DE10202065A1 - Use of organoboron compounds capable of reducing (hydro)peroxides to alcohols in cosmetic or dermatological compositions useful for preventing or treating (hydro)peroxide-induced skin damage - Google Patents

Abstract

Cosmetic or dermatological compositions comprise an oxygen or carbon radical scavenging antioxidant and a boron-containing compound (I) that can convert peroxides and hydroperoxides to alcohols without active radical formation.

Description

The invention relates to the use of peroxide decomposers and a combination of antioxidants and Peroxide decomposers by reduction without the formation of radicals Subsequent stages with the peroxides faster than the skin's own sulfur containing compounds with peroxides or hydroperoxides react, as well as cosmetic and dermatological preparations, that contain these peroxide decomposers.

The human skin is subject to certain aging processes, which partly relate to intrinsic processes (chronoaging) and partly due to exogenous factors (environmental, e.g. photoaging) are due. Additionally occur temporarily or also permanent changes in the complexion, such as acne, oily or dry skin, keratosis, rosaceae, photosensitive, inflammatory, erythematous, allergic or autoimmune reactive Reactions such as dermatoses, photodermatoses and others, their exact causes, as well as factors that influence them, often are only partially understood.

The exogenous factors include, in particular, sunlight or artificial radiation sources with a comparable spectrum, as well Compounds that can arise from the radiation, such as undefined reactive photo products, which are also radical or can be ionic. But these factors also count harmful or reactive compounds such as ozone, free radicals, for example the hydroxyl radical, singlet oxygen and others reactive oxygen or nitrogen compounds, Cigarette smoke, natural and synthetic toxins, and others that disrupt natural physiology or morphology of the skin. By Among other things, the influence of these factors leads to direct Damage to the DNA of the skin cells as well as the collagen, elastin or glycosaminoglycan molecules of the extracellular matrix which are responsible for the firmness of the skin. Furthermore signal transduction chains are influenced, at the end of which the Activation of harmful factors, e.g. B. matrix-degrading enzymes, stands. Important representatives of these enzymes are Matrix metalloproteinases (MMPs, e.g. collagenases, gelatinases, stromelysins), whose activity is additionally determined by TIMPs (tissue inhibitor of matrix metalloproteinases) can be regulated.

Furthermore, the harmful influences lead to damage on the cells of the skin itself. As a result of this is For example, the skin's ability to regenerate is reduced.

As a further consequence, inflammatory reactions can occur among other things, immunoregulatory compounds such as Interleukins, prostaglandins and histamines released. This attracts immunocompetent cells, among other things and intensifies the inflammatory response.

The consequences of aging are thinning of the skin, weaker Interlocking of the epidermis and dermis, reduction in the number of cells and the supplying blood vessels. Through the aging processes fine lines and wrinkles develop Skin becomes leathery, yellowish and sagging, it occurs Pigment disorders.

Antioxidant compounds are often found in dermatological or cosmetic preparations for protection against used the spoil. But they can also used to be harmful or undesirable oxidative Processes that take place in human or animal skin, to reduce. It is known that such processes occur in play an important role in skin aging. The skin is permanent oxidative stress through the formation of peroxides and Exposed to hydroperoxides, some from the outside environment derive from the skin, but are also partially formed endogenously. Around To counteract this stress, the skin has a large number of its own Protections. However, these protective mechanisms are not enough to completely prevent oxidative processes in the skin. On the contrary, it is generally assumed that it is these oxidative processes make a significant contribution to skin aging, but also to general or pathological changes in the skin Afford.

In particular, the importance of lipid peroxidation for the Aging generally recognized. The toxic effects of Lipid hydroperoxides and their decomposition products have been u. a. by W. A. Prior (ACS Sysup. Ser. (1985), 277, 77-96). For the decomposition of peroxides, hydroperoxides or Hydrogen peroxide are also related to various systems Cosmetics have been described, so the use of Metal phosphyrins (JP 3273082), phytic acid zinc salts (JP 08104635), Catalase (JP 08175035) and other enzymes (JP 67165553). Furthermore, JP 06345797 describes the use of cysteine-containing Dipeptides for bleaching the skin, for preventing Lipid peroxidation and for the decomposition of lipid peroxides known.

To support the endogenous protective mechanisms therefore antioxidant, d. H. effective as O or C radical scavengers Ingredients for cosmetic and dermatological preparations added (e.g. DE 197 39 349). So far, however effect actually achieved behind the hoped for. In particular, by increasing the amount of Antioxidant usually not a correspondingly higher antioxidant Achieve effect.

It was therefore the task of active ingredients for cosmetic or to provide dermatological preparations with which can significantly increase the antioxidant effect.

There was also the task of active ingredients for cosmetic or dermatological preparations to provide the skin protects against oxidative damage.

