DE19757826A1 - Use of chaotropic compounds for protection of skin against UV radiation e.g. during exposure to sunlight, phototherapy and photo-chemotherapy - Google Patents

Abstract

Chaotropic compounds (I) or topical cosmetic or dermatological compositions containing (I) are used for the protection of the skin against UV radiation. Use of one or more chaotropic compounds (I) or topical cosmetic or dermatological compositions containing (I) for the protection of the skin against UV radiation is new. An Independent claim is also included for topical cosmetic or dermatological compositions containing (I), UV filters (UVA and/or UVB) and/or inorganic pigments.

Description

The present invention relates to a use of chaotropic Compounds and chaotropic compounds containing topical Preparations for use in cosmetics, dermatology and medicine, in particular topical preparations.

For example, urea belongs to these chaotropic compounds. Urea is one of the natural moisturizing factors of the skin and will also as a component of cosmetic preparations for the hydration of the Stratum corneum used. He also has antibacterial and keratolytic Properties.

Furthermore, the damaging effect of the ultraviolet part of the Sun radiation to the skin is well known. While blasting with a Wavelength less than 290 nm (the so-called UVC range), from the Ozone layer can be absorbed in the earth's atmosphere, causing rays in the Range between 290 nm and 320 nm, the so-called UVB range, a UV erythema, visible or pronounced as a simple sunburn or even as more or less intense combustion.

As a maximum of the erythema efficiency of sunlight becomes the tighter Range indicated around 308 nm.  

For protection against UVB radiation, numerous compounds are known in which are derivatives of 3-Benzylidencamphers, 4-aminobenzoic acid, cinnamic acid, salicylic acid, benzophenone and also 2-phenylbenzimidazole is.

Also for the range between about 320 nm and about 400 nm, the so-called In the UVA range, it is important to have filter substances available even its rays can cause damage. So it has been proven that UVA radiation damage the elastic and collagen fibers of the Connective tissue causes what causes the skin to age prematurely, and that it causes numerous phototoxic and photoallergic reactions can be seen.

The damaging influence of UVB radiation can ver by UVA radiation be strengthened.

To protect against the rays of the UVA range therefore certain Derivatives of dibenzoylmethane whose photostability (Int. J. Cosm. Science 10, 53 (1988)) is not always given sufficiently.

The UV radiation can also lead to photochemical reactions, whereby then the photochemical reaction products in the skin metabolism intervention.

It is also known that healthy skin provides some protection against UV radiation possesses or can develop, which depends on the skin type very much may be different and referred to as self-protection of the skin becomes. Depending on the individual's UV sensitivity the skin starts therefore the erythema formation after different irradiation duration respectively after expiration of the self-protection period. The melanin content and melanin formation of the Skin has a strong influence on the self-protection time.  

As a measure of the UV sensitivity of the skin is the "minimal erythema threshold dose (MED) on the skin, resulting in the same radiance intensity, for example, in sunlight, different times, until the respective dose is reached, which triggers a visible erythema.

The usual, commonly used UV filter substances that affect the skin are applied and there show their effect, are characterized by have a good effect, but do not promote the self-protection of the skin and have also the disadvantage that it is sometimes difficult to make them more satisfying To incorporate into formulations. A further disadvantage is that the Each formulation should be applied directly before the UV irradiation and then it is not always guaranteed that they are also on the skin remain because they can be washed off, for example, while bathing.

The object of the invention was to provide protection against UV radiation, which avoids the disadvantages mentioned.

These objects are achieved according to the invention.

The invention relates to the use of a compound or several compounds from the group of chaotropic compounds as Active ingredients or cosmetic and dermatological topical preparations containing one or more compounds from the compound Group of chaotropic compounds as active ingredients for the protection of the skin against UV radiation, in particular for increasing the self-protection time of the skin against UV radiation.

Chaotropic compounds are known and described in the literature. you are structurally disruptive and disrupt the three-dimensional structure of the Hydrogen bonds in water and thus also in protein molecules.  

Preferred chaotropic substances are urea, guanidine, guanidine hydrochloride, Arginine, arginine hydrochloride, thiocyanates, especially the sodium and Potassium thiocyanate, or ammonium sulfate.

Especially preferred is urea.

In the UV radiation, it may, for. B. to UVA and / or UVB radiation act, for example, the natural UV radiation of sunlight.

When used topically, the chaotropic compounds enter the Skin and cause, for. B. after a short exposure time, for example a few hours or after repeated use, an increase in endogenous sunscreen.

This improvement, the z. B. by urea, an endogenous, or occurs in the skin occurring substance, expresses itself for example in the Increase in the MED so that the self-protection time of the skin against UV radiation is prolonged or higher UV radiation intensities better be tolerated.

The sun protection factor (LSF, often also, English usage adjusted, called SPF) indicates how much longer with the Sunscreen protected skin can be irradiated until the same Erythema reaction occurs as with unprotected skin (ie ten times as long as with unprotected skin at LSF = 10).

According to the invention, this sun protection factor is also increased.

