CN101291695A - Medical catheter tubes and process for production thereof - Google Patents
Medical catheter tubes and process for production thereof Download PDFInfo
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- CN101291695A CN101291695A CNA2006800386890A CN200680038689A CN101291695A CN 101291695 A CN101291695 A CN 101291695A CN A2006800386890 A CNA2006800386890 A CN A2006800386890A CN 200680038689 A CN200680038689 A CN 200680038689A CN 101291695 A CN101291695 A CN 101291695A
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- ethylene polymer
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- tetrafluoro ethylene
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Abstract
A medical catheter tube containing a tetrafluoroethylene polymer, which has a wall thickness of 0.1mm or below and exhibits a tensile strength (S1) at 1.0 mm displacement of 5.0N/mm<2> or above; and a process for the production of medical catheter tubes, characterized by molding a composition comprising both a tetrafluoroethylene polymer and a lubricant having high affinity for the polymer by paste extrusion. The invention provides thin-wall medical catheter tubes excellent in elongation resistance, kink resistance and internal cavity lubricity.
Description
Technical field
The present invention relates in medical offices such as hospital, be fit to the catheter tube for medical treatment and the manufacture method thereof that contain tetrafluoro ethylene polymer (hereinafter referred to as " PTFE ") of use.
As the patent application 2005-302099 of Japan number (application on October 17th, 2005) and the whole disclosure cross-references that comprise description, claim, accompanying drawing and summary of the patent application 2006-010472 of Japan number (application on January 18th, 2006) of related application, and these whole disclosures are incorporated in the application as a reference.
Background technology
For alleviate the patient animally, temporal burden, percutaneous inserts in blood vessel that operation has become main flow in recent years in the blood vessel of low invasion and attack of treatment that conduit carries out vascular lesion.For example can enumerate: the narrow positions of blood vessel dilating or since the blood vessel of thrombosis obturation in, apply negative pressure by conductive pipe, to external vascularization hands art of removing the percutaneous of thrombosis; Perform the operation in the blood vessel that is called as Embolization for injection embolization material such as the aneurysm of in cerebrovascular etc., finding or arteriovenous malformotion, hemangioma or coil.
Conduit for using in the operation in the vascularization operation of above-mentioned percutaneous or blood vessel for example requires following character:
(1) high operability and safety: fashionable to the body interpolation, injured blood vessel wall etc. does not make conduit arrive the character of biological intravital diseased region rapidly and correctly.For example, in order to conduit in blood vessel etc. when insertion or extraction etc. patient's operation positively be communicated to the position adjustments of leading section from base portion.
Specifically, as this position adjustments, can enumerate characteristic (anti-extensibility) that conduit do not extend and the moment of torsion of the revolving force that applies in order to the base portion of positively passing at conduit is passed on property etc.
(2) keeping and the reduction of the frictional resistance of surface of internal cavity of intracavity diameter: the tube cavity that forms in order to inner layer resin, easily inject medicaments such as contrast agent or embolization material to patient's biological intravital diseased region by conduit, perhaps for example in blood vessel, successfully remove thrombosis or fragment intravascular masses such as (foreign bodies) by attract waiting, or character (inner chamber lubricity) or resistance to pressure that other therapeutic appliance such as seal wire is passed through easily.
Specifically, along the seal wire of going ahead of the rest, injured blood vessel inwall etc. and the seal wire tracing ability that successfully inserts several times and extract out is necessary not in blood vessel of bending etc.In addition, the affinity for blood or tissue is necessary.And, arrive destination locations, do not extract out under the state of seal wire in catheter proximal end (tip), be necessary in the distortion position of blood vessel, the anti-kink that the crooked position conduit does not produce distortion.In addition, injured blood vessel wall and to keep the flexibility corresponding to the leading section of the shape of shape of blood vessel be necessary not.Should to reduce external diameter of pipe in order reducing with the frictional resistance of blood vessel wall further as far as possible, to reduce for the flow that suppresses medicament on the other hand or the flow resistance of intravascular mass and increase internal diameter, the internal layer (thin-walled property) that forms conduit as thin as a wafer is necessary.
In order to satisfy the above-mentioned requirements characteristic, this conduit for example is constituted as following structure: have and contain resin and/or elastomeric ectonexine and contain metal wire and/or the multilamellar of the enhancement layer of synthetic resin line, contain sufficient leading section of flexibility and more upright and more outspoken main part, from the leading section to the main part, have rigidity.
Particularly, make medicament or therapeutic appliance etc.,, for example use fluorothene polymer (fluororesin) as the constituent material of internal layer easily by inner chamber for by reducing the frictional resistance of surface of internal cavity.Specifically, particularly use the tetrafluoro ethylene polymer (PTFE) of resistance to chemical reagents, low frictional properties, electrical insulating property excellence mostly.
As the manufacture method of the conduit that uses PTFE, for example disclose in the patent documentation 1,2 and 3 after coating PTFE dispersion liquid carries out sintering on the heart yearns such as copper cash, form outer resin layer, then extract heart yearn out, obtain the method (infusion process) of conduit thus.
But, in the technology of above-mentioned patent documentation 1-3, owing to be not have orientation, thus there is poor tensile strength, or owing to insert, extract out the problem of seal wire lubricity reduction of the inner chamber that landing caused of PTFE particle several times the time.In addition, the conduit by patent documentation 1-3 obtains owing to be not have orientation, then can not get sufficient anti-kink, position adjustments (comprising anti-extensibility or the moment of torsion property passed on).Further, in order to obtain the PTFE tube of desired wall thickness, be necessary to repeat to be coated with several times dispersion liquid and sintering step, the result causes production efficiency poor, has the problem that produces local thickness's inequality owing to crawling in addition.
As the forming method of conduit, except the disclosed infusion process of above-mentioned patent documentation 1-3, also use extrusion moulding.And extrusion moulding mainly contains and melt extrudes molding and stick with paste extrusion molding.PTFE does not generally use to melt extrude molding and use the paste extrusion moulding because melt viscosity is very big.
For example, disclose in the patent documentation 4 and the pipe molding such as extruded by paste and extrude the PTFE resinoid, carried out sintering, used stretching device to stretch in the longitudinal direction then and carry out the PTFE resinoid pipe and the manufacture method thereof of thin-walled property.
The PTFE composition and method of making the same that contains amorphous fluoropolymer and fluorochemical of the hot strength excellence that can stick with paste extrusion molding is disclosed in the patent documentation 5.
