JP2015015978A - Tube structure and catheter using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tube structure capable of preventing change of a pitch of a metal braided body upon bending, and fray of the metal braided body upon tube cutting, and excellent in handleability and assemblability and to provide a catheter using the same.SOLUTION: A tube structure 10 includes: a tubular inner layer 11 comprising a thermosetting polyimide resin; an adhesion layer 12 formed on the outer periphery of the inner layer 11; a metal braided body 13 formed tubularly by braiding a metal wire 13a on the outer periphery of the adhesion layer 12, and having at least a part thereof on the adhesion layer 12 side which is buried into the adhesion layer 12; and an outer layer 14 for covering the metal braided body 13. A catheter has the tube structure 10.

Description

  The present invention relates to a tube structure and a catheter using the tube structure. More specifically, the present invention prevents changes in the braiding pitch (also simply referred to as pitch) of a metal braid during bending and fraying of the metal braid during tube cutting. The present invention relates to a tube structure excellent in handleability and assembly and a catheter using the same.

  In recent medical treatment, it is called a catheter in order to inject a drug solution or a contrast medium from outside into a predetermined part of a patient's body, to discharge a body fluid from the body, and to treat an affected area. A medical device with a flexible tube structure is used. Particularly in the treatment of cardiovascular diseases, conventionally, the affected area is opened by a surgeon's operation, and the affected area is excised and cleaned using a medical instrument such as a scalpel. However, in recent years, there have been an increasing number of cases in which an affected part is treated by inserting a catheter into the body and inserting a treatment instrument.

Such medical catheters are inserted into the patient's body using thin blood vessels or urethra, etc., so safety and accuracy are ensured so as not to damage blood vessel walls or living organs during the insertion process. It must have high operability that can be reached without kinking (bending and closing the internal flow path) at a predetermined site.
In addition to these, it is important to have lubricity for smoothly receiving a drug solution, a contrast medium injection, or other catheter insertion.

  In order to meet the above-described requirements regarding operability, conventionally, a catheter tube having a so-called reinforcing layer in which a metal wire is knitted into a resin hollow molded body has been used. For example, in Patent Document 1, “a resin layer made of a polymer material and a plurality of braided metal wires wound spirally, and a tubular braided body embedded in the resin layer; "The catheter tube provided with" is sufficiently rigid even if it is thin and can prevent kink to a high degree "(claim 1 and paragraph [0012]). Specifically, the catheter tube described in Patent Document 1 is formed of a polytetrafluoroethylene (PTFE) tube, a braided body, and a polyamide-based elastomer (for example, see Examples).

  Patent Document 2 discloses that “a base layer made of a polymer material, a flexible material made of a polymer material having a lower compression elastic modulus than the polymer material constituting the base layer, laminated on the base layer, and a predetermined thickness. A network embedded in a boundary position between the base layer and the flexible layer, and the base layer and the flexible layer have a substantially uniform thickness, and the network is While changing the speed of the catheter tube embedded with an inclination with respect to the boundary surface between the base layer and the flexible layer, and the inner tube provided with the net-like body on the outer peripheral surface, the die being heated A method of manufacturing a catheter tube is described that includes passing and embedding a portion of the mesh in the inner tube.

JP 2005-329552 A JP-A-2005-270507

  However, although the tube described in Patent Document 1 embeds the braided body in a resin layer made of a polymer material, the braided body frays when the tube is cut, and the handling property at the time of catheter preparation (simply referred to as handling property). In some cases, the connectivity when connecting the tubes (sometimes referred to as assembling properties) is not sufficient. Further, at the time of bending, the metal wire is displaced, the braided body moves, and the pitch may change. When the pitch of the braided body is changed, the reinforcement by the braided body becomes uneven, and even if the braided body can be manufactured, it is easy to kink and the operability as a catheter may be impaired.

  The present invention provides a tube structure excellent in handleability and assemblability by preventing a change in the braid pitch of the metal braid during bending and fraying of the metal braid during tube cutting, and a catheter using the same. To make it an issue.

In the production of the tube structure, when polytetrafluoroethylene is used as the resin for forming the inner layer, the friction coefficient is small, so it is difficult to place the metal wire at a predetermined position, and the metal wire is displaced. It cannot be knitted properly to form a braided body. For this reason, a metal wire can be arrange | positioned in a predetermined position by roughening the surface of the inner layer formed of polytetrafluoroethylene with a chemical or softening the inner layer itself. Further, as described in Patent Document 2, if the resin of the inner tube is a substantially thermoplastic polymer material, the inner layer can be softened by performing heat treatment after braiding the metal wire. .
However, when a polyimide resin is used as the resin for forming the inner layer, it is generally difficult to roughen the surface with a chemical because the polyimide resin is chemically stable as a characteristic. In addition, since polyimide resins generally have high heat resistance and are thermosetting, it is difficult to soften them by heat treatment. As described above, when a thermosetting polyimide resin is used as the resin for forming the inner layer, the surface of the metal braid is fixed at a predetermined position by roughening the surface by chemical treatment or softening by heat treatment. There was a problem that it was difficult to arrange in.

Under such circumstances, the present inventors have a rigidity comprising an inner layer made of a thermosetting polyimide resin excellent in physical strength, chemical resistance, etc., a metal braid, and an outer layer made of resin or elastomer. In order to develop a tube structure that balances the balance between flexibility and flexibility (also referred to as flexibility and bendability), the inventors have intensively studied means for fixing a metal wire (metal braided body) on the inner layer. As a result, an adhesive layer capable of adhering the inner layer and the outer layer is provided between the inner layer and the outer layer, and at least a part of the metal braided body (a part in the thickness direction on the inner layer side of the metal braided body) If the tube is buried between the inner layer and the outer layer, a tube structure in which the inner layer, the metal braided body and the outer layer are joined together is formed, and the pitch of the metal braided body hardly changes during bending. It has been found that the metal braid is not easily frayed even when the tube is cut. Moreover, the present inventors have found that this tube structure is easy to manufacture and can achieve both balance between rigidity and flexibility.
Based on these findings, the inventors have further studied and have come to make the present invention.

The object of the present invention has been achieved by the following means.
(1) A tubular inner layer made of a thermosetting polyimide resin, an adhesive layer formed on the outer periphery of the inner layer, a metal wire braided on the outer periphery of the adhesive layer, and formed into a tubular shape, and A tube structure comprising: a metal braid having at least a part of the adhesive layer side buried in the adhesive layer; and an outer layer covering the metal braid.
(2) The tube structure according to (1), wherein the polyimide resin is obtained by polymerizing pyromellitic dianhydride and an aromatic diamine.
(3) The tube structure according to (1) or (2), wherein the adhesive layer is made of a hot-melt adhesive.
(4) The thickness of the said adhesive layer is any one of (1)-(3) which is 1/2 times or more and 2 times or less of the dimension of the said metal wire in the radial direction of the said tube structure. Tube structure.
(5) The tube structure according to (3) or (4), wherein the hot melt adhesive has a melting point of 100 ° C. or higher and 200 ° C. or lower.
(6) The hot-melt adhesive has a melt volume flow rate (Melt Volume Flow Rate, ISO 1133) is at ^{5 cm} 3/10 minutes or more 100 cm ^3/10 minutes or less when a load is applied 2.16kg at 160 ° C. The tube structure according to any one of (3) to (5).
(7) The metal wire according to any one of (1) to (6), wherein the metal wire is formed of at least one metal selected from stainless steel, platinum, silver, a titanium alloy, and a nickel-titanium alloy. Tube structure.
(8) The tube structure according to any one of (1) to (7), wherein the metal wire has a tensile strength of 2300 MPa to 3000 MPa.
(9) The tube structure according to any one of (1) to (8), wherein the metal wire has a flat rectangular cross-sectional shape perpendicular to the axis.
(10) The tube structure according to (9), wherein the thickness of the adhesive layer is not less than 1 times and not more than 3/2 times the length of the metal wire in the thickness direction.
(11) The tube structure according to any one of (1) to (10), wherein the outer layer is made of a polyimide resin.
(12) The tube structure according to (11), wherein the outer layer is formed by electrodeposition coating.
(13) The tube structure according to any one of (1) to (10), wherein the outer layer is made of a thermoplastic elastomer.
(14) The tube structure according to (13), wherein the outer layer is formed by extrusion molding.
(15) The tube structure according to any one of (1) to (14), wherein the resin forming the outer layer has a Shore D hardness of 30 to 72.
(16) The tube structure according to any one of (1) to (15), wherein the outer diameter is 0.6 mm to 2.3 mm and the inner diameter is 0.4 mm to 2.0 mm.
(17) The tube structure according to any one of (1) to (16), which is for a catheter.
(18) A catheter using the tube structure according to any one of (1) to (17).
(19) The catheter according to (18), comprising a balloon provided on one end side of the tube structure and a suction syringe or a compression syringe connected to the other end of the tube structure via a connector.

