JP5331393B2 - Composite materials and medical tubing - Google Patents

Description

  The present invention relates to a composite material and a medical tube.

Conventionally, a medical tube is used as, for example, a treatment instrument tube (sheath) that is inserted into a treatment portion in the body through a channel tube of an endoscope. Such a medical tube is required to reduce the amount of insertion force by reducing sliding resistance with respect to a channel tube of an endoscope, for example.
For example, Patent Document 1 discloses a composite material including a polymer matrix consisting essentially of one or more thermoplastic polyesters and a finely divided lubricating granular material, and a catheter in which an insertion tube member is formed in the body by the composite material. Have been described.
In Patent Document 1, for example, a finely pulverized lubricating granular material made of graphite, molybdenum disulfide, or the like is mixed with a polymer matrix made of thermoplastic polyester, thereby reducing the coefficient of friction of the material and improving the insertion property of the treatment instrument tube. ing.
Japanese National Patent Publication No. 10-503103

However, the conventional composite materials and medical tubes as described above have the following problems.
In the technique described in Patent Document 1, a composite material having a lower friction than that of a polymer matrix can be obtained by mixing finely pulverized lubricating granular materials. However, since the particle shape is not controlled, the reduction in the friction coefficient is limited. Is. And according to patent document 1, the friction coefficient of this composite material is about 0.03-about 0.20, and has a big dispersion | variation.
As described above, when the friction coefficient varies and the friction coefficient increases, there is a problem that the amount of insertion force when the medical tube is inserted varies.
Medical tubes need to be quickly inserted into the body, and even after insertion, the insertion position must be finely adjusted by the operator's operation according to the treatment position. ing.

  The present invention has been made in view of the above problems, and provides a composite material and a medical tube that can improve the frictional properties of the surface of a composite material in which inorganic particles are kneaded into a base matrix. Objective.

In order to solve the above problems, the composite material of the present invention has a base matrix composed of one or more polymer materials and a blending ratio of 15 parts by weight to 75 parts by weight with respect to 100 parts by weight of the base matrix. It is configured to include one or more kinds of inorganic particles kneaded and having an average particle diameter of 0.1 μm to 30 μm and a circularity of 0.90 to 1.0.
According to this invention, the blending ratio, average particle diameter, and circularity of the inorganic particles to be kneaded are respectively 15 parts by weight to 75 parts by weight, 0.1 μm to 30 μm, and the circularity 0.90 to 1.0. By setting the following conditions, the surface friction coefficient can be reduced.
If the blending ratio of the inorganic particles is less than 15 parts by weight, the blending amount is small and the number of inorganic particles near the surface of the base matrix and in the vicinity of the surface becomes excessively small, so that the surface friction coefficient as a composite material increases. Further, when the blending ratio of the inorganic particles exceeds 75 parts by weight, there are too many inorganic particles and aggregation easily occurs, thereby increasing the unevenness on the surface of the composite material, resulting in a rough surface. As a result, the surface friction coefficient increases.
In addition, when the average particle size of the inorganic particles is less than 0.1 μm, the surface energy of the inorganic particles becomes too large, so that even when kneaded, the inorganic particles tend to aggregate. In such a condensed portion, the mechanical strength is significantly reduced. In addition, when the average particle size of the inorganic particles exceeds 30 μm, the average particle size is large, so that the unevenness of the surface of the composite material becomes large and the surface becomes rough, so the surface friction coefficient as the composite material increases. End up.
Moreover, when the circularity of the inorganic particles is less than 0.90, the sharp corners on the surface of the inorganic particles are excessive. Since these sharp corners are exposed on the surface of the base matrix, the contact resistance is increased, so that the surface friction coefficient as a composite material is increased.
The circularity e referred to in this specification is measured using a flow type particle image analyzer (manufactured by Sysmex Corporation) and is defined as follows.

e = (circumference of a circle having the same area as that of the particle projection image) / (perimeter of the particle projection image)
... (1)

According to this flow type particle image analyzer, the area and circumference of the inorganic particles are obtained by acquiring an enlarged image of the inorganic particles and performing the image processing, and the circularity is calculated based on the above equation (1). Is done.
For example, the circularity of a perfect circle is 1. In the example of a regular polygon, the regular hexagon is 0.952, the regular pentagon is 0.930, the square is 0.886, and the regular triangle is 0.777.

In the composite member of the present invention, it is preferable that the inorganic particles have a crystal structure of a graphite type structure or a molybdenum sulfide type structure.
In this case, the inorganic particles have a crystal structure of a graphite type structure or a molybdenum sulfide type structure, and these crystal structures are layered crystal structures, so that the inorganic particles on the surface of the composite material are easily sheared by an external force. . Thereby, the slip property of the surface of a composite material can be improved.

In the composite member of the present invention, the inorganic particles include aluminum oxide (Al ₂ O ₃ ), barium sulfate (BaSO ₄ ), tungsten oxide (WO ₃ ), tungsten (W), bismuth oxide (BiO ₃ ), and It is preferably any of silicon carbide (SiC).
In this case, since Al ₂ O ₃ , BaSO ₄ , WO ₃ , W, BiO ₃ and SiC are chemically stable, the bonding force at the interface between the inorganic particles and the base matrix is small. If it receives, slip will generate | occur | produce with respect to a base matrix, and the slipperiness | lubricity of the surface of a composite material can be improved.

