EP1204400A2

EP1204400A2 - Aqueous cosmetic composition

Info

Publication number: EP1204400A2
Application number: EP00965885A
Authority: EP
Inventors: Helmut Witteler; Axel Sanner; Bernhard Schlarb
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1999-08-19
Filing date: 2000-08-18
Publication date: 2002-05-15
Also published as: DE19939326A1; JP2003507399A; WO2001013863A3; WO2001013863A2; CN1374850A

Abstract

Disclosed is an aqueous cosmetic composition containing and emulsion polymer with a minimum temperature of film formation MFT that is determined in the absence of film forming auxiliaries and with at least one glass transition temperature Tg of the dried film, whereby 35 DEG C </= Tg </= 80 DEG C and Tg - MFT >/= 8 DEG C. The composition is especially a nail varnish or a hair fixative formulation.

Description

aqueous cosmetic composition

description

The present invention relates to an aqueous cosmetic composition, in particular in the form of a nail varnish or a hair setting formulation.

Nail care products, especially in the form of nail polishes, are among the most used decorative cosmetics. They usually contain a synthetic resin as a film former as well as inorganic or organic pigments or dyes. The nail polishes should have a high gloss, high hardness and good adhesion to substances containing keratin, such as fingernails, and should dry quickly at room temperature to form a non-sticky, uniform film. The high gloss and good adhesion should be maintained for as long as possible. In order for the nail polishes to be removed again with conventional nail polish removers, the film-forming resins used must be soluble in water-acetone mixtures. On the other hand, the film-forming resins should be insoluble in water or water-alcohol mixtures so that the nail polish does not dissolve when it comes into contact with water or when handling common household chemicals.

Nail varnishes with aqueous emulsion polymers are increasingly being used as binders. For example, EP-0424112 describes nail polish formulations which contain an emulsion polymer with a core / shell structure as a binder. The outer shell polymer has a softening temperature that is lower than that of the inner shell polymer. However, it has been shown that the nail polish compositions described therein have inadequate adhesion to substrates containing keratin, e.g. B. on fingernails, show and quickly lose their shine after drying.

DE-19727504 discloses aqueous cosmetic formulations, in particular nail polish formulations, which contain, as binders, an emulsion polymer which can be obtained by polymerizing a mixture of certain monomers in the presence of a polymer containing an ionic or ionogenic group. The formulations described have one sufficient adhesion to fingernails, but are not completely satisfactory when used as nail polish. The painted surfaces quickly lose their shine and disadvantageously show a sticky sensory impression.

The object of the invention is therefore to provide an aqueous cosmetic composition, in particular a water-based nail polish, which after drying leads to films with good adhesion to substrates containing keratin in particular, high gloss and high gloss retention and freedom from tack.

According to the invention, this object is achieved by an aqueous cosmetic composition which contains an emulsion polymer having a minimum film-forming temperature MFT determined in the absence of film-forming aids and at least one glass transition temperature T _{g of} the dried film, where

35 ° C <T _g <80 ° C and

T _g - MFT> 8 ° C.

This rule must apply to at least one glass transition temperature if the polymer has more than one glass transition temperature.

In preferred embodiments

40 ° C <T _g <65 ° C.

In preferred embodiments is also

T _g - MFT> 12 ° C,

preferably

T _g - MFT> 16 ° C,

particularly preferred

T _g - MFT> 18 ° C.

The emulsion polymer used according to the invention is characterized by its minimum film formation temperature, determined in the absence of film-forming aids, and the glass transition temperatures of the film which is obtained after drying. The minimum film-forming temperature is the limit temperature above which a plastic dispersion will dry during drying under a crack-free film. The minimum film formation temperature is determined under the conditions specified in DIN 53787. At the start of the measurement, the emulsion polymer has a solids content of 30 to 55% by weight. For the purposes of the present invention, the mean value from 10 independently carried out determinations is used as MFT. The determination is made in the absence of film-forming aids or coalescing or leveling agents, ie the specific MFT is an intrinsic property of the emulsion polymer under investigation. Of course, the formulated cosmetic composition can contain such auxiliary agents if desired.

The T _g is determined using a commercially available DSC calorimeter with a heating rate of 20 ° C on a film, which is applied by applying the emulsion in a dry film thickness of 100 μm to glass and drying at 23 ° C and 50% humidity is obtained.

In order to ensure reliable filming at body temperature and below, the person skilled in the art would have considered only emulsion polymers with a T _g of significantly less than 35 ° C. Surprisingly, it was found that the use of emulsion polymers which meet the above criteria as binders in z. B. nail polish formulations leads to products which show a good flow and good filming properties even at low temperatures, but after drying lead to films with high gloss retention, high hardness and without a sticky sensory impression.

In preferred embodiments of the cosmetic composition according to the invention, the emulsion polymer has a maximum particle size distribution in the range from 50 to 200 nm, preferably 80 to 150 nm. The particle size distribution is the plot of the total volume of all particles in a class against the particle diameter. Emulsion polymers with the specified particle size distribution lead to films with particularly high gloss and high gloss retention.

Emulsion polymers that can be used are obtained by polymerizing ethylenically unsaturated compounds (monomers) in a two-phase system with water as the continuous phase. A water-soluble initiator system is usually used to initiate the polymerization. In general, the aqueous phase contains emulsifiers and / or protective colloids. By suitable selection of the monomer composition and the amount and type of emulsifiers and / or protective colloids used, emulsion polymers are obtained whose MFT and T _g meet the conditions set out above.

