WO1996038125A1

WO1996038125A1 - COSMETIC OR DERMATOLOGICAL COMPOSITIONS CONTAINING OLIGOMERS OR POLYMERS OF α-HYDROXYCARBOXYLIC ACIDS

Info

Publication number: WO1996038125A1
Application number: PCT/EP1996/002354
Authority: WO
Inventors: Sven Gohla; Waltraud Kaden; Jürgen KIELHOLZ; Uta Kruse; Uta Meiring; Jens Nielsen; Franz STÄB; Florian Wolf
Original assignee: Beiersdorf Ag
Priority date: 1995-06-02
Filing date: 1996-05-31
Publication date: 1996-12-05
Also published as: DE19520237A1

Abstract

Cosmetic or dermatological compositions that contain an effective amount of one or several dissolved or suspended oligomers, and/or polymers, and/or co-oligomers and/or co-polymers of one or several α-hydroxycarboxylic acids having the general formula (I) and linked to each other according to the scheme (II) are useful to administer the monomer α-hydroxycarboxylic acids upon which they are based in cosmetic or dermatological compositions.

Description

description

Cosmetic or dermatological preparations containing oligomers or polymers of α-hydroxycarboxylic acids

The present invention relates to preparations in the field of cosmetic and dermatological skin and hair care, in particular those preparations with low irritation potential or cosmetic or dermatological preparations for prophylaxis, amelioration, elimination or avoidance of skin irritation. In a preferred embodiment, the present invention relates to cosmetic and dermatological preparations for the prophylaxis and treatment of cosmetic or dermatological skin changes such as e.g. skin aging. Furthermore, the present invention relates to preparations against the appearance of dry or rough skin.

Furthermore, the present invention relates to active substances and preparations containing such active substances for cosmetic and dermatological treatment or prophylaxis of erythematous, inflammatory, allergic or autoimmune-reactive symptoms, in particular dermatoses. Furthermore, the invention relates to the use of such active substances and preparations containing such active substances for immunostimulation of the skin, advantageously also for immunostimulation in the sense of treating injured skin, in particular for treating wounds.

Finally, the invention relates to preparations with extremely low so-called "stinging potential".

Skin care is primarily understood to mean that the natural function of the skin as a barrier against environmental influences (e.g. dirt, chemicals, microorganisms) and against the loss of the body's own substances (e.g. water, natural fats, electrolytes) is strengthened or restored. If this function is disturbed, there may be an increased absorption of toxic or allergenic substances or an infestation of microorganisms and, as a result, toxic or allergic skin reactions.

The aim of skin care is also to compensate for the loss of fat and water in the skin caused by daily washing. This is especially important when the natural regeneration ability is insufficient. In addition, skin care products are intended to protect against environmental influences, especially sun and wind, and to delay the signs of aging.

Medical topical compositions generally contain one or more medicaments in an effective concentration. For the sake of simplicity, for a clear distinction between cosmetic and medical use and corresponding products, reference is made to the legal provisions of the Federal Republic of Germany (e.g. cosmetics regulation, food and drug law).

The epidermis is richly equipped with nerves and nerve end devices such as Father Pacini lamellar bodies, Merkel cell neurite complexes and free nerve endings for pain, cold, heat sensation and itching.

In people with sensitive, sensitive or vulnerable skin, a neurosensory phenomenon called "stinging" (<engl.> "To sting" = injure, burn, pain) can be observed. This "sensitive skin" differs fundamentally from "dry skin" with thickened and hardened horny layers.

Typical reactions of "stinging" to sensitive skin are reddening, tension and burning of the skin as well as itching.

Itching in atopic skin and itching in skin diseases are to be regarded as a neurosensory phenomenon.

"Stinging 'phenomena can be regarded as disorders to be treated cosmetically. In contrast, severe itching, in particular severe itching in the case of atopy, can also be described as a more serious dermatological disorder. Typical disturbing neurosensory phenomena associated with the terms "stinging" or "sensitive skin" are reddening of the skin, tingling, tingling, tension and burning of the skin and itching. They can be caused by stimulating environmental conditions such as massage, tenside effects, weather influences such as sun, cold, dryness, but also moist heat, heat radiation and UV radiation, such as the sun.

In "Journal of the Society of Cosmetic Chemists" 28, pp. 197-209 (May 1977) P.J. Frosch and A.M. Kligman describe a method for estimating the "stinging potential" of topically administered substances. As positive substances, e.g. Lactic acid and pyruvic acid are used.

According to previous knowledge, such a sensitivity to very specific substances occurs individually in different ways. This means that a person who experiences "stinging effects" when in contact with a substance, for example lactic acid, is likely to experience it repeatedly with each further contact. The contact with other "Stingem" can also take place with one and the same person without any reaction.

The cosmetic and dermatological use of α-hydroxycarboxylic acids is known per se. For example, citric acid is used to buffer cosmetic and / or dermatological preparations, but also as a synergist for antioxidants in skin and hair cosmetics.

