JP2857238B2 - Cosmetics - Google Patents

Description

The present invention relates to cosmetics, and more particularly, to cosmetics.
The present invention relates to cosmetics, such as hair cosmetics and skin cosmetics, containing an aqueous composite polymer emulsion having excellent luster, water resistance, and film forming properties.

[Problems to be solved by conventional technology and invention]

Conventionally, 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 taken off by sweat or water, and the latter has poor oil resistance.
There was a problem that it was easy to remove with sebum and a volatile organic solvent had to be used as a solvent. For this reason, an aqueous polymer emulsion (latex) has been attracting attention as a film-forming substance having neither of these drawbacks.
At present, a polymer emulsion having sufficiently satisfactory properties such as film forming properties and water resistance has not been obtained.

[Means for solving the problem]

In view of such circumstances, the present inventors, gloss, water resistance, as a result of intensive research to obtain a polymer emulsion excellent in film-forming properties, specific aqueous composite polymer emulsion,
The present inventors have found that this is very effective in achieving the object, and have reached 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 multilayer structure composed of at least two layers having different chemical compositions, and the outermost layer polymer has a lower softening temperature than the inner layer polymer. Is contained in an amount of 1 to 60% by weight in terms of solid content.

Several aqueous composite polymer emulsions having a multilayer structure used in the present invention are known in the field of coatings.For example, GB 928,251 discloses a multilayer obtained by emulsion polymerization in three stages. The fact that the structured polymer latex becomes a water-based gloss paint material with good water resistance and excellent coating performance is disclosed in U.S. Pat.
No. 6,233 discloses an aqueous gloss paint composed of a polymer latex having a layer structure and an alkali-soluble styrene / maleic anhydride-based alternating copolymer, in which polymerization is performed in two or three stages. U.S. Pat.No. 3,236,79
No. 8 discloses that a copolymer latex of acrylonitrile and ethyl acrylate that has been polymerized stepwise becomes a latex paint material having excellent solvent resistance, but application examples in the cosmetics field are not found. Absent.

By taking a multilayer structure, it was difficult in the conventional blending method of kneading with a roll or the like, a glass transition temperature is high, and a combination of poorly compatible polymers and a glass phase-a crystal phase-a rubber phase Various combinations are possible, such as the formation of coexisting polymers. If the present inventors design the softening temperature of the polymer in the outermost layer to be lower than the softening temperature of the polymer in the inner layer, the film forming property will be higher than that of a polymer emulsion consisting of particles of uniform composition without a multilayer structure. It has been found that it is possible to achieve both goodness and high hardness of the coating film, and it can be suitably used as a cosmetic.

As a method for producing an aqueous composite polymer emulsion composed of particles having such a multilayer structure, a method in which emulsion polymerization is carried out 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 the Society of Color Materials, 50 (5), 267-275 (1977)).
etc). At that time, there is a case where the seed (seed) polymer forms an inner layer and a case where an outer layer is formed by selecting the kind of the monomer to be combined. In addition, polymer particles having an unclear layer structure may be obtained by seed polymerization, but an emulsion of such a polymer is not used in the present invention.

Further, it is also possible to design such that the polymers constituting the inner layer and the outer layer of the obtained polymer emulsion particles have different softening temperatures by selecting the type of the monomer to be used. The present invention is particularly characterized in that the polymer constituting the outermost layer has a lower softening temperature than the polymer constituting the inner layer. By adopting such a configuration, the outermost layer having a lower softening temperature when applied to the skin or hair becomes a continuous phase and exhibits a good film-forming property, and the inner layer having a higher softening temperature is formed inside the coating film. It is thought that a suitable coating film hardness can be imparted. Even if the polymer emulsion is designed so that the polymer constituting the outermost layer has a higher softening temperature than the polymer constituting the inner layer, the film formability and physical properties of the obtained coating film are not suitable for use in cosmetics. I can not say.

In the present invention, the softening temperature of the polymer of the outermost layer is preferably as low as possible in terms of film formability.However, if the temperature is too low, the film becomes sticky and lacks gloss retention, so that the temperature is -10 ° C.
Or more, more preferably 0 ° C. or more. When the polymer of the outermost layer has a high softening temperature (for example, room temperature or higher) and is difficult to form a film, the film forming property can be adjusted by appropriately using a film forming aid and a plasticizer.