According to the invention, a better protection of the skin, in particular in the sense achieved a prophylactic treatment before irradiation, but also at arising erythema, which is mitigated in its effects.  

In the usual for topical applications of cosmetics and dermatics single or multiple applications a day, especially one UV irradiation, according to the invention an increase in the UV protection is achieved by z. As a sunburn occurs only at higher radiation doses, or, when it forms, it is tempered.

It is particularly advantageous that the located in the skin chaotropic compounds, e.g. B. urea, so z. B. wash off as is often the case with sunscreen applied on the skin is.

Advantageous are chaotropic compounds and chaotropic according to the invention Compounds containing preparations also in the phototherapy or Photo chemotherapy, for example, with psoralen, used because they as the unpleasant side effect often mitigate or almost erythema completely suppress. This also applies to phototherapy for psoriasis and eczema.

According to the invention, chaotropic compounds are particularly advantageous Photodermatoses, e.g. B. PLD, atopic dermatitis or dry skin and used in aging skin.

In the latter two indications, the hydration effect forms chaotropic substances, especially urea, an additional advantage.

According to the invention, chaotropic compounds in the usual used in cosmetic and dermatological topical preparations which are intended for use on the skin or scalp.

The preparations according to the invention can chaotropic compounds z. In Amounts of from 0.01 to 30% by weight, preferably from 0.1 to 20% by weight,  in particular 1 to 10 wt .-%, each based on the Total weight of the preparations.

The invention also sunscreen of Pre-sun- but also after sun type, z. B. in repeated use, ie before a new Irradiation containing a chaotropic compound.

The application of these agents leads z. B. to the preferred desired Increasing the natural content of the skin to chaotropic compounds, the then effect protection according to the invention against UV radiation.

The pH of the preparations according to the invention can advantageously be acidic Range, with the pH range of 3.5-7 being preferred, more preferably from 4-5.

The consumer expects - not least because of the light of the public Discussed discussion about the so-called "ozone hole" - on the one hand reliable information from the manufacturer on the sun protection factor, on the other hand goes a tendency of consumer behavior to use products with higher and higher sun protection factors.

Since sunscreens are usually expensive, and some In addition, sunscreen filter substances are difficult in higher concentrations it is to incorporate cosmetic or dermatological preparations advantageous, according to the invention in a simple and inexpensive way too Preparations reach which at low concentrations conventional sunscreen filters nevertheless acceptable or even achieve high SPF values.

Advantageously, therefore, the preparations of the invention can also Sunscreen filter substances containing UV radiation in the UVA and / or in Absorb UVB range, the total amount of these filter substances  z. B. 0.1 wt .-% to 40 wt .-%, preferably 0.5 to 10 wt .-%, in particular especially 1 to 6 wt .-%, based on the total weight of Preparation. They are also called UV filters, UVA filters and UVB filters designated.

Such preparations according to the invention can be advantageous as suns serve as a protective agent. Furthermore, it is of great advantage according to the invention Preparations in all sports activities, namely sweaty, to use.

Emulsions according to the invention z. B. in the form of a sunscreen or a sunscreen milk are advantageous and contain z. As the mentioned Fats, oils, waxes and other fatty substances, as well as water and a Emulsifier, as is customary for such a type of formulation is used.

The UVB filters may be oil-soluble or water-soluble. Advantageous oil-soluble UVB filters are z. B .:

• 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-methoxycinnamate;
• - esters of salicylic acid, preferably Salicylic acid (2-ethylhexyl) ester, Salicylic acid (4-isopropylbenzyl) ester, salicylate;
• - 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-methoxybenzalmalonate (2-ethylhexyl) ester;
• 2,4,6-trianilino (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine.

Advantageous water-soluble UVB filters are z. B .:

• - Salts of 2-phenylbenzimidazole-5-sulfonic acid such as its sodium, potassium or their triethanolammonium salt, as well as 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-Benzylidencamphers, such as. B. 4- (2-oxo-3- bornylidenemethyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3- bornylidenemethyl) sulfonic acid and its salts.

The total amount of the UVB filter substances can advantageously 0.1 wt .-% to 30% by weight, preferably 0.5 to 10% by weight, in particular 1 to 6% by weight amount, based on the total weight of the preparation.

Advantageously, the preparations according to the invention can also Contain substances that absorb UV radiation in the UVA range. UVA filter, which can be advantageously used according to the invention are For example, derivatives of dibenzoylmethane, in particular 1- (4'-tert.Bu tylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione and 1-phenyl-3- (4'- isopropylphenyl) propane-1,3-dione.

The total amount of the UVA filter substances can advantageously 0.1 wt .-% to 30% by weight, preferably 0.5 to 10% by weight, in particular 1 to 6% by weight amount, based on the total weight of the preparation.  

Also, all the following sunscreen filter substances can preferably in the used for UVA or UVB filters and also the quantities indicated for mixtures.

Particularly advantageous sunscreen filter substances are dibenzoylmethane derivatives, for example 5-isopropyldibenzoylmethane (CAS No. 63250-25-9), which is characterized by its structure

and is sold by Merck under the trade mark Eusolex® 8020, and 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS No. 70356-09-1), which is characterized by the structure

and sold by Givaudan under the trademark Parsol® 1789.

