WO2011016140A1

WO2011016140A1 - Composite pigment and method for preparation thereof

Info

Publication number: WO2011016140A1
Application number: PCT/JP2009/064088
Authority: WO
Inventors: Takahiro Suzuki; Shinichi Matsufuji; Takehiko Kasai
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2009-08-04
Filing date: 2009-08-04
Publication date: 2011-02-10
Anticipated expiration: 2012-02-04
Also published as: JP6231275B2; JP2013501079A

Abstract

The present invention relates to a composite pigment comprising a stacking of at least two plate-like substrates and at least one UV filter material located at least in part between the at least two plate-like substrates. The composite pigment can be prepared by a method comprising a step of subjecting a plurality of substrates, at least one UV filter, and optionally a coloring pigment, to a hybridizer process. The composite pigment can be advantageously used as a component for a cosmetic composition.

Description

DESCRIPTION

COMPOSITE PIGMENT AND METHOD FOR PREPARATION THEREOF

TECHNICAL FIELD

The present invention relates to a composite pigment comprising a plurality of substrates each of which is in the form of a plate, UV filter (s) and optionally coloring pigment (s), as well as a method for preparing the composite pigment.

BACKGROUND ART

Many cosmetics include one or more UV filters in order to shield UV rays. In particular, skin cosmetics commonly include UV filters such as fine particles of Tiθ₂ for protecting the skin from UV rays together with other components such as extender pigments, e.g., talc, mica and kaolin.

However, fine particles of TiO₂ have a high friction coefficient such that they do not easily spread on the skin, so that an unpleasant feeling on use is given to the skin.

Furthermore, solid fine particles such as TiO₂ fine particles can easily aggregate and have poor dispersibility . Therefore, it is often difficult to uniformly disperse them in the form of primary particles in cosmetics. Therefore, the UV filtering property of the cosmetics including UV filtering fine particles is difficult to be enhanced.

In accordance with the variety of needs in cosmetics, various research and developments have been performed. In particular, for providing cosmetics with a good UV filtering property, many types of surface treatments or composite pigments of UV filters have been proposed.

For example, JP-A-H05-214257, JP-A-H05-230394 and JP-A-H09-99246 disclose composite pigments comprising a single plate core particle and fine particles of UV filter (s) covering the single plate core particle. However, these composite pigments have a poor feeling on use, and there are some risks that fine particles of UV filter (s) may detach from the composite pigments to penetrate into the skin via pores on the skin, which may give adverse effects to the skin because the barrier property of the skin is not strong in pores, and that UV filter (s) when it or they irritate can easily contact with the skin, which may also give adverse effects to the skin.

DISCLOSURE OF INVENTION

Thus, an objective of the present invention is to provide a novel composite pigment which can provide a better feeling on use and a better UV filtering effect with reduced risks of fine particles of UV filter (s) penetrating into the skin via pores on the skin, and of UV filter (s) when it or they irritate easily contacting the skin to affect the skin.

The above objective of the present invention can be achieved by a composite pigment comprising a stacking of at least two plate-like substrates and at least one UV filter material located at least in part between the at least two plate-like substrates.

It is preferable that the plate-like substrate has an aspect ratio of at least 5, and that the plate-like substrate has a length ranging from 0.3 μm to 30 μm.

It is preferable that the at least one UV filter material is in the form of a layer having a thickness of 0.03 μm to 10 μm.

The composite pigment according to the present invention may have a thickness of 0.2 μm to 25 μm.

The plate-like substrate may comprise at least one inorganic material and/or at least one organic material. The inorganic material may be selected from the group consisting of natural mica, synthetic mica, sericite, kaolin, talc, clay mineral, hydrotalcite, boron nitride, calcium carbonate, barium sulfate, titanium oxide, hydroxyapatite, silica, silicate, zinc oxide, magnesium sulfate, magnesium carbonate, magnesium trisilicate, aluminum oxide, aluminum silicate, calcium silicate, calcium phosphate, magnesium oxide, bismuth oxychloride, glass flake, and mixtures thereof. On the other hand, the organic material may be selected from the group consisting of (meth) acrylates , polyamides, silicones,

polyurethanes, polyethylenes, polypropylenes, polystyrenes,

polyhydroxyalkanoates, polycaprolactams, poly (butylene) succinates, polysaccharides, polypeptides, polyvinyl alcohols, polyvinyl resins, fluoropolymers, wax, amidosulfonic acid polyvalent metal salts, acylated amino acids, and mixtures thereof.

The UV filter material may be organic or inorganic. The UV filter material may comprise an organic filter selected from the group consisting of anthranilic derivatives; dibenzoylmethane

derivatives; cinnamic derivatives; salicylic derivatives; camphor derivatives; benzophenone derivatives; β, β-diphenylacrylate

derivatives; triazine derivatives; benzotriazole derivatives;

benzalmalonate derivatives; benzimidazole derivatives; imidazoline derivatives; bis-benzoazolyl derivatives; p-aminobenzoic acid

(PABA) and derivatives thereof;

methylenebis (hydroxyphenylbenzotriazole) derivatives; benzoxazole derivatives; screening polymers and screening silicones; dimers derived from α-alkylstyrene; 4, 4-diarylbutadienes; octocrylene and derivatives thereof, guaiazulene and derivatives thereof, rutin and derivatives thereof, flavonoids, biflavonoids, oryzanol and derivatives thereof, quinic acid and derivatives thereof, phenols, retinol, cysteine, aromatic amino acid, peptides having an

aromatic amino acid residue, and mixtures thereof. On the other hand, the UV filter material may comprise an inorganic UV filter selected from the group consisting of silicon carbide, metal oxides which may or may not be coated, and mixtures thereof. The weight ratio of said substrates to the at least one UV filter material may be 100:1 to 100:500.

The composite pigment according to the present invention may further comprise at least one coloring pigment.

The composite pigment according to the present invention can be prepared by a method comprising a step of subjecting a plurality of plate-like substrates, at least one UV filter, and optionally a coloring pigment, to a hybridizer process. The composite pigment according to the present invention can be contained in a cosmetic composition.

BRIEF DESCRIPTION OF DRAWINGS

Fig. 1 shows SEM images of a composite pigment including a

plurality of plate-like core substrates. Fig. 1 (a) shows an outer appearance of the composite pigment, and Fig. l(b) shows a cross sectional view of the composite pigment.

BEST MODE FOR CARRYING OUT OF THE INVENTION

After diligent research, the inventors have discovered that it is possible to obtain a new composite pigment providing a better feeling on use and a better UV filtering effect with reduced risks of fine particles of UV filter (s) penetrating into the skin via pores on the skin and of fine particles of UV filter (s) easily contacting the skin to affect the skin.

The new composite pigment according to the present invention comprises a stacking of at least two plate-like substrates and at least one UV filter material located at least in part between the at least two plate-like substrates.

A part of the UV filter (s) may also be present on the outer surface of the stacking of the substrates. In this case, the stacking of the substrates can function as a core of the composite pigment .

The composite pigment according to the present invention can have a thickness of 0.2 μm to 25 μm, preferably 0.4 μm to 20 μm, more preferably 0.4 μm to 15 μm.

Since the composite pigment according to the present invention includes a stacking of plate-like substrates, the composite pigment is not in the exact form of a plate but has a shape with roundness such as a bulge or a spindle. Therefore, the feeling on use will be improved as compared to a composite pigment which is in the form of a plate in which a single core plate is covered by UV filter (s), which would function as a sandpaper to give a bad feeling on use to the skin.

