# Patent

## Title
Heat-shrinkable tube having tearability

## Abstract

The present disclosure relates to a heat-shrinkable tube having tearability, which is made of a fluororesin, and particularly, to a heat-shrinkable tube having excellent tear straightness. Further, the present disclosure relates to a tube having high heat-shrinkage rate at low temperature. A tube including at least a fluororesin as a base resin, in which the thickness of the entanglement unit of a polymer observed on a cross-section in a longitudinal direction of the tube after being shrunk at 200° C. by 35% or more is 1 μm to 9 μm, has excellent tear straightness.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to Japanese Patent Application Nos. 2015-30043, 2015-23727, 2015-37064, 2015-50164, and 2015-52533, filed Feb. 1, 2015, Feb. 9, 2015, Feb. 26, 2015, Mar. 13, 2015, and Mar. 16, 2015, respectively, the disclosures of which are hereby incorporated in their entirety by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present disclosure relates to a heat-shrinkable tube having tearability, which is made of a fluororesin, and particularly to a tearable tube having heat-shrinkability, in which a material for the tube is composed of a thermoplastic fluororesin.
2. Background Art
Tubes having tearability have been used as a protective member until various articles came into use. Among them, tearable tubes made of a fluororesin have characteristics of the fluororesin such as heat resistance, chemical resistance, water and oil repellency, non-adherence, and self-lubricity, which may not be obtained by using tearable tubes made of a hydrocarbon-based synthetic resin. With these characteristics, the tearable tubes are used as protective tubes for precision instrument and electronic parts, or tubes for medical device introduction for introducing a catheter, a guide wire, and the like into the body, and assembly jigs such as a catheter, and when the tubes are no longer necessary, the tubes can be torn and removed. In particular, tearable tubes having heat-shrinkability enable internal articles to be securely protected, but the heat-shrinkage rate needs to be high in order to sufficiently adhere a heat-shrinkable tube to the internal articles. Further, the tubes are required to be easily torn without using a special instrument. Tearable tubes in the related art are provided with a cut on the surface in a longitudinal direction throughout the full length thereof, and are not easily torn at all.
International Publication No. WO2013/077452 suggests a tube which can be torn without requiring an excessive cut and has high heat-shrinkage rate. However, when the diameter of a tube to be needed is narrowed depending on the use, there is a problem in that the tear straightness becomes insufficient. When the diameter of the tube is narrow, it is difficult to uniformly apply force which cuts open (tears) the tube in a lateral direction to the tube. Even when tear force is non-uniformly applied, excellent tear straightness is needed in order to surely tear the tube throughout the full length thereof. In addition, when the tube is used as an assembly jig such as a catheter, high heat-shrinkability is required in addition to tear straightness, and simultaneously, since the tube affects the dimensional accuracy of a completely assembled catheter, dimensional accuracy when the tube is shrunk is required. Errors of several percentages (%) in both internal diameter and length when the tube is shrunk are significantly problematic.
PRIOR ART DOCUMENT
Patent Document
[Patent Document 1] International Publication No. WP2013/077452
SUMMARY OF THE INVENTION
Technical Problem to be Solved
In consideration of the above problems, an object of the present disclosure is to provide a tube which has a heat-shrinkability of 35% or more (more preferably 40% or more, even more preferably 44% or more, and particularly preferably 45% or more) at 200° C. and is excellent in tear straightness when the tube is shrunk, and then torn.
