WO2014027707A1 - Film de support médical du type feuille à nanofibre et son procédé de préparation - Google Patents

Film de support médical du type feuille à nanofibre et son procédé de préparation Download PDF

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WO2014027707A1
WO2014027707A1 PCT/KR2012/006536 KR2012006536W WO2014027707A1 WO 2014027707 A1 WO2014027707 A1 WO 2014027707A1 KR 2012006536 W KR2012006536 W KR 2012006536W WO 2014027707 A1 WO2014027707 A1 WO 2014027707A1
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Prior art keywords
support film
medical support
nanofiber sheet
electrospinning
present
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PCT/KR2012/006536
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English (en)
Korean (ko)
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김원일
권오형
박미란
김성환
Original Assignee
주식회사 원바이오젠
금오공과대학교 산학협력단
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Priority to PCT/KR2012/006536 priority Critical patent/WO2014027707A1/fr
Publication of WO2014027707A1 publication Critical patent/WO2014027707A1/fr

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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/4358—Polyurethanes
    • 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
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/02—Adhesive bandages or dressings
    • A61F13/0203—Adhesive bandages or dressings with fluid retention members
    • A61F13/0206—Adhesive bandages or dressings with fluid retention members with absorbent fibrous layers, e.g. woven or non-woven absorbent pads or island dressings
    • 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
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/02—Adhesive bandages or dressings
    • A61F13/0203—Adhesive bandages or dressings with fluid retention members
    • A61F13/0206—Adhesive bandages or dressings with fluid retention members with absorbent fibrous layers, e.g. woven or non-woven absorbent pads or island dressings
    • A61F13/0209—Adhesive bandages or dressings with fluid retention members with absorbent fibrous layers, e.g. woven or non-woven absorbent pads or island dressings comprising superabsorbent material
    • 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
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/02—Adhesive bandages or dressings
    • A61F13/0203—Adhesive bandages or dressings with fluid retention members
    • A61F13/0226—Adhesive bandages or dressings with fluid retention members characterised by the support layer
    • 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
    • A61L15/26—Macromolecular compounds obtained otherwise than 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/425—Porous materials, e.g. foams or sponges
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • 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
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces

Definitions

  • the present invention relates to a medical support film in the form of a nanofiber sheet prepared using electrospinning, and in particular, the fiber diameter is nanosized and made porous by using a hydrophilic polyurethane resin having moisture permeability as a main component. And a medical support film in the form of a nanofiber sheet.
  • wound dressings and patch agents applied to and applied to the skin include a support film as a support.
  • the wound dressing material includes, for example, an absorbent for absorbing and retaining an effluent and a support film as a support for supporting the absorbent.
  • the support film is required to have adequate moisture permeability and waterproofness, elongation rate and recovery rate.
  • polyvinyl chloride, a nonwoven fabric, etc. are used typically.
  • Polyvinyl chloride film (polyvinyl chloride) film is conventionally used as a support film, because of the low cost advantage is still widely used in wound dressings, such as disposable bands.
  • polyvinyl chloride film has a low moisture permeability, so when used for a long time, the skin is hydrated by moisture, and maceration occurs. It causes car damage, which can have a bad effect on the wound.
  • a method of increasing permeability by perforation of the film has been attempted, but perforation has another problem that bacteria do not enter the hole or become waterproof. have.
  • the polyvinyl chloride film when applied to the site, such as joints also have the problem of being easily lifted by the movement of the human body.
  • Nonwoven fabric supports and papers which are conventionally used as support films, are also inexpensive and easy to use. However, it does not have a protective function or waterproofness against bacteria or foreign substances, and has a problem in that it is easily dropped when applied to curved parts of the body. In addition, because the moisture permeability is too high to maintain the wound in a dry state there is a problem that the absorbent is attached to the wound surface causing damage to the new tissue during dressing exchange.
  • a polyurethane film having a waterproofness and a degree of moisture permeability is used in a dry process and a wet process method.
  • stacked the fabric of the elastic net form to the film manufactured by this is disclosed.
  • the polyurethane film manufactured by the dry processing method is excellent in water resistance but low in moisture permeability because of its non-porous structure.