Further, if a part of the UV filter (s) is present on the outer surface of a stacking of the plate-like substrates, a part of the better feeling on use of the composite pigment according to the present invention can be attributed to the fact that the UV filter (s) is/are firmly fixed on the stacking. Therefore, it is possible to reduce free UV filter (s) which have a high friction coefficient such that they do not easily spread on the skin, so that an unpleasant feeling on use is given to the skin. In addition, since the UV filter (s) can be spread and fixed on the surface of the stacking of the plate-like substrates, the UV filter (s) cannot aggregate but disperse in the form of primary- particles on that surface. Therefore, the UV filtering effects of the UV filter (s) can be enhanced.

Furthermore, since at least a part of at least one UV filter material is located between the substrates, the sandwiched UV filter material cannot directly contact with the skin. Therefore, the UV filter material between the substrates cannot penetrate into the skin via pores on the skin. In particular, if the UV filter irritates, a large amount of the UV filter cannot directly contact with the skin, because a part of the UV filter is captured between the substrates. Accordingly, the composite pigment according to the present invention is safer than a conventional composite pigment in which a single plate core is covered by UV filter (S) .

Hereafter, each of the elements constituting the composite pigment according to the present invention will be described in a detailed manner.

(Substrate)

The substrate to be used for the present invention has a shape of a plate. As long as the substrate is in the form of a plate, any substrate can be used. It is preferable that the substrate has an aspect ratio of at least 5, preferably more than 10, more

preferably more than 20, and more preferably more than 50. The aspect ratio can be determined by the average thickness and the average length according to the formula: aspect ratio =

length/thickness .

The plate-like substrate preferably has a length ranging from 0.3 μm to 30 μm, preferably 0.5 μm to 20 μm, more preferably 1 μm to 10 μm, and more preferably 2 μm to 5 μm.

The dimensions mentioned above are obtained by calculating the mean of the dimensions of one hundred substrates chosen on an image obtained with a scanning electron microscope.

The stacking of the substrates may be formed by aggregation of a plurality of plate-like plates which are randomly oriented.

However, it is preferable that the plate-like substrates are orderly oriented, and layered or piled at least in part,

preferably in total, sandwiching UV filter (s).

The material of the substrate is not limited. The material can be at least one inorganic material and/or at least one organic

material .

Preferably, the inorganic material can be selected from the group consisting of natural mica, synthetic mica, sericite, kaolin, talc, clay mineral, hydrotalcite, boron nitride, calcium carbonate, barium sulfate, titanium oxide, hydroxyapatite, silica, silicate, zinc oxide, magnesium sulfate, magnesium carbonate, magnesium trisilicate, aluminum oxide, aluminum silicate, calcium silicate, calcium phosphate, magnesium oxide, bismuth oxychloride, glass flake, and mixtures thereof. In particular, natural mica,

synthetic mica, sericite, kaolin, talc and mixtures thereof are preferable.

Preferably, the organic material can be selected from the group consisting of (meth) acrylates, polyamides, silicones,

polyurethanes, polyethylenes, polypropylenes, polystyrenes,

polyhydroxyalkanoates, polycaprolactams, . poly (butylene) succinates, polysaccharides, polypeptides, polyvinyl alcohols, polyvinyl resins, fluoropolymers, wax, amidosulfonic acid polyvalent metal salts, acylated amino acids, and mixtures thereof. As the fluoropolymers, for example, PTFE may be used. As the

amidosulfonic acid polyvalent metal salts, for example, N- lauroyltaurine calcium may be used. As the acylated amino acids, lauroyllysine may be used. In particular, polyamides such as

Nylon®, polyhydroxyalkanoates such as polylactic acids, and

mixtures thereof are preferable.

The substrate may or may not be coated. It is more preferable that the substrate is coated. The material of a coating of the substrate is not limited, but an organic material such as an amino acid, an N-acylamino acid, an amido, a silicone and a modified silicone, is preferable. As the organic material, mention may be made of lauroyllysine and acryl-modified silicone.

(Layer on Substrate)

The stacking of the plate-like substrates may be at least

partially covered by at least one layer comprising at least one UV filter. The layer, if present, is referred to as a coating layer. In order to provide the composite pigment according to the present invention with a shape with roundness such as a bulge or a spindle, it is preferable that the outer surface of a stacking of the plate-like substrates is covered with one or more coating layers. Preferably, 10% or more of .the outer surface is covered by the coating layer (s). More preferably, 50% or more of the outer surface is covered by the coating layer(s). More preferably, 80% or more of the outer surface is covered by the coating layer (s). Most preferably, the entire outer surface of a stacking of the plate-like substrates is covered by the coating layer(s).

The thickness of the coating layer may vary depending on several factors such as the size of the plate-like substrate. Typically, the thickness of the coating layer may range from 0.001 μm to 20 μm, preferably 0.01 μm to 15 μm, and more preferably from 0.03 μm to 10 μm, and more preferably from 0.1 μm to 5 μm.

If there are two or more coating layers on a stacking of the plate-like substrates, the thickness and the composition of the coating layers may be the same as or different from each other. The coating layer may comprise, other than the UV filter (s), any additional material (s) such as a coloring pigment and a binder, preferably a non-liquid binder. The additional material (s) may be present in an amount ranging from 1 to 50 wt% relative to the total weight of the UV filter (s) and the additional material (s). However, it is preferable that the coating layer (s) consist (s) of the UV filter(s) .

(UV Filters)

The composite pigment according to the present invention includes at least one UV filter at least in part between the plate-like substrates. Furthermore, as described above, the composite pigment according to the present invention may have at least one coating layer, which may comprise at least one UV filter, covering a stacking of the plate-like substrates. The UV filter (s) between the plate-like substrates and the UV filter (s) in the coating layer (s) may be the same or different, preferably the same.

The UV filter used for the present invention may be active in the UV-A and/or UV-B region. The UV filter may be hydrophilic and/or lipophilic and/or properly insoluble in solvents commonly used in cosmetics .

The UV filter may be in the form of a liquid or a solid such as a particle. If the UV filter is in the form of a solid particle, it is preferable that the UV filter is a fine particle such that the primary particle diameter thereof ranges from 1 nm to 5 μm, preferably 10 nm to 1 μm, more preferably 10 nm to 100 nm, and more preferably 10 nm to 20 nm.

If UV filter (s) in the form of fine particles is/are used, the composite pigment according to the present invention has an effect that it can provide not a white appearance but a transparent or clear appearance, because the fine particles do not aggregate but spread in and on the substrates. It should be noted that free fine particles of UV filter (s) easily aggregate to give a white appearance to the skin. The material of the UV filter (s) is not limited. The UV filter may be organic or inorganic. If two or more UV filters are used, the material (s) of the UV filters may be the same as or different from each other.

The organic UV filter may be selected from the group consisting of anthranilic derivatives; dibenzoylmethane derivatives; cinnamic derivatives; salicylic derivatives; camphor derivatives;

benzophenone derivatives; β, β-diphenylacrylate derivatives;

triazine derivatives; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazoline derivatives; bis-benzoazolyl derivatives; p-aminobenzoic acid (PABA) and

derivatives thereof; methylenebis (hydroxyphenylbenzotriazole) derivatives; benzoxazole derivatives; screening polymers and screening silicones; dimers derived from α-alkylstyrene; 4,4- diarylbutadienes; octocrylene and derivatives thereof, guaiazulene and derivatives thereof, rutin and derivatives thereof, flavonoids, biflavonoids, oryzanol and derivatives thereof, quinic acid and derivatives thereof, phenols, retinol, cysteine, aromatic amino acid, peptides having an aromatic amino acid residue, and mixtures thereof.

Mention may be made, as examples of organic UV filters, of those denoted below under their INCI names, and mixtures thereof.

Anthranilic derivatives: Menthyl anthranilate, marketed under the trademark "Neo Heliopan MA" by Haarmann and Reimer.

