WO1999053894A1

WO1999053894A1 - Cosmetic or dermatological preparations containing unsymmetrically substituted triazine derivatives, representing water-resistant sunscreen preparations in the form of oil/water emulsions

Info

Publication number: WO1999053894A1
Application number: PCT/EP1999/002575
Authority: WO
Inventors: Heinrich Gers-Barlag; Birgit Hargens; Anja MÜLLER
Original assignee: Beiersdorf Ag
Priority date: 1998-04-18
Filing date: 1999-04-16
Publication date: 1999-10-28
Also published as: EP1073411A1; JP2002512178A; DE19817296A1

Abstract

The invention relates to the use of combinations of active ingredients having a sunscreen action, consisting of a) one or more water-soluble UV filter substances, especially those which on their molecular backbone carry one or more sulphonic acid groups or sulphonate groups, and b) one or more unsymmetrically substituted s-triazine derivatives. These combinations are used to produce water-resistant sunscreen preparations in the form of oil/water emulsions.

Description

description

Cosmetic or dermatological preparations containing unsymmetrically substituted triazine derivatives, which waterproof light protection preparations in the form of

Represent O / W emulsions

The present invention relates to cosmetic and dermatological preparations containing unsymmetrically substituted triazine derivatives. The present invention relates to cosmetic and dermatological light protection preparations, in particular skin care cosmetic and dermatological light protection preparations. In a particularly preferred embodiment, the present invention relates to waterproof light protection preparations.

The damaging effect of the ultraviolet part of solar radiation on the skin is generally known. While rays with a wavelength shorter than 290 nm (the so-called UVC range) are absorbed by the ozone layer in the earth's atmosphere, rays in the range between 290 nm and 320 nm, the so-called UVB range, cause erythema simple sunburn or even more or less severe skin burns.

The narrower range around 308 nm is regarded as a maximum of the erythema effectiveness of sunlight.

Numerous compounds are known to protect against UVB radiation, most of which are derivatives of 3-benzylidene camphor, 4-aminobenzoic acid, cinnamic acid, salicylic acid, benzophenone and also 2-phenylbenzimidazole. can. It has been proven that UVA radiation leads to damage to the elastic and collagen fibers of the connective tissue, which causes the skin to age prematurely and can be seen as the cause of numerous phototoxic and photoallergic reactions. The damaging influence of UVB radiation can be intensified by UVA radiation.

However, UV radiation can also lead to photochemical reactions, in which case the photochemical reaction products intervene in the skin and cell metabolism.

Mostly such photochemical reaction products are radical compounds, e.g. Hydroxy radicals, hydroperoxy radicals and superoxide ions. Undefined radical photo products, which are created in the skin itself, can also display uncontrolled subsequent reactions due to their high reactivity. But also singlet oxygen, a non-radical excited state of the oxygen molecule, can occur with UV radiation, just as short-lived epoxies and many others. Singlet oxygen, for example, is characterized by increased reactivity compared to the triplet oxygen normally present (radical ground state). However, there are also excited, reactive (radical) triplet states of the oxygen molecule.

In order to prevent these reactions, additional antioxidants and / or free radical scavengers can be incorporated into the cosmetic or dermatological formulations.

UV absorbers or UV reflectors are most inorganic pigments that are known to be used in cosmetics to protect the skin from UV rays. These are oxides of titanium, zinc, iron, zirconium, silicon, manganese, aluminum, cerium and mixtures thereof, as well as modifications.

Sunscreen preparations are particularly often required and used on bathing beaches or in outdoor pools. It is then desirable that the light protection formulation is largely water-resistant, so that it is not washed off the skin or only to a small extent.

Higher sun protection factors, for example those located above LF 15, can generally only be achieved by using large amounts of UV filter substances. Should If a sun protection product has a high sun protection factor even after bathing, the UV filter substance on the skin in particular must be retained.

In itself it is annoying if the sun protection product has to be applied again after bathing. When bathing itself, the use of a washable light protection formulation can even be reckless and harmful to the skin, since water absorbs light poorly in the UVA and UVB range, and consequently does not represent any significant UV protection, not even for submerged skin areas.