In general, the following scheme applies to the mechanism of peroxide or hydroperoxide formation

While the usual antioxidants are essentially O or C radical scavengers, the object of the invention was to prevent skin damage more efficiently by intervening in the mechanism of this scheme. An ionic and reducing attack according to the following scheme was considered.

It has now been found that the use of a reducing acting peroxide decomposer has an excellent effect. It was also found that the use of a combination one antioxidant as a radical scavenger and one reducing acting peroxide decomposer an excellent synergistic Has an effect. The peroxide decomposer must be selected so that that it is significantly more reactive in vitro than it is acting skin's own, sulfur-containing compounds, such as Cystine or cysteine.

• a) mindestens einem als O- bzw. C-Radikal-Scavenger wirksamen Antioxidans und
• b) mindestens einer organischen, Bor-enthaltenden Verbindung, die Peroxide oder Hydroperoxide zu den entsprechenden Alkoholen ohne Bildung aktiver radikalischer Folgestufen reduziert.

In particular, the object described above was achieved with cosmetic or dermatological preparations which have an effective content of

• a) at least one antioxidant effective as an O- or C-radical scavenger and
• b) at least one organic, boron-containing compound which reduces peroxides or hydroperoxides to the corresponding alcohols without the formation of active radical subsequent steps.

The preparations according to the invention are particularly suitable to avoid or reduce skin damage caused by endogenous or exogenously formed peroxides or hydroperoxides.

Contain the cosmetic or dermatological preparations usually, based on the finished preparations, 0.001 to 30% by weight, preferably 0.01 to 10% by weight and in particular 1 to 5% by weight of antioxidant (a) and 0.001 to 30% by weight, preferably 0.01 to 10 wt .-% and in particular 1 to 5 wt .-% at least a peroxide or hydroperoxide decomposer (b).

The peroxide or hydroperoxide decomposers (b) have one significantly greater decomposing (reducing) effect than the skin's own Have compounds such as cystine or cysteine. Whether certain Suitable compounds for the use according to the invention, recognizes one in vitro z. B. that they are dissolved at room temperature in a molar concentration of 0.05 m / l in a polar or non-polar solvent after storage at 70 ° C for 30 minutes the peroxide or hydroperoxide concentration around at least 10%, in particular 20%, preferably 50% and reduce in particular 90%.

Another object of the present invention relates to Use of organic, boron-containing compounds b), the peroxides or hydroperoxides to the corresponding alcohols reduced without the formation of active radical subsequent stages, in cosmetic or dermatological preparations.

• a) mindestens einem als O- bzw. C-Radikal-Scavenger wirksamen Antioxidans und
• b) mindestens einer organischen, Bor-enthaltenden Verbindung, die Peroxide oder Hydroperoxide zu den entsprechenden Alkoholen ohne Bildung reaktiver radikalischer Folgestufen reduziert

in kosmetischen oder dermatologischen Zubereitungen. Another subject relates to the use of a combination of

• a) at least one antioxidant effective as an O- or C-radical scavenger and
• b) at least one organic, boron-containing compound which reduces peroxides or hydroperoxides to the corresponding alcohols without the formation of reactive radical subsequent steps

in cosmetic or dermatological preparations.

In particular, suitable boron-containing compounds b) are compounds of the formula (I)


in which the variables have the following meaning independently of one another:
R ¹ , R ² and R ³ :
Hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₂₀ alkoxycarbonyl, C ₁ -C ₁₂ alkylamino, C ₁ -C ₁₂ dialkylamino, aryl, heteroaryl, optionally substituted.

Examples of compounds of the formula (I) are:

Also suitable as b) are compounds of the formula (II):


in which R ^{1 has} the meaning given above.

Examples of compounds of the formula (II) are:

Suitable as b) are compounds of the formula (III):


in which R ¹ and R ^{2 have} the meaning given above.

Examples of compounds of the formula (III) are:

Suitable as b) are compounds of the formula (IV):


in which R ¹ and R ^{2 have} the meaning given above and R ¹ and R ² can be bridged by ring closure.

Suitable as b) are compounds of the formula (V):


in which R ¹ , R ² and R ^{3 have} the meaning given above.

Examples of compounds of the formula (V) are:

Compounds of the formula (VI) are suitable as b):


in which R ¹ , R ² and R ^{3 have} the meanings given above.

Examples of compounds of the formula (VI) are:

Suitable as b) are compounds of the formula (VII):


in which R ¹ , R ² and R ^{3 have} the meanings given above.

Examples of compounds of the formula VII are:

Suitable as b) are compounds of the formula (VIII):


in which the variables have the following meaning independently of one another:
R ¹ , R ² , R ³ and R ^{4 are} hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₁ -C ₁₂ Alkoxy, C ₁ -C ₂₀ alkoxycarbonyl, C ₁ -C ₁₂ alkylamino, C ₁ -C ₁₂ dialkylamino, aryl, heteroaryl, optionally substituted
X⊕ physiologically compatible cations, such as the alkali and alkaline earth metal salts or as optionally substituted ammonium salts.

