WO2015025626A1 - Material for medical tubes, and medical tube - Google Patents

Abstract

A material for medical tubes, which is obtained by melt-kneading a thermoplastic resin and a silicone oil. The silicone oil has a kinematic viscosity of from 1,000 mm²/s to 100,000 mm²/s (inclusive), and the content of the silicone oil is from 0.1 part by mass to 50 parts by mass (inclusive) per 100 parts by mass of the thermoplastic resin.

Description

Medical tube material and medical tube

The present invention relates to a medical tube material and a medical tube.
This application claims priority based on Japanese Patent Application No. 2013-170403 filed in Japan on August 20, 2013, the contents of which are incorporated herein by reference.

Medical tubes are used in many medical instruments such as endoscopes and catheters. As a medical tube, what shape | molded the thermoplastic resin, for example is used.
When used as a tube passing through the channel tube of an endoscope or used as a catheter, the surface frictional resistance of the medical tube is required to be small in order to reduce the insertion resistance. Therefore, a tube using a low friction material such as polytetrafluoroethylene is generally used (for example, Patent Document 1).

On the other hand, as a method of reducing the surface frictional resistance of the molded product of the thermoplastic resin, there is a method of adding silicone oil or silicone rubber (raw rubber).

Japanese Unexamined Patent Publication No. 2004-340364

However, according to studies by the present inventors, there are many problems in applying a method of adding silicone oil or silicone rubber (raw rubber) to a medical tube.
For example, when silicone oil is added to a thermoplastic resin, the thermoplastic resin and the silicone oil are separated from each other in the molded product, and the silicone oil tends to come out from the surface. In this case, when the tube is inserted into a channel tube of an endoscope or a living body, silicone oil may migrate (bleed) to the inner surface of the tube, and it is difficult to use the tube as a medical tube.
When silicone rubber is blended with the thermoplastic resin, the thermoplastic resin and the silicone rubber are easily separated during molding, and the moldability is poor. For example, there is a problem that a phenomenon called “eyes” occurs during extrusion molding and the tube surface becomes rough. This method is therefore not suitable for the production of medical tubes.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a medical tube material and a medical tube that have low surface frictional resistance, no bleeding problem, and good moldability.

The present inventors have made intensive studies, kinematic viscosity by adding 1000 mm ² / s or more 100,000 mm ² / s or less of the silicone oil in thermoplastic resin, by melt-kneading, bleeding and the moldability deteriorated It has been found that the surface frictional resistance can be reduced without causing problems.
The present invention is based on the above findings and has the following aspects.

A first aspect of the medical tube material of the present invention, a thermoplastic resin, it was melt-kneading a silicone oil, kinematic viscosity of the silicone oil is not more than 1000 mm ² / s or more 100,000 mm ² / s, the Content of silicone oil is 0.1 mass part or more and 50 mass parts or less with respect to 100 mass parts of said thermoplastic resins.

According to a second aspect of the present invention, the medical tubing of the first aspect, kinematic viscosity of the silicone oil may be not more than 1000 mm ² / s or more 30,000 mm ² / s.

According to the third aspect of the present invention, in the medical tube material according to the first aspect or the second aspect, the content of the silicone oil is 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin. The amount may be 50 parts by mass or less.

According to a fourth aspect of the present invention, in the medical tube material according to any one of the first to third aspects, the silicone oil is dimethyl silicone oil, methylphenyl silicone oil, and fluoro. It may be at least one selected from the group consisting of alkyl silicone oils.

According to the fifth aspect of the present invention, in the medical tube material according to any one of the first to fourth aspects, the thermoplastic resin may be a polypropylene resin.

The medical tube according to the sixth aspect of the present invention is obtained by molding the medical tube material according to any one of the first aspect to the fifth aspect into a tube shape.

According to the medical tube material and the medical tube of each aspect described above, it is possible to provide a medical tube material and a medical tube that have low surface friction resistance, no bleeding problem, and good moldability.

