Coated substrates and methods of forming coated substrates

Abstract

A coated substrate is disclosed, comprising a solvent-susceptible substrate and a polyester coating disposed on the solvent-susceptible substrate, wherein the polyester coating comprises a polyester copolymer of a polyol and a polyacid. A method of forming the coated substrate is disclosed, comprising the steps of: applying a solvated polyester material from a spray nozzle onto the solvent-susceptible substrate; and drying the solvated polyester material to form a polyester disposed on the solvent-susceptible substrate, wherein the solvated polyester material and the polyester coating comprise a polyester copolymer of a polyol and a polyacid.

Description

[Technical Field]

[0001] Related Applications

[0001] This application claims the benefit of and priority to U.S. Provisional Patent Application No. 63 / 408,989, entitled "Anisotropic Textiles, Devices, and Implants and Methods for Forming and Coated Articles and Methods for Forming Coated Articles," filed September 22, 2022, and incorporated herein by reference in its entirety.

[0002]

[0002] This application relates to coated substrates and methods of forming coated substrates. In particular, this application relates to coated substrates having a polyester or polyester urethane coating disposed on a solvent-sensitive substrate, and methods of forming coated substrates having a polyester coating disposed on a solvent-sensitive substrate. [Background technology]

[0003] Current prosthetic heart valves often pose significant risks to patients and have durability issues. Mechanical heart valves are prone to thrombosis, and their rigid structure disrupts native hemodynamics. Bioprosthetic heart valves achieve hemodynamic outcomes similar to those of native valves, but suffer from problems with calcification and leaflet degeneration, limiting valve durability and requiring repeated surgeries. In addition, bioprosthetic valves rely on chemical processing of bovine or porcine tissue, a process that poses significant regulatory burdens, high manufacturing costs, and challenges in scale-up. Chemical processing of bovine or porcine tissue consists of various processes, including decellularization, removal of antigenic components from xenografts, and fixation of the tissue with natural biopolymers to extend shelf life and stability. Fixation typically involves crosslinking collagen or gelatin natural biopolymers with formaldehyde or glutaraldehyde. Crosslinking collagen or gelatin makes the material more rigid, immunogenic, and resistant to degradation.

[0004]

[0004] Synthetic heart valves made from chemically defined polymers have the potential to replace the function of native valves due to their tunability, cost-effectiveness, and scalability. However, unlike native heart valve leaflets, thin polymer films are isotropic. They also often have low tear strength and suboptimal fatigue profiles. These films must meet stringent mechanical requirements that often conflict with their ability to function under hemodynamic conditions. Soft, elastic materials often lack sufficient tear strength and durability, while tough, durable materials are often too stiff for valvular function.

[0005]

[0005] In comparison, textiles distribute loads in a mesh-like manner and have higher tear strength while maintaining excellent flexural properties; however, current textiles are also typically isotropic and lack a mechanical profile similar to that of a natural heart valve leaflet and its function in terms of directional elastic modulus, flexural behavior, and creep.

[0006] Existing technologies for providing directional mechanical profiles focus on the fiber alignment of electrospun fibers, but this technology is difficult to scale and control compared to textile manufacturing. Furthermore, textiles are already incorporated into the manufacture of current prosthetic heart valves.

[0007] Weaving elastic thermoplastic polyurethanes is difficult, and known methods do not allow for control of the degree of elongation of the thermoplastic polyurethane during weaving.

[0008] Furthermore, thermoplastic polyurethanes are incompatible with many organic solvent-based secondary processes because they are soluble in many solvents. While the solubility of thermoplastic polyurethanes in various solvents can improve their processability, this solubility also limits their ability to be exposed to the same solvents in downstream manufacturing. Therefore, applying solvent-based coatings to textiles formed with thermoplastic polyurethanes in downstream secondary processes can be a hindrance, and it is often desirable to avoid applying solvents to thermoplastic polyurethane fibers that may enhance, solubilize, degrade, or reduce the properties or characteristics of the thermoplastic polyurethane fibers. Summary of the Invention [Problem to be solved by the invention]

[0008]

[0009] A textile-based material that does not suffer from the aforementioned drawbacks is desirable in the art. [Means for solving the problem]

[0009]

[0010] In one exemplary embodiment, the coated substrate includes a solvent-susceptible substrate and a polyester coating disposed on the solvent-susceptible substrate, the polyester coating including a polyester copolymer of a polyol and a polyacid.

[0010]

[0011] In another exemplary embodiment, a method of forming a coated substrate includes spraying a solvated polyester material from a spray nozzle onto a solvent-susceptible substrate and drying the solvated polyester material to form a polyester coating disposed on the solvent-susceptible substrate, wherein the solvated polyester material and the polyester coating comprise a polyester copolymer of a polyol and a polyacid.