Dibenzoylmethane derivatives: Butyl methoxydibenzoylmethane, marketed in particular under the trademark "Parsol 1789" by

Hoffmann-LaRoche; and Isopropyl dibenzoylmethane.

Cinnamic derivatives: Ethylhexyl methoxycinnamate, marketed in particular under the trademark "Parsol MCX" by Hoffmann-LaRoche; Isopropyl methoxycinnamate; Isopropoxy methoxycinnamate; Isoamyl methoxycinnamate, marketed under the trademark "Neo Heliopan E 1000" by Haarmann and Reimer; Cinoxate (2-ethoxyethyl-4-methoxy cinnamate) ; DEA Methoxycinnamate; Diisopropyl methylcinnamate; and Glyceryl ethylhexanoate dimethoxycinnamate. Salicylic derivatives: Homosalate (homomentyl salicylate),

marketed under the trademark "Eusolex HMS" by Rona/EM Industries; Ethylhexyl salicylate, marketed under the trademark "Neo Heliopan OS" by Haarmann and Reimer; Glycol salicylate; Butyloctyl

salicylate; Phenyl salicylate; Dipropyleneglycol salicylate, marketed under the trademark "Dipsal" by Scher; and TEA Salicylate, marketed under the trademark "Neo Heliopan TS" by Haarmann and Reimer .

Camphor derivatives, in particular, benzylidenecamphor

derivatives: 3-Benzylidene camphor, manufactured under the

trademark "Mexoryl SD" by Chimex; 4-Methylbenzylidene camphor, marketed under the trademark "Eusolex 6300" by Merck; Benzylidene camphor sulfonic Acid, manufactured under the trademark "Mexoryl SL" by Chimex; Camphor benzalkonium methosulfate, manufactured under the trademark "Mexoryl SO" by Chimex; Terephthalylidene dicamphor sulfonic acid, manufactured under the trademark "Mexoryl SX" by Chimex; and Polyacrylamidomethyl benzylidene camphor, manufactured under the trademark "Mexoryl SW" by Chimex.

Benzophenone derivatives: Benzophenone-1 (2,4- dihydroxybenzophenone) , marketed under the trademark "Uvinul 400" by BASF; Benzoρhenone-2 (Tetrahydroxybenzophenone) , marketed under the trademark "Uvinul D50" by BASF; Benzophenone-3 (2-hydroxy-4- methoxybenzophenone) or Oxybenzone, marketed under the trademark "Uvinul M40" by BASF; Benzophenone-4 (Hydroxymethoxy benzophonene sulfonic acid) , marketed under the trademark "Uvinul MS40" by

BASF; Benzophenone-5 (Sodium hydroxymethoxy benzophenone

Sulfonate) ; Benzophenone-6 (Dihydroxy dimethoxy benzophenone) ;

marketed under the trademark "Helisorb 11" by Norquay;

Benzophenone-8 , marketed under the trademark "Spectra-Sorb UV-24" by American Cyanamid; Benzophenone-9 (Disodium dihydroxy dimethoxy benzophenonedisulfonate) , marketed under the trademark "Uvinul DS- 49" by BASF; Benzophenone-12, and n-Hexyl 2- (4-diethylamino-2- hydroxybenzoyl ) benzoate . β, β-Diphenylacrylate derivatives: Octocrylene, marketed in

particular under the trademark "Uvinul N539" by BASF; and

Etocrylene, marketed in particular under the trademark "Uvinul N35" by BASF. Triazine Derivatives: Bis-Ethylhexyloxyphenol methoxyphenyl

triazine, marketed under the trademark "Tinosorb S" by Ciba-Geigy; Ethylhexyl triazone, marketed in particular under the trademark "Uvinul T150" by BASF; Diethylhexyl butamido triazone, marketed under the trademark "ϋvasorb HEB" by Sigma 3V; 2,4,6- Tris (dineopentyl 4 ' -aminobenzalmalonate) -s-triazine; and the symmetrical triazine screening agents described in U.S. Pat. No. 6,225,467, WO 2004/085412 (see compounds 6 and 9) or the document "Symmetrical Triazine Derivatives", IP.COM Journal, IP.COM INC, WEST HENRIETTA, NY, US (20 Sep. 2004), in particular the 2,4,6- tris (biphenyl) -1,3,5-triazines (especially 2,4,6-tris (biphenyl-4- yl) -1, 3, 5-triazine) and 2 , 4 , 6-tris ( terphenyl) -1, 3, 5-triazine, which is taken up again in WO 06/035000, WO 06/034982, WO

06/034991, WO 06/035007, WO 2006/034992 and WO 2006/034985.

Benzotriazole derivatives, in particular, phenylbenzotriazole derivatives: Drometrizole trisiloxane, marketed under the

trademark "Silatrizole" by Rhodia Chimie or "Mexoryl XL" by

L' Oreal; 2- (2, 4-dihydroxyphenyl) -2H-benzotriazole; 2- (2-hydroxy-5- tert-butylphenyl) -2H-benzotriazole; 2- (2-hydroxyphenyl) -2H- benzotriazole.

Benzalmalonate derivatives: Dineopentyl 4 ' -methoxybenzalmalonate, and Polyorganosiloxane comprising benzalmalonate functional groups, such as Polysilicone-15, marketed under the trademark "Parsol SLX" by Hoffmann-LaRoche .

Benzimidazole derivatives, in particular, phenylbenzimidazole derivatives: Phenylbenzimidazole sulfonic acid, marketed in

particular under the trademark "Eusolex 232" by Merck, and

Disodium Phenyl Dibenzimidazole tetrasulfonate, marketed under the trademark "Neo Heliopan AP" by Haarmann and Reimer.

Imidazoline derivatives: Ethylhexyl dimethoxybenzylidene

Dioxoimidazoline propionate. bis-Benzoazolyl derivatives: The derivatives as described in EP- 669,323 and U.S. Pat. No. 2,463,264. para-Aminobenzoic acid and derivatives thereof: PABA (p- Aminobenzoic acid) , Ethyl PABA, Ethyl dihydroxypropyl PABA,

Penthyl dimethyl PABA, Ethylhexyl dimethyl PABA, marketed in particular under the trademark "Escalol 507" by ISP, Glyceryl PABA, and PEG-25 PABA, marketed under the trademark "ϋvinul P25" by BASF.

Methylenebis (hydroxyphenylbenzotriazole) derivatives: Methylene bis-benzotriazolyl tetramethylbutylphenol, marketed in the solid form under the trademark "Mixxim BB/100" by Fairmount Chemical or in the micronized form in aqueous dispersion under the trademark "Tinosorb M" by Ciba Specialty Chemicals, and the derivatives as described in U.S. Pat. Nos . 5,237,071, 5,166,355, GB-2, 303, 549, DE-197,26,184 and EP-893,119.

Benzoxazole derivatives: 2, 4-bis [5-1 (dimethylpropyl)benzoxazol-2- yl- ( 4-phenyl) imino] -6- (2-ethylhexyl) imino-1, 3, 5-triazine, marketed under the trademark of Uvasorb K2A by Sigma 3V.

Screening polymers and screening silicones: The silicones

described in WO 93/04665.

Dimers derived from α-alkylstyrene : The dimers described in DE- 19855649.

4 , 4-Diarylbutadiene Derivatives: 1, 1-Dicarboxy (2, 2 ' - dimethylpropyl ) -4 , 4-diphenylbutadiene .

Octocrylene and derivatives thereof: Octocrylene.

Quaiazulene and derivatives thereof: Guaiazulene, and Sodium

Guaiazulene Sulfonate.

Rutin and derivatives thereof: Rutin, and Glucosylrutin.

