WO2011016143A1

WO2011016143A1 - Composite pigment and method for preparation thereof

Info

Publication number: WO2011016143A1
Application number: PCT/JP2009/064207
Authority: WO
Inventors: Takahiro Suzuki; Takehiko Kasai
Original assignee: L'oreal
Priority date: 2009-08-04
Filing date: 2009-08-04
Publication date: 2011-02-10
Also published as: JP2013501077A; JP6210680B2

Abstract

The present invention relates to a composite pigment comprising a porous substrate, said porous substrate being at least in part covered by at least one layer comprising at least one UV filter and/or at least one coloring pigment, said at least one UV filter and/or at least one coloring pigment being embedded in a matrix comprised of the same material (s) as the one(s) forming the substrate. The composite pigment can be prepared by a method comprising a step of subjecting a substrate with at least one collapsible surface, and at least one UV filter and/or at least one 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 porous core particle, and UV filter (s) and/or coloring pigment (s), as well as a method for preparing the composite pigment.

BACKGROUND ART

In accordance with the variety of needs in cosmetics, various research and developments have been performed. In particular, for powders for cosmetics, many types of surface treatments or composite powders have been proposed.

For example, JP-A-S63-110261 discloses composite pigments

comprising a porous core sphere particle having a rigid surface and fine particles covering the core particle.

However, these composite pigments have a poor feeling on use, and the UV filtering property deteriorates if fine solid UV filter particles are used to cover a core particle as compared to a simple mixture of the fine UV filter particles and the core particle .

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 or texture without deteriorating the UV filtering property when fine UV filter particles are used for covering a core particle to form the composite pigment.

The above objective of the present invention can be achieved by a composite pigment comprising a porous substrate, said porous substrate being at least in part covered by at least one layer comprising at least one UV filter and/or at least one coloring pigment, said at least one UV filter and/or at least one coloring pigment being embedded in a matrix comprised of the same material (s) as the one(s) forming the substrate.

The porous substrate may have a mean diameter ranging from 0.1 μm to 30 μm.

The above at least one layer may have a thickness of 0.03 μm to 10 μm. The above at least one layer may be porous, the porosity of said at least one layer being less than the porosity of the porous substrate. In particular, the above at least one layer may be solid.

The porous 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 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, magnesium hydroxide, bismuth oxychloride, kaolin, hydrotalcite, mineral clay, and mixtures thereof. 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, and mixtures thereof.

The coloring pigment may be chosen from titanium dioxide,

zirconium oxide, cerium oxide, zinc oxides, iron oxides, 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 UV filter may be organic or inorganic. The UV filter 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- diarylbutadiene derivatives; 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 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.

In the composite pigment according to the present invention, the weight ratio of said porous substrate to the UV filter (s) and/or coloring pigment(s) may be 100:1 to 100:500.

The composite pigment according to the present invention can be prepared by a method comprising a step of subjecting a porous substrate with at least one collapsible surface, and at least one UV filter and/or at least one 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 is a diagram showing hybrizidation using a particle with a collapsible surface and UV filters and/or coloring pigments.

Fig. 2 is a diagram showing hybrizidation using a particle with a non-collapsible surface and UV filters and/or coloring pigments. Fig. 3 is a SEM image of a porous particle with a collapsible surface used in Example 1.

Fig. 4 is a SEM image of a porous particle with non-collapsible surface used in Comparative Example 1.

BEST MODE FOR CARRYING OUT 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 or texture without deteriorating the UV filtering property, rather with improving the UV filtering effects, when fine UV filter particles are used for covering a core particle to form the composite pigment.

The new composite pigment according to the present invention comprises a porous substrate which is at least in part covered by at least one layer comprising at least one UV filter and/or at least one coloring pigment. The substrate and the layer function as a core and a coating, respectively, of the composite pigment. According to the present invention, the coating layer comprises a matrix which is composed of the same material (s) as the one(s) forming the substrate, and the UV filter (s) and/or coloring pigment (s) is /are embedded in the matrix.

The composite pigment according to the present invention can provide better a feeling on use or texture, because the UV

filter (s) and/or coloring pigment (s) are firmly fixed on the substrate, and therefore, it is possible to reduce free UV

filter (s) and/or coloring pigment (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 imparted to the skin.