In the composite member of the present invention, it is preferable that the base matrix is blended with 2 to 10 parts by weight of a thermoplastic resin obtained by graft polymerization of silicone.
In this case, since the silicone having low friction property is included in the base matrix, the friction on the surface of the composite material can be reduced by the silicone appearing on the surface of the composite material.
If the thermoplastic resin obtained by graft polymerization of silicone is less than 2 parts by weight, the blending amount is too small, so that the silicone on the surface of the base matrix decreases and the surface of the composite material cannot be reduced in friction. In addition, if the thermoplastic resin obtained by graft polymerization of silicone exceeds 10 parts by weight, the dimensional stability is deteriorated when molding the composite material, so that unevenness is likely to occur on the surface, and the friction of the surface of the composite material. Can not be reduced.

In the composite member of the present invention, the base matrix preferably contains 1 part by weight or more and 20 parts by weight or less of the fatty acid amide in the 100 parts by weight.
In this case, since the base matrix contains a fatty acid amide having a low friction property because it is a semi-solid lipophilic substance, friction on the surface of the composite material can be reduced.
When the amount of the fatty acid amide is less than 1 part by weight, the amount of the fatty acid amide on the surface of the base matrix decreases because the blending amount is too small, and the surface of the composite material cannot be reduced in friction. On the other hand, when the fatty acid amide exceeds 20 parts by weight, the viscosity in the molten state is lowered when the composite material is molded, and the dimensional stability is deteriorated. For this reason, unevenness is likely to occur on the surface, and the friction on the surface of the composite material cannot be reduced.

The medical tube of the present invention has a configuration using the composite material of the present invention.
According to this invention, since the composite material of the present invention is used, the same action as that of the composite material of the present invention is provided.

  According to the composite material and the medical tube of the present invention, the composite material obtained by kneading the inorganic particles into the base matrix contains the inorganic particles having a good circularity, thereby improving the surface friction characteristics. Play.

  Embodiments of the present invention will be described below with reference to the accompanying drawings. In all the drawings, even if the embodiments are different, the same or corresponding members are denoted by the same reference numerals, and common description is omitted.

[First Embodiment]
First, the composite material and the medical tube according to the first embodiment of the present invention will be described.
FIG. 1 is a schematic cross-sectional view along the axial direction showing a schematic configuration of the medical tube according to the first embodiment of the present invention. FIG. 2 is a schematic cross-sectional view of the vicinity of the surface of the medical tube according to the first embodiment of the present invention. 1 and 2 are schematic diagrams, and the dimensional ratio, number, and shape are exaggerated (the same applies to the following drawings).

As shown in FIG. 1, the medical tube 1 of the present embodiment is a flexible tube in which a tube body is formed in a cylindrical shape having an inner diameter d ₁ , an outer diameter d ₂ , and a length L. It can be used for a catheter or the like that is inserted into a channel tube of an endoscope and assists in the treatment of the affected area or the extraction of the affected area. As the inner diameter d ₁ , the outer diameter d ₂ , and the length L, for example, dimensions such as d ₁ = 1.7 (mm), d ₂ = 2.4 (mm), and L = 2000 (mm) may be adopted. it can.
As shown in FIG. 2, the tube main body of the medical tube 1 is formed from the composite material 10 of the present embodiment in which inorganic particles 10B are kneaded with a base matrix 10A made of one or more polymer materials in the above-described tube shape. It is formed by molding.

Examples of the base matrix 10A include polyethylene (PE) resin, polypropylene (PP) resin, polyester resin, polyurethane (PUR) resin, ethylene-vinyl acetate copolymer resin, ethylene-ethyl acrylate copolymer resin, styrene-butadiene. One selected from copolymer resins, various diene resins, fluorine resins (for example, perfluoroalkoxyalkane (PFA), ethylene-tetrafluoroethylene copolymer (ETFE), etc.), polyamide (PA) resins, or Two or more combinations can be employed.
As an example, the base matrix 10A of the present embodiment employs Pebax (registered trademark) 6333SN01 (manufactured by Arkema). This Pebax (registered trademark) 6333 is a polyether block amide copolymer having a hard segment made of PA and a soft segment made of polyether, and is a thermoplastic PA-based elastomer having high flexibility and rebound resilience. .

As the inorganic particles 10B, particles having an average particle size of 0.1 μm or more and 30 μm or less and a circularity of 0.90 or more and 1.0 or less are 15 parts by weight or more and 75 parts by weight or less with respect to 100 parts by weight of the base matrix 10A. Kneading at a blending ratio.
As the material of the inorganic particles 10B, appropriate inorganic particles having a layered crystal structure can be employed. Examples of such a layered crystal structure include a graphite type structure and a molybdenum sulfide type structure, and it is preferable to include one or more kinds of inorganic particles having these layered crystal structures.
Examples of the substance having a graphite type structure include graphite (C), boron nitride (BN), magnesium boride (MgB), magnesium diboride (MgB ₂ ), LiBC, HBC, C ₆ B _{2 and the} like. Can do.
Examples of the substance having a molybdenum sulfide type structure include tungsten disulfide (WS ₂ ), molybdenum disulfide (MoS ₂ ), and tantalum disulfide (TaS ₂ ).
As an example, the material of the inorganic particles 10B of the present embodiment employs MoS ₂ .

