Cosmetic composition formulated with an aqueous polymer emulsion

BACKGROUND OF THE INVENTION

Field of the Invention:

0001The present invention relates to aqueous polymer emulsions and more particularly to cosmetic compositions formulated therewith. The aqueous polymer emulsions provide a cosmetic composition with exceptional gloss, water-repellency, and film-forming properties.

Discussion of the Background

:

0002Conventional cosmetic compositions, such as for the hair or skin, are either water- or oil-based, and may contain a very large variety of additional ingredients. These include medicaments, abrasives, colorants, cleaners, and perfumes. To this end, see <u>Kirk-Othmer, Encyclopedia of Chemical Technology</u>, Third Edition, Vol. 7, pp. 143-176, hereby incorporated by reference.

0003A water soluble or oil soluble film-forming polymer is typically blended into cosmetic compositions. When a water soluble polymer is used, the cosmetic composition, after application thereof, is likely to be removed, e.g. by sweat, because of the poor water-resistance of the polymer. Conversely, when an oil soluble polymer is used, the cosmetic composition, after application thereof, is likely to be removed by sebum. These phenomena are known as cosmetic crumbling.

0004Various attempts have been made to overcome these problems. For instance, cosmetic compositions containing aqueous polymer emulsions have been tried. However, such conventional compositions suffer from an unsatisfactory gloss, inadequate film-forming properties, poor water-repellency, and/or storage instability (Japanese patent "kokoku" publication No. 60-9692 (Shiseido)). The development of various cosmetic compositions containing aqueous polymer emulsions which are outstanding in all of the aforementioned characteristics is therefore desired.

0005EP-A-0 424 112 relates to a nail makeup composition which contains 5 to 50 % by weight of an aqueous composite polymer emulsion. The polymer particles constituting this emulsion have a multilayered structure which is obtained by polymerizing one or more monomers (B) each having a polymerizable double bond in the presence of an aqueous vinyl polymer (A). To control the film forming properties of the polymer particles obtained thereby, it is possible to add a film forming aid or plasticizer to the composition.

0006US-4 423 031 discloses an aqueous dispersion type eye makeup preparation comprising from 20 to 50 % by weight of an aqueous emulsion on the basis of acrylate and methacrylate copolymers and, besides several auxiliaries, from 0.5 to 5 % by weight of at least one plasticizer, the balance being water.

0007US-3 763 073 discloses aqueous polymer emulsions with a solid content of 25 to 70 % produced by polymerizing monomers consisting essentially of ethylene and vinyl acetate in the presence of from 0,1 to 5 weight % based on the weight of the copolymer of a plasticizer (an ester).

Summary of the invention

0008One object of the present invention is to provide a cosmetic composition, in particular a nail enamel composition containing an aqueous polymer emulsion which has an excellent gloss, exceptional film-forming properties, avoids cosmetic crumbling and has prolonged storage stability.

0009One further object of the present invention is to provide the use of an aqueous polymer emulsion obtainable by polymerizing a monomer having a polymerizable double bond in the presence of a plasticizer or a film-forming auxiliary in a cosmetic composition, in particular in a nail enamel composition, which ensures excellent film-forming performance.

0010The foregoing and other objects, features, and advantages of the present invention will become apparent from the following detailed description and appended claims.

DETAILED DESCRIPTION OF THE INVENTION

0011According to the present invention, there is provided a cosmetic composition, in particular a nail enamel composition comprising an aqueous polymer emulsion in an amount of from 1 to 60% (as a solid content) based on the weight of the whole cosmetic composition, said

0012aqueous polymer emulsion being obtainable by polymerizing at least one monomer having a polymerizable double bond in the presence of a plasticizer or a film-forming auxiliary, being added in an amount of from 5 to 50 parts by weight per 100 parts by weight of the monomer and being selected from the group as specified in claim 1.

0013The present invention also relates to the use of the above aqueous polymer emulsion in cosmetic compositions, in particular nail enamel compositions.

0014The terminology "aqueous polymer emulsion" used herein means an emulsion including a solvent comprising water and, dispersed therein, a polymer. The polymer comprises the solid contents of the aqueous polymer emulsion. Preferably the solvent comprises at least 35% by volume water. More preferably, the solid content of the aqueous polymer emulsion is 25-65% by weight, still more preferably 35-55% by weight.

0015The monomer having a polymerizable double bond for use in the present invention may be a hydrophilic monomer or a hydrophobic monomer.

0016Representative examples of hydrophilic monomers include ethylenically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid; hydroxyl group-containing ethylenic monomers, such as hydroxyethyl acrylate, hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol monoacrylate, and polyethylene glycol monomethacrylate; ethylenic amides, such as acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide and N-diacetonacrylamide; and ethylenic amines or salts thereof, such as aminoethyl acrylate, aminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, N,N,N-trimethylaminoethyl acrylate, and N,N,N-trimethylaminoethyl methacrylate.

