DE10063867A1 - Compositions for protecting human skin and hair against the damaging effects of ultraviolet radiation, comprise new or known N-substituted anilinomethylene malonic acid derivatives - Google Patents

Abstract

Cosmetic and pharmaceutical compositions for protecting human skin and hair against the damaging effects of ultraviolet radiation, comprise N-substituted anilinomethylene malonic acid derivatives (I). Cosmetic and pharmaceutical compositions for protecting human skin and hair against the damaging effects of ultraviolet radiation comprise N-substituted anilinomethylene compounds of formula (I). R<1> = 1-20C alkyl, 2-20C alkenyl, 3-15C cycloalkyl, 6-12C aryl, aralkyl (with 6-12C aryl and 1-6C alkyl components) or 5-12C heteroaryl, all optionally substituted by 1-6C alkyl, 1-16C alkoxy, 6-12C aryloxy, NH2, OH, COOR<9>, CONR<10>R<11> and/or W or interrupted by ether oxygen; R<2> = COOR<9>, CONR<10>R<11>, CN or COR<9>; R<3> = COOR<12>, CONR<13>R<14>, CN or COR<12>; R<4>-R<8> = H, NH2, NO2 or R<1>; R<9>-R<14> = H or R<1>, provided that R<9> is not COOR<9>; W = a group of formula W1-W3; a, b = 0-3, provided that a+b = 3; A = a bond to the neighboring atom (sic); c = 1-10; and R<15> = an aliphatic, araliphatic, alicyclic or optionally substituted aromatic group with up to 18C atoms. An Independent claim is also included for the following compounds: 2-(N-methylanilinomethylene)-propanedioic acid di-n-propyl, di-1-methylethyl, di-n-butyl, di-2-methylpropyl, di-n-pentyl, di-3-methylbutyl, di-4-methylpentyl and di-2-ethylhexyl esters; 2-(N-ethylanilinomethylene)-propanedioic acid di-n-propyl, di-1-methylethyl, di-n-butyl, di-2-methylpropyl, di-n-pentyl and di-3-methylbutyl esters; 2-(N-propylanilinomethylene)-propanedioic acid di-n-propyl, di-1-methylethyl, di-n-butyl, di-2-methylpropyl and di-3-methylbutyl esters; 2-cyano-2-(N-methylanilino)-2-propenoic acid n-propyl, methylethyl, n-butyl, 2-methylpropyl, n-pentyl, 3-methylbutyl, n-hexyl, 4-methylpentyl and 2-ethylhexyl esters; 2-cyano-2-(N-ethylanilino)-2-propenoic acid n-propyl, methylethyl, n-butyl, 2-methylpropyl, n-pentyl, 3-methylbutyl, n-hexyl, 4-methylpentyl, n-octyl and 2-ethylhexyl esters; and 2-cyano-2-(N-propylanilino)-2-propenoic acid n-propyl, methylethyl, n-butyl, 2-methylpropyl, n-pentyl, 3-methylbutyl, n-hexyl, 4-methylpentyl, n-octyl and 2-ethylhexyl esters.

Description

The invention relates to cosmetic preparations for protecting human Skin and human hair from the damaging effects of ultraviolet Solar radiation, the new N-substituted contained in these preparations Anilinomethylene derivatives and their use as UV absorbers.

UV absorbers are compounds with a pronounced absorption capacity for the ultraviolet radiation. They are especially used as sunscreens in kosme tables and pharmaceutical preparations, but also to improve lighting durability of technical products such as paints, varnishes, plastics, Textiles, polymers such as B. polymers and copolymers of mono- and diolefins, Polystyrenes, polyurethanes, polyamides, polyesters, polyureas and polycarbonates, Packaging materials and rubbers used.

Depending on the wavelength, UV rays are converted into UV-A rays (320-400 nm, UV-A-I: 340-400 nm, UV-A-II: 320-340 nm) or UV-B rays (280-320 nm). The following applies in general: The damaging effect of UV rays on human beings Skin increases with decreasing wavelength and increasing duration of exposure.

UV rays can cause acute and chronic skin damage, the Type of damage depends on the wavelength of the radiation. So the UV-B Radiation a sunburn (erythema) up to severe skin burns cause. Reduced enzyme activities, weakened immune system systems, disorders of the DNA structure and changes in the cell membrane as damaging effects of UV-B rays are known. The UV-A rays penetrate in deeper layers of the skin and there can be the aging process of the skin accelerate. The shorter-wave UV-A-II radiation additionally increases the formation from sunburn. In addition, the UV-A radiation can be phototoxic or photo trigger allergic skin reactions.  

Very frequent and unprotected exposure of the skin to sunlight leads to Loss of skin elasticity and increased wrinkling. In extreme cases pathological skin changes up to skin cancer are observed.

Depending on the location of their absorption maxima, UV absorbers are converted into UV-A and UV-B absorber classified; is both UV-A and UV absorber UV-B absorbed, in this case one speaks of a UV-A / B broadband absorber.

The number of suitable UV-A absorbers is very limited and they have significant shortcomings:
For example, 4-tert-butyl-4'-methoxy-dibenzoylmethane and 4-isopropyl-dibenzoylmethane (DE-A 29 45 925) are not very stable to light. In addition, they have only a limited solubility in cosmetic oils, which can lead to problems in the formulation of cosmetic preparations. In addition, dibenzoylmethane derivative-containing sun protection products can leave stains that are extremely difficult to wash out on textiles.

The range of UV-B absorbers is significantly more extensive, but there are also shortcomings here:
So they partially, such. B. the 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, only over a relatively low absorption. Or they show, like the p-meth 2-ethylhexyl or isoamyl oxycinnamate, degradation reactions under irradiation conditions. With these filters, photo reactions are also observed in combination with 4-tert-butyl-4'-methoxy-dibenzoylmethane.

There is therefore a further need for light stabilizers for use in cosmetic and pharmaceutical preparations. We are looking for light-stable UV absorbers with strong absorption so that they effectively protect against damage from UV rays. Furthermore, it is sought that these UV absorbers also meet the following criteria for use in cosmetic sunscreens:

• - Compatibility with other UV absorbers under the influence of light
• - good solubility in cosmetic solutions in the case of crystalline UV absorbers agents and liquid, oil-soluble UV absorbers, such as. B. p-methoxy cinnamon Acid ethyl, isoamyl and isooctyl ester, ethylhexyl salicylate, homomenthyl salicylate, menthyl anthranilate, ethylhexyl p-aminobenzoate, 3,3-di phenyl-2-cyanoacrylic acid ethyl and ethylhexyl esters;
• - liquid, oil-soluble UV absorbers should be combined with other UV absorbers or cosmetic oil components can be mixed well;
• - water resistant UV protection;
• - Easy processing in cosmetic formulations and stability under conditions of use;
• - compatibility with cosmetic raw materials;
• - pH stability;
• - thermal stability;
• - no or easily washable discoloration of textiles;
• - Colorless and odorless
• - easily biodegradable  
• - not hazardous to water
• - low skin penetration
• - Refractive index <1.5 to improve transparency of emulsions to reach