Means to Solve the Technical Problem
As a result of extensive studies to achieve the object, the present inventors have found that excellent tear straightness was obtained when the thickness of the entanglement unit of a polymer constituting a tube reaches a specific range, thereby completing the present invention. That is, the present disclosure relates to a heat-shrinkable tube having tearability, including at least a fluororesin as a base resin, in which the entanglement thickness of a polymer observed at the cross-section in a longitudinal direction is 1 μm to 9 μm after the tube is shrunk by 35% or more at 200° C.
Effects of the Invention
Since the tube of the present disclosure has excellent tear straightness, even a tube having a small diameter, to which it is difficult to uniformly apply tear force when the tube is removed, can be easily torn and removed.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a flowchart illustrating an example of a manufacturing process of a tube of the present disclosure.
FIG. 2 is a view illustrating a method for observing the cross-section of the tube of the present disclosure.
FIG. 3 is a photograph of the cross-section of the tube of the present disclosure, which is shrunk by 35% or more at 200° C. in the longitudinal direction.
FIGS. 4A and 4B are cross-sectional schematic views of an expandable jig used in the expansion of the tube. FIG. 4A illustrates an expandable jig with a type which fixes both ends of the tube and FIG. 4B illustrates an expandable jig with a type which fixes only one end of the tube.
FIG. 5A is a view schematically illustrating a molecular state in the tube and FIG. 5B is a view illustrating the route of propagation when FIG. 5A is torn, when the tube of the present invention by dispersion control of ETFE dispersion particles is shrunk by 35% or more at 200° C.
FIG. 6 is a schematic view illustrating an example of a front tip Dulmage shape of a Dulmage screw.
FIG. 7A is a view schematically illustrating a molecular state in the tube and FIG. 7B is a view illustrating the route of propagation when FIG. 7A is torn, when the tube of the present disclosure by entanglement control of FEP molecules is shrunk by 35% or more at 200° C.
FIGS. 8A and 8B are views schematically illustrating the x-y cross-section of the tube of the present disclosure illustrated in FIG. 2. FIG. 8A is a schematic view of a portion of the tube in which the entanglement strength of the molecules by dispersion control of ETFE dispersion particles is controlled and FIG. 8B is a schematic view of a portion of the tube in which the entanglement strength of the molecules by entanglement control of FEP molecules is controlled.
FIG. 9 is a view explaining a gap of a screw of a twin-screw extruder.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A polymer material is present in a state where the molecular chains of the molecules constituting the material are entangled like a ball of thread. The entangled state of these molecules is maintained even in a molded body obtained by molding the polymer material, so that physical properties of the molded body are significantly affected by the entangled structure of the molecules. The present invention is an improvement of Patent Document 1, which was also filed by the Applicant of this disclosure to provide a heat-shrinkable tube having excellent tear straightness by controlling the entanglement strength of the molecules constituting the tube. The heat-shrinkable tube having excellent tear straightness of the present invention is characterized in that the thickness of the entanglement unit of a polymer observed at the cross-section in a longitudinal direction of the tube is 1 μm to 9 μm after the tube is shrunk by 35% or more at 200° C., more preferably 40% or more, even more preferably 44% or more, and particularly preferably 45% or more. Since the narrower the tube is, the more difficult it becomes to exhibit the shrinkage rate, it is preferred to achieve the shrinkage rate when the tube has an outer diameter of 1.40 mm or less.
