JPH0857034A - X-ray contrasting medical molding - Google Patents

Abstract

PURPOSE: To optionally control the nature of the material mainly constituting an excellent contrasting molding. CONSTITUTION: An X-ray contrasting halide polymer is uniformly dispersed in an X-ray-permeable polymer mainly constituting a contrasting molding to form a polymer mixture, e.g. a catheter.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a medical molded product having an X-ray contrast property.

[0002]

2. Description of the Related Art In medical devices such as catheters that are placed or inserted in the body, they are used for X purposes.
It is indispensable to have line contrast. Although plastics (polymer materials) are often used in medical devices, the polymer materials are basically light-transparent and X-ray transparent at the same time, and it is necessary to achieve the above-mentioned object by some means. Heretofore, as a method for imparting X-ray contrast property to plastics, it has been carried out to mix plastics with a heavy metal salt such as barium sulfate or bismuth bicarbonate, or an inorganic compound such as metal tungsten powder.

The use of these materials raises the following problems. For one, the essential characteristics of the material have made the medical device optically opaque and sometimes colored yellow or black, which is often undesirable. The specific problem becomes remarkable especially when a catheter is used. That is, the condition of the fluid existing in the pipe cannot be confirmed.

As a suboptimal measure for solving this problem, a catheter in which a resin containing a contrast material is put in a stripe shape is used. However, in order to secure a sufficient contrast property, it is necessary to increase the stripe width occupied by these contrast agents, and thus it has been difficult to easily confirm the contents.

On the other hand, studies have been conducted on a contrast-imparting material having transparency. Specifically, US Pat. No. 4,282,876 discloses an example in which a halogenated low molecular weight compound is plastically mixed by utilizing the fact that bromine and iodine have X-ray absorbing properties. However, this method cannot avoid the elution of the contrast agent, which is a problem in safety.

Further, Japanese Patent Laid-Open No. 6-23034 discloses a material using halogenated polyurethane, which has a contrast property and a light transmission property, and a catheter using the same. However, since it is necessary to newly synthesize a halogenated polyurethane in the present invention, it is not practical to synthesize one by one for each medical device having greatly different required physical properties. Further, since polyurethane uses a chain extender or a polyether as a soft segment, the content of halogen in the polymer does not become high, and the polyurethane tends to be insufficient in terms of X-ray contrast.

Further, there is a problem in molding process using the inorganic contrast agent. That is, since a large amount of metal powder or inorganic salt powder having high hardness is contained in the resin, abrasion of the die, nozzle, and screw of the molding machine cannot be avoided, which is an economical demerit.

[0008]

The present inventors have arrived at the present invention as a result of extensive studies on the above problems. The present invention is as follows.

(1) An X-ray contrasting medical molded article comprising a polymer mixture in which a halogenated polymer having X-ray contrasting property is uniformly dispersed in an X-ray transmitting polymer.

(2) The halogenated polymer having an X-ray contrast property is at least one of polyamide, epoxy resin, polyurethane, polyester, polycarbonate, urea resin, phenol resin and vinyl polymer. ) An X-ray contrast-enhanced medical molded article according to [4].

(3) The X-ray contrast-enhanced medical molded article according to any one of (1) to (2), wherein the halogen of the halogenated polymer having X-ray contrast is bromine and / or iodine.

(4) The halogenated polymer having the X-ray contrast property is an epoxy resin and / or polycarbonate derived from brominated diphenol (1).
An X-ray contrast-enhanced medical molded article according to any one of (3) to (3).

(5) The X-ray contrast-enhanced medical molded article according to any of (1) to (4) above, wherein the brominated diphenol is tetrabromobisphenol-A.

(6) The X-ray contrast-imaging medical molded article according to any one of (1) to (5), wherein the halogenated polymer having X-ray contrast is an epoxy resin represented by the following formula 1.

