Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
  • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
  • A61K8/496—Triazoles or their condensed derivatives, e.g. benzotriazoles
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/0241—Containing particulates characterized by their shape and/or structure
  • A61K8/025—Explicitly spheroidal or spherical shape
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
  • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/60—Particulates further characterized by their structure or composition
  • A61K2800/61—Surface treated
  • A61K2800/612—By organic compounds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/60—Particulates further characterized by their structure or composition
  • A61K2800/65—Characterized by the composition of the particulate/core
  • A61K2800/654—The particulate/core comprising macromolecular material

Definitions

• the present invention relates to a composite pigment comprising a small core particle which is at least partially covered by particulate organic solid UV filters, and in a particular embodiment further containing a large core particle, as well as a method for preparing the composite pigment.
• JP-A-H06-1709 discloses composite pigments comprising a core particle covered by fine particles of an inorganic UV filter.
• the composite pigments based on fine particles of an inorganic UV filter can provide good UV filtering effects for the UVB region (from 280 to 315 nm in wavelength). However, the UV filtering effects provided by these composite pigments based on inorganic UV filter(s) are insufficient in the UVA region (from 315 to 400 nm in wavelength).
• UVA light can give strong damages to the skin. Therefore, it is important for sun-care cosmetics to protect the skin from the UVA light.
• ZnO fine particles or organic liquid UV filters have been used in sun-care cosmetics to shield the UVA light.
• an objective of the present invention is to provide a novel composite pigment which is based on organic solid UV filter(s) and which can provide better UV filtering effects, in particular UVA filtering effects.
• Another objective of the present invention is to reduce or prevent possible adverse effects on the skin by the solid UV filters, while providing better UV filtering effects.
• Another objective of the present invention is to provide a composite pigment with enhanced UV shielding effects, in particular in the UVA region, based on organic UV filters, which is easy to formulate into and stabilized in cosmetics, and does not have poor texture when being applied onto the skin.
• a composite pigment comprising:
• the surface of the small core particle is at least in part covered with at least one coating layer comprising at least one particulate organic solid UV filter, and
• the small core particle contains at least one organic polymer.
• the coating layer on the small core particle may include at least one inorganic solid UV filter and/or at least one coloring pigment.
• the particulate organic solid UV filter may be selected from particulate organic UV screening agents of the oxalanilide type, of the triazine type, of the benzotriazole type; of the vinyl amide type; of the cinnamamide type; of the type comprising one or more benzazole and/or benzofuran or benzothiophene groups or of the indole type; of the aryl vinylene ketone type; of the phenylenebis(benzoxazinone) derivative type; or of the acrylonitrile amide, sulphonamide or carbamate derivative type.
• the inorganic solid UV filter may be selected from the group consisting of silicon carbide, metal oxides, and mixtures thereof.
• the particulate organic or inorganic solid UV filter may have a mean particle size of 1 nm to 50 nm, preferably 5 nm to 40 nm, and more preferably 10 nm to 30 nm.
• the inorganic solid UV filter may have at least one coating.
• the coating of the inorganic solid UV filter may comprise at least one compound selected from the group consisting of alumina, silica, aluminum hydroxide, silicones, silanes, fatty acids or salts thereof, fatty alcohols, lecithin, amino acids, polysaccharides, proteins, alkanolamines, waxes, (meth)acrylic polymers, organic UV filters, and (per)fluoro compounds.
• the coating layer on the small particle may have a thickness of 1 nm to 50 nm, preferably 5 nm to 40 nm, and more preferably 10 run to 30 nm.
• the coloring pigment may be selected from the group consisting of titanium dioxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydrate, ferric blue, aluminum powder, copper powder, silver powder, gold powder, barium sulfate, carbon black, pigments of D&C type, lakes, pearlescent pigments, silica, and mixtures thereof.
• the coating layer on the small particle may further comprise at least one additional UV filter, in particular at least one organic liquid UV filter.
• the small particle may further comprise at least one inorganic material and/or at least one organic material, preferably at least one organic material.
• the inorganic material may be selected from the group consisting of 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, aluminum oxide, aluminum silicate, calcium silicate, calcium phosphate, magnesium oxide, bismuth oxychloride, kaolin, hydrotalcite, mineral clay, synthetic clay, iron oxide, and mixtures thereof.
• the small core particle may comprise at least one copolystyrene, preferably styrene/acrylate copolymer and/or cross-linked styrene/methyl methacrylate copolymer.
• the composite pigment according to the present invention may further comprise at least one large core particle with a mean particle size of 2 ⁇ or more, preferably 3 um or more, more preferably 4 um or more, and even more preferably 5 um or more, wherein the surface of the large core particle is optionally at least in part covered with at least one coating layer comprising at least one selected from the group of consisting of particulate organic solid UV filters, inorganic solid UV filters and coloring pigments.
• the weight ratio of the small core particle(s) to the large core particle(s) may be 10:90 to 90:10, preferably 20:80 to 80:20, and more preferably 30:70 to 70:30.
• the weight ratio of the small core particle(s) to the particulate organic solid UV filter(s) may be 10:90 to 90:10, preferably 30:70 to 70:30, and more preferably 40:60 to 50:50.
• the weight ratio of the small core particle(s)/the large core particle(s)/the particulate organic solid UV filter® may be 20:50:30 to 50:20:30, preferably 35:15:50 to 15:35:50, and more preferably 10:20:70 to 20:10:70.
• the large core particle may comprise at least one inorganic material and/or at least one organic material, preferably at least one organic material.
• the inorganic material of the large core particle may be selected from the group consisting of 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, aluminum oxide, aluminum silicate, calcium silicate, calcium phosphate, magnesium oxide, bismuth oxychloride, kaolin, hydrotalcite, mineral clay, synthetic clay, iron oxide, and mixtures thereof.
• the organic material of the large core particle may be selected from the group consisting of poly(meth)acrylates, polyamides, silicones, polyurethanes, polyethylenes, polypropylenes, polystyrenes, copolystyrenes, polyhydroxyalkanoates, polycaprolactams, poly(butylene) succinates, polysaccharides, polypeptides, polyvinyl alcohols, polyvinyl resins, fluoropolymers, wax, amidosulfonic acid polyvalent metal salts, acylated amino acids, and mixtures thereof.
• polymethacrylate is preferable as the organic material for the large core particle.
• Methylmethacrylate polymer is more preferable.
• the small core particle may comprise at least one copolystyrene, preferably styrene/acrylate copolymer and/or cross-linked styrene/methyl methacrylate copolymer;
• the large core particle comprises at least one poly(meth)acrylate, preferably methyl methacrylate polymer; and the small core and large core particles are at least in part covered with at least one coating layer comprising at least one particulate organic solid UV filter selected from benzotriazole UV filters, preferably
• T 2 independently denotes a Q-C 18 alkyl radical which can be substituted by one or more radicals chosen from a Q-C 4 alkyl radical, a C5-C 12 cycloalkyl radical or an aryl residue.
• the particulate organic solid UV filter may be the molecule represented by the following formula:
• the composite pigment according to the present invention can be prepared by a method for preparing a composite pigment, comprising a step of subjecting:
• At least one small core particle with a mean particle size of more than 100 nm and of less than 1 um, preferably less than 600 nm, and more preferably less than 400 nm, wherein the small core particle contains at least one organic polymer;
• At least one large core particle with a mean particle size of 2 um or more, preferably 3 um or more, more preferably 4 um or more, and even more preferably 5 um or more;
• inorganic solid UV filters optionally at least one selected from the group consisting of inorganic solid UV filters, coloring pigments and additional UV filters
• Another objective of the present invention is to provide a cosmetic composition or a cosmetic agent with advantageous cosmetic and/or practical effects by using the composite pigment according to the present invention.
• the above objective can be achieved by incorporating the composite pigment according to the present invention into a cosmetic composition or a cosmetic agent for the photoprotection against UV radiation, in particular, the UV-A radiation.
• the composite pigment according to the present invention can be contained in a cosmetic composition, in particular in the form of a liquid, powdery or aerosol foam cosmetic composition.
• the new composite pigment according to the present invention comprises
• At least one small core particle with a mean particle size of less than 1 um wherein the surface of the small core particle is at least in part covered with at least one layer comprising at least one particulate organic solid UV filter, and wherein the small core particle contains at least one organic polymer.
