(en)A process for protecting human skin or hair against the harmful effects of ageing and environmental toxins involving contacting the skin or hair with a composition containing a Vaccinium plant extract.

1.ApplicationNumber: US-49621304-A
1.PublishNumber: US-2005095305-A1
2.Date Publish: 20050505
3.Inventor: ARIAS CARMEN
FABRY BERND
RULL PROUS SANTIAGO

4.Inventor Harmonized: ARIAS CARMEN(ES)
FABRY BERND(DE)
RULL PROUS SANTIAGO(ES)

5.Country: US
6.Claims:
(en)A process for protecting human skin or hair against the harmful effects of ageing and environmental toxins involving contacting the skin or hair with a composition containing a Vaccinium plant extract.

7.Description:
(en)FIELD OF THE INVENTION
This invention relates generally to the cosmetics field and, more particularly, to new preparations against the effects of ageing and environmental toxins on the skin and hair that are distinguished by an effective content of vaccinium extracts and to the use of the extracts against a number of effects which damage the skin and hair.
PRIOR ART
The desire for eternal youth and beauty existed even in ancient times. Whereas legend has it that Cleopatra regularly bathed in asses' milk—today we know about the effect of the proteins present in such milk—less well-off ladies had to hope that their wish would be heard by the gods. It has to be assumed that this was only rarely crowned with success. Nowadays, a youthful appearance and a skin virtually free from wrinkles is not the privilege of just a few, but is basically available to all women despite the occasionally considerable differences in the price of the preparations. Even if cosmetic chemistry cannot work miracles, knowledge of the biochemical processes in the cells of skin and hair has increased enormously in recent years. As a result, there are of course theories as to how damage caused by natural ageing or environmental influences can be prevented or eliminated. However, the demands that female (and increasingly male) consumers expect such anti-ageing preparations to sastisfy have also increased. Quite apart from the fact that, basically, the preparations are expected to have a “caring” character and to show optimal compatibility with the skin and, optionally, the mucosa, they are required to provide protection against UV radiation and environmental toxins, to stimulate the immune system and to have anti-inflammatory activity.
In this connection, reference is made, for example to German patent application DE 3027933 A1 (Inverni Della Beffa) which describes pharmaceutical preparations for topical application to the skin which contain vaccinium extracts with a high content of anthocyanosides as their active ingredient. These preparations stimulate the circulation and are used for healing wounds. European patent application EP 0 953 353 A1 (Laboratoires Pharmascience) describes the use of vaccinium extracts as anti-urease agents. International patent application WO 01/45648 (L'Oréal) relates to the use of plants of the genus Vaccinium for reducing or inhibiting the glycation of proteins in the skin or related structures. International patent application WO 99/55352 (Avon) proposes skin-whitening preparations which contain a synergistic combination of extract of licorice root and an antioxidant, for example vaccinium extract. Decorative cosmetics containing vaccinium extracts and oil components are proposed in International patent application WO 01/45662 (Laboratoires Seriobiologiques). French patent FR 2659556 B1 (Mu Lab Eurl) describes preparations containing extracts of blueberries and arnica. French patent FR 2612775 B1 (Thorel) reports on skin treatment preparations which, besides vitamin A, contain sources for sulfur, manganese and magnesium. These preparations preferably contain blueberry extracts and ascorbic acid. Finally, International patent application WO 96/30033 discloses vaccinium extracts in suitable formulations, for example tablets or capsules, which are used, for example, for cleaning surgical instruments.
Accordingly, the problem addressed by the present invention was to provide new anti-ageing preparations containing an active ingredient that would satisfy the complex requirement profile described above. In addition, with the BSE debate in mind, this “multifunction component” would be a vegetable product.


DESCRIPTION OF THE INVENTION
The present invention relates to anti-ageing preparations which are characterized in that they have an effective content of plant extracts of the genus Vaccinium.
It has surprisingly been found that plant extracts of the genus Vaccinium protect the skin and hair against attack by free radicals. Their anti-oxidative effect is distinctly superior to that of tocopherol and butyl hydroxytoluene and comparable with that of vitamin C. The extracts are also active against UV-A and UV-B radiation and, in particular, reduce the release of matrix metalloproteinases (MMPs), lactate dehydrogenase (LDH) and prostaglandins. They also have anti-inflammatory activity because they reduce the release of proteases, especially collagenases, and lessen the respiratory burst of human granulocytes without damaging them. The extracts stimulate the immune system of the skin, the growth and regeneration of fibroblasts and the synthesis of glucose-6-phosphate dehydrogenase (G6PD). Finally, they also promote the lipolysis of fats in the skin.
Accordingly, the present invention also relates to the use of plant extracts of the genus Vaccinium as agents for protecting the skin and hair against ageing and environmental influences in which they may be present in quantities of 0.001 to 1% by weight and preferably 0.005 to 0.01% by weight, based on the content of active substances.
Vaccinium Extracts
To botanists, the genus Vaccinium is a group of around 450 species of which Vaccinium myrtyllus , the bilberry or blueberry, is the most important. Other known species include Vaccinium angustifollium, Vaccinium arboreum, Vaccinium arctostaphylos, Vaccinium caespitosum, Vaccinium corymbosum, Vaccinium hirsutum, Vaccinium macrocarpum, Vaccinium ovatum, Vaccinium oxycoccus, Vaccinium stamineum, Vaccinium uliginosum and Vaccinium vitis idaea . The vaccinium extracts contain as active ingredients a mixture of at least 15 different anthocyanosides such as, for example, the following:


