JPH0840832A - Production of water-born manicure agent - Google Patents

Abstract

PURPOSE:To provide a production method for a water-born manicure agent which can give a coating layer having excellent color tone and gloss and improved resistance to water. CONSTITUTION:This manicure agent is produced by formulating a water-born pigment dispersion in which the pigments are dispersed in a medium containing, as dispersing agents, a surfactant of 12-20 HLB and/or an addition polymer of ethylenically unsaturated molecules containing alpha,beta-mono-ethylenically unsaturated acid of 100-l,000 acid value to a water-born resin emulsion. The surfactant is an EO adduct to a polyhydric alcohol ester, an EO adduct to a higher alcohol, an ionic surfactant such as sodium oleate, while the alpha,beta-mono-ethylenically unsaturated acid in the addition polymer is (meth)acrylic acid, maleic acid, or fumaric acid. Further, alpha,beta-mono-ethylenically unsaturated molecule is, for example, hydroxyalkyl (meth)acrylate, (meth)acrylamide, alkyl (meth)acrylate, styrene or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a nail varnish, more specifically, it is provided as a substantially aqueous nail varnish, and a resin film after curing is removed by water or a uniform mixture of water and an organic solvent. It relates to a process for the production of possible aqueous nail varnishes.

[0002]

2. Description of the Related Art Manicure agents used to enhance the appearance of nails are generally manufactured by dissolving a nitrocellulose-based lacquer in an organic solvent and further adding pigments or dyes of various tones. Such a nail varnish is used by evaporating the solvent after being applied to the nail, and gives a coating film (resin coating film) having excellent gloss in a short time.
On the other hand, the resin coating formed on the nail can be wiped off using an organic solvent such as toluene.

However, this type of manicure agent essentially contains an organic solvent, and there is a problem that the user sucks the organic solvent which volatilizes during use. Further, the coating film once formed is not easily removed by water,
It was necessary to wipe off with a large amount of organic solvent, which was not preferable for the health of the user. Further, the organic solvent may reduce the physiological functions of the nail and the skin. Therefore, it has been desired to develop an aqueous nail varnish which can remove the coating film after coating and drying with water or an aqueous solvent without using an organic solvent for coating. As such a nail polish,
For example, a manicure agent containing an acrylic resin emulsion described in JP-A-54-28836 and JP-A-60-166.
Manicure agents containing an aqueous polyurethane resin emulsion described in Japanese Patent No. 605 have been proposed.

On the other hand, in manufacturing a nail varnish, the step of adding a pigment to a resin emulsion has a great influence on the color tone and gloss of the coating film formed by the final nail varnish, or the performance such as water resistance. It has been known. In particular, this tendency is remarkable in the production of the aqueous nail varnish. For example, JP-B-55-43445 and JP-B-61-1043 disclose a method in which a pigment is added to an aqueous resin emulsion together with a surfactant and dispersed by a disper. However, there is a problem in that the pigment is not sufficiently dispersed and the gloss cannot be obtained for good color development. The average particle size of the pigment is 0.5 μ
A method has been proposed in which an aqueous pigment dispersion having a size of m or less is used as a colorant (Japanese Patent Laid-Open No. 4-103516). However, this method requires complicated steps for making the pigment fine particles.

In the field of water-based paints such as emulsion paints, a pigment is previously added to water together with a dispersant such as a surfactant and treated by a wet mill such as a sand mill to prepare an aqueous pigment dispersion, A method of adding this to an aqueous resin emulsion is known. However, this method requires the use of a large amount of a surfactant or the like as a dispersant, and thus there is a problem that the dispersant causes a problem of reducing the water resistance of the coating film.
For this reason, in the technical field to which nail polish belongs, it was considered difficult to mix the above-mentioned aqueous pigment dispersion liquid, which is generally used in the field of water-based paint, with a nail polish (JP-A-4-103516). (Upper right column of page 2).

[0006]

An object of the present invention is to prepare a water-based nail varnish by adding a pigment to a water-based resin emulsion, and to provide a water-based nail varnish which gives a coating film having excellent color tone and luster. It is to provide a manufacturing method. Another object of the present invention is to provide a method for producing an aqueous nail varnish by adding a pigment to an aqueous resin emulsion, which is a method for producing an aqueous nail varnish which gives a coating film having excellent water resistance. Still another object of the present invention is to provide a method for producing an aqueous nail varnish having the above characteristics by a simple operation.

[0007]

The present inventors have made diligent efforts to solve the above-mentioned problems, and as a result, used a specific surfactant and / or an addition polymer of a specific ethylenically unsaturated molecule as a dispersant. It has been found that an aqueous nail varnish which gives a coating film having excellent color tone and gloss and improved water resistance can be produced by dispersing the pigment by the above method and adding the obtained aqueous pigment dispersion to the aqueous resin emulsion.
The above knowledge is based on the common knowledge in the art that the water resistance of a coating film of a nail polish agent decreases when an aqueous pigment dispersant containing a surfactant or the like is used as the dispersant (JP-A-4-103516, page 2, upper right column). It was an unexpected finding.
The present invention has been completed based on the above findings.

That is, the present invention provides an aqueous pigment containing a surfactant having an HLB in the range of 12 to 20 and / or an addition polymer of an ethylenically unsaturated molecule containing an α, β-monoethylenically unsaturated acid as a dispersant. Disclosed is a method for producing an aqueous nail varnish, which comprises blending a dispersion with an aqueous resin emulsion. According to a preferred embodiment of the present invention, the method wherein the surfactant is selected from the group consisting of polyhydric alcohol ester EO adducts, higher alcohol EO adducts, and ionic surfactants; the molecular weight of the addition polymer is
The above method in the range of 1,000 to 30,000; the above method using the above surfactant and the above addition polymer as the dispersant;
The above method for use in the ratio of Furthermore, the present invention provides an aqueous nail varnish prepared by the above method.

The aqueous pigment dispersion used in the method for producing a nail varnish according to the present invention comprises an ethylene containing a surfactant having an HLB of 12 to 20 and / or an α, β-monoethylenically unsaturated acid as a dispersant. Containing an addition polymer of a polyunsaturated molecule,
It is characterized in that the pigment is dispersed in an aqueous solvent. As the aqueous solvent, water can be used alone, or a mixture of water and an aqueous organic solvent can be used. As the aqueous organic solvent, an organic solvent that gives a homogeneous mixture with water at an arbitrary ratio or a constant ratio can be used. Examples of such an aqueous organic solvent include volatile alcohols such as ethanol and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, and glycol solvents such as butyl cellosolve and butyl carbitol.

