JP2015525756A - Composite pigment and preparation method thereof - Google Patents

Abstract

The present invention comprises at least one small core particle having an average particle size of more than 100 nm and less than 1 μm, preferably less than 600 nm, more preferably less than 400 nm, and optionally an average particle size of 2 μm or more, preferably 3 μm or more, more preferably Comprises at least one large core particle of 4 μm or more, and even more preferably 5 μm or more, and the surface of the small core particle is at least partially by at least one coating layer comprising at least one particulate solid organic UV filter And the small core particles comprise at least one organic polymer. The composite pigments according to the invention can achieve an enhanced UV filter effect and safety, and optionally an enhanced coloring effect.

Description

  The present invention relates to a composite pigment comprising small core particles that are at least partially covered by a particulate solid organic UV filter, and in certain embodiments further comprising large core particles, and a method for preparing said composite pigment.

  Various research and development of powdery components such as pigments used in cosmetics have been conducted in accordance with the diverse needs of cosmetics. In particular, many types of surface treatments or composite powders have been proposed for cosmetic powders. For example, JP-A-H06-1709 discloses a composite pigment containing core particles covered with fine particles of an inorganic UV filter.

  A composite pigment based on fine particles of an inorganic UV filter can provide a good UV filter effect in the UVB region (wavelength of 280 to 315 nm). However, the UV filter effect obtained with such composite pigments based on inorganic UV filters is insufficient in the UVA region (wavelengths of 315 to 400 nm).

  UVA light can cause strong damage to the skin. Therefore, it is important for suncare cosmetics to protect the skin from UVA light. In general, ZnO particulates or liquid organic UV filters have been used in sun care cosmetics to shield UVA light.

JP-A-H06-1709 GB-A-2303549 EP-A-893119 WO95 / 22959 WO97 / 03642 GB2286774 EP743309 WO98 / 22447 GB2319523 EP-A-0790243 WO98 / 25922 US5687521 US5373037 US5362881 US5888481 U.S. Pat.No. 4,617,390 DE676103 CH350763 US5501850 US5961960 EP0669323 US5518713 US2463264 EP0921126 EP712855 JP04134042 JP04134043 EP0576974 FR2395023 JP01158090 EP0390683 JP04134041 FR2506156 EP0693471 FR2528420 FR2529887 EP0694521 FR2638354 EP0714880 JP04290882 FR-A 2 639 347 JP-87 166 517 WO93 / 10753 WO93 / 11095 WO95 / 05150 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 USP 5240975 U.S. Pat.No. 2,463,264 WO93 / 04665 DE-19855649 European Patent No. 0293795 JP-A-2-295912 U.S. Pat.No. 3,709,437 U.S. Pat.No. 3,937,364 U.S. Pat.No. 4,022,351 U.S. Pat.No. 4,1147,306 U.S. Pat.No. 4,184,615 U.S. Pat.No. 4,598,862 U.S. Pat.No. 4,615,467 U.S. Pat.No. 5,364,031

J. Am. Chem. Soc., 79, 5706-5708, 1957 J. Am. Chem. Soc., 82, 609-611, 1960 J. Chim. Phys., 64, 1602 (1967) E. Mariani et al., 16th IFSCC Congress, New York (1990) Cosmetics & Toiletries, February 1990, 105, 53-64

  However, fine particles of a solid UV filter such as ZnO may easily aggregate and have low dispersibility. Therefore, it is often difficult to uniformly disperse the fine particles of the solid UV filter in the form of primary particles in cosmetics such as sunscreen cosmetics. Therefore, it is difficult to improve the UV filter characteristics of cosmetics containing solid UV filter fine particles, particularly in the UVA region.

  Furthermore, the particulates of solid UV filters can adversely affect the skin, and solid UV filters can easily come into contact with the skin when irritating, and there are several risks that can also adversely affect the skin. In addition, there are concerns about ZnO fine particles due to their environmental toxicity.

  Furthermore, when a liquid organic UV filter is used, it is difficult to formulate into cosmetics and stabilize in cosmetics. In addition, liquid organic UV filters do not feel good when applied on the skin.

  Therefore, an object of the present invention is to provide a novel composite pigment based on a solid organic UV filter and capable of realizing a good UV filter effect, particularly a UVA filter effect.

  Another object of the present invention is to reduce or prevent the adverse effects on the skin caused by the expected solid UV filter while achieving a good UV filter effect.

  Another object of the invention is based on organic UV filters that are easy to formulate and stabilize in cosmetics and do not feel bad when applied on the skin, especially in the UVA region. It is to provide a composite pigment having a high effect.

Any of the above objects of the present invention
Comprising at least one small core particle having an average particle size greater than 100 nm and less than 1 μm, preferably less than 600 nm, more preferably less than 400 nm,
The surface of the small core particles is at least partially covered by at least one coating layer comprising at least one particulate solid organic UV filter;
Small core particles can be realized with composite pigments containing at least one organic polymer.

  The coating layer on the small core particles may comprise at least one solid inorganic UV filter and / or at least one color pigment.

  Particulate solid organic UV filters are oxalanilide type, triazine type, benzotriazole type; vinylamide type; cinnamamide type; type containing one or more benzazole groups and / or benzofuran group or benzothiophene group or indole type Aryl vinylene ketone type; phenylene bis (benzoxazinone) derivative type; or acrylonitrile amide, sulfonamide or carbamate derivative type particulate organic UV screening agents.

  The solid inorganic UV filter may be selected from the group consisting of silicon carbide, metal oxides, and mixtures thereof.

  The particulate solid organic or inorganic UV filter may have an average particle size of 1 nm to 50 nm, preferably 5 nm to 40 nm, more preferably 10 nm to 30 nm.

  The solid inorganic UV filter may have at least one coating layer.

  The coating layer of the solid inorganic UV filter is composed of alumina, silica, aluminum hydroxide, silicone, silane, fatty acid or salt thereof, fatty alcohol, lecithin, amino acid, polysaccharide, protein, alkanolamine, wax, (meth) acrylic polymer, organic UV It may contain at least one compound selected from the group consisting of a filter and a (per) fluoro compound.

  The coating layer on the small particles may have a thickness of 1 nm to 50 nm, preferably 5 nm to 40 nm, more preferably 10 nm to 30 nm.

  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 May be selected from the group consisting of silver powder, gold powder, barium sulfate, carbon black, D & C type pigments, lakes, pearlescent pigments, silica, and mixtures thereof.

  The coating layer on the small particles may further comprise at least one additional UV filter, in particular at least one liquid organic UV filter.

  The small particles may further comprise at least one inorganic material and / or at least one organic material, preferably at least one organic material.

  Inorganic materials include mica, synthetic mica, talc, sericite, boron nitride, glass flake, calcium carbonate, barium sulfate, titanium oxide, hydroxyapatite, silica, silicate, zinc oxide, magnesium sulfate, magnesium carbonate, magnesium trisilicate, Select from the group consisting of aluminum oxide, aluminum silicate, calcium silicate, calcium phosphate, magnesium oxide, bismuth oxychloride, kaolin, hydrotalcite, mineral clay, synthetic clay, iron oxide, and mixtures thereof It's okay.

  In a preferred embodiment of the invention, the small core particles may comprise at least one copolystyrene, preferably a styrene / acrylate copolymer and / or a crosslinked styrene / methyl methacrylate copolymer.

  According to a preferred embodiment, the composite pigment according to the invention further comprises at least one large core particle having an average particle size of 2 μm or more, preferably 3 μm or more, more preferably 4 μm or more, and even more preferably 5 μm or more. Well, the surface of the large core particle is optionally at least partially covered by at least one coating layer comprising at least one selected from the group consisting of particulate solid organic UV filters, solid inorganic UV filters and colored pigments. ing.

  The mass ratio of small core particles to large core particles may be 10:90 to 90:10, preferably 20:80 to 80:20, more preferably 30:70 to 70:30.

  The mass ratio of the small core particles to the particulate solid organic UV filter may be 10:90 to 90:10, preferably 30:70 to 70:30, more preferably 40:60 to 50:50.

  The mass ratio of small core particles / large core particles / particulate solid organic UV filter is 20: 50: 30-50: 20: 30, preferably 35: 15: 50-15: 35: 50, more preferably 10: It may be 20:70 to 20:10:70.

  The large core particles may comprise at least one inorganic material and / or at least one organic material, preferably at least one organic material.

  Inorganic materials for large core particles include mica, synthetic mica, talc, sericite, boron nitride, glass flake, calcium carbonate, barium sulfate, titanium oxide, hydroxyapatite, silica, silicate, zinc oxide, magnesium sulfate, magnesium carbonate, three Select from the group consisting of magnesium silicate, aluminum oxide, aluminum silicate, calcium silicate, calcium phosphate, magnesium oxide, bismuth oxychloride, kaolin, hydrotalcite, mineral clay, synthetic clay, iron oxide, and mixtures thereof It's okay.

  Organic materials for large core particles are poly (meth) acrylate, polyamide, silicone, polyurethane, polyethylene, polypropylene, polystyrene, copolystyrene, polyhydroxyalkanoate, polycaprolactam, poly (butylene) succinate, polysaccharide, polypeptide, polyvinyl alcohol , Polyvinyl resins, fluoropolymers, waxes, amidosulfonic acid polyvalent metal salts, acylated amino acids, and mixtures thereof.

  In particular, polymethacrylate is preferred as an organic material for large core particles. More preferred is methyl methacrylate polymer.

  In a preferred embodiment of the invention, the small core particles may comprise at least one copolystyrene, preferably a styrene / acrylate copolymer and / or a crosslinked styrene / methyl methacrylate copolymer, and the large core particles comprise at least one polystyrene. (Meth) acrylate, preferably comprising a methyl methacrylate polymer, wherein the small core particles and the large core particles are at least selected from benzotriazole UV filters, preferably methylene bis (hydroxyphenylbenzotriazole) derivatives having the following structure (4): At least partially covered by at least one coating layer comprising one kind of particulate solid organic UV filter:

Wherein, T ₂ are independently, C ₁ -C ₄ alkyl group, C ₅ -C ₁₂ cycloalkyl group, or one or more of which may be substituted by a group C ₁ is selected from aryl residue ~ Represents a _C18 alkyl group].

  More particularly, the particulate solid organic UV filter may be a molecule represented by the following formula:

  The above molecule has the scientific term 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], for example, INCI name: methylenebis-benzotriazolyl tetramethylbutylphenol sold by BASF under the trade name TINOSORB M or sold by Fairmount Chemical under the trade name MIXXIM BB100.

The composite pigment according to the present invention is
At least one small core particle having an average particle size greater than 100 nm and less than 1 μm, preferably less than 600 nm, more preferably less than 400 nm, and containing at least one organic polymer;
Optionally, at least one large core particle having an average particle size of 2 μm or more, preferably 3 μm or more, more preferably 4 μm or more, and even more preferably 5 μm or more,
At least one particulate solid organic UV filter;
Optionally, it can be prepared by a method of preparing a composite pigment comprising subjecting at least one selected from the group consisting of a solid inorganic UV filter, a colored pigment and an additional UV filter to a mechanochemical fusion process.

  Another object of the present invention is to provide cosmetic compositions or cosmetic agents with advantageous cosmetic and / or practical effects by using the composite pigments according to the present invention.

  The above object can be realized by introducing the composite pigment according to the invention into a cosmetic composition or cosmetic agent for photoprotection from UV irradiation, in particular UV-A irradiation.

  Thus, for example, the composite pigment according to the invention can be contained in a cosmetic composition, in particular in the form of a liquid, powder or aerosol foam.

  As a result of intensive studies, the present inventors have found that it is possible to obtain a novel composite pigment based on a particulate solid organic UV filter and capable of realizing a good UV filter effect, particularly a UVA filter effect. discovered.

The novel composite pigment according to the present invention is
Comprising at least one small core particle having an average particle size of less than 1 μm, the surface of the small core particle being at least partially covered by at least one layer comprising at least one particulate solid organic UV filter; The small core particles contain at least one organic polymer.

  Surprisingly, coatings containing particulate solid organic UV filters are miniaturized by using small core particles with an average particle size of less than 1 μm, and optionally large core particles, containing at least one organic polymer. Can be applied to the surface of the core particles, resulting in a better UV filter effect than bulk particulate solid organic UV filters, especially in the UVA region, especially when compared to the use of solid inorganic UV filters It has been discovered that the UV filter effect can be improved in the UVA region.

