DE4406024A1 - New and known benzazole cpds. as UV absorbers for sunscreens - Google Patents

Abstract

The use as UV absorbers in sunscreens of cpds. contg. at least 2 benzazolyl gps. per mol. (I) is new. Also claimed are cpds. (I) contg. 3 or 4 SO3Y gps. per mol.

Description

The invention relates to the use of compounds which are per molecule at least two benzazolyl radicals, z. B. at least two benzimidazol-2-yl radicals, ent as a UV absorber in sunscreens, as well as new benzazoles and a process for their preparation by reacting difunctional anilines with reactive carboxylic acid derivatives.

Depending on the wavelength, UV rays are emitted as 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) designated. In general: The damaging effect of UV rays on the human skin increases with decreasing wavelength and increasing duration of the Exposition.

Thus, UV rays can cause skin damage, with the UV-B radiation a sunburn (erythema) to severe skin burns can cause. Very frequent and unprotected irradiation of the skin with Sunlight also leads to a loss of skin elasticity and increased Wrinkling, overall premature aging of the skin. In extreme cases can be abnormal skin lesions up to skin cancer occur.

The UV-A radiation causes rapid, weak direct pigmentation of the skin. UV-A rays penetrate into deeper skin layers and can there the Speed up the aging process of the skin. The shorter-wave UV-A-II radiation supports the formation of sunburn. Furthermore, the UV-A radiation trigger phototoxic or photoallergic skin reactions. There exist ge  ensured links between UV-A exposure and increased skin cancer risk.

According to the location of their absorption maxima are UV absorbers for kosme tables and dermatological preparations in UV-A and UV-B absorbers divided.

There are a larger number of safe and effective UV-B absorbers, such as. B. p- Isooctyl methoxycinnamate, isoamyl p-methoxycinnamate, phenylbenzimide azole-Na-sulfonate and 3- (4'-methylbenzylidene) -campher.

The number of UV-A absorbers suitable for human skin protection is However, not only very limited, but these absorbers are also serious Disadvantages:

Dibenzoylmethane derivatives (4-t-butyl-methoxy-dibenzoylmethane and 4-isopropyl dibenzoylmethane) are not very light stable, d. H. their UV-A protection performance leaves rapidly after use. Furthermore, they have only a limited solubility in cosmetic oils, causing problems in the formulation of cosmetic oils Preparations can lead. The absorption maximum is in the less ge dangerous UV-A-I range. In addition, dibenzoylmethane derivative-containing Sunscreen products on textiles extremely difficult washable stains behind to let. It is also known that dibenzoylmethane photosensitizes the skin can favor.

Benzophenones are UV-B and UV-A broadband absorbers and in short wavy UV-A-II range only a relatively low absorption. Your solution It is also limited in cosmetic oils.

Menthyl-O-amino tozoate has very little absorption in the UV-A-Be rich.

Terephthalylidene-dibornanesulfonic acid has an absorption maximum in the UV-A I range at 345 nm.

Wanted are UV-A absorbers, which have an absorption maximum in the UV-A-II Range and are characterized by a strong absorption against the dangerous, Protect short-wave UV-A rays. In addition, these UV-A absorber should still meet the following criteria: excellent lightfastness, toxicological and dermatological safety, excellent thermal stability, very good Solubility in cosmetic solvents (oils, water, glycols, alcohol, etc.), Compatibility with cosmetic ingredients, pH-stable (4-9), problem-free Processability in cosmetic formulations and stability under applications conditions of use, compatibility with packaging materials, no staining of Textiles, but at least: Stains on textiles must wash out without any problem be bar; colorlessness and odor neutrality, freedom from tack and low Volatility.

In DRP-676 103, the sodium salt of phenylbenzimidazole sulfonic acid (Absorption maximum: 316 nm) and similar compounds as UV absorbers in Sunscreens recommended for human skin. The described Ver However, bonds do not have the desired light stability or the desired Absorption maximum.

Surprisingly, compounds have now been found which are not only due to their absorption maximum in the UV-A-II range, the dangerous UV Radiation absorb, but also have excellent light stability. If the compounds contain carboxyl and / or sulfo groups, the rises Water solubility after neutralization with common bases (eg sodium hydroxide, Potassium hydroxide, triethanolamine, monoethanolamine, tetrahydroxypropylethylenedi amine, tris (hydroxymethyl) aminomethane, etc.) considerably, resulting in an un problematic incorporation into cosmetic basics. It should be emphasized that also cosmetic or dermatological preparations with a low pH (up to pH 4) can be stably formulated without a Auskristalli sation. Preparations with a high UV absorber content (for example wise up to 20 wt .-%) are possible.

It is noticeable that the addition of a base until reaching a pH above Fig. 10 shows a shift of the absorption maximum towards the longer wavelength range  (for example from 335 to 355 nm) occurs. So it's possible if needed this protective function of the compounds to be used according to the invention in the Move UV-A-I range.

The invention thus relates to the use of compounds per Molecule containing at least two benzazolyl groups, as UV absorbers in Sunscreens, preferably in cosmetic and dermatological Präpa guess.