It is a schematic diagram explaining the evaluation method of the moldability of the medical tube of this invention. It is a schematic diagram explaining the measuring method of the surface friction coefficient of the medical tube of this invention. It is a top view explaining the installation position of a test piece in evaluating the transferability of the medical tube of the present invention. It is a side view which shows the state which laminated | stacked the test piece, the sheet | seat for transferability confirmation, and a weight in the case of evaluating the transferability of the medical tube of this invention.

<Medical tube material>
The medical tube material of the present invention is obtained by melt-kneading a thermoplastic resin and silicone oil.

The thermoplastic resin is not particularly limited. For example, polyethylene (PE) resin, ionomer resin (for example, ethylene-methacrylic acid copolymer ionomer resin), polypropylene (PP) resin, ultrahigh molecular weight PP, polybutene, 4-methylpentene. -1 polymer, cyclic polyolefin resin, styrene resin (eg, polystyrene, butadiene-styrene resin, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene (ABS) resin), polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyacetal , Polyphenylene oxide, polyvinyl acetate, polyvinyl alcohol, polymethyl methacrylate (PMMA), cellulose acetate, polyester resin (eg, polyethylene terephthalate, poly (Ethylene terephthalate, polytrimethylene terephthalate, etc.), polyamide (PA) resin, polyimide resin, fluororesin, polysulfone, polyethersulfone, polyarylate, polyetheretherketone, liquid crystal polymer, thermoplastic polyurethane, thermoplastic elastomer (for example, , Polyamide elastomers, polyester elastomers, etc.), biodegradable polymers, and copolymers thereof.

The PE resin may be any of low density PE, high density PE, linear low density PE, and ultra high molecular weight PE. The PP resin may be a homo PP, a random PP, or a block PP, and may have an atactic structure or a syndiotactic structure.

These thermoplastic resins may be used alone or in combination of two or more.
Among the above, as the thermoplastic resin, PP resin, polyamide elastomer, polyester elastomer, and PE resin are preferable, and PP resin is particularly preferable.

As the silicone oil, kinematic viscosity include: 1000 mm ² / s or more 100,000 mm ² / s is used. When the kinematic viscosity is 1000 mm ² / s or more, the silicone oil can be prevented from coming out of the surface of the molded product and causing bleeding. When the kinematic viscosity is 100000 mm ² / s or less, the moldability of the medical tube material is good and, for example, a phenomenon called “eye and eyes” hardly occurs during extrusion molding.
The kinematic viscosity of the silicone oil, 1000 mm ² / s or more 30,000 mm ² / s or less. The kinematic viscosity of silicone oil is a value measured at 25 ° C. and normal pressure.

The type of silicone oil is not particularly limited, and examples thereof include dimethyl silicone oil, methylphenyl silicone oil, fluoroalkyl silicone oil, and methyl hydrogen silicone. Modified silicones with functional groups introduced into these silicone oils (amino modification, epoxy modification, mercapto modification, carboxyl modification, polyether modification, phenol modification, methacryl modification, acrylic modification, carboxylic anhydride modification, carbinol modification, aralkyl modification , Silanol terminals, etc.) may be used. These may be used alone or in combination of two or more.
Among the above, dimethyl silicone oil, methylphenyl silicone oil, and fluoroalkyl silicone oil are preferable as the silicone oil, and dimethyl silicone oil is particularly preferable.

The content of silicone oil in the medical tube material is 0.1 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin. When the amount is 0.1 parts by mass or more, the effect of reducing the surface friction resistance by silicone oil is sufficiently obtained, and when the amount is 50 parts by mass or less, the problem of bleeding hardly occurs and the moldability is also good. In addition, the content of the silicone oil in the medical tube material is more preferably 5 parts by mass or more and 50 parts by mass or less, and further preferably 5 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin. It is as follows.

The medical tube material may further contain other components (optional components) other than the thermoplastic resin and the silicone oil as long as the effects of the present invention are not impaired, if necessary.

