BACKGROUND OF THE INVENTION

Field of the Invention

Tnis invention relates to improved surgical sutures having extremely high knot strength and to methods for their preparation. More particularly, the invention is directed to composite surgical sutures having a knot strength that enables them to be used over a range of suture sizes classified by the United States Pharmacopeia (USP).

Brief Description of the Prior Art

Surgical sutures are generally divided into two broad classes: (1) absorbable sutures, either natural or synthetic, which are absorbed by the body and (2) non-absorbable sutures, which remain in the body for prolonged periods of time or are removed when the wound heals.

From the patient's viewpoint, whether an absorbable or non-absorbable suture is employed, assuming no toxicity of the suture implant, it is a surgical dictum that the finest suture should be used and that the knot should have the least mass. This dictum is based upon the belief that problems in suture implants are directly related to the size of the suture and the bulk of the mass, i.e., the larger the bulk, the greater the probability of trouble in healing.

Undoubtedly, this was the rational for the original establishment of the USP classification which divides non-absorbable sutures into seventeen sizes: 10/0, 9/0, 3/0, 7/0, 6/0, 5/0, 4/0, 3/0, 2/0, 0, 1, 2, 3, 4, 5, 6, 7. A few additional

sizes are used which are not USP. Considering that silk was the most widely used non-absorbable suture in the mid-twenties and thirties, this size dif¬ ferentiation was based upon manufacturing. These seventeen sizes could be differentiated one from another by eye. If a finer differentiation were desired, it would not be accomplished becasue of the variation in the raw material as extruded by the silk worm. This classification has been quite useful. Obviously, the number of sizes cannot be considered "standardization" by any means. The sizes are numerous. Unfortunately, it has not been possible to coalesce size" because the finer sizes do not have the adequate knot break strength to substitute for the -next size.

A further long term problem in surgery is post-operative hernia. .It is a truism that scar tissue never achieves the tensile strength of normal tissue. Hernias have occurred many ,years post-operably through the scar. If a sαture were developed which would Leave as a residue a non- absorbable suture to support that scar tissue, it would undoubtedly decrease and most likely elim¬ inate the post-operative hernia as a complication.

Composite sutures having a reinforcing core are known in the prior art. None, however, achieve the aforementioned characteristics desired in a suture.

Accordingly, it is an object. of the invention to provide a surgical suture with knot strengths so great tnat suture of much less foreign material is left in the body.

Another object of the invention is to provide a surgical suture having a knot strength that renders it useful over a range of surgical sizes within the USP classification of graded suture sizes, and thus

OMP

having the ability to replace the USP graded scale of sizes with just a few finer sutures whose strength would cover the entire range.

A further object of the invention is to provide a composite suture which leaves a residue of non- absorbabie suture to support scar tissue and, therefore, decreases or eliminates post-operative hernia as a complication.

Another object of the invention is to provide a method of preparing surgical sutures having ex¬ tremely high knot strength whose surface char¬ acteristics can be tailored to meet desired properties.

A further object of the invention is to provide composite sutures capable of using needles which more closely approximate the outer diameter of the suture.

A further object of the invention is to provide a composite suture having lateral strength, that is, a suture stabilized against abrasion, kinking and/or fibrillation during knotting.

SUMMARY OF THE I E TIOM These and other objects of the invention are obtained by a sterile, surgical suture having an elongated core of a synthetic polymer having a knot tenacity of at least 7 grams/denier coated with a film and fiber-forming surgical material, said coated core, when constructed into a surgical suture of a particular USP grade size, having a knot strength exhibited by surgical sutures of said suture material at least two USP grade sizes larger. The elongated core of trie sutures of the inven¬ tion can be formed of any fioer-forming synthetic polymer, such as a polyamids, olyolefin, polyester

_ j_ _

and the Ii'<e, naving a straight pull tenacity of at least 15 grams/denier, preferably up to 70 or more grams/denier and a knot tenacity of at least 7 grams/denier, preferably up to 30 or more grams/- denier. By "knot tenacity" as used herein and in the appended claims is meant knot break strength divided by the denier. Unless the synthetic pol¬ ymer making up the suture core of the invention meets the aforementioned knot tenacity properties, the resulting coated core fails to provide a suture which achieves the desired objects of the invention.

