JPH0780745B2 - Nail enamel - Google Patents

Description

FIELD OF THE INVENTION This invention relates to nail enamel.

BACKGROUND ART Nail enamel is an enamel for giving gloss and color to nails.In a broad sense, in addition to the above, a base coat or nail enamel for improving the adhesion of nail enamel has a long gloss or color. An overcoat to improve is included. In the present invention, nail enamel is used in a broad sense.

The problems with nail enamel include not only basic performances such as improvement of gloss and color, durability, water resistance, and adhesion, but also ease of application, drying property, and hobby.

JP-A-57-56410 discloses a solution to the above problems.
Resin emulsion with an average particle size of 0.05 μm or less and an average particle size of 0.
Disclosed is a nail enamel using a resin emulsion of 1 μm or more in a specific distribution ratio. In this technique, the resin is used in an emulsion and solid particles are not used in a dispersed state. The resin emulsion is a film-forming component and should be called a technique for improving the film-forming component.

Japanese Unexamined Patent Publication (Kokai) No. 60-16910 discloses a technique in which silica powder having an average particle diameter of 0.01 to 30 μm is blended to obtain a nail enamel having a matte matte finish. This technique does not use resin fine particles, but relatively large particles are used. Inorganic fine powder cannot provide dryness, transparency and matte feeling when using fine resin particles.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention In addition to the above-mentioned basic performance required for nail enamel, the present invention provides a nail enamel with improved dryness without deteriorating the feeling of use, and a transparent feeling. The purpose is to provide a technique capable of delicately controlling the matte feeling.

Means for Solving the Problems The present invention relates to a nail enamel containing non-film-forming resin fine particles having an average particle diameter of 0.01 to 0.1 μm and a film-forming resin component.

By dispersing the non-film-forming resin fine particles in the nail enamel, it is possible to increase the non-volatile content while maintaining the ease of coating and thus accelerate the drying, and to obtain transparent fine particles having various refractive indices. Therefore, by adjusting the refractive index with the film-forming component, it is possible to delicately control the transparent feeling and the matte feeling.

The non-film-forming resin fine particles used in the present invention have an average particle diameter of 0.01 to 0.
The thickness is preferably 1 μm, more preferably 0.03 to 0.08 μm. This particle size is measured by an electron microscope, and if it exceeds 0.1 μm, it is particularly preferable that it is 10% or less in all particles.

If the average particle size is smaller than 0.01 μm, the viscosity of the nail enamel when used in the required amount will remarkably increase and the usability will decrease. On the other hand, if it exceeds 0.1 μm, durability, water resistance, adhesion, etc. are deteriorated, and desired gloss and matte finish cannot be obtained.

In solvent-based nail enamel, non-film-forming fine particles are usually crosslinked with a crosslinking agent so as not to be dissolved or swelled by the solvent (eg, various alcohols, ester solvents, aromatic solvents) in the nail enamel or polymerization solvent. The resins mentioned above are preferred. Further, in the water-based nail enamel, the non-film-forming fine particles do not necessarily have to be crosslinked, but have a high glass transition temperature so as not to cause fusion before use due to heat,
For example, it is preferably 70 ° C. or higher.

The monomer for synthesizing the non-film-forming fine particles that can be used in the present invention is not limited, but I) a carboxyl group-containing monomer such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid. II) Hydroxyl group-containing monomer such as 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, allyl alcohol, methallyl alcohol, etc .; III) Nitrogen-containing alkyl acrylates or methacrylates, such as dimethylamino acrylate, dimethylaminoethyl methacrylate, etc .; IV) Polymerizable amides, such as acrylamide, methacrylamide, etc .; Nitriles such as acrylonitrile and methacrylonitrile; VI) alkyl acrylates or methacrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate; VII) polymerizable aromatics Compounds such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene and the like; VIII) α-olefins such as ethylene, propylene and the like; IX) vinyl compounds such as vinyl acetate, vinyl propionate and the like; X) diene compounds, For example, butadiene, isoprene, etc .; XI) Ionic group-containing monomers such as sodium styrenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid, (3-sulfopropyl) Examples thereof include potassium methacrylate, N- (3-sulfopropyl) -N-methacryloxyethyl-N, N-dimethylammonium betaine and the like.

The above monomers may be used in combination with the crosslinkable monomer. The cross-linking agent is appropriately used so that the cross-linking monomer in 1 g of the polymer will be 10 ^{−6 to} 5 × 10 ⁻³ mol.

