JP6231275B2 - Composite pigment and preparation method thereof - Google Patents

Description

  The present invention relates to a composite pigment comprising a plurality of substrates each in the form of a plate, a UV shielding agent, and optionally a colored pigment, and a method for preparing the composite pigment.

Many cosmetics contain one or more UV screening agents to shield ultraviolet light. In particular, skin cosmetics generally contain a UV shielding agent such as fine particles of TiO _{2 that} protects the skin from ultraviolet rays together with other components such as extender pigments, such as talc, mica, and kaolin.

However, the fine particles of TiO ₂ have such a high coefficient of friction that they do not spread easily on the skin, giving an unpleasant feeling to the skin.

Furthermore, solid fine particles such as TiO ₂ fine particles may easily aggregate and have low dispersibility. Therefore, it is often difficult to uniformly disperse such particles in the cosmetic in the form of primary particles. Therefore, it is difficult to improve the UV shielding properties of cosmetics containing UV shielding fine particles.

  Various research and development are being carried out according to the diverse needs of cosmetics. In particular, in order to impart good UV shielding properties to cosmetics, many types of surface treatment agents or composite pigments for UV shielding agents have been proposed.

  For example, Japanese Patent Application Laid-Open Nos. 05-214257, 05-230394 and 09-99246 disclose composite pigments comprising a single plate core particle and UV shielding agent fine particles covering the single plate core particle. ing.

  However, these composite pigments do not have a feeling of use, and the fine particles of the UV screening agent may separate from the composite pigment and penetrate into the skin from the pores on the skin, and the skin barrier properties are not strong in the pores This can cause harmful effects on the skin. Also, since UV screening agents can easily come into contact with the skin, there is a risk that when UV screening agents are irritating, this contact may also have a deleterious effect on the skin.

JP 05-214257 JP 05-230394 JP 09-99246 U.S. Patent No. 6,225,467 WO 2004/085412 WO 06/035000 WO 06/034982 WO 06/034991 WO 06/035007 WO 2006/034992 WO 2006/034985 EP-669,323 U.S. Pat.No. 2,463,264 U.S. Pat.No. 5,237,071 U.S. Pat.No. 5,166,355 GB-2,303,549 DE-197,26,184 EP-893,119 WO 93/04665 DE-19855649 European Patent No. 0 293 795 JP 02-295912

"Symmetrical Triazine Derivatives", IP.COM Journal, IP.COM INC, WEST HENRIETTA, NY, US (September 20, 2004) Cosmetics & Toiletries, February 1990, 105, 53-64

  Therefore, the object of the present invention can provide a better feeling of use and a better UV shielding effect, the risk that the fine particles of the UV screening agent penetrate into the skin from the pores on the skin, and the UV screening agent is irritating It is to provide a novel composite pigment that has a reduced risk of easily contacting the skin when affected.

  The object of the present invention is to provide a composite pigment comprising a laminate comprising at least two plate-like substrates and at least one UV shielding agent at least partially disposed between at least two plate-like substrates. Can be realized.

  The plate-like substrate has an aspect ratio of at least 5, and the plate-like substrate preferably has a length in the range of 0.3 μm to 30 μm.

  The at least one UV screening agent is preferably 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 contain at least one inorganic material and / or at least one organic material. Inorganic materials include 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 flakes, and mixtures thereof. On the other hand, organic materials are (meth) acrylate, polyamide, silicone, polyurethane, polyethylene, polypropylene, polystyrene, polyhydroxyalkanoate, polycaprolactam, poly (butylene) succinate, polysaccharide, polypeptide, polyvinyl alcohol, polyvinyl resin, fluoropolymer , Waxes, amidosulfonic acid polyvalent metal salts, acylated amino acids, and mixtures thereof.

  The UV screening agent may be organic or inorganic. UV screening agents include anthranilic acid derivatives, dibenzoylmethane derivatives, cinnamic acid derivatives, salicylic acid derivatives, camphor derivatives, benzophenone derivatives, β, β-diphenyl acrylate derivatives, triazine derivatives, benzotriazole derivatives, benzalmalonic acid derivatives, benzimidazole derivatives , Imidazoline derivatives, bis-benzoazolyl derivatives, p-aminobenzoic acid (PABA) and its derivatives, methylenebis (hydroxyphenylbenzotriazole) derivatives, benzoxazole derivatives, shielding polymers and silicones, dimers derived from α-alkylstyrenes, 4 , 4-diarylbutadiene, octocrylene and its derivatives, guaiazulene and its derivatives, rutin and its derivatives, flavonoids, biflavonoids, oryzanol and its derivatives, key Acid and derivatives thereof, phenol, retinol, cysteine, aromatic amino acids, peptides having an aromatic amino acid residues, and may contain organic screening agent selected from the group consisting of mixtures. On the other hand, the UV screening agent may comprise an inorganic UV screening agent selected from the group consisting of silicon carbide, coated or uncoated metal oxides, and mixtures thereof. The weight ratio of the substrate to the at least one UV screening agent may be 100: 1 to 100: 500.

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

  The composite pigment according to the present invention can be prepared by a method including a step of subjecting a plurality of plate-like substrates, at least one UV shielding agent, and optionally a colored pigment to a hybridizer method.

  The composite pigment according to the invention can be included in a cosmetic composition.

It is a figure which shows the SEM image of the composite pigment containing the some plate-shaped core base material. FIG. 1 (a) shows the appearance of the composite pigment, and FIG. 1 (b) shows a cross-sectional view of the composite pigment.

  As a result of intensive studies, the present inventors have provided a better feeling of use and a better UV shielding effect, the risk that the fine particles of the UV screening agent penetrate into the skin from the pores on the skin, and the fine particles of the UV screening agent It has been discovered that it is possible to obtain new composite pigments that are easily contacted with the skin and have reduced risk of affecting the skin.

  The new composite pigment according to the present invention comprises a laminate comprising at least two plate-like substrates and at least one UV screening agent at least partly disposed between at least two plate-like substrates.

  Some of the UV screening agent may be present on the outer surface of the substrate laminate. In this case, the laminate of the base material can function as a core of the composite pigment.

  The composite pigment according to the present invention may 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 laminate of plate-like base materials, the composite pigment does not have a strict plate shape but has a rounded shape such as an expanded portion or a spindle shape. Therefore, it is in the form of a plate in which a single core plate is covered with a UV shielding agent, which improves usability compared to composite pigments that function like sandpaper and give the skin an unpleasant feeling of use. To do.