DE-OS 42 04 321 describes the use of longer-chain α-hydroxycarboxylic acids as active ingredients for cosmetic deodorants. US Pat. No. 4,363,815 describes the use of α-hydroxycarboxylic acids for the treatment of inflammatory skin symptoms. US Pat. No. 4,380,549 describes the use of α-hydroxycarboxylic acids to relieve the symptoms of dry skin. Other topical fields of application of the α-hydroxycarboxylic acids are also known, but these few examples already show that the α-hydroxycarboxylic acids are valuable substances effective on the skin, whether they are cosmetic or pharmaceutical applications.

However, the prior art lacked dosage forms for α-hydroxycarboxylic acids. It was therefore an object of the present invention, the subject ^"of the art to enrich in this regard and to develop new dosage forms for α-hydroxycarboxylic acids. Another task was to develop administration forms in which the α-hydroxycarboxylic acids do not interact with other substances of the cosmetic or dermatological formulations in which they are incorporated, but rather only develop their effect on the skin.

It is disadvantageous, however, that the safe amount of α-hydroxycarboxylic acids used can be limited in individual cases, since the "stinging" described above can occur in sensitive people even at concentrations below 0.5% by weight.

However, since it is desirable to enable even sensitive people to be given the cosmetic or dermatological administration of α-hydroxycarboxylic acids, it was an object of the present invention to develop cosmetic or dermatological preparations which contain or release α-hydroxycarboxylic acids, but which are released an extremely low "stinging potential", ideally should be practically free of "stinging effects".

Erythematous skin symptoms also appear as side effects in certain skin diseases or irregularities. For example, the typical rash in the appearance of acne is usually more or less reddened.

The task was therefore to remedy the disadvantages of the prior art. In particular, it was an object of the present invention to provide cosmetic or dermatological preparations in which the advantageous properties of the α-hydroxycarboxylic acids can be used to some extent, but without the disadvantage of any incompatibilities, such as stinging. Furthermore, active substances and preparations containing such active substances should be made available for cosmetic and dermatological treatment and / or prophylaxis of erythematous, inflammatory, allergic or autoimmune-reactive symptoms, in particular dermatoses.

Polymers of many .alpha.-hydroxycarboxylic acids, the linking of the monomers with one another via ester linkage of the .alpha.-hydroxy groups with the carboxyl groups, are known per se. Mainly those based on lactic acid and / or glycolic acid are used in surgery as resorbable sutures or implants. she are also used in cosmetics, but only there as a covering material. Their disadvantage is that they are not or only insufficiently soluble in most cosmetic and pharmaceutically acceptable solvents, which is why cosmetic or pharmaceutical use other than shell material has had to be ruled out until now. Another object of the present invention was to remedy this deficiency.

Surprisingly, it has been found, and this is the solution to all of these problems, that cosmetic or dermatological preparations containing an effective amount of one or more oligomers and / or polymers and / or co-oligomers and / or present in dissolved or suspended form Copolymers of one or more α-hydroxycarboxylic acids of the general formula

R "

I R'-C- COOH

I OH which according to the scheme

are linked to one another, R 'and R "being selected independently of one another from the group

(a1) H-,

(a2) branched or unbranched C-j_25-alkyl-,

(a3) with one or more carboxyl groups and / or hydroxyl groups and / or aldehyde groups and / or oxo groups (keto groups) branched or unbranched C 1-25 "alkyl

(a4) phenyl,

(a5) Phenyl- substituted with one or more carboxyl groups and / or hydroxyl groups and / or branched and / or unbranched C 25 -alkyl groups, or wherein the α-carbon atom of the α-hydroxycarboxylic acid with R 'and R "together form a

(a6) unsubstituted cycloalkyl group with 3 to 7 ring atoms or one

(a7) with one or more carboxyl groups and / or hydroxyl groups and / or oxo groups (keto groups) and / or branched and / or unbranched C- _| _25- Alkyl groups substituted cycloalkyl groups with 3 to 7 ring atoms forms, the number n for at least 40 wt .-% of the oligomers and / or polymers and / or co-oligomers and / or copolymers used is at least 4, and wherein R 'and R "of the individual α-hydroxycarboxylic acid units within a co-oligomer or co-polymer to R 'or R "of one or more α-hydroxycarboxylic acid units of the same co-oligomer or co-polymer may be identical or different, in dissolved or suspended form, the Remedy disadvantages of the prior art.

The use of an effective amount of one or more oligomers and / or polymers and / or co-oligomers and / or co-polymers of one or more α-hydroxycarboxylic acids of the general formula is also according to the invention

R "I R'-C- COOH I OH which according to the scheme

(a1) H-,

(a2) branched or unbranched C 25 25 alkyl,

(a3) with one or more carboxyl groups and / or hydroxyl groups and / or aldehyde groups and / or oxo groups (keto groups) branched or unbranched C 25 alkyl

(a4) phenyl,

(a5) Phenyl- substituted with one or more carboxyl groups and / or hydroxyl groups and / or branched and / or unbranched C- | _25-alkyl groups, or wherein the α-carbon atom of the α-hydroxycarboxylic acid together with R 'and R "together is one

(a6) unsubstituted cycloalkyl group with 3 to 7 ring atoms or one

(a7) with one or more carboxyl groups and / or hydroxyl groups and / or oxo groups (keto groups) and / or branched and / or unbranched C1.25-alkyl groups substituted cycloalkyl group with 3 to 7 ring atoms forms, the number n for at least 40 wt .-% of the oligomers and / or polymers and / or co-oligomers and / or copolymers used is at least 4, and wherein R 'and R "of the individual α-hydroxycarboxylic acid units within a co-oligomer or co-polymer to R 'or R "of one or more α-hydroxycarboxylic acid units of the same co-oligomer or co-polymer may be identical or different, to provide the underlying monomeric α- Hydroxycarboxylic acids in cosmetic or dermatological preparations.

