JPH10108906A - Catheter tube and catheter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catheter tube and a catheter being flexible and tightly bonded. SOLUTION: In catheter tube consisting of an outer tube and an inner tube and a catheter wherein a catheter tube and a catheter hub are bonded with an adhesive, the adhesive exhibits a vol. shrinkage factor of -3 to +8% and a viscosity of lower than 10 poises before curing and bonding parts are flexibly and tightly bonded.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a medical device used for a medical catheter or the like. More specifically, in bonding the catheter tubes to each other and the catheter tube and the catheter hub, by using the specified adhesive, the adhesion stability and reliability have been significantly improved, and the tightly bonded catheter tubes and Related to catheters.

[0002]

2. Description of the Related Art For medical devices such as catheters inserted into the trachea, gastrointestinal tract, urethra, blood vessels, and other body cavities and tissues, flash adhesives such as cyanoacrylates, ultraviolet curable adhesives, and visible light curable adhesives are generally used. Agents, cyanoacrylate adhesives, urethane adhesives, epoxy adhesives, epoxy adhesives, etc. have been used according to the purpose. In such a tube bonding assembly, a three-layer structure in which an adhesive is interposed between the inner tube and the outer tube is formed. That is, an adhesive such as adhesion between tubes or adhesion between a tube and a hub is arranged in a hollow cylindrical shape. In the bonding process, it is known that if the selection of adhesives and primers and the setting of pretreatment conditions are inappropriate, the possibility of occurrence of defects such as insufficient pressure resistance and leakage is increased even though the number is very small. ing.

For example, PTCA (Percutaneous Translu
In cases where extremely high levels of adhesive strength and reliability are required, such as balloon bonding of dilatation catheters, the selection of a suitable adhesive is one of the important technical issues.

For this reason, a high-strength adhesive has been selected. However, such high-strength adhesives generally have extremely high viscosity and are inferior in workability in the bonding process, and special attention and management are required for the bonding operation.

[0005] In addition to difficulties in terms of workability, there is a tendency to become extremely hard after curing, and as a result, the bonding site is solidified. Lossability).

It has also been pointed out that when a certain level of external force is applied to such a hard adhesive layer, a crack is generated in the adhesive layer, which may result in one of the causes of leakage.

[0007] In the tube bonding technology, there is a remarkable knowledge on the reliability of the bonding site, and it has already been introduced that the residual strain of the cured resin depends on the curing shrinkage ratio (Nakaezu, Adhesion Application Technology). 26-27, Nikkei Technical Books Co., Ltd., issued April 1, 1991).

That is, in a spiroorthoester-modified epoxy resin which is one of the so-called non-shrinkable monomers which are known to exhibit non-shrinkage during curing, the internal strain, shear strength and When the relationship between the peel strengths is determined, it is reported that the modified epoxy improves the peel strength by a factor of 3 to 4 although the shear strength slightly decreases.

By the way, the cure shrinkage means the volume shrinkage of the adhesive at the time of curing.

Further, in a cylindrical three-layer structure of an inner layer, an adhesive layer, and an outer layer in a catheter tube, if the curing shrinkage rate of the adhesive layer can be reduced, it is even more than a simple sheet-like adhesive structure. Needless to say, great effects can be expected.

It is considered that a great effect can be expected by using a modified adhesive having a reduced cure shrinkage as a means for suppressing the cure shrinkage. However, for example, an adhesive modified by blending a thermoplastic resin generally has a higher viscosity. For this reason, the cure shrinkage is improved according to the compounding amount, but in the case of tube bonding, the so-called adhesive wraparound becomes worse, and the reliability of the bonding as a whole is impaired, and the work of the bonding process However, it still had problems, such as marked deterioration in its properties, and its application was considerably limited.

As described above, in order to increase the adhesion force and improve the reliability of the catheter tube bonded in the form of a tube, the modified adhesive has a low curing shrinkage and a moderately low viscosity during the bonding operation. Is expected to appear.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, to enhance the workability of the bonding process, and to increase the peel strength of the bonding site when inserted into an organ in the body. Another object of the present invention is to provide a flexible and safe catheter tube and catheter.

[0014]

This and other objects are achieved by the present invention described below (1) to (6).

(1) In a catheter tube in which an outer layer catheter tube and an inner layer catheter tube are joined by an adhesive, the volume shrinkage rate of the adhesive upon curing is-
A catheter tube characterized by being 3% to + 8%.

(2) In a catheter in which a catheter tube and a catheter hub are joined by an adhesive,
A catheter having a volume shrinkage of -3% to + 8% upon curing of an adhesive.

