WO2022070722A1 - 内視鏡用可撓管、内視鏡型医療機器、及びこれらの製造方法 - Google Patents

内視鏡用可撓管、内視鏡型医療機器、及びこれらの製造方法 Download PDF

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Publication number
WO2022070722A1
WO2022070722A1 PCT/JP2021/031740 JP2021031740W WO2022070722A1 WO 2022070722 A1 WO2022070722 A1 WO 2022070722A1 JP 2021031740 W JP2021031740 W JP 2021031740W WO 2022070722 A1 WO2022070722 A1 WO 2022070722A1
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WIPO (PCT)
Prior art keywords
flexible tube
base material
layer
endoscope
polymer coating
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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/JP2021/031740
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English (en)
French (fr)
Japanese (ja)
Inventor
一馬 堀田
義博 中井
慎也 阿部
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Fujifilm Corp
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Fujifilm Corp
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Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Priority to EP21875025.5A priority Critical patent/EP4224236B1/en
Priority to JP2022553560A priority patent/JP7461493B2/ja
Priority to CN202180055386.4A priority patent/CN116018539A/zh
Publication of WO2022070722A1 publication Critical patent/WO2022070722A1/ja
Priority to US18/169,324 priority patent/US20230190076A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B1/00—Instruments for performing medical examinations of the interior of cavities or tubes of the body by visual or photographical inspection, e.g. endoscopes; Illuminating arrangements therefor
    • A61B1/00064—Constructional details of the endoscope body
    • A61B1/0011—Manufacturing of endoscope parts
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B1/00—Instruments for performing medical examinations of the interior of cavities or tubes of the body by visual or photographical inspection, e.g. endoscopes; Illuminating arrangements therefor
    • A61B1/00064—Constructional details of the endoscope body
    • A61B1/00071—Insertion part of the endoscope body
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
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    • A61B1/00064—Constructional details of the endoscope body
    • A61B1/00071—Insertion part of the endoscope body
    • A61B1/00078—Insertion part of the endoscope body with stiffening means
    • A—HUMAN NECESSITIES
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    • A61B1/005—Flexible endoscopes
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    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B23/00—Telescopes, e.g. binoculars; Periscopes; Instruments for viewing the inside of hollow bodies; Viewfinders; Optical aiming or sighting devices
    • G02B23/24—Instruments or systems for viewing the inside of hollow bodies, e.g. fibrescopes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61B1/00—Instruments for performing medical examinations of the interior of cavities or tubes of the body by visual or photographical inspection, e.g. endoscopes; Illuminating arrangements therefor
    • A61B1/005—Flexible endoscopes
    • A61B1/0051—Flexible endoscopes with controlled bending of insertion part
    • A61B1/0055—Constructional details of insertion parts, e.g. vertebral elements
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M25/00—Catheters; Hollow probes
    • A61M25/0009—Making of catheters or other medical or surgical tubes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M25/00—Catheters; Hollow probes
    • A61M25/0043—Catheters; Hollow probes characterised by structural features
    • A61M25/0045—Catheters; Hollow probes characterised by structural features multi-layered, e.g. coated
    • A—HUMAN NECESSITIES
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    • A61M25/00—Catheters; Hollow probes
    • A61M25/0043—Catheters; Hollow probes characterised by structural features
    • A61M25/005—Catheters; Hollow probes characterised by structural features with embedded materials for reinforcement, e.g. wires, coils, braids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2597/00—Tubular articles, e.g. hoses, pipes

Definitions

  • the present invention relates to a flexible tube for an endoscope, an endoscopic medical device, and a method for manufacturing these.
  • An endoscope is a medical device for observing a patient's body cavity, digestive tract, esophagus, etc. Since it is inserted into the body and used, it is desired that it does not damage the organs and does not cause pain or discomfort to the patient.
  • the flexible tube (flexible tube for endoscope) that constitutes the insertion part (structural part inserted into the body cavity) of the endoscope is spirally formed with a metal strip that bends softly.
  • a flexible tube base material having a spiral tube formed by winding and a tubular net body covering the spiral tube is adopted.
  • the perimeter of the flexible tube substrate is coated with a flexible resin or elastomer, which is optionally coated with a topcoat layer to irritate or scratch the inner surface of the esophagus, gastrointestinal tract, body cavity, etc. Has been devised so as not to give.
  • Patent Document 1 has a flexible tube base material made of a metal and a resin coating layer covering the outer periphery of the flexible tube base material, and these are possible.
  • endoscopes which has a primer layer containing an aminosilane coupling agent having a specific structure between the flexible tube base material and the resin coating layer, and contains a polyurethane elastomer at least on the side where the resin coating layer is in contact with the primer layer.
  • the present invention is a flexible tube for an endoscope having excellent elasticity, flexibility, and sufficient chemical resistance, and an endoscopic medical device provided with the flexible tube for an endoscope.
  • the challenge is to provide.
  • Another object of the present invention is to provide a method for manufacturing a flexible tube for an endoscope and a method for manufacturing an endoscope-type medical device.
  • the structure of the flexible tube base material can be further improved in elasticity. It has become clear that the structure of the network is important.
  • the present inventors use a mesh body made by braiding a metal wire as a tubular net body constituting a flexible tube base material, and control the porosity of the tubular net body to obtain flexibility. It has been found that the elasticity of the tube can be increased to a high level, and that the flexible tube has excellent flexibility and sufficient chemical resistance.
