WO2023276950A1 - 医療用処置材及びその製造方法 - Google Patents

医療用処置材及びその製造方法 Download PDF

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WO2023276950A1
WO2023276950A1 PCT/JP2022/025565 JP2022025565W WO2023276950A1 WO 2023276950 A1 WO2023276950 A1 WO 2023276950A1 JP 2022025565 W JP2022025565 W JP 2022025565W WO 2023276950 A1 WO2023276950 A1 WO 2023276950A1
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Prior art keywords
polymer
ethylenically unsaturated
unsaturated monomer
medical treatment
treatment material
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English (en)
French (fr)
Japanese (ja)
Inventor
義之 小山
智子 伊藤
賢一 中村
彩歌 大内
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Toagosei Co Ltd
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Toagosei Co Ltd
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Priority to CN202280038748.3A priority Critical patent/CN117396238A/zh
Priority to US18/571,487 priority patent/US20240277891A1/en
Priority to JP2023531938A priority patent/JPWO2023276950A1/ja
Publication of WO2023276950A1 publication Critical patent/WO2023276950A1/ja
Anticipated expiration legal-status Critical
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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
    • A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
    • A61L26/0052—Mixtures of macromolecular compounds
    • 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
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • 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
    • A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0061—Use of materials characterised by their function or physical properties
    • A61L26/008—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
    • A61L27/14—Macromolecular materials
    • A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and 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 a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2333/02—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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2333/04—Characterised by the use 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; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use 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; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2433/02—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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
    • C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones

Definitions

  • TECHNICAL FIELD The present disclosure relates to a medical treatment material and its manufacturing method, and more particularly to a medical treatment material that forms a hydrogel upon contact with water and its manufacturing method.
  • Patent Document 1 proposes a hydrogel-forming material as a medical treatment material that forms a hydrogel through hydrogen bonding between polyacrylic acid and polyvinylpyrrolidone.
  • an aqueous solution of either polyacrylic acid or polyvinylpyrrolidone is dried into a film, and the film is brought into contact with the other aqueous solution and then dried to form a hydrogel.
  • dry films and sponges that can form hydrogels by absorbing water are obtained.
  • the films and sponges thus obtained have the function of rapidly absorbing moisture such as blood and interstitial fluid on wet biological tissues such as wounds and hemostatic sites, swelling, and adhering to the biological tissues. .
  • the present disclosure has been made in view of the above circumstances, and its purpose is to provide a medical treatment material that has excellent adhesiveness to living tissue.
  • a medical treatment material containing a specific carboxyl group-containing polymer and a polymer capable of forming a hydrogen bond with this polymer is a biological tissue. It was found that it exhibits high adhesiveness to Specifically, the present disclosure provides the following means.
  • a medical treatment material that forms a hydrogel upon contact with water which is a polymer (A ) and a polymer (B) containing a structural unit derived from an ethylenically unsaturated monomer (mb) having a functional group E capable of forming a hydrogen bond with a carboxyl group (except for the polymer (A) ), and at least one of the polymer (A) and the polymer (B) contains the ethylenically unsaturated monomer (ma) and the ethylenically unsaturated monomer (mb) is a medical treatment material comprising structural units derived from different ethylenically unsaturated monomers (mc) (excluding ethylenically unsaturated monomers having a crosslinkable functional group).
  • the ethylenically unsaturated monomer (mc1) is at least one selected from the group consisting of acrylic acid dimer, acrylic acid trimer, acrylic acid tetramer, and ⁇ -carboxy-caprolactone mono(meth)acrylate.
  • ethylenically unsaturated monomer (mc) comprises an ethylenically unsaturated monomer (mc2) having no carboxyl group and the functional group E medical treatment materials.
  • the polymer (A) contains a structural unit derived from the ethylenically unsaturated monomer (mc), and the ethylenically unsaturated monomer (ma) constituting the polymer (A) and the ethylenically unsaturated monomer (mc) of the above [1] to [4], wherein the mass ratio ((ma)/(mc)) is 99.7/0.3 to 50/50.
  • Any medical treatment material is 99.7/0.3 to 50/50.
  • a method for producing a medical treatment material that forms a hydrogel upon contact with water comprising a step of obtaining a solid film containing one of polymer (A) and polymer (B) and a step of contacting the film-like solid with a solution containing the other polymer of the polymer (A) and the polymer (B), followed by drying, wherein the polymer (A ) is a polymer containing a structural unit derived from an ethylenically unsaturated monomer (ma) having a molecular weight of 115 or less having a carboxyl group, and the polymer (B) can form a hydrogen bond with the carboxyl group.
  • the polymer (A ) is a polymer containing a structural unit derived from an ethylenically unsaturated monomer (ma) having a molecular weight of 115 or less having a carboxyl group
  • a polymer (excluding the polymer (A)) containing a structural unit derived from an ethylenically unsaturated monomer (mb) having a functional group E, and the polymer (A) and the polymer ( At least one of B) is an ethylenically unsaturated monomer (mc) different from the ethylenically unsaturated monomer (ma) and the ethylenically unsaturated monomer (mb) (provided that the crosslinkable functional A method for producing a medical treatment material containing a structural unit derived from (excluding an ethylenically unsaturated monomer having a group).
