WO2023012440A1 - Cosmetic use of porous metal oxide microspheres for protection against blue light - Google Patents

Cosmetic use of porous metal oxide microspheres for protection against blue light Download PDF

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Publication number
WO2023012440A1
WO2023012440A1 PCT/FR2022/051561 FR2022051561W WO2023012440A1 WO 2023012440 A1 WO2023012440 A1 WO 2023012440A1 FR 2022051561 W FR2022051561 W FR 2022051561W WO 2023012440 A1 WO2023012440 A1 WO 2023012440A1
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WIPO (PCT)
Prior art keywords
skin
mucous membranes
appendages
microspheres
hair
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PCT/FR2022/051561
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French (fr)
Inventor
Michael David BURKE
Rupa Hiremath DARJI
David Herault
Bernd Herzog
Brigitte Lindemann
Solène MINE
Liangliang Qu
Keith TASK
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Basf Beauty Care Solutions France Sas
Basf Corporation
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Application filed by Basf Beauty Care Solutions France Sas, Basf Corporation filed Critical Basf Beauty Care Solutions France Sas
Publication of WO2023012440A1 publication Critical patent/WO2023012440A1/en

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    • 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
    • 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
    • A61K8/18—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
    • A61Q5/00—Preparations for care of the hair
    • 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
    • A61Q5/02—Preparations for cleaning the hair

Definitions

  • the present invention relates to the non-therapeutic cosmetic use of porous metal oxide microspheres to protect the skin, the skin appendages, in particular the hair, and/or the mucous membranes against the unsightly and/or unpleasant and/or uncomfortable effects of light. blue and/or to reduce and/or slow down the said effects on the skin, the skin appendages, in particular the hair, and/or the mucous membranes.
  • UV radiation represents a highly energetic part of the electromagnetic spectrum reaching the Earth's atmosphere. This region is subdivided into three wavelength bands: UVC ( ⁇ 280 nm), UVB (280-320 nm), and UVA (320-400 nm). While UVC is effectively blocked by oxygen, ozone and nitrogen molecules in the upper atmosphere and the majority of UVA passes the ozone layer of the stratosphere, UVB radiation is only partially absorbed by the atmosphere. stratospheric ozone. The infrared and visible regions account for the vast majority of solar emissions entering the atmosphere.
  • the visible spectrum is made up of a range of wavelength intervals of light that can be perceived by the human eye as colors.
  • the rainbow is a typical example of these different visible colors.
  • Solar radiation is composed of 25% to 30% blue light, depending on the reference solar spectrum. Blue light is therefore high energy visible light (HEV) with a wavelength in the range 401 nm to 500 nm.
  • HEV high energy visible light
  • the sun is the main source of natural blue light, but humans are also increasingly exposed to blue light from artificial sources, which vary widely in the distribution spectrum.
  • Blue LEDs emitting blue light in the 401 nm to 495 nm range are considered more dangerous than green and red LEDs.
  • the dominant wavelength of electronic devices has been estimated to be 448 nm (blue light), 535 nm (green light) and 599 (red light).
  • blue light has the most energetic wavelength of visible light, it penetrates the deepest into the skin, not only in the epidermis but also in the dermis generating oxidative stress and producing proteases which degrade the matrix extracellular dermis ⁇ Saint-Auret G, Kiening M, Haguet V, Suiierot M, Escaich S, Ramchurn R. The double nature of blue light on skin dependent pathways. IFSCC Congress Kunststoff. ID 560, 2018). In the stratum corneum, blue light contributes to the formation of carbonyl proteins which deteriorate the epidermal barrier and alter skin color Mizutani T, Sumida H, Sagawa Y, Okano Y, Masaki H.
  • the stratum corneum is weakened, for example due to its exposure to blue light, the skin barrier is broken and these insensible water losses increase.
  • the skin becomes dry and more vulnerable to external aggressions. Maintaining the water content via the role of the skin barrier is therefore essential for maintaining the functionalities and the aesthetic appearance of the skin.
  • Blue light at about 450 nm promotes keratinocyte differentiation and reduces the antioxidant capacity of fibroblasts (Opiander Cl, Hidding S, Werners FB, Born M, Paiiua N, Suschek CV. Effects of blue light irradiation on human dermal fibroblasts. J Photochem Photobioi B. May 3;103(2):118-25.2011). Other studies have shown that blue light increases the amount of reactive oxygen species (ROS), protein carbonyls, metalloproteinase-1 (MMPI) and 8-OHdG (8-oxo-7,8-dihydro -2'-deoxyguanosine). MMP-1 and 8-OHdG are associated with premature aging.
  • ROS reactive oxygen species
  • MMPI metalloproteinase-1
  • 8-OHdG 8-oxo-7,8-dihydro -2'-deoxyguanosine
  • MMPI is a metalloproteinase belonging to the family of enzymes involved in the degradation of the extracellular matrix, mainly dermal collagen including type I collagen, type IV collagen, fibronectin and laminins. Pollutants, UV or blue light can thus cause the expression of MMPI and can therefore lead to premature aging of the skin.
  • type I collagen is found in many human tissues such as tendons, ligaments, cornea and skin.
  • Type I collagen is the main collagen in the skin. It is part of the fibrillar collagens with collagen III and V. It is the collagen which gives the tissues their mechanical resistance, thus participating in a preponderant way in maintaining their firmness. Blue light by degrading collagen through MMPI helps to decrease skin firmness.
  • the physical appearance and phenotypic aspects of the keratinous fibers of the skin appendages, especially hair such as color, density, crimp, shine, volume, suppleness and style take an important place in social communication and communication. 'self esteem. From a functional point of view, the hair also has a role of protection of the scalp against external aggressions, and in particular against ultraviolet radiation and blue light. They also help maintain body temperature and provide tactile sensations.
  • the structural and functional qualities of the keratin fiber of the skin appendages, in particular the hair fiber deteriorate.
  • Hair and eyelashes are finer and more fragile.
  • the hair is also more difficult to comb and structure. Eyelashes and eyebrows are more difficult to set up and make up.
  • the aging of the keratin fiber of the skin appendages, in particular of the hair includes the aging of the keratin fiber, in particular of the hair, and the aging of the hair follicle.
  • the scalp which contains the hair follicles, also plays a very important role in the behavior and aging of the hair follicle and therefore in the quality and growth of the hair fibre.
  • the keratin fiber of the cutaneous appendages is an inert structure of the dander type. It is composed mainly of keratinized dead cells. Different types of keratin fibers are distinguished according to their location, their growth and their functions: eyelashes, eyebrows, body hair, in particular beard and mustache, and hair, also called hair fibers. In general, three major concentric parts constitute a keratin fibre: the medulla (or medullary canal) in the centre, the cortex at the level of the intermediate zone and finally the cuticle forming the surface scales. The cortical zone represents the major part of the hair shaft (90% of the total weight). It is the seat of pigmentation and gives the keratin fiber its physical and mechanical properties.
  • the cuticle is the protective envelope of the keratin fibre, made up of strongly keratinized non-pigmented cells forming the outer scales of the hair.
  • the medulla is located in the center of the hair shaft. It is made up of large anucleate cells, clear or slightly pigmented compared to cortical cells.
  • the organ allowing the synthesis of the keratin fiber of the cutaneous annexes and in particular of the hair is the hair follicle. It extends under the scalp in the case of hair and under the epidermis of the skin in the case of other keratinous fibers and can be divided into three segments of roughly similar length: the infundibulum or superficial segment, the isthmus or middle segment, bulb or lower segment.
  • the hair follicle is made up of living cells such as keratinocytes, fibroblasts and melanocytes and of extracellular matrix. The organization, the cellular and molecular interactions allow the synthesis of the hair shaft.
  • the hair shaft previously surrounded by cells, becomes free in the infundibulum at the height of the mouth of the sebaceous canal, an appendage which accompanies the hair follicle.
  • the keratin fiber of the cutaneous appendages, in particular capillary, visible at the root of the scalp for the hair or at the junction with the skin can be qualified as emerging fibre.
  • the fiber not visible at the root contained in the skin, in particular the scalp, can be qualified as pre-emergent fiber.
  • the average growth of a hair fiber lasts 3-4 years on average. Its growth rate is estimated at 1cm/month under normal average conditions.
  • the stem takes approximately 2 weeks from the seat of its creation to flush with the surface of the scalp.
  • An emergent stem of 6 cm takes about 6 months to form.
  • Blue light directly alters the structural and functional properties of the hair fiber.
  • aged hair is more damaged, finer and in particular is difficult to comb and shape compared to younger hair and is brittle, in particular split ends.
  • This loss of surface quality of the hair is visible and unsightly.
  • the hair also reflects less light and is thus visibly duller, less shiny, less luminous.
  • This aging also has an impact on hair loss which can result in a perception of fragility and hair loss over time. The hair thus appears less dense.
  • the other keratinous fibers of the skin appendages are exposed to the same phenomenon of aging altering their quality and their quantity, in a particularly unsightly and often undesirable way for the eyelashes, the eyebrows and the nails.
  • the mature melanocytes specialized in the synthesis of pigments transfer these pigments to the keratinocytes of the hair follicle, or cells of the matrix, which produce keratin fibre, in particular capillary.
  • the quantity of pigments transferred to the keratin fiber of the skin appendages, in particular the capillary decreases. This loss of pigmentation of the keratin fiber may be due to defects in the genesis of melanin or to the loss in number of melanocytes which produce it.
  • the speed and duration of the growth of the keratin stem, in particular the capillary also decreases as well as its diameter.
  • THE graying or whitening of the keratin fibers of the skin appendages, in particular the eyelashes, eyebrows, beard, mustache, hair, with age is the overall visual consequence of the pigmented and non-pigmented keratin stalks, the latter appearing white in color.
  • Lightening of the eyelashes, eyebrows, beard, mustache and hair may result from a dilution of the pigment, an increase in the frequency of keratinous fibers of the cutaneous appendages, in particular hair, which are not pigmented or an increase in the loss of pigmented keratinous fibres, in particular pigmented hair.
  • metal oxide microspheres have the property of protecting the skin, mucous membranes and cutaneous appendages against blue light, in particular by having an anti-blue light filter effect.
  • microspheres in fact have the unique ability, thanks to the presence of pores with a monodisperse or bimodal size distribution, in particular thanks to an ordered network of pores, of being able to target the reflection of a precise wavelength.
  • size of the pores and their quantity (porosity) as well as the size of the microspheres can be carefully chosen for this purpose thanks to the prior manufacture of a template/polymer model.
  • metal oxide microspheres having an average diameter D 50 measured by scanning electron microscopy (SEM) ranging from 1 ⁇ m to 30 ⁇ m, pores whose average diameter D 50 measured by electron microscopy at scanning (SEM) ranges from 50nm to 250nm and a porosity average measured by mercury porosimetry ranging from 0.4 to 0.65, could, when they are on the skin, the mucous membranes and/or the skin appendages, in particular prevent the transmission of blue light.
  • SEM scanning electron microscopy
  • microspheres 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 compositions, whether these are lipophilic or hydrophilic.
  • Another advantage is that the spheres can be used with the classic ingredients of cosmetic compositions,
  • Metal oxide spheres have already been described in patent applications WO2020/183108 and WO2020/182936 in the context of cosmetic applications. However, these applications do not describe or suggest the protective effect of these microspheres against blue light and its unsightly and/or unpleasant and/or uncomfortable effects.
  • the subject of the present invention is thus the non-therapeutic cosmetic use of porous microspheres comprising, advantageously constituted by, a metal oxide to protect the skin, the skin appendages, in particular the hair, and/or the mucous membranes against the unsightly effects and/or unpleasant and/or uncomfortable effects of blue light and/or to reduce and/or slow down the said effects on the skin, the skin appendages, in particular the hair, and/or the mucous membranes, and/or to prevent the occurrence of the said unsightly effects and/ or unpleasant and/or uncomfortable to blue light and/or to slow down its appearance, said microspheres having:
  • mucosa means the ocular mucosa, the vaginal mucosa, the uro-genital mucosa, the anal mucosa, the nasal mucosa and/or the buccal, labial and/or gingival mucosa, preferentially the mucous membranes most exposed to blue light, in particular the ocular and/or labial and/or nasal mucous membranes.
  • skin is understood to mean the skin of the face and of the body including the scalp and by “scalp” the temporal zones of the scalp, the frontal zone, the parietal zone and the vertex or vertex. of the skull.
  • cutaneous appendages means the hair, the eyelashes, the eyebrows, the beard, the mustache and/or the nails, preferentially the hair.
  • blue light means light having a wavelength ranging from 401 to 500 nm, advantageously from 415 to 490 nm, more advantageously from 420 to 480 nm, and in particular from 430 to 460 nm .
  • the use according to the invention is cosmetic, and preferentially by topical application on at least one zone concerned or a part of healthy skin, of healthy mucous membrane and/or of 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 intended for, in particular on, a skin healthy, in particular a healthy scalp, and/or healthy skin appendages, in particular healthy hair, and/or healthy mucous membranes.
  • the term “part of skin” and/or “zone of skin” referred to as “healthy” is understood to mean a part of the skin and/or a zone of skin, qualified as non-pathological by a dermatologist, c i.e.
  • topical application means applying the microspheres 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 or the mucous membranes, in particular by direct application, such as by massage with circular movements, or by vaporization of the microspheres on the surface of the area concerned of the skin and/or of the mucous membranes and/or of the skin appendages.
  • This protection is preferably evaluated when the skin and/or mucous membranes and/or skin appendages are exposed to blue light.
  • the protection of the skin and/or mucous membranes and/or skin appendages against the unsightly and/or unpleasant and/or uncomfortable effects of blue light can be assessed by analyzing the MMPI content in the dermis or epidermis or 8-OHdG content in the skin. This analysis is carried out by immunolabeling under the conditions indicated in example 2.
  • This analysis is in particular carried out on skin treated with the microspheres according to the invention subjected to blue light radiation, in particular at 85J/cm 2 (wavelength 401-500 nm of the visible light spectrum with a peak at 455 nm for 4 hours), and compared with the analysis results obtained with skin not treated with the microspheres according to the invention and subjected to similar blue light radiation, in particular as described in example 2.
  • the drop in the MMPI content in the dermis of the skin treated with the microspheres according to the invention is advantageously at least 10%, more advantageously at least 20%.
  • the decrease in the MMPI content in the epidermis of the skin treated with the microspheres according to the invention is advantageously at least 30%, more advantageously at least 50%.
  • the drop in the 8-OHdG content in the skin treated with the microspheres according to the invention is advantageously at least 20%, more advantageously at least 30%.
  • the "unsightly and/or unpleasant and/or uncomfortable effects of blue light" are advantageously chosen from aging of the skin and/or mucous membranes and/or skin appendages and/or alteration of skin and/or mucosal barrier and/or dehydration of the skin and/or mucous membranes and/or appendages and/or alteration of the biomechanical properties of the skin and/or mucous membranes and/or skin appendages.
  • the “unaesthetic effects of blue light” may consist of the appearance of unaesthetic irregularities in the relief, in particular the microrelief, and/or the texture of the skin, the mucous membranes and/or the skin appendages and/or irregularities in the color of the skin, mucous membranes and/or skin appendages, in particular making the complexion uneven.
  • the unsightly irregularities of the relief, in particular of the microrelief, and of the texture of the skin are wrinkles and fine lines, in particular frown lines and crow's feet, asperities and the rough appearance.
  • the irregularities in the color of the skin are pigmentary spots, in particular age spots or hyperpigmented or depigmented spots, pregnancy mask, redness, but also loss of radiance of the complexion, dull complexion and dark circles.
  • the unsightly effects of blue light on the skin and/or the mucous membranes are selected from among the alteration of the microrelief of the skin and/or the mucous membranes, the appearance of wrinkles and/or fine lines, the loss of radiance of the complexion, lack of uniformity of the complexion, the appearance of a dull complexion and/or dark circles and/or pigment spots, slackening of the skin and/or loss of tone and/or elasticity and /or firmness and/or density of the skin and/or mucous membranes and/or alteration of surface and/or texture and/or visual properties and any mixture thereof.
  • the unsightly effects of blue light on skin appendages, preferably hair are in particular the alteration of its visual properties and/or its surface and/or texture properties, (appearance of a dull, brittle appearance.
  • the unsightly effects also include the appearance of a brittle, crumbly, damaged appearance and/or difficulty in shaping them, in particular for the hair, comb, and/or split ends.
  • the unsightly effects of blue light on the mucous membranes include the appearance of a dull, cracked, withered and/or damaged appearance as well as scales.
  • the "unpleasant and/or uncomfortable effects of blue light” can consist of the appearance of a sensation of tightness, tension, tingling, tingling, and/or roughness of the skin and/or or the mucous membranes and/or the alteration of the sensory qualities of the skin and/or the mucous membranes and/or the cutaneous appendages, in particular the hair.
  • non-therapeutic cosmetic use of the microspheres according to the invention is to prevent and/or slow down
  • the prevention and/or reduction of the unsightly effects can be visualized and evaluated by microscopy and/or by analysis of high resolution photography with in particular measurement of the shine of the area of skin, mucous membrane and/or cutaneous appendages.
  • the prevention and/or slowing down of the loss of radiance of the complexion called “radiance” or “glow” in English can in particular be measured by an objective instrumental method.
  • This in vivo measurement method consists of taking high-resolution photographs in a cross-polarized configuration of the faces of volunteers at 45° before and after application of the tested product. Based on these digital photographs, an image analysis makes it possible to extract and quantify specific parameters (for example: L*, a*, b*, C, h°) related to color, brightness, the homogeneity, and the texture of the skin.
  • gloss in English can in particular be measured according to this method on the basis of high-resolution photographs in cross-polarized and parallel-polarized configuration of the face of the volunteers taken at 45° before and after application of the tested product. Based on these digital photographs, an image analysis makes it possible to extract and quantify specific parameters related to gloss such as specular gloss and contrast gloss.
  • insensible water losses means passive diffusion and insensible perspiration measured at the cutaneous or mucosal level. Also called transepidermal water loss or TEWL (transepidermal waterloss), transepidermal water loss can be measured by different methods, in particular in vivo, in particular via an evaporimeter, a tewameter, in particular in vitro, in particular by the open cylinder technique described in example 1 of patent application WO 2014/027163 and/or ex vivo .
  • the insensible water losses are measured by the technique described in example 1 of patent application WO 2014/027163 in an open cylinder and the reduction is determined relative to an untreated control.
  • water content of the skin and/or of the mucous membranes is understood to mean the quantity of water contained in the epithelia, in particular the epidermis and/or the epithelium of the mucous membranes. This content thus reflects the state of hydration.
  • There are various methods for measuring the water content of the skin and/or mucous membranes in particular in vivo and in particular via the corneometer, and/or by measuring desquamation via the corneofix, or in vitro, in particular via the measurement of the dielectric conductivity, in particular according to the method described in example 4 of patent application WO 2014/027163.
  • the term "prevent or slow down the loss of firmness” means a prevention and/or a slowing down for aesthetic purposes of the loss of firmness of the skin and/or mucous membranes subjected to blue light radiation. in particular by comparison between skin and/or mucous membranes treated with the aid of the microspheres according to the invention and subjected to blue light radiation and untreated skin and/or mucous membranes and subjected to blue light radiation or not subjected to blue light radiation.
  • the classic methods for measuring the firmness of the skin consist in measuring the depth of its possible deformations, while those aimed at measuring the elasticity of the skin consist in measuring its capacity to return to its initial state after torsion and/or deformation. .
  • the prevention or reduction of the loss of firmness can be measured according to conventional methods, in particular by in vivo measurement using a cutometer, a density meter, a torque meter or even a dynaskin associated with a dermatop and in particular by comparison between skin and/or mucous membranes treated with the microspheres according to the invention and subjected to blue light radiation and untreated skin and/or mucous membranes and subjected to light radiation blue or not subjected to blue light radiation.
  • the prevention or reduction of the loss of elasticity can be measured according to conventional methods, in particular by in vivo measurement, using a ballistometer or a corneovacuometer and in particular by comparison between skin and/or mucous membranes treated with the microspheres according to the invention and subjected to blue light radiation and untreated skin and/or mucous membranes and subjected to blue light radiation or not subjected to blue light radiation.
  • Conventional techniques for measuring the protection of cutaneous appendages make it possible to measure the capacity of the product evaluated to maintain a visual, structural or functional state of the cutaneous appendix subjected to blue light radiation, preferably of the keratin fiber subjected to radiation of blue light, still preferentially hair comparable to the state of a cutaneous appendix not subjected to blue light radiation, preferably keratin fiber not subjected to blue light radiation, more preferably hair not subjected to blue light radiation.
  • Conventional techniques can be carried out to test the effectiveness of the product evaluated in its solvent, or of a hair formula (shampoo, conditioner, masks, lotions, or other). They can be implemented on a skin appendix removed (ex vivo technique) or on a skin appendix in place on an individual (in vivo technique).
  • this technique involves observing the state and/or the quality of the cuticle, by visualization and quantification of loose scales as evidence of surface damage.
  • a damaged hair indeed presents a detachment of the scales whereas a protected hair appears smoother on the surface and its scales are sealed.
  • DSC Differential Scanning Calorimetry
  • the evaluation of the functional and mechanical properties of the hair is carried out by measuring elasticity, capacity for deformation, resistance of the hair in response to a tensile force. Parameters such as tensile strength, elastic modulus, breaking strength and breaking point are used to assess these biomechanical properties. These parameters testify to the state of the internal damage of the hair fiber.
  • a protected hair is a hair whose elastic and deformation properties are maintained.
  • Damaged hair is rough, harder to comb and more brittle when combed.
  • the protection of the hair can thus have a beneficial consequence on these styling properties, which can also be measured.
  • the styling evaluation methods which can be used according to the invention are:
  • the valuation methods used are:
  • structure of the skin appendages means the state of the skin appendages, in particular of the cuticle and even more preferably of the scales of the skin appendages.
  • the structure of the cutaneous appendages can thus be measured by the above-mentioned techniques of observation of the cuticle by electron microscopy and study of differential scanning calorimetry.
  • the term “visual properties of the cutaneous appendages” is understood to mean shine, luster and color.
  • the visual properties of the cutaneous appendages can in particular be evaluated by the visual sensory tests mentioned above.
  • biomechanical properties of the cutaneous appendages is understood to mean their qualities to the touch, in particular their softness, their silky and/or smooth character and their suppleness, as well as their resistance, their elasticity, their deformation and their strength as well as their ease of shaping and/or combing.
  • biomechanical properties of the skin and/or mucous membranes means their qualities to the touch, in particular their softness, their silky and/or smooth character and their suppleness, their tone, elasticity, firmness, density, their microrelief, their surface and/or textural and/or visual properties and/or their sensory qualities.
  • structure of the skin and/or mucous membranes means the state of the skin and/or mucous membranes, in particular of the skin barrier.
  • the term “visual properties of the skin and/or of the mucous membranes” is understood to mean the shine, the radiance and the color, in particular the radiance of the complexion and/or the homogeneity of the complexion.
  • biomechanical properties of the cutaneous appendages can be measured in particular by analyzing the force of tension on dry and/or damp hair and/or the styling evaluation methods and/or the tactile sensory tests mentioned above.
  • microspheres according to the invention are porous metal oxide microspheres.
  • Such microspheres are photonic, in particular they are photonic beads, which means that they exhibit a degree of periodic variations in color, in particular which have an impact on light waves including the perception of color, clarity, transparency, shine.
  • This is in particular due to the network of pores present in the microsphere, in particular an ordered network, more particularly a network of pores with a monodisperse size distribution, even more particularly of the order of a nanometer (in particular from 50 nm to 250 nm ).
  • hollow and non-porous microspheres would not have this capacity.
  • the porous microspheres according to the invention mainly contain the metal oxide.
  • they consist essentially in the metal oxide.
  • they consist exclusively of metal oxide.
  • the porous microspheres comprise between 60% and 99.9% of metal oxide, preferably at least 70%, more preferably at least 80%, more preferably at least 90%, more preferably 99.9% by weight per relative to the total weight of the microspheres.
  • the metal oxides include the oxides of transition metals, metalloids and earth metals compatible with cosmetic and/or dermatological use, such as for example oxide of silica, titanium, alumina, zirconia, cerium , iron, zinc oxide, indium oxide, tin oxide, chromium oxide, mixed metal oxide, combinations thereof.
  • the metal oxide is chosen from the group consisting of SiO 2 , TiO 2 , ZnO and their mixtures, advantageously it is SiO 2 .
  • the microspheres according to the invention contain only one metal oxide, preferably silica oxide.
  • the microspheres do not contain titanium oxide or zinc oxide.
  • the porous microspheres according to the invention may 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 spheres contain 0.3%, preferably 0.5%, preferably at least 1%, more preferably at least 5% by weight of light-absorbing agents, relative to the weight total of spheres.
  • the microspheres 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. Indeed, light absorbers such as TiCh can present a certain toxicity.
  • the inventors have surprisingly discovered that even without a light absorber, the microspheres 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, mucous membranes and/or skin appendages.
  • the porous microspheres according to the invention have an average diameter D 50 measured by scanning electron microscopy (SEM) ranging from 1 to 14 ⁇ m, in particular from 1.1 ⁇ m to 20 ⁇ m, advantageously from 1, 2 ⁇ m to 14 ⁇ m, in particular from 1.3 ⁇ m to 10 ⁇ m, more particularly from 1.5 to 4.5 ⁇ m, even more particularly from 1.6 ⁇ m to 4.4 ⁇ m, for example an average diameter chosen 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
  • 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.
  • the average pore diameter D50 of the microspheres measured by scanning electron microscopy (SEM) ranges from 80 nm to 250 nm, advantageously from 100 nm to 245 nm, in particular from 145 nm to 235 nm, more particularly from 180 nm to 225 nm, even more particularly from 195 nm to 217 nm, for example chosen from: 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85nm, 90nm, 95nm, 100nm, 105nm, HOnm, 115nm, 120nm, 125nm, 130nm, 135nm, 140nm, 145nm, 150nm, 155nm, 160nm, 165nm, 170nm,
  • SEM scanning electron microscopy
  • the porous microspheres have an average porosity 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 or 0.65, preferably ranging from 0.45 to 0.60, more preferably 0.50 to 0.60.
  • the size of the microspheres and/or the pores is a synonym of the diameter of the microspheres and/or the pores and is determined by scanning electron microscopy (SEM).
  • SEM scanning electron microscopy
  • average diameter of the microspheres and/or pores is meant the D50, meaning that half of the population is below and the other half is above. It is obtained by analyzing 50 to 70 microspheres and/or 50 to 70 pores of different microspheres by scanning electron microscopy using ImageJ image analysis software.
  • the average porosity of a microsphere refers to the total pore volume, as a fraction of the volume of the entire microsphere.
  • the average porosity can also be called "volume fraction". It is a dimensionless quantity.
  • 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 size distribution of the pores of the microspheres according to the invention is monodisperse or bimodal, advantageously monodisperse, more particularly ordered, even more particularly ordered and monodisperse.
  • microdisperse pore size distribution means a pore size distribution such that 90% of the surface delimited by the pore size distribution lies within the interval given by the average size ⁇ 5% of its value.
  • the microspheres according to the invention do not contain and/or are not used in combination with nanoparticles, in particular of titanium oxide and/or zinc oxide, and/or another anti-blue light filter and/or an anti-UV filter and/or a sunscreen and/or in a cosmetic composition which contains them.
  • nanoparticles in particular of titanium oxide and/or zinc oxide
  • the microspheres according to the invention are not used as a booster for anti-blue light filters and/or to increase the SPF (sun protection index) of a sunscreen composition.
  • the porous microspheres 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. According to a particular mode of the invention, the porous microspheres according to the invention do not comprise a coating layer on their surface containing a polyorganosiloxane, in particular a silicone compound.
  • porous microspheres comprising a metal oxide according to the invention can be prepared using a sacrificial polymer template. Such porous microspheres show a color observable by the human eye, in particular a blue color.
  • a color observable with the naked eye means a color that is observable by a majority of people. This can be for any sample of microspheres 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.
  • microspheres can be prepared by a method as described in patent application US2019/0076809 or in one of patent applications WO2020/183108 and WO2020/182936.
  • an aqueous colloidal dispersion containing particles of polymer and a metal oxide is prepared, the particles of polymer being typically at the nanometric scale.
  • the colloidal aqueous dispersion is then mixed in an oily continuous phase, for example with a microfluidic device, to produce a water-in-oil emulsion.
  • Aqueous emulsion droplets are obtained, collected and dried to form the microspheres containing the polymer and metal oxide nanoparticles.
  • the polymer nanoparticles (nanospheres) are then eliminated, for example by calcination, to provide particles spherical, microscale metal oxide containing a high degree of porosity and nanoscale pores.
  • the spheres can contain uniform pore diameters, due to the use of spherical and monodisperse polymer particles.
  • a drop of emulsion containing polymer nanospheres and a metal oxide is dried to remove the solvent, thereby producing a microsphere formed of polymer nanospheres with the metal oxide in interstitial spaces between the polymer nanospheres (model microspheres or templates or "direct structure").
  • the polymer nanospheres define an interstitial space. Calcination results in shrinkage of the polymer, thus providing a metal oxide microsphere with high porosity or large interstitial volume (inverse structure).
  • porous metal oxide microspheres are advantageously sintered, resulting in a continuous, consolidated, thermally and mechanically stable solid structure.
  • the formation of the droplets and their collection take place in the microfluidic device.
  • microfluidic devices are narrow channel devices having a microscale junction adapted to produce uniform droplets and connected to a collection reservoir.
  • Microfluidic devices contain, for example, a junction having a channel width ranging from 10 ⁇ m to about 100 ⁇ m. These devices are for example made of polydimethylsiloxane (PDMS) and can be prepared for example by soft lithography.
  • An emulsion can be prepared inside the device by pumping an aqueous dispersed phase and an oily continuous phase according to a defined ratio thus forming an emulsion by mixing the two phases.
  • an oil-in-water emulsion can be used.
  • the polymer is selected from the group consisting of poly(meth)acrylic acid, poly(meth)acrylates, polystyrenes, polyacrylamides, polyethylene, polypropylene, polylactic acid, polyacrylonitrile, as well as as their derivatives and their salts, their copolymers and their combinations.
  • the polymer is chosen from the group consisting of polystyrenes, for example a copolymer of polystyrene/acrylic acid, polystyrene/poly(ethylene glycol) methacrylate or polystyrene/styrene sulfonate.
  • the weight ratio (weight/weight) of polymer/metal oxide nanoparticles ranges, for example, from about 0.1/1 to about 10.0/1 or from about 0.5/1 to about 10.0/1.
