed. .

The volatile oil agent is not particularly limited as long as it is volatile at 1 atm, 25 ° C, and is generally used in cosmetics, and specific examples thereof include light liquid isomerized paraffin, decamethylcyclopentanthene Oxyalkane, octamethylcyclotetraoxane, dodecamethylcyclohexaoxane, methyltrimethylhydrazine, dimethylpolyoxane, decamethyltetraoxane, ethyltrioxane, etc. . Here, the light liquid isomerized paraffin may be used without being limited to the use as a basis for solubility.

The following are mentioned as a commercial item. As a light liquid isomerized paraffin, Isopar H (manufactured by Esso Chemical Co., Ltd.), isododecane (manufactured by Bayer Co., Ltd.), isohexadecane (manufactured by Uniqema Co., Ltd.), IP Solvent 1620MU, IP Solvent 2028MU, IP Solvent 2835 (The above is manufactured by Idemitsu Kosan Co., Ltd.), etc., as decamethylcyclopentaoxane, there are TFS405 (manufactured by Toshiba Silicone Co., Ltd.), SH245, DC345 (manufactured by Toray Dow Corning Co., Ltd.), KF-995 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc., as methyl trimethyl hydrazine oil, there are Silicone TMF-1.5 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc., as methyl polysiloxane, KF-96L-2CS (Shin-Etsu Chemical Industry) As a decamethyltetraoxane, there is KF-96L-1.5CS (manufactured by Shin-Etsu Chemical Co., Ltd.), and as an ethyl trioxane, there is SILSOFT ETS (manufactured by Momentive Performance Materials Co., Ltd.). Among them, the light liquid isomerized paraffin wax is excellent in the solubility of the cycloalkyl group-containing acrylic copolymer of the component (A), and a uniform cosmetic film can be obtained. These volatile oil agents may be used alone or in combination of two or more.

The blending amount of the volatile oil agent is not particularly limited. For example, in the case of a lip cosmetic, it is preferably from 10 to 90%, more preferably from 15 to 85%. When it mixes in this range, it is especially excellent in a makeup durability, a secondary adhesion prevention effect, and a usage feeling. Further, in the case of eyeliner cosmetics or eyelash cosmetics, it is preferably from 1 to 80%, more preferably from 1 to 70%. If it is within this range, it will not stick when finished, and it will form a film which is uniform and has high film strength, and it is excellent in glossiness. For eyeliner cosmetics, color chromaticity and its persistence are more excellent. For the cosmetic for eyelashes, the curling force and its durability are more excellent.

(powder)

Coloring can be carried out by blending the powder, and the drying speed can be accelerated to further suppress the stickiness at the time of makeup.

The powder may be a powder which is usually used for cosmetics, and may have a shape such as a plate shape, a spindle shape, or a needle shape, or a particle shape such as a mist, a fine particle or a pigment grade, or a particle structure such as a porous or non-porous material. It is not particularly limited, and inorganic powders, bright 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 may be used.

Iron blue, ultramarine blue, iron oxide, iron oxide yellow, iron oxide black, titanium oxide, zinc oxide, titanium ‧ titanium oxide sinter, cerium oxide, magnesium oxide, zirconium oxide, cerium oxide, magnesium carbonate, calcium carbonate , chromium oxide, chromium hydroxide, carbon black, aluminum citrate, magnesium citrate, calcium citrate, barium strontium citrate, aluminum magnesium citrate, aluminum magnesium metasilicate, mica, synthetic mica, synthetic sericite, sericite, Inorganic powders such as talc, anhydrous citric acid, muscovite, phlogopite, red mica, biotite, kaolin, barium sulfate, bentonite, montmorillonite, diatomaceous earth, hydroxyapatite, boron nitride, etc.; Bismuth, mica titanium, titanium oxide coated bismuth oxychloride, iron oxide coated mica, iron oxide coated mica titanium, iron blue coated mica titanium, carmine coated mica titanium, organic pigment coated mica titanium, iron oxide ‧ titanium oxide coated synthetic gold Mica, fish scale foil, titanium dioxide coated glass flakes, polyethylene terephthalate ‧ aluminum ‧ epoxide laminated powder, polyethylene terephthalate ‧ polyolefin laminated film powder, polyethylene terephthalate ‧ polymethyl methacrylate laminate Bright powder such as powder; polyamine resin, polyethylene resin, polyacryl resin, polyester resin, fluorine resin, cellulose resin, polystyrene resin, styrene-acrylic acid copolymer Copolymer resin such as resin, organic polymer resin powder such as polypropylene resin, polyfluorene oxide resin, urethane resin, organic powder such as N-mercapto amide acid; starch, silk powder, cellulose Natural organic powders such as powder, organic tar pigments, pigment pigments such as lake pigments of organic pigments; metal powders such as aluminum powder, gold powder, silver powder; fine titanium oxide coated with mica titanium, fine particle zinc oxide coated with mica titanium, Barium sulfate coated with mica titanium and other composite powders; nylon, polypropylene, polyester and other synthetic fibers, rayon (rayon) and other man-made fibers, cellulose and other natural fibers, acetate rayon and other semi-synthetic fibers, poly-p-phenylene A fiber such as a composite fiber in which ethylene formate and nylon are laminated in a layer form.

Further, these powders may be used in combination of two or more kinds, or may be a fluorine-based compound, a polyfluorene-based compound, a metal soap, lecithin, hydrogenated lecithin, collagen, a higher fatty acid, or a higher alcohol. One or two or more kinds of esters, waxes, waxes, fats and oils, hydrocarbons, surfactants, amino acid-based compounds, and water-soluble polymers are subjected to surface treatment by a known method. These powders may be used alone or in combination of two or more.

The coloring agent includes a coloring agent which can be used as a specific example of the above-mentioned powder, and a coloring agent which is usually used in cosmetics can be used, and it can be in the form of a spherical shape, a plate shape, a spindle shape, a needle shape, or the like. The particle size of the fine particles and the pigment grade, or the particle structure such as porous or non-porous, is not particularly limited, and white inorganic pigments, colored inorganic pigments, colored organic pigments, dyes, and bright pigments can be used. Metal powders, composite powders, etc.

More specifically, for example, one or more of the following may be used.

White inorganic pigments such as titanium oxide, zinc oxide, cerium oxide, and barium sulfate; colored inorganic pigments such as iron oxide, carbon black, chromium oxide, chromium hydroxide, iron blue, ultramarine blue, and iron oxide; mica titanium, bismuth oxychloride , organic pigment treatment of mica titanium, titanium dioxide coated mica, titanium dioxide coated synthetic phlogopite, titanium dioxide coated bismuth oxychloride, iron oxide mica titanium, iron blue treated mica titanium, carmine treated mica titanium, fish scale foil, titanium dioxide coated glass powder, poly Ethylene terephthalate ‧ aluminum ‧ epoxide laminated powder, polyethylene terephthalate ‧ polyolefin laminated film powder, polyethylene terephthalate ‧ polymethyl methacrylate laminated film powder, etc. Bright pigments such as resin laminated powder; 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 red 3, red 104, red 106, orange 205, yellow 4, yellow 5, green 3, blue 1 and other zirconium, hafnium or aluminum lake; aluminum powder, gold powder, Based powder metal powder; particulate titanium oxide coated mica titanium, particulate zinc oxide coated mica titanium, barium sulfate coated mica titanium, silicon dioxide containing titanium oxide, comprising zinc oxide, silicon dioxide and the like of the composite powder and the like.