Water-soluble UV filter substances are electrolytes which, in particular, destabilize O / W emulsions. In order to counteract this destabilization, polyethoxylated emulsifiers are used. However, these often have dermatological disadvantages, because the use of the usual cosmetic emulsifiers is harmless. Nevertheless, emulsifiers, like any chemical substance, can cause allergic or hypersensitive reactions in individual cases.

Although there are definitely advantageous cosmetic or dermatological preparations for protecting the skin from the harmful effects of the action of UV light, a frequently observed disadvantage is that the preparations are not or not sufficiently waterproof.

For waterproof light protection formulations, the prior art usually uses non-water-soluble UV filter substances, water-repellent raw materials (e.g. silicone oils in high concentrations) and / or film formers, in particular high-molecular compounds (e.g. PVP / hexadecene copolymers). This creates barriers between the UV filter substances on the skin and the water.

The disadvantage here is that the diffusion of the filter substances into the water is delayed, but cannot be completely prevented. Products of this type can therefore lose a considerable amount of protective effect when bathing for a long time.

The disadvantage here is that the diffusion of the filter substances into the water is delayed, but cannot be completely prevented. Products of this type can therefore lose a considerable amount of protective effect when bathing for a long time. But even through normal sweat development or wiping off this sweat and the light protection substances dissolved or dissolved therein, there can be a considerable reduction in light protection. UV filter substances, which are the structural motif, were presented by various authors

exhibit.

With regard to the C ₃ axis of the basic triazine body, both symmetrical substitution and asymmetrical substitution are conceivable. In this sense, symmetrically substituted s-triazines have three identical substituents and are represented, for example, by the 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester), analogous to the INCI nomenclature: octyltriazon, which is represented by the following structure:

H

As a result, s-triazine derivatives which are unsymmetrically substituted with respect to the C ₃ axis have different substituents, as a result of which the C ₃ symmetry is destroyed. For the purposes of the present invention, “symmetrical” or “asymmetrical” is always understood to be symmetrical or asymmetrical with respect to the C ₃ axis of the triazine base, unless something else was expressly mentioned.

For example, EP-A-570 838 describes unsymmetrically substituted s-triazine derivatives whose chemical structure is represented by the generic formula

NH ^ N. NH

R

N: N

NH

o- ~ X— R ₂ is reproduced, whereby

R represents a branched or unbranched C ₈ -alkyl radical, a C ₅ -C ₂ -cycloalkyl radical, optionally substituted with one or more dC - alkyl groups, X represents an oxygen atom or an NH group, Ri represents a branched or unbranched C 1 -C 8 ₈ -alkyl radical, a C ₅ -C ₂ cycloalkyl radical, optionally substituted with 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

-O— CH ₂ -CH- IR ₃

means in which

A represents a branched or unbranched d-cis-alkyl radical, a Cs-C ₂ -cycloalkyl or aryl radical, optionally substituted with one or more d-

C ₄ - alkyl groups, R _{3 represents} a hydrogen atom or a methyl group, n represents a number from 1 to 10, a branched or unbranched Ci-Cis-alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical, optionally substituted with one or more Cι- C - alkyl groups, when X represents the NH group, and a branched or unbranched C cis-alkyl radical, a Cs -C ₂ -cycloalkyl radical, optionally substituted with one or more dC ₄ - alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula

O— CH ₂ -CH-

IR ₃

-i n means in which

A represents a branched or unbranched d-cis-alkyl radical, a C ₅ -d ₂ -cycloalkyl or aryl radical, optionally substituted by one or more d-

C - 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.

Such s-triazine derivatives, which in contrast to 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltrimino) -tris-benzoic acid tris (2-ethylhexyl ester) improved by Characterize solubility in many oil components, according to the teaching of documents EP-A-821 937, EP-A-821 938, EP-A-821 939, EP-A-821 940 and EP-A-821 941 with different other light protection filters can be combined in cosmetic or dermatological preparations, in order to take account of certain technical facts, and sulfonated UV filter substances are also mentioned as optional components of the formulations mentioned in the abovementioned documents.