  • the thickness of the film becomes thick there is a problem that the moisture permeability falls rapidly.
  • the polyurethane film produced by the wet processing method may have a microporous structure and is excellent in terms of moisture permeability.
  • this is a manufacturing method of coating a polyurethane solution prepared by mixing a polyurethane resin and an organic solvent on a release paper, immersing in water and coagulating to have a microporous structure, which leaves residual solvent in the film. Therefore, there is a problem of causing allergy to the skin due to poor biocompatibility, and has a process problem that the manufacturing process is not environmentally friendly.
  • Korean Patent Registration No. 0821314 describes a method of manufacturing an elastic nonwoven fabric using a melt blown process using a bicomponent polymer.
  • This patent is characterized by a polyurethane-based elastomer as a core component to impart elasticity, and a method of manufacturing by introducing a heterogeneous elastomer as a cis component to prevent stickiness of the manufactured nonwoven fabric.
  • the size of the fiber diameter is larger than the nonwoven fabric produced by the electrospinning method, the flexibility is inferior to the nonwoven fabric produced by the electrospinning method.
  • Electrospinning is recognized as the most promising microfiber manufacturing technology.
  • NT nano-technology
  • electrospinning method applies a high voltage to the polymer solution, and the polymer jet is ejected by evaporating the solvent, resulting in nanoscale
  • a spinning method to obtain a fiber having a diameter it has a high specific surface area, porosity, high aspect ratio and flexibility, and it is easy to control the fiber diameter by controlling the spinning conditions.
  • Nanofibers manufactured by electrospinning method can be applied to various fields such as reinforcing agent, membrane material for high efficiency filter, functional fiber, military supplies using antifouling function, wound dressing, drug delivery system (DDS), scaffold for tissue engineering It is recently attracting attention as a processing method for medical materials having high added value.
  • DDS drug delivery system
  • the electrospinning system can be roughly divided into a solution supply part, a high voltage supply part, a collector part in which nanofibers are formed.
  • the radiation environment humidity, temperature
  • the solution supply part is composed of a syringe pump and a syringe (or nozzle) part for precisely discharging the solution at a constant speed, and can control the characteristics of the fiber according to the design of the shape, diameter, and material of the syringe needle.
  • the high voltage supply part is an insulated cable composed of a (+) pole that charges a polymer solution portion having a high dielectric constant and a (-) pole where the charged solution is collected in the form of nanofiber filaments, and controls voltage and current.
  • the collector portion in which the nanofibers are collected can adjust the arrangement of the nanofiber strands according to the design of its shape, movement, and speed, and also manufacture various materials according to the purpose.
  • the type of material used for electrospinning is generally in a well-dissolved solution state and has a great influence on fiber formation depending on the solution characteristics of the polymer used for electrospinning. Such solution characteristics include concentration, viscosity, surface tension, Conductivity, dielectric properties, volatility, and the like.
  • the concentration of the polymer solution is closely related to the viscosity. Since the viscosity is a measure of the entanglement and fluidity of the polymer chain, it is known as an important factor that affects the shape, diameter, and spraying speed of the fiber produced during electrospinning. have. Although there are differences depending on the polymer properties, it is reported that fibrosis is possible with a viscosity of about 0.5 to 50 poise. If the viscosity is too high or too low, fibrosis does not occur. Electrospinning is a technology that produces fibers of several nm to several micrometers by radiating a large potential difference between charged polymer and grounded current collector plate by applying electrostatic force to polymer solution or melt. It is a spinning technology that enables spinning with a high spinning speed and small amount, and at the same time obtains the form of nonwovens.
  • Korean Patent Laid-Open Publication No. 10-2012-0078329 discloses a technique for manufacturing a nonwoven fabric adhesive tape using the electrospinning method as described above.
  • a fiber having a relatively small fiber diameter can be obtained, thereby providing flexibility.
  • a polyether or polyester polyurethane chip has a temperature of 150 to 300 ° C. to produce a spinning solution and a problem that may cause deformation of the polymer material upon heating. .
  • calendering by applying a temperature of about 120 ° C.
