DE102008049955A1 - Titanium dioxide particles - Google Patents

Abstract

The present invention relates to hydrothermally treated titanium dioxide particles, aftertreated with a silica coating, wherein the content of SiO 2 in the coating 25 to 45 weight percent, based on the particles, and their preparation and use.

Description

The The present invention relates to titanium dioxide particles, their preparation and use.

The The present invention further relates to novel preparations for topical Application, in particular the self-tanning agent dihydroxyacetone in combination with the titanium dioxide particles according to the invention to protect the skin and / or hair against UV radiation.

Dihydroxyacetone (DHA) has been used as a self-tanning agent in cosmetics for many years. In recent years, the trend is also increasingly to combine self-tanning products with UV filters, for example, for day care. However, this has only been possible to a limited extent in the past, since DHA in combination with conventional inorganic UV filters, in particular TiO ₂ , shows a strong degradation during storage.

• – Abbau von DHA wenn dies in Formulierungen mit TiO₂ kombiniert wird
• – Farbreaktionen der TiO₂-Partikel mit DHA sowie mit weiteren organischen Molekülen in der Zubereitung
• – Vergrauung der Formulierungen bei UV-Bestrahlung.

Conventional micronized titanium dioxide particles are aftertreated to reduce the photocatalytic activity with inorganic oxides or hydroxides of the elements Al, Si, Zr, Ce and Fe. Particularly suitable here is the aftertreatment with Al ₂ O ₃ . In addition to the photo-catalytic activity, which leads to the degradation or destruction of the surrounding matrix when these products are used, further undesirable effects occur, in particular in cosmetic formulations:

• - Degradation of DHA when combined in formulations with TiO ₂
• - Color reactions of TiO ₂ particles with DHA and with other organic molecules in the preparation
• - Graying the formulations under UV irradiation.

Some of these effects, such as the graying or color reactions with, for example ascorbyl palmitate, can be reduced by various post-treatments of the titanium dioxide particles, for example, achieved by the qualities of the market products Parsol ^® TX DSM or UV Titan M263 by Kemira.

Parsol ^® TX is a white powder consisting of titanium dioxide of rutile crystal structure with a TiO ₂ content of 82.0 to 87.0 percent by weight, having an SiO ₂ coating with a SiO ₂ content of 5.10 to 5.14 weight percent and a dimethicone coating.

UV-TITAN M263 is a white powder consisting of titanium dioxide (88%) with an inorganic constituent of 7% of aluminum phosphate and an organic component of 3% of polyvinylpyrrolidone (INCI of the product: Titanium Dioxide, Alumina, Sodium Hexametaphosphate, Polyvinylpyrrolidone).

However, it has been found that even known conventional micronized titanium dioxide particles, as described above, which are provided with various post-treatments such as SiO ₂ and / or further aftertreatments, and these show good photocatalytic stability and / or low reactivities with other organic molecules, do not automatically compatible with dihydroxyacetone.

The The object of the invention is therefore to provide titanium dioxide particles as UV protectants containing dihydroxyacetone or dihydroxyacetone derivatives, especially with dihydroxyacetone, are compatible.

Now it was surprisingly found that it is possible certain titanium dioxide particles as UV protectants in cosmetic Use formulations containing dihydroxyacetone and thereby the degradation of the dihydroxyacetone in the cosmetic formulations compared to known titanium dioxide UV protectants to reduce or to prevent. Furthermore, it was found that these particular titanium dioxide particles also have the property of using color reactions of titanium dioxide To largely prevent organic compounds, the photocatalytic Activity and graying stability comparable remains to known titanium dioxide UV protectants.

The object is achieved by the coating of hydrothermally treated titanium dioxide particles with a SiO ₂ coating, wherein the content of SiO ₂ in the range of 25 to 45 weight percent, in particular 33 to 37 weight percent, most preferably 35 weight percent, based on the TiO ₂ content of the particles to be coated. It was not foreseeable for the skilled worker that focusing on a SiO ₂ content in the given ranges, the interaction of the titanium dioxide particles with dihydroxyacetone would be reduced so much. Further after-treatment with organic acids selected from the group consisting of stearic acid, lauric acid, caproic acid or palmitic acid, with polyols or with organosilicon compounds may likewise be advantageous.

A first subject of the present invention are therefore hydrothermally treated titanium dioxide particles, aftertreated with a silicon dioxide coating, wherein the content of SiO ₂ in the coating 25 to 45 weight percent, based on the TiO ₂ content of the particles to be coated. In particular, the content of SiO _{2 is} 33 to 37 percent by weight, very particularly preferably 35 percent by weight, based on the TiO ₂ content of the particles to be coated.

The product obtained is characterized by a water content of> 1.5 wt .-%. The water content can be determined, for example, by Karl Fischer titration as described in Eugen Scholz, Karl Fischer Titration, Springer-Verlag 1984 ,

The determination of the content of SiO ₂ is based on ICP-OES. The fluctuation range of the obtained values of the content of SiO ₂ is in the specified range of 25 to 45% by weight based on the titanium dioxide at plus / minus 0.25%.

ICP-OES stands for Inductively Coupled Plasma Optical Emission Spectrometry, ie inductively coupled plasma optical emission spectrometry. It is measured with the device Optima 3300DV from Perkin Elmer, with the method described in the experimental part of the description under the example SiO ₂ determination.

The Silica coating is said to be the titanium dioxide particles or with In other words, the particulate titanium dioxide, in particular the nanoparticulate titanium dioxide, as completely as possible cover.

The Titanium dioxide particles described have a primary particle size according to the Scherrer method in the range of 5 nm to 100 nm, preferably in the range 8 to 50 nm, and more preferably below 25 nm. Measurable in the transmission electron microscope dimensions of the nanoparticulate according to the invention Titanium dioxide is usually a length from 10 to 100 nm and a width of 5 to 70 nm. Preferably the length is in the range of 30 to 70 nm and the width in the range of 10 to 40 nm.

nanoparticles Within the meaning of the invention are particles whose three dimensions in Nanoscale present, d. H. <100 nm. These are the three dimensions of the primary particles.

Aggregate Within the meaning of the invention, an association of primary particles, by chemical or physical bonding, the external surface is significantly smaller than the sum of the calculated surfaces the individual particle, d. H. the primary particle. Aggregate within the meaning of the invention have dimensions of 30 nm to 150 nm.

agglomerates Within the meaning of the invention are an association of primary particles and / or aggregates, by chemical or physical bonding, the external surface is not significantly smaller is the sum of the calculated surfaces of the individual Particles, but the dimensions in areas between 0.1 microns and 100 microns are.

Of the Term titanium dioxide particle therefore includes both the primary particles, as well as aggregates or agglomerates. In the course of a grinding can the size of the mergers of the primary particles, to the desired size for the use can be adjusted in the respective application.

• a) Titandioxid-Partikel, d. h. sogenannte Titandioxid-Grundpartikel, hydrothermal behandelt werden,
• b) anschließend eine Siliciumdioxid-Beschichtung derart aufgebracht wird, dass der Gehalt SiO₂ in der Beschichtung 25 bis 45 Gewichtsprozent bezogen auf den TiO₂-Gehalt der zu beschichtenden Partikel beträgt und
• c) die Suspension getrocknet wird.

A process for producing the titanium dioxide particles according to the invention is characterized, for example, by the fact that

• a) titanium dioxide particles, ie so-called titanium dioxide base particles, are treated hydrothermally,
• b) then a silicon dioxide coating is applied such that the content of SiO ₂ in the coating 25 to 45 weight percent based on the TiO ₂ content of the particles to be coated, and
• c) the suspension is dried.

Hydrothermal treatment is the heating of an aqueous solution or suspension or dispersion in a closed container, optionally under pressure (cf. Ullmanns Enzyklopadie der Technischen Chemie, 4th Edition, 1978, Volume 15, p. 117 ff: K. Recker, Einkristallzüchtung ).

The hydrothermal treatment of the titanium dioxide base particles is preferably carried out at temperatures in the range of 40 to 360 ° C, preferably in the range of 80 to 220 ° C and particularly preferably in the range performed from 140 to 200 ° C.

By The Hydrothermalhehandlung it comes to the formation of stable nano-crystallites with uniform size and Shape. At low temperatures, "needle-shaped" crystallites are formed. As the temperature increases, the crystallites round. Make it up These are oval shapes that can reach up to round particles at very high temperatures walk. In addition, it comes to a uniform Crystal growth.

• – Ausbildung gleichmäßiger Kristallitgrößen mit enger Kornverteilung
• – Verhinderung von Sintereffekten (Bildung von unerwünschten Aggregaten).

Advantages of the hydrothermal treatment over a conventional thermal treatment (temperature treatment of a dried powder) are:

• - Formation of uniform crystallite sizes with narrow particle size distribution
• - Prevention of sintering effects (formation of undesirable aggregates).

Titanium dioxide may be in the form of rutile or anatase or in amorphous form, but preferably in the form of rutile and / or anatase. Preferred primary particle size of the titanium dioxide base particles is in the range of 5 to 50 nm. These are primary particles especially in anatase preferably round, while rutile primary particles often in needle or spindle shape up to ovals ("egg-shaped") occur. However, according to the invention also round rutile primary particles are used.

Titanium dioxide base particles can according to conventional methods, the expert are familiar, preferably wet-chemically produced.

The Silica coating in step b) may preferably be used as Sol-gel process to be performed, in particular preferably a water glass solution to a suspension of the Titanium dioxide is given.

there the sol-gel process is in an advantageous variant carried out at a constant pH. The constant maintained pH may be in a range of pH 2 to pH 11, wherein the pH preferably in the range of pH = 5 to pH = 8, particularly preferably in the range of pH = 6 to pH = 7.

A Another advantageous variant is the total addition of the aftertreatment necessary water glass at a pH = 7 to pH = 11 without constant pH. Subsequently, the pH is adjusted to a value of pH = 5 lowered to pH = 8, preferably to pH = 6 to pH = 7.

Further it is preferred if step b) at elevated temperature, preferably at a temperature in the range of 50 ° C to 110 ° C is performed.

at all mentioned variants of the specified method is a maturation period after completion of the coating advantageous. The maturing time should be between 1 h and 8 h, preferably 2 h to 4 h and at a temperature be carried out from 50 ° C to 110 ° C.

The from b) obtained directly for the preparation of preparations, containing the titanium dioxide particles according to the invention be used. However, the suspension can also be dried.

Further It may be beneficial in terms of later processing be when the product is subsequently ground. Here The usual nanoparticles can be used Grinding techniques are used.

• – UV-Absorption, insbesondere Breitband- bzw. UV-B-Absorption,
• – Transparenz im sichtbaren Licht (VIS),
• – gute, insbesondere erhöhte Photostabilität,
• – verringerte bzw. verhinderte Photoaktivität,
• – Silica-Oberfläche, die ggf. leicht, mit bekannten Techniken hydrophob modifiziert werden kann,
• – leichte Dispergierbarkeit in wässrigen und öligen Phasen,
• – in Kombinaton mit Dibenzoylmethan-Derivaten, insbesondere: – verringerte Verfärbung der Formulierung und/oder – nachlassende Verfärbung der Formulierung während der Lagerung und/oder – keine oder reduzierte Auskristallisation von Komplexen der Dibenzoylmethan-Derivate und/oder – erhöhte Lagerstabilität der Dibenzoylmethan-Derivate und/oder – verbesserte Lichtschutzwirkung, insbesondere nach Lagerung,
• – in Kombination mit Benzophenon-Derivaten, insbesondere 2-Hydroxy-4-Methoxy-Benzophenon, wird eine Stabilisierung der Benzophenon-Derivate beobachtet.

The nanoparticulate titanium dioxide according to the invention likewise has the advantageous properties of the comparison products from the prior art with regard to:

• UV absorption, in particular broadband or UV-B absorption,
• - transparency in visible light (VIS),
• Good, in particular increased photostability,
• Reduced or prevented photoactivity,
• - Silica surface, which may be easily modified hydrophobically with known techniques,
• Easy dispersibility in aqueous and oily phases,
• In combination with dibenzoylmethane derivatives, in particular: reduced coloration of the formulation and / or decreasing coloration of the formulation during storage and / or no or reduced crystallization of complexes of the dibenzoylmethane derivatives and / or increased storage stability of the dibenzoylmethane derivatives and or Improved light protection, especially after storage,
• - In combination with benzophenone derivatives, in particular 2-hydroxy-4-methoxy-benzophenone, stabilization of the benzophenone derivatives is observed.

The nanoparticulate titanium dioxide according to the invention according to claim 1, however, now shows in combination with Dihydoxyaceton a significantly reduced degradation of the DHA after Storage compared to conventional, previously known, titanium dioxide UV protection agents, d. H. it will be a reduced over the prior art significant destabilization of the self-tanner observed. It is therefore referred to as DHA compatible for the purposes of this invention. Furthermore, it has been shown that in combination with DHA no or only a minimal discoloration of the preparation after preparation and after 3 months storage at 40 ° C occurs.

there In particular, it has been shown to be simultaneous realization The above advantages may be advantageous if the nanoparticulate Titanium dioxide is doped with iron.

In a further embodiment of the invention, the nanoparticulate titanium dioxide, as described above, can be further modified by applying, in addition to the SiO ₂ coating, a further coating containing organic acids selected from the group of stearic acid, lauric acid, caproic acid or palmitic acid, polyols or organosilicon compounds.

Examples for polyols are glycerol, sorbitol, propylene glycol, pentanediol, Hexanediol, ethylhexyl glycerol, pentaerythritol, dipentaerythritol or trimethylolpropane.

silicone Organic Compounds are, for example, silicone oils, in the following also referred to as silicones, or alkyl silanes.

The Silicones are known to be organosilicon polymers or oligomers with straight-chain or cyclic, branched or crosslinked structure with different molecular weights, by polymerization and / or polycondensation of suitably functionalized silanes are formed essentially of recurring main units be in which the silicon atoms via oxygen atoms linked together (siloxane bond), where appropriate substituted hydrocarbon groups via a carbon atom are bonded directly to the silicon atoms. The most bawling Hydrocarbon groups are the alkyl groups and especially methyl, the fluoroalkyl groups, the aryl groups and especially phenyl and the alkenyl groups and especially vinyl. Other types of groups, either directly or via a hydrocarbon group can be bound to the siloxane, are in particular Hydrogen, the halogens and in particular chlorine, bromine or fluorine, the thiols, the alkoxy groups, the polyoxyalkylene groups (or polyethers) and in particular polyoxyethylene and / or polyoxypropylene, hydroxy groups or hydroxyalkyl groups, the optionally substituted amino groups, the amide groups, the acyloxy groups or acyloxyalkyl groups, the Hydroxyalkylamino groups or aminoalkyl groups, quaternary ammonium groups, amphoteric groups or betaine groups, anionic groups such as carboxylates, Thioglycolates, sulfosuccinates, thiosulfates, phosphates and sulfates, Of course, in no way Is restrictive (so-called 'organomodified' Silicone).

The organosilicon compounds suitable for the present invention for coating the nanoparticulate titanium dioxide coated with SiO ₂ as described above are preferably selected from alkylsilanes or silicone oils, for example octyltrimethylsilane, methicone, dimethicone or simethicone. Very particular preference is aftertreatment with simethicone. The outer coating is at least 0.25 weight percent of the compound used for the outer secondary coating, preferably from 0.5 wt .-% to 50 wt .-%, particularly preferably from 0.5 wt .-% to 15 wt .-%, based on the TiO ₂ Content of the particles to be coated.

The additional after-treatment reinforces the already described advantages of the particles according to the invention, especially the DHA compatibility.

Further preferred combinations of embodiments are in disclosed in the claims.

by virtue of The above advantages is another object of the present invention Invention, a preparation containing the inventive Titanium dioxide particles as described above.

in the The meaning of the present invention is in addition to the term preparation synonymous, the term mean or formulation used.

All Compounds or components used in the preparations can be either known or for sale Acquired or can be synthesized by known methods become.

at the preparations are in a variant of the invention to aqueous or oily dispersions. Preferred oils For example, natural oils such as sunflower oil; or the oils known for use in cosmetics such as isononyl isononanoate; Isopropyl palmitate, propylheptyl caprylate; Dicaprylyl carbonate, butylene glycol dicaprylate / dicaprate, isopropyl lauroyl sarcosinate, C12-15 alkyl benzoate (for example Tegosoft TN from Evonik), Capric / Caprylic triglyceride, Cyclopentasiloxanes or cyclohexasiloxanes.

at the preparations are preferably in a variant of the invention Topically applicable preparations, for example cosmetic or dermatological formulations. The preparations contain in this case a cosmetically or dermatologically suitable carrier and depending on the desired property profile optionally further suitable ingredients.

Further according to the invention are preferred preparations from the group fibers, textiles, including theirs Coatings, paints, coating systems, films and Packaging for the protection of food, plants or technical goods.

used can be nanoparticulate according to the invention Titanium dioxide, as described above, for incorporation into paints, Coating systems, films, packaging, fibers, textiles and Molded parts of rubber or silicone rubber, such as tires or insulators.

Next the advantages already mentioned above, the use of the invention Titanium dioxide particles in preparations which are emulsions, in particular also contribute to the stabilization of the emulsion. This can be done in usually the use of emulsifiers can be reduced or im Isolated case (Pickering emulsion), even entirely on the use of Emulsifiers are dispensed with. According to the invention are preferred therefore also emulsifier-free emulsions, which are the inventive contain nanoparticulate titanium dioxide.

The Titanium dioxide particles according to the invention can in the inventive preparations in proportions which are generally in the range from 0.1% by weight to 50% by weight. and preferably in proportions in the range of 0.5 Wt .-% to 20 wt .-% are, these proportions on the total weight the preparation are related.

1,3-Dihydroxyaceton (DHA) Preferred formulations contain dihydroxyacetone or a dihydroxyacetone derivative, most preferably dihydroxyacetone.

1,3-dihydroxyacetone (DHA)

The Concentration of DHA in the preparation is in the range of 1 to 12 weight percent, preferably 1.5 weight percent to 7.5 weight percent, particularly preferably at 2 wt .-% to 5 wt .-%, based on the preparation.

