JPH09110642A - Aqueous manicure preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous manicure preparation containing powder which is subjected to hydrophilizing treatment with a silylating agent having polyoxyethylene chain and an acrylic polymer emulsion and excellent in usability and coating film performance. SOLUTION: This aqueous manicure preparation contains 0.01-20wt.% powder which is subjected to hydrophilizing treatment with a silylating agent represented by the formula, (R<1> O)a R<2> bSiR<3> O(C2 H4 O)p (C3 H6 O)q R-<4> [R<1> is a 1-10C alkyl; R<2> is a 1-10C alkyl or phenyl; R<3> is a 2-5C divalent hydrocarbon; R<4> is H or 1-10C alkyl; (a) is 1-3; (b) is 0-2; (a+b)=3; (p) is 2-200; (q) is 0-200; (p+q)=3-200; (p)/(q)>1] and having polyoxyethylene chain and 2-60wt.% (based on solid content) acrylic polymer emulsion. The preparation is excellent in coating performance such as adhesiveness of make up, gloss, etc., and is free of occurrence of sediment and uneven color caused by aggregation of pigment and stable also in low viscosity and used as nail enamel, enamel top coat, enamel paste coat, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based nail enamel characterized in that a powder hydrophilized with a silylating agent having a polyoxyethylene chain is mixed with an acrylic polymer emulsion.

[0002]

2. Description of the Related Art Conventionally, nail enamel has been widely used as a makeup cosmetic for the toes, and its formulation is toluene,
Solvent-type products, mainly acetic acid esters, were the mainstream. However, with the recent increase in safety preference, nail polishes of a type that does not use an organic solvent, for example, water-based nail polishes (hereinafter referred to as “water-based nail polishes”) have come to be studied. In the case of water-based nail enamel, as in the case of conventional solvent-type nail enamel, the dispersion stability of the pigment is an important factor that determines the appearance quality and viscosity of the product, especially the dispersion of the pigment in the low viscosity range. Stabilization is an important issue in ensuring the usability of nail enamel. When adding a pigment to a water-based nail enamel, simply adding it untreated will cause aggregation, sedimentation, and color unevenness, and it will not be possible to obtain a satisfactory quality nail enamel. Methods of coating and compounding have been used. As a coating treatment method which has been conventionally used, silicone treatment (Japanese Patent Laid-Open No. 6-21163)
No. 0), treatment with a fluorine compound (JP-A-6-211).
631 publication) and the like.

[0003]

However, the surfactants used to disperse the above-mentioned powders reduce the adhesion of the nail varnish coating film, and especially water-based nail varnish also lower the water resistance. However, there is a drawback that the coating film is whitened and the coating film strength is lowered depending on the amount and type of the surfactant compounded. On the other hand, in the method of dispersing a pigment by a physical method described in JP-A-4-103516, in which a polymer emulsion and a pigment are pulverized together to obtain a high pigment dispersion state by micronizing the pigment, sedimentation of the pigment over time, It is difficult to completely solve the problem such as color unevenness, and in order to obtain a stable dispersion of the pigment, a method of increasing the viscosity of the product to stabilize the pigment has been used. However, there is a drawback that the usability of the product is poor and the function of the product is significantly deteriorated. Therefore, there has been a demand for the development of a powder composition capable of obtaining a high pigment dispersion effect in a low viscosity range without deteriorating the properties such as product adhesion and film strength.

[0004]

In view of the above situation, the present inventors have earnestly studied, and as a result, when a powder hydrophilized with a silylating agent having a polyoxyethylene chain and an acrylic polymer emulsion were blended, The inventors have found that a powder can be stably blended with a water-based nail enamel in a low viscosity range without impairing the properties such as product adhesiveness and film strength, and have completed the present invention. That is, the present invention provides a water-based nail enamel which is excellent in dispersion stability of a powder, in which a powder hydrophilized with a silylating agent having a polyoxyethylene chain and an acrylic polymer emulsion are blended. .