Another very advantageous sunscreen filter substance is the 4-Methylbenzyli dencampher, which is characterized by the structure

and sold by Merck under the Eusolex® 6300 brand. 4 Methylbenzylidene camphor is an extremely advantageous, under Normal conditions present as a solid sunscreen filter substance and is characterized by good UV filter properties.

Other Benzylidencampherderivate are very beneficial sunscreen filter substances, eg. B. the Benzylidencampher, which is characterized by the structure

and sold by the company Induchem under the brand name Unisol® S22.

Another particularly advantageous UV filter is the 4,4 ', 4' '- (1,3,5-triazine-2,4,6- triyltriimino) -tris-benzoic acid tris (2-ethylhexyl ester), synonym: 2,4,6-tris- [Anilino- (p-carbo-2'-ethyl-1'-hexyloxy)] - 1,3,5-triazine.  

This UVB filter substance is marketed by BASF Aktiengesellschaft under the brand name UVINUL® T 150 and is characterized by good UV absorption properties. UV filter substances, which are the structural motif

are also preferred.

In particular, s-triazine derivatives are preferred, their chemical structure by the generic formula

is reproduced, wherein
R is a branched or unbranched C ₁ -C ₁₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups,
X represents an oxygen atom or an NH group,
R _{1 is} a branched or unbranched C ₁ -C ₁₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a Group of formula

means in which
A is a branched or unbranched C ₁ -C ₁₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl or aryl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups,
R _{3 represents} a hydrogen atom or a methyl group,
n represents a number from 1 to 10,
R _{2 is} a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical optionally substituted by one or more C ₁ -C ₄ alkyl groups, when X represents the NH group, and a branched or unbranched C ₁ -C ₁₈ alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical optionally substituted by one or more C ₁ -C ₄ alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of formula

means in which
A is a branched or unbranched C ₁ -C ₁₈ -alkyl radical, a C ₅ -C ₁₂ -cycloalkyl or aryl radical, optionally substituted by one or more C ₁ -C ₄ -alkyl groups,
R _{3 represents} a hydrogen atom or a methyl group,
n represents a number from 1 to 10,
when X represents an oxygen atom.

The bis-resorcinyl triazine derivatives described in EP-A-775 698 are also preferably described, their chemical structure being defined by the generic formula

is reproduced, wherein R ₁ , R ₂ and A _{1 represent a} variety of organic radicals re.

Very advantageous bis-resorcinyl triazine derivatives are, for example, the following compounds:

wherein R _{3 represents} a hydrogen atom or a branched or unbranched alkyl group having 1 to 10 carbon atoms, in particular the 2,4-bis {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (4- methoxyphenyl) -1,3,5-triazine, which is characterized by the following structure:

Also advantageous is 2,4-bis - {[4- (3-sulfonato) -2-hydroxy-propyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine Sodium salt, which is characterized by the following structure:

Also advantageous is 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxy-propyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3, 5-triazine, which is characterized by the following structure:

Also advantageous is 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- [4- (2-methoxyethylcarboxyl) -phenylamino] -1,3, 5-triazine, which is characterized by the following structure:

Also advantageous is 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxy-propyloxy) -2-hydroxy] -phenyl} -6- [4- (2-ethyl-carboxyl) -phenylamino] -1,3,5-triazine, which is characterized by the following structure:

Also advantageous is 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} 6- (1-methylpyrrol-2-yl) -1,3,5-triazine which is characterized by the following structure:

Also advantageous is 2,4-bis - {[4-tris (trimethylsiloxy-silylpropyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine, which is characterized by the following structure is:

Also advantageous is the 2,4-bis - {[4- (2 '' - methylpropenyloxy) -2-hydroxy] phenyl} - 6- (4-methoxyphenyl) -1,3,5-triazine, which by the following structure marked is:

Also advantageous is the 2,4-bis - {[4- (1 ', 1', 1 ', 3', 5 ', 5', 5'-heptamethylsiloxy-2 "-methyl-propyloxy) -2-hydroxy ] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine, which is characterized by the following structure:

Yet another advantageous UV filter is 2,2'-methylene-bis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) -phenol), which is characterized by the chemical structural formula

is marked.