Further, since at least a part of at least one UV filter and/or coloring pigment according to the present invention is embedded in the layer, the embedded UV filter and/or coloring pigment cannot directly contact with the skin. Therefore, a smoother feeling on use can be obtained. Furthermore, the UV filter and/or coloring pigment cannot penetrate into the skin via pores on> the skin. In addition, even if the UV filter and/or coloring pigment

irritate (s), a large amount of the UV filter and/or coloring pigment cannot directly contact with the skin. Accordingly, the composite pigment according to the present invention is safer than a conventional composite pigment in which a sphere core is simply covered by UV filter(s) and/or coloring pigment(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 in the composite pigment according to the present invention is porous. The porosity of the substrate may be

characterized by a specific surface area of from 0.05 m²/g to 1500 m²/g, more preferably from 0.1 m²/g to 1300 m²/g, and more

preferably from 0.2 m²/g to 1000 m²/g according to the BET method.

It is preferable that the substrate is in the form of a particle, which may be referred to as a core or a core particle hereafter. This substrate preferably has a mean diameter ranging from 0.1 p to 30 μm, preferably 0.1 μm to 20 μm, and more preferably 0.1 μm to 10 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 material of the substrate is not limited. Thus, the porous substrate comprises at least one inorganic material and/or at least one organic material.

The inorganic material may be selected from the group consisting of 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, magnesium hydroxide, bismuth oxychloride, kaolin,

hydrotalcite, mineral clay, and mixtures thereof.

In particular, calcium carbonate, calcium phosphate, calcium silicate, barium sulfate, hydroxyapatite, a mixture (complex) of calcium carbonate and hydroxyapatite and a mixture (complex) of calcium carbonate and calcium phosphate are preferable.

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, and mixtures thereof.

In particular, polyamides such as Nylon® and polyhydroxyalkanoates such as polylactic acids are preferable.

(Layer on Substrate)

The porous substrate is at least partially covered by at least one layer comprising at least one UV filter and/or at least one coloring pigment. The layer may be refereed to as a coating layer. Preferably, 10% or more of the surface of the substrate is covered by the coating layer (s). More preferably, 50% or more of the surface is covered by the coating layer (s) . More preferably, 80% or more of the substrate is covered by the coating layer (s). Most preferably, the entire surface of the substrate 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 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 5μm.

If there are two or more coating layers on the substrate, the thickness and the composition of the layers may be the same as or different from each other.

The coating layer comprises a matrix, which can be the main component of the layer, composed of the same material (s) as the one(s) forming the porous substrate. The UV filter (s) and/or coloring pigment (s) is/are embedded in the matrix in the layer.

The coating layer may be porous. In this case, it is preferable that the porosity of the coating layer is less than the porosity of the porous substrate. On the other hand, the coating layer may be solid. The coating layer (s) may comprise, other than the matrix, UV filter (s) and/or the coloring pigment (s), and any additional material (s) such as a binder, preferably 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 additional

material (s) , UV filter (s) and coloring pigment (s). However, it is preferable that the layer (s) consists of the matrix, the UV filter (s) and/or the coloring pigment (s).

(UV Filters)

The layer (s) covering the porous substrate include (s) one or more UV filters. The UV filters may be active in the UV-A and/or UV-B region. The UV filters 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 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 on the substrate. It should be noted that free fine particles of UV filter (s) easily aggregate to impart a white appearance to the skin.

The material of the UV filter 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;

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; Benzophenone-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 "Uvasorb 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, β-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 "Uvinul 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 an 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

Dibenziiπidazole tetrasulfonate, Ethylhexyl triazone, bis- Ethylhexyloxyphenol methoxyphenyl triazine, Diethylhexyl butamido triazone, 2 , 4, 6-Tris (dineopentyl 4 ' -aminobenzalmalonate) -s- triazine, 2,4, β-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 nm 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 weights, 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 15nm,

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 T1O2SI3" 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-C₁₅ 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 ϋltrafine 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 said porous substrate 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)

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

The composite pigment comprising coloring pigment (s) 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 on the substrate. It should be noted that free coloring pigments easily aggregate to impart a dark appearance with low chroma to the skin.

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

Among the inorganic 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 size 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 said porous substrate 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 porous substrate with at least one

collapsible surface, and UV filter (s) and/or coloring pigment (s) to a hybridizer process.

The term "collapsible surface" -means a surface which has a

microstructure or microstructures which can collapse by any

mechanical stress to the surface. Examples of the microstructure include projections or protrudings having a length of from 0.001 μm to 10 μm, preferably from 0.001 μm to 1 μm, and more preferably 0.001 μm to 0.1 μm. Such a projection may be exemplified by a needle, a spindle, a pillar, a plate, a flake, a leaflet and the like. Accordingly, a preferred example of a porous substrate with at least one collapsible surface may be a particle with petal- flakes. 50% or more, preferably 70% or more, more preferably 90% or more, and most preferably 100%, of the surface of the substrate is collapsible.