In the present invention, the term “tubular” refers to a hollow body shape in which the outline has a cross-sectional shape such as a circle, an ellipse, or a polygon, and has an inner hole extending in the axial direction.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after the numerical value as a lower limit value and an upper limit value.

  According to the present invention, since the metal braided body is embedded and fixed and the inner layer, the metal braided body and the outer layer are bonded together, the pitch of the metal braided body during bending is set. It is possible to provide a tube structure and a catheter using the tube structure that are not easily changed and that the metal braided body is not easily frayed at the time of cutting the tube and is excellent in handling and assembling.

FIG. 1 is a schematic side view for explaining an example of the catheter of the present invention. FIG. 2 is a partially cutaway schematic perspective view of the tube structure of the present invention showing an example of a metal braid (not formed on the outer layer) braided on an adhesive layer. FIG. 3 is a schematic cross-sectional view showing a cross section of an example of the tube structure of the present invention. FIG. 4 is an enlarged schematic cross-sectional view showing a cross section of an example of the tube structure of the present invention.

  In the tube structure of the present invention, since the metal braid is formed of a metal wire in which at least a part of the adhesive layer is embedded in the adhesive layer, the metal braid is arranged and fixed at a predetermined position on the inner layer, The reinforcing property by the metal braided body becomes uniform, and the portion that is weak to bending becomes difficult to be formed in the tube structure of the present invention. In addition, a metal braid in which an adhesive layer in which the metal braid is embedded is joined to the inner layer formed of a thermosetting polyimide resin, the metal braid, and the outer layer in an integrated manner, and arranged and fixed at a predetermined position. In combination with the body, the tube structure of the present invention is considered to exhibit a balance between rigidity and flexibility. Therefore, the tube structure of the present invention is not easily changed in pitch of the metal braid during bending, and is not easily frayed during cutting of the tube, and is excellent in handling and assembling. Moreover, the tube structure of the present invention has both rigidity and flexibility that are well balanced and can exhibit high operability in the catheter or the like when used in, for example, a catheter or the like.

  The tube structure of the present invention having such characteristics can be used for various applications, for example, a medical catheter, a tube inserted as an endoscope lumen, a tracheal tube, an artificial dialyzer, a medical device, etc. Tube for analysis equipment such as a tube attached to an equipment for use or a column for a high performance liquid chromatograph apparatus. Among them, the tube structure of the present invention is preferably used as a tube of a medical device that requires high operability, and more preferably used as a tube of a medical catheter that requires particularly high operability, It is further suitable as a tube of a medical catheter that is inserted into a blood vessel or a peripheral nerve blood vessel and has excellent torque transmission and bending workability. Examples of such a medical catheter include a microcatheter, a guiding catheter, a contrast catheter, a thrombus aspiration catheter, a stenosis penetration catheter, a drug solution injection catheter, and the like.

  A catheter using the tube structure of the present invention will be described. As long as the medical catheter has at least one tube structure, other catheter components are not particularly limited. For example, it may or may not have a balloon or stent.

As shown in FIG. 1, an example of the catheter of the present invention includes a long tube structure 4, a balloon 3 provided on one end side of the tube structure 4, and a connector on the other end of the tube structure 4. A suction syringe or compression syringe 6 connected via 5 (for example, made of resin), and a short tube structure 2 connected to the balloon 3 on the side opposite to the tube structure 4. The tube structure 2, the balloon 3, and the tube structure 4 are connected by, for example, an adhesive. The suction syringe or the compression syringe 6 contains a medicine, for example, an X-ray contrast medium or a fluid for inflating the balloon 3. The medical catheter 1 includes a stent (not shown) made of metal or the like in the tube structures 2 and 4. The balloon 3 is made of rubber and can be inflated by press-fitting a fluid (liquid or gas). In the medical catheter 1, for example, the tube structure 4 on the proximal end side, the balloon 3 and the tube structure 2 on the distal end side have a total length of 1 to 1.8 mm.
In such a medical catheter 1, the tube structure of the present invention is suitably used as the tube structure 4 on the proximal end side and the tube structure 2 on the distal end side.

An example of the tube structure of the present invention is shown in FIG. 2 (the outer layer 14 is not shown) to FIG. 4, and a tubular inner layer 11 made of polyimide resin and an adhesive layer formed on the outer periphery of the inner layer 11 12 and a metal braided body formed by braiding a metal wire 13a on the outer periphery of the adhesive layer 12 and having at least part of the adhesive layer 12 side, that is, the inner layer 11 side buried in the adhesive layer 12 13 and an outer layer 14 covering the metal braided body 13.
2 to 4 are schematic views for facilitating understanding of the configuration of the tube structure 10, particularly the embedded state of the metal braided body 13, and the configuration of the tube structure 10 is not necessarily accurate. It is not shown. For example, the thickness of the outer layer 14 is exaggerated and thicker for easy understanding of the embedded state of the metal braided body 13.

  The catheter tube of the present invention has, for example, a polyimide resin layer as an inner layer, an adhesive layer on the outer periphery thereof, a metal wire braided thereon to provide a metal braided body, and the metal braided body is bonded by heating and melting. It can also be referred to as a hollow molded body provided with an outer layer that is embedded in a layer and further covers this metal braid.

The tube structure of the present invention has appropriate dimensions depending on the application and the like. The maximum outer diameter of the tube structure (hereinafter simply referred to as the outer diameter) is appropriately set according to the application and is not particularly limited. For example, in the case of a normal tube structure, 0.6 mm or more If the tube structure is 2.3 mm or less and a small diameter, it is set to 0.6 mm or less.
Further, the maximum inner diameter of the tube structure (hereinafter simply referred to as the inner diameter) is also appropriately set depending on the application and the like, and is not particularly limited, and is set to 0.4 mm or more, for example. On the other hand, the inner diameter is usually set to 2.0 mm or less.
In the tube structure of the present invention, since the inner layer is formed of a thermosetting polyimide resin, the strength (rigidity) of the tube structure and the outer layer and, for example, a “cross-section rectangular” metal wire, While maintaining flexibility, the diameter can be reduced to the above-mentioned outer diameter, and the thickness can be reduced to a substantially uniform thickness. In the present invention, the uniformity of the thickness of the tube structure is preferably, for example, the ratio of the thickness of the thickest part to the thinnest part of the tube structure (thickest part / thinnest part) is 1.5 or less, More preferably, it is 1.1-1.4.

