KR20110130404A - Make-up cosmetic containing acrylic copolymer having cycloalkyl group - Google Patents

Abstract

The present invention provides a makeup cosmetic having excellent gloss, adhesion and water resistance, and excellent makeup durability, preferably a cosmetic for lips, a cosmetic for eyelashes, and an eyeliner cosmetic containing a cycloalkyl group-containing acrylic copolymer. The cycloalkyl group-containing acrylic copolymer includes (a1) an acrylate or methacrylate containing a cycloalkyl group, a component (a2) an acrylate or methacrylate containing a straight or branched alkyl group having 8 to 12 carbon atoms, and / Or is obtained by polymerizing a monomer including an organopolysiloxane macromonomer containing a radical polymerizable group at one end of component (a3), and the compounding amount of component (a1) in the total amount of the constituent monomer is 50 to 90 mass%, component (a2) And / or the compounding quantity of component (a3) is 10-50 mass%, and it is a cycloalkyl group containing acrylic copolymer characterized by melt | dissolving in hard isoparaffin at least 30 mass% at 25 degreeC.

Description

Makeup cosmetics containing a cycloalkyl group-containing acrylic copolymer {MAKE-UP COSMETIC CONTAINING ACRYLIC COPOLYMER HAVING CYCLOALKYL GROUP}

The present invention relates to a makeup cosmetic containing a cycloalkyl group-containing acrylic copolymer, and more particularly to a makeup cosmetic containing a cycloalkyl group-containing acrylic copolymer dissolved in a volatile oil such as hard fluid isoparaffin, and preferably a lip cosmetic , Eyelash cosmetics, eyeliner cosmetics.

1) Acrylic copolymer

Acrylic resins represented by polymethyl methacrylate are widely used as organic glass materials and coating materials because they form a transparent and hard film and have good workability. However, acrylic resins have high polarity and are dissolved in organic solvents such as acetone, toluene, butyl acetate, and chloroform, but are insoluble in paraffin solvents such as hard-flow isoparaffin, isododecane, and the like. It was difficult to apply as. In particular, in the cosmetics, the use of the organic solvents described above is limited by the use of skin safety or pharmaceutical formulations. Therefore, it is desirable to develop acrylic resins that are soluble in paraffin solvents and silicone solvents that can be generally used in cosmetics. It was.

For example, an acrylic-silicone graft copolymer obtained by radical copolymerization of a dimethylpolysiloxane compound having a radical polymerizable group at one end of a molecular chain with a radical polymerizable monomer mainly composed of acrylates and / or methacrylates is contained. Cosmetics (for example, refer patent document 1) characterized by the above-mentioned, The cycloalkyl group containing monomer which has a double bond which can superpose | polymerize, and the monomer which has a double bond copolymerizable with this monomer, such as 2-ethylhexyl methacrylate, is comprised 1 to 60% by weight of an aqueous polymer emulsion as a component in terms of solid content (for example, refer to Patent Document 2) and the first block is formula CH ₂ = CH-COOR ₂ [wherein R ₂ represents a cycloalkyl group of C ₄ to C ₁₂ ], and the formula CH ₂ = C (CH ₃ ) -COOR ' _{2 wherein} R' ₂ is C At least one methacrylate monomer of [C ₄ -C ₁₂ cycloalkyl group], wherein the second block is obtained from an acrylic acid monomer and at least one monomer having a glass transition temperature of 20 ° C. or lower. A block polymer comprising one first block and at least one second block and a preparation method thereof (see Patent Document 3, for example) have been proposed.

Moreover, the acrylic lacquer which consists of a (co) polymer (A) and the organic solvent obtained by (co) polymerizing the vinyl monomer which contains the cycloalkyl ester of acrylic acid and / or the cycloalkyl ester of methacrylic acid in the ratio of 10 weight% or more in a vinyl monomer. The composition (for example, refer patent document 4) etc. are also reported.

In addition, recent applicants have described (A) acrylate and / or methacrylate containing a cycloalkyl group, and (B) acrylate and / or methacrylate and / or methacrylate containing a straight or branched alkyl group having 8 to 12 carbon atoms. (C) The acrylic copolymer obtained by superposing | polymerizing the monomer containing the organopolysiloxane macromonomer containing a radically polymerizable group in one terminal, 50-90 mass% of compounding quantities of a component (A) in a constituent monomer total amount, a component (B ) And / or (C) has a polymerization amount of 10 to 50% by mass, and a cycloalkyl group-containing acrylic copolymer, characterized by dissolving at least 30% by mass at 25 ° C in hard isoparaffin (see Patent Document 5). . However, this document was filed in Japan before February 27, 2009, which is the filing date of the patent application on which the priority claim of the present invention was applied, and was published after February 27, 2009. Although this document describes that the cycloalkyl group-containing acrylic copolymer can be used in cosmetics, it does not specifically disclose representative makeup cosmetics such as cosmetics for lips, cosmetics for eyelashes, eyeliner and the like.

2) About Makeup Cosmetics

Makeup cosmetics include lip cosmetics such as lipstick and lip gloss, eyelash cosmetics, eyeliner, foundation, face color, sports cover, and the like, and among these, the prior art of lip cosmetics, eyelash cosmetics and eyeliner, to which the present invention is suitable. This will be described below.

2-1) Lip Cosmetics

Conventionally, as a cosmetic for lips excellent in water resistance, oil resistance, a makeup lasting effect, and a secondary adhesion prevention effect, what mix | blended organic silicone resin and volatile oil is mentioned. For example, a technique in which an organic silicone resin having a specific structure and an average molecular weight and a volatile oil are blended (see Patent Document 6, for example), a volatile oil, a water-repellent polymer such as a silicone resin dissolved in the volatile oil, and dispersed in a volatile oil The wax and the technique which mix | blends the nonvolatile oil compatible with volatile oil (for example, refer patent document 7), etc. have been examined.

These techniques are cosmetics containing a mixture of organic silicone resins dissolved in volatile oils. The coating of organic silicone resins is formed by volatilization of a volatile emulsion after application, resulting in a cosmetic having excellent makeup lasting effect or secondary adhesion prevention effect. Since it was hard and lacked the flexibility of a makeup film, the burden on skin and lips was strong, and the glossiness of the coating film was lacking.

Therefore, development of a lip cosmetics which is excellent in color persistence and secondary sticking prevention effect over time, and has excellent glossiness, no burden, and smooth usability has been desired.

2-2) Eyeliner Cosmetic

Conventionally, the eyeliner cosmetics are cosmetics having a cosmetic effect that makes the eyes large and makes the eyes clear by applying to the eyes. In addition to the usability of ease of application, the cosmetic film is required to have uniformity of coating, high gloss and color development, and that the cosmetic film does not peel off or bleed over time. I am blending agent.

In addition, since eyeliner cosmetics are easy to apply to the eyes and it is necessary to quickly form a cosmetic film after application, a volatile solvent is used. Typical examples thereof include water, paraffinic solvents such as hard flow isoparaffin and isododecane, and silicone solvents such as cyclic organopolysiloxane and low molecular weight organopolysiloxane.

The film-forming agent is largely divided and used by dissolving in these solvents and dispersing in a solvent. Herein, the film-forming agent dispersed in a solvent is a suspension in which fine particles of a polymer substance are stably dispersed in water or an organic solvent, and includes a liquid obtained by polymerizing a monomer emulsified with a surfactant or an oily sap existing in nature. .

The use of the film-forming agent dissolved in the solvent can be uniformly applied to the eyes, and the use of the film-forming agent dispersed in the solvent can speed up the formation of the cosmetic film.

Examples of these blending techniques include oil-soluble film-forming resins and fluorine compound-treated powders to improve usability and sustainability of the cosmetic effect (see Patent Document 8, for example) and oil-in-water makeup cosmetics. By containing an emulsion resin having a film-forming ability in the inner phase, and excellent in water resistance, cold resistance, sebum resistance and oil resistance (see, for example, Patent Document 9), and volatile oil in the fat phase. It is easy to apply by dispersing a specific film-forming polymer in an aqueous phase to form a water-in-oil emulsion, and it is easy to apply, well spread, uniform, non-stick, and does not spread or diffuse (see, for example, Patent Document 10). ), And the like.

However, although the technique of patent document 8 can improve the intensity | strength and water resistance of a makeup film, and can improve the persistence of a makeup effect by using an oil-soluble film-forming resin and fluorine compound process powder, since the transparency of a makeup film is lacking, it is a coloring agent. There was a drawback that I could not show the original color taste and lack color development. In addition, when the oil-in-water makeup cosmetics contain oil-soluble resins and emulsion resins having a film-forming ability in the inner phase as described in Patent Literature 9, peeling and smearing of the makeup film can be prevented, and the makeup removal effect with the remover is prevented. However, in order to secure stability, a large amount of wax, natural clay minerals or surfactants must be blended, and as a result, it is difficult to obtain a cosmetic film having good color development due to turbidity of the cosmetic film. In particular, there is a drawback that, when the surfactant is increased, the makeup film is spread. In addition, in the technique of Patent Document 10 that forms a uniform makeup film without stickiness by dispersing a specific film forming polymer in a fat phase and dispersing a specific film-forming polymer in an aqueous phase, the uniformity of the makeup film is obtained. However, since the makeup film was soft and the adhesion was low, a satisfactory thing was not obtained in terms of makeup persistence over time.

In the prior art, the usability is good and the makeup film can be made uniform. However, since the transparency is insufficient, glossiness and color development cannot be obtained, and even if the strength of the makeup film is increased, it may peel off over time and lose the makeup effect in a large area. Therefore, there has been a demand for the development of an eyeliner cosmetic having a uniform makeup film, good glossiness and color development, and excellent durability of the makeup effect.

2-3) Cosmetics for Eyelashes

Conventionally, cosmetics for eyelashes are cosmetics that appear to be curled (curl effect), thick, thick (volume effect), or long (long effect) by applying to eyelashes. In order to sustain each effect, a film forming agent is mix | blended and the cosmetic film is prevented from falling.

Moreover, since the cosmetics for eyelashes are easy to apply to eyelashes, and it is necessary to form a cosmetic film | membrane after application | coating quickly, a volatile solvent is used similarly to an eyeliner.

As a technique using the film-forming agent, a technique of blending a film-forming resin and a film-forming polymer emulsion (for example, Patent Document 11), or a technique using trimethylsiloxy silicic acid and an acrylic-silicone graft copolymer (for example, For example, patent document 12) is mentioned, The technique used combining the film forming agent from which a kind differs has been examined.

However, in recent years, the cosmetics for eyelashes have been desired to securely obtain a plurality of effects, but it has been difficult to coexist with other effects that sustain the curl effect. For example, if you want to get a volume effect, a long effect and a curl effect, it is necessary to attach wax, powder, fiber, etc. to the eyelashes more, and make a firm makeup film to prevent the eyelashes from sagging due to heavy weight. . As a result, cracks in the make-up film come off due to movements such as eye blinks, and the peel-offs are lost, the volume effect and the long effect are also lost, and the transparency of the make-up film is lost, so the glossiness of the eyelashes may be lost. Also, because it is a hard makeup film, the feeling was not good either. In addition, the aqueous dispersion and the solvent dispersion of the film-forming agent can impart moderate strength to the curling film and maintain the curling effect. However, since the uniformity of the makeup film is not obtained, glossiness decreases and color development is poor. In some cases, the effect of making the eyes stand out could not be sufficiently obtained.

Therefore, the development of the eyelash cosmetic which is excellent in the curl effect and its sustainability, and has other effects at the same time is desired.

