WO2023054499A1 - 医療用コーティング剤及び医療機器 - Google Patents

医療用コーティング剤及び医療機器 Download PDF

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Publication number
WO2023054499A1
WO2023054499A1 PCT/JP2022/036236 JP2022036236W WO2023054499A1 WO 2023054499 A1 WO2023054499 A1 WO 2023054499A1 JP 2022036236 W JP2022036236 W JP 2022036236W WO 2023054499 A1 WO2023054499 A1 WO 2023054499A1
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polymer
meth
acrylate
glass transition
transition temperature
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English (en)
French (fr)
Japanese (ja)
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賢 田中
将太 谷口
賢一 中村
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Kyushu University NUC
Toagosei Co Ltd
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Kyushu University NUC
Toagosei Co Ltd
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Priority to US18/696,552 priority Critical patent/US20240390561A1/en
Priority to JP2023551616A priority patent/JPWO2023054499A1/ja
Publication of WO2023054499A1 publication Critical patent/WO2023054499A1/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
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/82—Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • 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
    • A61L27/28—Materials for coating prostheses
    • A61L27/34—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
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • 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
    • 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
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/08—Materials for coatings
    • 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
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/08—Materials for coatings
    • A61L29/085—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
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • 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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08—Materials for coatings
    • A61L31/10—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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • 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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified 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
    • A61L33/00—Antithrombogenic treatment of surgical articles, e.g. sutures, catheters, prostheses, or of articles for the manipulation or conditioning of blood; Materials for such treatment
    • A61L33/06—Use of macromolecular materials

Definitions

  • TECHNICAL FIELD The present disclosure relates to medical coating agents and medical devices, and more particularly to techniques for imparting biocompatibility to medical devices used in contact with biological components and biological tissues.
  • Patent Document 1 discloses the use of a polymer having structural units derived from 2-methoxyethyl acrylate as a biocompatible medical material.
  • Platelets and fibrinogen are considered to be the main components in blood involved in thrombus formation. Therefore, the present inventors considered that it is important to prevent these components from recognizing a medical device inserted into the body as a foreign body. That is, if the property of suppressing the adsorption of platelets and fibrinogen (hereinafter also referred to as "anti-adsorption”) can be sufficiently imparted to the surface of the base material, excellent antithrombotic properties can be imparted to medical devices, and biocompatibility can be improved. It can be said.
  • the present disclosure has been made in view of such circumstances, and its purpose is to provide a medical coating agent that has high platelet and fibrinogen anti-adsorption properties and excellent anti-thrombotic properties.
  • [1] Contains a polymer containing a structural unit (A) derived from an ethylenically unsaturated monomer having a urethane bond, impregnates the polymer with water, and measures the velocity using a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the polymer contained in the medical coating agent of the present disclosure has high antiadsorption of platelets and fibrinogen, and excellent antithrombogenicity. Therefore, by coating the base material of a medical device with the medical coating agent of the present disclosure, it is possible to provide a medical device with excellent antithrombotic properties.
  • (meth)acryl means acryl and/or methacryl
  • (meth)acrylate means acrylate and/or methacrylate
  • the medical coating agent of the present disclosure contains a structural unit (A) derived from an ethylenically unsaturated monomer having a urethane bond (-NH-COO-), and has a glass transition temperature of -25°C in a saturated water-containing state. It contains the following polymer (hereinafter also referred to as "polymer (P)").
  • the water interacting with the polymer (P) is, depending on the strength of the interaction with the polymer, "free water", It can take the form of “non-freezing water” and “intermediate water”.
  • “free water” refers to water that has a weak interaction with the polymer and has a freezing point of 0°C
  • non-freezing water refers to water that has a strong interaction with the polymer and has no detectable freezing point.
  • "Intermediate water” refers to water that interacts with the polymer intermediately between free water and antifreeze water (ie, interacts relatively slowly with the polymer) and has a freezing point below 0°C. Acquiring biocompatibility of the polymer is believed to be related to the fact that the hydrated polymer contains a large amount of intermediate water (see, for example, paragraphs 0003 and 0004 of JP-A-2016-35000). .