  The tube structure of the present invention has the above-described outer diameter and inner diameter, and the total thickness of the wall surface is set within a range that satisfies the above-described outer diameter and inner diameter. For example, when used for a general-purpose catheter, the total thickness of the wall surface is 150 μm in consideration of the fact that the tube structure has high strength and excellent rigidity, is less likely to cause kinking, and is limited by the finished outer diameter. The following is preferred. In recent years, there has been a demand for a catheter that has an inner diameter as large as possible and suppresses the outer diameter. In order to meet this requirement, the total thickness of the wall surface is preferably suppressed to 50 to 100 μm.

  The inner layer 11 is formed of a thermosetting polyimide resin having excellent physical strength, and balances rigidity and flexibility with the tube structure 10 in combination with the outer layer 14 and the metal braid 13 described later. Can be given well.

  The polyimide resin forming the inner layer 11 is not particularly limited as long as it is thermosetting (sometimes referred to as non-thermoplastic), and may be a commercially available product or an appropriately synthesized product. Such a polyimide resin is preferably obtained by polymerizing an aromatic dianhydride and an aromatic diamine. As a synthesis method, a polyamic acid generally comprising a condensation reaction of an aromatic diamine and an aromatic dianhydride is used. And a synthesis method by dehydration ring closure reaction. Examples of the ring-closing method include a method of adding a catalyst and a method of heating. In the present invention, it is preferable to form a polyimide layer on a metal core using a heating method.

The aromatic acid dianhydride forming the thermosetting polyimide resin is preferably an aromatic tetracarboxylic acid anhydride, and the aromatic tetracarboxylic acid anhydride is not particularly limited and those usually used can be used. For example, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, and derivatives thereof Is mentioned. In terms of easy availability, pyromellitic dianhydride is most preferable.
The aromatic diamine forming the thermosetting polyimide resin is not particularly limited, and examples thereof include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminobenzophenone, and 4,4 ′. -Diaminodiphenylmethane etc. are mentioned. 4,4′-diaminodiphenyl ether is preferred because it is easily available.
That is, the thermosetting polyimide resin is preferably one obtained by polymerizing pyromellitic dianhydride and an aromatic diamine.

  As a thermosetting commercially available polyimide resin, as a typical example, for example, “Pyre-ML (made by IST Co., product name)” and “UPILEX S (made by Ube Industries, product name) are used. Or the like.

  The inner layer 11 is not particularly limited, but has an inner diameter of, for example, 0.4 to 2.0 mm, preferably 0.6 to 1.8 mm, and has a thickness of, for example, 20 to 80 μm, preferably 30 to 60 μm. Yes.

  As shown in FIGS. 3 and 4, the adhesive layer 12 is provided on the inner layer 11 made of a thermosetting polyimide resin, and is at least one on the adhesive layer 12 side of the metal wire 13a of the metal braided body 13 to be described later. The part is buried, that is, the metal braided body 13 is buried and the metal braided body 13 is fixed. Further, the adhesive layer 12 causes the inner layer 11 and an outer layer 14 described later to adhere to each other. Therefore, the adhesive that forms the adhesive layer 12 may have any function as long as it has such a function, and a heat-meltable material can be used without any particular limitation.

  The adhesive that forms the adhesive layer 12 preferably has a melting point in the range of 100 to 200 ° C, and more preferably in the range of 105 to 180 ° C. When the melting point of the adhesive is in the range of 100 to 200 ° C., the heating temperature when the metal wire 13a is embedded in the adhesive layer 12 is low, the energy cost can be reduced, and the heat of the resin-based member of the apparatus for braiding the metal wire 13a Deterioration can be prevented and workability degradation due to melting of the adhesive layer can be prevented when coating as the outer layer 14 or during extrusion molding.

Adhesive forming the adhesive layer 12 is preferably melt volume flow rate when a load is applied 2.16kg (Melt Volume Flow Rate, ISO1133 ) is 5 to 100 cm ^3/10 min at 160 ° C.,. 8 to more preferably in the range of 90cm ^3/10 minutes. When the melt volume flow rate (sometimes referred to as MVFR) of the adhesive is within the above-mentioned range, the metal wire 13a can be easily embedded as desired, and the strength can be fixed.
Here, the MVFR of the adhesive is obtained by applying a load of 2.16 kg at a temperature of 160 ° C. and measuring the volume of the resin flowing out in 10 minutes in accordance with “Method B” described in ISO 1133. be able to.

  The adhesive used in the present invention is preferably a hot melt adhesive. The resin component of the hot-melt adhesive may be a thermoplastic resin, for example, a synthetic resin such as polyamide, acrylic, polyolefin, ethylene-vinyl acetate, chloroprene, or reactive urethane resin. Can be mentioned. Among these, polyamide-based ones are preferable in terms of good adhesiveness. As the polyamide-based thermoplastic resin, homopolymers or copolymers such as 6-nylon, 12-nylon, and 6,10-nylon can be used. Examples of the copolymer include commercially available platamide (trade name, manufactured by Arkema), amylan (trade name, manufactured by Toray), and Vestamelt (trade name, manufactured by Daicel Eponic).

  The thickness of the adhesive layer 12 is preferably at least 1/2 times the dimension in the thickness direction of the metal wire 13a to be braided, more preferably at least 2/3 times. The upper limit is not particularly limited. You may exceed 1 time the dimension of the thickness direction of the metal wire 13a. If the thickness of the adhesive layer 12 is ½ times or more, the metal wire 13a can be embedded as desired and fixed to strength. On the other hand, if the thickness of the adhesive layer 12 is too thick, the outer diameter becomes large. Therefore, it is preferably not more than twice the dimension in the thickness direction of the metal wire 13a, more preferably not more than 3/2 times. More preferably, it is 1 time or less. In the case where the metal wire has a flat cross section, it is preferably 1 to 3/2 times within the above range. The specific thickness of the adhesive 12 having such a relationship with the metal wire 13a is, for example, 0.015 to 0.045 mm when the metal wire has a round cross section and has a dimension of 0.03 mm. In the present invention, the thickness of the adhesive layer 12 refers to the thickness before the metal braid 13 is embedded.

  The “dimension in the thickness direction of the metal wire 13a” is a portion other than the knitted portion (overlapping portion) of the metal wire 13a, that is, the dimension of the metal wire 13a as a material. In the case of “type”, it means “diameter”, and as shown in FIG. 3 and the like, when the metal wire 13a is a so-called “cross-sectional flat type”, “cross-sectional rectangular shape along the thickness direction of the adhesive layer 12”. "Thickness (length)". For example, “the thickness of the adhesive layer 12 is one time the dimension of the metal wire 13a in the thickness direction” means that the thickness of the adhesive layer 12 is the diameter (cross-sectional round shape) or thickness of the metal wire 13a. "Means the same.

  The metal braid 13 reinforces the tube structure of the present invention and contributes to the tube structure 10 having both balanced rigidity and flexibility. The metal braided body 13 is formed on the outer periphery of the adhesive layer 12 by braiding a plurality of metal wires 13a, for example, in a spiral shape, and has a tubular shape as a whole. As such a metal braided body 13, for example, the number of braids (usually 8, 16), the braid density (number of pitches per unit length), and the like can be changed. As shown in FIG. 2, the metal braided body 13 formed by a shape and a knitting method in which the gap formed by the metal wire 13 a is rectangular is preferable. Although the number of the metal wires 13a used for the metal braid body 13 is not specifically limited, For example, 8-32 are mentioned. The tension when braiding the metal wire 13a is not particularly limited. For example, in the case of a stainless steel wire having a diameter of 0.03 mm, the metal wire 13a has a desired thickness of 50 g to 100 g. It is preferable at the point which can be buried. Here, “on the outer periphery of the adhesive layer” includes the case where the metal braid is entirely buried in the adhesive layer.