  • the present invention has been further studied and completed based on these findings.
  • a flexible tube for an endoscope having a flexible tubular flexible tube base material and a polymer coating layer covering the flexible tube base material.
  • the flexible tube base material has a spiral tube of a metal strip and a tubular network body in which a metal wire is braided to cover the spiral tube, and the pore ratio of the tubular network body is 2 to 10%.
  • a flexible tube for an endoscope having a primer layer containing a silane coupling agent between the flexible tube base material and the polymer coating layer.
  • ⁇ 3> The flexible tube for an endoscope according to ⁇ 1> or ⁇ 2>, wherein the polymer coating layer contains a thermoplastic elastomer.
  • ⁇ 4> The internal vision according to any one of ⁇ 1> to ⁇ 3>, wherein the polymer coating layer contains at least one thermoplastic elastomer of polyurethane elastomer, polyester elastomer and polyamide elastomer on the side in contact with the primer layer.
  • Flexible tube for mirror ⁇ 5> The flexible tube for an endoscope according to any one of ⁇ 1> to ⁇ 4>, wherein the metal constituting the flexible tube base material is stainless steel.
  • the flexible tube base material has a spiral tube of a metal strip and a tubular network body in which a metal wire is braided to cover the spiral tube, and the pore ratio of the tubular network body is 2 to 10.
  • a method for manufacturing an endoscopic medical device which comprises incorporating the flexible tube for an endoscope according to any one of ⁇ 1> to ⁇ 6> into an insertion portion of the endoscopic medical device.
  • the "porosity” is a value obtained by the calculation method described in Examples described later. Further, in the description of the present specification, "-" is used in the meaning of including the numerical values described before and after it as the lower limit value and the upper limit value.
  • the flexible tube for an endoscope of the present invention has excellent elasticity, excellent flexibility, and sufficient chemical resistance.
  • the flexible tube which is a structural part inserted into the body, has excellent elasticity, excellent flexibility, and sufficient chemical resistance. Therefore, the endoscopic medical device of the present invention can further reduce the burden on the subject during use, and can repeatedly perform high-precision examinations.
  • a flexible tube for an endoscope of the present invention a flexible tube for an endoscope having excellent elasticity, excellent flexibility, and sufficient chemical resistance can be obtained. ..
  • the flexible tube constituting this device shall have excellent elasticity, excellent flexibility, and sufficient chemical resistance. be able to. Therefore, according to the method for manufacturing an endoscopic medical device of the present invention, it is possible to obtain an endoscopic medical device that can further reduce the burden on the subject during use and can repeatedly perform high-precision examinations. can.
  • FIG. 3 is a cross-sectional view taken along the line BB of FIG. It is a partial cross-sectional view which shows the structure of one Embodiment of the tubular reticular formation which constitutes a flexible tube base material.
  • a preferred embodiment of an endoscope-type medical device incorporating a flexible tube for an endoscope of the present invention will be described by taking an electronic endoscope as an example.
  • the electronic endoscope incorporates the flexible tube for an endoscope of the present invention (hereinafter, the flexible tube for an endoscope may be simply referred to as a "flexible tube”), and this flexible tube is referred to in the body cavity.
  • the flexible tube for an endoscope may be simply referred to as a "flexible tube”
  • this flexible tube is referred to in the body cavity.
  • the electronic endoscope 2 is connected to an insertion unit 3 to be inserted into the body, a main body operation unit 5 connected to the base end portion of the insertion unit 3, and a processor device or a light source device. It is equipped with a universal code 6 to be inserted.
  • the insertion section 3 is a flexible tube 3a connected to the main body operation section 5, an angle section 3b connected to the flexible tube 3a, and an imaging device (not shown) for in-vivo imaging connected to the tip of the flexible tube 3b. It is composed of a built-in tip portion 3c.
  • the flexible tube 3a which occupies most of the length of the insertion portion 3, has flexibility over almost the entire length thereof, and in particular, the portion to be inserted into the body cavity or the like has a more flexible structure.
  • the flexible tube of the present invention has a flexible tubular flexible tube base material and a polymer coating layer that coats the flexible tube base material, and the flexible tube base material and the polymer coating layer. It has a primer layer containing a silane coupling agent between them.
  • the flexible tube base material has a spiral tube of a metal strip and a tubular network body in which a metal wire is braided to cover the spiral tube, and the pore ratio of the tubular network body is 2 to 10%. Is. The reason why the flexible tube of the present invention has excellent elasticity, flexibility, and sufficient chemical resistance is not clear, but it is presumed as follows.
  • the porosity of the tubular network of the braided structure constituting the flexible tube base material is 2 to 10%, and by having a primer layer containing a silane coupling agent on the flexible tube base material,
  • the polymer coating layer is formed, the polymer is densely coated in the pores of the tubular formation and on the surface of the tubular formation (outer circumference of the spiral tube).
  • the reaction area between the silane coupling agent and the polymer coating layer is increased, and the silane coupling agent and the polymer coating layer are effectively bonded or adhered to each other.
  • the spiral tube and the spiral tube are integrated when the flexible tube is bent, with the polymer coating layer and the spiral tube firmly adhered to each other via the tubular network filled with the polymer at high density.