Flavonoids: Robustin (isoflavonoid) , Genistein (flavonoid),

Tectochrysin (flavonoid), and Hispidone (flavonoid).

Biflavonoids : Lanceolatin A, Lanceolatin B, and Hypnumbiflavonoid A. Oryzanol and derivatives thereof: r-oryzanol. Quinic acid and derivatives thereof: Quinic acid. Phenols: Phenol. Retinols: Retinol. Cysteines: L-Cysteine.

Peptides having an aromatic amino acid residue: Peptides having tryptophan, tyrosine or phenylalanine.

The preferred organic UV screening agents are selected from:

Ethylhexyl methoxycinnamate, Homosalate, Ethylhexyl salicylate, Octocrylene, Phenylbenzimidazole sulfonic acid, Benzophenone-3, Benzophenone-4, Benzophenone-5, n-Hexyl 2- (4-diethylamino-2- hydroxybenzoyl) benzoate, 4-Methylbenzylidene camphor,

Terephthalylidene dicamphor sulfonic acid, Disodium phenyl

Dibenzimidazole Tetrasulfonate, Ethylhexyl triazone, bis- Ethylhexyloxyphenol Methoxyphenyl triazine, Diethylhexyl butamido triazone, 2 , 4, 6-tris (dineopentyl 4 ' -aminobenzalmalonate) -s- triazine, 2,4, 6-tris (diisobutyl 4 ' -aminobenzalmalonate) -s-triazine, 2, 4, 6-Tris (biphenyl-4-yl) -1, 3, 5-triazine, 2, 4, 6-Tris (terphenyl) - 1, 3, 5-triazine, Methylene bis-benzotriazolyl

Tetramethylbutylphenol, Drometrizole trisiloxane, Polysilicone-15, Dineopentyl 4 ' -methoxybenzalmalonate, 1, 1-Dicarboxy (2, 2 ' - dimethylpropyl) -4 , 4-diphenylbutadiene, 2, 4-bis [5-1

(dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6- (2- ethylhexyl) imino-1, 3, 5-triazine, and their mixtures.

More preferable organic UV filters are Ethylhexyl methoxycinnamate, Drometrizole trisiloxane, and mixtures thereof.

The inorganic UV filter may be selected from the group consisting of silicon carbide, metal oxides which may or may not be coated, and mixtures thereof.

Preferably, the inorganic UV filters are selected from pigments (mean size of the primary particles: generally from 5 nm and 100 nm, preferably from 10 nrα and 50 nm) formed of metal oxides which may or may not be coated, such as, for example, pigments formed of titanium oxide (amorphous or crystalline in the rutile and/or anatase form) , iron oxide, zinc oxide, zirconium oxide or cerium oxide, which are all UV photoprotective agents well known per se.

The pigments may or may not be coated. The coated pigments are pigments which have been subjected to one or more surface

treatments of chemical, electronic, mechanochemical and/or

mechanical nature with compounds such as described, for example, in Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53-64, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal alkoxides (titanium or aluminum alkoxides), polyethylene, silicones, proteins (collagen, elastin) , alkanolamines, silicon oxides, metal oxides or sodium

hexametaphosphate .

In a known manner, the silicones are organosilicon polymers or oligomers comprising a linear or cyclic and branched or

crosslinked structure, of variable molecular weight, obtained by polymerization and/or polycondensation of suitable functional silanes and essentially composed of a repetition of main units in which the silicon atoms are connected to one another via oxygen atoms (siloxane bond) , optionally substituted hydrocarbon radicals being connected directly to the said silicon atoms via a carbon atom.

The term "silicones" also encompasses the silanes necessary for their preparation, in particular alkylsilanes .

The silicones used for the coating of the pigments suitable for the present invention are preferably selected from the group consisting of alkylsilanes, polydialkylsiloxanes and

polyalkylhydrosiloxanes . More preferably still, the silicones are selected from the group consisting of octyltrimethylsilane, polydimethylsiloxanes and polymethylhydrosiloxanes .

Of course, the pigments formed of metal oxides may, before their treatment with silicones, have been treated with other surfacing agents, in particular with cerium oxide, alumina, silica, aluminum compounds, silicon compounds or their mixtures.

The coated pigments are more particularly titanium oxides coated: with silica, such as the product "Sunveil" from Ikeda,

with silica and with iron oxide, such as the product "Sunveil F" from Ikeda,

with silica and with alumina, such as the products "Microtitanium

Dioxide MT 500 SA" and "Microtitanium Dioxide MT 100 SA" from

Tayca, "Tioveil" from Tioxide and "Mirasun TiW 60" from Rhodia, with alumina, such as the products "Tipaque TTO-55 (B) " and

"Tipaque TTO-55 (A)" from Ishihara and "UVT 14/4" from Kemira, with alumina and with aluminum stearate, such as the product

"Microtitanium Dioxide MT 100 T, MT 100 TX, MT 100 Z or MT-Ol" from Tayca, the products "Solaveil CT-10 W" and "Solaveil CT 100" from Uniqema and the product "Eusolex T-AVO" from Merck,

with silica, with alumina and with alginic acid, such as the product "MT-100 AQ" from Tayca,

with aluminum stearate, such as the product "MT-100 TV" from Tayca, primary particle diameter is 15 nm,

with alumina and with aluminum laurate, such as the product

"Microtitanium Dioxide MT 100 S" from Tayca,

with iron oxide and with iron stearate, such as the product

"Microtitanium Dioxide MT 100 F" from Tayca,

with zinc oxide and with zinc stearate, such as the product

"BR351" from Tayca,

with silica and with alumina and treated with a silicone, such as the products "Microtitanium Dioxide MT 600 SAS", "Microtitanium

Dioxide MT 500 SAS" and "Microtitanium Dioxide MT 100 SAS" from

Tayca,

with silica, with alumina and with aluminum stearate and treated with a silicone, such as the product "STT-30-DS" from Titan Kogyo, with silica and treated with a silicone, such as the product "UV-

Titan X 195" from Kemira,

with alumina and treated with a silicone, such as the products

"Tipaque TTO-55 (S)" from Ishihara or "UV Titan M 262" from Kemira, with triethanolamine, such as the product "STT-65-S" from Titan

Kogyo,

with stearic acid, such as the product "Tipaque TTO-55 (C) " from

Ishihara, or with sodium hexametaphosphate, such as the product "Microtitanium Dioxide MT 150 W" from Tayca.

Other titanium oxide pigments treated with a silicone are

preferably TiO₂ treated with octyltrimethylsilane and for which the mean size of the individual particles is from 25 and 40 nm, such as that marketed under the trademark "T 805" by Degussa

Silices, TiO₂ treated with a polydimethylsiloxane and for which the mean size of the individual particles is 21 nm, such as that marketed under the trademark "70250 Cardre UF TiO2Sl3" by Cardre, anatase/rutile TiO₂ treated with a polydimethylhydrosiloxane and for which the mean size of the individual particles is 25 nm, such as that marketed under the trademark "Microtitanium Dioxide USP Grade Hydrophobic" by Color Techniques.

The uncoated titanium oxide pigments are, for example, marketed by Tayca under the trademarks "Microtitanium Dioxide MT500B" or

"Microtitanium Dioxide MT600B", by Degussa under the trademark "P 25", by Wacker under the trademark "Oxyde de titane transparent PW", by Miyoshi Kasei under the trademark "UFTR", by Tomen under the trademark "ITS" and by Tioxide under the trademark "Tioveil AQ".

The uncoated zinc oxide pigments are, for example:

those marketed under the trademark "Z-cote" by Sunsmart;

those marketed under the trademark "Nanox" by Elementis; and those marketed under the trademark "Nanogard WCD 2025" by

Nanophase Technologies.