It was therefore an object of the present invention to remedy all of these problems. A further object of the present invention was to provide light protection preparations which are notable for a high light protection action and good cosmetic and dermatological acceptance.

Surprisingly, all of these tasks are solved by the use of combinations of active ingredients which act as sunscreens

(a) one or more water-soluble UV filter substances, in particular those which carry one or more sulfonic acid groups or sulfonate groups on their molecular structure and

(b) one or more asymmetrically substituted s-triazine derivatives for the production of waterproof light protection preparations in the form of O / W emulsions

or the use of combinations of active ingredients which act to protect against light

(b) one or more asymmetrically substituted s-triazine derivatives for producing or increasing the water resistance of light protection preparations which are in the form of O / W emulsions. In an advantageous embodiment, the present invention relates to the use of combinations of active ingredients which act to protect against light

(b) one or more unsymmetrically substituted s-triazine derivatives, which are characterized in that the unsymmetrically substituted s-triazine derivative (s) are selected from the group of substances whose chemical structure is represented by the generic formula

NH, N. ^ NH

N: N

NH

O ^ ^ XR _{2 is} reproduced with

R represents a branched or unbranched C 1 -C ₈ -alkyl radical, a Cs-C ₁ -cycloalkyl radical, optionally substituted by one or more C 1 -C ₄ -alkyl groups, X represents an oxygen atom or an NH group, R _{T represents} a branched or unbranched C ₁ -C ₈ alkyl radical, a C ₃ -C ₂ cycloalkyl radical, optionally substituted with one or more CrC ₄ alkyl groups, or a

Hydrogen atom, an alkali metal atom, an ammonium group or a group of

formula

A- O- CH ₂ - CH- IR ₃

means in which A represents a branched or unbranched dC ₁₈ -alkyl radical, a Cs-Cir-cycloalkyl or aryl radical, optionally substituted by one or more d- C ₄ -alkyl groups,

R _{3 represents} a hydrogen atom or a methyl group, n represents a number from 1 to 10, a branched or unbranched C ₁ -C 8 alkyl radical, a C ₅ -C ₂ cycloalkyl radical, optionally substituted with one or more C ₁ -C ₄ alkyl groups , represents when X represents the NH group, and a branched or unbranched C ₁ -C 8 alkyl radical, a C ₃ -C ₂ cycloalkyl radical, optionally substituted with one or more dC ₄ alkyl groups, or a

Hydrogen atom, an alkali metal atom, an ammonium group or a group of

formula

A- O- CH ₂ -CH- R ₃

means in which

A represents a branched or unbranched d-cis-alkyl radical, a Cs-C ₁₂ -cycloalkyl or aryl radical, optionally substituted by one or more d-

C ₄ - alkyl groups, R _{3 represents} a hydrogen atom or a methyl group, n represents a number from 1 to 10, if X represents an oxygen atom, for the production of waterproof light protection preparations in the form of O / W emulsions.

In a particularly preferred embodiment, the present invention relates to the use of combinations of active ingredients which act to protect against light

(b) one or more asymmetrically substituted s-triazine derivatives, characterized in that the unsymmetrically substituted s-triazine derivative is chosen to be the dioctylbutylamidotriazone, the chemical structure of which is given by the formula 10

Nv.

is used to manufacture waterproof light protection preparations in the form of OAΛ emulsions.

Advantageous water-soluble UV filter substances in the sense of the present invention are in particular those which carry one or more sulfonic acid groups or sulfonate groups on their molecular structure. The following are particularly preferred:

The 2-phenylbenzimidazole-5-sulfonic acid and its salts, for example the sodium, potassium or its triethanolammonium salt

Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenon-5-sulfonic acid and their salts, for example the corresponding sodium, potassium or triethanolammonium salt:

SO ₃ H

OCH ₃ 11

Sulfonic acid derivatives of 3-benzylidene camphor, e.g. 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid and its salts, for example the corresponding sodium, potassium or triethanolammonium salt:

SO ₃ H

The 2-methyl-5- (2-oxo-3-bornylidenemethyl) benzenesulfonic acid and its salts, for example the corresponding sodium, potassium or triethanolammonium salt:

The 1, 4-di (2-oxo-10-sulfo-3-bornylidenemethyl-) benzene and its salts (the corresponding 10-sulfato compounds, e.g. the corresponding sodium, potassium or triethanolammonium salt), also as benzene -1, 4-di (2-oxo-3-bornylidenemethyl-10-sulfonic acid denotes:

Although water-soluble UV filter substances used according to the invention, which carry a sulfonic acid group or sulfonate group on their molecular structure, extremely 12

those UV filter substances which have two or more sulfonic acid groups or sulfonate groups on their molecular structure are often preferred.