Examples of compounds of the formula (VIII) are:

As alkyl radicals R ¹ to R ⁴ are branched or unbranched C ₁ -C ₂₀ alkyl chains, preferably methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl , n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl , 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2 -Ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl , n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl or n-eicosyl.

Particularly preferred alkyl radicals are methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 2-ethylhexyl.

As alkenyl radicals R ¹ to R ⁴ are branched or unbranched C ₂ -C ₁₀ alkenyl chains, preferably vinyl, propenyl, isopropenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 3-methyl-1-butenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl or 2-octenyl.

Preferred cycloalkyl radicals for R ¹ to R ⁴ are branched or unbranched C ₃ -C ₁₀ cycloalkyl chains such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclopropyl, 1-ethylcyclopropyl, 1-propylcyclopropyl, 1-butylcyclopropyl, 1-pentylcyclopropyl Called 1-methyl-1-butylcyclopropyl, 1,2-dimethylcyclypropyl, 1-methyl-2-ethylcyclopropyl, cyclooctyl, cyclononyl or cyclodecyl.

Preferred cycloalkenyl radicals for R ¹ to R ⁴ are branched or unbranched, C ₃ -C ₁₀ cycloalkenyl chains with one or more double bonds, such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, cycloheptenyl , Cycloheptatrienyl, Cyclooctenyl, 1,5-Cyclooctadienyl, Cyclooctatetraenyl, Cyclononenyl or Cyclodecyl called.

Cyclopropyl, cyclopentyl and cyclohexyl are particularly preferred. The cycloalkenyl and cycloalkyl radicals can optionally with one or more, for. B. 1 to 3 radicals such as halogen z. B. fluorine, chlorine or bromine, cyano, nitro, amino, C ₁ -C ₄ alkylamino, C ₁ -C ₄ dialkylamino, hydroxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or other radicals be substituted or 1 to 3 heteroatoms such as sulfur, nitrogen, the free valences of which may be saturated by hydrogen or C ₁ -C ₄ -alkyl or contain oxygen in the ring.

As alkoxy radicals for those with 1 to 12 carbon atoms, preferably with 1 to 8 carbon atoms.

Examples include:
methoxy
isopropoxy
1-Methylpropoxy-
n-pentoxy
3-methylbutoxy
2,2-dimethylpropoxy
1-methyl-1-ethylpropoxy
octyloxy
ethoxy
n-propoxy
n-butoxy
2-Methylpropoxy-
1,1-dimethylpropoxy
hexoxy
heptoxy
2-Ethylhexoxy-
Alkoxycarbonyl radicals are e.g. B. esters, the above-mentioned alkoxy radicals or residues of higher alcohols such. B. with up to 20 carbon atoms, such as iso-C ₁₅ alcohol.

Suitable mono- or dialkylamino residues are those which Contain alkyl radicals with 1 to 12 carbon atoms, such as. B. methyl, n-propyl, n-butyl, 2-methylpropyl, 1,1-dimethylpropyl, Hexyl, heptyl, 2-ethylhexyl, isopropyl, 1-methylpropyl, n-pentyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-methyl-1-ethylpropyl and octyl.

Aryl is to be understood as meaning aromatic rings or ring systems with 6 to 18 carbon atoms in the ring system, for example phenyl or naphthyl, which may have one or more radicals such as halogen, for. B. fluorine, chlorine or bromine, cyano, nitro, amino, C ₁ -C ₄ alkylamino, C ₁ -C ₄ dialkylamino, hydroxy, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or other radicals can be substituted. Optionally substituted phenyl, methoxyphenyl and naphthyl are preferred.

Heteroaryl residues are advantageously simple or condensed aromatic ring systems with one or more heteroaromatic 3- to 7-membered rings. As heteroatoms can one or more nitrogen, sulfur and / or oxygen atoms be contained in the ring or ring system.

As physiologically compatible cations, the cations are the Alkali and alkaline earth metal salts or the optionally substituted Suitable ammonium salts. Examples include those Trialkylammonium salts, such as tri (hydroxyalkyl) ammonium salts or the 2-methyl propane-1-ol-2-ammonium salts. There are also ammonium residues especially alkylammonium residues.

The selection from the aforementioned connection is made via the Conditions of skin compatibility or skin compatible Concentration and the effectiveness of the peroxide or hydroperoxide Decomposition. To do this, release the connection in question a polar solvent (e.g. acetic acid) or a non-polar solvent (e.g. toluene) in a molar concentration of 0.05 m / l and measures the rate of decomposition of one Peroxide or hydroperoxide after storage at 70 ° C for 30 minutes. The concentration of the peroxide or hydroperoxide should by at least 10%, in particular 20%, preferably 50% and in particular 90% lower.