Patent Document 1: Japanese Patent No. 2704730 Patent Document 2: Japanese Patent Application Laid-Open No. 8-231344 Patent Document 3: Japanese Unexamined Patent Publication No. 2008-31479 Patent Document 4: Japanese Patent Application Laid-Open No. 62-84165 Patent Document 5: Japanese Patent Application Laid-Open No. 2009-46662 Patent Document 6: Japanese Patent Application Laid-Open No. 9-124430 Patent Document 7: Japanese Patent Application Laid-Open No. 9-143034 Patent Document 8: Japanese Patent Application Laid-Open No. 2001-187715 Patent Document 9: Japanese Patent No. 3393903 Patent Document 10: Japanese Patent Application Laid-Open No. 10-203919 Patent Document 11: Japanese Patent Application Laid-Open No. 8-268841 Patent Document 12: Japanese Patent Application Laid-Open No. 7-196449

An object of the present invention is to provide a makeup cosmetic having excellent gloss, adhesion, and water resistance, and excellent makeup durability, containing the cycloalkyl group-containing alkyl copolymer described in Patent Document 5 relating to the applicant's development.

In particular, the lip cosmetics provide excellent lip cosmetics with excellent color persistence and secondary adhesion prevention over time, and are excellent in gloss, no burden, and smooth use, and the uniformity of the makeup film for the eyeliner cosmetics. In addition, to provide an eyeliner cosmetics with good gloss and color development and excellent persistence of the makeup effect, and for the eyelash cosmetics to provide an eyelash cosmetic having excellent curl effect and its sustainability and at the same time having other effects. will be.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, it discovered that the acryl-type copolymer containing the cycloalkyl group which has a specific structure can solve the said subject, and came to complete this invention.

That is, the present invention

(1) As an acryl-type copolymer obtained by superposing | polymerizing the monomer containing the following component (a1) and a component (a2) and / or a component (a3), the compounding quantity of a component (a1) is 50-90 in a constituent monomer total amount. A cycloalkyl group-containing acrylic copolymer, characterized in that the blending amount of the mass%, the component (a2) and / or the component (a3) is 10-50 mass%, and at least 30 mass% is dissolved in the hard-flow isoparaffin at 25 ° C. Makeup cosmetics containing,

Component (a1): Formula (I)

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a cycloalkyl group) and / or an acrylate and / or methacrylate represented by

Component (a2): Formula (II)

An acrylate and / or methacrylate represented by (wherein, R ₃ represents a hydrogen atom or a methyl group, and R ₄ represents a straight chain or branched alkyl group having 8 to 12 carbon atoms).

Component (a3): organopolysiloxane macromonomer containing a radical polymerizable group at one end

(2) A cycloalkyl group-containing acrylic copolymer obtained by polymerizing components (a1) and (a2), wherein the makeup cosmetic according to the above (1),

(3) Cycloalkyl group containing acrylic copolymer is obtained by superposing | polymerizing component (a1) and component (a3), The makeup cosmetics as described in said (1) characterized by the above-mentioned.

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

(5) Component (a3) has the following general formula (III)

(In formula, R <_5> represents a hydrogen atom or a methyl group, R <_6> -R <_12> represents a C1-C5 alkyl group each independently, m shows the integer of any of 1-10, n is 0-200 The makeup cosmetic according to any one of the above (1), (3) or (4), which is an organopolysiloxane macromonomer represented by any one of

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

(7) The weight average molecular weight by polystyrene conversion measured by the liquid gel permeation chromatography of a cycloalkyl group containing acrylic copolymer is 1.0 * 10 <^4> -2.0 * 10 <^5> , The said (1)-(6) characterized by the above-mentioned. The makeup cosmetics described in any one of

(8) The makeup cosmetic according to any one of the above (1) to (7), further comprising a volatile oil agent,

(9) the makeup cosmetic according to the above (8), wherein the volatile emulsion is hard flowing isoparaffin;

(10) The makeup cosmetic according to any one of the above (1) to (9), further comprising a powder containing or not containing a colorant;

(11) the makeup cosmetic according to any one of the above (1) to (10), which is a cosmetic for lips, an eyeliner cosmetic or a cosmetic for eyelashes;

(12) The makeup cosmetic according to the above (10), wherein as a cosmetic for lips, a liquid nonvolatile hydrocarbon oil is blended at 25 ° C,

(13) An eyeliner cosmetic or a cosmetic for eyelashes, wherein the powder containing a colorant contains silicic anhydride, the makeup cosmetic according to the above (10).

(1) cycloalkyl group-containing acrylic copolymer

The acryl-type copolymer of this invention is an acryl-type copolymer obtained by superposing | polymerizing the monomer containing the following (a1) and component (a2) and / or component (a3).

Component (a1): Formula (I)

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a cycloalkyl group) and / or an acrylate and / or methacrylate represented by

Component (a2): Formula (II)

An acrylate and / or methacrylate represented by (wherein, R ₃ represents a hydrogen atom or a methyl group, and R ₄ represents a straight chain or branched alkyl group having 8 to 12 carbon atoms).

Component (a3): organopolysiloxane macromonomer containing a radical polymerizable group at one end

As for the acryl-type copolymer of this invention, the compounding quantity of a component (a1) is 50-90 mass% (henceforth simply "%"), and the compounding quantity of a component (a2) and / or a component (a3) in a constituent monomer total amount. The copolymer is not particularly limited as long as it is a copolymer which is 10 to 50% and dissolved at least 30% at 25 ° C in hard flow isoparaffin.

In the present invention, the hard-flow isoparaffin in the definition of "dissolve at least 30% in a hard-flow isoparaffin at 25 ° C" is a mixture of hydrocarbons mainly composed of isoparaffins, and is a petroleum product distillation test prescribed in JIS K2254. The initial distillation temperature by the method is 166 ° C, the distillation end point has a distillation property of 202 ° C, and the kinematic viscosity at 37.8 ° C is 1.28 mm 2 / s. As a commercial item, there exists IP solvent 1620 (made by Idemitsu Kosan Corporation), for example.

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

Here, the acrylate and / or methacrylate containing a cycloalkyl group are 1 type (s) or 2 or more types of acrylates containing a cycloalkyl group, 1 type (s) or 2 or more types of methacrylates containing a cycloalkyl group, and these It contains a mixture of.

As a cycloalkyl group, it is a C5-C10 cycloalkyl group, Preferably it is a C6-C8 cycloalkyl group, Especially preferably, it is a cyclohexyl group.

Specific examples of the cycloalkyl group-containing acrylate or methacrylate include cyclohexyl acrylate, cyclohexyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, tricyclodecyl acrylate, tricyclodecyl methacrylate and tri Cyclodecanyl acrylate, tricyclo decanyl methacrylate, etc. are mentioned, These can be used 1 type, or 2 or more types. In particular, cyclohexyl methacrylate is particularly preferred because it has good radical polymerizability, high yield, and can obtain a copolymer having a preferable glass transition point for forming a hard film.

The acrylate and / or methacrylate containing a straight chain or branched alkyl group having 8 to 12 carbon atoms of component (a2) is a lipophilic polymerizable monomer, imparts flexibility and adhesion to the film, and hard rigid isoparaffin. It becomes a skeleton which raises the solubility to.

Here, the acrylate and / or methacrylate containing a C8-C12 linear or branched alkyl group is 1 type, 2 or more types of acrylate containing a C8-C12 linear or branched alkyl group, and has 8 carbon atoms 1 type, or 2 or more types of methacrylate containing a linear or branched alkyl group of -12, and mixtures thereof.

Examples of the linear or branched alkyl group having 8 to 12 carbon atoms include octyl, 2-ethylhexyl, nonyl, isononyl, lauryl and the like, preferably 2-ethylhexyl and lauryl, and particularly preferably 2-ethyl Hexyl.

As a specific example of the acrylate or methacrylate containing a C8-C12 linear or branched alkyl group, octyl acrylate, octyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isononyl acryl Acrylate, isononyl methacrylate, lauryl acrylate, lauryl methacrylate, and the like, and one or two or more thereof can be used, and 2-ethylhexyl methacrylate and lauryl methacrylate are preferable. Especially, 2-ethylhexyl methacrylate can improve solubility, and it is especially preferable.

The organopolysiloxane macromonomer containing a radically polymerizable group at one end of component (a3) includes, for example, an ester compound in which an organopolysiloxane is linked through a hydrocarbon group of divalent to acrylic acid or methacrylic acid. It can be used as a skeleton for imparting water resistance to the coating and increasing solubility in hard flow isoparaffin.

Specifically, the following formula (III)

(In formula, R <_5> represents a hydrogen atom or a methyl group, R <_6> -R <_12> represents a C1-C5 alkyl group each independently, m shows the integer of any of 1-10, n is 0-200 Organopolysiloxane macromonomer represented by any one of these) can be illustrated, These can be used individually by 1 type or in mixture of 2 or more types.

Here, as a C1-C5 alkyl group, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-pentyl etc. are mentioned.

More specifically, general formula (IV)

The dimethylpolysiloxane macromonomer represented by (In formula, R <_13> represents a hydrogen atom or a methyl group, R <_14> represents a C1-C5 alkyl group and n represents the integer of any one of 0-200.) .

When n which represents the repeating unit of a dimethylpolysiloxane group in Formula (III) is 0-200, since sufficient water resistance is obtained and a transparent and uniform film is obtained, it is preferable. n is 5-150, It is more preferable at the point which acquires water resistance and a uniform film | membrane.

Moreover, the cycloalkyl group containing acrylic copolymer of this invention can contain polymeric monomers other than said component (a1)-(a3) as an arbitrary component as long as it is a range which does not impair the effect of this invention. Although it does not specifically limit as polymerizable monomers other than components (a1)-(a3), Styrene, substituted styrene, vinyl acetate, acrylic acid, methacrylic acid, maleic anhydride, maleic acid ester, fumaric acid ester, vinyl chloride, vinyl chloride Leadene, ethylene, propylene, butadiene, acrylonitrile, fluorinated olefin, acrylamide, methacrylamide, methylacrylamide, methyl methacrylamide, dimethyl methacrylamide, N-isopropylacrylamide, N-vinylpyrrolidone , N-vinylacetamide, t-butyl acrylate, t-butyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl methacrylamide, 2- Acrylamide-2-dimethyl propane sulfonate etc. are mentioned.

The compounding ratio of the said component (a1)-(a3) and arbitrary monomers is as follows.

The compounding quantity of component (a1) is 50 to 90% of the constituent monomer total amount, and 50 to 80% is preferable. If it is less than 50%, the coating of sufficient hardness cannot be obtained, and if it exceeds 90%, the solubility with respect to hard-flow isoparaffin will worsen.

The compounding quantity of component (a2) and / or component (a2) is 10-50% of the constituent monomer total amount, and 15-45% is preferable. If it is less than 10%, solubility in hard-flowing isoparaffin becomes worse, and if it exceeds 50%, a coating of sufficient hardness cannot be obtained, and defects such as stickiness, stickiness, and film nonuniformity occur.

As a compounding quantity of the said arbitrary component, what is necessary is just 30% or less of range of the constituent monomer total amount, 20% or less is preferable, and it can mix | blend 0.01-10%, for example.

Moreover, the cycloalkyl group containing acrylic copolymer obtained by superposing | polymerizing 10-50% of component (a3) with respect to 50-90% of component (a1) can form the film with especially good water resistance, and 50-90% of component (a1) The cycloalkyl group-containing acrylic copolymer obtained by polymerizing components (a2) and (a3) in a proportion of 10 to 50% in total can form a film having hardness and water resistance.

