JP3009276B2 - Water based nail polish - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nail polish, and more particularly, to an aqueous nail polish different from a conventional nail polish using an organic solvent. The nail enamel in the present invention includes nail enamel, nail enamel base coat, nail enamel overcoat, and the like.

[0002]

2. Description of the Related Art Conventional nail polishes are mainly composed of resins such as nitrocellulose and alkyd resins as film-forming agents, and furthermore, plasticizers and organic solvents as main bases. However, although these organic solvent-based nail polishes are excellent in various properties as a film-forming agent, the use of organic solvents inflammability, solvent odor, and effects on the human body, particularly on the nail itself, etc. It has significant drawbacks.

[0003] In order to solve these drawbacks, aqueous nail polish which does not use an organic solvent has been proposed. For example, JP-A-54-28836 and JP-A-54-52736 disclose beauty nail preparations composed of an acrylic polymer emulsion. They are inferior in brush handling properties, film forming properties (particularly low-temperature film forming properties), and gloss of coating films.

Japanese Patent Application Laid-Open Nos. 56-131513 and 57-56410 disclose nail polish comprising an acrylic polymer microemulsion, and are obtained from these nail polish. The coating has the disadvantage that it is quite brittle against mechanical friction.

Further, Japanese Unexamined Patent Publication No. 56-131513 and Japanese Unexamined Patent Publication No. 62-63507 disclose a water-based nail polish of a peeling type, but have a drawback that they are easily peeled off in daily use. Yes, not practical.

[0006]

SUMMARY OF THE INVENTION In view of the above circumstances, the present inventors have developed a water-based beauty having advantages such as excellent luster, adhesion, water resistance, and coating strength, as well as flammability and no solvent odor. As a result of intensive studies to obtain nail varnish, we found that a polymer emulsion obtained by copolymerizing a silicone macromonomer with another monomer is particularly excellent in water resistance and is extremely effective as a film-forming component of an aqueous nail varnish. This has led to the present invention.

That is, the present invention provides a polymer emulsion obtained by copolymerizing a silicone macromonomer and a monomer having a polymerizable double bond as a solid content of 5 to 5%.
The present invention provides a water-based beautiful nail material characterized by containing 60% by weight.

The silicone macromonomer used for producing the polymer emulsion of the present invention has a siloxane bond in the molecular chain and a polymerizable unsaturated bond at the terminal of the molecular chain.
Those having a weight average molecular weight of about 00 are preferably used. Typical examples include those represented by the following general formula.

[0009]

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In the above formulas, R is hydrogen or a methyl group, and X is the following formula:

Embedded image Is a group represented by In each of the above formulas, the methyl group bonded to the Si atom may be an ethyl group, a phenyl group, or the like, or may be a methoxy group, an ethoxy group, or the like, and is not particularly limited to the above. .

On the other hand, monomers having a double bond capable of polymerizing with a silicone macromonomer (hereinafter, this monomer may be referred to as “addition type monomer”) include acrylic acid, methacrylic acid, and maleic acid. Unsaturated carboxylic acid monomers such as acids or anhydrides or salts thereof; methyl acrylate, ethyl acrylate, n-butyl acrylate,
(Meth) acrylic acid alkyl esters such as lauryl acrylate, methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate; unsaturated sulfonic acid monomers such as styrene sulfonic acid and 2-acrylamido-2-methylpropane sulfonic acid; Salts thereof; unsaturated phosphoric acid monomers such as vinylphosphonic acid and acid phosphoxyethyl (meth) acrylate; dialkylamino groups such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropylacrylamide (Meth) acrylic acid esters or (meth) acrylamides having a dialkylamino group such as N, N-dimethylaminostyrene or N, N-dimethylaminomethylstyrene; 4-vinylpyridine, 2-vinylpyridine Vinyl pi Lysines; or those quaternized with a known quaternizing agent such as alkyl halide, benzyl halide, alkyl or aryl sulfonic acid, or dialkyl sulfate; N- (3-sulfopropyl)-
N-methacryloyloxyethyl-N, N-dimethylammonium betaine; N-carboxymethyl-N-methacryloyloxyethyl-N, N-dimethylammonium betaine;

The polymer emulsion of the present invention is prepared by appropriately combining at least one or more of the above-mentioned silicone macromonomers and at least one or more addition-type monomers, and combining these with a known method, for example, using a known radical initiator and adding a reactive emulsifier. It can be obtained as an emulsifier-free polymer emulsion by the soap-free polymerization used or the aqueous medium heterogeneous polymerization containing no emulsifier.

In producing the polymer emulsion of the present invention, 0.5 to 15% by weight of the silicone macromonomer (hereinafter simply referred to as "%") and 8% of the addition type monomer are used.
Preferably, it is used at a rate of about 5 to 99.5%.

