JPH05310531A - Cosmetic - Google Patents

Abstract

(57) [Summary] [Constitution] An aqueous composite polymer emulsion having a multi-layer structure in which polymer particles constituting a polymer emulsion have at least two layers having different chemical compositions, and an inner layer containing a fluoropolymer is calculated as a solid content. Cosmetics containing 1 to 60% by weight. [Effect] It has excellent film-forming properties, water and oil repellency, does not flow or fall off due to sweat or sebum, does not easily make up makeup, and has a good feeling of use without stickiness.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic composition, and more specifically, a hair cosmetic composition and a skin cosmetic composition containing an aqueous vinyl resin emulsion excellent in gloss, film-forming property and water / oil repellency. Etc. regarding cosmetics.

[0002]

BACKGROUND OF THE INVENTION Various film-forming polymers have been used for cosmetics such as hair cosmetics, makeup cosmetics and medicated cosmetics. As the film-forming polymer, a water-soluble polymer or an oil-soluble polymer has been used, but in general, the former has poor water resistance and is easily removed by sweat or water, and the latter has poor oil resistance and is easily removed by sebum, There is also a problem that a volatile organic solvent has to be used as a solvent. Therefore, an aqueous polymer emulsion (latex) has been attracting attention as a film-forming substance that does not have the drawbacks of both. However, a polymer emulsion that is sufficiently satisfactory in properties such as gloss, film-forming property, and water / oil repellency is available. The current situation is that they have not been obtained.

[0003]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a specific aqueous complex polymer emulsion can be preferably used as a film-forming component of cosmetics. Invented. That is, the present invention is
The polymer particles constituting the polymer emulsion have a multilayer structure composed of at least two layers having different chemical compositions, and the inner layer contains an aqueous composite polymer emulsion containing a fluoropolymer in an amount of 1 to 60% by weight in terms of solid content. The featured cosmetic is provided.

Aqueous complex polymer emulsions having a multilayer structure used in the present invention are known in the field of coating materials. 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 example of application to cosmetics.

Due to the multi-layered structure, it was difficult to blend by the conventional technique of kneading with a roll.
Various combinations such as a combination of polymers having a high glass transition temperature and poor compatibility, and the 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, it is possible to achieve both good film-forming properties and a good feeling of use, such as non-sticky surface, as compared to a multilayer structure polymer emulsion that does not use a fluoropolymer for the inner layer. Further, they have found that they can be suitably used as cosmetics, because they have excellent water and oil repellency.

As a method for producing an aqueous composite polymer emulsion composed of particles having such a multilayer structure, a method of carrying out emulsion polymerization stepwise 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 (Journal of Coloring Materials, 50 (5), 267-275 (1
977) etc.), the same method can be used in the step of forming the inner layer in the present invention.

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 stickiness of the coating film does not occur even when 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.

The weight ratio of the polymer in the inner layer portion to the polymer in the outer layer portion is preferably 0.1 to 20 times by weight, more preferably 0.5 to 20 times the polymer in the inner layer portion.
5 times the weight. When it is less than 0.1 times by weight or more than 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. Seed polymerization is 1
By carrying out stepwise, a composite polymer emulsion having two layers of an inner layer and an outer layer can be obtained, but it is also possible to 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-based 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 hydrophilicity / hydrophobicity of the polymer obtained by polymerization and high / low of the softening temperature. By properly combining these, an aqueous composite polymer emulsion having a multilayer structure can be prepared by a known method such as emulsion polymerization using an emulsifier, seed emulsion polymerization, soap-free polymerization without using an emulsifier.

A particularly preferred aqueous composite 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 copolymerizable therewith. Monomers with bonds 85-9
Water was added to the organic solvent solution of the copolymer obtained by copolymerization with 9.5% by weight, and the organic solvent was distilled off to obtain a water-soluble vinyl resin emulsion (A). A monomer comprising 5 to 100% by weight of a fluorine-containing monomer having a heavy bond and 0 to 95% by weight of a monomer copolymerizable therewith.
It is an aqueous composite polymer emulsion obtained by polymerizing (B).