Suitable benzazolyl groups are, for example, benzothiazolyl groups, preferably example benzoxazolyl groups and in particular benzimidazolyl groups. The off pressure "at least two benzazolyl groups" in the context of the invention but be satisfied in the presence of a Benzdiazolylengruppe, d. H. links with a benzimidazolylene group, for example, according to the invention ver reversible. An example of such a connection would be z. B. the compound of formula

Preferred compounds to be used correspond to the formula

wherein
Z is an (l + n) -valent organic radical having one or more double bonds in such position as to complement the double bond systems of at least 2 of the square-chain radicals to a conjugated total system, and
XS, preferably O, in particular NR⁶,
R¹ is hydrogen, C₁-C₁₈-alkyl, C₁-C₄-alkoxy, C₅-C₁₅-aryl, C₂-C₁₈-acyloxy, SO₃Y or COOY,
R² to R⁵ independently of one another nitro or the meaning indicated under R¹,
R⁶ is hydrogen, C₁-C₄-alkyl or hydroxy-C₁-C₄-alkyl,
Y is hydrogen, Li, Na, K, NH₄, ½Ca, ½Mg, ¹ / ₃Al or the cation of an organic nitrogen base used to neutralize the free acid groups,
l is zero or an integer from 1 to 4,
m is zero or 1 and
n is an integer from 2 to 6
with the proviso that the sum l + n is a maximum of 6.

Compounds (I) to be used according to the invention are preferably those wherein Z

• a) an olefinically unsaturated aliphatic C₂-C₆ hydrocarbon radical (which may be interrupted by a C₅-C₁₂-arylene radical or a C₄-C₁₀-hetarylene radical), such as. For example, -CH = CH-, -CH = CH-CH = CH- or
• b) a C₅-C₁₅-arylene radical which may be interrupted by an olefinically unsaturated aliphatic C₂-C₆ hydrocarbon radical, such as. B. Phe nylene, biphenylene, naphthylene,
• c) a C₃-C₁₀-Hetarylenrest such. B. wherein
  R⁶ has the meaning given above,

wherein the radicals indicated under a) to c) by C₁-C₆-alkyl, C₁-C₆-alkoxy, Phenoxy, hydroxy, methylenedioxy groups or amino groups represented by 1 or 2 C₁-C₅-alkyl radicals may be substituted, may be substituted, means.

Compounds (I) to be used according to the invention are in particular those in Z is -CH = CH-, -CH = CH-CH = CH-,

stands.

Pharmaceutically acceptable benzazolyl compounds with only one Benz Azolylgruppe are known for example from DE-OS 35 33 308. you will be u. a. against hair loss, to combat skin diseases and the greasy Appearance of the skin, to combat dry skin and to treat the skin adverse effects of the sun recommended. A prophylactic use against the damaging effect of UV rays on human skin but not mentioned.

The compounds to be used according to the invention are known in some cases; however, the use according to the invention was not suggested. That's how it describes For example, US Pat. No. 2,463,264 discloses the use of some compounds disclosed in US Pat the definition I fall as optical brightener. The use against the damaging influence of UV rays on human skin is also here neither mentioned nor suggested.

Another object of the invention are compounds II of the formula (I) with the In that these compounds II per molecule 1, 3 or 4 SO₃Y groups ent hold.

The compounds I can be prepared by known processes or analogously to these known methods are produced. One of the possible process variants is the reaction of carboxylic acid derivatives with o-phenylenediamine, o-aminophe  nol or o-aminothiophenol at higher temperatures in high-boiling flavor th, such. As diphenyl ether and / or biphenyl or in inorganic acids such as Phosphoric acid or sulfuric acid. Sulfonic acid groups can be added either before Condensation by sulfonation of the aromatic amines or after the condensations by treatment with oleum, hot sulfuric acid or chlorosulfonic acid be introduced. According to another variant of the method are aldehydes with the aromatic amines reacted under oxidative conditions.

In a preferred embodiment, condensation and sulfonation completed in a single step: Chlorosulfonic acid is simultaneously reaction medium and reagent. Another object of the invention is thus a method for the preparation of compounds II by reacting compounds of formula

wherein
X and R¹ to R⁴ have the abovementioned meaning, but R¹ and R⁴ are neither COOY nor SO₃Y,
with a compound of the formula

wherein
D is -OH, -NH₂, -Cl or O-C₁-C₃-alkyl,
in chlorosulfonic acid at temperatures of 20 to 190 ° C.

The compounds to be used according to the invention can be used as UV absorbers in cosmetic or dermatological preparations in quantities, the passage of the UV rays through the applied film of the preparation prevent. This is the case when the cosmetic or dermatological Preparations 0.5 to 15, preferably 1 to 10, in particular 3 to 8 wt .-%, based on the total weight of the preparation according to the invention to containing connection.

The formulations containing the compounds to be used according to the invention Treatments can protect the skin and hair - especially through duration wave, coloring and bleaching already damaged hair - before UV Bestrah be used. These protect the skin from the UV radiation the nenden cosmetic or dermatological preparations may in the übli cherweise used application forms, d. H. as an oil-in-water or Water-in-oil emulsion as milk, lotion or cream, watery or watery alcoholic gel or lotion, aerosol, hydrodispersion gel (emulsifier-free) or any other usual cosmetic or dermatological preparation. For the Protecting the hair from UV rays are preferred preparations as a shampoo, Conditioner, cure, gel, lotion, spray and cream used.

The cosmetic and dermatological preparations can be used in these usually used ingredients such. As emulsifiers, interfaces active compounds, lanolin, vaseline, water, triglycerides of fatty acids, Polyethylene glycols, fatty alcohols, ethoxylated fatty alcohols, fatty acid esters (eg. Isopropyl palmitate, isooctyl stearate, adipic diisopropyl ester, etc.), natural or synthetic oils or waxes, pigments (eg, titanium dioxide, zinc oxide, Per gloss pigments, color pigments), thickeners (for example hydroxyethyl cellulose, Bentonite, etc.), preservatives, moisturizers, vitamins, silicone oils, Glycerol, ethyl alcohol, perfume oils.