In particular, it was surprising that the X-ray amorphous oxide pigments for the purposes of the present invention would lead to an increase in the sun protection factor. UV filters selected from the following group are particularly preferred:

• 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester)
• 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) - 1,3,5-triazine,
• - 2,4-bis - {[4- (3-sulfonato) -2-hydroxy-propyloxy) -2-hydroxy] -phenyl} -6- (4-me thoxyphenyl) -1,3,5-triazine sodium salt,
• 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxy-propyloxy) -2-hydroxy] -phenyl} -6- (4- methoxyphenyl) -1,3,5-triazine,
• 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- [4- (2-methoxyethyl carboxyl) -phenylamino] -1,3,5-triazine,
• 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxy-propyloxy) -2-hydroxy] -phenyl} -6- [4- (2-ethyl-carboxyl) -phenylamino] -1,3,5-triazine,
• 2,4-bis - {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (1-methylpyrrol-2-yl) - 1,3,5-triazine,  
• 2,4-bis - {[4-tris (trimethylsiloxy-silyl-propyloxy) -2-hydroxy] -phenyl} -6- (4- methoxyphenyl) -1,3,5-triazine,
• - 2,4-bis - {[4- (2 '' - methylpropenyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphe nyl) -1,3,5-triazine,
• 2,4-bis - {[4- (1 ', 1', 1 ', 3', 5 ', 5', 5'-heptamethylsiloxy-2 "-methyl-propyloxy) -2- hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine.

The preparations with a content of sunscreen filters are in itself produced in a known manner. Water-soluble UV filters may preferably be used in the aqueous phase, oil-soluble UV filter preferably in the fatty phase be incorporated.

The preparations according to the invention of the type of Pre-sun preparations may optionally also preferably contain inorganic pigments, the Protect the skin against UV radiation in a known manner.

Particularly preferred are hydrophobic inorganic pigments.

It had not been foreseen that the full activity of the chaotropic compounds would be preserved, because it can be suspected be that the chaotropic compounds, in particular urea, for example on the Surface of the hydrophobic inorganic pigments are adsorbed.

For example, M. Schmidt et al. Describe in "XPS studies of amino acid adsorbed on titanium dioxide surfaces,"Fresenius' Journal of Analytical Chemistry (1991) 341, p. 412-415, that certain amino acids are readily adsorbed by the surface of titanium dioxide particles. However, this work by no means provides an indication of the present invention and its advantageous properties. In addition, the TiO ₂ , which is quoted above, is not hydrophobic.

On the contrary, the above-quoted work would have suggested that by a Adsorption of the chaotropic compounds reduces their desired activity becomes.

In an unexpected way, however, it has been found that for the activity (which, for example, is reflected in the excellent values for the Skin moisture after application of chaotropic compounds such as urea containing formulations) no difference between For results mulierungen, which contain pigments of the invention and those who are free from it.

Furthermore, it is surprising that just hydrophobicized inorganic pigments have the advantageous properties of the invention, since chaotropic Compounds are described as pronounced hydrophilic substances.

Cosmetic and dermatological preparations according to the invention preferably contain inorganic pigments based on metal oxides and / or other sparingly soluble or insoluble metal compounds, in particular the oxides of titanium (TiO ₂ ), zinc (ZnO), iron (eg Fe ₂ O ₃ ). , Zirconium (ZrO ₂ ), silicon (SiO ₂ ), manganese (for example MnO), aluminum (Al ₂ O ₃ ), cerium (for example Ce ₂ O ₃ ), mixed oxides of the corresponding metals and mixtures such oxides. Particular preference is given to pigments based on TiO ₂ .

Prerequisite for the usability of inorganic pigments for the Purpose of the invention is of course the cosmetic or dermatological Safety of the underlying substances.

Substantially insignificant for the present invention is in which modifications such metal oxides are present. For example, TiO ₂ occurs naturally in three major modifications (rutile, anatase, and brookite), all of which are all equally suitable. The same applies to the modifications of iron oxides, etc.

It is advantageous, the particle diameter of the pigments used smaller than 100 nm to choose.

Preferably, the inorganic pigments are in hydrophobic form, d. h. that they are superficially treated water repellent. This upper Surface treatment may consist in that the pigments after itself be provided with a thin hydrophobic layer known methods.

One such method is, for example, that the hydrophobic surface layer after a reaction according to

n TiO ₂ + m (RO) ₃ Si-R '→ n TiO ₂ (surface)

is produced. n and m are stoichioms to be used at will trical parameters, R and R 'the desired organic radicals. example example in analogy to DE-OS 33 14 742 illustrated hydrophobized pigments are beneficial.

Advantageous TiO ₂ pigments are obtainable, for example, under the trade names T 805 (DEGUSSA) or M 262 (KEMIRA) or MT 100 T (TAYCA).

Advantageous SiO ₂ pigments can be chosen from the series of hydrophobic pigments marketed under the trade names AEROSIL (DEGUSSA), for example AEROSIL R 812 or AEROSIL R 972.

Preparations according to the invention are advantageous by a content of 0.1 to 10 wt .-%, in particular 0.5-5.0 wt .-% of inorganic pigments  in each case based on the total weight of the together setting.

Combination and preparations, in particular sunscreen preparations, which contain combinations of active substances of the various named active substance groups which protect against UV radiation are also preferably used according to the invention. These are the following combinations and preparations:

• a) chaotropic compounds and UV filters (UVA and / or UVB filters), or
• b) chaotropic compounds and inorganic pigments or
• c) chaotropic compounds and UV filters (UVA and / or UVB filters) and inorganic pigments.

It can be at least one compound from an active ingredient group can be selected, but also several can be used.