  • a polymer component of a medical treatment material that forms a hydrogel a polymer (A ) and a polymer (B) containing a structural unit derived from an ethylenically unsaturated monomer (mb) having a functional group E capable of forming a hydrogen bond with a carboxyl group, and further polymer (A) and at least one of the polymer (B) is a polymer containing a structural unit derived from an ethylenically unsaturated monomer (mc) to obtain a medical treatment material having excellent adhesiveness to living tissue. be able to.
  • (meth)acryl means acryl and/or methacryl.
  • (Meth)acrylate means acrylate and/or methacrylate.
  • the medical treatment material of the present disclosure is a medical treatment material that forms hydrogel upon contact with water.
  • the medical treatment material is a hydrogel-forming article that can be used as an anti-adhesion material, a hemostatic material, a wound dressing material, etc., and is, for example, a film-like, sponge-like, sheet-like or powdery hydrogel-forming material.
  • the medical treatment material of the present disclosure contains the following polymer (A) and polymer (B).
  • At least one of the polymer (A) and the polymer (B) contained in the medical treatment material of the present disclosure is an ethylenically unsaturated monomer (ma) and an ethylenically unsaturated monomer (mb). contains structural units derived from different ethylenically unsaturated monomers (mc) (excluding ethylenically unsaturated monomers having crosslinkable functional groups).
  • ⁇ Polymer (A)> (Ethylenically unsaturated monomer (ma))
  • Examples of the ethylenically unsaturated monomer (ma) constituting the polymer (A) include (meth)acrylic acid, crotonic acid, 2-ethylpropenoic acid and the like.
  • the ethylenically unsaturated monomer (ma) is preferably (meth)acrylic acid, and more preferably acrylic acid because it can form a hydrogel having higher adhesiveness to living tissue upon contact with water.
  • the content of structural units derived from the ethylenically unsaturated monomer (ma) is preferably 40% by mass or more, based on the total structural units constituting the polymer (A), and 50 It is more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
  • the content of structural units derived from the ethylenically unsaturated monomer (ma) is preferably 99.9% by mass or less, and 99.7% by mass, based on the total structural units constituting the polymer (A). % or less is more preferable, and 99.5% by mass or less is even more preferable.
  • the ethylenically unsaturated monomer (ma) constituting the polymer (A) may be of one type or two or more types.
  • the polymer (A) preferably contains a structural unit derived from the ethylenically unsaturated monomer (mc) together with the ethylenically unsaturated monomer (ma).
  • a structural unit derived from an ethylenically unsaturated monomer (mc) in the polymer (A) can be improved.
  • the ethylenically unsaturated monomer (mc) has only one ethylenically unsaturated group as a group involved in polymerization and is copolymerizable with the ethylenically unsaturated monomer (ma) is not particularly limited.
  • an ethylenically unsaturated monomer having a carboxyl group and a molecular weight of more than 115 (hereinafter also referred to as "unsaturated monomer (mc1)"), and a carboxyl group and Examples thereof include ethylenically unsaturated monomers having no functional group E (hereinafter also referred to as “unsaturated monomer (mc2)").
  • ⁇ Unsaturated monomer (mc1) examples include maleic acid, fumaric acid, itaconic acid, citraconic acid, cinnamic acid, (meth)acrylic acid dimer, (meth)acrylic acid trimer, (meth)acrylic acid tetramer, succinic acid mono (2-(meth)acryloyloxyethyl), monohydroxyethyl phthalate (meth)acrylate, ⁇ -carboxy-caprolactone mono(meth)acrylate, 4-carboxystyrene and the like.
  • unsaturated monomers (mc1) include maleic acid, fumaric acid, itaconic acid, citraconic acid, cinnamic acid, (meth)acrylic acid dimer, (meth)acrylic acid trimer, (meth)acrylic acid tetramer, succinic acid mono (2-(meth)acryloyloxyethyl), monohydroxyethyl phthalate (meth)acrylate,
  • the unsaturated monomer (mc1) is, among others, a group consisting of acrylic acid dimers, acrylic acid trimers, acrylic acid tetramers, and ⁇ -carboxy-caprolactone mono(meth)acrylates because of their high effect of improving adhesion to living tissue. At least one selected from can be preferably used.
  • ⁇ Unsaturated monomer (mc2) examples include (meth)acrylic acid alkyl esters, (meth)acrylic acid aliphatic cyclic esters, (meth)acrylic acid aromatic esters, and (meth)acrylic acid alkoxyalkyl esters. , (meth)acrylic acid hydroxyalkyl ester, polyalkylene glycol mono(meth)acrylate, and the like.
  • the (meth)acrylic acid alkyl ester is preferably a compound in which the alkyl group (R) in the alkyl ester portion (-COOR) has 1 to 12 carbon atoms, from the viewpoint of ensuring the water solubility of the polymer (A).
  • Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylic isobutyl acid, tert-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n (meth)acrylate -nonyl, isononyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate and the like.
  • aliphatic cyclic esters of (meth)acrylic acid include cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, Examples include isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate and dicyclopentanyl (meth)acrylate.
  • aromatic esters of (meth)acrylic acid include phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate and (meth)acrylate. and 3-phenoxypropyl acrylate.