  In the metal braid 13, the gap between the braids of the metal wire 13 a is converted by the area of a rectangle, for example, a rhombus when knitting, and is determined by the diameter and pitch of the metal wire 13 a. The smaller the gap, the greater the proportion of the metal wire 13a (metal braided body 13) occupying the outer surface of the tube structure 10, and the strength of the tube structure 10 increases. In the present invention, the area as the gap is not particularly specified, and can be freely designed by the operability of the tube structure 10 or the like. The pitch, which is the distance between adjacent metal wires 13a braided in the same direction, is not particularly limited, but an example thereof is 2 to 8 mm.

  The metal wire 13a is not particularly limited as long as it is made of metal, but stainless steel (hereinafter referred to as SUS steel), platinum (Pt), silver (Ag), titanium (Ti) alloy (Ni-Ti alloy) Except those) and those formed of various metals such as nickel-titanium (Ni-Ti) alloys are preferably used, and SUS steel is more preferably used.

The cross-sectional shape of the metal wire 13a perpendicular to the axis of the metal wire 13a is not particularly limited. In particular, when reducing the thickness of the tube structure, the “cross-section rectangular type” is suitable.
Although the diameter of the metal wire (also referred to as “round wire”) of “round cross section” is not particularly limited, it is, for example, 0.02 to 0.05 mm. On the other hand, the dimension of the metal wire (also referred to as a flat wire) of “square cross section” is not particularly limited, but the thickness (vertical) is 0.01 to 0.03 mm, particularly 0.010 mm, and the width (horizontal) is 0. 0.07 to 0.12 mm, particularly 0.08 to 0.10 mm, and the aspect ratio is not particularly limited.

  The metal wire 13a has a tensile strength of preferably 2300 MPa or more, and more preferably 2500 MPa or more, in that it is difficult to break even due to tension fluctuations when braided on the polyimide inner layer 11. On the other hand, the tensile strength of the metal wire 13a is preferably 3000 MPa or less, and more preferably 2800 MPa or less, from the viewpoint of preventing warping during tension fluctuation. Here, the tensile strength of the metal wire 13a is measured by the breaking strength in the tensile test shown in JIS Z 2241. The tensile strength of the metal wire 13a can be adjusted according to the pass schedule and the annealing conditions during wire drawing using a hard material.

  As shown in FIG. 3, a part of the metal braided body 13 is buried in the adhesive layer 12, and is preferably arranged on the inner layer 11 side without being buried in the inner layer 11. As a result, the metal braid body 13 is disposed and fixed at a predetermined position on the adhesive layer 12, and the metal braid body 13 is displaced when the tube structure 10 is bent, and when the tube is cut and the outer layer is formed. You can also prevent fraying. Therefore, the metal wire 13a only needs to be partially buried in the adhesive layer 12, and can prevent the metal braided body 13 from being displaced and frayed to a high degree. For example, as shown in FIG. It is preferable that at least 1/2 times the dimension in the thickness direction is buried in the adhesive layer 12, for example, it is more preferable that 2/3 times or more is buried in the adhesive layer 12 as shown in FIG. . On the other hand, even if the metal wire 13a is buried in the adhesive layer 12 so as to greatly exceed the entire metal wire 13a, it cannot be expected to improve the effect of preventing the metal braided body 13 from shifting and fraying, and the tube structure 10 is large. In terms of the diameter, it is preferable that the metal wire 13a is embedded in the adhesive layer 12 by 1 time or less of the dimension in the thickness direction of the metal wire 13a. Therefore, the knitted portion (overlapping portion) of the metal wire 13 a in the metal braided body 13 is preferably not completely buried in the adhesive layer 12.

  The outer layer 14 is formed of a resin, which will be described later, and can provide rigidity and flexibility to the tube structure 10 in a well-balanced manner together with the inner layer 11 made of thermosetting polyimide resin, the metal braid 13 and the like.

  As the resin forming the outer layer 14, a commercially available resin can be used without any particular limitation, and an appropriately synthesized resin can be used without any particular limitation. Such a resin is not particularly limited, and examples thereof include a thermosetting resin, a thermoplastic resin, and a thermoplastic elastomer. Specifically, examples of the thermosetting resin include polyimide, phenol resin, and melamine resin, and examples of the thermoplastic resin include polyamide resin, polyurethane resin, polyethylene resin, polyvinyl chloride resin, and polyester resin. Examples of the thermoplastic elastomer include a polyamide elastomer, a polyurethane elastomer, and a polyester elastomer. In particular, a thermoplastic resin and a thermoplastic elastomer are preferable, a thermoplastic elastomer is more preferable, and a polyamide elastomer is more preferable because it is highly flexible and can provide the tube structure 10 with high operability in cooperation with the resin forming the inner layer 11. Is more preferable. On the other hand, if attention is paid to thermosetting resin, polyimide resin is preferable.

The polyimide resin used for the outer layer of the tube structure of the present invention is not particularly limited as long as it is thermosetting, and may or may not be electrodeposition-coated. A polyimide resin can be used.
The polyamide resin used for the outer layer is not particularly limited, but examples of commercially available polyamide resins include “Amilan” (trade name, manufactured by Toray Industries, Inc.) and “Leona” (trade name, manufactured by Asahi Kasei Co., Ltd.). Similarly, the above-mentioned polyurethane resin is not particularly limited, and examples thereof include “Zoldix” (trade name, manufactured by DIC). Similarly, the polyethylene resin is not particularly limited, and examples thereof include “Novatech LL” (trade name, manufactured by Nippon Polyethylene Co., Ltd.). Similarly, the polyvinyl chloride resin is not particularly limited, and examples thereof include “Kane Vinyl” (trade name, manufactured by Kaneka Corporation). Similarly, the above-mentioned polyamide elastomer is not particularly limited, but representative examples include “Pebax” (trade name, manufactured by Arkema), “Daiamide, Bestamide E” (trade name, manufactured by Daicel Evonik), and the like. Similarly, the polyurethane elastomer is not particularly limited, and examples thereof include “Elastollan” (trade name, manufactured by BASF). Similarly, the above-mentioned polyester elastomer is not particularly limited, and examples thereof include “Belprene” (trade name, manufactured by Toyobo Co., Ltd.).

  The resin forming the outer layer 14 can be used without any particular limitation, for example, but the resin D alone has a Shore D hardness in that the tube structure 10 has high flexibility and excellent workability due to kink prevention. It is preferably 72 to 30, and more preferably 60 to 40. Here, the Shore D hardness is a value measured according to JIS Z 2246.

  Although the thickness of the outer layer 14 is not specifically limited, For example, in the thickness laminated | stacked on the part where the metal wire 13a of the metal braid body 13 overlapped, 0.02-0.06mm is preferable, 0.03-0 .05 mm is more preferable.

  The tube structure of the present invention having such a configuration can be manufactured by forming an inner layer, an adhesive layer, a metal braided body, and an outer layer. For example, the above-described tube structure 10 can be manufactured as follows.

First, the inner layer 11 is formed. The inner layer 11 only needs to be formed in a tubular shape having a desired inner diameter and thickness. For example, the polyimide resin or polyimide resin described above is applied to the outer peripheral surface of a metal core called a mandrel having a predetermined outer diameter. A varnish (paint) dissolved in a solvent can be applied to a specified thickness and baked to form.
Although there is no restriction | limiting in particular as a metal core used at this time, A stainless steel wire and a silver plating copper wire are suitable. In this way, the polyimide inner layer 11 can be formed.

Next, an adhesive is applied to the outer peripheral surface of the inner layer 11 to form the adhesive layer 12. The adhesive layer 12 is formed by applying an adhesive, preferably a solution in which a hot melt adhesive is dissolved in a solvent as desired, onto the inner layer 11 and then baking it to remove the solvent. Form. The solvent to be used is not particularly limited, and examples thereof include high boiling point solvents such as cresol, phenol, and 1-methyl-2-pyrrolidone.
The viscosity of the adhesive or solution is not particularly limited as long as it can be applied to the surface of the inner layer 11. For example, the viscosity at 25 ° C. is preferably 5 to 15 Pa · s.