The active compounds may preferably be in the amounts indicated above be used, but more preferably each with half of specified weight quantities.

However, the invention also relates to the following preparations with combinations of active substances according to the invention, Pre-sun preparations being preferred preparations:
Cosmetic and dermatological topical preparations containing

• a) chaotropic compounds and UV filters (UVA and / or UVB filters) or  
• b) chaotropic compounds and inorganic pigments or
• c) chaotropic compounds and UV filters (UVA and / or UVB filters) and inorganic pigments.

It can be at least one compound from an active ingredient group can be selected, but also several can be used.

The active compounds may preferably be in the abovementioned Amounts are used, but preferably each with half of indicated weight amounts.

The production of preparations according to the invention takes place according to the usual, familiar to the expert rules. Advantageously, the invention proper preparations in the form of emulsions, preferably W / O emulsions in front. However, it is also possible and may be advantageous according to the invention, to choose other types of formulations, for example hydrodispersions, Gels, oils, multiple emulsions, for example in the form of W / O / W or O / W / O emulsions, anhydrous ointments or ointment bases etc.

In simple emulsions are in the one phase finely dispersed, of a Emulsifier shell enclosed second phase droplets (water droplets in W / O or lipid vesicles in O / W emulsions). In a multiple emulsion (second degree), however, are in such droplets of fine disperse droplets emulsified in the first phase. In turn, even in these droplets can still fine disperse droplets (multiple third degree emulsion) and so on continued.

Just as you can with the simple emulsions of W / O or O / W emulsions speaks (water-in-oil or oil-in-water), there are multiple Emulsions W / O / W, O / W / O, O / W / O / W, W / O / W / O emulsions and so on.  

Multiple emulsions in which the respective inner and outer water phase or inner and outer oil phases are different in nature (ie z. B. W / O / W 'and O / W / O'-emulsions), are the preparation by Zweitopf method accessible. Such emulsions in which the inner and outer Water or oil phases are not different, are both by One or two-pot process available.

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

Methods for producing multiple emulsions are known per se to the person skilled in the art common. Thus, there are two-pot processes in which a simple emulsion (e.g. a W / O emulsion) and by adding a further phase (eg. a water phase) with a suitable emulsifier (eg an O / W emulsifier) into a multiple emulsion (eg, a W / O / W emulsion) becomes.

A second method is emulsifier mixtures with an oil phase and a water phase in a one-pot process into a multiple W / O / W emulsion to convict. The emulsifiers are dissolved in the oil phase and combined with the water phase. A prerequisite for such a method is that the HLB values (HLB = hydrophilic-lipophilic balance) of the used individual emulsifiers differ significantly from each other. Hydrodisper ions form dispersions of a liquid, semi-solid or solid inner (discontinuous) lipid phase in an external aqueous (continuous) Phase dar.

In contrast to O / W emulsions, which are characterized by a similar phase However, hydrodispersions are essentially free of Emulsifiers. Hydrodispersions, as well as emulsions, are metastable systems and are inclined to enter a state of two in themselves  to pass on coherent discrete phases. Prevented in emulsions the choice of a suitable emulsifier phase separation.

For hydrodispersions of a liquid lipid phase in an external aqueous Phase can, for example, the stability of such a system be ensured that a gel skeleton is built up in the aqueous phase, in which the lipid droplets are stably suspended.

It is possible and advantageous to use the inorganic pigment (s) and the chaotropic compounds at any point in the production of the Preparations (for example emulsion preparation for the emulsion mixture) admit. This can be pigment or pigments and chaotropic Compounds both separately and already added together zugege ben.

Preferably, the chaotropic compounds in the aqueous phases incorporated. The production takes place according to the usual procedures of Cosmetics or galenics.

Preference is given to preparations containing the active substances according to the invention which are used for Treatment and care of hands, face, hair and so on the scalp are determined.

Particularly advantageous preparations are also obtained when the Agents of the invention are combined with antioxidants. According to the invention, the preparations advantageously contain one or more Antioxidants. As a cheap, but nevertheless optional to use anti All oxidants can be used for cosmetic and / or dermatological purposes Applications used suitable or common antioxidants become.  

Particularly advantageous antioxidants are selected from the group consisting of
Amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carosin and their derivatives (eg anserine), Carotenoids, carotenes (eg, alpha-carotene, beta-carotene, lycopene) and their derivatives, lipoic acid and its derivatives (eg, dihydrolipoic acid), aurothioglucose, propylthiouracil, and other thiols (eg, thioredoxin, glutathione, cysteine , Cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, gamma-linoleyl, cholesteryl and glyceryl esters) and theirs Salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (eg Buthioninsulfoximine, Homozy steinsulfoximin, Buthioninsulfone, pentat, hexa, Heptahioninsulfoximin) in very low tolerated dosages (eg pmol to mmol / kg), furthermore (Met all) chasers (eg. Alpha-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), alpha hydroxy acids (eg, citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (eg gamma-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol their derivatives, vitamin C and derivatives (eg ascorbyl palmitates, Mg ascorbyl phosphates, ascorbyl acetates), tocopherols and derivatives (e.g. Vitamin E - acetate), vitamin A and derivatives (vitamin A - palmitate) as well as benzylic benzoic acid benzoate, flavonoids, eg. B. rutinic acid and its derivatives, chrysin, naringin, hesperidin, naringenin, hesperetin, morin, phloridzin, diosmin, neohesperidin dihydrochalcone, flavone and especially alpha-glucosylrutin, ferulic acid and its derivatives, butylhydroxytoluene, butylhydroxyanisole, fural glucitol, nordihydroguaiacetic acid, nordihydroguaja retsäure, Trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (eg ZnO, ZnSO ₄ ) selenium and its derivatives (eg selenium methionine), stilbenes and their derivatives (eg stilbene oxide, Trans Stilbene oxide) and the inventively suitable derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of said active substances.