Further, such a fluorine-based compound, a polyoxymethylene compound, a metal soap, a lecithin, a hydrogenated lecithin, a collagen, a hydrocarbon, a higher fatty acid, a higher alcohol, an ester, a wax, a wax, a surfactant, etc. may be used. One or two or more kinds of surface treatments are carried out.

Further, by containing anhydrous citric acid in the powder, a good product can be obtained in terms of accelerating the drying speed and not sticking when the makeup is finished. For example, for eyeliner cosmetics or eyelash cosmetics, it is also useful in terms of usability. Get a better product.

As the anhydrous citric acid, a user who is usually used for cosmetics can be used, and an amorphous structure, a hydrophobized person, or a crystal structure can be preferably used. The size of the particles is not particularly limited, and is preferably 1 nm to 50 μm, and more preferably 3 nm to 30 μm, as measured by a volume average particle diameter laser diffraction type particle size distribution measuring apparatus. If it is in this range, the feeling of use can be improved.

As a commercial item, Sylysia 550, Sylysia 770, Sylosphere C-1504 (manufactured by Fuji-Silysia Chemical Co., Ltd.), AEROSIL 200, AEROSIL 300, AEROSIL R972 (manufactured by Nippon Aerosil Co., Ltd.), Nipseal E-220 (Tosoh Silica Co., Ltd.) Manufacturing) and so on. These anhydrous citric acid may be used alone or in combination of two or more.

The amount of the powder to be blended is not particularly limited. For example, in the case of a lip cosmetic, it is 0.01 to 25%, preferably 0.1 to 20%. When it is in this range, it can satisfy the request of the makeup film, the color retention property, and the secondary adhesion prevention effect which are not turbid. Further, in the case of eyeliner cosmetics or eyelash cosmetics, it is preferably from 0.1 to 60%, and more preferably from 0.5 to 45%. If it is within this range, it can be colored, and it will not stick when finished, and it can form a film with uniform coating film strength, and it is excellent in glossiness. For eyeliner cosmetics, color rendering and its persistence can be obtained. More preferably, for the cosmetic for eyelashes, the curling force and its durability are more excellent.

Further, in the case where the powder contains anhydrous citric acid, for example, in the eyeliner cosmetic or the eyelash cosmetic, the amount of the anhydrous citric acid powder is from 3 to 100%, preferably from 6 to 40%.

(Liquid non-volatile hydrocarbon oil at 25 ° C)

For example, by further containing a non-volatile hydrocarbon oil which is liquid at 25 ° C in the lip cosmetic, the cycloalkyl-containing acrylic copolymer of the present invention can be imparted with a plasticizing effect to exhibit color retention and no The sense of burden is better. Wherein, preferably the viscosity at 98.9 deg.] C of 200 mm ² / s of the non-volatile hydrocarbon oils. Particularly preferred are heavy liquid isoparaffins or polybutenes, polyisobutylene. As a commercial item, Parleam 18, Parleam 24, Parleam 46 (above, manufactured by Nippon Oil & Fats Co., Ltd.), Polybutene 100R, Polybutene 300R, Polybutene 2000H (above, manufactured by Idemitsu Kosan Co., Ltd.), and the like can be exemplified. Further, one type or two or more types may be used as needed.

The blending amount of the liquid non-volatile hydrocarbon oil at 25 ° C is 0.5 to 50%, preferably 1 to 10%. If it is within this range, the person who satisfies the requirements in terms of color retention and no feeling of burden can be obtained.

(other ingredients)

Examples thereof include a volatile oil agent and an oil agent, a fiber, a film-forming dispersion, a surfactant, an aqueous component, an ultraviolet absorber, a humectant, and an anti-fading agent other than a liquid non-volatile hydrocarbon oil at 25 ° C. , antioxidants, defoamers, beauty ingredients, preservatives, spices, etc.

The details will be described below.

(Volatile oil agent and oil agent other than liquid non-volatile hydrocarbon oil at 25 ° C)

The oil agent other than the volatile oil agent and the non-volatile hydrocarbon oil which is liquid at 25 ° C can be used without any particular limitation as long as it is an oil component used in usual cosmetics, irrespective of the origin of animal oil, vegetable oil, synthetic oil, and the like. Or solid oil, semi-solid oil, liquid oil and other properties, such as hydrocarbons, oils and fats, waxes, hardened oils, ester oils, fatty acids, higher alcohols, polyoxyxides, fluorine-based oils, Lanolin derivatives, oil gelling agents, etc.

Specifically, the following one or two or more types can be used.

Liquid paraffin, α-olefin oligomer, squalane, petrolatum, ceresin, polyethylene wax, Fischer-Tropsch wax, paraffin wax, microcrystalline wax, ceresin, ethylene propylene copolymer, etc.; olive oil, castor oil, Oyster sauce, Australian walnut oil, lacquer wax and other oils; beeswax, carnauba wax, canary wax, cetyl wax, montan wax and other waxes; rosin acid pentaerythritol ester, dipentaerythritol fatty acid ester, cholesterol fatty acid ester, N - Laurel-L-glutamic acid bis(cholesteryl-behenyl-octyldodecyl) ester, isopropyl myristate, isopropyl palmitate, cetyl 2-ethylhexanoate, Octyl dodecyl myristate, tricaprylin, polyglyceryl diisostearate, polyglyceryl triisostearate, diisostearyl malate, neopentyl glycol dioctanoate, charge Esters such as joba oil; fatty acids such as stearic acid, lauric acid, myristic acid, behenic acid, isostearic acid, oleic acid; stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl Higher alcohols such as alcohol and behenyl alcohol; low degree of polymerization dimethyl polyoxyalkylene, high polymerization degree dimethyl polyoxyalkylene, methyl phenyl poly Oxane, alkoxy modified polyoxyalkylene, crosslinked organic polyoxane, fluorine modified polyoxyalkylene, etc.; perfluorodecane, perfluorooctane, perfluoropolyether, etc. Fluorine-based oils; lanolin, lanolin acetate, lanolin fatty acid isopropyl ester, lanolin alcohol and other lanolin derivatives; 12-hydroxystearic acid, palmitic acid dextrin, palmitic acid/2-ethylhexyl Acid dextrin, stearic acid dextrin, palmitic acid/stearic acid dextrin, oleic acid dextrin, isopalmitate dextrin, dextrin fatty acid ester of stearic acid dextrin, stearic acid sucrose, acetic acid hard A sucrose fatty acid ester of sucrose fatty acid, an oily gelling agent such as aluminum isostearate or calcium stearate.

(film forming dispersion)

The film-forming dispersion is not particularly limited as long as it is a state in which the polymer having the film forming ability is emulsified in an aqueous solvent or dispersed in an oily solvent, and is generally used in cosmetics. By. For example, the state of emulsifying in an aqueous solvent may be exemplified by an alkyl acrylate copolymer emulsion, an alkyl acrylate-styrene copolymer emulsion, a polyvinyl acetate emulsion, a vinyl pyrrolidone styrene copolymer emulsion, As a commercial item, YODOZOL 32A707, YODOZOL GH810F, YODOZOL GH800F (made by NSC Corporation of Japan), Plextol B-500 (made by ROHM GMBH), YODOZOL GH41F (made by NSC Corporation of Japan), Vinyblan 1080, Vinyblan 1128C, Vinyblan 1080M, Vinyblan 1080T, Vinyblan GV-5651, Vinyblan 1108S/W (Nissin Chemical Industry Co., Ltd.), ANTARA430 (manufactured by ISP). In addition, the alkyl acrylate-styrene copolymer emulsion is exemplified as a commercially available product, and Nissetsu U-3700A (manufactured by Japan Carbide Industries Co., Ltd.) is mentioned as a commercial item.