• a) <= 0,5:1 → nicht größer ist, als max. 50% (bevorzugt 25%) im Bezug auf den DHA-Abbau gleichen Formulierung ohne Zusatz von TiO₂.
• b) 0,5:1 → oder absolute DHA-Abbau bezogen auf die DHA Einsatzkonzentration <= 20% (bevorzugt <= 15%) ist.
• c) 1:1 → oder absolute DHA-Abbau bezogen auf die DHA Einsatzkonzentration <= 40% (bevorzugt <= 30%, besonders bevorzugt <= 20%) ist. > 1:2 → der absolute DHA-Abbau bezogen auf die DHA Einsatzkonzentration <= 50% (bevorzugt <= 40%, besonders bevorzugt <= 30%) ist.

These formulations are characterized in that the degradation of the DHA after storage for 3 months at 40 ° C in the dark at a use ratio of inventive TiO ₂ : DHA (wt .-%) of

• a) <= 0.5: 1 → is not greater than max. 50% (preferably 25%) in terms of DHA degradation same formulation without addition of TiO ₂ .
• b) 0.5: 1 → or absolute DHA degradation based on the DHA use concentration <= 20% (preferably <= 15%).
• c) 1: 1 → or absolute DHA degradation based on the DHA use concentration <= 40% (preferably <= 30%, particularly preferably <= 20%). > 1: 2 → the absolute DHA degradation based on the DHA use concentration <= 50% (preferably <= 40%, particularly preferably <= 30%).

In another embodiment of the present invention the preparation according to the invention in addition to dihydroxyacetone contain at least one more self-tanner.

Advantageous self-tanner may be used, inter alia:

5-Hydroxy-1,4-naphtochinon (Juglon) sowie das in den Henna-Blättern vorkommende 2-Hydroxy-1,4-naphtochinon (Lawson).Further, 5-hydroxy-1,4-naphthoquinone (juglone), which is extracted from the shells of fresh walnuts

5-hydroxy-1,4-naphthoquinone (juglone) and the 2-hydroxy-1,4-naphthoquinone (Lawson) found in henna leaves.

2-Hydroxy-1,4-naphtochinon (Lawson)

2-Hydroxy-1,4-naphthoquinone (Lawson)

The preparations according to the invention containing dihydroxyacetone, when applied to human skin, are prone to malodors, presumably due to degradation products of the dihydroxyacetone caused by side reactions themselves and by the products and which are perceived by the users as partly unpleasant. It has been found that these off-odors are avoided when using formaldehyde scavengers and / or flavonoids. Even with combined use with other self-tanner, as described above, the formation of off-odors can not be excluded. Therefore, the preparation according to the invention may preferably also contain formaldehyde scavengers and optionally flavonoids for improving the odor.

Preferably the formaldehyde scavenger is selected from Group of alkali metal, alkaline earth metal or ammonium bisulfite. Especially preferred is a preparation containing in combination DHA Plus, a Mixture of DHA, sodium bisulfite and magnesium stearate.

DHA Plus is a product blend containing sodium bisulfite, equivalent to Na ₂ S ₂ O ₅ or INCI: sodium disulfite, for the masking, elimination or neutralization of formaldehyde. The addition of sodium bisulfite in finished formulations significantly reduces or eliminates the unpleasant odor. DHA Plus is distributed by Merck, Darmstadt.

The optionally in the preparation according to the invention existing flavonoid acts additionally as a stabilizer for the self-tanner or self-tanning substances and / or reduces or avoids or improves warehouse-dependent False odors, which also contain added or auxiliary substances can arise.

Preferably it is a flavonoid in which one or more phenolic Hydroxy groups are blocked by etherification or esterification. For example, hydroxyethyl-substituted flavonoids, such as preferably troxerutin, troxequercetin, troxeisoquercetin or Troxeluteolin, and flavonoid-sulfate or flavonoid-phosphate, such as preferably rutinsulfates, as a particularly suitable flavonoids proved. Particularly preferred in the sense of the invention Uses are rutin sulfate and troxerutin. Very particularly preferred is the use of troxerutin.

The preferred flavonoids have a non-positively charged Flavangrundkörper. It is believed that by these flavonoids metal ions such. B. Fe ^{2 +} / Cu ^{2+ be} complexed and so auto-oxidation processes in fragrances or compounds whose degradation leads to malodors, prevented or reduced.

Especially preferred is a preparation containing DHA Rapid and / or sodium bisulfite contain. DHA Rapid is a product mixture containing dihydroxyacetone and Troxerutin, Merck, Darmstadt.

Corresponding premixes and preparations which contain formaldehyde scavengers and, if appropriate, flavonoids for improving the odor on the skin are described in the German patent application with the registration file DE 10 2007 013 368.7 whose content in this regard expressly also belongs to the disclosure content of the present application.

• – Vegetan Premium (INCI Dihydroxyacetone/Melanin) von Soliance,
• – MelanoBronze (INCI: Vitex agnus castus extract (and) acetyl tyrosine (and) glycerin (and) alcohol (and) water (aqua)) Mibelle AG Biochemistry.
• – Instabronze^® (INCI Dihydroxyaceton (DHA), N-acetyl tyrosine), Alban-Müller,
• – Substanzen welche penetrationsfördernd wirken, wie z. B. Leerliposome, Propylenglykol, Isohexadecan (Arlamol HD; Croda), Dimethylisosorbid (Arlasolve DMI; CRODA), Trimethylpentanediol/Adipic Acid/Isononanoic Acid Copolymer (INCI-Bezeichnung) oder (Lexorez TC-8, Index).

Furthermore, the titanium dioxides according to the invention can also be used with the following substances alone or in combination with DHA for tanning intensification:

• - Vegetan Premium (INCI Dihydroxyacetone / Melanin) from Soliance,
• - MelanoBronze (INCI: Vitex agnus castus extract (and) acetyl tyrosine (and) glycerol (and) alcohol (and) water (aqua)) Mibelle AG Biochemistry.
• - Instabronze ^® (INCI dihydroxyacetone (DHA), N-acetyl tyrosine), Alban Muller,
• - substances which promote penetration, such. Eg, empty liposomes, propylene glycol, isohexadecane (Arlamol HD, Croda), dimethylisosorbide (Arlasolve DMI, CRODA), trimethylpentanediol / adipic acid / isononanoic acid copolymer (INCI name), or (Lexorez TC-8, Index).

The Use of the nanoparticulate according to the invention Titanium dioxide for the stabilization of dihydroxyacetone or Dihydroxyacetonderivaten, in particular of dihydroxyacetone, is another object of present invention.

Further are also combinations of the invention Titanium dioxide particles with further particulate UV filters, both as a powder and as a dispersion or paste, the following Types possible.

In this case, both those from the group of titanium dioxides such. For example, coated titanium dioxide (for. Example Eusolex ^® T-2000, Eusolex ^® T-AQUA, Eusolex ^® T-AVO, Eusolex ^® T-OLEG), zinc oxides (eg. As Sachtotec® ^®), Eisenoxi de or else cerium oxides and / or zirconium oxides are preferred.

Furthermore, combinations with pigmentary Titandixoxid or zinc oxide are possible, wherein the particle size of these pigments is greater than or equal to 200 nm, for example COS Hombitec ^®.

Furthermore, it may be preferred according to the invention if the preparations contain inorganic UV filters which are prepared by customary methods, such as, for example, in US Pat Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53-64 described, were treated. Here, one or more of the following aftertreatment components may be selected: amino acids, beeswax, fatty acids, fatty acid alcohols, anionic surfactants, lecithin, phospholipids, sodium, potassium, zinc, iron or aluminum salts of fatty acids, polyethylenes, silicones, proteins (especially Collagen or elastin), alkanolamines, silica, alumina, other metal oxides, phosphates, such as sodium hexametaphosphate or glycerol.

• – unbehandelte Titandioxide wie z. B. die Produkte Microtitanium Dioxide MT 500 B der Fa. Tayca; Titandioxd P25 der Fa. Degussa,
• – Nachbehandelte mikronisierte Titandioxide mit Aluminiumoxid und Siliciumdioxid Nachbehandlung wie z. B. das Produkt „Microtitanium Dioxide MT 100 SA der Tayca; oder das Produkt „Tioveil Fin” der Fa. Uniqema,
• – Nachbehandelte mikronisierte Titandioxide mit Aluminiumoxid und/oder Aluminiumstearate/laurate Nachbehandlung wie z. B. Microtitanium Dioxide MT 100 T der Fa. Tayca, Eusolex T-2000 der Firma Merck,
• – Nachbehandelte mikronisierte Titandioxide mit Eisenoxid und/oder Eisenstearate Nachbehandlung wie z. B. das Produkt „Microtitanium Dioxide MT 100 F” der Fa. Tayca,
• – Nachbehandelte mikronisierte Titandioxide mit Siliciumdioxide, Aluminiumoxid und Silicon Nachbehandlung wie z. B. das Produkt ”Microtitanium Dioxide MT 100 SAS”, der Fa. Tayca,
• – Nachbehandelte mikronisierte Titandioxide mit Natrumhexametaphosphate, wie z. B. das Produkt ”Microtitanium Dioxide MT 150 W” der Fa. Tayca.

Preferably used further particulate UV filters are:

• - untreated titanium dioxides such. The products Microtitanium Dioxide MT 500 B from Tayca; Titanium Dioxide P25 from Degussa,
• Aftertreated micronised titanium dioxides with alumina and silica aftertreatment such. For example, the product "Microtitanium Dioxide MT 100 SA from Tayca; or the product "Tioveil Fin" from Uniqema,
• - Aftertreated micronized titanium dioxides with alumina and / or aluminum stearates / laurate aftertreatment such. B. Microtitanium Dioxide MT 100 T from. Tayca, Eusolex T-2000 from Merck,
• - Aftertreated micronized titanium dioxides with iron oxide and / or iron stearates aftertreatment such. B. the product "Microtitanium Dioxide MT 100 F" Fa. Tayca,
• - Aftertreated micronized titanium dioxides with silicas, alumina and silicon aftertreatment such. B. the product "Microtitanium Dioxide MT 100 SAS", the company Tayca,
• - Aftertreated micronized titanium dioxides with Natrumhexametaphosphate, such as. As the product "Microtitanium Dioxide MT 150 W" Fa. Tayca.

• – Octyltrimethoxysilane; wie z. B. das Produkt Tego Sun T 805 der Fa. Degussa,
• – Siliciumdioxid; wie z. B. das Produkt Parsol T-X der Fa. DSM,
• – Aluminiumoxid und Stearinsäure; wie z. B. das Produkt UV-Titan M160 der Fa. Kemira,
• – Aluminium und Glycerin; wie z. B. das Produkt UV-Titan der Fa. Kemira,
• – Aluminium und Silikonölen, wie z. B. das Produkt UV-Titan M262 der Fa. Kemira,
• – Natriumhexamethaphosphat und Polyvinylpyrrolidon,
• – Polydimethylsiloxane, wie z. B. das Produkt 70250 Cardre UF TiO2SI3” der Fa. Cardre,
• – Polydimethylhydrogensiloxane, wie z. B. das Produkt Microtitanium Dioxide USP Grade Hydrophobic” der Fa. Color Techniques.

The treated micronized titanium dioxides used for combination may also be post-treated with:

• - octyltrimethoxysilanes; such as B. the product Tego Sun T 805 from Degussa,
• - silica; such as B. the product Parsol TX from DSM,
• Alumina and stearic acid; such as B. the product UV titanium M160 Fa. Kemira,
• - aluminum and glycerin; such as B. the product UV titanium from. Kemira,
• - Aluminum and silicone oils, such as. B. the product UV titanium M262 Fa. Kemira,
• Sodium hexamethaphosphate and polyvinylpyrrolidone,
• - Polydimethylsiloxane, such as. Example, the product 70250 Cardre UF TiO2SI3 "the Fa. Cardre,
• - Polydimethylhydrogensiloxane, such as. Example, the product Microtitanium Dioxide USP Grade Hydrophobic "from the company Color Techniques.

• – Unbehandelte Zinkoxide wie z. B. das Produkt Z-Cote der Fa. BASF (Sunsmart), Nanox der Fa. Elementis
• – Nachbehandelte Zinkoxide wie z. B die folgenden Produkte: – ”Zinc Oxide CS-5” der Fa. Toshibi (ZnO nachbehandelt mit polymethylhydrogenosiloxane) – Nanogard Zinc Oxide FN der Fa. Nanophase Technologies – ”SPD-Z1” der Fa Shin-Etsu (ZnO nachbehandelt mit einem Silikongepfropften Acrylpolymer, dispergiert in Cyclodimethylsiloxane – ”Escalol Z100” der Fa ISP (Aluminiumoxid nachbehandeltes ZnO dispergiert in einer ethylhexyl methoxycinnamate/PVP-hexadecene/methicone copolymer Mischung) – ”Fuji ZNO-SMS-10” der Fa. Fuji Pigment (ZnO nachbehandelt mit Siliciumdioxid und Polymethylsilesquioxan); – Unbehandeltes Ceroxide Mikropigment z. B. mit der Bezeichnung ”Colloidal Cerium Oxide” der Fa Rhone Poulenc – Unbehandelte und/oder nachbehandelte Eisenoxide mit der Bezeichnung Nanogar der Fa. Arnaud.

Furthermore, the combination with the following products may also be advantageous:

• - Untreated zinc oxides such. For example, the product Z-Cote from BASF (Sunsmart), Nanox from the company Elementis
• - After-treated zinc oxides such. B the following products: - "Zinc Oxide CS-5" from Toshibi (ZnO aftertreated with polymethylhydrogenosiloxanes) - Nanogard Zinc Oxide FN from Nanophase Technologies - "SPD-Z1" from Shin-Etsu (ZnO aftertreated with a silicone grafted Acrylic polymer dispersed in cyclodimethylsiloxanes - "Escalol Z100" from ISP (alumina aftertreated ZnO dispersed in an ethylhexyl methoxycinnamate / PVP-hexadecenes / methicone copolymer blend) - "Fuji ZNO-SMS-10" from Fuji Pigment (ZnO aftertreated with silica and polymethylsilsquioxane), - Untreated cerium oxide micropigment, for example with the name "Colloidal Cerium Oxide" from Rhone Poulenc - Untreated and / or post-treated iron oxides with the name Nanogar from Arnaud.

exemplary can also mixtures of various metal oxides, such as. As titanium dioxide and cerium oxide with and without Nachbenhandlung used be such. As the product Sunveil A Fa. Ikeda. Furthermore may also be mixtures of alumina, silica and silicone post-treated titanium dioxide. Zinc oxide blends like z. B. the product UV titanium M261 Fa. Kemira in combination with used the UV-protecting agent according to the invention become.

These Inorganic UV filters are usually in an amount of 0.1 Percent by weight to 25 percent by weight, preferably 2 percent by weight - 10 Wt .-%, incorporated into cosmetic preparations. Especially It may be preferred when in emulsions in one phase a nanoparticulate according to the invention Titanium dioxide and in the other phase another inorganic UV filter is included.

worin R¹, R², R³ und R⁴, die identisch oder voneinander verschieden sind, Wasserstoff, eine geradkettige oder verzweigte C_1-8-Alkylgruppe oder eine geradkettige oder verzweigte C_{1- 8}-Alkoxygruppe bedeuten. Gemäß der vorliegenden Erfindung können selbstverständlich ein Dibenzoylmethanderivat oder mehrere Dibenzoylmethanderivate verwendet werden. Von den Dibenzoylmethanderivaten, auf die sich die vorliegende Erfindung spezieller bezieht, können insbesondere:

• – 2-Methyldibenzoylmethan,
• – 4-Methyldibenzoylmethan,
• – 4-Isopropyldigenzoylmethan,
• – 4-tert.-Butyldibenzoylmethan,
• – 2,4-Dimethyldibenzoylmethan,
• – 2,5-Dimethyldibenzoylmethan,
• – 4,4'-Diisopropyldibenzoylmethan,
• – 4,4'-Methoxy-tert.-butyldibenzoylmethan,
• – 2-Methyl-5-isopropyl-4'-methoxydibenzoylmethan,
• – 2-Methyl-5-tert.-butyl-4'-methoxydibenzoylmethan,
• – 2,4-Dimethyl-4'-methoxydibenzoylmethan und
• – 2,6-Dimethyl-4-tert.-butyl-4'-methoxydibenzoylmethan

genannt werden, wobei diese Aufzählung nicht einschränkend ist.Preferred preparations, in particular having light-protection properties, contain at least one further UV filter, in particular a dibenzoylmethane derivative. The dibenzoylmethane derivatives used in the context of the present invention are already well-known products, in particular in the abovementioned publications FR-A-2 326 405 . FR-A-2 440 933 and EP-A-0 114 607 are described. The dibenzoylmethane derivatives which can be used according to the invention can be chosen in particular from the dibenzoylmethane derivatives of the following formula:

wherein R ^1, R ^2, R ³ and R ^4, which are identical or different, represent hydrogen, a linear or branched C _1-8 alkyl group or a linear or branched C _{1- 8} alkoxy group mean. Of course, according to the present invention, a dibenzoylmethane derivative or a plurality of dibenzoylmethane derivatives may be used. Of the dibenzoylmethane derivatives to which the present invention more specifically relates, in particular:

• 2-methyldibenzoylmethane,
• 4-methyldibenzoylmethane,
• 4-isopropyldigenoylmethane,
• 4-tert-butyldibenzoylmethane,
• 2,4-dimethyldibenzoylmethane,
• 2,5-dimethyldibenzoylmethane,
• 4,4'-diisopropyldibenzoylmethane,
• 4,4'-methoxy-tert-butyldibenzoylmethane,
• 2-methyl-5-isopropyl-4'-methoxydibenzoylmethane,
• 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane,
• 2,4-dimethyl-4'-methoxydibenzoylmethane and
• - 2,6-dimethyl-4-tert-butyl-4'-methoxydibenzoylmethane

be mentioned, this list is not limiting.

Of the above dibenzoylmethane derivatives according to the invention, in particular the 4,4'-methoxy-t-butyldibenzoylmethane, and in particular the left under the trade name Eusolex ^® 9020 from Merck commercially 4,4'-methoxy-t-butyldibenzoylmethane, said Filter corresponds to the following structural formula:

One Another preferred dibenzoylmethane derivative is 4-isopropyldibenzoylmethane.

Further preferred compositions having further organic UV filters contain at least one benzophenone or benzophenone derivative, such as especially preferably 2-hydroxy-4-methoxybenzophenone (z. B. Eusolex ^® 4360) or 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (eg. as Uvinul ^® MS-40).

The or the dibenzoylmethane derivative (s) or the benzophenone derivative (s) can in the preparations according to the invention in proportions generally in the range of 0.1 Wt .-% to 10 wt .-% (weight percent) are and preferably in Proportions ranging from 0.3% to 5% by weight, these proportions being based on the total weight of the preparation are related.

