WO2017150950A1 - Dispersion en réseau de microfibrilles de bio-cellulose dans l'eau - Google Patents

Dispersion en réseau de microfibrilles de bio-cellulose dans l'eau Download PDF

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Publication number
WO2017150950A1
WO2017150950A1 PCT/KR2017/002358 KR2017002358W WO2017150950A1 WO 2017150950 A1 WO2017150950 A1 WO 2017150950A1 KR 2017002358 W KR2017002358 W KR 2017002358W WO 2017150950 A1 WO2017150950 A1 WO 2017150950A1
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Prior art keywords
biocellulose
water
composition
dispersion
skin
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PCT/KR2017/002358
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English (en)
Korean (ko)
Inventor
전승현
이설훈
강내규
허유진
김서연
Original Assignee
주식회사 엘지생활건강
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Priority claimed from KR1020170002301A external-priority patent/KR20170103628A/ko
Application filed by 주식회사 엘지생활건강 filed Critical 주식회사 엘지생활건강
Priority to US16/080,758 priority Critical patent/US20190060205A1/en
Priority to CN201780012462.7A priority patent/CN108697620A/zh
Priority to EP17760354.5A priority patent/EP3424487B1/fr
Priority to JP2018545610A priority patent/JP7004387B2/ja
Priority claimed from KR1020170027863A external-priority patent/KR101816792B1/ko
Priority claimed from KR1020170027721A external-priority patent/KR102349932B1/ko
Priority claimed from KR1020170027902A external-priority patent/KR102399486B1/ko
Publication of WO2017150950A1 publication Critical patent/WO2017150950A1/fr

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof

Definitions

  • the present invention relates to a cellulose water dispersion, a preparation method thereof, and a composition comprising the same.
  • the skin functions to block harmful substances from the outside environment and to prevent water loss.
  • Polymers including natural polymers, synthetic polymers and organic polymers applied to the skin protect the skin from the outside, deliver active ingredients to the skin, and act as a barrier to prevent moisture loss.
  • natural polymers such as cellulose, chitosan and polysaccharides have excellent biocompatibility and biodegradability, and play a role of moisturizing, elasticity, and skin protection on the skin.
  • cellulose used in the human body includes natural cellulose, cellulose derivatives, and biocellulose.
  • natural (natural) cellulose is in the form of powder of several tens of micrometers, insoluble in water, and is mainly used for scrubs and peeling gels.
  • a cellulose derivative can be obtained by substituting the hydroxy alcohol group of cellulose, and since cellulose itself is not dissolved in water, hydroxyethyl cellulose, carboxymethyl cellulose, etc. substituted so that it can be dissolved in water are included.
  • Such water-soluble cellulose is in the form of a polymer and is mainly used as a thickener.
  • Biocellulose is a cellulose microfiber synthesized from bacterial cellulose, which is mainly used in mask pack sheet because it is thinner than the plant-derived cellulose and has high crystallinity and high physical strength, but is synthesized in the form of gel or sheet. There are disadvantages to the formulation application.
  • Patent Document 1 Korean Patent Application Publication No. 10-2012-0123371 (Patent Document 1) and Japanese Patent Application Publication No. 2010-037199 (Patent Document 2)
  • the cellulose fiber is 1000 nm or less and has a number average fiber diameter of 2 to 150 nm, wherein the cellulose has a cellulose type I crystal structure, and the hydroxyl group on the C6 of the glucose unit in the cellulose molecule is selectively oxidized.
  • cellulose modified with an aldehyde group and a carboxyl group, and the cellulose can be used as a composition for cosmetics, thickeners / gelling agents, and sprays.
  • Patent Documents 1 and 2 can be used for thickeners / gelling agents to improve the prosthetic performance, dispersion stability, and flame resistance in the composition, but are suitable for expressing the merits based on cellulose in the skin.
  • Patent Document 1 discloses that it is preferable to use non-wood cellulose such as coniferous pulp, broadleaf pulp, cotton linter, cotton lint such as cotton lint, straw pulp, vargas pulp, and the like. Uses pulp.
  • the softwood pulp is used for the Example.
  • the length of the cellulose should be maintained at a micro size or more, and the fibers should be able to maintain a network even after being dispersed in water.
  • a top-down method is used. The pretreatment process is essential, and the cellulose length is randomly cut in this process, which may cause skin penetration when the final cellulose fiber enters the cosmetic.
  • it since it is difficult to form a network, it can be used as a thickener or a formulation stabilizer, but there is a limit to use as a cosmetic composition.
  • fine dust is classified into fine dust (PM10) having a diameter of 10 ⁇ m or less and ultrafine dust (PM2.5) having a diameter of 2.5 ⁇ m or less, depending on the size of the particles.
  • Fine dust is composed of ionic components such as nitrates, ammonium, sulfates, carbon compounds, and metal compounds generated by combustion. Repeated and prolonged exposure to fine dust in the air can cause serious diseases such as heart attack, asthma, bronchitis, pneumonia, and lung cancer.
  • skin exposure of fine dust causes serious problems such as dry skin, atopy, dermatitis.
  • fine dust not only impairs epidermal barrier function, exacerbates atopic dermatitis, but is directly related to skin aging, in which wrinkles and pigment spots are increased.
  • body hair including hair
  • nails and skin are made of structural proteins called keratin
  • these tissues are also called keratin structures.