  Since the particles of the solid organic UV filter are tightly bound on the small core particles, it is not possible for the UV filter, i.e. a large amount of single-particulate organic UV filter, to come into direct contact with the skin. Thus, the composite pigment according to the present invention is safer than bulk particulate solid organic UV filters.

  Furthermore, the composite pigment according to the present invention can be easily formulated into a cosmetic and stabilized therein, and the particulate organic UV filter essentially used in the composite pigment according to the present invention is not in liquid form. For this reason, it is possible to avoid deterioration of the texture when applied on the skin. In particular, the composite pigment according to the present invention has a high coefficient of friction so that the fine particles of the solid organic UV filter are firmly fixed on the core particle and thus do not spread easily on the skin, and gives a unpleasant feeling of use. Since fine particles can be reduced, a better feeling of use can be provided.

  Furthermore, the cosmetic composition or cosmetic comprising the composite pigment according to the present invention can exert advantageous cosmetic and / or practical effects due to the inclusion of the composite pigment according to the present invention. For example, the cosmetic composition according to the present invention has a good UV shielding effect, particularly in the UVA region. In addition, when the cosmetic composition is in a powder form, it has a smooth feeling of use due to a reduction in friction, an excellent concealing effect against skin defects such as pores and small wrinkles, a matting effect, and a good compactibility that is difficult to collapse. On the other hand, when the cosmetic composition is in a liquid form, visual optical effects such as a matte effect and a haze effect are also good.

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

(Small core particles)
The small core particles used in the composite pigment according to the invention are not limited as long as the small core particles have an average particle diameter or average particle diameter of more than 100 nm and less than 1 μm, preferably less than 600 nm, more preferably less than 400 nm. The small core particles may be in the form of solid or hollow particles, preferably hollow particles.

  The average particle diameter or average particle diameter herein is the arithmetic average diameter, and can be determined, for example, by calculating the average of the dimensions of 100 particles selected on an image obtained by scanning electron microscopy. .

  The small core particles can have any shape. For example, it is possible to use small core particles in the form of a plate having an aspect ratio of at least 5, preferably greater than 10, more preferably greater than 20, 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.

  When plate-like particles are used in the present invention, the plate-like particles preferably have a length in the range of more than 100 nm to less than 1 μm, preferably less than 600 nm, more preferably less than 400 nm.

  In a preferred embodiment, the small core particles are spherical.

  The material of the small core particles is not limited. The material of the small core particles contains at least one organic polymer and may further include at least one inorganic material.

  Organic polymers of small core particles are poly (meth) acrylate, polyamide, silicone, polyurethane, polyethylene, polypropylene, polystyrene, copolystyrene, polyhydroxyalkanoate, polycaprolactam, poly (butylene) succinate, polysaccharide, polypeptide, polyvinyl alcohol , Polyvinyl resins, 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. Polyamides such as Nylon (registered trademark), polyhydroxyalkanoates such as polylactic acid, poly (meth) acrylates such as polymethylmethacrylate, silicones, and mixtures thereof are more preferred.

  In particular, as the organic polymer, copolystyrene is preferable, and a styrene / acrylate copolymer and a crosslinked styrene / methyl methacrylate copolymer are more preferable. Therefore, as small core particles, for example, Sunspheres (small hollow particles formed from styrene / acrylate copolymer) marketed by Rohm and Haas, and SX859 (A) marketed by JSR Corporation (Japan) and SX866 (B) (small hollow particles formed from a crosslinked styrene / methyl methacrylate copolymer) is preferred.

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

The inorganic material and / or the organic material may be porous. The porosity of the material, by the BET ^{method, 0.05m 2 / g~1,500m 2 / g} , more preferably 0.1m ² / g~1,000m ² / g, more preferably 0.2m ² / g~500m ² / g Specific surface area.

  The small core particles may be pre-coated or uncoated.

  In certain embodiments, the small core particles are coated from the beginning. The material of the original coating layer of the small core particles is preferably, but not limited to, organic materials such as amino acids, N-acylamino acids, amides, silicones, and modified silicones. Examples of the organic material include lauroyl lysine and acrylic-modified silicone.

(Layer on small core particles)
The small core particles are at least partially covered by at least one layer comprising at least one particulate solid organic UV filter. The said layer may be called a coating layer. It is preferable that 10% or more of the surface of the small core particle can be covered with the coating layer. More preferably, 50% or more of the surface of the small core particles can be covered with the coating layer. More preferably, 80% or more of the small core particles can be covered with the coating layer. Most preferably, the entire surface of the small core particles can be covered by a coating layer.

  The thickness of the coating layer may vary depending on several factors such as the size of the small core particles. Usually, the thickness of the coating layer may be in the range of 1 nm to 50 nm, preferably 5 nm to 40 nm, more preferably 10 nm to 30 nm.

  When two or more coating layers are present on the small core particles, the thickness and composition of the coating layers may be the same or different from each other.

  In addition to the particulate solid organic UV filter, the coating layer may contain any additional materials such as colored pigments and / or additional UV filters, preferably solid inorganic UV filters. The additional material may be present in an amount ranging from 1 to 50% by weight relative to the total weight of the additional material and the particulate solid organic UV filter.

(Particulate solid organic UV filter)
As described above, the coating layer on the small core particles includes at least one particulate solid organic UV filter. When two or more kinds of particulate solid organic UV filters are used, they may be the same or different and are preferably the same. The term “UV filter” can be restated as “UV screening agent”.

  The particulate solid organic UV filter used in the present invention may be active in the UV-A and / or UV-B region, preferably in the UV-A region, or in the UV-A and UV-B region.

  A “particulate solid organic UV filter” is (1) in the form of solid particles at 25 ° C., insoluble in the medium of the composition of the present invention, and (2) absorption and / or reflection of UVA and / or UVB radiation and Means an organic molecule that blocks or at least limits contact of the irradiated keratin material (skin, hair, scalp) with the surface by diffusion.

  The term “solid” means a solid at 25 ° C. under 1 atmosphere.

  The particulate solid organic UV filter according to the invention preferentially has an average particle size ranging from 10 to 5 μm, more preferably from 10 nm to 2 μm, more particularly from 20 nm to 2 μm.

  The particulate solid organic UV filter according to the present invention can be made into the desired particulate form by any flexible means such as dry grinding or grinding in a solvent, sieving, atomization, pulverization or spraying.

  Examples of methods for micronizing insoluble particulate organic UV filters are disclosed in applications GB-A-2303549 and EP-A-893119, which are incorporated by reference and constitute an integral part of the description. The grinder used according to these documents may be an air jet mill, a bead mill, a vibration mill or a hammer mill, preferably a high speed stirring mill or impact mill, more particularly a rotary bead mill, a vibration mill ( vibrating mill), tube mill or rod mill.

  The composite pigment according to the present invention has an effect of giving a transparent or clear appearance because the fine particles of the particulate solid organic UV filter do not aggregate and spread on the core particles. It should be noted that the single particulates of the particulate solid organic UV filter can easily aggregate.

  The material of the particulate solid organic UV filter is not limited as long as it is organic. When two or more kinds of solid particulate organic UV filters are used, the materials of the particulate solid organic UV filters may be the same as or different from each other.

  The particulate solid organic UV screening agent according to the present invention comprises an oxalanilide type, a triazine type, a benzotriazole type; a vinylamide type; a cinnamamide type; one or more benzazole groups and / or a benzofuran group or a benzoyl group. Particular organic UV screening agents can be selected from types containing thiophene groups or indole types; aryl vinylene ketone types; phenylene bis (benzoxazinone) derivative types; or acrylonitrile amide, sulfonamide or carbamate derivative types.

  In the sense of use in the present invention, the term benzazole simultaneously encompasses benzothiazoles, benzoxazoles and benzimidazoles.

  Among the UV screening agents, mention may be made of the oxalanilide type according to the invention, corresponding to the following structure:

Wherein R ₁ and R ₂ are independently C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy. A preferred compound of formula (1) is N- (2-ethoxyphenyl) -N ′-(2-ethylphenyl) -ethanediamide]. These compounds are disclosed in patent application WO95 / 22959.

  For example, mention may be made of the commercial products Tinuvin 315 and Tinuvin 312 sold by the company Ciba-Geigy, each having the following structure:

  A preferred class of solid triazine UV absorbers are those having the following formula:

[Wherein R ₃ , R ₄ and R ₅ are independently H, OH, C ₁ -C ₁₈ alkoxy, NH ₂ , NH-R ₆ or N (R ₆ ) ₂ (R ₆ is C ₁ -C ₁₈ Is alkyl}, OR ₆ {R ₆ is C ₁ -C ₁₈ alkyl}, phenyl, phenoxy, or anilino, or pyrrole {each phenyl, phenoxy, or anilino, or pyrrolo moiety is OH, carboxy, CO Optionally substituted with 1, 2 or 3 substituents selected from —NH ₂ C ₁ -C ₁₈ alkyl or alkoxy}, C ₁ -C ₁₈ carboxyalkyl, C ₅ -C ₈ cycloalkyl, methyl Ridencamphor group, group — (CH═CH) _m C (═O) —OR ₆ (m is 0 or 1, R ₆ has the same meaning as above}, or group:

Or its corresponding alkali metal salts, ammonium salts, mono-, - di - or tri -C ₁ -C ₄ alkyl ammonium salts, mono -, di - or tri -C ₂ -C ₄ alkanolammonium salts, or C ₁ -C ₁₈ alkyl esters].

  These compounds are disclosed in WO97 / 03642, GB2286774, EP743309, WO98 / 22447 and GB2319523, which are incorporated by reference as an integral part of the description.

  Preferred compounds of formula (2) have the formula:

As well as 2,4,6-tris (diisobutyl-4'-aminobenzalmalonate) -s-triazine and 2,4-bis (diisobutyl-4-aminobenzalmalonate) -6- (4'-aminobenzylidene camphor) -s-triazine.

  Particularly preferred is bis-ethylhexyloxyphenol methoxyphenyl triazine marketed by Ciba-Geigy under the trademark “Tinosorb S”.

  Particularly preferred compounds of formula (2) are those having the following formula

Wherein the individual groups R ₇ are the same or different and are each hydrogen; alkali metal; ammonium group N (R ₈ ) ₄ where R ₈ is hydrogen or an organic group; C ₁ -C ₂₀ alkyl Or a polyoxyethylene group containing 1 to 10 ethylene oxide units, the terminal OH group of which may be etherified with a C _{1 to} C ₃ alcohol].

With respect to the compound of formula (30), when R ₇ is an alkali metal, it is preferred that it is potassium, or especially sodium, and R ₇ is a group N (R ₈ ) _{4 in} which R ₈ has its previously stated meaning. On one occasion, mono -, di - or tri -C ₁ -C ₄ alkyl ammonium salts, mono -, di - or tri -C ₂ -C ₄ alkanolammonium salts can, or a C ₁ -C ₂₀ alkyl esters preferably, R _7, when a C ₁ -C ₂₀ alkyl group, C ₆ -C ₁₂ alkyl groups, more preferably C ₈ -C ₉ alkyl group, especially 3,5,5-trimethylpentyl radical, or most particularly In this case, it is preferably a 2-ethylhexyl group, and when R ₇ is a polyoxyethylene group, this group preferably contains 2 to 6 ethylene oxide units.

  Among the triazine-type UV screening agents according to the invention, insoluble s-triazine derivatives carrying benzalmalonate groups and / or phenylcyanoacrylate groups, such as applications (incorporated by reference as an integral part of the description) Mention may also be made of those disclosed in EP-A-0790243.

Among these triazine type insoluble UV screening agents, the following compounds are more specifically mentioned:
-2,4,6-tris (diethyl 4'-aminobenzalmalonate) -s-triazine,
-2,4,6-tris (diisopropyl 4'-aminobenzalmalonate) -s-triazine,
-2,4,6-tris (dimethyl 4'-aminobenzalmalonate) -s-triazine,
-2,4,6-tris (ethyl α-cyano-4-aminocinnamic acid) -s-triazine.

  Among the triazine type UV screening agents according to the invention, an insoluble s-triazine derivative carrying a benzotriazole group and / or a benzothiazole group, for example the application WO 98 / (incorporated by reference and constitutes an integral part of the description) The one disclosed in 25922 can also be mentioned.