On the other hand, the softening temperature of the polymer in the inner layer is preferably higher than that of the polymer in the outermost layer by 10 ° C. or more. If the difference in the softening temperature is less than 10 ° C., it is difficult to achieve both the above-mentioned good film forming property and an appropriate coating film hardness.

Describing the weight ratio of the polymer of the inner layer portion and the outermost layer portion, the polymer of the outermost layer portion is
It is preferably 0.1 to 20 times by weight, more preferably 0.5 to 5 times by weight. If it is less than 0.1 times by weight or more than 20 times by weight, the properties of the polymer in the interior part or the outermost layer become more dominant, so that the effect as the above composite polymer emulsion cannot be expected.

If the seed polymerization is performed in one stage, a composite polymer emulsion composed of two layers, an inner layer and an outer layer, can be obtained. However, it is also possible to repeat the seed polymerization to obtain a composite polymer emulsion having a multilayer structure. In that case, the object of the present invention can be achieved if the softening temperature of the polymer constituting the outermost layer is set lower than the softening temperature of the polymer constituting the inner layer.

In the present invention, the polymer constituting the outer layer and the inner layer is obtained by polymerizing a monomer having a polymerizable double bond. The monomer used is not particularly limited, and examples thereof include (meth) acrylic acid such as methyl acrylate, ethyl acrylate, n-butyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate. Esters; styrene-based monomers such as styrene and chlorostyrene; N-substituted (meth) acrylamides such as t-butylacrylamide; and acrylonitrile, methacrylonitrile, and the like. One or more of these may be selected. it can.

Here, when the polymer constituting the inner layer is more hydrophobic than the polymer constituting the outer layer, it is easier to obtain the intended multilayer emulsion.

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. By appropriately 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, or aqueous medium heterogeneous polymerization without an emulsifier.

A particularly preferred aqueous composite polymer emulsion used in the present invention has 0.5 to 15% by weight of a monomer having a salt-forming group and having a polymerizable double bond, and a polymerizable double bond copolymerizable therewith. After adding water to an organic solvent solution of a copolymer obtained by copolymerizing 85 to 99.5% by weight of a monomer, in the presence of an aqueous vinyl resin (A) obtained by distilling off the organic solvent, An aqueous composite polymer emulsion obtained by polymerizing a monomer (B) having one or more polymerizable double bonds.

In the present invention, the monomer having a salt-forming group and having a polymerizable double bond used in the production of the aqueous vinyl resin (A) includes an anionic monomer, a cationic monomer, and an amphoteric monomer. Body and the like.

Examples of the anionic monomer include unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, and maleic acid, and anhydrides and salts thereof; unsaturated sulfonic acids such as styrene sulfonic acid and 2-acrylamido-2-methylpropane sulfonic acid. Acid monomers or salts thereof; and unsaturated phosphoric acid monomers such as vinylphosphonic acid and acid phosphoxyethyl (meth) acrylate.

Examples of the cationic monomer include (meth) acrylic esters or (meth) acrylamides having a dialkylamino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropylacrylamide; Styrenes having a dialkylamino group such as N-dimethylaminostyrene and N, N-dimethylaminomethylstyrene; vinylpyridines such as 4-vinylpyridine and 2-vinylpyridine; or alkyl halides and benzyl halides thereof. Examples thereof include those quaternized with a known quaternizing agent such as alkyl or aryl sulfonic acid, or dialkyl sulfate.

As an amphoteric monomer, N- (3-sulfopropyl) -N
-Methacryloyloxyethyl-N, N-dimethylammonium betaine, N-carboxymethyl-N-methacryloyloxyethyl-N, N-dimethylammonium betaine and the like.

Monomers having a polymerizable double bond that can be copolymerized with the monomer having a salt-forming group and a polymerizable double bond include methyl acrylate, ethyl acrylate, and n-butyl acrylate. (Meth) acrylates such as lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate; styrene monomers such as styrene and chlorostyrene; N-substituted (meth) such as t-butylacrylamide Acrylamide; and acrylonitrile, methacrylonitrile, and the like. One or more of these can be selected.

