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
  • A61K8/02—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
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/0241—Containing particulates characterized by their shape and/or structure
  • A61K8/0279—Porous; Hollow
• • 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
  • A61K8/04—Dispersions; Emulsions
  • A61K8/042—Gels
• • 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
  • A61K8/04—Dispersions; Emulsions
  • A61K8/06—Emulsions
  • A61K8/062—Oil-in-water emulsions
• • 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
  • A61K8/04—Dispersions; Emulsions
  • A61K8/06—Emulsions
  • A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone emulsions
• • 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
  • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
• • 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
  • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
  • A61K8/25—Silicon; Compounds thereof
• • 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
  • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
  • A61K8/27—Zinc; Compounds thereof
• • 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
  • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
  • A61K8/29—Titanium; Compounds thereof
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
  • A61Q1/02—Preparations containing skin colorants, e.g. pigments
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/005—Preparations for sensitive skin
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/008—Preparations for oily skin
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/02—Preparations for care of the skin for chemically bleaching or whitening the skin
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/08—Anti-ageing preparations
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
• • 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
  • A61K2800/41—Particular ingredients further characterized by their size
  • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
• • 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
  • A61K2800/42—Colour properties
  • A61K2800/43—Pigments; Dyes

Definitions

• the present invention relates to the cosmetic use of porous spheres with closed porosity of metal oxide to improve the aesthetic appearance and the comfort of the skin, of the skin appendages, in particular of the hair and/or of the mucous membranes, as well as said cosmetic compositions and the methods of cosmetic treatment which result therefrom.
• the present invention also relates to pharmaceutical compositions, in particular dermatological compositions, comprising porous spheres with closed porosity of metal oxide to improve the comfort of the skin, skin appendages and/or mucous membranes exhibiting a pathological state.
• Intrinsic factors contribute to their appearance, in particular stress, hormonal variations, taking weight, dieting, dehydration and aging.
• Genetics in particular the type of skin (sensitive, hyperseborrhoeic, reactive, etc.) and ethnic origin, for example Caucasian, Asian or African, also plays an important role in the appearance of certain manifestations.
• the unsightly cutaneous manifestations are in particular wrinkles and fine lines, such as, for example, frown lines and crow's feet. They can be expression lines or aging lines. These are initially superficial and then become deeper, such as the nasolabial folds.
• the cutaneous manifestations also include signs of loss of volume, in particular sagging skin, sagging facial contours leading to sagging facial features which give a sad or tired appearance, or even loss of density which results in thinner, more fragile skin, which is accompanied by a loss of radiance and/or a so-called dull complexion.
• unsightly skin manifestations also include manifestations of color, shine and pigmentation such as loss of evenness of complexion, radiance, dark circles, puffiness, redness, brown spots or age or white spots, in particular vitiligo, rosacea, pregnancy mask, melasma, nevus, angioma. They also include skin imperfections such as blackheads, visible pores, pimples, scars including acne marks, burn marks, wounds, stretch marks but also rough skin and flaking. At the level of the mucous membranes, the unsightly manifestations are generally signs of dehydration such as scales and/or cracks. At the level of the hair, the unsightly manifestations are generally dull, depigmented, brittle, difficult to comb hair, in particular unruly, with split ends.
• the blurring effect or "soft focus” in the cosmetics industry is used in anti-aging creams and in make-up. Skin surface imperfections such as fine lines and wrinkles make skin appear uneven by trapping light in the micro-crevices formed by wrinkles. The trapped light is then absorbed and generates dark spots which will appear on the surface of the skin.
• Total transmittance is influenced by light absorption and reflection while Haze is influenced by light scattering.
• Haze is an important appearance attribute as it directly affects human perception and plays an important role in consumer demand. It translates the degree of blurring or haze of a transparent material. Its value is expressed as a percentage. The higher its value, the greater the blurring.
• Porous metal oxide spheres have already been described in patent applications WO2020/183108 and WO2020/182936 in the context of cosmetic applications and in particular for improving the appearance of the skin, skin appendages and/or mucous membranes, in particular by masking unsightly manifestations.
• these spheres have an open porosity and therefore do not have closed pores as illustrated in FIG. IB.
• the % of closed pores by volume of these spheres is thus less than 5%.
• closed porosity porous spheres of metal oxide have an improved effect on masking imperfections compared to the open porosity porous spheres of the prior art. Indeed, such spheres have a higher value of total transmittance and of haze or diffusion (“haze”), thus making it possible to improve their blurring/masking (“soft focus”) property.
• haze total transmittance and of haze or diffusion
• soft focus blurring/masking
• such spheres are easier to formulate because the external formulation medium, and in particular the compounds present in this medium, cannot penetrate them, which allows them to keep a constant net refractive index regardless of the formulation medium and/or the type of formulation and therefore to avoid a modification of their optical property and therefore of their masking property depending on the formulation medium used.