The preparations according to the invention may of course contain one or more additional hydrophilic or lipophilic sunscreen filters which are in the UV-A range and / or UV-B range and / or IR and / or VIS range (absorber ) are effective. These additional filters can be used in particular under cinnamic acid derivatives, salicylic acid derivatives, camphor derivatives, triazine derivatives, β, β-diphenylacrylate derivatives, p-aminobenzoic acid derivatives, as well as polymeric filters and silicone filters described in the application WO-93/04665 be selected. Further examples of organic filters are in the patent application EP-A 0 487 404 specified. In the following, the named UV filters are usually named according to the INCI nomenclature.

• – para-Aminobenzoesäure und deren Derivate: PABA, Ethyl PABA, Ethyl dihydroxypropyl PABA, Ethylhexyl dimethyl PABA, z. B. vetrieben unter dem Namen ”Escalol 507” von der Fa. ISP, Glyceryl PABA, PEG-25 PABA, z. B. vetrieben unter dem Namen ”Uvinul P25” von der Fa. BASF.

In particular, here are:

• Para-aminobenzoic acid and its derivatives: PABA, ethyl PABA, ethyl dihydroxypropyl PABA, ethylhexyl dimethyl PABA, e.g. B. under the name "Escalol 507" from the company. ISP, glyceryl PABA, PEG-25 PABA, z. B. under the name "Uvinul P25" from BASF.

salicylates: Homosalate was sold under the name "Eusolex HMS" by the company Merck; Ethyl hexyl salicylates, e.g. B. operated under the Name "Neo Heliopan OS" from the company Haarmann and Reimer, dipropylene glycol salicylate, e.g. B. operated under the Name "Dipsal" from the company Scher, TEA salicylate, z. B. operated under the name "Neo Heliopan TS" of the company Haarmann and Reimer.

β, β-diphenylacrylates Derivatives: octocrylenes, e.g. B. operated under the name "Uvinul N539 "from BASF, Etocrylene, z. B. powered down the name "Uvinul N35" from BASF.

benzophenones Derivatives: Benzophenone-1, e.g. B. operated under the name "Uvinul 400 "; Benzophenone-2, e.g. B. operated under the name "Uvinul D50 "; Benzophenone-3 or oxybenzone, e.g. B. powered down the name "Uvinul M40"; Benzophenone-4, e.g. B. operated under the name "Uvinul MS40"; Benzophenone-9, z. B. operated under the name "Uvinul DS-49" of Fa. BASF, Benzophenone-5, Benzophenone-6, z. B. powered down the name "Helisorb 11" from Norquay, Benzophenone-8, z. B. sold under the name "Spectra-Sorb UV-24" of from American Cyanamid, benzophenone-12 n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate.

benzylidenecamphor Derivatives: 3-benzylidenecamphor, e.g. B. operated under the name "Mexoryl SD "from Chimex, 4-methylbenzylidenecamphor, e.g. B. operated under the name "Eusolex 6300" of Fa. Merck, Benzylidenecamphorsulfonsäure, z. B. vetrieben under the name "Mexoryl SL" from the company Chimex, Camphor benzalkonium methosulfate, z. B. operated under the name "Mexoryl SO "from Chimex, terephthalylidenedicamphorsulfonic acid, z. B. sold under the name "Mexoryl SX" of Chimex, Polyacrylamidomethylbenzylidenecamphor under the name "Mexoryl SW" from the company Chimex.

phenylbenzimidazole Derivatives: phenylbenzimidazolesulfonic acid, e.g. B. vetrieben under the name "Eusolex 232" from the company Merck, Disodium phenyl dibenzimidazole tetrasulfonate, e.g. B. vetrieben under the name "Neo Heliopan AP" from the Fa. Haarmann and Reimer.

phenylbenzotriazole Derivatives: Drometrizole trisiloxanes, e.g. B. operated under the name "Silatrizole" of Fa. Rhodia Chimie, Methylenebis (benzotriazolyl) tetramethylbutylphenol in solid form, e.g. B. operated under the name "MIXXIM BB / 100 "from the company Fairmount Chemical, or in micronized Form as aqueous dispersion, eg. B. operated under the Name "Tinosorb M" from the company Ciba Specialty Chemicals.

triazines Derivatives: ethylhexyltriazone, e.g. B. operated under the name "Uvinul T150 "from BASF, Diethylhexylbutamidotriazone, z. B. operated under the name "Uvasorb HEB" of from the company Sigma 3V, 2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazines.

Anthranilin Derivatives: menthyl anthranilate, e.g. B. operated under the name "Neo Heliopan MA "from Haarmann and Reimer.

imidazole Derivatives: Ethylhexyldimethoxybenzylidenedioxoimidazoline propionate.

benzalmalonate Derivatives: polyorganosiloxanes containing functional benzalmalonates Groups, such as B. polysilicone-15, z. B. operated under the name "Parsol SLX "from the Hoffmann LaRoche.

4,4-diarylbutadiene Derivatives: 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene.

benzoxazoles Derivatives: 2,4-bis [5- (1-dimethylpropyl) benzoxazol-2-yl (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazines, z. B. under the name Uvasorb K2A from the company Sigma 3 V and mixtures containing this.

Piperazine derivatives such as the compound

The Listed compounds are only examples specific. Of course, others can UV filters are used.

In particular, advantageous organic particulate UV filters, as you for example in the patent application WO 99/66896 are combined with the inventive particulate titanium dioxide particles.

The for combination with the UV protection agent according to the invention suitable organic UV-protective substances are preferred from the following list: Ethylhexyl salicylate, Octocrylene, butylmethoxydibenzoylmethane, phenylbenzimidazolesulfonic acid, benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate, 4-methylbenzylidenecamphor, terephthalylidenedicamphorsulphonic acid, Disodium phenyldibenzimidazoletetrasulfonate, methylenebis (benzotriazolyl) tetramethylbutylphenol, Ethylhexyl triazone, diethylhexyl butamido triazone, drometrizole trisiloxanes, polysilicones-15, 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadienes, 2,4-Bis [5-1 (dimethylpropyl) benzoxazol-2-yl (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazines and mixtures thereof.

These Organic UV filters are usually in an amount of 0.01 Weight percent to 20 weight percent, preferably 1 wt .-% - 10 Wt .-%, incorporated in formulations.

organic Overall, UV filters are generally in an amount of 0.01 Weight percent to 20 weight percent, preferably 0.5 weight percent to 20 wt .-%, incorporated in formulations.

wobei R¹ und R² ausgewählt sind aus

• – H
• – und OR¹¹, wobei OR¹¹ unabhängig voneinander steht für – OH – geradkettige oder verzweigte C₁- bis C₂₀-Alkyloxygruppen, – geradkettigen oder verzweigten C₃- bis C₂₀-Alkenyloxygruppen, – geradkettigen oder verzweigten C₁- bis C₂₀-Hydroxyalkoxygruppen, wobei die Hydroxygruppe(n) an ein primäre oder sekundäre Kohlenstoffatome der Kette gebunden sein können und weiter die Alkylkette auch durch Sauerstoff unterbrochen sein kann, und/oder – C₃- bis C₁₀-Cycloalkyloxygruppen und/oder C₃- bis C₁₂-Cycloalkenyloxygruppen, wobei die Ringe jeweils auch durch -(CH₂)_n-Gruppen mit n = 1 bis 3 überbrückt sein können und/oder, – Mono- und/oder Oligoglycosylreste,

mit der Maßgabe, dass mindestens ein Rest aus R¹ und R² steht für OR¹¹, und R³ steht für einen Rest OR¹¹ und
R⁴ bis R⁷ und R¹⁰ gleich oder verschieden sein können, und unabhängig voneinander stehen für

• – H
• – geradkettige oder verzweigte C₁- bis C₂₀-Alkylgruppen,
• – geradkettige oder verzweigte C₃- bis C₂₀-Alkenylgruppen,
• – geradkettige oder verzweigte C₁- bis C₂₀-Hydroxyalkylgruppen, wobei – die Hydroxygruppe an ein primäres oder sekundäres Kohlenstoffatom der Kette gebunden sein kann und weiter die Alkylkette auch durch Sauerstoff unterbrochen sein kann, und/oder
• – C₃- bis C₁₀-Cycloalkylgruppen und/oder C₃- bis C₁₂-Cycloalkenylgruppen, wobei die Ringe jeweils auch durch -(CH₂)_n-Gruppen mit n = 1 bis 3 überbrückt sein können und
• – R⁸ und R⁹ gleich oder verschieden sein können, und unabhängig voneinander stehen für
• – H
• – OR¹¹
• – geradkettige oder verzweigte C₁- bis C₂₀-Alkylgruppen,
• – geradkettige oder verzweigte C₃- bis C₂₀-Alkenylgruppen,
• – geradkettige oder verzweigte C₁- bis C₂₀-Hydroxyalkylgruppen, wobei die Hydroxygruppe an ein primäres oder sekundäres Kohlenstoffatom der Kette gebunden sein kann und weiter die Alkylkette auch durch Sauerstoff unterbrochen sein kann, und/oder
• – C₃- bis C₁₀-Cycloalkylgruppen und/oder C₃- bis C₁₂-Cycloalkenylgruppen, wobei die Ringe jeweils auch durch -(CH₂)_n-Gruppen mit n = 1 bis 3 überbrückt sein können.

Preferred formulations may also contain compounds of the formula I,

wherein R ¹ and R ^{2 are} selected from

• - H
• - and OR ¹¹ , wherein OR ^{11 is} independently of one another - OH - straight-chain or branched C ₁ - to C ₂₀ -alkyloxy groups, - straight-chain or branched C ₃ - to C ₂₀ -alkenyloxy groups, - straight-chain or branched C ₁ - to C ₂₀ -Hydroxyalkoxy groups, wherein the hydroxy group (s) may be bonded to a primary or secondary carbon atom of the chain and furthermore the alkyl chain may also be interrupted by oxygen, and / or - C ₃ - to C ₁₀ -cycloalkyloxy groups and / or C ₃ - to C ₁₂ -cycloalkenyloxy groups, it also being possible for the rings to be bridged by - (CH ₂ ) _n groups where n = 1 to 3 and / or - mono- and / or oligoglycosyl radicals,

with the proviso that at least one of R ¹ and R ² is OR ¹¹ , and R ³ is OR ¹¹ and
R ⁴ to R ⁷ and R ^{10 may be the} same or different, and independently of one another represents

• - H
• Straight-chain or branched C ₁ -C ₂₀ -alkyl groups,
• Straight-chain or branched C ₃ -C ₂₀ -alkenyl groups,
• Straight-chain or branched C ₁ -C ₂₀ -hydroxyalkyl groups, wherein - the hydroxy group can be bonded to a primary or secondary carbon atom of the chain and furthermore the alkyl chain can also be interrupted by oxygen, and / or
• C ₃ - to C ₁₀ -cycloalkyl groups and / or C ₃ - to C ₁₂ -cycloalkenyl groups, it also being possible for the rings to be bridged by - (CH ₂ ) _n groups where n = 1 to 3, and
• - R ⁸ and R ^{9 may be the} same or different, and independently of each other stand for
• - H
• - OR ¹¹
• Straight-chain or branched C ₁ -C ₂₀ -alkyl groups,
• Straight-chain or branched C ₃ -C ₂₀ -alkenyl groups,
• Straight-chain or branched C ₁ -C ₂₀ -hydroxyalkyl groups, where the hydroxy group may be bonded to a primary or secondary carbon atom of the chain and furthermore the alkyl chain may also be interrupted by oxygen, and / or
• - C ₃ - to C ₁₀ -cycloalkyl groups and / or C ₃ - to C ₁₂ -cycloalkenyl groups, wherein the rings may each be bridged by - (CH ₂ ) _n groups with n = 1 to 3.

advantages The preparations are in particular the UV light filtering Effect and good skin tolerance. additionally are the compounds described herein of the aforementioned formula colorless or faintly colored and lead so, unlike many known naturally occurring ones Flavonoids, not to discoloration of the preparations.

• – OH oder
• – geradkettige oder verzweigte C₁- bis C₂₀-Alkoxygruppen, vorzugsweise Methoxy, Ethoxy oder Ethylhexyloxy oder
• – Mono- und/oder Oligoglycosylreste, vorzugsweise Glucosylreste und
• – R¹ und/oder R² vorzugsweise stehen für
• – OH oder
• – geradkettige oder verzweigte C₁- bis C₂₀-Alkoxygruppen, vorzugsweise Methoxy, Ethoxy oder Ethylhexyloxy oder
• – Mono- und/oder Oligoglycosylreste, vorzugsweise Glucosylreste.

Among the flavonoids of the aforementioned formula to be used according to the invention, there are broadband UV filters, while other likewise preferred compounds of the aforementioned formula show an absorption maximum in the boundary region between the UV-B and the UV-A radiation. As UV-A-II filters, they therefore advantageously supplement the absorption spectrum of commercially available UV-B or UV-Al filters. Preferred compositions with photoprotective properties contain at least one compound of the aforementioned formula, wherein R ³ is

• - OH or
• Straight-chain or branched C ₁ -C ₂₀ -alkoxy groups, preferably methoxy, ethoxy or ethylhexyloxy or
• - Mono- and / or Oligoglycosylreste, preferably Glucosylreste and
• - R ¹ and / or R ² preferably stand for
• - OH or
• Straight-chain or branched C ₁ -C ₂₀ -alkoxy groups, preferably methoxy, ethoxy or ethylhexyloxy or
• - Mono- and / or Oligoglycosylreste, preferably Glucosylreste.

These preferred compounds are characterized by a particularly intense UV absorption off.

• – Mono- und/oder Oligoglycosylreste verbessern die Wasserlöslichkeit der erfindungsgemäß einzusetzenden Verbindungen;
• – geradkettige oder verzweigte C₁- bis C₂₀-Alkoxygruppen, insbesondere die langkettigen Alkoxyfunktionen, wie Ethylhexyloxy-Gruppen erhöhen die Öllöslichkeit der Verbindungen;

d. h. über die geeignete Auswahl der Substituenten kann die Hydrophilie bzw. Lipophilie der Verbindungen nch formel I gesteuert werden. Als Mono- oder Oligosaccharidreste bevorzugt sind dabei Hexosylreste, insbesondere Ramnosylreste und Glucosylreste. Aber auch andere Hexosylreste, beispielsweise Allosyl, Altrosyl, Galactosyl, Gulosyl, Idosyl, Mannosyl und Talosyl sind gegebenenfalls vorteilhaft zu verwenden. Es kann auch vorteilhaft sein, Pentosylreste zu verwenden. Die Glycosylreste können α- oder β-glycosidisch mit dem Grundkörper verbunden sein. Ein bevorzugtes Disaccharid ist beispielsweise das 6-O-(6-deoxy-α-L-mannopyranosyl)-β-D-glucopyranosid.In addition, such preferred compounds have advantages in the incorporation into the preparations:

• Mono- and / or Oligoglycosylreste improve the water solubility of the compounds to be used according to the invention;
• Straight-chain or branched C ₁ -C ₂₀ -alkoxy groups, in particular the long-chain alkoxy functions such as ethylhexyloxy groups, increase the oil-solubility of the compounds;

ie, via the appropriate choice of substituents, the hydrophilicity or lipophilicity of the compounds can be controlled nch formula I. Preferred mono- or oligosaccharide radicals are hexosyl radicals, in particular ramnosyl radicals and glucosyl radicals. However, other hexosyl radicals, for example allosyl, altrosyl, galactosyl, gulosyl, idosyl, mannosyl and talosyl, may also be advantageous to use. It may also be advantageous to use pentosyl radicals. The glycosyl residues can be linked to the basic structure by α- or β-glycosidic means. A preferred disaccharide is, for example, 6-O- (6-deoxy-α-L-mannopyranosyl) -β-D-glucopyranoside.

It has been found that the intensity of the UV absorption is high, especially when R ³ is straight-chain or branched C ₁ - to C ₂₀ -alkoxy groups, preferably methoxy, ethoxy or ethylhexyloxy, and R ⁸ and R ^{9 are} identical and are H or straight-chain or branched C ₁ - to C ₂₀ -alkoxy groups, preferably methoxy, ethoxy or ethylhexyloxy.

Therefore, preparations having light-protection properties comprising at least one compound of the aforementioned formula, which is characterized in that R ³ is straight-chain or branched C ₁ - to C ₂₀ alkoxy groups, preferably methoxy, ethoxy or ethylhexyloxy, and R ⁸ and R ^{9 are} identical are and stand for H or straight-chain or branched C ₁ - to C ₂₀ -alkoxy groups, preferably methoxy, ethoxy or ethylhexyloxy, particularly preferred according to the invention. In particular, it is preferred if and R ⁸ and R ⁹ stand for H.

The Compounds of the aforementioned formula are typically in amounts from 0.01% by weight to 20% by weight, preferably in amounts of 0.5% by weight up to 10% by weight and especially preferably in amounts of 1% by weight used to 8 wt .-%. It prepares the expert no Difficulties the quantities depending on the intended SPF of preparation to select accordingly.

By Combination of the titanium dioxide particles according to the invention with additional UV filters can protect against harmful Effects of UV radiation can be optimized. Optimized preparations can For example, the combination of organic UV filters 4'-methoxy-6-hydroxyflavone with 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione and Contain 3- (4'-methylbenzylidene) -dlkampfer.

• – Die Hydrophilie der Kapselwand kann unabhängig von der Löslichkeit des UV-Filters eingestellt werden. So können beispielsweise auch hydrophobe UV-Filter in rein wässrige Zubereitungen eingearbeitet werden. Zudem wird der häufig als unangenehm empfundene ölige Eindruck beim Auftragen der hydrophobe UV-Filter enthaltenden Zubereitung unterbunden.
• – Bestimmte UV-Filter, insbesondere Dibenzoylmethanderivate, zeigen in kosmetischen Zubereitungen nur eine verminderte Photostabilität. Durch Verkapselung dieser Filter oder von Verbindungen, die die Photostabilität dieser Filter beeinträchtigen, wie beispielsweise Zimtsäurederivate, kann die Photostabilität der gesamten Zubereitung erhöht werden.
• – In der Literatur wird immer wieder die Hautpenetration durch organische UV-Filter und das damit verbundene Reizpotential beim direkten Auftragen auf die menschliche Haut diskutiert. Durch die hier vorgeschlagene Verkapselung der entsprechenden Substanzen wird dieser Effekt unterbunden.
• – Allgemein können durch Verkapselung einzelner UV-Filter oder anderer Inhaltstoffe Zubereitungsprobleme, die durch Wechselwirkung einzelner Zubereitungsbestandteile untereinander entstehen, wie Kristallisationsvorgänge, Ausfällungen und Agglomeratbildung vermieden werden, da die Wechselwirkung unterbunden wird.