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

In a further particularly preferred embodiment, the present invention relates to light protection preparations in the form of O / W emulsions comprising active compound combinations

(b) one or more asymmetrically substituted s-triazine derivatives,

(c) one or more surface-active substances A, selected from the group of glucose derivatives, which are characterized by the structural formula

O

O— C— R ₄

/

H C

HO '

HO OR ₅

O

IR ₆ distinguish, wherein R _{4 represents} a branched or unbranched alkyl radical having 1 to 24 carbon atoms, where R _{5 represents} either a hydrogen atom or a branched or unbranched alkyl radical having 1 to 24 carbon atoms and where Rβ either represents a hydrogen atom or a branched or unbranched acyl radical Represents 1 to 24 carbon atoms, and.

(d) if desired, one or more surface-active substances B, selected from the group of substances of the general structural formula 13

Rj - O - f - CH ₂ - CH - CH ₂ --OH R ₉ n OR ₈ where R ₇ , Rβ and R ₉ are selected from the group comprising: H, branched or unbranched, saturated or unsaturated fatty acid residues with 8 to 24 carbon atoms, in which up to three aliphatic hydrogen atoms can be substituted by hydroxyl groups and n represents a number from 2 to 8.

In a further, very particularly preferred embodiment, the present invention relates to light protection preparations in the form of O / W emulsions comprising active ingredient combinations

(b) one or more asymmetrically substituted s-triazine derivatives,

O

II

O— C— R ₄

HO "0-R ₅

O

IR ₆ distinguish, wherein R _{4 represents} a branched or unbranched alkyl radical having 1 to 24 carbon atoms, where R _{5 represents} either a hydrogen atom or a branched or unbranched alkyl radical having 1 to 24 carbon atoms and where Rs either represents a hydrogen atom or a branched or unbranched acyl radical Represents 1 to 24 carbon atoms, and which

(d) if desired, one or more surface-active substances B, selected from the group of substances of the general structural formula 14

RT - O - CH ₂ - CH - CH ₂ --OH R ₉ n O - R ₈ where R ₇ , R ₈ and R ₉ are selected from the group which comprises: H, branched or unbranched, saturated or unsaturated fatty acid residues with 8 to 24 carbon atoms, in which up to three aliphatic hydrogen atoms can be substituted by hydroxyl groups and n represents a number from 2 to 8, and which

(e) are essentially free of polyethoxylated emulsifiers.

R ₄ is advantageously selected from the group of unbranched alkyl radicals, preference being given to the myristyl radical, the palmityl radical, the stearyl radical and the eicosyl radical.

R ₅ can advantageously represent a hydrogen atom, but is preferably selected from the group consisting of methyl, ethyl, propyl and isopropyl.

Re can advantageously represent a hydrogen atom, but can also advantageously be selected from the group consisting of myristoyl, palmitoyl, stearoyl and eicosoyl.

The surface-active substances A from the group methyl glucose monostearate (formula as below) will be or will be particularly advantageous.

O \ l OCC ₁₇ H35 H ₂ C

HOA ^^ - ^ - ^0-0 ^

O

I.

^H (A1)

Methyl glucose distearate (formula as below) 15

(A2),

and any mixtures thereof, for example approximately equimolar mixtures thereof, which are also referred to as methylglucose sesquistearate. Such methyl glucose sesquistearate is commercially available, for example, under the trade name Tego® Care PS from the company Th.Goldschmidt KG.