• a small core particle with a mean particle size of less than 1 um, wherein the small core particle contains at least one organic polymer, and optionally of a large core particle can provide a coating including particulate organic solid UV filter(s) to the surface of the small core particle, which thereby results in better UV filtering effects, in particular in the UVA region, than those provided by the bulk of particulate organic solid UV filter(s), and that the UV filtering effects, in particular in the UVA region, can be enhanced as compared to when using inorganic solid UV filter(s).
• the composite pigment according to the present invention is safer than the bulk of particulate organic solid UV filters.
• the composite pigment according to the present invention can be easy to formulate into and stabilized in cosmetics, and can avoid poor texture when being applied onto the skin, because the particulate organic UV filter(s) which are essentially used in the composite pigment according to the present invention is not in the form of a liquid.
• the composite pigment according to the present invention can provide a better feeling on use, because fine particles of organic solid UV filter(s) are firmly fixed on the core particles so that it is possible to reduce free fine particles which have a high friction coefficient such that they do not easily spread on the skin and provide an unpleasant feeling on use.
• a cosmetic composition or a cosmetic agent 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.
• the cosmetic composition according to the present invention has better UV shielding effects, in particular in the UVA region.
• the cosmetic composition if the cosmetic composition is in the form of a powder, it also has a smooth feeling on use due to reduced friction, superior hiding effects for skin defects such as pores and fine lines, matt effects and good compactability such that it is difficult to chip away.
• the cosmetic composition if the cosmetic composition is in the form of a liquid, it also has good visual optical effects such as matt and haze effects.
• each of the elements constituting the composite pigment and cosmetic composition according to the present invention will be described in a detailed manner.
• the small core particle to be used for the composite pigment according to the present invention is not limited, as long as the small core particle has a mean particle size or a mean particle diameter of more than 100 nm and less than 1 um, preferably less than 600 nm, and more preferably less than 400 nm.
• the small core particle may be in the form of a solid or hollow particle, preferably a hollow particle.
• the mean particle size or mean particle diameter here is an arithmetric mean diameter, and can be determined, for example, by calculating the average of the dimensions of one hundred particles chosen on an image obtained with a scanning electron microscope.
• the small core particle can be in any shape.
• the plate-like particle has a length ranging from more than 100 nm to less than 1 um, preferably less than 600 nm, and more preferably less than 400 nm.
• the small core particle has a spherical shape.
• the material of the small core particle is not limited.
• the material of the small core particle contains at least one organic polymer, and may further comprise at least one inorganic material.
• the organic polymer of the small core particle may be selected from the group consisting of poly(meth)acrylates, polyamides, silicones, polyurethanes, polyethylenes, polypropylenes, polystyrenes, copolystyrenes, polyhydroxyalkanoates, polycaprolactams, poly(butylene) succinates, polysaccharides, polypeptides, polyvinyl alcohols, polyvinyl resins, fluoropolymers, waxes, amidosulfonic acid polyvalent metal salts, acylated amino acids, and mixtures thereof.
• fluoropolymers for example, PTFE may be used.
• amidosulfonic acid polyvalent metal salts for example, N-lauroyltaurine calcium may be used.
• acylated amino acids for example,
• lauroyllysine may be used.
• Polyamides such as Nylon®, polyhydroxyalkanoates such as polylactic acids, poly(meth)acrylates such as polymethylmethacrylates, silicones, and mixtures thereof are more preferable.
• copolystyrene is preferable, and styrene/acrylate copolymer, and cross-linked styrene/methyl methacrylate copolymer are more preferable.
• small core particles for example, Sunspheres (small hollow particles made from styrene/acrylate copolymer) marketed by Rohm and Haas, as well as SX859(A) and SX866(B) (small hollow particles made from cross-linked styrene/ methyl methacrylate copolymer) marketed by JSR Corp. in Japan, are preferable.
• the inorganic material can be selected from the group consisting of mica, synthetic mica, talc, sericite, boron nitride, glass flakes, calcium carbonate, barium sulfate, titanium oxide, hydroxyapatite, silica, silicate, zinc oxide, magnesium sulfate, magnesium carbonate, magnesium trisilicate, aluminum oxide, aluminum silicate, calcium silicate, calcium phosphate, magnesium oxide, bismuth oxychloride, kaolin, hydrotalcite, mineral clay, synthetic clay, iron oxide, and mixtures thereof.
• natural mica, synthetic mica, sericite, kaolin, talc and mixtures thereof are preferable.
• the inorganic material and/or organic polymer may be porous.
• the porosity of the material may be characterized by a specific surface area of from 0.05 m 2 /g to 1,500 m 2 /g, more preferably from 0.1 m 2 /g to 1,000 m 2 /g, and more preferably from 0.2 m 2 /g to 500 m 2 /g according to the BET method.
• the small core particle may or may not be coated beforehand.
• the small core particle is originally coated.
• the material of an original coating of the small core particle is not limited, but an organic material such as an amino acid, an N-acylamino acid, an amido, a silicone and a modified silicone, may be preferable.
• an organic material such as lauroyl lysine and acryl-modified silicone.
• the small core particle is at least partially covered with at least one layer comprising at least one particulate organic solid UV filter.
• the layer may be referred to as a coating layer.
• 10% or more of the surface of the small core particle can be covered by the coating layer(s). More preferably, 50% or more of the surface of the small core particle can be covered by the coating layer(s). More preferably, 80% or more of the small core particle can be covered by the coating layer(s). Most preferably, the entire surface of the small core particle can be covered by the coating layer(s).
• the thickness of the coating layer may vary depending on several factors such as the size of the small core particle. Typically, the thickness of the coating layer may range from 1 nm to 50 nm, preferably 5 nm to 40 nm, and more preferably from 10 nm to 30 nm.
• the thickness and the composition of the coating layers may be the same as or different from each other.
• the coating layer(s) may comprise, other than the particulate organic solid UV filter(s), any additional material(s) such as coloring pigment(s) and/or additional UV filter(s), preferably inorganic solid UV filter(s).
• the additional material(s) may be present in an amount ranging from 1 to 50 wt% relative to the total weight of the additional material(s) and the particulate organic solid UV filter(s).
• the coating layer on the small core particle comprises at least one particulate organic solid UV filter. If two or more particulate organic solid UV filters are used, they may be the same or different, preferably the same.
• UV filters may be paraphrased with "UV screening agents”.
• the particulate organic solid UV filter used for 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.
• Particulate organic solid UV filter » means an organic molecule which (1) is under the form of solid particles at 25 °C and insoluble in the medium of the composition of the invention and (2) which allow by absorption, and/or reflection and/or diffusion of the UVA and/or UVB radiations allows to block or at least to limit the contact of the said radiations with the surface of keratinic materials (skin, hair, scalp).
• solid means solid at 25°C under 1 atm.
• the particulate organic solid UV filters according to the present invention have preferentially a mean particle size which varies from 10 to 5 ⁇ and more preferably from 10 nm to 2 ⁇ and more particularly from 20 nm to 2 ⁇ .
• the particulate organic solid UV filters according to the present invention can be brought to the desired particulate form by any ad hoc means, such as, in particular, dry milling or milling in a solvent medium, sieving, atomization, micronization or spraying.
• the milling device used according to these documents can be an airjet mill, bead mill, vibration mill or hammer mill and preferably a mill with high-speed stirring or an impact mill and more particularly a rotary bead mill, a vibrating mill, a tube mill or a rod mill.
• the composite pigment according to the present invention has an effect that of providing a transparent or clear appearance, because the fine particles of the particulate organic solid UV filter(s) do not aggregate but spread on the core particle.
• the material of the particulate organic solid UV filter(s) is not limited as long as it is organic. If two or more particulate organic solid UV filters are used, the material(s) of the particulate organic solid UV filters may be the same as or different from each other.
• the particulate solid organic UV screening agents in accordance with the present invention can be chosen in particular from particulate organic UV screening agents of the oxalanilide type, of the triazine type, of the benzotriazole type; of the vinyl amide type; of the cinnamamide type; of the type comprising one or more benzazole and/or benzofuran or benzothiophene groups or of the indole type; of the aryl vinylene ketone type; of the phenylenebis(benzoxazinone) derivative type; or of the acrylonitrile amide, sulphonamide or carbamate derivative type.
• the term benzazole simultaneously encompasses benzothiazoles, benzoxazoles and benzimidazoles.
• UV screening agents of the oxalanilide type in accordance with the invention, of those corresponding to the structure: in which Ri and R 2 , independently, are CrC 18 alkyl or Cj-C 18 alkoxy.
• a preferred compound of formula (1 ) is N-(2-ethoxyphenyl)-N'-(2-ethylphenyl)-ethanediamide. These compounds are disclosed in Patent Application WO 95/22959.
