WO2023188980A1 - 粒子含有ハイドロゲル - Google Patents

粒子含有ハイドロゲル Download PDF

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WO2023188980A1
WO2023188980A1 PCT/JP2023/005845 JP2023005845W WO2023188980A1 WO 2023188980 A1 WO2023188980 A1 WO 2023188980A1 JP 2023005845 W JP2023005845 W JP 2023005845W WO 2023188980 A1 WO2023188980 A1 WO 2023188980A1
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hydrogel
meth
mass
resin particles
porous resin
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French (fr)
Japanese (ja)
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栄作 佐藤
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Sekisui Kasei Co Ltd
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Sekisui Kasei Co Ltd
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Priority to US18/851,797 priority Critical patent/US20250213750A1/en
Priority to JP2024511429A priority patent/JP7753515B2/ja
Priority to CN202380043182.8A priority patent/CN119403888A/zh
Publication of WO2023188980A1 publication Critical patent/WO2023188980A1/ja
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/425—Porous materials, e.g. foams or sponges
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/52—Hydrogels or hydrocolloids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide

Definitions

  • the present invention relates to hydrogels.
  • Hydrogel is a polymer with high affinity for water that swells in an aqueous solvent. Hydrogels have various properties depending on their purpose, such as water absorption, swelling, moisture retention, adhesiveness, and electrical conductivity. It is used in a wide range of fields such as cosmetics and electricity.
  • Patent Document 1 discloses a hydrogel that includes a polymer matrix and water and has a specific network structure.
  • Patent Document 2 discloses a hydrogel containing 0.001 to 1% by mass of l-menthol, but if more than 1% by mass of l-menthol is added, the hydrogel becomes cloudy and l-menthol It was difficult to create a hydrogel with a high content of .
  • An object of the present invention is to provide a hydrogel that can stably disperse a large amount of volatile components and has excellent sustained release properties of volatile components.
  • the inventors conducted extensive research and found that by encapsulating volatile components in porous resin particles and dispersing them in the hydrogel, a large amount of volatile components can be stabilized in the hydrogel. It has been found that it is dispersible and has excellent sustained release properties of volatile components.
  • the hydrogel according to Item 1 or 2 wherein the content of the volatile component is 0.5 to 5% by mass based on 100% by mass of the hydrogel.
  • the hydrogel according to any one of items 1 to 4 comprising a polymer matrix, water, and a wetting agent.
  • the hydrogel according to Item 5 wherein the polymer matrix is made of a copolymer of a monofunctional monomer having one ethylenically unsaturated group and a crosslinkable monomer.
  • the polymer matrix is made of a copolymer of a monofunctional monomer having one ethylenically unsaturated group and a crosslinkable monomer.
  • the monofunctional monomer is at least selected from the group consisting of (meth)acrylamide, (meth)acrylic acid, N,N-dimethyl(meth)acrylamide, diacetone (meth)acrylamide, and tert-butylacrylamide sulfonic acid. 8.
  • FIG. 1 is a schematic plan view of one embodiment of a gel sheet.
  • FIG. 1B is a schematic cross-sectional view of the gel sheet of FIG. 1A taken along line 1B-1B.
  • (meth)acrylic refers to acrylic, methacrylic, or both. Therefore, (meth)acrylamide and/or N,N-dimethyl(meth)acrylamide means (1) acrylamide, methacrylamide, or both, (2) N,N-dimethylacrylamide, and N,N-dimethylmethacrylamide. Refers to amide, or both, or (3) both (1) and (2).
  • the hydrogel of the present invention is a hydrogel containing porous resin particles and a volatile component, and the porous resin particles have a pore diameter of 5 to 30 nm and an oil absorption of 50 to 700 ml/100 g.
  • the porous resin particles and the volatile component are preferably contained in the hydrogel as volatile component-containing particles in which the volatile component is supported in the porous resin particles.
  • the porous resin particles are not particularly limited as long as they have a porous structure, but are preferably water-insoluble.
  • the water-insoluble property of the resin particles includes not only the property that the resin particles themselves are water-insoluble, but also the property that the water-soluble acrylic resin, alginic acid resin, or amide resin becomes water-insoluble when crosslinked. means.
  • insoluble in water refers to the property of being in a suspended and/or dispersed state without being dissolved at a visual level after being added to water.
  • porous resin particles examples include acrylic resins, alginic acid resins, amide resins, and the like. Among these, porous resin particles made of acrylic resin are preferred.
