AU2003204676B2 - Process for Forming Dyed Braided Suture - Google Patents

Description

S&FRef: 520757D1

AUSTRALIA

PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT Name and Address of Applicant: Actual Inventor(s): Address for Service: Invention Title: Tyco Group S.A.R.L.

6 Avenue Emile Reuter L-2420 Luxembourg Luxembourg Jeffrey D Hutton Barry L. Dumican Spruson Ferguson St Martins Tower Level 31 Market Street Sydney NSW 2000 (CCN 3710000177) Process for Forming Dyed Braided Suture The following statement is a full description of this invention, including the best method of performing it known to me/us:- 5845c

TITLE

PROCESS FOR FORMING DYED BRAIDED SUTURE Background of the Invention Field of the Invention This invention relates to a braided polyester suture and a process for forming a dyed braided suture.

Related Background Art Braided sutures are well known in the art as disclosed, for example, in US Patent No. 5,019,093. Various natural and artificial polymeric materials have been used in manufacture of braided sutures, including surgical gut, silk, cotton, polyolefins, polyamides, polyglycolic acid and polyesters. Braided sutures are useful in applications where a strong, nonabsorbable suture is needed to permanently repair tissue. They are frequently used in cardiovascular surgery, as well as in ophthalmic and neurological procedures.

For various reasons it is desirable to provide sutures which are dyed to allow immediate suture brand and or type recognition by the surgical team or treating [R:\IEBZZ]520757DI speci.doc:GYM 2 physician Previously, braided yarns were formed from polymer filaments and then solution dyed. The braids were at a lower tenacity than the final product because it is easier to dye a less crystalline yarn.

Thereafter, the dyed braids were stretched to increase tenacity by making the yarn more crystalline. However, braided yarns are not dyed thoroughly by conventional solution dyeing techniques even at a lower tenacity prior to stretching. The braided yarns resist uniform penetration by dye solutions.

Recently, higher molecular weight polyester fibers formed from polyethylene terephthalate have been employed as suture material. Such fibers have a relatively high tenacity and a relatively high intrinsic viscosity. However, it has proven necessary to dye such fibers by boiling them in a dye soloution.

Even then, there is relatively low dye penetration into the fibers. To obtain thorough dye uptake by the polyester fibers it has usually proven necessary to apply dye solution at high pressure temperature to the fibers. At such elevated pressures and temperatures, however, both the dye and fiber can be degraded.

Accordingly, it is desired to provide a method for incorporating dye uniformly into a suture material free of the defects and deficiencies of the prior art.

These and other objects and advantages are achieved by forming a dyed braided suture by: blending a biocompatible colorant with an extrudable noh-broad desirable thermoplastic resin to form a uniform blend of said colorant resin; extruding the blend by melt spinning and colling to form filaments; drawing the filaments to increase crystallinity and moleuclar orientation; braiding the filaments; and converting the braided filaments into a suture.

The surface roughness of braided sutures is of great importance to surgeons.

Excessive roughness affects the knot-tying and knot-holding properties of the suture, causing an uneven movement known as "chattering". This characteristic increases the difficulty of accurately placing knots. In addition, the uneven force exerted on the suture during tying may lead to increased suture breakage. Typically, sutures are coated with a lubricating material, eg, polybutylate, to improve the handling characteristics of the sutures.

In one embodiment, the invention relates to an implantable medical device formed from yam filaments having a tenacity of from about 7 to about 11 g/denier and a percent elongation to break of less than about 30 percent, wherein said implantable medical device is produced from a polyester having an intrinsic viscosity greater than about 0.95.

In another embodiment, the invention relates to a method of forming a dyed braided polyester suture comprising the steps of blending a colorant with polyester yam filaments having a tenacity of from about 7 to about 11 g/denier and a percent elongation to break of less than about 30 percent, wherein the yarn filaments are produced from a polyester having an intrinsic viscosity greater than about 0.95.

Brief Description of the Drawings Figure 1 is a plan view of a system for extruding polyester filaments from bulk resin.

Figure 2 is a plan view of a system for drawing polyester filaments.

Detailed Description of the Invention The dyed braided polyester sutures of this invention are manufactured from yarn filaments produced from thermoplastic resins having an intrinsic viscosity greater than about 0.95. The intrinsic viscosity is preferably greater than about 0.95 but not greater than about 1.1.