  • cells recognize foreign substances, activating biological defense functions and causing rejection. Therefore, when a medical device comes into contact with a biological component or tissue during treatment or surgery, if the body recognizes the medical device as a foreign object, the body's defense function may act and interfere with treatment. be. For example, when a medical device comes into contact with blood, a thrombus is formed, which may hinder the function of the medical device or affect the living body. On the other hand, a polymer having intermediate water on its surface is unlikely to be recognized as a foreign substance by the living body, and is thought to exhibit excellent antithrombotic properties.
  • Platelets and fibrinogen are known components in blood that are involved in thrombus formation. Platelets are blood cells that are activated by foreign substances and aggregate on foreign substances to form thrombi (platelet thrombi), contributing to primary hemostasis in the process of hemostasis.
  • Fibrinogen, coagulation factor I is a protein that is converted to fibrin at the final stage of blood coagulation to form a coagulation clot and contributes to secondary hemostasis in the process of hemostasis. That is, platelets and fibrinogen are both major components that form thrombi, and it is considered important for biocompatibility (more specifically, antithrombotic properties) that these components are less likely to be adsorbed onto the polymer. .
  • the polymer (P) contained in the medical coating agent of the present disclosure easily retains intermediate water during hydration, and platelets and fibrinogen are adsorbed on the substrate surface coated with the polymer (P). can be sufficiently suppressed. It is believed that this allows the development of excellent antithrombotic properties.
  • the polymer (P) contains a structural unit derived from an ethylenically unsaturated monomer having a urethane bond (hereinafter also referred to as "monomer (M)").
  • the polymer (P) is preferably a (meth)acrylic polymer in that the reaction rate of the monomers can be easily increased and that it is easy to manufacture industrially.
  • the ratio of the structural units derived from the (meth)acrylic monomer preferably exceeds 50% by mass. , 60 mass % or more is more preferable, 70 mass % or more is still more preferable, 80 mass % or more is still more preferable, and 90 mass % or more is still more preferable.
  • the monomer (M) is preferably a compound capable of introducing a structure having a urethane bond into the side chain of the polymer, and is preferably a (meth)acrylic monomer having a urethane bond.
  • the monomer (M) is a (meth)acrylic monomer, it is preferable in that the reaction rate of the monomer can be easily increased.
  • the monomer (M) one type may be used alone, or two or more types may be used.
  • (methoxycarbonyl)aminoalkyl (meth)acrylate and the following general formula (I) can be used in that the glass transition temperature (Tg2) of the saturated water-containing polymer (P) can be sufficiently lowered.
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is an alkylene group having 1 to 5 carbon atoms or a group represented by "-(R 5 O) m -R 6 -" ( provided that R 5 is an alkylene group having 1 to 3 carbon atoms, R 6 is an alkylene group having 1 to 3 carbon atoms, m is an integer of 1 to 3), and R 3 is an alkylene group having 1 to 3 carbon atoms.
  • any hydrogen atom of the alkylene group may be substituted with an alkoxy group having 1 to 10 carbon atoms
  • R 4 is an alkoxy group having 1 to 10 carbon atoms
  • a compound represented by can be preferably used.
  • R 3 in the general formula (I) is such that any hydrogen atom of the alkylene group is substituted with an alkoxy group having 1 to 4 carbon atoms. is more preferred, and substitution with an alkoxy group having 1 to 2 carbon atoms is even more preferred.
  • R 4 in general formula (I) is more preferably an alkoxy group having 1 to 4 carbon atoms, still more preferably an alkoxy group having 1 to 2 carbon atoms.
  • (methoxycarbonyl) aminoalkyl (meth) acrylates include (methoxycarbonyl) aminomethyl (meth) acrylate, 2-((methoxycarbonyl) amino) ethyl (meth) acrylate, 3-((methoxycarbonyl) amino ) propyl (meth)acrylate and the like.
