Novel topical skin occlusive compositions and systems

Abstract

Novel compositions and systems for wound closure are disclosed. The compositions provide devices with improved flexibility and elasticity, making them easier to apply to the wound site or to the entire wound closure device. The invention also relates to novel platinum catalysts for use in such compositions. The catalysts provide rapid curing on topical surfaces, such as skin, adhering to such surfaces in approximately 2 to 5 minutes.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application is a continuation-in-part of co-pending U.S. Provisional Patent Application No. 16 / 885,361, filed May 28, 2020, and is related to U.S. Provisional Patent Applications Nos. 16 / 885,413 (Attorney Docket No. ETH6068USNP1), 16 / 885,426 (Attorney Docket No. ETH6069USNP1), 16 / 885,366 (Attorney Docket No. ETH6084USNP1), 16 / 885,375 (Attorney Docket No. ETH6085USNP1), all of which were filed May 28, 2020, and U.S. Nonprovisional Patent Application No. __________ (Attorney Docket No. ETH6084USCIP1, now filed herewith), all of which have a common assignee and are hereby incorporated by reference in their entireties.

[0002] (Technical field) The technical field to which this invention pertains is silicone-based wound closure compositions and devices, particularly silicone-based topical skin adhesives (TSAs) and systems. [Background technology]

[0003] In particular, there is a need for elastomeric topical skin adhesives for skin closure over moving body joints such as knees, wrists, and elbows.

[0004] Elastic versions of TSAs are particularly needed in orthopedic surgery. Active movement of the joint can compromise the quality of the closure at the interface between the adhesive and the skin. A watertight closure is also desirable in the product to reduce the possibility of post-surgical infection. The silicone type of adhesive, due to its elastic and sealing properties, is one solution to both of these two major customer requirements.

[0005] Silicones are known for their inertness and are commonly used in over-the-counter scar reduction products. Reduced skin reactions and improved cosmetic appearance are additional benefits offered by silicone-based TSAs. Summary of the Invention [Problem to be solved by the invention]

[0006] Thus, there is a need for elastomeric topical skin adhesives, particularly for closure of moving body parts and joints such as knees, wrists, elbows, etc. [Means for solving the problem]

[0007] Accordingly, novel catalyst compositions, silicone-based curable adhesive compositions, and wound closure systems are disclosed.

[0008] The composition includes a mixture of vinyl-terminated polydimethylsiloxane and polydimethylhydro-co-polydimethylsiloxane crosslinker, surface-treated silica particles as a binder, and optionally a novel, unconventional platinum catalyst with a common low-boiling organic solvent, such as an aliphatic organic solvent like hexane or its commercially available derivatives, and a SiH-terminated polydimethylsiloxane chain extender. The proposed silicone adhesive can dry on skin in less than 3 minutes at body temperature. The skin retention between the proposed silicone adhesive and skin is comparable to or better than that of typical cyanoacrylate-based TSA products. Unlike conventional cyanoacrylate-based TSA products, the silicone-based TSA of the present invention can be stretched up to 160% of its original length and fully recover to its original dimensions when combined with a conventional wound closure device.

[0009] Bond formation is enabled by a condensation reaction between silanol functional groups on the surface of the silica particles and OH functional groups on the skin. Silanol condensation tends to be slow at ambient temperatures, and the novel, unconventional catalyst allows this reaction to occur in a short period of time. The novel platinum-based catalyst also activates the vinyl silylation reaction, allowing the vinyl-terminated silicone polymer to simultaneously crosslink and undergo a condensation reaction.

[0010] In one embodiment, the present invention provides a crosslinkable silicone polymer having reactive functional groups; a silica-containing composition; a silicone crosslinker; a catalyst comprising a platinum tetramethyldivinyldisiloxane diethylmaleate complex having the formula: Pt[(CH2=CH)(CH3)2Si]2O·(COCH=CHCO)(C2H5O)2; The present invention relates to a composition comprising:

[0011] In the foregoing embodiment, the silica-containing composition may be added as a separate component, but more preferably it is contained in the crosslinkable silicone polymer. The coating composition may also contain a platinum catalyst.

[0012] Another aspect of the present invention is a medical device having a surface, at least a portion of which is coated with the novel silicone coating composition described above.

[0013] Yet another aspect of the present invention is a novel platinum catalyst for use in crosslinkable silicone coatings. The catalyst has the following formula: Contains platinum complexes with Pt[(CH2=CH)(CH3)2Si]2O·(COCH=CHCO)(C2H5O)2.

[0014] A further aspect of the present invention is the use of the compositions of the present invention as topical skin adhesives and in combination with wound closure devices as systems or kits for closing wounds.

[0015] In other embodiments, the compositions of the present invention are made under controlled viscosity requirements that limit or eliminate the need for organic solvent(s), as described below.

[0016] These and other aspects and advantages of the present invention will become more apparent from the following description. [Brief explanation of the drawings]

[0017] [Figure 1] 1 is a comparison of the NMR peaks of the Karstedt catalyst compared to the NMR peaks of the novel catalyst of the present invention. [Figure 2A] 1 illustrates the steps of the stretch test used to demonstrate the elasticity of the present invention. [Figure 2B] 1 illustrates the steps of the stretch test used to demonstrate the elasticity of the present invention. [Figure 2C] 1 illustrates the steps of the stretch test used to demonstrate the elasticity of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0018] The terms silicone and siloxane are conventionally used interchangeably in the art, and that usage is adopted herein.

[0019] Topical skin adhesive compositions and wound closure systems One aspect of the present invention relates to novel wound closure compositions that are particularly useful for closing lacerations and surgical incisions. These compositions are suitable for use as topical skin adhesives and as adhesives in combination with wound closure devices.

[0020] In one embodiment, the composition comprises a mixture of a crosslinkable siloxane polymer and a silica-containing composition, which may be added as a separate component, but more preferably is contained in the crosslinkable silicone polymer, a conventional silicone crosslinker, and a platinum catalyst. The silicone polymer component is blended with a conventional aromatic organic solvent, including, for example, an aliphatic organic solvent (e.g., hexane, heptane, or their commercially available derivatives), to form a coating solution or composition. Other solvents suitable for coating solutions include, but are not limited to, low molecular weight siloxanes, such as hexamethyldisiloxane.

[0021] The crosslinkable siloxane polymers useful in the compositions of the present invention have reactive or terminal functional groups, including, but not limited to, vinyl-terminated hydroxyl and acrylate functional groups. The crosslinkable siloxane polymers that can be used in the compositions of the present invention preferably include vinyl-terminated polydialkylsiloxanes or vinyl-terminated polyalkylarylsiloxanes. Examples include, but are not limited to, the following vinyl-terminated siloxane polymers: polydimethylsiloxane, polydiphenylsilane-dimethylsiloxane copolymer, polyphenylmethylsiloxane, polyfluoropropylmethyl-dimethylsiloxane copolymer, and polydiethylsiloxane. It is particularly preferred to use vinyl-terminated crosslinkable polymethylsiloxanes.

[0022] Crosslinkers that can be used in the compositions of the present invention include conventional silicone crosslinkers such as polymethylhydrosiloxane, polymethylhydro-co-polydimethylsiloxane, polyethylhydrosiloxane, polymethylhydrosiloxane-co-octylmethylsiloxane, and polymethylhydrosiloxane-co-methylphenylsiloxane. Preferred conventional crosslinkers for use in the compositions of the present invention are polymethylhydrosiloxane and polymethylhydro-co-polydimethylsiloxane. Accurate control of the crosslink density in the coatings of the present invention is achieved by precisely controlling the ratio of non-crosslinkable silicone polymer (e.g., polydimethylsiloxane) to the total crosslinked polymer. The total crosslinked polymer is formed by the reaction between a functionalized crosslinkable polymer and a crosslinker, for example, a vinylsilylation reaction between a vinyl-terminated polydimethylsiloxane and a polymethylhydrosiloxane, optionally in the presence of a platinum complex catalyst. Examples of such polymers include, but are not limited to, Gelest product code numbers DMS-V31, DMS-V33, DMS V-35, DMS V42, DMS-V46, DMS-V52, etc., available from Gelest, Inc., Morrisville, Pa. 19067. A typical molecular structure of vinyl-terminated polydimethyldisiloxane is as follows:

[0023] [ka] where n is defined by the molecular weight.