Patent documentation 1: TOHKEMY 2000-316977 number
Patent documentation 2: TOHKEMY 2000-51365 number
Patent documentation 3: TOHKEMY 2002-45428 number
Patent documentation 4: TOHKEMY 2004-340364 number
Patent documentation 5: TOHKEMY 2000-136280 number
Summary of the invention
The problem that invention will solve
The technology of above-mentioned patent documentation 4 from equipment such as giving of the importing of stretching device or stretching step import, the manufacturing cost aspect considers uneconomical.Further, only carry, put down in writing as the tensile break strength increase of the PTFE class pipe of purposes with fuel in the technology of patent documentation 4, and do not take in for the anti-extensibility of the hot strength under the desired small displacement of conduit with air-brake coupling hose for main.
The technology of above-mentioned patent documentation 5 for when suppressing to extrude the keeping of the single-layer sheet that obtains or filament by paste, the displacement in when batching is the technology of purpose, owing to be not multiwalled viewpoint, so do not take in for the thin-walled property of PTFE tube.Further, in this method, because the heat decomposition temperature of amorphous fluoropolymer is low, because the decomposition gas of the amorphous fluoropolymer during sintering might produce bubble at tube-surface, inner face, or since the stripping of low molecular weight compositions might exert an influence etc. to the organism fitness, so existing problems.
As mentioned above, anti-kink, the position adjustments of the conduit of the patent documentation 1-3 that obtains by infusion process are insufficient, do not take in for anti-extensibility, thin-walled property etc. by the conduit of sticking with paste the patent documentation 4,5 that extrusion moulding obtains in addition.Therefore, in any prior art, for example do not have as the great majority of the desired above-mentioned various character of use in the operation in the vascularization operation of percutaneous or blood vessel or a part of.
In view of above-mentioned present situation, problem purpose of the present invention is, excellent catheter tube for medical treatment that contains tetrafluoro ethylene polymer and the manufacture method thereof kept that has for the particularly thin-walled of the desired above-mentioned various character of conduit and anti-extensibility, anti-kink, inner chamber lubricity is provided.
The method of dealing with problems
The present invention has one or more following features in order to address the above problem.
(1) one of the present invention is characterized as catheter tube for medical treatment, and this conduit is the catheter tube for medical treatment that contains tetrafluoro ethylene polymer, it is characterized in that, wall thickness is below the 0.1mm, and the hot strength (S1) in 1.0mm when displacement is 5.0N/mm
2More than.
(2) preferred embodiment in, the fusing point peak of above-mentioned catheter tube for medical treatment is more than 320 ℃.
(3) of the present invention other be characterized as catheter tube for medical treatment, this conduit is the catheter tube for medical treatment that contains tetrafluoro ethylene polymer, it is characterized in that, wall thickness is that the following and birefringence (Δ n1) of 0.1mm is 2.5 * 10
-3More than.
(4) preferred embodiment in, the hot strength (S1) the during 1.0mm of above-mentioned catheter tube for medical treatment displacement is 5.0N/mm
2More than.
(5) preferred embodiment in, the hot strength (S1) the during 1.0mm of above-mentioned catheter tube for medical treatment displacement with the pass of birefringence (Δ n1) is:
S1≥170.0×Δn1+3.0
(6) of the present invention other be characterized as the catheter tube for medical treatment that hot strength is improved, it is the catheter tube for medical treatment that contains tetrafluoro ethylene polymer, it is characterized in that, by under coexistence for the high lubricant of the affinity of this tetrafluoro ethylene polymer, above-mentioned tetrafluoro ethylene polymer is stuck with paste extrusion molding, with the polymer particle that contains in the above-mentioned tetrafluoro ethylene polymer direction of principal axis orientation along above-mentioned conduit, then when above-mentioned conduit dry by the above-mentioned lubricant of volatilization, reduce the gap between above-mentioned polymer particle.
(7) preferred embodiment in, above-mentioned tetrafluoro ethylene polymer is orientated in the longitudinal direction.
(8) other the manufacture method that is characterized as above-mentioned any above-mentioned catheter tube for medical treatment of the present invention is characterized in that, extrudes by paste, will contain above-mentioned tetrafluoro ethylene polymer and for the composition molding of the high lubricant of the affinity of this polymer.
(9) preferred embodiment in, above-mentioned lubricant is the lubricant that contains fluorochemical.
(10) preferred embodiment in, above-mentioned lubricant is the lubricant that contains fluorochemical.
(11) preferred embodiment in, the boiling point of above-mentioned lubricant is more than 100 ℃.
(12) preferred embodiment in, poor (T1-T2) of the interfacial tension (T2) of the interfacial tension of above-mentioned tetrafluoro ethylene polymer (T1) and above-mentioned lubricant is less than 3.6dyne/cm.
(13) preferred embodiment in, the manufacture method of above-mentioned catheter tube for medical treatment further contains the drying steps that carries out more than the boiling point of above-mentioned lubricant.
(14) preferred embodiment in, behind above-mentioned drying steps, further contain the sintering step that more than the fusing point of above-mentioned tetrafluoro ethylene polymer, carries out.
(15) other the manufacture method that is characterized as catheter tube for medical treatment of the present invention, this method is the manufacture method that contains the catheter tube for medical treatment of tetrafluoro ethylene polymer, wherein, contains following each step:
(a) in order to make the polymer particle that contains in the above-mentioned tetrafluoro ethylene polymer direction of principal axis orientation along above-mentioned conduit, then under coexistence for the high lubricant of the affinity of above-mentioned tetrafluoro ethylene polymer, above-mentioned tetrafluoro ethylene polymer is stuck with paste extrusion molding, obtain managing the extrusion molding step of molded body
When (b) removing at least a portion of the above-mentioned lubricant that will contain in the aforementioned tube molded body, reduce the interparticle gap contained in the above-mentioned tetrafluoro ethylene polymer, more than the boiling point of above-mentioned lubricant, the aforementioned tube molded body is carried out exsiccant drying steps
(c) molten each other sticking in order to make between the particle that contains in the above-mentioned tetrafluoro ethylene polymer, more than the fusing point of above-mentioned tetrafluoro ethylene polymer the pipe molded body behind the above-mentioned drying steps is being carried out agglomerating sintering step.
The feature of above-mentioned each feature of the present invention and other and their effect are by the explanation of following embodiment as can be known.
The effect of invention
According to the present invention, obtain the catheter tube for medical treatment of thin-walled and anti-extensibility, anti-kink, inner chamber lubricity excellence.According to this conduit, can provide particularly to prevent owing to the reduction of the elongation of the conduit that the use in when operation, operation are caused and the inner chamber lubricity when inserting utensil, do not produce conduit and manufacture method thereof that operability reduces.