  • 2-((methoxycarbonyl)amino)ethyl acrylate is preferably used in that the glass transition temperature (Tg2) of the polymer (P) in a saturated water-containing state can be sufficiently lowered.
  • Specific examples of the compound represented by the general formula (I) include 2-(((2-methoxyethoxy)carbonyl)amino)ethyl (meth)acrylate, 2-(((2-ethoxyethoxy)carbonyl)amino ) ethyl (meth)acrylate, 2-(((2-propoxyethoxy)carbonyl)amino)ethyl (meth)acrylate, 2-((((1,3-dimethoxypropan-2-yl)oxy)carbonyl)amino) Ethyl (meth)acrylate, 2-((((1,3-diethoxypropan-2-yl)oxy)carbonyl)amino)ethyl (meth)acrylate, 2-((((1-methoxy-3-ethoxypropane -2-yl)oxy)carbonyl)amino)ethyl (meth)acrylate, 6-oxo-2,5,10-trioxa-7-azadodecane-12
  • the polymer (P) is composed of (methoxy derived from at least one compound (hereinafter also referred to as "monomer (m-1)") selected from the group consisting of carbonyl)aminoalkyl (meth)acrylates and compounds represented by the general formula (I) of the total structural units derived from the monomers constituting the polymer (P), preferably 10% by mass or more, more preferably 20% by mass or more, and 30% by mass or more. is more preferable, more preferably 50% by mass or more, and particularly preferably 60% by mass or more.
  • the polymer (P) may have only one type of structural unit derived from the monomer (m-1), or may have two or more types.
  • the polymer (P) may be composed only of structural units derived from the monomer (m-1), but for the purpose of adjusting the glass transition temperature of the polymer, etc., the effect of the present disclosure is obtained. It may further have a structural unit derived from a monomer other than the monomer (m ⁇ 1) (hereinafter also referred to as “other monomer”) within a range that does not impair it.
  • Examples of other monomers include monomers that do not have a urethane bond and are copolymerizable with the monomer (m-1).
  • Examples of such monomers include unsaturated carboxylic acids, unsaturated acid anhydrides, (meth)acrylic acid alkyl esters, aliphatic cyclic esters of (meth)acrylic acid, and aromatic (meth)acrylic acid.
  • Esters (meth)acrylic acid alkoxyalkyl esters, (meth)acrylic acid hydroxyalkyl esters, polyalkylene glycol mono(meth)acrylates, vinyl compounds having a heterocyclic structure, amino group-containing vinyl compounds, amide group-containing vinyl compounds, nitriles Examples include group-containing vinyl compounds, aromatic vinyl compounds, maleimide compounds, and the like.
  • unsaturated carboxylic acids such as (meth)acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, cinnamic acid, monohydroxyethyl succinate (meth)acrylate, ⁇ -carboxy -caprolactone mono(meth)acrylate, ⁇ -carboxyethyl(meth)acrylate, 4-carboxystyrene and the like.
  • unsaturated acid anhydrides include maleic anhydride, itaconic anhydride, and citraconic anhydride.
  • Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, ( meth)isobutyl acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate and 2-ethylhexyl (meth)acrylate.
  • 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 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, n-propoxyethyl (meth)acrylate, and n-(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.
  • Vinyl compounds having a heterocyclic structure include glycidyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate.
  • amino group-containing vinyl compounds include dimethylaminomethyl (meth)acrylate, diethylaminomethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 2-diethylaminoethyl (meth)acrylate, (meth)acryl 2-(di-n-propylamino)ethyl acid, 2-dimethylaminopropyl (meth)acrylate, 2-diethylaminopropyl (meth)acrylate, 2-(di-n-propylamino)propyl (meth)acrylate , 3-dimethylaminopropyl (meth)acrylate, 3-diethylaminopropyl (meth)acrylate, 3-(di-n-propylamino)propyl (meth)acrylate and the like.