Illustrative of synthetic polymer materials suitable for use as the c'ore of the suture of the invention are fiber-forming aromatic polyamides in which the chain extending bonds from each aromatic nucleus are essentiαLly coaxial or parallel and oppositely directed. The term "aromatic nucleus" is used herein to include individual enchained aromatic rings and fused-ring aromatic divalent radicals. The preferred polymers include carbo- cyclic aromatic polyamides containing up to 2 aromatic rings, including enchained non-fused rings (e.g. 4, ' -biphenylene) or fused rings (e.g. 1, 5-naρhthalene) per amide linkage. The chain- extending bonds from these aromatic rings are para- orienteJ and/or essentially coaxial or parallel and oppositely directed. highly preferred polyamides are characterized by recurring units of the formula:

( I ) I O O H H ^]

I I

wherein R and R' (when the chain extending bonds are essentially coaxial) are selected from the group of:

.-/ 1,4-phenylene, and

// \ 4,4'-biphenylene and R and R' (when the chain extending bonds are essentially parallel) are selected from the group

1,5-naphthylene, and

2, 6-naphthylene

R and R' may be the same -or different and may contain substituents on the aromatic nuclei.

Additional highly preferred polyamides of this invention are characterized by recurring units of the formula:

(II) I 0 H ^'

wherein R" is selected from the group of:

Similarly R" may contain substituents on the aromatic nuclei.

As previously stated, the aromatic nuclei of the polymers of this invention may bear substi¬ tuents. These substituents should be non-reactive during the polymerization and preferably also should be non-reactive (e.g. thermally) during sub¬ sequent processing of the polymer, e.g., heat treating of a shaped fiber thereof. Such reac¬ tivity is undesirable in that it may cause cross-

linkinσ of the polymer and may adversely effect the dope and/or fiber properties. Among the preferred non-reactive substituents may be names halogens (e.g., methoxy and ethoxy) , cyano, acetyl, and nitro. Other suitable substituents non-reactive during the polymerization will be evident to those skilled in the art and are contemplated herein pro¬ vided such do not adversely affect the desired properties of the dopes and/or fibers of this invention, e.g., due to factors such as steric hindrance. Generally, it is preferred that no more than two (a d more preferably no more than one) suitable substituents- be present per aromatic nucleus. However, more than two such substituents may suitably be present if trie substituent is a relatively small group e.g., methyl.

Both humo-and co-polyamides having substituted or unsubstituted aromatic nuclei, as described above, are well suited for the dopes and fibers of this invention. Random copolymers are preferred copolyraers . By the term "random" is meant that the conolymer consists of molecules containing large numbers of units comprised of two or more different types in irregular sequence. The units may be of AB (e.g., from p-aminobenzoyl chloride hydro- chloride), AA (e.g., from p-phenylenediamine or 2, ό-dichloro-p-phenylene diamirte), or BB (e.g., from terephthaloyl or 4, 4' -bibenzoyl chloride) type or mixtures of these, provided always that the requirements of stoichiometry for high polymer formation are met. It is not necessary that the relative numbers of the different types of the unit be the same in different molecules or even in different portions of a single molecule.

One or more of these polymers may suitably be

OM

used in the fibers of this invention, i.e., a single ho opolymer; a single copolymer; or homo- polymer and/or copolymer olends are suitable herein.

While the polymer chains described above consist essentially of amide links (- COHN -) and aromatic ring nuclei as described above, the poly¬ mers useful for preparing the core of this inven¬ tion may also comprise up to about 10 percent (mole basis) of units not conforming to the above-cited description, e.g., aromatic polyamide-forming units whose chain extending bonds are other than coaxial or parallel and oppositely directed, e.g., they may be metaoriented, or of linkages other than amide, e.g., urea or ester groups.