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 Co., Ltd. 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) is embedded or fixed on the other type of particle (e.g., core

particle) to form a composite particle. It is preferable that the particles have been subjected to electrostatic treatment (s) by shaking and the like 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 porous substrate with at least one collapsible surface, and the UV filter (s) and/or

coloring pigment (s), as well as other optional component (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 (lOO.m/sec) for about 5 minutes.

A porous substrate with at least one collapsible surface can be prepared in accordance with known methods or processes described in, for example, JP-A-2006-63062 or WO 2006/11661 describing the preparation of a petal-shaped porous calcium carbonate particle, and JP-A-2003-261796 or US-A-2004-11253 describing a porous magnesium hydroxide particle or a porous magnesium carbonate with projections in the form of leaflets.

It is possible .to use commercially available porous substrates with at least one collapsible surface, such as a petal-shaped complex of calcium carbonate and calcium phosphate with a primary particle size of 10 μm and a water absorbability of 1.6 ml/g sold as Poronex C marketed by Maruo Calcium Co., Ltd. in Japan; a petal type porous CaCO₃ as LDR CA marketed by New Lime Co., Ltd. and Toshiki Pigment Co., Ltd. in Japan; and a petal-shaped calcium carbonate with a primary particle size of 25 μm and a water absorbability of 4.6 ml/g sold as Florite R marketed by Tokuyama Corp. in Japan.

According to the present invention, as shown in Figure 1, the hybridizer process makes the collapsible surface of the porous substrate collapse, and collapsed parts are mixed with the UV filter (s) and/or coloring pigment (s) to form a coating layer of the substrate. Thus, the collapsed parts form the matrix of the coating layer.

Under mechanochemical fusion processes, objects which are made from the same material can easily and firmly bond together. Since the material of the matrix of the coating layer and the porous core substrate is the same, the coating layer and the core can be strongly bonded. Furthermore, the UV filter (s) and/or coloring pigment (s) entrapped in the matrix cannot detach from the substrate.

Since the collapsible surface collapses during the hybridizer process, the diameter or size of the substrate is considerably reduced after the hybridizer process. Typically, the diameter or size of the porous substrate with a collapsible surface is reduced by from 20 to 70%, preferably 30 to 60%, on average.

It should be noted that the diameter or size of a porous substrate with a non-collapsible surface can be slightly reduced when it is subjected to a hybridizer process. However, the reduction of the diameter or size of the substrate is from 1 to 20%, preferably 1 to 10%, on average. Furthermore, the UV filter (s) and/or coloring pigment are simply present on the surface of the substrate, as shown in Figure 2, and therefore some of the UV filter (s) and/or coloring pigment may easily detach from the substrate.

Therefore, by using a porous substrate with a collapsible surface for a hybridizer process, it is possible to obtain a composite pigment which has a relatively small size and strongly holds UV filter (s) and/or coloring pigment (s). Accordingly, it is possible to obtain a better feeling on use and safety because UV filter (s) and/or coloring pigment (s) are embedded in the coating layer and will not easily detach from the core to penetrate into the body through the pores on the skin, for example.

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 porous substrate 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 not only provide ordered array (e.g., uniform coverage) of the fine particles of the UV filter (s) and/or coloring pigment (s) on the porous substrate but also provides strong bonds at the surface of the porous substrate and a layer comprising the fine particles of the UV filter (s) and/or 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/or coloring effects, because the composite pigment can exhibit a good feeling on use as well as good UV filtering effects with a transparent or clear appearance and/or 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 (25⁰C) .

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 (0/W) , water-in-oil (W/O) , and multiple (e.g., W/O/W, polyol/0/W, and 0/W/O) 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 3 and Comparative Examples 1 and 2

The components shown in Tables 1 and 2 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 Examples 1 to 3 and Comparative Examples 1 and 2, the components shown in Tables 1 and 2 were mixed at the mixing ratio (the numerals in Tables 1 and 2 are based on parts by weight) shown in Tables 1 and 2 in a plastic bag by hand shaking for a short period of time. The mixture was put in the Hybridizer, and the rotor was revolved at 8,000 rpm (100 m/s linear velocity) for 5 minutes.

