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WO2008038503A1 - Adhésif ou agent de revêtement à base de chitosan photodurcissable de type mélange - Google Patents

Adhésif ou agent de revêtement à base de chitosan photodurcissable de type mélange Download PDF

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Publication number
WO2008038503A1
WO2008038503A1 PCT/JP2007/067417 JP2007067417W WO2008038503A1 WO 2008038503 A1 WO2008038503 A1 WO 2008038503A1 JP 2007067417 W JP2007067417 W JP 2007067417W WO 2008038503 A1 WO2008038503 A1 WO 2008038503A1
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WO
WIPO (PCT)
Prior art keywords
adhesive
coating agent
uvcc
composition
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2007/067417
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English (en)
Japanese (ja)
Inventor
Saburo Minami
Yoshiharu Okamoto
Yasuhiko Okamura
Yoshihiko Omura
Eiko Renbutsu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Omura Toryo Co Ltd
Nitto Denko Corp
Tottori University NUC
Original Assignee
Omura Toryo Co Ltd
Nitto Denko Corp
Tottori University NUC
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Filing date
Publication date
Application filed by Omura Toryo Co Ltd, Nitto Denko Corp, Tottori University NUC filed Critical Omura Toryo Co Ltd
Priority to JP2008536318A priority Critical patent/JP4955007B2/ja
Publication of WO2008038503A1 publication Critical patent/WO2008038503A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • A61L26/0066—Medicaments; Biocides
    • 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
    • A61L15/28—Polysaccharides or their derivatives
    • 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
    • A61L15/44—Medicaments
    • 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
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001—Use of materials characterised by their function or physical properties
    • A61L24/0015—Medicaments; Biocides
    • 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
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
    • A61L24/08—Polysaccharides
    • 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
    • A61L26/0023—Polysaccharides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
    • C09D105/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
    • C09J105/08—Chitin; Chondroitin sulfate; Hyaluronic acid; 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
    • A61L2300/23—Carbohydrates
    • A61L2300/232—Monosaccharides, disaccharides, polysaccharides, lipopolysaccharides
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/606—Coatings

Definitions

  • the present invention relates to a photocurable adhesive or coating used for a living body. Specifically, the present invention relates to a photocurable adhesive or coating agent containing a chitosan derivative having a photopolymerizable functional group and a photopolymerizable resin, particularly a medical adhesive or coating agent, and uses thereof.
  • gelatin-formaldehyde system uses harmful formaldehyde as a cross-linking agent, so its safety has been questioned.
  • the chitosan system had a problem in adhesive strength.
  • gelatin-formaldehyde-based fiber glue adhesives have restrictions on the time and timing until bonding. Therefore, the current situation is that the development of medical adhesives with excellent adhesiveness, biocompatibility, and convenience is still desired.
  • Patent Document 1 Japanese Patent Laid-Open No. 2005-154477
  • Non-Patent Document 1 Techniques in Gastrointestinal Endoscopy, 8, p.33-37, (2006). Int. J. Adhesion and adhesives, 16, p.17-20, (1996).
  • the problem to be solved by the present invention is to provide an adhesive or coating agent, particularly a medical adhesive or coating agent, which is excellent in adhesiveness, biocompatibility, convenience!
  • the inventors of the present invention have intensively studied to solve the above problems, and can solve the above problems by mixing a photopolymerizable resin with a chitosan derivative having a photopolymerizable functional group.
  • the inventors have found that a mold adhesive or coating agent can be obtained, and have completed the present invention. Since the chitosan derivative having a photopolymerizable functional group and a photopolymerizable resin are mixed, the adhesive or coating material of the present invention may be referred to as a “bend-type” photocurable chitosan-based adhesive or covering agent. it can.
  • the present invention provides the following:
  • a photocurable adhesive or coating agent comprising a chitosan derivative having a photopolymerizable functional group and a photopolymerizable resin
  • An ultraviolet curable adhesive or coating agent comprising a chitosan derivative having an ultraviolet polymerizable functional group and an ultraviolet polymerizable resin, wherein the chitosan derivative is represented by the following formula (I):
  • m, n are independently 0 ⁇ 1 ⁇ 1, 0 ⁇ m ⁇ l, 0 ⁇ ⁇ 1;
  • R1 is the following formula (II):
  • R2 is hydrogen or C;! 3 is an alkyl group
  • the ultraviolet-polymerizable resin is a glycerin monometatalylate resin (2)! / In (4), the displacement force, or the adhesive or coating agent according to item 1;
  • adhesives biocompatibility, convenience! /, Adhesives or coatings excellent in deviation, particularly medical adhesives, and uses thereof.