Description of drawings
[Fig. 1] Fig. 1 is the sketch map based on the conduit manufacture method of embodiments of the present invention.
Symbol description
1 metal core wire
2 conveying rollers
3 stick with paste extruder
4 extruder barrels
5 extruder plugs
6 die heads
7 centrepins
8 pipe molded bodys
9 the 1st drying ovens
10 the 2nd drying ovens
11 the 3rd drying ovens
12 sintering furnaces
The 13PTFE light-wall pipe
14 coiling machines
The specific embodiment
Based on embodiment the present invention is carried out specific description below.
1. the wall thickness of catheter tube for medical treatment
" wall thickness " of the catheter tube for medical treatment among the present invention is below the 0.10mm, is 0.005～0.10mm for example, is preferably 0.01～0.09mm, more preferably 0.02～0.08mm.Owing to can make the thin conduit of wall thickness in above-mentioned scope, for example,, can suppress the flow reduction of medicament or the flow resistance of intravascular mass even when the thin footpath of pipe, also can make internal diameter bigger.But if the wall thickness of conduit is too small then owing to cause frictional resistance in the operation of therapeutic appliance etc., the lubricity on tube cavity surface reduces, so not preferred.In addition, if the excessive then conduit of wall thickness is poor to the insertion of blood vessel, so not preferred.
2. the fusing point peak of catheter tube for medical treatment
To the fusing point not special provision of peak of the thin-walled catheter tube for medical treatment among the present invention, for example be more than 320 ℃, be preferably more than 322 ℃, more preferably more than 324 ℃.If the fusing point peak might produce bad problem on the position adjustments when inserting therapeutic appliance, so not preferred less than 320 ℃ of then easily displacements of pipe.The higher limit at fusing point peak is because high more preferred more, and not special provision for example is below 330 ℃, is preferably below 329 ℃, more preferably below 328 ℃.
3. the birefringence of catheter tube for medical treatment
Then birefringence is described.The molecularly oriented of plastic molded article forms by flowing or being shifted in the processing and forming, and produces anisotropy in various properties thus.Typical example is the anisotropy of refractive index.The difference of two different refractivities will observing in having optically anisotropic object is defined as birefringence.Be that birefringence represents that the difference of the refractive index of the perpendicular direction of certain direction is size poor of molecularly oriented.Usually the refractive index of the refractive index ratio of big expression one direction of birefringence and the vertical direction of this direction is big, and the molecularly oriented of a direction is than big with the molecularly oriented of the vertical direction of this direction.
The length direction of " birefringence (Δ n1) " among the present invention expression catheter tube for medical treatment and poor with the refractive index of the vertical circumferencial direction of length direction, birefringence is big more represents that then the anti-extensibility of length direction, anti-kink, inner chamber lubricity are high more.Reduce as if the too small then anti-extensibility of birefringence on the other hand, the elongation that might produce catheter tube for medical treatment thus, the result for example might produce bad problem on the position adjustments when therapeutic appliance such as conduit are inserted, so not preferred.Birefringent assay method as described later.
That is, the birefringence of the catheter tube for medical treatment among the present invention is limited to 2.5 * 10 down
-3More than, be preferably 2.7 * 10
-3More than, more preferably 3.0 * 10
-3More than.Above-mentioned birefringence if in above-mentioned scope then to not special provision of the upper limit, for example be 5.0 * 10
-2Below, more preferably 4.0 * 10
-2Below, more preferably 3.0 * 10
-2Below.
4. the hot strength of catheter tube for medical treatment
" hot strength (the S1) (N/mm during the 1.0mm displacement of the catheter tube for medical treatment among the present invention
2) with the relation of birefringence (Δ n1) " be
S1 〉=170.0 * Δ n1+3.0 is preferably
S1 〉=200.0 * Δ n1+3.0, more preferably
S1≥410.0×Δn1+3.0，
Above-mentioned relation is
During S1＜170.0 * Δ n1+3.0, because the orientation of PTFE particle is low, so might produce the elongation of catheter tube for medical treatment or because the reduction of the inner chamber lubricity that landing caused of PTFE particle, position adjustments or utensil when the result might produce therapeutic appliance such as seal wire and inserts insert ill bad problem, so not preferred.
To " hot strength " not special provision of the catheter tube for medical treatment among the present invention, when length direction is shifted at 1.0mm, be limited to 5.0N/mm down
2More than, be preferably 7.0N/mm
2More than, 10.0N/mm more preferably
2More than.If above-mentioned hot strength then to not special provision of the upper limit, for example is 150.0N/mm in above-mentioned scope
2Below, 100.0N/mm more preferably
2Below, 50.0N/mm more preferably
2Below.If the too small elongation that then might produce catheter tube for medical treatment of hot strength, the result for example might produce bad problem on the position adjustments when therapeutic appliance such as seal wire are inserted, so not preferred.
5. tetrafluoro ethylene polymer
The tetrafluoro ethylene polymer particle that contains in " tetrafluoro ethylene polymer " among the present invention preferably is orientated along the length direction of catheter tube for medical treatment as far as possible.In the notion of " by sticking with paste the direction of principal axis orientation that extrusion molding makes the above-mentioned conduit of polymer particle that contains in the above-mentioned tetrafluoro ethylene polymer " of the present invention, the orientation coefficient that for example contains the length direction of the conduit of measuring by the wide-angle x-ray diffraction shows as the situation (for example with reference to fluororesin handbook (handbook) (nineteen ninety, Nikkan Kogyo Shimbun's periodical, river, lining filial piety minister volume)) 0.2 or more.Think to be orientated by going up along its length, the gap turn narrow of adjacent particle, interparticle molten the gluing during sintering further promoted.Promptly extrude, because the flow orientation of tetrafluoro ethylene polymer particle obtains in the longitudinal direction promoting that molten sticking enhancing the between particle is so the hot strength of the pipe that obtains improves by paste.
Above-mentioned tetrafluoroethylene polymer powder, for example known have powder that obtains by pulverizing and the powder that obtains by emulsion polymerisation.In the embodiment, when generally in sticking with paste extrusion molding, using, consider the preferred PTFE fine powder that uses the powder that obtains by emulsion polymerisation from having easy Fibrotic characteristic aspect.
6. lubricant
As " lubricant " among the present invention, do not limit especially, for example, preferably use by this lubricant is made an addition in the fine powder, the paste that obtains can carry out extrusion molding, and with the lubricant of the affinity excellence of above-mentioned tetrafluoro ethylene polymer (containing tetrafluoroethylene polymer powder).