The antioxidants (a) are generally known per se Links. The antioxidants are advantageously selected from the groups of carotenoids, carotenes (e.g. α-carotene, β-carotene, Lycopene) and their derivatives, chlorogenic acid and their derivatives, Lipoic acid and its derivatives (e.g. dihydrolipoic acid), furthermore (Metal) chelators, EDTA, EGTA and their derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (e.g. Ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), Tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and Derivatives (vitamin A palmitate), butylated hydroxytoluene, Butylated hydroxyanisole, as well as others usually in cosmetic preparations antioxidants used.

The amount of the aforementioned antioxidants (a) in the finished Preparations are e.g. B. 0.001 to 30 wt .-%, preferably 0.01 to 10% by weight and in particular 1 to 5% by weight.

• - oxidativen Prozessen,
• - durch Strahlung oder reaktiven Verbindungen hervorgerufenen Prozessen.

The cosmetic and dermatological preparations according to the invention offer effective protection against

• - oxidative processes,
• - processes caused by radiation or reactive compounds.

The new cosmetic and dermatological formulations can composed of their other components as usual be and for the treatment, care and cleaning of the skin in serve cosmetics. The composition depends on this the effectiveness of the inhibitor, the penetration properties the active substance through the stratum corneum and its ability to form a depot in the skin.

• - vorzeitig gealteter Haut (z. B. Falten, Altersflecken, Teleangiektasien, Pigmentstörungen) und/oder vorzeitig gealterten Hautanhangsgebilden
• - strahlungsbedingten Hautschäden oder strahlungsbedingten negativen Veränderungen der Haut und/oder der Hautanhangsgebilde
• - umweltbedingten (Ozon, freie Radikale, Singulettsauerstoff, reaktive Sauerstoff- oder Stickstoffverbindungen, Zigarettenrauch, Toxine) Hautschäden oder umweltbedingten negativen Veränderungen der Haut und/oder der Hautanhangsgebilde
• - lichtempfindlichen, entzündlichen, erythematösen, allergischen oder autoimmunreaktiven Veränderungen der Haut und/oder der Hautanhangsgebilde (insbesondere Akne, fettige oder trockene Haut, Keratosen, Rosaceae, Dermatosen, atopisches Ekzem, seborrhoisches Ekzem, Photodermatosen, polymorphe Lichtdermatose)
• - defizitären, sensitiven oder hypoaktiven Zuständen der Haut und/oder der Hautanhangsgebilde
• - Juckreiz sowie
• - trockenen Hautzuständen und Hornschichtbarrierestörungen

möglich. Surprisingly, when the active ingredients or combination of active ingredients are used according to the invention, a cosmetically effective treatment but also prevention of

• - prematurely aged skin (e.g. wrinkles, age spots, telangiectasia, pigment disorders) and / or prematurely aged skin appendages
• - radiation-induced skin damage or radiation-related negative changes in the skin and / or the appendages of the skin
• - Environmentally related (ozone, free radicals, singlet oxygen, reactive oxygen or nitrogen compounds, cigarette smoke, toxins) skin damage or environmentally related negative changes in the skin and / or the appendages of the skin
• - Photosensitive, inflammatory, erythematous, allergic or autoimmune-reactive changes in the skin and / or the appendages of the skin (in particular acne, oily or dry skin, keratoses, rosaceae, dermatoses, atopic eczema, seborrheic eczema, photodermatoses, polymorphic light dermatosis)
• - deficient, sensitive or hypoactive conditions of the skin and / or the appendages of the skin
• - itching as well
• - Dry skin conditions and horny layer barrier disorders

possible.

The cosmetic and dermatological preparations in the usual for cosmetics Apply to the skin (and / or hair) in sufficient quantities applied.

For example, the active compounds according to the invention are described in cosmetic agents for cleaning the skin, such as bar soaps, Toilet soaps, core soaps, transparent soaps, luxury soaps, Deodorant soaps, cream soaps, baby soaps, skin protection soaps, abrasive soaps, Syndets, liquid soaps, pasty soaps, soft soaps, Washing pastes, liquid washing, showering and bathing preparations, e.g. B. Washing lotions, shower baths, shower gels, foam baths, Cream foam baths, oil baths, bath extracts, scrub preparations, in-situ Products, shaving foams, shaving lotions, shaving creams used.

They are also suitable for skin cosmetic preparations such as W / O or O / W skin and body creams, day and Night creams, sunscreens, after sun products, Hand care products, face creams, multiple emulsions, jellies, Microemulsions, liposome preparations, niosome preparations, Anti-wrinkle creams, facial oils, lipogels, sports gels, moisturizing creams, Bleaching creams, vitamin creams, skin lotions, skin care lotions, Ampoules, after shave lotions, pre-shaves, moisturizing lotions, Tanning lotions, cellulite creams, depigmenting agents, Massage preparations, body powder, facial tonic, deodorants, Antiperspirants, nose strips, antiacne agents, repellants and other.