  • this ratio is: 0.1/1, 0.5/1, 1.0/1, 1.5/1, 2.0/1, 2.5/1, 3.0/1, 3.5/1, 4.0/1, 5.0/1, 5.5/1, 6.0/1, 6.5/1, 7.0/1, 7, 5/2, 5, 8.0/1, 9.0/1 or 10.0/1, in particular 7.5/2.5.
  • the continuous oily phase comprises for example an organic solvent, a silicone oil or a fluorinated oil.
  • organic solvents include hydrocarbons, such as heptane, hexane, toluene, xylene as well as alcohols, such as methanol, ethanol, propanol, etc.
  • the emulsion droplets are collected, dried and the polymer is removed.
  • 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 polymer is removed according to conventional techniques, for example by calcination, pyrolysis or by a solvent.
  • the calcination is carried out according to one embodiment at temperatures ranging from 200°C to about 1200°C.
  • the calcination temperature is at least 200°C, preferably at least 500°C, more preferably at least 1000°C.
  • the calcination temperature from 200°C to about 700°C.
  • the calcination is carried out for an appropriate period, for example ranging from 0.1 hour to about 12 hours, preferably from 1 hour to 8 hours. In certain embodiments, the calcination is carried out for at least 0.1 hour, for at least 1 hour, for at least 5 hours or for at least 10 hours.
  • the liquid dispersion comprising the polymer and metal oxide nanoparticles is formed in an oily dispersed phase and in a continuous aqueous phase to form an oil-in-water emulsion.
  • the oily droplets can thus be collected and dried in the same way as the aqueous droplets.
  • a liquid dispersion comprising the polymer and metal oxide nanoparticles is prepared and is spray dried to form the polymer template/template microspheres without forming a liquid/liquid emulsion.
  • a liquid solution or dispersion is fed (eg, pumped) into an atomizing nozzle with a compressed gas inlet. Feed is pumped through the atomizing nozzle to form liquid droplets. The droplets are surrounded by a preheated gas in the evaporation chamber, resulting in the evaporation of the solvent to produce solid particles. The dried particles are transported by the drying gas through the cyclone and deposited in the collection chamber.
  • Usable gases include nitrogen and/or air.
  • the feed liquid contains an aqueous or oily phase, the polymer nanoparticles and the metal oxide.
  • the microspheres polymer template/template contain the polymer nanoparticles with the metal oxide in the interstitial spaces between the polymer nanoparticles.
  • the polymer nanoparticles define the interstitial spaces.
  • Spray drying techniques include inkjet spray drying methods.
  • air and/or gas can be considered as the continuous phase with a dispersed liquid phase (liquid-in-gas emulsion).
  • the spray drying includes an inlet temperature of at least 100°C, 105°C, 110°C, 115°C, 120°C, 130°C, 140°C, 150°C, C, 160°C or 170°C to 180°C, 190°C, 200°C, 210°C, 215°C or 220°C, in particular 100°C.
  • the feed rate is 1 mL/min, 2 mL/min, 5 mL/min, 6 mL/min, 8 mL/min, 10 mL/min, 12 mL/min, 14 mL/min or 16 mL/min to 18 mL/min, 20 mL/min, 22 mL/min, 24 mL/min, 26 mL/min, 28 mL/min or 30 mL/min, in particular it is 10 mL/min .
  • Spray drying techniques are described in particular for example in patent application U52016/0170091.
  • microspheres obtained are spherical or quasi-spherical and are on the micrometric scale.
  • the polymer nanoparticles used as model/templates are also spherical, on the nanometric scale, they are monodispersed and have an average diameter ranging from 50 nm to approximately 999 nm, advantageously from 50 nm to 500 nm, in particular from 100 nm to 400 nm.
  • the polymer nanoparticles have an average diameter of 50 nm, 75 nm, 100 nm, 130 nm, 160 nm, 190 nm, 210 nm, 240 nm, 270 nm, 300 nm, 330 nm, 360 nm, 390 nm , 410nm, 440nm, 470nm, 500nm, 530nm, 560nm, 590nm, 620nm, 650nm, 680nm, 710nm, 740nm, 770nm, 800nm, 830nm, 860nm, 890 nm, 910nm, 940nm, 970nm or 990nm.
  • the metal oxide used can also be in the form of particles, such particles then being able to be on the nanometric scale.
  • the dispersed metal oxide can be supplied in the form of metal oxide or in the form of a precursor of the metal oxide, such as for example by the sol-gel technique.
  • each droplet forms a single microsphere.
  • the pore diameters are dependent on the size of the polymer particles. A phenomenon of shrinkage or compaction may appear during the shrinkage of the polymer, producing pore sizes slightly smaller than the initial size of the polymer particles, for example ranging from 10% to 40% smaller than the size of the polymer particle initial.
  • the pore diameter is as uniform as were the shape and size of the polymer nanoparticles.
  • the porous sphere has a solid center at the core and porosity toward the outer surface of the sphere.
  • the porous spheres have a hollow center with increasing porosity toward the interior of the spheres.
  • the porosity is distributed uniformly throughout the volume of the microspheres.
  • the mean diameter of the microspheres is markedly larger than the mean diameter of the pores.
  • the average diameter of the microspheres is in general at least 5 times, preferentially at least 10 times, preferentially at less than 15 times, more preferably 20 times, more preferably 25 times greater than the average pore diameter.
  • the ratio of the average microsphere diameter to the average pore diameter is at least 5/1, at least 10/1, at least 15/1, at least 40/1, at least 50/ 1, at least 60/1, at least 70/1, at least 80/1, or at least 90/1.
  • Models of polymer microspheres comprising monodisperse polymer nanospheres can result in metal oxide microspheres having similar pores in diameter, once the polymer is removed.
  • most of the porous microspheres have a color observable with the naked eye, in particular a blue color.
  • the porous microspheres according to the present invention may or may not exhibit angle-dependent color.
  • an angle-dependent color is meant an observed color that depends on the angle of the incident light or the angle between the observer and the observed color area.
  • An angle-independent color means that the observed color does not depend substantively on the angle of the incident light or the angle between the observer and the observed color area.
  • Microspheres having an angle-dependent color can be obtained in particular by using monodispersed polymer nanospheres. They can also be obtained when the step of drying the liquid droplets to provide the model of the polymer microspheres is carried out gently, thus allowing the polymer nanospheres to become ordered. An ordered porosity is thus obtained (such as an ordered pore network and/or an ordered pore size distribution) and in particular with a monodisperse pore size distribution. Microspheres whose color is independent of the angle can be obtained when the step of drying the liquid droplets is carried out quickly, not allowing the polymer nanospheres to order themselves.
  • porous microspheres are themselves also monodispersed.
  • “Most of the microspheres” means the population of the microspheres. This can be an amount of > 0.1 mg, > 0.2 mg, > 0.3 mg, > 0.4 mg, > 0.5 mg, > 0.7 mg, > 1.0 mg, > 2.5 mg, > 5.0 mg, > 10.0 mg or > 25.0 mg. Most microspheres may be devoid of other compounds.
  • micro-scale On a micrometric scale or “micro-” is understood to mean a size ranging from about 1 ⁇ m to about 999 ⁇ m.
  • nano-scale or “nano-” is meant a size ranging from about 1 nm to about 999 nm.
  • the term “monodispersed” for the population of porous microspheres or of polymer nanospheres means particles which have a homogeneous shape and a homogeneous diameter.
  • the population of spheres is thus said to be monodisperse when 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% of the number of particles have a diameter of ⁇ 7%, ⁇ 6%, ⁇ 5%, ⁇ 4%, ⁇ 3%, ⁇ 2% or ⁇ 1% relative to the average diameter of the sphere population.
  • Removal of the monodispersed population of polymer nanospheres yields metal oxide microspheres having a population of pores having an average diameter.
  • microspheres according to the invention comprising a metal oxide are prepared by a method comprising the following steps:
  • the liquid droplets are aqueous.
  • the liquid droplets are oily.
  • the method comprises a continuous phase and the mixing of the liquid dispersion with this continuous phase to form an emulsion containing the dispersed droplets of liquid dispersion.
  • the continuous phase is oily and the mixture is carried out between the continuous oily phase and the aqueous liquid dispersion to form a water-in-oil emulsion containing aqueous droplets.
  • the continuous phase is aqueous and the mixture is carried out between the continuous aqueous phase and the oily liquid dispersion to form an oil-in-water emulsion containing lipid droplets.
  • the continuous phase is gaseous and the mixing is carried out between the continuous gaseous phase and the aqueous liquid dispersion to form a water-in-gas emulsion containing aqueous droplets.
  • the method comprises the subsequent steps of collecting the droplets, drying the droplets and removing the polymer nanospheres from the model of microspheres.
  • the porous microspheres are used alone, in particular in powder form (100%), or in composition, in particular cosmetic, at a concentration ranging from 0.01 to 20%, advantageously ranging from 0.1 to 5% , preferably ranging from 0.5% to 3%, still preferentially from 1% up to 2%, by weight relative to the total weight of the composition.
  • porous microspheres according to the invention can be used alone, in particular in the form of a cosmetic active ingredient or in a composition intended to be in contact with the skin, the appendages and/or the cutaneous mucous membranes, such as for example a cosmetic composition , preferably intended for topical application.
  • the active ingredient and/or the cosmetic compositions containing the porous spheres according to the invention are preferentially intended for the cosmetic protection of the skin, including the scalp as well as the skin appendages, preferentially the hair.
  • the spheres according to the invention can be incorporated into a cosmetic composition further comprising at least one cosmetically acceptable excipient.
  • the term “cosmetically acceptable” excipient is understood to mean a topically acceptable compound and/or solvent, that is to say not inducing an allergic response on contact with the skin, including the human scalp, the mucous membranes and skin appendages, non-toxic, non-stable, or their equivalents, undue.
  • the cosmetic composition according to the invention can be in any galenic form conventionally used for topical application to the skin including the scalp, mucous membranes and skin appendages, such as liquid or solid forms or even in the form of liquid under pressure.
  • They can in particular be formulated in the form of an aqueous or oily solution, in particular a lotion, a cream or an aqueous gel or an oily gel, in particular in a jar or in a tube, in particular a shower gel, a shampoo, an after- shampoo, milk, oil, emulsion, hydrogel, microemulsion or nanoemulsion, in particular oil-in-water or water-in-oil or multiple or silicone, a serum, a lotion, in particular in a glass or plastic bottle or in a dispenser bottle or in an aerosol or spray, an ampoule, a liquid or solid soap, a paste, an ointment, a mousse, a mask, a lacquer, a patch, an anhydrous product, preferably liquid, past
  • the cosmetic composition is chosen from the group consisting 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 mascara, a make-up pencil, a varnish, a powder, in particular a make-up powder, a stick, again preferably it is a a cream, serum or lotion.
  • the cosmetic composition according to the invention is at least slightly gelled and/or comprises an oily phase, preferably is of the oily composition or oil-in-water or water-in-oil emulsion or lotion type.
  • compositions according to the invention may contain any suitable solvent and/or any suitable vehicle and/or any suitable cosmetically acceptable excipient, optionally in combination with other compounds of interest.
  • the composition does not include a UV filter, in particular a sunscreen, and/or other anti-blue light filters.
  • the cosmetically acceptable excipient contains, for example, at least one compound chosen from the group consisting of preservatives, emollients, emulsifiers, surfactants, moisturizers, thickeners, conditioners, mattifying agents, stabilizers, antioxidants, texture agents, shine agents, film-forming agents, solubilizers, pigments, dyes and perfumes.
  • excipients are preferably chosen from the group consisting of amino acids and their derivatives, polyglycerols, esters, polymers and cellulose derivatives, Lanolin derivatives, phospholipids, lactoferrins, lactoperoxidases, stabilizers based on sucrose, vitamins E and its derivatives, natural and synthetic waxes, vegetable oils, triglycerides, unsaponifiables, phytosterols, vegetable esters, silicones and their derivatives, protein hydrolysates, Jojoba oil and its derivatives, lipo/water-soluble esters, betaines, aminoxides, plant extracts, sucrose esters, titanium dioxides, glycines, and parabens, and more preferably from the group consisting of butylene glycol, steareth -2, steareth-21, stearyl ether glycol-15, cetearyl alcohol, phenoxyethanol, methylparaben, ethylparaben, propylparaben, butylparab
  • these classes of ingredients include, but are not limited to, the following compounds: abrasive, absorbents, compounds for aesthetic purposes such as perfumes, pigments, dyes, essential oils, astringents, anti-acne agents, anti-flocculating agents, antifoaming agents, antimicrobial agents (for example: iodopropyl butylcarbamate), antioxidants, binders, biological additives, buffering agents, swelling agents, chelating agents, additives, biocidal agents, denaturants, thickeners, and vitamins, and derivatives or equivalents thereof, film forming materials, polymers, opacifying agents, pH adjusters, reducing agents, depigmenting or lightening agents (e.g. hydroquinone, kojic acid, ascorbic acid, magnesium ascorbyl phosphate, ascorbyl glucosamine), conditioning agents (eg humectants).
  • abrasive, absorbents compounds for aesthetic purposes such as perfumes, pigments, dyes
  • the microspheres according to the invention can be used, optionally in a composition cosmetic, as the sole agent for protecting the skin and/or appendages and/or mucous membranes against the unsightly and/or unpleasant and/or uncomfortable effects of blue light or in combination with other active agents having complementary and conventional in cosmetic compositions, such as those chosen from:
  • - moisturizing agents one or more agents promoting hydration such as a polysaccharide extracted from seeds of Cassia angustifoüa marketed under the name HyalurosmoothTM by the applicant, or an agent chosen from one of the combinations containing pullulan, hyaluronate of sodium and sodium alginate marketed under the name PatcH2OTM by the applicant or one or more of the compounds of the natural moisturizing factor or a natural extract of honey marketed by the applicant under the name MelhydranTM and/or a compound of the glucosyl glyceride family, in particular hexosyl glyceride, an extract of the pericarp of Litchi chinensis under the name LitezermTM by the applicant;
  • agents promoting hydration such as a polysaccharide extracted from seeds of Cassia angustifoüa marketed under the name HyalurosmoothTM by the applicant, or an agent chosen from one of the combinations containing pullulan, hyal
  • an agent stimulating the synthesis of fibronectin in particular an extract of maize, such an extract being in particular marketed by the applicant under the name DelinerTM;
  • an agent for protecting the fibroblast growth factor (FGF2) of the extracellular matrix against its degradation and/or its denaturation in particular an extract of Hibiscus A mecanicoscus as described in the patent application in the name of the applicant filed under the number FR0654316 and/or an agent for stimulating the growth of fibroblasts, for example a fermented soybean extract containing peptides, known under the name of PhytokineTM marketed by the applicant and also described in patent application EPI 119344 B1 (Laboratories Expanscience), and preferably a combination of these two extracts;
  • an agent stimulating the synthesis of laminin in particular a malt extract modified by biotechnology, such an extract being in particular marketed by the applicant under the name Basaline TM; and a lipid synthesis stimulating agent such as a potato extract (so/anum tuberosum) modified by biotechnology marketed by the applicant under the name LipidessenceTM;
  • Hyaluronan synthase 2 such as the plant extracts described in patent application FR2 893 252 Al and in particular an aqueous extract of Galanga Aipinia galanga) marketed under the name HyalufixTM by the applicant;
  • LXL lysyl oxidase like
  • anti-pollution agents such as an extract of leaves of A' rgania spinosa marketed under the name ArganylTM by the applicant or an extract of seeds of Moringa oleifera marketed under the name PurisoftTM by the applicant or else a root extract of Eperua falcata marketed under the name EperulineTM by the applicant;
  • an agent stimulating the synthesis of intracellular ATP in particular an extract of Laminaria digitata seaweed
  • an agent with overall anti-ageing action in particular anti-pigment spots, in particular niacinamide or vitamin B3;
  • an antibacterial and/or sebum regulating agent, and/or sebum absorber such as retinoids, sarcosine, zinc salts, in particular zinc gluconate, zinc salicylate, azelaic acid, and/or their derivatives and mixtures, an extract of Orthosiphon stamineus marketed under the name MAT XSTM Bright by the applicant, an extract of Bixa Orellana marketed under the name Bix'Activ TM by the applicant, the antibacterial extracts described in the application for patent FR2863893, and in particular a Boldo extract, in particular that marketed under the name BetapurTM by the applicant, or talc, - and any of their mixtures.
  • an antibacterial and/or sebum regulating agent, and/or sebum absorber such as retinoids, sarcosine, zinc salts, in particular zinc gluconate, zinc salicylate, azelaic acid, and/or their derivatives and mixtures
  • porous microspheres according to the present invention is particularly advantageous in that it allows an immediately effective and lasting action on any type of skin including the scalp, on the skin appendages, preferably the hair and on the mucous membranes.
  • the porous microspheres according to the invention are applied to at least one area of the body exposed to blue light, this or these areas preferably being a surface of the body chosen from the skin of the face, including the forehead, the cheeks, the nose, the temples, the T zone (forehead, nose and chin), under the eyes, the peri-orbital zone, in particular dark circles, the contour of the lips and /or the chin, the scalp, the neck, the back, the shoulders, the forearms, the thorax, the hands, the hair, the beard, the eyelashes, the eyebrows the bust, the legs, the feet, the armpits, hands, Vietnameselleté, stomach, arms, thighs, hips, buttocks, waist, torso.
  • the present invention thus also relates to a non-therapeutic cosmetic care process comprising the topical application to at least one area of skin and/or mucosa and/or skin appendages, in particular hair, of porous microspheres according to the invention, advantageously on all or part of the skin and/or the mucous membranes of the body and/or the face chosen from the scalp, the legs, thighs, arms, stomach, Vietnameselleté, neck, all or part of the face, forehead, chin, lips, lip contour, eye contour, the so-called "T" area of the face, and/or on all or part of the skin appendages, more preferably the hair, preferably on at least one surface chosen from a surface of the body chosen from the skin of the face, including the forehead, the cheeks, the nose, the temples, the T zone (forehead, nose and chin), under the eyes, the peri-orbital zone, in particular dark circles, the contour of the lips and/or the chin, the scalp, the neck, the back, the shoulders, the
  • microspheres according to the invention are particularly suitable for their uses on any type of skin, mucous membranes and/or appendages, in particular Caucasian, Asian, African as well as on any type of skin, in particular on young skin and/or showing the first signs of age and/or for mature skin, that is to say men or women aged at least 50, in particular menopausal women.
  • compositions according to the invention are preferably of the leave-in type.
  • the porous microspheres according to the invention are used in regular topical application and preferentially at least once a day, advantageously twice times a day.
  • the cosmetic composition is applied to the skin.
  • the microspheres can be used in powder but also in the form of a cosmetic ingredient formulated in liquid form.
  • the microspheres are then preferably suspended in glycerin 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 thereof , preferably a hydroglycolic mixture, more preferably containing a glycol chosen from butylene glycol, propylene glycol, caprylyl glycol, hexylene glycol and mixtures thereof.
  • the microspheres 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 non-therapeutic cosmetic care process comprising the application to at least one area of skin and/or mucosa and/or cutaneous appendages of porous microspheres comprising, advantageously consisting of, a metal oxide or of a cosmetic composition comprising them to protect the area of skin, skin appendages, in particular hair, and/or mucous membrane against the unsightly and/or unpleasant and/or uncomfortable effects of blue light and/or to reduce it and/or slow down said effects on this area of skin, skin appendages, in particular hair, and/or mucous membranes, and/or to prevent the occurrence of said unsightly and/or unpleasant and/or uncomfortable effects of blue light and/or or to slow down their appearance, the unsightly and/or unpleasant and/or uncomfortable effects being advantageously chosen from aging of the skin and/or of the mucous membranes and/or of the cutaneous appendages and/or alteration of the bar cutaneous and/or mucosal arrhythmia and/or dehydration of the skin
  • the cosmetic care process according to the invention comprises the selection of an area of skin and/or skin appendages, in particular hair, and/or mucous membrane likely to be subjected to radiation of blue light and/or which it is desired to protect against the unsightly and/or unpleasant and/or uncomfortable effects of blue light and/or to reduce and/or slow down said effects and/or which it is desired to prevent the occurrence of said unsightly and/or unpleasant effects and/or uncomfortable from blue light and/or to slow down its appearance, before application to said area of skin.
  • the cosmetic care process according to the invention is characterized in that the porous microspheres and/or the cosmetic composition comprising them are applied topically to all or part of the skin and/or the mucous membranes of the body and/or the face chosen from the scalp, legs, thighs, arms, stomach, Vietnameselleté, neck, all or part of the face, forehead, chin, lips, lip contour, eye contour, the so-called “T” zone of the face, and/or on all or part of the skin appendages, more preferably the hair.
  • the cosmetic care process according to the invention is characterized in that the porous microspheres and/or the cosmetic composition comprising them are as defined below:
  • the metal oxide is chosen from the group consisting of SiCh, TiCh, ZnO and their mixtures, advantageously it is SiO 2 ; and or - the microspheres have an average diameter D50 measured by scanning electron microscopy (SEM) ranging from 1.3 to 10 ⁇ m, in particular from 1.5 to 4.5 ⁇ m; and or
  • the average pore diameter D50 of the microspheres measured by scanning electron microscopy (SEM) ranges from 100 to 245 nm, in particular from 180 to 225 nm; and or
  • the microspheres do not contain and/or are not used in combination with another anti-blue light filter and/or an anti-UV filter and/or a sunscreen and/or in a cosmetic composition which contains it; and or
  • the porous microspheres are included in a cosmetic composition, at a content ranging from 0.01% to 20% by weight, advantageously from 0.1% to 5% by weight, again advantageously from 0.5% to 3% by weight , in particular from 1% to 2% by weight, relative to the total weight of the composition; and or
  • the cosmetic composition comprises at least one cosmetically acceptable excipient and that this composition is chosen from 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 mascara, a make-up pencil, a varnish, a powder, in particular a make-up powder, a stick.
  • this composition is chosen from 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 mascara, a make-up pencil, a varnish, a powder, in particular a make-up powder, a stick.
  • the cosmetic care process according to the invention is for preventing and/or slowing down
  • the invention also relates to a cosmetic treatment method for protecting the skin, the skin appendages, in particular the hair, and/or the mucous membranes against the unsightly and/or unpleasant and/or uncomfortable effects of blue light. and/or to reduce and/or slow down said effects on the skin, the skin appendages, in particular the hair, and/or the mucous membranes and/or including to prevent the occurrence of said unsightly and/or unpleasant and/or uncomfortable effects of light blue and/or to slow down its appearance, of an individual who needs/wants it, including the steps:
  • a copolymer of styrene and acrylic acid is prepared as follows: 230 mL of deionized (DI) water is added to a 3-neck reaction flask equipped with a thermometer, condenser, magnetic stirring and under nitrogen atmosphere. The water is heated to 80° C. and a quantity of 10 g of styrene is added with stirring, followed by a quantity of 100 mg of acrylic acid dissolved in a quantity of 10 ml of deionized water, by syringe. A quantity of 100 mg of ammonium persulfate is dissolved in 10 ml of deionized water and added by syringe into the mixture while stirring. The mixture is left under stirring for 24 hours at 80°C.
  • DI deionized
  • the polymer colloidal dispersion is allowed to cool to room temperature and is purified by centrifugation, thereby forming polystyrene nanospheres having an average particle size of 250 nm.
  • the colloidal aqueous dispersion of polystyrene is diluted in deionized water to a content of 7.5% by weight, relative to the total weight of the composition and 2.5% by weight of silica nanoparticles relative to the total weight of the composition are added to the mixture.
  • This dispersion therefore contains 7.5% by weight of polystyrene, 2.5% by weight of silica nanoparticles and 90% by weight of deionized water relative to the total weight of the composition.
  • the mixture is subjected to ultrasonic treatment to prevent particle agglomeration.
  • the aqueous dispersion is dried by atomization under a nitrogen atmosphere (inlet temperature: 100°C, outlet temperature: 45°C, feed rate: 10mL/min) to provide monodispersed model microspheres containing 75% by weight of polystyrene and 25% by weight of silica.
  • microspheres are then calcined in order to remove the polymer by placing them on a silicone plate, and by carrying out a rise in temperature from 40°C to 500°C at a rate of 2°C/min, then by maintaining the temperature of 500° C. for 2 hours, then finally lowering the temperature from 500° C. to 40° C. at a rate of 2° C./min.
  • the porous microspheres of monodispersed SiO 2 thus obtained have a mean diameter D 50 of 3.01 ⁇ 1.34 ⁇ m measured by scanning electron microscopy (SEM), mean pore diameter D 50 of 206 ⁇ 10 nm measured by scanning electron microscopy (SEM) and mean porosity measured by mercury porosimetry of 0.55.
  • the microspheres are blue in color.
  • Example 2 evaluation of skin protection against blue light on explants of human skin
  • Example 1 The microspheres obtained in Example 1 were incorporated into the Emulgade® CPE microemulsion gel marketed by BASF (INCI: Olus Oil (and) Glycerin (and) Lauryl Glucoside (and) Polyglyceryl-2-Dipolyhydroxystearate (and) Glyceryl Oleate ( and) Dicaprylyl Carbonate at a content of 1.5% by weight relative to the total weight of the composition, with vigorous stirring (composition according to the invention)
  • the spheres are inert, do not re-swell, and are in suspension in the medium The dispersion is better under strong agitation avoiding agglomerates
  • Table 1 The composition of the gel containing the microspheres is indicated in table 1 below
  • Skin explants were prepared from fresh abdominal biopsies obtained by plastic surgery (55-year-old women). THE skin explants were cultured for 6 days in a standard EMEM culture medium (Eagle's minimum essential medium), at 37° C., 5% CO2, in a humid atmosphere with a humidity rate of 95%.
  • EMEM culture medium Eagle's minimum essential medium
  • the explants were treated daily for 5 days by topical application of 2 mg/cm 2 of the composition according to the invention or of a placebo (Emulgade® CPE microemulsion gel marketed by BASF not containing the microspheres according to the invention ) (placebo control and blue light control). Then the explants in a Hanks' Balanced Salt Solution (HBSS) medium were irradiated (composition according to the invention and blue light control) with blue light at 85J/cm 2 (wavelength 401-500 nm of the visible light spectrum with a peak at 455 nm for 4 hours) using a solarbox® or were not irradiated (placebo control). The skin explants were then cultured one more day in the defined medium before analysis.
  • HBSS Hanks' Balanced Salt Solution
  • the MMPI and 8-OHdG contents of the skin explants were evaluated by immunostaining. Skin explants were cut into thin sections (5 ⁇ m) using a microtome (Leica RM2125, Leica Biosystems) and transferred to Superfrost® slides. MMPI was detected by a specific monoclonal antibody (monoclonal 36665 mouse clone, R&D Systems). 8-OHdG was detected by a monoclonal antibody (monoclonal mouse clone N45-1, Gentaur Genprice). The primary antibodies were revealed using the streptavidin/biotin and peroxidase method (Vector VIP Peroxidase H RP kit, Vector Laboratories Inc.).
  • Results are expressed as mean ⁇ standard deviation (SD; 3 explants per condition, 6 images per explant). The results are expressed as a percentage of the surface occupied by the coloration and were then normalized with respect to the blue light control condition. Statistical differences between these conditions were assessed using Student's t test. The significance level was set at 5% (p ⁇ 0.05). The “Statistics” column indicates the level of significance given the chosen p-value. The mention p ⁇ 0.05 thus designates a result that is significantly different from the chosen control. The mention p ⁇ 0.01 designates a result that is very significantly different from the chosen control.
  • Table 2 significant 8-OHdG content in the skin (P ⁇ 0.01).
  • the microspheres according to the invention reduce the content of 8-OHdG by 37% (P ⁇ 0.05). Table 3
  • Tinosorb® M marketed by BASF and consisting of a broad-spectrum UV filter based on the technology of micro organic particles.
  • -fine ICI name: Methylene Bis-Benzotriazolyl Tetramethylbutylphenol (and) water (and) Decyl Glucoside (and) Propylene Glycol (and) Xanthan Gum).
  • Tinosorb® M shows absorption over the entire UV range and even achieves protection in visible blue light.
  • Tinosorb® M at 4% by weight relative to the total weight of the composition in the Emulgade® CPE microemulsion gel marketed by BASF lowers the MMPI content in the dermis by 29% compared to the placebo control irradiated with blue light.
  • the microspheres according to the invention in a content of 1.5% by weight relative to the total weight of the composition show a similar range of protection.
  • composition containing the microspheres according to the invention shows good protection against the increase in the content of MMPI and 8-OHdG caused by blue light (401-500 nm with a peak at 455 nm) in the human skin.
  • Example 3 cosmetic compositions according to the invention
  • the porous microspheres used are those obtained in Example 1 in powder form.
  • Example 3a Fluid emulsion for the face
  • phase B by introducing phase B into phase A and stirring until completely dispersed.
  • the mixture is heated to 75-80°C as is phase C separately.
  • phase C is added to the mixture with stirring.
  • the mixture is left to cool with gentle stirring to ambient temperature and the compounds of phases E and F are added, one after the other.
  • the whole is homogenized for 2 min.
  • the pH is adjusted to 5.2.
  • the cream is prepared by the usual methods in the field well known to those skilled in the art, by mixing phases A and B previously heated to 75° C., then by adding phases C and D by mixing and adjusting the composition with phase E at a pH of 6.2 and at a viscosity of 15,000 mPas (measured with a Brookfield apparatus (RVT; 23° C., spindle TC; 20 revolutions per min).
  • the shampoo is prepared by the usual methods in the field well known to those skilled in the art, by mixing the 4 phases and adjusting the composition at a pH of 5.2 and at a viscosity of 2200 mPas (measured with a Brookfield apparatus (RVT; 23° C., spindle 5; 50 revolutions per min).

Abstract

The invention relates to the non-therapeutic cosmetic use of porous microspheres comprising a metal oxide for protecting the skin, skin appendages and/or mucous membranes against the unattractive and/or unpleasant and/or uncomfortable effects of blue light and/or to decrease and/or slow down the effects on the the skin, skin appendages and/or mucous membranes, the microspheres having: - an average diameter D50, as measured by scanning electron microscopy (SEM), of between 1 µm and 30 µm; - pores having an average diameter D50, as measured by scanning electron microscopy (SEM), of between 50 nm and 250 nm; and - an average porosity, as measured by mercury porosimetry, of between 0.40 and 0.65. The invention also relates to a non-therapeutic cosmetic care method comprising applying the porous microspheres, or a cosmetic composition comprising same, to the skin, mucous membranes and/or skin appendages.