  Next, the metal braid body 13 is embedded in the formed adhesive layer 12. There is no particular limitation on the method of embedding the metal wire 13a in the adhesive layer 12. For example, a method in which the metal wire 13a is knitted in a state where the adhesive layer 12 is softened, a method in which the metal braided body 13 is disposed on the adhesive layer 12 and then embedded in the adhesive layer 12, and the metal wire 13a is cured before the adhesive is cured. The method of weaving is mentioned.

As a method of weaving the metal wire 13a with the adhesive layer 12 softened, specifically, the metal wire 13a is formed on the adhesive layer 12 formed on the outer peripheral surface of the core metal via the inner layer 11 by a braiding machine. For example, after weaving under the above-mentioned conditions, after the braiding operation is performed in a state where the entire cored bar is heated above the melting point of the adhesive and the adhesive layer 12, that is, the adhesive is softened, using a heater or the like before weaving And air cooling or water cooling.
As a method of burying the metal braided body 13 on the adhesive layer 12 and then burying it in the adhesive layer 12, specifically, after the metal braided body 13 is knitted so as to have an inner diameter smaller than the outer diameter of the adhesive 12. A method of heating the entire cored bar to a temperature equal to or higher than the melting point of the adhesive by using a heater or the like to soften the adhesive layer 12 and then embed the metal wire 13a in the softened adhesive layer 12 to cool it.

The method of embedding the metal wire 13a in the adhesive layer 12 is preferably the above-described method in which the metal wire 13a is knitted with the adhesive layer 12 softened when the braiding pitch is 2 to 4 mm. When the braid pitch is 2 to 4 mm, when the metal braid body 13 is disposed on the adhesive layer 12 and then embedded in the adhesive layer 12, most of the heat from the heater is taken away by the metal wire 13a and the adhesive layer Therefore, a large amount of energy is easily consumed to embed the metal wire 13a.
In addition, the method of heating the contact bonding layer 12 is not specifically limited, For example, it can implement using a hot air gun, an electric heating furnace, a hot air circulation furnace, a high frequency induction heating furnace, etc.

  In this way, the metal braid 13 can be embedded in the adhesive layer 12 by burying at least a part of the metal wire 13a constituting the metal braid 13 on the adhesive layer 12 side.

Next, the outer layer 14 is formed on the metal braided body 13 embedded in the adhesive layer 12.
Specifically, when the outer layer 14 is formed of a thermoplastic resin or a thermoplastic elastomer, the outer layer 14 can be formed using an extrusion coating apparatus. Although the extrusion molding method at this time is not particularly limited, a method in which a thermoplastic resin melted from the die is pressed with a designated die (die) to form a film on the metal braided body 13 is used.
On the other hand, when the outer layer 14 is formed of a thermosetting resin, it is generally difficult to melt-mold like a thermoplastic resin. Therefore, the metal wire 13a is braided and a thermosetting resin, preferably polyimide. A method of applying and baking resin paint, electrodeposition coating that forms a resin layer by electrolysis by applying a voltage between a counter electrode and a paint in which thermosetting resin, preferably polyimide resin is dispersed in water The outer layer 14 can be formed by a method or the like. When the outer layer 14 is formed of a thermosetting resin, the thermosetting resin is applied onto the metal braided body 13 and baked. In the method of squeezing the paint with a die such as a die, the outer layer 14 is formed with a constant coating thickness. However, since the surface on which the metal wire 13a is knitted is non-uniform, it may be difficult to form a uniform coating layer. Therefore, among the above-described methods, the electrodeposition coating method is preferable when the more uniform outer layer 14 is formed of a thermosetting resin, preferably a polyimide resin.

  When the outer layer 14 is formed in this manner, the metal braid body 13 is embedded and fixed in the adhesive layer 12, so that the resin forming the outer layer 14 or its paint is extruded or applied onto the metal braid body 13. When arranging, particularly when extruding a thermoplastic resin, the metal braid 13 of the metal braid 13 is not easily displaced, and the workability for forming the outer layer 14 is excellent. Therefore, the tube structure 10 having high workability provided with the metal braided body 13 braided at a predetermined pitch is obtained.

Since the tube structure of the present invention has the above-described configuration, the metal braid, that is, the metal wire is firmly fixed to the adhesive layer, and the inner layer and the outer layer are also firmly adhered to each other. The outer layer is integrally formed in close contact. Therefore, the tube structure of the present invention is not easily displaced or frayed not only at the time of bending and cutting the tube, but also at the time of bonding with a catheter component such as a connector and a balloon, and moreover, the metal braid There is little damage due to misalignment and fraying, and handling and assembly are excellent.
In addition, the tube structure of the present invention is provided with a metal braided body braided at a predetermined pitch at a predetermined position because the metal braided body, that is, the metal wire is not easily displaced during the manufacture thereof, and is well balanced. It is hard to kink with its rigidity and flexibility.

  The catheter and tube structure of the present invention are not limited to the above-described example, and various modifications are possible within the scope that can achieve the object of the present invention. For example, in the tube structure, the inner layer, the adhesive layer, and the outer layer are all formed as a single layer, but in the present invention, the inner layer, the adhesive layer, and the outer layer may be formed independently as a plurality of layers.

  The present invention will be described below in more detail based on examples, but the present invention is not limited thereto.

Example 1
In Example 1, the tube structure 10 shown in FIG. 3 (where the metal wire 13a is a round wire) was manufactured using the metal braided body 13 shown in FIG.
A polyimide resin paint (trade name: Pyre-ML (model number RC-5057), manufactured by IST Co., Ltd.) is applied onto a cored bar of 1.0 mm outer diameter formed of stainless steel (SUS304), and 450 The inner layer 11 having a thickness of 0.040 mm was formed on the cored bar by baking at a temperature of 10 ° C. and repeating this 10 times.
The above-mentioned polyimide resin coating contains polyimide obtained by polymerizing pyromellitic dianhydride and 4,4′-diaminodiphenyl ether.

Then, hot-melt adhesive (trade name: Puratamido M-1276, manufactured by Arkema Inc., copolymerized polyamide resin, melting point 105 ℃, MVFR8cm ^3/10 minutes) so that 15% by weight concentration cresol A dissolved adhesive paint was prepared.

This was applied onto the inner layer 11 and baked at 300 ° C. This was repeated five times to form a 0.015 mm adhesive layer 12 on the inner layer 11.
Next, the adhesive layer 12 was softened by preheating in a high-frequency induction heating furnace at a furnace temperature of 200 ° C. Before the adhesive layer 12 is solidified, a diameter of 0.03 mm formed from stainless steel (SUS304) in a circular cross section is formed from above the adhesive layer 12 using a braiding machine. While being embedded in the adhesive layer 12 by setting a metal wire (round wire, tensile strength 2400 MPa) 13a with a pitch of 2 mm and a tension of 80 g (1/2 of the diameter of the metal wire 13a) Sixteen braids (embedded in the adhesive layer 12) were braided to form a metal braided body 13.

  Next, a thermoplastic polyamide elastomer (trade name: Pebax 7233, manufactured by Arkema Co., Ltd., with a solid content of 100% is used on the metal braid 13 by using a die having a die hole diameter of 1.330 mm by a pressure type extruder. The outer layer 14 having a coating thickness of 0.03 mm was formed by extruding Shore D hardness 72).

  In this way, a core layer-containing coating layer molded body having an inner diameter of 1.0 mm and an outer diameter of 1.290 mm was obtained, and this was stretched by 22% to remove the core metal, and the tube structure 10 of Example 1 was removed. Manufactured.

