WO2020017441A1 - Microneedle sheet - Google Patents

Microneedle sheet Download PDF

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Publication number
WO2020017441A1
WO2020017441A1 PCT/JP2019/027620 JP2019027620W WO2020017441A1 WO 2020017441 A1 WO2020017441 A1 WO 2020017441A1 JP 2019027620 W JP2019027620 W JP 2019027620W WO 2020017441 A1 WO2020017441 A1 WO 2020017441A1
Authority
WO
WIPO (PCT)
Prior art keywords
microneedle
skin
water
sheet according
lips
Prior art date
Application number
PCT/JP2019/027620
Other languages
French (fr)
Inventor
Gaurav Agarwal
Philippe Barbarat
Dominique Bordeaux
Yuanyuan Sun
Jean-Pascal Hirt
Original Assignee
L'oreal
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by L'oreal filed Critical L'oreal
Publication of WO2020017441A1 publication Critical patent/WO2020017441A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M37/00—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin
    • A61M37/0015—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin by using microneedles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M37/00—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin
    • A61M37/0015—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin by using microneedles
    • A61M2037/0023—Drug applicators using microneedles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M37/00—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin
    • A61M37/0015—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin by using microneedles
    • A61M2037/0046—Solid microneedles

Definitions

  • the present invention relates to a microneedle sheet comprising a plurality of microneedles which can be used for cosmetic treatments of skin.
  • the stratum comeum constitutes the main barrier to exogenous substances including small molecular weight materials.
  • exogenous substances permeating the skin must diffuse through the highly organized intercellular lipid bilayers of the stratum comeum.
  • This intercellular microroute which is lipophilic, is the primary pathway for exogenous substances to pass through the SC barrier by passive diffusion along a concentration gradient between a delivery vehicle and the SC. It is difficult for some exogenous substances to penetrate into the skin.
  • injections using a conventional needle In order to provide exogenous substances deeper into the skin, it is possible to perform injections using a conventional needle. However, such injections cause pain, and need to be performed by a professional such as a doctor. Thus, injections using a conventional needle are not common for cosmetic purposes.
  • microneedles have an advantage of potentially penetrating the SC without pain caused by the use of conventional needles for injections, and can be self-administered.
  • the surface of the skin or the lips is often colored or dyed.
  • makeup cosmetic products such as a foundation and a lip stick are widely used to color or dye the skin, in particular the skin of the face and the lips.
  • the coloring or dyeing by makeup cosmetic products is temporary and can be easily removed from the skin and the like with, for example, cleansing products.
  • the users of the makeup cosmetic products need to color the skin and/or the lips on a daily basis.
  • microneedles for coloring or dyeing the skin or the lips.
  • An objective of the present invention is to provide the surface of the skin or the lips with durable or long-lasting coloring effects without pain.
  • microneedle sheet comprising a substrate sheet and a plurality of microneedles on the substrate sheet, wherein the microneedles comprise (a) at least one water-soluble or water-dispersible polymer, and (b) at least one coloring agent. It is preferable that the microneedle be capable of providing the (b) coloring agent into the surface layer of the skin or the lips.
  • the microneedle be capable of penetrating into the skin or the lips to a depth of 200 microns or less, preferably 180 microns or less, and more preferably 160 microns or less.
  • the microneedle be in the shape of a cone.
  • the base of the cone of the microneedle may have a diameter of from 80 to 300 microns, preferably from 100 to 250 microns, and more preferably from 120 to 200 microns.
  • the microneedle may have a height of from 50 to 1000 microns, preferably from 100 to 750 microns, and more preferably from 150 to 500 microns.
  • the ratio of (the height of the cone)/(the diameter of the base of the cone) of the microneedle may be 1 or more, preferably 1.5 or more, and more preferably 2.0 or more.
  • the (a) water-soluble or water-dispersible polymer be dissolvable in the surface layer of the skin or the lips.
  • the (a) water-soluble or water-dispersible polymer may be selected from hyaluronic acids, monosaccharides, disaccharides, oligosaccharides, polysaccharides, dextrins, dextrans, polyethylene glycols, polyvinyl alcohols, poly(methylvinylether/maleic anhydride), polyvinylpyrrolidone, poly(methyl/vinyl ether/maleic acid) (PMVE/MA) and esters thereof, poly(methyl/vinyl ether/maleic anhydride) (PMVE/MAH), and mixtures thereof.
  • the (a) water-soluble or water-dispersible polymer may have a molecular weight of from 6,000 to 200,000 Dalton, preferably from 8,000 to 100,000 Dalton, and more preferably from 10,000 to 50,000 Dalton.
  • the (b) coloring agent may be selected from dyes, preferably natural dyes, and more preferably coloring plant extracts.
  • the amount of the (b) coloring agent may range from 0.01% to 30% by weight, preferably from 0.1% to 20% by weight, and more preferably from 1% to 10% by weight relative to the total weight of the microneedle.
  • the present invention also relates to a cosmetic process for skin or the lips comprising the steps of:
  • the cosmetic process according to the present invention is preferably for long-lasting coloring the surface of the skin or the lips.
  • the present invention also relates to a cosmetic use of the microneedle sheet according to the present invention for providing the skin or the lips with durable or long-lasting coloring effects.
  • one aspect of the present invention is a microneedle sheet comprising a substrate sheet and a plurality of microneedles on the substrate sheet, wherein the microneedles comprise (a) at least one water-soluble or water-dispersible polymer, and (b) at least one coloring agent.
  • microneedles do not cause any pain
  • the microneedle sheet according to the present invention can provide coloring effects without pain.
  • the (b) coloring agent in the microneedle sheet according to the present invention is provided into the skin or the lips, not on the skin or the lips, the (b) coloring agent cannot be removed by wiping the surface of the skin or the lips, and can remain in the surface layer of the skin or the lips. Therefore, the (b) coloring agent can provide the skin or the lips with durable or long-lasting coloring effects.
  • the coloring of the skin or the lips provided by the present invention can be performed for cosmetic purposes, such as modifications of optical appearance, for the skin or the lips.
  • the cosmetic purposes include, for example, makeup for the skin, but also encompass any other corrections or modifications of skin color disorders.
  • the skin color corrections may include to correct or erase skin color disorders, such as achromia, alopecia, vitiligo, scars, for example from acne, depigmented spot-areas, over-pigmented areas and spots, or also to attenuate dark circles under the eyes; or to modify the skin or lip tone.
  • the (b) coloring agent can be delivered to a deeper surface layer of the skin or the lips, by-passing the SC, which is not possible with topical applications of the coloring agent.
  • microneedle sheet according to the present invention can provide the surface of the skin or the lips with durable or long-lasting coloring effects without pain.
  • the present invention is convenient for cosmetic or non-therapeutic treatments.
  • microneedle sheet according to the present invention will be described in a detailed manner.
  • the microneedle sheet according to the present invention comprises a substrate sheet and a plurality of microneedles on the substrate sheet, wherein the microneedles comprise (a) at least one water-soluble or water-dispersible polymer, and (b) at least one coloring agent.
  • the microneedle sheet according to the present invention may be a cosmetic device, preferably a cosmetic device for a keratin substance, and more preferably a cosmetic device for the skin, in particular the skin of the face, as well as the lips. (Microneedles)
  • the microneedle sheet according to the present invention comprises a plurality of microneedles.
  • the microneedles are present on the surface of the substrate sheet.
  • the microneedles may be present on 50% or more, preferably 70% or more, and more preferably 90% or more of the surface of the substrate sheet.
  • microneedles be present on one of the surfaces of the substrate sheet.
  • microneedles of the microneedle sheet according to the present invention be designed to penetrate or enter into the stratum comeum of the skin, in particular the skin of the face, as well as the lips.
  • microneedles are solid, not hollow.
  • a microneedle can be any suitable size and shape to puncture the stratum comeum. It may be preferable that the microneedles be designed to pierce and cross the stratum comeum. The microneedles may be capable of creating openings in the stratum comeum.
  • the height of the microneedles may be altered so as to allow penetration into the epidermis and/or dermis of the skin, preferably into the upper dermis, and more preferably into the lower dermis.
  • microneedles are not limited as long as the shape is a“needle”. It will be apparent to those skilled in the art that the microneedles of the present invention can take any reasonable shape, including, but not limited to, cones, rods and/or pillars. As such, the microneedles may have the same diameter at the tip as at the base or may taper in diameter in the direction from the base to the tip.
  • the shape of the microneedle may be in the form of a triangular pyramid, a square pyramid or a pentagonal pyramid.
  • the microneedle may be in the form of a cylinder preferably with a tip which may be formed by diagonally cutting the cylinder.
  • microprotrusions as a type of microprotrusion or microprojection which is being employed. It will be understood by persons skilled in the art that in many cases the same inventive principles apply to the use of other microprotrusions or
  • microprojections to penetrate the skin may include, for example, microblades as described in U.S. Patent No. 6,219,574 and Canadian Patent Application No. 2,226,718, and edged microneedles as described in U.S. Patent No. 6,652,478.
  • the height or length of the microneedle of the microneedle sheet according to the present invention may be from 50 to 1000 microns, preferably from 100 to 750 microns, and more preferably from 150 to 500 microns.
  • the microneedle is in the form of a cone. It is preferable that the entire shape of each microneedle is in the form of a cone.
  • the cone may comprise a distal end such as a tip and a base.
  • the shape of the base may be a circle or oval.
  • the height or length of the cone of the microneedle of the microneedle sheet according to the present invention may be from 50 to 1000 microns, preferably from 100 to 750 microns, and more preferably from 150 to 500 microns.
  • the base of the cone of the microneedle of the microneedle sheet according to the present invention may have a diameter or width of from 80 to 300 microns, preferably from 100 to 250 microns, and more preferably from 120 to 200 microns. If the base of the cone of the microneedle of the microneedle sheet according to the present invention is in the shape of an oval or ellipse, the length of the major axis or width of the oval may be from 80 to 300 microns, preferably from 100 to 250 microns, and more preferably from 150 to 200 microns.
  • the microneedle may have an aspect ratio (length/width at base) of at least about 3 : 1 , at least about 2: 1 , or at least about 1 : 1.
  • the ratio of (the height of the cone)/(the diameter of the base of the cone) of the microneedle may be 1 or more, preferably 1.5 or more, and more preferably 2.0 or more.
  • the microneedles do not fracture by force when a pressure of insertion of less than 50.0 N/cm 2 , for example less than 20.0 N/em 2 , such as less than 10 N/cm 2 is exerted on the microneedles along their length.
  • the microneedle sheet according to the present invention in particular the microneedles of the microneedle sheet, have a Young modulus of 50 N/mm or more, preferably 55 N/mm or more, and more preferably 60 N/mm or more.
  • the microneedle is capable of penetrating into the skin or the lips to a depth of 200 microns or less, preferably 180 microns or less, and more preferably 160 microns or less.
  • the microneedle can be dissolvable or non-dissolvable. It is preferable that the microneedle be dissolvable, and more preferable dissolvable in water or an aqueous vehicle or medium.
  • The“dissolvable microneedle” is meant that the microneedle can be broken down or disintegrated inside the skin or lip by, for example, a natural moisturizing factor or external moisture.
  • the microneedle of the microneedle sheet according to the present invention comprises (a) at least one water-soluble or water-dispersible polymer.
  • water-soluble and water-dispersible mean soluble and dispersible, respectively, when being in contact with water.