Among the polymer emulsions of the present invention, particularly preferred are those having a volatility that allows 1 to 8% of a silicone macromonomer and 92 to 99% of an addition type monomer to be miscible with water such as methyl ethyl ketone and lower alcohol. A polymer emulsion obtained by copolymerizing in an organic solvent, adding water to an organic solvent solution of the obtained copolymer, and distilling off the organic solvent can be exemplified. In the organic solvent, in order to copolymerize the silicone macromonomer and the addition type monomer, a known radical initiator is used, and a copolymerization is performed by a known polymerization method such as a solution polymerization method, a bulk polymerization method, and a precipitation polymerization method. Just do it.

The nail polish of the present invention is prepared by blending the polymer emulsion obtained as described above as a film-forming base. The blending amount of the polymer emulsion in the aqueous nail polishes of the present invention is 5 to 60% (as solid content). If the blending amount is less than 5%, several coats may be required to obtain a practically necessary coating film, and if the blending amount exceeds 60%,
In some cases, the viscosity of the nail polish is increased, and a decrease in applicability such as brush handling properties may be observed.

[0016] In addition to the polymer emulsion as an essential component, pigments, dyes,
Preservatives, fragrances, plasticizers, film-forming auxiliaries, thickeners, wetting agents, defoamers, fillers and the like can be added.

As the pigments, in particular, R-221 and R-22
6, B-404, Y-401, and other known organic pigments. In addition to such organic colorants, titanium dioxide,
Inorganic substances such as brown iron oxide, red iron oxide, mica titanium bismuth oxychloride can also be used.

Known plasticizers and film-forming assistants such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, butyl carbitol, cellosolve acetate, butyl cellosolve acetate, butyl carbitol acetate and hexylene glycol are used. However, the amount is preferably about 0 to 15% from the viewpoint of storage stability of the polymer emulsion and water resistance of the coating film.

Known thickeners can be used, and organic thickeners such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyethylene oxide, methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, cationized guar gum, and cationized cellulose can be used. A thickener or an inorganic bentonite thickener can be used.

[0020]

When the polymer emulsion used in the present invention is used as a film-forming component of an aqueous nail polish, it can give a film having particularly excellent water resistance. Therefore, the nail polishes of the present invention using this polymer emulsion are excellent in gloss, adhesion, water resistance, coating strength, etc., and have excellent properties such as flammability and no solvent odor. ,
It can be used as a new water-based beautiful nail material that replaces the conventional organic solvent-based beautiful nail material.

[0021]

Next, the present invention will be described in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited to these Examples and the like.

Synthesis Example 1 50 parts of methyl ethyl ketone was charged into a reactor equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet tube.
Dissolved oxygen was removed by flowing nitrogen gas. On the other hand, 35 parts of methyl ethyl ketone, 4 parts of a silicone macromonomer represented by the following formula, and 5 parts of methyl methacrylate were added to the dropping funnel.
6 parts, n-butyl acrylate 36 parts, acrylic acid 4 parts and azobisisobutyronitrile 0.2 part were charged.

Under stirring, the temperature in the reactor was raised to 80 ° C., and a solution of the above monomer and radical initiator in methyl ethyl ketone was dropped from the dropping funnel over 2.5 hours. Two hours after the completion of the dropping of the monomer, azobisisobutyronitrile
A solution of 0.2 part dissolved in 10 parts methyl ethyl ketone was added. After aging at the same temperature for 3 hours, a solution obtained by dissolving 0.1 part of azobisisobutyronitrile in 5 parts of methyl ethyl ketone was added again, and the reaction was further continued for 5 hours to obtain a copolymer.

The silicone macromonomer used:

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A part of the obtained copolymer was isolated and its molecular weight was measured by gel permeation chromatography. As a result, the weight average molecular weight was 75,000. The calibration curve of gel permeation chromatography was prepared using polystyrene as a standard substance (solvent: tetrahydrofuran). After completion of the reaction, the copolymer solution was cooled to room temperature, neutralized by adding 5.6 parts of triethylamine, and further stirred at 300 rpm with 400 parts of ion-exchanged water.
Then, methyl ethyl ketone was distilled off at 40 ° C. under reduced pressure, and water was further distilled off at 50 ° C. to obtain a polymer emulsion having a solid content of 30%.

Example 1 (Composition) Polymer emulsion (obtained in Synthesis Example 1) 100 parts Pigment (red pigment R-226) 3 parts Deionized water 10 parts Hexylene glycol 8 parts Diethyl phthalate 2 parts Bentonite 0.5 part Fragrance 0.1 part Preservative 0.1 part Silicone defoamer 0.1 part

(Preparation method) Hexylene glycol and diethyl phthalate were added to ion-exchanged water, and after the pigment was dispersed therein, a polymer emulsion and other components were added. The mixture was uniformly stirred and mixed. Care was taken to produce an aqueous nail enamel.