  • FIG. 1 shows the FT / IR spectrum of UV-curable chitosan derivatives with different degrees of substitution of side chains.
  • chitosan is a raw material chitosan
  • chitin is a 100% acetylated sample of raw material chitosan.
  • the present invention provides a photocurable adhesive or coating agent comprising a chitosan derivative having a photopolymerizable functional group and a photopolymerizable resin.
  • light includes not only light rays such as visible light rays and ultraviolet rays but also electromagnetic waves such as X-rays.
  • Photopolymerizable functional groups and photopolymerizable resins are well known to those skilled in the art, and those skilled in the art can select and use them as appropriate.
  • Examples of the photopolymerizable functional group include a (meth) atalyloyl group, a butyl ether group, a cinnamoyl group, an azide group, and a maleimide group.
  • Examples of the photopolymerizable monomer resin include (meth) acrylic acid and hydroxyethyl.
  • (Meth) acrylate polyethylene glycol di (meth) acrylate, polyethylene glycol diglycidyl ether di (meth) acrylate, methacrylate, N-methoxymethyl acrylamide, N-dimethylaminoethyl (meth) acrylate, attaroyl
  • S such as morpholine, glycosylethyl methacrylate, 2-acrylamide-2-methylpropanesulfonic acid, N, N-dimethylacrylamide, N-butylpyrrolidone.
  • photopolymerizable polymer resins There are many types of photopolymerizable polymer resins, but systematically, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, copolymer (meth) acrylate, There are polybutadiene (meth) acrylate, silicon (meth) acrylate, and amino resin (meth) acrylate.
  • Examples of cationic polymerization include alicyclic epoxy resins and butyl ether resins.
  • photopolymerizable functional groups and photopolymerizable resins particularly widely used are UV-polymerizable functional groups and UV-polymerizable resins.
  • UV-curable chitosan derivatives having UV-polymerizable functional groups also referred to as UV-curable chitosan derivatives; hereinafter referred to as “UVCC”
  • UVCC UV-curable chitosan derivatives
  • the present invention will be described by taking a coating agent (hereinafter sometimes referred to as “the adhesive or coating agent of the present invention”) as an example.
  • the adhesive or coating agent of the present invention is limited to an ultraviolet curable adhesive or a coating material. is not.
  • the present invention provides an ultraviolet curable adhesive or coating agent containing UVCC and an ultraviolet polymerizable resin.
  • U used in the present invention is
  • VCC has an ultraviolet polymerization functional group in a part of the sugar residue of chitosan.
  • the position of the UV-polymerizable functional group is preferably // of chitosan, or may be a shifted part! /, But is preferably bonded to nitrogen at the 2-position of the sugar residue.
  • the UV-polymerizable functional group (hereinafter referred to as “R1”) that binds to the nitrogen at the 2-position of the sugar residue can cause a polymerization reaction upon UV irradiation.
  • R1 The UV-polymerizable functional group that binds to the nitrogen at the 2-position of the sugar residue can cause a polymerization reaction upon UV irradiation.
  • Power, Karu R1 is preferably a group derived from UV-polymerizable aldehyde.
  • a (meth) acrylic acid derivative having an aldehyde group capable of reacting with the amino group at the 2-position of chitosan is preferable.
  • the (meth) acrylic acid derivative may be any compound as long as it has an alicyclic group or methacryloyl group that cures when irradiated with ultraviolet rays.
  • Such aromatic aldehydes can be synthesized by methods known in the art (see, for example, J. Polym. S., Part A: Polym. Chem., Vol. 25, 3063-3077 (1987)) or JP 2005 — It can be carried out according to the method described in Example 1 of Japanese Patent No. 154477.
  • an aromatic aldehyde there is one represented by the following formula (II).