  • a single water-soluble or water-dispersible polymer may be used.
  • Two or more water-soluble or water-dispersible polymers may be used in combination.
  • the (a) water-soluble or water-dispersible polymer be soluble or dispersible in the skin or the lips.
  • the (a) water-soluble or water-dispersible polymer is capable of being dissolved or dispersed after insertion into the skin or the lips. Due to the solubility and dispersibility of the polymer, the microneedle of the microneedle sheet according to the present invention can effectively release the coloring agent in the microneedle.
  • Optional external water combined with the application of the microneedle sheet according to the present invention can be used to accelerate the dissolution or dispersion of the microneedle.
  • the (a) water-soluble or water-dispersible polymer be dissolvable in the surface layer of the skin or the lips.
  • the (a) water-soluble or water-dispersible polymer may be selected from hyaluronic acids (in particular lower molecular weight hyaluronic acid), monosaccharides, disaccharides, oligosaccharides, polysaccharides (including derivatives thereof such as cellulose and derivatives thereof, in particular hydroxymethylcellulose), dextrins, dextrans, polyethylene glycols, polyvinyl alcohols, poly(methylvinylether/maleic anhydride), polyvinylpyrrolidone, poly(methyl/vinyl ether/maleic acid) (PMVE/MA) and esters thereof, poly(methyl/vinyl ether/maleic anhydride) (PMVE/MAH), and mixtures thereof.
  • hyaluronic acids in particular lower molecular weight hyaluronic acid
  • monosaccharides include disaccharides, oligosaccharides, polysaccharides (including derivatives thereof such as cellulose and derivatives thereof, in particular hydroxy
  • the (a) water-soluble or water-dispersible polymer may have a molecular weight of from 6,000 to 200,000 Dalton, preferably from 8,000 to 100,000 Dalton, and more preferably from 10,000 to 50,000 Dalton.
  • the low molecular weight hyaluronic acid may have a molecular weight of 100 kDa or less, preferably 70 kDa or less, and more preferably 50 kDa or less.
  • the polyvinylpyrrolidone may have a molecular weight between 1 kDa and 300 kDa, preferably between 5 kDa and 200 kDa, and more preferably between 7 kDa and 100 kDa.
  • PMVE/MAH poly(methyl/vinyl ether/maleic anhydride)
  • the amount (solid basis) of the (a) water-soluble or water-dispersible polymer(s) in the microneedle of the microneedle sheet according to the present invention may be 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more, relative to the total weight of the microneedle.
  • the amount (solid basis) of the (a) water-soluble or water-dispersible polymer(s) in the microneedle of the microneedle sheet according to the present invention may be 100% by weight or less, preferably 90% by weight or less, and more preferably 80% by weight or less, relative to the total weight of the microneedle.
  • the amount (solid basis) of the (a) water-soluble or water-dispersible polymer(s) in the microneedle of the microneedle sheet according to the present invention may be from 50% to 100% by weight, preferably from 60% to 90% by weight, and more preferably from 70% to 80% by weight, relative to the total weight of the microneedle.
  • the microneedle of the microneedle sheet according to the present invention comprise at least one material which is swellable, more preferably water-swellable, and even more preferably swellable in the skin.
  • the above material may be a polymer which is swellable, more preferably water-swellable, and even more preferably swellable in the skin.
  • water-swellable means swellable when being in contact with water.
  • the above swellable material or polymer may have a high swellability such that it can swell to at least over 10 times in a l-hour in vitro incubation in a physiological saline solution or phosphate buffered saline, preferably at least 20 times in l-hour incubation, more preferably at least 30 times in l-hour incubation, even more preferably at least 40 times in l-hour incubation, and most preferably about 45-55 times in l-hour incubation. It may be preferable that at least the distal end portion of the microneedle swell upon insertion into the skin, more preferably within less than 1 hour, and even more preferably to at least 2 times within 24 hours after insertion into the skin.
  • the above swellable material preferably the above swellable polymer, may have a high viscoelasticity such that it can form a gel after the in vitro incubation in a physiological saline solution or phosphate buffered saline.
  • the above swellable material preferably the swellable polymer, is not water-soluble or not water-dispersible.
  • the above swellable material preferably the swellable polymer, may be a hydrogel-forming polymer.
  • the above swellable polymer may be selected from high molecular weight hyaluronic acids, cross-linked hyaluronic acids, cross-linked polyethylene glycol, polyethylene glycol cross- linked poly-lactic acid or poly-glycolic acid or poly-lactic-co-glycolic acid or poly dioxanone, poly(styrene)-block-poly(acrylic acid), polyethylene glycol cross-linked PMVE/MA, cross- linked polyvinylpyrrolidone, sodium starch glycolate; cellulose; natural and synthetic gums; alginates; sodium polyacrylate PEG-crosslinked poly(methyl/vinyl ether/maleic acid)
  • the high molecular weight hyaluronic acid may have a molecular weight of more than 500 kDa, preferably more than 1000 kDa, and more preferably more than 2100 kDa, and preferably less than 10000 kDa.
  • the molecular weight here means a number average molecular weight.
  • PMVE/MAH poly(methyl/vinyl ether/maleic anhydride)
  • the amount (solid basis) of the swellable material(s) in the microneedle of the microneedle sheet according to the present invention may be 1% by weight or more, preferably 5% by weight or more, and more preferably 10% by weight or more, relative to the total weight of the microneedle.
  • the amount (solid basis) of the swellable material(s) in the microneedle of the microneedle sheet according to the present invention may be 30% by weight or less, preferably 25% by weight or less, and more preferably 20% by weight or less, relative to the total weight of the microneedle.
  • the amount (solid basis) of the swellable material(s) in the microneedle of the microneedle sheet according to the present invention may be from 1% to 30% by weight, preferably from 5% to 25% by weight, and more preferably from 10% to 20% by weight, relative to the total weight of the microneedle.
  • a reduction in the amount of matrix, such as epidermis, in the skin tends to lead to a decrease in skin thickness and deterioration of skin elasticity, causing the formation of wrinkles.
  • the microneedle of the microneedle sheet according to the present invention comprises at least one swellable material, preferably at least one swellable polymer
  • the microneedle may be swellable such that it can improve the aesthetic appearance of the skin, in particular the face, by reducing the appearance of wrinkles.
  • the microneedle if it is swellable, it can swell in the skin to further increase the volume of the microneedle along with its absorption of, for example, water in the skin.
  • Such volume expansion beneath the skin surface of a wrinkle site can effectively push the wrinkles from inside the skin and makes the wrinkles become shallower and wider.
  • the wrinkles can be reduced or less noticeable.
  • the swellable microneedles may increase the amount of matrix in the skin to cause an increase of skin elasticity which results in the reduction of wrinkles on the skin.
  • the apical separation distance between each of the individual microneedles on a substrate sheet can be modified to ensure the penetration of the skin or the lips by the microneedles while having a sufficiently small separation distance to provide high transdermal transport rates.
  • the range of apical separation distances between microneedles can be in the range of 50-1000 pm, such as 100-800 pm or 200-600 pm. This may allow a compromise to be achieved between efficient penetration of the stratum comeum by as many microneedles as possible and the necessary margin for possible swelling of the microneedles if they are swellable.
  • the density of microneedles may be from 100 to 2000 microneedles/cm 2 , preferably 500 to 1500 microneedles/cm 2 , and even more preferably 800 to 1200
  • microneedles/ cm 2 microneedles/ cm 2 .
  • the microneedle of the microneedle sheet according to the present invention comprises (b) at least one coloring agent.
  • a single type of coloring agent may be used. Alternatively, two or more coloring agents may be used in combination.
  • microneedle sheet according to the present invention is capable of providing the (b) coloring agent into the surface layer of the skin or the lips.
  • coloring agent includes any synthetic or natural, or organic or inorganic, pigments, dyes or lakes, and any other colorants approved by CTFA and the FDA.
  • the (b) coloring agent may be water-soluble or water-dispersible, or oil-soluble or oil-dispersible or with limited solubility in water.
  • the (b) coloring agent may be selected from coloring pigments.
  • coloring pigments should be understood as meaning white or colored, inorganic or organic particles of any shape which are insoluble and are intended to color or dye the skin or the lips.
  • the pigments can be white or colored, inorganic and/or organic.
  • inorganic pigments that may be used, non-limiting mention may be made of titanium dioxide, optionally surface treated, zirconium or cerium oxide, as well as zinc, (black, yellow or red) iron or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, or metal powders, such as aluminum powder or copper powder.
  • the pigments can also be chosen from nanopigments formed of metal oxides, such as titanium dioxide, zinc oxide, iron oxide, zirconium oxide, and cerium oxide, and mixtures thereof.
  • nanopigments is understood to mean pigments having a mean particle size ranging from 1 n to 500 nm, such as particle sizes ranging from 10 nm to 100 nm.
  • Red 202 Calcium bis[2-(3-carboxy- 2-hydroxynephthylazo)-5-methylbenzenesulfonate
  • D&C type a pigment that may be used
  • Red 202 Calcium bis[2-(3-carboxy- 2-hydroxynephthylazo)-5-methylbenzenesulfonate
  • the organic pigment may also be a diketopyrrolopyrroles (DPP) such as the ones described in EP-A-542669, EP-A-787730, EP-A-787731 and WO-A- 96/08537.
  • DPP diketopyrrolopyrroles
  • the organic pigment may be selected from bio-pigments such as BioChromaDerm® or BioChromaEyes® provided from Biotic Phocea in France.
  • the coloring pigment may be chosen from metal oxides such as titanium dioxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, and chromium oxide; manganese violet; Prussian blue; ultramarine blue; chromium hydrate; ferric blue; aluminum powder; copper powder; carbon black; pigments of D&C type; lakes; pearlescent pigments; and mixtures thereof.
  • metal oxides such as titanium dioxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, and chromium oxide
  • manganese violet such as titanium dioxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, and chromium oxide
  • manganese violet such as titanium dioxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, and chromium oxide
  • manganese violet such as titanium dioxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, and chromium oxide
  • manganese violet such as titanium dioxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, and chro
  • pearlescent pigments should be understood as meaning iridescent particles of any shape, such as particles produced by certain shellfish in their shells or else synthesized.
  • the pearlescent agents can be chosen from white pearlescent agents, such as mica covered with titanium dioxide or with bismuth oxychloride; colored pearlescent agents, such as titanium oxide-coated mica covered with iron oxide, titanium oxide-coated mica covered with ferric blue or chromium oxide, or titanium oxide-coated mica covered with an organic pigment of the above-mentioned type; and pearlescent agents based on bismuth oxychloride.
  • the microneedle may include high refraction index particles, interference particles, reflection particles, and light absorbent particles, in particular non-transparent particles or particles modifying the path of light, as the coloring pigment, in order to prevent reflection.
  • Such particles can allow coloring or dermal-pigmenting of the skin or the lips thanks to the optical properties of the particles.
  • the (b) coloring agent may be selected from dyes.
  • the dyes may be selected from natural direct dyes and synthetic direct dyes.
  • a direct dye means a colored substance which does not require the use of an oxidizing agent in order to develop its color.
  • the (b) coloring agent may be selected from natural direct dyes.
  • natural direct dye is understood to mean any dye or dye precursor that is naturally occurring and is produced by extraction (and optionally purification) from a plant matrix or an animal such as an insect, optionally in the presence of natural compounds such as ash or ammonia.