Synthesis Example 2 In the same manner as in Synthesis Example 1, 4 parts of a silicone macromonomer represented by the following formula, 52 parts of methyl methacrylate, 40 parts of ethyl acrylate, 4 parts of acrylic acid, and 0.1 part of azobisisobutyronitrile were prepared. Two parts were polymerized in methyl ethyl ketone to obtain a copolymer.

The silicone macromonomer used:

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The weight average molecular weight of this copolymer is 80,0
00. Next, 5.6 parts of triethylamine was added to the copolymer to neutralize it, and the phase was inverted to water in the same manner as in Synthesis Example 1 to obtain a polymer emulsion having a solid content of 30%.

Example 2 (Composition) Polymer emulsion (obtained in Synthesis Example 2) 100 parts Pigment (red pigment R-226) 3 parts Deionized water 10 parts Hexylene glycol 10 parts Diethyl phthalate 3 parts Bentonite 0.5 part Fragrance 0.1 part Preservative 0.1 part Silicone defoamer 0.1 part

(Preparation method) Hexylene glycol and diethyl phthalate were added to ion-exchanged water, and after the pigment was dispersed therein, a polymer emulsion and other components were added. Care was taken to produce an aqueous nail enamel.

Synthesis Example 3 In the same manner as in Synthesis Example 1, 6 parts of a silicone macromonomer represented by the following formula, 53 parts of methyl methacrylate,
37 parts of butyl acrylate, 4 parts of acrylic acid and 0.2 part of azobisisobutyronitrile were polymerized in methyl ethyl ketone to obtain a copolymer.

The silicone macromonomer used:

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The weight average molecular weight of this copolymer is 78,0
00. Next, 5.6 parts of triethylamine was added to the copolymer for neutralization, and the phase was inverted to water in the same manner as in Synthesis Example 1 to obtain an anionic polymer emulsion having a solid content of 30%.

Example 3 (Composition) Polymer emulsion (obtained in Synthesis example 3) 100 parts Pigment (red pigment R-226) 3 parts Ion exchange water 10 parts Hexylene glycol 10 parts Diethyl phthalate 5 parts Bentonite 0.5 part Fragrance 0.1 part Preservative 0.1 part Silicone defoamer 0.1 part

(Preparation method) Hexylene glycol and diethyl phthalate were added to ion-exchanged water, and after the pigment was dispersed therein, a polymer emulsion and other components were added, and the mixture was uniformly stirred and mixed. Care was taken to produce an aqueous nail enamel.

Synthesis Example 4 In the same manner as in Synthesis Example 1, 4 parts of a silicone macromonomer represented by the following formula, 43 parts of methyl methacrylate, 45 parts of n-butyl acrylate, and 8 parts of N, N-dimethylaminoethyl methacrylate were replaced with methyl ethyl ketone. Polymerization was carried out in the solution to obtain a copolymer. The weight average molecular weight of this copolymer was 82,000.

The silicone macromonomer used:

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Next, 4.5 parts of lactic acid was added to the copolymer to neutralize it, and the phase was converted to water in the same manner as in Synthesis Example 1 to obtain a solid content of 25%.
% Cationic polymer emulsion was obtained.

Example 4 (Composition) Polymer emulsion (obtained in Synthesis Example 4) 100 parts Pigment (red pigment R-226) 3 parts Deionized water 10 parts Hexylene glycol 10 parts Diethyl phthalate 3 parts Cationized guar gum 0.5 part Fragrance 0.1 part Preservative 0.1 part Silicone defoamer 0.1 part

(Preparation method) Hexylene glycol and diethyl phthalate were added to ion-exchanged water, and after the pigment was dispersed therein, a polymer emulsion and other components were added. The mixture was uniformly stirred and mixed. Care was taken to produce an aqueous nail enamel.

Synthesis Example 5 In the same manner as in Synthesis Example 1, 4 parts of a silicone macromonomer represented by the following formula, 40 parts of methyl methacrylate, 48 parts of ethyl acrylate, and 8 parts of N, N-dimethylaminoethyl methacrylate were mixed in methyl ethyl ketone. Polymerization was performed to obtain a copolymer. The weight average molecular weight of this copolymer is 8
It was 000.

[0044]

Next, 4.5 parts of lactic acid was added to the copolymer to neutralize it, and the phase was converted to water in the same manner as in Synthesis Example 1 to obtain a solid matter of 30%.
% Cationic polymer emulsion was obtained.