Among the suitable aromatic polyamides may be named poly(p-benzamide) ; poly(p-phenylene terephthalamide) ; poly(2-chloro-p-ρhenylene terephthalamide) ; poly( 2, 6-dichloro-ρ-phenylene 2, 6-naphthalαmide) ; poly( -phenylene p; ' -biphenyldicarboxamid ) ; poly(p,p' -phenylene benzamide); poly(1, 5-naphthylene terephthalamide); ordered aromatic copolyamides such as e.g., copoly(p, p' -diarninobenzanilide terephthalamide) , and random copolyamides such as, e.g., copoly(p-benzamide/m-benzαmide) (95/5); and many others .

These aromatic polyamides generally have an inherent viscosity and prefereaoly greater than 1.0. Inherent viscosity (ninh) defined by the following equation: wherein (irel) represents the relative viscosity and C represents α concentration of 0.5 gram of the polymer in 100 ml of solvent. Exemplary of such aromatic polyamides are those known as the "Kevlar"

series, products of the DuPont corporation, which generally have α straight pull tenacity of about 18 to 25 grams ^' per denier and a knot tenacity of at least about 7 grams per denier. Further examples of such aromatic polyamides and their methods of preparation can be found, for instance, in U.S. Patent Wos. 3,063,966, 3,600,350, 3,671,542 and 3,819,587 all incorporated herein by reference.

Another example of a synthetic polymer suitable for use as the core of the suture of tne invention are high strength oolyolefins such as polyethylene which provides fioers having a straight pull tenac¬ ity of about 25-50 grams/denier and a knot tenacity of about 7 to 17 grams/denier. These polyolefin fibers are characterized by full chain extension and high crystallization and can be prepared: (1) by ultradrawing of the solidified crystalline poly¬ olefin material that is, by further development of the traditional cold drawing process, and (2) by extending the chains in random state (melt or solu¬ tion) and inducing them to crystallize in the ex¬ tended form subsequently. Polyole ins having these characteristics and their method of preparation are described in Keller, A. and Barhαm, P.J. "High Modulus Fibres", Plastics and Rubber International, February, Volume 6, No. 1 (1981), herein incor¬ porated by reference.

The core of the surgical suture of the in¬ vention can be either a monofilament or of multi- filament construction. The latter is ordinarily preferred since the coating of suture material subsequently applied generally exhibits stronger adhesion to multifilament cores. The liquified suture material coating tends to penetrate and fill the interstices of a multifilament core as well as

≠** ^* OM

coating the core, thereby anchoring the coating thereto. Multifilament cores can take the form of braids, twisted polyfilaments, yarns and the like.* It should be noted that while the synthetic polymer materials contemplated for use as the core of the composite sutures of the invention, have high axial strength, they are not ordinarily suitable for use as sutures since they do not possess the necessary lateral strength and, therefore, tend to abrade, kink and/or fibrillate during knotting. Coating of the core with α suture material pursuant to the present invention has been found to unexpectedly stabilize, i.e. provide lateral strength resistance against such action thereby rendering suitable for use as sutures these synthetic polymer fibers nor¬ mally unsuitable for such use.

The surgical suture material used to coat the core can be any film-forming material commonly used in the construction of absorbable and non- absorbable sutures. In general these suture materials when drawn into fibers exhibit straight tensile strengths of about 4 to 10 grαrαs/denier. Examples of the non-absorbable type suture materials are silk (fibroin), polyolefins, such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and nylon. Examples of absorbable type materials useful as the coating for * The suture material in the form of multi or monofilament yarn may also be present initially as a core around which the high strength yarn which eventually becomes the core in the finished suture is braided or twisted or it may be formed into a plied, twisted, braided or co-mingled construction with the high strength yarn.

the core include collagen and the synthetic ab¬ sorbable materials such as polyiαctide, poly- glycoiide and copolymers of lactide and glycolide with each other and with other reactive monomers such as those described, for instance, in U.S. Patent os. 3,636,952 and 2,683,136, which patents are herewith incorporated by reference. Such synthetic absorbable polymers are sometimes referred to herein as simply homopolymers and copolymers of l ctide and glycolide.

