WO2018194079A1 - 生体組織貼付けパッチ - Google Patents
生体組織貼付けパッチ Download PDFInfo
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- WO2018194079A1 WO2018194079A1 PCT/JP2018/015962 JP2018015962W WO2018194079A1 WO 2018194079 A1 WO2018194079 A1 WO 2018194079A1 JP 2018015962 W JP2018015962 W JP 2018015962W WO 2018194079 A1 WO2018194079 A1 WO 2018194079A1
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- WIPO (PCT)
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- positive electrode
- negative electrode
- battery
- active ingredient
- conductive layer
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
- A61N1/00—Electrotherapy; Circuits therefor
- A61N1/02—Details
- A61N1/04—Electrodes
- A61N1/0404—Electrodes for external use
- A61N1/0408—Use-related aspects
- A61N1/0428—Specially adapted for iontophoresis, e.g. AC, DC or including drug reservoirs
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
- A61N1/00—Electrotherapy; Circuits therefor
- A61N1/02—Details
- A61N1/04—Electrodes
- A61N1/0404—Electrodes for external use
- A61N1/0408—Use-related aspects
- A61N1/0428—Specially adapted for iontophoresis, e.g. AC, DC or including drug reservoirs
- A61N1/0448—Drug reservoir
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/0002—Galenical forms characterised by the drug release technique; Application systems commanded by energy
- A61K9/0009—Galenical forms characterised by the drug release technique; Application systems commanded by energy involving or responsive to electricity, magnetism or acoustic waves; Galenical aspects of sonophoresis, iontophoresis, electroporation or electroosmosis
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/70—Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug
- A61K9/7023—Transdermal patches and similar drug-containing composite devices, e.g. cataplasms
- A61K9/703—Transdermal patches and similar drug-containing composite devices, e.g. cataplasms characterised by shape or structure; Details concerning release liner or backing; Refillable patches; User-activated patches
- A61K9/7084—Transdermal patches having a drug layer or reservoir, and one or more separate drug-free skin-adhesive layers, e.g. between drug reservoir and skin, or surrounding the drug reservoir; Liquid-filled reservoir patches
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
- A61N1/00—Electrotherapy; Circuits therefor
- A61N1/02—Details
- A61N1/04—Electrodes
- A61N1/0404—Electrodes for external use
- A61N1/0408—Use-related aspects
- A61N1/0428—Specially adapted for iontophoresis, e.g. AC, DC or including drug reservoirs
- A61N1/0432—Anode and cathode
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
- A61N1/00—Electrotherapy; Circuits therefor
- A61N1/18—Applying electric currents by contact electrodes
- A61N1/20—Applying electric currents by contact electrodes continuous direct currents
- A61N1/30—Apparatus for iontophoresis, i.e. transfer of media in ionic state by an electromotoric force into the body, or cataphoresis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a biological tissue adhesive patch that is attached to a biological tissue and allows an active ingredient to penetrate into the biological tissue with a weak current, and a battery included in the biological tissue adhesive patch.
- Liquid and cream cosmetics and pharmaceuticals are widely used.
- a technique for attracting active ingredients of cosmetics and pharmaceuticals into a living body with a weak current has been attracting attention.
- a technique using a weak current is known to have an effect of enhancing cell activation and drug penetration, it requires an expensive and large-sized power supply device.
- a biological tissue affixing patch having a power supply device using a general dry battery is known.
- a power supply device using a general dry battery uses materials harmful to the dry battery and the power supply device, rare metals, and the like, there are problems of reducing environmental burden and simplifying disposal.
- Non-patent Document 1 A biological tissue affixing patch that does not require a power supply and has a low environmental load is also known.
- the living tissue affixing patch of Non-Patent Document 1 includes a biofuel cell.
- the present invention has been made in view of the above, and there is no need to change the form of liquid and cream chemical products that are widely used in the market. It aims at providing the biological tissue sticking patch which can suppress the self-discharge of a battery part, maintaining by.
- the biological tissue adhesive patch according to the present invention is a biological tissue adhesive patch that is used by being applied to a biological tissue, and is an active ingredient that is accommodated so as not to contact the battery part and the battery part.
- the battery component is brought into contact with the active ingredient to start a battery reaction.
- a biological tissue application patch capable of suppressing self-discharge can be provided.
- FIG. 1 is a plan view showing the configuration of the biological tissue sticking patch of the present embodiment.
- FIG. 2 is a diagram showing a state in which an active ingredient is brought into contact with the battery part by breaking the partition wall of the biological tissue sticking patch of FIG.
- FIG. 3 is a diagram illustrating a state in which the battery unit of FIG. 2 is used by being attached to a living tissue.
- FIG. 4 is a diagram schematically showing the configuration of the battery part in which the separator is separated into a positive electrode part separator and a negative electrode part separator.
- FIG. 5 is a diagram schematically showing a configuration of a battery part in which the conductive layer is separated into a positive electrode part conductive layer and a negative electrode part conductive layer.
- FIG. 6 is a flowchart showing a method for producing bacterially produced carbonized cellulose.
- FIG. 7 is a flowchart showing a step of supporting a catalyst on bacterially produced cellulose cellulose.
- FIG. 8 is a flowchart showing another method for manufacturing the positive electrode.
- FIG. 9 is a flowchart showing a method for manufacturing a negative electrode.
- FIG. 10 is an exploded perspective view of the battery unit of Examples 1 and 6.
- FIG. 11 is a cross-sectional view of the battery portion of Examples 1 and 6.
- FIG. 12 is a plan view illustrating a configuration of the biological tissue sticking patch according to the first embodiment.
- FIG. 13 is a diagram illustrating a configuration of the test apparatus.
- FIG. 13 is a diagram illustrating a configuration of the test apparatus.
- FIG. 14 is a diagram illustrating a state in which the battery unit is arranged in the test apparatus.
- FIG. 15 is a perspective view of the biological tissue sticking patch of Comparative Example 1.
- FIG. 16 is a cross-sectional view of the biological tissue sticking patch of Comparative Example 1.
- FIG. 17 is a graph showing the measurement results.
- FIG. 18 is an exploded perspective view of the battery unit of the second embodiment.
- FIG. 19 is a cross-sectional view of the battery unit of Example 2.
- FIG. 20 is an exploded perspective view of the battery parts of Examples 3 to 5.
- FIG. 21 is a cross-sectional view of the battery parts of Examples 3 to 5.
- FIG. 22 is an exploded perspective view of the battery unit of Examples 7 and 8.
- FIG. 23 is a cross-sectional view of the battery parts of Examples 7 and 8.
- FIG. 24 is a graph showing the measurement results.
- the biological tissue sticking patch of the present embodiment is a patch for allowing an active ingredient to penetrate into the living tissue by electricity generated by a reaction similar to that of a general magnesium-air battery.
- FIG. 1 is a plan view showing a configuration of a biological tissue sticking patch according to the present embodiment.
- a biological tissue patch 1 shown in FIG. 1 has a battery part 2 and an active ingredient 3.
- the battery part 2 and the active ingredient 3 are housed separately in the plastic pack 4.
- the battery unit 2 does not include an electrolyte required for a general battery, and is stored in a state where no battery reaction occurs.
- the active ingredient 3 may be liquid, cream, or gel as long as it functions as an electrolyte of the battery unit 2 when the biological tissue patch 1 is used.
- the separator of the battery part 2 is impregnated with the active ingredient 3, the active ingredient 3 acts as an electrolyte and the battery reaction starts.
- the plastic pack 4 includes a battery unit storage unit 42 that stores the battery unit 2 and an active ingredient storage unit 43 that stores the active ingredient 3.
- the battery part storage part 42 and the active ingredient storage part 43 are separated by a partition wall 41. Both ends 44 and 45 of the plastic pack 4 are sealed with a heat seal.
- a material of the plastic pack 4 for example, various materials such as vinyl, polystyrene, and acrylic can be used.
- polyvinyl chloride polyvinylidene chloride, polyvinyl alcohol, polystyrene, styrene / acrylonitrile copolymer, styrene / butadiene / acrylonitrile copolymer, high density polyethylene, medium density polyethylene, low density polyethylene, ethylene / acetic acid.
- vinyl copolymer polypropylene, homopolymer polyacetal, copolymer polyacetal, polymethyl methacrylate, polyester, PPS, polypropylene, cellophane, acetate, polycarbonate, nylon, and polyimide.
- the partition wall 41 is not particularly limited as long as the battery part 2 and the active ingredient 3 can be separated and accommodated.
- the battery unit storage unit 42 and the active ingredient storage unit 43 may be isolated by heat sealing, an adhesive, or a chuck.
- heat sealing is preferable from the viewpoint of complexity during production and cost.
- the biological tissue patch 1 can include structural members such as an exterior film, a case, an adhesive, and a metal foil, and elements required for a general magnesium-air battery. Conventionally known ones can be used.
- the active ingredient 3 When using the tissue patch 1, the active ingredient 3 is brought into contact with the battery unit 2.
- the active ingredient 3 plays the same function as the electrolyte, and the battery reaction starts in the battery part 2.
- the partition wall 41 As shown in FIG. 2, the partition wall 41 is broken to form an opening 46, and the active ingredient 3 is brought into contact with the battery unit 2.
- a method of breaking the partition wall 41 a method of applying pressure by pushing the active ingredient storage unit 43 storing the active ingredient 3 with a finger is preferable because it is easy and low in cost.
- the active ingredient storage unit 43 is folded in half and pushed to increase the pressure and break the partition wall 41.
- the method of breaking the partition wall 41 is not particularly limited, and examples thereof include a method of making a hole with a sharp needle or a toothpick, a method of cutting the partition wall 41 with scissors, and a method of tearing the partition wall 41 by hand.