The heat-shrinkable tube having tearability of the present invention is prepared by the process illustrated in FIG. 1 as an example. When the heat-shrinkable tube having characteristics of the present invention is to be manufactured, it is necessary to control the entanglement strength of the molecules as described below. When the entanglement strength of the molecules is to be controlled, there are usually two methods. One is to control the entanglement strength by dispersion control of an additive for enhancing tearability, and the other is to control the entanglement strength by entanglement control of the molecules of a base resin.
Hereinafter, the effects of the entanglement structure of the molecules on the tearability of the tube will be described using the drawings.
In FIG. 2, the method for observing the cross-section of the heat-shrinkable tube will be described. Here, the tube of the present disclosure is a tearable tube, so that the cross-section thereof may be observed by tearing the tube. When a tube 1 is torn, the tube 1 is torn in the z-axis direction (in FIG. 2, the longitudinal direction of the tube is defined as the z-axis direction) by applying tensile strength to a cutting line 11 placed at the center of the tube in a direction of widening the cutting line. As an example, FIG. 3 illustrates a photograph of the cross-section including the z-axis when the tube is torn in the z-axis.
A method for controlling the entanglement strength by dispersion control of the additive for enhancing tearability will be shown below.
In the heat-shrinkable tube having tearability according to the present disclosure, a fluororesin is at least used as a base resin. Hereinafter, the present will be describe by an example in which a copolymer (hereinafter, referred to as ‘FEP’) is used as a base resin, which includes tetrafluoroethylene and hexafluoropropylene as constituent monomers. When tearability is insufficient, a polymer which is incompatible with the base resin, or a filler as an additive for enhancing tearability may be added to the base resin.
Examples of the polymer which is incompatible with the base resin include a tetrafluoroethylene-ethylene copolymer (hereinafter, referred to as ‘ETFE’), a liquid crystal polymer, polyimide, polyether ether ketone, polyamide, and the like. Further, examples of the filler include various inorganic fillers, glass fiber, carbon fiber, and the like. The addition amount of the additive for enhancing tearability, which is added to FEP is preferably 20 wt % or less based on the total amount including FEP. When the addition amount is more than 20 wt %, the expansion rate of the tube may not be increased, and a high heat-shrinkage rate of 40% or more may not be obtained.
As an aspect of the present disclosure, for example, a tube obtained by using ETFE as an additive for enhancing tearability in FEP of a base resin will be described below.
The tube is molded by a process illustrated in FIG. 1. In a twin-screw extruder used for dispersing ETFE in FEP, a pattern and a gap are adjusted in order to finely disperse ETFE (hereinafter, referred to as ‘fine dispersion’). As illustrated in FIG. 9, a gap 8 refers to an interval of thread parts of a screw 7. It is preferred to provide the pattern of the screw with a staying part. This is molded into the tube by a single-screw extruder. The molded tube is expanded by using an expandable jig 2 illustrated in FIG. 4A. A tube 1 is allowed to pass through a pipe for regulating the outer diameter (hereinafter, referred to as ‘outer diameter regulating pipe 21’) to fix both ends of the tube 1 to sealing jigs 22 at both ends of the outer diameter regulating pipe 21 and seal the tube 1. The tube 1 is expanded in a diameter direction by injecting a compressed gas into the tube from an injection port 23 to pressurize the inside of the tube 1 while heating an expandable jig 2 which fixes the tube 1.