0017Representative examples of hydrophobic monomers include aromatic mono- or divinyl compounds, such as styrene, α-methylstyrene, chlorostyrene, alkylstyrene and divinylbenzene; acrylates and methacrylates, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, cyclohexyl acrylate and cyclohexyl methacrylate; vinyl cyanide compounds, such as acrylonitrile and methacrylonitrile; vinyl esters, such as vinyl acetate; vinyl halides, such as vinyl chloride and vinylidene chloride; ethylenically unsaturated fluoromonomers, such as trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3,4,4-hexafluorobutyl methacrylate, perfluorooctyl methacrylate and perfluorooctyl acrylate; and ethylenically unsaturated silicone macromonomers (i.e. polysilicones), such as represented by the following formulae (1),(2),(3),(4), and (5): <chemistry id="chem0001" num="0001"><img file="EP0568035B2_D0001.tif" /></chemistry><chemistry id="chem0002" num="0002"><img file="EP0568035B2_D0002.tif" /></chemistry><chemistry id="chem0003" num="0003"><img file="EP0568035B2_D0003.tif" /></chemistry><chemistry id="chem0004" num="0004"><img file="EP0568035B2_D0004.tif" /></chemistry>         CH₂=CR¹-COO-C₃H₆-Si(OX)₃     (5)

0018In the above formulae, R¹ represents a hydrogen atom or a methyl group; each of R² - R¹⁰ represents a lower alkyl group, a lower alkoxy group or a phenyl group ("lower" being C₁-C₆, preferably C₁-C₅, more preferably C₁-C₄); X represents a group of the following formula: <chemistry id="chem0005" num="0005"><img file="EP0568035B2_D0005.tif" /></chemistry> and n is an integer of from 1 to 500.

0019Only one monomer may be used, or two or more monomers may be used in combination. It is generally preferred to employ a mixture of from 0.01 to 30% of a hydrophilic monomer and from 70 to 99.99% of a hydrophobic monomer, and more preferred to employ a mixture of from 0.01 to 15% of a hydrophilic monomer and from 85 to 99.99% of a hydrophobic monomer.

0020The plasticizers or film-forming auxiliaries suitable for use in the present invention include cellosolve, methyl cellosolve and butyl cellosolve; carbitol, dimethylcarbitol, diethylcarbitol, butylcarbitol and dibutylcarbitol; as ethylene carbonate and propylene carbonate; cellosolve acetate, butyl cellosolve acetate, butylcarbitol acetate and sucrose acetate; hexanol, benzyl alcohol and phenethyl alcohol; hexylene glycol, ethylene glycol and propylene glycol; phthalic diesters, adipic diesters, succinic diesters, sebacic diesters, abietic esters, caprylic esters, caproic esters, acetic esters, enanthic esters, myristic esters and citric esters; sucrose benzoate; and diethylbenzene.

0021The plasticizer or film-forming auxiliary is added in an amount of from 5 to 50 parts by weight, preferably from 5 to 30 parts by weight, per 100 parts by weight of the monomer from the viewpoint of polymerization stability, storage stability, and water repellency and durability of a produced film.

0022The aqueous polymer emulsion for use in the present invention is obtainable by polymerizing the monomer in the presence of the plasticizer or film-forming auxiliary as defined above. According to desired use, the plasticizer or film-forming auxiliary may further be added to the produced aqueous polymer emulsion, i.e., the percent solids content may be adjusted in this manner or by addition of solvent. The solid content may also be adjusted by removal of solids, e.g., when the polymer is produced by emulsion polymerization.

0023In the polymerization, a polymerization initiator is generally added. The polymerization initiator is not particularly limited, and includes for example, organic polymerization initiators inclusive of hydroperoxides, such as cumene hydroperoxide, diisopropylbenzene hydroperoxide and paramenthane hydroperoxide; peroxides, such as benzoyl peroxide and lauroyl peroxide; and azo compounds, such as azobisisobutylonitrile, and inorganic polymerization initiators inclusive of persulfates, such as potassium persulfate, sodium persulfate and ammonium persulfate. Moreover, a redox polymerization initiator may be used in combination with a reducing agent, such as sodium bisulfite, ascorbic acid and salts thereof.

0024In the polymerization, further, a surfactant is preferably added for ensuring dispersion stability.

0025The surfactant for use in the present invention is not particularly limited, and includes anionic, cationic and nonionic surfactants. These surfactants may be used in combination. For example, a mixture of an anionic surfactant and a nonionic surfactant or a mixture of a cationic surfactant and a nonionic surfactant may be used in the present invention.