The amount of suture material coated onto the core will vary depending upon the constructon of the core, whether monofilament or multifilament, the number and tightness of braid or twist, the particular tensile strength and knot tenacity of the core, the particular suture material used as the coating and its nature, e.g. melt, solution or solid. In general, when the coating is a non- absorbable suture material, the coating will constitute about 5 to about 10% by weight of the coated core. On the other hand, when the coating is an absorbable suture material, the coating may constitute about 5 to 90% by weight of the coated core.

The coatings can be applied by a variety of suitable techniques well known in the coating art. For example, the coatings can be applied to the core by solution coating, melt coating, extrusion coating and the like.

In melt coating, for example, the uncoαted core under tension is slowly passed through α melt of the suture material and then through a die having an orifice smaller than the upper diameter speci¬ fication for the suture size desired, heated above the melting point of the coating materials, to trim

off excess coating material and shape the composite. Multiple coatings may be applied if necessary.

In solution coating, the suture material is dissolved in a suitable solvent and the core is slowly passed through the coating solution thus formed. The treated core is then passed con¬ tinuously through a tubular oven heated to an elevated temperature to evaporate the solvent and coalesce and solidify the suture material that remains .

A preferred coating technique when the core being coated is of multifilament construction comprises initially either solution coating or melt coating the multifilament core while the latter is held under a suitaole tension and allowing the liquified coating material to penetrate or infil¬ trate the interstices of the core, thereby forming roots which help anchor the coating of the core. A second layer of tne same suture material may then be applied to the impregnated core by any of the conventional coating methods.

In a typical extrusion coating process the core is passed through the cross-head die of a conven¬ tional wire coating extrusion apparatus. Pellets of the coating material are introduced into the plasti ication zone of the extruder wherein they are plasticized into α melt which is forced through the annular die of the extruder and onto the core.

Which coating technique is employed will usually depend upon the particular core utilized. Aromatic polyamide cores, for example, lend them¬ selves to melt or extrusion coating because of their high melting points. The high strength polyethylene cores, on the other hand, have

relatively low melting points, e.g. about 145°C, and must be treated differently. With them, solution coating of the monoor multi-filament cores is the chief method.

According to a preferred embodiment of the invention, when the core being coated is an aromatic polyamide, it is subjected to both a precoating stage and finish coating stage, each of which will be discussed below in more detail.

Impregnation/Precoating Stage

The impregnation/precoating operation of the invention can be conducted using a thread composed of a core made up of multifilaments of a suture material and a plurality of fibers of a synthetic polymer having a tenacity of at least 18 grams/- denier and knot tenacity of at least 7 grams/- denier. The thread can be -formed in the usual manner as by twisting, braiding, etc., a plurality of the synthetic polymer fibers around the suture material core. The thread, that is, the covered core is then heated to temperatures above the melting point of the multifilament core material passing it through any suitable oven during which passage the suture material melts and under the tension developed and/or applied exudes upward through the polyfilamentous synthetic polymer component and onto its surface. The amount of coating employed should be sufficient to not only fill all the interstices of the multifilament core component during the melting period but to also coat the surface of the yarn or thread component. Any excess coating material which may have melted out is trimmed off. While the heating of the covered core mixed yarns can be effected with or

MPI

^■ without stretching of the thread in some instances, a better final suture is obtained when the yarn is maintained under tension with little or no stretch applied at tiiis stage. It is at this stage that the basic solid coated core structure is developed.

The impregnated and coated core is then passed through a heated dye which trims coating nubs from the core and otlierwise smooths the external surface . of the thread. Stretch may also be applied during the smoothing operation, but again, best results are obtained with no or minimum stretch. The thread may oe passed through the heating oven or smoothing die as many tim'es s is necessary to obtain a smooth, nub-free surface. Advantageously, in smoothing down the nubs not only should excess surface coating be removed, but some of it should be used to fill the ups and down of the thread's surface in order to obtain a sufficiently smooth undercoat structure. If this is not done, the coating remaining on the surface follows the contours of the thread and any subsequently applied coating will follow these contours.

The temperatures employed in the heating oven will vary depending on the coating employed, the proportions of coating material to core, the speed at which the core is passed through the oven and whether the heating αnd/or smoothing is conducted under stretch conditions. As aforementioned, the temperature should be raised above the melting point to a level at which the coating material exudes through the thread as a gelatinous mass wnich can then be seen on the surface of the thread when it cools. Excessively high temperatures which tt in the coating material to α point where it runs off should be avoided as they tend to exude too

much coating material and fail to produce a solid case structure.

