The present invention also relates to processes for the preparation of said pigments and eudermic cosmetic make-up compositions comprising said pigments.

BACKGROUND OF THE INVENTION The use of cosmetic products for make-up date back to ancient time.

Presently the cosmetic science has developed a variety of sophisticated make-up compositions with high quality aesthetic effects.

Most of the present make-up compositions, particularly those for the periocular zone, contain inorganic pigments. Preferred inorganic pigments are the thermo-and photochemically stable iron oxides, available in main colors, whose proper combination with white pigments allow the formulation of any desired make- up formula.

Other inorganic pigments are chromium and manganese compounds, which are transition metal similar to iron thus bearing a multiplicity of oxidation levels.

These metal compounds display catalytic redox properties, therefore promote oxidative stress on skin by activating Fenton-like reactions which generate harmful free oxygenated radicals. The contact of iron and transition metals actually promote oxidative burdens and skin ageing, particularly if combined with light radiations, as described by Jurkiewicz B. A. and Buettner G. R. in Photochem Photobiol, 64 (6) : 918- 22 (1996).

An approach to the amelioration both end-use performance and the decrease of skin ageing due to the pigment has consisted in their coating with lipophilic substances. For example, silicones was used in US. 5458681, hydrogenated lecithin in US4622074, with fatty soaps in US4648908, silicone-containing compound and fatty acid ester in US05738841, hydrogenated lecithin in US4622074, in US6080424 by natural phospholipid and proteins.

Nonetheless, such lipid coatings may be depleted during the mixing steps at high temperatures required in order to melt the solid waxes and fats during the make- up manufacturing.

The pigments intended for the make-up may be pigments coated by a poly- oligomeric film, such as in EP00340103 by a crosslinked polybet alanine and polyhydric alcohol, in W009426711 by carbazol derivatives, in US6004541 by perfluoridated-derivatives, in US5989570 by a plasticizing oligomer plus a film- forming polymer, in US5968496 by an imidazolium derivative and a branched polyethylene glycol, in US5091013 by carbozylated polymers, and other synthetic compounds such as in US5788955, US5961989, W009636323, EP00875243.

Ideally, said cosmetic pigments should perform additional protectant activities when the make-up formulations containing them are applied to the skin.

Based on the above, a cosmetic make-up composition containing pigments showing non-aggressive behaviour and also characterized by a high mechanical stability throughout the manufacturing steps would be of great interest. Said pigments should be further characterized by good stability during storage and handling of the make-up compositions.

DETAILED DESCRIPTION OF THE INVENTION One of the purpose of the present invention is to avoid the skin ageing due to the contact of iron, chromium or manganese compounds of the pigments used for decorative purposes in make-up compositions by using iron-free pigments.

We have now found that the common white-colorlessfillers used in make-up compositions may be mixed and/or coated with vegetal complexes in order to obtain a safe colored pigment.

Therefore, the present invention relates to new pigments comprising : a) a white-colorless filler ; b) a lake formed by at least one vegetal substance in the form of a complex with at least one lake-forming ion and c) optionally one or more UV absorbers.

In the following description, the new pigments are called"phytopigments".

The whole phytopigUnent of the invention is a solid colored particle which is insoluble in either aqueous or oily medium.

In the phytopigments of the present invention, the white-colorless filler and the vegetal substance complexed with at least one lake-forming ion may be either mixed or separated, thus forming two layers.

Hence, according to a particular embodiment, the present invention relates to new pigments comprising : a) an inner core of a white-colorless filler ; b) an outer layer of at least a vegetal substance in the form of a complex with at least one lake-forming ion and c) optionally one or more UV absorbers.

Suitable white-colorless fillers for the purposes of the present invention are the well-known filler used in cosmetics. According to the present invention, the term "filler"designates any solid (micro) particle used in the manufacturing of cosmetic (especially make-up) formulations with the purpose of diluting the colored pigment (s) in order to attain the required chromatic value, as well as to impart the desired physical properties to the final composition. They are characterized by being inert, non-toxic, non-oxidizing (namely non containing transition metals with multiple valences, e. g. Fe, Cr) micronized compounds and include white metal oxides, inorganic salts, lamellar pigments, as well as white-colorless organic compounds such as natural or synthetic polymers.

Illustrative examples of metal oxides are the oxides of titanium, zinc, or cerium, optionally pre-coated with silica, alumina as well as salts and mixture thereof.

Illustrative examples of inorganic compounds are aluminium hydroxide sulphate, bentonite and montmorillonite, silica, aluminate silicate, magnesium aluminium silicate, sodium silicate, sodium magnesium silicate, calcium silicate, pumice powder, kaolin, barium sulphate, bismuth chloride oxide, calcium carbonate, calcium sulphate, zirconium oxide, cerium oxide and magnesium carbonate.

Illustrative examples of lamellar pigments are lauroyllysine, ceramic microparticles coated with zirconium powder, lamellar titanium dioxide, lamellar talc, boron nitride, mica (sericite), and lamellar bismuth oxychloride.

Illustrative examples of organic polymers are cellulose fibres, e. g. wood dust or cotton fibres, powdered silk, starch, expanded microspheres, e. g. of polyvinylidene/acrylonitrile copolymer, powdered polyethylene, powdered nylon, powdered silicone, powdered polypropylene, powdered polycarbonate, powdered urea-formaldehyde resin, powdered crosslinked gelatine, powdered collagen, powdered keratin, powdered polystyrene and powdered Teflon*.

The filler can also consist of any mixture of inorganic and/or organic fillers.

Suitable vegetal substances for the purposes of the present invention are those selected among plant molecules capable of forming stable complex with the lake- forming salts. Accordingly, said vegetal substances shall own at least one carbonyl group and one hydroxyl group, in vicinal or adjacent position (e. g. on two condensed aromatic rings ; on position 4 and 5 of a flavonoid structure ; on a beta-diketo- aliphatic chain) so to allow the formation of a bidentate complex with the lake- forming ions ; their ketoenolic synthones may also being used.

The vegetal substances preferably show a good solubility in an alkaline medium, from which they be precipitable by acidification at pH between 9 and 7 or lower.

The vegetal substances whose characteristics meet the above-indicated requisites belong to the following groups : -flavonoids -benzindenopyranones -open ring polyphenols -quinones -chlorophyllins -vegetal melanins.

Flavonoids are a large class of vegetal substances.

Illustrative examples of flavonoids are those contained in grape and in the peel of other edible fruits, thus containing flavanonols such as myricetin, flavones such as luteolin, flavandiols such as dihydroquercetin, as well as the flavanols. Grape contains also the anthocyanins and chalcones, which are the biosynthetic precursors of flavonoids and anthocyanins, the latter being slowly reverted to the corresponding chalcones when kept in neutral or slighly alcaline aqueous solution. Anthocyanins are the coloured matter of flowers and also occurring in coloured fruits and vegetables, including cyanidin and delphinidin, which may also be substituted as mono, di-saccharides, and position 3 may be acylated, e. g. with p-coumaric acid.