Description

Utilisations cosmétiques contre la lumière bleue de microspheres poreuses d'oxyde métallique Blue Light Cosmetic Uses of Porous Metal Oxide Microspheres
Domaine Technique Technical area
La présente invention concerne l'utilisation cosmétique non thérapeutique de microsphères poreuses d'oxyde métallique pour protéger la peau, les annexes cutanées, notamment les cheveux, et/ou les muqueuses contre les effets inesthétiques et/ou désagréables et/ou inconfortables de la lumière bleue et/ou pour en diminuer et/ou ralentir lesdits effets sur la peau, les annexes cutanées notamment les cheveux, et/ou les muqueuses. The present invention relates to the non-therapeutic cosmetic use of porous metal oxide microspheres to protect the skin, the skin appendages, in particular the hair, and/or the mucous membranes against the unsightly and/or unpleasant and/or uncomfortable effects of light. blue and/or to reduce and/or slow down the said effects on the skin, the skin appendages, in particular the hair, and/or the mucous membranes.
Technique antérieure Prior technique
Le spectre de radiation solaire est réparti sur différents intervalles de longueur d'onde incluant l'ultraviolet (UV; 100-400 nm), le visible (401- 700 nm) et la région infra-rouge (> 700 nm). Les radiations UV représentent une partie hautement énergétique du spectre électromagnétique atteignant l'atmosphère terrestre. Cette région est subdivisée en trois bandes de longueur d'onde: UVC (<280 nm), UVB (280-320 nm) et UVA (320-400 nm). Alors que les UVC sont efficacement bloqués par les molécules d'oxygène, d'ozone et d'azote de la haute atmosphère et que la majorité des UVA passent la couche d'ozone de la stratosphère, les radiations UVB sont uniquement partiellement absorbées par l'ozone stratosphérique. Les régions infra-rouge et visible comptent pour la plus grande majorité des émissions solaire qui pénètrent l'atmosphère. Le spectre visible est composé d'une gamme d'intervalles de longueur d'onde de lumière qui peut être perçue par l'œil humain sous la forme de couleurs. L'arc-en-ciel est un exemple typique de ces différentes couleurs visibles. La radiation solaire est composée de 25% à 30% de lumière bleue, en fonction du spectre solaire de référence. La lumière bleue est donc une lumière visible a haute energie (HEV) avec une longueur d'onde dans la gamme 401 nm à 500 nm. Le soleil est la source principale de lumière bleue naturelle, mais les êtres humains sont aussi de plus en plus exposés à la lumière bleue provenant de sources artificielles, qui varient largement dans le spectre de distribution. Les LEDs bleues émettant de la lumière bleue dans la gamme 401 nm à 495 nm sont considérées comme étant plus dangereuses que les LEDs vertes et rouges. La longueur d'onde dominante des dispositifs électroniques a été estimée comme étant 448 nm (lumière bleue), 535 nm (lumière verte) et 599 (lumière rouge). The solar radiation spectrum is spread over different wavelength ranges including the ultraviolet (UV; 100-400 nm), the visible (401-700 nm) and the infrared region (> 700 nm). UV radiation represents a highly energetic part of the electromagnetic spectrum reaching the Earth's atmosphere. This region is subdivided into three wavelength bands: UVC (<280 nm), UVB (280-320 nm), and UVA (320-400 nm). While UVC is effectively blocked by oxygen, ozone and nitrogen molecules in the upper atmosphere and the majority of UVA passes the ozone layer of the stratosphere, UVB radiation is only partially absorbed by the atmosphere. stratospheric ozone. The infrared and visible regions account for the vast majority of solar emissions entering the atmosphere. The visible spectrum is made up of a range of wavelength intervals of light that can be perceived by the human eye as colors. The rainbow is a typical example of these different visible colors. Solar radiation is composed of 25% to 30% blue light, depending on the reference solar spectrum. Blue light is therefore high energy visible light (HEV) with a wavelength in the range 401 nm to 500 nm. The sun is the main source of natural blue light, but humans are also increasingly exposed to blue light from artificial sources, which vary widely in the distribution spectrum. Blue LEDs emitting blue light in the 401 nm to 495 nm range are considered more dangerous than green and red LEDs. The dominant wavelength of electronic devices has been estimated to be 448 nm (blue light), 535 nm (green light) and 599 (red light).
Bien que les radiations ultraviolettes du soleil soient parmi les facteurs environnementaux préjudiciables les plus omniprésents dont la peau humaine doit se protéger, des avancées récentes ont souligné le rôle important de la lumière visible, et en particulier la lumière bleue, dans le vieillissement prématuré de la peau en raison de la génération d'un stress oxydatif {Nakashima Y, Ohta S, Wolf AM. Blue Hght-induced oxidative stress in live skin - Free Radie Bioi Med. Jui; 108:300-310, 2017). Cette publication mentionne que la lumière bleue, en particulier celle ayant la longueur d'onde la plus courte, pourrait contribuer au vieillissement de la peau de façon similaire aux UVA. Ainsi, en fonction de la lumière d'onde et de la dose appliquée, la lumière bleue influence les réponses physiologiques de la peau. Comme la lumière bleue a la longueur d'onde la plus énergétique de la lumière visible, elle pénètre le plus profondément dans la peau, non seulement dans l'épiderme mais également dans le derme générant un stress oxydatif et produisant des protéases qui dégradent la matrice extracellulaire du derme {Saint-Auret G, Kiening M, Haguet V, Suiierot M, Escaich S, Ramchurn R. The double nature of blue light on skin dependent pathways. IFSCC Congress Munich. ID 560, 2018). Dans la couche cornee, la lumière bleue contribue a la formation de protéines carbonylés qui détériorent la barrière épidermique et altèrent la couleur de la peau Mizutani T, Sumida H, Sagawa Y, Okano Y, Masaki H. Carbony/ated proteins exposed to UVA and to blue light generate reactive oxygen species through a type I photosensitizing reaction. J Dermatol Sci. Dec;84(3):314-321, 2016). La peau est un organe en contact constant avec l'extérieur. Elle joue donc un rôle d'échange mais aussi et surtout de barrière vis-à-vis de l'extérieur. La couche superficielle de la peau, appelée couche cornée, constitue le premier rempart protégeant la peau, sous la forme d'une fine pellicule. Celle-ci par sa nature hydrophobique constitue un rempart à la diffusion de l'eau, principal constituant des cellules et évitant ainsi la déshydratation. Néanmoins, il existe toujours des pertes d'eau dites transépidermales ou autrement dénommées pertes insensibles en eau. Si la couche cornée est affaiblie, par exemple en raison de son exposition à la lumière bleue, la barrière cutanée est rompue et ces pertes insensibles en eau augmentent. La peau devient sèche et plus vulnérable aux agressions extérieures. Le maintien de la teneur en eau via le rôle de la barrière cutanée est donc essentiel pour le maintien des fonctionnalités et l'aspect esthétique de la peau. Although ultraviolet radiation from the sun is among the most ubiquitous damaging environmental factors against which human skin must protect itself, recent advances have highlighted the important role of visible light, and in particular blue light, in premature skin aging. skin due to generation of oxidative stress {Nakashima Y, Ohta S, Wolf AM. Blue Hght-induced oxidative stress in live skin - Free Radie Bioi Med. Jun; 108:300-310, 2017). This publication mentions that blue light, especially that with the shortest wavelength, could contribute to skin aging in a similar way to UVA. Thus, depending on the wave light and the dose applied, blue light influences the physiological responses of the skin. As blue light has the most energetic wavelength of visible light, it penetrates the deepest into the skin, not only in the epidermis but also in the dermis generating oxidative stress and producing proteases which degrade the matrix extracellular dermis {Saint-Auret G, Kiening M, Haguet V, Suiierot M, Escaich S, Ramchurn R. The double nature of blue light on skin dependent pathways. IFSCC Congress Munich. ID 560, 2018). In the stratum corneum, blue light contributes to the formation of carbonyl proteins which deteriorate the epidermal barrier and alter skin color Mizutani T, Sumida H, Sagawa Y, Okano Y, Masaki H. Carbony/ated proteins exposed to UVA and to blue light generate reactive oxygen species through a type I photosensitizing reaction. J Dermatol Sci. Dec;84(3):314-321, 2016). The skin is an organ in constant contact with the outside. It therefore plays a role of exchange but also and above all of a barrier vis-à-vis the outside world. The superficial layer of the skin, called the stratum corneum, constitutes the first rampart protecting the skin, in the form of a thin film. This one by its hydrophobic nature constitutes a rampart with the diffusion of water, principal constituent of the cells and thus avoiding the dehydration. Nevertheless, there are always so-called transepidermal water losses or otherwise called insensible water losses. If the stratum corneum is weakened, for example due to its exposure to blue light, the skin barrier is broken and these insensible water losses increase. The skin becomes dry and more vulnerable to external aggressions. Maintaining the water content via the role of the skin barrier is therefore essential for maintaining the functionalities and the aesthetic appearance of the skin.
La lumière bleue à environ 450 nm favorise la différentiation des kératinocytes et réduit la capacité antioxydante des fibroblastes (Opiander Cl, Hidding S, Werners FB, Born M, Paiiua N, Suschek CV. Effects of blue light irradiation on human dermal fibroblasts. J Photochem Photobioi B. May 3;103(2):118-25. 2011). D'autres études ont démontrés que la lumière bleue augmente la quantité de dérivés réactifs de l’oxygène (ROS), de protéines carbonylés, de métalloprotéinase- 1 (MMPI) et de 8- OHdG (8-oxo-7,8-dihydro-2’-deoxyguanosine). Les MMP-1 et le 8-OHdG sont associés au vieillissement prématuré. En particulier MMPI est une métalloprotéinase appartenant à la famille des enzymes impliquées dans la degradation de la matrice extracellulaire, principalement le collagene du derme incluant le collagène de type I, le collagène de type IV, la fibronectine and les laminines. Les polluants, les UV ou la lumière bleue peuvent ainsi provoquer l'expression de MMPI et peuvent donc amener au vieillissement prématuré de la peau. Blue light at about 450 nm promotes keratinocyte differentiation and reduces the antioxidant capacity of fibroblasts (Opiander Cl, Hidding S, Werners FB, Born M, Paiiua N, Suschek CV. Effects of blue light irradiation on human dermal fibroblasts. J Photochem Photobioi B. May 3;103(2):118-25.2011). Other studies have shown that blue light increases the amount of reactive oxygen species (ROS), protein carbonyls, metalloproteinase-1 (MMPI) and 8-OHdG (8-oxo-7,8-dihydro -2'-deoxyguanosine). MMP-1 and 8-OHdG are associated with premature aging. In particular MMPI is a metalloproteinase belonging to the family of enzymes involved in the degradation of the extracellular matrix, mainly dermal collagen including type I collagen, type IV collagen, fibronectin and laminins. Pollutants, UV or blue light can thus cause the expression of MMPI and can therefore lead to premature aging of the skin.
On retrouve en particulier le collagène de type I dans de nombreux tissus humains tels que tendons, ligaments, cornée et peau. Le collagène de type I est le collagène majoritaire de la peau. Il fait partie des collagènes fibrillaires avec le collagène III et V. C'est le collagène qui confère aux tissus leur résistance mécanique, participant ainsi de façon prépondérante au maintien de leur fermeté. La lumière bleue en dégradant le collagène par l'intermédiaire de MMPI contribue à diminuer la fermeté de la peau.In particular, type I collagen is found in many human tissues such as tendons, ligaments, cornea and skin. Type I collagen is the main collagen in the skin. It is part of the fibrillar collagens with collagen III and V. It is the collagen which gives the tissues their mechanical resistance, thus participating in a preponderant way in maintaining their firmness. Blue light by degrading collagen through MMPI helps to decrease skin firmness.
Les signes les plus visibles du vieillissement prématuré de la peau causé par la lumière bleue apparaissent au niveau du visage : la peau se détend et les premières rides se forment et deviennent visibles. La fermeté et la densité de la peau et des muqueuses sont également dégradés lors du vieillissement prématuré induit par la lumière bleue. Au cours du vieillissement, la formation des fibres élastiques et des fibres de collagène diminue et sous l'action d'un stress oxydatif induit par exemple de la lumière bleue, sa dégradation par les MMPs et les élastases augmentent. Or, il a été observé que, sous l'effet du stress oxydant, une partie de la synthèse d'élastine dans le derme profond, est également augmentée et s'accumule de façon anarchique sous forme d'agrégat d'élastine, contribuant ainsi à la perte de l'élasticité. The most visible signs of premature skin aging caused by blue light appear on the face: the skin relaxes and the first wrinkles form and become visible. The firmness and density of the skin and mucous membranes are also degraded during premature aging induced by blue light. During ageing, the formation of elastic fibers and collagen fibers decreases and under the action of oxidative stress induced, for example, blue light, its degradation by MMPs and elastases increases. However, it has been observed that, under the effect of oxidative stress, part of the synthesis of elastin in the deep dermis is also increased and accumulates in an anarchic manner in the form of elastin aggregate, thus contributing to loss of elasticity.
L'apparence physique et les aspects phénotypiques des fibres kératiniques des annexes cutanées, notamment des cheveux tels que la couleur, la densité, la frisure, la brillance, le volume, la souplesse et le style prennent une place importante dans la communication sociale et l'estime de soi. D'un point de vue fonctionnel, les cheveux ont également un rôle de protection du cuir chevelu contre les agressions extérieures, et en particulier contre les rayonnements ultraviolets et de la lumière bleue. Ils permettent également de maintenir la température corporelle et de fournir des sensations tactiles. The physical appearance and phenotypic aspects of the keratinous fibers of the skin appendages, especially hair such as color, density, crimp, shine, volume, suppleness and style take an important place in social communication and communication. 'self esteem. From a functional point of view, the hair also has a role of protection of the scalp against external aggressions, and in particular against ultraviolet radiation and blue light. They also help maintain body temperature and provide tactile sensations.
Au cours du vieillissement, en particulier induit par la lumière bleue, les qualités structurales et fonctionnelles de la fibre kératinique des annexes cutanées notamment la fibre capillaire se détériorent. Les cheveux et les cils sont plus fins et plus fragiles. Les cheveux sont également plus difficiles à coiffer et à structurer. Les cils et sourcils sont plus difficiles à mettre en place et maquiller. Le vieillissement de la fibre kératinique des annexes cutanées notamment du cheveu comprend le vieillissement de la fibre kératinique notamment capillaire et le vieillissement du follicule pileux. Le cuir chevelu qui contient les follicules pileux joue un rôle également très important dans le comportement et le vieillissement du follicule pileux et par conséquent sur la qualité et la pousse de la fibre capillaire. During ageing, in particular induced by blue light, the structural and functional qualities of the keratin fiber of the skin appendages, in particular the hair fiber, deteriorate. Hair and eyelashes are finer and more fragile. The hair is also more difficult to comb and structure. Eyelashes and eyebrows are more difficult to set up and make up. The aging of the keratin fiber of the skin appendages, in particular of the hair, includes the aging of the keratin fiber, in particular of the hair, and the aging of the hair follicle. The scalp, which contains the hair follicles, also plays a very important role in the behavior and aging of the hair follicle and therefore in the quality and growth of the hair fibre.
La fibre kératinique des annexes cutanées est une structure inerte de type phanère. Elle est composée principalement de cellules mortes kératinisées. On distingue différents types de fibres kératiniques selon leur localisation, leur croissance et leurs fonctions : les cils, les sourcils, les poils notamment barbe et moustache et les cheveux également dénommés fibres capillaires. De manière générale, trois parties concentriques majeures constitue une fibre kératinique: la moelle (ou canal médullaire) au centre, le cortex au niveau de la zone intermédiaire et enfin la cuticule formant les écailles de surface. La zone corticale représente la majeure partie de la tige pilaire (90% du poids total). Elle est le siège de la pigmentation et confère à la fibre kératinique ses propriétés physiques et mécaniques. La cuticule est l'enveloppe protectrice de la fibre kératinique, formée de cellules fortement kératinisées non pigmentées formant les écaillés externes du cheveu. La moelle se trouve au centre de la tige pilaire. Elle est constituée de grandes cellules anucléées, claires ou peu pigmentées en comparaison des cellules corticales. The keratin fiber of the cutaneous appendages is an inert structure of the dander type. It is composed mainly of keratinized dead cells. Different types of keratin fibers are distinguished according to their location, their growth and their functions: eyelashes, eyebrows, body hair, in particular beard and mustache, and hair, also called hair fibers. In general, three major concentric parts constitute a keratin fibre: the medulla (or medullary canal) in the centre, the cortex at the level of the intermediate zone and finally the cuticle forming the surface scales. The cortical zone represents the major part of the hair shaft (90% of the total weight). It is the seat of pigmentation and gives the keratin fiber its physical and mechanical properties. The cuticle is the protective envelope of the keratin fibre, made up of strongly keratinized non-pigmented cells forming the outer scales of the hair. The medulla is located in the center of the hair shaft. It is made up of large anucleate cells, clear or slightly pigmented compared to cortical cells.
L'organe permettant la synthèse de la fibre kératinique des annexes cutanées et notamment capillaire est le follicule pileux. Il se prolonge sous le cuir chevelu dans le cas des cheveux et sous l'épiderme de la peau dans le cas des autres fibres kératiniques et peut être divisé en trois segments de longueur à peu près similaire : l'infundibulum ou segment superficiel, l'isthme ou segment médian, le bulbe ou segment inférieur. Le follicule pileux est constitué de cellules vivantes de type kératinocytes, fibroblastes et mélanocytes et de matrice extracellulaire. L'organisation, les interactions cellulaires et moléculaires permettent la synthèse de la tige pilaire. Elle est créée au niveau de la partie la plus profonde du follicule pileux : le bulbe, et croît en direction de la surface de la peau, notamment pour le cheveu à la surface du cuir chevelu. La tige pilaire auparavant entourée de cellules, devient libre dans l'infundibulum à hauteur de l'embouchure du canal sébacé, appendice qui accompagne le follicule pileux. La fibre kératinique des annexes cutanées notamment capillaire visible à la racine du cuir chevelu pour le cheveu ou à la jonction avec la peau peut être qualifiée de fibre émergente. La fibre non visible à la racine contenue dans la peau, notamment le cuir chevelu, peut être qualifiée de fibre pré-émergente. La croissance moyenne d'une fibre capillaire dure de 3-4 ans en moyenne. Sa vitesse de croissance est estimée à lcm/mois dans des conditions moyennes normales. La tige met environ 2 semaines depuis le siège de sa création à l'affleurement au niveau de la surface du cuir chevelu. Une tige émergente de 6 cm met environ 6 mois à être formée. The organ allowing the synthesis of the keratin fiber of the cutaneous annexes and in particular of the hair is the hair follicle. It extends under the scalp in the case of hair and under the epidermis of the skin in the case of other keratinous fibers and can be divided into three segments of roughly similar length: the infundibulum or superficial segment, the isthmus or middle segment, bulb or lower segment. The hair follicle is made up of living cells such as keratinocytes, fibroblasts and melanocytes and of extracellular matrix. The organization, the cellular and molecular interactions allow the synthesis of the hair shaft. It is created at the level of the deepest part of the hair follicle: the bulb, and grows towards the surface of the skin, in particular for the hair on the surface of the scalp. The hair shaft, previously surrounded by cells, becomes free in the infundibulum at the height of the mouth of the sebaceous canal, an appendage which accompanies the hair follicle. The keratin fiber of the cutaneous appendages, in particular capillary, visible at the root of the scalp for the hair or at the junction with the skin can be qualified as emerging fibre. The fiber not visible at the root contained in the skin, in particular the scalp, can be qualified as pre-emergent fiber. The average growth of a hair fiber lasts 3-4 years on average. Its growth rate is estimated at 1cm/month under normal average conditions. The stem takes approximately 2 weeks from the seat of its creation to flush with the surface of the scalp. An emergent stem of 6 cm takes about 6 months to form.
Avec le vieillissement, la qualité de la fibre des annexes cutanées diminue la rendant plus fragile au contact de son environnement. Un cheveu vieilli, en particulier prématurément, est un cheveu plus fin, plus abîme, plus cassant qu'un cheveu jeune. La chevelure manque de volume de brillance et de vitalité. With aging, the quality of the fiber of the skin appendages decreases, making it more fragile in contact with its environment. an aged hair, particularly prematurely, hair is finer, more damaged, more brittle than young hair. The hair lacks volume, shine and vitality.
La lumière bleue altère directement les propriétés structurelles et fonctionnelles de la fibre capillaire. Ainsi les cheveux vieillis sont plus abimés, plus fins et en particulier sont difficiles à coiffer et à mettre en forme comparés à des cheveux plus jeunes et sont cassants, notamment fourchus. Cette perte de qualité de surface des cheveux est visible et inesthétique. Les cheveux reflètent en effet également moins la lumière et sont ainsi visiblement plus ternes, moins brillants, moins lumineux. Ce vieillissement a également un impact sur la chute des cheveux ce qui peut en résulter une perception de fragilité et une perte des cheveux au cours du temps. La chevelure apparait ainsi comme moins dense. Les autres fibres kératiniques des annexes cutanées sont exposées au même phénomène de vieillissement altérant leur qualité et leur quantité, de manière particulièrement inesthétique et souvent non désirée pour les cils, les sourcils et les ongles. Blue light directly alters the structural and functional properties of the hair fiber. Thus, aged hair is more damaged, finer and in particular is difficult to comb and shape compared to younger hair and is brittle, in particular split ends. This loss of surface quality of the hair is visible and unsightly. The hair also reflects less light and is thus visibly duller, less shiny, less luminous. This aging also has an impact on hair loss which can result in a perception of fragility and hair loss over time. The hair thus appears less dense. The other keratinous fibers of the skin appendages are exposed to the same phenomenon of aging altering their quality and their quantity, in a particularly unsightly and often undesirable way for the eyelashes, the eyebrows and the nails.
En outre, au niveau du bulbe du follicule pileux notamment capillaire, les mélanocytes matures spécialisés dans la synthèse de pigments (mélanine) transfèrent ces pigments aux kératinocytes du follicule pileux, ou cellules de la matrice, qui produisent la fibre kératinique, notamment capillaire. Lors du vieillissement la quantité de pigments transférée à la fibre kératinique des annexes cutanées, notamment capillaire diminue. Cette perte de pigmentation de la fibre kératinique peut être due à des défauts de genèse de la mélanine ou à la perte en nombre de mélanocytes qui la produisent. La vitesse et la durée de la pousse de la tige kératinique, notamment capillaire diminue également ainsi que son diamètre. Toutes les tiges kératiniques des annexes cutanées, notamment capillaires ne perdent pas leur pigment de manière synchrone au cours du temps. Le grisonnement ou le blanchiment des fibres keratiniques des annexes cutanées, notamment des cils, sourcils, de la barbe, moustache, chevelure, avec l'âge est la conséquence visuelle globale des tiges kératiniques pigmentées et non-pigmentées, ces dernières apparaissant de couleur blanche. Un éclaircissement des cils, sourcils, barbe, moustache et chevelure peut résulter, d'une dilution du pigment, d'une augmentation de la fréquence de fibres kératiniques des annexes cutanées, notamment cheveux, non pigmentées ou d'une augmentation de la perte des fibres kératiniques pigmentées, notamment cheveux pigmentés. In addition, at the bulb of the hair follicle, in particular capillary, the mature melanocytes specialized in the synthesis of pigments (melanin) transfer these pigments to the keratinocytes of the hair follicle, or cells of the matrix, which produce keratin fibre, in particular capillary. During aging, the quantity of pigments transferred to the keratin fiber of the skin appendages, in particular the capillary, decreases. This loss of pigmentation of the keratin fiber may be due to defects in the genesis of melanin or to the loss in number of melanocytes which produce it. The speed and duration of the growth of the keratin stem, in particular the capillary, also decreases as well as its diameter. All the keratinous rods of the skin appendages, in particular capillaries, do not lose their pigment synchronously over time. THE graying or whitening of the keratin fibers of the skin appendages, in particular the eyelashes, eyebrows, beard, mustache, hair, with age is the overall visual consequence of the pigmented and non-pigmented keratin stalks, the latter appearing white in color. Lightening of the eyelashes, eyebrows, beard, mustache and hair may result from a dilution of the pigment, an increase in the frequency of keratinous fibers of the cutaneous appendages, in particular hair, which are not pigmented or an increase in the loss of pigmented keratinous fibres, in particular pigmented hair.
Il existe donc un besoin de trouver de nouveaux actifs cosmétiques permettant de protéger la peau et/ou les muqueuses et/ou les annexes cutanées contre la lumière bleue et ses effets inesthétiques et/ou désagréables et/ou inconfortables tels que son vieillissement prématuré et l'affaiblissement de la barrière cutanée. There is therefore a need to find new cosmetic active agents making it possible to protect the skin and/or the mucous membranes and/or the cutaneous appendages against blue light and its unsightly and/or unpleasant and/or uncomfortable effects such as its premature aging and the weakening of the skin barrier.
La Demanderesse a découvert que des microsphères d'oxyde métallique ont la propriété de protéger la peau, les muqueuses et les annexes cutanées contre la lumière bleue en ayant en particulier un effet de filtre anti-lumière bleue. The Applicant has discovered that metal oxide microspheres have the property of protecting the skin, mucous membranes and cutaneous appendages against blue light, in particular by having an anti-blue light filter effect.
De telles microsphères présentent en effet la capacité unique, grâce à la présence de pores de distribution de taille monodisperse ou bimodale, en particulier grâce à un réseau de pores ordonné, de pouvoir cibler la réflexion d'une longueur d'onde précise. En effet la taille des pores et leur quantité (porosité) ainsi que la taille des microsphères peuvent-être soigneusement choisies à cet effet grâce à la fabrication au préalable de gabarit/modèle de polymère. Ainsi, la Demanderesse a découvert que des microsphères d'oxyde métallique particulières ayant un diamètre moyen D50 mesuré par microscopie électronique à balayage (SEM) allant de 1 pm à 30 pm, des pores dont le diamètre moyen D50 mesuré par microscopie électronique à balayage (SEM) va de 50nm à 250nm et une porosité moyenne mesurée par porosimetrie au mercure allant de 0,4 a 0,65, pouvaient, lorsqu'elles se trouvent sur la peau, les muqueuses et/ou les annexes cutanées, en particulier empêcher la transmission de la lumière bleue. Such microspheres in fact have the unique ability, thanks to the presence of pores with a monodisperse or bimodal size distribution, in particular thanks to an ordered network of pores, of being able to target the reflection of a precise wavelength. In fact, the size of the pores and their quantity (porosity) as well as the size of the microspheres can be carefully chosen for this purpose thanks to the prior manufacture of a template/polymer model. Thus, the Applicant has discovered that particular metal oxide microspheres having an average diameter D 50 measured by scanning electron microscopy (SEM) ranging from 1 μm to 30 μm, pores whose average diameter D 50 measured by electron microscopy at scanning (SEM) ranges from 50nm to 250nm and a porosity average measured by mercury porosimetry ranging from 0.4 to 0.65, could, when they are on the skin, the mucous membranes and/or the skin appendages, in particular prevent the transmission of blue light.
Les microsphères selon l'invention offrent l'avantage de convenir à toutes les peaux quel qu'en soit le type, la carnation et l'éclat. Un autre avantage de la présente invention est que les sphères présentent une grande stabilité et sont utilisables sous forme de poudre ou en composition. Elles sont inertes ce qui permet de les formuler facilement dans toute nature de compositions cosmétiques, que celles-ci soient lipophiles ou hydrophiles. Un autre avantage est que les sphères sont utilisables avec les ingrédients classiques des compositions cosmétiques, The microspheres 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 compositions, whether these are lipophilic or hydrophilic. Another advantage is that the spheres can be used with the classic ingredients of cosmetic compositions,
Des sphères d'oxyde métalliques ont déjà été décrites dans les demandes de brevet W02020/183108 et WO2020/182936 dans le cadre d'applications cosmétiques. Toutefois ces demandes ne décrivent ni ne suggèrent l'effet protecteur de ces microsphères contre la lumière bleue et ses effets inesthétiques et/ou désagréables et/ou inconfortables.. Metal oxide spheres have already been described in patent applications WO2020/183108 and WO2020/182936 in the context of cosmetic applications. However, these applications do not describe or suggest the protective effect of these microspheres against blue light and its unsightly and/or unpleasant and/or uncomfortable effects.
Exposé de l'invention Disclosure of Invention
La présente invention a ainsi pour objet l'utilisation cosmétique non thérapeutique de microsphères poreuses comprenant, avantageusement constituée par, un oxyde métallique pour protéger la peau, les annexes cutanées, notamment les cheveux, et/ou les muqueuses contre les effets inesthétiques et/ou désagréables et/ou inconfortables de la lumière bleue et/ou pour en diminuer et/ou ralentir lesdits effets sur la peau, les annexes cutanées notamment les cheveux, et/ou les muqueuses, et/ou pour empêcher la survenance desdits effets inesthétiques et/ou désagréables et/ou inconfortables de la lumière bleue et/ou d’en ralentir l’apparition, lesdites microsphères ayant : The subject of the present invention is thus the non-therapeutic cosmetic use of porous microspheres comprising, advantageously constituted by, a metal oxide to protect the skin, the skin appendages, in particular the hair, and/or the mucous membranes against the unsightly effects and/or unpleasant and/or uncomfortable effects of blue light and/or to reduce and/or slow down the said effects on the skin, the skin appendages, in particular the hair, and/or the mucous membranes, and/or to prevent the occurrence of the said unsightly effects and/ or unpleasant and/or uncomfortable to blue light and/or to slow down its appearance, said microspheres having:
- un diamètre moyen D50 mesuré par microscopie électronique à balayage (SEM) allant de 1 pm à 30 pm, - des pores dont le diamètre moyen D50 mesure par microscopie électronique à balayage (SEM) va de 50nm à 250nm et - an average diameter D 50 measured by scanning electron microscopy (SEM) ranging from 1 μm to 30 μm, - pores whose average diameter D 50 measured by scanning electron microscopy (SEM) ranges from 50 nm to 250 nm and
- une porosité moyenne mesurée par porosimétrie au mercure allant de 0,40 à 0,65. - an average porosity measured by mercury porosimetry ranging from 0.40 to 0.65.