In the present invention, the compounding ratio of the monomer having a polymerizable double bond having a salt-forming group and the monomer having a polymerizable double bond copolymerizable with the monomer is 0.5 to 15% by weight of the former. 85 to 99.5% by weight, more preferably the former 2
-10% by weight, the latter 90-98% by weight. If the amount of the monomer having a salt-forming group and a polymerizable double bond is less than 0.5% by weight, a stable aqueous vinyl resin cannot be obtained. If the amount exceeds 15% by weight, practical water resistance is obtained. No resin is obtained.

To copolymerize a monomer having a polymerizable double bond having the above salt-forming group and a monomer having a polymerizable double bond copolymerizable therewith, a known radical initiator is used. May be copolymerized by a known polymerization method such as a solution polymerization method, a bulk polymerization method, and a precipitation polymerization method. Since the phase is changed to an aqueous phase later, it is preferable to immediately proceed to the next step after the polymerization using a solution polymerization method. After the polymerization, the copolymer obtained before the phase inversion to an aqueous system can be purified by a known method. The weight average molecular weight of the obtained copolymer is 10,000.
~ 500,000 is preferred, and 50,000-200,000 is more preferred. If the weight average molecular weight is less than 10,000, the physical properties of the coating film are poor, and if it exceeds 500,000, phase inversion becomes difficult, and an aqueous vinyl resin cannot be obtained.

When the copolymer and the salt-forming group are not ionized, ionization is performed with a neutralizing agent as necessary. When a monomer that is already a salt is used as the monomer having a salt-forming group and having a polymerizable double bond, ionization with a neutralizing agent is not necessary. It is preferable to ionize with a waving agent because it has less irritation to the skin and hair.

Known acids and bases may be used as the neutralizing agent depending on the type of the salt-forming group. Examples of the acid include hydrochloric acid,
Acid anhydrides such as sulfuric acid; and 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 obtained aqueous vinyl resin so that the pH of the aqueous vinyl resin is around neutrality.

In order to phase-convert the copolymer thus obtained into an aqueous resin and obtain 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 this is added to water. The organic solvent may be 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 it is 20 to 70% by weight.

Among the above-mentioned organic solvents, alcohol-based and / or ketone-based organic solvents having a boiling point lower than that of water and being miscible with water are preferable because phase inversion and distillation of the solvent can be carried out well. In the case of using the solvent polymerization method, the solvent for the polymerization can be arbitrarily selected. However, the use of the above-mentioned organic solvent is preferable because the steps from polymerization to phase inversion are simplified.

Examples of the alcohol solvent used in the present invention include methanol, ethanol, n-propanol, isopropanol and the like, and preferably isopropanol. Examples of the ketone-based solvent include acetone, methyl ethyl ketone, diethyl ketone, and the like, and preferred is 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 performed by a conventionally known method, and under stirring of the organic solvent solution, water may be added at a temperature of room temperature to 80 ° C, preferably room temperature to 60 ° C. . As described above, the organic vinyl solvent (A) is obtained by distilling off the organic solvent under normal pressure or reduced pressure after the phase inversion to the aqueous system.

Examples of the monomer (B) having one or more polymerizable double bonds to be polymerized in the presence of the aqueous vinyl resin (A) include methyl acrylate, ethyl acrylate, and n-butyl acrylate. , Lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-methacrylic acid
-Butyl, isobutyl methacrylate, t-methacrylate
(Meth) acrylates such as butyl; styrene,
Styrene-based monomers such as chlorostyrene; N-substituted (meth) acrylamides such as t-butylacrylamide;
And acrylonitrile, methacrylonitrile, and the like, and one or more of these can be selected.