  • 1 is the proportion of chitosan sugar residues whose amino group is at the 2-position (darcosamine), and m is the chitosan sugar residue whose 2-position is at the N-acetyl group (N-A). Cetyldarcosamine), and n is the ratio of the chitosan sugar residue in which the nitrogen (GlcN) at position 2 is substituted with the UV-polymerizable functional group R1.
  • Preferred values of 1, m, n are 0 ⁇ 1 ⁇ 1, 0 ⁇ m ⁇ l, 0 ⁇ ⁇ 1, and more preferred values of 1, m, n are 0 ⁇ 1 ⁇ 0.8, 0 ⁇ m ⁇ 0.8 and 0.2 ⁇ n ⁇ 0.8.
  • R1 in formula (I) is formula (II):
  • R2 in the R1 functional group is hydrogen or C;! To 3 alkyl group, and C;! To 3 alkyl group includes methyl, ethyl, propyl, and isopropyl.
  • V and R2 are preferably hydrogen or a methyl group.
  • R1 other than the above that can be used in the UVCC of the present invention includes 3 methoxy-4 1 (2 hydroxy 3 methacryloyloxypropoxy) benzyl, 3, 4 bis (2 hydroxy-3- methacryloyloxypropoxy) benzyl 3,5-bis (2hydroxy-3methacryloyloxypropoxy) benzyl, 3-methoxy-4-methacryloyloxybenzyl, 3,4-dimethacryloyloxybenzyl, 3,5-dimethacryloyloxybenzyl group, etc. (See Special Publication 2002-226503).
  • UVCC used for the adhesive or coating of the present invention can be obtained by adding an ultraviolet polymerizable functional group R1 to chitosan.
  • the addition of the R1 group to chitosan can be carried out, for example, according to the method outlined below or the method shown in Example 1 of the present specification).
  • the chitosan a commercially available chitosan may be used which can be obtained by deacetylating chitin by a known method, for example. First, chitosan is dissolved in a dilute organic acid aqueous solution such as formic acid or acetic acid, a hydrophilic solvent such as methanol is added, and then a solution of a (meth) acrylic acid derivative is added. Stir for about 6 to about 12 hours, then add a solution of a reducing agent such as sodium borohydride and stir for another about 6 to about 12 hours. These reaction temperatures may be from about 0 ° C. to room temperature.
  • the ratio of chitosan and (meth) acrylic acid derivative to be reacted depends on the desired degree of substitution of GlcN. For example, if the target value of n in the above formula (I) is 0.6, the molar ratio of the (meth) acrylic acid derivative to the GlcN residue of chitosan should be 1: 0 ⁇ 6! /.
  • UVCC in which R2 is hydrogen in the formula (II)
  • 2-hydroxy-3- (4-formyl-2-methoxy) phenoxypyrutalylate is used as a (meth) acrylic acid derivative having an aldehyde group.
  • 2-hydroxy 3- (4 formyl as a (meth) acrylic acid derivative having an aldehyde group 2-Methoxy) phenoxypropinoremethacrylate is used.
  • the UVCC used in the adhesive or coating agent of the present invention may be one kind or a combination of two or more kinds.
  • the amount of UVCC in the adhesive or coating of the present invention depends on the type of UVCC, the amount of other components (such as an ultraviolet polymerizable resin and a photopolymerization initiator), and the properties of the target adhesive or coating. Force that can be determined
  • the preferred amount of UVCC is from about 0.5 to about 5% by weight.
  • Another essential component of the adhesive or coating agent of the present invention is an ultraviolet polymerizable resin.
  • the present inventors prepared an adhesive containing UVCC, water, DMSO and a photopolymerization initiator (see JP-A-2005-154477), embedded the adhesive cured under the skin of the skin, When the tissue was examined, biocompatibility was shown, but the adhesive strength as an adhesive was weak, and water and DMSO were not involved in the curing reaction, so water and DMSO were liberated after polymerization. It was.
  • the above-mentioned drawbacks are overcome by using UVCC and an ultraviolet polymerizable resin in combination. In other words, mixing with UV-polymerizable resin improves adhesion and covering ability, and mixing UVCC with an ultraviolet-polymerizable resin alone may lower the inflammatory reaction in vivo. Proven.