As the pigment, for example, the pigment described in JP-A-4-103516 can be preferably used.
More specifically, Red 201, Red 202, Red 204
No., Red No. 205, Red No. 220, Red No. 226, Red No. 228
No., Red No. 405, Orange No. 203, Orange No. 204, Yellow 205
No., Yellow No. 401, Blue No. 404 and other organic pigments, Red No. 3,
Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow 202
No. 203, yellow No. 203, green No. 3, blue No. 1, zirconium, barium, or lake pigments such as aluminum lake, titanium oxide, zinc oxide, iron oxide, iron titanate, γ
-Inorganic pigments such as iron oxide, yellow iron oxide, loess, black iron oxide, carbon black, mango violet, cobalt violet, chromium oxide, chromium hydroxide, cobalt titanate, ultramarine blue and navy blue can be used.

As the surfactant having an HLB in the range of 12 to 20, any surfactant having an HLB value in the above specific range may be used. For example, sorbitan lauric acid monoester EO 4 Polyhydric alcohol ester EO adducts such as mole adducts and sorbitan oleic acid monoester EO 20 mole adducts, polyethylene glycol (400) polyethylene glycol monoesters such as lauric acid monoester, polyethylene glycol (1000) lauric acid diester Such as polyethylene glycol diester, higher alcohol EO adduct such as lauryl alcohol EO 10 mol adduct or oleyl alcohol EO 20 mol adduct, alkylphenol EO adduct such as nonylphenol EO 10 mol adduct, sodium oleate or potassium oleate Ionic surfactant etc. You can

The above surfactants may be used alone or in combination of two or more. When two or more kinds of surfactants are used in combination, a single HLB value out of the above range may be used, and a mixture of two or more kinds of surfactants may have an HLB value above. When it comes to the range, it is included in the scope of the present invention. If the HLB value is less than the above range, the dispersibility of the pigment is poor and precipitation may occur immediately in the aqueous pigment dispersion. Such precipitation is not preferable because redispersion by stirring becomes difficult. On the other hand, if the HLB value exceeds the above range, the water resistance of the coating film formed from the obtained nail varnish will deteriorate, which is not preferable.

The addition polymer of an ethylenically unsaturated molecule containing an α, β-monoethylenically unsaturated acid used as a dispersant is, for example, a hydrophilic α, β-unsaturated carboxylic acid such as methacrylic acid. An addition polymerization product of one or more α, β-monoethylenically unsaturated acids represented by acids can be used. Further, a copolymer of an ethylenically unsaturated monomer molecule such as an acrylic acid ester or a methacrylic acid ester and the above α, β-monoethylenically unsaturated acid may be used. In such a case, for example, α,
β-monoethylenically unsaturated acid as a monomer 12 to 50
It is preferable that the copolymer is used in an amount of 18% by weight, preferably 18 to 25% by weight, with the balance being an ethylenically unsaturated monomer.

Examples of the α, β-monoethylenically unsaturated acids include methacrylic acid, unsaturated acids such as acrylic acid, maleic acid, fumaric acid, aconitic acid, crotonic acid and itaconic acid, and itaconic acid and maleic acid. , Or half esters such as fumaric acid, for example, monomethyl itaconate, monobutyl itaconate, monomethyl fumarate, monobutyl maleate and the like can be used. As the ethylenically unsaturated molecule, either a hydrophilic ethylenically unsaturated molecule or a hydrophobic ethylenically unsaturated molecule may be used. As the hydrophilic ethylenically unsaturated molecule, for example, 2-
Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate,
Hydroxyalkyl esters of acrylic acid and methacrylic acid such as 2-hydroxypropyl acrylate; amides such as acrylamide, mecrylamide, n-methylacrylamide, n-methylolmethacrylamide, β-
Examples thereof include amines such as aminoethyl vinyl ether, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and dimethylaminoethyl vinyl ether.

As the hydrophobic ethylenically unsaturated molecule, for example, esters of acrylic acid and methacrylic acid such as methyl methacrylate, ethyl methacrylate, methyl acrylate and ethyl acrylate, and styrene can be used. The method for producing such an addition polymer may be a method well known to those skilled in the art. The method of the present invention includes, for example, an acid value of about 100 to 1,000 and a molecular weight of 1,000 to 30,00.
Those having a value of about 0 can be preferably used. When two or more addition polymers are used in combination, the average acid value and the average molecular weight of the polymer mixture may be within the above ranges. In addition, as a preferred embodiment of the present invention, there can be mentioned a case where the above addition polymer and the above surfactant are used in combination.

In the method of the present invention, an aqueous pigment dispersion is prepared by dispersing the above pigment in an aqueous solvent in the presence of the above dispersant, and the aqueous pigment dispersion is added to and mixed with an aqueous resin emulsion to give a nail polish. The feature is that the agent is manufactured. The concentration of the pigment in the aqueous pigment dispersion is 0.2 to 70% by weight,
The amount is preferably about 10 to 40% by weight, and such an aqueous pigment dispersion is used in an amount of about 10% by weight based on the aqueous resin emulsion.
A manicure agent can be manufactured by adding it so as to be about 0.1% by weight. To produce an aqueous pigment dispersion,
The pigment may be added to the aqueous solvent together with the above dispersant, and the pigment may be dispersed using a known device such as a sand mill or a homomixer. The dispersant may be used in an amount of 0.5 to 50% by weight, preferably 5 to 20% by weight, based on the pigment (dry weight). The aqueous pigment dispersion thus produced has an average particle size of about 5 μm or less, preferably 3 μm.
The following pigments are uniformly dispersed and have excellent storage stability.

The aqueous resin emulsion used in the method for producing a nail varnish according to the present invention is not particularly limited, and any one having a preferable property as a nail varnish may be used. As an example of such an aqueous resin emulsion, α, β-ethylenically unsaturated carboxylic acid,
One or more monomers selected from the group consisting of methacrylic acid esters, acrylic acid esters, and styrene;
An aqueous resin emulsion obtained by polymerizing with a reactive surfactant can be mentioned. The molecular weight of the resin contained in these emulsions is, for example, about 50,000 or more, preferably about 100,000 or more, for example, in the range of 200,000 to 1,000,000, preferably in the range of 500,000 to 800,000. Such emulsions can generally be prepared as emulsions containing 30 to 50% solids by weight.

As the α, β-ethylenically unsaturated carboxylic acid which can be used for producing the above resin, for example,
Methacrylic acid, acrylic acid, itaconic acid, and maleic acid may be mentioned. As the methacrylic acid ester, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate,
Mention may be made of heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, hexadecyl methacrylate, tertiary butyl methacrylate and 2-ethylhexyl methacrylate.