" lubricant " considered aspect high for the affinity of the bigger above-mentioned tetrafluoro ethylene polymer of molecular weight, the preferred lubricant of boiling point more than 100 ℃.Can use suitably as " lubricant " and to contain fluorochemical (fluorine series lubricant agent hereinafter referred to as), and boiling point is the lubricant more than 100 ℃.
In addition, to interfacial tension (T1) and poor (T1-T2) not special provision that contains the interfacial tension (T2) of the lubricant of fluorochemical of the tetrafluoro ethylene polymer among the present invention, but preferably less than 3.6dyne/cm.If the difference of interfacial tension is more than the 3.6dyne/cm, then, can not stick with paste extrusion molding continuously, so not preferred because the affinity variation of above-mentioned polymer and lubricant is stuck with paste rapid rising of punching press generation when extruding.Above-mentioned (T1-T2) is more little then preferred more, can be for more than the 0.1dyne/cm but consider from the boiling point aspect of lubricant.
As wherein said fluorine series lubricant agent, for example can enumerate PFO (100 ℃ of boiling points), perfluor (2-butyl tetrahydrofuran) (107 ℃ of boiling points), perfluor tri-butylamine (180 ℃ of boiling points) etc.
If boiling point is then volatile from lubricant less than 100 ℃, the mouldability aspect of sticking with paste when extruding is considered not preferred.In addition, after extruding, from can be positively from molded body drying remove the lubricant aspect and consider that then preferred boiling point is the lubricant below 220 ℃, preferred especially boiling point is 120～200 ℃ a lubricant.
7. compositions
In addition, for each ratio in the compositions that contains tetrafluoro ethylene polymer and the lubricant that contains fluorochemical, with respect to tetrafluoroethylene polymer powder 100 weight portions, lubricant can be in the scope of 10～100 weight portions, but consider from the extrusion molding aspect, preferred 25～85 weight portions, preferred especially 40～70 weight portions.
In addition, contain tetrafluoroethylene polymer powder and with the compositions of the lubricant of the affinity excellence of this tetrafluoroethylene polymer powder in, in the scope of not damaging performance, can contain x-ray contrast agent powder, dispersion stabilizer, viscosity modifier, surfactant, pH regulator agent etc.As the material of x-ray contrast agent powder, can use tungsten, gold, platinum, barium sulfate, bismuth oxide, hydroxy acid bismuth, bismuth subcarbonate, zirconium oxide, bismuth trioxide, tantalum, sodium iodide, silver-protein colloid, silver iodide-gelatin gels, thorium oxide (IV) colloidal sol, iodol alkane ketone sodium acetate, powder of stainless steel, titanium powder etc.
8. the manufacture method of conduit
Manufacture method as the catheter tube for medical treatment among the present invention, do not limit especially, the preferred use stuck with paste extrusion molding, sticks with paste extrusion molding and can use known method (for example with reference to fluororesin handbook (handbook) (nineteen ninety, Nikkan Kogyo Shimbun's periodical, river, lining filial piety minister are compiled)) in the past.
Fig. 1 represents the sketch map as the manufacture method of embodiments of the present invention.Contain in this manufacture method and stick with paste extrusion molding step (paste extrusion moulding), drying steps, sintering step.The manufacture method that method of the present invention also comprises the scope of the present invention that do not break away from claim record, above-mentioned embodiment is suitably changed.
Fig. 1 send machine 2, paste extruder 3, extruder barrel 4, extruder plug 5, die head 6, centrepin 7, pipe molded body the 8, the 1st drying oven the 9, the 2nd drying oven the 10, the 3rd drying oven 11, sintering furnace 12, PTFE light-wall pipe 13, coiling machine 14 to constitute by the volume of metal core wire 1.
Then extrude Overmoldedly, obtain managing molded body 8 by sticking with paste extruder 3 will contain above-mentioned lubricant on metal core wire PTFE compositions.Then, when regulating the speed, make this Overmolded pipe molded body 8 successively by the drying oven 9～11 of implementing dried, the sintering furnace 12 of implementing sintering processes, thereby obtain PTFE light-wall pipe 13 by coiling machine 14.In order to obtain desired external diameter, the PTFE tube of internal diameter, can appropriate change extruder barrel 4, extruder plug 5, die head 6, centrepin 7.
As the dried in the manufacture method of the present invention, do not limit especially, for example, under the temperature more than the boiling point of employed lubricant, carry out dried by drying oven 9～11, can from pipe molded body 8, remove lubricant thus.Can use common fire kiln or heated air circulation type drying oven in the drying oven 9～11.The dried of carrying out under the temperature of the boiling point that is lower than lubricant might crack or porous because of the bumping that remains in the lubricant in the pipe during owing to the aftermentioned sintering, so not preferred.
Further,, do not limit especially, for example more than the fusing point of PTFE, handle, consider it is preferred from making the molten each other sticking aspect of PTFE particle by sintering furnace 12 as the sintering processes in the manufacture method of the present invention.
The fusing point of PTFE is 320～330 ℃.Therefore, sintering processes, as under be limited to more than 340 ℃, be preferably more than 370 ℃, more than 400 ℃,, be below 650 ℃ more preferably in addition as the upper limit, be preferably below 620 ℃, more preferably 590 ℃ are carried out to get off.
Can use common heated type sintering furnace or heated air circulation type sintering furnace in the sintering furnace 12.If be lower than the temperature of the fusing point of PTFE,, may the stress fibrillation when batching cause cracking sometimes, so not preferred then because sintering is insufficient.
As mentioned above, one of feature of present embodiment is:
(i) by the PTFE compositions that contains the high lubricant of tetrafluoro ethylene polymer (PTFE) and affinity is stuck with paste extrusion molding, make polymer particle be orientated (corresponding to " tetrafluoro ethylene polymer is orientated in the longitudinal direction ") as far as possible in the longitudinal direction, and by utilize the high-affinity lubricant make particle the orientation homogenization (corresponding to " and by paste extrude with contain tetrafluoro ethylene polymer and for the composition molding of the high lubricant of the affinity of this polymer ")
This lubricant that volatilizees when (ii) dry reduces the gap (making the particle close mode by removing lubricant) of this polymer particle
(iii) make the part fusing of this PTFE during sintering, make between the particle of gap turn narrow molten each other sticking (the molten clayization of particle).Since molten each other sticking between the particle, so the conduit that is obtained by embodiment for example has excellent hot strength.