Monomers that can be used are e.g. B. -C-C ₃ o-alkyl (meth) acrylates, vinyl esters, vinyl aromatics and mixtures thereof. Preferred monomers are discussed below in connection with preferred aspects of the invention. Suitable protective colloids are hydrophilic polymers and copolymers, such as polyvinyl alcohols, polyacrylic acids, polyacrylamides, polyvinyl pyrrolidones, sulfonate-containing polyesters, sulfonate-containing polyamides, sulfonate-containing polyurethanes, carboxylate-containing PES, PA, PUR, sulfonate- or carboxylate-containing polyester amides. Hydrophilic protective colloids with ionic or ionogenic groups are preferred.

Particularly suitable emulsion polymers contain styrene and preferably at least one monomer selected from methyl methacrylate, n-butyl (meth) acrylate and tert-butyl (meth) acrylate and preferably at least one monomer selected from acrylic acid, methacrylic acid and crotonic acid.

In preferred embodiments, the emulsion polymer contains at least 2% by weight, preferably 2 to 50% by weight, in particular 3 to 25% by weight, based on the total monomer units, of units of a monomer of the formula I,

wherein R ¹ and R ² independently of one another represent a hydrogen atom or a methyl group and R ^{3 represents} C ₉ -C ₃₀ alkyl, in particular C ₁₂ -C ₂₂ alkyl. The radical R ³ can stand for branched, cyclic or linear alkyl, with linear alkyl being preferred.

Preferred examples of monomers of the formula I are esters of (meth) acrylic acid with C ₁₂ -C ₂₂ alcohols, such as lauryl acrylate, stearyl acrylate, lauryl methacrylate, stearyl methacrylate, esters of methyl methacrylic acid with C ₂ -C ₂₂ alcohols and also esters crotonic acid with C ₁₂ -C ₂₂ alcohols, of which lauryl acrylate, stearyl acrylate, lauryl methacrylate and / or stearyl methacrylate are particularly preferred. In preferred emulsion polymers, the total proportion of styrene units and units of monomers of the formula I, based on the total monomer units, is 15 to 80% by weight, in particular 30 to 60% by weight.

The emulsion polymer is preferably a multi-stage emulsion polymer which has at least one first polymer domain and at least one second polymer domain, the first polymer domain being composed of

5 to 50 parts by weight, preferably 8 to 30 parts by weight, of monomer units with at least one ionic or ionogenic group,

50 to 95 parts by weight, preferably 70 to 92 parts by weight, of neutral monomer units

and the second polymer domain is essentially composed of neutral monomer units.

The preferred emulsion polymer is multi-stage, i. H. it has two or more polymer domains. It can be obtained by emulsion polymerization of a monomer or monomer mixture constituting a higher polymer domain in the presence of the polymer of the preceding stage. A two-stage emulsion polymer is thus prepared by emulsion polymerizing a monomer mixture constituting the second polymer domain in the presence of a polymer consisting of the first polymer domain. The latter generally acts as a protective coloid in emulsion polymerization. The terms "first" and "second" polymer domains are introduced for ease of reference for the purposes of the present description. In the case of three- or multi-stage emulsion polymers, no particular arrangement of these domains relative to other domains is implied.

The first polymer domain is composed of 5 to 50 parts by weight of monomer units with at least one ionic or ionogenic group and 50 to 95 parts by weight of neutral monomer units. Monomer units with ionic or ionogenic groups are those which are derived from acidic or anionic, basic or cationic or amphoteric monomers. Ionic groups have a full ion charge or a multiple thereof. Ionogenic monomers can be converted into ionic groups by protonation / deprotonation or quaternization.

Anionic and cationic monomers can also be present simultaneously in the first polymer domain, it being possible for the two monomer types to be equimolar or one of the two monomer types to be present in a molar excess, so that the polymer thus produced is anionic or cationic to the outside. This can e.g. B. be useful if one of the two types of monomers brings about an additional advantage, such as improved adhesion or dispersion stability.

Anionic or acidic monomers are e.g. B. ethylenically unsaturated mono- or dicarboxylic acids, preferably with 3 to 6 carbon atoms, and polymerizable or copolymerizable acidic carboxylic acid derivatives, such as (meth) acrylic acid, crotonic acid, maleic acid and their anhydrides and half esters, fumaric acid and -haibester, itaconic acid; unsaturated sulfonic acid derivatives, such as styrene sulfonic acid, vinyl sulfonic acid, 2-acrylamido-2-methyl-propanesulfonic acid or their salts; unsaturated phosphorus or phosphonic acid derivatives, such as vinylphosphonic acid or the phosphoric acid monoesters of polymerizable alcohols, such as, for. B. Butanediol monoacrylate or hydroxyethyl methacrylate.

Ethylenically unsaturated mono- or dicarboxylic acids, such as acrylic acid, methacrylic acid and crotonic acid, are preferred anionic or acid monomers. These can advantageously be completely or partially neutralized.

Cationic or basic monomers are e.g. B. (meth) acrylic acid esters or amides of amino alcohols or diamines such as dialkylaminoalkyl (meth) acrylates or - (meth) acrylamides such as N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminopropylacrylamide, dialkylaminostyrenes, such as, for. B. N, N-dimethylaminostyrene and N, N-dimethylaminomethylstyrene, vinyl pyridines such as 4-vinylpyridine and 2-vinylpyridine, 1-vinylimidazole, and further compounds by reacting the above-mentioned basic monomers with known quaternizing reagents, such as alkyl halides, Benzyl halides, dialkyl sulfates, etc. can be produced. Examples of amphoteric monomers are N- (3-sulfopropyl) -N-meth-acryloyloxyethyl-N, N-dimethylammonium betaine and N-carboxymethyl-N-methacryloyloxyethyl-N, N-dimethylammonium betaine.