- the battery part 2 taken out from the battery part storage part 42 is attached to the living tissue 100 and used.
- the shapes of the tissue sticking patch 1 and the battery unit 2 are not particularly limited. For example, a patch shape, a face mask shape, an eye mask shape, a glove shape, a bandage shape, a bandage shape, or a poultice shape may be used.
- FIG. 4 is a diagram schematically showing an example of the configuration of the battery part 2 in which the separator is separated into a positive electrode part separator and a negative electrode part separator.
- the positive electrode part separator 203A and the negative electrode part separator 203B are not in contact with each other and are not provided with an electrolyte. 4 uses the positive electrode part separator 203A and the negative electrode part separator 203B attached to the living tissue 100 for use.
- FIG. 5 is a diagram schematically showing an example of the configuration of the battery unit 2 in which the conductive layer is separated into a positive electrode part conductive layer and a negative electrode part conductive layer.
- 5 includes a positive electrode 201, a negative electrode 202 including magnesium, a separator 203 disposed in contact with the positive electrode 201 and the negative electrode 202, and a negative electrode 202 in contact with the positive electrode 201.
- the positive electrode part conductive layer 204 ⁇ / b> A is disposed so as not to contact the positive electrode 202
- the negative electrode part conductive layer 204 ⁇ / b> B is disposed so as to be in contact with the negative electrode 202 and is not contacted with the positive electrode 201.
- 5 is different from a general magnesium-air battery, the separator 203 does not include an electrolyte. 5 uses the positive electrode portion conductive layer 204A and the negative electrode portion conductive layer 204B attached to the living tissue 100.
- the separator 203 and the conductive layer 204 may not be separated into a positive electrode unit and a negative electrode unit.
- the reaction represented by the following formula (1) proceeds when water contained in the active ingredient 3 comes into contact with oxygen in the air.
- the reaction represented by the following formula (2) proceeds. Specifically, magnesium constituting the negative electrode 202 emits electrons and dissolves in the active ingredient 3 as magnesium ions.
- the whole battery reaction is the following formula (3), which is a reaction for producing magnesium hydroxide.
- the theoretical electromotive force is about 2.7V. 4 and 5 show the compounds involved in the reaction together with the components of the battery unit 2.
- the positive electrode 201 a positive electrode used in a general magnesium-air battery can be used.
- carbon, metal, oxide, nitride, carbide, sulfide, and phosphide can be used. Two or more of these may be mixed.
- the positive electrode 201 can be produced by a known process in which carbon powder is molded with a binder. Since the binder generally uses a resin containing fluorine, hydrofluoric acid is generated when the positive electrode 201 is burned by disposal or the like. Therefore, there is room for improvement such as safety improvement and environmental load reduction. In this embodiment, the resin containing fluorine is unused by using bacterially produced cellulose carbon or cellulose nanofiber carbon for the positive electrode 201.
- the bacterial-produced carbonized cellulose used for the positive electrode 201 has a three-dimensional network structure of carbonized bacterial-produced cellulose.
- the average pore diameter is preferably 0.1 to 50 ⁇ m, and more preferably 0.1 to 2 ⁇ m. preferable.
- the average pore diameter is a value obtained by mercury porosimetry.
- the cellulose nanofiber carbon used for the positive electrode 201 has a three-dimensional network structure of carbonized cellulose nanofibers.
- the fiber diameter is preferably 5 to 500 nm, and more preferably 20 to 200 nm.
- the positive electrode 201 may carry a catalyst.
- Catalysts are metals, oxides, nitrides, carbides, sulfides, and phosphides. Two or more of these may be mixed.
- the metal iron, manganese, copper, nickel, silver, gold, platinum, cobalt, ruthenium, molybdenum, titanium, chromium, gallium, praseodymium, aluminum, silicon, and tin can be used.
- An alloy containing two or more of these may be used.
- As the oxide an oxide composed of one of the above metals or a composite oxide composed of two or more metals is preferable. In particular, iron oxide (Fe 2 O 3 ) is suitable.
- Iron oxide is preferable in that it exhibits particularly excellent catalytic performance and is not a rare metal.
- the metal oxide used as the catalyst is preferably an amorphous hydrate.
- the transition metal oxide hydrate described above may be used. More specifically, iron (III) -n hydrate may be used.
- n is the number of moles of H 2 O with respect to 1 mol of Fe 2 O 3 .
- Excellent performance is achieved by attaching (adding) nano-sized fine particles of iron oxide hydrate (Fe 2 O 3 .nH 2 O) to the surface of bacteria-produced carbonized cellulose of the positive electrode 201 with high dispersion.
- the content of the catalyst contained in the positive electrode 201 is 0.1 to 70% by weight, preferably 1 to 30% by weight, based on the total weight of the positive electrode 201.
- the reaction represented by the above formula (1) proceeds on the surface of the positive electrode 201. Therefore, it is important to generate a large amount of reaction sites inside the positive electrode 201, and the positive electrode 201 desirably has a high specific surface area.
- the specific surface area of the positive electrode 201 is preferably 200 m 2 / g or more, and more preferably 300 m 2 / g or more.
- the negative electrode 202 is comprised with a negative electrode active material.
- the negative electrode active material may be any material that can be used as a negative electrode material for a magnesium-air battery, that is, metal magnesium and a material containing magnesium.
- the negative electrode 202 may be made of, for example, metallic magnesium, a metallic magnesium sheet, or magnesium powder. Iron, zinc, aluminum, calcium, lithium, and sodium that can be used as metal-air batteries other than magnesium can also be used as the negative electrode material. It is most preferable to use magnesium from the viewpoint of safety and battery output.
- the separator 203, the positive electrode part separator 203 ⁇ / b> A, and the negative electrode part separator 203 ⁇ / b> B may be any substance that can contain the active ingredient 3 and does not have conductivity.
- Japanese paper, cotton, collagen, bacterial production gel, and bacterial production xerogel can be used. Since the bacterially produced xerogel is porous, the retention performance of the active ingredient 3 is high. Since the bacterial production xerogel is gelled when the active ingredient 3 is retained, it has excellent adhesion to living tissue.
- the separator is divided into the positive electrode separator 203A and the negative electrode separator 203B so as not to contact each other as in the battery unit 2 of FIG. This is because when the positive electrode part separator 203A and the negative electrode part separator 203B are in contact with each other, the battery reaction proceeds without passing through the living tissue, and the ion introduction effect of the active ingredient 3 is diminished.
- the conductive layer 204, the positive electrode portion conductive layer 204A, and the negative electrode portion conductive layer 204B are not particularly limited as long as they are conductive materials. Examples thereof include carbon cloth, carbon sheet, metal mesh, metal wire, conductive cloth, conductive rubber, and conductive polymer.
- the electric resistance value of the conductive layer 204 By adjusting the electric resistance value of the conductive layer 204, the speed of the battery reaction can be adjusted. When the resistance value of the conductive layer 204 is increased, the ion introduction speed of the active ingredient 3 becomes slow. In the case where pain is caused by ion introduction too early, the resistance value of the conductive layer 204 may be increased.
- the performance of the living tissue attaching patch 1 can be further improved if the conductive layer 204 has a liquid repellency.
- the conductive layer 204 does not have liquid repellency, the conductive layer 204 absorbs the active ingredient 3 and the battery reaction proceeds without passing through the living tissue. As a result, the ion introduction effect of the active ingredient 3 is reduced.
- the conductive layer 204 may be coated with a plastic film, a silicon-based silane compound, a fluorine-based resin, or a metal film.
- a plastic film is suitable because it is low in cost and excellent in workability.
- plastic film for example, various materials such as vinyl, polystyrene, and acrylic can be used.
- the copolymer include polypropylene, monopolymer polyacetal, copolymer polyacetal, polymethyl methacrylate, polyester, PPS, polypropylene, cellophane, acetate, polycarbonate, nylon, and polyimide.
- the conductive layer is divided into the positive electrode part conductive layer 204A and the negative electrode part conductive layer 204B and not in contact with each other as in the battery part 2 of FIG. . This is because when the positive electrode part conductive layer 204A and the negative electrode part conductive layer 204B are in contact with each other, the battery reaction proceeds without passing through the living tissue, and the ion introduction effect of the active ingredient 3 is diminished.
- the “active ingredient” of the present embodiment is a chemical solution that has an effect on a specific disease, and aims to cleanse, beautify, increase the appeal, change the appearance, and maintain healthy skin or hair.
- a chemical solution that has an effect on a specific disease, and aims to cleanse, beautify, increase the appeal, change the appearance, and maintain healthy skin or hair.
- the active ingredient 3 may be any substance that can move magnesium ions and hydroxide ions between the positive electrode 201 and the negative electrode 202 via the living tissue 100 or the separator 203.
- the active ingredient can include an aqueous solution containing organic and inorganic acids, derivatives thereof, and salts thereof.
- the active ingredient includes, for example, amino acid ions, chloride ions, citrate ions, lactate ions, succinate ions, phosphate ions, malate ions, pyrrolidone carboxylate ions, sulfococolate ions, sulfate ions, and nitrate ions. Ions, carbonate ions, and perchlorate ions.
- amino acids As amino acids, glycine, alanine, valine, leucine, isoleucine, phenylalanine, tyrosine, threonine, serine, proline, tryptophan, methionine, cysteine, aspartic acid, glutamic acid, asparagine, glutamine, lysine, arginine, histidine, hydroxyproline, cystine, And thyroxine.
- Examples of the cationic species include potassium ions, sodium ions, lithium ions, calcium ions, magnesium ions, and zinc ions.