  • quinone dyes such as lawsone and juglone
  • alizarin a dye that is added to the aqueous solution
  • purpurin a dye that is added to the aqueous solution
  • laccaic acid a dye that is added to the aqueous solution
  • carminic acid a dye that is added to the aqueous solution
  • kermesic acid a dye that is added to the aqueous solution
  • purpurogallin such as sodium sulfate
  • indigoids such as indigo, sorghum, isatin, betanin, curcuminoids (such as curcumin), spinulosin, various types of chlorophyll and chlorophyllin, hematoxylin, hematein, brazilein, brazilin, safflower dyes (such as carthamin), flavonoids (such as rutin, quercetin, catechin, epicatechin, morin, apigenidin, and sandalwood), anthocyans (such as apigeninidin and apigenin), carotenoids, tannins, orceins, santalins and cochineal carmine.
  • indigoids such as indigo, sorghum, isatin, betanin, curcuminoids (such as curcumin), spinulosin, various types of chlorophyll and chlorophyllin, hematoxylin, hematein, brazilein, brazilin, safflower dye
  • extracts or decoctions containing natural direct dye(s) in particular henna-based extracts, curcuma longa extract, sorghum leaf-sheath extract, haematoxylon campechianum extract, green tea extract, pine bark extract, cocoa extract, and logwood extract.
  • the natural direct dye be chosen from the group consisting of
  • curcuminoids santalins, chlorophyllin, haematoxylin, haematein, brazilein, brazilin, sorghum, laccaic acid, lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigoids, isatin, spinulosin, apigenin, orcein, betanin, flavonoids, anthocyans, and extracts or decoctions containing these compounds.
  • the natural direct dyes may be preferably chosen, for example, from
  • hydroxylated quinones indigoids, hydroxyflavones, santalins A and B, isatin and its derivatives, and brasilin and its hydroxylated derivative.
  • the hydroxylated quinones are preferably benzoquinones, naphthoquinones, and mono- or polyhydroxylated anthraquinones which are optionally substituted with groups such as alkyl, alkoxy, alkenyl, chloro, phenyl, hydroxyalkyl and carboxyl.
  • the naphthoquinones are preferably lawsone, juglone, flaviolin, naphthazarin,
  • naphthopurpurin lapachol, plumbagin, chloroplumbagin, droserone, shikonin, 2-hydroxy-3- methyl- 1, 4-naphthoquinone, 3, 5-dihydroxy-l, 4-naphthoquinone, 2, 5-dihydroxy- 1,4- naphthoquinone, 2-methoxy-5-hydroxy-l, 4-naphthoquinone and 3-methoxy-5-hydroxy-l,4- naphthoquinone.
  • the benzoquinones are preferably spinulosin, atromentin, aurentioglyocladin, 2, 5 -dihydroxy- 6-methylbenzoquinone, 2-hydroxy-3-methyl-6-methoxybenzoquinone, 2, 5-dihydroxy-3,6- diphenylbenzoquinone, 2,3-dimethyl-5-hydroxy-6-methoxybenzoquinone and 2,5-dihydroxy- 6-isopropylbenzoquinone.
  • the anthraquinones are preferably alizarin, quinizarin, purpurin, carminic acid, chrysophanol, kermesic acid, rhein, aloe emodin, pseudopurpurin, quinizarincarboxylic acid, frangula emodin, 2-methylquinizarin, l-hydroxyanthraquinone and 2-hydroxyanthraquinone.
  • the indigoids are preferably indigo, indirubin, isoindigo and Tyrian purple.
  • the hydroxyflavones are preferably quercetin and morin.
  • the (b) coloring agent may be selected from synthetic direct dyes.
  • synthetic direct dye is understood to mean any dye or dye precursor that is produced by chemical synthesis.
  • the direct dye can be selected from the group consisting of acidic (anionic) direct dyes, basic (cationic) direct dyes, and neutral (nonionic) direct dyes.
  • Non-limiting examples of synthetic dyes include (nonionic) neutral, anionic (acidic), and cationic (basic) dyes such as azo, methine, carbonyl, azine, nitro(hetero)aryl types or tri(hetero)arylmethane direct dyes, porphyrins and phthalocyanines, alone or as mixtures.
  • dyes of the family of the carbonyls mention may be made, for example, of synthetic dyes chosen from acridone, benzoquinone, anthraquinone, naphthoquinone, benzanthrone, anthranthrone, pyranthrone, pyrazolanthrone, pyrimidinoanthrone, flavanthrone, indanthrone, flavone, (iso)violanthrone, isoindolinone, benzimidazolone, isoquinolinone, anthrapyridone, pyrazoloquinazolone, perinone, quinacridone, quinophthalone, naphthalimide, anthrapyrimidine, diketopyrrolopyrrole or coumarin dyes.
  • synthetic dyes chosen from acridone, benzoquinone, anthraquinone, naphthoquinone, benzanthrone, anthranthrone, pyr
  • dyes of the family of the cyclic azines mention may in particular be made of azine, xanthene, thioxanthene, fluorindine, acridine, (di)oxazine, (di)thiazine or pyronine dyes.
  • nitro(hetero)aromatic dyes are more particularly nitrobenzene or nitropyridine direct dyes.
  • cationic or noncationic compounds optionally comprising one or more metals or metal ions, such as, for example, alkali and alkaline earth metals, zinc and silicon.
  • nitrobenzene dyes azo, azomethine or methine direct dyes
  • azacarbocyanines such as tetraazacarbocyanines (tetraazapentamethines), quinone and in particular anthraquinone, naphthoquinone or benzoquinone direct dyes, or azine, xanthene, triarylmethane, indoamine, phthalocyanine and porphyrin direct dyes, alone or as mixtures.
  • these synthetic direct dyes are chosen from nitrobenzene dyes, azo, azomethine or methine direct dyes and tetraazacarbocyanines (tetraazapentamethines); alone or as mixtures.
  • azo, azomethine, methine or tetraazapentamethine direct dyes which can be used according to the invention, of the cationic dyes described in Patent Applications WO 95/15144, WO 95/01772 and EP 714 954; FR 2 189 006, FR 2 285 851, FR-2 140 205, EP 1 378 544 and EP 1 674 073.
  • D represents a nitrogen atom or the -CH group
  • R l and R 2 which are identical or different, represent a hydrogen atom; a Ci-C 4 alkyl radical which can be substituted by a -CN, -OH or -NH 2 radical or can form, with a carbon atom of the benzene ring, an optionally oxygen-comprising or nitrogen-comprising heterocycle which can be substituted by one or more Ci-C 4 alkyl radicals; or a 4'-aminophenyl radical,
  • R 3 and R’ 3 which are identical or different, represent a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a cyano radical, a C1-C4 alkyl radical, a C1-C4 alkoxy radical or an acetyloxy radical,
  • X represents an anion, preferably chosen from chloride, methyl sulphate and acetate,
  • A represents a group chosen from the following structures:
  • R 4 represents a C 1 -C 4 alkyl radical which can be substituted by a hydroxyl radical
  • R 5 represents a hydrogen atom, a C1-C4 alkoxy radical or a halogen atom, such as bromine, chlorine, iodine or fluorine,
  • R 6 represents a hydrogen atom or a C1-C4 alkyl radical or forms, with a carbon atom in the benzene ring, a heterocycle which optionally comprises oxygen and/or is optionally substituted by one or more C1-C4 alkyl groups,
  • R 7 represents a hydrogen atom or a halogen atom, such as bromine, chlorine, iodine or fluorine,
  • X represents a cosmetically acceptable anion preferably chosen from chloride, methyl sulphate and acetate
  • E represents a group chosen from the following structures:
  • R’ represents a C 1 -C 4 alkyl radical
  • R’ represents a C 1 -C 4 alkyl radical.
  • the synthetic direct dye may be selected from fluorescent dyes. Two or more types of fluorescent dyes may be used in combination.
  • fluorescent dyes may make it possible to obtain, on dark hair, colors which are more visible than with conventional hydrophilic or hydrophobic direct dyes. Furthermore, these fluorescent dyes, when applied to dark hair, may also make it possible to lighten the hair without damaging it.
  • fluorescent dyes is understood to mean fluorescent compounds and optical brighteners.
  • the fluorescent dye is soluble in the skin or the lips.
  • Fluorescent dyes are fluorescent compounds which absorb visible radiation, for example, wavelengths ranging from 400 to 800 nm, and which are capable of re-emitting light in the visible region at a higher wavelength.
  • the fluorescent dyes useful for the present invention re-emit orange-colored fluorescent light. They exhibit, for instance, a maximum re-emission wavelength ranging from 500 to 700 nm.
  • Non-limiting examples of fluorescent dyes include compounds known in the art, for example, those described in Ullmann's Encyclopedia of Industrial Chemistry, Release 2004, 7th edition, “Fluorescent Dyes” chapter.
  • optical brighteners of the present disclosure also known under the name of "brighteners”, or “fluorescent brighteners”, or “fluorescent brightening agents” or “FWA”, or “fluorescent whitening agents”, or “whiteners”, or “fluorescent whiteners”, are colorless transparent compounds as they do not absorb in visible light but only in ultraviolet light (wavelengths ranging from 200 to 400 nanometers) and convert the energy absorbed into fluorescent light of higher wavelength emitted in the visible part of the spectrum, generally in the blue and/or green, that is to say in wavelengths ranging from 400 to 550 nanometers.
  • Optical brighteners are known in the art, for example, they are described in Ullmann's Encyclopedia of Industrial Chemistry (2002), “Optical Brighteners” and Kirk-Othmer
  • the fluorescent dyes which can be used in the present invention include compounds known from the art, for example, those described in French Patent No. 2 830 189.
  • Soluble fluorescent compounds that may especially be mentioned include those belonging to the following families: naphthalimides, coumarins, xanthenes and in particular
  • xanthenodiquinolizines and azaxanthenes naphtholactams; azlactones; oxazines; thiazines; dioxazines; azo compounds; azomethines; methines; pyrazines; stilbenes; ketopyrroles; and pyrenes.
  • the fluorescent dyes are preferred, more particularly, those re-emitting orange- colored fluorescent light.
  • the (a) direct dye may be selected from the group consisting of acidic direct dyes, basic direct dyes and neutral direct dyes, which covers all possible types of direct dyes, such as so-called nitro dyes and HC dyes.
  • Acidic direct dyes have an anionic moiety in their chemical structure.
  • Basic direct dyes have a cationic moiety in their chemical structure.
  • Neutral direct dyes are nonionic.
  • the (b) coloring agent may be selected from dyes, preferably natural direct dyes, and more preferably coloring plant extracts.
  • the coloring plant extracts here mean plant extracts which are capable of coloring.
  • coloring plant extracts mention may be made of: carrot extract, gardena florida fruit extract, saffron extract, orange extract, and tomato extract, in addition to those explained above for the natural direct dye.
  • the amount of the (b) coloring agent in the microneedle of the microneedle sheet according to the present invention is not limited.
  • the amount of the (b) coloring agent may be 0.01% by weight or more, preferably 0.1% by weight or more, and more preferably 1% by weight or more, relative to the total weight of the microneedle.
  • the amount of the (b) coloring agent may be 30% by weight or less, preferably 20% by weight or less, and more preferably 10% by weight or less, relative to the total weight of the microneedle.