  • the flexible tube of the present invention is excellent in elasticity because of the bending of the flexible tube. It has been clarified as an experimental fact that this improvement in elasticity becomes apparent when the silane coupling agent has an amino group, as shown in Examples described later. Although the reason for this is not clear, the molecular structure of the amino group responsible for the bond or adhesion between the silane coupling agent and the polymer coating layer is the bond or adhesion point with the polymer coating layer because the silane coupling agent has an amino group.
  • the porosity of the tubular net body of the braided structure is 2 to 10%, it is possible to sufficiently secure the contact area between the flexible tube base material and the polymer-coated layer and effectively improve the adhesion. It is considered that it can be made, has excellent chemical resistance, and the above-mentioned porosity also imparts sufficient flexibility to the flexible tube base material.
  • the flexible tube has a flexible tube base material having a metal as a constituent material as the innermost layer.
  • the flexible tube base material 14 is a tubular net body formed by braiding a metal wire around a spiral tube 11 formed by spirally winding a metal strip 11a on the innermost side. It is preferable that the 12 is covered and the bases 13 are fitted to both ends thereof.
  • the braided structure of the tubular net body 12 is not particularly limited, and any structure may be used as long as the metal wire is woven by regularly swapping the top and bottom. Examples of the braided structure include knitting (warp / weft), plain weave, twill weave, satin weave, and the like, and twill weave is preferable.
  • FIG. 5 is a partial cross-sectional view showing the configuration of one embodiment of the tubular net body 12 having a braided structure formed by twill weaving, and has a bundle having three holdings (a bundle composed of three metal wires 41). It is woven to form a hole 42 between the bundles.
  • the porosity of the tubular net 12 formed by braiding a metal wire is 2 to 10%, preferably 3 to 8%, more preferably 3 to 7%, from the viewpoint of elasticity of the flexible tube. ⁇ 6% is more preferable. It is preferable that the surface of the metal constituting the flexible tube base material 14 is subjected to an immobilization treatment in order to prevent corrosion.
  • the flexible tube base material 14 has a passivation film on the outer periphery (surface) thereof.
  • This mobilization process can be performed by a conventional method.
  • a metal surface can be surfaced by immersing it in a solution containing a strong oxidant such as nitric acid, heating it in air (oxygen) or water (steam), or anodizing it in a solution containing an oxidant.
  • a passivation film can be formed on the surface.
  • the metal constituting the flexible tube base material 14 is preferably stainless steel.
  • the spiral tube 11 formed by spirally winding the metal strip 11a on the innermost side and the tubular net body 12 formed by braiding a metal wire are preferably made of stainless steel.
  • the surface of stainless steel is usually in a state where chromium and oxygen (O 2 ) are combined to form a passivation film.
  • O 2 chromium and oxygen
  • a primer layer (not shown) is provided on the outer periphery of the flexible tube base material.
  • this primer layer contains a silane coupling agent.
  • silane coupling agent used in the present invention, a normal silane coupling agent applicable to the primer layer of a flexible tube for an endoscope can be widely adopted.
  • an aminosilane coupling agent (preferably a silane coupling agent having at least one of an unsubstituted amino group and a monosubstituted amino group) is preferable in order to further improve the elasticity.
  • the silane coupling agent include, but the present invention is not limited to these, the silane coupling agent used in Examples described later.
  • the content of the silane coupling agent in the primer layer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more.
  • the primer layer may be a layer made of a silane coupling agent.
  • the content of the aminosilane coupling agent in the silane coupling agent is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more. ..
  • the primer layer may be a layer made of an aminosilane coupling agent.
  • the coupling agent is not particularly limited as long as the effect of the present invention is not impaired, and for example, an aluminum coupling agent, a zirconium coupling agent and a titanium coupling agent. Agents are mentioned.
  • the thickness of the primer layer is much thinner than that of a normal adhesive layer (in other words, the concept of thickness cannot be recalled). That is, the primer layer containing the silane coupling agent is different from the adhesive layer which requires a certain layer thickness and softness for adhesion between the flexible tube base material and the polymer coating layer.
  • the flexible tube of the present invention has a polymer coating layer (a layer containing at least one of a resin and an elastomer) on the outer periphery of a flexible tube base material provided with a primer layer.
  • a polymer coating layer a layer containing at least one of a resin and an elastomer
  • the outer surface of the polymer coating layer 15 is coated with a top coat layer 16 containing fluorine or the like, which contributes to chemical resistance and the like.
  • a top coat layer 16 containing fluorine or the like, which contributes to chemical resistance and the like.
  • the polymer coating layer 15 and the top coat layer 16 are drawn thicker than the diameter of the flexible tube base material 14 in order to clearly show the layer structure.
  • the polymer coating layer may be a single layer or a multi-layer, and is preferably a multi-layer.
  • This polymer coating layer covers the outer peripheral surface of the flexible tube base material having the primer layer described above.
  • the polymer coating layer 15 is not a single layer, but covers the inner layer 17 that covers the entire peripheral surface of the flexible tube base material 14 around the axis, and the inner layer 17 that covers the entire peripheral surface of the inner layer 17 around the axis. It is a two-layer structure in which the outer layer 18 is laminated.
  • a soft polymer is used as the material of the inner layer 17, and a hard polymer is used as the material of the outer layer 18, but the present invention is not limited to these forms.
  • the polymer coating layer is a single layer, and different polymer coating layer forming materials are applied multiple times.