• the spheres according to the invention offer the advantage of being suitable for all skin types, regardless of type, complexion and radiance. Another advantage of the present invention is that the spheres have great stability and can be used in powder form or in composition. They are inert, which makes it possible to formulate them easily in any kind of cosmetic or dermatological compositions, whether these are lipophilic or hydrophilic.
• a subject of the present invention is thus the non-therapeutic cosmetic use of porous spheres with closed porosity comprising a metal oxide to improve the appearance and/or the comfort of the skin, of the skin appendages, in particular the hair, and/or of the mucous membranes.
• the size distribution of the closed pores of the spheres according to the invention is monodisperse or bimodal, advantageously monodisperse.
• the porous spheres with closed porosity according to the invention have an average diameter measured by scanning electron microscopy (SEM) ranging from 1 ⁇ m to 100 ⁇ m and/or an average porosity ranging from >0.10 to 0.80 and/or an average pore diameter, in particular of closed pores, measured by scanning electron microscopy (SEM) ranging from 50 nm to 800 nm, advantageously from 50 nm to 500nm.
• SEM scanning electron microscopy
• the porous spheres with closed porosity according to the invention have an average diameter measured by scanning electron microscopy (SEM) ranging from 1 ⁇ m to 100 ⁇ m and an average porosity ranging from >0.10 to 0.80 and an average diameter of pores, in particular of closed pores, measured by scanning electron microscopy (SEM) ranging from 50 nm to 800 nm.
• SEM scanning electron microscopy
• the metal oxide of the porous spheres with closed porosity according to the invention is chosen from silicon, titanium, aluminum, zirconium, cerium, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, mixed metal oxide and their combinations, preferentially silicon, titanium, aluminum and zinc oxide and their combinations, even more preferentially silicon oxide, titanium and their combinations. , particularly advantageously, silicon oxide.
• the porous spheres with closed porosity according to the invention comprise from 60% by weight to 99.9% by weight of metal oxide and from 0.1% by weight to 40% by weight of light-absorbing agents, by total weight of the spheres, advantageously from 0.1% by weight to 40% by weight of carbon black.
• the porous spheres with closed porosity according to the invention have an average diameter measured by scanning electron microscopy (SEM) ranging from 1 ⁇ m to 100 ⁇ m and an average pore diameter measured by scanning electron microscopy (SEM) ranging from 50 nm to 800 nm.
• SEM scanning electron microscopy
• the porous spheres with closed porosity according to the invention have an average diameter measured by scanning electron microscopy (SEM) ranging from 1 ⁇ m to 75 ⁇ m and an average porosity ranging from 0.45 to 0.70, preferentially from 0.5 to 0.65.
• SEM scanning electron microscopy
• the porous spheres with closed porosity according to the invention have an average diameter measured by scanning electron microscopy (SEM) ranging from 2.5 ⁇ m to 8 ⁇ m, an average porosity ranging from 0.45 to 0.70 and an average pore diameter, in particular of closed pores, measured by scanning electron microscopy (SEM) ranging from 100nm to 200nm.
• SEM scanning electron microscopy
• the use according to the invention is to reduce the visibility of unsightly manifestations of the skin, skin appendages and/or mucous membranes, in particular irregularities in the relief and/or texture of the skin, mucous membranes and/or skin appendages, and/or irregularities in the color of the skin and/or mucous membranes.
• the porous spheres with closed porosity according to the invention are present in a cosmetic composition, at a concentration ranging from 1x10 3 to 10% by weight, preferably from 0.5% to 5% by weight relative to the total weight of the composition.
• the use according to the invention is for improving the organoleptic properties of the cosmetic composition.
• a subject of the present invention is also a cosmetic care process for improving the appearance and/or the comfort of the skin, of the skin appendages, in particular the hair, and/or of the mucous membranes, comprising the topical application to at least one area of the skin and/or of the skin appendages and/or of the mucous membranes of porous spheres with closed porosity comprising a metal oxide and/or of a cosmetic composition comprising them.
• porous spheres with closed porosity are as described above.
• the cosmetic care process according to the invention is for reducing the visibility of unsightly manifestations of the skin, skin appendages and/or mucous membranes, in particular irregularities in the relief and/or texture of the skin, mucous membranes and/or appendages. cutaneous, and/or irregularities in the color of the skin and/or mucous membranes.
• the area of skin of the body and/or the appendix of the skin and/or mucosa is chosen from the skin of the face, including the forehead, the cheeks, the nose, the temples, the so-called "T" area (forehead, nose and chin), under the eyes, the periorbital area, in particular dark circles, the chin, the scalp, the neck, the back, the shoulders, the arms, the forearms, the thorax, the hands, the hair, the beard, eyelashes, eyebrows, bust, in particular the neckline, stomach and/or armpits, legs, feet, hands, neck, thighs, hips, buttocks, waist, torso, lip contour, hair, hair and/or ocular, labial and/or oral mucosa, preferably the skin of the face, hands, neckline.