The invention relates to cosmetic sunscreen preparations using N-substituted anilionomethylene derivatives of the formula I in which the C = C double bond is in the E or Z configuration,

wherein
R ¹ C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₃ -C ₁₅ cycloalkyl, C ₆ -C ₁₂ aryl, C ₆ -C ₁₂ - ar-C ₁ -C ₆ alkyl, C ₅ -C ₁₂ heteroaryl, the substituents mentioned with C ₁ -C ₆ alkyl, C ₁ -C ₁₆ alkoxy, C ₆ -C ₁₂ aryloxy, amino, hydroxy, COOR ⁹ , CONR ¹⁰ R ¹¹ , a Group W may be substituted or interrupted by ether oxygen,
R ² COOR ⁹ , CONR ¹⁰ R ¹¹ , CN, COR ⁹
R ³ COOR ¹² , CONR ¹³ R ¹⁴ , CN, COR ¹²
R ⁴ to R ⁸ independently of one another are hydrogen, amino, nitro or the meaning given under R ¹
R ⁹ to R ¹⁴ independently of one another have hydrogen or the meaning given under R ¹ , where R ⁹ cannot again stand for the group COOR ⁹ ,
W silanes, oligosilanes and polysiloxanes of the general formulas W ^I to W ^III
W ^I SiR ¹⁵ _a (OSiR ¹⁵ ₃ ) _b ,
a 0, 1, 2 or 3
b 3, 2, 1 or 0
a + b 3

A is a bond to the neighboring atom
c 1-10
R ^{15 is} an open-chain or branched aliphatic, araliphatic, cycloaliphatic or optionally substituted aromatic radical, each having up to 18 carbon atoms
mean.

Compounds of the formula are preferred

wherein
R ¹ optionally substituted alkyl;
R ² COOR ⁹ , CN, COR ⁹ ;
R ³ COOR ¹² , CN, COR ¹² ;
R ⁹ , R ¹² independently of one another are an open-chain or branched aliphatic, araliphatic, cycloaliphatic or optionally substituted aromatic radical, each having up to 18 carbon atoms
means.

Compounds of the formula are particularly preferred

wherein
R ^{1 is} an optionally substituted, open-chain or branched aliphatic radical with up to 8 C atoms;
R ² COOR ⁹ ; CN;
R ³ COOR ¹² , CN;
R ⁹ , R ¹² independently of one another are an open-chain or branched aliphatic radical having up to 18 C atoms
mean.

Examples of alkyl radicals R ¹ and R ⁹ -R ¹⁴ are branched or unbranched C ₁ -C ₁₂ 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, Called 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl.

The use of substituted arylaminomethylene derivatives of the general Structure A as a UV filter for protecting polymers is known from US Pat. No. 3,079,366 known.

For N-substituted anilionomethylene derivatives of structure A in which R ^{1 is} hydrogen, the use as UV-A absorber in cosmetic sun protection preparations is mentioned in EP A 895 776 and EP A 852 137.

Likewise used as UV-A filters in EP A 832 641 are benzoxazole-substituted aryl aminomethylene-N-substituted anilionomethylene derivatives of structure B mentioned.

Furthermore aminomethylene derivatives according to the general structure C from cyclohexane-1,3-dione (a), 1,3-dioxane-4,6-dione (b), 3,4-dihydro-2H-pyran 2,4-dione (c) and 1,3-disubstituted barbituric acid (d) as UV absorbers wrote (WO 98/14423).

Due to their enzyme-inhibiting effect, the use of N-substituted Anilionomethylene derivatives of the structure of formula I in antibacterial skin care products described in DE A 30 18 132.  

Cosmetic and pharmaceutical sunscreen preparations using N-substituted anilionomethylene derivatives of formula I as UV-B filters are there against not yet known.

The N-substituted anilionomethylene derivatives of the formula I can by alky lation of anilinomethyl derivatives II unsubstituted with amino nitrogen Organyl halides, sulfates or p-toluenesulfonates analogous to known processes are produced, cf. this z. B. Milata, V., Collect. Czech. Chem. Commun. 54 713 (1989); Abdalla, G.M., J. Heterocyclic Chem. 27, 1201 (1990); Giral, L. Eur. J. Med. Chem. 22, 3 u. 139 (1987).

The compounds II used as starting materials are by implementation of the corre sponding anilines with orthoformic acid esters and malonic acid esters, cyanoacetic acid acid esters, acetoacetic esters, acetylacetone, benzoylacetone, malononitrile or Pivaloylacetonitrile accessible. Instead of ethyl orthoformate and Diethyl malonate can advantageously also be the ethoxymethylene malon acid diethyl ester can be used.

If substituted anilines are available on the amino group, these can be substituted by Heating with orthoformic acid esters and malonic acid esters, cyanoacetic acid esters, Acetoacetic esters, acetylacetone, benzoylacetone, malononitrile or pivaloyl acetonitrile directly to the N-substituted anilionomethylene derivatives of the formula I. be implemented.  

The higher alkyl esters of the formula I can also be obtained from the methyl or ethyl esters can be obtained by transesterification with higher alcohols.

The N-substituted anilionomethylene derivatives of the formula I are notable for a strong absorption in the UV-B range and also show a recorded lightfastness.

Surprisingly, the N-substituted anilionomethylene derivatives lead the Formula I in cosmetic preparations for the photostabilization of UV absorbers with lower UV light stability (see Tab. 2). So with N-substituted Anilionomethylene derivatives of formula I an improvement in photostability z. B. the UV-B filter reaches p-methoxycinnamic acid 2-ethylhexyl or isoamyl ester.

Although the absorption maximum of the N-substituted anilionomethylene Derivatives of formula I is in the UV-B range, they also cause a stabilization lization of the very light-unstable UV-A absorber 4-tert-butyl-4'-methoxydiben zoylmethan. A combination of the UV filters p-methoxy-cinnamic acid 2- ethylhexyl or isoamyl ester with 4-tert-butyl-4'-methoxy-dibenzoylmethane in cosmetic preparations by the N-substituted anilionomethylene derivatives I stabilized.

Sunscreen preparations with improved photostability are achieved by Use of 0.1-10 wt .-%, preferably 1-10 wt .-%, p-methoxycinnamic acid-2-ethyl hexyl ester, p-methoxycinnamic acid isoamyl ester or 4-tert-butyl-4'-methoxy-di benzoylmethane with 0.1-10% by weight of a compound of formula I.

Cosmetic formulations with increased light stability can also be produced by a combination of three of dibenzoylmethane derivatives and p-methoxycinnamic acid estem with N-substituted anilionomethylene derivatives of the formula I through use from Z. B. 0.1-5 wt .-% 4-tert-butyl-4'-methoxy-dibenzoylmethane, preferably 1 to 3% by weight, 0.1 to 10% by weight of 2-ethythexyl p-methoxycinnamate, preferably 1.0  to 7.5% by weight, and at least 0.2% by weight of a compound of the formula I before adds 1.0 to 6.0% by weight, preferably in the ratio I part of dibenzoylmethane derivative, 2 Parts of p-methoxycinnamic acid ester and 2 parts of compound I.

Another very photo is advantageous to this combination of three stable UV absorber, such as B. 2-Ethylhexyl-2-cyano-3,3'-diphenyl acrylate, methyl benzylidene camphor, phenylbenzimidazole sulfonic acid, 2,2 '- (1,4-phenylene) -bis-1H benzimidazole-4,6-disulfonic acid monosodium salt, ethylhexyl salicylate, homosali cylate, benzophenone derivatives, such as oxybenzone, or triazine compounds, such as octyl triazon to add.