[0015]

Embedded image

(Wherein Br is bromine, Me is a methyl group, P is
h represents a phenyl group, and n represents an arbitrary integer. )

(7) The X-ray contrast-imaging medical product according to any one of (1) to (3) above, wherein the halogenated polymer having X-ray contrast is a polyamide and / or polyester derived from brominated dicarboxylic acid. Molded product.

(8) The X-ray contrast-enhanced medical molded article according to any one of (1) to (3) and (7) above, wherein the brominated dicarboxylic acid is tetrabromobutele (iso) phthalic acid.

(9) The X-ray contrast-enhanced medical molded article according to any one of (1) to (8), which has a tubular shape.

The present invention will be described in more detail below. The halogenated polymer having an X-ray contrast property used in the present invention has a halogen substituent such as bromine or iodine as an atomic group, and the halogen content is preferably 20 wt% or more. Of these, bromine is particularly preferable as the substituent in terms of stability to light and heat.

Specifically, as the halogenated polymer,
Radical polymer synthesized from halogenated styrene, halogenated phenyl (meth) acrylate, etc., polyamide derived from halogenated (iso, tere) phthalic acid, halogenated diphenols, polyester, polycarbonate, polyurethane, thermoplastic Examples thereof include thermoplastic polymers such as epoxy resins, phenol resins, thermosetting epoxy resins, and thermosetting polymers such as urea resins.

Among these, epoxy resins, polycarbonates, etc. using halogenated diphenol or halogenated dicarboxylic acid as a raw material monomer, particularly in terms of availability, price, halogen content, etc. of the raw material monomer or polymer.
Urea resin, polyester and polyamide are preferable.

The epoxy resin in the present invention means a polymer obtained by reacting a halogenated diphenol with a halogenated epoxide such as chloropropylene oxide or chlorobutylene oxide. The polycarbonate is synthesized by reacting a halogenated diphenol with phosgene or the like.

Specific examples of suitable halogenated diphenols include tetrabromobisphenol-A, tetrabromobisphenol-F, tetrabromobiphenol, di (hydroxydibromophenyl) ether, di (hydroxydibromophenyl) methane and the like. . Among them, tetrabromobisphenol-A is preferable from the economical aspect. In the present invention, it is free to copolymerize bisphenol-A, bisphenol-F, di (hydroxyphenyl) ether and di (hydroxyphenyl) methane together with tetrabromobisphenol-A within a range that does not reduce the contrast property.

The polyamide and polyester used in the present invention are synthesized by polycondensation of dicarboxylic acid and diamine or diol, and the following halogenated monomers are specifically used. Examples of the halogenated dicarboxylic acid include tetrabromtere (iso) phthalic acid, tribromutere (iso) phthalic acid, brominated naphthalene dicarboxylic acid, etc. As the halogenated diol such as aromatic diamine and the like, the above halogenated diphenol such as tetrabromobisphenol-A can be used.

It should be noted that the above-mentioned monomer group is merely an example, and the present invention is not limited to this. For example, a polyester composed of a combination of tetrabromoterephthalic acid and ethylene glycol, or a combination of tetrabromoterephthalic acid and trimethylhexamethylenediamine is used. It is free to use a polymer synthesized by combining a halogenated monomer and a non-halogenated monomer such as the following polyamide, or a polyester composed of a combination of terephthalic acid and tetrabromobisphenol-A.

The X-ray transparent polymer in the present invention is X
A polymer that does not contain heavy atoms and has line-contrast ability,
Usually commercially available polyamides, polyesters and their elastomers, polyethylene, polypropylene,
Polyolefin such as SBS and SEBS, and thermoplastic polymer such as polyurethane are used.

In the present invention, to uniformly disperse a halogenated polymer having an X-ray contrast property in an X-ray permeable polymer does not necessarily mean that the polymer is in a molecularly dispersed state, and both polymers are incompatible systems. Including the phase separation state that occurs in
Further, it includes a case where a halogenated polymer having X-ray contrast property is kneaded and dispersed as an organic filler.