In particular, it could not have been foreseen that the use according to the invention would not only reduce the "stinging potential" of the α-hydroxycarboxylic acids to practically zero even for sensitive people, but that the full activity of the α-hydroxycarboxylic acids would also be retained.

It was also surprising that the present invention opens up the possibility of producing stable and reliable dosage forms for α-hydroxycarboxylic acids which release the active ingredient.

It was known to use polymers or copolymers of lactic acid and / or glycolic acid in cosmetics, namely as a covering material for active ingredient-containing microcapsules. For example, EP-OS 447 318 describes compositions for the cosmetic or pharmaceutical care of the upper skin layers, which contain polymeric, biodegradable nanoparticles in a suitable carrier, which coat an oily active substance. Among the above-mentioned The polymeric coating materials described also include poly (L) lactic acid, poly (DL) lactic acid, polyglycolic acid and copolymers of lactic and glycolic acid. However, there is no indication in the direction of the present invention in that document.

It was particularly surprising that cosmetic or dermatological preparations according to the invention, in particular when the oligomers, polymers, co-oligomers and / or copolymers according to the invention are incorporated into an oil phase, are stable against depolymerization (or de-oligomerization) and their advantageous First have an effect on human skin. Since the oligomers, polymers, co-oligomers and / or copolymers according to the invention gradually release the monomers on which they are based, they are particularly suitable as depot systems or for sustained release.

The oligomers, polymers, co-oligomers and / or co-polymers according to the invention also have the advantage, surprisingly, even if their hydrolysis to the underlying monomers has not yet taken place or has not yet taken place completely, to increase the skin moisture.

Accordingly, the invention also relates to a process for stabilizing an effective amount of one or more oligomers and / or polymers and / or co-oligomers and / or co-polymers of one or more α-hydroxycarboxylic acids of the general formula

R "I R'-C- COOH I OH which according to the scheme

(a1) H-,

(a2) branched or unbranched C 25 25 alkyl,

(a3) branched or unbranched C- _| substituted with one or more carboxyl groups and / or hydroxyl groups and / or aldehyde groups and / or oxo groups (keto groups) _25-alkyl

(a4) phenyl,

(a6) unsubstituted cycloalkyl group with 3 to 7 ring atoms or one (a7) with one or more carboxyl groups and / or hydroxyl groups and / or oxo groups (keto groups) and / or branched and / or unbranched C- _| _25- Alkyl group-substituted cycloalkyl group with 3 to 7 ring atoms, the number n being at least 4 for at least 40% by weight of the oligomer and / or polymer and / or co-oligomer and / or co-polymer used, and wherein R 'and R "of the individual α-hydroxycarboxylic acid units within a co-oligomer or co-polymer to form R' or R" of one or more α-hydroxycarboxylic acid units of the same co-oligomer or co-polymer are identical or different can be in cosmetic or dermatological preparations against depolymerization or deoligomerization by hydrolysis, characterized in that the oligomers and / or polymers and / or co-oligomers and / or copolymers used are incorporated into an oil phase.

The α-hydroxycarboxylic acids on which the oligomers and / or polymers and / or co-oligomers and / or co-polymers are based are advantageously selected from the group of α-hydroxyalkanoic acids, which in turn is particularly advantageous from the group of C2- _-Alkyl carboxylic acids can be selected.

It is particularly preferred to choose oligomers and / or polymers and / or co-oligomers and / or copolymers of glycolic acid, lactic acid, α-hydroxybutyric acid and / or α-hydroxyvaleric acid.

For example, oligo- or polyglycolides are characterized by their structure

Oligo- or polylactides are characterized by their structure

Co-oligo- or copolymers of lactic acid and glycolic acid are characterized, for example, by a structure according to

the sum of the numbers k and j corresponds to the number n. It is clear to the person skilled in the art that the arrangement of the co-monomers in a co-oligomer or co-polymer can be carried out in blocks, alternating, randomly distributed or according to other arrangement principles. All of these types of arrangement can be used advantageously according to the invention.

Oligo- or poly-2-hydroxybutyrates are characterized by the structure

out,

Oligo- or poly-2-hydroxyvalerates are characterized by the structure

According to the invention, it is advantageous to choose those α-hydroxycarboxylic acids present as enantiomers as basic constituents of the oligomers or polymers which are more beneficial to skin care than their optical antipodes, for example L-lactic acid.

R-lactic acid (≡ D-lactic acid) S-lactic acid (≡ L-lactic acid)

However, it can also be more advantageous for other reasons, for example the sheer availability of the starting materials, to make a free choice from two enantiomers, to choose any desired enantiomer mixture or also a racemate

The number n for at least 40% by weight of the oligomer and / or polymer and / or co-oligomer and / or co-polymer used is advantageously at least 8, preferably 10. The upper limit for n can in principle remain open, but nevertheless values for n of 60 to 1,000, in particular 200, have proven to be advantageous. However, polymers which consist of at least 40% by weight of approximately 60,000 monomer units and those which consist of at least 40% by weight of approximately 100,000 monomer units can also be used advantageously.