- active ingredients include, for example, sodium salts of amino acids, sodium chloride, potassium chloride, magnesium chloride, sodium citrate, magnesium citrate, sodium lactate, magnesium lactate, calcium lactate, sodium succinate, magnesium succinate, apples
- active ingredients include sodium acid, magnesium malate, sodium pyrrolidonecarboxylate, magnesium pyrrolidonecarboxylate, zinc sulfocolate, potassium aluminum sulfate (alum), seawater, and hot spring water.
- magnesium ions and hydroxide ions Even if it is an active ingredient that does not cause migration of magnesium ions and hydroxide ions, the above-mentioned sodium salts of amino acids, sodium chloride, potassium chloride, magnesium chloride, sodium citrate, magnesium citrate, sodium lactate, magnesium lactate , Calcium lactate, sodium succinate, magnesium succinate, sodium malate, magnesium malate, sodium pyrrolidone carboxylate, magnesium pyrrolidone carboxylate, zinc sulfocolate, potassium aluminum sulfate (alum), sea water, and hot spring water Then, magnesium ions and hydroxide ions may be moved.
- the active ingredient is almost all pharmaceuticals that are generally marketed by the method of containing magnesium acid, sodium pyrrolidonecarboxylate, magnesium pyrrolidonecarboxylate, zinc sulfocolate, potassium aluminum sulfate (alum), seawater, and hot spring water. Quasi-drugs, cosmetics and supplements can be used.
- pharmaceuticals for example, pharmaceuticals, quasi drugs, cosmetics, and supplements include the following.
- anti-aging effects include uric acid, glutathione, meatonin, polyphenol, melanoidin, astaxanthin, kinetin, epigallocatechin gallate, coenzyme Q10, vitamins, superoxide dismutase, mannitol, quercetin, catechin and derivatives thereof, rutin And derivatives thereof, button pi extract, yashajitsu extract, melissa extract, rahan fruit extract, dibutylhydroxytoluene, and butylhydroxyanisole.
- Examples of those having a whitening effect include whitening agents and anti-inflammatory agents.
- the whitening agent has the effect of preventing the darkening of skin caused by sunburn and the generation of spots and freckles caused by pigmentation.
- Whitening agents include, for example, arbutin, ellagic acid, linoleic acid, vitamin C and its derivatives, kojic acid, tranexamic acid, placental extract, chamomile extract, licorice extract, age extract, seaweed extract, seaweed extract, Kujijin extract, keiquette extract, gokahi extract, rice bran extract, wheat germ extract, saicin extract, hawthorn extract, sunpens extract, shirayuri extract, peonies extract, sempukuka extract, soybean extract, tea Examples include an extract, molasses extract, juniper extract, grape extract, hop extract, micaika extract, mokka extract, and yukinoshita extract.
- the anti-inflammatory agent has an action of suppressing inflammation of the hot flashes and erythema after sunburn.
- Anti-inflammatory agents include, for example, sulfur and its derivatives, glycyrrhizic acid and its derivatives, glycyrrhetinic acid and its derivatives, Artea extract, Ahibatagisou extract, chamomile extract, goldfish extract, watercress extract, comfrey extract, salvia Examples include extracts, sicon extracts, perilla extracts, shikaraba extracts, and gentian extracts.
- Examples of those having a peeling and brightening effect include ⁇ -hydroxy acid, salicylic acid, sulfur, and urea.
- substances having a slimming effect include substances having effects such as blood circulation promotion, for example, plant extracts such as ginger, chili pepper, and clara root, carbon dioxide, vitamin E, and derivatives thereof.
- proteins such as elastin and keratin and derivatives thereof and hydrolysis and salts thereof, amino acids such as glycine, serine, asoaraginic acid, glutamic acid, arginine and theanine and derivatives thereof, sorbitol, Erythritol, trehalose, inositol, glucose, sucrose and derivatives thereof, dextrin and derivatives thereof, saccharides such as honey, D-pantenol and derivatives thereof, sodium lactate, sodium pyrrolidonecarboxylate, sodium hyaluronate, mucopolysaccharide, urea, Examples include phospholipids, ceramides, auren extracts, ginger extracts, ginger extracts, nematode extracts, mallow extracts, marronnier extracts, and quince extracts.
- amino acids such as glycine, serine, asoaraginic acid, glutamic acid, arginine and theanine and derivatives thereof, sorbi
- Examples of those having a hair repairing effect include isopropylmethylphenol, ginkgo biloba extract, L-menthol, carpronium chloride, diphenhydramine hydrochloride, cashew (Tuldokudami), glycyrrhizic acid (dipotassium), salicylic acid, dialkylmonoamine derivatives, gyoza, cephalanthin,
- Examples include ginseng, assembly, chigetsu carrot, ginseng, chili pepper, toki, trehalose, nicotinic acid / nicotinic acid amide, vitamin E (tocopherol), hinokitiol, placenta extract, and pentadecanoic acid glyceride.
- substances having a skin conditioning effect include substances intended to improve rough skin such as barrier function improvement or damage healing.
- the skin conditioning effect include ceramides, cholesterols, amine derivatives, caffeine, chicken crown extract, shell extract, royal jelly, silk protein and degradation products thereof, derivatives thereof, lactoferrin and degradation products thereof, Mucopolysaccharides such as chondroitin sulfate and hyaluronic acid and their salts, collagen, yeast extract, lactic acid bacteria extract, bifidobacteria extract, fermentative metabolic extract, ginkgo biloba extract, barley extract, assembly extract, lysium extract , Carrot extract, arnica extract, turmeric extract, eucalyptus extract, gama extract, scorpion extract, rosemary extract, glycol extract, citric acid, lactic acid, malic acid, tartaric acid, and succinic acid .
- Examples of those having a relaxing effect include lavender, rosemary, sandalwood, oris, bitter orange, cypress, and orange oil.
- medical agents may be used individually by 1 type, and may be used in combination of 2 or more type.
- cosmetics include lotion, milky lotion, beauty essence, cream, cream pack, massage cream, cleansing cream, cleansing gel, face washing foam, sunscreen, styling gel, shampoo, body shampoo, hair setting gel, fragrance, and Examples include hair dyes. According to these cosmetics, effects of anti-aging, whitening, peeling / brightening, slimming, moisturizing, hair restoration, hair growth, skin conditioning, relaxation, and UV protection can be obtained.
- these cosmetics may be used alone or in combination of two or more.
- FIG. 6 is a flowchart showing a method for producing bacterially produced carbonized cellulose.
- step S101 a gel in which cellulose nanofibers are dispersed is produced in predetermined bacteria.
- the freezing step of step S102 the gel produced by the bacteria is frozen to obtain a frozen body.
- the drying step of step S103 the frozen body is dried in vacuum.
- Bacterial xerogel is obtained by the above process.
- the carbonization step of step S104 the bacteria-produced xerogel is heated and carbonized in an atmosphere of gas in which cellulose does not burn. Thereby, a bacteria-produced carbonized cellulose is obtained.
- the gel means a solid that has lost fluidity due to a three-dimensional network structure of nanostructures in which the dispersion medium is a dispersoid. Specifically, it means a dispersion having a shear modulus of 10 2 to 10 6 Pa.
- an aqueous system such as water (H 2 O) can be used.
- the dispersion medium of the gel may be carboxylic acid, methanol (CH 3 OH), ethanol (C 2 H 5 OH), propanol (C 3 H 7 OH), n-butanol, isobutanol, n-butylamine, dodecane,
- Organic systems such as saturated fatty acids, ethylene glycol, heptane, hexadecane, isoamyl alcohol, octanol, isopropanol, acetone, and glycerin can be used. Two or more of these may be mixed.
- Gels produced by bacteria have a basic structure of nano-order nanofibers (fibrous substances having a diameter of 1 nm to 1 ⁇ m and a length of 100 times or more of the diameter).
- the positive electrode 201 produced using this gel has a high specific surface area. Since it is desirable that the positive electrode 201 of the biological tissue patch 1 has a high specific surface area, it is preferable to use a gel produced by bacteria. Specifically, the cathode 201 having a specific surface area of 300 m 2 / g or more can be synthesized by using a gel produced by bacteria.
- the bacteria-producing gel has a structure in which fibers are entangled in a coil shape and a mesh shape, and further has a structure in which nanofibers formed by bacterial growth are branched. Therefore, the positive electrode 201 produced from a bacteria-producing gel achieves excellent stretchability with a strain at the elastic limit of 50% or more. Therefore, the positive electrode 201 manufactured using a bacterial production gel can improve the adhesion with a living tissue.
- Bacteria include known ones, such as Acetobacter xylinum subsp. Scrofermenta, Acetobacter xylinum ATCC 23768, Acetobacter xylinum ATCC 23769, Acetobacter pasturinus ATCC 10245, Acetobacter xylinum ATCC 148551, Acetobacter Examples include acetic acid bacteria such as Bacter xylinum ATCC 11142 and Acetobacter xylinum ATCC 10821. Alternatively, it may be a bacterium produced by culturing various mutant strains created by mutating the above-mentioned bacteria by a known method using NTG (nitrosoguanidine) or the like.
- the bacteria-producing gel is accommodated in a suitable container such as a test tube, and the bacteria-producing gel is frozen by cooling the periphery of the test tube in a coolant such as liquid nitrogen.
- the method for freezing the bacteria-producing gel is not particularly limited as long as the gel dispersion medium can be cooled below the freezing point, and may be cooled in a freezer or the like.
- the dispersion medium loses fluidity and the dispersoid cellulose is fixed, and a three-dimensional network structure is constructed.
- cellulose that is a dispersoid is not fixed by freezing, the dispersoid aggregates in the subsequent drying step as the dispersion medium evaporates. Therefore, a sufficient high specific surface area cannot be obtained, and it becomes difficult to produce a high-performance positive electrode 201.
- the drying step is a step in which the frozen body obtained in the freezing step is dried, and cellulose, which is a dispersoid maintaining or constructing a three-dimensional network structure, is taken out from the dispersion medium.