The compounds to be used according to the invention can be used as the only UV absorbers in the corresponding preparations; However, they can also be used in combination with other UV absorbers - in particular UV-B absorbers to obtain a UV-A + B broadband absorption or under weakly light-stable dibenzoylmethane derivatives (eg., Butyl methoxydibenzoyl-methane or p-). Methoxy-cinnamic acid-isopropyl ester) to stabilize them - use. Examples of games for such connections include
p-aminobenzoic acid
ethoxylated p-aminobenzoic acid ethyl ester (25 mol)
p-dimethylaminobenzoic acid 2-ethyl ester
p-aminobenzoic acid ethyl ester (2 moles) N-propoxylated
p-Aminobenzoesäureglycerinester
Salicylic acid homomenthylester
Salicylic acid 2-ethylhexyl ester
triethanolamine
4-isopropylbenzyl
anthranilate
Diisopropylzimtsäureethylester
p-Methoxyzimtsäure2-ethylhexyl
Diisopropylzimtsäuremethylester
p-methoxycinnamic acid isoamyl ester
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 salts
N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) -aniliniummethylsulfat
Tetraphthalylidene-dibornanesulfonic acid and salts
4-t-butyl-4'-methoxy-benzoylmethane
β-imidazole-4 (5) -acrylic acid (urocanic acid)
2-hydroxy-4-methoxybenzophenone
2-hydroxy-4-methoxybenzophenone-5-sulfonic acid
Dihydroxy-4-methoxybenzophenone
2,4-dihydroxybenzophenone
tetrahydroxy
2,2'-dihydroxy-4,4'-dimethoxybenzophenone
2-hydroxy-4-n-octoxybenzophenone
2-hydroxy-4-metoxy-4'-methylbenzophenone
α- (2-oxoborn-3-ylidene) -tolyl-4-sulfonic acid and salts
3- (4'-methylbenzylidene) -d, l-camphor
3-benzylidene-d, l-camphor
4-isopropyldibenzoylmethane
2,4,6-trianilino- (p-carbo-2'-ethylhexyl-1'-oxy) -1,3,5-triazine
Particularly suitable UV-B absorbers are
p-methoxycinnamic acid 2-ethylhexyl ester,
p-methoxycinnamic acid isoamyl ester,
2-phenylbenzimidazole sulfonic acid and
3- (4'-methylbenzylidene) -d, l-camphor.

The parts given in the following examples are parts by weight, Pro cents are by weight.  

Examples example 1 Phenylenbisbenzimidazoltetrasulfonsäure

108 parts of purified o-phenylenediamine are concentrated in 500 parts H₂SO₄. entered and 800 parts of chlorosulfonic added dropwise. The mixture is heated for 15 min. At 120 ° C, with continuous release of HCl, cooled to 70 ° C and treated with 83 parts of terephthalic acid. The reaction mixture continues to liberate HCl and is heated to 180 ° C. After a reaction time of 30 min. At this temperature is cooled to 80 ° C and added to 2500 parts of ice. The precipitated crystals are filtered off, taken up in sodium hydroxide solution and heated with activated charcoal. After precipitation with H₂SO₄ and drying of the crystals in vacuo, 210 parts of product. This product contains by RP-HPLC (MeOH / H₂O) 99% of the title substance and about 1% of trisulfonic acid. According to NMR, the sulfonic acid groups are in meta position to each other. (For comparison of the NMR data, it is essential to adjust the pH, since the shift values of the compounds presented here are strongly pH-dependent.) The melting point is <280 ° C.
λ max = 208; E ^1% _{1 cm} = 1142; λ max = 256; E ^1% _{1 cm} = 280.2; λ max = 335; E ^1% _{1 cm} = 745.

Analogous to this method are used instead of terephthalic acid:

• - phthalic acid
• - isophthalic acid
• - trimellitic acid
• - pyromellitic acid

Example 2 Phenylenbisbenzimidazoltrisulfonsäure

Following the procedure of Example 1, but keeping the reaction temperature below 70 ° C, the trisulfonated product is obtained in the main, which can be characterized by RP-HPLC isolation by NMR spectroscopy.
λ max = 206; E ^1% _{1 cm} = 650; λ max = 254; E ^1% _{1 cm} = 162; λ max = 335; E ^1% _{1 cm} = 756.

Example 3 Phenylenbisbenzimidazoldisulfonsäure

550 parts of concentrated sulfuric acid (96%) are introduced and successively entered 108 parts of o-phenylenediamine. The reaction is exothermic and the mixture is heated to 95-100 ° C. At this temperature, 83 parts of terephthalic acid are added and the total mixture heated at 200 ° C for 5 h. After cooling to 100-120 ° C is poured onto 1000 parts of ice and stirred for 1 h. The green to brown precipitate is filtered off, taken up in NaOH and heated with 20 parts of activated carbon for 1 h under reflux. After filtration, the pH is adjusted to 1.5 to 2 with H₂SO₄ and filtered off the light precipitate. The product is slurried with methanol, filtered off and dried.
λ max = 218; E ^1% _{1 cm} = 1057; λ max = 256; E ^1% _1cm = 424; λ max = 351; E ^1% _{1 cm} = 1289.

Analogously, phenylenebisbenzoxazoledi-sulfonic acid is prepared from o-hydroxyaniline and terephthalic acid.
λ max = 203; E ^1% _{1 cm} = 1395; λ max = 323; E ^1% _{1 cm} = 907; λ max = 337; E ^1% _{1 cm} = 897.