• a subject of the present invention is also the cosmetic compositions containing these porous spheres with closed porosity, in particular for the uses mentioned, and optionally a cosmetically acceptable excipient.
• the cosmetic composition according to the invention is in the form of a serum, a lotion, a cream, a shampoo, a conditioner, an oil, a milk, an ointment, a paste, a mousse, an emulsion, a hydrogel, a shower gel, a mask, a lacquer, a spray, a wax, a powder, in particular make-up, or a stick.
• the cosmetic composition according to the invention is in the form of a slightly gelled composition and/or comprises an oily phase, preferably it is of the oily composition or oil-in-water or water-in-oil emulsion or lotion type.
• the present invention also relates to pharmaceutical compositions, in particular dermatological compositions containing these porous spheres with closed porosity, and optionally an excipient pharmaceutically acceptable, in particular dermatologically acceptable.
• the present invention also relates to a pharmaceutical composition according to the invention, preferably dermatological, for its use to improve the comfort of the skin, appendages and / or mucous membranes, in particular having a pathological state, in particular manifested by a loss of homogeneity and / or deregulation and / or irregularity of the color, complexion, sebum secretion and / or relief, such as hyperpigmented, hypopigmented, hyperseborrheic skin , reactive, inflammatory, atopic, in particular skin affected by vitiligo, melanoma, rosacea, telangiectasia, acne, rosacea, urticaria, psoriasis, herpes, impetigo, ecthyma, erysipelas, and/or with wounds and/or scars, in particular acne, pimples, boils, varicose veins, melasma, follicles itis, abscesses, any combination
• the present invention also relates to the use of porous spheres with closed porosity according to the invention for the preparation of a pharmaceutical composition according to the invention, preferably dermatological, intended to improve the comfort of the skin, appendages and/or mucous membranes, in particular having a pathological state, in particular manifested by a loss of homogeneity and/or a deregulation and/or an irregularity of the color, of the complexion, of the secretion of sebum and/or of the relief, such as hyperpigmented, hypopigmented, hyperseborrheic, reactive, inflammatory, atopic skin, in particular skin affected by vitiligo, melanoma, rosacea, telangiectasia, acne, rosacea, urticaria, psoriasis, herpes, impetigo, ecthyma, erysipelas, and/or presenting wounds and/or scars, in particular acne, pimples , boils, varicos
• the use according to the invention is preferentially cosmetic, and by topical application to at least one zone concerned or a part of healthy skin, healthy mucous membrane and/or healthy skin appendages, preferentially the hair, preferentially in humans.
• the term “cosmetic use” means a non-therapeutic, non-pharmaceutical use of the spheres according to the invention, preferably on healthy skin, in particular a healthy scalp, and/or healthy skin appendages, in particular healthy hair, and/or healthy mucous membranes.
• part of skin, preferably scalp, and/or mucosa and/or skin appendages, and/or area of skin, preferably scalp, and/or mucosa and/or so-called "healthy" skin appendages means a part of the skin, preferably scalp, and/or mucosa and/or skin appendages, and/or an area of skin, preferably scalp, and/or mucosa and/or skin appendages qualified non-pathological by a dermatologist, that is to say, which does not present with infection, inflammation, in particular in the form of sunburn, disease or skin conditions such as folliculitis, candidiasis, psoriasis, ichthyosis, eczema, acne, impetigo, boils, abscesses, herpes, ecthyma, erysipelas or dermatitis, varicose veins, rosacea or telangiectasia, pathology
• topical application means applying the spheres according to the present invention optionally in the form of active ingredient and / or composition on the surface of the skin including the scalp, the skin appendages in particular the hair, and / or the mucous membranes in particular by direct application or by vaporization.
• the term “improving the appearance” means reducing or reducing the visibility of the unsightly manifestations, in particular masking them, hiding them, preferentially those present on the face, in particular by filling and/or by optical effect.
• "unsightly manifestations” are unsightly irregularities in the relief and/or texture of the skin, mucous membranes and/or skin appendages and/or irregularities in the color of the skin, mucous membranes and/or skin appendages.
• the unsightly irregularities in the relief and texture of the skin are wrinkles and fine lines, in particular frown lines and crow's feet, asperities, blackheads, dilated pores, rough appearance, marks and scars, in particular those due to injuries, acne, pimples, burns and/or stretch marks.
• the irregularities in the color of the skin are pigment spots, in particular white or dark spots, in particular age spots or hyperpigmented or depigmented spots, pregnancy mask, moles, melanomas, freckles, redness, but also loss of complexion radiance, dull complexion, dark circles and puffiness, rosacea, rosacea.