Au sens de la présente invention, on entend par « muqueuse », la muqueuse oculaire, la muqueuse vaginale, la muqueuse uro-génitale, la muqueuse anale, la muqueuse nasale et/ou la muqueuse buccale, labiale et/ou gingivale, préférentiellement les muqueuses les plus exposées à la lumière bleue, notamment les muqueuses oculaires et/ou labiales et/ou nasales. Within the meaning of the present invention, the term "mucosa" means the ocular mucosa, the vaginal mucosa, the uro-genital mucosa, the anal mucosa, the nasal mucosa and/or the buccal, labial and/or gingival mucosa, preferentially the mucous membranes most exposed to blue light, in particular the ocular and/or labial and/or nasal mucous membranes.
Au sens de la présente invention, on entend par « peau », la peau du visage et du corps incluant le cuir chevelu et par « cuir chevelu » les zones temporales du cuir chevelu, la zone frontale, la zone pariétale et le vertex ou sommet du crâne. Within the meaning of the present invention, the term “skin” is understood to mean the skin of the face and of the body including the scalp and by “scalp” the temporal zones of the scalp, the frontal zone, the parietal zone and the vertex or vertex. of the skull.
Au sens de la présente invention, on entend par « annexes cutanées » les cheveux, les cils, sourcils, la barbe, la moustache et/ou les ongles, préférentiellement les cheveux. Within the meaning of the present invention, the term "cutaneous appendages" means the hair, the eyelashes, the eyebrows, the beard, the mustache and/or the nails, preferentially the hair.
Au sens de la présente invention, on entend par « lumière bleue », la lumière ayant une longueur d'onde allant de 401 à 500nm, avantageusement de 415 à 490nm, plus avantageusement de 420 à 480nm, et en particulier de 430 à 460 nm. Within the meaning of the present invention, the term "blue light" means light having a wavelength ranging from 401 to 500 nm, advantageously from 415 to 490 nm, more advantageously from 420 to 480 nm, and in particular from 430 to 460 nm .
L'utilisation selon l'invention est cosmétique, et préférentiellement par application topique sur au moins une zone concernée ou une partie de peau saine, de muqueuse saine et/ou d'annexes cutanées saines, préférentiellement les cheveux, préférentiellement chez l'homme. The use according to the invention is cosmetic, and preferentially by topical application on at least one zone concerned or a part of healthy skin, of healthy mucous membrane and/or of healthy skin appendages, preferentially the hair, preferentially in humans.
Au sens de la présente invention, on entend par « utilisation cosmétique » une utilisation non thérapeutique, non pharmaceutique des sphères selon l'invention, préférentiellement destinée à, en particulier sur, une peau saine, notamment un cuir chevelu sain, et/ou des annexes cutanées saines, en particulier des cheveux sains, et/ou des muqueuses saines.Within the meaning of the present invention, the term "cosmetic use" means a non-therapeutic, non-pharmaceutical use of the spheres according to the invention, preferably intended for, in particular on, a skin healthy, in particular a healthy scalp, and/or healthy skin appendages, in particular healthy hair, and/or healthy mucous membranes.
Au sens de la présente invention, on entend par « partie de peau » et/ou « zone de peau » dite « saine », une partie de la peau et/ou une zone de peau, qualifiée de non pathologique par un dermatologue, c'est-à-dire qui ne présente pas d'infection, d'inflammation, notamment sous forme de coup de soleil, de maladie ou d'affections cutanées telle que folliculite, candidose, psoriasis, ichtyose, impétigo, eczéma, acné, furoncles, abcès, herpès, ecthyma, érysipèle ou dermatite, de varice, de couperose ou de télangiectasie, de pathologies ou de plaies ou de blessures ou de brûlure ou ne souffre pas d'élastose solaire, qui n'est pas une peau réactive ou à tendance atopique. Il s'agit en particulier d'une partie de peau et/ou de muqueuse constituée de cellules qualifiées de « normales » par un médecin, c'est-à-dire de cellules non cancéreuses. Within the meaning of the present invention, the term “part of skin” and/or “zone of skin” referred to as “healthy” is understood to mean a part of the skin and/or a zone of skin, qualified as non-pathological by a dermatologist, c i.e. which does not present with infection, inflammation, in particular in the form of sunburn, disease or skin conditions such as folliculitis, candidiasis, psoriasis, ichthyosis, impetigo, eczema, acne, boils , abscess, herpes, ecthyma, erysipelas or dermatitis, varicose veins, rosacea or telangiectasia, pathologies or wounds or wounds or burns or does not suffer from solar elastosis, which is not reactive skin or to atopic tendency. It is in particular a part of skin and/or mucosa made up of cells qualified as “normal” by a doctor, that is to say non-cancerous cells.
Le terme « application topique », utilisé ici, signifie appliquer les microsphères selon la présente invention éventuellement sous forme d'ingrédient actif et/ou de composition, sur la surface de la peau incluant le cuir chevelu, les annexes cutanées notamment les cheveux et/ou les muqueuses, notamment par application directe, tel que par massage avec des mouvements circulaires, ou par vaporisation des microsphères sur la surface de la zone concernée de la peau et/ou des muqueuses et/ou des annexes cutanées. The term “topical application”, used here, means applying the microspheres 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 or the mucous membranes, in particular by direct application, such as by massage with circular movements, or by vaporization of the microspheres on the surface of the area concerned of the skin and/or of the mucous membranes and/or of the skin appendages.
Au sens de la présente invention, on entend par « protéger la peau et/ou les muqueuses et/ou les annexes cutanées», maintenir au moins partiellement la structure et/ou les propriétés visuelles et/ou les propriétés biomécaniques et/ou les propriétés de surface et/ou de texture et/ou les qualités sensorielles de la peau et/ou des muqueuses et/ou des annexes cutanées, préférentiellement des fibres kératiniques, encore préférentiellement des cheveux. Cette protection est préférentiellement evaluee lorsque la peau et/ou les muqueuses et/ou les annexes cutanées sont exposées à la lumière bleue. Within the meaning of the present invention, the term “protect the skin and/or the mucous membranes and/or the cutaneous appendages”, at least partially maintain the structure and/or the visual properties and/or the biomechanical properties and/or the properties surface and/or texture and/or the sensory qualities of the skin and/or of the mucous membranes and/or of the cutaneous appendages, preferentially of keratin fibres, more preferentially of the hair. This protection is preferably evaluated when the skin and/or mucous membranes and/or skin appendages are exposed to blue light.
En particulier la protection de la peau et/ou des muqueuses et/ou des annexes cutanées contre les effets inesthétiques et/ou désagréables et/ou inconfortables de la lumière bleue peut être évaluée par analyse de la teneur en MMPI dans le derme ou l'épiderme ou de la teneur en 8-OHdG dans la peau. Cette analyse est réalisée par immunomarquage dans les conditions indiquées dans l'exemple 2. In particular, the protection of the skin and/or mucous membranes and/or skin appendages against the unsightly and/or unpleasant and/or uncomfortable effects of blue light can be assessed by analyzing the MMPI content in the dermis or epidermis or 8-OHdG content in the skin. This analysis is carried out by immunolabeling under the conditions indicated in example 2.
Cette analyse est en particulier réalisée sur une peau traitée par les microsphères selon l'invention soumise à un rayonnement de lumière bleue, en particulier à 85J/cm2 (longueur d'onde 401-500 nm du spectre de lumière visible avec un pic à 455 nm pendant 4 heures), et comparé aux résultats d'analyse obtenus avec une peau non traitée par les microsphères selon l'invention et soumise à un rayonnement de lumière bleue similaire, en particulier tel que décrit dans l'exemple 2. This analysis is in particular carried out on skin treated with the microspheres according to the invention subjected to blue light radiation, in particular at 85J/cm 2 (wavelength 401-500 nm of the visible light spectrum with a peak at 455 nm for 4 hours), and compared with the analysis results obtained with skin not treated with the microspheres according to the invention and subjected to similar blue light radiation, in particular as described in example 2.
La baisse de la teneur en MMPI dans le derme de la peau traitée par les microsphères selon l'invention est avantageusement d'au moins 10%, plus avantageusement d'au moins 20%. The drop in the MMPI content in the dermis of the skin treated with the microspheres according to the invention is advantageously at least 10%, more advantageously at least 20%.
La baisse de la teneur en MMPI dans l'épiderme de la peau traitée par les microsphères selon l'invention est avantageusement d'au moins 30%, plus avantageusement d'au moins 50%. The decrease in the MMPI content in the epidermis of the skin treated with the microspheres according to the invention is advantageously at least 30%, more advantageously at least 50%.
La baisse de la teneur en 8-OHdG dans la peau traitée par les microsphères selon l'invention est avantageusement d'au moins 20%, plus avantageusement d'au moins 30%. The drop in the 8-OHdG content in the skin treated with the microspheres according to the invention is advantageously at least 20%, more advantageously at least 30%.
Selon la présente invention, les « effets inesthétiques et/ou désagréables et/ou inconfortables de la lumière bleue » sont avantageusement choisis parmi le vieillissement de la peau et/ou des muqueuses et/ou des annexes cutanées et/ou l'altération de la barrière cutanée et/ou mucosale et/ou la déshydratation de la peau et/ou des muqueuses et/ou des annexes cutanées et/ou l'alteration des propriétés biomecaniques de la peau et/ou des muqueuses et/ou des annexes cutanées. According to the present invention, the "unsightly and/or unpleasant and/or uncomfortable effects of blue light" are advantageously chosen from aging of the skin and/or mucous membranes and/or skin appendages and/or alteration of skin and/or mucosal barrier and/or dehydration of the skin and/or mucous membranes and/or appendages and/or alteration of the biomechanical properties of the skin and/or mucous membranes and/or skin appendages.
En particulier les « effets inesthétiques de la lumière bleue » peuvent consister en l'apparition d'irrégularités inesthétiques du relief, en particulier du microrelief, et/ou de la texture de la peau, des muqueuses et/ou des annexes cutanées et/ou d'irrégularités de la couleur de la peau, des muqueuses et/ou des annexes cutanées, en particulier rendant le teint inhomogène. In particular, the “unaesthetic effects of blue light” may consist of the appearance of unaesthetic irregularities in the relief, in particular the microrelief, and/or the texture of the skin, the mucous membranes and/or the skin appendages and/or irregularities in the color of the skin, mucous membranes and/or skin appendages, in particular making the complexion uneven.
Selon la présente invention, les irrégularités inesthétiques du relief, en particulier du microrelief, et de la texture de la peau sont les rides et les ridules notamment la ride du lion et de la patte d'oie, les aspérités et l'aspect rugueux. According to the present invention, the unsightly irregularities of the relief, in particular of the microrelief, and of the texture of the skin are wrinkles and fine lines, in particular frown lines and crow's feet, asperities and the rough appearance.
Selon la présente invention, les irrégularités de la couleur de la peau sont les taches pigmentaires, en particulier les taches de vieillesse ou des taches hyperpigmentées ou dépigmentées, le masque de grossesse, les rougeurs, mais également la perte d'éclat du teint, le teint terne et les cernes. According to the present invention, the irregularities in the color of the skin are pigmentary spots, in particular age spots or hyperpigmented or depigmented spots, pregnancy mask, redness, but also loss of radiance of the complexion, dull complexion and dark circles.
Selon un mode préférentiel, les effets inesthétiques de la lumière bleue sur la peau et/ou les muqueuses sont sélectionnés parmi l'altération du microrelief de la peau et/ou des muqueuses, l'apparition des rides et/ou ridules, la perte d'éclat du teint, le manque d'homogénéité du teint, l'apparition d'un teint terne et/ou de cernes et/ou de taches pigmentaires, le relâchement cutanée et/ou la perte de tonicité et/ou d'élasticité et/ou de fermeté et/ou de densité de la peau et/ou des muqueuses et/ou l'altération des propriétés de surface et/ou de texture et/ou visuelle et tout mélange de ceux-ci. According to a preferential mode, the unsightly effects of blue light on the skin and/or the mucous membranes are selected from among the alteration of the microrelief of the skin and/or the mucous membranes, the appearance of wrinkles and/or fine lines, the loss of radiance of the complexion, lack of uniformity of the complexion, the appearance of a dull complexion and/or dark circles and/or pigment spots, slackening of the skin and/or loss of tone and/or elasticity and /or firmness and/or density of the skin and/or mucous membranes and/or alteration of surface and/or texture and/or visual properties and any mixture thereof.
Les effets inesthétiques de la lumière bleue sur les annexes cutanées, préférentiellement des cheveux, sont en particulier l'altération de ses propriétés visuelle et/ou de ses propriétés de surface et/ou de texture, ( apparition d un aspect terne, cassant. Pour les poils et cheveux, les effets inesthétiques incluent également l'apparition d'un aspect cassant, friable, abimé et/ou de difficulté à les mettre en forme, notamment pour les cheveux, à les coiffer, et/ou de pointes fourchues. The unsightly effects of blue light on skin appendages, preferably hair, are in particular the alteration of its visual properties and/or its surface and/or texture properties, (appearance of a dull, brittle appearance. For hair and hair, the unsightly effects also include the appearance of a brittle, crumbly, damaged appearance and/or difficulty in shaping them, in particular for the hair, comb, and/or split ends.
Les effets inesthétiques de la lumière bleue sur les muqueuses sont notamment l'apparition d'un aspect terne, craquelé, flétri et/ou abimé ainsi que de squames. The unsightly effects of blue light on the mucous membranes include the appearance of a dull, cracked, withered and/or damaged appearance as well as scales.
Selon la présente invention, les « effets désagréables et/ou inconfortables de la lumière bleue » peuvent consister en l'apparition d'une sensation de tiraillement, de tension, de fourmillements, de picotements, et/ou de rugosité de la peau et/ou des muqueuses et/ou l'altération des qualités sensorielles de la peau et/ou des muqueuses et/ou des annexes cutanées en particulier des cheveux. According to the present invention, the "unpleasant and/or uncomfortable effects of blue light" can consist of the appearance of a sensation of tightness, tension, tingling, tingling, and/or roughness of the skin and/or or the mucous membranes and/or the alteration of the sensory qualities of the skin and/or the mucous membranes and/or the cutaneous appendages, in particular the hair.
Ainsi avantageusement l'utilisation cosmétique non thérapeutique des microsphères selon l'invention est pour prévenir et/ou ralentir Thus advantageously the non-therapeutic cosmetic use of the microspheres according to the invention is to prevent and/or slow down
- l'apparition de rides et/ou ridules et/ou de tâches pigmentaires sur la peau et/ou les muqueuses, et/ou - the appearance of wrinkles and/or fine lines and/or pigment spots on the skin and/or mucous membranes, and/or
- la perte d'éclat du teint de la peau et/ou des muqueuses et/ou le manque d'homogénéité du teint de la peau et/ou des muqueuses et/ou- loss of radiance in the complexion of the skin and/or mucous membranes and/or lack of uniformity in the complexion of the skin and/or mucous membranes and/or
- le relâchement cutanée et/ou - sagging skin and/or
-la perte de tonicité et/ou d'élasticité et/ou de fermeté et/ou de densité de la peau et/ou des muqueuses et/ou -loss of tone and/or elasticity and/or firmness and/or density of the skin and/or mucous membranes and/or
- le blanchiment et/ou grisonnement des annexes cutanées et/ou - whitening and/or graying of the skin appendages and/or
- la déshydratation et/ou les pertes insensibles en eau de la peau et/ou des muqueuses et/ou - dehydration and/or transepidermal water loss from the skin and/or mucous membranes and/or
- l'altération du microrelief de la peau et/ou des muqueuses et/ou - alteration of the microrelief of the skin and/or mucous membranes and/or
- l'altération des propriétés de surface et/ou de texture et/ou visuelle et/ou des qualités sensorielles de la peau et/ou des muqueuses et/ou des annexes cutanées en particulier des cheveux. Cette utilisation n'est pas pour améliorer l'aspect et/ou le confort de la peau et/ou des annexes cutanées et/ou des muqueuses, notamment par effet de masquage, mais est pour empêcher la survenance des effets inesthétiques et/ou désagréables et/ou inconfortables de la lumière bleue ou tout le moins d'en ralentir l'apparition. - the alteration of the surface properties and/or of texture and/or visual and/or of the sensory qualities of the skin and/or of the mucous membranes and/or of the cutaneous appendages in particular of the hair. This use is not to improve the appearance and/or comfort of the skin and/or skin appendages and/or mucous membranes, in particular by masking effect, but is to prevent the occurrence of unsightly and/or unpleasant effects and/or uncomfortable from blue light or at the very least to slow down its appearance.
De manière générale, la prévention et/ou diminution des effets inesthétiques peut être visualisée et évaluée par microscopie et/ou par analyse de photographie haute résolution avec notamment mesure de la brillance de la zone de peau, muqueuse et/ou annexes cutanées. In general, the prevention and/or reduction of the unsightly effects can be visualized and evaluated by microscopy and/or by analysis of high resolution photography with in particular measurement of the shine of the area of skin, mucous membrane and/or cutaneous appendages.
La prévention et/ou ralentissement de la perte d'éclat du teint dit « radiance » ou « glow » en anglais peut notamment être mesurée par une méthode instrumentale objective. Cette méthode de mesure in vivo consiste à prendre des photographies hautes résolution en configuration polarisée croisées du visage des volontaires à 45° avant et après application du produit testé. Sur la base de ces photographies numériques, une analyse d’image permet d’extraire et de quantifier des paramètres spécifiques (par exemple : L*, a*, b*, C, h°) reliés à la couleur, l’éclat, l’homogénéité, et la texture de la peau. The prevention and/or slowing down of the loss of radiance of the complexion called “radiance” or “glow” in English can in particular be measured by an objective instrumental method. This in vivo measurement method consists of taking high-resolution photographs in a cross-polarized configuration of the faces of volunteers at 45° before and after application of the tested product. Based on these digital photographs, an image analysis makes it possible to extract and quantify specific parameters (for example: L*, a*, b*, C, h°) related to color, brightness, the homogeneity, and the texture of the skin.
De même, la brillance dite « gloss » en anglais peut notamment être mesurée selon cette méthode sur la base de photographies hautes résolution en configuration polarisée croisées et polarisée parallèles du visage des volontaires prises à 45° avant et après application du produit testé. Sur la base de ces photographies numériques, une analyse d’image permet d’extraire et de quantifier des paramètres spécifiques reliés à la brillance tels que la brillance spéculaire et la brillance de contraste. Similarly, the so-called "gloss" in English can in particular be measured according to this method on the basis of high-resolution photographs in cross-polarized and parallel-polarized configuration of the face of the volunteers taken at 45° before and after application of the tested product. Based on these digital photographs, an image analysis makes it possible to extract and quantify specific parameters related to gloss such as specular gloss and contrast gloss.
Au sens de la présente invention, on entend par « pertes insensibles en eau », la diffusion passive et perspiration insensible mesurée au niveau cutanée ou mucosale. Egalement dénommée pertes transépidermiques en eau ou TEWL (transepidermal waterloss), les pertes insensibles en eau peuvent etre mesurées par differentes methodes notamment in vivo en particulier via un évaporimètre, un tewamètre, notamment in vitro, en particulier par la technique en cylindre ouvert décrite dans l'exemple 1 de la demande de brevet WO 2014/027163 et/ou ex vivo. Ainsi, par exemple, les pertes insensibles en eau sont mesurées par la technique décrite dans l'exemple 1 de la demande de brevet WO 2014/027163 en cylindre ouvert et la diminution est déterminée par rapport à un témoin non traité. Cette technique s'inspire de celles décrites dans les publications Lieb et al. « A new in vitro method for transepidermai water loss : a possible method for moisturizer evaluation », J. Soc. Cosmet. Chem. , March 1988, 39, 107-109 et Strussmann et al. « Water waper permeability of skin care products in relation to molecular and environmental influence », Int. Jounal of Cosmetic Science, 1993, 15, 227-233. Néanmoins effectué sous étuve et donc en atmosphère sèche et à température élevée (45°C), ce test accentue et amplifie le phénomène de pertes insensibles en eau, permettant une mesure dans des conditions particulièrement sévères.Within the meaning of the present invention, the term “insensible water losses” means passive diffusion and insensible perspiration measured at the cutaneous or mucosal level. Also called transepidermal water loss or TEWL (transepidermal waterloss), transepidermal water loss can be measured by different methods, in particular in vivo, in particular via an evaporimeter, a tewameter, in particular in vitro, in particular by the open cylinder technique described in example 1 of patent application WO 2014/027163 and/or ex vivo . Thus, for example, the insensible water losses are measured by the technique described in example 1 of patent application WO 2014/027163 in an open cylinder and the reduction is determined relative to an untreated control. This technique is inspired by those described in the publications Lieb et al. “A new in vitro method for transepidermal water loss: a possible method for moisturizer evaluation”, J. Soc. Cosmetic. Chem. , March 1988, 39, 107-109 and Strussmann et al. "Water waper permeability of skin care products in relation to molecular and environmental influence", Int. Journal of Cosmetic Science, 1993, 15, 227-233. Nevertheless, carried out in an oven and therefore in a dry atmosphere and at high temperature (45°C), this test accentuates and amplifies the phenomenon of insensible water losses, allowing measurement under particularly severe conditions.
Au sens de la présente invention, on entend par « teneur en eau de la peau et/ou des muqueuses », la quantité d'eau contenue dans les épithélia, en particulier l'épiderme et/ou l'épithélium des muqueuses. Cette teneur traduit ainsi l'état d'hydratation. Il existe différentes méthodes de mesure de la teneur en eau de la peau et/ou des muqueuses, notamment in vivo et en particulier via le cornéomètre, et/ou par la mesure de la desquamation via le cornéofix, ou in vitro, notamment via la mesure de la conductivité diélectrique, en particulier selon la méthode décrite dans l'exemple 4 de la demande de brevet WO 2014/027163. Within the meaning of the present invention, the term “water content of the skin and/or of the mucous membranes” is understood to mean the quantity of water contained in the epithelia, in particular the epidermis and/or the epithelium of the mucous membranes. This content thus reflects the state of hydration. There are various methods for measuring the water content of the skin and/or mucous membranes, in particular in vivo and in particular via the corneometer, and/or by measuring desquamation via the corneofix, or in vitro, in particular via the measurement of the dielectric conductivity, in particular according to the method described in example 4 of patent application WO 2014/027163.
Au sens de la présente invention, on entend par « prévenir ou ralentir la perte de fermeté » une prévention et/ou un ralentissement à des fins esthétiques de la perte de fermeté de la peau et/ou des muqueuses soumise à un rayonnement de lumière bleue en particulier par comparaison entre de la peau et/ou des muqueuses traitée a l'aide des microsphères selon l'invention et soumise à un rayonnement de lumière bleue et de la peau et/ou des muqueuses non traitée et soumise à un rayonnement de lumière bleue ou non soumise à un rayonnement de lumière bleue. Within the meaning of the present invention, the term "prevent or slow down the loss of firmness" means a prevention and/or a slowing down for aesthetic purposes of the loss of firmness of the skin and/or mucous membranes subjected to blue light radiation. in particular by comparison between skin and/or mucous membranes treated with the aid of the microspheres according to the invention and subjected to blue light radiation and untreated skin and/or mucous membranes and subjected to blue light radiation or not subjected to blue light radiation.
Les méthodes de mesure classiques de la fermeté de la peau consistent à mesurer la profondeur de ses déformations possibles, tandis que celles visant à mesurer l'élasticité de la peau consistent à mesurer sa capacité à revenir à son état initial après torsion et/ou déformation. The classic methods for measuring the firmness of the skin consist in measuring the depth of its possible deformations, while those aimed at measuring the elasticity of the skin consist in measuring its capacity to return to its initial state after torsion and/or deformation. .
La prévention ou diminution de la perte de fermeté peut être mesurée selon les méthodes classiques notamment par mesure in vivo à l'aide d'un cutomètre, d'un densiscore, d'un torquemètre ou encore d'un dynaskin associé à un dermatop et en particulier par comparaison entre de la peau et/ou des muqueuses traitée à l'aide des microsphères selon l'invention et soumise à un rayonnement de lumière bleue et de la peau et/ou des muqueuses non traitée et soumise à un rayonnement de lumière bleue ou non soumise à un rayonnement de lumière bleue. La prévention ou diminution de la perte de l'élasticité peut être mesurée selon les méthodes classiques notamment par mesure in vivo, à l'aide d'un ballistomètre ou d'un cornéovacuomètre et en particulier par comparaison entre de la peau et/ou des muqueuses traitée à l'aide des microsphères selon l'invention et soumise à un rayonnement de lumière bleue et de la peau et/ou des muqueuses non traitée et soumise à un rayonnement de lumière bleue ou non soumise à un rayonnement de lumière bleue. The prevention or reduction of the loss of firmness can be measured according to conventional methods, in particular by in vivo measurement using a cutometer, a density meter, a torque meter or even a dynaskin associated with a dermatop and in particular by comparison between skin and/or mucous membranes treated with the microspheres according to the invention and subjected to blue light radiation and untreated skin and/or mucous membranes and subjected to light radiation blue or not subjected to blue light radiation. The prevention or reduction of the loss of elasticity can be measured according to conventional methods, in particular by in vivo measurement, using a ballistometer or a corneovacuometer and in particular by comparison between skin and/or mucous membranes treated with the microspheres according to the invention and subjected to blue light radiation and untreated skin and/or mucous membranes and subjected to blue light radiation or not subjected to blue light radiation.
Les techniques classiques de mesure de protection des annexes cutanées permettent de mesurer la capacité du produit évalué à maintenir un état visuel, structurel ou fonctionnel de l'annexe cutanée soumis à un rayonnement de lumière bleue, préférentiellement de la fibre kératinique soumise à un rayonnement de lumière bleue, encore préférentiellement du cheveu comparable a l'etat d'une annexe cutanee non soumise a un rayonnement de lumière bleue, préférentiellement de la fibre kératinique non soumise à un rayonnement de lumière bleue, encore préférentiellement du cheveu non soumis à un rayonnement de lumière bleue. Conventional techniques for measuring the protection of cutaneous appendages make it possible to measure the capacity of the product evaluated to maintain a visual, structural or functional state of the cutaneous appendix subjected to blue light radiation, preferably of the keratin fiber subjected to radiation of blue light, still preferentially hair comparable to the state of a cutaneous appendix not subjected to blue light radiation, preferably keratin fiber not subjected to blue light radiation, more preferably hair not subjected to blue light radiation.
Les techniques classiques peuvent se réaliser pour tester l'efficacité du produit évalué dans son solvant, ou d'une formule capillaire (shampooing, après-shampooings, masques, lotions, ou autre). Elles peuvent être mises en oeuvre sur une annexe cutanée prélevée (technique ex vivo) ou sur une annexe cutanée en place sur un individu (technique in vivo). Conventional techniques can be carried out to test the effectiveness of the product evaluated in its solvent, or of a hair formula (shampoo, conditioner, masks, lotions, or other). They can be implemented on a skin appendix removed (ex vivo technique) or on a skin appendix in place on an individual (in vivo technique).
A titre d'exemple des méthodes utilisées pour évaluer la protection des annexes cutanées, préférentiellement des fibres kératiniques et encore préférentiellement des cheveux, on peut citer: By way of example of the methods used to evaluate the protection of the cutaneous appendages, preferentially of the keratinous fibers and still preferentially of the hair, one can quote:
- l'observation de la cuticule par microscopie électronique : il s'agit par cette technique d'observer l'état et/ou la qualité de la cuticule, par visualisation et quantification des écailles décollées comme témoin de l'endommagement de surface. Un cheveu endommagé présente en effet un décollement des écailles alors qu'un cheveu protégé apparait plus lisse en surface et ses écailles sont scellées. - observation of the cuticle by electron microscopy: this technique involves observing the state and/or the quality of the cuticle, by visualization and quantification of loose scales as evidence of surface damage. A damaged hair indeed presents a detachment of the scales whereas a protected hair appears smoother on the surface and its scales are sealed.
- L'étude de la calorimétrie différentielle à balayage (DSC : Differential Scanning Calorimetry) : cette méthode permet de déterminer les endommagements internes du cheveu par des mesures de la température de dénaturation ou de l'enthalpie et ainsi respectivement l'évaluation de la stabilité des protéines non hélicoïdales formant le ciment de la matrice ou des kératines (alpha-hélices) du cortex. Plus la température ou l'enthalpie est basse, plus l'endommagement du cheveu est important. Un cheveu protégé est en effet un cheveu stable à la température. - The study of differential scanning calorimetry (DSC: Differential Scanning Calorimetry): this method makes it possible to determine the internal damage of the hair by measurements of the temperature of denaturation or the enthalpy and thus respectively the evaluation of the stability non-helical proteins forming the cement of the matrix or keratins (alpha-helices) of the cortex. The lower the temperature or enthalpy, the greater the damage to the hair. A protected hair is indeed a temperature stable hair.
- L'analyse de la force de tension sur cheveux secs et/ou humides : l'évaluation des propriétés fonctionnelles et mécaniques du cheveu est effectuée par des mesures d'elasticite, de capacité de deformation, de résistance du cheveu en réponse à une force de tension. Les paramètres tels que la force de tension, le module élastique, la force de rupture et le point de rupture permettent d'évaluer ces propriétés biomécaniques. Ces paramètres témoignent de l'état de l'endommagement interne de la fibre capillaire. Un cheveu protégé est un cheveu dont les propriétés élastiques et de déformations sont maintenues. - Analysis of the tension force on dry and/or damp hair: the evaluation of the functional and mechanical properties of the hair is carried out by measuring elasticity, capacity for deformation, resistance of the hair in response to a tensile force. Parameters such as tensile strength, elastic modulus, breaking strength and breaking point are used to assess these biomechanical properties. These parameters testify to the state of the internal damage of the hair fiber. A protected hair is a hair whose elastic and deformation properties are maintained.
Des cheveux abîmés sont rugueux, plus difficiles à coiffer et plus cassants au coiffage. La protection des cheveux peut ainsi avoir une conséquence bénéfique sur ces propriétés de coiffage, laquelle peut également être mesurée. Damaged hair is rough, harder to comb and more brittle when combed. The protection of the hair can thus have a beneficial consequence on these styling properties, which can also be measured.
A titre d'exemple, les méthodes d'évaluation de coiffage qui peuvent être utilisées selon l'invention sont : By way of example, the styling evaluation methods which can be used according to the invention are:
- L'évaluation de la force de coiffage sur cheveux secs et/ou mouillés : évaluation biophysique de la facilité de coiffage des cheveux par mesure de la force générée lors du passage d'un peigne. Une force élevée de coiffage témoigne d'un cheveu abîmé. Les produits sont testés pour leurs propriétés de facilitation du coiffage ou de démêlage des cheveux. Des cheveux non endommagés car protégés sont des cheveux plus faciles à coiffer et à démêler. - Evaluation of the styling force on dry and/or wet hair: biophysical evaluation of the ease of combing the hair by measuring the force generated during the passage of a comb. High styling strength indicates damaged hair. Products are tested for their styling or hair detangling properties. Hair that is not damaged because it is protected is hair that is easier to comb and detangle.
