DE19737497C2 - Aqueous skin cleanser in emulsion form - Google Patents

Description

Field of the Invention

The invention relates to aqueous skin cleaning emulsions containing hydrophilized glycosides, oil cores per and possibly fatty alcohols.

State of the art

A wide variety of ingredients are used in the field of decorative cosmetics. A typical makeup composition contains, for example, glycerol monostearate, cetyl alcohol, stea rinsic acid, paraffin oil, cetyl stearyl octanoate, octyl palmitate, talc, titanium dioxide, iron oxides, propylene glycol, polysorbate, xanthan, magnesium aluminum silicate, glycerin, perfume oils, preservatives and water. There are waxes, dyes, emulsifiers and thickeners in mascara or mascara medium included. In addition to dyes, waxes and oil bodies, lipsticks also contain above all Mica titanium dioxide and recently also silicone compounds. Eyeshadows usually pose Mixtures of dyes with mica or titanium dioxide, which contain talc, Paraffin oil, kaolin, metal soaps, wax alcohols and emulsifiers can contain. Kajal pencils hold for example iron oxides, vegetable oils, waxes, fatty acids, talc and emulsifiers. Ent Talking cosmetic cleaning agents must therefore have a variety of completely different substances Remove as completely as possible from the skin, i.e. typical waxes, oils and silicone compounds dissolve and at the same time solubilize pigments such as mica or titanium dioxide. Furthermore, must They should be as mild as possible to avoid reddening of the skin or not at all To cause eye mucosal irritation. Preparations such as those used for are disclosed, for example, in EP-B1 0705592, either in the form of lotions, if appropriate Cotton carriers, or offered as creams. Here the consumer also has the Desire that the products, which are always emulsions, are adequate Have storage stability and in particular do not separate irreversibly when heated.

Accordingly, the complex object of the present invention has been to clean the skin to provide in emulsion form that have a high cleaning ability both against waxes, oils, silicone compounds as well as pigments, except are well tolerated by the skin and mucous membranes and at the same time have a particularly high storage capacity have bility.

Description of the invention

The invention relates to skin cleansers in emulsion form, containing

• a) alkyl and / or alkenyl oligoglycoside glycerol ether and
• b) Oil body.

Surprisingly, it was found that the agents have a high cleaning power for waxes, oils and pigments and, in particular, silicone compounds, having an exceptionally good skin and are compatible with the mucous membranes of the eye and do not separate in the heat. The invention includes the finding that the storage stability is further improved by adding fatty alcohols becomes; at the same time, the consistency of the preparations is increased.

Alkyl and / or alkenyl oligoglycoside glycerol ether

Alkyl and / or alkenyl oligoglycoside glycerol ethers are known nonionic, hydrophilized glycosides which can be obtained by the relevant preparative organic chemistry processes and preferably follow the general formula (I),

R ¹ O- [G] _p - [Gly] _q (I)

in which R ^{1 is} an alkyl and / or alkenyl radical having 1 to 22, preferably 4 to 18 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms, Gly is a glycerol radical and p and q are, independently of one another, numbers from 1 to 10 . The preparation of the emulsifiers is based on the corresponding glycosides, which are reacted with glycerol glycide, glycerol carbonate or directly with glycerol or technical oligoglycerols. Relevant methods are described in German patent applications DE-A1 43 17 472, DE-A1 43 35 947 and DE-A1 43 35 956. It is also possible to carry out the glycerol ethers by condensing alkyl glycosides, fatty alcohols and the above-mentioned glycerol components, as described in DE-A1 44 46 446. This last reaction immediately contains mixtures which contain the glycoside glycerol ethers together with fatty alcohols and portions of free glycosides.

The alkyl and / or alkenyl oligoglycoside component can differ from aldoses or ketoses with 5 or 6 Carbon atoms, preferably derived from glucose. The preferred alkyl and / or alkenyl oligo Glycoside glycerol ethers are thus alkyl and / or alkenyl oligoglucoside glycerol ethers. The index number p in general formula (I) gives the degree of oligomerization (DP), i.e. H. the distribution of mono and oli goglycosides and stands for a number between 1 and 10. While p in a given compound must always be an integer and here can assume the values p = 1 to 6, the value p is for a certain glycoside glycerol ether an analytically calculated calculated size, most of the time represents a fractional number. Alkyl and / or alkenyl oligoglycoside glycerol ethers are preferred with an average degree of oligomerization p of 1.1 to 3.0. For application technology In view of this, preference is given to those alkyl and / or alkenyl oligoglycoside glycerol ethers whose oligomerization degree is less than 1.7 and is in particular between 1.2 and 1.4.