  • (meth)acrylate alkoxyalkyl esters include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, n-propoxyethyl (meth)acrylate, n-butoxyethyl (meth)acrylate, Methoxypropyl (meth)acrylate, ethoxypropyl (meth)acrylate, n-propoxypropyl (meth)acrylate, n-butoxypropyl (meth)acrylate, methoxybutyl (meth)acrylate, ethoxy (meth)acrylate Butyl, n-propoxybutyl (meth)acrylate and n-butoxybutyl (meth)acrylate.
  • (meth)acrylic acid hydroxyalkyl esters include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. -hydroxybutyl, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
  • Polyalkylene glycol mono(meth)acrylates include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate and polyethylene glycol-polypropylene glycol mono(meth)acrylate.
  • the unsaturated monomer (mc2) is an alkyl (meth)acrylic acid ester, an aliphatic cyclic (meth)acrylic acid ester, an aromatic (meth)acrylic acid ester and an alkoxy (meth)acrylic acid. At least one selected from the group consisting of alkyl esters is preferred. Among these, the unsaturated monomer (mc2) is preferably a (meth)acrylic acid alkyl ester because of its high effect of improving adhesiveness to living tissue.
  • the (meth)acrylic acid alkyl esters constituting the polymer (A) compounds in which the alkyl group (R) has 1 to 8 carbon atoms are preferable, and compounds in which the carbon number is 1 to 4 are more preferable.
  • the (meth)acrylic acid alkyl esters constituting the polymer (A) may be of one type or two or more types.
  • the polymer (A) contains a structural unit derived from an ethylenically unsaturated monomer (mc), the ethylenically unsaturated monomer (ma) and the ethylenically unsaturated monomer constituting the polymer (A)
  • the mass ratio ((ma)/(mc)) to the body (mc) is preferably 99.7/0.3 to 50/50.
  • the mass ratio of the ethylenically unsaturated monomer (ma) and the ethylenically unsaturated monomer (mc) is within the above range, the adhesiveness of the obtained hydrogel to living tissue is highly improved, which is preferable. is.
  • the mass ratio of the ethylenically unsaturated monomer (ma) and the ethylenically unsaturated monomer (mc) constituting the polymer (A) is 99.7/0.3 to 60/40. is more preferably 99.5/0.5 to 70/30, even more preferably 99.5/0.5 to 80/20.
  • the ethylenically unsaturated monomers (mc) constituting the polymer (A) may be of one type or two or more types.
  • the unsaturated monomer (mc1) is used as the ethylenically unsaturated monomer (mc)
  • the introduction amount of the ethylenically unsaturated monomer (mc) in the polymer (A) is reduced. (That is, while increasing the amount of the ethylenically unsaturated monomer (ma) introduced), it is preferable in that the effect of improving the adhesiveness of the hydrogel to the living tissue can be sufficiently obtained.
  • the polymer (A) may be a crosslinked polymer or a polymer having a weight average molecular weight of 100,000 or more (hereinafter also referred to as "high molecular weight polymer (AH)").
  • the crosslinked polymer is preferably used as the polymer (A) because of its superior swelling property upon contact with moisture and adhesiveness to living tissue.
  • the polymer (A) as a crosslinked polymer can be preferably used when the polymer (B) contains a structural unit derived from the ethylenically unsaturated monomer (mc).
  • the polymer (A) is a crosslinked polymer
  • the polymer (A) is an ethylenically unsaturated monomer having a crosslinkable functional group (hereinafter also referred to as "unsaturated monomer (md)"). It preferably contains a structural unit derived from.
  • the crosslinkable functional group possessed by the unsaturated monomer (md) is preferably a polymerizable unsaturated group or a self-crosslinkable functional group.
  • the unsaturated monomer (md) includes a polyfunctional polymerizable monomer having two or more ethylenically unsaturated groups, and a self-crosslinkable functional group (e.g., hydrolyzable silyl group, etc.).
  • polyfunctional polymerizable monomers include polyfunctional (meth)acrylate compounds, polyfunctional alkenyl compounds, compounds having both a (meth)acryloyl group and an alkenyl group, and the like.
  • the ethylenically unsaturated monomer having a crosslinkable functional group is preferably a polyfunctional alkenyl compound because a uniform crosslinked structure can be easily obtained.
  • polyfunctional alkenyl compounds include polyfunctional allyl ether compounds such as trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, tetraallyloxyethane, and polyallyl saccharose; Polyfunctional allyl compounds such as diallyl phthalate; Polyfunctional vinyl compounds such as divinylbenzene; Allyl (meth)acrylate, isopropenyl (meth)acrylate, butenyl (meth)acrylate, pentenyl (meth)acrylate, (meth)acrylate Examples include alkenyl group-containing (meth)acrylic acid compounds such as 2-(2-vinyloxyethoxy)ethyl acrylate. Among these polyfunctional alkenyl compounds, polyfunctional allyl ether compounds having a plurality of allyl ether groups in the molecule are particularly preferred.
  • self-crosslinking monomers include hydrolyzable silyl group-containing vinyl monomers.