Example 4 2,2'-Bisbenzimidazoldisulfonsäure

44 parts of oxalic acid diamide and 108 parts of o-phenylenediamine are dissolved in 300 parts Submitted ethylene glycol and heated to reflux. The resulting ammonia gas is absorbed in a wash bottle with hydrochloric acid. Once about 16 parts Ammonia are absorbed, the reaction mixture is cooled and washed with 100 parts of water added. The precipitated product is after filtration and Drying immediately used in the next stage.

For this purpose, 23.4 parts of this 2,2'-bisbenzimidazole in 100 parts conc. H₂SO₄ dissolved and the mixture with 55 parts of fuming (30%) sulfuric acid and heated to 100-120 ° C. After 3 hours, the mixture is reduced to 500 parts of ice given, with a greenish fluorescence is recognizable. The filtrate is with Sodium hydroxide neutralized and decolorized with activated charcoal. After narrowing the Lö Solution and drying gives a pale yellow, excellent water-soluble Na triumsalz of the title compound, which shows a blue-red fluorescence in solution.

Example 5 Sunscreen Milk (O / W)

From a UV-A absorber according to formula (I), a 20% preliminary solution, neutralized with sodium hydroxide, prepared. Of this preliminary solution, 20% used, resulting in an active content of 4.00% UV-A absorber in the final form corresponds to lation.  

Used components

Alugel 30 DF: aluminum distearate, supplier 21
Arlacel 581: glycerol mono- and distearate and polyethylene glycol stearate, supplier 4
Arlacel 165: glycerol stearate / polyethylene glycol (MG 100) stearate mixture, supplier 4
Arlamol HD: isohexadecane, supplier 4
Arlatone T: Oleate of ethoxylated sorbitol, supplier 5
Arosol: phenoxyethanol, supplier 1
Baysilone Fluid PK 20: Silicone Oil, Supplier 5
Concretes Gel MIO: mineral oil, supplier 13
Carbopol 940: polyacrylic acid, supplier 2
Carbopol 941: polyacrylic acid, supplier 2
Carbopol 1342: polyacrylate, supplier 2
Carbopol ETD 2001: acrylic acid copolymer, supplier 2
Cetiol MM: myristyl myristate, supplier 3
Cetiol S: dioctylcyclohexane, supplier 3
Cetiol V: decyl oleate, supplier 3
Cetiol OE: dicapryl ether, supplier 3
Cetiol SN: cetyl / stearyl isononanoate, supplier 3
Cremophor NP 14: nonylphenol etherified with 14 moles of ethylene oxide, supplier 6
Cutina CBS: glycerin stearate, cetyl / stearyl alcohol, cetyl palmitate, coconut glycerides, supplier 3
Cutina FS 45: palmitic / stearic acid mixture, supplier 3
Cutina MD: Glycerine Stearate, Supplier 3
Dehymuls HR E 7: ethoxylated hydrogenated castor oil, supplier 3
Dehyquart A: cetyltrimethylammonium chloride, supplier 3
Elfacos C 26: hydroxyoctacosanyl-hydroxystearate, supplier 19
Elfacos E 200: ethylene glycol / dodecyl glycol polyether with methoxy end groups, supplier 19
Elfacos ST 9: ethylene glycol / dodecyl glycol pdyether, supplier 19
Eumulgin B 1: cetyl / stearyl alcohol, etherified with 12 moles of ethylene oxide, supplier 3
Eumulgin B 2: cetyl / stearyl alcohol, etherified with 20 moles of ethylene oxide, supplier 3
Eusolex 6007: octyl N, N-dimethyl-p-aminobenzoate, supplier 17
Euxyl K 100: 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one and benzyl alcohol, supplier 13
Genapol LRO fl .: sodium lauryl sulphate, supplier 12
Heliopane, type AV: p-methoxycinnamic acid isooctyl ester, supplier 1
Heliopan, type E 1000: isoamyl p-methoxycinnamate, supplier 1
Lameform TGI: Triglycerol diisostearate, supplier 3
Lamepon S: protein / coconut fatty acid condensate, potassium salt, supplier 3
Lanette O: cetyl / stearyl alcohol mixture, supplier 3
Mulsifan RT 203/80: fatty alcohol polyglycol ether, supplier 9
Myritol 318: caprylic / capric triglyceride, supplier 3
Natrosol 250 HHR: hydroxyethyl cellulose, supplier 15
Neo Heliopan, Type BB: 2-hydroxy-4-methoxybenzophenone, supplier 1
Neo Heliopan, type Hydro: phenylbenzimidazole sulphonic acid, supplier 1
Nutrilan L: protein hydrolyzate, Na salt, supplier 3
Octocrylene: α-phenyl-β-cyanocinnamic acid isooctyl ester, supplier 6
Permulgin: wax, supplier 18
Phenonip: Mixture of p-hydroxybenzoic acid esters, supplier 11
Protegin WX: Combination of non-ionic fatty acid esters of polyvalent alcohols with waxes and purified saturated hydrocarbons, supplier 10
Quaternium-18 hectorite: propylene carbonate, supplier 13
Solbrol P: propyl p-hydroxybenzoate, supplier 5
Solbrol M: p-hydroxybenzoic acid methyl ester, supplier 5
Tagat S: polyoxyethylene glycol monostearate, supplier 10
Tegin M: glycerol stearate, supplier 10
Texapon MG 3: magnesium lauryl sulfate / disodium lauryl sulfosuccinate, supplier 3
Tioveil MOTG: 40% by weight aqueous dispersion of titanium dioxide, supplier 20
Trilon B fl .: tetrasodium ethylenediaminetetraacetic acid, supplier 6
Uvinul MS 40: p-hydroxybenzophenone, supplier 6
Uvinul P 25: Polyethylene glycol ester of p-aminobenzoic acid, supplier 6
Uvinul T 150: triazinyl-p-aminobenzoic acid isooctyl ester, supplier 6
Veegum Ultra: magnesium aluminum silicate. Supplier 14