- L'étude des forces de friction pour la rugosité de la surface des cheveux : évaluation des forces de friction d'une mèche de cheveu au passage de barres métalliques. Des cheveux abimés sont rugueux et présentent des forces de friction plus importantes que des cheveux non abîmés. Des cheveux protégés sont plus lisses et présenter une baisse des forces de friction. - The study of the friction forces for the roughness of the surface of the hair: evaluation of the friction forces of a lock of hair as it passes through metal bars. Damaged hair is rough and exhibits greater frictional forces than undamaged hair. Protected hair is smoother and has lower frictional forces.
- L'analyse de la résistance au coiffage : évaluation de l'état de casse des cheveux après coiffages répétés d'une mèche de cheveu. Des cheveux abîmes sont plus facilement cassants lors du coiffage répété. Des cheveux protégés cassent moins. - Analysis of resistance to styling: evaluation of the state of hair breakage after repeated styling of a lock of hair. Hair chasms are more easily brittle during repeated styling. Protected hair breaks less.
Les cheveux abîmés apparaissent rugueux, cassants, difficiles à coiffer, ternes. La protection des cheveux permet de maintenir les qualités sensorielles de cheveux sains non endommagés : cheveux lisses, doux, faciles à démêler, faciles à coiffer, faciles à mettre en forme, brillants, plus forts, plus résistants. Damaged hair appears rough, brittle, unmanageable, dull. Hair protection helps maintain the sensory qualities of healthy, undamaged hair: smooth, soft, easy to detangle, easy to comb, easy to style, shiny, stronger, more resistant.
A titre d'exemple, les méthodes d'évaluation utilisées sont : By way of example, the valuation methods used are:
- Tests sensoriels sur mèches de cheveux, réalisés par des volontaires externes entraînés à définir leurs sensations visuelles ou tactiles. - Sensory tests on locks of hair, carried out by external volunteers trained to define their visual or tactile sensations.
- Tests d'évaluation par des experts (coiffeurs) ou d'auto-évaluation par questionnaires consommateurs. L'efficacité d'un produit dans sa formule est évaluée selon des critères de qualité visuelle ou tactiles perceptibles de la chevelure. - Assessment tests by experts (hairdressers) or self-assessment by consumer questionnaires. The effectiveness of a product in its formula is evaluated according to visual or tactile quality criteria perceptible to the hair.
Selon l'invention, on entend « par structure des annexes cutanées » l'état des annexes cutanées, notamment de la cuticule et encore préférentiellement des écailles des annexes cutanées. La structure des annexes cutanées peut ainsi se mesurer par les techniques ci-dessus mentionnées d'observation de la cuticule par microscopie électronique et d'étude de la calorimétrie différentielle à balayage According to the invention, “structure of the skin appendages” means the state of the skin appendages, in particular of the cuticle and even more preferably of the scales of the skin appendages. The structure of the cutaneous appendages can thus be measured by the above-mentioned techniques of observation of the cuticle by electron microscopy and study of differential scanning calorimetry.
Selon l'invention, on entend par « propriétés visuelles des annexes cutanées», la brillance, l'éclat et la couleur. Les propriétés visuelles des annexes cutanées peuvent notamment être évaluées par les tests sensoriels visuels ci-dessus mentionnés. According to the invention, the term “visual properties of the cutaneous appendages” is understood to mean shine, luster and color. The visual properties of the cutaneous appendages can in particular be evaluated by the visual sensory tests mentioned above.
Selon l'invention, on entend par « propriétés biomécaniques des annexes cutanées », leurs qualités au toucher, notamment leur douceur, leur caractère soyeux et/ou lisse et leur souplesse, ainsi que leur résistance, leur élasticité, leur déformation et leur force ainsi que leur facilité de mise en forme et/ou coiffage. Selon l'invention, on entend par « propriétés biomecaniques de la peau et/ou des muqueuses », leurs qualités au toucher, notamment leur douceur, leur caractère soyeux et/ou lisse et leur souplesse, leur tonicité, élasticité, fermeté, densité, leur microrelief, leurs propriétés de surface et/ou de texture et/ou visuelle et/ou leurs qualités sensorielles. According to the invention, the term “biomechanical properties of the cutaneous appendages” is understood to mean their qualities to the touch, in particular their softness, their silky and/or smooth character and their suppleness, as well as their resistance, their elasticity, their deformation and their strength as well as their ease of shaping and/or combing. According to the invention, the term “biomechanical properties of the skin and/or mucous membranes” means their qualities to the touch, in particular their softness, their silky and/or smooth character and their suppleness, their tone, elasticity, firmness, density, their microrelief, their surface and/or textural and/or visual properties and/or their sensory qualities.
Selon l'invention, on entend « par structure de la peau et/ou des muqueuses » l'état de la peau et/ou des muqueuses, notamment de la barrière cutanée. According to the invention, “structure of the skin and/or mucous membranes” means the state of the skin and/or mucous membranes, in particular of the skin barrier.
Selon l'invention, on entend par « propriétés visuelles de la peau et/ou des muqueuses», la brillance, l'éclat et la couleur, notamment l'éclat du teint et/ou l'homogénéité du teint. According to the invention, the term “visual properties of the skin and/or of the mucous membranes” is understood to mean the shine, the radiance and the color, in particular the radiance of the complexion and/or the homogeneity of the complexion.
Les propriétés biomécaniques des annexes cutanées peuvent se mesurer notamment par l'analyse de la force de tension sur cheveux secs et/ou humides et/ou les méthodes d'évaluation de coiffage et/ou les tests sensoriels tactiles ci-dessus mentionnées. The biomechanical properties of the cutaneous appendages can be measured in particular by analyzing the force of tension on dry and/or damp hair and/or the styling evaluation methods and/or the tactile sensory tests mentioned above.
Les microsphères selon l'invention sont des microsphères d'oxyde métallique poreuses. De telles microsphères sont photoniques, en particulier ce sont des billes photoniques, ce qui signifie qu'elles présentent un degré de variations périodiques de couleur, notamment qui ont un impact sur les ondes lumineuses incluant la perception de la couleur, de la clarté, de la transparence, de la brillance. Ceci est en particulier dû au réseau de pores présent dans la microsphère, en particulier un réseau ordonné, plus particulièrement un réseau de pores de distribution de taille monodisperse, encore plus particulièrement de l'ordre du nanomètre (en particulier de 50 nm à 250 nm). Ainsi des microsphères creuses et non poreuses n'auraient pas cette capacité. The microspheres according to the invention are porous metal oxide microspheres. Such microspheres are photonic, in particular they are photonic beads, which means that they exhibit a degree of periodic variations in color, in particular which have an impact on light waves including the perception of color, clarity, transparency, shine. This is in particular due to the network of pores present in the microsphere, in particular an ordered network, more particularly a network of pores with a monodisperse size distribution, even more particularly of the order of a nanometer (in particular from 50 nm to 250 nm ). Thus hollow and non-porous microspheres would not have this capacity.
Les microsphères poreuses selon l'invention contiennent principalement l'oxyde métallique. De manière avantageuse, elles sont constituées essentiellement en l'oxyde métallique. De maniéré preferentielle, elles sont exclusivement constituées d'oxyde métallique. The porous microspheres according to the invention mainly contain the metal oxide. Advantageously, they consist essentially in the metal oxide. Preferably, they consist exclusively of metal oxide.
De manière avantageuse, les microsphères poreuses comprennent entre 60 % et 99,9% d'oxyde métallique, préférentiellement au moins 70%, encore préférentiellement au moins 80%, encore préférentiellement au moins 90%, encore préférentiellement 99,9% en poids par rapport au poids total des microsphères. Advantageously, the porous microspheres comprise between 60% and 99.9% of metal oxide, preferably at least 70%, more preferably at least 80%, more preferably at least 90%, more preferably 99.9% by weight per relative to the total weight of the microspheres.
Selon l'invention, les oxydes métalliques incluent les oxydes de métaux de transition, les métalloïdes et métal terreux compatibles avec une utilisation cosmétique et/ou dermatologique, comme par exemple oxyde de silice, de titane, d'alumine, de zircone, de cérium, de fer, oxyde de zinc, oxyde d'indium, oxyde d'étain, oxyde de chrome, oxyde métallique mixte, leurs combinaisons. Préférentiellement l'oxyde métallique est choisi dans le groupe constitué par SiO2, TiO2, ZnO et leurs mélanges, avantageusement il s'agit de SiO2. According to the invention, the metal oxides include the oxides of transition metals, metalloids and earth metals compatible with cosmetic and/or dermatological use, such as for example oxide of silica, titanium, alumina, zirconia, cerium , iron, zinc oxide, indium oxide, tin oxide, chromium oxide, mixed metal oxide, combinations thereof. Preferably, the metal oxide is chosen from the group consisting of SiO 2 , TiO 2 , ZnO and their mixtures, advantageously it is SiO 2 .
Selon un mode particulièrement avantageux, les microsphères selon l'invention ne contiennent qu'un oxyde métallique, préférentiellement l'oxyde de silice. According to a particularly advantageous mode, the microspheres according to the invention contain only one metal oxide, preferably silica oxide.
Selon un mode alternatif, les microsphères ne contiennent pas d'oxyde de titane ni d'oxyde de zinc. According to an alternative mode, the microspheres do not contain titanium oxide or zinc oxide.
Dans un mode de réalisation avantageux, les microsphères poreuses selon l'invention peuvent comprendre par exemple de 60% en poids à 99,9% en poids d'oxyde de métal et de 0,1% en poids à 40% en poids d'agents absorbeurs de lumière, en poids total des sphères. Selon un mode de réalisation de l'invention, les sphères contiennent de 0,3%, préférentiellement 0,5%, préférentiellement au moins 1%, encore préférentiellement au moins 5% en poids d'agents absorbeurs de lumière, par rapport au poids total des sphères. Selon un mode alternatif et preferentiel, les microspheres selon l'invention ne contiennent pas d'absorbeur de lumière et/ou la composition cosmétique qui les contient ne contient pas non plus d'absorbeur de lumières. En effet les absorbeurs de lumière tels que TiCh peuvent présenter une certaine toxicité. Or les inventeurs ont découvert de façon surprenante que même sans absorbeur de lumière les microsphères selon l'invention ont un effet immédiat de filtre anti-lumière bleue. In an advantageous embodiment, the porous microspheres according to the invention may 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. According to one embodiment of the invention, the spheres contain 0.3%, preferably 0.5%, preferably at least 1%, more preferably at least 5% by weight of light-absorbing agents, relative to the weight total of spheres. According to an alternative and preferred mode, the microspheres 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. Indeed, light absorbers such as TiCh can present a certain toxicity. However, the inventors have surprisingly discovered that even without a light absorber, the microspheres according to the invention have an immediate anti-blue light filter effect.
De manière avantageuse, le ou les agents absorbeurs de lumière sont sélectionnés dans le groupe consistant en les pigments organiques et inorganiques, compatibles avec une application cosmétique et/ou dermatologique, en particulier sur la peau, les muqueuses et/ou les annexes cutanées. Advantageously, 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, mucous membranes and/or skin appendages.
Selon un mode préférentiel avantageux, les microsphères poreuses selon l'invention ont un diamètre moyen D50 mesuré par microscopie électronique à balayage (SEM) allant de 1 à 14 pm, en particulier de 1,1 pm à 20 pm, avantageusement de 1,2 pm à 14 pm, en particulier de 1,3 pm à 10 pm, plus particulièrement de 1,5 à 4,5 pm, encore plus particulièrement de 1,6 pm à 4,4 pm, par exemple un diamètre moyen choisi parmi 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 ou 30 pm. Ainsi, il ne s'agit pas de nanosphères afin d'éviter leur pénétration dans les couches profondes de la peau et/ou des muqueuses et d'avoir préférentiellement un effet surface. Les microsphères selon l'invention avantageusement restent donc à la surface de la peau et/ou des muqueuses et ou des annexes cutanées. According to an advantageous preferential mode, the porous microspheres according to the invention have an average diameter D 50 measured by scanning electron microscopy (SEM) ranging from 1 to 14 μm, in particular from 1.1 μm to 20 μm, advantageously from 1, 2 μm to 14 μm, in particular from 1.3 μm to 10 μm, more particularly from 1.5 to 4.5 μm, even more particularly from 1.6 μm to 4.4 μm, for example an average diameter chosen 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. Thus, they are not nanospheres in order to avoid their penetration into the deep layers of the skin and/or 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.
Dans un mode préférentiel de l'invention, le diamètre moyen D50 de pores des microsphères mesuré par microscopie électronique à balayage (SEM) va de 80 nm à 250 nm, avantageusement de 100 nm à 245 nm, en particulier de 145nm a 235 nm, plus particulièrement de 180 nm a 225 nm, encore plus particulièrement de 195 nm à 217 nm, par exemple choisi parmi : 50 nm, 55nm, 60 nm, 65nm, 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, 135 nm, 140 nm, 145 nm, 150 nm, 155 nm, 160 nm, 165 nm, 170 nm,In a preferred mode of the invention, the average pore diameter D50 of the microspheres measured by scanning electron microscopy (SEM) ranges from 80 nm to 250 nm, advantageously from 100 nm to 245 nm, in particular from 145 nm to 235 nm, more particularly from 180 nm to 225 nm, even more particularly from 195 nm to 217 nm, for example chosen from: 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85nm, 90nm, 95nm, 100nm, 105nm, HOnm, 115nm, 120nm, 125nm, 130nm, 135nm, 140nm, 145nm, 150nm, 155nm, 160nm, 165nm, 170nm,
175 nm, 180 nm, 185 nm, 190 nm, 191 nm, 192 nm, 193 nm, 194 nm,175nm, 180nm, 185nm, 190nm, 191nm, 192nm, 193nm, 194nm,
195 nm, 196 nm, 197 nm, 198 nm, 199 nm, 200 nm, 201 nm, 202 nm,195nm, 196nm, 197nm, 198nm, 199nm, 200nm, 201nm, 202nm,
203 nm, 204 nm, 205 nm, 206 nm, 207 nm, 208 nm, 209 nm, 210 nm,203nm, 204nm, 205nm, 206nm, 207nm, 208nm, 209nm, 210nm,
211 nm, 212 nm, 213 nm, 214 nm, 215 nm, 216 nm, 217 nm, 218 nm,211nm, 212nm, 213nm, 214nm, 215nm, 216nm, 217nm, 218nm,
219 nm, 220 nm, 225nm, 230 nm, 235 nm, 240 nm, 245 nm ou 250 nm.219nm, 220nm, 225nm, 230nm, 235nm, 240nm, 245nm or 250nm.
Dans un mode préférentiel de l'invention, les microsphères poreuses ont une porosité moyenne choisie parmi : 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 ou 0,65, préférentiellement allant de 0,45 à 0,60, encore préférentiellement 0,50 à 0,60. In a preferred mode of the invention, the porous microspheres have an average porosity 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 or 0.65, preferably ranging from 0.45 to 0.60, more preferably 0.50 to 0.60.
Selon l'invention, la taille des microsphères et/ou des pores est un synonyme du diamètre des microsphère et/ou des pores et est déterminée par microscopie électronique à balayage (SEM). On entend par diamètre moyen des microsphères et/ou des pores (ou taille moyenne) la D50, signifiant que la moitié de la population est en dessous et l'autre moitié est au-dessus. Elle est obtenue par analyse de 50 à 70 microsphères et/ou 50 à 70 pores de différentes microsphères par microscopie électronique à balayage en utilisant un logiciel d'analyse ImageJ image. According to the invention, the size of the microspheres and/or the pores is a synonym of the diameter of the microspheres and/or the pores and is determined by scanning electron microscopy (SEM). By average diameter of the microspheres and/or pores (or average size) is meant the D50, meaning that half of the population is below and the other half is above. It is obtained by analyzing 50 to 70 microspheres and/or 50 to 70 pores of different microspheres by scanning electron microscopy using ImageJ image analysis software.
La porosité moyenne d'une microsphère désigne le volume total des pores, en tant que fraction du volume de la microsphère entière. La porosité moyenne peut également être dénommée « fraction volumique ». C'est une grandeur adimensionnelle. The average porosity of a microsphere refers to the total pore volume, as a fraction of the volume of the entire microsphere. The average porosity can also be called "volume fraction". It is a dimensionless quantity.
Une analyse en porosimétrie au mercure est utilisée pour caractériser la porosité des sphères. La porosimétrie au mercure consiste à appliquer une pression contrôlée dans l'échantillon a mesurer immerge dans le mercure. La pression extérieure est appliquée afin que le mercure pénètre dans les pores/trous du matériel. La quantité de pression nécessaire est inversement proportionnelle à la taille des pores/trous. Le porosimètre au mercure fournit alors un volume et des distributions de taille des pores. Le porosimètre à mercure génère des distributions de taille de volume et de pores à partir des données de pression par rapport aux données d'intrusion générées par l'instrument à l'aide de l'équation de Washburn.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.
Avantageusement la distribution de taille des pores des microsphères selon l’invention est monodisperse ou bimodale, avantageusement monodisperse, plus particulièrement ordonné, encore plus particulièrement ordonné et monodisperse. Advantageously, the size distribution of the pores of the microspheres according to the invention is monodisperse or bimodal, advantageously monodisperse, more particularly ordered, even more particularly ordered and monodisperse.
On entend par « distribution de taille des pores monodisperse » une distribution de taille de pores telle que 90 % de la surface délimitée par la distribution de taille des pores se situe dans l’intervalle donné par la taille moyenne ±5 % de sa valeur. The term “monodisperse pore size distribution” means a pore size distribution such that 90% of the surface delimited by the pore size distribution lies within the interval given by the average size ±5% of its value.
Dans un mode de réalisation avantageux, les microsphères selon l'invention ne contiennent pas et/ou ne sont pas utilisées en combinaison avec des nanoparticules, en particulier d'oxyde de titane et/ou d'oxyde de zinc, et/ou un autre filtre anti-lumière bleue et/ou un filtre anti-UV et/ou un filtre solaire et/ou dans une composition cosmétique qui en contient. Ainsi les microsphères selon l'invention ne sont pas utilisées en tant que booster des filtres anti-lumière bleue et/ou pour augmenter le SPF (indice de protection solaire) d'une composition solaire. In an advantageous embodiment, the microspheres according to the invention do not contain and/or are not used in combination with nanoparticles, in particular of titanium oxide and/or zinc oxide, and/or another anti-blue light filter and/or an anti-UV filter and/or a sunscreen and/or in a cosmetic composition which contains them. Thus the microspheres according to the invention are not used as a booster for anti-blue light filters and/or to increase the SPF (sun protection index) of a sunscreen composition.
Dans un mode de réalisation avantageux, les microsphères poreuses selon l'invention ne comportent pas de couche d'enrobage sur leur surface contenant un composé hydrophobe. Dans un mode de réalisation particulièrement avantageux, les sphères poreuses selon l'invention ne comportent pas de couche d'enrobage sur leur surface. Selon un mode particulier de l'invention les microspheres poreuses selon l'invention ne comportent pas de couche d'enrobage sur leur surface contenant un polyorganosiloxane, en particulier un composé siliconé. In an advantageous embodiment, the porous microspheres 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. According to a particular mode of the invention, the porous microspheres according to the invention do not comprise a coating layer on their surface containing a polyorganosiloxane, in particular a silicone compound.
Les microsphères poreuses comprenant un oxyde métallique selon l'invention peuvent être préparées en utilisant un modèle polymérique sacrificiel. De telles microsphères poreuses montrent une couleur observable par l'œil humain, en particulier une couleur bleue. The porous microspheres comprising a metal oxide according to the invention can be prepared using a sacrificial polymer template. Such porous microspheres show a color observable by the human eye, in particular a blue color.
On entend par «une couleur observable à l'œil nu », une couleur qui est observable par une majorité des personnes. Cela peut être pour tout échantillon de microsphères distribuées sur une surface donnée, par exemple, sur 1 cm2, 2 cm2, 3 cm2, 4 cm2, 5 cm2 ou 6 cm2, 7 cm2, 8 cm2, 9 cm2, 10 cm2, 11 cm2, 12 cm2, 13 cm2, 14 cm2 ou 15 cm2. Cela peut aussi signifier que c'est observable par le modèle standard d'observation CIE 1931 2° et/ou par le modèle standard d'observation CIE 1964 10°. Le fond d'observation de la couleur peut être de différente sorte par exemple blanc, noir, ou tout intermédiaire entre le noir et le blanc. “A color observable with the naked eye” means a color that is observable by a majority of people. This can be for any sample of microspheres 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.
Les microsphères peuvent être préparées par un procédé tel que décrit dans la demande de brevet US2019/0076809 ou dans l'une des demandes de brevet W02020/183108 et WO2020/182936. The microspheres can be prepared by a method as described in patent application US2019/0076809 or in one of patent applications WO2020/183108 and WO2020/182936.
Ainsi, selon un mode de réalisation, une dispersion colloïdale aqueuse contenant des particules de polymère et un oxyde métallique est préparée, les particules de polymère étant typiquement à l'échelle nanométrique. La dispersion aqueuse colloïdale est alors mélangée dans une phase continue huileuse, par exemple avec un dispositif microfluidique, pour produire une émulsion eau-dans-huile. Des gouttelettes aqueuses d'émulsion sont obtenues, collectées et séchées pour former les microsphères contenant les nanoparticules de polymère et d'oxyde métallique. Les nanoparticules (nanosphères) de polymère sont ensuite éliminées, par exemple par calcination, pour fournir des particules sphériques, d'echelle micrometrique d'oxyde métallique contenant un haut degré de porosité et des pores d'échelle nanométriques. Les sphères peuvent contenir des diamètres de pores uniformes, du fait de l'utilisation de particules de polymères sphériques et monodispersées. Thus, according to one embodiment, an aqueous colloidal dispersion containing particles of polymer and a metal oxide is prepared, the particles of polymer being typically at the nanometric scale. The colloidal aqueous dispersion is then mixed in an oily continuous phase, for example with a microfluidic device, to produce a water-in-oil emulsion. Aqueous emulsion droplets are obtained, collected and dried to form the microspheres containing the polymer and metal oxide nanoparticles. The polymer nanoparticles (nanospheres) are then eliminated, for example by calcination, to provide particles spherical, microscale metal oxide containing a high degree of porosity and nanoscale pores. The spheres can contain uniform pore diameters, due to the use of spherical and monodisperse polymer particles.
Par exemple une goutte d'émulsion contenant des nanosphères de polymère et un oxyde métallique est séchée pour retirer le solvant, produisant ainsi une microsphère formée de nanosphères de polymère avec l'oxyde métallique dans des espaces interstitiels entre les nanosphères de polymère (microsphères modèles ou gabarits ou « structure directe »).Les nanosphères de polymère définissent un espace interstitiel. La calcination aboutit au retrait du polymère, fournissant ainsi une microsphère d'oxyde métallique ayant une haute porosité ou un grand volume interstitiel (structure inverse). For example, a drop of emulsion containing polymer nanospheres and a metal oxide is dried to remove the solvent, thereby producing a microsphere formed of polymer nanospheres with the metal oxide in interstitial spaces between the polymer nanospheres (model microspheres or templates or "direct structure"). The polymer nanospheres define an interstitial space. Calcination results in shrinkage of the polymer, thus providing a metal oxide microsphere with high porosity or large interstitial volume (inverse structure).
Les microsphères d'oxyde métallique poreuses sont avantageusement frittées, conduisant à une structure solide continue, consolidée, stable thermiquement et mécaniquement. The porous metal oxide microspheres are advantageously sintered, resulting in a continuous, consolidated, thermally and mechanically stable solid structure.
Dans certains modes de réalisation, la formation des gouttelettes et leur collecte s'effectuent dans le dispositif microfluidique. In certain embodiments, the formation of the droplets and their collection take place in the microfluidic device.
Des dispositifs microfluidiques sont par exemple des dispositifs à canal étroit ayant une jonction à échelle microscopique adaptée pour produire des gouttelettes uniformes et connectées à un réservoir de récupération.Examples of microfluidic devices are narrow channel devices having a microscale junction adapted to produce uniform droplets and connected to a collection reservoir.
Les dispositifs microfluidiques contiennent par exemple une jonction ayant une largeur de canal allant de 10 pm à environ 100 pm. Ces dispositifs sont par exemple faits de polydiméthylsiloxane (PDMS) et peuvent être préparé par exemple par lithographie douce. Une émulsion peut être préparée à l'intérieur du dispositif en pompant une phase dispersée aqueuse et une phase continue huileuse selon un rapport défini formant ainsi une émulsion en mélangeant les deux phases. De manière alternative, une émulsion huile-dans-eau peut être utilisée. De maniéré preferentielle, le polymere est sélectionne dans le groupe consistant en l'acide poly(méth)acrylique, les poly(méth)acrylates, les polystyrènes, les polyacrylamides, le polyéthylène, le polypropylène, l'acide polylactique, le polyacrylonitrile, ainsi que leurs dérivés et leurs sels, leurs copolymères et leurs combinaisons. Préférentiellement, le polymère est choisi dans le groupe constitué de polystyrènes, par exemple un copolymère de polystyrène/acide acrylique, polystyrène/méthacrylate de poly(éthylène glycol) ou polystyrène/sulfonate de styrène. Microfluidic devices contain, for example, a junction having a channel width ranging from 10 μm to about 100 μm. These devices are for example made of polydimethylsiloxane (PDMS) and can be prepared for example by soft lithography. An emulsion can be prepared inside the device by pumping an aqueous dispersed phase and an oily continuous phase according to a defined ratio thus forming an emulsion by mixing the two phases. Alternatively, an oil-in-water emulsion can be used. Preferably, the polymer is selected from the group consisting of poly(meth)acrylic acid, poly(meth)acrylates, polystyrenes, polyacrylamides, polyethylene, polypropylene, polylactic acid, polyacrylonitrile, as well as as their derivatives and their salts, their copolymers and their combinations. Preferably, the polymer is chosen from the group consisting of polystyrenes, for example a copolymer of polystyrene/acrylic acid, polystyrene/poly(ethylene glycol) methacrylate or polystyrene/styrene sulfonate.
Le rapport pondéral (poids/poids) de nanoparticules de polymère/oxyde métallique va par exemple d'environ 0,1/1 à environ 10,0/1 ou d'environ 0,5/1 à environ 10,0/1. De manière avantageuse ce rapport est de : 0,1/1, 0,5/1, 1,0/1, 1,5/1, 2,0/1, 2,5/1, 3,0/1, 3,5/1, 4,0/1, 5,0/1, 5,5/1, 6,0/1, 6,5/1, 7,0/1, 7, 5/2, 5, 8,0/1, 9,0/1 ou 10,0/1, en particulier de 7, 5/2, 5.The weight ratio (weight/weight) of polymer/metal oxide nanoparticles ranges, for example, from about 0.1/1 to about 10.0/1 or from about 0.5/1 to about 10.0/1. Advantageously, this ratio is: 0.1/1, 0.5/1, 1.0/1, 1.5/1, 2.0/1, 2.5/1, 3.0/1, 3.5/1, 4.0/1, 5.0/1, 5.5/1, 6.0/1, 6.5/1, 7.0/1, 7, 5/2, 5, 8.0/1, 9.0/1 or 10.0/1, in particular 7.5/2.5.
La phase huileuse continue comprend par exemple un solvant organique, une huile silicone ou une huile fluorée. Selon l'invention le terme « huile » désigne une phase organique non miscible avec l'eau. Les solvants organiques incluent les hydrocarbures, tels que l'heptane, l'hexane, le toluène, le xylène ainsi que les alcools, tels que le méthanol, l'éthanol, le propanol, etc. The continuous oily phase comprises for example an organic solvent, a silicone oil or a fluorinated oil. According to the invention, the term “oil” denotes an organic phase which is immiscible with water. Organic solvents include hydrocarbons, such as heptane, hexane, toluene, xylene as well as alcohols, such as methanol, ethanol, propanol, etc.
Les gouttelettes d'émulsion sont collectées, séchées et le polymère est retiré. The emulsion droplets are collected, dried and the polymer is removed.
Le séchage est réalisé selon les techniques classiques, par exemple par irradiation aux microondes, dans un four thermique, sous vide, en présence d'un agent déshydratant/absorbant ou un mélange de ces techniques. 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.
Le polymère est retiré selon les techniques classiques par exemple par calcination, pyrolyse ou par un solvant. La calcination est effectuée selon un mode de réalisation à des températures allant de 200°C à environ 1200°C. Selon un mode de réalisation, la température de calcination est d'au moins 200°C, preferentiellement au moins 500°C, encore préférentiellement au moins 1000°C. De manière alternative la température de calcination de 200°C à environ 700°C. La calcination est effectuée pendant une durée appropriée par exemple allant de 0,1 heure à environ 12 heures, préférentiellement de 1 heure à 8 heures. Dans certains modes de réalisation, la calcination est effectuée pendant au moins 0,lheure, pendant au moins 1 heure, pendant au moins 5 heures ou pendant au moins 10 heures. The polymer is removed according to conventional techniques, for example by calcination, pyrolysis or by a solvent. The calcination is carried out according to one embodiment at temperatures ranging from 200°C to about 1200°C. According to one embodiment, the calcination temperature is at least 200°C, preferably at least 500°C, more preferably at least 1000°C. Alternatively the calcination temperature from 200°C to about 700°C. The calcination is carried out for an appropriate period, for example ranging from 0.1 hour to about 12 hours, preferably from 1 hour to 8 hours. In certain embodiments, the calcination is carried out for at least 0.1 hour, for at least 1 hour, for at least 5 hours or for at least 10 hours.
De manière alternative, la dispersion liquide comprenant les nanoparticules de polymère et d'oxyde métallique est formée en phase dispersée huileuse et en phase aqueuse continue pour former une émulsion huile-dans-eau. Les gouttelettes huileuses peuvent ainsi être collectées et séchées de la même façon que les gouttelettes aqueuses.Alternatively, the liquid dispersion comprising the polymer and metal oxide nanoparticles is formed in an oily dispersed phase and in a continuous aqueous phase to form an oil-in-water emulsion. The oily droplets can thus be collected and dried in the same way as the aqueous droplets.
