DE29522041U1 - Elastomeric block copolymer catheter balloons - Google Patents

Description

MAIWALD 'GMBH'

PATENT ATTORNEYS

Reference number Our reference

New German S 7252

Utility model application

Munich

Dr. Walter Maiwald

Patent Attorney

European Patent Attorney

European Trademark Attorney

Dr. Volker Hamm

Dr. Stefan Michalski

Patent attorneys

European Trademark Attorneys

Loerrach

Dr. Walter Maiwald
European Patent Attorney

in collaboration with: Schulze & Althoff
law firm

Munich,

18 December 1998

Scimed Life Systems, Inc.
One Scimed Place, Maple Grove, Minnesota 55311-1566, V.St.A.

Elastomeric block copolymer catheter balloons

Background of the invention

Balloons mounted on the distal ends of catheters are widely used in medical treatment. The balloon can be used to expand a vessel into which the catheter is inserted or to force the opening of a blocked vessel. The strength and size requirements of the balloons vary greatly depending on the intended use of the balloon and the size of the vessel into which the catheter is inserted. Perhaps the most demanding applications for such balloons are in balloon angioplasty.

. PO BOX 330523 · 80065 MUNICH

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TELEPHONE +49/(0)89-74 72 66-0 · FAX +49/(0)89-77 64 24 · VOICE +49/(0)89-74 72 &oacgr;&oacgr; 10

_n ~.~ Email: maiwald @ maiwald-partner. com

S IZbZ NOTE UUL _{Managing Director:Dr} . waiter Maiwald · HRB No. 111307

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where catheters are inserted over long distances into extremely small vessels and are used to open stenoses in blood vessels by inflating the balloon. These applications require extremely thin-walled, high-strength, and relatively inelastic balloons with predictable inflation characteristics. Thin walls are necessary because the wall and waist thicknesses of the balloons limit the minimum diameter of the distal end of the catheter, and thus determine the limits of the vessel size that can be treated by the method and ease of passing the catheter through the vascular system. High strength is necessary because the balloon is used to rupture a stenosis and the thin wall must not burst under the high internal pressures necessary to perform this task. The balloon should have some elasticity so that the diameter can be regulated when inflated to allow the surgeon to change the diameter of the balloon as necessary to treat individual lesions; However, this elasticity must be relatively low so that the diameter can be easily controlled. Small pressure changes must not cause large changes in the diameter.

While angioplasty balloons are considered inelastic relative to balloons used for most other applications, there is a general classification of such balloons in the art based on their expandability or "compliance" relative to one another. As used herein, the "non-compliant" balloons are the least elastic, increasing in diameter by about 2-7%, typically about 5%, as the balloon is pressurized from an inflation pressure of about 6 atm. to a pressure of about 12 atm., i.e., they have an "expansion" of about 5% over that pressure range. "Semi-compliant" balloons have slightly larger expansions, generally from 7-16% and typically from 7-12% over the same pressure range. "Yielding" balloons are even more expandable, with expansions generally in the range of 16-40% and typically about 21% over the same pressure range. Maximum expansions, i.e. expansion from nominal diameter to burst, of different balloon materials can be significantly higher than the percentage expansions discussed above because the wall strengths and hence

the burst pressures vary widely between balloon materials. The inflation range of 6-12 atm is used in the present application to enable a direct comparison of the compliance characteristics of different balloons.

The strength of the polymer materials used in the balloons varies widely. The strongest balloons are also the least elastic, made from highly orientable polymers, such as polypropylene, polyethylene terephthalate or other phthalate polyesters or copolyesters and nylons. Wall tear strengths are usually 20,000-50,000 psi. Commercial angioplasty balloons made from such materials with nominal diameters in the range of 1.5-4.5 mm have expansions in the non-compliant to semi-compliant range, and can often be subjected to pressures of 16 atm or higher without danger of bursting (actual burst pressures may exceed 20 atm). In general, however, wall strength decreases as compliance increases. Other semi-compliant and compliant balloons are made from less highly orientable polymers, such as ethylene vinyl acetate, polyvinyl chloride, olefin copolymers, and ionomer resins. The wall strengths of balloons made from these less orientable materials are even lower than those made from highly orientable polymers. They are typically in the range of 6000-15000 psi, resulting in lower maximum inflation pressures of 9-10 atm.