Examples of acrylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate,
Octyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, hexadecyl acrylate, tertiary butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate,
β-hydroxyethyl acrylate, diethylene glycol acrylate, polyethylene glycol acrylate, β-hydroxypropyl acrylate, glycidyl acrylate, ethylene glycol acrylate, diethylene glycol acrylate, triethylene glycol acrylate, diethylaminoethyl acrylate,
7-amino-3,7-dimethyloctyl acrylate, 2-cyanoethyl acrylate, and β-ethoxyethyl acrylate can be used.

As the acrylic ester, aryl acrylate, alkoxycarbonyl acrylate,
Benzyl acrylate, 3-acryloxy-2-hydroxypropyltrimethylammonium chloride, sulfoacrylate, pentachlorophenyl acrylate, 2-chloroethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, fluoroalkyl acrylate, benzoyloxyalkyl acrylate, tetrahydrofur Furyl acrylate, trimethylolpropane triacrylate, pentaerythritol acrylate, 1 ・
4-Butanediol diacrylate, 1,6-hexanediol diacrylate, and sulfopropyl acrylate can also be used. However, the monomer used is not limited to the above-mentioned monomers, and any α, β-ethylenically unsaturated carboxylic acid monomer, methacrylic acid ester monomer, or acrylic acid ester monomer well known to those skilled in the art can be used. Can be used. You may use 1 type (s) or 2 or more types of these monomers.

As the reactive surfactant, it is possible to polymerize with at least one of the above-mentioned monomers, and it has a surface-active ability by itself, or imparts a surface-active ability to the resin obtained by the polymerization. If it has a property,
Any may be used. For example, alkylphenoxy polyethylene glycol acrylate, acidic phosphoric acid methacrylic acid ester, alkylarylphenoxy polyethylene glycol, sodium-ω-cryloyloxyalkyl (trialkyl) ammonium-paratoluene sulfonate, sodium-polystyrene phenyl ether sulfate, dimethylaminoethyl. Quaternary methacrylate, sodium-sulfosuccinic acid alkylalkenyl ester, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether sulfonate, alkylphenoxyethoxyethyl sulfonate,
Examples thereof include sodium-dialkyl sulfosuccinate and alkyl diphenyl ether disulfonate. Reactive surfactants are generally used in a proportion of 1 to 30% by weight, based on the total weight of the abovementioned monomers.

The resin obtained by the polymerization of these monomers and the reactive surfactant is self-emulsifying, and is characterized in that it gives a stable aqueous resin emulsion without using an emulsifier. However, emulsion polymerization is performed using an emulsifier of 2% by weight or less, preferably 1% by weight or less, based on the total weight of the resin, for the purpose of making the oil droplets finer and improving the mechanical stability of the emulsion. May be. As the emulsifier, sodium alkyl sulfate, ammonium alkyl sulfate, sodium alkyl sulfate ester, sodium alkylbenzene sulfonate, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether and the like can be used.

Among the above resins, resins having an acid group such as carboxylic acid and sulfonic acid and having a neutralization value in the range of 10 to 100 can be preferably used. If the neutralization value of the resin exceeds 100, the water resistance of the resin film after curing may deteriorate, while if the neutralization value of the resin is less than 10, coarse particles increase or product stability is impaired. I have something to do. Generally, the pH of the aqueous resin emulsion obtained by emulsion-polymerizing the above-mentioned monomer and reactive surfactant is in the range of 7 to 10, but in the emulsion produced by emulsion polymerization, all or part of the acid groups are It may exist in a dissociated state. In the present specification, the neutralization value means a hydroxylation necessary for neutralizing a free acid contained in 1 g of a resin for a resin having a carboxylic acid as an acid group and a resin having an acid group other than the carboxylic acid. The number of milligrams of potassium. Two or more kinds of the above resins may be mixed and used, and in that case, the neutralization value of the resin mixture may be within the above range.

As an example of the method for producing the above-mentioned aqueous resin emulsion, for example, a reaction vessel to which an emulsifier such as sodium α-olefinsulfonate is dissolved in water is added and heated, and then the above-mentioned reactive surfactant and methacrylic acid are added. Acid esters, acrylic acid esters, monomers such as styrene, molecular weight regulators such as lauryl mercaptan, and emulsifiers mixed with water and emulsifiers such as sodium α-olefin sulfonate, and emulsified, for example, with a catalyst such as ammonium persulfate In addition, a method of reacting can be mentioned. However, any method known to those skilled in the art may be used as the method for producing the above resin, and the method is not limited to the above method.

Another aqueous resin emulsion that is preferably used in the method for producing a nail varnish according to the present invention is 0.1 to 50 parts by weight of an ethylenically unsaturated monomer (a) having a hydroxyl group in the molecule and an ethylenically unsaturated monomer (b). ) 100 to 100 parts by weight of the monomer mixture containing 50 to 99.9 parts by weight of colloidal silica.
(c) An aqueous resin emulsion obtained by polymerization in an aqueous dispersion medium in the coexistence of 0.5 to 100 parts by weight (solid content conversion) can be mentioned.

As the ethylenically unsaturated monomer (a) having a hydroxyl group in the molecule used for producing the above resin,
For example, 2-hydroxyethyl (meth) acrylate, 2-
Hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate Etc. can be mentioned. These can be used alone or in combination of two or more.

As the monomer contained in the monomer mixture other than the ethylenically unsaturated monomer (a) having a hydroxyl group in the molecule, any monomer may be used as long as it is a monomer copolymerizable with the monomer (a). However, the ethylenically unsaturated monomer (b) can be preferably used. Examples of the ethylenically unsaturated monomer (b) include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate and n-amyl (meth) acrylate. , Isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth)
Acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth)
(Meth) acrylic acid esters such as acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and hydroxypropyl (meth) acrylate; vinyl esters such as vinyl acetate and vinyl propionate; (meth) acrylonitrile; Aromatic vinyls such as styrene, 2-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, vinylanisole, vinylnaphthalene, and divinylbenzene; (meth) acrylamide, N-methylol (meth) acrylamide, diacetoneacrylamide, etc. Amides; vinylidene chloride,
Vinylidene halides such as vinylidene fluoride; ethylene, propylene, isoprene, butadiene, vinylpyrrolidone, vinyl chloride, vinylamide, chloroprene and the like can be used.

The above ethylenically unsaturated monomers (b) may be used alone or in admixture of two or more. In addition, ethylenically unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, and itaconic acid, which are copolymerizable with alkenylbenzene, may be used. In the compound names exemplified above, (meth) acrylate,
(Meth) acrylic acid, (meth) acrylonitrile and (meth) acrylamide are respectively methacrylate, acrylate; methacrylic acid, acrylic acid; methacrylonitrile, acrylonitrile; methacrylamide,
Means acrylamide.