All mentioned UV filters can also be used in encapsulated form. In particular, it is advantageous to use organic UV filters in encapsulated form. In detail, there are the following advantages:

• - The hydrophilicity of the capsule wall can be adjusted independently of the solubility of the UV filter. For example, hydrophobic UV filters can also be incorporated into purely aqueous preparations. In addition, the often perceived as unpleasant oily impression when applying the hydrophobic UV filter containing preparation is suppressed.
• Certain UV filters, in particular dibenzoylmethane derivatives, show only reduced photostability in cosmetic preparations. By encapsulating these filters or compounds that affect the photostability of these filters, such as cinnamic acid derivatives, the photostability of the entire formulation can be increased.
• In the literature, the skin penetration through organic UV filters and the associated irritation potential during direct application to the human skin is discussed again and again. The encapsulation of the corresponding substances proposed here prevents this effect.
• - Generally, by encapsulation of individual UV filters or other ingredients preparation problems me, caused by interaction of individual preparation components with each other, such as crystallization processes, precipitation and agglomeration are avoided because the interaction is suppressed.

Therefore it may be preferred according to the invention, if a or more of the compounds according to formula I or (which formula I) the above-mentioned UV filter in encapsulated form available. It is advantageous if the capsules are so small that they can not be observed with the naked eye. To achieve the o. G. Effects it is still required that the capsules are sufficiently stable and the encapsulated drug (UV filter) not or only to a small extent to the environment.

Suitable capsules may have walls of inorganic or organic polymers. For example, in US 6,242,099 B1 describe the preparation of suitable capsules with walls of chitin, chitin derivatives or polyhydroxylated polyamines. Capsules which are particularly preferred for use in accordance with the invention have walls which are formed by a SolGel process, as described in applications WO 00/09652 . WO 00/72806 and WO 00/71084 described can be obtained. Again, capsules whose walls are made up of silica gel (silica, undefined silicon oxide hydroxide) are preferred. The production of such capsules is known to the skilled worker, for example, from the cited patent applications, whose contents are expressly also part of the subject of the present application.

there are the capsules in preparations according to the invention preferably contained in such amounts, which ensure that the encapsulated UV filters in the amounts specified above in the preparation is present.

Furthermore, the preparations according to the invention may also contain dyes and colored pigments. The dyes and pigments can be selected from the corresponding positive list of the Cosmetics Regulation or EC List of cosmetic colorants. In most cases, they are identical to the food-approved dyes. Examples of advantageous color pigments are titanium dioxide, mica, iron oxides (eg Fe ₂ O ₃ , Fe ₃ O ₄ , FeO (OH)) and / or tin oxide. Advantageous dyes are, for example, carmine, Berlin blue, chrome oxide green, ultramarine blue and / or manganese violet. It is particularly advantageous to choose the dyes and / or color pigments from the following list. The Color Index numbers (CIN) are the Rowe Color Index, 3rd Edition, Society of Dyers and Colourists, Bradford, England, 1971 taken.

It may also be favorable to choose as the dye one or more substances from the following group:
2,4-dihydroxyazobenzene, 1- (2'-chloro-4'-nitro-1'phenylazo) -2-hydroxynaphthalene, ceric red, 2- (4-sulfo-1-naphthylazo) -1-naphthol-4-sulfonic acid, Calcium salt of 2-hydroxy-1,2'-azonaphthalene-1'-sulfonic acid, calcium and barium salts of 1- (2-sulfo-4-methyl-1-phenylazo) -2-naphthylcarboxylic acid, calcium salt of 1- (2- Sulfo-1-naphthylazo) -2-hydroxynaphthalene-3-carboxylic acid, aluminum salt of 1- (4-sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid, aluminum salt of 1- (4-sulfo-1-naphthylazo) -2-naphthol-3,6-disulfonic acid, 1- (4-sulfo-1-naphthylazo) -2-naphthol-6,8-disulfonic acid, aluminum salt of 4- (4-sulfo-1-phenylazo) -2- ( 4-sulfophenyl) -5-hydroxy-pyrazolone-3-carboxylic acid, aluminum and zirconium salts of 4,5-dibromofluorescein, aluminum and zirconium salts of 2,4,5,7-tetrabromofluorescein, 3 ', 4', 5 ', 6'-Tetrachloro-2,4,5,7-tetrabromo-fluorescein and its aluminum salt, aluminum salt of 2,4,5,7-tetraiodofluorescein, aluminum salt of quinophthalone-disulfonic acid, aluminum salt of indigo-disulfonic acid, red and the like and black iron oxide (CIN: 77,491 (red) and 77,499 (black)), iron oxide hydrate (CIN: 77,492), manganese ammonium diphosphate, and titanium dioxide.

Further advantageous are oil-soluble natural dyes, such as z. As paprika extract, β-carotene or cochineal.

Also advantageous for the purposes of the present invention are gel creams with a content of pearlescent pigments or interference pigments, in particular those pigments whose compatibility with dihydroxyacetone has already been established. Particularly preferred are the pearlescent pigments or interference pigments, which are based on a platelet-shaped substrate and coated with titanium dioxide and / or iron oxide (Fe ₂ O ₃ ) and optionally have a final SiO ₂ layer.

Particularly preferred pigments are, for. As the pigments available from Merck under the trade names Timiron® ^®, Colorona® ^{®, ®} or Dichrona® Sirona ^®.

The Total amount of dyes and coloring pigments. will be beneficial from the range of z. 0.1% to 30% by weight, preferably from 0.5 wt% to 15 wt%, especially from 1.0 wt% to 10 Gew.% Selected, in each case based on the total weight of Preparations.

The protective effect against oxidative stress or against the The influence of radicals can be further improved if the Preparations containing one or more antioxidants.

There are many known and proven substances in the literature that can be used as antioxidants, e.g. For example, amino acids (eg, glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles, (eg urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their Derivatives (eg anserine), carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and derivatives thereof, chlorogenic acid and its derivatives, lipoic acid and derivatives thereof (eg dihydrolipoic acid), aurothioglucose, Propylthiouracil and other thiols (e.g., thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl , γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (eg buthionine sulfoximines, homocysteinsulfoximine, buthionine sulfones , Penta-, hexa-, heptathionine sulfoximine) in very poor compatibility doses (eg. Pmol to μmol / kg), further (metal) chelators (eg, α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g., citric acid, lactic acid, malic acid), humic acid, bile acids , Bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives, vitamin C and derivatives (eg ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg vitamin E). acetate), vitamin A and derivatives (eg vitamin A palmitate) and benzylic resin, rutinic acid and derivatives thereof, α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordohydroguajaretic acid, tri-hydroxybutyrophenone, quercitin, Uric acid and its derivatives, mannose and its derivatives, zinc and its derivatives (eg ZnO, ZnSO ₄ ), selenium and its derivatives (eg selenium methionine), stilbenes and their derivatives (eg stilbene oxide, trans stilbene oxide).

worin
R¹ aus der Gruppe -C(O)CH₃, -CO₂R³, -C(O)NH₂ und -C(O)N(R⁴)₂ ausgewählt werden kann,
X O oder NH,
R² lineares oder verzweigtes Alkyl mit 1 bis 30 C-Atomen,
R³ lineares oder verzweigtes Alkyl mit 1 bis 20 C-Atomen,
R⁴ jeweils ungabhängig voneinander H oder lineares oder verzweigtes Alkyl mit 1 bis 8 C-Atomen,
R⁵ lineares oder verzweigtes Alkyl mit 1 bis 8 C-Atomen oder lineares oder verzweigtes Alkoxy mit 1 bis 8 C-Atomen und
R⁶ lineares oder verzweigtes Alkyl mit 1 bis 8 C-Atomen bedeutet, vorzugsweise Derivate der 2-(4-Hydroxy-3,5-dimethoxybenzyliden)-malonsäure und/oder 2-(4-Hydroxy-3,5-dimethoxybenzyl)-malonsäure, besonders bevorzugt 2-(4-Hydroxy-3,5-dimethoxybenzyliden)-malonsäure-bis-(2-ethylhexyl)ester (z. B. Oxynex^® ST Liquid) und/oder 2-(4-Hydroxy-3,5-dimethoxybenzy)-malonsäure-bis-(2-ethylhexyl)ester (z. B. RonaCare^® AP). Die genannten Verbindungen der Formel A oder B sind auch vorteilhafte Photostabilisatoren für organische UV-Filter, aber auch anderen photosensitiven Verbindungen, wie beispielsweise Parfum oder Farbstoffe.Suitable antioxidants are also compounds of the formulas A or B.

wherein
R ^{1 can be selected} from the group -C (O) CH ₃ , -CO ₂ R ³ , -C (O) NH ₂ and -C (O) N (R ⁴ ) ₂ ,
X is O or NH,
R ^{2 is} linear or branched alkyl having 1 to 30 C atoms,
R ^{3 is} linear or branched alkyl having 1 to 20 C atoms,
R ^{4 are} each independently of one another H or linear or branched alkyl having 1 to 8 C atoms,
R ^{5 is} linear or branched alkyl having 1 to 8 C atoms or linear or branched alkoxy having 1 to 8 C atoms and
R ⁶ denotes linear or branched alkyl having 1 to 8 C atoms, preferably derivatives of 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid and / or 2- (4-hydroxy-3,5-dimethoxybenzyl) - malonic acid, particularly preferably 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid-bis (2-ethylhexyl) ester (z. B. Oxynex ^® ST Liquid) and / or 2- (4-hydroxy-3, 5-dimethoxybenzy) malonic acid-bis (2-ethylhexyl) ester (z. B. RonaCare ^® AP). The said compounds of formula A or B are also advantageous photostabilizers for organic UV filters, but also other photosensitive compounds such as perfume or dyes.

Mixtures of antioxidants are also suitable for use in the cosmetic preparations according to the invention. Known and commercial mixtures are, for example, mixtures comprising, as active ingredients, lecithin, L - (+) -. Ascorbyl palmitate and citric acid (for example (for example Oxynex ^® AP), natural tocopherols, L -. (+) - ascorbyl palmitate, L (+) - ascorbic acid and citric acid (. for example Oxynex ^® K LIQUID), tocopherol extracts from natural sources, L - (+) - ascorbyl palmitate, L - (+) - ascorbic acid and citric acid (. for example Oxynex L LIQUID ^®) , DL-α-tocopherol, L - (+) - ascorbyl palmitate, citric acid and lecithin (. for example Oxynex ^® LM) or butylhydroxytoluene (BHT), L - (+) -. ascorbyl palmitate and citric acid (for example Oxynex ^® 2004 ).

The preparations according to the invention may contain vitamins as further ingredients. Preference is given to vitamins and vitamin derivatives selected from vitamin A, vitamin A propionate, vitamin A palmitate, vitamin A acetate, retinol, vitamin B, thiamin chloride hydrochloride (vitamin B ₁ ), riboflavin (vitamin B ₂ ), nicotinamide , Vitamin C (ascorbic acid), Vitamin D, Ergocalciferol (Vitamin D ₂ ), Vitamin E, DL-α-tocopherol, To copherol E acetate, tocopherol hydrogen succinate, vitamin K ₁ , esculin (vitamin P active ingredient), thiamine (vitamin B ₁ ), nicotinic acid (niacin), pyridoxine, pyridoxal, pyridoxamine, (vitamin B ₆ ), pantothenic acid, biotin, folic acid and Cobalamin (vitamin B ₁₂ ) in the cosmetic preparations according to the invention, particularly preferably vitamin A palmitate, vitamin C, DL-α-tocopherol, tocopherol E acetate, nicotinic acid, pantothenic acid and biotin.

The Preparations according to the invention can In addition, other usual skin-friendly or skin-care Contain active ingredients. This can in principle all the Be a specialist known drugs.

Especially preferred active ingredients are pyrimidinecarboxylic acids and / or Aryl oximes.

worin R¹ ein Rest H oder C1-8-Alkyl, R² ein Rest H oder C1-4-Alkyl und R³, R⁴, R⁵ sowie R⁶ jeweils unabhängig voneinander ein Rest aus der Gruppe H, OH, NH₂ und C1-4-Alkyl sind. Bevorzugt werden Pyrimidincarbonsäuren eingesetzt, bei denen R² eine Methyl- oder eine Ethylgruppe ist und R¹ bzw. R⁵ und R⁶ H sind. Insbesondere bevorzugt werden die Pyrimidincarbonsäuren Ectoin ((S)-1,4,5,6-Tetrahydro-2-methyl-4-pyrimidin-carbonsäure) und Hydroxyectoin ((S,S)-1,4,5,6-Tetrahydro-5-hydroxy-2-methyl-4-pyrimidin-carbonsäure) eingesetzt. Dabei enthalten die erfindungsgemäßen Zubereitungen derartige Pyrimidincarbonsäuren vorzugsweise in Mengen bis zu 15 Gew.-%.In this case, a pyrimidinecarboxylic acid according to formula II below is preferably used,

wherein R ^{1 is} a radical H or C 1-8 -alkyl, R ^{2 is} a radical H or C 1-4 -alkyl and R ³ , R ⁴ , R ⁵ and R ^{6 are} each independently a radical from the group H, OH, NH ₂ and C1-4 alkyl. Preference is given to using pyrimidinecarboxylic acids in which R ^{2 is} a methyl or an ethyl group and R ¹ or R ⁵ and R ^{6 are} H. Particular preference is given to the pyrimidinecarboxylic acids ectoine ((S) -1,4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acid) and hydroxyectoine ((S, S) -1,4,5,6-tetrahydrocarboxylic acid). 5-hydroxy-2-methyl-4-pyrimidine-carboxylic acid). The preparations according to the invention contain such pyrimidinecarboxylic acids, preferably in amounts of up to 15% by weight.

Among the aryl oximes, 2-hydroxy-5-methyllaurophenone oxime, which is also referred to as HMLO, LPO or F5, is preferably used. Its suitability for use in cosmetic products, for example, from the German patent application DE-A-41 16 123 known. Preparations containing 2-hydroxy-5-methyllaurophenone oxime are accordingly suitable for the treatment of skin diseases which are associated with inflammation. It is known that such preparations z. B. for the treatment of psoriasis, different types of eczema, irritative and toxic dermatitis, UV dermatitis and other allergic and / or inflammatory diseases of the skin and the skin appendages can be used. Preparations according to the invention which contain aryloximes, preferably 2-hydroxy-5-methyllaurophenone oxime, show surprising antiinflammatory suitability. The preparations preferably contain 0.01% by weight to 10% by weight of the aryloxime, and it is particularly preferred if the preparation contains from 0.05% by weight to 5% by weight of aryloxime.

All compounds described herein or components used in the preparations can be used, are either known and commercially available Acquired or can be synthesized by known methods become.

The Preparations according to the invention can prepared by methods well known to those skilled in the art are, in particular, according to the methods used for the preparation of oil-in-water emulsions or Serve water-in-oil emulsions.

One Another object of the present invention is a method for the preparation of a preparation which is characterized is that titanium dioxide particles, as described above, with a cosmetically or dermatologically suitable carrier and optionally weiteen ingredients, as described above, is mixed.

These Preparations may be in particular in the form of simple or complicated emulsions (O / W, W / O, O / W / O or W / O / W), such as Creams, milks, gels or gel creams, powders and solid sticks and optionally, they may be formulated as aerosols be in the form of foams or sprays. Preferably These preparations are in the form of an O / W emulsion.

The cosmetic preparations according to the invention can be used as a preparation for protecting the human epidermis or the hair against UV radiation, for skin care, as a sunscreen, self tanning or make-up products are used.

It should be noted that in the inventive Sunscreen formulations comprising a vehicle of the type an oil-in-water emulsion, the aqueous Phase (which in particular contains the hydrophilic filters) generally from 50% to 95%, and preferably from 70% to, by weight 90 wt .-%, based on the total formulation, the oil phase (containing in particular the lipophilic filters) 5% by weight to 50 wt .-% and preferably 10 wt .-% to 30 wt .-%, based to the entire formulation and the (co) emulsifier or the (co) emulsifiers From 0.5% to 20% by weight, and preferably from 2% to 10% by weight, based on the entire formulation.

Suitable are preparations for an external Application, for example as a cream, lotion, gel, or as a solution, which can be sprayed on the skin. For an internal application are dosage forms such as capsules, Dragees, powders, tablet solutions or solutions suitable.

When Use of the preparations according to the invention be z. B. called: solutions, suspensions, emulsions, PIT emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, surfactant-containing cleaning preparations, oils, aerosols and sprays. Other applications are z. As sticks, shampoos and shower rooms. The preparation can be any conventional Carriers, excipients and optionally other active ingredients be added.

preferable Excipients come from the group of preservatives, antioxidants, Stabilizers, solubilizers, vitamins, colorants, Odor.

Anoint, Pastes, creams and gels can be the usual carriers included, for. B. animal and vegetable fats, waxes, paraffins, Starch, tragacanth, cellulose derivatives, polyethylene glycols, Silicones, bentonites, silicic acid, talc and zinc oxide or Mixtures of these substances.

powder and sprays can be the usual carriers included, for. Lactose, talc, silicic acid, aluminum hydroxide, Calcium silicate and polyamide powder or mixtures of these substances. Sprays can also use the usual Propellant, z. As chlorofluorocarbons, propane / butane or Dimethyl ether.

solutions and emulsions may be the usual carriers such as solvents, solubilizers and emulsifiers, z. As water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, Benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butylglycol, oils, especially cottonseed oil, peanut oil, corn oil, Olive oil, castor oil and sesame oil, glycerol fatty acid esters, Polyethylene glycols and fatty acid esters of sorbitan or Mixtures of these substances included.

suspensions can the usual carriers like liquid diluents, e.g. As water, ethanol or Propylene glycol, suspending agent, e.g. B. ethoxylated isostearyl alcohols, Polyoxyethylene sorbitol esters and polyoxyethylene sorbitan esters, microcrystalline Cellulose, aluminum metahydroxide, bentonite, agar-agar and tragacanth or mixtures of these substances.