Examples of advantageous commercial products are:

Resomer R 104 / Boehringer Ingelheim, oligo- (D, L) -lactic acid (main component: n = 12, n _max »50. Average value for n« ^■ 20.

Resomer L 104 oligo (L) -lactic acid, values similar to R 104

Resomer R 207 oligo (D, L) -lactic acid Average value for n «60,000

Oligo (DL-lactate-co-glycolate) (50:50), average value for n * 8; j * k ^■ ■ The content of the oligomers, co-oligomers, polymers and / or copolymers in the cosmetic or pharmaceutical preparations is advantageously 0.01-20% by weight, preferably 0.5-5% by weight, particularly preferably 1 , 5 - 2.5 wt .-%, each based on the total weight of the cosmetic or pharmaceutical preparations.

According to the invention, it is preferred to incorporate the oligomer or co-oligomers, polymers and / or copolymers in dissolved form into cosmetic formulations. To this end, the person skilled in the art can make a non-inventive selection from a large number of known solvents which are generally known for the given substance class. It was surprising, however, that partially or completely esterified polybasic carboxylic acids would prove to be particularly advantageous solvents for the oligomers, co-oligomers, polymers and / or co-polymers according to the invention.

Such esters are advantageously chosen from the group of cosmetically or pharmaceutically acceptable substances of the general structural formula

AOOC-X-COOB, where X is selected from the group consisting of up to four carboxylic acid groups and up to four carboxylic acid alkyl ester groups -COOD, -COOE, -COOF and up to four hydroxyl groups, branched and or unbranched alkylene groups with up to six C. -Atoms and the group of the types substituted with up to four carboxylic acid groups and up to four carboxylic acid alkyl ester groups -COOD, -COOE, -COOF and up to four hydroxyl groups

where A, B, D, E and F represent branched or unbranched alkyl groups with up to five carbon atoms.

Preferred esters are triethyl citrate

CH -COO- Et I HO- C- COO- Et I CH ₂ -COO- Et as well as the diethyl phthalate.

It has surprisingly been found that these esters are not only good solvents for the oligomers, polymers, co-oligomers and / or copolymers according to the invention, but also stabilize them against depolymerization or deoligomerization.

In addition, these esters, preferably the citric acid esters, act synergistically with the oligomers, polymers according to the invention in relation to the cosmetic or dermatological action of the α-hydroxycarboxylic acids, in particular in relation to the caring effect, especially in relation to the action against skin aging. Co-oligomers and / or copolymers together.

The weight ratio of the oligomers, polymers, co-oligomers and / or copolymers on the one hand to the above-described stabilizing esters on the other hand is advantageously in the range from about 1:10 to 10: 1, preferably about 1: 4 to 2 : 1, particularly preferably about 3: 7.

It is known, for example from DE-GbM 88 04 423, to use corresponding citric acid esters as plasticizers for polyiactides / glycolides and similar polymers. The cosmetic or pharmaceutical use according to the invention was neither suggested nor anticipated by DE-GbM 88 04 423, which relates to surgical materials. In addition, DE-GbM 88 04 423 recommends acetone as the solvent, which is neither cosmetically nor pharmaceutically acceptable.

However, it is also advantageous to use silicone oils such as dimethicone as solvents for the oligomers, polymers, co-oligomers and / or copolymers according to the invention.

The oligomers, polymers, co-oligomers or copolymers according to the invention are remarkably stable in cosmetic and pharmaceutical preparations and largely decompose only on human skin to form the underlying oligomers, which then become available to the skin with all its advantageous properties. It is also possible and possibly advantageous to use suspensions of the oligomers, polymers, co-oligomers and / or co-polymers according to the invention.

Before the solution or suspension process, it can be advantageous to precede a micronization process, it being preferred to prefer the micronization with cooling, for example at temperatures below -78 ° C., in particular at temperatures below -150 ° C. at approx. -190 ° C.

The dissolving process is preferably carried out by means of strong agitation, for example in an ultra-turrax. It can also be advantageous to add a wetting agent or an antistatic agent during the solution or suspension process.

Preparations according to the invention are produced in accordance with the usual rules familiar to those skilled in the art. The preparations according to the invention are advantageously in the form of emulsions, preferably O / W emulsions. However, it is also possible and advantageous according to the invention to select other types of formulation, for example W / O emulsions, hydrodispersions, gels, oils, multiple emulsions, for example in the form of W / O / W or OW / O emulsions, anhydrous ointments or ointment bases etc.

In simple emulsions, finely dispersed droplets of the second phase (water droplets in W / O or lipid vesicles in O / W emulsions) are contained in one phase and enclosed by an emulsifier shell. In contrast, in a multiple emulsion (second degree), finely dispersed droplets of the first phase are emulsified in such droplets. These droplets can also have finer disperse droplets (third degree multiple emulsion) and so on.

Just as the simple emulsions are called W / O or O / W emulsions (water-in-oil or oil-in-water), there are W / O / W, O / W / O in multiple emulsions -, O / W / O / W, W / O / V / O emulsions and so on.