  Furthermore, when a part of the UV shielding agent is present on the outer surface of the plate-like substrate laminate, one end of the better use feeling of the composite pigment according to the present invention is that the UV shielding agent is firmly fixed on the laminate. By being done. Thus, it is possible to reduce free UV screening agents that have a high coefficient of friction that does not spread easily on the skin and therefore give the skin an undesirable feeling of use. In addition, since the UV screening agent can be spread and fixed on the surface of the plate-like substrate laminate, the UV screening agent does not aggregate and is dispersed in the form of primary particles on the surface. Therefore, the UV shielding effect of the UV shielding agent can be enhanced.

  Furthermore, since at least a portion of the at least one UV screening agent is disposed between the substrates, the UV screening agent sandwiched therebetween does not come into direct contact with the skin. Therefore, the UV screening agent between the substrates does not penetrate the skin from the pores on the skin. In particular, when the UV screening agent is irritating, a part of the UV screening agent is trapped between the substrates, so that a large amount of the UV screening agent does not come into direct contact with the skin. Therefore, the composite pigment according to the present invention is safer than the conventional composite pigment in which a single plate core is covered with a UV shielding agent.

  Below, each element which comprises the composite pigment by this invention is explained in full detail.

(Base material)
The substrate to be used in the present invention has a plate shape. Any substrate may be used as long as the substrate is in the form of a plate. The substrate preferably has an aspect ratio of at least 5, preferably greater than 10, more preferably greater than 20, and more preferably greater than 50. The aspect ratio can be obtained from the average thickness and the average length according to the formula of aspect ratio = length / thickness.

  The plate-like substrate preferably has a length in the range of 0.3 μm to 30 μm, preferably 0.5 μm to 20 μm, more preferably 1 μm to 10 μm, more preferably 2 μm to 5 μm.

  The above-mentioned dimensions can be obtained by calculating the average of the dimensions of 100 substrates selected in the image obtained with the scanning electron microscope.

  A laminate of base materials may be produced by agglomerating a plurality of randomly oriented plate-like base materials. However, it is preferable that the plate-like substrate is regularly oriented, and at least a part, preferably the whole, is layered or stacked with the UV shielding agent interposed therebetween.

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

  Preferably, the inorganic material is 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 flakes, and mixtures thereof. In particular, natural mica, synthetic mica, sericite, kaolin, talc, and mixtures thereof are preferred.

  Preferably, the organic material is (meth) acrylate, polyamide, silicone, polyurethane, polyethylene, polypropylene, polystyrene, polyhydroxyalkanoate, polycaprolactam, poly (butylene) succinate, polysaccharide, polypeptide, polyvinyl alcohol, polyvinyl resin, It may be selected from the group consisting of fluoropolymers, waxes, amidosulfonic acid polyvalent metal salts, acylated amino acids, and mixtures thereof. For example, PTFE can be used as the fluoropolymer. As an amidosulfonic acid polyvalent metal salt, for example, N-lauroyl taurine calcium can be used. Lauroyl lysine can be used as an acylated amino acid. Particularly preferred are polyamides such as Nylon (registered trademark), polyhydroxyalkanoates such as polylactic acid, and mixtures thereof.

  The substrate may be either coated or uncoated. More preferably, the substrate is coated. The material of the coating material for the base material is not limited, but organic materials such as amino acids, N-acylamino acids, amides, silicones, and modified silicones are preferable. Examples of the organic material include lauroyl lysine and acrylic-modified silicone.

(Layer on substrate)
The laminate of plate-like substrates can be at least partially covered by at least one layer comprising at least one UV screening agent. If present, the layer is referred to as the coating layer. In order to make the composite pigment according to the present invention have a round shape such as an expanded portion or a spindle shape, it is preferable to cover the outer surface of the plate-like substrate laminate with one or more coating layers. It is preferable to cover 10% or more of the outer surface with a coating layer. More preferably, 50% or more of the outer surface is covered with a coating layer. More preferably, 80% or more of the outer surface is covered with a coating layer. Most preferably, the entire outer surface of the plate-like substrate laminate is covered with a coating layer.

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

  When two or more coating layers are present on the laminate of the plate-like substrate, the thickness and composition of the coating layers may be the same as or different from each other.

  In addition to the UV screening agent, the coating layer may contain any additional materials such as colored pigments and binders, preferably non-liquid binders. The additional material may be present in an amount ranging from 1 to 50 wt% based on the combined weight of the UV screening agent and the additional material. However, the coating layer is preferably made of a UV shielding agent.

(UV shielding agent)
The composite pigment according to the present invention contains at least one UV shielding agent at least partially between the plate-like substrates. Furthermore, as described above, the composite pigment according to the present invention may include at least one coating layer that may include at least one UV shielding agent that covers the laminate of the plate-like substrate. The UV shielding agent between the plate-like substrates and the UV shielding agent in the coating layer may be the same or different, and are preferably the same.

  The UV screening agent used in the present invention may have activity in the UV-A and / or UV-B region. UV screening agents may be hydrophilic and / or lipophilic and / or correspondingly insoluble in solvents commonly used in cosmetics.

  The UV screening agent may be in the form of a liquid or a solid such as a particle. When the UV screening agent is in the form of solid particles, the UV screening agent has a primary particle size ranging from 1 nm to 5 μm, preferably 10 nm to 1 μm, more preferably 10 nm to 100 nm, more preferably 10 nm to 20 nm. Preferably, the fine particles are fine.

  When using a UV screening agent in the form of fine particles, the composite pigment according to the present invention does not aggregate and spreads in and on the base material, so the composite pigment has a transparent or clear appearance instead of a white appearance It has the effect that can be shown. It should be noted that single particles of UV screening agent aggregate easily and give the skin a white appearance.

  The material of the UV screening agent is not limited. The UV screening agent may be organic or inorganic. When two or more UV screening agents are used, the UV screening material may be the same as or different from each other.

  Organic UV screening agents include anthranilic acid derivatives, dibenzoylmethane derivatives, cinnamic acid derivatives, salicylic acid derivatives, camphor derivatives, benzophenone derivatives, β, β-diphenyl acrylate derivatives, triazine derivatives, benzotriazole derivatives, benzalmalonic acid derivatives, benzimidazoles Derivatives, imidazoline derivatives, bis-benzoazolyl derivatives, p-aminobenzoic acid (PABA) and its derivatives, methylene bis (hydroxyphenylbenzotriazole) derivatives, benzoxazole derivatives, shielding polymers and silicones, α-alkylstyrene derived dimers, 4, 4-diarylbutadiene, octocrylene and its derivatives, guaiazulene and its derivatives, rutin and its derivatives, flavonoids, biflavonoids, oryzanol and its derivatives, quinic acid Beauty derivatives thereof, phenol, retinol, cysteine, aromatic amino acids, aromatic amino acid residues containing peptide, and may be those selected from the group consisting of mixtures.