Among these compounds, the following can be specified more specifically:
-2,4,6-tris [(3 '-(benzotriazol-2-yl) -2'-hydroxy-5'-methyl) phenylamino] -s-triazine,
-2,4,6-tris [(3 '-(benzotriazol-2-yl) -2'-hydroxy-5'-tert-octyl) phenylamino] -s-triazine.

  A preferred class of solid (benzo) triazole UV absorbers are those having the formula:

[Wherein T ₁ is C ₁ -C ₁₈ alkyl, or preferably hydrogen, and T ₂ is hydrogen, hydroxyl, or C ₁ -C ₁₂ cycloalkyl or aryl, such as phenyl, preferably α, α- C ₁ -C ₁₈ alkyl optionally substituted with dimethylbenzyl. C ₁ -C ₁₈ alkyl group may be branched be linear, for example, methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, tert- butyl, tert- octyl, n- amyl, n- hexyl, n- heptyl, n- octyl, isooctyl, n- nonyl, n- decyl, n- undecyl, an n- dodecyl, tetradecyl, hexadecyl or octadecyl, C ₅ -C ₁₂ cycloalkyl group, For example, cyclopentyl, cyclohexyl or cyclooctyl, and an aryl group is, for example, phenyl or benzyl].

  As examples of compounds of formula (31), mention may be made of the commercial products Tinuvin 328, 320, 234 and 350 from Ciba-Geigy having the following structure:

Among the insoluble organic UV screening agents of the benzotriazole type according to the invention, the compounds disclosed in patents US5687521, US5373037 and US5362881, in particular [2,4′-dihydroxy-3- (2H-benzotriazol-2-yl) -5- (1,1,3,3-tetramethylbutyl) -2 '-(n-octoxy) -5'-benzoyl]
Diphenylmethane (sold under the name Mixxim PB30 by Fairmount Chemical, with the following structure):

  A further preferred class of solid (benzo) triazole UV absorbers are those having the formula:

[Wherein T ₂ has the aforementioned meaning].

  An even more preferred class of solid triazole UV absorbers are those having the formula:

[Wherein T ₂ has the above-mentioned meaning, and is preferably methyl, t-butyl, or —C (CH ₃ ) ₂ —CH ₂ —C (CH ₃ ) ₃ . Accordingly, preferred solid triazole UV absorbers are as follows:

  More specifically, the particulate solid organic UV filter will be a molecule of the formula

The scientific term is 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], for example, trade name TINOSORB from BASF. INCI name: Methylenebisbenzotriazolyl tetramethylbutylphenol sold under the trade name MIXIM BB100 sold by Fairmount Chemical Co.

A preferred class of amide UV absorbers containing solid vinyl groups are those having the formula
_{R 9 - (Y) m -CO} -C (R 10) = C (R 11) -N (R 12) (R 13) (34)
[Wherein R ₉ is C ₁ -C ₁₈ alkyl, preferably C ₁ -C ₅ alkyl, or OH, C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy, or R ₆ is as defined above. Phenyl optionally substituted with 1, 2 or 3 substituents selected from CO-OR ₆ having; R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are the same or different; Each is C ₁ -C ₁₈ alkyl, preferably C ₁ -C ₅ alkyl, or hydrogen; Y is N or O; m has its previously defined meaning].

  Preferred compounds of formula (34) are 4-octyl-3-penten-2-one, ethyl-3-octylamino-2-butenoate, 3-octylamino-1-phenyl-2-buten-1-one, and 3-dodecylamino-1-phenyl-2-buten-1-one.

  A preferred class of solid cinnamide amide UV absorbers are those having the formula

Wherein R ₁₄ is hydroxy or C ₁ -C ₄ alkoxy, preferably methoxy or ethoxy; R ₁₅ is hydrogen or C ₁ -C ₄ alkyl, preferably methyl or ethyl; R ₁₆ is -(CONH) _m -phenyl, where m has the previously described meaning, and the phenyl group is OH, C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy, or R ₆ has the previously described meaning. Optionally substituted with 1, 2 or 3 substituents selected from CO—OR ₆ having R ₁₆ is preferably phenyl, 4-methoxyphenyl, or phenylaminocarbonyl group].

  Mention may also be made of cinnamamide dimers such as those disclosed in patent US5888481, such as compounds having the following structure:

  Compounds of formula (1)-(35) are known. The compound of formula (30) is described in US Pat. No. 4,617,390 along with its preparation.

  Particulate solid organic UV filters are benzotriazole derivatives, in particular phenylbenzotriazole derivatives, such as marketed under the trademark `` Silatrizole '' by Rhodia Chimie or under the trademark `` Mexoryl XL '' by L'Oreal, Drometrizol trisiloxane as shown below is preferred.

  Among benzazole type insoluble organic screening agents, mention may be made of one of the following formulas:

[Wherein each X symbol independently represents an oxygen atom, a sulfur atom or an NR ₂ group,
Each Z symbol independently represents a nitrogen atom or a CH group;
Each R ₁ symbol independently represents an OH group, a halogen atom, optionally a linear or branched C _1-8 alkyl group containing a silicon atom, or a linear or branched C _1-8 alkoxy group. Represent,
Each numerical value m independently has a value of 0, 1 or 2,
n represents an integer of 1 to 4 including both ends,
p is equal to 0 or 1,
Each numerical value q is independently equal to 0 or 1,
Each R ₂ symbol independently represents a hydrogen atom or a benzyl group, or a linear or branched C _1-8 alkyl group optionally containing a silicon atom;
A represents a group having a valence n selected from:

Wherein W represents N or CH, and each R ₃ symbol independently represents a halogen atom or a linear or branched C _1-4 alkyl group, an alkoxy group or a hydroxyl group,
R ₄ represents a hydrogen atom or a linear or branched C _1-4 alkyl group, and c = 0 to 4, d = 0 to 3, e = 0 or 1, and f = 0 to 2] .

  These compounds are described in particular in patent DE676103 and CH350763, patent US5501850, patent US5961960, patent application EP0669323, patent US5518713, patent US2463264, paper J. Am. Chem. Soc., 79, pages 5706-5708, 1957. Am. Chem. Soc., 82, 609-611, 1960, disclosed in patent application EP0921126 and patent application EP712855.

  Examples of preferred compounds of formula (7) include 2-arylbenzazole, 2- (benzoxazol-2-yl) -4-methylphenol, 2- (1H-benzimidazol-2-yl) -4-methoxyphenol Or mention may be made of the family of 2- (benzothiazol-2-yl) phenols, which compounds can be prepared, for example, according to the method disclosed in patent CH350763.

  Examples of preferred compounds of formula (7) include benzimidazolyl benzazole, 2,2'-bisbenzimidazole, 5,5 ', 6,6'-tetramethyl-2,2'-bisbenzimidazole, 5,5' -Dimethyl-2,2'-bisbenzimidazole, 6-methoxy-2,2'-bisbenzimidazole, 2- (1H-benzimidazol-2-yl) -benzothiazole, 2- (1H-benzimidazole-2 -Yl) benzoxazole and the family of N, N′-dimethyl-2,2′-bisbenzimidazole, these compounds can be prepared according to the procedures disclosed in patents US5961960 and US2463264 .

  Examples of preferred compounds of formula (7) include phenylenebenzazole, 1,4-phenylenebis (2-benzooxa-zolyl), 1,4-phenylenebis (2-benzimidazolyl), 1,3-phenylenebis (2- Benzoxazolyl), 1,2-phenylenebis (2-benzoxazolyl), 1,2-phenylenebis (benzimidazolyl), 1,4-phenylenebis (N- (2-ethylhexyl) -2-benzimidazolyl) And the family of 1,4-phenylenebis (N-trimethylsilylmethyl-2-benzimidazolyl) and these compounds are described in patent US2463264 and publication J. Am. Chem. Soc., 82, 609 (1960). And J. Am. Chem. Soc., 79, 5706-5708 (1957).

  Examples of preferred compounds of formula (7) include benzofuranyl benzoxazole, 2- (2-benzofuranyl) benzoxazole, 2- (benzofuranyl) -5-methylbenzoxazole and 2- (3-methyl-2-benzofuranyl) Mention may be made of the family of benzoxazoles, and these compounds can be prepared according to the procedure disclosed in patent US5518713.

  Preferred compounds of formula (8) include, for example, 2,6-diphenyl-1,7-di-hydrobenzo [1,2-d; 4,5-d ′] diimidazole, corresponding to the following formula:

Or 2,6-distyryl-1,7-dihydrobenzo [1,2-d; 4,5-d '] di-imidazole or 2,6-di (p-tert-butylstyryl) -1,7-dihydro Mention may be made of benzo [1,2-d; 4,5-d ′] diimidazole and these compounds can be prepared according to application EP0669323.

  As preferred compounds of formula (9), mention may be made of 5,5′-bis (2-phenylbenzimidazole) of the formula:

This preparation is described in J. Chim. Phys., 64, 1602 (1967).

  Among these solid organic compounds that shield UV radiation, 2- (1H-benzoimidazol-2-yl) benzoxazole, 6-methoxy-2,2'-bisbenzimidazole, 2- (1H-benzimidazole-2 -Yl) benzothiazole, 1,4-phenylenebis (2-benzoxazolyl), 1,4-phenylenebis (2-benzimidazolyl), 1,3-phenylene-bis (2-benzoxazolyl), 1 , 2-phenylenebis (2-benzoxazolyl), 1,2-phenylenebis (2-benzimidazolyl) and 1,4-phenylenebis (N-trimethylsilylmethyl-2-benzimidazolyl) are even more preferred.

  Among the aryl vinylene ketone type solid organic screening agents, mention may be made of those corresponding to any of the following formulas (10) and (11):

[Where:
n ′ = 1 or 2,
B is an aryl group selected from the following formulas (a ′) to (d ′) in formula (10) when n ′ = 1 or in formula (11), or when n ′ = 2 Is a group selected from the following formulas (e ′) to (h ′)]:

[Where:
Each R ₈ symbols are independently, OH group, a halogen atom, optionally linear or branched C _{1 to 6} alkyl groups containing a silicon atom and linear or branched C ₁ containing a silicon atom by _{Represents a -6} alkoxy group, a linear or branched _C1-5 alkoxycarbonyl group, or a linear or branched _C1-6 alkylsulfonamide group optionally containing a silicon atom or an amino acid functional group,
p ′ represents an integer of 0 to 4 including both ends,
q ′ represents 0 or 1,
R ₅ represents hydrogen or an OH group,
R ₆ represents hydrogen, a linear or branched C _1-6 alkyl group optionally containing a silicon atom, a cyano group, a C _1-6 alkylsulfonyl group, or a phenylsulfonyl group,
R ₇ comprises a linear or branched C _1-6 alkyl group optionally comprising a silicon atom or a phenyl group capable of forming a bicycle, optionally substituted with one or two R ₄ groups. Represent,
Alternatively, R ₆ and R ₇ together form a bicyclic or tricyclic C _2-10 hydrocarbonaceous residue, optionally by one or more nitrogen, sulfur and oxygen atoms. is blocked, it is possible to include another carbonyl, optionally substituted with a linear or branched C ₁ -C ₈ alkyl sulfonamido group, but if containing a silicon atom or an amino functional group by, where n '= In the case of 1, R ₆ and R ₇ do not form a camphor nucleus].