[0024] The molecular weight of the silicone polymer used can be estimated based on the relationship between viscosity and molecular weight (page 11, SILICONE FLUIDS: STABLE, INERT MEDIA ENGINEERING AND DESIGN PROPERTIES, Catalog published by Gelest, Inc. 11 East Steel Rd. Morrisville, PA 19067). For molecular weights (M) > 2,500, which correlate to kinematic viscosity μ expressed in centistokes (cSt) at 25°C, the A.J. Barry relationship can be used to estimate the molecular weight M of the silicone as follows: log μ cSt =1.00+0.0123M 0.5 (Published by A.J. Barry in Journal of Applied Physics 17 1020 (1946))

[0025] Under appropriate conditions, vinyl-terminated polydimethylsiloxane reacts with a polymethylhydrosiloxane crosslinker in the presence of a platinum catalyst, and the vinyl-terminated polydimethylsiloxane linear polymers are fully crosslinked to one another as a result of this reaction. The amount of polymethylhydrosiloxane crosslinker is in stoichiometric excess relative to the vinyl-terminated polydimethylsiloxane base polymer. It is believed that the excess SiH functional groups in the crosslinker react with OH functional groups on the surface of, for example, a polymeric suture, such as human skin, to form Si-O-C bonds at elevated temperatures, or Si-O-Fe bonds in the case of steel needles. The resulting covalent bond between the silicone coating and the device adhesively attaches the coating to a given surface as a result of this reaction.

[0026] The polymethylhydrosiloxane crosslinker or crosslinkers used in the practice of the present invention have a molecular weight of about 1000 to about 3000, preferably about 1400 to about 2100. Examples of the present polymeric crosslinkers include, but are not limited to, Gelest product code numbers HMS-991 and HMS-992, available from Gelest, Inc. (Morrisville, Pa. 19607). A typical molecular structure of a polymethylhydrosiloxane crosslinker is as follows:

[0027] [ka] where n is defined by the molecular weight.

[0028] Polymethylhydro-co-polydimethylsiloxane may also be used as a crosslinker in the novel coatings of the present invention. Examples of this polymer include, but are not limited to, Gelest product code numbers HMS-301 and HMS-501. The molecular weight of this siloxane polymer crosslinker is typically about 900 to about 5,000, preferably about 1,200 to about 3,000. A typical molecular structure of a polymethylhydro-co-polydimethylsiloxane crosslinker is as follows:

[0029] [ka] where n and m are defined by the molecular weight.

[0030] Silica-containing composition As used herein, silica-containing compositions described for use with the present invention include silica materials from commercially available compositions that contain silica as a separate component (such as surface-treated silica) or in a crosslinkable silicone polymer mixture.

[0031] As a separate component, silica is incorporated into the compositions of the present invention to act as a binder to skin and other substrate materials. It is believed that the OH groups on the surface of the silica particles react with OH functional groups on the surface of substrate materials, including human skin, under certain conditions, as shown below.

[0032] [ka]

[0033] Silica particles are incorporated into crosslinkable silicone polymers. To enable their compatibility with the polysiloxane polymer matrix, which prevents phase separation, the silica particles require a hexamethylsilyl surface treatment. One example of a treated silica is hexamethyldisilazane-treated silica, i.e., trimethylsilyl surface-treated silica filler (Gelest SIS6962.0).

[0034] For silicone polymers that already contain silica, these may be obtained from commercially available sources, such as silica-containing compositions selected from reactive silica-containing silicone bases, including HCR (high consistency rubber) bases and LSR (liquid silicone rubber) bases, with LSR bases being preferred. Other commercially available examples of this material include, but are not limited to, Wacker 401-10, 401-20, and 401-40 bases, and liquid silicone rubber bases. Commercially available examples of this material include, but are not limited to, Bluestar Silbione LSR 4370 base. These types of commercially available silicone rubber bases are prepared by mixing surface-treated silica fillers with vinyl-terminated polydimethylsiloxane polymers of various molecular weights. Surface treatments may be performed in situ during the mixing process to improve compatibility between the filler and the polysiloxane polymer.

[0035] catalyst Karstedt of GE Silicone invented a highly active platinum catalyst in the early 1970s (U.S. Patent No. 3,775,452). Vinyl-terminated polydimethylsiloxane can react with polymethylhydrosiloxane-containing crosslinkers in less than one minute at ambient temperature using only 10 ppm of Karstedt's catalyst. Conventional platinum catalysts do not allow the reaction between OH groups on the surface of silica particles and OH functional groups on the surface of a substrate. This type of condensation reaction tends to be slow at ambient conditions, and typical catalysts for this reaction include organic amines and catalysts such as tin dilaurate. Trace amounts of condensation catalysts can quench the catalytic activity of the platinum catalyst, a phenomenon known in the silicone industry as platinum poisoning. To enable rapid adhesion formation between silicone and a given substrate material, a novel platinum-equivalent catalyst is needed to activate OH condensation between silica particles and the substrate material. The novel platinum-based catalyst of the present invention can simultaneously activate both vinyl silylation and OH condensation.

[0036] The new catalyst is prepared by reacting Karstedt's catalyst with diethyl maleate according to Scheme 1. The new platinum tetramethyldivinyldisiloxane diethyl maleate catalyst enables both vinylsilylation and condensation reactions. It is called a "dual-functional silicone catalyst."

[0037] [ka]

[0038] The novel catalysts of the present invention may be prepared by mixing Karstedt's catalyst in xylene solution with a low concentration of vinylcyclohexanol in xylene solution at ambient temperature for a time effective to complete the reaction, e.g., 30 minutes, as indicated by a change in color of the reaction mixture from clear to light brown.

[0039] The resulting catalyst solution containing the novel catalyst of the present invention is ready for use in compositions useful as topical skin adhesives. The formula of the resulting platinum complex catalyst (platinum tetramethyldivinyldisiloxane diethylmaleate complex) is: Pt[(CH2=CH)(CH3)2Si]2O·(COCH=CHCO)(C2H5O)2.

[0040] It should be noted that the resulting catalytic reaction mixture contains a small amount of the reaction product divinyltetramethyldisiloxane. This component is a low-boiling component that does not affect the catalyst and evaporates quickly. Therefore, purification of the catalytic mixture to remove divinyltetramethyldisiloxane is optional, and its presence at ultra-low concentrations is not believed to affect the crosslinking reaction of the crosslinkable silicone polymer. The novel catalyst of the present invention also activates bond formation between silanol groups on the surface of the silica filler and OH functional groups on a given surface; that is, the catalyst can activate two reactions. This allows the crosslinkable components in the silicone coating to cure, rapidly forming a coating film at the desired curing temperature and providing bonding to a given substrate, such as human skin.

[0041] Solvents for viscosity reduction Some commercially available filler-reinforced cross-linkable silicone polymers (silicone-based rubbers) have high viscosities, typically greater than 500,000 and up to several million cP. Mixing and applying such high-viscosity materials onto the skin is impossible, and low-toxicity organic solvents are required to reduce the viscosity.

[0042] For this purpose, low-temperature aliphatic solvents are used. Typical examples include, but are not limited to, pentane, heptane, hexane, and mixtures thereof. The organic solvent is added at a concentration sufficient to effectively blend the silicone polymer components into a homogeneous solution. The total solvent concentration is 10% to 30%, depending on the original viscosity of the base rubber. Ultra-low boiling point solvents, such as n-butane and isopentane, can also be used to provide a sprayable formulation of the silicone adhesive.