  • UV-polymerizable resins are known, and any resin may be used. By appropriately selecting the solvent, it is possible to use not only water-soluble resins but also water-insoluble resins. Further, the ultraviolet polymerizable resin may be in the form of a monomer or a polymer. Examples of the UV-polymerizable resin that can be used in the adhesive or coating of the present invention include methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate, keihylic acid, methacrylamide, attalyloylmorpholine, and N-methyl.
  • the UV-polymerizable resin used in the adhesive or coating agent of the present invention is preferably one that has low toxicity to living organisms, or one that is hypoallergenic!
  • the ultraviolet polymerizable resin used in the adhesive or coating agent of the present invention may be one kind or a combination of two or more kinds.
  • the amount of the UV polymerizable resin in the adhesive of the present invention is determined according to the type of the UV polymerizable resin, the amount of other components (such as UVCC and a photopolymerization initiator), and the properties of the target adhesive.
  • the preferred amount of UV-polymerizable resin is greater than 0% by weight and up to about 95.7% by weight.
  • a photopolymerization initiator may be used.
  • Various photopolymerization initiators are known, and any substance can be used as long as it generates a radical that becomes a polymerization initiation group upon irradiation with light.
  • Photopolymerization initiators that can be used in the adhesive or coating agent of the present invention include hydroxyketone-based, aminoketone-based, and bisacinorefhosphoxide-based materials, such as benzophenone, benzoinethyl ether, Acetophenone, benzoin methyl ether, hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylphenylpropanone 1 [4 (2-hydroxyethoxy) phenyl] 2 hydroxy-2-methylpropanone, etc. in the visible light region
  • the initiator having an absorption maximum include camphorquinone and a metaguchisen polymerization initiator.
  • the photopolymerization initiator used in the adhesive or coating agent of the present invention is preferably a photopolymerization initiator that has low toxicity to the living body or low irritation.
  • photopolymerization initiators include, for example, Irgacure (registered trademark) 2959 (2 hydroxy 1 [4 (hydroxyethoxy) phenyl] 2-methyl-1 propanone).
  • IrlOOO Irgacure (registered trademark) 1000; Chino 'Specialty Chemicals Co., Ltd.
  • Ir819 Irgacure (registered trademark) 819; Chino' Specialty Chemicals Co., Ltd.
  • Ir 184 Irgacure (registered trademark)) 184; Chinoku 'Specialty Chemicals Co., Ltd.
  • the amount of GLM is less than 50% by weight, water-soluble photopolymerization It is preferable to use a combination of initiators (for example, Irgacure 2959).
  • the photopolymerization initiator used in the adhesive or coating agent of the present invention may be one kind or a combination of two or more kinds.
  • the amount of the photopolymerization initiator in the adhesive or coating of the present invention includes the type of photopolymerization initiator, the amount of other components (UVCC, UV-polymerizable resin, etc.), and the target adhesive or coating agent.
  • the preferred amount of photoinitiator is from about 0.5 to about 4% by weight, although it can be determined depending on the properties. When an electron beam or the like is used as a light source, it is not always necessary to add a photopolymerization initiator.
  • UVCC may not dissolve well in the adhesive or coating of the present invention.
  • the UVCC is blended after it is dissolved in a substance that is highly soluble or highly dispersible in UVCC.
  • substances with high solubility or dispersibility of UVCC include acetic acid (aqueous solution), methacrylic acid (aqueous solution), acrylic acid (aqueous solution), DMSO, etc.
  • acetic acid aqueous solution
  • methacrylic acid aqueous solution
  • acrylic acid aqueous solution
  • DMSO 2-acrylamido-2-methylpropanesulfonic acid
  • AMPS is one of UV-polymerizable acidic substances.
  • the amount of the substance capable of dissolving or dispersing UVCC to the adhesive or coating agent of the present invention may be an amount that can dissolve or disperse UVCC.
  • the AMPS aqueous solution is strongly acidic, it is preferable to mix it so that it is neutralized when mixed with UVCC and the pH of the mixed solution is about 4 to about 8, and further about 6 to about 7. For example, it is preferred to use from about 3.8 to about 45% by weight of a 3% aqueous solution for the adhesive or coating of the present invention.
  • Preferable amount of each component in the adhesive or coating of the present invention described above! / is just a guideline, and UVCC does not precipitate or precipitate when mixed, Any amount is acceptable.