Particularly advantageous for the purposes of the present invention may be oil-soluble Antioxidants are used.

The amount of antioxidants (one or more compounds) in the Preparations is preferably 0.001 to 30 wt .-%, especially preferably 0.01-10 wt .-%, in particular 0.1-5 wt .-%, based on the Total weight of the preparation.

If vitamin E and / or its derivatives are the antioxidant (s) It is advantageous if their respective concentrations are within the range of 0.001-10 wt%, based on the total weight of the formulation choose.

If vitamin A, or vitamin A derivatives, or carotenes or their derivatives which represent antioxidants or antioxidants, it is advantageous to their respective Concentrations in the range of 0.001-10 wt .-%, based on the Total weight of the formulation to choose.

It is also advantageous to the compositions auxiliaries and / or additives Incorporate, which increase the stability or from the galenical point of view Improve or change the quality of the compositions.

The cosmetic preparations according to the invention can be cosmetic Contain excipients, such as those commonly used in such preparations be, for. B. preservatives, bactericides, deodorizing Substances, antiperspirants, insect repellents, vitamins, agents for ver foaming, dyes, coloring pigments, Thickening agents, softening substances, moisturizing and / or  moisturizing substances, fats, oils, waxes or other common stock parts of a cosmetic formulation such as alcohols, polyols, polymers, Foam stabilizers, electrolytes, organic solvents or silicone probe rivate.

Also advantageous are those cosmetic and dermatological Preparations in the form of a sunscreen, a pre-sun or After-sun product available. Advantageously, these additionally contain minde at least one UVA filter and / or at least one UVB filter.

Furthermore, such inventive cosmetic and dermatolo are particularly advantageous in the form of a sun protection product, a pre-sun or after-sun product and additionally to the UVA filter (s) and / or the UVB filter (s) contain several antioxidants.

All quantities, percentages or parts are, if not stated otherwise, on the weight, in particular on the total weight of Preparations or the respective mixture.

The examples illustrate advantageous embodiments of the present invention represents:

The following sunscreen filters are used:
Uvinul T 150 (BASF):
4,4 ', 4''- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester), synonymous: 2,4,6-tris [anilino- (p-carbo-2'-ethyl-1'-hexyloxy)] - 1,3,5-triazine
Eusolex 232 (Merck):
phenylbenzimidazolesulfonic
Parsol 1789 (Givaudan):
4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS # 70356-09-1)
Eusolex 6300 (Merck):
4-methylbenzylidenecamphor

example 1 Sun cream, O / W, SPF 20

Wt .-% cyclomethicone 3.00 Glyceryl stearate + PEG-30 stearate 2.00 Wool alcohol 0.10 glyceryl stearate 3.00 isopropyl palmitate 2.00 octyldodecanol 1.00 C _12-15 alkyl benzoate 2.00 glycerin 3.00 cetyl alcohol 3.00 myristate 2.00 Uvinul T150 4.50 urea 2.00 butylmethoxydibenzoylmethane 2.00 phenylbenzimidazolesulfonic 3.00 tocopheryl acetate 0.50 EDTA solution (20%) 0.50 NaOH (45%) q.s. ethyl alcohol 4.00 preservative q.s. Perfume q.s. Hydrophobic TiO ₂ 2.00 water ad 100.00

Example 2 Sun cream, O / W, SPF 8

Wt .-% cyclomethicone 3.00 Glyceryl stearate + PEG-30 stearate 2.00 glyceryl stearate 3.00 isopropyl palmitate 2.00 octyldodecanol 3.00 glycerin 3.00 cetyl alcohol 3.00 phenylbenzimidazolesulfonic 1.00 Methyl Benzylidene Camphor 4.00 urea 5.00 butylmethoxydibenzoylmethane 2.00 tocopheryl acetate 0.50 EDTA solution (20%) 0.50 NaOH (45%) q.s. ethyl alcohol 1.50 preservative q.s. Perfume q.s. TiO ₂ 2.00 water ad 100.00