• a preferred class of solid triazine UV absorbers is that having the formula:
• Preferred com ounds of formula (2) are those having one of the formulae:
• R 7 are the same or different and each is hydrogen; an alkali metal; an ammonium group N(Rg) 4 in which 3 ⁇ 4 is hydrogen or an organic radical; C1-C20 alkyl; or a polyoxyethylene radical which contains from 1 to 10 ethylene oxide units and the terminal OH group of which may be etherified by a Q-C3 alcohol.
• R 7 when R 7 is an alkali metal it is preferably potassium or, especially sodium; when R 7 is the group N(Rs) 4 in which Rs has its previous meaning, it is preferably a mono-, di- or tri-Ci-C 4 alkylammonium salt, a mono-, di- or tri-C2-C 4
• alkanolammonium salt or a C1-C20 alkyl ester thereof when Rs is a C1-C20 alkyl group, it is preferably a C 6 -C 12 alkyl group, more preferably a C8-C9 alkyl group, especially a
• phenylcyanoacrylate groups such as those disclosed in Application EP-A-0 790 243 (which is incorporated by reference as an integral part of the content of the description). Mention will more particularly be made, among these insoluble UV screening agents of the triazine type, of the following compounds: - 2,4,6-tris(diethyl 4'-ammobenzalmalonate)-s-triazine,
• UV screening agents of the triazine type in accordance with the invention of insoluble s-triazine derivatives carrying benzotriazole and/or benzothiazole groups, such as those disclosed in Application WO 98/25922 (which is incorporated by reference to forms an integral part of the content of the description).
• a preferred class of solid (benzo triazole UV absorbers is that having the formula:
• Tj is Q-Qs alkyl or, preferably, hydrogen
• T 2 is hydrogen, hydroxyl, or Ci-Cu alkyl, optionally substituted by Q-C 12 cycloalkyl or an aryl such as phenyl, preferably
• the - s alkyl groups can be linear or branched and are, 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, n-dodecyl, tetradecyl, hexadecyl or octadecyl; the C5-C12 cycloalkyl groups are, for example, cyclopentyl, cyclohexyl or cyclooctyl; and the aryl groups are, for example, phenyl or benzyl. Mention may
• a further preferred class of solid (benzo)triazole UV absorbers is that having the formula:
• a still further preferred class of solid triazole UV absorbers is that having the formula:
• a preferred class of solid vinyl group-containing amide UV absorbers is that having the formula:
• R9-(Y)m-CO-C(R 10 ) C(Rn)-N(R 12 )(R 13 ) in which R 9 is Q-C 18 alkyl, preferably C ⁇ -Cs alkyl, or phenyl optionally substituted by one, two or three substituents selected from OH, Ci-C 18 alkyl, Q-C 18 alkoxy or CO-ORe in which Re has its previous meaning; R 10 , R lls Ri 2 and R 13 are the same or different and each is Ci-C 18 alkyl, preferably Q-Cs alkyl, or hydrogen; Y is N or O; and m has its previous meaning.
• Preferred compounds of formula (34) are 4-octyl-3-penten-2-one, emyl-3-oc1ylamino-2-butenoate, 3 -octylamino- 1 -phenyl-2-buten- 1 -one and 3 -dodecylarnino- 1 -phenyl-2-buten- 1 -one.
• a preferred class of solid cinnamic acid amide UV absorbers is that having the formula: in which R 14 is hydroxy or Q-C 4 alkoxy, preferably methoxy or ethoxy; R 15 is hydrogen or C 1 -C 4 alkyl, preferably methyl or ethyl; and Ri 6 is -(CONH) m -phenyl in which m has its previous meaning and the phenyl group is optionally substituted by one, two or three substituents selected from OH, Ci-C ⁇ alkyl, Q-Qs alkoxy or CO-ORe in which Re has its previous meaning.
• R 16 is phenyl, 4-methoxyphenyl or the phenylaminocarbonyl group.
• the compounds of formula (1) to (35) are known.
• the compounds of formula (30) are described, together with their production, in U.S. Pat. No. 4,617,390.
• the particulate organic solid UV filter(s) be a benzotriazole derivative, in particular, a phenylbenzotriazole derivative such as a drometrizole trisiloxane, marketed under the trademark "Silatrizole” by Rhodia Chimie or "Mexoryl XL” by L'Oreal, as represented below.
• a benzotriazole derivative such as a drometrizole trisiloxane, marketed under the trademark "Silatrizole” by Rhodia Chimie or "Mexoryl XL” by L'Oreal, as represented below.
• each of the X symbols independently represents an oxygen or sulphur atom or an NR 2 group
• each of the Z symbols independently represents a nitrogen atom or a CH group
• each of the Ri symbols independently represents an OH group, a halogen atom, a linear or branched C 1-8 alkyl group, optionally comprising a silicon atom, or a linear or branched C 1-8 alkoxy group,
• each of the numbers m independently has the value 0, 1 or 2
• n an integer between 1 and 4 inclusive
• p is equal to 0 or 1
• each of the numbers q is independently equal to 0 or 1 ,
• each of the R 2 symbols independently represents a hydrogen atom or a benzyl or linear or branched C 1-8 alkyl group, optionally comprising a silicon atom,
• A represents a radical with a valency n chosen from those of formulae:
• each of the R 3 symbols independently represents a halogen atom or a linear or branched C 1-4 alkyl or alkoxy group or a hydroxyl group,
• N,N'-dimemyl-2,2'-bisberizirnidazole it being possible for these compounds to be prepared according to the procedures disclosed in Patents US 5 961 960 and US 2 463 264.
• n' l or 2
• each of the R$ symbols independently represents an OH group, a halogen atom, a linear or branched C 1-6 alkyl group optionally comprising a silicon atom, a linear or branched C 1-6 alkoxy group optionally comprising a silicon atom, a linear or branched C 1-5 alkoxycarbonyl group, or a linear or branched C 1-6 alkylsulphonamide group optionally comprising a silicon atom or an amino acid functional group,
• p' represents an integer between 0 and 4 inclusive
• q' represents 0 or 1
• R 5 represents hydrogen or an OH group
• Re represents hydrogen, a linear or branched C 1-6 alkyl group optionally comprising a silicon atom, a cyano group, a C 1-6 alkylsulphonyl group or a phenylsulphonyl group,
• R 7 represents a linear or branched C 1-6 alkyl group optionally comprising a silicon atom or a phenyl group which can form a bicycle and which is optionally substituted by one or two R4 radicals,
• n' 1, which screen out UV radiation and which have a mean particle size of between 10 nm and 5 ⁇ , of the following families:
• JP 04 134 043 for example 2-(4-methox benzylidene)indan-l-one:
• JP 04 134 043 for example 2-(4-methoxybenzylidene)-3,4-dihydro-2H-naphthalen-l-one;
• EP 0 390 683 for example 4-(4-memox benzylidene)-2,2,5,5-te1xamethyldihydrofuran-3-one:
• R representing a divalent aromatic residue chosen from the following formulae (e") to (h"):
• each of the R 9 symbols independently represents an OH group, a halogen atom, a linear or branched C 1-6 alkyl group optionally comprising a silicon atom, a linear or branched C 1-6 alkoxy group optionally comprising a silicon atom, a linear or branched C 1-5 alkoxycarbonyl group, or a linear or branched C 1-6 alkylsulphonamide group optionally comprising a silicon atom or an amino acid functional group,
• p represents an integer between 0 and 4 inclusive
• q" represents 0 or 1.
• R 10 represents a linear or branched C 1- alkyl group
• n 0, 1 or 2
• Rn represents a single bond or a linear or branched, divalent -C30 alkylene or C 3 -C 30 alkenylene radical which can carry one or more hydroxyl substituents and which can comprise, in the carbonaceous chain, one or more heteroatoms chosen from oxygen, nitrogen and silicon atoms
• R 12 represents an -OR 14 or -NHR 14 radical
• R 13 represents a linear or branched Ci-C 30 alkyl radical or a phenyl ring which is unsubstituted or substituted by Q-C 4 alkyl or alkoxy radicals,
• R 14 represents a linear or branched Ci-C 30 alkyl or C 3 -C 30 alkenyl radical which can carry one or more hydroxyl substituents and which can comprise, in the carbonaceous chain, one or more heteroatoms chosen from oxygen, nitrogen and silicon atoms.