[0043] Chain extenders for low viscosity vinyl-terminated polydimethylsiloxane-based polymers For commercially available filler-reinforced crosslinkable silicone polymers (silicone-based rubbers) with high viscosities ranging from 100,000 centipoise (cP) to several million cP (e.g., 1 million to 20 million cP), a (low molecular weight) vinyl-terminated polydimethylsiloxane (<300 cP) may be added along with a low-temperature aliphatic solvent to improve its mixing and application properties. SiH-terminated polydimethylsiloxane is added as a chain extender to polymerize low-molecular weight vinyl-terminated polydimenthylsiloxane. The SiH-terminated polydimethylsiloxane-based polymer has a molecular weight of 1,000 to 100,000, preferably 3,000 to 10,000.

[0044] Examples of this type of polymer include, but are not limited to, Gelest product code numbers DMS-H21, DMS-H31, etc. A typical molecular structure of SiH terminated polydimethyldisiloxane is shown below:

[0045] [ka]

[0046] The silicone polymer and novel platinum catalyst are dispersed in a low-boiling organic solvent to form a coating solution. Low-temperature aliphatic solvents are used for silicone dispersions. Aromatic solvents and hexamethyldisiloxane are commonly used for silicone dispersions. Typical examples include, but are not limited to, pentane, heptane, hexane, and mixtures thereof. The organic solvent is added at a concentration sufficient to effectively blend the silicone polymer components into a homogeneous coating solution. The total solvent concentration is about 80% to about 99% by weight, more typically about 85% to about 93% by weight, depending on the coating thickness requirements. Those skilled in the art will understand that the coating thickness can be manipulated by varying the solids content of the coating solution.

[0047] The order of component addition is important. A typical coating composition is prepared in the following manner: If silica is added as a separate component, the vinyl-terminated polydimethylsiloxane is dispersed with the surface-treated silica in a first solution, such as hexamethyldisiloxane, for up to two hours until completely homogenous (Solution 2). Heptane is then added (Solution 3) and mixed for an additional hour before adding the polymethylhydrosiloxane crosslinker. After all catalysts are added as the final component, the solution is thoroughly blended for an additional hour.

[0048] In the following paragraphs, weight percent refers to the weight percent of the total solids content in the coating solution. The novel coating compositions of the present invention contain sufficient amounts of polymeric components, silica-containing compositions, crosslinkers, catalysts, and solvents to effectively provide silicone coatings with high flexibility and durability.

[0049] Typically, the amount of silica in the coating solution is about 5% to about 40% by weight (total solids), more typically about 10% to about 30% by weight (total solids), and preferably about 15% to about 25% by weight (total solids). The amount of crosslinkable silicone polymer is typically about 60% to about 95% by weight (total solids), more typically about 70% to about 90% by weight (total solids), and preferably about 75% to about 85% by weight (total solids). The amount of silicone crosslinker is typically about 1% to about 15% by weight (total solids), more typically about 2% to about 10% by weight (total solids), and preferably about 3% to about 8% by weight (total solids). The amount of platinum catalyst based on total solids in the novel silicone coating compositions of the present invention (elemental platinum in total solids) is typically from about 0.06% to about 0.003% by weight, more typically from about 0.04% to about 0.008% by weight, and preferably from about 0.03% to about 0.01% by weight.

[0050] The amount of organic solvent in the compositions of the present invention is typically about 0% to about 30% by weight, more typically about 10% to about 20% by weight, and preferably about 12% to about 18% by weight. Those skilled in the art will understand that the amount of solvent present in the novel coating compositions of the present invention will vary depending on several factors, and that the amount of solvent in the coating composition will be selected to produce an effective coating. Typical factors to consider include the application method, curing method, coating equipment used, ambient conditions, thickness, etc. It will be understood that each component of the coating compositions of the present invention may be composed of a blend of these components. For example, two or more crosslinkable silicone polymers having different functional groups and / or molecular weights may be used.

[0051] The compositions of the present invention are well suited for wound closure applications such as topical skin adhesives. Generally, these compositions have been demonstrated to cure to a non-tacky character or feel at temperatures of about 19°C. At temperatures of about 28°C, the compositions cure for about 2-5 minutes.

[0052] As described above and as will be understood by those skilled in the art, the silicone composition of the present invention cures into a film that is neither sticky nor tacky in a few minutes.In contrast, some silicone adhesives, such as silicone pressure-sensitive adhesives (PSAs), are inherently sticky or tacky, and are intended to remain so throughout the adhesive's usable life.Such usable life of tacky silicone PSAs can be several years or more.The non-stickiness of the compositions and examples of the present invention is measured by ASTM C679.

[0053] Generally, ASTM C679 involves lightly touching the surface of a curable sealant to a polyethylene film at regular intervals until the sealant does not adhere to the film and the film appears clean when peeled from the surface. More specifically, a strip of polyethylene film is placed on the surface of the cured elastomer, and a 30g weight is placed on the film. The weight is left in place for 30 seconds, then removed, the polyethylene strip is removed, and the film is examined for sealant adhesion. The length of time from when the sealant is first applied to a given surface until no more sealant is taken up by the film is called the tack-free time, which is the point at which the film exhibits non-tacky properties and is evidence that the sealant has cured.

[0054] Upon setting, the hardenable compositions of the present invention exhibit extensible, flexible, and elastic properties that make them particularly useful for application to wound closure over flexible joints, such as knees, elbows, etc. Optionally, in combination with various wound closure devices, the hardenable compositions of the present invention can be applied to any wound closure, including wounds over flexible joints or wounds that do not span flexible joints, such as in typical surgical closures, for example, to any tissue region of the body, abdomen, arms, legs, shoulders, back region, or the like.

[0055] The compositions of the present invention may be applied directly onto the wound as a hardenable liquid or hardenable semi-liquid, flowable composition, or may be applied onto a porous, flowable composition-permeable wound closure device.

[0056] Wound Closure System As noted above, the compositions of the present invention are suitable for use in combination with wound closure devices.

[0057] Wound closure devices suitable for use in the present invention include any device configured to close a wound. The most useful wound closure devices are wound closure strips, tapes, patches, or any other material suitable for closing a wound, most preferably strips. Preferably, the wound closure device is porous to allow the flowable polymerizable adhesive to penetrate the device and properly bond to the tissue surface to be bonded.

[0058] The wound closure device includes a wound-facing surface and an upper surface. The wound-facing surface may further include an adhesive, such as a pressure-sensitive adhesive (PSA), applied to at least a portion of the wound-facing surface. The PSA is useful for initial proximity to the wound. The wound closure device is preferably porous. As used herein, "porous" means either that the bulk of the wound closure device has pores, such that a subsequently applied polymerizable adhesive composition is soaked up, i.e., absorbed, by the bulk material, or that the bulk of the wound closure device has voids (such as a mesh or screen), such that a subsequently applied polymerizable adhesive composition is soaked up, i.e., absorbed, by the bulk material or passes directly through the bulk material without being absorbed. For example, in the case of a woven material, "porous" is generally used to mean that the applied adhesive composition penetrates and passes through the gaps between the fibers, but not necessarily through the fibers themselves. Preferably, the wound closure device is a mesh strip.

[0059] Such porosity (or other properties, such as hydrophobicity or hydrophilicity) further allows for polymerization initiators or rate modifiers to be loaded into or onto the wound closure device prior to use to initiate the subsequently applied polymerizable adhesive composition. Such porosity also preferably allows air and liquid to pass through the wound closure device, either through the pores themselves or through voids in the bulk material. Depending on the degree of porosity and / or the size of the openings, the porosity of such meshes, or the ability of air and liquid to permeate through the mesh, may be tailored to remain or be absent after formation of the final composite material. Because they are intended for use in covering wounds, such as on biological tissue, wound closure devices are also preferably non-toxic. Therefore, wound closure devices should be biocompatible with the desired substrate (e.g., tissue, skin, organs, etc.), preferably of a material that is government-approved or generally considered safe for the desired purpose. By way of example, a suitable wound closure device is a mesh material, as disclosed in US Patent Application Nos. 2006 / 0009099 and 2005 / 0182443, which are incorporated herein by reference in their entireties.