As mentioned above, the lubricant that the affinity of utilization and PTFE is high is orientated polymer particle along its length, on the other hand by this lubricant of volatilization, shorten interparticle distance, improve interparticle molten sticking effect, and the design that improves hot strength is based on present inventor's design of opinion alone.And above-mentioned patent documentation 5 discloses the PTFE compositions that contains fluoropolymer polymer.But, the fluoropolymer polymer of the document use with amorphous state, performance is as the binding agent function aspects of so-called PTFE polymer particle, the function that is had with " lubricant that contains fluorochemical " of the embodiment of the invention described above of the molten clayization that mainly contains the orientation that helps particle and particle itself is different.
9. evaluation methodology
Evaluation of estimate described in this description refers to the value of measuring by following method.
(mouldability)
External diameter of pipe when the laser microdiameter of use Takikawa Engineering Co., Ltd. system extrudes paste is measured with online online mode.With respect to the average tube external diameter, observe+during the above external diameter of 0.03mm, mouldability is judged to be *, during less than 0.03mm, mouldability is judged to be zero.
(anti-elongation test: hot strength)
Use the smart mechanism of Toyo Co., Ltd. to make made Strograph EII, implementing anti-elongation test under apart from 50mm, chuck speed 100mm/min between force cell 50N, chuck.As anti-elongation load, the stress value (N/mm when adopting aforementioned tube to extend 1.0mm along its length
2).
(conduit wall thickness)
Use the laser microdiameter of Takikawa Engineering Co., Ltd. system, external diameter of pipe and heart yearn are directly measured.Wall thickness is calculated by following formula.
(wall thickness/mm)=(external diameter of pipe/mm-heart yearn footpath/mm)/2
(fusing point peak)
Use Shimadzu Scisakusho Ltd's system differential scanning calorimetry device under the condition of 10 ℃/minute of programming rates, stream of nitrogen gas atmosphere gasification (30mL/ minute), to measure.To melt the peak of caloric receptivity as the fusing point peak.
(boiling point of lubricant)
Use Hewlett Packard society's system gas chromatogram (GC System HP6890 series) that boiling point is measured.
(birefringence)
Describe for birefringent assay method.Birefringence is represented with following formula.
Δn＝Re/t
Wherein, Δ n is a birefringence, and Re is phase contrast (unit for example is mm (millimeter)), and t is thickness of sample (unit for example is mm (millimeter)).Can practical measurement be to postpone and thickness of sample, when described delay represents to be clipped in 2 blocks of mensuration light in the polaroid by sample, the phase contrast that produces owing to the refractivity in the sample.Postpone to use the simple and easy delay analyzer of prince's instrumentation machine Co., Ltd.'s system to be measured.Thickness adopts the measured value of above-mentioned conduit wall thickness.
(interfacial tension of powder)
The interfacial tension of tetrafluoroethylene polymer powder (T1) is taken passages in the 4th edition V/33 of polymer handbook (polymerhandbook) (18.6dyne/cm).The interfacial tension (T2) that contains the lubricant of fluorochemical is used Jitian to make system DUNOUY ' the S PRECISION TENSIONMETER of society of institute and is measured under 23 ℃, the state of relative humidity 50%.
(anti-kink test)
Use the system E-Z of Shimadzu Scisakusho Ltd tester, implementing anti-kink test under apart from 120mm, chuck speed 50mm/min between force cell 1N, chuck.Kink length is calculated by following formula.
(kink length/mm)=(the initial stage ring length/mm)-(tensile elongation during kink/mm)
Visual judgement during kink.The short more then anti-kink of kink length is excellent more.
(inner chamber lubricity test)
Use the smart mechanism of Toyo Co., Ltd. to make made Strograph EII, the ring of three all φ 16.5mm is set, behind the pure water ascending pipe, make seal wire reciprocal for 50 times with stroke 25mm, test speed 500mm/min at the pipe front end.With the index of the seal wire turnover stress after the stress of primary seal wire turnover and 50 times back and forth as the inner chamber lubricity.The more little then inner chamber of the difference lubricity of the stress after initial stage and 50 times back and forth is excellent more.
Embodiment
Though hereinafter specific embodiment and the comparative example that the present invention relates to is specifically described, the present invention is not limited to these embodiment.In following each embodiment and comparative example, except specifying, all the other use above-mentioned each device shown in Figure 1 to make conduit.
(embodiment 1)
In vial, add PTFE fine powder A (trade name: Polyflon (Port リ Off ロ Application) PTFEF-207, Da Jin ( ィ キ Application) industrial society system) 100 weight portions and lubricant A (trade name: KoseiSol (コ-セ ゾ-Le) FC-1, good fortune become business Co., Ltd. system, 120 ℃ of boiling points, interfacial tension 15.5dune/cm) 56 weight portions, in temperature chamber, left standstill under 50 ℃ 24 hours, after carrying out ripening thus, be cooled to room temperature, mix by vibration then.After the mixing,, adopt in the preforming usefulness barrel of 18mm φ and compress 5 minutes method with the pressure of 1.0MPa in order to obtain preform.Further in order to remove the bubble of preform, a preform that obtains is added in the barrel of extrusion shaping machine, the pressure that closing cap applies 28MPa carries out 30 seconds secondary preforming.The internal diameter of sticking with paste the extruder barrel 4 of extruder 3 is that the external diameter of 18mm, extruder plug 5 is 12mm, uses the die head 6 of internal diameter 0.60mm, the centrepin 7 of external diameter 0.56mm in addition, and barrel and die head temperature are set at 30 ℃ respectively.
Then, from sticking with paste extruder 3 with drawing velocity 1.5mm/ minute extruding pipe molded body 8, make this pipe molded body 8 through being set at 240 ℃ the 1st drying oven 9, being set at 300 ℃ the 2nd drying oven 10, being set at 420 ℃ the 3rd drying oven 11, being set at 540 ℃ sintering furnace 12, batch with 3.0m/ minute speed by coiling machine 14, make the PTFE light-wall pipe 13 of external diameter 0.58mm, internal diameter 0.52mm.
Mouldability when paste is extruded is zero.Hot strength when the 1.0mm of the PTFE light-wall pipe that mensuration obtains is shifted is 7.0N/mm
2Measuring kink length is 43mm.In addition, 1 of the inner chamber lubricity test reciprocal stress is that 0.48N, 50 reciprocal stress are 0.47N.