Table 1

Table 2

Core UV Filter

SiO₂ POMP TiO₂

Comp . Ex. 1 100 - 40

Comp. Ex. 2 - 100 40

CaCO₃: Petal type porous CaCO₃, which has the shape shown in

Figure 3, marketed as LDR CA by New Lime Co., Ltd. and Toshiki Pigment Co., Ltd. in Japan

BiOCl: Petal type porous bismuth oxychloride

HAP: Porous hydroxyapatite marketed by Maruo Calcium Co., Ltd, in Japan SiO₂: Porous spherical silica which has the shape shown in Figure

4

POMP: Porous polyamide marketed by Ube Industries, Ltd.

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

[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) for Examples 1 to 3 and Comparative Examples 1 and 2. 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 3. In Table 3, [Mixture] means a mixture of the components shown in Tables 1 and 2 which has not yet been subjected to the hybridizer process.

Table 3

Before (μm) After (μm) After/Before [Mixture] [Composite Pigment] Ratio (%)

Ex. 1 9.0 4.9 55

Ex. 2 3.8 1.7 44

Ex. 3 1.7 1.2 69

Comp. Ex. 1 3.5 3.2 91

Comp. Ex. 2 11.3 10.2 90

It is clear from Table 3 that the particle size of each of the core particles having a collapsible surface used in Examples 1 to 3 is reduced by 31 to 56%, due to the collapse by the hybridizer process, whereas the particle size of each of the core particles having no collapsible surface used in Comparative Examples 1 and 2 is reduced by only 9 to 10%.

TWC Foundation

A Two Way Cake (TWC) foundation including the "mixture" before the above hybridization process or a composite pigment obtained by the above hybridization process was prepared for each of Examples 1 to 3 and Comparative Examples 1 and 2 by mixing the mixture or composite pigment with the components shown in Table 4. Table 4

In Table 4, "Mixture" means a mixture of the components shown in Tables 1 and 2 which has not yet been subjected to the hybridizer process, and "Composite Pigment" means a composite pigment

obtained by the hybridizer process for the components shown in Tables 1 and 2.

[Friction Coefficient Determination]

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

foundation as follows.

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 a 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. The return strokes were repeated 5 times and the MIU was averaged from the 10 sets of MIU data in each forward and backward movement. The measurement was repeated three times, and the obtained results were averaged.

The results are shown in Table 5. In Table 5, [Mixture] means a TWC foundation including a mixture of the components shown in Tabled 1 and 2 which has not yet been subjected to the hybridizer process, and [Composite Pigment] means a TWC foundation including a composite pigment obtained by the hybridizer process for the components shown in Tables 1 and 2.

Table 5

Ratio (%): (Friction coefficient [Composite Pigment] )/ (Friction coefficient [Mixture] ) *100

It is clear from Table 5 that the cosmetics comprising the

composite pigments of Examples 1 to 3 have friction coefficients lower than those of the cosmetics comprising the mixtures of

Examples 1 to 3, whereas the cosmetics comprising the composite pigments of Comparative Examples 1 and 2 have friction

coefficients higher than those of the cosmetics comprising the mixtures of Comparative Examples 1 and 2.

Accordingly, cosmetics comprising the composite pigment according to the present invention can provide a smooth feeling on use which is better than that of conventional cosmetics.

[UVA and UVB Absorbance Determination]

Absorbance of UV waves was measured by use of a UV/VIS

spectrophotometer type V-550 (JASCO, Japan) for the TWC foundation 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 tapes attached onto 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 6 and 7. In Tables 6 and 7,

[Mixture] means a TWC foundation including a mixture of the components shown in Tables 1 and 2 which has not yet been

subjected to the hybridizer process, and [Composite Pigment] means a TWC foundation including a composite pigment obtained by the hybridizer process for the components shown in Tables 1 and 2.

Table 6

UVB

[Mixture] [Composite Pigment] Ratio (%)

Ex. 1 0.86 0.97 112

Ex. 2 1.03 1.05 102

Ex. 3 1.02 1.06 103

Comp. Ex. 1 1.18 1.06 90

Comp. Ex. 2 0.88 0.70 80

Ratio ( % ) : ( UV absorbance [ Composite Pigment ] ) / ( UV absorbance

[Mixture] ) * 100

Table 7

UVA

[Mixture] [Composite Pigment] Ratio (%)

Ex. 1 0.61 0.68 111

Ex. 2 0.71 0.76 107

Ex. 3 0.73 0.75 103

Comp. Ex. 1 0.83 0.78 94

Comp . Ex. 2 0.63 0.58 92

Ratio(%):(UV absorbance [Composite Pigment] )/ (UV absorbance

[Mixture] ) *100

It is clear from Tables 6 and 7 that the cosmetics comprising the composite pigments of Examples 1 to 3 have improved UV filtering effects as compared to those comprising the mixtures of Examples 1 to 3, whereas the cosmetics comprising the composite pigments of Comparative Examples 1 and 2 have inferior UV filtering effects as compared to those comprising the mixtures of Comparative Examples 1 and 2. Accordingly, the cosmetic comprising the composite pigment according to the present invention can provide a UV filtering effect which is better than that of conventional cosmetics. This can be attributed to the good dispersion of the UV filter (s) on the core particle in the composite pigment used in Examples 1 to 3

Examples 4 to 6

Example 1 was repeated to obtain a composite pigment for Examples 4 to 6 except that the components shown in Table 8 (the numerals in Table 8 are based on parts by weight) were used for Examples 4 to 6.