Although the weight average molecular weight in particular of the cycloalkyl group containing acrylic copolymer of this invention is not restrict | limited, The thing of the range of 1.0 * 10 <^4> -2.0 * 10 <^5> is preferable. If it is this range, the film formation ability which makes a uniform film | membrane can be exhibited. The weight average molecular weight is measured by liquid gel permeation chromatography (GPC) using tetrahydrofuran as the eluent and using a calibration curve and a refractive index detector made of a straight chain polystyrene standard.

(2) Production method of cycloalkyl group-containing acrylic copolymer

The cycloalkyl group-containing acrylic copolymer of the present invention employs the above-mentioned components (a1) to (a3) and optionally other monomers as constituent monomers, and is known in a known polymerization method in the presence of an organic solvent and in the absence of water. It can be obtained by random polymerization. Although not particularly limited, organic peroxides such as benzoyl peroxide and lauroyl peroxide, α, α'-azobisisobutyronitrile, 2, 2'-azobis (2,4-dimethylvaleronitrile), 2 What is necessary is just to superpose | polymerize in presence of radical polymerization initiators, such as azo-type compounds, such as 2'- azobis (2-methylbutyronitrile), and persulfate type polymerization initiators, such as potassium persulfate and ammonium persulfate, and the solution polymerization method , Suspension polymerization, bulk polymerization, precipitation polymerization, or the like can be used. Among these, especially the solution polymerization method is preferable because it is easy to adjust the molecular weight of the acryl-type copolymer obtained to an optimal range.

As an organic solvent used at the time of superposition | polymerization of the cycloalkyl group containing acrylic copolymer of this invention, For example, aromatic hydrocarbons, such as benzene, toluene, xylene, ketones, such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, butyl acetate, etc. Alcohols such as esters, isopropanol, ethanol and methanol, and one or two or more thereof can be used in combination. Moreover, it can also superpose | polymerize in paraffin type solvents, such as hard-flowing isoparaffin, isododecane, and isohexadecane.

The polymerization reaction temperature of the cycloalkyl group-containing acrylic copolymer of the present invention is not particularly limited as long as it is a usable temperature range of an ordinary radical polymerization initiator, but is usually in the range of 40 to 120 ° C. Although reaction time changes with radical polymerization initiator, the kind of monomer, and reaction temperature to be used, it is the range of 2 to 24 hours normally. If the polymerization time is too short, the amount of remaining 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 such as another hydrocarbon, ester or triglyceride while being dissolved in a paraffin solvent when reacted, or solvent substitution may be performed with another oil. The acrylic copolymer composition containing a cycloalkyl group in such a useful form is also included in component (A) of the present invention. Moreover, the solvent of a solution can be removed and a cycloalkyl group containing acrylic copolymer can be taken out as a solid, and also the obtained cycloalkyl group containing acrylic copolymer can be used as a cycloalkyl group containing acrylic copolymer solution by melt | dissolving in hard-flowing isoparaffin. Said cycloalkyl group containing acrylic copolymer and its solution can also be used in mixture of 2 or more types.

(3) makeup cosmetics

The cycloalkyl group-containing acrylic copolymer is suitable as a component of make-up cosmetics such as lip cosmetics such as lipstick and lip gloss, eye makeup cosmetics such as eyeliner, and eyelash cosmetics, face color and foundation, and in particular, lip cosmetics and eyeliner It can use suitably as a cosmetics for eyelashes.

The makeup cosmetic of the present invention usually contains the cycloalkyl group-containing acrylic copolymer and a volatile emulsion. In addition, if necessary, powders (including colorants) which are components normally used in cosmetics, oily components other than volatile emulsions, fibers, film-forming dispersions, surfactants, aqueous components, ultraviolet absorbers, moisturizers, anti-fading agents, oxidation An inhibitor, an antifoamer, a cosmetic component, a preservative, a fragrance | flavor, etc. can be mix | blended suitably in the range which does not impair the effect of this invention.

For example, it is preferable to set it as the following formulation about the cosmetics for lips, the cosmetics for eyelashes, and the eyeliner cosmetics.

(Lip cosmetics)

(A) Cycloalkyl group-containing acrylic copolymer of the present invention

(B) volatile emulsion

(C) powder containing a coloring agent, and as needed

(D) Liquid nonvolatile hydrocarbon oil at 25 ° C

(Cosmetic and eyeliner for eyelashes)

(A) Cycloalkyl group-containing acrylic copolymer of the present invention

(B) volatile emulsions, and

(C) powder containing or not containing colorant

As (C), it is more preferable to contain silicic acid anhydride.

Hereinafter, each component is demonstrated in detail.

(Cycloalkyl group-containing acrylic copolymer)

The cycloalkyl group-containing acrylic copolymer is as described above.

The blending amount of the cycloalkyl group-containing acrylic copolymer is usually 0.1 to 40% as a solid (but 0.1 to 30% in the case of a lip cosmetic), preferably 1 to 25%, and more preferably about 2 to 20%. have. If it is this range, for example, it will become especially excellent in the cosmetics for lips in the point of color persistence, secondary sticking prevention effect, and no feeling of burden with time. Moreover, in the cosmetics for eyelashes, there is no stickiness at the time of finishing, a uniform and high coating film strength is formed, and the thing excellent in glossiness, curling force, and its durability are obtained. In addition, in the eyeliner cosmetics, a cosmetic film with a high uniformity and a high coating film strength is formed, which is easy to draw lines, and has excellent glossiness, color development, and durability.

The cycloalkyl group-containing acrylic copolymer is used by dissolving in a volatile oil, and in particular, by dissolving in a hard fluid isoparaffin. It is preferable to make the density | concentration in the volatile emulsion of a cycloalkyl group containing acrylic copolymer into 15 to 50%.

(Volatile emulsion)

The volatile emulsion acts as a solvent of the cycloalkyl group-containing acrylic copolymer, facilitates blending of the cycloalkyl group-containing acrylic copolymer, and as a result, stickiness during finishing is suppressed, and a uniform film is formed.

The volatile emulsion is not particularly limited as long as it is volatile at 1 atm and 25 ° C., and is usually used for cosmetics. Specifically, the hard flow isoparaffin, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, Methyl trimethicone, dimethyl polysiloxane, decamethyl tetrasiloxane, ethyl trisiloxane, etc. are mentioned. The hard flow isoparaffin can be used here without being limited to what was used as a criterion of solubility.

The following are mentioned as a commercial item. Examples of the hard flow isoparaffin include isoper H (manufactured by Eso Chemical Co., Ltd.), isododecane (manufactured by Bayer Corporation), isohexadecane (manufactured by Unikema), IP Solvent 1620MU, IP Solvent 2028MU, IP Solvent 2835 (above, Idemitsuko Examples of decamethylcyclopentasiloxane, such as acid company), include TFS405 (manufactured by Toshiba Silicone Co., Ltd.), SH245, DC345 (manufactured by Torre Dow Corning), KF-995 (manufactured by Shin-Etsu Chemical Co., Ltd.), and silicone TMF-1.5 ( As methyl polysiloxane, such as Shin-Etsu Chemical Co., Ltd., such as KF-96L-2CS (manufactured by Shin-Etsu Chemical Co., Ltd.), and KF-96L-1.5CS (manufactured by Shin-Etsu Chemical Co., Ltd.), such as decamethyltetrasiloxane, are SILSOFT ETS (Moment). Creative Performance Materials, Inc.). Especially, hard fluid isoparaffin is preferable in the point that the solubility of the cycloalkyl group containing acrylic copolymer of component (A) is good, and a uniform makeup film is obtained. These volatile emulsions can use the 1 type (s) or 2 or more types as needed.

Although the compounding quantity of a volatile oil agent is not specifically limited, For example, in the case of the cosmetic for lips, 10 to 90% is preferable and 15 to 85% is more preferable. When it mix | blends in this range, it becomes especially excellent from the viewpoint of a makeup lasting effect, a secondary adhesion prevention effect, and a usability. Moreover, in the case of an eyeliner cosmetics and the cosmetics for eyelashes, 1 to 80% is preferable, and 1 to 70% is more preferable. If it is this range, there will be no stickiness at the time of finishing, a film which will be uniform and high in film strength will be formed, and it will be excellent in glossiness, and it will be excellent in color development and its sustainability in eyeliner cosmetics, and curling power and its in cosmetics for eyelashes. More excellent persistence is obtained.

(Powder)

By mix | blending powder, it can be colored, a drying speed can be made faster, and stickiness of a finish can be suppressed more.

The powder may be any powder used in general cosmetics, and is not particularly limited by the shape of plate, fusiform, needle, or the like, the particle diameter of aerosols, fine particles, or pigments, or the particle structure of porous or nonporous, or the like. Inorganic powders, bright powders, metal powders, organic powders, pigment powders, composite powders, fibers and the like can be used.

More specifically, the following 1 type, or 2 or more types can be used.

Royal Blue, Ultramarine Blue, Bengala, Iron Sulfate, Black Iron Oxide, Titanium Oxide, Zinc Oxide, Titanium / Titanium Oxide Sintered Product, Cerium Oxide, Magnesium Oxide, Zirconium Oxide, Antimony Oxide, Magnesium Carbonate, Calcium Carbonate, Chromium Oxide, Chromium Hydroxide, Carbon Black, aluminum silicate, magnesium silicate, calcium silicate, barium silicate, aluminum magnesium silicate, magnesium aluminum silicate, mica, synthetic mica, synthetic sericite, sericite, talc, silicic anhydride, mica, gold mica, red mica, biotite, kaolin Inorganic powders such as barium sulfate, bentonite, smectite, diatomaceous earth, hydroxyapatite and boron nitride;

Bismuth oxychloride, mica titanium, titanium oxide coating Bismuth oxychloride, iron oxide coating mica, iron oxide coating mica titanium, wire coating mica titanium, carmine coating mica titanium, organic pigment coating mica titanium, iron oxide, titanium oxide coating synthetic gold mica, young silver Bright powders such as titanium dioxide coated glass flakes, polyethylene terephthalate, aluminum epoxy laminate, polyethylene terephthalate polyolefin laminated film, polyethylene terephthalate polymethyl methacrylate laminated film, etc .;

Copolymer resins such as polyamide resin, polyethylene resin, polyacrylic resin, polyester resin, fluorine resin, cellulose resin, polystyrene resin, styrene-acryl copolymer resin, polypropylene resin, silicone resin, urethane Organic powders such as organic polymer resin powder such as resin and N-acylicin;

Pigment powders such as natural organic powders such as starch, silk powder and cellulose powder, organic tar pigments, and lake pigments of organic pigments;

Metal powders such as aluminum powder, gold powder and silver powder;

Composite powders such as fine particle titanium oxide coated mica titanium, fine particle zinc oxide coated mica titanium and barium sulfate coated mica titanium;

Synthetic fibers such as nylon, polypropylene, polyester, artificial fibers such as rayon, natural fibers such as cellulose, semisynthetic fibers such as acetate dog, and fibers such as composite fibers in which polyethylene terephthalate and nylon are laminated in layers.

In addition, these powders may be used in combination of two or more kinds thereof. Fluorine compounds, silicone compounds, metal soaps, lecithins, hydrogenated lecithins, collagen, higher fatty acids, higher alcohols, esters, waxes, lead, fats and oils, hydrocarbons, and interfaces. The surface treatment may be performed by a well-known method using 1 type, or 2 or more types, such as an activator, an amino acid type compound, and a water-soluble polymer. These powder can use 1 type (s) or 2 or more types as needed.