  • a method of covering the surface with a raw material such as silicon or using a volatile organic solvent or the like has been widely used.
  • this method does not take into account the characteristics of the cuticle layer, which is scaled on the outermost surface of the keratinous structure, and the cuticle layer is very fragile, when the raw material used for keratin protection is separated from the keratin surface. Often the cuticle layer was damaged. Accordingly, there is a need for a keratin construct care composition that protects the keratin while at the surface of the keratin structure but does not damage the cuticle layer.
  • the problem to be solved by the present invention has a length and diameter of the cellulose microfibers without fear of penetration of the skin, while maintaining the network structure even when formulated as a water-dispersible composition, cellulose microfibers excellent in water absorption and elasticity enhancing ability It is to provide a microfiber dispersion.
  • the problem to be solved by the present invention has the length and diameter of the cellulose microfibers without fear of skin penetration, while maintaining the network structure even when formulated as a water-dispersible composition, it can block fine dust as well as ultra-fine dust
  • the present invention provides an excellent cellulose microfiber dispersion.
  • the problem to be solved by the present invention is to provide a keratin structure protective biocellulose microfiber water dispersion network composition and a method for preparing the keratin structure to protect their keratin but does not damage the cuticle layer.
  • the problem to be solved by the present invention is to provide a water absorption and elasticity of the above-described cellulose microfiber microfiber dispersion dispersion, fine dust blocking use, or keratin structure protection use.
  • the problem to be solved by the present invention is to provide a method of applying the above-described cellulose microfiber microfiber dispersion to the human body to absorb water and enhance elasticity, to block fine dust, or to protect a keratin structure.
  • the present invention is the alcohol group of the biocellulose is substituted with a carboxyl group, preferably the maximum diameter 60-100 nm and the number average diameter 30-60 nm of the individual microfibers in the dispersion, used as a raw material
  • the dispersed biocellulose microfiber network dispersion, a method for preparing the same, a composition, a use of the dispersion and a composition, and a dispersion and a composition are characterized in that the length of the prepared biocellulose is maintained and dispersed in a water phase to form a network. It provides a method of applying to the human body.
  • the present inventors selected biocellulose as a cellulose raw material, oxidized the biocellulose to substitute the alcohol group of the biocellulose, and limited the diameter and length of the biocellulose to obtain a biocellulose microfiber network dispersion.
  • the obtained biocellulose microfiber network dispersion has a length and network structure similar to that of biocellulose before oxidation and is dispersed in an aqueous phase, and is advantageous for human body, such as skin seizure, high water retention, increased elasticity, reduced skin friction and It was found to have increasing power.
  • the present invention was completed based on the usefulness of the biocellulose microfiber network dispersion to the human application, such as cosmetics or quasi-drugs.
  • the present inventors selected biocellulose as a cellulose raw material, oxidized the biocellulose to substitute the alcohol group of the biocellulose, and limited the diameter and length of the biocellulose to obtain a biocellulose microfiber network dispersion.
  • the obtained biocellulose microfiber network dispersion has a length and a dense network structure similar to that of biocellulose before oxidation and is dispersed in an aqueous phase and prevents infiltration of fine dust and ultrafine dust without penetrating into the skin. It was confirmed that it can be formulated into a composition of various formulations dispersed in the aqueous phase and completed the present invention.
  • the present inventors selected biocellulose as a cellulose raw material, oxidized the biocellulose to substitute the alcohol group of the biocellulose with a carboxyl group, and when limiting the diameter and length of the biocellulose, the water phase was similar to the length of the biocellulose before the oxidation. It has the effect of protecting the keratin structure while maintaining the network structure and not penetrating the skin, and also does not damage the cuticle layer during the removal process, and can be dispersed in the aqueous phase and formulated into various formulation compositions. It confirmed and completed this invention.
  • the 'network' means a three-dimensional network structure between cellulose microfibers.
  • the 'aqueous phase' means a phase including water in the solvent, and if water is included in the solvent, it is not limited to including other solvents besides water. For example, an aqueous solution is also included.
  • the term 'skin-settlement' means that the water-dispersible biocellulose microfiber network dispersion is applied on the skin surface while maintaining the structural, physicochemical and / or water dispersible properties of the microfibers.
  • the 'moisture retention capacity' refers to a force or ability to attract moisture around the dispersed biocellulose microfiber network dispersion and / or a force or ability to maintain ambient moisture. Moisture retention capacity and water absorption capacity to moisturizing ability are proportional to each other. Therefore, it exhibits high water absorption capacity or moisturizing ability.
  • the 'elasticity' means a resistance to external force applied, the same meaning as the 'resilience', and reflects the compactness of the surface structure. It means that the film forming ability of the water-dispersible biocellulose microfiber network dispersion and the resistance to external force of the object to which the water-dispersed biocellulose microfiber network dispersion is applied are increased, improved or improved.
  • the 'gradual power' means the ability to increase viscosity. It means that the water-dispersible biocellulose microfiber network dispersion has the ability to increase the viscosity while maintaining the structural and physicochemical characteristics of the microfibers.
  • the 'friction force' is a force that interferes with the movement of the object touching the contact surface, the skin friction force is reflected in the skin roughness.
  • the degree to which the movement of the object touching the contact surface to which the water-dispersed biocellulose microfiber network dispersion is applied is reduced, which means that the softness is increased, improved or improved, or the roughness is reduced.