Suppliers

1. Haarmann & Reimer GmbH, Holzminden
2. BF Goodrich Comp., Neuss
3. Henkel KGaA, Dusseldorf
4. ICI Specialty Chemicals, Frankfurt
5. Bayer AG, Leverkusen
6. BASF, Ludwigshafen
7. Sutton Lab. Inc., Chatham, NJ, USA
8. Gattefoss', Saint-Priest C'dex
9. Zschimmer & Schwarz GmbH, Lahnstein
10. Goldschmidt AG, Essen
11. Nipa Lab. Ltd., Pontypridd Mid Glam, Wales, UK
12. Hoechst AG, Frankfurt
13. Schülke & Mayr GmbH, Norderstedt
14. RT Vanderbilt Company Inc., Norwalk, USA
15. Hercules Inc., Wilmington, Del, USA
16. Givaudan-Roure GmbH, Geneva
17. E. Merck, Darmstadt
18. Koster Keunen Holland BV, Bladel, NL
19. Akzo Chemie GmbH, Düren
20. Tioxide Chemicals Ltd., Billingham, Cleveland, UK
21. Chemische Werke Bärlocher, Munich

ingredients % A) Cutina FS 45 2.00 Eumulgin B 1 0.25 Eumulgin B 2 0.25 Cutina MD 2.00 Lanette O 2.80 Myritol 318 5.00 Paraffin oil 65 cp 3.00 Arosol 0.80 Solbrol P 0.10 p-Methoxyzimtsäureisooctylester 3.00 p-methoxycinnamate 3.00 Neo Heliopan, type BB 1.50 B) water, dist. 51.05 Carbopol 941 0.30 Sodium hydroxide, 10% in water 2.45 1,2-propylene glycol 2.00 Solbrol M 0.20 UV-A absorber according to formula (I) used as a 20% solution after neutralization with sodium hydroxide 20.00 corresponds to active substance: 4.00% @ C) perfume oil 0.30

Part A: Melt at about 75 to 80 ° C.

Part B: Disperse Carbopol lump-free in water, with sodium hydroxide solution neutralize, add the remaining ingredients and bring to about 95 ° C heat.

Add Part B with stirring to Part A and stir to room temperature. At approx. Add 30 ° C part C. Check pH value (7.0-7.5).

Example 6 Sun protection lotion (O / W)

From the UV absorber according to formula (I) was a 20% preliminary solution, neutrali Siert with sodium hydroxide, prepared. 15% of this solution was used which corresponds to an active content of 3.00% UV-A absorber in the final formulation speaks.

ingredients % A) Arlacel 165 | 3,00 Eumulgin B 2 1.00 Lanette O 2.00 Myritol 318 4.00 Cetiol OE 6.00 Concrete Gel MIO and Quaternium-18 Hectorite (3.00) Phenonip 0.20 Cutina CBS 2.00 p-Methoxyzimtsäureisooctylester 7.00 4-methylbenzylidene-camphor 1.00 Zinc oxide neutral 5.00 B) water, dist. 45,90 Veegum Ultra 1.00 Natrosol 250 HHR 0.30 Glycerin 85% 3.00 Phenonip 0.30 UV-A absorber according to formula (I) used as a 20% solution after neutralization with sodium hydroxide 15.00 corresponds to active substance: 3.00% @ C) perfume oil 0.30

Preparation Method

Part A: Melt at about 80 ° C, then carefully neutral zinc oxide disperse.

Part B: Heat without Veegum and Natrosol to about 90 ° C, then Veegum and Natrosol dispersing. Add part B with stirring to part A. Stir to room temperature.

Part C: Add part C at 30 ° C and then homogenize. Check pH value (7.0-7.5).

Example 7 Sunscreen cream (O / W)

From the UV-A absorber according to formula (I) was a 20% pre-solution, new tralized with sodium hydroxide, prepared. Of this preliminary solution, 20% used, resulting in an active content of 4.00% UV-A absorber in the final form corresponds to lation.

ingredients % A) Tegin M 3.00 Tagat S 2.30 Lanette O 3.50 Paraffin oil 65 cp 4.00 Arlamol HD 3.50 Cetiol MM 2.00 Phenonip 0.20 p-Methoxyzimtsäureisooctylester 4.00 p-methoxycinnamate 4.00 B) water, dist. 16.85 Phenonip 0.20 Neo Heliopan, type Hydro, used as a 15% solution after neutralization with sodium hydroxide / phenylbenzimidazole sulfonic acid 6.70 corresponds to active substance: 1.00% @ UV-A absorber according to formula (I) used as a 20% solution after neutralization with sodium hydroxide 20.00 corresponds to active substance: 4.00% @ 1,2-propylene glycol 2.00 C) water, dist. 25,00 Carbopol 940 0.40 Sodium hydroxide, 10% in water 2.05 D) perfume oil 0.30

Preparation Method

Part A: Melt at about 80 ° C.

Part B: Heat to about 90 ° C. Add part B with stirring to part A. On Stir room temperature.

Part C: Disperse Carbopol lump-free in water with sodium hydroxide. Neutralize solution to a gel at about 60 ° C to part A / B give.