• polyvalent metal salts for example, Ca 2+ , Zn 2+ , Mg 2+ , Ba 2+ , Al 3+ or Zr 4+
• polyvalent metal salts of sulphonated derivatives of benzylidenecamphor such as those disclosed in Application FR-A 2 639 347
• polyvalent metal salts of sulphonated derivatives of benzimidazole such as those disclosed in
• Application EP-A-893 119 or the 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 as disclosed in Patent Applications WO 93/10753,
• a preferred class of particulate solid sulfonated benzirnidazole UV absorbers is that having the formula:
• M is hydrogen or an alkali metal, preferably sodium, an alkaline earth metal, such as magnesium or calcium, or zinc.
• Q-Qs alkyl groups may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-amyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, tetradecyl, hexydecyl or octadecyl; and Q-Qs alkoxy groups include methoxy, ethoxy, propoxy, butoxy, n-hexoxy, n-heptoxy, n-octoxy, iso-octoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dodecoxy, te
• d-C 18 carboxyalkyl includes carboxymethyl, carboxyethyl, carboxypropyl, carboxyisopropyl, carboxybutyl, carboxyisobutyl, carboxybutyl, carboxyamyl, carboxyhexyl, carboxyheptyl, carboxyoctyl, carboxyisooctyl, carboxynonyl, carboxydecyl, carboxyundecyl, carboxydodecyl, carboxytetradecyl, carboxyhexadecyl and carboxyoctadecyl, carboxymethyl being preferred.
• C 5 -C 8 cycloalkyl includes cyclopentyl, cyclohexyl and cyclooctyl.
• the particulate organic solid 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.
• particulate organic solid UV filter(s) is selected from
• the particulate organic solid UV filter(s) may be used in the composite pigment according to the present invention in proportions such that the weight ratio of the small core particle to the particulate organic solid UV filter(s) is 10:90 to 90:10, preferably 30:70 to 80:20, and more preferably 40:60 to 50:50.
• the coating layer(s) on the small core particle may comprise at least one inorganic solid UV filter. If two or more inorganic solid UV filters are used, they may be the same or different, preferably the same.
• the inorganic solid UV filter used for 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. It is preferable that the active UV filtering region of the inorganic solid UV filter and that of the particulate organic solid UV filter be complementary to each other, in order to provide comprehensive UV protection. For example, it is preferable that the inorganic solid UV filter be active at least in the UV-B region and the particulate organic solid UV filter be active at least in the UV-A region.
• the inorganic solid UV filter may be hydrophilic and/or lipophilic.
• the inorganic solid UV filter is completely insoluble in solvents such as water and ethanol commonly used in cosmetics.
• solid means solid at 25°C under 1 arm.
• the inorganic solid UV filter be in the form of a fine particle such that the mean (primary) particle diameter thereof ranges from 1 nm to 50 nm, preferably 5 nm to 40 nm, and more preferably 10 nm to 30 nm.
• the mean (primary) particle size or mean (primary) particle diameter here is an arithmetic mean diameter.
• the inorganic solid UV filter may be selected from the group consisting of silicon carbide, metal oxides which may or may not be coated, and mixtures thereof.
• the inorganic solid UV filters are selected from pigments (mean size of the primary particles: generally from 5 nm to 50 nm, preferably from 10 nm to 50 nm) formed of metal oxides, such as, for example, pigments formed of titanium oxide (amorphous or crystalline in the rutile and/or anatase form), iron oxide, zinc oxide, zirconium oxide or cerium oxide, which are all UV photoprotective agents well known per se.
• the inorganic solid UV filters are selected from titanium oxide, zinc oxide, and more preferably titanium oxide.
• the inorganic solid UV filter may or may not be coated.
• the inorganic solid UV filter may have at least one coating.
• the coating may comprise at least one compound selected from the group consisting of alumina, silica, aluminum hydroxide, silicones, silanes, fatty acids or salts thereof (such as sodium, potassium, zinc, iron or aluminum salts), fatty alcohols, lecithin, amino acids, polysaccharides, proteins, alkanolarnines, waxes such as beeswax, (meth)acrylic polymers, organic UV filters, and (per)fluoro compounds.
• the coating includes at least one organic UV filter.
• a dibenzoylmethane derivative such as butyl methoxydibenzoylmethane (Avobenzone) and
• TINOSORB M Bis-Benzotriazolyl Tetramethylbutylphenol marketed as "TINOSORB M" by BASF may be preferable.
• the silicones in the coating(s) may be organosilicon polymers or oligomers comprising a linear or cyclic and branched or cross-linked structure, of variable molecular weight, obtained by polymerization and/or polycondensation of suitable functional silanes and essentially composed of a repetition of main units in which the silicon atoms are connected to one another via oxygen atoms (siloxane bond), optionally substituted hydrocarbon radicals being connected directly to the said silicon atoms via a carbon atom.
• silanes also encompasses silanes necessary for their preparation, in particular alkylsilanes.
• the silicones used for the coating(s) can preferably be selected from the group consisting of alkylsilanes, polydialkylsiloxanes and polyalkylhydrosiloxanes. More preferably still, the silicones are selected from the group consisting of octyltiimethylsilane, polydimethylsiloxanes and polymethylhydrosiloxanes.
• the inorganic solid UV filters made of metal oxides may, before their treatment with silicones, have been treated with other surfacing agents, in particular with cerium oxide, alumina, silica, aluminum compounds, silicon compounds or their mixtures.
• the coated inorganic solid UV filter may have been prepared by subjecting the inorganic solid UV filter to one or more surface treatments of a chemical, electronic, mechanochemical and/or mechanical nature with any of the compounds as described above, as well as polyethylenes, metal alkoxides (titanium or aluminum alkoxides), metal oxides, sodium hexametaphosphate, and those shown, for example, in Cosmetics & Toiletries, February 1990, Vol. 105, pp. 53-64.
• coated inorganic solid UV filters may be titanium oxides coated:
• silica such as the product "Sunveil" from Ikeda
• silica and with alumina such as the products "Microtitanium Dioxide MT 500 SA” from Tayca, “Tioveil” from Tioxide, and “Mirasun TiW 60" from Rhodia;
• iron oxide and with iron stearate, such as the product "Microtitanium Dioxide MT 100 F" from Tayca;
• silica with silica, with alumina and with aluminum stearate and treated with a silicone, such as the product "STT-30-DS" from Titan Kogyo;
• stearic acid such as the product "Tipaque TTO-55 (C)" from Ishihara; or
• sodium hexametaphosphate such as the product "Microtitanium Dioxide MT 150 W” from Tayca.
• titanium oxide pigments treated with a silicone are preferably Ti0 2 treated with
• coated Ti0 2 can be used as the coated inorganic UV filter:
• Stearic acid (and) Aluminum Hydroxide (and) Ti0 2 such as the product "MT-100 TV" from Tayca, with a mean primary particle diameter of 15 nm;
• Dimethicone and) Stearic Acid (and) Aluminum Hydroxide (and) Ti0 2 , such as the product "SA-TTO-S4" from Miyoshi Kasei, with a mean primary particle diameter of 15 nm;
• Silica (and) Ti0 2 such as the product "MT-100 WP" from Tayca, with a mean primary particle diameter of 15 nm;
• Dimethicone (and) Silica (and) Aluminum Hydroxide (and) Ti0 2 such as the product "MT-Y02" and “MT-Y-110 M3S” from Tayca, with a mean primary particle diameter of 10 nm;
• Dimethicone (and) Aluminum Hydroxide (and) Ti0 2 such as the product "SA-TTO-S3" from Miyoshi Kasei, with a mean primary particle diameter of 15 nm;
• Dimethicone (and) Alumina (and) Ti0 2 such as the product "UV TITAN Ml 70" from Sachtleben, with a mean primary particle diameter of 15 nm; and
• Silica and) Aluminum Hydroxide (and) Alginic Acid (and) Ti0 2 , such as the product "MT-100 AQ" from Tayca, with a mean primary particle diameter of 15 nm.
• Ti0 2 coated with at least one organic UV filter is more preferable.
• Avobenzone (and) Stearic Acid (and) Aluminum Hydroxide (and) Ti0 2 such as the product "HXMT-IOOZA” from Tayca, with a mean primary particle diameter of 15 nm, can be used.
• the uncoated titanium oxide pigments are, for example, marketed by Tayca under the trademarks "Microtitanium Dioxide MT500B” or “Microtitanium Dioxide MT600B", by Degussa under the trademark “P 25”, by Wacker under the trademark Oxyde de titane transparent PW”, by Miyoshi Kasei under the trademark “UFTR”, by Tomen under the trademark “ITS” and by Tioxide under the trademark "Tioveil AQ”.