  • Fine dust blocking effect refers to particulate matter having a diameter of 10 ⁇ m or less, and includes ultrafine dust having a diameter of 2.5 ⁇ m or less.
  • the 'fine dust blocking' means that the fine dust is attached or adsorbed directly to the skin or to prevent or suppress the penetration of fine dust into the skin, which means that the fine dust is easily removed.
  • the 'keratin structure' is a human organ or tissue consisting of a structural protein called keratin, such as nails, toenails, hair, and the like.
  • keratin structure protection' refers to the protection of the keratin structure from physical and chemical damage or dropping by any cause outside the keratin structure, the external physical and chemical during the regeneration, recovery and treatment of the damaged keratin structure Protection from negative effects, protection of the human tissue comprising the keratin construct, in particular the cuticle layer, and the like, in the process of removing the dispersion or composition comprising the same from the keratin construct, and the like.
  • the water-dispersible bio cellulose microfibers in particular, form a network on the surface of the keratin structure to prevent the surface keratin layer from falling off, and stably bind to the surface of the keratin, thus being removed without damaging the surface of the keratin.
  • the characteristics of the water-dispersible biocellulose microfiber network dispersions described above are maintained or improved in compositions comprising the water-dispersible biocellulose microfiber network dispersions.
  • the water-dispersible biocellulose microfiber network dispersion according to the present invention uses biocellulose as a cellulose raw material.
  • 'Biocellulose' used in the present invention refers to bacterial cellulose that synthesizes cellulose microfibers directly through bacterial culture.
  • it is distinguished from cellulose derived from plants such as kenaf, hemp, rice, bacas, and bamboo.
  • Available bacteria include, for example, the genus Acetobacter, Rhizibium and Agrobacterium, and when grown in a medium containing nutrients for bacterial culture, bacterial cellulose is formed at the interface of the culture.
  • Culture methods include static cultivation and agitated cultivation.
  • the stationary culture method is a method in which bacteria are first implanted in a medium and then incubated in a flask for about 10 days in a shelf or the like.
  • Another method, shaking culture is a method of culturing while stirring at a constant rate in a shaking incubator through a liquid medium. It is also possible to purchase and use a commercially available biocellulose without using the bacterial culture.
  • Biocellulose has a three-dimensional network, has a high degree of crystallinity (84-89%), and has sufficient pores.
  • the length of the biocellulose is tens to tens of micrometers and has a constant, ie even diameter of length distribution.
  • the alcohol group of the biocellulose according to the present invention is substituted with a carboxyl group.
  • At least 0.8 mmol / g cellulose, more preferably at least 1.0 mmol / g cellulose, of all alcohol groups contained in the biocellulose is substituted with a carboxyl group.
  • Substitution of the alcohol group of the biocellulose with a carboxyl group may be performed by various methods in the art, and may be achieved by, for example, adding and stirring an oxidizing agent and biocellulose to distilled water in which an N-oxyl compound is dissolved.
  • the alcohol group of the biocellulose since the alcohol group of the biocellulose is substituted with a carboxyl group, it exhibits a negative charge due to the carboxyl group.
  • negative charges of -30 mV or less are shown, more preferably -50 mV or less, and still more preferably -60 mV or less. Most preferably a negative charge of -60 mV to -90 mV.
  • the negative charge of the water-dispersible biocellulose microfiber network dispersion according to the present invention repels the negative charge of the fine dust, thereby reducing the fine dust adhesion.
  • the number average diameter of the individual microfibers in the water-dispersible biocellulose microfiber network dispersion according to the present invention is 0.1-200 nm, preferably 1-150 nm, more preferably 20-100 nm, most preferably 30-60 nm. to be.
  • it is advantageous for human application for example, it is advantageous for use as a cosmetic composition and quasi-drug composition, especially when it is 30 ⁇ 60 nm, while forming a network structure, the advantage of being able to express a unique function without being pushed during application It effectively blocks fine dust without penetrating the skin.
  • the maximum diameter of the individual microfibers in the water dispersion biocellulose microfiber network dispersion according to the present invention is 0.1 to 200 nm, preferably 1 to 150 nm, more preferably 20 to 100 nm, most preferably 60 to 100 nm.
  • it is advantageous for human application for example, it is advantageous for use as a cosmetic composition and quasi-drug composition, and when it is more than 200 nm, it may be pushed out during application.
  • the length of the individual microfibers in the water dispersion biocellulose microfiber network dispersion according to the present invention is similar to the length of the biocellulose used as a raw material.
  • the microfibers according to the present invention maintain the length of the biocellulose used as a raw material.
  • the 'length is... Length and... Similar ”to“ maintain length ”means that there is no substantial difference from the length of the biocellulose used as the raw material, and substantially no difference means that the difference between the lengths is ⁇ 10% or less, ⁇ 5% or less, ⁇ 1% or less, ⁇ 0.1% or less, most preferably ⁇ 0.01% or less.
  • the process of cutting the fine fibers is not included, and thus the length of the biocellulose as a raw material is almost maintained.
  • the water-dispersible biocellulose microfiber network dispersion according to the present invention when added to an aqueous solution, maintains the structural and physicochemical characteristics and / or water dispersibility as microfibers, and in particular, maintains the biocellulose intact network and stably disperses. Has characteristics.