  Examples of organic UV screening agents include those indicated by their INCI names below and mixtures thereof.

Anthranilate derivative: Menthyl anthranilate marketed under the trademark “Neo Heliopan MA” by Haarmann and Reimer.

Dibenzoylmethane derivatives: in particular butylmethoxydibenzoylmethane marketed under the trademark “Parsol 1789” by Hoffmann-LaRoche; and isopropyldibenzoylmethane.

Cinnamic acid derivatives: in particular ethylhexyl methoxycinnamate; isopropyl methoxycinnamate; isopropoxy methoxycinnamate; marketed by Hoffmann-LaRoche under the trademark "Parsol MCX" "Neo Heliopan E 1000" by Haarmann and Reimer Isoamyl methoxycinnamate commercially available under the trade name; Synoxate (2-ethoxyethyl-4-methoxycinnamate); DEA methoxycinnamate; Diisopropyl methylcinnamate; and Glyceryl ethyl hexamethoxycinnamate.

Salicylic acid derivatives: homosalate marketed under the trademark "Eusolex HMS" by Rona / EM Industries; homomentil salicylate; ethylhexyl salicylate marketed under the trademark "Neo Heliopan OS" by Haarmann and Reimer; glycol salicylate; salicylic acid Butyloctyl; phenyl salicylate; dipropylene glycol salicylate marketed under the trademark “Dipsal” by Scher; and TEA salicylate marketed under the trademark “Neo Heliopan TS” by Haarmann and Reimer.

Camphor derivatives, especially benzylidene camphor derivatives: 3-benzylidene camphor manufactured by Chimex under the trademark "Mexoryl SD"; 4-methylbenzylidene camphor marketed by Merck under the trademark "Eusolex 6300"; "Mexoryl SL by chimex Benzylidene camphor sulfonic acid manufactured under the trademark ''; camphor benzalkonium methosulfate manufactured under the trademark `` Mexoryl SO '' by Chimex; terephthalidene diene manufactured under the trademark `` Mexoryl SX '' by Chimex Camphorsulfonic acid; and polyacrylamidomethylbenzylidene camphor manufactured by Chimex under the trademark “Mexoryl SW”.

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 (hydroxymethoxybenzophenone sulfone marketed under the trademark “Uvinul MS40” by BASF Acid); benzophenone-5 (sodium hydroxymethoxybenzophenone sulfonate); benzophenone-6 (dihydroxydimethoxybenzophenone) marketed under the trademark `` Helisorb 11 '' by Norquay; under the trademark `` Spectra-Sorb UV-24 '' by American Cyanamid Commercially available benzophenone-8; "Uvinul DS by BASF Benzophenone-9 (disodium dihydroxydimethoxybenzophenone disulfonate); benzophenone-12, and n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate.

β, β-diphenyl acrylate derivatives: in particular octocrylene marketed under the trademark “Uvinul N539” by BASF; and ethocrylene marketed under the trademark “Uvinul N35” in particular by BASF.

Triazine derivatives: bis-ethylhexyloxyphenol methoxyphenyl triazine marketed under the trademark `` Tinosorb S '' by Ciba-Geigy; ethylhexyl triazone specially marketed under the trademark `` Uvinul T150 '' by BASF; `` Uvasorb by Sigma 3V Diethylhexylbutamidotriazone marketed under the trademark `` HEB ''; 2,4,6-tris (dineopentyl 4′-aminobenzalmalonate) -s-triazine; and US Pat.No. 6,225,467, WO 2004 / Symmetrical triazine blockade as described in 085412 (see compounds 6 and 9) or document `` Symmetrical Triazine Derivatives '', IP.COM Journal, IP.COM INC, WEST HENRIETTA, NY, US (September 20, 2004) Agents, in particular 2,4,6-tris (biphenyl) -1,3,5-triazine (especially 2,4,6-tris (biphenyl-4-yl) -1,3,5-triazine), and WO 06/035000, WO 06/034982, WO 06/034991, WO 06/035007, WO 2006/034992 and W O 2,4,6-Tris (terphenyl) -1,3,5-triazine, also featured in 2006/034985.

Benzotriazole derivatives, especially phenylbenzotriazole derivatives: Drometrizole trisiloxane marketed under the trademark `` Silatrizole '' by Rhodia Chimie or `` Mexoryl XL '' by L'Oreal; 2- (2,4-dihydroxy Phenyl) -2H-benzotriazole; 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole; 2- (2-hydroxyphenyl) -2H-benzotriazole.

Benzalmalonic acid derivatives: 4'-methoxybenzalmalonate dineopentyl, and polyorganosiloxanes containing benzalmalonic acid functional groups, such as Polysilicone-15 marketed under the trademark "Parsol SLX" by Hoffmann-LaRoche.

Benzimidazole derivatives, in particular phenylbenzimidazole derivatives: phenyldibenzimidazole sulfonic acid marketed in particular under the trademark “Eusolex 232” by Merck and phenyldibenzimidazole marketed under the trademark “Neo Heliopan AP” by Haarmann and Reimer Disodium tetrasulfonate.

Imidazoline derivative: ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate.

Bis-benzoazolyl derivatives: derivatives as described in EP-669,323 and US Pat. No. 2,463,264.

Para-aminobenzoic acid and its derivatives: PABA (p-aminobenzoic acid), ethyl PABA, ethyldihydroxypropyl PABA, pentyldimethyl PABA, especially ethylhexyldimethyl PABA, glyceryl PABA marketed under the trademark `` Escalol 507 '' by ISP PEG-25 PABA marketed under the trademark “Uvinul P25” by BASF.

Methylene bis (hydroxyphenylbenzotriazole) derivatives: solid form sold under the trademark "Mixxim BB / 100" by Fairmount Chemical or micronized form in aqueous dispersion under the trademark "Tinosorb M" by Ciba Specialty Chemicals Methyllenbis-benzotriazolyltetramethylbutylphenol and derivatives as described in US 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) marketed under the trademark Uvasorb K2A by Sigma 3V ) Imino-1,3,5-triazine.

Shielding polymer and shielding silicone: Silicone described in WO 93/04665.

α-alkylstyrene-derived dimer: A dimer according to DE-19855649.

4,4-Diarylbutadiene derivative: 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene.

Octocrylene and its derivatives: Octocrylene.

Guaiazulene and its derivatives: Guaiazulene and sodium guaiazulene sulfonate.

Rutin and its derivatives: rutin and glucosyl rutin.