  • the polymer-coated layer is a multi-layer.
  • the polymer coating layer preferably contains a thermoplastic elastomer
  • specific examples of the thermoplastic elastomer include a fluoroelastomer, a polyolefin elastomer, an acrylic elastomer, a styrene elastomer, a polyphenylene oxide elastomer, a polyurethane elastomer, a polyester elastomer, and a polyamide elastomer.
  • the thermoplastic elastomer include a fluoroelastomer, a polyolefin elastomer, an acrylic elastomer, a styrene elastomer, a polyphenylene oxide elastomer, a polyurethane elastomer, a polyester elastomer, and a polyamide elastomer.
  • the polymer coating layer has a multi-layer structure of two or more layers
  • at least the innermost layer is at least one of polyurethane elastomer, polyester elastomer and polyamide elastomer. It preferably contains a thermoplastic elastomer, more preferably a polyurethane elastomer.
  • the polymer coating layer of the single layer contains at least one thermoplastic elastomer of a polyurethane elastomer, a polyester elastomer and a polyamide elastomer, and polyurethane.
  • the polymer coating layer preferably contains at least one thermoplastic elastomer of polyurethane elastomer, polyester elastomer and polyamide elastomer on the side in contact with the primer layer, and more preferably contains polyurethane elastomer.
  • polyurethane elastomer As the polyurethane elastomer used for the polymer coating layer, a normal polyurethane elastomer applicable to the formation of a flexible tube can be adopted.
  • This polyurethane elastomer is usually obtained by reacting a polyisocyanate, a polyol and a chain extender.
  • the polyurethane elastomer is preferably a random copolymer or a block copolymer composed of a soft segment formed by the reaction of the polymer polyol and the polyisocyanate and a hard segment formed by the reaction of the chain extender and the polyisocyanate, and is a block copolymer. Is more preferable.
  • polyether polyurethane elastomer a polyether polyurethane elastomer, a polyester polyurethane elastomer and a polycarbonate polyurethane elastomer are preferable, and a polyether polyurethane elastomer is more preferable.
  • the above-mentioned polyether polyurethane elastomer is preferably an elastomer composed of a soft segment formed by a reaction between a polyether polyol and a polyisocyanate and the above-mentioned hard segment, that is, a polyurethane elastomer containing a polyether in the soft segment. It is preferred that this soft segment is free of ester and carbonate bonds.
  • the polyester polyurethane elastomer is preferably an elastomer composed of a soft segment formed by the reaction of a polyester polyol and a polyisocyanate and the above-mentioned hard segment, that is, a polyurethane elastomer containing polyester in the soft segment. It is preferred that this soft segment does not contain ether or carbonate bonds.
  • the polycarbonate polyurethane elastomer is preferably an elastomer composed of a soft segment formed by the reaction of a polycarbonate polyol and a polyisocyanate and the above-mentioned hard segment, that is, a polyurethane elastomer containing polycarbonate in the soft segment. It is preferred that this soft segment does not contain ether or ester bonds.
  • polyisocyanate examples include diphenylmethane diisocyanate, hexamethylene diisocyanate, trizine diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate.
  • polyether polyol examples include polytetramethylene ether glycol, polydimethylene ether glycol, polytrimethylene ether glycol, polypropylene ether glycol, polyhexamethylene ether glycol and polyneopentyl ether glycol.
  • the polyester polyol is obtained by a polycondensation reaction between a dicarboxylic acid and a polyol (preferably a diol).
  • a diol preferably a diol
  • the diol used for producing the polyester polyol include ethylene polyol (for example, ethanediol), propylene polyol (1,3-propanediol), 1,3-butanediol, 1,4-butanediol, and neopentyl polyol.
  • 1,5-pentanediol), 1,6-hexanediol, polycaprolactone diol and the like can be mentioned, and these can be used alone or in combination.
  • examples of the dicarboxylic acid include adipic acid, sebacic acid, dimer acid and the like, and examples thereof include those used alone or in combination.
  • examples of the polycaprolactone diol include Praxel 205, Praxel 205H (trade name, manufactured by Daicel Chemical Industries, Ltd.), TONE 0200, TONE 0201 (trade name, manufactured by Union Carbide), and Praxel 208 (trade name, manufactured by Daicel Chemical Industries, Ltd.). (Manufactured by Kogyo Co., Ltd.) and the like.
  • polycarbonate polyol examples include polyethylene carbonate diol, polytetramethylene carbonate diol, and polyhexamethylene carbonate diol.
  • Examples of the chain extender include aliphatic linear diols having 2 to 6 carbon atoms such as ethanediol, 1,4-butanediol, and 1,6-hexanediol, and 1,4-bis (hydroxyethoxy). Examples include benzene. Amines such as hexamethylenediamine, isophoronediamine, tolylenediamine, monoethanolamine and the like can also be used in combination as necessary. As the polyurethane elastomer according to the above embodiment, for example, the disclosure of JP-A-2005-015643 can be referred to. The polyurethane elastomer may be used alone or in combination of two or more.
  • the polyester elastomer a normal polyester elastomer applicable to the formation of a flexible tube can be used. That is, the polyester elastomer used in the present invention is a copolymer composed of a hard segment made of crystalline polyester and a soft segment made of polyether or polyester. Examples of the hard segment include polybutylene terephthalate, polyethylene terephthalate, and the like. Examples of the soft segment include polytetramethylene glycol, polyalkylene glycol such as polypropylene glycol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, polyester such as polycaprolactone, and the like.