0026Representative examples of nonionic surfactants include polyethylene oxide alkyl ethers, polyethylene oxide alkylphenyl ethers and polyethylene oxide - polypropylene oxide block copolymers. Representative examples of anionic surfactants include alkylbenzene sulfonates, alkylnaphthalene sulfonates and polyethylene oxide alkyl ether sulfates. Representative examples of cationic surfactants include primary, secondary and tertiary amine salts and quaternary ammonium salts having an aliphatic hydrocarbon residue.

0027The surfactant is preferably added in an amount of up to 5 parts by weight, more preferably up to 3 parts by weight per 100 parts by weight of the monomer. When the amount of added surfactant exceeds 5 parts by weight, film properties and film adhesion are likely to become poor.

0028In the polymerization of the monomer, a chain transfer agent may be added. Representative examples of chain transfer agents include mercaptans, such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan and t-tetradecyl mercaptan; xanthogen disulfides, such as dimethylxanthogen disulfide, diethylxanthogen disulfide and diisopropylxanthogen disulfide; thiuram disulfides, such as tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetrabutylthiuram disulfide; halogenated hydrocarbons, such as carbon tetrachloride and ethylene bromide; hydrocarbons, such as pentaphenylethane; unsaturated cyclic hydrocarbon compounds, such as acrolein, methacrolein, allyl alcohol, 2-ethylhexyl thioglycolate, turbinolene, α-terpinene, gamma-terpinene, dipentene, a-methylstyrene dimer (preferably containing at least 50 parts by weight of 2-4-diphenyl-4-methyl-1-pentene), 9,10-dihydroanthracene, 1,4-dihydronaphthalene, indene and 1,4-cyclohexadiene; and unsaturated heterocyclic compounds, such as xanthene and 2,5-dihydrofuran. These may be used either alone, or in combination.

0029In the present invention, the polymerization of the monomer is conducted according to the conventional polymerization techniques, such as emulsion polymerization, solution polymerization, bulk polymerization, precipitation polymerization or soap-free polymerization. The solid content of the aqueous polymer emulsion can then be adjusted in the manner previously mentioned.

0030The polymer of the aqueous polymer emulsion produced by the above described polymerization preferably has a weight average molecular weight of 10,000 to 200,000, more preferably in the range of from 10,000 to 100,000, even more preferably 20,000 to 80,000, still more preferably 25,000-60,000.

0031Either only one aqueous polymer emulsion or two or more aqueous polymer emulsions may be blended into the cosmetic composition of the present invention. When two or more aqueous polymer emulsions are blended into the cosmetic composition, the blending may be effected so as to combine two or more polymers respectively having different glass transition temperatures or different average molecular weight.

0032The aqueous polymer emulsion is blended as a film-forming base material into the cosmetic composition of the present invention in an amount of from 1 to 60% by weight (below referred to simply as "%") relative to the weight of the whole cosmetic composition, in terms of the weight of solid contents. When the amount is less than 1%, the effect of the present invention cannot be attained. On the other hand, when the amount exceeds 60%, the viscosity of the cosmetic composition is so high that it becomes difficult to prepare cosmetics and apply the resultant cosmetics to the skin and hair.

0033In addition to the above components, other components generally used as a cosmetic component, such as an oil, a humectant, an ultraviolet absorbing agent, a chelating agent, a pH control agent, an antiseptic, a thickener, a dye, a pigment and a perfume, may be blended into the cosmetic composition of the present invention, as long as the effect of the present invention is not adversely affected. The cosmetic composition of the present invention can be formulated into various cosmetic forms according to conventional methods. See, generally, <u>Kirk-Othmer</u>, ibid., for useful additives and cosmetic forms.

0034As a humectant, use is made of, for example, ethylene glycol, diethylene glycol, triethylene glycol and polyethylene glycols higher than tri; propylene glycol, dipropylene glycol and polypropylene glycols higher than tri; butylene glycols such as 1,3-butylene glycol and 1,4-butylene glycol; polyglycerols such as glycerol, diglycerol and polyglycerols higher than di; sugaralcols such as sorbitol, mannitol, xylitol and maltitol; ethylene oxide (hereinafter referred to as EO) and propylene oxide (hereinafter referred to as PO) adducts of glycerols; EO and PO adducts of sugaralcohols; monosaccharides such as galactose and fructose, and their EO and PO adducts; polysaccharides such as maltose and lactose, and their EO and PO adducts; sodium pyrrolidone carboxylate, polyoxyethylene methyl glucosides (mols of added EO = 10, 20, etc.), basic amino acids and urea. These humentants provide the skin with moistness when incorporated in amounts of 0.01 to 30%, and especially 0.1 to 10%.

0035As a pigment, use is made of an organic pigment, such as 12120, 73360, 74160 and 11680 (Color Index, CI), or an inorganic pigment, such as titanium dioxide, brown iron oxide, red iron oxide, mica titanium and bismuth oxychloride.