Furthermore, surprisingly in cosmetic preparations by Ver use of N-substituted anilionomethylene derivatives of the formula I in com combination with other UV filters a synergistic increase in the sun protection factor reached (see Tab. 3-5). For example, a cosmetic emulsion that both a compound of formula I and 4-tert-butyl-4'-methoxy-dibenzoylmethane contains a significantly higher sun protection factor than it does the addition of light protection factors of the emulsions with the individual components can be expected. Combinations of three or more UV filters under Ver use of N-substituted anilionomethylene derivatives according to formula I with Di benzoylmethane derivatives and other UV-B filters, such as methylbenzylidene camphor, Octocrylene, salicylates, benzophenones and phenylbenzimidazole sulfonic acid, as well with microfine pigments such as zinc oxide and titanium dioxide, synergistic Er increases in the sun protection factor. The UV filter combinations mentioned are exemplified and not limited to the above combinations ver stand.

The invention thus also relates to the use of the N-substituted Anilionomethylene derivatives according to formula I in combination with conventional UV Absorbers to strengthen protection against damaging UV radiation via the Degree of protection provided by using equal amounts of conventional filters or the  N-substituted anilionomethylene derivatives according to formula I is achieved alone (synergistic effect).

Synergies of the N-substituted anilionomethylene derivatives I with other non-UV Light absorbing components for improved protection against UV light is expected.

According to the corresponding calculations, the N-substituted anilionomethylene Derivatives I expected to be easily biodegradable.

The N-substituted anilionomethylene derivatives of the formula I can in particular in cosmetic and pharmaceutical sunscreens, hair products care and day care with UV protection, but also as an anti-aging agent for technical products are used.

They have good solubility in cosmetic solvents and in fluids oil-soluble UV absorbers. The N-substituted anilionomethylene derivatives Formula I can be easily incorporated into cosmetic preparations.

Sun protection products should be waterproof so that they have sufficient UV protection for grant the user, especially children, after swimming or bathing is accomplished. The UV absorbers of formula I meet these requirements due to of their hydrophobic character to a particular extent and are therefore particularly suitable especially for the formulation of water-resistant sun protection products.

Liquid N-substituted anilionomethylene derivatives of the formula I are also suitable as a solvent for solid UV filters, for example but not limiting the following compounds are mentioned: camphor derivatives (e.g. benzylidene camphor and methylbenzylidene camphor), triazine derivatives (e.g. octyltriazine, Dioctylbutamide triazine, bis (ethylhexyloxy, hydroxy) phenyl, methoxyphenyltriazine), Benzophenone derivatives (e.g. oxybenzone), dibenzoylmethane derivatives (e.g. butylmethoxydibenzoylmethane).  The solution properties of the N-substituted aniliono Methylene derivatives according to formula I can be increased if they are combined with others liquid components of cosmetic preparations, including other liquid UV filter, can be combined. However, examples are not given restrictive: ethylhexyl p-methoxycinnamate, isoamyl p-methoxycinnamate, ethyl hexylsalicylate, octocrylene, menthylanthanate, fatty alcohol esters, fatty acid esters, Alkyl benzoates etc.

The present invention also relates to new N-substituted anilionomethylene derivatives corresponding to formula I and their use as UV absorbers, in particular in cosmetic preparations. The following N-substituted anilio nomethylene derivatives of the formula I are new:
2- (N-Methylanilinomethylen) -propandisäuredi-n-propyl ester
2- (N-Methylanilinomethylen) -propandisäuredi 1-methylethyl ester
2- (N-Methylanilinomethylen) -propandisäuredi-n-butyl ester
2- (N-Methylanilinomethylen) -propandisäuredi-2-methylpropyl ester
2- (N-Methylanilinomethylen) -propandisäuredi n-pentyl
2- (N-Methylanilinomethylen) -propandisäuredi-3-methylbutyl ester
2- (N-Methylanilinomethylen) -propandisäuredi-4-methylpentyl ester
2- (N-Methylanilinomethylen) -propandisäuredi 2-ethylhexyl
2- (N-Ethylanilinomethylen) -propandisäuredi-n-propyl ester
2- (N-Ethylanilinomethylen) -propandisäuredi 1-methylethyl ester
2- (N-Ethylanilinomethylen) -propandisäuredi-n-butyl ester
2- (N-Ethylanilinomethylen) -propandisäuredi-2-methylpropyl ester
2- (N-Ethylanilinomethylen) -propandisäuredi n-pentyl
2- (N-Ethylanilinomethylen) -propandisäuredi-3-methylbutyl ester
2- (N-Propylanilinomethylen) -propandisäuredi-n-propyl ester
2- (N-Propylanilinomethylen) -propandisäuredi 1-methylethyl ester
2- (N-Propylanilinomethylen) -propandisäuredi-n-butyl ester
2- (N-Propylanilinomethylen) -propandisäuredi-2-methylpropyl ester
2- (N-Propylanilinomethylen) -propandisäuredi-3-methylbutyl ester
2-cyano-3- (N-methylanilino) -2-propenoic acid n-propyl ester
2-cyano-3- (N-methylanilino) -2-propenoic acid, methylethyl ester
2-cyano-3- (N-methylanilino) -2-propenoic acid n-butyl ester
2-cyano-3- (N-methylanilino) -2-propenoic acid 2-methylpropyl ester
2-cyano-3- (N-methylanilino) -2-propenoic acid n-pentyl
2-cyano-3- (N-methylanilino) -2-propenoic acid-3-methylbutyl ester
2-cyano-3- (N-methylanilino) -2-propenoic acid, n-hexyl
2-cyano-3- (N-methylanilino) -2-propenoic acid 4-methylpentytester
2-cyano-3- (N-methylanilino) -2-propenoic acid 2-ethylhexyl ester
2-cyano-3- (N-ethylanilino) -2-propenoic acid n-propyl ester
2-cyano-3- (N-ethylanilino) -2-propenoic acid, methylethyl ester
2-cyano-3- (N-ethylanilino) -2-propenoic acid n-butyl ester
2-cyano-3- (N-ethylanilino) -2-propenoic acid 2-methylpropyl ester
2-cyano-3- (N-ethylanilino) -2-propenoic acid n-pentyl
2-cyano-3- (N-ethylanilino) -2-propenoic acid-3-methylbutyl ester
2-cyano-3- (N-ethylanilino) -2-propenoic acid, n-hexyl
2-cyano-3- (N-ethylanilino) -2-propenoic acid 4-methylpentyl ester
2-cyano-3- (N-ethylanilino) -2-propenoic acid, n-octyl
2-cyano-3- (N-ethylanilino) -2-propenoic acid 2-ethylhexyl ester
2-cyano-3- (N-propylanilino) -2-propenoic acid n-propyl ester
2-cyano-3- (N-propylanilino) -2-propenoic acid, methylethyl ester
2-cyano-3- (N-propylanilino) -2-propenoic acid n-butyl ester
2-cyano-3- (N-propylanilino) -2-propenoic acid 2-methylpropyl ester
2-cyano-3- (N-propylanilino) -2-propenoic acid n-pentyl
2-cyano-3- (N-propylanilino) -2-propenoic acid-3-methylbutyl ester
2-cyano-3- (N-propylanilino) -2-propenoic acid, n-hexyl
2-cyano-3- (N-propylanilino) -2-propenoic acid 4-methylpentyl ester
2-cyano-3- (N-propylanilino) -2-propenoic acid, n-octyl
2-cyano-3- (N-propylanilino) -2-propenoic acid 2-ethylhexyl ester

The absorbers of the formula I prevent use in cosmetics or pharmaceuticals zeutischen preparations the passage of UV rays through the applied Preparation film.