Generally speaking, when the impregnation/ precoating operation is conducted under stretch conditions, distribution of the coating material throughout the thread and exudation to the surface occurs at lower temperatures than when no stretch is applied. It is important to note, however, that giving the core a high level of stretch in the impregnation/precoating operation reduces or elim¬ inates the ability to apply stretch in the sub¬ sequent finish coating stage, in accordance with the preferred embodiment of the invention described below, where it may be used to adjust finished suture properties such as break elongation by additional heat treatment of the highly stretched precoated thread.

The optimum melting temperatures employed in the impregnation/precoating operation will depend primarily upon which suture coating material is employed. The smoothing die temperature will also be above the melting point of the coating material and below the melting point of the core. Usually it will conform closely to the temperature employed in the impregnation/precoating stage preferably about 5 to 15 degrees below that used in the irapregnation/precoating stage.

Finish Coating Stage

In the preferred embodiment of the invention, the final stage in obtaining the composite suture structure is to melt extrude coating material onto the smoothed impregnated/precoated thread. Any of the conventional extrusion apparatuses can be employed for this purpose. The smooth precoated

threαd is simply fed through the extrusion coating die and coated with additional coating material of the same type as used in the impregnation/ precoating stage. As aforementioned, it is important to note that the smooth impregnated/ precoated thread subjected to the coating stage be essentially free of an undulating surface. The extrusion temperatures employed in the impregnation/ precoating stage although it has been found that the higher the extrusion coating temperature, other conditions being equal, the greater the finished suture diameter. This is due to decreased melt viscosity with increased 'temperature which results in increased polymer flow under a given applied force.

The following examples are included to further illustrate the novel composite sutures of the ^" invention and their preparation. In the examples, reference is made to the following drawings wherein: Fig. 1 is a schematic drawing of an apparatus useful in the impregnation/precoating stage of the present invention; Fig. 2 is a schematic drawing of an apparatus useful in the extrusion coating of the suture impregnated and precoated by use of the apparatus of Fig. 1; and Fig. 3 is a cross-section of the extrusion die in Fig. 2 on a larger scale.

■-xample I

Directing attention to the drawings, using a conventional New England Butt braider machine 4 strands of "Kevlαr", a tradenamed material of DuPont DeNemours, of 30-50 denier having a straight pull tenacity of approximately 7.5 grams per denier are braided around a single core of continuous 40 denier polypropylene having a straight pull tenac-

-15-

ity of approximately 4 grams/denier. The raw braid tnus formed is wound around a reel 2, and fed through a tensioner 4, about α feed roll (Godet) 6, guide 8 and into α heated 10 cm long tubular oven. The lumen of an extrusion coating die without feed serve this purpose and is designated Heated Zone I in Fig. 1. A draw roll (Godet) 13 pulls the raw braid through the oven without stretch, that is, at a stretch ratio (SR) of 1:1. The Heated Zone I is maintained at α temperature of 230°C. Under these conditions all the polypropylene melts and is entirely distributed throughout the braid inter¬ stices and onto the surface of the braid. No solid polypropylene core residue remains.

As th ^' braid emerges from Heated Zone I, large quantities of excess polypropylene which have melted out are trimmed off manually. The braid then continues through a Guide 15 to Heated Zone II which contains a smoothing die 17 having a 0.2 mm diameter that trims and smooths down nubs that are formed on the braid. Heated Zone II is maintained at a temperature of about 220°C for the smoothing operation. The smoothed braid is pulled through Heated Zone II by a draw roll (Godet) 19 and onto receiving reel 21. The speed at which the braid passes through both Heated Zone I and II is approximately 1-1.8 M/min. The precoated braid is passed through the smoothing die 17 three times so as to obtain an impregnated/precoated braid of the desired smoothness.