As the colloidal silica (c), for example,
Amorphous silica particles having a particle size of about 4 to 100 nm and negatively charged and dispersed in water to form a colloid can be used. Either colloidal silica on the acidic side or the basic side can be used, and it may be appropriately selected and used according to various conditions at the time of polymerization. As a typical colloidal silica, Snowtex XS, same as above-XL,
Same as -20, same as -30, same as -40, same as -50, same as -C,
Same as -N, same as -S, same as -20L (both are trade names,
Examples thereof include colloidal silica on the basic side such as Nissan Chemical Industry Co., Ltd., or colloidal silica on the acidic side such as Snowtex-O 2 and the same as above-OL (all are trade names, manufactured by Nissan Chemical Industry Co., Ltd.). Further, equivalent colloidal silica is supplied from Catalysts & Chemicals Industry Co., Ltd., DuPont Co., Nalco Chemical Co., etc.

In producing the above aqueous resin emulsion, an ethylenically unsaturated monomer having a hydroxyl group in the molecule
The amount of (a) is 0.1 to 100 parts by weight of the monomer mixture.
50 parts by weight is suitable. Also, the monomer (a)
Monomers other than, for example, ethylenically unsaturated monomers
The amount of (b) may be 50 to 99.9 parts by weight per 100 parts by weight of the monomer mixed solution. Although not limited to a particular theory, the role of the ethylenically unsaturated monomer (a) having a hydroxyl group in the molecule in the above polymerization reaction is that the hydroxyl group (OH) in the monomer is the surface of the colloidal silica (SiOH). It is believed that this is due to the formation of a complex between the ethylenically unsaturated monomer (b) and the colloidal silica (c) by hydrogen bonding with. If the amount of the monomer (a) is less than 0.1 part by weight, the bond with the colloidal silica may be insufficient and complex formation may not be expected. When doing so, there may be a problem such as a decrease in water resistance. Further enhance the effect of the monomer (a),
From the viewpoint of excellent water resistance, the amount of the monomer (a) is preferably in the range of 1 to 20 parts by weight per 100 parts by weight of the monomer mixed solution.

The amount of the colloidal silica (c) is 0.5 in terms of solid content based on 100 parts by weight of a monomer mixed solution containing an ethylenically unsaturated monomer (a) having a hydroxyl group in the molecule.
~ 100 parts by weight. The amount of colloidal silica (c) is 0.5
If the amount is less than parts by weight, the effects of silica, such as durability, solvent resistance, moisture permeability, and blocking resistance, may not be exerted and may not be practical. On the other hand, if it exceeds 100 parts by weight, the transparency of the coating film is impaired due to the influence of colloidal silica, while the hardness increases but the coating film becomes brittle, the mechanical strength decreases, and peeling easily occurs. May cause harmful effects. The effect of silica is more exerted, and from the viewpoint of good film-forming property, the amount of colloidal silica (c) is 2 to 50 in terms of solid content based on 100 parts by weight of the mixed solution.
It is preferable to set the range of parts by weight.

The above aqueous resin emulsion is, for example,
Put a predetermined amount of colloidal silica and pure water in the reaction vessel,
Next, the surfactant is added in an amount of 0.1-
After adding 10 parts by weight, preferably 0.5 to 3 parts by weight, a predetermined amount of an ethylenically unsaturated monomer having a hydroxyl group in the molecule
It can be produced by dropping a monomer mixture liquid containing (a) all at once or continuously. In this case, the monomer mixture liquid may be mixed with water and a surfactant in advance to form an emulsion.

Examples of the surfactant include sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium alkyl diphenyl ether disulfonate, sodium alkyl naphthalene sulfonate, sodium dialkyl sulfosuccinate, sodium stearate, potassium oleate, sodium dioctyl sulfosuccinate. , Sodium polyoxyethylene alkyl ether sulphate, sodium polyoxyethylene alkyl ether sulphate, sodium polyoxyethylene alkyl phenyl ether sulphate, etc. anionic surfactant; anionic surfactants such as sodium dialkyl sulfosuccinate, sodium stearate, sodium oleate Surfactant: polyoxyethylene lauryl ether, polyoxyethylene octyl phe Nonionic surfactants such as polyether ether, polyoxyethylene oleyl phenyl ether, polyoxyethylene nonylphenyl ether, oxyethylene / oxypropylene block copolymer; cationic surfactants such as lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride Can be mentioned. When the amount of the surfactant is less than 0.1 part by weight, the polymerization stability of the product tends to be lowered, and when it exceeds 10 parts by weight, the water resistance of the coating film may be lowered.

The polymerization temperature will differ depending on the type of monomer used and the type of polymerization initiator used, but it is usually suitable to set it in the range of 30 to 90 ° C. As the polymerization initiator, for example,
Persulfates such as hydrogen peroxide, ammonium persulfate and potassium persulfate; Azo initiators such as azobisisobutyronitrile; Organic peroxides such as cumene hydroperoxide and t-butyl hydroperoxide; Examples of the redox initiator include a combination of a sulfate or a peroxide and a metal ion such as iron ion, a reducing agent such as sodium sulfoxylate, sodium pyrosulfite, and L-ascorbic acid. These initiators are used in an amount of, for example, 0.1 to 4 parts by weight based on 100 parts by weight of the total solid content.

As another aqueous resin emulsion,
The polymer dispersed particles of the aqueous resin emulsion have the following two phases:
(A) having a linear, branched or cyclic alkyl group (meth)
Acrylic acid alkyl esters, aromatic vinyl compounds,
And an A-phase comprising a polymer of at least one kind of monomer selected from monomers having two or more polymerizable unsaturated groups in the molecule; and (B) having a linear, branched or cyclic alkyl group ( (Meth) acrylic acid alkyl esters,
Aromatic vinyl compound and 2 polymerizable unsaturated groups in the molecule
At least one kind of monomer selected from those having at least one and preferably 0.5 to 90 parts by weight with respect to 100 parts by weight of all monomers used in the B-phase, a carboxyl group, an amide group and / or It contains a B-phase composed of a copolymer with a monomer having a hydroxyl group, the weight ratio of the A-phase to the B-phase is 5/95 to 95/5, and the glass transition temperature of the A-phase and the B-phase is Are respectively -20 to + 70 ° C and -60 to + 70 ° C, the glass transition temperature difference between both phases is 0 to 60 ° C, and
An aqueous resin emulsion having a glass transition temperature of the A-phase or higher than the glass transition temperature of the B-phase can be used.