Soap can the usual carriers like Alkali salts of fatty acids, salts of fatty acid monoesters, Fatty acid protein hydrolysates, isothionates, lanolin, Fatty alcohol, vegetable oils, plant extracts, glycerin, sugar or mixtures of these substances.

surfactant Cleaning products can be the usual carriers such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic monoesters, Fatty acid protein hydrolysates, isothionates, imidazolinium derivatives, Methyl taurates, sarcosinates, fatty acid amide ether sulfates, Alkylamidobetaines, fatty alcohols, fatty acid glycerides, fatty acid diethanolamides, vegetable and synthetic oils, lanolin derivatives, ethoxylated Glycerin fatty acid esters or mixtures of these substances.

facial and body oils can be the usual Carriers such as synthetic oils such as fatty acid esters, fatty alcohols, Silicone oils, natural oils such as vegetable oils and oily extracts, paraffin oils, Lanolin oils or mixtures of these substances.

Further typical cosmetic applications are also lipsticks, lip balms, Mascara, eye liner, eye shadow, blush, powder, emulsion and wax make up and sunscreen, pre-sun and after-sun preparations.

To the preferred forms of preparation according to the invention include in particular emulsions.

invention Emulsions are advantageous and contain z. As mentioned fats, oils, Waxes and other fatty substances, as well as water and an emulsifier, as he usually does for such a type of preparation is used.

• – Mineralöle, Mineralwachse
• – Öle, wie Triglyceride der Caprin- oder der Caprylsäure, ferner natürliche Öle wie z. B. Rizinusöl;
• – Fette, Wachse und andere natürliche und synthetische Fettkörper, vorzugsweise Ester von Fettsäuren mit Alkoholen niedriger C-Zahl, z. B. mit Isopropanol, Propylenglykol oder Glycerin, oder Ester von Fettlkoholen mit Alkansäuren niedriger C-Zahl oder mit Fettsäuren;
• – Silikonöle wie Dimethylpolysiloxane, Diethylpolysiloxane, Diphenylpolysiloxane sowie Mischformen daraus.

The lipid phase can advantageously be selected from the following substance group:

• - mineral oils, mineral waxes
• - Oils such as triglycerides of capric or caprylic, further natural oils such. Castor oil;
• Fats, waxes and other natural and synthetic fats, preferably esters of fatty acids with lower C-number alcohols, e.g. With isopropanol, propylene glycol or glycerol, or esters of fatty alcohols with alkanoic acids of low C number or with fatty acids;
• - Silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms thereof.

The oil phase of the emulsions, oleogels or hydrodispersions or lipodispersions in the context of the present invention is advantageously chosen from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a Chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched Alcohols of a chain length of 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acid and saturated and / or unsaturated, branched and / or unbranched Alcohols of a chain length of 3 to 30 carbon atoms. Such ester oils can then be chosen favorably from the Group isopropyl myristate, isopropyl 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-hexadecyl stearate, 2-octyl dodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate as well as synthetic, semi-synthetic and natural mixtures such esters, e.g. B. jojoba oil.

Further the oil phase can be chosen advantageously from the group of branched and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ethers, the group the saturated or unsaturated, branched or unbranched alcohols, and the fatty acid triglycerides, namely the triglycerol esters of saturated and / or unsaturated branched and / or unbranched alkanecarboxylic acids of a Chain length of 8 to 24, in particular 12-18 C atoms. The fatty acid triglycerides may be, for example be chosen advantageously from the group of synthetic, semisynthetic and natural oils, e.g. Olive oil, sunflower oil, Soybean oil, peanut oil, rapeseed oil, almond oil, Palm oil, coconut oil, palm kernel oil and the like more.

Also any mixtures of such oil and wax components are advantageous to use in the context of the present invention. It may also be advantageous to use waxes, for example Cetyl palmitate, as the sole lipid component of the oil phase use.

Advantageously, the oil phase is selected from the group consisting of 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C _12-15 alkyl benzoate, caprylic capric acid triglyceride, dicapryl ether.

Particularly advantageous are mixtures of C _12-15 -alkyl benzoate and 2-ethylhexyl isostearate, mixtures of C _12-15 -alkyl benzoate and isotridecyl isononanoate and mixtures of C _12-15 -alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate.

From The hydrocarbons are paraffin oil, squalane and squalene advantageous to use in the context of the present invention.

Advantageous The oil phase may also contain a cyclic content or linearly silicone oils or completely consist of such oils, although it is preferred except the silicone oil or silicone oils an additional content of other oil phase components to use.

Advantageous Cyclomethicone (Octamethylcyclotetrasiloxan) as according to the invention to used silicone oil. But also other silicone oils are advantageous for the purposes of the present invention to use for example, hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).

Especially also advantageous are mixtures of cyclomethicone and isotridecyl isononanoate, from cyclomethicone and 2-ethylhexyl isostearate.

The aqueous phase of the invention Preparations optionally contains advantageous alcohols, Diols or polyols of 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 analogous products, furthermore lower C number alcohols, e.g. Ethanol, Isopropanol, 1,2-propanediol, glycerol and in particular one or more Thickener, which or which are chosen advantageous can be selected from the group silicon dioxide, aluminum silicates, Polysaccharides or their derivatives, for. Hyaluronic acid, Xanthan gum, hydroxypropyl methylcellulose, particularly advantageous from the group of polyacrylates, preferably a polyacrylate from the Group of so-called carbopols, for example carbopols of the types 980, 981, 1382, 2984, 5984, each alone or in combination.

Especially Mixture of the abovementioned solvents are used. For alcoholic solvents, water can be another Be part of it.

invention Emulsions are advantageous and contain z. As mentioned fats, oils, Waxes and other fatty substances, as well as water and an emulsifier, as he usually does for such a type of formulation is used.

In a preferred embodiment, the inventive Preparations hydrophilic surfactants.

The Hydrophilic surfactants are preferably selected from the group the alkylglucosides, acyl lactylates, betaines and cocoamphoacetates.

Particularly according to the invention Advantageously used alkyl glycosides are selected from the group octylglucopyranoside, nonylglucopyranoside, decylglucopyranoside, Undecylglucopyranoside, dodecylglucopyranoside, tetradecylglucopyranoside and hexadecyl glucopyranoside.

It is likewise advantageous to employ natural or synthetic raw materials and assistants or mixtures which are distinguished by an effective content of the active ingredients used according to the invention, for example Plantaren ^® 1200 (Henkel KGaA), Oramix NS ^® 10 (Seppic).

auszeichnen, wobei R¹ einen verzweigten oder unverzweigten Alkylrest mit 1 bis 30 Kohlenstoffatomen bedeutet und M⁺ aus der Gruppe der Alkaliionen sowie der Gruppe der mit einer oder mehreren Alkyl- und/oder mit einer oder mehreren Hydroxyalkylresten substituierten Ammoniumionen gewählt wird bzw. dem halben Äquivalent eines Erdalkalions entspricht.In turn, the acyl lactylates are advantageously selected from the group of substances which are defined by the structural formula

in which R ^{1 is} a branched or unbranched alkyl radical having 1 to 30 carbon atoms and M ^{+ is selected} from the group of the alkali metal ions and the group of ammonium ions substituted by one or more alkyl and / or by one or more hydroxyalkyl radicals or half Equivalent to an alkaline earth metal equivalent.

For example, sodium is advantageous, for example the product Pathionic ^® ISL from the American Ingredients Company.

For the group of betaine, for example capramidopropylbetaine advantageous for example the product Tego ^® betaine 810 from Th. Goldschmidt AG.

, Sodium, for example, selected as inventively advantageous cocoamphoacetate as under the name Miranol ^® Ultra C32 from Miranol Chemical Corp. is available.

The preparations according to the invention are advantageously characterized in that the one or more hydrophilic surfactants in concentrations of 0.01-20 wt .-%, preferably 0.05-10 wt .-%, particularly preferably 0.1-5 wt .-%, each based on the total weight of the preparation, is present or present.

To Application are the cosmetic according to the invention and dermatological preparations in the usual for cosmetics Applied to the skin and / or hair in sufficient quantity.

Cosmetic and dermatological preparations according to the invention can be present in various forms. So they can z. For example, a solution, an anhydrous preparation, an emulsion or microemulsion of the water-in-oil (W / O) type or of the oil-in-water (O / W) type, a multiple emulsion, for example of the Waser-in type. Oil-in-water (W / O / W), a gel, a solid stick, an ointment or even an aerosol represent. It is also advantageous to present Ectoine in encapsulated form, e.g. In collagen matrices and other common encapsulating materials, e.g. As encapsulated cellulose, in gelatin, wax matrices or liposomally encapsulated. In particular wax matrices like those in the DE-OS 43 08 282 have been described, have turned out to be favorable. Preference is given to emulsions. O / W emulsins are especially preferred. Emulsions, W / O emulsions and O / W emulsions are available in the usual way.

When Emulsifiers, for example, the well-known W / O and O / W emulsifiers are used. It is beneficial to more usual Co-emulsifiers in the preferred according to the invention O / W emulsions to use.

When Particularly preferred emulsifier according to the invention for O / W emulsions, the commercial product Ceralution C of the company Sasol proved.

According to the invention advantageous are selected as co-emulsifiers, for example, O / W emulsifiers, mainly from the group of substances with HLB values of 11-16, especially advantageous with HLB values of 14.5-15.5, if the O / W emulsifiers have saturated radicals R and R '. Do the O / W emulsifiers unsaturated radicals R and / or R 'on, or are Isoalkylderivate, the preferred HLB value of such emulsifiers also lower or above lie.

It is advantageous, the fatty alcohol ethoxylates from the group of ethoxylated Stearyl alcohol, cetyl alcohols, cetylstearyl alcohols (cetearyl alcohols) to choose. Particularly preferred are: polyethylene glycol (13) stearyl ether (Steareth-13), polyethylene glycol (14) stearyl ether (steareth-14), Polyethylene glycol (15) stearyl ether (steareth-15), polyethylene glycol (16) stearyl ether (Steareth-16), polyethylene glycol (17) stearyl ether (steareth-17), polyethylene glycol (18) stearyl ether (Steareth-18), polyethylene glycol (19) stearyl ether (steareth-19), Polyethylene glycol (20) stearyl ether (steareth-20), polyethylene glycol (12) isostearyl ether (Isosteareth-12), polyethylene glycol (13) isostearyl ether (isosteareth-13), Polyethylene glycol (14) isostearyl ether (isosteareth-14), polyethylene glycol (15) isostearyl ether (Isosteareth-15), polyethylene glycol (16) isostearyl ether (isosteareth-16), Polyethylene glycol (17) isostearyl ether (isosteareth-17), polyethylene glycol (18) isostearyl ether (Isosteareth-18), polyethylene glycol (19) isostearyl ether (isosteareth-19), Polyethylene glycol (20) isostearyl ether (isosteareth-20), polyethylene glycol (13) cetyl ether (Ceteth-13), polyethylene glycol (14) cetyl ether (Ceteth-14), polyethylene glycol (15) cetyl ether (Ceteth-15), polyethylene glycol (16) cetyl ether (ceteth-16), polyethylene glycol (17) cetyl ether (Ceteth-17), polyethylene glycol (18) cetyl ether (ceteth-18), polyethylene glycol (19) cetyl ether (Ceteth-19), polyethylene glycol (20) cetyl ether (Ceteth-20), polyethylene glycol (13) isocetyl ether (Isoceteth-13), polyethylene glycol (14) isocetyl ether (isoceteth-14), Polyethylene glycol (15) isocetyl ether (Isoceteth-15), polyethylene glycol (16) isocetyl ether (Isoceteth-16), polyethylene glycol (17) isocetyl ether (isoceteth-17), Polyethylene glycol (18) isocetyl ether (isoceteth-18), polyethylene glycol (19) isocetyl ether (Isoceteth-19), polyethylene glycol (20) isocetyl ether (Isoceteth-20), Polyethylene glycol (12) oleyl ether (Oleth-12), polyethylene glycol (13) oleyl ether (Oleth-13), polyethylene glycol (14) oleyl ether (Oleth-14), polyethylene glycol (15) oleyl ether (Oleth-15), polyethylene glycol (12) lauryl ether (Laureth-12), polyethylene glycol (12) isolauryl ether (Isolaureth-12), polyethylene glycol (13) cetyl stearyl ether (ceteareth-13), Polyethylene glycol (14) cetyl stearyl ether (ceteareth-14), polyethylene glycol (15) cetyl stearyl ether (Ceteareth-15), polyethylene glycol (16) cetyl stearyl ether (ceteareth-16), Polyethylene glycol (17) cetyl stearyl ether (ceteareth-17), polyethylene glycol (18) cetyl stearyl ether (Ceteareth-18), polyethylene glycol (19) cetyl stearyl ether (Ceteareth-19), Polyethylene glycol (20) cetylstearyl ether (Ceteareth-20).

It is also advantageous to choose the fatty acid ethoxylates of the following group:
Polyethylene glycol (20) stearate, polyethylene glycol (21) stearate, polyethylene glycol (22) stearate, polyethylene glycol (23) stearate, polyethylene glycol (24) stearate, polyethylene glycol (25) stearate, polyethylene glycol (12) isostearate, polyethylene glycol (13) isostearate, polyethylene glycol ( 14) isostearate, polyethylene glycol (15) isostearate, polyethylene glycol (16) isostearate, polyethylene glycol (17) isostearate, polyethylene glycol (18) isostearate, polyethylene glycol (19) isostearate, polyethylene glycol (20) isostearate, polyethylene glycol (21) isostearate, polyethylene glycol (22) iso stearate, polyethylene glycol (23) isostearate, polyethylene glycol (24) isostearate, polyethylene glycol (25) isostearate, polyethylene glycol (12) oleate, polyethylene glycol (13) oleate, polyethylene glycol (14) oleate, polyethylene glycol (15) oleate, polyethylene glycol (16) oleate, Polyethylene glycol (17) oleate, polyethylene glycol (18) oleate, polyethylene glycol (19) oleate, polyethylene glycol (20) oleate,

When ethoxylated alkyl ether carboxylic acid or its salt can Advantageously, the sodium laureth-11-carboxylate can be used. When Alkyl ether sulfate can be advantageously used sodium laureth 1-4 sulfate become. As the ethoxylated cholesterol derivative, polyethylene glycol (30) may advantageously be cholesteryl ether be used. Also, polyethylene glycol (25) sojasterol has become proven. As ethoxylated triglycerides can Advantageously, the polyethylene glycol (60) Evening Primrose Glycerides be used (Evening Primrose = evening primrose).

Farther is advantageous, the Polyethylenglycolglycerinfettsäureester from the group polyethylene glycol (20) glyceryl laurate, polyethylene glycol (21) glyceryl laurate, polyethylene glycol (22) glyceryl laurate, Polyethylene glycol (23) glyceryl laurate, polyethylene glycol (6) glyceryl caprate / cprinate, Polyethylene glycol (20) glyceryl oleate, polyethylene glycol (20) glyceryl isostearate, Polyethylene glycol (18) glyceryl oleate (cocoate to choose.

It is also cheap, the sorbitan esters from the group Polyethylene glycol (20) sorbitan monolaurate, polyethylene glycol (20) sorbitan monostearate, Polyethylene glycol (20) sorbitan monoisostearate, polyethylene glycol (20) sorbitan monopalmitate, Polyethylene glycol (20) to choose sorbitan monooleate.

As optional, but according to the invention optionally advantageous W / O emulsifiers can be used:
Fatty alcohols having 8 to 30 carbon atoms, monoglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 8 to 24, in particular 12-18 C atoms, diglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of one chain length from 8 to 24, in particular 12-18 C-atoms, monoglycerol ethers of saturated and / or unsaturated, branched and / or unbranched alcohols of a chain length of 8 to 24, in particular 12-18 C-atoms, diglycerol ether of saturated and / or unsaturated, branched and or unbranched alcohols of a chain length of 8 to 24, in particular 12-18 C-atoms, propylene glycol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a chain length of 8 to 24, in particular 12-18 C-atoms and sorbitan esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids of a Ke length of 8 to 24, in particular 12-18 C atoms.

Especially advantageous W / O emulsifiers are glyceryl monostearate, glyceryl monoisostearate, Glyceryl monomyristate, glyceryl monoeate, diglyceryl monostearate, Diglyceryl monoisostearate, propylene glycol monostearate, propylene glycol monoisostearate, Propylene glycol monocaprylate, propylene glycol monolaurate, sorbitan monoisostearate, Sorbitan monolaurate, sorbitan monocaprylate, sorbitan monoisooleate, Sucrose distearate, cetyl alcohol, stearyl alcohol, arachidyl alcohol, Behenyl alcohol, isobehenyl alcohol, selachyl alcohol, chimyl alcohol, Polyethylene glycol (2) stearyl ether (steareth-2), glyceryl monolaurate, Glyceryl monocaprinate, glyceryl monocaprylate.

According to the invention preferred Preparations are particularly suitable for protecting human skin UV-induced aging and oxidative stress, d. H. against damage by radicals, as z. B. by Sunlight, heat or other influences be generated. She lies in different, for this Application commonly used dosage forms in front. Thus, it can be used especially as a lotion or emulsion, such as Cream or milk (O / W, W / O, O / W / O, W / O / W), in the form of oily-alcoholic, oily-aqueous or aqueous-alcoholic gels or solutions, be present as solid pins or formulated as an aerosol.

The Preparation may contain cosmetic adjuvants present in this Type of preparations commonly used, such as z. Thickening agents, emollients, humectants, surfactants, emulsifiers, preservatives, Foaming agents, perfumes, waxes, lanolin, propellants, Dyes and / or pigments containing the agent itself or the Dye skin, and others in cosmetics usually used ingredients.

you may be an oil as a dispersing or solubilizing agent, Wax or other fat, a low mono alcohol or a lower polyol or mixtures thereof. To the particularly preferred monoalcohols or polyols Ethanol, i-propanol, propylene glycol, glycerol and sorbitol.

A preferred embodiment of the invention is an emulsion which is used as a protective cream or Milk is present and in addition to the compound or compounds of formula I, for example, fatty alcohols, fatty acids, fatty acid esters, especially triglycerides of fatty acids, lanolin, natural and synthetic oils or waxes and emulsifiers in the presence of water.

Further preferred embodiments provide oily lotions based on natural or synthetic oils and waxes, lanolin, fatty acid esters, especially triglycerides of fatty acids, or oily-alcoholic lotions based on a lower alcohol, such as ethanol, or a glycerol, such as propylene glycol, and / or a polyol, such as glycerol, and oils, Waxes and fatty acid esters, such as triglycerides of fatty acids, represents.