• the uncoated zinc oxide pigments are, for example:
• coated zinc oxide pigments are, for example:
• Nanophase Technologies those marketed under the trademark “Nanogard Zinc Oxide FN” by Nanophase Technologies (as a).
• Escalol Z100 those marketed under the trademark "Escalol Z100" by ISP (alumina-treated ZnO dispersed in an ethylhexyl methoxycinnamate/PVP-hexadecene copolymer/methicone mixture);
• the uncoated cerium oxide pigments are marketed, for example, under the trademark "Colloidal Cerium Oxide” by Rhone-Poulenc.
• the uncoated iron oxide pigments are, for example, marketed by Arnaud under the trademarks "Nanogard WCD 2002 (FE 45B)", “Nanogard Iron FE 45 BL AQ”, “Nanogard FE 45R AQ” and “Nanogard WCD 2006 (FE 45R)", or by Mitsubishi under the trademark "TY-220”.
• the coated iron oxide pigments are, for example, marketed by Arnaud under the trademarks "Nanogard WCD 2008 (FE 45B FN)", “Nanogard WCD 2009 (FE 45B 556)", “Nanogard FE 45 BL 345" and “Nanogard FE 45 BL” or by BASF under the trademark "Oxyde de fer transparent”.
• Coated inorganic solid UV filters are preferable, because the UV filtering effects of the inorganic solid UV filters can be enhanced.
• the coating(s) may function as a binder for fixing the UV filters on a small core particle.
• the composite pigment according to the present invention has an effect of not providing a white appearance but a transparent or clear appearance, because the fine particles of the inorganic solid UV filters do not aggregate but spread on the core particle. It should be noted that free fine particles of inorganic solid UV filter(s) easily aggregate to give a white appearance to the skin.
• the inorganic solid UV filter(s) may be used in the composite pigment according to the present invention in proportions such that the weight ratio of the small core particle(s) to the inorganic solid UV filter(s) is 10:90 to 90: 10, preferably 30:70 to 70:30, and more preferably 40:60 to 50:50.
• the coating layer(s) on the small core particle may comprise at least one coloring pigment.
• coloring pigment(s) should be understood as meaning white or colored, inorganic or organic particle(s) of any shape which is/are insoluble and is/are intended to color a composition comprising them.
• the composite pigment according to the present invention has an effect of providing a clearer appearance with high chroma, because the coloring pigments do not aggregate but spread on the substrate. It should be noted that free coloring pigments easily aggregate to give a dark appearance with low chroma to the skin. Therefore, the color of the cosmetics including coloring pigments can be opaque and dark. On the other hand, the composite pigment according to the present invention can provide clear and bright color tone.
• the pigments can be white or colored, inorganic and/or organic and generally have a mean particle size greater or equal to 1 ⁇ .
• inorganic pigments that may be used, non-limiting mention may be made of titanium dioxide, optionally surface treated, zirconium or cerium oxide, as well as zinc, (black, yellow or red) iron or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, barium sulfate, or metal powders, such as aluminum, copper, silver or gold powder.
• the particle size of the coloring pigment is not limited.
• the coloring pigment may have a mean particle size of from 100 nm to less than 1 um, preferably from 100 nm to less than 500 nm, and more preferably from 100 nm to less than 300 nm. Since particles of coloring pigment(s) can be firmly bonded on the small core particle, the coloring pigment(s) cannot penetrate into the skin via pores on the skin. In addition, even if the coloring pigment(s) irritate, a large amount of the coloring pigment(s) cannot directly contact with the skin, because they are present only on the small core particle. Accordingly, the composite pigment according to the present invention is safer than the bulk of coloring pigments.
• organic pigments that may be used, non-limiting mention may be made of carbon black, pigments of D&C type and lakes, such as lakes-based on cochineal carmine and on barium, strontium, calcium or aluminum.
• Red 202 (Calcium
• the coloring pigment is chosen from titanium dioxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydrate, ferric blue, aluminum powder, copper powder, silver powder, gold powder, barium sulfate, carbon black, pigments of D&C type, lakes, pearlescent pigments, and mixtures thereof.
• pearlescent pigments should be understood as meaning iridescent particles of any shape, such as particles produced by certain shellfish in their shells or else synthesized.
• the pearlescent agents can be chosen from white pearlescent agents, such as mica covered with titanium dioxide or with bismuth oxychloride; colored pearlescent agents, such as titanium oxide-coated mica covered with iron oxide, titanium oxide-coated mica covered with ferric blue or chromium oxide, or titanium oxide-coated mica covered with an organic pigment of the abovementioned type; and pearlescent agents based on bismuth oxychloride.
• the composite pigment according to the present invention can provide a better feeling on use, because fine particles of coloring pigment(s), if used, can be firmly fixed on the small core particles so that it is possible to reduce free fine particles which have a high friction coefficient such that they do not easily spread on the skin and provide an unpleasant feeling on use.
• the coloring pigment(s) may be used in the composite pigment according to the present invention in proportions such that the weight ratio of the small core particle to the coloring pigment(s) is 50:50 to 90:10, preferably 50:50 to 80:20, and more preferably 50:50 to 70:30. (Additional UV Filter)
• the coating layer on the small core particle may further comprise at least one additional UV filter. If two or more additional UV filters are used, they may be the same or different, preferably the same.
• the additional UV filter used for 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.
• 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 solid and liquid, respectively, at 25°C under 1 arm.
• the additional UV filter may be made from at least one organic or inorganic material, preferably at least one organic material.
• the additional UV filter(s) may be selected from the group consisting of anthranilic derivatives; dibenzoylmethane derivatives; cinnamic derivatives; salicylic derivatives; camphor derivatives; benzophenone derivatives; ⁇ , ⁇ -diphenylacrylate derivatives; triazine derivatives; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazoline derivatives; bis-benzoazolyl derivatives; p-aminobenzoic acid (PABA) and derivatives thereof; benzoxazole derivatives; screening polymers and screening silicones; dimers derived from a-alkylstyrene; 4,4-diarylbutadienes; octocrylene and derivatives thereof, guaiazulene and derivatives thereof, rutin and derivatives thereof, flavonoids, biflavonoids, oryzanol and derivatives thereof, quinic acid and derivatives thereof, phenols
• Ethylhexyl methoxycinnamate marketed in particular under the trademark "Parsol MCX” by Hoffmann-La Roche
• isopropyl methoxycinnamate isopropoxy methoxycinnamate
• isoamyl methoxycinnamate marketed under the trademark "Neo Heliopan E 1000” by Haarmann and Reimer
• cinoxate (2-ethoxyethyl-4-methoxy cinnamate)
• DEA methoxycinnamate diisopropyl methylcinnamate
• - Salicylic derivatives Homosalate (homomentyl salicylate), marketed under the trademark “Eusolex HMS” by Rona EM Industries; ethylhexyl salicylate, marketed under the trademark “Neo Heliopan OS” by Haarmann and Reimer; glycol salicylate; butyloctyl salicylate; phenyl salicylate; dipropyleneglycol salicylate, marketed under the trademark “Dipsal” by Scher; and TEA salicylate, marketed under the trademark "Neo Heliopan TS” by Haarmann and Reimer.
• benzylidenecamphor derivatives in particular, benzylidenecamphor derivatives: 3-benzylidene camphor, manufactured under the trademark “Mexoryl SD” by Chimex; 4-methylbenzylidene camphor, marketed under the trademark “Eusolex 6300” by Merck; benzylidene camphor sulfonic acid, manufactured under the trademark “Mexoryl SL” by Chimex; camphor benzalkonium
• 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
• Octocrylene marketed in particular under the trademark "Uvinul N539” by BASF
• Etocrylene marketed in particular under the trademark "Uvinul N35” by BASF.
• Triazine derivatives diethylhexyl butamido triazone, marketed under the trademark "Uvasorb HEB” by Sigma 3V; 2,4,6-tris(dineopentyl 4'-ammobenzalmalonate)-s-triazine.
• Benzalmalonate derivatives Dineopentyl 4'-methoxybenzalmalonate, and polyorganosiloxane comprising benzalmalonate functional groups, such as polysilicone-15, marketed under the trademark "Parsol SLX” by Hofrmann-LaRoche.
• phenylbenzimidazole derivatives in particular, phenylbenzimidazole derivatives: Phenylberizimidazole sulfonic acid, marketed in particular under the trademark “Eusolex 232” by Merck, and disodium phenyl dibenzimidazole tetrasulfonate, marketed under the trademark "Neo Heliopan AP” by Haarmann and Reimer.