De manière alternative, une dispersion liquide comprenant les nanoparticules de polymère et d'oxyde métallique est préparée et est séchée par atomisation pour former les microsphères gabarit / modèle de polymère sans former une émulsion liquide/liquide. Dans certains modes de réalisation des techniques de séchage par atomisation, une solution ou dispersion liquide est alimentée (par exemple pompée) dans une buse d'atomisation avec une entrée de gaz compressée. L'alimentation est pompée à travers la buse d'atomisation pour former des gouttelettes de liquide. Les gouttelettes sont entourées par un gaz préchauffé dans la chambre d'évaporation, résultant en l'évaporation du solvant pour produire des particules solides. Les particules séchées sont transportées par le gaz de séchage à travers le cyclone et déposées dans la chambre de collecte. Les gaz utilisables incluent l'azote et/ou l'air. Alternatively, a liquid dispersion comprising the polymer and metal oxide nanoparticles is prepared and is spray dried to form the polymer template/template microspheres without forming a liquid/liquid emulsion. In some embodiments of spray drying techniques, a liquid solution or dispersion is fed (eg, pumped) into an atomizing nozzle with a compressed gas inlet. Feed is pumped through the atomizing nozzle to form liquid droplets. The droplets are surrounded by a preheated gas in the evaporation chamber, resulting in the evaporation of the solvent to produce solid particles. The dried particles are transported by the drying gas through the cyclone and deposited in the collection chamber. Usable gases include nitrogen and/or air.
Dans un mode de réalisation du procédé de séchage par atomisation, le liquide d'alimentation contient une phase aqueuse ou huileuse, les nanoparticules de polymère et l'oxyde métallique. Les microsphères gabarit / modèle de polymere contiennent les nanoparticules de polymere avec l'oxyde de métal dans les espaces interstitiels entre les nanoparticules de polymère. Les nanoparticules de polymère définissent les espaces interstitiels. Les techniques de séchage par atomisation incluent les méthodes de séchage par atomisation à jet d'encre. In one embodiment of the spray drying process, the feed liquid contains an aqueous or oily phase, the polymer nanoparticles and the metal oxide. The microspheres polymer template/template contain the polymer nanoparticles with the metal oxide in the interstitial spaces between the polymer nanoparticles. The polymer nanoparticles define the interstitial spaces. Spray drying techniques include inkjet spray drying methods.
Dans les techniques de séchage par atomisation, l'air et/ou le gaz peut être considéré comme la phase continue avec une phase liquide dispersée (émulsion liquide-dans-gaz). Dans certains modes de réalisations, le séchage par atomisation comprend une température d'admission d'au moins 100° C, 105° C, 110° C, 115° C, 120° C, 130° C, 140° C, 150° C, 160°C ou 170°C à 180° C, 190°C, 200° C, 210° C, 215° C ou 220° C, en particulier de 100°C. Dans certains modes de réalisations la vitesse d'alimentation est de 1 mL/min, 2 mL/min, 5 mL/min, 6 mL/min, 8 mL/min, lOmL/min, 12 mL/min, 14 mL/min ou 16 mL/min à 18 mL/min, 20 mL/min, 22 mL/min, 24 mL/min, 26 mL/min, 28 mL/min ou 30 mL/min, en particulier elle est de 10 mL/min. Les techniques de séchage par atomisation sont en particulier décrites par exemple dans la demande de brevet U52016/0170091. In spray drying techniques, air and/or gas can be considered as the continuous phase with a dispersed liquid phase (liquid-in-gas emulsion). In some embodiments, the spray drying includes an inlet temperature of at least 100°C, 105°C, 110°C, 115°C, 120°C, 130°C, 140°C, 150°C, C, 160°C or 170°C to 180°C, 190°C, 200°C, 210°C, 215°C or 220°C, in particular 100°C. In some embodiments the feed rate is 1 mL/min, 2 mL/min, 5 mL/min, 6 mL/min, 8 mL/min, 10 mL/min, 12 mL/min, 14 mL/min or 16 mL/min to 18 mL/min, 20 mL/min, 22 mL/min, 24 mL/min, 26 mL/min, 28 mL/min or 30 mL/min, in particular it is 10 mL/min . Spray drying techniques are described in particular for example in patent application U52016/0170091.
Les microsphères obtenues sont sphériques ou quasi sphériques et sont à l'échelle micrométrique. Les nanoparticules de polymère employées comme modèle/gabarits sont aussi sphériques, à l'échelle nanométrique, elles sont monodispersées et ont un diamètre moyen allant de 50 nm à environ 999 nm, avantageusement de 50nm à 500nm, en particulier de lOOnm à 400nm. De manière avantageuse, les nanoparticules de polymère ont un diamètre moyen de 50 nm, 75nm, 100 nm, 130 nm, 160 nm, 190 nm, 210 nm, 240 nm, 270 nm, 300 nm, 330 nm, 360 nm, 390 nm, 410 nm, 440 nm, 470 nm, 500 nm, 530 nm, 560 nm, 590 nm, 620 nm, 650 nm, 680 nm, 710 nm, 740 nm, 770 nm, 800 nm, 830 nm, 860 nm, 890 nm, 910 nm, 940 nm, 970 nm ou 990 nm. L'oxyde métallique utilise peut aussi etre sous forme de particules, de telles particules pouvant être alors à l'échelle nanométrique. The microspheres obtained are spherical or quasi-spherical and are on the micrometric scale. The polymer nanoparticles used as model/templates are also spherical, on the nanometric scale, they are monodispersed and have an average diameter ranging from 50 nm to approximately 999 nm, advantageously from 50 nm to 500 nm, in particular from 100 nm to 400 nm. Advantageously, the polymer nanoparticles have an average diameter of 50 nm, 75 nm, 100 nm, 130 nm, 160 nm, 190 nm, 210 nm, 240 nm, 270 nm, 300 nm, 330 nm, 360 nm, 390 nm , 410nm, 440nm, 470nm, 500nm, 530nm, 560nm, 590nm, 620nm, 650nm, 680nm, 710nm, 740nm, 770nm, 800nm, 830nm, 860nm, 890 nm, 910nm, 940nm, 970nm or 990nm. The metal oxide used can also be in the form of particles, such particles then being able to be on the nanometric scale.
L'oxyde métallique en dispersion peut être fourni sous forme d'oxyde métallique ou sous la forme d'un précurseur de l'oxyde métallique, comme par exemple par la technique sol-gel. The dispersed metal oxide can be supplied in the form of metal oxide or in the form of a precursor of the metal oxide, such as for example by the sol-gel technique.
Le séchage des gouttelettes de polymère/oxyde métallique suivi du retrait du polymère permet d'obtenir des microsphères ayant des cavités uniformes (pores). En général, dans les procédés décrits, chaque gouttelette forme une seule microsphère. Les diamètres des pores sont dépendants de la taille des particules de polymère. Un phénomène de rétrécissement ou compaction peut apparaitre lors du retrait du polymère, produisant des tailles de pores légèrement plus petits que la taille initiale des particules de polymères, par exemple allant de 10% à 40% plus petits que la taille de la particule de polymère initiale. Le diamètre des pores est aussi uniforme que l'étaient la forme et la taille des nanoparticules de polymère. Drying of the polymer/metal oxide droplets followed by shrinkage of the polymer results in microspheres having uniform cavities (pores). In general, in the methods described, each droplet forms a single microsphere. The pore diameters are dependent on the size of the polymer particles. A phenomenon of shrinkage or compaction may appear during the shrinkage of the polymer, producing pore sizes slightly smaller than the initial size of the polymer particles, for example ranging from 10% to 40% smaller than the size of the polymer particle initial. The pore diameter is as uniform as were the shape and size of the polymer nanoparticles.
Dans certains modes de réalisation, la sphère poreuse a un centre solide au cœur et une porosité vers la surface extérieure de la sphère. In some embodiments, the porous sphere has a solid center at the core and porosity toward the outer surface of the sphere.
Dans d'autres modes de réalisation les sphères poreuses ont un centre vide avec une porosité qui augmente en direction de l'intérieur des sphères. In other embodiments the porous spheres have a hollow center with increasing porosity toward the interior of the spheres.
Dans certains modes de réalisation, il existe ainsi un gradient de porosité vers le centre ou vers l'extérieur de la sphère. In certain embodiments, there is thus a porosity gradient towards the center or towards the outside of the sphere.
Dans d'autres modes préférentiels de l'invention, la porosité est distribuée de manière uniforme dans tout le volume des microsphères. In other preferred embodiments of the invention, the porosity is distributed uniformly throughout the volume of the microspheres.
Dans la microsphère poreuse selon l'invention, le diamètre moyen des microsphères est nettement plus large que le diamètre moyen des pores. Par exemple, le diamètre moyen des microsphères est en général d'au moins 5 fois, préférentiellement au moins 10 fois, préférentiellement au moins 15 fois, encore preferentiel lement 20 fois, encore preferentiel lement 25 fois plus grand que le diamètre moyen des pores. In the porous microsphere according to the invention, the mean diameter of the microspheres is markedly larger than the mean diameter of the pores. For example, the average diameter of the microspheres is in general at least 5 times, preferentially at least 10 times, preferentially at less than 15 times, more preferably 20 times, more preferably 25 times greater than the average pore diameter.
Dans certains modes de réalisation, le rapport du diamètre moyen des microsphères sur le diamètre moyen des pores est d'au moins 5/1, au moins 10/1, au moins 15/1, au moins 40/1, au moins 50/1, au moins 60/1, au moins 70/1, au moins 80/1, ou au moins 90/1. In some embodiments, the ratio of the average microsphere diameter to the average pore diameter is at least 5/1, at least 10/1, at least 15/1, at least 40/1, at least 50/ 1, at least 60/1, at least 70/1, at least 80/1, or at least 90/1.
Les modèles de microsphères de polymères comprenant des nanosphères de polymères monodispersées peuvent aboutir à des microsphères d'oxyde métallique ayant des pores similaires en diamètre, une fois le polymère est retiré. Models of polymer microspheres comprising monodisperse polymer nanospheres can result in metal oxide microspheres having similar pores in diameter, once the polymer is removed.
De manière préférentielle, la plupart des microsphères poreuses présente une couleur observable à l'œil nu, en particulier une couleur bleue. Preferably, most of the porous microspheres have a color observable with the naked eye, in particular a blue color.
Les microsphères poreuses selon la présente invention peuvent présenter une couleur dépendante ou non de l'angle. On entend par «une couleur dépendante de l'angle » une couleur observée qui dépend de l'angle de la lumière incidente ou de l'angle entre l'observateur et la zone de couleur observée. Une couleur indépendante de l'angle signifie que la couleur observée ne dépend substantivement pas de l'angle de la lumière incidente ou de l'angle entre l'observateur et la zone de couleur observée.The porous microspheres according to the present invention may or may not exhibit angle-dependent color. By "an angle-dependent color" is meant an observed color that depends on the angle of the incident light or the angle between the observer and the observed color area. An angle-independent color means that the observed color does not depend substantively on the angle of the incident light or the angle between the observer and the observed color area.
Des microsphères ayant une couleur dépendante de l'angle peuvent être obtenues notamment en utilisant des nanosphères de polymère monodispersées. Elles peuvent aussi être obtenues quand l'étape de séchage des gouttelettes liquides permettant de fournir le modèle des microsphères de polymère est réalisée doucement, permettant ainsi nanosphères de polymère de s'ordonner. On obtient ainsi une porosité ordonnée (tel qu'un réseau de pores ordonné et/ou une distribution de taille de pores ordonnée) et en particulier avec une distribution de taille de pores monodisperse. Des microspheres dont la couleur est indépendante de l'angle peuvent être obtenues quand l'étape de séchage des gouttelettes liquides est réalisée rapidement, ne permettant pas aux nanosphères de polymère de s'ordonner. Microspheres having an angle-dependent color can be obtained in particular by using monodispersed polymer nanospheres. They can also be obtained when the step of drying the liquid droplets to provide the model of the polymer microspheres is carried out gently, thus allowing the polymer nanospheres to become ordered. An ordered porosity is thus obtained (such as an ordered pore network and/or an ordered pore size distribution) and in particular with a monodisperse pore size distribution. Microspheres whose color is independent of the angle can be obtained when the step of drying the liquid droplets is carried out quickly, not allowing the polymer nanospheres to order themselves.
De manière avantageuse, les microsphères poreuses sont elles-mêmes également monodispersées. Advantageously, the porous microspheres are themselves also monodispersed.
On entend par « la plupart des microsphères », la population des microsphères. Il peut s'agit d'une quantité de > 0,1 mg, > 0,2 mg, > 0,3 mg, > 0,4 mg, > 0,5 mg, > 0,7 mg, > 1,0 mg, > 2,5 mg, > 5,0 mg, > 10,0 mg ou > 25,0 mg. La plupart des microsphères peut être dénuée d'autres composés. “Most of the microspheres” means the population of the microspheres. This can be an amount of > 0.1 mg, > 0.2 mg, > 0.3 mg, > 0.4 mg, > 0.5 mg, > 0.7 mg, > 1.0 mg, > 2.5 mg, > 5.0 mg, > 10.0 mg or > 25.0 mg. Most microspheres may be devoid of other compounds.
On entend par « à l'échelle micrométrique » ou « micro- » une taille allant d'environ 1 pm à environ 999 pm. On entend par « à l'échelle nanométrique » ou « nano- » une taille allant d'environ 1 nm à environ 999 nm. The term “on a micrometric scale” or “micro-” is understood to mean a size ranging from about 1 μm to about 999 μm. By “nano-scale” or “nano-” is meant a size ranging from about 1 nm to about 999 nm.
On entend par « monodispersé » pour la population des microsphères poreuses ou de nanosphères de polymère des particules qui ont une forme homogène et un diamètre homogène. La population de sphères est ainsi dite monodispersée quand 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% ou 99% du nombre de particules ont un diamètre de ± 7%, ± 6%, ± 5%, ± 4%, ± 3%, ± 2% ou ± 1% par rapport au diamètre moyen de la population des sphères. The term “monodispersed” for the population of porous microspheres or of polymer nanospheres means particles which have a homogeneous shape and a homogeneous diameter. The population of spheres is thus said to be monodisperse when 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% of the number of particles have a diameter of ± 7%, ±6%, ±5%, ±4%, ±3%, ±2% or ±1% relative to the average diameter of the sphere population.
Le retrait de la population monodispersée de nanosphères de polymère fournis des microsphères d'oxyde métallique ayant une population de pores ayant un diamètre moyen. Removal of the monodispersed population of polymer nanospheres yields metal oxide microspheres having a population of pores having an average diameter.
Ainsi les microsphères selon l'invention comprenant un oxyde métallique sont préparées par une méthode comprenant les étapes suivantes : Thus the microspheres according to the invention comprising a metal oxide are prepared by a method comprising the following steps:
- Former une dispersion liquide de nanoparticules de polymère et d'un oxyde métallique ; - Former des gouttelettes liquides de la dispersion ; - Form a liquid dispersion of polymer nanoparticles and a metal oxide; - Form liquid droplets of the dispersion;
- Sécher les gouttelettes liquides des microsphères comprenant les nanosphères de polymère et l'oxyde métallique ; - Drying the liquid droplets of the microspheres comprising the polymer nanospheres and the metal oxide;
- Retirer les nanosphères de polymère des microsphères modèles pour fournir les sphères poreuses d'oxyde métallique. - Remove the polymer nanospheres from the model microspheres to provide the porous metal oxide spheres.
Selon un mode avantageux, les gouttelettes liquides sont aqueuses. Selon une alternative les gouttelettes liquides sont huileuses. According to an advantageous mode, the liquid droplets are aqueous. Alternatively, the liquid droplets are oily.
Selon un mode préférentiel, la méthode comprend une phase continue et le mélange de la dispersion liquide avec cette phase continue pour former une émulsion contenant les gouttelettes de dispersion liquide dispersées. Selon un mode particulier, la phase continue est huileuse et le mélange est effectué entre la phase huileuse continue et la dispersion liquide aqueuse pour former une émulsion eau-dans-huile contenant des gouttelettes aqueuses. According to a preferred mode, the method comprises a continuous phase and the mixing of the liquid dispersion with this continuous phase to form an emulsion containing the dispersed droplets of liquid dispersion. According to a particular mode, the continuous phase is oily and the mixture is carried out between the continuous oily phase and the aqueous liquid dispersion to form a water-in-oil emulsion containing aqueous droplets.
Selon un mode alternatif, la phase continue est aqueuse et le mélange est effectué entre la phase aqueuse continue et la dispersion liquide huileuse pour former une émulsion huile-dans-eau contenant des gouttelettes lipidiques. According to an alternative mode, the continuous phase is aqueous and the mixture is carried out between the continuous aqueous phase and the oily liquid dispersion to form an oil-in-water emulsion containing lipid droplets.
Selon encore un autre mode alternatif, la phase continue est gazeuse et le mélange est effectué entre la phase gazeuse continue et la dispersion liquide aqueuse pour former une émulsion eau-dans-gaz contenant des gouttelettes aqueuses. According to yet another alternative mode, the continuous phase is gaseous and the mixing is carried out between the continuous gaseous phase and the aqueous liquid dispersion to form a water-in-gas emulsion containing aqueous droplets.
Selon un mode avantageux, la méthode comprend les étapes subséquentes de collecte des gouttelettes, de séchage des gouttelettes et de retrait des nanosphères de polymère du modèle de microsphères. According to an advantageous mode, the method comprises the subsequent steps of collecting the droplets, drying the droplets and removing the polymer nanospheres from the model of microspheres.
Selon la présente invention, les microsphères poreuses sont utilisées seules, notamment sous forme de poudre (100%), ou en composition, notamment cosmétique, à une concentration allant de 0,01 à 20%, avantageusement allant de 0,1 à 5%, de préférence allant de 0,5% à 3%, encore preferentiellement de 1% jusqu'à 2%, en poids par rapport au poids total de la composition. According to the present invention, the porous microspheres are used alone, in particular in powder form (100%), or in composition, in particular cosmetic, at a concentration ranging from 0.01 to 20%, advantageously ranging from 0.1 to 5% , preferably ranging from 0.5% to 3%, still preferentially from 1% up to 2%, by weight relative to the total weight of the composition.
Les microsphères poreuses selon l'invention peuvent être utilisées seules, notamment sous la forme d'un ingrédient actif cosmétique ou dans une composition destinée à être en contact avec la peau, les annexes et/ou les muqueuses cutanées, comme par exemple une composition cosmétique, préférentiellement destiné(e) à une application par voie topique. The porous microspheres according to the invention can be used alone, in particular in the form of a cosmetic active ingredient or in a composition intended to be in contact with the skin, the appendages and/or the cutaneous mucous membranes, such as for example a cosmetic composition , preferably intended for topical application.
L'ingrédient actif et/ou les compositions cosmétiques contenant les sphères poreuses selon l'invention sont préférentiellement destinées à la protection cosmétique de la peau, incluant le cuir chevelu ainsi que les annexes cutanées, préférentiellement les cheveux. The active ingredient and/or the cosmetic compositions containing the porous spheres according to the invention are preferentially intended for the cosmetic protection of the skin, including the scalp as well as the skin appendages, preferentially the hair.
Dans un autre mode de réalisation, les sphères selon l'invention peuvent être incorporées dans une composition cosmétique comprenant en outre au moins un excipient cosmétiquement acceptable. In another embodiment, the spheres according to the invention can be incorporated into a cosmetic composition further comprising at least one cosmetically acceptable excipient.
On entend au sens de la présente invention par excipient « cosmétiquement acceptable » un composé et/ou solvant topiquement acceptable, c'est-à-dire n'induisant pas de réponse allergique au contact de la peau, incluant le cuir chevelu humain, les muqueuses et les annexes cutanées, non toxique, non instable, ou leurs équivalents, indue. Within the meaning of the present invention, the term “cosmetically acceptable” excipient is understood to mean a topically acceptable compound and/or solvent, that is to say not inducing an allergic response on contact with the skin, including the human scalp, the mucous membranes and skin appendages, non-toxic, non-stable, or their equivalents, undue.
La composition cosmétique selon l'invention, peut se présenter sous toutes les formes galéniques classiquement utilisées pour une application topique sur la peau incluant le cuir chevelu, les muqueuses et les annexes cutanées, telles que les formes liquides ou solides ou même sous la forme de liquide sous pression. Elles peuvent notamment être formulées sous la forme d'une solution, aqueuse ou huileuse, notamment une lotion, une crème ou un gel aqueux ou un gel huileux, notamment en pot ou en tube, notamment un gel douche, un shampoing, un après-shampoing, un lait, une huile, une émulsion, un hydrogel, une microémulsion ou une nanoémulsion, notamment huile-dans-eau ou eau-dans-huile ou multiple ou siliconee, un serum, une lotion, notamment en flacon de verre, de plastique ou en flacon doseur ou en aérosol ou en spray, une ampoule, un savon liquide ou solide, une pâte, une pommade, une mousse, un masque, une laque, un patch, un produit anhydre, de préférence liquide, pâteux ou solide, par exemple sous forme de bâtonnet notamment en stick ou en poudres, préférentiellement, une crème, un sérum ou une lotion. The cosmetic composition according to the invention can be in any galenic form conventionally used for topical application to the skin including the scalp, mucous membranes and skin appendages, such as liquid or solid forms or even in the form of liquid under pressure. They can in particular be formulated in the form of an aqueous or oily solution, in particular a lotion, a cream or an aqueous gel or an oily gel, in particular in a jar or in a tube, in particular a shower gel, a shampoo, an after- shampoo, milk, oil, emulsion, hydrogel, microemulsion or nanoemulsion, in particular oil-in-water or water-in-oil or multiple or silicone, a serum, a lotion, in particular in a glass or plastic bottle or in a dispenser bottle or in an aerosol or spray, an ampoule, a liquid or solid soap, a paste, an ointment, a mousse, a mask, a lacquer, a patch, an anhydrous product, preferably liquid, pasty or solid, for example in the form of a stick, in particular in a stick or in powders, preferably a cream, a serum or a lotion.
Il peut également s'agir d'un produit de maquillage ou d'un produit de démaquillage. En particulier, la composition cosmétique est choisie dans le groupe constitué par un sérum, une lotion, une crème, un shampoing, un après-shampoing, une huile, un lait, une pommade, une pâte, une mousse, une émulsion, un hydrogel, un gel douche, un masque, une laque, un spray, une cire, un mascara, un crayon de maquillage, un vernis, d'une poudre, notamment de maquillage, d'un stick, encore préférentiellement il s'agit d'une crème, d'un sérum ou d'une lotion. Il peut également s'agir d'une poudre, notamment de maquillage, un fond de teint de stick, de compositions pour les soins de la barbe, après rasage et/ou épilation. Selon un mode avantageux la composition cosmétique selon l'invention est au moins légèrement gélifiée et/ou comprend une phase huileuse, préférentiellement est de type composition huileuse ou émulsion huile-dans-eau ou eau-dans-huile ou lotion. It may also be a make-up product or a make-up removal product. In particular, the cosmetic composition is chosen from the group consisting 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 mascara, a make-up pencil, a varnish, a powder, in particular a make-up powder, a stick, again preferably it is a a cream, serum or lotion. It may also be a powder, in particular for make-up, a stick foundation, compositions for beard care, after shaving and/or depilation. According to an advantageous mode, the cosmetic composition according to the invention is at least slightly gelled and/or comprises an oily phase, preferably is of the oily composition or oil-in-water or water-in-oil emulsion or lotion type.
Les compositions selon l'invention peuvent contenir tout solvant approprié et/ou tout véhicule approprié et/ou tout excipient approprié cosmétiquement acceptable, éventuellement en combinaison avec d'autres composés d'intérêts. The compositions according to the invention may contain any suitable solvent and/or any suitable vehicle and/or any suitable cosmetically acceptable excipient, optionally in combination with other compounds of interest.
Avantageusement la composition ne comprend pas de filtre UV, en particulier de filtre solaire, et/ou d'autres filtres anti-lumière bleue. Advantageously, the composition does not include a UV filter, in particular a sunscreen, and/or other anti-blue light filters.
De ce fait, pour ces compositions, l’excipient cosmétiquement acceptable contient par exemple au moins un composé choisi parmi le groupe consistant en les conservateurs, les emollients, les émulsifiants, les tensioactifs, les hydratants, les épaississants, les conditionneurs, les agents matifiants, les stabilisants, les antioxydants, les agents de texture, les agents de brillance, les agents filmogènes, les solubilisants, les pigments, les colorants et les parfums. Ces excipients sont de préférence choisis parmi le groupe consistant en les acides aminés et leurs dérivés, les polyglycérols, les esters, les polymères et dérivés de cellulose, les dérivés de Lanoline, les phospholipides, les lactoferrines, les lactoperoxidases, les stabilisants à base de sucrose, les vitamines E et ses dérivés, les cires naturelles et synthétiques, les huiles végétales, les triglycérides, les insaponifiables, des phytostérols, les esters végétaux, les silicones et ses dérivés, les hydrolysats de protéines, l'huile de Jojoba et ses dérivés, les esters lipo/hydrosolubles, les bétaïnes, les aminoxides, les extraits de plantes les esters de Saccharose, les dioxydes de Titane, les glycines, et les parabens, et encore de préférence parmi le groupe consistant en le butylène glycol, le stéareth-2, le stéareth-21, le glycol-15 stéaryl éther, le cétéaryl alcool, le phénoxyéthanol, le méthylparaben, l'éthylparaben, le propylparaben, le butylparaben, le butylène glycol, les tocophérols naturels, la glycérine, le dihydroxycetyl sodium phosphate, l'isopropyl hydroxycétyl éther, le glycol stéarate, le triisononanoin, l'octyl cocoate, le polyacrylamide, l'isoparaffine, le laureth-7, un carbomer, le propylène glycol, le glycérol, le bisabolol, une diméthicone, l'hydroxyde de sodium, le PEG 30-dipolyhydroxystérate, les caprique/caprylique triglycérides, le cétéaryl octanoate, le dibutyl adipate, l'huile de pépin de raisin, l'huile de jojoba, le sulfate de magnésium, l'EDTA, une cyclométhicone, la gomme de xanthane, l'acide citrique, le lauryl sulfate de sodium, les cires et les huiles minérales, l'isostéaryl isostéarate, le dipélargonate de propylène glycol, l'isostéarate de propylène glycol, le PEG 8, Beeswax, les glycérides d'huile de palme hydrogénée, l'huile de lanoline, l'huile de sesame, le cetyl lactate, le lanoline alcool, l'huile de ricin, le dioxyde de titane, le lactose, le saccharose, le polyéthylène basse densité, une solution isotonique salée. Therefore, for these compositions, the cosmetically acceptable excipient contains, for example, at least one compound chosen from the group consisting of preservatives, emollients, emulsifiers, surfactants, moisturizers, thickeners, conditioners, mattifying agents, stabilizers, antioxidants, texture agents, shine agents, film-forming agents, solubilizers, pigments, dyes and perfumes. These excipients are preferably chosen from the group consisting of amino acids and their derivatives, polyglycerols, esters, polymers and cellulose derivatives, Lanolin derivatives, phospholipids, lactoferrins, lactoperoxidases, stabilizers based on sucrose, vitamins E and its derivatives, natural and synthetic waxes, vegetable oils, triglycerides, unsaponifiables, phytosterols, vegetable esters, silicones and their derivatives, protein hydrolysates, Jojoba oil and its derivatives, lipo/water-soluble esters, betaines, aminoxides, plant extracts, sucrose esters, titanium dioxides, glycines, and parabens, and more preferably from the group consisting of butylene glycol, steareth -2, steareth-21, stearyl ether glycol-15, cetearyl alcohol, phenoxyethanol, methylparaben, ethylparaben, propylparaben, butylparaben, butylene glycol, toco natural pherols, glycerin, dihydroxycetyl sodium phosphate, isopropyl hydroxycetyl ether, glycol stearate, triisononanoin, octyl cocoate, polyacrylamide, isoparaffin, laureth-7, a carbomer, propylene glycol, glycerol , bisabolol, dimethicone, sodium hydroxide, PEG 30-dipolyhydroxysterate, capric/caprylic triglycerides, cetearyl octanoate, dibutyl adipate, grapeseed oil, jojoba oil, magnesium, EDTA, a cyclomethicone, xanthan gum, citric acid, sodium lauryl sulphate, waxes and mineral oils, isostearyl isostearate, propylene glycol dipelargonate, propylene glycol isostearate, PEG 8, Beeswax, hydrogenated palm oil glycerides, lanolin, sesame oil, cetyl lactate, lanolin alcohol, castor oil, titanium dioxide, lactose, sucrose, low density polyethylene, isotonic saline solution.
De nombreux ingrédients cosmétiquement actifs sont connus par l’homme du métier pour améliorer l'aspect de la peau et/ou la protéger. L’homme du métier sait formuler les compositions cosmétiques ou dermatologiques pour obtenir les meilleurs effets. D’autre part les composés décrits dans la présente invention peuvent avoir un effet de synergie lorsqu'ils sont combinés les uns aux autres. Ces combinaisons sont également couvertes par la présente invention. Le CTFA Cosmetic Ingredient Handbook, Second Edition (1992) décrit différents ingrédients cosmétiques et pharmaceutiques utilisés couramment dans l'industrie cosmétique et pharmaceutique, qui sont en particulier adaptés à une utilisation topique. Des exemples de ces classes d'ingrédients comprennent, sans en être limité les composés suivants: abrasif, absorbants, composé à but esthétique tel que les parfums, les pigments, les colorants, les huiles essentielles, les astringents, les agents anti-acné, les agents anti- floculants, les agents antimousse, les agents antimicrobiens (par exemple: iodopropyl butylcarbamate), les antioxydants, les liants, les additives biologiques, les agents tampon, les agents gonflants, les agents chélatants, les additifs, les agents biocides, les dénaturants, les épaississants, et les vitamines, et les dérivés ou équivalents de ceux-ci, les matériaux formant des films, les polymères, les agents opacifiants, les ajusteurs de pH, les agents réducteurs, les agents dépigmentants ou éclaircissants (par exemple : hydroquinone, acide kojique, acide ascorbique, magnésium ascorbyl phosphate, ascorbyl glucosamine), les agents de conditionnement (par exemple : les humectants). Many cosmetically active ingredients are known to those skilled in the art for improving the appearance of the skin and/or protecting it. A person skilled in the art knows how to formulate cosmetic or dermatological compositions to obtain the best effects. On the other hand the compounds described in the present invention can have a synergistic effect when they are combined with each other. These combinations are also covered by the present invention. The CTFA Cosmetic Ingredient Handbook, Second Edition (1992) describes various cosmetic and pharmaceutical ingredients commonly used in the cosmetic and pharmaceutical industry, which are particularly suitable for topical use. Examples of these classes of ingredients include, but are not limited to, the following compounds: abrasive, absorbents, compounds for aesthetic purposes such as perfumes, pigments, dyes, essential oils, astringents, anti-acne agents, anti-flocculating agents, antifoaming agents, antimicrobial agents (for example: iodopropyl butylcarbamate), antioxidants, binders, biological additives, buffering agents, swelling agents, chelating agents, additives, biocidal agents, denaturants, thickeners, and vitamins, and derivatives or equivalents thereof, film forming materials, polymers, opacifying agents, pH adjusters, reducing agents, depigmenting or lightening agents (e.g. hydroquinone, kojic acid, ascorbic acid, magnesium ascorbyl phosphate, ascorbyl glucosamine), conditioning agents (eg humectants).