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 emulsion (A), an anionic monomer,
Examples include cationic monomers and 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-dimethylaminopropylacrylamide or other dialkylamino group-containing (meth) acrylic acid ester or (meth) acrylamides; Styrenes having a dialkylamino group such as N-dimethylaminostyrene and N, N-dimethylaminomethylstyrene; vinylpyridines such as 4-vinylpyridine and 2-vinylpyridine; or their 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-
Examples thereof include dimethylammonium betaine, N-carboxymethyl-N-methacryloyloxyethyl-N, N-dimethylammonium betaine and the like.

Examples of the monomer having a polymerizable double bond which can be copolymerized with the monomer having a salt forming group and a polymerizable double bond include methyl acrylate, ethyl acrylate and acrylic acid. (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 compounding 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 monomer 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 wt%, a stable aqueous vinyl resin emulsion cannot be obtained, and if it exceeds 15 wt%, a practical resin having water resistance cannot be obtained.

To copolymerize the above-mentioned monomer having a polymerizable double bond having a salt-forming group and 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 poor, and when it exceeds 500,000, phase inversion becomes difficult and an aqueous vinyl resin emulsion 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 hair 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, but it is desirable to neutralize the resulting aqueous vinyl resin emulsion so that the pH of the emulsion is near 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 an alcohol, a ketone, an ester or an ether, and water is added thereto. 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 emulsion (A) is obtained by distilling off the organic solvent under normal pressure or reduced pressure.

The fluorine-based monomer having a polymerizable double bond in the monomer (B) to be polymerized in the presence of the aqueous vinyl resin emulsion (A) is trifluoroethyl methacrylate, 2,2, 3,3-Tetrafluoropropyl methacrylate, 2,2,3,3,4,4-hexafluorobutyl methacrylate, perfluorooctyl methacrylate, perfluorooctyl acrylate, etc. may be mentioned, and one or more of them may be selected. be able to. 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-substituted (meth) acrylamides such as t-butylacrylamide; and acrylonitrile and methacrylic acid. Examples thereof include ronitrile and the like, and these can be selected from one kind or two or more kinds.

The mixing ratio of the fluorine-containing monomer having a polymerizable double bond in the monomer (B) and the monomer to be copolymerized with it is 5 to 100% by weight of the former and 0 to 95% by weight of the latter. %, More preferably 30-70% by weight of the former and 30-70% by weight of the latter.
% By weight. When the amount of the fluorine-based monomer is less than 5% by weight, the effect of introducing fluorine is not exhibited, and the effects of preventing stickiness, water repellency and oil repellency are lost.

As the polymerization method, the above-mentioned monomer (B) and a known radical initiator may be added to the aqueous vinyl resin emulsion (A) for polymerization. Radical initiators are water-soluble radical initiators such as potassium persulfate, sodium persulfate, 2,2'-azobis (2-amidinopropane) dichloride, 2,2'-azobis (2,4-dimethylvaleronitrile),
Either or both of the oil-soluble radical initiators such as 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 emulsion (A). .. The polymerization temperature can be freely set in consideration of the decomposition rate of the initiator. Monomer (B)
It is preferable that the total amount of the resin component and the monomer (B) in the aqueous vinyl resin emulsion (A) 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 (B)
The amount of the resin used in the aqueous vinyl resin emulsion (A) is preferably 0.05 to 10 times by weight, more preferably 0.2 to 2 times.
It is twice the weight. If less than 0.05 times by weight, newly generated monomer
Since the proportion of the copolymer (B) is too low, 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, one or more monomers (B) can be polymerized in the presence of the aqueous vinyl resin emulsion (A) without using an emulsifier, but if a stable aqueous composite polymer emulsion is obtained. If it is difficult to do so, add a water-soluble solvent such as an alcohol solvent such as methanol or ethanol, or a ketone solvent such as acetone or methyl ethyl ketone to the system to perform polymerization, and distill off after the polymerization to obtain a stable aqueous composite polymer emulsion. It is easy to get hit. In this case, for example, the monomer
(B) and the above water-soluble solvent may be mixed in advance, and this may be added to the aqueous vinyl resin emulsion (A). The aqueous composite polymer emulsion thus obtained has good film-forming properties, water / oil repellency and anti-stickiness when used as a cosmetic.