[0060] The wound closure device may be a woven fabric or mesh / web material. Suitable woven fabric materials may be formed from either synthetic or natural materials. Such woven fabric materials may be formed from either woven or nonwoven fabrics or materials. The wound closure device may be, for example, any suitable polymeric film, plastic foam (including open-cell foam), woven fabric, knitted fabric, nonwoven fabric, mixtures thereof, etc. In particular, suitable wound closure devices may therefore be prepared from, for example, nylon, polyolefins such as polyethylene, polypropylene, ethylene propylene copolymers, and ethylene butylene copolymers, acrylic, rayon, polyurethane, polyurethane foam, polystyrene, plasticized polyvinyl chloride, polyesters such as polyethylene terephthalate (PET), polyamides, polylactic acid, polyglycolic acid, polycaprolactone, blends of the above copolymers, natural materials such as cotton, silk, and linen, polytetrafluoroethylene (PTFE), biovascular materials, collagen, Gore-Tex®, DACRON®, etc. Preferred wound closure device materials are those that contain OH functional groups on their surface, either naturally occurring or by surface treatments that impart OH functional groups ("OH surface treatments"). These materials include, but are not limited to, polyester, nylon, acrylic, rayon, polyurethane, polyurethane foam, polystyrene, polyester, polyethylene terephthalate (PET), polyamide, polylactic acid, polyglycolic acid, polycaprolactone, copolymer mixtures of the above, and cotton, silk, and linen. Suitable OH surface-treated materials that impart OH functional groups to their surfaces include, but are not limited to, OH surface-treated PTFE, OH surface-treated polypropylene, and OH surface-treated polyethylene.

[0061] The wound closure device may be formed from synthetic, semi-synthetic, or natural organic materials. Thus, for example, the mesh may be formed from synthetic or natural polymeric materials but not from materials such as metals (such as silver, steel, etc.) or glass or ceramics. The wound closure device may be either biodegradable or non-biodegradable. The wound closure device is preferably tear-resistant.

[0062] The wound closure device may have a thickness of about 0.1 mm to about 25 mm, hi another embodiment, the wound closure device has a thickness of about 0.5 mm to about 20 mm, preferably about 0.7 mm to about 10 mm, and most preferably about 1 mm to about 5 mm.

[0063] When the wound closure device is a strip, the strip may be about 2 cm to about 40 cm in length, preferably about 10 to about 30 cm, and most preferably 25 cm, and the strip may be 0.1 to about 8 cm in width, preferably about 2 to 6 cm, and more preferably about 4 cm.

[0064] The wound closure device may be selected to be elastic or to have some memory effect. In such embodiments, the elastic properties of the mesh may desirably provide some pressure or stress at the application site, for example, to maintain wound edge approximation. Similarly, in embodiments where such an additional degree of pressure or stress at the application site is not desired, the mesh may be selected to be less elastic or non-elastic.

[0065] Wound closure devices can be either biodegradable or non-biodegradable. "Biodegradable" means that the mesh biodegrades in vivo over time, thereby eliminating the need for physical removal of the mesh after a period of time. Thus, for example, a biodegradable mesh would biodegrade in an in vivo environment over a period of about one week to about five years. A non-biodegradable material would not biodegrade in an in vivo environment within about five years. Such non-biodegradable materials would therefore require physical removal of the wound closure device at a desired time, rather than slowly degrading over time or naturally shedding from the tissue.

[0066] The wound closure device may include one or more chemicals located therein or thereon. For example, one or more chemicals may be dispersed in or on the wound closure device, such as chemically bonded, physically bonded, absorbed, or adsorbed thereto. Such chemicals that may be present in or on the wound closure device include, but are not limited to, any suitable, and preferably compatible, additives that enhance the performance of the composite structure. Such additional chemicals may be bioactive or non-bioactive. Accordingly, suitable other chemicals include, but are not limited to, colorants (such as inks, dyes, and pigments), fragrances, protective coatings that do not chemically strip, temperature-sensitive agents, pharmaceuticals, wound healing agents, antimicrobial agents, etc. [Example]

[0067] Example 1: Novel platinum catalyst (synthesis procedure) 44.50 g of Gelest SIP6831.2 (2.2% platinum divinyltetramethyldisiloxane complex in xylene, Karstedt catalyst) was mixed with 2 g of diethyl maleate for 24 hours at ambient temperature. Samples were removed for NMR testing after 3 hours, 18 hours, and 24 hours, and the 3-hour NMR spectrum is shown in Figure 1.

[0068] The formulation of the new catalyst is evidenced in Scheme 1, which is based on NMR spectroscopic identification. The Karstedt catalyst exhibits a NMR spectrum of approximately -6111 ppm. 195 It is known to be a Pt signal characteristic.

[0069] As shown in the NMR spectrum of this mixture at 3 hours in Figure 1, after mixing the mixture of Example 1 for 3 hours, a new 195 A Pt signal was observed along with the original signal of the Karstedt catalyst at -6111 ppm. The intensity of the new signal increased over time, while the intensity of the signal of the Karstedt catalyst simultaneously decreased.

[0070] Example 2. Preparation of a silicone-based topical skin adhesive Generally, like most commercially available platinum-cured silicone materials, silicone-based topical skin adhesives are delivered in a two-part kit by mixing equal amounts of a part A component and a part B component.

[0071] Briefly, vinyl-terminated polydimethylsiloxane was mixed with platinum tetramethyldivinyldisiloxane diethylmaleate catalyst, silica particles, and optionally an aliphatic organic solvent using a high-speed mixer to form Part A of the kit. Vinyl-terminated polydimethylsiloxane was mixed with polymethylhydro-co-polydimethylsiloxane crosslinker, silica particles, and optionally an aliphatic organic solvent using a high-speed mixer to form Part B of the kit.

[0072] Equal amounts of the two-part kit were mixed using a static mixer and then applied to the surface of a substrate such as skin. The two-part kit mixture cured within 5 minutes at body temperature, as determined by loss of viscosity or tackiness of the applied silicone.

[0073] Part A 40 g of vinyl-terminated polydimethylsiloxane (Gelest DMSV41) and 10 g of surface-treated silica particles (Gelest SIS6962.0) were mixed with 2.6 g of the catalyst obtained in Example 1 using a high-speed centrifugal mixer (FlackTek DAC150 FV-K) at 3470 rpm for 5 minutes.

[0074] Part B 40 g of vinyl-terminated polydimethylsiloxane (Gelest DMSV41) and 10 g of surface-treated silica particles (Gelest SIS6962.0) were mixed together with 3.34 g of polymethylhydro-co-polydimethylsiloxane (Gelest HMS301) using a high-speed centrifugal mixer (FlackTek DAC150 FV-K) at 3470 rpm for 5 minutes.

[0075] Example 3. Preparation of a silicone-based topical skin adhesive using commercially available silica-containing silicone raw materials. Part A 90 g of E-Kem44 experimental base (containing a vinyl-terminated polydimethylsilicone-based polymer and fume silica particles) was mixed with 4.72 g of the catalyst obtained in Example 1, 9.0 g of a low molecular weight vinyl-terminated polydimethylsilicone-based polymer (Gelest DMS V21), and 26 g of hexane using a high-speed centrifugal mixer (FlackTek DAC150 FV-K) at 3470 rpm for 5 minutes.

[0076] Part B Using a high-speed centrifugal mixer (FlackTek DAC150 FV-K) at 3470 rpm for 5 minutes, 81 g of E-Kem44 experimental base (containing a vinyl-terminated polydimethylsilicone-based polymer and fume silica particles) was mixed with 8.1 g of polymethylhydrosiloxane crosslinker (Gelest DMS H991), 2.7 g of SiH-terminated polydimethylsiloxane chain extender (Gelest DMS H21), and 10.2 g of hexane.

[0077] Control Examples: Control examples without silica binder and use of conventional Karstedt catalyst Part A 40 g of vinyl-terminated polydimethylsiloxane (Gelest DMSV41) was mixed with 2.6 g of Karstedt catalyst xylene solution (1% Gelest SIP 6831.2 in xylene) using a high-speed centrifugal mixer (FlackTek DAC150 FV-K) at 3470 rpm for 5 min.