Part D: Perfume the emulsion at approx. 30 ° C. Check the pH value (7,0- 7.5).

Example 8 Sunscreen cream (O / W)

Of the UV-A absorber according to formula (I), a 20% preliminary solution, neutralized with sodium hydroxide, prepared. Of this preliminary solution, 25% used, resulting in an active content of 5.00% UV-A absorber in the End formulation corresponds.

ingredients % A) Cutina FS 45 2.00 Eumulgin B 1 0.25 Eumulgin B2 0.25 Cutina MD 2.00 Lanette O 3.00 Myritol 318 5.00 Cetiol SN 3.00 Arosol 0.80 Solbrol P 0.10 p-methoxycinnamate 5.00 p-Methoxyzimtsäureisooctylester 3.00 4-methylbenzylidene-camphor 1.00 octyl salicylate 3.00 butylmethoxydibenzoylmethane 1.00 B) distilled water. 40,90 Carbopol 940 0.40 Sodium hydroxide, 10% in water 1.80 1,2-propylene glycol 2.00 Solbrol M 0.20 UV-A absorber according to formula (I) used as a 20% solution after neutralization with sodium hydroxide 25,00 Active substance: 5.00% @ C) perfume oil 0.30

Preparation Method

Part A: Melt at about 80 ° C.

Part B: Carbopol lump-free disperse in water, remaining constituents Add and heat to about 90 ° C. Then part B with stirring Give part A Stir to room temperature.

Part C: Perfume the emulsion at about 30 ° C. Check pH (7.0-7.5).

Example 9 Sunscreen milk (W / O)

The UV-A absorber according to formula (I) was a 30% preliminary solution, neutralized with triethanolamine, prepared. Of this preliminary solution, 6.7% used, giving an active content of 2.00% UV-A absorber in the End formulation corresponds.

ingredients % A) Lamiform TGI 4.00 Dehymuls HR E 7 4.00 Cetiol S 12,00 Paraffin oil 65 cp 8.50 Permulgin 3220 1.00 p-Methoxyzimtsäureisooctylester 5.00 p-methoxycinnamate 5.00 isopropyldibenzoylmethane 1.00 B) water, dist. 49.65 1,2-propylene glycol 2.00 triethanolamine 0.35 Phenonip 0.50 UV-A absorber, according to general formula (I), used as a 30% solution after neutralization with triethanolamine 6.70 corresponds to active substance: 2.00% @ C) perfume oil 0.30

Preparation Method

Part A: Melt at about 80 ° C.

Part B: Combine ingredients. Check the pH of the water phase (7.0-7.5). Heat to about 90 ° C. Slowly add Part B while stirring Give part A Stir to room temperature.

Part C: Perfume the emulsion at about 35 ° C, then homogenize Sieren.

Example 10 Sunscreen lotion (W / O)

The UV-A absorber according to formula (I) was a 30% preliminary solution, neutralized with triethanolamine, prepared. Of this preliminary solution, 20% used, resulting in an active content of 3.00% UV-A absorber in the End formulation corresponds.

ingredients % A) Elfacos E 200 3.00 Elfacos ST 9 1.00 Elfacos C 26 1.00 Paraffin oil 65 cp 6.00 Isopropyldiisostearat 7.00 p-Methoxyzimtsäureisooctylester 7.00 octyl salicylate 5.00 Tioveil MOTG, 40% dispersion 12.50 B) water, dist. 43,40 Trilon B fl. 0.30 Glycerin 86% 3.00 Phenonip 0.50 UV-A absorber according to formula (I), used as a 30% solution after neutralization with triethanolamine 10.00 corresponds to active substance: 3.00 @ C) perfume oil 0.30

Preparation Method

Part A: Melt at about 80 ° C and stir well.

Part B: Heat to about 90 ° C. Add part B with stirring to part A. On Stir room temperature.

Part C: Perfume at about 30 ° C, then homogenize.

Example 11 Sunscreen Cream (W / O)

The UV-A absorber according to formula (I) was a 30% preliminary solution, neutralized with triethanolamine, prepared. From this preliminary solution, 10% used, resulting in an active content of 3.00% UV-A absorber in the End formulation corresponds.

ingredients % A) Protegin WX 23.00 Alugel 30 DF 0.50 Paraffin oil 34 cp 3.00 Solbrol R 0.05 p-Methoxyzimtsäureisooctylester 5.00 octocrylene 7.00 menthyl 4.00 Eusolex 6007 4.00 B) water, dist. 37.30 Solbrol M 0.15 magnesium sulfate 0.40 Sorbitol 70% 5.00 UV-A absorber according to general formula (I), used as a 30% solution after neutralization with triethanolamine 10.00 corresponds to active substance: 3.00 @ C) perfume oil 0.30

Preparation Method

Part A: Dissolve alugel with heating in paraffin oil. The remaining Add ingredients and melt at about 80 ° C.

Part B: Heat to about 90 ° C. Add Part B with stirring to Part A and Stir to room temperature.

Part C: perfume the cream at about 30 ° C and then perfume homogenize.

Example 12 Sunscreen lotion (W / O)

The UV-A absorber according to formula (I) was a 30% preliminary solution, neutralized with triethanolamine, prepared. From this preliminary solution, 10% used, resulting in an active content of 3.00% UV-A absorber in the End formulation corresponds.

ingredients % A) Arlacel 581 3.50 Arlatone T 0.75 Cetiol S 12,00 Paraffin oil 34 cp 5.50 Permulgin 3220 1.00 p-Methoxyzimtsäureisooctylester 5.00 p-methoxycinnamate 5.00 Uvinul T 150 1.00   B) water, dist. 53,20 1,2-propylene glycol 2.00 triethanolamine 0.35 Phenonip 0.40 UV-A absorber according to formula (I), used as a 30% solution after neutralization with triethanolamine 10.00 corresponds to active substance: 3.00 @ C) perfume oil 0.30

Preparation Method

Part A: Melt at about 80 ° C.