[0011]

[0012] Further aspects of the subject matter of the present disclosure are illustrated by the following items:

[0013] A coated substrate comprising a solvent-susceptible substrate and a polyester coating disposed on the solvent-susceptible substrate, wherein the polyester coating comprises a polyester copolymer of a polyol and a polyacid.

[0012]

[0014] The coated substrate of the preceding item, wherein the solvent-sensitive substrate is selected from the group consisting of polyurethane, thermoplastic polyurethane, polyacrylate, rubber, low-density polyethylene, high-density polyethylene, polycarbonate, polypropylene, polystyrene, acrylonitrile-butadiene-styrene, poly(L-lactic acid), poly(D,L-lactic acid), polycaprolactone, poly(delta-valerolactone), poly(ethylene glycol), poly(glycerol sebacate), poly(glycerol sebacate)urethane, poly(glycerol sebacate)alginate, poly(glycerol sebacate)urethane-alginate, polydimethylsiloxane, polycaprolactone-polyurethane blend, polycaprolactone, poly(lactic acid-co-glycolic acid), poly(glycolic acid), styrene block copolymer, polyvinylidene fluoride, and combinations thereof.

[0013]

[0015] The coated substrate of any of the preceding items, wherein the substrate is selected from the group consisting of a fiber, a yarn, a textile, an anisotropic textile, a plurality of electrospun fibers, an electrospun mat, a film, a membrane, a three-dimensional scaffold, a device or device component, and combinations thereof.

[0014]

[0016] The coated substrate of any of the preceding items, wherein the solvent-sensitive substrate is a thread.

[0017] The coated substrate of any of the preceding items, wherein the solvent-sensitive substrate is a textile.

[0015]

[0018] The coated substrate of any of the preceding items, wherein the solvent-sensitive substrate is an anisotropic textile.

[0019] The coated substrate according to any of the preceding items, wherein the anisotropic textile comprises warp yarns having an elastic modulus of 0.2 MPa to 50 MPa and weft yarns having an elastic modulus of 50 MPa to 500 MPa, and the elastic modulus of the warp yarns is at least 50% higher than the elastic modulus of the weft yarns.

[0016]

[0020] The coated substrate of any of the preceding items, wherein the polyester coating reduces the porosity of the textile.

[0021] Item 10. The coated substrate of any of the preceding items, wherein the polyester coating is a conformal coating that maintains the porosity of the textile.

[0017]

[0022] The coated substrate of any of the preceding items, wherein the solvent-susceptible substrate is a plurality of electrospun fibers.

[0023] The coated substrate of any of the preceding items, wherein the solvent-sensitive substrate is an electrospun mat.

[0018]

[0024] The coated substrate of any of the preceding items, wherein the polyester coating reduces the porosity of the electrospun mat.

[0025] The coated substrate of any of the preceding items, wherein the polyester coating is a conformal coating that maintains the porosity of the electrospun mat.

[0019]

[0026] The coated substrate of any of the preceding items, wherein the substrate is a film.

[0027] The coated substrate of any of the preceding items, wherein the substrate is a three-dimensional scaffold.

[0028] The coated substrate of any of the preceding items, wherein the substrate is a device or device component.

[0020]

[0029] 2. The coated substrate of any of the preceding items, wherein the device or device component is selected from the group consisting of a heart valve leaflet, a heart valve replacement implant, a transcatheter valve replacement system, a cardiac patch, a vascular seal, a ligament repair, a tendon repair, an organ tissue engineering scaffold, a hernia mesh, an adhesion barrier, a dural repair membrane, a dural replacement membrane, a muscle repair, a rotator cuff repair, a sensor, a wearable sensor, a wound dressing, a skin patch, a cosmetic patch, a wearable patch, a drug delivery device, a wearable drug delivery device, and combinations thereof.

[0021]

[0030] The coated substrate of any of the preceding items, wherein the polyester coating further comprises at least one therapeutic agent.

[0031] 2. The coated substrate of any of the preceding items, wherein the polyester coating further comprises an additive selected from the group consisting of animal-derived proteins, human-derived proteins, recombinant proteins, synthetic extracellular matrix proteins, peptides, proteoglycans, glycosaminoglycans, polysaccharides, surfactants, thixotropic agents, plasticizers, nanoparticles, leveling agents, wetting agents, electrically conductive agents, stabilizers, lubricants, antioxidants, and combinations thereof.

[0022]

[0032] The coated substrate of any of the preceding items, further comprising an electrospun mesh disposed on the solvent-susceptible substrate.

[0033] The coated substrate of any of the preceding items, wherein the boundary between the solvent-susceptible substrate and the polyester coating is an integral interphase boundary, where the polyester coating wets or intermixes with the solvent-susceptible substrate.