In addition, the active compounds according to the invention can be used in cosmetic Hair care products such as hair treatments, hair lotions, Hair rinses, hair emulsions, tip fluids, leveling agents for Perms, hot oil treatment preparations, conditioners, Setting lotions, shampoos, hair tinting and coloring agents, hair sprays, Hair dryer lotions, lotions, gloss sprays, hair brilliants, Hair styling products, hair lotions, alopecia care products and others be used.

The cosmetic or dermatological preparations can each depending on the application as a spray (pump spray or aerosol), foam, Gel, gel spray, lotion, cream, mousse, ointment, suspensions or Powder can be prepared.

It is also advantageous to have the active ingredients in encapsulated form to present, e.g. B. as cellulose encapsulation, in gelatin, with Polyamides, in niosomes, wax matrices, with cyclodextrins or encapsulated liposomally.

The preparations according to the invention generally contain others Excipients, as are usually found in such preparations be used, e.g. B. preservatives, bactericides, perfumes, Anti-foaming agents, dyes, pigments, Thickeners, surface-active substances, emulsifiers, softening substances, softeners, fats, oils, waxes or other common ingredients of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, Foam stabilizers, solubilizers, electrolytes, organic Acids, organic solvents or silicone derivatives.

The preparations according to the invention can be used in addition to mentioned additives contain other compounds that antioxidant, as radical scavenger, skin moisturizing or -Humidifying, anti-inflammatory, anti-inflammatory or anti-allergic act to complement or reinforce their effect. In particular, these compounds can be selected from the Group of vitamins, plant extracts, alpha and Beta hydroxy acids, ceramides, anti-inflammatory, anti-microbial or UV filtering substances, as well as their derivatives and mixtures it.

Preparations according to the invention can also be advantageous Contain substances that contain UV radiation in UV-B and / or UV-A Absorb area.

The lipid phase is advantageously selected from the group of substances of mineral oils, mineral waxes, branched and / or unbranched hydrocarbons and waxes, triglycerides of saturated and / or unsaturated, branched and / or unbranched C ₈ -C ₂₄ alkane carboxylic acids; they can be selected from synthetic, semi-synthetic or natural oils such as olive oil, palm oil, almond oil or mixtures; Oils, fats or waxes, esters from saturated and / or unsaturated, branched and / or unbranched C ₃ -C ₃₀ alkane carboxylic acids and saturated and / or unsaturated, branched and / or unbranched C ₃ -C ₃₀ alcohols, from aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched C ₃ -C ₃₀ alcohols, for example isopropyl myristate, isopropyl stearate, hexyldecyl stearate, oleyl oleate; also synthetic, semi-synthetic and natural mixtures of such esters such as jojoba oil, alkyl benzoates or silicone oils such as. B. cyclomethicone, dimethylpolysiloxane, diethylpolysiloxane, octamethylcyclotetrasiloxane and mixtures thereof or dialkyl ether.

The aqueous phase of the preparations according to the invention contains optionally advantageous alcohols, diols or polyols lower Carbon number, and their ethers, preferably ethanol, isopropanol, Propylene glycol, glycerin, ethylene glycol monoethyl ether.

Known W / O- are preferably used as emulsifiers also O / W emulsifiers such as polyglycerol esters, sorbitan esters or partially esterified glycerides into consideration.

Particularly suitable solubilizers are ethoxylated ones Sorbitan esters, ethoxylated lanolin alcohols and ethoxylated To call castor oil.

Usual native and synthetic thickeners or gel formers in formulations are cross-linked polyacrylic acids and their Derivatives, polysaccharides such as xanthan gum or alginates, Carboxymethyl cellulose or hydroxycarboxymethyl cellulose, hydrocolloids such as gum arabic or motmorillonite minerals such as bentonite or fatty alcohols, polyvinyl alcohol and polyvinyl pyrrolidone.

The usual propellants for aerosols according to the invention Propellants in question, for example propane, butane, pentane and other.

example 1 Measurement of peroxide decomposition

According to the experimental setup given below according to the invention listed in Tables 1 and 2 using compounds compared to cystine and cysteine investigated their peroxide-decomposing effect.

test description

• 1. 0,05 molare Lösung von tert.-Butylhydroperoxid in CD₃COOD
• 2. 0,055 molare Lösung des potentiellen Hydroperoxid-Zersetzers in CD₃COOD

The following solutions were made:

• 1. 0.05 molar solution of tert-butyl hydroperoxide in CD ₃ COOD
• 2. 0.055 molar solution of the potential hydroperoxide decomposer in CD ₃ COOD