  • hydrolyzable silyl group-containing vinyl monomers include vinylsilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and vinyldimethylmethoxysilane; trimethoxysilylpropyl (meth)acrylate; Silyl group-containing (meth)acrylic acid esters such as triethoxysilylpropyl (meth)acrylate and methyldimethoxysilylpropyl (meth)acrylate; trimethoxysilylpropyl vinyl ether, vinyl trimethoxysilylundecanoate and the like.
  • the amount of the structural unit is 0.01% by mass with respect to the total structural units constituting the polymer (A).
  • the above is preferable, and 0.1% by mass or more is more preferable.
  • the amount of structural units derived from the unsaturated monomer (md) contained in the polymer (A) is preferably 5% by mass or less with respect to the total structural units constituting the polymer (A). % by mass or less is more preferable, and 1% by mass or less is even more preferable.
  • the unsaturated monomers (md) constituting the polymer (A) may be of one type or two or more types.
  • a commercially available product can also be used as the crosslinked polymer.
  • examples of such commercially available products include, for example, the trade names of Junron (registered trademark) PW-120, Junron PW-121, Junron PW-312S (manufactured by Toagosei Co., Ltd.), Carbopol (registered trademark) 934P NF, and Carbopol. 981, Carbopol Ultrez 10, Carbopol Ultrez 30 (manufactured by Lubrizol) and the like.
  • the high molecular weight polymer (AH) is preferably a polymer having no structural unit (mc1).
  • the weight average molecular weight (Mw) of the high molecular weight polymer (AH) is not particularly limited, but from the viewpoint of ensuring mechanical strength and thickening effect, it is preferably 5 ⁇ 10 5 or more, more preferably 1 ⁇ 10. It is 6 or more, more preferably 1.8 ⁇ 10 6 or more. From the viewpoint of handleability, Mw of the high molecular weight polymer (AH) is preferably 1 ⁇ 10 7 or less, more preferably 8 ⁇ 10 6 or less, and still more preferably 5 ⁇ 10 6 or less. .
  • the molecular weight of the high-molecular-weight polymer (AH) is a polystyrene-equivalent value measured by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent after the carboxyl group is methylated with trimethylsilyldiazomethane.
  • the polymer (B) is not particularly limited as long as it has a functional group E capable of forming a hydrogen bond with the carboxyl group of the polymer (A) and is different from the polymer (A).
  • the functional group E include an amide group, a cyano group, a carbonyl group, an amino group, and a hydroxyl group.
  • the functional group E possessed by the polymer (B) may be of one type or two or more types.
  • the functional group E is, among others, an amide group and/or Alternatively, a hydroxyl group is preferred, and an amide group is particularly preferred.
  • the polymer (B) having an amide group can preferably be produced by polymerization using an ethylenically unsaturated monomer having an amide group as the ethylenically unsaturated monomer (mb).
  • Ethylenically unsaturated monomers having an amide group include, for example, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N-methyl(meth)acrylamide , N-vinyl-2-pyrrolidone, 1-vinyl-4-methyl-2-pyrrolidone, and the like.
  • polymer (B) having a hydroxyl group examples include polyethylene glycol (commercially available, such as Macrogol 4000, Macrogol 6000 and Macrogol 20000 manufactured by NOF Corporation), polyoxyethylene hydrogenated castor oil (commercially available, such as BASF Cremophor RH40 manufactured by Nikko Chemical Co., Ltd.; HCO-40 and HCO-60 manufactured by Nikko Chemical Co., Ltd.); be done.
  • polyethylene glycol commercially available, such as Macrogol 4000, Macrogol 6000 and Macrogol 20000 manufactured by NOF Corporation
  • polyoxyethylene hydrogenated castor oil commercially available, such as BASF Cremophor RH40 manufactured by Nikko Chemical Co., Ltd.; HCO-40 and HCO-60 manufactured by Nikko Chemical Co., Ltd.
  • the polymer (B) having a hydroxyl group is preferably polyethylene glycol.
  • the content of the structural units derived from the ethylenically unsaturated monomer having the functional group E is 70% by mass or more with respect to the total structural units constituting the polymer (B). is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 97% by mass or more.
  • a crosslinked polymer or a polymer having a weight average molecular weight of 10,000 or more (hereinafter also referred to as "high molecular weight polymer (BH)") can be preferably used.
  • BH can be used more preferably.
  • the polymer (B) is at least one selected from the group consisting of polyvinylpyrrolidone, polyacrylamide and polymethacrylamide. More preferably at least one selected from the group consisting of polyvinylpyrrolidone and polyacrylamide in terms of excellent polymerizability of the constituent monomers and easy production of the polymer (B). .
  • the polymer (B) may further contain a structural unit derived from the ethylenically unsaturated monomer (mc) together with the ethylenically unsaturated monomer (mb). Further containing a structural unit derived from an ethylenically unsaturated monomer (mc) in the polymer (B) is preferable in that the adhesiveness to living tissue can be improved.
  • Specific examples of the ethylenically unsaturated monomer (mc) include the same monomers as exemplified in the description of the polymer (A).
  • the polymer (B) contains an ethylenically unsaturated monomer (mc)
  • the mass ratio ((mb)/(mc)) of is preferably 99.7/0.3 to 50/50.
  • the mass ratio of the ethylenically unsaturated monomer (mb) and the ethylenically unsaturated monomer (mc) is within the above range, it is preferable because the effect of improving the adhesiveness of the resulting hydrogel to living tissue is high. is.