As a coloring agent, the coloring agent normally used for cosmetics is used, including what can be used as a coloring agent in the specific example of the said powder, The particle diameters, such as spherical shape, plate shape, fusiform shape, needle shape, mist shape, fine particle, pigment grade, Or it is not specifically limited to particle structures, such as porous and nonporous, White inorganic pigments, colored inorganic pigments, colored organic pigments, dyes, bright pigments, metal powders, complex powders, etc. can be used. have.

More specifically, the following 1 type, or 2 or more types can 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, bluish blue, ultramarine, and bengalla;

Titanium Titanium, Bismuth Oxychloride, Organic Pigmented Mica Titanium Dioxide, Titanium Dioxide Coated Mica, Titanium Dioxide Coated Synthetic Mica, Titanium Dioxide Coated Bismuth Oxide, Iron Oxide Titanium Oxide, Tapping Mica, Carmine Treated Mica Titanium Bright pigments such as titanium coated glass powder, polyethylene terephthalate aluminum epoxy laminate powder, polyethylene terephthalate polyolefin laminated film powder, polyethylene terephthalate polymethyl methacrylate laminated film powder, and the like.

Organic pigments such as red 201, red 202, red 205, red 226, red 228, orange 203, orange 204, blue 404 and yellow 401;

Organic pigments such as zirconium, barium or aluminum lake such as red 3, red 104, red 106, orange 205, yellow 4, yellow 5, green 3 and blue 1;

Metal powders such as aluminum powder, gold powder and silver powder;

Composite powders such as fine particle titanium oxide coated mica titanium, fine particle zinc oxide coated mica titanium, barium sulfate coated mica titanium, titanium oxide containing silicon dioxide and zinc oxide containing silicon dioxide.

In addition, these are surface-treated using one or two or more of fluorine compounds, silicone compounds, metal soaps, lecithin, hydrogenated lecithin, collagen, hydrocarbons, higher fatty acids, higher alcohols, esters, waxes, lead, surfactants, and the like. You may carry out.

In addition, by containing silicic anhydride in the powder, a good one is obtained in that the drying speed is increased and there is no stickiness of the finish. For example, an eyeliner cosmetic or a cosmetic for eyelashes can obtain a better one.

As the silicic anhydride, those used in general cosmetics can be used, and those having an amorphous structure, hydrophobized one, or having a crystal structure can be preferably used. Although the size of particle | grains is not specifically limited, When measuring by a volume average particle diameter laser diffraction type particle size distribution measuring apparatus, 1 nm-50 micrometers are preferable, and 3 nm-30 micrometers are more preferable. If it is this range, a thing with a more favorable feeling will be obtained.

As a commercial item, Sylcia 550, Sylcia 770, Silospair C-1504 (manufactured by Fujisilician Chemical Co., Ltd.), AEROSIL 200, AEROSIL 300, AEROSIL R972 (manufactured by Nippon Aerosil Co., Ltd.) Nipsil E-220 (manufactured by Tosso Silica) Can be mentioned. These silicic anhydrides can use 1 type (s) or 2 or more types as needed.

Although the compounding quantity of powder is not specifically limited, For example, in the case of the cosmetic for lips, it is 0.01 to 25%, and 0.1 to 20% is preferable. If it is this range, a satisfactory thing will be obtained from the point of providing the cosmetic film with good coloration without blur, color persistence, and a secondary adhesion prevention effect. Moreover, in an eyeliner cosmetics and the cosmetics for eyelashes, 0.1 to 60% is preferable, More preferably, it is 0.5 to 45%. If it is this range, it can be colored, there is no stickiness at the time of finishing, a film with a uniform, high coating film strength is formed, it is excellent in glossiness, and the eyeliner cosmetics are more excellent in color development and its sustainability, and it is obtained for eyelashes In cosmetics, the curling power and the durability thereof are more excellent.

When silicic anhydride is contained in the powder, for example, in the eyeliner cosmetics and the eyelash cosmetic, the blending amount in the powder of silicic anhydride is 3 to 100%, preferably 6 to 40%.

(Non-volatile hydrocarbon oil liquid at 25 ° C)

For example, the lip cosmetics further contain a liquid nonvolatile hydrocarbon oil at 25 ° C., which can impart a plasticizing effect to the cycloalkyl group-containing acrylic copolymer of the present invention, thereby producing color persistence and no burden. desirable. Especially, the nonvolatile hydrocarbon oil whose viscosity in 98.9 degreeC is 200 mm <2> / s is preferable. In particular, heavy flow isoparaffin, polybutene, and polyisobutene are preferable. Examples of commercially available products include pearlim 18, pearlim 24, pearlim 46 (above, manufactured by Nippon Yushi Co., Ltd.), polybutene 100R, polybutene 300R, polybutene 2000H (above, manufactured by Idemitsu Kosan Co., Ltd.), and the like. In addition, these can use 1 type (s) or 2 or more types as needed.

The compounding quantity of the liquid nonvolatile hydrocarbon oil at 25 degreeC is 0.5 to 50%, Preferably it is 1 to 10%. If it is this range, a satisfactory thing will be obtained by the point of color persistence and no burden.

(Other ingredients)

Emulsions other than volatile oils and liquid nonvolatile hydrocarbon oils at 25 ° C, fibers, film-forming dispersions, surfactants, aqueous components, ultraviolet absorbers, humectants, anti-fading agents, antioxidants, antifoams, cosmetic ingredients, preservatives, fragrances, etc. Can be mentioned.

It demonstrates concretely below.

(Emulsions other than volatile emulsions and liquid nonvolatile hydrocarbon oils at 25 ° C)

Oils other than volatile oils and nonvolatile hydrocarbon oils which are liquid at 25 ° C can be used without particular limitations as long as they are oils normally used in cosmetics, and can be used for animal oils, vegetable oils, synthetic oils, etc. Hydrocarbons, fats and oils, lead oils, cured oils, ester oils, fatty acids, higher alcohols, silicone oils, fluorine oils, lanolin derivatives, oily gelling agents and the like can be used irrespective of their properties.

Specifically, the following 1 type, or 2 or more types can be used.

Hydrocarbons such as liquid paraffin, α-olefin oligomer, squalene, petrolatum, ceresin wax, polyethylene wax, Fischerthrop wax, paraffin wax, microcrystalline wax, ozokerite wax, and ethylene propylene copolymer;

Fats and oils, such as olive oil, castor oil, mink oil, macadamia nut oil, and wax;

Lead, such as beeswax, carnauba wax, candelilla wax, sperm, and montan wax;

Rosin acid pentaerythrite ester, dipentaerythrite fatty acid ester, cholesterol fatty acid ester, N-lauroyl-L-glutamic acid di (cholesteryl behenyl octyldodecyl), myristic acid isopropyl, palmitic acid Sopropyl, 2-ethylhexanoate, octyldodecyl myristate, glyceryl trioctanoate, polyglyceryl diisostearate, polyglyceryl triisostearate, diisostearyl malate, neopentyl glycol dioctanoate, jojoba Esters such as oils;

Fatty acids such as stearic acid, lauric acid, myristic acid, behenic acid, isostearic acid and oleic acid;

Higher alcohols such as stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol and behenyl alcohol;

Silicones such as low-polymerization dimethylpolysiloxane, high-polymerization dimethylpolysiloxane, methylphenylpolysiloxane, alkoxy-modified polysiloxane, crosslinked organopolysiloxane, and fluorine-modified polysiloxane;

Fluorine emulsions such as perfluorodecane, perfluorooctane, and perfluoropolyether;

Lanolin derivatives such as lanolin, lanolin acetate, lanolin fatty acid isopropyl and lanolin alcohol;

Dextrin fatty acid esters of 12-hydroxystearic acid, palmitic acid dextrin, palmitic acid / 2-ethylhexanoate dextrin, stearic acid dextrin, palmitic acid / stearic acid dextrin, oleic acid dextrin, isopalmitic acid dextrin, isostearic acid dextrin, stearic acid Oily gelling agents such as sucrose, sucrose fatty acid ester of sucrose stearate, aluminum isostearate and calcium stearate.

(Film forming dispersion)

As the film-forming dispersion, the polymer having the film-forming ability is in a state of being emulsified in an aqueous solvent or in a state of being dispersed in an oil-based solvent, and is not particularly limited as long as it is usually used in cosmetics, and any of them can be used. For example, in the state of being emulsified in an aqueous solvent, an alkyl acrylate copolymer emulsion, an alkyl acrylate copolymer emulsion, a polyvinyl acetate emulsion, a vinylpyrrolidone styrene copolymer emulsion is mentioned, and a commercial item is an uridosol 32A707. , Yodosol GH810F, Yodosol GH800F (manufactured by Nippon N-SC), Flexitol B-500 (manufactured by ROHM GMBH), Yodosol GH41F (manufactured by Nippon N-SC), Vinnibran 1080, Vinnibran 1128C, Beanie Bran 1080M, BiniBran 1080T, BiniBran GV-5651, BiniBran 1108S / W (Nisshin Chemical Co., Ltd.), ANTARA430 (ISP company make) is mentioned. In addition, the thing of the state disperse | distributed in an oil-based solvent can mention the alkyl acrylate styrene copolymer emulsion, As a commercial item, NISSETSU U-3700A (made by Nippon Carbide Co., Ltd.) is mentioned.

(Surfactants)

As surfactant, any surfactant can be used as long as it is surfactant used for the general cosmetics, and a nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant, etc. are mentioned.

As the nonionic surfactant, for example, glycerin fatty acid ester and its alkylene glycol adduct, polyglycerol fatty acid ester and its alkylene glycol adduct, propylene glycol fatty acid ester and its alkylene glycol adduct, sorbitan fatty acid ester and its alkyl Lenglycol adduct, fatty acid ester of sorbitol and its alkylene glycol adduct, polyalkylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyalkylene alkyl ether, glycerin alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene curing Castor oil, lanolin alkylene glycol adducts, polyoxyalkylene alkyl co-modified silicones, polyether-modified silicones, and the like.

As the anionic surfactant, for example, inorganic and organic salts of fatty acids such as stearic acid and lauric acid, alkylbenzene sulfates, alkylsulfonates, α-olefinsulfonates, dialkylsulfosuccinate salts, α-sulfonated fatty acid salts and acylmethyltaurine Salt, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate, N-acyl amine salt, o-alkyl substituted malate, alkyl sulfo Succinate salt etc. are mentioned.

Examples of the cationic surfactant include alkylamine salts, polyamines and alkanolamine fatty acid derivatives, alkyl quaternary ammonium salts, and cyclic quaternary ammonium salts.

Amphoteric surfactants include those of the carboxylic acid type, the sulfate ester type, the sulfonic acid type, and the phosphate ester type of the amine acid type or the betaine type, and those that are safe for human body can be used. For example, N, N-dimethyl-N-alkyl-N-carboxymethylammoniumbetaine, N, N-dialkylaminoalkylenecarboxylic acid, N, N, N-trialkyl-N-sulfoalkylene Ammonium betaine, N, N-dialkyl-N, N-bis (polyoxyethylene sulfate) ammonium betaine, 2-alkyl-1-hydroxyethyl-1-carboxymethylimidazolinium betaine, lecithin and the like Can be mentioned.