The measuring solutions were prepared from this by mixing 350 µl of solution 1 and 350 µl of the respective solution 2; the measurement solution was then placed in an NMR tube and transferred to the NMR device. The solutions were always prepared and the measurements were carried out at 22 ° C. Before the measurement, the solutions were stored in a thermostat at 70 ° C for 30 minutes. All measurements were carried out on the INOVA 500 500 MHz NMR spectrometer from Varian. A ¹ H-NMR spectrum and a 2D-HSQC ( ¹ H / ¹³ C) spectrum were recorded from each measurement solution. Tert.-butyl hydroperoxide and tert.-butanol each had very closely spaced CH ₃ proton signals; the signals were assigned to tBuOOH or tBuOH using the 2D HSQC spectra. The relative proportions of the two components were determined by integration via the signal of the corresponding components in the ¹ H spectrum or the cross peaks in the HSQC spectrum (Lit: W. Wilker et al. Magn. Reson. Chem. 31, 287-292 (1993 )).

350 µl of 0174 (A80) and 350 µl of the other samples were mixed. Toluene-d8 (= N) or CD ₃ COOD (= S) was used as LM.

Examples Examples of cosmetic preparations

Recipes 1 to 13 - Soft Skin Fluid % W / W Ceteareth-6 and Stearyl Alcohol 2.50 Ceteareth-25 2.50 Hydrogenated Coco-Glycerides 1.50 PEG-40 dodecyl glycol copolymer 3.00 Dimethicone 3.00 Phenethyl dimethicone 2.00 Cyclomethicone 1.00 Cetearyl octanoate 5.00 Avocado Oil 1.00 Sweet Almond Oil 2.00 Wheat Germ Oil 0.80 Panthenol USP 1.00 phytantriol 0.20 Tocopheryl Acetate 0.30 Propylene glycol 5.00 Peroxide decomposer according to Examples 1 to 6 1.00 Sodium ascorbyl phosphate 2.00 Perfume qs Preservative qs Aqua ad 100 % W / W Cetearyl alcohol 1.00 Glyceryl stearate 1.50 Stearyl alcohol 1.50 Cetyl palmitate 2.00 Tocopheryl Acetate 0.50 Dimethicone 8.00 Ceteareth-6 and Stearyl Alcohol 3.00 Octyl methoxycinnamate 5.00 propylene glycol 8.00 panthenol 1.00 Evening Primrose Oil 3.00 PEG-7 Hydrogenated Castor Oil 6.00 Glyceryl oleates 1.00 Phenethyl dimethicone 3.00 Beeswax 1.50 Locust Bean Gum 0.80 Silkpowder 0.80 borax 0.10 Preservative qs Perfume qs Peroxide decomposer according to Examples 1 to 6 1.20 Aqua ad 100 % W / W PEG-7 Hydrogenated Castor Oil 6.00 PEG-40 Hydrogenated Castor Oil 0.50 Isopropyl palmitate 7.00 PEG-45 / Dodecyl Glycol Coplymer 2.00 Jojoba Oil 3.00 Magnesium stearate 0.60 Octyl methoxycinnamate 8.00 C12-15 alkyl benzoates 5.00 Titanium Dioxide 4.00 Propylene glycol 5.00 EDTA 0.20 Preservative qs Sodium ascorbyl phosphate 1.00 Tocopheryl Acetate 0.50 Peroxide decomposer according to Examples 1 to 6 0.05 Perfume qs Aqua ad 100 % W / W Mineral Oil 7.50 Cetearyl octanoate 2.50 Aluminum stearate 0.25 Magnesium stearate 0.25 Microdrystalline wax H 0.50 Cetearyl alcohol 1.00 Lanolin alcohol 1.50 Mineral Alcohol and Lanolin Alcohol 1.50 PEG-7 Hydrogenated Castor Oil 0.75 PEG-45 / Dodecyl Glyocol Copolymer 2.00 Tocopheryl Acetate 3.50 Ceteareth-6 and Stearyl Alcohol 2.00 Ceteareth-25 2.00 Trilauret-4 phosphate 1.00 hydroxyethyl 0.20 propylene glycol 7.50 Magnesium sulfates 0.25 Peroxide decomposer according to Examples 1 to 6 2.00 Aqua ad 100 % W / W Ceteareth-25 13,00 PEG-7 glyceryl cocoate 20.00 Octyl dodecanol 5.00 Sodium ascorbyl phosphate 0.50 Peroxide decomposer according to Examples 1 to 6 0.80 Preservative qs Aqua ad 100 % W / W PEG-40 Hydrogenated Castor Oil 1.00 Bisabolol rac. 0.10 Propylene glycol 8.00 panthenol 0.50 Water and Tocopheryl Acetate and Polysorbate 80 and Caprylic / Capric Triglyceride and Lecithin 3.00 Preservative qs Perfume qs Carbomer 0.50 Peroxide decomposer according to Examples 1 to 6 0.80 Triethanolamine 0.70 Aqua ad 100 % W / w silica 5.00 Dimethicone 10.00 Cetearyl octanoate 40,00 Caprylic / Capric triglycerides 8.00 Phenethyl dimethicone 2.00 Mineral Oil 26.00 Sweet Almond Oil 5.00 Tocopheryl Acetate 