In general, the vaccinium extracts contain 20 to 25% by weight of anthocyanosides, 5 to 10% by weight of tannins and small quantities of various alkaloids (for example myrtin and epimyrtin), phenolic acids and glycosides containing quercitrin, isoquercitrin and hyperoside.
Extraction
The extracts may be prepared by methods known per se, i.e. for example by aqueous, alcoholic or aqueous/alcoholic extraction of the plants or parts thereof. Particulars of suitable conventional extraction processes, such as maceration, remaceration, digestion, agitation maceration, vortex extraction, ultrasonic extraction, countercurrent extraction, percolation, repercolation, evacolation (extraction under reduced pressure), diacolation and solid/liquid extraction under continuous reflux in a Soxhlet extractor, which are familiar to the expert and which may all be used in principle, can be found, for example, in Hagers Handbuch der pharmazeutischen Praxis (5th Edition, Vol. 2, pp. 1026-1030, Springer Verlag, Berlin-Heidelberg-New York 1991). Percolation is advantageous for industrial use. Fresh plants or parts thereof are suitable as the starting material although dried plants and/or plant parts which may be mechanically size-reduced before extraction are normally used. Any size reduction methods known to the expert, for example freeze grinding, may be used. Preferred solvents for the extraction process are organic solvents, water (preferably hot water with a temperature above 80° C. and more particularly above 95° C.) or mixtures of organic solvents and water, more particularly low molecular weight alcohols with more or less high water contents. Extraction with methanol, ethanol, pentane, hexane, heptane, acetone, propylene glycols, polyethylene glycols, ethyl acetate and mixtures and water-containing mixtures thereof thereof is particularly preferred. The extraction process is generally carried out at 20 to 100° C., preferably at 30 to 90° C. and more particularly at 60 to 80° C. In one preferred embodiment, the extraction process is carried out in an inert gas atmosphere to avoid oxidation of the ingredients of the extract. This is particularly important where extraction is carried out at temperatures above 40° C. The extraction times are selected by the expert in dependence upon the starting material, the extraction process, the extraction temperature and the ratio of solvent to raw material, etc. After the extraction process, the crude extracts obtained may optionally be subjected to other typical steps, such as for example purification, concentration and/or decoloration. If desired, the extracts thus prepared may be subjected, for example, to the selective removal of individual unwanted ingredients. The extraction process may be carried out to any degree, but is usually continued to exhaustion. Typical yields (=extract dry matter, based on the quantity of raw material used) in the extraction of dried leaves are in the range from 3 to 15 and more particularly 6 to 10% by weight. The present invention includes the observation that the extraction conditions and the yields of the final extracts may be selected according to the desired application. These extracts, which generally have active substance contents (=solids contents) of 0.5 to 10% by weight), may be used as such, although the solvent may also be completely removed by drying, more particularly by spray or freeze drying, a deep red colored solid remaining behind. The extracts may also be used as starting materials for producing the pure active substances mentioned above unless they can be synthesized by a more simple and inexpensive method. Accordingly, the active substance content in the extracts may be from 5 to 100% by weight and is preferably from 50 to 95% by weight. The extracts themselves may be present as water-containing preparations and/or as preparations dissolved in organic solvents and as spray-dried or freeze-dried water-free solids. Suitable organic solvents in this connection are, for example, aliphatic alcohols containing 1 to 6 carbon atoms (for example ethanol), ketones (for example acetone), halogenated hydrocarbons (for example chloroform or methylene chloride), lower esters or polyols (for example glycerol or glycols).
Anti-Ageing Preparations
The preparations according to the invention are normally formulated as creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compounds, stick preparations, powders or ointments. These preparations may also contain mild surfactants, oil components, emulsifiers, pearlizing waxes, consistency factors, thickeners, superfatting agents, stabilizers, polymers, silicone compounds, fats, waxes, lecithins, phospholipids, biogenic agents, UV protection factors, antioxidants, deodorants, antiperspirants, antidandruff agents, film formers, swelling agents, insect repellents, self-tanning agents, tyrosine inhibitors (depigmenting agents), hydrotropes, solubilizers, perservatives, perfume oils, dyes and the like as further auxiliaries and additives.
Surfactants
Suitable surfactants are anionic, nonionic, cationic and/or amphoteric or zwitterionic surfactants which may be present in the preparations in quantities of normally about 1 to 70% by weight, preferably 5 to 50% by weight and more preferably 10 to 30% by weight. Typical examples of anionic surfactants are soaps, alkyl benzenesulfonates, alkanesulfonates, olefin sulfonates, alkylether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and salts thereof, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as, for example, acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (particularly wheat-based vegetable products) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they may have a conventional homolog distribution although they preferably have a narrow-range homolog distribution. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers and mixed formals, optionally partly oxidized alk(en)yl oligoglycosides or glucuronic acid derivatives, fatty acid-N-alkyl glucamides, protein hydrolyzates (particularly wheat-based vegetable products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they may have a conventional homolog distribution, although they preferably have a narrow-range homolog distribution. Typical examples of cationic surfactants are quaternary ammonium compounds, for example dimethyl distearyl ammonium chloride, and esterquats, more particularly quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are all known compounds. Information on their structure and production can be found in relevant synoptic works, cf. for example J. Falbe (ed.), “Surfactants in Consumer Products”, Springer Verlag, Berlin, 1987, pages 54 to 124 or J. Falbe (ed.), “Katalysatoren, Tenside und Mineralöladditive (Catalysts, Surfactants and Mineral Oil Additives)”, Thieme Verlag, Stuttgart, 1978, pages 123-217. Typical examples of particularly suitable mild, i.e. particularly dermatologically compatible, surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and/or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, α-olefin sulfonates, ether carboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines, amphoacetals and/or protein fatty acid condensates, preferably based on wheat proteins.
Oil Components
Suitable oil components are, for example, Guerbet alcohols based on fatty alcohols containing 6 to 18 and preferably 8 to 10 carbon atoms, esters of linear C 6-22 fatty acids with linear or branched C 6-22 fatty alcohols or esters of branched C 3-13 carboxylic acids with linear or branched C 6-22 fatty alcohols such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. Also suitable are esters of linear C 6-22 fatty acids with branched alcohols, more particularly 2-ethyl hexanol, esters of C 18-38 alkylhydroxycarboxylic acids with linear or branched C 6-22 fatty alcohols (cf. DE 197 56 377 A1), more especially Dioctyl Malate, esters of linear and/or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols, triglycerides based on C 6-10 fatty acids, liquid mono-, di- and triglyceride mixtures based on C 6-18 fatty acids, esters of C 6-22 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, more particularly benzoic acid, esters of C 2-12 dicarboxylic acids with linear or branched alcohols containing 1 to 22 carbon atoms or polyols containing 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C 6-22 fatty alcohol carbonates, such as Dicaprylyl Carbonate (Cetiol® CC) for example, Guerbet carbonates based on C 6-18 and preferably C 8-10 fatty alcohols, esters of benzoic acid with linear and/or branched C 6-22 alcohols (for example Finsolv® TN), linear or branched, symmetrical or nonsymmetrical dialkyl ethers containing 6 to 22 carbon atoms per alkyl group, such as Dicaprylyl Ether (Cetiol® OE) for example, ring opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicone, silicon methicone types, etc.) and/or aliphatic or naphthenic hydrocarbons such as, for example, squalane, squalene or dialkyl cyclohexanes.
Emulsifiers
Suitable emulsifiers are, for example, nonionic surfactants from at least one of the following groups:
products of the addition of 2 to 30 mol ethylene oxide and/or 0 to 5 mol propylene oxide onto linear C 8-22 fatty alcohols, onto C 12-22 fatty acids, onto alkyl phenols containing 8 to 15 carbon atoms in the alkyl group and onto alkylamines containing 8 to 22 carbon atoms in the alkyl group; alkyl and/or alkenyl oligoglycosides containing 8 to 22 carbon atoms in the alk(en)yl group and ethoxylated analogs thereof; addition products of 1 to 15 mol ethylene oxide onto castor oil and/or hydrogenated castor oil; addition products of 15 to 60 mol ethylene oxide onto castor oil and/or hydrogenated castor oil; partial esters of glycerol and/or sorbitan with unsaturated, linear or saturated, branched fatty acids containing 12 to 22 carbon atoms and/or hydroxycarboxylic acids containing 3 to 18 carbon atoms and addition products thereof onto 1 to 30 mol ethylene oxide; partial esters of polyglycerol (average degree of self-condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5,000), trimethylolpropane, pentaerythritol, sugar alcohols (for example sorbitol), alkyl glucosides (for example methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (for example cellulose) with saturated and/or unsaturated, linear or branched fatty acids containing 12 to 22 carbon atoms and/or hydroxycarboxylic acids containing 3 to 18 carbon atoms and addition products thereof onto 1 to 30 mol ethylene oxide; mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE 1165574 PS and/or mixed esters of fatty acids containing 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol, mono-, di- and trialkyl phosphates and mono-, di- and/or tri-PEG-alkyl phosphates and salts thereof, wool wax alcohols, polysiloxane/polyalkyl/polyether copolymers and corresponding derivatives, block copolymers, for example Polyethyleneglycol-30 Dipolyhydroxystearate; polymer emulsifiers, for example Pemulen types (TR-1, TR-2) of Goodrich; polyalkylene glycols and glycerol carbonate.