[0023]

[0034] The coated substrate of any of the preceding items, wherein the boundary between the solvent-susceptible substrate and the polyester coating is a non-integral interfacial boundary where the polyester coating is essentially free of intermixing with or wetting into the solvent-susceptible substrate.

[0024]

[0035] 2. The coated substrate of any of the preceding items, wherein the polyester copolymer is selected from the group consisting of poly(glycerol sebacate), poly(glycerol sebacate)urethane, poly(glycerol adipate), poly(glycerol adipate)urethane, poly(glycerol suberate), poly(glycerol suberate)urethane, poly(glycerol succinate), poly(glycerol succinate)urethane, poly(pentanediol sebacate), poly(pentanediol sebacate)urethane, poly(pentanediol adipate), poly(pentanediol adipate)urethane, poly(pentanediol suberate), poly(pentanediol suberate)urethane, poly(pentanediol succinate), poly(pentanediol succinate)urethane, copolymers thereof, thermoset polymers thereof, and combinations thereof.

[0025]

[0036] The coated substrate of any of the preceding items, wherein the polyester copolymer comprises a polyester urethane formed with a diisocyanate selected from the group consisting of hexamethylene diisocyanate, lysine diisocyanate, and combinations thereof.

[0026]

[0037] A method of forming a coated substrate, the method comprising the steps of spraying a solvated polyester material from a spray nozzle onto a solvent-susceptible substrate and drying the solvated polyester material to form a polyester coating disposed on the solvent-susceptible substrate, wherein the solvated polyester material and the polyester coating comprise a polyester copolymer of a polyol and a polyacid.

[0027]

[0038] The method according to the preceding item, wherein the distance between the spray nozzle and the solvent-sensitive substrate is at least 12 cm.

[0039] The method according to any of the preceding items, wherein the distance between the spray nozzle and the solvent-sensitive substrate is at least 15 cm.

[0028]

[0040] The method of any of the preceding items, wherein the solvated polyester material is sprayed at a flow rate of less than 1 mL / min.

[0041] The method according to any of the preceding items, wherein the flow rate is 0.5 mL / min or less.

[0029]

[0042] The method of any of the preceding items, wherein the solvated polyester material is sprayed in 10 or fewer successive passes.

[0043] The method of any of the preceding items, wherein the solvated polyester material is solvated in 100% acetone. [Brief explanation of the drawings]

[0030] [Figure 1A]

[0044] FIG. 1 illustrates the surface morphology of an anisotropic textile before poly(glycerol sebacate) urethane coating, according to one embodiment of the present disclosure. [Figure 1B]

[0045] FIG. 1 illustrates the surface morphology of an anisotropic textile after poly(glycerol sebacate) urethane coating, according to one embodiment of the present disclosure. [Figure 2A]

[0046] FIG. 1 shows the surface morphology of an electrospun mat before poly(glycerol sebacate) urethane coating, according to one embodiment of the present disclosure. [Figure 2B]

[0047] FIG. 1 shows the surface morphology of an electrospun mat after two cycles of poly(glycerol sebacate) urethane coating, according to an embodiment of the present disclosure. [Figure 2C]

[0048] FIG. 1 shows the surface morphology of an electrospun mat after four cycles of poly(glycerol sebacate) urethane coating, according to an embodiment of the present disclosure. [Figure 2D]

[0049] FIG. 1 shows the surface morphology of an electrospun mat after 10 cycles of poly(glycerol sebacate) urethane coating, according to an embodiment of the present disclosure. [Figure 3]

[0050] 1 illustrates an anisotropic heart valve replacement implant leaflet according to one embodiment of the present disclosure. [Figure 4]

[0051] 1 is a graph illustrating the mechanical profile of an anisotropic textile according to one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0031]

[0052] Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same parts.

[0053] Embodiments of the present disclosure can reduce manufacturing costs, reduce potential points of failure in the resulting device, provide practical customizability, extend service life, or provide a combination thereof, as compared to coated substrates and methods of forming coated substrates lacking one or more features of the present invention.

[0032]

[0054] 1A-B and 2A-D, in one embodiment, the coated substrate 1 includes a solvent-susceptible substrate 10 and a polyester coating 20 disposed on the solvent-susceptible substrate 10.

[0033]

[0055] As used herein, "solvent-sensitive substrate" refers to a substrate formed of a material that dissolves upon sustained contact with FDA Class 3 solvents, such as, but not limited to, acetone, propyl acetate, ethyl acetate, methyl acetate, butanol, butyl acetate, pentanol, propanol, etc. for less than 12 hours, causing the solvent-sensitive substrate to lose 15% or more of its mass, overall dimensions, or surface shape.