Examples of compounds of formula (10) where n ′ = 1, shields UV radiation and has an average particle size of 10 nm to 5 μm can include the following families:
-Styryl ketone type compounds disclosed in application JP04134042, for example 1- (3,4-dimethoxyphenyl) -4,4-dimethylpent-1-en-3-one:

-Benzylidene cineol type compounds such as those described in the article of 16th IFSCC Congress, New York (1990) by E. Mariani et al., For example, 1,3,3-trimethyl-5- (4-methoxybenzylidene)- 2-Oxabicyclo [2.2.2] octane-6-one:

-Benzylidene chromanone type compounds such as those disclosed in application JP04134043, for example 3- (4-methoxybenzylidene) -2,3,4a, 8a-tetrahydro-chromen-4-one:

-Benzylidenethiochromanone type compounds such as those disclosed in application JP04134043, for example 3- (4-methoxybenzylidene) -2,3,4a, 8a-tetrahydro-chromene-4-thione:

Benzylidene quinuclidinone type compounds such as those disclosed in application EP0576974, for example 4-methoxybenzylidene-1-azabicyclo [2.2.2] octane-3-one:

-Benzylidenecycloalkanone type compounds such as those disclosed in application FR2395023, for example 2- (4-methoxybenzylidene) cyclopentanone and 2- (4-methoxybenzylidene) cyclohexanone:

-Benzylidenehydantoin type compounds such as those disclosed in application JP01158090, for example 5- (3,4-dimethoxybenzylidene) imidazolidine-2,4-dione:

-Benzylideneindanone type compounds such as those disclosed in application JP04134043, for example 2- (4-methoxybenzylidene) indan-1-one:

-Benzylidenetetralone type compounds such as those disclosed in application JP04134043, for example 2- (4-methoxybenzylidene) -3,4-dihydro-2H-naphthalen-1-one:

-Benzylidenefuranone type compounds such as those disclosed in application EP0390683, for example 4- (4-methoxybenzylidene) -2,2,5,5-tetramethyldihydrofuran-3-one:

-Benzylidenebenzofuranone type compounds such as those disclosed in application JP04134041, such as 2-benzylidenebenzofuran-3-one:

-Benzylideneindanedione type compounds, for example 2- (3,5-di (tert-butyl) -4-hydroxybenzylidene) indane-1,3-dione:

-Benzylidenebenzothiofuranone type compounds such as those disclosed in application JP04134043, for example 2-benzylidenebenzo [b] thiophen-3-one:

-Compounds of the benzylidene barbitur type, such as 5- (4-methoxybenzylidene) -1,3-dimethylpyrimidine-2,4,6-trione:

-Benzylidenepyrazolone type compounds such as 4- (4-methoxybenzylidene) -5-methyl-2-phenyl-2,4-dihydropyrazol-3-one:

-Benzylideneimidazolone type compounds, for example 5- (4-methoxybenzylidene) -2-phenyl-3,5-dihydroimidazol-4-one:

-Chalcone type compounds, such as 1- (2-hydroxy-4-methoxyphenyl) -3-phenylpropenone:

-Benzylidenone compounds disclosed in document FR2506156, for example 3-hydroxy-1- (2-hydroxy-4-methoxyphenyl) -3-phenylpropenone:

Examples of compounds of formula (10) that are insoluble at n ′ = 2, are insoluble, block UV radiation and have an average particle size of 10 nm to 5 μm include the following families:

-Phenylenebis (methylidenenorcamph) type compounds disclosed in document EP0693471, for example 1,4-phenylenebis {3-methylidenebicyclo [2.2.1] heptan-2-one}:

-Phenylenebis (methylidene camphor) type compounds disclosed in document FR2528420, for example 1,4-phenylenebis {3-methylidene-1,7,7-trimethylbicyclo [2.2.1] heptan-2-one} :

Or 1,3-phenylenebis {3-methylidene-1,7,7-trimethylbicyclo [2.2.1] heptan-2-one}:

-Phenylene bis (methylidene camphorsulfonamide) type compounds such as those disclosed in the document FR2529887, such as 1,4-phenylene bis {3,3'-methylidene camphor-10,10'-ethylsulfonamide or -(2-Ethylhexyl) sulfonamide}:

-Phenylenebis (methylidene cineol) type compounds described in E. Mariani et al., 16th IFSCC Congress, New York (1990), such as 1,4-phenylenebis {5-methylidene-3,3- Dimethyl-2-oxa-bicyclo [2.2.2] octane-6-one}:

-Phenylenebis (methylideneketotricyclodecane) type compounds disclosed in application EP0694521, for example 1,4-phenylenebis (octahydro-4,7-methano-6-inden-5-one):

-Phenylenebis (alkylene ketone) type compounds such as those disclosed in application JP04134041, such as 1,4-phenylenebis (4,4-dimethylpent-1-en-3-one):

-Phenylenebis (methylidenefuranone) type compounds disclosed in application FR2638354, for example 1,4-phenylenebis (4-methylidene-2,2,5,5-tetramethyldihydrofuran-3-one):

-Phenylenebis (methylidenequinuclidinone) type compounds such as those disclosed in application EP0714880, such as 1,4-phenylenebis {2-methylidene-1-azabicyclo [2.2.2] octane-3-one} :

Examples of compounds of formula (11) include the following families:
-Bis (benzylidene) cycloalkanone type compounds, for example 2,5-di (benzylidene) cyclopentanone:

-Gamma-pyrone type compounds disclosed in document JP04290882, for example 2,6-bis (3,4-dimethoxyphenyl) pyran-4-one:

  Of these aryl vinylene ketone type insoluble organic compounds that block UV radiation, compounds of formula (10) where n ′ = 2 are even more preferred.

  Among the phenylenebis (benzoxazinone) type solid organic shielding agents, those corresponding to the following formula (12) can be mentioned:

[In the formula, R representing a divalent aromatic residue selected from the following formulas (e ″) to (h ″) is included].

[Where:
Each R ₉ symbols, independently, OH group, a halogen atom, optionally linear or branched C _{1 to 6} alkyl groups containing a silicon atom and linear or branched C ₁ containing a silicon atom by _{Represents a -6} alkoxy group, a linear or branched _C1-5 alkoxycarbonyl group, or a linear or branched _C1-6 alkylsulfonamide group optionally containing a silicon atom or an amino acid functional group,
p '' represents an integer of 0 to 4 including both ends,
q ″ represents 0 or 1.]

Examples of compounds of formula (12) that are insoluble, shield from UV radiation and have an average particle size of 10 nm to 5 μm include the following derivatives:
-2,2'-p-phenylenebis (3,1-benzoxazin-4-one) (commercial product Cyasorb UV-3638 from Cytec),
-2,2 '-(4,4'-biphenylene) bis (3,1-benzoxazin-4-one),
-2,2 '-(2,6-naphthylene) bis (3,1-benzoxazin-4-one).

  Among the acrylonitrile amide, sulfonamide or carbamate derivative type solid organic screening agents, mention may be made of those corresponding to the following formula (13):

[Where:
R ₁₀ represents a linear or branched C _1-8 alkyl group,
n '''has a value of 0, 1 or 2;
X ₂ has the formula _{- (C = O) -R 11} - (C = O) -, - SO 2 -R 11 -SO 2 - or _{- (C = O) -OR 11} -O- (C = O) -Represents a divalent group,
Y represents an a- (C═O) —R ₁₂ group or —SO ₂ R ₁₃ group,
R ₁₁ can carry a single bond or one or more hydroxyl substituents, and contains one or more heteroatoms selected from an oxygen atom, a nitrogen atom and a silicon atom in the carbon-based chain. may represents a linear or branched divalent C ₁ -C ₃₀ alkylene or C ₃ -C ₃₀ alkenylene group,
R ₁₂ represents -OR ₁₄ group or -NHR ₁₄ group,
R ₁₃ represents a linear or branched C _{1 to} C ₃₀ alkyl group or a phenyl ring which is unsubstituted or substituted with a C _{1 to} C ₄ alkyl group or an alkoxy group,
R ₁₄ can carry one or more hydroxyl substituents and can contain one or more heteroatoms selected from oxygen, nitrogen and silicon atoms in the carbon-based chain. represents a linear or branched C ₁ -C ₃₀ alkyl or C ₃ -C ₃₀ alkenylene group.

  Only the isomer in which the cyano substituent is cis to the para-aminophenyl substituent is represented by formula (13) above, but it should be understood that this formula also includes the corresponding trans isomer. For each of the two double bonds, independently, the cyano and para-aminophenyl substituents can be in cis or trans configuration relative to each other.

  For example, a dimer of 2-ethylhexyl 2-cyano-3- [4- (acetylamino) phenyl] acrylate having the formula:

Another specific family of solid organic screening agents according to the present invention includes polyvalent metal salts of sulfonic acid or carboxylic acid organic screening agents (e.g. Ca ²⁺ , Zn ²⁺ , Mg ²⁺ , Ba ²⁺ , Al ³⁺ Or Zr ⁴⁺ ), for example polyvalent metal salts of sulfonated derivatives of benzylidene camphor, such as those disclosed in application FR-A 2 639 347; polyvalent metal salts of sulfonated derivatives of benzimidazole, such as application EP- Disclosed in A-893 119; or polyvalent metal salts of cinnamic acid derivatives, such as those disclosed in application JP-87 166 517.

  Mention may also be made of metal or ammonium or substituted ammonium complexes of UV-A and / or UV-B organic screening agents disclosed in patent applications WO93 / 10753, WO93 / 11095 and WO95 / 05150.

  A preferred class of particulate solid sulfonated benzimidazole UV absorbers are those having the formula

  [Wherein M is hydrogen or an alkali metal, preferably sodium, an alkaline earth metal such as magnesium, calcium or zinc].

In the compounds of formula (1) ~ (35), C 1 ~C 18 alkyl groups are methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, tert- butyl, n- amyl, n- hexyl, n - heptyl, n- octyl, isooctyl, n- nonyl, n- decyl, n- undecyl, n- dodecyl and tetradecyl, Hekishideshiru, or octadecyl well as C ₁ -C ₁₈ alkoxy groups, methoxy, ethoxy, propoxy, It may be butoxy, n-hexoxy, n-heptoxy, n-octoxy, isooctoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dodecoxy, tetradecoxy, hexadecoxy, or octadecoxy, with methoxy and ethoxy being preferred.

The C ₁ -C ₁₈ carboxyalkyl, carboxymethyl, carboxyethyl, carboxypropyl, carboxy isopropyl, carboxybutyl, carboxyalkyl isobutyl, carboxy amyl, carboxymethyl hexyl, carboxymethyl heptyl, carboxymethyl octyl, carboxymethyl isooctyl, Karubokishinoniru, carboxydecyl, Examples include carboxyundecyl, carboxydodecyl, carboxytetradecyl, carboxyhexadecyl, and carboxyoctadecyl, with carboxymethyl being preferred.

The C ₅ -C ₈ cycloalkyl, cyclopentyl, cyclohexyl, and cyclooctyl.

  The particulate solid organic UV filter may be selected from the group consisting of benzotriazole derivatives, oxanilide derivatives, triazine derivatives, triazole derivatives, vinyl group-containing amides, cinnamic acid amides, and sulfonated benzimidazoles.

  It is also preferred that the particulate solid organic UV filter is selected from solid forms of methylene bis (hydroxyphenylbenzotriazole) derivatives.

  Methylenebis-benzotriazolyltetramethylbutylphenol, for example 2,2′-methylenebis [6- (2H-benzotriazol-2-yl] sold in solid form under the trademark “Mixxim BB / 200” by Fairmount Chemical Company ) -4-methyl-phenol], or the trademark “Tinosorb M” by BASF or “Mixxim BB / 100” by Fairmount Chemical in the form of a finely divided powder in aqueous dispersion. 2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], and US Pat. Nos. 5,237,071, 5,166,355, GB-2,303,549 Derivatives described in DE-197, 26, 184 and EP-893, 119 are particularly preferred.

  The particulate solid organic UV filter has a mass ratio of small core particles to the particulate solid organic UV filter in the composite pigment according to the present invention of 10:90 to 90:10, preferably 30:70 to 80:20, more preferably. May be used in a ratio of 40:60 to 50:50.

(Solid inorganic UV filter)
As described above, the coating layer on the small core particles may include at least one solid inorganic UV filter. When two or more kinds of solid inorganic UV filters are used, they may be the same or different and are preferably the same.

  The solid inorganic UV filter used in the present invention may be active in the UV-A and / or UV-B region, preferably in the UV-B region, or in the UV-A and UV-B region. The active UV filter regions of the solid inorganic UV filter and the particulate solid organic UV filter are preferably complementary to each other in order to achieve comprehensive UV protection. For example, it is preferred that the solid inorganic UV filter is active in at least the UV-B region and the particulate solid organic UV filter is active in at least the UV-A region. The solid inorganic UV filter may be hydrophilic and / or lipophilic. Solid inorganic UV filters are completely insoluble in solvents commonly used in cosmetics, such as water and ethanol. The term “solid” means a solid at 1 atmosphere 25 ° C.

  The solid inorganic UV filter is preferably in the form of fine particles whose average (primary) particle diameter ranges from 1 nm to 50 nm, preferably from 5 nm to 40 nm, more preferably from 10 nm to 30 nm. The average (primary) particle size or average (primary) particle diameter herein is the arithmetic average diameter.