The individual expansion and maximum pressure characteristics of a balloon are also influenced by both the polymer type and the conditions under which the balloon is inflated. Angioplasty balloons are usually made by inflating a tube of polymeric materials at a temperature above its transition temperature. For any given balloon material there is a range of achievable expansions that depend on the conditions chosen for inflating the balloon.

US Patent 4,906,244 (Pinchuck) describes balloons made of nylon materials (i.e. aliphatic polyamide), such as nylon 12, nylon 11, nylon 9,

Nylon 6/9 and Nylon 6/6. As with all other polymeric materials, the expansions of these balloons can be controlled within a range by controlling inflation conditions such as initial tubing dimensions, pre-stretch, ring expansion ratio and specified heat treatment conditions. The data in this source show that compliance characteristics ranging from non-compliant to semi-compliant characteristics can be achieved and that wall strengths greater than 15,000 can be obtained. The source suggests that higher compliances can be achieved with nylon materials, but there is no indication as to whether other nylons or other balloon manufacturing conditions can be used.

It was also proposed in U.S. Patent 4,254,774 (Boretos) to make balloons from thermoplastic elastomers, and polyamide elastomers were mentioned among a number of possible balloon materials proposed in U.S. Patent 5,250,069 (Nobuyoshi et al.). However, there are a number of such thermoplastic elastomer polymers, and prior to this invention it was expected that the performance of balloons made from these materials would generally be neither better nor higher than the average compliance of balloons made from ordinary thermoplastic polymers such as polyethylene ionomer, polyvinyl chloride, polyethylene or ethylene vinyl acetate.

In US Patent 5,290,306, polyester ether and polyetheresteramide polymers with Shore D hardnesses below 55 were proposed for use as a sheath or coextruded outer layer for a biaxially oriented nylon or polyethylene terephthalate (PET) balloon to provide the balloon with improved softness and pinprick and abrasion resistance.

Polyurethane block copolymers with a flexural modulus of about 190,000 and a limiting elongation of 250% are disclosed as balloon materials in EP 0592885, where the use of polyester block copolymers or polyamide block copolymers is also mentioned, but no suggestion is made that such alternative copolymers can be used in a useful manner when

whose flexural modulus is substantially lower or whose ultimate elongation is substantially higher than that of the disclosed polyurethane block copolymers.

Summary of the invention

New balloon materials that possess a unique combination of physical properties including non-compliant, semi-compliant and compliant expansion properties, suitable flexibility and high tensile strength are made from special thermoplastic elastomer block copolymers characterized as follows:

The block copolymer is made up of hard sections made of polyester or polyamide and soft sections made of polyether;

the polyester hard sections consist of polyesters of terephthalic acid and a C ₂ -C ₄ -DiOl,

the polyamide hard sections are polyamides of carboxylic acids with C ₆ or higher, preferably C ₁₀ -C ₁₂ , and organic diamines with C ₆ or higher, preferably C ₁₀ -C ₁₂ , or of aliphatic ω-amino-a-acids with C ₆ or higher, preferably C ₁₀ -C ₁₂ , and

the polyether soft sections are polyethers of diols with C ₂ -C ₁₀ , preferably C ₄ -C ₆ ;

the block copolymer has a low flexural modulus, namely less than 150,000 psi, preferably less than 120,000 psi;

the block copolymer has a hardness of less than 60 according to Shore D hardness; and

the weight percentage of the block polymer corresponding to the hard sections is between about 50% and about 95%.

Balloons with compliant to semi-compliant expansion profiles with wall strengths in excess of 15,000 psi, often in excess of 20,000 psi, can be made from such polymers. The high strength of balloons made from these polymers allows the construction of low profile catheters, and the low flexural modulus contributes to the soft feel found in the balloons of this invention compared to those made from other high strength polymer materials. Low profile catheters made with balloons of the invention exhibit very good initial traversal, good trackability, and good re-traversal after initial inflation.

Description of the drawings

Figure 1 shows a plot of the expansion from nominal diameter to burst of various balloons of the invention made from a polyimide/polyetherpolyester block copolymer using various ring expansion ratios to form the balloon.

Fig. 2 shows a plot as in Fig. 1 using a different polyamide/polyetherpolyester block copolymer to form the balloon according to the invention.