  • the water-dispersible biocellulose microfiber network dispersion according to the present invention can be formulated into a water-dispersible composition.
  • the 'water dispersion composition' refers to a composition including water as a solvent, and a composition in which a water-dispersible biocellulose microfiber network dispersion is dispersed in an aqueous phase.
  • the composition may be aqueous phase alone, water-in-oil type, oil-in-water type, or multiple emulsions, but is not limited thereto.
  • the water-dispersible biocellulose microfiber network dispersions according to the present invention may be prepared by various methods known in the art, and are not limited to specific methods. However, since biocellulose is used as a raw material, a top-down pretreatment process for miniaturization is not required. For example, the process of cutting the microfibers is not included.
  • it may be prepared by the following steps.
  • N-oxyl compounds include, for example, 2,2,6,6-tetramethyl-1-piperidine-oxy radicals (TEMPO);
  • TEMPO 2,2,6,6-tetramethyl-1-piperidine-oxy radicals
  • 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine-oxy radical (4-hydroxy TEMPO) is etherified with alcohol or esterified with carboxylic acid or sulfonic acid 4-hydroxyTEMPO derivatives which impart proper hydrophobicity; Or azaadamantane-type nitrooxy radicals; At least one of these may be selected, most preferably, 2,2,6,6-tetramethyl-1-piperidine-oxy radical (TEMPO) can be used.
  • TEMPO 2,2,6,6-tetramethyl-1-piperidine-oxy radical
  • the amount of N-oxyl compound to be used is not particularly limited as long as it is a catalyst amount capable of microfiberizing biocellulose.
  • 0.01 to 100 mmol, preferably 0.01 to 50 mmol, and particularly preferably about 0.05 to 30 mmol may be used for 1 g of cellulose-based dry material.
  • halogen, hypohalogenic acid, ahalogenic acid, perhalogenic acid or salts thereof, halogen oxide, halogen peroxide and the like are preferably used.
  • chlorine, hypochlorous acid, chlorous acid, perchloric acid or its salts, chlorine oxide, chlorine peroxide are preferred, and most preferably sodium hypochlorite can be used.
  • Sodium hypochlorite is economical in terms of the cost of producing microfibers, which is particularly desirable because of the low cost and low environmental load which are most common in current industrial processes.
  • the amount of oxidant used can be selected in a range capable of promoting an oxidation reaction. For example, 0.5 to 500 mmol, preferably 0.5 to 50 mmol, and particularly preferably about 2.5 to 25 mmol, may be used for 1 g of cellulose-based dry material.
  • bromide is substantially not used.
  • substantially not used' means using 0.1 mmol or less, preferably 0.01 mmol or less, and more preferably 0.001 mmol or less, based on 1 g of the biocellulose dry material.
  • Bromide such as bromine chloride
  • the method for producing a water-dispersible biocellulose dispersion according to the present invention can smoothly proceed the oxidation reaction even under mild conditions of room temperature of about 15 to 30 ° C.
  • the reaction time of the oxidation reaction can be appropriately set and is not particularly limited, but is, for example, 0.5 to 60 hours, preferably 1 to 50 hours, particularly preferably about 24 to 48 hours.
  • the water-dispersible biocellulose microfiber network dispersion according to the present invention can be utilized as a composition for various uses, and in particular can be used as a cosmetic composition and quasi-drug composition.
  • the water-dispersible biocellulose microfiber network dispersion according to the present invention is excellent in skin adhesion and does not penetrate into the skin, and may be used as a cosmetic composition and quasi-drug composition applied to the human body, preferably the skin.
  • the water-dispersible biocellulose microfiber network dispersion according to the present invention is characterized by being dispersed in the water phase to form a network, which is particularly useful in compositions comprising the water phase.
  • the water-dispersible biocellulose microfiber network dispersion according to the present invention has skin seating properties, water retention capacity, increased elasticity, and thickening power, softness improvement ability, and thus can be used for these applications.
  • the water-dispersible biocellulose microfiber network dispersion according to the present invention or a composition comprising the same may be used for moisture enhancement or elasticity enhancement.
  • the water-dispersible biocellulose microfiber network dispersion according to the present invention has excellent skin adhesion and does not penetrate into the skin, and thus has an excellent effect on blocking fine dust.
  • the water-dispersible biocellulose microfiber network dispersion according to the present invention or a composition comprising the same may be used for blocking fine dust.
  • the water-dispersible biocellulose microfiber network dispersion according to the present invention has excellent skin adhesiveness and does not penetrate into the skin, and thus has an excellent effect on protecting keratin structures.
  • the water-dispersible biocellulose microfiber network dispersion or composition comprising the same according to the present invention can be used for protecting keratin structures.
  • the present invention is a biocellulose microfiber network dispersion, preferably a maximum diameter of 60 to 100 nm, number average diameter of 30 to 60 nm, dispersion of water-dispersible biocellulose microfiber network, characterized in that the network is dispersed in the water phase It provides a cosmetic composition comprising a sieve.
  • the cosmetic composition of the present invention can also be used as a functional cosmetic.
  • cosmetic cosmetic is a product that has a professional therapeutic function of the drug is introduced into the cosmetic, unlike the general cosmetic products having a professional functionality with emphasis on the bioactive efficacy, effect, for example It refers to cosmetics prescribed by Ordinance of the Ministry of Health and Welfare such as products that help to whiten skin, products that help to improve skin wrinkles, products that burn skin finely or protect skin from ultraviolet rays.