  • the mass ratio of the ethylenically unsaturated monomer (mb) and the ethylenically unsaturated monomer (mc) constituting the polymer (B) is 99.7/0.3 to 60/40. It is more preferably 99.5/0.5 to 70/30, even more preferably 99.5/0.5 to 80/20.
  • the ethylenically unsaturated monomers (mc) constituting the polymer (B) may be of one type or two or more types.
  • the polymer (A) is an ethylenically unsaturated monomer (mc ) preferably contains a structural unit derived from
  • Polyvinylpyrrolidone as the polymer (B) is typically a polymer composed of N-vinyl-2-pyrrolidone and further contains a structural unit derived from an ethylenically unsaturated monomer (mc). good too. Further, polyvinylpyrrolidone as the polymer (B) is a monomer different from N-vinyl-2-pyrrolidone and the ethylenically unsaturated monomer (mc) (for example, It may contain a structural unit derived from an unsaturated monomer (md)).
  • polyvinylpyrrolidone the content of structural units derived from a monomer different from N-vinyl-2-pyrrolidone and ethylenically unsaturated monomer (mc) is, with respect to all structural units constituting polyvinylpyrrolidone, 3% by mass or less is preferable, and 1% by mass or less is more preferable.
  • polyacrylamide is typically a polymer composed of acrylamide and may further contain a structural unit derived from an ethylenically unsaturated monomer (mc).
  • polyacrylamide as the polymer (B) is a monomer different from acrylamide and ethylenically unsaturated monomer (mc) (e.g., unsaturated monomer ( It may contain a structural unit derived from md)).
  • the content of structural units derived from monomers different from acrylamide and ethylenically unsaturated monomers (mc) is preferably 3% by mass or less with respect to all structural units constituting polyacrylamide. , 1% by mass or less is more preferable.
  • Polymethacrylamide is typically a polymer composed of methacrylamide, and may further contain a structural unit derived from an ethylenically unsaturated monomer (mc).
  • polymethacrylamide as the polymer (B) is a monomer different from methacrylamide and ethylenically unsaturated monomer (mc) (e.g., unsaturated monomer structure (md)) may be included.
  • the content of structural units derived from a monomer different from methacrylamide and ethylenically unsaturated monomer (mc) is 3% by mass with respect to all structural units constituting polymethacrylamide. The following are preferable, and 1 mass % or less is more preferable.
  • the weight average molecular weight (Mw) of the high molecular weight polymer (BH) is not particularly limited, but from the viewpoint of ensuring mechanical strength and thickening effect. , preferably 1 ⁇ 10 4 or more, more preferably 3 ⁇ 10 4 or more, and still more preferably 5 ⁇ 10 4 or more. From the viewpoint of handleability, Mw of the high molecular weight polymer (BH) is preferably 1 ⁇ 10 8 or less, more preferably 5 ⁇ 10 7 or less, and still more preferably 3 ⁇ 10 7 or less. .
  • the molecular weight of the polymer (B) is a polystyrene conversion value measured by GPC.
  • the total amount of the polymer (A) and the polymer (B) contained in the medical treatment material of the present disclosure is a medical treatment material that can form a hydrogel with excellent adhesiveness to living tissue and has excellent mechanical strength. From the viewpoint of obtaining the treatment material, it is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and even more preferably 95% by mass or more, relative to the total amount of the medical treatment material.
  • the content of polymer (A) and polymer (B) is 20 to 500 parts by mass of polymer (B) per 100 parts by mass of polymer (A). It is preferable to adjust When the content of the polymer (A) and the polymer (B) is within the above range, the effect of improving the mechanical strength is high, and it is preferable in that a hydrogel exhibiting excellent adhesiveness to living tissue can be formed. is. From such a viewpoint, the content of the polymer (A) and the polymer (B) is such that the polymer (B) is 30 to 400 parts by mass with respect to 100 parts by mass of the polymer (A). More preferably, the amount is 50 to 300 parts by mass.
  • the polymerization method for producing polymer (A) and polymer (B) is not particularly limited.
  • Polymer (A) and polymer (B) are prepared by polymerizing monomers by employing known radical polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization. Obtainable.
  • a polymerization initiator eg, an azo compound
  • the desired product is polymerized by heating to 40 to 250 ° C. A polymer can be obtained.
  • the polymer (A) is a polymer containing a structural unit derived from an ethylenically unsaturated monomer (ma) and a structural unit derived from an ethylenically unsaturated monomer (mc)
  • the polymer (B) is a polymer containing a structural unit derived from an ethylenically unsaturated monomer (mb)
  • the polymer (A) is an ethylenically unsaturated monomer (ma) It is a polymer containing structural units derived from, the polymer (B) is a structural unit derived from the ethylenically unsaturated monomer (mb), a structural unit derived from the ethylenically unsaturated monomer (mc)
  • the polymer (A) is a polymer comprising a structural unit derived from an ethyl
  • the embodiment (1) and the embodiment (3) are preferable from the viewpoint of obtaining a hydrogel-forming material having excellent adhesion to living tissue, and the ethylenically unsaturated monomer (ma) and ethylene
  • the above embodiment (1) is particularly preferred, and the above embodiment (1) is important.