According to the medical tube 1 having such a configuration, the composite material 10 in which the base matrix 10A is kneaded with a blending ratio of 15 parts by weight to 75 parts by weight with respect to 100 parts by weight of the base matrix 10A is molded. Therefore, the inorganic particles 10B are dispersed inside the medical tube 1, and a part of the inorganic particles 10B is exposed to the outer surface 1a as shown in FIG. Further, although not particularly illustrated, the inorganic particles 10B are exposed on the inner surface 1b as well. In the following description, the outer surface 1a and the inner surface 1b indicate surfaces including the inorganic particles 10B exposed on the surface of the base matrix 10A.
Thus, when the medical tube 1 is inserted into, for example, an endoscope channel tube or a wire is inserted into the medical tube 1, the inner surface of the channel tube, the wire surface, the outer surface 1a, Since the inorganic particles 10B dispersed and exposed on the inner surface 1b are in contact with each other and slip, the surface friction coefficient of the medical tube 1 can be reduced.
In addition, since the inorganic particles 10B have an average particle size of 0.1 μm or more and 30 μm or less and a size and shape with a circularity of 0.90 or more and 1.0 or less, even if the inorganic particles 10B are exposed. Since the outer surface 1a and the inner surface 1b are kept in a fine uneven state, smooth contact is possible, and the surface friction coefficient as the medical tube 1 can be reduced.
Moreover, since the material of the inorganic particle 10B has MoS ₂ having a graphite-type structure which is a layered crystal structure, shear slip occurs in the inorganic particle 10B when stress is applied from the contact object. Therefore, the frictional force at the contact portion is reduced as compared with the same shape of inorganic particles in which no shear slip occurs.

When the blending ratio of the inorganic particles 10B is less than 15 parts by weight, the blending amount is small, so that the inorganic particles 10B exposed to the outer surface 1a and the inner surface 1b become too small, and the friction coefficient on the outer surface 1a and the inner surface 1b The friction coefficient of the material of 10A is almost determined. For this reason, the surface friction coefficient of the medical tube 1 cannot be reduced so much from the friction coefficient determined by the material of the base matrix 10A.
When the blending ratio of the inorganic particles 10B exceeds 75 parts by weight, the inorganic material 10B is too much in the composite material 10, and aggregation is likely to occur between the inorganic particles 10B, and the inorganic exposed to the outer surface 1a and the inner surface 1b. The apparent particle diameter of the particle 10B increases. For this reason, the unevenness | corrugation of the outer surface 1a and the inner surface 1b increases, and since the outer surface 1a and the inner surface 1b will be in the rough state, the surface friction coefficient as the medical tube 1 will become large.

When the average particle diameter of the inorganic particles 10B is less than 0.1 μm, the surface energy of the inorganic particles becomes too large, and thus the inorganic particles tend to be aggregated even when kneaded. In such a condensed portion, the mechanical strength is significantly reduced. In addition, when the average particle size of the inorganic particles 10B exceeds 30 μm, the average particle size is large, so that the irregularities on the outer surface 1a and the inner surface 1b become large, and the outer surface 1a and the inner surface 1b become rough. The coefficient of friction will increase.
Moreover, when the circularity of the inorganic particles 10B is less than 0.90, the sharp corners on the surface of the inorganic particles 10B are excessive. Since these sharp corners are exposed on the outer surface 1a and the inner surface 1b, the contact resistance is increased, so that the surface friction coefficient is increased.
Here, the circularity is an evaluation scale of the degree of roundness of the particle, and means the circularity e calculated from the above formula (1).

  Thus, since the composite material 10 of this embodiment has improved surface friction characteristics, the surface friction coefficient of the outer surface 1a and the inner surface 1b of the medical tube 1 using the composite material 10 is reduced. Thus, when the medical tube 1 is inserted into the endoscope channel tube or a wire is inserted into the medical tube 1, it is possible to reduce the force at the time of insertion and insertion.

[Second Embodiment]
Next, a medical tube according to a second embodiment of the present invention will be described.
FIG. 3 is a schematic cross-sectional view of the vicinity of the surface of the medical tube according to the second embodiment of the present invention.

The medical tube 1A of the present embodiment has the same shape as the medical tube 1 of the first embodiment, and the tube body is formed using the composite material 11 instead of the composite material 10. .
As shown in FIG. 3, the composite material 11 is obtained by kneading inorganic particles 11B in a base matrix 11A made of one or more polymer materials.
Hereinafter, a description will be given centering on differences from the first embodiment.

As the material of the base matrix 11A, any material that can be used for the base matrix 10A of the first embodiment can be used. In the present embodiment, a matrix resin 11a made of PE resin in which high density polyethylene (HDPE) and linear low density polyethylene (LLDPE) are blended at a blending ratio of 90/10 and silicone 11c are graft polymerized. What consists of the thermoplastic resin 11b is employ | adopted.
The blending ratio of the thermoplastic resin 11b is 2 parts by weight or more and 10 parts by weight or less in 100 parts by weight of the base matrix 11A.
As an example of such a base matrix 11A, for example, HDPE is HB130R (trade name; manufactured by Nippon Polyethylene Co., Ltd.), and LLDPE is UE320 (trade name; manufactured by Nippon Polyethylene Co., Ltd.), a matrix resin 11a, and silicone 11c. As the thermoplastic resin 11b obtained by graft polymerization, a constitution of BY27-202H (trade name; manufactured by Toray Dow Corning Co., Ltd.) obtained by graft polymerization of silicone on low density polyethylene (LDPE) can be employed. .