  • Cosmetic compositions of the present invention are conventional auxiliaries in the cosmetic field, such as fatty substances, organic solvents, solubilizers, thickeners, gelling agents, emollients, antioxidants, suspending agents, stabilizers, foaming agents, fragrances, interfaces Active agents, water, ionic or nonionic emulsifiers, fillers, metal ion sequestrants, chelating agents, preservatives, vitamins, blockers, wetting agents, essential oils, dyes, pigments, hydrophilic or lipophilic active agents, lipid vesicles, as well as cosmetics It may be used as a component of general cosmetics or functional cosmetics, together with auxiliary agents commonly used in the cosmetic or dermatological fields, such as any other ingredients conventionally used in the art.
  • Cosmetics comprising the cosmetic composition according to the present invention may be prepared in any formulation commonly prepared in the art, for example, solutions, suspensions, emulsions, pastes, gels, creams, lotions, powders, soaps, It may be formulated as a surfactant-containing cleansing, oil, powder foundation, emulsion foundation, wax foundation, spray, and the like, but is not limited thereto. More specifically, flexible lotion, astringent lotion, nutrition lotion, nutrition cream, massage cream, moisture cream, moisture gel cream, lotion, gel, essence, eye cream, peel-off mask pack, cleansing cream, cleansing foam, cleansing water, It may be prepared in the form of a pack, ointment, stick, patch, spray or powder.
  • the water-dispersible cellulose microfiber network dispersion according to the present invention may include 0.0001 to 10, preferably 0.0001 to 5, more preferably 0.0005 to 5 dry weight percent, based on the total weight of the cosmetic composition.
  • the present invention is a biocellulose microfiber network dispersion, preferably a maximum diameter of 60 to 100 nm, number average diameter of 30 to 60 nm, dispersion of water-dispersible biocellulose microfiber network, characterized in that the network is dispersed in the water phase Provided is a quasi-drug composition comprising a sieve.
  • the 'quasi drug' is used for the purpose of treating, alleviating, treating or preventing a symptom that is harmful to humans or animals, and has a weak effect on the human body or does not directly act on the human body,
  • an article corresponding to one of the agents used for sterilization, insecticide and similar purposes for the prevention of infections the apparatus being used for the purpose of diagnosing, treating, alleviating, treating or preventing diseases of humans or animals, Non-machines or devices, and articles used for the purpose of pharmacologically affecting the structure and function of humans or animals except articles other than instruments, machines or devices, and include external skin preparations and personal care products.
  • the 'skin external preparation' refers to a solid, semi-solid or liquid external preparation that can be easily applied to the skin by mixing the drug with various bases such as oils, petroleum jelly, lanolin, glycerol and the like.
  • External formulations are not particularly limited, but may include, for example, powder, gel, ointment, cream, liquid or aerosol formulations.
  • the water-dispersible cellulose microfiber network dispersion according to the present invention may comprise 0.0001 to 10, preferably 0.0001 to 5, more preferably 0.0005 to 5 dry weight percent, based on the total weight of the quasi-drug composition.
  • the water-dispersible biocellulose microfiber network dispersion or the composition comprising the same according to the present invention has a skin seizure property, water retention capacity, an increase in elasticity, and an ability to improve thickening and softness, and thus can be used as a useful method based thereon.
  • the water-dispersible biocellulose microfiber network dispersion according to the present invention or a composition comprising the same may be used as a method of enhancing moisture or increasing elasticity by applying to a human body.
  • the human body preferably includes skin.
  • the application may be included without limitation as long as it affects the human body directly or indirectly, for example, may be applied to the human body.
  • the water-dispersible biocellulose microfiber network dispersion or the composition comprising the same according to the present invention has a fine dust blocking ability, and can be used in a useful method based on these.
  • the water-dispersible biocellulose microfiber network dispersion according to the present invention or a composition containing the same may be used as a method for blocking fine dust.
  • the human body preferably includes skin.
  • the application may be included without limitation as long as it affects the human body directly or indirectly, for example, may be applied to the human body.
  • the water-dispersible biocellulose microfiber network dispersion according to the present invention or the composition comprising the same has a keratin structure protection ability, and can be used in a useful manner based on these.
  • the human body preferably includes skin.
  • the application may be included without limitation as long as it affects the human body directly or indirectly, for example, may be applied to the human body.
  • the water-dispersible biocellulose microfiber network dispersions or compositions comprising them according to the invention can be used for the protection of various keratin structures, for example when applied to hair pre-shampoo compositions, shampoos, rinses, treatments Formula, wax, gel, spray, mousse, hair lotion, hair pack, hair essence, hair cream, research hair dye, temporary hair dye, pump, nonwoven and sheet.
  • hair pre-shampoo compositions shampoos, rinses, treatments
  • wax, gel, spray, mousse, hair lotion, hair pack, hair essence, hair cream, research hair dye, temporary hair dye, pump, nonwoven and sheet for example, when applied to nails or toenails, it may be formulated with one or more selected from the group consisting of base, nail polish, top coat, nutrients, reinforcing agents and gels for nail trimming or protection.