Detailed description of the invention

The preferred balloons of this invention are made of polyamide/polyether block copolymers. The polyamide/polyether block copolymers are commonly identified with the acronym &Rgr;&Egr;&Bgr;&Agr; (polyether block amide). The polyamide and polyether portions of these block copolymers may be linked together by amide bonds, but particularly preferred are ester-linked, sectioned polymers, i.e., polyamide/polyetherpolyester. Such polyamide/polyether/polyester block copolymers are formed by a polycondensation reaction in molten

• · ♦·

·

zene state from a dicarboxyl polyamide and a polyether diol. The result is a short-chain polyester made up of blocks of polyamide and polyether. The polyamide and polyether blocks are not miscible. Therefore, the materials are characterized by a two-phase structure: on the one hand, a thermoplastic region consisting primarily of polyamide and on the other hand, an elastomer region rich in polyether. The polyamide sections are semi-crystalline at room temperature. The generalized chemical formula for the polyester polymers can be represented by the following formula:

HO-(C-PA-C-O—PE-O)-H O O

where PA represents a polyamide segment, PE is a polyether section and the serial number &eegr; is between 5 and 10.

The polyamide sections consist of suitable aliphatic polyamides, such as nylon 12, 11.9, 6/12, 6/11, 6/9 or 6/6. Nylon 12 sections are particularly preferred. The polyamide sections can also be based on aromatic polyamides, but in this case significantly lower compliance characteristics are to be expected. The polyamide sections have a relatively low molecular weight, generally within 500-8000, preferably 2000-6000, and most preferably about 3000-5000.

The polyether sections consist of aliphatic polyethers having at least 2 and not more than 10 linear saturated aliphatic carbon atoms between the ether linkages. Preferably, the ether sections have 4-6 carbons between the ether linkages, and most preferably they are poly(tetramethylene ether) sections. Examples of other polyethers that can be used instead of the preferred tetramethylene ether sections include polyethylene glycol, polypropylene glycol, poly(pentamethylene ether) and poly(hexa-

methylene ether). The hydrocarbon portions of the polyethers may optionally be branched. An example is the polyether of 2-ethylhexanediol. In general, such branches will not contain more than two carbon atoms. The molecular weight of the polyether portions is suitably between about 400 and 2500, preferably between 650 and 1000.

The weight ratio of polyamide to polyether in the polyamide/polyether polyesters desirably used in the invention should be in the range of 50/50 to 95/5, preferably between 60/30 and 92/08, and most preferably between 70/30 and 90/10.

Polyamide/polyetherpolyesters are sold commercially under the trademark PEBAX by Atochem North America, Inc., Philadelphia PA. Examples of suitable commercially available polymers are the Pebax® 33 series polymers with Shore D hardnesses of 60 and above, particularly Pebax® 7033 and 6333. These polymers are composed of nylon 12 sections and poly(tetramethylene ether) sections in weight ratios of about 90/10 and about 80/20, respectively. The average molecular weight of the individual sections of nylon 12 is in the range of about 3000 to 5000 g/mol and that of the poly(tetramethylene ether) sections is in the range of about 750-1250 for the 6333 polymer and about 500-800 for the 7033 polymer. The inherent viscosities of these polymers are in the range of 1.33 to 1.50 dl/g.

In general, Pebax® 7033 polymer type balloons exhibit non-compliant to semi-compliant limit behavior, and Pebax® 63333 polymer type balloons exhibit semi-compliant to compliant behavior depending on the balloon forming conditions.

While the Pebax® type polyamide/polyetherpolyesters are particularly preferred, it is also possible to use other PEBA polymers having the physical properties specified herein and obtain similar compliance, strength and softness characteristics in the finished balloon.

As an alternative to polyamide elastomers, it is also possible to use polyester/polyether segmented block copolymers and obtain similar balloon properties. Such polymers are composed of at least two polyester and at least two polyether segments. The polyether segments are the same as the polyamide/polyether block copolymers previously described as useful in the invention. The polyester segments are polyesters of terephthalic acid and a diol of two to four carbons.

Preferred polyester/polyether block copolymers are poly(butylene terephthalate)-B/oc&poly(tetramethylene oxide) polymers such as Arnitel EM 740 sold by DSM Engineering Plastics. Hytrel polymers sold by DuPont which meet the physical and chemical specifications used here may also be used but are less preferred.