The coated zinc oxide pigments are, for example:

those marketed under the trademark "Oxide Zinc CS-5" by Toshiba

(ZnO coated with polymethylhydrosiloxane) ;

those marketed under the trademark "Nanogard Zinc Oxide FN" by

Nanophase Technologies (as a 40% dispersion in Finsolv TN, C₁₂-Ci_S alkyl benzoate) ;

those marketed under the trademark "Daitopersion Zn-30" and

"Daitopersion Zn-50" by Daito (dispersions in oxyethylenated polydimethylsiloxane/cyclopolymethylsiloxane comprising 30% or 50% of zinc nanooxides coated with silica and

polymethylhydrosiloxane) ; those marketed under the trademark "NFD Ultrafine ZnO" by Daikin (ZnO coated with phosphate of perfluoroalkyl and copolymer based on perfluoroalkylethyl as a dispersion in cyclopentasiloxane) ; those marketed under the trademark "SPD-Zl" by Shin-Etsu (ZnO coated with silicone-grafted acrylic polymer dispersed in

cyclodimethylsiloxane) ;

those marketed under the trademark "Escalol ZlOO" by ISP (alumina- treated ZnO dispersed in the ethylhexyl methoxycinnamate/PVP- hexadecene copolymer/methicone mixture); and

those marketed under the trademark "Fuji ZnO-SMS-IO" by Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane) / those marketed under the trademark "Nanox Gel TN" by Elementis (ZnO dispersed at 55% in C₁₂-C₁₅ alkyl benzoate with hydroxystearic acid polycondensate) .

The uncoated cerium oxide pigments are marketed, for example, under the trademark "Colloidal Cerium Oxide" by Rhone-Poulenc.

The uncoated iron oxide pigments are, for example, marketed by Arnaud under the trademarks "Nanogard WCD 2002 (FE 45B)",

"Nanogard Iron FE 45 BL AQ", "Nanogard FE 45R AQ" or "Nanogard WCD 2006 (FE 45R)", or by Mitsubishi under the trademark "TY-220".

The coated iron oxide pigments are, for example, marketed by Arnaud under the trademarks "Nanogard WCD 2008 (FE 45B FN)", "Nanogard WCD 2009 (FE 45B 556)", "Nanogard FE 45 BL 345" or "Nanogard FE 45 BL" or by BASF under the trademark "Oxyde de fer transparent" .

Mention may also be made of mixtures of metal oxides, in

particular of titanium dioxide and of cerium dioxide, including the mixture of equal weights of titanium dioxide coated with silica and of cerium dioxide coated with silica marketed by Ikeda under the trademark "Sunveil A", and also the mixture of titanium dioxide and of zinc dioxide coated with alumina, with silica and with silicone, such as the product "M 261" marketed by Kemira, or coated with alumina, with silica and with glycerol, such as the product "M 211" marketed by Kemira. The coated pigments are preferable because the coating may

function as a binder for fixing the pigments on or in the

substrates. In particular, titanium oxide coated with aluminum stearate such as the product "MT-100 TV" from Tayca is preferable.

The UV filter (s) may be used in the composite pigment according to the present invention in proportions such that the weight ratio of the substrates to the UV filter (s) is 100:1 to 100:500, preferably 100:5 to 100:400, more preferably 100:10 to 100:200, more

preferably 100:10 to 100:100, more preferably 100:10 to 100:50, and more preferably 100:10 to 100:30.

(Coloring Pigments)

As described above, the composite pigment according to the present invention may comprise at least one coloring pigment, preferably in the coating layer covering a stack of the plate-like substrates.

The term "coloring pigment (s)" should be understood as meaning white or colored, inorganic or organic particle (s) of any shape which are insoluble and are intended to color the composition.

If coloring pigment (s) is/are used, the composite pigment

according to the present invention has an effect in that it can provide a clearer appearance with high chroma, because the

coloring pigments do not aggregate but spread in and/or on the substrates. It should be noted that free coloring pigments easily aggregate to give a dark appearance with low chroma to the skin.

The pigments can be white or colored, inorganic and/or organic.

Among the organic pigments that may be used, non-limiting mention may be made of titanium dioxide, optionally surface treated, zirconium or cerium oxide, as well as zinc, (black, yellow or red) iron or chromium oxide, manganese violet, ultramarine blue,

chromium hydrate and ferric blue, or metal powders, such as

aluminum powder or copper powder. The pigments can also be chosen from nanopigments formed of metal oxides, such as titanium dioxide, zinc oxide, iron oxide, zirconium oxide, and cerium oxide, and mixtures thereof. The term "nanopigments" is understood to mean pigments having a mean particle size ranging from 1 nm to 500 nm, such as particle sizes ranging from 10 nm to 100 nm.

Among organic pigments that may be used, non-limiting mention may be made of carbon black, pigments of D&C type and lakes, such as lakes-based on cochineal carmine and on barium, strontium, calcium or aluminum. For example, Red 202 (Calcium bis [2- (3-carboxy-2- hydroxynephthylazo) -5-methylbenzenesulfonate) may be used as the pigment of D&C type.

Preferably, the coloring pigment is chosen from titanium dioxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydrate, ferric blue, aluminum powder, copper powder, carbon black,

pigments of D&C type, lakes, pearlescent pigments, and mixtures thereof.

The term "pearlescent pigments" should be understood as meaning iridescent particles of any shape, such as particles produced by certain shellfish in their shells or else synthesized.

The pearlescent agents can be chosen from white pearlescent agents, such as mica covered with titanium dioxide or with bismuth

oxychloride; colored pearlescent agents, such as titanium oxide- coated mica covered with iron oxide, titanium oxide-coated mica covered with ferric blue or chromium oxide, or titanium oxide- coated mica covered with an organic pigment of the abovementioned type; and pearlescent agents based on bismuth oxychloride.

The coloring pigment (s) may be used in the composite pigment according to the present invention in proportions such that the weight ratio of the substrates to the coloring pigment (s) is 100:1 to 100:500, preferably 100:5 to 100:400, more preferably 100:10 to 100:200, more preferably 100:10 to 100:100, more preferably 100:10 to 100:50, and more preferably 100:10 to 100:30.

(Method for Preparing Composite Pigment)

The composite pigment according to the present invention can be prepared by subjecting a plurality of substrates each of which is in the form of a plate, UV filter (s), and optionally additional material (s) such as coloring pigment (s) to a hybridizer process.

The hybridizer process was developed in the 1980s. The hybridizer process is a class of mechanochemical fusion processes in which strong mechanical power is applied to a plurality of particles to cause a mechanochemical reaction to form a composite particle.

According to the hybridizer process, the mechanical power is imparted by a high speed rotor which can have a diameter from 10 cm to 1 m, and can rotate at a speed of 1,000 rpm to 100,000 rpm. Therefore, the hybridizer process can be defined as a

mechanochemical fusion process using such a high speed rotor. The hybridizer process is performed in air or under dry conditions. Thus, due to the high speed rotation of the rotor, high speed air flow may be generated near the rotor. However, some liquid materials may be subjected to the hybridizer process together with solid materials. The term "hybridizer process" has been used as a technical term.

The hybridizer process can be performed by using a hybridization system marketed by, for example, Nara Machinery in Japan, in which at least two types of particles, typically core particles and fine particles, are fed into a hybridizer equipped with a high speed rotor having a plurality of blades in a chamber under dry

conditions, and the particles are dispersed in the chamber and mechanical and thermal energy (e.g., compression, friction and shear stress) are imparted to the particles for a relatively short period of time such as 1 to 10 minutes, preferably 1 to 5 minutes. As a result, one type of particles (e.g., fine particles) are embedded or fixed on the other type of particles (e.g., core particles) to form a composite particle. It is preferable that the particles have been subjected to electrostatic treatment (s) such as shaking to form an "ordered mixture" in which one type of particles is spread to cover the other type of particle. The hybridizer process can also be performed by using a theta composer marketed by Tokuju Corporation in Japan.