Example 5 (Composition) Polymer emulsion (obtained in Synthesis Example 5) 100 parts Pigment (red pigment R-226) 3 parts Ion exchange water 10 parts Hexylene glycol 10 parts Diethyl phthalate 5 parts Cationized guar gum 0.5 part Fragrance 0.1 part Preservative 0.1 part Silicone defoamer 0.1 part

(Preparation method) Hexylene glycol and diethyl phthalate were added to ion-exchanged water, and after the pigment was dispersed therein, a polymer emulsion and other components were added, and the mixture was uniformly stirred and mixed. Care was taken to produce an aqueous nail enamel.

Synthesis Example 6 In the same manner as in Synthesis Example 1, 6 parts of a silicone macromonomer represented by the following formula, 40 parts of methyl methacrylate, 46 parts of ethyl acrylate, and 8 parts of N, N-dimethylaminoethyl methacrylate were mixed in methyl ethyl ketone. Polymerization was performed to obtain a copolymer. The weight average molecular weight of this copolymer is 7
It was 8,000.

[0049]

Next, 4.5 parts of lactic acid was added to the copolymer to neutralize it, and the phase was changed to water in the same manner as in Synthesis Example 1 to obtain a solid matter of 31%.
% Cationic polymer emulsion was obtained.

Example 6 (Composition) Polymer emulsion (obtained in Synthesis Example 6) 100 parts Pigment (red pigment R-226) 3 parts Ion exchange water 10 parts Hexylene glycol 10 parts Diethyl phthalate 5 parts Cationized guar gum 0.5 part Fragrance 0.1 part Preservative 0.1 part Silicone defoamer 0.1 part

(Preparation method) Hexylene glycol and diethyl phthalate are added to ion-exchanged water, and after the pigment is dispersed therein, a polymer emulsion and other components are added. Care was taken to produce an aqueous nail enamel.

Comparative Example 1 Commercially available DIANAL LX-125 (anionic acrylic emulsion containing no silicone macromonomer as a constituent unit, instead of the polymer emulsion of the present invention,
A water-based nail enamel was produced with the same formulation as in Example 1 except that 35% solids, manufactured by Mitsubishi Rayon) was used.

Comparative Example 2 Commercially available Primal AC-61 (anionic acrylic emulsion containing no silicone macromonomer as a constituent unit, solid content 46.5%, Rohm and Haas Co., Ltd.) was used in place of the polymer emulsion of the present invention. A water-based nail enamel was produced with the same formulation as in Example 1 except for the use of Nail Enamel.

Test Examples The aqueous nail enamels obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were tested for their dryness, gloss, adhesion, water resistance,
The abrasion resistance and odor were evaluated. Table 1 shows the results.

(Evaluation method) (1) Drying property A sample is applied to a nail with a nail enamel brush under the conditions of a temperature of 25 ° C. and a relative humidity of 60%, and the touch drying time is measured. : Within 3 minutes △: 3 to 6 minutes ×: 6 minutes or more

(2) Hikarizawa At the time of drying evaluation, the gloss of the dried coating film after 30 minutes is visually evaluated.

(3) Adhesiveness At the time of evaluation of dryness, the adhesiveness to nails after 30 minutes was evaluated by scraping the film from the surface with a microspatula.

(4) Water resistance A sample was uniformly applied to a nylon plate having a size of 0.5 × 15 × 40 mm with a nail enamel brush and dried at a temperature of 25 ° C. and a relative humidity of 60% for 1 hour. The film is immersed in water at 35 ° C. for 1 hour, and the presence or absence of deterioration of the coating film (white turbidity, swelling, softening, peeling, etc.) is evaluated.

(5) Abrasion resistance In the evaluation of the drying property, the dried coating film after 30 minutes was coated with a cotton cloth.
Observe the state after rubbing 0 times.

(6) Odor Sensory evaluation of the odor at the mouth of nail enamel bin. still,
The evaluation items (2) to (6) were determined as follows. ◎: extremely good ○: good △: normal ×: poor

(Result)

As is evident from the results, the nail polish of the present invention using the polymer emulsion of the present invention is superior to the comparative product using the conventional polymer emulsion in terms of adhesiveness, water resistance, abrasion resistance and the like. It was excellent.

Continued on the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) A61K ^7/ 04-7/047

Claims (2)

(57) [Claims] 1. A water-based nail comprising a polymer emulsion obtained by copolymerizing a silicone macromonomer and a monomer having a polymerizable double bond and containing 5 to 60% by weight as a solid content. Fees. 2. A polymer emulsion obtained by copolymerizing 0.5 to 15% by weight of a silicone macromonomer and 85 to 99.5% by weight of a monomer having a polymerizable double bond. 2. The water-based beautiful nail material according to claim 1.