• the unsightly manifestations are selected from wrinkles, fine lines, blackheads, pores visible, loss of complexion radiance, dullness, dark circles, puffiness, pigment spots and any combination thereof.
• the unsightly manifestations of the cutaneous appendages, preferentially of the hair, are dull, brittle.
• the manifestations also include the brittle, crumbly, damaged appearance and/or the difficulty in shaping them, in particular for the hair, in combing them, and/or split ends.
• the unsightly manifestations of the mucous membranes include a dull, cracked, withered and/or damaged appearance as well as scales.
• the improvement in unsightly manifestations can be visualized and evaluated by microscopy and/or by high-resolution photography analysis with, in particular, measurement of the shine of the area of skin, mucosa and/or skin appendages.
• the metal oxides include transition metal oxides, metalloids and earth metals compatible with cosmetic and/or dermatological use, such as for example silica, titanium, alumina, zirconia, cerium, iron oxide, zinc oxide, indium oxide, tin oxide, chromium oxide, mixed metal oxide, combinations thereof.
• the metal oxide is preferably chosen from the group consisting of SiO 2 , TiO 2 , ZnO and their mixtures, advantageously from the group consisting of SiO 2 , TiO 2 and ZnO, more advantageously from the group consisting of SiO 2 , ZnO and their mixtures, even more advantageously from the group consisting of SiO 2 and ZnO, in particular it is SiO 2 .
• the metal oxides do not include TiO 2 and/or a mixture of several metal oxides.
• the porous spheres with closed porosity according to the invention in particular of which at least 90% of the pores are closed pores, have an average diameter measured by scanning electron microscopy (SEM) ranging from 1 ⁇ m to 100 ⁇ m and an average pore diameter measured by scanning electron microscopy (SEM) ranging from 50 nm to 800 nm and comprise at least 70% metal oxide.
• SEM scanning electron microscopy
• the porous spheres with closed porosity according to the invention can comprise, for example, from 60% by weight to 99.9% by weight of metal oxide and from 0.1% by weight to 40% by weight of light-absorbing agents, by total weight of the spheres.
• the porous spheres with closed porosity according to the invention contain 0.3%, preferably 0.5%, preferably at least 1%, more preferably at least 5% by weight of light-absorbing agents, relative to the total weight of the spheres.
• the porous spheres with closed porosity according to the invention do not contain any light absorber and/or the cosmetic composition which contains them does not contain any light absorber either.
• light absorbers such as TiCh can present a certain toxicity.
• the inventors have surprisingly discovered that even without a light absorber, the microspheres or spheres according to the invention have an immediate anti-blue light filter effect.
• the light-absorbing agent(s) are selected from the group consisting of organic and inorganic pigments, compatible with a cosmetic and/or dermatological application, in particular on the skin, the mucous membranes and/or the skin appendages, more particularly it is carbon black.
• the porous spheres with closed porosity according to the invention have an average diameter measured by scanning electron microscopy (SEM) ranging from 0.5 ⁇ m to 100 ⁇ m, advantageously from 1 ⁇ m to 100 ⁇ m. in this case they are microspheres.
• SEM scanning electron microscopy
• they are not nanospheres in order to avoid their penetration into the deep layers of the skin and/or of the mucous membranes and to preferentially have a surface effect.
• THE microspheres according to the invention therefore advantageously remain on the surface of the skin and/or of the mucous membranes and/or of the skin appendages.
• micro-scale By “on a micrometric scale” or “micro-” is meant a size ranging from about 0.5 ⁇ m to about 999 ⁇ m.
• nano-scale By “nano-scale” or “nano-” is meant a size ranging from about 1 nm to about 999 nm.
• the porous spheres with closed porosity according to the invention have an average diameter measured by scanning electron microscopy (SEM) ranging from 1 ⁇ m to 75 ⁇ m, preferentially from 2 ⁇ m to 70 ⁇ m, preferentially from 3 ⁇ m to 65 ⁇ m, from 4 ⁇ m to 60 ⁇ m, from 5 ⁇ m to 55 ⁇ m or from 5 ⁇ m to 50 ⁇ m, more preferably from 10 ⁇ m to 25 ⁇ m, for example an average diameter measured by micro scanning electron microscope (SEM) selected from 1 pm, 2 pm, 3 pm, 4 pm, 5 pm, 6 pm, 7 pm, 8 pm, 9 pm, 10 pm, 11 pm, 12 pm, 13 pm, 14 pm, 15 pm, 16 pm, 17 pm, 18 pm, 19 pm, 20 pm, 21 pm, 22 pm, 23 pm, 24 pm, 25 pm 26 pm, I pm, 28 pm, 29 pm or 30 pm.