.It is considered important that the block copolymers have a Shore D hardness of at least 60 and a flexural modulus of no more than about 150,000 in order to obtain the desired combination of strength, compliance and softness characteristics characterizing the balloons of the invention. Preferably, the Shore D hardness is in the range of 65 to 75 and the flexural modulus is in the range of 50,000 to 120,000. The preferred polymers useful in the invention are also characterized by a high elongation at break of about 300% or higher, and a tear strength of at least 6000 psi.

The balloons of the invention are made using known techniques for forming catheter balloons. For coronary angioplasty catheter balloons (balloon diameters of about 1.5-4.0 mm), individual wall thicknesses of less than 0.001 inch, preferably less than 0.0007 inch, are readily obtained. Wall strengths for such balloons are well over 15,000, typically at least 18,000 psi, and in most cases in the range of about 20,000 to 32,000 psi. For peripheral angioplasty, balloons up to 10 mm in diameter can be used, and in these cases somewhat thicker walls can be used. Even with a 10 mm balloon, wall thicknesses of about 0.0015 mm or less can be achieved.

to provide balloons with burst pressures of at least 10 atm. Suitably, balloons are formed by expanding a tubing material at a ring expansion ratio (mold diameter/inner tubing diameter) of between 3 and 8, preferably between 4 and 7.

The following examples illustrate the manufacture and unique properties of the balloons of the present invention.

EXAMPLES

HOSE EXTRUSION.

All tubing mentioned in Examples 1-9, 11 and 13 were made from Atochem Pebax® 7033 and Pebax® 6333 by extrusion. Prior to extrusion, the polymer pellets were dried to less than 0.10 wt.% moisture content. The tubing was extruded through seven temperature controlled extruder zones in a melt temperature range of 200 ^° C to 220 ^° C with the feed gate hot. Extrusion conditions were based on the manufacturer's recommended polymer processing conditions. After the polymer material was extruded from the die in tubular form, it was passed through a small air gap and cooled in a deionized water bath maintained at about 65 ^° F. A puller was used to pull the tubing through the water bath. After passing through the puller, the extruded tubing was cut or spooled into 8 inch sections. A variety of hose sizes have been manufactured using this process.

EXAMPLE 1

The product in this example is a 2.25 mm balloon made of Pebax® 7033. This polymer has a Shore D hardness of 69, a flexural modulus of 67000, a tear strength of 8300 psi and an elongation at break of 400%. The tubing sections have a

outer diameter of 0.0270 inches and an inner diameter of 0.0179 inches. To form a 2.25 mm balloon with a body length of 20 mm, a mold was used that had dimensions that allowed the tube to inflate to the appropriate body size and inner balloon particle diameters.

After the tubing section was secured in the mold, the mold was placed in a fixture. The tubing section extended beyond the end of the mold and was fed to a Touhy clamp through which nitrogen gas was introduced into the interior cavity of the tubing at 280 psi, placing tension on the tubing. The tubing section at the lower end of the mold was clamped closed so that pressure was maintained within the tubing section. The mold was then gradually immersed in a controlled manner into a deionized hot water bath maintained at 9O ⁰ C (± 1 ⁰ C) to a point just above the proximal waist of the mold. The balloon was formed by radial expansion with internal pressure using a ring expansion ratio of 5.1. After balloon formation, the mold was removed from the hot water bath and cooled for approximately 10 sec. in a deionized water bath maintained at about 10 ⁰ C.

Balloons prepared in this manner were subjected to standard burst tests, which involved measuring the double wall thickness of the deflated balloon, inflating the balloon at incremental pressures, and measuring the outer diameter after each step until the balloon burst. Burst strength, expansion, and balloon wall strength were calculated from the data obtained. Averaged results are shown in Table 1.

EXAMPLE 2

The product of this example is a 3.00 mm balloon made of Pebax® 7033. The tubing sections had an outer diameter of 0.0290 inches and an inner diameter of 0.0179 inches. A 3.00 mm mold was used to manufacture the balloons

These 3.00 mm balloons were prepared using the same procedure as in Example 1, except for the water bath temperature and internal inflation pressure. The water bath temperature and pressure were maintained at 95°C and 300 psi, respectively. The ring expansion ratio of the balloon was 6.2. The results of the burst, expansion and wall strength tests are also shown in Table 1.