As a polymerization method, the monomer (B) and a known radical initiator may be added to the aqueous vinyl resin (A) for polymerization. Radical initiators include water-soluble radical initiators such as potassium sulfate and sodium persulfate 2,2'-azobis (2-amidinopropane) dichloride; 2,2'-azobis (2,4-dimethylvaleronitrile); One or both of oil-soluble radical initiators such as 2'-azobisisobutyronitrile can be used in combination.
When a water-soluble initiator is used, the polymerization can be carried out by a usual emulsion polymerization technique. When an oil-soluble initiator is used, it may 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 such that the total amount of the resin component and the monomer (B) in the aqueous vinyl resin (A) is
A range that is 50% by weight or less is preferable. If it exceeds 50% by weight, it is difficult to obtain a stable aqueous composite polymer emulsion. The amount of the monomer (B) used is based on the aqueous vinyl resin (A).
The content is preferably 0.05 to 10 times by weight, more preferably 0.2 to 2 times by weight of the resin content therein. If the amount is less than 0.05 times by weight, the ratio of the newly formed (co) polymer of the monomer (B) is too low, so that 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 manner, one or more monomers (B) can be polymerized in the presence of the aqueous vinyl resin (A) without using an emulsifier, but a stable aqueous composite polymer emulsion can be obtained. If it is difficult, a water-soluble solvent such as an alcoholic solvent such as methanol or ethanol, or a ketone-based solvent such as acetone or methyl ethyl ketone is added to the system to carry out polymerization, followed by distilling off after completion of the polymerization to obtain a stable aqueous composite polymer emulsion. Cheap. In this case, for example, the monomer (B) and the water-soluble solvent may be mixed in advance and added to the aqueous vinyl resin (A).

The aqueous composite polymer emulsion thus obtained is
When used as a cosmetic, it has suitable film formability and coating film strength. Further, since the composition does not contain an emulsifier component such as a surfactant, the obtained coating film has excellent water resistance.

Although the microstructure of the obtained aqueous composite polymer emulsion particles is not yet clear, the monomer (B) is obtained in the second stage of polymerization, that is, in the presence of the aqueous vinyl resin (A) obtained by inverting the aqueous phase. )), The aqueous vinyl resin (A)
Is acting as a dispersion stabilizer for the droplets of the monomer (B) and the resulting polymer particles, or the aqueous vinyl resin (A) acts as a seed to absorb the monomer (B) and perform polymerization. It seems either. In any case,
In the resulting polymer emulsion, the aqueous vinyl resin (A) has an ionic group and is relatively hydrophilic, so it exists near the surface of the particle or in the outer layer, and the monomer (B)
The (co) polymer is believed to form the center or inner layer of the particles.

The physical properties of the aqueous vinyl resin (A) and the (co) polymer of the monomer (B) can be arbitrarily designed by appropriately selecting the monomer. ) Of the monomer (B) (co)
More favorable results are obtained when the temperature is designed to be lower than the softening temperature of the polymer. In particular, the softening temperature of the resin component in the aqueous vinyl resin (A) is preferably -10 ° C or higher,
More preferably, it is 0 ° C. or higher. If the softening temperature is lower than -10 ° C, the coating film becomes sticky and lacks gloss retention. Further, in order to exhibit the above-mentioned effects, that is, to achieve compatibility between film formability and coating film hardness, a (co) polymer of a monomer (B) polymerized in the presence of an aqueous vinyl resin (A) Is preferably 10 ° C. or higher than the softening temperature of the resin component in the aqueous vinyl resin (A).

In the present invention, the softening temperature is a value obtained by measuring the temperature at the starting point of thermal deformation of a specimen of 0.1 to 0.2 mm × 3 mm × 20 mm using a thermal stress strain measuring device (TMA) (heating rate 5 ° C.). / mi
n).

In the cosmetic of the present invention, the 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, and when the amount is more than 60% by weight, the viscosity of the cosmetic becomes high, and it becomes difficult to formulate and apply it to skin and hair.

In the cosmetic of the present invention, oils, surfactants, moisturizers, ultraviolet absorbers, chelating agents, pH generally used as cosmetic components in addition to the above essential components, as long as the effects of the present invention are not impaired. Components commonly used in cosmetics such as adjusters, preservatives, thickeners, dyes, pigments, and fragrances can be appropriately compounded. In addition, the cosmetic of the present invention is for hair and skin,
It is used in medicinal forms such as sunscreens and the like in aqueous, emulsifying and aerosol forms, but is particularly preferably used as eye makeup cosmetics such as eye shadow and mascara.

〔Example〕

Next, the present invention will be specifically described with reference to synthesis examples of an aqueous composite polymer emulsion and working examples of cosmetics, but it goes without saying that the present invention is not limited to these.

All parts and percentages in the examples are by weight unless otherwise specified.

Synthesis Example 1 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.
Dissolved oxygen was removed by flowing nitrogen gas.