Flavonoids: Lobustin (isoflavonoid), genistein (flavonoid), tectocricin (flavonoid) and hispidone (flavonoid).

Biflavonoids: Lanseoratin A, Lanseoratin B and Hypnane biflavonoid A.

Oryzanol and its derivatives: Γ-oryzanol.

Quinic acid and its derivatives: quinic acid.

Phenol: Phenol.

Retinol: Retinol.

Cysteine: L-cysteine.

Aromatic amino acid residue-containing peptide: A peptide having tryptophan, tyrosine or phenylalanine.

Preferred organic UV blockers are selected from:
Ethylhexyl methoxycinnamate, homosalate, ethylhexyl salicylate, octocrylene, phenylbenzimidazolesulfonic acid, benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate, 4- Methylbenzylidene camphor, terephthalylidene camphor sulfonic acid, disodium phenyldibenzimidazole tetrasulfonate, ethylhexyltriazone, bis-ethylhexyloxyphenol methoxyphenyltriazine, diethylhexylbutamide 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, methylenebis-benzotriazolyltetramethylbutylphenol, drometrizol 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 mixtures thereof.

  More preferred organic UV screening agents are ethylhexyl methoxycinnamate, drometrizol trisiloxane, and mixtures thereof.

  The inorganic UV screening agent may be selected from the group consisting of silicon carbide, coated or uncoated metal oxides, and mixtures thereof.

  Inorganic UV screening agents are pigments composed of coated or uncoated metal oxides (average primary particle size: generally 5 nm to 100 nm, preferably 10 nm to 50 nm), e.g. UV photoprotectors that are all well known per se It is preferably selected from pigments composed of titanium oxide (amorphous or rutile and / or anatase crystalline), iron oxide, zinc oxide, zirconium oxide or cerium oxide.

  The pigment may be coated or uncoated. Coated pigments include, for example, compounds such as those described in Cosmetics & Toiletries, February 1990, 105, pp. 53-64, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins , Fatty acid sodium, potassium, zinc, iron, or aluminum salt, metal alkoxide (titanium or aluminum alkoxide), polyethylene, silicone, protein (collagen, elastin), alkanolamine, silicon oxide, metal oxide, or sodium hexametaphosphate A pigment that has been subjected to one or more surface treatments of chemical, electronic, mechanochemical and / or mechanical properties used.

  As is known, silicones are organosilicon polymers or oligomers containing linear or cyclic, branched or cross-linked structures that can vary in molecular weight and polymerize and / or polycondensate suitable functional silanes. In principle, silicon atoms are bonded to each other by oxygen atoms (siloxane bonds), and in some cases, a repeating repeating main unit in which a substituted hydrocarbon group is directly bonded to the silicon atom by a carbon atom. Consists of

  The term “silicone” also includes the silanes required for their preparation, especially alkyl silanes.

  The silicone used for coating the pigments suitable for the present invention is preferably selected from the group consisting of alkylsilanes, polydialkylsiloxanes, and polyalkylhydrosiloxanes. Even more preferably, the silicone is selected from the group consisting of octyltrimethylsilane, polydimethylsiloxane, and polymethylhydrosiloxane.

  Pigments composed of metal oxides are naturally treated with other surfacing agents, in particular cerium oxide, alumina, silica, aluminum compounds, silicon compounds, or mixtures thereof before being treated with silicone. May be.

More specifically, the coated pigment is the following titanium oxide.
Products covered with silica, such as the product "Sunveil" from Ikeda
Products that are coated with silica and iron oxide, such as the product "Sunveil F" from Ikeda
Takeka products "Microtitanium Dioxide MT 500 SA" and "Microtitanium Dioxide MT 100 SA", Tioxide product "Tioveil", Rhodia product "Mirasun TiW 60", etc., which are coated with silica and alumina,
Products coated with alumina, such as Ishihara Sangyo's products "Tipaque TTO-55 (B)" and "Tipaque TTO-55 (A)", Kemira's "UVT 14/4",
Takeka's products "Microtitanium Dioxide MT 100 T, MT 100 TX, MT 100 Z or MT-01", Uniqema's products "Solaveil CT-10 W" and "Solaveil CT 100", Merck's products "Eusolex T-AVO", etc. , Coated with alumina and aluminum stearate,
Takeka's product "MT-100 AQ", etc., coated with silica, alumina and alginic acid,
Takeka's product `` MT-100 TV '' etc., coated with aluminum stearate, primary particle size is 15 nm,
Takeka's product “Microtitanium Dioxide MT 100 S”, etc., coated with alumina and aluminum laurate,
Takeka's product `` Microtitanium Dioxide MT 100 F '', etc., coated with iron oxide and iron stearate,
Takeka's product "BR351", etc., coated with zinc oxide and zinc stearate,
Takeka's products `` Microtitanium Dioxide MT 600 SAS '', `` Microtitanium Dioxide MT 500 SAS '', `` Microtitanium Dioxide MT 100 SAS '', etc., which are coated with silica and alumina and treated with silicone,
Titanium industry product "STT-30-DS", etc., coated with silica, alumina, and aluminum stearate and treated with silicone,
Kemira's product `` UV-Titan X 195 '' etc., coated with silica and treated with silicone,
Ishihara's product "Tipaque TTO-55 (S)" or Kemira's product "UV Titan M 262", etc. coated with alumina and treated with silicone,
Products coated with triethanolamine, such as the product “STT-65-S” from Titanium Industry,
Products coated with stearic acid, such as the product “Tipaque TTO-55 (C)” of Ishihara Sangyo, or products coated with sodium hexametaphosphate, such as the product “Microtitanium Dioxide MT 150 W” of Teika.

Other titanium oxide pigments treated with silicone, is treated with octyltrimethylsilane, TiO ₂ average size of the individual particles is 25 to 40 nm, for example, commercially available under the trademark "T 805" by Degussa Silices TiO ₂ that has been treated with polydimethylsiloxane and whose individual particles have an average size of 21 nm, such as that sold under the trademark “70250 Cardre UF TiO2SI3” by Cardre, treated with polydimethylhydrosiloxane Anatase / rutile TiO ₂ , whose individual particles have an average size of 25 nm, such as those sold by Color Techniques under the trademark “Microtitanium Dioxide USP Grade Hydrophobic”.

  The uncoated titanium oxide pigments are, for example, Miyoshi, the trademark of “Microtitanium Dioxide MT500B” or “Microtitanium Dioxide MT600B” by Teika, the trademark “P 25” by Degussa, and the trademark “Oxyde de titane transparent PW” by Wacker. It is marketed under the “UFTR” trademark by Kasei, under the “ITS” trademark by Tomen, and under the “Tioveil AQ” trademark by Tioxide.