(Aqueous component)

As an aqueous component, any component may be used as long as it is a component soluble in water, and for example, alcohols such as ethyl alcohol and isopropylene alcohol; Glycols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol and polyethylene glycol; Glycerols, such as glycerin, diglycerol, and polyglycerol; Sugars such as sorbitol, maltitol, sucrose, starch sugar and lactitol; Water-soluble such as guar gum, sodium chondroitin sulfate, sodium hyaluronate, gum arabic, sodium alginate, carrageenan, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyvinyl polymer, polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylate Polymers; Salts such as sodium chloride, magnesium chloride and sodium lactate; Plant extracts such as aloe bella, witch hazel, hamamaris, cucumber, lemon, lavender, and rose; and the like.

(Moisturizer)

As a humectant, Natural thing, such as guar gum, sodium chondroitin sulfate, sodium hyaluronate, gum arabic, sodium alginate, carrageenan; Semisynthetic systems such as methyl cellulose, hydroxyethyl cellulose and carboxymethyl cellulose; Synthetic systems such as carboxyvinyl polymers, alkyl addition carboxyvinyl polymers, polyvinyl alcohols, polyvinylpyrrolidones, and sodium polyacrylates; And other proteins, mucopolysaccharides, collagen, elastin, keratin and the like.

(Other UV absorbers, antioxidants, etc.)

Examples of the ultraviolet absorber include benzophenone series, PABA series, cinnamic acid series, salicylic acid series, 4-tert-butyl-4'-methoxydibenzoylmethane, oxybenzone, and the like. As antioxidants, for example, α-tocopherol and ascorbic acid. As a cosmetic component, vitamins, an anti-inflammatory agent, a herbal medicine etc. are mentioned, for example, As a preservative, paraoxybenzoic acid ester, phenoxyethanol, 1,2-pentanediol, etc. are mentioned, for example.

(Shaping, shape, etc.)

Although the make-up cosmetics of this invention are not specifically limited as a formulation, A water-in-oil type | mold, an oil-in-water type | mold, an oil type, and a powder type are mentioned. In addition, an oil type | mold is a cosmetics which make the oil component which is a liquid, semi-solid, or solid emulsion or oil-soluble compound into a continuous phase, and does not contain water substantially. In addition, a form etc. can be selected suitably according to a use.

For example, the formulation for the lip cosmetic is not particularly limited, but an oil type or a water-in-oil type in which the external appearance becomes oily from the point of color persistence or glossiness is preferable. Examples of the shape include solid, semi-solid, and liquid, and can be used as lipstick, lip gloss, lip treatment, lip cream, foundation lip base, lipstick overcoat, and the like.

As the eyeliner cosmetic, an oil type is preferable. As a form, a liquid, semisolid, solid, etc. are mentioned. As cosmetics for eyelashes, an oil type is preferable. As a form, a liquid, semisolid, etc. are mentioned, It can be used as a mascara, a mascara overcoat, a mascara base, etc.

Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not limited to these illustrations.

I Cycloalkyl Group-Containing Acrylic Copolymer

[Production Example 1]

[Synthesis of cycloalkyl group-containing acrylic copolymer (1)]

In a four-neck separable flask (hereinafter referred to simply as a "flask") with a reflux condenser, thermometer, nitrogen inlet tube, and stirring device, 22.5 g of cyclohexyl methacrylate, 7.5 g of 2-ethylhexyl methacrylate, and 70 g of toluene After the addition of nitrogen gas and introducing nitrogen gas into a sufficiently nitrogen atmosphere, the mixture was heated to 100 ° C, and 0.15 g of α, α'-azobisisobutyronitrile (hereinafter referred to as AIBN) was added to reflux for 3 hours to polymerize. I was. Methanol was inject | poured into the obtained reaction material, the acrylic copolymer was precipitated, and the deposit was isolate | separated by filtration, and it vacuum-dried and obtained 27.4 g of cycloalkyl-group containing acrylic copolymer solid content. The weight average molecular weight by polystyrene conversion was 5.0x10 <^4> .

[Production Example 2]

[Synthesis of 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 to make a sufficiently nitrogen atmosphere, and then warmed up to 100 ° C, and 0.15 g of AIBN was added. It was polymerized by refluxing for time. Methanol was inject | poured into the obtained reaction material, the acrylic copolymer was precipitated, and the deposit was isolate | separated by filtration, and it dried under vacuum and obtained the cycloalkyl-group containing acrylic copolymer solid content 25.5g. The weight average molecular weight by polystyrene conversion was 3.7x10 <^4> .

[Manufacture example 3]

[Synthesis of 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 to make a sufficiently nitrogen atmosphere, then warmed up to 100 ° C., and 0.15 g of AIBN was added to the flask. It was polymerized by refluxing for time. Methanol was inject | poured into the obtained reaction material, the acrylic copolymer was precipitated, and the deposit was isolate | separated by filtration, and it dried under vacuum and obtained 23.8g of cycloalkyl-group containing acrylic copolymer solid content. The weight average molecular weight by polystyrene conversion was 4.7x10 <^4> .

[Production Example 4]

[Synthesis of cycloalkyl group-containing acrylic copolymer (4)]

22.5 g of cyclohexyl methacrylate, 7.5 g of methacryl-modified dimethylpolysiloxane macromonomers of the following formula (V) and 70 g of toluene were added to the flask, and nitrogen gas was introduced to make a sufficiently nitrogen atmosphere, and then heated to 80 ° C. 0.15 g of α, α'-azobisisobutyronitrile (hereinafter referred to as AIBN) was added thereto, and the mixture was refluxed for 5 hours to polymerize. Methanol was inject | poured into the obtained reaction material, the acrylic copolymer was precipitated, and the deposit was isolate | separated by filtration, and it dried under vacuum and obtained 13.4g of cycloalkyl-group containing acrylic copolymer solid content. The weight average molecular weight by polystyrene conversion was 5.2x10 <^4> .

[Production Example 5]

[Synthesis of cycloalkyl group-containing acrylic copolymer (5)]

22.5 g of cyclohexyl methacrylate, 7.5 g of methacryl-modified dimethylpolysiloxane macromonomers of the following formula (VI) and 70 g of toluene were added to the flask, and nitrogen gas was introduced to make a sufficiently nitrogen atmosphere, and then heated to 100 ° C. 0.15 g of AIBN was added and refluxed for 3 hours to polymerize. Toluene was distilled off in the evaporator of the obtained reaction material, and it vacuum-dried to obtain 26.6 g of cycloalkyl group containing acrylic copolymer solid content. The weight average molecular weight in polystyrene conversion was 6.7 × 10 ⁴ .

Production Example 6

[Synthesis of cycloalkyl group-containing acrylic copolymer (6)]

22.5 g of cyclohexyl methacrylate, 7.5 g of methacryl-modified dimethylpolysiloxane macromonomers of the following formula (VII), and 70 g of toluene were added to the flask, and nitrogen gas was introduced to make a sufficiently nitrogen atmosphere, and then heated to 80 ° C. 0.15 g of AIBN was added and refluxed for 5 hours to polymerize. Methanol was inject | poured into the obtained reaction material, the acrylic copolymer was precipitated, and the deposit was isolate | separated by filtration, and it vacuum-dried and obtained 29.1 g of cycloalkyl-group containing acrylic copolymer solid content.

[Manufacture example 7]

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

21 g of cyclohexyl methacrylate, 4.5 g of 2-ethylhexyl methacrylate, 4.5 g of methacryl-modified dimethylpolysiloxane macromonomer of formula (VI) and 70 g of toluene were added to the flask, and nitrogen gas was introduced to provide a nitrogen atmosphere. After heating to 80 ° C, 0.15 g of AIBN was added and refluxed for 5 hours to polymerize. Methanol was inject | poured into the obtained reaction material, the acrylic copolymer was precipitated, and the deposit was isolate | separated by filtration, and it vacuum-dried to obtain 11.0 g of cycloalkyl group containing acrylic copolymer solid content. The weight average molecular weight by polystyrene conversion was 6.2x10 <^4> .

[Manufacture example 8]

As a result of synthesizing according to the above synthesis method using each combination shown in the following (8) to (12) as a raw material, a cycloalkyl group-containing acrylic copolymer was obtained.

(8) 50% of cyclohexyl methacrylate and 50% of methacryl modified dimethylpolysiloxane macromonomers of the formula (VI),

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

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

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

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

(Manufacture comparative example 1)

[Synthesis of poly (cyclohexyl methacrylate)]

30 g of cyclohexyl methacrylate and 70 g of toluene were added to the flask, nitrogen gas was introduced to a sufficient nitrogen atmosphere, then heated to 100 ° C, and 0.15 g of AIBN was added to reflux for 3 hours to polymerize. Methanol was inject | poured into the obtained reaction material, the acrylic polymer was precipitated, and the deposit was isolate | separated by filtration, and it vacuum-dried and obtained 29.9 g of poly (cyclohexyl methacrylate) solid content.

(Manufacture comparative example 2)

[Synthesis of cycloalkyl group-containing acrylic copolymer (8)]

15 g of cyclohexyl methacrylate, 15 g of ethyl acrylate, and 70 g of toluene were added to the flask, nitrogen gas was introduced to a sufficient nitrogen atmosphere, then heated to 100 ° C, and 0.15 g of AIBN was added to reflux for 3 hours. I was. Methanol was inject | poured into the obtained reaction material, the acrylic polymer was precipitated, and the deposit was isolate | separated by filtration, and it dried in vacuum and obtained the cycloalkyl group containing acrylic copolymer.

(Manufacture comparative example 3)

[Synthesis of cycloalkyl group-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, nitrogen gas was introduced to a sufficient nitrogen atmosphere, then heated to 100 ° C, and 0.15 g of AIBN was added for 3 hours. It was polymerized by reflux. Methanol was inject | poured into the obtained reaction material, the acrylic polymer was precipitated, and the deposit was isolate | separated by filtration, and it dried under vacuum and obtained 22.2g of cycloalkyl-group containing acrylic copolymer solid content.

(Manufacture comparative example 4)

[Synthesis of cycloalkyl group-containing acrylic copolymer (10)]

15 g of cyclohexyl methacrylate, 15 g of t-butyl methacrylate, and 70 g of toluene were added to the flask, and nitrogen gas was introduced to obtain a sufficient nitrogen atmosphere, and then heated to 100 ° C, and 0.15 g of AIBN was added thereto for 3 hours. It was polymerized by reflux. Methanol was inject | poured into the obtained reaction material, the acrylic copolymer was precipitated, and the deposit was isolate | separated by filtration, and it vacuum-dried and obtained 19.6g of cycloalkyl-group containing acrylic copolymer solid content.

(Manufacture comparative example 5)

[Synthesis of cycloalkyl group-containing acrylic copolymer (11)]

22.5 g of cyclohexyl methacrylate, 7.5 g of t-butyl methacrylate, and 70 g of toluene were added to the flask, nitrogen gas was introduced to make a sufficiently nitrogen atmosphere, and then heated to 100 ° C, and 0.15 g of AIBN was added thereto. It was polymerized by refluxing for 3 hours. Methanol was inject | poured into the obtained reaction material, the acrylic polymer was precipitated, and the deposit was isolate | separated by filtration, and it vacuum-dried and obtained 23.8g of cycloalkyl-group containing acrylic copolymer solid content.