  • Amide group-containing vinyl compounds include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N-methylol(meth)acrylamide, and the like.
  • nitrile group-containing vinyl compounds include cyanomethyl (meth)acrylate, 1-cyanoethyl (meth)acrylate, 2-cyanoethyl (meth)acrylate, 1-cyanopropyl (meth)acrylate, and 2-(meth)acrylate.
  • aromatic vinyl compounds include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, vinylxylene, methylstyrene, ethylstyrene, butylstyrene, methoxystyrene, hydroxystyrene, isopropenylphenol, vinylbenzoic acid and vinylnaphthalene. be done.
  • Maleimide compounds include maleimide and N-substituted maleimide compounds.
  • N-substituted maleimide compounds include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, N-tert-butylmaleimide and the like.
  • N-alkyl-substituted maleimides N-cycloalkyl-substituted maleimides such as N-cyclopentylmaleimide and N-cyclohexylmaleimide; N-aralkyl-substituted maleimides such as N-benzylmaleimide; N-phenylmaleimide, N-(4-hydroxyphenyl)maleimide , N-(4-acetylphenyl)maleimide and N-(4-methoxyphenyl)maleimide.
  • monomers that have a urethane bond and can be copolymerized with the monomer (m-1) can also be used.
  • examples of such monomers include 2-((ethoxycarbonyl)amino)ethyl(meth)acrylate and 2-((isopropoxycarbonyl)amino)ethylacrylate.
  • other monomers include (meth)acrylic acid alkyl esters, (meth)acrylic acid aliphatic cyclic esters, (meth) It is preferably at least one selected from the group consisting of aromatic esters of acrylic acid, alkoxyalkyl (meth)acrylates, amino group-containing vinyl compounds, and amide group-containing vinyl compounds, and alkyl (meth)acrylates. At least one selected from the group consisting of esters and (meth)acrylic acid alkoxyalkyl esters is more preferred.
  • Other monomers are, among others, from the group consisting of (meth)acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms and (meth)acrylic acid alkoxyalkyl esters having an alkoxyalkyl group having 3 to 12 carbon atoms. At least one selected is preferable, and an alkoxyalkyl (meth)acrylate having an alkoxyalkyl group having 3 to 12 carbon atoms is more preferable, and an alkoxyalkyl (meth)acrylate having an alkoxyalkyl group having 3 to 4 carbon atoms. Esters are more preferred, and 2-methoxyethyl (meth)acrylate is particularly preferred.
  • the polymer (P) is selected from the group consisting of an alkyl (meth)acrylate having an alkyl group of 1 to 12 carbon atoms and an alkoxyalkyl (meth)acrylate having an alkoxyalkyl group of 3 to 12 carbon atoms.
  • the proportion of structural units derived from the monomer (N) is the polymer (P ) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, relative to all structural units derived from the monomers constituting ).
  • the unit constituting the polymer (P) 90% by mass or less is preferable, 80% by mass or less is more preferable, 70% by mass or less is still more preferable, 50% by mass or less is even more preferable, and 40% by mass or less is even more preferable, based on the total structural units derived from the polymer. preferable.
  • the polymer (P) preferably contains 10% by mass or more of the structural unit (A) relative to the total structural units of the polymer (P).
  • the ratio of the structural unit (A) in the polymer (P) is within the above range, the substrate coated with the medical coating agent of the present disclosure can be sufficiently imparted with the effect of suppressing the adsorption of platelets and fibrinogen. This is preferable in that a medical device having excellent antithrombotic properties can be obtained.
  • the proportion of the structural unit (A) in the polymer (P) is more preferably 20% by mass or more, more preferably 30% by mass or more, relative to the total structural units of the polymer (P). , more preferably 50% by mass or more, and even more preferably 60% by mass or more.
  • the polymer (P) is a copolymer of the monomer (M) and another monomer having no urethane bond
  • the polymer (P) is a random copolymer or a block copolymer. and graft copolymers.