Cosmetic and dermatological formulations in the sense of this invention ent hold one or more common UV-A, UV-B and / or broadband filters as Individual substances or in any mixtures with each other, in the lipid phase and / or in the aqueous phase. You are a satisfactory pro in every way products, which are surprisingly characterized by high UV-A protection distinguish a high sun protection factor.

This is generally the case if the preparations are 0.5 to 15, preferably 1 up to 10, in particular 2 to 7,% by weight (based on the total weight of the accessories equation) contain compound I.

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

This kosme serves to protect skin and hair from UV radiation tables and pharmaceutical preparations can usually be used in the there are application forms, d. H. as an oil-in-water, water-in-oil or ge mixed emulsion, as milk, as a lotion or cream, aerosol, hydrodispersion or oil gel (emulsifier free), spray, foam, solution, powder, grease stick or any  other common cosmetic or pharmaceutical preparation. For the protection of Hair before UV rays are preferred preparations as shampoo, conditioner, Cure, gel, lotion, spray or cream used.

Accordingly, the preparations according to the invention, depending on their structure, used for example as skin protection cream, cleansing milk, suns protective lotion, nutrient cream, day or night cream, etc. It may be possible Lich and advantageous, the preparations according to the invention as a basis for phar to use pharmaceutical formulations. Those are particularly preferred cosmetic and dermatological preparations in the form of a skin care or make-up product.

The cosmetic and dermatological agents according to the invention are used Preparations on the skin and / or hair in the manner customary for cosmetics applied in sufficient quantity. Such cosmetic ones are particularly preferred and dermatological preparations in the form of a sunscreen available.

The cosmetic and dermatological preparations according to the invention can contain cosmetic auxiliaries, as are usually used in such preparations. z. B .:
Emulsifiers, surface-active compounds, lanolin, petroleum jelly, water, fats (e.g. triglycerides of fatty acids, polyethylene glycols, fatty alcohols, ethoxylated fatty alcohols, fatty acid esters (e.g. isopropyl palmitate, isooctyl stearate, adipic acid diisopropyl ester, etc.), natural or synthetic oils or Waxes, pigments (e.g. titanium dioxide, zinc oxide, pearlescent pigments, color pigments), thickeners (e.g. hydroxyethyl cellulose, carboxymethyl cellulose, bentonite etc.), foam stabilizers, film formers, dyes, electrolytes, pH regulators, preservatives, bactericides , Moisturizers, vitamins and biogenic agents (e.g. plant extracts and protein hydrolyzates), silicone derivatives, alcohols and polyols (e.g. ethyl alcohol, isopropanol, glycerin), perfume oils, polymers such as e.g. polyacrylates, polyurethanes, polyglycerides, polyvinylyls , Alkene and alkyne polymers, polysaccharides, polyvinylpyrrolidone, substances to prevent foaming, antioxidants, electrolytes, organic solvents, complexing agents, repellents, glycerides and radical scavengers such as. B. HALS (= "Hindered Amine Light Stabilizers") or phenol derivatives.

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

• - mineral oils, mineral waxes
• - Oils, such as triglycerides of capric or caprylic acid, as well as natural oils such as B. castor oil;
• - Fats, waxes and other natural and synthetic fat bodies, preferred wise esters of fatty acids with low C alcohols, e.g. B. with Isopro panol, propylene glycol or glycerin, or esters of fatty alcohols Low C number alkanoic acids or with fatty acids;
• - alkyl benzoate;
• - silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpoly siloxanes and mixed forms thereof.

The oil phase of the emulsions, oleogels or hydrodispersions or lipodispers ions in the sense of the present invention is advantageously selected from the group the ester of saturated and / or unsaturated, branched and / or uns branched alkane carboxylic acids with a chain length of 3 to 30 carbon atoms and saturated ten and / or unsaturated, branched and / or unbranched alcohols Chain length of 3 to 30 carbon atoms, from the group of aromatic esters Carboxylic acids and saturated and / or unsaturated, branched and / or uns branched alcohols with a chain length of 3 to 30 carbon atoms. Such ester oils can then advantageously be selected from the group of isopropyl myristate, iso propyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-  Decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyldodecyl dentate, oleyl oleate, Oleylerucat, Erucyloleat, Erucylerucat as well as synthetic, semi-synthetic and natural mixtures of such esters, e.g. B. Jojoba oil.

Furthermore, the oil phase can advantageously be selected from the group of the branched ones and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ethers, the group of saturated or unsaturated, branched or unbranched Alcohols, as well as the fatty acid triglycerides, especially the triglycerol esters saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids Chain length of 8 to 24, especially 12 to 18 carbon atoms. The fatty acid tri For example, glycerides can advantageously be selected from the group of synthetic, semi-synthetic and natural oils, e.g. B. olive oil, sunflowers oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and same more.

Any mixtures of such oil and wax components are also advantageous use in the sense of the present invention. It can also be used if necessary be parcel waxes, for example beeswax and its derivatives, as sole Use 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 _12-15 alkylbenzoate, caprylic capric acid triglyceride, dicaprylyl ether.

Mixtures of C _12-15 alkyl benzoate and 2-ethylhexyl iso stearate, mixtures of C _12-15 alkyl benzoate and isotridecyl isononanoate, and mixtures of C _12-15 alkyl benzoate, 2-ethyl hexyl isostearate and isotridecyl isononanoate are particularly advantageous.

Of the hydrocarbons, paraffin oil, squalane and squalene are advantageous in To use the sense of the present invention.

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

Cyclomethicone (octamethylcyclotetrasiloxane) is advantageous as according to the invention silicone oil to be used. But other silicone oils are also beneficial to use for the purposes of the present invention, for example hexamethyl cyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).

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

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

• - Alcohols, diols or polyols with a low C number and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol. Ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and similar products, furthermore alcohols with a low C number, e.g. As ethanol, isopropanol, 1,2-propanediol, glycerol and in particular one or more thickeners, which or which can advantageously be selected from the group consisting of silicon dioxide.
  Aluminum silicates, polysaccharides or their derivatives, e.g. B. 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, 382, 2984, 5984, each individually or in combination.

Advantageously, the cosmetic and dermatological preparations according to the invention contain, in addition to the UV-A, UV-B and / or broad band filters used, although not necessarily, 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 (e.g. Fe ₂ O ₃ ), zirconium (ZrO ₂ ). Silicon (SiO ₂ ). Manganese (e.g. MnO), aluminum (Al ₂ O ₃ ), cerium (e.g. Ce ₂ O ₃ ), mixed oxides of the corresponding metals and mixtures of such oxides. These pigments are X-ray amorphous or non-X-ray amorphous. Pigments based on TiO _{2 are} particularly preferred.