FIG. 5A schematically illustrates a molecular state in the tube when the tube prepared as explained above is shrunk. The ETFE dispersion particle 3 is present in a state where the particle is stretched in a longitudinal direction of the tube (the longitudinal direction of the tube is defined as the z-axis direction in FIG. 5A) after the tube is extrusion molded, and then, the void is generated at a portion of the interface between FEP 4 and the ETFE dispersion particle 3 by expanding the inner diameter of the tube. The void portion generated by the expansion is in a state where FEP 4 and the ETFE dispersion particle 3 are dissociated, and is in a state where the entanglement of molecules is cut off. A plurality of voids is present in the tube by finely dispersing ETFE. Further, the state where FEP molecules are entangled becomes a state where the entanglement of FEP molecules is easily disentangled by expansion because a portion 4a where FEP molecules are entangled and a portion 4b where molecules are not entangled are present after the tube is extrusion molded. Specifically, since the fluororesin FEP has low cohesive force among the molecular chains, the molecular chains are easily slipped and the molecular chains are slid by expansion in a portion where FEP molecules are slightly entangled, so that the entanglement of FEP molecules becomes easily disentangled.
After the expanded tube is shrunk, the state where the entanglement of molecules in a portion of voids generated at the interface between FEP 4 and ETFE dispersion particle 3 is cut off is maintained. Since there is no entanglement of molecules in the portion of voids, the force for disentangling the entanglement of molecules (hereinafter, referred to as ‘entanglement strength of molecules’) is 0. Further, in a portion of the state where the entanglement of FEP molecules is easily disentangled, the entanglement strength of molecules is close to 0. A bundle of FEP molecules, which are surrounded by a portion where the entanglement strength of molecules is 0 and a portion where the entanglement strength is weak, are formed at in the tube after being shrunk. When a cutting line is placed in the end portion of the tube and tear force is added to the cutting line as a starting point, the split is propagated along the bundles of FEP molecules. FIG. 5B illustrates the route 5 of propagation when FIG. 5A is torn.
In a tube in which the entanglement strength of molecules is controlled by control of dispersion of ETFE dispersion particles 3, bundles of molecules may be actually observed on the cross-section including the z-axis (FIG. 3 (cross-section of the tube after being shrunk)).
Hereinafter, a method for controlling the entanglement strength of molecules by controlling entanglement of FEP molecules will be shown. When the entanglement of FEP molecules is to be controlled, there are usually two methods.
The first is a method of disentangling the entanglement of FEP molecules in an extrusion mold while suppressing ETFE from aggregating. Specifically, FEP in which ETFE is finely dispersed is used, and furthermore, a Dulmage screw is used as an example of the method of suppressing ETFE from aggregating. As a Dulmage screw, a shape is selected considering that shear force may be lowered as much as possible while suppressing the aggregation. FIG. 6 illustrates an example of the shape of the front tip of the Dulmage screw (Dulmage 6). A mold having a structure suppressing the shear rate between the dies in the screw is used. The shear force is suppressed by suppressing the shear rate, so that the entanglement of entangled molecules is disentangled in the screw part.
The second is a method of reducing the entanglement of molecules at the outlet of the extrusion mold. Specifically, molding is carried out by setting the Draw-Down-Ratio (DDR) to a large value during the extrusion molding. The DDR is obtained by the following equation.