  • the porous resin particles made of acrylic resin are porous resin particles made of a polymer of a monomer mixture, and the monomer mixture is crosslinked with a monofunctional (meth)acrylic acid ester as a monomer. Examples include those containing a sexual monomer.
  • Examples of the monofunctional (meth)acrylate ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, ( Hexyl (meth)acrylate, Heptyl (meth)acrylate, Octyl (meth)acrylate, Nonyl (meth)acrylate, Decyl (meth)acrylate, Undecyl (meth)acrylate, Dodecyl (meth)acrylate, (meth) ) glycidyl acrylate, methoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, (meth)acrylic acid Methoxyethylene glycol, butoxytriethylene glycol (meth)
  • monofunctional (meth)acrylic esters may be used alone or in combination of two or more.
  • the monofunctional (meth)acrylic ester used in the present invention is preferably a C1-C4 (carbon number 1-4) alkyl ester of (meth)acrylic acid, and methyl methacrylate is particularly preferred.
  • the content of the monofunctional (meth)acrylic ester in the monomer mixture is in the range of 1 to 50% by mass, preferably in the range of 10 to 50% by mass.
  • the content of the monofunctional (meth)acrylic acid ester in the monomer mixture is within the range of 1 to 50% by mass, the crosslinkable monomer is sufficiently contained in the monomer mixture. Therefore, sufficient porosity can be imparted to the porous resin particles, the specific surface area can be increased, and the bulk specific gravity of the porous resin particles can be reduced.
  • crosslinkable monomer a known crosslinkable monomer having two or more ethylenically unsaturated groups can be used.
  • crosslinkable monomer examples include ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, allyl(meth)acrylate, trimethylolpropane tri(meth)acrylate, and pentaerythritol tetra( Examples include (meth)acrylic crosslinkable monomers such as meth)acrylate; vinyl crosslinkable monomers such as divinylbenzene, divinylnaphthalene, diallyl phthalate, and derivatives thereof. Among these, (meth)acrylic crosslinkable monomers are preferred, and ethylene glycol di(meth)acrylate is more preferred. These crosslinkable monomers may be used alone or in combination of two or more.
  • the content of the crosslinkable monomer in the monomer mixture is within the range of 50 to 99% by mass, and more preferably within the range of 50 to 90% by mass.
  • the content of the crosslinkable monomer in the monomer mixture is within the range of 50 to 99% by mass, sufficient porosity can be imparted to the porous resin particles and the specific surface area can be increased. , and the bulk specific gravity of the porous resin particles can be reduced.
  • the monomer mixture may contain other monomers other than the above-mentioned monofunctional (meth)acrylic acid ester and the crosslinkable monomer, as long as it does not affect the specific surface area of the porous resin particles of the present invention. May include the body.
  • the pore diameter of the porous resin particles is 5 to 30 nm, preferably 10 to 20 nm. If the average pore diameter is less than 5 nm, there is a risk that permeation of volatile components into the porous resin particles may be inhibited. Moreover, when the pore diameter exceeds 30 nm, the rate of release of volatile components from the porous resin particles becomes faster, and there is a possibility that the sustained release of volatile components in the hydrogel may deteriorate. Note that the pore diameter means the average pore diameter obtained from the nitrogen desorption isotherm based on the BJH method.
  • the nitrogen desorption isotherm is measured for the resin particles to be measured using a specific surface area/pore distribution measuring device (Tristar II 3020, manufactured by Shimadzu Corporation), and the nitrogen desorption isotherm is measured using the BJH method (Barrett, Pore diameter (average pore diameter) can be calculated based on E.P.; Joyner, L.G.; Halenda, P.P., J.Am.Chem.Soc.73, 373 (1951) .
  • the oil absorption amount of the porous resin particles is 50 to 700 ml/100 g, preferably 100 to 700 ml/100 g. It is preferable that the oil absorption amount is 50 ml/100 g or more because a large amount of volatile components can be supported in the porous resin particles. When the oil absorption amount exceeds 700 ml/100 g, the number of voids inside the porous resin particles increases, and there is a possibility that sufficient particle strength cannot be ensured. Note that the oil absorption amount can be measured based on the measurement method of JIS K 5101-13-2.
  • the pore volume of the porous resin particles is preferably 0.30 to 0.90 ml/g, more preferably 0.40 to 0.70 ml/g. It is preferable that the pore volume is 0.30 ml/g or more, since a large amount of volatile components can be supported in the porous resin particles. Further, it is preferable that the pore volume is 0.90 ml/g or less because the particle strength of the porous resin particles does not decrease. Note that in this specification, the pore volume refers to the pore volume per unit mass, and in the present invention, it refers to the pore volume obtained from the nitrogen desorption isotherm using the BJH method.