  • the polymer (P) is preferably a random copolymer from the viewpoint of uniformly introducing a structure having a urethane bond into the entire polymer to enhance the effect of improving the antithrombotic property.
  • the weight average molecular weight (Mw) of the polymer (P) is preferably in the range of 2,000 to 2,000,000. When the Mw is 2,000 or more, it is possible to sufficiently secure the mechanical strength of the coating layer formed using the medical coating agent. Moreover, when Mw is 2,000,000 or less, it is possible to prevent the viscosity of the medical coating agent from becoming too high, and to ensure coatability and handleability.
  • the Mw of the polymer (P) is more preferably 5,000 or more, still more preferably 10,000 or more, still more preferably 30,000 or more, still more preferably 50,000 or more.
  • the upper limit of Mw of the polymer (P) is more preferably 1,500,000 or less, still more preferably 1,000,000 or less.
  • Mw of a polymer is a standard polystyrene conversion value obtained using a gel permeation chromatography (GPC).
  • the polymerization method for producing the polymer (P) is not particularly limited.
  • the polymer (P) can be obtained by polymerizing monomers by employing known radical polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization and bulk polymerization.
  • a polymerization initiator eg, an azo compound
  • a polymer can be obtained.
  • isolating and/or purifying the polymer obtained by the polymerization reaction known methods can be employed for these treatments.
  • the glass transition temperature (Tg1) of the polymer (P) in a dry state is not particularly limited, but is, for example, 20°C or lower, preferably 10°C or lower.
  • the lower limit of the glass transition temperature (Tg1) of the polymer (P) in a dry state is also not particularly limited, and is -70°C or higher, for example.
  • the glass transition temperature of the polymer (P) is a value measured by a differential scanning calorimeter (DSC) under the condition of a heating rate of 5° C./min.
  • DSC differential scanning calorimeter
  • the polymer (P) has a glass transition temperature (Tg2) of -25°C or less in a saturated water content state. If the glass transition temperature (Tg2) of the polymer (P) in a saturated water content state is higher than ⁇ 25° C., the anti-adsorption property of platelets and fibrinogen cannot be sufficiently imparted to the substrate surface, and the desired antithrombotic property cannot be obtained. There is concern that it will not be possible to provide From the viewpoint of sufficiently enhancing the anti-adsorption properties of platelets and fibrinogen, the glass transition temperature (Tg2) of the polymer (P) in a saturated water content state is preferably ⁇ 30° C. or less, more preferably ⁇ 40° C. or less, and ⁇ 50° C. More preferred are: The lower limit of the glass transition temperature (Tg2) of the polymer (P) in a saturated water content state is not particularly limited, and is, for example, -100°C or higher.
  • the glass transition temperature (Tg2) of the polymer (P) in a saturated water content state is adjusted to a value within the desired temperature range by adjusting the type and amount of the monomers constituting the polymer (P). be able to.
  • the glass transition temperature of the homopolymer composed of the monomer (M) used in the production of the polymer (P) in a saturated water-containing state is higher than the desired temperature, the saturation of the homopolymer
  • the glass transition temperature (Tg2) of the polymer (P) in a saturated water-containing state can be adjusted.
  • the difference ⁇ Tg is preferably 30° C. or higher, more preferably 35° C. or higher.
  • the medical coating agent of the present disclosure may further contain components different from the polymer (P) (hereinafter also referred to as “other components”) depending on the purpose of use.
  • the medical coating agent of the present disclosure is liquid, one aspect of the medical coating agent is a polymer composition in which the polymer (P) is optionally dissolved or dispersed in a solvent.
  • a solvent capable of dissolving the polymer (P) is preferably used as the solvent.
  • the solvent contained in the medical coating agent of the present disclosure is preferably an organic solvent. Specific examples include alcohols such as methanol, ethanol, n-propanol and isopropanol; ketones such as acetone and methyl ethyl ketone; ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, tetrahydrofuran and dioxane; esters such as ether acetate and ethyl acetate; amide solvents such as N,N-dimethylformamide (DMF) and N,N-dimethylacetamide; hydrocarbons such as n-hexane, cyclohexane, toluene and xylene; is mentioned.