Multiple emulsions in which the respective inner and outer water phases or inner and outer oil phases are of different types (for example W / O / W and O / W / O 'emulsions) are accessible to the preparation by two-pot processes. Such emulsions, in which the inner and outer water or oil phases are not different, can be obtained both by one and two-pot processes.

The second degree multiple emulsions are sometimes referred to as "bimultiple systems", such third degrees as "trimultiple systems" etc. (W.Seifriz, Studies in Emulsions, J.Phys.Chem., 29 (1925) 738-749).

Processes for producing multiple emulsions are known per se to the person skilled in the art. There are two-pot processes in which a simple emulsion (e.g. a W / O emulsion) is introduced and, by adding another phase (e.g. a water phase) with a corresponding emulsifier (e.g. an O / W emulsifier) into a multiple emulsion (e.g. a W / O / W emulsion) is transferred.

A second method consists in converting emulsifier mixtures with an oil phase and a water phase into a multiple W / O / W emulsion in a one-pot process. The emulsifiers are dissolved in the oil phase and combined with the water phase. A prerequisite for such a process is that the HLB values (HLB = hydrophilic-lipophilic balance) of the individual emulsifiers used differ significantly from one another.

Hydrodispersions are dispersions of a liquid, semi-solid or solid inner (discontinuous) lipid phase in an outer aqueous (continuous) phase.

In contrast to O / W emulsions, which are characterized by a similar phase arrangement, hydrodispersions are essentially free of emulsifiers. Like other emulsions, hydro dispersions represent metastable systems and are inclined to change into a state of two discrete phases that are coherent. In emulsions, the choice of a suitable emulsifier prevents phase separation.

In the case of hydrodispersions of a liquid lipid phase in an outer aqueous phase, the stability of such a system can be ensured, for example, by building a gel structure in the aqueous phase in which the lipid droplets are stably suspended. Such preparations have proven to be extremely advantageous and particularly stable. Advantageous thickeners for this purpose are carbopols, polysaccharide-based thickeners and bentonites. Particularly advantageous preparations are also obtained if the active compounds according to the invention are combined with antioxidants and / or other substances which counteract cell aging. According to the invention, the preparations advantageously contain one or more antioxidants. All of the antioxidants suitable or customary for cosmetic and / or dermatological applications are used as inexpensive, but nevertheless optional anti-oxidants.

The antioxidants are particularly advantageously selected from the group consisting of

Amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-camosine and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. α-carotene, ß-carotene, lycopene) and their derivatives, lipoic acid and their derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl -, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilaurylthiodipropionate, distearylthiodipropionate, thiodipropionic acid and their derivatives (esters, Ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (e.g. buthionine sulfoximines, homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, heptahionine sulfoximine) in very low tolerable dosages (e.g. pmol to μmol / kg), also (metal) -Chela gates (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-linolenic acid, linoleic acid, oleic acid), folic acid and their Derivatives, ubiquinone and ubiquinol, their derivatives, vitamin C and its derivatives (eg ascorbyl palmitate, Mg - ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and Konyferyl benzoate of benzoin, rutinic acid and its derivatives, ferulic acid and its derivatives, butylated hydroxytoluene, butylated hydroxyanisole, fural gluctol, nordihydroguajak resinic acid, nordihydroguajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, eg zinc and its derivatives, mannose and its derivatives, mannose and its derivatives, mannose and its derivatives, znose and its derivatives, mannose and its derivatives, z its derivatives (eg selenium methionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide) and the invent derivatives according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active ingredients. Oil-soluble antioxidants can be used particularly advantageously for the purposes of the present invention.

The amount of the antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.05-20% by weight, in particular 1-10% by weight, based on the total weight of the preparation.

If vitamin E and / or its derivatives represent the antioxidant (s), it is advantageous to choose their respective concentrations from the range of 0.001-10% by weight, based on the total weight of the formulation.

If vitamin A or vitamin A derivatives or carotenes or their derivatives represent the antioxidant or antioxidants, it is advantageous to use their respective concentrations in the range from 0.001-10% by weight, based on the total weight of the formulation, to choose.

Cttronic acid, salicylic acid, other β-hydroxycarboxylic acids, biotin and the like can advantageously be used as other substances which counteract cell aging.

The cosmetic preparations according to the invention can contain cosmetic auxiliaries as are usually used in such preparations, e.g. Preservatives, bactericides, deodorizing substances, irritant substances, antiperspirants, insect repellents, vitamins, anti-foaming agents, dyes, pigments with a coloring effect, thickeners, softening substances, moisturizing and / or moisturizing substances, fats, Oils, waxes or other common components of a cosmetic formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.

The preparations according to the invention can also advantageously contain substances which absorb UV radiation in the UVB range, the total amount of the filter substances being, for example, 0.1% by weight to 30% by weight, preferably 0.5 to 10% by weight. %, in particular 1 to 6% by weight, based on the total weight of the preparation, in order to provide cosmetic preparations which protect the skin from the entire range of ultraviolet radiation, and in which the stinging of the α-hydroxycarboxylic acids or α-keto carboxylic acids are prevented or drastically reduced. The pH of the preparations according to the invention can advantageously be set in the acidic range, the pH range from 3.5 to 7 being preferred, particularly preferably from 4 to 6, very particularly about 5.5. The stability of the oligomers, polymers, co-oligomers and / or copolymers according to the invention is additionally increased by buffering.