Preferably, the polyester employed in this invention is polyethylene terephthalate (PET). If desired, bulk [R:\LIBZZ]520757D1 speci.doc:GYM 4 resin in the form of granules, chips or pellets of a suitable PET are made into yarn filaments via a conventional extrusion process. Bulk PET with suitable properties may be obtained commercially from, for example, Shell Chemical Co., Apple Grove, WV distributed under the designation Cleartuf EB 1040 and Traytuf 106C and DSM Engineering Plastics, Evansville, IN under the designation Arnite A06 100.

Alternatively, polyester yarn with suitable properties may be obtained commercially from, for example, Hoechst Celanese under the trade name Trevira High Tenacity type 712 or 787. The intrinsic viscosity of such yarn samples is from 1.04 to 1.07.

Preferably, the tenacity of the yarn filaments is from about 7.5 to about 10.5 g/denier, the percent elongation to break is less than about 25 percent and the polymers from which the fibers are made have an intrinsic viscosity greater than about 0.95 but no greater than about 1.1.

Most preferably, the tenacity of the yarn filaments is from about 8 to about 10 g/denier, the percent elongation to break is less than about 20 percent and the polymers from which the fibers are made have an intrinsic viscosity greater than about 0.95 but no greater than about 1.i.

The polyester yarns are made from filaments having a denier in the range from about 0.2 to about 6, preferably from about 1.2 to about 3.4, most preferably from about 1.4 to about 3.1. The polyester filaments are extruded as yarns having a denier in the range from about 20 to about 500, preferably from about 20 to about 350. The yarns are generally either conventionally twisted or entangled prior to braiding.

5 In one embodiment twisted PET yarns can be braided into sutures using conventional braid constructions having a sheath and optionally a core. Typical braid constructions are disclosed in U.S. Patent No.

5,019,093, issued May 28, 1991, the disclosure of which is incorporated herein by reference. Preferred braid constructions have the parameters recited in Table 1 as follows: Table 1: Preferred Braid Constructions Suture Size No. of Sleeve Yarns Sleeve Yarns (denier/ filament) Core Yarn (denier/ filament) Picks/ Inch 5 16 250/50 1000/200 52 2 16 140/68 840/408 57 1 12 140/68 630/306 52 0 12 100/34 300/102 42 8 140/68 None 39 3-0 8 80/16 None 39 4 70/34 None 39 4 40/8 8 30/20 None 33 4 30/20 None 32 4 20/10 3 20/10 None 67 After the braids have been assembled, they are preferably stretched in the presence of heat.

Preferably, the temperature range for such stretching is from about 150 0 C to about 250 0 C. Typically, length of the braided sutures increases by about 6% to about 33% of their original length.

6 The surface of the stretched braids can sometimes be unduly smooth after such treatment. An unduly smooth suture surface can make it difficult to grasp the suture and tie a desired knot. Also, stretching can greatly stiffen the braid imparting undesirable handling properties to the suture. In order to allow better control of the suture during tying it is preferred to conduct additional processing of the suture to provide appropriate surface roughness and lessen fiber stiffness to allow the surgeon to have better feel of the suture and permit easier knotting.

To further enhance the feel of the suture, the stretched braid may be surface-etched to break any adhesions present on the braid surface and to soften the braid. Such etching is conducted by applying a reactive compound such as sodium hydroxide or the like to the surface of the braid. To further control the feel of the suture surface, the braid can be passed under a matte roller or the like. The surface etching and matte roller treatments can further improve the surface feel of the braid to facilitate knot tying.

Optionally, the braided polyester sutures are treated with a coating material to impart improved handling to the treated braid. The preferred coating material is silastic rubber.

The braid is then formed into a suture by attaching a needle, packaging the product and then sterilizing with ionizing radiation, ethylene oxide or the like.

The filaments in the final suture product may have a molecular weight less than the molecular weight of the original polymer. It is believed that the sterilizing treatment, heating and/or stretching treatments conducted during processing of the filaments into a 7 suture may break polymer chains and reduce molecular weight.

The improved sutures of this invention, as compared to commercially available sutures, have significantly improved tensile strength.

In another embodiment of this invention, the polyester yarns are used in providing an implantable medical device. Examples of such a device is a mesh, a graft, a ligament replacement and a tendon replacement. A mesh, or net formed from polyester yarns is typically used in surgical repair of hernias. The enhanced tenacity of the polyester yarns of this invention provides the mesh with superior strength. A graft is a knitted or woven tubular article used in replacement of blood vessels. The enhanced tenacity of the polyester yarns of this invention allows construction of a graft with thinner walls and greater flexibility. Ligament and tendon replacements comprise multiple strands of polyester yarns that have been braided, for which the yarns of the present invention provide superior strength.