Table 8

Ca(p): Petal type porous CaCO₃, which has the shape shown in

Red: Red 202

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

OMC: Ethylhexyl methoxycinnamate

Mexoryl: Drometrizole trisiloxane

Lipstick

A lipstick was prepared by mixing a base, the components of which are shown in Table 9, with the composite pigment according to Examples 4 to 6 or the mixture of components corresponding to the composite pigment of Examples 4 to 6 such that the coloring pigment (Red 202) corresponds to 0.1wt% of the lipstick, with a tricylinder roller at 90°C. Table 9

[Color Determination]

Color (L ,a ,b ) of each of the lipsticks according to Examples 4 to 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 10-12. In Tables 10-12, [Mixture] means a lipstick including a mixture of the components shown in Table 8 which has not yet been subjected to the hybridizer process, and [Composite Pigment] means a lipstick including a composite pigment obtained by the hybridizer process for the components shown in Table 8.

Table 10

Table 11

[Mixture] [Composite Pigment]

Ex. 4 43.71 49.76

Ex. 5 44.06 49.85

Ex. 6 44.15 50.98

Table 12

It is clear from Tables 10-12 that the cosmetics comprising the composite pigments of Examples 4 to 6 have higher a^* and b^* values as compared to those comprising a simple mixture of components corresponding to the composite pigment.

Accordingly, cosmetics 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 porous substrate, said porous substrate being at least in part covered by at least one layer comprising at least one UV filter and/or at least one coloring pigment, said at least one UV filter and/or at least one coloring pigment being embedded in a matrix comprised of the same material (s) as the one(s) forming the substrate.

2. The composite pigment according to Claim 1, wherein the porous substrate has a mean diameter ranging from 0.1 μm to 30 μm.

3. The composite pigment according claim 1 or 2, wherein the at least one layer has a thickness of 0.03 μm to 10 μm.

4. The composite pigment according to any one of Claims 1 to 3, wherein the said at least one layer is porous, the porosity of said at least one layer being less than the porosity of the porous substrate.

5. The composite pigment according to any one of Claims 1 to 4, wherein the said at least one layer is solid.

6. The composite pigment according to any one of Claims 1 to 5, wherein the porous 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 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, magnesium hydroxide, bismuth oxychloride, kaolin, hydrotalcite, mineral clay, 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, polyhydroxyalkanoates, polycaprolactams, poly (butylene) succinates, polysaccharides, polypeptides, polyvinyl alcohols, polyvinyl resins, and mixtures thereof.

9. The composite pigment according to any one of Claims 1 to 8, wherein the at least one coloring pigment is chosen from titanium dioxide, zirconium oxide, cerium oxide, zinc oxides, iron oxides, 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.

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

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

least one UV filter comprises an organic filter selected from the group consisting of anthranilates; dibenzoylmethane

derivatives; cinnamic derivatives; salicylic derivatives;

camphor derivatives; benzophenone derivatives; β,β- diphenylacrylate derivatives; triazine derivatives;

benzotriazole derivatives; benzalmalonate derivatives;

benzimidazole derivatives; imidazolines; 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.

12. The composite pigment according to Claim 10 or 11, wherein the at least one UV filter 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.

13. The composite pigment according to any one of Claims 1 to 12, wherein the weight ratio of said porous substrate to the UV filter(s) and/or coloring pigment (s) is 100:1 to 100:500.

14. A method for preparing a composite pigment according to any

one of Claims 1 to 13, comprising a step of subjecting a porous substrate with at least one collapsible surface, and at least one UV filter and/or at least one coloring pigment, to a hybridizer process.

15. The method according to Claim 14, wherein the collapsible

surface has a plurality of projections having a length of from 0.001 μm to 10 μm.

16. The method according to Claim 14 or 15, wherein the mean

diameter of the porous substrate is reduced after the porous substrate is subjected to the hybridizer process.

17. 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 any one of Claims 14 to 16,