Ethylene Oxide Addition Products
The addition products of ethylene oxide and/or propylene oxide onto fatty alcohols, fatty acids, alkylphenols or onto castor oil are known commercially available products. They are homolog mixtures of which the average degree of alkoxylation corresponds to the ratio between the quantities of ethylene oxide and/or propylene oxide and substrate with which the addition reaction is carried out. C 12/18 fatty acid monoesters and diesters of addition products of ethylene oxide onto glycerol are known as lipid layer enhancers for cosmetic formulations from DE 2024051 PS.
Alkyl and/or Alkenyl Oligoglycosides
Alkyl and/or alkenyl oligoglycosides, their production and their use are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols containing 8 to 18 carbon atoms. So far as the glycoside unit is concerned, both monoglycosides in which a cyclic sugar unit is attached to the fatty alcohol by a glycoside bond and oligomeric glycosides with a degree of oligomerization of preferably up to about 8 are suitable. The degree of oligomerization is a statistical mean value on which the homolog distribution typical of such technical products is based.
Partial Glycerides
Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, hydroxystearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride, oleic acid monoglyceride, oleic acid diglyceride, ricinoleic acid monoglyceride, ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic acid diglyceride, linolenic acid monoglyceride, linolenic acid diglyceride, erucic acid monoglyceride, erucic acid diglyceride, tartaric acid monoglyceride, tartaric acid diglyceride, citric acid monoglyceride, citric acid diglyceride, malic acid monoglyceride, malic acid diglyceride and technical mixtures thereof which may still contain small quantities of triglyceride from the production process. Addition products of 1 to 30 and preferably 5 to 10 mol ethylene oxide onto the partial glycerides mentioned are also suitable.
Sorbitan Esters
Suitable sorbitan esters are sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitan dierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitan sesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate and technical mixtures thereof. Addition products of 1 to 30 and preferably 5 to 10 mol ethylene oxide onto the sorbitan esters mentioned are also suitable.
Polyglycerol Esters
Typical examples of suitable polyglycerol esters are Polyglyceryl-2 Dipolyhydroxystearate (Dehymuls® PGPH), Polyglycerin-3-Diisostearate (Lameform® TGI), Polyglyceryl-4 Isostearate (Isolan® GI 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-3 Diisostearate (Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010/90), Polyglyceryl-3 Cetyl Ether (Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403), Polyglyceryl Dimerate Isostearate and mixtures thereof. Examples of other suitable polyolesters are the mono-, di- and triesters of trimethylolpropane or pentaerythritol with lauric acid, cocofatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like optionally reacted with 1 to 30 mol ethylene oxide.
Anionic Emulsifiers
Typical anionic emulsifiers are aliphatic fatty acids containing 12 to 22 carbon atoms such as, for example, palmitic acid, stearic acid or behenic acid and dicarboxylic acids containing 12 to 22 carbon atoms such as, for example, azelaic acid or sebacic acid.
Amphoteric and Cationic Emulsifiers
Other suitable emulsifiers are zwitterionic surfactants. Zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example cocoacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. Ampholytic surfactants are also suitable emulsifiers. Ampholytic surfactants are surface-active compounds which, in addition to a C 8/18 alkyl or acyl group, contain at least one free amino group and at least one —COOH— or —SO 3 H— group in the molecule and which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C 12/18 acyl sarcosine. Finally, cationic surfactants are also suitable emulsifiers, those of the esterquat type, preferably methylquaternized difatty acid triethanolamine ester salts, being particularly preferred.
Fats and Waxes
Typical examples of fats are glycerides, i.e. solid or liquid, vegetable or animal products which consist essentially of mixed glycerol esters of higher fatty acids. Suitable waxes are inter alia natural waxes such as, for example, candelilla wax, carnauba wax, Japan wax, espartograss wax, cork wax, guaruma wax, rice oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax), uropygial fat, ceresine, ozocerite (earth wax), petrolatum, paraffin waxes and microwaxes; chemically modified waxes (hard waxes) such as, for example, montan ester waxes, sasol waxes, hydrogenated jojoba waxes and synthetic waxes such as, for example, polyalkylene waxes and polyethylene glycol waxes. Besides the fats, other suitable additives are fat-like substances, such as lecithins and phospholipids. Lecithins are known among experts as glycerophospholipids which are formed from fatty acids, glycerol, phosphoric acid and choline by esterification. Accordingly, lecithins are also frequently referred to by experts as phosphatidyl cholines (PCs). Examples of natural lecithins are the kephalins which are also known as phosphatidic acids and which are derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids. By contrast, phospholipids are generally understood to be mono- and preferably diesters of phosphoric acid with glycerol (glycerophosphates) which are normally classed as fats. Sphingosines and sphingolipids are also suitable.
Pearlizing Waxes
Suitable pearlizing waxes are, for example, alkylene glycol esters, especially ethylene glycol distearate; fatty acid alkanolamides, especially cocofatty acid diethanolamide; partial glycerides, especially stearic acid monoglyceride; esters of polybasic, optionally hydroxysubstituted carboxylic acids with fatty alcohols containing 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; fatty compounds, such as for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates which contain in all at least 24 carbon atoms, especially laurone and distearylether; fatty acids, such as stearic acid, hydroxystearic acid or behenic acid, ring opening products of olefin epoxides containing 12 to 22 carbon atoms with fatty alcohols containing 12 to 22 carbon atoms and/or polyols containing 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.
Consistency Factors and Thickeners
The consistency factors mainly used are fatty alcohols or hydroxyfatty alcohols containing 12 to 22 and preferably 16 to 18 carbon atoms and also partial glycerides, fatty acids or hydroxyfatty acids. A combination of these substances with alkyl oligoglucosides and/or fatty acid N-methyl glucamides of the same chain length and/or polyglycerol poly-12-hydroxystearates is preferably used. Suitable thickeners are, for example, Aerosil® types (hydrophilic silicas), polysaccharides, more especially xanthan gum, guar-guar, agar-agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, also relatively high molecular weight polyethylene glycol monoesters and diesters of fatty acids, polyacrylates (for example Carbopols® and Pemulen types [Goodrich]; Synthalens® [Sigma]; Keltrol types [Kelco]; Sepigel types [Seppic]; Salcare types [Allied Colloids]), polyacrylamides, polymers, polyvinyl alcohol and polyvinyl pyrrolidone. Other consistency factors which have proved to be particularly effective are bentonites, for example Bentone® Gel VS-5PC (Rheox) which is a mixture of cyclopentasiloxane, Disteardimonium Hectorite and propylene carbonate. Other suitable consistency factors are surfactants such as, for example, ethoxylated fatty acid glycerides, esters of fatty acids with polyols, for example pentaerythritol or trimethylol propane, narrow-range fatty alcohol ethoxylates or alkyl oligoglucosides and electrolytes, such as sodium chloride and ammonium chloride.
Superfatting Agents
Superfatting agents may be selected from such substances as, for example, lanolin and lecithin and also polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the fatty acid alkanolamides also serving as foam stabilizers.
Stabilizers
Metal salts of fatty acids such as, for example, magnesium, aluminium and/or zinc stearate or ricinoleate may be used as stabilizers.
Polymers
Suitable cationic polymers are, for example, cationic cellulose derivatives such as, for example, the quaternized hydroxyethyl cellulose obtainable from Amerchol under the name of Polymer JR 400®, cationic starch, copolymers of diallyl ammonium salts and acrylamides, quaternized vinyl pyrrolidone/vinyl imidazole polymers such as, for example, Luviquat® (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides such as, for example, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen (Lamequat® L, Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers such as, for example, amodimethicone, copolymers of adipic acid and dimethylaminohydroxypropyl diethylenetriamine (Cartaretine®, Sandoz), copolymers of acrylic acid with dimethyl diallyl ammonium chloride (Merquat® 550, Chemviron), polyaminopolyamides as described, for example, in FR 2252840 A and crosslinked water-soluble polymers thereof, cationic chitin derivatives such as, for example, quaternized chitosan, optionally in microcrystalline distribution, condensation products of dihaloalkyls, for example dibromobutane, with bis-dialkylamines, for example bis-dimethylamino-1,3-propane, cationic guar gum such as, for example, Jaguar®CBS, Jaguar®C-17, Jaguar®C-16 of Celanese, quaternized ammonium salt polymers such as, for example, Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 of Miranol.
Suitable anionic, zwitterionic, amphoteric and nonionic polymers are, for example, vinyl acetate/crotonic acid copolymers, vinyl pyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinylether/maleic anhydride copolymers and esters thereof, uncrosslinked and polyol-crosslinked polyacrylic acids, acrylamidopropyl trimethylammonium chloride/acrylate copolymers, octylacrylamide/methyl methacrylate/tert.-butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, polyvinyl pyrrolidone, vinyl pyrrolidone/vinyl acetate copolymers, vinyl pyrrolidone/dimethylaminoethyl methacrylate/vinyl caprolactam terpolymers and optionally derivatized cellulose ethers and silicones. Other suitable polymers and thickeners can be found in Cosm. Toil., 108, 95 (1993).
Silicone Compounds
Suitable silicone compounds are, for example, dimethyl polysiloxanes, methylphenyl polysiloxanes, cyclic silicones and amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone compounds which may be both liquid and resin-like at room temperature. Other suitable silicone compounds are simethicones which are mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates. A detailed overview of suitable volatile silicones can be found in Todd et al. in Cosm. Toil. 91, 27 (1976).
UV Protection Factors and Antioxidants
UV protection factors in the context of the invention are, for example, organic substances (light filters) which are liquid or crystalline at room temperature and which are capable of absorbing ultraviolet radiation and of releasing the energy absorbed in the form of longer-wave radiation, for example heat. UV-B filters can be oil-soluble or water-soluble. The following are examples of oil-soluble substances:
3-benzylidene camphor or 3-benzylidene norcamphor and derivatives thereof, for example 3-(4-methylbenzylidene)-camphor as described in EP 0693471 B1; 4-aminobenzoic acid derivatives, preferably 4-(dimethylamino)-benzoic acid-2-ethylhexyl ester, 4-(dimethylamino)-benzoic acid-2-octyl ester and 4-(dimethylamino)-benzoic acid amyl ester; esters of cinnamic acid, preferably 4-methoxycinnamic acid-2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid-2-ethylhexyl ester (Octocrylene); esters of salicylic acid, preferably salicylic acid-2-ethylhexyl ester, salicylic acid-4-isopropylbenzyl ester, salicylic acid homomenthyl ester; derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4′-methylbenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone; esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di-2-ethylhexyl ester; triazine derivatives such as, for example, 2,4,6-trianilino-(p-carbo-2′-ethyl-1′-hexyloxy)-1,3,5-triazine and Octyl Triazone as described in EP 0818450 Alor Dioctyl Butamido Triazone (Uvasorb® HEB); propane-1,3-diones such as, for example, 1-(4-tert.butylphenyl)-3-(4′-methoxyphenyl)-propane-1,3-dione; ketotricyclo(5.2.1.0)decane derivatives as described in EP 0694521 B1.