Although the fine structure of the obtained aqueous composite polymer emulsion particles is not clear yet, it is present in the presence of the aqueous vinyl resin emulsion (A) obtained by the second stage polymerization, that is, phase inversion in an aqueous system. When polymerizing the monomer (B),
Whether the aqueous vinyl resin emulsion (A) acts as a dispersion stabilizer for the droplets of the monomer (B) and the resulting polymer particles, or the aqueous vinyl resin emulsion (A) acts as a seed and the monomer (B) It seems that either of them is absorbed to carry out the polymerization. In any case, the water-based vinyl resin emulsion 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 emulsion (A) and the polymer of the monomer (B) can be arbitrarily designed by appropriately selecting the monomer. The softening temperature of the resin component is preferably −30 ° C. or higher, more preferably −10 ° C. or higher. Softening temperature is -30
If the temperature is lower than ℃, the coating film becomes a little sticky, which leads to a decrease in usability. In the present invention, the softening temperature is a value obtained by measuring the temperature at the thermal deformation start point of a sample piece of 0.1 to 0.2 mm x 3 mm x 20 mm using a thermal stress strain measuring device (TMA) (heating rate 5 ° C). / Min).

In the cosmetic of the present invention, the above-mentioned aqueous composite polymer emulsion is used as a film-forming base, and its content is 1 to 60% by weight (as solid content). When the amount is less than 1% by weight, it is difficult to obtain a practically sufficient coating film,
If it exceeds 60% by weight, the viscosity of the cosmetic material becomes high, and it becomes difficult to formulate it or apply it to the skin and hair. In the cosmetics of the present invention, pigments, dyes, preservatives, fragrances, plasticizers, film forming aids 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.

[0026]

EXAMPLES Next, the present invention will be specifically described with reference to synthesis examples of aqueous complex polymer emulsions and examples of cosmetics of the present invention, 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, 54 parts of methyl methacrylate,
42 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. Two hours after the dropping of the monomer was completed, 0.2 part of azobisisobutyronitrile was added to 10 parts of methyl ethyl ketone.
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 its molecular weight was measured by gel permeation chromatography, and its weight average molecular weight was 80,000.
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 emulsion having a solid content of 25%. A part of the obtained aqueous vinyl resin emulsion is dried to take out the resin,
The softening temperature of the resin was 18 ° C when measured with a thermal stress strain measuring device (TMA / SS-10 manufactured by Seiko Instruments Inc.).

A reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet tube was charged with 200 parts of the above aqueous vinyl resin emulsion and 100 parts of water, and nitrogen gas was passed to remove dissolved oxygen. On the other hand, in the dropping funnel 2,2,3,3-
20 parts of tetrafluoropropyl methacrylate, 30 parts of t-butyl methacrylate, 100 parts of ethanol, and 0.2 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) were charged. 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, 0.2 parts of potassium persulfate was added to 10 parts of water.
Part dissolved solution was added. The reaction was aged for 6 hours at the same temperature to complete the polymerization reaction. After cooling 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 complex polymer emulsion having a solid content of 35%. A part of the obtained aqueous complex polymer emulsion was dried, the resin was taken out, and the softening temperature of the resin was measured with a thermal stress strain measuring device (TMA / SS-10 manufactured by Seiko Denshi Kogyo Co., Ltd.). Two softening temperatures were observed at 78 ° C.

Synthesis Example 2 A reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen introducing tube was charged with 200 parts of the aqueous vinyl resin emulsion synthesized in Synthesis Example 1 and 100 parts of water, and nitrogen gas was added. And dissolved oxygen was removed. On the other hand, 20 parts of trifluoroethyl methacrylate, 10 parts of t-butyl methacrylate, 30 parts of n-butyl methacrylate, ethanol were added to the dropping funnel.
90 parts, 2,2'-azobis (2,4-dimethylvaleronitrile)
0.2 parts were loaded. 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. Raise the temperature inside the reactor to 60 ° C,
The reaction was aged for 6 hours at the same temperature to complete the polymerization reaction. Ethanol and water were distilled off in the same manner as in Synthesis Example 1 to obtain a solid content.
A 35% aqueous complex polymer emulsion was obtained. The softening temperature of the resin in the obtained aqueous complex polymer emulsion was 19
℃ and 45 ℃.

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 emulsion having a solid content of 25% was obtained. A part of the obtained aqueous vinyl resin emulsion 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 water-based vinyl resin emulsion and 27 parts of water, and nitrogen gas was flowed to remove dissolved oxygen. On the other hand, 12 parts of perfluorooctyl methacrylate, 18 parts of t-butyl methacrylate, 100 parts of ethanol, and 2,2'-azobis were added to the dropping funnel.
0.1 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 -8 ° C and 83 ° C.