0036A dispersant for such a pigment may also be incorporated in the cosmetic composition of the present invention, which includes an anionic surfactant, such as soap, zinc laurate, zinc myristate, magnesium myristate, zinc palmitate, magnesium stearate, zinc stearate, aluminum stearate, calcium stearate, sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium cetyl sulfate, triethanolamine polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, polyoxyethylene lauryl ether phosphoric acid, sodium polyoxyethylene lauryl ether phosphate, polyoxyethylene cetyl ether phosphoric acid, sodium polyoxyethylene cetyl ether phosphate, polyoxyethylene stearyl ether phosphoric acid, polyoxyethylene oleyl ether phosphoric acid, sodium polyoxyethylene oleyl ether phosphate, polyoxyethylene alkylphenyl ether phosphoric acid, triethanolamine polyoxyethylene alkylphenyl ether phosphate, sodium polyoxyethylene alkylphenyl ether phosphate, lauroylsarcosine sodium salt and soybean phospholipid. Further, the pigment dispersant includes a cationic surfactant, such as stearyltrimethylammonium chloride, distearyldimethylammonium chloride, benzalkonium chloride, benzethonium chloride, stearyldimethylbenzylammonium chloride, cetylpyridinium chloride, alkylisoquinolinium bromide and domiphene bromide.

0037Still further, the pigment dispersant may include an amphoteric surfactant, such as sodium β-laurylaminopropionate, betaine lauryldimethylaminosulfate and 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine.

0038The pigment dispersant may also include a nonionic surfactant, such as self-emulsifiable glycerol monostearate, lipophilic glycerol monostearate, lipophilic glycerol monooleate, ethylene glycol monostearate, propylene glycol monostearate, propylene glycol dioleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, sucrose fatty acid esters, undecylenic acid monoethanolamide, lauric acid diethanolamide, coconut oil fatty acid diethanolamide, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, myristyl lactate, cetyl lactate, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene stearic acid amide, polyoxyethylene glycerol monostearate, polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitan monolaurate (20EO), polyoxyethylene sorbitan monopalmitate (20EO), polyoxyethylene sorbitan monostearate (6EO), polyoxyethylene sorbitan monostearate (20EO), polyoxyethylene sorbitol hexastearate, polyoxyethylene sorbitan monooleate (20EO), polyoxyethylene sorbitan trioleate (20EO), polyoxyethylene sorbitol tetraoleate, polyoxyethylene sorbitol beeswax, polyoxyethylene castor oil, polyoxyethylene hardened castor oil and polyoxyethylene lanolin.

0039As the thickener, use is made of an organic thickener, such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyethylene oxide, methyl cellulose, hydroxyethyl cellulose, cationated guar gum and cationated cellulose, an inorganic bentonite thickener and a water-containing oxide, such as boehmite.

0040A cosmetic composition formulated with the aqueous emulsion of the present invention, after application thereof to the skin and hair, exhibits exceptional gloss, excellent film stability, water repellency, and film-forming properties, and is not flowed or removed by sweat or sebum, that is, is free from cosmetic crumbling.

0041By virtue of these advantages, the cosmetic composition of the present invention finds wide applications in various foundations, makeup cosmetics (such as eye shadow, eyeliner, eyebrow pencil, mascara and nail enamel), skin cosmetics (such as pack, lipstick, rouge and sun screen), hair cosmetics, medical cosmetics and the like.

0042Among them, especially preferred are nail enamels, mascaras, eye shadows, foundations and packs.

0043In the manufacture of nail enamels or mascaras, it is preferred to incorporate the aqueous polymer emulsion in amounts (as a solid content) from 1 to 60 wt%, preferably from 10 to 50 wt%, and particularly from 30 to 50 wt% based on the total weight of the composition, and the humectant in amounts from 0.01 to 10 wt%, preferably 0.1 to 5 wt% based on the total weight of the composition.

0044In the manufacture of foundations or eye shadows, it is preferred to incorporate the aqueous polymer emulsion in amounts (as a solid content) from 1 to 30 wt%, preferably from 1 to 15 wt% based on the total weight of the composition, and the humectant in amounts from 0.01 to 30 wt%, preferably 0.1 to 10 wt% based on the total weight of the composition.

0045In the manufacture of packs, it is preferred to incorporate the aqueous polymer emulsion in amounts (as a solid content) from 20 to 50 wt%, preferably from 30 to 40 wt% based on the total weight of the composition, and the humectant in amounts from 0.01 to 10 wt%, preferably 0.5 to 10 wt% based on the total weight of the composition.

PREFERRED EMBODIMENTS OF THE INVENTION

0046Having generally described this invention, a further understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only and are not intended to be limiting unless otherwise specified.