Example 3 Sun Milk, O / W

Wt .-% Trilaureth-4 phosphate 0.75 Triceteareth-4 phosphate 1.00 Glyceryl stearate + PEG-100 stearate 1.00 Glyceryl stearate + ceteareth-20 0.80 glyceryl 0.50 isopropyl palmitate 3.00 Glycerol caprylate / caproate 5.00 ("Caprilic / Capric Triglycerides") @ cetyl alcohol 1.00 xanthan gum 0.30 L-arginine 5.00 octyl 6.00 butylmethoxydibenzoylmethane 0.50 methylbenzylidene 3.00 phenylbenzimidazolesulfonic 4.00 butylhydroxytoluene 0.06 EDTA solution (20%) 0.50 NaOH q.s. preservative q.s. Hydrophobic TiO ₂ 3.00 water ad 100.00

Example 4 Sun Milk, O / W

Wt .-% cyclomethicone 2.00 Cetearyl Alcohol + PEG-40 Hydrogenated Castor Oil + Sodium Cetearyl Sulfate 2.50 glyceryl 1.00 Glycerol caprylate / caproate 2.00 ("Caprilic / Capric Triglycerides") @ octyl 3.00 castor oil 4.00 glycerin 3.00 Carbomer 0.23 hydroxypropyl methylcellulose 0.30 PVP / hexadecene copolymer 1.50 Methylbenzylidene Camphor 4.00 urea 10.00 Uvinul T 150 3.00 butylmethoxydibenzoylmethane 2.00 butylhydroxytoluene 0.03 EDTA solution (20%) 0.50 NaOH q.s. preservative q.s. Perfume q.s. Hydrophobic TiO ₂ 1.50 water ad 100.00

Example 5 Sun Milk, O / W

Wt .-% stearic acid 2.00 cetyl palmitate 1.00 Glycerol caprylate / caproate 2.0 ("Caprilic / Vapric Triglycerides") @ sorbitan 1.00 sorbitan 1.50 Paraffin oil, DAB 9 1.29 cetearyl 0.80 glycerin 3.00 2-hydroxy-4-methoxybenzophenone 1.00 octyl 5.00 methylbenzylidene 1.00 butylhydroxytoluene 0.06 simethicone 0.20 Polyethylengllycol-150 3.00 triethanolamine 0.85 urea 7.00 Carbomer 0.10 ethyl alcohol 3.00 preservative q.s. Perfume q.s. TiO ₂ 2.00 water ad 100.00

Example 6 Sun cream, O / W, SPF 20

Wt .-% cyclomethicone 3.00 Glyceryl stearate + PEG-30 stearate 2.00 Wool alcohol 0.10 glyceryl stearate 3.00 isopropyl palmitate 2.00 octyldodecanol 1.00 C _12-15 alkyl benzoate 2.00 glycerin 3.00 cetyl alcohol 3.00 myristate 2.00 Uvinul T150 4.50 urea 4.00 butylmethoxydibenzoylmethane 2.00 phenylbenzimidazolesulfonic 3.00 tocopheryl acetate 0.50 EDTA solution (20%) 0.50 NaOH (45%) q.s. ethyl alcohol 4.00 preservative q.s. Perfume q.s. Hydrophobic TiO ₂ 2.00 water ad 100.00

Example 7 Sun cream, O / W

Wt .-% cyclomethicone 3.00 Glyceryl stearate + PEG-30 stearate 2.00 glyceryl stearate 3.00 isopropyl palmitate 2.00 octyldodecanol 3.00 glycerin 3.00 cetyl alcohol 3.00 phenylbenzimidazolesulfonic 1.00 octyl 5.00 Uvinul T150 2.00 urea 8.00 butylmethoxydibenzoylmethane 0.50 tocopheryl acetate 0.50 EDTA solution (20%) 0.50 NaOH q.s. ethyl alcohol 1.50 preservative q.s. Perfume q.s. TiO ₂ 1.00 water ad 100.00

Example 8 Sun Milk, O / W

Wt .-% Trilaureth-4 phosphate 0.75 Triceteareth-4 phosphate 1.00 Glyceryl stearate + PEG-100 stearate 1.00 Glyceryl stearate + ceteareth-20 0.80 glyceryl 0.50 isopropyl palmitate 3.00 Glycerol caprylate / caproate 5.0 ("Caprilic / Capric Tetriglyceride") @ cetyl alcohol 1.00 urea 4.00 xanthan gum 0.30 octyl 6.00 butylmethoxydibenzoylmethane 0.50 methylbenzylidene 3.00 phenylbenzimidazolesulfonic 4.00 butylhydroxytoluene 0.06 EDTA solution (20%) 0.50 NaOH q.s. preservative q.s. Hydrophobic TiO ₂ 3.00 water ad 100.00

Example 9 Sun Milk, O / W

Wt .-% cyclomethicone 2.00 Cetearyl Alcohol + PEG-40 Hydrogenated Castor Oil + Sodium Cetearyl Sulfate 2.50 Glyyceryllanolat 1.00 Glycerol caprylate / caproate 2.00 ("Caprilic / Capric Triglycerides") @ octyl 3.00 castor oil 4.00 glycerin 3.00 Carbomer 0.23 hydroxypropyl methylcellulose 0.30 PVP / hexadecene copolymer 1.50 Uvinul T 150 4.00 butylmethoxydibenzoylmethane 2.00 urea 8.00 methylbenzylidene 3.50 butylhydroxytoluene 0.03 EDTA solution (20%) 0.50 NaOH q.s. preservative q.s. Perfume q.s. Hydrophobic TiO ₂ 1.50 water ad 100.00