1.00 phytantriol 0.30 Peroxide decomposer according to Examples 1 to 6 1.50 tocopherol 0.50 Perfume 0.70 % W / W silica 5.00 Dimethicone 10.00 Cetearyl octanoate 30.00 isopropyl myristate 5.00 Caprylic / Capric triglycerides 10.00 Phenethyl dimethicone 5.00 Mineral Oil 25,70 Jojoba Oil 5.00 Tocopheryl Acetate 1.00 phytantriol 0.30 Peroxide decomposer according to Examples 1 to 6 1.50 tocopherol 0.50 Perfume 1.00 % W / W Beeswax 12,00 Hydrogenated Coco Glycerides 5.00 Ricinus Oil 40,00 Isopropylpalmitate 10.00 Mineral Oil 7.50 Candellila wax 8.00 Phenethyl dimethicone 5.00 Tocopheryl Acetate 1.00 Peroxide decomposer according to Examples 1 to 6 1.50 petrolatum 5.00 Benzophenone-3 5.00 % W / W PEG-40 Hydrogenated Castor Oil 2.00 Menthyl lactate 0.20 Alcohol 5.00 PEG-7 glyceryl cocoate 2.00 Witch Hazel 5.00 allantoin 0.10 Bisabolol rac. 0.20 propylene glycol 5.00 Tocopheryl Acetate 1.00 Sodium ascorbyl phosphate 0.20 Panthenol USP 0.50 Lactic Acid (80%) 0.20 Peroxide decomposer according to Examples 1 to 6 2.50 Perfume qs Aqua ad 100 % W / W Ceteareth-6 and Stearyl Alcohol 9.00 Dimethicone 5.00 Cetearyl octanoate 8.00 Macadamia Nut Oil 5.00 propylene glycol 5.00 Aqua 53,00 Sicovit White E 171 8.00 Sicomet Brown 70 13E 3717 2.00 Tocopheryl Acetate 0.20 Peroxide decomposer according to Examples 1 to 6 0.50 Perfume qs Benzophenone-3 4.30 % W / W Ceteareth-6 and Stearyl Alcohol 7.00 Ceteareth-25 5.00 Dimethicone 5.00 Cetearyl octanoate 8.00 Macadamia Nut Oil 5.00 propylene glycol 5.00 Aqua 53,00 Sicovit Weiss E 171 8.00 Sicomet Braun 70 13E 3717 1.00 Tocopheryl Acetate 0.20 Peroxide decomposer according to Examples 1 to 6 0.50 Perfume qs Benzophenone-3 4.30 % W / W Cetearyl octanoate 38,00 Caprylic / Capric triglycerides 28,20 Evening Primrose Oil 3.00 Macadamia Nut Oil 5.00 Isopropylpalmitate 5.00 dimeticones 3.00 Octyl methoxycinnamate 8.00 Octocrylene 5.00 Benzophenone-3 2.00 Tocopheryl Acetate 2.00 phytantriol 0.10 Peroxide decomposer according to Examples 1 to 6 0.50 Tocopheryl Acetate 0.20 Perfume qs % W / W Cocoamidopropyl betaine 5.00 Potassium Coco-Hydrolyzed Animal Protein 7.00 PEG-40 Hydrogenated Castor Oil 2.00 Polyquaternium-44 7.70 Tocopheryl Acetate 1.00 Bisabolol rac. 0.20 panthenol 1.00 Perfume 0.50 Hydroxyethyl cellulose 2.00 Peroxide decomposer according to Examples 1 to 6 1.00 propylene glycol 5.00 Jojoba wax 3.00 Aqua ad 100 % W / W Ceteareth-6 and Stearyl Alcohol 2.00 Ceteareth-25 1.00 Cetearyl octanoate 6.00 Ceteareth-3 2.00 Cetearyl alcohol 6.00 phytantriol 1.00 Propylene glycol 4.00 Polyquaternium-11 5.00 Tocopheryl Acetate 1.00 panthenol 1.00 Retinyl acetates 0.50 Perfume qs Peroxide decomposer according to Examples 1 to 6 1.20 Preservative qs Aqua ad 100 % W / W Polyethylene glycol-6 30.00 Polyethylene glycol-75 45,00 Paraffinum Liquidum 0.50 PEG-40 Hydrogenated Castor Oil 1.00 glycerin 14.00 Benzophenone-3 2.00 Tocopheryl Acetate 1.00 phytantriol 0.10 Peroxide decomposer according to Examples 1 to 6 1.00 Perfume qs Aqua ad 100 % W / W Alcohol 45,00 Aloe Vera (10x conc.) 1.00 panthenol 1.00 Tocopheryl Acetate 0.50 PEG-40 Hydrogenated Castor Oil 0.50 allantoin 0.10 Hydrolyzed animal protein 1.50 1- (4-chlorophenoxy) -1- (1H-imidazolyl) -3,3 dimethyl-2-butanone 0.30 Perfume 0.10 Peroxide decomposer according to Examples 1 to 6 1.00 Aqua ad 100 % W / W PEG-40 Hydrogenated Castor Oil 0.80 Alcohol 20.00 farnesol 0.08 Menthyl lactate 0.06 1,2 propylene glycol 3.20 Benzophenone-4 1.20 PEG-7 glyceryl cocoate 0.80 Tocopheryl Acetate 0.05 Peroxide decomposer according to Examples 1 to 6 0.01 Perfume qs Aqua 13.80 butane 60,00 % W / W Aminomethyl propanol 0.40 Dimethicone copolyol 0.03 Alcohol 43.67 pentanes 13,20 Acrylates / Acrylamide Copolymer 3.40 Tocopheryl Acetate 1.00 Peroxide decomposer according to Examples 1 to 6 0.01 Perfume qs Butane 2.40 Iso-Butane 35,90

