CA1280256C

CA1280256C - Caprolactone polymer for suture coating

Info

Publication number: CA1280256C
Application number: CA000517738A
Authority: CA
Inventors: Kenneth Alan Messier; Joseph David Rhum
Original assignee: Pfizer Hospital Products Group Inc
Current assignee: Teleflex CT Devices Inc
Priority date: 1985-09-11
Filing date: 1986-09-09
Publication date: 1991-02-19
Anticipated expiration: 2008-02-19
Also published as: JPS6260557A; ATE47669T1; AU595235B2; JPH0212106B2; EP0214861A1; US4624256A; EP0214861B1; AU6254286A; DE3666668D1

Abstract

Caprolactone Polymer For Suture Coating Abstract High molecular weight caprolactone polymers are coated on surgical sutures to improve suture properties such as smooth surface, single knot slipdown, two throw knot slipdown for repositioning, and three throw knot security.

Description

12~02~6 - 1 ~ 4680-393 The invention relates to surgical sutures comprising a braided multifilament of a biocompatible material coated with a lubricating agent. More particularly, the invention relates to sutures coated with high molecular weight polycaprolactone or a high molecular weight copoly~ler of at least 90~ by weight of caprolactone.
Coating of braided sutures with lubricating agents to improve knot slipdown properties is known in the art. For instance, U.S. Patent No. 4,080,969 discloses coating braided polyglycolic acid filaments with diglycolate polyesters. U.S. Patent No. 4,027,676 provides a coating for sutures comprising a bio-absorbable film-forming polymer, the bioabsorbable lubricant polyalkylene glycol and a hydrophobic material. U.S. Patent No. 3,867,190 relates to polyglycolic acid sutures coated with a copolymer of lactic and glycolic acid. This patent also mentions incorporation of caprolactone in glycolide sutures.
The formed copolymer contains not more than 15~ by weight of caprolactone. Use of such copolymer in coating of sutures is not suggested.
U.S. Patent No. 3,942,532 describes polyester multifilament sutures coated with polycaprolactone Nia~ Polyol D-560 having a low molecular weight of about 2,000 and a melt viscosity at 60C of 500 centipoise.
It is an object of the invention to provide a suture having a smooth surface/ good single knot slipdown, two throw knot slipdown for repositioning, and three throw knot security.

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In accordance with the invention, there is provided a surgical suture of a braided multifilament biocompatible, bioabsorbable material coated with a lubricating agent selected from the group consisting of S high molecular weight polycaprolactone, a high molecular weight copolymer derived from at least 90~ by weight of caprolactone and the remainder another biodegradable monomer, and a blend of at least 50~ by weight of said polycaprolactone or said copolymer and up to 50% by weight of another biodegradable lubri-cating agent, based on the combined weights of the lubricating agents. The homopolymer or copolymer of caprolactone has a melt viscosity at 60C of at least about 50,000 cen~ipoise (cps) or is a solid.
Generally, the lubricating agent or agents are present in an amount of about 0.5 to 10~ by weight based on the suture.
The invention also provides for a needled surgical suture wherein a novel coated suture as described above is threaded through or fitted with a surgical needle, and a surgical suture package comprising a sterile enclosure containing a sterile needled coated surgical suture as previously described.
According to the invention, any conventional bioabsorbable suture material may be used. Sutures must be biocompatible such that they do not cause any adverse reactions in living tissue. The sutures of the invention are bioabsorbable such that they are slowly absorbed in living tissue. Examples of suitable bioabsorbable suture materials are collagen, poly-(glycolic acid), poly(lactic acid), poly(hydroxybutyric acid), chitosan, chitin, carboxymethylcellulose etc.
Preferably, the suture is made of poly(glycolic _3_ ~2~