Further, it is selected from (meth) acrylic acid alkyl esters having a linear, branched or cyclic alkyl group, an aromatic vinyl compound, and a monomer having two or more polymerizable unsaturated groups in the molecule. Emulsion polymerization of at least one type of monomer to obtain an A-phase, and then in the presence of the A-phase polymer, a (meth) acrylic acid alkyl ester having a linear, branched or cyclic alkyl group, an aromatic Group vinyl compound and at least one kind of monomer selected from monomers having two or more polymerizable unsaturated groups in the molecule, and preferably 0.5 per 100 parts by weight of all monomers used in the B-phase.
To 90 parts by weight of a carboxyl group, an amide group and / or a hydroxyl group-containing monomer are polymerized to form B-
Produced by obtaining a phase copolymer, wherein the dispersed particles of the emulsion include A-phase and B-phase, and the weight ratio of A-phase and B-phase is 5/95 to 95/5, The glass transition temperatures of A-phase and B-phase are -20 to + 70 ° C and -60 to + 70 ° C, respectively,
It is also possible to use an aqueous resin emulsion in which the glass transition temperature difference between both phases is 0 to 60 ° C. and the glass transition temperature of the A-phase is not less than the glass transition temperature of the B-phase.

In the above aqueous resin emulsion,
The A-phase is selected from (meth) acrylic acid alkyl esters having a linear, branched or cyclic alkyl group, an aromatic vinyl compound, and a monomer having two or more polymerizable unsaturated groups in the molecule. It includes a polymer produced by polymerizing at least one kind of monomer. Examples of the (meth) acrylic acid alkyl ester having a linear, branched or cyclic alkyl group in the A-phase include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate and n-butyl ( (Meth) acrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, isohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl ( Examples thereof include (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and octadecyl (meth) acrylate. Aromatic vinyl compounds include styrene and α
Styrene and its derivatives such as -methylstyrene, p-tert-butylstyrene, p-methylstyrene can be used.

The monomer having two or more polymerizable unsaturated groups in the molecule is ethylene glycol di (meth).
Examples thereof include acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, divinylbenzene and trivinylbenzene. The B-phase is selected from (meth) acrylic acid alkyl esters having a linear, branched or cyclic alkyl group, an aromatic vinyl compound, and a monomer having two or more polymerizable unsaturated groups in the molecule. It includes a copolymer produced by copolymerizing at least one kind of monomer and a monomer having a carboxyl group, an amide group and / or a hydroxyl group. That is, the copolymer contained in the B-phase is obtained by copolymerizing, in addition to the monomer used for producing the A-phase, a monomer having a functional group such as a carboxyl group, an amide group and / or a hydroxyl group. It is manufactured.

Examples of the monomer containing a carboxyl group include ethylenically unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid and itaconic acid. As the amide group-containing monomer, (meth) acrylamide, N-methylol (meth) acrylamide, N-alkoxymethyl (meth) acrylamide, or the like can be used. The hydroxyl group-containing monomer includes 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono ( Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate.

In the production of the above aqueous resin emulsion, since the polymers contained in the A-phase and the B-phase are both produced by emulsion polymerization, unlike the solution polymerization, the B-phase polymer is generally used. Does not need to be highly water soluble.
The polymer contained in the B-phase has, for example, a weight average molecular weight of 20.
It is preferably 10,000 or more, and more preferably 250,000 or more, from the viewpoint of drying property, water resistance, durability of the coating film. The upper limit of the weight average molecular weight of the polymer contained in the B-phase is not particularly limited, but from the viewpoint of film formability, for example, 2 million or less, and more generally 1 million or less is used. It is suitable.
Incidentally, the molecular weight of the polymer contained in the B-phase, only the polymer contained in the B-phase was produced under the same conditions, and the obtained polymer was dried and dissolved in tetrahydrofuran, followed by gel permeation method. It can be determined by measuring polystyrene as a standard substance with [for example, SYSTEM-11 (manufactured by Shodex), column: KF804 × 3 pieces].

Although not limited to a particular theory, B-
The carboxyl group, amide group and / or hydroxyl group of the monomer used for producing the polymer contained in the phase have the function of enhancing the stability of emulsion particles containing the A-phase and the B-phase. The monomer having a carboxyl group, an amide group and / or a hydroxyl group used for producing the polymer contained in the B-phase is 0.5 to 90 parts by weight, preferably 1 part by weight based on 100 parts by weight of all the monomers used in the B-phase. To 50 parts by weight, more preferably 2 to 20 parts by weight. The ratio of monomers having a carboxyl group, an amide group and / or a hydroxyl group is 0.5 with respect to 100 parts by weight of all monomers used in the B-phase.
If the amount is less than the weight part, the polymerization stability may be deteriorated and gelation may occur during the polymerization, or the compoundability of other additives may be deteriorated. On the other hand, a carboxyl group,
The proportion of the monomer having an amide group and / or a hydroxyl group is
If it exceeds 90 parts by weight with respect to 100 parts by weight of all the monomers used in the B-phase, the water resistance of the coating film may be significantly deteriorated.

The weight ratio of A-phase to B-phase is, for example, 5/95.
It may be in the range of up to 95/5. If the weight ratio is less than 5/95, the resulting coating may lose flexibility when immersed in water and may become extremely brittle. Also, if this weight ratio exceeds 95/5, in the presence of the A-phase polymer,
During emulsion polymerization of the B-phase polymer, the monomer having a carboxyl group, an amide group and / or a hydroxyl group acts as an aggregating agent between the particles, which may make the polymerization difficult. From the viewpoint of excellent drying property, film forming property and adhesiveness, A-
The weight ratio of the phase to the B-phase (A / B) is preferably 10/90 to 70
/ 30, more preferably 20/80 to 50/50.

The Tg of the A-phase is in the range of -20 to + 70 ° C, and the Tg of the B-phase is in the range of -60 to + 70 ° C. If the Tg of the A-phase is less than -20 ° C, the film formed by the aqueous resin emulsion may cause whitening due to water immersion, and the effect of protecting the nail is lost, which is not preferable. On the other hand, for A-phase
If the Tg exceeds + 70 ° C, only the monomer having no functional group is used in the polymerization of the A-phase, and the stability of the emulsion during the polymerization tends to be poor and gelation tends to occur.
If a large amount of a surfactant or the like is used to prevent this, there arises a problem that the water resistance of the coating is rather deteriorated. On the other hand, when the Tg of the B-phase is less than -60 ° C, the water resistance of the obtained coating may be poor, and when it exceeds + 70 ° C, the obtained coating tends to be hard. A cross-linking agent or the like can be used to prevent the hardening of the coating film, but the use of the cross-linking agent deteriorates the film forming property and deteriorates the water resistance.