[0034]

[0056] The polyester coating 20 disposed on the solvent-susceptible substrate 10 comprises a polyester copolymer of a polyol and a polyacid. As used herein, "polyester copolymer of a polyol and a polyacid" refers to a polyester polymer formed by copolymerization of at least one polyol and at least one diacid. The polyester may be crosslinked with a diisocyanate. The polyester copolymer of a polyol and a polyacid may be a bioabsorbable polymer. The polyol may be any suitable species, including, but not limited to, glycerin, pentanediol, butanediol, propanediol, isopentyldiol, ethylene glycol, sorbitol, xylitol, or combinations thereof. The polyacid may be any suitable species, including, but not limited to, diacids. Suitable diacids may include, but are not limited to, sebacic acid, diacids having a chain length shorter than sebacic acid, such as, but not limited to, adipic acid, succinic acid, suberic acid, or combinations thereof, or combinations of any of the foregoing diacids.

[0035]

[0057] The solvent-susceptible substrate 10 may be formed from any suitably selected material, including, but not limited to, polyurethane, thermoplastic polyurethane, polyacrylate, rubber, low-density polyethylene, high-density polyethylene, polycarbonate, polypropylene, polystyrene, acrylonitrile-butadiene-styrene, poly(L-lactic acid), poly(D,L-lactic acid), polycaprolactone, poly(delta-valerolactone), poly(ethylene glycol), poly(glycerol sebacate), poly(glycerol sebacate)urethane, poly(glycerol sebacate)alginate, poly(glycerol sebacate)urethane-alginate, polydimethylsiloxane, polycaprolactone-polyurethane blend, polycaprolactone, poly(lactic acid-co-glycolic acid), poly(glycolic acid), styrene block copolymer, polyvinylidene fluoride, or combinations thereof.

[0036]

[0058] The solvent-susceptible substrate 10 may be any suitable article, including, but not limited to, a fiber, a yarn, a textile 30 (FIGS. 1A-B), an anisotropic textile, a plurality of electrospun fibers, an electrospun mat 40 (FIGS. 2A-D), a film, a membrane, a three-dimensional scaffold, a device or device component, or a combination thereof. Suitable devices or device components may include, but are not limited to, a heart valve leaflet 50 (FIG. 3), a heart valve replacement implant, a transcatheter valve replacement system, a cardiac patch, a vessel seal, a ligament repair, a tendon repair, an organ tissue engineering scaffold, a hernia mesh, an adhesion barrier, a dural repair membrane, a dural replacement membrane, a muscle repair, a rotator cuff repair, a sensor, a wearable sensor, a wound dressing, a skin patch, a cosmetic patch, a wearable patch, a drug delivery device, a wearable drug delivery device, or a combination thereof. The heart valve leaflet 50 may include a single leaflet, two leaflets, three leaflets, or any suitable number of leaflets.

[0037]

[0059] As used herein, "textile" is broadly construed. A generally accepted and commonly used definition of a textile-derived product is any material or component made of intertwined filaments, fibers, extrudates, or multifilament yarns. A textile component product or article can be defined in any of the following ways: raw, semi-processed, processed, semi-finished, finished, semi-finished, or finished product composed of textile components. A "textile" referred to herein can be a component or a finished product. As used herein, "textile" and "textile component" are not limited to their traditional source or connotation of fiber-based "fabric" or textile. "Textiles" and "textile components" can include any use of materials for design purposes, including further processing or treating fiber, yarn, film-fiber, extruded sheet, composite, thread, or filament-based raw material components into two-dimensional or three-dimensional intermediate or final articles using known textile form factor engineering techniques, including, but not limited to, knitting, braiding, weaving, nonwoven processing, staple, film, laminated sheet, extrusion, film lamination, or composite multilayer processing. This includes endo- and exogenous medical-surgical implant devices, such as tissue-engineered scaffold grafts and planar articles like valve leaflets 50. These planar articles may be further processed, but are not limited to, die-cut, cut, stamped, or laser-machined. "Textiles" and "textile components" may be made from a variety of materials derived from distinct primary sources, including, but not limited to, natural animals, processed animals, natural plants / vegetables, processed plants / vegetables; inorganic minerals (such as, but not limited to, metals and oxides) or inorganic polymers (such as, but not limited to, carbon fiber, glass, and bioglass); regenerated man-made or synthetic / lab-derived sources, and manufactured or bio-derived recombinant synthetic and biopolymer sources.Furthermore, "textile engineering" is considered to be the field of material form factor engineering that uses such natural and / or synthetic material processing, scientific and materials engineering principles, and polymer chemistry principles to produce or improve engineered articles, components, products, or materials, including, but not limited to, medical devices and other commercially recognized "textile" components. Textiles described or referred to herein are considered to be permanent, synthetic, environmentally non-degradable, non-biodegradable, biodegradable, or bioabsorbable. Biodegradable and bioabsorbable may include, but are not limited to, lactide, glycolide, glycerol esters, or other degradable biopolymers, including, but not limited to, polymers that degrade under aerobic or anaerobic conditions by microbial action, attack by bodily fluid enzymes, aided hydrolysis, or a combination thereof.