Further illustrative examples of flavonoids are the oligomeric proanthocyanidins (OPC), precondensed oligomer of flavanols, i. e. (+)-catechin and (-)-epicatechin, which are commonly extracted from grape seed, pine bark, cocoa and other vegetal sources rich in flavan-3-ols in the free, glucosylated, esterified, or condensed forms. Galloylated catechin monomers are typically extracted from green tea or Catechu gambir, which contain (+)-gallocatechin (GC), (+)-gallocatechin gallate (GCG), (-)-epigallocatechin (EGC) and (-)-epigallocatechin gallate (EGCG).

Further illustrative examples of flavonoids are the flavanones and flavonols, also known as citrus bioflavonoids because of the high content thereof in Citrus spp, although being widely found throughout the plant kingdom. Flavanones such as hesperetin, naringenin and glycosides thereof are typically found in citrus peels. An almost ubiquitary flavonols is quercetin, quit widespread in plants although being conveniently extracted from Aesculum hippocastanum whose glycosides include the 3-rhamnoside (quercetrin) and the 3-rutinoside (rutin), the latter occurring in a variety of plants, including tobacco, tea, eucalyptus, grapes, etc., being commercially available in highly purified forms from several vegetable sources.

Mixed flavonoids are found in several plants, such as morin and maclurin (which is a benzophenones) in old fustic (Morus tinctoria), chrysin from the heartwood of Pinus monticula, or the complex flavonoid mixture found in Chrysanthemum and goldenrod.

Other vegetal compounds which are suitable for our purposes include the plant polyphenols which are biogenetically correlated with flavonoid, e. g. the benzyndenpyranones, i. e. polycyclic substances tipically occurring in some tropical plants.

Illustrative examples are brazilein and hydroxybrazilein, the former obtained from Cesalpinacee spp. such as brazilwood and sappanwood, the latter is also know as haematoxyilin and commonly extracted from logwood.

Other vegetal compounds suitable for our purposes also include the phytoalexins (open ring polyphenols), for instance dihydroxyphenols such as hydroxytyrosol and its esters (oleuropein, verbascoside, etc.) found in olive fruit and leaves ; protocathechuic acid found in most higher woody plants and in wheat ; and protocathechuic aldehyde, found in vanilla.

Further illustrative examples of open ring polyphenols are gallic acid and its derivatives, which may be obtained from hydrolysis of plants rich in tannins, such as nutgalls. Tannins (alias tannic acid) are also classified as ellagitannins or gallotannins, the latter releasing gallic acid by hydrolysis treatment.

Other vegetal compounds suitable for our purposes include the vegetal quinones, which comprise anthraquinones, dianthrones, and naphtoquinones Illustrative vegetal anthraquinones are rhein, emodin, aloe-emodin, parietin, the frangulines, crysophanol and its glucoside (crysophanein), the cascarosides, and the reduced forms (anthracenons and anthrols) and glucosides thereof, occurring in different proportion in rhubarb, senna, cascara and frangula, as well as in some lichens ; aloin and aloe-emodin from aloe ; and morindon from Coprosma australis.

The anthraquinones are historically represented by alizarin and related compounds, such as ruberetic acid and purpurin, from Rubia tinctoria and other rubiacee.

Illustrative vegetal quinons are the dianthrones, i. e. dimeric anthrones such hypericin from Hypericum p. and the sennosides from senna.

Further illustrative vegetal quinones are napthtoquinones such as lawsone from henna ; juglone from walnut ; alkannin from Alkanna and its enantiomer,

shikonin ; the lapachols frcm Tabebuias spp. (e. g."pau d'arco") ; and plumbagins from Plumbago spp.

Other vegetal compounds suitable for our purposes include chlorofillines. The well-known metal-porphyrines are ubiquitary pigments of the green plants, which contain chlorophyl A and B, converted by the hydrolysis of the phytolic residue and/or by ion exchange in the water-soluble Mg-chlorophyillin (olive green) and Cu- chlorofillin (bright green). Source of chlorofillins for our purpose are the commercially available Mg-or Cu-chlorofillins (food color E-140). Nevertheless, hydrolized vegetal extracts rich in chlorophyl can be used.

Other vegetal compounds suitable for our purposes are the vegetal melanins.

Examples of vegetal melanins are the"phytomelanins"resulting from the polymerization of plant polyphenols, and the micomelanins called"naphtomelanins", i. e. the broad photoabsorbing biopolymers containing naphthalene groups, which are tipically produced by selcted fungi strains.

Suitable phytomelanins for the purpose of the present invention may be either extracted from plant sources, as disclosed in WO00/09616, or more conveniently obtained by synthesis from vegetal monomers alone, in combination or in conjunction with eumelanin precursors, as disclosed in our copending application PCT/IB00/01276.

Suitable micomelanins for the purpose of the present invention may be either extracted from fungi, or more conventiely obtained by chemical or enzymatic synthesis from dihydroxynaphthalene alone, in combination or in conjunction with eumelanin or phytomelanin precursors, as disclosed in our pending application M12000A 1513.

The vegetal compounds suitable for our purpose may occur either in the free form (aglycones) or as natural occurring esters and ethers (e. g. glycosides, galates, and the like) as well as in oligomeric form (e. g. proanthocyanidins and viniferins).

Glycosides are the 0-derivatives of the plant polyphenols in the plain form (aglycones), generally substituted in one or two hydroxy groups in the 3, 5 or 7

positions with naturally occurring mono-di-or trisaccarides, such as ruthoside, galactoside, rhamnoside, glucoside, sophoroside, rhamnoglucoside, and the like.

According to a preferred aspect of the present invention, the vegetal compounds may be in form of titred plant extracts with known chemical composition, such as those obtained by standardized extraction methods from vegetal sources, either in solid form, e. g. dry extracts, or in liquid form, e. g. hydroalcoholic or alkaline solution.

Even though other vegetal substances may be used, the afore mentioned ones are particularly preferred for make-up compositions due to the best balance of optimum requisites : the photostability of the insoluble complexes, the availability of the extract or purified fractions or the isolated pure compound as well as the synthetic equivalent. The vegetal compounds as enriched fraction or even as pure compounds offer the advantage of producing pigments particularly stabile and with bright color.

According to the present invention the term"lake-forming ions"designates inert ions which can form polydentate complexes with the aforementioned vegetal substances.

Suitable lake-forming ions are those selected among water soluble salts of aluminum and zinc in either cationic or amphoteric form, as well as from titanium and alkaline-earthy metal salts. In some cases, tin salts from soluble stannous (Sn2+) and stannic (Sn4+) salts may be used as lake-forming ions.

Examples of such salts are the sulphates, nitrates, chlorides and acetates of aluminum, zinc, titanium, magnesium, calcium, strontium and barium salts.

Further example of the inert metal salts are some alkaline amphoteric complexes, such as sodium or potassium aluminate and zincate.

In a particularly preferred embodiment of the present invention, said salts are reacted with an alkaline solution comprising the vegetal substances, and the acid- base reaction provides soluble non-toxic salts (e. g. NaCI) which can be washed away from the insoluble precipitated complex, i. e. the phytopigment.

In a further preferred embodiment of the present invention, the pigments are formed without mixing a filler suspension to the alkaline solution of the vegetal substances. The aforementioned alkaline solution, which generally comprise a moderate excess of alkalies with respect to the stechiometric value necessary to dissolve the vegetal pigment, is thereby mixed to an aqueous (or hydroalcoholic) solution of the soluble salts of lake-forming ions until neutral or slighly acidic pH.