(Example 2)
In Example 2, the tube structure 10 shown in FIG. 4 was manufactured using the metal braided body 13 shown in FIG.
A polyimide resin paint (trade name: Pyre-ML (model number RC-5057), manufactured by IST Co., Ltd.) is applied onto a cored bar of 1.0 mm outer diameter formed of stainless steel (SUS304), and 450 The inner layer 11 having a thickness of 0.040 mm was formed on the cored bar by baking at a temperature of 10 ° C. and repeating this 10 times.
Then, hot-melt adhesive (trade name: Puratamido M-1276, manufactured by Arkema Inc., copolymerized polyamide resin, melting point 105 ℃, MVFR8cm ^3/10 minutes) so that 15% by weight concentration cresol A dissolved adhesive paint was prepared.
This was applied onto the inner layer 11 and baked at 300 ° C., and this was repeated five times to form a 0.010 mm adhesive layer 12 on the inner layer 11.
Next, the adhesive layer 12 was softened by preheating in a high-frequency induction heating furnace at a furnace temperature of 200 ° C. Before the adhesive layer 12 is solidified, the cross-sectional flat angle (the length in the thickness direction is 0.010 mm (the thickness of the formed adhesive layer 12 is A metal wire 13a (flat wire, tensile strength 2400 MPa) 13a having the same length in the thickness direction of the metal wire 13a (one time as long as the length in the thickness direction) and a width direction length of 0.075 mm) is formed at a pitch of 2 mm. The metal braided body 13 was formed by braiding 16 pieces while setting the tension to 80 g and embedding it in the adhesive layer 12 (the entire metal wire 13a was buried in the adhesive layer 12).

Next, a thermoplastic polyamide elastomer (trade name: Pebax 7233, manufactured by Arkema Co., Ltd., with a solid content of 100% is used on the metal braid 13 by a die having a die hole diameter of 1.240 mm by a pressure type extruder. The outer layer 14 having a coating thickness of 0.03 mm was formed by extruding Shore D hardness 72).
In this way, a core layer-containing coating layer molded body having an inner diameter of 1.0 mm and an outer diameter of 1.200 mm was obtained, and this was stretched by 22% to remove the core metal, and the tube structure 10 of Example 2 was removed. Manufactured.

Example 3
A hot melt adhesive (trade name: platamide M-1425F, manufactured by Arkema Co., Ltd., copolymerized polyamide resin, melting point 155 ° C.) was used instead of the hot melt adhesive (trade name: platamide M-1276). A tube structure with an inner diameter of 1.0 mm and an outer diameter of 1.200 mm was manufactured in the same manner as Example 2 except for the above.

Example 4
Instead of hot melt adhesive (trade name: Platamido M-1276), hot melt adhesive (trade name: Grilon CR8, manufactured by MMS Japan Co., Ltd., copolymerized polyamide (nylon 6/12) resin, melting point 180 A tube structure having an inner diameter of 1.0 mm and an outer diameter of 1.200 mm was manufactured in the same manner as in Example 2 except that [° C., MVFR measurement impossible] was used.

(Example 5)
Hot-melt adhesive (trade name: Puratamido M-1276) hot melt adhesive instead: use (trade name Puratamido H038, manufactured by Arkema Inc., polyamide resin, melting point 118 ℃, MVFR35cm ^3/10 minutes) A tube structure having an inner diameter of 1.0 mm and an outer diameter of 1.200 mm was manufactured in the same manner as in Example 2 except that.

(Example 6)
Hot-melt adhesive (trade name: Puratamido M-1276) hot melt adhesive instead: use (trade name Puratamido H106, manufactured by Arkema Inc., polyamide resin, melting point 117 ℃, MVFR90cm ^3/10 minutes) A tube structure having an inner diameter of 1.0 mm and an outer diameter of 1.200 mm was manufactured in the same manner as in Example 2 except that.

(Example 7)
Hot-melt adhesive (trade name: Puratamido M-1276) hot melt adhesive in place of (trade name: Puratamido M-1757, Arkema Co., polyamide resin, melting point 113 ℃, MVFR19cm ^3/10 min) A tube structure having an inner diameter of 1.0 mm and an outer diameter of 1.200 mm was manufactured in the same manner as Example 2 except that was used.

(Example 8)
The above-described polyimide resin paint (product name: Pyre-ML (model number RC-5057)) on which the inner layer 11 was formed was applied seven times on the metal braid 13 formed while being embedded in the adhesive layer 12 in the same manner as in Example 2. The outer layer 14 having a coating thickness of 0.030 mm was formed by baking. In this way, a core layer-containing coating layer molded body having an inner diameter of 1.0 mm and an outer diameter of 1.200 mm was obtained, and this was stretched by 22% to remove the core metal, and the tube structure 10 of Example 8 was removed. Manufactured.

Example 9
The metal braid body 13 formed while being embedded in the adhesive layer 12 in the same manner as in Example 2 was subjected to electric field degreasing to clean the surface of the metal wire 13a, and then a polyimide resin paint for electrodeposition coating (trade name: Elecoat) , Manufactured by Shimizu Corporation) was electrodeposited to form an outer layer 14 having a coating thickness of 0.03 mm. In this way, a core layer-containing coating layer molded body having an inner diameter of 1.0 mm and an outer diameter of 1.200 mm was obtained, and this was stretched by 22% to remove the core metal, and the tube structure 10 of Example 9 was removed. Manufactured.

(Example 10)
Example except that instead of the thermoplastic polyamide elastomer (trade name: Pebax 7233), a thermoplastic polyamide elastomer (trade name: Pebax 6333, manufactured by Arkema Co., Ltd., Shore D hardness 61 at 100% solid content) was used. In the same manner as in Example 2, a tube structure having an inner diameter of 1.0 mm and an outer diameter of 1.200 mm was manufactured.

(Example 11)
Example except that instead of the thermoplastic polyamide elastomer (trade name: Pebax 7233), a thermoplastic polyamide elastomer (trade name: Pebax 5533, manufactured by Arkema Co., Ltd., Shore D hardness 52 at 100% solid content) was used. In the same manner as in Example 2, a tube structure having an inner diameter of 1.0 mm and an outer diameter of 1.200 mm was manufactured.

(Example 12)
Example except that instead of the thermoplastic polyamide elastomer (trade name: Pebax 7233), a thermoplastic polyamide elastomer (trade name: Pebax 4033, manufactured by Arkema Co., Ltd., Shore D hardness 39 at 100% solid content) was used. In the same manner as in Example 2, a tube structure having an inner diameter of 1.0 mm and an outer diameter of 1.200 mm was manufactured.

(Example 13)
Example except that instead of the thermoplastic polyamide elastomer (trade name: Pebax 7233), a thermoplastic polyamide elastomer (trade name: Pebax 3533, manufactured by Arkema Co., Ltd., Shore D hardness 29 at 100% solid content) was used. In the same manner as in Example 2, a tube structure having an inner diameter of 1.0 mm and an outer diameter of 1.200 mm was manufactured.

(Example 14)
In the same manner as in Example 2, an inner layer 11 made of polyimide resin having a thickness of 0.040 mm was formed on a core metal having an outer diameter of 0.6 mm made of stainless steel (SUS304), and then an adhesive layer having a thickness of 0.010 mm. 12 was formed with a hot-melt adhesive (trade name: Platamide M-1276), and a metal braid 13 was further formed. Next, a thermoplastic polyamide elastomer (trade name: Pebax 7233) was extruded onto the metal braided body 13 using a die having a die hole diameter of 0.840 mm by a pressure die extruder, and an outer layer having a coating thickness of 0.03 mm. 14 was formed. In this way, a cored-layer coating layer molded body having an inner diameter of 0.6 mm and an outer diameter of 0.800 mm was obtained, and this was stretched by 22% to remove the cored bar, and the tube structure 10 of Example 14 was removed. Manufactured.