  • the nitrogen desorption isotherm is measured for the resin particles to be measured using a specific surface area/pore distribution measuring device (Tristar II 3020, manufactured by Shimadzu Corporation), and the nitrogen desorption isotherm is measured using the BJH method (Barrett, Calculating the pore volume (integrated pore volume) based on E.P.; Joyner, L.G.; Halenda, P.P., J. Am. Chem. Soc. 73, 373 (1951)) I can do it.
  • a specific surface area/pore distribution measuring device Tristar II 3020, manufactured by Shimadzu Corporation
  • the specific surface area of the porous resin particles is preferably 50 to 300 m 2 /g, more preferably 80 to 200 m 2 /g. It is preferable that the specific surface area is 50 m 2 /g or more because the porous resin particles can absorb a large amount of volatile components. It is preferable that the specific surface area is 300 m 2 /g or less because the particle strength of the porous resin particles does not decrease. Note that in this specification, the specific surface area refers to the surface area per unit mass, and in the present invention, refers to the specific surface area obtained by the BET method (N 2 ).
  • the specific surface area can be measured by the BET method (N2) according to the BET method (nitrogen adsorption method) described in ISO 9277 1st edition JIS Z 8830:2001.
  • the BET nitrogen adsorption isotherm of the resin particles to be measured is measured using a specific surface area/pore distribution measuring device (Tristar II3020, manufactured by Shimadzu Corporation), and the BET nitrogen adsorption isotherm is compared from the nitrogen adsorption amount using the BET multipoint method. Surface area can be calculated.
  • the bulk specific gravity of the porous resin particles is preferably 0.20 to 0.70 g/ml, more preferably 0.30 to 0.60 g/ml. It is preferable that the bulk specific gravity is 0.20 g/ml or more because the particle strength of the porous resin particles does not decrease. It is preferable that the bulk specific gravity is 0.70 g/ml or less, since a large amount of volatile components can be supported in the porous resin particles.
  • the bulk specific gravity refers to the solidified apparent specific gravity measured using Powder Tester Model PT-E manufactured by Hosokawa Micron Corporation.
  • the volume average particle diameter of the porous resin particles is preferably in the range of 0.50 to 100 ⁇ m, more preferably in the range of 1.0 to 50 ⁇ m, and more preferably in the range of 2.0 to 30 ⁇ m. It is particularly preferable. When it is within the above range, the volatile components can be effectively permeated into the porous resin particles.
  • 0.1 g of resin particles were dispersed in 10 ml of a 0.1% by mass nonionic surfactant aqueous solution using a particle size distribution measuring device (Multicizer 4e (manufactured by Beckman Coulter)). The volume average particle diameter is calculated from the average value in the volume-based particle size distribution of 100,000 particles.
  • Porous resin particles are produced by suspending and polymerizing a monomer mixture containing a monofunctional (meth)acrylic acid ester and a crosslinkable monomer in an aqueous medium in the presence of an organic solvent, and then removing the organic solvent. It can be manufactured by
  • the content of porous resin particles in the hydrogel is preferably 0.50 to 10% by mass, more preferably 1.0 to 6.0% by mass, based on 100% by mass of the hydrogel.
  • the content of the porous resin particles is within the above range, it becomes possible to add a large amount of volatile components to the hydrogel without impairing the mechanical strength and flexibility of the hydrogel.
  • Volatile component Volatile component
  • Volatile components include fragrances, spices, essential oils, etc., and these can be used alone or in combination of two or more.
  • Flavors and spices include, for example, citrus essential oils such as l-menthol, orange oil, lemon oil, grapefruit oil, lime oil, tangerine oil, lavender oil, mandarin oil, and pergamot oil; sage, rosemary, perilla, and basil. Spice oils such as , ginger, and wasabi; Oleoresins obtained by solvent extraction of these; Aromatic vegetable oils such as coffee oil, roasted nut oils, and sesame oil; Natural oils such as vanillin, maltol, linalool, graniol, citral, and limonene Alternatively, synthetic fragrance compounds may be mentioned.
  • citrus essential oils such as l-menthol, orange oil, lemon oil, grapefruit oil, lime oil, tangerine oil, lavender oil, mandarin oil, and pergamot oil
  • sage rosemary, perilla, and basil.