In the above aqueous resin emulsion, the Tg difference between the A-phase and the B-phase is in the range of 0 to 60 ° C., and the Tg of the A-phase is the same as the Tg of the B-phase. Alternatively, it is preferably higher than the Tg of the B-phase. A-phase Tg is better than B-phase
If it is lower than Tg or the Tg difference exceeds 60 ° C,
The water resistance of the coating may deteriorate. A-phase Tg is + 20 ~
The range of + 70 ° C. is preferable from the viewpoint of obtaining a coating film having high hardness and excellent durability. In addition, Tg of B-phase
Is preferably in the range of −10 to + 50 ° C. from the viewpoint that a composition having excellent film-forming properties can be obtained and the resulting coating film has excellent adhesion. The Tg can be calculated from the Tg of the homopolymer of each of the monomers constituting the copolymer and the weight ratio of the copolymer using the Fox equation.

The above aqueous resin emulsion is produced by the emulsion polymerization method. The emulsion polymerization method is not particularly limited, and any known emulsion polymerization method may be used. For example, it can be produced by first emulsion-polymerizing the polymer constituting the A-phase and then emulsion-polymerizing the polymer constituting the B-phase in the presence of the A-phase. A-phase and B-
In order to add the monomer, which is a raw material for producing the polymer constituting the phase, to the reaction system, the monomer may be dropped into the reaction system in one batch, continuously or in a divided manner in any polymerization.
In this case, the monomer is mixed beforehand with water and a surfactant,
It may be dropped as an emulsion. Further, when carrying out the polymerization of the B-phase, a polymerization initiator may be added if necessary. The polymerization temperature varies depending on the type of the monomer and the polymerization initiator used, but is generally in the range of 30 to 90 ° C.
Furthermore, during emulsion polymerization, a chain transfer agent such as mercaptan may be added to control the molecular weight. From the viewpoint of the denseness of the obtained coating film, the particle size of the emulsion composition is optimally about 0.01 to 0.3 μm.

An aqueous polyurethane emulsion can be used as another aqueous resin emulsion which is preferably used in the method for producing a nail polish of the present invention. As the polyurethane, those having a neutralization value in the range of 10 to 80 and polymerized and produced in the absence of a tertiary amine can be preferably used. Such polyurethanes have, for example, 2 to 20 acid groups per polyurethane repeating unit. The polyurethane is generally manufactured as an aqueous resin emulsion having a solid content of 5 to 60% by weight.

Among the above-mentioned polyurethanes, particularly preferred polyurethanes are polyurethanes having an acid group such as carboxylic acid, sulfonic acid, sulfuric acid ester or phosphoric acid ester, and metal salts thereof. In the aqueous resin emulsion, all or some of the acid groups may be present in a dissociated state. The molecular weight of these polyurethanes is
It ranges from about 10,000 to about 1,000,000, preferably from about 50,000 to about 100,000. When two or more polyurethanes are mixed and used, the neutralization value of the mixture of the two or more polyurethanes produced by polymerization may be within the above range.

Of these, polyurethane having a carboxylic acid group is particularly preferably used. For example, the neutralization value of polyurethane is in the range of 10 to 80, preferably 20 to 50.
Polyurethanes in the range can be used. In the case of a polyurethane having a carboxylic acid group, if the neutralization value exceeds 80, the water resistance of the cured resin film may deteriorate. On the other hand, when the neutralization number is less than 20, it may be difficult to prepare polyurethane as an aqueous emulsion.

To give an example of the method for producing these polyurethanes, for example, polypropylene glycol as a diol compound, isophorone diisocyanate as a diisocyanate compound, in an organic solvent such as acetone,
A prepolymer is produced by using dimethylolpropionic acid as a polyhydroxycarboxylic acid, and a basic compound such as sodium hydroxide is added to the prepolymer to emulsify it. The organic solvent may be distilled off while polymerizing and reducing the pressure.

Examples of the diol compound include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, trimethylene glycol, 1,3-butylene glycol, tetramethylene glycol, hexamethylene glycol, hydrogenated bisphenol A and bisphenol A. Low molecular weight glycol such as ethylene oxide or propylene oxide adduct of
Polyethers such as polyethylene glycol and polypropylene glycol which are polyols, polyester which is a condensation product of ethylene glycol and adipic acid, polyester which is a condensation product of hexanediol and adipic acid, polyester which is a condensation product of ethylene glycol and phthalic acid, And polycaprolactone.
As chain extenders, polyols such as ethylene glycol and propylene glycol; ethylenediamine, propylenediamine, hexamethylenediamine, tolylenediamine, xylylenediamine, diphenyldiamine, diaminodiphenylmethane, diaminocyclohexylmethane, piperazine, isophoronediamine, etc. Diamines; and water.

As the diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-
Phenylene diisocyanate, xylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-
Biphenylene diisocyanate, 3,3'-dimethoxy-4,
Examples thereof include 4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, and isophorone diisocyanate.

As the polyhydroxycarboxylic acid, 2,2-
Mention may be made of dimethylolpropionic acid, 2,2-dimethylolbutyric acid, and 2,2-dimethylolvaleric acid. In addition, examples of the base compound used in the production of polyurethane include sodium hydroxide, potassium hydroxide, lithium hydroxide, monoethanolamine, diethanolamine, triethanolamine and the like. Any of these glycols, chain extenders, diisocyanates and polyhydroxycarboxylic acids may be used in a mixture at any ratio. All of these components are listed for illustrative purposes and are not intended to be limiting and, optionally, glycols, chain extenders, diisocyanates, polyhydroxycarboxylic acids well known to those skilled in the art. You can

Although several examples of the aqueous resin emulsion preferably used for the aqueous nail polish of the present invention have been described in detail, the aqueous resin emulsion is not limited to the above, and those skilled in the art can use the aqueous resin emulsion. All that is available is within the scope of this invention. It is also possible to use one of these aqueous resin emulsions or a combination of two or more thereof. A person skilled in the art can select an appropriate aqueous resin emulsion without impairing the purpose and effect of the present invention by referring to the above description and changing or modifying them if necessary. Also, for the above aqueous resin emulsion,
You may add and use a small amount of non-aqueous resin.