The powder hydrophilized with a silylating agent having a polyoxyethylene chain (hereinafter referred to as "mother powder") used in the present invention may be any powder incorporated in cosmetics, for example, , As inorganic powder, talc, kaolin,
Synthetic mica, magnesium carbonate, calcium carbonate, aluminum silicate, magnesium silicate, magnesium aluminum silicate, anhydrous silicic acid, barium sulfate, bentonite, smectite, titanium oxide, zinc oxide, aluminum oxide, red iron oxide, iron oxide yellow, black oxide Examples thereof include iron, titanium monoxide, chromium oxide, dark blue, ultramarine blue, iron oxide mica, iron oxide mica titanium, mica titanium, bismuth oxychloride, titanium yellow, and boron nitride. Examples of the organic powder include tar dyes, nylon powder, polyethylene powder, methylmethacrylate, polytetrafluoroethylene powder, wool powder, silk powder, crystalline cellulose, and the like. A composite one can be used. Furthermore, among the above-mentioned powders, in the water-based nail enamel containing an acrylic polymer emulsion, inorganic powders which are significantly aggregated and precipitated,
In particular, titanium oxide, iron oxide and composite powder containing them,
As a mother powder, it is particularly preferable because a remarkable effect can be obtained.

The silylating agent having a polyoxyethylene chain used in the present invention is not particularly limited as long as it has a polyoxyethylene chain, and is represented by the following general formula (1). Silylating agents are preferred. _{^{(R 1 O) a R 2}} b SiR 3 O (C 2 H 4 O) p (C 3 H 6 O) q R 4 ... (1) ( wherein, R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ² is an alkyl group having 1 to 10 carbon atoms or a phenyl group, R ³ is a divalent hydrocarbon group having 2 to 5 carbon atoms, and R ⁴ is hydrogen or 1 to carbon atoms.
An alkyl group of 10, a is an integer of 1 to 3, b is an integer of 0 to 2, and a + b is 3. p is an integer of 2 to 200,
q is an integer of 0 to 200, and p + q is an integer of 3 to 200. Moreover, p / q is 1 or more. )

Specifically, for example, (CH
₃ O) ₃ SiC ₃ H ₆ O (C ₂ H ₄ O) ₁₀ H, (CH ₃ O) ₃ S
_{iC 3 H 6 O (C 2} H 4 O) 10 CH 3, (CH 3 CH 2 O) 3 S
_{iC 3 H 6 O (C 2} H 4 O) 20 (C 3 H 6 O) 10 CH 3, (C
_{H 3 O) 3 SiC 3 H} 6 O (C 2 H 4 O) 30 C 2 H 5, (C
_{H 3) (CH 3 O)} 2 SiC 3 H 6 O (C 2 H 4 O) 5 C 3 H 7,
(CH ₃ O) ₃ SiC ₄ H ₈ O (C ₂ H ₄ O) ₁₀ C ₄ H ₉ , (C
₄ H ₉ O) (CH ₃ ) ₂ SiC ₅ H ₁₀ O (C ₂ H ₄ O) ₂₀ C
H ₃ and the like. These silylating agents may be used alone or in combination of two or more as required.

The hydrophilized powder using the silylating agent having a polyoxyethylene chain of the present invention is prepared by dispersing the powder in water, alcohol or a mixture thereof, and adding water, alcohol or the like to the dispersion. A wet method in which a silylating agent dissolved in these mixed solutions is added, and after stirring treatment or ball mill treatment, moisture is removed, drying, heat treatment, and pulverization are carried out,
It can be obtained by a conventionally known method such as a dry method in which a silylating agent is sprayed on the powder, and the powder is dried and heat-treated.

The treatment amount of the silylating agent having a polyoxyethylene chain varies depending on the shape and type of the mother powder, the type of treating agent and the treating method, and is not particularly limited, but the coating film performance and viscosity are stable over time. In terms of sex, 0.0 with respect to the mother powder
1 to 20.0% by weight (hereinafter simply referred to as [%]) is preferable, and 0.1 to 10.0% is more preferable.

The blending amount of the treated powder is not particularly limited, but it is preferably 0.01 to 20%, more preferably 0.01 to 15% in terms of usability during coating. These treated powders may be used alone or in combination of two or more as required.