  • Spice oils such as , ginger, and wasabi
  • Oleoresins obtained by solvent extraction of these
  • Aromatic vegetable oils such as coffee oil, roasted
  • l-menthol is preferred, and as the l-menthol, in addition to natural menthol, synthetic menthol, menthol-containing essential oils such as peppermint oil, peppermint oil, and spearmint oil can be used singly or in combination.
  • essential oils examples include cypress essential oil, cypress essential oil, cedar essential oil, and pine essential oil.
  • the content of volatile components in the hydrogel is preferably 0.50 to 5.0% by mass, more preferably 1.0 to 3.0% by mass, based on 100% by mass of the hydrogel. It is preferable that the content of volatile components is 0.50% by mass or more, since a hydrogel with excellent sustained release properties of volatile components can be obtained. It is preferable that the volatile component content is 5.0% by mass or less, since there is less possibility that the volatile component will precipitate into the hydrogel.
  • the above volatile components can be optionally used as a solvent solution diluted with a solvent.
  • the solvent is not particularly limited as long as it is uniformly miscible with the volatile components, but ester oils, silicone oils, hydrocarbon oils, waxes, and the like are preferred.
  • Neolite 100P manufactured by Kyukyu Alcohol Kogyo Co., Ltd.
  • KAK HL manufactured by Kyukyu Alcohol Kogyo Co., Ltd.
  • the volatile component concentration is 20% by mass or more.
  • the content of the solvent in the hydrogel is preferably 0 to 5.0% by mass based on 100% by mass of the hydrogel.
  • the content of the solvent is within the above range, a large amount of volatile components can be supported in the porous resin particles, and a hydrogel with excellent sustained release properties of volatile components can be obtained, which is preferable.
  • Porous resin particles carrying a volatile component can be obtained by mixing a volatile component or a solvent solution containing a volatile component with porous resin particles and stirring the mixture. .
  • the stirring time is not particularly limited, but is approximately 0.50 to 12 hours.
  • the mass ratio ((A):(B)) of (A) volatile component to (B) porous resin particles is 1:1 to The ratio is 1:4, preferably 1:2 to 1:2.5.
  • volatile components can be supported in the porous particles, and a hydrogel with excellent sustained release properties of volatile components can be obtained.
  • the hydrogel of the present invention preferably contains a polymer matrix, water, and a wetting agent.
  • the polymer matrix is preferably contained in an amount of 10 to 40% by weight, more preferably 15 to 30% by weight, in 100% by weight of the hydrogel.
  • the content is 10% by mass or more, the hydrogel has sufficient shape retention and is unlikely to be too soft or break easily.
  • the content is 40% by mass or less, the flexibility of the hydrogel is unlikely to be impaired.
  • the polymer matrix is not particularly limited as long as it can form a network structure and contain at least water to form a gel.
  • it can be formed from a copolymer of a monofunctional monomer having one ethylenically unsaturated group and a crosslinkable monomer.
  • the monofunctional monomer is not particularly limited as long as it has one ethylenically unsaturated group, but is preferably a water-soluble monomer.
  • monofunctional monomers include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, dialkyl(meth)acrylamide such as N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, Alkyl (meth)acrylamides such as N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide; N-hydroxyethyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, etc.
  • One type is preferably used, but it is not limited to this.
  • These monofunctional monomers may be used alone or in combination of two or more.
  • vinylamide monofunctional monomers such as N-vinylpyrrolidone, N-vinylacetamide, and N-vinylformamide
  • nonionic monomers such as allyl alcohol
  • Functional monomers, styrene monomers, etc. can be used. These monofunctional monomers may be used alone or in combination of two or more.
  • the content of structural units derived from monofunctional monomers in the hydrogel is preferably in the range of 10 to 40% by mass, more preferably 15 to 35% by mass, based on 100% by mass of the hydrogel. preferable. It is preferable that the content of the structural unit derived from the monofunctional monomer is within the above range from the viewpoint of the shape, adhesive strength, handleability, and flexibility of the hydrogel.
  • the content is 10% by mass or more, there is less risk of deterioration in shape stability due to a small amount of monofunctional monomer, and the cohesive force and the retention force of the hydrogel itself do not decrease, resulting in a moderate amount of A hydrogel with adhesive strength is obtained.
  • the content is 40% by mass or less, a hydrogel having appropriate adhesive strength can be obtained, and the flexibility of the hydrogel is unlikely to be impaired.
  • crosslinkable monomer it is preferable to use a monomer having two or more polymerizable double bonds in the molecule.