[0038]

[0060] The use of two different fibers, soft and strong, in two orthogonal directions in the fabric allows the resulting textile to have biomimetic anisotropy. As used herein, "soft" refers to a modulus of elasticity below 50 MPa, while "strong" refers to a modulus of elasticity above 50 MPa, with a modulus of 50 MPa being considered the transition point between "soft" and "strong." This mechanical anisotropy has the potential to promote efficient bending, opening, and closure while maintaining high tear strength. This textile anisotropy is believed to mimic the collagen and elastin fiber orientation and mechanical performance of native tissue valve leaflets 50. During systole, blood flow pushes the leaflets 50 open, forming corrugations behind the leaflets. As the leaflets 50 open during systole, the elastin fibers relax, and the collagen fibers become crimped, compressed, and misaligned. During diastole, back pressure forces the leaflets 50 to close. When the leaflets 50 are closed during diastole, the elastin fibers are elongated and stretched, while the collagen fibers are aligned and uncurled. The elastic fibers can be approximated by soft elastic synthetic fibers, and the collagen fibers can be approximated by tough synthetic fibers.

[0039]

[0061] Using a textile that combines two different fibers with different mechanical properties as the scaffold for the valve leaflets 50 can mimic the anisotropy observed in native valve tissue. The anisotropy in mechanical properties promotes valve function and long-term durability. Using soft yarns in the axial direction facilitates opening and closing of the valve leaflets 50, while using tough yarns in the circumferential direction maintains the overall mechanical integrity, lifespan, and tear strength of the valve leaflets 50. Combining textiles with polyester coatings can also enhance the mechanical properties of synthetic valve leaflets 50 by forming a tough-soft composite instead of a flat polymer film. The mechanical flexibility of the fibers used in the warp (axial) direction may facilitate the structure's ability to open and close in response to changes in blood pressure while secured to the valve base / delivery system. To increase the axial compliant region, a series of warp yarns with varying flexibility can also be employed. This technique can also be employed in the weft (circumferential) direction, where different fiber toughnesses can be advantageous to create regions of tunable strength.

[0040]

[0062] In one embodiment, the coated substrate 1 is an anisotropic textile 30 comprising warp yarns having a modulus of elasticity between 0.2 MPa and 50 MPa and weft yarns having a modulus of elasticity between 50 MPa and 500 MPa, the modulus of the warp yarns being at least 50% higher than the modulus of the weft yarns. The warp yarns or the weft yarns or both may have non-circular cross-sections. For embodiments having yarns with a modulus of 0.2 MPa to 50 MPa, the modulus may be any suitable subrange thereof, including, but not limited to, 0.2 MPa to 0.5 MPa, alternatively 0.2 MPa to 1.0 MPa, alternatively 0.5 MPa to 1.5 MPa, alternatively 1 MPa to 2 MPa, alternatively 1.5 MPa to 2.5 MPa, alternatively 0.2 MPa to 10 MPa, alternatively 2 MPa to 15 MPa, alternatively 5 MPa to 15 MPa, alternatively 10 MPa to 20 MPa, alternatively 15 MPa to 25 MPa, alternatively 20 MPa to 30 MPa, alternatively 25 MPa to 35 MPa, alternatively 30 MPa to 40 MPa, alternatively 35 MPa to 45 MPa, alternatively 40 MPa to 50 MPa, any subrange thereof, or combination thereof. Alternatively, a high modulus yarn having a comparable modulus under physiological strain (10-30% strain) may be substituted. For embodiments having yarns with a modulus of 50 MPa to 500 MPa, the modulus may be any suitable subrange thereof, including, but not limited to, 50 MPa to 150 MPa, alternatively 50 MPa to 100 MPa, alternatively 75 MPa to 125 MPa, alternatively 90 MPa to 150 MPa, alternatively 100 MPa to 150 MPa, alternatively 100 MPa to 200 MPa, alternatively 150 MPa to 250 MPa, alternatively 200 MPa to 300 MPa, alternatively 250 MPa to 350 MPa, alternatively 300 MPa to 400 MPa, alternatively 350 MPa to 450 MPa, alternatively 400 MPa to 500 MPa, these subranges, or combinations thereof.

[0041]

[0063] The weft yarns may be formed of any suitable weft material, including, but not limited to, polyethylene terephthalate, polyetheretherketone, polyetherketoneketone [just checked, should this be mentioned twice?], polyvinylidene fluoride, polypropylene, poly(glycolic acid), poly(lactic-co-glycolic acid), ultra-high molecular weight polyethylene, and combinations thereof. The warp yarns may be formed of any suitable warp material, including, but not limited to, thermoplastic polyurethane, polyurethane, poly(glycerol sebacate), poly(glycerol sebacate)urethane, poly(glycerol sebacate)alginate, poly(glycerol sebacate)urethane-alginate, polydimethylsiloxane, polycaprolactone-polyurethane blend, styrene block copolymer, and combinations thereof.