Acid groups or tertiary amino groups can be converted into ionic groups by salt formation or quaternization reaction.

Neutral monomer units derive from neutral monomers, i.e. H. Monomers without ionic or ionogenic groups. The neutral monomers also include the monomers of the formula I. The emulsion polymer generally contains further neutral monomers, which can advantageously be divided into main monomers and different monomers (comonomers).

As preferred main monomers z. B.

Cι-C ₈ alkyl (meth) acrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate; Vinyl esters of Ci-Cig-alkane carboxylic acids, in particular Ci-Cg-alkane carboxylic acids, such as vinyl acetate, vinyl propionate, vinyl laurate, vinyl stearate, vinyl neodecanoate;

Vinyl aromatics, such as preferably styrene, α- and β-methylstyrene, α-butylstyrene, 4-butylstyrene, 4-decylstyrene; or cite mixtures thereof.

Aliphatic olefins having 2 to 8 carbon atoms and one or two olefinic double bonds, such as butadiene, isoprene and chloroprene, and also ethylene, propylene and isobutylene can also be mentioned. Aliphatic olefins with two double bonds are less preferred main monomers.

Particularly preferred main monomers are styrene, methyl methacrylate, n-butyl (meth) acrylate and / or tert-butyl (meth) acrylate.

Suitable comonomers are e.g. B. hydroxyl-containing monomers such as hydroxyalkyl (meth) acrylates, e.g. B. hydroxypropyl or hydroxyethyl (meth) acrylate, amides or substituted amides of ethylenically unsaturated mono- or dicarboxylic acids, for. B. acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, and the etherified with Ci-Cβ-monohydric alcohols N-methylolacrylamides and N-methylolmethacrylamides. Crosslinking monomers, e.g. B. with two vinyl groups can also be used, preferably these are used in the second polymer domain. Nitriles and vinyl halides should also be mentioned. Examples of nitriles are acrylonitrile and methacrylonitrile. The vinyl halides are chlorine, fluorine or bromine-substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.

The second polymer domain is predominantly made up of neutral monomer units. It is preferably composed of 60 to 100 parts by weight of units of the main monomers mentioned above and 0 to 40 parts by weight of units of different monomers. The proportion of ionic monomer units is preferably below 5%.

In a preferred emulsion polymer, the first polymer domain is composed of

5 to 40 parts by weight of monomer units with at least one ionic or ionogenic group, 2 to 50 parts by weight, preferably 10 to 30 parts by weight, units of monomers of the formula I,

10 to 93 parts by weight, preferably 40 to 85 parts by weight, units of Ci-Cβ-Alkylfmethjacrylaten, vinyl esters of Ci-Cig-alkane carboxylic acids, vinyl aromatics or mixtures thereof, and - 0 to 40 parts by weight of units of which various monomers,

and the second polymer domain built up from

- 60 to 100 parts by weight of units of Cx-Cg-alkyl (meth) acrylates, vinyl esters of Ci-Cig-carboxylic acids, vinyl aromatics or mixtures thereof, and 0 to 40 parts by weight of units of different monomers.

The weight ratio of the first polymer domain to the second polymer domain is preferably in the range from 10:90 to 60:40, in particular 30:70 to 50:50.

The weight average molecular weight (M _w ) of the polymer forming the first polymer domain is preferably above 10,000, particularly preferably from 20,000 to 200,000 (determined by gel permeation chromatography, using polystyrene as standard and tetrahydrofuran as eluent). The polymer which forms the first polymer domain can be prepared by any polymerization process, but preferably by solution polymerization.

Suitable solvents for the solution polymerization of the first polymer domain are, for. B. those with a boiling point below 100 ° C at 1 bar or those that form an azeotrope with water, which, if desired, can be easily separated by distillation from the aqueous polymer dispersion or polymer solution. In individual cases, leveling agents can also advantageously be added to the solvent. A later addition of these tools can be superfluous.

Examples of solvents include. B. alcohols or ketones with up to 8 carbon atoms, such as butanol, isobutanol, propanol, ethanol, methanol and methyl ethyl ketone.

The polymerization of the ethylenically unsaturated monomers can e.g. B. in a known manner by anionic or preferably radical polymerization, preferably in the presence of initiators. As radical initiators are z. B. azobiscarboxamides, azobiscarbonsitriles, peracid esters or peroxides. The amount of the initiator is preferably 0.2 to 5% by weight, particularly preferably 0.5 to 3% by weight, based on the monomers. The polymerization temperature is preferably 50 to 150 ° C, particularly preferably 70 to 130 ° C. Optionally, regulators, for. B. mercaptoethanol, tertiary dodecylmercapane, ethylhexylthioglycolate or diisopropylxanthogen sulfide, preferably in amounts of 0 to 3 wt .-%, based on the monomers, are added.

The polymer forming the first polymer domain can be prepared in one or more stages. In particular, e.g. B. first a polymer with a high acid content and in the presence of which then a polymer with a lower acid content can be produced, as described for. B. is described in EP-A-320865. In the present invention, the multi-stage production usually brings no further advantages, so that the one-stage production is preferred. During the polymerization, the monomers can be initially introduced or, preferably, metered in continuously.

The polymer forming the first polymer domain is obtained as a dispersion or preferably solution in the organic solvent. The solids content is preferably 50 to 95% by weight, in particular 60 to 85% by weight. In the presence of the polymer forming the first polymer domain, the emulsion polymerization is then carried out to produce the multistage emulsion polymer. The emulsion polymerization can be carried out in the usual manner, for. B. at temperatures of 30 to 95 ° C in the presence of a water-soluble initiator. Suitable initiators are e.g. As sodium, potassium and ammonium persulfate, tert-butyl hydroperoxide, water-soluble azo compounds or redox initiator systems. When using hydrogen peroxide as initiator, small amounts of heavy metal salts, such as Cu (II) or Fe (III) salts, are preferably used.

