JPH05148122A - Water-based manicure - Google Patents

Abstract

PURPOSE:To provide a water-base manicure excellent in stain resistance, gloss, adherability, water resistance and coating film strength, also having such advantages as non-ignitability and no solvent odor. CONSTITUTION:The objective manicure contains 5-60wt.%, on a solid basis, of a water-based composite polymer emulsion where the constituent polymer particles have at least two-layer structure differing in chemical composition from each other having the inner layer consisting of a fluoropolymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based nail enamel different from conventional nail enamel 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 a resin such as nitrocellulose as a film forming agent, an alkyd resin, a plasticizer and an organic solvent as a main base. Occupy However, although these organic solvent-based nail enamel are excellent in various properties as a coating film forming agent, they are serious in flammability, solvent odor, influence on human body due to use of organic solvent, particularly adverse effect on nail itself. It has certain drawbacks. In order to solve these drawbacks, water-based nail polishes that do not use organic solvents have been proposed. For example, JP-A-54-28836,
Japanese Patent Application Laid-Open No. 54-52736 discloses a nail enamel made of an acrylic polymer emulsion, but as far as the inventors of the present invention have made additional tests, they have good brushing properties and film-forming properties (especially low-temperature composition). It is inferior in film properties) and gloss of the coating film.

Further, JP-A-56-131513 and JP-A-57-131513
Japanese Patent No. 56410 discloses a nail enamel comprising an acrylic polymer microemulsion, but the coating film obtained has a drawback that it is quite fragile against mechanical friction. Further, JP-A-56-131513 and JP-A-62-63507 disclose a peeling type water-based nail enamel, but it has a drawback that it is easily peeled off in everyday use, and it is practical. Not really.

[0004]

In view of such circumstances, the present inventors have advantages such as excellent stain resistance, gloss, adhesiveness, water resistance, coating strength, flammability and no solvent odor. As a result of intensive studies to obtain a water-based nail enamel, the present inventors have found that a specific aqueous complex polymer emulsion is extremely effective in achieving this object, and completed the present invention. That is, the present invention provides an aqueous composite polymer emulsion in which the polymer particles constituting the polymer emulsion have a multi-layer structure consisting of at least two layers having different chemical compositions, and the inner layer is a fluoropolymer in terms of solid content of 5 to 5. A water-based nail enamel containing 60% by weight is provided.

A number of water-based composite polymer emulsions having a multilayer structure used in the present invention are known in the paint field. For example, in British Patent No. 928,251, emulsion polymerization is carried out in three stages. The obtained multi-layered polymer latex can be used as a water-based glossy paint material having good water resistance and excellent coating performance, and US Pat. No. 3,256,233 discloses that polymerization is carried out in two or three stages. An aqueous gloss paint consisting of a polymer latex having a layer structure formed and an alternating styrene / maleic anhydride-based copolymer which is soluble in alkali is further disclosed in U.S. Pat. No. 3,236,798. It is described that the copolymer latex of acrylonitrile and ethyl acrylate is a latex paint material with excellent solvent resistance. There is no application example in the field of cosmetics such as nails.

Due to the multi-layer structure, it was difficult to blend by a conventional technique such as kneading with a roll.
Various combinations such as a combination of polymers having a high glass transition temperature and poor compatibility with each other and a formation of a polymer in which a glass phase, a crystal phase and a rubber phase coexist are possible. By using a fluoropolymer as the polymer of the inner layer, the inventors of the present invention have achieved stain resistance, good film-forming property, and high coating film hardness as compared with a multi-layered polymer emulsion which does not use a fluoropolymer for the inner layer. It has been found that it is easy to satisfy both requirements, and that it can be suitably used as a nail varnish. As a method for producing an aqueous composite polymer emulsion composed of particles having such a multilayer structure, a method of performing stepwise emulsion polymerization in an aqueous medium is generally known. For example, there is a method in which the inner layer and the outer layer are formed by combining monomers having different compositions by so-called seed emulsion polymerization (Color Materials Society, 50 (5), 267-275 (1977), etc.). At that time, the seed can be selected by selecting the type of monomer to be combined.
The polymer may form the inner layer or the outer layer. In addition, seed polymerization may give polymer particles having an unclear layer structure, but emulsions of such polymers are not used in the present invention.