As the crosslinkable monomer, ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,
4-butanediol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol diacrylate,
Pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol dimethacrylate, glycerol diacrylate, glycerol acryloxy dimethacrylate, 1,1,1- Trishydroxymethylethane diacrylate, 1,1,1-trishydroxymethylethane triacrylate, 1,1,1-trishydroxymethylethane dimethacrylate, 1,1,1
-Trishydroxymethylethanetrimethacrylate,
1,1,1-Trishydroxymethylpropane diacrylate, 1,1,1-Trishydroxymethylpropane triacrylate, 1,1,1-Trishydroxymethylpropane dimethacrylate, 1,1,1-Trishydroxymethylpropane triacrylate Examples thereof include methacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate and divinylbenzene.

A specific resin particularly preferable as the non-film-forming resin fine particles can be obtained by polymerizing monomers such as methyl methacrylate, styrene, ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and divinylbenzene.

The non-film-forming resin fine particles can be produced, for example, by emulsion polymerization. In emulsion polymerization, a monomer may be polymerized using a water-soluble initiator in the presence of an emulsifier.

The emulsifying agent for emulsion polymerization is not limited to the emulsifying agent, but includes the followings.

(1) Anionic emulsifier For example, sodium alkylsulfate, sodium dialkylsulfosuccinate, sodium alkylbenzenesulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate (2) Cationic emulsifier For example, lauryl trimethyl ammonium chloride ( 3) Nonionic emulsifiers such as polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene resin acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene-polyoxypropylene block copolymer (4) Zwitterionic emulsifier (5) Oligomer, polymer emulsifier Reester resin, epoxy resin, acrylic resin As an initiator, it is obtained by combining an organic azo compound, persulfate hydrogen peroxide and an inorganic water-soluble initiator with a reducing agent such as bisulfite, ferrous salt and ascorbic acid. Redox type initiators may be mentioned.

Since the obtained polymer is obtained as fine particles, it may be blended in the nail enamel as it is, or may be obtained as agglomerated particles by removing the solvent by an appropriate method. As a method for removing the solvent, a heating method, a vacuum distillation method, a spray drying method, a freeze drying method, a salting out method or the like may be appropriately used.

The obtained agglomerated particles may be directly mixed with the components for nail enamel and kneaded under a strong shearing force to disintegrate, or may be pulverized in advance. Alternatively, the powder may be once pulverized and then redispersed in a non-aqueous solvent for use.

The film-forming resin component that can be used in the present invention is a film-forming component that has been commonly used in nail enamel, such as polyvinyl acetate, nitrocellulose, alkyd resin, acrylic resin, amino resin, etc., alone or in combination.

These film-forming resin components may be used as an aqueous emulsion or may be used in a state of being dissolved in an organic solvent.

Non-film-forming resin particles have a solid content of 0.
The amount is 1 to 10% by weight, preferably 0.5 to 5% by weight. 0.1
If it is less than 10% by weight, the effect is small, and if it is more than 10% by weight, the film becomes brittle.

The nail enamel of the present invention may be prepared as an aqueous emulsion-dispersion type or as an organic solvent type.

As the organic solvent, ethyl acetate generally used for nail enamel, ester solvents such as butyl acetate, ethanol, alcohol solvents such as isopropyl alcohol,
Examples thereof include ketone solvents such as acetone and methyl ethyl ketone, alkylene glycol alkyl ether solvents such as ethyl cellosolve, aromatic solvents such as toluene, and hydrocarbon solvents such as hexane and cyclohexane.

In the nail enamel of the present invention, other components generally added to the nail enamel, for example, a colorant, a gloss imparting agent, a viscosity modifier, a plasticizer, an antifoaming agent, a preservative, an emulsion dispersion stabilizer, a perfume, an antifreezing agent. , A moisturizing agent, an antioxidant, an ultraviolet absorber and the like may be appropriately mixed.

Hereinafter, the present invention will be described with reference to Reference Examples and Examples.
In the reference examples and examples, all "parts" indicate parts by weight.

Reference Example 1 (Production of Non-Film Forming Resin Fine Particles I) In 2 Kolben equipped with a stirrer, nitrogen introducing tube, temperature control device, condenser, decanter, bishydroxyethyl taurine 134 parts, neopentyl glycol 130 parts, azelaic acid 236 parts, 186 parts of phthalic anhydride and 27 parts of xylene were charged and the temperature was raised. Water generated by the reaction was removed by azeotropic reflux with xylene. The temperature was raised to 190 ° C. over about 2 hours from the start of refluxing, stirring and dehydration were continued until the acid value corresponding to the carboxylic acid became 145, and the temperature was cooled to 140 ° C.

Next, the temperature of the reaction solution was maintained at 140 ° C., and “CARDURA E1
314 parts of "0" (versic acid glycidyl ester manufactured by Shell Co.) was added dropwise over 30 minutes, and then the reaction was terminated by continuing stirring for 2 hours. The resulting polyester resin has an acid value of 5
9, the hydroxyl value was 90, M1054.