  However, the thermoplastic resin 11b is not limited to the olefin resin as described above, and any resin can be used as long as it is a thermoplastic resin that can be employed in the base matrix 10A exemplified in the first embodiment. Also good.

Similar to the inorganic particles 10B of the first embodiment, the inorganic particles 11B have an average particle size of 0.1 μm to 30 μm and a circularity of 0.90 to 1.0, and the base matrix 10A is 100 wt. Kneading at a blending ratio of 15 parts by weight or more and 75 parts by weight or less with respect to parts.
In addition, as the material of the inorganic particles 11B, any material that can be used for the inorganic particles 10B of the first embodiment can be similarly used.
In the present embodiment, as an example, BN having a graphite type crystal structure is employed.

According to the medical tube 1A having such a configuration, the composite material 11 in which the base matrix 11A is kneaded at a blending ratio of 15 parts by weight to 75 parts by weight with respect to 100 parts by weight of the base matrix 11A is molded. Therefore, as in the first embodiment, the surface friction coefficient as the medical tube 1A can be reduced.
Furthermore, in the medical tube 1A of the present embodiment, the base matrix 11A is blended with 2 parts by weight or more and 10 parts by weight or less of the thermoplastic resin 11b obtained by graft polymerization of the silicone 11c, so that the base matrix 11A has low friction. And the silicone 11c is exposed on the outer surface 1a and the inner surface 1b. This also reduces the surface friction coefficient of the base matrix 11A of the outer surface 1a and the inner surface 1b of the medical tube 1A. As a result, the friction characteristics are further improved in combination with the improvement of the friction characteristics by the inorganic particles 11B.

  When the thermoplastic resin 11b is less than 2 parts by weight, the blending amount is too small, and the silicone 11c on the outer surface 1a and the inner surface 1b is reduced, and the surface of the composite material 11 cannot be reduced in friction. Further, if the thermoplastic resin 11b exceeds 10 parts by weight, the dimensional stability is deteriorated when the composite material 11 is molded, so that irregularities are likely to occur on the outer surface 1a and the inner surface 1b, and the outer surface 1a and inner The friction of the surface 1b cannot be reduced.

[Third Embodiment]
Next, a medical tube according to a third embodiment of the present invention will be described.
FIG. 4 is a schematic cross-sectional view of the vicinity of the surface of the medical tube according to the third embodiment of the present invention.

The medical tube 1 </ b> B of the present embodiment has the same shape as the medical tube 1 of the first embodiment, and the tube body is formed using the composite material 12 instead of the composite material 10. .
As shown in FIG. 4, the composite material 12 is obtained by kneading inorganic particles 11B in a base matrix 12A made of one or more polymer materials.
The following description will focus on differences from the first and second embodiments.

The base matrix 12A is formed by blending a fatty acid amide 12b, which is a semisolid lipophilic substance, with the matrix resin 11a of the second embodiment.
The compounding ratio of the fatty acid amide 12b is 1 part by weight or more and 20 parts by weight or less in 100 parts by weight of the base matrix 12A.
As an example of such fatty acid amide 12b, Kao wax 85P (trade name; manufactured by Kao Corporation) can be employed.

According to the medical tube 1B having such a configuration, the composite material 12 in which the inorganic particles 11B are kneaded at a blending ratio of 15 parts by weight to 75 parts by weight with respect to 100 parts by weight of the base matrix 12A is molded. Therefore, as in the first embodiment, the surface friction coefficient as the medical tube 1B can be reduced.
Furthermore, in the medical tube 1B of the present embodiment, the base matrix 12A is blended with 1 to 20 parts by weight of the fatty acid amide 12b having low friction because it is a semi-solid lipophilic substance. The fatty acid amide 12b is exposed on the outer surface 1a and the inner surface 1b. This also reduces the surface friction coefficient of the base matrix 12A of the outer surface 1a and the inner surface 1b of the medical tube 1B. As a result, the friction characteristics are further improved in combination with the improvement of the friction characteristics by the inorganic particles 11B.

  If the fatty acid amide 12b is less than 1 part by weight, the blending amount is too small, and the fatty acid amide 12b on the outer surfaces 1a and 1b decreases, and the surface of the composite material 12 cannot be reduced in friction. On the other hand, when the fatty acid amide 12b exceeds 20 parts by weight, the viscosity in the molten state is lowered when the composite material 12 is molded, so that the dimensional stability is deteriorated. For this reason, irregularities are likely to occur on the outer surface 1a and the inner surface 1b, and friction cannot be reduced on the outer surface 1a and the inner surface 1b.

[Fourth Embodiment]
Next, a medical tube according to a fourth embodiment of the present invention will be described.
The medical tube 1C of the present embodiment has the same shape as the medical tube 1 of the first embodiment, and the tube main body is formed using the composite material 13 instead of the composite material 10. .
As shown in FIG. 2, the composite material 13 uses inorganic particles 13B instead of the inorganic particles 10B of the composite material 10 of the first embodiment.
Hereinafter, a description will be given centering on differences from the first embodiment.

As the inorganic particles 13B, particles having an average particle size of 0.1 μm or more and 30 μm or less and a circularity of 0.90 or more and 1.0 or less are 15 to 75 parts by weight with respect to 100 parts by weight of the base matrix 10A. Kneading at a blending ratio.
The material of the inorganic particles 13B includes one or more inorganic particles of aluminum oxide (Al ₂ O ₃ ), barium sulfate (BaSO ₄ ), tungsten oxide (WO ₃ ), tungsten (W), and bismuth oxide (BiO ₃ ). Things can be adopted.