Part B: Combine ingredients. Check the pH of the water phase (7.0-7.5). Heat to about 90 ° C. Slowly add Part B while stirring Give part A Stir to room temperature.

Part C: Perfume the emulsion at about 35 ° C, then homogenize Sieren.

Example 13 Lip protection cream (W / O)

The UV-A absorber according to formula (I) was a 30% preliminary solution, neutralized with triethanolamine, prepared. From this preliminary solution, 10% used, resulting in an active content of 3.00% UV-A absorber in the End formulation corresponds.

ingredients % A) Protegin WX 23.00 Alugel 30 DF 0.50 Paraffin oil 34 cp 5.00 Cetiol V 3.00 Solbrol P 0.05 p-Methoxyzimtsäureisooctylester 8.00 butylmethoxydibenzoylmethane 1.00 B) water, dist. 43.30 Solbrol M 0.15 magnesium sulfate 0.40 Sorbitol 70% 5.00 UV-A absorber according to formula (I), used as a 30% solution after neutralization with triethanolamine 10.00 corresponds to active substance: 3.00% @ C) perfume oil 0.30

Preparation Method

Part A: Dissolve alugel with heating in paraffin oil. The remaining Added ingredients and melt at about 80 ° C.

Part B: Heat to about 90 ° C. Add Part B with stirring to Part A and Stir to room temperature.

Part C: perfume the cream at about 30 ° C and then homogenize Sieren.

Example 14 Sunscreen hydrodispersion gel, emulsifier-free

The UV-A absorber according to formula (I) was a 30% preliminary solution, neutralized with triethanolamine, prepared. From this preliminary solution, 10% used, resulting in an active content of 3.00% UV-A absorber in the End formulation corresponds.

ingredients % A) water, dist. 75.00 Carbopol 1342 1.00 triethanolamine 1.20 B) UV-A absorber according to formula (I), used as a 30% solution after neutralization with triethanolamine 10.00 corresponds to active substance: 3.00  @ C) p-Methoxycinnamic acid isooctyl ester 3.00 p-methoxycinnamate 3.00 Neo Heliopan, type BB 1.00 isopropyl 3.00 Baysilon oil PK 20 2.00 Phenonip 0.50 perfume oil 0.30

Preparation Method

Part A: Carbopol lump-free in the water and dispersed with triethanol neutralize amine.

Part B: Introduce UV-A Absorber Solution in Part A.

Part C: Neo Heliopan, type BB in Heliopan, type AV and type E 1000 to solve. Add the remaining ingredients and part C with stirring to Part A / B. Homogenize (colloid mill) and check the pH (7.0-7.5).

Example 15 Sunscreen

The UV-A absorber according to formula (I) was a 30% preliminary solution, neutralized with triethanolamine, prepared. Of this preliminary solution, 13.3% used, resulting in an active content of 4.00% UV-A absorber in the End formulation corresponds.

ingredients % A) ethyl alcohol 5.00 Water, dist. 55,30 1,2-propylene glycol 5.00 D-panthenol 0.50 Carbopol ETD 2001 1.10 B) water 5.00 triethanolamine 2.30 C) Neo Heliopan, type Hydro, used as a 30% solution after neutralization with triethanolamine / phenylbenzimidazole sulfonic acid 10.00 corresponds to active substance: 3.00 @ UV-A absorber according to formula (I), used as a 30% solution after neutralization with triethanolamine 13,30 corresponds to active substance: 4.00 @ D) Cremophor NP 14 1.20 perfume oil 0.30

Preparation Method

Part A: Dissolve constituents in the water, disperse Carbopol without lumps.

Part B: Dissolve triethanolamine in water and part B with stirring to part A. give.

Part C: The sunscreen filter solutions with stirring to the gel part A / B give.

Part D: Mix perfume oil with Cremophor and stir in and pH check (7.0-7.5).

Example 16 Sunscreen spray, non-aerosol

The UV-A absorber according to formula (I) was a 30% preliminary solution, neutralized with triethanolamine, prepared. From this prelude were 23.35% used, resulting in an active content of 7.00% UV-A absorber in the End formulation corresponds.

ingredients % A) ethyl alcohol 30.00 perfume oil 0.10 B) water, dist. 39,80 Neo Heliopan, type Hydro, used as a 15% solution after neutralization with sodium hydroxide / phenylbenzimidazole sulfonic acid 6.75   corresponds to active substance: 1.00% @ UV-A absorber according to formula (I), used as a 30% solution after neutralization with triethanolamine 23.35 corresponds to active substance: 7.00%

Preparation Method

Part A: Dissolve the perfume oil in the alcohol.

Part B: Mix ingredients. Add part B to part A and mix.

Example 17 Hair shampoo with sunscreen

The UV-A absorber according to formula (I) was a 30% preliminary solution, neutralized with triethanolamine, prepared. Of this preliminary solution, 3.35% used, giving an active content of 1.00% UV-A absorber in the End formulation corresponds.

ingredients % A) Genapol LRO fl. 18,00 Texapon MG 3 36,00 Lamepon S. 6.00 p-methoxycinnamate 1.00 perfume oil 0.60   B) distilled water. 34,60 Euxyl K 100 0.15 UV absorber according to formula (I), used as a 30% solution after neutralization with triethanolamine 3.35 corresponds to active substance: 1.00% @ Sodium hydroxide, 10% in water 0.10 sodium chloride 0.20

Preparation Method

Part A: Mix ingredients.