(embodiment 2)
(make the PTFE light-wall pipe similarly to Example 1 trade name: Fluorinert (Off ロ リ Na-ト) FC-40, Sumitomo 3M Co., Ltd. system, 155 ℃ of boiling points, surface tension 16.0dyne/cm) 56 weight portions except adding lubricant B.Mouldability when paste is extruded is zero.Hot strength when the 1.0mm of the PTFE light-wall pipe that mensuration obtains is shifted is 7.6N/mm
2The kink length of measuring is 42mm.In addition, 1 of the inner chamber lubricity test reciprocal stress is that 0.45N, 50 reciprocal stress are 0.47N.
(embodiment 3)
Except adding lubricant C (trade name: Fluorinert FC-43, Sumitomo 3M Co., Ltd. system, 174 ℃ of boiling points, surface tension 16.0dyne/cm) 56 weight portions, make the PTFE light-wall pipe similarly to Example 1.Mouldability when paste is extruded is zero.Hot strength when the 1.0mm of the PTFE light-wall pipe that mensuration obtains is shifted is 6.4N/mm
2The kink length of measuring is 45mm.In addition, 1 of the inner chamber lubricity test reciprocal stress is that 0.43N, 50 reciprocal stress are 0.45N.
(embodiment 4)
Except adding PTFE fine powder B (trade name: Polyflon PTFE F-201, Daikin Industries society system) 100 mass parts, make the PTFE light-wall pipe similarly to Example 1.Mouldability when paste is extruded is zero.Hot strength when the 1.0mm of the PTFE light-wall pipe that mensuration obtains is shifted is 7.8N/mm
2The kink length of measuring is 42mm.In addition, 1 of the inner chamber lubricity test reciprocal stress is that 0.50N, 50 reciprocal stress are 0.48N.
(embodiment 5)
Except the die head of the centrepin that adopts external diameter 0.46mm, internal diameter 0.50mm, make the PTFE light-wall pipe similarly to Example 2.Mouldability when paste is extruded is zero.Hot strength when the 1.0mm of the PTFE light-wall pipe that mensuration obtains is shifted is 9.7N/mm
2The kink length of measuring is 34mm.In addition, 1 of the inner chamber lubricity test reciprocal stress is that 0.60N, 50 reciprocal stress are 0.58N.
(comparative example 1)
Repeat the coating and the sintering of PTFE dispersion liquid (trade name: PTFEAD-1, Asahi Glass Co., Ltd's system) by silver-plated annealed copper wire, make the PTFE light-wall pipe of external diameter 0.58mm, internal diameter 0.52mm diameter 0.52mm.Hot strength when the 1.0mm of the PTFE light-wall pipe that mensuration obtains is shifted is 4.3N/mm
2The kink length of measuring is 56mm.In addition, 1 of the inner chamber lubricity test reciprocal stress is that 0.48N, 50 reciprocal stress are 0.73N.
(comparative example 2)
Except adding lubricant D (trade name: Fluorinert FC-77, Sumitomo 3M Co., Ltd. system, 97 ℃ of boiling points, surface tension 15.0dyne/cm) 56 weight portions, make the PTFE light-wall pipe similarly to Example 1.But can not evenly extrude, stick with paste when extruding mouldability for *, above-mentioned silver-plated annealed copper wire fracture in the molding.
(comparative example 3)
Except adding lubricant E (trade name: Isopar (ァ ィ ソ パ) M, Exxon Mobil (ェ Network ソ Application モ-PVC Le) Co., Ltd.'s system, 198 ℃ of boiling points, interfacial tension) 56 weight portions, make the PTFE light-wall pipe similarly to Example 1.But PTFE particle fibrillation can not evenly be extruded, stick with paste when extruding mouldability for *, above-mentioned silver-plated annealed copper wire fracture in the molding.
Above result is as shown in table 1.
By the result of each embodiment in the table 1 and comparative example as can be known, stick with paste and extrude, then can suppress the reduction of mouldability, anti-kink, anti-extensibility and inner chamber lubricity by in the tetrafluoroethene polymer powder, adding the lubricant that contains fluorochemical.Particularly aspect anti-extensibility, the orientation effect of PTFE particle of extruding realization by paste is big.Be this be because, the orientation by the PTFE particle and molten sticking shows big intensity for external force, anti-kink, anti-extensibility, inner chamber lubricity improve.
In following embodiment and comparative example,,, use above-mentioned each device shown in Figure 1 to make conduit except specifying with similarly above-mentioned.
(embodiment 6)
In vial, add PTFE fine powder A (trade name: Polyflon PTFE F-207, Daikin Industries society system) 100 weight portions and lubricant A (trade name: Fluorinert FC-40, Sumitomo 3M Co., Ltd. system, 155 ℃ of boiling points, surface tension 16.0dyne/cm) 56 weight portions, in temperature chamber, left standstill under 50 ℃ 24 hours, after carrying out ripening thus, be cooled to room temperature, mix by vibration then.This lubricant A contains for the high perfluor-tetrahydrofuran class fluorochemical of the affinity of tetrafluoro ethylene polymer, and boiling point is more than 150 ℃.
After the mixing,, adopt in the preforming usefulness barrel of 18mm φ and compress 5 minutes method with the pressure of 1.0MPa in order to obtain preform.Further in order to remove the bubble of preform, a preform that obtains is added in the barrel of extrusion shaping machine, the pressure that closing cap applies 28MPa carries out 30 seconds secondary preforming.The internal diameter of sticking with paste the extruder barrel 4 of extruder 3 is that the external diameter of 18mm, extruder plug 5 is 12mm, uses the die head 6 of internal diameter 0.60mm, the centrepin 7 of external diameter 0.56mm in addition, and barrel and die head temperature are set at 30 ℃ respectively.
Then, from sticking with paste extruder 3 with drawing velocity 1.5mm/ minute extruding pipe molded body 8, make this pipe molded body 8 through being set at 240 ℃ the 1st drying oven 9, being set at 300 ℃ the 2nd drying oven 10, being set at 420 ℃ the 3rd drying oven 11, being set at 540 ℃ sintering furnace 12, batch with 3.0m/ minute speed by coiling machine 14, make the PTFE light-wall pipe 13 of external diameter 0.58mm, internal diameter 0.52mm.
The birefringence of the PTFE light-wall pipe that mensuration obtains is 1.3 * 10
-2Hot strength when measuring the 1.0mm displacement is 7.6N/mm
2The kink length of measuring is 42mm.In addition, 1 of the inner chamber lubricity test reciprocal stress is that 0.45N, 50 reciprocal stress are 0.47N.