According to the medical tube 1C having such a configuration, the composite material 13 in which the base matrix 10A is kneaded at a blending ratio of 15 parts by weight or more and 75 parts by weight or less with respect to 100 parts by weight of the base matrix 10A is formed. Therefore, similarly to the first embodiment, the inorganic particles 13B are exposed on the outer surface 1a and the inner surface 1b of the medical tube 1C.
Since such inorganic particles 13B are chemically stable, the bonding force at the interface with the base matrix 10A is small, and the outer surface 1a and the inner surface 13B are exposed to the inorganic particles 13B exposed on the outer surface 1a and the inner surface 1b. When an external force along the surface 1b is applied, the inorganic particles 13B slip with respect to the base matrix 10A. As a result, the friction characteristics of the outer surface 1a and the inner surface 1b are improved.

Below, the Example of each said embodiment is described with a comparative example.
FIG. 5 is a schematic explanatory view for explaining a measuring apparatus and a measuring method used for measuring the surface friction coefficient of the composite material. FIG. 6 is a schematic explanatory diagram for explaining a measuring device and a measuring method for the amount of insertion force of a medical tube. FIG. 7 is a bar graph showing the measurement results of the surface friction coefficient and insertion force amount of each example and each comparative example. The horizontal axis indicates the numbers of the example and the comparative example as actual 1, ratio 1, etc., respectively. The vertical axis represents the surface friction coefficient and the amount of insertion force (N).

[Examples 1 to 7 of the first embodiment]
Table 1 shows the configurations of the base matrix 10A and the inorganic particles 10B of the medical tubes 1 of Examples 1 to 7 of the first embodiment, together with the configurations of the base matrix and inorganic particles of the medical tubes of Comparative Examples 1 to 6. Show.
The manufactured medical tubes have the same shape, and the inner diameter d ₁ , the outer diameter d ₂ , and the length L are d ₁ = 1.7 (mm) and d ₂ = 2.4 (mm), respectively. L = 2000 (mm) (common to the following examples and comparative examples).

As shown in Table 1, Examples 1 to 7 all employ Pebax (registered trademark) 6333SN01 (manufactured by Arkema) for the base matrix 10A (resin 1) and MoS ₂ for the inorganic particles 10B. .
In Examples 1 to 3, the blending ratio of the inorganic particles 10B with respect to 100 parts by weight of the base matrix 10A was 15 parts by weight, and the circularity of the inorganic particles 10B was 0.90. However, the average particle diameter of the inorganic particles 10B was set to 0.10 μm, 20 μm, and 30 μm in Examples 1, 2, and 3, respectively.
In Examples 4 and 5, the blending ratio of the inorganic particles 10B with respect to 100 parts by weight of the base matrix 10A was 15 parts by weight, and the average particle diameter of the inorganic particles 10B was 30 μm. However, the circularity of the inorganic particles 10B was 1.00 and 0.95, respectively.
In Example 6, the compounding ratio of the inorganic particles 10B with respect to 100 parts by weight of the base matrix 10A was 40 parts by weight, and the average particle diameter and circularity of the inorganic particles 10B were 30 μm and 0.90, respectively.
In Example 7, the blending ratio of the inorganic particles 10B with respect to 100 parts by weight of the base matrix 10A was 75 parts by weight, and the average particle diameter and circularity of the inorganic particles 10B were 30 μm and 0.90, respectively.

  Here, the value measured by the particle size distribution analyzer SALD-7100 (made by Shimadzu Corporation) was adopted as the average particle size. Moreover, the value measured using the flow type particle image analyzer (made by Sysmex Corporation) was employ | adopted for circularity. The measurement method of the average particle diameter and the circularity is common to the other examples and comparative examples.

In Comparative Example 1, the tube main body is formed using only the base matrix 10A.
In Comparative Examples 2 to 4, the blending ratio of the inorganic particles 10B with respect to 100 parts by weight of the base matrix 10A was 15 parts by weight in common. However, the average particle diameter of the inorganic particles 10B was 50 μm, 0.05 μm, and 30 μm in Comparative Examples 2, 3, and 4, respectively. In addition, the circularity of the inorganic particles 10B was set to 0.90, 0.90, and 0.80 in Comparative Examples 2, 3, and 4, respectively.
In Comparative Example 5, the blending ratio of the inorganic particles 10B with respect to 100 parts by weight of the base matrix 10A was 5 parts by weight, and the average particle size and circularity of the inorganic particles 10B were 30 μm and 0.90, respectively.
In Comparative Example 6, the blending ratio of the inorganic particles 10B with respect to 100 parts by weight of the base matrix 10A was 90 parts by weight, and the average particle diameter and circularity of the inorganic particles 10B were 10 μm and 0.90, respectively.
That is, Comparative Example 1 does not include the inorganic particles 10B, Comparative Examples 2 and 3 are the average particle size of the inorganic particles 10B, and Comparative Example 4 is the circularity of the inorganic particles 10B. Thus, Comparative Examples 5 and 6 are examples that are not included in the scope of the present invention in terms of the blending ratio of the inorganic particles 10B.

  Each of these Examples and Comparative Examples was evaluated by measuring the surface friction coefficient of the composite material and the amount of insertion force when inserting the tube body formed of each composite material into the bent tube. These measurement methods are the same in the following other examples and comparative examples.