  • crosslinkable monomers include N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, (poly)ethylene glycol di(meth)acrylate, (poly) Polyfunctional (meth)acrylamides or (meth)acrylates such as propylene glycol di(meth)acrylate, (poly)glycerin di(meth)acrylate, (poly)glycerin tri(meth)acrylate, tetraallyloxyethane, diallylammonium chloride, etc.
  • crosslinkable monomer having two or more polymerizable double bonds in the molecule it has two or more (meth)acryloyl groups or vinyl groups, as described in Japanese Patent No. 2803886, Polyglycerin derivatives, which are polyfunctional compounds having a molecular weight of 400 or more, can also be used.
  • the content of the structural unit derived from the crosslinkable monomer in the hydrogel is preferably within the range of 0.010% by mass to 0.50% by mass, and 0.010% by mass based on 100% by mass of the hydrogel. More preferably, the amount is from % by mass to 0.10% by mass. It is preferable that the content of the structural unit derived from the crosslinkable monomer is within the above range from the viewpoint of the shapeability, adhesive strength, handleability, and flexibility of the hydrogel. When the content is 0.010% by mass or more, there is less risk of deterioration in shape stability due to low crosslinking density, and the cohesive force and holding power of the hydrogel itself do not decrease, resulting in appropriate adhesive strength. A hydrogel having the following properties is obtained.
  • the content is 0.50% by mass or less, a hydrogel having appropriate adhesive strength can be obtained, and the flexibility of the hydrogel is unlikely to be impaired.
  • the content of water in the hydrogel is not particularly limited, but is preferably 10 to 60% by mass, more preferably 15 to 30% by mass, based on 100% by mass of the hydrogel.
  • the water content is 10% by mass or more, the water content relative to the equilibrium water content of the hydrogel does not become too low, and there is little risk of deterioration (for example, swelling, etc.) due to the hygroscopicity of the hydrogel.
  • the water content is 60% by mass or less, the water content does not become too large relative to the equilibrium water content of the hydrogel, and the risk of deterioration (for example, shrinkage, etc.) due to drying of the hydrogel is unlikely to occur.
  • wetting agents are not particularly limited, and include diols such as ethylene glycol, triethylene glycol, 1,6-hexanediol, 1,9-nonanediol, propylene glycol, butanediol; glycerin, pentaerythritol, sorbitol, etc.
  • Trivalent or higher polyhydric alcohols Trivalent or higher polyhydric alcohols; polyhydric alcohol condensates such as polyethylene glycol, polypropylene glycol, polyglycerin; polyhydric alcohol modified products such as polyoxyethylene glycerin; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyhydric alcohols Polyoxyethylene alkyl ethers such as oxyethylene isostearyl ether and polyoxyethylene methyl glucoside; polyoxypropylene alkyls such as polyoxypropylene lauryl ether, polyoxypropylene stearyl ether, polyoxypropylene isostearyl ether, and polyoxypropylene methyl glucoside; Polyoxyalkylene alkyl ethers such as ether; monosaccharides such as xylose, arabinose, glucose, galactose, and mannose; disaccharides such as sucrose, maltose, cellobiose, and lactose; oligos
  • polyhydric alcohols that are liquid in the temperature range in which the hydrogel is used (for example, around 20°C when used indoors), and specifically, polyhydric alcohols such as ethylene glycol, triethylene glycol, and propylene glycol are used. , polypropylene glycol, polyethylene glycol, polyglycerin, glycerin, and the like are suitable.
  • the content of the wetting agent in the hydrogel is not particularly limited, but is preferably in the range of 20 to 70% by mass, and preferably in the range of 30 to 60% by mass, based on 100% by mass of the hydrogel. More preferred.
  • the content of the wetting agent is 20% by mass or more, the obtained hydrogel has a moisturizing ability and evaporation of water is also suppressed, which improves the stability of the hydrogel over time, which is preferable.
  • the content of the wetting agent is 70% by mass or less, since the wetting agent does not bleed out from the surface of the hydrogel, and a decrease in adhesive strength due to bleedout is suppressed.
  • the hydrogel can also optionally contain an electrolyte, which can impart electrical conductivity to the hydrogel.
  • the content of the electrolyte in the hydrogel is preferably 0.050 to 10% by mass, and 0.10 to 6.0% by mass, based on 100% by mass of the hydrogel. It is more preferable that it is mass %. It is preferable that the electrolyte content is 0.050% by mass or more because the impedance of the hydrogel sheet decreases and the conductivity becomes good.
  • the content of the electrolyte in the hydrogel is too large, it will be difficult to dissolve the electrolyte in the hydrogel, and there is a risk that crystals will precipitate inside the gel and dissolution of other components will be inhibited. . Further, the conductivity reaches a ceiling, and further addition is no longer beneficial from the viewpoint of imparting conductivity.