In the nail enamel of the present invention, an aqueous composite polymer emulsion whose inner layer is a fluoropolymer is 5 in terms of solid content.
It is characterized by containing ~ 60% by weight. By doing so, the layer structure in the particles is more easily clarified, and when the coating film is formed, a large number of fluorine groups are distributed on the air surface side, so that stain resistance and good film-forming property and high coating property are obtained. Compatibility of film hardness becomes easy. In the present invention, it is advantageous in terms of film forming property that the softening temperature of the polymer of the outer layer is as low as possible. By using a fluoropolymer as the polymer of the inner layer, the coating film does not become sticky even if the softening temperature of the polymer of the outer layer is 0 ° C. or lower. However, when the temperature is lower than -30 ° C, a little stickiness occurs, but it is greatly different from the case where the fluoropolymer is not used as the polymer of the inner layer. Regarding the weight ratio of the polymer in the inner layer portion and the polymer in the outer layer portion, the polymer in the outer layer portion is preferably 0.1 to 20 times by weight, more preferably 0.5 to 5 times by weight, the polymer of the inner layer portion. Less than 0.1 times by weight and
When it exceeds 20 times by weight, the properties of the polymer in the inner layer portion or the outer layer portion become more predominant, so that the effect as the above-mentioned composite polymer emulsion cannot be expected.
Incidentally, if the seed polymerization is carried out in one step, a composite polymer emulsion consisting of two layers of an inner layer and an outer layer can be obtained, but it is also possible to further repeat the seed polymerization to obtain a composite polymer emulsion having a multilayer structure. In that case, one or all of the inner layers may be a fluoropolymer.

In the present invention, the polymer constituting the outer layer is obtained by polymerizing a monomer having a polymerizable double bond. The monomer used is not particularly limited and includes, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n methacrylate.
-(Meth) acrylic acid esters such as butyl; styrene-based monomers such as styrene and chlorostyrene; N-substituted (meth) acrylamides such as t-butylacrylamide; and acrylonitrile and methacrylonitrile. It can be selected from one kind or two or more kinds.

The inner layer can be obtained by polymerizing a fluorine-containing monomer having a polymerizable double bond alone or a monomer having a polymerizable double bond which can be copolymerized therewith. As the fluorine-based monomer used, trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3,4,4-hexafluorobutyl methacrylate, perfluorooctyl methacrylate, Examples thereof include, but are not limited to, perfluorooctyl acrylate and the like. As the monomer to be copolymerized with the fluorine-based monomer, the same monomer as the above-mentioned monomer used as the polymer for the outer layer can be mentioned, but it is highly hydrophobic in order to obtain the intended multilayer structure emulsion. It is preferable to use a monomer.

Therefore, the monomer to be used may be selected in consideration of the hydrophilicity / hydrophobicity of the polymer obtained by polymerization and the high / low softening temperature. It is possible to prepare an aqueous complex polymer emulsion having a multilayer structure by a known method such as emulsion polymerization using an emulsifier, seed emulsion polymerization, soap-free polymerization without using an emulsifier by appropriately combining these. Soap-free polymerization, which is not used, is preferred.

A particularly preferred aqueous complex polymer emulsion used in the present invention is 0.5 to 15% by weight of a monomer having a salt-forming group and having a polymerizable double bond, and a polymerizable double polymer capable of being copolymerized therewith. Monomers with bonds 85-9
After adding water to an organic solvent solution of a copolymer obtained by copolymerizing with 9.5% by weight, the organic solvent is distilled off to obtain a water-soluble vinyl resin (A) in the presence of a polymerizable double polymer. An aqueous complex polymer emulsion obtained by polymerizing a monomer (B) comprising 5 to 100% by weight of a fluorine-containing monomer having a bond and 0 to 95% by weight of a monomer copolymerizable therewith. ..