According to the present invention, a plurality of plate-like substrates and UV filter (s) as well as optionally additional material (s) such as coloring pigment (s) if necessary, can be fed into such a hybridizer to form a composite pigment. The

hybridizer process can be performed by using a rotor rotating at about 8,000 rpm (100 m/sec) for about 5 minutes.

If both UV filter (s) and coloring pigment (s) are used for the composite pigment according to the present invention, they can be used in proportions such that the weight ratio of the substrates to the UV filter (S) and coloring pigment (s) is 100:1 to 100:500, preferably 100:5 to 100:400, more preferably 100:10 to 100:200, more preferably 100:10 to 100:100, more preferably 100:10 to

100:50, and more preferably 100:10 to 100:30.

The hybridizer process enables to provide a composite pigment in which at least one UV filter, and optionally at least one coloring pigment, is sandwiched by a plurality of plate-like substrates.

In other words, the UV filter is located at least in part between the plate-like substrates.

Further, the hybridizer process can reduce the size of the plate- like substrate, a smoother feeling on use can be provided by the composite pigment prepared by the hybridizer process.

Furthermore, the hybridizer process can provide an ordered array (e.g., uniform coverage) of the UV filter (s) and optionally

coloring pigment (s) on a stack of plate-like substrates, and strong bonding at the outer surface between the stack and a layer comprising the UV filter(s) and optionally coloring pigment(s).

It should be noted that the hybridizer process is quite different from other processes using, for example, a beads mill and a jet mill. In fact, a beads mill causes pulverization or aggregation of core particles, and a jet mill causes pulverization of core particles and uniform coating of a core particle by fine particles,

If necessary, an additional process for further coating the

composite pigment by additional UV filter (s) and/or coloring material (s) may be performed. As a result of this additional process, the composite pigment according to the present invention may be coated with a further layer comprising UV filter (s) and/or coloring material (s) , preferably consisting of UV filter (s) and/or coloring material (s) .

(Cosmetic Composition)

The composite pigment, as described above, can be present in the composition according to the present invention in an amount ranging from 0.01% to 99% by weight, preferably 0.1% to 50% by weight, and more preferably 1% to 30% by weight, relative to the total weight of the composition.

Preferably, the composite pigment according to the present

invention can be used in cosmetic compositions to be applied to keratin substances such as skin, hair, and nails, providing UV shielding effects, and optionally coloring effects, because the composite pigment can exhibit a good feel on use as well as good UV filtering effects possibly with a transparent or clear

appearance optionally with good coloring effects such as a more transparent or clear coloring, without the risk of affecting the keratin substances.

The cosmetic composition according to the present invention may further comprise a filler and an oil.

As used herein, the term "filler" should be understood as meaning colorless natural or synthetic particles of any shape which are insoluble in the medium of the composition, whatever the

temperature at which the composition is manufactured. Thus, the filler is different from the coloring pigment as described above.

The fillers may be inorganic or organic and of any shape (for instance, platelet, spherical, and oblong shapes) and with any crystallographic form (for example, sheet, cubic, hexagonal, orthorhombic, and the like) . Examples of suitable additional fillers include, but are not limited to, talc; mica; silica;

kaolin; powders of polyamide such as Nylon®; poly-β-3-alanine powders; polyethylene powders; polyurethane powders, such as the powder formed of hexamethylene diisocyanate and trimethylol hexyllactone copolymer sold under the name Plastic Powder D-400 by Toshiki; the powders formed of tetrafluoroethylene polymers (Teflon®) ; lauroyllysine; starch; boron nitride; polymeric hollow microspheres, such as microspheres of poly (vinylidene

chloride) /acrylonitrile, for example Expancel© (Nobel Industrie), and microspheres of acrylic acid copolymers; silicone resin

powders, for example, silsesquioxane powders (for instance,

silicone resin powders disclosed in European Patent No. 0 293 795 and Tospearls® from Toshiba); poly(methyl methacrylate) particles; precipitated calcium carbonate; magnesium carbonate; basic

magnesium carbonate; hydroxyapatite; hollow silica microspheres; glass microcapsules; ceramic microcapsules; metal soaps derived from organic carboxylic acids comprising from 8 to 22 carbon atoms, for example, from 12 to 18 carbon atoms, such as zinc stearate, magnesium stearate, lithium stearate, zinc laurate, and magnesium myristate; barium sulphate; and mixtures thereof.

The filler may be present in the composition in an amount ranging from 0.1% to 80% by weight, with respect to the total weight of the composition, for example, from 1% to 25% by weight, or from 3% to 15% by weight.

The term "oil" is understood to mean a fatty substance which is liquid at ambient temperature (25°C) .

Use may be made, as oils which can be used in the composition of the invention, for example, of hydrocarbon oils of animal origin, such as perhydrosqualene (or squalane) ; hydrocarbon oils of

vegetable origin, such as triglycerides of caprylic/capric acids, for example those marketed by Stearineries Dubois or those

marketed under the trademarks Miglyol 810, 812 and 818 by Dynamit Nobel, or oils of vegetable origin, for example sunflower, maize, soybean, cucumber, grape seed, sesame, hazelnut, apricot,

macadamia, arara, coriander, castor, avocado or jojoba oil or shea butter oil; synthetic oils; silicone oils, such as volatile or non-volatile polymethylsiloxanes (PDMSs) comprising a linear or cyclic silicone chain which are liquid or paste at ambient

temperature; fluorinated oils, such as those which are partially hydrocarbon and/or silicone, for example those described in JP-A- 2-295912; ethers, such as dicaprylyl ether (CTFA name); and esters, such as benzoate C₁₂-C₁₅ fatty alcohols (Finsolv TN from Finetex) ; arylalkyl benzoate derivatives, such as 2-phenylethyl benzoate (X- Tend 226 from ISP) ; amidated oils, such as isopropyl N- lauroylsarcosinate (Eldew SL-205 from Ajinomoto), and their- mixtures .

The oily phase can also comprise one or more fatty substances selected, for example, from fatty alcohols (cetyl alcohol, stearyl alcohol, cetearyl alcohol), fatty acids (stearic acid) or waxes (paraffin wax, polyethylene waxes, carnauba wax, beeswax) . The oily phase can comprise lipophilic gelling agents, surfactants or also organic or inorganic particles.

The oily phase can preferably represent from 1 to 70% of oil by weight, with respect to the total weight of the composition.

The composition according to the present invention may further comprise at least one additional conventional cosmetic ingredient which may be chosen, for example, from hydrophilic or lipophilic gelling and/or thickening agents, surfactants, antioxidants, fragrances, preservatives, neutralizing agents, sunscreens,

vitamins, moisturizing agents, self-tanning compounds, antiwrinkle active agents, emollients, hydrophilic or lipophilic active agents, agents for combating pollution and/or free radicals, sequestering agents, film-forming agents, dermo-decontracting active agents, soothing agents, agents which stimulate the synthesis of dermal or epidermal macromolecules and/or which prevent their decomposition, antiglycation agents, agents which combat irritation, desquamating agents, depigmenting agents, antipigmenting agents, propigmenting agents, NO-synthase inhibitors, agents which stimulate the

proliferation of fibroblasts and/or keratinocytes and/or the differentiation of keratinocytes, agents which act on

microcirculation, agents which act on energy metabolism of the cells, healing agents, and mixtures thereof.