De manière particulièrement avantageuse, les microsphères selon l'invention peuvent être utilisées, éventuellement dans une composition cosmétique, comme seul agent de protection de la peau et/ou des annexes et/ou des muqueuses contre les effets inesthétiques et/ou désagréables et/ou inconfortables de la lumière bleue ou en combinaison avec d'autres agents actifs ayant des propriétés complémentaires et classiques dans les compositions cosmétiques comme par exemple ceux choisis parmi : In a particularly advantageous manner, the microspheres according to the invention can be used, optionally in a composition cosmetic, as the sole agent for protecting the skin and/or appendages and/or mucous membranes against the unsightly and/or unpleasant and/or uncomfortable effects of blue light or in combination with other active agents having complementary and conventional in cosmetic compositions, such as those chosen from:
- les agent hydratants : un ou plusieurs agents favorisant l'hydratation tels qu'un polysaccharide extrait de graines de Cassia angustifoüa commercialisée sous le nom de Hyalurosmooth™ par la demanderesse, ou un agent choisi parmi une des combinaisons contenant du pullulan, du hyaluronate de sodium et de l'alginate de sodium commercialisé sous le nom de PatcH2O™ par la demanderesse ou encore un ou plusieurs des composés du facteur naturel d'hydratation (Natural Moisturizing Factor) ou un extrait naturel de miel commercialisé par la demanderesse sous le nom de Melhydran™ et/ou un composé de la famille des glucosyl glycérides, en particulier l'hexosyl glycéride, un extrait de péricarpe de Litchi chinensis sous le nom Litchiderm™ par la demanderesse; - moisturizing agents: one or more agents promoting hydration such as a polysaccharide extracted from seeds of Cassia angustifoüa marketed under the name Hyalurosmooth™ by the applicant, or an agent chosen from one of the combinations containing pullulan, hyaluronate of sodium and sodium alginate marketed under the name PatcH2O™ by the applicant or one or more of the compounds of the natural moisturizing factor or a natural extract of honey marketed by the applicant under the name Melhydran™ and/or a compound of the glucosyl glyceride family, in particular hexosyl glyceride, an extract of the pericarp of Litchi chinensis under the name Litchiderm™ by the applicant;
- un agent stimulant la synthèse de fibronectine, en particulier un extrait de mais, un tel extrait étant notamment commercialisé par la demanderesse sous le nom DelinerTM ; - an agent stimulating the synthesis of fibronectin, in particular an extract of maize, such an extract being in particular marketed by the applicant under the name Deliner™;
- un agent de protection du facteur de croissance des fibroblastes (FGF2) de la matrice extracellulaire contre sa dégradation et/ou sa dénaturation, notamment un extrait d'Hibiscus Abeimoscus tel que décrit dans la demande de brevet au nom de la demanderesse déposée sous le numéro FR0654316 et/ou un agent de stimulation de croissance des fibroblastes par exemple un extrait de soja fermenté contenant des peptides, connu sous le nom de PhytokineTM commercialisé par la demanderesse et également décrit dans la demande de brevet EPI 119344 B1 (Laboratoires Expanscience), et preferentiellement une combinaison de ces deux extraits; - an agent for protecting the fibroblast growth factor (FGF2) of the extracellular matrix against its degradation and/or its denaturation, in particular an extract of Hibiscus Abeimoscus as described in the patent application in the name of the applicant filed under the number FR0654316 and/or an agent for stimulating the growth of fibroblasts, for example a fermented soybean extract containing peptides, known under the name of PhytokineTM marketed by the applicant and also described in patent application EPI 119344 B1 (Laboratories Expanscience), and preferably a combination of these two extracts;
- un agent stimulant la synthèse de laminine, en particulier un extrait de malt modifié par biotechnologie, un tel extrait étant notamment commercialisé par la demanderesse sous le nom Basaline TM ; et un agent stimulant de la synthèse des lipides comme un extrait de pomme de terre (so/anum tuberosum) modifié par biotechnologie commercialisé par la demanderesse sous le nom Lipidessence™ ; - an agent stimulating the synthesis of laminin, in particular a malt extract modified by biotechnology, such an extract being in particular marketed by the applicant under the name Basaline TM; and a lipid synthesis stimulating agent such as a potato extract (so/anum tuberosum) modified by biotechnology marketed by the applicant under the name Lipidessence™;
- un agent stimulant l'expression et/ou l'activité de la Hyaluronane synthase 2 (HAS2) tel que les extraits végétaux décrits dans la demande de brevet FR2 893 252 Al et en particulier un extrait aqueux de Galanga Aipinia galanga) commercialisé sous le nom Hyalufix™ par la demanderesse ; - an agent stimulating the expression and/or the activity of Hyaluronan synthase 2 (HAS2) such as the plant extracts described in patent application FR2 893 252 Al and in particular an aqueous extract of Galanga Aipinia galanga) marketed under the name Hyalufix™ by the applicant;
- un agent stimulant la synthèse de lysyl oxydase like (LOXL) tel que ceux décrits dans la demande de brevet FR2855968, et en particulier un extrait d'aneth commercialisé sous le nom Lys'lastine™ par la demanderesse ;- an agent stimulating the synthesis of lysyl oxidase like (LOXL) such as those described in patent application FR2855968, and in particular a dill extract marketed under the name Lys'lastine™ by the applicant;
- un ou plusieurs agents anti-pollution tels qu'un extrait de feuilles dA' rgania spinosa commercialisé sous le nom d'Arganyl™ par la demanderesse ou un extrait de graines de Moringa oleifera commercialisé sous le nom de Purisoft™ par la demanderesse ou encore un extrait de racine d'Eperua falcata commercialisé sous le nom de Eperuline™ par la demanderesse ; - one or more anti-pollution agents such as an extract of leaves of A' rgania spinosa marketed under the name Arganyl™ by the applicant or an extract of seeds of Moringa oleifera marketed under the name Purisoft™ by the applicant or else a root extract of Eperua falcata marketed under the name Eperuline™ by the applicant;
- un agent stimulant la synthèse d'ATP intracellulaire, notamment un extrait d'algue Laminaria digitata ; - an agent stimulating the synthesis of intracellular ATP, in particular an extract of Laminaria digitata seaweed;
- un agent à action globale anti-âge, notamment antitaches pigmentaires en particulier la niacinamide ou vitamine B3; - an agent with overall anti-ageing action, in particular anti-pigment spots, in particular niacinamide or vitamin B3;
- un agent antibactérien et/ou de régulation du sébum, et/ou absorbeur de sébum tels que les rétinoïdes, la sarcosine, les sels de zinc en particulier le gluconate de zinc, salicylate de zinc, acide azélaique, et/ou leurs derives et melanges, un extrait d'Orthosiphon stamineus commercialisé sous le nom de MAT XS™ Bright par la demanderesse, un extrait de Bixa Orellana commercialisé sous le nom de Bix'Activ ™ par la demanderesse, les extraits antibactériens décrits dans la demande de brevet FR2863893, et en particulier un extrait de Boldo notamment celui commercialisé sous le nom Betapur™ par la demanderesse, ou du talc, - et l’un quelconque de leurs mélanges. - an antibacterial and/or sebum regulating agent, and/or sebum absorber such as retinoids, sarcosine, zinc salts, in particular zinc gluconate, zinc salicylate, azelaic acid, and/or their derivatives and mixtures, an extract of Orthosiphon stamineus marketed under the name MAT XS™ Bright by the applicant, an extract of Bixa Orellana marketed under the name Bix'Activ ™ by the applicant, the antibacterial extracts described in the application for patent FR2863893, and in particular a Boldo extract, in particular that marketed under the name Betapur™ by the applicant, or talc, - and any of their mixtures.
L'utilisation des microsphères poreuses selon la présente invention, est particulièrement avantageuse en ce qu'elle permet une action immédiatement efficace et durable sur tout type de peaux incluant cuir chevelu, sur les annexes cutanées, préférentiellement les cheveux et sur les muqueuses. The use of porous microspheres according to the present invention is particularly advantageous in that it allows an immediately effective and lasting action on any type of skin including the scalp, on the skin appendages, preferably the hair and on the mucous membranes.
De manière préférentielle, les microsphères poreuses selon l'invention, préférentiellement sous la forme d'une composition cosmétique selon l'invention sont appliquées sur au moins une zone du corps exposée à la lumière bleue, cette ou ces zones étant préférentiellement une surface du corps choisie parmi la peau du visage, incluant le front, les joues, le nez, les tempes, la zone T (front, nez et menton), sous les yeux, la zone péri orbitale, en particulier les cernes, le contour des lèvres et/ou le menton, le cuir chevelu, le cou, le dos, les épaules, les avant-bras, le thorax, les mains, les cheveux, la barbe, les cils, les sourcils le buste, les jambes, les pieds, les aisselles, les mains, le décolleté, le ventre, les bras, les cuisses, les hanches, les fesses, la taille, le torse. Preferably, the porous microspheres according to the invention, preferably in the form of a cosmetic composition according to the invention, are applied to at least one area of the body exposed to blue light, this or these areas preferably being a surface of the body chosen from the skin of the face, including the forehead, the cheeks, the nose, the temples, the T zone (forehead, nose and chin), under the eyes, the peri-orbital zone, in particular dark circles, the contour of the lips and /or the chin, the scalp, the neck, the back, the shoulders, the forearms, the thorax, the hands, the hair, the beard, the eyelashes, the eyebrows the bust, the legs, the feet, the armpits, hands, décolleté, stomach, arms, thighs, hips, buttocks, waist, torso.
La présente invention a ainsi également pour objet un procédé de soin cosmétique non thérapeutique comprenant l'application par voie topique sur au moins une zone de peau et/ou de muqueuse et/ou d'annexes cutanées, notamment de cheveux, des microsphères poreuses selon l'invention, avantageusement sur tout ou partie de la peau et/ou des muqueuses du corps et/ou du visage choisie parmi le cuir chevelu, les jambes, les cuisses, les bras, le ventre, le decollete, le cou, tout ou partie du visage, le front, le menton, les lèvres, le contour des lèvres, le contour des yeux, la zone dite « en T » du visage, et/ou sur tout ou partie des annexes cutanées, plus préférentiellement les cheveux, préférentiellement sur au moins une surface choisie parmi une surface du corps choisie parmi la peau du visage, incluant le front, les joues, le nez, les tempes, la zone T (front, nez et menton), sous les yeux, la zone péri orbitale, en particulier les cernes, le contour des lèvres et/ou le menton, le cuir chevelu, le cou, le dos, les épaules, les avant-bras, le thorax, les mains, les cheveux, la barbe, les cils, les sourcils, le buste, les jambes, les pieds, les aisselles, les mains, le décolleté, le ventre, les bras, les cuisses, les hanches, les fesses, la taille, le torse, et les cheveux. The present invention thus also relates to a non-therapeutic cosmetic care process comprising the topical application to at least one area of skin and/or mucosa and/or skin appendages, in particular hair, of porous microspheres according to the invention, advantageously on all or part of the skin and/or the mucous membranes of the body and/or the face chosen from the scalp, the legs, thighs, arms, stomach, décolleté, neck, all or part of the face, forehead, chin, lips, lip contour, eye contour, the so-called "T" area of the face, and/or on all or part of the skin appendages, more preferably the hair, preferably on at least one surface chosen from a surface of the body chosen from the skin of the face, including the forehead, the cheeks, the nose, the temples, the T zone (forehead, nose and chin), under the eyes, the peri-orbital zone, in particular dark circles, the contour of the lips and/or the chin, the scalp, the neck, the back, the shoulders, the front -arms, chest, hands, hair, beard, eyelashes, eyebrows, chest, legs, feet, armpits, hands, neckline, stomach, arms, thighs, hips , buttocks, waist, torso, and hair.
Les microsphères selon l'invention conviennent particulièrement pour leurs utilisations sur tout type de peau, muqueuses et/ou annexes, notamment Caucasienne, Asiatique, africaine ainsi que sur toute nature de peau, en particulier sur peau jeune et/ou présentant les premiers signes de l'âge et/ou pour les peaux matures, c'est-à-dire les hommes ou les femmes ayant au moins 50 ans, en particulier les femmes ménopausées. The microspheres according to the invention are particularly suitable for their uses on any type of skin, mucous membranes and/or appendages, in particular Caucasian, Asian, African as well as on any type of skin, in particular on young skin and/or showing the first signs of age and/or for mature skin, that is to say men or women aged at least 50, in particular menopausal women.
Les compositions cosmétiques selon l'invention sont préférentiellement de type sans rinçage. The cosmetic compositions according to the invention are preferably of the leave-in type.
De manière avantageuse, les microsphères poreuses selon l'invention, préférentiellement sous la forme d'une composition destinée à une application topique, préférentiellement cosmétique selon l'invention, sont utilisées en application topique régulière et préférentiellement au moins une fois par jour, avantageusement deux fois par jour. De manière préférentielle, la composition cosmétique est appliquée sur la peau. Advantageously, the porous microspheres according to the invention, preferentially in the form of a composition intended for topical application, preferentially cosmetic according to the invention, are used in regular topical application and preferentially at least once a day, advantageously twice times a day. Preferably, the cosmetic composition is applied to the skin.
Les microsphères peuvent être utilisées en poudre mais aussi sous la forme d'un ingrédient cosmétique formulé sous forme liquide. Pour leur formulation comme ingrédient cosmétique, les microsphères sont alors preferentiellement mises en suspension dans la glycerine et/ou dans un autre solvant, notamment polaire tel que l'eau, les alcools, notamment le propanediol, les glycols notamment le butylène glycol, le propylène glycol, les polyols ou un mélange de ceux-ci, préférentiellement un mélange hydroglycolique, encore préférentiellement contenant un glycol choisi parmi le butylène glycol, le propylène glycol, le caprylyl glycol, l'hexylène glycol et leurs mélanges. De manière particulièrement avantageuse, les microsphères selon l'invention sont mises en suspension dans une solution aqueuse contenant de la glycérine, de l'hexylène glycol, du caprylyl glycol ou un de leur mélange. The microspheres can be used in powder but also in the form of a cosmetic ingredient formulated in liquid form. For their formulation as a cosmetic ingredient, the microspheres are then preferably suspended in glycerin 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 thereof , preferably a hydroglycolic mixture, more preferably containing a glycol chosen from butylene glycol, propylene glycol, caprylyl glycol, hexylene glycol and mixtures thereof. In a particularly advantageous manner, the microspheres according to the invention are suspended in an aqueous solution containing glycerin, hexylene glycol, caprylyl glycol or a mixture thereof.
L'invention a également pour objet un procédé de soin cosmétique non thérapeutique comprenant l'application sur au moins une zone de peau et/ou de muqueuse et/ou d'annexes cutanées de microsphères poreuses comprenant, avantageusement constituée par, un oxyde métallique ou d'une composition cosmétique les comprenant pour protéger la zone de peau, d'annexes cutanées, notamment de cheveux, et/ou de muqueuse contre les effets inesthétiques et/ou désagréables et/ou inconfortables de la lumière bleue et/ou pour en diminuer et/ou ralentir lesdits effets sur cette zone de peau, d'annexes cutanées notamment de cheveux, et/ou de muqueuses, et/ou pour empêcher la survenance desdits effets inesthétiques et/ou désagréables et/ou inconfortables de la lumière bleue et/ou d’en ralentir l’apparition, les effets inesthétiques et/ou désagréables et/ou inconfortables étant avantageusement choisis parmi le vieillissement de la peau et/ou des muqueuses et/ou des annexes cutanées et/ou l'altération de la barrière cutanée et/ou mucosale et/ou la déshydratation de la peau et/ou des muqueuses et/ou des annexes cutanées et/ou l'altération des propriétés biomécaniques de la peau et/ou des muqueuses et/ou des annexes cutanées, lesdites microsphères ayant : - un diamètre moyen D50 mesure par microscopie électronique a balayage (SEM) allant de 1 pm à 30 pm, The invention also relates to a non-therapeutic cosmetic care process comprising the application to at least one area of skin and/or mucosa and/or cutaneous appendages of porous microspheres comprising, advantageously consisting of, a metal oxide or of a cosmetic composition comprising them to protect the area of skin, skin appendages, in particular hair, and/or mucous membrane against the unsightly and/or unpleasant and/or uncomfortable effects of blue light and/or to reduce it and/or slow down said effects on this area of skin, skin appendages, in particular hair, and/or mucous membranes, and/or to prevent the occurrence of said unsightly and/or unpleasant and/or uncomfortable effects of blue light and/or or to slow down their appearance, the unsightly and/or unpleasant and/or uncomfortable effects being advantageously chosen from aging of the skin and/or of the mucous membranes and/or of the cutaneous appendages and/or alteration of the bar cutaneous and/or mucosal arrhythmia and/or dehydration of the skin and/or mucous membranes and/or skin appendages and/or alteration of the biomechanical properties of the skin and/or mucosa and/or skin appendages, said microspheres having: - an average diameter D50 measured by scanning electron microscopy (SEM) ranging from 1 μm to 30 μm,
- des pores dont le diamètre moyen D50 mesuré par microscopie électronique à balayage (SEM) va de 50nm à 250nm et - pores whose average diameter D50 measured by scanning electron microscopy (SEM) ranges from 50 nm to 250 nm and
- une porosité moyenne mesurée par porosimétrie au mercure allant de 0,40 à 0,65. - an average porosity measured by mercury porosimetry ranging from 0.40 to 0.65.
Avantageusement le procédé de soin cosmétique selon l'invention comprend la sélection d'une zone de peau et/ou d'annexes cutanées, notamment de cheveux, et/ou de muqueuse susceptible d'être soumis à un rayonnement de lumière bleue et/ou que l'on souhaite protéger contre les effets inesthétiques et/ou désagréables et/ou inconfortables de la lumière bleue et/ou en diminuer et/ou en ralentir lesdits effets et/ou dont on souhaite empêcher la survenance desdits effets inesthétiques et/ou désagréables et/ou inconfortables de la lumière bleue et/ou d’en ralentir l’apparition, avant l’application sur ladite zone de peau. Advantageously, the cosmetic care process according to the invention comprises the selection of an area of skin and/or skin appendages, in particular hair, and/or mucous membrane likely to be subjected to radiation of blue light and/or which it is desired to protect against the unsightly and/or unpleasant and/or uncomfortable effects of blue light and/or to reduce and/or slow down said effects and/or which it is desired to prevent the occurrence of said unsightly and/or unpleasant effects and/or uncomfortable from blue light and/or to slow down its appearance, before application to said area of skin.
Avantageusement le procédé de soin cosmétique selon l'invention est, caractérisé en ce que les microsphères poreuses et/ou la composition cosmétique les comprenant sont appliqués par voie topique sur tout ou partie de la peau et/ou des muqueuses du corps et/ou du visage choisie parmi le cuir chevelu, les jambes, les cuisses, les bras, le ventre, le décolleté, le cou, tout ou partie du visage, le front, le menton, les lèvres, le contour des lèvres, le contour des yeux, la zone dite « en T » du visage, et/ou sur tout ou partie des annexes cutanées, plus préférentiellement les cheveux. Advantageously, the cosmetic care process according to the invention is characterized in that the porous microspheres and/or the cosmetic composition comprising them are applied topically to all or part of the skin and/or the mucous membranes of the body and/or the face chosen from the scalp, legs, thighs, arms, stomach, décolleté, neck, all or part of the face, forehead, chin, lips, lip contour, eye contour, the so-called “T” zone of the face, and/or on all or part of the skin appendages, more preferably the hair.
Avantageusement le procédé de soin cosmétique selon l'invention est caractérisé en ce que les microsphères poreuses et/ou la composition cosmétique les comprenant sont tels que définis ci-dessous : Advantageously, the cosmetic care process according to the invention is characterized in that the porous microspheres and/or the cosmetic composition comprising them are as defined below:
- l'oxyde métallique est choisi dans le groupe constitué par SiCh, TiCh, ZnO et leurs mélanges, avantageusement il s'agit de SiO2 ; et/ou - les microspheres ont un diamètre moyen D50 mesure par microscopie électronique à balayage (SEM) allant de 1,3 à 10 pm, en particulier de 1,5 à 4,5 pm ; et/ou - the metal oxide is chosen from the group consisting of SiCh, TiCh, ZnO and their mixtures, advantageously it is SiO 2 ; and or - the microspheres have an average diameter D50 measured by scanning electron microscopy (SEM) ranging from 1.3 to 10 μm, in particular from 1.5 to 4.5 μm; and or
- le diamètre moyen D50 de pores des microsphères mesuré par microscopie électronique à balayage (SEM) va de 100 à 245 nm, en particulier de 180 à 225 nm ; et/ou - the average pore diameter D50 of the microspheres measured by scanning electron microscopy (SEM) ranges from 100 to 245 nm, in particular from 180 to 225 nm; and or
- les microsphères ne contiennent pas et/ou ne sont pas utilisées en combinaison avec un autre filtre anti-lumière bleue et/ou un filtre anti-UV et/ou un filtre solaire et/ou dans une composition cosmétique qui en contient ; et/ou - the microspheres do not contain and/or are not used in combination with another anti-blue light filter and/or an anti-UV filter and/or a sunscreen and/or in a cosmetic composition which contains it; and or
- les microsphères poreuses sont comprises dans une composition cosmétique, à une teneur allant de 0,01% à 20% en poids, avantageusement de 0,1% à 5% en poids, encore avantageusement de 0,5% à 3% en poids, en particulier de 1% à 2 % en poids, par rapport au poids total de la composition ; et/ou - the porous microspheres are included in a cosmetic composition, at a content ranging from 0.01% to 20% by weight, advantageously from 0.1% to 5% by weight, again advantageously from 0.5% to 3% by weight , in particular from 1% to 2% by weight, relative to the total weight of the composition; and or
- la composition cosmétique comprend au moins un excipient cosmétiquement acceptable et que cette composition est choisie parmi un sérum, une lotion, une crème, un shampoing, un après-shampoing, une huile, un lait, une pommade, une pâte, une mousse, une émulsion, un hydrogel, un gel douche, un masque, une laque, un spray, une cire, un mascara, un crayon de maquillage, un vernis, d'une poudre, notamment de maquillage, d'un stick. - the cosmetic composition comprises at least one cosmetically acceptable excipient and that this composition is chosen from 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 mascara, a make-up pencil, a varnish, a powder, in particular a make-up powder, a stick.
Avantageusement le procédé de soin cosmétique selon l'invention est pour prévenir et/ou ralentir Advantageously, the cosmetic care process according to the invention is for preventing and/or slowing down
- l'apparition de rides et/ou ridules et/ou de tâches pigmentaires sur la peau et/ou les muqueuses, et/ou - the appearance of wrinkles and/or fine lines and/or pigment spots on the skin and/or mucous membranes, and/or
- la perte d'éclat du teint de la peau et/ou des muqueuses et/ou le manque d'homogénéité du teint de la peau et/ou des muqueuses et/ou- loss of radiance in the complexion of the skin and/or mucous membranes and/or lack of uniformity in the complexion of the skin and/or mucous membranes and/or
- le relâchement cutanée et/ou -la perte de tonicité et/ou d'elasticite et/ ou de fermete et/ou de densite de la peau et/ou des muqueuses et/ou - sagging skin and/or -loss of tone and/or elasticity and/or firmness and/or density of the skin and/or mucous membranes and/or
- le blanchiment et/ou grisonnement des annexes cutanées et/ou - whitening and/or graying of the skin appendages and/or
- la déshydratation et/ou les pertes insensibles en eau de la peau et/ou des muqueuses et/ou - dehydration and/or transepidermal water loss from the skin and/or mucous membranes and/or
- l'altération du microrelief de la peau et/ou des muqueuses et/ou - alteration of the microrelief of the skin and/or mucous membranes and/or
- l'altération des propriétés de surface et/ou de texture et/ou visuelle et/ou des qualités sensorielles de la peau et/ou des muqueuses et/ou des annexes cutanées en particulier des cheveux. - the alteration of the surface properties and/or of texture and/or visual and/or of the sensory qualities of the skin and/or of the mucous membranes and/or of the cutaneous appendages in particular of the hair.
De manière avantageuse, l'invention a également pour objet une méthode de traitement cosmétique pour protéger la peau, les annexes cutanées, notamment les cheveux, et/ou les muqueuses contre les effets inesthétiques et/ou désagréables et/ou inconfortables de la lumière bleue et/ou pour en diminuer et/ou ralentir lesdits effets sur la peau, les annexes cutanées notamment les cheveux, et/ou les muqueuses et/ou dont pour empêcher la survenance desdits effets inesthétiques et/ou désagréables et/ou inconfortables de la lumière bleue et/ou d’en ralentir l’apparition, d'un individu qui en a besoin/qui le souhaite comprenant les étapes : Advantageously, the invention also relates to a cosmetic treatment method for protecting the skin, the skin appendages, in particular the hair, and/or the mucous membranes against the unsightly and/or unpleasant and/or uncomfortable effects of blue light. and/or to reduce and/or slow down said effects on the skin, the skin appendages, in particular the hair, and/or the mucous membranes and/or including to prevent the occurrence of said unsightly and/or unpleasant and/or uncomfortable effects of light blue and/or to slow down its appearance, of an individual who needs/wants it, including the steps:
- L'identification sur l'individu d'une zone de peau et/ou d'annexes cutanées, notamment de cheveux, et/ou de muqueuse susceptible d'être soumis à un rayonnement de lumière bleue et/ou que l'on souhaite protéger contre les effets inesthétiques et/ou désagréables et/ou inconfortables de la lumière bleue et/ou en diminuer et/ou en ralentir lesdits effets, et/ou dont on souhaite empêcher la survenance desdits effets inesthétiques et/ou désagréables et/ou inconfortables de la lumière bleue et/ou d'en ralentir l'apparition et - The identification on the individual of an area of skin and/or cutaneous appendages, in particular hair, and/or mucous membrane likely to be subjected to blue light radiation and/or that one wishes protect against the unsightly and/or unpleasant and/or uncomfortable effects of blue light and/or reduce and/or slow down said effects thereof, and/or the occurrence of said unsightly and/or unpleasant and/or uncomfortable effects from which it is desired to prevent blue light and/or to slow down its appearance and
- L'application topique sur cette zone de peau et/ou d'annexes cutanées, notamment de cheveux, et/ou de muqueuse d'une composition cosmétique contenant les microsphères selon l'invention en une quantité efficace pour protéger cette zone de peau et/ou d'annexes cutanées, préférentiellement de cheveux, et/ ou de muqueuse contre les effets inesthétiques et/ou désagréables et/ou inconfortables de la lumière bleue et/ou pour en diminuer et/ou ralentir les effets, et/ou pour empêcher la survenance desdits effets inesthétiques et/ou désagréables et/ou inconfortables de la lumière bleue et/ou pour en ralentir l’apparition à savoir avantageusement en une teneur en microsphères allant de 0,01 à 20%, avantageusement allant de 0,1 à 5%, de préférence allant de 0,5% à 3%, encore préférentiellement de 1% jusqu'à 2%, en poids par rapport au poids total de la composition. - Topical application to this area of skin and/or skin appendages, in particular hair, and/or mucosa of a cosmetic composition containing the microspheres according to the invention in an amount effective for protecting this area of skin and/or skin appendages, preferably hair, and/or mucous membrane against the unsightly and/or unpleasant and/or uncomfortable effects of blue light and/or for reducing and/or slowing it down the effects, and/or to prevent the occurrence of said unsightly and/or unpleasant and/or uncomfortable effects of blue light and/or to slow down its appearance, namely advantageously in a content of microspheres ranging from 0.01 to 20% , advantageously ranging from 0.1 to 5%, preferably ranging from 0.5% to 3%, more preferably from 1% to 2%, by weight relative to the total weight of the composition.
D’autres buts, caractéristiques et avantages de l’invention apparaîtront clairement à l’homme de l’art suite à la lecture de la description explicative qui fait référence à des exemples qui sont donnés seulement à titre d’illustration et qui ne sauraient en aucune façon limiter la portée de l’invention. Other aims, characteristics and advantages of the invention will appear clearly to those skilled in the art following reading of the explanatory description which refers to examples which are given solely by way of illustration and which cannot in no way limit the scope of the invention.
Les exemples font partie intégrante de la présente invention et toute caractéristique apparaissant nouvelle par rapport à un état de la technique antérieure quelconque à partir de la description prise dans son ensemble, incluant les exemples, fait partie intégrante de l’invention dans sa fonction et dans sa généralité. Ainsi, chaque exemple a une portée générale. D’autre part, dans les exemples, tous les pourcentages sont donnés en poids, sauf indication contraire, la température est exprimée en degré Celsius sauf indication contraire, et la pression est la pression atmosphérique, sauf indication contraire.
Figure imgf000049_0001
The examples form an integral part of the present invention and any feature appearing new with respect to any state of the prior art from the description taken as a whole, including the examples, forms an integral part of the invention in its function and in its generality. Thus, each example is general in scope. On the other hand, in the examples, all the percentages are given by weight, unless otherwise indicated, the temperature is expressed in degrees Celsius unless otherwise indicated, and the pressure is atmospheric pressure, unless otherwise indicated.