Suitable water-soluble substances are
2-phenylbenzimidazole-5-sulfonic acid and alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts thereof; sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and salts thereof; sulfonic acid derivatives of 3-benzylidene camphor such as, for example, 4-(2-oxo-3-bornylidenemethyl)-benzene sulfonic acid and 2-methyl-5-(2-oxo-3-bornylidene)-sulfonic acid and salts thereof.

Typical UV-A filters are, in particular, derivatives of benzoyl methane such as, for example, 1-(4′-tert.butylphenyl)-3-(4′-methoxyphenyl)-propane-1,3-dione, 4-tert.butyl-4′-methoxydibenzoyl methane (Parsol® 1789) or 1-phenyl-3-(4′-isopropylphenyl)-propane-1,3-dione and the enamine compounds described in DE 19712033 A1 (BASF). The UV-A and UV-B filters may of course also be used in the form of mixtures. Particularly favorable combinations consist of the derivatives of benzoyl methane, for example 4-tert.butyl-4′-methoxydibenzoylmethane (Parsol® 1789) and 2-cyano-3,3-phenylcinnamic acid-2-ethyl hexyl ester (Octocrylene) in combination with esters of cinnamic acid, preferably 4-methoxycinnamic acid-2-ethyl hexyl ester and/or 4-methoxycinnamic acid propyl ester and/or 4-methoxycinnamic acid isoamyl ester. Combinations such as these are advantageously combined with water-soluble filters such as, for example, 2-phenylbenzimidazole-5-sulfonic acid and alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts thereof.
Besides the soluble substances mentioned, insoluble light-blocking pigments, i.e. finely dispersed metal oxides or salts, may also be used for this purpose. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide and also oxides of iron, zirconium oxide, silicon, manganese, aluminium and cerium and mixtures thereof. Silicates (talcum), barium sulfate and zinc stearate may be used as salts. The oxides and salts are used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have a mean diameter of less than 100 nm, preferably between 5 and 50 nm and more preferably between 15 and 30 nm. They may be spherical in shape although ellipsoidal particles or other non-spherical particles may also be used. The pigments may also be surface-treated, i.e. hydrophilicized or hydrophobicized. Typical examples are coated titanium dioxides, for example Titandioxid T 805 (Degussa) and Eusolex® T2000 (Merck). Suitable hydrophobic coating materials are, above all, silicones and, among these, especially trialkoxyoctylsilanes or simethicones. So-called micro- or nanopigments are preferably used in sun protection products. Micronized zinc oxide is preferably used. Other suitable UV filters can be found in P. Finkel's review in SÖFW-Journal 122, 543 (1996) and in Parf. Kosm. 3, 11 (1999).
Besides the two groups of primary sun protection factors mentioned above, secondary sun protection factors of the antioxidant type may also be used. Secondary sun protection factors of the antioxidant type interrupt the photochemical reaction chain which is initiated when UV rays penetrate into the skin. Typical examples are amino acids (for example glycine, histidine, tyrosine, tryptophane) and derivatives thereof, imidazoles (for example urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (for example anserine), carotinoids, carotenes (for example α-carotene, β-carotene, lycopene) and derivatives thereof, chlorogenic acid and derivatives thereof, liponic acid and derivatives thereof (for example dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (for example thioredoxine, glutathione, cysteine, cystine, cystamine and glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters thereof) and their salts, dilaurylthiodipropionate, distearylthiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (for example butionine sulfoximines, homocysteine sulfoximine, butionine sulfones, penta-, hexa- and hepta-thionine sulfoximine) in very small compatible dosages (for example pmole to μmole/kg), also (metal) chelators (for example α-hydroxyfatty acids, palmitic acid, phytic acid, lactoferrine), α-hydroxy acids (for example citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (for example γ-linolenic acid, linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C and derivatives thereof (for example ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (for example vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, α-glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butyl hydroxyanisole, nordihydroguaiac resin acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, Superoxid-Dismutase, zinc and derivatives thereof (for example ZnO, ZnSO 4 ), selenium and derivatives thereof (for example selenium methionine), stilbenes and derivatives thereof (for example stilbene oxide, trans-stilbene oxide) and derivatives of these active substances suitable for the purposes of the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids).
Biogenic Agents
In the context of the invention, biogenic agents are, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, (deoxy)ribonucleic acid and fragmentation products thereof, β-glucans, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts, for example prune extract, bambara nut extract, and vitamin complexes.
Deodorants and Germ Inhibitors
Cosmetic deodorants counteract, mask or eliminate body odors. Body odors are formed through the action of skin bacteria on apocrine perspiration which results in the formation of unpleasant-smelling degradation products. Accordingly, deodorants contain active principles which act as germ inhibitors, enzyme inhibitors, odor absorbers or odor maskers.
Germ Inhibitors
Basically, suitable germ inhibitors are any substances which act against gram-positive bacteria such as, for example, 4-hydroxybenzoic acid and salts and esters thereof, N-(4-chlorophenyl)-N′-(3,4-dichlorophenyl)-urea, 2,4,4′-trichloro-2′-hydroxydiphenylether (triclosan), 4-chloro-3,5-dimethylphenol, 2,2′-methylene-bis-(6-bromo-4-chlorophenol), 3-methyl-4-(1-methylethyl)-phenol, 2-benzyl-4-chlorophenol, 3-(4-chlorophenoxy)-propane-1,2-diol, 3-iodo-2-propinyl butyl carbamate, chlorhexidine, 3,4,4′-trichlorocarbanilide (TTC), antibacterial perfumes, thymol, thyme oil, eugenol, clove oil, menthol, mint oil, farnesol, phenoxyethanol, glycerol monocaprate, glycerol monocaprylate, glycerol monolaurate (GML), diglycerol monocaprate (DMC), salicylic acid-N-alkylamides such as, for example, salicylic acid-n-octyl amide or salicylic acid-n-decyl amide.
Enzyme Inhibitors
Suitable enzyme inhibitors are, for example, esterase inhibitors. Esterase inhibitors are preferably trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and, in particular, triethyl citrate (Hydagen® CAT). Esterase inhibitors inhibit enzyme activity and thus reduce odor formation. Other esterase inhibitors are sterol sulfates or phosphates such as, for example, lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and esters thereof, for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester, hydroxycarboxylic acids and esters thereof, for example citric acid, malic acid, tartaric acid or tartaric acid diethyl ester, and zinc glycinate.
Odor Absorbers
Suitable odor absorbers are substances which are capable of absorbing and largely retaining the odor-forming compounds. They reduce the partial pressure of the individual components and thus also reduce the rate at which they spread. An important requirement in this regard is that perfumes must remain unimpaired. Odor absorbers are not active against bacteria. They contain, for example, a complex zinc salt of ricinoleic acid or special perfumes of largely neutral odor known to the expert as “fixateurs” such as, for example, extracts of ladanum or styrax or certain abietic acid derivatives as their principal component. Odor maskers are perfumes or perfume oils which, besides their odor-masking function, impart their particular perfume note to the deodorants. Suitable perfume oils are, for example, mixtures of natural and synthetic fragrances. Natural fragrances include the extracts of blossoms, stems and leaves, fruits, fruit peel, roots, woods, herbs and grasses, needles and branches, resins and balsams. Animal raw materials, for example civet and beaver, may also be used. Typical synthetic perfume compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Examples of perfume compounds of the ester type are benzyl acetate, p-tert.butyl cyclohexylacetate, linalyl acetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Ethers include, for example, benzyl ethyl ether while aldehydes include, for example, the linear alkanals containing 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal. Examples of suitable ketones are the ionones and methyl cedryl ketone. Suitable alcohols are anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons mainly include the terpenes and balsams. However, it is preferred to use mixtures of different perfume compounds which, together, produce an agreeable fragrance. Other suitable perfume oils are essential oils of relatively low volatility which are mostly used as aroma components. Examples are sage oil, camomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime-blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, ladanum oil and lavendin oil. The following are preferably used either individually or in the form of mixtures: bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice, citrus oil, mandarin oil, orange oil, allylamyl glycolate, cyclovertal, lavendin oil, clary oil, β-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat.
Antiperspirants
Antiperspirants reduce perspiration and thus counteract underarm wetness and body odor by influencing the activity of the eccrine sweat glands. Aqueous or water-free antiperspirant formulations typically contain the following ingredients:
astringent active principles, oil components, nonionic emulsifiers, co-emulsifiers, consistency factors, auxiliaries in the form of, for example, thickeners or complexing agents and/or non-aqueous solvents such as, for example, ethanol, propylene glycol and/or glycerol.