(3) The catheter tube or catheter according to (1) or (2), wherein the viscosity of the adhesive before curing is lower than 10 poise.

(4) The catheter tube or catheter according to (1) to (3), wherein the adhesive is a medically acceptable adhesive.

(5) The adhesive is a cationic photocurable type ultraviolet curable adhesive, a photoradical curable type ultraviolet curable adhesive, a photocationically curable visible light curable adhesive, a photoradical curable visible light curable adhesive, cyano A modified adhesive obtained by mixing a non-shrinkable monomer with at least one selected from the group consisting of an acrylate adhesive, a urethane adhesive, and an epoxy adhesive (1) to
The catheter tube or catheter according to (4).

(6) The catheter tube or catheter according to (5), wherein the non-shrinkable monomer is at least one selected from the group consisting of a bicyclo ortho ester monomer, a spiro ortho ester monomer and a spiro ortho carbonate monomer.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

According to the present invention, the volume shrinkage upon curing is -3 in the bonding of the tubes constituting the catheter tube and between the catheter tube and the catheter hub.
By using a medically acceptable adhesive having a% to + 8% and a viscosity before curing of less than 10 poise, a safe catheter tube and catheter having a tightly and flexibly bonded joint can be obtained.

Next, the adhesive used in the present invention will be described.

Specific examples of the adhesive constituting the present invention include a photo-cation-curable UV-curable adhesive, a photo-radical-curable UV-curable adhesive, a photo-cation-curable visible-light-curable adhesive, and a photo-radical-curable adhesive. It is obtained by blending a non-shrinkable monomer with one or more adhesives selected from visible light curing adhesives, cyanoacrylate adhesives, urethane adhesives, or epoxy adhesives (hereinafter referred to as elementary adhesives). Modified adhesive.

The modified adhesive may contain a compound containing a filler such as a contrast agent or a pigment, if necessary, but must be medically acceptable.

Here, medically acceptable means "guidelines for basic biological testing of medical devices and materials".
1995 commentary; supervision of the medical device development section of the Pharmaceutical Affairs Bureau of the Ministry of Health and Welfare, Pharmaceutical Daily, and "Pharmaceutical Pharmacopoeia of the thirteenth edition, Plastic Pharmaceutical Container Testing Method" and other standards.

As the non-shrinkable monomer that can be blended in the adhesive of the present invention, three basic skeletons are known among polymerizable ring-opening monomers having a covalent bond (Nanbu and Endo, Adhesive application technology, pp. 21-24, published by Nikkei Technical Books Co., Ltd., issued on April 1, 1991).

The following are representative non-shrinkable monomers that can be used in the present invention: a. Bicyclo orthoester monomer (BOE)

[0029]

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B. Spiro orthoester monomer (S
OE system)

[0031]

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[0032]

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[0033]

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[0034]

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C. Spiro orthocarbonate monomer (SOC)

[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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In addition to these compounds,

[0042]

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[0043]

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[0044]

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And the like.

As the catheter to which the present invention can be applied, the following catheters (1) to (6) can be exemplified. In any case, a so-called three-layer structure in which an adhesive is disposed in a (hollow) cylindrical shape between the inner tube and the outer tube, such as adhesion between tubes or adhesion between a tube and a hub, is formed.

(1) Vascular microcatheters, such as a PTCA vascular dilatation catheter, a cerebral blood vessel or abdominal blood vessel microcatheter, and a microcatheter with a distal guide wire.

(2) Catheters that are inserted or placed in ordinary blood vessels, such as angiographic catheters, dilators or introducer indwelling needles, IVH catheters, and thermodilution catheters.

(3) gastric tube catheter, feeding catheter,
Catheters that are inserted or placed in the digestive tract orally or nasally, such as tubes for tube feeding.

(4) Oxygen catheter, oxygen cannula, endotracheal tube tube and cuff, tracheostomy tube tube and cuff, and intratracheal suction catheter, etc. are inserted or placed in the airway or trachea orally or nasally. Catheters.

(5) Urethral catheter, urinary catheter,
Catheters that are inserted or placed in the urethra or ureter, such as balloon catheters and balloons.

(6) Suction catheter, drainage catheter,
Catheters inserted or placed in various body cavities, organs, and tissues such as rectal catheters.

Among the above catheters, the present invention is preferably applied to a microcatheter which requires a high degree of adhesive strength at the bonding site and its reliability. In particular, the catheter front portion is made of a plurality of materials. PT
CA dilatation catheters and brain / abdominal microcatheters.