The composition according to the present invention may be in various forms, for example, suspensions, dispersions, solutions, gels, emulsions, such as oil-in-water (O/W) , water-in-oil (W/0) , and multiple (e.g., W/O/W, polyol/O/W, and O/W/0) emulsions, creams, foams, sticks, dispersions of vesicles, for instance, of ionic and/or nonionic lipids, two-phase and multi-phase lotions, sprays, powders, and pastes. The composition may be anhydrous, for example, it can be an anhydrous paste or stick. The composition may also be a leave-in composition.

According to one embodiment, the composition according to the present invention may be in the form of an anhydrous composition such as a liquid or solid oily composition or a powdery

composition.

According to another embodiment, the composition according to the present invention may be in the form of, for example, a compact powder, a lotion, a serum, a milk, a cream, a base foundation, an undercoat, a make-up base coat, a foundation, a face powder, cheek rouge, a lipstick, a lip cream, an eye shadow, an eyeliner, a loose powder, a concealer, a nail coat, mascara, a sunscreen and the like.

It is to be understood that a person skilled in the art can choose the appropriate presentation form, as well as its method of preparation, on the basis of his/her general knowledge, taking into account the nature of the constituents used, for example, their solubility in the vehicle, and the application envisaged for the composition.

EXAMPLES

The present invention will be described in more detail by way of examples, which however should not be construed as limiting the scope of the present invention.

Examples 1 to 4 and Comparative Examples 1 to 4

The components shown in Table 1 were subjected to a hybridizer process using a Hybridizer equipped with a high speed rotor having a plurality of blades in a chamber in dry conditions, marketed by Nara Machinery Co., Ltd. in Japan to obtain a composite pigment.

In detail, for each of Production Examples 1 to 4 (Pl to P4 in Table 1) , the components shown in Table 1 were mixed at the mixing ratio (the numerals in Table 1 are based on parts by weight) shown in Table 1 in a plastic bag by hand shaking for a short period of time. The mixtures obtained after the hand shaking according to Production Examples 1 to 4 were labeled as Comparative Examples 1 to 4, respectively. The obtained mixture was put in the

Hybridizer, and the rotor was revolved at 8,000 rpm (100 m/s linear velocity) for 5 minutes. The composite pigments thus obtained after the hybridizer process were labeled as Examples 1 to 4, respectively.

Table 1

Mica 1^*: Synthetic mica

Mica 2^*: Synthetic mica coated with lauroyllysine

Mica 3^*: Synthetic mica coated with acryl silicone

TiO₂: MT-100 TV marketed by Tayca Corporation in Japan

OMC: Ethylhexyl methoxycinnamate

Mexoryl: Drometrizole trisiloxane

[Particle Size Change Determination]

The change in the particle size before and after the hybridizer process was measured by a MASTERSIZER 2000 (Malvern Industries Ltd., UK). The particle size before the hybridizer process corresponds to the particle size of a "mixture" in which UV filter (s) is/are spread to cover the core particle after the hand shaking.

The results are shown in Table 2. The particle size before and after the hybridizer process correspond to those of Comparative Examples 1 to 4 and Examples 1 to 4, respectively. Table 2

Particle Particle

Ratio (%) Size (μm) Size (μm)

Comp. Ex. 1 2.8 Ex. 1 1.8 64

Comp. Ex 2 5.7 Ex. 2 4.3 76

Comp . Ex. 3 15.2 Ex. 3 10.0 66

Comp. Ex. 4 17.8 Ex. 4 11.6 65

Ratio (%): (Particle size [Example] )/ (Particle size [Comparative Example] ) *100

It is clear from Table 2 that the particle size of each core particle is reduced by 24 to 36%, due to the collapse of the core particle by the hybridizer process.

Since the particle size of Examples 1 to 4 is smaller than that of Comparative Examples 1 to 4, Examples 1 to 4 can provide a

smoother texture.

TWC Foundation

A Two Way Cake (TWC) foundation including any of Examples 1 to 4 or any of Comparative Examples 1 to 4 was prepared by mixing the components shown in Table 3.

Table 3

[Friction Coefficient Determination] Friction Coefficient (MIU) was measured for the TWC foundation by use of a Tribomaster type TL201Sa (Trinity Lab., Inc., Japan).

30 mg to 50 mg of the TWC foundation was deposited on a synthetic leather sheet fixed on the test stage of the Tribomaster by double faced tape. A cubic aluminum probe with a 1 cm x 1 cm square head was also covered with the synthetic leather sheet and used for spreading the TWC foundation in a straight way for a distance of 2.0 cm at a speed of 1 cm/sec. Return strokes were repeated 5 times and the MIU was averaged from the 10 sets of MIU data in each forward and backward. The measurement was repeated three times, and the obtained results were averaged.

The results are shown in Table 4.

Table 4

MIU MIU Ratio (%)

Comp. Ex. 1 0.48 Ex. 1 0.47 97

Comp . Ex 2 0.43 Ex. 2 0.42 96

Comp . Ex. 3 0.44 Ex. 3 0.43 97

Comp . Ex. 4 0.45 Ex. 4 0.43 97

Ratio (%): (Friction coefficient [Example] )/( Friction coefficient [Comparative Example] ) *100

It is clear from Table 4 that the cosmetics comprising the

composite pigments of Examples 1 to 4 have friction coefficients lower than those of the cosmetics comprising the mixtures of

Comparative Examples 1 to 4.

Accordingly, cosmetics comprising the composite pigment according to the present invention can provide a smoother feeling on use than conventional cosmetics comprising a simple mixture of

components corresponding to the composite pigment.

[UVA and UVB Absorbance Determination]

Absorbance of UV waves was measured for the TWC foundation by use of a UV/VIS spectrophotometer type V-550 (JASCO, Japan) as follows 6.0 mg of the TWC foundation was spread evenly by a finger on a 10 cm² tacky surface area of double faced tape attached on a

transparent plastic sheet. The TWC foundation was covered with another transparent plastic sheet for sandwiching the powder sample. This test sheet was set in the V-550 sheet cell holder and the absorbance was measured from 260 nm to 400 nm. The averaged absorbance by the powder sample of 0.6 mg/cm² in the ranges of 260 nm to 320 nm and 320 nm to 400 nm were used for the values of the absorbance of UVB and UVA, respectively.

The results are shown in Tables 5 and 6.

Table 5

UVB

Absorbance Absorbance Ratio (%)

Comp. Ex .1 0.95 Ex. 1 0.97 102

Comp. Ex 2 1.14 Ex. 2 1.16 103

Comp. Ex .3 1.38 Ex. 3 1.50 109

Comp. Ex .4 1.22 Ex. 4 1.56 129

Ratio(%):(UV absorbance [Example] )/ (UV absorbance [Comparative Example] ) *100

Table 6

UVA

Absorbance Absorbance Ratio (%)

Comp . Ex. 1 0.66 Ex. 1 0.68 102

Comp. Ex 2 0.77 Ex. 2 0.75 98

Comp. Ex. 3 0.77 Ex. 3 0.93 121

Comp. Ex. 4 0.69 Ex. 4 0.96 138

It is clear from Tables 5 and 6 that the cosmetics comprising the composite pigments of Examples 1 to 4 have better or equivalent (98%) UV filtering effects, in particular in the UVB region, as compared to those comprising the mixtures of Comparative Examples 1 to 4.

Accordingly, the cosmetic comprising the composite pigment according to the present invention can provide a UV filtering effect which is equal to or better than that of conventional cosmetics comprising a simple mixture of components corresponding to the composite pigment. This can be attributed to good

dispersion of UV filter (s) on and in the composite pigment

according to the present invention.