- the frozen body is dried in a vacuum, and the frozen dispersion medium is sublimated from the solid state.
- the drying step is performed, for example, by storing the obtained frozen body in a suitable container such as a flask and evacuating the container. By disposing the frozen body in a vacuum atmosphere, the sublimation point of the dispersion medium is lowered, and a substance that does not sublime at normal pressure can be sublimated.
- the degree of vacuum in the drying step varies depending on the dispersion medium used, but is not particularly limited as long as the degree of vacuum allows the dispersion medium to sublime.
- the degree of vacuum is preferably 1.0 ⁇ 10 ⁇ 6 to 1.0 ⁇ 10 ⁇ 2 Pa. Further, heat may be applied using a heater or the like during drying. In the method of drying in the atmosphere, the dispersion medium changes from solid to liquid and from liquid to gas.
- Bacteria-produced carbonized cellulose has a conductive three-dimensional network structure. Bacteria-produced carbonized cellulose has high conductivity, corrosion resistance, high stretchability, and a high specific surface area, and is suitable as the positive electrode 201 of the biological tissue patch 1.
- the bacteria-produced xerogel may be baked and carbonized in an inert gas atmosphere at 500 degrees Celsius to 2000 degrees Celsius, more preferably 900 degrees Celsius to 1800 degrees Celsius.
- the gas that does not burn cellulose include inert gases such as nitrogen gas and argon gas.
- the gas used may be a reducing gas such as hydrogen gas or carbon monoxide gas, or carbon dioxide gas. Carbon dioxide gas or carbon monoxide gas, which has an activation effect on the carbon material and can be expected to be highly activated, is more preferable.
- FIG. 7 is a flowchart showing a process of supporting a catalyst on bacterially produced carbonized cellulose.
- the bacterial-produced carbonized cellulose obtained by the above-described production method is impregnated with an aqueous solution of a metal salt that serves as a catalyst precursor.
- the bacteria-produced carbonized cellulose containing the metal salt is heat-treated.
- a preferable metal as the metal salt is at least one metal selected from iron, manganese, copper, nickel, silver, gold, platinum, cobalt, ruthenium, molybdenum, titanium, chromium, gallium, praseodymium, aluminum, silicon, and tin. is there. Iron is preferred because of its low environmental impact and high electrode performance.
- a conventionally known method can be used. For example, a method in which bacterially produced carbonized cellulose is impregnated with an aqueous solution of transition metal chloride or transition metal nitrate and evaporated to dryness, followed by hydrothermal synthesis in water at high temperature and high pressure, transition metal chloride or transition to bacterially produced cellulose There are a precipitation method in which an aqueous solution of a metal nitrate is impregnated and an alkaline aqueous solution is dropped therein, or a sol-gel method in which a transition metal alkoxide solution is impregnated in a transition metal alkoxide solution and hydrolyzed.
- the conditions of each method by these liquid phase methods are well-known, and these well-known conditions can be applied. Since the transition metal oxide can be supported in a highly dispersed state, these liquid phase methods are desirable.
- the metal oxide supported by the liquid phase method is in an amorphous state because crystallization has not progressed.
- a crystalline metal oxide can be obtained by heat-treating the precursor in an amorphous state at a high temperature of about 500 degrees Celsius in an inert atmosphere. Such a crystalline metal oxide exhibits high performance even when used as a positive electrode catalyst.
- the precursor powder obtained when the above amorphous precursor is dried at a relatively low temperature of about 100 to 200 degrees Celsius is in a hydrated state while maintaining an amorphous state.
- the metal oxide hydrate is formally Me x O y ⁇ nH 2 O (where Me means the above metal, x and y are the number of metals and oxygen contained in the metal oxide molecule, respectively). Where n is the number of moles of H 2 O per mole of metal oxide).
- a metal oxide hydrate obtained by such low-temperature drying can be used as a catalyst.
- An amorphous metal oxide (hydrate) has a large surface area because sintering has hardly progressed, and the particle size is as small as about 30 nm. This is suitable as a catalyst, and by using this, excellent battery performance can be obtained.
- the particle diameter may be about 100 nm due to particle aggregation.
- the particle diameter (average particle diameter) is a value obtained by observing with a scanning electron microscope (SEM) or the like, measuring the diameter of particles per 10 ⁇ m square (10 ⁇ m ⁇ 10 ⁇ m), and calculating the average value. .
- the metal oxide catalyst that has been heat-treated particularly at high temperature aggregates the particles, it may be difficult to add the catalyst in a highly dispersed state on the surface of the bacterially produced cellulose.
- the amorphous precursor may be dried at a relatively low temperature of about 100 degrees Celsius to 200 degrees Celsius.
- the cathode 201 can be cut out into a desired rectangle (for example, 30 mm ⁇ 20 mm).
- Bacteria-producing carbonized cellulose obtained by the above production method is fragile and may be difficult to process into a desired shape. Therefore, by using another manufacturing method shown below, it becomes easy to process the bacteria-produced carbonized cellulose into a sheet.
- FIG. 8 is a flowchart showing another method for manufacturing the positive electrode 201.
- Steps S301 to S304 are the same as the method for producing the bacterially produced carbonized cellulose described in FIG. After step S304, a process of supporting the catalyst on the bacterially produced cellulose cellulose described in FIG. 7 may be performed.
- step S305 the bacterially produced cellulose cellulose obtained in steps S301 to S304 is pulverized.
- step S306 the bacteria-producing gel obtained in step S301 is pulverized.
- step S307 the bacteria-producing cellulose pulverized in step S305 and the bacteria-producing gel pulverized in step S306 are mixed.
- the pulverization process is performed using, for example, a mixer, a homogenizer, an ultrasonic homogenizer, a high-speed rotary shearing stirrer, a colloid mill, a roll mill, a high-pressure jet disperser, a rotating ball mill, a vibrating ball mill, a planetary ball mill, or an attritor.
- the production gel and the bacterial production carbonized cellulose are made into a powder or slurry.
- the bacterial-produced gel and the bacterial-produced carbonized cellulose preferably have a secondary particle size of 100 nm to 5 mm, more preferably 1 ⁇ m to 1 mm.
- the secondary particle diameter is pulverized to 100 nm or less, the co-continuous structure of the nanofiber is broken, and it becomes difficult to obtain a sufficient binding force and conductive path, and the electrical resistance increases. Because.
- the secondary particle diameter is 5 mm or more, the bacteria-producing gel functioning as a binder is not sufficiently dispersed, and it becomes difficult to maintain the positive electrode in a sheet form.
- the bacterially produced carbonized cellulose has a high porosity and low density, it is difficult to handle when the bacterially produced carbonized cellulose is pulverized alone, because the powder of the bacterially produced cellulose carbonized during or after the pulverization. Therefore, it is preferable to impregnate bacteria-produced carbonized cellulose with a solvent before pulverization.
- the solvent used here is not particularly limited, for example, may be used an aqueous, such as water (H 2 O).
- the solvent is carboxylic acid, methanol (CH 3 OH), ethanol (C 2 H 5 OH), propanol (C 3 H 7 OH), n-butanol, isobutanol, n-butylamine, dodecane, unsaturated fatty acid,
- Organic systems such as ethylene glycol, heptane, hexadecane, isoamyl alcohol, octanol, isopropanol, acetone and glycerin can be used. Two or more of these may be mixed.
- the mixing step can be omitted, which is preferable.
- the mixture prepared by the above pulverization process and mixing process is in the form of a slurry.
- this mixed slurry is applied to the separators 203 and 203A or the conductive layers 204 and 204A.
- the drying step of step S309 the applied mixed slurry is dried.
- the mixed slurry may be applied to either the separator 203, 203A or the conductive layers 204, 204A.
- the xerogel absorbs the solvent at the time of coating and gels. Therefore, it is preferable to apply the mixed slurry to the conductive layers 204 and 204A.
- a thermostatic bath a vacuum dryer, an infrared dryer, a hot air dryer, or a suction dryer may be used.
- a suction dryer By performing suction filtration using an aspirator or the like, it can be quickly dried.
- the mixed slurry may be dried to form a sheet and then processed into a desired shape.
- the obtained sheet-like bacteria-produced carbonized cellulose is cut into a desired rectangle (for example, 30 mm ⁇ 20 mm) with a punching blade, a laser cutter, or the like to form the positive electrode 201.
- the material cost such as a piece generated by the cutting process increases.
- the positive electrode 201 may be produced using cellulose nanofiber carbon instead of bacterially produced cellulose.
- the production method using cellulose nanofiber carbon is the same as the production method using bacterially produced cellulose cellulose.
- the solution containing cellulose nanofibers is frozen to obtain a frozen body.
- the frozen body is dried in vacuum to obtain a dried body.
- the dried body is heated and carbonized in a gas atmosphere in which cellulose does not burn. Thereby, cellulose nanofiber carbon is obtained.
- Cellulose nanofiber carbon produced by this production method has a fibrous network structure.
- This cellulose nanofiber carbon has a conductive three-dimensional network structure, and has physical property values, characteristics, and performance equivalent to those of bacterially produced cellulose.
- Cellulose nanofiber carbon is processed into a plate or sheet and cut into a desired shape to form a positive electrode 201.
- a positive electrode 201 may be manufactured by preparing a slurry from cellulose nanofiber carbon, applying the slurry, and drying the slurry.
- the pulverization step the cellulose nanofiber carbon produced as described above is pulverized.
- the mixing step the cellulose nanofiber solution and the pulverized cellulose nanofiber carbon are mixed. Thereby, a slurry-like mixture is obtained.
- this mixed slurry is applied to the separators 203 and 203A or the conductive layers 204 and 204A and dried.