  • An embodiment in which the coalescence (B) is a high-molecular-weight polymer (BH) is more preferred.
  • the medical treatment material of the present disclosure further contains components different from the polymer (A) and the polymer (B) (hereinafter also referred to as “other components”) depending on the purpose of use. good too.
  • Other components include, for example, antibacterial agents, anti-inflammatory agents, blood coagulants, anticoagulants, local anesthetics, various drugs such as vasoconstrictors and vasodilators, as well as polymer (A) and polymer (B ) and a water-soluble polymer (C) different from ).
  • one or more can be contained.
  • the content of other components can be appropriately selected according to each component within a range that does not impair the effects of the present disclosure.
  • the water-soluble polymer (C) includes water-soluble polymers that can be generally used as thickeners, and specific examples include polysaccharides.
  • polysaccharides include cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and hydroxypropylmethylcellulose; mucopolysaccharides such as hyaluronic acid and chondroitin sulfate; water-soluble natural products such as carrageenan, pectin, locust bean gum, guar gum, xanthan gum and welan gum.
  • Polymeric polysaccharides and salts thereof (eg, sodium salts) and the like are included.
  • the water-soluble polymer (C) is preferably hyaluronic acid or a salt thereof.
  • the number average molecular weight of the water-soluble polymer (C) is, for example, 200,000 or more.
  • the molecular weight of the water-soluble polymer (C) is a polystyrene conversion value measured by GPC.
  • the content of the water-soluble polymer (C) is 100 parts by mass of the total amount of the polymer (A) and the polymer (B). On the other hand, it is preferably 0.01 to 50 parts by mass.
  • the content of the water-soluble polymer (C) is more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the total amount of the polymer (A) and the polymer (B), and 0.5 parts by mass. Part by mass or more is more preferable.
  • the upper limit of the content of the water-soluble polymer (C) is more preferably 20 parts by mass or less, and 15 parts by mass or less with respect to 100 parts by mass of the total amount of the polymer (A) and the polymer (B). is more preferred.
  • the water-soluble polymer (C) one type may be used alone, or two or more types may be used in combination.
  • Method [1] A method [2] in which a solid film containing one of polymer (A) and polymer (B) is brought into contact with a solution containing the other polymer and then dried.
  • the aqueous solution of the polymer (A) and the aqueous solution of the polymer (B) are simply mixed, the carboxyl group of the polymer (A) and the functional group E of the polymer (B) Hydrogen bonds form hydrogels very quickly.
  • the hydrogel thus obtained has insufficient water solubility and swelling properties, and is inferior in adhesiveness to living tissue.
  • a medical treatment material exhibiting excellent water solubility and water swellability can be produced.
  • a film-like solid material containing one of polymer (A) and polymer (B) (hereinafter also referred to as "first polymer”) is prepared.
  • first polymer a film-like solid material containing one of polymer (A) and polymer (B)
  • first polymer for preparing the film-like solid, for example, a solution drying method, a heat press method, and the like can be used. Among these, the solution drying method is preferable because it can suppress the generation of air bubbles and can produce a smooth film.
  • a polymer solution hereinafter also referred to as "first polymer solution”
  • first polymer solution is prepared by dissolving the first polymer in a solvent, and then the first polymer is It is preferable to apply the solution to the support and dry it.
  • the first polymer that constitutes the film-like solid may be the polymer (A) or the polymer (B).
  • Examples of the solvent for dissolving the first polymer include water, a mixture of a water-soluble organic solvent and water, and a water-soluble organic solvent.
  • Examples of water-soluble organic solvents include methanol, ethanol, and acetone.
  • As the solvent for dissolving the first polymer among these, water, ethanol, or a mixture of water and ethanol is preferable.
  • the polymer concentration in the first polymer solution is not particularly limited, but is, for example, 0.01 to 10% by mass, preferably 0.1 to 5% by mass.
  • a method for forming a film-like solid on a support is not particularly limited, and a known film-forming method can be adopted.
  • a solid film containing the first polymer can be formed on the support by coating the support with the first polymer solution and preferably heating to remove the solvent.
  • the heating temperature is, for example, 50 to 120° C.
  • the heating time is, for example, 0.1 to 5 hours.
  • the heat treatment may be performed under reduced pressure or under ventilation.
  • the thickness of the solid film formed on the support is, for example, 1 to 5,000 ⁇ m.
  • the water content of the solid film is, for example, 10% by mass or less.
  • a film-like solid material formed on the support and a polymer different from the first polymer (hereinafter also referred to as "second polymer”) among the polymer (A) and the polymer (B) is dissolved in a solvent (hereinafter also referred to as "second polymer solution").
  • the solvent for dissolving the second polymer include the same solvents as those exemplified as the solvent for dissolving the first polymer.
  • the polymer concentration in the second polymer solution is, for example, 0.1 to 30 mass %, preferably 1 to 20 mass %.
  • the method of bringing the solid film containing the first polymer into contact with the second polymer solution is not particularly limited.
  • Examples of the method of bringing the solid film into contact with the polymer solution include a method of applying, dropping, or spraying the second polymer solution on the surface of the solid film, and a method of applying the solid film to the second polymer solution.