(Manufacture comparative example 6)

[Synthesis of Acryl-Silicon Graft Polymer]

100 g of toluene was added to a four-neck separable flask equipped with a reflux condenser, thermometer, nitrogen inlet tube, and dropping funnel, methyl methacrylate 40 g, n-butyl methacrylate 20 g, and methacryl-modified dimethyl of formula (VI). Nitrogen gas was introduce | transduced into the reaction solution which melt | dissolved 40 g of polysiloxane macromonomers, 50 g of toluene, and 1.5 g of t-butylperoxy-2-ethylhexanoate uniformly, and it is dripped at 100 degreeC under nitrogen atmosphere. After completion of the dropwise addition, the mixture was refluxed for 5 hours to polymerize. Methanol was poured into the obtained reaction product to precipitate and precipitate the acrylic-silicon graft polymer, and the precipitate was separated by filtration and dried in vacuo to obtain 78.5 g of an acrylic-silicon graft polymer solid.

(evaluation)

Solubility in the hard fluid isoparaffin (IP solvent 1620 (manufactured by Idemitsu Kosan Co., Ltd.), flash point 49 ° C) of the acrylic copolymers of Production Examples 1 to 7 and Production Comparative Examples 1 to 6, the transparency and strength of the film, etc. Evaluated accordingly. The results are shown in Tables 1 and 2.

<Evaluation method>

(1) Solubility in light flowing isoparaffin (IP solvent 1620 (manufactured by Idemitsu Kosan Co., Ltd.))

70 mass parts of hard-flowing isoparaffins were added and mixed with 30 mass parts of acrylic copolymers of manufacture examples 1-7 and manufacture comparative examples 1-6, and the solubility in 25 degreeC was evaluated by the following evaluation criteria.

(Double-circle): It melt | dissolves transparently.

(Circle): It looks a little cloudy but melt | dissolves.

(Triangle | delta): Although it melt | dissolves in part, an insoluble acrylic copolymer precipitates.

X: It does not melt.

(2) film transparency

30 mass% acrylic copolymer solution of Preparation Example and Comparative Comparative Example dissolved in hard-flow isoparaffin was prepared on a glass plate with a 100 μm applicator, dried and the film of the acrylic copolymer was prepared, and the transparency of the coating was visually observed. Evaluated.

○: transparent

△: slightly cloudy but visible translucent

×: cloudy and opaque

(3) hardness of film

The thin film of 30 mass% acrylic copolymers of Preparation Examples 1 to 7 and Comparative Comparative Examples 1 to 6 dissolved in hard-flowing isoparaffin was prepared using a 100 μm applicator on a glass plate, and then dried to prepare a film of the acrylic copolymer. And pencil hardness tests were carried out in accordance with the method of JIS-K5400.

From the results of Preparation Examples 1 to 7 of Table 1, it was found that the cycloalkyl group-containing acrylic copolymer of the present invention had good solubility in hard-flowing isoparaffins, and the coating was high in transparency and rigid, and was excellent as a film forming agent. . It was also confirmed that the five types of cycloalkyl group-containing acrylic copolymers described in Production Example 8 were also dissolved in hard-flow isoparaffin to form a transparent film. On the other hand, it was confirmed that the acrylic copolymers of Production Comparative Examples 1 to 5 did not dissolve in hard flow isoparaffin and were not suitable as a film forming agent. In addition, the acrylic-silicone graft polymer of Preparation Comparative Example 6 is a polymer described in Patent Document 1, which is too soft to obtain a film of sufficient hardness, and confirmed that defects such as stickiness, stickiness, and film nonuniformity may occur. It was.

Lip cosmetic

[Examples 1-8 and Comparative Examples 1-5] Oily Liquid Lipstick

An oily liquid lipstick of the composition shown in Table 3 is prepared by the following manufacturing method, and a. Color persistence over time, b. (2) preventing secondary attachment; Glossiness d. No burden, e. The smooth usability was evaluated and the result was shown in Table 3 together.

* 1: The cycloalkyl group containing acrylic copolymer of manufacture example 1 (1)

* 2: The cycloalkyl group containing acrylic copolymer of manufacture example 2 (2)

* 3: The cycloalkyl group containing acrylic copolymer of manufacture example 3 (3)

* 4: Acrylic polymer of the manufacture comparative example 1

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

* 6: Nisset U-3700A (manufactured by Nippon Carbide Co., Ltd.), 50% rigid liquid isoparaffin solution

※ 7: IP solvent 2028 (made by Idemitsu Kosan Corporation)

* 8: AEROSIL 300 (made by Nippon Aero Real)

※ 9: BENTONE 38 (manufactured by Elementis)

※ 10: Polybutene 2000H (made by Idemitsu Kosan Corporation)

(Production method)

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

B: The components (9)-(15) are added to A, and it mixes and disperse | distributes uniformly.

C: After defoaming, it fills the container with a coating body.

(Assessment Methods)

Each sample was tested for use by 20 specialized panels. Each panel is different from d, d and e for immediately after application and no color transition when tissue is turned off 10 minutes after application for me, and for 6 hours after application for observation. The evaluation was made in six stages, and the average value was calculated from the total ratings of the panel power supplies of each sample, and the result was determined by the following four stage criteria. In the table, the judgment result and the average value of the rating in () were described.

<Sensory evaluation item>

end. Color persistence over time

I. Secondary attachment prevention effect

All. Gloss

la. No burden

hemp. Smooth feeling

<Absolute evaluation criteria>

(Rating): (evaluation)

6 points: very good

5 points: good

4 points: slightly good

3 points: Normal

2 points: Slightly bad

1 point: Poor

<Four-stage judgment standard>

(Judgement): (Average score of rating)

◎: more than 5 points

(Circle): 3 points or more and 5 points or less

△: more than 2 points and 3 points or less

×: 2 points or less

As can be seen from the results of Table 3, the oil-based liquid lipstick of Examples 1 to 8 of the present invention compared to the oil-based liquid lipstick of Comparative Examples 1 to 5 over time, color persistence, secondary adhesion prevention effect, It was excellent in glossiness, no burden, and smooth usability. In particular, Example 6 in which an olefin polymer and / or polyolefin which is a liquid nonvolatile hydrocarbon oil at 25 ° C. was blended was excellent in terms of color persistence and no burden. On the contrary, in Comparative Example 1 in which the cycloalkyl group-containing acrylic copolymer of the present invention was not blended, the film was not formed, so the color persistence was poor, and the secondary adhesion preventing effect was not seen. In the comparative example 2 which did not mix | blend a volatile oil agent, a cosmetic film was not able to form a sufficient film, and the satisfactory thing was not obtained in terms of a secondary adhesion prevention effect and no burden. In Comparative Example 3 using an acrylic polymer instead of the cycloalkyl group-containing acrylic copolymer of the present invention, trimethylsiloxysilic acid was used instead of the cycloalkyl group-containing acrylic copolymer of the present invention because of the lack of uniformity of the makeup film. In the used Comparative Example 4, since the flexibility of the makeup film is insufficient, there is no burden. In Comparative Example 5 using the dispersion of the alkyl acrylate-styrene copolymer instead of the cycloalkyl group-containing acrylic copolymer of the present invention, the flexibility and uniformity of the makeup film It was insufficient, and the satisfactory thing was not obtained from the point of glossiness and no burden.

Example 9 Oily Stick Shape Lipstick

(ingredient) (%)

(1) Polyethylene wax ※ 11 6

(2) Candelilla Wax 6

(3) tri2-ethylhexanoate cetyl 30

(4) Cycloalkyl group-containing acrylic copolymer * 2 1

(5) Isododecane ※ 12 remaining amount

(6) Trimethylsiloxysilicate solution * 5 1

(7) decamethylcyclopentasiloxane 5

(8) PEG-9 polydimethylsiloxyethyldimethicone 1

(9) silylated silicic anhydride * 13 2

(10) Bengala Cloth Mica Titanium * 14 5

(11) Red 202 0.1

(12) Yellow No. 4 0.1

(13) Refined Avocado Oil 0.1

14.Spice 0.5

※ 11: PERFORMALENE 500 (manufactured by New Phase Technology Co., Ltd.)

※ 12: Isododecane (manufactured by Bayer Corporation)

※ 13: AEROSIL R972 (made by Nippon Aerosil)

※ 14: Dimethyl polysiloxane 3% treatment

(Production method)

A: The component (4) and the component (5) are melt | dissolved uniformly.

B: A, components (1) to (3) and components (6) to (8) are dissolved by heating at 95 ° C uniformly.

The components (9)-(14) are added to C: B, and it mixes and disperse | distributes uniformly.

D: After defoaming C, it fills a container.

(evaluation)

The oil-based stick lipstick thus obtained was evaluated in the same manner as in Examples 1 to 8, and was excellent in color persistence, secondary adhesion preventing effect, glossiness, no burden, and smooth usability over time.

Example 10 Oily Paste Lip Gloss

(ingredient) (%)

(1) palmitic acid dextrin 3

(2) Heavy flow isoparaffin ※ 15 30

(3) Cycloalkyl group-containing acrylic copolymer solution * 16 50

(4) Isodo decane ※ 11 balance

(5) Titanium oxide coated glass powder ※ 17 5

(6) Honey 0.01

※ 15: Pearllim 18 (made by Nippon Yushi Corporation)

* 16: 30% hard-flow isoparaffin solution of the cycloalkyl group-containing acrylic copolymer (3) of Preparation Example 3.

* 17: Metashine 1080RC-R (manufactured by Nippon Itagara Co., Ltd.)

(Production method)

A: The components (1) to (4) are dissolved by heating at 95 ° C uniformly.

B: The components (5)-(6) are added to A, and it mixes and disperse | distributes uniformly.

C: After defoaming, it fills a tube container.

(evaluation)

The oily paste-like lip gloss thus obtained was evaluated in the same manner as in Examples 1 to 8, and was excellent in color persistence, secondary adhesion preventing effect, glossiness, no burden, and smooth feeling over time.

Example 11 Oily Solid Lip Balm

(ingredient) (%)

(1) ceresin waxin 18

(2) Vaseline 30

(3) glyceryl 2-ethylhexanoate 5

(4) Glyceryl triisostearate 10

(5) Cycloalkyl group-containing acrylic copolymer * 18 1

(6) Cycloalkyl group-containing acrylic copolymer ※ 19 1

(7) Isohexadecane ※ 20 residues

(8) ethanol 0.5

(9) Polyethylene terephthalate, aluminum, epoxy laminated powder 1

(10) Titanium Oxide * 21 0.1

(11) tocopherol acetate 0.1

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

* 19: The cycloalkyl group containing acrylic copolymer of manufacture example 5 (5)

※ 20: Isohexadecane (made by Unikema Corporation)

※ 21: 5% perfluoropolyether treatment

(Production method)

A: The components (1) to (7) are dissolved by heating at 95 ° C uniformly.

B: Components (8)-(11) are added to A, and it mixes and disperse | distributes uniformly.

C: After defoaming, just fill the container.

(evaluation)

The oily solid lip balm thus obtained was evaluated in the same manner as in Examples 1 to 8, and was excellent in color persistence, secondary adhesion preventing effect, glossiness, no burden, and smooth feeling over time.

Example 12 Water-in-oil type paste lipstick

(ingredient) (%)

(1) palmitate dextrin 2

(2) residual amount of α-olefin oligomer

(3) decamethylcyclopentasiloxane 5

(4) Polyoxyethylene-methyl polysiloxane copolymer 1

(5) sesquioleate sorbitan 5

(6) Cycloalkyl group-containing acrylic copolymer ※ 22 0.5

(7) Isodo Deccan ※ 12 1

(8) purified water 20

(9) Red 226 0.3

(10) Titanium Oxide * 21 0.1

* 22: The cycloalkyl group containing acrylic copolymer of manufacture example 6 (6)

(Production method)

A: The components (1) to (7) are dissolved by heating at 95 ° C uniformly.