In the present invention, as the monomer having a salt-forming group and having a polymerizable double bond used in the production of the aqueous vinyl resin (A), an anionic monomer, a cationic monomer, Examples include amphoteric monomers. Examples of the anionic monomer include unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid and maleic acid, or their anhydrides or salts; unsaturated sulfonic acids such as styrenesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid. Acid monomers or salts thereof; unsaturated phosphoric acid monomers such as vinylphosphonic acid and acid phosphoxyethyl (meth) acrylate. As the cationic monomer, N, N
-Dimethylaminoethyl (meth) acrylate, N, N-
(Meth) acrylic acid ester or (meth) acrylamide having a dialkylamino group such as dimethylaminopropylacrylamide; Styrene having a dialkylamino group such as N, N-dimethylaminostyrene, N, N-dimethylaminomethylstyrene; Vinyl pyridines such as 4-vinyl pyridine and 2-vinyl pyridine; or alkyl halides, benzyl halides,
Examples thereof include those quaternized with a known quaternizing agent such as alkyl or aryl sulfonic acid or dialkyl sulfate. As the amphoteric monomer, N- (3-sulfopropyl) -N-methacryloyloxyethyl-N, N-dimethylammonium betaine, N-carboxymethyl-N-
Examples thereof include methacryloyloxyethyl-N, N-dimethylammonium betaine.

As the monomer having a polymerizable double bond which can be copolymerized with the monomer having a salt-forming group and having a polymerizable double bond, methyl acrylate, ethyl acrylate, acrylic acid can be used. (Meth) acrylic acid esters such as n-butyl, lauryl acrylate, methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate; styrene-based monomers such as styrene and chlorostyrene; N such as t-butylacrylamide -Substituted (meth) acrylamide; as well as acrylonitrile, methacrylonitrile and the like, which may be selected from one kind or two or more kinds thereof.

In the present invention, the mixing ratio of the monomer having a salt-forming group and having a polymerizable double bond to the monomer having a polymerizable double bond capable of being copolymerized with the former is 0.5
˜15% by weight, the latter 85 to 99.5% by weight, more preferably 2 to 10% by weight of the former and 90 to 98% by weight of the latter. The amount of the monomer having a salt-forming group and having a polymerizable double bond is 0.5.
If it is less than 15% by weight, a stable aqueous vinyl resin cannot be obtained, and if it exceeds 15% by weight, a resin having practical water resistance cannot be obtained.

To copolymerize the above-mentioned monomer having a salt forming group and having a polymerizable double bond with a monomer having a polymerizable double bond capable of being copolymerized therewith, a known method is known. Copolymerization may be carried out by a known polymerization method such as a solution polymerization method, a bulk polymerization method or a precipitation polymerization method using a radical initiator. Since the phase will be changed to an aqueous system later, it is preferable to move to the next step immediately after the polymerization using a solution polymerization method. It is also possible to purify the copolymer obtained after the polymerization and before the phase inversion to an aqueous system by a known method. The weight average molecular weight of the obtained copolymer is preferably 10,000 to 500,000, and 50,000 to 200,000.
Is more preferable. When the weight average molecular weight is less than 10,000, the physical properties of the coating film are inferior, and when it exceeds 500,000, phase inversion becomes difficult and an aqueous vinyl resin cannot be obtained.

When the salt-forming group of the copolymer is not ionized, it is ionized with a neutralizing agent if necessary. As the monomer having a salt-forming group and having a polymerizable double bond, when a monomer that has already become a salt is used, ionization with a neutralizing agent is unnecessary, but if not, medium It is preferable to ionize with a solvating agent because it is less irritating to nails and skin. As the neutralizing agent, a known acid or base may be used depending on the type of salt-forming group. Examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid; organic acids such as acetic acid, propionic acid, lactic acid, succinic acid and glycolic acid. Examples of the base include tertiary amines such as trimethylamine and triethylamine, ammonia, sodium hydroxide and the like. The degree of neutralization is not particularly limited,
It is desirable to neutralize the resulting aqueous vinyl resin so that the pH of the aqueous vinyl resin is around neutral.