acid) or a glycolic acid copolymer containing at least 85% glycolic acid units.
The primary lubricating agent of the invention is high molecular weight polycaprolactone or a h~gh molecular weight copolymer of at least 90~ by weight of caprolactone and at most 10~ by weight of another biodegradable monomer. Examples of such biodegradable monomers are glycolic acid, a glycolide, lactic acid, a lactide, p-dioxanone, valerolactone and other lactones derived from linear aliphatic hydroxycarboxylic acids, ~ -hydroxybutyric acid, ethylene carbonate, ethylene oxide, propylene oxide, propylene carbonate, malic acid ester lactones, succinic acid, adipic acid and other linear aliphatic dicarboxylic acids, and linear aliphatic diols such as butanediol and hexanediol.
High molecular weight polycaprolactone may be made by conventional methods for the polymerization of ~-caprolactone. Suitable polycaprolactones are commercially available, e.g. PCL-300 and PCL-700 of Union Carbide Corporation, also known by the brand names Tone*P-300 and Tone P-700, respectively, having weight average molecular weights of about 15,000 and about 40,000, respectively, as reported by the manufacturer. Copolvmers of caprolactone and another monomer may be made by conventional polymerization techniques, e.g. as described in U.S. Patent No.
4,190,720.
When reference is made hereafter to polycapro-lactone, this will include the above-described co-polymers of caprolactone containing 10% or less of abiodegradable comonomer.
The high molecular weight polycaprolactone is applied to the multifilament suture generally from a solution in a solvent for polycaprolactone such as methylene chloride. Other known solvents for * Trademark 12~3~2~1~

polycaprolactone may be used such as carbon tetrachloride, chloroform, ethyl acetate, cyclohexanone, methyl ethyl ketons, toluene, and xylene. The concentration of the polycaprolactone irl the solvent may range from 1 to 10~ by weight based on the solvent. Generally, about 5 g commercially available polycaprolactone per 100 ml of solvent is used. The preferred concentration will provide a readily flowable composition the solvent of which is not difficult to evaporate after the coating is applied, and will deposit the desired amount of poly-caprolactone on the suture.
The sutures are immersed in the coating solution for 0.1 to 10 minutes, preferably about 0.2-3 minutes, and air dried at room temperature or, if desired, at slightly higher temperatures. The immersion may be carried out by batch dipping a skein or by continuously passing a continuous length of yarn through the coating solution.
The primary lubricating agent, high molecular weight polycaprolactone, may be mixed with other lubricating agents in an amount of up to 50~ by weight of the combined lubricating agents. Examples of such other lubricating agents are poly(ethylene oxide), partially oxidized polyethylene wax, N,N'-ethylene diamine bis-stearamide, C10-C30 fatty acid esters of sterols such as cholesterol and lanosterol, and polyalkylene glycols such as a copolymer of ethylene glycol and propylene glycol.
The coating composition may also contain other components for other purposes including dyes, stabilizers against oxidation or degradation caused by radiation, antibiotics, antiseptics, analgesics, anesthetics, anti-inflammatory agents, growth or healing promoting agents and other pharmaceutically active ingredients.

~Z~ i6 Polycaprolactone is known to be a non-toxic material that degrades 510wly in living tissue to form an innocuous metabolizable intermediate.
The following examples illustrate the invention.
Examples 1-15 and 20 are comparative examples and Examples 16-19 are examples according to the invention.
Examples 1-19 Uncoated sutures of polyglycolic acid (18 inch long) were immersed in 100 ml of coating solution. The solvent, percentage by weight of coating material in solution, percentage coating by weight on the coated suture, and the size of the sutures are listed in Table 1.
The sutures were immersed in the coating solution for 2 to 3 minutes and air dried at room temperature.
The percentage coating was calculated by weighing the suture on an analytical balance before and after coating and is given in Table 1 as percent of total weight of the coated suture. After air drying, the coated sutures were stored in a desiccator.