• PABA p-aminobenzoic acid
• ethyl PABA Ethyl dihydroxypropyl PABA
• pentyl dimethyl PABA ethylhexyl dimethyl PABA
• glyceryl PABA glyceryl PABA
• PEG-25 PABA marketed under the trademark "Uvinul P25” by BASF.
• Dimers derived from a-alkylstyrene The dimers described in DE-19855649.
• Rutin and derivatives thereof Rutin and glucosylrutin.
• Flavonoids Robustin (isoflavonoid), genistein (flavonoid), tectochrysin (flavonoid), and hispidone (flavonoid).
• Phenol Phenol
• Peptides having an aromatic amino acid residue Peptides having tryptophan, tyrosine or phenylalanine.
• the preferred organic additional UV filter(s) is selected from:
• a more preferable organic UV filter is butyl methoxydibenzoylmethane (Avobenzone).
• the additional UV filter is an organic liquid UV filter.
• the material of the organic liquid UV filter(s) is not limited as long as it is organic. If two or more organic liquid UV filters are used, the material(s) of the organic liquid UV filters may be the same as or different from each other.
• Ethylhexyl methoxycinnamate marketed in particular under the trademark "Parsol MCX” by Hoffmann-La Roche
• isopropyl methoxycinnamate isopropoxy methoxycinnamate
• isoamyl methoxycinnamate marketed under the trademark "Neo Heliopan E 1000” by Haarmann and Reimer
• cinoxate (2-ethoxyethyl-4-methoxy cinnamate)
• DEA methoxycinnamate diisopropyl methylcinnamate
• - Salicylic derivatives Homosalate (homomentyl salicylate), marketed under the trademark “Eusolex HMS” by Rona/EM Industries; ethylhexyl salicylate, marketed under the trademark “Neo Heliopan OS” by Haarmann and Reimer; glycol salicylate; butyloctyl salicylate; phenyl salicylate; dipropyleneglycol salicylate, marketed under the trademark “Dipsal” by Scher; and TEA salicylate, marketed under the trademark "Neo Heliopan TS” by Haarmann and Reimer.
• Octocrylene marketed in particular under the trademark "Uvinul N539” by BASF
• Etocrylene marketed in particular under the trademark "Uvinul N35” by BASF.
• the preferred organic liquid additional UV filter(s) may be selected from:
• ethylhexyl methoxycinnamate homosalate, ethylhexyl salicylate, octocrylene, polysilicone-15.
• the additional UV filter(s) may be used in the composite pigment according to the present invention in proportions such that the weight ratio of the small core particle to the additional UV filter(s) is 50:50 to 90:10, preferably 50:50 to 80:20, and more preferably 50:50 to 70:30.
• the large core particle to be used for the composite pigment according to the present invention is not limited, as long as the large core particle has a mean particle size or a mean particle diameter of 2 um or more, preferably 3 um or more, more preferably 4 um or more, and even more preferably 5 um or more.
• the mean particle size of the large core particle may be limited to 50 um or less, preferably 30 um or less, and more preferably 20 um or less, and even more preferably 10 um or less.
• the mean particle size or mean particle diameter here is an arithmetic mean diameter, and can be determined, for example, by calculating the average of the dimensions of one hundred particles chosen on an image obtained with a scarining electron microscope.
• the large core particle may be hollow or solid. It may be preferable to use solid large particle.
• the large particle can be in any shape.
• the plate-like particle have a length ranging from 2 um or more, preferably 3 um or more, more preferably 4 um or more, and even more preferably 5 um or more, to 50 um or less, preferably 30 um or less, and more preferably 20 um or less, and even more preferably 10 um or less.
• the large core particle has a spherical shape.
• the material of the large core particle is not limited.
• the material can be at least one inorganic material and/or at least one organic material, preferably at least one organic material.
• the inorganic material and/or organic material may be hollow or porous.
• the porosity of the inorganic material and/or organic material may be hollow or porous.
• material may be characterized by a specific surface area of from 0.05 m7g to 1,500 m7g, more preferably from 0.1 m 2 /g to 1,000 m 2 /g, and more preferably from 0.2 m 2 /g to 500 m 2 /g according to the BET method.
• the inorganic material can be selected from the group consisting of mica, synthetic mica, talc, sericite, boron nitride, glass flakes, calcium carbonate, barium sulfate, titanium oxide, hydroxyapatite, silica, silicate, zinc oxide, magnesium sulfate, magnesium carbonate, magnesium trisilicate, aluminum oxide, aluminum silicate, calcium silicate, calcium phosphate, magnesium oxide, bismuth oxychloride, kaolin, hydrotalcite, mineral clay, synthetic clay, iron oxide, and mixtures thereof. Natural mica, synthetic mica, sericite, kaolin, talc, silica and mixtures thereof are more preferable. In particular, silica particles such as P-1500 marketed by JGC C&C are preferable as inorganic large particles.
• the organic material can be selected from the group consisting of poly(meth)acrylates, polyamides, silicones, polyurethanes, polyethylenes, polypropylenes, polystyrenes, copolystyrenes, polyhydroxyalkanoates, polycaprolactams, poly(butylene) succinates, polysaccharides,
• polypeptides polyvinyl alcohols, polyvinyl resins, fluoropolymers, waxes, amidosulfonic acid polyvalent metal salts, acylated amino acids, and mixtures thereof.
• fluoropolymers for example, PTFE may be used.
• amidosulfonic acid polyvalent metal salts for example, N-lauroyltaurine calcium may be used.
• acylated amino acids lauroyllysine may be used.
• Polyamides such as Nylon®, polyhydroxyalkanoates such as polylactic acids, poly(meth)acrylates such as polymethylmethacrylates, silicones, fluoropolymers, and mixtures thereof are more preferable.
• polymethylmethacrylate particles such as MR-7GC marketed by Soken in Japan
• polyamide particles such as SP-500 marketed by Toray, Orgasol marketed by Arkema
• PTFE particles such as Ceridust 9205F marketed by Clariant
• the large core particle may or may not be coated beforehand.
• the large core particle is originally coated.
• the material of an original coating of the large core particle is not limited, but an organic material such as an amino acid, an N-acylamino acid, an amido, a silicone, a modified silicone and a polyolefin, is preferable.
• the organic material mention may be made of lauroyl lysine, acryl-modified silicone and polyethylene.
• silica particles coated with polyethylene such as ACEMATT OK412 marketed by Degussa may be preferable as coated (inorganic) large particles.
• the weight ratio of the small core particle(s) to the large core particle(s) may be 10:90 to 90: 10, preferably 20:80 to 80:20, and more preferably 30:70 to 70:30.
• particle(s)/the particulate organic solid UV filter(s) may be 20:50:30 to 50:20:30, preferably 35:15:50 to 15:35:50, and more preferably 10:20:70 to 20:10:70.
• the composite pigment according to the present invention may satisfy the following requirements:
• the small core particle comprises at least one copolystyrene, preferably styrene/acrylate copolymer and/or a cross-linked styrene/methyl methacrylate copolymer;
• the large particle comprises at least one poly(meth)acrylate, preferably methyl methacrylate polymer; and the small core and large core particles are at least in part covered with at least one coating layer comprising at least one particulate orgamc solid UV filter selected from benzotriazole UV filters, preferably methylenebis(hydroxyphenylbenzotriazole) derivatives with the following structure:
• T 2 independently denotes a C C ⁇ alkyl radical which can be substituted by one or more radicals chosen from a Q-CJ, alkyl radical, a C 5 -C 12 cycloalkyl radical or an aryl residue, and more preferably selected from the group consisting of:
• the composite pigment according to the present invention can be prepared by subjecting at least one small core particle with a mean particle size of more than 100 nm and of less than 1 urn, preferably less than 600 nm, and more preferably less than 400 nm, wherein the small core particle contains at least one organic polymer; optionally at least one large core particle with a mean particle size of 2 um or more, preferably 3 um or more, more preferably 4 um or more, and even more preferably 5 um or more;
• inorganic solid UV filters optionally at least one selected from the group consisting of inorganic solid UV filters, coloring pigments and additional UV filters
• the small core particle, the large core particle, the particulate organic solid UV filter, the inorganic solid UV filter, the coloring pigment, and the additional UV filter are as explained above.
• Mechanochemical fusion process means a process in which mechanical power such as impact force, friction force or shear force is applied to a plurality of subjects to cause fusion between the subjects.