The medical tube material of the present invention can be produced by melt-kneading a thermoplastic resin, silicone oil, and optional components as required. By melt-kneading the thermoplastic resin and the silicone oil, the silicone oil is finely dispersed in the thermoplastic resin.
The melt kneading can be performed using a known kneading apparatus such as a single screw extruder or a twin screw extruder.
The melt-kneading is performed at a temperature equal to or higher than the melting point of the thermoplastic resin to be used (when a plurality of thermoplastic resins are used, the temperature is equal to or higher than the melting point of the thermoplastic resin having the highest melting point).
The kneading temperature is preferably less than the thermal decomposition temperature of the thermoplastic resin to be used (when using a plurality of thermoplastic resins, it is lower than the thermal decomposition temperature of the thermoplastic resin having the lowest thermal decomposition temperature).

The medical tube material of the present invention is molded into a tube shape and used as a medical tube.
The molded product obtained by molding the medical tube material of the present invention has a small surface friction resistance because silicone oil is dispersed in the thermoplastic resin. Therefore, when the molded product obtained by molding the medical tube material of the present invention into a tube shape is used as a tube or a catheter that passes through the channel tube of the endoscope, the insertion resistance is reduced.

The silicone oil in the thermoplastic resin is less likely to appear on the surface of the molded product. Therefore, even when the molded product is used as a tube or a catheter that passes through the channel tube of an endoscope, the problem of bleeding (transfer of silicone oil into the channel tube or the living body) hardly occurs.

The medical tube material of the present invention has good moldability, for example, a phenomenon called “eye and eye” hardly occurs during extrusion molding, and a molded product having a smooth surface can be obtained.
Therefore, the medical tube material of the present invention is useful for manufacturing a medical tube.
Moreover, the molded product which shape | molded the medical tube material of this invention in the tube shape is useful as a medical tube.

<Medical tube>
The medical tube of this invention shape | molds the above-mentioned medical tube material in tube shape.
The medical tube material can be molded by a known molding method such as extrusion molding or injection molding as a thermoplastic resin molding method.
The shape of the tube is a shape corresponding to the use of the medical tube. Examples of the use of the medical tube include a catheter and a treatment instrument tube for an endoscope.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
The raw materials used in Examples and Comparative Examples are as follows.

<Raw material> [Thermoplastic resin]
Polypropylene: Product name “BC8”, manufactured by Nippon Polypro.
Polyamide elastomer: Product name “PEBAX6333”, manufactured by Arkema.
Polyester elastomer: Product name “Hytrel 6377”, manufactured by Toray DuPont.

[Silicone oil]
S1: Dimethyl silicone, kinematic viscosity 10000 mm ² / s, product name “KF96-1000cs”, manufactured by Shin-Etsu Silicone.
S2: Dimethyl silicone, kinematic viscosity 12500 mm ² / s, product name “360MF-12500 cps”, manufactured by Toray Dow Corning.
S3: Dimethyl silicone, kinematic viscosity 1000 mm ² / s, product name “KF96-1000cs”, manufactured by Shin-Etsu Silicone.
S4: Dimethyl silicone, kinematic viscosity 30000 mm ² / s, product name “KF96-30000cs”, manufactured by Shin-Etsu Silicone.
S5: Dimethyl silicone, kinematic viscosity 50000 mm ² / s, product name “KF96-50000cs”, manufactured by Shin-Etsu Silicone.
S6: Dimethyl silicone, kinematic viscosity 100000 mm ² / s, product name “KF96-100000cs”, manufactured by Shin-Etsu Silicone.
S7: Methyl phenyl silicone, kinematic viscosity 3000 mm ² / s, product name “KF50-3000cs”, manufactured by Shin-Etsu Silicone.
S8: Fluoroalkyl silicone, kinematic viscosity 10000 mm ² / s, product name “FL100-10000cs”, manufactured by Shin-Etsu Silicone.
S11: Dimethyl silicone, kinematic viscosity 10 mm ² / s, product name “KF96-10cs”, manufactured by Shin-Etsu Silicone.
S12: Dimethyl silicone, kinematic viscosity over 1000000 mm ² / s, product name “X-21-3043”, manufactured by Shin-Etsu Silicone.