(embodiment 7)
Except the die head of the centrepin that adopts external diameter 0.56mm, internal diameter 0.61mm, make the PTFE light-wall pipe similarly to Example 6.The birefringence of the PTFE light-wall pipe that mensuration obtains is 6.4 * 10
-3Hot strength when measuring the 1.0mm displacement in addition is 7.0N/mm
2The kink length of measuring is 43mm.In addition, 1 of the inner chamber lubricity test reciprocal stress is that 0.48N, 50 reciprocal stress are 0.47N.
(embodiment 8)
Except the die head of the centrepin that adopts external diameter 0.56mm, internal diameter 0.58mm, make the PTFE light-wall pipe similarly to Example 6.The birefringence of the PTFE light-wall pipe that mensuration obtains is 8.9 * 10
-3Hot strength when measuring the 1.0mm displacement in addition is 6.4N/mm
2The kink length of measuring is 45mm.In addition, 1 of the inner chamber lubricity test reciprocal stress is that 0.43N, 50 reciprocal stress are 0.45N.
(embodiment 9)
Except adding PTFE fine powder B (trade name: Fluon PTFE CD090, Asahi Glass Co., Ltd's system) 100 mass parts, make the PTFE light-wall pipe similarly to Example 6.The birefringence of the PTFE light-wall pipe that mensuration obtains is 1.3 * 10
-2Hot strength when measuring the 1.0mm displacement in addition is 5.9N/mm
2The kink length of measuring is 46mm.In addition, 1 of the inner chamber lubricity test reciprocal stress is that 0.50N, 50 reciprocal stress are 0.48N.
(embodiment 10)
Except adding PTFE fine powder C (trade name: Teflon (テ Off ロ Application) PTFE 640-J, Mitsui DuPont Fluorochemicals (テ ュ Port Application Off ロ ロ ケ ミ カ Le) Co., Ltd.'s system) 100 mass parts, make the PTFE light-wall pipe similarly to Example 6.The birefringence of the PTFE light-wall pipe that mensuration obtains is 1.2 * 10
-2Hot strength when measuring the 1.0mm displacement in addition is 7.0N/mm
2The kink length of measuring is 42mm.In addition, 1 of the inner chamber lubricity test reciprocal stress is that 0.49N, 50 reciprocal stress are 0.47N.
(embodiment 11)
Except the die head of the centrepin that adopts external diameter 0.46mm, internal diameter 0.50mm, make the PTFE light-wall pipe similarly to Example 6.The birefringence of the PTFE light-wall pipe that mensuration obtains is 1.2 * 10
-2Hot strength when measuring the 1.0mm displacement in addition is 9.7N/mm
2The kink length of measuring is 34mm.In addition, 1 of the inner chamber lubricity test reciprocal stress is that 0.60N, 50 reciprocal stress are 0.58N.
Below in order to compare with embodiment 6-11,4-8 makes conduit as a comparative example.Identical with embodiment 6,7,9 respectively aspect comparative example 4,7,8 external diameters, internal diameter, the wall thickness at PTFE.Comparative example 5 is identical with embodiment 11 aspect the external diameter of PTFE, internal diameter, wall thickness.
In the comparative example, aspect the coating of carrying out PTFE and sintering with adopt that to stick with paste the extrusion molding step different with embodiment 6-10 dry, sintering step.Further, in the comparative example, do not make with lubricator.
(comparative example 4)
Repeat the coating and the sintering of PTFE dispersion liquid D (trade name: PTFE dispersion (デ ィ ス パ-ジ ョ Application) AD-1, Asahi Glass Co., Ltd's system) by silver-plated annealed copper wire, make the PTFE light-wall pipe of external diameter 0.58mm, internal diameter 0.52mm diameter 0.52mm.The birefringence of the PTFE light-wall pipe that mensuration obtains is 2.0 * 10
-3Hot strength when the 1mm that measures is shifted in addition is 4.3N/mm
2The kink length of Ce Dinging is 56mm in addition.In addition, 1 of the inner chamber lubricity test reciprocal stress is that 0.48N, 50 reciprocal stress are 0.73N.
(comparative example 5)
Except the silver-plated annealed copper wire to diameter 0.42mm be coated with sintering, similarly make the PTFE light-wall pipe with comparative example 4, obtain the PTFE light-wall pipe of external diameter 0.48mm, internal diameter 0.42mm.The birefringence of the PTFE light-wall pipe that mensuration obtains is 2.1 * 10
-3Hot strength when measuring the 1mm displacement in addition is 4.1N/mm
2The kink length of Ce Dinging is 48mm in addition.In addition, 1 of the inner chamber lubricity test reciprocal stress is that 0.61N, 50 reciprocal stress are 0.84N.
(comparative example 6)
Similarly make the PTFE light-wall pipe with comparative example 4, obtain the PTFE light-wall pipe of external diameter 0.46mm, internal diameter 0.42mm.The birefringence of the PTFE light-wall pipe that mensuration obtains is 2.3 * 10
-3Hot strength when measuring the 1mm displacement in addition is 3.7N/mm
2The kink length of Ce Dinging is 62mm in addition.In addition, 1 of the inner chamber lubricity test reciprocal stress is that 0.63N, 50 reciprocal stress are 1.15N.
(comparative example 7)
Except using PTFE dispersion liquid E (trade name: Teflon dispersion 30, Mitsui Du PontFluorochemicals Co., Ltd. system), similarly make the PTFE light-wall pipe with comparative example 4.The birefringence of the PTFE light-wall pipe that mensuration obtains is 2.2 * 10
-3Hot strength when measuring the 1mm displacement in addition is 4.1N/mm
2The kink length of measuring is 58mm.In addition, 1 of the inner chamber lubricity test reciprocal stress is that 0.52N, 50 reciprocal stress are 0.80N.
(comparative example 8)
Except using PTFE dispersion liquid F (trade name: Polyflon PTFE dispersion D-1E, Daikin Industries society system), similarly make the PTFE light-wall pipe with comparative example 4.The birefringence of the PTFE light-wall pipe that mensuration obtains is 2.2 * 10
-3Hot strength when measuring the 1mm displacement in addition is 4.0N/mm
2The kink length of measuring is 55mm.In addition, 1 of the inner chamber lubricity test reciprocal stress is that 0.50N, 50 reciprocal stress are 0.77N.
More than, the measurement result of each pipe that is obtained by embodiment 6-11 and comparative example 4-8 is as shown in table 2.