• the mechanochemical fusion process may be performed by, for example, an apparatus comprising a rotating chamber and a fixed inner piece with a scraper, such as a mechanofusion system marketed by Hosokawa Micron Corporation in Japan.
• the hybridizer process was developed in the 1980s.
• the hybridizer process is a class of mechanochemical fusion processes in which strong mechanical power is applied to a plurality of particles to cause a mechanochemical reaction to form a composite particle.
• the mechanical power is imparted by a high-speed rotor which can have a diameter from 10 cm to 1 m, and can rotate at a speed of 1,000 rpm to 100,000 rpm. Therefore, the hybridizer process can be defined as a mechanochemical fusion process using such a high-speed rotor.
• the hybridizer process is performed in air or under dry conditions. Thus, due to the high-speed rotation of the rotor, high-speed air flow may be generated near the rotor. However, some liquid materials may be subjected to the hybridizer process together with solid materials.
• the term "hybridizer process" has been used as a technical term.
• the hybridizer process can be performed by using a hybridization system marketed by, for example, Nara Machinery in Japan, in which at least two types of particles, typically core particles and fine particles, are fed into a hybridizer equipped with a high-speed rotor having a plurality of blades in a chamber under dry conditions, and the particles are dispersed in the chamber and mechanical and thermal energy (e.g., compression, friction and shear stress) are imparted to the particles for a relatively short period of time such as 1 to 10 minutes, preferably 1 to 5 minutes.
• one type of particles e.g., fine particles
• the other type of particles e.g., core particle
• the particles have been subjected to electrostatic treatment(s) such as shaking to form an "ordered mixture" in which one type of particles is spread to cover the other type of particles.
• electrostatic treatment(s) such as shaking
• the hybridizer process can also be performed by using a theta composer marketed by Tokuju Corporation in Japan.
• the hybridizer process can also be performed by using a Composi Hybrid or a Mechano Hybrid marketed by Nippon coke.
• small core particles, large core particles and particulate organic solid UV filter(s) as well as optionally additional material(s) such as inorganic solid UV filter(s), coloring pigment(s) and/or additional UV filter(s) if necessary can be fed into such a hybridizer to form a composite pigment.
• the hybridizer process can be performed by using a rotor rotating at about 8,000 rpm (100 m/sec) for about 3 minutes.
• the small core particle(s) and the large core particle(s) can be used in proportions such that the weight ratio of the small core particle(s) to the large core particle(s) is 10:90 to 90:10, preferably 20:80 to 80:20, and more preferably 30:70 to 70:30.
• particle(s)/the particulate organic solid UV filter(s) may be 20:50:30 to 50:20:30, preferably 35:15:50 to 15:35:50, and more preferably 10:20:70 to 20:10:70.
• particle(s)/the particulate organic solid UV filter(s) may be 50:20:30 or 35:15:50.
• the mechanochemical fusion process in particular the hybridizer process, enables to provide a composite pigment in which small core particles are at least in part covered by at least one layer comprising at least one particulate organic solid UV filter, and optionally at least one inorganic solid UV filter and or at least one coloring pigment and/or at least one additional UV filter wherein the small core particle comprises at least one organic polymer.
• the surface of the large core particles may also be at least in part covered by at least one layer comprising at least one selected from the group consisting of particulate organic solid UV filters, inorganic solid UV filters, coloring pigments and additional UV filters.
• the mechanochemical fusion process in particular the hybridizer process, can provide ordered array (e.g., uniform coverage) of particulate organic solid UV filter(s), and optionally at least one inorganic solid UV filter and/or at least one coloring pigment and/or at least one additional UV filter on small core particles and provides strong bonds at the surface of the small core particle and a coating layer comprising the particulate organic solid UV filter(s), and optionally inorganic solid UV filter(s) and/or coloring pigment(s) and/or additional UV filter(s).
• ordered array e.g., uniform coverage
• particulate organic solid UV filter(s) and optionally at least one inorganic solid UV filter and/or at least one coloring pigment and/or at least one additional UV filter on small core particles and provides strong bonds at the surface of the small core particle and a coating layer comprising the particulate organic solid UV filter(s), and optionally inorganic solid UV filter(s) and/or coloring pigment(s) and/or additional UV filter(s).
• the particulate organic solid UV filter, and optionally the inorganic solid UV filter and/or the additional UV filter and/or the coloring pigment can be effectively bound on the surface of the small core particle(s) due to the anchor effects by the collision of the large core particle(s) to the small core particle(s). Therefore, the UV filtering effects, and optionally coloring effects, can be further enhanced.
• the mechanochemical fusion process in particular the hybridizer process, is quite different from other processes using, for example, a beads mill and a jet mill.
• a beads mill causes pulverization or aggregation of core particles
• a jet mill causes pulverization of core particles and uniform coating of a core particle by fine particles is difficult to be formed.
• the composite pigment according to the present invention may be coated with a further layer comprising UV filter(s) and/or coloring material(s), preferably consisting of UV filter(s) and/or coloring material(s).
• the composite pigment, as described above, according to the present invention can be present in the cosmetic composition according to the present invention in an amount ranging from 0.01% to 99% by weight, preferably f om 0.1% to 50% by weight, and more preferably from 1% to 30% by weight, relative to the total weight of the composition.
• the composite pigment according to the present invention can be used in cosmetic compositions to be applied to keratin substances such as skin, hair, and nails, providing superior UV shielding effects, and optionally coloring effects, because the composite pigment can exhibit good UV filtering effects possibly with a transparent or clear appearance and/or good coloring effects such as more transparent or clearer and more bright coloring, without the risk of affecting keratin substances.
• the composite pigment according to the present invention is easy to be formulated into and can be stabilized in cosmetic compositions. Since the composite pigment according to the present invention can reduce free particles which have a high friction coefficient such that they do not easily spread on the skin and provide an unpleasant feeling on use, the cosmetic composition according to the present invention has reduced friction, and therefore, can provide the effect of a better feeling on use.
• the cosmetic composition according to the present invention may further comprise at least one filler and/or at least one oil.
• filler should be understood as meaning colorless natural or synthetic particles of any shape which are insoluble in the medium of the composition, whatever the temperature at which the composition is manufactured. Thus, the filler is different from the coloring pigment as described above.
• the fillers may be inorganic or organic and of any shape(for instance, platelet, spherical, and oblong shapes) and with any crystallographic form (for example, sheet, cubic, hexagonal, orthorhombic, and the like).
• suitable additional fillers include, but are not limited to, talc; mica; silica; kaolin; powders of polyamide such as Nylon®; poly-P-3-alanine powders;
• polyethylene powders polyurethane powders, such as the powder formed of hexamethylene diisocyanate and trimethylol hexyllactone copolymer sold under the name Plastic Powder D-400 by Toshiki; the powders formed of tetrafluoroethylene polymers (Teflon®); lauroyllysine; starch; boron nitride; polymeric hollow microspheres, such as microspheres of poly(vinylidene chloride)/acrylonitrile, for example Expancel® (Nobel Industrie), and microspheres of acrylic acid copolymers; silicone resin powders, for example, silsesquioxane powders (for instance, silicone resin powders disclosed in European Patent No. 0293 795 and Tospearls® from Toshiba);
• poly(methyl methacrylate) particles precipitated calcium carbonate; magnesium carbonate; basic magnesium carbonate; hydroxyapatite; hollow silica microspheres; glass microcapsules; ceramic microcapsules; metal soaps derived from organic carboxylic acids comprising from 8 to 22 carbon atoms, for example, from 12 to 18 carbon atoms, such as zinc stearate, magnesium stearate, lithium stearate, zinc laurate, and magnesium myristate; barium sulphate; and mixtures thereof.
• the filler may be present in the composition in an amount ranging from 0.1% to 80% by weight, with respect to the total weight of the composition, for example, from 1% to 25% by weight, or from 3% to 15% by weight.
• oil is understood to mean a fatty substance which is liquid at ambient temperature (25°C).