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~2~30;;~6 The abbreviations and trademarks in Table 1 stand for the following:
PEO: poly(ethylene oxide) PGA: poly~glycolic acid) Plurocol*P-4010: poly(propylene glycol~
PVA: poly(vinyl alcohol) PVP: poly(vinyl pyrrolidone) Petrac*165: wax Petrac*215: partially oxidized polyethylene wax (Petrochemicals Company Inc.) PEG: poly(ethylene glycol) Kemamide *N,N'-ethylene diamine bis-stearamide PCL: polycaprolactone Super Sterol*Ester: cholesterol and lanosterol esters of a mixture of C10-C30 fatty acids esters, supplied by CRODA Inc.
The melt viscosity of PCL (Tone P300) was measured with a Brookfield RVT viscometer having a No. 7 spindle at 20 and 50 rpm. The polymer was melted in a beaker and surrounded by a temperature controlled water bath, the temperature of which was measured with an electronic thermometer sensitive to + 0.1C. The viscosity was 51,200 cps at 60C. PCL (Tone P700)) is solid at 60C. The molecular weight of PCL (Tone P700) was determined by gel permeation chromatography and was found to be 100,000 IPolYstyrene equivalent in dichloromethane).
Table 2 sets out the properties of the coated sutures of Table 1.
The general texture and feel of a suture such as flexibility, smoothness and hardness was observed by handling the suture and drawing between fingers.
Typical observations as set out in Table 2 are stiff, silky, waxy.

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The slipdown property of a suture was determined by tieing tightly a two-throw square knot, then grasping the long ears and pulling apart. If the suture was drawn through the knot, giving the appearance of the knot slipping down the braid, it was marked as excellent (exc.), qood, or acceptable (acc.) depending on the ease of slipdown. If the knot seized or was difficult to slip down, the suture was marked as locks, poor, or rachety, depending on the difficulty of slip down.
The slipdown property was also tested under wet conditions by immersion of the unknotted suture in water for 5 seconds and immediately testing thereafter.
The knot security of a suture was tested by tying firmly a triple throw square knot and pulling the suture from a patient's side until the knot slipped or the suture broke. If the knot slipped, knot security was marked poor. If the suture broke without slip, the knot was sufficient to hold the suture at the knot and was marked acceptable in Table 2.
The knot security was tested under wet conditions by immersion of the unknotted suture in water for 5 seconds and immediately testing thereafter.
The wet knot slipdown was tested by tieing tightly a two-throw granny knot and slipping down the knot.
The knot was then wetted by rubbing with fingers dipped in water. An attempt was then made to slip the knot down further. If the knot slipped both dry and wet, the suture was marked as acceptable, good, or excellent depending on the ease of the slip. If the knot slippad dry but not wet, the suture was marked as locking. If the slip was poor wet and dry and locking was difficult to determine, the suture was marked poor, or rachety.

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Comparative Example 20 An uncoated suture of polyglycolic acid (54 inch long), size 3-0 was immersed in lO0 ml of coating solution comprising 95.0 ml methylene chloride and 5.00 g of Tone polyester 0240 (formerly Niax Polyol D560) of Union Carbide Corporation. The manufacturer specifies a molecular weight o~ 2000 and a viscosity of 500 cps at 60C. for Tone polyester 0240.
The coating solution was obtained by dissolving the Tone polyester 0240 at room temperature in a 200 ml beaker in 3 minutes using a magnetic stirrer.
The suture was immersed in the coating solution for one minute and air-dried at room temperature. The ~ coating on the suture was 5.9.
Knot slip and knot security were determined as follows.
Knot Result 2 throw square slips about 0.5 inch, slip down locks and breaks 203 throw square locks slipdown 2 throw granny acceptable slip slipdown (dry) 2 throw granny acceptable slip 25slipdown (wet)

Claims

1. A surgical suture comprising a braided multi-filament of a biocompatible, bioadsorbable material coated with a lubricating agent, wherein said lubricating agent is selected from (1) a high molecular weight homopolymer of caprolactone, (2) a high molecular weight copolymer of at least 90% by weight of caprolactone and the remainder another biodegradable monomer, and (3) a blend of at least 50% by weight of said homopolymer or said copolymer of caprolactone and up to 50% by weight of another biodegradable lubricating agent, said homopolymer or copolymer of caprolactone having a melt viscosity at 60°C of at least about 50,000 centi-poise or being solid.