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 parts of azobisisobutyronitrile were charged into a dropping funnel.

Under stirring, the temperature inside the reactor was raised to 80 ° C., and a solution of the above monomer and radical initiator in methyl ethyl ketone was dropped from the dropping funnel over 2.5 hours. Finish dropping monomer 2
After an hour, a solution of 0.2 parts of azobisisobutyronitrile in 10 parts of methyl ethyl ketone was added. After aging at the same temperature for 3 hours, a solution prepared by dissolving 0.1 part of azobisisobutyronitrile in 5 parts of methyl ethyl ketone was added again.
The reaction was continued for an hour to obtain a copolymer.

A part of the obtained copolymer was isolated, and the molecular weight was measured by gel permeation chromatography. As a result, the weight average molecular weight was 75,000. The calibration curve of gel permeation chromatography was prepared using polystyrene as a standard substance (solvent: tetrahydrofuran).

After the completion of the reaction, the copolymer solution was cooled to room temperature, 5.6 parts of triethylamine was added for neutralization, and 400 parts of ion-exchanged water was further added with stirring at 300 rpm, and then methyl ethyl ketone was distilled off at 40 ° C. under reduced pressure. The water was distilled off at 50 ° C. to obtain a water-based vinyl resin having a solid content of 25%.

In a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet tube, 200 parts of the aqueous vinyl resin and 100 parts of water
Was charged and nitrogen gas was flowed to remove dissolved oxygen.

Meanwhile, 50 parts of isobutyl methacrylate was added to the dropping funnel,
75 parts of methanol were charged.

Under stirring, the methanol solution of the monomer was dropped into the reactor over 1 hour by a dropping funnel. After the temperature in the reactor was raised to 70 ° C., a solution prepared by dissolving 0.2 part of potassium persulfate in 10 parts of water was added. Aged at the same temperature for 6 hours,
The polymerization reaction was completed. After cooling the inside of the reactor to 50 ° C., methanol and water were distilled off under reduced pressure at 50 ° C. to obtain an aqueous composite polymer emulsion having a solid content of 35%.

A part of the obtained aqueous composite polymer emulsion was dried to take out the resin, and the softening temperature of the resin was measured with a thermal stress / strain measuring device (TMA / SS-10 manufactured by Seiko Instruments Inc.). Two softening temperatures were observed at 51 ° C.
The softening temperature of the resin component of the aqueous vinyl resin alone was 22 ° C. when measured separately.

Synthesis Example 2 In the same manner as in Synthesis Example 1, methyl methacrylate 40 parts,
52 parts of ethyl acrylate, 8 parts of N, N-dimethylaminoethyl methacrylate were polymerized in methyl ethyl ketone,
A copolymer was obtained. The weight average molecular weight of this copolymer is 8
It was 2,000.

Next, 4.5 parts of lactic acid was added to the copolymer for neutralization, and the phase was inverted to water in the same manner as in Synthesis Example 1, to obtain an aqueous vinyl resin having a solid content of 25%.

In the same reactor as in Synthesis Example 1, 200 aqueous vinyl resins were added.
And 100 parts of water, nitrogen gas was flown to remove dissolved oxygen.

On the other hand, 40 parts of methyl methacrylate were charged into the dropping funnel, and the monomer was dropped into the reactor over 1 hour from the dropping funnel with stirring. After the temperature in the reactor was raised to 70 ° C., a solution prepared by dissolving 0.2 part of potassium persulfate in 10 parts of water was added. After aging at the same temperature for 6 hours, the polymerization reaction was completed. Water was 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 temperatures of the resins in the obtained aqueous composite polymer emulsion were 21 ° C and 98 ° C. The softening temperature of the resin component of the aqueous vinyl resin alone was 20 ° C.

Synthesis Example 3 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 aqueous vinyl resin synthesized in Synthesis Example 2 and 100 parts of water, and nitrogen gas was passed to dissolve the resin. Oxygen was removed.

On the other hand, 40 parts of styrene, ethanol part, 2,
0.2 part of 2'-azobis (2,4-dimethylvaleronitrile) was charged.

Under stirring, an ethanol solution of the monomer and the radical initiator was dropped into the reactor over 1 hour from a dropping funnel. The temperature in the reactor was raised to 60 ° C., and the reactor 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 temperatures of the resin in the obtained aqueous composite polymer emulsion were 19 ° C and 92 ° C.