  
    
      
        
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The entanglement of molecules in the diameter direction of the tube may be decreased by increasing DDR. Herein, it is typically described that molding is achieved by setting DDR to 3 to 15 (Fluoro-resin Handbook P. 250, published by Nikkan Kogyo Shimbun, Ltd.) when a fluororesin tube is extrusion molded. However, in the heat-shrinkable tube having tearability of the present disclosure, it is preferred to set DDR to 50 or more. In the tube molded by doing so, a portion in which FEP molecules are slightly entangled in a diameter direction is present in a large amount.
However, when a tube extrusion molded by enlarging the DDR is processed with a heat-shrinkable tube, it is known that the tube is greatly shrunk in a longitudinal direction when the heat-shrinkage working of the tube. Even when the DDR is 30, it is known that shrinkage by 5% or more occurs (the official gazette of Japanese Patent Application Laid-Open No. 1999-323053), and molding in which the DDR is set to 50 or more has not been performed until now. Even in the tube of the present disclosure, when the tube is used as an assembly jig of a catheter, a large shrinkage in the longitudinal direction becomes a problem. Accordingly, it has been contrived that a heat-shrinkable tube which is not shrunk in a longitudinal direction may be obtained even in the tube extrusion molded by using the expandable jig 2 illustrated in FIG. 4B to expand the tube, and thus enlarging the DDR. The tube 1 is put into an outer diameter regulating pipe 21 by mounting a movable sealing jig 24 to one end of the tube 21. Thereafter, the inside of the tube is sealed by mounting the other end of the tube 1 to the sealing jig 22 fixed at the outer diameter regulating pipe 21. The tube 1 is expanded in a diameter direction by injecting a compressed gas into the tube from an injection port 23 to pressurize the inside of the tube 1 while heating an expandable jig 2 which fixes the tube 1. The outer diameter of the movable sealing jig 24 is smaller than the inner diameter of the outer diameter regulating pipe 21 and the tube 1 may move while sliding in the regulating pipe, so that expansion may be achieved while removing the distortion when the tube is molded in a longitudinal direction.
FIG. 7A schematically illustrates a molecular state in the tube when the tube prepared by adjusting particularly the entanglement state of molecules as explained above is shrunk. When compared with FIG. 5B, the number of ETFE dispersion particles 3 is small and a portion 4b in which there is no entanglement of FEP molecules is present in a large amount. When compared with the case where the entanglement strength of molecules is controlled by dispersion control of ETFE dispersion particles 3, the portion in which the entanglement strength of molecules is 0 is present in a small amount, and the portion in which the entanglement strength of molecules is weak is present in a large amount. In the tube after being shrunk, a bundle of FEP molecules surrounded by a portion in which the entanglement strength of molecules is weak and a portion in which the entanglement strength of molecules is 0 are formed. FIG. 7B illustrates the route 5 of tearing propagation when FIG. 7B is torn. The tearing of the tube is propagated along with the bundle of FEP molecules.
Even in the tube in which the entanglement strength of molecules is controlled by the entanglement control of FEP molecules, a bundle of molecules are observed on the cross-section including the z-axis in the same manner as in the tube in which the entanglement strength of molecules is controlled by dispersion control of the ETFE dispersion molecules.
When the addition amount of ETFE to be added to FEP is small, ETFE dispersion molecules 3 are sparsely present, and a bundle of FEP molecules are mostly formed by only the entanglement control of FEP molecules. As described above, it is possible to obtain a heat-shrinkable tube having a bundle of FEP molecules surrounded by a portion in which the entanglement strength of molecules is weak in the tube after being shrunk by controlling the entanglement strength of molecules by the entanglement control of FEP molecules even when the amount of an additive is reduced or no additive is used.