The ions will be partially reacted with the vegetal substances to form the vegetal complexes, whilst the ion excess is converted into the corresponding oxide and hydrated oxide. As an example, aluminium and/or zinc salts precipited by an alkaline solution of a vegetal substance end up in a phytopigment which is an intimate admixture of the vegetal complex (lake) with alumina hydrate and/or zinc oxide, respectively.

The choice of the pair inorganic pigment-vegetal substances mainly depends on the desired color of the vegetal complex. In that sense the alkaline-earthy vegetal complexes generally display a blues shift when compared with the equivalent Al-, Zn-and Ti-complexes, which in turns hold a more covalent bound with the vegetal substance when compared with the partially ionic bound in Mg, Ca, Sr and Ba chelates. The proportion of ionicity decreases the HOMO-LUMO distance (i. e. the energy gap between the High Occupied Molecular Orbital and the Low Unoccupied Molecular Orbital) of the conjugated moiety of the anionic form of the vegetal substance, which in turns explain the bathochromic shift (blue shift) of the alkaline- earthy vegetal complexes compared to the Al-, Zn-or Ti-complexes.

Nothewothy, the black pigment with a black (or grayish-black) color was attained by carefully selecting complementary colors in due proportion, thus with repeated trials on the proportion of the alkaline solution of the vegetal compound in admixture and, simultaneously, on the chosen of the lake-forming salts, which also affect both the chroma and the value of the single components.

The phytopigment of the present invention may be prepared by lacquering procedures which are well known to those are skilled on the art.

A preferred procedure is the direct precipitation. In this case the white- colorless fillers are suspended in a solution formed by the alkaline salts of the vegetal substance, then the phytopigments are precipitated by adding said suspension to a solution of lake-forming ion, e. g. the soluble acidic salt of the Al, Zn, Ti, alkaline- earthy metals, or of mixture thereof.

Further preferred methods are based on co-precipitation or pre-coating procedures. An illustrative example of these procedures comprises the solubilization of both the vegetal substance as alkaline salt and the aluminium or zinc ions, as sodium or potassium aluminate or zincate. The filler is thereby suspended into the alkaline solution and gradually brought to a pH between 9. 5 and 10. 5 by the addition of a mineral acid. The soluble acidic salts of Al, Zn, alkaline-earthy metals (e. g.

CaC12) or mixture thereof are then slowly added to the warm slurry, finally neutralized with a mineral acid.

A further example of this procedure comprises the pre-coating with Al3+, Zn2+, Ti4+ or alkaline-earthy oxide-hydroxides, formed by suspending the filler in water, heating at 40-90°C, followed by the addition of an aqueous acidic solution of a water-soluble salt of Al or Zn. Simultaneously, a mineral alkali or acid is added to maintain pH around 5 to 9 until the precipitation takes place, then the pigment slurry is lacquered by precipitation of a vegetal substance with soluble acidic salt of the Al, Zn, alkaline-earthy metals, or mixture thereof, in order to form a firmly adhering vegetal lake.

The phytopigments of the invention may be also produced by other lacquering techniques.

An example of laquering techniques includes the formation of complexes by the use of alkaline-earthy hydroxides, i. e. by mixing a reactive suspension of the lacquering salt (s) (e. g. Ca (OH) 2) with a slightly alkaline or hydroalcoholic solution of the vegetal substances, followed by neutralization by addition of an inorganic acid, bicarbonates or carbon dioxide solutions.

Other examples of laquering techniques are those which make use of the vegetal substances in neutral or slightly acidic aqueous solution, therey suspended or

solubilized by heating, for examples at 70° to 95°C. This solution is added with the filler and stirred at this temperature until at least part of the vegetal substance are absorbed onto the filler. The soluble salts of lake-forming ions (also known as mordants) are then mixed under stirring, the slurry is heated and stirred, eventually neutralized, to provide the phytopigment of invention.

Other examples of laquering techniques are those where the lake-forming ions (mordants) are first reacted with the filler in a aqueous suspension at high temperature (e. g. 50° to 95° C), then added with the solution or suspension of vegetal substances in neutral or slightly acidic aqueous or hydroalcoholic solution, thereby stirred and eventually neutralized, to provide the phytopigments of invention.

Other examples of laquering techniques are the direct reaction of a solution of lake-forming ions (mordants), thereby admixed with the vegetal substances, either neutral or slightly acidic aqueous or hydroalcoholic suspension or solution under heating and stirring, generally followed by neutralization.

The phytopigments of the invention may be also produced by further lacquering techniques which are well-known to those skilled in the field. The use of different lacquering techniques causes only minor modifications to the pigmentary features of the products obtained according to the present invention.

It may be useful to carry out an hydrolytic and or oxidative pre-treatment of the vegetal substance prior to use. For example the anthraquinoids kept in alkaline solution with a slow stream of air increase the anthraquinones content by the oxidation of the reduced forms (anthranols and anthrones), or enhance the haematoxyilin/haematein ratio in the logwood extract. The anaerobic alkaline pre- treatment may also increase the redness of proantocyanosides and the browness of catechins ; or convert the blue-violet anthocyanins in the yellow-green chalcones ; or fully hydrolizes extract containing chlorophylls into chlorophyllins.

The slurry of phytopigments obtained in aqueous suspension shall be then washed, dried and finally micronized. The washing may be carried out with water or carbonate solution (C02 or NaHCO2 aqs) at any temperature from about 20 to 90°C.

A final washing with a water-soluble organic solvents (e. g. acetone) may be applied

to speed the drying step up. The drying may be carried out at any temperature between 30 and 150°C, preferably at 80-130°C and under vacuum or by atomization, followed by grinding. The micronization is generally not applied since the base pigment used for the coating are preferably used as micron-like size particles.

The invention also relates to cosmetic or dermatological compositions comprising the phytopigments described above.

The wide color range of the phytopigments of the present invention allows the preparation of a variety of cosmetic compositions, namely make-up compositions.

The compositions according to the invention may also comprise any cosmetically acceptable ingredients. The expression"cosmetically acceptable ingredients"designate in the present specification products which are suitable for their use in cosmetic treatments, for example those included in the INCI list drawn by the European Cosmetic Toiletry and Perfumery Association (COLIPA) and issued in 96/335/EC"Annex to Commission Decision of 8 May 1996".

Among preferred cosmetic ingredients there may be pigment and dyes of natural and synthetic origin to complement the color of make-up compositions.

Illustrative examples of synthetic pigment and dyes are organic the D&C organic colorants generally used in cosmetics, such as Cl 45, 170, Cl 15, 585, CI 45, 380, CI 15, 510, Cl 45, 370, CI 45, 410 ; CI 15, 630, CI 15, 850 : 1 ; CI 15, 850 : 2, CI 19, 140, CI 12, 085, CI 45, 425, CI 15, 985, CI 73, 360, CI 45, 430, CI 77, 266, CI 75, 470.

Illustrative example of natural and semi-synthetic pigment and dyes are carotenoids, xanthophyll, caramel, natural and synthetic eumelanins, carmine, red yacca gum, dracorubin (dragon blood), monascus red, and further vegetal or animal colors.