The acrylic polymer emulsion used in the present invention is a copolymer composed of one or more selected from acrylic acid, methacrylic acid or their alkyl esters or derivatives. As monomers, acrylic acid, methyl acrylate, ethyl acrylate, acrylic acid amide, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, N, N-dimethylamino Ethyl acrylate, acrylonitrile,
Methacrylic acid, ethyl methacrylate, methacrylic acid amide, n-propyl methacrylate, n-butyl methacrylate,
Examples thereof include isobutyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, hydroxyethyl methacrylate and N, N-dimethylaminoethyl methacrylate. Moreover, when copolymerizing these monomers, styrene, vinyl acetate, etc. may be copolymerized. The structure of the obtained polymer may be one-layered or multi-layered. In addition, examples of the production method include soap-free polymerization using a reactive emulsifier, and emulsifier-free polymerization in which the necessary monomers are polymerized by a known method such as an emulsifier-free heterogeneous polymerization in an aqueous medium.

The blending amount of the above acrylic polymer emulsion is not particularly limited, but preferably 2 to 6 in terms of solid content in terms of film forming ability and usability during coating.
It is 0%, more preferably 5 to 40%. This acrylic polymer emulsion may contain one or two
More than one species can be used.

In addition to the above-mentioned essential components, the nail enamel of the present invention may be blended with pigments, dyes or other powders for cosmetics. These powders may be used as they are, but of course, if necessary, they may be treated with an oil agent, silicone, a fluorine compound, a surfactant or the like and blended.
Further, if necessary, a surfactant for dispersing the pigment, a resin, a film forming aid, a viscosity adjusting agent (gelling agent), a water-soluble polymer, a preservative, an antifoaming agent, a plasticizer, an antioxidant, and a fragrance. , An ultraviolet absorber, a beauty ingredient, purified water and the like can be appropriately mixed.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the water-based nail enamel of the present invention include nail enamel, enamel top coat, enamel base coat and the like.

[0015]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Production Example 1. Treated powder Titanium oxide (Ishihara Sangyo Co., Ltd., trade name CR-50) 1
00 g was dispersed in 40 g of methanol to form a uniform slurry. To this slurry, 10 g of a 10% aqueous solution of a silylating agent having a polyoxyethylene chain represented by the following formula was added,
The treatment was performed with a ball mill for 5 minutes. The treated slurry was dried under reduced pressure and then heat-treated at 100 ° C. for 1 hour. This was washed with ethanol, dried and then pulverized to obtain titanium oxide whose surface was hydrophilized. _{(CH 3 O) 3 SiC 3} H 6 O (C 2 H 4 O) n CH 3 ( wherein, a n = 30 to 34.)

Production Example 2 Treated powder Titanium oxide (Ishihara Sangyo Co., Ltd., trade name CR-50) 1
00 g was dispersed in 40 g of methanol to form a uniform slurry. 50 g of a 30% aqueous solution of the silylating agent having a polyoxyethylene chain used in Production Example 1 was added, and the mixture was treated with a ball mill for 5 minutes. The slurry after the treatment was dried under reduced pressure, and then heat-treated at 100 ° C. for 1 hour. This was washed with ethanol, dried and then pulverized to obtain titanium oxide whose surface was hydrophilized.

Production Example 3 Treated powder Nylon powder (Toray Industries, Inc., trade name Nylon SP-
500) 100 g in a mixer, 3 g of a silylating agent having a polyoxyethylene chain represented by the following formula, and 10 g of purified water
What was melt | dissolved in was mixed for 10 minutes, adding spraying.
This was dried under reduced pressure, then heat-treated at 100 ° C. for 1 hour, washed with ethanol, dried and pulverized to obtain a nylon powder whose surface was hydrophilized. _{(CH 3 O) 3 SiC 3} H 6 O (C 2 H 4 O) r (C 3 H 6 O) t
CH ₃ (In the formula, r / t = 2.5 to 3.5 and r + t = 25 to 35.)