FIGS. 8A and 8B schematically illustrate a portion of the x-y cross-section of the tube in FIG. 2. FIG. 8A is a schematic view of a tube in which the entanglement strength of molecules is controlled by dispersion control of ETFE dispersion particles 3, illustrating that ETFE dispersion particles 3 are scattered in FEP 4 of the base resin. FIG. 8B is a schematic view of a tube in which the entanglement strength of molecules by the entanglement control of FEP molecules is controlled, illustrating that a point 4b in which FEP molecules are not entangled is present in the base resin 4 in which FEP molecules are less entangled. The ETFE dispersion particle 3 of FIG. 8A and the point 4b in which FEP molecules of FIG. 8B are not entangled become a point in which the entanglement strength of molecules is 0 or close to 0, so that there is a base resin 4 having a larger entanglement strength of molecules than those of the particle 3 and the point 4 therebetween. The thickness of the bundle of FEP molecules surrounded by a portion in which the entanglement strength of molecules is weak and a portion in which the entanglement strength of molecules is 0 (hereinafter, referred to as ‘thickness of the entanglement unit of a polymer’) depends on the interval between the ETFE dispersion particle 3 or the point 4b in which FEP molecules are not entangled. The thickness of the entanglement unit of the polymer is mutually related to the tear straightness of the tube. If excellent tear straightness is imparted to the tube which is shrunk by 35% or more at 200° C., the thickness of the entanglement unit of the polymer needs to be 1 μm to 9 μm. The thickness is preferably 1 μm to 9 μm, more preferably 1 μm to 6 μm, and particularly preferably 1 μm to 4 μm.
When the thickness of the entanglement unit of the polymer is too large, it means that the entanglement strength of molecules is 0 or the interval between the points close to 0 is large, and the direction of tearing propagation fluctuates, and thus, tear straightness deteriorates. Further, when the thickness of the entanglement unit of the polymer is too small, it means that the strength of the entire tube is also small, which is not preferred because it becomes difficult to perform processing or treatment such as expansion of the tube.
EXAMPLE
(Measurement of Thickness of Entanglement Unit of Polymer)
The thickness of the entanglement unit of the polymer was calculated by measuring the shape of the cross-section of the tube in a longitudinal direction, and indicating the shape of the cross-section as a waveform. Hereinafter, the thickness will be described with reference to FIG. 3. The cross-section was measured in a vertical direction (referred to as the z-direction in the measurement of the surface shape) by using a confocal microscope (Lasertec Corporation, H1200, Objective lens 100× magnification) to scan the cross-section in the y-direction in FIG. 3. A center line was drawn by calculating a central value of the width in the z-direction of the waveform in the measurement range. The central value was calculated, except for a peak having the highest value and a peak having the smallest value of the waveform, which could be obtained in the measurement range. An interval from a point where the central line intersects with the waveform to a point where the next central line intersects with the waveform, that is, the length of the central line, which is the width of a mountain or valley, was defined as the thickness of the entanglement unit of the polymer.
(Test of Tear Straightness)
Even when a tube with a small diameter was torn, the measurement was performed by the following method in order to more clearly determine whether sufficient tear straightness could be obtained. A cutting line with a length of 40 mm was drawn at one end portion of a sample with a length of 1,000 mm. A jig was used to draw cutting line in parallel to the longitudinal direction of the tube at the center of the tube. The tube was torn at a rate of 200 mm/min from the cut portion to the other end portion of the tube. The weight of each of the two torn tubes was measured to obtain the ratio of the weights. It can be determined that tear straightness is high when the ratio is close to 50% to 50%. When the tube with a small diameter is to be torn, the ratio needs to be set within a range between 50% to 50% and 45% to 55%. Tear straightness is enhanced by setting the ratio within a range between 50% to 50% and 48% to 52%, furthermore within a range between 50% to 50% and 49% to 51%.
Example 1
(Manufacture of Molding Material)
A tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer (Du Pont-Mitsui Fluorochemicals Co., Ltd, FEP-130J) and a tetrafluoroethylene-ethylene copolymer (ETFE: Asahi Glass Co., Ltd, C-55AP) were mixed at an FEP/ETFE weight ratio=80/20, and the resulting mixture was sufficiently stirred by a tumbler. The mixture was introduced into a twin-screw extruder having a cylinder diameter of 20 mm, and was extruded at a screw rotation number of 45 rpm and a die temperature of 320° C. to obtain a molded pellet. For the screw, a pattern with four staying parts partially provided was used, and a combination of a gap of 0.5 mm was used.
(Molding of Sample Tube)