The surface-active substances B are also selected with particular advantage from the group of compounds in which n assumes the value 3 and R ₃ , R ₄ and R ₅ are selected independently of one another from the group which comprises: H, branched or unbranched , saturated or unsaturated fatty acid residues with 14 to 20 carbon atoms, in particular the structures listed below:

R ₇ - C— O-CH ₂ -CH— CH ₂ -O-CH ₂ -CH— CH ₂ -O— CH -CH— CH ₂ -O— C— R ₉ l | III | ι

O OH OH OH o

(B1),

An approximately equimolecular mixture of the compounds A2 and B1 has turned out to be the preferred emulsifier combination according to the invention, the radicals R ₇ and R ₉ in B1 preferably both denoting a stearate radical. Such emulsifier combinations are available as "Polyglyceryl (3) -methylglucose distearate" (PGMS) under the trade name Tego Care® 450 from the company Th. Goldschmidt KG.

Preparations according to the invention and the uses described according to the invention help the described disadvantages of the prior art in a surprising manner 16

Way off. According to the invention, higher sun protection factors can be achieved than the prior art would have suggested.

Furthermore, the prior art did not suggest that waterproof preparations are obtainable according to the invention which can achieve considerably higher water resistance than preparations of the prior art, which means that high sun protection factors can still be achieved even after bathing, for example.

Preparations according to the invention are produced according to the usual rules familiar to the person skilled in the art.

The total amount of the water-soluble UV filter substance or substances in the finished cosmetic or dermatological preparations is advantageously chosen in the range from 0.1-10.0% by weight, preferably 0.5-6.0% by weight on the total weight of the preparations.

The total amount of 2-phenylbenzimidazole-5-sulfonic acid (if it is this substance which is to be used as a sulfonated UV filter substance in the sense of the present invention) or its salts in the finished cosmetic or dermatological preparations is advantageously from the range of 0.1-10.0% by weight, preferably 0.5-6.0% by weight, based on the total weight of the preparations.

The total amount of 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (if it is this substance which is to be used as a sulfonated UV filter substance in the sense of the present invention) or its salts in the finished cosmetic or dermatological preparations is advantageously obtained the range of 0.1-10.0% by weight, preferably 0.5-6.0% by weight, based on the total weight of the preparations.

The total amount of 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid (if it is this substance which is to be used as a sulfonated UV filter substance in the sense of the present invention) or its salts in the finished cosmetic or dermatological preparations is advantageous selected from the range of 0.1-10.0% by weight, preferably 0.5-6.0% by weight, based on the total weight of the preparations. 17

The total amount of 2-methyl-5- (2-oxo-3-bornylidenemethyl) benzenesulfonic acid (if it is this substance which is to be used as a sulfonated UV filter substance in the sense of the present invention) or its salts in the finished cosmetic or dermatological preparations are advantageously selected from the range from 0.1 to 10.0% by weight, preferably 0.5 to 6.0% by weight, based on the total weight of the preparations.

The total amount of benzene-1,4-di (2-oxo-3-bornylidenemethyl-10-sulfonic acid (if it is this substance which is to be used as a sulfonated UV filter substance in the sense of the present invention) or its salts in the Finished cosmetic or dermatological preparations are advantageously chosen from the range of 0.1-10.0% by weight, preferably 0.5-6.0% by weight, based on the total weight of the preparations.

The total amount of one or more asymmetrically substituted s-triazine derivatives, in particular dioctylbutylamidotriazone, in the finished cosmetic or dermatological preparations is advantageously in the range from 0.1 to 15.0% by weight, preferably 0.5 to 8.0% by weight .-% selected, based on the total weight of the preparations.

Cosmetic and dermatological preparations according to the invention advantageously also 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 (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 of such oxides. It is particularly preferred to use pigments based on TiO ₂ .

It is particularly advantageous within the meaning of the present invention, although not mandatory, if the inorganic pigments are in hydrophobic form, i.e. that they have been treated to be water-repellent on the surface. 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 after a rectification n Ti0 ₂ + m (RO) ₃ Si-R "-> n TiO ₂ (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 MT 100 T from TAYCA, M 160 from Kemira and T 805 from Degussa.

The cosmetic and / or dermatological light protection formulations according to the invention can be composed as usual and can be used for cosmetic and / or dermatological light protection, also for the treatment, care and cleaning of the skin and / or hair and as a make-up product in decorative cosmetics.