  • a solvent you may use individually by 1 type and may use it in combination of 2 or more type.
  • ingredients that may be incorporated into the medical coating agent of the present disclosure include solvents, as well as various agents such as antibacterial agents, anti-inflammatory agents, and antioxidants. 1 type or multiple types can be used for other components. 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 content of the polymer (P) is based on 100 parts by mass of the total amount of solids contained in the medical coating agent (that is, components other than the solvent in the medical coating agent). , preferably 50 parts by mass or more, more preferably 70 parts by mass or more, still more preferably 80 parts by mass or more, even more preferably 90 parts by mass or more, and even more preferably 95 parts by mass or more.
  • the solid content concentration in the medical coating agent (here, the volume of the solvent used to prepare the medical coating agent, The mass ratio of the components) is not particularly limited, but is preferably 0.001 to 30 (w/v)%.
  • the solid content concentration is preferably 0.01 to 25 (w/v)%, still more preferably 0.05 to 20 (w/v)%.
  • the medical device of the present disclosure is obtained by coating a substrate with the medical coating agent of the present disclosure described above. A part or all of the surface of the medical device of the present disclosure is coated with the polymer (P) contained in the medical coating agent of the present disclosure. Therefore, the anti-adsorption property of platelets and fibrinogen is high, and the anti-thrombotic property is excellent.
  • the base material of the medical device to which the medical coating agent of the present disclosure is applied is not particularly limited.
  • materials that constitute the base material include various materials such as resins, rubbers, metals, glass, and ceramics.
  • resins for example, polycarbonate, polyethylene terephthalate, polyvinyl chloride, polyethylene, polypropylene, polymethylpentene, polyurethane, poly(meth)acrylate, polystyrene, polyacetal, polysulfone, polyethersulfone, fluorine resin (polyfluoride vinylidene, polyethylene tetrafluoride, etc.), acrylonitrile-butadiene-styrene (ABS) resin, polyamide, ethylene-vinyl acetate resin and the like.
  • rubber include silicone rubber and urethane rubber.
  • metals include various metal materials such as stainless steel, titanium, and aluminum.
  • the material that constitutes the base material of the medical device may be a mixture of two or more materials.
  • the method of coating the substrate surface with the medical coating agent of the present disclosure is not particularly limited.
  • the medical coating agent when the medical coating agent is in a solution state, at least a part of the substrate surface becomes a polymer (P ) can be obtained.
  • the coating method can be appropriately set according to the shape of the base material, purpose of use, etc.
  • coating methods include bar coaters, applicators, doctor blades, dip coaters, roll coaters, spin coaters, flow coaters, knife coaters, comma coaters, reverse coaters, die coaters, lip coaters, gravure coaters, micro gravure coaters, Various coating methods such as inkjet can be used.
  • the coating amount of the medical coating agent can be appropriately selected according to the application, material, etc. of the medical device so that the thickness of the coating layer formed by the medical coating agent is within the desired range.
  • the medical device whose substrate surface is coated with the medical coating agent of the present disclosure is not particularly limited, and can be applied to various medical devices. Specifically, stents, catheters, blood bags, blood transfusion instruments, surgical instruments, dental instruments, blood circulation devices, blood purification devices, plasma separation devices, artificial blood vessels, artificial organs (e.g., artificial heart-lung, artificial kidney, etc.) ) can be exemplified.
  • the medical coating agent of the present disclosure when applying the medical coating agent of the present disclosure to medical devices, the purpose and application are not particularly limited.
  • the medical coating agent of the present disclosure may be used as an antimicrobial/antifouling coating agent.
  • the present disclosure as a material for coating the substrate of medical devices that are used in direct contact with blood can be applied preferably.