The prepared pellet was used to mold the tube by using the twin-screw extruder having a cylinder diameter of 20 mm. As the screw, a full-flight screw was used, and the tube was molded at a screw rotation number of 10 rpm, a die temperature of 390° C., and a draw down ratio (DDR) of 10 according to the sizing plate method. A tube with an internal diameter of 0.5 mm, an outer diameter of 0.9 mm, and a thickness of 0.2 mm was obtained.
(Expansion of Sample Tube)
The molded tube was cut into a length of 1,000 mm by mounting the tube onto an expandable jig which is the same type as in FIG. 4A, and injecting pressurized nitrogen into the internal part of the jig while heating the jig from the external part of the jig to expand the inner diameter of the tube. The outer diameter of the tube was 1.33 mm.
(Shrinkage of Sample Tube)
Ten tubes were arbitrarily taken out from the expanded sample tubes, the inner diameters were measured, and then the tubes were heated for 20 minutes and heat-shrunk in a thermostat at 200° C., thereby producing sample tubes. The shrinkage rate was calculated by measuring the inner diameter after the shrinkage.
Example 2
(Manufacture of Molding Material)
The tube was manufactured in the same manner as in Example 1, except that the materials were mixed at an FEP/ETFE weight ratio=90/10 for the FEP/ETFE weight ratio.
(Molding of Sample Tube)
The tube was molded at a draw down ratio (DDR) of 10 by using a Dulmage screw in the screw for the single-screw extruder. The tube was molded by setting the other conditions to be the same as in Example 1.
(Expansion•Shrinkage of Sample Tube)
The experiment was carried out under the same conditions as in Example 1. The outer diameter of the tube after the expansion was 1.39 mm.
Example 3
(Manufacture of Molding Material)
The tube was manufactured in the same manner as in Example 1, except that the materials were mixed at an FEP/ETFE weight ratio=97/3 for the FEP/ETFE weight ratio.
(Molding of Sample Tube)
The tube was molded at a draw down ratio (DDR) of 50 by using a Dulmage screw in the screw for the single-screw extruder. The tube was molded by setting the other conditions to be the same as in Example 1.
(Expansion of Sample Tube)
The molded tube was cut into a length of 1,000 mm by mounting the tube onto an expandable jig which is the same type as in FIG. 4B, and injecting pressurized nitrogen into the internal part of the jig while heating the jig from the external part of the jig to expand the inner diameter of the tube. The outer diameter of the tube was 1.36 mm.
(Shrinkage of Sample Tube)
The experiment was carried out under the same conditions as in Example 1.
Comparative Examples 1 to 3
(Manufacture of Molding Material)
A tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer (Du Pont-Mitsui Fluorochemicals Co., Ltd, FEP-130 J) and a tetrafluoroethylene-ethylene copolymer (ETFE: Asahi Glass Co., Ltd, C-55AP) were mixed at each weight ratio, and the mixture was introduced into a twin-screw extruder having a cylinder diameter of 20 mm, and was extruded at a screw rotation number of 45 rpm and a die temperature of 320° C. to obtain a molded pellet. For the screw, a pattern with a gap of −1.5 mm (a portion at which the screw was overlapping was 1.5 mm) and a staying part not provided was used.
(Molding of Sample Tube)
The manufactured pellet was used to mold the tube by using the twin-screw extruder having a cylinder diameter of 20 mm. As the screw, a full-flight screw was used, and the tube was molded at a screw rotation number of 10 rpm, a draw down ratio (DDR) of 10, and a die temperature of 390° C. according to the sizing plate method. A tube with an internal diameter of 0.5 mm, an outer diameter of 0.9 mm, and a thickness of 0.2 mm was obtained.
(Expansion of Sample Tube)
The molded tube was cut into a length of 1,000 mm by mounting the tube onto an expandable jig which is the same type as in FIG. 4A, and injecting pressurized nitrogen into the internal part of the jig while heating the jig from the external part of the jig to expand the inner diameter of the tube.
(Shrinkage of Sample Tube)
Ten tubes were arbitrarily taken out from the expanded sample tubes, the inner diameters were measured, and then the tubes were heated for 20 minutes and heat-shrunk in a thermostat at 200° C., thereby producing sample tubes. The shrinkage rate was calculated by measuring the inner diameter after the shrinkage.
For each sample tube manufactured, the thickness of the entanglement unit of the molecule was obtained based on the above-described method of measuring the thickness of the entanglement unit of the molecule. Further, tear straightness was measured based on the above-described method of testing tear straightness. The result is shown in Table 1.