  • the amount of the (b) coloring agent may range from 0.01% to 30% by weight, preferably from 0.1% to 20% by weight, and more preferably from 1% to 10% by weight relative to the total weight of the microneedle.
  • At least one of the microneedles of the microneedle sheet according to the present invention may further comprise at least one cosmetic active ingredient.
  • a single cosmetic active ingredient may be used.
  • Two or more cosmetic active ingredients may be used in combination.
  • the type of the cosmetic active ingredient is not limited.
  • an anti-aging agent may be used as the cosmetic active ingredient.
  • anti-oxidant examples include moisturizers, free- radical scavengers, keratolytic agents, vitamins, anti-elastase and anti-collagenase agents, protides, fatty acid derivatives, steroids, trace elements, bleaching agents, extracts of algae and of planktons, enzymes and coenzymes, flavonoids and ceramides, and mixtures thereof.
  • the amount of the cosmetic active ingredient(s) in the microneedle of the microneedle sheet according to the present invention is not limited, and may be from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight, and more preferably from 0.1% to 1% by weight, relative to the total weight of the microneedle.
  • the amount of the cosmetic active ingredient(s) in the microneedle of the microneedle sheet according to the present invention be less than 0.01% by weight, relative to the total weight of the microneedle.
  • the microneedle of the microneedle sheet according to the present invention may include no cosmetic active ingredient.
  • the microneedle sheet according to the present invention comprises a substrate sheet on which the microneedles are present or placed.
  • the substrate sheet of the microneedle sheet according to the present invention may comprise at least one water-soluble or water dispersible polymer, as explained above.
  • the above explanations for the water-soluble or water-dispersible polymer which is comprised in the microneedles of the microneedle sheet can apply to the water-soluble or water- dispersible polymer which may be comprised in the substrate sheet.
  • the amount (solid basis) of the water-soluble or water-dispersible polymer(s) in the substrate sheet of the microneedle sheet according to the present invention may be 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more, relative to the total weight of the substrate sheet.
  • the amount (solid basis) of the water- soluble or water-dispersible polymer(s) in the substrate sheet of the microneedle sheet according to the present invention may be 100% by weight or less, preferably 90% by weight or less, and more preferably 80% by weight or less, relative to the total weight of the substrate sheet.
  • the amount (solid basis) of the water-soluble or water-dispersible polymer(s) in the substrate sheet of the microneedle sheet according to the present invention may be from 50% to 100% by weight, preferably from 60% to 90% by weight, and more preferably from 70% to 80% by weight, relative to the total weight of the substrate sheet.
  • the substrate sheet may be water-soluble or water-dispersible.
  • the substrate sheet and the microneedles may be integrated.
  • the substrate sheet and the microneedles may comprise at least one common water-soluble or water dispersible polymer.
  • the substrate sheet and the microneedles can be a single element comprising at least one common water-soluble or water-dispersible polymer.
  • the single element can be prepared by using the same water-soluble or water-dispersible polymer(s).
  • the substrate sheet also comprise at least one coloring agent as explained above. If the substrate sheet comprises at least one coloring agent, the coloring agent may be conveyed to the skin or lips via the microneedles.
  • the substrate sheet may be different or distinct from the microneedles.
  • the substrate sheet and the microneedles may be made from different materials.
  • the substrate sheet may be, for example, chosen from masks, wipes, patches, and in general all types of porous substrate sheets.
  • these substrate sheets have an oblong structure, namely with a thickness smaller than the dimensions of the plane in which they are defined.
  • the substrate sheet may be water-insoluble or water-indispersible.
  • the substrate sheet may be cut so as to be in the form of a disc, a mask, a towel, a glove, a precut roll, or any other form suitable for a cosmetic use.
  • microneedle sheet according to the present invention there is no limitation regarding how to prepare the microneedle sheet according to the present invention. It is possible to prepare the microneedle sheet according to the present invention based on conventional technology such as molding, 3D printing and droplet bom air blowing.
  • microneedle sheet according to the present invention can be prepared, for example, by a process comprising the steps of molding a composition comprising at least one water-soluble or water-dispersible polymer and at least one coloring agent, as explained above.
  • the microneedle sheet according to the present invention can be prepared by a process comprising the steps of
  • the mold may be made from organic materials such as polyamides and silicones and inorganic materials such as aluminum and iron.
  • At least one evaporable liquid ingredient may be included in the above composition, if necessary, in order to enhance the fluidity of the composition.
  • the evaporable liquid ingredient are not limited, but may preferably be water and alcohol such as ethanol.
  • the amount of the evaporable liquid ingredient(s) may be 10% by weight or more, preferably 20% by weight or more, and more preferably 30% by weight or more, relative to the total weight of the composition.
  • the amount of the evaporable liquid ingredient(s) may be 98% by weight or less, preferably 95% by weight or less, and more preferably 90% by weight or less, relative to the total weight of the composition.
  • the amount of the evaporable liquid ingredient(s) may be from 10% to 98% by weight, preferably from 20% to 95% by weight, and more preferably from 30% to 90% by weight, relative to the total weight of the composition.
  • the amount of the water-soluble or water-dispersible polymer(s) in the above composition may be from 2% to 90% by weight, preferably from 5% to 50% by weight, and more preferably from 5% to 30% by weight relative to the total weight of the composition.
  • the amount of the coloring agent(s) in the above composition may be from 0.01% to 20% by weight, preferably from 0.05% to 10% by weight, and more preferably from 0.1% to 5% by weight relative to the total weight of the composition.
  • the above composition may include at least one additional polymer such as the above-explained swellable polymer and/or at least one cosmetic active ingredient as explained above.
  • the shape of the microneedle sheet according to the present invention is not limited, and it may be any shape such as the shape of the lips or a shape suitable for application under the eyes, depending on the application target of the microneedle sheet.
  • the microneedle sheet according to the present invention may be a cosmetic device, preferably a cosmetic device for skin or the lips, and more preferably a cosmetic device for delivering at least one coloring agent more into the surface layer of the skin, in particular the face, as well as the lips, preferably into the epidermins, and more preferably into the stratum comeum.
  • the microneedle sheet according to the present invention can be used for (non-therapeutic) cosmetic treatments, preferably cosmetic treatments for skin, and more preferably cosmetic treatments for coloring skin or the lips, in particular for durable or long-lasting coloring.
  • the cosmetic process according to the present invention may comprise the steps of applying onto the skin or the lips the microneedle sheet according to the present invention, pressing the microneedle sheet to the skin or the lips, and removing the microneedle sheet from the skin or the lips.
  • the pressing time may be selected depending on the purpose of the cosmetic process.
  • the pressing time may vary as long as it is sufficient for the microneedles of the microneedle sheet according to the present invention to dissolve in the skin or the lips.
  • the cosmetic process for skin according to the present invention may be intended for long- lasting coloring of the surface of the skin or the lips.
  • coloring agent(s) is/are inserted by the present invention into the surface layer of the skin or the lips, the coloring agent(s) are difficult to be removed from the surface of the skin or lips, even by wiping with cleansing products. Therefore, the present invention can provide durable or long-lasting coloring effects. Also, the use of microneedle sheet according to the present invention does not cause any pain.
  • the present invention can provide the surface of the skin or the lips with durable or long-lasting coloring effects without pain.
  • the present invention may also be used to provide eye blow with color effects by, for example, applying the microneedle sheet according to the present invention onto the skin under eye blow.
  • the present invention also relates to a cosmetic use of the microneedle sheet according to the present invention for providing the skin or the lips with durable or long-lasting coloring effects.
  • Example 1 The ingredients for Example 1 shown in Table 1 were mixed to obtain a mixture.
  • microneedles in the cavities were demolded as a microneedle sheet having a plurality of microneedles.
  • the shape of the microneedles was a cone and the dimensions (average values) of the cone is shown in Table 2.
  • the pitch between two cones on the microneedle sheet was 476 pm.
  • the microneedle sheet according to Example 1 was applied on the surface of a frozen human skin sample with a thickness of 700 pm, pressed onto the skin sample with a thumb for 20 seconds. After pressing, the microneedle sheet was removed from the surface of the skin sample. Then, the skin was wiped off with a tissue to remove any coloring material form the surface of the skin. The microneedle array of the microneedle sheet and the surface of the skin sample were visually observed with a microscope. It was observed that microneedle tips were disappeared (dissolved), and that the total length of the microneedle was reduced from 350 pm to 203 pm. Also, it was observed that the skin surface was dyed with blue color even after wiping, which indicated that blue dye was penetrated into the skin surface layer. As a result, it was found that microneedles can be used for providing the skin with durable or long-lasting coloring effects.

Abstract

The present invention relates to a microneedle sheet comprising a substrate sheet and a plurality of microneedles on the substrate sheet, wherein the microneedles comprise (a) at least one water-soluble or water-dispersible polymer and (b) at least one coloring agent. The microneedle sheet according to the present invention can provide the surface of the skin or the lips with durable or long-lasting coloring effects without pain.

Description

DESCRIPTION
MICRONEEDLE SHEET TECHNICAL FIELD
The present invention relates to a microneedle sheet comprising a plurality of microneedles which can be used for cosmetic treatments of skin.
BACKGROUND ART
The stratum comeum (SC) constitutes the main barrier to exogenous substances including small molecular weight materials. In general, exogenous substances permeating the skin must diffuse through the highly organized intercellular lipid bilayers of the stratum comeum. This intercellular microroute, which is lipophilic, is the primary pathway for exogenous substances to pass through the SC barrier by passive diffusion along a concentration gradient between a delivery vehicle and the SC. It is difficult for some exogenous substances to penetrate into the skin.
In order to provide exogenous substances deeper into the skin, it is possible to perform injections using a conventional needle. However, such injections cause pain, and need to be performed by a professional such as a doctor. Thus, injections using a conventional needle are not common for cosmetic purposes.
The concept of using a micro-structured device with a plurality of microneedles to breach the stratum comeum (SC) barrier was first proposed in the l970s. The production of microneedle arrays has been described in the art, for example in WO 2008/139786, WO 2009/040548, WO 2015/147040 and WO 2016/076442. Microneedles have an advantage of potentially penetrating the SC without pain caused by the use of conventional needles for injections, and can be self-administered.
On the other hand, for cosmetic purposes, the surface of the skin or the lips is often colored or dyed. For example, makeup cosmetic products such as a foundation and a lip stick are widely used to color or dye the skin, in particular the skin of the face and the lips. The coloring or dyeing by makeup cosmetic products is temporary and can be easily removed from the skin and the like with, for example, cleansing products. Thus, the users of the makeup cosmetic products need to color the skin and/or the lips on a daily basis.
So far, there has been no idea to use microneedles for coloring or dyeing the skin or the lips.
DISCLOSURE OF INVENTION
An objective of the present invention is to provide the surface of the skin or the lips with durable or long-lasting coloring effects without pain.
The above objective can be achieved by a microneedle sheet comprising a substrate sheet and a plurality of microneedles on the substrate sheet, wherein the microneedles comprise (a) at least one water-soluble or water-dispersible polymer, and (b) at least one coloring agent. It is preferable that the microneedle be capable of providing the (b) coloring agent into the surface layer of the skin or the lips.
It is preferable that the microneedle be capable of penetrating into the skin or the lips to a depth of 200 microns or less, preferably 180 microns or less, and more preferably 160 microns or less.