  • the "polyester elastomer” preferably does not contain a urethane bond in the molecule and does not contain an amide bond.
  • One type of polyester elastomer may be used alone, or two or more types may be used in combination.
  • polyamide elastomer As the above-mentioned polyamide elastomer, a conventional polyamide elastomer applicable to the formation of a flexible tube can also be used. In the present invention, it is preferable that the polyamide elastomer does not contain a urethane bond and does not contain an ester bond.
  • One type of polyamide elastomer may be used alone, or two or more types may be used in combination.
  • thermoplastic elastomer used in the present invention include the thermoplastic elastomers (fluoroelastomer-containing elastomer, polyolefin elastomer, polyurethane elastomer, polyester elastomer, and polyamide elastomer) used in Examples described later. Not limited to these.
  • the content of the thermoplastic elastomer in the polymer coating layer is 50% by mass or more, and when the polymer coating layer is a multi-layer, the content of the thermoplastic elastomer in the innermost layer is 50% by mass or more. It is preferable, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more.
  • the polymer coating layer may be a layer made of a thermoplastic elastomer, and when the polymer coating layer is a multi-layer, the innermost layer is a layer made of a thermoplastic elastomer. You may.
  • the total content of the polyurethane elastomer, polyester elastomer and polyamide elastomer contained in the thermoplastic elastomer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably. Is 90% by mass or more, and may be 100% by mass.
  • this polymer is particularly effective as long as the effect of the present invention is not impaired.
  • vinyl polymers such as acrylic resins and styrene resins and condensation polymers such as polyesters and polyamides can be mentioned.
  • the layer other than the innermost layer preferably contains at least one thermoplastic elastomer of polyurethane elastomer, polyester elastomer and polyamide elastomer. These thermoplastic elastomers can be appropriately combined to form a layer having desired physical properties.
  • the layers other than the innermost layer more preferably contain a polyester elastomer and a polyamide elastomer from the viewpoint of further enhancing elasticity.
  • each of the above elastomers that can be used for the polymer coating layer preferably has a molecular weight of 10,000 to 1,000,000, more preferably 20,000 to 500,000, and particularly preferably 30,000 to 300,000.
  • the molecular weight of the elastomer means the weight average molecular weight unless otherwise specified.
  • the weight average molecular weight can be measured by GPC as a polystyrene-equivalent molecular weight.
  • a GPC device HLC-8220 (trade name, manufactured by Tosoh Corporation) was used, and the eluent used was chloroform for a polyester elastomer, NMP (N-methyl-2-pyrrolidone) for a polyurethane elastomer, and a polyamide elastomer.
  • m-cresol / chloroform manufactured by Shonan Wako Junyaku Co., Ltd.
  • the column is G3000HXL + G2000HXL (both trade names, manufactured by Tosoh Co., Ltd.)
  • the flow rate is 1 mL / min at 23 ° C, and it is detected by RI. ..
  • the polymer coating layer 15 is preferably formed to have a substantially uniform thickness in the longitudinal direction (axial direction) of the flexible tube base material 14.
  • the thickness of the polymer coating layer 15 is, for example, 0.2 mm to 1.0 mm, and the outer diameter D of the flexible tube 3a is, for example, 11 to 14 mm.
  • the thicknesses of the inner layer 17 and the outer layer 18 are formed so that the ratio of the thicknesses of the inner layers 17 and 18 to the total thickness of the polymer coating layer 15 changes in the axial direction of the flexible tube base material 14. ing.
  • the thickness of the inner layer 17 is larger than the thickness of the outer layer 18 with respect to the total thickness of the polymer coating layer 15. Is also big. Then, the thickness of the inner layer 17 gradually decreases from one end 14a toward the other end 14b side (base end side) attached to the main body operation unit 5, and on the other end 14b side, the thickness of the outer layer 18 is larger than that of the inner layer 17. It is larger than the thickness of.
  • the ratio of the thickness of the inner layer 17 to the one end 14a is the maximum, and the ratio of the thickness of the outer layer 18 to the other end 14b is the maximum.
  • Thickness of inner layer 17 The thickness of the outer layer 18 can be, for example, 9: 1 at one end 14a and, for example 1: 9 at the other end 14b. From both ends 14a to 14b, the thicknesses of both layers are changed so that the ratio of the thicknesses of the inner layer 17 and the outer layer 18 is reversed.
  • the flexibility of the flexible tube 3a can be changed in the axial direction so that there is a difference in hardness between one end 14a side and the other end 14b side, the one end 14a side is soft and the other end 14b side is hard.
  • the thickness ratio at one end is preferably 5:95 to 40:60 (inner layer: outer layer), and the thickness ratio at the other end is 95: 5 to 60:40 (inner layer: outer layer). It is preferable to do so.
  • the ratio of the thickness of the inner layer 17 and the outer layer 18 is set to the range of 5:95 to 95: 5, it is possible to precisely control the extrusion amount of the thinner polymer.
  • the difference in 100% modulus value which is an index showing the hardness after molding, is preferably 1 MPa or more, and more preferably 3 MPa or more.
  • top coat layer 16 In the flexible tube of the present invention, a top coat layer 16 is arranged on the outer periphery of the polymer coating layer 15 as needed.