  • AOI was added dropwise from the dropping funnel while maintaining the internal temperature at 10°C or lower.
  • the temperature was raised to room temperature (25° C.) and stirring was continued overnight.
  • 10 mL of saturated aqueous sodium bicarbonate solution was added dropwise to the flask to terminate the reaction.
  • 200 mL of the internal liquid was transferred to a separatory funnel to separate the organic layer and the aqueous layer.
  • 30 mL of ethyl acetate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade
  • Tg1 of polymer in dry state ⁇ Measurement of glass transition temperature (Tg1) of polymer in dry state> Each obtained polymer was dried overnight under reduced pressure conditions of 60° C. and 1000 Pa. Each dried polymer was weighed in an aluminum pan. After that, using a differential scanning calorimeter (measuring equipment: DSC214Polyma manufactured by NETZSCH, measurement atmosphere: under air atmosphere), the temperature was cooled from 100 ° C. to -80 ° C. at a rate of 5 ° C./min, and -80 ° C. After holding for 5 minutes, the temperature was raised to 100°C. Thereby, the glass transition temperature (Tg1) of the polymer in a dry state was determined.
  • DSC214Polyma manufactured by NETZSCH measurement atmosphere: under air atmosphere
  • Tg2 glass transition temperature
  • the glass transition temperature (Tg2) of the polymer in a saturated water-containing state was obtained from the DSC curve when the endothermic peak top due to melting of ice appeared at 0°C.
  • a syringe needle was inserted through the three-way cock, and argon was blown into the solution at 100 mL/min for 30 minutes to deoxygenate it. After that, the three-way cock was closed to seal the test tube.
  • the test tube was inserted into a heat block set at 60°C to initiate polymerization. The temperature of the heat block was appropriately adjusted so that the internal temperature was 60°C. After 3 hours, the test tube was cooled in an ice bath to stop the polymerization. Using a mixed solvent of hexane and acetone at a mass ratio of 3:7 as a solvent for reprecipitation purification, reprecipitation purification of the reaction solution was performed twice.
  • the recovered polymer was purified by reprecipitation to obtain a polymer A.
  • the weight average molecular weight was 71,300.
  • the glass transition temperature of the polymer A in a dry state is 7° C.
  • the glass transition temperature in a saturated water content state is ⁇ 30° C.
  • the difference ⁇ Tg between the glass transition temperature in a saturated water content state and the glass transition temperature in a dry state is 37° C.
  • the saturated water content was 12.0% by mass.
  • the weight average molecular weight was 100,800. Further, the glass transition temperature of the polymer B in a dry state is -10°C, the glass transition temperature in a saturated water content state is -60°C, and the difference ⁇ Tg between the glass transition temperature in a saturated water content state and the glass transition temperature in a dry state is 50°C. , the saturated water content was 31.5% by mass.
  • the glass transition temperature of the polymer C in a dry state is -11°C
  • the glass transition temperature in a saturated water content state is -60°C
  • the difference ⁇ Tg between the glass transition temperature in a saturated water content state and the glass transition temperature in a dry state is 49°C.
  • the saturated water content was 30.0% by mass.
  • the glass transition temperature of the polymer D in a dry state is -22°C
  • the glass transition temperature in a saturated water content state is -62°C
  • the difference ⁇ Tg between the glass transition temperature in a saturated water content state and the glass transition temperature in a dry state is 40°C.
  • the saturated water content was 22.4% by weight.
  • the glass transition temperature of the polymer E in a dry state is -30°C
  • the glass transition temperature in a saturated water content state is -61°C
  • the difference ⁇ Tg between the glass transition temperature in a saturated water content state and the glass transition temperature in a dry state is 31°C.
  • the saturated water content was 14.5% by mass.
  • the glass transition temperature of the polymer F in a dry state is -23°C
  • the glass transition temperature in a saturated water content state is -42°C
  • the difference ⁇ Tg between the glass transition temperature in a saturated water content state and the glass transition temperature in a dry state is 19°C.