[0042]

[0064] In substrates that are porous, such as, but not limited to, textiles 30, membranes, or electrospun mats 40, the polyester coating 20 may reduce the porosity of the solvent-susceptible substrate 10 or may be a conformal coating that maintains the porosity of the solvent-susceptible substrate 10.

[0043]

[0065] In one embodiment, the polyester coating 20 further comprises at least one therapeutic agent.

[0066] The polyester coating 20 further comprises additives, including, but not limited to, animal-derived proteins, human-derived proteins, recombinant proteins, synthetic extracellular matrix proteins, peptides, proteoglycans, glycosaminoglycans, polysaccharides, surfactants, thixotropic agents, plasticizers, nanoparticles, leveling agents, wetting agents, electrically conductive agents, stabilizers, lubricants, antioxidants, or combinations thereof.

[0044]

[0067] In one embodiment, the coated substrate 1 further comprises an electrospun mesh disposed on the solvent-susceptible substrate 10 .

[0068] The interface between the solvent-susceptible substrate 10 and the polyester coating 20 may be an integral interphase boundary, where the polyester coating 20 wets or intermixes with the solvent-susceptible substrate 10, or it may be a non-integral interfacial boundary, where the polyester coating 20 is essentially free of intermixing or wetout with the solvent-susceptible substrate 10. As used herein, "essentially free" indicates that less than 10% of the surface area at the interface is free of intermixing or wetout. Without being bound by theory, it is believed that an integral interphase boundary increases the bond between the solvent-susceptible substrate 10 and the polyester coating 20, reducing the likelihood of interfacial failure modes such as delamination or cracking.

[0045]

[0069] The polyester copolymer may have any suitable material composition, including, but not limited to, poly(glycerol sebacate), poly(glycerol sebacate)urethane, poly(glycerol adipate), poly(glycerol adipate)urethane, poly(glycerol suberate), poly(glycerol suberate)urethane, poly(glycerol succinate), poly(glycerol succinate)urethane, poly(pentanediol sebacate), poly(pentanediol sebacate)urethane, poly(pentanediol adipate), poly(pentanediol adipate)urethane, poly(pentanediol suberate), poly(pentanediol suberate)urethane, poly(pentanediol succinate), poly(pentanediol succinate)urethane, copolymers thereof, thermoset polymers thereof, or combinations thereof. In one embodiment, the polyester copolymer may include a polyester urethane formed with a diisocyanate selected from the group consisting of hexamethylene diisocyanate, lysine diisocyanate, and combinations thereof.

[0046]

[0070] In one embodiment, a method of forming a coated substrate 1 includes spraying a solvated polyester material from a spray nozzle onto a solvent-susceptible substrate 10 and drying the solvated polyester material to form a polyester coating 20 disposed on the solvent-susceptible substrate 10.

[0047]

[0071] The spray nozzle may be positioned at any suitable distance from the solvent-susceptible substrate 10 during application of the solvated polyester material, including a distance of at least 12 cm, alternatively at least 15 cm, alternatively at least 18 cm, or alternatively between 12 cm and 24 cm.

[0048]

[0072] The solvated polyester material can be sprayed onto the solvent-susceptible substrate 10 at any suitable flow rate, including, but not limited to, a flow rate of less than 1 mL / min, alternatively less than 0.75 mL / min, alternatively less than 0.5 mL / min, alternatively less than 0.25 mL / min, or alternatively less than 0.10 mL / min.

[0049]

[0073] The solvated polyester material can be sprayed onto the solvent-susceptible substrate 10 in any suitable number of consecutive passes, including, but not limited to, 10 or fewer consecutive passes, alternatively 9 or fewer consecutive passes, alternatively 8 or fewer consecutive passes, alternatively 7 or fewer consecutive passes, alternatively 6 or fewer consecutive passes, or alternatively 5 or fewer consecutive passes.

[0050]

[0074] The solvated polyester material may be solvated in any suitable solvent, including, but not limited to, 100% acetone, an FDA Class 3 solvent with volatility equal to or greater than acetone, or a combination thereof, other than a 1:1 mixture of acetone and propyl acetate.

[0051]

[0075] Without being bound by theory, it is believed that polyester coatings 20 applied by spray coating are superior in terms of improved adhesion compared to dip coating. Furthermore, improved adhesion is believed to be due to improved control of the amount of solvent that contacts the solvent-susceptible substrate 10 during the spray process compared to the dip process. Specifically, during spray coating, aerosolized solvated polyester droplets travel through the air for a predetermined flight time before landing on the polyester material or solvent-susceptible substrate 10. This promotes evaporation of some of the solvent before reaching the solvent-susceptible substrate 10, resulting in less solvent being delivered to the solvent-susceptible substrate 10 overall than with dip coating. With dip coating, more solvent is present and in contact with the solvent-susceptible substrate 10 for a longer period of time, increasing the solubilizing effects of the organic solvent and adversely affecting the solvent-susceptible substrate 10.