Emulsion Examples (Production of aqueous polymer emulsions)

0047Hereinbelow, "parts" means "parts by weight", and "%" means "% by weight".

Emulsion Example 1

0048A reactor is equipped with an agitator, a reflux condenser, a dropping funnel, a thermometer and a nitrogen introduction tube. 150 parts of water, 3 parts of sodium lauryl sulfate and 0.5 part of potassium persulfate are charged into the reactor. Nitrogen gas is passed through the contents of the reactor to remove any oxygen dissolved in the contents. Then, 78 parts of styrene, 22 parts of 2-ethylhexyl acrylate, 10 parts of butylcarbitol acetate and 2.0 parts of n-dodecyl mercaptan are put in the dropping funnel.

0049The temperature of the reactor is elevated to 70°C, and the monomer-containing contents of the dropping funnel are added dropwise, with stirring, over a period of 3 hours. After the dropwise addition, the resultant reaction mixture is aged for 3 hours. Thereafter, some aggregates are removed to obtain an emulsion having a solid content of 45%.

0050The thus obtained emulsion contained a copolymer, which had a glass transition temperature (Tg) of 52°C as measured using DSC and had a weight average molecular weight (Mw) of 28,000 as measured by GPC (reference: polystyrene).

00514 parts of dibutyl phthalate was added to 100 parts of the above emulsion, and agitated for 30 minutes by means of a disperser, thereby obtaining an aqueous polymer emulsion (1) having a solid content of 43%.

Emulsion Example 2

0052Charged into the reactor as used in Example 1 are 150 parts of water, 3.0 parts of polyoxyethylene nonylphenyl ether, 0.5 part of potassium persulfate, 98 parts of isobutyl methacrylate, 2 parts of hydroxyethyl methacrylate, 10 parts of acetyltriethyl citrate, 13 parts of carbitol and 2.5 parts of n-dodecyl mercaptan. Nitrogen gas is then passed through the contents of the reactor to remove any oxygen dissolved in the contents.

0053The temperature of the contents of the reactor is elevated to 70°C with stirring, and polymerization is performed over a period of 3 hours. The resultant reaction mixture is aged for 3 hours at the same temperature. Thereafter, some aggregates are removed to obtain an aqueous polymer emulsion (2) having a solid content of 44%.

0054The thus obtained aqueous polymer emulsion is subjected to the same measurements as in Example 1. The emulsion contained a copolymer, with a glass transition temperature (Tg) of 60°C and a weight average molecular weight (Mw) of 32,000.

Emulsion Example 3

0055Charged into the reactor as used in Referential Example 1 are 150 parts of water, 2.0 parts of sodium dodecylbenzenesulfonate, 0.5 part of ammonium persulfate, 55 parts of methyl methacrylate, 33 parts of n-butyl acrylate, 10 parts of styrene, 2 parts of acrylic acid, 5 parts of dibutyl phthalate and 2.5 parts of n-dodecyl mercaptan. Nitrogen gas is passed through the contents of the reactor to remove any oxygen dissolved in the contents.

0056The temperature of the contents of the reactor is elevated to 70°C with stirring, and polymerization is performed over a period of 3 hours. The resultant reaction mixture is aged for 3 hours at the same temperature. Thereafter, some aggregates are removed to obtain an emulsion having a solid content of 41%.

0057The thus obtained emulsion is subjected to the same measurements as in Example 1. The emulsion contained a copolymer, with a glass transition temperature (Tg) of 30°C and a weight average molecular weight (Mw) of 28,000.

005815 parts of butyl cellosolve is added to 100 parts of the above emulsion, and agitated for 30 minutes by means of a disperser, thereby obtaining an aqueous polymer emulsion (3) having a solid content of 36%.

Emulsion Example 4

0059Charged into the reactor as used in Referential Example 1 are 150 parts of water, 0.5 part of sodium polyoxyethylene lauryl ether sulfate, 0.5 part of potassium persulfate, 63 parts of methyl methacrylate, 21 parts of 2-ethylhexyl acrylate, 10.0 parts of styrene, 3 parts of hydroxyethyl methacrylate, 3 parts of acrylic acid, 10 parts of diisobutyl adipate and 2.5 parts of n-dodecyl mercaptan.

0060The mixture is then treated as in Example 3.

0061After the resultant reaction mixture is aged for 3 hours at the same temperature, some aggregates are removed to obtain an emulsion having a solid content of 46%.

0062The thus obtained emulsion is subjected to the same measurements as in Example 1. The emulsion contained a copolymer, having a glass transition temperature (Tg) of 52°C and a weight average molecular weight (Mw) of 32,000.

006315 parts of diethylcarbitol is added to 100 parts of the above emulsion, and agitated for 30 minutes by means of a disperser, thereby obtaining an aqueous polymer emulsion (4) having a solid content of 40%.