  • the material of the top coat layer is not particularly limited, but urethane paint, acrylic paint, fluorine paint, silicone paint, epoxy paint, polyester paint and the like are applied.
  • the main purpose of using the topcoat layer is to protect and polish the surface of the flexible tube, to impart slipperiness, and to impart chemical resistance. Therefore, the topcoat layer preferably has a high elastic modulus, a smooth surface, and excellent chemical resistance.
  • a method for manufacturing a flexible tube for an endoscope includes forming a primer layer containing a silane coupling agent and a polymer coating layer in this order on the outer periphery of a flexible tube base material made of a metal. It is sufficient to include forming a primer layer containing a silane coupling agent and a polymer coating layer in this order on at least a part of the outer periphery of the flexible tube base material, and silane coupling also on the inner circumference of the flexible tube base material.
  • a primer layer containing an agent and a polymer coating layer may be formed.
  • the flexible tube base material can be produced by a usual method except that a metal wire is braided to form a tubular network having a porosity of 2 to 10%.
  • a tubular network having a desired porosity can be obtained by controlling the outer diameter, number of holdings, pitch, etc. of the metal wire.
  • a flexible tube base material can be obtained by producing and covering the spiral tube with this tubular network.
  • a primer layer is first formed on the flexible tube base material.
  • a silane coupling agent is dissolved in a solvent to prepare a coating liquid, and this coating liquid is applied to or sprayed on the outer periphery of the flexible tube base material, or the flexible tube base is contained in the coating liquid. It can be formed by forming a coating film on at least the outer periphery of the flexible tube base material by immersing the material, and then drying the coating film by a conventional method (for example, drying at a high temperature of about 100 ° C.). ..
  • the solvent used for the coating liquid an alcohol solvent such as methanol and ethanol, a ketone solvent such as acetone and methyl ethyl ketone, an ester solvent such as ethyl acetate, a hydrocarbon solvent such as toluene, or a mixed solution thereof can be used, and these can be used. It is preferable to mix water with the solvent in order to promote the hydrolysis of the silane coupling agent.
  • the coating liquid may be prepared to be acidic (for example, pH 1 to 4 at 25 ° C.) or alkaline (for example, pH 9 to 11 at 25 ° C.).
  • the content of the silane coupling agent in the coating liquid is not particularly limited, and may be, for example, 0.01 to 2% by mass, 0.02% by mass or more and less than 0.5% by mass, and 0. It may be 03% by mass or more and less than 0.4% by mass.
  • the coating liquid may contain a surfactant, a catalyst, etc. in addition to the silane coupling agent, the solvent, and the pH adjuster.
  • the coating liquid is more preferably composed of a silane coupling agent and a solvent. In the present invention, there may be a portion not covered with the primer layer in a part of the outer periphery of the flexible tube base material as long as the effect of the present invention is not impaired (that is, a part of the primer layer is defective. May have occurred.).
  • the flexible tube base material is degreased and washed with an alkaline solution, a surfactant aqueous solution, an organic solvent, or the like. Further, after the above washing, it is preferable to further wash with water or warm water.
  • the formation of the polymer coating layer will be described by taking the case where the polymer coating layer has a two-layer structure as an example.
  • the flexible tube having a two-layer structure in which the polymer coating layer is composed of an inner layer and an outer layer is, for example, a first polymer material constituting the inner layer (for example, a polymer material containing a thermoplastic elastomer) and a second polymer constituting the outer layer.
  • the material can be obtained by melt-kneading and extruding around the flexible tube base material on which the above-mentioned primer layer is formed, and coating the flexible tube base material.
  • An embodiment in which the polymer coating layer is one layer or three or more layers can also be obtained by appropriately changing the layer structure with reference to the following method.
  • the continuous molding machine 20 includes a well-known extrusion portion 21 and 22 including a hopper, screws 21a and 22a, a head portion 23 for coating and molding a polymer coating layer 15 on the outer peripheral surface of the flexible tube base material 14, and cooling. It is preferable to use a unit 24, a transport unit 25 (supply drum 28 and a take-up drum 29) for transporting the connecting flexible tube base material 31 to the head portion 23, and a control unit 26 for controlling these. ..
  • the head portion 23 is preferably composed of a nipple 32, a die 33, and a support 34 that fixedly supports them.
  • a configuration example of such an apparatus for example, the apparatus described in FIGS. 3 to 5 of JP-A-2011-72391 can be used.
  • the molding temperature is preferably set in the range of 150 ° C to 300 ° C.
  • the temperature of each of the first polymer material 39 and the second polymer material 40 can be increased by heating and adjusting the temperature of the heating portion in the apparatus. In addition, the higher the rotation speed of the screws 21a and 22a, the higher the temperature. , The temperature of each of the first polymer material 39 and the second polymer material 40 can be further increased, and the fluidity of each can be increased.
  • the molding thicknesses of the inner layer 17 and the outer layer 18 are each formed. Can be adjusted.
  • the process of molding the polymer coating layer 15 on the connected flexible tube base material 31 with the continuous molding machine 20 will be described.
  • the continuous molding machine 20 performs the molding step, the first one in a molten state from the extrusion portions 21 and 22
  • the polymer material 39 and the second polymer material 40 are extruded into the head portion 23.
  • the transport section 25 operates to transport the connected flexible tube base material 31 to the head section 23.