Production Example 4 Treated powder talc (Matsumura Sangyo Co., Ltd., trade name High Filler K-5)
μ) 100 g was dispersed in 40 g of methanol to obtain a uniform slurry. 10 g of a 5% aqueous solution of the silylating agent having a polyoxyethylene chain used in Production Example 1 was added, and the mixture was treated with a ball mill for 5 minutes. The treated slurry was dried under reduced pressure and then heat-treated at 100 ° C. for 1 hour. This was washed with ethanol, dried and then pulverized to obtain talc whose surface was hydrophilized.

Production Example 5 Acrylic polymer emulsion Various monomers, 70 parts by weight of methyl methacrylate (hereinafter simply referred to as "part"), 10 parts of styrene, 16 parts of 2-ethylhexyl methacrylate, 4 parts of acrylic acid in a dropping funnel.
Parts, 35 parts of methyl ethyl ketone (solvent), and 2 parts of dimethyl azobisisobutyrate are added, and this is added dropwise to 50 parts of methyl ethyl ketone heated to 80 ° C. over 2 hours, followed by stirring for 2 hours. In order to complete the polymerization, 2 parts of dimethyl azobisisobutyrate and 10 parts of methyl ethyl ketone are added and the reaction is continued for 3 hours. Then, the mixture was cooled to room temperature, neutralized by adding 5.6 parts of triethylamine, and water was added with stirring to 400
Add parts and mix. This was distilled under reduced pressure to remove methyl ethyl ketone and then concentrated to obtain an acrylic polymer emulsion having a solid content of 40%.

Examples 1 to 3 and Comparative Examples 1 to 5 Water-based nail enamel A water-based nail enamel having the composition shown in Table 1 was prepared, and the makeup lasting (difficulty peeling and difficulty of application) and usability (good elongation) were obtained. ), Gloss, sedimentation and color unevenness were evaluated by the following methods. Table 1 also shows the results.

[0021]

[Table 1]

* 1: 1% silicon treated titanium oxide * 2: 1% fluororesin treated titanium oxide * 3: polyoxyethylene alkyl ether

(Production Method) Examples 1 to 3 and Comparative Examples 1 to 5 A. Components 1 to 11 are mixed and stirred. B. Ingredients 12 to 14 are mixed and stirred, A is uniformly dispersed therein, and finally deaerated and filled in a container to obtain a product.

(Evaluation Method and Criteria) 1. Sensory evaluation Each sample was subjected to a usage test by 20 specialized panels, and the durability of makeup (difficulty to peel off and apply), usability (spreadability), and gloss were evaluated using (1) absolute evaluation criteria in 5 grades. The average value of the scores for each sample was (2)
Evaluation was performed using a four-level evaluation standard. (1) Absolute evaluation criteria 5 points: Very good 4 points: Good 3 points: Normal 2 points: Somewhat poor 1 point: Poor (2) Four-step evaluation criteria A: 4.0 to 5.0 points O: 3. 0 to less than 4.0 points Δ: 2.0 to less than 3.0 points ×: 1.0 to less than 2.0 points

2. Evaluation of sedimentation and color unevenness Each sample was filled in a glassy transparent container and set in a constant temperature bath at 40 ° C. for 2 weeks to confirm the presence or absence of sediment and color unevenness in the appearance. The evaluation was performed according to the following criteria. Judgment criteria ◎: No change. ◯: Slight sedimentation or uneven color is observed. Δ: Sedimentation and color unevenness are observed. X: Severe sedimentation and uneven color are observed.

As is clear from the above results, the water-based nail enamel of Examples 1 to 3 relating to the product of the present invention is caused by the aggregation of the pigment as compared with the water-based nail enamel of Comparative Examples 1 to 5. Settling,
It can be seen that no color unevenness is observed, and that it has far superior properties in all aspects of coating film function such as makeup retention and gloss, and usability. On the other hand, the water-based nail enamel of Comparative Example was not satisfactory in terms of coating function and usability such as cosmetic retention and gloss, as well as the appearance of the pigment was significantly impaired.

Example 4 Water-based base coat (component) (%) 1. Polymer emulsion of Production Example 9 90.0 2. Purified water balance 3. Film forming aid 6.5 4. Suitable amount of plasticizer 5. Preservative proper amount 6. Defoamer proper amount 7. Appropriate amount of flavor 8. Treated powder of Production Example 4 3.0 (Production method) Components 1 to 8 are mixed and stirred, deaerated, and filled in a container to obtain a product.