Preparations according to the invention can also advantageously serve as sunscreens.

Emulsions according to the invention e.g. in the form of a sun protection cream or sun protection milk are advantageous and contain e.g. the fats, oils, waxes and other fat bodies mentioned, as well as water and an emulsifier, as is usually used for such a type of formulation.

The lipid phase can advantageously be selected from the following group of substances:

Oils, such as triglycerides of capric or caprylic acid, but preferably castor oil; Fats, waxes and other natural and synthetic fat bodies, preferably esters of fatty acids with alcohols of low C number, e.g. with isopropanol, propylene glycol or glycerin, or esters of fatty alcohols with low C number alkanoic acids or with fatty acids; Alkyl benzoates;

Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.

The aqueous phase of the preparations according to the invention may advantageously contain

Alcohols, diols or polyols of low C number, and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analogous products, furthermore alcohols with a low C number, for example ethanol, isopropanol, 1, 2-propanediol, glycerol and in particular one or more thickeners, which one or more can advantageously be selected from the group consisting of silicon dioxide, aluminum silicates, polysaccharides or their derivatives, for example hyaluronic acid, xanthan gum, hydroxypropyl methyl cellulose, particularly advantageously from the group of polyacrylates, are preferred a polyacrylate from the group of the so-called carbopoles, for example carbopoles of types 980, 981, 1382, 2984, 5984, each individually or in combination.

The cosmetic or dermatological sunscreen preparations advantageously contain inorganic pigments, in particular micropigments, e.g. in amounts of 0.1% by weight to 30% by weight, preferably in amounts of 0.5% by weight to 10% by weight, but in particular 1% by weight to 6% by weight on the total weight of the preparations.

In addition to the combinations according to the invention, it is advantageous according to the invention to use oil-soluble UVA filters and / or UVB filters in the lipid phase and / or water-soluble UVA filters and / or UVB filters in the aqueous phase.

The light protection formulations according to the invention can advantageously contain substances which absorb UV radiation in the UVB range, the total amount of the filter substances e.g. 0.1% by weight to 30% by weight, preferably 0.5 to 10% by weight, in particular 1 to 6% by weight, based on the total weight of the preparations, in order to provide cosmetic preparations places that protect the skin from the entire range of ultraviolet radiation. They can also serve as sunscreens.

The UVB filters can be oil-soluble or water-soluble. Advantageous oil-soluble UVB filter substances include:

- 3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3-benzylidene camphor;

- 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid (2-ethylhexyl ester, 4- (dimethylamino) benzoic acid amyl ester;

- Esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester;

- Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;

Esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di (2-ethylhexyl) ester;

- 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3,5-triazine.

Advantageous water-soluble UVB filter substances include: - Salts of 2-phenylbenzimidazole-5-sulfonic acid such as its sodium, potassium or triethanammonium salt, and the sulfonic acid itself;

- Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;

- Sulfonic acid derivatives of 3-benzylidene camphor, e.g. 4- (2-oxo-3-bornylidenemethyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bomylidenemethyl) sulfonic acid and their salts.

The list of the UVB filters mentioned, which can be used in combination with the active compound combinations according to the invention, is of course not intended to be limiting.

It can also be advantageous to combine the combinations according to the invention with UVA filters which have hitherto usually been contained in cosmetic preparations. These substances are preferably derivatives of dibenzoylmethane, in particular 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione and 1-phenyI- 3- (4'-isopropylphenyl) propane-1,3-dione. These combinations or preparations containing these combinations are also the subject of the invention. The quantities used for the UVB combination can be used.

It is also advantageous to combine the active ingredient combinations according to the invention with other UVA and / or UVB filters.

The total amount of UVA filter substances can advantageously be 0.1% by weight to 30% by weight, preferably 0.5 to 10% by weight, in particular 1 to 6% by weight, based on the total weight of the preparation, in order to provide cosmetic preparations which protect the skin from the entire range of ultraviolet radiation and in which the stinging of the α-hydroxycarboxylic acids or α-ketocarboxylic acids is prevented or drastically reduced.

Cosmetic and dermatological preparations which are in the form of a sunscreen, a pre-soleil or apres-soleil product are also advantageous. These advantageously also contain at least one UVA filter and / or at least one UVB filter.

Furthermore, cosmetic and dermatological preparations which are in the form of a sunscreen, a pre-soleil or apres-soleil product are also particularly advantageous. product and in addition to the UVA filter (s) and / or the UVB filter (s)

Filters contain one or more antioxidants.

Cosmetic and dermatological preparations according to the invention preferably contain inorganic pigments based on metal oxides and / or other metal compounds which are sparingly soluble or insoluble in water, in particular the oxides of titanium TΪO2), zinc (ZnO), iron (eg Fβ2θ3), zirconium (Zrθ2), Silicon (Siθ2), manganese (e.g. MnO), aluminum (AI2O3), cerium (e.g. Cβ2θ3), mixed oxides of the corresponding metals and mixtures of such oxides. It is particularly preferred to use pigments based on TiO 2

A prerequisite for the use of inorganic pigments for the purposes of the invention is, of course, the cosmetic or dermatological harmlessness of the underlying substances.