It is preferable that the microneedle be in the shape of a cone. The base of the cone of the microneedle may have a diameter of from 80 to 300 microns, preferably from 100 to 250 microns, and more preferably from 120 to 200 microns.
The microneedle may have a height of from 50 to 1000 microns, preferably from 100 to 750 microns, and more preferably from 150 to 500 microns.
The ratio of (the height of the cone)/(the diameter of the base of the cone) of the microneedle may be 1 or more, preferably 1.5 or more, and more preferably 2.0 or more.
It is preferable that the (a) water-soluble or water-dispersible polymer be dissolvable in the surface layer of the skin or the lips.
The (a) water-soluble or water-dispersible polymer may be selected from hyaluronic acids, monosaccharides, disaccharides, oligosaccharides, polysaccharides, dextrins, dextrans, polyethylene glycols, polyvinyl alcohols, poly(methylvinylether/maleic anhydride), polyvinylpyrrolidone, poly(methyl/vinyl ether/maleic acid) (PMVE/MA) and esters thereof, poly(methyl/vinyl ether/maleic anhydride) (PMVE/MAH), and mixtures thereof.
The (a) water-soluble or water-dispersible polymer may have a molecular weight of from 6,000 to 200,000 Dalton, preferably from 8,000 to 100,000 Dalton, and more preferably from 10,000 to 50,000 Dalton.
The (b) coloring agent may be selected from dyes, preferably natural dyes, and more preferably coloring plant extracts. The amount of the (b) coloring agent may range from 0.01% to 30% by weight, preferably from 0.1% to 20% by weight, and more preferably from 1% to 10% by weight relative to the total weight of the microneedle.
The present invention also relates to a cosmetic process for skin or the lips comprising the steps of:
applying onto the skin or the lips the microneedle sheet according to the present invention; pressing the microneedle sheet to the skin or the lips; and
removing the microneedle sheet from the skin or the lips. The cosmetic process according to the present invention is preferably for long-lasting coloring the surface of the skin or the lips.
The present invention also relates to a cosmetic use of the microneedle sheet according to the present invention for providing the skin or the lips with durable or long-lasting coloring effects. BEST MODE FOR CARRYING OUT THE INVENTION
After diligent research, the inventors have discovered that it is possible to provide the surface of the skin or the lips with durable or long-lasting coloring effects without pain, by using microneedles.
Thus, one aspect of the present invention is a microneedle sheet comprising a substrate sheet and a plurality of microneedles on the substrate sheet, wherein the microneedles comprise (a) at least one water-soluble or water-dispersible polymer, and (b) at least one coloring agent.
Since microneedles do not cause any pain, the microneedle sheet according to the present invention can provide coloring effects without pain.
Since the (b) coloring agent in the microneedle sheet according to the present invention is provided into the skin or the lips, not on the skin or the lips, the (b) coloring agent cannot be removed by wiping the surface of the skin or the lips, and can remain in the surface layer of the skin or the lips. Therefore, the (b) coloring agent can provide the skin or the lips with durable or long-lasting coloring effects.
The coloring of the skin or the lips provided by the present invention can be performed for cosmetic purposes, such as modifications of optical appearance, for the skin or the lips. The cosmetic purposes include, for example, makeup for the skin, but also encompass any other corrections or modifications of skin color disorders. The skin color corrections may include to correct or erase skin color disorders, such as achromia, alopecia, vitiligo, scars, for example from acne, depigmented spot-areas, over-pigmented areas and spots, or also to attenuate dark circles under the eyes; or to modify the skin or lip tone.
Thanks to the microneedles, the (b) coloring agent can be delivered to a deeper surface layer of the skin or the lips, by-passing the SC, which is not possible with topical applications of the coloring agent.
Thus, the microneedle sheet according to the present invention can provide the surface of the skin or the lips with durable or long-lasting coloring effects without pain.
The present invention is convenient for cosmetic or non-therapeutic treatments.
Hereafter, the microneedle sheet according to the present invention will be described in a detailed manner.
[Microneedle Sheet]
The microneedle sheet according to the present invention comprises a substrate sheet and a plurality of microneedles on the substrate sheet, wherein the microneedles comprise (a) at least one water-soluble or water-dispersible polymer, and (b) at least one coloring agent.
The microneedle sheet according to the present invention may be a cosmetic device, preferably a cosmetic device for a keratin substance, and more preferably a cosmetic device for the skin, in particular the skin of the face, as well as the lips. (Microneedles)
The microneedle sheet according to the present invention comprises a plurality of microneedles.
The microneedles are present on the surface of the substrate sheet. The microneedles may be present on 50% or more, preferably 70% or more, and more preferably 90% or more of the surface of the substrate sheet.
It is preferable that the microneedles be present on one of the surfaces of the substrate sheet.
It is preferable that the microneedles of the microneedle sheet according to the present invention be designed to penetrate or enter into the stratum comeum of the skin, in particular the skin of the face, as well as the lips.
It is preferable that the microneedles are solid, not hollow.
A microneedle can be any suitable size and shape to puncture the stratum comeum. It may be preferable that the microneedles be designed to pierce and cross the stratum comeum. The microneedles may be capable of creating openings in the stratum comeum.
If necessary, the height of the microneedles may be altered so as to allow penetration into the epidermis and/or dermis of the skin, preferably into the upper dermis, and more preferably into the lower dermis.
The shape of the microneedles is not limited as long as the shape is a“needle”. It will be apparent to those skilled in the art that the microneedles of the present invention can take any reasonable shape, including, but not limited to, cones, rods and/or pillars. As such, the microneedles may have the same diameter at the tip as at the base or may taper in diameter in the direction from the base to the tip.
For example, the shape of the microneedle may be in the form of a triangular pyramid, a square pyramid or a pentagonal pyramid. Alternatively, the microneedle may be in the form of a cylinder preferably with a tip which may be formed by diagonally cutting the cylinder.
Thus, reference is made to "microneedles" as a type of microprotrusion or microprojection which is being employed. It will be understood by persons skilled in the art that in many cases the same inventive principles apply to the use of other microprotrusions or
microprojections to penetrate the skin. Other microprotrusions or microprojections may include, for example, microblades as described in U.S. Patent No. 6,219,574 and Canadian Patent Application No. 2,226,718, and edged microneedles as described in U.S. Patent No. 6,652,478.
The height or length of the microneedle of the microneedle sheet according to the present invention may be from 50 to 1000 microns, preferably from 100 to 750 microns, and more preferably from 150 to 500 microns.
According to one embodiment of the present invention, the microneedle is in the form of a cone. It is preferable that the entire shape of each microneedle is in the form of a cone. The cone may comprise a distal end such as a tip and a base. The shape of the base may be a circle or oval.
The height or length of the cone of the microneedle of the microneedle sheet according to the present invention may be from 50 to 1000 microns, preferably from 100 to 750 microns, and more preferably from 150 to 500 microns.
The base of the cone of the microneedle of the microneedle sheet according to the present invention may have a diameter or width of from 80 to 300 microns, preferably from 100 to 250 microns, and more preferably from 120 to 200 microns. If the base of the cone of the microneedle of the microneedle sheet according to the present invention is in the shape of an oval or ellipse, the length of the major axis or width of the oval may be from 80 to 300 microns, preferably from 100 to 250 microns, and more preferably from 150 to 200 microns.
The microneedle may have an aspect ratio (length/width at base) of at least about 3 : 1 , at least about 2: 1 , or at least about 1 : 1. The ratio of (the height of the cone)/(the diameter of the base of the cone) of the microneedle may be 1 or more, preferably 1.5 or more, and more preferably 2.0 or more.
Preferably, the microneedles do not fracture by force when a pressure of insertion of less than 50.0 N/cm2, for example less than 20.0 N/em2, such as less than 10 N/cm2 is exerted on the microneedles along their length.
It is also preferable that the microneedle sheet according to the present invention, in particular the microneedles of the microneedle sheet, have a Young modulus of 50 N/mm or more, preferably 55 N/mm or more, and more preferably 60 N/mm or more.
It is preferable that the microneedle is capable of penetrating into the skin or the lips to a depth of 200 microns or less, preferably 180 microns or less, and more preferably 160 microns or less.
The microneedle can be dissolvable or non-dissolvable. It is preferable that the microneedle be dissolvable, and more preferable dissolvable in water or an aqueous vehicle or medium.
The“dissolvable microneedle” is meant that the microneedle can be broken down or disintegrated inside the skin or lip by, for example, a natural moisturizing factor or external moisture.
The microneedle of the microneedle sheet according to the present invention comprises (a) at least one water-soluble or water-dispersible polymer. Here, the terms“water-soluble” and “water-dispersible” mean soluble and dispersible, respectively, when being in contact with water. A single water-soluble or water-dispersible polymer may be used. Two or more water-soluble or water-dispersible polymers may be used in combination.
It is preferable that the (a) water-soluble or water-dispersible polymer be soluble or dispersible in the skin or the lips. Thus, in one embodiment of the present invention, the (a) water-soluble or water-dispersible polymer is capable of being dissolved or dispersed after insertion into the skin or the lips. Due to the solubility and dispersibility of the polymer, the microneedle of the microneedle sheet according to the present invention can effectively release the coloring agent in the microneedle. Optional external water combined with the application of the microneedle sheet according to the present invention can be used to accelerate the dissolution or dispersion of the microneedle.
It is preferable that the (a) water-soluble or water-dispersible polymer be dissolvable in the surface layer of the skin or the lips.
The (a) water-soluble or water-dispersible polymer may be selected from hyaluronic acids (in particular lower molecular weight hyaluronic acid), monosaccharides, disaccharides, oligosaccharides, polysaccharides (including derivatives thereof such as cellulose and derivatives thereof, in particular hydroxymethylcellulose), dextrins, dextrans, polyethylene glycols, polyvinyl alcohols, poly(methylvinylether/maleic anhydride), polyvinylpyrrolidone, poly(methyl/vinyl ether/maleic acid) (PMVE/MA) and esters thereof, poly(methyl/vinyl ether/maleic anhydride) (PMVE/MAH), and mixtures thereof.
The (a) water-soluble or water-dispersible polymer may have a molecular weight of from 6,000 to 200,000 Dalton, preferably from 8,000 to 100,000 Dalton, and more preferably from 10,000 to 50,000 Dalton.
The low molecular weight hyaluronic acid may have a molecular weight of 100 kDa or less, preferably 70 kDa or less, and more preferably 50 kDa or less.
The polyvinylpyrrolidone may have a molecular weight between 1 kDa and 300 kDa, preferably between 5 kDa and 200 kDa, and more preferably between 7 kDa and 100 kDa.
The poly(methyl/vinyl ether/maleic acid) (PMVE/MA) and esters thereof, and
poly(methyl/vinyl ether/maleic anhydride) (PMVE/MAH) are known as Gantrez-type polymers.
The amount (solid basis) of the (a) water-soluble or water-dispersible polymer(s) in the microneedle of the microneedle sheet according to the present invention may be 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more, relative to the total weight of the microneedle. The amount (solid basis) of the (a) water-soluble or water-dispersible polymer(s) in the microneedle of the microneedle sheet according to the present invention may be 100% by weight or less, preferably 90% by weight or less, and more preferably 80% by weight or less, relative to the total weight of the microneedle. Thus, the amount (solid basis) of the (a) water-soluble or water-dispersible polymer(s) in the microneedle of the microneedle sheet according to the present invention may be from 50% to 100% by weight, preferably from 60% to 90% by weight, and more preferably from 70% to 80% by weight, relative to the total weight of the microneedle.