Example 1 (Eyeshadow) A cream type eyeshadow having the following composition was produced by the following production method. <Composition> Paraffin wax 3.0% Stearic acid 3.0 Liquid paraffin 8.5 Lanolin 1.0 Sorbitan monostearate 1.5 Glycerin 5.5 Triethanolamine 1.5 Hydroxyethyl cellulose 0.5 Aqueous complex polymer emulsion (Synthesis example 1, solid content 35%) 10.0 Pearl pigment 10.0 Ultramarine blue 2.0 Deionized water Residual amount Fragrance Amount Preservative Amount <Production method> Hydroxyethyl cellulose, glycerin, and triethanolamine are dissolved in ion-exchanged water, and then heated to uniformly disperse the pearl pigment and ultramarine blue. Then, heat and dissolve the oil phase component such as paraffin wax,
The mixture is added to the aqueous phase while stirring and emulsified. After cooling
The aqueous complex polymer emulsion obtained in Synthesis Example 1, a fragrance and a preservative are added to obtain a blue cream type eye shadow. This eye shadow was excellent in both water repellency and oil repellency and had a good feeling in use without stickiness.

Example 2 (Mascara) A mascara having the following composition was manufactured by the manufacturing method shown below. <Composition> Aqueous complex polymer emulsion (Synthesis example 2, solid content 35%) 45.0% Black iron oxide 15.0 Kaolin 10.0 Xanthan gum 0.5 Polyoxyethylene sorbitan monooleate 1.5 Glycerin 5.0 Ion-exchanged water Residual amount Fragrance amount Preservative amount <Production method> Xanthan gum, kaolin, and the aqueous composite polymer emulsion obtained in Synthesis Example 2 were added to ion-exchanged water, and the mixture was stirred and mixed uniformly, and then a colored paste containing black iron oxide, glycerin, and polyoxyethylene sorbitan monooleate. Is added and mixed evenly, and a flavor and a preservative are added to give a black mascara. This mascara was excellent in water resistance (sweat).

Example 3 (Eyeliner) A liquid film type eyeliner having the following composition was produced by the following production method. <Composition> Aqueous complex polymer emulsion (Synthesis example 3, solid content 35%) 60.0% Carbon black 5.0 Titanium dioxide 2.0 Polyoxyethylene sorbitan monostearate 1.0 Glycerin 3.0 Hydroxyethyl cellulose 1.0 Ion-exchanged water Residual amount Fragrance amount Preservative Small amount <Production method> Polyoxyethylene sorbitan monostearate is dissolved in ion-exchanged water, carbon black and titanium dioxide are mixed therein, and uniformly dispersed using a colloid mill. Glycerin, hydroxyethyl cellulose, and the aqueous composite polymer emulsion obtained in Synthesis Example 3 are added to and uniformly mixed, and finally, a fragrance and a preservative are added to give a black film-type eyeliner. This eyeliner was excellent in water resistance (sweat).

[0035]

The aqueous composite polymer emulsion according to the present invention is excellent in film-forming property, water repellency and oil repellency, and the cosmetic composition of the present invention containing the emulsion may flow by sweat or sebum, It is a cosmetic that does not fall off and does not easily lose makeup, and at the same time has a good feeling of use without stickiness. Since the cosmetics of the present invention have such characteristics, various foundations, eye makeups, eyeliners, eyebrow, eye makeup cosmetics such as mascara, packs, lipsticks, blushers, hair coloring agents, and sunscreens. It can be widely applied to skin cosmetics such as screen agents, hair cosmetics, and medicated cosmetics.

Claims (2)

[Claims] 1. An aqueous complex polymer emulsion having a multi-layer structure in which polymer particles constituting a polymer emulsion have at least two layers having different chemical compositions, and an inner layer contains a fluoropolymer in an amount of 1 to 60 weight% in terms of solid content. % Of cosmetics. 2. The aqueous complex polymer emulsion comprises a salt having a salt-forming group and a monomer having a polymerizable double bond 0.5 to 15
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. In the presence of the aqueous vinyl resin emulsion (A) obtained by distilling off, a fluorine-based monomer having a polymerizable double bond 5 to 10
The cosmetic according to claim 1, which is an aqueous composite polymer emulsion obtained by polymerizing a monomer (B) containing 0% by weight.