B: The component (8) is added to A and emulsifies. Thereafter, the components (9) to (10) are added and mixed uniformly.

C: After defoaming, it fills a tube container.

(evaluation)

The water-in-oil type paste lipstick obtained in this way was evaluated in the same manner as in Examples 1 to 8, and was excellent in color persistence, secondary adhesion preventing effect, glossiness, no burden, and smooth feeling over time.

Example 13 Water-in-oil Type Paste Lipstick Base

(ingredient) (%)

(1) palmitate dextrin 5

(2) residual amount of α-olefin oligomer

(3) sesquioleic acid sorbitan 5

(4) Cycloalkyl group-containing acrylic copolymer ※ 23 0.5

(5) Isodo Deccan ※ 12 1

(6) purified water 10

(7) Red 218 0.05

(8) nylon fiber 0.1

* 23: The cycloalkyl group containing acrylic copolymer of manufacture example 7 (7)

(Production method)

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

B: Components (6) to (8) are added to A to emulsify.

C: After defoaming, it fills a tube container.

(evaluation)

The water-in-oil type paste-like lipstick base thus obtained was evaluated in the same manner as in Examples 1 to 8, and was excellent in color persistence, no burden, and smooth usability over time.

Ⅱ Eye Liner Cosmetic

[Examples 14-17, Comparative Examples 6-9] Eyeliner (oil type liquid)

The eyeliner of the prescription shown in Table 4 was prepared by the following manufacturing method, and sensory evaluation was performed by the following method about the glossiness as a cosmetic effect with respect to the uniformity of a makeup film, and the bleeding and peeling as a persistence of a makeup film with respect to color development. It was. The results are also shown in Table 4.

※ 24: IP solvent 1620 (made by Idemitsu Kosan Corporation)

※ 25: The cycloalkyl group containing acrylic copolymer (1) of manufacture example 1 was melt | dissolved in hard-flowing isoparaffin (IP solvent 1620), and it was made into 40% solution.

※ 26: Opanol B-100 (made by BASF Corporation)

* 27: Silicone KF-9021 (manufactured by Shin-Etsu Chemical Co., Ltd.) (solid content 50% decamethylcyclopentasiloxane solution)

* 28: ester gum HP (manufactured by Warakawa Chemical Co., Ltd.)

* 29: Nisset U-3700A (manufactured by Nippon Carbide Co., Ltd.)

* 30: 3% fluoroalkylalkoxysilane treatment

※ 31: AEROSIL R976S (made by Nippon Aero Real)

※ 32: AEROSIL 300 (made by Nippon Aero Real)

(quite)

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

B: The components (11)-(16) are added to A, and it mixes uniformly.

C: Fill B with a container to make a product.

(Assessment Methods)

Each of the samples was evaluated by the sensory evaluation panel of ten people in the following evaluation items (a) using the absolute evaluation criteria in seven steps, and the average value of each sample was evaluated using (2) four-step evaluation criteria. It judged by. In addition, in Table 4, the average value of the grade in the judgment and () was described.

In addition, about evaluation items d and e, after apply | coating a sample along the outline of an eye, the panel was made to live normally, and the cosmetic effect after 12 hours passed was evaluated.

(Evaluation item)

a. Uniformity of the cremation membrane

b. Gloss

c. Color

d. No smearing (persistence)

e. No peeling off (persistence)

(1) absolute evaluation criteria

(Rating): (evaluation)

6: very good

5: Good

4: slightly good

3: normal

2: a little bad

1: bad

0: very bad

(2) Four levels of judgment criteria

(Average Point): (Judgement)

Exceed 5 points: Very good: ◎

3 points or more and 5 points or less: Good: ○

More than 1 point and less than 3 points: Slightly poor: △

1 point or less: Poor: ×

As can be seen from the results in Table 4, since the eyeliners of Examples 14 to 17 which are the present invention can draw lines smoothly as compared to the eyeliners of Comparative Examples 6 to 9, uniformity of the makeup film is obtained, and the glossiness is obtained. The cosmetic effect of color development was excellent, and the cosmetic effect of no bleeding or peeling was obtained even after 12 hours, and it had much superior characteristics in all respects.

On the other hand, in Comparative Example 6 in which polyisobutylene is used instead of the cycloalkyl group-containing acrylic copolymer of the present invention, it is difficult to adhere uniformly because of lack of smoothness at the time of use, which is satisfactory in terms of uniformity and glossiness of the makeup film. Nothing was obtained.

In Comparative Example 7, in which a trimethylsiloxysilicate solution was used instead of the cycloalkyl group-containing acrylic copolymer of the present invention, the cosmetic film lacked the flexibility and the eye movement could not be followed, so that a part of the cosmetic film was peeled off. Since the uniformity of a makeup film | membrane also falls, what was satisfactory in the point of glossiness and color development was not obtained, and there existed a problem in the usability which is difficult to draw because lack of smoothness.

Moreover, in the comparative example 8 which uses pentaerythritol rosin in place of the cycloalkyl group containing acrylic copolymer of this invention, there exists stickiness of a makeup film at the time of use, the uniformity of a makeup film worsens, glossiness falls, and a satisfactory thing is obtained. I didn't lose.

In addition, in Comparative Example 9, in which a hard flow isoparaffin dispersion of acrylic-styrene copolymer resin is used instead of the cycloalkyl group-containing acrylic copolymer of the present invention, since the thickness of the makeup film is not sufficiently obtained, the smoothness of the makeup film is insufficient. Since the transparency of the makeup film is also inferior, there is a problem in usability such that satisfactory things are not obtained in terms of glossiness and color development, and difficulty in drawing due to lack of smoothness.

[Examples 18 to 23]

Instead of the cycloalkyl group-containing acrylic copolymer solution used in Example 14, the cycloalkyl group-containing acrylic copolymers (2) to (7) obtained in Production Examples 2 to 7 were dissolved in hard-flowing isoparaffin (IP solvent 1620) to 40% solution. As a result of evaluating the mascara obtained by the manufacturing method similar to Example 14, it was excellent in the uniformity of a makeup film, high glossiness and color development, and there was no peeling and bleeding, and it was excellent in the persistence of a makeup effect. Table 5 shows the prescription and the result.

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 (Oil Type Liquid)

(ingredient) (%)

(1) Cycloalkyl group-containing acrylic copolymer solution * 33 10

(2) palmitate dextrin 4

(3) polyethylene wax 4

(4) paraffin wax 2

(5) Methyl paraoxybenzoate 0.1

(6) Hard Flow Isoparaffin ※ 24 13.5

(7) Dimethyl distearyl ammonium hectorite * 34 2.5

(8) Propylene Carbonate 0.5

(9) Decamethylcyclopentasiloxane ※ 35 residual quantity

(10) Silicon-based compound treated iron oxide * 36 15

(11) Fluorine-based compound treated sericite * 30 5

(12) Fluorine-based compound treated talc * 30 8

(13) Silicon-based compound treated mica ※ 36 0.5

(14) silylated silicic anhydride * 31 2

(15) Soluble Rosemary Extract 0.1

* 33: The cycloalkyl group-containing acrylic copolymer (4) of Preparation Example 4 was dissolved in hard-flow isoparaffin (IP solvent 1620) to obtain a 15% solution.

* 34: Dimethyl distearyl ammonium modified synthetic sodium silicate and magnesium: Lucentite SAN (manufactured by Cope Chemical Co., Ltd.)

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

※ 36: 4% dimethylpolysiloxane treatment

(Production method)

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

B: The components (7)-(15) are added to A, and it mixes uniformly.

C: B was filled in the container and the planetary eyeliner was obtained.

(evaluation)

The oily liquid eyeliner obtained as described above was excellent in the uniformity of the makeup film, had a high glossiness and color development, had no peeling and smearing, and was excellent in the persistence of the makeup effect.

Example 25 Eyeliner (Water-in-Water Liquid)

(ingredient) (%)

(1) Cycloalkyl group-containing acrylic copolymer solution * 37 20

(2) hard-flowing isoparaffin ※ 24 residues

(3) silylated silicic anhydride * 31 7

(4) Silicate anhydride * 32 1

(5) Benzyldimethyl stearylammonium modified synthetic sodium silicate magnesium ※ 38 0.5

(6) Dimethyl distearyl ammonium hectorite * 39 0.5

(7) Dimethyl Polysiloxane (20cs) 1

(8) PEG-9 polydimethylsiloxyethyldimethicone * 40 0.1

(9) Silicon-based compound black iron oxide * 41 15

(10) purified water 2

(11) Vinylpyrrolidone Styrene Copolymer Polymer Emulsion * 42 5

(12) phenoxyethanol 0.1

(13) 1, 2-pentanediol 0.1

(14) ethyl alcohol 3

(15) tocopherol acetate 0.1

(16) Soluble Rosemary Extract 0.1

* 37: The cycloalkyl group-containing acrylic copolymer (1) of Preparation Example 1 was dissolved in a hard-flow isoparaffin (IP solvent 1620) to obtain a 20% solution.

* 38: Lucentite SSN (manufactured by Cope Chemical Co., Ltd.)

※ 39: Benton 38V BC (Elementary company)

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

※ 41: Methylhydrogenpolysiloxane 2% treatment

※ 42: ANTARA 430 (manufactured by ISP)

(quite)

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

B: The components (10)-(16) are added and it mixes and melts uniformly.

C: B is added to A to emulsify.

D: Fill C into a container to obtain the product.

(evaluation)

The water-in-oil type liquid eyeliner obtained as described above was excellent in the uniformity of the makeup film, had a high glossiness and color development, had no peeling and smearing, and was excellent in the persistence of the makeup effect.

Ⅲ Cosmetics for Eyelashes

Examples 26 to 30 and Comparative Examples 10 to 12 Mascara (oil type liquid)

Mascara of the prescription shown in Table 6 was prepared by the following manufacturing method, and the sensory evaluation was performed by the following method about the glossiness, the curl up effect, the curling effect, and the uniformity of a makeup film. The results are also shown in Table 6.

※ 43: IP solvent 1620 (made by Idemitsu Kosan Corporation)

* 44: The cycloalkyl group-containing acrylic copolymer (1) of Preparation Example 1 was dissolved in hard-flow isoparaffin (IP solvent 1620) to obtain a 40% solution.

* 45: Silicone KF-9021 (manufactured by Shin-Etsu Chemical Co., Ltd.)

* 46: Ester gum HP (manufactured by Warakawa Chemical Co., Ltd.)

* 47: Nisset U-3700A (manufactured by Nippon Carbide Co., Ltd.)

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

* 49: AEROSIL 300 (made by Nippon Aero Real)

(quite)

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

B: Components (8)-(12) are added to A, and it mixes uniformly.

C: After cooling B, it fills a container and makes a product.

(Assessment Methods)

Each of the samples was evaluated by the sensory evaluation panel of 10 persons in the following steps (a) using the absolute evaluation criteria (7) using the absolute evaluation criteria, and the average value of each sample was evaluated using the (2) four-step evaluation criteria. Determined. In addition, in Table 6, the average value of the grade in the judgment and () was described.

In addition, evaluation item I evaluated immediately after application | coating, and about evaluation item a, d, d, and hemp, the sample was apply | coated to an eyelash to make a panel normal life, and the cosmetic effect after 12 hours was evaluated.