In order to invert the phase of the copolymer thus obtained into an aqueous resin to form an aqueous resin, the copolymer is made into a solution of an organic solvent such as alcohol, ketone, ester or ether, and water is added to the solution. And the organic solvent is distilled off.
The concentration of the organic solvent solution is appropriately determined depending on the composition and molecular weight of the copolymer, but is usually 10 to 80% by weight, preferably 20 to 70% by weight. Among the above-mentioned organic solvents, alcohol-based and / or ketone-based organic solvents are preferable because the phase inversion can be performed well. In the case of the solution polymerization method, the solvent for the polymerization can be arbitrarily selected, but it is preferable to use the organic solvent as described above because the steps from the polymerization to the phase inversion can be simplified. Examples of the alcohol-based solvent used in the present invention include methanol, ethanol, n-propanol, isopropanol and the like, with isopropanol being preferred. Examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, and the like, and preferably methyl ethyl ketone. These may be used alone or in combination of two or more.

The phase inversion from the organic solvent solution to the aqueous system as described above can be carried out by a conventionally known method, and water is stirred at room temperature to 80 ° C., preferably room temperature to 60 ° C. Just add it. In this way, after phase inversion into the water system,
The aqueous vinyl resin (A) can be obtained by distilling off the organic solvent under normal pressure or reduced pressure.

As the fluorine-based monomer having a polymerizable double bond in the monomer (B) to be polymerized in the presence of the aqueous vinyl resin (A), trifluoroethyl methacrylate, 2,2,3 1,3-tetrafluoropropyl methacrylate, 2,2,3,3,4,4-hexafluorobutyl methacrylate, perfluorooctyl methacrylate, perfluorooctyl acrylate, etc., and one or more of them may be selected. You can Examples of the monomer copolymerizable with these fluorine-based monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate. , (Meth) acrylic acid esters such as isobutyl methacrylate and t-butyl methacrylate; styrene-based monomers such as styrene and chlorostyrene; N- such as t-butylacrylamide
Substituted (meth) acrylamide; as well as acrylonitrile, methacrylonitrile and the like can be mentioned, and these can be selected from one kind or two or more kinds.

The proportion of the fluorine-containing monomer having a polymerizable double bond in the monomer (B) and the monomer to be copolymerized therewith is such that the former is 5 to 100% by weight and the latter is 0 to 95% by weight. %, More preferably 30-70% by weight of the former and 30-70% by weight of the latter.
% By weight. If the amount of the fluorine-based monomer is less than 5% by weight, the effect of introducing fluorine is not exhibited and the stain resistance becomes insufficient.
As the polymerization method, the above-mentioned monomer is added to the aqueous vinyl resin (A).
Polymerization may be performed by adding (B) and a known radical initiator. Radical initiators are water-soluble radical initiators such as potassium persulfate, sodium persulfate, 2,2'-azobis (2-amidinopropane) dichloride, 2,2'-azobis (2,4-
Either one or both of oil-soluble radical initiators such as dimethylvaleronitrile) and 2,2′-azobisisobutyronitrile can be used in combination. When a water-soluble initiator is used, it can be polymerized by a usual emulsion polymerization method, and when an oil-soluble initiator is used, it can be dissolved in a monomer solution and added to the aqueous vinyl resin (A).
The polymerization temperature can be freely set in consideration of the decomposition rate of the initiator. The amount of the monomer (B) used is preferably in a range such that the total amount of the resin component in the aqueous vinyl resin (A) and the monomer (B) is 50% by weight or less based on the whole system. If it exceeds 50% by weight, it is difficult to obtain a stable aqueous composite polymer emulsion. Also, the monomer
The amount of (B) used is 0.05 to 0.5% of the resin content in the aqueous vinyl resin (A).
The amount is preferably 10 times by weight, more preferably 0.2 to 2 times by weight. If the amount is less than 0.05 times by weight, the ratio of the newly produced copolymer of the monomer (B) is too low, and the intended purpose cannot be achieved.
If it exceeds 10 times by weight, it is difficult to obtain a stable aqueous composite polymer emulsion. In this way, aqueous vinyl resin
It is possible to polymerize one or more monomers (B) in the presence of (A) without using an emulsifier, but if a stable aqueous complex polymer emulsion is difficult to obtain, use methanol or ethanol in the system. It is easy to obtain a stable aqueous composite polymer emulsion by adding a water-soluble solvent such as an alcohol solvent such as or a ketone solvent such as acetone or methylethylketone to carry out polymerization, and distilling off after completion of the polymerization. In this case, for example, the monomer (B) and the above water-soluble solvent may be mixed in advance and added to the aqueous vinyl resin (A).