TABLE 1










Comparative
Comparative
Comparative



Example 1
Example 2
Example 3
Example 1
Example 2
Example 3






















FEP
80
90
97
90
80
70


blending


ratio


ETFE
20
10
3
10
20
30


blending


ratio


Thickness
2
6
7
13
12
8


of


Entanglement


Unit of


Molecule


Tear
50:50
49:51
51:49
33:67
39:61
48:52


straightness
∘
∘
∘
x
x
∘


(wt %)


Shrinkage
44%
46%
45%
45%
42%
20%


rate









For the tubes in Examples 1 to 3 of the present disclosure, a heat-shrinkage rate of 40% or more was obtained at 200° C., and the thickness of the entanglement unit of the polymer was 1 μm to 9 μm. The ratio of the weights of the torn tubes, which exhibits tear straightness of the tube, was between 50% to 50% and 49% to 51%, and excellent tear straightness may be obtained. In contrast, a heat-shrinkage rate of 40% or more could be obtained in the tubes of Comparative Examples 1 and 2 for the heat-shrinkable tube having tearability in the related art, but since the thickness of the entanglement unit of the polymer was too large, sufficient tear straightness could not be obtained, and the weight ratio exceeded a weight ratio of 45% to 55%, which is a reference in which sufficient tear straightness is obtained even when a tube with a small diameter is torn. In Comparative Example 3, tear straightness was obtained, but the tube was not expanded by 20% or more, and a heat-shrinkage rate of 40% or more could not be obtained (the shrinkage rate was 21% even after the tube was heated at 200° C. for 1 hour).
Example 4
(Manufacture of Molding Material)
A tube was manufactured in the same manner as in Example 3, except that a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (hereinafter, referred to as ‘PFA’.) (Du Pont-Mitsui Fluorochemicals Co., Ltd, PFA-340 J) and C-55 AP were mixed at a PFA/ETFE weight ratio=97/3.
(Molding of Sample Tube)
The tube was molded in the same manner as in Example 3.
(Expansion of Sample Tube)
The tube was expanded in the same manner as in Example 3. The outer diameter of the tube was 1.18 mm.
(Shrinkage of Sample Tube)
The experiment was performed in the same manner as in Example 3. As a result of measuring the manufactured sample tubes, respectively, the thickness of the entanglement unit of the polymer, the tear straightness, and the shrinkage rate were 8 μm, 52:48, and 35%, respectively. Regardless of the type of fluororesin, a correlation between the thickness of the entanglement unit of the polymer and the tear straightness was shown.
INDUSTRIAL APPLICABILITY
A tearable tube made of the fluororesin of the present disclosure has high heat-shrinkability and good tear straightness, and thus, is easily mounted during the processing and removed after the use, and is suitable as an assembly jig such as a catheter.
DESCRIPTION OF REFERENCE NUMBERS
1: Tube, 2: Expandable jig, 21: Outer diameter regulating pipe, 22: Sealing jig, 23: Injection port, 24: Movable sealing jig, 3: ETFE dispersion particle, 4: FEP, 5: Route of tearing propagation, 6: Dulmage, 7: Screw, 8: Gap

## Claims

1. A heat-shrinkable tube having tearability, comprising at least a fluororesin as a base resin,
wherein the tube has a shrinkage rate of 35% or more when heated at 200° C., and a thickness of an entanglement unit of a polymer observed on a cross-section in a longitudinal direction of the tube after being shrunk at 200° C. by 35% or more is 1 μm to 9 μm.

2. The tube of claim 1, wherein the tube has an outer diameter of 1.39 mm.

3. The tube of claim 1, wherein the tube has a shrinkage rate of 40% or more when heated at 200° C., and a thickness of an entanglement unit of a polymer observed on a cross-section in a longitudinal direction of the tube after being shrunk at 200° C. by 40% or more is 1 μm to 9 μm.

4. The tube of claim 3, wherein the fluororesin is a copolymer comprising tetrafluoroethylene and hexafluoropropylene as constituent monomers.

5. The tube of claim 3, wherein a ratio exhibiting tear straightness is in a range between 50% to 50% and 48% to 52%.

6. The tube of claim 3, wherein the tube has an outer diameter of 1.39 mm.

7. The tube of claim 1, wherein the fluororesin is a copolymer comprising tetrafluoroethylene and hexafluoropropylene as constituent monomers.

8. The tube of claim 7, wherein a ratio exhibiting tear straightness is in a range between 50% to 50% and 48% to 52%.

9. The tube of claim 7, wherein the tube has an outer diameter of 1.39 mm.

10. The tube of claim 1, wherein a ratio exhibiting tear straightness is in a range between 50% to 50% and 48% to 52%.

11. The tube of claim 10, wherein the tube has an outer diameter of 1.39 mm.

12. A heat-shrinkable tube having tearability, comprising at least a fluororesin as a base resin,
wherein the tube has a shrinkage rate of 44% or more when heated at 200° C., and a thickness of an entanglement unit of a polymer observed on a cross-section in a longitudinal direction of the tube after being shrunk at 200° C. by 44% or more is 1 μm to 9 μm.

13. The tube of claim 12, wherein the fluororesin is a copolymer comprising tetrafluoroethylene and hexafluoropropylene as constituent monomers.

14. The tube of claim 12, wherein a ratio exhibiting tear straightness is in a range between 50% to 50% and 48% to 52%.

15. The tube of claim 12, wherein the tube has an outer diameter of 1.39 mm.