2. A suture according to claim 1, wherein said lubricating agent is a high molecular weight homopolymer of caprolactone.

3. A suture according to claim 1, wherein said lubricating agent is a high molecular weight copolymer of at least 90% by weight of caprolactone and the remainder another biodegradable monomer selected from the group consisting of glycolic acid, a glycolide, lactic acid, a lactide, p-dioxanone, lactones derived from linear aliphatic hydroxycarboxylic acids,?-hydroxybutyric acid, ethylene carbonate, ethylene oxide, propylene oxide, propylene carbonate, malic acid ester lactones, succinic acid, linear aliphatic dicarboxylic acids, linear aliphatic diols and mixtures thereof.

4. A suture according to claim 1, wherein said lubricating agent is a blend of at least 50% by weight of said homopolymer or said copolymer of caprolactone and up to 50% by weight of another biodegradale lubricating agent selected from the group consisting of poly(ethylene oxide), partially oxidized polyethylene wax, N,N'ethylenediamine bis-stearamide, C10-C30 fatty acid ester of sterols, copolymers of ethylene glycol and propylene glycol, and mixtures thereof.

5. A suture according to claim 4, wherein said other bio-degradable lubricating agent in (3) is a mixture of sterol esters of C10-C30 fatty acids.

6. A suture according to claim 5, wherein said sterol is a mixture of cholesterol and lanosterol.

7. A suture according to claim 1, wherein said biocom-patible material is absorbable by the body.

8. A suture according to claim 2, 3 or 5, wherein said biocompatible material is adsorbable by the body.

9. A suture according to claim 1, wherein said biocom-patible material is poly(glycolic acid) or a copolymer containing at least 85% glycolic acid units.

10. A suture according to claim 2, 3 or 5, wherein said biocompatible material is poly(glycolic acid) or a copolymer con-taining at least 85% glycolic acid units.

11. A suture according to claim 1, wherein said lubricating agent is present in an amount of 0.5 to 10% by weight based on the weight of the suture.

12. A suture according to claim 2, 3 or 4, wherein said lubricating agent is present in an amount of 0.5 to 10% by weight based on the weight of the suture.

13. A suture according to claim 5, or 7, wherein said lubricating agent is present in an amount of 0.5 to 10% by weight based on the weight of the suture.

14. A needled surgical suture comprising at least one filament of a biocompatible material coated with a lubricating agent, wherein said lubricating agent is selected from (1) a high molecular weight homopolymer of caprolactone, (2) a high molecular weight copolymer of at least 90% by weight of caprolactone and the remainder another biodegradable monomer, and (3) a blend of at least 50% by weight of said homopolymer or said copolymer of caprolactone and up to 50% by weight of another biodegradable lubricating agent, said homopolymer or copolymer of caprolactone having a melt viscosity at 60°C of at least about 50,000 centi-poise.

15. A needled surgical suture according to claim 14, wherein said biocompatible material is poly(glycolic acid) or a copolymer containing at least 85% glycolic acid units.

16. A surgical suture package comprising a sterile enclosure containing a sterile needled surgical suture, the suture com-prising at least one filament of a biocompatible material coated with a lubricating agent, wherein said lubricating agent is selected from (1) a high molecular weight homopolymer of capro-lactone, (2) a high molecular weight copolymer of at least 90% by weight of caprolactone and the remainder another biodegradable monomer, and (3) a blend of at least 50% by weight of said homo-polymer or copolymer of caprolactone and up to 50% by weight of another biodegradable lubricating agent, said homopolymer or copolymer of caprolactone having a melt viscosity at 60°C of at least about 50,000 centipoise or being solid.

17. A package according to claim 16, wherein said bio-compatible material is poly(glycolic acid) or a copolymer con-taining at least 85% glycolic acid units.