[0052]

[0076] Simply dip-coating the solvent-sensitive substrate 10 in a solution of the polyester material or spray-coating it using standard spray techniques can result in the solvent-sensitive substrate 10 dissolving and losing its original shape. Optimization of the spray-coating process can include, but is not limited to, increasing the distance between the spray nozzle and the solvent-sensitive substrate 10 to facilitate solvent evaporation during transport and reduce solvent buildup on the solvent-sensitive substrate 10, reducing the flow rate to the spray nozzle, reducing the number of spray-coating passes to facilitate solvent evaporation, drying the solvent-sensitive substrate 10 between spray-coating passes, rotating solvents to increase the evaporation rate, or combinations thereof. [Example]

[0053]

[0077] Example 1

[0078] Referring to Figures 1A, 1B, and 4, a woven textile consisting of polyethylene terephthalate weft yarns and thermoplastic polyurethane (Pellethane 5863-85A from Lubrizol) warp yarns was spray-coated with poly(glycerol sebacate) urethane to form an anisotropic composite structure. A dual-feed Sonotek ultrasonic spray nozzle was loaded with a 15% poly(glycerol sebacate) urethane solution (100% acetone as the solvent). The solution was sprayed at 0.5 mL / min for four cycles at a distance of 15 cm from the substrate. After 24 hours of curing at room temperature, the composite structure was tested for tensile properties in both the weft and warp directions using an MTS CRITERION® 42 mechanical testing instrument on Type V dogbone specimens strained at 10 mm / min. The elastic modulus of this composite structure was 5 MPa in the warp direction and 92 MPa in the weft direction, indicating that the anisotropic properties remained even after coating (comparison with a human aortic valve is shown in Figure 4). The elastic modulus was calculated from the slope of the linear portion of the curve measured in Figure 4. As shown in Figure 1B, the poly(glycerol sebacate) urethane-coated textile was observed under a scanning electron microscope, which showed that the structure of the textile, which has both thermoplastic polyurethane fibers and thermoplastic polyurethane fibers, remained intact.

[0054]

[0079] Example 2

[0080] Referring to Figures 2A-D, electrospun mats (Figure 2A) containing thermoplastic polyurethane fibers (Pellethane 5863-85A, manufactured by Lubrizol) with fiber diameters of 1-2 μm and thicknesses of 15-30 μm were spray-coated with poly(glycerol sebacate) urethane to form composite structures. A dual-feed Sonotek ultrasonic spray nozzle was loaded with a 15% poly(glycerol sebacate) urethane solution (100% acetone as the solvent). This solution was sprayed at 0.5 mL / min at a distance of 15 cm from the substrate. One electrospun mat was sprayed twice (two cycles) (Figure 2B), another was sprayed four times (Figure 2C), and the third was sprayed 10 times (Figure 2D). As observed in Figures 2B-D, all three substrates maintained the original structure of the electrospun mat beneath the poly(glycerol sebacate) urethane layer after curing at room temperature for 24 h.

[0055]

[0081] While the foregoing specification illustrates and describes exemplary embodiments, it will be apparent to those skilled in the art that various changes can be made and equivalents substituted for elements thereof without departing from the scope of the invention. In addition, many modifications can be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is not intended that the invention be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but rather, it is intended to include all embodiments falling within the scope of the appended claims.

Claims

1. A coated substrate, a solvent-sensitive substrate; a polyester coating disposed on the solvent-susceptible substrate; Including, A coated substrate, wherein the polyester coating comprises a polyester copolymer of a polyol and a polyacid.

2. 2. The coated substrate of claim 1, wherein the solvent-susceptible substrate is selected from the group consisting of polyurethane, thermoplastic polyurethane, polyacrylate, rubber, low-density polyethylene, high-density polyethylene, polycarbonate, polypropylene, polystyrene, acrylonitrile-butadiene-styrene, poly(L-lactic acid), poly(D,L-lactic acid), polycaprolactone, poly(delta-valerolactone), poly(ethylene glycol), poly(glycerol sebacate), poly(glycerol sebacate)urethane, poly(glycerol sebacate)alginate, poly(glycerol sebacate)urethane-alginate, polydimethylsiloxane, polycaprolactone-polyurethane blend, polycaprolactone, poly(lactic acid-co-glycolic acid), poly(glycolic acid), styrene block copolymer, polyvinylidene fluoride, and combinations thereof.