  • the fibrous nonwoven fabric is stiff and easily broken by pressure and temperature during calendering. There is a problem that can cause brittleness.
  • the micropores formed on the fibrous web are destroyed by the heat and pressure of calendering, and thus, the moisture permeability and flexibility of the medical film may be reduced.
  • the present invention is to solve the problems of the conventional medical support film described above, an object of the present invention is to have a nano-size fiber diameter using electrospinning, a lot of fine pores are formed, excellent moisture permeability, To provide a medical support film in the form of a nanofiber sheet excellent in flexibility and flexibility.
  • the present invention is excellent in elasticity in the longitudinal direction, transverse direction, by forming more pores than the conventional non-fiber film of the nanofiber form excellent elasticity, moisture permeability and good flexibility medical support film and a method of manufacturing the same It aims to provide.
  • the hydrophilic polyurethane resin solution concentration of 0.1 to 50% by weight, voltage 5 to 100 kV, discharge rate of the solution 0.1 to 10 ml / hr, spinning distance 3 to 60 cm, humidity 30 to 80% Spinning under electrospinning conditions to obtain a nonwoven fabric in the form of a nanofiber sheet;
  • a medical support film in the form of a porous nanofiber sheet prepared by the above method and an external preparation such as a dressing material, a patch, an adhesive band, and the like including the support film.
  • medical use is meant to include all that can be applied to the human body or animals for the purpose of treatment, treatment, protection, and the like, regardless of whether the law is classified as medical.
  • a hydrophilic polyurethane resin having a moisture-permeable water-proof function as a main component and a method of impregnating the water by mixing with a hydrophilic water-soluble polymer that is easily dissolved in water and then electrospun, compared to conventional nanofiber non-woven medical film of the porosity In this way, it is possible to produce a medical support film having excellent flexibility, moisture permeability, mechanical properties, and excellent elasticity in both directions.
  • the method of the present invention can control the size of the pores and the number of pores on the surface of the fiber nonwoven web according to the content of the water-soluble polymer having a hydrophilic, various kinds of medical support film of the nanofiber sheet form having different mechanical properties It can manufacture.
  • the manufacturing method of the present invention can minimize the amount of the residual organic solvent by the step of impregnating in water, compared to the conventional medical support film has excellent biocompatibility, and can reduce the skin allergic reaction of the conventional nonwoven fabric, It can be used in a wide range of applications as compared to polyurethane medical support films made by polyvinyl chloride, dry and wet processes.
  • Medical support film in the form of a nanofiber sheet obtained according to the present invention is a non-woven fabric made of a conventional melt blown (melt blown) process and the non-woven fabric in the form of a non-woven fabric undergoing a calendering process after the electrospun by melting the polymer at a high temperature
  • the diameter of the fiber is smaller than the support film, it is a non-woven fabric with a very high specific surface area, flexible, and three-dimensional porosity, so it can easily adhere to joints or curved wounds, It has the advantage of not falling off easily.
  • FIG. 1 is a system configuration diagram of the electrospinning apparatus used in the embodiment of the present invention.
  • Ventilation hole 8 Heater (solvent volatilization promotion)
  • Figure 2 is a scanning electron micrograph (SEM) of the medical support film of the nanofiber sheet prepared in an embodiment of the present invention.
  • Figure 3 is a photograph showing the cytotoxicity test results of the medical support film of the nanofiber sheet prepared by Preparation Example (c) of the present invention.
  • a hydrophilic polyurethane resin is a main component, and water-soluble polymers such as ethylene oxide / popylene oxide block copolymer are introduced and mixed, followed by electrospinning.
  • a fiber nonwoven fabric is obtained, and the nanofiber nonwoven fabric is impregnated with a solvent to dissolve and remove the water-soluble polymer component, followed by drying to prepare a medical support film in the form of a nanofiber sheet.
  • the method for producing a medical support film in the form of a nanofiber sheet of the present invention comprises the steps of making a mixed polymer solution; Electrospinning to obtain a nonwoven fabric in the form of a nanofiber sheet; Impregnating with a solvent and then drying to obtain a medical support film in the form of a nanofiber sheet having porosity.
  • each step will be described in detail.