A particularly suitable example of natural pigment is the vegetal charcoal (Carbo vegetabilis). In a preferred embodiment of the present invention the Carbo vegetabilis used in the composition of invention is previously treated as a phytopigment, i. e. dispersed in a alkaline solution (containing or non-containing the

vegetal substances) and the alkaline slurry is precipitated by mixing with a acidic lake-forming salts.

As brief illustrative example, the fine powder of Carbo vegetabilis is dispersed in NaOH IN and the slurry is mixed with Aids, or ZnCl2, or mixture thereof, then washed, filtered, dried and grinded. A black pigment with higher bulk density and consistency than the original charcoal is thereby obtained.

As further brief illustrative example, the above operation is repeated but using a alkaline solution further comprising anthocyanins in a quantity of 10% by weight, based on the total weight of the final pigment.

The composition of this invention provides for the use of 0. 1-99% of other cosmetically acceptable components such as oils, waxes, surfactants, silicones, perfluorides, other non-coated or differently coated powder, fragrances, dyes or coloured pigments, or other base materials as INCI. The base materials with natural origin are preferred in this invention, the ones with vegetal origin being more preferred.

Further preferred cosmetic ingredients to the face, eyes or lips may comprise from 5 to 98% weight of a fatty body selected from the group consisting of an oil and a mixture of an oil and a wax, e. g. paraffin oil, petrolatum oil, mineral oil having a boiling point between 310° and 410° C, purcellin oil, perhydrosqualene, calophyllum oil, sweet almond oil, palm oil, avocado oil, olive oil, ricin oil, wheat germ oil, dimethylpolysiloxane, butyl myristate, isopropyl myristate, cetyl myristate, isopropyl palmitate, butyl stearate, hexadecyl stearate, isopropyl stearate, octyl stearate, isocetyl stearate, decyl oleate, hexyl laurate, propylene glycol dicaprylate, diisopropyl adipate, oleyl alcohol, linoleic alcohol, linolenic alcohol, isostearyl alcohol, octyl dodecanol, isopropyl lanolate, isocetyl lanolate, glycol octanoate, glycerol octanoate, glycol decanoate, glycerol decanoate and cetyl ricinoleate, said wax comprising a member selected from the group consisting of a microcrystalline wax, paraffin wax, petrolatum wax, ozokerit, montan wax, beeswax, spermaceti wax, lanolin wax, lanolin alcohols, hydrogenated lanolin, hydroxylated lanolin, acetylated lanolin, lanolin fatty acids, alcohol of acetylated lanolin, candellila wax,

carnauba wax, Japan wax cocoa butter, hydrogenated ricin oil, hydrogenated palm oil, hydrogenated tallow, hydrogenated coconut oil, polyethylene wax, propylene glycol monomyristate, myristyl myristate, silicone wax, cetyl alcohol, stearyl alcohol, mono-, di-and triglycerides solid at 25° C, stearyl monoethanolamide, rosin, glycol abietate, glycerol abietate, sucroglyceride, and the oleates, myristates, lanolates, stearates and dihydroxy stearates of calcium, magnesium, zinc and aluminium.

The pigment of invention are characterized by a distinctive color (alias hue), by its chroma, which is the purity, saturation or intensity of a hue ; as well as by its value, which is the extent to which a colour reflects or absorbs light.

The pigments also have a typical tinting strength, i. e. its dominant effect on a pigment mixtures, as each pigment is relatively transparent or opaque, thus affecting the final color when mixed with other pigment or filler. Those which reflect a greater quantity of light or have a high intensity make'high key'colours.

The phytopigments of our invention are generally characterized by a low tinting strength, therefore the make-up composition comprising thereof shall make little if any use of additional white pigments or fillers.

The phytopigments of the invention can be employed alone or in combination with white pigments and fillers in make-up compositions in any amounts between 0. 1 and 70 % by weight. One or more kind of the phytopigments, according to the different possible solutions of the invention, may be present in said compositions.

Typical make-up compositions are eye shadow pencils (pigment content from about 5 to 15%), mascara (pigment content from about 10 to 70%), eye shadow powder compacts (pigment content from about 20 to 70%), liquid compositions for eye shadow and eye makeup (pigment content from about 7 to 15%), lipsticks (pigment content from about 10 to 20%), lip gloss cream (pigment content from about 10 to 15%), make-up in pencil form (pigment content from about 15 to 25%), make-up powder compacts (pigment content from about 10 to 50%), make-up emulsions (pigment content from about 5 to 10°s/o), make-up gel (pigment content from about 1 to 5%), sunlight protection emulsions and tanning emulsions (pigment

content from about 5 to 1) %), foam bath concentrates with color gloss (pigment content from about 0. 1 to %), skin care lotions (pigment content from about 0. 1 to 2%).

In a further preferred embodiment of the present invention the phytopigments may be eventually post-coated with further organic substances, the post-coating may be performed either on the wet phytopigment or, more preferably, on the final phytopigment after dying and grinding.

Illustrative examples of organic substances suitable for the post-coating treatment are silicone, triethanolamine stearate, sodium hexametaphosphate, lecithin and hydrogenated lecithin, fatty acid and alkaline or earthy-alkaline salts thereof, and mixture thereof. Further examples of organic substances suitable for the post-coating treatment are polymers such silicones, poly-beta-alanines, perfluoridated polymers, carbazole polymers, polyhydric alcohol, polyimidazoles, and mixture thereof.

Any specific post-coating may offer a distinctive advantage and performance features. For example the post-coating with carboxypolymers pigment produce a higher power of holding moisture, the peptide oligomers improve the resistance to moisture by reducing the effect of stickiness by hydroscopicity while increasing the adhesion capacity of the make-up products ; the organosilicones increase both water repellence and spreading ; whilst the use of lecithin improve the skin adhesion. The post-coating with perfluorated substances ameliorate the UV-protection ; the polymer containing ethylenic unsaturation and acrylic, methacrylic, allylic, methallylic or vinyl homopolymers or copolymers increase the shelf life ; the organosilicons enhance smooth feel and the adhesion to the skin ; whilst silicone compounds in combination with hydrocarbon compounds improve the adhesion capacity of the make-up while possessing good cosmetic properties when applied to the skin. The post-coating with fatty acid soaps renders the phytopigments water-repellent while giving refreshment and/or smoothness to the cosmetic make-up comprising thereof.

The substances used to carried out the post-coating onto the phytopigments may need the presence of a soluble metal salt in order to be grafted to the pigment surface. Generally the quantity of lake-forming salts present in the phytopigments is

sufficient to perform the aforementioned task, otherwise a new layer of these salts may be formed afterwards.

The phytopigments of the present invention are characterized by excellent lightfastness rating, capability of the pigment to resist fading (discoloration) when targeted with light radiations.

Notheworhty, the lightfastness ratings may be expressed, for example, as provided by the American Society for testing and materials in"Standard Test Methods for Lightfastness of Pigments Used in Artists'Paints", ASTM D 5098, for example by method C : exposure in xenon-arc lightfastness apparatus.