- FIG. 9 is a flowchart showing a method for manufacturing the negative electrode 202.
- step S401 a metal powder containing predetermined magnesium, a binder, and a conductive aid are mixed.
- the mixed slurry obtained by mixing is applied to the separators 203 and 203B or the conductive layers 204 and 204B.
- the drying step of step S403 the applied mixed slurry is dried.
- the manufacturing method of FIG. 9 can reduce the material cost compared to a method of cutting a magnesium foil into a predetermined shape, and a thin and flexible negative electrode 202 can be manufactured.
- a magnetic stirrer, a stirrer, a mixer, a rotating and rotating mixer, a vacuum stirring and defoaming mixer, a mixer, a homogenizer, an ultrasonic homogenizer, a high-speed rotary shearing stirrer, a colloid mill, a roll mill, and a high-pressure jet dispersion Using a machine, a rotating ball mill, a vibrating ball mill, a planetary ball mill, or an attritor, a slurry containing a metal powder containing magnesium, a binder, and a conductive additive is prepared.
- the metal powder containing magnesium to be mixed can be pure magnesium or an alloy mainly composed of magnesium.
- the magnesium-based alloy include AZ31, AZ31B, AZ61, AZ91, AMX601, AMX602, AZX611, AZX612, AM50, AM60, and LZ91.
- the metal powder containing magnesium it is possible to use a conventional method for synthesizing magnesium powder.
- a conventional method for synthesizing magnesium powder For example, water atomization method, gas atomization method, centrifugal atomization method, melt spinning method, rotating electrode method, stamp mill method, ball mill method, mechanical alloying method, oxide reduction method, chloride reduction method, wet metallurgy method, Examples include an electrolytic carbonyl reaction method and a hydrogen plasma irradiation method.
- the particle size of the metal powder containing magnesium is preferably 10 nm to 5 ⁇ m, and preferably 20 nm to 2 ⁇ m. This is because when the particles are too large, it is difficult to make contact between the particles when coating and drying are performed, and the electrical conductivity is lowered. When the particles are too fine, the oxidation reaction proceeds and magnesium may be inactivated. In some cases, the rapid progress of the oxidation reaction may burn magnesium metal and lead to fire accidents.
- the binder to be mixed is not particularly limited as long as the particles bind to each other after the slurry drying step.
- the pulverized bacterially produced cellulose used for the production of the positive electrode 201 is suitable as a binder because a structure in which nanofibers are entangled three-dimensionally binds a metal powder containing magnesium firmly.
- Bacteria-produced cellulose is a material necessary for synthesizing the positive electrode 201. Therefore, the same material can be used for the positive electrode 201 and the negative electrode 202, which is advantageous in terms of cost.
- conductive assistant to be mixed for example, bacteria-produced cellulose carbon, carbon powder, and conductive polymer are good, and conductive polymer having high binding property with metal powder containing magnesium is preferable.
- conductive polymers include aliphatic conjugated polyacetylene, aromatic conjugated poly (p-phenylene), mixed conjugated poly (p-phenylene vinylene), polythienylene vinylene, and heterocyclic ring.
- Examples include conjugated polypyrrole, polythiophene, polyethylenedioxythiophene (PEDOT), heteroatom-containing polyaniline, double-chain conjugated polyacene, polyfluorene, and two-dimensional conjugated graphene.
- PEDOT which has good conductivity and excellent environmental stability in a conductor state, is suitable.
- a solvent in addition to the metal powder containing magnesium, the binder, and the conductive additive.
- the solvent is not particularly limited, and for example, an aqueous system such as water (H 2 O) can be used.
- carboxylic acid methanol (CH 3 OH), ethanol (C 2 H 5 OH), propanol (C 3 H 7 OH), n-butanol, isobutanol, n-butylamine, dodecane, unsaturated fatty acid
- Organic systems such as ethylene glycol, heptane, hexadecane, isoamyl alcohol, octanol, isopropanol, acetone and glycerin can be used. Two or more of these may be mixed.
- the mixed slurry may be applied to either the separators 203 and 203B or the conductive layers 204 and 204B, but it is preferable to apply the mixed slurry to the conductive layers 204 and 204B in the same manner as the positive electrode 201.
- a drying process may be performed after both the positive electrode slurry and the negative electrode slurry are applied to the conductive layer 204.
- the negative electrode 202 can be formed by a known method.
- the negative electrode 202 is manufactured by forming a metal magnesium foil into a predetermined shape.
- FIG. 10 is an exploded perspective view of the battery unit 2 of the first embodiment
- FIG. 11 is a cross-sectional view of the battery unit 2 of the first embodiment.
- the battery unit 2 of Example 1 includes a positive electrode 201, a negative electrode 202, a separator 203, and a conductive layer 204.
- bacterially produced carbonized cellulose was used for the positive electrode 201.
- preparation of the battery part 2 of Example 1 is demonstrated.
- Bacteria-producing carbonized cellulose used for the positive electrode 201 was obtained by the following method.
- a bacterial cellulose gel produced by Acetobacter xylinum (acetobacter xylinum) is used as a bacterial production gel, and the bacterial production gel is completely immersed in liquid nitrogen in a foamed polystyrene box for 30 minutes. Freeze. After completely freezing the bacterial production gel, the frozen bacterial production gel is taken out on a petri dish and dried in a vacuum of 10 Pa or less by a freeze dryer (manufactured by Tokyo Science Instrument Co., Ltd.) to obtain a bacterial production xerogel. Obtained. After drying in vacuum, the bacteria-producing xerogel was carbonized by baking at 1200 degrees Celsius for 2 hours in a nitrogen atmosphere to obtain bacteria-producing cellulose.
- the bacterially produced carbonized cellulose was confirmed to be a single phase of carbon (C, PDF card No. 01-071-4630) by XRD measurement.
- the PDF card number is a card number of a PDF (Powder Diffraction File) which is a database collected by the International Center for Diffraction Data (ICDD).
- ICDD International Center for Diffraction Data
- the positive electrode 201 was prepared by cutting out the resulting bacterially produced cellulose carbonized into a 30 mm ⁇ 20 mm rectangle using a punching blade, a laser cutter, or the like.
- the negative electrode 202 was prepared by cutting a commercially available metal magnesium foil (thickness 200 ⁇ m, manufactured by Niraco) into a 30 mm ⁇ 20 mm rectangle with a punching blade, a laser cutter, or the like.
- the separator 203 was prepared by cutting a commercially available cellulose-based cotton (Ben cotton, manufactured by Asahi Kasei) into a 30 mm ⁇ 50 mm rectangle with a punching blade, a laser cutter, or the like.
- the conductive layer 204 was prepared by cutting a commercially available carbon cloth (manufactured by Toray) into a 30 mm ⁇ 50 mm rectangle using a punching blade, a laser cutter, or the like.
- the battery unit 2 was prepared as follows. First, the positive electrode 201 and the negative electrode 202 are stacked on the conductive layer 204, and the positive electrode 201 and the negative electrode 202 are sandwiched between the conductive layer 204 and the separator 203. At this time, the positive electrode 201 and the negative electrode 202 are prevented from contacting each other. Subsequently, using a sewing machine, 1 mm inner sides of the outer periphery of the positive electrode 201 and the negative electrode 202 were sewn and pressure-bonded to obtain the battery unit 2.
- FIG. 12 is a plan view showing the configuration of the biological tissue sticking patch 1 of Example 1.
- FIG. A biological tissue sticking patch 1 shown in FIG. 12 has the same configuration as that shown in FIG. 1, and has a battery part 2 and an active ingredient 3 housed separately in a plastic pack 4.
- Active ingredient 3 was prepared as follows. A carbonic acid aqueous solution having a pH of 8.8 and an L-ascorbic acid (vitamin C) aqueous solution having a concentration of 100 ⁇ mol / ml were mixed to prepare a pH of about 7.4. In Example 1, L-ascorbic acid was used as an active ingredient, but the present invention is not limited to this.
- the battery part 2 and the active ingredient 3 were housed separately in the plastic pack 4 as follows. First, the battery section 2 is inserted into a 10 cm ⁇ 10 cm polyethylene film pack (made by Nippon Matai) that is not sealed on one side, and a partition wall 41 is formed by applying heat sealing to a location 5 cm from the back. Then, the battery part 2 was sealed. Then, after injecting the active ingredient 3 from the opening part of the plastic pack 4 using the vacuum injection apparatus (made by Fine Flow Laboratory), the opening part was heat-sealed.
- a 10 cm ⁇ 10 cm polyethylene film pack made by Nippon Matai
- a partition wall 41 is formed by applying heat sealing to a location 5 cm from the back. Then, the battery part 2 was sealed. Then, after injecting the active ingredient 3 from the opening part of the plastic pack 4 using the vacuum injection apparatus (made by Fine Flow Laboratory), the opening part was heat-sealed.
- the tissue tissue patch 1 with the battery part 2 and the active ingredient 3 sealed in the plastic pack 4 is placed in a dark room where the room temperature is maintained at 25 degrees Celsius. After storage for a week, the battery reaction was started and used.
- the active ingredient storage part 43 in which the active ingredient 3 is sealed is folded in half at a broken line 47, pressure is applied with a finger to break the partition wall 41, and the active ingredient 3 is transferred to the battery part 2. Soaked enough. When the active ingredient 3 soaks into the battery part 2, the active ingredient 3 also functions as an electrolytic solution, and the battery reaction starts. When it was confirmed that the separator 203 of the battery unit 2 was wetted with the active ingredient 3, the one end 44 of the plastic pack 4 sealing the battery unit 2 was broken by hand, and the battery unit 2 was taken out.
- the taken-out battery part 2 was placed in the test apparatus shown in FIG. 13, and the skin permeability of the active ingredient 3 to the test piece (rat skin) was confirmed.