For this purpose, the polymer forming the first polymer domain can be placed in water or another aqueous medium and / or added to the water together with monomers to be polymerized during the emulsion polymerization. In a preferred production method, water is added to the solution of the polymer and then the organic solvent used for its production is predominantly distilled off. The aqueous solution or dispersion of the first polymer domain obtained in this way is used in the production of the second polymer domain by emulsion polymerization.

If the first polymer domain comprises acid groups or anhydride groups, some or preferably all of these are converted into salt groups before or during the transfer into the aqueous phase, ie. H. neutralized.

Suitable neutralizing agents are on the one hand mineral bases such as sodium carbonate or potassium carbonate and ammonia, on the other hand organic bases such as amino alcohols, e.g. B. 2-amino-2-methyl-1-propanol (AMP), triethanolamine, triisopropanolamine (TIPA), monoethanolamine, diethanolamine, tri [(2-hydroxy) -l-propyl] amine, 2-amino-2- methyl-1,3-propanediol (AMPD) or 2-amino-2-hydroxymethyl-1,3-propanediol and diamines, such as lysine.

In emulsion polymerization, in addition to the polymer forming the first polymer domain, no further emulsifiers, protective colloids or other dispersing aids are generally required; however, these can be added.

In a particularly preferred embodiment, auxiliaries which reduce the viscosity are added during and after the emulsion polymerization. These are preferably ionic compounds, in particular salts, which are derived from organic acids or bases. Examples include lysine hydrochloride and sodium citrate. The aqueous cosmetic compositions according to the invention can be in a variety of forms, e.g. B. as cosmetic emulsions, lotions, body lotions, hand lotions, ointments, creams, gels, make-ups, anti-wrinkle creams, lotions and ointments, solubilisates, oils, bath oils, shampoos, soaps, liquid soaps, washing creams, washing gels, shower gels, cleaning preparations Cleansing milk, skin protection formulations, hand protection creams and ointments, occupational protection creams and ointments, sticks, lipsticks, deodorant sticks, deodorants, mascara, eyeshadow, nail varnishes, watery nail varnishes, sun protection formulations, UV protection formulations, sun protection creams, sun protection gels, after sun pre-pares Shaving foams, shaving creams and lotions, after-shave preparations, hygiene formulations and rinses, mouthwash, toothpastes and medicinal skin preparations. Preferred embodiments of the cosmetic composition according to the invention relate to hair cosmetic formulations, hair care products and hair setting agents, in particular hair sprays, setting lotions, setting cream, foam setting agents, hair mousse, hair gel, agents for treating dandruff and hair loss, and hair restoration agents. A particularly preferred embodiment of the cosmetic composition according to the invention is a water-based nail polish.

The aqueous cosmetic composition according to the invention preferably contains less than 10% by weight of volatile organic substances. “Volatile organic substances” are understood to mean those with a boiling point below 300 ° C. Such substances can serve as leveling agents, for example.

The emulsion polymer defined at the outset can be present in the aqueous cosmetic composition as the sole polymer or in a mixture with other polymers. By mixing with other polymers, the solubility or redispersibility in water or aqueous media can be controlled. Especially in applications that require water solubility or redispersibility in water, such as. B. in hair cosmetic formulations, such as hair setting formulations, the emulsion polymer according to the invention can be mixed with a water-soluble or water-redispersible polymer. Examples of suitable water-soluble polymers are ionic polyamides, polyurethanes and polyesters and homopolymers and copolymers of ethylenically unsaturated monomers. Cosmetic ingredients are known, for example, under the trade names Amerhold, Ultrahold, Ultrahold Strong, Luviflex VBM, Luvimer, Luviskol, Luviskol Plus, Luviset PUR, Acronal, Acudyne, Stepanhold, Lovocryl, Versatyl, Amphomer or Eastman AQ. Some of these polymers will be water soluble or redispersible only with the help of suitable neutralizing agents.

The water-soluble polymer can be used in any amount, e.g. B. up to 95 wt .-%, based on the sum of the polymers used. Surprisingly, even with small amounts of water-soluble polymer in a mixture with the emulsion polymer defined at the outset, a mixture redispersible in water is obtained.

The aqueous cosmetic compositions according to the invention can contain further constituents, e.g. B. colorants such as pigments or dyes, surfactants, dispersants, wetting agents, thickeners, hair conditioners, humectants, leveling agents, preservatives, antifoams, chelating agents, buffers and UV absorbers. The selection of suitable components of this type for the respective application is within the scope of the expert knowledge in the cosmetic field.

The pigments or dyes used should be relatively lightfast and not leak. Pearlescent substances such as mica (mica), guanine, bismuth oxychloride or titanium dioxide on mica can also be used. Many examples of suitable pigments and dyes can be found in Madison G. de Navarre, The Chemistry and Manufacture of Cosmetics, Vol. 4, pp. 996-998 (2nd ed.). Further suitable colorants are described in DE-4240743A, DE-19538700A, DE-19614637A, DE-19640619A, DE-19705960A, DE-19705962A, DE-19715995A, DE-19802234A, EP-0686674A, US-4009136, US-4487855, US-4612343 and US-5131916.