The aqueous composite polymer emulsion thus obtained has good stain resistance, suitable film-forming property and coating strength when used as a nail enamel. In addition, since it does not contain an emulsifier component such as a surfactant, the resulting coating film has excellent water resistance.

Although the fine structure of the obtained aqueous composite polymer emulsion particles is not clear yet, the aqueous vinyl resin (A) obtained by the second stage polymerization, that is, phase inversion into an aqueous system.
When the monomer (B) is polymerized in the presence of, the aqueous vinyl resin (A) acts as a dispersion stabilizer for the droplets of the monomer (B) and the produced polymer particles, or resin
It seems that (A) acts as a seed and absorbs the monomer (B) to carry out polymerization. In any case, the water-based vinyl resin in the finished polymer emulsion
Since (A) has an ionic group and is relatively hydrophilic, it is present near the surface of the particle or in the outer layer portion, and the polymer of the monomer (B) is considered to form the central portion or inner layer of the particle.

The physical properties of the aqueous vinyl resin (A) and the polymer of the monomer (B) can be arbitrarily designed by appropriately selecting the monomer, but the softening of the resin component in the aqueous vinyl resin (A) is possible. The temperature is preferably −30 ° C. or higher, more preferably −10 ° C.
That is all. If the softening temperature is less than -30 ° C, the coating film becomes slightly sticky and lacks gloss retention. In the present invention, the softening temperature is 0.1 to 0.2 mm × using a thermal stress strain measurement device (TMA).
This is a value obtained by measuring the temperature at the thermal deformation start point of a 3 mm × 20 mm sample piece (heating rate 5 ° C./min).

In the water-based nail enamel of the present invention, the above aqueous composite polymer emulsion is used as a film-forming base, and its content is 5 to 60% by weight (as solid content). If the amount is less than 5% by weight, multiple coats are required to obtain a practically necessary coating film, and if the amount is more than 60% by weight, the viscosity of the nail varnish becomes high, and the application of the brush release property, etc. Sexual deterioration is seen. In the water-based nail enamel of the present invention, a pigment, a dye, an antiseptic, a fragrance, a plasticizer, a film forming aid, and the like can be blended in addition to the above-mentioned aqueous composite polymer emulsion. As the plasticizer and the film forming aid, known ones such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, butyl carbitol, cellosolve acetate, butyl cellosolve acetate, butyl carbitol acetate can be used, but the storage of the aqueous composite polymer emulsion can be used. From the standpoint of stability and water resistance of the coating film, the blending amount is preferably about 0 to 15% by weight.

[0025]

EXAMPLES Next, the present invention will be described in detail with reference to synthetic examples of aqueous complex polymer emulsions, examples of aqueous nail enamel and comparative examples, but the present invention is not limited to these. All parts and% in the examples are by weight unless otherwise specified.