Emulsion Example 5

0064Charged into the reactor as used in Referential Example 1 are 150 parts of water, 0.5 part of sodium polyoxyethylene lauryl ether sulfate, 0.5 part of ammonium persulfate, 60 parts of methyl methacrylate, 25 parts of 2-ethylhexyl acrylate, 10.0 parts of styrene, 3 parts of hydroxyethyl methacrylate, 2 parts of acrylic acid, 10 parts of diisobutyl adipate and 2.5 parts of n-dodecyl mercaptan.

0065The mixture is treated as in Example 3.

0066After the resultant reaction mixture is aged for 3 hours at the same temperature, some aggregates are removed to obtain an emulsion having a solid content of 45%.

0067The thus obtained emulsion is subjected to the same measurements as in Example 1. The emulsion contained a copolymer, having a glass transition temperature (Tg) of 45°C and a weight average molecular weight (Mw) of 32,000.

006820 parts of dimethylcarbitol is added to 100 parts of the above emulsion, and agitated for 30 minutes by means of a disperser, thereby obtaining an aqueous polymer emulsion (5) having a solid content of 37.5%.

Emulsion Example 6

0069Charged into the reactor as used in Referential Example 1 are 125 parts of water, 3.0 parts of sodium lauryl sulfate, 0.5 part of ammonium persulfate, 73 parts of styrene, 27 parts of 2-ethylhexyl acrylate, 7.0 parts of dibutyl phthalate, 15 parts of butyl cellosolve, and 1.0 part of butyl mercaptan.

0070The mixture is treated as in Example 3.

0071After the resultant reaction mixture is aged for 3 hours at the same temperature, some aggregates are removed to obtain an aqueous polymer emulsion (6) having a solid content of 47%.

0072The thus obtained aqueous polymer emulsion is subjected to the same measurements as in Example 1. The emulsion contained a copolymer, having a glass transition temperature (Tg) of 40°C and a weight average molecular weight (Mw) of 57,000.

Emulsion Example 7 (Comparative)

0073Charged into the reactor as used in Referential Example 1 are 125 parts of water, 3.0 parts of sodium lauryl sulfate, 0.5 part of ammonium persulfate, 73 parts of styrene, 27 parts of 2-ethylhexyl acrylate, and 1.0 part of butyl mercaptan.

0074The mixture is treated as in Example 3.

0075After the resultant reaction mixture is aged for 3 hours at the same temperature, some aggregates were removed to obtain an emulsion having a solid content of 47%.

0076The thus obtained emulsion is subjected to the same measurements as in Example 1. The emulsion contained a copolymer, having a glass transition temperature (Tg) of 40°C and a weight average molecular weight (Mw) of 57,000.

0077Dibutyl phthalate and butyl cellosolve are then added to the above emulsion in amounts of 7 parts and 15 parts, respectively, per 100 parts of the monomer contained in the emulsion, and agitated for 30 minutes by means of a disperser, thereby obtaining an aqueous polymer emulsion (7) having a solid content of 42.6 %.

Cosmetic Example 1 (eye shadow)

0078An eye shadow of the following formulation is prepared by the below described procedure.

Formulation:

0079<tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Component</entry><entry namest="col2" nameend="col2" align="center">Parts by weight</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">microcrystalline wax</entry><entry namest="col2" nameend="col2" align="center">3.0</entry></row><row><entry namest="col1" nameend="col1" align="left">stearic acid</entry><entry namest="col2" nameend="col2" align="center">3.0</entry></row><row><entry namest="col1" nameend="col1" align="left">liquid paraffin</entry><entry namest="col2" nameend="col2" align="center">8.5</entry></row><row><entry namest="col1" nameend="col1" align="left">lanolin</entry><entry namest="col2" nameend="col2" align="center">1.0</entry></row><row><entry namest="col1" nameend="col1" align="left">sorbitan monostearate</entry><entry namest="col2" nameend="col2" align="center">1.5</entry></row><row><entry namest="col1" nameend="col1" align="left">glycerol</entry><entry namest="col2" nameend="col2" align="center">5.5</entry></row><row><entry namest="col1" nameend="col1" align="left">triethanolamine</entry><entry namest="col2" nameend="col2" align="center">1.5</entry></row><row><entry namest="col1" nameend="col1" align="left">methyl cellulose</entry><entry namest="col2" nameend="col2" align="center">0.5</entry></row><row><entry namest="col1" nameend="col1" align="left">aqueous polymer emulsion (1)</entry><entry namest="col2" nameend="col2" align="center">10.0</entry></row><row><entry namest="col1" nameend="col1" align="left">pearl pigment</entry><entry namest="col2" nameend="col2" align="center">10.0</entry></row><row><entry namest="col1" nameend="col1" align="left">ultramarine blue</entry><entry namest="col2" nameend="col2" align="center">2.0</entry></row><row><entry namest="col1" nameend="col1" align="left">ion exchange water</entry><entry namest="col2" nameend="col2" align="center">balance</entry></row><row><entry namest="col1" nameend="col1" align="left">perfume</entry><entry namest="col2" nameend="col2" align="center">trace</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">antiseptic</entry><entry namest="col2" nameend="col2" align="center">trace</entry></row></tbody></tgroup></table></tables>