  • the extruded portions 21 and 22 are in a state of constantly extruding the first polymer material 39 and the second polymer material 40 and supplying them to the head portion 23, and are extruded from the extruded portions 21 and 22 to the gates 35 and 36.
  • the 1-polymer material 39 and the 2nd polymer material 40 merge through the edges and are supplied in an overlapping state through the polymer passage 38 to the molding passage 37. As a result, a two-layer molded polymer coating layer 15 in which the inner layer 17 using the first polymer material 39 and the outer layer 18 using the second polymer material 40 are overlapped is formed.
  • the connected flexible tube base material 31 is formed by connecting a plurality of flexible tube base materials 14 (a primer layer is formed on the outer periphery of the flexible tube base material 14), and is formed in the forming passage 37.
  • the polymer coating layer 15 is continuously formed on the plurality of flexible tube base materials 14.
  • the control unit 26 is used for switching the discharge amounts of the extrusion portions 21 and 22.
  • the control unit 26 is based on the ratio of the thickness of one flexible tube base material 14 on the other end 14b side (base end side) to the one end 14a side (tip side) of the next flexible tube base material 14. ), It is preferable to switch the discharge amount of the extrusion portions 21 and 22 so as to be the ratio of the thickness.
  • the thickness of the outer layer gradually increases from one end side to the other end side. It is preferable that the extrusion portions 21 and 22 are controlled.
  • the connected flexible tube base material 31 on which the polymer coating layer 15 is molded to the end is removed from the continuous molding machine 20, and then the joint member 30 is removed from the flexible tube base material 14, and each flexible tube base material is removed. It is separated into 14. Next, the top coat layer 16 is coated on the polymer coating layer 15 on the separated flexible tube base material 14, and the flexible tube 3a is completed. The completed flexible tube 3a is transported to the assembly process of the electronic endoscope.
  • a functional layer may be interposed between the layers constituting the multi-layer.
  • the flexible tube of the present invention can be widely applied to endoscopic medical devices.
  • it can be applied to an endoscope equipped with a clip or a wire at the tip of the endoscope, or an instrument equipped with a basket or a brush.
  • the endoscope-type medical device is a medical device having the above-mentioned endoscope as a basic structure, as well as a remote-controlled medical device, etc., which has a flexible insertion part and is used by being introduced into the body. It means that it includes a wide range of medical or medical equipment.
  • the endoscope-type medical device of the present invention has the flexible tube for an endoscope of the present invention incorporated in the insertion portion thereof. That is, the method for manufacturing an endoscopic medical device of the present invention includes incorporating the flexible tube for an endoscope of the present invention into an insertion portion of the endoscopic medical device.
  • a solution having a water / ethanol mass ratio of 5/75 was prepared.
  • the coupling agent shown in Table 1 below was dissolved in this solution to a concentration of 8.9 g / kg to prepare a coating solution for forming a primer layer.
  • Preparation of coating liquid for forming adhesive layer 100 g of polyester polyurethane (trade name: N-2304, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 10 g of polyisocyanate (trade name: Coronate, manufactured by Nippon Polyurethane Industry Co., Ltd.) were dissolved in 1 kg of methyl ethyl ketone to prepare a coating liquid for forming an adhesive layer.
  • polyester polyurethane trade name: N-2304, manufactured by Nippon Polyurethane Industry Co., Ltd.
  • polyisocyanate trade name: Coronate, manufactured by Nippon Polyurethane Industry Co., Ltd.
  • a flexible tube having the structure shown in FIG. 2 was produced.
  • the polymer coating layer has a single-layer structure or a two-layer structure as shown in Table 1 below.
  • a spiral tube 11 is formed by using a metal strip 11a made of stainless steel, and the spiral tube 11 is covered with a tubular net body 12 made of braided stainless steel fibers (metal wire).
  • a tube base material was prepared.
  • the wire diameter (outer diameter of the metal wire 41) is set to 0.1 mm and the core material diameter is set to 10.5 mm.
  • a tubular net body 12 having a pore ratio shown in Table 1 below was obtained.
  • a flexible tube base material was produced by covering the outer periphery of the spiral tube 11 with the tubular net body 12 thus obtained.
  • the flexible tube base material has a length of 80 cm and a diameter of 12 mm.
  • a passivation layer is formed on the surface of this stainless steel flexible tube by an annealing treatment (heat treatment) at the time of forming the spiral tube 11 and the tubular network 12.
  • the adhesive layer forming solution prepared above was uniformly applied to the outer periphery of the stainless steel flexible tube base material, and dried at room temperature for 2 hours. Then, it was further heat-treated at 150 ° C. for 2 hours to prepare a flexible tube base material having an adhesive layer on the outer periphery (resin-coated surface). The thickness of the adhesive layer was about 80 ⁇ m.
  • the outer periphery of the flexible tube base material provided with the primer layer or the adhesive layer is extruded and coated with an elastomer as shown in Table 1 below (molding temperature: 200 ° C.), and can be used for endoscopes having a polymer coating layer.
  • a flexible tube was made.
  • the thickness of the polymer coating layer was 0.4 mm (in the case of a two-layer structure, the combined thickness of the two layers was 0.4 mm).
  • the polymer coating layer was two layers (Examples 1 to 39, 44 to 46 and Comparative Examples 1 to 31)
  • the 90 ° peel strength was measured by peeling between the flexible tube base material and the polymer coating layer at a constant rate of 2 mm / min in the axial direction along a notch having a width of 1 cm (this measured value X).