[0078] Part B 40 g of vinyl-terminated polydimethylsiloxane (Gelest DMSV41) was mixed with 3.34 g of polymethylhydro-co-polydimethylsiloxane (Gelest HMS301) using a high-speed centrifugal mixer (FlackTek DAC150 FV-K) at 3470 rpm for 5 minutes.

[0079] Example 4. Test Sample Preparation and Description of Test Procedures Test Procedure Preparation of Wound Closure Strip Test Samples: An 8" x 11" synthetic substrate (or biosubstrate) was cut into two halves measuring 4" x 11". A 1" wide PSA (pressure sensitive adhesive) coated polyester mesh was placed along the cut line to hold the two halves together. The two-part silicone TSA composition described above was mixed and applied evenly onto the mesh using a conventional rubber spatula to cover the entire area of ​​the mesh.

[0080] Holding strength test: This test evaluated the force required to separate a PSA-coated mesh and a substrate that approximated the applied silicone TSA composition. The method was based on ASTM F2458: Standard Test Method for Wound Closure Strength of Tissue Adhesives and Sealants.

[0081] A synthetic substrate (Mylar) was used for testing, and selected samples were also tested on pig skin. The width of the synthetic substrate was 1 inch, the pig skin was 2 inches, and the strain rate was 20 inches / minute.

[0082] Peel test T-peel strength testing was performed according to ASTM F2256: Standard Test Method for Strength Properties of Tissue Adhesives in T-Peel with Tension Loading.

[0083] The average peel strength of mesh coated with silicone-based TSA in a T-peel configuration is performed at a strain rate of 10 inches / minute.

[0084] Holding strength test sample Synthetic substrate, polyester film (0.05 inch thick Duralar® film), Graphics Plastics, Maple Heights, OH An 8-inch x 11-inch piece of Duralar® polyester film was cut into two halves measuring 4 inches x 11 inches. A 1.5-inch-wide PSA (pressure-sensitive adhesive)-coated polyester mesh (Lot No. 16204, Innovize, St. Paul, MN) was placed along the cut line to hold the two half specimens together. Each of the two-part silicone TSA compositions in each of the following examples (Example 2, Example 3, and Control) was mixed and applied evenly to the mesh using a conventional rubber spatula, covering the entire area of ​​the mesh. The samples were allowed to dry at 31°C for 2-5 minutes. 5, 1-inch-wide strips of each coated mesh sample were cut for testing.

[0085] Bio-based material (pig skin) A 2 inch by 8 inch pig skin sample was cut into two halves measuring 2 inches by 4 inches. A 1.5 inch wide PSA (pressure sensitive adhesive) coated polyester mesh was placed along the cut line to hold the two halves together. A two-part silicone TSA composition (Example 3) was mixed and applied evenly onto the mesh using a conventional rubber spatula to cover the entire area of ​​the mesh.

[0086] Peel test sample Synthetic substrate (polyester film, 0.05 inch thick Duralar® film, Graphics Plastics, Maple Heights, OH) A 5" x 5" PSA (pressure-sensitive adhesive) coated polyester mesh (Lot No. 16204, Innovize, St. Paul, MN) was placed on a polyester substrate of the same dimensions. Each of the two-part silicone TSA compositions of the following examples was mixed (Example 2, Example 3, and Control) and applied evenly to the mesh using a conventional rubber spatula to cover the entire area of ​​the mesh. After each of the coated mesh samples was dried, a 1-inch wide specimen was cut for testing.

[0087] Biomatrix (arm of a 55-year-old Asian male) A 3 inch x 1 inch PSA (pressure sensitive adhesive) coated onto polyester mesh was placed on the left arm of a 55-year-old Asian male. Each of the two-part silicone TSA compositions of the following examples was mixed (Example 3 and Control) and applied evenly onto the mesh using a conventional rubber spatula to cover the entire area of ​​the mesh.

[0088] Bio-based material (pig skin) A 5" x 1.5" PSA (pressure sensitive adhesive) coated polyester mesh (Lot #16204, Innovize, St. Paul, MN) was placed on a piece of pig skin of approximately the same dimensions. The two-part silicone TSA composition of Example 3 was mixed and applied evenly onto the mesh using a conventional rubber spatula to cover the entire area of ​​the mesh.

[0089] Stretching test sample A 5-inch x 5-inch PSA (pressure-sensitive adhesive)-coated polyester mesh (Lot No. 16204, Innovize, St. Paul, MN) was placed on a Teflon substrate. A two-part silicone TSA composition was mixed (Example 3) and applied evenly onto the mesh using a conventional rubber spatula to cover the entire area of ​​the mesh. The silicone-coated polyester mesh was peeled from the Teflon substrate after 1 hour. Five, 1-inch wide silicone-coated mesh specimens were cut for testing.

[0090] Performance test results: 1a: Retention test (synthetic substrate) Retention tests on polyester film were performed for the compositions of Examples 2 and 3, along with a control example, and the results are summarized in Table 1.

[0091] [Table 1]

[0092] Referring to Table 1, it can be seen that retention on polyester substrates is significantly better for the inventive examples made from polysiloxane polymers and commercial bases compared to conventional crosslinkable silicone polymers using Karstedt catalysts.

[0093] 1b: Retention test results (bio-based substrates) A pig skin retention test was performed on the composition of Example 3, The results are summarized in Table 2.

[0094] [Table 2]

[0095] Referring to Table 2, it is shown that the holding power of the silicone-based TSA on pig skin is comparable to that of a cyanoacrylate-based commercial product, which is about 10 lbs.

[0096] 2a: Peel test results (synthetic substrate) Peel testing of the TSA compositions on a synthetic substrate (polyester) was performed using the compositions of Example 2 and Example 3, along with a control example, and the results are summarized in Table 3.

[0097] [Table 3]

[0098] Referring to Table 3, it can be seen that the average and maximum peel forces for polyester substrates are significantly better for the inventive examples made from polysiloxane polymers and commercial bases compared to the conventional crosslinkable silicone polymers using Karstedt catalysts.

[0099] 2b: Peel test results (bio-based substrate) Stripping tests of TSA on human skin were performed for Example 3 and the control example, and the results are summarized in Table 4.

[0100] [Table 4]

[0101] The release force of the silicone TSA made in Example 3 of the present invention is significantly higher than that of the control example, and the release force of the silicone TSA on human skin is very similar to that of the same material on a polyester substrate (see Table 3).

[0102] 2b: Peel test results (bio-based substrate) Peel testing of TSA on pig skin was performed in Example 3 and the results are summarized in Table 4a.

[0103] [Table 5]

[0104] 3: Stretching test results Example 3 was stretched to 160% of its original length. The dimensions of the test specimen were measured before and after stretching, and the images are shown in Figures 2A, 2B, and 2c.

[0105] With reference to these figures, the test results show that Example 3 can be stretched to 160% of its original dimensions and fully recover. In a separate test not shown, a cyanoacrylate-coated polyester mesh sample could be stretched to only 101% of its original dimensions. That is, 1% stretch was sufficient to cause permanent deformation.

[0106] Example - Solventless (SF) In some embodiments, the use of organic solvent-free mixing compositions is more desirable. Such embodiments include situations where the contents of a mixing device, such as a double-barrel syringe, are made with a solvent and the contents of the syringe may leak past the syringe seal or the solvent may evaporate. The inventors have discovered that by substituting low molecular weight (3000-9000) vinyl-terminated polydimethylsiloxanes and / or low molecular weight (3000-9000) hydride-terminated polydimethylsiloxanes, suitable compositions are possible without the use of organic solvents. Both of these types of low molecular weight vinyl-terminated polydimethylsiloxane compounds or low molecular weight hydride-terminated polydimethylsiloxane compounds have viscosities in the range of 40-150 cPs. The inventors have demonstrated that these solvent-free formulations can reduce the viscosity of high-viscosity silicone bases, which typically have viscosities greater than 500,000 and up to several million centipoise.