For use, the cosmetic and dermatological preparations according to the invention are applied to the skin and / or the hair in a sufficient amount in the manner customary for cosmetics.

Those cosmetic and dermatological preparations which are in the form of a sunscreen are particularly preferred. These can advantageously additionally contain at least one further UVA filter and / or at least one further UVB filter and / or at least one inorganic pigment, preferably an inorganic micropigment.

The cosmetic and dermatological preparations according to the invention can contain cosmetic auxiliaries as are usually used in such preparations, for example preservatives, bactericides, perfumes, substances for preventing foaming, dyes, pigments which have a coloring effect, thickeners, moisturizing and / / or moisturizing substances, fats, oils, waxes or other usual components of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives. 19

An additional level of antioxidants is generally preferred. According to the invention, all the antioxidants suitable or customary for cosmetic and / or dermatological applications can be used as favorable antioxidants.

The antioxidants are advantageously selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocanic acid) and their derivatives, peptides such as D, L-camosin, D-camosin, L- Camosin and its derivatives (e.g. Anserin), carotenoids, carotenes (e.g. α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid 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, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (e.g. buthionine sulfoximines, homocysteine sulfoximine, buthionine Penta-, hexa-, heptathioninsulfoximine) in very low tolerable doses (e.g. pmol to μmol / kg), also (metal) chelators (eg α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-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 (e.g. γ-linolenic acid, linoleic acid, oleic acid), folic acid 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 (eg vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoate of benzoin, rutinic acid and its derivatives, α-glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, butylated hydroxytoluene, butylated hydroxyanisole , Nordihydroguajak resin acid, Nordihydroguajaretsäure, trihydroxybutyrophenon, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (eg ZnO, ZnSO) Sele n and its derivatives (e.g. Selenomethionine), stilbenes and their derivatives (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these active substances which are suitable according to the invention.

The amount of the aforementioned 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. 20th

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 dehvate 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.

The lipid phase can advantageously be selected from the following group of substances: mineral oils, mineral waxes

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 oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions for the purposes of the present invention is advantageously selected from the group of esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms, from the group of esters from aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 C atoms. Such ester oils can then advantageously be selected from the group of isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononylisononanoate, 2-ethylhexyl, ethyl-2-ethylhexyl, ethyl-2-ethylhexyl 2-octyldodecyl palmitate, oleyl oleate, olerlerucate, erucyl oleate, erucylerucate and synthetic, semi-synthetic and natural mixtures of such esters, for example jojoba oil. 21

Furthermore, the oil phase can advantageously be chosen from the group of branched and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols, and also the fatty acid triglycerides, especially the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12 - 18 carbon atoms. The fatty acid triglycerides can, for example, advantageously be selected from the group of synthetic, semisynthetic and natural oils, e.g. Olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.

Any mixtures of such oil and wax components can also be used advantageously for the purposes of the present invention. It may also be advantageous to use waxes, for example cetyl palmitate, as the sole lipid component of the oil phase.

The oil phase is advantageously selected from the group consisting of 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C ₁₂ -i ₅ -alkyl benzoate, caprylic capric acid triglyceride, dicaprylyl ether.

Particularly advantageous are mixtures of C ₂ -ιs benzoate and 2-ethylhexyl isostearate, mixtures of C _12- i ₅ -alkyl benzoate and isotridecyl isononanoate and mixtures of Cι. ₂ 15-alkylbenzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate.

Of the hydrocarbons, paraffin oil, squalane and squalene can be used advantageously for the purposes of the present invention.

The oil phase can advantageously also contain cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or the silicone oils.

Cyclomethicone (octamethylcyclotetrasiloxane) is advantageously used as the silicone oil to be used according to the invention. But other silicone oils are also advantageous in the sense of 22

to use the present invention, for example hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).

Mixtures of cyclomethicone and isotridecyl isononanoate, cyclomethicone and 2-ethylhexyl isostearate are also particularly advantageous.