Referring to Fig. 2, reel 31 of smooth impregnated/precoated braid prepared as above is passed through tensioner 33, to feed roll (Godet) 35 which feeds the braid through guide 37 into extrusion coating die apparatus indicated generally

OMP

BAD ORIGINAL '

as 39. Polypropylene chips are melted in heated reservoir 41 maintained at a temperature of 260°C and the melt is forced by means of extruding weights 43 applied at α force of 0.233 kg to a piston 45 into and through the extrusion coating die.

Directing particular attention to Fig. 3, the extruding coating apparatus is comprised of a holder indicated generally as 47 which houses a hollow lumen member 49 a spinneret 57 having an outlet 52. The lumen member 49 essentially positioned within the holder 47 so as to provide an annular chamber 53. A gasket 55 seals one end of the member 49 within the holder while the other end is supported by slotted plate 60. The lumen member contains an inlet 59 and an outlet 61. Between outlet 61 and outlet 52 of the spinneret 57 is positioned a hollow needle 63. The impregnated/ precoated thread 65 passes consecutively through lumen member 49, hollow needle 59, outlet 52 and is coated with melt as it emerged from the die. The coating die is maintained at a coating temperature of 235°C.

The coated filament is then taken up on draw roll 48 which applies stretch. Tension is let down on draw roll 50 which is run more slowly than draw roll 48. The yarn velocity is 1.43 M/min. and the total stretch ratio (SR) is 1.02. The finished suture is finally wound around receiving reel 51.

The result is a finished composite suture with a 5/0 diameter "Kevlar" core accounting for approx¬ imately 90% of the cross-sectional area and exhib¬ iting a knot break strength of about 3.2 pounds. A knot break strength of 3.2 pounds is equivalent to USP limits -of size 2.0 monofilament suture. Thus,

N -

-13-

the composite suture prepared can be used as a 5/0, 4/0, or 3/0 suture.

Example II

Tiie process of Example I is repeated substi¬ tuting a polyethylene terephthalate core for poly¬ propylene core and extrusion coating in extrusion coating die apparatus 39 with polyethylene ter¬ ephthalate. The result is a composite suture having a 5/0 diameter "Kevlαr" core accounting for approximately 90% of the cross-sectional volume coated with polyethylene terephthalate exhibiting a knot break strength of about 3.5 pounds which is a knot brek strength above the USP limits for a 2/0 size suture. Therefore, the composite suture pre¬ pared could be used for sizes 5/0, 4/0, 3/0 and 2/0 according to the physician's wishes.

Example III

Fibroin (silk) is dissolved in α aqueous solu¬ tion of 62% zinc chloride to give a solution having fibroin weight % concentrations in the range of 5-20%. The resulting solution is maintained at approximately its boiling point and "Kevlar" yarn of Example I is pulled through the solution at a constant rate as to fully impregnate and coat the yarn. The impregnated and coated yarn is then dried by passing it through a tubular oven main¬ tained at heating temperatures up to 130°C. The heat treatment evaporates the solvent and helps to form a continuous fibroin film. The composite suture is then washed with cold water to remove residual zinc chloride.

The resulting composite suture with a size 5/0 "Kevlαr" core containing approximately 5% by weight fibroin exhibits a knot break strength of approx¬ imately 3.5 pounds which is equivalent to a silk

OfVf

suture of size 2.0. In other words, the silk- coated "Kevlar" composite suture could be used instead of silk in the following sizes: 5/0, 4/0, 3/0 and 2/0.

Example IV

A size 5/0 high strength fully chain-extended polyethylene multifilament yarn having a straight pull tenacity of 50 grams/denier and a knot ten¬ acity of 15 grams/denier is pulled through a 10% solution of polyethylene terephthalate in a solvent mixture of methylene chloride containing 31% by weight hexafluoroisopropanol and then passed through a die to trim off excess solution. The coated core is dried in air and the process re¬ peated to build up the coating to α final composite suture containing 10% oy weight polyethylene tere¬ phthalate. The composite is washed with water and dried again. The resulting composite suture could be used for sizes 5/0, 4/0, 3/0, 2/0 and 1/0.