  • the electrolyte is not particularly limited, and includes, for example, alkali metal halides such as sodium halides (e.g., sodium chloride), lithium halides, and potassium halides; alkaline earth metal halides such as magnesium halides and calcium halides; Examples include other metal halides. Further, hypochlorites, chlorites, chlorates, perchlorates, sulfates, carbonates, nitrates, and phosphates of various metals are also suitably used as the electrolyte.
  • alkali metal halides such as sodium halides (e.g., sodium chloride), lithium halides, and potassium halides
  • alkaline earth metal halides such as magnesium halides and calcium halides
  • hypochlorites, chlorites, chlorates, perchlorates, sulfates, carbonates, nitrates, and phosphates of various metals are also suitably used as the electrolyte.
  • inorganic salts such as ammonium salts and various complex salts; salts of monovalent organic carboxylic acids such as acetic acid, benzoic acid, and lactic acid; salts of polyvalent organic carboxylic acids such as tartaric acid; phthalic acid, succinic acid, and adipine Monovalent or divalent or more monovalent salts of polycarboxylic acids such as acids, citric acid; metal salts of organic acids such as sulfonic acids and amino acids; organic ammonium salts, etc. are also suitable.
  • a base such as sodium hydroxide may be appropriately added to the hydrogel for the purpose of adjusting the pH.
  • the hydrogel may optionally contain other additives.
  • Other additives include, for example, rust preventives, antifungal agents, antioxidants, dispersants, antifoaming agents, stabilizers, surfactants, colorants, and the like.
  • the hydrogel of the present invention may further include an intermediate base material embedded along the in-plane direction.
  • the in-plane direction of the hydrogel refers to any direction within a plane perpendicular to the thickness direction of the hydrogel. Having an intermediate base material leads to reinforcement of the hydrogel and improvement of shape retention during cutting.
  • a hydrogel with an intermediate base material embedded along the in-plane direction can be interchangeably expressed as a composite material comprising a hydrogel and an intermediate base material embedded along the in-plane direction of the hydrogel. You can also do it.
  • the intermediate base material is not particularly limited, but includes nonwoven fabrics, woven fabrics, paper, films, and the like.
  • natural fibers such as cellulose, silk, and hemp
  • synthetic fibers such as polyester, nylon, rayon, polyethylene, polypropylene, and polyurethane, or blends thereof can be used, and a binder may be optionally used. It may also be optionally colored.
  • the method for producing the nonwoven fabric is not particularly limited, but examples include a dry method, a wet method, a spunbond method, a melt blown method, an air laid method, a chemical bond method, a thermal bond method, a needle punch method, and a hydroentangling method. It is more preferable to adopt a manufacturing method according to the basis weight, material, etc., and to have no unevenness in basis weight for controlling the position of the intermediate base material.
  • the woven fabric is also not particularly limited, and can be selected as appropriate, such as plain weave, tricot, and raschel.
  • the basis weight of the nonwoven fabric or woven fabric is not particularly limited as long as it can obtain predetermined physical properties as an intermediate base material, but is preferably 10 to 100 g/m 2 , for example.
  • the gel sheet can be reinforced.
  • the basis weight is 100 g/m 2 or less, the intermediate base material does not become too hard and does not impair the followability and conductivity of the hydrogel to the skin.
  • the thickness of the intermediate base material is too thick, the liquid permeability will be poor, and if it is too thin, it may not be possible to reinforce the gel sheet, etc., as in the case where the basis weight is too small. It will be set appropriately taking into consideration. Preferably it is within the range of 0.050 mm to 2.0 mm. Further, it is more preferably 0.050 mm to 0.50 mm, and particularly preferably 0.080 mm to 0.30 mm.
  • the thickness of the hydrogel of the present invention is appropriately selected depending on the application, and is, for example, within the range of 0.20 mm to 2.0 mm. In one preferred embodiment, the thickness of the hydrogel of the invention is between 0.30 mm and 1.2 mm.
  • the hydrogel of the present invention can stably disperse a large amount of volatile components and has excellent sustained release properties of volatile components.
  • the hydrogel of the present invention Since the hydrogel of the present invention has excellent flexibility and water retention, it can be used in a wide variety of fields such as medical care, cosmetics, food, chemistry, civil engineering, agriculture, bioengineering, and sports-related fields.
  • it can be used as a biological electrode hydrogel, a cooling gel, a cosmetic face mask, a cell culture medium, etc.