Uncoated zinc oxide pigments are, for example,
Those marketed under the trademark "Z-cote" by Sunsmart,
Those marketed under the trademark "Nanox" by Elementis,
It is marketed under the trademark “Nanogard WCD 2025” by Nanophase Technologies.

The coated zinc oxide pigment is, for example,
Those marketed under the trademark "Oxide Zinc CS-5" by Toshiba (ZnO coated with polymethylhydrosiloxane),
What is marketed by Nanophase Technologies under the trademark “Nanogard Zinc Oxide FN” (as a 40% dispersion in Finsolv TN, a C ₁₂ -C ₁₅ alkyl benzoate),
Those marketed under the trademarks `` Daitopersion Zn-30 '' and `` Daitopersion Zn-50 '' by Daito Kasei (containing 30% or 50% zinc nanooxide coated with silica and polymethylhydrosiloxane, Dimethylsiloxane / cyclopolymethylsiloxane dispersion),
Those marketed by Daikin Industries under the trademark "NFD Ultrafine ZnO" (ZnO as a cyclopentasiloxane dispersion coated with a copolymer based on perfluoroalkyl phosphate ester and perfluoroalkylethyl),
Commercially available under the trademark "SPD-Z1" by Shin-Etsu Chemical Co., Ltd. (ZnO coated with silicone graft acrylic polymer dispersed in cyclodimethylsiloxane),
What is marketed under the trademark "Escalol Z100" by ISP (ethyl hexyl methoxycinnamate / PVP-hexadecene copolymer / alumina-treated ZnO dispersed in methicone mixture) and "Fuji ZnO-SMS-10" Those marketed under the trademark (ZnO coated with silica and polymethylsilsesquioxane),
It is marketed by Elementis under the trademark “Nanox Gel TN” (ZnO dispersed at 55% in C ₁₂ -C ₁₅ alkyl benzoate containing hydroxystearic acid polycondensate).

  Uncoated cerium oxide pigments are commercially available, for example, under the trademark “Colloidal Cerium Oxide” by Rhone-Poulenc.

  Uncoated iron oxide pigments, for example, under the trademark “Nanogard WCD 2002 (FE 45B)”, “Nanogard Iron FE 45 BL AQ”, “Nanogard FE 45R AQ” or “Nanogard WCD 2006 (FE 45R)” by Arnaud. Or marketed under the trademark “TY-220” by Mitsubishi.

  Coated iron oxide pigments, for example, under the trademark “Nanogard WCD 2008 (FE 45B FN)”, “Nanogard WCD 2009 (FE 45B 556)”, “Nanogard FE 45 BL 345” or “Nanogard FE 45 BL” by Arnaud. Or marketed by BASF under the trademark “Oxyde de fer transparent”.

  Mixtures of metal oxides, in particular titanium dioxide, including a mixture of titanium dioxide coated with silica and cerium dioxide coated with silica, sold under the trademark "Sunveil A" by Ikeda. A mixture of titanium dioxide with cerium dioxide, or a mixture of titanium dioxide with zinc dioxide coated with alumina, silica and silicone, for example the product “M 261” marketed by Kemira, or coated with alumina, silica and glycerol Mention may also be made of mixtures with zinc dioxide, for example the product “M 211” marketed by Kemira.

  Coated pigments are preferred because the coating may function as a binder that fixes the pigment on or in the substrate. In particular, titanium oxide coated with aluminum stearate is preferred, such as the product “MT-100 TV” from Teika.

  The UV screening agent has a weight ratio of the substrate to the UV screening agent in the composite pigment according to the present invention of 100: 1 to 100: 500, preferably 100: 5 to 100: 400, more preferably 100: 10 to 100: 200, more preferably 100: 10-100: 100, more preferably 100: 10-100: 50, more preferably 100: 10-100: 30.

(Color pigment)
As described above, the composite pigment according to the present invention may contain at least one coloring pigment in the coating layer that preferably covers the laminate of the plate-like substrate.

  The term “color pigment” is to be understood as meaning white or colored inorganic or organic particles of any shape which are insoluble and which color the composition.

  When a colored pigment is used, the composite pigment of the present invention has an effect that the colored pigment does not agglomerate and spreads in and / or on the substrate, so that a clear appearance with high saturation can be obtained. It should be noted that free colored pigments aggregate easily and give the skin a dull appearance with low saturation.

  The pigment may be a white or colored inorganic and / or organic pigment.

  Among the inorganic pigments that can be used, but not limited to, titanium dioxide, zirconium oxide or cerium oxide and zinc, (black, yellow, or red) iron oxide or chromium oxide, manganese purple, which are optionally surface-treated. , Ultramarine blue, chromium hydroxide hydrate, and ferric blue, or metal powders such as aluminum powder and copper powder. The pigment can also be selected from nanopigments composed of metal oxides such as titanium dioxide, zinc oxide, iron oxide, zirconium oxide, cerium oxide, and combinations thereof. The term “nanopigment” is understood to mean a pigment having an average particle size in the range of 1 nm to 500 nm, for example in the range of 10 nm to 100 nm.

  Among the organic pigments that can be used, carbon black, D & C type pigments and lakes, such as cochineal carmine-based and barium, strontium, calcium, or aluminum-based lakes, can be mentioned without limitation. For example, Red 202 (calcium bis [2- (3-carboxy-2-hydroxynaphthylazo) -5-methylbenzenesulfonate) can be used as a D & C type pigment.

  Color pigments include titanium dioxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, chromium oxide, manganese purple, ultramarine blue, chromium hydroxide hydrate, ferric blue, aluminum powder, copper powder, carbon black, It is preferably selected from D & C type pigments, lakes, pearlescent pigments, and mixtures thereof.

  The term “pearl foil pigment” should be understood to mean iridescent particles of any shape, such as particles produced or otherwise synthesized within a shell by a particular shellfish.

  Pearlescent agent is a white pearlescent agent such as mica coated with titanium dioxide or bismuth oxychloride; mica coated with titanium oxide coated with iron oxide, coated with titanium oxide Colored pearlescent agents such as mica coated with ferric blue or chromium oxide, mica coated with titanium oxide coated with the above-mentioned organic pigments; and pearls mainly composed of bismuth oxychloride A brightener can be selected.

  In the composite pigment according to the present invention, the color pigment has a weight ratio of the substrate to the color pigment of 100: 1 to 100: 500, preferably 100: 5 to 100: 400, more preferably 100: 10 to 100: 200, More preferably, it can be used at a ratio of 100: 10 to 100: 100, more preferably 100: 10 to 100: 50, more preferably 100: 10 to 100: 30.