Synthesis Example 1 50 parts of methyl ethyl ketone was charged into a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen introducing tube, and nitrogen gas was passed to remove dissolved oxygen. On the other hand, 35 parts of methyl ethyl ketone, 56 parts of methyl methacrylate,
40 parts of n-butyl acrylate, 4 parts of acrylic acid and 0.2 part of azobisisobutyronitrile were charged. With stirring, the temperature inside the reactor was raised to 80 ° C., and a methyl ethyl ketone solution of the above monomer and radical initiator was added dropwise from a dropping funnel over 2.5 hours. 2 hours after the addition of the monomer was completed, 0.2 part of azobisisobutyronitrile was added to methyl ethyl ketone 10 parts.
Part dissolved solution was added. After aging at the same temperature for 3 hours,
A solution prepared by again dissolving 0.1 part of azobisisobutyronitrile in 5 parts of methyl ethyl ketone was added, and the reaction was continued for further 5 hours to obtain a copolymer. A part of the obtained copolymer was isolated, and the molecular weight was measured by gel permeation chromatography. The weight average molecular weight was 75,000.
Met. The calibration curve for gel permeation chromatography was prepared using polystyrene as a standard substance (solvent: tetrahydrofuran). The copolymer solution after completion of the reaction was cooled to room temperature, neutralized by adding 5.6 parts of triethylamine, further 400 parts of ion-exchanged water was added with stirring at 300 rpm, and then methyl ethyl ketone was distilled off at 40 ° C. under reduced pressure. Further, the mixture was concentrated by distilling off water at 50 ° C to obtain an aqueous vinyl resin having a solid content of 25%. A part of the obtained aqueous vinyl resin was dried, the resin was taken out, and the softening temperature of the resin was measured by a thermal stress strain measuring device (Seiko Denshi Kogyo's TAM / SS-10) to be 22 ° C. ..

The above aqueous vinyl resin was placed in a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet tube.
200 parts and 100 parts of water were charged and nitrogen gas was passed to remove dissolved oxygen. Meanwhile, the dropping funnel was charged with 25 parts of 2,2,3,3-tetrafluoropropyl methacrylate, 25 parts of t-butyl methacrylate, 100 parts of ethanol, and 0.2 parts of 2,2'-azobis (2,4-dimethylvaleronitrile). It is. With stirring, an ethanol solution of the above monomer was dropped into the above reactor with a 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 reaction was aged for 6 hours at the same temperature to complete the polymerization reaction. After cooling the inside of the reactor to 50 ° C., the mixture was concentrated by distilling off ethanol and water at 50 ° C. under reduced pressure to obtain an aqueous composite polymer emulsion having a solid content of 35%. A part of the obtained aqueous composite polymer emulsion was dried, the resin was taken out, and the softening temperature of the resin was measured by a thermal stress strain measuring device (TMA / SS-10 manufactured by Seiko Denshi Kogyo Co., Ltd.). 7
Two softening temperatures were observed at 4 ° C.

Synthesis Example 2 The aqueous vinyl resin synthesized in Synthesis Example 1 was placed in a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen introducing tube.
200 parts and 100 parts of water were charged and nitrogen gas was flowed to remove dissolved oxygen. On the other hand, 20 parts of perfluorooctyl methacrylate, 15 parts of t-butyl methacrylate were added to the dropping funnel,
25 parts of n-butyl methacrylate, 90 parts of ethanol, 2,2 '
-0.2 parts of azobis (2,4-dimethylvaleronitrile) was charged. Under stirring, the ethanol solution of the above-mentioned monomer and radical initiator was dropped into the above reactor over 1 hour from a dropping funnel. The temperature inside the reactor was raised to 60 ° C., and the mixture was aged at the same temperature for 6 hours to complete the polymerization reaction. Ethanol and water were distilled off in the same manner as in Synthesis Example 1 to obtain an aqueous composite polymer emulsion having a solid content of 35%. The softening temperature of the resin in the obtained aqueous composite polymer emulsion was 24 ° C and 55 ° C.

Synthesis Example 3 34.5 parts of methyl methacrylate was prepared in the same manner as in Synthesis Example 1,
57 parts of n-butyl acrylate and 8.5 parts of N, N-dimethylaminoethyl methacrylate were polymerized in methyl ethyl ketone to obtain a copolymer. The weight average molecular weight of this copolymer was 82,000. Next, this copolymer was mixed with succinic acid 3.2.
Parts to neutralize and invert to water in the same manner as in Synthesis Example 1,
An aqueous vinyl resin having a solid content of 25% was obtained. A part of the obtained aqueous vinyl resin was dried, the resin was taken out, and the softening temperature of the resin was measured and found to be -10 ° C.