Then, equipped with a stirrer, a cooler and a temperature controller 1
In a reaction vessel, 372 parts of deionized water, 30 parts of the polyester resin obtained above and 2.8 parts of dimethylethanolamine were charged and dissolved while maintaining the temperature at 80 ° C under stirring, and 4.5 parts of azobiscyanovaleric acid was deionized. A solution of 45 parts of water and 4.3 parts of dimethylethanolamine was added.

Then, a mixed solution of 160 parts of methyl methacrylate and 40 parts of ethylene glycol dimethacrylate was added dropwise over 60 minutes. After dropping, further azobis cyanovaleric acid
1.5 parts of deionized water 15 parts and dimethylethanolamine 1.4
When dissolved in 1 part, the mixture was stirred at 80 ° C. for 60 minutes, and a resin fine particle dispersion having a nonvolatile content of 35% and a particle diameter of 0.065 μm was obtained.

Reference Example 4 The aqueous dispersion of the resin fine particles I obtained in Reference Example 1 was dried with a spray dryer, and 20 parts of the obtained aggregated particles were mixed with 22 parts of ethyl acetate, 16 parts of butyl acetate, 6 parts of ethanol and 36 parts of toluene. The resulting mixture was placed in a solvent and the mixture was vigorously stirred with a homomixer to obtain a solvent dispersion of resin fine particles. The average particle size of the resin particles in the dispersion was 0.066 μm with an electron microscope.

Reference Example 2 (Production of non-film-forming resin fine particles II) Water dispersion of non-film-forming resin fine particles II having an average particle diameter of 0.062 μm was carried out in the same manner as in Reference Example 1 except that 160 parts of styrene was used instead of methyl methacrylate. A liquid was obtained.

Reference Example 5 A solvent dispersion was obtained from the aqueous dispersion of resin fine particles II obtained in Reference Example 2 in the same manner as in Reference Example 4. Average particle size is 0.063
was μm.

Reference Example 3 (Production of non-film-forming resin particles III) As in Reference Example 1, except that 10 parts of polyester resin, 0.8 part of dimethylethanolamine used for neutralizing the polyester resin and 182 parts of methyl methacrylate were used. Non-film-forming resin fine particles III having an average particle diameter of 0.190 μm were obtained.

Reference Example 6 A solvent dispersion was obtained in the same manner as in Reference Example 4 from the aqueous dispersion of the resin fine particles III obtained in Reference Example 3. Average particle size is 0.198
was μm.

Examples 1-2 and Comparative Example 1 Aqueous nail enamel was obtained according to the formulation shown in Table-1.

The components are mixed by stirring at room temperature. The obtained aqueous nail enamel was evaluated by the following methods.

Feel of use: Sensory evaluation was performed.

○: Easy to wet △: Normal ×: Difficult to wet Dryability: Coat the glass plate with a doctor blade (film thickness: 0.
25 mm) Drying time was evaluated.

◯: Good (within 3 minutes) Δ: Normal (within 6 minutes) X: Poor (6 minutes or more) Mochi: Based on sensory evaluation during use

◯: Good Δ: Normal ×: Poor Finish: Visual evaluation of appearance Ease of removal with a remover: Sensory evaluation during use.

○: Easy to remove △: Normal ×: Difficult to remove Remover component Example 3 and Comparative Examples 2 and 3 Solvent-type nail enamel was obtained with the following formulation.

Evaluation was carried out in the same manner as in Example 1, and the results shown in Table 2 were obtained.

EFFECTS OF THE INVENTION When the non-film-forming resin fine particles of the present invention are blended with a nail enamel, the gloss and color basically required for the nail enamel are improved, durability, water resistance, adhesiveness, and easy coating are maintained. However, the drying property can be improved. Further, since transparent resin particles can be obtained, it is possible to control delicate hue and luster from the difference between the refractive index and the refractive index of the film-forming resin.

Claims (5)

[Claims] 1. A nail enamel containing non-film-forming resin fine particles and a film-forming resin component, wherein the non-film-forming resin fine particles are made of a cross-linked resin having a glass transition temperature of 70 ° C. or more and an average particle diameter of 0.01. Nail enamel with particles of ~ 0.1 μm. 2. A non-film-forming resin obtained by copolymerizing a crosslinkable monomer having two or more ethylenically unsaturated bonds in a molecule with a monomer having one ethylenically unsaturated bond. The listed nail enamel. 3. The nail enamel according to claim 1, wherein the film-forming resin component is selected from polyvinyl acetate, nitrocellulose, alkyd resin, acrylic resin and amino resin. 4. The nail enamel according to claim 1, which contains non-film-forming resin fine particles in a solid content of 0.1 to 10% by weight. 5. The nail enamel according to claim 1, which contains a film-forming component in a solid content of 5 to 50% by weight.