(Preparation method of 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, a UV screening agent, and optionally additional materials such as colored pigments, to a hybridizer method.

  The hybridizer method was developed in the 1980s. The hybridizer method is a part of a mechanochemical fusion method in which a mechanical force is applied to a large number of particles to cause a mechanochemical reaction to produce composite particles.

  According to the hybridizer method, the mechanical force is applied by a high-speed rotor that can have a diameter of 10 cm to 1 m and can rotate at a speed of 1,000 rpm to 100,000 rpm. Therefore, the hybridizer method can be defined as a mechanochemical fusion method using such a high-speed rotor. The hybridizer method is carried out in air or under dry conditions. Therefore, since the rotor rotates at a high speed, a high-speed air flow can be generated near the rotor. However, some liquid materials can be subjected to the hybridizer method with solid materials. The term “hybridizer method” is used as a technical term.

  The hybridizer method can be performed using, for example, a hybridization system marketed by Nara Machinery Co., Ltd. in Japan. In this system, at least two kinds of particles, usually core particles and fine particles, are dried under dry conditions. In a chamber with a high-speed rotor having a plurality of blades to disperse the particles in the chamber and to give the particles mechanical and thermal energy (e.g., compression, friction, and shear stress) 1-10. Minutes, preferably 1 to 5 minutes. As a result, one type of particles (eg, fine particles) is embedded or fixed on the other type of particles (eg, core particles) to form composite particles. The particles are preferably subjected to electrostatic treatment such as shaking to generate an “ordered mixture” in which one type of particles spreads and covers the other type of particles. The hybridizer method can also be carried out using a theta composer marketed by the Deoksugaku workshop in Japan.

  According to the present invention, a plurality of plate-like substrates, a UV shielding agent, and optionally additional materials such as coloring pigments are supplied to such a hybridizer to produce a composite pigment. be able to. The hybridizer method can be performed for about 5 minutes using a rotor rotating at about 8,000 rpm (100 m / sec).

  When both UV screening agents and colored pigments are used in the composite pigments according to the invention, these materials have a substrate to UV screening agent and coloring pigment weight ratio of 100: 1 to 100: 500, preferably 100: 5 to 100: 400, more preferably 100: 10-100: 200, more preferably 100: 10-100: 100, more preferably 100: 10-100: 50, more preferably 100: 10-100: 30 Can be used in any proportion.

  The hybridizer method makes it possible to obtain a composite pigment in which at least one UV shielding agent and optionally at least one coloring pigment are sandwiched between a plurality of plate-like substrates. In other words, at least a part of the UV shielding agent is disposed between the plate-like substrates.

  Furthermore, in the hybridizer method, the size of the plate-like substrate can be reduced, and a smoother feeling can be provided by the composite pigment prepared by the hybridizer method.

  Further, in the hybridizer method, the UV shielding agent and, if necessary, the colored pigment are regularly arranged (for example, uniformly covered) on the laminate of the plate-like base material, and the laminate, the UV shielding agent, and optionally the coloring pigment are included. The adhesion on the outer surface between the layers can be strengthened.

  It should be noted that the hybridizer method is completely different from other methods using, for example, a bead mill or a jet mill. Actually, the bead mill causes fine pulverization or agglomeration of the core particles, and in the jet mill, the core particles are finely pulverized, and the coating of the core particles with the fine particles is not uniform.

  If desired, additional methods of further coating the composite pigment with additional UV screening agents and / or coloring materials may be performed. As a result of this additional method, the composite pigment according to the invention may be coated with another layer comprising a UV screening agent and / or a coloring material, preferably consisting of a UV screening agent and / or a coloring material.

(Cosmetic composition)
The composite pigment as described above is contained in the composition according to the present invention in an amount of 0.01% to 99% by weight, preferably 0.1% to 50% by weight, more preferably 1% to 30% by weight of the total weight of the composition. May be present in an amount of.

  Preferably, the composite pigment according to the present invention has a good UV shielding effect that may be accompanied by a clear or clear appearance with a good coloring effect such as a more transparent or clear coloring, in addition to a good feeling of use. Can be used in cosmetic compositions applied to keratin materials such as skin, hair, nails, etc. to provide a UV blocking effect and optionally a coloring effect. Can do.

  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 to mean any form of colorless natural or synthetic particles that are insoluble in the medium of the composition at any temperature. Therefore, the filler is different from the colored pigment as described above.

  The filler may be inorganic or organic and may be of any shape (e.g., sheet, cubic, hexagonal, orthorhombic, etc.) (e.g. platelets, spheres, and ellipses). Status). Examples of suitable additional fillers include, but are not limited to, talc; mica; silica; kaolin; polyamide powder such as Nylon®; poly-β-3-alanine powder; polyethylene powder; polyurethane powder, for example , A powder composed of hexamethylene diisocyanate and a trimethylol hexyl lactone copolymer sold by Toshiki under the name Plastic Powder D-400; a powder composed of tetrafluoroethylene polymer (Teflon®); lauroyl Lysine; starch; boron nitride; polymeric hollow microspheres such as poly (vinylidene chloride) / acrylonitrile microspheres such as Expancel® (Nobel Industrie), and acrylic acid copolymer microspheres; silicone resin powders such as Silsesquioxane powders (e.g. silicone resin powders disclosed in EP 0 293 795, and And Toshiba's Tospearls®); poly (methyl methacrylate) particles; precipitated calcium carbonate; magnesium carbonate; basic magnesium carbonate; hydroxyapatite; hollow silica microspheres; glass microcapsules; ceramic microcapsules; 8-22 Metal soaps derived from organic carboxylic acids containing from 10 to 18 carbon atoms, such as zinc stearate, magnesium stearate, lithium stearate, zinc laurate, and magnesium myristate; barium sulfate; and These mixtures are mentioned.

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

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

Oils that can be used in the compositions of the invention include, for example, animal-derived hydrocarbon oils such as perhydrosqualene (or squalane); plant-derived hydrocarbon oils such as caprylic / capric triglycerides, For example, those marketed by Sterineries Dubois or marketed by Dynamite Nobel under the trademarks Miglyol 810, 812 and 818, or plant-derived oils such as sunflower oil, corn oil, soybean oil, cucumber oil, grapes Seed oil, sesame oil, hazelnut oil, apricot oil, macadamia nut oil, arara oil, coriander oil, castor oil, avocado oil, jojoba oil, shea butter oil; synthetic oil; silicone oil, for example, liquid at ambient temperature Or a paste, volatile or non-volatile polymethylsiloxane (PDMS) containing linear or cyclic silicone chains; fluorinated oils, eg For example, a part of which is hydrocarbon and / or silicone, for example, those described in JP-A No. 02-295912; ethers such as dicaprylyl ether (CTFA name); C _{12 to} C ₁₅ aliphatic alcohol benzoate ( Esters such as Finetex's Finsolv TN); arylalkyl benzoates such as 2-phenylethyl benzoate (ISP's X-Tend 226); amidated oils such as N-lauroyl sarcosine isopropyl (Ajinomoto Erdeu SL-205); And mixtures thereof.