Under named test, a pigments with a lightfastness rating equalling I is considered"excellent"in term of lightfastness, with a rating of 11 as"very good", with a reating of III is classified as with"fair lightfastness", whereas the rating of IV represents the"poor lightfastness"or"fugitive"behaviour.

The lightfastness test is designed to measure the amount of time that the pigment remains visibly unchanged on exposure to natural light in normal situations of display. However, to accelerate the fading process to within practical time limits, lightfastness is measured by exposing the paint to unusually strong and prolonged artificial light.

The original blue wool test for lightfastness requires the pigment sample to be exposed to direct sunlight alongside patches of wool (mounted in a blue wool textile fading card), each dyed with a blue that fades in light at a different rate. When the paint just begins to discolor, the wool card is used to judge the amount of light it has received ; this gives the blue wool standard for the paint's lightfastness. The modern way is to use a xenon arc fadeometer to test the pigment, as this instrument measures precisely the amount of illumination the sample has received. Filters are used to adjust the xenon light to match the spectrum received from the sun.

The blue wool test measures 8 levels of lightfastness, from 8 (extremely lightfast) to 1 (fugitive), but the lightfastness ratings are conventionally expressed by the following rating scheme : ABC

8 900 1 7 300 1 6 100 II 5 33 III 4 10 III 3 3. 6 IV 2 1. 2 IV 1 0. 4 IV wherein A is the value from the blue wool test ; B are the megalux hours of exposure before fading becomes noticeable (NB exposure to 8 hours of normal room lighting (200 lux) every day for one year equals about 1. 2 megalux) ; and C are the aforementioned four groups of lightfastness rating.

The phytopigments of the present invention are generally characterized by a lightfastness rating comprised between II and III, with few examples of lightfastness rating 1. It could therefore be useful to protect the compositions comprising them for example, by avoiding the exposure to light during storage, handling and displaying the finished make-up compositions.

Alternatively, said make-up compositions are either packed in opaques containers or within packaging which are transparent to visible light but not to UV-A radiations and/or to low visible wavelenght light.

In a preferred embodiment of the present invention, the phytopigment are associated with UV absorbers (sunscreens) in order to prevent or delay the fading (discoloration) of the finished make-up composition from light radiations. By this meaning, the pigment of the present invention may increase of at least one class of the blue wool test (A), given as a measure of their lightfastness rating.

Suitable UV absorber for the purposes of the present invention are selected among substances capable of quenching the UV-radiation, so that to improve the lightfastness rating of the phytopigments.

The invention also relates to the combination of a phytopigment according to the invention with a UV filter and cosmetic or dermatological compositions comprising said combination.

The UV absorbers used to minimize fading of the pigment of the present invention may be conceived in two different forms : (i) in a co-precipitated form with the pigment or (ii) in combination with the phytopigment in the cosmetic composition.

The (i) form above may for instance be produced by lacquering one or more suitable UV absorber along to the vegetal substances during the preparation of the phytopigment.

UV absorbers suitable for the (i) form are the sunscreen agents exhibiting chemical properties similar to those of the vegetal substances used in the preparation of the pigment, i. e. forming water-soluble alkaline salts by reaction with aqueous alkali such NaOH or amine and, moreover, precipitating as insoluble salts by addition of Al3+, Zn2+, Ti4+ and alkaline-earthy metal ions.

The formation of insoluble lakes comprising the UV absorbers above may be conveniently performed along with step of lacquering, i. e in the same alkaline solution containing one or more vegetal substance and the core pigment or filler.

Alternatively, the formation of insoluble lakes of the W absorbers may be carried out in a separate step by lacquering techniques, for example on the wet or dried phytopigment.

Particularly suitable examples of such UV absorbers are the sulphonated sunscreen agents, thus bearing a sulphonic acid groups or sulphonate groups as a part of their molecular skeleton, as this moiety renders the substance freely soluble in aqueous solution and the alkaline salt are readily formed by addition of alkali, said salt are in turn substituted by the Al3+, Zn2, Ti4+ and alkaline-earthy metal ions to form an insoluble lake.

Illustrative examples of sulphonated UV absorbers are 3- (4'- sulphobenzyliden) canfora, 2-phenylbenzymidazol-5-sulphonic acid, 2, 4-phenylen- bis (benzymidazol-5-sulphonic acid), 2-hydroxy-4-methoxybenzophenone-5-

sulphonic, 4-(2-oxo-3-bc rnylidenemethyl) benzenesulphonic acid, 2-methyl-5- (2- oxo-3-bomylidenemethy !) sulp'ionic acid. Of course these water-soluble substances may be added either in their acid form or as the commercially available salts, such as sodium, potassium or triethanolammonium salts.

Other suitable examples of such UV absorbers are sunscreen agents bearing either a free carboxy group or a 2-hydroxybenzophenone, thus capable of precipitating as unsoluble lakes with Al3+, Zn2, Ti4 and alkaline-earthy metal ions.

Examples of such W absorbers are 4-aminobenzoic acid (PABA) ; cinnamic acid and 4-methoxy cinnamic acid, and salts thereof ; and 2-hydroxybenzophenone derivatives, such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'- methylbenzophenone and 2, 2'-dihydroxy-4-methoxybenzophenone.

Differently from the sulphonated UV absorbers, the latter UV-absorbers generally produce yellow lake with Al-+, Zn2, Ti4 and alkaline-earthy metal ions, as the conjugated system of molecular orbital is shifted at lower field of absorbance by the formation of a ion pair thereof. In such a case, the composition comprising phytopigment shall be adjusted to match the required color tone.

The ratio of UV absorbers to vegetal substances to be precipitated in the phytopigment of the present invention ranges from 5 : 1 to 1 : 50 w/w, preferably from 2 : 1 to 1 : 20 w/w, in particular from 1 : 2 to 1 : 10 w/w, in order to provide an efficient antifading activity on the pigment according to the invention.

UV absorbers suitable for the anti-fading activity according to (ii) are either oil-soluble or water-soluble sunscreens working on the UV-B and/or UV-A ranges.

Illustrative examples of UV absorbers, besides the afore mentioned suncreens, are oil-soluble substances such as, for example : 3-benzylidenecamphor derivatives, preferably 3- (4-methylbenzylidene) camphor and 3-benzylidenecamphor ; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, amyl 4- (dimethylamino) benzoate, ethyl 4- [bis [hydroxypropyl] aminobenzoate and glyceryl-4-aminobenzoate ; esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxy cinnamate and isopentyl 4- methoxycinnamate ; esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-

isopropylbenzyl salicylate, homosalate (3, 3, 5-trimethylcyclohexylsalicylate) and homomenthyl salicylate ; esters of benzylidenemalonic acid, preferably 2-ethylhexyl 4-methoxybenzylidenemalonate ; and 2, 4, 6-trianilino-(p-carbo-2'-ethyl-1'-hexyloxy)- 1, 3, 5-triazine ; derivatives of gallic acid such as digalloyl trioleate ; UV-A suncreens which are derivatives of dibenzoylmethane, in particular 1- (4'-tert-butylphenyl)-3- (4'-methoxyphenyl) propane-1, 3-dione and 1-phenyl-3- (4'-isopropylphenyl) propane- 1, 3-dione ; and miscellaneous compounds such as 2-ethylhexyl 2-cyano-3, 3- diphenylacrylate and methyl anthranilate.