As shown in FIG. 5, the surface friction coefficient is measured by a moving base 51 that reciprocates with the measurement sample fixed, a weight 52 for pressing the measurement counterpart member 52 with a constant load against the measurement sample, The measurement was performed using a friction coefficient measuring device 50 including a load converter 54 that measures a friction force from a measurement sample acting on the mating member 52. HEIDON (trade name; manufactured by Shinto Kagaku Co., Ltd.) was used as the friction coefficient measuring device 50 in this measurement.
In this measurement, the sample base 60 manufactured from the composite material is fixed to the moving base 51, and the moving base 51 is driven to reciprocate in a state where the measurement counterpart member 52 is pressed against the sample base 60 by the weight 52. The load converter 54 measures the frictional force acting on the measurement counterpart member 52 from the sample base material 60. The dynamic friction coefficient was calculated from the change in the friction force, and the surface friction coefficient of the sample base material 60 was evaluated.
Here, the material of the measurement counterpart member 52 is PTFE (polytetrafluoroethylene).

A stress measuring device 70 shown in FIG. 6 was used for measuring the amount of insertion force.
The stress measuring device 70 includes a channel tube 74 made of cylindrical PTFE having an inner diameter of 3.2 mm, an outer diameter of 4.4 mm, and a length of 400 mm, which is fitted into a channel guide 75 having a bent shape. A stress sensing measuring device 78 having a tube fixing metal rod 77 for pushing out a measurement sample S of a medical tube is disposed.
Here, the channel tube 74 is actually used in an endoscope.
The channel guide 75 has a pipe diameter of 5 mm, and includes a straight portion 75a, a curved portion 75b, and a straight portion 75c having a length of 125 mm from the entrance side. The curvature radius (R in FIG. 6) outside the curved portion 75b is 50 mm, and the length of this curved portion is 39.25 mm. As a result, the straight portions 75a and 75c are bent 90 ° within the drawing sheet.

First, as the measurement sample S, the medical tube of each example and each comparative example was cut and the length was adjusted to 400 mm. Then, the rear end side of the measurement sample S is fixed to the front end of the tube fixing metal rod 77, inserted into the channel tube 74, and set at the tube installation position 76 that is inserted by 20 mm from the inlet of the linear portion 75a in the initial state. .
From this state, the measurement sample S is repeatedly inserted 10 times into the channel tube 74 at a moving stroke of 300 mm and a moving speed of 50 mm / sec.
When the measurement sample S advances into the channel tube 74, an insertion resistance is generated due to the tip Sa contacting the inner wall of the channel tube 74 positioned at the curved portion 5b of the channel guide 75, for example.
Then, the maximum insertion force in this repeated insertion was detected by a stress sensing measuring device 78 to which the tube fixing metal rod 77 was connected, and the average value of 10 times was taken as the amount of insertion force.

These measurement results and determination results are shown in Table 1 and FIG. The determination of the surface friction coefficient is in the range of 0 to 0.13, and the determination of the insertion force amount is in the range of 0N to 0.45N. The results are ○ (good) and × (outside the allowable range). (The following table is the same).
In the following, the surface friction coefficient may be represented by the symbol μ _sf , the insertion force amount may be represented by the symbol F _f , and the measured value may be represented by (μ _sf , F _f ). For example, (0.06, 0.30 N) means μ _sf = 0.06 and F _f = 0.30 (N).

According to Table 1, the maximum values of μ _sf and F _f were (0.33, 0.78 N) in the case of Comparative Example 1.
The measurement results of Examples 1 to 3 were (0.06, 0.30N), (0.07, 0.33N), and (0.08, 0.34N). In Examples 1 to 3, since the average particle size was changed from 0.10 μm to 30 μm with the minimum blending ratio (15 parts by weight) and the minimum circularity (0.90) of the inorganic particles 10B, μ _sf , Both F _f increased with an increase in the average particle diameter, but in Example 3 at the maximum, μ _sf was about 0.24 times and F _f was about 0.44 times that of Comparative Example 1. .
The measurement results of Examples 4 and 5 were (0.05, 0.28N) and (0.07, 0.32N). In Examples 4 and 5, the minimum blending ratio (15 parts by weight) of the inorganic particles 10B and the maximum average particle size (30 μm) were used, and the circularity was changed to 1.00 and 0.95. When combined with the results of Example 3, it is a measurement example when the circularity is increased from 0.90 to 1.00 in the order of Examples 3, 5, and 4. From these measurement results, the circularity is It can be seen that μ _sf and F _f decrease with increase. That is, in these three examples, μ _sf and F _{f of} Example 3 are the largest.
The measurement results of Examples 6 and 7 were (0.07, 0.33N) and (0.10, 0.39N). In Examples 6 and 7, the inorganic particles 10B have the minimum circularity (0.90) and the maximum average particle size (30 μm), and the blending ratio is changed to 40 parts by weight and 70 parts by weight. When combined with the results of Example 3, it is a measurement example when the blending ratio is increased from 15 parts by weight to 75 parts by weight in the order of Examples 3, 6, and 7. From these measurement results, inorganic particles 10B are obtained. In Example 7, where the blending ratio of _sf is the largest, μ _sf and F _f are maximized. Moreover, although Example 7 was the largest in Examples 1-7, compared with the comparative example 1, ( _{micro | micron |} mu) _sf was about 0.30 time and _Ff was about 0.5 times.
The measurement results of Examples 1 to 7 were all good results within the allowable range.
Further, the variation of μ _sf in Examples 1 to 7 is as extremely small as 0.05 (= 0.10−0.05).