Representative polymers applicable as a specific substrate constituting the catheter tube include, for example, polyolefin, modified polyolefin, halogenated polyolefin, polyvinyl chloride, polystyrene, various poly (meth) acrylates and polyacrylates. , Various engineering polymers such as polyacrylonitrile, polyether, polyurethane, polyamide (polyamide elastomer), polyester (polyester elastomer), polycarbonate, polyimide, phenolic resin, amino-epoxy resin, cellulose derivative, silicone, and various rubber materials. As a material of the catheter, a polymer which is usually used can be exemplified. Furthermore, these block or graft polymers, polymer alloys, multilayered tubes and combinations thereof, and compounds containing fillers or pigments such as contrast agents, if necessary, may be included in the material of the present invention. it can.

The present invention can be applied to a certain material or material constituting a catheter tube, but can be applied to a wider range of materials than a conventional tube material in which peeling or leaking easily occurs to other materials or materials. Options are born.

Representative resins applicable as a specific substrate constituting a hub to which the present invention can be applied include, for example, polyolefins, modified polyolefins, halogenated polyolefins, polyvinyl chloride, polystyrene, and various types of polyolefins. Examples include (meth) acrylate, polyacrylate, polyacrylonitrile, polyether, polyurethane, various engineering polymers such as polyamide (polyamide elastomer), polyester (polyester elastomer), polycarbonate, and polyimide, and silicone. Since the catheter hub is generally manufactured by injection molding, among the above-mentioned resins, injection-molded grades are preferable. Particularly preferably,
Polyamide (polyamide elastomer) and polycarbonate.

In the present invention, the above non-shrinkable monomer is blended with the above-mentioned various adhesives and formulated into a modified adhesive. The prescription which exhibits the effect of the present invention is a case where the volume shrinkage ratio of the adhesive during curing is -3% to + 8%. If the shrinkage rate is higher than -3%, leakage or peeling may occur at a low rate due to an increase in strain of the adhesive layer after bonding, and the reliability is poor.

On the other hand, if it exceeds + 8%, the decrease in shear strength, which is generally one index of adhesive strength, cannot be ignored.
Although the adhesion due to expansion is increased, the bonding strength as a whole is often reduced.

In the case of ordinary adhesives, it can be said that, in order to soften the cured adhesive layer, the curing shrinkage generally becomes large. In other words, if many flexible chemical structural components are blended in the molecular design and prescription of the adhesive, the softening can be achieved, but disadvantageously, the volume shrinkage becomes large.

The method of incorporating the non-shrinkable monomer into various adhesives also differs depending on the type of adhesive. In the case of a two-pack type, it is blended with the liquid on the side that does not cause deterioration or deterioration due to the blending of non-shrinkable monomer. In the case where there is no influence such as deterioration, it is recommended to mix the liquid with the higher viscosity liquid. This is because the non-shrinkable monomer generally has a low viscosity, so that it is better to mix the two liquids so as to reduce the difference in viscosity, thereby improving workability during use.

In the case of the one-pack type, the formulation is performed after confirming the reactivity with the non-shrinkable monomer.

If the base adhesive has reactivity with the non-shrinkable monomer and the reaction speed is slow, the base adhesive is formulated into a two-pack type in which the base adhesive is liquid A and the non-shrinkable monomer is liquid B. You can also.

In many cases, a photocurable adhesive that cures with ultraviolet light or visible light requires a reaction with a non-shrinkable monomer. In such a case, a reaction catalyst, a sensitizer, a chain extender, and the like are blended and formulated so that the reaction curing proceeds smoothly.

On the other hand, IPN (inter-penetrating polymer
In the case of a modified adhesive in which the base adhesive and the non-shrinkable monomer react independently as in (r network) to form a mutually penetrating polymer chain, the respective reactions should proceed simultaneously and smoothly. It is also one of the preferred embodiments to incorporate a reaction modifier that preferably adjusts one or both reaction rates.

In the present invention, as the non-shrinkable monomer to be added to the base adhesive constituting the modified adhesive, it is preferable to use an orthoester-based expandable monomer, and the modified adhesive has a viscosity before curing of 10 poise. Preferably it is lower. More preferably, it is 1 poise or less.

It is known that those who are involved in the technology relating to the molecular design and prescription of an adhesive generally have an inverse correlation between the strength of the adhesive, the flexibility of the bonded portion after curing, and the viscosity before curing. . That is, when an epoxy-based adhesive for obtaining high strength is formulated, generally, the adhesive tends to have a high viscosity before curing, and the adhesive layer after curing tends to be considerably hard. this is,
In order to achieve high strength, the molecular skeleton of the constituents of each component must be inevitably hardened, and the viscosity of the adhesive tends to increase.