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

  The oily phase may preferably represent 1 to 70% oil by weight of the total weight of the composition.

  The composition according to the invention may further comprise at least one additional conventional cosmetic ingredient, such as a hydrophilic or lipophilic gelling agent and / or thickener, a surfactant, Antioxidants, fragrances, preservatives, neutralizers, sunscreens, vitamins, moisturizers, self-tanning compounds, wrinkle-inhibiting active agents, mitigating agents, hydrophilic or lipophilic active agents, contamination and / or free radical removal agents Sequestering, sequestering agents, film formers, dermo-decontracting active agents, soothing agents, stimulating the synthesis of dermal or epidermal polymers and / or preventing their degradation Drugs, antiglycation agents, agents that remove irritation, desquamating agents, depigmenting agents, antipigmenting agents, propigmenting agents ), NO synthase inhibitor Pesticides, agents that stimulate fibroblast and / or keratinocyte proliferation and / or keratinocyte differentiation, agents that act on the microcirculation, agents that affect cellular energy metabolism, healing agents, and mixtures thereof You can choose from.

  The composition according to the invention can be in various forms, e.g. suspensions, dispersions, solutions, gels, oil-in-water (O / W), water-in-oil (W / O), and multiple (e.g. W / O / W, polyol / O / W, O / W / O) emulsions, emulsions, creams, foams, sticks, vesicle dispersions, eg ionic and / or nonionic lipid dispersions, biphasic And can be multiphase lotion, spray, powder, paste. The composition may be anhydrous, for example, an anhydrous paste or stick. The composition may be a composition that does not wash away.

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

  According to another embodiment, the composition according to the invention comprises, for example, a compact powder, a lotion, a serum, an emulsion, a cream, a base foundation, a makeup undercoat, a makeup base coat, a foundation, a powdery powder, a blusher, a lipstick, It can be in the form of lip balm, eye shadow, eyeliner, loose powder, concealer, nail coat, mascara, sunscreen and the like.

  Those skilled in the art will select the appropriate formulation and method of preparation based on their general knowledge, taking into account the nature of the ingredients used, e.g., the solubility of the ingredients in the medium and the application envisioned for the composition. can do.

(Example)
The invention will be described in more detail by way of example, but should not be construed as limiting the scope of the invention.

(Examples 1 to 4 and Comparative Examples 1 to 4)
Using a hybridizer equipped with a high-speed rotor having a plurality of blades in a room under dry conditions, which is marketed by Nara Machinery Co., Ltd. in Japan, the components shown in Table 1 are subjected to the hybridizer method to form a composite pigment. Got.

  Specifically, for each of Production Examples 1 to 4 (P1 to P4 in Table 1), the components shown in Table 1 were placed in a plastic bag and shaken by hand for a short time to obtain the mixing ratios shown in Table 1 (Table 1). The number 1 is mixed by weight). The mixtures obtained after hand shaking according to Production Examples 1 to 4 are referred to as Comparative Examples 1 to 4, respectively. The obtained mixture was put into a hybridizer, and the rotor was rotated at 8,000 rpm (linear speed 100 m / s) for 5 minutes. The composite pigments thus obtained after being subjected to the hybridizer method are referred to as Examples 1 to 4, respectively.

Mica 1 ^*: Synthesis Maikamaika 2 ^* Synthesis is coated with lauroyl lysine Maikamaika 3 ^*: synthetic mica that is coated with an acrylic silicone
TiO ₂ : MT-100 TV marketed by Teika Corporation in Japan
OMC: Ethylhexyl methoxycinnamate
Mexoryl: Drometrizol trisiloxane

[Measurement of particle size change]
The change in particle size before and after being subjected to the hybridizer method was measured by MASTERSIZER 2000 (Malvern Industries Ltd. UK). The particle size before being subjected to the hybridizer method corresponds to the particle size of the “mixture” in which the UV screening agent spreads and covers the core particles after hand shaking.

  The results are shown in Table 2. The particle sizes before and after being subjected to the hybridizer method correspond to the particle sizes of Comparative Examples 1 to 4 and Examples 1 to 4, respectively.

Ratio (%): (particle diameter [example]) / (particle diameter [comparative example]) × 100

  From Table 2, it is clear that the particle size of each core particle was reduced by 24 to 36% because the core particle was collapsed by the hybridizer method.

  Since the particle size of Examples 1-4 is smaller than the particle size of Comparative Examples 1-4, in Examples 1-4, a smoother texture can be obtained.

TWC Foundation A 2-way cake (TWC) foundation containing any of Examples 1-4 or any of Comparative Examples 1-4 was prepared by mixing the components shown in Table 3.

[Determination of friction coefficient]
The tribomaster type TL201Sa (Trinity Lab, Japan) was used to measure the coefficient of friction (MIU) of the TWC foundation.

  A TWC foundation 30 mg to 50 mg was placed on a synthetic leather sheet fixed with a double-sided tape on a test stand of a tribomaster. A cubic aluminum probe with a 1 cm × 1 cm square tip was also covered with a synthetic leather sheet, and the probe was used to spread the TWC foundation straight up to a distance of 2.0 cm at a speed of 1 cm / sec. The return process was repeated 5 times, and the MIU was averaged from 10 sets of MIU data for each forward and return journey. The measurement was repeated three times and the results obtained were averaged.

  The results are shown in Table 4.

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

  From Table 4, it is clear that cosmetics containing the composite pigments of Examples 1-4 have a lower coefficient of friction than cosmetics containing the mixtures of Comparative Examples 1-4.

  Therefore, a cosmetic product containing the composite pigment according to the present invention can provide a smoother feeling than conventional cosmetics containing a simple mixture of components corresponding to the composite pigment.

[Determination of UVA and UVB absorbance]
Using a V-550 ultraviolet-visible spectrophotometer (JASCO, Japan), the UV absorbance of the TWC foundation was measured as follows.