Figure imgf000049_0001
Exemple 1 : Microsphères de silice poreuses Example 1: Porous Silica Microspheres
Un copolymère de styrène et d'acide acrylique est préparé comme suit : une quantité de 230 mL d'eau désionisée (DI) est ajoutée dans un ballon de réaction à 3 cols équipé d'un thermomètre, d'un condenseur, d'une agitation magnétique et sous atmosphere azotee. L'eau est chauffée a 80°C et une quantité de 10g de styrène est ajoutée sous agitation, suivi d'une quantité de 100 mg d'acide acrylique dissoute dans une quantité de 10ml d'eau désionisée, à la seringue. Une quantité de 100 mg of de persulfate d'ammonium est dissoute dans 10 ml d'eau désionisée et ajoutée à la seringue dans le mélange sous agitation. Le mélange est laissé sous agitation pendant 24 heures à 80°C. La dispersion colloïdale de polymère est mise à refroidir à température ambiante et est purifiée par centrifugation, formant ainsi les nanosphères de polystyrène ayant une taille moyenne de particules de 250 nm. La dispersion aqueuse colloïdale de polystyrène est diluée dans l'eau désionisée à une teneur de 7,5% en poids, par rapport au poids total de la composition et 2,5 % en poids de nanoparticules de silice par rapport au poids total de la composition sont ajoutées au mélange. Cette dispersion contient donc 7,5 % en poids de polystyrène, 2,5% en poids de nanoparticules de silice et 90% en poids d'eau désionisée par rapport au poids total de la composition. Le mélange est soumis à un traitement par ultrasons pour prévenir l'agglomération de particules. A copolymer of styrene and acrylic acid is prepared as follows: 230 mL of deionized (DI) water is added to a 3-neck reaction flask equipped with a thermometer, condenser, magnetic stirring and under nitrogen atmosphere. The water is heated to 80° C. and a quantity of 10 g of styrene is added with stirring, followed by a quantity of 100 mg of acrylic acid dissolved in a quantity of 10 ml of deionized water, by syringe. A quantity of 100 mg of ammonium persulfate is dissolved in 10 ml of deionized water and added by syringe into the mixture while stirring. The mixture is left under stirring for 24 hours at 80°C. The polymer colloidal dispersion is allowed to cool to room temperature and is purified by centrifugation, thereby forming polystyrene nanospheres having an average particle size of 250 nm. The colloidal aqueous dispersion of polystyrene is diluted in deionized water to a content of 7.5% by weight, relative to the total weight of the composition and 2.5% by weight of silica nanoparticles relative to the total weight of the composition are added to the mixture. This dispersion therefore contains 7.5% by weight of polystyrene, 2.5% by weight of silica nanoparticles and 90% by weight of deionized water relative to the total weight of the composition. The mixture is subjected to ultrasonic treatment to prevent particle agglomeration.
La dispersion aqueuse est séchée par atomisation sous atmosphère d'azote (température d'admission : 100°C, température de sortie : 45°C, vitesse d'alimentation : lOmL/min) pour fournir des microsphères modèles monodispersées contenant 75% en poids de polystyrène et 25% en poids de silice. The aqueous dispersion is dried by atomization under a nitrogen atmosphere (inlet temperature: 100°C, outlet temperature: 45°C, feed rate: 10mL/min) to provide monodispersed model microspheres containing 75% by weight of polystyrene and 25% by weight of silica.
Ces microsphères modèles sont alors calcinées afin d'enlever le polymère en les plaçant sur une plaque de silicone, et en réalisant une montée en température de 40°C à 500°C à une vitesse de 2°C/min, puis en maintenant la température de 500°C pendant 2 heures, puis enfin en baissant la température de 500°C à 40°C à une vitesse de 2°C/min. Les microsphères poreuses de SiO2 monodispersées ainsi obtenues ont un diamètre moyen D50 de 3,01 ± 1,34 pm mesure par microscopie électronique à balayage (SEM), un diamètre moyen de pores D50 de 206 ± 10 nm mesuré par microscopie électronique à balayage (SEM) et une porosité moyenne mesurée par porosimétrie au mercure de 0,55. Les microsphères sont de couleur bleue. These model microspheres are then calcined in order to remove the polymer by placing them on a silicone plate, and by carrying out a rise in temperature from 40°C to 500°C at a rate of 2°C/min, then by maintaining the temperature of 500° C. for 2 hours, then finally lowering the temperature from 500° C. to 40° C. at a rate of 2° C./min. The porous microspheres of monodispersed SiO 2 thus obtained have a mean diameter D 50 of 3.01 ± 1.34 µm measured by scanning electron microscopy (SEM), mean pore diameter D 50 of 206 ± 10 nm measured by scanning electron microscopy (SEM) and mean porosity measured by mercury porosimetry of 0.55. The microspheres are blue in color.
Exemple 2 : évaluation de protection de la peau contre la lumière bleue sur des expiants de peau humaine Example 2: evaluation of skin protection against blue light on explants of human skin
Les microsphères obtenues à l'exemple 1 ont été incorporées dans le gel en microémulsion Emulgade® CPE commercialisée par BASF (INCI: Olus Oil (et) Glycérine (et) Lauryle Glucoside (et) Polyglycéryl-2- Dipolyhydroxystéarate (et) Glycéryle Oléate (et) Dicaprylyle Carbonate à une teneur de 1,5% en poids par rapport au poids total de la composition, sous forte agitation (composition selon l'invention). Les sphères sont inertes, ne regonflent pas, et sont en suspension dans le milieu. La dispersion est meilleure sous forte agitation en évitant les agglomérats. La composition du gel contenant les microsphères est indiquée dans le tableau 1 ci-dessous The microspheres obtained in Example 1 were incorporated into the Emulgade® CPE microemulsion gel marketed by BASF (INCI: Olus Oil (and) Glycerin (and) Lauryl Glucoside (and) Polyglyceryl-2-Dipolyhydroxystearate (and) Glyceryl Oleate ( and) Dicaprylyl Carbonate at a content of 1.5% by weight relative to the total weight of the composition, with vigorous stirring (composition according to the invention) The spheres are inert, do not re-swell, and are in suspension in the medium The dispersion is better under strong agitation avoiding agglomerates The composition of the gel containing the microspheres is indicated in table 1 below
Tableau 1
Figure imgf000051_0001
Table 1
Figure imgf000051_0001
Des expiants de peau ont été préparés à partir de biopsies abdominales fraîches obtenues par chirurgie plastique (femmes de 55 ans). Les expiants de peau ont ete cultives 6 jours dans un milieu de culture standard EMEM (milieu minimum essentiel d'Eagle), à 37°C, 5% CO2, dans une atmosphère humide avec un taux d'humidité de 95%. Skin explants were prepared from fresh abdominal biopsies obtained by plastic surgery (55-year-old women). THE skin explants were cultured for 6 days in a standard EMEM culture medium (Eagle's minimum essential medium), at 37° C., 5% CO2, in a humid atmosphere with a humidity rate of 95%.
Les expiants ont été traités tous les jours pendant 5 jours par application topique de 2mg/cm2 de la composition selon l'invention ou d'un placebo (gel en microémulsion Emulgade® CPE commercialisée par BASF ne contenant pas les microsphères selon l'invention) (contrôle placébo et contrôle lumière bleue). Puis les expiants dans un milieu solution saline équilibrée de Hanks (Hanks' Balanced Salt Solution (HBSS)) ont été irradiés (composition selon l'invention et contrôle lumière bleue) avec de la lumière bleue à 85J/cm2 (longueur d'onde 401-500 nm du spectre de lumière visible avec un pic à 455 nm pendant 4 heures) en utilisant une solarbox® ou n'ont pas été irradiées (contrôle placébo). Les expiants de peau ont ensuite été cultivés une journée de plus dans le milieu défini avant analyse. The explants were treated daily for 5 days by topical application of 2 mg/cm 2 of the composition according to the invention or of a placebo (Emulgade® CPE microemulsion gel marketed by BASF not containing the microspheres according to the invention ) (placebo control and blue light control). Then the explants in a Hanks' Balanced Salt Solution (HBSS) medium were irradiated (composition according to the invention and blue light control) with blue light at 85J/cm 2 (wavelength 401-500 nm of the visible light spectrum with a peak at 455 nm for 4 hours) using a solarbox® or were not irradiated (placebo control). The skin explants were then cultured one more day in the defined medium before analysis.
Les teneurs en MMPI et 8-OHdG des expiants de peau ont été évaluées par immunomarquage. Les expiants de peau ont été coupés en fines sections (5 pm) en utilisant un microtome (Leica RM2125, Leica Biosystems) et transférés sur lames Superfrost®. MMPI a été détecté par un anticorps monoclonal spécifique (monoclonal 36665 clone de souris, R&D Systems). 8-OHdG a été détecté par un anticorps monoclonal (monoclonal clone N45-1 de souris, Gentaur Genprice). Les anticorps primaires ont été révélés en utilisant la méthode streptavidine/biotine et peroxydase (Vector VIP Peroxidase H RP kit, Vector Laboratories Inc.). La coloration a été observée par microscope optique (Leica DMLB, Leica Microsystems ou Olympus BX43, Olympus Life Science). Les images ont été analysées en utilisant le logiciel d'analyse d'image (CellAD imaging systems, Olympus Life Science). La qualité et la viabilité des expiants de peau ont été évaluées par le marquage trichrome de Masson et contrôlées par analyse microscopique. The MMPI and 8-OHdG contents of the skin explants were evaluated by immunostaining. Skin explants were cut into thin sections (5 µm) using a microtome (Leica RM2125, Leica Biosystems) and transferred to Superfrost® slides. MMPI was detected by a specific monoclonal antibody (monoclonal 36665 mouse clone, R&D Systems). 8-OHdG was detected by a monoclonal antibody (monoclonal mouse clone N45-1, Gentaur Genprice). The primary antibodies were revealed using the streptavidin/biotin and peroxidase method (Vector VIP Peroxidase H RP kit, Vector Laboratories Inc.). Staining was observed by optical microscope (Leica DMLB, Leica Microsystems or Olympus BX43, Olympus Life Science). Images were analyzed using image analysis software (Cell A D imaging systems, Olympus Life Science). The quality and viability of explants from skin were assessed by Masson's trichrome staining and checked by microscopic analysis.
Les résultats sont exprimés par la moyenne ± la déviation standard (SD; 3 expiants par condition, 6 images par expiant). Les résultats sont exprimés en pourcentage de la surface occupée par la coloration et ont été ensuite normalisés par rapport à la condition contrôle lumière bleue. Les différences statistiques entre ces conditions ont été évaluées en utilisant le test t de Student. Le seuil de signification a été fixé à 5% (p<0,05). La colonne « Statistique » indique le niveau de significativité compte tenu de la valeur p choisie. La mention p<0.05 désigne ainsi un résultat significativement différent du contrôle choisi. La mention p<0,01 désigne un résultat très significativement différent du contrôle choisi. Les résultats concernant les teneurs en 8-OHdG et en MMPI dans l'épiderme et dans le derme sont rassemblés respectivement dans les tableaux 2 à 4 ci-dessous. Tableau 2
Figure imgf000053_0001
significative de la teneur en 8-OHdG dans la peau (P<0,01). Les microsphères selon l'invention font baisser la teneur en 8-OHdG de 37% (P<0,05). Tableau 3
Figure imgf000054_0001
Results are expressed as mean ± standard deviation (SD; 3 explants per condition, 6 images per explant). The results are expressed as a percentage of the surface occupied by the coloration and were then normalized with respect to the blue light control condition. Statistical differences between these conditions were assessed using Student's t test. The significance level was set at 5% (p<0.05). The “Statistics” column indicates the level of significance given the chosen p-value. The mention p<0.05 thus designates a result that is significantly different from the chosen control. The mention p<0.01 designates a result that is very significantly different from the chosen control. The results concerning the contents of 8-OHdG and of MMPI in the epidermis and in the dermis are collated respectively in Tables 2 to 4 below. Table 2
Figure imgf000053_0001
significant 8-OHdG content in the skin (P<0.01). The microspheres according to the invention reduce the content of 8-OHdG by 37% (P<0.05). Table 3
Figure imgf000054_0001
Les expiants exposés à la lumière bleue ont montrés une augmentation significative de la teneur en MMPI dans l'épiderme (P<0,01). Les microsphères selon l'invention font baisser la teneur en MMPI dans l'épiderme de 55% (P<0,01). Explants exposed to blue light showed a significant increase in MMPI content in the epidermis (P<0.01). The microspheres according to the invention lower the MMPI content in the epidermis by 55% (P<0.01).
Tableau 4
Figure imgf000054_0002
Table 4
Figure imgf000054_0002
Les expiants exposés à la lumière bleue ont montrés une augmentation significative de la teneur en MMPI dans le derme (P<0,01). Les microspheres selon l'invention font baisser la teneur en MMPI dans le derme de 23% (P<0,05). Explants exposed to blue light showed a significant increase in MMPI content in the dermis (P<0.01). THE microspheres according to the invention lower the MMPI content in the dermis by 23% (P<0.05).
Ces résultats ont été également comparés avec les résultats sur la teneur en MMPI dans le derme obtenus avec des expiants traités par une composition contenant le Tinosorb® M commercialisé par BASF et constitué par un filtre UV à large spectre basé sur la technologie des particules organique micro-fine (nom INCI :Methylene Bis-Benzotriazolyl Tetramethylbutylphenol (et) eau (et) Décyl Glucoside (et) Propylène Glycol (et) Gomme de Xanthane). Le Tinosorb® M montre une absorption sur toute la gamme des UV range et atteint même une protection dans la lumière bleue visible. Tinosorb® M à 4% en poids par rapport au poids total de la composition dans le gel en microémulsion Emulgade® CPE commercialisée par BASF fait baisser de 29% la teneur en MMPI dans le derme comparé au contrôle placebo irradié avec de la lumière bleue. Les microsphères selon l'invention en une teneur de 1,5% en poids par rapport au poids total de la composition montrent une gamme de protection similaire. These results were also compared with the results on the MMPI content in the dermis obtained with explants treated with a composition containing Tinosorb® M marketed by BASF and consisting of a broad-spectrum UV filter based on the technology of micro organic particles. -fine (INCI name: Methylene Bis-Benzotriazolyl Tetramethylbutylphenol (and) water (and) Decyl Glucoside (and) Propylene Glycol (and) Xanthan Gum). Tinosorb® M shows absorption over the entire UV range and even achieves protection in visible blue light. Tinosorb® M at 4% by weight relative to the total weight of the composition in the Emulgade® CPE microemulsion gel marketed by BASF lowers the MMPI content in the dermis by 29% compared to the placebo control irradiated with blue light. The microspheres according to the invention in a content of 1.5% by weight relative to the total weight of the composition show a similar range of protection.
Ainsi l'application par voie topique de la composition contenant les microsphères selon l'invention montre une bonne protection contre l'augmentation de teneur en MMPI et 8-OHdG provoqués par la lumière bleue (401-500nm avec un pic à 455nm) dans la peau humaine. Thus the topical application of the composition containing the microspheres according to the invention shows good protection against the increase in the content of MMPI and 8-OHdG caused by blue light (401-500 nm with a peak at 455 nm) in the human skin.
Exemple 3 : compositions cosmétiques selon l'invention Example 3: cosmetic compositions according to the invention
Les microsphères poreuses utilisées sont celles obtenues dans l'exemple 1 sous forme de poudre. The porous microspheres used are those obtained in Example 1 in powder form.
Exemple 3a) : Emulsion fluide pour le visage Example 3a): Fluid emulsion for the face
Tableau 5
Figure imgf000055_0001
Figure imgf000056_0001
connu de l'homme du métier, en introduisant la phase B dans la phase A et en agitant jusqu'à parfaite dispersion. Le mélange est chauffé à 75- 80°C de même que la phase C séparément. Puis la phase C est ajoutée au mélange sous agitation. Le mélange est laissé à refroidir sous agitation douce à température ambiante et les composés des phases E et F sont ajoutés, les uns après les autres. L'ensemble est homogénéisé pensant 2 min. Le pH est ajusté à 5,2. Table 5
Figure imgf000055_0001
Figure imgf000056_0001
known to those skilled in the art, by introducing phase B into phase A and stirring until completely dispersed. The mixture is heated to 75-80°C as is phase C separately. Then phase C is added to the mixture with stirring. The mixture is left to cool with gentle stirring to ambient temperature and the compounds of phases E and F are added, one after the other. The whole is homogenized for 2 min. The pH is adjusted to 5.2.
Exemple 3b) : Crème pour le visage Tableau 6
Figure imgf000056_0002
Figure imgf000057_0001
Example 3b): Face Cream Table 6
Figure imgf000056_0002
Figure imgf000057_0001
La crème est préparée par les méthodes usuelles dans le domaine bien connu de l'homme du métier, en mélangeant les phases A et B préalablement chauffées à 75°C, puis en ajoutant les phases C et D en mélangeant et en ajustant la composition avec la phase E à un pH de 6,2 et à la viscosité de 15 000 mPas (mesurée avec un appareil Brookfield (RVT ; 23°C, spindle TC ; 20tours par min). The cream is prepared by the usual methods in the field well known to those skilled in the art, by mixing phases A and B previously heated to 75° C., then by adding phases C and D by mixing and adjusting the composition with phase E at a pH of 6.2 and at a viscosity of 15,000 mPas (measured with a Brookfield apparatus (RVT; 23° C., spindle TC; 20 revolutions per min).
Exemple 3c) : shampoing Example 3c): shampoo
Tableau 7
Figure imgf000057_0002
Table 7
Figure imgf000057_0002
Le shampoing est préparé par les méthodes usuelles dans le domaine bien connu de l'homme du métier, en mélangeant les 4 phases et en ajustant la composition à un pH de 5,2 et à la viscosité de 2200 mPas (mesurée avec un appareil Brookfield (RVT ; 23°C, spindle 5 ; 50tours par min). The shampoo is prepared by the usual methods in the field well known to those skilled in the art, by mixing the 4 phases and adjusting the composition at a pH of 5.2 and at a viscosity of 2200 mPas (measured with a Brookfield apparatus (RVT; 23° C., spindle 5; 50 revolutions per min).

Claims

Revendications Claims
1. Utilisation cosmétique non thérapeutique de microsphères poreuses comprenant, avantageusement constituée par, un oxyde métallique pour protéger la peau, les annexes cutanées, notamment les cheveux, et/ou les muqueuses contre les effets inesthétiques et/ou désagréables et/ou inconfortables de la lumière bleue et/ou pour en diminuer et/ou ralentir lesdits effets sur la peau, les annexes cutanées notamment les cheveux, et/ou les muqueuses, lesdites microsphères ayant : 1. Non-therapeutic cosmetic use of porous microspheres comprising, advantageously consisting of, a metal oxide to protect the skin, the skin appendages, in particular the hair, and/or the mucous membranes against the unsightly and/or unpleasant and/or uncomfortable effects of blue light and/or to reduce and/or slow down the said effects on the skin, the skin appendages, in particular the hair, and/or the mucous membranes, the said microspheres having:
- un diamètre moyen D50 mesuré par microscopie électronique à balayage (SEM) allant de 1 pm à 30 pm, - an average diameter D 50 measured by scanning electron microscopy (SEM) ranging from 1 μm to 30 μm,
- des pores dont le diamètre moyen D50 mesuré par microscopie électronique à balayage (SEM) va de 50nm à 250nm et - pores whose average diameter D 50 measured by scanning electron microscopy (SEM) ranges from 50 nm to 250 nm and
- une porosité moyenne mesurée par porosimétrie au mercure allant de 0,40 à 0,65. - an average porosity measured by mercury porosimetry ranging from 0.40 to 0.65.
2. Utilisation selon la revendication 1, caractérisée en ce que les effets inesthétiques et/ou désagréables et/ou inconfortables sont choisis parmi le vieillissement de la peau et/ou des muqueuses et/ou des annexes cutanées et/ou l'altération de la barrière cutanée et/ou mucosale et/ou la déshydratation de la peau et/ou des muqueuses et/ou des annexes cutanées et/ou l'altération des propriétés biomécaniques de la peau et/ou des muqueuses et/ou des annexes cutanées. 2. Use according to claim 1, characterized in that the unsightly and / or unpleasant and / or uncomfortable effects are chosen from aging of the skin and / or mucous membranes and / or skin appendages and / or alteration of the skin and/or mucosal barrier and/or dehydration of the skin and/or mucous membranes and/or skin appendages and/or alteration of the biomechanical properties of the skin and/or mucosa and/or skin appendages.
3. Utilisation selon la revendication 1 ou 2, pour prévenir et/ou ralentir3. Use according to claim 1 or 2, to prevent and/or slow down
- l'apparition de rides et/ou ridules et/ou de tâches pigmentaires sur la peau et/ou les muqueuses, et/ou - the appearance of wrinkles and/or fine lines and/or pigment spots on the skin and/or mucous membranes, and/or
- la perte d'éclat du teint de la peau et/ou des muqueuses et/ou le manque d'homogénéité du teint de la peau et/ou des muqueuses et/ou- loss of radiance in the complexion of the skin and/or mucous membranes and/or lack of uniformity in the complexion of the skin and/or mucous membranes and/or
- le relâchement cutanée et/ou -la perte de tonicité et/ou d'elasticite et/ou de fermete et/ou de densite de la peau et/ou des muqueuses et/ou - sagging skin and/or -loss of tone and/or elasticity and/or firmness and/or density of the skin and/or mucous membranes and/or
- le blanchiment et/ou grisonnement des annexes cutanées et/ou - whitening and/or graying of the skin appendages and/or
- la déshydratation et/ou les pertes insensibles en eau de la peau et/ou des muqueuses et/ou - dehydration and/or transepidermal water loss from the skin and/or mucous membranes and/or
- l'altération du microrelief de la peau et/ou des muqueuses et/ou - alteration of the microrelief of the skin and/or mucous membranes and/or
- l'altération des propriétés de surface et/ou de texture et/ou visuelle et/ou des qualités sensorielles de la peau et/ou des muqueuses et/ou des annexes cutanées en particulier des cheveux. - the alteration of the surface properties and/or of texture and/or visual and/or of the sensory qualities of the skin and/or of the mucous membranes and/or of the cutaneous appendages in particular of the hair.
4. Utilisation selon l'une quelconque des revendications 1 à 3, caractérisée en ce que l'oxyde métallique est choisi dans le groupe constitué par SiO2, TiO2, ZnO et leurs mélanges, avantageusement SiO2. 4. Use according to any one of claims 1 to 3, characterized in that the metal oxide is chosen from the group consisting of SiO 2 , TiO 2 , ZnO and their mixtures, advantageously SiO 2 .
5. Utilisation selon l'une quelconque des revendications 1 à 4, caractérisée en ce que les microsphères ont un diamètre moyen D50 mesuré par microscopie électronique à balayage (SEM) allant de 1,3 à 10 pm, en particulier de 1,5 à 4,5 pm. 5. Use according to any one of claims 1 to 4, characterized in that the microspheres have an average diameter D50 measured by scanning electron microscopy (SEM) ranging from 1.3 to 10 μm, in particular from 1.5 to 4.5 pm.
6. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que le diamètre moyen D50 de pores des microsphères mesuré par microscopie électronique à balayage (SEM) va de 100 à 245 nm, en particulier de 180 à 225 nm. 6. Use according to any one of the preceding claims, characterized in that the mean pore diameter D50 of the microspheres measured by scanning electron microscopy (SEM) ranges from 100 to 245 nm, in particular from 180 to 225 nm.
7. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que les microsphères ne contiennent pas et/ou ne sont pas utilisées en combinaison avec un autre filtre anti-lumière bleue et/ou un filtre anti-UV et/ou un filtre solaire et/ou dans une composition cosmétique qui en contient. 7. Use according to any one of the preceding claims, characterized in that the microspheres do not contain and/or are not used in combination with another anti-blue light filter and/or an anti-UV filter and/or a sunscreen and/or in a cosmetic composition which contains it.
8. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que la lumière bleue a une longueur d'onde allant de 401 à 500nm, avantageusement de 415 à 490nm, plus avantageusement de 420 à 480nm, et en particulier de 430 à 460 nm. 8. Use according to any one of the preceding claims, characterized in that the blue light has a wavelength ranging from 401 to 500 nm, advantageously from 415 to 490 nm, more advantageously from 420 to 480 nm, and in particular from 430 to 460nm.
9. Utilisation selon l'une quelconque des revendications precedentes, caractérisée en ce que les microsphères poreuses sont comprises dans une composition cosmétique, à une teneur allant de 0,01% à 20% en poids, avantageusement de 0,1% à 5% en poids, encore avantageusement de 0,5% à 3% en poids, en particulier de 1% à 2 % en poids, par rapport au poids total de la composition. 9. Use according to any one of the preceding claims, characterized in that the porous microspheres are included in a cosmetic composition, at a content ranging from 0.01% to 20% by weight, advantageously from 0.1% to 5% by weight, again advantageously from 0.5% to 3% by weight, in particular from 1% to 2% by weight, relative to the total weight of the composition.
10. Utilisation selon la revendication 9, caractérisée en ce que la composition cosmétique comprend au moins un excipient cosmétiquement acceptable et que cette composition est choisie parmi un sérum, une lotion, une crème, un shampoing, un après-shampoing, une huile, un lait, une pommade, une pâte, une mousse, une émulsion, un hydrogel, un gel douche, un masque, une laque, un spray, une cire, un mascara, un crayon de maquillage, un vernis, d'une poudre, notamment de maquillage, d'un stick. 10. Use according to claim 9, characterized in that the cosmetic composition comprises at least one cosmetically acceptable excipient and that this composition is chosen from a serum, a lotion, a cream, a shampoo, a conditioner, an oil, a milk, ointment, paste, mousse, emulsion, hydrogel, shower gel, mask, lacquer, spray, wax, mascara, make-up pencil, varnish, powder, in particular make-up, a stick.
11. Procédé de soin cosmétique non thérapeutique comprenant l'application sur au moins une zone de peau et/ou de muqueuse et/ou d'annexes cutanées de microsphères poreuses comprenant, avantageusement constituée par, un oxyde métallique ou d'une composition cosmétique les comprenant pour protéger la zone de peau, d'annexes cutanées, notamment de cheveux, et/ou de muqueuse contre les effets inesthétiques et/ou désagréables et/ou inconfortables de la lumière bleue et/ou pour en diminuer et/ou ralentir lesdits effets sur cette zone de peau, d'annexes cutanées notamment de cheveux, et/ou de muqueuses, les effets inesthétiques et/ou désagréables et/ou inconfortables étant avantageusement choisis parmi le vieillissement de la peau et/ou des muqueuses et/ou des annexes cutanées et/ou l'altération de la barrière cutanée et/ou mucosale et/ou la déshydratation de la peau et/ou des muqueuses et/ou des annexes cutanées et/ou l'altération des propriétés biomecaniques de la peau et/ou des muqueuses et/ou des annexes cutanées, lesdites microsphères ayant : 11. Non-therapeutic cosmetic care process comprising the application to at least one area of skin and/or mucosa and/or skin appendages of porous microspheres comprising, advantageously consisting of, a metal oxide or a cosmetic composition comprising to protect the area of skin, skin appendages, in particular hair, and/or mucous membrane against the unsightly and/or unpleasant and/or uncomfortable effects of blue light and/or to reduce and/or slow said effects on this area of skin, skin appendages, in particular hair, and/or mucous membranes, the unsightly and/or unpleasant and/or uncomfortable effects being advantageously chosen from aging of the skin and/or of the mucous membranes and/or of the appendages and/or alteration of the cutaneous and/or mucosal barrier and/or dehydration of the skin and/or mucous membranes and/or cutaneous appendages and/or alteration of biomechanical properties of the skin and/or mucous membranes and/or skin appendages, said microspheres having:
- un diamètre moyen D50 mesuré par microscopie électronique à balayage (SEM) allant de 1 pm à 30 pm, - an average diameter D50 measured by scanning electron microscopy (SEM) ranging from 1 μm to 30 μm,
- des pores dont le diamètre moyen D50 mesuré par microscopie électronique à balayage (SEM) va de 50nm à 250nm et - pores whose average diameter D50 measured by scanning electron microscopy (SEM) ranges from 50 nm to 250 nm and
- une porosité moyenne mesurée par porosimétrie au mercure allant de 0,40 à 0,65. - an average porosity measured by mercury porosimetry ranging from 0.40 to 0.65.
12. Procédé de soin cosmétique selon la revendication 11, caractérisé en ce que les microsphères poreuses et/ou la composition cosmétique les comprenant sont appliqués par voie topique sur tout ou partie de la peau et/ou des muqueuses du corps et/ou du visage choisie parmi le cuir chevelu, les jambes, les cuisses, les bras, le ventre, le décolleté, le cou, tout ou partie du visage, le front, le menton, les lèvres, le contour des lèvres, le contour des yeux, la zone dite « en T » du visage, et/ou sur tout ou partie des annexes cutanées, plus préférentiellement les cheveux. 12. Cosmetic care process according to claim 11, characterized in that the porous microspheres and/or the cosmetic composition comprising them are applied topically to all or part of the skin and/or mucous membranes of the body and/or of the face. chosen from the scalp, legs, thighs, arms, stomach, décolleté, neck, all or part of the face, forehead, chin, lips, lip contour, eye contour, so-called “T” zone of the face, and/or on all or part of the skin appendages, more preferably the hair.
13. Procédé de soin cosmétique selon l'une quelconque des revendications 11 ou 12, caractérisé en ce que les microsphères poreuses et/ou la composition cosmétique les comprenant sont tels que définis dans l'une quelconque des revendications 4 à 7 et 9 à 10. 13. Cosmetic care process according to any one of claims 11 or 12, characterized in that the porous microspheres and/or the cosmetic composition comprising them are as defined in any one of claims 4 to 7 and 9 to 10 .
14. Procédé de soin cosmétique selon l'une quelconque des revendications 11 à 13, pour prévenir et/ou ralentir 14. Cosmetic care process according to any one of claims 11 to 13, for preventing and/or slowing down
- l'apparition de rides et/ou ridules et/ou de tâches pigmentaires sur la peau et/ou les muqueuses, et/ou - the appearance of wrinkles and/or fine lines and/or pigment spots on the skin and/or mucous membranes, and/or
- la perte d'éclat du teint de la peau et/ou des muqueuses et/ou le manque d'homogénéité du teint de la peau et/ou des muqueuses et/ou- loss of radiance in the complexion of the skin and/or mucous membranes and/or lack of uniformity in the complexion of the skin and/or mucous membranes and/or
- le relâchement cutanée et/ou - sagging skin and/or
-la perte de tonicité et/ou d'élasticité et/ ou de fermeté et/ou de densité de la peau et/ou des muqueuses et/ou - le blanchiment et/ou grisonnement des annexes cutanées et/ou -loss of tone and/or elasticity and/or firmness and/or density of the skin and/or mucous membranes and/or - whitening and/or graying of the skin appendages and/or
- la déshydratation et/ou les pertes insensibles en eau de la peau et/ou des muqueuses et/ou - dehydration and/or transepidermal water loss from the skin and/or mucous membranes and/or
- l'altération du microrelief de la peau et/ou des muqueuses et/ou - l'altération des propriétés de surface et/ou de texture et/ou visuelle et/ou des qualités sensorielles de la peau et/ou des muqueuses et/ou des annexes cutanées en particulier des cheveux. - alteration of the microrelief of the skin and/or mucous membranes and/or - alteration of the surface properties and/or texture and/or visual and/or sensory qualities of the skin and/or mucous membranes and/ or skin appendages, in particular hair.
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