The Preparation according to the invention can also be used as alcoholic Gel containing one or more lower alcohols or polyols, such as ethanol, propylene glycol or glycerin, and a thickening agent, such as Silica covered. The oily-alcoholic gels also contain natural or synthetic oil or Wax.

The Solid pens are made of natural or synthetic Waxing and oiling, fatty alcohols, fatty acids, fatty acid esters, Lanolin and other fatty substances.

is a preparation prepared as an aerosol, is used in the Usually the usual propellants, such as alkanes, fluoroalkanes and chlorofluoroalkanes.

The Cosmetic preparation can also protect the hair against photochemical Damage used to make changes Color shades, a discoloration or damage mechanical Kind of preventing. In this case, suitable packaging takes place as a shampoo, lotion, gel or emulsion for rinsing, taking the respective preparation before or after shampooing, before or after dyeing or decolouring or before or after the permanent wave is applied. It can also be a preparation as Lotion or gel for hairdressing and treatment, as a lotion or gel for brushing or laying a water wave, as a hair coat, Permanent wave agent, dyeing or decolorizing agent the hair can be chosen. The preparation with light protection properties may contain various adjuvants used in this type of medium, such as surfactants, active agents, thickeners, polymers, softening agents, preservatives, foam stabilizers, Electrolytes, organic solvents, silicone derivatives, oils, Waxes, anti-grease agents, dyes and / or pigments containing the agent dye yourself or your hair or others for that Hair care commonly used ingredients.

The Preparations as described above, may be mentioned contain necessary or optional ingredients or comprise, consist essentially of, or consist of.

in the The following is the invention by way of examples closer explained.

Examples

Example of SiO ₂ determination or determination of the after-treatment substance containing Si.

0.1 g to 0.5 g of the sample (weighed accurately to 0.0001), depending on the expected content of Si, are mixed in a small platinum crucible with 5 g of soda / borax mixture 7 + 1 and about 30 minutes open minded. After cooling, leached out to the melt in 50 ml of dilute hydrochloric acid cold, transferred the approach in a 250 ml volumetric flask, filled up with double-distilled water to the brand and gently shakes (CO ₂ ) by. Depending on the content, the determination of the silica is carried out either directly or after appropriate dilution (the maximum digesting agent concentration for the measurement on the ICP-OES is 2%). A chemical blanket is mandatory.

The Calibration is done using standard solutions whose Matrix of the sample matrix corresponds.

The device (ICP-OES) from Perkin Elmer, Optima 3300DV, is measured using the operating instructions of the device. The SiO ₂ content is determined here on the total particles, ie the values are below the specified values for the SiO ₂ content based on the TiO ₂ content of the particles to be coated.

For the calculation Si → SiO2 2.119 SiO2 · 1,220 = simethicone

Reagents and solutions used:

• Soda, anhydrous, p. a.
• Borax, sodium tetraborate, p. a.
• Hydrochloric acid, p. a. 1 + 1 diluted with bidistilled water

Example 1 Preparation of nano-TiO ₂ without hydrothermal treatment as comparison:

Example 1a Preparation of a Titanium Dioxide with Iron Doping and 35% SiO ₂ Post-Treatment

x l of an aqueous suspension of metatitanic acid containing about 370 g of TiO ₂ / l are mixed with 0.9 × 1 of water and 50% strength sodium hydroxide solution, heated to boiling temperature while stirring and kept at the temperature for 2 hours. The resulting sodium titanate is washed and adjusted with water to a content of about 100-110 g TiO ₂ / l.

The titanate is heated to 60 ° C. It is then acidified with 30% HCl to pH 2, then stirred for 45 min at the temperature and the pH. An amount of a known FeCl ₃ solution is added such that the content of Fe is 0.09%, based on TiO ₂ .

With water and 30% hydrochloric acid, contents of 45 g HCl / l and 90 g TiO ₂ / l are subsequently adjusted and the suspension is kept at 85 ° C. with stirring for 6 h ("peptization").

The peptized suspension is slowly added to pH 5.5 with 50% NaOH neutralized and diluted to 50 g / l.

Subsequently, the suspension is mixed at 80 ° C with sodium silicate solution (concentration: about 270 g SiO ₂ / l) and kept the rising pH with dilute sulfuric acid constant at pH 9.0.

After addition of the entire waterglass solution, a pH of 6.5 is set with H ₂ SO ₄ and the suspension is allowed to mature for 2 hours at the temperature and the pH with stirring. The suspension obtained contains about 6.7% product.

Example 1b:

The obtained from Example 1a test product is filtered off and washed with Water is washed to a conductivity <100 μS / cm. Of the obtained filter cake contains about 18% product.

Example 1c:

The test product obtained from Example 1b is dried. It is a hydrophilic TiO ₂ with 35% silica.

Example 2: Preparation of nano-TiO ₂ with hydrothermal treatment

Preparation of a hydrothermally treated titanium dioxide with iron doping and 35% SiO ₂ post-treatment:

x l of an aqueous suspension of metatitanic acid containing about 370 g of TiO ₂ / l are mixed with 0.9 × 1 of water and 50% strength sodium hydroxide solution, heated to boiling temperature while stirring and kept at the temperature for 2 hours. The resulting sodium titanate is washed and adjusted with water to a content of about 100-110 g TiO ₂ / l.

The titanate is heated to 60 ° C. It is then acidified with 30% HCl to pH 2, then stirred for 45 min at the temperature and the pH. With water and 30% hydrochloric acid, contents of 45 g HCl / l and 90 g TiO ₂ / l are subsequently adjusted and the suspension is kept at 85 ° C. with stirring for 6 h ("peptization").

The peptized suspension is slowly neutralized to pH 5.5 with 50% NaOH and reduced to 50 g / l diluted and subjected to a hydrothermal treatment in the pressure vessel at 180 ° C for a period of 2 h.

Subsequently, the suspension is mixed at 80 ° C with sodium silicate solution (concentration: about 270 g SiO ₂ / l) and kept the rising pH with dilute sulfuric acid constant at pH 9.0. After addition of the entire waterglass solution, a pH of 6.5 is set with H ₂ SO ₄ and the suspension is allowed to mature for 2 hours at the temperature and the pH with stirring. The product is filtered off and washed with water to a conductivity <100 μS / cm. The resulting filter cake is slurried with water and contains about 10.5% product.

Example 2a:

3.8 kg of the washed suspension from Example 2 are dried and ground. The product is a hydrophilic TiO ₂ (hydrothermally treated) with 35% silica.

Example 2b: Post-treatment with simethicone

To 3.8 kg of the washed suspension from Example 2a (corresponding to 402 g of starting material), 134 g of Silsoft Simethicone Emulsion, Fa. Momentive (30% simethicone) (corresponding to 10% of active substance, based on starting material) are slowly added with stirring and for 30 Stirred for another minute. The suspension is dried and ground. The product is a hydrophobic TiO ₂ with 35% silica and 10% simethicone.

Example 3:

Example 3a: Compatibility with DHA in cosmetic formulation - discoloration after storage for 3 months at room temperature in the dark:

O / W test formulation used: trade name INCI % % A TiO ₂ according to the invention 5.00 1.00 Tego Care 150 GLYCERYL STEARATE, STEARETH-25, CETETH-20; STEARYL ALCOHOL 8.00 8.00 Lanette O CETEARYL ALCOHOL 1.50 1.50 Tegosoft liquid CETEARYL ETHYLHEXANOATE 5.00 5.00 Miglyol 812N CAPRYC / CAPRYLIC TRIGLYVCERIDE 5.00 5.00 Abil wax 2434 STEAROXY DIMETHICONE 1.00 1.00 DC 200 (100 cs) DIMETHICONE 0.50 0.50 Propylparaben PROPYLPARABEN 0.05 0.05 B 1,2-propanediol PROPYLENE GLYCOL 3.00 3.00 methylparaben METHYL PARABEN 0.15 0.15 water AQUA 55,80 62,80 C DHA dihydroxyacetone 5.00 2.00 water AQUA 10.00 10.00 100.00 100.00

• 1. 5 Gew.-% DHA pur ohne TiO₂
• 2. 5 Gew.-% DHA mit 5 Gew.-% TiO₂ nach Beispiel 2a
• 3. 5 Gew.-% DHA mit 5 Gew.-% TiO₂ Beispiel 3a
• 4. 5 Gew.-% DHA mit 5 Gew.-% Parsol T-X
• 5. 5 Gew.-% DHA mit 5 Gew.-% UV Titan M 263

For the storage test, the above-mentioned test formulation with 5% by weight of DHA together with different titanium dioxide qualities is investigated:

• 1.5% by weight of pure DHA without TiO ₂
• 2. 5 wt .-% DHA with 5 wt .-% TiO ₂ according to Example 2a
• 3. 5% by weight of DHA with 5% by weight of TiO ₂ Example 3a
• 4. 5 wt% DHA with 5 wt% Parsol TX
• 5. 5% by weight of DHA with 5% by weight of UV titanium M 263

The formulations are examined in the Minolta Chromameter CR-400 (illuminant C, observer 2 °) and show the following values: test L * (C) a * (C) b * (C) dL * (C) da * (C) db * (C) dE * ab (C) 1 76.92 -0.47 -0.52 - - - - 2 76.97 -0.55 0.61 0.05 -0.08 1.13 1.13 3 76.64 -0.5 0.45 -0.28 -0.03 0.97 1.01 4 70.14 0.41 7.53 -6.78 0.88 8.05 10.56 5 70.45 0.41 14.41 -6.47 0.88 14.94 16.3

The used market products (test formulations 4 and 5) show a strong discoloration after 3 months storage at 40 ° C. The particulate titanium dioxides according to the invention are visually unchanged with minor deviations from Test Formulation 1.

Example 3b: DHA degradation in test formulations

DHA is analyzed by an enzymatic determination method and is based on the following reaction:

• NADH = reduced nicotinamide adenine dinucleotide.

reagents:

Dihydroxyacetone (Merck), glycylglycine (Merck), (NH 4) ₂ SO ₄ (Merck), sucrose (Merck), NADH-Na ₂ (Merck) di-Sodium hydrogen phosphate dihydrate (Merck), sodium dihydrogen phosphate dihydrate (Merck), zinc chloride (Merck), glycerol dehydrogenase (Unitika Enzyms LTD).

DHA assay:

Determination of DHA concentration in a formulation based on the enzymatic DHA assay described below is based on the following reaction of dihydroxyacetone: DHA + NADH + H + → NAD + + glycerol

• A. Probenpuffer-Lösung: 1,06 g Glycylglycin, 0,42 g (NH₄)₂SO₄ und 10,0 g Sucrose werden in demineralisiertem Wasser gelöst und der pH-Wert wird mit NaOH-Lösung (10%) auf 9.0 eingestellt und die Probe auf ein Volumen von 100 ml aufgefüllt.
• B. NADH-Na₂-Lösung: 0.060 g NADH-Na₂ wird in 10.0 ml demineralisiertem Wasser gelöst.
• C. Puffer für die Glycerin Dehydrogenase-Lösung: a. 4.43 g Di-natriumhydrogenphosphat, b. 3.90 g Natriumdihydrogenphosphat-Dihydrat, c. 100.0 g Sucrose d. 0.003 g Zinkchlorid.

NADH shows an absorption coefficient of 365 nm. The enzyme glycerol dehydrogenase catalyses the above-mentioned reaction of dihydroxyacetone with NADH. The more DHA present, the more NADH is reacted in the reaction, and the NADH absorption at 365 nm decreases.

• A. Sample buffer solution: 1.06 g glycylglycine, 0.42 g (NH ₄ ) ₂ SO ₄ and 10.0 g sucrose are dissolved in demineralised water and the pH is adjusted to 9.0 with NaOH solution (10%) set and the sample on a volume of 100 ml filled.
• B. NADH-Na ₂ solution: 0.060 g NADH-Na ₂ is dissolved in 10.0 ml demineralized water.
• C. Buffer for glycerol dehydrogenase solution: a. 4.43 g of di-sodium hydrogen phosphate, b. 3.90 g sodium dihydrogen phosphate dihydrate, c. 100.0 g sucrose d. 0.003 g of zinc chloride.

• D. Glycerin-Dehydrogenase-Lösung: 10 mg Glycerindehydrogenase in 1 ml GlycerinDehydrogenasePuffer (Lösung C).
• E. DHA-Standards: 0.200 g DHA (Art.-No. 1.10150 Merck) wird in 100 ml demineralisiertem Wasser gelöst. Diese Lösung wird 1:10 verdünnt. Der Standard wird zweifach, unabhängig von einander, hergestellt. Die Abweichung beider Standards vom therotischen DHA-Gehalt muss 100% +/– 5% betragen.

All the substances mentioned are dissolved in 800 ml of demineralized water and the solution is adjusted to a pH of 7.0 with 1 N hydrochloric acid or sodium hydroxide solution. Thereafter, the volume of the sample is made up to 1000 ml with demineralized water.

• D. Glycerol dehydrogenase solution: 10 mg glycerol dehydrogenase in 1 ml glycerol dehydrogenase buffer (solution C).
• E. DHA Standards: 0.200 g DHA (Art. No. 1.10150 Merck) is dissolved in 100 ml demineralized water. This solution is diluted 1:10. The standard is produced twice, independently of each other. The deviation of both standards from the therotic DHA content must be 100% +/- 5%.

Sample preparation:

0.5 g-1.0 g of the test emulsion is placed in a calibrated 100 ml of flask weighed. 60 ml of hot (70 ° C) demineralized Water is poured in and it is stirred, taking the temperature at 60 ° C for 15 minutes constant remains.

If The solution has cooled down to the calibration mark refilled. The solutions obtained are over Filter a membrane filter to clear solution. From This solution has a volume of 0.1 ml for DHA determination used.

Measurement conditions:

• Cary 300 UV-Vis Spectrophotometer (Varian) (Wavelength = 365 nm, d = 1 cm).

As a reference demineralized water is used. Pitettenprozedur: Blank value solution Sample / standard solution sample buffer 1.00 ml 1.00 ml NADH-Na ₂ 0.10 ml 0.10 ml Demineralised water 2.00 ml 1.90 ml Sample or standard - 0.10 ml

The Absorption of these solutions is E1 (measurement 5 minutes after Mixture) The solutions are mixed as described above and measure before the enzyme is added. For every Sample is the absorbance before enzyme addition E1.

subsequent Add the glycerol dehydrogenase solution 0.01 ml each.

V

= Totalvolumen: 3.11 ml

v

= Probenvolumen: 0.1 ml

ε

= ε (NADH Na₂) = 3.42 l·mmol^–1·cm^–1

MW

= Molmasse (DHA): 90.08 g/mol

EW

= Probenlösungkonzentration (g/L)

The absorption of these solutions is E2 (measurement after 15 minutes after addition of the enzyme solution). ΔE = E1 - E2

V

= Total volume: 3.11 ml

v

= Sample volume: 0.1 ml

ε

= ε (NADH Na ₂ ) = 3.42 l · mmol ^-1 · cm ^-1

MW

= Molecular weight (DHA): 90.08 g / mol

EW

= Sample solution concentration (g / L)

Content of DHA [wt% in test formulation] logo CNRS logo INIST AE x V x MW x 100 ε · d · v · 1000 · EW (g / L)

• RT = Raumtemperatur

Typ anorganischer Filter/DHA Gehalt anorganischer UV-Filter DHA-Gehalt DHA-Gehalt Initialwert DHA-Gehalt Nach 3 Monaten bei RT (% Zerfall) DHA-Gehalt Nach 3 Monaten bei 40°C (% Zerfall) DHA (pur) 0% 5% 4,8 4,9 (0) 4,3 (10) DHA (pur) 0% 2% 1,9 2,0 (0) 1,7 (10) Parsol TX (TiO2/SiO2) 5% 5% 4.9 3.9 (20) 1.8 (63) Parsol TX (TiO2/SiO2) 1% 2% 1.9 1.7 (10) 1.1 (42) Kemira M263 5% 5% 4.2 2.4 (43) 0.3 (93) Kemira M263 1% 2% 1.8 1.5 (16) 0.7 (61) Eusolex T-VP 0608/8 (35% SiO2) 5% 5% 4,8 4,2 (13) 3,0 (38) Eusolex T-VP 0608/8 (35% SiO2) 1% 2% 1,9 1,8 (5,3) 1,7 (11) Eusolex T-VP 0608/10 (35% SiO2+ 10% Simethicone) 5% 5% 4,8 4,2 (13) 3,2 (33) Eusolex T-VP 0608/10 (35% SiO2+ 10% Simethicone) 1% 2% 2,0 1,9 (5,0) 1,7 (15) Rezepturbeispiel 1: Sonnenschutz Softcreme (O/W) Rohstoff (INCI) Gew.-% A Produkt aus Beispiel 2a 3,00 Steareth-10, Steareth-7, Stearyl alcohol 2,00 Glyceryl stearate, Ceteth-20 2,00 Glyceryl stearate 3,00 Microwax 1,00 Oleyl oleate 6,00 Cetearyl octanoate 14,00 Caprylic/capric triglyceride 4,00 Propylparaben 0,05 B Propylene glycol 4,00 Allantoin 0,20 Wasser 60,60 Methylparaben 0,15 With this described enzyme-based method, degradation is determined in the following test formulations using the test formulation described in Example 3a, abbreviated Eusolex T-VP 0608/08, and 3b, abbreviated Eusolex T-VP 0608/10.