The aqueous phase of the preparations according to the invention optionally advantageously contains

Alcohols, diols or polyols of low C number, and also 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 analog products, furthermore alcohols of 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, poiysaccharides or their derivatives, e.g. Hyaluronic acid, xanthan gum, hydroxypropylmethyl cellulose, particularly advantageously from the group of polyacrylates, preferably a polyacrylate from the group of so-called carbopoles, for example carbopoles of types 980, 981, 1382, 2984, 5984, in each case 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 further 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, is in particular 1 to 6% by weight, based on the total weight of the preparations, in order to 23

To provide metallic preparations that protect the skin from the entire range of ultraviolet radiation. They can also serve as sunscreens.

The other 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;

The list of the further UVB filters mentioned, which can be used in combination with the active substance 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 further 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'-methoxyphenyr) propane-1,3-dione and 1-phenyl-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 further UVA and / or UVB filters. 24

example 1

% By weight

Methyl glucose sesquistearate 5.00

Caprylic / Capric Acid Triglycerides 10.00

Cι _2- i ₅ alkyl benzoates 5.00

Dicaprylyl ether 5.00

Silicone oil 1, 00

Dioctylbutylamidotriazon 6.00

Xanthan gum 0.40

Glycerin 3.00

Dyes, preservatives q.s.

Water ad 100.00

25

Example 2

% By weight

Polyglyceryl (3) methyl glucose distearate 4.00

Sorbitan monstearate 2.00

Caprylic / capric acid triglycerides 5.00

Cι _2- i ₅ alkyl benzoates 5.00

Dicaprylyl ether 5.00

Silicone oil 1, 00

Dioctylbutylamidotriazon 4.00 t-Butylphenyl-methoxyphenylpropanedione 2.00

Octyltriazon 2.00

4-methylbenzylidene camphor 3.00

Sodium 2-hydroxy-4-methoxybenzophenone 2.00

5-sulfonate

Sodium hydroxide solution 0.30

Xanthan gum 0.20

Carbomer 0.20

Glycerin 5.00

Butylene glycol 5.00

Glycine 1.00

Dyes, preservatives qs

Water ad 100.00

26

Example 3

% By weight

Polyglyceryl (3) methyl glucose distearate 3.00

Sorbitan monstearate 1, 00

Caprylic / capric acid triglycerides 5.00

2-octyldodecanol 5.00

Dioctylbutylamidotriazon 4.00

TiO ₂ 2.00

Sodium hydroxide solution 0.30

Carbomer 0.30

Glycerin 10.00

Dyes, preservatives q.s. Water ad 100.00

Example 4

% By weight

Methyl glucose sesquistearate 3.00

Polyglyceryl (3) methyl glucose distearate 3.00

Cι ₂ -i5-alkyl benzoates 8.00

Dicaprylyl ether 5.00

Silicone oil 1, 00

Dioctylbutylamidotriazon 6.00

Urocanic acid 1.00

Sodium hydroxide solution 0.20

Xanthan gum 0.10

Carbomer 0.20

Butylene glycol 5.00

Glycine 1.00

Dyes, preservatives qs water ad 100.00 27

Example 5

% By weight

Polyglyceryl (3) methyl glucose distearate 5.00

Caprylic / capric acid triglycerides 3.00

2-octyldodecanol 3.00

Dicaprylyl ether 3.00

Silicone oil 1, 00

Dioctylbutylamidotriazon 4.00 t-Butylphenyl-methoxyphenylpropandion 1, 50

TiO ₂ 2.00

Sodium 2-hydroxy-4-methoxybenzophenone 2.00

5-sulfonate

Caustic soda 0.70

Carbomer 0.40

Glycerin 3.00

Glycine 1.00

Dyes, preservatives qs

Water ad 100.00

Claims

28 patent claims

1. Use of sunscreen-active combinations of active ingredients

(b) one or more asymmetrically substituted s-triazine derivatives for the production of waterproof light protection preparations in the form of O / W emulsions.