In the present invention, since the compound can be compounded in the molecular form of a monomer or a low-molecular oligomer, the increase in viscosity due to the compounding is slight or even reduced in some cases. Further, in the case of a PTCA dilatation catheter or the like in which the flexibility of the bonding site directly affects the trackability of the catheter, it can be prescribed for any of low contraction, non-contraction and low expansion, and has a low viscosity.

In general, when a low-viscosity formulation is used, the cure shrinkage increases, and the adhesive tends to be disadvantageous. As described above, the compounding and curing of the orthoester-based expandable monomer can be said to be specific from the viewpoint of general prescription techniques, and it is possible to provide an undesired balance in tube adhesion.

Next, the adhesion between tubes or between a tube and a hub in the present invention will be described.

Introducing (injecting) the adhesive into the gap between the adherends
It is a technique known to those skilled in the art to pre-treat the surface of the bonding site before doing so. As a typical pretreatment of the adherend, there is firstly removal of a foreign substance that adversely affects the adhesion attached to the surface of the adherend, such as cleaning and polishing. In addition, chemical treatment or surface modification aimed at improving the affinity between the surface of the adherend and the adhesive has been widely applied.

Typical treatment / modification methods are polishing, ultraviolet /
Examples include physical treatment (active gas) such as ozone, corona, and plasma, and primer treatment. In selecting a suitable pretreatment for the adherend to be used, there are some technical approaches, but in practice, a suitable method is set from empirical or trial and error methods among conventionally known methods. I often go.

As described above, it is important that the catheter tube and the hub, which are members to be subjected to the bonding step, are cleaned and removed of foreign substances and the like that adversely affect the bonding force. In addition, in the case of a material that is difficult to adhere to itself such as polyethylene or polyester, or in the case of a PTCA dilatation catheter that requires a high bonding strength for the catheter to be used, various types of materials are used in order to further increase the bonding strength. In many cases, an adhesive is injected after the surface treatment and surface modification.

A typical processing method will be described below.

A. Cleaning method: dipping (stationary, stirring, ultrasonic), spray, steam bath, wiping b. Abrasive; abrasive paper / sand blast c. Chemical treatment; acid-alkali etching, surface modification with oxidant d. Physical treatment (active gas); treatment / reforming with gas activated by ultraviolet rays, ozone, plasma, etc., corona treatment, flame treatment, etc. e. Primer treatment; silane compounds, etc. Cleaning, surface treatment / modification, etc.
Hub), the adhesive is introduced into the joint gap formed by the combination. The introduction method can also be carried out using a syringe, a dispenser, or the like. In the case of an epoxy type or the like, the pot life of the adhesive is suitably set, and the modified adhesive of the present invention is fixed so as not to receive an external impact after injection. After curing is completed, the thermosetting reaction is completed in a heating oven or the like. The same two-component type urethane-based modified adhesive can be bonded by almost the same operation.

On the other hand, in the cyanoacrylate-based modified adhesive of the present invention, it cures quickly after the adhesive is injected. Further, in the case of the modified adhesive of the present invention which is an ultraviolet curing system or a visible light curing system, rapid curing similarly occurs by irradiation with ultraviolet light or visible light. In any case, since the curing reaction is easily hindered by oxygen in the air, the bonding operation in an atmosphere of an inert gas such as nitrogen or argon is often preferable as necessary.

[0076]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 20 parts by weight of 3-methyl-1,5,7,11-t was added to 100 parts by weight of a bisphenol epoxy photocationically curable adhesive (manufactured by Nagase Chiba).
etraoxaspiro [5,5] undecane
(SOC expandable monomer) to obtain a modified adhesive. The volume shrinkage of the modified adhesive at the time of curing is 1%,
The viscosity was 0.9 poise (the volume shrinkage was calculated from the quotient of the specific gravity in the solid state after curing and the specific gravity in the liquid state before curing, and the viscosity was measured at 25 ° C. using an E-type viscometer. Measured in).

Next, a nylon inner tube (outer diameter of 0.1 mm) was used.
55 mm, inner diameter 0.35 mm) and a nylon outer tube (outer diameter 0.90 mm, inner diameter 0.58 mm) were overlapped with each other, adhered with the modified adhesive, and photocured to obtain a catheter tube of Example 1.

Next, the other end of the obtained catheter tube other than the adhesive end was heat-sealed to prepare a sample.
100 samples thus obtained were put into water, respectively, and pressurized (15 kg / cm ² ) from the end other than the bonded end of the outer tube, and the presence or absence of leak was confirmed. I couldn't see it.