• RT = room temperature

Type of inorganic filter / DHA Content of inorganic UV filters DHA content DHA content initial value DHA level After 3 months at RT (% decay) DHA content After 3 months at 40 ° C (% decay) DHA (pure) 0% 5% 4.8 4.9 (0) 4.3 (10) DHA (pure) 0% 2% 1.9 2.0 (0) 1.7 (10) Parsol TX (TiO2 / SiO2) 5% 5% 4.9 3.9 (20) 1.8 (63) Parsol TX (TiO2 / SiO2) 1% 2% 1.9 1.7 (10) 1.1 (42) Kemira M263 5% 5% 4.2 2.4 (43) 0.3 (93) Kemira M263 1% 2% 1.8 1.5 (16) 0.7 (61) Eusolex T-VP 0608/8 (35% SiO2) 5% 5% 4.8 4.2 (13) 3.0 (38) Eusolex T-VP 0608/8 (35% SiO2) 1% 2% 1.9 1.8 (5.3) 1.7 (11) Eusolex T-VP 0608/10 (35% SiO2 + 10% Simethicone) 5% 5% 4.8 4.2 (13) 3.2 (33) Eusolex T-VP 0608/10 (35% SiO2 + 10% Simethicone) 1% 2% 2.0 1.9 (5.0) 1.7 (15) Formulation Example 1: Sunscreen Soft Cream (O / W) Raw material (INCI) Wt .-% A Product from Example 2a 3.00 Steareth-10, Steareth-7, Stearyl alcohol 2.00 Glyceryl stearate, ceteth-20 2.00 Glyceryl stearate 3.00 Microwax 1.00 Oleyl oleates 6.00 Cetearyl octanoate 14.00 Caprylic / capric triglycerides 4.00 Propylparaben 0.05 B Propylene glycol 4.00 allantoin 0.20 water 60.60 methylparaben 0.15

production:

Heat phase A and phase B to 80 ° C. Slowly add phase B to phase A while stirring, homogenize and cool with stirring. Formulation Example 2: Sunscreen Soft Cream (O / W) Raw material (INCI) % A Product from Example 2b 10.00 Steareth-10, steareth-7, stearyl alcohol 3.00 Glyceryl stearate, ceteth-20 3.00 Glyceryl stearate 3.00 Microwax 1.00 Oleyl oleates 4.00 Cetearyl octanoate 10.50 Caprylic / capric triglycerides 4.00 Propylparaben 0.05 B Propylene glycol 4.00 allantoin 0.20 water 57.10 methylparaben 0.15

production:

Heat phase A and B to 80 ° C. Slowly add phase B to phase A with stirring, homogenize and cool while stirring. Formulation Example 3: Sunscreen Lotion (O / W) Raw material (INCI) % A Octocrylene 6.00 Butyl methoxydibenzoylmethane 2.00 Polyglyceryl-3-methylglucose distearate 4.00 Ethylhexyl stearate 8.00 Cetearyl isononanoate 2.00 PVP / eicosene copolymer 1.00 Tocopheryl acetate 1.00 B Xanthan gum 0.30 Sodium cetearyl sulfate 1.00 glycerin 5.00 water 65.70 C Product from Example 2a 4.00 D Phenoxyethanol, butylparaben, ethylparaben, propylparaben, methylparaben 1.00

production:

Heat phase A to 80 ° C. Pre-swell the Keltrol of phase B in the water, then add the remaining raw materials and heat to 80 ° C. Homogenize phase A to phase B and homogenize for 2 minutes (hand blender): cool with stirring and add phase C at 35 ° C. Homogenize again for 1 min (hand blender). Cool to room temperature and stir in phase D. Formulation Example 4: Sunscreen Lotion (O / W) A Steareth-10, steareth-7, stearyl alcohol 3.00 Glyceryl stearate, ceteth-20 3.00 Cetearyl octanoate 13,00 Glyceryl stearate 3.00 Oleyl oleates 7.00 Microwax 1.00 Caprylic / capric triglycerides 6.00 preservative qs Butyl methoxydibenzoylmethane 2.00 B 33% aqueous dispersion of the product out Example 2a 16.70 Propylene glycol 4.00 allantoin 0.20 water ad 100 preservative qs C water 10.00 dihydroxyacetone 4.00

production:

Heat phase A to 75 ° C and phase B to 80 ° C. Slowly stir phase B into phase A. Homogenize and cool while stirring. Formulation Example 5: Sunscreen Spray Lotion (O / W) A Product from Example 2b 5.00 Ethylhexyl methoxycinnamate, BHT 7.50 Benzophenone-3 2.50 PEG-100 stearate, glyceryl stearate 2.80 PPG-1-PEG-9 lauryl glycol ether 0.40 Dicapryl ether 4.50 Steareth-10 0.50 Stearyl alcohol 0.60 Dimethicone 2.00 B Dimethicone copolyol phosphate 2.50 Chitosan glycolate 2.00 glycerin 2.50 water ad 100 C PPG-1 trideceth-6, polyquaternium-37, propylene glycol dicaprylate / dicaprate 0.40 D preservative qs Demineralized water 10.00 Dihydroxyacetone 3.00

production:

phase Add A except for the titanium dioxide and heat to 60 ° C. Slowly incorporate titanium dioxide into the molten oil phase. Heat phase B-1 to 60 ° C, then phase B-2 with stirring Disperse. Phase A with high energy input into the phase Stir in B Cool with stirring, and at 40 ° C add phase C. Homogenize and stir Add phase D.

Formulation example 6

in the The following are exemplary recipes for cosmetic Preparations given in the same way with titanium dioxide after Example 2a or 2b are obtained (in the table jewels as titanium called dioxide). Otherwise, the INCI names the commercial compounds indicated.

UV-Pearl, OMC stands for the preparation with the INCI name:
Water (for EU: Aqua), ethylhexyl methoxycinnamate, silica, PVP, chlorphenesin, BHT; this composition is commercially available under the name Eusolex ^® UV Pearl ^TM OMC from Merck KGaA, Darmstadt.

The other UV pearls listed in the tables are each assembled analogously, with OMC being replaced by the specified UV filters. TABLE 1 W / O emulsions (numbers in% by weight) 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1-9 1-10 Titanium dioxide 3 2 5 10 7 4 15 1 3 3 Butylmethoxydibenzoylmethane 5 3 2 1 2 1 1 Zinc oxide 5 2 UV Pearl, OMC 30 15 15 15 15 15 15 15 15 15 Polyglyceryl-3 dimerates 3 3 3 3 3 3 3 3 3 3 Cera Alba 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Hydrogenated Castor Oil 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Paraffinium Liquidum 7 7 7 7 7 7 7 7 7 7 Caprylic / Capric Triglycerides 7 7 7 7 7 7 7 7 7 7 Hexyl Laurate 4 4 4 4 4 4 4 4 4 4 PVP / eicosene copolymer 2 2 2 2 2 2 2 2 2 2 Propylene glycol 4 4 4 4 4 4 4 4 4 4 Magnesium sulphates 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 tocopherol 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Tocopheryl acetate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Cyclomethicone 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 propylparabens 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Methyl parabens 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Water ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 Table 1 (continued) 1-11 1-12 1-13 1-14 1-15 1-16 1-17 1-18 Titanium dioxide 3 5 2 4 3 1 2 5 Benzylidene malonate polysiloxanes 1 0.5 Methylene bis-benztriazolyl tetramethylbutylphenol 1 1 0.5 Dihydroxyavcetone 5 3 2 5 1 3 7 2 Polyglyceryl-3 dimerates 3 3 3 3 Cera Alba 0.3 0.3 0.3 0.3 2 2 2 2 Hydrogenated Castor Oil 0.2 0.2 0.2 0.2 Paraffinium Liquidum 7 7 7 7 Caprylic / Capric Triglycerides 7 7 7 7 Hexyl Laurate 4 4 4 4 PVP / eicosene copolymer 2 2 2 2 Propylene glycol 4 4 4 4 Magnesium sulphates 0.6 0.6 0.6 0.6 tocopherol 0.5 0.5 0.5 0.5 Tocopheryl acetate 0.5 0.5 0.5 0.5 1 1 1 1 Cyclomethicone 0.5 0.5 0.5 0.5 propylparabens 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Methyl parabens 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Dicocoyl Pentyerythrityl Citrate (and) Sorbitan Sesquioleate (and) Cera Alba (and) Aluminum Stearate 6 6 6 6 PEG-7 Hydrogenated Castor Oil 1 1 1 1 Zinc stearate 2 2 2 2 Oleyl erucate 6 6 6 6 Decyl Oleate 6 6 6 6 Dimethicone 5 5 5 5 tromethamine 1 1 1 1 glycerin 5 5 5 5 allantoin 0.2 0.2 0.2 0.2 water ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 Table 1 (continued) 1-19 1-20 1-21 1-22 _1- 23 1-24 1-25 1-26 1-27 1-28 1-29 Titanium dioxide 1 2 5 1 3 4 5 2 3 3 3 Benzylidene malonate polysiloxanes 1 1 1 Methylene bis-benztriazolyl tetramethylbutylphenol 1 2 1 1 Zinc oxide 5 2 UV Pearl OMC 5 5 5 5 7 5 5 5 5 5 8th UV Pearl, OCR 10 5 UV-Pearl, ethylhexyl dimethylPABA 10 UV Pearl, Homosalates 10 UV-Pearl, Ethylhexyl salicylate 10 UV-Pearl, OMC, BP-3 10 UV-Pearl, OCR, BP-3 10 UV-Pearl, ethylhexyl dimethyl PABA, BP-3 10 UV Pearl, Homosalates, BP-3 10 UV-Pearl, ethyl hexyl salicylate, BP-3 10 Butylmethoxydibenzoylmethane 2 UV-Pearl OMC, 4-methylbenzylidene camphor 25 Polyglyceryl-3 dimerates 3 3 3 3 3 3 3 3 3 3 3 Cera Alba 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Hydrogenated Castor Oil 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Paraffinium Liquidum 7 7 7 7 7 7 7 7 7 7 7 Caprylic / Capric Triglycerides 7 7 7 7 7 7 7 7 7 7 7 Hexyl Laurate 4 4 4 4 4 4 4 4 4 4 4 PVP / eicosene copolymer 2 2 2 2 2 2 2 2 2 2 2 Propylene glycol 4 4 4 4 4 4 4 4 4 4 4 Magnesium sulphates 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 tocopherol 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Tocopheryl acetate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Cyclomethicone 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 propylparabens 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Methyl parabens 0.1 5 0.1 5 0.1 5 0.1 5 0.1 5 0.1 5 0.1 5 0.1 5 0.1 5 0.1 5 0.1 5 Water ad 100 Table 2: O / W emulsions, figures in% by weight 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 2-9 2-10 Titanium dioxide 3 2 5 2 5 2 5 2 5 3 Methylene bis-benztriazolyl tetramethylbutylphenol 1 2 1 Butylmethoxydibenzoylmethane 3 3 3 3 3 3 3 3 3 3 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid-bis (2-ethyl-hexyl) ester 1 5 4 6 7 2 1 4-Methylbenzylidene Camphor 2 3 4 3 2 Stearyl Alcohol (and) Steareth-7 (and) Steareth-10 3 3 3 3 3 3 3 3 3 3 Glyceryl Stearate (and) Ceteth-20 3 3 3 3 3 3 3 3 3 3 Microwax 1 1 1 1 1 1 1 1 1 1 Cetearyl octanoate 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 Caprylic / Capric Triglycerides 6 6 6 6 6 6 6 6 6 6 Oleyl Oleate 6 6 6 6 6 6 6 6 6 6 Propylene glycol 4 4 4 4 4 4 4 4 4 4 propylparabens 0,0 5 0,0 5 0,0 5 0,0 5 0,0 5 0,0 5 0,0 5 0,0 5 0,0 5 0,0 5 Methyl parabens 0.1 5 0.1 5 0.1 5 0.1 5 0.1 5 0.1 5 0.1 5 0.1 5 0.1 5 0.1 5 tromethamine 1.8 Water ad 100 ad 100 ad 100 Ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 Table 2 (continued) 2-11 2-12 2-13 2-14 2-15 2-16 2-17 2-18 Titanium dioxide 3 1 2 5 4 3 2 5 Benzylidene malonate polysiloxanes 1 0.5 Methylene bis-benztriazolyl tetramethylbutylphenol 1 1 0.5 Butylmethoxydibenzoylmethane 3 3 3 3 3 3 3 3 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid-bis (2-ethyl-hexyl) ester 1 5 4 6 7 Zinc oxide 2 UV Pearl, OMC 15 15 15 30 30 30 15 15 4-Methylbenzylidene Camphor 3 Phenylbenzimidazole sulfonic acid 4 Stearyl Alcohol (and) Steareth-7 (and) Steareth-10 3 3 3 3 Glyceryl stearate 3 3 3 3 Microwax 1 1 1 1 Cetearyl octanoate 11.5 11.5 11.5 11.5 Caprylic / Capric Triglycerides 6 6 6 6 14 14 14 14 Oleyl Oleate 6 6 6 6 Propylene glycol 4 4 4 4 Glyceryl Stearate SE 6 6 6 6 Stearic acid 2 2 2 2 Persea Gratissima 8th 8th 8th 8th propylparabens 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Methyl parabens 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 tromethamine 1.8 glycerin 3 3 3 3 Water ad 100 ad 100 Ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 Table 2 (continued) 2-19 2-20 2-21 2-22 2-23 2-24 2-25 2-26 2-27 2-28 Titanium dioxide 10 5 7 8th 2 1 3 3 6 2 Benzylidene malonate polysiloxanes 1 2 1 1 1 0.5 Butylmethoxydibenzoylmethane 3 3 3 3 3 3 3 3 3 3 Octocrylene 1 5 4 6 7 2 1 Methylene bis-benztriazolyl tetramethylbutylphenol 1 2 1 1 1 0.5 Zinc oxide 5 2 2 UV Pearl, OMC 15 15 15 15 15 15 15 15 15 15 Caprylic / Capric Triglycerides 14 14 14 14 14 14 14 14 14 14 Glyceryl Stearate SE 6 6 6 6 6 6 6 6 6 6 Stearic acid 2 2 2 2 2 2 2 2 2 2 Persea Gratissima 8th 8th 8th 8th 8th 8th 8th 8th 8th 8th propylparabens 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Methyl parabens 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 glycerin 3 3 3 3 3 3 3 3 3 3 Water ad 100 ad 100 ad 100 Ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100

Table 3: Gels, numbers in wt% 3-1 3-2 3-3 3-4 3-5 3-6 3-7 3-8 3-9 3-10 a = aqueaous gel Titanium dioxide 5 2 5 1 1 1 1 1 3 3 Butylmethoxydibenzoylmethane 2 2 2 2 2 2 2 2 2 2 Dihydroxyacetone 1 5 4 6 7 2 1 Benzylidene malonate polysiloxanes 1 1 2 1 1 Methylene bis-benztriazolyl tetramethylbutylphenol 1 1 2 1 Zinc oxide 2 5 2 UV Pearl, ethylhexyl methoxycinnamate 30 15 15 15 15 15 15 15 15 15 4-Methylbenzylidene Camphor 2 Prunus Dulcis 5 5 5 5 5 5 5 5 5 5 Tocopheryl acetate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Caprylic / Capric Triglycerides 3 3 3 3 3 3 3 3 3 3 octyldodecanol 2 2 2 2 2 2 2 2 2 2 Decyl Oleate 2 2 2 2 2 2 2 2 2 2 PEG-8 (and) Tocopherol (and) Ascorbyl Palmitate (and) Ascorbic Acid (and) Citric Acid 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 sorbitol 4 4 4 4 4 4 4 4 4 4 Polyacrylamide (and) C13-14 isoparaffin (and) laureth-7 3 3 3 3 3 3 3 3 3 3 propylparabens 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Methyl parabens 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 tromethamine 1.8 Water ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 Table 3 (continued) 3-11 3-12 3-13 a = aqueaous gel Titanium dioxide 3 1 2 Benzylidene malonate polysiloxanes 1 0.5 Methylene bis-benztriazolyl tetramethylbutylphenol 1 1 0.5 Butylmethoxydibenzoylmethane 2 2 2 2- (4-hydroxy-3,5-dimethoxybenzylidene) malonic acid-bis (2-ethyl-hexyl) ester 1 5 4 Zinc oxide 2 UV Pearl, ethylhexyl methoxycinnamate 15 15 15 Prunus Dulcis 5 5 5 Tocopheryl acetate 0.5 0.5 0.5 Caprylic / Capric Triglycerides 3 3 3 octyldodecanol 2 2 2 Decyl Oleate 2 2 2 PEG-8 (and) Tocopherol (and) Ascorbyl Palmitate (and) Ascorbic Acid (and) Citric Acid 0.05 0.05 0.05 sorbitol 4 4 4 Polyacrylamide (and) C13-14 isoparaffin (and) laureth-7 3 3 3 Carbomer propylparabens 0.05 0.05 0.05 Methyl parabens 0.15 0.15 0.15 allantoin tromethamine Water ad 100 ad 100 Ad 100 Table 3 (continued) 3-14 3-15 3-16 3-17 3-18 3-19 3-20 3-21 Titanium dioxide 1 5 3 1 2 8th 12 1 Butylmethoxydibenzoylmethane 2 2 2 2 2 2 2 2 UV Pearl, OMC 15 10 10 10 10 15 10 UV Pearl, OCR 10 UV-Pearl, OMC, Methylene bis-benztriazolyl tetramethylbutylphenol 7 6 UV-Pearl, ethylhexyl salicylate, butylmethoxydibenzoylmethane 10 Disodium phenyl dibenzimidazole tetrasulfonates 3 3 3 Phenylbenzimidazole sulfonic acid 2 2 3 3 Prunus Dulcis 5 5 5 Tocopheryl acetate 0.5 0.5 0.5 Caprylic / Capric Triglycerides 3 3 3 octyldodecanol 2 2 2 Decyl Oleate 2 2 2 PEG-8 (and) Tocopherol (and) Ascorbyl Palmitate (and) Ascorbic Acid (and) Citric Acid 0.05 0.05 0.05 sorbitol 4 4 4 5 5 5 5 5 Polyacrylamide (and) C13-14 isoparaffin (and) laureth-7 3 3 3 Carbomer 1.5 1.5 1.5 1.5 1.5 propylparabens 0.05 0.05 0.05 Methyl parabens 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 allantoin 0.2 0.2 0.2 0.2 0.2 tromethamine 2.4 2.4 2.4 2.4 2.4 Water Ad 100 Ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 ad 100 Formulation example 7: Sunscreen spray with tanning intensification A) Ceralution ^® C; Fa. Sasol 15.0% B) product according to Example 2a 5.0% Ethylhexyl methoxycinnamate 08.04% Ethyl hexyl salicylates 08.04% Tocopheryl acetate 0.6% Cyclomethicone 1.0% C12-15 alkyl benzoates 02.05% Tridecyl salicylates 02.05% C) dihydroxyacetone 3% Water (Aqua), Deionized ad 100 Water (Aqua), Deionized with 4% Avicel CL 611 25.0% (Microcrystalline cellulose (and) cellulose gum) D) preservative qs

Preparation: Phase B is slowly added to Phase A with stirring at room temperature. After that Phase C is added. Subsequently, the phase D is added.