(surfactant)

The surfactant may be any surfactant used in cosmetics, and examples thereof include a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant.

Examples of the nonionic surfactant include glycerin fatty acid esters and alkylene glycol adducts thereof, polyglycerin fatty acid esters and alkylene glycol adducts thereof, propylene glycol fatty acid esters, and alkylene glycol adducts thereof. , sorbitan fatty acid esters and alkylene glycol adducts thereof, fatty acid esters of sorbitol and alkylene glycol adducts thereof, polyalkylene glycol fatty acid esters, sucrose fatty acid esters, polyoxyalkylenes Alkyl ether, glyceryl alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene hardened castor oil, lanolin alkanediol adduct, polyoxyalkylene alkyl co-modified polyoxyl, Polyether modified polyfluorene 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, and dialkylsulfonates. Succinate, α-sulfonated fatty acid salt, mercaptomethyl taurate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl Ether phosphate, polyoxyethylene alkylphenyl ether phosphate, N-decylamino acid salt, o-alkyl substituted malate, alkyl sulfosuccinate, and the like.

Examples of the cationic surfactant include an alkylamine salt, a polyamine, an alkanolamine fatty acid derivative, an alkyl quaternary ammonium salt, and a cyclic quaternary ammonium salt.

As the amphoteric surfactant, those having an amino acid type or a betaine type, a carboxylic acid type, a sulfate type, a sulfonic acid type, or a phosphate type can be used for human safety. For example, N,N-dimethyl-N-alkyl-N-carboxymethylammonium betaine, N,N-dialkylaminoalkylenecarboxylic acid, N,N,N-trialkyl- N-sulfoalkylammonium betaine, N,N-dialkyl-N,N-bis(polyoxyethylene sulfate) ammonium betaine, 2-alkyl-1-hydroxyethyl-1-carboxymethylimidazole Betaine, lecithin, etc.

(aqueous ingredient)

The water-soluble component may be any component as long as it is a component soluble in water, and examples thereof include alcohols such as ethanol and isopropyl alcohol; propylene glycol, 1,3-butylene glycol, dipropylene glycol, and polyethylene glycol; Alcohols; glycerols such as glycerin, diglycerin, polyglycerin; saccharides such as sorbitol, maltitol, sucrose, starch sugar, lactitol; ancient gum, sodium chondroitin, sodium hyaluronate, gum arabic, sodium alginate, Water-soluble polymer such as carrageenan, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyvinyl polymer, polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylate; chlorination Salts such as sodium, magnesium chloride, and sodium lactate; plant extracts such as aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender, rose, etc., and water.

(moisturizer)

Examples of the humectant include: natural gum, sodium chondroitin sulfate, sodium hyaluronate, gum arabic, sodium alginate, carrageenan, and the like; methyl cellulose, hydroxyethyl cellulose, carboxymethyl fiber Semi-synthetic system such as carboxy group; carboxyvinyl polymer, alkyl-added carboxyvinyl polymer, polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylate, etc.; other proteins, mucopolysaccharides, collagen , elastin, keratin and so on.

(Others, UV absorbers, antioxidants, etc.)

Examples of the ultraviolet absorber include benzophenone-based, PABA (para-aminobenzoic acid), cinnamic acid, salicylic acid, and 4-tert-butyl-4'-methoxy. Examples of the antioxidant include, for example, α-tocopherol and ascorbic acid, and examples of the cosmetic component include vitamins, anti-inflammatory agents, and natural medicines. Examples of the agent include p-hydroxybenzoic acid ester, phenoxyethanol, and 1,2-pentanediol.

(dosage form, form, etc.)

The dosage form of the cosmetic cosmetic of the present invention is not particularly limited, and examples thereof include a water-in-oil type, an oil-in-water type, an oil type, and a powder type. In addition, the oily type refers to a cosmetic in which a liquid, semi-solid or solid oil agent or an oily component as an oil-soluble compound is formed into a continuous phase, and substantially does not contain water. Further, the form and the like can be appropriately selected depending on the use.

For example, as the lip cosmetic, the dosage form is not particularly limited, and from the viewpoint of color retention or gloss, it is preferred that the external phase is an oily oil-based or water-in-oil type. Examples of the shape include a solid form, a semi-solid form, and a liquid form, and can be used as a lipstick, a lip gloss, a lip balm, a lip cream, a lip base cream for a primer, a lipstick protective layer, and the like.

Further, as the eyeliner cosmetic, an oily type is preferred. Examples of the form include a liquid form, a semi-solid form, and a solid form. As a cosmetic for eyelashes, an oily type is preferred. Examples of the form include a liquid form, a semi-solid form, and the like, and can be used as a mascara, a mascara protective layer, a mascara primer, and the like.

Hereinafter, the present invention will be specifically described by way of examples, but the technical scope of the present invention is not limited to the examples.

I. Manufacture of a cycloalkyl-containing acrylic copolymer [Manufacturing Example 1] [Synthesis of a cycloalkyl-containing acrylic copolymer (1)]

Add 22.5 g of cyclohexyl methacrylate and 7.5 g of 2-ethyl methacrylate to a four-neck separable flask (hereinafter also referred to as "flask") equipped with a reflux condenser, a thermometer, a nitrogen introduction tube, and a stirring device. Hexyl hexyl ester and 70 g of toluene were introduced into a nitrogen atmosphere after introducing nitrogen gas, and then heated to 100 ° C, and 0.15 g of α,α'-azobisisobutyronitrile (hereinafter referred to as AIBN) was added thereto, and refluxed for 3 hours. Perform polymerization. Methanol was injected into the obtained reaction product, and the acrylic copolymer was precipitated and precipitated, and the precipitate was separated by filtration, and then vacuum-dried to obtain 27.4 g of a cycloalkyl group-containing acrylic copolymer solid content component. The weight average molecular weight in terms of polystyrene was 5.0 × 10 ⁴ .

[Manufacturing Example 2] [Synthesis of a cycloalkyl group-containing acrylic copolymer (2)]

15 g of cyclohexyl methacrylate, 15 g of 2-ethylhexyl methacrylate and 70 g of toluene were added to the flask, and nitrogen gas was introduced thereto to sufficiently adjust to a nitrogen atmosphere. After heating to 100 ° C, 0.15 g was added. The AIBN was refluxed for 3 hours for polymerization. Methanol was injected into the obtained reaction product, and the acrylic copolymer was precipitated and precipitated, and the precipitate was separated by filtration, and then vacuum-dried to obtain 25.5 g of a cycloalkyl group-containing acrylic copolymer solid content component. The weight average molecular weight in terms of polystyrene was 3.7 × 10 ⁴ .

[Manufacturing Example 3] [Synthesis of a cycloalkyl group-containing acrylic copolymer (3)]

21 g of cyclohexyl methacrylate, 9 g of 2-ethylhexyl methacrylate and 70 g of toluene were added to the flask, and nitrogen gas was introduced thereto to sufficiently adjust to a nitrogen atmosphere. After heating to 100 ° C, 0.15 g was added. The AIBN was refluxed for 3 hours for polymerization. Methanol was injected into the obtained reaction product, and the acrylic copolymer was precipitated and precipitated, and the precipitate was separated by filtration, and then vacuum-dried to obtain 23.8 g of a cycloalkyl group-containing acrylic copolymer solid content component. The weight average molecular weight in terms of polystyrene was 4.7 × 10 ⁴ .