EXAMPLE 3

The product of this example is a 3.00 mm balloon made of Pebax® 7033. The tubing sections had an outer diameter of 0.0316 inches and an inner diameter of 0.0179 inches. An appropriately sized mold was used to form the balloons. In this example, 9O ⁰ C water bath temperature and 400 psi internal inflation pressure were used. The test results shown in Table 1 show that these balloons had a higher burst pressure than those of the previous examples.

EXAMPLE 4

The product of this example is a 3.00 mm balloon made of Pebax® 7033. The tubing sections had an outer diameter of 0.0320 inches and an inner diameter of 0.0215 inches. A 3.00 mm mold was used to make the balloons. The same molding conditions as described in Example 2 were used, except that the tubing was pre-stretched at room temperature prior to forming the balloons. The pre-stretch stretch ratio λ in this example was 1.5. The test results of this example are shown in Table 1.

Table 1: Burst and expansion test results of Pebax® 7033 material (average of at least 5 balloons).

Example balloon
size
[mm] singles
wall thickness
[Inch] Place
pressure
[psi] expansion
88 psi - Burst
[%] expansion
88-132psi
[%] expansion
88-176psi
[%] Wall
strength
[psi] 1 2.25 0.00042 230 21.3 4.2 10.9 25400 2 3.00 0.00047 230 12.7 3.2 7.1 29200 3 3.00 0.00060 260 12.8 3.6 6.9 25900 4 3.00 0.00049 220 23.5 4.4 9.0 26300

EXAMPLE 5

Balloons of 2.0-3.0 mm diameter were made from Pebax® 7033 using ring expansion ratios of 4.5, 5.1 and 6.7. The balloons were gradually expanded at 37 ⁰ C until they burst. The results, plotted in Fig. 1, show semi-compliant curves with very high burst strengths of 15-18 atm and maximum expansions at burst of 24%-45%.

EXAMPLE 6

In this example, the balloons were made from Pebax® 6333. This polymer has a Shore D hardness of 63, a flexural modulus of 49,000, a tear strength of 8,100 psi, and an elongation at break of 300%. The same balloon molding procedure as in Example 1 was used, except as noted below. The product of this example is a 2.5 mm balloon. The tubing sections had an outer diameter of 0.0316 inches and an inner diameter of 0.0179 inches. A 2.5 mm mold was used to make the balloons. In this example, a 95 ^° C water bath and an internal inflation pressure of 300 psi were used. The ring expansion ratio to inflate the balloon was 5.5. The burst, expansion rate, and wall strength results are shown in Table 2.

EXAMPLE 7

Pebax® 6333 tubing with an outer diameter of 0.0310 inches and an inner diameter of 0.0170 inches was used to make 3.00 mm balloons. The water bath temperature was 9O ⁰ C and the internal inflation pressure was 300 psi. The ring expansion ratio to inflate the balloon was 6.9. The test results are shown in Table 2.

Table 2: Burst and expansion test results of Pebax® 6333 material (average of at least five balloons)

Example! balloon
size
[mm] singles
wall thickness
[Inch] Place
pressure
[psi] expansion
88 psi - Burst
[%] expansion
88-132psi
[%] expansion
88-176psi
[%] Wall
strength
[psi] 6 2.25 0.00058 220 33.7 3.4 17.4 19900 7 3.00 0.00049 210 17.1 4.2 9.7 26100

EXAMPLE 8

Balloons of 2.25-3.0 mm diameter were made from Pebax® 6333 using ring expansion ratios of 4.2, 5.5 and 6.9. The balloons were gradually expanded at 37 ⁰ C until they burst. The results, plotted in Fig. 2, show semi-compliant and compliant curves with burst strengths of 11.5-14 atm and expansions at burst of 23%-69%.

EXAMPLE 9

The products in this example are 3.00 mm balloons made of Pebax® 6333. The tubing sections had an outer diameter of 0.0350 inches and an inner diameter of

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9 ·

diameter of 0.0190 inches. A 3.00 mm mold was used to make the balloons. Portions of the tubing sections were pre-stretched to a stretch ratio of 2 (λ=2) prior to forming the balloons. The pre-stretched portions were on either side of a central 8 mm unstretched section which was protected by a clamp during the pre-stretching process. The unstretched central section was then formed into a balloon body 20 mm long and 3.00 mm in diameter by pressure expansion in a mold as in the previous examples. The water bath temperature was 95 ⁰ C and the expansion pressure was 340 psi. The balloons prepared in this manner had a ring expansion ratio of 6.2, a single body wall thickness of between 0.0006 and 0.0007 inches, a distal waist wall thickness of between 0.0014 and 0.0021 inches, and a proximal waist wall thickness of between 0.0014 and 0.0018 inches. The burst pressure of the balloons was approximately 270 psi. The balloon expansion behavior was semi-compliant.