It may be possible that the microneedle of the microneedle sheet according to the present invention comprise at least one material which is swellable, more preferably water-swellable, and even more preferably swellable in the skin. The above material may be a polymer which is swellable, more preferably water-swellable, and even more preferably swellable in the skin. Here, the term“water-swellable” means swellable when being in contact with water. The above swellable material or polymer may have a high swellability such that it can swell to at least over 10 times in a l-hour in vitro incubation in a physiological saline solution or phosphate buffered saline, preferably at least 20 times in l-hour incubation, more preferably at least 30 times in l-hour incubation, even more preferably at least 40 times in l-hour incubation, and most preferably about 45-55 times in l-hour incubation. It may be preferable that at least the distal end portion of the microneedle swell upon insertion into the skin, more preferably within less than 1 hour, and even more preferably to at least 2 times within 24 hours after insertion into the skin.
The above swellable material, preferably the above swellable polymer, may have a high viscoelasticity such that it can form a gel after the in vitro incubation in a physiological saline solution or phosphate buffered saline. The gel exhibits a high elastic modulus G’, a high viscous modulus G”, a Tangent (d) (Tangent (d) = G”/G’) of less than 1, and a high consistency G* (G*2=G’2 + G”2) even at low frequency (0.01 Hz) in a dynamic frequency sweep test with a Rheometer.
In one embodiment, the above swellable material, preferably the swellable polymer, is not water-soluble or not water-dispersible.
In another embodiment, the above swellable material, preferably the swellable polymer, may be a hydrogel-forming polymer.
The above swellable polymer may be selected from high molecular weight hyaluronic acids, cross-linked hyaluronic acids, cross-linked polyethylene glycol, polyethylene glycol cross- linked poly-lactic acid or poly-glycolic acid or poly-lactic-co-glycolic acid or poly dioxanone, poly(styrene)-block-poly(acrylic acid), polyethylene glycol cross-linked PMVE/MA, cross- linked polyvinylpyrrolidone, sodium starch glycolate; cellulose; natural and synthetic gums; alginates; sodium polyacrylate PEG-crosslinked poly(methyl/vinyl ether/maleic acid)
(PMVE/MA) and esters thereof, PEG-crosslinked poly(methyl/vinyl ether/maleic anhydride) (PMVE/MAH) and esters thereof, and mixtures thereof.
The high molecular weight hyaluronic acid may have a molecular weight of more than 500 kDa, preferably more than 1000 kDa, and more preferably more than 2100 kDa, and preferably less than 10000 kDa.
Unless otherwise defined, the molecular weight here means a number average molecular weight.
The poly(methyl/vinyl ether/maleic acid) (PMVE/MA) and esters thereof, and
poly(methyl/vinyl ether/maleic anhydride) (PMVE/MAH) are known as Gantrez-type polymers.
The amount (solid basis) of the swellable material(s) in the microneedle of the microneedle sheet according to the present invention may be 1% by weight or more, preferably 5% by weight or more, and more preferably 10% by weight or more, relative to the total weight of the microneedle. The amount (solid basis) of the swellable material(s) in the microneedle of the microneedle sheet according to the present invention may be 30% by weight or less, preferably 25% by weight or less, and more preferably 20% by weight or less, relative to the total weight of the microneedle. Thus, the amount (solid basis) of the swellable material(s) in the microneedle of the microneedle sheet according to the present invention may be from 1% to 30% by weight, preferably from 5% to 25% by weight, and more preferably from 10% to 20% by weight, relative to the total weight of the microneedle. A reduction in the amount of matrix, such as epidermis, in the skin tends to lead to a decrease in skin thickness and deterioration of skin elasticity, causing the formation of wrinkles.
If the microneedle of the microneedle sheet according to the present invention comprises at least one swellable material, preferably at least one swellable polymer, the microneedle may be swellable such that it can improve the aesthetic appearance of the skin, in particular the face, by reducing the appearance of wrinkles.
In other words, if the microneedle is swellable, it can swell in the skin to further increase the volume of the microneedle along with its absorption of, for example, water in the skin. Such volume expansion beneath the skin surface of a wrinkle site can effectively push the wrinkles from inside the skin and makes the wrinkles become shallower and wider. Thus, the wrinkles can be reduced or less noticeable.
Accordingly, the swellable microneedles may increase the amount of matrix in the skin to cause an increase of skin elasticity which results in the reduction of wrinkles on the skin.
The apical separation distance between each of the individual microneedles on a substrate sheet can be modified to ensure the penetration of the skin or the lips by the microneedles while having a sufficiently small separation distance to provide high transdermal transport rates.
In one embodiment, the range of apical separation distances between microneedles can be in the range of 50-1000 pm, such as 100-800 pm or 200-600 pm. This may allow a compromise to be achieved between efficient penetration of the stratum comeum by as many microneedles as possible and the necessary margin for possible swelling of the microneedles if they are swellable.
In one embodiment, the density of microneedles may be from 100 to 2000 microneedles/cm2, preferably 500 to 1500 microneedles/cm2, and even more preferably 800 to 1200
microneedles/ cm2.
(Coloring Agent)
The microneedle of the microneedle sheet according to the present invention comprises (b) at least one coloring agent. A single type of coloring agent may be used. Alternatively, two or more coloring agents may be used in combination.
It is preferable that the microneedle sheet according to the present invention is capable of providing the (b) coloring agent into the surface layer of the skin or the lips.
In the present invention, "coloring agent" includes any synthetic or natural, or organic or inorganic, pigments, dyes or lakes, and any other colorants approved by CTFA and the FDA.
In the present invention, the (b) coloring agent may be water-soluble or water-dispersible, or oil-soluble or oil-dispersible or with limited solubility in water.
In one embodiment, the (b) coloring agent may be selected from coloring pigments. The term "coloring pigments" should be understood as meaning white or colored, inorganic or organic particles of any shape which are insoluble and are intended to color or dye the skin or the lips.
The pigments can be white or colored, inorganic and/or organic.
Among the inorganic pigments that may be used, non-limiting mention may be made of titanium dioxide, optionally surface treated, zirconium or cerium oxide, as well as zinc, (black, yellow or red) iron or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, or metal powders, such as aluminum powder or copper powder. The pigments can also be chosen from nanopigments formed of metal oxides, such as titanium dioxide, zinc oxide, iron oxide, zirconium oxide, and cerium oxide, and mixtures thereof. The term "nanopigments" is understood to mean pigments having a mean particle size ranging from 1 n to 500 nm, such as particle sizes ranging from 10 nm to 100 nm.
Among the organic pigments that may be used, non-limiting mention may be made of carbon black, pigments of D&C type and lakes, such as lakes based on cochineal carmine and on barium, strontium, calcium or aluminum. For example, Red 202 (Calcium bis[2-(3-carboxy- 2-hydroxynephthylazo)-5-methylbenzenesulfonate) may be used as the pigment of D&C type.
The organic pigment may also be a diketopyrrolopyrroles (DPP) such as the ones described in EP-A-542669, EP-A-787730, EP-A-787731 and WO-A- 96/08537.
The organic pigment may be selected from bio-pigments such as BioChromaDerm® or BioChromaEyes® provided from Biotic Phocea in France.
Preferably, the coloring pigment may be chosen from metal oxides such as titanium dioxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, and chromium oxide; manganese violet; Prussian blue; ultramarine blue; chromium hydrate; ferric blue; aluminum powder; copper powder; carbon black; pigments of D&C type; lakes; pearlescent pigments; and mixtures thereof.
The term "pearlescent pigments" should be understood as meaning iridescent particles of any shape, such as particles produced by certain shellfish in their shells or else synthesized.
The pearlescent agents can be chosen from white pearlescent agents, such as mica covered with titanium dioxide or with bismuth oxychloride; colored pearlescent agents, such as titanium oxide-coated mica covered with iron oxide, titanium oxide-coated mica covered with ferric blue or chromium oxide, or titanium oxide-coated mica covered with an organic pigment of the above-mentioned type; and pearlescent agents based on bismuth oxychloride.
In one embodiment, the microneedle may include high refraction index particles, interference particles, reflection particles, and light absorbent particles, in particular non-transparent particles or particles modifying the path of light, as the coloring pigment, in order to prevent reflection. Such particles can allow coloring or dermal-pigmenting of the skin or the lips thanks to the optical properties of the particles.
In another embodiment, the (b) coloring agent may be selected from dyes. The dyes may be selected from natural direct dyes and synthetic direct dyes. A direct dye means a colored substance which does not require the use of an oxidizing agent in order to develop its color.
In one embodiment, the (b) coloring agent may be selected from natural direct dyes.
The expression "natural direct dye" is understood to mean any dye or dye precursor that is naturally occurring and is produced by extraction (and optionally purification) from a plant matrix or an animal such as an insect, optionally in the presence of natural compounds such as ash or ammonia.
As natural direct dyes, mention may be made of quinone dyes (such as lawsone and juglone), alizarin, purpurin, laccaic acid, carminic acid, kermesic acid, purpurogallin,
protocatechaldehyde, indigoids such as indigo, sorghum, isatin, betanin, curcuminoids (such as curcumin), spinulosin, various types of chlorophyll and chlorophyllin, hematoxylin, hematein, brazilein, brazilin, safflower dyes (such as carthamin), flavonoids (such as rutin, quercetin, catechin, epicatechin, morin, apigenidin, and sandalwood), anthocyans (such as apigeninidin and apigenin), carotenoids, tannins, orceins, santalins and cochineal carmine.
It is also possible to use extracts or decoctions containing natural direct dye(s), in particular henna-based extracts, curcuma longa extract, sorghum leaf-sheath extract, haematoxylon campechianum extract, green tea extract, pine bark extract, cocoa extract, and logwood extract.
It is preferable that the natural direct dye be chosen from the group consisting of
curcuminoids, santalins, chlorophyllin, haematoxylin, haematein, brazilein, brazilin, sorghum, laccaic acid, lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigoids, isatin, spinulosin, apigenin, orcein, betanin, flavonoids, anthocyans, and extracts or decoctions containing these compounds. Alternatively, the natural direct dyes may be preferably chosen, for example, from
hydroxylated quinones, indigoids, hydroxyflavones, santalins A and B, isatin and its derivatives, and brasilin and its hydroxylated derivative.
The hydroxylated quinones are preferably benzoquinones, naphthoquinones, and mono- or polyhydroxylated anthraquinones which are optionally substituted with groups such as alkyl, alkoxy, alkenyl, chloro, phenyl, hydroxyalkyl and carboxyl.
The naphthoquinones are preferably lawsone, juglone, flaviolin, naphthazarin,
naphthopurpurin, lapachol, plumbagin, chloroplumbagin, droserone, shikonin, 2-hydroxy-3- methyl- 1, 4-naphthoquinone, 3, 5-dihydroxy-l, 4-naphthoquinone, 2, 5-dihydroxy- 1,4- naphthoquinone, 2-methoxy-5-hydroxy-l, 4-naphthoquinone and 3-methoxy-5-hydroxy-l,4- naphthoquinone.