  • a method of immersion and the like can be mentioned.
  • a liquid layer comprising the second polymer solution is formed on the film-like solid by dripping the second polymer solution onto the surface of the film-like solid, and the liquid layer is formed on the film-like solid for a predetermined time (for example, 10 minutes). ⁇ 180 minutes) Let stand.
  • the thickness of the liquid layer is not particularly limited, it is, for example, 0.1 to 50,000 ⁇ m.
  • the first polymer in the solid film is gradually dissolved in the second polymer solution to form a hydrogel.
  • the amount of the second polymer solution brought into contact with the film-like solid is such that a crosslinked structure is appropriately formed in the resulting hydrogel.
  • the number of moles of the functional group E possessed by the polymer (B) is preferably 0.1 to 10 mol, more preferably 0.2 to 1 mol, per 1 mol of the carboxyl group possessed by the polymer (A). It is preferable to adjust the amounts of the solid film and the second polymer solution and the polymer concentration so that the amount is 8 mol, more preferably 0.5 to 2 mol.
  • the water-soluble polymer (C) may contain a film-like solid substance, and the second polymer solution may contain the water-soluble polymer (C). good too.
  • the second polymer solution contains the water-soluble polymer (C)
  • the water-soluble polymer (C) is blended in advance with the second polymer solution, and the second polymer containing the water-soluble polymer (C) is prepared.
  • the solution may be brought into contact with the film-like solid, or the water-soluble polymer (C) may be added to the second polymer solution after contacting the film-like solid with the second polymer solution. good.
  • the second polymer solution contains the water-soluble polymer (C), and the second polymer solution containing the water-soluble polymer (C) in advance is more preferably brought into contact with the solid film.
  • the content of the water-soluble polymer (C) in the second polymer solution is 100 mass of the second polymer. It is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, even more preferably 0.5 to 15 parts by mass.
  • the resulting hydrogel is dried to obtain the desired dry product.
  • a method for drying the hydrogel is not particularly limited, and a known drying treatment method can be appropriately employed.
  • the freezing temperature is, for example, -70°C to -5°C, preferably -60°C to -5°C.
  • Drying treatment by freeze-drying is preferably carried out at room temperature under reduced pressure.
  • the pressure during freeze-drying is, for example, 50 Pa or less, preferably 20 Pa or less, and more preferably 10 Pa or less.
  • dry means a state in which water is completely removed as well as a state in which water remains in the drying process.
  • the moisture content of the dried body obtained by the drying treatment is, for example, 10% by mass or less, preferably 5% by mass or less.
  • the thickness of the dried body is, for example, 0.1 to 50,000 ⁇ m.
  • a solid film containing one of polymer (A) and polymer (B) is brought into contact with a solution containing the other polymer and then dried to form a solid film. It is possible to obtain a dried body having
  • a solvent that dissolves the polymer in the solution containing the polymer (A) (hereinafter also referred to as “polymer solution A”) and the solution containing the polymer (B) (hereinafter also referred to as “polymer solution B”)
  • the solvent include the same solvents as those exemplified as the solvent for dissolving the first polymer. Among these, from the viewpoint of efficiently performing the drying process, it is preferable to use water alone.
  • the polymer concentration is, for example, 0.001 to 5% by mass, preferably 0.01 to 1% by mass.
  • the content of each of the polymer (A) and the polymer (B) is 20 parts by mass of the polymer (B) per 100 parts by mass of the polymer (A). It is preferable to adjust the amount and concentration of the polymer solution A and the polymer solution B so as to be 500 parts by mass.
  • the amount of the polymer (A) and the polymer (B) is more preferably 30 to 400 parts by mass of the polymer (B) with respect to 100 parts by mass of the polymer (A). It is more preferable to set the amount to 300 parts by mass.
  • the same specific examples as the water-soluble polymer (C) exemplified above can be mentioned.
  • hyaluronic acid or a salt thereof can be preferably used.
  • the amount of the water-soluble polymer (C) used is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the polymer (A). , more preferably 0.5 to 15 parts by mass.
  • the water-soluble polymer (C) is preferably used as an aqueous solution.
  • the mixed liquid containing the polymer (A), the polymer (B) and the water-soluble polymer (C) obtained above is subjected to a drying treatment to obtain the desired dried product.
  • the drying treatment is preferably freeze-drying. Freeze-drying can be performed according to a conventional method. For example, the mixed solution is placed in a mold, frozen, and the molded frozen product is freeze-dried to obtain a target product (dry body) having a desired shape.
  • the moisture content of the dried product is, for example, 10% by mass or less, preferably 5% by mass or less.
  • the medical treatment material of the present disclosure is a solid substance in a dry state (that is, a dry substance) before use, and when it comes into contact with water, it absorbs water and swells to become a hydrogel (that is, a swollen substance).
  • the medical treatment material of the present disclosure is a dry body having flexibility before contact with water, and changes from a dry body to a swollen body upon contact with water, thereby exhibiting adhesiveness to living tissue.
  • water includes water, water-soluble organic solvents (ethanol, etc.), body fluids (blood, interstitial fluid, etc.), and mixtures thereof.
  • the medical treatment material of the present disclosure does not have bioabsorbability and is gradually decomposed and solubilized under physiological conditions, so it is highly safe and can be left in the body.