[0107] In these embodiments, the Part A composition typically comprises a silicone base (containing a vinyl-terminated polydimethylsilicone base polymer and fumed silica particles) in the range of 60-95 wt. % for controlling a Part A viscosity of 45,000-75,000 cPs (or 30-100 wt. % for controlling a Part A viscosity of 15,000-45,000 cPs, or 0-40 wt. % for controlling a Part A viscosity of 75,000-105,000 cPs), 5-15 wt. % of a 3000-9000 cPs vinyl-terminated polydimethylsiloxane, and 100-250 ppm of elemental platinum contributed by the catalyst of the present invention, Pt[(CH2=CH)(CH3)2Si]2O·(COCH=CHCO)(C2H5O)2.

[0108] The Part B composition typically comprises a silicone base (containing a vinyl-terminated polydimethylsilicone base polymer and fumed silica particles) in the range of 60-80 wt. % for controlling a Part B viscosity of 45,000-75,000 cPs (or 0-30 wt. % for controlling a Part B viscosity of 15,000-45,000 cPs, or 70-100 wt. % for controlling a Part B viscosity of 75,000-105,000 cPs), 10-40 wt. % polymethylhydro-co-polydimethylsiloxane crosslinker, and 3-12 wt. % hydride-terminated polydimethylsiloxane.

[0109] Typically, the viscosities of both the Part A composition and the Part B composition independently range between 25,000 and 100,000 cPs before mixing, and Parts A and B result in similar viscosities when used in combination with each other around low, medium, or high viscosity levels.

[0110] Example 1-SF: Novel Platinum Catalyst (Synthesis Procedure) 2.7g of diethyl maleate was mixed with 3.6g of diethyl ether and 3.6g of Gelest SIP6830.3 (3.0% platinum divinyltetramethyldisiloxane complex in vinyl-terminated polydimethylsiloxane, Karstedt catalyst - no xylene solvent) for 24 hours at ambient temperature. Next, 64.9g of Gelest SIP6830.3 was added to the mixture, and the mixture was mixed for an additional 72 hours with the container open. Finally, 928.8g of vinyl-terminated polydimethylsiloxane (Gelest DMS V21) was added and mixed for an additional 4 hours. The novel platinum catalyst masterbatch contained the novel catalyst with 2055 ppm elemental platinum, with the remainder essentially being vinyl-terminated polydimethylsiloxane.

[0111] Example 2-SF, (low viscosity) (15,000 to 45,000 cPs) Part A Using a high-speed centrifugal mixer (FlackTek DAC150 FV-K) at 3470 rpm for 3 minutes, 90 g of Elkem 55 experimental base (also known as Elkem Silbione 4020-55, containing vinyl-terminated polydimethylsilicone-based polymer and fumed silica particles) was mixed with 10 g of Example 1-SF. The composition had a viscosity of 32,090 cPs (see Example 7a-SF).

[0112] Part B Using a high-speed centrifugal mixer (FlackTek DAC150 FV-K) at 3470 rpm for 3 minutes, 90 g of Elkem 55 experimental base was mixed with 9.0 g of polymethylhydro-co-polydimethylsiloxane crosslinker (Gelest HMS H301) and 3.0 g of SiH-terminated polydimethylsiloxane chain extender (Gelest DMS H21). The composition had a viscosity of 31,160 cPs (see Example 7a-SF).

[0113] Example 3 - SF, Medium Viscosity (45,000-75,000 cPs) Part A Using a high-speed centrifugal mixer (FlackTek DAC150 FV-K) at 3470 rpm for 3 minutes, 115 g of Elkem 55 experimental base was mixed with 20 g of Elkem 44 experimental base (also known as Elkem Silbione 4020-44, which contains a vinyl-terminated polydimethylsilicone-based polymer and fumed silica particles) and 15 g of Example 1-SF. The composition had a viscosity of 57,900 cPs (see Example 7a-SF).

[0114] Part B Using a high-speed centrifugal mixer (FlackTek DAC150 FV-K) at 3470 rpm for 3 minutes, 80 g of Elkem 44 experimental base was mixed with 20 g of Elkem 55 experimental base, 42 g of polymethylhydro-co-polydimethylsiloxane crosslinker (Gelest HMS151), and 8.0 g of SiH-terminated polydimethylsiloxane chain extender (Gelest DMS H21). The composition had a viscosity of 61,500 cPs (see Example 7a-SF).

[0115] Example 4-SF, high viscosity (75,000-105,000 cPs) Part A Using a high-speed centrifugal mixer (FlackTek DAC150 FV-K) at 3470 rpm for 3 minutes, 90 g of Elkem 55 Lab Base was mixed with 45 g of Elkem 44 Lab Base and 15 g of Example 1-SF. The composition had a viscosity of 84,000 cPs. (See Example 7a-SF.)

[0116] Part B Using a high-speed centrifugal mixer (FlackTek DAC150 FV-K) at 3470 rpm for 3 minutes, 100 g of Elkem 44 experimental base was mixed with 42 g of polymethylhydro-co-polydimethylsiloxane crosslinker (Gelest HMS H151) and 8.0 g of SiH-terminated polydimethylsiloxane chain extender (Gelest DMS H21). The composition had a viscosity of 94,800 cPs (see Example 7a-SF).

[0117] Example 5-SF: Adhesion Performance Test Sample Preparation: Holding strength test sample Synthetic substrate, polyester film (0.05 inch thick Duralar® film), Graphics Plastics, Maple Heights, OH A 1.5-inch wide PSA (pressure-sensitive adhesive)-coated polyester mesh (Lot No. 16204, Innovize, St. Paul, MN) was placed along the cut line to hold together two half specimens of the 4-inch x 11-inch Duralar film described above. The two-part silicone TSA compositions in each of the following examples (Example 2-SF, Example 3-SF, Example 4-SF) were mixed and applied evenly to the mesh using a conventional rubber spatula, covering the entire area of ​​the mesh. The specimens were cured at 31°C for 1-3 minutes and maintained at this temperature overnight. 5 One-inch-wide strip specimens of each coated mesh specimen were then cut for testing.

[0118] Peel test sample Synthetic substrate (polyester film, 0.05 inch thick Duralar® film, Graphics Plastics, Maple Heights, OH) A 5" x 5" PSA (pressure-sensitive adhesive) coated polyester mesh (Lot No. 16204, Innovize, St. Paul, MN) was placed on a polyester substrate of the same dimensions. Each of the two-part silicone TSA compositions from the following examples was mixed (Example 2-SF, Example 3-SF, Example 4-SF) and applied evenly to the mesh using a conventional rubber spatula, covering the entire area of ​​the mesh. Each of the coated mesh samples was allowed to cure overnight (i.e., for at least 8 hours) at 31°C before cutting 1-inch wide specimens for testing.

[0119] Stretching test sample A 5-inch x 5-inch PSA (pressure-sensitive adhesive)-coated polyester mesh (Lot No. 16204, Innovize, St. Paul, MN) was placed on a polyethylene substrate. Two-part silicone TSA compositions (Example 2-SF, Example 3-SF, and Example 4-SF) were mixed and applied evenly to the mesh using a conventional rubber spatula to cover the entire area of ​​the mesh. The silicone-coated polyester mesh was peeled from the Teflon substrate after 1 hour. Five, 1-inch wide silicone-coated mesh specimens were cut for testing.

[0120] Example 6-SF. Description of Test Procedure Viscosity measurement: Viscosity measurements were performed on Example 2-SF, Example 3-SF, and Example 4-SF using a Brookfield DV II+CP viscometer. Spindle 12 was used for all measurements, with a speed of 1 RPM.

[0121] Curing time measurement ASTM C679: Standard Test Method for Tack-Free Time of Elastomeric Sealants. The test consists of lightly touching the surface of the curable sealant to a polyethylene film at regular intervals until the sealant does not adhere itself to the film and the film appears clean when peeled from the surface. More specifically, a strip of polyethylene film is placed on the surface of the cured elastomer, and a 30 g weight is placed on the film. The weight is left in place for 30 seconds and then removed, the polyethylene strip is removed, and the film is examined for sealant adhesion. The length of time from when the sealant is first applied to a given surface until no more sealant is taken up by the film is called the tack-free time, and is the point at which the film exhibits non-tacky properties and is also evidence that the sealant has cured.