• SEM scanning electron microscopy
• the porous spheres with closed porosity according to the invention have an average diameter measured by scanning electron microscopy (SEM) ranging from 1.3 ⁇ m to 10 ⁇ m, more particularly from 1.5 to 9.9 ⁇ m, even more particularly from 2.5 ⁇ m to 8 ⁇ m, for example an average diameter chosen from 1 ⁇ m, 2 ⁇ m, 2.6 ⁇ m, 2.9 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6pm, 6.7pm, 7pm, 8pm, 9pm, 10pm.
• SEM scanning electron microscopy
• the average diameter of pores, in particular of closed pores, of the porous spheres with closed porosity according to the invention, measured by scanning electron microscopy (SEM), ranges from 50 nm to 800 nm, advantageously from 50 nm to 500 nm, advantageously from 80 nm to 250 nm, advantageously from 100 nm to 245 nm, in particular from 100 nm to 200 nm, more particularly from 145 nm to 180 nm, more particularly from 150 nm to 160 nm, even more particularly from 150 nm to 155 nm, for example chosen from: 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, 105 nm, HOnm, 115 nm, 120 nm, 125 nm, 130 nm m, 135
• the porous spheres according to the invention have an average diameter measured by scanning electron microscopy (SEM) ranging from 1.3 ⁇ m to 10 ⁇ m, more particularly from 1.5 to 9.9 ⁇ m, even more particularly from 2.5 ⁇ m to 8 ⁇ m, for example an average diameter chosen from 1 ⁇ m, 2 ⁇ m, 2.6 ⁇ m, 2.9 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 6 ⁇ m 7 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m; and an average porosity chosen from 0.45, 0.47, 0.49, 0.50, 0.51, 0.53, 0.55, 0.57, 0.59, 0.61, 0.63, 0.65, 0.67, 0.69 or 0.70; and an average pore diameter measured by scanning electron microscopy (SEM) from 100 nm to 200 nm, more particularly from 145 nm to 180 nm, more particularly from 150 nm to 160 nm, even more particularly from 150
• SEM
• the mean diameter of the spheres is markedly larger than the mean diameter of the pores.
• the average diameter of the spheres is in general at least 25 times, preferentially at least 30 times, preferentially at least 35 times, more preferentially 4 times greater than the average diameter of the pores.
• the ratio of the average sphere diameter to the average pore diameter is at least 40/1, at least 50/1, at least 60/1, at least 70/1, at least 80/1, at least 90/1, at least 100/1, at least 110/1, at least 120/1, at least 130/1, at least
• the porous spheres with closed porosity according to the invention have an average porosity ranging from >0.10 to 0.80, in particular chosen from: 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.60, 0.61, 0.62, 0.63, 0.64, 0.65, 0.66, 0.67, 0.68, 0.69 or 0.70, preferably ranging from 0.45 to 0.70, more preferably 0.50 to 0.65.
• the size of the spheres and/or the pores is a synonym of the diameter of the spheres and/or the pores and is determined by scanning electron microscopy (SEM).
• the mean diameter of the spheres and/or the pores (or mean size) is understood to mean the mean diameter of the spheres and/or the pores, which can be supplemented by measuring the standard deviation. It is obtained by analyzing 100 to 150 spheres and/or 50 to 70 pores of different spheres by scanning electron microscopy using image analysis software in particular ImageJ software.
• the average porosity of a sphere refers to the total pore volume, as a fraction of the volume of the entire sphere.
• the average porosity can also be called "volume fraction". It is a dimensionless quantity. It is calculated by the ratio between the volume of the unoccupied space (inside the pores) and the total volume of the sphere.
• a porous silica sphere according to the invention having an average diameter of 7.6 ⁇ m and containing closed pores with an average diameter of 165 nm has an average porosity of 0.8.
• the diameter of the pores is determined by the diameter D50 of the polymers of nanoparticles which compose it. The larger the diameter D50 of the nanoparticle polymers that compose it, the larger the average diameter of the pores.
• the concentration of the nanoparticles is adjusted according to the average diameter of the spheres that it is desired to obtain. The higher the concentration of nanoparticles, the larger the size of the spheres.
• a mercury porosimetry analysis is used to characterize the porosity of the spheres.
• Mercury porosimetry consists of applying a controlled pressure in the sample to be measured immersed in mercury. External pressure is applied so that the mercury penetrates the pores/holes of the material. The amount of pressure needed is inversely proportional to the size of the pores/holes.
• the mercury porosimeter then provides pore volume and size distributions. The mercury porosimeter generates volume and pore size distributions from pressure data against intrusion data generated by the instrument using Washburn's equation.
• the spheres according to the invention do not contain and/or are not used in combination with an anti-blue light filter and/or an anti-UV filter and/or a sunscreen and/or in a cosmetic composition which contains them.