It is advantageous to choose the particle diameter of the pigments used to be less than 100 nm.

According to the invention, the inorganic pigments are in hydrophobic form, that is to say that they have been surface-treated to be water-repellent. This surface treatment can consist in that the pigments are provided with a thin hydrophobic layer by methods known per se.

One such method consists, for example, in that the hydrophobic surface layer according to a reaction

n Tiθ2 + m (RO) 3Si-R '-> n ΗO2 (surface)

is generated, n and m are stoichiometric parameters to be used at will, R and R 'are the desired organic radicals. For example, hydrophobized pigments shown in analogy to DE-OS 33 14 742 are advantageous.

Advantageous TiO 2 pigments are available, for example, under the trade names T 805 (DEGUSSA) or M 262 (KEMIRA) or M 160 (KEMIRA) or MT 100 T (TAYCA). Advantageous SiO 2 pigments can be selected from the range of hydrophobic pigments sold under the trade names AEROSIL (DEGUSSA), for example AEROSIL R 812 or AEROSIL R 972.

Preparations according to the invention are advantageously characterized by a content of 0.1 to 10% by weight, in particular 0.5 to 5.0% by weight, of hydrophobic inorganic pigments, in each case based on the total weight of the composition.

In the following examples, advantageous embodiments of the present invention are listed.

example 1

% By weight

Cetyl stearyl isononanoate, PEG-20 cetyl stearyl ether, cetyl stearyl alcohol, glyceryl stearate, glycerol, cetyl palmitate, PEG-12 cetyl stearyl ether, benzoic acid 15.00

Cetyl stearyl isononanoate 4.00

Dicapryl ether 7.00

Glycerin 3.00

Carbopol 2984 0.40

Resomer 104 (30% by weight) in dimethicone copolyol 6.60

NaOH (! 0 wt% in H ₂ O) 1.60

Perfume, preservatives, anti-oxidants q.s.

Water ad 100.00

Example 2

% By weight

Cetyl stearyl isononanoate 4.00

Dicapryl ether 7.00

Glycerin 3.00

Carbopol 2984 0.40

Resomer 104 (30% by weight) in triethyl citrate 6.60

NaOH (! 0 wt.% In H ₂ O) 1.60

Perfume, preservatives, anti-oxidants q.s.

Water ad 100.00 Example 3

% By weight

Polyglycerol methyl glucose distearate 4.50

Glycerol monolaurate 0.75

Octanoic / decanoic acid triglycerides 1.00

Octyldodecanol 2.00

Isopropyl stearate 2.00

Glycerin 3.00

Myristyl alcohol 1.75

Cetyl alcohol 4.50

Carbomerpol 2984 0.10

Resomer 104

(30% by weight in triethyl citrate / dimethicone copolyol 1: 1) 6.60

NaOH 0.09

Perfume, preservatives, antioxidants q.s.

Water ad 100.00

Example 4

% By weight

PEG-40 stearate 1.00

Glycerol monostearate 2.00

Octanoic / decanoic acid triglycerides 4.30

Octyldodecanol 1.00

Ci ₂ -Ci ₅ alkyl benzoates 1, 00

Glycerin 6.00

Myristyl alcohol 1.75

Cetyl alcohol 3.00

NaCI 2.40

Resomer 104 (30% by weight in triethyl citrate) 6.60

Cyclomethicone 3.00

Perfume, preservatives, anti-oxidants q.s.

Water ad 100.00 Example 5

% By weight

Wool wax alcohol 0.10

Octanoic / decanoic acid triglycerides 1, 00

Octyldodecanol 1.00

Ci ₂ -Ci ₅ alkyl benzoates 2.00

Butylene glycol 2.00

Cetylstearyl alcohol 1.00

Diglyceryl monocaprate 0.10

Glycine 0.35

Resomer 104 (30% by weight in tributyl citrate) 6.60

Panthenol 0.15

NaOH 0.27

Ethanol 5.00

Perfume, preservatives, anti-oxidants q.s.

Water ad 100.00

Claims

Claims:

1. Cosmetic or dermatological preparations containing an effective amount of one or more oligomers and / or polymers and / or co-oligomers and / or co-polymers of one or more α-hydroxycarboxylic acids of the general formula present in dissolved or suspended form

which according to the scheme

are linked to one another, R 'and R "being selected independently of one another from the group (a1) H-,

(a2) branched or unbranched C- _| _25-alkyl,

(a3) branched or unbranched C- | _25-alkyl- (a4) phenyl-, substituted with one or more carboxyl groups and / or hydroxyl groups and / or aldehyde groups and / or oxo groups (keto groups),

(a5) with one or more carboxyl groups and / or hydroxyl groups and / or branched and / or unbranched C- _| _25-alkyl groups substituted phenyl, or wherein the α-carbon atom of the α-hydroxycarboxylic acid with R ^* and R "together is an (a6) unsubstituted cycloalkyl group with 3 to 7 ring atoms or (a7) with one or more carboxyl groups and / or hydroxyl groups and / or oxo groups (keto groups) and / or branched and / or unbranched C1.25-alkyl groups which form substituted cycloalkyl groups with 3 to 7 ring atoms, the number n representing at least 40% by weight of the oligomers and / or polymers used and / or co-oligomers and / or co-polymers is at least 4, and wherein R 'and R "of the individual α-hydroxycarboxylic acid units within a co-oligomer or co-polymer to R' or R" are one or more α-Hydroxycarboxylic acid units of the same co-oligomer or co-polymer may be identical or different.