The list of mentioned UV absorbers, which can be used in combination with the phytopigments, is illustrative only and it is not intended to be limiting.

The total amount of UV absorber being used in the cosmetic compositions of the present invention ranges, from 0. 1% by weight to 30% by weight, preferably 0. 5 to 10% by weight, in particular 1 to 6% by weight, based on the total weight of the formulations, in order to provide both anti-fading activity on the phytopigment and to protect the skin from the entire range of ultraviolet radiation.

In the following examples all parts and proportions are by weight and the solutions have 1M concentration, unless otherwise indicated.

EXAMPLES B) Examples 1-86-Phvotopigments on alumina The vegetal substances are solubilized in a mixture of water and an appropriate amount ofNaOH ION. Then a quantity of the white-colorless filler is admixed and suspended under stirring. This slurry is then added dropwise into a beaker fitted with a mechanical stirrer containing an aqueous solution of the lake- forming ions ("precipitants") and the mixture is kept for 10 minutes under stirring.

The slurry is then filtered and the filtrate is washed with warm deionized water, until soluble salts are removed. Finally, the resulting cake is dried at 80°C and grinded, thereby obtaining a colored pigment powder.

A variety of phytopigments are prepared with alumina (A1203*nH20), then coated with the vegetal complex. Noteworthy, similar pigment with different white- colorless substrates are prepared in further Examples.

The vegetal substances used are either in the form of extracts or as highly purified active ingredients, and thereafter precipitated on the substrate, to provide phytopigments as described in the following Tables I, II, III and IV. TABLE I Exam VEGETAL SUBSTANCE(s) (a) NaOH Al2O3(b) % Coating PRECIPITANT(s) PIGMENT ple extract or pure substance Notes q.ty 10 N q.ty (a)(a+b)100 substance q.ty COLOR N° (type/title) (*) (g) (ml) (g) (w/w%) (type) (ml) (aprox definition) 1 Rutin 3H2O NF XI - 7,5 9 67,5 10% AlCl3 27 gold<BR> 2 Rutin 3H2O DAB8 - 7,5 9 67,5 10% AlCl3 27 gold<BR> 3 Rutin 3H2O 95% - 7,5 9 67,5 10% AlCl3 27 gold-yellow<BR> 4 Rutin 3H2O NF XI - 7,5 10 67,5 10% AlCl3+CaCl21/2 10+100 gold-yellow<BR> 5 Rutin 3H2O 95% - 5 6,5 45 10% ZnCl2 75 gold-yellow<BR> 6 Old fustic extract (40% sol.) - 5 4,5 5 29% AlCl3 15 goldenrod<BR> 7 Old fustic extract (40% sol.) - 5 4,5 5 29% CaCl21/2 40 peru<BR> 8 Curcumin 90% - 2 5 10 17% AlCl3 15 orange-yellow<BR> 9 Curcumin 90% - 3 10 10 23% ZnCl21/2 110 orange-gold<BR> 10 Curcurnin 90% - 3 10 10 23% ZnCl21/2 110 orange<BR> 11 Rhubarb 115 anthraquinones - 5 10 15 25% CaCl21/2 150 tan4<BR> 12 Rhubarb 11% anthraquinones - 5,2 10 12 30% CaCl21/2 150 sandybrown<BR> 13 Rhubarb 11% anthraquinones (a) 5,2 10 12 30% CaCl21/2 150 darkgoldenroad<BR> 14 Rhubarb 11% anthraquinones - 6 10 16 27% AlCl3+CaCl21/2 10+100 chocolate<BR> 15 Rhubarb 11% anthraquinones - 5 5 20 20% ZnCl21/2 50 rosy brown<BR> 16 Rhubarb 11%+Lawsone 99% - 7,5+2,5 7,5 27 27% CaCl21/2 100 orange-peru<BR> 17 Frangula 19% anthraquinones - 4 8 6 40% CaCl21/2 100 saddlebrown<BR> 18 Frangula 19% anthraquinones - 6 6 30 17% CaCl21/2 75 leather<BR> 19 Frangula 19% anthraquinones (a) 1 2,5 3 25% CaCl21/2 35 reddish leather<BR> 20 Frangula 19% anthraquinones - 3,2 4,5 13 20% AlCl3+CaCl21/2 5+25 redidish leather<BR> 21 Frangula 19% anthraquinones - 5 5 20 20% AlCl3+CaCl21/2 1+80 golden-leather TABLE II a osa MEN k o 0 o ed- fireb 5 o ooof) ndia 00 in 21 lig 4 gra@ 1 6 6 m + ~s U D 2 i +1 T(s) 1 10 z substance AlCl3+CaCl21/2 CaCl21/2 AlCl3+CaCl21/2 AlCl3+CaCl21/2 AlCl3+CaCl21/2 U aC Cl 28% Ca 8% Zn@ 10% AlC u er- cl "' NaOH Al2O3(b) % otes q.ty 10 N q.ty (a)/(@ (*) (g) (ml) (g) (w - 5 5 13 - 1+0,5 6 13 - 2+0,5 5 13 b) 4+0,3 10 26 - 2 2 15 - 5,5 10 9 - 4 4 4,5 - 3 5 90 - 4 4 45 - 1 3 10 - 1 3 10 - 1 3 10 - 0,7+0,5 1 3 - 0,4+0,6 1,3 3 - 1+0,5 1,5 4 - 0,5+0,5 1 1 - 0,5+0,5 1 4 z (s) @ w NC gaz 90 . 5 substanc@ rcumin 90 rcumin 90 rcumin 90 gula 19% B g 9 S X em he con xtra N° @ 27 Rhubarb 11%+1 28 Frangula 19%+1 29 Aloin 90% 30 Sandalwood ext 31 Sandalwood ext 41 Brazilwood extr 42 Alizarine+Frang 43 Eumelanin (10% TABLE III 0 finitio nroad cl C -0 0 c p saim orang substance q.ty (type) (ml) AlCl3+CaCl21/2 2,5+20 CaCl21/2 8 AlCl3+CaCl21/2 3+60 CaCl21/2 60 AlCl3+CaCl21/2 3+40 AlCl3+CaCl21/2 10+90 CaCl21/2 15 AlCl3 12 AlCl3+CaCl21/2 2+40 AlCl3 7,5 CaCl21/2 15 ~ S 0% 3% U} @3(b) 12 11 O =r N a Z ~ ~s 0, O ,2+0,6 ,7+1,4 ,1+2,2 6 0, 0, 0 0 o (s)(a) (b), ( (c), ( w ce tu g ua 1@ a a X m : Exam VEGETAL ple extract or pure s@ N° (tpye/titl@ 44 Eumelanin (10%)+Frang@ 45 Eumelanin (10%)+Frang@ 46 Eumelanin (10%)+Frang@ 47 Hypericum Extract+Frang 48 Hypericum extract+Frang 49 Hypericum extract+Frang 50 Eumelanin (10%)+Brazil 51 Eumelanin (10%)+Brazil 52 Eumelanin (10%)+Brazil 53 Brazilwood extract+Fran 54 Brazilwood extract+Fran 55 Hypericum extr.+Brazilw 56 Hypericum extr.+Brazilw 57 Hypericum extr.+Brazilw 58 Proanthocyanosides 90% 59 Proanthocyanosides 90% 60 Proanthocyanosides 90% 61 Proanthocyanosides 90% 62 Loogwood+Frangula+Ru 63 Phytomelanin A 10% sol 64 Phytomelanin A 10% sol 65 Phytomelanin B 10% sol TABLE IV Exam VEGETAL SUBSTANCE(s) (a) NaOH Al2O3(b) % Coating PRECIPITANT(s) PIGMENT ple extract or pure substance Notes q.ty 10 N q.ty (a)/(a+b)100 substance q.ty COLOR N° (type/title) (*) (g) (ml) (g) (w/w%) (type) (ml) (aprox definition) 66 Logwood extract - 3 4 3 50% AlCl3 15 darkblue-purple<BR> 67 Logwood extract+Rutin 95% - 1+0,1 2,5 3 27% AlCl3 9 black-blue<BR> 68 Logwood extract (a) 2 5 1,5 57% AlCl3+CaCl21/2 20+4 black-blue<BR> 69 Logwood+Rutin NFXI - 1,25+0,5 5 2,5 41% AlCl3 16 dark olivedrab<BR> 70 Logwood+Rutin NFXI - 0,6+0,3 1,5 1,3 41% AlCl3 4,2 Olivedrab<BR> 71 Logwood+Rutin NFXI - 0,5+0,3 1 1 44% AlCl3 3 grayish black<BR> 72 Logwood extract - 2 4 1,5 57% AlCl3+CaCl2 20+4 pithpuff4<BR> 73 ChlorophyllinA(Cu) - 1 4 20 5% CaCl21/2 50 mediumseegreen<BR> 74 ChlorophyllinA(Cu)+Brazilwood extr. - 0,5+4,5 5 5 67% AlCl3 50 black-violet<BR> 75 ChlorophyllinA(Cu)+Brazilwood extr. - 1,2+6,3 7,5 1 88% CaCl21/2 100 black-green<BR> 76 ChlorophyllinA(Cu)+Brazilwood extr. - 2+8 10 10 50% CaCl21/2 130 black-green<BR> 77 Alkannet extract type D - 1,5 1,2 1,2 50% AlCl3 4 dark blueviolet<BR> 78 Alkannet extract type C - 1,5 1 1,5 50% CaCl21/2 15 black-blue<BR> 79 Alkannet extract type C - 1,5 1,2 1,5 50% AlCl3 4 black-blue<BR> 80 Alkannet extract type D - 1,5 1 1,5 50% CaCl21/2 15 medium blue<BR> 81 Antocyanins (20% solution) - 1 2 1 50% CaCl21/2 30 dark navajo<BR> 82 Antocyanins (20%)+Soluble coffee - 2+1,5 2 100% AlCl3 7 gray-black<BR> 83 Antocyanins (20%)+Rutin NFXI 6+0,2 1,25 100% AlCl3 4 gray-black<BR> 84 Antocyanins (20%)+Rutin NFXI - 2+1 4 100% AlCl3 14 dark oilverdrab<BR> 85 Antocyanins (20%)+Eumelanin (10%) - 8+0,8 1,7 100% AlCl3 6 dark gray<BR> 86 Autocyanins (powder) - 5 5 100% ZnCl21/2 50 dark gray