• the spheres according to the invention are not used as a booster for anti-blue light filters and/or for increasing the SPF (sun protection factor) of a sunscreen composition.
• the porous spheres according to the invention do not comprise a coating layer on their surface containing a hydrophobic compound. In a particularly advantageous embodiment, the porous spheres according to the invention do not include a coating layer on their surface.
• the porous spheres according to the invention do not comprise a coating layer on their surface containing a polyorganosiloxane, in particular a silicone compound.
• the porous spheres comprising a metal oxide can be prepared using a mold made of polymers commonly referred to as a “polymer template” or sacrificial polymer model. Such porous spheres show a color observable by the human eye, that is to say a color observable with the naked eye, or can appear white.
• a color observable with the naked eye means a color that is perceived by a majority of people. This can be for any sample of spheres according to the invention distributed over a given surface, for example, over 1 cm 2 , 2 cm 2 , 3 cm 2 , 4 cm 2 , 5 cm 2 or 6 cm 2 , 7 cm 2 , 8 cm 2 , 9 cm 2 , 10 cm 2 , 11 cm 2 , 12 cm 2 , 13 cm 2 , 14 cm 2 or 15 cm 2 . It can also mean that it is observable by the CIE 1931 Standard Observing Model 2° and/or by the CIE 1964 Standard Observing Model 10°.
• the color observation background can be of different kinds, for example white, black, or any intermediate between black and white.
• Step 1 liquid droplets are generated from a dispersion of particles, said dispersion comprising first particles (a) comprising a polymer and second particles (b) comprising a metal oxide or a metal oxide precursor.
• This dispersion of particles is advantageously an aqueous dispersion at a pH in the range 8-10, in particular a colloidal dispersion.
• Step 2 the droplets are dried so as to remove the solvent in order to provide dry spheres in the form of a matrix of the second particles (b) or of the sol-gel matrix (b) within which there are first particles (a).
• first particles (a) There is indeed a self-assembly between the first particles (a) and the second particles (b) or the sol-gel matrix (b) to form spheres having a matrix based on metal oxide or metal oxide precursor in which the polymer particles (a) are embedded.
• the spheres obtained are recovered, for example by filtration or centrifugation.
• the drying is carried out according to conventional techniques, for example by microwave irradiation, in a thermal oven, under vacuum, in the presence of a dehydrating/absorbing agent or a mixture of these techniques.
• the spheres according to the invention can be used, optionally in a cosmetic or pharmaceutical composition, preferably dermatological, as the sole agent for improving the appearance, in particular the unsightly manifestations and/or the comfort of the skin, appendages and/or mucous membranes, or in combination with other active agents having the same properties or complementary and conventional properties in cosmetic or dermatological compositions, such as those chosen from:
• the porous spheres according to the invention are used in regular topical application and preferentially at least once a day, advantageously twice a day.
• the cosmetic composition is applied to the skin.
• the spheres can be used in powder but also in the form of a cosmetic ingredient formulated in liquid form.
• the spheres are then preferentially placed in suspension in glycerine and/or in another solvent, in particular polar solvent such as water, alcohols, in particular propanediol, glycols in particular butylene glycol, propylene glycol, polyols or a mixture of these, preferentially a mixture hydroglycolic, more preferably containing a glycol chosen from butylene glycol, propylene glycol, caprylyl glycol, hexylene glycol and mixtures thereof.
• the spheres according to the invention are suspended in an aqueous solution containing glycerin, hexylene glycol, caprylyl glycol or a mixture thereof.
• the invention also relates to a cosmetic treatment method for improving the appearance and/or the comfort of the skin, of the skin appendages, in particular the hair, and/or of the mucous membranes, of an individual who needs/wants it, comprising the steps:
• a cosmetic composition containing the spheres according to the invention in an amount effective to improve the appearance and/or comfort of this area of skin and/or mucous membranes and/or skin appendages, preferably hair, namely advantageously in a content of spheres comprised between 1x10 3 to 100% by weight, and advantageously ranging from 1x10 -2 to 9 5%, preferably ranging from 0.01% to 80%, more preferably from 0.05% up to 50%, preferably from 0.1% up to 30%, preferably up to 20%, even more preferably up to 10%, and even more preferably from 0.5% to 5% by weight relative to the total weight of the composition.
• the spheres according to the invention can also be used to improve the comfort of the skin, the mucous membranes and/or the cutaneous appendages presenting a pathology.
• the skin, the mucous membranes and/or the cutaneous appendages are preferentially altered, in particular in the context of a pathology selected from the group consisting of reactive, inflammatory, atopic skin, hyperpigmented, hypopigmented, hyperseborrheic skin, in particular skin affected by vitiligo, melanoma, rosacea, telangiectasia, acne, rosacea, urticaria, psoriasis, herpes, impetigo, ecthyma, erysipelas, and/or presenting sores and/or or scars including acne, pimples, boils, varicose veins, melasma, folliculitis, abscesses, any combination thereof.