<Example 1>
100 parts by mass of polypropylene and 10 parts by mass of silicone oil S1 were melt-kneaded with a biaxial extruder (screw outer diameter φ = 30 mm) to obtain a pellet-like kneaded product. The melt kneading was performed at a rotation speed of 200 rpm and changing the set temperature in the order of 80 ° C.-180 ° C.-220 ° C.
The following evaluation was performed about the obtained kneaded material. The results are shown in Table 1.

[Evaluation of formability]
Formability was evaluated by the procedure shown in FIG.
The obtained kneaded product was molded under the following conditions using a single screw extruder 1 (screw outer diameter φ = 20 mm) equipped with a tube die 2 to obtain a tube 3.
(Molding condition)
Number of revolutions: 20 rpm.
Tube die 2 cap dimensions: 5 mm outer diameter, 3 mm inner diameter.
Molding speed: 3 m / min.
Tube 3 dimensions: 3 mm outer diameter, 2 mm inner diameter.

The above molding was carried out continuously for 10 hours, and during this time, the occurrence of the eyes (particulate resin pieces) 4 at the mouth part of the tube die 2 was visually observed. Formability was evaluated according to the following criteria based on the number of times 4 occurred in the eye part and adhered to the base part. Here, the corner 4 was removed from the base portion whenever it occurred.
(Judgment criteria)
A: Occurrence of 0 times in eyes and molding during 10 hours molding.
○: The number of occurrences was once in the eyes and molding during 10 hours.
X: The number of occurrences in the eye during molding for 10 hours is 2 times or more.

[Evaluation of surface lubricity]
The tube obtained by the evaluation of formability was cut from one place in the circumferential direction at one end to the other end along the length direction, spread from the cut portion, formed into a sheet, and fixed to a heat press machine. Hot pressing was performed under the conditions of 20 ° C. and 20 ° C. The obtained sheet was cut to obtain a sheet-like test piece of 120 mm × 20 mm × 1 mm.
Using the obtained test piece, the surface friction coefficient was measured with reference to JIS K7125.

The procedure for measuring the surface friction coefficient will be described with reference to FIG. For the measurement, a test piece 10 is installed, the table 5 is movable parallel to the installation surface, a reinforcing plate 6 that fixes the test piece 10 to the table 5, and a mating member 7 that is placed on the test piece 10. A friction coefficient measuring device composed of a weight 8 for pressing the mating member 7 with a constant load against the test piece 10 and a load cell 9 connected to the mating material 7 was used. The test piece 10 is fixed to the table 5 and moves together with the table 5. The test piece 10 fixed to the table 5 is subjected to a vertical load by the weight 8 and comes into contact with the mating member 7. When the table 5 is translated in the direction opposite to the load cell 9 side (in the direction of the arrow in the figure), friction occurs on the contact surface between the test piece 10 and the mating member 7. The frictional force at this time is converted into a dynamic friction coefficient by the load cell 9. This dynamic friction coefficient was defined as “surface friction coefficient”. The smaller the surface friction coefficient, the higher the surface lubricity (the smaller the surface friction resistance).
In the measurement of the surface friction coefficient, the material of the mating material 7 is SUS, the size of the contact surface of the mating material 7 to the test piece 10 is 10 mm × 10 mm, the weight 8 (the load at the time of measurement) is 50 g, and the table 5 The moving speed was 100 mm / min.

The surface lubricity was evaluated from the above measurement results according to the following criteria.
(Judgment criteria)
A: Surface friction coefficient is less than 0.2.
○: The surface friction coefficient is 0.2 or more and less than 0.3.
X: Surface friction coefficient is 0.3 or more.

[Evaluation of migration]
The tube obtained by the evaluation of formability was cut from one place in the circumferential direction at one end to the other end along the length direction, spread from the cut portion, formed into a sheet, and fixed to a heat press machine. Hot pressing was performed under the conditions of 20 ° C. and 20 ° C. The obtained sheet was cut to obtain a sheet-like test piece of 30 mm × 30 mm × 1 mm.
Using the obtained test piece, the migration was measured by the procedure shown in FIGS. 3A and 3B. FIG. 3A is a top view for explaining the installation position of the test piece 14. FIG. 3B is a side view showing a state in which the test piece 14, the transferability confirmation sheets 11, 12 and the weight 13 are stacked.