3. 10. The coated substrate of claim 1, wherein the solvent-susceptible substrate is selected from the group consisting of a fiber, a yarn, a textile, an anisotropic textile, a plurality of electrospun fibers, an electrospun mat, a film, a membrane, a three-dimensional scaffold, a device or device component, and combinations thereof.

4. the solvent-sensitive substrate is Warp yarns having an elastic modulus of 0.2 MPa to 50 MPa; A weft yarn having an elastic modulus of 50 MPa to 500 MPa. The anisotropic textile comprises the modulus of elasticity of the warp yarns is at least 50% higher than the modulus of elasticity of the weft yarns; The coated substrate according to claim 3 .

5. The coated substrate of claim 3 , wherein the solvent-sensitive substrate comprises the textile and the polyester coating reduces the porosity of the textile.

6. 4. The coated substrate of claim 3, wherein the solvent-sensitive substrate comprises the textile and the polyester coating is a conformal coating that maintains the porosity of the textile.

7. 4. The coated substrate of claim 3, wherein the solvent-susceptible substrate comprises the electrospun mat, and the polyester coating reduces the porosity of the electrospun mat.

8. 4. The coated substrate of claim 3, wherein the solvent-susceptible substrate comprises the electrospun mat and the polyester coating is a conformal coating that maintains the porosity of the electrospun mat.

9. 4. The coated substrate of claim 3, wherein the solvent-sensitive substrate comprises the device or device component selected from the group consisting of a heart valve leaflet, a heart valve replacement implant, a transcatheter valve replacement system, a cardiac patch, a blood vessel seal, a ligament repair, a tendon repair, an organ tissue engineering scaffold, a hernia mesh, an adhesion barrier, a dural repair membrane, a dural replacement membrane, a muscle repair, a rotator cuff repair, a sensor, a wearable sensor, a wound dressing, a skin patch, a cosmetic patch, a wearable patch, a drug delivery device, a wearable drug delivery device, and combinations thereof.

10. The coated substrate of claim 1 , wherein the polyester coating further comprises at least one therapeutic agent.

11. 10. The coated substrate of claim 1, wherein the polyester coating further comprises an additive selected from the group consisting of animal-derived proteins, human-derived proteins, recombinant proteins, synthetic extracellular matrix proteins, peptides, proteoglycans, glycosaminoglycans, polysaccharides, surfactants, thixotropic agents, plasticizers, nanoparticles, leveling agents, wetting agents, electrically conductive agents, stabilizers, lubricants, antioxidants, and combinations thereof.

12. The coated substrate of claim 1 further comprising an electrospun mesh disposed on the solvent-susceptible substrate.

13. 10. The coated substrate of claim 1, wherein the boundary between the solvent-susceptible substrate and the polyester coating is an integral interphase boundary where the polyester coating wets or intermixes with the solvent-susceptible substrate.

14. 10. The coated substrate of claim 1, wherein the boundary between the solvent-susceptible substrate and the polyester coating is a non-integral interfacial boundary in which the polyester coating is essentially free of intermixing with or wetting into the solvent-susceptible substrate.

15. 2. The coated substrate of claim 1, wherein the polyester copolymer is selected from the group consisting of poly(glycerol sebacate), poly(glycerol sebacate)urethane, poly(glycerol adipate), poly(glycerol adipate)urethane, poly(glycerol suberate), poly(glycerol suberate)urethane, poly(glycerol succinate), poly(glycerol succinate)urethane, poly(pentanediol sebacate), poly(pentanediol sebacate)urethane, poly(pentanediol adipate), poly(pentanediol adipate)urethane, poly(pentanediol suberate), poly(pentanediol suberate)urethane, poly(pentanediol succinate), poly(pentanediol succinate)urethane, copolymers thereof, thermoset polymers thereof, and combinations thereof.

16. 16. The coated substrate of claim 15, wherein the polyester copolymer comprises a polyester urethane formed with a diisocyanate selected from the group consisting of hexamethylene diisocyanate, lysine diisocyanate, and combinations thereof.

17. 1. A method of forming a coated substrate, comprising: spraying the solvated polyester material from a spray nozzle onto a solvent-sensitive substrate; drying the solvated polyester material to form a polyester coating disposed on the solvent-susceptible substrate; Including, The method wherein the solvated polyester material and the polyester coating comprise a polyester copolymer of a polyol and a polyacid.

18. 18. The method of claim 17, wherein the distance between the spray nozzle and the solvent-susceptible substrate is at least 12 cm.

19. 18. The method of claim 17, wherein the solvated polyester material is sprayed at a flow rate of less than 1 mL / min.

20. 20. The method of claim 17, wherein the solvated polyester material is sprayed in 10 or fewer successive passes.

21. 18. The method of claim 17, wherein the solvated polyester material is solvated with 100% acetone.

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