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

  Solid inorganic UV filters are pigments formed with metal oxides (average primary particle size: generally 5 nm to 50 nm, preferably 10 nm to 50 nm), e.g. oxidation, which is a UV photoprotectant that is all well known per se. It is preferably selected from pigments formed from titanium (amorphous or rutile and / or anatase crystalline), iron oxide, zinc oxide, zirconium oxide or cerium oxide. Preferably, the solid inorganic UV filter is selected from titanium oxide, zinc oxide, more preferably titanium oxide.

  The solid inorganic UV filter may be coated or uncoated. The solid inorganic UV filter may have at least one coating layer. The coating layer is made of alumina, silica, aluminum hydroxide, silicone, silane, fatty acid or salt thereof (sodium salt, potassium salt, zinc salt, iron salt, aluminum salt, etc.), fatty alcohol, lecithin, amino acid, polysaccharide, protein, alkanol It may contain at least one compound selected from the group consisting of amines, waxes such as beeswax, (meth) acrylic polymers, organic UV filters, and (per) fluoro compounds.

  The coating layer preferably contains at least one organic UV filter. Organic UV filters in the coating layer include dibenzoylmethane derivatives such as butylmethoxydibenzoylmethane (abovobenzone) and 2,2'-methylenebis [6- (2H-benzotriazole) commercially available as "TINOSORB M" from BASF -2-yl) -4- (1,1,3,3-tetramethyl-butyl) phenol] (methylenebis-benzotriazolyl tetramethylbutylphenol) may be preferred.

  As is known, the silicone in the coating layer may be an organosilicon polymer or oligomer containing a linear or cyclic, branched or cross-linked structure that may vary in molecular weight, with appropriate functionality. Mainly obtained by polymerization and / or polycondensation of silane, wherein silicon atoms are bonded to each other by oxygen atoms (siloxane bonds), and in some cases, substituted hydrocarbon groups are directly bonded to the silicon atoms by carbon atoms. It consists essentially of repeating units.

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

  The silicone used in the coating layer may preferably be 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.

  Of course, solid inorganic UV filters composed of metal oxides may be treated with other surfacing agents, in particular cerium oxide, alumina, silica, aluminum compounds, silicon compounds, or before being treated with silicone. And may be treated with a mixture thereof.

  A coated solid inorganic UV filter can be obtained by combining this solid inorganic UV filter with any of the compounds described above as well as polyethylene, metal alkoxides (titanium alkoxides or aluminum alkoxides), metal oxides, sodium hexametaphosphate, and for example, Cosmetics & Toiletries, 1990. Prepared by subjecting to surface treatment of one or more chemical, electronic, mechanochemical and / or mechanical properties, along with those shown in February, 105, 53-64 Also good.

The coated solid inorganic UV filter
Titanium oxide coated with silica, such as “Sunveil” from Ikeda Bussan Co., Ltd.
Titanium oxide coated with silica and iron oxide, such as “Sunveil F” from Ikeda Bussan Co., Ltd .;
Titanium oxide coated with silica and alumina, such as the product "Microtitanium Dioxide MT 500 SA" from Teika Corporation, the product "Tioveil" from Tioxide, and the product "Mirasun TiW 60" from Rhodia;
Titanium oxide coated with alumina, such as Ishihara Sangyo Co., Ltd.'s products "Tipaque TTO-55 (B)" and "Tipaque TTO-55 (A)" and Kemira's product "UVT 14/4";
Takeka's products "Microtitanium Dioxide MT 100 T, MT 100 TX, MT 100 Z or MT-01", Uniqema's "Solaveil CT-10 W" and "Solaveil CT 100", and Merck's "Eusolex" Titanium oxide coated with alumina or aluminum stearate, such as T-AVO;
Titanium oxide coated with alumina or aluminum laurate, such as the product "Microtitanium Dioxide MT 100 S" from Teika Corporation;
Titanium oxide coated with iron oxide or iron stearate, such as the product "Microtitanium Dioxide MT 100 F" from Teika Corporation;
Titanium oxide coated with zinc oxide or zinc stearate, such as Takeka's product "BR351";
Titanium products such as "Microtitanium Dioxide MT 600 SAS", "Microtitanium Dioxide MT 500 SAS", and "Microtitanium Dioxide MT 100 SAS", etc., titanium oxide coated with silica and alumina and treated with silicone;
Titanium oxide coated with silica, alumina and aluminum stearate and treated with silicone, such as product "STT-30-DS" of Titanium Industry Co., Ltd .;
Titanium oxide coated with silica and treated with silicone, such as Kemira's product UV-Titan X 195;
Titanium oxide coated with alumina and treated with silicone, such as "Tipaque TTO-55 (S)" from Ishihara Sangyo Co., Ltd. or "UV Titan M 262" from Kemira;
Titanium oxide coated with triethanolamine, such as the product "STT-65-S" from Titanium Industry Co., Ltd .;
Ishihara Sangyo Co., Ltd. product “Tipaque TTO-55 (C)” etc., titanium oxide coated with stearic acid, or Teika Co., Ltd. product “Microtitanium Dioxide MT 150 W” etc. are coated with sodium hexametaphosphate. Titanium oxide may also be used.

Other titanium oxide pigments treated with silicone are treated with octyltrimethylsilane, TiO ₂ whose individual particles have an average particle size of 25-40 nm, for example marketed under the trademark “T 805” by Degussa Silices TiO ₂ treated with polydimethylsiloxane and whose individual particles have an average particle size of 21 nm, such as those sold under the trademark “70250 Cardre UF TiO ₂ Si ₃ ” by Cardre, Anatase / rutile TiO ₂ treated with polydimethylhydrosiloxane and having an average particle size of 25 nm, such as those marketed under the trademark “Microtitanium Dioxide USP Grade Hydrophobic” by Color Techniques Is preferred.

Preferably, the following coated TiO ₂ may be used as a coated inorganic UV filter:
An average primary particle diameter of 15 nm, stearic acid (and) aluminum hydroxide (and) TiO ₂ , such as a product “MT-100 TV” of Teika Co., Ltd.
Dimethicone (and) stearic acid (and) aluminum hydroxide (and) TiO ₂ such as Miyoshi Kasei's product `` SA-TTO-S4 '' with an average primary particle diameter of 15 nm,
Silica (and) TiO <sub>2</sub> such as the product `` MT-100 WP '' of Teika Co., Ltd. with an average primary particle diameter of 15 nm,
Dimethicone (and) silica (and) aluminum hydroxide (and) TiO ₂ , such as products `` MT-Y02 '' and `` MT-Y-110 M3S '' of Teika Co., Ltd. having an average primary particle diameter of 10 nm
Dimethicone (and) aluminum hydroxide (and) TiO ₂ such as Miyoshi Kasei's product `` SA-TTO-S3 '' with an average primary particle diameter of 15 nm,
Dimethicone (and) alumina (and) TiO ₂ such as Sachtleben's product "UV TITAN M170" with an average primary particle diameter of 15 nm, and Teka's product "MT-100 AQ" with an average primary particle diameter of 15 nm Such as silica (and) aluminum hydroxide (and) alginic acid (and) TiO ₂ .

From the viewpoint of UV filter capability, TiO ₂ coated with at least one organic UV filter is more preferable. For example, avobenzone (and) stearic acid (and) aluminum hydroxide (and) TiO ₂ such as a product “HXMT-100ZA” manufactured by Teika Co., Ltd. having an average primary particle diameter of 15 nm may be used.

  The uncoated titanium oxide pigment is, for example, a trademark of “Microtitanium Dioxide MT500B” or “Microtitanium Dioxide MT600B” by Teika Corporation, a trademark of “P 25” by Degussa, and “Oxyde de titane transparent PW” by Wacker. It is marketed under the trademark "UFTR" by Miyoshi Kasei Co., Ltd., "ITS" by Tomen, and "Tioveil AQ" 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, and
It is marketed under the trademark “Nanogard WCD 2025” by Nanophase Technologies.

The coated zinc oxide pigment is, for example,
What is marketed under the trademark "Oxide Zinc CS-5" by Toshiba Corporation (ZnO coated with polymethylhydrosiloxane),
The Nanophase Technologies Corporation (as C ₁₂ ~C ₁₅ Finsolv 40% dispersion in TN benzoic acid alkyl) "Nanogard Zinc Oxide FN" trademark those commercially available,
Those marketed by Daito Kasei Kogyo Co., Ltd. under the trademarks `` Daitopersion Zn-30 '' and `` Daitopersion Zn-50 '' (containing 30% or 50% zinc nanooxide coated with silica and polymethylhydrosiloxane, (Ethyleneated polydimethylsiloxane / cyclopolymethylsiloxane dispersion)
Those marketed under the trademark "NFD Ultrafine ZnO" by Daikin Industries, Ltd. (ZnO coated with a perfluoroalkyl phosphate ester and a copolymer based on perfluoroalkylethyl as a cyclopentasiloxane dispersion),
What is marketed 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 (alumina-treated ZnO dispersed in ethylhexyl methoxycinnamate / PVP-hexadecene copolymer / methicone mixture), and Fuji ZnO-SMS- 10 "(ZnO coated with silica and polymethylsilsesquioxane), marketed by Elementis under the" Nanox Gel TN "trademark (hydroxystearic acid polycondensate) C ₁₂ -C ₁₅ ZnO dispersed at 55% in alkyl benzoate containing)
It is.

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

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

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

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

  The coated solid inorganic UV filter is preferable because it can enhance the UV filter effect of the solid inorganic UV filter. In addition, the coating layer can function as a binder to fix the UV filter on the small core particles.

  When a solid inorganic UV filter in the form of fine particles is used, the composite pigment according to the present invention has an effect of giving a transparent or clear appearance instead of a white appearance because the fine particles of the solid inorganic UV filter do not aggregate and spread on the core particles. Have. It should be noted that the solid particulates of the solid inorganic UV filter aggregate easily and give the skin a white appearance.

  The solid inorganic UV filter has a mass ratio of small core particles to the solid inorganic UV filter in the composite pigment according to the present invention of 10:90 to 90:10, preferably 30:70 to 70:30, more preferably 40:60. May be used in a ratio of ~ 50: 50.

(Color pigment)
As described above, the coating layer on the small core particles may include at least one color pigment.

  The term “color pigment” should be understood to mean any shape of white or colored inorganic or organic particles that are insoluble and that color the compositions containing them.

  When the color pigment is used, the composite pigment according to the present invention is effective in that the color pigment does not agglomerate and spreads on the base material, thereby providing a clearer appearance with high saturation. It should be noted that free colored pigments easily aggregate and give the skin a dull appearance with low saturation. Therefore, the color of cosmetics containing colored pigments can be opaque and dark. On the other hand, the composite pigment according to the present invention can give a clear and bright color tone.

  The pigment may be white or colored, inorganic and / or organic, and generally has an average particle size of 1 μm or more.

  Among the inorganic pigments that can be used, but not limited to, titanium dioxide, zirconium oxide or cerium oxide, and optionally zinc oxide, (black, yellow, or red) iron oxide or chromium oxide, manganese Mention may be made of purple, ultramarine blue, chromium hydroxide hydrate, and ferric blue, barium sulfate, or metal powder such as aluminum powder, copper powder, silver powder or gold powder.

  The particle size of the color pigment is not limited. In certain embodiments, the colored pigment may have an average particle size of from 100 nm to less than 1 μm, preferably from 100 nm to less than 500 nm, more preferably from 100 nm to less than 300 nm.

  Since the colored pigment particles can adhere firmly onto the small core particles, the colored pigment cannot penetrate into the skin from the pores on the skin. Furthermore, even if the color pigment is stimulated, it is only present on the small core particles, so a large amount of color pigment cannot be in direct contact with the skin. Therefore, the composite pigment according to the present invention is safer than the aggregate of colored pigments.

  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, silver powder, It is preferably selected from gold powder, barium sulfate, carbon black, D & C type pigments, lakes, pearlescent pigments, and mixtures thereof.

  The term “pearlescent pigment” should be understood to mean any iridescent particles of any shape, such as particles produced or otherwise synthesized by a certain shellfish.