Suitable astringent active principles of antiperspirants are, above all, salts of aluminium, zirconium or zinc. Suitable antihydrotic agents of this type are, for example, aluminium chloride, aluminium chlorohydrate, aluminium dichlorohydrate, aluminium sesquichlorohydrate and complex compounds thereof, for example with 1,2-propylene glycol, aluminium hydroxyallantoinate, aluminium chloride tartrate, aluminium zirconium trichlorohydrate, aluminium zirconium tetrachlorohydrate, aluminium zirconium pentachlorohydrate and complex compounds thereof, for example with amino acids, such as glycine. Oil-soluble and water-soluble auxiliaries typically encountered in antiperspirants may also be present in relatively small amounts. Oil-soluble auxiliaries such as these include, for example,
inflammation-inhibiting, skin-protecting or pleasant-smelling essential oils, synthetic skin-protecting agents and/or oil-soluble perfume oils.

Typical water-soluble additives are, for example, preservatives, water-soluble perfumes, pH adjusters, for example buffer mixtures, water-soluble thickeners, for example water-soluble natural or synthetic polymers such as, for example, xanthan gum, hydroxyethyl cellulose, polyvinyl pyrrolidone or high molecular weight polyethylene oxides.
Film Formers
Standard film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinyl pyrrolidone, vinyl pyrrolidone/vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid and salts thereof and similar compounds.
Antidandruff Agents
Suitable antidandruff agents are Pirocton Olamin (1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2-(1H)-pyridinone monoethanolamine salt), Baypival® (Climbazole), Ketoconazol® (4-acetyl-1-{4-[2-(2,4-dichlorophenyl) r-2-(1H-imidazol-1-ylmethyl)-1,3-dioxylan-c-4-ylmethoxyphenyl}-piperazine, ketoconazole, elubiol, selenium disulfide, colloidal sulfur, sulfur polyethylene glycol sorbitan monooleate, sulfur ricinol polyethoxylate, sulfur tar distillate, salicylic acid (or in combination with hexachlorophene), undecylenic acid, monoethanolamide sulfosuccinate Na salt, Lamepon® UD (protein/undecylenic acid condensate), zinc pyrithione, aluminum pyrithione and magnesium pyrithione/dipyrithione magnesium sulfate.
Swelling Agents
Suitable swelling agents for aqueous phases are montmorillonites, clay minerals, Pemulen and alkyl-modified Carbopol types (Goodrich). Other suitable polymers and swelling agents can be found in R. Lochhead's review in Cosm. Toil. 108, 95 (1993).
Insect Repellents
Suitable insect repellents are N,N-diethyl-m-toluamide, pentane-1,2-diol or Ethyl Butylacetylaminopropionate.
Self-Tanning Agents and Depigmenting Agents
A suitable self-tanning agent is dihydroxyacetone. Suitable tyrosine inhibitors which prevent the formation of melanin and are used in depigmenting agents are, for example, arbutin, ferulic acid, koji acid, coumaric acid and ascorbic acid (vitamin C).
Hydrotropes
In addition, hydrotropes, for example ethanol, isopropyl alcohol or polyols, may be used to improve flow behavior. Suitable polyols preferably contain 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols may contain other functional groups, more especially amino groups, or may be modified with nitrogen. Typical examples are
glycerol; alkylene glycols such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1000 dalton; technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10 such as, for example, technical diglycerol mixtures with a diglycerol content of 40 to 50% by weight; methylol compounds such as, in particular, trimethylol ethane, trimethylol propane, trimethylol butane, pentaerythritol and dipentaerythritol; lower alkyl glucosides, particularly those containing 1 to 8 carbon atoms in the alkyl group, for example methyl and butyl glucoside; sugar alcohols containing 5 to 12 carbon atoms, for example sorbitol or mannitol, >sugars containing 5 to 12 carbon atoms, for example glucose or sucrose; amino sugars, for example glucamine; dialcoholamines, such as diethanolamine or 2-aminopropane-1,3-diol.