X-ray amorphous oxide pigments are metal oxides or semimetal oxides, which contribute to X-ray diffraction experiments have no or no discernible crystal structure let know. Such pigments are often obtainable by flame reaction, at for example, in that a metal or semimetal halide with hydrogen and Air (or pure oxygen) is converted into a flame.

In cosmetic, dermatological or pharmaceutical formulations X-ray amorphous oxide pigments as thickening and thixotropic agents, flow auxiliaries for emulsion and dispersion stabilization and as a carrier (for example to increase the volume of finely divided powders or powders) set.

Known and often used in cosmetic or dermatological galenics X-ray amorphous oxide pigments are the silicon oxides of the type Aerosil® (CAS- No. 7631-85-9). Aerosile® available from DEGUSSA company stand out by small particle size (e.g. between 5 and 40 nm), the particles being spherical particles of very uniform dimensions can be seen. macroscopic  Aerosile® are recognizable as loose, white powder. In the sense of the present X-ray amorphous silicon dioxide pigments are particularly advantageous, and among these, those of the Aerosil® type are preferred.

Examples of advantageous Aerosil® grades are Aerosil® 0X50. Aerosil® 130, Aerosil® 150, Aerosil® 200, Aerosil® 300, Aerosil® 380, Aerosil® MQX 80. Aerosil® MOX 170, Aerosil® COK 84, Aerosil® R 202, Aerosil® R 805, Aerosil® R 812, Aerosil® R 972, Aerosil® R 974, Aerosil® R 976.

According to the invention contain cosmetic or dermatological light protection accessories riding 0.1 to 20 wt .-%, advantageously 0.5 to 10 wt .-%, especially before adds 1 to 5% by weight of X-ray amorphous oxide pigments.

The non-X-ray amorphous inorganic pigments are present according to the invention partially in hydrophobic form, i.e. that is, they are water-repellent on the surface acts. This surface treatment can consist of the pigments provided with a thin hydrophobic layer by methods known per se become.

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

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

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

Advantageous TiO ₂ pigments are available, for example, from Degussa under the trade name T 805, advantageous TiO ₂ / Fe ₂ O ₃ mixed oxides under the trade name T 817.

The total amount of inorganic pigments, especially hydrophilic and hydrophobic inorganic micropigments in the finished cosmetic or dermatological preparations are advantageously in the range from 0.1 to 30 wt .-%, preferably 0.1 to 10.0, in particular 0.5 to 6.0 wt .-% selected, be drew on the total weight of the preparations.

An additional content of antioxidants in the cosmetic according to the invention and dermatological preparations are generally preferred. Fiction According to can be cheap antioxidants all for cosmetic and / or dermatolo uses suitable or customary antioxidants become.

The antioxidants are advantageously selected from the group consisting of amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D. -Carnosine, L-carnosine and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. a-carotene, b-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives ( e.g. dihydrolipoic acid), aurothioglucose, propyl thiouracil and other ihiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, Butyl and lauryl, palmitoyl, oleyl, y-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), Phenolic acid amides of phenolic benzylamines (e.g. homovanillic acid, 3,4-dihydroxyphenyl acetic acid, ferulic acid, sinapic acid, caffeic acid, dihydro ferulic acid, dihydro coffee acid, vanillomandelic acid or 3,4-dihydroxymandelic acid amides of 3,4-dihydroxybenzyl-, 2,3,4-trihydroxy-benzyl- or 3, 4,5-trihydroxybenzylamine) and sulfoximine compounds (e.g. B. Buthioninsulfoximine, Homocysteinsulfoximin, Buthioninsulfone, Penta-, Hexa-, Heptathioninsulfoximin) in very low tolerable doses (z. B. pmol to ~ imol / kg), also (metal) - chelators (z. B. α-hydroxyfatty acids, palmitic acid , Phytic acid, lactoferrin), α-hydroxy acids (e.g. 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 its 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) as well as coniferyl benzoate of benzoin, rutinic acid and its derivatives, α-glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, butylated hydroxytoluene, butylated hydroxyanisole, nordihydroguanay resinic acid, Nordihydro guajaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (e.g. B. ZnO, ZnSO ₄ ), selenium and its derivatives (e.g. selenium methionine), stilbenes and their derivatives (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides) , Nucleosides, peptides and lipids) of these active ingredients.

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 to 20 wt .-%, in particular 1 to 10 wt .-%, based on the total weight the preparation.

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

If vitamin A, or vitamin A derivatives, or Caroline or their derivatives, the or the antioxidants are advantageous, their respective concentrations from the range of 0.001 to 10 wt .-%, based on the total weight of the Wording to choose.  

In addition, skin whitening agents can also be used in the cosmetic preparations be used. Benzaldoximes can preferably be used as skin whitening agents with at least one aromatic hydroxy or alkoxy group, benzo-condensed or heterocyclically fused 2-hydrazino-1,3-thiazoles, 2-thio-1,3,4-heterodia zoles, their anionic or cationic salts and mixtures thereof, koji acid, kojic acid derivatives, ascorbic acid, ascorbic acid derivatives, hydroquinone, Hydroquinone derivatives, sulfur-containing molecules (e.g. glutathione or cysteine) or other synthetic or natural active ingredients for skin lightening arrive, the latter also in the form of an extract from plants (e.g. tocopherols and derivatives, arbutin [e.g. B. from Bearberry extract], Aloesin [z. B. from aloe extract], Grapefruit extract and rice extract) can be used.

The cosmetic and dermatolo according to the invention advantageously contain formulations also complexing agents (e.g. from the class of Amino-polycarboxylic acids, aromatic hydroxy and amino derivatives, enolates).

In addition, the cosmetic and dermatological preparations can also be anti have inflammatory agents which consist of the compound classes of salicylic, Acetic and propionic acid derivatives, the pyrazoles, fenams and oxicams come.

Furthermore, the cosmetic and dermatological preparations can contain auxiliaries Cooling and refreshing effect, such as B. menthol and derivatives derived therefrom, contain.

The amounts of cosmetic or dermatological auxiliary and carriers and perfume may vary depending on the type of each Product can be easily determined by a specialist simply by trying it out.