(Example 15)
In the same manner as in Example 2, an inner layer 11 made of polyimide resin having a thickness of 0.040 mm is formed on a cored bar made of stainless steel (SUS304) having an outer diameter of 1.8 mm, and then an adhesive layer having a thickness of 0.010 mm. 12 was formed with a hot-melt adhesive (trade name: Platamide M-1276), and a metal braid 13 was further formed. Next, a thermoplastic polyamide elastomer (trade name: Pebax 7233) was extruded onto the metal braided body 14 using a die having a die hole diameter of 2.040 mm by a pressure die extruder, and an outer layer having a coating thickness of 0.03 mm. 14 was formed. In this way, a core layer-containing coating layer molded body having an inner diameter of 1.8 mm and an outer diameter of 2.000 mm was obtained, and this was stretched by 22% to remove the core metal, and the tube structure 10 of Example 15 was removed. Manufactured.

(Example 16)
Sectional flat angle formed of stainless steel (SUS304) (length in the thickness direction is 0.010 mm) (the thickness of the formed adhesive layer 12 is the same as the length in the thickness direction of the metal wire 13a (length in the thickness direction) 1)), and a metal wire (flat wire, tensile strength 2400 MPa) 13a having a width of 0.075 mm) embedded in the adhesive layer 12 with a pitch of 8 mm and a tension of 80 g (the metal wire 13a A tube structure having an inner diameter of 1.0 mm and an outer diameter of 1.200 mm was manufactured in the same manner as in Example 2 except that the metal braided body 13 was formed by braiding 16 pieces (the whole was buried in the adhesive layer 12).

(Comparative Example 1)
A polyimide resin paint (trade name: Pyre-ML (model number RC-5057), manufactured by IST Co., Ltd.) is applied onto a cored bar of 1.0 mm outer diameter formed of stainless steel (SUS304), and 450 The inner layer 11 having a thickness of 0.055 mm was formed on the core bar by baking at a temperature of 12 ° C. and repeating this 12 times.
Next, using a braiding machine, a metal wire (round wire, tensile strength 2400 MPa) 13a having a circular cross section made of stainless steel (SUS304) 13a is set at a pitch of 2 mm and a tension of 80 g, and the inner layer 11 Sixteen braids were braided on top to form a metal braided body 13.
Next, a thermoplastic polyamide elastomer (trade name: Pebax 7233, manufactured by Arkema Co., Ltd., with a solid content of 100% is used on the metal braid 13 by using a die having a die hole diameter of 1.330 mm by a pressure type extruder. The outer layer 14 having a coating thickness of 0.03 mm was formed by extruding Shore D hardness 72).
In this way, a core layer-containing coating layer molded body having an inner diameter of 1.0 mm and an outer diameter of 1.290 mm was obtained, and this was stretched by 22% to remove the core metal to produce a tube structure of Comparative Example 1. did.

(Comparative Example 2)
A polyimide resin paint (trade name: Pyre-ML (model number RC-5057), manufactured by IST Co., Ltd.) is applied onto a cored bar of 1.0 mm outer diameter formed of stainless steel (SUS304), and 450 The inner layer 11 having a thickness of 0.050 mm was formed on the cored bar by baking at 11 ° C. and repeating this 11 times.
Next, using a braiding machine, a metal wire 13a (flat wire, tensile strength 2300 MPa) 13a having a flat cross section (length in the thickness direction is 0.010 mm, length in the width direction is 0.075 mm) made of stainless steel (SUS304) A metal braided body 13 was formed by braiding 16 pieces on the inner layer 11 with a pitch of 2 mm and a tension of 80 g.
Next, a thermoplastic polyamide elastomer (trade name: Pebax 7233, manufactured by Arkema Co., Ltd., with a solid content of 100% is used on the metal braid 13 by a die having a die hole diameter of 1.240 mm by a pressure type extruder. The outer layer 14 having a coating thickness of 0.03 mm was formed by extruding Shore D hardness 72).
In this manner, a core layer-containing coating layer molded body having an inner diameter of 1.0 mm and an outer diameter of 1.200 mm was obtained, and this was stretched by 22% to remove the core metal to produce a tube structure of Comparative Example 2. did.

(Comparative Example 3)
In the same manner as in Example 2, an inner layer 11 made of polyimide resin having a thickness of 0.050 mm was formed on a core metal having an outer diameter of 0.6 mm made of stainless steel (SUS304), and then a metal braided body 13 was formed. Formed. Next, a thermoplastic polyamide elastomer (trade name: Pebax 7233) was extruded onto the metal braided body 13 using a die having a die hole diameter of 0.840 mm by a pressure die extruder, and an outer layer having a coating thickness of 0.03 mm. 14 was formed. In this manner, a core layer-containing coating layer molded body having an inner diameter of 0.6 mm and an outer diameter of 0.800 mm was obtained, and this was stretched by 22% to remove the core bar to produce a tube structure of Comparative Example 3. did.

(Comparative Example 4)
In the same manner as in Example 2, an inner layer 11 made of polyimide resin having a thickness of 0.050 mm was formed on a cored bar made of stainless steel (SUS304) having an outer diameter of 1.8 mm, and then a metal braided body 13 was formed. Formed. Next, a thermoplastic polyamide elastomer (trade name: Pebax 7233) was extruded onto the metal braided body 14 using a die having a die hole diameter of 2.040 mm by a pressure die extruder, and an outer layer having a coating thickness of 0.03 mm. 14 was formed. In this way, a core layer-containing coating layer molded body having an inner diameter of 1.8 mm and an outer diameter of 2.000 mm was obtained, and this was stretched by 22% to remove the core metal to produce a tube structure of Comparative Example 4. did.

(Comparative Example 5)
A metal wire (flat wire, tensile strength 2300 MPa) 13a having a flat cross section (thickness in the thickness direction of 0.010 mm, width in the length of 0.075 mm) formed of stainless steel (SUS304) at a pitch of 8 mm and tension. Is set to 80 g, and the metal braided body 13 is formed by braiding 16 pieces on the inner layer 11. The covering layer with a cored bar having an inner diameter of 1.0 mm and an outer diameter of 1.200 mm is the same as in Comparative Example 2. A molded body was obtained, and this was stretched by 22%, and the cored bar was pulled out to produce a tube structure of Comparative Example 5.

  Table 1 shows the inner diameter, outer diameter, and pitch of the manufactured tube structures of Examples 1 to 16 and Comparative Examples 1 to 5, and the melting point, MVFR, tensile strength, and Shore D hardness measured by the measurement method described above. .

(Metal braid misalignment and fraying)
The deviation and fraying of the metal braids in the manufactured tube structures of Examples 1 to 16 and Comparative Examples 1 to 5 were evaluated as follows for deviation during bending and fraying during tube cutting. The results are shown in Table 1.