EXAMPLE 10

The material used in this example was Arnitel EM 740, distributed by DSM Engineering Pasties. This polymer had a Shore hardness of 74D, a flexural modulus of 120,000 psi, a tensile strength of 6400 psi, and an elongation at break of 340%. 2.25 mm balloons were made from tubing with dimensions of outer diameter = 0.0270 inches and inner diameter = 0.0179 inches. The tubing was pulled at two ends and the balloon body section was left unstretched as described in Example 9. The mold temperature was 80 ⁰ C. The mold pressure was 290 psi. The mold tension was 50 grams. The balloon properties are shown in Table 3."

Table 3: Burst and expansion test results of Arnitel EM 740 material

Example balloon
size
[mm] Singles-
wall thickness
[Inch] Place
pressure
[psi] expansion
88 psi - Burst
[%] expansion
88-132psi
[%] expansion
88-176psi
[%] Wall
strength
[psi] 11 2.25 0.00041 238 34 6.2 16.7 25700

EXAMPLE 11

The material used in this example was Pebax® 7033. The mold temperature was 95 ⁰ C. The mold pressure was 500 psi. 2.00 mm balloons were made from tubing sections as detailed below. All tubing sections were stretched at room temperature at various stretch ratios and initial tubing dimensions. The units of inner and outer diameter are inches.

a: The hose was stretched with a stretch ratio of &lgr; = 2.5 at the beginning: inner diameter = 0.0130 outer diameter = 0.0252 at the end: inner diameter = 0.0087 outer diameter = 0.0177

b: The hose was stretched with a stretch ratio of &lgr; = 3.0 at the beginning: inner diameter = 0.0132 outer diameter = 0.0252 at the end: inner diameter = 0.0081 outer diameter = 0.0162

c: The hose was stretched with a stretch ratio of &lgr; = 4.5 at the beginning: inner diameter = 0.0132 outer diameter = 0.0262 at the end: inner diameter = 0.0064 outer diameter = 0.0136

The properties of the resulting balloons are given in Table 4.

• *

Table 4: Burst and expansion test results of Pebax 7033 material

Example balloon
size
[mm] Singles-
wall thickness
[Inch] Place
pressure
[psi] expansion
88 psi - Burst
[%] expansion
88-132psi
[%] expansion
88-176psi
[%] Wall
strength
[psi] 12a 2.0 0.00058 279 14.6 4.0 6.5 18900 12 b 2.0 0.00060 279 14.6 3.5 6.6 18300 12c 2.0 0.00062 353 22.2 3.0 5.4 22600

EXAMPLE 12

The material used in this example was Arnitel EM 740 poly(butylene terephthalate)-i?/oc&-poly(tetramethylene oxide). 2.75 mm balloons were made from tubing with dimensions: outer diameter = 0.0390 inches and inner diameter = 0.0230 inches. The tubing was stretched at room temperature to λ = 4.8. The dimensions of the stretched tubing were: outer diameter = 0.0250 inches and inner diameter = 0.0200 inches. The mold temperature was 80 ⁰ C. The mold pressure was 490 psi. The mold stress was 30 grams. The properties of the resulting balloons are given in Table 5.

Table 5: Burst and expansion rate test results of Arnitel EM 740 material.

Example balloon
size
[mm] singles
wall thickness
[Inch] Place
pressure
[psi] expansion
88 psi - Burst
[%] expansion
88-132psi
[%] expansion
88-176psi
[%] Wall
strength
[psi] 13 2.75 0.00066 265 43.9 8.0 18.2 21700

&bull; t φ <

EXAMPLE 13

Pebax 7033 tubing with dimensions of 0.0198 inch outer diameter and 0.0339 inch inner diameter was pulled at room temperature with a central region protected by an inserted subtubing approximately 0.018 inch in diameter and 1.0 inch long. The tubing was pulled out until an 8 mm central region remained undrawn. Ten sterilized balloons (3.0 mm in diameter and 20 mm long) with an average double wall thickness of 0.00142 inch were prepared by radially expanding the 8 mm central tubing sections at 95 ⁰ C. The resulting burst pressure was 270-280 psi and the expansion was 9% in the range of 88-176 psi and 16% in the range of 88-235 psi.