  • a medical treatment material of the present disclosure is particularly suitable as various medical treatment materials such as an anti-adhesion material, a hemostatic material, and a wound dressing.
  • the shape of the medical treatment material of the present disclosure is not particularly limited, and can be used in the form of film, sponge, sheet, powder, and the like. Further, the medical treatment material of the present disclosure may be provided in a state of being held on a support, or may be provided in a state of being included in a package such as a film.
  • the shape and material of the support are not particularly limited, but examples thereof include fabrics such as woven fabrics and non-woven fabrics; Since the medical treatment material of the present disclosure has high mechanical strength and excellent flexibility, it can be preferably used as a hydrogel-forming film or a hydrogel-forming sponge.
  • polymer G After 10 hours from the polymerization initiation point, cooling of the polymerization reaction liquid was started, and after the internal temperature was lowered to 25° C., a reaction liquid containing a polymer was obtained. This reaction solution was dried at 100° C. for 24 hours or more under reduced pressure conditions to remove volatile matter to obtain a polymer (hereinafter also referred to as “polymer G”).
  • Example 1 A silicone rubber sheet (thickness 10 mm) having an opening of 25 mm x 7 mm was placed on a polypropylene base material of 50 mm x 50 mm, and 1.5 mL of 1.2% polymer A aqueous solution was cast and heated at 70°C for 20 minutes. It was dried for a period of time to prepare a polymer A film. Next, 0.6 mL of a 4.6% polyvinylpyrrolidone (hereinafter also referred to as "PVP”) aqueous solution and 0.4% sodium hyaluronate (hereinafter also referred to as "HA”) were applied to the surface of the polymer A film.
  • PVP polyvinylpyrrolidone
  • HA sodium hyaluronate
  • a mixed solution of 0.9 mL of the aqueous solution was dropped onto the surface of the polymer A film, allowed to stand for 60 minutes, and then frozen at -50°C.
  • a hydrogel-forming sponge size: 25 mm x 7 mm x 7 mm
  • Examples 2 to 9 and Comparative Example 1 A hydrogel-forming sponge was obtained as a medical treatment material by performing the same operation as in Example 1, except that the types of raw materials were as described in Table 1.
  • ⁇ AA acrylic acid
  • MAA methacrylic acid
  • M-5300 ⁇ -carboxy-caprolactone mono (meth) acrylate (n ⁇ 2) [manufactured by Toagosei Co., Ltd., Aronix (registered trademark) M-5300 ]
  • VP N-vinyl-2-pyrrolidone
  • AAm acrylamide
  • BA n-butyl acrylate
  • PAA crosslinked polyacrylic acid [Carbopol 934P NF manufactured by Lubrizol]
  • ⁇ HA Sodium hyaluronate [Kewpie Co., Ltd., Hyaluronsan HA-LQH]
  • At least one of the polymer (A) and the polymer (B) has a structural unit derived from the ethylenically unsaturated monomer (mc) Hydrogels of Examples 1 to 9
  • the forming sponge had a high adhesive force to the skin of 3.0 N/cm 2 or more, and was excellent in usability.
  • a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer (acrylic acid dimer, ⁇ -carboxy-caprolactone mono (meth) acrylate) having a molecular weight of more than 115 as the ethylenically unsaturated monomer (mc)
  • the structural unit derived from the ethylenically unsaturated monomer (mc) was added to the polymer (A) rather than the polymer (B). It can be said that the introduction can increase the adhesive strength to the skin.

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6440421A (en) * 1987-08-05 1989-02-10 Sekisui Chemical Co Ltd Medical sheetlike tacky agent
US20050003012A1 (en) * 2001-09-01 2005-01-06 Karl-Heinz Woller Gel matrix consisting of polyacrylic acid and polyvinyl pyrrolidone
JP2007217313A (ja) * 2006-02-15 2007-08-30 Hisamitsu Pharmaceut Co Inc 凝集力向上及び徐放化の外用貼付剤
JP2009040685A (ja) * 2005-11-04 2009-02-26 Toagosei Co Ltd 貼付剤
WO2014065291A1 (ja) * 2012-10-23 2014-05-01 Koyama Yoshiyuki ハイドロゲル形成材
WO2021059689A1 (ja) * 2019-09-27 2021-04-01 積水化成品工業株式会社 ハイドロゲル

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6440421A (en) * 1987-08-05 1989-02-10 Sekisui Chemical Co Ltd Medical sheetlike tacky agent
US20050003012A1 (en) * 2001-09-01 2005-01-06 Karl-Heinz Woller Gel matrix consisting of polyacrylic acid and polyvinyl pyrrolidone
JP2009040685A (ja) * 2005-11-04 2009-02-26 Toagosei Co Ltd 貼付剤
JP2007217313A (ja) * 2006-02-15 2007-08-30 Hisamitsu Pharmaceut Co Inc 凝集力向上及び徐放化の外用貼付剤
WO2014065291A1 (ja) * 2012-10-23 2014-05-01 Koyama Yoshiyuki ハイドロゲル形成材
WO2021059689A1 (ja) * 2019-09-27 2021-04-01 積水化成品工業株式会社 ハイドロゲル

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