In a further embodiment of the invention a braided suture is formed from yarn filaments having a weight average molecular weight of greater than 35,000, a tenacity of greater than about 6 grams/denier, an elongation to break less than about 35% and a boiling water shrinkage from about 0.5 to about In this embodiment the filaments have a weight average molecular weight preferably greater than 40,000 and, most preferably, from about 42,000 to 45,000. The tenacity of the filaments is preferably greater than 7 grams/denier and most preferably from about 7 grams/denier to about 8.5 grams/denier. The percent elongation to break is preferably less than 25%, most 8 preferably less than 20%. The filaments may have a hot air shrinkage at 350 0 C from about 3 to 5% of the original length.

The filaments are typically extruded in bundles (yarns) havinging a denier from about 20 to about 500 and preferably are twisted to about 4-15 turns per inch.

The twisted yarns are braided into sutures using conventional braid construction having a sheath and, optionally, a core according to, for example, U.S.

Patent No. 5,019,093. Alternatively, a spiral braid pattern may be used as described in U.S. Patent No.

4,959,069 and U.S. Patent No. 5,059,213. The braided suture may be stretched as before to increase length from about 9 to 28% over initial length. An absorbable or nonabsorbable coating can also be applied.

If desired to further enhance surface feel the stretched braid can be surface-etched and/or matte rolled. A needle is thereafter attached, the suture packaged and the product is sterilized.

The molecular weight of the filaments in the sterilized suture may be significantly less than that of the original filaments since processing and sterilization can break polymer chains.

The examples which follow are intended to illustrate certain preferred embodiments of the invention, and no limitation of the invention is implied.

EXAMPLE 1 Extrusion of PET Yarns A PET yarn extrusion system employed in the invention is illustrated in Figure 1. Bulk PET resin (type TTF 9 l006C, available from Shell Chemical Co.) having an intrinsic viscosity of 1.04 was dried overnight in an oven at 110-130 0 C under a vacuum of less than 2 Torr.

The oven was brought to atmospheric pressure with dry air. The dried resin was transferred to feed hopper of the extrusion system and introduced into extruder barrel 20 which is 0.75 inches in diameter and inches long via an extrusion screw (not shown). The extruder barrel contained three heating zones (or extrusion zones) zones i, 2 and 3. The heated and softened resin from the extruder was fed into a metering pump (melt pump) 25, and from melt pump 25 the extruded resin was fed into spin head Spin head 30 houses a spin pack comprising filtering media (screens) and a spinnerette containing from 16 to holes (not shown) for forming the individual filaments of the yarn. The extruded filaments exited the spinnerette through hot collar 40, and were then air-cooled until they solidified. The resulting yarn was then passed through a finish applicator over two rotating godets 70 and 80, and was collected on precision, winder 90 as the yarn exited the second godet 80. The denier of the yarn at this point was 354.

The operating parameters for the extrusion system are shown in Table 2.

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10 Table 2 Station Units Value Extrusion Screw Rotations/Minute 42 Extrusion Zone 1 Temperature °C 320 Extrusion Zone 2 Temperature OC 320 Extrusion Zone 3 Temperature °C 320 Melt Pump 25 Temperature °C 310 Melt Pump Size cc/Revolution 0.584 Melt Pump Rate Rotations/Minute 25.9 Spin Pack Pressure Pounds/ Sq. Inch 2764 Spinnerette Number of Holes 28 Spinnerette Mils Hole Diameter Hot Collar 40 Temperature oC 250 First Godet 70 Temperature oC Ambient First Godet 70 Surface Speed 1500 (fpm) Second Godet 80 Temperature oC Ambient Second Godet 80 Surface Speed 1507 (fpm) EXAMPLE 2 Drawing of Yarn Extruded in Example 1 After a six-day lag time the yarn extruded in Example 1 was drawn. Drawing was conducted by passing the extruded yarn 100 around multiple rotating rolls, as illustrated in Figure 2. The drawing action was initiated by passing yarn 100 first over a roll (godet) 110 having a first, lower rotational speed and then over godets 120 and 130 having successively higher rotational speeds. Drawing occurred predominantly between godet 120 and godet 130 and was facilitated by 11 heating the godets. The drawn yarn was entangled in air jet entangler 140 and then wound onto precision winder 150. The yarn drawing conditions are shown in Table 3.