The alkyl or alkenyl radical R ¹ can be derived from primary alcohols having 1 to 11, preferably 8 to 10, carbon atoms. Typical examples are methanol, butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucoside glycerol ethers of chain length C ₈ -C ₁₀ (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol by distillation and with a proportion of less than 6% by weight C ₁₂ - Alcohol can be contaminated and alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above. Alkyl oligo glucoside glycerol ethers based on hardened C _12/14 coconut oil alcohol with a DP of 1 to 3 are preferred.

The glycerol component can be monomeric and / or oligomeric (degree of self-condensation q = 1 to 10). Oligomeric glycerol ethers are preferably obtained if technical oligoglycerols are used as starting materials instead of glycerol. Products of this type are preferably used when particularly hydrophilic glycerol ethers with HLB values above 15 are to be used. The bond between the glycerol component and the glycoside base body takes place predominantly via the primary hydroxyl group; however, secondary etherification of secondary hydroxyl groups can also occur. From a technical application perspective, glycoside glycerol ethers of the formula (I) have proven to be particularly advantageous in which R ^{1 is} an alkyl radical having 12 to 14 or 16 to 18 carbon atoms, p is a number from 1.1 to 1.6 and q is 1 stands.

Oil body

Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C ₆ -C ₂₂ fatty acids with linear C ₆ -C ₂₂ fatty alcohols, esters of branched C ₆ -C ₁₃ carboxylic acids are, for example, oil bodies with linear C ₆ -C ₂₂ fatty alcohols, esters of linear C ₆ -C ₂₂ fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of linear and / or branched fatty acids with polyhydric alcohols (such as propylene glycol, dimer diol or Trimer triol) and / or Guerbet alcohols, triglycerides based on C ₆ -C ₁₀ fatty acids, liquid mono- / di- / triglyceride mixtures based on C ₆ -C ₁₈ fatty acids, esters of C ₆ -C ₂₂ fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, especially benzoic acid, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear C ₆ -C ₂₂ fatty alcohol carbonates, Guer bet carbonates, esters of benzoic acid with linear and / or branched ten C ₆ -C ₂₂ alcohols, dialkyl ethers, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons.

Fatty alcohols

Fatty alcohols are to be understood as primary aliphatic alcohols of the formula (II)

R ² OH (II)

in which R ^{2 represents} an aliphatic, linear or branched hydrocarbon radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds. Typical examples are calcium alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolenyl alcohol, linolenyl alcohol, linolenyl alcohol and brassidyl alcohol and their technical mixtures, the z. B. in the high pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. Technical fatty alcohols with 12 to 18 carbon atoms are preferred, such as coconut, palm, palm kernel or tallow fatty alcohol. In a particularly preferred embodiment of the invention, fatty alcohols are used which have the same alkyl chain length as the glycoside glycerol ethers, for example, cetylstearyl alcohol in combination with cetylstearylglycoside glycerol ether.

Make-up remover

The cleaning emulsions can also be used to remove make-up be used.

Make-up removers for the eyes and sensitive skin areas are preferred

• a) 1 to 10, preferably 2 to 5% by weight of alkyl and / or alkenyl oligoglycoside glycerol ether,
• b) 10 to 80, preferably 20 to 50 wt .-% oil body, and
• c) up to 20, preferably 5 to 20% by weight of fatty alcohols,

with the proviso that the quantities with water and other usual auxiliary and Add additives to 100% by weight. The agents usually have a water content of 10 to 90, preferably 20 to 70 wt .-% and can be used both as low viscosity emulsions or available as creams. In a special embodiment, the production of eye cleansing suitable carrier, such as cotton or viscose soaked with the preparations and so put on the market.

Industrial applicability

The preparations according to the invention have excellent cleaning properties Skin cosmetic tolerance and are extremely stable in storage. The preparations can other mild auxiliaries and additives as surfactants, co-emulsifiers, superfatting agents, stabilizers, Consistency enhancers, thickeners, silicone compounds, biogenic agents, preservatives, Contain hydrotropes, solubilizers, perfume oils, dyes and the like.