  Pearlescent agent is a white pearlescent agent such as mica covered with titanium dioxide or bismuth oxychloride; mica covered with titanium oxide covered with iron oxide, coated with titanium oxide Colored pearlescent agents such as mica covered with ferric blue or chromium oxide, or mica coated with titanium oxide covered with organic pigments of the type described above; and based on bismuth oxychloride It can be selected from pearlescent agents.

  The composite pigment according to the present invention can firmly fix the color pigment fine particles (when used) on the small core particles, and thus has a high coefficient of friction that does not easily spread on the skin, and has an unpleasant feeling of use. Since it is possible to reduce the amount of fine particles provided, a better feeling of use can be provided.

  In the composite pigment according to the present invention, the color pigment has a mass ratio of small core particles to the color pigment of 50:50 to 90:10, preferably 50:50 to 80:20, more preferably 50:50 to 70:30. May be used at a ratio of

(Additional UV filter)
As described above, the coating layer on the small core particles may further include at least one additional UV filter. When two or more additional UV filters are used, they may be the same or different and are preferably the same.

  Additional UV filters used in the present invention may be active in the UV-A and / or UV-B region, preferably in the UV-A region, or in the UV-A and UV-B regions. The additional UV filter may be hydrophilic and / or lipophilic.

  The additional UV filter may be solid or liquid, preferably liquid. The terms “solid” and “liquid” mean a solid and a liquid at 25 ° C. under 1 atmosphere, respectively. The additional UV filter may be made of at least one organic or inorganic material, preferably at least one organic material.

  Additional UV filters 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 derivatives thereof, benzoxazole derivatives, blocking polymers and blocking silicones, dimers derived from α-alkylstyrenes, 4,4-diarylbutadienes, octocrylene and the like Derivatives, guaiazulene and its derivatives, rutin and its derivatives, flavonoids, biflavonoids, oryzanol and its derivatives, quinic acid and its derivatives, phenol, retinol, cysteine, Aromatic amino acids, aromatic amino acid residues containing peptide, as well, may be selected from the group consisting of mixtures.

  Examples of additional organic UV filters include those indicated below by their INCI names 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-La Roche; and isopropyldibenzoylmethane.

  Cinnamic acid derivatives: ethyl hexyl methoxycinnamate; isopropyl methoxycinnamate; isopropoxy methoxycinnamate; sold in particular by Hoffmann-La Roche under the trademark “Parsol MCX”; “Neo Heliopan E 1000 by Haarmann and Reimer "Isoamyl methoxycinnamate, commercially available under the trademark"; synoxate (2-ethoxyethyl-4-methoxycinnamate); DEA methoxycinnamate; diisopropyl methylcinnamate; and glyceryl ethyl hexacinnamate dimethoxycinnamate.

  Salicylic acid derivatives: homosalate marketed under the trademark “Eusolex HMS” by Rona / EM Industries; homohexyl salicylate; ethylhexyl salicylate marketed under the trademark “Neo Heliopan OS” by Haarmann and Reimer; glycol salicylate; butyloctyl salicylate Phenyl salicylate; dipropylene glycol salicylate marketed under the trademark “Dipsal” by Scher; and TEA salicylic acid 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 sold under the trademark "Eusolex 6300" by Merck; "Mexoryl SL Benzylidene camphorsulphonic acid manufactured under the trademark ''; camphorbenzalkonium methosulfate manufactured under the trademark `` Mexoryl SO '' by Chimex; terephthalidene disulfide 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 derivative: diethylhexylbutamide triazone marketed by Sigma 3V under the trademark “Uvasorb HEB”; 2,4,6-tris (dineopentyl 4′-aminobenzalmalonate) -s-triazine.

  Benzotriazole derivatives, especially phenylbenzotriazole derivatives: branched and straight chain 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylpheno, and those described in USP 5240975.

  Benzalmalonate derivatives: 4'-methoxybenzalmalonate dineopentyl, and polyorganosiloxanes containing benzalmalonic acid functionality, 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.

  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.

  Blocking polymer and blocking silicone: Silicone described in WO93 / 04665.

  Dimer derived from α-alkylstyrene: a dimer described in DE-19855649.

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

  Guaiazulene and its derivatives: Guaiazulene and sodium guaiazulene sulfonate.

  Rutin and its derivatives: rutin and glucosyl rutin.

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

  Biflavonoids: lanceolatin A, lanceolatin 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: Peptide having tryptophan, tyrosine or phenylalanine.

Preferred additional organic UV filters are selected from:
Butylmethoxydibenzoylmethane, ethylhexyl methoxycinnamate, homosalate, ethylhexyl salicylate, octocrylene, phenylbenzimidazolesulfonic acid, benzophenone-3, benzophenone-4, benzophenone-5, n-hexyl 2- (4-diethylamino-2-hydroxy Benzoyl) benzoate, 4-methylbenzylidene camphor, terephthalylidene dican full 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, methylenebis- Benzotriazolyltetramethylbutylphenol, 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. A more preferred liquid organic UV filter is butylmethoxydibenzoylmethane (Avobenzone).

  In a preferred embodiment, the additional UV filter is a liquid organic UV filter.

  The material of the liquid organic UV filter is not limited as long as it is organic. When two or more kinds of liquid organic UV filters are used, the materials of the liquid organic UV filters may be the same as or different from each other.

Among the additional liquid organic UV filters, we can mention:
-Cinnamic acid derivatives: ethyl hexyl methoxycinnamate; isopropyl methoxycinnamate; isopropoxy methoxycinnamate; marketed under the trademark `` Parsol MCX '' by Hoffmann-La Roche in particular; Isoamyl methoxycinnamate commercially available under the trademark Heliopan E 1000; Synoxate (2-ethoxyethyl 4-methoxycinnamate); DEA methoxycinnamate; Diisopropyl methylcinnamate; and Ethylhexane dimethoxycinnamate Glyceryl acid.
-Salicylic acid derivatives: homosalate marketed under the trademark `` Eusolex HMS '' by Rona / EM Industries; homohexyl salicylate; ethyl hexyl salicylate marketed under the trademark `` Neo Heliopan OS '' by Haarmann and Reimer; glycol salicylate; Butyloctyl salicylate; phenyl salicylate; dipropylene glycol salicylate sold under the trademark “Dipsal” by Scher; and TEA salicylic acid marketed under the trademark “Neo Heliopan TS” by Haarmann and Reimer.
β, β-diphenyl acrylate derivatives: Octocrylene sold in particular under the trademark “Uvinul N539” by the company BASF; and etocrylene specifically marketed under the trademark “Uvinul N35” by the company BASF.
A polyorganosiloxane containing benzalmalonate functional groups, for example Polysilicone-15 marketed under the trademark “Parsol SLX” by the company Hoffmann-LaRoche.

Preferred additional liquid organic UV filters are
It may be selected from ethylhexyl methoxycinnamate, homosalate, ethylhexyl salicylate, octocrylene, polysilicone-15.

  The additional UV filter in the composite pigment according to the invention has a mass ratio of small core particles to the additional UV filter of 50:50 to 90:10, preferably 50:50 to 80:20, more preferably 50:50. May be used at a ratio of ~ 70: 30.

(Large core particles)
The large core particles to be used in the composite pigment according to the present invention, as long as the large core particles have an average particle diameter or average particle diameter of 2 μm or more, preferably 3 μm or more, more preferably 4 μm or more, and even more preferably 5 μm or more. , Not limited. The average particle size of the large core particles may be limited to 50 μm or less, preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 10 μm or less.

  In the present specification, the average particle diameter or the average particle diameter is an arithmetic average diameter, and can be obtained, for example, by calculating an average size of 100 particles selected on an image obtained by a scanning electron microscope. .

  The large core particles may be hollow or solid. In some cases, it is preferable to use solid large particles.

  The large particles may have any shape. For example, it is possible to use large particles in the form of plates having an aspect ratio of at least 5, preferably greater than 10, more preferably greater than 20, 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.

  When plate-like particles are used in the present invention, the plate-like particles are 2 μm or more, preferably 3 μm or more, more preferably 4 μm or more, even more preferably 5 μm or more, 50 μm or less, preferably 30 μm or less, more preferably 20 μm. Hereinafter, it is even more preferable that the length is in the range of 10 μm or less.

  In a preferred embodiment, the large core particles have a spherical shape.

  The material of the large core particles is not limited. The material may be at least one inorganic material and / or at least one organic material, preferably at least one organic material.

The inorganic material and / or the organic material may be hollow or porous. The porosity of the material, by the BET ^{method, 0.05m 2 / g~1,500m 2 / g} , more preferably 0.1m ² / g~1,000m ² / g, more preferably 0.2m ² / g~500m ² / g Specific surface area.

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

  In particular, silica particles such as P-1500 marketed by JGC C & C are preferred as the inorganic large particles.

  Preferably, the organic material is poly (meth) acrylate, polyamide, silicone, polyurethane, polyethylene, polypropylene, polystyrene, copolystyrene, polyhydroxyalkanoate, polycaprolactam, poly (butylene) succinate, polysaccharide, polypeptide, polyvinyl alcohol, It may be selected from the group consisting of polyvinyl resins, 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. Polyamides such as Nylon (registered trademark), polyhydroxyalkanoates such as polylactic acid, poly (meth) acrylates such as polymethyl methacrylate, silicones, fluoropolymers, and mixtures thereof are more preferred.

  In particular, polymethyl methacrylate particles such as MR-7GC marketed by Soken Chemical Co., Ltd. (Japan), polyamide particles such as SP-500 marketed by Toray Industries, Inc., Orgasol marketed by Arkema, and PTFE particles such as Ceridust 9205F marketed by Clariant are preferred as organic large core particles.

  The large core particles may be pre-coated or uncoated. In certain embodiments, the large core particles are coated from the beginning. The material of the original coating layer of the large core particles is not limited, but organic materials such as amino acids, N-acylamino acids, amides, silicones, modified silicones and polyolefins are preferable. Examples of the organic material include lauroyl lysine, acrylic-modified silicone, and polyethylene.

  In particular, silica particles coated with polyethylene such as ACEMATT OK412 marketed by Degussa may be preferred as coated (inorganic) large particles.

  In the composite pigment according to the present invention, the mass ratio of the small core particles to the large core particles may be 10:90 to 90:10, preferably 20:80 to 80:20, more preferably 30:70 to 70:30. .

  In certain embodiments, the mass ratio of small core particles / large core particles / particulate solid organic UV filter is 20:50:30 to 50:20:30, preferably 35:15:50 to 15:35:50. More preferably, it may be 10:20:70 to 20:10:70.

  In a preferred embodiment, the mass ratio of small core particles / large core particles / particulate solid organic UV filter may be 50:20:30 or 35:15:50.

In a preferred embodiment, the composite pigment according to the invention can meet the following requirements:
The small core particles comprise at least one copolystyrene, preferably a styrene / acrylate copolymer, and / or a crosslinked styrene / methyl methacrylate copolymer,
The large particles comprise at least one poly (meth) acrylate, preferably methyl methacrylate polymer,
The small core particles and the large core particles comprise at least one coating layer comprising a benzotriazole UV filter, preferably at least one particulate solid organic UV filter selected from methylene bis (hydroxyphenylbenzotriazole) derivatives having the structure Is at least partially covered by:

Wherein, T ₂ are independently, C ₁ -C ₄ alkyl group, C ₅ -C ₁₂ cycloalkyl group, or one or more of which may be substituted by a group C ₁ is selected from aryl residue To _C18 alkyl group, more preferably selected from the group consisting of:

(Preparation method of composite pigment)
The composite pigment according to the present invention is
At least one small core particle having an average particle size greater than 100 nm and less than 1 μm, preferably less than 600 nm, more preferably less than 400 nm, and containing at least one organic polymer;
Optionally, at least one large core particle having an average particle size of 2 μm or more, preferably 3 μm or more, more preferably 4 μm or more, and even more preferably 5 μm or more,
At least one particulate solid organic UV filter;
Optionally, it can be prepared by subjecting at least one selected from the group consisting of solid inorganic UV filters, colored pigments and additional UV filters to a mechanochemical fusion process.

  The small core particles, the large core particles, the particulate solid organic UV filter, the solid inorganic UV filter, the color pigment, and the additional UV filter are as described above.

  A mechanochemical fusion process refers to a process in which a large number of objects are subjected to mechanical force such as impact force, friction force or shear force to cause fusion between the objects.