[Manufacturing Example 4] [Synthesis of a cycloalkyl-containing acrylic copolymer (4)]

22.5 g of cyclohexyl methacrylate, 7.5 g of a methacrylic acid modified dimethyl polyoxyalkylene macromonomer of the following formula (V), and 70 g of toluene were added to the flask, and nitrogen gas was introduced and sufficiently adjusted. After the nitrogen atmosphere, the mixture was heated to 80 ° C, and 0.15 g of α,α'-azobisisobutyronitrile (hereinafter referred to as AIBN) was added, and the mixture was refluxed for 5 hours to carry out polymerization. Methanol was injected into the obtained reaction product, and the acrylic copolymer was precipitated and precipitated, and the precipitate was separated by filtration, and then vacuum-dried to obtain 13.4 g of a cycloalkyl group-containing acrylic copolymer solid content component. The weight average molecular weight in terms of polystyrene was 5.2 × 10 ⁴ .

[化8]

[Manufacturing Example 5] [Synthesis of a cycloalkyl-containing acrylic copolymer (5)]

To the flask, 22.5 g of cyclohexyl methacrylate, 7.5 g of a methacrylic acid modified dimethyl polyoxyalkylene macromonomer of the following formula (VI), and 70 g of toluene were added, and nitrogen gas was introduced and sufficiently adjusted. After the nitrogen atmosphere, the mixture was heated to 100 ° C, 0.15 g of AIBN was added, and the mixture was refluxed for 3 hours to carry out polymerization. The obtained reactant was distilled off by evaporation to remove toluene, and then vacuum-dried to obtain 26.6 g of a cycloalkyl group-containing acrylic copolymer solid content component. The weight average molecular weight in terms of polystyrene was 6.7 × 10 ⁴ .

[Chemistry 9]

[Manufacturing Example 6] [Synthesis of a cycloalkyl-containing acrylic copolymer (6)]

22.5 g of cyclohexyl methacrylate, 7.5 g of a methacrylic acid modified dimethyl polyoxyalkylene macromonomer of the following formula (VII), and 70 g of toluene were added to the flask, and nitrogen gas was introduced and sufficiently adjusted. After heating in a nitrogen atmosphere, the mixture was heated to 80 ° C, 0.15 g of AIBN was added, and the mixture was refluxed for 5 hours to carry out polymerization. Methanol was injected into the obtained reaction product, and the acrylic copolymer was precipitated and precipitated, and the precipitate was separated by filtration, followed by vacuum drying to obtain 29.1 g of a cycloalkyl group-containing acrylic copolymer solid content component.

[化10]

[Manufacturing Example 7] [Synthesis of a cycloalkyl group-containing acrylic copolymer (7)]

21 g of cyclohexyl methacrylate, 4.5 g of 2-ethylhexyl methacrylate, 4.5 g of the methacrylic acid modified dimethyl polyoxyalkylene macromonomer of the above formula (VI) were added to the above flask. After 70 g of toluene was introduced and nitrogen gas was introduced and the nitrogen atmosphere was sufficiently adjusted, the mixture was heated to 80 ° C, 0.15 g of AIBN was added, and the mixture was refluxed for 5 hours to carry out polymerization. Methanol was injected into the obtained reaction product, and the acrylic copolymer was precipitated and precipitated, and the precipitate was separated by filtration, and then vacuum-dried to obtain 11.0 g of a cycloalkyl group-containing acrylic copolymer solid content component. The weight average molecular weight in terms of polystyrene was 6.2 × 10 ⁴ .

[Manufacturing Example 8]

Each of the combinations shown in the following (8) to (12) is used as a raw material, and the synthesis is carried out in accordance with the above synthesis method. As a result, a cycloalkyl group-containing acrylic copolymer can be obtained.

(8) 50% of cyclohexyl methacrylate and 50% of the methacrylic acid modified dimethyl polyoxyalkylene macromonomer of the above formula (VI),

(9) 50% cyclohexyl methacrylate and 50% lauryl methacrylate,

(10) 75% of cyclohexyl methacrylate and 25% of lauryl methacrylate,

(11) 60% of cyclohexyl methacrylate and 40% of 2-ethylhexyl methacrylate, and

(12) methacrylic acid modified dimethyl polyoxyalkylene macromonomer of formula (IV) wherein cyclohexyl methacrylate and n=150, R ₁₃ is CH ₃ group, and R ₁₄ is C ₄ H ₉ group .

(Manufacturing Comparative Example 1) [Synthesis of poly(cyclohexyl methacrylate)]

30 g of cyclohexyl methacrylate and 70 g of toluene were added to the flask, and nitrogen gas was introduced thereto to sufficiently adjust the atmosphere to nitrogen atmosphere. After heating to 100 ° C, 0.15 g of AIBN was added, and the mixture was refluxed for 3 hours to carry out polymerization. Methanol was injected into the obtained reaction product, and the acrylic polymer was precipitated and precipitated, and the precipitate was separated by filtration, followed by vacuum drying to obtain 29.9 g of a poly(cyclohexyl methacrylate) solid content component.

(Manufacturing Comparative Example 2) [Synthesis of a cycloalkyl-containing acrylic copolymer (8)]

15 g of cyclohexyl methacrylate, 15 g of ethyl acrylate and 70 g of toluene were added to the flask, and nitrogen gas was introduced thereto to sufficiently adjust the atmosphere to nitrogen. After heating to 100 ° C, 0.15 g of AIBN was added and refluxed for 3 hours. Perform polymerization. Methanol was injected into the obtained reaction product, and the acrylic polymer was precipitated and precipitated, and the precipitate was separated by filtration, and then vacuum-dried to obtain a cycloalkyl group-containing acrylic copolymer.

(Manufacturing Comparative Example 3) [Synthesis of a cycloalkyl-containing acrylic copolymer (9)]

50 g of cyclohexyl methacrylate, 50 g of n-butyl methacrylate and 70 g of toluene were added to the flask, and nitrogen gas was introduced thereto to sufficiently adjust to a nitrogen atmosphere. After heating to 100 ° C, 0.15 g of AIBN was added. The polymerization was carried out by refluxing for 3 hours. Methanol was injected into the obtained reaction product, and the acrylic polymer was precipitated and precipitated, and the precipitate was separated by filtration, followed by vacuum drying to obtain 22.2 g of a cycloalkyl group-containing acrylic copolymer solid content component.

(Manufacturing Comparative Example 4) [Synthesis of a cycloalkyl group-containing acrylic copolymer (10)]

15 g of cyclohexyl methacrylate, 15 g of tributyl methacrylate and 70 g of toluene were added to the flask, and nitrogen gas was introduced thereto to sufficiently adjust the atmosphere to nitrogen. After heating to 100 ° C, 0.15 g of AIBN was added. The polymerization was carried out by refluxing for 3 hours. Methanol was injected into the obtained reaction product, and the acrylic copolymer was precipitated and precipitated, and the precipitate was separated by filtration and dried under vacuum to obtain 19.6 g of a cycloalkyl group-containing acrylic copolymer solid component.

(Manufacturing Comparative Example 5) [Synthesis of a cycloalkyl-containing acrylic copolymer (11)]

22.5 g of cyclohexyl methacrylate, 7.5 g of butyl methacrylate and 70 g of toluene were added to the flask, and nitrogen gas was introduced thereto to sufficiently adjust the atmosphere to nitrogen. After heating to 100 ° C, 0.15 g of AIBN was added. The polymerization was carried out by refluxing for 3 hours. Methanol was injected into the obtained reaction product, and the acrylic polymer was precipitated and precipitated, and the precipitate was separated by filtration, followed by vacuum drying to obtain 23.8 g of a cycloalkyl group-containing acrylic copolymer solid content component.