  • the adhesive or coating agent of the present invention may contain other components, for example, an aqueous or non-aqueous solvent such as water or DMSO depending on the purpose. Furthermore, it may contain a disinfectant, a local anesthetic, a wound treatment, epidermal growth factor, and other medicinal ingredients.
  • an aqueous or non-aqueous solvent such as water or DMSO depending on the purpose.
  • it may contain a disinfectant, a local anesthetic, a wound treatment, epidermal growth factor, and other medicinal ingredients.
  • the adhesive or coating agent of the present invention can also be used for adhesion and coating of substances other than living organisms.
  • the adhesive or coating agent of the present invention can be used as a medical product by selecting a component having low toxicity or irritation to the living body or non-toxicity.
  • the adhesive or coating agent of the present invention can be applied to a desired part of a living body.
  • the term “medical use” includes not only human medical treatment but also veterinary use.
  • the adhesive or coating of the present invention has an adhesive strength or covering ability that can withstand practical use when used on a living body such as skin, and has a sufficient flexibility after curing and has a sealing property. Is excellent.
  • the adhesive or coating agent of the present invention is excellent in hemostatic effect.
  • the adhesive or coating of the present invention is effective for skin adhesion and coating.
  • the adhesive or coating agent of the present invention is also suitable as a medical coating material.
  • a preferable use as a medical coating agent is a use as a wound protective agent.
  • the wound protection agent include antibacterial agents such as mercurochrome, iodine tincture, chlorhexidine dalconate, benzalkonium chloride, alkyldiaminoethinoglycine, penicillin, gentamicin, chloramphenicol, tetracycline, neomycin, and lidocaine.
  • Local anesthetics such as xylocaine, mer force in, and carbo force in may also be included.
  • the wound protective agent may include an anti-inflammatory agent such as indomethacin and a growth factor such as epidermal growth factor (EGF)! /.
  • EGF epidermal growth factor
  • the adhesive or coating agent of the present invention as a medical coating material may be a sealer at the catheter insertion position. Furthermore, the adhesive or coating material of the present invention as a medical coating material can be used as a sealer for a teat mouth and a teat tube.
  • the adhesive or coating agent of the present invention is highly useful in the field of cosmetic surgery because of its high transparency after curing.
  • the adhesive, coating, medical adhesive, and medical coating material of the present invention into various forms. These may be formulated as powder and dissolved in water or DMSO before use, or may be formulated in a tube. Since the adhesive or coating of the present invention is photocurable, it is preferable to formulate it in a light-shielding sealed container!
  • an ordinary ultraviolet irradiation device is sufficient.
  • the adhesive or coating agent of the present invention can reach a sufficient adhesive strength or exhibit a sufficient covering ability by uv irradiation within a few seconds.
  • the adhesive or coating agent of the present invention has been described mainly with respect to the ultraviolet curable adhesive or coating agent.
  • the photopolymerizable functional group, the photocurable resin, or the photopolymerization initiator, and others it goes without saying that by selecting these components, it is possible to obtain an adhesive or a coating that is cured by visible light, electron beam or the like.
  • Those skilled in the art can appropriately select and use such photopolymerizable functional groups, photocurable resins, and photopolymerization initiators.
  • the present invention also includes an adhesive or a coating agent that is cured by such visible light or electron beam.
  • the photocurable adhesive or coating agent containing the chitosan derivative having a photopolymerizable functional group of the present invention and a photopolymerizable resin includes those that can be cured by visible light.
  • the ultraviolet curable adhesive or coating agent containing a chitosan derivative having an ultraviolet polymerizable functional group and an ultraviolet polymerizable resin of the present invention includes those that can be cured by visible light.
  • the adhesive or coating material of the present invention that can be cured by visible light is preferable because irradiation light is visible light that is gentle to the living body when applied to the living body.
  • the visible light polymerizable functional groups that can be used in the adhesive or coating agent of the present invention that is cured by visible light are not limited to those exemplified above.