Preservatives


Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the silver complexes known under the name of Surfacine® and the other classes of compounds listed in Appendix 6, Parts A and B of the Kosmetikverordnung (“Cosmetics Directive”).
Perfume Oils and Aromas
Suitable perfume oils are mixtures of natural and synthetic perfumes. Natural perfumes include the extracts of blossoms (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, orange), roots (nutmeg, angelica, celery, cardamom, costus, iris, calmus), woods (pinewood, sandalwood, guaiac wood, cedarwood, rosewood), herbs and grasses (tarragon, lemon grass, sage, thyme), needles and branches (spruce, fir, pine, dwarf pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials, for example civet and beaver, may also be used. Typical synthetic perfume compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Examples of perfume compounds of the ester type are benzyl acetate, phenoxyethyl isobutyrate, p-tert.butyl cyclohexylacetate, linalyl acetate, dimethyl benzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, ethylmethyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Ethers include, for example, benzyl ethyl ether while aldehydes include, for example, the linear alkanals containing 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal. Examples of suitable ketones are the ionones, α-isomethylionone and methyl cedryl ketone. Suitable alcohols are anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons mainly include the terpenes and balsams. However, it is preferred to use mixtures of different perfume compounds which, together, produce an agreeable perfume. Other suitable perfume oils are essential oils of relatively low volatility which are mostly used as aroma components. Examples are sage oil, camomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime-blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, ladanum oil and lavendin oil. The following are preferably used either individually or in the form of mixtures: bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice, citrus oil, mandarin oil, orange oil, allylamyl glycolate, cyclovertal, lavendin oil, clary oil, β-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat.
Suitable aromas are, for example, peppermint oil, spearmint oil, aniseed oil, Japanese anise oil, caraway oil, eucalyptus oil, fennel oil, citrus oil, wintergreen oil, clove oil, menthol and the like.
Dyes
Suitable dyes are any of the substances suitable and approved for cosmetic purposes as listed, for example, in the publication “Kosmetische Färbemittel” of the Farbstoffkommission der Deutschen Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pages 81 to 106. Examples include cochineal red A (C.I. 16255), patent blue V (C.I. 42051), indigotin (C.I. 73015), chlorophyllin (C.I. 75810), quinoline yellow (C.I. 47005), titanium dioxide (C.I. 77891), indanthrene blue RS(C.I. 69800) and madder lake (C.I. 58000). Luminol may also be present as a luminescent dye. These dyes are normally used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.
The total percentage content of auxiliaries and additives may be from 1 to 50% by weight and is preferably from 5 to 40% by weight, based on the particular preparations. The preparations may be produced by standard hot or cold processes and are preferably produced by the phase inversion temperature method.
EXAMPLES
In the following tests, an extract of Vaccinium myrtyllus with an active substance content of 25% by weight (from Cognis) was used as the test substance.
A. Activity Against Free Radicals
The effectiveness of the test substances against free radicals was tested by various chemical and biochemical methods:
Method A A first test was carried out using diphenylpicrylhydrazyl (DPPH°) which is a relatively stable radical that forms a purple-colored solution. The optical density (DO) at 513 nm was determined. Method B Hydroxyl radicals were released from hydrogen peroxide in the presence of iron(II) ions and EDTA and were used to oxidize deoxyribose. The oxidation product forms a pink-colored compound with thiobarbituric acid. Its concentration corresponds to the optical density at 532 nm. A test was conducted to determine whether less deoxyribose is oxidized, i.e. whether fewer free radicals are released, in the presence of the test products. Method C The test just described was conducted in the absence of EDTA to determine the suitability of the test substances for forming inactive iron complexes. Method D Xanthine oxidase is an enzyme which is released through oxidative stress and catabolizes the decomposition of the purine bases adenine and guanine into uronic acid and superoxide anions. The superoxide anions dismute into hydrogen peroxide and oxygen either spontaneously or in the presence of Superoxid Dismutase. The quantity of superoxide anion can be determined by NBT reduction via the optical density at 490 nm. A test was conducted to determine whether fewer superoxide anions are generated or more anions are destroyed in the presence of the test substances.

The results are set out in Table 1 and represent the EC50 values in % (w/v).
TABLE 1 Effect against free radicals (figures = % -rel.) Method Ex. Test product A B C D 1 Vaccinium extract 0.0014 0.252 0.91 0.6 C1 Tocopherol 0.0067 n.d. n.d. No effect C2 Ascorbic acid 0.0013 0.261 0.9 0.591 C3 BHT* 0.0500 n.d. n.d. No effect *BHT = butylhydroxytoluene

The results suggest that the Vaccinium myrtyllus extract has anti-oxidative activity which is far superior to that of tocopherol and BHT and comparable with that of vitamin C. In the absence of EDTA, the test substance has a particularly high potential for quenching hydroxyl ions which shows that it forms stable iron complexes. Finally, it has a high potential for preventing the reduction of BT by superoxide anions.
B. Protection of Cells Against UVA Radiation
The object of the following in vitro tests was to determine whether vaccinium extract would protect human fibroblasts against oxidative stress and, more particularly, against the effects of UVA rays. UVA was selected as the stress factor because the rays penetrate into the dermis where they lead above all to lipoperoxidation of the cytoplasm membranes. The lipoperoxides formed are split into malonaldialdehydes (MDA) which are responsible for the crosslinking of many biomolecules such as, for example, proteins (enzyme inhibition) or nuclein bases (mutagenesis). To carry out the test, a fibroblast culture was mixed with foetal calf serum and, 2 days later, inoculated with the test substances. After incubation for 36 h at 37° C./5% by vol. CO 2 , the nutrient medium was replaced by an electrolyte solution and the fibroblasts were damaged by a predetermined dose of UVA (3-15 J/cm 2 ). After the exposure, the quantity of MDA formed was determined in the supernatant solution by reaction with thiobarbituric acid while the content of proteins in the cell homogenizate was determined by Bradford's method. The results are set out in Table 2 as %-rel against the standard. Table 2 shows the mean value of two series of measurements involving triple determination.
TABLE 2 Activity against UVA rays (figures = % -rel.) Conc. Ex. Test product % w/v MDA released Cell proteins C4 Control without UVA 0 100 C5 Control with UVA 100 101 2 Vaccinium extract 0.005 90 94

The results show that the vaccinium extract has a lastingly positive effect in combating oxidative stress without damaging the fibroblasts.
C. Protecting cells against UVB radiation
The function of this test was to show that vaccinium extracts have anti-inflammatory properties for human keratinocytes. UVB was selected as the stress factor because the rays produce cutaneous inflammation (erythemas, oedemas) by activating enzymes that release arachidonic acid, such as phospholipase A2 (PLA2) for example. This results not only in damage to the membranes, but also in the formation of inflammatory substances, such as prostaglandins of the PGE2 type for example. The influence of UVB rays on keratinocytes was determined in vitro through the release of cytoplasmatic enzymes, such as LDH (lactate dehydrogenase) for example, which runs parallel to the cell damage and the formation of PGE2. To carry out the test, a fibroblast culture was mixed with foetal calf serum and inoculated with the test substances 2 days later. After incubation for 36 h at 37° C. and a CO 2 level of 5% by vol., the nutrient medium was replaced by an electrolyte solution and the fibroblasts were damaged with a particular dose of UVB (50 mJ/cm 2 ). The quantity of keratinocytes was determined after trypsination via a cell counter while the LDH concentration was enzymatically determined. The results are set out in Table 3 which shows the activity in %-rel. against a standard as the mean value of two test series involving double determination.
TABLE 3 Effect against UVB rays (figures - % -rel.) Conc. LDH PGE2 Ex. Test product % w/v Cell DNA released released V6 Control without UVB 100 0 0 C7 Control with UVB 31 100 100 3 Vaccinium extract 0.005 57 88 72