  • hydrophilic polyurethane resin 100 parts by weight of hydrophilic polyurethane resin; 0.5-50 parts by weight of a polymer having hydrophilicity and water solubility; And 20 to 100 parts by weight of the organic solvent is mixed to make a mixed polymer solution.
  • the hydrophilic polyurethane resin was synthesized using solution polymerization using methyl ethyl ketone and dimethylformamide as co-solvents.
  • a polyol for imparting hydrophilicity a polyol in the form of polyethylene glycol or an ethylene oxide / propylene oxide block copolymer, or both may be used together.
  • the content of hydrophilic group ethylene oxide is important for imparting hydrophilicity, which is described in “Journal of Cellular Plastics 1976; 12; 285 ”“ Journal of Cellular Plastics 1983; 19; 259 ”, US Pat. No. 4,008,189 (1975.11.4) and the like. Therefore, most preferably, it is preferable to introduce a hydrophilic channel into the chemical structure of the polyurethane by synthesizing by introducing polyethylene glycol.
  • Isocyanates which react with such polyols and short diols, which are chain extenders, to synthesize polyurethanes can be used with aromatic, aliphatic and cycloaliphatic isocyanates or mixtures thereof. have.
  • One kind selected from the group consisting of tetramethylene-xylene diisocyanate may be used alone or two or more kinds may be used together. Most preferably, methylene diphenyl isocyanate may be used as the isocyanate.
  • the hydrophilic polyurethane resin, polyethylene glycol and / or ethylene oxide / propylene oxide block copolymer polyol (ethylene oxide / propylene oxide block copolyol) and methylene diphenyl diisocyanate (methylene Diphenyl diisocyanate) was used to synthesize the reaction.
  • polyethylene oxide Preferably polyethylene oxide; Ethylene oxide / propylene oxide block copolymers; Polyvinylpyrrolidone; And one or more selected from the group consisting of polyvinyl alcohol (polyvinyl alcohol). More preferably, polyethylene oxide and ethylene oxide / propylene oxide block copolymers (F-68, F-87, F-88, F-108, and F- having excellent miscibility with polyurethane resins and excellent solubility in organic solvents). 127 BASF Corporation) can be used.
  • the content of ethylene oxide is 80% or more, the molecular weight is 8,400g / mol or more, the HLB (hydrophilic-lipophilic balance) is 25 or more, and the F-68 (BASF Co., Ltd.), which is widely used for medical purposes, is used. It is good. In a preferred embodiment of the present invention, F-68 was used.
  • the polymer which has hydrophilicity and water solubility within 0.5-50 weight part with respect to 100 weight part of polyurethane resins. More preferably, 1 to 40 parts by weight is good considering the viscosity of the final mixed solution. In the case of F-68 is mixed more than 40 parts by weight of the viscosity of the mixed solution is difficult to spin, and the mechanical properties of the finally prepared nanofiber sheet medical support film may be lowered.
  • the polymer having hydrophilicity and water solubility is formed with a hydrophilic polyurethane resin in the next step, and then dissolved and removed by a solvent to impart porosity to the nanofiber nonwoven fabric.
  • the organic solvent is preferably dimethylformamide; Methyl ethyl ketone; Ethyl acetate; Butyl acetate; Toluene; Alcohols; And tetrahydrofuran (THF), one or two or more selected from the group consisting of. Most preferably, dimethylformamide (DMF) having excellent miscibility with water and excellent solubility in polyurethane resin is used.
  • the organic solvent dissolves a polymer having water solubility and hydrophilicity with the hydrophilic polyurethane resin, thereby making a mixed polymer solution suitable for the next step of electrospinning. At this time, the polymer should be uniformly dissolved in the organic solvent for electrospinning.
  • the mixed polymer solution Since the uniform nanofiber form is obtained in a uniform solution state during electrospinning, the mixed polymer solution must be completely dissolved to be free of impurities. In the embodiment of the present invention by using a stirrer at room temperature for 24 hours at 50 ⁇ 100 RPM to stir completely so as not to produce bubbles as possible. If there are bubbles in the mixed solution, it is better to remove the bubbles completely because it is difficult to obtain uniform fibers during spinning. At this time, in order to remove a bubble, you may go through a well-known defoaming process.