(Evaluation item)

end. Glossiness Persistence

I. Curl up effect

All. Curling effect

la. Persistence of Volume Effect

hemp. Persistence of the uniformity of the makeup

(1) absolute evaluation criteria

(Rating): (evaluation)

6: very good

5: Good

4: slightly good

3: normal

2: a little bad

1: bad

0: very bad

(2) Four levels of judgment criteria

(Average Point): (Judgement)

Exceed 5 points: Very good: ◎

3 points or more and 5 points or less: Good: ○

More than 1 point and less than 3 points: Slightly poor: △

1 point or less: Poor: ×

As can be seen from the results in Table 6, the mascara of Examples 26 to 30, which is the present invention, is very easy to apply and has good adhesion, and immediately after application, the makeup film has a uniform and glossy feeling, and a curl-up effect is also obtained. The sustainability was very good. In particular, Example 30 had a significant volume effect.

On the other hand, in Comparative Example 10, in which a trimethylsiloxysilicate solution is used instead of the cycloalkyl group-containing acrylic copolymer solution of the present invention, since a firm makeup film is obtained, flexibility is not obtained, the uniformity of the makeup film over time is achieved. By this deterioration, satisfactory in terms of glossiness, curling effect, and uniformity of the makeup film were not obtained, and in addition, low adhesion was not obtained.

In Comparative Example 11, in which pentaerythritol rosin is used instead of the cycloalkyl group-containing acrylic copolymer of the present invention, since the makeup film is sticky, the eyelashes are clumped together to reduce the uniformity of the makeup film, resulting in poor glossiness. Result. In addition, since the adhesion is so high that the eyelashes are heavy and sagging, satisfactory results have not been obtained in terms of the curling effect.

In addition, in Comparative Example 12 in which the hard-flowing isoparaffin dispersion of acrylic-styrene copolymer resin is used instead of the cycloalkyl group-containing acrylic copolymer solution of the present invention, it is difficult to adhere uniformly because of lack of smooth usability. No satisfactory one was obtained in terms of film uniformity and glossiness. Moreover, since the strength of the makeup film was also insufficient, a satisfactory thing was not obtained in terms of the makeup effect such as a curl up effect or a curling effect and its persistence.

In addition, when the mascara of Examples 26 to 30 were applied overlaid (constantly applied with ten applicators), the volume effect could also be obtained without impairing the uniformity or curling effect of the makeup film. The stickiness of the makeup film was so strong that the eyelashes clump together, the uniformity of the makeup film was not obtained, or the flexibility of the makeup film was low, resulting in poor feeling.

[Examples 31 to 36]

Instead of the cycloalkyl group-containing acrylic copolymer solution used in Example 26, the cycloalkyl group-containing acrylic copolymers (2) to (7) obtained in Production Examples 2 to 7 were dissolved in hard-flowing isoparaffin (IP solvent 1620) to 40% solution. When the mascara obtained by the manufacturing method similar to Example 26 was used using the thing made into the above, the uniformity of a makeup film was high, there was glossiness, the curling effect was also acquired, and these persistence was also excellent. Table 7 shows the prescription and the result.

The following Examples 37-40 were also evaluated similarly to Examples 26-30 and Comparative Examples 10-12.

Example 37 Mascara (Oil-in-Water Emulsified Liquid)

(ingredient) (%)

(1) stearic acid 3

(2) carnauba wax 1

(3) beeswax 1

(4) paraffin wax 1

(5) Cycloalkyl group-containing acrylic copolymer solution * 50 10

(6) Hard Flow Isoparaffin * 43 0.5

(7) Self-emulsifying glycerin monostearate 1

(8) Sucrose Fatty Acid Ester ※ 51 2

(9) Monooleic acid polyoxyethylene sorbitan (20E.O.) 1.3

(10) sesquioleate sorbitan 0.5

(11) iron oxide black 5

(12) Silic anhydride * 52 0.1

(13) Silic anhydride * 53 0.1

(14) triethanolamine 1.2

(15) 1, 3-butylene glycol 8

(16) 1, 2-pentanediol 0.1

(17) Methyl paraoxybenzoate 0.2

(18) Alkyl polyacrylate copolymer emulsion * 54 10

(19) Polyvinyl acetate emulsion * 55 0.5

(20) Beauty agent (peony extract) 0.03

(21) Refining water level

* 50: The cycloalkyl group-containing acrylic copolymer (4) of Preparation Example 4 was dissolved in hard-flow isoparaffin (IP solvent 1620) to obtain a 20% solution.

※ 51: Sugar wax S-10E (made by Daiichi Pharmaceutical Co., Ltd.)

※ 52: Silysia 550 (manufactured by Fuji-Silysia Chemical)

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

* 54: YODOZOL GH810F (50% solids) (manufactured by Nippon N & S Corporation)

※ 55: Vinibran GV-5651 (solid content 40%) (made by Nisshin Chemical Co., Ltd.)

(quite)

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

B: The components (12)-(21) are heated and mixed uniformly.

C: B is added to A and emulsified at 80 degreeC.

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

(evaluation)

The oil-in-water emulsion type mascara obtained as mentioned above was excellent in the uniformity of a makeup film, and was excellent in the makeup effect of glossiness, a curl effect, a volume feeling, and its sustainability.

Example 38 Mascara (oil type liquid) (long rush type)

(ingredient) (%)

(1) Cycloalkyl group-containing acrylic copolymer solution * 44 48.6

(2) Candelilla resin * 56 3

(3) hard-flowing isoparaffin ※ 43 remaining

(4) palmitate dextrin 1.4

(5) Microcrystalline Waxes 2

(6) ceresin 3

(7) beeswax 2

(8) Trimethylsiloxysilicate solution * 45 1

(9) Dimethyl distearyl ammonium hectorite * 48 10

(10) Silicate anhydride * 52 7

(11) Silicate anhydride * 53 3

(12) Fluorine-based compound black iron oxide * 57 5

(13) Fluorine-based compound treated talc ※ 57 5

(14) Nylon fiber * 58 3

※ 56: Candera resin E-1 (made by Nippon Natural Products)

* 57: 3% fluoroalkylalkoxysilane treatment

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

(quite)

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

B: Component (9) is added to A and mixed.

C: The components (10)-(14) are added to B, and it mixes uniformly.

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

(evaluation)

The oil-based mascara obtained as mentioned above was excellent in the uniformity of a makeup film, and was excellent in the makeup effect of the glossiness, a curl effect, a long rush effect, and a volume effect, and its sustainability.

Example 39 Mascara (Water-in-oil Emulsified Liquid)

(ingredient) (%)

(1) decamethylcyclopentasiloxane 5

(2) Hard Flowing Isoparaffins * 43 5

(3) Cycloalkyl group-containing acrylic copolymer solution * 44 12.5

(4) PEG-9 polydimethylsiloxyethyldimethicone * 59 2

(5) Dimethyl distearyl ammonium hectorite * 48 5

(6) Mishyu Silicate ※ 52 3

(7) Silicon-based compound black iron oxide * 60 5

(8) talc 5

(9) Alkyl polyacrylate copolymer emulsion * 54 10

(10) Polyvinyl Acetate Emulsion * 55 10

(11) 1, 3-butylene glycol 7

(12) Methyl paraoxybenzoate 0.1

(13) remaining amount of purified water

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

※ 60: Dimethyl polysiloxane 4% treatment

(quite)

A: The components (1) to (4) are mixed uniformly.

B: Components (5)-(8) are added to A, and it mixes.

C: The components (9)-(13) are added to B, and it emulsifies at normal temperature.

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

(evaluation)

The water-in-oil emulsified mascara obtained as described above was excellent in the uniformity of the makeup film, and was excellent in the makeup effect such as glossiness, curl effect, volume effect, and its sustainability.

Example 40 Mascara Base (Oil Type Liquid)

(ingredient) (%)

(1) palmitate dextrin 6

(2) hard-flowing isoparaffin ※ 43 remaining

(3) isododecane 5

(4) Cycloalkyl group-containing acrylic copolymer solution * 61 50

(5) Mica Titanium 3

(6) Dimethyl distearyl ammonium hectorite * 46 5

(7) Mist anhydrous silicate * 62 2

(8) mica 3

(9) titanium oxide coated glass powder 1

(10) talc 20

※ 61: The cycloalkyl group containing acrylic copolymer (1) of manufacture example 1 was melt | dissolved in hard-flowing isoparaffin (IP solvent 1620), and it was set as 15% solution.

※ 62: AEROSIL R972 (made by Nippon Aerosil)

(quite)

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

B: Fill A into a container, cool to obtain a product.

(evaluation)

The oil-based mascara base obtained as mentioned above was excellent in the uniformity of a makeup film, easy to apply commercially available mascara, and was excellent in the makeup effect of a curl effect, a volume effect, and its sustainability.

The cycloalkyl group-containing acrylic copolymer of the present invention is characterized by dissolving in volatile oils such as hard fluid isoparaffin, and the coating has high film strength and excellent transparency, adhesion and water resistance.

Therefore, when the cycloalkyl group-containing acrylic copolymer of the present invention is blended into a cosmetic, a cosmetic excellent in gloss, adhesion and water resistance, and excellent in cosmetic persistence is obtained, and is particularly suitable as a makeup cosmetic.

For example, as an eyeliner cosmetic, it is excellent in the uniformity of a makeup film, has high glossiness and color development, does not have a bleeding or peeling, and is excellent in the persistence of a makeup effect. Moreover, as a cosmetics for eyelashes, it is excellent in the curl effect and its persistence, and is excellent in the uniformity and glossiness of a makeup film. Moreover, as a cosmetic for lips, it is excellent in the color persistence and the secondary adhesion prevention effect with time, and it is excellent in glossiness, no burden, and a smooth usability.

Claims (13)

As an acryl-type copolymer obtained by superposing | polymerizing the monomer containing the following component (a1) and a component (a2) and / or a component (a3), the compounding quantity of a component (a1) is 50-90 mass% in the constituent monomer total amount, Make-up containing a cycloalkyl group-containing acrylic copolymer, characterized in that the compounding amount of the component (a2) and / or the component (a3) is 10 to 50% by mass, and is dissolved at least 30% by mass at 25 ° C in hard flow isoparaffin. Cosmetics.
Component (a1): Formula (I)
[Formula 1]

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a cycloalkyl group) and / or an acrylate and / or methacrylate represented by
Component (a2): Formula (II)
(2)

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

(In formula, R <_5> represents a hydrogen atom or a methyl group, R <_6> -R <_12> represents a C1-C5 alkyl group each independently, m shows the integer of any of 1-10, n is 0-200 The makeup cosmetics characterized by the above-mentioned. The makeup cosmetic according to any one of claims 1 to 5, wherein the component (a1) is cyclohexyl methacrylate. The weight average molecular weight by polystyrene conversion measured by the liquid gel permeation chromatography of a cycloalkyl group containing acrylic copolymer is 1.0 * 10 <^4> -2.0 * 10 <^5> , The system of any one of Claims 1-6. Makeup cosmetics. The makeup cosmetic according to any one of claims 1 to 7, further comprising a volatile emulsion. The makeup cosmetic according to claim 8, wherein the volatile emulsion is hard flowing isoparaffin. The makeup cosmetic according to any one of claims 1 to 9, further comprising a powder containing or not containing a colorant. The makeup cosmetic according to any one of claims 1 to 10, which is a cosmetic for lips, an eyeliner cosmetic or a cosmetic for eyelashes. The makeup cosmetic according to claim 10, wherein a liquid nonvolatile hydrocarbon oil is blended at 25 ° C as a cosmetic for lips. The makeup cosmetic according to claim 10, wherein the powder containing a colorant contains silicic anhydride as an eyeliner cosmetic or a cosmetic for eyelashes.