The results show that the test substances significantly reduce the harmful effects of UVB rays and, in particular, reduce the release of LDH and PGE2.
D. Effectiveness Against Proteases
In the event of inflammation, skin proteases, for example collagenase, are released from the polymorphonuclear neutrophilic granulocytes or macrophages. A similar process takes place in the skin of elderly people on exposure to UV rays. As already mentioned, the proteases—also known as matrix metalloproteases (MMPs) through their content of central zinc ions—catalyze the fragmentation of connective tissue proteins. The test substances were tested for collagenase inhibition using bacterial collagenase (clostridium histolyticum) on gelatin marked with fluorochromium (FITA, Calbiochem) as a natural nutrient medium. The incubation time was 60 mins. at 20° C.; the hydrolysis of the substrate was monitored by fluorescence at 393 nm (excitation at 328 nm). The results are set out in Table 4 as the collagenase inhibition in %.
TABLE 4 Collagenase inhibition (figures = % -rel.) Concentration % (w/v) Ex. Test product 0.005 0.01 0.05 4 Vaccinium extract 12 44 71

The results show that the vaccinium extract has a significant inhibiting effect depending on concentration.
E. Inhibition of Human MMP-1 Synthesis
The ability of vaccinium extract to reduce the toxic effect of UVA rays was investigated. The in vitro system used was a culture of dermal fibroblasts. The release of MMP-1 from those fibroblasts under the influence of UV radiation was determined. To carry out the test, a fibroblast culture was prepared using foetal calf serum and, 2 days later, was inoculated with the test substances. After incubation for 36 h at 37° C. and a CO 2 level of 5% by volume, the nutrient medium was replaced by an electrolyte solution and the fibroblasts were damaged by a predetermined dose of UVB radiation (50 mJ/cm 2 ). The MMPs were determined using a kit of the type marketed by Amersham under the name of RPN2610. The results are set out in Table 5. The results are expressed as the quantity of MMPs in ng/ml from a test series with triple determination.
TABLE 5 MMP Inhibition (figures = % -rel.) MMPs Example Test product Conc.(% w/v) Without UVA With UVA C8 Control 49 ± 9 199 ± 25 5 Vaccinium 0.005 38 ± 7 161 ± 22 extract

The results show that vaccinium extract lastingly reduces the release of MMP on exposure to UVA radiation.
F. Anti-Inflammatory Activity
In the course of cutaneous inflammation, leucocytes, such as the polymorphonuclear neutrophilic granulocytes (PMNs) for example, are stimulated by peptides, such as cytokinins for example, to emit messenger substances, such as leucotriene for example, which are released from activated or necrotic cells in the dermis. These activated PMNs release not only pro-inflammatory cytokinins, leucotrienes and proteases, but also ROS, such as superoxides and hypochlorite anions for example, of which the function is to destroy penetrated pathogenic germs or fungi. This activity of the PMNs during the inflammation is known as so-called respiratory burst and can lead to additional damage in the tissue. To investigate to what extent the test extracts can prevent or reduce the respiratory burst, a cell line of human leukaemic granulocytes of these PMNs was incubated together with the test substances at 37° C. and 5% by vol. CO 2 . After the respiratory burst had been initiated by addition of a yeast extract (zymosan) to the cell solution, the release of superoxide anions was determined through their reaction with luminol. The results are set out in Table 6 which shows the cell counts and the quantity of ROS released in %-rel to the standard as the mean value of a series of measurements involving triple determination.
TABLE 5 Anti-inflammatory activity Conc. Ex. Test product (% w/v) Cell counts ROS released C9 Control 0 100 100 6 Vaccinium extract 0.001 102 ± 1 35 ± 25

The results show that vaccinium extract has a strong inhibiting influence on the respiratory burst of human granulocytes but does not damage the granulocytes.
G. Regenerative and Growth-Stimulating Activity
After incubation for 72 h in a nutrient solution, fibroblasts form saturated monolayers, the fibroblasts cease their activity and growth stops. The cell fuel adenosine triphosphate (ATP), which is essentially formed in the mitochondria, is needed to activate certain enzymes which, for example, control the cell skeleton, the ionic channels, the uptake of nutrients and a large number of other important biological processes. The protein content of the cells was determined by Bradford's method [cf. Anal. Biochem. 72, 248-254 (1977)]. Glutathione (GSH) is a special protein which is produced by the cells for protection against oxidative stress and environmental poisons, more particularly against heavy metals. The three amino acids involved in the reduced form of GSH are linked to special cytoplasmatic enzymes which need ATP for activation. An increase in the GSH concentration leads to an increase in the glutatione-S-transferase activity, a detoxifying enzyme. The GHS content was determined by Hissin's method [cf. Anal. Biochem. 74, 214-226 (1977]. The growth-stimulating effect of vaccinium extract was tested on human fibroblasts. In a first series of tests, the fibroblasts were incubated in a nutrient medium for 1 day at 37° C./5% by vol. CO 2 , the nutrient medium was replaced by a medium which contained the test substance and the fibroblasts were incubated for another 3 days at 37° C. The protein content of the cells and the ATP concentration were then determined. The survival-stimulating effect was determined in a second series of tests. To this end, the fibroblasts were incubated first for 3 days at 37° C. in a nutrient solution and then for 3 days at the same temperature in a test solution. The protein content of the cells and the GSH concentration were then determined. The results are set out in Table 7 in %-rel. against a blank sample and represent the results of 3 series of measurements involving triple determination.
TABLE 7 Growth- and survival-stimulating effect (figures = % -rel.) Conc. Test series 1 Test series 2 Ex. Test Product % w/v Proteins ATP Proteins GSH C10 Blank 0 100 100 100 100 7 Vaccinium extract 0.005 105 111 104 108

The results show that the test substances stimulate the metabolism in regard to growth and protection of the fibroblasts.
H. Effectiveness Against Ageing of the Skin
The enzyme glucose-6-phosphate dehydrogenase (G6PDH) catalyzes the first step of the “pentose shunt” in which a major constituent of DNA, namely deoxyribose, is formed. In this first step, glucose-6-phosphate (G6P) is converted by G6PDH into 6-phosphatogluconate (6PG). At the same time, the co-enzyme needed for this conversion, NADP, is reduced to NADPH2 which in turn is capable of catalyzing a number of other biological reactions such as, for example, the recycling of glutathione or the synthesis of lipids. Reduced glutathione protects many enzymes having SH groups and cells against oxidative stress, such as UV exposure for example. The G6PDH content is thus an important parameter for cell protection and skin renewal. The G6PDH activity was determined in vitro on human fibroblasts by Okada's enzymatic method; the DNA content was determined by Desaulniers' method. The results are set out in Table 8 which shows the results of three series of measurements involving triple determination in %-rel against a blank.
TABLE 8 Stimulation of G6PGH activity (figures = % -rel.) Conc. Test series 1 Test series 2 Ex. Test Product % w/v Proteins ATP Proteins GSH C11 Blank 0 100 100 100 100 8 Vaccinium extract 0.005 104 108 11 109

I. Immunostimulation

Immunostimulation is the umbrella term for biochemical processes in which messenger substances, such as β-glucans for example, stimulate the body's own defences, for example for binding and secreting toxins and accelerating the renewal of skin cells. It is known that organisms lose this ability with increasing age. Immunostimulation can be observed in vitro on human leucocytes activated beforehand with a yeast extract (zymosan) [cf. Capsoni et al., Int. J. Immunopharm. 10(2), 121-133 (1998)]. A culture of polymorphonuclear neutrophilic granulocytes (PMNs) was incubated with the vaccinium extract for 24 h at 37° C./5% by vol. CO 2 . The addition of zymosan initiated the respiratory burst. After 30 mins, the PMN count was determined with an automatic cell counter while the quantity of reactive oxygen species (ROS) released in the supernatant liquid was spectroscopically determined with luminol. The results are set out in Table 9 as %-rel against the standard. Table 9 shows the mean value of two series of measurements involving triple determination.
TABLE 9 Immunostimulation (figures in % rel.) Conc. Ex. Test product % w/v No. of leucocytes ROS released V12 Blank 0 100 100 9 Vaccinium extract 0.005 88 91