  • the visible light polymerizable resin that can be used in the adhesive or coating agent of the present invention that is cured by visible light includes monofunctional or polyfunctional (meth) acrylate, for example, hydroxyethyl (meth) acrylate, hydroxy Long chain alkyl (meth) acrylates such as propyl (meth) acrylate, methyl (meth) acrylate, methoxypolyethylene glycol methacrylate, stearyl methacrylate, butanediol (meth) acrylate, glycidyl methacrylate , 2-Acrylamide-2-Methylpropane sulfonic acid, methacrylamide, triethylenedalicol dimetatalylate (Tri-EDMA), 2, 2-bis (p-2'-hydroxy 1 3'-methacryloxypropoxyphene Nole) propane (Bis—GMA), 2,2-bis (4-methacryloxy polyester) Kishifue two Norre) propane (Bis- MPEPP), G (
  • Decane (TCDDMA) and the like are exemplified, but not limited thereto.
  • This Visible light polymerizable resins that have low toxicity or low irritation to living organisms are preferred.
  • Long-chain alkynole (meth) atalylate such as methoxypolyethylene glycol metatalylate and stearyl metatalylate, butanediol (meta ) Atarylate, glycidyl metatalylate, 2-acrylamide-2-methylpropanesulfonic acid, and the like, but are not limited thereto.
  • Visible light polymerization initiators that can be used in the adhesives or coatings of the present invention that are cured by visible light include eosin Y, coumarin, rose bengal, erythemacin, camphorquinone, 9 fluorenone, titanocene compounds such as biscyclohexane. Examples thereof include, but are not limited to, pentagebirubis (difluoropyroylenyl) titanium. Among them, camphorquinone, 9fluorenone, etc., which are preferred as visible light polymerization initiators that have low toxicity or low irritation to living organisms, are not limited to these.
  • a normal visible light irradiation device is sufficient as the irradiation device used for curing the adhesive or coating material of the present invention with visible light to obtain an adhesive or coating material.
  • These visible light irradiation conditions can be appropriately selected by those skilled in the art according to the types and amounts of the individual components and the uses of the adhesive and the covering material.
  • Those skilled in the art will readily manufacture the adhesives or coatings of the present invention that are cured by visible light, based on the general knowledge and capabilities and explanations of the UV curable adhesives or coatings described above, Can be used.
  • acetic anhydride and aldehyde to be added is adjusted to 0 to 1 molar equivalent per darcosamine residue of chitosan, and ultraviolet curable chitosan derivatives having different functional group substitution degrees (DS) are obtained.
  • Table 1 shows reagent addition amounts and derivative abbreviations.
  • test solution 1 The purified UVCC was dissolved with the following composition 1 to give test solution 1. Water and DMSO were added to UVCC, stirred until dissolved, and a photopolymerization initiator was added to obtain Test Solution 1. [0044] [Table 2]
  • Photopolymerization initiator M000 1 Irgacure 1000 (weight ratio 1) is used as the photopolymerization initiator.
  • the purified UVCC was dissolved in the following composition 2 to prepare test solution 2.
  • 3% AMPS (9g) was added to UVCC (lg) and stirred for! ⁇ 2 days to make UVCC emulsion or solution.
  • Table 4 summarizes the results of testing the solubility of purified UVCC in DMSO, 2% acetic acid aqueous solution, 3% AMPS aqueous solution, and 3% AMPS aqueous solution + GLM.
  • GLM (20 g) was added and stirred until homogeneous to obtain a single brown transparent UVCC 'resin mixed solution.
  • Test solution 2 was prepared by adding 20% DMSO solution of photopolymerization initiator so that the amount of polymerization initiator was 2% of GLM.
  • the ratio of Ir819 and Irl84 was 1: 5 (weight ratio).
  • Composition 2 is merely an example, and UVCC is about 0.5 to about 5% by weight, 3% AMPS is about 3.8 to about 45%, GLM is less than about 95.7% by weight (UVCC precipitates and precipitates) If the photoinitiator is in the range of about 0.5 to about 4% by weight, a test solution mixed in the same manner as above can be obtained.
  • composition 1.b 1% derivative Z% AcOH.
  • composition 2. e dissolves but has high viscosity and is easily separated
  • Horse skin was collected from the waste horse and cut into 5 cm (H) x 2 cm ( W ) after shaving.
  • a pseudo-incision was created by making an incision of about 7 mm in the lateral direction in the center.
  • About 100 a 1 of the test solution of Composition 1 and Composition 2 was applied to the incision, and UV irradiation was performed for 4 seconds at an irradiation distance of 10 mm to cure the test solution and close the incision site.