Surfactants or dispersants or wetting agents are often used as surface-active agents in nail coating preparations in order to support the uniform distribution of the pigment. Inorganic pigments are usually hydrophilic and can be easily dispersed in an aqueous emulsion system. Organic pigments are generally hydrophobic and sometimes require a dispersing or wetting agent that reduces the surface tension and enables an even distribution. A list of suitable surface-active agents can be found in Encyclopedia of Chemical Technology, Surfactants, Vol. 19, p. 584 (1969), and the choice to be made in each case lies within the specialist knowledge and ability. Particularly suitable surfactants are alkoxylated silicones, which can be added during or after the preparation of the emulsion polymer. Thickeners are used to prevent separation and sedimentation. Suitable thickeners are, for example, natural gums, such as guar, gum arabic, cellulose and cellulose derivatives, silicates, such as V-gum ^(R) , clays, such as stearalkonium hectorite, and synthetic polymers, such as acrylates, e.g. B. Carbopol ^(R) and Acrys- sols < ^R) .

Suitable hair conditioning agents are known under the CTFA name "Polyquaternium".

As a humectant such. B. mono- and polyglycols, mono- and polyglycerols, sugar alcohols, alkylene oxides and polyalkylene oxides, in particular ethylene and propylene oxides (EO and PO), saccharides, glucosides, amino acids, urea and adducts of EO or PO with the compounds mentioned. The humectants transfer moisture to the skin and are generally used in amounts of 0.01 to 30% by weight, preferably 0.1 to 10% by weight, based on the cosmetic composition.

Leveling agents can be added to lower the temperature at which the film can form. The leveling agents therefore only serve a purpose during film formation. These are usually organic substances with a boiling point between 30 and 300 ° C.

A group of suitable leveling agents includes the glycol ethers, such as ethylene glycol aminobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether. Other suitable leveling agents are ethylene glycol butyl ether acetate, propylene glycol butyl ether, ethyl 3-ethoxypropionate, 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol, 1,2-propylene glycol 1-monomethyl ether, ethyl acetate and toluene. Trade names of leveling agents based on these substances are Dowanol PnB, Eastman EEPS and Solvenon PM.

Preservatives are frequently used to prevent bacterial and fungal growth during the storage of the nail coating preparations. Commonly used preservatives, e.g. B. lower alkyl esters of p-hydroxybenzoic acid, such as methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, butyl p-hydroxybenzoate and hexyl p-hydroxybenzoate, 5-chloro-2-methyl-3- (2H ) -isothiazolon, 2-methyl-3- (2H) -isothiazolone, organic salts, such as potassium sorbate, inorganic salts, such as mercury salts, and formaldehyde and formaldehyde-releasing compounds. Suitable anti-foaming agents can be used to prevent foaming and blistering during manufacture and application to the nails. Examples of suitable antifoam agents are organopolysiloxanes and substituted organopolysiloxanes, such as methyl silicone and diethyl silicone, silicon dioxide, mixtures of silicon and silicon dioxide, and of organopolysiloxanes and silicon dioxide and polyoxyethylene-polyoxypropylene condensates.

Chelating agents remove heavy metal ions that can affect the stability of nail polishes. Suitable chelating agents are ethylenediaminetetraacetic acid (EDTA) and its mono- and tetrasodium salt and tetrasodium pyrophosphate.

If necessary, the nail polish formulation is buffered so that the pH is preferably between 6 and 10.

UV absorbers serve to prevent harmful effects of UV rays on the polymer, fading of the pigment or dye and brittleness of the nail coating film. A list of suitable UV absorbers can be found in Encyclopedia of Chemical Technology, UV Absorbers, Vol. 21, pp. 115-122 (1969).

The cosmetic composition is preferably present in the cosmetic composition in amounts of 0.5 to 70% by weight, preferably 20 to 65% by weight, particularly preferably 25 to 50% by weight, calculated as a solid resin, based on the total weight of the cosmetic composition. If the amount used is less than 0.5%, the effect of the present invention cannot be obtained.

The dispersion of the emulsion polymer contains little coagulum and has fine disperse particles.

After filming, the aqueous cosmetic compositions, in particular nail polish compositions, are no longer soluble in water / ethanol mixtures (EtOH: 0 to 50% by weight), have good film-forming properties, good gloss and in particular good adhesion to keratin containing substrates, e.g. B. fingernails.

A nail polish formulation according to the invention usually contains one or more ingredients which are known to the person skilled in the art under the following CTFA names: Acetyl Tributyl Citrate, Acetyl Triethyl Citrate, Acrylates Copolyπter, Alcohol, Alcohol Denat., Aluminum Powder, Amyl Acetate, Apricot (Prunus Armeniaca) Kernel Oil, Benzophenone-1, Benzophenone-3, Bismuth Oxychloride, Butyl Acetate, n-Butyl Alcohol, Calcium Pantothenate, Camphor, Carmine, Cellulose Acetate Butyrate, Citric Acid, D&C Red No. 6, D&C Red No. 6 Barium Lake, D&C Red No. 7, D&C Red No. 7 Calcium Lake, D&C Red No. 17, D&C Red No. 30, D&C Red No. 30 Lake, D&C Red No. 33, D&C Red No. 34, D&C Red No. 34 Calcium Lake, D&C Violet No. 2, D&C Yellow No. 5 Aluminum Lake, D&C Yellow No. 5 Zirconium Lake, Diacetone Alcohol, Dibutyl Phthalate, Diglycerin, Diisobutyl Adipate, Dimethicone, Dimethiconol, Dimethicone Copolyol and its Derivatives, Amodimethicone and its Derivatives, Dioleyl Tocopheryl Methylsilanol, Drometrizole, Ethyl Acetate, Etocrylene, F 1, FD&C Blue No. 1 Aluminum Lake, FD&C Yellow No. 5, FD&C Yellow No. 5 Aluminum Lake, Ferric Ammonium Ferrocyanide, Ferric Ferrocyanide, Formaldehyde, Gelatin, Glycerin, Guanine, Heptane, Hydrolyzed Keratin, Iron Oxides, Isobutyl Acetate, Isopropyl Alcohol, Isostearoyl Hydrolyzed Collagen, Malic Acid, Methoxyisopropanol, Methylparaben, Mica, Nitrocellulose Phosphoric Acid, Phthalic Anhydride / Glycerin / Glycidyl Decanoate Copolymer, Phthalic Anhydride / Trimellitic Anhydride / Glycols Copolymer, Polyvinyl Alcohol, Polyvinyl Butyral, PPG-8 Polyglyceryl-2 Ether, Propyl Acetate, Propylene Glycol, Propylparaben, SD Alcohol 40, SD Alcohol 40 -B, Silica, Silver, Stearalkonium Bentonite, Stearalkonium Hectorite, Stearyl Glycyrrhetinate, Styrene / Acrylates / Acrylonitrile Copolymer, Styrene / Acrylates Copolymer, Sucrose Acetate Isobutyrate, Sucrose Benzoate, Tin Oxide, Titanium Dioxide, Tocopheryl Acetate, Tocyl Toluene, Tocopheryl Tolene / Epoxy Resin, Tosylamide / Formaldehyde Resin, Water, Zinc Myristate.