(1) Displacement of metal braid during bending (indicated as “displacement during bending” in Table 1)
The manufactured tube structures of Examples 1 to 16 and Comparative Examples 1 to 5 were wound around a mandrel having a specified diameter once and a tensile force was applied to both ends.
In the evaluation, the wound part of the tube structure was observed with a magnifying glass (8 times), and whether or not the metal wires 13a were displaced and the metal wires 13a were in contact with each other was determined based on the following criteria.
○: No contact between the metal wires 13a was confirmed at the wrapping portion. Δ: One or two contact points between the metal wires 13a were confirmed at the wrapping portion, but it was practically used as a medical catheter tube. , What is acceptable ×: contact between the metal wires 13a was confirmed in more than two places at the winding part

(2) Fraying of metal wire at the time of cutting the tube (in Table 1, “Fraying at the time of cutting”)
The manufactured tube structures of Examples 1 to 16 and Comparative Examples 1 to 5 were cut in an oblique direction.
In the evaluation, the cut surface of the tube structure was observed with a magnifying glass (8 times), and the fraying condition of the metal wire 13a and the state of the cut portion due to fraying were determined according to the following criteria.
○: The metal wire 13a was not frayed at the cut portion, and it was good Δ: The metal wire 13a was frayed at the cut portion, but the cut portion was not lifted and practically acceptable as a tube of a medical catheter What is possible ×: The metal wire 13a frayed at the cut portion and the cut portion was lifted

(Rigidity and flexibility)
The rigidity and flexibility of the manufactured tube structures of Examples 1 to 16 and Comparative Examples 1 to 5 were evaluated as follows, and the results are shown in Table 1. That is, the rigidity is the tube structure under test. (Length: 500 mm) One end of the tube structure is fixed with a chuck, the other end is fixed with a chuck, a torque gauge is attached to the tip, and one end is rotated in the circumferential direction around the axis of the tube structure. The torque transmitted to the torque gauge was read with the gauge and evaluated.
The rigidity is excellent when it has the following torque value (cN / m) according to the inner diameter of the tube structure.
(1) When the inner diameter of the tube structure is 0.4 mm or more and 0.8 mm or less, the torque is 0.07 cN / m or more. (2-1) The inner diameter of the tube structure exceeds 0.8 mm and is 1.5 mm or less. When a round wire is used as the wire 13a, 0.23 cN / m or more. (2-2) When the inner diameter of the tube structure is more than 0.8 mm and 1.5 mm or less, and a flat wire is used as the metal wire 13a, the wire is 0.3. 25 cN / m or more (3) When the inner diameter of the tube structure exceeds 1.5 mm and is 2.0 mm or less, the torque is 0.30 cN / m or more

Flexibility was evaluated by preparing mandrels with different diameters, winding the test tube structure for one turn, and measuring the minimum mandrel radius at which the tube structure broke and kinked.
Flexibility is excellent when the mandrel radius is as follows according to the inner diameter of the tube structure.
(1) When the inner diameter of the tube structure is 0.4 mm or more and 0.6 mm or less, the radius of the mandrel is less than 7 mm. (2) When the inner diameter of the tube structure is more than 0.6 mm and 1.0 mm or less, the radius of the mandrel Is less than 10 mm. (3) When the inner diameter of the tube structure exceeds 1.0 mm and is 2.0 mm or less, the mandrel radius is less than 17 mm.

(Thickness uniformity)
The thickness uniformity of the manufactured tube structures of Examples 1 to 16 and Comparative Examples 1 to 5 was evaluated as follows. That is, a tube structure (length: 20 mm) was buried in a resin and polished, a cross-section was taken out and observed with a microscope (400 times), and the thickness of the tube structure was measured. The ratio of the thickness of the thickest part to the thinnest part (thickest part / thinnest part) was calculated. The results are shown in Table 1.

  As shown in Table 1, the tube structures 10 of Examples 1 to 16 in which the adhesive layer 12 is provided between the inner layer 11 and the outer layer 14 and a part of the metal braid body 13 is embedded in the adhesive layer 12 are as follows. In either case, neither the displacement of the metal braid 13 during bending nor fraying of the metal braid 13 during tube cutting could be confirmed. Moreover, even when the tube structure 10 of Example 16 has a large pitch of 8 mm, and the tube structure 10 of Examples 1 to 16 also forms the outer layer 14, the metal braid 13 is also displaced. The metal wire 13a was embedded in a state of being braided almost uniformly. Therefore, it turned out that it is excellent in handling property and assembling property.

  On the other hand, in the tube structures of Comparative Examples 1 to 4, it was confirmed that the metal braid 13 was displaced during bending and the metal braid 13 was frayed when the tube was cut. As practically acceptable. In addition, rigidity, flexibility, and thickness uniformity were inferior to the tube structures of the examples. In Comparative Example 5, the metal braid was displaced during bending, the metal braid was frayed when the tube was cut, and the metal braid was also frayed when forming the outer layer, and the metal wire was embedded in a biased state. Thus, it turned out that the tube structure of the comparative example 5 is inferior to handleability and assembly property. Further, the tube structure of Comparative Example 5 was inferior in rigidity, flexibility and thickness uniformity to the tube structure of the example.

(Operability)
Each of the tube structures 10 of Examples 1 to 16 includes an inner layer 11 made of a thermosetting polyimide resin, a metal braided body 13, and an outer layer 14 made of resin, and as described above, a metal braided body. 13 was embedded in the adhesive layer 12 in a state of being braided almost uniformly without slipping and fraying. In addition, all the tube structures 10 were excellent in rigidity, flexibility, and thickness uniformity. Therefore, it can be understood that medical catheters manufactured using these tube structures 10 are difficult to kink and have excellent operability.

DESCRIPTION OF SYMBOLS 1 Medical catheter 2 Tip side tube structure 3 Balloon 4 Base end side tube structure 5 Resin connector 6 Suction syringe or compression syringe 10 Tube structure 11 Inner layer 12 Adhesive layer 13 Metal braid 13a Metal wire 14 Outer layer

Claims (19)

  A tubular inner layer made of a thermosetting polyimide resin, an adhesive layer formed on the outer periphery of the inner layer, a metal wire braided on the outer periphery of the adhesive layer, and formed into a tubular shape, and the adhesive layer A tube structure comprising: a metal braid having at least a part of the side buried in the adhesive layer; and an outer layer covering the metal braid.   The tube structure according to claim 1, wherein the polyimide resin is obtained by polymerizing pyromellitic dianhydride and an aromatic diamine.   The tube structure according to claim 1 or 2, wherein the adhesive layer is made of a hot-melt adhesive.   The tube structure according to any one of claims 1 to 3, wherein a thickness of the adhesive layer is ½ to 2 times the dimension of the metal wire in the radial direction of the tube structure.   The tube structure according to claim 3 or 4, wherein the hot melt adhesive has a melting point of 100 ° C or higher and 200 ° C or lower. The hot-melt adhesives, 160 ° C. melt volume flow rate when a load is applied 2.16kg in (Melt Volume Flow Rate, ISO1133) is ^{5 cm} 3/10 minutes or more 100 cm ^3/10 min or less is claim 3 The tube structure according to any one of -5.   The tube structure according to any one of claims 1 to 6, wherein the metal wire is made of at least one metal selected from stainless steel, platinum, silver, a titanium alloy, and a nickel-titanium alloy.   The tube structure according to any one of claims 1 to 7, wherein the metal wire has a tensile strength of 2300 MPa or more and 3000 MPa or less.   The tube structure according to any one of claims 1 to 8, wherein the metal wire has a flat rectangular cross-sectional shape perpendicular to the axis.   The tube structure according to claim 9, wherein a thickness of the adhesive layer is not less than 1 times and not more than 3/2 times the length of the metal wire in the thickness direction.   The tube structure according to claim 1, wherein the outer layer is made of a polyimide resin.   The tube structure according to claim 11, wherein the outer layer is formed by electrodeposition coating.   The tube structure according to any one of claims 1 to 10, wherein the outer layer is made of a thermoplastic elastomer.   The tube structure according to claim 13, wherein the outer layer is formed by extrusion molding.   The tube structure according to any one of claims 1 to 14, wherein the resin forming the outer layer has a Shore D hardness of 30 to 72.   The tube structure according to any one of claims 1 to 15, wherein the outer diameter is 0.6 mm or more and 2.3 mm or less and the inner diameter is 0.4 mm or more and 2.0 mm or less.   It is an object for catheters, The tube structure of any one of Claims 1-16.   A catheter using the tube structure according to any one of claims 1 to 17.   The catheter according to claim 18, comprising a balloon provided on one end side of the tube structure, and a suction syringe or a compression syringe connected to the other end of the tube structure via a connector.

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