2. Light protection preparations in the form of O / W emulsions containing active ingredient combinations

(b) one or more asymmetrically substituted s-triazine derivatives,

O ll

O— C— R ₄

H ₂ C

HθΛ ^ - ^ - ^ ° - R =

O

IR ₆ , where R represents a branched or unbranched alkyl radical having 1 to 24 carbon atoms, where R _{5 represents} either a hydrogen atom or a branched or unbranched alkyl radical having 1 to 24 carbon atoms and where Rg either represents a hydrogen atom or a branched or unbranched acyl radical having 1 represents up to 24 carbon atoms, and.

(d) if desired, one or more surface-active substances B, selected from the group of substances of the general structural formula 29

CH ₂ - CH - CH ₂ -OH R ₉ n

OR ₈ where R ₇ , R _& and R ₉ are selected from the group comprising: H, branched or unbranched, saturated or unsaturated fatty acid residues having 8 to 24 carbon atoms, in which up to three aliphatic hydrogen atoms are substituted by hydroxyl groups can and n represents a number from 2 to 8.

3. Use according to claim 1 or light protection preparations according to claim 2, characterized in that the unsymmetrically substituted s-triazine derivative (s) are selected from the group of substances whose chemical structure is represented by the generic formula

NH, Ns NH

N N

NH

0 N (-R _{2 is} reproduced, where

R represents a branched or unbranched C ₈ -alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical, optionally substituted with one or more C 1 -C 4 alkyl groups, X represents an oxygen atom or an NH group, Ri represents a branched or unbranched d -Ciβ-alkyl radical, a C ₅ -C ₁₂ cycloalkyl radical, optionally substituted with one or more dC - alkyl groups, or a

Hydrogen atom, an alkali metal atom, an ammonium group or a group of

formula 30th

-O— CH ₂ - CH-

IR ₃

means in which

A represents a branched or unbranched C 1 -C ₈ -alkyl radical, a Cs-C ₂ -cycloalkyl or aryl radical, optionally substituted with one or more d-

C ₄ - alkyl groups, R _{3 represents} a hydrogen atom or a methyl group, n represents a number from 1 to 10,

R _{2 represents} a branched or unbranched C 1 -C ₈ alkyl radical, a C ₅ -C ₂ cycloalkyl radical, optionally substituted with one or more dC ₄ alkyl groups, if X represents the NH group, and a branched or unbranched d C ₈ alkyl, a C ₅ -C ₂ cycloalkyl, optionally substituted with one or more dC ₄ alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula

-O- CH; -CH- R ₃

means in which

A represents a branched or unbranched d -CC ₈ alkyl radical, a C ₅ -d ₂ cycloalkyl or aryl radical, optionally substituted with one or more d- 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.

4. Use according to claim 1 or light protection preparations according to claim 2, characterized in that the dioctylbutylamidotriazon is chosen as the asymmetrically substituted triazine derivative. 31

5. Use according to claim 1 or light protection preparations according to claim 2, characterized in that the total amount of one or more asymmetrically substituted s-triazine derivatives, in particular of dioctylbutylamidotriazone, in the finished cosmetic or dermatological preparations from the range 0.1-15, 0% by weight, preferably 0.5-8.0% by weight, is selected, based on the total weight of the preparations.

6. Use according to claim 1 or light protection preparations according to claim 2, characterized in that the surface-active substances A from the group methyl glucose monostearate (formula as below)

(A1)

Methyl glucose distearate (formula as below)

O II

(A2),

and any mixtures thereof, for example approximately equimolar mixtures thereof (methyl glucose sesquistearate).

7. Use according to claim 1 or light protection preparations according to claim 2, characterized in that the surface-active substances B selected from the group of compounds in which n assumes the value 3 and R ₃ , R ₄ and R ₅ independently of one another. 32

others are selected from the group consisting of: H, branched or unbranched, saturated or unsaturated fatty acid residues with 14 to 20 carbon atoms, in particular the structures listed below:

R ₇ - C— O-CH ₂ -CH— CH ₂ -O-CH ₂ -CH— CH ₂ -O— CH ₂ -CH— CH ₂ -O— C — Rg l | III ll

O OH OH OH o

(B1),

8. Use according to claim 1 or light protection preparations according to claim 2, characterized in that the surface-active substances A and B represent the approximately equimolecular mixture, which is referred to as polyglyceryl (3) methyl glucose distearate.