[0122] Peel test T-peel strength testing was performed according to ASTM F2256: Standard Test Method for Strength Properties of Tissue Adhesives in T-Peel with Tension Loading.

[0123] The average peel strength of mesh coated with silicone-based TSA in a T-peel configuration is performed at a strain rate of 10 inches / minute.

[0124] Holding strength test: This test evaluated the force required to separate a PSA-coated mesh and a substrate that approximated the applied silicone TSA composition. The method was based on ASTM F2458: Standard Test Method for Wound Closure Strength of Tissue Adhesives and Sealants.

[0125] A synthetic substrate (Mylar) was used for the test. The width of the synthetic substrate was 1 inch and the strain rate was 20 inches / minute.

[0126] Example 7-SF. Performance Test Results: 7a-SF.Viscosity measurement The viscosity measurement results for Example 2-SF, Example 3-SF, and Example 4-SF are summarized in Table 1a-SF.

[0127] [Table 6]

[0128] 7b-SF.Curing time measurement During peel test specimen preparation, cure time measurements were performed on the compositions of Ex. 2-SF, Ex. 3-SF, and Ex. 4-SF, and the results are summarized in Table 1b-SF.

[0129] [Table 7]

[0130] The foregoing demonstrates that the compositions of the present invention can cure in less than two minutes.

[0131] 7c-SF: Retention test results (synthetic base material) Retention tests on polyester film were performed for the compositions of Example 2-SF, Example 3-SF, and Example 4-SF, and the results are summarized in Table 1c-SF.

[0132] [Table 8]

[0133] Referring to Table 1c-SF, it can be seen that retention on polyester substrates is significantly better for the inventive examples made from polysiloxane polymers and commercial bases compared to the conventional crosslinked silicone polymers using Karstedt catalysts (control examples, Table 1).

[0134] 7d-SF: Peel test results (synthetic substrate) Peel testing of TSA compositions on synthetic substrates (polyester) was performed using the compositions of Example 2-SF, Example 3-SF, and Example 4-SF, and the results are summarized in Table 1d-SF.

[0135] [Table 9]

[0136] Referring to Table d-SF, it can be seen that the average peel force on polyester substrates is significantly better for the inventive examples made from polysiloxane polymers and commercial bases compared to the conventional crosslinked silicone polymers using Karstedt catalysts (Control Examples, Table 3).

[0137] 7e-SF: Extension test results Ex. 2-SF, Ex. 3-SF and Ex. 4-SF were able to be stretched to 160% of their original length and were able to recover to their original dimensions.

[0138] As demonstrated, the novel compositions, wound closure systems, and catalysts of the present invention offer numerous advantages over the prior art. The compositions allow for the formulation of medical-grade silicone adhesives that are particularly suitable for human skin. The compositions provide a durable, resilient structure that provides both mechanical and adhesive properties. The catalyst provides dual-cure catalysis, allowing crosslinking of polysiloxane chains to rapidly form a film while forming adhesive properties on a given hydroxyl-containing substrate. In the presence of the novel dual-functional catalyst, silanol functional groups on the surface of the silicone filler in the composition react with hydroxyl functional groups on a given surface, providing adhesive properties to the novel silicone-based adhesive.

[0139] While the present invention has been shown and described with reference to detailed embodiments thereof, it will be understood by those skilled in the art that various changes in form and detail of the invention may be made therein without departing from the spirit and scope of the invention as claimed.

[0140] [Embodiment] (1) A composition comprising: a crosslinkable silicone polymer having reactive functional groups; a silica-containing composition; a silicone crosslinker; a catalyst comprising a platinum tetramethyldivinyldisiloxane diethylmaleate complex having the formula: Pt[(CH2=CH)(CH3)2Si]2O·(COCH=CHCO)(C2H5O)2; A composition comprising: (2) The composition of claim 1, wherein the crosslinkable silicone polymer is selected from the group consisting of vinyl-terminated polydialkylsiloxanes, vinyl-terminated polydimethylsiloxanes, vinyl-terminated polydiphenylsilane-dimethylsiloxane copolymers, vinyl-terminated polyphenylmethylsiloxanes, vinyl-terminated polyfluoropropylmethyl-dimethylsiloxane copolymers, vinyl-terminated polydiethylsiloxanes, and SiH-terminated polydimethyldisiloxanes. (3) The composition of claim 1, wherein the crosslinkable silicone polymer comprises a vinyl-terminated polydimethylsiloxane. 4. The composition of claim 1, wherein the silica-containing composition comprises a trimethylsilyl surface-treated silica filler. (5) The composition of claim 1, wherein the silica-containing composition is selected from commercially available reactive silica-containing silicone bases, including HCR (high consistency rubber) bases and LSR (liquid silicone rubber) bases.

[0141] (6) The composition of claim 5, wherein the silica-containing composition is liquid silicone rubber-based. 7. The composition of claim 1, wherein the silicone crosslinker is selected from the group consisting of polymethylhydrosiloxane, polymethylhydro-co-polydimethylsiloxane, polyethylhydrosiloxane, polymethylhydrosiloxane-co-octylmethylsiloxane, and polymethylhydrosiloxane-co-methylphenylsiloxane. (8) The composition of claim 1, wherein the silicone crosslinker comprises polymethylhydrosiloxane, polymethylhydro-co-polydimethylsiloxane, and combinations thereof. (9) The composition of embodiment 1, wherein the composition further comprises about 0% to about 30% by weight of an organic solvent, based on the weight of the composition. 10. The composition of claim 1, wherein the composition comprises from about 1 wt. % to about 15 wt. % of the silicone crosslinker, based on total solids; and the coating composition further comprises from about 0 wt. % to about 30 wt. % of an organic solvent, based on the weight of the coating composition.

[0142] 11. The composition of claim 1, wherein the coating composition comprises about 0.003 wt. % to about 0.06 wt. % of the platinum catalyst based on total solids, and the coating composition further comprises about 0 wt. % to about 30 wt. % of an organic solvent based on the weight of the coating composition. 12. The composition of claim 1, wherein the coating composition further comprises a solvent selected from the group consisting of pentane, hexane, heptane, a mixture of low molecular weight olefins, and combinations thereof. (13) Platinum tetramethyldivinyldisiloxane diethylmaleate complex having the following formula: Pt[(CH2=CH)(CH3)2Si]2O·(COCH=CHCO)(C2H5O)2; composition. 14. The coating composition of claim 1, wherein the composition is curable at a temperature of about 19 degrees. 15. The coating composition of claim 14, wherein the composition is curable at a temperature of about 28° C. in about 2 to 5 minutes.

[0143] (16) A kit comprising: a) a wound closure device; b) a composition according to embodiment 1. (17) The kit of embodiment 16, wherein the wound closure device is a wound closure strip. (18) The kit of embodiment 17, wherein the wound closure strip is selected from the group consisting of mesh, polymeric film, plastic foam (including open-cell foam), woven fabric, knitted fabric, nonwoven fabric, and combinations thereof. (19) The kit of embodiment 18, wherein the wound closure strip is a mesh. (20) The kit of embodiment 19, wherein the wound closure device comprises a material selected from the group consisting of polyester, nylon, acrylic, rayon, polyurethane, polyurethane foam, polystyrene, polyester, polyethylene terephthalate (PET), polyamide, polylactic acid, polyglycolic acid, polycaprolactone, and mixtures thereof; cotton, silk, and linen; and surface-treated materials that impart OH functional groups to their surfaces, including, but not limited to, OH-surface-treated PTFE, OH-surface-treated polypropylene, and OH-surface-treated polyethylene.