Claims (16)

1. Cosmetic or dermatological preparations, characterized by a content of a) at least one antioxidant effective as an O- or C-radical scavenger and b) at least one organic, boron-containing compound which reduces peroxides or hydroperoxides to the corresponding alcohols without the formation of active radical subsequent steps. 2. Cosmetic or dermatological preparations according to Claim 1, characterized in that, based on the finished preparations, 0.001 to 30% by weight of antioxidant (a) and 0.001 to 30% by weight of at least one containing boron Compound (b) included. 3. Cosmetic or dermatological preparations according to Claim 1, characterized in that as a peroxide or hydroperoxide decomposer (b) contain compounds, the in vitro at room temperature, dissolved in a molar Concentration of 0.05 m / l in a polar or non-polar Solvent after storage at 70 ° C for 30 minutes Peroxide or hydroperoxide concentration by at least 10% to reduce. 4. Use of an organic, boron-containing compound, the peroxides or hydroperoxides to the corresponding Alcohols without the formation of active radicals Subsequent stages reduced, in cosmetic or dermatological Preparations. 5. Use a combination of a) at least one antioxidant effective as an O- or C-radical scavenger and b) at least one organic, boron-containing compound which reduces peroxides or hydroperoxides to the corresponding alcohols without the formation of reactive radical subsequent steps in cosmetic or dermatological preparations. 6. Use according to claim 4 and / or 5 to avoid Skin damage due to endogenous or exogenous Factors of peroxides or hydroperoxides formed. 7. Use according to claim 4 and / or 5 for subsequent Elimination and / or relief of skin damage through Peroxides or hydroperoxides. 8. Use according to one of claims 4 and / or 5, characterized characterized in that 0.001 to 30 wt .-% of Boron-containing compound b) is used. 9. Boron-containing compound according to one of the preceding claims, characterized in that a compound of the formula (I)


in which the variables have the following meaning independently of one another:
R ¹ , R ² and R ³ :
Hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₂₀ alkoxycarbonyl, C ₁ -C ₁₂ alkylamino, C ₁ -C ₁₂ dialkylamino, aryl, heteroaryl, optionally substituted. 10. Boron-containing compound according to one of the preceding claims, characterized in that a compound of formula (II)


used, in which R ^{1 has} the meaning given above. 11. Boron-containing compound according to one of the preceding claims, characterized in that a compound of formula (III)


used, in which R ¹ and R ^{2 have} the meaning given above. 12. Boron-containing compound according to one of the preceding claims, characterized in that a compound of the formula (IV)


uses, in which R ¹ and R ^{2 have} the meaning given above and R ¹ and R ² may be bridged by ring closure. 13. Boron-containing compound according to one of the preceding claims, characterized in that a compound of the formula (V)


used, in which R ¹ , R ² and R ^{3 have} the meanings given above. 14. Boron-containing compound according to one of the preceding claims, characterized in that a compound of the formula (VI)


used, in which R ¹ , R ² and R ^{3 have} the meanings given above. 15. Boron-containing compound according to one of the preceding claims, characterized in that a compound of formula (VII)


used, in which R ¹ , R ² and R ^{3 have} the meanings given above. 16. Boron-containing compound according to one of the preceding claims, characterized in that a compound of the formula (VIII)


where the variables have the following meaning independently of one another:
R ¹ , R ² , R ³ and R ⁴
Hydrogen, C ₁ -C ₂₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₂₀ alkoxycarbonyl, C ₁ -C ₁₂ alkylamino, C ₁ -C ₁₂ dialkylamino, aryl, heteroaryl, optionally substituted
X⊕ physiologically compatible cations, such as the alkali and alkaline earth metal salts or as optionally substituted ammonium salts.