(Manufacturing Comparative Example 6) [Synthesis of Acrylic-Polyoxired Graft Polymer]

Add 100 g of toluene to a four-neck separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a dropping funnel to uniformly dissolve 40 g of methyl methacrylate and 20 g of n-butyl methacrylate. Introducing 40 g of a reaction solution of 40 g of the above-mentioned methacrylic acid modified dimethyl polyoxyalkylene macromonomer of the formula (VI), 50 g of toluene and 1.5 g of tributyl butyl peroxy-2-ethylhexanoate It was added dropwise at 100 ° C under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was refluxed for 5 hours to carry out polymerization. Methanol was injected into the obtained reactant to precipitate an acrylic acid-polyoxyl graft polymer, and the precipitate was separated by filtration and vacuum dried to obtain 78.5 g of an acrylic acid-polyoxyl graft polymer solid component. .

(Evaluation)

The acrylic copolymers of Production Examples 1 to 7 and Comparative Examples 1 to 6 were evaluated in the light liquid isomerized paraffin (IP Solvent 1620 (manufactured by Idemitsu Kosan Co., Ltd.), and the ignition point was 49 ° C). Solubility, transparency and strength of the film. The results are shown in Tables 1 and 2.

[Table 1]

[Table 2]

<Evaluation method> (1) Solubility in light liquid isomerized paraffin (IP Solvent 1620 (manufactured by Idemitsu Kosan Co., Ltd.))

To 30 parts by mass of the acrylic copolymers of Production Examples 1 to 7 and Comparative Examples 1 to 6, 70 parts by mass of a light liquid isomerized paraffin was added and mixed, and the solubility at 25 ° C was evaluated based on the following evaluation criteria. .

◎: Transparent dissolution.

○: It was slightly turbid, but dissolved.

Δ: A part of the acrylic copolymer which was dissolved but not dissolved was sedimented.

×: Not dissolved.

(2) Transparency of the film

The production example dissolved in the light liquid isomerized paraffin and the 30% by mass acrylic copolymer solution of the comparative example were formed into a film on a glass plate by an applicator of 100 μm, and then dried to prepare an acrylic copolymer. The film was visually evaluated for transparency of the film.

○: transparent

Δ: visible slightly turbid but translucent

×: turbid and opaque

(3) hardness of the film

The production examples 1 to 7 dissolved in the light liquid isomerized paraffin and the 30% by mass acrylic copolymer solution of Comparative Examples 1 to 6 were formed into a film on a glass plate by an applicator of 100 μm, and then dried. A film of an acrylic copolymer was prepared, and a pencil hardness test was carried out in accordance with the method of JIS-K5400.

From the results of Production Examples 1 to 7 of Table 1, it is understood that the cycloalkyl group-containing acrylic copolymer of the present invention has good solubility in a light liquid isomerized paraffin, and the film transparency is high and hard. The film forming agent is excellent. Further, the five kinds of cycloalkyl group-containing acrylic copolymers described in Production Example 8 were also found to be dissolved in the light liquid isomerized paraffin to form a transparent film. On the other hand, it was confirmed that the acrylic copolymers of Comparative Examples 1 to 5 were not dissolved in the light liquid isomerized paraffin, and were not suitable as a film forming agent. Further, the acrylic-polyfluorene-oxygen graft polymer of Comparative Example 6 was produced as the polymer described in Patent Document 1, but it was confirmed that the film was too soft to obtain sufficient hardness, and may be sticky or sticky, and the film may be Disadvantages such as unevenness.

Lip cosmetics [Examples 1 to 8 and Comparative Examples 1 to 5] Oily liquid lipstick

The oily liquid lipstick having the composition shown in Table 3 was prepared by the following production method, and for each sample, A. time-lapse color retention, B. anti-secondary adhesion effect, C. glossiness, D. no burden, E. The evaluation of the smooth use was carried out, and the results are also shown in Table 3.

[table 3]

*1: The cycloalkyl group-containing acrylic copolymer of Production Example 1 (1)

*2: The cycloalkyl group-containing acrylic copolymer of Production Example 2 (2)

*3: The cycloalkyl group-containing acrylic copolymer of Production Example 3 (3)

*4: The acrylic polymer of Comparative Example 1 was produced.

*5: Silicon KF-7312 (manufactured by Shin-Etsu Chemical Co., Ltd.), 50% decamethylcyclopentaoxane solution

*6: Nissetsu U-3700A (manufactured by Carbide Industries, Japan), 50% light liquid isomerized paraffin solution

*7: IP Solvent 2028 (made by Idemitsu Kosan Co., Ltd.)

*8: AEROSIL 300 (manufactured by Japan Aerosil Co., Ltd.)

*9: BENTONE 38 (manufactured by Elementis)

*10: Polybutene 2000H (manufactured by Idemitsu Kosan Co., Ltd.)

(Production method)

A: The components (1) to (8) are uniformly dissolved.

B: Add components (9) to (15) in A, and uniformly mix and disperse.

C: After defoaming B, it was filled in a container with an applicator.

(evaluation method)

Each sample was tested by 20 panelists. Each member of the group evaluated C, D, and E immediately after application. For B, the evaluation did not change color when wiped with tissue paper after 10 minutes after application. For A, observe 6 hours after application. The evaluation is performed on the basis of the above-mentioned absolute evaluation criteria, and the score is given in six levels according to the following absolute evaluation criteria, and the average value is calculated based on the total value of the scores of the samples of all the members of the group, and is determined according to the following four levels. The benchmark is judged. The table shows the judgment result and the average value of the score in ().

<Functional evaluation item>

A. Temporal color retention

B. Prevent secondary adhesion

C. Gloss

D. No burden

E. Smooth use

<Absolute Evaluation Benchmark>

<Level determination criteria>

As is clear from the results of Table 3, the oily liquid lipsticks of Examples 1 to 8 of the present invention have color retention, secondary adhesion prevention, glossiness, and glossiness as compared with the oily liquid lipsticks of Comparative Examples 1 to 5. It has no sense of burden and is excellent in smooth use. In particular, Example 6 in which an olefin polymer and/or a polyolefin which is a non-volatile hydrocarbon oil which is liquid at 25 ° C is blended is excellent in color retention and no burden. On the other hand, in Comparative Example 1 in which the cycloalkyl group-containing acrylic copolymer of the present invention was not blended, no film was formed, so that the color retention property was inferior and no secondary adhesion prevention effect was observed. In Comparative Example 2 in which the volatile oil agent was not formulated, the cosmetic film could not form a sufficient film, and it was not possible to obtain a satisfactory effect against the secondary adhesion effect and the feeling of no burden. Further, in Comparative Example 3 in which an acrylic polymer was used in place of the cycloalkyl group-containing acrylic copolymer of the present invention, since the cosmetic film lacked uniformity, it was not possible to obtain a satisfactory feeling in glossiness, and trimethylnonyloxy group was used. In Comparative Example 4 in which decanoic acid was used in place of the cycloalkyl group-containing acrylic copolymer of the present invention, since the cosmetic film lacked flexibility, it was not possible to obtain a satisfactory feeling in terms of no burden, and an alkyl acrylate-styrene copolymer was used. In Comparative Example 5 in which the dispersion liquid was used in place of the cycloalkyl group-containing acrylic copolymer of the present invention, the cosmetic film lacked flexibility and uniformity, and was not satisfactory in terms of glossiness and no burden.