Notes (*) on Tables 1. II, Ill, and IV : (a) treatment : the alkaline solution of the vegetal substance (1% in NaOH 0. 5N) was pretreated by air injection for 1 hour ; (b) treatment : the reaction mixture (i. e. the phytopigment slurry) was heated and stirred at 60-70° C for further 15 minutes prior to washing, filtration, drying and grinding ; (c) treatment : the filtrate was washed with warm carbonate water ; (d') Eumelanin (10% solution) was obtained by air injection onto a solution of vegetal L-dopa 10% w/v in NaOH IN for 24 h ; (d") Phyomelanin A (10% solution) was obtained by air injection onto a solution of quercetin 10% w/v in NaOH IN for 24h ; (d"') Phyomelanin B (10% solution) was obtained by air injection onto a solution of gallic acid 10% w/v in NaOH IN for 24h.

Example 87-Phytopigments by the use of amphoteric lake-forming salts Into a 500 ml beaker fitted with a mechanical stirrer, I g of a rutin trihydrated is solubilized in a mixture of 200 ml of water and 12 ml of NaOH IN. The solution is heated to 50-60°C and added with 3 g of NaAlO2 (5 ml of 60 g/1 solution). A dispersion of 10 g of alumina in 200 ml of water is then admixed. The slurry is kept under stirring for 30 minutes, then slowly acidificated by the dropwise addition of HCI 3N in 30 minutes at 50-55° C, until pH is stabilized at 10. 5. The slurry is added with 6 ml water solution of CaCl2 0. 5M. After 20 minutes under stirring, the slow acidification with HCI is carried out until pH 9-10, and then continued until neutral pH. The slurry is hot filtered, washed, dried at 80°C and grinded, thereby obtaining a yellow pigment.

Example 88-Phytopigments bv pre-forming the lake on the substrate Into a 500 ml beaker fitted with a mechanical stirrer are suspended 3 g of zinc oxide in 200 ml of deionized water and heated, with stirring, at 75° C. Then NaOH IN is added to pH 8, and 10 ml of solution AlCI3 1M is added dropwise together with NaOH IN, in order to throughout maintain the pH around 8. The slurry is stirred for 1 hour, then added with a solution of 1 g of a rutin trihydrated in 200 ml of water

and 12 ml ofNaOH IN."he slurry is stirred at 80-90° C, filtered, washed water, dried and grinded, to provide a yellow pigment powder.

Example 89-Phvtopigments with a coprecipitated UV-adsorber The procedure of the Examples 1-96 was applied to a solution of 3 g of curcumin and 1 g of 2-phenylbenzimidazole-5-sulphonic acid (Neo Heliopan Hydro, Haarmann&Reimer, Holzminden, Germany) in 40 ml of NaOH IN, with 10 g of alumina and 13 ml of AICl3 1M, to provide a orange-yellow pigment.

Example 90-Phytopigments with a coprecipitated UV-adsorber Same as Example 89 but with 4 g of anthocyanins and 150 ml of CaCl2 0. 5M instead of curcumin and All3, respectively, to provide a brown pigment.

Example 91 - Phytopigments with a coprecipitated UV-adsorber The procedure of the Examples 1-96 was applied to a solution of 6 g of fustic acid extract (by dry weight) and 1. 5 g of 2-hydroxy-4-methoxybenzophenone (Neo HeliopanW BB, H&R, Holzminden, Germany) in 90 ml of NaOH IN, with 10 g of alumina and 30 ml of Aids 1M, to provide a yellow pigment.

Example 92-Phytopigments with a coprecipitated UV-adsorber Same as Example 89 but with 5 g of brazilwood extract aand 80 ml of ZnCl2 0. 5M instead of curcumin and AlCI3, respectively, to provide a red-scarlet pigment.

Example 93-Phvtopigments on mica Same as the Example 4 but with mica (sericite) as substrate instead of alumina, thereby using the same proportion as (a)/ (a+b) % by weight.

