JP2918660B2 - 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 vinyl resin excellent in luster, water resistance, film forming properties, and the like.

[Problems to be Solved by Conventional Techniques and Inventions] Conventionally, various film-forming polymers have been used in 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]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that an aqueous vinyl resin obtained by a specific method can be suitably used as a film-forming component of cosmetics, and have reached the present invention.

That is, the present invention relates to a monomer having a salt-forming group and having a polymerizable double bond of 0.5 to 15% by weight, and a monomer having a polymerizable double bond copolymerizable with the monomer of 85 to 99.5% by weight. % Of an aqueous vinyl resin obtained by adding water to an organic solvent solution of a copolymer obtained by copolymerizing
The present invention provides a cosmetic characterized by containing 化粧 60% by weight (as solid content).

Examples of the monomer having a salt-forming group and having a polymerizable double bond used in the production of the aqueous vinyl resin of the present invention include anionic monomers, cationic monomers, and amphoteric monomers. Can be

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 oxyethyl (meth) acrylate.

As the cationic monomer, N, N-dimethylaminoethyl (meth) acrylate, (meth) acrylic acid ester having a dialkylamino group such as N, N-dimethylaminopropylacrylamide or (meth) acrylamides; N-dimethylaminostyrene, styrenes having a dialkylamino group such as N, N-dimethylaminomethylstyrene; 4-vinylpyridine, vinylpyridines such as 2-vinylpyridine, or alkyl halide, benzyl halide thereof, 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-methacryloyloxyethyl-N, N-dimethylammonium betaine and the like can be mentioned.

Examples of the monomer having a polymerizable double bond copolymerizable with the monomer having a salt-forming group and having 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-based monomers such as styrene and chlorostyrene; N-substituted (meth) such as t-butylacrylamide Acrylamide; and acrylonitrile, methacrylonitrile, and the like, and 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 salt-forming group of the copolymer is 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,
Inorganic acids such as sulfuric acid; and organic acids such as acetic acid, propionic acid, lactic acid, and glycolic acid. Examples of the base include tertiary amines such as trimethylamine and triethylamine, ammonia, sodium hydroxide and the like. There is no particular limitation on the degree of neutralization, but the pH of the obtained aqueous vinyl resin
Is preferably neutralized so as to be near neutrality.

In order to phase-convert the copolymer thus obtained to 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 water is added thereto. 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 the solution polymerization method, the solvent for polymerization can be arbitrarily selected, but it is preferable to use the above-mentioned organic solvent 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 as described above to an aqueous system can be performed by a conventionally known method, and the organic solvent solution is stirred, and water may be added at a temperature of room temperature to 80 ° C, preferably room temperature to 60 ° C. .

In the present invention, the softening temperature of the resin component of the aqueous vinyl resin can be arbitrarily set depending on the monomer composition of the copolymer, but is preferably -10 ° C or higher, more preferably 0 ° C or higher. If the softening temperature is lower than 0 ° C., the coating film becomes sticky and lacks gloss retention. On the other hand, when the softening temperature increases, the coating film tends to become brittle, but this can be solved by adding a small amount of a plasticizer and a film-forming aid.

In the cosmetic of the present invention, the aqueous vinyl resin is used as a film-forming base, and the content of the aqueous vinyl resin in the cosmetic of the present invention is 1 to 60% by weight (as solid content). desirable. 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.

The aqueous vinyl resin in the present invention is different from an aqueous emulsion polymer obtained by emulsion polymerization using an ordinary emulsifier, has a feature that it does not contain an emulsifier, and is excellent in film-forming properties and water resistance.

〔Example〕

Next, the present invention will be specifically described with reference to synthesis examples of water-based vinyl resins 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 part of azobisisobutyronitrile were charged into a dropping funnel.

Under stirring, the temperature in 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 dissolved 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 its molecular weight was measured by gel permeation chromatography. As a result, the weight average molecular weight was 72,000. The calibration curve of gel permeation chromatography was prepared using polystyrene as a standard substance.

After the completion of the reaction, the copolymer solution was cooled to room temperature, neutralized by adding 5.6 parts of triethylamine, and after adding 300 parts of ion-exchanged water with stirring at 300 rpm, 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 30%.

Synthesis Example 2 In the same manner as in Synthesis Example 1, 45 parts of methyl methacrylate,
47 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 85,0
00.

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 30%.

Synthesis Example 3 Ethyl methacrylate 50 parts in the same manner as in Synthesis Example 1
45 parts of ethyl acrylate and 5 parts of N, N-dimethylaminopropylacrylamide were polymerized to obtain a copolymer. However, isopropyl alcohol was used as a polymerization solvent instead of methyl ethyl ketone. The weight average molecular weight of this copolymer was 63,000.

Next, 2.3 parts of glycolic acid was added to the copolymer to neutralize it, and the phase was converted to water in the same manner as in Synthesis Example 1 to obtain an aqueous vinyl resin having a solid content of 30%.

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

<Composition> Microcrystalline wax 3.0% Stearic acid 3.0 Liquid paraffin 10.0 Lanolin 1.0 Sorbitan monostearate 1.5 Glycerin 4.0 Triethanolamine 1.5 Deionized water 51.5 Methylhydroxypropylcellulose 0.5% Aqueous vinyl resin (Synthesis example 1) 12.0 Pearl pigment 10.0 Ultramarine blue 2.0 Appropriate amount of fragrance Preservative Appropriate amount <Production method> Dissolve methylhydroxypropylcellulose, glycerin, and triethanolamine in ion-exchanged water, and then heat to uniformly disperse the pearl pigment and ultramarine blue. Next, an oil phase component such as microcrystalline wax is dissolved by heating and added to the aqueous phase with stirring to emulsify. After cooling, an aqueous vinyl resin, 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 vinyl resin (Synthesis Example 2) 50.0% Black iron oxide 15.0 Talc 10.0 Hydroxyethylcellulose 2.0 Polyoxyethylene sorbitan monooleate 1.5 Glycerin 5.0 Ion-exchange water 16.5 Perfume Appropriate Preservative Appropriate <Production method> Hydroxyethylcellulose in ion-exchange water After adding talc and an aqueous vinyl resin, and stirring and mixing uniformly, a colored paste composed of black iron oxide, glycerin, and polyoxyethylene sorbitan monooleate is added and uniformly mixed, and a fragrance and a preservative are added to obtain a black color. Use mascara.

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

<Composition> Aqueous vinyl resin (Synthesis Example 3) 68.0% carbon black 5.0 titanium dioxide 2.0 polyoxyethylene sorbitan monostearate 1.0 glycerin 3.0 hydroxyethylcellulose 1.0 ion-exchanged water 20.0 perfume proper amount preservative proper amount <Production method> Ethylene sorbitan monostearate is dissolved, and carbon black and titanium dioxide are mixed and uniformly dispersed using a colloid mill. Glycerin, hydroxyethylcellulose and an aqueous vinyl resin 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.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-63-108013 (JP, A) JP-A-62-281809 (JP, A) JP-A-54-151139 (JP, A) JP-A-2- 221214 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) A61K 7/00-7/50

Claims (1)

(57) [Claims] (1) 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
A cosmetic comprising 1 to 60% by weight (as solid content) of an aqueous vinyl resin obtained by distilling off an organic solvent.