Procedure:

0080Methyl cellulose, glycerol and triethanolamine are dissolved in ion exchange water, and heated. Subsequently, pearl pigment and ultramarine blue are uniformly dispersed in the solution, thereby obtaining an aqueous phase dispersion. Then, oil phase components including microcrystalline wax are heated so as to obtain a solution, and this solution is added to the above aqueous phase dispersion under agitation to effect emulsification. The resultant emulsion is cooled, and the aqueous polymer emulsion (1), perfume and antiseptic are added to the cooled emulsion. Thus, a blue creamy eye shadow is obtained.

0081The thus obtained eye shadow exhibited excellent gloss and water (sweat) repellency.

Cosmetic Example 2 (mascara)

0082A mascara of the following formulation is prepared by the below described procedure.

Formulation:

0083<tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Component</entry><entry namest="col2" nameend="col2" align="center">Parts by weight</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">aqueous polymer emulsion (2)</entry><entry namest="col2" nameend="col2" align="center">45.0</entry></row><row><entry namest="col1" nameend="col1" align="left">black iron oxide</entry><entry namest="col2" nameend="col2" align="center">15.0</entry></row><row><entry namest="col1" nameend="col1" align="left">talc</entry><entry namest="col2" nameend="col2" align="center">10.0</entry></row><row><entry namest="col1" nameend="col1" align="left">methyl hydroxypropyl cellulose</entry><entry namest="col2" nameend="col2" align="center">2.0</entry></row><row><entry namest="col1" nameend="col1" align="left">polyoxyethylene sorbitan monooleate</entry><entry namest="col2" nameend="col2" align="center">1.5</entry></row><row><entry namest="col1" nameend="col1" align="left">glycerol</entry><entry namest="col2" nameend="col2" align="center">5.0</entry></row><row><entry namest="col1" nameend="col1" align="left">ion exchange water</entry><entry namest="col2" nameend="col2" align="center">balance</entry></row><row><entry namest="col1" nameend="col1" align="left">perfume</entry><entry namest="col2" nameend="col2" align="center">trace</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">antiseptic</entry><entry namest="col2" nameend="col2" align="center">trace</entry></row></tbody></tgroup></table></tables>

Procedure:

0084Methyl hydroxypropyl cellulose, talc and aqueous polymer emulsion (2) are added to ion exchange water, and uniformly blended under agitation. Subsequently, a color paste comprised of black iron oxide, glycerol and polyoxyethylene sorbitan monooleate is added, and uniformly blended. Further, the perfume and antiseptic are added to obtain a black mascara.

0085The thus obtained mascara exhibited excellent gloss and water (sweat) repellency.

Cosmetic Example 3 (eyeliner)

0086A liquid, film-forming type eyeliner of the following formulation was prepared by the below described procedure.

Formulation:

0087<tables id="tabl0003" num="0003"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Component</entry><entry namest="col2" nameend="col2" align="center">Parts by weight</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">aqueous polymer emulsion (3)</entry><entry namest="col2" nameend="col2" align="center">58.0</entry></row><row><entry namest="col1" nameend="col1" align="left">carbon black</entry><entry namest="col2" nameend="col2" align="center">6.0</entry></row><row><entry namest="col1" nameend="col1" align="left">titanium dioxide</entry><entry namest="col2" nameend="col2" align="center">3.0</entry></row><row><entry namest="col1" nameend="col1" align="left">polyoxyethylene sorbitan monostearate</entry><entry namest="col2" nameend="col2" align="center">1.0</entry></row><row><entry namest="col1" nameend="col1" align="left">glycerol</entry><entry namest="col2" nameend="col2" align="center">3.0</entry></row><row><entry namest="col1" nameend="col1" align="left">methyl cellulose</entry><entry namest="col2" nameend="col2" align="center">1.0</entry></row><row><entry namest="col1" nameend="col1" align="left">ion exchange water</entry><entry namest="col2" nameend="col2" align="center">balance</entry></row><row><entry namest="col1" nameend="col1" align="left">perfume</entry><entry namest="col2" nameend="col2" align="center">trace</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">antiseptic</entry><entry namest="col2" nameend="col2" align="center">trace</entry></row></tbody></tgroup></table></tables>

Procedure:

0088Polyoxyethylene sorbitan monostearate is dissolved in ion exchange water to obtain a solution. Carbon black and titanium oxide are blended into the solution, and uniformly dispersed by the use of a colloid mill. Glycerol, methyl cellulose and aqueous polymer emulsion (3) are added to the dispersion, and uniformly blended. Finally, the perfume and antiseptic are added, thereby obtaining a black, film-forming type eyeliner.