• oils which can be used in the composition of the invention for example, of hydrocarbon oils of animal origin, such as perhydrosqualene (or squalane); hydrocarbon oils of vegetable origin, such as triglycerides of caprylic/capric acids, for example those marketed by Stearineries Dubois or those marketed under the trademarks Miglyol 810, 812 and 818 by
• Dynamit Nobel or oils of vegetable origin, for example sunflower, maize, soybean, cucumber, grape seed, sesame, hazelnut, apricot, macadamia, arara, coriander, castor, avocado or jojoba oil or shea butter oil; synthetic oils; silicone oils, such as volatile or non-volatile polymethylsiloxanes (PDMSs) comprising a linear or cyclic silicone chain which are liquid or paste at ambient temperature; fluorinated oils, such as those which are partially hydrocarbon and/or silicone, for example those described in JP-A-2 -295912; ethers, such as dicaprylyl ether (CTFAname); and esters, such as benzoate C 12 -C 15 fatty alcohols (Finsolv TN from Finetex); arylalkyl benzoate derivatives, such as 2-phenylethyl benzoate (X-Tend 226 from ISP); amidated oils, such as isopropyl N-lauroylsarcosinate (Elde
• the oily phase can also comprise one or more fatty substances selected, for example, from fatty alcohols (cetyl alcohol, stearyl alcohol, cetearyl alcohol), fatty acids (stearic acid) or waxes (paraffin wax, polyethylene waxes, carnauba wax, beeswax).
• fatty alcohols cetyl alcohol, stearyl alcohol, cetearyl alcohol
• fatty acids stearic acid
• waxes paraffin wax, polyethylene waxes, carnauba wax, beeswax
• the oily phase can comprise lipophilic gelling agents, surfactants or also organic or inorganic particles.
• the oily phase can preferably represent from 1 to 70% of oil by weight, with respect to the total weight of the composition.
• composition according to the present invention may further comprise at least one additional conventional cosmetic ingredient which may be chosen, for example, from hydrophilic or lipophilic gelling and/or thickening agents, surfactants, antioxidants, fragrances, preservatives, neutralizing agents, sunscreens, vitamins, moisturizing agents, self-tanning compounds, antiwrinkle active agents, emollients, hydrophilic or lipophilic active agents, agents for combating pollution and/or free radicals, sequestering agents, film-forming agents, dermo-decontracting active agents, soothing agents, agents which stimulate the synthesis of dermal or epidermal macromolecules and/or which prevent their decomposition, antiglycation agents, agents which combat irritation, desquamating agents, depigmenting agents, antipigmenting agents,
• additional conventional cosmetic ingredient which may be chosen, for example, from hydrophilic or lipophilic gelling and/or thickening agents, surfactants, antioxidants, fragrances, preservatives, neutralizing agents, sunscreens, vitamins, moisturizing agents
• propigmenting agents NO-synthase inhibitors, agents which stimulate the proliferation of fibroblasts and/or keratinocytes and/or the differentiation of keratinocytes, agents which act on microcirculation, agents which act on energy metabolism of the cells, healing agents, and mixtures thereof.
• the composition according to the present invention may be in various forms, for example, suspensions, dispersions, solutions, gels, emulsions, such as oil-in- water (O/W), water-in-oil (W/O), and multiple (e.g., W/O/W, polyol/O/W, and 0/W/O) emulsions, creams, foams, sticks, dispersions of vesicles, for instance, of ionic and/or nonionic lipids, two-phase and multi-phase lotions, sprays, powders, and pastes.
• the composition may be anhydrous, for example, it can be an anhydrous paste or stick.
• the composition may also be a leave-in composition.
• the cosmetic composition according to the present invention may be in the form of a powdery composition or a liquid or solid composition, such as an oily-solid cosmetic composition or an anhydrous composition.
• the powdery cosmetic composition according to the present invention can have reduced friction which provides a smooth feeling to use, and can have good compactability which provides high stability against physical impact, due to the inclusion of the composite pigment according to the present invention.
• the powdery cosmetic composition according to the present invention can show preferable cosmetic effects such as good fitting to the skin, homogeneous appearance, hiding the color of the skin, hiding the pores and lines on the skin, making the pores and lines on the skin less remarkable, and matt appearance, due to the inclusion of the composite pigment according to the present invention.
• the liquid cosmetic composition according to the present invention can show good visual optical effects such as matt and haze effects, due to the inclusion of the composite pigment according to the present invention.
• the powdery and liquid cosmetic composition according to the present invention has better UV filtering effects, and optionally better coloring effects, in addition to reduce the risk of fine particles of inorganic solid UV filter(s) and optional coloring pigment(s) penetrating into the skin via pores on the skin.
• the cosmetic composition according to the present invention may be in the form of, for example, a compact powder, a lotion, a serum, a milk, a cream, a base foundation, an undercoat, a make-up base coat, a foundation, a face powder, cheek rouge, a lipstick, a lip cream, an eye shadow, an eyeliner, a loose powder, a concealer, a nail coat, mascara, a sunscreen and the like.
• the cosmetic composition according to the present invention may be in the form of a foam.
• the cosmetic composition according to the present invention can be packaged in a foam dispenser. It can involve either products referred to as "aerosols" dispensed from a pressurized container by means of a propellant gas and thus forming a foam at the time of their dispensing, or products dispensed from a container by means of a mechanical pump connected to a dispensing head where the passage of the cosmetic composition through the dispensing head transforms it into a foam in the area of the outlet orifice of such a head at the latest.
• aerosols products dispensed from a pressurized container by means of a propellant gas and thus forming a foam at the time of their dispensing
• products dispensed from a container by means of a mechanical pump connected to a dispensing head where the passage of the cosmetic composition through the dispensing head transforms it into a foam in the area of the outlet orifice of such a head at the latest.
• the dispenser can be an aerosol furthermore containing the cosmetic composition according to the present invention; and a propellant gas.
• propellant means any compound that is gaseous at a temperature of 20°C and at atmospheric pressure, and that can be stored under pressure in liquid or gaseous form in an aerosol container.
• the propellant may be chosen from optionally halogenated volatile hydrocarbons, such as n-butane, propane, isobutane, pentane or a halogenated hydrocarbon, and mixtures thereof. Carbon dioxide, nitrous oxide, dimethyl ether (DME), nitrogen or compressed air may also be used as propellant. Mixtures of propellants may also be used. Dimethyl ether and/or non-halogenated volatile hydrocarbons are preferably used.
• the propellant gas which can be used may be chosen among the previously mentioned gases and in particular among carbon dioxide, nitrogen, nitrogen oxide, dimethyl ether, volatile
• the cosmetic composition according to the present invention can be in a "pump bottle” type foam dispenser.
• These dispensers include a dispensing head for delivering the cosmetic composition, a pump and a plunger tube for transferring the cosmetic composition from the container, into the head, for dispensing the product.
• the foam is formed by forcing the cosmetic composition to pass through a material including a porous substance such as a sintered material, a filtering grid of plastic or metal, or similar structures.
• Tinosorb-M was marketed by BASF as an aqueous dispersion, Tinosorb-M was dried out to evaporate water in the liquid to obtain a powder of methylene bis-benzotriazolyl
• the obtained powder was used for the above-hybridizer process.
• As Control the dried Tinosorb-M was used.
• a solvent was prepared by mixing isododecane and polyhydroxystearic acid such that the concentration of polyhydroxystearic acid was 3 wt%.
• the obtained sample was put into a quartz cell having a 2 mm light pathway.
• the UV absorbance of the sample in the wavelength of from 280 to 315 nm (UV-B) and from 315 to 400 nm (UV-A) was measured by use of a UV/VIS spectrophotometer type V-550 (JASCO, Japan).
• Example 1 Since a relatively large amount of the 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. Since organic UV filter particles easily form aggregations which are difficult to show good UV absorption, it is surprising to observe that a relatively large amount of the powdery organic UV filter (Dried Tinosorb-M) can exert higher UV-A and UB-B absorbance for the composite pigment according to Example 1. Since Comparative Examples 1 and 2 use Ti0 2 , the UV-A and UB-B absorbance of the composite pigments according to Comparative Examples 1 and 2 is smaller than those of the composite pigments according to Example 1 and 2, respectively. This tendency did not change even though the large core particle in Comparative Examples 1 and 2 was replaced with the polyamide particle. [Visible Light Transmittance Evaluation]
• Visible light transmittance of each of the composite pigments according to Examples 1 and 2, and each of Comparative Examples 1 to 4 was measured by use of a UV/VIS spectrophotometer type V-550 (JASCO, Japan) as follows.
• a solvent was prepared by mixing isododecane and polyhydroxystearic acid such that the concentration of polyhydroxystearic acid was 3 wt%.
• the obtained sample was put into a quartz cell having a 2 mm light pathway.
• the transmittance in the visible light region of the sample in the wavelength of from 400 to 700 nm was measured by use of a UV VIS spectrophotometer type V-550 (JASCO, Japan).
• the total transmission value was obtained as an average of transmittance in the visible light region in the wavelength of from 400 to 700 nm.

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• 2012
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