COMPARISON EXAMPLES

COMPARISON EXAMPLES A-C

The material used in this example was Pebax 3533. This polymer has a Shore D hardness of 35 and a flexural modulus of 2800. Balloons were made by expanding tubing with inner diameter = 0.0330 inches and outer diameter = 0.0480 inches. The mold temperature was 66 ⁰ C. The mold pressure was 80 psi. Expansion and burst tests were performed at room temperature (22 ⁰ C). Balloon properties are shown in Table 6.

Table 6: Burst and expansion test results of Pebax 3533 material.

Comparison
example Balloon size
[mm] Single wall thickness
[Inch] Place
pressure
[psi] expansion
10-place
[%] Wall
strength
[psi] A 1.50 0.00495 75 67 450 B 2.00 0.00218 50 89 900 C 2.50 0.00185 40 73 1060

i*9

COMPARISON EXAMPLE D

The material used in this example was Pebax 5533. This polymer has a Shore D hardness of 55 and a flexural modulus of 29,000. 3.00 mm balloons were made from tubing sections with an inner diameter of 0.0190 inches and an outer diameter of 0.0360 inches. The mold temperature was 87.5 ^° C. The mold pressure was 300 psi. Portions of the tubing sections were pre-stretched to a stretch ratio of 2 (λ=2) prior to forming the balloons. The pre-stretched sections were on either side of an 8 mm long central unstretched section which was protected during the stretching process by a subtube as in Example 13. The unstretched central section was then formed in a mold by expansion under pressure to form a balloon 20 mm long and 3.0 mm in diameter. The balloon properties are given in Table 7.

Table 7: Burst and expansion test results of Pebax 5533 material

Compare-
Example balloon
size
[mm] singles
wall thickness
[Inch] Place
pressure
[psi] expansion
88 psi - Burst
[%] expansion
88-132psi
[%] expansion
29.4-place
[%] Wall
strength
[psi] D 3.00 0.00073 132 17.0 17.0 44.3 10700

COMPARISON EXAMPLES E-G

The material used in this example was Riteflex 640 poly(butylene terephthalate)-5/8-poly(tetramethylene oxide). This polymer has a Shore D hardness of 40 and a flexural modulus of 12300. The balloons were made by expanding tubing with an inner diameter of 0.0360 inches and an outer diameter of 0.0430 inches. The mold temperature was 80 ⁰ C. The mold pressure was 80 psi. The balloon properties are given in Table 8.

&bull;&diams; ·

Table 8: Burst and expansion test results of Riteflex 640 material

Comparison
example Balloon size
[mm] Single wall thickness
[Inch] Place
pressure
[psi] expansion
10-place
[%] Wall-
strength
[psi] E 1.50 0.00216 80 66 1100 F 1.75 0.00105 65 52 2100 G 2.25 0.00088 60 62 3020

Claims (30)