0089The thus obtained eyeliner exhibited excellent gloss and water (sweat) repellency.

Cosmetic Examples 4 - 6 and Comparative Cosmetic Example 1 (nail enamel)

0090Nail enamels of the formulations shown in Table 1 are prepared according to the following procedure.

Procedure:

0091The pigment is dispersed in ion exchange water, and then, aqueous polymer emulsions (4) - (7) and other components are added to the dispersion. The resultant mixture is uniformly blended under agitation, and degassed, thereby obtaining an aqueous nail enamel.

0092The thus obtained nail enamels are evaluated with respect to (a) adhesion, (b) water repellency and (c) abrasion resistance according to the following methods and criteria:

Evaluation Method

(a) Adhesion

0093The nail enamel is applied to the nail with a nailbrush or the like under the conditions such that the ambient temperature and relative humidity were 25°C and 60%, respectively, and dried to obtain a film on the surface of the nail. 30 minutes later, the film is scraped with a microspatula, and the scraping degree (resistance to scraping) is visually inspected.

(b) Water repellency

0094The nail enamel is uniformly applied to a nylon plate of 0.5 x 15 x 40 mm with a nail enamel brush, and dried for one hour under the conditions such that the ambient temperature and relative humidity were 25°C and 60%, respectively, thereby obtaining a film on the surface of the plate. Subsequently, the film-containing plate is immersed in water of 35°C for one hour, and the degradation degree (resistance to degradation, e.g., clouding, swelling, softening, peeling, etc.) of the film is visually checked.

(c) Abrasion resistance

0095The above-mentioned 30 min. dried film is rubbed with a cotton cloth 50 times, and the degree of abrasion (resistance to abrasion) is visually inspected.

0096The evaluation results are also shown in Table 1. <tables id="tabl0004" num="0004"><img file="EP0568035B2_D0006.tif" /></tables>

0097As apparent from the results of Table 1, the cosmetic compositions according to the present invention are superior to the comparative cosmetic composition.

Cosmetic Example 7:

(Creamy foundation)

0098Ingredients (1) to (4) were blended, to which ingredient (5) was added for dispersion, and while stirring, a mixture of ingredients (6) to (9) was slowly added thereto for emulsification to obtain a creamy foundation. <tables id="tabl0005" num="0005"><img file="EP0568035B2_D0007.tif" /></tables>

Cosmetic Example 8:

(Facial pack)

0099A facial pack having the following formulation was prepared. <tables id="tabl0006" num="0006"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Aqueous polymer emulsion (2)</entry><entry namest="col2" nameend="col2" align="center">70 wt%</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyethylene glycol 4000</entry><entry namest="col2" nameend="col2" align="center">2</entry></row><row><entry namest="col1" nameend="col1" align="left">polyoxyethylene methylglucoside (20 EO adduct)¹⁾</entry><entry namest="col2" nameend="col2" align="center">3</entry></row><row><entry namest="col1" nameend="col1" align="left">Xanthan gum</entry><entry namest="col2" nameend="col2" align="center">0.5</entry></row><row><entry namest="col1" nameend="col1" align="left">Squalane</entry><entry namest="col2" nameend="col2" align="center">3</entry></row><row><entry namest="col1" nameend="col1" align="left">Ethanol</entry><entry namest="col2" nameend="col2" align="center">7.7</entry></row><row><entry namest="col1" nameend="col1" align="left">Perfume</entry><entry namest="col2" nameend="col2" align="center">0.5</entry></row><row><entry namest="col1" nameend="col1" align="left">Preservative</entry><entry namest="col2" nameend="col2" align="center">suitable amount</entry></row><row><entry namest="col1" nameend="col1" align="left">Sorbitan monostearate²⁾</entry><entry namest="col2" nameend="col2" align="center">0.5</entry></row><row><entry namest="col1" nameend="col1" align="left">polyoxyethylene sorbitan monostearate³⁾ (20 EO adduct)</entry><entry namest="col2" nameend="col2" align="center">0.2</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Water</entry><entry namest="col2" nameend="col2" align="center">balance</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Total</entry><entry namest="col2" nameend="col2" align="center">100 wt%</entry></row></tbody></tgroup><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col2" align="justify">note: 1) GlucamE-20® (product of Amerchol Corp.)</entry></row><row><entry namest="col1" nameend="col2" align="justify">2) Rheodol SPS10® (product of Kao Corporation)</entry></row><row><entry namest="col1" nameend="col2" align="justify">3) Rheodol TWS120® (product of Kao Corporation)</entry></row></tbody></tgroup></table></tables>