The N-substituted anilionomethylene derivatives I can be used individually or as a mixture in the corresponding preparations; they can also be used in combination with UV absorbers of other substance classes. The list of UV absorbers mentioned below, which can be used for the purposes of the present invention, is of course not intended to be limiting.
p-aminobenzoic acid and its salts
p-aminobenzoate
p-dimethylaminobenzoic acid 2-ethylhexyl ester
p-aminobenzoate
p-Aminobenzoesäureglycerinester
Salicylic acid homomenthylester
Salicylic acid 2-ethylhexyl ester
triethanolamine
4-isopropylbenzyl
anthranilate
Diisopropylzimtsäureethylester
p-methoxycinnamic acid 2-ethylhexyl ester
Diisopropylzimtsäuremethylester
p-methoxycinnamate
p-methoxycinnamic acid diethanolamine salt
p-methoxycinnamic acid isopropyl ester
2-ethylhexyl 2-cyano-3,3-diphenyl
Ethyl 2-cyano-3,3'-diphenylacrylate
2-phenylbenzimidazole sulfonic acid and its salts
3- (4'-trimethylammonium) -benzylidene-bornan-2-one methyl sulfate
Terephthalylidene-dibornanesulfonic acid and its salts (Mexoryl SX)
4-tert-butyl-4'-methoxy-dibenzoylmethane (avobenzone)
b-imidazole-4 (5) -acrylic acid (urocanic acid)
2-hydroxy-4-methoxybenzophenone
2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts
Dihydroxy-4-methoxybenzophenone
2,4-dihydroxybenzophenone
tetrahydroxy
2,2'-dihydroxy-4,4'-dimethoxybenzophenone
2-hydroxy-4-n-octoxybenzophenone
2-hydroxy-4-methoxy-4'-methylbenzophenone
3- (4'-Sulfo) benzylidene-bornan-2-one and its salts
3- (4'-methylbenzylidene) -d, 1-camphor
4-Isopropyldibenzoylinethan
2,4,6-trianilino- (p-carbo-2'-ethylhexyl-1'-oxy) -1,3,5-triazine
Phenol, 2- (2H-benzotriazol-2-yl) methyl-6- (2-methyl-3- (1,3,3,3-tetramethyl-1- (trimethylsilyl) disiloxanyl) propyl (dromitrizole trisiloxanes)
Benzylidenmalonatpolysiloxan
4,4 '- [(6- [4 - ((1,1-dimethylethyl) aminocarbonyl) phenylaminoj-1,3,5-triazine-2,4-diyl) diimino] bis (2-ethylhexyl benzoate)
2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol
2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl) -6- (methoxyphenyl) -1,3,5) triazine
2,2 '- (1,4-phenylene) -bis-1H-benzimidazole-4,6-disulfonic acid monosodium salt
N- (2 and 4) - [(2-oxoborn-3-ylidene) methyl] benzyl] acrylamide polymer
Polysiloxanmalonate
Glycerylethylhexanoatedimethoxycinnamat
Disodium 2,2'-dihydroxy-4,4'-dimethoxy-5,5'-disulfobenzophenone
Dipropylenglycolsalicylat
Natriumhydroxyrnethoxybenzophenonsulfonat

Particularly suitable UV absorbers are:
p-aminobenzoic acid and its salts
p-aminobenzoate
p-dimethylaminobenzoic acid 2-ethylhexyl ester
Salicylic acid homomenthylester
Salicylic acid 2-ethylhexyl ester
p-methoxycinnamic acid 2-ethylhexyl ester
p-methoxycinnamate
2-ethylhexyl 2-cyano-3,3-diphenyl
2-phenylbenzimidazole sulfonic acid and its salts
3- (4'-trimethylammonium) -benzylidene-bornan-2-one methyl sulfate
Terephthalylidene-dibornanesulfonic acid and its salts (Mexoryl SX)
4-tert-butyl-4'-methoxy-dibenzoylmethane (avobenzone)
b-imidazole-4 (5) -acrylic acid (urocanic acid)
2-hydroxy-4-methoxybenzophenone
2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts
3- (4'-Sulfo) benzylidene-bornan-2-one and its salts
3- (4'-methylbenzylidene) -d, 1-camphor
2,4,6-trianilino- (p-carbo-2'-ethylhexyl-1'-oxy) -1,3,5-triazine
Phenol, 2- (2H-benzotriazol-2-yl) methyl-6- (2-methyl-3- (1,3,3,3-tetramethyl-1- (trimethylsilyl) disiloxanyl) propyl (dromitrizole trisiloxanes)
Benzylidenmalonatpolysiloxan
4,4 '- [(6- [4 - ((1,1-Dimethylethyl) aminocarbony1) phenylamino] -1,3,5-triazine-2,4-diyl) dümino] bis (2-ethylhexyl benzoate)
2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol
2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (methoxyphenyl) -1,3,5) triazine
2,2 '- (1,4-phenylene) -bis-1H-benzimidazole-4,6-disulfonic acid monosodium salt
N- (2 and 4) - [(2-oxoborn-3-ylidene) methyl] benzyl] acrylamide polymer

It can also be advantageous to use polymer-bound or polymeric UV absorbers To use preparations according to the present invention, in particular those as described in WO A1 92/20690.

Furthermore, the N-substituted anilionomethylene Derivatives I also with UV absorbers used for technical product protection  will combine. Examples of such UV absorbers mainly correspond to Ver bonds from the series of benzotriazoles, benzophenones and malonic esters.

The following examples are intended to illustrate the present invention without restrict them. All quantities, proportions and percentages are so far not otherwise specified, on the weight and the total amount or on the Ge total weight of the preparations.

Unless otherwise stated, the N was separated or cleaned substituted anilionomethylene derivatives by crystallization, distillation or Column chromatography on silica gel 60 (elution with n-hexane / ethyl acetate (5-10): 1).  

Examples example 1 2- (anilinomethylene) -propandisäurediethylester

46.5 g (0.5 mol) of aniline and 108 g (0.5 mol) of diethylethoxymethylene malonate Heated to 100 ° C for 3 hours. After cooling to about 60 ° C, 280 g of n-hexane added and cooled to 10 ° C. The resulting crystals are suctioned off. 112.5 g (85.5% of theory) of 2 - [(phenylamino) methylene] propanedioic acid are obtained diethyl ester with a melting point of 52-53 ° C.

Example 2 3-anilino-2-cyano-2-ethylhexyl-2-propenensäure

9.3 g (0.1 mol) of aniline, 14.8 g (0.1 mol) of triethyl orthoformate and 19.7 g (0.1 mol) of 2-ethylhexyl cyanoacetate are heated to 150.degree. Ethanol is first distilled off within 2 hours and then the product (bp _1mbar = 201 ° C.) is distilled. 23.4 g (75% of theory) of 2-cyano-3-phenylamino-acrylic acid 2-ethylhexyl ester are obtained.

Examples 3-18 General procedure for the preparation of 2- (N-alkylanilinomethylene) propane diacid dialkyl esters and 3-N-alkylanilino-2-cyano-2-propenoic acid esters Method A (alkylation)

0.15 mol of dialkyl 2- (anilinomethylene) propanedioate or 3-anilino-2-cyano-2- propenic acid esters are dissolved in 120 ml dimethylformamide and 6.6 g (0.165 mol) Sodium hydride (60%) added. Then 0.165 mol of alkyl is metered in halide within 60 minutes at 20 ° C.

To complete the reaction, the mixture is stirred for 3 hours at room temperature. Then 600 ml of methyl tert-butyl ether and 1000 ml of water are added to the reaction mix, separate the phases and extract the aqueous phase twice with 200 ml each Methyl tert-butyl. The combined organic phases are ge with water wash, dried with sodium sulfate and concentrated on a rotary evaporator. The residue obtained is by crystallization, distillation or column chromatography graphic cleaned.

Method B (condensation)

1 mol of N-alkylaniline, 148 g (1 mol) of triethyl orthoformate and 1 mol of cyanoacetic acid Acid alkyl esters are heated to 150 ° C and within about 120 minutes Distilled off ethanol. The product is then cleaned in a suitable manner.

Method C (transesterification)

0.05 mol of diethyl 2- (N-alkylanilinomethylene) -2-propanedioate or 3-N-alkyl anilino-2-cyano-2-propenoic acid ethyl ester, 100 g higher alcohol and 0.3 g tetra ethyl orthotitanate are heated under reflux for 8 hours. After the end of the reaction  the excess higher alcohol is distilled off under reduced pressure. The accumulating residue is by crystallization, distillation or column chro matography cleaned.