Example V

Example I is repeated substituting a poly- glycolic cid (PGA) core for the polypropylene core and PGA resin for the polypropylene chips. The resulting "Kevlar"/polyglycolic acid composite has α minimum knot break strength in the range of 1550-1700 grams. Since commercial non-absorbable "Prolene" sutures of size 3/0 has α knot strength of 1550-1650 grams, this means that a size 3/0 "Kevlar"/ρolyglycolic acid suture will retain the knot break strength of 3/0 "Prolene" after ab¬ sorption of all the polyglycolic acid. Thus, the "Kevlar"/ρolyglycolic acid suture prepared could be used for sized 3/0, 4/0 and 5/ϋ.

Wnen 6/0 size "Kevlar" reinforcing core is used with a non-reinforcing PGΛ coating, the core by

itself will give α knot strength midway between size 4/0 and 5/0 based on "Prolene" knot strength but above the USP standards for 4/0. Thus, PGA coated "Kevlαr" composites with α 6/0 core could be used for size 6/0, 5/0 and possible size 4/0.

With size 7/0 reinforcing core and PGA non- supportive coating 6/0 strength is obtained. Thus, PGA coated, 7/0 core "Kevlar" can be used for sizes 6/0 and 7/0.

Using high strength, extended chain poly¬ ethylene having 50 gram/denier straight breaking tenacity, with approximately 1/3 of this converting to knot tenacity, a 5/0 size reinforcing high strength polyethylene core of about 0.140 mm in diameter will impart at least the knot strength of a 2/ϋ suture to the composite. Thus, a PGA-coated high strength polyethylene 5/0 core can be used to make sizes 2/0, 3/0, 4/0 and 5/0 absorbable, non- absorbable composite sutures.

With high strength polyethylene 6/0"size re¬ inforcing core of about 0.90 m diameter and a non- supporting PGA coating, the core itself will pro¬ vide enough knot strength for sizes 4/0, 5/0 and 6/0 based on the knot strength of "Prolene".

With high strength polyethylene 7/0 size rein¬ forcing core of about .060 - .065 mm in diameter and non-reinforcing PGA coating, the core itself will give knot strength sufficient for 5/0, 6/0 and 7/0 composites based on the knot strengths of "Prolene".

With higher strength materials or by increasing the knot strength of the materials mentioned here, a wider spectrum ^' of sizes could be covered with the same fine sized reinforcing core.

In commercial production, needles may be

αttached to one end of the composite sutures of the invention and the sutures may be packed in sterile containers. Inasmuch as the sutures are stable for long periods of time without a conditioning fluid, the sutures may be dry packed in glass tubes or plastic envelopes. Conditioning fluid may be used to assure maintenance of sterility or as a rust preventing medium for the needle. Eyeless needles are preferred since they cause less tissue damage. Conveniently, the composite sutures of the present invention are formed at convenient lengths, attached to eyeless needle, wound on reels if desired, and placed in containers such as plastic envelopes. The sutures may then be sterilized with ethylene oxide or other conventional gaseous sterilizing agents in accordance with known practices. Alternatively, the sutures may be seal J in the envelopes and then sterilized by using heat and radiation including x-rays, gamma rays, electrons, neutrons, etc.

Another advantage offered by the composite sutures of the invention is that .needles of smaller diameter can be attached thereto. In accordance with this feature of the invention the outside cover or coating of suture material at the end of the composite suture is removed by any suitable means as, for instance, by dissolving the cover using a solvent which solubilizes the cover but not the core. The core at the end of the suture is thereby exposed and onto the core is attached as, for instance, by swagging a needle of smaller outer diamter than would be used with a suture of the same outer diameter. Tne following example illustrates this feature of applicants' invention:

Exαmple VI The end of a composite suture prepared according to the general procedure of Example I and having an outer diameter of approximately 0.012 inch is dipped one-eighth inch into boiling xylene until the polypropylene cover softens. The poly¬ propylene cover is then manually scrapped off to expose the 5/0 "Kevlar" core. A 0.014 inch diam¬ eter needle is swαgged onto the core to provide a suture with α needle having a cross-sectional area reduced approximately two-thirds that of needles required for sutures having a 0.012 inch diameter.

- _TA O OR1GMAL