  • the water-dispersible biocellulose microfiber network dispersion of the present invention maintains the length of the biocellulose raw material and maintains the fiber network even after being formulated with the composition, and the fine fibers formed on the skin have excellent skin adhesion, water absorption and elasticity effect. There is an effect to improve the softness, it can be very useful as a quasi-drug and cosmetics.
  • FIG. 1 is a photograph of cellulose microfibers of (a) Comparative Example 1 and (b) a water dispersion of cellulose microfibers network dispersion after chemical treatment of Example 1.
  • FIG. 1 is a photograph of cellulose microfibers of (a) Comparative Example 1 and (b) a water dispersion of cellulose microfibers network dispersion after chemical treatment of Example 1.
  • Example 2 is a photograph of a wood-based cellulose dispersion of Comparative Example 2 at a concentration of (a, b) 0.05, 0.015%; (c, d) It is a photograph of the water-dispersed biocellulose microfiber network dispersion of Example 1 at a concentration of 0.05, 0.015%.
  • FIG. 3 is a SEM photograph of pig skin before and after applying Example 1.
  • Figure 4 is a graph showing the contact angle change of water with time in the pig skin coated with cellulose according to the (a) Example and Comparative Example, and (b) a micrograph of the initial contact angle.
  • Example 5 is a graph showing friction force data measured after applying Example 1 to the skin.
  • Example 7 is a graph showing changes in contact angle of water with time in pig skin to which Comparative Example 5 and Example 2 are applied.
  • Example 8 is a SEM photograph of (a) a pig skin coated with Comparative Example 6, and (b) a SEM photograph of a pig skin coated with 0.01 dry weight of Example 1, (c, d) 0.05 dry weight of Example 1 SEM image of the skin of pigs coated.
  • Example 9 is a SEM photograph of (a) 0.05 dry weight% of Example 1 applied to pig skin and then coated with fine dust thereon, (b) SEM photograph of coated Comparative Example 6 to pig skin and then coated with fine dust thereon to be.
  • Figure 10 (a) SEM image (top) and fluorescence micrograph (bottom) (a) 0.05 dry weight% Comparative Example 7 was applied to the pig skin after applying Comparative Example 6 to the pig skin and the replacement fine dust on it (b) SEM image (top) and fluorescence micrograph (bottom) coated with replacement fine dust thereon (c) 0.05 dry weight% SEM image coated with replacement fine dust on pig skin after application of Example 1 to pig skin (top) And fluorescence micrographs (below).
  • FIG. 11 is a photograph taken by scanning electron microscopy (SEM) of an essence of an O / W emulsifier type containing a biocellulose microfiber water dispersion network prepared according to Example 6 on a human hair surface.
  • SEM scanning electron microscopy
  • FIG. 12 is a photograph of an essence of an O / W emulsifier type containing a biocellulose microfiber water dispersion network prepared according to Example 6, treated on a surface of a human nail, and dried and measured by a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • biocellulose Egycostec, Mita Parkdan
  • sodium hypochlorite 2,2,6,6-tetramethyl-1-piperidine-N-oxy radical (hereinafter referred to as TEMPO) catalyst
  • TEMPO 2,2,6,6-tetramethyl-1-piperidine-N-oxy radical
  • the diameter of the microfibers in the thus obtained biocellulose microfiber network dispersion was 60-100 nm in diameter, number average diameter 30-60 nm, and length was length of biocellulose (Easy Kostech, Mita Park Group). was maintained
  • Example 1 has a microfiber network structure
  • SEM scanning electron microscope
  • Example 1 is a biocellulose microfiber network dispersion prepared according to Preparation Example 1 described above.
  • Comparative Example 1 was prepared by putting a biocellulose sheet in distilled water and stirring.
  • Comparative Example 2 synthesized wood-based cellulose in the same manner as in Example 1. SEM photographs are shown in Figs. 1A and 2A and 2B.
  • Comparative Example 3 was prepared by putting carboxymethyl cellulose, which is a water-soluble cellulose commonly used as a cosmetic, in distilled water and stirring.
  • Comparative Example 4 was prepared by putting hydroxyethyl cellulose, a water-soluble cellulose commonly used as a cosmetic, in distilled water and stirring.
  • Comparative Example 5 is an essence formulation without Example 1.
  • Example 2 is an essence formulation comprising 0.015% dry weight of a water-dispersed biocellulose microfiber network dispersion according to Example 1.
  • Example 3 is an essence formulation comprising 0.03 dry weight percent of water-dispersed biocellulose microfiber network dispersion according to Example 1.
  • Comparative Example 2 which is a result of synthesizing wood-based cellulose raw material (Whatman, filter paper, 1005-110) in the same manner as in Preparation Example 1, was confirmed by SEM.
  • Diluting Comparative Example 2 to 0.05 dry weight% is shown in a of FIG. 2, and diluting to 0.015 dry weight% is shown in b of FIG. 2. As can be seen in Figures 2a and 2b, it shows a needle-like structure and does not form a network.
  • Example 1 has a number average diameter of 30-60 nm while maintaining a few tens of microns in length, showing a structure that forms an interfiber network even at low concentrations You can see that. Through this, it was confirmed that the wood-based cellulose and the bio-cellulose have different structures in terms of network formation, and thus also have different functions.