  • the peel strength was measured with a force gauge (unit: N / cm).
  • the 90 ° peel strength was measured in the same manner using a flexible tube for an endoscope that was not immersed in an aqueous solution of peracetic acid (measured value Y). For all flexible tubes, 90 ° peel strength was measured under the same conditions.
  • the ratio of the measured value X to the measured value Y (%, 100 ⁇ X / Y) was obtained and evaluated by applying it to the following criteria. "C" or higher is a pass.
  • Ratio is 80% or more
  • B Ratio is 60% or more and less than 80%
  • C Ratio is 40% or more and less than 60%
  • D Ratio is less than 40% (Polymer coating layer is peeled off during immersion in peracetic acid aqueous solution (Including those that have been lost)
  • the polymers used for the polymer coating layer are as follows.
  • PU1 Polyester polyurethane elastomer (trade name: Pandex T-8185, manufactured by DIC Corporation)
  • PU2 Polyester polyurethane elastomer (trade name: Miractran E380, manufactured by Nippon Polyurethane Industry Co., Ltd.)
  • PU3 Polyester Polyurethane Elastomer (Product name: Miractran E480, manufactured by Nippon Polyurethane Industry Co., Ltd.)
  • PU4 Polycarbonate Polyurethane Elastomer (Product name: Pandex T-9280, manufactured by DIC Corporation)
  • PE1 Polyester elastomer (trade name: Perprene P-40B, manufactured by Toyobo Co., Ltd.)
  • PA1 PA1: PA1: Polyamide elastomer (trade name: Pevacs 4533, manufactured by Arkema)
  • Fluorine-containing elastomer Daiel T-530 (trade name), Polyolefin elastomer manufactured by Daikin Industries, Ltd .: Zelas MC707 (trade name), manufactured by Mitsubishi Chemical Corporation
  • the coupling agents used for the primer layer are as follows.
  • A-1 Aluminum sec-butoxide (trade name: ASBD, manufactured by Kawaken Fine Chemicals Co., Ltd.)
  • A-2) Aluminum Tris Acetylacetone (Product name: Organix AL-3100, manufactured by Matsumoto Fine Chemical Co., Ltd.)
  • A-3) Aluminum Bisethylacetate Acetate Monoacetylacetone (Product name: Organix AL-3200, manufactured by Matsumoto Fine Chemical Co., Ltd.)
  • A-5) Aluminum Octadecylacetacetate diisopropilate (trade name: Plenact AL-M, manufactured by Ajinomoto Fine Techno Co., Ltd.)
  • Z-1 Zirconium Tetra n-Propoxide (Product Name: Organix ZA-45, manufactured by Matsumoto Fine Chemical Co., Ltd.)
  • Z-2 Zirconium tetra n-butoxide (trade name: Olgatics ZA-65, manufactured by Matsumoto Fine Chemical Co., Ltd.)
  • Z-3 Zirconium tetraacetylacetonate (trade name: Olgatics ZC-150, manufactured by Matsumoto Fine Chemical Co., Ltd.)
  • Z-4 Zirconium Lactate Ammonium Salt (Product Name: Olga Chix ZC-300, manufactured by Matsumoto Fine Chemical Co., Ltd.)
  • Z-5) Zirconium stearate tri-n-butoxide (trade name: Organix ZC-320, manufactured by Matsumoto Fine Chemicals)
  • T-1 Tetra n-butyl titanate (trade name: Organix TA-21, manufactured by Matsumoto Fine Chemical Co., Ltd.)
  • T-2 n-Butyl titanate dimer (trade name: Organix TA-23, manufactured by Matsumoto Fine Chemical Co., Ltd.)
  • T-3 Isopropyltriisostearoyl titanate (trade name: Plenact TTS, manufactured by Ajinomoto Fine-Techno)
  • T-4 Dioctylvis (ditridecyl) phosphate titanate (trade name: Plenact 46B, manufactured by Ajinomoto Fine-Techno)
  • T-5 Diisopropylbis (Dioctylpyrophosphate) titanate (trade name: Plenact 38S, manufactured by Ajinomoto Fine-Techno)
  • the flexible tubes of Comparative Examples 1, 4, 7, 10 and 13 having a porosity below the lower limit specified in the present invention were inferior in flexibility.
  • the flexible tubes of Comparative Examples 2, 3, 5, 6, 8, 9, 11, 12, 14 and 15 in which the porosity exceeds the upper limit specified in the present invention were inferior in elasticity.
  • the flexible tubes of Comparative Examples 16 to 30 have a primer layer made of a coupling agent other than the silane coupling agent.
  • the flexible pipes of Comparative Examples 16 to 30 had a porosity satisfying the provisions of the present invention, but were inferior in elasticity.
  • the flexible tube of Comparative Example 31 having an adhesive layer instead of the primer layer was inferior in elasticity and chemical resistance.
  • the flexible tubes (Examples 1 to 50) of the present invention are excellent in elasticity, excellent in flexibility, and have sufficient chemical resistance. From the comparison between the results of Examples 1 to 11 and the results of Examples 12 to 39, when the aminosilane coupling agent is used as the silane coupling agent, the porosity is controlled to raise the elasticity to a higher level. It turns out that it can be enhanced.

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