By the result of each embodiment in the table 2 and comparative example as can be known, if birefringent value is 2.5 * 10
-3More than, then be (with reference to " the PTFE wall thickness " of table 2 etc.) and the anti-extensibility (with reference to " hot strength " of table 1) and anti-kink (with reference to " the kink length " of the table 2) excellence of thin-walled, the reduction of inner chamber lubricity be inhibited (with reference to " seal wire stress (1 time is back and forth) and (50 times are reciprocal) " of table 2).Promptly, show big intensity for external force, thereby the reduction of anti-kink, anti-extensibility, inner chamber lubricity is inhibited by the orientation effect and the fusion of PTFE particle.
Claims (15)
1. a catheter tube for medical treatment contains tetrafluoro ethylene polymer, it is characterized in that, wall thickness is below the 0.1mm, and the hot strength (S1) in 1.0mm when displacement is 5.0N/mm
2More than.
2. the described catheter tube for medical treatment of claim 1 is characterized in that, the fusing point peak is more than 320 ℃.
3. a catheter tube for medical treatment contains tetrafluoro ethylene polymer, it is characterized in that, wall thickness is below the 0.1mm, and birefringence (Δ n1) is 2.5 * 10
-3More than.
4. the described catheter tube for medical treatment of claim 3 is characterized in that, the hot strength (S1) during the 1.0mm displacement is 5.0N/mm
2More than.
5. each described catheter tube for medical treatment in the claim 1～4 is characterized in that, the hot strength (S1) of described catheter tube for medical treatment when 1.0mm is shifted with the pass of birefringence (Δ n1) is:
S1≥170.0×Δn1+3.0。
6. the catheter tube for medical treatment that improves of a hot strength, contain tetrafluoro ethylene polymer, it is characterized in that, under coexisting at the lubricant high to the affinity of this tetrafluoro ethylene polymer, described tetrafluoro ethylene polymer is stuck with paste extrusion molding, make the polymer particle that contains in the described tetrafluoro ethylene polymer direction of principal axis orientation, then when the described conduit of drying along described conduit, by making described lubricant volatilization, make the gap turn narrow between described polymer particle.
7. each described catheter tube for medical treatment in the claim 1～6 is characterized in that described tetrafluoro ethylene polymer is orientated along its length.
8. a method of making each described catheter tube for medical treatment in the claim 1～7 is characterized in that, extrudes by paste, will contain described tetrafluoro ethylene polymer and to the composition molding of the high lubricant of the affinity of this polymer.
9. the described manufacture method of claim 8, wherein, described tetrafluoroethylene polymer powder is the tetrafluoroethylene polymer powder by the emulsion polymerisation manufactured.
10. claim 8 or 9 described manufacture methods, wherein, described lubricant is the lubricant that contains fluorochemical.
11. each described manufacture method is characterized in that in the claim 8～10, the boiling point of described lubricant is more than 100 ℃.
12. each described manufacture method is characterized in that in the claim 8～11, poor (T1-T2) of the surface tension (T2) of surface tension of described tetrafluoro ethylene polymer (T1) and described lubricant is less than 3.6dyne/cm.
13. each described manufacture method in the claim 8～12 wherein, also is included in the drying steps that carries out more than the boiling point of described lubricant.
14. the described manufacture method of claim 13 wherein, behind described drying steps, also is included in the sintering step that carries out more than the fusing point of described tetrafluoro ethylene polymer.
15. the manufacture method of a catheter tube for medical treatment, described catheter tube for medical treatment contains tetrafluoro ethylene polymer, and this method comprises:
(a) extrusion molding step, for making the polymer particle that contains in the described tetrafluoro ethylene polymer direction of principal axis orientation along described conduit, under coexistence, described tetrafluoro ethylene polymer is stuck with paste extrusion molding and obtained managing molded body for the high lubricant of the affinity of described tetrafluoro ethylene polymer;
(b) drying steps, for at least a portion of the described lubricant that will contain in the described pipe molded body is removed, make the interparticle gap turn narrow that contains in the described tetrafluoro ethylene polymer simultaneously, more than the boiling point of described lubricant, described pipe molded body is carried out drying;
(c) sintering step, molten each other sticking in order to make between the particle that contains in the described tetrafluoro ethylene polymer, more than the fusing point of described tetrafluoro ethylene polymer the pipe molded body behind the described drying steps is being carried out sintering.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005302099 | 2005-10-17 | ||
| JP302099/2005 | 2005-10-17 | ||
| JP010472/2006 | 2006-01-18 |
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| Publication Number | Publication Date |
|---|---|
| CN101291695A true CN101291695A (en) | 2008-10-22 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800386890A Pending CN101291695A (en) | 2005-10-17 | 2006-10-17 | Medical catheter tubes and process for production thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107428958A (en) * | 2016-03-20 | 2017-12-01 | 株式会社润工社 | Polyfluortetraethylene pipe |
| CN108327213A (en) * | 2018-02-06 | 2018-07-27 | 苏州海维尔医疗器械有限公司 | Superslide seal wire external coating is dissolved former and its method for coating |
| CN111655322A (en) * | 2018-01-31 | 2020-09-11 | 株式会社钟化 | Catheter handle and catheter with same |
| WO2021025814A1 (en) | 2019-08-07 | 2021-02-11 | Zeus Industrial Products, Inc. | Catheter comprising ptfe liner |
| CN113386316A (en) * | 2021-06-11 | 2021-09-14 | 河北工业大学 | Method for preparing multi-cavity tube based on hot stretching technology |
-
2006
- 2006-10-17 CN CNA2006800386890A patent/CN101291695A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107428958A (en) * | 2016-03-20 | 2017-12-01 | 株式会社润工社 | Polyfluortetraethylene pipe |
| CN107428958B (en) * | 2016-03-20 | 2019-10-22 | 株式会社润工社 | Polyfluortetraethylene pipe |
| CN111655322A (en) * | 2018-01-31 | 2020-09-11 | 株式会社钟化 | Catheter handle and catheter with same |
| CN108327213A (en) * | 2018-02-06 | 2018-07-27 | 苏州海维尔医疗器械有限公司 | Superslide seal wire external coating is dissolved former and its method for coating |
| WO2021025814A1 (en) | 2019-08-07 | 2021-02-11 | Zeus Industrial Products, Inc. | Catheter comprising ptfe liner |
| EP3986492A4 (en) * | 2019-08-07 | 2023-07-19 | Zeus Company Inc. | Catheter comprising ptfe liner |
| CN113386316A (en) * | 2021-06-11 | 2021-09-14 | 河北工业大学 | Method for preparing multi-cavity tube based on hot stretching technology |
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