The benzoquinones are preferably spinulosin, atromentin, aurentioglyocladin, 2, 5 -dihydroxy- 6-methylbenzoquinone, 2-hydroxy-3-methyl-6-methoxybenzoquinone, 2, 5-dihydroxy-3,6- diphenylbenzoquinone, 2,3-dimethyl-5-hydroxy-6-methoxybenzoquinone and 2,5-dihydroxy- 6-isopropylbenzoquinone.
The anthraquinones are preferably alizarin, quinizarin, purpurin, carminic acid, chrysophanol, kermesic acid, rhein, aloe emodin, pseudopurpurin, quinizarincarboxylic acid, frangula emodin, 2-methylquinizarin, l-hydroxyanthraquinone and 2-hydroxyanthraquinone.
The indigoids are preferably indigo, indirubin, isoindigo and Tyrian purple.
The hydroxyflavones are preferably quercetin and morin.
In another embodiment, the (b) coloring agent may be selected from synthetic direct dyes.
The expression "synthetic direct dye" is understood to mean any dye or dye precursor that is produced by chemical synthesis.
The direct dye can be selected from the group consisting of acidic (anionic) direct dyes, basic (cationic) direct dyes, and neutral (nonionic) direct dyes.
Non-limiting examples of synthetic dyes include (nonionic) neutral, anionic (acidic), and cationic (basic) dyes such as azo, methine, carbonyl, azine, nitro(hetero)aryl types or tri(hetero)arylmethane direct dyes, porphyrins and phthalocyanines, alone or as mixtures.
More particularly, the azo dyes comprise an -N=N- functional group, the two nitrogen atoms of which are not simultaneously involved in a ring. However, it is not ruled out for one of the two nitrogen atoms of the -N=N- sequence to be involved in a ring.
The dyes of the family of the methines are more particularly compounds comprising at least one sequence chosen from >C=C< and -N=C<, the two atoms of which are not
simultaneously involved in a ring. However, it is specified that one of the nitrogen or carbon atoms of the sequences can be involved in a ring. More particularly, the dyes of this family result from compounds of the following types: true methine (comprising one or more of the above-mentioned -C=C- sequences); azomethine (comprising at least one or more -C=N- sequences) with, for example, the azacarbocyanines and their isomers, the diazacarbocyanines and their isomers, the tetraazacarbocyanines; mono- and diarylmethane; indoamines (or diphenylamines); indophenols; indoanilines.
As regards the dyes of the family of the carbonyls, mention may be made, for example, of synthetic dyes chosen from acridone, benzoquinone, anthraquinone, naphthoquinone, benzanthrone, anthranthrone, pyranthrone, pyrazolanthrone, pyrimidinoanthrone, flavanthrone, indanthrone, flavone, (iso)violanthrone, isoindolinone, benzimidazolone, isoquinolinone, anthrapyridone, pyrazoloquinazolone, perinone, quinacridone, quinophthalone, naphthalimide, anthrapyrimidine, diketopyrrolopyrrole or coumarin dyes.
As regards the dyes of the family of the cyclic azines, mention may in particular be made of azine, xanthene, thioxanthene, fluorindine, acridine, (di)oxazine, (di)thiazine or pyronine dyes.
The nitro(hetero)aromatic dyes are more particularly nitrobenzene or nitropyridine direct dyes.
As regards the dyes of porphyrin or phthalocyanine type, use may be made of cationic or noncationic compounds optionally comprising one or more metals or metal ions, such as, for example, alkali and alkaline earth metals, zinc and silicon.
Mention may be made, as examples of synthetic direct dyes which are particularly suitable, of nitrobenzene dyes, azo, azomethine or methine direct dyes, azacarbocyanines, such as tetraazacarbocyanines (tetraazapentamethines), quinone and in particular anthraquinone, naphthoquinone or benzoquinone direct dyes, or azine, xanthene, triarylmethane, indoamine, phthalocyanine and porphyrin direct dyes, alone or as mixtures. More preferably still, these synthetic direct dyes are chosen from nitrobenzene dyes, azo, azomethine or methine direct dyes and tetraazacarbocyanines (tetraazapentamethines); alone or as mixtures.
Mention may be made, among the azo, azomethine, methine or tetraazapentamethine direct dyes which can be used according to the invention, of the cationic dyes described in Patent Applications WO 95/15144, WO 95/01772 and EP 714 954; FR 2 189 006, FR 2 285 851, FR-2 140 205, EP 1 378 544 and EP 1 674 073.
Thus, mention may very particularly be made of the cationic direct dyes corresponding to the following formulae:
Figure imgf000013_0001
in which:
D represents a nitrogen atom or the -CH group,
Rl and R2, which are identical or different, represent a hydrogen atom; a Ci-C4 alkyl radical which can be substituted by a -CN, -OH or -NH2 radical or can form, with a carbon atom of the benzene ring, an optionally oxygen-comprising or nitrogen-comprising heterocycle which can be substituted by one or more Ci-C4 alkyl radicals; or a 4'-aminophenyl radical,
R3 and R’3, which are identical or different, represent a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a cyano radical, a C1-C4 alkyl radical, a C1-C4 alkoxy radical or an acetyloxy radical,
X represents an anion, preferably chosen from chloride, methyl sulphate and acetate,
A represents a group chosen from the following structures:
Figure imgf000013_0002
in which R4 represents a C1-C4 alkyl radical which can be substituted by a hydroxyl radical;
Figure imgf000013_0003
in which:
R5 represents a hydrogen atom, a C1-C4 alkoxy radical or a halogen atom, such as bromine, chlorine, iodine or fluorine,
R6 represents a hydrogen atom or a C1-C4 alkyl radical or forms, with a carbon atom in the benzene ring, a heterocycle which optionally comprises oxygen and/or is optionally substituted by one or more C1-C4 alkyl groups,
R7 represents a hydrogen atom or a halogen atom, such as bromine, chlorine, iodine or fluorine,
Di and D2, which are identical or different, represent a nitrogen atom or the -CH group, m = 0 or 1 ,
X represents a cosmetically acceptable anion preferably chosen from chloride, methyl sulphate and acetate, E represents a group chosen from the following structures:
Figure imgf000014_0001
in which R’ represents a C1-C4 alkyl radical;
when m = 0 and when Di represents a nitrogen atom, then E can also denote a group with the following structure:
Figure imgf000014_0002
in which R’ represents a C1-C4 alkyl radical.
The synthetic direct dye may be selected from fluorescent dyes. Two or more types of fluorescent dyes may be used in combination.
The use of some fluorescent dyes may make it possible to obtain, on dark hair, colors which are more visible than with conventional hydrophilic or hydrophobic direct dyes. Furthermore, these fluorescent dyes, when applied to dark hair, may also make it possible to lighten the hair without damaging it.
As used herein, the term "fluorescent dyes" is understood to mean fluorescent compounds and optical brighteners. In at least one embodiment, the fluorescent dye is soluble in the skin or the lips.
Fluorescent dyes are fluorescent compounds which absorb visible radiation, for example, wavelengths ranging from 400 to 800 nm, and which are capable of re-emitting light in the visible region at a higher wavelength.
According to one embodiment, the fluorescent dyes useful for the present invention re-emit orange-colored fluorescent light. They exhibit, for instance, a maximum re-emission wavelength ranging from 500 to 700 nm.
Non-limiting examples of fluorescent dyes include compounds known in the art, for example, those described in Ullmann's Encyclopedia of Industrial Chemistry, Release 2004, 7th edition, "Fluorescent Dyes" chapter.
The optical brighteners of the present disclosure, also known under the name of "brighteners", or "fluorescent brighteners", or "fluorescent brightening agents" or "FWA", or "fluorescent whitening agents", or "whiteners", or "fluorescent whiteners", are colorless transparent compounds as they do not absorb in visible light but only in ultraviolet light (wavelengths ranging from 200 to 400 nanometers) and convert the energy absorbed into fluorescent light of higher wavelength emitted in the visible part of the spectrum, generally in the blue and/or green, that is to say in wavelengths ranging from 400 to 550 nanometers.
Optical brighteners are known in the art, for example, they are described in Ullmann's Encyclopedia of Industrial Chemistry (2002), "Optical Brighteners" and Kirk-Othmer
Encyclopedia of Chemical Technology (1995): "Fluorescent Whitening Agents". The fluorescent dyes which can be used in the present invention include compounds known from the art, for example, those described in French Patent No. 2 830 189.
Soluble fluorescent compounds that may especially be mentioned include those belonging to the following families: naphthalimides, coumarins, xanthenes and in particular
xanthenodiquinolizines and azaxanthenes; naphtholactams; azlactones; oxazines; thiazines; dioxazines; azo compounds; azomethines; methines; pyrazines; stilbenes; ketopyrroles; and pyrenes.
If present, the fluorescent dyes are preferred, more particularly, those re-emitting orange- colored fluorescent light.
In terms of ionic nature, the (a) direct dye may be selected from the group consisting of acidic direct dyes, basic direct dyes and neutral direct dyes, which covers all possible types of direct dyes, such as so-called nitro dyes and HC dyes. Acidic direct dyes have an anionic moiety in their chemical structure. Basic direct dyes have a cationic moiety in their chemical structure. Neutral direct dyes are nonionic.
In a preferred embodiment, the (b) coloring agent may be selected from dyes, preferably natural direct dyes, and more preferably coloring plant extracts.
The coloring plant extracts here mean plant extracts which are capable of coloring. As coloring plant extracts, mention may be made of: carrot extract, gardena florida fruit extract, saffron extract, orange extract, and tomato extract, in addition to those explained above for the natural direct dye.
The amount of the (b) coloring agent in the microneedle of the microneedle sheet according to the present invention is not limited.
The amount of the (b) coloring agent may be 0.01% by weight or more, preferably 0.1% by weight or more, and more preferably 1% by weight or more, relative to the total weight of the microneedle. The amount of the (b) coloring agent may be 30% by weight or less, preferably 20% by weight or less, and more preferably 10% by weight or less, relative to the total weight of the microneedle. Thus, the amount of the (b) coloring agent may range from 0.01% to 30% by weight, preferably from 0.1% to 20% by weight, and more preferably from 1% to 10% by weight relative to the total weight of the microneedle.
(Cosmetic Active Ingredient)
According to one embodiment, at least one of the microneedles of the microneedle sheet according to the present invention may further comprise at least one cosmetic active ingredient. A single cosmetic active ingredient may be used. Two or more cosmetic active ingredients may be used in combination.
The type of the cosmetic active ingredient is not limited. For example, an anti-aging agent may be used as the cosmetic active ingredient.
As examples of the anti-aging agent, mention may be made of anti-oxidant, moisturizers, free- radical scavengers, keratolytic agents, vitamins, anti-elastase and anti-collagenase agents, protides, fatty acid derivatives, steroids, trace elements, bleaching agents, extracts of algae and of planktons, enzymes and coenzymes, flavonoids and ceramides, and mixtures thereof.
The amount of the cosmetic active ingredient(s) in the microneedle of the microneedle sheet according to the present invention is not limited, and may be from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight, and more preferably from 0.1% to 1% by weight, relative to the total weight of the microneedle.
It is also possible that the amount of the cosmetic active ingredient(s) in the microneedle of the microneedle sheet according to the present invention be less than 0.01% by weight, relative to the total weight of the microneedle. In one embodiment, the microneedle of the microneedle sheet according to the present invention may include no cosmetic active ingredient.
(Substrate Sheet)
The microneedle sheet according to the present invention comprises a substrate sheet on which the microneedles are present or placed.