The following examples illustrate the invention. In the examples, all percentages are by weight.

Examples

Examples 1A, 1B, IC, 1D; Comparative Example IV:

Preparation of the polymer forming the first polymer domain by solution polymerization

In a glass flask equipped with a reflux condenser, anchor stirrer, dropping funnels and thermostatted oil bath, the template specified below is placed in a nitrogen atmosphere. ter stirring heated to 85 ° C. After the temperature has been reached, feed 2 indicated below is started and metered in over 5 hours. 15 minutes after the start of feed 2, feed 1 indicated below is started and metered in within 3.5 hours. The polymer solution is then cooled to 80 ° C. and neutralized with feed 3 within 30 minutes. Then stirring is continued for 30 min. The polymer solution is then dispersed by stirring feed 4 within 1 hour. A distillate is then removed at an internal flask temperature of up to 100 ° C. The compositions and characteristics are given in Table 1.

Table 1

The K value (also Fikentscher constant) is calculated from the solution viscosity of polymers and is explained in the specialist literature, for example by H.-G. Elias, Macromolecules, Vol. 1, Hüthig & Wepf, Heidelberg 1990, pp. 98 f. Examples 2A, 2B, 2C; Comparative Example 2:

Production of the multistage polymer by emulsion polymerization of a monomer mixture in the presence of the polymer forming the first polymer domain

The template is heated to 85 ° C. with stirring in a nitrogen atmosphere. Feed 1 is metered in in 10 minutes. After 85 ° C is reached, 20% of feed 3 are added. Feed 2 is then metered in in 2 hours and the rest of feed 3 in 2.5 hours. The mixture is then stirred at 85 ° C for 1 hour and then cooled to room temperature. The compositions and characteristics are given in Table 2.

Table 2:

1

To measure the glass transition temperature T _g , the sample is heated from room temperature to 120 ° C, then cooled to -60 ° C and then heated again to 120 ° C. When heating up

The glass transition temperature is measured at -60 ° C to 120 ° C. All heating and cooling processes are carried out at a rate of 20 ° C / min.

The particle size distribution was determined with a photon correlation spectroscope, model Autosicer 2c from Malvern Instruments. With this device, the total volume of all particles in a class is plotted against the particle diameter; that's the particle size distribution.

r

example

Probande

The poly ditives ent

28.25%

0.57% 2.43%

2.83%

65.92% This na nes test paintwork is, we dried underwent

Table 3: Test of the nail polish formulations

++ exceeds the requirements + meets the requirements does not meet the requirements

¹ commercially available water-based nail polish, binder containing acrylate

² commercially available water-based nail polish, binder containing polyurethane

Examples 4 to 17

formulations

With the following formulations, cosmetic preparations are obtained which meet the requirements for the particular application in a particular degree.

Example 4, hairspray

Polymer dispersion from Example 2B 3 g

Water ad 100 g

Mirapol 550 (CAS No. 26590-05-6) 3 g propylene glycol 2 g

Alkamuls EL 719 (trademark from Rhodia,

CAS-No. 61791-12-6) 2 g

Gluadin AGP (trademark from Henkel, hydrolyzed

Wheat protein, CAS no. 70084-87-6) 2 g Mirasil DMCO (trademark from Rhodia,

CAS-No. 64365-23-7) 0.5 g

Preservative q. s.

Perfume oil q. s.

Dye q. s.