^On the adhesive surface area of 10 cm ² of double-sided tape affixed on a transparent plastic sheet, 6.0 mg of TWC foundation was spread evenly with fingers. The powder sample was sandwiched between the TWC foundation covered with another transparent plastic sheet. This test sheet was set in a V-550 sheet cell holder, and the absorbance was measured at 260 nm to 400 nm. The average of absorbance in the range of 260 nm to 320 nm and 320 nm to 400 nm with a powder sample of 0.6 mg / cm ² was used as the absorbance value of UVB and UVA, respectively.

  The results are shown in Tables 5 and 6.

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

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

  From Table 5 and Table 6, the cosmetic containing the composite pigments of Examples 1 to 4 has a better or equivalent UV shielding effect (98%), especially in the UVB region, compared to the cosmetic containing the mixture of Comparative Examples 1 to 4. ) Is obvious.

  Therefore, a cosmetic containing the composite pigment according to the present invention can obtain a UV shielding effect equivalent to or better than that of a conventional cosmetic containing a simple mixture of components corresponding to the composite pigment. This is because the UV screening agent is moderately dispersed on and in the composite pigment according to the present invention.

(Example 5)
The preparation of the composite pigment according to Example 1 was repeated under the condition that kaolin was replaced with lauroyl lysine plate.

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

The composite pigment according to Example 5 was confirmed to include a plurality of lauroyl lysine plates as cores with a part of the UV shielding agent (TiO ₂ ) sandwiched therebetween.

  Since the composite pigment according to the present invention is no longer strictly in the form of a plate, as shown in FIG. 1, the feeling on the skin can be made better than the conventional plate-like composite pigment.

(Example 6 and Comparative Example 6)
The preparation of the composite pigment according to Example 1 and the mixture according to Comparative Example 1 was 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 referred to as Example 6 and Comparative Example 6, respectively.

Ca (b): Massive form of CaCO ₃ , Omyapure 35LM-OG marketed by Omya, Australia
Red: Red 202
Mexoryl: Drometrizol trisiloxane

Lipstick The bases whose ingredients are shown in Table 8 are mixed with the composite pigment of Example 6 or the mixture of Comparative Example 6 at 90 ° C. with a three cylinder roller so that the colored pigment (Red 202) is 0.1 wt% of the lipstick. Lipsticks were prepared by mixing at

[Determination of UVA and UVB absorbance]
Using a V-550 ultraviolet-visible spectrophotometer (JASCO, Japan), the UV wave absorbance of each lipstick was measured as follows for the lipstick.

150 mg of lipstick was poured onto a 4 cm ² square area on a transparent plastic sheet surrounded by a double-sided tape affixed to the transparent plastic sheet. A test sheet was prepared by covering the lipstick with another transparent plastic sheet and sandwiching the paste sample therebetween. The average of the absorbance in the range of 260 nm to 320 nm and 320 nm to 400 nm with a paste sample of 150 mg / 4 cm ² was used as the absorbance value of UVB and UVA, respectively. The results are shown in Table 9 and Table 10.

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

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

  From Tables 9 to 10, it is clear that the cosmetic containing the composite pigment of Example 6 has a higher UV absorbance than the cosmetic containing the mixture of Comparative Example 6.

  Thus, a cosmetic product comprising a composite pigment according to the present invention achieves a better UV shielding effect obtained even from a colored pigment, compared to a conventional cosmetic product comprising a simple mixture of components corresponding to the composite pigment. be able to.

[Measure color]
Using DATACOLOR 600 (Applied Color Systems Inc., USA), the colors (L ^* , a ^* , b ^* ) of the lipsticks according to Example 6 and Comparative Example 6 were measured as follows.

2.5 g of lipstick was poured into an aluminum dish (25 mm (L) × 23 mm (W) × 4 mm (D)) and cooled to harden the paste. L ^* , a ^* and b ^* of the test sample were measured from the top of the paste.

  The results are shown in Tables 11-13.

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

  Therefore, a cosmetic product containing the composite pigment according to the present invention can obtain a higher quality color with higher saturation than a conventional cosmetic product containing a simple mixture of components corresponding to the composite pigment.

Claims (6)

Having an aspect ratio of at least 5 and a length in the range of 0.3 μm to 30 μm, and natural mica, synthetic mica, sericite, kaolin, talc, hydrotalcite, boron nitride, calcium carbonate, barium sulfate, titanium oxide , Hydroxyapatite, silica, zinc oxide, magnesium sulfate, magnesium carbonate, aluminum oxide, aluminum silicate, calcium silicate, calcium phosphate, magnesium oxide, bismuth oxychloride, glass flakes, and mixtures thereof A plurality of plate-like inorganic base materials composed of an inorganic material ;
Primary particle diameter of 1 nm to 5 [mu] m, including the step of subjecting at least one UV screening agent to the hybridizer method,
A method for preparing a composite pigment, wherein the UV screening agent is contained in a layer having a thickness of 0.03 μm to 10 μm and at least partially covers the plate-like inorganic substrate, and has a thickness of 0.2 μm to 25 μm . At least one UV screening agent is an organic or inorganic, process for the preparation of composite pigments according to claim 1, wherein. At least one UV screening agent is anthranilic acid derivative, dibenzoylmethane derivative, cinnamic acid derivative, salicylic acid derivative, camphor derivative, benzophenone derivative, β, β-diphenylacrylate derivative, triazine derivative, benzotriazole derivative, benzalmalonic acid derivative , Benzimidazole derivatives, imidazoline derivatives, bis-benzoazolyl derivatives, p-aminobenzoic acid (PABA) and its derivatives, methylenebis (hydroxyphenylbenzotriazole) derivatives, benzoxazole derivatives, shielding polymers and silicones, α-alkylstyrene-derived dimers 4,4-diarylbutadiene, octocrylene and its derivatives, guaiazulene and its derivatives, rutin and its derivatives, flavonoids, biflavonoids, oryzanol and its Conductor, quinic acid and derivatives thereof, phenol, retinol, cysteine, aromatic amino acids, aromatic amino acid residues containing peptide, as well, including organic UV screening agent selected from the group consisting of mixtures of claim 2, wherein Preparation method of composite pigment. Preparation of a composite pigment according to claim 2 or 3 , wherein the at least one UV screening agent comprises an inorganic UV screening agent selected from the group consisting of silicon carbide, coated or uncoated metal oxides, and mixtures thereof. Method. The preparation method of the composite pigment as described in any one of Claim 1 to 4 whose weight ratio of the said plate-shaped inorganic base material to at least 1 sort (s) of UV shielding agent is 100: 1-100: 500. The method for preparing a composite pigment according to any one of claims 1 to 5 , wherein at least one color pigment is further subjected to a hybridizer method.