Table 1

Example 19

Sun protection soft cream (O / W), waterproof

production method

Part A: Heat to approx. 85 ° C.
Part B: Weigh raw materials without Carbopol. Disperse Carbopol with Ultra Turrax. Heat to approx. 85 ° C. Add B to A.
Part C: Add immediately to A / B and then homogenize hot (Ultra Turrax). Let cool while stirring.
Part D: Add and stir.

Example 20

Sun protection lotion (O / W)

production method

Part A: Heat to approx. 85 ° C.
Part B: Weigh raw materials without Carbopol. Disperse Carbopol with Ultra Turrax. Heat to approx. 85 ° C. Add B to A.
Part C: Add immediately to A / B and then homogenize hot (Ultra Turrax). Let cool while stirring.
Part D: Add and stir.

Example 21

Sun protection milk (O / W)

production method

Part A: Heat to 80-85 ° C.
Part B: Heat to 80-85 ° C, add Part B to Part A while stirring.
Part C: Disperse Carbopol in the water and neutralize with NaOH while stirring. Add part C at approx. 60 ° C while stirring. Let cool to RT.
Part D: Add and stir.

Example 22

Sun protection lotion (O / W)

production method

Part A: Heat to 80-85 ° C.
Part B: Heat to 80-85 ° C, add Part B to Part A while stirring.
Part C: Disperse Carbopol in the water and neutralize with NaOH while stirring. Add part C at approx. 60 ° C while stirring. Let cool to RT.
Part D: Add and stir.

Example 23

Sun protection lotion (O / W)

production method

Part A: Dissolve UV absorber according to formula 1 in the oils or liquid UV filters (heating up to approx. 70 ° C). Allow to cool to approx. 30 ° C, add the remaining ingredients apart from Carbopol and Pemulen and mix at room temperature (stir for approx. 5 minutes). Stir in Carbopol and Pemulen.
Part B: Dissolve Solbrole in phenoxyethanol while heating. Mix with water and glycerin, add to part A while stirring. Approximately Stir for 60 minutes.
Part C: Add to A / B, homogenize with the Ultra Turrax.

Example 24

Sun protection cream (W / O), waterproof

production method

Part A: Heat to approx. 85 ° C.
Part B: Heat to approx. 85 ° C (without zinc oxide; disperse zinc oxide with the Ultra Turrax). Add B to A Allow to cool with stirring, then homogenize.

Example 25

Sun protection soft cream (W / O),

production method

Part A: Heat to approx. 85 ° C.
Part B: Heat to approx. 85 ° C (without zinc oxide; disperse zinc oxide with the Ultra Turrax). Add B to A. Let cool while stirring.
Part C: Add and then homogenize

Example 26

Sun protection milk (W / O)

production method

Part A: Heat to approx. 85 ° C.
Part B: Heat to approx. 85 ° C. Add B to A. Let cool while stirring.
Part C: Add and then homogenize.

Example 27

Day care cream with UV protection

production method

Part A: Heat to 80 ° C.
Part B: Heat to 80 ° C. Add to part A while stirring.
Part C: Disperse Carbopol in water and neutralize with sodium hydroxide solution. Add to part A / B at approx. 55 ° C.
Part D: Add at RT and homogenize.

Example 28

Sunscreen Spray

production method

Part A: Dissolve Lara Care A-200 in the other ingredients of Part A while stirring.
Part B: Weigh in all raw materials (without Pemulen) and dissolve the crystalline sub with heating. Disperse the pemules. Add part B to part A and homogenize for 1 minute.
Add part C + D and homogenize again with the Ultra Turrax for 1-2 minutes.

Example 29

Sun protection hydrodispersion gel (Balm)

production method

Part A: Disperse Carbopol in water and neutralize with sodium hydroxide solution.
Part B: Add to Part A while stirring.
Part C: Dissolve crystalline constituents from part C while heating (max. 40 ° C) in the other raw materials and add to part A / B. Mix well and then homogenize. (Homozenta).

Example 30

Hair conditioner with UV filters

production method

Part A: Heat to 80 ° C.
Part B: Heat to 80 ° C. Add to part A while stirring.
Part C: Add at 40 ° C and cool to RT.

Determination of photostability

From a 5% solution of the UV filter to be tested or a combination with other commercially available UV absorbers such as OMC (octyl methoxycinnamate) and / or BMDM (tert-butyl methoxy dibenzoyl methane), 20 µl are evenly spread over 10 cm ² a glass plate with a roughened surface. After a storage time of 30 minutes in the dark, the sample is irradiated in a Suntest device with a solar standard filter and global sensor for 140 minutes with an irradiance of 765 W / m ² . During the irradiation, the glass plates are on the cooled bottom of the sun tester. A total of 4 glass plates are irradiated at the same time. After the end of irradiation, the samples are rinsed with ethanol from the glass plates into a 25 ml volumetric flask. In the samples thus obtained, the light stabilizer content is determined by means of a photometer or HPLC. At the same time, blank samples are applied to the glass plates as indicated above and then rinsed and measured like the irradiated samples.

Table 1

SPF regulations, recipes and production of those for the SPF regulations used emulsions A-G  

manufacturing

Table 3

manufacturing

Table 4

manufacturing

Table 5

Claims (14)