Example 5

The preparation of a composite pigment according to Example 1 was repeated providing that kaolin was replaced with lauroyllysine plates .

The obtained composite pigment was observed by FIB (focused ion beam) -SEM before and after cutting the composite pigment by a Ga ion beam. The SEM images of the composite pigment before and after the cutting are shown in Figure 1, as Figure 1 (a) and Figure l(b), respectively.

It was confirmed that the composite pigment according to Example 5 includes a plurality of lauroyllysine plates as cores sandwiching a part of the UV filter (TiO₂) .

Since the composite pigment according to the present invention is no longer in the form of a plate, as shown in Figure 1, it can provide a better feeling on use on the skin, as compared to a conventional plate-like composite pigment.

Example 6 and Comparative Example 6

The preparation of a composite pigment according to Example 1 and a mixture according to Comparative Example 1 were repeated except that the components shown in Table 7 were used. In Table 7, P6 means Production Example 6. The obtained composite pigment and mixture were labeled as Example 6 and Comparative Example 6, respectively. Table 7

Ca(b): CaCθ₃ in the form of a block, Omyapure 35 LM-OG,

marketed by Omya in Australia

Red: Red 202

Mexoryl: Drometrizole trisiloxane

Lipstick

A lipstick was prepared by mixing a base, the components of which are shown in Table 8, with the composite pigment according to Example 6 or the mixture according to Comparative Example 6 such that the coloring pigment (Red 202) corresponds to 0.1wt% of the lipstick, with a tricylinder roller at 90⁰C.

Table 8

[UVA and UVB Absorbance Determination] Absorbance of UV waves of each lipstick was measured for the lipstick by use of a UV/VIS spectrophotometer type V-550 (JASCO, Japan) as follows.

150 mg of the lipstick was poured on a 4 cm² square area on a transparent plastic sheet surrounded by double faced tapes attached onto the transparent plastic sheet. The lipstick was covered with another transparent plastic sheet for sandwiching the paste sample to prepare a test sheet. The averaged absorbance by the paste sample of 150mg/4cm² in the ranges of 260 nm to 320 nm and 320 nm to 400 nm were used for the values of the absorbance of UVB and UVA, respectively. The results are shown in Tables 9 and 10.

Table 9

UVB

Absorbance Absorbance Ratio (%)

Comp. Ex. 6 2.06 Ex. 6 2.31 112

Ratio(%):(UV absorbance [Example 6]) /(UV absorbance [Comparative Example 6])*100

Table 10

UVA

Absorbance Absorbance Ratio (%)

Comp. Ex. 6 0.88 Ex. 6 0.93 106

Ratio(%):(UV absorbance [Example 6] ) / (UV absorbance [Comparative Example 6])*100

It is clear from Tables 9-10 that the cosmetic comprising the composite pigment of Example 6 has a higher UV absorbance as compared to that comprising the mixture of Comparative Example 6,

Accordingly, cosmetics comprising the composite pigment according to the present invention can provide a better UV filtering effect which is even derived from a coloring pigment compared to

conventional cosmetics comprising a simple mixture of components corresponding to the composite pigment.

[Color Determination] Color (L^*, a", b^*) of each of the lipsticks according to Example 6 and Comparative Example 6 was measured by using a DATACOLOR 600 (Applied Color Systems Inc., US) as follows.

2.5g of the lipstick was poured into an aluminum pan

(25mm (L) *23mm(W) *4mm(D) ) and cooled to solidify the paste. The L^* a^* and b^* of the test sample were measured from the top of the paste.

The results are shown in Tables 11-13.

Table 11

L^*

Comp. Ex. 6 41. Ex. 6 43 .54

Table 12 a

Comp. Ex. 6 44. 06 I Ex. 51 .58

Table 13 b^*

Comp. Ex. 6 15. 06 I Ex. 6 22 .42

It is clear from Tables 11-13 that the cosmetic comprising the composite pigment of Example 6 has significantly higher a^* and b^* values as compared to that comprising the mixture of Comparative Example 6.

Accordingly, the cosmetic comprising the composite pigment

according to the present invention can provide a better color with higher chroma compared to conventional cosmetics comprising a simple mixture of components corresponding to the composite pigment .

Claims

1. A composite pigment comprising a stacking of at least two

plate-like substrates and at least one UV filter material located at least in part between the at least two plate-like substrates.

2. The composite pigment according to Claim 1, wherein the plate- like substrate has an aspect ratio of at least 5.

3. The composite pigment according to Claim 1 or 2, wherein the plate-like substrate has a length ranging from 0.3 μm to 30 μm.

4. The composite pigment according to any one of Claims 1 to 3, wherein the at least one UV filter material is in the form of a layer having a thickness of 0.03 μm to 10 μm.

5. The composite pigment according to any one of Claims 1 to 4 , wherein the composite pigment has a thickness of 0.2 μm to 25 μm.

6. The composite pigment according to any one of Claims 1 to 5, wherein the plate-like substrate comprises at least one

inorganic material and/or at least one organic material.

7. The composite pigment according to Claim 6, wherein the

inorganic material is selected from the group consisting of natural mica, synthetic mica, sericite, kaolin, talc, clay mineral, hydrotalcite, boron nitride, calcium carbonate, barium sulfate, titanium oxide, hydroxyapatite, silica, silicate, zinc oxide, magnesium sulfate, magnesium carbonate, magnesium trisilicate, aluminum oxide, aluminum silicate, calcium silicate, calcium phosphate, magnesium oxide, bismuth oxychloride, glass flake, and mixtures thereof.

8. The composite pigment according to Claim 6 or 7, wherein the organic material is selected from the group consisting of

(meth) acrylates, polyamides, silicones, polyurethanes,

polyethylenes, polypropylenes, polystyrenes,

9. The composite pigment according to any one of Claims 1 to 8, wherein the at least one UV filter material is organic or inorganic.

10. The composite pigment according to Claim 9, wherein the at

least one UV filter material comprises an organic filter selected from the group consisting of anthranilic derivatives; dibenzoylmethane derivatives; cinnamic derivatives; salicylic derivatives; camphor derivatives; benzophenone derivatives;

β, β-diphenylacrylate derivatives; triazine derivatives;

benzotriazole derivatives; benzalmalonate derivatives;

benzimidazole derivatives; imidazoline derivatives; bis- benzoazolyl derivatives; p-aminobenzoic acid (PABA) and

derivatives thereof; methylenebis (hydroxyphenylbenzotriazole) derivatives; benzoxazole derivatives; screening polymers and screening silicones; dimers derived from α-alkylstyrene; 4,4- diarylbutadienes; octocrylene and derivatives thereof,

guaiazulene and derivatives thereof, rutin and derivatives thereof, flavonoids, biflavonoids, oryzanol and derivatives thereof, quinic acid and derivatives thereof, phenols, retinol, cysteine, aromatic amino acid, peptides having an aromatic amino acid residue, and mixtures thereof.

11. The composite pigment according to Claim 9 or 10, wherein the at least one UV filter material comprises an inorganic UV filter selected from the group consisting of silicon carbide, metal oxides which may or may not be coated, and mixtures thereof.

12. The composite pigment according to any one of Claims 1 to 11, wherein the weight ratio of said substrates to the at least one UV filter material is 100:1 to 100:500.

13. The composite pigment according to any one of Claims 1 to 12, wherein it further comprises at least one coloring pigment.

14. A method for preparing a composite pigment according to any one of Claims 1 to 13, comprising a step of subjecting a plurality of plate-like substrates, at least one UV filter, and optionally a coloring pigment, to a hybridizer process.

15. A cosmetic composition comprising a composite pigment

according to any one of Claims 1 to 13 or a composite pigment prepared by the method according to Claim 14.