  • the amount of the organic solvent added to 100 parts by weight of the hydrophilic polyurethane resin is preferably 20 to 100 parts by weight, more preferably 50 to 70 parts by weight, considering the viscosity of the final mixed solution and the concentration of the hydrophilic polyurethane resin. It is good to use wealth.
  • nanofiber refers to a fiber having an ultra-fine structure having a diameter of about 10 to 5,000 nm.
  • the electrospinning system shown in Figure 1 is a DC high voltage generator capable of supplying a voltage of 0 ⁇ 40 kV (DC High Voltage Generator [40 kV / 3mA], Chungpa EMT Co.) (not shown); Plate type support jack (200 x 200 mm, stainless steel) (not shown) or rotating drum type (metal drum, 400 (w) x 216 ( ⁇ ) mm, stainless steel) collector plate ( 4); Drum speed controller unit (0 to 176 rpm) (not shown); A syringe pump (KDS220, KD Scientific Inc.) 5, which controls the polymer solution at a constant volume and flow rate; Hamilton81620 gastight syringe, 10.0 ml, USA (2), Hamilton91022 metal hub needle, 22 Guage [length: 50.8 mm, inner diameter: 0.41 mm], USA scientific Inc., USA).
  • KDS220 KD Scientific Inc.
  • the electrospinning system of the present invention is designed in such a way that the syringe pump and the solution discharging device are connected by the long piston 1 and pushed out of the chamber, thereby reducing the risk of malfunction of the machine and the human body occurring under high voltage. Moreover, there is a syringe holder 3 to fix the solution dispensing apparatus (syringe), and height (up and down) and distance adjustment (left and right) are possible.
  • the electrospinning system of the present invention is a humidity control air conditioner (6), a solvent volatilization and fibrosis promoting heater (8), exhaust system (7) for removing volatile solvent in order to maintain the environment in the chamber to the best conditions for electrospinning Reproducible and stable electrospinning is possible.
  • Electrospinning in the present invention preferably using a drum collector plate that rotates using the electrospinning device shown in FIG.
  • Electrospinning in the present invention is preferably, the concentration of 0.1 ⁇ 50% by weight of the mixed solution, voltage 5 ⁇ 100 kV, discharge rate of the solution of 0.1 ⁇ 10 ml / h, spinning distance 3 ⁇ 50 cm and humidity of 1 ⁇ 30% Carry out under electrospinning conditions. Under these conditions, it is possible to produce a medical support film in the form of a nanofiber sheet of the present invention by mass spinning.
  • the nanofiber sheet-shaped nonwoven fabric obtained in the step was impregnated in a solvent at 25-100 ° C. for 5 to 24 hrs to dissolve and remove the hydrophilic polymer having water solubility, and then dried in a drying oven at 25-100 ° C. Obtaining a medical support film in the form of a nanofiber sheet having a porosity.
  • the solvent to be impregnated preferably, any one solvent or two or more mixed solvents selected from the group consisting of water and alcohols are used.
  • dimethylformamide (DMF)
  • water is most preferable as the impregnated solvent to remove the DMF remaining in the nanofiber sheet.
  • Dimethylformamide (DMF) is an organic solvent having excellent compatibility with water, and is widely used to coagulate a polyurethane resin mixed with dimethylformamide in preparing a film using a synthetic leather or a wet process.
  • the temperature of impregnated water is 25-100 degreeC, More preferably, it is 30-60 degreeC, Most preferably, it is 40-50 degreeC.
  • the temperature of the impregnated water is less than 25 °C when using F-68 has a problem that it takes a long time to remove the components of the F-68 melted
  • the medical support film in the form of nanofiber sheet is dried ( The medical support film may be deformed while being contracted.
  • the impregnation time is most preferably 5 to 24 hours.
  • the temperature to dry after impregnation becomes like this.
  • it is 25-100 degreeC, More preferably, it is 25-60 degreeC, Most preferably, 30-40 degreeC is good.
  • the drying temperature is 60 ° C.
  • shrinkage of the medical support film may occur while the micropores may be reduced, thereby decreasing functionality such as moisture permeability, flexibility, and the like, which should be provided as a medical film.