- the test apparatus shown in FIG. 13 includes a donor unit 701 and a receiver unit 702.
- the test piece 600 is sandwiched between the donor unit 701 and the receiver unit 702 and is used by being fixed by a fastener 703.
- plastic, metal, glass, ceramics, or the like can be used as the material of the donor unit 701 and the receiver unit 702.
- Teflon registered trademark
- the receiver unit 702 was filled with an aqueous solution adjusted to pH 7.4 with a phosphate buffer from a sampling port 707. Constant temperature water of 35 degrees Celsius was circulated through the jacket portion 706 provided in the test apparatus.
- a stirrer 704 was placed in the receiver unit 702, and stirring was continued gently using a magnetic stirrer 705.
- the test piece 600 is an anesthetized rat with pentobarbital fixed on the back surface, the abdominal skin is removed, the fat is peeled off, and then hydrated with a phosphate buffer solution of pH 7.4 for 30 minutes.
- the donor part 701 side was made into the stratum corneum side, and the receiver part 702 side was made into the dermis side.
- the test piece 600 to which the battery part 2 that has started the battery reaction is attached is placed in contact with the phosphate buffer filled in the lower part of the receiver part 702.
- the active ingredient 3 oozes out into the phosphate buffer through the test piece 600.
- the solution was taken out from the donor unit 701 at regular intervals, and the cumulative permeation amount for the test piece 600 was calculated.
- Concentration measurement was performed by high performance liquid chromatography (manufactured by Agilent Technologies).
- the column used was Agilent Poshell 120 EC-C18, 4.6 ⁇ 100 mm.
- the mobile phase used was a solution of 20 mmol dihydrogen phosphate buffer (KH 2 PO 4 ) adjusted to pH 2.5 with o-phosphoric acid and 60% methanol / 40% acetonitrile.
- the flow rate was measured at 1.5 mL / min, and the detection wavelength was 243.5 nm.
- Example 1 The measurement result of Example 1 will be described later together with the measurement result of Comparative Example 1 below.
- FIG. 15 is a perspective view of the biological tissue sticking patch of Comparative Example 1
- FIG. 16 is a cross-sectional view of Comparative Example 1.
- Example 1 As a comparative example that does not have a battery part, a biological tissue adhesive patch 501 using only the separator and the active ingredient similar to those in Example 1 was prepared.
- the biological tissue affixing patch 501 was prepared by cutting a commercially available cellulose-based cotton (Ben cotton, manufactured by Asahi Kasei) into a 30 mm ⁇ 50 mm rectangle using a punching blade, a laser cutter, or the like, as in Example 1.
- the living tissue adhesive patch 501 was impregnated with the same active ingredients as in Example 1.
- the active ingredient was prepared by mixing an aqueous carbonate solution having a pH of 8.8 and an aqueous L-ascorbic acid (vitamin C) solution having a concentration of 100 ⁇ mol / ml so that the pH was about 7.4. It is a thing.
- FIG. 17 shows the measurement results of Example 1 and Comparative Example 1.
- FIG. 17 also shows the measurement results of Examples 2 to 6 and Comparative Examples 2 to 3 described later.
- Example 1 the cumulative permeation amount of L-ascorbic acid increased with time. This is thought to be because ionized L-ascorbic acid was introduced into the living tissue simultaneously with the movement of hydroxide ions into the living tissue accompanying the battery reaction.
- Example 2 18 is an exploded perspective view of the battery unit 2 of the second embodiment, and FIG. 19 is a cross-sectional view of the battery unit 2 of the second embodiment.
- Example 2 differs from Example 1 in that it includes a positive electrode separator 203A and a negative electrode separator 203B that are spaced apart.
- Two separators 203 of Example 1 were cut out into a 30 mm ⁇ 20 mm rectangle using a punching blade, a laser cutter, or the like, to form a positive electrode separator 203A and a negative electrode separator 203B.
- the preparation method, experimental apparatus, and evaluation method of the biological tissue patch 1 are the same as in Example 1.
- Example 2 the cumulative permeation amount of L-ascorbic acid at each time is increased as compared with Example 1 and Comparative Example 1.
- Example 1 not only the living tissue but also the movement of ions through the separator 203 was performed, and the effect of ion introduction was suppressed.
- Example 2 by separating the separator into the positive electrode separator 203A and the negative electrode separator 203B, the movement of ions through the living tissue was promoted, and the effect of ion introduction was increased.
- Example 3 20 is an exploded perspective view of the battery unit 2 of the third embodiment, and FIG. 21 is a cross-sectional view of the battery unit 2 of the third embodiment.
- Example 3 differs from Example 2 in that the conductive layer 204 is laminated with a plastic film. Specifically, a polyethylene film (manufactured by Thermo Co., Ltd.) is cut into two rectangles of 34 mm ⁇ 54 mm with a punching blade, laser cutter, etc., one of which is the upper surface water-repellent layer 205A and the other is the contact surface water-repellent layer 205B. did.
- the polyethylene film of the contact surface water-repellent layer 205B was provided with a circular contact portion 205C having a diameter of 10 mm by a punching blade, a laser cutter, or the like so that the positive electrode 201 and the negative electrode 202 and the conductive layer 204 were in contact with each other.
- the conductive layer 204 was subjected to water repellent treatment by sandwiching the conductive layer 204 between the upper surface water repellent layer 205A and the contact surface water repellent layer 205B and heat-sealing.
- Example 3 the cumulative permeation amount of L-ascorbic acid at each time is increased as compared with Examples 1, 2 and Comparative Example 1.
- the conductive layer 204 absorbed the active ingredient 3, and ions were moved through the conductive layer 204, so that the effect of ion introduction was suppressed.
- the conductive layer 204 was subjected to water repellent treatment, thereby suppressing the absorption of the active ingredient 3 in the conductive layer 204 and promoting the movement of ions through the living tissue.
- Example 4 The configuration of the battery unit 2 of Example 4 is the same as that of Example 3.
- Example 4 is different from Example 3 in that the positive electrode separator 203A and the negative electrode separator 203B are not made of cellulose-based cotton but use bacterial-produced xerogel.
- Bacterial production xerogel was synthesized by the same synthesis method as in Example 1. Two pieces of bacteria-produced xerogel were cut out into a 30 mm ⁇ 20 mm rectangle using a punching blade, a laser cutter, or the like, and these were used as a positive electrode separator 203A and a negative electrode separator 203B.
- Example 4 the cumulative amount of L-ascorbic acid permeation at each time increased compared to Examples 1 to 3 and Comparative Example 1.
- Example 4 by using a bacterially produced xerogel for the separator, the absorption performance of the active ingredient 3 of the separator is increased, and further, after the bacterially produced xerogel has absorbed the active ingredient 3, it has excellent flexibility. The adhesion between the living tissue and the battery unit 2 was improved.
- Example 5 The configuration of the battery unit 2 of Example 5 is the same as that of Examples 3 and 4.
- the point which used the bacteria production xerogel for the positive electrode part separator 203A and the negative electrode part separator 203B is the same as Example 4.
- Example 5 is different from Example 4 in that the positive electrode 201 and the negative electrode 202 were applied to the conductive layer 204 by using the manufacturing method of FIGS.
- Example 5 A method for manufacturing the positive electrode 201 of Example 5 will be described.
- a bacterial production gel and a bacterial production carbonized cellulose are prepared.
- the bacterial-produced carbonized cellulose was impregnated with water, and then the bacterial-produced gel and the bacterial-produced carbonized cellulose having a weight ratio of 1: 1 were stirred with a homogenizer (manufactured by SMT) for 12 hours.
- the positive electrode slurry obtained in the mixing step was applied to the conductive layer 204 subjected to water repellent treatment with a thickness of 3 mm and a width of 30 mm ⁇ 20 mm using a squeegee.
- a method for manufacturing the negative electrode 202 of Example 5 will be described.
- flame retardant magnesium AZX612 manufactured by Gonda Metal
- the flame-retardant magnesium AZX612 was irradiated with hydrogen plasma by a metal nanoparticle production apparatus (manufactured by Atotech), thereby synthesizing nanoparticles of flame-retardant magnesium AZX612.
- the average particle diameter was about 100 nm, and it was confirmed from the results of ICP emission analysis that no compositional deviation occurred even when the particles were formed.
- Bacteria-producing gel was used as a binder for the negative electrode 202.
- a bacterial production gel is prepared in the same manner as in Example 1.
- the bacteria-producing gel was stirred with a homogenizer (manufactured by SMT) for 12 hours to obtain a slurry-like bacteria-producing gel.
- an aqueous dispersion (5.0% by weight, Orgacon EL-P-5015, manufactured by Sigma-Aldrich) composed of a mixture of polyethylene dioxythiophene and polyanionic poly (styrenesulfonate) was used. .
- the metal powder containing magnesium, the slurry-like bacteria-producing gel, and the above-mentioned conductive aid were stirred for 24 hours using a ball mill.
- the negative electrode slurry obtained in the mixing step was applied to the conductive layer 204 after applying the positive electrode slurry in a thickness of 3 mm and a width of 30 mm ⁇ 20 mm using a squeegee.
- the conductive layer 204 to which the positive electrode slurry and the negative electrode slurry were applied was dried at 60 degrees Celsius for 24 hours using a thermostatic bath to obtain the positive electrode 201 and the negative electrode 202.
- Example 4 In the same manner as in Example 4, a positive electrode separator 203A and a negative electrode separator 203B were prepared, and pressure-bonded with a sewing machine to prepare a battery unit 2.
- Example 5 compared to Examples 1 to 4 and Comparative Example 1, the cumulative permeation amount of L-ascorbic acid at each time is increased.