  • Example 1 0.03 dry weight of Example 1 was applied to the skin when applied to the skin to confirm whether it is seated on the skin (2cm x 2cm), then dried and confirmed by SEM. As can be seen in Figure 3, it was confirmed that the cellulose microfiber network dispersion was stably applied to the surface of the pig skin, through which proved that the microfibers were formed on the skin surface and seated.
  • Comparative Examples 2, 3, 4 and Example 1 were applied to the skin of pigs at 0.5% by dry weight, dried, and then dropped in water to measure contact angles. Initial contact angle was shown in the order of Comparative Example 4> Comparative Example 2> Comparative Example 3> Example 1, the smaller the contact angle means that it has a hydrophilic property.
  • Example 1 the change of the contact angle with time is shown in FIG.
  • the contact angle is sharply reduced, which means that the water-dispersed cellulose microfibers attract water quickly, thereby confirming the excellent moisturizing ability by increasing the water retention of the water-dispersible cellulose microfibers.
  • Example 2 After preparing the essence formulation (Comparative Example 5, Example 2) according to the presence / absence of cellulose microfiber dispersion in order to confirm the water retention of the water-dispersible cellulose microfiber network dispersion formulation (wt% is shown in Table 2). After applying to the pig skin, the water was dropped and dried to measure the contact angle. As a result, it was confirmed that the contact angle reduction in the formulation containing Example 1 was large over time (FIG. 7). This is because cellulose microfibers retain the property of attracting and absorbing water even if they are included in the formulation.
  • the elasticity measurement experiment was conducted to confirm the efficacy of the synthesized Example 1. After dissolving gelatin at a certain concentration in a well plate, the gel was hardened to form a gel. After dispersing the cellulose microfiber network dispersion, the elasticity was measured using a texture analyzer. In the universal physical analyzer, a specimen of a size smaller than the area of the gelatine gel was mounted, and the pressure was lowered by pressing down the gelatine gel at a constant speed. When the elasticity is increased, the structure of the surface is dense, and thus the principle of increasing the resistive force when pressed with a constant force is used.
  • Example 1 of Comparative Example 2 and 0.03 dry weight% were measured by the following In-vitro elasticity evaluation method, the treatment of Example 1 increased by about 20% compared to the treatment of Comparative Example 2. It was found that the applied cellulose microfibers increased the elasticity effect while forming a film. In addition, as a result of confirming the degree of elasticity improvement to 10 general people, it was confirmed that there is a significant increase.
  • Example 1 is a biocellulose microfiber network dispersion prepared according to Preparation Example 1 described above.
  • Comparative Example 6 is distilled water.
  • Comparative Example 7 is xanthan gum which is a water-soluble polymer.
  • Comparative Example 8 is an essence formulation without Example 1.
  • Comparative Example 9 is a skin formulation without Example 1.
  • Example 4 is an essence formulation comprising Example 1 at 0.05 dry weight percent.
  • Example 5 is a skin formulation comprising Example 1 at 0.05 dry weight percent.
  • Example 1 was applied to the skin when applied to the skin to confirm whether it is placed on the skin (2cm x 2cm), then dried and confirmed by SEM. As can be seen in Figure 1, it was confirmed that the skin surface of the pig skin is also coated with the biocellulose microfiber water dispersion network composition, through which proved that the microfibers formed on the surface of the skin is seated. In addition, when the interface between the coated and uncoated portions was measured to determine how much the dry weight of Example 1 was applied to 0.05% by weight, the coated portions were all covered with the biocellulose microfiber water dispersion network composition. It was confirmed. This confirms that when the biocellulose microfiber water dispersion network composition is applied to the skin, most of the skin is covered so that fine dust does not adhere to the skin.
  • Example 1 In order to confirm the charge of Example 1, an essence formulation shown in Table 3 was prepared, and zeta potentials of Comparative Example 8, Example 1, and Example 4 were measured. Table 4 shows the surface charge values of Examples 1 and 4 and Comparative Example 8. In the case of Example 1, the surface charge value showed a negative charge at ⁇ 77.5 mV, and in Example 2, the negative charge was stable at ⁇ 70.7 mV. However, Comparative Example 8 showed -7.1 mV. In the case of zeta potential measurement, a value between -20 mV and +20 mV cannot be regarded as showing a stable charge, and thus, in Comparative Example 8, it cannot be said to show a negative charge. Therefore, since the carboxyl group of the biocellulose microfiber water dispersion network composition has a negative charge, it was confirmed that the negative charge is stable even when applied to the formulation.
  • Example 1-5 um of replacement fine dust was applied together with the untreated control and dried, SEM And fluorescence microscopy confirmed that the replacement fine dust was in direct contact with the skin surface.
  • fluorescence microscopy the replacement fine dust is treated with red fluorescence, the skin is treated with green fluorescence, and the applied water-soluble polymer and biocellulose microfiber water dispersion are not fluorinated. It was confirmed that the skin directly contacted.
  • the formulations shown in Table 4 prepared a skin formulation containing the biocellulose microfiber water dispersion network composition and confirmed the degree of fine dust adhesion. Apply artificial sebum to PMMA plate in the amount of 1.3 mg / cm 2 and dry it, and then apply and dry the test product on artificial sebum dried in the same amount. Subsequently, after exposing 1-5 um of replacement fine dust for 5 minutes, the fine dust image attached to the PMMA plate was confirmed and evaluated.