Table 3 Item Units Value Godet 110 Temperature OC Ambient Godet 110 Surface Speed (fpm) 500 Godet 120 Temperature OC 77 Godet 120 Surface Speed (fpm) 507 Godet 130 Temperature oC '160 Godet 130 Surface Speed (fpm) 2895 Properties of the drawn fiber were measured on an Instron Tensile Tester, Model 1130, equipped with cord and yarn clamps. The initial specimen length was inches and the test was run at 10 inches of extension per minute. The results were as shown in Table 4.

Table 4 Item Value Units Denier 64.5 Tenacity 8.73 g/denier Breaking Elongation 14.6 percent 12 EXAMPLE 3 Braided Polyester Sutures The drawn yarn produced in Example 2 was formed into a suture as follows: Yarn samples were plied at 3 turns per inch and then braided on a New England Butt 8 carrier braider (not shown) at 38.6 picks per inch.

The braid was then hot stretched in a tunnel between opposed matte surfaced godets numbered and (2) under the conditions shown in Table 5. The braid was stretched 21%.

Table Item Units Value Godet 1 Temperature oC 200 Godet 1 Surface Speed (fpm) 14 Tunnel Temperature OC 231 Godet 2 Temperature oC 200 Godet 2 Surface Speed (fpm) 17 The stretched braid was softened by treatment in 3% NaOH aqueous solution maintained at 82.2 0 C for minutes. The softened braid was then washed and rinsed. The washed braid was then immersed in a solution of 5% silastic rubber and benzoyl peroxide as actives in a xylene solvent to coat the braid. The silastic rubber-coated braid was next cured in an oven at 170 0 C and converted into a suture by attaching a needle, packaging and finally sterilizing with ethylene oxide. The properties of the suture were as in Table 6.

13 Table 6 Property Measured Value Units Diameter 0.315 mm Denier 930 Tenacity"l 7.45 g/denier Breaking Elongation 14.0 percent Knot PullV 2.93 Kg o Tenacity was determined by a straight pull of a sample using a 10 inch gauge length and 10 inch per minute crosshead speed. "Cord and yarn" clamps were used for this purpose.

O Knot pull was determined by tying a sample in a "surgeon's knot" around a piece of rubber tubing and testing as in determining tenacity.

The suture had an excellent feel, did not exhibit "chattering" during use and provided reduced tendency to break during knot tying.

EXAMPLE 4 Extrusion of PET Yarn Bulk PET, sold as Arnite A06 100 and available from DSM Engineering Plastics, having an intrinsic viscosity of 1.07 (tetrachloroethoxyphenol) was processed as described in Example 1 under the operating parameters shown in Table 7 as follows:

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14 Table 7 Station Units Value Extrusion Screw Rotations/Minute 42 Extrusion Zone 1 Temperature OC 315 Extrusion Zone 2 Temperature OC 315 Extrusion Zone 3 Temperature OC 315 Melt Pump 25 Temperature oC 289 Melt Pump Size cc/Revolution 0.584 Melt Pump Rate Rotations/Minute 24.9 Spin Pack Pressure Pounds/Sq. Inch 3425 Spinnerette Number of Holes 28 Spinnerette Mils Hole Diameter Hot Collar 40 Temperature oC 250 First Godet 70 Temperature "C Ambient First Godet 70 Surface Speed 1500 (fpm) Second Godet 80 Temperature oC Ambient Second Godet 80 Surface Speed 1507 (fpm) Fiber was taken up on precision winder 90 as it exited second godet 80. The was 341.

denier of the yarn at this point EXAMPLE Drawing of Extruded Yarn of Example 4 After a lag time of three days, the extruded yarn of Example 4 was drawn as described in Example 2, using the drawing conditions shown in Table 8.

15 Table 8

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Item Units Value Godet 110 Temperature OC Ambient Godet 110 Surface Speed (fpm) 500 Godet 120 Temperature OC 77 Godet 120 Surface Speed (fpm) 507 Godet 130 Temperature OC 160 Godet 130 Surface Speed (fpm) 2900 Drawn fiber was taken up on precision winder 150 as it exited godet 130. The properties of the drawn fiber are shown in Table 9.