The above-mentioned aqueous pigment dispersion and the aqueous resin emulsion may be mixed by adding a necessary amount of the aqueous pigment dispersion to the aqueous resin emulsion and then manually stirring or mixing with a mixer. Since the above aqueous pigment dispersion has excellent compatibility with the aqueous resin emulsion, a uniform nail polish can be immediately produced by a simple mixing operation. The aqueous nail varnish produced by the method of the present invention is generally produced as an aqueous composition having a pH in the range of 3 to 11. For adjusting the pH, amines such as ammonia and triethanolamine, and a pH adjusting agent such as sodium hydroxide may be used. Further, dyes such as organic dyes; dispersion aids (anti-settling agents) such as bentonite and montmorillonite;
Drugs such as vitamin E; UV absorbers; bactericides; preservatives;
Perfume; for example, phthalic acid-based or phosphoric acid-based plasticizer; for example, glycol-based film-forming agent; for example, silicon-based film-forming agent; or for example, acrylic resin, smectite-based clay mineral, thickener such as xanthan gum, etc. But it's okay. These additives can be added in the proportions used for ordinary nail polish, and are used, for example, in the range of 0.1 to 10% by weight.

The nail varnish produced by the method of the present invention is substantially provided as an aqueous composition, but the organic solvent used for the production of the aqueous resin emulsion is contained in a trace amount as long as it does not cause skin irritation or the like. It may have been done. Examples of such an organic solvent include acetone and N-methyl-2-pyrrolidone. Further, a small amount of a volatile aqueous organic solvent can be added for the purpose of accelerating the drying of the resin film of the above-mentioned nail polish and for the purpose of sterilization. Examples of such a volatile aqueous organic solvent include ethanol and isopropanol. These organic solvents are 10% by weight, based on the total weight of the nail varnish.
Used below.

The nail varnish produced by the method of the present invention may be brushed on the nails in the same manner as the conventionally known non-aqueous nail varnish at the time of use. The nail varnish after coating is toughened by drying and curing in a short time. Gives a resin coating. 0 on nails.
When the nail polish of the present invention is applied in a thickness of about 04 mm, the curing time of the resin coating is generally about 10 to 30 at room temperature.
Minutes. It takes about 10 hours to completely cure,
The Knoop hardness in that case is about 3. The coating after curing, without using the organic solvent that was used conventionally,
It can be removed with water or a homogeneous mixture of water and an organic solvent.

Examples of the organic solvent contained in the homogeneous mixture of water and the organic solvent used for removing the coating film include acetone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol tertiary butyl ether. , Ethylene glycol monophenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol diphenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, diethylene glycol dimethyl ether, diethylene glycol Lumpur diethyl ether, diethylene glycol dibutyl ether, may be mentioned diethylene glycol diphenyl ether, or mixtures thereof.

Further, ethanol, isopropanol, butanol, benzyl alcohol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether,
Propylene glycol monophenyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, propylene glycol diphenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, Dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol diphenyl ether, propanol, propylene glycol methyl ether acetate, propylene glycol tertiary butyl ether, propylene glycol ethyl ether Le acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, and 3-methyl-3-methoxybutyl acetate or may be a mixture thereof or the like.

These organic solvents include those which form a uniform mixture with water at an arbitrary ratio, and those which form a uniform mixture with water only in a fixed ratio. Of these, it is preferable to use, for example, 5 to 80% by weight of ethanol-water. For example, the coating film can be easily removed by wiping several times with a cloth impregnated with water or a uniform mixture of an organic solvent and water, gauze, absorbent cotton, tissue paper or the like. However, the coating film (resin coating film) formed by the nail varnish produced by the method of the present invention can be removed by using the above organic solvent alone or using a commonly used organic solvent such as toluene. is there.

[0060]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. (1) Aqueous pigment dispersions according to the method of the present invention were prepared in the amounts shown in Table 1 below. A homomixer was used as a processing device, and treatment was carried out at room temperature for 30 minutes to prepare a dispersion liquid having an average particle diameter of 0.2 μm.

[0061]

[Table 1]

(Note 1) sorbitan lauric acid monoester EO 4 mol adduct (HLB 13.3) (Note 2) oleyl alcohol EO 20 mol adduct (HLB 1
5.3) (Note 3) Potassium oleate (HLB 20.0) (Note 4) Sorbitan oleic acid monoester (HLB 4.3) (Note 5) Nonylphenol EO 5.5 mol adduct (HLB 1
0.5) (Note 6) Polymer A: Stirrer, reflux condenser A solution polymerization of acrylic acid was carried out in a 4-neck flask with a moon. After the polymerization was completed, heat was applied to volatilize the solvent, and the solution was added to an aqueous potassium hydroxide solution. And neutralized. This polymerization solution has a solid content of 40% by weight and pH
It was 7.2, and the average molecular weight of the polymer was 4,800. (Note 7) Polymer B: (Note 6) except that solution polymerization of acrylic acid and maleic acid was performed instead of acrylic acid in (Note 6)
The same operation was performed. The polymerization solution has a solid content of 30% by weight,
The pH was 7.5, and the average molecular weight of the polymer was 8,200.

(2) Manicure agents 1 to 7 were produced in accordance with the formulations shown in Table 2 below using the above aqueous dispersions 1 to 7.
The method for producing the aqueous resin emulsion used for each nail polish was as follows, and the nail polish was produced by adding a predetermined amount of the above aqueous dispersion to the aqueous resin emulsion and manually stirring at room temperature. (A) Production of Aqueous Acrylic Resin Emulsion A The following monomer composition: 3% methacrylic acid, 40% ethyl acrylate, 37% methyl methacrylate, styrene 2
Using 0%, a conventional emulsion polymerization method using sodium dodecylbenzenesulfonate was performed. Ammonia water is added as a neutralizer to adjust the pH to 7.5, acid value 20, active ingredient
A 40% styrene-acrylic resin emulsion was prepared.

(B) Production of core-shell type aqueous emulsion B (acrylic resin / core + acrylic resin outer layer) A core-shell type aqueous resin emulsion is produced according to the method described in JP-A-3-133916 (page 110). did. A reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet tube was charged with 50 parts of methyl ethyl ketone, and nitrogen gas was passed to remove dissolved oxygen. Meanwhile, add 35 parts of methyl ethyl ketone and 5 parts of methyl methacrylate to the dropping funnel.
6 parts, 40 parts of n-butyl acrylate, 4 parts of acrylic acid and 0.2 part of azobisisobutyronitrile were charged.