Example 10 Sun Milk, O / W

Wt .-% stearic acid 2.00 cetyl palmitate 1.00 Glycerol caprylate / caproate 2.00 ("Caprilic / Capric Triglycerides") @ sorbitan 1.00 sorbitan 1.50 Paraffin oil, DAB 9 1.29 cetearyl 0.80 glycerin 3.00 2-hydroxy-4-methoxybenzophenone 1.00 butylmethoxybenzoylmethane 2.00 methylbenzylidene 1.00 butylhydroxytoluene 0.06 simethicone 0.20 urea 8.00 Polyethylene glycol-150 3.00 triethanolamine 0.85 Carbomer 0.10 ethyl alcohol 3.00 preservative q.s. Perfume q.s. Hydrophobic TiO ₂ 2.00 water ad 100.00

Example 11 O / W / O emulsion

Wt .-% glyceryl 4.00 Cetearylisononaoat 20.00 stearic acid 2.00 Uvinul® T150 2.00 Parsol® 1789 3.00 NaOH ad pH 7.0 urea 5.00 Dyes, perfume, preservatives q.s. water ad 100.00

The UV filters are dissolved in the oil phase and with the remaining oil phase united. Water is added and the system is heated to 40 ° C. NaOH is added until a pH of 7 is reached, after which it is released Room temperature cooled.  

Example 12 Sun cream, O / W

Wt .-% Polyglyceryl-2 polyhydroxystearate 5.00 Hydrogenated Coco Glycerides (Softisan 100) 3.00 glycerin 3.00 Wax, microcrystalline (Lunacera S) 0.50 magnesium sulfate 0.70 mineral oil 12,00 Caprylyl ether 8.00 Uvinul T150 3.00 Cetearyl isononanoate 6.00 urea 3.00 Eusolex 232 1.5 Parsol 1789 2.0 Titanium dioxide, hydrophobic 1.0 Preservative, perfume q.s. Water, demin. ad 100.00

Example 13 Sunscreen lotion, W / O

Wt .-% Polyglyceryl-2 polyhydroxystearate 5.00 magnesium stearate 0.05 butylene 5.00 Hydroxyoctacosanyl hydroxystearates (Elfacos C26 (CTFA)) 1.00 magnesium sulfate 0.50 Isohexadecan 7.00 Capric / caprylic triglycerides 5.00 cetearyl 14.00 Uvinul T 150 5.00 urea 7.5 Parsol 1789 1.0 Eusolex 6300 4.0 Preservative, perfume q.s. water ad 100.00

Claims (9)

1. Use of one or more compounds from the Group of chaotropic compounds as active ingredients or cosmetic and dermatological topical preparations containing one or more compounds from the group of chaotropic compounds as active ingredients to protect the skin against UV radiation. 2. Use according to claim 1 of one or more compounds Compounds from the group of chaotropic compounds as Active ingredients or cosmetic and dermatological, topical Preparations containing one or more compounds Compounds from the group of chaotropic compounds as Active ingredients to protect the skin against UV radiation by increasing the self-protection time of the skin against UV radiation. 3. Use of combinations of

• a) chaotropic compounds and UV filters (UVA and / or UVB filters), or
• b) chaotropic compounds and inorganic pigments or
• c) chaotropic compounds and UV filters (UVA and / or UVB filters) and inorganic pigments
  to protect the skin against UV radiation.

4. Use of cosmetic and dermatological topical preparations containing combinations of

• a) chaotropic compounds and UV filters (UVA and / or UVB filters), or
• b) chaotropic compounds and inorganic pigments or
• c) chaotropic compounds and UV filters (UVA and / or UVB filters) and inorganic pigments
  to protect the skin against UV radiation.

5. Cosmetic and dermatological topical preparations containing

• a) chaotropic compounds and UV filters (UVA and / or UVB filters), or
• b) chaotropic compounds and inorganic pigments or
• c) chaotropic compounds and UV filters (UVA and / or UVB filters) and inorganic pigments.

6. Use according to claims 1 and 4, characterized that the preparations chaotrope compounds in amounts of 0.01 to 30 wt .-%, preferably 0.1 to 20 wt .-%, in particular 1 to 10 Wt .-%, in each case based on the total weight of Preparations. 7. Use according to claim 4, characterized in that the Total amount of UV filter substances 0.1% by weight to 40% by weight, preferably 0.5 to 10% by weight, in particular 1 to 6% by weight, based on the total weight of the preparation. 8. Use according to claim 4, characterized in that the Amount of inorganic pigments 0.1 to 10 wt .-%, in particular 0.5-5 wt .-%, each based on the total weight of Preparations, amounts. 9. uses or preparations according to claims 1 to 6, characterized in that the chaotropic compound is urea.