A reactor similar to that used in Synthesis Example 1 was charged with 200 parts of the above-mentioned aqueous vinyl resin and 27 parts of water, and nitrogen gas was flowed to remove dissolved oxygen. On the other hand, 15 parts of trifluoroethyl methacrylate and 15 parts of t-butyl methacrylate were added to the dropping funnel.
Parts, 100 parts of ethanol, and 0.1 part of 2,2'-azobis (2,4-dimethylvaleronitrile). Under stirring, the ethanol solution of the above-mentioned monomer and radical initiator was dropped into the above reactor over 1 hour from a dropping funnel. Inside the reactor
The temperature was raised to 60 ° C. and the mixture was aged at the same temperature for 6 hours to complete the polymerization reaction. Ethanol and water were distilled off in the same manner as in Synthesis Example 1 to obtain an aqueous composite polymer emulsion having a solid content of 35%. The softening temperature of the resin in the obtained aqueous composite polymer emulsion was -8 ° C and 76 ° C.

Synthesis Example 4 500 parts of water and 40 parts of lauryl methacrylate were placed in a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen introducing tube.
Part, benzyl methacrylate 48 parts, dimethylaminoethyl methacrylate 12 parts, glycolic acid 70% aqueous solution 8.3
And 2.0 parts of potassium persulfate were charged, and nitrogen gas was passed to remove dissolved oxygen. While stirring, the temperature inside the reactor was raised to 70 ° C., the reaction was continued at the same temperature for 5 hours, and then concentrated by distilling off water to obtain an aqueous vinyl resin having a solid content of 25%. A part of the obtained aqueous vinyl resin was dried, the resin was taken out, and the softening temperature of the resin was measured and found to be -9 ° C.

A reactor similar to that used in Synthesis Example 1 was charged with 200 parts of the above-mentioned aqueous vinyl resin and 27 parts of water, and nitrogen gas was flowed to remove dissolved oxygen. On the other hand, 25 parts of 2,2,3,3-tetrafluoropropyl methacrylate, 25 parts of t-butyl methacrylate, 100 parts of ethanol, and 2,2'-azobis were added to the dropping funnel.
0.2 part of (2,4-dimethylvaleronitrile) was charged. Under stirring, the ethanol solution of the above-mentioned monomer and radical initiator was dropped into the above reactor over 1 hour from a dropping funnel. The temperature inside the reactor was raised to 60 ° C., and the mixture was aged at the same temperature for 6 hours to complete the polymerization reaction. Ethanol and water were distilled off in the same manner as in Synthesis Example 1 to obtain an aqueous composite polymer emulsion having a solid content of 35%. The softening temperature of the resin in the obtained aqueous composite polymer emulsion was -11 ° C and 75 ° C.

Examples 1 to 4 Aqueous nail enamel was produced with the following formulation. still,
In Examples 1 to 4, the aqueous complex polymer emulsions obtained in Synthesis Examples 1 to 4 were used. In the production method, a film forming aid and a plasticizer were added to ion-exchanged water, the pigment was dispersed therein, the aqueous composite polymer emulsion and other components were added, and the mixture was uniformly stirred and mixed, and finally deaerated. The amounts of the film forming aid and the plasticizer used were adjusted so that the film forming temperature of the aqueous nail enamel was almost constant.

Treatment Aqueous complex polymer emulsion (35% solid content) 100 parts Pigment (red pigment R-226) 3 parts Ion-exchanged water 10 parts Film forming aid (carbitol) Appropriate amount (0-10 parts) Plasticizer ( Diethyl phthalate) Appropriate amount (0-10 parts) Perfume 0.1 part Preservative Appropriate amount Silicone defoamer Appropriate amount Comparative Example 1 2,2,3,3-Tetrafluoropropyl methacrylate 25 parts of Synthesis Example 1, t- An aqueous composite polymer emulsion was obtained in the same manner as in Synthesis Example 1 except that 50 parts of t-butyl methacrylate was used instead of 25 parts of butyl methacrylate. An aqueous nail enamel having the same formulation as in Example 1 was produced using this aqueous complex polymer emulsion.