The results show that the test substances stimulate the immune system and lastingly strengthen the body's own defences, more particularly the skin cells.
J. Activation of Lipolysis
Lipolysis is understood to be the removal of triglycerides from the adipocytes. Crucial importance attaches to the triglyceride lipase which converts the glycerides into free fatty acids and glycerol which are then carried away via the circulation system. The fatty acids can then be burnt, for example, in the muscle cells and hence serve as energy stores. To investigate lipolytic activity, adipocytes were isolated from human subcutaneous tissue [cf. Rodbell, J. Biol. Chem. 239(2), 375-380 (1964)]. The corresponding cultures were inoculated with the test substances and incubated for 90 mins. at 37° C. The quantity of glycerol released in the supernatant liquid was spectroscopically determined [cf. Carpene et al., J. Pharmacol. (Paris), 12(2), 219-224 (1981)]. The results are set out in Table 10 as %-rel. against the standard and represent the average value of two series of measurements involving triple determination.
TABLE 10 Lipolysis (figures in % -rel.) Conc. Ex. Test product % w/v Glycerol released C13 Blank 0 0 10 Vaccinium extract 0.005 8

The results show that the test substances stimulate lipolysis and hence contribute towards accelerating the availability of cell fuel.
Various formulations for skin treatment preparations containing vaccinium extracts are set out in Table 11.
TABLE 11 Examples for cosmetic preparations (water, preservative to 100% by weight) Composition (INCI) 1 2 3 4 5 6 7 8 9 10 Emulgade ® SE 5.0 5.0 4.0 — — 5.0 5.0 4.0 — — Glyceryl Sterate (and) Ceteareth 12/20 (and) Cetearyl Alcohol (and) Cetyl Palmitate Eumulgin ® B1 — — 1.0 — — — — 1.0 — — Ceteareth-12 Lameform ® TGI — — — 4.0 — — — — 4.0 — Polyglyceryl-3 Isostearate Dehymuls ® PGPH — — — — 4.0 — — — — 4.0 Polyglyceryl-2 Dipolyhydroxystearate Monomuls ® 90-O 18 — — — 2.0 — — — — 2.0 — Glyceryl Oleate Cetiol ® HE — — — — 2.0 — — — — 2.0 PEG-7 Glyceryl Cocoate Cetiol ® OE — — — 5.0 6.0 — — — 5.0 6.0 Dicaprylyl Ether Cetiol ® PGL — — 3.0 10.0 9.0 — — 3.0 10.0 9.0 Hexyldecanol (and) Hexyldecyl Laurate Cetiol ® SN 3.0 3.0 — — — 3.0 3.0 — — — Cetearyl Isononanoate Cetiol ® V 3.0 3.0 — — — 3.0 3.0 — — — Decyl Oleate Myritol ® 318 — — 3.0 5.0 5.0 — — 3.0 5.0 5.0 Coco Caprylate Caprate Bees Wax — — — 7.0 5.0 — — — 7.0 5.0 Nutrilan ® Elastin E20 2.0 — — — — 2.0 — — — — Hydrolyzed Elastin Nutrilan ® I-50 — 2.0 — — — — 2.0 — — — Hydrolyzed Collagen Gluadin ® AGP — — 0.5 — — — — 0.5 — — Hydrolyzed Wheat Gluten Gluadin ® WK — — — 0.5 0.5 — — — 0.5 0.5 Sodium Cocoyl Hydrolyzed Wheat Protein Euperlan ® PK 3000 AM — — — — — — — — — — Glycol Distearate (and) Laureth-4 (and) Cocamidopropyl Betaine Arlypon ® F — — — — — — — — — — Laureth-2 Vaccinium extract 1.0 1.0 1.0 1.0 1.0 2.0 2.0 2.0 2.0 2.0 Hydagen ® CMF 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Chitosan Magnesium Sulfate Hepta Hydrate — — — 1.0 1.0 — — — 1.0 1.0 Glycerin (86% by weight) 3.0 3.0 5.0 5.0 3.0 3.0 3.0 5.0 5.0 3.0 Composition (INCI) 11 12 13 14 15 16 17 18 19 20 Dehymuls ® PGPH 4.0 3.0 — 5.0 — — — — — — Polyglyceryl-2 Dipolyhydroxystearate Lameform ® TGI 2.0 1.0 — — — — — — — — Polyglyceryl-3 Diisostearate Emulgade ® PL 68/50 — — — — 4.0 — — — 3.0 — Cetearyl Glucoside (and) Cetearyl Alcohol Eumulgin ® B2 — — — — — — — 2.0 — — Ceteareth-20 Tegocare ® PS — — 3.0 — — — 4.0 — — — Polyglyceryl-3 Methylglucose Distearate Eumulgin VL 75 — — — — — 3.5 — — 2.5 — Polyglyceryl-2 Dipolyhydroxystearate (and) Lauryl Glucoside (and) Glycerin Bees Wax 3.0 2.0 5.0 2.0 — — — — — — Cutina ® GMS — — — — — 2.0 4.0 — — 4.0 Glyceryl Stearate Lanette ® O — — 2.0 — 2.0 4.0 2.0 4.0 4.0 1.0 Cetearyl Alcohol Antaron ® V 216 — — — — — 3.0 — — — 2.0 PVP/Hexadecene Copolymer Myritol ® 818 5.0 — 10.0 — 8.0 6.0 6.0 — 5.0 5.0 Cocoglycerides Finsolv ® TN — 6.0 — 2.0 — — 3.0 — — 2.0 C12/15 Alkyl Benzoate Cetiol ® J 600 7.0 4.0 3.0 5.0 4.0 3.0 3.0 — 5.0 4.0 Oleyl Erucate Cetiol ® OE 3.0 — 6.0 8.0 6.0 5.0 4.0 3.0 4.0 6.0 Dicaprylyl Ether Mineral Oil — 4.0 — 4.0 — 2.0 — 1.0 — — Cetiol ® PGL — 7.0 3.0 7.0 4.0 — — — 1.0 — Hexadecanol (and) Hexyldecyl Laurate Bisabolol 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Vaccinium extract 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Hydagen ® CMF 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Chitosan Copherol ® F 1300 0.5 1.0 1.0 2.0 1.0 1.0 1.0 2.0 0.5 2.0 Tocopherol/Tocopheyl Acetate Neo Heliopan ® Hydro 3.0 — — 3.0 — — 2.0 — 2.0 — Sodium Phenylbenzimidazole Sulfonate Neo Heliopan ® 303 — 5.0 — — — 4.0 5.0 — — 10.0 Octocrylene Neo Heliopan ® BB 1.5 — — 2.0 1.5 — — — 2.0 — Benzophenone-3 Neo Heliopan ® E 1000 5.0 — 4.0 — 2.0 2.0 4.0 10.0 — — Isoamyl p-Methoxycinnamate Neo Heliopan ® AV 4.0 — 4.0 3.0 2.0 3.0 4.0 — 10.0 2.0 Octyl Methoxycinnamate Uvinul ® T 150 2.0 4.0 3.0 1.0 1.0 1.0 4.0 3.0 3.0 3.0 Octyl Triazone Zinc Oxide — 6.0 6.0 — 4.0 — — — — 5.0 Titanium Dioxide — — — — — — — 5.0 — — Glycerin (86% by weight) 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 (1, 6) Soft cream, (2, 3, 7, 8) Moisturizing emulsion, (4, 5, 9, 10) Night cream (11) W/O sun protection cream, (12-14) W/O sun protection lotion, (15, 18, 20) O/W sun protection lotion, (16, 17, 19) O/W sun protection cream