  The mechanochemical fusion process can be performed by an apparatus including a rotating chamber and a fixed internal part having a scraper, such as, for example, a mechanofusion system marketed by Hosokawa Micron Corporation of Japan.

  It is preferable to use a hybridizer process as the mechanochemical fusion process.

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

  According to the hybridizer process, the mechanical force is imparted 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. Thus, the hybridizer process can be defined as a mechanochemical fusion process using such a high speed rotor. The hybridizer process 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 a hybridizer process with solid materials. The term “hybridizer process” is used as a technical term.

  The hybridizer process can be carried out, for example, by using 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, Supply to a hybridizer with a high speed rotor with multiple blades in a chamber under dry conditions, disperse the particles in the chamber, and apply mechanical and thermal energy (e.g., compression, friction, and shear stress) to the particles For 1 to 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 form an “ordered mixture” in which one type of particle spreads and covers the other type of particle. The hybridizer process can also be carried out by using a theta composer marketed by Tokuju Corporation in Japan.

  The hybridizer process can also be carried out by using a composite hybrid or mechano hybrid marketed by Nippon Coke Kogyo Co., Ltd.

  According to an embodiment of the invention, for example, small core particles, large core particles, particulate solid organic UV filters, and optionally solid inorganic UV filters, colored pigments and / or additional UV filters. Additional materials such as can be fed into such a hybridizer to produce a composite pigment. The hybridizer method can be carried out using a rotor rotating at about 8,000 rpm (100 m / sec) for about 3 minutes.

  According to an embodiment of the present invention, the small core particles and the large core particles have a mass ratio of the small core particles to the large core particles of 10:90 to 90:10, preferably 20:80 to 80:20, more preferably. May be used in a ratio of 30:70 to 70:30.

  In certain embodiments, the mass ratio of small core particles / large core particles / particulate solid organic UV filter is 20:50:30 to 50:20:30, preferably 35:15:50 to 15:35:50. More preferably, it may be 10:20:70 to 20:10:70.

  In a preferred embodiment, the mass ratio of small core particles / large core particles / particulate solid organic UV filter may be 50:20:30 or 35:15:50.

  A mechanochemical fusion process, in particular a hybridizer method, wherein the small core particles comprise at least one particulate solid organic UV filter, and optionally at least one solid inorganic UV filter and / or at least one colored pigment and / or Alternatively, composite pigments can be produced that are at least partially covered by at least one layer comprising at least one additional UV filter, wherein the small core particles comprise at least one organic polymer. When large core particles are used, the surface of the large core particles also includes at least one comprising at least one selected from the group consisting of a particulate solid organic UV filter, a solid inorganic UV filter, a color pigment and an additional UV filter. It may be at least partially covered by one layer.

  In addition, the mechanochemical fusion process, in particular the hybridizer method, comprises a particulate solid organic UV filter, and optionally at least one solid inorganic UV filter and / or at least one colored pigment and / or on small core particles. Can provide a regular array of at least one additional UV filter (e.g., uniform coating), provides a strong bond to the surface of small core particles, particulate solid organic UV filters, and optionally solid inorganic UV filters And / or a coating layer comprising colored pigments and / or additional UV filters.

  When large core particles are used in combination with small core particles according to the present invention, the particulate solid organic UV filter, as well as possibly solid inorganic, due to the anchor effect of collision of the large core particles with the small core particles UV filters and / or additional UV filters and / or colored pigments can be effectively bound on the surface of the small core particles. Therefore, the UV filter effect and, if necessary, the coloring effect can be further enhanced.

  It should be noted that the mechanochemical fusion process, particularly the hybridizer method, is quite different from other methods using, for example, bead mills or jet mills. In fact, the bead mill causes fine pulverization or agglomeration of the core particles, and the jet mill causes fine pulverization of the core particles, and the coating of the core particles with fine particles is difficult to be formed uniformly.

  If desired, an additional process of further coating the composite pigment with a UV filter and / or coloring material may be performed. As a result of this additional process, the composite pigment according to the invention may be coated with another layer comprising UV filters and / or colored materials, preferably consisting of UV filters and / or colored materials.

(Cosmetic composition)
In the cosmetic composition according to the present invention, the composite pigment as described above according to the present invention is 0.01% by mass to 99% by mass, preferably 0.1% by mass to 50% by mass, more preferably, relative to the total mass of the composition. It may be present in an amount ranging from 1% to 30% by weight.

  Preferably, the composite pigment according to the present invention can be used in a cosmetic composition applied to keratin materials such as skin, hair, nails and the like, and can provide a UV shielding effect and optionally a coloring effect, Composite pigments show a good UV shielding effect, which may be accompanied by a clear or clear appearance and / or a good coloring effect such as more transparent or clear and bright coloring, without the risk of affecting keratin materials Because you get. Furthermore, the composite pigment according to the present invention can be easily formulated into a cosmetic composition and stabilized in the cosmetic composition.

  Since the composite pigment according to the present invention has a high coefficient of friction, does not spread easily on the skin, and can reduce free particles that give an unpleasant feeling of use, the cosmetic composition according to the present invention reduces friction and therefore more Good usability effect can be realized.

  The cosmetic composition according to the present invention may comprise at least one filler and / or at least one 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 have any shape (e.g., sheet-like crystal, cubic crystal, hexagonal crystal, orthorhombic crystal, etc.) (e.g. platelet, spherical, And oval). 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 formed of hexamethylene diisocyanate and trimethylol hexyl lactone copolymer sold by Toyo Pigment Co. under the name Plastic Powder D-400; formed 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 powder, for example silsesquioxane powder [for example disclosed in EP 0293795 Silicone resin powder, and Toshiba Tospearls (registered trademark)]; poly (methyl methacrylate) particles; precipitated calcium carbonate; magnesium carbonate; basic magnesium carbonate; hydroxyapatite; hollow silica microspheres; glass microcapsules; ceramic micro Capsules; metal soaps derived from organic carboxylic acids containing 8 to 22 carbon atoms, such as 12 to 18 carbon atoms, such as zinc stearate, magnesium stearate, lithium stearate, zinc laurate, and magnesium myristate Barium sulfate; and mixtures thereof.

  The filler is present in the composition in an amount ranging from 0.1% to 80% by weight, for example 1% to 25% by weight, or 3% to 15% by weight relative to the total weight of the composition. Good.

  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 present invention include, for example, hydrocarbon oils of animal origin such as perhydrosqualene (or squalane); hydrocarbon oils of plant origin, such as caprylic / capric acid 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 or jojoba oil or 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; fluorine Chemical oils, for example, those partially hydrocarbons and / or silicones, for example, those described in JP-A-2-295912; ethers such as dicaprylyl ether (CTFA name); C ₁₂ -C ₁₅ fatty alcohols Esters such as benzoic acid esters (Finetex's Finsolv TN); benzoic acid arylalkyl derivatives such as 2-phenylethyl benzoate (ISP's X-Tend 226); N-lauroylsarcosine isopropyl (Eldew SL-205 from Ajinomoto Co., Inc.) Amidated oils, and the like, as well as mixtures thereof.

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

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

  The composition according to the present invention comprises, for example, hydrophilic or lipophilic gelling agents and / or thickeners, surfactants, antioxidants, fragrances, preservatives, neutralizing agents, sunscreen agents, vitamins, moisturizers. , Self-tanning compounds, wrinkle control active agents, relaxation agents, hydrophilic or lipophilic active agents, contamination and / or free radical scavengers, sequestering agents, film forming agents, dermo-decontracting active agents ), Skin soothing agents, agents that stimulate the synthesis of dermal or epidermal polymers and / or prevent their degradation, antiglycation agents, agents that remove irritation, desquamating agents ), Depigmenting agent, antipigmenting agent, pigmentation promoting agent, NO synthase inhibitor, fibroblast and / or keratinocyte proliferation and / or keratinocyte differentiation Stimulate And at least one conventional additional cosmetic component that can be selected from drugs that act on the microcirculation, drugs that affect cellular energy metabolism, healing agents, and mixtures thereof. May be included.

  Compositions according to the present invention may be in various forms, such as suspensions, dispersions, solutions, gels, oil-in-water (O / W), water-in-oil (W / O), and multiple (e.g., W / O / W, polyol / O / W, and O / W / O) emulsions, such as emulsions, creams, foams, sticks, vesicle dispersions such as ionic and / or nonionic lipid dispersions, biphasic and Can be multiphase lotions, sprays, powders, and pastes. 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 cosmetic composition according to the present invention may be in the form of a powdered composition such as an oily solid cosmetic composition or an anhydrous composition, or a liquid or solid composition.

  In particular, the powdery cosmetic composition according to the present invention, which includes the composite pigment according to the present invention, can realize a smooth feeling of use with reduced friction and high stability against physical impact. Can have sex.

  Furthermore, the powdery cosmetic composition according to the present invention comprises a composite pigment in a specific amount according to the present invention, so that it has good compatibility with the skin, a homogeneous appearance, skin color hiding, pores on the skin and Preferred cosmetic effects such as a matting effect that hides wrinkles, makes pores and wrinkles on the skin inconspicuous can be shown.

  On the other hand, the liquid cosmetic composition according to the present invention can exhibit visual optical effects such as a good matting effect and a haze effect by including the composite pigment in a specific amount according to the present invention.

  In any case, the powdered and liquid cosmetic composition according to the present invention is more in addition to reducing the risk of solid inorganic UV filters and optional colored pigment particulates penetrating into the skin through pores on the skin. Has a good UV filter effect, and optionally a better coloring effect.

  According to another embodiment, the cosmetic composition according to the present 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, Lipstick, lip balm, eye shadow, eyeliner, loose powder, concealer, nail coat, mascara, sunscreen, etc. can be used.

  According to another embodiment, the cosmetic composition according to the present invention may be in the form of a foam.

  According to this embodiment, the cosmetic composition according to the present invention can be packed in a foam dispenser. The composition is dispensed from the pressurized container by the propellant gas and thus from the container by a product called an “aerosol” that forms a foam at the moment of dispensing, or by a pump mechanism connected to the dispensing head. Any of the products to be dispensed, wherein the cosmetic composition is passed through the dispensing head, may be converted to foam at the outlet opening of the head at the latest.

  According to a first variant, the dispenser may be an aerosol further containing a cosmetic composition according to the invention and a propellant gas. For the purposes of the present invention, the term “propellant” is any compound that is gaseous at a temperature of 20 ° C. and atmospheric pressure and can be stored under pressure in a liquid or gaseous form in an aerosol container. Means. The propellant may be selected from optionally halogenated volatile hydrocarbons such as n-butane, propane, isobutane, pentane or halogenated hydrocarbons, and mixtures thereof. Carbon dioxide, nitrous oxide, dimethyl ether (DME), nitrogen or compressed air can also be used as a propellant. A mixture of propellants can also be used. Dimethyl ether and / or non-halogenated volatile hydrocarbons are preferably used.

  The propellant gases that can be used are, among others, carbon dioxide, nitrogen, nitrogen oxides, dimethyl ether, volatile hydrocarbons such as butane, isobutane, propane and pentane, and mixtures thereof. You can choose from.

  According to another variant, the cosmetic composition according to the invention may be a “pump bottle” type foam dispenser. These dispensers include a dispensing head for delivering the cosmetic composition, a pump, and a plunger tube for moving the cosmetic composition from the container into the head for the purpose of dispensing the product. The foam is formed by passing the cosmetic composition through a material comprising a porous material, such as a sintered material, a plastic or metal filter grid, or similar structure.

  Such dispensers are known to those skilled in the art and are described in the following patents: U.S. Pat.No. 3,709,437 (Wright), U.S. Pat.No. 3,937,364 (Wright), U.S. Pat.No. 4,022,351 (Wright), U.S. Pat. US Pat. No. 4,1147,306 (Bennett), US Pat. No. 4,184,615 (Wright), US Pat. No. 4,598,862 (Rice), US Pat. No. 4,615,467 (Grogan et al.), And US Pat. No. 5,364,031 (Tamiguchi et al.).

  The person skilled in the art, based on his general knowledge, taking into account the nature of the components used, e.g. the solubility of the components in the medium, and the application envisaged for the composition, as well as the appropriate presentation forms and their preparation It should be understood that a method can be selected.