Moreover, the measurement results of Comparative Examples 2 and 3 were (0.30, 0.75N) and (0.25, 0.71N). Comparative Examples 2 and 3 are examples in which the minimum blending ratio (15 parts by weight) and the minimum circularity (0.90) of the inorganic particles 10B are 50 μm and 0.05 μm, respectively. These measurement results show that μ _sf is about 3.8 times and about 3.1 times, and F _f is about 2.2 times and about 2.1 times, respectively, with respect to Example 3. That is, even if the average particle size is larger than 30 μm or smaller than 0.10 μm, μ _sf and F _f are remarkably increased and are outside the allowable range. Moreover, the value close | similar to the comparative example 1 which is not mix | blending the inorganic particle 10B is shown rather than Examples 1-3, and it turns out that the reduction effect of frictional force is scarce.
Comparative Examples 4 and 5 are examples in which the degree of circularity and the blending ratio were 0.80 and 5 parts by weight, respectively, and Comparative Example 6 was 10 μm and 90 μm in average particle diameter and blending ratio, respectively. It is an example at the time of setting it as a weight part. The measurement results of Comparative Examples 4 to 6 were (0.26, 0.72N), (0.27, 0.74N), and (0.25, 0.72N). Since any of the average particle diameter, the circularity, and the blending ratio of the inorganic particles 10B is outside the scope of the present invention, μ _sf is about 2.5 times and about 2.5 times that of Example 7, respectively. 2.7 times, about 2.5 times, and F _f are about 1.8 times, about 1.9 times, and about 1.8 times, which are out of the allowable range.

[Examples 8 to 10 of the second embodiment]
Table 2 shows the configurations of the base matrix 11A and the inorganic particles 11B of the medical tubes 1A of Examples 8 to 10 of the second embodiment, along with the configurations of the base matrix and inorganic particles of the medical tubes of Comparative Examples 7 and 8. Show.

As shown in Table 2, Examples 8 to 10 and Comparative Examples 7 and 8 are all made of matrix resin 11a, HB130R (trade name; manufactured by Nippon Polyethylene Co., Ltd.), UE320 (trade name; Nippon Polyethylene Co., Ltd.). Made by blending at a ratio of 90/10 to the thermoplastic resin 11b (resin 2) obtained by graft polymerization of silicone 11c using BY27-202H (trade name; manufactured by Toray Dow Corning Co., Ltd.) Yes. In addition, the inorganic particles 11B were made of BN, the average particle size was 30 μm, the circularity was 0.90, and the blending ratio with respect to 100 parts by weight of the base matrix 11A was 15 parts by weight.
The blending ratios of the silicone 11c and the thermoplastic resin 11b in the base matrix 11A in Comparative Example 7, Examples 8, 9, 10 and Comparative Example 8 are 1 part by weight, 2 parts by weight, 5 parts by weight, 10 parts, respectively. The weight was changed to 15 parts by weight.

These measurement results and determination results are shown in Table 2 and FIG.
According to Table 2, the measurement results of Comparative Example 7, Examples 8, 9, 10, and Comparative Example 8 were (0.16, 0.53N), (0.07, 0.28N), and (0. 05, 0.26N), (0.08, 0.36N), and (0.17, 0.58N).
From the measurement results of Examples 8 to 10, it is understood that when the thermoplastic resin 11b is 2 parts by weight or more and 10 parts by weight or less, both μ _sf and F _f are determined to be good. Further, even if the conditions other than the material of the inorganic particles are the same as those of the measurement result of Example 3, the result is substantially the same or better.
Further, the variation of μ _sf in Examples 8 to 10 is as extremely small as 0.03 (= 0.08−0.05).
Moreover, from the measurement results of Comparative Examples 7 and 8, it can be seen that when the blending ratio of the thermoplastic resin 11b is less than 2 parts by weight and more than 10 parts by weight, it is outside the allowable range. In Comparative Examples 7 and 8, compared to Example 10 in which the maximum measurement result is obtained among Examples 8 to 10, μ _sf is about twice, about 2.1 times, and F _f is about 1. It is 5 times and about 1.6 times, which is a marked increase, and it can be seen that the measurement result of Comparative Example 1 is closer.

[Examples 11 to 13 of the third embodiment]
The structures of the base matrix 12A and the inorganic particles 11B of the medical tube 1B of Examples 11 to 13 of the third embodiment are shown in Table 3 together with the structure of the base matrix and the inorganic particles of the medical tube of Comparative Example 9.

As shown in Table 3, in Examples 11 to 13 and Comparative Example 9, both HB130R (trade name; manufactured by Nippon Polyethylene Co., Ltd.), UE320 (trade name; manufactured by Nippon Polyethylene Co., Ltd.) are used in the matrix resin 11a. Kao wax 85P (trade name; manufactured by Kao Corporation) is used for the fatty acid amide 12b (resin 2). The inorganic particles 11B have a material of BN, an average particle size of 30 μm, a circularity of 0.90, and a blending ratio of 15 parts by weight with respect to 100 parts by weight of the base matrix 12A.
And the compounding ratio of the fatty acid amide 12b in the base matrix 12A in Examples 11, 12, 13 and Comparative Example 9 was changed to 1 part by weight, 15 parts by weight, 20 parts by weight and 30 parts by weight, respectively.