Example 5, sunscreen gel

Polymer dispersion from Example 2B 1. .2 g) 1

Water ad f 30. 4 g Carbopol 980 (trademark from B.F. Goodrich, CTFA name Carbomer) 1. .2 g

Ethanol, 98%, denatured 4. .0 g

Uvinul MS 40 (BASF) 3. , 0 g

2-amino-2- (hydroxymethyl) -1, 3-propanediol 4. , 0 g Trilon B liquid (from BASF, tetrasodium EDTA solution) 0.3 g

Aloe vera gel concentrate, 10: 1 0. .5 g

D-panthenol 0. .5 g

Perfume oil 0. .2 g bisabolol 0,. 1 g

Cremophor A 25 (trademark from BASF,

CTFA name Ceteareth-25) 1.2 g

¹ Quantity based on solid resin Example 6, sunscreen spray

Cyclomethicone DC 345 (trademark from Dow Corning, cyclic oligodimethylsiloxane) 55.60 polysynlanes (trademark from Polyesther,

CAS-No. 61693-08-1) 8.00 g polymer dispersion from Example 2B, spray-dried, 50% in abs. Ethanol disperses 3 g sunflower oil 3.50 g vitamin E acetate 0.25 g Tenox 6 (from Eastman Chemical,

Mixture of corn oil, glyceryl oleate, propylene glycol,

Phenol derivatives, propyl gallate, citric acid) 0.15 g fragrance 0.50 g

Diisopropyl adipate 5.00 g

Octyl methoxycinnamate 7.50 g

Oxybenzone (CAS No. 131-57-7) 4.00 g

Octylsalicylate 5.00 g ethoxy diglycol (CAS No. 111-90-0) 7.50 g

Example 7, After-Sun Moisture Spray

Polymer dispersion from Example 2B 1.00 gl ¹ deionized water ad 84.60 g

Luviquat mono CP (trademark from BASF, CTFA name

Hydroxyethyl cetyldimonium phosphate) 2.00 g

D-panthenol 0.50 g

Propylene glycol 5.00 g Silicones DC 190 (trademark from Dow Corning, CTFA name Dimethicone Copolyol Acetate) 0.50 g Prodew 200 (trademark from Ajinomoto,

Mixture of sodium lactate, pyrrolidone carboxylic acid sodium salt, sorbitol, hydrolyzed collagen, proline) 2.00 g

Dimethyloldimethylhydantoin (CAS No. 6440-58-0) 0.50 g Cremophor RH 40 (trademark from BASF,

CAS-No. 61788-85-0) 0.30 g

Fragrance 0.10 g ¹ Quantity based on solid resin

Example 8, lipstick

Candelilla (Euphorbia cerifera) wax (CAS No. 8006-44-8) 4.75 g

Beeswax 1.20 g

Ozokerite 7.20 g Polymer from Example 2B 1.00 g

Microcrystalline Wax SP 96 (trademark from Strahl &

Pitsch, CAS no. 63231-60-7) 7.00 g Abil Wax 2440 (trademark from Goldschmidt, CTFA name Behenoxy Dimethicone) 3.40 g

Isopropyl alcoholate 3.40 g

Lanolin 5.75 g

Isostearyl behenate 2.30 g Cetiol LC (trademark from Henkel, CTFA name Coco-caprylate / caprate) 12.45 g

Limnanthes alba seed oil 15.4 g

Myristyl myristate 7.60 g PPG-2 myristyl ether propionate (CAS No. 74775-06-7) 9.55 g Micapoly UV Shadow (from Centerchem, mixture of mica, titanium dioxide, cyclomethicone, dimethiconol, isododecane, ethylene-vinyl acetate)

Copolymer, iron oxide) 3.00 g

Lanolin 4.00 g

Perfluorodecalin (CAS No. 306-94-5) 3.00 g pigments q.s.

Example 9, Hair Pomade

Petrolatum (CAS No. 8009-03-8) 66.2 g polymer dispersion from Example 2B 0.8 g Schercemol DID (trademark from Scher Chemicals,

Diisopropyldilinoleates) 20.0 g of Schercemol BE (from Scher Chemicals,

Beuca erucate, CAS-No. 18312-32-8) 9.0 g cetyl alcohol 4.2 g

Propylparaben 0.1 g

Perfume oil 0.5 g

Dyes q.s.

Example 10, hair mascara

composed of components A, B, C, D

Component A

Crodafos CES (trademark from Croda, mixture of cetearyl alcohol, dicetyl phosphate, ceteth-10 phosphate) 4.00 g Volpo S-2 (trademark from Croda, CTFA name

Steareth-2) 0.50 g Volpo S-10 (trademark from Croda, CTFA name

Steareth-10) 1.00 g

Beeswax 6.50 g Carnauba wax 1.25 g polychol 5 (from Croda,

CTFA name Laneth-5) 0.50 g

Stearyl alcohol 1.00 g

Component B

Polymer dispersion from Example 2B 3.00 g) 1

Water ad 57.81 g polyvinylpyrrolidone K-30 1.00 g Natrolsol 250 HHR (from Aqualon,

Hydroxethyl cellulose) 0.10 g

Potassium hydroxide 0.19 g

Na ₂ EDTA 0.10 g Colorona Bordeaux (trademark from Rona / E. Merck,

Mixture of mica and iron oxides) 12.00 g

Propylene glycol 6.00 g

Component C

Hydrotriticum PVP (trademark from Croda, copolymer from

PVP and hydrolyzed wheat protein) 4.00 g

Potassium hydroxide 0.05 g

Component D

Germaben II (watermark from Sutton, mixture of

Propylene glycol, diazolidinyl urea, methyl urea, methyl paraben and propyl paraben) 1.00 g ^l based on solid resin

Example 11, aqueous hair spray

Ultrahold Strong (trademark from BASF, copolymer of acrylic acid, ethyl acrylate, N-tert-butylacrylamide) 4 g) 1

Luvimer 100 P (trademark from BASF, copolymer of ethyl acrylate, tert-butyl acrylate and methacrylic acid) 0.5 g

Polymer dispersion from Example 2B 3.5 g) 1

2-Amino-2-methyl-l-propanol ad pH 9 water ad 100 g

Perfume oil q. s.

¹ Quantity based on solid resin

Example 12, Predominantly Alcoholic Hair Spray

Luvimer 100 P (trademark from BASF, copolymer of ethyl acrylate, tert-butyl acrylate and methacrylic acid) 3 g Polymer dispersion from Example 2B lg

2-amino-2-methyl-l-propanol 0.7 g

Ethanol ad 50 g

Propane / butane ad 100 g perfume oil q. s.