1. Cosmetic and pharmaceutical preparations for protecting human skin and hair from the damaging effects of ultraviolet solar radiation using N-substituted anilionomethylene derivatives of the formula I in which the C = C double bond is in the E or Z configuration,
wherein
R ¹ C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₃ -C ₁₅ cycloalkyl, C ₆ -C ₁₂ aryl, C ₆ -C ₁₂ aryl, C ₁ -C ₆ alkyl, C ₅ -C ₁₂ heteroaryl, the substituents mentioned with C ₁ -C ₆ alkyl, C ₁ -C ₁₆ alkoxy, C ₆ -C ₁₂ aryloxy, amino, hydroxy, COOR ⁹ , CONR ¹⁰ R ¹¹ , a Group W can be substituted or interrupted by ether oxygen,
R ² COOR ⁹ , CONR ¹⁰ R ¹¹ , CN, COR ⁹
R ³ COOR ¹² , CONR ¹³ R ¹⁴ , CN, COR ¹²
R ⁴ to R ⁸ independently of one another are hydrogen, amino, nitro or the meaning given under R ¹
R ⁹ to R ¹⁴ independently of one another have hydrogen or the meaning given under R ¹ , where R ⁹ cannot again stand for the group COOR ⁹ ,
W silanes, oligosilanes and polysiloxanes of the general formulas W ^I to W ^III
W ^I SiR ¹⁵ _a (OSiR ¹⁵ ₃ ) _b
a 0, 1, 2 or 3
b 3, 2, 1 or 0
a + b 3
A is a bond to the neighboring atom
c 1-10
R ^{15 is} an open-chain or branched aliphatic, araliphatic, cyclo aliphatic or optionally substituted aromatic radical, each having up to 18 carbon atoms
mean. 2. Cosmetic and pharmaceutical sunscreen preparations according to claim 1
wherein
R ¹ optionally substituted alkyl;
R ² COOR ⁹ , CN, COR ⁹ ;
R ³ COOR ¹² , CN, COR ¹² ;
R ⁹ , R ¹² independently of one another are an open-chain or branched aliphatic, araliphatic, cycloaliphatic or optionally substituted aromatic radical, each having up to 18 carbon atoms
means. 3. Cosmetic and pharmaceutical sunscreen preparations according to claims 1 and 2
wherein
R ^{1 is} an optionally substituted, open-chain or branched aliphatic radical with up to 8 C atoms;
R ² COOR ⁹ ; CN;
R ³ COOR ¹² CN;
R ⁹ , R ¹² independently of one another are an open-chain or branched aliphatic radical with up to 18 carbon atoms
mean. 4. Cosmetic and pharmaceutical sunscreen preparations according to the An Proverbs 1 to 3 with the additional use of UV-B and UV-A Absorbers. 5. Cosmetic and pharmaceutical sunscreen preparations according to the An sayings 1 to 4 wherein as UV-B and UV-A filter compounds from the Groups of cinnamates, salicylates, p-aminobenzoates, benzophenones, di phenyl acrylates, camphor derivatives, triazines, benzylidene malonates, benzo triazoles, benzimidazoles, dibenzoylmethanes, polymer filters and silicone filter mean. 6. Cosmetic and pharmaceutical sunscreen preparations according to the An sayings 1 to 5 wherein as UV-B and UV-A filters in particular p-methoxy 2-ethylhexyl cinnamate, isoamyl p-methoxycinnamate, 4-methyl benzylidene camphor, 2-phenylbenzimidazole sulfonic acid, salicylic acid-2-ethyl hexyl ester, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, 2,2 '- (1,4-phenylene) - bis-1H-benzimidazole-4,6-disulfonic acid monosodium salt, 4-tert-butyl-4'- mean methoxydibenzoylmethane.   7. Cosmetic and pharmaceutical sunscreen preparations according to the An Proverbs 1 to 6 in which inorganic pigments based on Metal oxides, especially the oxides of titanium, zinc and iron, ent are holding. 8. Cosmetic and pharmaceutical sunscreen preparations according to the An Proverbs 1 to 7 which continue to contain cosmetic auxiliaries such as fats, emul gators, thickeners, emollients, organic solvents, polymers, sili kone, organic solvents, antioxidants, perfumes, preservatives substances, vitamins, complexing agents, skin lightening agents, plant extracts, Colorants and coolants and refreshments included. 9. Cosmetic and pharmaceutical sunscreen preparations according to the An sayings 1 to 8 in the form of emulsion, milk, lotion or cream, Aerosol, hydrodispersion or oil gel, spray, foam, solution, powder, fat pen or as any other common cosmetic or pharmaceutical accessory horse riding. 10. Cosmetic and pharmaceutical sunscreen preparations according to the An sayings 1 to 8 which are available as a waterproof formulation. 11. Connections from the group
2- (N-Methylanilinomethylen) -propandisäuredi-n-propyl ester
2- (N-Methylanilinomethylen) -propandisäuredi 1-methylethyl ester
2- (N-Methylanilinomethylen) -propandisäuredi-n-butyl ester
2- (N-Methylanilinomethylen) -propandisäuredi-2-methylpropyl ester
2- (N-Methylanilinomethylen) -propandisäuredi n-pentyl
2- (N-Methylanilinomethylen) -propandisäuredi-3-methylbutyl ester
2- (N-Methylanilinomethylen) -propandisäuredi-4-methylpentyl ester
2- (N-Methylanilinomethylen) -propandisäuredi 2-ethylhexyl
2- (N-Ethylanilinomethylen) -propandisäuredi-n-propyl ester
2- (N-Ethylanilinomethylen) -propandisäuredi 1-methylethyl ester
2- (N-Ethylanilinomethylen) -propandisäuredi-n-butyl ester
2- (N-Ethylanilinomethylen) -propandisäuredi-2-methylpropyl ester
2- (N-Ethylanilinomethylen) -propandisäuredi n-pentyl
2- (N-Ethylanilinomethylen) -propandisäuredi-3-methylbutyl ester
2- (N-Propylanilinomethylen) -propandisäuredi-n-propyl ester
2- (N-Propylanilinomethylen) -propandisäuredi 1-methylethyl ester
2- (N-Propylanilinomethylen) -propandisäuredi-n-butyl ester
2- (N-Propylanilinomethylen) -propandisäuredi-2-methylpropyl ester
2- (N-Propylanilinomethylen) -propandisäuredi-3-methylbutyl ester
2-cyano-3- (N-methylanilino) -2-propenoic acid n-propyl ester
2-cyano-3- (N-methylanilino) -2-propenoic acid, methylethyl ester
2-cyano-3- (N-methylanilino) -2-propenoic acid n-butyl ester
2-cyano-3- (N-methylanilino) -2-propenoic acid 2-methylpropyl ester
2-cyano-3- (N-methylanilino) -2-propenoic acid n-pentyl
2-cyano-3- (N-methylanilino) -2-propenoic acid-3-methylbutyl ester
2-cyano-3- (N-methylanilino) -2-propenoic acid, n-hexyl
2-cyano-3- (N-methylanilino) -2-propenoic acid 4-methylpentyl ester
2-cyano-3- (N-methylanilino) -2-propenoic acid 2-ethylhexyl ester
2-cyano-3- (N-ethylanilino) -2-propenoic acid n-propyl ester
2-cyano-3- (N-ethylanilino) -2-propenoic acid, methylethyl ester
2-cyano-3- (N-ethylanilino) -2-propenoic acid n-butyl ester
2-cyano-3- (N-ethylanilino) -2-propenoic acid 2-methylpropyl ester
2-cyano-3- (N-ethylanilino) -2-propenoic acid n-pentyl
2-cyano-3- (N-ethylanilino) -2-propenoic acid-3-methylbutyl ester
2-cyano-3- (N-ethylanilino) -2-propenoic acid, n-hexyl
2-cyano-3- (N-ethylanilino) -2-propenoic acid 4-methylpentyl ester
2-cyano-3- (N-ethylanilino) -2-propenoic acid, n-octyl
2-cyano-3- (N-ethylanilino) -2-propenoic acid 2-ethylhexyl ester
2-cyano-3- (N-propylanilino) -2-propenoic acid n-propyl ester
2-cyano-3- (N-propylanilino) -2-propenoic acid, methylethyl ester
2-cyano-3- (N-propylanilino) -2-propenoic acid n-butyl ester
2-cyano-3- (N-propylanilino) -2-propenoic acid 2-methylpropyl ester
2-cyano-3- (N-propylanilino) -2-propenoic acid n-pentyl
2-cyano-3- (N-propylanilino) -2-propenoic acid-3-methylbutyl ester
2-cyano-3- (N-propylanilino) -2-propenoic acid, n-hexyl
2-cyano-3- (N-propylanilino) -2-propenoic acid 4-methylpentyl ester
2-cyano-3- (N-propylanilino) -2-propenoic acid, n-octyl
2-cyano-3- (N-propylanilino) -2-propenoic acid 2-ethylhexyl ester 12. The use of compounds according to claim 1 as a solvent for other crystalline UV filters. 13. The use of compounds according to claim 1 for photostabilization other UV filter. 14. The use of compounds according to claim 1 in combination with conventional UV absorbers for synergistic enhancement of the photo protective effect in cosmetic and pharmaceutical light protection accessories TION.