INCI Ceralution ^® C:

Aqua (and) Capric / Caprylic triglycerides (and) Glycerol (and) Ceteareth-25 (and) Sodium Dicocoylethylenediamine PEG-15 Sulfates (and) Sodium Lauroyl Lactylate (and) Behenyl Alcohol (and) Glyceryl Stearate (and) Glyceryl Stearate Citrate (and) and) gum arabic (and) xanthan gum (and) phenoxyethanol (and) methylparaben (and) ethylparaben (and) butylparaben (and) isobutylparaben Formulation example 8: sunscreen lotion (O / W); A % Stearyl Alcohol (and) Steareth-7 3.00 (and) steareth-10 Glyceryl Stearate (and) Ceteth-20 3.00 Cetearyl octanoate 15.50 Glyceryl stearate 3.00 Oleyl Oleate 7.00 Microwax 1.00 Caprylic / Capric Triglycerides 6.00 B Product according to Example 2b 5.00 Propylene glycol 4.00 preservative qs Water, demineralized ad 100.00

production:

Stir the titanium dioxide in phase B and heat to 80 ° C. Heat phase A to 75 ° C. Slowly add phase B to phase A while stirring, homogenize and cool with stirring. Recipe Example 9: Self Tanning Lotion (W / O) raw material INCI [%] A Titanium dioxide according to the invention 3.00 Abil EM 97 (1) BIS-PEG / PPG-14/14 DIMETHICONE, 1.50 Cyclopentasiloxane Abil EM 90 (1) CETYL PEG / PPG-10/1 DIMETHICONE 1.30 Mirasil CM 5 (2) CYCLOMETHICONE 13,00 Ceraphyl 368 (3) ETHYLHEXYL PALMITATE 2.00 SFE 839 (4) Cyclopentasiloxane, 7.00 DIMETHICONE / vinyldimethicone CROSSPOLYMER Tegosoft DEC (1) DIETHYLHEXYL CARBONATE 5.00 Perfume oil Babylon (5) PERFUME 0.30 B Water, demineralized AQUA (WATER) ad 100 DHA (6) dihydroxyacetone 5.00 1,2-propanediol (6) PROPYLENE GLYCOL 31.50 Glycerin, anhydrous (6) GLYCERINE 3.00 Magnesium sulfate heptahydrate (6) MAGNESIUM SULFATE 2.00 Ethanol 96% pure (6) ALCOHOL 8.00 preservative qs

production:

Homogeneously disperse the TiO2 in phase A. Dissolve the magnesium sulfate heptahydrate in the water of phase B, weigh the remaining raw materials and mix. Phase B slowly in Phase A with stirring add (with the MFR stirrer at 300-400 rpm) then again 2 min. stir at 1200 rpm. Homogenize (with the MFR stirrer for 2 min at 2000 rpm).

Sources:

• (1) Degussa Goldschmidt AG
• (2) Rhodia GmbH
• (3) ISP Global Technologies
• (4) GE Silicones Holland
• (5) drom
• (6) Merck KGaA / ^Rona®
• (7) Nipa Laboratories GmbH

Formulation example 10: Day cream with DHA Rapid + UV filter (O / W) ingredients INCI [%] A Inventive TiO 2 4:00 Eusolex OCR (5) OCTOCRYLENE 3:00 Eusolex 9020 (5) BUTYL METHOXYDIBENZOYLMETHANE 1:50 Tego Care 150 (1) GLYCERYL STEARATE, STEARETH-25, CETETH-20, 8:00 STEARYL ALCOHOL Lanette O (2) CETEARYL ALCOHOL 1:50 Tegosoft liquid (1) CETEARYL ETHYLHEXANOATE 5:00 Miglyol 812 N (3) CAPRYLIC / CAPRIC TRIGLYCERIDE 5:00 Abil wax 2434 (1) STEAROXY DIMETHICONE 1.20 Dow Corning 200 (100 cs) (4) DIMETHICONE 12:50 RonaCare ^® AP (5) BIS-ETHYLHEXYL HYDROXYDIMETHOXY 12:50 BENZYLMALONATE preservative qs B 1,2-Propanediol (5) PROPYLENE GLYCOL 3:00 preservative qs Water, demineralized AQUA (WATER) ad 100 C DHA Rapid (5) DIHYDROXYACETONE, TROXERUTINE 5:00 Water, demineralized AQUA (WATER) 10:00 D (6) PERFUME qs

Procedure:

phase Heat A and Phase B to 80 ° C. Phase B slowly in phase A stir. Homogenize.

Under Stirring cool. Add phase C at 40 ° C.

suppliers:

• (1) Degussa Goldschmidt AG
• (2) Cognis GmbH
• (3) Sasol Germany GmbH
• (4) Dow Corning
• (5) Merck KGaA / ^Rona®
• (6) Bell Flavors & Fragrances

Recipe example 11: Self-tanning care with UV protection (O / W) ingredients INCI [%] A Inventive TiO 2 1:50 Imwitor 900 (1) GLYCERYL STEARATE 4:00 Stearic acid (2) STEARIC ACID 1:50 Cetyl alcohol (2) CETYL ALCOHOL 1:50 Arlamol S 7 (3) CYCLOMETHICONE, PPG-15 STEARYL ETHER 12:50 Lanol 99 (4) ISONONYL ISONONANOATE 11:00 Dow Corning 200 (100 cs) (5) DIMETHICONE 2:00 RonaCare ^® tocopherol acetate (2) TOCOPHERYL ACETATE 12:50 Simulgel EG (6) SODIUM ACRYLATE, SODIUM ACRYOYL DIMETHYL 1:00 TAURATE COPOLYMER, ISOHEXADECANE, POLYSORBATE 80 B Rhodicare XC (7) XANTHAN GUM 12:30 Glycerol, anhydrous (2) GLYCERIN 1:00 Water, demineralized AQUA (WATER) ad 100 C dihydroxyacetone (2) dihydroxyacetone 3:00 preservative qs Water, demineralized AQUA (WATER) 8:00 pm D Eusolex UV-Pearls ^{® TM} OMC (2) AQUA (WATER), ETHYLHEXYL METHOXYCINNAMATE SILICA, PVP, CHLOROPHENESINE, BHT 13.80

production:

phases Heat A and B separately to 75 ° C. Phase B while stirring enter in phase A.

Under Stirring cool and at 30 ° C in succession incorporate phases C and D.

With Citric acid adjust the pH to 4-4.5.

Manufacturer:

• (1) Sasol Germany GmbH
• (2) Merck KGaA / ^Rona®
• (3) Uniqema
• (4) Seppic
• (5) Dow Corning
• (6) Gattefossé GmbH
• (7) Rhodia GmbH (8) Nipa Laboratories GmbH

Formulation Example 12: Self-Tanning Gel Emulsion (W / Si) raw material INCI [%] A Dow Corning 5225C (1) CYCLOPENTASILOXANE, PEG / PPG-18/18 20.00 DIMETHICONE DM-fluid-A-6cs (2) DIMETHICONE 4.00 soybean oil (3) GLYCINE SOY (SOYBEAN OIL) 2.00 RonaCare ^® tocopherol acetate (4) TOCOPHERYL ACETATE 0.50 B TiO ₂ according to the invention (example 2a) 2.50 RonaCare ^® Ectoin (4) ECTOIN 0.30 1,2-propanediol (4) PROPYLENE GLYCOL 30.00 dipropylene (5) DIPROPYLENE GLYCOL 10.00 sodium chloride (4) SODIUM CHLORIDE 1.00 Ethanol 96% pure (4) ALCOHOL 5.00 1% Caramel 250 in water (6) CARAMEL 2.50 1% FD & C Yellow No. 6 in water (5) AQUA (WATER), CI 15985 (FD & C YELLOW NO. 6) 0.25 Water, demineralized AQUA (WATER) ad 100 C dihydroxyacetone (4) dihydroxyacetone 3.50 Water, demineralized AQUA (WATER) 10.00 D Perfume (7) PERFUME qs

production:

The dissolved phase B slowly with stirring to phase A (at about 400 rpm with the MFR stirrer).

Then add phase C and phase D. Then stir for approx. 1 min. At 900 rpm.
Homogenize (1 min at 2000 rpm with the MFR stirrer)

Sources:

• (1) Dow Corning
• (2) S. Black GmbH
• (3) Gustav Heess GmbH
• (4) Merck KGaA / ^Rona®
• (5) BASF AG
• (7) drom

Recipe Example 13: Light & Sparkling Self Tanning Cream (OMI) ingredients INCI [%] A TiO ₂ according to the invention (example 2b) 1.50 Montanov 68 (1) CETEARYL ALCOHOL, CETEARYL GLUCOSIDE 4:00 Lanette O (2) CETEARYL ALCOHOL 1:00 Span 60 (3) SORBITAN STEARATE 1:50 Cosmacol ELI (4) C12-13 ALKYL LACTATE 4:00 Cosmacol EMI (4) DI-C12-13 ALKYL MALATE 2:50 Arlamol HD (3) Isohexadecane 3:00 RonaCare ^® Tocopherol Acetate (5) TOCOPHERYL ACETATE 12:50 B Ronastar ^® Silver (5) CALCIUM ALUMINUM BOROSILICATE, SILICA, 1:00 CI 77891 (TITANIUM DIOXIDE), TIN OXIDE RonaCare ^® Ectoin (5) ECTOIN 12:50 Glycerol, anhydrous (5) GLYCERIN 3:00 preservative qs Water, demineralized AQUA (WATER) ad 100 C Sepigel 305 (1) LAURETH-7, POLYACRYLAMIDE, C13-14 ISOPARAFFIN 0.60 D DHA Plus (5) DIHYDROXYACETONE, SODIUM METABISULFITE, 2:00 MAGNESIUM STEARATE Water, demineralized AQUA (WATER) 4:00 e Perfume (7) PERFUME qs

production:

phase Heat A and B separately to 75 ° C. Phase A below Add stirring to phase B. At 50 ° C, phase C too Add phase A / B and homogenize. At 40 ° C phases D and E in succession, cool to RT with stirring.

Suppliers:

• (1) Seppic
• (2) Cognis GmbH
• (3) Uniqema
• (4) Nordmann & Rassmann
• (5) Merck KGaA / ^Rona®
• (6) Nipa Laboratories GmbH
• (7) drom

Formulation example 14: Self-tanning lotion (O / W) (spray or impregnation solution for wipes) ingredients INCI [%] A Inventive TiO ₂ 1:00 Prisorine 2021 (2) ISOPROPYL ISOSTEARATE 8:00 Prisorine 2034 (2) PROPYLENE GLYCOL ISOSTEARATE 1:00 Arlasolve 200 (2) Isoceteth-20 3.78 Arlacel 987 (1) SORBITAN ISOSTEARATE 1.12 Atlas G-2330 (1) Sorbeth-30 1:50 B dihydroxyacetone (3) dihydroxyacetone 5:00 Water, demineralized AQUA (WATER) ad 100 Arlasolve DMI (1) DIMETHYL ISOSORBIDE 3:00 C preservative qs 1,2-propanediol (3) PROPYLENE GLYCOL 12:56 D Perfume (4) PERFUME qs

production:

phase Mix until everything is homogeneous. Mix phase B until a transparent one Solution is obtained.

phase Add A to phase B with stirring. Homogenize. pH Set value to approx. 4.

phase C & D with stirring to admit.

Suppliers:

• (1) Uniqema
• (2) Uniqema Chemie GmbH
• (3) Merck KGaA / ^Rona®
• (4) Parfex
• (5) ISP Global Technologies

Formulation Example 15: Day Care Cream DUO-ACTIV (O / W) raw material INCI [%] A (1) Inventive TiO ₂ 2.00 Eusolex ^® 9020 (1) BUTYL METHOXYDIBENZOYLMETHANE 2.00 Eusolex ^® OCR (1) OCTOCRYLENE 1.00 Arlacel 165 VP (2) GLYCERYL STEARATE, PEG-100 STEARATE 10.00 cetyl alcohol (1) cetyl alcohol 2.00 Cetiol B (3) DIBUTYL ADIPATE 15.00 Paraffin liquid (1) PARAFFINUM LIQUIDUM (MINERAL OIL) 9.00 Shea butter stuck (4) BUTYROSPERMUM PARKII (SHEA BUTTER) 2.00 Dow Corning 200 Fluid (350 cs) (5) DIMETHICONE 0.50 antioxidant qs preservative qs B RonaCare ^® Ectoin (1) ECTOIN 0.30 Karion FP, liquid (1) SORBITOL 3.00 Glycerin, anhydrous (1) GLYCERIN 2.00 complexing qs preservative qs Water, demineralized AQUA (WATER) ad 100 C dihydroxyacetone (1) dihydroxyacetone 3.00 erythrulose (6) ERYTHRULOSE 1.50 Water, demineralized AQUA (WATER) 10.00

production:

phase A to 75 ° C, phase B to 80 ° C. Phase B stir slowly into phase A.

Homogenize and cool with stirring. At 40 ° C phase Stir in C

Sources:

• (1) Merck KGaA / ^Rona®
• (2) Uniqema
• (3) Cognis GmbH
• (4) H. Erhard Wagner GmbH
• (5) Dow Corning
• (6) PENTAPHARM / DSM

Formulation example 16: sun protection cream high protection (O / W) ingredients INCI [%] A 33% oily dispersion of the TiO ₂ according to the invention 13:00 Eusolex ^® OCR (1) OCTOCRYLENE 10:00 Eusolex ^® 9020 (1) BUTYL METHOXYDIBENZOYLMETHANE 4:00 Eosolex ^® 4360 (1) BENZOPHENONE-3 4:00 Emulgade F (2) SODIUM CETEARYL SULFATE, CETEARYL ALCOHOL, 3:00 PEG-40 CASTOR OIL Tegin (3) GLYCERYL STEARATE SE 1:50 Syncrowax HGLC (4) C18-36 ACID TRIGLYCERIDE 1:50 Softisan 100 (5) HYDROGENATED COCO-GLYCERIDES 1:50 Dow Corning 345 (6) CYCLOMETHICONE 6:00 am X-Tend 226 (7) PHENYLETHYL BENZOATE 4:50 Antaron V-216 (7) PVP / HEXADECENE COPOLYMER 1:00 Oxynex ST Liquid (1) DIETHYLHEXYL SYRINGYLIDENEMALONATE 12:50 preservative qs B Eusolex ^® 232 (1) PHENYLBENZIMIDAZOLE SULFONIC ACID 3:00 Triethanolamine (1) TRIETHANOLAMINE 1.60 Keltrol RD (9) XANTHAN GUM 12:20 RonaCare ^® Ectoin (1) ECTOIN 12:10 Glycerol, anhydrous (1) GLYCERIN 5:00 complexing qs preservative qs Water, demineralized AQUA (WATER) ad 100 Perfume PERFUME qs

Eusolex 232 in water and disperse good. With triethanolamine neutralize until a clear solution is obtained.

Keltrol in phase B water with stirring until dispersing a homogeneous "gel" is present, then with stirring Add the remaining ingredients of Phase B and for as long stir at RT until a homogeneous phaser is present. phase Mix A and stir briefly at RT.

phase Heat A and B separately to 80 ° C, stir phase A underneath Add to phase B and homogenize.

Under Cool the mixture to RT (check pH value should be pH 7). Add perfume under stirring.

suppliers:

• (1) Merck KGaA / ^Rona®
• (2) Cognis GmbH
• (3) Degussa Goldschmidt AG
• (4) Croda GmbH
• (5) Sasol Germany GmbH
• (6) Dow Corning
• (7) ISP Global Technologies
• (8) BASF AG
• (9) C.P. Kelco

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - DE 102007013368 [0068]
• FR 2326405 A [0080]
• FR 2440933 A [0080]
• EP 0114607 A [0080]
• WO 93/04665 [0085]
• EP 0 487 404 A [0085]
• WO 99/66896 [0100]
• US 6242099 B1 [0115]
• WO 00/09652 [0115]
• WO 00/72806 [0115]
• WO 00/71084 [0115]
• - DE 4116123 A [0131]
• - DE 4308282 [0174]

Cited non-patent literature

• Eugen Scholz, Karl Fischer Titration, Springer-Verlag 1984 [0013]
• - Ullmanns Enzyklopadie der Technischen Chemie, 4th Edition, 1978, Volume 15, page 117 ff: K. Recker, Single Crystal Growth [0023]
• - Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53-64 [0074]
• - Rowe Color Index, 3rd Edition, Society of Dyers and Colourists, Bradford, England, 1971 [0117]

Claims (14)

Hydrothermally treated titanium dioxide particles, aftertreated with a silicon dioxide coating, wherein the content of SiO ₂ in the coating 25 to 45 weight percent, based on the TiO ₂ content of the particles to be coated. Titanium dioxide particles according to claim 1, wherein in addition to the SiO ₂ coating, a further coating is applied containing organic acids selected from the group of stearic acid, lauric acid, caproic acid or palmitic acid, polyols or organosilicon compounds. Titanium dioxide particles according to claim 1 or 2, characterized characterized in that the titanium dioxide is doped with iron. Titanium dioxide particles according to one or more of Claims 2 to 3, characterized in that the organosilicon Compound is selected from silicone oils or Alkylsilanes. Preparation containing titanium dioxide particles after one of claims 1 to 4. Preparation according to claim 5, characterized in that that it is an aqueous or oily dispersion is. Preparation according to claim 5, characterized in that that it is a topically applicable preparation. Preparation according to claim 5, characterized in that that it is a preparation selected from the group Fibers, textiles, including their coatings, Paints, coating systems, films and packaging for the protection of food, plants or technical goods is. Preparation according to claim 5, 6 or 7, characterized the preparation is dihydroxyacetone or a dihydroxyacetone derivative contains. Preparation according to claim 9, characterized that the concentration of Dihydroxyaxeton or Dihydroxyacetonderivat in the range of 1 to 12 weight percent, based on the preparation. Preparation according to one or more of the claims 5 to 10, characterized in that the preparation at least contains an organic UV filter Preparation according to one or more of the claims 5 to 11, characterized in that the preparation one or contains several antioxidants. Process for the preparation of a preparation according to one or more of claims 7 and 9 to 12, characterized characterized in that titanium dioxide particles after at least one of claims 1 to 4 with a cosmetically or dermatologically suitable carrier and optionally other ingredients is mixed. Use of the titanium dioxide particles after one or several of claims 1 to 4 for the stabilization of dihydroxyacetone or derivatives of the dihydroxyacetone.