  • the saturated water content was 7.7% by mass.
  • the glass transition temperature of the polymer G in a dry state is -10°C
  • the glass transition temperature in a saturated water content state is -58°C
  • the difference ⁇ Tg between the glass transition temperature in a saturated water content state and the glass transition temperature in a dry state is 48°C.
  • the saturated water content was 23.4% by mass.
  • the glass transition temperature of the polymer H in a dry state is -12°C
  • the glass transition temperature in a saturated water content state is -46°C
  • the difference ⁇ Tg between the glass transition temperature in a saturated water content state and the glass transition temperature in a dry state is 34°C.
  • the saturated water content was 6.6% by mass.
  • the glass transition temperature of polymer I in a dry state is -18°C
  • the glass transition temperature in a saturated water content state is -50°C
  • the difference ⁇ Tg between the glass transition temperature in a saturated water content state and the glass transition temperature in a dry state is 32°C.
  • the saturated water content was 31.9% by mass.
  • the glass transition temperature of polymer J in a dry state is 2° C.
  • the glass transition temperature in a saturated water content state is ⁇ 20° C.
  • the difference ⁇ Tg between the glass transition temperature in a saturated water content state and the glass transition temperature in a dry state is 22° C.
  • the saturated water content was 5.7% by mass.
  • the glass transition temperature of the polymer K in a dry state is 18° C.
  • the glass transition temperature in a saturated water content state is ⁇ 8° C.
  • the difference ⁇ Tg between the glass transition temperature in a saturated water content state and the glass transition temperature in a dry state is 26° C.
  • the saturated water content was 4.5% by mass.
  • the glass transition temperature of the polymer L in a dry state is -37°C
  • the glass transition temperature in a saturated water content state is -60°C
  • the difference ⁇ Tg between the glass transition temperature in a saturated water content state and the glass transition temperature in a dry state is 23°C.
  • the saturated water content was 8.4% by mass.
  • ⁇ Fibrinogen adsorption amount test (MicroBCA assay)> 0.2 (w / v) % each polymer solution (Example 1: acetone solution, Comparative Examples 1 and 2: ethyl acetate solution, Examples 2 to 9 and Comparative Example 3: methanol solution) was prepared, was used as a medical coating agent. 15 ⁇ L of each medical coating agent is dropped into each well of a 96-well plate (manufactured by Corning, general assay plate polypropylene 96-well perfect plate flat bottom non-sterile), left to dry for 3 days, and a coating substrate 1 for evaluation is obtained. Obtained.
  • PET polyethylene terephthalate
  • the spin coating conditions were 500 rpm, 5 s ⁇ 1,500 rpm, 10 s ⁇ 1,500 to 4,000 rpm (slope), 5 s ⁇ 4,000 rpm, 10 s ⁇ 4,000 to 0 rpm (slope), 5 s.
  • a coating substrate 2 for evaluation was obtained for each medical coating agent.
  • the resulting coated base material 2 for evaluation was cut into an 8 mm square, and 200 ⁇ L of plasma solution adjusted to a platelet seeding density of 4 ⁇ 10 7 /cm 2 was placed on each of the cut coated base materials 2 for evaluation. After culturing at 37° C. for 1 hour, the coating substrate 2 for evaluation was washed twice with PBS( ⁇ ).
  • the evaluation coating substrate 2 was immersed in a 1% glutaraldehyde PBS(-) solution and allowed to stand overnight at 4°C.
  • the coating substrate 2 for evaluation was taken out, washed first with PBS(-), then washed with an aqueous solution obtained by mixing PBS(-) and water at a volume ratio of 1:1, and finally with pure water in this order. washed.
  • the coating substrate for evaluation 2 was immersed in the target cleaning liquid for 10 minutes.
  • Table 1 shows the properties of the polymers used in Examples 1-9 and Comparative Examples 1-3, the evaluation results of the medical coating agents, and the evaluation results of Comparative Example 4.
  • Tg2 glass transition temperature

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