  • the medical support film of the nanofiber sheet form of the present invention prepared as described above has a diameter of 10 to 2,000 nm, the average diameter of the nanofibers may have a range of 10 to 1,000 nm, most preferably The average diameter can be in the range of 100-800 nm.
  • the medical support film of the present invention may preferably have a thickness of 50 ⁇ 200 ⁇ m range, most preferably 100 ⁇ 150 ⁇ m range.
  • Figure 2 is a scanning electron micrograph (SEM) of the medical support film in the form of a nanofiber sheet prepared by the embodiment.
  • the medical support film in the form of the nanofiber sheet of the present invention is a porous film having many pores, which is more excellent in elasticity, flexibility, and moisture permeability than the conventional medical support film in the form of nonwoven fabric, and remains in the film by a process impregnated with water.
  • the amount of organic solvent is minimized to have excellent biocompatibility.
  • compared to the conventional non-woven fabric has a property that extends freely in both directions (lateral, longitudinal direction) can be usefully used in areas with many movements and curved areas such as joints.
  • the support film of the present invention may be used as a support for a dressing material, a patch, an adhesive band, and the like, and may be widely used as a support in fields requiring elasticity, moisture permeability, flexibility, and biocompatibility.
  • Hydrophilic polyurethane resin in the present invention was synthesized using a solution polymerization method using methyl ethyl ketone (methy ethyl ketone) and dimethylformamide (dimetylformaide) as a co-solvent, specifically Hydrophilic polyurethane resin was prepared by the method.
  • a hydrophilic ethylene oxide / propylene oxide block copolymer was added, and the mixture was stirred at room temperature using a stirrer. The mixture was stirred at ⁇ 100 RPM to completely dissolve while avoiding bubbles as much as possible to form a mixed polymer solution for electrospinning. Specifically, a mixed solution was prepared under the conditions shown in Table 2 below.
  • Each of the mixed polymer solutions of Preparation Examples (a) to (d) prepared in the composition shown in Table 2 of Example 2 was electrospun to obtain a nonwoven fabric in the form of a nanofiber sheet.
  • the electrospinning system shown in FIG. 1 was used, and specific process factors were fixed at a voltage of 25 kV, a spinning distance of 10 cm, a fluid speed of 5 ml / hr, a drum rotation speed of 20 RPM, and radiated for 4 hours, and a chamber (chamber).
  • the conditions in) were advanced while maintaining the temperature in the range of 20 to 28 ° C and humidity of 30 to 50%.
  • the nanofiber sheet obtained in the above (1) was impregnated with water to dissolve and remove the water-soluble polymer F-68, and then dried in a drying oven to obtain a final product. After distilled water was maintained at 40 ° C., it was impregnated for 24 hours, and the prepared specimen was fixed with pins at the left, right, top, and bottom of the specimen so that no shrinkage occurred during drying, followed by drying at 30 ° C. for 12 hours. Proceeded. At this time, the temperature of the impregnated water was to maintain 40 ⁇ 50 °C.
  • the present invention provides a more porous structure by dissolving and removing the water-soluble polymer through the process of impregnating with water, thereby increasing the flexibility, further improving the functionality as a medical support film, and also remaining organic in the medical support film showing toxicity By removing the solvent, biocompatibility can be further improved.
  • the cytotoxicity test results of the support film finally obtained by Preparation Example (c) of the present invention are shown in FIG. 3.
  • the medical support film in the form of the nanofiber sheet prepared in the present invention was confirmed to have almost no cytotoxicity with cell viability of 80% or more, which was judged to be excellent in biocompatibility. This result is considered to be the result of removing toxic residual organic solvent by water impregnation process.
  • the thickness of the film was measured at five places using a dial type micrometer and the average value was shown.
  • the prepared specimens were measured according to JIS-K-6401 using a tensile tester (Universal Test Machine, USA, Instron) for the longitudinal and transverse directions, respectively. A total of 10 measurements were taken for each specimen to represent the mean value.