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

(Examples 1 and 2, control, and comparative examples 1 to 4)
Using a hybridizer equipped with a high-speed rotor having a plurality of blades in a chamber under dry conditions, marketed by Nara Machinery Co., Ltd. in Japan, the components shown in Table 1 were subjected to the hybridizer process. Composite pigments according to 1 and 2 and Comparative Examples 1 to 4 were obtained.

  Specifically, for each of Examples 1 and 2 and Comparative Examples 1 to 4, 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 (the numbers in Table 1). Is mixed by mass part). The mixture was put into a hybridizer, and the rotor was rotated at 8,000 rpm (linear speed 100 m / s) for 3 minutes to obtain composite pigments according to Examples 1 and 2 and Comparative Examples 1 to 4.

  Since Tinosorb-M was commercially available as an aqueous dispersion by BASF, the Tinosorb-M was dried to evaporate water in the liquid to obtain methylenebis-benzotriazolyl tetramethylbutylphenol powder. The obtained powder was used in the above hybridizer process.

  As a control, dried Tinosorb-M was used.

[UV absorbance evaluation]
The absorbance of the ultraviolet wave of each composite pigment according to each of Examples 1 and 2 and Comparative Examples 1 to 4 and the absorbance of the ultraviolet wave of the organic UV filter as a control were measured using a V-550 type ultraviolet-visible spectrophotometer (JASCO Corporation). , Japan) and measured as follows.

  A solvent was prepared by mixing isododecane and polyhydroxystearic acid so that the concentration of polyhydroxystearic acid was 3% by weight.

  Each composite pigment according to Examples 1 and 2 and Comparative Examples 1 to 4 and the control powder were dispersed or dissolved in the above solvent by using ultrasound for 1 minute in the sample (Example 1). Samples were obtained such that the concentration of the composite pigment (of 2 and 2 and Comparative Examples 1-4) or the organic UV filter (control) was 0.1% by weight. If there were still aggregates, sonication was repeated.

  The obtained sample was put in a quartz cell having a light path of 2 mm. The UV absorbance of samples having wavelengths of 280 to 315 nm (UV-B) and 315 to 400 nm (UV-A) was measured using a V-550 type ultraviolet-visible spectrophotometer (JASCO Corporation, Japan).

  The results are shown in the columns of “UV-A” and “UV-B” in Table 1.

  From a comparison of Examples 1 and 2 with the control, it is clear that the composite pigments according to Examples 1 and 2 have enhanced UV-A and UV-B absorbance. In particular, UV-A absorbance is enhanced over UV-B absorbance.

  Since a relatively large amount of organic UV filter is used in Example 1, the UV-A and UV-B absorbance values of Example 1 are higher than those of Example 2. Organic UV filter particles easily form aggregates, which makes it difficult to exhibit good UV absorbance, so a relatively large amount of powdered organic UV filter (dried Tinosorb-M It is surprising to observe that) can give higher UV-A and UV-B absorbance.

Since Comparative Examples 1 and 2 use TiO ₂ , the composite pigments according to Comparative Examples 1 and 2 have lower UV-A and UV-B absorbance than the composite pigments according to Examples 1 and 2, respectively. Even when the large core particles of Comparative Examples 1 and 2 were replaced with polyamide particles, this tendency was not changed.

[Visible light transmittance evaluation]
The visible light transmittance of each composite pigment according to each of Examples 1 and 2 and Comparative Examples 1 to 4 was measured as follows using a V-550 type ultraviolet-visible spectrophotometer (JASCO Corporation, Japan). did.

  A solvent was prepared by mixing isododecane and polyhydroxystearic acid so that the concentration of polyhydroxystearic acid was 3% by weight.

  Each composite pigment according to Examples 1 and 2 and Comparative Examples 1 to 4 and the control powder were dispersed or dissolved in the above solvent by using ultrasound for 1 minute in the sample (Example 1). Samples were obtained such that the concentration of the composite pigment (of 2 and 2 and Comparative Examples 1-4) or the organic UV filter (control) was 0.1% by weight. If there were still aggregates, sonication was repeated.

  The obtained sample was put in a quartz cell having a light path of 2 mm. The transmittance in the visible light region of the sample having a wavelength of 400 to 700 nm was measured using a V-550 type ultraviolet-visible spectrophotometer (JASCO Corporation, Japan). The value of the total transmittance was obtained as the average transmittance in the visible light region having a wavelength of 400 to 700 nm.

The result is shown in the column of “total transmittance ^* ” in Table 1.

  From a comparison of Examples 1 and 2 with Comparative Examples 1-4, it is clear that the composite pigments according to Examples 1 and 2 have better transparency in the visible light region than those according to Comparative Examples 1-4. Therefore, when the composite pigments according to Examples 1 and 2 are used in a cosmetic product, it is possible to give better transparency to the cosmetic product as compared with the use of the composite pigments according to Comparative Examples 1 to 4.

  Next, some examples of the formulation of the cosmetic composition according to the present invention are shown below.

(Example 3) Aerosol foam for skin care

(Example 4) Loose powder

Claims (26)

Comprising at least one small core particle having an average particle size greater than 100 nm and less than 1 μm, preferably less than 600 nm, more preferably less than 400 nm,
The surface of the small core particles is at least partially covered by at least one coating layer comprising at least one particulate solid organic UV filter;
The small core particles comprise at least one organic polymer;
Composite pigment.   The composite pigment according to claim 1, wherein the coating layer on the small core particles comprises at least one solid inorganic UV filter and / or at least one coloring pigment.   The particulate solid organic UV filter is an oxalanilide type, triazine type, benzotriazole type; vinylamide type; cinnamamide type; a type containing one or more benzazole groups and / or benzofuran groups or benzothiophene groups or indoles 3. A composite pigment according to claim 1 or 2, selected from: type; aryl vinylene ketone type; phenylene bis (benzoxazinone) derivative type; or acrylonitrile amide, sulfonamide or carbamate derivative type particulate organic UV screening agent.   4. The composite pigment according to claim 2, wherein the solid inorganic UV filter is selected from the group consisting of silicon carbide, metal oxide, and a mixture thereof.   The composite pigment according to any one of claims 1 to 4, wherein the particulate solid organic or inorganic UV filter has an average particle size of 1 nm to 50 nm, preferably 5 nm to 40 nm, more preferably 10 nm to 30 nm.   6. The composite pigment according to any one of claims 2 to 5, wherein the solid inorganic UV filter has at least one coating layer.   The coating layer of the solid inorganic UV filter is made of alumina, silica, aluminum hydroxide, silicone, silane, fatty acid or salt thereof, fatty alcohol, lecithin, amino acid, polysaccharide, protein, alkanolamine, wax, (meth) acrylic polymer, 7. The composite pigment according to claim 6, comprising at least one compound selected from the group consisting of an organic UV filter and a (per) fluoro compound.   The composite pigment according to any one of claims 1 to 7, wherein the coating layer on the small core particles has a thickness of 1 nm to 50 nm, preferably 5 nm to 40 nm, more preferably 10 nm to 30 nm.   The color pigment is titanium dioxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, chromium oxide, manganese purple, ultramarine blue, chromium hydroxide hydrate, ferric blue, aluminum powder, copper 9. Any one of claims 2 to 8, selected from the group consisting of powder, silver powder, gold powder, barium sulfate, carbon black, D & C type pigment, lake, pearlescent pigment, silica, and mixtures thereof. The composite pigment described in 1.   10. The composite pigment according to any one of claims 1 to 9, wherein the coating layer on the small core particles further comprises at least one additional UV filter, in particular at least one liquid organic UV filter.   11. The composite pigment according to any one of claims 1 to 10, wherein the small core particles further contain at least one inorganic material.   The inorganic material is mica, synthetic mica, talc, sericite, boron nitride, glass flake, calcium carbonate, barium sulfate, titanium oxide, hydroxyapatite, silica, silicate, zinc oxide, magnesium sulfate, magnesium carbonate, magnesium trisilicate. Selected from the group consisting of: aluminum oxide, aluminum silicate, calcium silicate, calcium phosphate, magnesium oxide, bismuth oxychloride, kaolin, hydrotalcite, mineral clay, synthetic clay, iron oxide, and mixtures thereof, Item 12. The composite pigment according to Item 11.   13. A composite pigment according to any one of claims 1 to 12, wherein the small core particles comprise at least one copolystyrene, preferably a styrene / acrylate copolymer and / or a crosslinked styrene / methyl methacrylate copolymer. Further comprising at least one large core particle having an average particle size of 2 μm or more, preferably 3 μm or more, more preferably 4 μm or more, and even more preferably 5 μm or more,
The surface of the large core particle is optionally at least partially covered by at least one coating layer comprising at least one selected from the group consisting of a particulate solid organic UV filter, a solid inorganic UV filter, and a color pigment. 14. The composite pigment according to any one of claims 1 to 13, wherein   15. The mass ratio of the small core particles to the large core particles is 10:90 to 90:10, preferably 20:80 to 80:20, more preferably 30:70 to 70:30. Composite pigments.   The mass ratio of the small core particles: the particulate solid organic UV filter is 10:90 to 90:10, preferably 30:70 to 70:30, more preferably 40:60 to 50:50. The composite pigment according to 14 or 15.   The mass ratio of the small core particles / the large core particles / the particulate solid organic UV filter is 20: 50: 30-50: 20: 30, preferably 35: 15: 50-15: 35: 50, more preferably The composite pigment according to any one of claims 14 to 16, wherein is 10:20:70 to 20:10:70.   18. A composite pigment according to any one of claims 14 to 17, wherein the large core particles comprise at least one inorganic material and / or at least one organic material, preferably at least one organic material.   The inorganic material is mica, synthetic mica, talc, sericite, boron nitride, glass flake, calcium carbonate, barium sulfate, titanium oxide, hydroxyapatite, silica, silicate, zinc oxide, magnesium sulfate, magnesium carbonate, magnesium trisilicate. Selected from the group consisting of: aluminum oxide, aluminum silicate, calcium silicate, calcium phosphate, magnesium oxide, bismuth oxychloride, kaolin, hydrotalcite, mineral clay, synthetic clay, iron oxide, and mixtures thereof, Item 19. A composite pigment according to Item 18.   The organic material is poly (meth) acrylate, polyamide, silicone, polyurethane, polyethylene, polypropylene, polystyrene, copolystyrene, polyhydroxyalkanoate, polycaprolactam, poly (butylene) succinate, polysaccharide, polypeptide, polyvinyl alcohol, polyvinyl resin. 19. The composite pigment of claim 18, selected from the group consisting of: a fluoropolymer, a wax, an amidosulfonic acid polyvalent metal salt, an acylated amino acid, and mixtures thereof.   21. A composite pigment according to claim 20, wherein the organic material is a poly (meth) acrylate, preferably a methyl methacrylate polymer. The small core particles comprise at least one copolystyrene, preferably a styrene / acrylate copolymer and / or a crosslinked styrene / methyl methacrylate copolymer;
The large core particles comprise at least one poly (meth) acrylate, preferably methyl methacrylate polymer;
The small core particles and the large core particles are benzotriazole UV filters, preferably the following structure:

[Wherein T ₂ is independently C ₁ -C ₄ alkyl group, C ₅ -C ₁₂ cycloalkyl group or C which may be substituted by one or more groups selected from aryl residues. _At least partially covered by at least one coating layer comprising at least one particulate solid organic UV filter selected from methylene bis (hydroxyphenylbenzotriazole) derivatives having _{1 to} C ₁₈ alkyl groups] The composite pigment according to any one of claims 14 to 21. The composite pigment according to any one of claims 1 to 22, wherein the particulate solid organic UV filter is as follows.

At least one small core particle having an average particle size greater than 100 nm and less than 1 μm, preferably less than 600 nm, more preferably less than 400 nm, comprising at least one organic polymer;
An optional at least one large core particle having an average particle size of 2 μm or more, preferably 3 μm or more, more preferably 4 μm or more, and even more preferably 5 μm or more;
At least one particulate solid organic UV filter;
A method of preparing a composite pigment, optionally comprising subjecting at least one selected from the group consisting of a solid inorganic UV filter, a colored pigment and an additional UV filter to a mechanochemical fusion process.   A cosmetic composition, in particular in the form of a liquid, powder or aerosol foam, comprising the composite pigment according to any one of claims 1 to 23.   A cosmetic agent for photoprotection from UV irradiation, comprising at least one composite pigment according to any one of claims 1 to 23.