These measurement results and determination results are shown in Table 3 and FIG.
According to Table 3, the measurement results of Examples 11, 12, and 13 and Comparative Example 9 were (0.07, 0.27N), (0.06, 0.26N), and (0.09, 0. 37N) and (0.20, 0.62N).
From the measurement results of Examples 11 to 13, it can be seen that when the fatty acid amide 12b is 1 part by weight or more and 20 parts by weight or less, both μ _sf and F _f are determined to be good. Further, even if the conditions other than the material of the inorganic particles are the same as those of the measurement result of Example 3, the result is substantially the same or better.
Moreover, the variation of μ _sf in Examples 11 to 13 is as extremely small as 0.03 (= 0.09−0.06).
Moreover, from the measurement result of Comparative Example 9, it can be seen that when the blending ratio of the thermoplastic resin 11b exceeds 20 parts by weight, it is outside the allowable range. In Comparative Example 9, μ _sf is about 2.2 times and F _f is about 1.7 times that of Example 13 in which the maximum measurement result is obtained among Examples 11 to 13, and the increase is markedly increased. It can be seen that the measurement result of Comparative Example 1 is closer.

[Examples 14 to 19 of the fourth embodiment]
Table 4 shows the configurations of the base matrix 10A and the inorganic particles 13B of the medical tubes 1C of Examples 14 to 19 of the fourth embodiment.

As shown in Table 4, in each of Examples 14 to 19, Pebax (registered trademark) 6333SN01 (manufactured by Arkema) was adopted as the base matrix 10A (resin 1). The inorganic particles 13B had an average particle size of 30 μm, a circularity of 0.90, and a blending ratio of 100 parts by weight of the base matrix 10A to 15 parts by weight.
The materials of the inorganic particles 13B in Examples 14, 15, and 16 were Al ₂ O ₃ , BaSO ₄ , SiC, WO ₃ , W, and BiO ₃ , respectively.

These measurement results and determination results are shown in Table 4 and FIG.
According to Table 4, the measurement results of Examples 14, 15, 16, 17, 18, and 19 were (0.11, 0.42N), (0.10, 0.40N), (0.12, 0.43N), (0.11, 0.41N), (0.13, 0.45N), and (0.12, 0.42N).
Although it was slightly larger than the measurement results of Examples 14 to 19, it was a good result within the allowable range.
In addition, the variation of μ _sf in Examples 14 to 19 is as extremely small as 0.02 (= 0.12-0.10).
Also, compared to Comparative Example 1, μ _sf is about 0.33 times, about 0.30 times, about 0.36 times, about 0.33 times, about 0.39 times, about 0.36 times, F It can be seen that _f is about 0.53 times, about 0.51 times, about 0.55 times, about 0.53 times, about 0.58 times, and about 0.54 times, which are markedly reduced.

  It should be noted that all the components described in the above embodiments can be implemented in appropriate combination within the scope of the technical idea of the present invention.

It is typical sectional drawing which follows the axial direction which shows schematic structure of the medical tube which concerns on the 1st Embodiment of this invention. It is typical sectional drawing of the surface vicinity of the medical tube which concerns on the 1st Embodiment of this invention. It is typical sectional drawing of the surface vicinity of the medical tube which concerns on the 2nd Embodiment of this invention. It is typical sectional drawing of the surface vicinity of the medical tube which concerns on the 3rd Embodiment of this invention. It is a schematic explanatory drawing explaining the measuring apparatus and measuring method which were used for the surface friction coefficient measurement of a composite material. It is a schematic explanatory drawing explaining the measuring apparatus and measuring method of the amount of insertion force of a medical tube. It is a bar graph which shows the measurement result of the surface friction coefficient of each Example and each comparative example, and insertion force amount.

Explanation of symbols

1, 1A, 1B, 1C Medical tube 1a Outer surface 1b Inner surface 10, 11, 12, 13 Composite material 10A, 11A, 12A Base matrix 10B, 11B, 13B Inorganic particles 11a Matrix resin 11b Thermoplastic resin 11c Silicone 12b Fatty acid Amide

Claims (6)

A base matrix made of one or more polymer materials;
One or more types having an average particle size of 0.1 μm or more and 30 μm or less and a circularity of 0.90 or more and 1.0 or less kneaded at a blending ratio of 15 parts by weight or more and 75 parts by weight or less with respect to 100 parts by weight of the base matrix A composite material characterized by containing inorganic particles.   2. The composite material according to claim 1, wherein the inorganic particles have a crystal structure of a graphite type structure or a molybdenum sulfide type structure. The inorganic particles are any one of aluminum oxide (Al ₂ O ₃ ), barium sulfate (BaSO ₄ ), tungsten oxide (WO ₃ ), tungsten (W), bismuth oxide (BiO ₃ ), and silicon carbide (SiC). 2. The composite material according to claim 1, wherein the composite material is provided.   The thermoplastic resin obtained by graft polymerization of silicone in the base matrix is blended in an amount of 2 to 10 parts by weight of the 100 parts by weight. Composite material.   The composite material according to claim 1, wherein the base matrix contains 1 to 20 parts by weight of a fatty acid amide in the 100 parts by weight.   The medical tube using the composite material in any one of Claims 1-5.

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