[Example 9] Oily stick lipstick

*11: PERFORMALENE 500 (manufactured by New Phase Technologies)

*12: Isododecane (manufactured by Bayer)

*13: AEROSIL R972 (manufactured by Japan Aerosil Co., Ltd.)

*14: 3% treatment with dimethyl polyoxane

(Production method)

A: The component (4) and the component (5) were uniformly dissolved.

B: A and the components (1) to (3) and the components (6) to (8) were uniformly heated and dissolved at 95 °C.

C: Adding components (9) to (14) to B, and uniformly mixing and dispersing.

D: After defoaming C, it is filled into a container.

(Evaluation)

The oily stick-like lipstick obtained in this manner was evaluated in the same manner as in Examples 1 to 8. As a result, the color retention property, the secondary adhesion preventing effect, the glossiness, the feeling of no burden, and the smooth feeling of use were excellent.

[Example 10] Oily cream lip gloss

*15: Parleam 18 (manufactured by Nippon Oil & Fats Co., Ltd.)

*16: 30% light liquid isomerized paraffin 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: The components (1) to (4) were uniformly heated and dissolved at 95 °C.

B: Add components (5) to (6) in A, and uniformly mix and disperse.

C: After defoaming B, it was filled into a tubular container.

(Evaluation)

The oily cream lip gloss obtained in this manner was evaluated in the same manner as in Examples 1 to 8. As a result, the color retention property, the secondary adhesion prevention effect, the glossiness, the feeling of no burden, and the smooth feeling of use were excellent.

[Example 11] oily solid lip cream

*18: The cycloalkyl group-containing acrylic copolymer of Production Example 4 (4)

*19: The cycloalkyl group-containing acrylic copolymer of Production Example 5 (5)

*20: isohexadecane (manufactured by Uniqema)

*21: Perfluoropolyether 5% treatment

(Production method)

A: The components (1) to (7) were uniformly heated and dissolved at 95 °C.

B: Add components (8) to (11) to A, and uniformly mix and disperse.

C: After defoaming B, it was filled into a can container.

(Evaluation)

The oily solid lip cream obtained in this manner was evaluated in the same manner as in Examples 1 to 8, and as a result, color retention, secondary adhesion prevention, glossiness, no burden, and smooth use were observed. Excellent.

[Example 12] Water-in-oil type cream lipstick

*22: The cycloalkyl group-containing acrylic copolymer of Production Example 6 (6)

(Production method)

A: The components (1) to (7) were uniformly heated and dissolved at 95 °C.

B: The component (8) was added to A to carry out emulsification. Thereafter, components (9) to (10) were added and uniformly mixed.

C: After defoaming B, it was filled into a tubular container.

(Evaluation)

The water-in-oil type cream-like lipstick obtained in this manner was evaluated in the same manner as in Examples 1 to 8, and as a result, color retention, secondary adhesion prevention, glossiness, no burden, and smooth use were observed. Excellent feeling.

[Example 13] Water-in-oil type cream-like lipstick base

*23: The cycloalkyl group-containing acrylic copolymer of Production Example 7 (7)

(Production method)

A: The components (1) to (5) were uniformly heated and dissolved at 95 °C.

B: Emulsification was carried out by adding components (6) to (8) to A.

C: After defoaming B, it was filled into a tubular container.

(Evaluation)

The water-in-oil type cream-like lipstick primer obtained in this manner was evaluated in the same manner as in Examples 1 to 8. As a result, the color retention property, the feeling of no load, and the smooth feeling of use were excellent.

II Eyeliner Cosmetics [Examples 14 to 17, Comparative Examples 6 to 9] Eyeliner (oily liquid)

The eyeliner of the formulation shown in Table 4 was prepared by the following method, and the uniformity of the cosmetic film, the glossiness and color development as a makeup effect, and the non-staining and non-flaking of the cosmetic film were carried out by the following method. Functional evaluation. The results are also shown in Table 4.

[Table 4]

*24: IP Solvent 1620 (made by Idemitsu Kosan Co., Ltd.)

*25: The cycloalkyl group-containing acrylic copolymer (1) of Production Example 1 was dissolved in a light liquid isomerized paraffin (IP Solvent 1620) to prepare a 40% solution.

*26: Oppanol B-100 (manufactured by BASF)

*27: Silicon KF-9021 (manufactured by Shin-Etsu Chemical Co., Ltd.) (10% methylcyclopentaoxane solution with a solid content of 50%)

*28: Ester Gum HP (manufactured by Arakawa Chemical Industries, Ltd.)

*29: Nissetsu U-3700A (manufactured by Carbide Industries, Japan) (50% light-weight liquid isomerized paraffin solution with solid content)

*30: fluoroalkyl alkoxy decane 3% treatment

*31: AEROSIL R976S (manufactured by Japan Aerosil Co., Ltd.)

*32: AEROSIL 300 (manufactured by Japan Aerosil Co., Ltd.)

(method of law)

A. The components (1) to (10) are heated to 110 ° C and uniformly dissolved.

B. Add ingredients (11) to (16) to A and mix them evenly.

C. Fill the B into a container to make a product.

(evaluation method)

For each sample, the following evaluation items were used for the evaluation items of the following a to e; (1) The absolute evaluation criteria were evaluated in 7 levels, and the average of the scores of the respective samples was determined using the (2) 4 level determination criteria. Further, in Table 4, the judgment and the average value of the score are described in ().

Further, for the evaluation items d and e, the panel members were allowed to live normally after applying the sample along the contour of the eye, and the makeup effect after 12 hours was evaluated.

(evaluation project)

a. Uniformity of the cosmetic film

b. Gloss

c. Color rendering

d. no blooming (sustainability)

e. No peeling (sustainability)

(1) Absolute evaluation criteria

(2) Level 4 criteria

As is clear from the results of Table 4, the eyeliners of Examples 14 to 17 of the present invention can be smoothly drawn compared with the eye lines of Comparative Examples 6 to 9, so that the uniformity of the cosmetic film can be obtained, and the glossiness, The color-developing effect is excellent, and the makeup effect of no blooming or peeling after 12 hours can be obtained, and it has excellent characteristics in all respects.

On the other hand, in Comparative Example 6 in which polyisobutylene was used in place of the cycloalkyl group-containing acrylic copolymer of the present invention, there was a lack of smoothness in use, so that it was difficult to uniformly adhere, and it was impossible to obtain a uniformity or glossiness of the cosmetic film. Meet the requirements.

Further, in Comparative Example 7 in which a trimethyldecyloxydecanoic acid solution was used in place of the cycloalkyl group-containing acrylic copolymer of the present invention, since the cosmetic film lacked flexibility and could not follow the eye movement, the cosmetic film Some of them are peeled off, and the uniformity of the cosmetic film is also lowered. Therefore, the glossiness and the color rendering degree are not satisfactory, and the smoothness is lacking, so that there is a problem in the usability that is difficult to draw.

Further, in Comparative Example 8 in which cyclamate pentaerythritol was used in place of the cycloalkyl group-containing acrylic copolymer of the present invention, the cosmetic film was sticky when used, the uniformity of the cosmetic film was deteriorated, and the glossiness was also lowered, and the satisfactory one could not be obtained. .