When a halogenated polymer having an X-ray contrast property is used as an organic filler, its particle size is 0.01 μm.
m to 50 μm is desirable, more preferably 0.1 μm
To 10 μm is desirable. Further, since the filler is melt-kneaded, it is desirable that it is further thermosetting, but when the molding temperature is lower than the melting point or softening point of the polymer constituting the filler, even a thermoplastic polymer can be used as a filler. Can be used.

As a method for producing a medical molded article composed of a polymer mixture in which the halogenated polymer having X-ray contrast property of the present invention is uniformly dispersed, various methods including conventionally known methods can be used. Further, for example, X of the present invention
A medical molded article may be produced by combining a polymer mixture in which a halogenated polymer having a line contrast property is uniformly dispersed, with another resin.

As a specific example of the method for producing a medical molded article of the present invention, when the medical molded article is a tubular molded article,
There are a method of molding the polymer mixture as it is into a tube shape, a method of putting one or several pieces in parallel with the axial direction of the tube, a method of putting in a linear shape (striped shape, etc.), a method using a melt multilayer molding method, and the like. .

When the medical molded product of the present invention is a two-dimensional molded product (film, sheet, etc.), it is a (multilayer) extrusion molded product, and when it is a three-dimensional molded product (tube-shaped molded product, etc.), the polymer Examples thereof include injection molding in which the mixture is used as it is or in a linear or layered form (multilayer).

The X-ray contrast-enhanced medical molded product produced by the above-mentioned method is not molded by the halogenated polymer having X-ray contrast property alone. Therefore, the physical properties of the medical-molded product (for example, Flexibility, breaking strength, etc.) are extremely easy to control. That is, by combining the physical properties of the material (X-ray transparent polymer) mainly constituting the molded product to which the contrast property is given and the physical properties of the halogenated polymer, the final target physical property of the medical molded product can be arbitrarily set. You can control it.

Specific examples of the X-ray contrast-enhanced medical molded article of the present invention include catheters such as indwelling needle catheters, guiding catheters, PTCA catheters, and enteral feeding tubes.

[0035]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

(Example 1) Epoxy resin derived from tetrabromobisphenol-A and epichlorohydrin (Toto Kasei Co., Ltd., YPB, bromine content 53 wt%)
And nylon 6 (1030B, Ube Industries, Ltd.) were melt-kneaded at a weight ratio of 1: 1 and extruded from a hollow nozzle to obtain a tube having an outer diameter of 1.2 mm and an inner diameter of 0.9 mm.

At the molding temperature of 250 ° C., the epoxy resin was sufficiently dissolved and well mixed with Nylon 6 in the present tube, but it was white and not molecularly dispersed.

Further, the X-ray contrast property of this tube is determined by AAMI.
When tested according to the method described in Standards, IV, and Catheter Standards, the presence of a tube was confirmed up to an aluminum plate thickness of 6 mm, and it was shown that sufficient contrast was imparted.

Example 2 The same bromine-containing epoxy resin as in Example 1 was made into a powder having an average particle size of 30 μm by a ball mill. After modifying the powder with a titanate surface treatment agent, 2
Using a shaft extruder, melt-kneading 40 wt% amount into polybutadiene (RB-830, manufactured by Japan Synthetic Rubber Co., Ltd.),
It was a polymer mixture. The mixture is extruded from a hollow nozzle using a single-screw extruder, the outer diameter is 1.2 mm, the inner diameter is 0.9 m.
m tubes were obtained.

When the molding temperature of this tube is 105 ° C.,
Since the epoxy resin did not soften or melt, it was uniformly dispersed in the tube with an average particle size of 30 μm.

In addition, the X-ray contrast of this tube was evaluated in Example 1.
When examined in the same manner as above, the presence of a tube was confirmed up to an aluminum plate thickness of 7 mm, and sufficient contrast was confirmed.