Example 1 A cream type eye shadow having the following composition was produced by the following production method.

<Composition> Beeswax 2.5% Stearic acid 2.5 Liquid paraffin 10.0 Lanolin 1.0 Sorbitan monostearate 1.5 Glycerin 4.0% Triethanolamine 1.5 Deionized water 50.5 Methylhydroxypropylcellulose 0.5 Dibutyl phthalate 2.0 Aqueous composite polymer emulsion (Synthesis example 1) 12.0 Pearl pigment 10.0 Group Blue 2.0 Perfume Appropriate amount Preservatives Appropriate amount <Production method> Methylhydroxypropylcellulose, glycerin, and triethanolamine are dissolved in ion-exchanged water, and then heated to uniformly disperse the pearl pigment and ultramarine blue. Next, an oil phase component such as beeswax is heated and dissolved, and added to the aqueous phase while stirring to emulsify. After cooling, an aqueous composite polymer emulsion, dibutyl phthalate, a fragrance and a preservative are added to give a blue cream-type eyeshadow.

Example 2 A mascara having the following composition was produced by the following production method.

<Composition> Aqueous composite polymer emulsion (Synthesis Example 2) 50.0% Black iron oxide 15.0 Talc 10.0 Hydroxyethylcellulose 2.0 Polyoxyethylene sorbitan monooleate 1.5 Diethyl phthalate 4.0 Glycerin 5.0 Ion-exchange water 12.5 Perfume Appropriate Preservative Appropriate <Production method > Add hydroxyethylcellulose, talc, diethyl phthalate and aqueous composite polymer emulsion to ion-exchanged water, stir and mix uniformly, then add colored paste consisting of black iron oxide, glycerin, polyoxyethylene sorbitan monooleate, and mix And add flavor and preservative to give a black mascara.

Example 3 A liquid film type eyeliner having the following composition was produced by the following production method.

<Composition> Aqueous composite polymer emulsion (Synthesis example 3) 68.0% Carbon black 5.0 Titanium dioxide 2.0 Polyoxyethylene sorbitan monostearate 1.0 Glycerin 2.0 Diethyl phthalate 4.0 Hydroxyethyl cellulose 1.0 Ion-exchange water 17.0 Perfume Appropriate Preservative Appropriate Method> Polyoxyethylene sorbitan monostearate is dissolved in ion-exchanged water, and carbon black and titanium dioxide are mixed therein and uniformly dispersed using a colloid mill. Glycerin, hydroxyethylcellulose, diethyl phthalate and an aqueous composite polymer emulsion are added thereto, mixed uniformly, and finally a fragrance and a preservative are added to obtain a black film type eyeliner.

The present invention relates to eye makeup cosmetics such as other foundations, eye shadows, eyeliners, eyebrows, and mascaras, packs, lipsticks, blushers, hair coloring agents, skin cosmetics such as sunscreen agents, and hair cosmetics. It is widely applied to medicated cosmetics.

Continuation of the front page (56) References JP-A-3-133916 (JP, A) JP-A-4-103509 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) A61K 7 / 00-7/50

Claims (3)

(57) [Claims] An aqueous composite polymer emulsion wherein the polymer particles constituting the polymer emulsion have a multilayer structure composed of at least two layers having different chemical compositions, and wherein the outermost layer polymer has a lower softening temperature than the inner layer polymer. A cosmetic comprising 1 to 60% by weight in terms of solid content. 2. 0.5 to 15% by weight of a monomer having a salt-forming group and having a polymerizable double bond, and 85 to 99.5% by weight of a monomer having a polymerizable double bond copolymerizable therewith. After adding water to the organic solvent solution of the copolymer obtained by copolymerizing
Aqueous composite polymer obtained by polymerizing monomer (B) having one or more polymerizable double bonds in the presence of aqueous vinyl resin (A) obtained by distilling off organic solvent A cosmetic comprising 1 to 60% by weight of an emulsion in terms of solid content. 3. The softening temperature of the aqueous vinyl resin (A) is lower than the softening temperature of the (co) polymer of the monomer (B) having one or more polymerizable double bonds. 3. The cosmetic according to claim 2, which is low.