[0144] (21) A combination of equal parts of Part A and Part B, Part A comprises 60 to 95 weight percent of a vinyl-terminated polydimethylsilicone-based polymer and fumed silica particles; 5 to 15 weight percent vinyl-terminated polydimethylsiloxane having a molecular weight in the range of 3,000 to 9,000; 100 to 250 ppm of elemental platinum contributed by the catalyst Pt[(CH2=CH)(CH3)2Si]2O·(COCH=CHCO)(C2H5O)2; Part B comprises 60 to 80 weight percent of a vinyl-terminated polydimethylsilicone-based polymer and fumed silica particles; 10 to 40 wt. % of a polymethylhydro-co-polydimethylsiloxane crosslinker; and 3 to 12 wt. % of a hydride-terminated polydimethylsiloxane having a molecular weight in the range of 3,000 to 9,000. (22) A combination of equal parts of Part A and Part B, Part A comprises 30 to 100 weight percent of a vinyl-terminated polydimethylsilicone-based polymer and fumed silica particles; 5 to 15 weight percent vinyl-terminated polydimethylsiloxane having a molecular weight in the range of 3,000 to 9,000; 100 to 250 ppm of elemental platinum contributed by the catalyst Pt[(CH2=CH)(CH3)2Si]2O·(COCH=CHCO)(C2H5O)2; Part B comprises 0 to 30 weight percent of a vinyl-terminated polydimethylsilicone-based polymer and fumed silica particles; 10 to 40 wt. % of a polymethylhydro-co-polydimethylsiloxane crosslinker; and 3 to 12 wt. % of a hydride-terminated polydimethylsiloxane having a molecular weight in the range of 3,000 to 9,000. (23) A combination of equal parts of Part A and Part B, Part A comprises 0 to 40 weight percent of a vinyl-terminated polydimethylsilicone-based polymer and fumed silica particles; 5 to 15 weight percent vinyl-terminated polydimethylsiloxane having a molecular weight in the range of 3,000 to 9,000; 100 to 250 ppm of elemental platinum contributed by the catalyst Pt[(CH2=CH)(CH3)2Si]2O·(COCH=CHCO)(C2H5O)2; Part B comprises 70 to 100 weight percent of a vinyl-terminated polydimethylsilicone-based polymer and fumed silica particles; 10 to 40 wt. % of a polymethylhydro-co-polydimethylsiloxane crosslinker; and 3 to 12 wt. % of a hydride-terminated polydimethylsiloxane having a molecular weight in the range of 3,000 to 9,000.

Claims

1. 1. A composition comprising: a crosslinkable silicone polymer having reactive functional groups; a silica material; a silicone crosslinker; A catalyst, the catalyst having the following formula: Pt[(CH ２ =CH)(CH ３ ) ２ Si] ２ O・(COCH=CHCO)(C ２ H ５ O) ２ a catalyst comprising a platinum tetramethyldivinyldisiloxane diethylmaleate complex having the formula: A composition comprising:

2. 2. The composition of claim 1, wherein the crosslinkable silicone polymer is selected from the group consisting of vinyl-terminated polydialkylsiloxanes, vinyl-terminated polydimethylsiloxanes, vinyl-terminated polydiphenylsilane-dimethylsiloxane copolymers, vinyl-terminated polyphenylmethylsiloxanes, vinyl-terminated polyfluoropropylmethyl-dimethylsiloxane copolymers, vinyl-terminated polydiethylsiloxanes, and SiH-terminated polydimethyldisiloxanes.

3. The composition of claim 1 , wherein the crosslinkable silicone polymer comprises a vinyl-terminated polydimethylsiloxane.

4. The composition of claim 1 , wherein the silica material comprises a trimethylsilyl surface-treated silica filler.

5. 2. The composition of claim 1, wherein the silicone crosslinker is selected from the group consisting of polymethylhydrosiloxane, polymethylhydro-co-polydimethylsiloxane, polyethylhydrosiloxane, polymethylhydrosiloxane-co-octylmethylsiloxane, and polymethylhydrosiloxane-co-methylphenylsiloxane.

6. The composition of claim 1, wherein the silicone crosslinker comprises polymethylhydrosiloxane, polymethylhydro-co-polydimethylsiloxane, and combinations thereof.

7. 10. The composition of claim 1, wherein the composition further comprises no more than 30% by weight of an organic solvent, based on the weight of the composition, or is free of said organic solvent.

8. 10. The composition of claim 1, wherein the composition comprises 1 wt % to 15 wt % of the silicone crosslinker, based on total solids, and the composition further comprises no more than 30 wt % of an organic solvent, based on the weight of the composition, or no organic solvent.

9. 10. The composition of claim 1, wherein the composition comprises 0.003 wt. % to 0.06 wt. % of the catalyst based on total solids, and the composition further comprises no more than 30 wt. % of an organic solvent based on the weight of the composition, or no organic solvent.

10. 10. The composition of claim 1, wherein the composition further comprises a solvent selected from the group consisting of pentane, hexane, heptane, and combinations thereof.

11. The composition of claim 1 , wherein the composition is curable at a temperature of 19 degrees.

12. The composition of claim 11, wherein the composition is curable at a temperature of 28 degrees in 2 to 5 minutes.

13. A kit comprising: a) a wound closure device; b) the composition of claim 1.

14. The kit of claim 13 , wherein the wound closure device is a wound closure strip.

15. 15. The kit of claim 14, wherein the wound closure strip is selected from the group consisting of mesh, polymeric film, plastic foam (including open-cell foam), woven fabric, knitted fabric, nonwoven fabric, and combinations thereof.

16. 16. The kit of claim 15, wherein the wound closure strip is a mesh.

17. 14. The kit of claim 13, wherein the wound closure device comprises (i) a material selected from the group consisting of polyester, nylon, acrylic, rayon, polyurethane, polyurethane foam, polystyrene, polyester, polyethylene terephthalate (PET), polyamide, polylactic acid, polyglycolic acid, polycaprolactone, and mixtures thereof, cotton, silk, and linen, and (ii) a material for OH surface treatment to impart OH functional groups to the surface thereof.

18. The kit of claim 17, wherein the material for the OH surface treatment comprises OH surface-treated PTFE, OH surface-treated polypropylene, and / or OH surface-treated polyethylene.

19. A combination of equal weights of Part A and Part B, Part A comprises 60 to 95 wt. % of a vinyl terminated polydimethylsilicone-based polymer greater than 500,000 cP and fumed silica particles; 5 to 15 wt. % of a vinyl-terminated polydimethylsiloxane less than 300 cP having a molecular weight in the range of 3,000 to 9,000; 100 to 250 ppm elemental platinum contributed by the catalyst; Part B comprises 60 to 80 weight percent of a vinyl-terminated polydimethylsilicone-based polymer and fumed silica particles; 10 to 40 wt. % of a polymethylhydro-co-polydimethylsiloxane crosslinker; 3 to 12 weight percent of a hydride-terminated polydimethylsiloxane having a molecular weight in the range of 3,000 to 9,000.

20. A combination of equal weights of Part A and Part B, Part A comprises 30 to 95 wt. % of a vinyl terminated polydimethylsilicone-based polymer greater than 500,000 cP and fumed silica particles; 5 to 15 wt. % of a vinyl-terminated polydimethylsiloxane less than 300 cP having a molecular weight in the range of 3,000 to 9,000; 100 to 250 ppm elemental platinum contributed by the catalyst; Part B comprises 0 to 30 weight percent of a vinyl-terminated polydimethylsilicone-based polymer and fumed silica particles; 10 to 40 wt. % of a polymethylhydro-co-polydimethylsiloxane crosslinker; 3 to 12 weight percent of a hydride-terminated polydimethylsiloxane having a molecular weight in the range of 3,000 to 9,000.

21. A combination of equal weights of Part A and Part B, Part A comprises 0-40 wt. % of a vinyl terminated polydimethylsilicone-based polymer greater than 500,000 cP and fumed silica particles; 5 to 15 wt. % of a vinyl-terminated polydimethylsiloxane less than 300 cP having a molecular weight in the range of 3,000 to 9,000; 100 to 250 ppm elemental platinum contributed by the catalyst; Part B comprises 70 to 87 weight percent of a vinyl-terminated polydimethylsilicone-based polymer and fumed silica particles; 10 to 27 weight percent of a polymethylhydro-co-polydimethylsiloxane crosslinker; 3 to 12 weight percent of a hydride-terminated polydimethylsiloxane having a molecular weight in the range of 3,000 to 9,000.

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