The substrate sheet of the microneedle sheet according to the present invention may comprise at least one water-soluble or water dispersible polymer, as explained above. In other words, the above explanations for the water-soluble or water-dispersible polymer which is comprised in the microneedles of the microneedle sheet can apply to the water-soluble or water- dispersible polymer which may be comprised in the substrate sheet.
For example, the amount (solid basis) of the water-soluble or water-dispersible polymer(s) in the substrate sheet of the microneedle sheet according to the present invention may be 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more, relative to the total weight of the substrate sheet. The amount (solid basis) of the water- soluble or water-dispersible polymer(s) in the substrate sheet of the microneedle sheet according to the present invention may be 100% by weight or less, preferably 90% by weight or less, and more preferably 80% by weight or less, relative to the total weight of the substrate sheet. Thus, the amount (solid basis) of the water-soluble or water-dispersible polymer(s) in the substrate sheet of the microneedle sheet according to the present invention may be from 50% to 100% by weight, preferably from 60% to 90% by weight, and more preferably from 70% to 80% by weight, relative to the total weight of the substrate sheet.
Thus, the substrate sheet may be water-soluble or water-dispersible.
The substrate sheet and the microneedles may be integrated.
For example, the substrate sheet and the microneedles may comprise at least one common water-soluble or water dispersible polymer. Thus, in one embodiment, the substrate sheet and the microneedles can be a single element comprising at least one common water-soluble or water-dispersible polymer. Preferably, the single element can be prepared by using the same water-soluble or water-dispersible polymer(s).
It may be preferable that the substrate sheet also comprise at least one coloring agent as explained above. If the substrate sheet comprises at least one coloring agent, the coloring agent may be conveyed to the skin or lips via the microneedles. On the other hand, the substrate sheet may be different or distinct from the microneedles. For example, the substrate sheet and the microneedles may be made from different materials. In this case, the substrate sheet may be, for example, chosen from masks, wipes, patches, and in general all types of porous substrate sheets. Preferably, these substrate sheets have an oblong structure, namely with a thickness smaller than the dimensions of the plane in which they are defined.
Thus, the substrate sheet may be water-insoluble or water-indispersible.
The substrate sheet may be cut so as to be in the form of a disc, a mask, a towel, a glove, a precut roll, or any other form suitable for a cosmetic use.
[Preparation]
There is no limitation regarding how to prepare the microneedle sheet according to the present invention. It is possible to prepare the microneedle sheet according to the present invention based on conventional technology such as molding, 3D printing and droplet bom air blowing.
The microneedle sheet according to the present invention can be prepared, for example, by a process comprising the steps of molding a composition comprising at least one water-soluble or water-dispersible polymer and at least one coloring agent, as explained above.
In one embodiment, the microneedle sheet according to the present invention can be prepared by a process comprising the steps of
(a) providing a mold with cavities corresponding to a negative of the microneedles,
(b) filling a composition comprising at least one water-soluble or water-dispersible
polymer and at least one coloring agent, as explained above, into the cavities,
(c) solidifying the composition, for example, by drying at room temperature (and
optionally heating) for a period of time such as several hours to form the
microneedles, and
(d) removing the microneedle sheet from the mold.
The mold may be made from organic materials such as polyamides and silicones and inorganic materials such as aluminum and iron.
At least one evaporable liquid ingredient may be included in the above composition, if necessary, in order to enhance the fluidity of the composition. Examples of the evaporable liquid ingredient are not limited, but may preferably be water and alcohol such as ethanol.
The amount of the evaporable liquid ingredient(s) may be 10% by weight or more, preferably 20% by weight or more, and more preferably 30% by weight or more, relative to the total weight of the composition. The amount of the evaporable liquid ingredient(s) may be 98% by weight or less, preferably 95% by weight or less, and more preferably 90% by weight or less, relative to the total weight of the composition. Thus, the amount of the evaporable liquid ingredient(s) may be from 10% to 98% by weight, preferably from 20% to 95% by weight, and more preferably from 30% to 90% by weight, relative to the total weight of the composition. The amount of the water-soluble or water-dispersible polymer(s) in the above composition, which is preferably capable of flowing, and more preferably is in the form of a liquid, may be from 2% to 90% by weight, preferably from 5% to 50% by weight, and more preferably from 5% to 30% by weight relative to the total weight of the composition.
The amount of the coloring agent(s) in the above composition, which is preferably fluidable, and more preferably is in the form of a liquid, may be from 0.01% to 20% by weight, preferably from 0.05% to 10% by weight, and more preferably from 0.1% to 5% by weight relative to the total weight of the composition.
If necessary, the above composition may include at least one additional polymer such as the above-explained swellable polymer and/or at least one cosmetic active ingredient as explained above.
The shape of the microneedle sheet according to the present invention is not limited, and it may be any shape such as the shape of the lips or a shape suitable for application under the eyes, depending on the application target of the microneedle sheet.
[Cosmetic Process and Use]
The microneedle sheet according to the present invention may be a cosmetic device, preferably a cosmetic device for skin or the lips, and more preferably a cosmetic device for delivering at least one coloring agent more into the surface layer of the skin, in particular the face, as well as the lips, preferably into the epidermins, and more preferably into the stratum comeum.
The microneedle sheet according to the present invention can be used for (non-therapeutic) cosmetic treatments, preferably cosmetic treatments for skin, and more preferably cosmetic treatments for coloring skin or the lips, in particular for durable or long-lasting coloring.
Thus, the cosmetic process according to the present invention may comprise the steps of applying onto the skin or the lips the microneedle sheet according to the present invention, pressing the microneedle sheet to the skin or the lips, and removing the microneedle sheet from the skin or the lips.
The pressing time may be selected depending on the purpose of the cosmetic process. For example, the pressing time may vary as long as it is sufficient for the microneedles of the microneedle sheet according to the present invention to dissolve in the skin or the lips.
The cosmetic process for skin according to the present invention may be intended for long- lasting coloring of the surface of the skin or the lips.
Since coloring agent(s) is/are inserted by the present invention into the surface layer of the skin or the lips, the coloring agent(s) are difficult to be removed from the surface of the skin or lips, even by wiping with cleansing products. Therefore, the present invention can provide durable or long-lasting coloring effects. Also, the use of microneedle sheet according to the present invention does not cause any pain.
Therefore, the present invention can provide the surface of the skin or the lips with durable or long-lasting coloring effects without pain. The present invention may also be used to provide eye blow with color effects by, for example, applying the microneedle sheet according to the present invention onto the skin under eye blow.
Thus, the present invention also relates to a cosmetic use of the microneedle sheet according to the present invention for providing the skin or the lips with durable or long-lasting coloring effects.
EXAMPLES
The present invention will be described in a more detailed manner by way of examples. However, these examples should not be construed as limiting the scope of the present invention. The examples below are presented as non-limiting illustrations in the field of the present invention.
Example 1
[Preparation]
The ingredients for Example 1 shown in Table 1 were mixed to obtain a mixture.
Immediately after mixing, the mixture was poured into the cavities of a mold which correspond to the shape of microneedles. After drying at room temperature to remove water, microneedles in the cavities were demolded as a microneedle sheet having a plurality of microneedles.
Table 1
Figure imgf000019_0001
The shape of the microneedles was a cone and the dimensions (average values) of the cone is shown in Table 2.
Table 2
Figure imgf000019_0002
The pitch between two cones on the microneedle sheet was 476 pm. [Evaluation] The microneedle sheet according to Example 1 was applied on the surface of a frozen human skin sample with a thickness of 700 pm, pressed onto the skin sample with a thumb for 20 seconds. After pressing, the microneedle sheet was removed from the surface of the skin sample. Then, the skin was wiped off with a tissue to remove any coloring material form the surface of the skin. The microneedle array of the microneedle sheet and the surface of the skin sample were visually observed with a microscope. It was observed that microneedle tips were disappeared (dissolved), and that the total length of the microneedle was reduced from 350 pm to 203 pm. Also, it was observed that the skin surface was dyed with blue color even after wiping, which indicated that blue dye was penetrated into the skin surface layer. As a result, it was found that microneedles can be used for providing the skin with durable or long-lasting coloring effects.

Claims

1. A microneedle sheet comprising a substrate sheet and a plurality of microneedles on the substrate sheet, wherein the microneedles comprises:
(a) at least one water-soluble or water-dispersible polymer; and
(b) at least one coloring agent.
2. The microneedle sheet according to Claim 1 , wherein the microneedle is capable of providing the (b) coloring agent into the surface of the skin or the lips.
3. The microneedle sheet according to Claim 1 or 2, wherein the microneedle is capable of penetrating into the skin or the lips to a depth of 200 microns or less, preferably 180 microns or less, and more preferably 160 microns or less.
4. The microneedle sheet according to any one of Claims 1 to 3, wherein the
microneedle is in the shape of a cone.
5. The microneedle sheet according to Claim 4, wherein the base of the cone of the microneedle has a diameter of from 80 to 300 microns, preferably from 100 to 250 microns, and more preferably from 120 to 200 microns.
6. The microneedle sheet according to Claim 4 or 5, wherein the microneedle has a height of from 50 to 1000 microns, preferably from 100 to 750 microns, and more preferably from 150 to 500 microns.
7. The microneedle sheet according to any one of Claims 4 to 6, wherein the ratio of (the height of the cone)/(the diameter of the base of the cone) of the microneedle is 1 or more, preferably 1.5 or more, and more preferably 2.0 or more.
8. The microneedle sheet according to any one of Claims 1 to 7, wherein the (a) water- soluble or water-dispersible polymer is dissolvable in the surface layer of the skin or the lips.
9. The microneedle sheet according to any one of Claims 1 to 8, wherein the (a) water- soluble or water-dispersible polymer is selected from hyaluronic acids,
monosaccharides, disaccharides, oligosaccharides, polysaccharides, dextrins, dextrans, polyethylene glycols, polyvinyl alcohols, poly(methylvinylether/maleic anhydride), polyvinylpyrrolidone, poly(methyl/vinyl ether/maleic acid) (PMVE/MA) and esters. thereof, poly(methyl/vinyl ether/maleic anhydride) (PMVE/MAH), and mixtures thereof.
10. The microneedle sheet according to any one of Claims 1 to 9, wherein the (a) water- soluble or water-dispersible polymer has a molecular weight of from 6,000 to 200,000 Dalton, preferably from 8,000 to 100,000 Dalton, and more preferably from 10,000 to 50,000 Dalton.
11. The microneedle sheet according to any one of Claims 1 to 10, wherein the (b)
coloring agent is selected from dyes, preferably natural direct dyes, and more preferably coloring plant extracts.
12. The microneedle sheet according to any one of Claims 1 to 11, wherein the amount of the (b) coloring agent ranges from 0.01% to 30% by weight, preferably from 0.1% to 20% by weight, and more preferably from 1% to 10% by weight relative to the total weight of the microneedle.
13. A cosmetic process for skin or the lips comprising the steps of:
applying onto the skin or the lips the microneedle sheet according to any one of
Claims 1 to 12;
pressing the microneedle sheet to the skin or the lips; and
removing the microneedle sheet from the skin or the lips.
14. The cosmetic process according to Claim 13 for long-lasting coloring the surface of the skin or the lips.
15. A cosmetic use of the microneedle sheet according to any one of Claims 1 to 12 for providing the skin or the lips with durable or long-lasting coloring effects.
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