First, the transferability confirmation sheet 11 was placed on a horizontal plane, and a test piece 14 was placed thereon as shown in FIG. 3A. On top of that, another sheet for confirming migration 12 and a weight 13 were sequentially placed to obtain the state shown in FIG. 3B. As the transferability confirmation sheets 11 and 12, a PET film was used, and the weight (load) of the weight 13 was 100 g.
After maintaining the state shown in FIG. 3B at 80 ° C. for 500 hours, it was visually observed whether or not the oil transfer marks 11 and 12 had oil marks, and the transferability was evaluated according to the following criteria.
(Judgment criteria)
◯: There was no oil mark on the transferability confirmation sheets 11 and 12.
X: Oil traces were found on the migration confirmation sheets 11 and 12.

<Examples 2 to 15 and Comparative Examples 1 to 7>
A kneaded material was prepared in the same manner as in Example 1 except that the type of thermoplastic resin and the type and blending amount of silicone oil were changed as shown in Tables 1 to 3, and evaluation of moldability, surface lubricity, and migration was performed. Went. The results are shown in Tables 1 to 3.

As shown in the above results, with respect to the thermoplastic resin 100 parts by mass, kinematic viscosity of 1000 mm ² / s or more 100,000 mm ² / s or less preferred silicone oil were added 50 parts by mass or less than 0.1 part by weight Examples 1-15 The kneaded product could be formed into a tube shape with good moldability. The obtained tube had a small surface friction coefficient and high surface lubricity as compared with Comparative Examples 5 to 7 in which no silicone oil was added. Moreover, the transfer to the PET film of silicone oil was not seen.

On the other hand, in Comparative Example 1 using a silicone oil having a kinematic viscosity of 10 mm ² / s, the silicone oil was transferred from the tube to the PET film.
In Comparative Example 2 using a silicone oil having a kinematic viscosity exceeding 1000000 mm ² / s, the moldability of the kneaded product was poor.
In Comparative Example 3 in which the addition amount of the silicone oil was 0.05 parts by mass with respect to 100 parts by mass of the thermoplastic resin, the effect of improving the surface lubricity of the tube was not so much seen.
In Comparative Example 4 in which the amount of silicone oil added was 70 parts by mass with respect to 100 parts by mass of the thermoplastic resin, the moldability of the kneaded product was poor. Moreover, the silicone oil moved from the tube to the PET film.

According to the medical tube material and the medical tube of the above-described embodiment, it is possible to provide a medical tube material and a medical tube that have low surface friction resistance, no bleeding problem, and good moldability.

DESCRIPTION OF SYMBOLS 1 Single-screw extruder 2 Tube die 3 Tube 4 Eye 5 A table 6 Reinforcement board 7 Counterpart material 8 Weight 9 Load cell 10 Test piece 11 Migration confirmation sheet 12 Migration confirmation sheet 13 Weight 14 Test piece

Claims (6)

1. It is made by melt-kneading a thermoplastic resin and silicone oil,
   Kinematic viscosity of the silicone oil is not more than 1000 mm ² / s or more 100,000 mm ² / s,
   A medical tube material in which the content of the silicone oil is 0.1 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.
2. The kinematic viscosity of the silicone oil is not more than 1000 mm ² / s or more 30,000 mm ² / s, the material for the medical tube of claim 1.
3. The medical tube material according to claim 1 or 2, wherein a content of the silicone oil is 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin.
4. The medical tube material according to any one of claims 1 to 3, wherein the silicone oil is at least one selected from the group consisting of dimethyl silicone oil, methylphenyl silicone oil, and fluoroalkyl silicone oil. .
5. The medical tube material according to any one of claims 1 to 4, wherein the thermoplastic resin is a polypropylene resin.
6. A medical tube obtained by molding the medical tube material according to any one of claims 1 to 5 into a tube shape.

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