  • the UV irradiation device is EYE CURE LIGHT
  • the tensile strength measuring instrument Measurement Innovator (Aiko Engineering Co., Ltd.) was used, and the traction machine was Test Stand Model— 1356 (Aiko Engineering Co., Ltd.). The pulling speed is expressed as 5 mm / min, the tensile strength is expressed as N (Newton), and the tensile strength is defined as the load applied when the incision point fixed with the test solution is opened by pulling the test piece.
  • the results of the test solution of composition 1 are shown in Table 5, and the results of the test solution of composition 2 are shown in Table 6. [0050] [Table 5]
  • CA medical adhesive
  • test solutions 100 1 each of test solutions were poured into a 96-microwell plate, irradiated with ultraviolet rays, and a disk-shaped UVCC cured product with a diameter of about 6 mm and a height of about 2 mm was used as an embedded test piece.
  • mice female, 8 weeks old, weight 25 ⁇ 5 g
  • Nembutal 50 mg / kg, administered intraperitoneally
  • a pocket for sample embedding was created in a pocket-like shape, and a hardened sample was embedded in the subcutaneous pocket, and the incision wound was sutured by simple stitching with 40 nylon sutures and used as a test model.
  • the sampled tissue was fixed in formalin, embedded in norafine, and sliced into slices.
  • the slices were stained with hematoxylin-eosin and used as histological specimens.
  • the smaller the number the smaller the inflammatory reaction and the higher the biocompatibility.
  • Table 7 shows the results of counting the number of inflammatory cells in the test solution composition 1 cured product embedment test
  • Table 8 shows the results of the inflammatory cell count in the test solution composition 2 test curable material embedding test.
  • A neutrophils
  • B fibroblasts
  • C Ryukyu (li, pamphlet, plasma cells, etc.) o
  • CA medical adhesive
  • AS surgical absorbable suture
  • DM so,.
  • UVCC of 1, 2, 5, 6, 7, 8 are surgical adhesive (CA) and Compared to the surgical absorbable suture (AS), the total number of inflammatory cells around the implant is rather small and it is judged that there is no severe inflammatory reaction. In addition, there were few inflammatory reactions compared to GLM, a biocompatible material. In particular, the cured product with UVCC of 6 (GlcNAcO. 4-GlcNPs 0.6) showed mild results for the living body with the smallest total number of inflammatory cells.
  • Diaphragmatic hernia The diaphragm ruptures and the abdominal intestinal tract moves into the thoracic cavity. The intestinal tract is returned to the abdominal cavity by surgery, a drain is placed in the chest cavity, and the drain is removed on the second day. Install the drain again, and immediately after removing the air, apply about 100 ⁇ of the test solution of composition 2 (UVCC No. 6) to the skin puncture hole, irradiate with UV for 4 seconds at an irradiation distance of 10 mm, and cure and cut the test solution. The place was occluded.
  • composition 2 UVCC No. 6
  • EYE CURE LIGHT SPOT UP 150M (Eye Graphics Co., Ltd.) was used as the UV irradiation device, and a short arc metal halide lamp was used as the UV lamp.
  • a short arc metal halide lamp was used as the UV lamp.
  • the entire skin of the sutured part was similarly sealed. After that, there was no recurrence of pneumothorax, and it was completely cured.
  • Resins having the compositions shown in Table 9 were prepared. Visible light irradiation device: Elipar (trademark) Fr ee Light2 (3M ESPE) (High power LED photopolymerizer; light intensity 1000mW / cm 2 ; irradiation wavelength: 430-4 80 nm), a light guide diameter of 8 mm and an irradiation distance of about 1 cm was irradiated for 10 to 20 seconds to obtain a rubber-like cured product.
  • Elipar trademark
  • Fr ee Light2 3M ESPE
  • UVCC is a substance with sufficient performance as an ideal bioadhesive, and mixing with existing resin has been shown to have the effect of reducing the biostimulation of the resin alone.