Typical examples of suitable mild, i.e. H. Surfactants that are particularly compatible with the skin are fatty alcohol poly glycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, Fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, ether carboxylic acids, alkyl oligoglucosides, Fatty acid glucamides, alkylamido betaines and / or protein fatty acid condensates, the latter preferably based on wheat proteins.

Examples of suitable co-emulsifiers are nonionic surfactants from at least one of the following groups:

• 1. Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear Fatty alcohols with 8 to 22 carbon atoms, on fatty acids with 12 to 22 carbon atoms and on alkylphenols with 8 to 15 carbon atoms in the alkyl group;
• 2. C _12/18 fatty acid _monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol;
• 3. Glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated Fatty acids with 6 to 22 carbon atoms and their ethylene oxide addition products;
• 4. Alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxy analogs;
• 5. Addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil;
• 6. Polyol and especially polyglycerol esters such as. B. polyglycerol polyricinoleate or polyglyce rinpoly-12-hydroxystearate. Mixtures of compounds of several are also suitable of these substance classes;
• 7. Addition products of 2 to 15 moles of ethylene oxide with castor oil and / or hardened castor oil;
• 8. Partial esters based on linear, branched, unsaturated or saturated C _6/22 fatty acids, ricinoleic acid as well as 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. Methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g. cellulose);
• 9. trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates;
• 10. wool wax alcohols;
• 11. Polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;
• 12. Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 11 65 574 and / or mixed esters of fatty acids with 6 to 22 carbon atoms, methyl glucose and Polyols, preferably glycerin as well
• 13. Polyalkylene glycols.

The adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters as well as sorbitan mono- and diesters of fatty acids or with castor oil are known, commercially available products. These are homologous mixtures of which average degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. C _12/18 fatty acid _monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE-PS 20 24 051 as refatting agents for cosmetic preparations.

C _8/18 alkyl mono- and oligoglycosides, their preparation and their use are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms. With regard to the glycoside residue, both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to preferably about 8 are suitable. The degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.

Zwitterionic surfactants can also be used as emulsifiers. Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylamino propyl-N, N-dimethylammonium glycinate, for example coconut acylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylate -hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. Suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C _8/18 alkyl or acyl group, contain at least one free amino group and at least one COOH or SO ₃ H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are the N-coconut alkyl aminopropionate, the coconut acylaminoethyl aminopropionate and the C _12/18 acyl sarcosine. In addition to the ampholytic emulsifiers, quaternary emulsifiers are also suitable, those of the esterquat type, preferably methylquaternized difatty acid triethanolamine ester salts, being particularly preferred.

Substances such as lanolin and lecithin as well as polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and Fatty acid alkanolamides are used, the latter at the same time as foam stabilizers serve.

The main consistency agents are fatty alcohols with 12 to 22 and preferably 16 to 18 Carbon atoms and also partial glycerides into consideration. A combination of these is preferred Substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or Polyglycerol poly-12-hydroxystearates. Suitable thickeners are, for example, polysaccha ride, especially xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, also higher molecular weight polyethylene glycol mono- and diesters of Fatty acids, polyacrylates, polyacrylamides, polyvinyl alcohol and polyvinyl pyrrolidone, surfactants such as  for example ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as Pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with a narrow homolog distribution or Alkyl oligoglucosides as well as electrolytes such as table salt and ammonium chloride.

Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones as well as amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl modified silicone compounds that are both liquid and resinous at room temperature can lie. Typical examples of fats are glycerides. a. Beeswax, Carnauba wax, candelilla wax, montan wax, paraffin wax or micro waxes if necessary in Combination with hydrophilic waxes, e.g. B. cetylstearyl alcohol or partial glycerides in question. As Stabilizers can metal salts of fatty acids such. B. magnesium, aluminum and / or zinc stearate can be used. Examples of biogenic active ingredients are tocopherol and tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phy tantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plants to understand extracts and vitamin complexes. Montmorillo can be used as swelling agent for aqueous phases nite, clay minerals, pemules and alkyl modified carbopol types are used.