Further, in Comparative Example 9 in which the light-weight liquid isomerized paraffin dispersion of the acrylic-styrene copolymer resin was used in place of the cycloalkyl group-containing acrylic copolymer of the present invention, the thickness of the cosmetic film could not be sufficiently obtained, and thus the cosmetic film lacked smoothness. Since the transparency of the cosmetic film is also inferior, the glossiness or the color rendering degree cannot be obtained, and the smoothness is lacking, so that there is a problem in the usability that is difficult to draw.

[Examples 18 to 23] In place 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 dissolved in a light liquid. When a 40% solution was prepared by using paraffin wax (IP solvent 1620), mascara was obtained by the same manufacturing method as in Example 14, and the mascara was evaluated. As a result, the uniformity of the cosmetic film was excellent and the gloss was high. Sense or coloration, and no peeling or blooming, and the cosmetic effect is excellent in persistence. The formulations and their results are shown in Table 5. [table 5]

The following Examples 24 and 25 were also evaluated in the same manner as in Examples 14 to 17 and Comparative Examples 6 to 9.

[Example 24] Eyeliner (oily liquid type)

*33: The cycloalkyl group-containing acrylic copolymer (4) of Production Example 4 was dissolved in a light liquid isomerized paraffin (IP Solvent 1620) to prepare a 15% solution.

*34: dimethyl distearyl ammonium modified synthetic sodium citrate ‧ magnesium: Lucentite SAN (manufactured by CO-OP Chemical Co., Ltd.)

*35: Silicon KF-995 (manufactured by Shin-Etsu Chemical Co., Ltd.)

*36: dimethyl polyoxane 4% treatment

(Production method)

A. The components (1) to (6) are dissolved by heating.

B. Add ingredients (7) to (15) in A and mix them evenly.

C. Fill B into the container to obtain an oily eyeliner.

(Evaluation)

The oily liquid eyeliner makeup film obtained as described above is excellent in uniformity, has a high glossiness or coloration, and has no peeling or blooming, and is excellent in persistence of a makeup effect.

[Example 25] Eyeliner (water-in-oil type liquid)

*37: The cycloalkyl group-containing acrylic copolymer (1) of Production Example 1 was dissolved in a light liquid isomerized paraffin (IP Solvent 1620) to prepare a 20% solution.

*38: Lucentite SSN (manufactured by CO-OP Chemical Co., Ltd.)

*39: BENTONE 38V BC (manufactured by Elementis)

*40: KF-6028P (manufactured by Shin-Etsu Chemical Co., Ltd.)

*41: 2% treatment of methyl hydrogenated polyoxyalkylene

*42: ANTARA 430 (made by ISP)

(method of law)

A. The components (1) to (3) are dissolved by heating at 110 ° C, and (4) to (9) are added for mixing.

B. Add ingredients (10) to (16), and mix and dissolve them evenly.

C. Add B to A to carry out emulsification.

D. Fill C into a container to make a product.

(Evaluation)

The water-in-oil type liquid eyeliner makeup film obtained as described above is excellent in uniformity, has a high glossiness or coloration, and has no peeling or blooming, and is excellent in durability of a makeup effect.

III eyelash cosmetics [Examples 26 to 30 and Comparative Examples 10 to 12] Mascara (oily liquid type)

The mascara of the formulation shown in Table 6 was prepared by the following method, and the glossiness, the curling lifting effect, the curl holding effect, and the uniformity of the cosmetic film were evaluated by the following methods. The results are also shown in Table 6.

[Table 6]

*43: IP Solvent 1620 (made by Idemitsu Kosan Co., Ltd.)

*44: The cycloalkyl group-containing acrylic copolymer (1) of Production Example 1 was dissolved in a light liquid isomerized paraffin (IP Solvent 1620) to prepare a 40% solution.

*45: Silicon KF-9021 (manufactured by Shin-Etsu Chemical Co., Ltd.) (10% methylcyclopentaoxane solution with a solid content of 50%)

*46: Ester Gum HP (manufactured by Arakawa Chemical Industries, Ltd.)

*47: Nissetsu U-3700A (manufactured by Carbide Industries, Japan) (50% light solid liquid isomerized paraffin solution)

*48: BENTONE 38V BC (manufactured by ELEMENTIS)

*49: AEROSIL 300 (manufactured by Japan Aerosil Co., Ltd.)

(method of law)

A. The components (1) to (7) are heated to 110 ° C and uniformly dissolved.

B. Add ingredients (8) to (12) to A and mix them evenly.

C. B is cooled and filled into a container to make a product.

(evaluation method)

For each sample, the following evaluation items of A to E were used for evaluation of each sample, and the evaluation was performed in 7 levels using the (1) absolute evaluation criteria, and the average of the scores of the respective samples was determined using the (2) 4 level determination criteria. Further, in Table 6, the judgment is described and the average value of the score is described in ().

Further, the evaluation item B was evaluated immediately after the application, and the evaluation items A, C, D, and E were applied to the eyelashes, and the group members were allowed to live normally, and the makeup effect after 12 hours was evaluated.

(evaluation project)

A. Persistence of gloss

B. curling effect

C. curling retention effect

D. Sustainability of the abundance effect

E. The continuity of the uniformity of the cosmetic film

(1) Absolute evaluation criteria

(2) Level 4 criteria

As is clear from the results of Table 6, the mascara of Examples 26 to 30 which are the products of the present invention is very easy to apply, and the adhesion is also good. Since the smear is applied, the makeup film is uniform and shiny, and the curling effect can be obtained. And the sustainability of these is very excellent. In particular, Example 30 is also quite full of effects.

On the other hand, in Comparative Example 10 in which a trimethyl decyloxy phthalic acid solution was used instead of the cycloalkyl group-containing acrylic copolymer solution of the present invention, a firm cosmetic film was obtained, but flexibility could not be obtained, so that makeup was obtained. The uniformity of the film is lowered over time, so that the glossiness, the curl holding effect, and the uniformity of the cosmetic film cannot be obtained, and the adhesion is also low, so that the effect of the fullness cannot be obtained.

Further, in Comparative Example 11 in which cyclamate pentaerythritol was used in place of the cycloalkyl group-containing acrylic copolymer of the present invention, since the cosmetic film was sticky, the eyelashes were agglomerated with each other, resulting in a decrease in uniformity of the cosmetic film and glossiness. Also poor. Moreover, since the adhesion is too high, the eyelashes are heavy and droop, so that the curling retention effect cannot be obtained.

Further, in Comparative Example 12 in which the light-weight liquid isomerized paraffin dispersion of the acrylic-styrene copolymer resin was used in place of the cycloalkyl group-containing acrylic copolymer solution of the present invention, it was difficult to uniformly use due to lack of smooth useability. Adhesion, which is not satisfactory in terms of the uniformity or gloss of the cosmetic film. Further, since the strength of the cosmetic film is also insufficient, the cosmetic effect of the curling lifting effect or the curl holding effect and the sustainability thereof cannot be obtained.

Moreover, if the mascara of Examples 26 to 30 is applied repeatedly (using the smear tool for 10 times), the fullness effect can be obtained without impairing the uniformity of the cosmetic film or the curling retention effect, but if the smear is repeated, In Examples 10 to 12, the makeup film was too sticky, and the eyelashes were agglomerated with each other, and the uniformity of the cosmetic film could not be obtained, or the softness of the cosmetic film was also low, so that the feeling of use was also poor.

[Examples 31 to 36]

The cycloalkyl group-containing acrylic copolymers (2) to (7) obtained in Production Examples 2 to 7 were dissolved in a light liquid instead of the cycloalkyl group-containing acrylic copolymer solution used in Example 26. The mascara was obtained by the same method as that of Example 26, and the mascara was evaluated in the same manner as in Example 26, and the uniformity of the cosmetic film was high and shiny. The curl holding effect can also be obtained, and the persistence is also excellent. The formulations and their results are shown in Table 7.