  • the hydrogel of the present invention can be used as a biological electrode in a monitoring device or a device for performing treatment using electrical stimulation, a return electrode for an electrosurgical device, an adhesive tape, or a wound dressing.
  • the hydrogel of the embodiment of the present invention can be produced by uniformly dispersing each of the above-mentioned materials other than water and a polymerization initiator in water, and heating or irradiating the resulting mixed solution with ultraviolet rays. It is composed of a gelled product obtained by polymerization and crosslinking.
  • the polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, and any known thermal polymerization initiator or photopolymerization initiator for polymerizing acrylic monomers can be used.
  • the content of the polymerization initiator is not particularly limited, but it is preferably 0.010% by mass or more, and 1.0% by mass or more based on 100% by mass of the total amount of the obtained hydrogel (the total amount of the above-mentioned compounded liquid). It is preferably less than % by mass.
  • the cumulative irradiation amount of ultraviolet rays varies depending on the content of the polymerization initiator, etc., but is preferably in the range of 800 to 10,000 mJ/ cm2 , and 2,000 to 10,000 mJ/cm2. More preferably, it is within the range of cm2 .
  • the reaction rate of the non-crosslinkable monomer and the crosslinkable monomer can be adjusted as appropriate.
  • the hydrogel of the above embodiment of the present invention can be formed into a desired shape such as a sheet by pouring the blend into a container with a desired shape, such as a bottomed container with a substantially rectangular cross section, and polymerizing it by heating or UV irradiation. It can be formed into.
  • the shape of the hydrogel formed into a sheet can be any shape depending on the purpose, and examples include, but are not limited to, a substantially rectangular shape, a substantially circular shape, and the like.
  • the sheet-like hydrogel will be referred to as a "hydrogel sheet" or simply a "gel sheet.”
  • the process for producing a hydrogel sheet with an intermediate base material is not particularly limited, and detailed conditions vary depending on the composition of the hydrogel, the material, thickness, etc. of the intermediate base material.
  • the intermediate base material is held in the air with a certain level of tension applied to minimize the vertical deformation of the intermediate base material, and the blended liquid is poured onto the upper and lower sides of the intermediate base material.
  • FIG. 1A shows a schematic plan view of an embodiment of the gel sheet
  • FIG. 1B shows a cross-sectional view of the gel sheet of FIG. 1A along line 1B-1B.
  • the gel sheet 1 includes the hydrogel 2 of the present invention, and an intermediate base material 3 is embedded along the in-plane direction of the hydrogel 2, and the intermediate base material 3 is a nonwoven fabric or a woven fabric.
  • the base film 4 is provided on one side of the gel sheet 1
  • the top film 5 is provided on the back side of the side on which the base film 4 is provided, but the base film 4 and the top film 5 may be omitted. good.
  • the base film 4 for example, a resin film made of resin such as polyester, polyolefin, polystyrene, polyurethane, paper, paper laminated with the resin film, etc. can be used.
  • the surface of the base film 4 in contact with the gel sheet 1 is preferably subjected to a mold release treatment.
  • the mold release treatment include silicone coating, and particularly preferred is a baking-type silicone coating in which a crosslinking and curing reaction is performed using heat or ultraviolet light.
  • a baking-type silicone coating in which a crosslinking and curing reaction is performed using heat or ultraviolet light.
  • biaxially stretched PET (polyethylene terephthalate) film, OPP (stretched polypropylene) film, etc. are particularly preferred.
  • the top film 5 it is basically possible to use the same material as the base film, but when polymerizing by irradiating ultraviolet rays etc. from above with the top film provided, it is necessary to In order not to interfere with polymerization, it is preferable to select a film made of a material that does not block light.
  • Example 1 Preparation of volatile component-containing particles Using a stirring/mixing container, dissolve 1% by mass of the volatile component l-menthol in 1% by mass of the solvent Neolite 100P (manufactured by Kyukyu Alcohol Kogyo Co., Ltd.) as shown in Table 1. , a solvent solution of volatile components was obtained.
  • the solvent solution was prepared with reference to our patent No. 5812374, and had an average pore diameter of 18 nm, oil absorption of 150 ml/100 g, pore volume of 0.40 ml/g, specific surface area of 80 m 2 /g, and bulk specific gravity of 0.40 g/ml. , was added little by little to 2% by mass of particles A having a parameter of a volume average particle diameter of 8 ⁇ m, and after stirring, volatile component-containing particles were obtained.