Hydrotropes such as ethanol, isopropyl alcohol or polyols can also be used to improve the flow behavior. Polyols that come into consideration here preferably have 2 to 15 carbon atoms and at least two hydroxyl groups. Typical examples are

• - glycerin;
• Alkylene glycols such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, Hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1,000 daltons;
• - Technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10 such as technical diglycerol mixtures with a diglycerol content of 40 to 50% by weight;
• Methyl compounds, such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, Pentaerythritol and dipentaerythritol;
• - Lower alkyl glucosides, especially those with 1 to 8 carbons in the alkyl radical such as wise methyl and butyl glucoside;
• Sugar alcohols with 5 to 12 carbon atoms, such as sorbitol or mannitol,
• - Sugar with 5 to 12 carbon atoms such as glucose or sucrose;
• - aminosugars such as glucamine.

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, para benzene, pentanediol or sorbic acid. The extracts of flowers (lavender, Roses, jasmine, neroli), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, corian  the, caraway, juniper), fruit peels (bergamot, lemon, oranges), roots (Macis, Angelica, Celery, cardamom, costus, iris, calmus), woods (sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), needles and twigs (spruce, fir, pine, Mountain pine), resins and balms (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Next animal raw materials, such as musk, civet and castoreum, are also suitable. As synthetic or semi-synthetic perfume oils come from ambroxan, eugenol, isoeugenol, citronellal, Hydroxycitronellal, geraniol, citronellol, geranyl acetate, citral, ionone and methyl ionone.

As dyes, the substances suitable and approved for cosmetic purposes can be used be used, such as the dye in the publication "Cosmetic Colorants" Commission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, pp. 81-106 are put together. These dyes are usually used in concentrations of 0.001 to 0.1 % By weight, based on the mixture as a whole.

The total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40% by weight on the middle - amount. The agents can be produced by customary cold or hot processes respectively; the phase inversion temperature method is preferably used.

Examples

The following recipe examples are water with 100% by weight.

Claims (9)

1. Aqueous skin cleanser in emulsion form, containing

• a) alkyl and / or alkenyl oligoglycoside glycerol ether and
• b) Oil body.

2. Composition according to claim 1, characterized in that they contain alkyl and / or alkenyl oligoglycoside glycerol ethers of the formula (I),
R ¹ O [G] _p - [Gly] _q (I)
in which R ^{1 is} an alkyl and / or alkenyl radical having 1 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms, Gly is a glycerol radical and p and q are, independently of one another, numbers from 1 to 10. 3. Compositions according to claims 1 and 2, characterized in that they contain glycoside glycerol ethers of the formula (I) in which R ¹ for an alkyl radical having 12 to 14 carbon atoms, p for numbers from 1.1 to 1.6 and q for 1 stands. 4. Composition according to claims 1 and 2, characterized in that they contain glycoside glycerol ethers of the formula (I) in which R ^{1 is} an alkyl radical having 16 to 18 carbon atoms, p is a number from 1.1 to 1.6 and q is 1 stands. 5. Composition according to claims 1 to 4, characterized in that they contain oil bodies which are selected from the group formed by Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C ₆ -C ₂₀ -fatty acids with linear C ₆ -C ₂₀ fatty alcohols, esters of branched C ₆ -C ₁₃ -carboxylic acids with linea ren C ₆ -C ₂₀ fatty alcohols, esters of linear C ₆ -C ₁₀ fatty acids with branched Alcohols, esters of linear and / or branched fatty acids with polyhydric alcohols and / or Guerbet alcohols, triglycerides based on C ₆ -C ₁₀ fatty acids, esters of C ₆ -C ₂₂ fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids of vegetable oils, branched get primary Alko, substituted cyclohexanes, Guerbet carbonates, dialkylethene, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic coal water materials. 6. Composition according to claims 1 to 5, characterized in that they further contain fatty alcohols of the formula (II),
R ² OH (II)
in which R ^{2 represents} an aliphatic, linear or branched hydrocarbon radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds. 7. Composition according to claim 6, characterized in that they contain fatty alcohols which are the same Have alkyl chain length like the glycoside glycerol ether. 8. Composition according to claims 1 to 7, characterized in that it

• a) 1 to 10% by weight of alkyl and / or alkenyl oligoglycoside glycerol ether,
• b) 10 to 80 wt .-% oil body
• c) 1 to 20 wt .-% fatty alcohols

contain, with the proviso that the amounts with water and other conventional auxiliaries and additives add up to 100 wt .-%. 9. Composition according to claims 1 to 8, characterized in that it has a water content of 10 have up to 90 wt .-%.