• a pathology selected from the group consisting of reactive, inflammatory, atopic skin, hyperpigmented, hypopigmented, hyperseborrheic skin, in particular skin affected by vitiligo, melanoma,
• the spheres according to the invention are in the form of a pharmaceutical composition further comprising a pharmaceutically acceptable excipient and are present in the pharmaceutical composition in a sphere content of between 1x10 3 to 100% by weight, and advantageously ranging from 1x10 -2 to 95%, preferably ranging from 0.01% to 80%, more preferably from 0.05% up to 5 0%, preferably from 0.1% up to 30%, preferably up to 20%, more preferably up to 10%, and even more preferably from 0.5% to 5% by weight relative to the total weight of the composition.
• FIG. IA represents a cross-sectional view of a sphere according to the invention with closed porosity
• FIG. IB a view of a porous sphere of the prior art, in particular according to applications WO2020/183108 and WO2020/182936.
• FIG. 2 shows an SEM image of a porous sphere according to the invention obtained according to example 1 (top image) as well as a cross section of this sphere (bottom image).
• FIG. 3 shows an SEM image of a porous sphere according to the invention obtained according to example 2 (top image) as well as a cross section of this sphere (bottom image).
• Figure 4 shows an SEM image of a porous sphere according to the invention obtained according to example 7.
• Example 1 Porous silica spheres with closed porosity according to the invention
• An aqueous dispersion of positively charged poly(meth)acrylate nanoparticles with a diameter D 50 of 210nm measured by dynamic light scattering (DLS) was diluted to 1% (w/w) with deionized water and 3% (w/w) of negatively charged silica nanoparticles having a diameter D 50 of 7nm measured by SEM were added. The mixture was sonicated for 30 seconds to prevent agglomeration.
• the dispersion loaded with nanoparticles and the oily phase (continuous oily phase containing 2% (w/w) of polyethylene-glycol-co-perfluoro polyester surfactant in fluorinated oil) were each injected into a microfluidic device having a junction making it possible to obtain a droplet size of 50 ⁇ m via syringes associated with pumps. The whole is left to equilibrium until monodisperse droplets are produced. These are then collected in a tank.
• the collected droplets are then dried in an oven at 50° C. for 4 hours to provide dry spheres (dry powder). These spheres are then calcined by placing them on a silicone plate, and heating them from room temperature to 500°C for a period of 4 hours, then maintaining the temperature at 500°C for 2 hours. The spheres are left to cool at room temperature for 4 hours.
• the porous monodispersed silica oxide spheres with closed porosity thus obtained have an average diameter of 15 microns measured by scanning electron microscopy (SEM) and an average porosity measured by mercury porosimetry of 0.55.
• FIG. 2 An SEM image of one of the obtained spheres (top image) together with its cross-section (bottom image) is presented in Fig. 2.
• the cross-section clearly shows the interior of the sphere structure comprising a relatively monodisperse and ordered closed pore network. 97% by volume of the pores of these spheres are closed pores.
• Example 1 can be repeated by carrying out the drying step by microwave irradiation, by drying under vacuum and/or in the presence of a dehydrating agent.
• Example 2 Porous silica spheres with closed porosity according to the invention obtained by atomization
• An aqueous suspension of positively charged spherical nanoparticles of methyl methacrylate copolymer and 2-(methacryloyloxy)ethyl]trimethylammonium chloride having a diameter D 50 measured by dynamic light scattering (DLS) measurement of 210 nm and negatively charged silica nanoparticles (average diameter measured by scanning electron microscopy (SEM) of 7 nm) was prepared.
• the aqueous suspension is dried by atomization under a nitrogen atmosphere (inlet temperature: 100° C., outlet temperature: 45° C., feed rate: 10 mL/min, atomization gas pressure 40 mm) using a BÜCHI laboratory size atomizer.
• microspheres obtained are then calcined in a muffle furnace, in order to sinter and densify the silica nanoparticles and to remove the polymer, by placing them on a silicone plate and by carrying out a temperature rise from ambient temperature to 550° C. for a period of 5 hours, then by maintaining the temperature at 550° C. for 2 hours, then finally by lowering the temperature from 550° C. to ambient temperature for a period of 3 hours.
• the porous microspheres with closed porosity of monodisperse SiCh thus obtained have an average diameter of 2.9 ⁇ m (with standard deviation of 1.5 ⁇ m) measured by scanning electron microscopy (SEM), an average pore diameter of 165 nm measured by scanning electron microscopy (SEM) and an average porosity measured by mercury porosimetry of 0.55. 94% by volume of the pores of these spheres are closed pores.