  • the obtained liquid mixture was dropped onto a silicone-coated PET film (base film) with a thickness of 100 ⁇ m, and a nylon-based woven fabric and a silicone-coated thick film were placed on top of the dropped liquid mixture.
  • a PET film (top film) with a thickness of 38 ⁇ m was placed on the plate to spread the blended liquid uniformly and fixed to a thickness of 0.90 mm.
  • the hydrogel sheet of Example 1 with a thickness of 0.90 mm was obtained by irradiating this mixed solution with ultraviolet rays at an energy amount of 3000 mJ/cm 2 using a metal halide lamp.
  • Examples 2 to 10 The hydrogels of Examples 2 to 10 were produced in the same manner as Example 1, except that the mass % of each component was changed as shown in Table 1.
  • Comparative Examples 1 to 4 The hydrogels of Comparative Examples 1 to 4 were produced in the same manner as in Example 1, except that the mass % of each component was changed as shown in Table 1. In Comparative Examples 1, 2, and 4, hydrogels could not be produced because the volatile components could not be stably dispersed and precipitated in the hydrogels.
  • Examples 1 to 10 and Comparative Examples 1 to 4 are as follows.
  • ⁇ AAM acrylamide ⁇ AA: acrylic acid
  • ⁇ DMAA N,N-dimethylacrylamide
  • ⁇ MBAA N,N'-methylenebisacrylamide
  • ⁇ l-menthol menthol JP COS (manufactured by Takasago International Corporation)
  • ⁇ Lavender oil LAVENDER GEL SK F 2263 (manufactured by Inoue Fragrance Manufacturing Co., Ltd.)
  • ⁇ Citrus oil CITRUS GEL SK F 2264 (manufactured by Inoue Fragrance Manufacturing Co., Ltd.)
  • ⁇ Neolite 100P Isodecyl neopentanoate (manufactured by Kyukyu Alcohol Kogyo Co., Ltd.)
  • Particle A porous resin particles
  • Score 1 Odorless Score 2: I could smell a faint odor when I peeled off the protective film and brought my nose close to the gel surface
  • Score 3 I could smell the odor when I turned over the protective film
  • Score 4 I could smell the odor when I turned over the protective film I felt it strongly

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CN117482267A (zh) * 2023-12-01 2024-02-02 广东爱车小屋电子商务科技有限公司 一种水基凝胶固体香薰及其制备方法

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JPH05339102A (ja) * 1992-06-04 1993-12-21 Sekisui Chem Co Ltd 揮発性有効成分を放出する積層体
JP2001279119A (ja) * 2000-03-30 2001-10-10 Shiseido Co Ltd ゲル状芳香剤組成物
JP2003070898A (ja) * 2001-09-04 2003-03-11 Life Kea Giken Kk 貼付剤とその製造方法
WO2014050177A1 (ja) * 2012-09-26 2014-04-03 積水化成品工業株式会社 多孔質樹脂粒子、多孔質樹脂粒子の製造方法、およびその用途
JP2021050337A (ja) * 2014-11-20 2021-04-01 ブローダ・テクノロジーズ・カンパニー・リミテッドＢｒｏｄａ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｃｏ．， Ｌｔｄ． 水溶性超分子複合体
JP2021147543A (ja) * 2020-03-19 2021-09-27 積水化成品工業株式会社 ハイドロゲル

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Publication number Priority date Publication date Assignee Title
JPH05339102A (ja) * 1992-06-04 1993-12-21 Sekisui Chem Co Ltd 揮発性有効成分を放出する積層体
JP2001279119A (ja) * 2000-03-30 2001-10-10 Shiseido Co Ltd ゲル状芳香剤組成物
JP2003070898A (ja) * 2001-09-04 2003-03-11 Life Kea Giken Kk 貼付剤とその製造方法
WO2014050177A1 (ja) * 2012-09-26 2014-04-03 積水化成品工業株式会社 多孔質樹脂粒子、多孔質樹脂粒子の製造方法、およびその用途
JP2021050337A (ja) * 2014-11-20 2021-04-01 ブローダ・テクノロジーズ・カンパニー・リミテッドＢｒｏｄａ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｃｏ．， Ｌｔｄ． 水溶性超分子複合体
JP2021147543A (ja) * 2020-03-19 2021-09-27 積水化成品工業株式会社 ハイドロゲル

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Publication number Priority date Publication date Assignee Title
CN117482267A (zh) * 2023-12-01 2024-02-02 广东爱车小屋电子商务科技有限公司 一种水基凝胶固体香薰及其制备方法

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