Example 3 Poly (trimethylhexamethylene) tetrabromoterephthalamide was melt-kneaded with polycarbonate at a weight ratio of 4: 6 to obtain a phase-separated polymer mixture. The mixture is injection molded, 80 × 25 × 3 m
m strips were obtained.

When the contrast property of the plate was examined, the existence of the plate was confirmed up to an aluminum thickness of 3 mm, and it was confirmed that sufficient contrast property was imparted.

Example 4 A tube having an outer diameter of 1.2 mm and an inner diameter of 0.9 mm was produced in the same manner as in Example 1 except that polyethylene tetrabrom terephthalate was used as the halogenated polymer.

When the X-ray contrast property of this tube was examined, the presence of the tube was confirmed up to an aluminum plate thickness of 8 mm, and it was shown that sufficient contrast property was imparted.

Comparative Example A polyurethane having an X-ray contrast property (halogen content 20 wt%) was synthesized according to the method disclosed in JP-A-6-23034, and the outer diameter was 1.2 m.
A single tube having a diameter of m and an inner diameter of 0.9 mm was prepared. Regarding the X-ray contrast property of this tube, the existence of the tube was confirmed up to an aluminum plate thickness of 10 mm.

[0047]

The X-ray contrast-enhanced medical molded article of the present invention is
Since it is not formed of a single halogenated polymer having a line contrast property, it is extremely easy to control the physical properties of a medical molded product. That is, by combining the physical properties of the material (X-ray transparent polymer) mainly constituting the molded product to which the contrast property is given and the physical properties of the halogenated polymer, the final target physical property of the medical molded product can be arbitrarily set. You can control it.

Specific examples of the X-ray contrast-enhanced medical molding of the present invention include catheters such as an indwelling needle catheter, a guiding catheter, a PTCA catheter, and an enteral feeding tube.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideaki Kito 1500 Inoguchi, Nakai-cho, Ashigarashami-gun, Kanagawa Terumo Corporation (72) Inventor Kenji Ishikawa 1500, Inoguchi, Nakai-cho, Ashigagami-gun, Kanagawa Terumo Corporation

Claims (9)

[Claims] 1. An X-ray contrast-enhancing medical molded article comprising a polymer mixture obtained by uniformly dispersing a halogenated polymer having X-ray contrast properties in an X-ray permeable polymer. 2. The halogenated polymer having X-ray contrast property is at least one of polyamide, epoxy resin, polyurethane, polyester, polycarbonate, urea resin, phenol resin, vinyl polymer. The X-ray contrast-enhanced medical molded article described. 3. The halogen of the halogenated polymer having an X-ray contrast property is bromine and / or iodine.
The X-ray contrastable medical molded article according to claim 2. 4. The X-ray contrast-imaging medical molding according to claim 1, wherein the halogenated polymer having X-ray contrast property is an epoxy resin and / or a polycarbonate derived from brominated diphenol. Goods. 5. The X-ray contrast-enhanced medical molded article according to claim 1, wherein the brominated diphenol is tetrabromobisphenol-A. 6. The X-ray contrast-enhanced medical molded article according to claim 1, wherein the X-ray contrast-enhanced halogenated polymer is an epoxy resin represented by the following formula 1. Embedded image (In the formula, Br represents bromine, Me represents a methyl group, Ph represents a phenyl group, and n represents an arbitrary integer.) 7. The X-ray contrast-enhanced medical molded article according to claim 1, wherein the halogenated polymer having X-ray contrast is a polyamide and / or polyester derived from brominated dicarboxylic acid. . 8. The X-ray contrast-imaging medical molded article according to any one of claims 1 to 3 and 7, wherein the brominated dicarboxylic acid is tetrabromtere (iso) phthalic acid. 9. The X-ray contrast-enhanced medical-use molded article according to claim 1, which has a tubular shape.