• Another sphere was obtained having an average diameter of 2.9 ⁇ m and an average pore diameter of 210 nm was obtained according to the same protocol by simply changing the content of nanoparticles:
• An SEM image of one of the spheres obtained (top image) as well as its cross section (bottom image) is presented in Figure 3.
• the cross section clearly shows the interior of the structure of the sphere comprising a network of relatively monodisperse and ordered closed pores. 96% by volume of the pores of these spheres are closed pores.
• Example 3 Porous silica spheres with closed porosity according to the invention obtained by atomization
• An aqueous suspension of positively charged spherical nanoparticles of methyl methacrylate copolymer and 2-(methacryloyloxy)ethyl]trimethylammonium chloride having a diameter D 5o measured by dynamic light scattering (DLS) measurement of 210 nm and negatively charged silica nanoparticles (mean diameter measured by scanning electron microscopy (SEM) of 7 nm) was prepared.
• the aqueous suspension is dried by atomization under a nitrogen atmosphere (inlet temperature: 100° C., outlet temperature: 45° C., feed rate: 10 mL/min, atomization gas pressure 40 mm) using a BÜCHI laboratory size atomizer.
• microspheres obtained are then calcined in a muffle furnace, in order to sinter and densify the silica nanoparticles and to remove the polymer, by placing them on a silicone plate and by carrying out a temperature rise from ambient temperature to 550° C. for a period of 5 hours, then by maintaining the temperature at 550° C. for 2 hours, then finally by lowering the temperature from 550° C. to ambient temperature for a period of 3 hours.
• the porous microspheres with closed porosity of monodisperse SiCh thus obtained have an average diameter of 7.6 ⁇ m (with standard deviation of 3.5 ⁇ m) measured by scanning electron microscopy (SEM), an average pore diameter of 165 nm measured by scanning electron microscopy (SEM) and a average porosity measured by mercury porosimetry of 0.55. At least 90% by volume of the pores of these spheres are closed pores.
• Example 4 Porous silica spheres with closed porosity according to the invention containing carbon black
• Example 1 The product of Example 1 was physically mixed with an aqueous dispersion of carbon black or carbon black powder at different weight contents.
• the porous spheres obtained contained carbon black in a content of 0.5%, 1%, 2%, 3%, 4% and 5% by weight, relative to the total weight of the particles.
• a quantity of 0.5 mg of porous spheres of Example 1 are placed in a 20 ml clear glass bottle having a surface area at the bottom of 6 cm 2 . The blue color is observed with the naked eye.
• a sample of porous spheres is prepared according to example 1 with the exception of the weight ratio of the polymer/silica which is 2/1.
• the sample prepared has a green color observable with the naked eye.
• Example 6 porous titanium spheres
• aqueous suspension of negatively charged spherical polystyrene nanoparticles having a diameter D 50 measured by dynamic light scattering (DLS) measurement of 197 nm and positively charged titanium nanoparticles (average diameter measured by scanning electron microscopy (SEM) of 15 nm) was prepared.
• the aqueous suspension is dried by atomization under a nitrogen atmosphere (inlet temperature: 100° C., outlet temperature: 45° C., feed rate: 10 mL/min, atomization gas pressure 55 mm) using a BÜCHI laboratory size atomizer.
• microspheres obtained are then calcined in a muffle furnace, in order to sinter and densify the titanium nanoparticles and to remove the polymer, by placing them on a silicone plate and by raising the temperature from ambient temperature to 300°C for a period of 4 hours, then by maintaining the temperature at 300°C for 6 hours, then by raising the temperature to 550°C for a period of 2 hours, then by maintaining the temperature at 550°C for 2 hours, then finally lowering the temperature from 550°C to room temperature for a period of 4 hours.
• the porous microspheres with closed porosity of TiCh thus obtained have an average diameter of 2.8 ⁇ m measured by scanning electron microscopy (SEM) with a standard deviation of 1.5 ⁇ m, an average pore diameter of 142 nm with a standard deviation of 15 nm measured by scanning electron microscopy (SEM) and an average porosity measured by mercury porosimetry of 0.55. 95% by volume of the pores of these spheres are closed pores.
• Example 7 Porous silica spheres with closed porosity according to the invention obtained by sol-gel process
• An aqueous suspension of positively charged spherical nanoparticles of methyl methacrylate copolymer and 2-(methacryloyloxy)ethyl]trimethylammonium chloride having a measured dynamic light scattering (DLS) diameter D 5 o of 254 nm and tetramethyl orthosilicate (TMOS) silica precursor was mixed at a pH in the range 2-5.
• the aqueous suspension is dried by atomization under a nitrogen atmosphere (inlet temperature: 100° C., outlet temperature: 45° C., feed rate: 10mL/min, atomizing gas pressure 40 mm) using a BÜCHI lab-size atomizer.

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