The temperature of the inside of the reactor under stirring was raised to 80 ° C., and a methyl ethyl ketone solution of the above monomer and radical initiator was added dropwise from the dropping funnel over 0.5 hour. Two hours after the dropping of the monomer was completed, a solution prepared by dissolving 0.2 parts of azobisisobutyronitrile in 10 parts of methyl ethyl ketone was added. After aging at the same temperature for 3 hours, 0.1 parts of azobisisobutyronitrile dissolved in 5 parts of methyl ethyl ketone was added again, and the reaction was continued for 5 hours to obtain a copolymer. After completion of the reaction, the copolymer solution was cooled to room temperature, 5.6 parts of triethylamine was added for neutralization, 400 parts of ion-exchanged water was further added with stirring at 300 rpm, and methyl ethyl ketone was distilled off under reduced pressure at 40 ° C. 5 more
The reaction solution was concentrated by distilling off water at 0 ° C to
25% aqueous vinyl resin was obtained.

After stirring, the above-mentioned aqueous vinyl resin 2 was placed in a reactor equipped with a reflux condenser, a dropping funnel, a thermometer and a nitrogen introducing tube.
00 parts and 100 parts of water were charged, and nitrogen gas was introduced to remove dissolved oxygen. On the other hand, 50 parts of isobutyl methacrylate and 75 parts of methanol were charged into the dropping funnel, and the methanol solution of the above monomer was dropped into the above reactor with stirring by the dropping funnel over 1 hour. After heating the inside of the reactor to 70 ° C., a solution prepared by dissolving 0.2 parts of potassium persulfate in 10 parts of water was added. The polymerization reaction was completed by aging at the same temperature for 6 hours. After cooling the inside of the reactor to 50 ° C, reduce the pressure to 50 ° C.
The mixture was concentrated by distilling off methanol and water at.
Ammonia water was added as a neutralizing agent to adjust the pH to 7.3 to obtain a core-shell type aqueous emulsion having a solid content of 35%.

(C) Manufacture of core-shell type aqueous emulsion C (colloidal silica core + acrylic resin outer layer) In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 85.8 parts of pure water and Emal O (stock) (Made by Kao)
0.5 copies, Snowtex O (manufactured by Nissan Chemical Industries, Ltd.)
5.0 parts (in terms of solid content) were charged, the mixture was stirred in a nitrogen atmosphere, the temperature was adjusted to 72 ° C., and 0.5 part of ammonium persulfate was added. Next, 22.2 parts of styrene and 33. of methyl methacrylate.
0 parts, normal butyl acrylate 39.8 parts, methacrylic acid 2.0 parts, methacrylic acid hydroxyethyl ester
2.0 parts and 1.0 part of acrylamide were continuously dropped into the reaction vessel over 3 hours. After completion of the dropping, aging was carried out for 3 hours. Then, the mixture was cooled to room temperature, ammonium water was added as a neutralizing agent to adjust the pH to 8.0, and a core-shell type aqueous emulsion having a solid content of 50% was obtained.

(D) Method for producing polyurethane D Polypropylene glycol (molecular weight 1,000) 186.60 was added to a reactor equipped with a reflux condenser, a thermometer and a stirrer.
g, isoporone diisocyanate 87.20 g, dimethylolpropionic acid 14.30 g, and acetone 190.00 g were charged, and a urethanization reaction was performed while maintaining the temperature at 80 to 100 ° C. to prepare a prepolymer. This prepolymer was emulsified by pouring it into 699.38 g of an aqueous solution containing 0.62 g of sodium hydroxide while mixing with a homomixer, and immediately 5 g of hexamethylenediamine was added to carry out a polymerization reaction. By the end of the reaction, 698.25 g of water was added, and acetone was recovered under reduced pressure to obtain an aqueous polyurethane resin emulsion having a solid content of 30%.

[0069]

[Table 2]

(3) The results of performance evaluation of the above-mentioned nail polish agents 1 to 9 are shown in Table 3 below. The method of each performance evaluation is as follows. (A) Appearance 50 ml of the nail polish of Examples 1 to 9 in a 100 ml wide-mouthed stopper bottle.
Each of them was placed in a constant temperature bath kept at a temperature of 45 ± 2 ° C. After 48 hours, remove the sample from the constant temperature bath and leave it at room temperature for 24 hours,
The state of appearance was observed. (Evaluation) Pigment is uniformly dispersed- (○) Pigment is partially precipitated- (△) Pigment is completely precipitated- (×)

(B) Dispersibility by shaking 50 ml of the nail varnish of Examples 1-9 was placed in a 100 ml wide-mouthed stopper bottle.
Each of them was placed in a constant temperature bath kept at a temperature of 45 ± 2 ° C. 120
After a lapse of time, the sample was taken out of the constant temperature bath and allowed to stand at room temperature for 24 hours, and then shaken for 30 seconds on a rotary shaker manufactured by Sinix Co., Ltd., and the appearance state at this time was observed and evaluated. (Evaluation) Pigment is uniformly dispersed- (○) Pigment is partially precipitated- (△) Pigment is completely precipitated- (×)

(C) Finishing The nail polish was uniformly applied with a fixed amount of the nail polish agent of Examples 1 to 9 by nail printing. 60 at a temperature of 20 ° C and a relative humidity of 60%
After allowing to stand for drying for a minute, the dispersibility of the pigment in the coating film was visually observed and evaluated. (Evaluation) The pigment is uniformly dispersed and finished without unevenness. -(○) Part of the pigment is not evenly dispersed and slight unevenness remains-(△) Pigment is poorly dispersed and unevenness remains-(x)

[0073]

[Table 3]

[0074]

INDUSTRIAL APPLICABILITY According to the method of the present invention, a nail varnish prepared by using an aqueous pigment dispersion liquid containing a specific dispersant is
It is useful because it gives a coating film excellent in gloss and color tone. The nail varnish produced by the method of the present invention has the surprising feature that the coating film has excellent water resistance, even though it is produced using the aqueous pigment dispersion liquid containing a surfactant. .

Claims (7)

[Claims] 1. A surfactant having HLB in the range of 12 to 20 and / or
Alternatively, an aqueous pigment dispersion containing an addition polymer of an ethylenically unsaturated molecule containing an α, β-monoethylenically unsaturated acid having an acid value in the range of 100 to 1,000 as a dispersant is blended with an aqueous resin emulsion. And a method for producing an aqueous nail varnish. 2. The method of claim 1 wherein said surfactant is selected from the group consisting of polyhydric alcohol ester EO adducts, higher alcohol EO adducts, and ionic surfactants. 3. The molecular weight of the addition polymer is 1,000 to 30,0.
The method of claim 1 in the range of 00. 4. The method according to claim 1, wherein the surfactant and the addition polymer are used as a dispersant. 5. The dispersant is added to the dry weight of the pigment.
The method according to any one of claims 1 to 4, which is used in a proportion of 0.5 to 50% by weight. 6. An aqueous nail varnish produced by the method according to any one of claims 1 to 5. 7. The aqueous nail varnish according to claim 5, which has improved water resistance.