- Example 5 since the positive electrode 201 and the negative electrode 202 were applied to the conductive layer 204, the adhesive strength with the conductive layer 204 was strong, the resistance value was reduced, and ion introduction by the battery reaction was promoted.
- Example 6 The configuration of the battery unit 2 of Example 6 is the same as that of Example 1.
- Example 6 differs from Example 1 in that cellulose nanofiber carbon is used for the positive electrode 201 instead of bacterially produced cellulose carbonized.
- the cellulose nanofiber carbon used for the positive electrode 201 was obtained by the following method.
- cellulose nanofibers manufactured by Nippon Paper Industries Co., Ltd.
- 1 g of cellulose nanofibers and 10 g of ultrapure water were stirred with a homogenizer (manufactured by SMT) for 12 hours to obtain a cellulose nanofiber solution in which cellulose nanofibers were dispersed.
- a homogenizer manufactured by SMT
- the test tube containing the cellulose nanofiber solution was immersed in liquid nitrogen for 30 minutes to completely freeze the cellulose nanofiber solution.
- the frozen cellulose nanofiber solution was taken out on a petri dish and dried in a vacuum of 10 Pa or less by a freeze dryer (manufactured by Tokyo Science Instrument Co., Ltd.) to obtain a dried cellulose nanofiber.
- the cellulose nanofibers were carbonized by carbonizing the cellulose nanofibers by firing at 600 degrees Celsius for 2 hours in a nitrogen atmosphere.
- This cellulose nanofiber carbon was confirmed to be a single phase of carbon (C, PDF card No. 01-071-4630) by XRD measurement.
- C PDF card No. 01-071-4630
- SEM observation it was confirmed that the cellulose nanofiber carbon was a co-continuous body in which nanofibers having a diameter of 70 nm were continuously connected. It was 690 m ⁇ 2 > / g when the BET specific surface area of the cellulose nanofiber carbon was measured with the BET apparatus.
- the porosity of the cellulose nanofiber carbon was measured by the mercury intrusion method, it was 99% or more.
- the preparation method, experimental apparatus, and evaluation method of the biological tissue patch 1 are the same as in Example 1.
- Example 6 the cumulative amount of L-ascorbic acid permeation at each time increased compared to Comparative Example 1. Also, it can be seen that the cumulative permeation amount of L-ascorbic acid at each time is comparable to that in Example 1. This is because the cellulose nanofiber carbon used for the positive electrode 201 has an excellent specific surface area, as in the case of bacterially produced cellulose, and suppresses battery overvoltage due to the fibrous network structure of cellulose nanofiber carbon, This is because ion introduction was promoted.
- Comparative Example 2 The configuration of the battery unit 2 of Comparative Example 2 is the same as that of Example 1. Comparative Example 2 is different from Example 1 in that carbon (Ketjen Black EC600JD), which is known as an electrode of an air electrode of a general magnesium-air battery, is used as Comparative Example 2. Specifically, ketjen black powder (made by Lion) and polytetrafluoroethylene (PTFE) powder (made by Daikin) are sufficiently pulverized and mixed using a roughing machine at a weight ratio of 50:30:20, Roll forming was performed to prepare a sheet-like electrode having a thickness of 0.5 mm. A sheet-like electrode was cut out at 30 mm ⁇ 20 mm to obtain a positive electrode of Comparative Example 2.
- carbon Keltjen Black EC600JD
- PTFE polytetrafluoroethylene
- the preparation method, test apparatus, and evaluation method of the biological tissue patch 1 are the same as those in Example 1.
- Comparative Example 2 showed a smaller value of the cumulative permeation amount of L-ascorbic acid at each time than Examples 1-6. Moreover, when the positive electrode of Comparative Example 2 was observed after the measurement, a part of the positive electrode collapsed, and contamination with carbon powder was confirmed in the living tissue.
- Comparative Example 3 In Comparative Example 3, the battery part 2 of Example 1 and the active ingredient 3 were stored in contact with each other. Specifically, in Comparative Example 3, after preparing the biological tissue application patch 1 as in Example 1, the partition wall 41 was broken and the active ingredient 3 was sufficiently infiltrated into the battery unit 2, and then the room temperature was 25 degrees. Stored in a maintained darkroom for 1 week. Thereafter, the battery part 2 was taken out and evaluated in the same manner as in Example 1.
- Comparative Example 3 showed a smaller cumulative permeation amount of L-ascorbic acid at each time than Examples 1-6 and Comparative Examples 1-2.
- Comparative Example 3 since the active ingredient 3 was stored in a state where the battery part 2 was infiltrated, deterioration due to self-discharge of the battery, corrosion of the negative electrode, alteration of the active ingredient 3 and the like occurred.
- FIG. 22 is an exploded perspective view of the battery unit 2 of the seventh embodiment
- FIG. 23 is a cross-sectional view of the battery unit 2 of the seventh embodiment.
- Example 7 differs from Example 1 in that it includes a positive electrode part conductive layer 204A and a negative electrode part conductive layer 204B that are spaced apart.
- Two conductive layers 204 of Example 1 were cut into a 30 mm ⁇ 20 mm rectangle using a punching blade, a laser cutter, or the like, to form a positive electrode portion conductive layer 204A and a negative electrode portion conductive layer 204B.
- the preparation method, experimental apparatus, and evaluation method of the biological tissue patch 1 are the same as in Example 1.
- FIG. 24 shows the measurement results of Example 7 and Example 8 described later.
- FIG. 24 also shows the measurement results of Examples 1 and 6 and Comparative Examples 1 to 3 described above.
- Example 7 the cumulative amount of L-ascorbic acid permeation at each time increased compared to Example 1 and Comparative Example 1.
- Example 1 not only living tissue but also movement of electrons through the conductive layer 204 was performed, and the effect of ion introduction was suppressed.
- Example 7 by dividing the conductive layer into the positive electrode portion conductive layer 204A and the negative electrode portion conductive layer 204B, the movement of electrons through the living tissue was promoted, and the effect of ion introduction was increased.
- Example 8 The configuration of the battery unit 2 of Example 8 is the same as that of Example 7.
- Example 7 is different from Example 7 in that a bacterially produced xerogel is used for the separator 203 and that the positive electrode 201 and the negative electrode 202 are applied to the positive electrode part conductive layer 204A and the negative electrode part conductive layer 204B.
- Bacteria-producing xerogel was synthesized by the same synthesis method as in Example 1.
- the bacterially produced xerogel was cut into a 30 mm ⁇ 50 mm rectangle using a punching blade, a laser cutter, or the like, and the cut bacteria producing xerogel was used as the separator 203.
- Example 8 produced the positive electrode 201 and the negative electrode 202 using the manufacturing method of FIGS. Specifically, in Example 8, as in Example 5, a positive electrode slurry and a negative electrode slurry were prepared. In the coating process, using a squeegee, the positive electrode slurry is applied to the positive electrode conductive layer 204A with a thickness of 3 mm and a width of 30 mm ⁇ 20 mm, and the negative electrode slurry is applied to the negative electrode conductive layer 204B with a thickness of 3 mm and a width of 30 mm ⁇ Application was performed at 20 mm. After the coating step, the positive electrode part conductive layer 204A and the negative electrode part conductive layer 204B were dried at 60 degrees Celsius for 24 hours using a thermostatic bath, and the positive electrode 201 and the negative electrode 202 were obtained.
- the preparation method, experimental apparatus, and evaluation method of the biological tissue patch 1 are the same as in Example 1.
- Example 8 the cumulative amount of L-ascorbic acid permeation increased at each time as compared with Example 7.
- the positive electrode 201 and the negative electrode 202 were applied to the positive electrode part conductive layer 204A and the negative electrode part conductive layer 204B, the adhesive strength between the positive electrode part conductive layer 204A and the negative electrode part conductive layer 204B was strong, and the resistance value was high. The ion introduction by the battery reaction was promoted.
- the biological tissue sticking patch 1 is accommodated so that the battery part 2 and the active ingredient 3 do not come into contact with each other, and effective when the biological tissue sticking patch 1 is used.
- the biological tissue sticking patch 1 is used.
- the self-discharge of the battery unit 2 is suppressed and the active component 3 is kept fresh during storage. And an excellent ion introduction effect can be obtained.
- the battery part 2 and the active ingredient 3 are separated and contained in the plastic pack 4 in an integrated manner, but the battery part 2 and the active ingredient 3 may be separately housed and stored.