  • Essence formulations were prepared and evaluated in the formulations shown in Table 3 (unit: weight percent). If fine dust adheres directly to the skin, it becomes difficult to clean and reduce cleaning efficiency. Therefore, a formulation comprising a certain amount of biocellulose microfiber network water dispersion and a composition comprising the biocellulose microfiber network water dispersion is applied to the skin, 1-5 ⁇ m of replacement fine dust is applied thereon, and washed with lukewarm water. The fine dust cleaning rate was evaluated by measuring the images before and after applying the fine dust.
  • the biocellulose microfiber water dispersion network was weighed in purified water, and then sufficiently wetted, and then uniformly dispersed at 1500 rpm for 30 minutes or more using a disper. Thereafter, raw materials 2 to 5 were added thereto, heated to 60 ° C., pre-weighed and mixed with raw materials 7 to 8 heated to 60 ° C., and then mixed at a homomixer at 4500 rpm for 10 minutes. After defoaming, filtration and cooling to complete the formulation.
  • the essence of the O / W emulsifier type containing the biocellulose microfiber water dispersion network prepared according to Example 6 was treated on the surface of human hair and nails and dried, followed by hair and nails using a scanning electron microscope (SEM). The surface was observed. 11 and 12, it was confirmed that the biocellulose microfiber dispersion network formed on the surface of the hair and nail surface covering the surface by forming a mesh-like network on the surface .
  • Table 8 shows the results of measuring the hair cross-sectional area before and after the essence treatment of the biocellulose microfiber water dispersion network-containing O / W emulsifier type prepared according to Example 6 with respect to the hair sample of Experimental Example 1.
  • the average cross-sectional area of the ten hair samples increased by about 8% from about 4012 mm 2 before the essence treatment to about 4350 mm 2 after the essence treatment. Therefore, even after the essence formulation is dried on the hair surface, it can be confirmed that the biocellulose microfiber water dispersion network is stably applied, thereby increasing the thickness of the hair.

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Abstract

La présente invention concerne une dispersion en réseau de microfibrilles de bio-cellulose dans l'eau, les microfibrilles de bio-cellulose ayant des groupes carboxyliques substitués à des groupes d'alcool ont un diamètre moyen en nombre de 30 à 60 nm avec un diamètre maximal de 60 à 100 nm, et étant dispersées dans une phase aqueuse tout en formant un réseau. La dispersion en réseau de microfibrilles de bio-cellulose dans l'eau selon la présente invention présente une excellente compatibilité avec la peau et a pour effet de permettre à la peau d'augmenter son absorption d'eau, son élasticité et son lissé. De plus, non seulement la dispersion en réseau de microfibrilles de bio-cellulose dans l'eau forme des micro-réseaux sur la peau pour empêcher les micro-poussières d'être amenées en contact direct avec la peau, mais également des charges négatives de la dispersion en réseau repoussent ces micro-poussières pour réduire la fixation des micro-poussières, de telle sorte que la présente invention peut être largement utilisée dans le développement d'une variété de compositions pour bloquer efficacement les micro-poussières. En outre, la dispersion de la présente invention a pour effet de former un réseau puissant sur une structure de kératine telle que les cheveux et les ongles des mains et des pieds pour protéger la structure de kératine, et de n'exercer aucun dommage sur la couche de cuticule superficielle de la structure de kératine même pendant son retrait.
PCT/KR2017/002358 2016-03-03 2017-03-03 Dispersion en réseau de microfibrilles de bio-cellulose dans l'eau WO2017150950A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US16/080,758 US20190060205A1 (en) 2016-03-03 2017-03-03 Networked dispersion of biocellulose microfibrils in water
CN201780012462.7A CN108697620A (zh) 2016-03-03 2017-03-03 生物纤维素微纤维水分散体的网络组合物
EP17760354.5A EP3424487B1 (fr) 2016-03-03 2017-03-03 Dispersion en réseau de microfibrilles de bio-cellulose dans l'eau
JP2018545610A JP7004387B2 (ja) 2016-03-03 2017-03-03 バイオセルロース微細繊維水分散体ネットワーク組成物

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KR10-2016-0025765 2016-03-03
KR20160025765 2016-03-03
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KR20160100603 2016-08-08
KR10-2016-0100599 2016-08-08
KR1020170002301A KR20170103628A (ko) 2016-03-03 2017-01-06 셀룰로오스 나노섬유 수분산체 조성물
KR10-2017-0002301 2017-01-06
KR10-2017-0027863 2017-03-03
KR1020170027863A KR101816792B1 (ko) 2016-03-03 2017-03-03 바이오셀룰로오스 미세섬유 수분산체 네트워크 조성물
KR10-2017-0027902 2017-03-03
KR1020170027721A KR102349932B1 (ko) 2016-08-08 2017-03-03 케라틴 구조체 보호용 바이오셀룰로오스 미세섬유 수분산체 네트워크 조성물
KR10-2017-0027721 2017-03-03
KR1020170027902A KR102399486B1 (ko) 2016-08-08 2017-03-03 미세먼지 차단용 바이오셀룰로오스 미세섬유 수분산체 네트워크 조성물

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KR102222152B1 (ko) * 2019-02-14 2021-03-03 류지만 미세먼지 제거용 기능성 마스크팩 및 이의 제조방법
KR20200099636A (ko) * 2019-02-14 2020-08-25 류지만 미세먼지 제거용 기능성 마스크팩 및 이의 제조방법

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