2. Use of an effective amount of one or more oligomers and / or polymers and / or co-oligomers and / or co-polymers of one or more α-hydroxycarboxylic acids of the general formula

R "I R'-C- COOH I OH which according to the scheme

(a2) branched or unbranched C- _| _25-alkyl,

(a3) with one or more carboxyl groups and / or hydroxyl groups and / or Al¬ dehydgruppen and / or oxo groups (keto groups) substituted branched or unbranched C _j _25-alkyl (a4) phenyl,

(a5) with one or more carboxyl groups and / or hydroxyl groups and / or branched and / or unbranched C- _| _25-alkyl groups substituted phenyl, or where the α-carbon atom of the α-hydroxycarboxylic acid with R 'and R "together is an (a6) unsubstituted cycloalkyl group with 3 to 7 ring atoms or one (a7) with one or more carboxyl groups and / or hydroxyl groups and / or oxo groups (keto groups) and / or branched and / or unbranched C 1-25 alkyl groups, substituted cycloalkyl groups with 3 to 7 ring atoms, the number n representing at least 40% by weight of the oligomer (s) used and / or Polymers and / or co-oligomers and / or co-polymers is at least 4, and where R 'and R "of the individual α-hydroxycarboxylic acid units within a co-oligomer or co-polymer to R' or R" is one or of several α-hydroxycarboxylic acid units of the same co-oligomer or co-polymer may be identical or different, for the purpose of providing the underlying monomeric α-hydroxycarboxylic acids in cosmetic or dermatological preparations.

3. Preparations according to claim 1 or use according to claim 2, characterized gekenn¬ characterized in that the oligomers, polymers, co-oligomers and / or copolymers underlying α-hydroxycarboxylic acids are selected from the group of α-hydroxyalkanoic acids.

4. Preparations according to claim 1 or use according to claim 2, characterized ge indicates that the oligomers, polymers, co-oligomers and / or copolymers underlying α-hydroxycarboxylic acids are selected from the group glycolic acid, lactic acid, α-hydroxybutyric acid and α-hydroxyvaleric acid.

5. Preparations according to claim 1 or use according to claim 2, characterized ge indicates that the number n for at least 40 wt .-% of the oligo or mers used and / or polymers and / or co-oligomers and / or co- Polymer is at least 8, preferably 10.

6. Preparations or use according to claim 5, characterized in that n is a maximum of 100,000.

7. Preparations according to claim 1 or use according to claim 2, characterized ge indicates that the oligomers, polymers, co-oligomers and / or copolymers in combination with one or more cosmetically or pharmaceutically acceptable substances of the general structural formula

AOOC-X-COOB are present, where X is selected from the group consisting of up to four carboxylic acid groups and up to four carboxylic acid alkyl ester groups -COOD, -COOE, -COOF and up to four hydroxy groups, branched and or unbranched alkylene groups with up to six C-atoms and the group of the types substituted with up to four carboxylic acid groups and up to four carboxylic acid alkyl ester groups -COOD, -COOE, -COOF and up to four hydroxyl groups

8. Preparations or use according to claim 7, characterized in that the triethyl citrate is chosen as the substance of the general structural formula AOOC-X-COOB.

9. Process for stabilizing an effective amount of one or more oligomers and / or polymers and / or co-oligomers and / or co-polymers of one or more α-hydroxycarboxylic acids of the general formula

which according to the scheme

(a1) H-,

(a2) branched or unbranched C 1-25 alkyl,

dehydgruppen (a3) with one or more carboxyl groups and / or hydroxyl groups and / or Al¬ and / or oxo groups (keto groups) substituted branched or unbranched C _j _25 alkyl

(a4) phenyl,

(a5) with one or more carboxyl groups and / or hydroxyl groups and / or ver¬ branched and / or unbranched C _j _25-alkyl substituted phenyl, or wherein the α-carbon atom of the α-hydroxycarboxylic acid having R 'and R "together form a

(a6) unsubst ^'rtuierte cycloalkyl group having 3 to 7 ring atoms or a

(a7) with one or more carboxyl groups and / or hydroxyl groups and / or oxo groups (keto groups) and / or branched and / or unbranched Cj.25-alkyl groups substituted cycloalkyl group with 3 to 7 ring atoms, the number n being at least 40 % By weight of the oligomer and / or polymer and / or co-oligomer and / or co-polymer used is at least 4, and where R 'and R "of the individual α-hydroxycarboxylic acid units within a co-oligomer or co-polymer are identical to R' or R" of one or more α-hydroxycarboxylic acid units of the same co-oligomer or co-polymer or can also be different, in cosmetic or dermatological preparations against depolymerization or deoligomerization by hydrolysis, characterized in that the oligomers and / or polymers and / or co-oligomers and / or copolymers used are incorporated into an oil phase.