Part B: Dissolve constituents in the water. Add part B with stirring to part A. Stir until homogeneous product is formed and pH check (7.0-7.5).

Example 18 Hair gel with sunscreen

The UV-A absorber according to formula (I) was a 30% preliminary solution, neutralized with triethanolamine, prepared. From this preliminary solution, 10% used, giving an active content of 3.00% UV-A absorber in the final form corresponds to lation.

ingredients % A) water, dist. 25,60 Glycerin 86% 26.00 Carbopol ETD 2001 1.50 B) distilled water. 3.00 triethanolamine 3.20 C) Neo Heliopan, type Hydro, used as a 30% solution after neutralization with triethanolamine / phenylbenzimidazole sulfonic acid 6.70 corresponds to active substance: 2.00% @ UV-A absorber according to formula (I), used as a 30% solution after neutralization with triethanolamine 10.00 corresponds to active substance: 3.00% @ Uvinul MS 40 1.50 Water, dist. 20.00 D) Mulsifan RT 203/80 1.20 perfume oil 0.30

Preparation Method

Part A: Dissolve ingredients in the water and Carbopol lump-free disperse.

Part B: Dissolve triethanolamine in the water. Part B with stirring to Part A give.

Part C: Mix ingredients and stir into Gel Part A / B give.

Part D: Mix the perfume oil with Mulsifan, stir in part A / B / C and mix Check pH value (7.0-7.5).

Example 19 Leave-on hair conditioner, transparent, with sunscreen

The UV-A absorber according to formula (I) was a 30% preliminary solution, neutralized with triethanolamine, prepared. Of this preliminary solution, 3.35% used, giving an active content of 1.00% UV-A absorber in the End formulation corresponds.

ingredients % A) water, dist. 81.50 Natrosol 250 HHR 0.70 ethyl alcohol 5.00 Uvinul P 25 5.00   UV-A absorber according to formula (I) used as a solution after neutralization with triethanolamine 3.35 corresponds to active substance: 1.00% @ B) Nutrilan L. 2.00 Dehyquart A 0.20 Phenonip 0.50 triethanolamine 0.25 C) Mulsifan RT 203/80 1.20 perfume oil 0.30

Preparation Method

Part A: Heat water to approx. 85 ° C. Sprinkle in Natrosol and under strong Stir to room temperature. Add remaining ingredients.

Part B: Weigh in part A and stir.

Part C: Mix Mulsifan with perfume oil, add to part A / B, stir well and check the pH (7.0-7.5).

Claims (9)

1. Use of compounds containing at least two per molecule Benzazolylgruppen, as UV absorbers in sunscreens. 2. Use according to claim 1, wherein the compounds of formula correspond, in which
Z represents an (I + n) -valent organic radical having one or more double bonds in such position as to complement the double bond systems of at least 2 of the square-cornered radicals to a total conjugated system, and
XS, preferably O, in particular NR⁶,
R¹ is hydrogen C₁-C₁₈-alkyl, C₁-C₄-alkoxy, C₅-C₁₅-aryl, C₂-C₁₈-acyloxy, SO₃Y or COOY,
R² to R⁵ independently of one another nitro or the meaning indicated under R¹,
R⁶ is hydrogen, C₁-C₄-alkyl or hydroxy-C₁-C₄-alkyl,
Y is hydrogen, Li, Na, K, NH₄, ½Ca, ½Mg, ¹ / ₃Al or the cation of an organic nitrogen base used to neutralize the free acid groups,
l is zero or an integer from 1 to 4,
m is zero or 1 and
n is an integer from 2 to 6
with the proviso that the sum l + n is a maximum of 6. 3. Use according to claim 2, wherein Z

• a) an olefinically unsaturated aliphatic C₂-C₆ hydrocarbon radical which may be interrupted by a C₅-C₁₂ arylene radical or a C₄-C₁₀ hetarylene radical,
• b) a C₅-C₁₅-arylene radical which may be interrupted by an olefinically unsaturated aliphatic C₂-C₆ hydrocarbon radical, or
• c) a C₃-C₁₀-hetarylene radical,

where the radicals indicated under a) to c) can be substituted by C₁-C₆-alkyl, C₁-C₆alkoxy, phenoxy, hydroxy, methylenedioxy groups or amino groups which may be substituted by 1 or 2 C₁-C₅-alkyl radicals,
means. 4. Use according to claim 2, wherein Z is selected from the group consisting of -CH = CH-, -CH = CH-CH = CH- or wherein R⁶ has the meaning given above,
is selected. 5. Compounds according to claims 1 to 4 with the proviso that the Compounds per molecule contain 1, 3 or 4 SO₃Y groups. 6. phenylene-1,4-bisbenzimidazole-3,3 ', 5,5'-tetrasulfonic acid and its salts. 7. Phenylene-1,4-bisbenzimidazole-3,5,5'-trisulfonic acid and its salts. 8. A process for the preparation of the compounds according to claim 5 by reacting compounds of the formula wherein
X and R¹ to R⁴ have the abovementioned meaning, but R¹ and R⁴ are neither COOY nor SO₃Y,
with a compound of the formula wherein
D is -OH, -NH₂, -Cl or O-C₁-C₃-alkyl,
in chlorosulfonic acid at temperatures of 20 to 190 ° C.