  • the present invention provides adhesives and coatings that are excellent in all of adhesiveness, biocompatibility, and convenience, especially medical adhesives and coatings, and uses thereof. ! /, I can use S for IJ.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Engineering & Computer Science (AREA)
  • Animal Behavior & Ethology (AREA)
  • Materials Engineering (AREA)
  • Public Health (AREA)
  • Hematology (AREA)
  • Surgery (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Materials For Medical Uses (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un adhésif ou un agent de revêtement, en particulier un adhésif ou agent de revêtement médical ayant un excellent caractère adhésif, une excellente biocompatibilité et une excellente commodité d'utilisation. L'invention concerne également l'utilisation d'un tel adhésif ou agent de revêtement. De façon spécifique l'invention concerne un adhésif ou agent de revêtement photodurcissable contenant un dérivé de chitosan ayant un groupe fonctionnel photopolymérisable et une résine photopolymérisable.
PCT/JP2007/067417 2006-09-27 2007-09-06 Adhésif ou agent de revêtement à base de chitosan photodurcissable de type mélange Ceased WO2008038503A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
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JP2011006571A (ja) * 2009-06-25 2011-01-13 Dic Corp 接着剤、及びラミネートフィルム
JP2011160959A (ja) * 2010-02-09 2011-08-25 Tottori Univ 新規キチン誘導体
JP2016535810A (ja) * 2013-09-30 2016-11-17 エルジー・ケム・リミテッド ラジカル硬化型接着剤組成物、これを含む偏光板および光学部材
WO2020215297A1 (fr) * 2019-04-26 2020-10-29 四川大学 Liquide précurseur du type jet à base de polyuréthane d'un pansement hydrogel photodurcissable et son procédé de préparation
CN120758227A (zh) * 2025-08-29 2025-10-10 江苏瑞洋安泰新材料科技有限公司 一种阻燃型改性ms密封胶及其制备方法

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JP2000109501A (ja) * 1998-09-30 2000-04-18 Daishin Kagaku Kk Ｎ−アルキルキトサン誘導体の製造方法、ｎ−アルキルキトサン誘導体、およびこれを用いた重合体
JP2002226503A (ja) * 2001-01-30 2002-08-14 Daishin Kagaku Kk Ｎ−アルキルキトサン誘導体の製造方法、ｎ−アルキルキトサン誘導体、およびこれを用いた重合体
WO2003090765A1 (fr) * 2002-04-23 2003-11-06 Netech Inc. Compositions medicinales contenant un derive de chitosan photo-reticulable
JP2005154477A (ja) * 2003-11-20 2005-06-16 Tottori Univ 紫外線硬化型キトサン誘導体を用いた医療用接着剤および医療用被覆剤

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US20100056462A1 (en) * 2005-05-13 2010-03-04 Netech Inc. Medical composition for promotion of skin regeneration

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JP2000109501A (ja) * 1998-09-30 2000-04-18 Daishin Kagaku Kk Ｎ−アルキルキトサン誘導体の製造方法、ｎ−アルキルキトサン誘導体、およびこれを用いた重合体
JP2002226503A (ja) * 2001-01-30 2002-08-14 Daishin Kagaku Kk Ｎ−アルキルキトサン誘導体の製造方法、ｎ−アルキルキトサン誘導体、およびこれを用いた重合体
WO2003090765A1 (fr) * 2002-04-23 2003-11-06 Netech Inc. Compositions medicinales contenant un derive de chitosan photo-reticulable
JP2005154477A (ja) * 2003-11-20 2005-06-16 Tottori Univ 紫外線硬化型キトサン誘導体を用いた医療用接着剤および医療用被覆剤

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011006571A (ja) * 2009-06-25 2011-01-13 Dic Corp 接着剤、及びラミネートフィルム
JP2011160959A (ja) * 2010-02-09 2011-08-25 Tottori Univ 新規キチン誘導体
JP2016535810A (ja) * 2013-09-30 2016-11-17 エルジー・ケム・リミテッド ラジカル硬化型接着剤組成物、これを含む偏光板および光学部材
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WO2020215297A1 (fr) * 2019-04-26 2020-10-29 四川大学 Liquide précurseur du type jet à base de polyuréthane d'un pansement hydrogel photodurcissable et son procédé de préparation
CN120758227A (zh) * 2025-08-29 2025-10-10 江苏瑞洋安泰新材料科技有限公司 一种阻燃型改性ms密封胶及其制备方法

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