Table 9 Item Value Units Denier 60.9 Tenacity 8.86 g/denier Breaking Elongation 12.7 percent EXAMPLE 6 Braided Polyester Sutures The drawn yarn produced in Example 5 was converted to a suture as follows: Yarn samples were two plied at 3 turns per inch and then braided on a New England Butt 8 carrier braider. The braid was then hot stretched under the conditions shown in Table 10 to stretch the braid 33%.

16 Table Item Units Value Godet 1 Temperature OC Ambient Godet 1 Surface Speed (fpm) 44.8 Tunnel Temperature OC 254 Godet 2 Temperature oC 23 Godet 2 Surface Speed (fpm) -59.-8 The stretched braids were softened and coated as described in Example 3. The properties of the finished braids are shown in Table 11.

Table 11 Property Measured Value Units Diameter 0.335 mm Denier 1017 Tenacity 7.1 g/denier Breaking Elongation 14.9 percent Knot Pull 3.2 Kg Other variations and modifications of this invention will be obvious to those skilled in the art. This invention is not limited except as set forth in the following claims.

Claims (13)

1. An implantable medical device formed from yam filaments having a tenacity of from about 7 to about 11 g/denier and a percent elongation to break of less than about percent, wherein said implantable medical device is produced from a polyester having an intrinsic viscosity greater than about 0.95.

2. The implantable medical device of claim 1, wherein said implantable medical device is selected from the group consisting of a mesh, a graft, a ligament replacement and a tendon replacement.

3. The implantable medical device of claim 2, wherein the yar filaments have a tenacity of from about 7.5 to about 10.5 g/denier and a percent elongation to break of less than 25 percent and are produced from a polyester having an intrinsic viscosity greater than about 0.95 but no greater than about 1.1.

4. The implantable medical device of claim 3, wherein the yam filaments have a tenacity of from about 8 to about 10 g/denier and a percent elongation to break of less than about 20 percent. The implantable medical device of any one of claims 1 to 4, wherein the implantable medical device is a braided polyester suture having been surface etched to enhance feel.

6. The braided polyester suture of claim 5, wherein the braided polyester suture is selected from one of the following constructions numbered 1 to Construction Braid No. of Sleeve Yams Core Yam Picks/2.54cm No. Size Sleeve (denier/Filament) (denier/filament) (inch) Yarns 1 5 16 250/50 1000/200 52 2 2 16 140/68 840/408 57 3 1 12 140/68 630/306 52 4 0 12 100/34 300/102 42 2-0 8 140/68 None 39 6 3-0 8 80/16 None 39 7 4-0 4 70/34 None 39 4 40/8 8 5-0 8 30/20 None 33 9 6-0 4 30/20 None 32 4 20/10

7-0 3 20/10 None 67 7. The braided polyester suture of claim 6, wherein the yam filaments have a tenacity of from about 7.5 to about 10.5 g/denier and a percent elongation to break of less [R:\LIBZZ]520757Dlspeci.doc:GYM than about 25 percent and are produced from a polyester having an intrinsic viscosity greater than about 0.95 but no greater than about 1.1.

8. The braided polyester suture of claim 7, wherein the yam filaments have a tenacity of from about 8 to about 10 g/denier and a percent elongation to break of less than about 20 percent.

9. The implantable medical device of any one of claims 1 to 8, which is a braided polyester suture having been passed under a matte roller. The implantable medical device of any one of claims 1 to 9, which is a braided polyester suture having a coating of silastic rubber.

11. An implantable medical device formed from polyester yar filaments substantially as hereinbefore described with reference to the accompanying drawings.

12. A method of forming an implantable medical device formed from polyester yar filaments comprising the steps substantially as hereinbefore described with reference to the accompanying drawings.

13. A method of forming a dyed braided polyester suture comprising the steps of blending a colorant with polyester yam filaments having a tenacity of from about 7 to about 11 g/denier and a percent elongation to break of less than about 30 percent, wherein the yam filaments are produced from a polyester having an intrinsic viscosity greater than about 0.95.

14. The method of claim 13, wherein the polyester is polyethylene terephthalate (PET). A dyed braided suture made from the process of claim 13 or 14.

16. The implantable medical device of any one of claims 1 to 11, wherein the polyester is polyethylene terephthalate (PET). Dated 13 December, 2005 Tyco Group S.A.R.L. Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON [R:\LIBZZ]520757Dlspeci.doc:GYM