Claims It is claimed: 1. A balloon for a medical device formed from a piece of polymer tubing by radial expansion of the tubing under pressure, the polymer being a thermoplastic elastomer block copolymer characterized as follows: the block copolymer comprises two or more hard sections of a polyester or polyamide and two or more soft sections of polyether; the polyester hard sections are polyesters made from terephthalic acid and a C ₂ -C ₄ -DiOl, the polyamide hard sections are polyamides from carboxylic acids of C ₆ or higher and organic diamines of C ₆ or higher or from aliphatic go-amino-a-acids of C ₆ or higher, and the polyether soft sections are polyethers from C ₂ -C ₁₀ diols, the block copolymer has a flexural modulus of less than about 150,000 psi; the block copolymer has a hardness of greater than 60 on the Shore D scale; and the percentage by weight of the block polymer attributable to the hard sections is between about 50% and about 95%. 2. The balloon of claim 1, wherein the block copolymer has a Shore D hardness in the range of 65 to 75 and a flexural modulus in the range of 50,000-120,000 psi. 3. Balloon according to claim 1, wherein the hard sections of the block copolymer consist of polyamide sections. 4. Balloon according to claim 3, wherein the block copolymer is represented by the following formula: HO-(C-PA-CO-PE-O) _n -H Ö O in which PA is a polyamide section with a molecular weight in the range of 500 to 8000; PE is a polyether section with a molecular weight in the range of 500 to 2500 and the serial number η is between 5 and 10. 5. Balloon according to claim 4, wherein the block copolymer portion PA consists of an aliphatic polyamide of one or more aliphatic C ₁₀ -C ₁₂ acids and one or more aliphatic C ₁₀ -C ₁₂ diamines or of an aliphatic C ₁₀ -C ₁₂ co-amino-a-acid. 6. Balloon according to claim 4, wherein the polyamide portion PA is selected from the group consisting of nylon 12, nylon 11, nylon 9, nylon 6, nylon 6/12, nylon 6/11, nylon 6/9 and nylon 6/6. 7. Balloon according to claim 4, wherein the polyamide portion PA consists of nylon 12 with a molecular weight of 3000-5000, and the polyether portion PE consists of a poly(tetramethylene ether) with a molecular weight between 500 and 1250 . 8. Balloon according to claim 4, wherein the polyamide sections PA comprise between 80 and 90 wt.% of the polyamide/polyetherpolyester. 9. The balloon of claim 1, wherein said polyether portion is selected from the group consisting of poly(tetramethylene ether), poly(pentamethylene ether) and poly(hexamethylene ether). 10. The balloon of claim 1, wherein the wall strength of the balloon is at least 15,000 psi. 11. The balloon of claim 10, wherein the wall thickness on a single wall basis is no more than 0.0015 inches and said wall strength is greater than 18,000 psi. 12. The balloon of claim 11, wherein said wall thickness is not more than 0.0009 inches. 13. The balloon of claim 10, wherein said wall strength is greater than 20,000 psi. 14. A balloon according to claim 1 having a compliant to semi-compliant expansion profile, wherein when the inflation pressure is increased from 6 atm to 12 atm, the balloon expands from a nominal diameter at 6 atm pressure to an enlarged diameter at 12 atm pressure which is at least 7% larger than said nominal diameter. 15. A balloon according to claim 14, wherein the increased diameter at 12 atm is at least 10% larger than said nominal diameter. 16. The balloon of claim 14, wherein the increased diameter is at least 16% larger than said nominal diameter. 17. A balloon according to claim 14 having a nominal diameter of between 1.5 mm and 10.0 mm, wherein the balloon has a burst pressure of at least 10 atm. 18. Balloon according to claim 1 having a nominal diameter between 1.5 mm and 4.0 mm, wherein the balloon has a burst pressure of at least 12 atm. 24 19. The balloon of claim 1, wherein the hard portions of the block copolymer are polyester portions. 20. The balloon of claim 1, wherein the block copolymer is poly(butylene terephthalate) ß/oc/c-poly(tetramethylene oxide). 21. The balloon of claim 1, wherein the block copolymer is further characterized by a tear strength of at least 6000 psi and an elongation at break of at least 300%. 22. A dilatation catheter having an elongated tubular body, a balloon attached to the distal end thereof and means for inflating the balloon, wherein the balloon is a balloon according to claim 1. 23. A medical device balloon formed from a length of polymer tubing by radially expanding the tubing under pressure according to any preceding claim, wherein the balloon has proximal and distal waisted portions and a central body portion, and said tubing portion has proximal and distal portions expanded to a reduced diameter and an unstretched central portion, and wherein said radial expansion of said tubing occurs in a mold such that the balloon body is formed from the unstretched central portion of the tubing and the proximal and distal waisted portions of the balloon are formed from the stretched proximal and distal portions of the tubing, and wherein the polymer is a block polyamide/polyether or a polyester/polyether copolymer. 24. The balloon of claim 23, wherein the tube is radially expanded at a ring expansion ratio between 3 and 8. 25. The balloon of claim 23, wherein the tube is radially expanded at a ring expansion ratio between 4 and 7. 26. The balloon of claim 23, wherein the polymer has a Shore D hardness of at least 60 and a flexural modulus of less than 150,000 psi. 27. The balloon of claim 26, wherein the polymer has a tear strength of at least 6000 psi and an elongation at break of at least 300%. 28. The balloon of claim 23, wherein the balloon is not heat set and has a wall strength of at least 20,000 psi. 29. The balloon of claim 23, wherein the expansion of said proximal and distal portions occurs at ambient temperature. 30. Balloon according to claim 23, wherein said polymer is a polyamide/polyether/polyester.