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Abstract
Description
本実施形態の生体組織貼付けパッチは、一般的なマグネシウム空気電池と同様な反応によって発生させた電気により、生体組織の内部に有効成分を浸透させるためのパッチである。
次に、電池部2の構成について説明する。
正極201は、一般的なマグネシウム空気電池で使用される正極を用いることができる。例えば、カーボン、金属、酸化物、窒化物、炭化物、硫化物、及びリン化物を使用することができる。これらを2種類以上混合しても良い。正極201は、カーボン粉末をバインダーで成形する公知のプロセスで作製できる。バインダーは一般的にフッ素を含有した樹脂が用いられているので、廃棄等により正極201を燃焼させるとフッ酸が発生する。そのため、安全性向上及び環境負荷低減といった改善の余地が存在している。本実施形態では、バクテリア産生炭化セルロースまたはセルロースナノファイバーカーボンを正極201に用いることで、フッ素を含有した樹脂を未使用とした。正極201に用いるバクテリア産生炭化セルロースは、炭化したバクテリア産生セルロースの三次元ネットワーク構造を有し、例えば、平均孔径が0.1~50μmであることが好ましく、0.1~2μmであることが更に好ましい。平均孔径は水銀圧入法により求めた値である。正極201に用いるセルロースナノファイバーカーボンは、炭化したセルロースナノファイバーの三次元ネットワーク構造を有し、例えば、繊維径が5~500nmであることが好ましく、20~200nmであることが好適である。
負極202は負極活物質で構成する。負極活物質は、マグネシウム空気電池の負極材料として用いることができる材料、つまり、金属マグネシウム、マグネシウム含有物質を含むものであればよい。負極202は、例えば、金属マグネシウム、金属マグネシウムのシート、またはマグネシウム粉末から構成すればよい。マグネシウム以外の金属空気電池として用いることができる鉄、亜鉛、アルミニウム、カルシウム、リチウム、およびナトリウムも負極材料として用いることができる。安全性及び電池出力の面からマグネシウムを用いるのが最も好適である。
セパレータ203、正極部セパレータ203A、および負極部セパレータ203Bは、有効成分3を含有することが可能で、且つ、導電性を有していない物質であればよい。例えば、和紙、コットン、コラーゲン、バクテリア産生ゲル、及びバクテリア産生キセロゲルを用いることができる。バクテリア産生キセロゲルは、多孔質のため、有効成分3の保持性能が高い。バクテリア産生キセロゲルは、有効成分3を保持するとゲル化するため、生体組織との密着性に優れている。
導電層204、正極部導電層204A、および負極部導電層204Bは、導電性を有する物質であれば特に限定されるものではない。例えば、カーボンクロス、カーボンシート、金属メッシュ、金属線、導電性クロス、導電性ゴム、及び導電性高分子が挙げられる。導電層204の電気抵抗値を調整することによって、電池反応の速度を調整できる。導電層204の抵抗値を大きくすると、有効成分3のイオン導入の速度は緩やかになる。イオン導入が早すぎて痛みを生じる場合は、導電層204の抵抗値を大きくすれば良い。
次に、有効成分について説明する。
次に、正極の製造方法について説明する。
次に、負極の製造方法について説明する。
次に、電池部2の構成、電池部2の各要素の材料、及び作製方法を変えた実施例とその評価結果について説明する。
図10は実施例1の電池部2の分解斜視図であり、図11は実施例1の電池部2の断面図である。
図15は比較例1の生体組織貼付けパッチの斜視図であり、図16は比較例1の断面図である。
図18は実施例2の電池部2の分解斜視図であり、図19は実施例2の電池部2の断面図である。
図20は実施例3の電池部2の分解斜視図であり、図21は実施例3の電池部2の断面図である。
実施例4の電池部2の構成は実施例3と同様である。
実施例5の電池部2の構成は実施例3,4と同様である。正極部セパレータ203A及び負極部セパレータ203Bにバクテリア産生キセロゲルを使用した点は実施例4と同じである。
実施例6の電池部2の構成は実施例1と同様である。実施例6は、正極201にバクテリア産生炭化セルロースではなく、セルロースナノファイバーカーボンを使用した点で実施例1と異なる。
比較例2の電池部2の構成は実施例1と同様である。比較例2は、正極を一般的なマグネシウム空気電池の空気極の電極として公知であるカーボン(ケッチェンブラックEC600JD)を使用した点で実施例1と異なる。具体的には、ケッチェンブラック粉末(ライオン製)およびポリテトラフルオロエチレン(PTFE)粉末(ダイキン製)を50:30:20の重量比で、らいかい機を用いて十分に粉砕および混合し、ロール成形して、厚さ0.5mmのシート状電極を作製した。シート状電極を30mm×20mmで切り抜き比較例2の正極を得た。
比較例3は、実施例1の電池部2と有効成分3を接触させた状態で保管したものである。具体的には、比較例3では、実施例1と同様に生体組織貼付けパッチ1を作製した後、隔壁41を破り、有効成分3を電池部2まで十分に染み込ませた後に、室温25度に維持された暗室に1週間保管した。その後、電池部2を取出し、実施例1と同様に評価を実施した。
図22は実施例7の電池部2の分解斜視図であり、図23は実施例7の電池部2の断面図である。
実施例8の電池部2の構成は実施例7と同様である。セパレータ203にバクテリア産生キセロゲルを使用した点、正極201及び負極202を正極部導電層204A及び負極部導電層204Bに塗布して作製した点で実施例7と異なる。
2…電池部
201…正極
202…負極
203…セパレータ
203A…正極部セパレータ
203B…負極部セパレータ
204…導電層
204A…正極部導電層
204B…負極部導電層
205A…上面撥水層
205B…接触面撥水層
205C…接触部
3…有効成分
4…プラスチックパック
41…隔壁
42…電池部保管部
43…有効成分保管部
100…生体組織
Claims (9)
- 生体組織に貼り付けて使用する生体組織貼付けパッチであって、
電池部と、
前記電池部に接触しないように収容された有効成分と、を有し、
当該生体組織貼付けパッチを使用するときは、前記電池部に前記有効成分を接触させて電池反応を開始させることを特徴とする生体組織貼付けパッチ。 - 隔壁を備えて前記電池部及び前記有効成分を隔離して一体で収容する容器を有し、
当該生体組織貼付けパッチを使用するときは、前記隔壁の少なくとも一部を除去して前記電池部に前記有効成分を接触させることを特徴とする請求項1に記載の生体組織貼付けパッチ。 - 前記電池部は、
正極と、
負極と、
導電層と、
電解質を含んでいないセパレータと、を有し、
前記セパレータに前記有効成分を含浸させて電池反応を開始させることを特徴とする請求項1又は2に記載の生体組織貼付けパッチ。 - 前記セパレータは、前記正極と接触し、前記負極とは接触しないように配置された正極部セパレータと、前記負極と接触し、前記正極とは接触しないように配置された負極部セパレータと、を有し、
前記正極部セパレータ及び前記負極部セパレータが前記生体組織に接触した状態で使用することを特徴とする請求項3に記載の生体組織貼付けパッチ。 - 前記導電層は撥液性を有することを特徴とする請求項4に記載の生体組織貼付けパッチ。
- 前記導電層は、前記正極と接触し、前記負極とは接触しないように配置された正極部導電層と、前記負極と接触し、前記正極とは接触しないように配置された負極部導電層と、を有し、
前記正極部導電層及び前記負極部導電層が前記生体組織に接触した状態で使用することを特徴とする請求項3に記載の生体組織貼付けパッチ。 - 前記セパレータは、キセロゲルで構成されることを特徴とする請求項3に記載の生体組織貼付けパッチ。
- 前記正極は、三次元ネットワーク構造の炭化セルロースを含むことを特徴とする請求項3に記載の生体組織貼付けパッチ。
- 前記負極は、マグネシウム、亜鉛、アルミニウム、鉄、カルシウム、リチウム、ナトリウムの少なくともいずれか1つを含むことを特徴とする請求項3に記載の生体組織貼付けパッチ。
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CN113543753A (zh) * | 2019-03-04 | 2021-10-22 | 国立大学法人东北大学 | 眼用医疗器械的水分的吸收或排出方法及眼用医疗器械 |
US12239527B2 (en) | 2019-03-04 | 2025-03-04 | Tohoku University | Method of absorbing or discharging water of ophthalmic medical device and ophthalmic medical device |
JPWO2020178964A1 (ja) * | 2019-03-04 | 2020-09-10 | ||
CN113543753B (zh) * | 2019-03-04 | 2024-04-19 | 国立大学法人东北大学 | 眼用医疗器械的水分的吸收或排出方法及眼用医疗器械 |
JP7352979B2 (ja) | 2019-03-04 | 2023-09-29 | 国立大学法人東北大学 | 眼用医療機器の水分の吸収又は排出方法及び眼用医療機器 |
WO2021149111A1 (ja) * | 2020-01-20 | 2021-07-29 | 日本電信電話株式会社 | 球状ナノカーボン繊維集合体の製造方法、カーボンナノロッドの製造方法およびグラフェンナノリボンの製造方法 |
JPWO2021149111A1 (ja) * | 2020-01-20 | 2021-07-29 | ||
CN114945403A (zh) * | 2020-01-21 | 2022-08-26 | 株式会社离子用具 | 生物电池治疗器具 |
WO2021149769A1 (ja) * | 2020-01-21 | 2021-07-29 | 株式会社イオンギア | 生体電池治療具 |
JP2021112467A (ja) * | 2020-01-21 | 2021-08-05 | 賢司 小蒲 | 生体電池治療具 |
JPWO2021250742A1 (ja) * | 2020-06-08 | 2021-12-16 | ||
WO2021250741A1 (ja) * | 2020-06-08 | 2021-12-16 | 日本電信電話株式会社 | アイライナー用液状化粧料 |
JP7368782B2 (ja) | 2020-06-08 | 2023-10-25 | 日本電信電話株式会社 | 睫毛用化粧料 |
JP7368781B2 (ja) | 2020-06-08 | 2023-10-25 | 日本電信電話株式会社 | アイライナー用液状化粧料 |
JPWO2021250741A1 (ja) * | 2020-06-08 | 2021-12-16 | ||
WO2021250742A1 (ja) * | 2020-06-08 | 2021-12-16 | 日本電信電話株式会社 | 睫毛用化粧料 |
WO2022255232A1 (ja) * | 2021-05-29 | 2022-12-08 | 株式会社イオンギア | 生体電池式イオン導入部材及びシート状基材 |
WO2023228378A1 (ja) * | 2022-05-26 | 2023-11-30 | 日本電信電話株式会社 | 生体組織貼付けパッチ |
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EP3613465B1 (en) | 2022-01-26 |
JPWO2018194079A1 (ja) | 2020-04-09 |
JP6824392B2 (ja) | 2021-02-03 |
CN110418662A (zh) | 2019-11-05 |
CN110418662B (zh) | 2024-03-12 |
EP3613465A4 (en) | 2021-02-17 |
US20200121915A1 (en) | 2020-04-23 |
US11717671B2 (en) | 2023-08-08 |
EP3613465A1 (en) | 2020-02-26 |
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