Comparative Example 2 20 parts of perfluorooctyl methacrylate of Synthesis Example 2,
Instead of 15 parts of t-butyl methacrylate and 25 parts of n-butyl methacrylate, 25 parts of t-butyl methacrylate,
An aqueous composite polymer emulsion was obtained in the same manner as in Synthesis Example 2 except that 35 parts of n-butyl methacrylate was used.
An aqueous nail enamel having the same formulation as in Example 1 was produced using this aqueous complex polymer emulsion.

Comparative Example 3 15 parts of trifluoroethyl methacrylate of Synthesis Example 3, t
An aqueous composite polymer emulsion was obtained in the same manner as in Synthesis Example 3 except that 30 parts of t-butyl methacrylate was used instead of 15 parts of -butyl methacrylate. An aqueous nail enamel having the same formulation as in Example 1 was produced using this aqueous complex polymer emulsion.

Comparative Example 4 Synthesis Example 4 was repeated except that 50 parts of t-butyl methacrylate was used instead of 25 parts of 2,2,3,3-tetrafluoropropyl methacrylate and 25 parts of t-butyl methacrylate of Synthesis Example 4. In the same manner, an aqueous complex polymer emulsion was obtained. An aqueous nail enamel having the same formulation as in Example 1 was produced using this aqueous complex polymer emulsion.

The physical properties of the nail enamel obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were evaluated by the following methods. The results are shown in Table 1. Evaluation method (1) Stain resistance A sample is applied to a nail with a nail enamel brush, and the state of stain of the coating film after one day is observed. ◎: No stain ○: Almost no stain △: Slight stain ×: Very stain (2) Drying property Apply the sample to the nail with a nail enamel brush under the conditions of temperature 25 ° C and relative humidity 60%, and touch it with your finger. Measure the drying time. ◯: Within 3 minutes Δ: 3 to 6 minutes ×; 6 minutes or more (3) Light exposure In the dryness evaluation, the gloss of the dried coating film after 30 minutes is visually evaluated. (4) Adhesiveness At the time of dryness evaluation, the adhesiveness to the nail after 20 minutes is evaluated by scraping off the film from the surface with a micro spatula. (5) Water resistance The sample was evenly applied to a nylon plate with a size of 0.5 × 15 × 40 mm with a nail enamel brush, dried for 1 hour at a temperature of 25 ° C and a relative humidity of 60%, and then placed in water at 35 ° C for 1 hour. It is immersed for a period of time and evaluated for deterioration of the coating film (white turbidity, swelling, softening, peeling, etc.). (6) Abrasion resistance At the time of dryness evaluation, a dry coating film after 30 minutes was
Observe the condition after rubbing 00 times. (7) Smell Sensory evaluation of scent with the mouth of nail enamel bottle.

The evaluation items (3) to (7) were judged as follows. ◎: Very good ○: Good △: Normal ×: Poor

[0040]

[Table 1]

As is clear from Table 1, the water-based nail enamel according to the present invention exhibits satisfactory performance in each property required as a nail enamel.

Claims (3)

[Claims] 1. An aqueous complex polymer emulsion having a multi-layer structure in which the polymer particles constituting the polymer emulsion are composed of at least two layers having different chemical compositions, and the inner layer is a fluoropolymer in an amount of 5 to 60 weight% in terms of solid content. % Water-based nail varnish. 2. The method for producing an aqueous composite polymer emulsion is a soap-free polymerization method.
The listed water-based nail polish. 3. The aqueous complex polymer emulsion comprises a monomer having a salt-forming group and a polymerizable double bond of 0.5 to 15 monomers.
After adding water to the organic solvent solution of the copolymer obtained by copolymerizing the weight% and the monomer having a polymerizable double bond capable of copolymerizing 85 to 99.5% by weight, the organic solvent is added. Obtained by polymerizing a monomer (B) containing 5 to 100% by weight of a fluorine-containing monomer having a polymerizable double bond in the presence of an aqueous vinyl resin (A) obtained by distillation. The water-based nail enamel of claim 1, which is an aqueous complex polymer emulsion.