Next, in order to examine the flexibility of the joint, a simple blood vessel running model having an outer diameter of 2.5 mm, an inner diameter of 1.0 mm, and a total length of 100 cm made of a bent polyvinyl chloride tube of the catheter tube of Example 1 was used. After inserting,
We proceeded smoothly to the exit.

(Comparative Example 1) Bisphenol epoxy photocationically curable adhesive (manufactured by Nagase Chiba Co., Ltd.) (volume shrinkage at curing: -5%, viscosity: 10 poise) The measurement was carried out as described above. A tube of Comparative Example 1 was obtained by the same operation using the same tube as in Example 1.

Next, the obtained catheter tube was treated in the same manner as in Example 1, and the presence or absence of a leak was confirmed by the same operation. Leaks were found in three tubes.

Next, when the obtained catheter tube was inserted into the simple blood vessel running model used in Example 1, the joint between the tube and the tube was caught by the bent portion of the simple blood vessel running model and could not reach the outlet. How.

Table 1 shows the differences between Example 1 and Comparative Example 1.

[0085]

[Table 1]

Example 2 Using the adhesive used in Example 1, a predetermined amount of the above adhesive was dropped onto a nylon catheter tube １．０ having an outer diameter of 1.0 mm and an inner diameter of 0.75 mm. The catheter was inserted into an adhesive hole of a nylon hub having an inner diameter of 1.20 mm and light-cured to obtain a catheter of Example 2.

Next, the end of the tube other than the adhesive end of the obtained catheter was heat-sealed to prepare a sample.
100 samples thus obtained were put into water, respectively, and pressurized (15 kg / cm ² ) from the end other than the bonded end of the outer tube, and the presence or absence of leak was confirmed. I couldn't see it.

(Comparative Example 2) A catheter of Comparative Example 2 was obtained in the same manner as in Example 2 using the adhesive used in Comparative Example 1.

Next, the obtained catheter was treated in the same manner as in Example 2, and the presence or absence of a leak was confirmed by the same operation as in Example 2. As a result, a leak was found in two of the catheters.

Table 1 shows the difference between Example 2 and Comparative Example 2.

[0091]

[Table 2]

[0092]

As described above, in the catheter tube of the present invention, the volume shrinkage ratio when the adhesive portion in which the non-shrinkable monomer is blended and modified is cured is -3% to + 8%. It is preferable that the internal strain at the joining portion is low, and the shear strength and the peel strength are well balanced. Also,
In general, a so-called adhesive wraparound is good in tube bonding, since a low viscosity prescription can be made. In addition, the bonding site in the cured state can be designed with relatively flexible molecules, and as a result, the bonding site can also be designed with a flexible material. For example, when the bonding site is used for balloon bonding of a PTCA dilatation catheter, the catheter trackability ( Excellent crossability is also obtained. That is, since a microcatheter having a flexible distal end can be provided, the peeling resistance is significantly improved in combination with the effect of reducing the resistance at the time of insertion into the body. As described above, the catheter of the present invention has effects of improving operability, reducing damage to tissue mucosa, and reducing patient pain, and is extremely useful.

Claims (6)

[Claims] In a catheter tube in which an outer catheter tube and an inner catheter tube are joined by an adhesive, a volume shrinkage ratio of the adhesive upon curing is -3% or more.
+ 8%. 2. A catheter in which a catheter tube and a catheter hub are joined by an adhesive, wherein the volume shrinkage of the adhesive upon curing is -3% to + 8%. 3. The catheter tube or catheter according to claim 1, wherein the viscosity of the adhesive before curing is lower than 10 poise. 4. The catheter tube or catheter according to claim 1, wherein the adhesive is a medically acceptable adhesive. 5. The adhesive according to claim 1, wherein said adhesive is a photo-cation-curable ultraviolet-curable adhesive, a photo-radical-curable ultraviolet-curable adhesive, a photo-cation-curable visible-light curable adhesive, a photo-radical-curable visible light-curable adhesive, The catheter tube according to any one of claims 1 to 4, wherein the catheter tube is a modified adhesive obtained by compounding a non-shrinkable monomer with at least one selected from the group consisting of a system adhesive, a urethane system adhesive, and an epoxy system adhesive. Or a catheter. 6. The catheter tube or catheter according to claim 5, wherein the non-shrinkable monomer is at least one selected from the group consisting of a bicyclo ortho ester monomer, a spiro ortho ester monomer and a spiro ortho carbonate monomer.