The water-based base coat of the present invention was excellent in usability, no aggregation or settling of powder with time was observed, and was excellent in adhesion, which is a function as a base coat.

Example 5 Matte type water-based nail enamel (component) (%) 1. Polymer Emulsion of Production Example 15.0 2. Resin A * 4 15.0 3. Purified water Remaining amount 4. Film forming aid 4.5 5. Suitable amount of plasticizer 6. Preservative proper amount 7. Defoamer proper amount 8. Perfume proper amount 9. Benton 0.5 10. Treated powder of Production Example 3 5.0 11. Red 226 0.4 12. Treated powder of Production Example 1.5 * 4: Jonson Polymer 68 Co., Ltd. Jonkuryl 68: Styrene-acrylic copolymer (manufacturing method) A. Ingredients 3, 9-12 are mixed and stirred. B. Ingredients 1, 2, 4 to 8 are mixed and stirred, and A is uniformly dispersed therein, deaerated, and filled in a container to obtain a product.

The matt type water-based nail enamel of the present invention has excellent usability, no aggregation or settling of powder with time is observed, and excellent adhesiveness which is a function of the nail enamel. .

Example 6 Water-based nail enamel (ingredient) (%) 1. Polymer emulsion of Production Example 5 70.0 2. Purified water balance 3. Film forming aid 4.5 4. Suitable amount of plasticizer 5. Preservative proper amount 6. Defoamer proper amount 7. Appropriate amount of flavor 8. Benton 0.5 9. Red 226 0.4 10. Processed Powder of Production Example 1 0.1 (Production Method) A. Components 2, 9, 10 are mixed and stirred. B. Ingredients 1, 3 to 8 are mixed and stirred, A is uniformly dispersed therein, deaerated, and filled in a container to obtain a product.

The water-based nail enamel of the present invention was excellent in usability, no aggregation or settling of powder with time was observed, and was excellent in adhesiveness, which is a function as a nail enamel.

[0033]

EFFECTS OF THE INVENTION The water-based nail enamel of the present invention is excellent in coating film performance such as makeup retention and gloss, and no sedimentation or color unevenness caused by pigment aggregation is observed. It was stable even at low viscosities that were not obtained, and greatly improved usability.

Claims (6)

[Claims] 1. A water-based nail enamel wherein a powder hydrophilized with a silylating agent having a polyoxyethylene chain and an acrylic polymer emulsion are blended. 2. The water-based nail enamel according to claim 1, wherein the silylating agent having a polyoxyethylene chain is a silylating agent represented by the following general formula (1). _{^{(R 1 O) a R 2}} b SiR 3 O (C 2 H 4 O) p (C 3 H 6 O) q R 4 ... (1) ( wherein, R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ² is an alkyl group having 1 to 10 carbon atoms or a phenyl group, R ³ is a divalent hydrocarbon group having 2 to 5 carbon atoms, and R ⁴ is hydrogen or 1 to carbon atoms.
An alkyl group of 10, a is an integer of 1 to 3, b is an integer of 0 to 2, and a + b is 3. p is an integer of 2 to 200,
q is an integer of 0 to 200, and p + q is an integer of 3 to 200. Moreover, p / q is 1 or more. ) 3. The water-based nail enamel according to claim 1 or 2, wherein the amount of the acrylic polymer emulsion is 2 to 60% by weight in terms of solid content. 4. The water-based nail enamel according to claim 1, 2 or 3, wherein the treatment amount of the silylating agent having a polyoxyethylene chain is 0.01 to 20% by weight based on the powder to be treated. . 5. A blending amount of the powder hydrophilized with a silylating agent having a polyoxyethylene chain is 0.01 to 20% by weight.
The water-based nail enamel according to claim 1, 2, 3, or 4. 6. A powder which has been hydrophilized with a silylating agent having a polyoxyethylene chain is an inorganic powder.
The water-based nail enamel according to claim 3, 4, or 5.