Example 94-Phytopigments on titanium dioxide Same as the Example 4 but with 10 g titanium dioxide (rutile) as substrate instead of 67. 5 alumina ( (a)/ (a+b) % = 43% by weight).

Example 95-Phytopigments on zinc oxide Same as the Example 4 but with 40 g zinc oxide as substrate instead of 67. 5 alumina ((a)/(a+b)%=16% by weight) Example 96-Phvtopigments on microcristalline cellulose Same as the Example 4 but with microcristalline cellulose as substrate instead of alumina, thereby using the same proportion as (a)/ (a+b) % by weight.

Example 97-Phytopigments on powdered silk Same as the Example 4 but with powdered silk as substrate instead of alumina, thereby using the same proportion as (a)/ (a+b) % by weight.

Post-coating Example 1 5 g of pigment of Example 4 are suspended in 5 ml of 4 % aqueous solution of Al2 (SO4) 3, heated at 50° C and stirred for 15 minutes. Then 10 ml of 1% solution of lecithin in water kept at pH 9 (by diluted HCI) are slowly added to the mixture, which is stirred for 15 minutes at 50° C. The pigment is filtered, dried in oven at 80° and milled.

Post-coating Example 2 5 g of pigment of Example 5 are suspended in 10 ml water under stirring and added with 0. 1 g of hydrogenated lecithin is added, then the mixture is heated at 70° C until complete dispersion of the lecithin. Then 1 ml of a 20% solution of ZnS04 in water is slowly added and the mixture is stirred for 15 minutes. The pigment is filtered, dried and milled.

Post-coating Example 3 Same as the Post-coating Example 2 but with the pigment of Example 83 and sodium stearate instead of hydrogenated lecithin Post-coating Example 4 5 of the pigment of Example 71 are suspended in 10 ml of a 1% aqueous solution of carboxymethyl cellulose in water and stirred for 15 minutes at 60°C. The pigment is filtered, dried and milled.

Post-coating Example 5 5 g of the pigment of Example 28 are stirred in 10 ml of a 1% solution sodium polyacrylate in water. The mixture is filtered, dried and milled. Then, 10 ml of an aqueous solution AICI3 0. IM is dropped into the dispersion under stirred for 15 minutes. The pigment is filtered, dried and milled.

Post-coating Example 6

2 g of pigment of Example 80 are suspended in 10 ml benzene containing 0. 10 g of methyl hydrodienepolysiloxane and stirred for 5 minutes. The mixture is dried under vacuum until solvent removal and the pigment is milled.

Post-coating Example 7 5 g of pigment of Example 82 are suspended in 10 ml ethanol containing 0. 1 g Fomblin HC/P2. The mixture is dried under vacuum until solvent removal and milled.

Post-coating Example 8 2. 5 g of the pigment of Post-coating Example 7 are suspended in 10 ml of a 1% aqueous solution of Al (NO) 3 and stirred for 15 minutes. The pigment is filtered, dried and milled.

Post-coating Example 9 5 g of pigment of Example 55 are suspended in 10 ml benzene and 0. 15 g of dimethylpolysiloxysilazane (n=30 ; Mw/Mn=1. 15). The mixture is dried at 80° C to remove benzene completely and then heated at 115° C for 3 hours.

Applicative Examples 1-3-Lipstick 100 g of lipsticks may contain : Appl. Ex. 1 Appl. Ex. 2 Appl. Ex. 3 Castor Oil 3. 10 3. 10 3. 10 Polybutene 0. 64 0. 64 0. 64 Isopropyl Palmitate 9. 28 9. 28 9. 28 Caprylic/Capric/Isostearic/Adipic Triglycerides2. 02 2. 02 2. 02 Candelilla Wax 7. 59 7. 59 7. 59 Medium Chain Triglyceride Oil 1. 66 1. 66 1. 66 Cetyl Ricinoleate 5. 50 5. 50 5. 50 Modified Beeswax 3. 26 3. 26 3. 26 Ozokerit 2. 88 2. 88 2. 88 Lanolin Oil 2. 00 2. 00 2. 00 Carnauba Wax 0. 46 0. 46 0. 46

Glycerol 12. 5 12. 5 12. 5 Panthenol 5. 00 5. 00 5. 00 Glyceryl Monostearate 2. 77 2. 77 2. 77 Propylene Glycol/Glyceryl Oleate (1 : 1 ratio) 4. 70 4. 70 4. 70 Lecithin 1. 03 1. 03 1. 03 Ascorbyl Palmitate 0. 50 0. 50 0. 50 Propylparaben 0. 10 0. 10 0. 10 2-Ethylhexyl salicylate (UVA-absorber) 3. 00 3. 00 3. 00 Butyl methoxydibenzoylmethane (UVB-abs) 2. 00 2. 00 2. 00 Phytopigment of Example 24 30. 0 Phytopigment of Example 19-24. 4 Phytopigment of Example 34--14. 0 Phytopigment of Example 8-5. 6 16. 0 Applicative Examples 4-6-Eve shadows 100 g of emulsions for eyelids may contain : Appl. Ex. 4 Appl. Ex. 5 Appl. Ex. 6 Carnauba wax 1. 10 1. 10 1. 10 Partially hydrogenated soybean oil 1. 90 1. 90 1. 90 Palm oil 1. 94 1. 94 1. 94 Triethanolamine stearate 5. 05 5. 05 5. 05 PEG-1000 10. 00 10. 00 10. 00 Talc (magnesium silicate) 0. 70 0. 70 0. 70 Phytopigment of Example 84 2. 00 Phytopigment of Example 52 9. 60 4. 10 Phytopigment of Example 76 3. 60 3. 60 Phytopigment of Example 94-1. 50 2. 30 Phytopigment of Example 73--9. 50 Phytopigment of Example 72-9. 40 8. 50 White pigment Ti02 (rutile) 1. 3

Sodium polymethacrylate 0. 50 0. 50 0. 50 Preservatives 0. 50 0. 50 0. 50 Demineralized water qb to 100 to 100 to 100 Applicative Examples 7-9-Foundations 100 g of emulsions used as foundation may contain : Appl. Ex. 7 Appl. Ex. 8 Appl. Ex. 9 Triethanolamine stearate 2. 55 2. 55 2. 55 Mono-and di-glycerol stearate 0. 46 0. 46 0. 46 Talc (magnesium silicate) 1. 93 1. 93 i. 93 Phytopigment of Example 89 5. 50 2. 50 Phytopigment of Example 90 4. 00 6. 70 Phytopigment of Example 92 6. 50 5. 80 Phytopigment of Example 801. 103. 10 Phytopigment of Post-coating Example 2--4. 50 Phytopigment of Post-coating Example 5--4. 00 Phytopigment of Post-coating Example 3--7. 20 White pigment Ti02 (rutile)--1. 00 2-Ethylhexyl salicylate (UVA-absorber)--2. 50 Micronized Nylon 7. 01 7. 00 7. 00 Mix of PEG-6 and PEG-32 6. 10 6. 10 6. 10 Cyclomethycone 13. 00 13. 00 13. 00 Propylenglycol 5. 00 5. 00 5. 00 Glycerol 4. 50 4. 50 4. 50 Demineralized water qb to 100 to 100 to 100