  • the prepared specimens were measured according to ASTM E96-94 (Desiccant Method) using a thermo-hygrostat, and the conditions were 37 ⁇ 1 ° C. and relative humidity was 50 ⁇ 5%, measured five times for each specimen. The average value is shown.
  • a cell culture test was conducted to confirm cellular reactivity of the prepared specimens. Experimental methods were used in ISO 10993 Biological evaluation of medical devices-Part 5: Test for in vitro cytotoxicity, Test on extracts. Cell lines were used for fibroblasts (L-929, Korea Cell Line Bank).
  • a medical polyurethane film manufactured by a wet process (G company, South Korea) was used as a comparative example for comparing the physical properties. Physical properties were measured in the same manner as described above, and the results are shown in Table 3 below.
  • Comparative Example 2 is a medical support film prepared by using a wet process in order to impart microporosity
  • the moisture permeability is very low and the cell survival rate is very low. It can be seen that the biocompatibility is poor. This shows the greatest disadvantage that can cause allergic reactions such as rash, redness when applied to the human body.
  • the medical support film in the form of the nanofiber sheet of the present invention has excellent moisture permeability, flexibility, and biocompatibility as compared with a polyurethane medical support manufactured using a conventional nonwoven fabric form or a dry and wet process. It can be used as a substitute, as well as a medical or non-medical use in a variety of fields that require such physical properties, such as medical elastic adhesive band.

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  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Biomedical Technology (AREA)
  • Vascular Medicine (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Hematology (AREA)
  • Materials Engineering (AREA)
  • Epidemiology (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Nonwoven Fabrics (AREA)
  • Materials For Medical Uses (AREA)

Abstract

La présente invention concerne un film de support médical du type feuille à nanofibre préparé par filage électrostatique, et son procédé de préparation. La présente invention prépare un film de support médical du type feuille à nanofibre qui est poreux et a un diamètre de fibre de taille nanométrique, par : introduction d'un polymère soluble dans l'eau, tel qu'un copolymère séquencé d'oxyde d'éthylène/oxyde de propylène, dans une résine de polyuréthane hydrophile, qui est un constituant principal, pour les mélanger ; filage électrostatique du mélange obtenu pour obtenir un tissu non tissé de nanofibre ; infiltration du tissu non tissé de nanofibre dans un solvant pour dissoudre et éliminer un constituant polymère hydrophile ; et séchage du produit obtenu. Le film de support médical obtenu selon la présente invention a une élasticité longitudinale et transversale remarquable, a une excellente élasticité et une excellente transpiration d'humidité en raison d'une structure poreuse à l'intérieur du film, et présente une biocompatibilité remarquable en raison de la quantité résiduelle réduite d'un solvant organique.
PCT/KR2012/006536 2012-08-16 2012-08-16 Film de support médical du type feuille à nanofibre et son procédé de préparation WO2014027707A1 (fr)

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CN106948164A (zh) * 2017-03-08 2017-07-14 杭州安诺过滤器材有限公司 由纳米连续多孔结构的聚乳酸纤维构成的薄膜及其制备方法
CN111188128A (zh) * 2020-01-06 2020-05-22 陕西科技大学 一种具有微支撑的透气薄膜的制备方法
CN114083877A (zh) * 2021-11-19 2022-02-25 联润翔（青岛）纺织科技有限公司 纳米纤维复合面料及其生产方法
CN114920552A (zh) * 2022-05-20 2022-08-19 湘潭大学 一种二维纳米片的制备工艺

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106948164A (zh) * 2017-03-08 2017-07-14 杭州安诺过滤器材有限公司 由纳米连续多孔结构的聚乳酸纤维构成的薄膜及其制备方法
CN111188128A (zh) * 2020-01-06 2020-05-22 陕西科技大学 一种具有微支撑的透气薄膜的制备方法
CN114083877A (zh) * 2021-11-19 2022-02-25 联润翔（青岛）纺织科技有限公司 纳米纤维复合面料及其生产方法
CN114083877B (zh) * 2021-11-19 2023-12-22 联润翔（青岛）纺织科技有限公司 纳米纤维复合面料及其生产方法
CN114920552A (zh) * 2022-05-20 2022-08-19 湘潭大学 一种二维纳米片的制备工艺

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