Example 13 Hairspray (Polymer Combination)

Polymer dispersion from Example 2B 1 g Luviskol VA 37 (trademark from BASF, copolymer from

Vinyl pyrrolidone and vinyl acetate) 8 g

Water 5.5 g

Ethanol ad 37.5 g

Dimethyl ether ad 100 g of perfume oil q. s.

Example 14, care foam

Polymer dispersion from Example 2B 1.5 g) 1 Luviflex Soft (trademark from BASF, copolymer from

Methacrylic acid and ethyl acrylate) 4 g

2-amino-2-methyl-l-propanol 2.0 g Cremophor A 25 (trademark from BASF,

CTFA name Ceteareth-25) 0.2 g Luviquat Mono CP (trademark from BASF, CTFA name

Hydroxyethyl cetyldimonium phosphate) 0.5 g

Perfume oil q. s.

Preservatives q. s.

Water ad 90 g propane / butane ad 100 g ¹ Quantity based on solid resin

Example 15, aqueous nail polish

Polymer dispersion from Example 2B 36 g) 1

Isopropanol 5.5 g

Propylene glycol monomethyl ether 8.5 g Rouge Covasorb W 3768 (trademark from Wackherr,

CAS-No. 2379-74-0) 0.5 g Silicones DC 556 (trademark from Dow Corning,

CTFA name Phenyl Trimethicone) 0.2 g

Methyl paraben q. s.

Propyl paraben q. s.

Perfume oil qs ^x Quantity based on solid resin Example 16 Nail Polish (Polymer Blend)

Polymer dispersion from Example 2B 24 g

Gantrez ES-435 (trademark from ISP, copolymer of vinyl methyl ether and maleic acid dibutyl ester,

50% ethanolic solution) 24 g) 1

Castor oil 2 g

Ethanol 47.5 g

Diethyl phthalate 2 g 9,10-anthracenedione (CAS No. 81-48-1) 0.5 g

Perfume oil qs ¹ Quantity based on solid resin

Example 17, Nail Polish (Polymer Mixture)

Polymer dispersion from Example 2B 36 g

Antaron WP-660 (trademark from ISP, copolymer from

Vinylyrrolidone and C ₃₀ olefin) 12 g

Castor oil 2 g ethanol 47.5 g

Diethyl phthalate 2 g

9,10-anthracenedione (CAS No. 81-48-1) 0.5 g

Perfume oil q. s.

Claims

claims

1. Aqueous cosmetic composition containing an emulsion polymer with a minimum film-forming temperature MFT determined in the absence of film-forming aids and at least one glass transition temperature T _{g of} the dried film, where

35 ° C <T _g <80 ° C and

T _g - MFT> 8 ° C.

2. The composition of claim 1, wherein the maximum of the particle size distribution of the emulsion polymer in the range of

50 to 200 nm.

3. The composition according to claim 1 or 2, wherein the emulsion polymer contains at least 2% by weight of units of a monomer of the formula I,

where R ¹ and R ² independently represent a hydrogen atom or a methyl group and R ^{3 represents} Cg-C ₃ o-alkyl.

4. The composition of claim 3, wherein the monomer of formula I is lauryl acrylate, stearyl acrylate, lauryl methacrylate and / or stearyl methacrylate.

5. Composition according to one of the preceding claims, wherein the emulsion polymer is a multi-stage emulsion polymer which has at least one first polymer domain and at least one second polymer domain, the first polymer domain being composed of

5 to 50 parts by weight of monomer units with at least one ionic or ionogenic group and

50 to 95 parts by weight of neutral monomer units and the second polymer domain is essentially composed of neutral monomer units.

6. The composition of claim 5, wherein the monomers with 5 ionic or ionogenic group are ethylenically unsaturated mono- or dicarboxylic acids.

7. The composition of claim 6, wherein the carboxylic acid groups are completely or partially neutralized. 0

8. The composition according to any one of claims 5 to 7, wherein the first polymer domain is composed of

5 to 40 parts by weight of monomer units with at least one ionic or ionogenic group,

2 to 50 parts by weight of units of monomers of the formula I 0-10 to 93 parts by weight of units of C 1 -C ₈ -alkyl (meth) acrylates, vinyl esters of C 1 -C 4 -alkane carboxylic acids, vinyl aromatics or mixtures thereof, and

0 to 40 parts by weight of units of different monomers,

and the second polymer domain is constructed from

60 to 100 parts by weight of units of C ₁ -C ₈ -alkyl (meth) - 30 acrylates, vinyl esters of Cx-Cig-carboxylic acids, vinyl aromatics or mixtures thereof, and

0 to 40 parts by weight of units of different monomers. 35

9. The composition according to any one of claims 5 to 8, wherein the weight ratio of the first polymer domain to the second polymer domain is in the range of 10:90 to 60:40.

40 10. Composition according to one of the preceding claims, which contains 20 to 90 wt .-% water.

11. The composition according to any one of the preceding claims, which contains at least one additive consisting of colorants, 45 surfactants, dispersants, wetting agents, thickeners, hair conditioning agents, humectants, leveling agents, preservatives, antifoams, chela- tising agents, buffers, UV absorbers, film-forming polymers and mixtures thereof is selected.

12. Composition according to one of the preceding claims in the form of a nail varnish or a hair setting formulation.

13. Use of an emulsion polymer as defined in one of claims 1 to 9, as a film-forming agent in a cosmetic composition, in particular in aqueous compositions.