[Table 7]

The following Examples 37 to 40 were also evaluated in the same manner as in Examples 26 to 30 and Comparative Examples 10 to 12.

[Example 37] Mascara (oil-in-water emulsion type)

*50: The cycloalkyl group-containing acrylic copolymer (4) of Production Example 4 was dissolved in a light liquid isomerized paraffin (IP Solvent 1620) to prepare a 20% solution.

*51: Sugar Wax S-10E (manufactured by First Industrial Pharmaceutical Co., Ltd.)

*52: Sylysia 550 (manufactured by Fuji-Silysia Chemical Co., Ltd.)

*53: Nipseal E-220 (manufactured by Nippon Silica Industrial Co., Ltd.)

*54: YODOZOL GH810F (solid content is 50%) (manufactured by NSC Japan)

*55: Vinyblan GV-5651 (40% solid content) (manufactured by Nissin Chemical Industry Co., Ltd.)

(method of law)

A. The components (1) to (10) are dissolved by heating at 110 ° C, and the component (11) is added and uniformly mixed.

B. Warm the ingredients (12) to (21) and mix them evenly.

C. B was added to A, and emulsification was carried out at 80 °C.

D. C is cooled and filled into a container to make a product.

(Evaluation)

The oil-in-water emulsified mascara obtained as described above is excellent in uniformity of the cosmetic film, and has excellent glossiness, curling effect, and a full-bodied cosmetic effect and durability.

[Example 38] Mascara (oily liquid type) (long type)

*56: Indigenous resin E-1 (manufactured by Natural Products, Japan)

*57: fluoroalkyl alkoxy decane 3% treatment

*58: Nylon fiber 6.3T-2MM (manufactured by Chubu-Pile Co., Ltd.)

(method of law)

A. The components (4) to (8) are heated and mixed at 90 ° C, and the components (1) to (3) are added, and the mixture is heated and dissolved at 110 ° C.

B. Add component (9) to A and mix.

C. Add ingredients (10) to (14) to B and mix them evenly.

D. C is cooled and filled into a container to make a product.

(Evaluation)

The oily mascara-based cosmetic film obtained as described above is excellent in uniformity of the uniformity, and has a glossiness, a curling effect, a slimming effect, a makeup effect of a bulkiness effect, and an excellent durability.

[Example 39] Mascara (water-in-oil emulsified liquid)

*59: KF-6028P (manufactured by Shin-Etsu Chemical Co., Ltd.)

*60: dimethyl polyoxane 4% treatment

(method of law)

A. Mix the ingredients (1) to (4) uniformly.

B. Add ingredients (5) to (8) to A and mix them.

C. Add components (9) to (13) to B, and emulsify at room temperature.

D. C is cooled and filled into a container to make a product.

(Evaluation)

The water-in-oil emulsified mascara obtained as described above is excellent in uniformity of the uniformity of the makeup film, and has a glossiness, a curling effect, a full-bodied effect, and a sustained effect.

[Example 40] Mascara base (oily liquid type)

*61: The cycloalkyl group-containing acrylic copolymer (1) of Production Example 1 was dissolved in a light liquid isomerized paraffin (IP Solvent 1620) to prepare a 15% solution.

*62: AEROSIL R972 (manufactured by Japan Aerosil Co., Ltd.)

(method of law)

A. The components (1) to (4) are uniformly mixed and dissolved at 110 ° C, and the components (5) to (10) are added and uniformly mixed.

B. Fill A into a container and cool to make a product.

(Evaluation)

The oil-based mascara-based makeup film obtained as described above is excellent in uniformity, and the commercially available mascara is easily applied repeatedly, and the curling effect, the makeup effect of the full-bodied effect, and the persistence are excellent.

[Industrial availability]

The cycloalkyl group-containing acrylic copolymer of the present invention is characterized in that it is dissolved in a volatile oil agent such as a light liquid isomerized paraffin, and has a high film 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 into a cosmetic, a cosmetic having excellent glossiness, adhesion, and water resistance and excellent cosmetic durability can be obtained, and is particularly suitable as a cosmetic.

For example, as an eyeliner cosmetic, the cosmetic film is excellent in uniformity, has a high glossiness or coloration, and is free from blooming or peeling, and is excellent in persistence of a makeup effect.

Moreover, as a cosmetic for eyelashes, the curling effect and the durability thereof are excellent, and the uniformity and glossiness of the cosmetic film are excellent. In addition, the lip cosmetic is excellent in color retention and secondary adhesion prevention effect, and is excellent in glossiness, no burden, and smooth feeling of use.

Claims (13)

A cosmetic cosmetic containing a cycloalkyl group-containing acrylic random copolymer, wherein the cycloalkyl group-containing acrylic random copolymer is characterized in that it comprises the following components (a1) and (a2); / or the monomer of the component (a3) is obtained by polymerization, and the amount of the component (a1) in the total amount of the monomers is 50 to 90% by mass, and the amount of the component (a2) and/or the component (a3) is adjusted. 10 to 50% by mass, and at least 30% by mass dissolved in a light liquid isomerized paraffin at 25 ° C; component (a1): acrylate and/or methacrylate represented by formula (I) (wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a cycloalkyl group); and component (a2): an acrylate and/or a methacrylate represented by the formula (II) [Chemical 2] (wherein R ₃ represents a hydrogen atom or a methyl group, R ₄ represents a linear or branched alkyl group having a carbon number of 8 to 12); and component (a3): an organic polyfluorene having a radical polymerizable group at one terminal Oxysilane macromonomer. The cosmetic of claim 1, wherein the cycloalkyl-containing acrylic random copolymer is obtained by polymerizing the components (a1) and (a2). The cosmetic preparation of claim 1, wherein the cycloalkyl group-containing acrylic random copolymer is obtained by polymerizing the component (a1) and the component (a3). The cosmetic preparation of claim 1, wherein the cycloalkyl group-containing acrylic random copolymer is obtained by polymerizing the component (a1), the component (a2), and the component (a3). The cosmetic of any one of 3 and 4, wherein the component (a3) is an organopolyoxyalkylene macromonomer represented by the following formula (III), [Chemical 3] (wherein R ₅ represents a hydrogen atom or a methyl group, R ₆ to R ₁₂ each independently represent an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 to 10, and n represents an integer of 0 to 200; ). The cosmetic preparation according to any one of claims 1 to 4, wherein the component (a1) is cyclohexyl methacrylate. The cosmetic of any one of claims 1 to 4, wherein the polystyrene-equivalent weight average molecular weight measured by liquid phase gel permeation chromatography of the cycloalkyl-containing acrylic random copolymer is 1.0 ×10 ⁴ ~2.0×10 ⁵ . The cosmetic of any one of claims 1 to 4, wherein the volatile oil is further formulated. The cosmetic of claim 8 wherein the volatile oil is a light liquid isoparaffin. The cosmetic of any one of claims 1 to 4, wherein the powder with or without a colorant is further formulated. The cosmetic makeup according to any one of claims 1 to 4, which is a lip cosmetic, an eyeliner cosmetic or an eyelash cosmetic. The cosmetic of claim 10, which is a lip cosmetic, and is formulated as a liquid non-volatile hydrocarbon oil at 25 °C. The cosmetic of claim 10, which is a cosmetic for eyeliner or eyelash, and the powder containing the colorant contains anhydrous citric acid.